{"text": "In the crystal, hydrogen bonds connect the mol\u00adecules into double layers, which are connected to each other by halogen bonds.The title compound was synthesized by a new type of reaction using Mg2 as a new catalyst and a possible mechanism for this reaction is proposed. The six-membered ring adopts a half-chair conformation. In the crystal, hydrogen bonds connect the mol\u00adecules into double layers, which are connected to each other by halogen bonds. The Hirshfeld surface analysis revealed that the most important contributions for the crystal packing are from O\u22efH/H\u22efO (35.8%), Cl\u22efCl (19.6%), Cl\u22efH/H\u22efCl (17.0%), H\u22efH (8.3%), C\u22efO/O\u22efC (4.3%), Cl\u22efO/O\u22efCl (4.2%) and O\u22efO (4.1%) contacts.The mol\u00adecular and crystal structures of the title compound, C The reaction scheme is shown in Fig.\u00a015,5-Di\u00adchloro-6-hy\u00addroxy\u00addihydro\u00adpyrimidine-2,4\u2005\u00c5  x, y\u00a0+\u00a01, z; (ii) x, \u2212y\u00a0+\u00a02, z\u00a0+\u00a0A\u22efO1i hydrogen bond also involves O1i with a H4A\u22efO1i distance of 3.058\u2005(2)\u2005\u00c5  \u2212x, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01; (v) x, \u2212y\u00a0+\u00a02, z\u00a0\u2212\u00a0A\u22efO2iii  with an N1\u22efO2iii distance of 2.793\u2005(2)\u2005\u00c5. The hydrogen bonds connect the mol\u00adecules into double layers parallel to the (100) plane, as shown in Fig.\u00a04vi [3.3670\u2005(9)\u2005\u00c5] and Cl2\u22efCl2vii  connect the layers, forming a three-dimensional framework.The hydrogen-bond system is shown in Fig.\u00a03\u00c5 Table\u00a02. In the Crystal Explorer 17.5  to 0.986 (blue) a.u., as illustrated in Fig.\u00a05dnorm plot indicate inter\u00admolecular contacts involving the hydrogen and halogen bonds. The brightest red spots correspond to the strongest hydrogen bonds, N1\u2014H1A\u22efO2 and O3\u2014H3\u22efO2  until the components were completely dissolved. Crystallization occurred with isothermal evaporation of the resulting solution at room temperature for several weeks, giving colourless needle-shaped crystals, composition according to chemical analysis : C, 24.12/24.14; H, 2.04/2.03; Cl, 35.64/35.63; N, 14.07/14.08; O, 24.13/24.12. Crystals suitable for a X-ray structural analysis were extracted manually from this batch.The title compound was synthesized by adding 5\u2005mg of uracil (Sigma Aldrich) to 1\u2005ml of 1\u2005mol\u2005l4\u2212 does not react with HCl while TcO4\u2212 is actively reduced  and possibly through radical substitution.We suggest a possible mechanism of the observed reaction. Typically, ReOUiso(H) = 1.2Ueq(C)]. O- and N-bound H atoms were refined isotropically [Uiso(H) = 1.2Ueq].Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020011809/zq2257sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020011809/zq2257Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020011809/zq2257Isup3.cmlSupporting information file. DOI: 2025758CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A linear gold-atom geometry defined by phosphane-P and thiol\u00adate-S atoms is found in the title compound. The packing is stabilized by a combination of fluoro\u00adbenzene-C\u2014H\u22efO(meth\u00adoxy), phenyl-C\u2014H\u22efF, phenyl-C\u2014H\u22efS(thiol\u00adate) and phenyl-C\u2014H\u22ef\u03c0 inter\u00adactions to generate a three-dimensional network. 26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494\u2005(8)\u2005\u00c5] and thiol\u00adate-S [2.3007\u2005(8)\u2005\u00c5] atoms to define a close to linear geometry [P\u2014Au\u2014S = 176.10\u2005(3)\u00b0]. The thiol\u00adate ligand is orientated so that the meth\u00adoxy-O atom is directed towards the Au atom, forming an Au\u22efO close contact of 2.986\u2005(2)\u2005\u00c5. In the crystal, a variety of inter\u00admolecular contacts are discerned with fluoro\u00adbenzene-C\u2014H\u22efO(meth\u00adoxy) and phenyl-C\u2014H\u22efF inter\u00adactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C\u2014H\u22efS(thiol\u00adate) and phenyl-C\u2014H\u22ef\u03c0 inter\u00adactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C\u22efH/H\u22efC but this is less than the H\u22efH contacts, at 44.9%. Other significant contributions to the surface come from H\u22efF/F\u22efH [8.1%], H\u22efS/S\u22efH [6.9%] and H\u22efO/O\u22efH [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C\u2014H\u22ef\u03c0(fluoro\u00adbenzene) and fluoro\u00adbenzene-C\u2014H\u22efC(imine) inter\u00adactions , and from the fluoro\u00adbenzene-C\u2014H\u22efF and phenyl-C\u2014H\u22efO inter\u00adactions , the latter leading to the dimeric aggregate.The title phosphanegold(I) thiol\u00adate, C The deviation of the P1\u2014Au\u2014S1 angle of 176.10\u2005(3)\u00b0 from the ideal 180\u00b0 is related to the close approach of the O1 atom, i.e. Au\u22efO1 = 2.986\u2005(2)\u2005\u00c5, as the O1 atom is directed towards the gold atom. The elongation of the C1\u2014S1 bond to 1.762\u2005(3)\u2005\u00c5 and the shortening of the C1\u2014N1 bond to 1.262\u2005(4)\u2005\u00c5 with respect to the comparable bonds in the neutral thio\u00adcarbamide mol\u00adecules, i.e. S=C(OMe)N(H)Ar R3PAu[SC(OR\u2032)=NAr]. However, a less common form is known whereby the N-bound aryl ring is orientated towards the gold atom rather than the alk\u00adoxy-oxygen atom =NPh], i.e. with Au\u22efO via pairwise fluoro\u00adbenzene-C\u2014H\u22efO1 and phenyl-C\u2014H\u22efF1 contacts Fig.\u00a02a). The dimeric aggregates are connected into a three-dimensional architecture by phenyl-C\u2014H\u22efS1 inter\u00adactions, with the phenyl-H atom involved in the latter inter\u00adaction, i.e. H13, also participating in a C\u2014H\u22ef\u03c0(fluoro\u00adbenzene) inter\u00adaction and so may be considered bifurcated. The two remaining contacts are of the type phenyl-C\u2014H\u22ef\u03c0 so the fluoro\u00adbenzene ring accepts two contacts, one to either side of the ring. A view of the unit-cell contents is shown in Fig.\u00a02b).Several directional inter\u00admolecular points of contact between mol\u00adecules are noted in the extended structure of (I)dnorm , where the cooperative phenyl-C13\u2014H13\u22ef\u03c0(C2\u2013C7) inter\u00adaction is shown as a distinctive orange \u2018pothole\u2019 on the shape-index-mapped Hirshfeld surface in Fig.\u00a04b). Although the phenyl-C22\u2014H22\u22ef\u03c0(C2\u2013C7) inter\u00adaction was not manifested on the Hirshfeld surface mapped over dnorm, this inter\u00adaction shows up as blue \u2018bump\u2019 and orange \u2018pothole\u2019 near the H22 atom and Cg1(C2\u2013C7) centroid, respectively, in Fig.\u00a05a). Simultaneously, a fluoro\u00adbenzene-C7\u2014H7\u22efC1(imine) contact, Table\u00a02dnorm surface in Fig.\u00a05b). The presence of the phenyl-C24\u2014H24\u22ef\u03c0(C11\u2013C16) contact is evidenced through faint red spots in Fig.\u00a06a) and the orange \u2018pothole\u2019 in Fig.\u00a06b) on the dnorm and shape-index mapped Hirshfeld surface, respectively. In addition to the C\u2014H\u22ef\u03c0 contacts listed in Table\u00a01In order to understand further the inter\u00adactions operating in the mol\u00adecular packing of (I)a), and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efF/F\u22efH, H\u22efS/S\u22efH and H\u22efO/O\u22efH contacts are shown in Fig.\u00a08b)\u2013(f), respectively. The percentage contributions for the different inter\u00adatomic contacts to the Hirshfeld surface are summarized in Table\u00a03b) features a beak-shaped peak tipped at de + di \u223c2.3\u2005\u00c5. This tip corresponds to a methyl-H8C\u22efH33(phen\u00adyl) contact and has a distance 0.1\u2005\u00c5 shorter than the sum of their van de Waals radii, Table\u00a02c) with two symmetric spikes at de + di \u223c2.4\u2005\u00c5. The tips of pseudo-mirrored sharp spikes at de + di \u223c2.4\u2005\u00c5 represent the shortest H\u22efF/F\u22efH contacts (8.1%), Fig.\u00a08d), and correspond to the phenyl-C36\u2014H36\u22efF1 contact in Table\u00a01de + di \u223c2.7 and \u223c2.5\u2005\u00c5, respectively, Fig.\u00a08e) and (f), these types of contacts only contribute 6.9 and 3.2%, respectively, to the total inter\u00adatomic contacts. The accumulated contribution of the remaining six different inter\u00adatomic contacts is around 6.0% and these do not have a significant influence on the mol\u00adecular packing.The overall two-dimensional fingerprint plot of (I)et al., 2017via the long-range corrected \u03c9B97XD functional combining the D2 version of Grimme\u2019s dispersion model  are listed in Table\u00a04The inter\u00adaction energies in the crystal of (I)\u22121). This is followed by the phenyl-C36\u2014H36\u22efF1 and phenyl-C3\u2014H3\u22efO1 inter\u00adactions , which lead to the dimeric aggregate in Fig.\u00a02a). The other directional contacts outlined in Supra\u00admolecular features contribute minor stabilization energies to the mol\u00adecular packing  while the pairwise weak phenyl-C15\u2014H15\u22ef\u03c0(C21\u2013C26) and phenyl-C32\u2014H32\u22ef\u03c0(C11\u2013C16) inter\u00adactions, which were identified through the Hirshfeld surface analysis, have a greater stabilization energy .The greatest stabilization energy arises from the phenyl-C22\u2014H22\u22ef\u03c0(C2\u2013C7) and fluoro\u00adbenzene-C7\u2014H7\u22efC1(imine) inter\u00adactions =NC6H4Y-3]. Selected geometric parameters for these are given in Table\u00a056 residues, which vary by up to nearly 15\u00b0. Finally, there is an isostructural relationship between (I)Y = Cl compound 1H and 13C{1H} NMR spectra were recorded in CDCl3 solution on a Bruker Ascend 400\u2005MHz NMR spectrometer  with chemical shifts relative to tetra\u00admethyl\u00adsilane; the 31P{1H} NMR spectrum was recorded in CDCl3 solution on the same instrument but with the chemical shift recorded relative to 85% aqueous H3PO4 as the external reference. IR spectra were measured on a Bruker Vertex 70v FTIR spectrophotometer  from 4000 to 400\u2005cm\u22121. Elemental analyses were performed on a Leco TruSpec MicroCHN Elemental Analyser .All chemicals and solvents were used as sourced without further purification. Melting points were determined on a Biobase automatic melting point apparatus MP450 . M HCl. The resulting mixture was extracted using chloro\u00adform, yielding colourless crystals after 3 weeks standing. Yield: 0.421\u2005g (91%), m.p. 334.0\u2013334.5\u2005K. Analysis calculated for C8H8FNOS: C, 51.88; H, 4.35; N, 7.56%. Found: C, 51.49; H, 4.46; N, 7.42%. IR (cm\u22121): 3241 (br) \u03bd(N\u2014H), 1438 (s) \u03bd(C\u2014N), 1150 (s) \u03bd(C\u2014O), 1048 (s) \u03bd (C=S). 1H NMR : \u03b4 8.88 , 7.29\u20136.87 , 4.15  ppm. 13C{1H} NMR : \u03b4 189.4 (Cq), 162.8 , 138.5 (aryl-C1), 130.2 , 116.8 (aryl-C6), 112.2 , 109.1 (aryl-C2), 58.9 (OCH3) ppm.The thiol precursor, LH, was prepared from the reaction of 3-fluoro\u00adphenyl iso\u00adthio\u00adcyanate  and MeOH  in the presence of NaOH  followed by the addition of excess 1 3PAuCl precursor was prepared from the reduction of KAuCl4 using sodium sulfite, followed by the addition of a stoichiometric amount of tri\u00adphenyl\u00adphosphane. The precipitate was used as isolated.The Ph3PAuCl  in aceto\u00adnitrile (20\u2005ml), LH  in aceto\u00adnitrile (20\u2005ml) was added and the solution was stirred for 3\u2005h. The solution was left for slow evaporation at room temperature, yielding colourless crystals after 2 weeks. Yield: 0.273\u2005g (85%), m.p. 408.0\u2013408.5\u2005K. Analysis calculated for C26H22AuFNOPS: C, 48.53; H, 3.45; N, 2.18%. Found: C, 48.73; H, 3.56; N, 1.97%. IR (cm\u22121): 1575 (s) \u03bd(C=N), 1122 (s) \u03bd(C\u2014O), 1100 (s) \u03bd(C\u2014S). 1H NMR : \u03b4 7.55\u20137.43 , 6.95\u20136.89 , 6.63\u20136.61 , 6.39\u20136.36 , 3.90  ppm. 13C{1H} NMR : \u03b4 165.4 (Cq), 163.2 , 152.8 , 134.3 , 131.7 , 129.7 , 129.3 , 129.1 , 117.8 , 109.3 , 109.1 , 55.5 (OCH3) ppm. 31P{1H} NMR : \u03b4 38.8 ppm.NaOH  in water (5\u2005ml) was added to a suspension of PhUiso(H) set to 1.2\u20131.5Ueq(C). The maximum and minimum electron density peaks of 1.17 and 1.22\u2005e\u2005\u00c5\u22123, respectively, are located 0.97 and 0.69\u2005\u00c5, respectively, from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989020009469/hb7932sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020009469/hb7932Isup2.hklStructure factors: contains datablock(s) I. DOI: 2015568CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "PThe crystal structure of 4-allyl-2-meth\u00adoxy-6-nitro\u00adphenol, which crystallizes in the centrosymmetric space group  10H11NO4, which was synthesized via nitration reaction of eugenol  with a mixture of nitric acid and sulfuric acid, consists of three independent mol\u00adecules of similar geometry. Each mol\u00adecule displays an intra\u00admolecular hydrogen bond involving the hydroxide and the nitro group forming an S(6) motif. The crystal cohesion is ensured by inter\u00admolecular C\u2014H\u22efO hydrogen bonds in addition to \u03c0\u2013\u03c0 stacking inter\u00adactions between the aromatic rings [centroid\u2013centroid distances = 3.6583\u2005(17)\u20134.0624\u2005(16)\u2005\u00c5]. The Hirshfeld surface analysis and the two-dimensional fingerprint plots show that H\u22efH (39.6%), O\u22efH/H\u22efO (37.7%), C\u22efH/H\u22efC (12.5%) and C\u22efC (4%) are the most important contributors towards the crystal packing.The asymmetric unit of the title compound, C The benzene rings of mol\u00adecules Mol-N2 and Mol-N3 are approximately parallel to each other [dihedral angle 10.60\u2005(7)\u00b0], and roughly perpendicular to that of Mol-N1 . A strong intra\u00admolecular O\u2014H\u22efO hydrogen bond involving a nitro O atom and the H atom of the hydroxide group forming an S(6) motif is observed in each mol\u00adecule \u2005\u00c5; Cg2\u22efCg3ii = 3.6613\u2005(18)\u2005\u00c5; Cg3\u22efCg3iii = 4.0624\u2005(16)\u2005\u00c5; symmetry codes: (i) 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; (ii) 1\u00a0+\u00a0x, y, z; (iii) \u2212x, \u2212y, 1\u00a0\u2212\u00a0z].In the crystal, the mol\u00adecules are connected by inter\u00admolecular C12s Table\u00a01 and 3 \u25b8.et al., 2007Crystal Explorer 17.5 . The shape-index of the Hirshfeld surface is a tool to visualize the \u03c0\u2013\u03c0 stacking inter\u00adactions . The red spots in Fig.\u00a04a correspond to the strong C\u2014H\u22efO hydrogen-bond inter\u00adactions in the crystal structure; in Mol-N1 two of them involve the O atoms of the meth\u00adoxy (O1) and nitro (O3) groups as acceptors with allyl H atoms (C22B\u2013 H22B\u22efO1 and C12B\u2014H12B\u22efO3), while the other is due to the inter\u00adatomic inter\u00adaction between the aromatic H9 donor atom and the nitro O7 oxygen atom (C9\u2014H9\u22efO7). The longer O\u2014H\u22efO hydrogen bonds and O\u22efO inter\u00adactions are characterized by smaller red spots close to each other on the surface, where the faint red spot indicating the O\u2014H\u22efO inter\u00adactions is associated with the longest O\u22efO contact of 2.96\u2005(3)\u2005\u00c5 in Mol-N1 and Mol-N3. In Mol-N2, the red spots correspond to C\u2014H\u22efO (C9\u2014H9\u22efO7 and C12A\u2014H12A\u22efO12) and C\u2014H\u22efC (C20\u2014H20B\u22efC11A) hydrogen-bond inter\u00adactions. The corresponding fingerprint plots for each of the independent mol\u00adecules and for the entire asymmetric unit, showing characteristic pseudo-symmetric wings in the de and di diagonal axes, and those delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC and C\u22efC contacts are illustrated in Fig.\u00a06b), which is reflected in the widely scattered points of high density due to the large hydrogen-atom content of the mol\u00adecule. The contribution from the O\u22efH/H\u22efO contacts (31.7%), corresponding to C\u2014H\u22efO and O\u2014H\u22efO inter\u00adactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter\u00adaction with de + di \u2243 2.5\u00c5 . In the absence of weak C\u2014H\u22ef\u03c0 inter\u00adactions in the crystal, the pair of characteristic wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts (7.7% contribution) have a symmetrical distribution of points , with the tips at de + di \u2243 2.65\u2005\u00c5. The distribution of points in the de = di \u2243 1.6\u2005\u00c5 range in the fingerprint plot delineated into C\u22efC contacts  indicates the existence of weak \u03c0\u2013\u03c0 stacking inter\u00adactions between the phenyl rings, which are indicated by adjacent red and blue triangles in the shape-index map . The small contribution of the other weak inter\u00admolecular O\u22efO, N\u22efH/H\u22efN, C\u22efO/O\u22efC, C\u22efN/N\u22efC and N\u22efO/O\u22efN contacts has a negligible effect on the packing.In order to explore the nature of the inter\u00admolecular contacts and their role in the crystal packing, Hirshfeld surfaces  as eluent. The reaction mixture was diluted with di\u00adchloro\u00admethane, washed with brine (3 \u00d7 10\u2005mL), dried over anhydrous Na2SO4 and concentrated under vacuum. The crude product was subjected to chromatography on a silica-gel column with n-hexa\u00adne/AcOEt (9:1 v/v) as eluent to afford the title compound as a reddish-orange liquid. Reddish-orange crystals formed spontaneously with a yield of 56%. Good quality crystals suitable for single crystal X-ray diffraction analysis were obtained by slow evaporation of an n-hexa\u00adne:AcOEt solution, m.p. = 317\u2013319\u2005K.In a 250\u2005mL flat-bottom flask containing a stirred solution of eugenol  and di\u00adchloro\u00admethane (60\u2005mL), a mixture of concentrated sulfuric acid (0.78\u2005mL) and concentrated nitric acid (0.80\u2005mL) was added dropwise for 30\u2005min at 273\u2005K. The complete disappearance of the starting product was confirmed by means of thin layer chromatography using \u22121): 3235, 3080, 3016, 2971, 2910, 1638, 1537, 1392, 1331, 1262, 1128, 1059, 909, 763. The FT\u2013IR spectrum  \u03b4 10.7 , 7.53 , 6.99 , 6.01\u20135.88 , 5.19\u20135.13 , 3.96 , 3.39\u20133.37 . 13C NMR  \u03b4 149.87, 144.90, 135.95, 133.66, 131.24, 118.63, 117.16, 115.11, 114.29, 56.72, 39.41. FTMS\u2013ESI, m/z: 208.04616 (100%) [C10H11NO4].Uiso(H) = 1.2 Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups. The hydroxyl H atoms were located in a difference-Fourier map and refined freely. The two allyl groups of Mol-N2 and Mol-N3 are disordered over two sets of sites with refined occupancy ratios of 0.648\u2005(8):0.352\u2005(8) and 0.668\u2005(9):0.332\u2005(9) respectively. One outlier (100) was omitted in the cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020002601/rz5270sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020002601/rz5270Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002601/rz5270Isup3.cmlSupporting information file. DOI: 1986157CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Its crystal structure was determined at 100\u2005K. Both weak intra\u00admolecular O\u2014H\u22efO and inter\u00admolecular O\u2014H\u22efS hydrogen bonding can be observed.The title compound is an example of an  22H22O2S2, 1, represents an example of an ortho-vanillin-based functionalized di\u00adthio\u00adether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. This di\u00adthio\u00adacetal 1 crystallizes in the ortho\u00adrhom\u00adbic space group Pbca. The phenyl rings of the benzyl groups and that of the vanillin unit form dihedral angles of 35.38\u2005(6) and 79.77\u2005(6)\u00b0, respectively. The crystal structure, recorded at 100\u2005K, displays both weak intra\u00admolecular O\u2014H\u22efO and inter\u00admolecular O\u2014H\u22efS hydrogen bonding.The title compound, C R)(H)\u2013S\u2013  motif are synthesized by nucleophilic substitution of geminal dihalides X\u2013C(R)(H)\u2013X in the presence of thiol\u00adate RS\u2212 nSH , yielding geminal di\u00adthio ethers, also called acyclic and cyclic thio\u00adacetals  Fe(CO)2(\u03ba1-BzSCH2SBz)]+, the 1:1 adduct [Hg2(NO3)2\u00b7BzSCH2SBz)], the dinuclear PdI complex [ClPd(\u03bc2-BzSCH2SBz)2PdCl], and the monodimensional coordination polymer [Ag2(BzSCH2SBz)2](ClO4)2 built upon dinuclear [Ag(\u03bc2-BzSCH2SBz)2Ag]2+ units  as the starting material. This hy\u00addroxy\u00adlated aldehyde is present in the extracts and essential oils of many plants. Several papers describe also its use (in its deprotonated vanillinato form or as a Schiff base-derived ligand) in coordination chemistry  and 1.8189\u2005(12)\u2005\u00c5 are comparable with those of [BzSC(H)(C6H4NO2-p)SBz] [1.823\u2005(3) and 1.8262\u2005(19)\u2005\u00c5], but are elongated compared with those of bis\u00ad(benzyl\u00adsulfan\u00adyl)methane (CSD TUQPAX) , but considerably more acute than in [BzSCH2SBz] [117.33\u2005(7)\u00b0]. There is a weak intra\u00admolecular O1\u22efH2 contact of 2.17\u2005(2)\u2005\u00c5 between the H atom of the phenolic hydroxyl group and the O-atom of the meth\u00adoxy group SBz] , O2\u22efS1 = 3.1315\u2005(13)\u2005\u00c5] similar to those reported for 4--1,2-benzene\u00addiol , while the O\u2014H\u22efS angle is more acute [139.0\u2005(17) \u00b0] Fig.\u00a03. This O2The benzylic methyl\u00adene group on sulfur atom S2 inter\u00adacts with the \u03c0-cloud of the phenyl part of the vanillin unit through a C\u2014H\u22ef\u03c0 inter\u00adaction Table\u00a01. The secet al., 2016et al., 2003et al., 2005et al., 2013et al., 2013et al., 2018et al., 20131.There are several other examples of structurally characterized related di\u00adthioethers bearing hy\u00addroxy substituents that give rise to the formation of supra\u00admolecular networks. Selected examples found in the Cambridge Structural Database -1,3-di\u00adthiane (WADROY) and 2-(3-hy\u00addroxy\u00adphen\u00adyl)-1,3-di\u00adthiane (KALJUD) exhibit, like 1, only inter\u00admolecular O\u2014H\u22efS hydrogen bonding, the para-derivative 2-(4-hy\u00addroxy\u00adphen\u00adyl)-1,3-di\u00adthiane (KALKAK) features solely inter\u00admolecular phenolic O\u2014H\u22efH bonding .Note that in di\u00adthio\u00adether compounds with phenolic aryl groups as encountered in The reaction scheme for the synthesis of the title compound is illustrated in Fig.\u00a043 (10\u2005mL) and extracted with di\u00adchloro\u00admethane (3 \u00d7 10\u2005mL). The combined extracts were washed with H2O (3 \u00d7 20\u2005mL) and dried over Na2SO4. Evaporation of the solvent in vacuo gave a solid product, which was further purified by column chromatography. The product was obtained as a white solid, Yield: 83% (430\u2005mg). X-ray quality crystals were obtained by keeping a di\u00adchloro\u00admethane:hexane (1:1) mixture of 1 at 278\u2005K for 3\u20134\u2005d. 1H NMR  \u03b4 7.26\u20137.19 , 6.86 , 6.78 , 5.83 , 5.13 , 3.88 , 3.79 , 3.64 .13C{1H} NMR  \u03b4 146.5 (CqOH), 142.8 (CqOCH3), 137.8 (SCH2Cq), 129.1 (SCH2CCH), 128.4 (SCH2CCHCH), 126.9 (SCH2CCHCHCH), 125.3 (S2CHCq), 120.9 (S2CHCqCH), 119.9 (S2CHCqCHCH), 110.0 (CHCqOCH3), 56.1 (OCH3), 44.8 (S2CH), 36.7 (S2CH2). IR (ATR) cm\u22121: 3419 (O\u2014H), 1430-1612 (C=C). 1054 and 1264 (C\u2014O), 766 (C\u2014S). HRMS: (ESI) m/z calculated for C22H22O2S2Na [M + Na]+ 405.0953, found 405.0965.3-Meth\u00adoxy\u00adsalicyl\u00adaldehyde , benzyl mercaptan , and conc. HCl (2\u2005mL) were added to a flask at 273\u2005K. The mixture was stirred for 60\u2005min at room temperature. After the reaction was complete, the resulting mixture was neutralized with 10% aq NaHCOUiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C-meth\u00adyl). The phenolic proton H2 was refined independently.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020002091/vm2228sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002091/vm2228Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002091/vm2228Isup3.cmlSupporting information file. DOI: 1983985CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure as well as the Hirshfeld surface were analysed for this benzo\u00adthia\u00adzine derivative with potential analgesic activity. 10H8ClNO5S, which has potential analgesic activity, crystallizes in space group P21/n. The benzo\u00adthia\u00adzine ring system adopts an inter\u00admediate form between sofa and twist-boat conformations. The coplanarity of the ester substituent to the bicyclic fragment is stabilized by an O\u2014H\u22efO intra\u00admolecular hydrogen bond. In the crystal, hydrogen bonds of type N\u2014H\u22efO(SO2) link the mol\u00adecules into zigzag chains extending along the b-axis direction. Neighbouring chains are linked by both O\u2014H\u22efCl and C\u2014H\u22efCl inter\u00adactions. A Hirshfeld surface analysis was used to compare different types of inter\u00admolecular inter\u00adactions, giving contributions of O\u22efH/H\u22efO = 42.0%, C\u22efH/H\u22efC = 17.3%, Cl\u22efH/H\u22efCl = 14.2%, H\u22efH = 11.1%.The title compound, C H-2\u03bb6,1-benzo\u00adthia\u00adzine-3-carbox\u00adyl\u00adates are known to be highly active analgesics \u2005\u00c5, \u0398 = 111.6\u2005(5)\u00b0, \u03a8 = 192.1\u2005(6)\u00b0. The ester substit\u00aduent is essentially coplanar to the C7\u2014C8 endocyclic double bond [the C7\u2014C8\u2014C9\u2014O2 torsion angle is 3.0\u2005(7)\u00b0] as a result of the stabilizing influence of the O1\u2014H1O\u22efO2 intra\u00admolecular hydrogen bond (Table\u00a01S(6) in terms of graph-set theory since the six atoms comprise a intra\u00admolecular hydrogen-bonded motif. The formation of the O\u2014H\u22efO hydrogen bond causes some elongation of the C9\u2014O2 and C7\u2014C8 bonds as compared with typical values of 1.210\u2005\u00c5 (Csp2=O bond) and 1.326\u2005\u00c5 (Csp2\u2014Csp2 bond), respectively  for the same reason. The methyl group is located in an anti-periplanar position to the C8\u2014C9 bond [the C10\u2014O3\u2014C9\u2014C8 torsion angle is \u2212178.4\u2005(4)\u00b0]. The noticeable steric repulsion between chlorine and the hydroxyl group . The crs Table\u00a01 in the  was added, the mixture was boiled and stored for 15\u2005h at room temperature. The reaction mixture was diluted with cold water and acidified with 1\u2005N HCl to pH = 4. The solid methyl 5-chloro-4-hy\u00addroxy-2,2-dioxo-1H-2\u03bb6,1-benzo\u00adthia\u00adzine-3-carboxyl\u00adate was filtered, washed with water, and dried in air. Yield 2.43g (84%); colourless crystals; m.p. 464\u2013466\u2005K.Methyl (chloro\u00adsulfon\u00adyl)acetate  was added dropwise under stirring to a solution of methyl 6-chloro\u00adanthranilate  and tri\u00adethyl\u00adamine  in CHK) Fig.\u00a05. After 1Uiso(H) = 1.5Ueq for methyl and hydroxyl groups and with C\u2014H = 0.93\u2005\u00c5, N\u2014H = 0.88\u2005\u00c5, Uiso(H) = 1.2Ueq for all other hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020012566/pk2647sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012566/pk2647Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012566/pk2647Isup3.cmlSupporting information file. DOI: 2032151CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Bnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds form chains of mol\u00adecules extending along the a-axis direction which are connected to their inversion-related counterparts by C\u2014HBnz\u22efClDchlphy  hydrogen bonds and C\u2014HDchlphy\u22ef\u03c0 (ring) inter\u00adactions. These double chains are further linked by C\u2014HDchlphy\u22efOThz hydrogen bonds to form stepped layers approximately parallel to (012).The title compound contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00adchloro\u00adphenyl\u00admethyl\u00adidene units in which the di\u00adhydro\u00adthia\u00adzine ring adopts a screw-boat conformation. In the crystal, inter\u00admolecular C\u2014H 24H27Cl2NOS, contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00adchloro\u00adphenyl\u00admethyl\u00adidene units in which the di\u00adhydro\u00adthia\u00adzine ring adopts a screw-boat conformation. In the crystal, inter\u00admolecular C\u2014HBnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds form chains of mol\u00adecules extending along the a-axis direction, which are connected to their inversion-related counterparts by C\u2014HBnz\u22efClDchlphy  hydrogen bonds and C\u2014HDchlphy\u22ef\u03c0 (ring) inter\u00adactions. These double chains are further linked by C\u2014HDchlphy\u22efOThz hydrogen bonds, forming stepped layers approximately parallel to (012). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (44.7%), C\u22efH/H\u22efC (23.7%), Cl\u22efH/H\u22efCl (18.9%), O\u22efH/H\u22efO (5.0%) and S\u22efH/H\u22efS (4.8%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, C\u2014HDchlphy\u22efOThz, C\u2014HBnz\u22efOThz and C\u2014HBnz\u22efClDchlphy hydrogen-bond energies are 134.3, 71.2 and 34.4\u2005kJ\u2005mol\u22121, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap. The two carbon atoms at the end of the nonyl chain are disordered in a 0.562\u2005(4)/0.438\u2005(4) ratio.The title compound, C These mol\u00adecules exhibit a wide range of biological applications, indicating that the 1,4-benzo\u00adthia\u00adzine moiety is a potentially useful template in medicinal chemistry research with therapeutic applications in the anti\u00admicrobial (Armenise B (S1/N1/C1/C6\u2013C8), adopts a screw-boat conformation with puckering parameters QT = 0.5581\u2005(16)\u2005\u00c5, \u03b8 = 69.76\u2005(18)\u00b0 and \u03c6 = 334.3\u2005(2)\u00b0. The planar rings, A (C1\u2013C6) and C (C10\u2013C15) are oriented at a dihedral angle of 88.45\u2005(7)\u00b0. Atoms Cl1, Cl2 and C9 are almost co-planar with ring C being displaced by 0.0247\u2005(6), \u22120.0732\u2005(9) and \u22120.0274\u2005(2)\u2005\u00c5, respectively.The title compound contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00adchloro\u00adphenyl\u00admethyl\u00adidene units Fig.\u00a01, in whicBnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds link the mol\u00adecules, forming chains extending along the a-axis direction, which are connected to their inversion-related counterparts by C\u2014HBnz\u22efClDchlphy  hydrogen bonds and C\u2014HDchlphy\u22ef\u03c0 (ring) inter\u00adactions   Table\u00a01 and 3 \u25b8.Crystal Explorer 17.5 . The two pairs of wings in the fingerprint plot delineated into Cl\u22efHl/H\u22efCl contacts  have an unsymmetrical distribution of points due to a third wing, with the edges at de + di = 2.74\u2005\u00c5 (for the long wing), de + di = 2.92\u2005\u00c5 (for the short wing) and de + di = 3.53\u2005\u00c5 . The pair of wings in the fingerprint plot delineated into O\u22efH/H\u22efO contacts  has a pair of spikes with the tips at de + di = 2.22\u2005\u00c5. Finally, the wings in the fingerprint plot delineated into S\u22efH/H\u22efS contacts  have the tips at de + di = 2.99\u2005\u00c5.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be \u221253.7 (Eele), \u221213.6 (Epol), \u2212161.9 (Edis), 119.0 (Erep) and \u2212134.3 (Etot) for C\u2014HDchlphy\u22efOThz, 25.6 (Eele), \u22125.7 (Epol), \u221262.1 (Edis), 23.1 (Erep) and \u221271.2 (Etot) -4-nonyl-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one ring.The optimized structure of the title compound, (I)et al., 2016II gave 14 hits.A search in the Cambridge Structural Database , 29\u00b0 (APAJUY), 28\u00b0 (SAVTUH), 26\u00b0 (WOCFUS) and 25\u00b0 (COGRUN). By contrast, in both EVIYIT and OMEGEU, the benzo\u00adthia\u00adzine unit is nearly planar with the corresponding dihedral angle being about 4\u00b0.The largest set contains Z)-2--2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one (1.5\u2005mmol), potassium carbonate (2.7\u2005mmol) and tetra-n-butyl ammonium bromide (0.14\u2005mmol) in DMF (20\u2005mL) was added 1-bromo\u00adnonane (2.6\u2005mmol). Stirring was continued at room temperature for 24\u2005h. The mixture was filtered and the solvent removed. The residue obtained was washed with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate\u2013hexane (9/1) as eluent. Colourless crystals were isolated when the solvent was allowed to evaporate (yield = 79%).To a solution of (Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020001036/lh5943sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020001036/lh5943Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001036/lh5943Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020001036/lh5943Isup4.cmlSupporting information file. DOI: 1980073CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the mean planes of the benzene ring and that of the twisted piperidine ring is 39.89\u2005(7)\u00b0. In the crystal, weak C\u2014H\u22efO inter\u00adactions link the mol\u00adecules into infinite chains along the  13H16ClNO, contains a methyl\u00adpiperidine ring in the stable chair conformation. The mean plane of the twisted piperidine ring subtends a dihedral angle of 39.89\u2005(7)\u00b0 with that of the benzene ring. In the crystal, weak C\u2014H\u22efO inter\u00adactions link the mol\u00adecules along the a-axis direction to form infinite mol\u00adecular chains. H\u22efH inter\u00adatomic inter\u00adactions, C\u2014H\u22efO inter\u00admolecular inter\u00adactions and weak dispersive forces stabilize mol\u00adecular packing and form a supra\u00admolecular network, as established by Hirshfeld surface analysis.The title compound, C The C1\u2014N1\u2014C6\u2014O1 and O1\u2014C6\u2014C7\u2014C8 torsion angles are \u2212167.4\u2005(2) and 50.7\u2005(3)\u00b0, respectively. The C1\u2014C2\u2014C3\u2014C13 torsion angle [177.7\u2005(2)\u00b0] reveals the anti-periplanar (+ap) orientation of the methyl group with respect to the piperidine ring.The mol\u00adecular structure of the title compound, which features a chloro\u00adbenzene ring and a methyl\u00adpiperidine ring, is shown in Fig.\u00a01x\u00a0\u2212\u00a01, y, z), forming chains parallel to the a axis (Table\u00a01a). Weak C\u2014H\u22ef\u03c0 close contacts between H5A and the benzene ring of an adjacent  mol\u00adecule provide linkage between inversion-related  chains (Table\u00a01b). Analysis of the Hirshfeld surface  = 1.5Ueq(C-meth\u00adyl) or 1.2Ueq(C) for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020001930/jj2221sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020001930/jj2221Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001930/jj2221Isup3.cmlSupporting information file. DOI: 1973841CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing of the title mol\u00adecular salt, in which the tin atom lies on a crystallographic inversion centre, is dominated by N\u2014H\u22efCl hydrogen bonds. 5H7N2)2[SnCl6], the cation is protonated at the pyridine N atom and the complete dianion is generated by a crystallographic centre of symmetry. In the crystal, N\u2014H\u22efCl hydrogen bonds link the components into a three-dimensional network built up from the stacking of alternate cationic and anionic layers. The nature of the inter\u00admolecular inter\u00adactions has been analysed in terms of the Hirshfeld surfaces of the cations and the anions. The thermal behaviour and the Raman spectrum of the title compound are reported.In the title mol\u00adecular salt, (C For example, in these hybrid materials, the organic part can have non-linear optical properties  and an organic cation +2\u00b7[SnCl6]2\u2212, crystallizes in the triclinic space group PCompound (I)P Fig.\u00a01.et al., 2018i.e. none of the chloride ions are bridging although they do accept N\u2014H\u22efCl hydrogen bonds from the organic cations, which ensures charge balance.In the synthesis, the oxidation number of tin changes from +2 to +4 such that the resultant tin(IV) atom is hexa\u00adcoordinated by chlorine atoms, generating a weakly distorted octa\u00adhedron in which the metal ion lies on a crystallographic inversion centre: the length of the Sn\u2014Cl bonds varies from 2.4216\u2005(4) to 2.4474\u2005(5)\u2005\u00c5. As for the Cl\u2014Sn\u2014Cl angles, the discrepancy of about \u00b1 1\u00b0 [89.109\u2005(18)\u201390.805\u2005(16)\u00b0] compared to the 90\u00b0 value angle of a regular octa\u00adhedron shows that the angular distortion is very small. These values are comparable to those of the same anion associated with other types of cations  to 1.405\u2005(3)\u2005\u00c5 and the C\u2014N bond lengths are 1.341\u2005(3)\u2005\u00c5 and 1.344\u2005(2)\u2005\u00c5. The values of the C\u2014C\u2014C angles in the pyridinium ring vary from 118.9\u2005(2) to 120.9\u2005(2)\u00b0 whereas the C\u2014N\u2014C angle is 124.30\u2005(18)\u00b0: the larger angle can be attributed to the protonation of the N atom. These values are comparable with those of the same cation associated with other types of anions (Rao a). The inter\u00admolecular inter\u00adactions in (I)PLATON  in the crystal of (I)A\u22efCl1 and N2\u2014H2B\u22efCl2 hydrogen bonds generates a chain of rings propagating along the [001] direction with a graph-set pattern of et al., 1990b). The cohesion between chains is ensured by \u03c0-stacking inter\u00adactions between centrosymmetrically related aromatic rings of the cations: Cg1\u22efCg1 = 3.552\u2005(13)\u2005\u00c5; inter-planar angle \u03b1 = 0.0\u2005(11)\u00b0; slippage = 1.246\u2005\u00c5. We also note the presence of a Y\u2014X\u22efCg1 type inter\u00adaction between Sn1\u2014Cl2 and Cg1 at an X\u22efCg distance of 3.6581\u2005(11)\u2005\u00c5 [Fig.\u00a02a)].The combination of N2\u2014H2Crystal Explorer 17 a)] shows red spots corresponding to H\u22efCl/Cl\u22efH close contacts, which are due to the N\u2014H\u22efCl hydrogen bonds. The presence of the adjacent red and blue triangles in Fig.\u00a03b) demonstrates the presence of the Cg1\u22efCg1 and Sn\u2014Cl2\u22efCg1 inter\u00adactions. The contribution of different kinds of inter\u00adatomic contacts to the Hirshfeld surfaces of the individual cations and anions is shown in the fingerprint plots in Fig.\u00a04Y\u2014X\u22ef type (N\u22efCl and C\u22efCl), 6.6% of \u03c0\u2013\u03c0 stacking type (C\u22efC and C\u22efN/N\u22efC), 15.6% of C\u2014H\u22ef\u03c0 type (C\u22efH/H\u22efC), 6.2% of N\u2014H\u22ef\u03c0 type (N\u22efH/H\u22efN) and 21.1% of H\u22efH van der Waals inter\u00adactions. The two-dimensional fingerprint analysis for the anionic moieties reveals that hydrogen bonds (Cl\u22efH) represent 93.8%, Y\u2014X\u22ef\u03c0 type inter\u00adactions represent 4.4% (Cl\u22efN and Cl\u22efC) and van der Waals inter\u00adactions of the Cl\u22efCl type represent 1.8% of the surface contacts.The Hirshfeld surface 2\u2212 anions are associated with special positions and an organic\u2013inorganic layered structure lying parallel to the (001) plane results.A search of the Cambridge Structural Database .Crystalline cohesion in RIGDER and (I)2 atmosphere at a heating rate of 10\u00b0C min\u22121 in the temperature range from 25 to 500\u00b0C. The thermogram of (I)supporting information) shows that the compound loses 64.4% of its mass in the temperature range of 270\u2013304\u00b0C. The mass loss can be attributed to the degradation of the organic entity and two chlorine atoms 1H NMR (\u03b4 ppm), 400\u2005MHz, CDCl3): 8.16 , 7.95\u20137.89 , 7.03 , 6.84 . 13C NMR (\u03b4 ppm), 125\u2005MHz, CDCl3): 154.6 (quat C Py), 144.4 (CH Py), 136.1 (CH Py), 113.8 (CH Py), 112.5 (CH Py).Tin(II) chloride dihydrate (2.25\u2005mmol) was mixed with 2-amino\u00adpyridine (0.94\u2005mmol) and a few drops of hydro\u00adchloric acid in an aliquot of distilled water in 1:1 molar ratio was added. After stirring, the mixture was poured into a vial  that was put in an oven for three days at 393\u2005K. Upon cooling, prism-shaped crystals of (I)\u22121. The Py, \u03bd, \u03b4, \u03b3 and \u03c4 are: pyridine ring, stretching, in-plane bending, out-of-plane bending and torsion, respectively. RS (cm\u22121): 3334 \u03bd(N\u2014H), 3215 \u03bd (N\u2014H), 3106 \u03bd(C\u2014H), 1657 \u03bd(py)+\u03b4(N\u2014H)+\u03b4(NH2), 1620 \u03bd(py), 1542 \u03bd(py), 1472 \u03bd(py)+\u03b4(C\u2014H), 1412 \u03bd(py)+\u03b4(C\u2014H), 1378 \u03bd(py)+\u03b4(C\u2014H), 1324 \u03bd(py)+\u03b4(C\u2014H), 1239 \u03bd(py)+\u03b4(C\u2014H), 1164 \u03b4(py)+\u03b4(C\u2014H), 1120 \u03b4(py)+\u03b4(C\u2014H), 996 \u03b4(py), 846 Pyridine ring breathing+\u03b3(C\u2014H), 623 \u03b3(py), 551 \u03b3(py), 406 \u03b3(py), 384 \u03b3(py), 305 \u03bd1 (Sn\u2014Cl), 216 \u03bd2 (Sn\u2014Cl), 106 \u03c4(py)+ \u03bd(N\u2014H\u22efCl) Uiso(H) = 1.2Ueq(C)]; the pyridine N\u2014H atom was located in a difference map and its position was freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902000941X/hb7922sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902000941X/hb7922Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902000941X/hb7922sup3.jpgSupporting information file. DOI: Click here for additional data file.10.1107/S205698902000941X/hb7922sup4.docxSupporting information file. DOI: 1904730CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Theoretical calculations suggested that the new bis\u00ad(hy\u00addroxy\u00adimine) will exhibit histone de\u00adacetyl\u00adase SIRT2, histone de\u00adacetyl\u00adase class III and histone de\u00adacetyl\u00adase SIRT1 activities, and will act as inhibitor to aspulvinone di\u00admethyl\u00adallyl\u00adtransferase, de\u00adhydro- 47H32N2O2\u00b7C6H4Cl2, contains two anil fragments in the enol\u2013enol form, exhibiting intra\u00admolecular O\u2014H\u22efN hydrogen bonds. The two hy\u00addroxy\u00adnaphthalene ring systems are approximately parallel to each other with a dihedral angle of 4.67\u2005(8)\u00b0 between them, and each ring system makes a large dihedral angle [55.11\u2005(11) and 48.50\u2005(10)\u00b0] with the adjacent benzene ring. In the crystal, the bis\u00ad(anil) mol\u00adecules form an inversion dimer by a pair of weak C\u2014H\u22efO inter\u00adactions. The dimers arrange in a one-dimensional column along the b axis via another C\u2014H\u22efO inter\u00adaction and a \u03c0\u2013\u03c0 stacking inter\u00adaction between the hy\u00addroxy\u00adnaphthalene ring system with a centroid\u2013centroid distance of 3.6562\u2005(16)\u2005\u00c5. The solvent 1,2-di\u00adchloro\u00adbenzene mol\u00adecules are located between the dimers and bind neighbouring columns by weak C\u2014H\u22efCl inter\u00adactions. Theoretical prediction of potential biological activities was performed, which suggested that the title anil compound can exhibit histone de\u00adacetyl\u00adase SIRT2, histone de\u00adacetyl\u00adase class III and histone de\u00adacetyl\u00adase SIRT1 activities, and will act as inhibitor to aspulvinone di\u00admethyl\u00adallyl\u00adtransferase, de\u00adhydro-l-gulonate deca\u00adrboxylase and gluta\u00adthione thiol\u00adesterase.The bis\u00ad(anil) mol\u00adecule of the title compound, C According to the PASS program \u2013 computer prediction of biological activities  and gluta\u00adthione thiol\u00adesterase (71%).Schiff bases formed by the condensation of salicyl\u00adaldehydes with amines are also known as anils. They often exhibit potent anti\u00adbacterial, anti\u00adproliferative and anti\u00adtoxic properties  forms large dihedral angles of 78.80\u2005(10) and 61.41\u2005(9)\u00b0, respectively, with the benzene C14\u2013C19 and C31\u2013C36 rings. Each hy\u00addroxy\u00adnaphthalene ring system also forms a large dihedral angle with the adjacent benzene ring . Both fragments of the hy\u00addroxy\u00adnaphthalene Schiff bases are in the enol form, forming intra\u00admolecular O\u2014H\u22efN hydrogen bonds (Table\u00a01In the title bis\u00ad(anil) mol\u00adecule, two hy\u00addroxy\u00adnaphthalene ring systems are approximately parallel to each other with a dihedral angle of 4.67\u2005(8)\u00b0 between them Fig.\u00a01. The 9H-s Table\u00a01.via a pair of weak C\u2014H\u22efO inter\u00adactions . Di\u00adchloro\u00adbenzene mol\u00adecules are located between the dimers and bind the neighboring columns by weak C\u2014H\u22efCl inter\u00adactions  mol\u00adecules form an inversion dimer s Table\u00a01.et al., 2016via the condensation of the corresponding di\u00adamine and an appropriate hy\u00addroxy\u00adaldehyde dianiline according to the literature  = 1.2Ueq(C)], while the H atoms of the OH groups were localized in a difference-Fourier map and refined with Uiso(H) = 1.5Ueq(O).Crystal data, details of data collection, and results of structure refinement are summarized in Table\u00a0210.1107/S2056989020012104/is5554sup1.cifCrystal structure: contains datablock(s) general, I. DOI: 10.1107/S2056989020012104/is5554Isup2.hklStructure factors: contains datablock(s) I. DOI: 2019265CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Compounds 1 and 2 crystallize, respectively, in space group P21/c with Z\u2032 = 2 and in space group Pbca with Z\u2032 = 1. The crystals of compound 1 contain neutral and anionic Bmphfp mol\u00adecules, and form a one-dimensional hydrogen-bonded chain motif. The crystals of compound 2 contain anionic Bmphfp mol\u00adecules, which form a complex three-dimensional hydrogen-bonded network with the ethyl\u00adenedi\u00adamine and water mol\u00adecules.The crystal structures of two salt crystals of 2,2-bis\u00ad(4-methyl\u00adphen\u00adyl)hexa\u00adfluoro\u00adpropane (Bmphfp) with amines, namely, dipyridinium 4,4\u2032-dibenzoate 4,4\u2032-di\u00adbenzoic acid, 2C Inter\u00adestingly, one of the two Bmphfp mol\u00adecules is neutral and the other is anionic. The C\u2014O bond lengths of the carb\u00adoxy groups are summarized in Table\u00a01A and B are in the neutral and divalent anionic forms, respectively. The two benzene rings are twisted with respect to each other, forming dihedral angles of 72.19\u2005(6) and 69.98\u2005(6)\u00b0. On the other hand, compound 2 crystallizes in the ortho\u00adrhom\u00adbic space group Pbcn. The asymmetric unit comprises one Bmphfp anion, one ethyl\u00adenedi\u00adammonium cation and one water mol\u00adecule . The C\u2014O bond lengths shown in Table\u00a01Compound it Fig.\u00a01a. Interle Fig.\u00a01b. The C1, the pyridine mol\u00adecules form strong N\u2014H\u22efO hydrogen bonds with the carboxyl groups of Bmphfp mol\u00adecule B (Table\u00a02a). The neutral (A) and anionic (B) Bmphfp mol\u00adecules form a one-dimensional hydrogen-bonded chain motif along the a-axis direction . The lengths of the negative charge-assisted O\u2014H\u22efO hydrogen bonds, 2.5732\u2005(13) and 2.5125\u2005(13)\u2005\u00c5, are shorter than in the common carboxyl dimer [2.643\u2005\u00c5; the mean value calculated from 505 research hits in the Cambridge Structural Database \u2005\u00c5 (C\u22efF) and 2.696\u2005(1)\u2005\u00c5 (F\u22efF), respectively.In the crystal of compound B Table\u00a02a. The non Fig.\u00a02b. The l2, one carb\u00adoxy\u00adlic group of the Bmphfp mol\u00adecule is linked to an ethyl\u00adenedi\u00adammonium cation by two N\u2014H\u22efO hydrogen bonds. The N\u22efO inter\u00adatomic distances are 2.7749\u2005(14) and 2.8015\u2005(14)\u2005\u00c5, respectively (Table\u00a03a). Therefore, five of the six hydrogen-atom donors of the ethyl\u00adenedi\u00adammonium cations are connected to Bmphfp mol\u00adecules, resulting in a complex three-dimensional hydrogen-bonding network. The water mol\u00adecule is linked to both Bmphfp and ethyl\u00adenedi\u00adamine mol\u00adecules via two O\u2014H\u22efO and one N\u2014H\u22efO hydrogen bonds. Thus, the water mol\u00adecules are highly stabilized by these inter\u00admolecular inter\u00adactions in the crystal structure . Weak C\u2014H\u22efF and F\u22efF inter\u00adactions are observed between Bmphfp mol\u00adecules, resulting inter\u00adatomic distances of 3.493\u2005(1)\u2005\u00c5 (C\u22efF) and 2.890\u2005(1)\u2005\u00c5 (F\u22efF), respectively. In compound 2, the Bmphfp mol\u00adecules do not form a discrete 1-D hydrogen bond chain motif as observed in compound 1 because the one carboxyl group is terminated by an ethyl\u00adenedi\u00adamine mol\u00adecule.In the crystal of compound y Table\u00a03. The othy Table\u00a03a. Therere Fig.\u00a03b. Weak et al., 2007CrystalExplorer17  compared to mol\u00adecule A. Thus, mol\u00adecule B is more closely packed with the surrounding mol\u00adecules in the crystal than mol\u00adecule A. This may be due to the difference in the ionic state between neutral mol\u00adecule A and anionic mol\u00adecule B. Compound 1 (mol\u00adecule A and B) has strong hydrogen-bonding inter\u00adactions, with similar but slightly weaker inter\u00adactions for compound 2. The contributions to the Hirshfeld surface for 2 are listed in Table\u00a06Hirshfeld surfaces benzene hexa\u00adfluoro\u00adpropane, pyridine and ethyl\u00adenedi\u00adamine were purchased from TCI Co., Ltd. (Japan). 2,2-Bis(4-methyl\u00adphen\u00adyl)hexa\u00adfluoro\u00adpropane  was dissolved in methanol 10\u2005mL. The Bmphfp solution was mixed into 5\u2005mL of a 1.0 sp2\u2014H = 0.86, Nsp3\u2014H = 0.89\u2005\u00c5 with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989020005575/lh5959sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989020005575/lh59591sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989020005575/lh59592sup3.hklStructure factors: contains datablock(s) 2. DOI: 1998170, 1998169CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The PtII atoms in both mol\u00adecules adopt distorted square-planar geometries, coordinated by one C and two N atoms from the tridentate 2\u2032,6\u2032-di\u00adfluoro-6-[3-(pyridin-2-yl\u00adoxy)phen\u00adyl]-2,3\u2032-bi\u00adpyridine ligand and a chloride anion: the C and Cl atoms are trans. In the crystal, C\u2014H\u22efCl/F hydrogen bonds, F\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent A and B mol\u00adecules and between pairs of inversion-related B mol\u00adecules lead to the formation of a two-dimensional supra\u00admolecular network lying parallel to the ab plane. The sheets are stacked along the c-axis direction and linked by F\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions between pairs of inversion-related A mol\u00adecules, forming a three-dimensional supra\u00admolecular network. The photoluminescence quantum efficiency of the title compound in the blue\u2013green region of the visible region (\u03bbmax = 517 and 544\u2005nm) is estimated to be \u223c0.2\u20130.3, indicating that the title compound could be a suitable candidate as the emitting material in organic light-emitting diode (OLED) applications.The title compound, [Pt(C The average length [1.949\u2005(4)\u2005\u00c5] of the Pt\u2014C bonds is slightly shorter than that [2.042\u2005(3)\u2005\u00c5] of the Pt\u2014N bonds because of back bonding between the metal and the anionic C atom of the ligand. The Cl1 and Cl2 atoms deviate from the mean plane consisting of the Pt and coordinated N/C atoms [r.m.s. deviations = 0.013\u2005(1) (A) and 0.017\u2005(1)\u2005\u00c5 (B)] with deviations of 0.700\u2005(6)\u2005\u00c5 for A and 0.720\u2005(6)\u2005\u00c5 for B.The asymmetric unit of the title compound, Pt\u2005\u00c5, Cl2\u22efCg8 = 3.455\u2005(2)\u2005\u00c5; green dashed lines in Fig.\u00a01Cg4 and Cg8 are the centroids of the N3/C17\u2013C21 and N6/C38\u2013C42 rings, respectively] between the coordinated chloride ion and the pyridine ring with fluorine substituents are also observed. Mol\u00adecules A and B are inter\u00adlinked by a C\u2014H\u22efCl inter\u00adaction (Table\u00a02A and 9.64\u2005(11)\u00b0 for B. However, the terminal di\u00adfluoro-pyridine ring is tilted by 46.08\u2005(9) for A and 46.96\u2005(8)\u00b0 for B with respect to phenyl\u00adpyridine ring plane. This distortion may be caused by the intra\u00admolecular Cl\u22ef\u03c0 inter\u00adaction described above. The pyridine ring of the pyridine-2-yl\u00adoxy group is slightly tilted by 22.09\u2005(13) for A and 19.70\u2005(13)\u00b0 for B relative to the phenyl\u00adpyridine ring plane.In each mol\u00adecule, there are intra\u00admolecular C\u2014H\u22efCl/F inter\u00adactions, contributing to the stabilization of the mol\u00adecular structure Table\u00a02. Moreoven Table\u00a02. In the A and B mol\u00adecules and between pairs of inversion-related B mol\u00adecules lead to the formation of a two-dimensional supra\u00admolecular network lying parallel to the ab plane. In addition, this network is consolidated by halogen\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions  between pairs of inversion-related B mol\u00adecules. These sheets are stacked along the c-axis direction and connected by F\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions  between pairs of inversion-related A mol\u00adecules, resulting in the formation of a three-dimensional supra\u00admolecular network.In the crystal structure, inter\u00admolecular C\u2013H\u22efCl/F hydrogen bonds Table\u00a02 and 2 \u25b8 The bright blueish-green emission of the title compound in solution is dominated by phospho\u00adrescence as supported by an excited-state lifetime of more than 1\u2005ms. Emission maxima appear at 517 and 544\u2005nm at room temperature, as shown in Fig.\u00a04SciFinder , gave two hits. These are the reports of the crystal structures and photophysical properties of the free ligands for 2\u2032,6\u2032-di\u00adfluoro-6-[3-(pyridin-2-yl\u00adoxy)phen\u00adyl]-2,3\u2032-bi\u00adpyridine and 2\u2032,6\u2032-dimeth\u00adoxy-6-[3-(pyridin-2-yl\u00adoxy)phen\u00adyl]-2,3\u2032-bi\u00adpyridine phen\u00adyl]-2,3\u2032-bi\u00adpyridine 2, 2  and xylene (10\u2005ml) was refluxed (433\u2005K) for 48\u2005h under an N2 flow. The xylene was removed by distillation and the crude product was purified by silica gel column chromatography  to give the title compound as a yellow solid in 40% yield. Orange\u2013red crystals suitable for X-ray crystallography analysis were obtained from a CH2Cl2/hexane solution by slow evaporation. 1H NMR  \u03b4 9.91 , 8.20, 7.97 , 7.90\u20137.84 , 7.50\u20137.42 , 7.30\u20137.22 , 7.06 , 6.97-6.91 . 13C NMR  \u03b4 206.5, 167.3, 156.4, 155.9, 151.0, 148.1, 146.6, 146.5, 140.1, 139.0, 125.7, 125.0, 121.0, 118.4, 118.3, 117.6, 115.9, 106.0, 105.9, 105.7, 105.6. Analysis calculated for C21H12ClF2N3OPt: C 42.69; H 2.05; N 7.11%; found: C 42.70, H 2.06, N 7.09%.The title compound was synthesized as follows: A mixture of the ligand , PtClUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021000128/hb7960sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989021000128/hb7960Isup2.hklStructure factors: contains datablock(s) I. DOI: 2053861CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-019-47062-2, published online 22 July 2019Correction to: This Article contains errors in the Results section where,\u201cIt was noted that the vessel diameter of the untreated veins was (on average?) 132% higher than that of the treated veins , indicating that the treated veins were thinner.\u201dshould read:\u201cIt was noted that the vessel diameter of the untreated veins was 132% higher than that of the treated veins , indicating that the treated veins were thinner.\u201d\u201cAdditionally, the (average?) RNV vessel diameter was estimated to be 29.83\u2009\u00b1\u20094.17\u2009\u00b5m, which was 97.77% thinner than choroidal vessels (59.00\u2009\u00b1\u200911.47\u2009\u00b5m), p\u2009<\u20090.05.\u201dshould read:\u201cAdditionally, the RNV vessel diameter was estimated to be 29.83\u2009\u00b1\u20094.17\u2009\u00b5m, which was 97.77% thinner than choroidal vessels (59.00\u2009\u00b1\u200911.47\u2009\u00b5m), p\u2009<\u20090.05.\u201d"}
{"text": "II ion is coordinated in a distorted octa\u00adhedral [FeN4O2] environment by two di\u00adcyano\u00adaurate anions, two water mol\u00adecules and two partially protonated 1,2-di(4-pyrid\u00adyl)ethyl\u00adene mol\u00adecules. Di\u00adcyano\u00adaurate anions bridge the FeII cations, forming infinite chains, which propagate along the a-axis direction. The chains are connected via aurophillic inter\u00adactions with two non-coordinated di\u00adcyano\u00adaurate anions for each FeII ion.In the title compound, the Fe 2][Au(CN)2]2\u00b7bpe\u00b72H2O}n , the FeII ion is coordinated in a distorted octa\u00adhedral [FeN4O2] environment by two di\u00adcyano\u00adaurate anions, two water mol\u00adecules and two partially protonated 1,2-di(4-pyrid\u00adyl)ethyl\u00adene mol\u00adecules. Di\u00adcyano\u00adaurate anions bridge the FeII cations, forming infinite chains, which propagate along the a-axis direction. The chains are connected via aurophilic inter\u00adactions with two non-coordinated di\u00adcyano\u00adaurate anions for each FeII ion. The polymeric chains inter\u00adact with each other via \u03c0\u2013\u03c0 stacking between the guest bpe mol\u00adecules and multiple hydrogen bonds.In the title compound [Fe(bpe)(Hbpe)Au(CN) These layers are supported by N-donor aromatic ligands . Di-, tetra- and octa\u00adcyano\u00admetallic  anions have been introduced to develop coordination compounds of this kind. It has been shown that the inclusion of guest mol\u00adecules can significantly influence the temperature, completeness and step character of spin transition in complexes belonging to this class (Hbpe)Au(CN)2](Au(CN)2)2\u00b7bpe\u00b72H2O in which the FeII ions are stabilized in the high-spin (HS) state.Here we describe the crystal structure of a new cyano\u00admetallic FeP4O2] octa\u00adhedral environment \u2005\u00c5, N5\u2014H5A\u22efN5i = 176\u00b0; Table\u00a01The title compound crystallizes in the triclinic nt Fig.\u00a01 formed bII coordination environment is \u03a3|90\u00a0\u2212\u00a0 \u03b8| = 6.8\u00b0, where \u03b8 are cis-N\u2014Fe\u2014N or cis-N\u2014Fe\u2014O angles. Two CN\u2212 anions bridge the Fe2+ and Au+ cations [Fe1\u22efAu1 = 5.280\u2005(3)\u2005\u00c5], creating a one-dimensional polymer, Fe1\u2014N1\u2014C1 = 172.8\u2005(7)\u00b0, N1\u2014C1\u2014Au1 = 179.1\u2005(8)\u00b0 and C1\u2014Au1\u2014C1 = 180.0\u00b0, leading to a very slight deviation from linearity of the chains. This chain binds one guest bpe and two guest water mol\u00adecules per FeII centre.The deviation from the ideal octa\u00adhedral geometry of the Fe2]\u2212 counter-ions are connected with the polymeric chains by aurophilic inter\u00adactions and C7\u22efN2B hydrogen bonds . These free counter-ions are disordered over two positions with Au1\u2014Au2A = 3.324\u2005(1)\u2005\u00c5 and Au1\u2014Au2B = 3.101\u2005(5)\u2005\u00c5. The polymeric chains are connected to each other via \u03c0\u2013\u03c0 inter\u00adactions \u2005\u00c5, \u03b1 = 10.3\u00b0, offset = 1.043\u2005\u00c5, where Cg1 and Cg2 are the centroids of the N4/C4\u2013C8 and N6/C16\u2013C20 rings, respectively, and Cg3\u22efCg4 = 3.794\u2005(6)\u2005\u00c5, \u03b1 = 6.8\u00b0, offset = 1.835\u2005\u00c5, where Cg3 and Cg4 are the centroids of N5/C11\u2013C15 and N6ii/ Cii16\u2013C20 rings, respectively]. Guest bpe mol\u00adecules are additionally linked to the polymeric chains by hydrogen bonds with coordinated water mol\u00adecules . One of the guest water mol\u00adecules forms hydrogen bonds with the coord\u00adinated water [Fig.\u00a03A\u22efO2 = 156\u00b0] and weak hydrogen bonds with free di\u00adcyano\u00adaurate counter-ions  and free di\u00adcyano\u00adaurate counter-ions . Hydrogen-bonding parameters are summarized in Table\u00a01The structure is characterized by the presence of several different kinds of weak inter\u00adactions that create a three-dimensional supra\u00admolecular framework. Two free  \u00adbis\u00ad(2-phenyl\u00adpyrazine)\u00adbis\u00ad(aqua)\u00adiron(II)gold(I) bis\u00ad(cyano)\u00adgold(I)]  in water (0.5\u2005ml), the second was a mixture of water/ethanol  and the third layer was a solution of 1,2-di(4-pyrid\u00adyl)ethyl\u00adene (0.05\u2005mmol) and [Fe(OTs)2]\u00b76H2O  in ethanol (0.5\u2005ml) with 0.2\u2005ml of water. After two weeks, red crystals grew in the second layer; the crystals were collected and kept in the mother solution prior to measurement.Crystals of the title compound were prepared by the slow diffusion method between three layers in a 3\u2005ml tube. The first layer was a solution of K[Au(CN)iUso(H) = 1.2Uiso(C), Uiso(H) = 1.2Uiso(N), Uiso(H) = 1.5Uiso(O). Uaniso values for all C and N atoms in the guest di\u00adcyano\u00adaurate anions and the O2 and O3 water mol\u00adecules were constrained to be equal using the EADP command. Distances N3A\u2014C3A and N2A\u2014C2A were restrained to a target of 1.15\u2005\u00c5 and distances Au2A\u2014C3A and Au2A\u2014C2A were restrained to a target of 1.99\u2005\u00c5 using the DFIX command. The following distances were restrained to be equal using the SADI command: C2A\u2014N2A and C2B\u2014N2B; Au1\u2014C2A and Au1\u2014C2B; C3A\u2014N3A and C3B\u2014N3B; Au1\u2014C3A and Au1\u2014C3B; C2A\u2014C3A and C2B\u2014C3B.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020006738/tx2022sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020006738/tx2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 2004716CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the mean plane of the anthra\u00adquinone ring system and the dioxepine ring in the title compound is 16.29\u2005(8)\u00b0. The packing is consolidated by C\u2014H\u22efO, \u03c0\u2013\u03c0 and C=O\u22ef\u03c0 inter\u00adactions. 17H12O4, was synthesized from the dye alizarin. The dihedral angle between the mean plane of the anthra\u00adquinone ring system (r.m.s. deviation = 0.039\u2005\u00c5) and the dioxepine ring is 16.29\u2005(8)\u00b0. In the crystal, the mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming sheets lying parallel to the ab plane. The sheets are connected through \u03c0\u2013\u03c0 and C=O\u22ef\u03c0 inter\u00adactions to generate a three-dimensional supra\u00admolecular network. Hirshfeld surface analysis was used to investigate inter\u00admolecular inter\u00adactions in the solid-state: the most important contributions are from H\u22efH (43.0%), H\u22efO/O\u22efH (27%), H\u22efC/C\u22efH (13.8%) and C\u22efC (12.4%) contacts.The title compound, C The colour of anthra\u00adquinone-based compounds can be modified by the type and position of the substituents attached to the anthra\u00adquinone nucleus P21/n with one mol\u00adecule in the asymmetric unit: it consists of three fused six-membered rings and one seven-membered ring as shown in Fig.\u00a01Compound (I)q2 = 0.896\u2005(2)\u2005\u00c5, \u03c62 = 113.50\u2005(12)\u00b0, q3 = 0.358\u2005(2)\u2005\u00c5, and \u03c63 = 217.8\u2005(3)\u00b0. These metrics indicate that the ring adopts a screw boat conformation. The C\u2014O and C=O bond lengths lie within the ranges 1.355\u2005(2)\u20131.457\u2005(2)\u2005\u00c5 and 1.216\u2005(2)\u20131.226\u2005(2)\u2005\u00c5, respectively, confirming their single and double-bond character.A puckering analysis of the seven-membered ring yielded the parameters B\u22efO1 hydrogen bonds form inversion dimers with an A\u22efO3 contacts, thereby generating corrugated chains of mol\u00adecules . A C17\u2014H17B\u22efO2 hydrogen bond links the chains together (Table\u00a01b and 2c), forming sheets propagating in the ab plane. These sheets are supported by extensive \u03c0\u2013\u03c0 contacts between adjacent rings, with centroid-to-centroid distances Cg1\u22efCg2 = 3.599\u2005(2) and Cg2\u22efCg3 = 3.683\u2005(2)\u2005\u00c5  and weak C12=O1\u22ef\u03c0 [oxygen\u2013centroid distance = 3.734\u2005(2)\u2005\u00c5] inter\u00adactions es Fig.\u00a02a. A C17r Table\u00a01b and 2cns Fig.\u00a03, linkinget al., 2016viz. 1-hy\u00addroxy-2-meth\u00adoxy-6-methyl  and two-dimensional fingerprint plots  shows the mol\u00adecular electrostatic potential surface generated using TONTO with a STO-3G basis set in the range \u22120.050 to 0.050 a.u. within the Hartree\u2013Fock level of theory. Mol\u00adecular sites evidenced in red correspond to positive potential energy and in blue to negative potential energy de and di diagonal axes. The most important inter\u00adaction is H\u22efH, contributing 43% to the overall crystal packing, which is reflected in Fig.\u00a05b as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule, with small split tips at de \u2243 di \u2243 1.2\u2005\u00c5. The contribution from the O\u22efH/H\u22efO contacts (27%) [note that the O\u22efH interactions make a larger contribution (14.6%) than the H\u22efO interactions (12.4%)], corresponding to C\u2014H\u22efO inter\u00adactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter\u00adaction, de + di \u2243 2.35\u2005\u00c5 . The significant contribution from C\u22efH/H\u22efC contacts (13.8%) to the Hirshfeld surface of (I)d, with de + di \u22432.55\u2005\u00c5. The distribution of points in the de = di \u2243 1.75\u2005\u00c5 range in the fingerprint plot delineated into C\u22efC contacts indicates the existence of weak \u03c0\u2013\u03c0 stacking inter\u00adactions between the central anthracene ring and the C6\u2013C11 and C1\u2013C4/C13\u2013C14 rings . Aromatic \u03c0\u2013\u03c0 inter\u00adactions are indicated by adjacent red and blue triangles in the shape-index map and also by the flat region around these rings in the Hirshfeld surfaces mapped over curvedness in Fig. S1c.As illustrated in Fig.\u00a05\u2005\u00c5 Fig.\u00a05c. The sgs Fig.\u00a04b and 5ede + di \u2243 3.2\u2005\u00c5 in Fig.\u00a05f.The contribution of 3.2% from C\u22efO/O\u22efC contacts is due to the presence of short inter\u00adatomic C=O\u22ef\u03c0 contacts, and is apparent as the pair of parabolic tips at N hydro\u00adchloric acid, extracted with chloro\u00adform (3 \u00d7 30\u2005ml) and then chromatographed on a silica gel column with di\u00adchloro\u00admethane/petroleum ether (1/1) as eluent, which yielded 200\u2005mg (35%) of 1,2-propyl\u00adene\u00addioxy\u00adanthra\u00adquinone as a yellow compound  was treated with 1,3-di\u00adbromo-propane  in di\u00admethyl\u00adformamide (30\u2005ml) in the presence of anhydrous potassium carbonate  with stirring and heated to 393\u2005K for 24\u2005h. The reaction mixture was evaporated to dryness under vacuum and the resulting crude product was acidified with 12\u2005nd Fig.\u00a06. Colourl1H NMR : \u03b4 (ppm): 8.21 , 7.95 , 7.72 , 7.26 , 4.48 , 4.43 , 2.34 ; 13C NMR : \u03b4 (ppm): 182.9, 182.5, 157.3, 151.3, 135.2, 133.9, 133.4, 132.6, 129.6, 127.1, 126.5, 126.0, 125.9, 123.3, 70.5, 70.2, 30.0. Analysis calculated for C17H12O4: C, 72.85%; H, 4.32%; found: C, 72.82%; H, 4.29%.Uiso(H) = 1.2Ueq(C). The reflection (011), affected by the beam-stop, was removed during refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020003965/hb7899sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020003965/hb7899Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003965/hb7899Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020003965/hb7899sup4.docxSupplementary figures: Hirshfeld surface analysis. DOI: 1991271CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the title compound, the packing is driven by O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efN hydrogen-bond inter\u00adactions along with \u03c0\u2013\u03c0 stacking inter\u00adactions. 10H8N8\u00b72H2O or H2bmtz\u00b72H2O , the asymmetric unit consists of one-half mol\u00adecule of H2bmtz and one water mol\u00adecule, the whole H2bmtz mol\u00adecule being generated by a crystallographic twofold rotation axis passing through the middle point of the 1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine moiety. In the crystal, N\u2014H\u22efO, N\u2014H\u22efN, O\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions link the components into a three-dimensional supra\u00admolecular network. Hirshfeld surface analysis was used to further investigate the inter\u00admolecular inter\u00adactions in the crystal structure.In the title compound, C Many compounds of this class are bioactive (Jubeen I) is shown in Fig.\u00a012bmtz and one water mol\u00adecule, in which the whole mol\u00adecule of the H2bmtz is generated by a crystallographic twofold rotation axis passing through the middle point of the 1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine moiety. The H2bmtz mol\u00adecule is therefore not planar (r.m.s. deviation from planarity = 0.598\u2005\u00c5) with a C4\u2014C5\u2014N3\u2014N4i torsion angle of 178.46\u2005(14)\u00b0 . The pyrimidine rings are twisted with respect to each other, making a dihedral angle of 43.67\u2005(9)\u00b0. The 1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine moiety adopts a twist-boat conformation with a C5\u2014N3\u2014N4i\u2014C5i torsion angle of \u221241.17\u2005(17)\u00b0. The N3\u2014N4i and C5\u2014N4 bond lengths of 1.423\u2005(2) and 1.395\u2005(2)\u2005\u00c5, confirm their single-bond character, while the C3\u2014N5 bond length of 1.278\u2005(2)\u2005\u00c5, is consistent with a double bond \u2005\u00c5]. At the same time, the water mol\u00adecules are connected by O\u2014H\u22efO hydrogen bonds  make a less significant contribution. The contribution of the H\u22efO/O\u22efH (9.0%) contacts (i.e. C\u2014H\u22efO and O\u2014H\u22efO) and other contacts such as C\u22efC (7.1%) (i.e. \u03c0\u2013\u03c0 stacking), H\u22efC/C\u22efH (6.1%) and N\u22efN (4.7%) make a small contribution to the entire Hirshfeld surface.To further qu\u00adantify the nature of the inter\u00admolecular inter\u00adactions present in the crystal structure, Hirshfeld surfaces -1,2,4,5-tetra\u00adzine]bis\u00ad[bis\u00ad(tri\u00adphenyl\u00adphosphine)cop\u00adper(I)] bis\u00ad(tetra\u00adfluorido\u00adborate) di\u00adchloro\u00admethane solvate -1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine][\u03bc2-(di\u00adcyano\u00adethen\u00adyl\u00ad\u00adidene)amido][(di\u00adcyano\u00adethenyl\u00adidene)amido]\u00adaceto\u00adnitrile\u00addisilver(I)] .All commercially available chemicals and solvents were of reagent grade and were used as received without further purification. HUiso(H) = 1.2Ueq(C). The 1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine and water H atoms were located in difference-Fourier maps and were constrained to N\u2014H = 0.86 \u00b1 0.01\u2005\u00c5 with Uiso(H) = 1.2Ueq(N) and O\u2014H = 0.84 \u00b1 0.01\u2005\u00c5 with Uiso(H) = 1.5Ueq(O), respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020002765/hb7895sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020002765/hb7895Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002765/hb7895Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002765/hb7895Isup4.cmlSupporting information file. DOI: 1986751CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound contains two independent mol\u00adecules, consisting of perimidine and phenol units, which are linked through an N\u2014H\u22efO hydrogen bond. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds are observed in both independent mol\u00adecules. 17H14N2O, contains two independent mol\u00adecules each consisting of perimidine and phenol units. The tricyclic perimidine units contain naphthalene ring systems and non-planar C4N2 rings adopting envelope conformations with the C atoms of the NCN groups hinged by 44.11\u2005(7) and 48.50\u2005(6)\u00b0 with respect to the best planes of the other five atoms. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds may help to consolidate the mol\u00adecular conformations. The two independent mol\u00adecules are linked through an N\u2014H\u22efO hydrogen bond. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (52.9%) and H\u22efC/C\u22efH (39.5%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The asymmetric unit of the title compound, C H Perimidines are defined as peri-naphtho-fused pyrimidines , carried out at the B3LYP/6-311G  level, are compared with the experimentally determined mol\u00adecular structure in the solid state.I, contains two crystallographically independent mol\u00adecules each consisting of perimidine and phenol units, where the tricyclic perimidine units contain naphthalene ring systems and non-planar C4N2 rings  and B\u2032 (N1A/N2A/C1A/C9B\u2013C11B) rings gave the parameters q2 = 0.9280\u2005(12)\u2005\u00c5, q3 = 0.1829\u2005(12)\u2005\u00c5, QT = 0.9459\u2005(13)\u2005\u00c5, \u03b82 = 75.85\u2005(15)\u00b0 and \u03c6 2= 134.47\u2005(18)\u00b0 for B and q2 = 0.5320\u2005(11)\u2005\u00c5, q3 = 0.3791\u2005(11)\u2005\u00c5, QT = 0.6533\u2005(14)\u2005\u00c5, \u03b82 = 54.33\u2005(12)\u00b0 and \u03c6 2= \u22125.47\u2005(13)\u00b0 for B\u2032; both rings adopt envelope conformations, where atoms C1A and C1B are at the flap positions and at distances of 0.6044\u2005(12) and \u22120.6590\u2005(13)\u2005\u00c5, respectively, from the best planes through the other five atoms. The C4N2 rings may alternatively be described as being hinged about the N\u22efN vectors with the N1A/C1A/N2A and N1B/C1B/N2B planes being inclined by 44.11\u2005(7) and 48.50\u2005(6)\u00b0, respectively, to the best planes through the other five atoms (N1A/N2A/C9A\u2013C11A) and (N1B/N2B/C9B\u2013C11B). Rings A (C2A\u2013C7A), C (C10A\u2013C15A), D (C9A/C10A/C15A\u2013C18A) and A\u2032 (C2B\u2013C7B), C\u2032 (C10B\u2013C15B), D\u2032 (C9B/C10B/C15B\u2013C18B) are oriented at dihedral angles of A/C = 76.78\u2005(4), A/D = 78.49\u2005(4), C/D = 2.09\u2005(3)\u00b0 and A\u2032/C\u2032 = 88.43\u2005(3), A\u2032/D\u2032 = 88.31\u2005(3), C\u2032/D\u2032 = 3.26\u2005(4)\u00b0. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds  analysis  have the tips at de + di = 2.50\u2005\u00c5. The scattered points in the pair of spikes in the fingerprint plot delineated into H\u22efO/O\u22efH  have a symmetrical distribution with the tips at de + di = 2.49\u2005\u00c5. The H\u22efN/N\u22efH contacts  have a distribution of points with the tips at de + di = 2.72\u2005\u00c5. Finally, the C\u22efC inter\u00adactions  are reflected in Fig.\u00a04f as low density wings with the tips at de + di = 3.60\u2005\u00c5.The shape-index of the HS is a tool to visualize the \u03c0\u2013\u03c0 stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no \u03c0\u2013\u03c0 inter\u00adactions. Fig.\u00a03dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions in Fig.\u00a05a\u2013c, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are recorded in Table\u00a03\u03c3 is for the evaluation of both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig.\u00a06H-perimidin-2-yl)phenol ring. The energy band gap [\u0394E = ELUMO - EHOMO] of the mol\u00adecule is 1.4933\u2005eV, the frontier mol\u00adecular orbital energies EHOMO and ELUMO being \u22123.2606 and \u22121.7673\u2005eV, respectively.The optimized structure of the title compound, I, are II phenol product (Rf = 0.70 in hexa\u00adne/ethyl acetate (1:0.5), yield: 97% A significant qu\u00adantity of the colourless monocrystalline product was obtained by the slow evaporation of the solvent after 15 days.0.35\u2005mol (1.48\u2005g) of 1,8-di\u00adaminona\u00adphthalene and 18.8\u2005mmol (2\u2005ml) of salicyl\u00adaldehyde were introduced into a 250\u2005ml flask and 30\u2005ml of ether were added thereto. The mixture was stirred magnetically for 3 days. The grey precipitate that formed was recovered by filtration, washed with ether, rinsed with ethanol and dried under B\u00fcchner. The resulting brownish powder was recrystallized several times from ethanol to obtain colourless 2- = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in are summarized in Table\u00a0410.1107/S2056989020005939/lh5957sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005939/lh5957Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020005939/lh5957Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020005939/lh5957Isup4.cmlSupporting information file. DOI: 1976884CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The metalated species were characterized in situ by NMR spectroscopy and in two cases isolated as crystalline solids. Single\u2010crystal XRD studies revealed the presence of salt\u2010like structures with strongly interacting ions. Synthetic applications of K[(R2N)2P(BH3)] were studied in reactions with a 1,2\u2010dichlorodisilane and CS2, which afforded either mono\u2010 or difunctional phosphine boranes with a rare combination of electronegative amino and electropositive functional disilanyl groups on phosphorus, or a phosphinodithioformate. Spectroscopic studies gave a first hint that removal of the borane fragment may be feasible.Metalation of secondary diaminophosphine boranes by alkali metal amides provides a robust and selective access route to a range of metal diaminophosphide boranes M[(R It\u2032s just so plain borane: Alkali metal diaminophosphide boranes, which can be selectively prepared by metalation of PH\u2010substituted precursors with non\u2010nucleophilic amides, were for the first time isolated and characterized crystallographically. Their synthetic application as highly functional nucleophilic building blocks is illustrated in metatheses with a dichlorodisilane and the formation of a stable carbon disulfide adduct. I or diorganophosphide boranes II ,Ib,c/IIb,c)3Si, IdIb/IIb) parent (Ic/IIc) and silylated phosphides (Id) are special because their ability to undergo electrophilic post\u2010functionalization of reactive P\u2212H and P\u2212Si bonds after the initial metathesis step makes them essentially polyfunctional building blocks.Typical phosphide reagents carry usually chemically inert alkyls or aryls 2P(Fe(CO)4]KIII, R=Et, Ph) and [(Me2N)(Ph3C)P(W(CO)5]KIV) containing metal\u2010stabilized mono\u2010 or diamino\u2010phosphido ligands were generated as spectroscopically detectable entities by deprotonation of PH\u2010substituted precursor complexes and shown to react as P\u2010centered nucleophiles. The significance of diaminophosphide boranes as synthetic intermediates was first recognized by the group of Knochel,1\u2009a] that had been generated in situ by lithium reduction of a chlorophosphine borane precursor but was neither positively identified nor further characterized (Scheme\u20051\u2009a]) and lithium diethylaminophosphide borane (Li[1\u2009a]) can be alternatively accessed through metalation of a secondary diaminophosphine borane precursor 2PCl and LiBH42N)2PCl with Me2S\u22c5BH3  furnished only inseparable mixtures of 2\u2009b with Me2NH\u22c5BH3 (10\u201320\u2005mol\u2009%). As the by\u2010product did not interfere with the subsequent metalation reactions, the mixtures were used without further purification. Reactions aiming at the generation of phosphides were carried out in THF, diethyl ether, or mixtures thereof, and reaction monitoring and product identification was generally achieved in situ by multinuclear  NMR spectroscopy. We found that reliable and highly selective generation  of phosphide boranes M[1\u2009b\u2013f] was feasible by treating the PH\u2010substituted precursors 2\u2009b\u2013e with a slight excess of a non\u2010nucleophilic alkali amide such as lithium di(isopropyl)amide (LDA) or a metal hexamethyldisilazide (MHMDS=MN(SiMe3)2, M=Li, Na, K, Scheme\u20052\u2009b with NaHDMS in a THF/ether mixture and with KHMDS in the presence of a crown ether permitted also the isolation of first crystalline diaminophosphide boranes of composition Na[1\u2009b]\u22c5THF and K[1\u2009b] , respectively. Both products were characterized by single\u2010crystal X\u2010ray diffraction studies (see further below).To deepen our insight into the formation of diaminophosphide boranes, we tested the routes reported for accessing Li[1\u2009c] and heterocyclic derivatives like K[1\u2009d], K[1\u2009e], while selective lithiation of heterocyclic secondary diaminophosphine borane 2\u2009e was best accomplished with LDA. Metalation of the secondary diazaphospholene borane 2\u2009f turned out a borderline case. Treatment with KHMDS produced detectable amounts of the expected, highly moisture and air sensitive phosphide K[1\u2009f], which was identified by spectroscopic data and chemical trapping with a proton source. However, both deprotonation and recovery of the secondary phosphine borane were in this case unselective and produced side\u2010products that could neither be successfully identified nor separated. We relate the difficulties encountered in the generation of K[1\u2009f] to the unusual electronic structure of unprotected secondary diazaphospholenes, which display a hydride reactivity that contrasts the behavior of alkyl and arylphosphines and is associated with an \u201cUmpolung\u201d of the P\u2212H bond.Moreover, using KHMDS for deprotonation enabled both the generation of a sterically congested diaminophosphide reagent like K,1\u2009c] but proceeded unselectively and irreproducibly with heterocyclic substrates. The use of Grignard reagents was tested with sterically uncongested diaminophosphine boranes 2\u2009a,b. While MeMgCl converted both substrates cleanly into the corresponding phosphides, EtMgBr was found to be unreactive.Application of other deprotonating reagents than amides gave erratic results. Metalation with 3\u2009a,b3\u2009b, which afforded a low yield of the metalation product K[1\u2009b] along with a main product later identified4\u2009b  4\u2009b and substantial amounts of unidentified by\u2010products. We have currently no concise explanation for the varying selectivity, even if it is tempting to relate the observed changes to different sterics of the substrates.Exploring the reduction of chlorophosphine boranes 1\u2009b\u2013f] comes from 31P and 11B\u2005NMR spectra. The signals display the expected multiplet structures arising from spin\u2010coupling between 11B (I=3/2) and 31P (I=1/2) nuclei and lack a characteristic splitting due to 1JPH coupling across a P\u2212H bond. As previously noted1\u2009a] and K[1\u2009a], the 31P\u2005NMR chemical shifts of specimens with identical diaminophosphide units show metal\u2010dependent changes, and the presence of a cation sequestering reagent like dibenzo\u201018\u2010crown\u20106 induces increases in \u03b431P of potassium phosphide boranes K by 10 to 15\u2005ppm. Both effects suggest the presence of tight contact ion pairs in solution. The non\u2010uniform trends observed  discredit a simplistic assumption that declining covalency in the phosphorus\u2010metal bonding with growing size of the metal ion induces a deshielding of the 31P nucleus. The 11B\u2005NMR signals of M[1\u2009a\u2013f] display positive \u201cmetalation shifts\u201d (\u0394\u03b411B +5 to +11\u2005ppm) and numerically reduced 1JP11B coupling constants relative to the corresponding secondary phosphine borane precursors 2\u2009a\u2013f. The same trends hold for dialkyl and diarylphosphide boranes  and an unusually low shift for sterically congested M[1\u2009c] . A concise explanation for these effects is yet lacking.The diagnostically most valuable information for the identification of metalated diaminophosphide boranes M[ 11B I=3/ and 31P  11B I=3/ and 31P 1\u2009b] (space group P1\u203e) and monoclinic K[1\u2009b] (space group P21/c) and important metrical parameters are displayed in Figures\u2005Graphical representations of the results of single\u2010crystal X\u2010ray diffraction studies on triclinic Na(THF)\u2009b (space1\u2009b] contain dimeric units assembled from two anionic diaminophosphide borane and two cationic Na(THF) fragments  to 2.39(2)\u2005\u00c5) and a weaker contact to a B\u2212H bond of the adjacent borane in the same unit (Na\u2010H 2.69(2)\u2005\u00c5). Interactions of this type have precedence in the structures of alkyl/arylphosphide boranes[1\u2009b] the dimeric units to form one\u2010dimensionally infinite strands aligned parallel to the crystallographic a\u2010axis. If we count the \u03b72\u2010bound borane as one ligand, the metal ions exhibit an irregular pseudo\u2010[4+1] coordination geometry in which the weak \u201cintramolecular\u201d B\u2212H interaction is aligned roughly opposite to the oxygen atom of the THF ligand. The phosphorus atom displays a distorted tetrahedral coordination with bond angles from 103.1(1)\u00b0 (N1\u2212P1\u2212B1) to 118.8(1)\u00b0 (Na1\u2212P1\u2212B1). The P\u2212B and P\u2212N distances are in the range of single bonds, with the deviation of 0.053(2)\u2005\u00c5 between the P\u2212N distances reflecting the different coordination numbers of the nitrogen atoms. While the Na1\u2212O1 distance of 2.311(1)\u2005\u00c5 is a close match to the sum of covalent radii (2.32(11)\u2005\u00c5Crystals of Na(THF)\u2009b contaie boranes15, 171\u2009b] contains two independent anionic units and two cations which aggregate, as in the sodium analogue, via K\u22c5\u22c5\u22c5N and K\u22c5\u22c5\u22c5P interactions to form strongly puckered six\u2010membered cyclic arrays . The coordination sphere of the linking metal ion is completed by additional contacts to a \u03b73\u2010bound borane unit (H\u22c5\u22c5\u22c5K2 2.645(27) to 2.762(31)\u2005\u00c5) from the second next dimeric unit in the row, which reinforce the supramolecular assembly and give rise to the formation of a double stranded array of heterocyclic units extending along the crystallographic b\u2010axis. Completion of the coordination sphere of the N2\u2010coordinated potassium ion is accomplished by weaker BH\u22c5\u22c5\u22c5K interactions (H\u22c5\u22c5\u22c5K1 2.69(3) to 3.04(3)\u2005\u00c5) with borane units from adjacent, parallel strands. These secondary interactions result ultimately in the formation of two\u2010dimensional layers, which extend in the crystallographic a,b\u2010plane and are held together by van\u2010der\u2010Waals interactions. The P\u2212N (1.697(2) to 1.741(2)\u2005\u00c5) and P\u2212B distances (1.935(4), 1.947(3)\u2005\u00c5 are similar as in Na(THF)[1\u2009b] and correspond to single bonds. The P\u22c5\u22c5\u22c5K (3.301(1), 3.352(1)\u2005\u00c5) and N\u22c5\u22c5\u22c5K distances (2.849(2) to 2.961(2)\u2005\u00c5) exceed the reported sum of covalent radii (P\u2212K 3.10(15), N\u2212K 2.74(13)\u2005\u00c5Crystalline K and K[1\u2009e] afforded exclusively monosubstitution products , even when the nucleophile was employed in excess  or crystalline solids  and characterized by analytical and spectroscopic data. The 1H, 11B, 13C and 31P\u2005NMR spectra are unremarkable and confirm the proposed constitution. The 29Si NMR spectrum of 7 is peculiar as the expected multiplet (representing the X\u2010part of an ABX spin system) degenerates accidentally to a simple doublet. One of the two expected 29Si NMR signals of 6\u2009e stayed undetected for unknown reasons.To explore the feasibility of this approach, we studied reactions of diaminophosphide boranes with commercially available 1,2\u2010dichloro\u20101,1,2,2\u2010tetramethyldisilane s Scheme\u2005. In cont6\u2009e and 7 were further confirmed by single\u2010crystal X\u2010ray diffraction studies. Crystals of 7 \u00b0 and 180\u00b0, Figures\u20056\u2009e holds likewise two independent molecules, both of which exhibit, however, a nearly eclipsed conformation around the Si\u2212Si bond. The chlorine and phosphorus atoms in one molecule adopt a gauche\u2010orientation . The N\u2010heterocyclic rings exhibit similar twist conformations as in borane\u2010free diazaphospholidines7 are unremarkable and suggest the presence of normal single bonds. The P\u2212N distances in both complexes are shorter than in free acyclic or N\u2010heterocyclic phosphines,octane (DABCO).11B\u2005NMR spectroscopy as the expected bis\u2010borane adduct of DABCO  which lacks the characteristic broadening arising from spin\u2010coupling to a quadrupolar 11B nucleus and is tentatively assigned to the targeted borane\u2010free diphosphino\u2010disilane. In addition, signals attributable to unknown borane\u2010free phosphorus\u2010containing species  and bis(diethylamino)phosphine  were detected, and the 11B\u2005NMR spectrum revealed further the presence of residual 7 . The product distribution observed can be explained by assuming that de\u2010protection is in principle feasible but remains incomplete and is accompanied by P\u2212Si bond cleavage arising from adventitious hydrolysis. Attempts to isolate any of the de\u2010protected phosphorus\u2010containing products remained unsuccessful.The 1,2\u2010diphosphino\u2010disilane representing the backbone of 1\u2009a] with carbon dioxide and carbon disulfide. While the former gave rise to an intractable colorless solid that could as yet not be unambiguously characterized, the reaction with CS2 proceeded cleanly to afford a soluble species which was isolated as a red, air and moisture stable crystalline solid after work\u2010up and recrystallization from ether/pentane. Analytical and MS data are in accordance with the formation of phosphinodithioformate borane 8  to 3.435(2)\u2005\u00c5, K\u22c5\u22c5\u22c5O (2.820(2)\u2005\u00c5), and weaker contacts to a remote sulfur and two hydrogen atoms of a \u03b72\u2010coordinated borane unit (K\u22c5\u22c5\u22c5S 3.806(2)\u2005\u00c5, K\u22c5\u22c5\u22c5H 2.62(6), 2.85(6)\u2005\u00c5). The anion is built around a phosphorus atom with distorted tetrahedral and a carbon atom with planar coordination. The P\u2212N (1.653(4), 1.663(3)\u2005\u00c5) and P\u2212B (1.915(6)\u2005\u00c5) distances are still shorter than in 6\u2009e, 7 but remain in the range of single bonds. The P\u2212C (1.849(4)\u2005\u00c5) and C\u2212S (1.680(54), 1.687(4)\u2005\u00c5) distances match those reported for zwitterionic triaminophosphonio dithioformates (R2N)3P+\u2013CS2\u2212 (P\u2212C 1.848(4), 1.849(2)\u2005\u00c5; C\u2212S 1.651(4) to 1.675(3)\u2005\u00c52N)3P+\u2013CS2Me (P\u2212C 1.852(5)\u2005\u00c52N)2P\u2013CS2\u2013P(NR2)2 containing a tri\u2010coordinate P atom (P\u2212C 1.895(4)\u2005\u00c52 fragment are rather insensitive to the nature of the P substituents.Considering all interactions together, the potassium ions can be assigned a [5+3] coordination sphere arising from close contacts to the sulfur atoms of two \u03bcIn this work, we established the metalation of secondary diaminophosphine boranes with alkali metal amides as broadly applicable and robust access route to nucleophilic diaminophosphide building blocks based on both acyclic and N\u2010heterocyclic molecular frameworks. Hexamethyldisilazides emerged as reagents of choice because of their ability to react as universally applicable bases which allow free selection of alkali metals. Alternative approaches to the target molecules, such as metalation of the diaminophosphine boranes with organometallic reagents or reductive metalation of P\u2010chloro\u2010substituted precursors, worked well in selected cases but gave generally erratic results. Moreover, borane complexes of diazaphospholenes materialized as critical substrates, which reacted unselectively to afford low yields of spectroscopically detectable metalation products beside unidentified by\u2010products. We presume that this behavior reflects the pertinent hydride character of the P\u2212H bonds in the free phosphines.Beyond previous findings, sodium and potassium dimethylaminosphosphide boranes were for the first time isolated as room\u2010temperature\u2010stable solids. Their crystallographic characterization reveals the presence of salt\u2010like structures that are distinguished by intimate interactions between ions of opposite charge via a combination of dative M\u22c5\u22c5\u22c5N and M\u22c5\u22c5\u22c5P and agostic M\u22c5\u22c5\u22c5H\u2212B contacts. While both types of interactions are not unprecedented for aryl and alkyl phosphide boranes, the availability of additional nitrogen donor centers increases the density of the interaction network.Last, but not least, the potential of diaminophosphide boranes to act as synthetic building blocks is illustrated by their conversion into phosphine boranes that are distinguished by a combination of electronegative amino and electropositive functional silyl groups. Initial studies indicate that removal of the borane units is in principle feasible, and we are currently striving to develop reliable synthetic protocols to accomplish this task.2O, toluene) or by using a solvent purification system . NMR spectra were recorded on Bruker Avance 250 or Avance 400 instruments. Chemical shifts in 1H\u2005NMR spectra were referenced to TMS using the residual signals of the deuterated solvent =1.73\u2005ppm; \u03b4(C6D6)=7.15\u2005ppm) as secondary reference. NMR Spectra of heteronuclei were referenced using the \u039e\u2010scale\u039e=25.145020\u2005MHz, 13C; \u039e=19.867187\u2005MHz, 29Si), BF3Et2O  and 85\u2009% H3PO4  as secondary references. Coupling constants involving boron refer to 11B isotopomers, with 1:1:1:1 multiplets being denoted as q. The product composition in metalation experiments was derived from analysis of the 1H\u2005NMR signals of the N\u2010substituents of 1\u2009b\u2013f. Elemental analyses were carried out with an Elementar Micro Cube elemental analyzer. Mass spectra were obtained with a Bruker Daltonics Mikrotof\u2010Q\u2010Mass spectrometer. Phosphine boranes 2\u2009a,2\u2009e3\u2009aAll reactions were carried out under an atmosphere of inert Argon and in flame\u2010dried glassware if not mentioned otherwise. Solvents were dried by distillation from alkali metals  at T=130(2) K. The structures were solved by direct methods [1\u2009b], K[1\u2009b], 6\u2009e, 7, 8) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.Deposition numbers\u2005Bis(dimethylamino)phosphine borane (2\u2009b): Method A: PCl3 (0.1\u2005mL 1.14\u2005mmol) was added under stirring to a cooled (\u221278\u2009\u00b0C) solution of P(NMe2)3 (0.42\u2005mL 2.29\u2005mmol) in Et2O (50\u2005mL). Stirring was continued while the solution was allowed to warm to ambient temperature. The solution was cooled again to \u221278\u2009\u00b0C and BH3\u22c5SMe2  was added. The mixture was stirred for 1\u2005h at \u221278\u2009\u00b0C and allowed to warm to RT. After cooling once more to \u221278\u2009\u00b0C, LiAlH4  was added. The mixture was stirred for 1\u2005h at \u221278\u2009\u00b0C, allowed to warm to RT, and stirred for further 24\u2005h. Water (0.5\u2005mL) was added and volatiles were evaporated under reduced pressure. The solid residue was extracted with hexane (20\u2005mL). The extract was dried (Na2SO4) and solids were removed by filtration. Evaporation of the solvent under reduced pressure afforded 2\u2009b as colorless solid which melted around RT . Method B: PCl3 (0.49\u2005mL 5.6\u2005mmol), P(NMe2)3 (2.00\u2005mL 11.2\u2005mmol) and BH3\u22c5SMe2  were reacted in Et2O (30\u2005mL) as described under A. Li[BEt3H]  was added. The mixture was allowed to warm to RT and stirred for further 18\u2005h. Volatiles were evaporated under reduced pressure and the residue was taken up in pentane (150\u2005mL). The resulting mixture was filtered over Celite. Evaporation of the solvent under reduced pressure gave 2\u2009b as colorless oil , which contained according to NMR measurements 10 to 20\u2009% dimethylamine borane. 31P{1H} NMR (C6D6): \u03b4=89.2\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221240.2\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=5.96 , 2.27 , 1.42\u2005ppm ; 13C{1H} NMR (C6D6): \u03b4=38.5\u2005ppm ; MS(ESI): m/z=119.08 .Bis(diisopropylamino)phosphine borane (2\u2009c): LiBH4  was added to a stirred solution of (iPr2N)2PCl  in Et2O (25\u2005mL). The mixture was stirred for 1\u2005h. Volatiles were evaporated under reduced pressure and the residue extracted with hexane (4\u00d720\u2005mL). The combined extracts were filtered, the filtrate concentrated under reduced pressure, and the product isolated by crystallization at \u221224\u2009\u00b0C . 31P{1H} NMR (C6D6): \u03b4=46.3\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221235.6\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=6.70 , 3.43 , 1.61 , 1.10 , 0.98\u2005ppm ; 13C{1H} NMR (C6D6): \u03b4=46.4\u2005ppm , 22.6 ; MS(ESI): m/z=246.2 [M+]; C12H32BN2P (246.19\u2005g\u2009mol\u22121): calcd C 58.55 H 13.10 N 11.38, found C 58.28 H 12.84 N 11.13.1,3\u2010Bis\u20101,3,2\u2010diazaphospholidine borane (2\u2009d): NaBH4  was added under stirring to a cooled (0\u2009\u00b0C) solution of 2\u2010chloro\u20101,3\u2010bis1,3,2\u2010diazaphospholidine  in MeCN (10\u2005mL). The mixture was stirred for 24\u2005h and during this time allowed to warm slowly to RT. Water (0.5\u2005mL) was added, volatiles evaporated under reduced pressure and the residue extracted with toluene (75\u2005mL). The extract was dried (Na2SO4) and filtered. Evaporation of the filtrated gave 2\u2009d as yellow solid . 31P{1H} NMR (C6D6): \u03b4=75.3\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221239.8\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=7.35 , 6.98 , 6.91 , 3.21\u20132.88 , 2.48 , 2.10 , 1.2\u2005ppm ; 13C{1H} NMR (C6D6): \u03b4=139.3 , 138.0 , 129.1 , 128.6 , 49.1 , 18.7 , 18.5\u2005ppm ; MS ((+)\u2010ESI): m/z=337.14 [MK+\u2013BH3]; C18H26BN2P (312.19\u2005g\u2009mol\u22121): calcd C 69.25 H 8.39 N 8.97, found C 69.00 H 8.51 N 8.68.1,3\u2010Bis\u20101,3,2\u2010diazaphospholene borane (2\u2009f): NaBH4  was added to a suspension of 2\u2010bromo\u20101,3\u2010bis\u20101,3,2\u2010diazaphospholene  in MeCN (50\u2005mL). The mixture was stirred for 18\u2005h, filtered, and evaporated to dryness. The residue was washed with pentane and dried in vacuum to afford 477\u2005mg (77\u2009%) of crude 2\u2009f. Further purification was feasible by extracting the crude product with benzene, filtration, and evaporation of the filtrate to dryness. 31P{1H} NMR (C6D6): \u03b4=79.8\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221240.2\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=8.10 , 7.01\u20136.82 , 5.37 , 2.43 , 2.10 , 1.6\u2005ppm ; 13C{1H} (C6D6): \u03b4=138.7 , 137.4 , 136.4 , 129.0 , 128.4 , 127.8 , 118.8 , 19.3 , 18.5\u2005ppm ; MS ((+)\u2010ESI): m/z=310.19 [M+], 311.19 [M+H+]; C18H24BN2P (310.19\u2005g\u2009mol\u22121): calcd C 69.70 H 7.80 N 9.03, found C 68.45 H 7.88 N 9.06. The reason for the low carbon content is not known.Chloro\u2010bis(dimethylamino)phosphine borane (3\u2009b): BH3\u22c5SMe2  was added under stirring to a cooled (0\u2009\u00b0C) solution of (Et2N)2PCl  in Et2O (10\u2005mL). After 30\u2005min, the solution was allowed to warm to RT and stirred for further 18\u2005h. The solvent was then removed under reduced pressure and the residue dissolved in hexane (10\u2005mL). After reaction control by 31P\u2005NMR, enough BH3\u22c5SMe2  to convert unreacted starting material and more hexane (10\u2005mL) were added. Filtering the mixture over Celite and removal of the solvent under reduced pressure gave 3\u2009b as yellow oil . The product is thermally unstable and decomposes even below room temperature; it must be used immediately and cannot be stored.31P{1H} NMR (C6D6): \u03b4=139.7\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221236.0\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=2.27 , 1.59\u2005ppm ; 13C{1H} (C6D6): \u03b4=36.7\u2005ppm . The thermal instability precluded obtaining a meaningful elemental analysis.General procedure for the metalation of secondary diaminophosphine boranes 2\u2009b,d,f with alkali metal bis(trimethylsilyl)amides: MHMDS  was added to a 0.06\u20130.2\u2009m solution of the secondary diaminophosphine borane in THF or [D8]THF (1 to 2\u2005mL). The solution was stirred for 10\u2005min at RT. An aliquot of the reaction mixture was then transferred to an NMR tube and characterized by multinuclear NMR spectroscopy. Conversion to the metalation product was derived from evaluation of the integrals in 1H\u2005NMR spectra. Deprotonation at phosphorus was in all cases confirmed by the disappearance of the characteristic signal splitting due to 1JPH.1\u2009b]: Conversion 86\u2009%. 31P{1H} NMR (C6D6): \u03b4=145.9\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221234.6\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=2.73 , 0.64\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=43.8\u2005ppm .Li[1\u2009b]: Conversion 90\u2009%. 31P{1H} NMR (C6D6): \u03b4=145.0\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221234.3\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=2.76 , 0.66\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=44.9\u2005ppm .Na[1\u2009b]: Conversion 84\u2009%. 31P{1H} NMR (C6D6): \u03b4=142.9\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221232.9\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=2.7 , 0.70\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=44.3\u2005ppm .K[1\u2009f]: conversion 70\u2009%. 31P{1H} NMR (C6D6): \u03b4=201.6\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221229.5\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=7.00\u20136.63 , 5.54 , 2.46\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=127.6 , 121.9 , 127.8 , 117.6 , 19.5\u2005ppm .K[Isolation of sodium bis(dimethylamino)phosphide borane Na[1\u2009b]: A solution of Na[1\u2009b] was prepared as described above from NaHMDS  and 2\u2009b  in THF (2\u2005mL). Storage at \u221224\u2009\u00b0C produced colorless, highly air and moisture sensitive crystals, which were separated by decantation (no yield determined) and characterized by NMR spectroscopy (see Table\u2005Isolation of potassium bis(dimethylamino)phosphine borane K[1\u2009b]: KHMDS  and dibenzo\u201018\u2010crown\u20106  were added to a solution of 2\u2009b  in a mixture of Et2O (3\u2005mL) and THF (7\u2005mL) was carried out as described above. The mixture was stirred for 5\u2005min. Storage at \u221224\u2009\u00b0C produced colorless, highly air and moisture sensitive crystals, which were separated by decantation (no yield determined) and characterized by NMR spectroscopy  was evaporated to dryness. A solution of 2\u2009b  in [D8]THF (1\u2005mL) was added. The solution was stirred for 5\u2005min and then analyzed by multinuclear NMR spectroscopy : \u03b4=142.4\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221233.0\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=2.58 , 0.45\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=43.4\u2005ppm .General procedure for the metalation of secondary diaminophosphine boranes 2\u2009c,e: The metalation agent ][1\u2009c]: 1.2\u2005equiv. KHMDS and 1.0\u2005equiv. dibenzo\u201018\u2010crown\u20106; for Li[1\u2009e]: 1.33\u2005equiv. LDA; for [K(dibenzo\u201018\u2010crown\u20106)][1\u2009e]: 2.0\u2005equiv. KHMDS and 1.0\u2005equiv. dibenzo\u201018\u2010crown\u20106) was added to a 3\u20136\u2005mm solution of the secondary diaminophosphine borane in Et2O (20 to 25\u2005mL). After stirring for 1\u2005h, volatiles were removed under reduced pressure. The residue was dissolved in [D8]THF or C6D6 and characterized by multinuclear NMR spectroscopy. 31P and 11B\u2005NMR data are included in Table\u200531P{1H} NMR spectra. Deprotonation at phosphorus was in all cases confirmed by the disappearance of the characteristic signal splitting due to 1JPH.1\u2009c]: Conversion >98\u2009%. 31P{1H} NMR (C6D6): \u03b4=61.8\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221232.9\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=3.56 , 1.12 , 1.02 , 0.33\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=47.3 , 23.9\u2005ppm : \u03b4=\u22120.39\u2005ppm (s).Li[1\u2009c]: 31P{1H} NMR (C6D6): \u03b4=53.4\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221229.5\u2005ppm ; 1H\u2005NMR (C6D6): \u03b4=3.75 , 1.43 , 1.23 , 0.47\u2005ppm ; 13C{1H} NMR (C6D6): \u03b4=47.9 , 24.7 , 24.2\u2005ppm .K[1\u2009c]: Conversion 94\u2009%. 31P{1H} NMR (C6D6): \u03b4=68.5\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221230.4\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=6.97\u20136.84 , 4.22\u20134.14 , 3.61 , 1.13 , 1.04 , 0.76\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=120.7 , 110.7 , 68.6 , 67.3 , 47.3 , 24.1\u2005ppm .[K(dibenzo\u201018\u2010crown\u20106)][1\u2009e]: 31P{1H} NMR (C6D6): \u03b4=185.7\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221232.2\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=6.97 , 4.1 , 3.99 , 3.26 , 1.22 , 1.18\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=150.6 , 149.1 , 143.1 , 124.1 , 122.9 , 54.2 , 27.4 , 25.0\u201324.5\u2005ppm .Li[1\u2009e]: 31P{1H} NMR (C6D6): \u03b4=187.7\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221229.9\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=6.94 , 4.22\u20133.80 , 3.16 , 1.25\u20131.12\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=150.5 , 149.4 , 143.3 , 124.3 , 123.1 , 122.7 , 54.4 , 27.3 , 25.5 , 25.2 , 24.1 , 23.1\u2005ppm .K[1\u2009e]: 31P{1H} NMR (C6D6): \u03b4=197.3\u2005ppm ; 11B{1H} NMR (C6D6): \u03b4=\u221229.8\u2005ppm ; 1H\u2005NMR ([D8]THF): \u03b4=6.95 , 6.82 , 4.27\u20134.04 ,3.98 , 3.84 , 3.22 , 1.20 , 1.15 , 0.67\u2005ppm ; 13C{1H} NMR ([D8]THF): \u03b4=142.2 , 122.1 , 118.8 , 108.8 , 66.6 , 65.3 , 52.6 , 25.6 , 22.9 , 22.7\u2005ppm .[K(dibenzo\u201018\u2010crown\u20106)] was prepared as described above from 2\u2009a , KHMDS  and Et2O (15\u2005mL). CS2  was added through a microliter syringe. The solution was stirred for 18\u2005h. The solvent was evaporated under reduced pressure. The remaining work\u2010up was carried out in air. The residue extracted with Et2O (10\u2005mL). The extract was filtered in air over Celite, and pentane (10\u2005mL) was added. Storing the solution at \u221224\u2009\u00b0C afforded 8 as red crystalline solid . 31P{1H} NMR (C6D6): \u03b4=93.4\u2005ppm (broad); 11B{1H} NMR \u03b4=\u221234.0\u2005ppm (broad); 1H\u2005NMR (C6D6): \u03b4=3.35 , 3.20 , 1.19 , 1.07\u2005ppm ; 13C{1H} NMR (C6D6): \u03b4=42.0 (broad), 14.4 , detection of the CS2\u2010carbon atom was precluded by low S/N; C9H22BKN2PS2\u22c50.5 H2O (313.3\u2005g\u2009mol\u22121): calcd C 34.50 H 7.72 N 8.94 S 20.47; found C 33.85 H 7.49 N 8.67 S 19.93. The deviation between calculated and found analytical data is presumably due to a higher water content of the hygroscopic sample ; MS ((\u2212)\u2010ESI): m/z=264.11 [(M\u2212K)\u2212].The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The title compound exists in the crystal as a dimer of ion pairs. Hydrogen bonding and weak \u03c0\u2013\u03c0 inter\u00adactions along with N\u2014H\u22ef\u03c0 inter\u00adactions are involved in consolidating this cluster. The three-dimensional crystal structure consists of stepped stacks of dimers of ion pairs associated by C\u2014H\u22ef\u03c0(ring) and slipped \u03c0-stacking inter\u00adactions. 21H15N2+\u00b7C7H5O2\u2212, 2-phenyl-1H-phenanthroimidazole and benzoic acid form an ion pair complex. The system is consolidated by hydrogen bonds along with \u03c0\u2013\u03c0 inter\u00adactions and N\u2014H\u22ef\u03c0 inter\u00adactions between the constituent units. For a better understanding of the crystal structure and inter\u00admolecular inter\u00adactions, a Hirshfeld surface analysis was performed.In the title compound, C The space group is monoclinic, P21/n and two asymmetric units, two M1+ ions and two benzoate ions, are combined in an inversion dimer of ion pairs \u00b0] to one another and the torsional angle C1\u2014O1\u2014N1\u2014C22 is 78.24 (su?)\u00b0. Unit A is stabilized by hydrogen bonds \u2005\u00c5].The structure of the title compound is shown in Fig.\u00a01A units are associated through weak, slipped, \u03c0-stacking inter\u00adactions between the C9\u2013C14 benzene rings and N1/C22/N2/C21/C8 imidazole rings across inversion centers .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020005344/mw2157sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005344/mw2157Isup2.hklStructure factors: contains datablock(s) I. DOI: 1997348CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C(6) chains propgagating along [001].The title compound consists of two fluoro\u00adphenyl groups and one butyl group equatorially oriented on a piperidine ring, which adopts a chair conformation. The dihedral angle between the mean planes of the phenyl rings is 72.1\u2005(1)\u00b0. In the crystal, weak N\u2014H\u22efO and C\u2014H\u22efF inter\u00adactions, which form  21H23F2NO, consists of two fluoro\u00adphenyl groups and one butyl group equatorially oriented on a piperidine ring, which adopts a chair conformation. The dihedral angle between the mean planes of the phenyl rings is 72.1\u2005(1)\u00b0. In the crystal, N\u2014H\u22efO and weak C\u2014H\u22efF inter\u00adactions, which form R22[14] motifs, link the mol\u00adecules into infinite C(6) chains propagating along [001]. A weak C\u2014H\u22ef\u03c0 inter\u00adaction is also observed. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H\u22efH (53.3%), H\u22efC/C\u22efH (19.1%), H\u22efF/F\u22efH (15.7%) and H\u22efO/O\u22efH (7.7%) contacts. Density functional theory geometry-optimized calculations were compared to the experimentally determined structure in the solid state and used to determine the HOMO\u2013LUMO energy gap and compare it to the UV\u2013vis experimental spectrum.The title compound, C Ramachandran et al., 2007et al., 2020Piperidin-4-one compounds have various biological properties and have applications as anti-viral, antitumor, and antihistaminic agents As part of our studies in this area, we now describe the synthesis and structure of the title compound, C1/cP2 with one mol\u00adecule in the asymmetric unit \u2005\u00c5, \u03b8 = 6.56\u2005(15)\u00b0, \u03c6 = 356.9\u2005(14)\u00b0. The dihedral angles for the C1\u2013C5/N1  piperidine (A), C6\u2013C11 fluorophenyl (B) and C12\u2013C17 fluorophenyl (C) rings are A/B = 65.50\u2005(8), A/C = 73.87\u2005(8) and B/C = 72.11\u2005(8)\u00b0. The substituents on the piperidine ring adopt equatorial orientations with the keto oxygen atom being anti-clinal [O1\u2014C3\u2014C2\u2014C1 = \u2212124.44\u2005(16)\u00b0]. The butyl group lies in a syn-periplanar orientation [O1\u2014C3\u2014C2\u2014C18 = 0.7\u2005(2)] while the fluoro\u00adphenyl groups are both anti-clinal [N1\u2014C5\u2014C6\u2014C7 = \u2212148.28\u2005(13) and N1\u2014C1\u2014C12\u2014C17 = \u221275.42\u2005(16)\u00b0]. The sum of the bond angles around N1 is 336.8\u00b0, which is consistent with sp3 hybridization for this atom it Fig.\u00a01. In the C(6) chains (via the N\u2014H\u22efO bond) along [001]. Some longer C\u2014H\u22efO and C\u2014H\u22efF contacts are also present as well as a single weak C\u2014H\u22ef\u03c0 inter\u00adaction n Table\u00a01.CrystalExplorer17.5 . The curvedness of the HS can be used to divide the mol\u00adecular surface into contact patches with each neighbouring mol\u00adecule thereby using it to define a coordination number in the crystal .A Hirshfeld surface (HS) analysis  are the most important inter\u00adactions , presumably because of the large hydrogen content of (I)de + di) < 1.19\u2005\u00c5. The pair of wings for the H\u22efC/C\u22efH contacts  is in the region 1.04\u2005\u00c5 < (de + di) < 1.58\u2005\u00c5 and includes the weak C\u2014H\u22ef\u03c0 inter\u00adaction. The H\u22efF/F\u22efH contacts  are seen as a pair of wings in the region 1.04\u2005\u00c5 < (de + di) < 1.38\u2005\u00c5. The wings for the H\u22efO/O\u22efH contacts  are in the region of 0.88\u2005\u00c5 < (de + di) < 1.20\u2005\u00c5 while the blunt wings in the plot for F\u22efF contacts  are in the region 1.60\u2005\u00c5 < (de + di) < 1.70\u2005\u00c5. The C\u22efC contacts  make a negligible 0.1% contribution and are viewed as a dash pattern pointing diagonally left. The O\u22efO contacts  make no contribution to the HS. The most significant of these contributions to the overall Hirshfeld surface are shown in Figure S3 in the supporting information.Two-dimensional fingerprint plots show the relative contributions of the various types of contacts to the Hirshfeld surface for (I)ns Fig.\u00a04b, presuts Fig.\u00a04f; 2.6% ts Fig.\u00a04g make ats Fig.\u00a04h make nWebMo Pro \u00b0 with respect to each other.A density functional theory (DFT) geometry-optimized calculation for (I)supplementary Table S2. Both the HOMO and HOMO\u22121 are localized largely on the piperidine ring. For the LUMO, LUMO+1 and LUMO+2, the orbitals are delocalized over the piperidine ring as well as both phenyl rings. The observed UV/vis absorption spectrum . The molar extinction coefficients, \u220a, are 1.12 and 2.50\u2005l\u2005mol\u22121 cm\u22121, respectively. We tentatively assign the first absorption band envelope at 256\u2005nm to overlapping contributions from HOMO \u2192 LUMO (energy gap 5.71\u2005eV), HOMO \u2192 LUMO+1 (5.83\u2005eV) and HOMO\u22121 \u2192 LUMO (5.82\u2005eV). The band at 216\u2005nm is assigned to overlapping contributions from HOMO \u2192 LUMO+2 (5.89\u2005eV), HOMO\u22121 \u2192 LUMO+1 (5.95\u2005eV) and HOMO\u22121 \u2192 LUMO+2 (6.01\u2005eV).The calculated energies (eV) for the frontier mol\u00adecular orbitals are shown in Fig.\u00a05um Fig.\u00a06 shows twet al.. 2016et al., 2001t(3)-pentyl-r(2),c6)-di\u00adphenyl\u00adpiperidin-4-one ,c(6)-di\u00adphenyl\u00adpiperidin-4-one ,c(6)-bis\u00ad(4-fluoro\u00adphen\u00adyl)piperidin-4-one : found C 74.24, H 6.16, N 4.03; calculated C 73.45, H 6.75, N 4.08; melting point 381.5\u2005K.A mixture of ammonium acetate , 4-fluoro\u00adbenzaldehyde  and 2-hepta\u00adnone  in distilled ethanol was heated first to boiling. After cooling, the viscous liquid obtained was dissolved in ether (200\u2005ml) and shaken with 100\u2005ml concentrated hydro\u00adchloric acid. The precipitated hydro\u00adchloride of 3-butyl-2,6-bis\u00ad(4-fluoro\u00adphen\u00adyl)piperidin-4-one was removed by filtration and washed first with a 50\u2005ml mixture of ethanol and ether (1:1) and then with ether to remove most of the coloured impurities. The resulting yellowish base was liberated from an alcoholic solution by adding aqueous ammonia (15\u2005ml) and then diluted with water (200\u2005ml). Then, 1.0\u2005g of the crude sample was dissolved in 100\u2005ml of absolute alcohol, warmed until the sample dissolved, and 2.0\u2005g of animal charcoal added in the resulting solution. The hot solution was filtered and the procedure repeated again. The filtered solution was left for 48\u2005h and colourless prisms of (I)\u22121) (KBr): 3287 (\u03bdN\u2014H), 3134, 2929, 2866 (\u03bdC\u2014H), 1702 (\u03bdC=O), 1605, 1508 (\u03bdC=C), 793 (\u03bdC\u2014Cl); 1H NMR : \u03b4 7.01\u20137.45 , 4.04 , 3.68 , 2.67 , 2.56 , 2.0 (NH proton), 0.95\u20131.0 CH2(3), 1.09\u20131.15 CH2(2), 1.59\u20131.63 CH2(1), 0.74, ; 13C NMR : \u03b4 129.16, 129.38, 128.18, 128.10, 115.64, 115.56, 115.43, 115.35 (aromatic carbon atoms), 138.52 and 137.64 (aromatic ipso carbon atoms), 66.33 (C2), 57.50 (C3), 208.7 (C4), 51.63 (C5), 61.08 (C6), 24.30 C18H2, 29.71 C19H2, 22.75 C20H2, 13.81 C21H3.FT\u2013IR (cmUiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied in all cases.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020004636/hb7882sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020004636/hb7882Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020004636/hb7882sup3.docxTheoretical chemistry data and Hirshfeld figures. DOI: 1994539CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Hirshfeld surface and simultaneous TGA\u2013DTA analyses are also describedThe mol\u00adecular and crystal structure of bis\u00ad, crystallizes with one half mol\u00adecule in the asymmetric unit of the monoclinic unit cell. The complex adopts an octa\u00adhedral coordination geometry with two mutually trans benzyl-2-(heptan-4-yl\u00adidene)hydrazine-1-carboxyl\u00adate ligands in the equatorial plane with the axial positions occupied by N-bound thio\u00adcyanato ligands. The overall conformation of the mol\u00adecule is also affected by two, inversion-related, intra\u00admolecular C\u2014H\u22efO hydrogen bonds. The crystal structure features N\u2014H\u22efS, C\u2014H\u22efS and C\u2014H\u22efN hydrogen bonds together with C\u2014H\u22ef\u03c0 contacts that stack the complexes along the b-axis direction. The packing was further explored by Hirshfeld surface analysis. The thermal properties of the complex were also investigated by simultaneous TGA\u2013DTA analyses.The title centrosymmetric Ni The coordination chemistry of benzyl carbazate Schiff base complexes has gained importance not only from the inorganic point of view, but also because of their biological and thermal properties. In the course of our recent studies on such complexes, we reported the cobalt(II) complex of a Schiff base derived from benzyl carbazate and heptan-4-one with thio\u00adcyanates as the charge-compensating ligands \u00b0. Bond lengths and angles in the closely related Ni and Co complexes are generally similar, although the Ni1\u2014N1 bond [2.1332\u2005(12)\u2005\u00c5] is significantly shorter here than the corresponding Co1\u2014N11 and Co2\u2014N21 vectors [2.206\u2005(5) and 2.248\u2005(6)\u2005\u00c5 respectively].The title compound, N\u22efS1 and weaker C8\u2014H8\u22efS1 and C10\u2014H10A\u22efS1 hydrogen bonds, Table\u00a01bc diagonal, Fig.\u00a02B\u22efS1 hydrogen bonds link adjacent mol\u00adecules into rows along the b-axis direction, Fig.\u00a03a, through C2\u2014H2A\u22efCg3, C\u2014H\u22ef\u03c0 contacts, Fig.\u00a04Cg3 is the centroid of the C3\u2013C8 phenyl ring. These contacts combine to stack mol\u00adecules of the complex in a regular fashion along the b-axis direction, Fig.\u00a05In the crystal structure, atom S1 acts as a trifurcated acceptor forming N2\u2014H21 were obtained using Hirshfeld surface analysis  and (b). Bold red circles on the Hirshfeld surfaces correspond to the N\u2014H\u22efS hydrogen bonds while the weaker C\u2014H\u22efS and C\u2014H\u22ef\u03c0 contacts appear as faint red circles. Fingerprint plots, Fig.\u00a07Further details of the inter\u00admolecular inter\u00adactions in 1. Simultaneous TGA\u2013DTA analyses were recorded in air on a Perkin\u2013Elmer SII Thermal Analyser over the temperature range 50\u2013800\u00b0C. With the equipment used here, the TGA curve shows the temperature range but not the individual peak temperatures. However, peak temperatures can be seen in the DTA curve. In the first step of decomposition, the weight loss of 74% occurs over the temperature range 115\u2013260\u00b0C (TGA). This corresponds to the loss of the Schiff base ligands to form NiII thio\u00adcyanate as an inter\u00admediate. This was marked by both endothermic (170\u00b0C) and exothermic peaks (190 and 210\u00b0C) in the DTA curve. As the thermal analysis was carried out under a dynamic flowing air atmosphere, the S and N atoms are oxidized to SO2 and NO2, while nickel ultimately forms nickel oxide. Similar decomposition processes have been observed in our recent wok on numerous similar complexes, see for example NHN=C(CH2)2 unit produced only two hits. One was our own report of the ligand benzyl 2-cyclo\u00adpentyl\u00adidenehydrazine\u00adcarboxyl\u00adate -1-ethyl 8-methyl 7-(2-(benzyl\u00adoxycarbon\u00adyl)hydrazono)oct-2-enedioate, 2\u00b76H2O,  dissolved in 10\u2005mL of doubly distilled water was added to this solution. The resulting blue solution was layered with heptan-4-one (dipropyl ketone) and the solution changed to a green colour. The final solution was left to evaporate at room temperature. After slow evaporation, bluish\u2013green rhombus-shaped crystals suitable for X-ray diffraction analysis were collected, washed with doubly distilled water and air-dried.Equimolar amounts of ammonium thio\u00adcyanate  and benzyl carbazate  were dissolved in methanol (10\u2005mL). Nickel nitrate, Ni and 3Ag2(F) \u21923Tg1(P) transitions, respectively, supporting the six-coordinate octa\u00adhedral geometry around the NiII cation  spectrometer using tetra\u00admethyl\u00adsilane as an inter\u00adnal reference. Chemical shifts are expressed in parts per million (ppm): 0.84\u20130.88 and 1.33\u20132.20 ppm: CH3 and CH2 groups, respectively; \u2013OCH2 proton: 5.08 ppm; aromatic protons multiplets 7.29\u20137.34 ppm; NH: 9.882 ppm.The Simultaneous TGA\u2013DTA analyses were recorded in air on a PerkinElmer SII Thermal Analyser over the temperature range 50-800\u00b0C.Uiso(H) = 1.2Ueq(N). All C-bound H atoms were refined using a riding model with d(C\u2014H) = 0.95\u2005\u00c5, Uiso = 1.2Ueq(C) for aromatic 0.99\u2005\u00c5, Uiso = 1.2Ueq(C) for CH2 and 0.98\u2005\u00c5, Uiso = 1.5Ueq(C) for CH3 H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020004260/vm2230sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020004260/vm2230Isup2.hklStructure factors: contains datablock(s) I. DOI: 1993291CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the complex mol\u00adecule, the tetra\u00addentate ligand N1,N3-bis\u00ad[methyl\u00adene]-2,2-di\u00admethyl\u00adpropane-1,3-di\u00adamine coordinates to the FeII ion through the N atoms of the 1,2,3-triazole moieties and aldimine groups. Two thio\u00adcyanate anions, coordinating through their N atoms, complete the coordination sphere of the central ion. In the crystal, neighbouring mol\u00adecules are linked through weak C\u2014H\u22ef\u03c0, C\u2014H\u22efS and C\u2014H\u22efN inter\u00adactions into a two-dimensional network extending parallel to (011). The inter\u00admolecular contacts were qu\u00adanti\u00adfied using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H\u22efH (35.2%), H\u22efC/C\u22efH (26.4%), H\u22efS/S\u22efH (19.3%) and H\u22efN/N\u22efH (13.9%).The unit cell of the title compound, [Fe The average trigonal distortion parameters \u03a3 = \u03a3112(|90\u00a0\u2212\u00a0\u03c6i|), where \u03c6i is the angle N\u2014Fe\u2014N\u2032 , where \u03b8i is the angle generated by superposition of two opposite faces of an octa\u00adhedron . The volume of the [FeN6] coordination polyhedron is 12.4\u2005\u00c53.The Fens Fig.\u00a01. The aveB\u22efCgi of 3.330\u2005(3)\u2005\u00c5 \u2005\u00c5] with a thio\u00adcyanate anion. This, together with the C4\u2014H4B\u22efC27ii and C4\u2014H4B\u22efN10ii inter\u00adactions [3.709\u2005(3) and 3.617\u2005(3)\u2005\u00c5] involving the C\u2261N group of the anion, links the dimers into a supra\u00admolecular chain propagating parallel to [01iii = 3.603\u2005(3)\u2005\u00c5] and triazole groups [C19\u2014H19A\u22efN7iii = 3.311\u2005(3)\u2005\u00c5] of neighbouring complex mol\u00adecules, forming a two-dimensional supra\u00admolecular array extending parallel to (011).Neighbouring complex mol\u00adecules form dimers through double weak contacts C18\u2014H181] Fig.\u00a02. These cCrystal Explorer  to 1.8236 (blue) a.u. The pale-red spots symbolize short contacts and negative dnorm values on the surface correspond to the inter\u00adactions described above. The overall two-dimensional fingerprint plot is illus\u00adtrated in Fig.\u00a03dnorm are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efS/S\u22efH, and H\u22efN/N\u22efH contacts, and the two-dimensional fingerprint plots are presented in Fig.\u00a04Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using et al., 2016II thio\u00adcyanate complexes, derivatives of a 1,3-di\u00adamino\u00adpropanes and N-substituted 1,2,3-triazole aldehydes, viz. DURXEV, ADAQUU, ADAREF and solvatomorphs ADAROP and ADARUV 4(NCS)2] dissolved in a minimum amount of boiling methanol with a minimum amount of ascorbic acid. The formed yellow solution was slowly cooled to ambient temperature. The formed orange crystals were subsequently filtered off. Elemental analysis calculated (%) for C27H28FeN10S2: C, 52.94; H, 4.61; N, 22.87; S, 10.47; found: C, 52.88; H, 4.37; N, 22.40; S, 10.35. IR vKBr (cm\u22121): 1615 (C=N), 2071, 2115 (NCS).The ligand of the title compound was obtained Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020012608/wm5580sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012608/wm5580Isup3.cdxSupporting information file. DOI: 2032292CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, centrosymmetric, eight-membered {\u22efHNCS}2 synthons are formed by thio\u00adamide-N\u2014H\u22efS(thio\u00adamide) hydrogen bonds.The title hydrazine carbodi\u00adthio\u00adate features an almost planar C 13H18N2OS2, is constructed about a central and almost planar C2N2S2 chromophore (r.m.s. deviation = 0.0263\u2005\u00c5); the terminal meth\u00adoxy\u00adbenzene group is close to coplanar with this plane [dihedral angle = 3.92\u2005(11)\u00b0]. The n-butyl group has an extended all-trans conformation . The most prominent feature of the mol\u00adecular packing is the formation of centrosymmetric eight-membered {\u22efHNCS}2 synthons, as a result of thio\u00adamide-N\u2014H\u22efS(thio\u00adamide) hydrogen bonds; these are linked via meth\u00adoxy-C\u2013H\u22ef\u03c0(meth\u00adoxy\u00adbenzene) inter\u00adactions to form a linear supra\u00admolecular chain propagating along the a-axis direction. An analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots point to the significance of H\u22efH (58.4%), S\u22efH/H\u22efS (17.1%), C\u22efH/H\u22efC (8.2%) and O\u22efH/H\u22efO (4.9%) contacts in the packing. The energies of the most significant inter\u00adactions, i.e. the N\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions have their most significant contributions from electrostatic and dispersive components, respectively. The energies of two other identified close contacts at close to van der Waals distances, i.e. a thione\u2013sulfur and meth\u00adoxy\u00adbenzene\u2013hydrogen contact  and between methyl\u00adene-H atoms , are largely dispersive in nature.The title hydrazine carbodi\u00adthio\u00adate, C The meth\u00adoxy\u00adbenzene ring forms a dihedral angle of 3.92\u2005(11)\u00b0 with the central residue indicating a close to co-planar relationship. The C9\u2014O1\u2014C6 \u2014C7 dihedral angle of 176.9\u2005(3)\u00b0 indicates that the meth\u00adoxy substituent lies almost in the plane of the benzene ring to which it is connected. The configuration about the C2=N2 imine bond [1.278\u2005(3)\u2005\u00c5] is E and this bond length is significantly shorter than the C1\u2014N1 bond [1.330\u2005(3)\u2005\u00c5]; the N1\u2014N2 bond length is 1.378\u2005(3)\u2005\u00c5. There is a large disparity in the C1\u2014S1 [1.662\u2005(3)\u2005\u00c5] and C1\u2014S2 [1.745\u2005(3)\u2005\u00c5] bond lengths, which correlate with significant double-bond character in the former; the C10\u2014S2 bond length at 1.793\u2005(3)\u2005\u00c5 is longer than each of these. The thione character of the C1\u2014S1 bond is also reflected in the range of angles subtended at the C1 atom, which are systematically wider for those involving the thione-S1 atom, i.e. S1\u2014C1\u2014S2 [126.35\u2005(16)\u00b0] and S1\u2014C1\u2014N1 [120.9\u2005(2)\u00b0], cf. S2\u2014C1\u2014N1 [112.76\u2005(19)\u00b0]. The thio\u00adamide-N\u2014H and thio\u00adamide-S atoms have a syn disposition. Finally, the n-butyl group has an extended, all-trans conformation as seen in the S2\u2014C10\u2014C11\u2014C12 [\u2212173.2\u2005(3)\u00b0] and C10\u2014C11\u2014C12\u2014C13 [180.0\u2005(4)\u00b0] torsion angles.The mol\u00adecular structure of (I)via an eight-membered {\u22efHNCS}2 synthon, the mol\u00adecular packing is largely devoid of directional inter\u00adactions  inter\u00adactions, Fig.\u00a02a), being the only other identified supra\u00admolecular association. Globally, chains pack without specific inter\u00adactions between them, Fig.\u00a02b). An analysis of the weak non-covalent contacts within and connecting chains is given in the Analysis of the Hirshfeld surfaces.With the exception of thio\u00adamide-N\u2014H\u22efS(thio\u00adamide) hydrogen bonding between centrosymmetrically related mol\u00adecules, Table\u00a01et al., 2019Crystal Explorer 17 a)\u2013(e), respectively; the percentage contributions from the different inter\u00adatomic contacts are summarized in Table\u00a02b), a short inter\u00adatomic H\u22efH contact involving methyl\u00adene-H10B with a symmetry-related mate  and occurring between supra\u00admolecular chains aligned along the a axis, is observed as a single peak at de + di \u223c 2.2\u2005\u00c5. In the fingerprint delineated into S\u22efH/H\u22efS contacts, shown in Fig.\u00a06c), the pair of well-defined spikes at de + di \u223c 2.5\u2005\u00c5 arise as a result of the prominent inter\u00admolecular N\u2014H\u22efS inter\u00adaction. The points corresponding to S\u22efH/H\u22efS contacts involving the thione-S1 and meth\u00adoxy\u00adbenzene-H4 atoms, occurring within the supra\u00admolecular chain shown in Fig.\u00a02a), albeit at nearly van der Waals separations , and reflected as an electrostatic inter\u00adaction in the Hirshfeld surface plotted over the electrostatic potential of Fig.\u00a04d) are at distances equal to or greater than the sum of van der Waals radii, the presence of characteristic wings is the result of the inter\u00admolecular methy\u00adoxy-C\u2014H\u22ef\u03c0(meth\u00adoxy\u00adbenzene) contact. The points corresponding to inter\u00adatomic O\u22efH/H\u22efO contacts illustrated in the corres\u00adponding fingerprint plot of Fig.\u00a06e), also show a pair of forceps-like tips at de + di \u223c 2.8\u2005\u00c5, i.e. at van der Waals distances. The contribution from the other inter\u00adatomic contacts summarized in Table\u00a02The overall two-dimensional fingerprint plot for (I)Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep)  level of theory. The nature and strength of the inter\u00admolecular inter\u00adactions in terms of their energies are qu\u00adanti\u00adtatively summarized in Table\u00a03Eele, Edisp and Etot components, respectively; the radius of the cylinder is proportional to the magnitude of the inter\u00adaction energies. This is reflected in the relatively thick red cylinders corresponding to the electrostatic inter\u00adactions via the N\u2014H\u22efS hydrogen bonding in Fig.\u00a07a) and the thick green cylinders corresponding to the strong dispersive inter\u00adactions provided by the methy\u00adoxy-C\u2014H\u22ef\u03c0(meth\u00adoxy\u00adbenzene) inter\u00adactions in Fig.\u00a07b).The pairwise inter\u00adaction energies between mol\u00adecules in the crystal of (I)6H4C(H)=NN(H)C(=S)SR. These are of the R = Me Reflecting the inter\u00adest in the chemistry of hydrazine carbodi\u00adthio\u00adates related to (I)S-butyl\u00addithio\u00adcarbazate (SBuDTC). An ethano\u00adlic solution (28\u2005ml) of 4-meth\u00adoxy\u00adbenzaldehyde  was added directly to the SBuDTC in situ. This mixture was heated to 323\u2005K with continuous stirring for 30\u2005min. The yellow product (I)13H18N2OS2: C, 55.3; H, 6.4; N, 9.9; S, 22.7. Found: C, 55.9; H, 6.6; N, 9.8; S, 23.2. FT\u2013IR (cm\u22121): 3120 \u03bd(NH), 2927 \u03bd(CH), 1600 \u03bd(C=N), 1248 and 1107 \u03bd(COC), 1017 \u03bd(NN), 861 \u03bd(CSS). MS: calculated m/z = 282; Found m/z = 282. 1H NMR : \u03b4 13.11 , 8.15 , 6.97, 7.02, 7.61, 7.78 (ArH), 3.76 , 3.14 , 1.58 , 1.36 , 0.86 . 13C{1H} NMR : \u03b4 196.96 (C=S), 146.87 (C=N), 161.90, 129.65, 126.36, 115.00 (ArC), 55.86 (OCH3), 33.19, 31.05, 22.10 (CH2), 14.07 (CH3). NMR data were measured on a JOEL ECX500 FT NMR spectrometer.In an ice-bath, carbon di\u00adsulfide  was added dropwise to an absolute ethanol (35\u2005ml) solution comprising KOH  and hydrazine hydrate . After 30\u2005min, 1-bromo\u00adbutane  was added. The solution was stirred at 278\u2005K for 1\u2005h to form Uiso(H) set to 1.2Ueq(C). The N-bound H atom was located in a difference-Fourier map but was refined with a N\u2014H distance restraint of 0.86\u2005(1)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020000328/hb7887sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000328/hb7887Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000328/hb7887Isup3.cmlSupporting information file. DOI: 1977066CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "V with the dihedral angle between the phthalazin-1-one and mesityl residues being 83.26\u2005(4)\u00b0. Mol\u00adecules assemble into a linear, supra\u00admolecular tape by phthalazinone-C6-C\u2014H\u22efO(sulfoxide) and \u03c0\u2013\u03c0 stacking inter\u00adactions.The mol\u00adecule in the title crystal has the shape of the letter  17H16N2O3S {systematic name: 2-[\u00adsulfon\u00adyl]-1,2-di\u00adhydro\u00adphthalazin-1-one}, features a tetra\u00adhedral sulfoxide-S atom, connected to phthalazin-1-one and mesityl residues. The dihedral angle [83.26\u2005(4)\u00b0] between the organic substituents is consistent with the mol\u00adecule having the shape of the letter V. In the crystal, phthalazinone-C6-C\u2014H\u22efO(sulfoxide) and \u03c0\u2013\u03c0 stacking [inter-centroid distance = 3.5474\u2005(9)\u2005\u00c5] contacts lead to a linear supra\u00admolecular tape along the a-axis direction; tapes assemble without directional inter\u00adactions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of the C\u2014H\u22efO and \u03c0-stacking inter\u00adactions but, also H\u22efH and C\u2014H\u22efC contacts. The calculation of the inter\u00adaction energies indicate the importance of dispersion terms with the greatest energies calculated for the C\u2014H\u22efO and \u03c0-stacking inter\u00adactions.The X-ray crystal structure of the title phthalazin-1-one derivative, C H)-one derivatives are a group of di\u00adaza\u00adheterobicycles that are noteworthy for their inter\u00adesting medicinal applications. Thus, this class of compound has been reported to possess a wide variety of biological properties such as anti-diabetic , anti-inflammatory and analgesic -one-based drugs are in use -ones, have also been reported -one was described. In the present study, the title compound, 2-[\u00adsulfon\u00adyl]-1,2-di\u00adhydro\u00adphthalazin-1-one, (I)Phthalazin-1\u00b0 for N1\u2014S1\u2014C1, involving the singly-bonded N1 and C1 atoms, to a wide 118.39\u2005(6)\u00b0, for O1\u2014S1\u2014O2, involving the doubly-bonded sulfoxide-O1, O2 atoms. The organic residues lie to the opposite side of the mol\u00adecule to the SO2 residue, forming dihedral angles of 67.35\u2005(4)\u00b0 [phthalazin-1-one with r.m.s. deviation = 0.0105\u2005\u00c5] and 49.79\u2005(6)\u00b0 [mesit\u00adyl]. The dihedral angle between the organic residues of 83.26\u2005(4)\u00b0 indicates a close to orthogonal relationship. The N2\u2014N1\u2014C10\u2014O3 torsion angle of \u2212179.88\u2005(12)\u00b0 indicates a co-planar arrangement for these atoms, which allows for the close approach of the N2 and O3 atoms, i.e. 2.6631\u2005(15)\u2005\u00c5, suggestive of a stabilizing contact \u2005\u00c5 and C10\u2014N1 = 1.4003\u2005(17)\u2005\u00c5. In each of the C17=N2 [1.2911\u2005(18)\u2005\u00c5] and C10=O3 [1.2175\u2005(15)\u2005\u00c5] bonds, double-bond character is noted. The bond angles about the N1 atom are non-symmetric, with the endocyclic N2\u2014N1\u2014C10 angle of 126.97\u2005(11)\u2005\u00c5 being significantly wider than the exocyclic N2\u2014N1\u2014S1 [113.93\u2005(9)\u2005\u00c5] and C10\u2014N1\u2014S1 [118.89\u2005(8)\u2005\u00c5] angles.The mol\u00adecule of (I)6-C\u2014H\u22efO(sulfoxide) contacts, Table\u00a01a). The \u03c0-stacking occurs between centrosymmetrically related phthalazinone rings, i.e. between the N2C4 and C6i rings with an inter-centroid distance = 3.5474\u2005(9)\u2005\u00c5, angle of inclination = 1.17\u2005(7)\u00b0 for symmetry operation (i) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z. As shown in Fig.\u00a02b), the tapes inter-digitate along the c-axis direction allowing for putative \u03c0-stacking between mesityl rings but, the inter-centroid separation is long at 4.1963\u2005(8)\u2005\u00c5. The assemblies shown in Fig.\u00a02b) stack along the a-axis direction, again without directional inter\u00adactions between them, Fig.\u00a02c).The formation of a supra\u00admolecular tape sustained by phthal\u00ada\u00adzinone-CCrystal Explorer 17 ,(b), the presence of diminutive red spots near methyl-C7 and benzene-H5 are indicative of inter\u00admolecular C\u2014H\u22efC contacts as C\u2014H\u22ef\u03c0 contacts are not preferred because of the V-shaped mol\u00adecular geometry of (I)6 ring on the dnorm-mapped Hirshfeld surface in Fig.\u00a03b) is indicative of short intra-chain C\u22efC contacts [Table\u00a02a)] and is consistent with the significant contribution from \u03c0\u2013\u03c0 stacking between centrosymmetrically related phthalazinone-N2C4 and C6 rings, encompassing connections between phthalazinone-C6 rings [3.6657\u2005(9)\u2005\u00c5 with angle of inclination = 0.03\u2005(7)\u00b0]. The involvement of the methyl-C8 atom in C\u2014H\u22efO [to provide links between the chains shown in Fig.\u00a02b)] and C\u2014H\u22efC contacts, Table\u00a02c). The blue and red regions corres\u00adponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential shown in Fig.\u00a04In order to probe the inter\u00adactions between mol\u00adecules of (I) al. 2019. In addia)\u2013(e), respectively; the percentage contributions from the different inter\u00adatomic contacts to the Hirshfeld surfaces are summarized in Table\u00a03A atoms, Table\u00a02de + di \u223c2.2\u2005\u00c5 in the fingerprint plot delineated into H\u22efH contacts, Fig.\u00a05b). In the fingerprint plot delineated into O\u22efH/H\u22efO contacts illustrated in Fig.\u00a05c), a pair of forceps-like tips at de + di \u223c2.3\u2005\u00c5, indicate the inter\u00admolecular C\u2014H\u22efO inter\u00adaction involving the phthalazinone-H12 and sulfoxide-O2 atoms, whereas the other inter\u00adatomic O\u22efH/H\u22efO contacts are merged within the plot and appear as a pair of intense blue spikes at de + di \u223c2.8\u2005\u00c5. Despite the observation that inter\u00admolecular C\u2014H\u22ef\u03c0 contacts are usually preferred by methyl groups, none are found involving those substituted at (C1\u2013C6) benzene ring in the crystal due to the V-shaped geometry. Rather, the involvement of methyl-C7 and H5A atoms, and benzene-C5 and H7C atoms [to provide links between the chains shown in Fig.\u00a02b)] in C\u2014H\u22efC inter\u00adactions, Table\u00a02de + di \u223c2.8\u2005\u00c5 in the fingerprint plot delineated into C\u22efH/H\u22efC contacts, Fig.\u00a05d). The presence of \u03c0\u2013\u03c0 stacking inter\u00adactions between symmetry-related phthalazinone-N2C4 and C6 rings is also evident as the arrow-shaped distribution of points around de, di \u223c1.8\u2005\u00c5 in the fingerprint plot delineated into C\u22efC contacts, Fig.\u00a05e). The contribution from other inter\u00adatomic contacts, summarized in Table\u00a02The overall two-dimensional fingerprint plots for (I)Eele), polarization (Epol), dispersion (Edis) and exchange\u2013repulsion (Erep) following Turner et al.  level of theory. The nature and strength of the inter\u00admolecular inter\u00adactions in terms of their energies are qu\u00adanti\u00adtatively summarized in Table\u00a042C4 and C6 rings and the short inter\u00adatomic O1\u22efH14 contact have the greatest energy. The short inter\u00adatomic C5\u22efH7C, O3\u22efH8A and C10\u22efH8A contacts also have significant inter\u00adaction energies due to their participation in inversion-related contacts. Lower energies, compared to above inter\u00adactions, are calculated for the H12\u22efH9A, C7\u22efH5 and O1\u22efH9C contacts.The pairwise inter\u00adaction energies between the mol\u00adecules within the crystal of (I) al. 2017. The eneEele, Edisp and Etot, respectively. The images emphasize the importance of dispersion inter\u00adactions in the mol\u00adecular packing.Fig.\u00a06H)-one et al., 20182CCH3)3\u00b74H2O  was added with constant stirring to an ethanol solution (20\u2005ml) of (III) . The resulting mixture was refluxed for 3\u2005h in an oil bath. The obtained colourless solution was concentrated to afford a colourless precipitate, which was filtered, dried under suction and further dried in vacuo over CaCl2. The precipitates were dissolved in ethanol, the resultant colourless solution was filtered and left at room temperature for 48\u2005h to obtain colourless crystals of (I)2-{[2-hydrazinyl\u00adidene]meth\u00adyl}benzoic acid (III) was obtained by a method reported earlier (Asegbeloyin Uiso(H) set to 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989020005101/lh5956sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005101/lh5956Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020005101/lh5956Isup3.cmlSupporting information file. DOI: 1996401CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound belongs to the class of neutral pyridine aroylhydrazone complexes. In the crystal, \u03c0\u2013\u03c0 stacking leads to dimerization of the complex mol\u00adecules, which, in turn, are connected by weak C\u22efO and C\u22efC inter\u00adactions, thus giving rise to a supra\u00admolecular layered architecture. 17H18N3O4)2]\u00b7CH4O\u00b7C2H6O, contains two complex mol\u00adecules related by an inversion centre, plus one methanol and one ethanol solvent molecule per complex molecule. In each complex, two deprotonated pyridine aroylhydrazone ligands {3,4,5-trimeth\u00adoxy-N\u2032-[1-(pyridin-2-yl)ethyl\u00adidene]benzohydrazide} coordinate to the ZnII ion through the N atoms of the pyridine group and the ketamine, and, additionally, through the O atom of the enolate group. In the crystal, dimers are formed by \u03c0\u2013\u03c0 inter\u00adactions between the planar ligand moieties, which are further connected by C\u22efO and C\u22efC inter\u00adactions. The inter\u00admolecular inter\u00adactions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most important contributions for the crystal packing are from H\u22efH (44.8%), H\u22efC/C\u22efH (22.2%), H\u22efO/O\u22efH (18.7%) and C\u22efC (3.9%) inter\u00adactions.The unit cell of the title compound, [Zn(C These dynamic reversible properties have led to the exploration of charged and neutral spin-crossover iron(II) and iron(III) complexes, some with multifunctional properties /24, where \u03b8i is the angle generated by superposition of two opposite faces of the octa\u00adhedron /12, where \u03c6i is the deviation from 90\u00b0 of the cis-N\u2014Zn\u2014N angles in the coordination sphere \u2005\u00c5. In the dimer, the Zn\u22efZni separation is 7.612\u2005(2)\u2005\u00c5   \u2212x, \u2212y, \u2212z\u00a0+\u00a01] = 3.100\u2005(5)\u2005\u00c5 (Table\u00a01ii inter\u00addimer separation of 6.965\u2005(5)\u2005\u00c5. It is worth noting that a related FeII pyridine-based complex with butyl substituents consisting of uniform supra\u00admolecular chains with Fe\u22efFe separation of 7.676\u2005\u00c5 has previously been described \u2005\u00c5 and b = 13.8056\u2005(8)\u2005\u00c5. There are inter\u00adchain contacts C33\u22efC34iii/C34\u22efC33iii , below the sum of the van der Waals radii, between the meth\u00adoxy groups of neighbouring supra\u00admolecular chains at 3.385\u2005(5)\u2005\u00c5.The ligand mol\u00adecules exhibit slipped parallel \u03c0\u2013\u03c0 stacking between coplanar ligands of neighbouring mol\u00adecules, thus forming a dimeric structure; the closest C4\u22efC61] Fig.\u00a02. Neighbo\u00c5 Table\u00a01, with thiv  between the ethanol methyl group and a meth\u00adoxy methyl group is 3.300\u2005(5)\u00c5. Additionally, neighbouring mol\u00adecules of ethanol are mutually bound forming dimers with C36\u22efC37v and O10\u22efC37v  contacts with distances of 3.227\u2005(5) and 2.751\u2005(2)\u2005\u00c5, respectively. Furthermore, the co-crystallized mol\u00adecules of methanol form O\u2014H\u22efO hydrogen bonds with the meth\u00adoxy group of the ligand, with an O9\u22efO2 separation between the O atoms of 2.776\u2005(4)\u2005\u00c5.The neutral nature of the complex mol\u00adecule and therefore the absence of anions and, on the other hand, the relatively large size of the planar rigid substituents prevent the formation of a tightly packed lattice. Therefore, inter\u00admolecular voids are filled by the co-crystallized mol\u00adecules of ethanol, which act as bridges connecting the closest complex mol\u00adecules by O\u2014H\u22efN hydrogen bonding, with the distance between the donor and acceptor atoms O10\u22efN6 equal to 2.825\u2005(5)\u2005\u00c5. The contact C15\u22efC37CrystalExplorer17.5 software  to 2.2951 (blue) a.u. The pale-red spots symbolize short contacts and negative dnorm values on the surface correspond to the inter\u00adactions described above. The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a03dnorm are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, and C\u22efC contacts, and the two-dimensional fingerprint plots are presented in Fig.\u00a04The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were undertaken using et al., 2016N\u2032-[1-(pyridin-2-yl)ethyl\u00adidene]benzohydrazide ethyl\u00adidene]benzohydrazide ethyl\u00adidene]benzohydrazide ethyl\u00adidene]benzohydrazide  to 177.76\u00b0 (MAKLES), while inter\u00admediate values of 168.09 and 170.56\u00b0 are observed for PATXAK and HIGPOD, respectively.A search of the Cambridge Structural Database  to give a colourless complex. A pale-yellow solution was obtained after deprotonation with NEt3 (1\u2005mmol). The neutral complex was isolated by slow cooling the solution to ambient temperature and subsequently by filtering off the yellowish crystals. Elemental analysis calculated (%) for C37H46N6O10Zn: C 55.54, H 5.79, N 10.50; found: C 55.86, H 5.31, N 10.84. IR \u03bdKBr (cm\u22121): 1617 (N=C\u2014O), 1588, 1461 (C=Npy + C=CAr), 1252 (C\u2014O). MS ESI m/z (relative intensity): theoretically calculated 721.19 [M + H+] (100.0%). Found 721.21 [M + H+] (100.0%). TGA (up to 400\u2005K) expected weight loss for EtOH + MeOH: 9.8%; found: 9.5%.The complex was obtained by condensation of 3,4,5-tri\u00admeth\u00adoxy\u00adbenzohydrazide (1\u2005mmol) and acetyl pyridine (1.1\u2005mmol) in a mixture of absolute MeOH and EtOH (1:1) overnight in the presence of two drops of glacial acetic acid. The ligand obtained Uiso(H) = 1.2\u20131.5Ueq(C). None of the hydrogen atoms of the methanol or ethanol molecules could be located.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020000857/tx2017sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020000857/tx2017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000857/tx2017Isup3.cdxSupporting information file. DOI: 1979477CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif.The title mol\u00adecule is planar with an r.m.s. deviation for all non-hydrogen atoms of 0.018\u2005\u00c5. An intra\u00admolecular O1\u2014H1\u22efO5 hydrogen bond involving the adjacent hydroxyl and nitro groups closes an  8H7NO5, is planar with an r.m.s. deviation for all non-hydrogen atoms of 0.018\u2005\u00c5. An intra\u00admolecular O\u2014H\u22efO hydrogen bond involving the adjacent hy\u00addroxy and nitro groups forms an S(6) ring motif. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming chains propagating along the b-axis direction. The chains are linked by C\u2014H\u22efO hydrogen bonds, forming layers parallel to the bc plane. The layers are linked by a further C\u2014H\u22efO hydrogen bond, forming slabs, which are linked by C=O\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular structure. Hirshfeld surface analysis was used to investigate inter\u00admolecular inter\u00adactions in the solid state. The mol\u00adecule was also characterized spectroscopically and its thermal stability investigated by differential scanning calorimetry and by thermogravimetric analysis.The title compound, C Several synthetic routes for the synthesis of entacapone have been reported , was synthesized and its spectroscopic and structural features were studied. There are two reasons for this study, one is connected with the utilization of crystal structures in the identification of materials in the solid state, and the other is to build a library of structurally related compounds of entacapone that will be utilized in a future crystallization study.The title compound is a key starting material in the preparation of entacapone  ring motif. The mol\u00adecule is planar  with the maximum deviation from the mean plane being 0.038\u2005(1)\u2005\u00c5 for atom O5. The bonds lengths and bond angles are close to those found for similar structures (see \u00a74. Database survey).The mol\u00adecular structure of the title compound I, mol\u00adecules are linked by inter\u00admolecular bifurcated hydrogen bonds involving the hydroxyl group. Details of the hydrogen bonding together with the symmetry codes are given in Table\u00a01ialdehyde hydrogen bonds [2.6989\u2005(12)\u2005\u00c5] link the mol\u00adecules into chains with a C(8) motif. Each oxygen atom is involved in one or more inter\u00admolecular hydrogen bonds, except for the O5nitro atom, which is involved only in the intra\u00admolecular hydrogen bond. Each mol\u00adecule is connected by six adjacent mol\u00adecules through strong O1\u2014H1\u22efO3aldehyde and weak C7\u2014H7\u22efO4iinitro and C8\u2014H8A\u22efO3iiialdehyde hydrogen bonds, forming undulating layers parallel to the bc plane, enclosing two type of ring motifs \u2013 B\u22efO4ivnitro, forming slabs \u2005\u00c5] and C2\u2014O1\u22ef\u03c0 [3.353 (su?) \u00c5] close contacts  Fig.\u00a02. The laybs Fig.\u00a03. Moreovets Fig.\u00a04 are preset al., 2016viz. a tin complex of the 4-hy\u00addroxy-3-meth\u00adoxy-5-nitro\u00adbenzaldehyde with a deprotonated hydroxyl group and benzyl anions -2-cyano-3--N,N-di\u00adethyl\u00adprop-2-enamide 1,3-di\u00admethyl-3,7-di\u00adhydro-1H-purine-2,6-dione monohydrate -2-cyano-3--N,N-di\u00adethyl\u00adprop-2-enamide pyridine-4-carboxamide -2-cyano-3--N,N-di\u00adethyl\u00adprop-2-enamide pyrazine-2-carboxamide -2-cyano-3--N,N-di\u00adethyl\u00adprop-2-enamide acetamide , while the most negative region is around the carbonyl oxygen atom . Those two atoms are involved in the shortest inter\u00admolecular hydrogen bond in the crystal structure (O1\u2014H1\u22efO3i), where O1\u22efO3i = 2.6989\u2005(12)\u2005\u00c5; see Table\u00a01Electrostatic potentials were calculated using ce Fig.\u00a07 in the ece Fig.\u00a07a, whileom Fig.\u00a07b. Those3 (10.5\u2005ml) was added dropwise over 30\u2005min. The reaction mixture was stirred for 30\u2005min at 283\u2013288\u2005K and 30\u2005min at 293\u2013298\u2005K. The suspension was then filtered and the crystals obtained were washed with water (3 \u00d7 20\u2005ml). The crystals were dried in a vacuum dryer  to obtain pure yellow compound I . Yellow block-like crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of a solution in acetone after 10\u2005d at room temperature.4-Hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde  was dissolved in acetic acid (200\u2005ml) and the solution was cooled to 283\u2013288\u2005K and 65% HNOSpectroscopic analysis:I  and 125.8\u2005MHz (13C) in CD3OD ; see Tables 2The structure of compound I Fig.\u00a08 was confI was investigated in the solid state by differential scanning calorimetry (DSC) and by thermogravimetric analysis (TGA). DSC analysis was performed on a TA Instruments Discovery DSC in a closed aluminium pan (40\u2005\u00b5L) under nitro\u00adgen flow (50\u2005ml\u2005min\u22121) and a heating rate of 10\u00b0C min\u22121 in the temperature range 25\u2013300 \u00b0C  and a heating rate of 10\u00b0C min\u22121 in the temperature range 25\u2013300\u00b0C  technique. It shows a broad band at about 3200\u2005cm\u22121, which corresponds to the O\u2014H stretching vibrations. Strong stretching vibrations of C=O  and C\u2014O (aromatic ether) appear at 1683 and 1266\u2005cm\u22121, respectively. Bands corresponding to N\u2014O asymmetric and symmetric stretching modes can be found at 1547 and 1366\u2005cm\u22121, respectively. Characteristic weak overtones of the aromatic ring can be seen at 1800\u20131700\u2005cm\u22121.The IR spectrum Fig.\u00a012 of compoUiso(H) = 1.5Ueq(O) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020000225/su5534sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020000225/su5534Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000225/su5534Isup3.cmlSupporting information file. DOI: 1957893CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I tricarbonyl complexes bearing ester-substituted bi\u00adpyridine or bi\u00adquinoline ligands is reported.The structural comparison of two Mn fac-bromido\u00adtricarbon\u00adylmangan\u00adese(I), [MnBr(C16H16N2O4)(CO)3], I, and fac-bromido\u00adtricarbon\u00adylmanganese(I), [MnBr(C24H20N2O4)(CO)3], II. In both complexes, the manganese(I) atom adopts a distorted octa\u00adhedral coordination sphere defined by three carbonyl C atoms, a Br\u2212 anion and two N atoms from the chelating \u03b1-di\u00adimine ligand. Both complexes show fac configurations of the carbonyl ligands. In I, the complex mol\u00adecules are linked by C\u2014H\u22efBr hydrogen bonds and aromatic \u03c0\u2013\u03c0 contacts. In II, intra\u00admolecular C\u2014H\u22efO hydrogen bonds are present as well as inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions.The crystal structures of two manganese(I) complexes with ester-substituted bi\u00adpyridine or bi\u00adquinoline supporting ligands are reported, namely,  We successfully compared their crystal structures and photophysical properties. As expected, a CT band shift in the visible region was confirmed, depending on the size of the \u03c0-conjugation system in \u03b1-di\u00adimine ligands. This finding will provide information in the future design of suitable complexes for a variety of photoreactions  and 2.047\u2005(2)\u2005\u00c5, while in II, the Mn\u2014N bond lengths are 2.063\u2005(2) and 2.068\u2005(2)\u2005\u00c5. In I and II, the fac configuration of three CO ligands around the central manganese(I) atom is in agreement with their IR data. On the basis of their bond parameters, all CO ligands have typical triple-bond characters.The mol\u00adecular structures of compounds I (C3\u2014Mn1\u2014N1\u2014C8 and C2\u2014Mn1\u2014N2\u2014C9) are \u2212169.17\u2005(15) and 168.81\u2005(14)\u00b0, respectively; the corresponding torsion angles in II (C3\u2014Mn1\u2014N1\u2014C12 and C2\u2014Mn1\u2014N2\u2014C13) are \u2212147.52\u2005(16) and 147.08\u2005(17)\u00b0, respectively  in debqn, and the equatorial CO ligands (C3\u2261O3 and C2\u2261O2). On the basis of similar steric hindrance, comparable torsion angles [150.4\u2005(15) and \u2212150.7\u2005(5)\u00b0] have been also observed in the related ReI complex \u2005\u00c5 and C10\u2014C11 = 1.392\u2005(3)\u2005\u00c5] are considerably longer than the corresponding one in II [C10\u2014C11 = 1.364\u2005(4)\u2005\u00c5 and C14\u2014C15 = 1.368\u2005(4)\u2005\u00c5]. This difference in structural parameters may eventually affect the intra\u00admolecular hydrogen-bond formation.Despite similar mol\u00adecular skeletons, only g Table\u00a02. The C\u2014CI, complex mol\u00adecules are linked by pairs of weak C\u2014H\u22efBr hydrogen bonds (Table\u00a01Cg1\u22efCg2iii = 3.683\u2005(1)\u2005\u00c5; Cg1 and Cg2 are the centroids of the N1/C4\u2013C8 and N2/C9\u2013C13 rings, respectively; symmetry code: (iii) 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z], forming a three-dimensional supra\u00admolecular structure \u2005\u00c5 and Cg5\u22efCg6iv = 4.002\u2005(2)\u2005\u00c5; Cg3, Cg4, Cg5 and Cg6 are the centroids of the C4\u2013C9, C16\u2013C21, N1/C8\u2013C12 and N2/C13\u2013C17 rings, respectively; symmetry code: (iv) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z]. These inter\u00adactions lead to the formation of a three-dimensional network structure 3(N-N)], some structures have been reported  complexes with a bidentate bi\u00adpyridine derivative ligand (N-N) of the form et al. .The ligands, debpy and debqn, were prepared as described by Chandrasekharam  al. 2011 and Hoer al. 2006. The ligSynthesis of I and II: Compounds I and II were handled and stored in the dark to minimize exposure to light. For the synthesis of I, [MnBr(CO)5]  and debpy  were dissolved in CHCl3 (10\u2005ml). The reaction mixture was stirred at 313\u2005K for 14\u2005h under N2. After the solvent was evaporated under reduced pressure, an excess of Et2O (30\u2005ml) was added to the solution; then, the solution was allowed to stand at 253\u2005K overnight. The resultant precipitate was collected by filtration, washed with Et2O, and then dried under vacuum . Red crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of I for one week. FTIR (KBr pellet): \u03bdCO /cm\u22121 = 2028, 1918 (br) (C\u2261O), 1730 (C=O). UV\u2013vis (CHCl3): \u03bb /nm (\u220a /M\u22121 cm\u22121) = 483\u2005(3700), 367\u2005(4100), 318\u2005(21000), 247\u2005(24000).5]  and debqn  for 20\u2005h afforded II . Purple crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of II for one week. FTIR (KBr pellet): \u03bdCO /cm\u22121 = 2016, 1942, 1926 (C\u2261O), 1725 (C=O). UV\u2013vis (CHCl3): \u03bb /nm (\u220a /M\u22121 cm\u22121) = 548\u2005(3200), 383\u2005(19000), 276\u2005(37000).A similar reaction between [MnBr(CO)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020010750/dj2012sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989020010750/dj2012Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020010750/dj2012Isup4.molSupporting information file. DOI: 10.1107/S2056989020010750/dj2012IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020010750/dj2012IIsup5.molSupporting information file. DOI: 2021226, 2021225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex, a newly synthesized dye, the metal atom is coordinated by two N atoms and two O atoms from two bidentate (E)-1-[diazen\u00adyl]naphthalen-2-olate ligands.In the title Cu 16H8Br3N2O)2]\u00b7C2H6OS, the CuII atom is tetra\u00adcoordinated in a square-planar coordination, being surrounded by two N atoms and two O atoms from two N,O-bidentate (E)-1-[diazen\u00adyl]naphthalen-2-olate ligands. The two N atoms and two O atoms around the metal center are trans to each other, with an O\u2014Cu\u2014O bond angle of 177.90\u2005(16)\u00b0 and a N\u2014Cu\u2014N bond angle of 177.8\u2005(2)\u00b0. The average distances between the CuII atom and the coordinated O and N atoms are 1.892\u2005(4) and 1.976\u2005(4)\u2005\u00c5, respectively. In the crystal, complexes are linked by C\u2014H\u22efO hydrogen bonds and by \u03c0\u2013\u03c0 inter\u00adactions involving adjacent naphthalene ring systems [centroid\u2013centroid distance = 3.679\u2005(4)\u2005\u00c5]. The disordered DMSO mol\u00adecules inter\u00adact weakly with the complex mol\u00adecules, being positioned in the voids left by the packing arrangement of the square-planar complexes. The DMSO solvent mol\u00adecule is disordered over two positions with occupancies of 0.70 and 0.30.In the title compound, [Cu(C The N\u2014Cu\u2014N bond angle is 177.8\u2005(2)\u00b0. The two Cu\u2014O distances are 1.882\u2005(4) and 1.892\u2005(4)\u2005\u00c5. All bond lengths are similar to those observed in similar crystal structures  shows a multiplet around 7 and 8 ppm attributed to the aromatic protons. The IR spectrum of the complex shows the vibration bands: \u03bd(N=N); 1360\u2005cm\u22121, \u03bd(C\u2014N): 1149\u2005cm \u22121, \u03bd(C\u2014Br): 645\u2005cm\u22121, \u03bd(C\u2014O): 1207\u2005cm\u22121 (aromatic), \u03bd(C=C): 1498\u2005cm\u22121 (aromatic), \u03bd(C\u2014H): 2945\u2005cm\u22121 (aromatic), \u03bd(Cu\u2014N): 417\u2005cm\u22121, \u03bd(Cu-O): 558\u2005cm\u22121. The UV\u2013Vis spectrum measured in CH2Cl2 (10 \u22125 M), shows three absorption bands: an intense band at 268\u2005nm (\u220a = 29.94 108 M\u22121 cm\u22121) attributed to intra-ligand charge-transfer transition, a band at 382\u2005nm (\u220a = 79.21 107 M\u22121 cm\u22121) associated with the azo form of the ligand and a band at 462\u2005nm (\u220a = 63.84 107 M\u22121 cm\u22121) attributed to metal\u2013ligand charge transfer.The complex, bis-1--2-naphtho\u00adlatecopper(II), was obtained by mixing 1\u2005mmol of 1--2-naphthol dissolved in 20\u2005ml of THF with 0.5\u2005mmol of Cu(OAc)Uiso(H) = 1.2 Ueq(C). An absorption correction was not applied in view of the very small size of the crystal [0.1 \u00d7 0.09 \u00d7 0.08\u2005mm]. The DMSO solvent mol\u00adecule shows disorder over two positions with final occupancies of 0.70 and 0.30. The disordered atoms were modelled as anisotropic using EADP restraints. H atoms of the disordered DMSO were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020001863/tx2018sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020001863/tx2018Isup2.hklStructure factors: contains datablock(s) I. DOI: 1983017CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cationic layers are made up from two types of [Na(H2O)6] octa\u00adhedra that form linear 1\u221e[Na(H2O)4/2(H2O)2/1] chains linked by dimeric [Na(H2O)2/2(H2O)4/1]2 units on both sides of the chains. The isolated trigonal\u2013pyramidal sulfite anions are connected to the cationic layers through an intricate network of O\u2014H\u22efO hydrogen bonds, together with a remarkable O\u2014H\u22efS hydrogen bond, with an O\u22efS donor\u2013acceptor distance of 3.2582\u2005(6)\u2005\u00c5, which is about 0.05\u2005\u00c5 shorter than the average for O\u2014H\u22efS hydrogen bonds in thio\u00adsalt hydrates and organic sulfur com\u00adpounds of the type Y\u2014S\u2014Z . Structural relationships between monoclinic Na2SO3(H2O)7 and ortho\u00adrhom\u00adbic Na2CO3(H2O)7 are discussed in detail.The monoclinic crystal structure of Na Indeed, the two hepta\u00adhydrates show not only a close metrical relationship , as a corrosion inhibitor in aqueous media, as a bleaching agent, as a solubilizing agent for cellulose, straw and wood in the pulp and paper industry, or as an additive in dying processes. In the USA alone, the production of sodium sulfite reached 150 000 tons in 2002 7 were grown by recrystallization of a commercial anhydrous sample  from an aqueous solution at room tem\u00adper\u00adature by slow evaporation over the course of several days. In order to remove adherent mother liquor, the crystals were placed on filter paper and subsequently immersed in Paratone oil. The crystal under investigation was cleaved from a larger specimen.Colourless prismatic crystals of Na2SO3(H2O)7 was originally solved and refined in the space group P121/n1 (No. 14), with lattice parameters a = 11.8576\u2005(8), b = 7.2197\u2005(5), c = 12.6965\u2005(9)\u2005\u00c5 and \u03b2 = 106.7938\u2005(17)\u00b0 at 100\u2005K . The values for the lattice parameters at 100\u2005K are in good agreement with the previous study, with values of a = 11.922, b = 7.260, c = 12.765\u2005\u00c5 and \u03b2 = 107.22\u00b0 obtained at room temperature from Weissenberg film data 7 7, using the matrix 7 and \u03b2-Na2CO3(H2O)7. All H atoms present in the crystal structure of Na2SO3(H2O)7 were located in a difference Fourier map and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a022SO3(H2O)7, all atoms  are located on general sites. The two sodium cations are surrounded by six water mol\u00adecules, defining a distorted octa\u00adhedral coordination polyhedron in each case. The Na\u2014O distances range from 2.3690\u2005(6) to 2.4952\u2005(6)\u2005\u00c5 (Table\u00a03[6]\u2014O of 2.44\u2005(11)\u2005\u00c5 calculated for 5520 individual bonds \u2013176.42\u2005(2)\u00b0 for Na1 and 165.81\u2005(2)\u2013174.23\u2005(2)\u00b0 for Na2, and for cis O atoms in the range 81.464\u2005(19)\u2013101.74\u2005(2)\u00b0 for Na1 and 81.51\u2005(2)\u2013103.23\u2005(2)\u00b0 for Na2. The two types of [Na(H2O)6] octa\u00adhedra show a different linkage pattern. Octa\u00adhedra centred by Na1 share common edges 4/2(H2O)2/1] chains running parallel to [001], whereas octa\u00adhedra centred by Na2 make up dimeric [Na2(H2O)2/2(H2O)4/1]2 units by sharing an edge (O5 and O5iii). In both cases, the corresponding Na\u2014O bonds to the shared O atoms at the edges are the shortest in the respective octa\u00adhedron. The dimeric units connect adjacent chains by sharing the terminal water mol\u00adecules (O9 and O7) on both sides of the chains (corner-sharing links). This way, the sodium\u2013water octa\u00adhedra are assembled by edge- and corner-sharing into an infinite layer extending parallel to (100) .In the crystal structure of Na\u00c5 Table\u00a03, with me0) Fig.\u00a01a.IV atom occupying the pyramidal position. Atom S1 is 0.5912\u2005(4)\u2005\u00c5 above the basal plane formed by atoms O1, O2 and O3. The S\u2014O bond lengths are in a narrow range 1.5224\u2005(5)\u20131.5338\u2005(5)\u2005\u00c5 [mean 1.527\u2005(6)\u2005\u00c5], just like the O\u2014S\u2014O angles . Again, these values are in good agreement with the grand mean SIV\u2014O bond length of 1.529\u2005(15)\u2005\u00c5 calculated for 90 bonds and with the O\u2014SIV\u2014O angles in the range \u223c99\u2013107\u00b0 with a mean value of \u223c104\u00b0 4/2(H2O)2/1] chains .The sulfite anion has the characteristic trigonal\u2013pyramidal configuration, with the Sns Fig.\u00a02a.a). Based on the donor\u2013acceptor distances between 2.7204\u2005(7) and 2.9110\u2005(8)\u2005\u00c5 (Table\u00a04a). Thereby, atom O1 is the acceptor of three, O2 of four and O3 of three hydrogen bonds. It is worth noting that the S\u2014O bond lengths reflect this situation nicely, with S1\u2014O2 = 1.5338\u2005(5)\u2005\u00c5 being about 0.01\u2005\u00c5 longer than the remaining two. The O9 water mol\u00adecule, bonded to Na1, Na2 and via H9A to O2, lacks a clearcut hydrogen bond for its second H atom (H9B), which points to H6B of the O6\u2014H6B\u22efO3 hydrogen bond \u00b7H2O 2]\u00b72.25H2O (S2O5) 7 7 and ortho\u00adrhom\u00adbic Na2CO3(H2O)7 (Table\u00a012O)6] octa\u00adhedra  is present in the carbonate, likewise situated at x \u2243 0, b). The carbonate groups do not show pyramidalization 2/2(H2O)4/1]2 dimers.The close structural relationship between monoclinic Na7 Table\u00a01 becomes ll Fig.\u00a02b. The c2O)2/2(H2O)4/1]2 dimers in the layers. Whereas in the sulfite structure, the dimers at y \u2243 0 and y \u2243 c-glide plane 7, to NH4SO3(H2O) 6 6, which is built up from [Mg(H2O)6] octa\u00adhedra and isolated SO3 pyramids within a lattice of the space group type R3, and with Mg and S atoms both located on threefold rotation axes, there are two independent water mol\u00adecules that donate, apart from one water\u2013water hydrogen bond, three water\u2013Osulfite hydrogen bonds to each sulfite O atom, com\u00adparable to O1 and O3 in Na2SO3(H2O)7, but with shorter O\u22efO distances  than in the latter. An electron deformation density study of MgSO3(H2O)6 6 nor NH4SO3(H2O) contain O\u2014H\u22efS or N\u2014H\u22efS hydrogen bonds.Crystal structures with sulfite groups anchored exclusively by hydrogen bonds are at present restricted to the title com\u00adpound Na2SO4(H2O)7  has a com\u00adpletely different arrangement of the principal building units. Its crystal structure is com\u00adprised of [Na(H2O)]6 octa\u00adhedra concatenated by edge- and corner-sharing into a three-dimensional network with isolated tetra\u00adhedral sulfate anions hydrogen bonded to the chains. Also, for sodium com\u00adpounds with analogous trigonal\u2013pyramidal oxoanions and the same charge, i.e.XO32\u2212, with X = Se and Te, no phases related structurally or com\u00adpositionally to Na2SO3(H2O)7 are known. For Na2SeO3, the anhydrous form  is made up from [NaO6] octa\u00adhedra and trigonal\u2013pyramidal SeO32\u2212 anions 5 5 . These structures are based on two- or three-dimensional assemblies of [NaO5] polyhedra (Se) and [NaO6] octa\u00adhedra (Se and Te), to which SeO3/TeO3 groups are bonded via two (Se) or one (Te) O atom. The [NaO6] octa\u00adhedra in these two salts share common faces and edges but no vertices. As pointed out by Philippot et al. (19792TeO3(H2O)5 and confirmed also for Na2SeO3(H2O)5 7 structure and vice versa. A further com\u00adparison with other hydrated sodium com\u00adpounds com\u00adprised of related oxo anions shows no close structural relationship to the title hepta\u00adhydrate. For example, Na al. 1979 for Na2T10.1107/S2053229620004404/ep3004sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2053229620004404/ep3004Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2053229620004404/ep3004sup3.txtCIF with full numerical data (setting P121/n1). DOI: Click here for additional data file.10.1107/S2053229620004404/ep3004Isup4.cmlSupporting information file. DOI: 1993827CCDC reference:"}
{"text": "Within the sheets, very weak \u03c0\u2013\u03c0 stacking inter\u00adactions occur. The Hirshfeld surface analysis and fingerprint plots reveal that the crystal structure is dominated by H\u22efH (37.1%) and C\u22efH (30.1%) contacts.In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in the formation of sheets along the  14H12INO, was synthesized by condensation of 2-hy\u00addroxy-3-methyl\u00adbenzaldehyde and 2-iodo\u00adaniline, and crystallizes in the ortho\u00adrhom\u00adbic space group P212121. The 2-iodo\u00adphenyl and benzene rings are twisted with respect to each other, making a dihedral angle of 31.38\u2005(2)\u00b0. The mol\u00adecular structure is stabilized by an O\u2014H\u22efN hydrogen bond, forming an S(6) ring motif. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in the formation of sheets along the a-axis direction. Within the sheets, very weak \u03c0\u2013\u03c0 stacking inter\u00adactions lead to additional stabilization. The Hirshfeld surface analysis and fingerprint plots reveal that the crystal structure is dominated by H\u22efH (37.1%) and C\u22efH (30.1%) contacts. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. The crystal studied was refined as a two-component inversion twin.The title compound, C We report here the synthesis and the crystal and mol\u00adecular structures of the title compound, along with the results of a Hirshfeld surface analysis.In the present study, a new Schiff base, S(6) ring motif, which stabilizes the mol\u00adecular structure and induces the Schiff base atoms  to be coplanar with the methyl\u00adphenol moiety. Of this planar unit (r.m.s deviation = 0.0274\u2005\u00c5), atoms O1 and N1 show the largest deviations from planarity in positive and negative directions [O1 = 0.035\u2005(4)\u2005\u00c5 and N1 = \u22120.060\u2005(4)\u2005\u00c5]. The C7\u2014N1 and C13\u2014O1 bonds of the title compound are the most important indicators of the tautomeric type. The C13\u2014O1 bond is of double-bond character for the keto\u2013amine tautomer, whereas this bond displays single-bond character in the enol\u2013imine tautomer. In addition, the C7\u2014N1 bond is also a double bond in the enol\u2013imine tautomer and a single bond length in the keto\u2013amine tautomer. In the title compound, the enol\u2013imine form is favored over the keto-amine form, as indicated by the C13\u2014O1 [1.352\u2005(6)\u2005\u00c5] and C7\u2014N1 [1.286\u2005(8)\u2005\u00c5] bonds, whose lengths indicate a high degree of single-bond and double-bond character, respectively. The shortest C\u2014C distance (C3\u2014C4) is 1.344\u2005(11)\u2005\u00c5 in the C1\u2013C6 ring with the weighted average ring bond distance being 1.376\u2005(11)\u2005\u00c5 for this ring.Depending on the tautomers, two types of intra\u00admolecular hydrogen bonds are observed in Schiff bases: O\u2014H\u22efN in enol\u2013imine and N\u2014H\u22efO in keto\u2013amine tautomers. Most of these compounds are non-planar. The title compound, (I)a-axis direction by C2\u2014H2\u22efCg2i inter\u00adactions (Table\u00a01Cg1\u22efCg2ii of 4.093\u2005(2)\u2005\u00c5  of the title compound are illustrated in Fig.\u00a04a and red areas on phenyl rings mapped with shape-index  correspond to the H\u22ef\u03c0 contacts resulting from hydrogen bond C\u2014H\u22ef\u03c0(ring)  Table\u00a01 and \u03c0\u2013\u03c0 et al., 2016E)-2-[(2-iodo\u00adphenyl\u00adimino)\u00admeth\u00adyl]phenol gave six hits: bis\u00adcopper(II) bis\u00adimino]\u00admeth\u00adyl}phenolato)bis\u00ad(iso\u00adthio\u00adcyan\u00adato)\u00addiiron(III) methanol solvate bis\u00ad(m-methano\u00adlato)tetra\u00adkis\u00adimino]\u00admeth\u00adyl}phenolato)bis\u00ad(iso\u00adthio\u00adcyanato)\u00adtetra\u00adiron(III) di\u00adchloro\u00admethane solvate  in ethanol (20\u2005ml) and 2-iodo\u00adaniline  in ethanol (20\u2005ml). The reaction mixture was stirred for 4\u2005h under reflux. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. Hydroxyl H atoms were placed according to a difference-Fourier map and were freely refined. The crystal studied was refined as a two-component inversion twin. This reflection file contains the non-overlapping reflections of the two twin components as well as the overlapping reflections. The BASF parameter for this two-component twin refined to \u22120.03242\u2005(8).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020011974/zl2795sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020011974/zl2795Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020011974/zl2795Isup3.cmlSupporting information file. DOI: 2026445CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Alzheimer\u2019s disease (AD)-related tauopathy can be measured with CSF phosphorylated tau (pTau) and tau PET. We aim to investigate the associations between these measurements and their relative ability to predict subsequent disease progression.18F-florbetapir or 18F-florbetaben), 18F-flortaucipir (FTP) PET, CSF measurements, structural MRI, and cognition, we examined inter-relationships between these biomarkers and their predictions of subsequent FTP and cognition changes.In 219 cognitively unimpaired and 122 impaired Alzheimer\u2019s Disease Neuroimaging Initiative participants with concurrent amyloid-\u03b2 (A\u03b2) PET  were 4 times more prevalent (p\u2009<\u2009\u00a00.001) than abnormal FTP only individuals (6.8%). Furthermore, among individuals on the AD pathway, CSF pTau/A\u03b240 mediates the association between A\u03b2 PET and FTP PET accumulation, but FTP PET is more closely linked to subsequent cognitive decline than CSF pTau/A\u03b240.The use of a CSF pTau/A\u03b240 may be a superior measure of tauopathy compared to CSF pTau alone, and CSF pTau/A\u03b240 enables detection of tau accumulation at an earlier stage than FTP among A\u03b2+ individuals.Together, these findings suggest that CSF pTau/A\u03b2 Extracellular amyloid-\u03b2 (A\u03b2) peptides in cortical A\u03b2 plaques and intracellular phosphorylated tau protein as neurofibrillary tangles are key hallmarks of Alzheimer\u2019s disease (AD) that can be measured in vivo with positron emission tomography (PET) imaging and biofluid markers including plasma and cerebrospinal fluid (CSF) assays. The relationship between CSF A\u03b2 and A\u03b2 PET in AD has been widely reported \u20138, but r42 in the A\u03b2\u2212 range ) associated with CSF A\u03b242 in A\u03b2 PET\u2212 participants, whereas no association was found in A\u03b2+ participants  sample of 384 A\u03b2\u2212 participants  and A\u03b2+  participants.CSF A\u03b2tus Fig.\u00a0a, b. Bef40 , CSF pTau/A\u03b240 , and tau PET in Temporal-metaROI  and entorhinal  in A\u03b2+ participants. Notably, the association with A\u03b2 PET increased from rho value 0.38 when using CSF pTau alone to 0.60 using the CSF pTau/A\u03b240 .We found A\u03b2 PET was significantly associated with CSF and PET tau measurements, which were driven by A\u03b2+ individuals. Baseline A\u03b2 PET was positively associated with CSF pTau , A\u03b2\u2212 and A\u03b2+ participants were classified as tau normal (T\u2212)/abnormal (T+) using CSF pTau or CSF pTau/A\u03b240 or tau PET thresholds, dividing the whole cohort into A\u2212/T\u2212, A\u2212/T+, A+/T\u2212, and A+/T+ groups. Few A\u03b2\u2212 participants had abnormal CSF pTau/A\u03b240 (7.6%) and temporal tau PET (5.3%), whereas A\u03b2+ participants showed a 3.0\u20134.5 times higher percentage of abnormal CSF pTau/A\u03b240 (32.6%) and temporal tau PET (24.0%) than A\u03b2\u2212 participants /abnormal (+) on CSF pTau or CSF pTau/A\u03b240 (PTAU+/\u2212) and entorhinal or Temporal-metaROI FTP SUVR (FTP+/\u2212). Abnormal CSF pTau only had higher prevalence  than abnormal CSF pTau/A\u03b240 only in A\u03b2\u2212 participants, whereas abnormal CSF pTau/A\u03b240 only had marginally higher prevalence  than abnormal CSF pTau only in A\u03b2+ participants. CSF pTau/A\u03b240  were positively associated with temporal tau PET across all participants. A\u03b2+ participants were responsible for this relationship because no association was found in A\u03b2\u2212 participants  . The results were similar for entorhinal tau PET , CSF pTau/A\u03b240 , and Temporal-metaROI tau PET  were all associated with subsequent tau PET increase (\u0394FTP) in A\u03b2+ participants . CSF pTau/A\u03b240-involved pathways  explained 70% of the association  between A\u03b2 PET and \u0394FTP increase in A\u03b2+ participants.The latent variable model demonstrated that the direct association between A\u03b2 and \u0394FTP increase in A\u03b2+ participants was not significant after including the CSF pTau/A\u03b2FTP Fig.\u00a0d, reduci\u03b2std\u2009=\u2009\u2212\u20090.41 ), CSF pTau/A\u03b240 , and Temporal-metaROI tau PET  were all associated with subsequent cognitive decline in A\u03b2+ participants  remained predictive when all variables were added into one multivariate model. The results were similar for entorhinal tau PET. In contrast, only CSF pTau/A\u03b240  was associated with subsequent cognitive decline in A\u03b2\u2212 participants.Baseline A\u03b2 PET  Tau PET associations with CSF pTau/A\u03b240 were highest in medial and lateral temporal regions. (3) Associations between A\u03b2 PET, CSF pTau/A\u03b240, and tau PET  were substantially driven by A\u03b2 PET-positive individuals. (4) Among these A\u03b2+ individuals, most participants (66%) were concordant on CSF pTau/A\u03b240 and Temporal-metaROI tau PET, but among discordant individuals, those with abnormal CSF pTau/A\u03b240 and normal tau PET were 4 times more prevalent (26.7%) than those with abnormal tau PET and normal CSF pTau/A\u03b240 (6.8%). (5) Among these A\u03b2+ individuals, baseline A\u03b2 PET, CSF pTau/A\u03b240, and tau PET were all associated with subsequent tau PET increase, while CSF pTau/A\u03b240 significantly mediates the association between A\u03b2 PET and tau PET . (6) Only tau PET was predictive of longitudinal cognitive decline when baseline A\u03b2 PET, CSF pTau/A\u03b240, and\u00a0tau PET were put in one multivariate model.This study had several primary findings: (1) use of a CSF pTau/A\u03b242 , but it is possible that early and late changes in CSF A\u03b240 may contribute to the tau-related effects we observed.Our motivation to adjust CSF pTau measurements was based on our observation that A\u03b2 PET-negative individuals had abnormal (\u201cpositive\u201d) CSF pTau that correlated positively with high  CSF A\u03b242 Fig.\u00a0c, suggesiversity , 16, and42 alone , 17\u201319, 42 alone . However studies \u201351 have al study  observed40 and tau PET were stronger in ROIs in the temporal lobe than other areas such as frontal and occipital lobes that accumulate tau in later stages of disease [40 and tau PET was primarily driven by A\u03b2 PET positivity and less influenced by clinical diagnosis  in the A\u03b2\u2212 individuals, which was in line with previous reports [40 or tau PET) was rarely (5.3\u20137.9%) abnormal in the A\u03b2\u2212 range  and40 ratio improves the sensitivity to detect CSF tau by adjusting for individual differences in CSF production. Furthermore, although PET and CSF measures of tau are broadly concordant in the majority (76%) of individuals when measured dichotomously, our findings support recent work [In summary, we found that the use of a CSF pTau/A\u03b2ent work  indicatient work . Among aAdditional file 1:Figure\u00a0S1. The ROC analysis using the Youden index classifying 280 A\u03b2- ADNI cognitively unimpaired (CU) participants and 183 A\u03b2\u2009+\u2009ADNI MCI and AD patients as the endpoint to define the cutoff \u22651.25 for Temporal-metaROI FTP SUVR. AUC: 0.876 . Among these 463 ADNI participants, 217 (47%) participants were included in the analyses of the manuscript. Figure\u00a0S2. Histograms of Temporal-metaROI FTP SUVRs of (A) all 775 ADNI participants, (B) 280 A\u03b2- ADNI CU participants and (C) 183 A\u03b2\u2009+\u2009ADNI MCI and AD patients with tau PET scan. Red dotted line is the cutoff of Temporal-metaROI FTP SUVR 1.25. Figure\u00a0S3. The ROC analysis using the Youden index classifying 280 A\u03b2- ADNI CU participants and 183 A\u03b2\u2009+\u2009ADNI MCI and AD patients as the endpoint to define the cutoff \u22651.21 for entorhinal FTP SUVR. AUC: 0.891 . Figure\u00a0S4. Histograms of entorhinal FTP SUVRs of (A) all 775 ADNI participants, (B) 280 A\u03b2- ADNI CU participants and (C) 183 A\u03b2\u2009+\u2009ADNI MCI and AD patients with tau PET scan. Red dotted line is the cutoff of entorhinal FTP SUVR 1.21. Figure\u00a0S5. The ROC analysis using the Youden index classifying 320 A\u03b2- ADNI CU participants and 429 A\u03b2\u2009+\u2009ADNI MCI and AD patients as the endpoint to define the cutoff \u226522 for CSF p-Tau. AUC: 0.865 . Among these 749 ADNI participants, 212 (28%) participants were included in the analyses of the manuscript. Figure\u00a0S6. Histograms of CSF p-Tau of (A) all 1534 ADNI participants, (B) 320 A\u03b2- ADNI CU participants and (C) 429 A\u03b2\u2009+\u2009ADNI MCI and AD patients with CSF p-Tau measurement. Red dotted line is the cutoff of CSF p-Tau 22. Figure\u00a0S7. The ROC analysis using the Youden index classifying 169 A\u03b2- ADNI CU participants and 160 A\u03b2\u2009+\u2009ADNI MCI and AD patients as the endpoint to define the cutoff \u22650.0012 for CSF p-Tau/A\u03b240 ratio. AUC: 0.976 . Among these 329 ADNI participants, 201 (61%) participants were included in the analyses of the manuscript. Figure\u00a0S8. Histograms of CSF p-Tau/A\u03b240 for (A) all 447 ADNI participants, (B) 169 A\u03b2- ADNI CU participants and (C) 160 A\u03b2\u2009+\u2009ADNI MCI and AD patients with CSF p-Tau/A\u03b240. Red dotted line is the 0.0012 cutoff for the CSF p-Tau/A\u03b240 ratio. Figure\u00a0S9. Cross-sectional associations between CSF MASS A\u03b242 and CSF p-Tau. The vertical gray dashed line reflects the abnormal threshold of CSF p-Tau. Abbreviations: p-Tau\u2009=\u2009phosphorylated tau; A\u03b2\u2009=\u2009amyloid-\u03b2; CU\u2009=\u2009cognitively unimpaired; MCI\u2009=\u2009mild cognitive impairment; AD\u2009=\u2009Alzheimer\u2019s disease. Figure\u00a0S10. Regions with significant association between CSF P-tau and FTP tau in (A) A\u03b2+, (B) CU and (C) non-demented participants. Abbreviations: Spearman rho\u2009=\u2009Spearman\u2019s correlation coefficient; p-Tau\u2009=\u2009phosphorylated tau; A\u03b2\u2009=\u2009amyloid-\u03b2; FTP\u2009=\u200918F-flortaucipir; SUVR\u2009=\u2009standardized uptake value ratio; CU\u2009=\u2009cognitively unimpaired; MCI\u2009=\u2009mild cognitive impairment; AD\u2009=\u2009Alzheimer\u2019s disease. Figure\u00a0S11. Cross-sectional associations between A\u03b2 PET, CSF p-Tau/A\u03b240 and entorhinal tau PET. (A). Associations between baseline entorhinal tau PET and A\u03b2 PET. Associations between baseline CSF p-Tau/A\u03b240 and entorhinal tau PET in the whole cohort (B), A\u03b2- (C) and A\u03b2\u2009+\u2009(D) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: A\u03b2\u2009=\u2009amyloid-\u03b2; A\u2009=\u2009A\u03b2 PET; \u2212\u2009=\u2009negative; +\u2009=\u2009positive; AD\u2009=\u2009Alzheimer\u2019s disease; CU\u2009=\u2009cognitively unimpaired; FTP\u2009=\u200918F-flortaucipir; MCI\u2009=\u2009mild cognitive impairment. Figure\u00a0S12. Cross-sectional associations between A\u03b2 PET, CSF pTau/A\u03b240 and tau PET using alternative cutoffs. Associations between baseline A\u03b2 PET and (A) CSF pTau, (B) CSF pTau/A\u03b240 and (C) temporal tau PET. Associations between baseline CSF pTau and CSF pTau/A\u03b240 in the whole cohort (D), A\u03b2- (E) and A\u03b2\u2009+\u2009(F) participants. Associations between baseline CSF pTau/A\u03b240 and Temporal-metaROI tau PET in the whole cohort (G), A\u03b2- (H) and A\u03b2\u2009+\u2009(I) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: A\u03b2\u2009=\u2009amyloid-\u03b2; A\u2009=\u2009A\u03b2 PET; \u2212\u2009=\u2009negative; +\u2009=\u2009positive; AD\u2009=\u2009Alzheimer\u2019s disease; CU\u2009=\u2009cognitively unimpaired; FTP\u2009=\u200918F-flortaucipir; MCI\u2009=\u2009mild cognitive impairment; pTau\u2009=\u2009phosphorylated tau; PTAU\u2009=\u2009CSF pTau or CSF pTau/A\u03b240 ratio; SUVR\u2009=\u2009standardized uptake value ratio; T\u2009=\u2009CSF pTau or CSF pTau/A\u03b240 or tau PET. Figure\u00a0S13. Cross-sectional associations between A\u03b2 PET, CSF p-Tau/A\u03b240 and entorhinal tau PET using alternative cutoffs. (A). Associations between baseline entorhinal tau PET and A\u03b2 PET. Associations between baseline CSF p-Tau/A\u03b240 and entorhinal tau PET in the whole cohort (B), A\u03b2- (C) and A\u03b2\u2009+\u2009(D) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: A\u03b2\u2009=\u2009amyloid-\u03b2; A\u2009=\u2009A\u03b2 PET; \u2212\u2009=\u2009negative; +\u2009=\u2009positive; AD\u2009=\u2009Alzheimer\u2019s disease; CU\u2009=\u2009cognitively unimpaired; FTP\u2009=\u200918F-flortaucipir; MCI\u2009=\u2009mild cognitive impairment."}
{"text": "The three-mol\u00adecule aggregates are connected into a supra\u00admolecular tape by amide-N\u2014H\u22efO(amide) hydrogen bonding.In the title 1:2 co-crystal,  14H14N4O2\u00b72C7H5ClO2, comprises two half mol\u00adecules of oxalamide (4LH2), as each is disposed about a centre of inversion, and two mol\u00adecules of 4-chloro\u00adbenzoic acid (CBA), each in general positions. Each 4LH2 mol\u00adecule has a (+)anti\u00adperiplanar conformation with the pyridin-4-yl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angles between the respective central core and the pyridyl rings being 68.65\u2005(3) and 86.25\u2005(3)\u00b0, respectively, representing the major difference between the independent 4LH2 mol\u00adecules. The anti conformation of the carbonyl groups enables the formation of intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bonds, each completing an S(5) loop. The two independent CBA mol\u00adecules are similar and exhibit C6/CO2 dihedral angles of 8.06\u2005(10) and 17.24\u2005(8)\u00b0, indicating twisted conformations. In the crystal, two independent, three-mol\u00adecule aggregates are formed via carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding. These are connected into a supra\u00admolecular tape propagating parallel to [100] through amide-N\u2014H\u22efO(amide) hydrogen bonding between the independent aggregates and ten-membered {\u22efHNC2O}2 synthons. The tapes assemble into a three-dimensional architecture through pyridyl- and methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) and CBA-C\u2014H\u22efO(amide) inter\u00adactions. As revealed by a more detailed analysis of the mol\u00adecular packing by calculating the Hirshfeld surfaces and computational chemistry, are the presence of attractive and dispersive Cl\u22efC=O inter\u00adactions which provide inter\u00adaction energies approximately one-quarter of those provided by the amide-N\u2014H\u22efO(amide) hydrogen bonding sustaining the supra\u00admolecular tape.The asymmetric unit of the title 1:2 co-crystal, C The formation of such O\u2014H\u22efN hydrogen bonding is consistent with literature precedent, which indicates a very high propensity for these hydrogen-bonding patterns between carb\u00adoxy\u00adlic acids and pyridyl entities, at least in the absence of competing supra\u00admolecular synthons  hydrogen bonds are formed instead , each in a general position. Pairs of 4LH2 and CBA mol\u00adecules are connected via carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding, Table\u00a01i.e. 4LH2(CBA)2, as shown in Fig.\u00a01The crystallographic asymmetric unit of (I)4LH2 mol\u00adecule is centrosymmetric, the central C2N2O2 chromophore in each is strictly planar. As is usually found in these mol\u00adecules \u2005\u00c5] and C14\u2014C14ii [1.539\u2005(2)\u2005\u00c5] bond lengths are longer than usual owing to the electronegative substituents connected to both carbon atoms . The conformation of each 4LH2 mol\u00adecule is (+)anti\u00adperiplanar whereby the pyridin-4-yl residues lie to either side of the planar region of the mol\u00adecule. The dihedral angles between the respective central core and the N1- and N3-pyridyl rings are 68.65\u2005(3) and 86.25\u2005(3)\u00b0, respectively. This represents the greatest conformational difference between the 4LH2 mol\u00adecules and is emphasized in the overlay diagram of Fig.\u00a02anti, enabling the formation of intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bonds that complete S(5) loops, Table\u00a01As each 2 group is 8.06\u2005(10)\u00b0 for the O3-mol\u00adecule indicating a closer to co-planar mol\u00adecule than for the O5-mol\u00adecule for which the equivalent dihedral angle is 17.24\u2005(8)\u00b0. Consistent with the carb\u00adoxy\u00adlic acid assignment, the C15\u2014O3(carbon\u00adyl) bond length of 1.2172\u2005(17)\u2005\u00c5 is considerably shorter than the C15\u2014O4(hy\u00addroxy) bond of 1.3196\u2005(16)\u2005\u00c5; the bonds of the O5-benzoic acid follow the same trend with C22\u2014O5 of 1.2173\u2005(17)\u2005\u00c5 compared with C22\u2014O6 of 1.3181\u2005(16)\u2005\u00c5. As seen from Fig.\u00a02To a first approximation, the two independent CBA mol\u00adecules in (I)a axis by amide-N\u2014H\u22efO(amide) hydrogen bonding and concatenated, centrosymmetric 10-membered {\u22efHNC2O}2 synthons, Fig.\u00a03a). The tapes are consolidated into a three-dimensional architecture by pyridyl- and methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) and CBA-C\u2014H\u22efO(amide) inter\u00adactions, Fig.\u00a03b).The formation of two independent, three-mol\u00adecule aggregates has already been noted above in the crystal of (I)Crystal Explorer 17  hydrogen bonds. Analogous calculations were also performed on the symmetry expanded N1- and N3-oxalamide mol\u00adecules, hereafter 4LH2-I and 4LH2-II, respectively, and on the independent O3- and O5-chloro\u00adbenzoic acid mol\u00adecules, hereafter CBA-I and CBA-II, respectively. The dnorm distances for short contacts identified through the Hirshfeld surface analysis are given in Table\u00a02The calculation of the Hirshfeld surfaces and two-dimensional fingerprint plots were accomplished with the program dnorm maps showing red spots ranging from moderate to strong intensity are illustrated in Fig.\u00a04O\u22efN1(pyrid\u00adyl) in 3M-I, carb\u00adoxy\u00adlic-O6\u2013H6O\u22efN3(pyrid\u00adyl) in 3M-II as well as the inter\u00adactions between amide-N2\u2013H2N\u22efO2(amide) and amide-N4\u2014H4N\u22efO1(amide) in 3M-I and 3M-II, respectively, while relatively weaker inter\u00adactions with moderately to weakly intense red spots between amide-C7\u22efCl1, pyridyl-C1\u2014H1\u22efO3(carboxy\u00adlic acid), pyridyl-C2\u2014H2\u22efO3(carb\u00adoxy\u00adlic acid), methyl\u00adene-C\u2014H6A\u22efO3(carb\u00adoxy\u00adlic acid), amide-O1\u22efCl1 in 3M-I, and Cl2\u22efC14(amide), methyl\u00adene-C13\u2014H13A\u22efO5(carboxylic acid), pyridyl-C8\u2014H8\u22efO5(carb\u00adoxy\u00adlic acid), pyridyl-C9\u2014H9\u22efO5(carb\u00adoxy\u00adlic acid), Cl2\u22efO2(amide) in 3M-II are observed. As well, spots due to benzene-C27\u2014H27\u22efO1(amide) are seen, i.e. providing connections between 3M-I and 3M-II.Several dnorm maps for 3M-I and 3M-II exhibit similarity for the corresponding 4LH2 and CBA mol\u00adecules with the exception of CBA-II. Pairs of CBA-II are aligned around an inversion centre with Cl2 and H25 being directly opposite each other, ostensibly forming an eight-membered heterosynthon despite the distance being longer than the cut-off value of 2.84\u2005\u00c5  for the independent 4LH2 and CBA mol\u00adecules in (I)A\u22efO3, C7\u22efCl1, Cl2\u22efC14, O1\u22efCl1 and Cl2\u22efO2 contacts are indeed electrostatic in nature, as shown from the red (electronegative) and blue (electropositive) regions on the ESP maps despite being relatively less intense when compared to those arising from the classical hydrogen bonds.To establish the nature of the inter\u00admolecular inter\u00adactions, particularly for the weaker contacts, a mapping of the electrostatic potential (ESP) was performed over the Hirshfeld surfaces through DFT-B3LYP/6-31G basis set  are comparable to the data obtained from Gaussian 16, in which Cl1, O1, Cl2 and O2 possess charges of +0.0054, \u22120.0147, +0.0054 and \u22120.0125 atomic units (a.u.), respectively; while the C7 and C14 atoms each exhibit a weak electrostatic potential charge of +0.0251 and +0.0263 a.u., respectively. Therefore, the C7\u22efCl1 and C14\u22efCl2 inter\u00adactions are dispersive in nature. On the other hand, the apparent charge complementarity between the Cl2 and H25 atoms, which align around a centre of inversion as described above, indicate the existence of an electrostatic inter\u00adaction between two CBA-II mol\u00adecules, Fig.\u00a05d).Of particular inter\u00adest is the observation that the chlorine atom inter\u00adacts with the amide-C=O residue through an electron-deficient \u03c3-hole region. To complement the ESP findings on these O\u22efCl and C\u22efCl contacts, non-covalent inter\u00adaction plots were generated for the relevant pairwise mol\u00adecules using 4LH2-I, 4LH2-II, CBA-I, CBA-II, 3M-I and 3M-II. The overall fingerprint plots for the specified mol\u00adecules/aggregates are shown in Fig.\u00a08a) and those decomposed into H\u22efO/O\u22efH/ H\u22efC/C\u22efH, H\u22efN/N\u22efH and H\u22efCl/Cl\u22efH plots are shown in Fig.\u00a08b)-(e).The two-dimensional fingerprint plots were generated in order to qu\u00adantify the close contacts for di + de distances shorter than the sum of the respective van der Waals radii of 2.61, 2.64 and 2.84\u2005\u00c5 . For 3M-I, the di + de values for the H\u22efO/O\u22efH and H\u22efN contacts are, respectively, tipped at \u223c1.98, \u223c1.95 and \u223c1.68\u2005\u00c5, and are attributed to -N2\u2014H2N\u22efO2-, -O1\u22efH4N- and -N1\u22efH4O- contacts, respectively. The analogous contacts for 3M-II are tipped at 1.95\u2005\u00c5 for -H4N\u22efO1-, \u223c1.98\u2005\u00c5 for -O2\u22efH2N- and \u223c1.64\u2005\u00c5 for -N3\u22efH6O-. For H\u22efCl/Cl\u22efH in 3M-II, the contacts are each tipped at \u223c2.80\u2005\u00c5 owing to the pair of -H25\u22efCl2- and -Cl2\u22efH25- inter\u00adactions. As for the H\u22efH and H\u22efC/ C\u22efH contacts, their di + de distances are longer than the sum of their respective van der Waals radii of 2.18 and 2.79\u2005\u00c5, and hence contribute little to the overall packing of the crystal despite providing the predominant surface contacts.The overall fingerprint plot of the individual components and the corresponding three-mol\u00adecule aggregates exhibit a paw-like profile with asymmetric spikes indicating the inter-dependency of the inter\u00admolecular inter\u00adactions between mol\u00adecules to sustain the packing. The 3M-I and 3M-II aggregates display almost identical fingerprint profiles which, upon decomposition, can be delineated into H\u22efH , H\u22efC/C\u22efH , H\u22efO/O\u22efH [21.2 and 20.7%], H\u22efCl/Cl\u22efH [7.5 and 10.8%], H\u22efN/N\u22efH [6.4 and 3.8%] and other minor contacts [10.0 and 10.7%]. A detailed analysis on the corresponding decomposed fingerprint plots shows that only the H\u22efO/O\u22efH and H\u22efN/N\u22efH contacts for both 3M-I and 3M-II as well as H\u22efCl/Cl\u22efH for 3M-II have 4LH2-I and 4LH2-II mol\u00adecules exhibit similar fingerprint profiles with only slight differences in the contact distributions. In order of dominance, these are H\u22efH (36.3% for 4LH2-I and 33.8% for 4LH2-II), H\u22efO/O\u22efH , H\u22efC/C\u22efH (21.4 and 21.2%), H\u22efN/N\u22efH (11.0 and 8.3%), H\u22efCl (1.7 and 6.1%) and other minor contacts (6.0 and 7.8%). There is no major deviations in the di + de distances cf. 3M-1 and 3M-II, with only the H\u22efO/O\u22efH as well as N\u22efH contacts being shorter than the sums of their respective van der Waals radii. Each of 4LH2-I and 4LH2-II have di + de of about 1.98\u2005\u00c5 for H\u22efO/O\u22efH and \u223c1.64\u2005\u00c5 for N\u22efH contacts.The individual X\u22efH- rather than -H\u22efX-, as evidenced most notably from the distribution for O\u22efH  versus H\u22efO  and Cl\u22efH  vs H\u22efCl . The inclination arises due to the lack of hydrogen-bond donor atoms in the CBA-I and CBA-II mol\u00adecules, other than the carb\u00adoxy\u00adlic acid groups, so they act primarily as hydrogen-bond acceptors. Among the contacts, O\u22efH and H\u22efN for CBA-I have di + de distances of \u223c2.40 and \u223c1.64\u2005\u00c5, respectively, each being shorter than the sum of the respective van der Waals radii, while the same is true for H\u22efO/O\u22efH, H\u22efN and H\u22efCl/Cl\u22efH contact for CBA-II with di + de distances of \u223c2.38, \u223c1.62 and \u223c2.82\u2005\u00c5, respectively.As for the individual CBA-I and CBA-II mol\u00adecules, major contacts comprise H\u22efH (23.7% for CBA-I and 22.1% for CBA-II), H\u22efC/C\u22efH , H\u22efO/O\u22efH (17.7 and 17.9%), H\u22efCl/Cl\u22efH (16.8 and 17.5%), H\u22efN (5.3 and 4.4%) and other minor contacts (15.7 and 13.9%). A detailed analysis of the corresponding contacts shows all major inter\u00adactions for CBA-I and CBA-II are more inclined toward -Crystal Explorer 17  and amide-N4\u2014H4N\u22efO1(amide) hydrogen bonds has the greatest energy among all close contacts present in the crystal with an inter\u00adaction energy (Eint) of \u221261.9\u2005kJ\u2005mol\u22121. This is followed by the seven-membered heterosynthon formed between 4LH2-II and CBA-II through the carb\u00adoxy\u00adlic acid-O4\u2014H4O\u22efN1(pyrid\u00adyl) hydrogen bond with the supporting pyridyl-C\u2014H8\u22efO5(carbon\u00adyl) contact so that Eint = \u221252.0\u2005kJ\u2005mol\u22121. For the analogous contact between 4LH2-I and CBA-I but lacking the supporting pyridyl-C\u2014H\u22efO5(carbon\u00adyl) contact, it is gratifying to note the inter\u00adaction energy is correspondingly less, i.e. Eint = \u221249.4\u2005kJ\u2005mol\u22121. The inter\u00adactions between amide-C7\u22efCl1 and amide-O1\u22efCl1, summing to Eint of \u221216.6\u2005kJ\u2005mol\u22121, are also significant, as are the inter\u00adactions between methyl\u00adene-C\u2013H6A\u22efO3(amide) and pyridyl-C2\u2013H2\u22efO3(amide) with Eint = \u221215.8\u2005kJ\u2005mol\u22121. The equivalent inter\u00adactions surrounding the 4LH2-II mol\u00adecule follow the same trends and give similar energies, Table\u00a03Eint of \u22128.7\u2005kJ\u2005mol\u22121. Finally, the C27\u2014H27\u22efO1(amide) inter\u00adaction exhibits an Eint of \u221220.4\u2005kJ\u2005mol\u22121.The calculation of the inter\u00adaction energies for all pairwise inter\u00adacting mol\u00adecules was performed through Eele) as highlighted by the rod-shaped energy framework with a zigzag topology due to the combination of several strong inter\u00adactions, Fig.\u00a09a). Specifically, the combination of inter\u00adactions between 4LH2-I and CBA-I through the terminal O4\u2014H4O\u22efN1 hydrogen bonding as well as between 4LH2-II and CBA-II via O6\u2014H6O\u22efN3 and C8\u2014H8\u22efO5 inter\u00adactions leads to the formation of the core framework parallel to (101). The overall Eele of these inter\u00adactions is much greater than that associated with the ten-membered synthons formed by a combination of N2\u2014H2N\u22efO2 and N4\u2014H4N\u22efO1 hydrogen bonds as evidenced from the relatively small rod radius in the energy model of the latter inter\u00adactions, which align in a parallel fashion along the b axis, Fig.\u00a09a).The crystal of (I)2O}2 synthon along with the peripheral C7\u22efCl1/O1\u22efCl1 and C14\u22efCl2/O2\u22efCl2 inter\u00adactions which lead to a ladder-like topology, Fig.\u00a09b). The combination of the electrostatic and dispersion forces results in an enhancement of the influence of the ten-membered synthons which supersedes the energy force for the terminal carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds as seen in the total energy framework, Fig.\u00a09c).Apart from the electrostatic forces, the crystal is also sustained by substantial dispersion forces, which are mainly associated with the ten-membered {\u22efHNC4LH2 and mono-functional carb\u00adoxy\u00adlic acids; one exception was noted in the Chemical context. A different situation pertains when bi-functional carb\u00adoxy\u00adlic acids are employed in co-crystal formation. In these circumstances, e.g. when the carb\u00adoxy\u00adlic acid is bis\u00ad(carb\u00adoxy\u00admeth\u00adyl)urea and diglycineoxamide urea  hydrogen bonds, involving both pyridyl rings, leading to three-mol\u00adecule aggregates, is an almost universal trait when co-crystals are formed between N,N\u2032-bis\u00ad(pyridin-4-ylmeth\u00adyl)oxalamide (4LH2) was prepared according to a literature procedure: m.p.: 486.3\u2013487.6\u2005K; lit. 486\u2013487\u2005K  was mixed with 4-chloro\u00adbenzoic acid  and the mixture was then ground for 15\u2005min in the presence of a few drops of methanol. The procedure was repeated twice. Colourless blocks were obtained through careful layering of toluene (1\u2005ml) on an N,N-di\u00admethyl\u00adformamide (1\u2005ml) solution of the ground mixture. M.p.: 456.9\u2013458.6\u2005K. IR (cm\u22121): 3211 \u03bd(N\u2014H), 3052\u20142935 \u03bd(C\u2014H), 1669\u20131604 \u03bd(C=O), 1492 \u03bd(C=C), 1419 \u03bd(C\u2014N), 794 \u03bd(C\u2014Cl).The precursor, Uiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located from a difference-Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020000572/hb7889sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000572/hb7889Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000572/hb7889Isup3.cmlSupporting information file. DOI: 1978104CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The inter\u00admolecular inter\u00adactions at play were characterized via Hirshfeld surface analysis and fingerprint plots, highlighting the evident role of C\u2014H\u22efO, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions in the formation of the observed crystal structure.The structural analysis of a phenyl\u00adindolizine-based drug, namely methyl 3-(4-flurobenzo\u00adyl)-7-methyl-2-phenyl\u00adindolizine-1-carboxyl\u00adate (I) was carried out; this drug shows an inhibitory action towards  24H18FNO3, crystallizes in the monoclinic centrosymmetric space group 1/nP2 and its mol\u00adecular conformation is stabilized via C\u2014H\u22efO intra\u00admolecular inter\u00adactions. The supra\u00admolecular network mainly comprises C\u2014H\u22efO, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions, which contribute towards the formation of the crystal structure. The different inter\u00admolecular inter\u00adactions have been further analysed via Hirshfeld surface analysis and fingerprint plots.The title compound, C The heterocycle is substituted at the carbon atoms C6, C7 and C8 with a meth\u00adoxy carbonyl group, a phenyl ring , and a fluoro\u00adbenzoyl ring , respectively \u2005\u00c5]. The dihedral angle between the mean plane through ring Cg3 \u2005\u00c5, 157\u00b0; C15\u22efO3iii = 3.519\u2005(4)\u2005\u00c5, 137\u00b0; symmetry codes: (ii) x, y\u00a0\u2212\u00a01, z; (iii) x, y\u00a0+\u00a01, z] and C1\u2014H1\u22ef\u03c0(C15)ii , forming ribbons along the [010] direction, as shown by the green shading in Fig.\u00a03via C11\u2014H11B\u22efF1v , C11\u2014H11A\u22ef\u03c0(C5) , C11\u2014H11C\u22ef\u03c0(C8)  (CN), etc.Structural details of compounds such as CAJTAI  , 4-methyl\u00adpyridine (2) , 2-bromo-1-(4-fluoro\u00adphen\u00adyl)ethan-1-one (3) , and tri\u00adethyl\u00adamine  in 4.5\u2005mL of aceto\u00adnitrile were added to a 10\u2005mL microwave tube under a nitro\u00adgen atmosphere  of the title compound  =1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020003837/xi2021sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020003837/xi2021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003837/xi2021Isup3.cmlSupporting information file. DOI: 1865697CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the mol\u00adecular packing, mol\u00adecules are assembled into supra\u00admolecular layers in the  32H30N4O2S4, is generated by a crystallographic twofold axis that bis\u00adects the di\u00adsulfide bond. The mol\u00adecule is twisted about this bond with the C\u2014S\u2014S\u2014C torsion angle of 90.70\u2005(8)\u00b0 indicating an orthogonal relationship between the symmetry-related halves of the mol\u00adecule. The conformation about the imine bond [1.282\u2005(2)\u2005\u00c5] is E and there is limited delocalization of \u03c0-electron density over the CN2C residue as there is a twist about the N\u2014N bond [C\u2014N\u2014N\u2014C torsion angle = \u2212166.57\u2005(15)\u00b0]. An intra\u00admolecular hydroxyl-O\u2014H\u22efN(imine) hydrogen bond closes an S(6) loop. In the crystal, methyl\u00adene-C\u2014H\u22ef\u03c0(tol\u00adyl) contacts assemble mol\u00adecules into a supra\u00admolecular layer propagating in the ab plane: the layers stack without directional inter\u00adactions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of H\u22efH contacts, which contribute 46.7% of all contacts followed by H\u22efC/C\u22efH contacts [25.5%] reflecting, in part, the C\u2014H\u22ef\u03c0(tol\u00adyl) contacts. The calculation of the inter\u00adaction energies confirm the importance of the dispersion term and the influence of the stabilizing H\u22efH contacts in the inter-layer region.The complete mol\u00adecule of the title hydrazine carbodi\u00adthio\u00adate derivative, C S-alkyl-di\u00adthio\u00adcarbazate derivatives with heterocyclic aldehydes and ketones to form mol\u00adecules of the general formula RSC(=S)N(H)N=C(R\u2032)R\u2032\u2032, where R\u2032, R\u2032\u2032 = alkyl and aryl. These mol\u00adecules are effective ligands for a variety of metals and the motivation for complexation largely stems from the promising biological activity exhibited by the derived metal complexes \u2005\u00c5 to the other side; symmetry operation (i): 1\u00a0\u2212\u00a0x, y, z. The C1\u2014S1 bond length of 1.7921\u2005(17)\u2005\u00c5 is significantly longer than the C1\u2014S2 bond of 1.7463\u2005(17)\u2005\u00c5, which is ascribed to the S1 atom participating in the S1\u2014S1i bond of 2.0439\u2005(8)\u2005\u00c5; each C1\u2014S bond is shorter than the C9\u2014S2 bond length of 1.8308\u2005(18)\u2005\u00c5.The crystallographic asymmetric unit of (I)E-conformation), N1\u2014N2 and C2=N2 bond lengths is 1.282\u2005(2), 1.409\u2005(2) and 1.286\u2005(2)\u2005\u00c5, respectively, and suggests limited delocalization of \u03c0-electron density over this residue which is consistent with a twist about the N1\u2014N2 bond as seen in the C1\u2014N1\u2014N2\u2014C2 torsion angle of \u2212166.57\u2005(15)\u00b0. The presence of an intra\u00admolecular hydroxyl-O\u2014H\u22efN(imine) hydrogen bond, Table\u00a01i\u2014C1i torsion angle being 90.70\u2005(8)\u00b0 and the dihedral angle between the two CNS2 planes being 88.22\u2005(3)\u00b0.The sequence of C1=N1 . Layers stack along the c axis without directional inter\u00adactions between them, Fig.\u00a02b).In the crystal, the only directional contact identified in the geometric analysis of the mol\u00adecular packing employing dnorm surface, electrostatic potential  and two-dimensional fingerprint plot calculations were performed for (I)Crystal Explorer 17 , i.e. near the imine-C2 and tolyl ring, centroid designated Cg1, correspond to the C2\u22efO1, C2\u22efC4 short contacts  inter\u00adaction, Table\u00a01A\u22ef\u03c0(tol\u00adyl) inter\u00adaction shows up as a distinctive orange \u2018pothole\u2019 on the shape-index-mapped Hirshfeld surface, Fig.\u00a03b).The Hirshfeld surface analysis comprising a), the faint red spots appearing near the tolyl-H12, methyl\u00adene-H9B and phenol-H8 atoms correlate with the faint red spots near the sulfanyl-S1, hydrazine-N1 and tolyl-C11 atoms, and correspond to the intra-layer tolyl-C12\u2014H12\u22efS1(sulfan\u00adyl), methyl\u00adene-C9\u2014H9B\u22efN1(hydrazine) and phenol-C8\u2014H8\u22efC11(tol\u00adyl) inter\u00adactions, Table\u00a02b), with the blue and red regions corresponding to positive and negative electrostatic potentials, respectively.In the views of Fig.\u00a04de and di diagonal axes for the overall fingerprint plot, Fig.\u00a05a); those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efS/S\u22efH, H\u22efO/O\u22efH, N\u22efC/C\u22efN and H\u22efN/N\u22efH contacts are illustrated in Fig.\u00a05b)\u2013(g), respectively. The percentage contributions for the different inter\u00adatomic contacts to the Hirshfeld surface are summarized in Table\u00a03de = di \u223c2.4\u2005\u00c5, Fig.\u00a05b). The tip of this H\u22efH contact corresponds to an inter-layer H6\u22efH14 contact with a distance of 2.39\u2005\u00c5, Table\u00a02de + di \u223c2.7\u2005\u00c5 in Fig.\u00a05c). The H\u22efS/S\u22efH contacts contribute 13.6% and appear as two sharp-symmetric wings at de + di \u223c2.8\u2005\u00c5, Fig.\u00a05d). This feature reflects the intra-layer tolyl-C12\u2014H12\u22efS1(sulfan\u00adyl) inter\u00adaction, Table\u00a02de + di \u223c2.8\u2005\u00c5, Fig.\u00a05e); this separation is \u223c0.08\u2005\u00c5 longer than the sum of their van der Waals radii. Although both N\u22efC/C\u22efN and H\u22efN/N\u22efH contacts appear at de + di \u223c2.6\u20132.8\u2005\u00c5 in the respective fingerprint plots, Fig.\u00a05f) and (g), their contributions to the overall Hirshfeld surface are only 3.6 and 3.4%, respectively. The contributions from the other inter\u00adatomic contacts summarized in Table\u00a03The corresponding two-dimensional fingerprint plots for the calculated Hirshfeld surface of (I)d,p) basis set with the B3LYP function. The total energy comprises four terms: i.e. the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies and these were calculated in Crystal Explorer 17  occurs within the intra-layer region and arises from the combination of C\u2014H\u22ef\u03c0, C\u22efO and C\u22efC short contacts as well as weak C\u2014H\u22efN/C inter\u00adactions. The second most significant energy of stabilization within the intra-layer region involves a major contribution from the tolyl-C12\u2014H12\u22efS1(sulfan\u00adyl) inter\u00adaction (dominated by Edis) with a total energy of \u221229.7\u2005kJ\u2005mol\u22121. In addition, a long-range H6\u22efH16B contact is observed within the intra-layer region with a H\u22efH separation of 2.44\u2005\u00c5.In the present analysis, the pairwise inter\u00adaction energies between the mol\u00adecules in the crystal of (I)Edis energy term also makes the major contribution to the energies of stabilization in the inter-layer region, with the separation between mol\u00adecules in the inter-layer region being H\u22efH contacts. The maximum energy is not found for the shortest H6\u22efH14 contact (\u20139.5\u2005kJ\u2005mol\u22121), Table\u00a02\u22121), each with a distance of 2.51\u2005\u00c5. Views of the energy framework diagrams down the b axis are shown in Fig.\u00a06Edis in the stabilization of the crystal.The R group, i.e. R = Me S-4-methyl\u00adbenzyl\u00addithio\u00adcarbazate (10\u2005mmol) and salicyl\u00adaldehyde (10\u2005mmol) in \u223c30\u2005ml of aceto\u00adnitrile for about 2\u2005h Uiso(H) set to 1.2Ueq(C). The O-bound H atom was located in a difference-Fourier map, but was refined with an O\u2014H = 0.84\u00b10.01\u2005\u00c5 distance restraint, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989020008762/hb7929sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020008762/hb7929Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008762/hb7929Isup3.cmlSupporting information file. DOI: 2013050CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The nickel(II) ion in 1 is octa\u00adhedrally coordinated by the O atoms of two water mol\u00adecules, two O atoms from O-monodentate 6-fluoro\u00adnicotinate ligands and two N atoms from bridging 4,4\u2032-bi\u00adpyridine ligands.A one-dimensional nickel(II) coordination polymer with the mixed ligands 6-fluoro\u00adnicotinate (6-Fnic) and 4,4\u2032-bi\u00adpyridine , namely, [Ni(H catena-poly[[di\u00adaqua\u00adbis\u00ad(6-fluoro\u00adpyridine-3-carboxyl\u00adato-\u03baO)nickel(II)]-\u03bc-4,4\u2032-bi\u00adpyri\u00addine-\u03ba2N:N\u2032] trihydrate], {[Ni(6-Fnic)2(H2O)2]\u00b73H2O}n, (1), was prepared by the reaction of nickel(II) sulfate hepta\u00adhydrate, 6-fluoro\u00adnicotinic acid (C6H4FNO2) and 4,4\u2032-bi\u00adpyridine (C10H8N2) in a mixture of water and ethanol. The nickel(II) ion in 1 is octa\u00adhedrally coordinated by the O atoms of two water mol\u00adecules, two O atoms from O-monodentate 6-fluoro\u00adnicotinate ligands and two N atoms from bridging 4,4\u2032-bi\u00adpyridine ligands, forming a trans isomer. The bridging 4,4\u2032-bi\u00adpyridine ligands connect symmetry-related nickel(II) ions into infinite one-dimensional polymeric chains running in the [11, the polymeric chains and lattice water mol\u00adecules are connected into a three-dimensional hydrogen-bonded network via strong O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, leading to the formation of distinct hydrogen-bond ring motifs: octa\u00admeric R88(24) and hexa\u00admeric R86(16) loops.A one-dimensional nickel(II) coordination polymer with the mixed ligands 6-fluoro\u00adnicotinate (6-Fnic) and 4,4\u2032-bi\u00adpyridine , namely,  On the other hand, no metal complexes of other fluorinated analogues of nicotinate  have been reported so far.Although metal complexes with nicotinate have been well-studied and documented \u00b73H2O} (1). The synthesis was carried out in a mixture of water and ethanol in the hope that the coord\u00adinated water mol\u00adecules would complete the coordination sphere around the nickel(II) ion and participate in the formation of various hydrogen-bond motifs within the hydrogen-bonded framework, along with the anti\u00adcipated lattice water mol\u00adecules. Furthermore, we wanted to explore the effect of the probable weak inter\u00admolecular inter\u00adactions involving the aromatic F atoms (for example C\u2014H\u22efF inter\u00adactions) on the assembly of the polymeric chains in the crystal packing.In this work, we report the synthesis and characterization of the first metal complex with 6-fluoro\u00adnicotinate \u2013 the one-dimensional nickel(II) coordination polymer {. In this way, a trans isomer is formed (N2i\u2014Ni1\u2014N2 = 180\u00b0)  ions into an infinite one-dimensional polymeric chain extending in the [12(H2O)2]\u00b73H2O}.As the nickel(II) ion and the lattice water mol\u00adecule (atom O4) are situated on an inversion center and a twofold axis, respectively, the asymmetric unit of \u00b0) Fig.\u00a01. The 6-fon Fig.\u00a02. There acis pairs of the ligating atoms [89.65\u2005(6)\u201390.87\u2005(6)\u00b0]. The Ni1\u2014O1 bond length [2.1067\u2005(16)\u2005\u00c5] is somewhat longer than the Ni1\u2014O2 and Ni1\u2014N2 bond lengths , which is in agreement with the fact that the water mol\u00adecules are bound in the axial positions of the octa\u00adhedron. The Ni\u2014Oc (c = carboxyl\u00adate) bond lengths in 1 are comparable to those seen in the related nickel(II) complexes with 6-chloro\u00adnicotinate  ligands  ion is slightly distorted, as indicated by the angles for the The 4,4\u2032-bypyridine ring is not coplanar with the coordinated water mol\u00adecule atom O1, but it is rotated slightly (approximately 4\u00b0) about the Ni1\u2014N2 bond, as is evident from the torsion angles Ni1\u2014N2\u2014C7\u2014C8 [176.35\u2005(19)\u00b0] and Ni1\u2014N2\u2014C11\u2014C10 [\u2212176.03\u2005(18)\u00b0]. The values of these torsion angles ought to be 180\u00b0 in the case of coplanarity of the 4,4\u2032-bi\u00adpyridine ring and the O1 atom of the coordinated water mol\u00adecule.1 mainly features strong O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds (Table\u00a01Cg1\u22efCg1(\u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01) = 3.8148\u2005(16)\u2005\u00c5; dihedral angle between the planes = 0.00\u2005(14)\u00b0; slippage = 1.792\u2005\u00c5 and Cg1\u22efCg2 = 3.8798\u2005(16)\u2005\u00c5; dihedral angle between the planes = 11.68\u2005(13)\u00b0; slippage = 1.917\u2005\u00c5; Cg1 and Cg2 are the centroids of the 6-fluoro\u00adnicotinate pyridine (N1/C1\u2013C5) and 4,4\u2032-bi\u00adpyridine (N2/C7\u2013C11) rings, respectively]. The strong hydrogen bonds link the polymeric chains and the lattice water mol\u00adecules into an infinite three-dimensional network. The structure can be better analysed if viewed down the [1Cg1\u22efCg1].The extended structure of s Table\u00a01 and \u03c0\u2013\u03c0 rk Fig.\u00a03. While b1  coordination polymers containing bridging 4,4\u2032-bi\u00adpyridine and pyridinedi\u00adcarboxyl\u00adate ligands, there are only two structurally similar one-dimensional nickel(II) polymers with 4,4\u2032-bi\u00adpyridine and pyridine\u00adcarboxyl\u00adate . Both the coordinated (two) and lattice (three) water mol\u00adecules were released in the same step . The two small endothermic peaks in the DSC curve (63 and 115\u00b0C) suggest that the process of the water evolution is not straightforward and that the water mol\u00adecules are differently bound in 1 (coordinated vs lattice). Indeed, the polymeric chains and lattice water mol\u00adecules are assembled into a hydrogen-bonded three-dimensional structure (see Supra\u00admolecular features). It is therefore not surprising that the release of some water mol\u00adecules affects the whole hydrogen-bonded structure and leads to its complete collapse in a single, not well-resolved thermal step. The thermal decomposition of 1 continues in a broad step (observed mass loss 56.7%) in the wide temperature range of 150\u2013570\u00b0C (without any well-defined peaks in the DSC curve), which probably corresponds to the complete degradation of 1. The remaining residue at 600\u00b0C is most probably NiO.The thermal stability of \u22121 on a Perkin\u2013Elmer Spectrum TwoTM FTIR spectrometer in the ATR mode. The PXRD trace was recorded on a Philips PW 1850 diffractometer, Cu K\u03b1 radiation, voltage 40\u2005kV, current 40\u2005mA, in the angle range 5\u201350\u00b0 (2\u03b8) with a step size of 0.02\u00b0. Simultaneous TGA/DSC measurements were performed at a heating rate of 10\u00b0C min\u22121 in the temperature range 25\u2013600\u00b0C, under a nitro\u00adgen flow of 50\u2005mL\u2005min\u22121 on an Mettler-Toledo TGA/DSC 3+ instrument. Approximately 2\u2005mg of the sample were placed in a standard alumina crucible (70\u2005\u00b5l).All chemicals for the synthesis were purchased from commercial sources  and used as received without further purification. The IR spectrum was obtained in the range 4000\u2013400\u2005cm1, suitable for X-ray diffraction measurements, were obtained. These were collected by filtration, washed with their mother liquor and dried in vacuo. Yield: 0.0483\u2005g (45%). Selected IR bands (ATR) : 3351 [\u03bd(O\u2014H)], 3088 [\u03bd(C\u2014H)], 1607 [\u03bd(C=O)], 1558, 1475, 1415, 1392, 1368  .6-Fluoro\u00adnicotinic acid  was dissolved in distilled water (5\u2005ml), 4,4\u2032-bi\u00adpyridine  was dissolved in ethanol (2\u2005mL) and nickel(II) sulfate hepta\u00adhydrate  was dissolved in distilled water (2\u2005mL). The solutions of the two ligands were first mixed together under stirring. The resulting solution was then slowly added to the nickel(II) sulfate solution under stirring. The pH of the final solution was adjusted to 7 by adding an ammonia solution dropwise. The obtained, clear solution was left to evaporate slowly at room temperature for approximately three weeks until light\u2013blue crystals of Uiso(H) = 1.2Ueq(C) for aromatic H atoms]. Water H atoms were found in difference-Fourier maps, O\u2014H distances were restrained to an average value of 0.82\u2005\u00c5 using DFIX and DANG instructions and they were refined isotropically [Uiso(H) = 1.2Ueq(O)].Crystal data, data collection and structure refinement details are summarized in Table\u00a02The highest difference peak is 0.92\u2005\u00c5 away from the O3 atom and the deepest difference hole is 0.50\u2005\u00c5 away from the Ni1 atom.10.1107/S2056989020003023/xi2024sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020003023/xi2024Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003023/xi2024sup3.docxTGA, DSC and IR data. DOI: 1988000CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Five-minute epoxy serves as a waterproof case enabling the operation of our supercapacitors while submerged underwater and a gel electrolyte extends cycling stability to 10,000 cycles with ~90% capacitance retention.Fired brick is a universal building material, produced by thousand-year-old technology, that throughout history has seldom served any other purpose. Here, we develop a scalable, cost-effective and versatile chemical synthesis using a fired brick to control oxidative radical polymerization and deposition of a nanofibrillar coating of the conducting polymer poly (PEDOT). A fired brick\u2019s open microstructure, mechanical robustness and ~8\u2009wt% \u03b1-Fe Fired brick is a universal building material, produced by thousand-year-old technology, which throughout history has seldom served any other purpose. Here, the authors show that bricks can store energy after chemical treatment to convert their iron oxide content into conducting polymer nanofibers. This masonry building block is commonly found in various red tones and mostly comprised of fused particles of silica (SiO2), alumina (Al2O3) and hematite (\u03b1-Fe2O3)2. The red color of a brick originates from hematite, a pigment first utilized by humans 73,000 years ago4 and serving today as a low-cost naturally abundant inorganic precursor for catalysts5, magnets6, and alloys7. State-of-the-art energy storage materials are also produced from hematite. For example, FeNx, FeP, and Li5FeO4 are synthesized via anionic or cationic exchange for potassium-ion batteries, Zn\u2013air batteries, pseudocapacitors, and lithium-ion batteries11; electrochemical transformation of hematite leads to FeOOH supercapacitor anodes12.Fired brick, typically used for construction and architectural esthetics, is one of the most durable materials with a 5000-year history dating back to Neolithic China13. Chemistries enabled by hematite provide an opportunity for developing cutting-edge functionalities on a fired brick where 8\u2009wt% \u03b1-Fe2O3 content and a 3D porous microstructure afford an ideal substrate for engineering a mechanically robust electrode. Here, we develop a supercapacitor using a brick\u2019s hematite microstructure as reactant to vapor-deposit a nanofibrillar coating of the conducting polymer poly (PEDOT). Vapor-phase synthesis leads to PEDOT coatings exhibiting a high electronic conductivity14 and facile charge transfer, making it an ideal route for producing electrodes15. This synthesis utilizes a brick\u2019s open microstructure and thermal stability to permeate acid and monomer vapor through its pores at 160\u2009\u00b0C to control \u03b1-Fe2O3 dissolution and Fe3+ hydrolysis with concomitant oxidative radical polymerization.This work is inspired by our recently published rust-assisted vapor phase polymerization\u22122 and energy density of 222\u2009\u00b5Wh\u2009cm\u22122 at a current density of 0.5\u2009mA\u2009cm\u22122. This two-electrode-based measurement is collected using 1\u2009M H2SO4 aqueous electrolyte under 1\u2009V operating voltage window. To mimic a \u201cbrick-mortar-brick\u201d structure, a supercapacitor is modified using a quasi-solid-state electrolyte /1\u2009M H2SO4) that also plays the role of binder and separator. Our devices are water-resistant because they are coated with an epoxy encapsulating layer that protects them enabling charge storage at temperatures between \u221220 and 60\u2009\u00b0C. A supercapacitor is stable in ambient conditions undergoing 10,000 charge\u2013discharge cycles with ~100% coulombic efficiency and ~90% capacitance retention. Moreover, a supercapacitor brick module is produced reaching a 3.6\u2009V voltage window by connecting three devices in series.A symmetric brick-based supercapacitor shows an areal capacitance of 1.60\u2009F\u2009cm2O3 at 160\u2009\u00b0C with HCl vapor; this process liberates Fe3+ ions, promotes hydrolysis and initiates precipitation of colloidal 1D FeOOH nuclei  and acid (HCl) where the former leads to oxidative radical polymerization and the latter, to acid-catalyzed polymerization . Using a HCl vapor concentration less than 4.8\u2009mM leads to an incomplete reaction because both oxidative radical polymerization and acid-catalyzed polymerization are impeded  exhibiting 2\u2126 two-point probe electrical resistance and nanofibers characterized by a ~30\u2009\u00b5m length and ~190\u2009nm diameter  evaporation, (2) dissolution, (3) hydrolysis, and (4) polymerization. A blue PEDOT coating is visible on a brick 4\u2009h after initiating a reaction and its thickness increases inversely proportional with electrical resistance until the end of reaction at 14\u2009h. An extended polymerization time increases the polymer coating\u2019s two-point probe electrical resistance  sizes and porosities are investigated  with different gravel SiO sizes anted Fig.\u00a0 that fac\u20133 with dses Fig.\u00a0. These tses Fig.\u00a0. Porositsly Fig.\u00a0. Our polsly Fig.\u00a0 and pattsly Fig.\u00a0 as demonsly Fig.\u00a0. Note th2O3 particles enables deposition of PEDOT coatings on customized substrates such as concrete road pavers  weighing 249\u2009mg and carrying 6.97\u2009mg PEDOT is fabricated into an electrode with one 1\u2009cm\u2009\u00d7\u20090.5\u2009cm face exposed . The electrode exhibits a quasi-rectangular shaped three-electrode cyclic voltammogram and a capacitance of 2.61\u2009F\u2009cm\u22122 (187\u2009F\u2009g\u22121 based on PEDOT\u2019s mass) at 2\u2009mV\u2009s\u22121 in 1\u2009M H2SO4  arise due to iron species in brick and disappears as scan rate increases to 25\u2009mV\u2009s\u22121 because Faradaic processes in PEDOT are faster than those occurring from solid Fe2O3  than sodium sulfate (0.878\u2009F\u2009cm\u22122) at 25\u2009mV\u2009s\u22121  vs. Na+ (5.19\u2009\u00d7\u200910\u22128\u2009m2\u2009V\u22121\u2009s\u22121) or a lower electrical resistance caused by doping at low pH14. We probed this behavior further using electrochemical impedance spectroscopy. Nyquist plots and an equivalent circuit diagram demonstrate a significantly lower ion diffusion resistance for H2SO4 (1.7\u03a9) vs. Na2SO4 (4.6\u03a9) and minimal change in electrode material electrical resistance at low pH . Diffraction patterns remain unchanged demonstrating that most inorganic species in a brick remain unaffected by synthesis and electrochemical cycling  and Al (1.97\u2009\u00b5g\u2009mL\u22121) in the electrolyte after cycling, these concentrations are equivalent to mass losses (based on the entire brick) of 0.0127 and 0.0075\u2009wt% for \u03b1-Fe2O3 and Al2O3, respectively. These results confirm that inorganic species in a brick are preserved after electrochemical cycling.To quantify dissolution of a brick\u2019s \u03b1-Fe2SO4 aqueous electrolyte  encompassing two PEDOT-coated bricks and a separator and its total mass (499\u2009mg) includes 13.94\u2009mg of PEDOT. Nyquist plot shows an aggregated internal resistance of 3\u03a9 and a line with a ~45\u00b0 slope between semicircle and low-frequency domain (Warburg region)  leading to a device areal capacitance of 1.59\u2009F\u2009cm\u22122 calculated using the electrode area directly in contact with separator (0.5\u2009cm2)  serve as electrodes in a symmetric supercapacitor (1\u2009cm\u2009\u00d7\u20090.5\u2009cm\u2009\u00d7\u20090.5625\u2009cm) using 1\u2009M Hyte Fig.\u00a0. A devicm2) Fig.\u00a0. In our \u22122 current density in a 1\u2009V window  as well as areal energy and power densities of 222 and 0.25\u2009mW\u2009cm\u22122, respectively (394\u2009\u00b5Wh\u2009cm\u22123 and 0.44\u2009mW\u2009cm\u22123 for volumetric). High power density (12.5\u2009mW\u2009cm\u22122) is obtained at a current density of 25\u2009mA\u2009cm\u22122 albeit with lowered capacitance (0.706\u2009F\u2009cm\u22122) and energy density (98\u2009\u00b5Wh\u2009cm\u22122) because ion transport in our thick electrode is limited (shown by high IR drop of 0.4\u2009V). Our device works in an extended voltage window (1.2\u2009V) resulting in cyclic voltammograms and galvanostatic charge\u2013discharge curves that retain shape  during galvanostatic charge-discharge experiments at 0.5\u2009mA\u2009cmitance 0.06\u2009F\u2009cm\u22122\u2009V during2SO4 gel that binds PEDOT-coated bricks and serves as electrolyte and separator  containing 13.94\u2009mg of PEDOT. In a tensile test, our electrode\u2013gel\u2013electrode structure withstands a shearing force equal to 1000 times the device\u2019s weight20  and areal energy density (121\u2009\u00b5Wh\u2009cm\u22122) originating from PEDOT-coated brick electrodes are calculated from galvanostatic charge\u2013discharge curves ; cyclic voltammograms also show capacitive behavior  using a poly/1\u2009M Htor Fig.\u00a0. The gelior Fig.\u00a0. The absces Fig.\u00a0.\u22122)  with ~87% capacitance retention , methanol (\u226599.8%), and hydrochloric acid (37%) are purchased from Sigma-Aldrich; sulfuric acid (AR) is purchased from Macron. The PEDOT:PSS solution (Clevios PH 1000) is purchased from Heraeus company. All chemicals are used without further purification. Platinum foil  is purchased from Alfa Aesar and utilized for engineering electrode leads and Celgard 3501 membrane is used as a separator. Fired bricks are purchased from local hardware stores: The Home Depot Inc. , Lowe\u2019s Inc.  and Menards Inc. . Road pavers are purchased from Menards Inc.  and all construction materials used for developing electrodes are cut using a diamond saw. Red cement color (\u03b1-Fe2O3 particles) produced by NewLook Inc. is purchased from The Home Depot Inc.  and serves as an oxidant source for developing chemical syntheses. Materials for making concrete  include commercial-grade Quikrete Portland cement (Type I/II) , Quikrete all-purpose sand (Internet #100318450Model # 115251Store SKU #137263) and Pavestone multi-purpose patio/paver base .Chlorobenzene (99%), 3,4-ethylenedioxythiophene (97%), poly (Rs), electrode material resistance (Rm), material capacitance (Cm), double-layer capacitance (Cdl), and constant phase element (CPE). Here, Rs reflects the electrolyte ionic mobility and Rm represents the electrical resistance of the electrode. Powder X-ray diffraction spectra of brick powders pulverized by mortar and pestle are obtained in a Bruker d8 Advance X-ray diffractometer at room temperature, with a Cu K\u03b1 radiation source (\u03bb\u2009=\u20091.5406\u2009\u00c5) and LynxEyeXe detector. The sample holder is a background-free silicon disk rotating at 30\u2009rpm when collecting data with a 0.02\u00b0 scan step at 40\u2009kV and 40\u2009mA. Current\u2013voltage tests are performed on a 3D printed two-point probe station with two gold probes separated by 2\u2009mm23. Water absorption experiments are performed as described in ASTM C67/C67M-18 except brick samples are 1\u2009cm\u2009\u00d7\u20090.5\u2009cm\u2009\u00d7\u20090.28\u2009cm in size. Inductively coupled plasma mass spectrometry is performed on a Perkin Elmer ELAN DRC II ICP\u2013MS. Samples for testing are obtained from electrolytes (5\u2009mL 1\u2009M H2SO4) after three-electrode cyclic voltammetry experiments and are diluted to 1/100 with Mili-Q water before analyses. External calibration curves are obtained with IV-ICPMS-71A standard solution purchased from Inorganic Ventures, Inc.Scanning electron micrographs and energy-dispersive X-ray spectra are collected with a JEOL 7001LVF FE-SEM. Two-point probe resistance measurements are carried out using a Fluke 177 True RMS digital multimeter with 3\u2009mm distance between two probes. Thermogravimetric analysis is conducted on a Discovery TGA (TA Instruments). Cyclic voltammetry, galvanostatic charge\u2013discharge measurements and electrochemical impedance spectroscopy are performed in a BioLogic VMP3 multipotentiostat. For electrochemical impedance spectroscopy, the sinusoidal disturbance is 10\u2009mV with frequencies scanned between 100\u2009kHz and 0.1\u2009Hz. A Nyquist plot shows real impedance Z\u2032 vs. imaginary impedance \u2212Z\u2032\u2032 under a sinusoidal disturbance at the open circuit potential. Fitting of Nyquist plot using an equivalent circuit diagram contains solution resistance (2SO4 (1\u2009M) is then carried out by pipetting acid on the inner wall under vigorous stirring to prevent carbonization of poly. Stirring minimizes localized heating and is carried out for 1\u2009h resulting in a homogeneous, translucent, and colorless solution.The gel electrolyte is formulated using 1\u2009g of poly powder dissolved in 10\u2009mL deionized water under vigorous stirring at 90\u2009\u00b0C and cooled to around 50\u2009\u00b0C. Dropwise addition of 1\u2009g of concentrated HBrick is cut using a diamond saw (\u00b10.03\u2009cm error) into the following 4 different sizes: 1.00\u2009cm\u2009\u2a2f\u20090.50\u2009cm\u2009\u2a2f\u20090.28\u2009cm (for studying synthesis and electrochemistry), 1.27\u2009cm\u2009\u2a2f\u20091.27\u2009cm\u2009\u2a2f\u20090.20\u2009cm (for patterning), 2.00\u2009cm\u2009\u2a2f\u20091.00\u2009cm\u2009\u2a2f\u20091.00\u2009cm  and 10.16\u2009cm\u2009\u2a2f\u20096.77\u2009cm\u2009\u2a2f\u20095.72\u2009cm . A brick is thrice washed with deionized water to remove surface dust then dried at 160\u2009\u00b0C for 1\u2009h and cooled to room temperature.The syntheses of all types of 1\u2009cm\u2009\u2a2f\u20090.5\u2009cm\u2009\u2a2f\u20090.28\u2009cm brick are performed in a 25\u2009mL Teflon-lined stainless-steel autoclave as shown in Fig.\u00a0A brick (1.27\u2009cm\u2009\u2a2f\u20091.27\u2009cm\u2009\u2a2f\u20090.20\u2009cm) is patterned using a polyimide tape mask. Synthesis is carried out at 150\u2009\u00b0C for 14\u2009h in a 125\u2009mL Teflon-lined stainless-steel autoclave containing 1\u2009mL of a 0.85\u2009M EDOT solution in chlorobenzene and 0.6\u2009mL of 12\u2009M HCl  with a large brick (10.16\u2009cm\u2009\u2a2f\u20096.77\u2009cm\u2009\u2a2f\u20095.72\u2009cm). The reaction is carried out using 15\u2009mL of 12\u2009M HCl and 15\u2009mL of a 0.85\u2009M EDOT in chlorobenzene solution at 150\u2009\u00b0C for 6\u2009h Fig.\u00a0.2O3 particles to a concrete surface  for 3\u2009s, then dried in air. Synthesis is performed at 150\u2009\u00b0C for 14\u2009h in a 125\u2009mL Teflon-lined stainless-steel autoclave loaded with 1\u2009mL of a 0.45\u2009M EDOT in chlorobenzene solution and 0.1\u2009mL of 12\u2009M HCl.We produce a PEDOT coating on concrete by applying \u03b1-Fe\u22121 poly/1\u2009M H2SO4) is pipetted onto two 1\u2009cm\u2009\u2a2f\u20090.5\u2009cm\u2009\u2a2f\u20090.28\u2009cm PEDOT-coated bricks (100\u2009\u00b5L each brick on the 1\u2009cm\u2009\u2a2f\u20090.5\u2009cm face). This electrolyte is allowed to impregnate for 12\u2009h at ambient conditions  forming a semidry gel layer. An additional 25\u2009\u00b5L of gel electrolyte is added serving as a binder between two bricks to assemble a sandwich-type supercapacitor. A device is dried in ambient conditions  for 1\u2009h before sealing with epoxy . This electrolyte is allowed to stabilize for 12\u2009h at ambient conditions ; this process is repeated for all brick electrodes resulting in a thick gel layer  in 1\u2009mL of 1\u2009M HSupplementary InformationPeer Review FileDescription of Additional Supplementary FilesSupplementary Movie 1"}
{"text": "The complex has hexa\u00adgonal layers of Cs3Yb3 with THF ligands and Me3Si groups in between the layers.Reduction of (C 5:\u03b75-1-(tri\u00admethyl\u00adsil\u00adyl)cyclo\u00adpenta\u00addien\u00adyl]caesium(I)ytterbium(II)], [CsYb(C8H13Si)3(C4H8O)]n or [(THF)Cs(\u03bc-\u03b75:\u03b75-Cp\u2032)3YbII]n was synthesized by reduction of a red THF solution of (C5H4SiMe3)3YbIII with excess Cs metal and identified by X-ray diffraction. The compound crystallizes as a two-dimensional array of hexa\u00adgons with alternating CsI and YbII ions at the vertices and cyclo\u00adpenta\u00addienyl groups bridging each edge. This, based off the six-electron cyclo\u00adpenta\u00addienyl rings occupying three coordination positions, gives a formally nine-coordinate tris\u00ad(cyclo\u00adpenta\u00addien\u00adyl) coordination environment to Yb and the Cs is ten-coordinate due to the three cyclo\u00adpenta\u00addienyl rings and a coordinated mol\u00adecule of THF. The complex comprises layers of Cs3Yb3 hexa\u00adgons with THF ligands and Me3Si groups in between the layers. The Yb\u2014C metrical parameters are consistent with a 4f14 YbII electron configuration.The green compound poly[(tetra\u00adhydro\u00adfuran)\u00adtris\u00ad[\u03bc-\u03b7 However, the Cs reductions yielded polymeric complexes of general formula [Cp\u2032\u2032M(\u03bc-Cp\u2032\u2032)2Cs(THF)2]n where the Cs cation has coord\u00adin\u00adated THF and cyclo\u00adpenta\u00addienide ligands. Attempts to extend this chemistry to smaller rare-earth metals by reduction of Cp\u20323Ln  showed evidence of LnII in solution; however, the reduction products were highly unstable and decomposed even at 238\u2005K.The new +2 oxidation states for the rare-earth metals Y, La, Ce, Pr, Gd, Tb, Ho, Er, and Lu were recently discovered by reduction of CpC8 Fig.\u00a01 3Yb]n, 1 (Cp\u2032 = C5H4SiMe3) was isolated by reduction of the Cp\u20323YbIII complex ][Cp\u20323YbII] (crypt = 2.2.2-cryptand), which was fully characterized as a 4f14 YbII complex, Table\u00a023Ln reduction chemistry, the difference in Ln\u22efCp(centroid) distances between the LnIII and LnII complexes provides important information on the electronic configuration of the lanthanide ion  distances for reduction of 4fnLnIII ions to 4fn+1LnII ions range from 0.1 to 0.2\u2005\u00c5  distance is characteristic of a 4f13 YbIII reduction to a 4f14 YbII ion. In contrast, LnII ions with 4nf5d1 configurations where the additional electron populates a d-orbital instead of the an f-orbital have differences of only 0.02\u20130.05\u2005\u00c5 \u22efYb\u22efCp\u2032(centroid) and 109.0\u2013121.4\u00b0 Cp\u2032(centroid)\u22efCs\u22efCp\u2032(centroid) angles generate the undulation of the hexa\u00adgons shown in Fig.\u00a06The side view of these layers in Fig.\u00a061 are shorter than the 3.278 and 3.435\u2005\u00c5 Cs\u22efCp\u2032\u2032(centroid) distances in [(THF)2Cs][(\u03bc-\u03b75:\u03b75-Cp\u2032\u2032)2UII(\u03b75-Cp\u2032\u2032)]n,  distances in {[(Me3Si)2NCs]2\u00b7[(C5H5)2Fe)] 0.5\u00b7(C6H5Me)}n,  distances in [(THF)2Cs(\u03bc3-O)3{[Ti(C5Me5)]3-(\u03bc3-CCH2)}] 2UII(\u03b75-Cp\u2032\u2032)]n 3{[Ti(C5Me5)]3(\u03bc3-CCH2)}] , 3.197\u2005(1), and 3.268\u2005(2)\u2005\u00c5 Cs\u22efCp\u2032(centroid) distances in 1 differs from that of the [(THF)2Cs][(\u03bc-\u03b75:\u03b75-Cp\u2032\u2032)2MII(\u03b75-Cp\u2032\u2032)]n, complexes , which comprise zigzag chains of \u2013M\u2013(\u03bc-Cp\u2032\u2032)\u2013Cs\u2013(\u03bc-Cp\u2032\u2032)\u2013 repeat units with a terminal Cp\u2032\u2032 attached to M and two terminal THF ligands attached to Cs  coordination like Yb in 1, but the Cs is coordinated by only two cyclo\u00adpenta\u00addienyl ligands to give a bent metallocene Cp\u2032\u20322Cs(THF)2 sub-structure with these larger rings.The extended structure of et al., 2016x moieties with various types of cyclo\u00adpenta\u00addienyl rings (Cpx): [Na(\u03bc-\u03b75:\u03b75-C5H5)3YbII]n 2YbII2(\u03bc-\u03b75:\u03b75-Cp\u2032\u2032)2]n Yb(\u03bc-I)(\u03bc-\u03b75:\u03b75-C5Me5)Yb(C5Me5)]n (Ph2Pz)(THF)]n  3YbII]n 3SmII] is similar 2UII(\u03b75-Cp\u2032\u2032)]n 2NCs]2[(C5H5)2Fe)]\u00b70.5(C6H5Me)}n 3{[Ti(C5Me5)]3(\u03bc3-CCH2)}] Li]n  in THF (2\u2005mL) to excess Cs as a smear produced a green solution. This was stirred for 15\u2005min at room temperature and then layered at the bottom of a vial below an Et2O (10\u2005mL) layer for crystallization at \u221235\u00b0C. After 1\u2005d, X-ray quality dark-green crystals of [(THF)Cs(\u03bc-\u03b75:\u03b75-Cp\u2032)3YbII]n were isolated. A small number of crystals were obtained and used for crystallographic analysis. Too little sample was available for other characterization.In an argon-filled glovebox, addition of a red solution of Cp\u20325:\u03b75-Cp\u2032)3YbII]n, 1 are summarized in Table\u00a03Uiso(H) values of 1.2Ueq(C) for CH2 and aromatic hydrogens and 1.5Ueq(C) for CH3 hydrogens with C\u2014H distances of 0.99 (CH2), 0.95 (aromatic), and 0.98\u2005\u00c5 (CH3).Crystal data and structure refinement for [(THF)Cs I. DOI: 10.1107/S2056989020008051/zl2785Isup2.hklStructure factors: contains datablock(s) I. DOI: 2010185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Lolium multiflorum L.) including a cultivar , bred to accumulate larger concentrations of Mg.Magnesium (Mg) deficiency (known as grass tetany) is a serious metabolic disorder that affects grazing ruminants. We tested whether Mg-fertiliser can increase Mg concentration of Italian ryegrasses (2.6H2O). Under field conditions, the three cultivars in the CE condition and cv. Alamo were grown at two sites, and four rates of MgSO4 fertiliser application rates (0\u2013200\u00a0kg\u00a0ha\u22121 MgO). Multiple grass cuts were taken over two-years.Under controlled environment (CE) conditions, three cultivars  were grown in low-nutrient compost at six fertiliser rates (0\u20131500\u00a0\u03bcM MgClp\u2009<\u20090.05) smaller than cv. Alamo. The effect of Mg-fertiliser rate on DM yield was not significant (p\u2009\u2265\u20090.05).Grass Mg concentration increased with increasing Mg-fertiliser application rates in all cultivars and conditions. Under field conditions, cv. Bb2067 had 11\u201373% greater grass Mg concentration and smaller forage tetany index (FTI) than other cultivars across the Mg-fertiliser application rates, sites and cuts. Grass dry matter (DM) yield of cv. Bb2067 was significantly  contains supplementary material, which is available to authorized users. Grazing landscapes and ruminant livestock have a dominant role in the environmental, economic and food security of many countries, especially in temperate regions. For example, in 2017/18, 72% of the UK\u2019s land area (17.5\u00a0M\u00a0ha) was utilised for agriculture; of that area the proportion of grazing land was 35% permanent grass, 22% sole rights rough grazing, 6.9% common land rough grazing, and 6.5% temporary grass DEFRA . These g\u22121 DM for cattle, and 900 and 1200\u00a0mg\u00a0kg\u22121 DM for sheep  and potassium (K+) ions, which is termed as the forage tetany index (FTI)  is divided by the atomic weight and multiplied by the valence of the respective elements).In livestock, ~70% of Mg is stored in the skeleton and this pool is not easily mobilised when dietary Mg intake is reduced (Martens and Stumpff FTI) Eq.  (Kemp anFTI) Eq. . The risFTI) Eq. . AnnuallFTI) Eq. .1\\docume+ in the soil solution suppresses the absorption of Mg2+ by plant roots  digestibility which accelerates rumen passage and reducing the ruminal absorption of Mg Suttle . This iss Elliot .\u22121 DM\u2009\u00b1\u2009SD) reported include: grass hay 1400\u2009\u00b1\u2009520, grass silage 1700\u2009\u00b1\u2009540, clover silage 2300\u2009\u00b1\u2009750, lucerne hay 1700\u2009\u00b1\u2009270, maize silage 2200\u2009\u00b1\u2009690 (Suttle \u22121 DM) in New Zealand  synthetic variety called Magnet  with increased grass Mg concentration was bred by the Welsh Plant Breeding Station in the 1970s  containing low nutrient media . Plants were watered every other day with Hortimix standard. In total there were 18 trays, each containing 8 plants of each line, randomly assigned to the central part of the tray. These plants were surrounded by cv. RvP plants to act as guard rows.The CE experiment was conducted at the Sutton Bonington Campus of the University of Nottingham in 2016. Three cultivars, cv. Bb2067, cv. Bb2068 and cv. RvP were sown on 09 August 2016 in 576 cell trays  in compost  with a topping of fine horticultural grade silver sand (Dejex Supplies Ltd). The trays were transferred to a controlled environment room  and watered every other day with HortiMix standard (Dejex Supplies Ltd) at 10\u00a0ml\u00a0L2.6H2O. These were applied as 1\u00a0L per tray of a liquid feed based on Hoagland\u2019s media, containing 0.25\u00a0mM KH2P04, 0.5\u00a0mM KOH, 0.75\u00a0mM MgCl2.6H2O, 0.75\u00a0mM H2SO4, 0.1\u00a0mM FeNaEDTA, 2\u00a0mM Ca(NO3)2.4H2O, 2\u00a0mM NH4NO3, 30\u00a0\u03bcM H3BO3, 10\u00a0\u03bcM MnSO4.4H2O, 1\u00a0\u03bcM ZnSO4.7H2O, 3\u00a0\u03bcM CuSO4.5H2O, and 0.5\u00a0\u03bcM Na2MoO4.2H2O. The pH was maintained at 6.4.Thirty seven days after transplanting, the plants were cut leaving ~1\u00a0cm of aerial tissue. The cut plants were then watered every other day with 6\u00a0Mg treatments at 0, 75, 188, 375, 750 and 1500\u00a0\u03bcM MgCl3 and analysed by ICP-MS as described by Thomas et al.  and Edinburgh, Scotland  across two years (2017\u20132018). The soil type at Aberystwyth is well drained loam over gravel in the Eutric Endoskeleti-Eutric Cambisols  was added at a rate of 60\u00a0kg\u00a0ha\u22121 prior to the first cut (March 2017), and then at 100, 100, and 60\u00a0kg\u00a0ha\u22121 after cuts 1, 2, 3, respectively,\u00a0and then 35\u00a0kg\u00a0ha\u22121 after all subsequent cuts. No fertiliser was added after the final cut. The Mg fertiliser was applied in April 2017 and March 2018 as magnesium sulphate (MgSO4) at MgO equivalent rates of 0, 50, 100, and 200\u00a0kg\u00a0ha\u22121. Reagent grade\u2009\u2265\u200997% anhydrous MgSO4  was dissolved in warm water and applied with a calibrated knap sack sprayer after the first sward management cutting. Magnesium fertiliser application rates were scaled in relation to a recommendation of 50\u2013200\u00a0kg\u00a0ha\u22121 of MgO application every 3\u20134\u00a0years when exchangeable soil Mg\u2009is\u00a0<\u200926\u00a0mg\u00a0L\u22121  HNO3 and analysed using ICP-MS  at the University of Nottingham  were collected with an auger, using a \u201cW\u201d transect across each site to determine baseline soil physico-chemical properties. Soil samples were also collected from the 16 treatments (samples from the centre of each of four replicate plots were composited) at the beginning of June 2018, after the second Mg-fertiliser application. The baseline soil pH (in water), and exchangeable Mg, Ca and K were analysed at Lancrop Laboratory  while the second-year soil pH, and exchangeable Mg, Ca and K concentrations were\u00a0analysed at the University of Nottingham. At both laboratories, a similar procedure was followed. Thus, 5\u00a0mg of <2\u00a0mm sieved soil was dissolved in 25\u00a0mL of 1\u00a0Data were compiled in MS Excel and Access. For field experiments where repeated observations  were made, statistical analyses were conducted using R  was addressed by the use of a linear mixed model. Two models were considered. In the first (sphericity assumption) where the correlation between the residuals for any two measures on the same unit were treated as uniform. In the second an exponential autocorrelation for successive measurements was assumed. The two models were fitted using the nlme package  as shown in the Online Resource (Sup Table 2.6H2O), the grass Mg concentration  was 4966\u2009\u00b1\u2009880 (cv. Bb2067), 3115\u2009\u00b1\u20091018 (cv. Bb2068), and 3889\u2009\u00b1\u2009878 (cv. RvP). At the zero Mg application rate, the grass Mg concentration  was 2366\u2009\u00b1\u2009381 (cv. Bb2067), 1382\u2009\u00b1\u2009343 (cv. Bb2068), and 1629\u2009\u00b1\u2009320 (cv. RvP). There was no significant interaction effect of cultivar \u00d7 Mg application rate on grass Mg concentration (p\u2009\u2265\u20090.05) (Table Grass Mg concentration increased with increasing Mg application rate (p\u2009\u2265\u20090.05) decrease with increasing Mg application rate (Table p\u2009<\u20090.01) as shown in the Online Resource Sup Table p\u2009\u2265\u20090.05, Table The FTI did not significantly (te Table . Cultivate Table . At the \u22121 at Aberystwyth and 193\u00a0mg\u00a0L\u22121 at Edinburgh (Table p\u2009<\u20090.05) due to the application of MgSO4 (Table \u22121) for control plots was 80 at Aberystwyth and 177 at Edinburgh. The increase in the exchangeable soil Mg concentration at Aberystwyth was 20%, 39%, and 74%, and at Edinburgh was 10%, 12% and 32%, at Mg-fertiliser application rates of 50, 100 and 200\u00a0kg MgO ha\u22121, respectively. Baseline exchangeable soil Ca and K concentration, and soil pH were below the recommended optimal for forage cultivation at both sites  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table \u22121), the grass Mg concentrations  were 2637\u2009\u00b1\u2009506 , 1674\u2009\u00b1\u2009314 , 2009\u2009\u00b1\u2009454 , and 1907\u2009\u00b1\u2009431 . At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 2104\u2009\u00b1\u2009495 , 1543\u2009\u00b1\u2009423 , 1786\u2009\u00b1\u2009457 , and 1787\u2009\u00b1\u2009490 . In 2018, at the largest Mg-fertiliser application rate, the grass Mg concentrations  were 2990\u2009\u00b1\u2009628 (cv. Bb2067), 2414\u2009\u00b1\u2009671 (cv. Bb2068), 2691\u2009\u00b1\u2009624 (cv. Alamo), and 2563\u2009\u00b1\u2009643 (cv. RvP). At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 2545\u2009\u00b1\u2009589 (cv. Bb2067), 2201\u2009\u00b1\u2009694 (cv. Bb2068), 2101\u2009\u00b1\u2009572 (cv. Alamo) and 2050\u2009\u00b1\u2009553 (cv. RVP)  cultivar \u00d7 Mg-fertiliser application rate, cultivar \u00d7 cutting date, and Mg-fertiliser rate \u00d7 cutting date interaction effect on grass Mg concentration. In 2017, there was cultivar \u00d7 cutting date, and Mg-fertiliser rate \u00d7 cutting date interaction effect on grass Mg concentration. There was no significant (p\u2009\u2265\u20090.05) cultivar \u00d7 Mg-fertiliser application rate \u00d7 cutting date interaction effect on the grass Mg concentration in either year  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table p\u2009<\u20090.05) affected by cultivar, cutting date, and cultivar \u00d7 cutting date interaction in 2017 and 2018, but the effect of Mg-fertiliser rate on FTI was only significant in 2018. There was no statistically significant (p\u2009\u2265\u20090.05) cultivar \u00d7 Mg-fertiliser rate, Mg-fertiliser rate \u00d7 cutting date, or cultivar \u00d7 Mg-fertiliser rate \u00d7 cutting date, interaction effect on the FTI  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table \u22121), the grass Mg concentrations  were 2801\u2009\u00b1\u2009521 , 1698\u2009\u00b1\u2009410 , 2122\u2009\u00b1\u2009514  and 1945\u2009\u00b1\u2009433 . At the zero Mg-fertiliser application rate the grass Mg concentrations  were 2337\u2009\u00b1\u2009478 , 1354\u2009\u00b1\u2009304 (cv. Bb2068), 1732\u2009\u00b1\u2009438  and 1632\u2009\u00b1\u2009386 . In 2018, at the largest Mg-fertiliser application rate, the grass Mg concentrations  were 4205\u2009\u00b1\u2009746 (cv. Bb2067), 2578\u2009\u00b1\u2009503 (cv. Bb2068), 3094\u2009\u00b1\u2009726 (cv. Alamo) and 2965\u2009\u00b1\u2009707 (cv. RvP). At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 3239\u2009\u00b1\u2009531 , 2103\u2009\u00b1\u2009395 (cv. Bb2068), 2526\u2009\u00b1\u2009498 (cv. Alamo) and 2437\u2009\u00b1\u2009480 (cv. RVP)  affected by cultivar, Mg-fertiliser application rate and cutting date. The cultivar \u00d7 cutting date, and Mg-fertiliser application rate \u00d7 cutting date interaction effect on grass Mg concentration was significant (p\u2009<\u20090.05) in both years. There was significant (p\u2009<\u00a00.05) cultivar \u00d7 Mg-fertiliser rate \u00d7 cutting date interaction effect on grass Mg concentration in 2018 but not in 2017  except the one between cv. Alamo and cv. RvP in 2017 as shown in the Online Resource (Sup Table p\u2009<\u20090.05) affected by cultivar, Mg-fertiliser application rate and cutting date. Cultivar \u00d7 cutting date, and Mg-fertiliser rate \u00d7 cutting date interaction effect was significant (p\u2009<\u20090.05) on FTI in 2017 and 2018. There was no significant (p\u2009\u2265\u20090.05) cultivar \u00d7 Mg-fertiliser, and cultivar \u00d7 Mg-fertiliser rate \u00d7 cutting date interaction effect on FTI in both years  were 21.0\u2009\u00b1\u20090.7 (cv. Bb2067), 21.0\u2009\u00b1\u20090.7 (cv. Bb2068), 24.5\u2009\u00b1\u20092 (cv. Alamo), and 22.9\u2009\u00b1\u20091.0 (cv. RvP) in 2017. At the largest Mg-fertiliser application rate (200\u00a0kg\u00a0ha\u22121), total dry matter yields  were 21.0\u2009\u00b1\u20090.9 (cv. Bb2067), 21.2\u2009\u00b1\u20090.9 (cv. Bb2068), 24.1\u2009\u00b1\u20090.5 (cv. Alamo), and 23.3\u2009\u00b1\u20090.9 (cv. RvP). In 2018, at the zero Mg-fertiliser application rate, total dry matter yields  were 6.6\u2009\u00b1\u20090.6 (cv. Bb2067), 6.4\u2009\u00b1\u20090.5 (cv. Bb2068), 8.7\u2009\u00b1\u20090.7 (cv. Alamo), and 8.2\u2009\u00b1\u20090.8 (cv. RvP). At the largest Mg-fertiliser application rate, total dry matter yields  were 6.9\u2009\u00b1\u20090.3 (cv. Bb2067), 6.7\u2009\u00b1\u20090.5 (cv. Bb2068), 9\u2009\u00b1\u20090.6 (cv. Alamo), and 9.1\u2009\u00b1\u20090.3 (cv. RvP)  were 19.8\u2009\u00b1\u20090.5 (cv. Bb2067), 19.6\u2009\u00b1\u20090.9 (cv. Bb2068), 21.8\u2009\u00b1\u20091.6 (cv. Alamo), and 19.9\u2009\u00b1\u20091.5 (cv. RvP). At the largest Mg-fertiliser application rate, total dry matter yields  were 19.6\u2009\u00b1\u20091.4 (cv. Bb2067), 19.7\u2009\u00b1\u20090.7 (cv. Bb2068), 20.4\u2009\u00b1\u20090.6 (cv. Alamo), and 20.2\u2009\u00b1\u20091.6 (cv. RvP). In 2018, at the zero Mg-fertiliser application rate, total dry matter yields  were 7.8\u2009\u00b1\u20090.2 (cv. Bb2067), 8\u2009\u00b1\u20090.1 (cv. Bb2068), 9.4\u2009\u00b1\u20090.8 (cv. Alamo), and 9.3\u2009\u00b1\u20090.3 (cv. RvP). At the largest Mg-fertiliser application rate, dry matter yields  were 7.5\u2009\u00b1\u20091 (cv. Bb2067), 8.3\u2009\u00b1\u20090.2 (cv. Bb2068), 9.1\u2009\u00b1\u20090.1 (cv. Alamo), and 8.4\u2009\u00b1\u20090.4 (cv. RvP)  interaction effects of cultivar \u00d7 Mg-fertiliser application rate, cultivar \u00d7 cutting date, cultivar \u00d7 Mg-fertiliser or cultivar \u00d7 Mg-fertiliser rate \u00d7 cutting date on the grass biomass yield at both sites in both years. There was a highly significant (p\u2009<\u20090.01) negative correlation between grass biomass yield and Mg concentration. The correlation between grass DM yield and Mg concentration at Aberystwyth was , and at Edinburgh was .There were no significant (4) application rate for all the cultivars in 2017 and 2018  more S in its biomass than the other three Italian ryegrass cultivars. Planned contrasts among the cultivars mean S concentration were significant (p\u2009<\u20090.01) except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table p\u2009<\u20090.05) affected by cultivar, Mg-fertiliser application rate, cutting date, and by the interaction effect of cultivar \u00d7 cutting date and Mg-fertiliser rate \u00d7 cutting date, in 2017 and 2018 (Table p\u2009<\u20090.05) affected by cultivar, Mg-fertiliser application rate and cutting date. The cultivar \u00d7 Mg-fertiliser application rate, and cultivar \u00d7 cutting date interaction effect on grass S concentration was significant (p\u2009<\u20090.05) in 2018 but not in 2017 (Table p\u2009<\u20090.05) in both years. There was no significant (p\u2009\u2265\u20090.05) cultivar \u00d7 Mg-fertiliser application rate \u00d7 cutting date interaction effect on grass S concentration , the grass S concentrations  were 3257\u2009\u00b1\u2009703 (cv. Bb2067), 2738\u2009\u00b1\u2009476 , 2790\u2009\u00b1\u2009697 (cv. Alamo) and 2838\u2009\u00b1\u2009595 (cv. RvP). At the zero Mg-fertiliser application rate the grass S concentrations  were 2814\u2009\u00b1\u2009588 , 2540\u2009\u00b1\u2009512 (cv. Bb2068), 2599\u2009\u00b1\u2009561 (cv. Alamo) and 2662\u2009\u00b1\u2009573 (cv. RvP). In 2018, at the largest Mg-fertiliser application rate, the grass S concentrations  were 3970\u2009\u00b1\u2009845 (cv. Bb2067), 3266\u2009\u00b1\u2009592 (cv. Bb2068), 3345\u2009\u00b1\u2009429 (cv. Alamo) and 3382\u2009\u00b1\u2009604 (cv. RvP). At the zero Mg-fertiliser application rate, the grass S concentrations  were 3309\u2009\u00b1\u2009601 , 3155\u2009\u00b1\u2009575 (cv. Bb2068), 2861\u2009\u00b1\u2009637 (cv. Alamo) and 2830\u2009\u00b1\u2009639 (cv. RVP) , the grass S concentrations  were 4063\u2009\u00b1\u2009844 , 3153\u2009\u00b1\u2009600 , 3510\u2009\u00b1\u2009860  and 3372\u2009\u00b1\u2009782 . At the zero Mg-fertiliser application rate the grass S concentrations  were 3393\u2009\u00b1\u20091033 , 2638\u2009\u00b1\u2009819 (cv. Bb2068), 2973\u2009\u00b1\u2009898  and 2931\u2009\u00b1\u2009904 (cv. RVP). In 2018, at the largest Mg-fertiliser application rate, the grass S concentrations  were 4303\u2009\u00b1\u2009908 (cv. Bb2067), 3292\u2009\u00b1\u2009813 (cv. Bb2068), 3526\u2009\u00b1\u2009909 (cv. Alamo) and 3502\u2009\u00b1\u2009820 (cv. RVP). At the zero Mg-fertiliser application rate, the grass S concentrations  were 3154\u2009\u00b1\u2009747 , 2885\u2009\u00b1\u2009645 (cv. Bb2068), 2835\u2009\u00b1\u2009627 (cv. Alamo) and 2742\u2009\u00b1\u2009614 (cv. RVP)  for the field experiment. There are a range of potential Mg resources including dolomitic limestone  of cv. Bb2067 in these trials in 2017 was well above that perennial ryegrass under conservation sward management and comparable to cv. Alamo under farmer management. There is a need to transfer cv. Bb2067 Mg-accumulating trait into the cultivars that yield larger biomass  ratio in lush grasses with large N in spring during lambing season when animal requirement for S increases ESM 2(XLSX 149\u00a0kb)ESM 3(XLSX 14\u00a0kb)ESM 4(XLSX 12\u00a0kb)ESM 5(XLSX 9\u00a0kb)ESM 6(XLSX 12\u00a0kb)"}
{"text": "The structure of the title compound is stabilized by the presence of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. Other inter\u00adactions such as C\u2014H\u22ef\u03c0 are also important in the analysis of the Hirshfeld surface. Mol\u00adecular docking studies show this compound to be a potential anti\u00adcoagulant agent. 21H17N3O5, consists of three rings, A, B and C, linked by amide bonds with the benzene rings A and C being inclined to the mean plane of the central benzene ring B by 2.99\u2005(18) and 4.57\u2005(18)\u00b0, respectively. In the crystal, mol\u00adecules are linked via N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming fused R22(18), R34(30), R44(38) rings running along [R33(37) and R33(15) rings along [001]. Hirshfeld analysis was undertaken to study the inter\u00admolecular contacts in the crystal, showing that the most significant contacts are H\u22efO/O\u22efH (30.5%), H\u22efC/C\u22efH (28.2%) and H\u22efH (29.0%). Two zones with positive  potentials and two zones with negative  potentials promote the N\u2014H\u22efO inter\u00adactions in the crystal. An evaluation of the mol\u00adecular coupling of the title compound and the protein with enzymatic properties known as human coagulation factor Xa (hfXa) showed the potential for coupling in three arrangements with a similar minimum binding energy, which differs by approximately 3 kcal mol\u22121 from the value for the mol\u00adecule Apixaban, which was used as a positive control inhibitor. This suggests the title compound exhibits inhibitory activity.The title compound, C Some amino\u00adbenzamide derivatives present high efficiencies in their non-linear optical properties  and C  form dihedral angles of of 2.99\u2005(18) and 4.57\u2005(18)\u00b0, respectively, with the mean plane of the central ring B . In turn, the amide groups C8/N2/C7(O3)/C1 (r.m.s deviation = 0.0081\u2005\u00c5) and C15/N3/C14(O4)/C10 (r.m.s deviation = 0.0101\u2005\u00c5), which link the rings, are inclined by 37.72\u2005(15) and 29.35\u2005(16)\u00b0, respectively, to ring B. The nitro group forms an angle of 5.3\u2005(2)\u00b0 with ring A while the meth\u00adoxy group is approximately coplanar with ring C, forming an angle of 1.1\u2005(5)\u00b0. The mol\u00adecule is formed by three main planes resulting from the planes that form the rings with the B ring resembling a fallen step between A and C. All bond lengths  \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a01; (ii) \u2212x, y\u00a0+\u00a0z\u00a0+\u00a01] form fused a). In turn, playing the role of complementary inter\u00adactions in crystal growth, other C\u2014H\u22efO-type inter\u00adactions  link the mol\u00adecules at their ends, ensuring their stability in the growth process. Together with the N\u2014H\u22efO inter\u00adactions, they contribute to the formation of additional fused b). Weak C21\u2014H21B\u22efCg1 inter\u00adactions occur, where Cg1 is the centroid of the C1\u2013C6 benzene ring, with a H21B\u22efCg1 distance of 2.83\u2005\u00c5.The crystalline packing in compound (I)CrystalExplorer program . The overall two-dimensional fingerprint plot , and those delineated into by H\u22efO/O\u22efH, H\u22efH, H\u22efC/C\u22efH, C\u22efC, N\u22efC/C\u22efN, H\u22efN/N\u22efH, O\u22efO, O\u22efC/C\u22efO, and N\u22efO/O\u22efN contacts are illustrated in Fig.\u00a04b\u2013j, respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction corresponds to H\u22efO/O\u22efH contributing 30.5% to the overall crystal packing, as shown in Fig.\u00a04b. The pair of spikes in the fingerprint plot have a symmetrical distribution of high-density points with the tip at de + di = 1.98\u2005\u00c5. The H\u22efH inter\u00adactions, shown in Fig.\u00a04c, contribute 29.0% to the total crystal packing and appear as widely dispersed points of high density due to the large hydrogen-atom content of the mol\u00adecule with the rounded tip at de + di = 1.20\u2005\u00c5. The presence of C\u2014H\u22ef\u03c0 inter\u00adactions is shown as a pair of characteristic wings on the fingerprint plot , delineated into H\u22efC/C\u22efH contacts (28.2% contribution to the HS) having the tip at de + di = 2.84\u2005\u00c5. These results reveal the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play major roles in the crystal packing  using the ot Fig.\u00a04a, and tot Fig.\u00a04d, delinGauss09W  level of theory, to obtain a qualitative analysis and the Multiwfn 3.6 program for a qu\u00adanti\u00adtative analysis  of (I)Autodock Vina 4.2.6 d Table\u00a02. Compound Table\u00a02, which det al., 20162-azan\u00adyl)phen\u00adyl](phenyl-\u03bb2-azan\u00adyl)methanone as the main skeleton gave 76 hits. Seven structures containing the [3-(benzoyl-\u03bb2-azan\u00adyl)phen\u00adyl](phenyl-\u03bb2-azan\u00adyl)methanone framework with nitro and meth\u00adoxy groups as substituents similar to the title compound were found, viz., N-{3-[N\u2032-(2-meth\u00adoxy\u00adphen\u00adyl)carbamo\u00adyl]-5-methyl-2-meth\u00adoxy\u00adphen\u00adyl}-2-meth\u00adoxy-5-methyl-3-nitro\u00adbenzamide carbamo\u00adyl]-5-methyl-2-meth\u00adoxy\u00adphen\u00adyl}-2-hy\u00addroxy-5-methyl-3-nitro\u00adbenzamide amino]\u00adbenzo\u00adyl}amino)-2-meth\u00adoxy\u00adbenzoate]aqua\u00adsodium methanol solvate] benzamide (ii) , previously synthesized, was subjected to an acyl\u00adation reaction in 3-nitro\u00adbenzoyl chloride (a)  under chloro\u00adform reflux conditions to obtain compound (I)3-Amino-\u22121) = 3338, 3285 (N\u2014H), 3076, 2969, 1650, 1637 (C=O), 1585 (C=C), 1526, 1510, 1434, 1353 (NO2), 1316, 1301, 1241, 1137, 1026, 898, 829, 819, 721, 683\u2005cm\u22121. The UV\u2013Vis spectrum for (I)M) was obtained in DMF with a maximum of 273\u2005nm (0.62 absorption). MS , m/z [M+] calculated for C21H17N3O5+: 391.12 (100%) and 392.12 (23.1%); found: 391.10 and 392.10 (25.1%).FT\u2013IR (ATR): \u03c5 (cmUiso(H) = 1.2Ueq(parent atom) or 1.5Ueq(C). After refinement, ROTAX suggested twinning by a 180\u00b0 about [100]. This law was used to generate an hklf5 format reflection file. Refinement against this file improved R factors and residual Q peaks\u00b7BASF refined to 0.090\u2005(4)Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020013730/dj2013sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020013730/dj2013Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020013730/dj2013sup3.pdfSynthesis and characterization of (I). DOI: Click here for additional data file.10.1107/S2056989020013730/dj2013Isup4.cmlSupporting information file. DOI: 2016019CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The phenyl rings in the [C24H38N4O2Te2]2+ cation are in a cis arrangement to enable this species to participate in Te\u22efCl cation\u2013anion inter\u00adactions. There are also C\u2014H\u22efO inter\u00adactions involving the dimethyl sulfoxide ligands and numerous cation\u2013anion and anion\u2013anion C\u2014H\u22efCl inter\u00adactions, which link the ions into a complex three-dimensional array.In the title salt, di-\u03bc-oxido-bis\u00ad{2,6-bis\u00ad[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]phenyl-\u03ba This might be due to the formation of the highly stable tellurenium(II) cation where the Te is T-shaped and involved in a three-centered, four-electron bond. While checking the reproduc\u00adibility of the reaction, in one instance, because of the adventitious uptake of oxygen, the reaction unexpectedly resulted in the isolation of the title compound, which contains the ditelluroxonium(IV) cation 2, 2 with the PdCl3(DMSO) anion. It is worth noting that Furukawa and coworkers have reported a similar diorganotelluroxonium(IV) cation namely, 2\u00b7PF6, by the reaction of the diorganotelluride 2Te with the oxidizing agent NOPF6 ]\u22122, 3, crystallizes in the triclinic space group P2 there is a cis arrangement of the aryl rings of the attached 2,6-[(di\u00admethyl\u00adamino)\u00admeth\u00adyl)]phenyl substituents 2C6H3Te(\u03bc-O)]2+\u00b7PF6\u2212, wherein the cation lies on a center of inversion and thus the aryl groups are in a trans configuration \u20132.495\u2005(2)\u2005\u00c5 for 2, are in good agreement with the values observed in 2+\u00b7PF6\u2212 [2.475\u2005(5)\u20132.486\u2005(5)\u2005\u00c5] \u00b0 and those between the Te2O2 plane and the aryl rings are 88.77\u2005(8) and 85.00\u2005(8)\u00b0, indicating that the two aryl groups are not coplanar, and are too far apart to form \u03c0\u2013\u03c0 stacking inter\u00adactions (the closest contact is between C1 and C1A at 3.672\u2005\u00c5). Thus, the driving force for the adoption of this sterically unfavorable cis conformation appears to be the formation of Te\u22efCl cation\u2013anion inter\u00adactions, which would not be possible if the trans conformation were adopted. In this case, there is a short Te2\u22efCl3 contact of 3.386\u2005(1)\u2005\u00c5 and longer contacts of 3.833\u2005(1)\u2005\u00c5 (Te2\u22efCl2) and 3.991\u2005(1)\u2005\u00c5 (Te1\u22efCl5) 2C6H3Te(\u03bc-O)]2+\u00b7PF6\u2212, no such cation\u2013anion inter\u00adactions are present and hence the more sterically favorable trans conformation is adopted. In the other two related structures containing the Te2O22+ core dication, the same cis configuration is adopted to allow the formation of inter\u00adionic Te\u22efO inter\u00adactions  cation and key geometrical data are listed in Table\u00a01ts Fig.\u00a01. This isIn addition to the Te\u22efCl cation\u2013anion inter\u00adactions mentioned above, there are also C\u2014H\u22efO inter\u00adactions involving the DMSO ligands and numerous cation\u2013anion and anion\u2013anion C\u2014H\u22efCl inter\u00adactions Table\u00a02, which l2O22+ core. The first report on the mol\u00adecular structure of a diorganotelluroxonium(IV) cation was made by Furukawa and co-workers 2C6H3Te(\u03bc-O)]2+ charge-balanced as the PF6\u2212 salt. Beckmann and coworkers reported the mol\u00adecular structure of [(6-Ph2P(O)-Ace-5-) Te(\u03bc-O)]2\u00b72OTf +: 336.0545, found: 336.0541.Yield: 59%; m.p. 444\u2013446\u2005K; Ueq(C) [1.5Ueq(CH3)] and C\u2014H distances ranging from 0.95 to 0.99\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020011482/hb7941sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020011482/hb7941Isup2.hklStructure factors: contains datablock(s) I. DOI: 1563166CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Complexes 1 and 2 both contain the \u2018diamond core\u2019 motif found previously in a number of iron, copper, and manganese high-valent bis-oxo compounds. The flexibility in the propyl linker in the ligand scaffold of 2, as compared to that of the ethyl linker in 1, results in more elongated Mn\u2014N bonds, as one would expect. The Mn\u2014Mn distances and Mn\u2014O bond lengths support an MnIV oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are consistent with the local pseudo-octa\u00adhedral geometry.The addition of  The isolation and crystallographic characterization of the bis-oxo complexes 1 and 2 . The Mn ion of 1 is in a pseudo-octa\u00adhedral environment, with small deviations in the O\u2014Mn\u2014N angles relative to an ideal octa\u00adhedral geometry: O1\u2014Mn1\u2014N1 = 93.76\u2005(12), O1\u2014Mn1\u2014N2 = 92.13\u2005(12), O1\u2014Mn1\u2014N3 = 174.90\u2005(12), and O1\u2014Mn1\u2014N4 = 95.77\u2005(12)\u00b0. As is true for all diamond cores, the O1\u2014Mn1\u2014O1\u2032 angle is slightly compressed at 85.53\u2005(12)\u00b0. Metrical parameters, Mn1\u2014O1 = 1.829\u2005(3)\u2005\u00c5 and Mn1\u2014O1\u2032= 1.835\u2005(3)\u2005\u00c5 \u2005\u00c5] is slightly longer than that involving the secondary amine [Mn1\u2014N3 = 2.111\u2005(4)\u2005\u00c5]. The Mn1\u22efMn1\u2032 separation of 2.6899\u2005(15)\u2005\u00c5, falls within the normal range (2.6 to 2.8\u2005\u00c5) for bis-oxo-bridged MnIVMnIV dimers containing a diamond core. Complex 1 crystallizes with two crystallographically equivalent tetra\u00adphenyl\u00adborate counter-ions and two crystallographically equivalent water mol\u00adecules. The water mol\u00adecule is disordered over two sites with site occupancies refined to 0.870\u2005(12) and 0.130\u2005(12) for O2 and O2B respectively, with the applied constraint that both together give 100% occupancy.Complex \u00c5 Table\u00a01 fall wit2 also sits on an inversion center , making the two Mn atoms crystallographically equivalent. There is disorder in the position of the propyl linker carbon atoms . The site occupancies of N3, C1\u2013C3 and N3B, C1B\u2013C3B refined to 0.804\u2005(5) and 0.196\u2005(5), respectively, with the constraint of both together giving 100% occupancy. The Mn ion of 2 is again in a pseudo-octa\u00adhedral environment, with small deviations in O\u2014Mn\u2014N angles relative to ideal octa\u00adhedral geometry: O1\u2014Mn1\u2014N1 = 106.39\u2005(7), O1\u2014Mn1\u2014N2 = 174.90\u2005(7), O1\u2014Mn1\u2014N3 = 89.11\u2005(13), and O1\u2014Mn1\u2014N4 = 103.70\u2005(6)\u00b0. Again, as is true for all diamond cores, the O1\u2014Mn1\u2014O1\u2032 angle of 2 is slightly compressed at 85.98\u2005(7)\u00b0, and is similar to that in 1. Metrical parameters, Mn\u2014O1 = 1.8325\u2005(15) and Mn\u2014O1\u2032 = 1.8349\u2005(15)\u2005\u00c5, are also similar to those found in 1, and fall within the reported range (1.8 to 1.9\u2005\u00c5) for oxo-bridged MnIV complexes. The pyridine nitro\u00adgen atoms are once again further from the Mn ions than expected for a formal Mn\u2014N bond, but are oriented towards Mn at distances of Mn1\u2014N1 = 2.3251\u2005(18)\u2005\u00c5 and Mn1\u2014N4 = 2.3522\u2005(18)\u2005\u00c5. This bond elongation is likely to be due to steric inter\u00adference from the methyl groups at the 6-position of the pyridine rings. The nitro\u00adgens on the amine arms are much closer to the Mn center, and fall within the normal Mn\u2014N range (1.9 to 2.1\u2005\u00c5) for MnIV. The Mn\u2014N distance involving the tertiary amine [Mn1\u2014N2 = 2.1828\u2005(18)\u2005\u00c5] is noticeably longer than that involving the secondary amine [Mn1\u2014N3= 2.133\u2005(6)\u2005\u00c5]. The large difference between these bond lengths in 2, relative to those of 1, likely reflects the increased flexibility of the propyl linker in 2. The Mn1\u2014Mn1\u2032 distance [2.6825\u2005(7)\u2005\u00c5] in 2 is essentially the same as that found in 1, and falls within the normal range (2.6 to 2.8\u2005\u00c5) for bis-oxo-bridged MnIVMnIV dimers containing a diamond core. Complex 2 crystallizes with two tetra\u00adphenyl\u00adborate counter-ions and two diethyl ether mol\u00adecules per cation.Complex 1 and 2 are analogous to other reported MnIVMnIV(\u03bc-O)2 dimers. The Mn1\u2014Mn1\u2032 distances of 2.6899\u2005(15)\u2005\u00c5 in 1 and 2.6825\u2005(7)\u2005\u00c5 in 2 are comparable to other literature examples  and 1.8325\u2005(15)\u2005\u00c5 for 2 are also similar to literature reported values for MnIVMnIV(\u03bc-O)2 dimers , MeCN (CaH2), and CH2Cl2 (CaH2) were dried and distilled prior to use. Et2O was rigorously degassed and purified using solvent purification columns housed in a custom stainless steel cabinet and dispensed by a stainless steel Schlenk-line (GlassContour). Complexes 3 and 4 were synthesized as described by Coggins et al.  or 1.5Ueq(C-meth\u00adyl). For the disordered water mol\u00adecule in complex 1, the water was set-up as a rigid group free to rotate and move during refinement, with DFIX restraints between O and H and between both H per water. The displacement parameters of O2 and O2B were made the same with the EADP constraint. Hydrogen-atom isotropic displacement parameters were fixed at 1.5 times that of the water oxygen atoms. For the disorder in complex 2, the geometry of both groups was set to be similar with the \u2018SAME\u2019 option. Displacement parameters of N3-N3B, C1-C1B, C2-C2B, and C3-C3B were restrained with the SIMU command at 0.005 strength.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020004557/cq2034sup1.cifCrystal structure: contains datablock(s) global, Complex1, Complex2. DOI: 10.1107/S2056989020004557/cq2034Complex1sup4.hklStructure factors: contains datablock(s) Complex1. DOI: 10.1107/S2056989020004557/cq2034Complex2sup5.hklStructure factors: contains datablock(s) Complex2. DOI: 1994292, 1994291CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Enzyme promiscuity has important implications in the field of biocatalysis. In some cases, structural analogues of simple metabolic building blocks can be processed through entire pathways to give natural product derivatives that are not readily accessible by chemical means. In this study, we explored the plasticity of the aurachin biosynthesis pathway with regard to using fluoro\u2010 and chloroanthranilic acids, which are not abundant in the bacterial producers of these quinolone antibiotics. The incorporation rates of the tested precursor molecules disclosed a regiopreference for halogen substitution as well as steric limitations of enzymatic substrate tolerance. Three previously undescribed fluorinated aurachin derivatives were produced in preparative amounts by fermentation and structurally characterized. Furthermore, their antibacterial activities were evaluated in comparison to their natural congener aurachin D. Room for a halogen: The plasticity of the aurachin biosynthetic pathway in the myxobacterium S. erecta was explored for the use of fluoro\u2010 and chloroanthranilic acids. Incorporation of the unnatural precursors was quantified. Three fluorinated aurachin analogues were produced in sufficient quantity to enable their antibacterial activities to be assessed. Nature is a rich source of bioactive compounds, which have been optimized during evolution regarding their affinity to cellular targets.Stigmatella aurantiaca and later also found in other Stigmatella spp. as well as members of the actinomycete genera Rhodococcus and Streptomyces.[11]\u00a0Their structural relatedness to the known respiratory chain inhibitor 2\u2010heptyl\u20104\u2010hydroxyquinoline\u2010N\u2010oxide (HQNO) suggested early on that the aurachins might interfere with electron transport processes.6fb complex.1) and C (2).The aurachins are a large family of prenylated quinolone antibiotics, which were first discovered in cultures of the myxobacterium ptomyces.\u00a0Their st19F NMR spectroscopy.To explore this yet underexplored chemical space, we considered precursor\u2010directed biosynthesis as a viable option to introduce functional groups at these positions. Isotopic labelling studiesStigmatella erecta strain, which had been confirmed as an authentic aurachin producer.S. erecta in the presence of halogenated anthranilic acids, irrespective of the fluorine or chlorine substitution pattern. This may hint at interferences with tryptophan metabolism, as recently reported for mycobacteria.S. erecta, like many other myxobacteria, does not grow homogeneously in liquid media, but is known to form cellular aggregates.S. erecta, the amounts of biosynthesized aurachins were normalized to the production of myxothiazol A. This known secondary metabolite from S. erectaThe feeding studies were conducted in shaken Erlenmeyer flasks with a In accordance with previous studies, the addition of anthranilic acid was found to have a positive effect on aurachin production.19F NMR guided fractionation . The recovery of 6\u2010chloroaurachin D remained unsuccessful despite repeated attempts.In order to enable full NMR\u2010based structural characterization, feeding studies were repeated on multilitre scale to produce sufficient quantities of some aurachin analogues. Owing to the very low production titres that were achieved  and a laborious chromatographic separation process Figure\u2005, only th1\u2009a (0.5\u2005mg) originated from a 10\u2010L culture of S. erecta grown in the presence of 3\u2010fluoroanthranilic acid. The [M+H]+ ion peak of 1\u2009a possesses a m/z value of 382.2546, corresponding to a molecular formula of C25H32NOF and 10 double bond equivalents. UV maxima at 241, 321 and 333\u2005nm as well as NMR data  of the purified compound are almost consistent with those of 1,1H NMR spectrum of 1\u2009a features only three aromatic signals with a distinctive coupling pattern characteristic for a 3\u2010fluoroanthranilate\u2010derived moiety. COSY and HMBC experiments confirmed the presence of a farnesyl chain and a methyl group, which are connected to the assumed quinolone core of 1\u2009a at C\u20103 and C\u20102, respectively. Thus, 1\u2009a was identified as 8\u2010fluoroaurachin D.Compound 1\u2009b after multi\u2010step HPLC. The high\u2010resolution ESI\u2010MS spectrum confirmed the same molecular formula as 1\u2009a as well as similar UV maxima at 249, 321 and 331\u2005nm . A comparison of 1H NMR spectra corroborated that 1\u2009a and 1\u2009b are indeed structurally similar, but not identical. The differences pertained to the aromatic region. Following an analysis of their multiplicities and coupling constants, the aromatic proton signals of 1\u2009b could be assigned to a spin system for a 1,2,4\u2010trisubstituted benzene ring. Further interpretation of 1D and 2D NMR data  then led to the conclusion that 1\u2009b represents 7\u2010fluoroaurachin D.The extract from the 4\u2010fluoroanthranilic acid culture yielded 0.3\u2005mg of compound 1\u2009c was purified from a culture that had been supplied with 5\u2010fluoroanthranilic acid, yielding 0.3\u2005mg of material. Again, high\u2010resolution ESI\u2010MS and UV data pointed to an aurachin D derivative bearing a single fluorine substituent . The substitution pattern with the halogen at C\u20106 position of the quinolone ring was deduced from the heteronuclear coupling observed in the 1H NMR spectrum .Compound 1\u2009a\u2013c are equipotent to 1  was grown in modified Zein medium . To facilitate the recovery of secreted aurachins, adsorber resin XAD7HP (2\u2009% w/v) was added prior to sterilization. The medium was inoculated with seed culture (10\u2009% v/v inoculum) and the fermentation was conducted in an incubator shaker at 30\u2009\u00b0C and 130\u2005rpm for 7\u2005days. Anthranilic acid or its halogenated derivatives were supplemented as filter\u2010sterilized aqueous solutions (33\u2005mg\u2009L\u22121) after inoculation of the medium. For extraction the adsorber resin was separated from the culture broth by filtration, washed with water and retained compounds eluted three times with acetone and methanol. The extract was dried and used for relative quantification or compound purification.Quantitative analysis: For relative quantification experiments, the dried extracts of 1.5\u2005L cultures were resuspended in methanol, filtered and supplied to LC\u2010ESI\u2010MS  in positive mode. HPLC flow rate was 0.4\u2005mL\u2009min\u22121 on a Nucleodur RP 18 ec column  and a gradient from 5 to 98\u2009% acetonitrile in water supplemented with 0.1\u2009% formic acid over 10\u2005min, followed by 5\u2005min at 98\u2009% acetonitrile. All analyses were carried out at a capillary voltage of 4.5\u2005kV, desolvation gas (N2) temperature of 220\u2009\u00b0C, with a dry gas (N2) flow rate of 12\u2005L\u2009min\u22121.Compound purification: Dried raw extracts were resuspended in 60\u2009% aqueous methanol (100\u2005mL) and extracted three times with dichloromethane (60\u2005mL). Aurachins were exclusively present in the dichloromethane fraction. The purification continued on a Shimadzu HPLC system (LC\u201020AD) equipped with a diode array detector (SPD\u2010M20A). The initial separation was carried out on a VarioPrep C18 Gravity column  by two consecutive isocratic elutions with pure methanol and 90\u2009% aqueous methanol, respectively. The aqueous eluent was supplemented with 0.1\u2009% (v/v) trifluoroacetic acid and the flow rates were set to 4\u2005mL\u2009min\u22121. For 1\u2009c, an additional purification on a Nucleodur gravity column  was performed (60\u2009% to 100\u2009% acetonitrile in water supplemented with 0.1\u2009% (v/v) trifluoroacetic acid within 10\u2005min, followed by 100\u2009% acetonitrile for additional 10\u2005min), at a flow rate of 2\u00a0mL\u2009min\u22121. NMR spectra were acquired at 300\u2005K on a Bruker AV 700 Avance III HD (CryoProbe) or on a Bruker AV 600 Avance III HD (CryoProbe). Compounds were dissolved in methanol\u20104d, which also served as internal standard to calibrate spectra to \u03b4H=3.31\u2005ppm and \u03b4C=49.0\u2005ppm. 19F NMR spectra were referenced to residual trifluoroacetic acid at \u03b4F=\u221276.5\u2005ppm.8\u2010Fluoroaurachin D (1\u2009a): 1H NMR : \u03b4=8.02 , 7.43 , 7.30 , 5.09 , 5.04 , 4.98 , 3.40 , 2.51 , 2.10 , 2.03 , 1.92 , 1.87 , 1.81 , 1.60 , 1.55 , 1.49\u2005ppm ; 13C NMR : \u03b4=177.8 (C\u20104), 153.3 , 150.4 (C\u20102), 136.1 (C\u20103\u2032), 135.9 (C\u20107\u2032), 132.0 (C\u201011\u2032), 130.1 (C\u20108a), 127.1 (C\u20104a), 125.3 (C\u20106\u2032), 125.3 (C\u201010\u2032), 123.9 , 123.5 (C\u20102\u2032), 121.7 (C\u20103), 122.0 , 116.7 , 40.8 (C\u20108\u2032), 40.7 (C\u20104\u2032), 27.8 (C\u20109\u2032), 27.2 (C\u20105\u2032), 25.8 (C\u201012\u2032), 24.8 (C\u20101\u2032), 18.0 (C\u20109), 17.6 (C\u201015\u2032), 16.3 (C\u201013\u2032), 16.2\u2005ppm (C\u201014\u2032); 19F NMR : \u03b4=133.5\u2005ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 &bk:[M+H]+; found: 382.2546.7\u2010Fluoroaurachin D (1\u2009b): 1H NMR : \u03b4=8.25 , 7.16 , 7.11 , 5.09 , 5.05 , 4.99 , 3.38 , 2.45 , 2.10 , 2.02 , 1.94 , 1.87 , 1.80 , 1.61 , 1.55 , 1.51\u2005ppm ; 13C NMR : \u03b4=177.9 (C\u20104), 165.8 , 150.0 (C\u20102), 141.4 (C\u20108a), 135.9 (C\u20107\u2032), 135.7 (C\u20103\u2032), 132.0 (C\u201011\u2032), 129.5 (C\u20105),125.4 (C\u201010\u2032), 125.2 (C\u20106\u2032), 123.9 (C\u20102\u2032), 121.9 (C\u20104a), 120.8 (C\u20103), 113.3 (C\u20106), 103.4 (C\u20108), 40.8 (C\u20104\u2032), 40.8 (C\u20108\u2032), 27.8 (C\u20109\u2032), 27.2 (C\u20105\u2032), 25.7 (C\u201012\u2032), 24.4 (C\u20101\u2032), 18.3 (C\u20109), 17.7 (C\u201015\u2032), 16.1 (C\u201013\u2032), 16.0\u2005ppm (C\u201014\u2032); 19F NMR : \u03b4=109.3\u2005ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 [M+H]+; found: 382.2549.6\u2010Fluoroaurachin D (1\u2009c): 1H NMR : \u03b4=7.84 , 7.56 , 7.45 , 5.09 , 5.05 , 4.99 , 3.40 , 2.47 , 2.09 , 2.02 , 1.94 , 1.88 , 1.81 , 1.61 , 1.55 , 1.51\u2005ppm ; 13C NMR : \u03b4=177.7 (C\u20104), 160.5 , 150.0 (C\u20102), 137.2 (C\u20108a), 136.1 (C\u20103\u2032), 135.9 (C\u20107\u2032), 132.1 (C\u201011\u2032), 125.4 (C\u20106\u2032), 125.3 (C\u201010\u2032), 126.2 (C\u20104a), 123.6 (C\u20102\u2032), 121.6 (C\u20108), 121.3 (C\u20107), 120.8 (C\u20103), 110.1 (C\u20105), 40.8 (C\u20104\u2032), 40.7 (C\u20108\u2032), 27.8 (C\u20109\u2032), 27.3 (C\u20105\u2032), 25.8 (C\u201012\u2032), 24.8 (C\u20101\u2032), 18.3 (C\u20109), 17.6 (C\u201015\u2032), 16.3 (C\u201013\u2032), 16.1\u2005ppm (C\u201014\u2032); 19F NMR : \u03b4=119.2\u2005ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 [M+H]+; found: 382.2541.Antibacterial activity screening: An agar diffusion assay was performed with the purified compounds 1 and 1\u2009a\u2013c to test their antimicrobial activities against Escherichia coli SG458, Pseudomonas aeruginosa SG137, Staphylococcus aureus (MRSA) 134/94 and Mycobacterium vaccae IMET 10670. For this purpose, 50\u2005\u03bcL compound test solution (500\u2005\u03bcg\u2009mL\u22121 in DMSO) was pipetted into agar plates with pre\u2010punched 9\u2005mm holes. Ciprofloxacin (5\u2005\u03bcg\u2009L\u22121) was used as positive control.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Scientific Reports 10.1038/srep40064, published online 06 January 2017Correction to: This Article contains errors in Figure\u00a0A) A total of 40 mice were subcutaneously inoculated with H460 and H460/MX20 cells (\u22485\u2009\u00d7\u2009106) in the right flank, respectively. (B) The changes in tumor volume and body weight over time following the implantation. Data points represented the mean\u2009\u00b1\u2009SD of tumor volumes and body weight from each group. n\u2009=\u200920. (C) Solid tumor formation rate of H460 and H460/MX20 cells (100%). (D) The selected cell xenografts were cut into about 5\u00a0mm\u2009\u00d7\u20095\u00a0mm and fixed with 10% neutral formalin. (E) ABCG2 expression analysis by immunohistochemistry in tumor tissues collected from H460 and H460/MX20 cell xenografts.\u201d\u201c(should read:A) A total of 40 mice were subcutaneously inoculated with H460 and H460/MX20 cells (\u2248 5\u2009\u00d7\u2009106) in the right flank, respectively.  The changes in tumor volume and body weight over time following the implantation. Data points represented the mean\u2009\u00b1\u2009SD of tumor volumes and body weight from each group. n\u2009=\u200920. (D) Solid tumor formation rate of H460 and H460/MX20 cells (100%). (E) The selected cell xenografts were cut into about 5\u00a0mm\u2009\u00d7\u20095\u00a0mm and fixed with 10% neutral formalin. (F) ABCG2 expression analysis by immunohistochemistry in tumor tissues collected from H460 and H460/MX20 cell xenografts.\u201d\u201c(The correct Figure"}
{"text": "Slc17a9, P2x7r, and P2y2r was increased concomitant with an increase in extracellular ATP levels. Furthermore, compressive force decreased the osteoblast differentiation capacity of MC3T3\u2010E1 cells. shRNA knockdown of Slc17a9 in MC3T3\u2010E1 cells reduced levels of extracellular ATP and also led to increased osteoblast differentiation after the application of compressive force as assessed by qPCR analysis of osteoblast markers such as Runx2, Osterix, and alkaline phosphatase (ALP) as well as ALP activity. Consistent with these observations, knockdown of P2x7r or P2y2r by siRNA partially rescued the downregulation of osteoblast differentiation markers, caused by mechanical loading. In conclusion, our results demonstrate that VNUT is expressed in osteoblasts and that VNUT inhibits osteoblast differentiation in response to compressive force by mechanisms related to ATP release and P2X7R and/or P2Y2R activity.Osteoblasts release adenosine triphosphate (ATP) out of the cell following mechanical stress. Although it is well established that extracellular ATP affects bone metabolism via P2 receptors [such as purinergic receptor P2X7 (P2X7R) and purinergic receptor P2Y2 (P2Y2R)], the mechanism of ATP release from osteoblasts remains unknown. Recently, a vesicular nucleotide transporter  that preserves ATP in vesicles has been identified. The purpose of this study was to elucidate the role of VNUT in osteoblast bone metabolism. mRNA and protein expression of VNUT were confirmed in mouse bone and in osteoblasts by quantitative real\u2010time PCR (qPCR) and immunohistochemistry. Next, when compressive force was applied to MC3T3\u2010E1 cells by centrifugation, the expression of  In this study, we show that VNUT (SLC17A9), a vesicular nucleotide transporter, regulates osteoblast differentiation in response to mechanical loading. Mechanical loading promotes adenosine triphosphate (ATP) exocytosis via VNUT. Extracellular ATP subsequently inhibits osteoblast differentiation via activation of P2X7 and/or P2Y2 receptors. Thus, VNUT modulation of purinergic signaling contributes to the regulation of bone metabolism by mechanical loading. ALPalkaline phosphataseATPadenosine triphosphate P2X1Rpurinergic receptor P2X1P2X7Rpurinergic receptor P2X7P2Y2Rpurinergic receptor P2Y2qPCRquantitative real\u2010time PCRSLC17A9solute carrier family 17 member 9VNUTvesicular nucleotide transporterBone homeostasis is maintained by the balanced activity of bone\u2010forming osteoblasts and bone\u2010resorbing osteoclasts. Mechanical stress and loading are key factors for the regulation of bone homeostasis . OsteoblMechanical loading induces multiple cellular events in osteoblasts. A major effect of mechanical loading on osteoblasts is the efflux of adenosine triphosphate (ATP) into the extracellular space , 13, 14.Solute carrier family 17 member 9 (SLC17A9) was recently identified as a vesicular nucleotide transporter (VNUT), essential for ATP secretion from adrenal PC12 cells . ATP canHere, we report that VNUT is expressed in osteoblasts where it plays a role in ATP secretion as well as osteoblast differentiation.\u22121 penicillin\u2013streptomycin . Osteoblast differentiation was induced by culturing cells in an osteogenic medium containing 50\u00a0\u03bcg\u00b7mL\u22121 ascorbic acid  and 10\u00a0mm \u03b2\u2010glycerophosphate  for 7\u00a0days. Cells were treated with 1, or 10\u00a0\u03bcm clodronate (Sigma\u2010Aldrich). Ionomycin  treatments were performed at 1\u00a0\u03bcm. Brefeldin A  was used at 10\u00a0\u03bcm. HEK293T cells  were cultured in Dulbecco's modified Eagle's medium (DMEM)  supplemented with 10% FBS (Biosera Nuaill\u00e9) and 100\u00a0U\u00b7mL\u22121 penicillin\u2013streptomycin .MC3T3\u2010E1 cells, a mouse calvarial osteoblast cell line, were obtained from Riken Bio Resource Center . MC3T3\u2010E1 cells were maintained in \u03b1\u2010minimal essential medium  supplemented with 10% FBS  and 100\u00a0U\u00b7mL5 cells per well in 12\u2010well plates. Medium was changed into 4\u2010(2\u2010hydroxyethyl)\u20101\u2010piperazineethanesulfonic acid (HEPES)\u2010buffered DMEM without bicarbonate , supplemented with 18\u00a0\u00b5m of hydrochloric acid  to stabilize pH and then cells placed in an incubator  at 37\u00a0\u00b0C for 1\u00a0h. The plates were subsequently centrifuged at 4.4\u00a0\u00d7\u00a010\u22122\u00a0N\u00b7cm\u22122 (5.0\u00a0g\u00b7cm\u22122) or 8.8\u00a0\u00d7\u00a010\u22122\u00a0N\u00b7cm\u22122 (9.0\u00a0g\u00b7cm\u22122) using a PlateSpin II centrifuge  in the incubator at 37\u00a0\u00b0C for 12\u00a0h. Compressive force by weights was also previously described . Boxed areas in the  left panel are shown as magnified images in the right panel. Scale bars indicate 20 \u00b5m  and 100 \u00b5m  respectively.Click here for additional data file.Fig. S2. Immunocytochemistry with VNUT antibodies. (A) MC3T3\u2010E1 cells are immunostained with Rabbit VNUT antibody preabsorbed with VNUT blocking antigen peptide (Control) or VNUT antibody (Rabbit). (B) MC3T3\u2010E1 cells stably expressing control scrambled shRNA or shRNA against murine Slc17a9 were stained with VNUT antibody (Rabbit), rhodamine phalloidin, or DAPI. (C) MC3T3\u2010E1 cells were transfected with V5\u2010tagged VNUT and immunostained with VNUT antibody (Rabbit or Guinea pig), and anti\u2010V5 antibody and DAPI. Scale bars indicate 100 \u00b5m, scrambled shRNA, Scr; shRNA against murine Slc17a9, Sh.Click here for additional data file.Fig. S3. Knock down of VNUT does not alter extracellular ATP levels in the absence of mechanical force. Extracellular ATP levels from MC3T3\u2010E1 cells stably expressing control scrambled shRNA or shRNA against Slc17a9. Scrambled shRNA, Scr; shRNA against murine Slc17a9, sh. Data are expressed as the mean\u00a0\u00b1\u00a0SD (n\u00a0=\u00a03). Statistical analysis was performed with unpaired t\u2010test. *P\u00a0< 0.05 or **P\u00a0<\u00a00.01 versus control.Click here for additional data file.Fig. S4. Inhibition of Vnut function does not affect cell proliferation of MC3T3\u2010E1 cells. MC3T3\u2010E1 cells were plated into 96\u2010well plates and incubated with 0, 1.0, or 10 \u03bcM clodronate. Cell proliferation was assessed on day 1, 2, or 3 using a Cell Counting Kit\u20108 (DOJINDO).Click here for additional data file."}
{"text": "IVX5}\u2212  synthon to a pocket\u2010based ligand to provide supramolecular design using halogen\u22c5\u22c5\u22c5halogen interactions within an FeIII system that has the potential to undergo spin crossover (SCO). By removing the solvent from the crystal lattice, we \u201cswitch on\u201d halogen\u22c5\u22c5\u22c5halogen interactions between neighboring molecules, providing a supramolecular cooperative pathway for SCO. Furthermore, changes to the halogen\u2010based interaction allow us to modify the temperature and nature of the SCO event.We have added the {Re Inorganic synthon controls SCO behavior: Incorporating an {ReIVX5}\u2212 synthon into an FeIII system provides a highly directional supramolecular design using halogen\u22c5\u22c5\u22c5halogen interactions. Removal of solvent from the crystal lattice \u201cswitches on\u201d these interactions, providing a long\u2010range cooperative pathway ideal for an SCO event. In practice we found that the transition metal preferentially occupies pocket 2, giving a mer\u2010coordinated system with the general formula [ReIVX5(\u03bc\u2010Rpch)Fe(R\u2019\u2010Im)3] where H2Rpch has the formula (E)\u2010N\u2019\u2010(2\u2010hydroxy\u20103\u2010R\u2010benzylidene)pyrazine\u20102\u2010carbohydrazide, and R\u2019\u2010Im has the formula 1\u2010R\u2019\u2010imidazole \u2010(8) (see ESI), showed that the SCO properties of the FeIII center could be readily modified. Crystal structures are labelled with the general name \u201c(Compound)w/d_TEMP\u201d, where w or d denotes \u201cwet\u201d (solvated) or \u201cdry\u201d (desolvated) crystals, and TEMP is the temperature of the structural determination.Whilst the use of the {ReX1)w_100 shows that the complex crystallizes in the space group C2/c with Z=8. Complex (1) was chosen as a representative of the series with structural details of complexes (1)\u2013(4) including halogen bond parameters in the ESI. The asymmetric unit contains a [ReBr5(\u03bc\u2010MeOpch)Fe(Me\u2010Im)3] complex with the {ReIVBr5} synthon bound to a nitrogen atom of the pyrazine ring of the deprotonated MeOpch ligand. The central FeIII ion is coordinated to the ligand through an azine nitrogen (N1), a carbonyl oxygen (O3), and a hydroxy oxygen (O1), whilst three additional Me\u2010Im co\u2010ligands complete the coordination sphere through nitrogen atoms N5, N9, and N7. In addition to this there were two interstitial MeCN molecules within the lattice connected through nonclassical hydrogen bonds. The shortest intermolecular Br\u22c5\u22c5\u22c5Br distance was 4.663\u2005\u00c5 and is therefore too long to be considered a halogen bond, and is unlikely to contribute to information exchange.4O2 coordination sphere of the FeIII ion is often observed in SCO active compounds,1)w_280. FeIII\u2212N bond lengths are characteristic of the spin state (LS\u22481.95\u2005\u00c5 and HS\u22482.15\u2005\u00c5)1) using a SQUID magnetometer revealed an SCO active system with an incomplete transition occurring between 220\u2005K and 90\u2005K, from fully HS to only 22\u2009% of molecules in the HS electronic configuration with T1/2=155\u2005K d_100 crystallized in the same space group, C2/c, with the same neutral metal complex in the asymmetric unit. However, the average Fe\u2212N bond length (1.982\u2005\u00c5) indicated the complex was now at least partially in the LS state; it was also observed that the sample had desolvated (between measurements) with loss of the interstitial MeCN molecules  whilst retaining crystallinity. Crystallographic data were also collected at 140, 180, 230 and 280\u2005K and by plotting the adjusted change in unit cell volume (see ESI for details) against the temperature the SCO event clearly correlates with the changes in the crystal structure , however the loss of the solvent leads to reorientation of molecules in the crystal resulting in a significant shortening of the Br\u22c5\u22c5\u22c5Br distances, \u201cswitching on\u201d a type I halogen bond .A more detailed investigation revealed that, by removing the lattice solvent and therefore the hydrogen bonding, halogen\u22c5\u22c5\u22c5halogen interactions become the dominant supramolecular effect Figure\u2005. In the 2)\u2013(4) were then synthesized to characterize the importance of these halogen\u22c5\u22c5\u22c5halogen interactions. The modifications are summarized in Table\u20052). Complex (2)w_100 also crystallized in the space group C2/c with the neutral metal complex now [ReCl5(\u03bc\u2010MeOpch)Fe(Me\u2010Im)3] together with two MeCN molecules in the asymmetric unit. Analysis of the Fe\u2212N bond lengths (average: 2.111\u2005\u00c5) shows the iron(III) center to be in the HS state at 100\u2005K. In this solvated sample there is again no appreciable halogen\u22c5\u22c5\u22c5halogen interaction, with the shortest Cl\u22c5\u22c5\u22c5Cl distance at 4.539\u2005\u00c5. Despite the apparent HS structure, magnetic investigation revealed that at 100\u2005K the FeIII is mostly LS (74\u2009% LS)  with the halogen bond \u201cswitching on\u201d upon loss of solvent. Since this sample lost crystal quality during desolvation, the exact nature of the halogen\u22c5\u22c5\u22c5halogen interaction could not be clearly defined. Previous work has ordered the strength of halogen bonds as F < Cl <Br < I.1). Both events start at 230\u2005K from a \u03c7T value of \u22485.8\u2005cm3\u2009mol\u22121\u2005K, however the T1/2 value is 33\u2005K lower (T1/2=124\u2005K) for (2) consistent with the gradual nature of the crossover which occurs over a wider temperature range (130\u2005K and 170\u2005K for (1) and (2), respectively).Complexes (2)\u2013 were the3) was produced by changing the non\u2010coordinated MeO group on the primary\u2010ligand for the sterically larger EtO group. (3)w_180 crystallized with a similar unit cell and packing, but in P21/n due to loss of C\u2010centering. The asymmetric unit thus contains two [ReBr5(\u03bc\u2010EtOpch)Fe(Me\u2010Im)3] complexes and a single molecule of MeCN. Both crystallographically independent complexes appear to be HS at 180\u2005K with the average Fe\u2010N lengths of 2.116\u2005\u00c5 and 2.101\u2005\u00c5 for Fe1 and Fe2, respectively. In the complex containing Fe2 there is evidence of a weak type II halogen bond , which is missing for the molecule containing Fe1, thus only half the molecules in the crystal lattice can utilize a halogen bond mediated process. Upon complete solvent loss, sample (3)d_180 undergoes a transformation to a structure with only one [ReBr5(\u03bc\u2010EtOpch)Fe(Me\u2010Im)3] molecule in the asymmetric unit. In this case the halogen\u22c5\u22c5\u22c5halogen interaction is stronger than previously observed  involving all molecules in the crystal. SCO events are highly sensitive and this slight change in peripheral substituent from MeO to EtO is enough to modify the SCO properties.1/2=98\u2005K  which replaces the methyl group on the imidazole\u2010based secondary ligand, R\u2019, with a larger ethyl group crystallizes without interstitial solvent, (4)d_180. In the case of (3) only one additional CH2 unit was added to the molecule in a position placing it at a maximum distance from the {ReX5}\u2212 synthon. However, in complex (4) a total of three additional CH2 units were introduced pushing the molecules further apart. In addition, a methyl group on one imidazole points directly into the {ReX5}\u2212 synthon . This results in a desolvated complex lacking halogen\u22c5\u22c5\u22c5halogen interactions and therefore without the desired SCO behavior  rule out the possibility that removing solvent alone is enough to induce SCO properties and provide further evidence that in these systems a halogen\u22c5\u22c5\u22c5halogen interaction is required. This highlights the key role of halogen bond mediated information exchange and demonstrates the potential for halogen bonding within SCO research.The results for the desolvated complex  to (11) and compounds (1) to (4), with the CoIII analogues, compounds (5) to (8), presented in the ESI along with the full details of the analytical equipment.The experimental section below covers the ligands (4)2ReBr6  and H2MeOpch  were dissolved in a mixture of 2\u2010propanol/acetone  and heated to 75\u2009\u00b0C for 2 hours. After cooling to room temperature, the solvent volume was reduced to \u224880\u2005mL and the orange precipitate collected via filtration and dried in vacuo. Yield: 1.34\u2005g (87\u2009%). C29H48Br5N5O3Re (1098.44\u2005g\u2009mol\u22121): Calculated C: 31.7\u2009%, H: 4.4\u2009%, N: 6.4\u2009%, Found: C: 31.0\u2009%, H: 4.3\u2009%, N: 6.1\u2009%. IR (\u03bd\u02dccm\u22121): 2960 (m), 2932 (w), 2872 (w), 1683 (s), 1608 (w), 1528 (m), 1462 (s), 1406 (m), 1377 (m), 1353 (m), 1244 (vs), 1148 (s), 1077 (s), 968 (m), 952 (m), 905 (m), 881 (m), 781 (m), 629 (w), 482 (m). UV/Vis: (MeCN) (\u03bb nm)=201, 220, 305, 339, 357 (sh), 590.(NBu4)2ReCl6  and H2MeOpch  were dissolved in a mixture of 2\u2010propanol/acetone  and heated to 75\u2009\u00b0C for 6 hours. After cooling to room temperature, the solution was filtered and left to stand under an inert atmosphere. After six days orange needles were collected via filtration and dried in vacuo. Yield: 0.067\u2005g (67\u2009%). C29H48Cl5N5O3Re (997.35\u2005g\u2009mol\u22121): Calculated C: 42.2\u2009%, H: 6.4\u2009%, N: 7.0\u2009%, Found: C: 40.9\u2009%, H: 6.4\u2009%, N: 7.0\u2009%. IR (\u03bd\u02dccm\u22121): 3490 (vw), 2960 (s), 2932 (m), 2873 (m), 1682 (vs), 1608 (m), 1576 (w), 1533 (s), 1464 (vs), 1407 (m), 1377 (m), 1354 (s), 1282 (s), 1246 (vs), 1147 (vs), 1076 (s), 1024 (m), 952 (s), 906 (m), 881 (m), 835 (w), 817 (w), 783 (m), 739 (vs), 486 (m), 344 (s). UV/Vis: (MeCN) (\u03bb nm)=200, 221, 292, 353 (sh).(NBu4)2ReBr6  and H2EtOpch  were dissolved in a mixture of 2\u2010propanol/acetone  and heated to 70\u2009\u00b0C for 3 hours. After cooling to room temperature, the solvent volume was reduced to \u224810\u2005mL and the orange precipitate collected via filtration and dried in vacuo. Yield: 0.064\u2005g (82\u2009%). C30H49Br5N5O3Re (1113.48\u2005g\u2009mol\u22121): Calculated C: 32.4\u2009%, H: 4.4\u2009%, N: 6.3\u2009%, Found: C: 32.6\u2009%, H: 4.5\u2009%, N: 6.3\u2009%. IR (\u03bd\u02dccm\u22121): 3298 (vw), 2953 (w), 2928 (w), 2868 (w), 1708 (s), 1607 (m), 1513 (s), 1461 (s), 1403 (s), 1377 (m), 1354 (m), 1255 (vs), 1153 (vs), 1111 (m), 1057 (s), 1023 (s), 948 (m), 922 (w), 882 (s), 778 (m), 732 (vs), 581 (s), 486 (s), 443 (w). UV/Vis: (MeCN) (\u03bb nm)=221, 265, 305, 339, 357 (sh).(NBu4)2\u22c56\u2009H20  in MeCN (5\u2005mL) was slowly added to a solution of (NBu4)[ReBr5(H2MeOpch)] (9)  and 1\u2010Me\u2010Im  in MeCN (5\u2005mL). The reddish\u2010brown clear solution was sealed and left to stand for three weeks until dark brown needle crystals were formed. Yield: 5\u2005mg (48\u2009%). C25H28Br5FeN10O3Re (1158.2\u2005g\u2009mol\u22121): Calculated C: 25.9\u2009%, H: 2.4\u2009%, N: 12.1\u2009%, Found: C: 26.5\u2009%, H: 2.7\u2009%, N: 12.7\u2009%. IR (\u03bd\u02dccm\u22121): 3123 (w), 1589 (m), 1536 (m), 1515 (m), 1466 (w), 1431 (s), 1349 (s), 1287 (m), 1252 (s), 1231 (m),1213 (m), 1156 (m), 1087 (vs), 1020 (w), 969 (w), 948 (m), 923 (w), 825 (w), 785 (w), 750 (vs), 655 (s), 618 (m), 584 (s), 509 (w), 416 (s), 370 (m). UV/Vis: (MeCN) (\u03bb nm)=216, 281, 337, 350, 360.A solution of Fe(ClO4)2\u22c56\u2009H20  in MeCN (5\u2005mL) was slowly added to a solution of (NBu4)[ReCl5(H2MeOpch)] (10)  and 1\u2010Me\u2010Im  in MeCN (5\u2005mL). The reddish\u2010brown clear solution was sealed and left to stand for eight days until dark brown needle crystals were formed. Yield: 6\u2005mg (54\u2009%). C25H28Cl5FeN10O3Re (1158.2\u2005g\u2009mol\u22121): Calculated C: 32.1\u2009%, H: 3.0\u2009%, N: 15.0\u2009%, Found: C: 31.2\u2009%, H: 3.0\u2009%, N: 14.7\u2009%. IR (\u03bd\u02dccm\u22121): 2959 (vw), 2932 (vw), 2834 (vw), 1599 (s), 1548(s), 1509 (m), 1436 (s), 1354 (s), 1298 (m), 1242 (s), 1219 (vs), 1157 (s), 1081 (m), 1020 (w), 971 (w), 921 (w), 856 (m), 741 (vs), 629 (w), 552 (m), 492 (w), 442 (m), 404 (m), 360 (w). UV/Vis: (MeCN) (\u03bb nm)=205, 282, 326 (sh), 338, 381, 477.A solution of Fe(ClO4)2\u22c56\u2009H20  in MeCN (10\u2005mL) was slowly added to a solution of (NBu4)[ReBr5(H2EtOpch)] (11)  and 1\u2010Me\u2010Im  in MeCN (10\u2005mL). The reddish\u2010brown clear solution was sealed and left to stand for four days until dark brown block crystals were formed. Yield: 5\u2005mg (48\u2009%). C26H31Br5FeN10O3Re (1172.67\u2005g\u2009mol\u22121): Calculated C: 26.6\u2009%, H: 2.6\u2009%, N: 11.9\u2009%, Found: C: 26.1\u2009%, H: 2.4\u2009%, N: 12.1\u2009%. IR (\u03bd\u02dccm\u22121): 3117 (w), 1606 (w), 1588 (m), 1532 (w), 1433 (m), 1391 (m), 1350 (m), 1280 (w), 1254 (s), 1211 (m), 1157 (m), 1086 (vs), 1023 (m), 946 (m), 901 (w), 844 (m), 783 (w), 741 (vs), 655 (s), 616 (m), 569 (m), 510 (m), 463 (w), 432 (m), 365 (w). UV/Vis: (MeCN) (\u03bb nm)=195, 208, 221, 307, 335, 355, 388 (sh).A solution of Fe(ClO4)2\u22c56\u2009H20  in MeCN (10\u2005mL) was slowly added to a solution of (NBu4)[ReBr5(H2MeOpch)] (9)  and 1\u2010Et\u2010Im  in MeCN (15\u2005mL). The reddish\u2010brown clear solution was sealed and left to stand for one day until dark brown block crystals were formed. Yield: 31\u2005mg (43\u2009%). C28H34Br5CoN10O3Re (1153.26\u2005g\u2009mol\u22121): Calculated C: 26.9\u2009%, H: 2.6\u2009%, N: 11.3\u2009%, Found: C: 26.6\u2009%, H: 2.7\u2009%, N: 11.3\u2009%. IR (\u03bd\u02dccm\u22121): 3118 (w), 2976 (vw), 934 (vw), 1589 (m), 1550 (m), 1531 (m), 1462 (m), 1426 (m), 1350 (s), 1278 (m), 1245 (m), 1230 (m), 1215 (m), 1182 (w), 1158 (m), 1087 (vs), 1020 (m), 958 (m), 945 (m), 838 (m), 798 (w), 744 (vs), 660 (s), 590 (m), 567 (m), 512 (m), 431 (m), 359 (s). UV/Vis: (MeCN) (\u03bb nm)=191, 209, 274 (sh), 338, 363, 392.A solution of Fe should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Correction to: JA Clin Rep 6, 62 (2020)https://doi.org/10.1186/s40981-020-00368-xFollowing the publication of the original article , the autWe thought that the coefficient 0.0031 was the Bunsen coefficient of oxygen to water measured at 37\u2009\u00b0C, but it turned out that the Bunsen coefficient was the coefficient obtained by converting the value measured at the relevant temperature to 0\u2009\u00b0C under 1\u2009atm conditions.As a result, we determined that the formula calculated below is appropriate when temperature correction is performed at 37\u2009\u00b0C.From:In lieu of Eq. (1), we propose a new temperature correction formula: CaO2 (ml/dl) = 1.58 \u00d7 Hb (g/dl) \u00d7 SaO2 + 0.0031 \u00d7 PaO2 (mmHg) at 37 \u00b0C and 1 atm.To:2 (ml/dl) = 1.58 \u00d7 Hb (g/dl) \u00d7 SaO2 + 0.0035 \u00d7 PaO2 (mmHg) at 37 \u00b0C and 1 atm.In lieu of Eq. (1), we propose a new temperature correction formula: CaOThe authors apologise for this error."}
{"text": "N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline), the ligand coordinates in a mono-tridentate fashion, and both metal atoms have fivefold coordination spheres with distorted shapes.In the cadmium(II) and zinc(II) complexes of the tetra\u00adkis-substituted pyrazine ligand,  N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline)-\u03ba3N2,N1,N6}cadmium(II), [CdI2(C36H40N6)], (I), of the ligand N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline) (L), is generated by a twofold rotation symmetry; the twofold axis bis\u00adects the cadmium atom and the nitro\u00adgen atoms of the pyrazine ring. The ligand coordinates in a mono-tridentate manner and the cadmium atom has a fivefold CdN3I2 coordination environment with a distorted shape. In the zinc(II) complex, dichlorido{N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline)-\u03ba3N2,N1,N6}zinc(II) di\u00adchloro\u00admethane 0.6-solvate, [ZnCl2(C36H40N6)]\u00b70.6CH2Cl2, (II), ligand L also coordinates in a mono-tridentate manner and the zinc atom has a fivefold ZnN3Cl2 coordination environment with a distorted shape. It crystallized as a partial di\u00adchloro\u00admethane solvate. In the crystal of I, the complex mol\u00adecules are linked by weak C\u2014H\u22efI contacts, forming ribbons propagating along [100]. In the crystal of II, the complex mol\u00adecules are linked by a series of C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers lying parallel to the (1The whole mol\u00adecule of the cadmium(II) complex, di\u00adiodido\u00ad{ N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline) (L), whose synthesis and crystal structure have been described in the preceding publication I2 (I), of the ligand N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-methyl\u00adaniline) (L), is illustrated in Fig.\u00a013I2 coordination environment with a distorted shape . The \u03c45 parameter for the fivefold coordination of atom Cd1 is 0.14  complex, Cdpyrazine (TPPZ), viz. complex pyrazine)\u00adbis\u00ad(iodo)\u00adcadmium(II) \u2005\u00c5 in I, while the Cd\u2014I bond lengths are ca 2.741 and 2.727\u2005\u00c5 compared to 2.7038\u2005(3)\u2005\u00c5 in I. The N-methyl\u00adaniline groups on the non-coordinated side of the ligand are linked by intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions Cl2\u00b70.6(CH2Cl2) (II), is illustrated in Fig.\u00a03L coordinates in a mono-tridentate manner and the zinc atom, Zn1, has a fivefold ZnN3Cl2 coordination environment with a distorted shape . The \u03c45 parameter for atom Zn1 is 0.30.The mol\u00adecular structure of the zinc(II) complex, Znpyrazine-N,N\u2032,N\u2032\u2032]zinc(II): a monoclinic polymorph pyrazine]\u00adtetra\u00adchloro\u00addizinc(II): one hydrated \u00adbis\u00ad\u00addodeca\u00adchloro\u00adtetra\u00adaqua\u00addeca\u00adzinc \u2005\u00c5 in II, while the Zn\u2014Cl bond lengths vary from ca 2.232 to 2.343\u2005\u00c5 compared to 2.2251\u2005(10) and 2.2425\u2005(11)\u2005\u00c5 in II.A search of the CSD for a ZnNL differs in the two complexes  with respect to ring E (ring Ci in I).The conformation of the ligand es Fig.\u00a04. The oriI is shown in Fig.\u00a05a-axis direction  contact of 3.045\u2005(5)\u2005\u00c5 and do not participate in any significant inter\u00admolecular inter\u00adactions with the complex mol\u00adecule. There are Zn\u2014Cl\u22ef\u03c0(pyrazine) contacts present, which link inversion-related mol\u00adecules, forming dimers  distance of ca 3.987\u2005\u00c5 and a Zn\u2014Cl\u22efcentroid angle of ca. 170.96\u00b0. In complex II, the corresponding Cl\u22efcentroid(pyrazine ring) distance and Zn\u2014Cl\u22efcentroid angle are 3.683\u2005(2)\u2005\u00c5 and 155.96\u2005(6)\u00b0, respectively  through white to blue . A summary of the short inter\u00admolecular contacts in the crystal structures of I and II is given in Table\u00a06The Hirshfeld surface analysis  mapped over dnorm, and the two-dimensional fingerprint plots are given in Fig.\u00a08a) correspond to the I\u22efH contacts, which give a pair of spikes in the fingerprint plot  at de + di \u2243 3.0\u2005\u00c5, contributing 14.2% to the HS. The H\u22efH contacts contribute 63.4% and the C\u22efH contacts 18.0%. Any other atom\u2013atom contacts contributed less than 2% and have not been included here.For complex ot Fig.\u00a08b at deII, the Hirshfeld surface mapped over dnorm, is shown in Fig.\u00a09a, and that for the complex itself and the solvent mol\u00adecule in Figs.\u00a09b and 9c, respectively. The faint red spots correspond to the Cl\u22efH contacts in the crystal. These give a pair of spikes in the fingerprint plots, at de + di \u2243 2.7\u2005\u00c5, contributing 22.7%, in the compound  and at de + di \u2243 2.7\u2005\u00c5, contributing 18.1%, in the complex . For the solvent mol\u00adecule, a single sharp spike is observed (de + di \u2243 2.8\u2005\u00c5) with a contribution of 59.6% to the HS . The H\u22efH contacts contribute 55.1, 59.4 and 25.2% to the Hirshfeld surfaces of the compound, the complex and the solvent mol\u00adecule, respectively, while the C\u22efH contributions are 17.7, 18.8 and 6.8%, respectively. Any other atom\u2013atom contacts contributed less than 2% and have not been included here.For compound d Fig.\u00a010a and atx Fig.\u00a010b. For tS Fig.\u00a010c. The HN,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032-tetra\u00adkis\u00ad(N-meth\u00adylaniline) L, have been described in the preceding publication Synthesis of the complex \u00b70.6(CH2Cl2) (II)Synthesis of the complex \u00b70.6CH2Cl2 (743.99\u2005g\u2005mol\u22121): calculated C 60.50, H 5.68, N 11.65%; found C 60.66, H 5.78, N 11.93%.To a solution of ZnClUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a07II the _diffrn_reflns_Laue_measured_fraction_full of 0.939 is below the required minimum of 0.95. For II, a small number of low-angle reflections, either in the shadow of the beam-stop or with bad agreement, were omitted during the final cycles of refinement.With the STOE IPDS I, a one-circle diffractometer, for the triclinic system often only 93% of the Ewald sphere is accessible. Hence, for compound 10.1107/S2056989020001644/xi2022sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989020001644/xi2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020001644/xi2022IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1982100, 1982099CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Aspalathus linearis) has various health benefits. Two case studies have associated chronic Rooibos consumption with conventional prescription medications, including atorvastatin (ATV), with hepatotoxicity. Statins act by inhibiting hydroxymethylglutaryl\u2010coenzyme A reductase, a rate\u2010limiting enzyme in cholesterol synthesis. Although rare, statins are potentially hepatotoxic. The aim was to investigate interactions between aspalathin\u2010rich Rooibos extract GRT\u2122 and ATV\u2010induced hepatotoxicity in C3A liver cells cultured with and without palmitate. Effects of co\u2010treatment of GRT\u2009+\u2009ATV on cell viability, oxidative stress, apoptosis, mitochondrial integrity, and cellular reactive oxygen species (ROS) production were assessed. Significantly increased ROS production was observed in cells exposed to ATV and palmitate. Combination therapy of GRT\u2009+\u2009ATV also showed significant increases in ROS production. Under palmitate\u2010treated conditions, ATV\u2010induced significant apoptosis which was not ameliorated by GRT\u2009+\u2009ATV co\u2010treatment. Despite studies purporting hepatoprotection from Rooibos, our study showed that GRT was unable to modulate ATV\u2010induced hepatotoxic effects in this model.Rooibos ( Effects of rooibos extract (GRT) and atorvastatin (ATV) treatments on reactive oxygen species (ROS) production in C3A cells without palmitate and cells treated with 500\u2009\u00b5M palmitate for 24\u2009hrs. The addition of GRT failed to ameliorate ROS production induced by ATV treatment. Scientific evidence confers multiple health benefits to Rooibos, such as anti\u2010inflammatory ;\u00a0Ajuwon et al.,\u00a0ATV\u00a0is considered a \u201cblockbuster drug\u201d as the best\u2010selling prescription drug in history, with lifetime sales of USD 148,744 million between 1996 and 2016 .22.1l\u2010glutamine , the combination thereof hereafter referred to as growth medium. Cells were seeded at a density of 11\u2009\u00d7\u2009104 cells per ml\u00a0and incubated in humidified air at 37\u00b0C with 5% CO2. Replacement of culture media was done every 2\u20133 days. Cells were sub\u2010cultured to 70\u201380% confluence  was purchased from the American Type Culture Collection (ATCC). Eagle's modified essential medium , 10% vol/vol fetal bovine serum  and 1% vol/vol\u00a0nfluence . Palmitanfluence ,\u00a02015.An aspalathin\u2010rich unfermented Rooibos extract (Afriplex GRT\u2122) was obtained from Afriplex (Pty) Ltd , ATV was obtained from Sigma\u2010Aldrich , and palmitate was obtained from Sigma\u2010Aldrich . These, and all other chemicals for experimental use were of cell culture grade. Stock solutions were prepared in dimethyl sulfoxide (DMSO) and final working concentrations of treatments contained not more than 0.25% vol/vol DMSO.3\u2010\u20102,5\u2010diphenyl tetrazolium bromide , 2\u2032,7\u2032\u2010dichlorofluorescein , 5,5\u2032,6,6\u2032\u2010tetrachloro\u20101,1\u2032,3,3\u2032\u2010tetraethylbenzimidazolylcarbocyanine iodide , and propidium iodide  were obtained from Sigma, Stanheim, Germany.Annexin V  and caspase 3/7  were obtained from Thermo Fisher Scientific, Johannesburg, South Africa.2.2C3A liver cells, with palmitate or without palmitate, were exposed to ATV (10 and 25\u2009\u00b5M) and Afriplex GRT\u2122 (0.01 and 0.1\u2009mg/ml) and a combination thereof  for 24\u2009hr. Pretreatment with palmitate (500\u2009\u00b5M) for 24\u2009hr was used to simulate hyperlipidaemia in vitro  version 1.05. Three replicates per treatment were assessed in three independent experiments.Cellular metabolic activity was assessed using an MTT cell viability assay Mosmann,\u00a0. C3A cel2.44 cells per ml in 200\u2009\u00b5l growth medium per well in a black 96\u2010well clear bottom plate and cultured and treated as per Figure\u00a02 in humified air). Fluorescent readings were recorded using a SpectraMax i3x multi\u2010mode microplate reader at an excitation wavelength of 485\u2009nm and an emission wavelength of 535\u2009nm. Results were generated on SoftMax Pro Data Acquisition and Analysis Software (RRID:SCR_014240), version 7.0.2. Three replicates per treatment were assessed in three independent experiments. Reactive oxygen species production was calculated relative to cell viability which was assessed by an MTT assay.Oxidative stress was assessed by DCF staining  and data were compared using one\u2010way analysis of variance, followed by a Tukey post hoc test. Data are presented as mean\u2009\u00b1\u2009standard deviation\u00a0and 33.1p\u2009<\u2009.001). Combination treatment of ATV (10 and 25\u2009\u00b5M) with GRT (0.01 and 0.1\u2009mg/ml) did not ameliorate ATV\u2010induced cytotoxicity. A significant difference was noted between the monotherapy treatment groups and the combination treatment groups: GRT1 (94.05\u2009\u00b1\u200923.21%) showed significantly increased (p\u2009<\u2009.01) MTT activity compared with ATV1\u2009+\u2009GRT1 (61.85\u2009\u00b1\u200913.18%), whilst GRT2 (97.48\u2009\u00b1\u200924.32%) showed significantly greater activity compared with ATV1\u2009+\u2009GRT2  and ATV2\u2009+\u2009GRT2 .Figure\u00a0p\u2009<\u2009.001; 25\u2009\u00b5M ATV\u2009=\u200916.58\u2009\u00b1\u200913.99%; p\u2009<\u2009.001). The adverse effect of ATV was not improved by the combination treatment with GRT at either concentration. GRT1 (91.92\u2009\u00b1\u200933.19%) increased (p\u2009<\u2009.001) MTT activity compared with ATV1\u2009+\u2009GRT1 (39.92\u2009\u00b1\u200917.87%), and GRT2 (96.56\u2009\u00b1\u200930.92%) showed higher activity compared with ATV1\u2009+\u2009GRT2  and ATV2\u2009+\u2009GRT2 .In palmitate\u2010treated C3A cells  intracellular ROS compared with the vehicle control (100.00\u2009\u00b1\u200927.52%). Co\u2010treatment of GRT\u2009+\u2009ATV had a significant (p\u2009<\u2009.001) additive effect to the ATV\u2010induced intracellular ROS production compared with GRT2 (89.96\u2009\u00b1\u200940.96%) and ATV2 monotherapy (ATV2\u2009+\u2009GRT2\u2009=\u2009845.00\u2009\u00b1\u2009589.60%).In cells not exposed to palmitate as shown in Figure\u00a0p\u2009<\u2009.05) and 25\u2009\u00b5M ATV  significantly increasing intracellular ROS compared with the palmitate control (100.00\u2009\u00b1\u200919.07%). In combination, GRT at the concentrations used did not moderate ATV\u2010induced ROS production. A significant difference was seen between GRT monotherapy (137.80\u2009\u00b1\u200974.29% for GRT1 and 131.40\u2009\u00b1\u200987.18% for GRT2) compared with their respective combination treatment groups: ATV1\u2009+\u2009GRT1\u2009=\u2009306.80\u2009\u00b1\u2009192.20% (p\u2009<\u2009.05); ATV1\u2009+\u2009GRT2\u2009=\u2009296.10\u2009\u00b1\u2009102.00% (p\u2009<\u2009.05); ATV2\u2009+\u2009GRT2\u2009=\u20091493.00\u2009\u00b1\u2009278.40% (p\u2009<\u2009.001). However, there was a significant difference (p\u2009<\u2009.001) between the ATV2 and ATV2\u2009+\u2009GRT2 treatment groups.With palmitate treatment Figure\u00a0, ATV\u2010ind3.3p\u2009<\u2009.05), ATV1 , and ATV2  treatment significantly reduced relative mean fluorescence intensity compared with the vehicle control (100.00\u2009\u00b1\u20098.76%). Figure\u00a0p\u2009<\u2009.05).In cells not exposed to palmitate, Figure\u00a03.4p\u2009<\u2009.01) and ATV2  significantly decreased the number of viable cells compared with the vehicle control (86.33\u2009\u00b1\u20094.63%). The addition of GRT at either concentration was unable to protect these cells against ATV toxicity. GRT1 monotherapy significantly increased the percentage of viable cells compared with ATV1\u2009+\u2009GRT1 combination therapy . Similarly, GRT2 monotherapy significantly increased (p\u2009<\u2009.001) the percentage of viable cells compared with ATV2\u2009+\u2009GRT2 combination therapy .In the absence of palmitate Figure\u00a0, the addp\u2009<\u2009.01) in the percentage of early apoptotic cells when GRT2 (9.17\u2009\u00b1\u20093.25%) and ATV2\u2009+\u2009GRT2 (0.33\u2009\u00b1\u20090.52%) were compared  and ATV2 group  showed significantly less prevalence of early apoptosis as compared with the vehicle control group (5.83\u2009\u00b1\u20092.04%). The combination of GRT1 and GRT2 did not significantly improve ATV1 or ATV2\u2010induced apoptosis.There was a significant difference  more late apoptotic cells compared the vehicle control (7.83\u2009\u00b1\u20092.79%), as did the ATV2 group , which showed the greatest percentage of late apoptotic of all the treatment groups in the normal condition. Compared with ATV1\u2009+\u2009GRT1 (35.17\u2009\u00b1\u200919.28%), GRT1 (8.00\u2009\u00b1\u20099.90%) showed a significant (p\u2009<\u2009.01) decrease in the prevalence of late apoptotic cells. The GRT2 group (12.50\u2009\u00b1\u20096.06%) showed a significant (p\u2009<\u2009.001) decrease compared with\u00a0ATV2\u2009+\u2009GRT2 (64.83\u2009\u00b1\u20098.98%).Cells in late apoptosis, not treated with palmitate Figure\u00a0, showed p\u2009<\u2009.01) decreased percentage of cells relative to the palmitate control group (13.00\u2009\u00b1\u20095.73%). Further, ATV2\u2009+\u2009GRT2 (3.17\u2009\u00b1\u20090.98%) showed significantly decreased (p\u2009<\u2009.001) percentage of early apoptotic cells compared with\u00a0the GRT2 monotherapy group (11.67\u2009\u00b1\u20092.58%). Figure\u00a0In terms of the percentage of viable cells in the simulated hyperlipidaemic condition, there was no statistical differences between any of the different treatment groups Figure\u00a0. Althoug3.5p\u2009<\u2009.001) caspase 3/7 activity compared with the vehicle control (100.00\u2009\u00b1\u20093.67%), as did the ATV2 group . The difference between GRT1 (100.90\u2009\u00b1\u20094.44%) and ATV1\u2009+\u2009GRT1 (168.70\u2009\u00b1\u200945.81%) was significant (p\u2009<\u2009.001), as was the difference between GRT2 (101.80\u2009\u00b1\u200941.78%) and ATV1\u2009+\u2009GRT2  and GRT2 and ATV2\u2009+\u2009GRT2 (283.20\u2009\u00b1\u2009135.00%). There was also a significant (p\u2009<\u2009.001) difference between ATV2 and ATV2\u2009+\u2009GRT2.Figure\u00a0p\u2009<\u2009.001) caspase 3/7 activity compared with\u00a0the palmitate control group (100.00\u2009\u00b1\u200914.83%) in the hyperlipidaemic condition. The addition of GRT2 had a seemingly additive effect on the ATV monotherapy groups  as compared with their combination therapy counterparts: ATV1\u2009+\u2009GRT1\u2009=\u2009155.50\u2009\u00b1\u200938.90% (p\u2009<\u2009.001); ATV1\u2009+\u2009GRT2\u2009=\u2009126.20\u2009\u00b1\u200929.90% (p\u2009<\u2009.001); and ATV2\u2009+\u2009GRT2\u2009=\u2009114.70\u2009\u00b1\u200921.82% (p\u2009<\u2009.01). Similarly, GRT2 monotherapy showed significantly increased (p\u2009<\u2009.001) caspase 3/7 activity compared with the ATV1\u2009+\u2009GRT2 and ATV2\u2009+\u2009GRT2 combination therapy groups.Figure\u00a04Aspalathus linearis) is commonly prepared as a herbal infusion and has a number of health properties including antioxidant, hepatoprotective, and metabolic effects  and caspase activation.In cells not pretreated with palmitate, both 10\u00a0and 25\u2009\u00b5M ATV caused a significant decrease in relative MTT activity, while GRT alone showed no difference at the concentrations used after 24\u2009hr. In combination, GRT did not modulate the toxicity induced by ATV in terms of MTT activity. The same trend was noted in the palmitate\u2010treated cells. Taken together, this suggests that GRT did not have a modulating effect on ATV\u2010induced toxicity in terms of MTT activity.In the normal condition, as expected GRT did not induce ROS production. The higher concentration of ATV (25\u2009\u00b5M) increased ROS production, and co\u2010treatment with 0.1\u2009mg/ml GRT further exacerbated this effect. In the hyperlipidaemic condition, a similar trend was seen: GRT alone did not induce ROS production, however 25\u2009\u00b5M ATV treatment, both alone and in combination with GRT, increased ROS. Shu et al.  attribut4\u2212 . This is an important redox component of the mitochondrial electron transport chain, responsible for synthesizing ATP. Reducing the biosynthesis of CoQ9/10 in the liver affects mitochondrial oxygen consumption and increases cellular ROS production, thought to be a major causal factor for statin\u2010induced adverse effects (Rundek, Naini, Sacco, Coates, & DiMauro,\u00a0In contrast, other studies have demonstrated hepatoprotective effects for Rooibos against CClAlong with increased ROS, high\u2010dose ATV decreased mitochondrial membrane potential in both the normal and palmitate\u2010treated C3A cells. GRT could not attenuate the toxicity of the ATV in terms of mitochondrial membrane potential changes. The loss of mitochondrial membrane integrity and subsequent release cytochrome C from the inner membrane of the mitochondrion initiates the intrinsic apoptotic pathway culminating in the activation of caspase 3/7 (Brentnall, Rodriguez\u2010Menocal, De Guevara, Cepero, & Boise,\u00a05This study found that ATV was concentration\u2010 and time\u2010dependently hepatotoxic to C3A liver cells and this hepatotoxic effect was exacerbated by the addition of palmitate pretreatment. ATV toxicity was associated with decreased mitochondrial membrane potential, increased ROS production, as well as increased caspase 3/7 activity. GRT was unable to protect against the ATV\u2010induced mitochondrial dysfunction and the consequent induced toxicity. The findings from the current study suggest that concurrent supplementation with GRT appears to be ineffective at protecting C3A liver cells against ATV\u2010induced toxicity in vitro. However, given the complexity of bioavailability and pharmacokinetics of complex mixtures, such as plant extracts, it is difficult to accurately extrapolate in vitro results to a clinical setting. Despite this, our findings suggest that it is unlikely that GRT will exhibit sufficient hepatoprotective effects in patients with ATV\u2010related hepatotoxicity.The authors hereby confirm that Professors Louw and Muller have a research interest in Afriplex GRT, a pharmaceutical grade GMP aspalathin\u2010enriched unfermented rooibos extract."}
{"text": "BioMed Research International has retracted the article titled \u201cPositive Effects against UV-A Induced Damage and Oxidative Stress on an In Vitro Cell Model Using a Hyaluronic Acid Based Formulation Containing Amino Acids, Vitamins, and Minerals\u201d [The CTR (16\u2009h) and CTR (32\u2009h) panels appear to be identicalThe M-HA (48\u2009h) and M-HA (96\u2009h) appear to be identicalSkink\u00f2 E (48\u2009h) and Skink\u00f2 E (96\u2009h) appear to be identicalSkink\u00f2 E (72\u2009h) and CTR (96\u2009h) appear to be identicalThe same cluster of cells can be seen in Skink\u00f2 E (48\u2009h), Skink\u00f2 E (72\u2009h), and Skink\u00f2 E (96\u2009h).inerals\u201d . As raisinerals\u201d , there aThe authors said that the duplications between M-HA (48\u2009h) and M-HA (96\u2009h) and CTR (96) and Skink\u00f2 E (72\u2009h) were mistakes introduced during manuscript preparation. A satisfactory explanation was not provided for the remaining concerns and the article is therefore being retracted with the agreement of the editorial board. The authors do not agree to retraction."}
{"text": "Scientific Reports 10.1038/s41598-020-77199-4, published online 18 November 2020Correction to: In this Article, the legend of Figure\u00a04 is incorrect:https://www.graphpad.com/support/faq/prism-842-release-notes/). (d) Schematic representation of the mRNA sequence of human CPT2 (hCPT2). hCPT2 has two uORFs in its 5\u2019UTR. A luciferase-reported assay for the detection of hCPT2 5\u2032UTR in HUVECs treated with vehicle, PERKI, TGF-\u03b21, or TGF-\u03b21\u2009+\u2009PERKI for 4\u00a0h or 8\u00a0h (n\u2009=\u20094 per groups) was performed. P-values were determined using the unpaired t-test. In all bar graphs, the mean\u2009\u00b1\u2009SEM are shown. In all box-and-whiskers\u2019 plots, mean values are provided. \u203bp\u2009<\u20090.05; one-way ANOVA with Bonferroni post hoc analysis.\u201d\u201cInduction of EndoMT is suppressed by PERK inhibition. (a) Morphology of human umbilical vein endothelial cells (HUVECs) treated with vehicle, 1\u00a0\u03bcM PERK inhibitor (PERKI), TGF-\u03b21, and TGF-\u03b21\u2009+\u2009PERKI for 8\u00a0h. (b) mRNA expression of UPR, EndoMT, and FAO-related genes in HUVECs treated with vehicle (n\u2009=\u20096), PERKI (n\u2009=\u20093), TGF-\u03b21 (n\u2009=\u20093), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20093). Gene expression was detected using qRT-PCR. \u03b2-actin was used as an internal control. (c) mRNA expression of UPR, EndoMT, and the FAO-related genes in HUVECs treated with vehicle, PERKI, TGF-\u03b21, or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20094 per group). This graph was drawn by Graph Pad Prism8.4.2. . (d) Schematic representation of the mRNA sequence of hCPT2. hCPT2 has two uORFs in its 5\u2019UTR. A luciferase-reported assay for the detection of hCPT2 5\u2032UTR in HUVECs treated with vehicle, PERKI, TGF-\u03b21, or TGF- \u03b21\u2009+\u2009PERKI for 4\u00a0h or 8\u00a0h (n\u2009=\u20094 per groups) was performed. P-values were determined using the unpaired t-test. In all bar graphs, the mean\u2009\u00b1\u2009SEM are shown. In all box and whiskers\u2019 plots, mean values are provided. p\u2009<\u20090.05; one way ANOVA with Bonferroni post hoc analysis.\u201d\u201cInduction of EndoMT is suppressed by PERK inhibition. (a) Morphology of human umbilical vein endothelial cells (HUVECs) treated with vehicle, 1\u00a0\u03bcM PERK inhibitor (PERKI), TGF-\u03b21, and TGF-\u03b21\u2009+\u2009PERKI for 8\u00a0h. (b) mRNA expression of UPR, EndoMT, and FAO-related genes in HUVECs treated with vehicle (n\u2009=\u20096), PERKI (n\u2009=\u20093), TGF-\u03b21 (n\u2009=\u20093), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20093). Gene expression was detected using qRT-PCR. \u03b2-actin was used as an internal control. (c) Protein expression of human CPT2 (hCPT2) in HUVECs treated with vehicle, PERKI, TGF-\u03b21, or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20094 per group). This graph was drawn by Graph Pad Prism8.4.2. . In all bar graphs, the mean\u2009\u00b1\u2009SEM are shown. In all box-and-whiskers\u2019 plots, mean values are provided. \u203bp\u2009<\u20090.05; one-way ANOVA with Bonferroni post hoc analysis.\u2019\u2019\u201cTranslation of CPT2 is induced by PERK. (a) Flow cytometry-based quantification of BODIPY 493/503 staining in HUVECs treated with vehicle (n\u2009=\u20098), PERKI (n\u2009=\u20094), TGF-\u03b21 (n\u2009=\u20094), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20094). (b) Quantification of the mitochondrial metabolic activity of HUVECs treated with vehicle (n\u2009=\u20099), PERKI (n\u2009=\u20094), TGF-\u03b21 (n\u2009=\u20095), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20095), using resazurin. These graphs were drawn by Graph Pad Prism8.4.2. . In all bar graphs, the mean\u2009\u00b1\u2009SEM are shown. In all box-and-whiskers\u2019 plots, mean values are provided. p\u2009<\u20090.05; one-way ANOVA with Bonferroni post hoc analysis.\u201d\u201cTransport of neutral lipids from the cytosol into the mitochondria is induced by PERK. (a) Flow cytometry-based quantification of BODIPY 493/503 staining in HUVECs treated with vehicle (n\u2009=\u20098), PERKI (n\u2009=\u20094), TGF-\u03b21 (n\u2009=\u20094), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20094). (b) Quantification of the mitochondrial metabolic activity of HUVECs treated with vehicle (n\u2009=\u20099), PERKI (n\u2009=\u20094), TGF-\u03b21 (n\u2009=\u20095), or TGF-\u03b21\u2009+\u2009PERKI (n\u2009=\u20095), using resazurin. These graphs were drawn by Graph Pad Prism8.4.2. (freely available software after purchasing,"}
{"text": "The three-mol\u00adecule aggregates are connected into a supra\u00admolecular tape along [111] by amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonding.In the title 1:2 co-crystal a three-mol\u00adecule aggregate,  14H14N4O2\u00b72C7H5ClO2, comprises a half-mol\u00adecule of oxalamide (4LH2), being located about a centre of inversion, and a mol\u00adecule of3-chloro\u00adbenzoic acid (3-ClBA) in a general position. From symmetry, the 4LH2 mol\u00adecule has a (+)anti\u00adperiplanar conformation with the 4-pyridyl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angle between the core and pyridyl ring being 74.69\u2005(11)\u00b0; intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bonds are noted. The 3-ClBA mol\u00adecule exhibits a small twist as seen in the C6/CO2 dihedral angle of 8.731\u2005(12)\u00b0. In the mol\u00adecular packing, three-mol\u00adecule aggregates are formed via carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding. These are connected into a supra\u00admolecular tape along [111] through amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonding. Additional points of contact between mol\u00adecules include pyridyl and benzoic acid-C\u2014H\u22efO(amide), methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) and C\u2014Cl\u22ef\u03c0(pyrid\u00adyl) inter\u00adactions so a three-dimensional architecture results. The contributions to the calculated Hirshfeld surface are dominated by H\u22efH (28.5%), H\u22efO/O\u22efH (23.2%), H\u22efC/C\u22efH (23.3%), H\u22efCl/Cl\u22efH (10.0%) and C\u22efCl/C\u22efCl (6.2%) contacts. Computational chemistry confirms the C\u2014Cl\u22ef\u03c0 inter\u00adaction is weak, and the importance of both electrostatic and dispersion terms in sustaining the mol\u00adecular packing despite the strong electrostatic term provided by the carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds.The asymmetric unit of the title 1:2 co-crystal, C As is normal for nLH2 mol\u00adecules \u2005\u00c5; symmetry code: (i) 1\u00a0\u2212\u00a0x, \u2212 y, \u2212 z] bond length is considered long, an observation ascribed to the electronegative substituents bound to the sp2-C7 atom. The conformation of the 4LH2 mol\u00adecule is (+)anti\u00adperiplanar so the 4-pyridyl residues lie to either side of the planar region of the mol\u00adecule. The dihedral angle between the central core and the N1-pyridyl ring is 74.69\u2005(11)\u00b0. Owing to the anti-disposition of the amide groups intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bonds are formed which complete S(5) loops, Table\u00a01The 4LH2 and two symmetry-related 3-ClBA mol\u00adecules via carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding, Table\u00a01via amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds Fig.\u00a02a). These give rise to 22-membered {\u22efNC4NH\u22efOCOH}2 synthons. Additional stability to the hydrogen-bonding arrangement is provided by supporting benzoic acid-C14\u2014H\u22efO(amide) inter\u00adaction which lead to non-symmetric 10-membered {\u22efHC3O\u22efHNC2O}2 synthons, which flank the larger 22-membered rings. Further, a complementary C\u2014Cl\u22ef\u03c0(pyrid\u00adyl) contact is noted, as detailed in Table\u00a01et al., 2008et al., 2016b). The tapes are connected into a supra\u00admolecular layer by relatively short pyridyl-C1\u2014H\u22efO(amide) contacts, Fig.\u00a02c). A three-dimensional architecture results when benzoic acid-C12\u2014H\u22efO(amide) and methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions are taken into consideration, Fig.\u00a02d). In this scheme, the amide-O1 atom participates in three pivotal C\u2014H\u22efO inter\u00adactions.The most distinctive feature of the mol\u00adecular packing is the association between i.e. that sustained by the carb\u00adoxy\u00adlic acid-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds, and for the individual components, viz. the full mol\u00adecule of 4LH2 and 3-ClBA, with the use of CrystalExplorer17 , amide-N2\u2014H2N\u22efO2(carbon\u00adyl), pyr\u00adid\u00adyl-C1\u2014H1\u22efO1(amide), benzene-C14\u2014H14\u22efO1(amide), benzene-C12\u2014H12\u22efO1(amide) and methyl\u00adene-C6\u2014H6A\u22efO3(hydrox\u00adyl); the dnorm distances for these short contacts are given in Table\u00a02PLATON analysis  indicating the contact distance that is slightly less than the sum of the van der Waals radii d,p), as available in CrystalExplorer17. The analysis indicates that the Cl\u22ef\u03c0 inter\u00adaction is weak in nature as evidenced from the white spot around the \u03c3-hole region about the Cl1 atom in Fig.\u00a04a) as well as the faint-red spot around the centre of the \u03c0-ring centre, Fig.\u00a04b). A detailed study on the localized electrostatic charges shows that the \u03c3-hole of Cl1 is about \u22120.0072 a.u. while the pyridyl \u03c0-hole is about \u22120.1270 a.u. indicating that the inter\u00adaction is rather dispersive in nature. This observation is in contrast with other charge complementary inter\u00adactions as shown from the intense blue (i.e. electropositive) and red (i.e. electronegative) regions on the electrostatic surface map. For instance, the amide-N2\u2014H2N\u22efO2(carbon\u00adyl) hydrogen bond has a point-to-point electrostatic charge of 0.1438 a.u. for H2N and \u22120.0622 a.u. for O2, suggestive of a strong inter\u00adaction, while benzene-C14\u2014H14\u22efO1(amide) shows complementary charges of 0.0427 and \u22120.0486 a.u. for H14 and O1, respectively, being indicative of a relatively weaker inter\u00adaction. Among all the identified close contacts, hydroxyl-O3\u2014H3O\u22efN1(pyrid\u00adyl) is considered to be the strongest exhibiting a marked difference in the electrostatic charge of 0.2919 a.u. for H3O and \u22120.0727 a.u. for N1.To verify the nature of the Cl\u22ef\u03c0 contact in (I)i.e. 4LH2 and 3-ClBA, were subjected to fingerprint analysis for qu\u00adanti\u00adfication of the close contacts for each entity, Fig.\u00a05a). Overall (I)b)\u2013(f); others contacts amount to 6.6%, constituting contacts less than 2.0% each. Among those contacts for (I)di + de contact distances tipped at ca 1.94 and 2.08\u2005\u00c5, respectively, significantly less than their respective sums of van der Waals radii of 2.61 and 2.79\u2005\u00c5; the remaining contacts occur at distances greater than their corresponding sums of van der Waals radii.The three-mol\u00adecule-aggregate of (I)4LH2 and 3-ClBA mol\u00adecules. The key difference between these and that for (I)4LH2, the major contacts comprise H\u22efH (34.5%), H\u22efO/O\u22efH (22.1%), H\u22efC/C\u22efH (20.3%), H\u22efN/N\u22efH (8.4%), H\u22efCl/Cl\u22efH (6.4%) and C\u22efCl (5.0%). A detailed analysis on the corresponding contacts reveals that the -H\u22efO- and -H\u22efC- contacts are slightly more dominant over the -O\u22efH- and -C\u22efH- counterparts with the distribution of the contacts being 12.7 and 11.2% versus 9.4 and 9.1%, while the opposite is true for the -H\u22efN- contact with a distribution of 0.6% as compared to 7.8% for -N\u22efH-. The stark difference in the dominance for H\u22efN/N\u22efH is likely due to the amide-H forming a hydrogen bond to O(carbon\u00adyl) rather than to a nitro\u00adgen acceptor. Among the major contacts, -H\u22efO- and -N\u22efH- display minimum di + de distances of about 1.94 and 1.60\u2005\u00c5, respectively, which are significantly shorter than the sums of the respective van der Waals radii as compared to the -O\u22efH- and -H\u22efN- counterparts of 2.24 and 3.62\u2005\u00c5, respectively. A similar observation is noted for -H\u22efC- (\u223c2.66\u2005\u00c5) despite the deviation from the sum of the van der Waals radii (2.79\u2005\u00c5) being less significant.A similar paw-like fingerprint profile is observed for the overall fingerprint plots of the individual X\u22efY- for some close contacts , with the distribution being 15.0, 14.4, 10.5 and 5.5% for O\u22efH, C\u22efH, Cl\u22efH and Cl\u22efC, respectively, compared to 8.5, 8.5, 1.4 and 1.0% for the corresponding H\u22efO, H\u22efC, H\u22efCl and C\u22efCl counterparts. In term of di + de contact distances, the key values are reciprocal to those for 4LH2 owing to the inter\u00addependency of inter\u00adactions as mentioned previously.As for the individual 3-ClBA mol\u00adecule, the major contacts in the overall fingerprint plot can be delineated into H\u22efO/O\u22efH (23.5%), H\u22efC/C\u22efH (22.9%), H\u22efH (21.8%), H\u22efCl/Cl\u22efH (11.9%), C\u22efCl/Cl\u22efC (6.5%) and H\u22efN/N\u22efH (4.6%). The trend of dominance is more inclined towards -CrystalExplorer17  hydrogen bond has the greatest inter\u00adaction energy (Eint) with the value being \u221248.0\u2005kJ\u2005mol\u22121, and this is followed by the dimeric amide-N2\u2014H2N\u22efO2(carbon\u00adyl), benzene-C14\u2014H14\u22efO1(amide) and Cl1\u22ef\u03c0 inter\u00adactions, with a combined Eint of \u221238.7\u2005kJ\u2005mol\u22121, the 16-membered {\u22efOCNC3CH\u22ef} heterosynthon involving pyridyl-C1\u2014H1\u22efO1(amide) inter\u00adactions (\u221224.6\u2005kJ\u2005mol\u22121), benzene-C12\u2014H12\u22efO1(amide) and pyridyl-C4\u2014H4\u22efC11(benzene) with a combined Eint of \u221224.0\u2005kJ\u2005mol\u22121, methyl\u00adene-C6\u2014H6A\u22efO3(hydrox\u00adyl) (\u221215.8\u2005kJ\u2005mol\u22121) as well as the benzene-C10\u22efC10(benzene) inter\u00adaction with (\u221215.0\u2005kJ\u2005mol\u22121). Inter\u00adestingly, the strongest hydroxyl-O3\u2014H3O\u22efN1(pyrid\u00adyl) inter\u00adaction in this crystal has an Eint value that is only slightly less than that of \u221249.4 and \u221252.0\u2005kJ\u2005mol\u22121) (two independent mol\u00adecules) displayed by an equivalent O\u2014H\u22efN hydrogen bond complemented by a supporting pyridyl-C\u2014H\u22efO(carbon\u00adyl) inter\u00adaction in the isomeric 2:1 co-crystal of 4LH2 with 4-ClBA O\u22efN1(pyrid\u00adyl) inter\u00adaction is the main foundation of the framework as evidenced from the thick cylindrical rods with other, relatively, thinner rods which ramify owing to various other O\u22efH inter\u00adactions, Fig.\u00a06a). The O\u22efH inter\u00adactions together with other complementary inter\u00adactions are found to contribute to the dispersion energy framework which forms a similar topology as the electrostatic energy framework, Fig.\u00a06b). The combination of the other electrostatic and dispersion forces supersedes the strong inter\u00adaction energy from the hydroxyl-O3\u2014H3O\u22efN1(pyrid\u00adyl) hydrogen bonding and leads to the overall energy framework illustrated in Fig.\u00a06c) without dominant inter\u00adactions in a given direction. It is inter\u00adesting to note that despite being an isomeric analogue to the 4LH2\u00b72(4-ClBA) co-crystal .The co-crystal system is governed by a combination of electrostatic and dispersion forces leading to a three-dimensional wire mesh-like energy framework as shown in Fig.\u00a064LH2\u00b72(4-ClBA) 2 synthons, as highlighted in Fig.\u00a07The aforementioned analogue of (I)et al., 2019a and IIb. This is compensated by a reduction in the H\u22efCl/Cl\u22efH contacts by 4.9 and 5.6%. One possible reason for the increase in O\u22efH/H\u22efO contacts in (I)cf. (II) relates to the participation of the carbonyl-O atom in formal hydrogen bonding to the amide-N\u2014H group and the prominent role of the amide-O1 atom in providing points of contact between mol\u00adecules.A comparison of the percentage contributions by the most prominent contacts to the respective Hirshfeld surfaces of (I)N,N\u2032-bis\u00ad[(pyridin-4-yl)meth\u00adyl]oxalamide (4LH2) was prepared according to a literature procedure: M.p. 486.3\u2013487.6\u2005K; lit. 486\u2013487\u2005K  was mixed with 3-ClBA  and the mixture was then ground for 15\u2005min in the presence of a few drops of methanol. The procedure was repeated twice. Colourless blocks were obtained through careful layering of toluene (1\u2005ml) on an N,N-di\u00admethyl\u00adformamide solution (1\u2005ml) of the ground mixture. M.p. 436.6\u2013437.7\u2005K. IR (cm\u22121): 3280 \u03bd(N\u2014H), 3070\u20132919 \u03bd(C\u2014H), 1703\u20131656 \u03bd(C=O), 1524 \u03bd(C=C), 1415 \u03bd(C\u2014N), 753 \u03bd(C\u2014Cl).The precursor, Uiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located from a difference-Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.86\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020006568/wm5558sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020006568/wm5558Isup2.hklStructure factors: contains datablock(s) I. DOI: 2004094CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reportshttps://doi.org/10.1038/s41598-020-74140-7, published online 19 October 2020.Correction to: The Supplementary Information file that accompanies this Article contained errors in Supplementary Table 13, where values were rounded incorrectly.In the column \u2018Exercise\u2009+\u2009Supplement Pre\u2019, in the row \u2018Blood Pressure\u2019\u201c102 (10.4)\u201dnow reads:\u201c102.0 (10.4)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Pre\u2019, in the row \u2018Heart Rate\u2019\u201c127 (10.2)\u201dnow reads:\u201c127.2 (10.2)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Pre\u2019, in the row \u2018Lean Muscle Mass (pounds)\u2019\u201c123 (22.7)\u201dnow reads:\u201c123.1 (22.7)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Pre\u2019, in the row \u2018Fluid Intelligence RT\u2019\u201c514 (114)\u201dnow reads:\u201c514.5 (114)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Pre\u2019, in the row \u2018Executive Function RT\u2019\u201c695 (133)\u201dnow reads:\u201c693.5 (133)\u201dIn the same Supplementary Table 13, in the column \u2018Exercise\u2009+\u2009Supplement Post\u2019, in the row \u2018Heart Rate\u2019\u201c122 (9.6)\u201dnow reads:\u201c122.6 (9.6)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Post\u2019, in the row \u2018Lean Muscle Mass (pounds)\u2019\u201c126 (22.8)\u201dnow reads:\u201c126.5 (22.8)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Post\u2019, in the row \u2018Fluid Intelligence RT\u2019\u201c493 (97.1)\u201dnow reads:\u201c491.4 (97.1)\u201dIn the column \u2018Exercise\u2009+\u2009Supplement Post\u2019, in the row \u2018Executive Function RT\u2019\u201c639 (124)\u201dnow reads:\u201c638.5 (124)\u201dIn the same Supplementary Table 13, in the column \u2018Exercise\u2009+\u2009Placebo Pre\u2019, in the row \u2018Heart Rate\u2019\u201c126 (9.6)\u201dnow reads:\u201c126.1 (9.6)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Pre\u2019, in the row \u2018Lean Muscle Mass (pounds)\u2019\u201c123 (23.2)\u201dnow reads:\u201c122.8 (23.2)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Pre\u2019, in the row \u2018Fluid Intelligence RT\u2019\u201c496 (111)\u201dnow reads:\u201c496.4 (111)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Pre\u2019, in the row \u2018Executive Function RT\u2019\u201c684 (136)\u201dnow reads:\u201c683.6 (136)\u201dFinally, in the same Supplementary Table 13, in the column \u2018Exercise\u2009+\u2009Placebo Post\u2019, in the row \u2018Heart Rate\u2019\u201c125 (9.7)\u201dnow reads:\u201c124.4 (9.7)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Post\u2019, in the row \u2018Lean Muscle Mass (pounds)\u2019\u201c124 (22.1)\u201dnow reads:\u201c124.2 (22.1)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Post\u2019, in the row \u2018Fluid Intelligence RT\u2019\u201c505 (82)\u201dnow reads:\u201c504.8 (82)\u201dIn the column \u2018Exercise\u2009+\u2009Placebo Post\u2019, in the row \u2018Executive Function RT\u2019\u201c643 (143)\u201dnow reads:\u201c643.8 (143)\u201dAdditionally, in the legend of Supplementary Table 13 the formulas for computing the values in the Abstract were omitted,\u201cRT is reaction time in milliseconds.\u201dnow reads:\u201cRT is reaction time in milliseconds. The values in this table were used to derive the values in the abstract of the manuscript. Exercise effects reported in the abstract were derived by computing the percent change for the Exercise\u2009+\u2009Placebo group: (Exercise\u2009+\u2009Placebo Post\u2014Exercise\u2009+\u2009Placebo Pre)/Exercise\u2009+\u2009Placebo Pre. Multimodal fitness and nutritional intervention effects reported in the abstract were derived by computing a relative difference percent change: [(Exercise\u2009+\u2009Supplement Post\u2014Exercise\u2009+\u2009Supplement Pre)/Exercise\u2009+\u2009Supplement Pre]-[(Exercise\u2009+\u2009Placebo Post\u2014Exercise\u2009+\u2009Placebo Pre)/Exercise\u2009+\u2009Placebo Pre].\u201dThe original version of Supplementary Table 13 appears below as Table As a result of the errors in Supplementary Table 13, in the Abstract,\u201cThe exercise intervention alone improved several dimensions of physical fitness  and cognitive function . Relative to exercise training alone, the multimodal fitness and nutritional intervention further improved working memory (+\u20099.0%), fluid intelligence reaction time (\u2212\u20097.7%), processing efficiency (+\u20091.8%), heart rate (\u2212\u20092.4%) and lean muscle mass (+\u20091.5%).\u201dnow reads:\u201cThe exercise intervention alone improved several dimensions of physical fitness  and cognitive function . Relative to exercise training alone, the multimodal fitness and nutritional intervention further improved working memory (+\u200911.2%), fluid intelligence reaction time (\u2212\u20096.2%), processing efficiency (+\u20094.3%), heart rate (\u2212\u20092.3%) and lean muscle mass (+\u20091.6%).\u201dThese errors have now been corrected in the PDF and HTML versions of the Article, and in the Supplementary Information file that accompanies the Article."}
{"text": "Talaromyces\u00a0cellulolyticus (TcXyn30B), is a bifunctional enzyme with glucuronoxylanase and xylobiohydrolase activities. In the present study, crystal structures of the native enzyme and the enzyme\u2013product complex of TcXyn30B expressed in Pichia\u00a0pastoris were determined at resolutions of 1.60 and 1.65\u00a0\u00c5, respectively. The enzyme complexed with 22\u2010(4\u2010O\u2010methyl\u2010\u03b1\u2010d\u2010glucuronyl)\u2010xylobiose (U4m2X) revealed that TcXyn30B strictly recognizes both the C\u20106 carboxyl group and the 4\u2010O\u2010methyl group of the 4\u2010O\u2010methyl\u2010\u03b1\u2010d\u2010glucuronyl side chain by the conserved residues in GH30\u20107 endoxylanases. The crystal structure and site\u2010directed mutagenesis indicated that Asn\u201093 on the \u03b22\u2010\u03b12\u2010loop interacts with the non\u2010reducing end of the xylose residue at subsite\u20102 and is likely to be involved in xylobiohydrolase activity. These findings provide structural insight into the mechanisms of substrate recognition of GH30\u20107 glucuronoxylanase and xylobiohydrolase.Xylanase B, a member of subfamily 7 of the GH30 (glycoside hydrolase family 30) from  TcXyn30B is a bifunctional xylanase with endo\u2010glucuronoxylanase and exo\u2010xylobiohydrolase activities. The present study determined the crystal structure of the TcXyn30B\u2010product complex. A 4\u2010O\u2010methyl\u2010\u03b1\u2010d\u2010glucuronyl moiety\u2010binding pocket required for glucuronoxylanase activity and Asn\u201093 (which is likely involved in xylobiohydrolase activity) was structurally characterized. The present study provides insight into the mechanisms of substrate recognition of a bifunctional xylanase. GH30\u20107subfamily 7 of the glycoside hydrolase family 30GH30\u20108subfamily 8 of the glycoside hydrolase family 30MeGlcAO\u2010methyl\u2010d\u2010glucuronic acid\u03b1\u20101,2\u2010linked\u20104\u20104m2XU2\u2010(4\u2010O\u2010methyl\u2010\u03b1\u2010d\u2010glucuronyl)\u2010xylobiose23XxylotriosenU4m2XX2\u2010MeGlcA\u2010xylooligosaccarides24m2XXU2\u2010MeGlcA\u2010xylotriose2d\u2010xylopyranosyl residues linked by \u03b2\u20101,4\u2010glycosidic bonds, which are further decorated with side\u2010chain residues, such as \u03b1\u20101,2\u2010 and/or \u03b1\u20101,3\u2010linked\u2010l\u2010arabinofuranose, and \u03b1\u20101,2\u2010linked\u20104\u2010O\u2010methyl\u2010d\u2010glucuronic acid (MeGlcA). Glucuronoxylanase (https://www.qmul.ac.uk/sbcs/iubmb/) is an appendage\u2010dependent endoxylanase that must recognize an \u03b1\u20101,2\u2010linked MeGlcA common to glucuronoxylans for hydrolysis. Glucuronoxylanase cleaves the glucuronoxylan main chain at the second glycosidic linkage from the MeGlcA substituent toward the reducing end to produce 22\u2010MeGlcA\u2010xylooligosaccarides . The enzyme is classified into glycoside hydrolase family (GH) 30 subfamilies 7 and 8 (GH30\u20107 and 30\u20108) in the CAZy database (http://www.cazy.org) , , 8, 4m2Xh XU4m2X .O\u2010methyl group of MeGlcA   and XYN VI glucuronoxylanase [TcXyn30B  and its mutant enzyme whose Asn\u201093 was replaced by Ala (TcXyn30B\u2010His N93A) were prepared. The glucuronoxylanase activities of TcXyn30B\u2010His and TcXyn30B\u2010His N93A for beechwood xylan were 10.9\u00a0\u00b1\u00a00.5 and 12.0\u00a0\u00b1\u00a00.2\u00a0U\u00b7mg\u22121, respectively. By contrast, the xylobiohydrolase activities of TcXyn30B\u2010His and TcXyn30B\u2010His N93A for X3 were 0.290\u00a0\u00b1\u00a00.006 and 0.0987\u00a0\u00b1\u00a00.004\u00a0U\u00b7mg\u22121, respectively. The kinetic parameters for each enzyme activity of TcXyn30B\u2010His and TcXyn30B\u2010His N93A are shown in Table\u00a0Km and kcat values for the xylobiohydrolase activity could not be determined because the initial rate of xylose production from X3 was not saturated even at a substrate concentration of 16\u00a0mm. However, the three\u2010fold reduction of the kcat/Km value in the N93A mutant suggests that Asn\u201093 could contribute to increased catalytic efficiency for xylobiohydrolase activity but is not essential. These results also support the hypothesis that Asn\u201093 interacts with the non\u2010reducing end of xylose residue at the subsite \u20102.To evaluate the role of Asn\u201093 in nU4m2X from xylan requires the binding of substrate at subsite \u20103 onward. When the TcXyn30B model was superimposed on the EcXynA model complexed with XU4m2X, a steric clash between non\u2010reducing end of XU4m2X and Asn\u201093 of TcXyn30B was observed . The black arrow indicates the position of TcXyn30B.Fig. S3. Crystals of TcXyn30B complexed with U4m2X.Fig. S4.Fo\u2010Fc omit maps (blue) contoured at 3.0\u00a0\u03c3 for sugar chains. N\u2010linked carbohydrate moieties. Sugar chains linked Asn\u201060, Asn\u201088, Asn\u2010334, Asn\u2010346 and Asn\u2010412 are shown. Atoms are coloured as: C of N\u2010linked sugar chain residues, purple; C of TcXyn30B, brown; O, red; N, blue.Fig. S5. Orientations of U4m2X bound to TcXyn30B and XU4m2X bound to EcXynA. The model of TcXyn30B with U4m2X was superimposed on EcXynA with XU4m2X (PDB ID: https://doi.org/10.2210/pdb2Y24/pdb). The distances are given in \u00c5.Click here for additional data file."}
{"text": "The square-planar and trigonal\u2013bipyramidal coordination environments around platinum and arsenic, respectively, are significantly distorted with the largest outliers being 173.90\u2005(13) and 106.98\u2005(14)\u00b0 for platinum and arsenic in (1), and 173.20\u2005(14)\u00b0 and 94.20\u2005(9)\u00b0 for (2), respectively. One intra\u00admolecular and four classical inter\u00admolecular hydrogen-bonding inter\u00adactions are observed in the crystal structure of (1), which give rise to an infinite three-dimensional network. A similar situation  is observed in the crystal structure of (2). Various \u03c0-inter\u00adactions are present in (1) between the platinum(II) atom and the centroid of one of the five-membered rings formed by Pt, As, C, N, O with a distance of 3.7225\u2005(7)\u2005\u00c5, and between the centroids of five-membered  rings of neighbouring mol\u00adecules with distances of 3.7456\u2005(4) and 3.7960\u2005(6)\u2005\u00c5. Likewise, weak \u03c0-inter\u00adactions are observed in (2) between the platinum(II) atom and the centroid of one of the five-membered rings formed by Pt, As, C, N, O with a distance of 3.8213\u2005(2)\u2005\u00c5, as well as between the Cl atom and the centroid of a symmetry-related five-membered ring with a distance of 3.8252\u2005(12)\u2005\u00c5. Differences between (2) and the reported polymorph [Miodragovi\u0107 et al.  atom in the crystal structures of chlorido\u00ad[dihy\u00addroxybis\u00ad(1-imino\u00adeth\u00adoxy)arsanido-\u03ba al. 2013. Angew.  Cl] (1), and [Pt(C6H14AsN2O4)Cl], (2), expand on this work and form part of an ongoing study on arsenoplatins, their solid- and solution-state behaviour and evaluation thereof.The structures reported here,  while there are slight differences for the N\u2014Pt1\u2014As1 and N\u2014Pt\u2014Cl1 bond angles: 85.18\u2005(11) and 89.42\u2005(11)\u00b0 for (1), and 87.25\u2005(10) and 86.05\u2005(10)\u00b0 for (2) , and 93.28\u2005(11) and 92.34\u2005(11)\u00b0 for (1) and 94.16\u2005(11) and 92.53\u2005(10)\u00b0 for (2) . The As1\u2014Pt1\u2014Cl1 bond angles also vary being 174.79\u2005(3) and 178.51\u2005(3)\u00b0 for (1) and (2). The bond angles around arsenic are all in a similar range but have more variation in some of the angles, for instance 126.42\u2005(10) and 130.05\u2005(11)\u00b0 (O6\u2014As1\u2014Pt1), 90.24\u2005(9) and 94.20\u2005(9)\u00b0 (O2\u2014As1\u2014Pt1), and 95.35\u2005(10) and 93.12\u2005(8)\u00b0 (O1\u2014As1\u2014Pt1) for (1) and (2), respectively. The trigonal\u2013 bipyramidal coord\u00adination environment around arsenic is distorted in both mol\u00adecules with a \u03c45 parameter value of 0.794 and 0.711 for (1) and (2). Thus, the As atom in (2) shows a slightly higher distortion than in (1).When comparing the mol\u00adecules of (1), six hydrogen-bonding inter\u00adactions are observed  and one intra\u00admolecular (O6\u2014H6\u22efO2), as illustrated in Fig.\u00a02iii = 2.750\u2005(4)\u2005\u00c5], which generates an infinite chain along the c-axis direction , defined by the platinum(II) atom of one mol\u00adecule to the centroid of the  ring with a Pt\u22efcentroid distance of 3.7225\u2005(7)\u2005\u00c5, by the centroid of the  ring to the centroid of the   ring of an adjacent mol\u00adecule with a distance of 3.7456\u2005(4)\u2005\u00c5, and by the centroid of the  ring to the centroid of another   ring with a distance of 3.7960\u2005(6)\u2005\u00c5  is likewise stabilized by one intra\u00admolecular (O6\u2014H6\u22efO1) and five inter\u00admolecular  hydrogen-bonding inter\u00adactions (Table\u00a022), one from Pt1 to the centroid of Pt1,As1,O1,C1,N1 with a distance of 3.8213\u2005(2)\u2005\u00c5 and the other from Cl1 to a symmetry-related centroid  with a distance of 3.8252\u2005(12)\u2005\u00c5  and (2) pack differently due to the presence of different alkyl chains  was added to a 125\u2005ml solution of 9:1 (v:v) CH3CN/H2O. The mixture was stirred at 363\u2005K. Once the K2PtCl4 had dissolved, As2O3  was added to the solution and refluxed at 363\u2005K for 48\u2005h. The mixture was then filtered, and the filtrate was left to stand at room temperature. Crystals suitable for X-ray crystallography were obtained by slow evaporation. Yield: 301\u2005mg (66%). 1H NMR : \u03c3 = 7.30 , 6.69 , 1.75  ppm. 13C NMR : \u03c3 =172 (CN), 23 (CH3) ppm. 195Pt NMR : \u03c3 = \u22123590.62 ppm. UV/Vis = \u03bb = 285\u2005nm, \u220a = 4029\u2005dm3\u2005mol\u22121 cm\u22121. Analysis calculated: C, 10.55; H, 2.21; N, 6.15. Found: C, 10.64; H, 2.22; N, 6.09%.KSynthesis of 22PtCl4  was added to a 50\u2005ml solution of 9:1 (v:v) H2O/CH3CH2CN. The mixture was stirred at room temperature. Once the K2PtCl4 had dissolved, As2O3  was added to the solution and was stirred at room temperature for 96\u2005h. The solution was cooled in an ice bath and then filtered. The filtrate was left to stand at room temperature. Crystals suitable for X-ray crystallography were obtained by slow evaporation. Yield: 278\u2005mg (56%). 1H NMR : \u03b4 = 8.89 , 7.99 , 2.48 , 1.04 . 13C NMR : \u03b4 = 176.18 (CN), 24.53 (CH2), 11.70 (CH3). 195Pt NMR  = \u22123591.52. UV/Vis: \u03bbmax = 270\u2005nm, \u220a = 4231\u2005L\u2005mol\u22121 cm\u22121. Analysis calculated C, 14.90; H, 2.92; N, 5.79. Found: C, 14.82; H, 2.91; N, 5.76.KUiso(H) = 1.5Ueq(C) and 1.2Ueq(C)]. The OH and NH hydrogen atoms were located in a difference-Fourier map and their positional parameters were constrained with O\u2014H = 0.84\u2005(2)\u2005\u00c5 and N\u2014H = 0.89\u2005(2)\u2005\u00c5 for (1), and N\u2014H = 0.87\u2005(2)\u2005\u00c5 for (2) with O\u2014H distances fixed at 0.82\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O). For (2), the c versus FoF plot proved ten reflections to be outliers, and they were removed from the refinement as systematic errors.Crystal data and details of data collections and structure refinements are summarized in Table\u00a0310.1107/S2056989019016463/wm5532sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 1938096, 1938095CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Serotonin 2A receptors, the molecular target of psychedelics, are expressed by neuronal and vascular cells, both of which might contribute to brain haemodynamic characteristics for the psychedelic state.Aiming for a systemic understanding of psychedelic vasoactivity, here we investigated the effect of N-(2-hydroxybenzyl)-2,5-dimethoxy-4-cyanophenylethylamine \u2013 a new-generation agonist with superior serotonin 2A receptor selectivity \u2013 on brain-supplying neck-arterial blood flow.We recorded core body temperature and employed non-invasive, collar-sensor based pulse oximetry in anesthetised mice to extract parameters of local blood perfusion, oxygen saturation, heart and respiration rate. Hypothesising an overlap between serotonergic pulse- and thermoregulation, recordings were done under physiological and elevated pad temperatures.N-(2-hydroxybenzyl)-2,5-dimethoxy-4-cyanophenylethylamine  significantly increased the frequency of heart beats accompanied by a slight elevation of neck-arterial blood flow. Increasing the animal-supporting heat-pad temperature from 37\u00b0C to 41\u00b0C enhanced the drug\u2019s effect on blood flow while counteracting tachycardia. Additionally, N-(2-hydroxybenzyl)-2,5-dimethoxy-4-cyanophenylethylamine promoted bradypnea, which, like tachycardia, quickly reversed at the elevated pad temperature. The interrelatedness of N-(2-hydroxybenzyl)-2,5-dimethoxy-4-cyanophenylethylamine\u2019s respiro-cardiovascular effects and thermoregulation was further corroborated by the drug selectively increasing the core body temperature at the elevated pad temperature. Arterial oxygen saturation was not affected by N-(2-hydroxybenzyl)-2,5-dimethoxy-4-cyanophenylethylamine at either temperature.Our findings imply that selective serotonin 2A receptor activation modulates systemic cardiovascular functioning in orchestration with thermoregulation and with immediate relevance to brain-imminent neck (most likely carotid) arteries. As carotid branching is a critical last hub to channel cardiovascular output to or away from the brain, our results might have implications for the brain haemodynamics associated with psychedelia. Lysergic acid diethylamide (LSD) pressure . In animpressure  as well escribed . Beyond d (2ARs) , with gld (2ARs) . 5-HT2ARresearch , yet ourors e.g. . Also, iors e.g. , making 2AR agonist with 100-fold preference for 5-HT2ARs over a plethora of non-5-HT2R targets -2,5-dimethoxy-4-cyanophenylethylamine (25CN-NBOH), a recently developed selective 5-HT targets . We test targets . To avoi targets , experimion e.g. , we expeN\u2009=\u200941) were bred in-house at the Central Biomedical Services of Imperial College London. They were housed in individually ventilated cages with a 12:12\u2009h light/dark cycle and maintained at an ambient temperature of 21\u2009\u00b1\u20092\u00b0C at 55\u2009\u00b1\u200910% humidity. Mice were provided with standard rodent-chow pellets  and water ad libitum.All experimental procedures performed at Imperial College London were in accordance with the United Kingdom Animal Scientific Procedures Act (1986) under Home Office Personal and Project licences , following appropriate ethical review. Adult mice of both sexes and with mixed (non-inbred) genetic background  was dissolved in isotonic saline and applied subcutaneously (<10\u2009mL/kg). The dose used (1.5\u2009mg/kg) was found optimal for a 5-HTtwitches . ExperimPulse oximetry was performed in anaesthetised mice using the rodent-specific MouseOx Plus collar-sensor system . Anaesthesia was induced in an anaesthesia chamber  at 2\u20132.5% isoflurane and, following the loss of the righting reflex, maintained via two-port mask supply at 1.5\u20132.0% concentration. Body temperature was maintained by a feedback-loop controlled heat-pad , which drew input from a thermosensor attached to the heat-pad\u2019s surface, controlling for physiological and elevated (37\u00b0C and 41\u00b0C) pad temperatures, respectively. The collar-sensor was placed around the shaved necks of the animals to read oxygen saturation , heart rate (beats per minute (bpm)), respiration rate (breaths per minute (brpm)) and pulse distention of carotid arteries . Pulse dgroup and pad temperature as between-subject factors and time as within-subject factor) and analysed for main effects, interaction and contrast. Significant interactions were followed by Bonferroni-corrected multiple comparisons. For cross-parameter comparability, results were normalised to their respective baseline average and depicted as fold of baseline.Pulse oximetry 1 Hz readouts \u2013 as aggregated in 5-minute bins \u2013 and core body temperature measurements were analysed via SPSS-implemented three-factorial repeated measures analysis of variance (ANOVA) , pulse distention remained relatively stable throughout the 40-minute recording period. This contrasts with 25CN-NBOH-treated mice \u2009=\u20093.51, p\u2009=\u20090.001), group \u2009=\u20093.51, p\u2009\u2a7d\u20090.001), time \u00d7 group \u2009=\u200916.37, p\u2009\u2a7d\u20090.001), as well as time\u2009\u00d7\u2009group\u2009\u00d7\u2009temperature \u2009=\u20094.99, p\u2009=\u20090.005): Bonferroni-corrected post-hoc analysis revealed significant group differences from 25CN-NBOH treated animals  at any of the four post-injection measurements for both temperature conditions  for 37\u00b0C: 0.98\u2009\u00b1\u20090.017 vs. 1.05\u2009\u00b1\u20090.03 (5\u2009min), p\u2009=\u20090.021; 0.97\u2009\u00b1\u20090.019 vs. 1.04\u2009\u00b1\u20090.026 (10\u2009min), p\u2009=\u20090.036; 0.96\u2009\u00b1\u20090.019 vs. 1.04\u2009\u00b1\u20090.026 (15\u2009min), p\u2009=\u2009.022; 0.96\u2009\u00b1\u20090.021 vs. 1.049\u2009\u00b1\u20090.026 (20\u2009min), p=0.028; for 41\u00b0C: 0.97\u2009\u00b1\u20090.01 vs. 1.05\u2009\u00b1\u20090.015 (5\u2009min), p\u2009=\u20090.005; 0.97\u2009\u00b1\u20090.012 vs. 1.15\u2009\u00b1\u20090.027 (10\u2009min), p\u2009\u2a7d\u20090.001; 0.96\u2009\u00b1\u20090.012 vs. 1.15\u2009\u00b1\u20090.024 (15\u2009min), p\u2009\u2a7d\u20090.001; 0.96\u2009\u00b1\u20090.013 vs. 1.15\u2009\u00b1\u20090.037 (20\u2009min), p\u2009\u2a7d\u20090.001). At an increased pad temperature, the 25CN-NBOH-induced increase in arterial distension was much more pronounced (NBOH 37\u00b0C vs. 41\u00b0C: p\u2009=\u20090.026 (5\u2009min); p\u2009=\u20090.031 (10\u2009min); p\u2009=\u20090.029 (15\u2009min); p\u2009=\u20090.036 (20\u2009min)). For the saline-treated control mice, no such temperature effect could be found (control 37\u00b0C vs. 41\u00b0C: p\u2009=\u20090.93 (5\u2009min); p\u2009=\u20090.85 (10\u2009min); p\u2009=\u20090.92 (15\u2009min); p\u2009=\u20090.99 (20\u2009min)). Mean absolute values of arterial distension for the pre- versus post-injection intervals (given in \u03bcm) are presented in For isoflurane-anaesthetised control animals at both 37\u00b0C and 41\u00b0C pad temperatures \u2009=\u200965.76, p\u2009\u2a7d\u20090.001). Furthermore, a significant time\u2009\u00d7\u2009group interaction \u2009=\u20094.59, p\u2009\u2a7d\u20090.001) and a significant time\u2009\u00d7\u2009treatment\u2009\u00d7\u2009temperature interaction \u2009=\u20093.93, p\u2009=\u20090.029) indicated the temporal changes in heart rate differed between both groups in a temperature-dependent manner. Bonferroni-corrected post-hoc comparisons revealed the significant time\u2009\u00d7\u2009group interaction was due to an 25CN-NBOH-induced tachycardia at all four post-injection measurements for the 37\u00b0C condition : 1.05\u2009\u00b1\u20090.018 vs. 1.12\u2009\u00b1\u20090.018 (5\u2009min), p\u2009=\u20090.041; 1.07\u2009\u00b1\u20090.02 vs. 1.18\u2009\u00b1\u20090.027 (10\u2009min), p\u2009\u2a7d\u20090.001; 1.08\u2009\u00b1\u20090.026 vs. 1.19\u2009\u00b1\u20090.031 (15\u2009min), p\u2009=\u20090.01; 1.08\u2009\u00b1\u20090.03 vs. 1.19\u2009\u00b1\u20090.032 (20\u2009min), p\u2009=\u20090.016) and at the first post-injection measurement for the 41\u00b0C condition : 1.07\u2009\u00b1\u20090.016 vs. 1.13\u2009\u00b1\u20090.026 (5\u2009min), p\u2009=\u20090.044). Accordingly, temperature-dependent heart rate differences in 25CN-NBOH-treated animals could be detected at the 15- and 20-minute measurements and as a trend for the 10-minute measurement (NBOH 37\u00b0C vs. 41\u00b0C: p\u2009=\u20090.095 (10\u2009min); p\u2009=\u20090.015; 40\u2009min (15\u2009min): p\u2009=\u20090.029; p\u2009=\u20090.014 (20\u2009min)). Mean absolute values for the pre- versus post-injection intervals (given in bpm) are shown in Isoflurane-anesthetised mice overall exhibited a tendency for an increase of heart rate over time \u2009=\u200947.46, p\u2009\u2a7d\u20090.001). There was a significant main effect group \u2009=\u20098.27, p\u2009=\u20090.007) and a significant time\u2009\u00d7\u2009group interaction \u2009=\u20093.21, p\u2009=\u20090.03). Following up on the time\u2009\u00d7\u2009group interaction, 25CN-NBOH significantly decreased the respiration rate at all four post-injection measurements of the 37\u00b0C condition : 0.96\u2009\u00b1\u20090.041 vs. 0.88\u2009\u00b1\u20090.038 (5\u2009min), p\u2009=\u20090.01; 0.91\u2009\u00b1\u20090.041 vs. 0.78\u2009\u00b1\u20090.053 (10\u2009min), p\u2009=\u20090.014; 0.87\u2009\u00b1\u20090.048 vs. 0.72\u2009\u00b1\u20090.046 (15\u2009min), p\u2009=\u20090.025; 0.87\u2009\u00b1\u20090.051 vs. 0.7\u2009\u00b1\u20090.048 (20\u2009min), p\u2009=\u20090.01), but only as a trend at the 5-minute post-injection measurement of the 41\u00b0C condition (0.94\u2009\u00b1\u20090.015 vs. 0.86\u2009\u00b1\u20090.025 (5\u2009min), p\u2009=\u20090.073). Mean absolute values for the pre- versus post-injection intervals (given in brpm) are listed in Isoflurane-anesthetised mice overall exhibited a tendency for a decrease of respiration rate over time \u2009=\u20093.24, p\u2009=\u20090.05) (group and time\u2009\u00d7\u2009group (\u00d7 temperature) interactions turned out insignificant, indicating that blood oxygenation was not affected by 25CN-NBOH or its interaction with the pad temperature. Mean absolute values for the pre- versus post-injection intervals (given in % saturation) are presented in Overall, there was a slight tendency for blood oxygenation to decrease during anaesthesia, as implied by a significant main effect \u2009=\u20090.05) . Main efn\u2009=\u20096\u20139 per group), the core body temperature was quantified via a rectal probe. Over the 40-minute observation period, the rectal temperature was noted to slightly increase across study groups \u2009=\u200936.53, p\u2009\u2a7d\u20090.001). Time\u2009\u00d7\u2009treatment interaction likewise was significant \u2009=\u20099.13, p\u2009=\u20090.006), with a marginal contribution from pad temperature \u2009=\u20091.85, p\u2009=\u20090.095). Follow-up analysis revealed the time\u2009\u00d7\u2009group interaction was driven by 25-NBOH favouring body warming during the last intervals of recording at 42\u00b0C : 1.006\u2009\u00b1\u20090.0019 vs. 1.014\u2009\u00b1\u20090.005 (16\u2009min), 1.0053\u2009\u00b1\u20090.003 vs. 1.014\u2009\u00b1\u20090.005 (18\u2009min), and 1.005\u2009\u00b1\u20090.002 vs. 1.02\u2009\u00b1\u20090.005 (20\u2009min), each p\u2009\u2a7d\u20090.05)  . Mean abime, F1, 5\u2009=\u200936.532AR agonist 25CN-NBOH and investigated its effect on the parameters of neck-arterial blood flow.Serotonin secreted into the blood stream is a major tissue hormone with a variety of actions on the cardiovascular system and, when released from the brain stem\u2019s raphe nuclei, also mediates the neuronal regulation of blood pressure . Assumin2AR-related vasoconstriction in the cutaneous bed, which interferes with heat dissipation  dynamic characteristics for psychedelia.In summary, our results show that 25CN-NBOH induces a temperature-dependant increase in heart rate, a decrease in respiration rate and an increase in arterial blood flow, as measured by pulse oximetry drawn from brain-supplying (most likely carotid) arteries. At present, 25CN-NBOH is the most selective 5-HTeceptors . Given t"}
{"text": "Trypanosoma. While the common cap\u20100 (m7GpppN) shows a rather simple methylation pattern, the Trypanosoma cap\u20104 displays seven distinguished additional methylations within the first four nucleotides. The study of essential biological functions mediated by these unique structural features of the cap\u20104 and thereby of the metabolism of an important class of human pathogenic parasites is hindered by the lack of reliable preparation methods. Herein we describe the synthesis of custom\u2010made nucleoside phosphoramidite building blocks for m62Am and m3Um, their incorporation into short RNAs, the efficient construction of the 5\u2032\u2010to\u20105\u2032 triphosphate bridge to guanosine by using a solid\u2010phase approach, the selective enzymatic methylation at position N7 of the inverted guanosine, and enzymatic ligation to generate trypanosomatid mRNAs of up to 40 nucleotides in length. This study introduces a reliable synthetic strategy to the much\u2010needed cap\u20104 RNA probes for integrated structural biology studies, using a combination of chemical and enzymatic steps.Eukaryotic mRNAs possess 5\u2032 caps that are determinants for their function. A structural characteristic of 5\u2032 caps is methylation, with this feature already present in early eukaryotes such as  Highly methylated mRNA caps are encountered in Trypanosoma. A solid\u2010phase\u2010based chemoenzymatic approach makes these RNAs synthetically accessible, thereby facilitating the study of the metabolism of, and essential biological functions mediated by these unique structural features found in this important class of human pathogenic parasites. This is an essential step for export out of the nucleus.Posttranscriptional processing adds another layer of information to RNA. This affects mRNA splicing,Our growing understanding of the functionality of 5\u2032 caps and the consequences of disrupting cap\u2010dependent biochemical processes that result in severe medical disorders make 5\u2032 caps attractive for the development of novel pharmaceutic and therapeutic approaches.7GpppN), which is typically for lower eukaryotes, cap\u20101 (m7GpppNm) and cap\u20102 (m7GpppNmNm), which are typically for higher eukaryotes.O\u2010methyl group. Recent studies have shown that 2\u2032\u2010O\u2010methylations play a key role in cellular discrimination of endogenous from pathogenic RNA.Trypanosomatidae family from the Trypanosomatida order and the Kinetoplastida class.Significant structural diversity is encountered for mRNA 5\u2032 caps. The most common caps in eukaryotes are cap\u20100 (mp\u2010(m62Am)(Am)(Cm)(m3Um)) first by the phosphoramidite solid\u2010phase method. The 5\u2032\u2010phosphorylated tetranucleotide was then chemically coupled with m7GDP to yield the cap\u20104 structure.Trypanosoma cruzi trans\u2010spliced leader (SL) RNA of a specific 39\u2010nucleotide (nt) sequence that harbors the unique hypermethylated cap\u20104 structure.The study of essential biological functions mediated by these unique structural features of cap\u20104 and thereby of the metabolism of an important class of human pathogenic parasites is hindered by the lack of reliable preparation methods. To the best of our knowledge, only the chemical synthesis of the terminal four\u2010nucleotide fragment of cap\u20104 has been published thus far. This was accomplished by obtaining the tetranucleotide fragment  in pyridine. Finally, phosphitylation was executed with 2\u2010cyanoethyl\u2010N,N\u2010diisopropylchlorophosphoramidite (CEP\u2010Cl) in the presence of N,N\u2010diisopropylethylamine (DIPEA). Starting from nucleoside 1, our route provides phosphoramidite 3 with 45\u2009% overall yield in three transformations involving two chromatographic purifications; in total, 0.85\u2005g of compound 3 was prepared over the course of this study.The functionalization of commercially available 2\u2032\u2010O\u2010methyladenosine 4 into the desired m6Am phosphoramidite 9 involved six reactions, which are summarized in Scheme\u20055 with N,N\u2032\u2010bis[(dimethylamino)methylene]hydrazine (BDMAMH) dihydrochlorided\u2010ribofuranosyl)\u20106\u2010purine 6, which was converted quantitatively into N,N,2\u2032\u2010O\u2010trimethyladenosine 7 with ethanolic dimethylamine. Compound 7 was tritylated to give compound 8, and finally phosphitylated with CEP\u2010Cl in the presence of DIPEA. Starting from nucleoside 4, our route provides phosphoramidite 9 in 46\u2009% overall yield over five steps involving five chromatographic purifications; in total, 0.75\u2005g of compound 9 was prepared during the course of this study.The functionalization of commercially available 2\u2032\u2010O\u2010pivaloyloxymethyl (PivOM)\u2010protected nucleoside phosphoramidites, we optimized our protocol for the implementation of standard 2\u2032\u2010O\u2010tert\u2010butyldimethylsilyl (TBDMS) and/or 2\u2032\u2010O\u2010[(triisopropylsilyl)oxy]methyl (TOM) phosphoramidites  methyltransferase) following a protocol previously established by us  and S\u2010ribosyl homocysteine lyase (LuxS) were added to the reaction mixture to enzymatically degrade the byproduct S\u2010adenosylhomocysteine, which is a strong inhibitor of methyltransferases.The N7\u2010methyl group was efficiently enzymatically added by means of the methyltransferase Ecm1 (Am)(Cm)(m3Um) synthetic oligonucleotide.We developed a practical route toward hypermethylated cap\u20104 RNAs. This included the three\u2010 and five\u2010step syntheses of mO\u2010\u20102\u2032\u2010O\u2010methyl\u20103\u2010N\u2010methyluridine (2)5\u2032\u2010: 2\u2032\u2010O\u2010Methyluridine (1)  was dissolved in dry dimethyl sulfoxide (2\u2005mL). Sodium hydride  was added to the reaction mixture and stirred at room temperature under argon atmosphere until bubbling stopped. Then, methyl iodide  was added dropwise. The solution was stirred for another 5\u2005h. All volatiles were evaporated under high vacuum. The residue was co\u2010evaporated once with methanol and twice with pyridine before it was dissolved in anhydrous pyridine (1\u2005mL). Dimethoxytrityl chloride  and 4\u2010dimethylaminopyridine  were added. The reaction solution was stirred under argon at room temperature overnight before the reaction was quenched by adding methanol. All volatiles were evaporated, the residue was diluted in methylene chloride and was washed three times with a solution of 5\u2009% citric acid, once with a saturated sodium bicarbonate solution, and once with a saturated sodium chloride solution. The product was isolated after column chromatography (100:0.1 to 100:0.5 methylene chloride/methanol). Yield: 0.24\u2005g (54\u2009%) of 2 as white foam. 1H\u2005NMR : \u03b4=3.15 , 3.24\u20133.36 ), 3.44 ), 3.75 ), 3.80\u20133.58 ), 3.94\u20134.00 ), 4.19\u20134.255 ), 5.22 ), 5.39 ), 5.84 ), 6.90 ), 7.21\u2013737 ), 7.80\u2005ppm ); 13C\u2005NMR : \u03b4=27.3 , 55.0 ), 58.0 ), 62.3 (C(5\u2032)), 68.4 ), 82.4 ), 82.8 ), 88.7 ), 100.5 ), 113.4 ), 127.0 ), 127.61 ), 127.80 ), 129.9 , 138.4 ); HRMS (ESI) m/z calcd: 597.2207 [M+Na]+; found: 597.2219.O\u2010Dimethoxytrityl\u20102\u2032\u2010O\u2010methyl\u20103\u2010N\u2010methyluridine\u20103\u2032\u2010(2\u2010cyanoethyl\u2010diisopropylphosporamidite) (3)5\u2032\u2010: Compound 2  was dried under high vacuum and vented with argon. The solid was dissolved in dry methylene chloride (6\u2005mL) and treated with N,N\u2010diisopropylethylamine  and 2\u2010cyanoethyl\u2010N,N\u2010diisopropyl\u2010chlorophosphoramidite . The reaction solution was stirred for 4\u2005h at room temperature. Afterward, the reaction was quenched by adding 1\u2005mL of methanol. It then was diluted with methylene chloride (1:10), washed with saturated sodium bicarbonate solution and with a saturated sodium chloride solution. The product was isolated by column chromatography . Yield: 0.27\u2005g (84\u2009%) of 3 as white foam. 1H\u2005NMR : \u03b4=0.96 , 1.08\u20131.12 , 2.33 , 2.57 , 3.25 , 3.35\u20133.6 , NCH\u2010(CH3)2, PO\u2010CH), 3.53 ), 3.73 ), 3.68\u20133.71 ), 4.15\u20134.19 ), 4.36\u20134.42 ), 4.51\u20134.56 ), 5.21\u20135.26 ), 5.93\u20135.97 ), 6.74\u20136.79 ), 7.16\u20137.35 ), 7.88\u20137.99\u2005ppm ); 31P\u2005NMR : \u03b4=150.17; 150.73\u2005ppm; HRMS (ESI): m/z calcd: 775.3466 [M+H]+; found: 775.3472.O\u2010methyladenosine (5)3\u2032,5\u2032\u2010Diacetyl\u20102\u2032\u2010: 2\u2032\u2010O\u2010Methyladenosine  was co\u2010evaporated with pyridine, before dimethylformamide (1.4\u2005mL), dry pyridine (0.7\u2005mL), acetic anhydride  and 4\u2010dimethylaminopyridine  were added. The reaction solution was stirred at 0\u2009\u00b0C for 3\u2005hours. The reaction progress was controlled by TLC (5\u2009% methanol in methylene chloride). Methanol (0.5\u2005mL) was added to quench the reaction. Then all volatiles were removed by distillation under high vacuum (70\u2009\u00b0C) before the residue was co\u2010evaporated once with pyridine and three times with toluene. This crude product was directly used for the next reaction. For analytical analysis the product was further purified by column chromatography (1\u2009% methanol in methylene chloride). Yield: 0.64\u2005g (98\u2009%) of 5 as white solid. 1H\u2005NMR : \u03b4=2.04, 2.14 CO\u2010CH3, O(3\u2032)CO\u2010CH3)), 3.28 ), 4.21\u20134.38 \u2010H, Ha,b\u2010C(5\u2032)), 4.88 ), 5.49\u20135.51 ), 6.03 ), 7.34 , 8.16  or H\u2010C(2)), 8.38\u2005ppm  or H\u2010C(8)); 13C\u2005NMR : \u03b4=20.9, 21.0 \u2010CO\u2010CH3, O(3\u2032)\u2010CO\u2010CH3), 59.5 ), 63.2 ), 80.3 ), 81.2 ), 87.7 ), 139.5  or C(2)), 153.5\u2005ppm  or C(8)); HRMS (ESI): m/z calcd: 366.1408 [M+H]+; found: 366.1414.O\u2010methylfuranosyl)\u20106\u2010purine (6)9\u2010 was co\u2010evaporated with pyridine and treated with N,N\u2010bis[(dimethylamino)methylene]hydrazine dihydrochloride . Yield: 0.47\u2005g (76\u2009%) of 6 as white foam. 1H\u2005NMR : \u03b4=2.05, 2.16 , H3C\u2010CO\u2010OO(3\u2032)), 3.31 ), 4.28\u20134.44 , Ha,b\u2010C(5\u2032)), 4.92 ), 5.53\u20135.56 ), 6.24 ), 7.34 , 8.96  or H\u2010C(2)), 9.03 or H\u2010C(8)), 9.63\u2005ppm ; 13C\u2005NMR : \u03b4=21.16, 21.19 \u2010CO\u2010CH3, O(3\u2032)\u2010CO\u2010CH3), 59.0 ), 63.7 ), 71.3 ), 80.4 ), 80.8 ), 86.8 ), 141.9 , 146.8  or C(8)), 152.8\u2005ppm  or C(2)); HRMS (ESI): m/z calcd: 418.1470 [M+H]+; found: 418.1475.N6\u2010\u2010Dimethyl)\u20102\u2032\u2010: Compound 6  was suspended in 33\u2009% dimethylamine solution in ethanol (3\u2005mL) and stirred under argon atmosphere at room temperature for 48\u2005h. During that time, the white suspension turned into a clear solution. All volatiles were removed under vacuum. Further processing was done without further purification. For analytical reasons the crude product was purified by column chromatography . Yield: 0.34\u2005g (98\u2009%) of 7 as white foam. 1H\u2005NMR : \u03b4=3.31 ), 3.46 2\u2010N), 3.53\u20133.71 , Ha,b\u2010C(5\u2032)), 3.98 ), 4.33\u20134.34 , H\u2010O(5\u2032)), 5.24 ), 5.33\u2013537 ), 6.03 ), 8.22  or H\u2010C(2)), 8.40\u2005ppm  or H\u2010C(8)); 13C\u2005NMR : \u03b4=37.8 , 57.4 ), 61.3 ), 68.7 ), 82.4 ), 85.6 ), 86.3 ), 138.3  or C(8)), 151.9\u2005ppm  or C(2)); HRMS (ESI): m/z calcd: 310.1510 [M+H]+; found: 310.1515.O\u2010Dimethoxytrityl\u20106\u2010\u2010dimethyl)\u20102\u2032\u2010: Compound 7  together with 4\u2010(dimethylamino)\u2010pyridine  were co\u2010evaporated with pyridine. The residue was diluted in dry pyridine (8\u2005mL). 4,4\u2032\u2010O\u2010Dimethoxytrityl chloride  was dried for 2\u2005h on high vacuum before it was added to the reaction solution, and the mixture was stirred overnight at room temperature together with molecular sieves under argon atmosphere. The reaction was quenched with methanol (0.5\u2005mL) before all volatiles were removed under reduced pressure. The residue was co\u2010evaporated three times with toluene. Afterward the product was purified by column chromatography . Another column chromatography (12\u201325\u2009% acetone in toluene) can be necessary to further improve purity. Yield: 0.382\u2005g (81\u2009%) of 8 as white foam. 1H\u2005NMR : \u03b4=3.20 \u2010Ha,b), 3.31\u20133.59 , 3.73 ), 4.06 ), 4.41 , H\u2010C(2\u2032)), 5.25 ), 6.06 ), 6.78\u20136.88 ), 7.16\u20137.40 ), 8.18  or H\u2010C(2)), 8.26\u2005ppm  or H\u2010C(8)); 13C\u2005NMR : \u03b4=38.8 , 55.5 ), 59.3 ), 63.4 ), 70.1 ), 83.5 ), 83.9 ), 86.6 ), 113.4 ), 127.0 ), 128.1 ), 128.4 ), 130.4 ), 136.0  or C(8)), 152.8\u2005ppm  or C(2)); HRMS (ESI): m/z calcd: 612.2817 [M+H]+; found: 612.2822.O\u2010Dimethoxytrityl\u20106\u2010\u2010N\u2010dimethyl)\u20102\u2032\u2010,N\u2010diisopropylphosphoramidite) (9): Compound 8  was dried under high vacuum for several hours and ventilated with argon. The solid was dissolved in dry methylene chloride (10\u2005mL), and treated with N,N\u2010diisopropylethylamine  and 2\u2010cyanoethyl N,N\u2010diisopropylchlorophosphoramidite . The reaction solution was stirred under argon atmosphere for 3.5\u2005hours at room temperature. Then methanol (2\u2005mL) was added and the solution was stirred for another 20\u2005minutes. The solution was diluted with methylene chloride (1:10) and washed with saturated sodium bicarbonate solution and saturated sodium chloride solution. The product was isolated by column chromatography . Yield: 551\u2005mg (77\u2009%) of white foam. 1H\u2005NMR : \u03b4=1.06\u20131.07 2), 1.19\u20131.22 2), 2.38\u20132.40 , 2.65\u20132.68 , 3.31\u20133.35 ), 3.48\u20133.69 , H3C\u2010O(2\u2032), N\u2010(CH3)2, N\u2010CH, P\u2010O\u2010CH2), 3.80\u20133.79 ), 3.87\u20133.98 (mP\u2010O\u2010CH2\u2010), 4.33\u20134.39 ), 4.55\u20134.67 ), H\u2010C(3\u2032)), 6.13\u20136.15 ), 6.80\u20136.84 ), 7.20\u20137.35 ), 7.44\u20137.47 ), 7.92\u20137.97  or H\u2010C(2)), 8.30\u20138.28\u2005ppm  or H\u2010C(8)); 31P\u2005NMR : \u03b4=150.21, 150.91\u2005ppm; HRMS (ESI): m/z calcd: 812.3895 [M+H]+; found: 812.3901.N,N\u2010bis[(Dimethylamino)methylene]hydrazine dihydrochloride:1H\u2005NMR : \u03b4=3.00 , 8.36\u2005ppm .Guanosine 5\u2032\u2010diphosphate di\u2010tributylammonium salt: DOWEX\u201050WX8 200\u2013400 resin (H+ form) was filtered with nanopure water using a glass frit (pore size 16\u201340\u2005\u03bcm) to remove small particles. Afterward, guanosine 5\u2032\u2010diphosphate disodium salt  was dissolved in water (4\u2005mL) and eluted through a column  packed with 2\u2005cm of wet DOWEX\u201050WX8 200\u2013400 for 10\u2005minutes. After filtration into a flask with 25\u2005mL ethanol at 0\u2009\u00b0C, tributylamine  was added. The solution was stirred while the column was rinsed with water until pH was about 7\u20138 before all volatiles were removed under high vacuum. To preserve a dry powder further co\u2010evaporations (three times with ethanol and two times with dioxane) were performed. The resulting white solid was directly used without further purifications. Yield: 0.70\u2005g (86\u2009%) of a white solid. 1H\u2005NMR : \u03b4=0.89 , 1.29 , 1.55 , 2.86 , 3.92\u20134.05 , H2\u2010C(5\u2032)), 4.27 ), 4.47 ), 5.68 ), 6.62 , 7.89 ), 10.6\u2005ppm ; 31P\u2005NMR : \u03b4=\u221210.20 (d), \u221210.85\u2005ppm (d).RNA solid\u2010phase synthesis: All RNAs were assembled on an ABI392 synthesizer using 2\u2032\u2010O\u2010TOM nucleoside phosphoramidites (ChemGenes Corporation) and CPG supports (2\u2032\u2010tBDSilyl Guanosine (n\u2010PAC) 3\u2032\u2010lcaa CPG 1000\u2005\u00c5, 2\u2032\u2010tBDSilyl Adenosine (n\u2010PAC) 3\u2032\u2010lcaa CPG 1000\u2005\u00c5, \u224840\u2005\u03bcmol\u2009g\u22121 ChemGenes Corporation). Standard RNA synthesis cycle: detritylation (120\u2005s) with dichloroacetic acid/1,2\u2010dichloroethane (4:96); coupling (2.0\u2005min) with phosphoramidites/acetonitrile (0.1\u2009m) and benzylthiotetrazole/acetonitrile (0.3\u2009m); capping  with Cap A: 4\u2010(dimethylamino)pyridine in acetonitrile (0.5\u2009m) and Cap B: acetic anhydride/sym\u2010collidine/acetonitrile (2:3:5); oxidation (1.0\u2005min) with iodine (20\u2005mm) in tetrahydrofuran (THF)/pyridine/H2O (35:10:5). Commercially available modified nucleoside building blocks: 2\u2032\u2010O\u2010methyl adenosine and 2\u2032\u2010O\u2010methyl cytidine (ChemGenes Corporation), were incorporated using modified synthesis cycles with longer coupling times (6\u2005min).RNA phosphitylation, hydrolysis, oxidative amidation was performed in analogy to ref.\u2005m aqueous triethylammonium bicarbonate, 5\u2005mL water and 4\u2005mL acetonitrile) over a period of 5\u2005min. This treatment was repeated four times. The solid support was then rinsed with 20\u2005mL of acetonitrile before being dried under vacuum for several hours. Oxidative amidation was done by incubation with 0.5\u2005mL of a solution containing 600\u2005mg imidazole, 2\u2005mL N,O\u2010bis(trimethylsilyl)acetamide, 4\u2005mL anhydrous acetonitrile, 4\u2005mL bromotrichloromethane and 0.4\u2005mL trimethylamine for 30\u2005min. This treatment was repeated four times. The solid support was intensively rinsed with dry acetonitrile. Finally, Gpp attachment was achieved by application of 0.5\u2005mL of coupling solution  over 8\u2005h at room temperature. This treatment was repeated three times.Gppp\u2010capped RNA deprotection: The solid supports with the Gppp\u2010capped and otherwise fully protected oligos were rinsed with DBU in acetonitrile , then washed with acetonitrile and dried. Cleavage from the support and base deprotection was effected by treating the solid support with a 1:1 mixture of 40\u2009% aqueous methylamine and 30\u2009% aqueous ammonia (AMA) in a screw\u2010cap vial for 2\u2005h at 40\u2009\u00b0C. The resulting suspensions were filtered and the filtrates dried. Removal of 2\u2032\u2010O silyl protecting groups was carried out with of 1\u2009m tetrabutylammonium fluoride trihydrate in THF (1\u2005mL) for 6\u2005h at 40\u2009\u00b0C. The reaction was quenched by the addition of 1\u2009m triethylammonium acetate solution  and then concentrated to approximately 1\u2005mL. This viscous solution was desalted by size exclusion chromatography on a HiPrep 26/10 Sephadex G25 column . The crude products were evaporated and re\u2010dissolved in water (1\u2005mL). Quality assessment of the crude Gppp\u2010capped RNAs via anion\u2010exchange HPLC on a Dionex DNAPac PA\u2010100 column (4\u00d7250\u2005mm); conditions: flow 1\u2005mL\u2009min\u22121; eluent A: 25\u2005mm Tris hydrochloride, 6\u2009m urea, pH\u20058.0, eluent B: 500\u2005mm sodium perchlorate, 25\u2005mm Tris hydrochloride, 6\u2009m urea, pH\u20058.0; gradient: 0\u201360\u2009% B in 45\u2005minutes; temperature: 40\u2009\u00b0C, UV detection at 260\u2005nm. The Gppp\u2010capped RNAs were isolated by anion\u2010exchange HPLC on a Dionex DNAPac PA\u2010100 column (4\u00d7250\u2005mm); Conditions: flow 1\u2005mL\u2009min\u22121; eluents: see above; temperature 40\u2009\u00b0C; UV detection at 260\u2005nm. The product fractions were diluted with an equal amount of triethylammonium bicarbonate buffer  and loaded onto equilibrated C18 Sep\u2010Pak (Waters Corporation). The cartridge was washed with water and the RNA was eluted with acetonitrile/water (1:1). All volatiles were evaporated and the residue re\u2010dissolved in water (1\u2005mL). Yields were determined UV photometrically. The quality of the product was analyzed via anion\u2010exchange HPLC as described above and by reversed\u2010phase LC\u2013ESI\u2010MS.Enzymatic N7 methylation of Gppp\u2010RNA: The enzymatic transformation was conducted in analogy to refs.\u200510 (4\u2005nmol) was dissolved in buffer  followed by the addition of an aqueous solution of S\u2010adenosylmethionine , and the addition of water to obtain a total volume of 68.8\u2005\u03bcL. To the mixed solution, enzymes were added successively ). The mixture was incubated for 45\u2005min at 37\u2009\u00b0C. The solution was extracted twice with an equal volume of chloroform/isoamyl alcohol solution . The organic layers were rewashed twice with an equal volume of water. The aqueous layers were combined and lyophilized, to eliminate remaining organic solvents. Analysis of the methylation reaction and purification of the product was performed by anion\u2010exchange chromatography (conditions see above). The integrity of the product was confirmed by LC\u2013ESI mass spectrometry (conditions see below).Enzymatic ligation of cap\u20104 RNA. The 38\u2010nt T.\u2005cruzi cap\u20104 RNA was prepared by splinted enzymatic ligation of an 11\u2010nt cap\u20104 RNA and a chemically synthesized 5\u2032\u2010phosphorylated 27\u2010nt RNA by using T4 DNA ligase (Thermo Fisher) in analogy to ref.\u2005m of RNA fragment 10 (8\u2005nmol), 12.5\u2005\u03bcm of RNA fragment 11 (10\u2005nmol), and 12.5\u2005\u03bcm of a 20\u2010nt DNA splint oligonucleotide  were heated at 70\u2009\u00b0C for 2\u2005min and passively cooled to room temperature. Afterward water was added up to a total volume of 560\u2005\u03bcL before 10\u00d7 ligation buffer  and PEG  was added. T4 DNA ligase  was added to a final concentration of 0.5\u2005U\u2009\u03bcL\u22121 in a total volume of 0.8\u2005mL before the mixture was incubated for 2\u2005h at 37\u2009\u00b0C. Ligation was stopped by chloroform/isoamyl alcohol  extraction. After lyophilization and re\u2010dissolving, analysis of the ligation reaction and purification of the ligation products were performed by anion\u2010exchange chromatography (conditions see above). The integrity of product was confirmed by LC\u2013ESI mass spectrometry (conditions see below).Mass spectrometry of cap\u20104 RNA. All experiments were performed on a Finnigan LCQ Advantage MAX ion trap instrument connected to a Thermo Fisher Ultimate 3000 system. RNA sequences were analyzed in negative\u2010ion mode with a potential of \u22124\u2005kV applied to the spray needle. LC: sample , column  at 21\u2009\u00b0C; flow rate: 0.1\u2005mL\u2009min\u22121; eluent A: Et3N (8.6\u2005mm), 1,1,1,3,3,3\u2010hexafluoroisopropanol (100\u2005mm) in H2O (pH\u20058.0); eluent B: MeOH; gradient: 0\u2013100\u2009% B in A within 20\u2005min; UV detection at 254\u2005nm.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "In this paper,The corrected footnote for Table 2 is as follows:Solution 1:1000\u2009mL volume; 20\u2009mg/1000\u2009mL concentration.Solution 2:100\u2009mL volume; 20\u2009mg/100\u2009mL concentration."}
{"text": "N,N-di\u00admethyl\u00adformamide mol\u00adecules are linked to the cations by C\u2014H\u22efO contacts.In the crystal, each cation is connected to two anions by N\u2014H\u22ef Br hydrogen bonds, forming an  17H18N3S+\u00b7Br\u2212\u00b7C3H7NO, the central thia\u00adzolidine ring adopts an envelope conformation with puckering parameters Q(2) = 0.310\u2005(3)\u2005\u00c5 and \u03c6(2) = 42.2\u2005(6)\u00b0. In the crystal, each cation is connected to two anions by N\u2014H\u22ef Br hydrogen bonds, forming an R42(8) motif parallel to the , C\u22efH/H\u22efC (17.9%) and Br\u22efH/H\u22efBr (7.0%) inter\u00adactions, as concluded from a Hirshfeld analysis.In the cation of the title salt, C The C=N double bond [N1=C4 = 1.272\u2005(4)\u2005\u00c5] is in a Z configuration. The dihedral angle between the mean planes of the benzene (C5\u2013C10) and phenyl (C12\u2013C17) rings is 83.95\u2005(18)\u00b0 and they make dihedral angles of 16.60\u2005(17) and 87.42\u2005(17)\u00b0, respectively, with the mean plane of the thia\u00adzolidine ring. The N2\u2014N1\u2014C4\u2014C5 bridge that links the thia\u00adzolidine and 4-methyl\u00adbenzene rings has a torsion angle of \u2212176.8\u2005(3)\u00b0.As shown in Fig.\u00a01N,N-di\u00admethyl\u00adformamide mol\u00adecules are linked to the cations by C\u2014H\u22efO contacts  shows the 2D fingerprint plot of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode while those delineated into H\u22efH, C\u22efH/H\u22efC and Br\u22efH/H\u22efBr contacts are given in Fig.\u00a07b\u2013d, respectively. The most significant inter\u00admolecular inter\u00adactions are the H\u22efH inter\u00adactions (55.6%) . The reciprocal C\u22efH/H\u22efC inter\u00adactions appear as two symmetrical broad wings with de + di \u2243 2.6\u2005\u00c5 and contribute 17.9% to the Hirshfeld surface . The reciprocal Br\u22efH/H\u22efBr inter\u00adaction with a 7.0% contribution is seen as branch of sharp symmetrical spikes at diagonal axes de + di \u2243 2.2\u2005\u00c5 . Furthermore, there are also O\u22efH/H\u22efO (3.2%), S\u22efH/H\u22efS (4.6%), N\u22efC/C\u22efN (3.8%), N\u22efH/H\u22efN (2.9%), S\u22efC/C\u22efS (2.4%), C\u22efC (1.5%), Br\u22efC/C\u22efBr (0.2%), Br\u22efS/S\u22efBr (0.2%), N\u22efN (0.4%) and N\u22efS/S\u22efN (0.5%) contacts  Fig.\u00a07b. The rce Fig.\u00a07c. The r\u2005\u00c5 Fig.\u00a07d. Furths Table\u00a03.et al., 2016et al., 1994et al., 1994et al., 1994et al., 1993aet al., 1993bet al., 1995et al., 1994p-toluene\u00adsulfonate. In all three structures, the most disordered fragment of these mol\u00adecules is the asymmetric C atom and the Cl atom attached to it. The disorder of the cation in the racemate corresponds to the presence of both enanti\u00adomers at each site in the ratio 0.821\u2005(3):0.179\u2005(3). The system of hydrogen bonds connecting two cations and two anions into 12-membered rings is identical in the racemic and in the optically active crystals. YITCEJ  contacts also contribute to the mol\u00adecular packing. In the crystal of ZIJQAN, the cations, anions and water mol\u00adecules are linked into a three-dimensional network, which forms cross layers parallel to the (120) and  in ethanol (20\u2005ml) was added 4-methyl\u00adbenzaldehyde (1\u2005mmol). The mixture was refluxed for 2\u2005h and then cooled. The reaction product precipitated from the reaction mixture as colorless crystals, was collected by filtration, washed with cold acetone , and recrystallized from di\u00admethyl\u00adformamide to obtain single crystals.1H NMR  : 2.33 ; 4.55 ; 4,88 ; 5.60 ; 7.28\u20137.98 ; 8.41 ; 10.33 . 13C NMR : 21.27; 45.36; 55.90; 127.79; 128.69; 128.86; 129.09; 129.46; 130.21; 137.50; 141.68; 151.04; 167.50. MS (ESI), m/z: 296.40 [C17H18N3S]+ and 79.88 Br\u2212.Uiso(H) = 1.2 or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020012712/jy2001sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012712/jy2001Isup2.hklStructure factors: contains datablock(s) I. DOI: 1837125CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, corrugated layers of mol\u00adecules extending along the ab plane are generated by C\u2014H\u22efO hydrogen bonds. The inter\u00admolecular inter\u00adactions were qu\u00adanti\u00adfied by Hirshfeld surface analysis and two-dimensional fingerprint plots. The most significant contributions to the crystal packing are from H\u22efH (42.3%), H\u22efO/O\u22efH (34.5%) and H\u22efC/ C\u22efH (17.6%) contacts. Mol\u00adecular orbital calculations providing electron-density plots of the HOMO and LUMO as well as mol\u00adecular electrostatic potentials (MEP) were computed, both with the DFT/B3LYP/6\u2013311\u2005G++ basis set. A mol\u00adecular docking study between the title mol\u00adecule and the COVID-19 main protease (PDB ID: 6LU7) was performed, showing that it is a good agent because of its affinity and ability to adhere to the active sites of the protein.In the mol\u00adecular structure of the title compound, C The C14 atom is at the envelope flap position, and it deviates from the least-square plane through the remaining four atoms by 0.070\u2005(2)\u2005\u00c5. The other oxazolidine ring (N3/O7/C18\u2013C20) has a twisted conformation along the C20\u2014C19 bond, with puckering parameters Q(2) = 0.1732\u2005(18)\u2005\u00c5 and \u03c6(2) = 299.7\u2005(6)\u00b0. The dihedral angles between the mean planes of the oxazolidine rings and the quinoline ring systems are 38.04\u2005(9)\u00b0 for (N2/O2/C12\u2013C14) and 57.34\u2005(8)\u00b0 for (N3/O7/C18\u2013C20). The mol\u00adecular conformation is stabilized by an intra\u00admolecular C20\u2014H20B\u22efO4 contact  ring motif.In the title mol\u00adecule Fig.\u00a01, the phect Fig.\u00a01, produciA\u22efO3i and C17\u2014H17A\u22efO6ii hydrogen bonds between methyl\u00adene groups and carbonyl O atoms as well as C19\u2014H19B\u22efO3iii hydrogen bonds lead to the formation of corrugated layers extending parallel to (001)  Fig.\u00a02. Notableet al., 2016et al., 2015et al., 2015et al., 2019bS(6) ring. In the crystal structure, inversion dimers linked by pairs of weak C\u2014H\u22efO inter\u00adactions generate R22(6) loops. In UHUHAI, the two rings of the quinoline system have a dihedral angle of 2.28\u2005(8)\u00b0 between their mean planes. The plane of the attached benzene ring is inclined to the plane of the quinoline system by 7.65\u2005(7)\u00b0. There is a short intra\u00admolecular C\u2014H\u22efO contact involving the carbonyl group. In XOFGAD, the mol\u00adecule is essentially planar with the mean plane of the ethyl acetate group making a dihedral angle of 5.02\u2005(3)\u00b0 with the ethyl 6-chloro-2-eth\u00adoxy\u00adquinoline mean plane. There is an intra\u00admolecular C\u2014 H\u22efO hydrogen bond forming an S(6) graph-set motif. Weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are observed in this crystal structure.A search of the Cambridge Structural Database  to 1.1337 (blue) a.u. . The pale-red spots symbolize short contacts and negative dnorm values on the surface and correspond to the C\u2014H\u22efO inter\u00adactions (Table\u00a01b). The convex blue regions symbolize hydrogen-donor groups and the concave red regions hydrogen-acceptor groups. The absence of adjacent red and blue triangles in the shape-index map, which generally indicate \u03c0\u2013\u03c0 inter\u00adactions, reveals that this kind of inter\u00adaction is not present in the title compound. The curvedness map was generated in the range \u22124.0 to 4.0\u2005\u00c5 . It shows large regions of green with a relatively flat (i.e. planar) surface area while the blue regions demonstrate areas of curvature. The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a04a, with those delineated into H\u22efH, H\u22efO/O\u22efH, H\u22efC/ C\u22efH, H\u22efN/N\u22efH and C\u22efN/N\u22efC contacts associated with their relative contributions to the Hirshfeld surface given in Fig.\u00a04a\u2013f, respectively. The most important inter\u00admolecular inter\u00adactions are H\u22efH, contributing 42.3% to the overall crystal packing. H\u22efO/O\u22efH contacts arising from inter\u00admolecular C\u2014H\u22efO hydrogen bonding . The pair of wings in the fingerprint plot delineated into H\u22efC/ C\u22efH contacts (17.6% contribution to the Hirshfeld surface) have a nearly symmetrical distribution of points, with the tips at de + di \u223c2.54\u2005\u00c5. The contributions of the other contacts to the Hirshfeld surface are negligible, i.e. H\u22efN/N\u22efH of 2.0% and C\u22efN/N\u22efC of 1.2%.Hirshfeld surface analysis was used to qu\u00adantify the inter\u00admolecular contacts of the title compound, using u. Fig.\u00a03a. The ps Table\u00a01. The shas Table\u00a01b. The c\u2005\u00c5 Fig.\u00a03c. It shg Table\u00a01 make a 3\u2005\u00c5 Fig.\u00a04c. The pGAUSSIAN 09  using the standard B3LYP functional and 6\u2013311G++  basis-set calculations  map Fig.\u00a06 was calcet al., 2020PyRx AutoDock Vina Wizard. The inter\u00admolecular inter\u00adactions between the title compound and the target protein were visualized by using the Discovery Studio 2020 Client program  values for nine different poses of the ligand docked onto receptor 6LU7 are listed in Table\u00a03\u22121) energy and nine active hydrogen-bonding sites. The 2D and 3D visuals of the inter\u00admolecular inter\u00adactions for the best binding pose of the title compound docked into macromolecule 6LU7 can be seen in Fig.\u00a07A mol\u00adecular docking study was performed to determine possible inter\u00admolecular inter\u00adactions between the COVID-19 main protease (PDB ID: 6LU7) and the title mol\u00adecule. The crystal structure of COVID-19 main protease in a complex with an inhibitor N3 was taken from the RSCB Protein Data Bank  tetra-n-butyl\u00adammonium bromide (TBAB). The reaction mixture was stirred at 363\u2005K for 9\u2005h in DMF. After removal of formed salts by filtration, DMF was evaporated under reduced pressure, and the residue obtained was dissolved in di\u00adchloro\u00admethane. The organic phase was dried over Na2SO4 and then concentrated in vacuo. The resulting mixture was chromatographed on a silica gel column [eluent: ethyl acetate/hexane (2/8 v/v)]. Colourless single crystals of the title compound were obtained by slow evaporation of an ethanol solution.A solution of 0.8\u2005g (4.23\u2005mmol) of 2-oxo-1,2-di\u00adhydro\u00adquinoline-4-carb\u00adoxy\u00adlic acid in 30\u2005ml of DMF was mixed with 1.5\u2005g (8.46\u2005mmol) bis\u00ad(2-chloro\u00adeth\u00adyl)amine hydro\u00adchloride, 2.33\u2005g  KCrystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020015960/wm5588sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020015960/wm5588Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020015960/wm5588Isup3.cmlSupporting information file. DOI: 2048734CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex with 1,2-bi(4-pyrid\u00adyl)ethane is reported. The Zn cation is coordinated by two N atoms from the 1,2-bi(4-pyrid\u00adyl)ethane unit and four O atoms from two mandelate anions in a slight distorted octa\u00adhedral coordination geometry.The synthesis and characterization of a new mandelato Zn II compound, [Zn(C8H7O3)2(C12H12N2)]n, the Zn cation is coordinated by two N atoms from 1,2-bis\u00ad(pyridin-4-yl)ethane unit and four O atoms from two mandelate [or hy\u00addroxy(phen\u00adyl)acetate] anions in a slightly distorted octa\u00adhedral coordination geometry. The 1,2-bis\u00ad(pyridin-4-yl)ethane unit bridges two ZnII cations, related by an inversion centre, to form a polymeric chain along [110]. The crystal structure features extensive O\u2014H\u22efO and weak C\u2014H \u22efO hydrogen bonds, with C\u2014H \u22ef \u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions also being present. The centroid\u2013centroid distance between the phenyl ring of the mandelate group and the 1,2-bis\u00ad(pyridine-4-yl)ethane moiety is 4.951\u2005(2)\u2005\u00c5. The 1,2-bis\u00ad(pyridin-4-yl)ethane ligand is disordered over two positions, with a refined occupancy of 0.578\u2005(14) for the major component.In the title polymeric Zn There is an inversion centre located at the mid-point of the ethane C\u2014C bond in the 1,2-bis\u00ad(4-pyridin-4-yl)ethane mol\u00adecule. Each ZnII cation is coord\u00adinated by two N atoms from two 1,2-bis\u00ad(4-pyridin-4-yl)ethane mol\u00adecules in a trans arrangement and four O atoms from two mandelate anions in a slightly distorted octa\u00adhedral coordination geometry, as shown in Table\u00a012+ cation form five-membered chelate rings via an oxygen atom of the OH group [Zn\u2014O3 = 2.1013\u2005(15)\u2005\u00c5] and an oxygen atom of the carboxyl group [Zn\u2014O1= 2.0290\u2005(14)\u2005\u00c5]. The ZnII cations are linked together via 1,2-bis\u00ad(4-pyridin-4-yl)ethane bridges, forming a polymeric chain along [110].The asymmetric unit of the title compound comprises one Znii =2.572\u2005(2)\u2005\u00c5] , 3.378\u2005(3), and 3.064\u2005(3)\u2005\u00c5, respectively (Table\u00a02A\u22efCg5iv = 3.781\u2005(2)\u2005\u00c5 and C12\u2032\u2013H12B\u22efCg5ii = 3.649\u2005(8)\u2005\u00c5, Table\u00a02Cg5\u22efCg3iv between the centroids of the phenyl ring (C3\u2013C8) of the mandelate group and of the 1,2-bis\u00ad(pyridine-4-yl)ethane moiety (C9\u2013C13) [symmetry code: (iv) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0The crystal structure features extensive O\u2014H\u22efO hydrogen bonding [O3\u22efO2\u00c5] Fig.\u00a02, establiy Table\u00a02. In addiet al., 2016catena-[[\u03bc-oxido(phen\u00adyl)acetato]\u00adzinc(II) perchlorate monohydrate] (phen\u00adyl)acetato]{\u03bc-4-[2-(pyridin-4-yl)eth\u00adyl]pyridine}\u00adnickel(II)], isostructural with the title compound, has also been reported ethane]\u00adbis\u00ad(2-hy\u00addroxy-2-phenyl\u00adacetato)\u00adzinc(II)] ethane moiety were found in the Cambridge Structural Database 2 , 1,2-bi(4-pyrid\u00adyl)ethane  and mandelic acid  were mixed in deionized water. The mixture was placed in a 25\u2005mL Teflon linear reactor and heated at 423\u2005K in an autoclave for 24\u2005h. The resulting solution was slowly cooled to room temperature. Yellow transparent single crystals of the title compound were obtained in 75% yield (based on Zn).Zn(NOUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms\u00b7The hy\u00addroxy H atoms, which could not be located in a difference-Fourier map, were included in idealized calculated positions that gave the most sensible geometry.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020014322/cq2039sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020014322/cq2039Isup2.hklStructure factors: contains datablock(s) I. DOI: 2040978CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "After H2O2 treatment, SHIP2 inhibition enhanced phosphatase and tensin homologue activity, which, in turn, affected phosphoinositide 3\u2010kinase/protein kinase B and mitogen\u2010activated protein kinase/extracellular signal\u2010regulated kinase activation.Azzi investigated the effects of SH2\u2010domain containing phosphatidylinositol\u20103,4,5\u2010trisphosphate 5\u2010phosphatase (SHIP2) inhibition by AS1938909 on H 2O2\u2010mediated AKT and mitogen\u2010activated protein kinase/extracellular signal\u2010regulated kinase pathway activation. In addition, SHIP2 inhibition enhances reactive oxygen species generation. Interestingly, I found that SHIP2 inhibition and H2O2 treatment enhance lipid and protein phosphatase activity of PTEN. Pharmacological targeting or RNA interference(RNAi) mediated knockdown of PTEN rescues extracellular signal\u2010regulated kinase and AKT activation. Using a series of pharmacological and biochemical approaches, I provide evidence that crosstalk between SHIP2 and PTEN occurs upon an increase in oxidative stress to modulate the activity of mitogen\u2010activated protein kinase and phosphoinositide 3/ATK pathways.Phosphatidylinositol \u2010trisphosphate P3) is required for protein kinase B (AKT) activation. The level of PIP3 is constantly regulated through balanced synthesis by phosphoinositide 3\u2010kinase (PI3K) and degradation by phosphoinositide phosphatases phosphatase and tensin homologue (PTEN) and SH2\u2010domain containing phosphatidylinositol\u20103,4,5\u2010trisphosphate 5\u2010phosphatase 2 (SHIP2), known as negative regulators of AKT. Here, I show that SHIP2 inhibition in cervical cancer cell lines alters H \u0394\u03a8mmitochondrial membrane potentialAKTprotein kinase BAS19AS1938909CCK\u20108Cell Counting Kit\u20108DAPI4\u2032,6\u2010diamidino\u20102\u2010phenylindole dihydrochlorideDCF2',7'\u2010dichlorofluoresceinDCFDAdichlorofluorescein diacetateDMEMDulbecco's modified Eagle's mediumERendoplasmic reticulumERKextracellular signal\u2010regulated kinase2O2Hhydrogen peroxideMAPKmitogen\u2010activated protein kinasePARPPoly (ADP\u2010ribose) polymerasep\u2010phosphorylatedPHpleckstrin homologyPIP3Phosphatidylinositol \u2010trisphosphatePPIP2Phosphatidylinositol \u2010bisphosphatePI3Kphosphoinositide 3\u2010kinasePLC\u03b4phospholipase C, deltaPTENphosphatase and tensin homologueRNAiRNA interferenceROSreactive oxygen speciesSEMstandard error of the meanSHCSrc homology 2 domain\u2010containing proteinSHIP2SH2\u2010domain containing phosphatidylinositol\u20103,4,5\u2010trisphosphate 5\u2010phosphatase 22O2) is the main substance used to study oxidative stress at the cellular level. Experimental evidence exists for H2O2\u2010mediated ROS production that activates several signaling pathways, among which are mitogen\u2010activated protein kinase (MAPK) and phosphatidylinositol 3\u2010kinase (PI3K)/protein kinase B (Akt), which promote cell growth and survival \u20102\u2010thiophene\u2010carboxamide (AS1949490), a small\u2010molecule drug that was previously characterized from a high\u2010throughput screen  (Fisher Scientific), SHIP2 inhibitor AS19 from Sigma (Cat. No. SML1022), HHEK293T and HeLa cells were obtained from S. Schurmans . SiHa cells were obtained from S. Kateryna (GIGA\u2010University of Liege).\u22121d\u2010glucose supplemented with 10% FBS, 100\u00a0U\u00b7mL\u22121 penicillin, 100\u00a0U\u00b7mL\u22121 streptomycin and 1% l\u2010glutamine (Gibco). Cells between 3 and 10 passages were used. All cultures were maintained at 37\u00a0\u00b0C in a humidified 5% CO2 incubator. Unless otherwise stated, each cell was treated with 10\u00a0\u00b5m SHIP2 inhibitor AS1949490 or equivalent volume of DMSO as a control for 24\u00a0h.Cells were grown as recommended in DMEM containing 4.5\u00a0g\u00b7Lm. Cells were seeded overnight at equal density, 15\u00a0000 cells per well in a 96\u2010well plate. Upon 24\u00a0h treatment with DMSO as vehicle or SHIP2 inhibitor (10\u00a0\u03bcm), DCFDA was supplemented to the growth medium and incubated for 30\u00a0min at 37\u00a0\u00b0C. Stained cells were rinsed with warm basal DMEM and incubated again for 1\u00a0h in fresh medium. Where indicated, pyruvate pretreatment (5\u00a0mm) for 1\u00a0h was followed by H2O2 (1\u00a0mm). Fluorescent signal detection was measured using Tecan Infinite M200 PRO Multi\u2010Detection Microplate Reader (Tecan Life Science) or VICTOR\u2122 X Series Multilabel Plate Readers (PerkinElmer) set to 485\u2010nm excitation and 530\u2010nm emission wavelength.Cytoplasmic ROS levels were measured using the fluorescent probe 2\u2032,7\u2032\u2010DCFDA in a final concentration of 25\u00a0\u03bcm MitoTracker Red for 30\u00a0min at 37\u00a0\u00b0C. With different treatments, cells were fixed using ice\u2010cold methanol at \u221220\u00a0\u00b0C during 10\u00a0min. After three washes with PBS, cells were then incubated with DAPI (0.1\u00a0\u00b5g\u00b7mL\u22121). Images were captured using Leica TCS SP5 microscope and processed with imagej .Cells were plated overnight on glass coverslips in 24\u2010well plates (150\u00a0000 cells/well) followed by treatment with vehicle or SHIP2 inhibitor for 24\u00a0h. For mitochondria staining, live cells were supplemented with 100\u00a0nm siRNA. Twenty\u2010four hours later, the medium was replaced, then treated with vehicle or SHIP2 inhibitor for 24\u00a0h where indicated. The following siRNAs were used, ON\u2010TARGET plus SMART pool siRNA against PTEN (#L003023\u201000\u20100005) and a control siRNA (#D\u2010001810\u201010\u201005).siRNA transfection was performed using Dharmafect 4 according to the manufacturer's instruction (Dharmacon). In brief, cells were plated a day before at 50% confluence. They were then transfected with 75\u00a0nPlasmid transfection was performed using Lipofectamine 3000 according to the manufacturer's instructions. The following plasmid constructs GFP\u2013SHIP2, GFP\u2013BTK\u2013PH, GFP\u2013TAPP1\u2013PH and GFP\u2013phospholipase C, delta (PLC\u03b4)\u2013PH were obtained from S. Schurmans .m NaCl, 1.0% Nonidet P\u201040, 0.5% sodium deoxycholate, 0.1% SDS, 50\u00a0mm Tris\u2013HCl, pH 8.0), containing protease and phosphatase inhibitors (ROCHE). Protein samples were collected by centrifugation  at 4\u00a0\u00b0C. Sample concentrations were quantified using Bio\u2010Rad Protein Assay according to the manufacturer's instructions. Equal amounts of protein extract were loaded and separated by SDS/PAGE and then transferred to nitrocellulose membranes. The membranes were blocked for 60\u00a0min at room temperature with 5% BSA in Tris\u2010buffered saline supplemented with 0.05% Tween 20. Membranes were then incubated with primary antibodies overnight at 4\u00a0\u00b0C, followed by horseradish peroxidase\u2010labeled secondary antibodies. Labeled proteins were visualized with an enhanced chemiluminescence system (Fisher Scientific). Optical densities of proteins were determined using imagej.Cells were first washed with PBS and then resuspended in radioimmunoprecipitation assay buffer  #4377, ERK #4695, PARP #9542, Phospho\u2010MEK1/2 (Ser217/221) #9121, MEK1/2 #9122, phosphor\u2010Pten S380 #9551, Pten #5959, vinculin #13901 and phospho\u2010SHC (Tyr239/240) #2434]. Horseradish peroxidase\u2010linked secondary antibodies, Rabbit A0545 and Mouse A9044, were from Sigma. Actin and SHC were from Santa Cruz Biotechnology . Anti\u2010SHIP2 Ig was a gift from C. Erneux .m H2O2 for 4\u00a0h and treated with WST\u20108 for 1\u00a0h at 37\u00a0\u00b0C. The absorbance at 450\u00a0nm (A450\u00a0nm) was then measured using Tecan Infinite M200 PRO Multi\u2010Detection Microplate Reader.Cell viability was measured using Cell Counting Kit\u20108 (CCK\u20108) . Cells were first seeded overnight at equal density, 15\u00a0000 cells per well in a 96\u2010well plate. They were then treated with vehicle or SHIP2 inhibitor for 24\u00a0h followed by 1\u00a0mm SHIP2 inhibitor for 24\u00a0h. Upon 1\u00a0mm H2O2 treatment during 90\u00a0min, MitoTell\u2122 Orange solution was added and incubated for 30\u00a0min at 37\u00a0\u00b0C. Assay buffer B was then added. Fluorescence was then measured using Infinite M200 PRO Multi\u2010Detection Microplate Reader. Excitation wavelength was set at 540\u00a0nm and emission wavelength at 590\u00a0nm. Quantification was performed relative to control untreated cells. HeLa cells treated with carbonyl cyanide m\u2010chlorophenyl hydrazone 20\u00a0\u00b5m  were used as a control.\u0394\u03a8m measurement was performed using Cell Meter\u2122 Mitochondrion Membrane Potential Assay Kit (AAT Bioquest #22805). HeLa cells were seeded overnight at equal density, 10\u00a0000 cells per well in a 96\u2010well plate, then treated with vehicle or 10\u00a0\u00b5graphpad prism 7 Software . Data were presented as mean\u00a0\u00b1\u00a0SD. For comparisons of three or more conditions, one\u2010way ANOVA with Tukey's honestly significant difference post\u00a0hoc test was used. Differences less than 0.05 were considered statistically significant.Statistical analyses were performed using The author declares no conflict of interest.AA conceived and designed the experiments; acquired, analyzed, and interpreted the data; and wrote the manuscript.Fig. S1.  RNA levels of SHIP2 and PTEN in different cell lines . See also The Human Protein Atlas (https://www.proteinatlas.org/ENSG00000165458\u2010INPPL1/cell and https://www.proteinatlas.org/ENSG00000171862\u2010PTEN/cell).Fig. S2. SHIP2 inhibition alters AKT activation upon H2O2 treatment in SiHa cells. (A) SiHa cells were first treated with vehicle or SHIP2 inhibitor for 48\u00a0h, followed by 1\u00a0mM H2O2 for 6 h. Cell lysates were analyzed for the indicated antibodies. H2O2 treatment was performed in biological triplicates for vehicle and SHIP2\u2010inhibited cells. (B) The ROS scavenger pyruvate prevents H2O2\u2010induced cell death. SiHa cells were first treated with vehicle or SHIP2 inhibitor for 48\u00a0h, followed by pyruvate (5\u00a0mM) for 2\u00a0h, and then treated with 1\u00a0mM H2O2 for 4 h. Cell lysates were analyzed for the indicated antibodies. (C) SiHa cells were treated as in (B); then cell viability was measured with CCK\u20108 assays. After 5\u00a0h of 1\u00a0mM H2O2, cells were treated with WST\u20108 for 1\u00a0h at 37\u2009\u00b0C. The A450\u00a0nm was measured with a microplate reader. Data are the means\u00a0\u00b1\u00a0SEM from two independent experiments, each in four replicates. One\u2010way ANOVA, F\u00a0=\u00a092.1, P\u00a0<\u00a00.0001. Tukey's multiple comparisons test, **P\u00a0\u02c2\u00a00.01.Fig. S3. H2O2 induces SHIP2 clusters formation. (A) HeLa cells were first transfected with GFP plasmid alone as a control or with GFP\u2013SHIP2. Twenty\u2010four hours later, cells were treated with vehicle or SHIP2 inhibitor for 24\u00a0h, then followed by 1\u00a0mM H2O2 for 1\u00a0h. Cells were then fixed and mounted. Scale bar: 10\u00a0\u03bcM. (B) HeLa cells were treated with a vehicle or AS19 for 24\u00a0h and subsequently followed by AKT activator (SC79), 20\u00a0\u00b5M for 2\u00a0h and 1\u00a0mM H2O2 for 4\u00a0h. Total lysates were analyzed for the indicated antibodies.Fig. S4. SHIP2 inhibition enhances PIP2 accumulation. HeLa cells were first transfected with plasmid GFP\u2010tagged PLC\u03b4\u2010PH domain; 6\u00a0h later they were treated with vehicle or AS19 for 24\u00a0h, then fixed and mounted. Fluorescent images of PIP2 levels are shown. Scale bar: 10\u00a0\u03bcM. C\u2010, vehicle\u2010treated cells.Click here for additional data file.Appendix S1. Original uncropped western blot figures. Some pictures are with additional samples data. However, these samples are not related to the results of this article (please see where indicated).Click here for additional data file."}
{"text": "Mthphn\u22efOMthphn (Mthphn = meth\u00adoxy\u00adphen\u00adyl) hydrogen bonds form corrugated layers parallel to (100) that are connected along the a axis by C\u2014H\u22ef\u03c0(ring) and \u03c0\u2013\u03c0 stacking inter\u00adactions.In the crystal structure, C\u2014H 20H21N3O3, the allyl substituent is rotated out of the plane of its attached phenyl ring [torsion angle 100.66\u2005(15)\u00b0]. In the crystal, C\u2014HMthphn\u22efOMthphn (Mthphn = meth\u00adoxy\u00adphen\u00adyl) hydrogen bonds lead to the formation of (100) layers that are connected into a three-dimensional network by C\u2014H\u22ef\u03c0(ring) inter\u00adactions, together with \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.7318\u2005(10)\u2005\u00c5] between parallel phenyl rings. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (48.7%) and H\u22efC/C\u22efH (23.3%) inter\u00adactions. Computational chemistry reveals that the C\u2014HMthphn\u22efOMthphn hydrogen bond energy is 47.1\u2005kJ\u2005mol\u22121. The theoretical structure, optimized by density functional theory (DFT) at the B3LYP/ 6\u2013311\u2005G level, is compared with the experimentally determined mol\u00adecular structure. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.In the title mol\u00adecule, C The allyl group is rotated out of the plane of the A ring as indicated by the C3\u2014C4\u2014C7\u2014C8 torsion angle of 100.66\u2005(15)\u00b0. Both meth\u00adoxy groups are virtually coplanar with their attached rings with C3\u2014C2\u2014O2\u2014C20 and C17\u2014C16\u2014O3\u2014C19 torsion angles, respectively, of 5.04\u2005(16) and 3.73\u2005(16)\u00b0. There are no unusual bond lengths or bond angles in the mol\u00adecule.The title mol\u00adecule is non-planar Fig.\u00a01, with thMthphn\u22efOMthphn (Mthphn = meth\u00adoxy\u00adphen\u00adyl) hydrogen bonds  inter\u00adactions \u2005\u00c5  layers are formed by C\u2014Hs Table\u00a01. These as Table\u00a01 as well \u2005\u00c5 Fig.\u00a03.Crystal Explorer 17.5 , and near O3 indicate their roles in hydrogen bonding; they also appear as blue and red regions corresponding to positive (hydrogen-bond donors) and negative (hydrogen-bond acceptors) potentials on the HS mapped over electrostatic potential rm Fig.\u00a04, the whia, and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efN/N\u22efH, H\u22efO/O\u22efH, C\u22efC, N\u22efC/C\u22efN, O\u22efC/C\u22efO and O\u22efN/N\u22efO contacts  has the tips at de + di = 2.68\u2005\u00c5. The pair of scattered points of spikes in the fingerprint plot delineated into H\u22efN/N\u22efH contacts  has a distribution of points with small and slightly larger tips at de + di = 2.72 and 2.70\u2005\u00c5, respectively. The H\u22efO/O\u22efH contacts  have a symmetric distribution of points with the tips at de + di = 2.48\u2005\u00c5. The C\u22efC contacts, Fig.\u00a07f, have an arrow-shaped distribution of points with the tip at de = di = 1.68\u2005\u00c5. Finally, N\u22efC/C\u22efN , O\u22efC/C\u22efO  and O\u22efN/N\u22efO  inter\u00adactions contribute only 1.0%, 0.9% and 0.6%, respectively, to the overall HS and thus have minor significance.The overall two-dimensional fingerprint plot, Fig.\u00a07\u22efN Fig.\u00a07g, O\u22efC/C\u22efO Fig.\u00a07h and O\u22ef\u22efO Fig.\u00a07i inter\u00adet al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated as \u221220.6 (Eele), \u22125.7 (Epol), \u221249.3 (Edis), 35.4 (Erep) and \u221247.1 (Etot).The inter\u00admolecular inter\u00adaction energies were calculated using a CE\u2013B3LYP/6\u201331G energy model available in GAUSSIAN 09  using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations  are shown in Fig.\u00a08EHOMO and ELUMO, electronegativity (\u03c7), hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3).The highest-occupied mol\u00adecular orbital (HOMO) and the lowest-unoccupied mol\u00adecular orbital (LUMO) together with the energy gap between them . Colourless crystals were isolated when the solvent was allowed to evaporate (yield: 88%).To a solution of 4-allyl-2-meth\u00adoxy-1-(prop-2-yn\u00adyloxy) benzene  in anhydrous aceto\u00adnitrile, 1-azido-4-meth\u00adoxy\u00adbenzene  and 10\u2005mg copper (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020006994/wm5559sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020006994/wm5559Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006994/wm5559Isup3.cdxSupporting information file. DOI: 2005277CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-017-04775-6, published online\u00a003 July 2017Correction to: This Article contains errors in Table 1, where the mean hatching dates and corresponding standard deviations (SD) have been incorrectly listed.The \u2018Mean (SD)\u2019 reported for Species \u2018Little auk\u2019, Colony \u2018Bj\u00f8rndalen (Isfjorden)\u2019 change for the date \u20182007, jul-10\u2019,\u201c(4.3)\u201dshould read:\u201c(5.6)\u201dThe \u2018Mean (SD)\u2019 for Species \u2018Little auk\u2019, Colony \u2018Bj\u00f8rndalen (Isfjorden)\u2019 change for the date \u20182008, jul-09\u2019,\u201c(3.2)\u201dshould read:\u201c(4.5)\u201dThe \u2018Mean (SD)\u2019 for Species \u2018Little auk\u2019, Colony \u2018Bj\u00f8rndalen (Isfjorden)\u2019 change for the date \u20182009, jul-12\u2019,\u201c(2)\u201dshould read:\u201c(3.5)\u201dIn the same Table 1, the \u2018Hatching Dates\u2019 and their associated \u2018Mean (SD)\u2019 Species \u2018Br\u00fcnnich\u2019s guillemot\u2019, Colony \u2018Diabasodden (Isfjorden)\u2019 change for the year \u20182014\u2032,\u201cjul-01 (7.9)\u201dshould read:\u201cjul-07 (3.7)\u201dThe \u2018Hatching Dates\u2019 and their associated \u2018Mean (SD)\u2019 Species \u2018Br\u00fcnnich\u2019s guillemot\u2019, Colony \u2018Diabasodden (Isfjorden)\u2019 change for the year \u20182015\u2032,\u201cjun-22 (10.7)\u201dshould read:\u201cjul-03 (5.9)\u201dLastly, in the same Table 1, the \u2018Hatching Dates\u2019 and their associated \u2018Mean (SD)\u2019 Species \u2018Br\u00fcnnich\u2019s guillemot\u2019, Colony \u2018Ossian sarsfjellet (Kongsfjorden)\u2019 change for the year 2014.\u201cjun-29 (6.3)\u201dshould read:\u201cjul-06 (5.4)\u201dThe \u2018Hatching Dates\u2019 and their associated \u2018Mean (SD)\u2019 Species \u2018Br\u00fcnnich\u2019s guillemot\u2019, Colony \u2018Ossian sarsfjellet (Kongsfjorden)\u2019 change for the year 2015,\u201cjun-23 (9.2)\u201dshould read:\u201cjul-02 (7.1)\u201dThe correct Table"}
{"text": "The title compound, 2-(2-(meth\u00adoxy\u00adcarbon\u00adyl)-3,6-bis\u00ad(meth\u00adoxy\u00admeth\u00adoxy)phen\u00adyl)acetic acid, was synthesized as an inter\u00admediate for a possible total synthesis of the isocoumarin 3-methyl-3,5,8-trihy\u00addroxy-3,4-di\u00adhydro\u00adisocoumarin. 14H18O8, (I), the meth\u00adoxy\u00adcarbonyl [\u2013C(=O)OCH3] and the acetic acid [\u2013CH2C(=O)OH] groups are inclined to the benzene ring by 79.24\u2005(11) and 76.71\u2005(13)\u00b0, respectively, and are normal to each other with a dihedral angle of 90.00\u2005(13)\u00b0. In the crystal, mol\u00adecules are linked by a pair of O\u2014H\u22efO hydrogen bonds forming the familiar acetic acid inversion dimer. The dimers are linked by two C\u2014H\u22efO hydrogen bonds and an offset \u03c0\u2013\u03c0 inter\u00adaction [inter\u00adcentroid distance = 3.6405\u2005(14)\u2005\u00c5], forming layers lying parallel to the (10In the title compound, C Ceratocystis fimbriata species. The latter are pathogenic agents responsible for the infections of coffee and plane trees , is a key inter\u00admediate for the proposed total synthesis of 3-methyl-3,5,8-trihy\u00addroxy-3,4-di\u00adhydro\u00adisocoumarin, and its synthesis is illustrated in Fig.\u00a011), which was first brominated to give compound 2. The latter was then reacted with NaH and ClCH2OCH3 to give compound 3, so protecting the hydroxyl groups. Reacting 3 with tetra\u00admethyl\u00adpiper\u00adidene with n-butyl\u00adlithium and CH2(CO2CH3)2 resulted in the formation of compound 4. Finally 4 was reacted with various qu\u00adanti\u00adties of KOH in methanol/water (2:1) to give the title compound, I. The highest yield (81%) was obtained by reacting 20 equivalents of KOH in methanol/water (2:1) at 298\u2005K under stirring for 16\u2005h. Inter\u00adestingly, the same reaction with reflux for 30 minutes yielded the diacid, 2-(carb\u00adoxy\u00admeth\u00adyl)-3,6-di\u00adhydroxy\u00adbenzoic acid (5), with a yield of 82%  forming an inversion dimer with an B\u22efO6ii and C11\u2014H11A\u22efO1iii) and offset \u03c0\u2013\u03c0 inter\u00adactions between inversion-related benzene rings, so forming layers lying parallel to (10B\u22efO4iv) and a C\u2014H\u22ef\u03c0 inter\u00adaction to form a supra\u00admolecular framework (Table\u00a01Cg\u22efCgiii = 3.6405\u2005(14)\u2005\u00c5, where Cg is the centroid of the C1\u2013C6 benzene ring; inter\u00adplanar distance = 3.5911\u2005(9)\u2005\u00c5; offset = 0.597\u2005\u00c5; symmetry code: (iii) \u2212x, \u2212y\u00a0+\u00a01, \u2212z.In the crystal of if Fig.\u00a03. The dimk Table\u00a01. Detailset al., 2007CrystalExplorer17.5  through white to blue . The energy frameworks , dispersion (Edis) and total energy (Etot) components, respectively. The radius of the cylinder is proportional to the magnitude of the inter\u00adaction energy.The Hirshfeld surface analysis  , O\u22efH/H\u22efO (41.1%) , C\u22efH/H\u22efC (7.2%)  and C\u22efC (2.7%)  contacts. The inter\u00admolecular contacts are therefore almost equally distributed between electrostatic and dispersion forces, as shown in Fig.\u00a07a and 7b. The energy frameworks  Fig.\u00a06b, O\u22efH/H%) Fig.\u00a06c, C\u22efH/H%) Fig.\u00a06d and C\u22ef%) Fig.\u00a06e contacks Fig.\u00a07 were adja. The individual energy components, electrostatic (Eele), polarization (Epol), dispersion (Edis) and repulsion (Erep) energies and the sum of these components (Etot) for the inter\u00adactions relative to a reference mol\u00adecule (*) are shown in Fig.\u00a08b.The calculation of the energy framework results in a colour-coded mol\u00adecular cluster related to the specific inter\u00adaction energy, see Fig.\u00a08et al., 2016et al., 2018H-2-benzo\u00adpyran-1-one phen\u00adyl)acetic acid gave zero hits.I is illustrated in Fig.\u00a012\u20135 and I are available in the PhD thesis of Tiouabi (2005I were obtained by slow evaporation of a solution in acetone-d6.The synthesis of compound uabi 2005. It can Uiso(H) = 1.5Ueq(OH and C-meth\u00adyl) and 1.2Ueq(C) for other H-atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a04Intensity data were measured using a Stoe IPDS I, a one-circle diffractometer. For the triclinic system often only 93% of the Ewald sphere is accessible, which explains why the alert diffrn_reflns_laue_measured_fraction_full value (0.942) below minimum (0.95) is given. This involves 155 random reflections out of the expected 2692 for the IUCr cutoff limit of sin\u2005\u03b8/\u03bb = 0.60.10.1107/S2056989020007987/ex2033sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989020007987/ex2033Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007987/ex2033Isup3.cmlSupporting information file. DOI: 2009890CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound comprises two mol\u00adecules in the asymmetric unit. Inter\u00admolecular C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds lead to a three-dimensional network structure. 10H15NO2S, comprises two mol\u00adecules in the asymmetric unit. The S=O bond lengths of the sulfonamide functional group range from 1.428\u2005(2) to 1.441\u2005(2)\u2005\u00c5, with S\u2014C bond lengths of 1.766\u2005(3)\u2005\u00c5 (for both mol\u00adecules in the asymmetric unit), and S\u2014N bond lengths of 1.618\u2005(2) and 1.622\u2005(3)\u2005\u00c5, respectively. When both mol\u00adecules are viewed down the N\u2014S bond, the propyl group is gauche to the toluene moiety. In the crystal structure, mol\u00adecules of the title compound are arranged in an intricate three-dimensional network that is formed via inter\u00admolecular C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. The crystal structure was refined from a crystal twinned by inversion.The crystal structure of the title sulfonamide, C Commonly referred to as \u2018sulfa drugs\u2019, these mol\u00adecules have been in clinical use since 1968  and butyrylcholinesterase (BChE) inhibitors . The S=O bond lengths of the sulfonamide functional group range from 1.428\u2005(2) to 1.441\u2005(2)\u2005\u00c5, which fall within expected values. The S\u2014C bond lengths are 1.766\u2005(3)\u2005\u00c5 for both mol\u00adecules, and the S\u2014N bond lengths are 1.618\u2005(2) and 1.622\u2005(3)\u2005\u00c5. The O\u2014S\u2014O bond angles are 119.49\u2005(13) and 118.26\u2005(13)\u00b0, with N\u2014S\u2014C bond angles of 106.86\u2005(13) and 108.27\u2005(13)\u00b0. The two independent mol\u00adecules differ in the orientation of the propyl chain and the H atom attached to the N atom, however, in each case with the propyl chain being gauche to a sulfonamide oxygen atom and to the toluene moiety when the mol\u00adecules are viewed down the N1\u2014S1 bond  and the sulfonamide oxygen atom O1 or O1A are 60.5\u2005(3) and 57.3\u2005(2)\u00b0, respectively. The groups bonded to the sulfur atom of both sulfonamide groups adopt slightly distorted tetra\u00adhedral environments with fourfold coordination \u03c44 descriptors of 0.94 for both S1 and S1A  atoms of a nearby mol\u00adecule. These classic hydrogen-bonding inter\u00adactions form ribbons of the title compound that lie parallel to the ab plane. These inter\u00adactions have D\u22efA distances of 2.925\u2005(3) and 2.968\u2005(3)\u2005\u00c5, with D\u2014H\u22efA angles of 161\u2005(3) and 172\u2005(3)\u00b0. The inter\u00admolecular C\u2014H\u22efO hydrogen bonding inter\u00adactions  to 3.594\u2005(4)\u2005\u00c5, and D\u2014H\u22efA angles ranging from 152.8 to 170.2\u00b0. Specific\u00adally, the C8(H8B)\u22efO2A, C8A(H8AA)\u22efO2 and C6(H6)\u22efO1A inter\u00adactions contribute to the stabilization of the supra\u00admolecular ribbons. The inter\u00adaction between C3A(H3A) and O2A links the supra\u00admolecular ribbons into an intricate three-dimensional network  to a stirring mixture of propyl\u00adamine  and p-toluene\u00adsulfonyl chloride  in 10\u2005ml of tetra\u00adhydro\u00adfuran. The reaction mixture was stirred at room temperate for 24\u2005h under a nitro\u00adgen atmosphere. After acidification with 5 M HCl and dilution with 15\u2005ml of di\u00adchloro\u00admethane, the organic layer was washed with water and brine. The aqueous layers were back extracted with 10\u2005ml of di\u00adchloro\u00admethane. The combined organic layers were then combined, dried over anhydrous sodium sulfate, and evaporated to dryness. The liquid residue was triturated with diethyl ether, placed in a freezer for 48\u2005h and, after isolation via vacuum filtration, the product was obtained as colorless crystals .The title compound was prepared by the dropwise addition of 0.59 et al., 2013Uiso(H) = 1.2Ueq(C) for methyl\u00adene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups. Hydrogen atoms bonded to nitro\u00adgen atoms were located using electron density difference maps, and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020007756/wm5567sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020007756/wm5567Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007756/wm5567Isup3.cmlSupporting information file. DOI: 2008411CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are stacked along the b axis via a \u03c0\u2013\u03c0 inter\u00adaction between the benzene rings.The title compound, [Na 6F5BH3)(C4H8O)2]2, represents a dimeric structure of sodium and organoborohydride, located about a centre of inversion. The Na\u22efB distances of 2.7845\u2005(19) and 2.7494\u2005(18)\u2005\u00c5 were apparently longer than the Li\u22efB distances (2.403\u20132.537\u2005\u00c5) of the lithium organotri\u00adhydro\u00adborates in the previous reports. Moreover, an inter\u00adaction between the sodium atom and one fluorine atom on the 2-position of the benzene ring is observed [Na\u2014F = 2.6373\u2005(12)\u2005\u00c5]. In the crystal, the dimeric mol\u00adecules are stacked along the b-axis via a \u03c0\u2013\u03c0 inter\u00adaction between the benzene rings.The title compound, [Na(\u03bc-C Such a chelation mode was also observed in the previously reported dimeric structure of lithium tri\u00adhydro\u00adborates.The title compound Fig.\u00a01 represeni\u2014F5 = 2.6373\u2005(12)\u2005\u00c5] is much shorter than the sum of van der Waals radii (3.74\u2005\u00c5), indicating the presence of a sodium\u2013halogen inter\u00adaction. Such a halogen\u2013metal inter\u00adaction is also observed in bromoaryl-substituted lithium tri\u00adhydro\u00adborate \u2005\u00c5; symmetry code: (ii) \u2212x\u00a0+\u00a01, \u2212y\u00a0\u2212\u00a01, \u2212z] is slightly longer than the sum of van der Waals radii (3.39\u2005\u00c5), suggesting that the B\u22efF inter\u00adaction is weak. The distance between the closest hydrogen atom (H4) and centroid of the C6F5 ring is 3.343\u2005\u00c5, indicating the absence of C\u2014H\u22ef\u03c0 inter\u00adactions.In the crystal, the dimeric mol\u00adecules are stacked along the et al., 2019et al., 2010et al., 1998As described above, there is only one example of structural analysis on a sodium alkyl\u00adtris\u00adboronate complex BH2\u00b7S(CH3)2  in THF (20\u2005mL) at 333\u2005K for 5\u2005h. The supernatant solution of the reaction mixture was separated and dried under vacuum. The obtained colourless solid was redissolved into 1\u2005mL of THF, and 10\u2005mL of hexane was layered on it. This solution was stored at 243\u2005K overnight and 1.55\u2005g (51%) of colourless crystals were obtained. 19F NMR : \u03b4 \u2212134.72 , \u2212162.85 , \u2212165.17 ; 11B NMR : \u03b4 \u221236.71 .The title compound was prepared by the reaction of NaH  and (CUiso(H) = 1.2Ueq(C), while the H atoms on boron were refined isotrop\u00adically [refined B\u2014H = 1.08\u2005(3)\u20131.13\u2005(2)\u2005\u00c5].Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989019017201/is5529sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019017201/is5529Isup3.hklStructure factors: contains datablock(s) I. DOI: 1973896CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "CPNC crystallizes in the monoclinic non-centrosymmetric space group Cc and adopts an s-cis conformation with respect to the ethyl\u00adenic double bonds (C=O and C=C). The crystal packing features C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions whose percentage contribution was qu\u00adanti\u00adfied by Hirshfeld surface analysis. Quantum chemistry calculations including geometrical optimization and mol\u00adecular electrostatic potential (MEP) were analysed by density functional theory (DFT) with a B3LYP/6\u2013311\u2005G++ basis set.A new conjugated carbazole chalcone compound, ( The experimental and theoretical studies and chemical reactivity analysis are discussed.In a continuation of our studies \u2005\u00c5 , 1.223\u2005\u00c5 (DFT)] and carbon\u2013carbon double bond \u2005\u00c5 , 1.348\u2005\u00c5 (DFT)]. The CPNC mol\u00adecule is twisted slightly at the C21\u2014C22 bond, with a C20\u2014C21\u2014C22\u2014C27 torsion angle of \u221210.4\u2005(3)\u00b0 . The experimental and theoretical C15\u2014C16\u2014C19\u2014C20 torsion angles are 158.6\u2005(3) and 178.8\u00b0, respectively. The 9-phenyl\u00adcarbazole C13\u2014N1 bond is also observed to be twisted .There is also a twist [dihedral angle = 25.30\u2005(17)\u00b0] between the mean planes of the nitro\u00adphenyl group  and the enone unit . Meanwhile, the enone bridge forms dihedral angles of 31.52\u2005(18) and 21.77\u2005(16)\u00b0, respectively, with the C13\u2013C18 phenyl ring and the 9H-carbazole unit and the C13\u2013C18 phenyl ring subtend a dihedral angle of 53.26\u2005(10)\u00b0, which is similar to the dihedral angle of 53.8\u2005(3) between the bridge aromatic ring and the 9H-carbazole unit in the related compound 2-[4-(9H-carbazol-9-yl)benzyl\u00adidene]-2,3-di\u00adhydro\u00adinden-1-one \u00b0 . This planar nature is possibly due to steric repulsion by the hydrogen atoms of the aromatic rings, leading to a small \u03c0-electron delocalization. However, the phenyl ring of the 9-phenyl\u00adcarbazole moiety subtends a large dihedral angle to the nitro\u00adbenzene group of 56.74\u2005(10)\u00b0 , which tends to suppress the extension of the conjugation effect through the enone moiety.The 9)\u00b0 Fig.\u00a01c. This )\u00b0 Fig.\u00a01d, whichb-axis direction via C15\u2014H15A\u22efO1 inter\u00adactions  sites in the red-coloured region, while the blue colour indicates the electrophilic (electron-deficient) site localized on the hydrogen atom. These reactive sites are responsible for inter\u00admolecular inter\u00adactions where the red and blue spots suggest the strongest repulsion site (electrophilic attack) and strongest attraction site (nucleophilic attack), respectively. The MEP results are further supported by the electrostatic potential contour map showing the iso-surface lines shown in Fig.\u00a06b where the red lines refer to the strong electron-withdrawing atoms such as in carbonyl and nitro substituents.The reactive sites of a mol\u00adecule can be investigated using mol\u00adecular electrostatic potential (MEP) analysis phen\u00adyl]prop-2-en-1-one benzyl\u00adidene]indan-1-one \u00b0] indicates a slight twist, which is which comparable to that in ISADOW [C8\u2014C10\u2014C11\u2014C12 = 178.6\u2005(2)\u00b0].A search of the Cambridge Structural Database carbazole (5\u2005mmol) were dissolved in 20\u2005mL of methanol and then a catalytic amount of sodium hydroxide solution  was added dropwise under continuous stirring for about 5\u20136\u2005h at room temperature until a precipitate formed. This was filtered off, washed successively with distilled water and recrystallized from acetone solution, yielding orange block-shaped crystals suitable for X-ray diffraction analysis.4\u2032-Nitro\u00adaceto\u00adphenone (5\u2005mmol) and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020002054/ex2028sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020002054/ex2028Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002054/ex2028Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002054/ex2028sup3.docxSI Comparison between the calculated optimized and X-ray geometrical parameters for the CPNC compound. DOI: 1967669CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Trypanosoma brucei has been greatly facilitated by using CRISPR/Cas9 as a genome editing tool. To date, this has entailed using a limited number of cell lines that are stably transformed to express Cas9 and T7 RNA polymerase (T7RNAP). It would be desirable, however, to be able to use CRISPR/Cas9 for any trypanosome cell line.Generation of knockouts and in situ tagging of genes in We describe a sequential transfection expression system that enables transient expression of the two proteins, followed by delivery of PCR products for gRNAs and repair templates. This procedure can be used for genome editing without the need for stable integration of the Cas9 and T7RNAP genes. Trypanosoma brucei entails creating cell lines which express (either constitutively or inducibly) both Cas9 to generate a DNA double-strand break and T7RNAP for the transcription of guide RNAs from a DNA template [T. brucei [The establishment of genome editing by CRISPR/Cas9 in trypanosomatids has greatly increased the ease with which knockouts can be generated, as two copies of a non-essential gene can often be deleted in a single round of transfection. The system most widely used for template \u20134. The o. brucei . FurtherT. brucei. The plasmid All-in-one-Cas9  in T. brucei Lister 427 procyclic forms that already expresses Cas9 and T7RNAP constitutively (Lister 427/Cas9) [To test the functionality of the plasmid, we used the LeishGEdit software  to desig27/Cas9) . This gaFor genome editing by transient expression of Cas9 and T7RNAP, we tested two different transfection schemes. Initially, all components were transfected simultaneously: the circular plasmid pAi1C9 encoding Cas9 and T7RNAP, the DNA template for in vivo transcription of a guide RNA, and the DNA repair template harbouring mNG for C-terminal tagging and a hygromycin resistance gene. This procedure gave few hygromycin-resistant clones, only 10 clones in total, from 4 separate transfections. These clones either did not express mNG (4 clones), or expressed it as a cytoplasmic protein 2 clones) or expressed it correctly localised to the flagellum (4 clones). Examples are shown in Fig.\u00a0 clones oWe therefore tested sequential transfections in which we first used pAi1C9 to enable expression of Cas9 and T7RNAP. A second transfection 20\u00a0h later provided the templates for the gRNA and the mNG repair construct. The same electroporation conditions were used for the plasmid and the templates , which are non-essential genes in cultured procyclic form . brucei . Genotyp7T. b. brucei 427 procyclic forms were transfected with 10\u00a0\u00b5g pAi1C9 dissolved in 100\u00a0\u00b5l TbBSF transfection buffer [2 for 20\u00a0h.4\u2009\u00d7\u200910n buffer . Cells wn buffer  supplemeThe entire culture from the first transfection was centrifuged at 1700\u00a0g for 5\u00a0min, the supernatant discarded and the cells resuspended in 100\u00a0\u00b5l TbBSF transfection buffer containing the pooled PCR products (see protocol for PCRs below). For tagging, one sgRNA template (targeted to the 3\u2032 end of the ORF) and one repair template (hygromycin resistance) were provided; to generate the knockouts, we provided two sgRNA templates (targeted to the 5\u2032 and 3\u2032 ends of the ORF) and two repair templates (hygromycin and neomycin resistance genes).\u22121\u00a0Hygromycin B and/or 15\u00a0\u2009\u00b5g\u00a0\u2009ml\u22121\u00a0Geneticin; stable clones were obtained 2\u00a0weeks post selection.Transfection was performed as described above and the cells were transferred to 10\u00a0ml SDM79 supplemented with 10% FBS. The cells were diluted 1:5, 1:50 and 1:500 in conditioned medium (fresh medium\u2009+\u200920% supernatant of a log-phase culture) and distributed into 24-well plates (1\u00a0ml in each well). Transformants were selected using 25\u2009\u00a0\u00b5g\u2009\u00a0ml1\u00a0\u03bcl G00 primer (0.5\u00a0\u03bcM)4\u00a0\u03bcl 5\u2009x\u2009Phusion HF buffer0.5\u00a0\u03bcl dNTP mix (250\u00a0\u03bcM)1\u00a0\u03bcl sgRNA primer (0.5\u00a0\u03bcM)0.2\u00a0\u03bcl Phusion High-Fidelity DNA polymerase (0.4U)2O13.3\u00a0\u03bcl H1st PCR: template for sgRNAs; two 20\u00a0\u00b5l reactions per target.30\u2032\u2032, 98\u00a0\u00b0C10\u2032\u2032, 98\u00a0\u00b0C30\u2032\u2032, 60\u00a0\u00b0C15\u2032\u2032, 72\u00a0\u00b0Cgo to step 2, 35 cycles in total10\u2032, 72\u00a0\u00b0Chold at 10\u00a0\u00b0CProgram:2\u00a0\u03bcl 60\u00a0ng pPOTv7 mNG (hygro or G418) plasmid8\u00a0\u03bcl 5\u2009x\u2009Phusion HF buffer1\u00a0\u03bcl dNTP mix (250\u00a0\u03bcM)2\u00a0\u03bcl Upstream forward primer (0.5\u00a0\u03bcM)2\u00a0\u03bcl Downstream reverse KO/TAG primer (0.5\u00a0\u03bcM)0.4\u00a0\u03bcl Phusion High-Fidelity DNA polymerase (0.4U)2O24.6\u00a0\u03bcl H2nd PCR: template for resistance gene; two 40\u00a0\u00b5l reactions per resistance gene5\u2032, 94\u00a0\u00b0C30\u2032\u2032, 94\u00a0\u00b0C30\u2032\u2032, 65\u00a0\u00b0C2\u203230\u2032\u2032, 72\u00a0\u00b0Cgo to step 2, 40 cycles in total10\u2032, 72\u00a0\u00b0Chold at 10\u00a0\u00b0CProgram:Reactions were performed with reagents from New England Biolabs: Phusion High-Fidelity DNA polymerase (M0530S), 5\u2009x\u2009 Phusion HF buffer (B0519S) and dNTP mix N0447S). Cycling conditions are identical to those previously published 47S. Cycl.1st PCR:PCR reactions were pooled and extracted with 1 volume water-saturated phenol (pH 8), followed by extraction with 1 volume chloroform. DNA was precipitated from the aqueous phase by addition of 0.1 volume 3\u00a0M sodium acetate, pH 5.2, and 3 volumes ice-cold ethanol. The DNA was pelleted by centrifugation, washed twice with 1\u00a0ml 80% ethanol, air-dried at room temperature, dissolved in 40\u00a0\u03bcl Milli-Q-water and stored at \u2212\u200920\u00a0\u00b0C until transfection.G00: aaaagcaccgactcggtgccactttttcaagttgataacggactagccttattttaacttgctatttctagctctaaaacPDEB1 3\u2032 sgRNA primer:gaaattaatacgactcactataggTGAAGAAGTCAGTTGACCGGgttttagagctagaaatagcTrypanin 5\u2032 sgRNA primer:gaaattaatacgactcactataggCAAAAACGAGAAGAGCCTACgttttagagctagaaatagcTrypanin 3\u2032 sgRNA primer:gaaattaatacgactcactataggAGGTGTTGTGGTTCACACGTgttttagagctagaaatagcGPI8 5\u2032 sgRNA primer:gaaattaatacgactcactataggCGGTTGCAAAAAACGAATGCgttttagagctagaaatagcGPI8 3\u2032 sgRNA primer:gaaattaatacgactcactataggGGTATGTCCCATCAGTTGGAgttttagagctagaaatagcTrypanin upstream forward primer:TACTTTTCAGACTGCATCGTGGCGTACCCCgtataatgcagacctgctgcTrypanin downstream reverse KO primer:CTGCAACAAAGCCGTAACTTGGAACAACCAccggaaccactaccagaaccPDEB1 downstream forward primer:ACGAGTTCTGGCAACAACAGCAGTACTCGTggttctggtagtggttccggPDEB1 downstream reverse TAG:ATCACCATTGACAAGAACGTACATCTACCAccaatttgagagacctgtgcGPI8 upstream forward primer:TTGGATCAGGCGCTTGCATATTTATTTCCAgtataatgcagacctgctgcGPI8 downstream reverse KO primer:AGTTTCAGGAAGGAAGTTCGTTTTTCTCCTccggaaccactaccagaaccT. brucei cell line. Moreover, in contrast to stable integration of the CRISPR/Cas9 machinery, transient transfection does not require additional selectable markers and it has the added advantage that it circumvents possible Cas9 toxicity. In addition to using Cas9 for deletion, mutation, tagging or integration of ectopic copies, this procedure could also be adapted for nuclease inactive Cas9 variants for targeting RNAs or epigenetic modifications [Transient transfection with pAi1C9 gives rise to fewer clones than cell lines that are stably transformed with the T7RNAP and Cas9 genes. It has the advantage, however, that it can be applied to any ications , 15.Additional file 1: Validation of knockout (KO) clones. A+B Trypanin-KO (Tb427.10.6350). A Clonal selection of stable transformants in 24-well plates. Dilutions from transfected pool cultures and number of cells seeded are indicated. Circles depict wells containing cells with successful (green filled circle) or unsuccessful (\u25cb) genome editing. B Assessment of editing by genotyping PCR and agarose gel electrophoresis. Genes amplified from genomic DNA and target loci are indicated. Lanes corresponding to validated KO clones are marked with green circles. C+D GPI8-KO (Tb427.10.13860) in a cell line allowing inducible expression of an ectopic copy of GPI8. C as in A. D as in B. E List of primers used for genotyping PCRs of Trypanin-KO (left panels) and GPI8-KO (right panels)."}
{"text": "The heterocyclic portion of the tetra\u00adhydro\u00adiso\u00adquinoline unit is planar and an intra\u00admolecular N\u2014H\u22efN hydrogen bond and a C\u2014H\u22ef\u03c0(ring) inter\u00adaction help to determine the overall conformation. In the crystal, O\u2014H\u22efO hydrogen bonds form inversion dimers, which are connected by C\u2014H\u22efO hydrogen bonds, forming layers parallel to  inter\u00adaction help to determine the overall conformation. In the crystal, a layer structure with the layers parallel to (10In the title mol\u00adecule, C A puckering analysis \u2005\u00c5, \u03b8 = 128.52\u2005(14)\u00b0 and \u03c6 = 286.46\u2005(18)\u00b0. The conformation of this ring approximates an envelope with C3 as the flap.The title compound crystallizes in space group it Fig.\u00a01. The C5/g Table\u00a01 and placts Fig.\u00a01. AlthougA\u22efO1 hydrogen bonds (Table\u00a01i and O1\u22efO2i  contacts of 2.8774\u2005(16) and 2.8674\u2005(14)\u2005\u00c5 , respectively. The dimers are connected by C13\u2014H13\u22efO2 hydrogen bonds  Figs. 2 and 3 \u25b8.et al., 2016et al., 2010et al., 2017a2CO2CH3 group on sulfur , the sites of the inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds can be seen on the left side near the bottom and at the top, respectively. A weaker point of inter\u00adaction is at O3 on the lower right of the diagram, which might indicate a weak, inter\u00admolecular C4\u2014H4B\u22efO3 hydrogen bond since the O\u22efH distance is 2.605\u2005(15)\u2005\u00c5. The surfaces mapped over shape-index  and curvedness  show a relatively flat region over the C23\u2013C28 benzene ring in the latter and a red triangular area over the edge of the ring in the former. This is suggestive of a C\u2014H\u22ef\u03c0(ring) inter\u00adaction and can be identified with the C20\u2014H20A\u22efCg3 inter\u00adaction noted in Section 2. The fingerprint plots derived from the Hirshfeld surface enable the apportionment of the inter\u00admolecular inter\u00adactions into specific sets. Fig.\u00a05a displays the plot for all inter\u00adactions while Fig.\u00a05b\u20135d show those delineated into H\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions, which constitute 47.3%, 11.8% and 10.6% of the total inter\u00adactions, respectively.Hirshfeld surface analysis is an effective means of probing inter\u00admolecular inter\u00adactions -thione (10\u2005mmol), N-phenyl-2-chloro\u00adacetamide (10\u2005mmol) and sodium acetate trihydrate  in ethanol (100\u2005mL) was heated under reflux for one hour. The precipitate that formed after standing at room temperature overnight was collected, washed with water, dried in air and then recrystallized from ethanol to afford the title compound in the form of colorless crystals. Yield: 4.00\u2005g, 82%; m. p.: 470-472\u2005K.A mixture of 7-acetyl-4-cyano-1,5-dimethyl-6-hy\u00addroxy-8-phenyl-5,6,7,8-tetra\u00adhydro\u00adiso\u00adquinoline-3 and 7.02\u20137.04 (J = 8\u2005Hz) can be attributed to the aromatic protons.With regard to the \u22121): 3522 (OH); 3277 (NH); 3058 ; 2920, 2970, 2991 ; 2217 (C\u2261N); 1694 ; 1667 .IR : 10.22 ; 7.53\u20137.55 ; 7.23\u20137.29 ; 7.17\u20137.20 ; 7.02\u20137.04 ; 4.84 ; 4.52\u20134.54 ; 4.09\u20134.19 ; 3.25\u20133.29 ; 2.94\u20132.96 ; 2.89\u20132.94 , 2.11 ; 1.92 ; 1.28 .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021000372/vm2243sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021000372/vm2243Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021000372/vm2243Isup3.cmlSupporting information file. DOI: 2055318CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-019-48199-w, published online 23 August 2019Correction to: The original version of this Article contained errors.In Table 1, in the penultimate column the incorrect symbol for Chi-square was used in the column heading.2 (df)c\u201d\u201cxnow reads:2 (df)c\u201d\u201c\u03c715 and LC30 were incorrectly reported, due to mistranscription of the exponent values. As a result, the originally reported values were three orders of magnitude too high.Further, Table 3 contained an error. The standard errors for the control, LCr, the values for \u2018Control (Mean\u2009\u00b1\u2009SE)\u2019, \u2018LC15 (Mean\u2009\u00b1\u2009SE)\u2019 and \u2018LC30 (Mean\u2009\u00b1\u2009SE)\u2019,For the parameter \u201c0.302\u2009\u00b1\u20095.413a, 0.275\u2009\u00b1\u20095.022b and 0.196\u2009\u00b1\u20093.035b\u201dnow read:\u201c0.302\u2009\u00b1\u20090.0054a, 0.275\u2009\u00b1\u20090.0050b and 0.196\u2009\u00b1\u20090.0030b\u201d\u03bb, the values for \u2018Control (Mean\u2009\u00b1\u2009SE)\u2019, \u2018LC15 (Mean\u2009\u00b1\u2009SE)\u2019 and \u2018LC30 (Mean\u2009\u00b1\u2009SE)\u2019,For the parameter \u201c1.353\u2009\u00b1\u20097.325a, 1.317\u2009\u00b1\u20096.617b and 1.217\u2009\u00b1\u20093.695b\u201dnow read:\u201c1.353\u2009\u00b1\u20090.0073a, 1.317\u2009\u00b1\u20090.0066b and 1.217\u2009\u00b1\u20090.0037b\u201d.1, but although the correct Equations were used for calculations, the incorrect Equations were included in the original version of the Article.In the Materials and Methods section under subsection \u2018Data Analysis\u2019, Equations (8) and (9) were incorrectly reported. The authors used the notation provided in the original study describing these Equations. This study was subsequently correctedTherefore, Equation\u00a0(8),In addition, Equation\u00a0(9),now reads:In the same subsection, under Equation\u00a0(9):81 using TWOSEX-MS Chart with 100,000 replicates53,82.\u201d\u201cPopulation growth (mean and standard error) was calculated through paired bootstrap testnow reads:81 using TWOSEX-MSChart with 100,000 replicates53,82.\u201d\u201cPopulation parameters were calculated and compared through paired bootstrap testReferences 78 and 79 were incomplete and were incorrectly listed as \u2018Finney, D. \u2019 and \u2018Huang, Y. B. & Chi, H. The age-stage, two-sex life table with an offspring sex ratio dependent on female age (2011)\u2019 respectively. The correct references are given below.Finney, D. J. Probit Analysis. Cambridge University Press, Cambridge (1971).Journal of Agriculture and Forestry60(4), 337\u2013345 (2011).Huang, Y. B. & Hsin Chi. The age-stage, two-sex life table with an offspring sex ratio dependent on female age. Furthermore, in the Supplementary Materials file, the title,CHS1) in melon aphid, Aphis gossypii\u201d\u201cImpact of low-dose buprofezin on the biological traits and expression profile of chitin synthase 1 gene (now reads:CHS1) in melon aphid, Aphis gossypii\u201d\u201cImpact of low lethal concentrations of buprofezin on biological traits and expression profile of chitin synthase 1 gene (These errors have now been corrected in the HTML and PDF versions of this Article, and in the accompanying Supplementary Materials.Supplementary file1"}
{"text": "H-pyrrol-2-yl]acetate dihydrate, Na+\u00b7C15H14NO3\u2212\u00b72H2O, contains two sodium cations, two organic anions and two water mol\u00adecules. The title compound exhibits analgesic, anti-inflammatory and anti\u00adpyretic activities.The asymmetric unit of the title two-dimensional polymer, sodium 2-[1-methyl-5-(4-methyl\u00adbenzo\u00adyl)-1 H-pyrrol-2-yl]acetate dihydrate, Na+\u00b7C15H14NO3\u2212\u00b72H2O, contains two sodium cations, two organic anions (A and B) and two water mol\u00adecules. The coordination geometry around the sodium cations corresponds to a distorted octa\u00adhedron. Each pair of sodium cations (A\u2013A or B\u2013B) is chelated by two bridging anions coordinated by the O atoms of the deprotonated carb\u00adoxy\u00adlic groups, and each sodium atom is coordinated by an O atom of a third anion, which connects pairs of sodium atoms, and a water mol\u00adecule. As a result, a two-dimensional polymer is formed in the crystal. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyze the inter\u00admolecular contacts present in the crystal.The asymmetric unit of the title compound, sodium 2-[1-methyl-5-(4-methyl\u00adbenzo\u00adyl)-1 The coordination geometry around the sodium cations corresponds to a distorted octa\u00adhedron. Each pair of sodium cations (A\u2013A or B\u2013B) is chelated by two bridging anions coordinated by the O atoms of the deprotonated carb\u00adoxy\u00adlic groups, and each sodium atom is coordinated by an O atom of a third anion, which connects pairs of sodium atoms, and a water mol\u00adecule. As a result, a two-dimensional polymer is formed in the crystal , 2.416\u2005(2) and 2.441\u2005(2)\u2005\u00c5 while the Na\u2014Owater distances are on average slightly longer, being in the range 2.364\u2005(2)\u20132.607\u2005(3)\u2005\u00c5. It is worth noting that the terminal atom O2B does not inter\u00adact with a sodium cation.The sodium salt of the Cte Fig.\u00a01. The asyal Fig.\u00a02. The Na\u2014A, 1.243\u2005(3) and 1.250\u2005(3)\u2005\u00c5 in anion B] are very similar to each other and are slightly elongated in comparison with the standard value of 1.210\u2005\u00c5 of a carbonyl group  and 1.250\u2005(3)\u2005\u00c5 in anion A and \u221229.0\u2005(4)\u00b0 in mol\u00adecule B. The relative orientation of the toluene ring with respect to the pyrrole ring, neither planar nor perpendicular, is given by the the C6\u2014C8\u2014C9\u2014C10 torsion angle: 41.3\u2005(4)\u00b0 in mol\u00adecule A and \u221238.2\u2005(4)\u00b0 in mol\u00adecule B. Such an orientation mainly minimizes the inter\u00admolecular H\u22efH repulsions.The toluene substituent is in a synperiplanar conformation with respect to the C5\u2014C6 bond of the pyrrole ring: the C5\u2014C6\u2014C8\u2014C9 torsion angle is 26.9\u2005(4)\u00b0 in mol\u00adecule In the crystal, O\u2014H\u22efO hydrogen bonds Table\u00a01 are formCrystal Explorer 17.5  to 1.384 (blue). The areas colored red on the dnorm-mapped Hirshfeld surfaces acetate skeleton yielded only two hits, 2-meth\u00adoxy\u00adphenyl 2-{2-[1-methyl-5-(4-methyl\u00adbenzo\u00adyl)pyrrol-2-yl]acetamido}\u00adacetate tetra\u00adkis\u00addicopper(II)  or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021000414/zq2259sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021000414/zq2259Isup2.hklStructure factors: contains datablock(s) I. DOI: 2055407CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Oxm\u22efNOxm, O\u2014HHydr\u22efOHydr, O\u2014H\u2032Hydr\u22efOHydr and O\u2014HOxm\u22efOHydr hydrogen bonds link the mol\u00adecules into infinite chains along the c-axis direction.The phenyl rings are almost oriented perpendicularly. In the crystal, inter\u00admolecular O\u2014H N-hy\u00addroxy\u00adimino)-1,2-di\u00adphenyl\u00adethanol], C14H13NO2, consists of hy\u00addroxy phenyl\u00adaceto\u00adphenone and oxime units, in which the phenyl rings are oriented at a dihedral angle of 80.54\u2005(7)\u00b0. In the crystal, inter\u00admolecular O\u2014HOxm\u22efNOxm, O\u2014HHydr\u22efOHydr, O\u2014H\u2032Hydr\u22efOHydr and O\u2014HOxm\u22efOHydr hydrogen bonds link the mol\u00adecules into infinite chains along the c-axis direction. \u03c0\u2013\u03c0 contacts between inversion-related of the phenyl ring adjacent to the oxime group have a centroid\u2013centroid separation of 3.904\u2005(3)\u2005\u00c5 and a weak C\u2014H\u22ef\u03c0(ring) inter\u00adaction is also observed. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (58.4%) and H\u22efC/C\u22efH (26.4%) contacts. Hydrogen bonding and van der Waals contacts are the dominant inter\u00adactions in the crystal packing.The title compound [systematic name: 2-( The dihedral angle between the oxime plane C (O1/N1/C7) and phenyl rings A and B are 39.48\u2005(9) and 80.11\u2005(14)\u00b0, respectively. The base of the oxime moiety is approximately coplanar with the A phenyl ring plane, as indicated by the O1\u2014N1\u2014C7\u2014C1 torsion angle of 1.0\u2005(3)\u00b0. In the oxime moiety, the O1\u2014N1 [1.4026\u2005(18)\u2005\u00c5] bond length and the O1\u2014N1\u2014C7 [115.36\u2005(14)\u00b0] bond angle may be compared with the corresponding values of O1\u2014N2 [1.423\u2005(3)\u2005\u00c5], O2\u2014N3 [1.396\u2005(3)\u2005\u00c5], O2\u2014N3\u2014C10 [111.5\u2005(2)\u00b0] and O1\u2014N2\u2014C9 [109.4\u2005(2)\u00b0] in the glyoxime moiety reported in 1-\u00adpropane-1,2-dione dioxime  and a weak C\u2014H\u22ef\u03c0(ring) inter\u00adaction  powder was purchased from Merck, and crystallized by slow evaporation from a concentrated solution in ethanol as colourless crystals at room temperature.The alpha-benzoinoxime [ABO (CUiso(H) = 1.2Ueq(C). The hydrogen attached to O2 is disordered over two sites (H2 and H2\u2032) in a 0.5:0.5 ratio and was refined with restraints.Experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0310.1107/S2056989020016163/pk2654sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020016163/pk2654Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020016163/pk2654Isup3.cmlSupporting information file. DOI: 2049764CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The quinoline moiety of the title quinoline carboxamide derivative is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry. 26H25N3O, is described. The quinoline moiety is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry, certainly not planar. Both intra- and inter\u00admolecular hydrogen bonds are present. Hirshfeld surface analysis and lattice energies were used to investigate the inter\u00admolecular inter\u00adactions.The structure of the title quinoline carboxamide derivative, C The mean plane of this ring makes a dihedral angle of 7.49\u2005(13)\u00b0 with the mean plane of the benzene ring of the quinoline moiety. The angles between the mean planes of the quinoline ring and the benzene rings with pivot atoms C321 and C411 are 28.99\u2005(11) and 59.16\u2005(11)\u00b0 respectively. The dihedral angle between the mean plane of these benzene rings is 64.71\u2005(14)\u00b0.An ellipsoid plot for compound anti conformation placing the quinoline ring trans in relation to the ring with pivot atom C321. The amide group atoms are essentially coplanar with the quinoline ring with deviations of \u22120.034\u2005(3), (C31), \u22120.009\u2005(2) (O31), 0.009\u2005(2), (N32) and 0.145\u2005(3)\u2005\u00c5 (C321). The geometric arrangement of the amide permits the formation of an intra\u00admolecular hydrogen bond between the amine hydrogen atom and the carboxyl group of the amide, N41\u2014H41\u22efO31; geometric parameters are given in Table\u00a01The amide group attached to C3 is coplanar with the quinoline ring system. The C\u2014N rotamer of the amide has an sp3 hybridization of N41. An inspection of the amine bond lengths shows that there is a slight asymmetry of the electronic distribution around it: C4\u2014N41 = 1.364\u2005(3)\u2005\u00c5 while N41\u2014C411 = 1.437\u2005(4)\u2005\u00c5, suggesting there is higher density between the nitro\u00adgen and the carbon atom of the quinoline ring system. However, these bonds and angles are typical for a Cquinoline\u2013NH\u2013C\u2013R group, see the Database Survey below. As a consequence of the screw-boat pucker of the pyridine ring, the C4\u2014N41 bond is displaced from the pyridine mean plane with a deviation of 0.159\u2005(2)\u2005\u00c5 for N41; atom C411 is displaced by 0.965\u2005(3)\u2005\u00c5 and consequently, the N41\u2014C411 bond lies further from the mean plane.The secondary amine has a slightly pyramidal geometry, certainly not planar. The angles C411\u2014N41\u2014C4, C41\u2014N41\u2014H41 and C411\u2014N41\u2014H41 are 125.7\u2005(2), 112\u2005(2) and 115\u2005(2)\u00b0, respectively, the sum of which (352.7\u00b0) is less than 360\u00b0; in addition, atom H41 lies 0.41\u2005(3)\u2005\u00c5 out of the C4/N41/C411 mean plane, confirming the x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01), hydrogen bonds, forming C6 chains which run parallel to the a-axis formed by the action of the 21 screw axis at (x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01) hydrogen bond, Table\u00a01B\u22efO31, both involve atom O31 as an acceptor and link the chains described above to form a sheet which extends along the b-axis direction.In the crystal, the mol\u00adecules are linked by N32\u2014H32\u22efN1, polarization (Epol = \u221252.8\u2005kJ\u2005mol\u22121), dispersion (Edisp = \u2212251.6\u2005kJ\u2005mol\u22121) and repulsion (Erep = 210.4\u2005kJ\u2005mol\u22121). The dispersive energy contributes the most to the total stabilization energy of the lattice, in addition to the C\u2014H\u22efO hydrogen bonds, and to the C\u2014H\u22ef\u03c0 inter\u00adaction. The stabilization energy comes from six sub-structural motifs made by the mol\u00adecule pairs I to VI that are shown in Figs.\u00a03\u22121 for the lattice, half of it, \u2212184.7\u2005kJ\u2005mol\u22121 attributed to the  mol\u00adecule. That energy corresponds approximately to 88% of the total stabilization energy of the network.Hirshfeld surfaces , there are high percentages of C\u22efH/H\u22efC close contacts (27.0%) and of N\u22efH/H\u22efN close contacts (6.5%), see Table\u00a02The percentages of atom\u22efatom close contacts taken from the FP plot , as can be identified by the red spots in the Hirshfeld Surface  hydrogen bonds, forming C6 chains which run parallel to the a-axis direction, formed by the action of the 21 screw axis at (x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01) hydrogen bond, Figs. 3The nitro\u00adgen atom N32 acts as a donor for N1 (N32\u2014H32\u22efN1). N1 also acts as an acceptor for C6, making a C6\u2014H6\u22efN1 hydrogen bond, seen as a red spot in Fig.\u00a09c-axis direction, as a result of the propagation of the mol\u00adecule pairs IVa/IVb depicted in Fig.\u00a06In addition, the C\u2014H\u22ef\u03c0 inter\u00adaction can also be identified in the HS of the mol\u00adecule, Fig.\u00a09Va/Vb and VIa/VIb, which are also illustrated in Figs. 7x, y, z (green-coloured mol\u00adecule) and \u2212x\u00a0+\u00a0y\u00a0+\u00a01, z\u00a0\u2212\u00a0x\u00a0+\u00a0y\u00a0+\u00a01, z\u00a0+\u00a0Va/Vb and x\u00a0\u2212\u00a0y\u00a0+\u00a0z\u00a0+\u00a01/x\u00a0\u2212\u00a0y\u00a0+\u00a0z\u00a0+\u00a01 for VIa/VIb. Although these mol\u00adecules do not exhibit atom\u22efatom close contacts, each pair provides a significant contribution to the overall lattice stabilization energy of \u221214.5 and \u221211.3\u2005kJ\u2005mol\u22121, respectively for V and VI. The grey mol\u00adecules drawn in this figure indicate a possible pathway for electronic delocalization within the network of mol\u00adecules.Apart from the sub-structural motifs described, there are two extra mol\u00adecule pairs, identified as et al., 2016et al., 2007N,N-di\u00admethyl\u00adamino)\u00adpropyl\u00adamino]-3-nitro\u00adquinoline; Boyd et al., 19921, viz. 1.325 and 1.335\u2005\u00c5 for the two mol\u00adecules in the asymmetric unit of SEZJIR and 1.320\u2005\u00c5 in PABPUD. The corresponding value in 1 is 1.364\u2005(3)\u2005\u00c5.A search of the Cambridge Structural Database -N-(5-fluoro-1H-indazol-3-yl)quinolin-4-amine methanol solvate; Haile et al., 2016ar\u00adyl\u2014N distances lie in the range 1.396 to 1.438\u2005\u00c5 with an average value of 1.418\u2005\u00c5 and an average Cquinoline\u2014N\u2014Csp3ar\u00adyl/ angle of 126.105\u00b0. In the second case, the Csp3ar\u00adyl/\u2014N distances lie in the range 1.439 to 1.478\u2005\u00c5 with an average value of 1.458\u2005\u00c5, with an average Cquinoline\u2014N\u2014Csp3ar\u00adyl/ angle of 123.98\u00b0.The situation is more complex for the N\u2014Cet al. sulfan\u00adyl]-N-phenyl\u00adquinolin-4-amine; Florke & Egold, 2016et al., 2000N-[2-(2-phenyl\u00advin\u00adyl)phen\u00adyl]quinolin-4-amine; Mphahlele & Mphahlele, 2011As noted above, the conformation around the amino N atom is slightly pyramidal. In their paper on bond lengths in organic compounds, Allen  al. 2006 discuss N-(4-fluoro\u00adphen\u00adyl)-6-methyl\u00adquinoline-3-carboxamide; Govender et al., 2018N-isopropyl-6-methyl-2-phenyl\u00adquino\u00adline-3-carboxamide; Benzerka et al., 20101.There are two compounds in the database which have an amide group attached to C3, GICGIL  were refined. The latter was refined since it is involved in a short contact with H32, which is attached to N32. Although in the riding model for H2 the H-atom position is within the highest contour on the difference map, it is not at the centre. In the refined model it is. The H\u22efH distances are 1.87 and 1.93\u2005\u00c5 for the riding and refined models, respectively. The angles around C2 are N1\u2014C2\u2014C3 = 125.9\u2005(3) and 125.9\u00b0(3); N\u2014C2\u2014H2 = 117 and 111.9\u2005(17)\u00b0 and C3\u2014C2\u2014H2 = 117 and 122.2\u2005(17)\u00b0 for riding and refined H atoms, respectively. In the case of H32, the N32\u2014H32 distance changes from 0.89\u2005(3) to 0.90\u2005(4)\u2005\u00c5 and the angle C31\u2014N32\u2014H32 changes from 120\u2005(2) to 119\u2005(2)\u00b0 for riding to refined, respectively, which are really insignificant shifts. Hence, in this case the short contact does induce a shift in the angular position of H2 from its calculated position.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020000298/zl2767sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000298/zl2767Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000298/zl2767sup3.tifSpectra. DOI: 1879928CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "After annealing 52Rh/48Fe(001) bilayers above 600\u00a0\u00b0C the \u03b1l\u02b9 phase increases in grain size and either develops into \u03b1h\u02b9 with high magnetization  or remains in the \u03b1l\u02b9 phase. In contrast to \u03b1l\u02b9, the \u03b1h\u02b9\u2009\u2194\u2009\u03b1\u02ba transition in the \u03b1h\u02b9 films is completely suppressed. When the annealing temperature of the 45Rh/55Fe(001) samples is increased from 450 to 800\u00a0\u00b0C the low-magnetization nanocrystalline \u03b1l\u02b9 films develop into high crystalline perfection epitaxial \u03b1h\u02b9(001) layers, which have a high magnetization of\u2009~\u20091,275\u00a0emu/cm3. \u03b1h\u02b9(001) films do not undergo a transition to an antiferromagnetic \u03b1\u02ba phase. In 68Rh/32Fe(001) samples above 500\u00a0\u00b0C non-magnetic epitaxial \u03b3(001) layers grow on the Fe(001) interface as a result of the solid-state reaction between the epitaxial \u03b1l\u02b9(001) and polycrystalline Rh films. Our results demonstrate not only the complex nature of chemical interactions at the low-temperature synthesis of the nfm-B2 and \u03b1l\u02b9 phases in Rh/Fe(001) bilayers, but also establish their continuous link with chemical mechanisms underlying reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transitions.Here we first report results of the start of the solid-state reaction at the Rh/Fe(001) interface and the structural and magnetic phase transformations in 52Rh/48Fe(001), 45Rh/55Fe(001), 68Rh/32Fe(001) bilayers from room temperature to 800\u00a0\u00b0C. For all bilayers the non-magnetic nanocrystalline phase with a B2 structure (nfm-B2) is the first phase that is formed on the Rh/Fe(001) interface near 100\u00a0\u00b0C. Above 300\u00a0\u00b0C, without changing the nanocrystalline B2 structure, the phase grows into the low-magnetization modification \u03b1 K\u03b1\u02ba\u2192\u03b1\u02b9\u2009~\u2009100\u00a0\u00b0C between antiferromagnetic (AFM) \u03b1\u02ba and ferromagnetic (FM) \u03b1\u02b9 phases in a narrow (0.48\u2009<\u2009xRh\u2009<\u2009056) concentration interval in chemically ordered B2-FeRh alloys1. This transition is accompanied by an isotropic volume expansion of\u2009~\u20091% of the B2-FeRh unit cell, which not only radically changes the magnetic properties, but also changes the entropy3 and resistivity4. The magnetostructural \u03b1\u02ba\u2009\u2192\u2009\u03b1\u02b9 (AFM-FM) transition gives existence to the giant magnetostriction5 large magnetoresistance7 and magnetocaloric effects8 in B2-FeRh alloys. Numerous studies of bulk samples indicate that the starting temperature TK\u03b1\u02ba\u2192\u03b1\u02b9 and characteristics of the \u03b1\u02ba\u2009\u2192\u2009\u03b1\u02b9 transition may be modified by variations the magnetic field10, microstructure11, thermal treatment12, energetic ion irradiation13, stress14 and hydrostatic pressure17 and can also be tuned over a wide temperature range (100\u2013600\u00a0K) by chemical substitution18. Although bulk B2-FeRh samples exhibit a sharp transition with a small thermal hysteresis, thin films and nanoparticles often have an incomplete and broad asymmetrical hysteresis AFM-FM transition34. The starting transition temperature TK\u03b1\u02ba\u2192\u03b1\u02b9 and magnetic properties in B2-FeRh films depend not only on compositional variations34, but are also highly sensitive to the type of substrate35, the thickness of the thin film samples30, the nature underlayers36 and the capping layers31. Significant stresses arise at the film/substrate interface24, which makes it possible to control the magnetic and electrical transport properties of B2-FeRh films on ferroelectric substrates40 by varying the external electric field. Many groups using magnetron sputtering or molecular beam epitaxy achieved epitaxial B2-FeRh(001) films grown on MgO(001) crystalline substrates. In most studies high-temperature heat treatments above 600\u00a0\u00b0C were used to obtain the high crystalline quality of chemically B2-ordered phase33. However, chemical interactions of Rh with Fe and solid-state synthesis of the Rh-Fe phases at the Rh/Fe interface remain completely uninvestigated.An intriguing feature of the equilibrium diagram of the Fe-Rh system is the existence of the low-temperature transition at TRh\u2009<\u2009056) concentration interval and the reaction products for 45Rh/55Fe(001) and 68Rh/32Fe(001) samples lie in Fe-rich and Rh-rich regions of the Fe\u2013Rh system. The main purpose of this article is to show the complex and intricate nature of the B2-FeRh phases synthesis, which begins to form on the Rh/Fe interface at\u2009~\u2009100\u00a0\u00b0C.In this work, we describe the solid-state reactions between polycrystalline Rh with epitaxial Fe(001) films in 52Rh/48Fe(001), 45Rh/55Fe(001) and 68Rh/32Fe(001) bilayers with 52Rh:48Fe, 45Rh:55Fe and 68Rh:32Fe atomic ratios, respectively. Under these conditions, the reaction products of 52Rh/48Fe(001) fall into the \u00a0transition and a high-ferromagnetic \u03b1h\u02b9 with a magnetization\u2009~\u20091,220\u00a0emu/cm3 and with a completely depressed \u03b1h\u02b9\u2009\u2192\u2009\u03b1\u02ba transition. As the annealing temperature increases above 600\u00a0\u00b0C the reaction products contain a mixture of epitaxial \u03b1l\u02b9(001) and \u03b1h\u02b9(001) grains. Figure\u00a04(Ta)/K40 and the MS(Ta)/MS0 relative magnetization as a function of the annealing temperature Ta {where for 52Rh/48Fe(001) samples K40\u2009=\u20092.4\u2219105\u00a0erg\u00a0cm3 and MS0\u2009=\u2009825\u00a0emu/cm3, see \u201ca the constant K4(Ta) monotonically decreases and becomes zero within experimental accuracy after annealing at 800\u00a0\u00b0C. This means that the first magnetic anisotropy constant K1 of the B2\u2014ordered FeRh phase is zero or less than the measurement error (0.2\u2009\u00d7\u2009104\u00a0erg/cm3). A value of K1\u2009~\u20090 is\u00a0consistent with\u00a0the FeRh single films exhibiting an in-plane easy axis of magnetization with no measurable magnetocrystalline anisotropy41. Therefore, the K4(Ta)/K40 dependence can be used to find the thickness, magnetization and magnetic moment of the reacted Fe(001) layer after annealing at Ta /K40 and the relative magnetization MS(Ta)/MS0 decrease identically as the annealing temperature increases up 300\u00a0\u00b0C. The synchronous decrease of the K4(Ta)/K40 and MS(Ta)/MS0 values clearly proves the onset of the slow mixing of the Rh and Fe layers and the synthesis of the nonferromagnetic B2-FeRh(001) phase (nfm-B2) on the Rh/Fe(001) interface, whose volume increases with an increase in annealing temperature to 300\u00a0\u00b0C. Above 300\u00a0\u00b0C the magnetization increases to MS/MS0\u2009~\u20091, which indicates a phase transformation of the nfm-B2 to the ferromagnetic \u03b1l\u02b9 phase. From Fig.\u00a0l\u02b9/Fe (001) has the magnetization of the initial sample MS0\u2009=\u2009825\u00a0emu/cm3 (MS/MS0\u2009~\u20091) in the temperature range (350\u2013500\u00a0\u00b0C), which means that only the Fe atoms contribute to the saturation magnetization of \u03b1l\u02b9-FeRh. Surprisingly, after annealing at 550\u00a0\u00b0C, the saturation magnetization decreases to 660\u00a0emu/cm3 (~\u200920%), but the reaction product layer participates completely in the reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transition  film at the \u03b1l\u02b9-FeRh(001)/Fe(001) interface. Therefore, a possible explanation is the deformation of some \u03b1l\u02b9-grains with a loss of ferromagnetic order. However, the question about the exact origin of the decrease of MS/MS0 at 550\u00a0\u00b0C remains open. All of the 52Rh/48Fe (001) samples had the same temperature dependencies of the magnetization MS (Ta) up to 600\u00a0\u00b0C. However, after annealing above 600\u00a0\u00b0C the magnetizations of MS sharply increased and assumed values that centered either around MS1\u2009~\u20091,220\u00a0emu/cm3  or MS2\u2009~\u2009940\u00a0emu/cm3   of the synthesized layer B2-FeRh in the Rh/B2-FeRh/Fe (001) trilayer by the torque method at room temperature, after annealing at temperature Ta and after cooling in liquid nitrogen mN(Ta). To characterize the reversible \u03b1\u02b9\u2009\u2194\u2009\u03b1\u02ba transition, we introduce the value \u03b7\u2009=\u20091\u00a0\u2212\u00a0mN(Ta)/m(Ta) for which \u03b7\u2009=\u20090 is absence of transition and \u03b7\u2009=\u20091 is perfect transition (see \u201ca) of the \u03b1\u02b9\u2009\u2194\u2009\u03b1\u02ba transition which has values (200\u2013300\u00a0\u00b0C) \u03b7\u2009=\u20090, (400\u2013600\u00a0\u00b0C) \u03b7\u2009>\u20090.95 and (700\u2013800\u00a0\u00b0C) \u03b7\u2009=\u20090 for the (B) samples and \u03b7\u2009=\u20090.95\u20130.8 for the (A) samples in the specified temperature ranges. In the temperature interval 200\u2013300\u00a0\u00b0C, the equality \u03b7\u2009=\u20090 is determined by the formation of a non-magnetic nfm-B2 phase. Although the \u03b1l\u02b9 (001) layer is located between the Rh and Fe (001) layers and grows epitaxial on the surface of Fe (001) in the (400\u2013600\u00a0\u00b0C) interval it has a reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transition with a low residual magnetization  samples. We hypothesize that the \u03b1\u02b9 phase has two B2-ordered polymorphic modifications having similar lattice parameters, but different magnetic properties. In the first modification the \u03b1l\u02b9 phase has a low magnetization about 825\u00a0emu/cm3, which is defined only by the Fe atoms with the Rh atoms not contributing to the magnetization, and the \u03b1l\u02b9 undergoes a complete reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transition  samples, the Fe atoms supposedly polarize the Rh and the Rh atoms make the contribution to the saturation magnetization 1,220\u00a0emu/cm3 and in the \u03b1h\u02b9 phase the \u03b1h\u02b9\u2009\u2194\u2009\u03b1\u02ba transition is completely suppressed  and with an increase in annealing temperature the phase sequence 52Rh/48Fe\u2009\u2192\u2009(~\u2009100\u00a0\u00b0C) nfm-B2\u2009\u2192\u2009(300\u00a0\u00b0C) \u03b1l\u02b9\u2009\u2192\u2009(600\u00a0\u00b0C) \u03b1l\u02b9 or \u03b1h\u02b9 is formed as shown in Fig.\u00a0In experiments, all 52Rh/48Fe001) samples, after annealing each in a temperature range of 100\u2013800\u00a0\u00b0C, were subjected to an investigation of the \u03b1\u02b9\u2009\u2194\u2009\u03b1\u02ba transition, consisting of measurements of the magnetic moment m layers on the MgO(001) surface. The K4(Ta)/K40 and MS/MS0 dependencies (where for 45Rh/55Fe(001) samples K40\u2009=\u20092.5\u00a0\u00d7\u00a0105\u00a0erg\u00a0cm3 and MS0\u2009=\u2009875\u00a0emu/cm3, see \u201cl\u02b9(001) with\u00a0low magnetization (MS/MS0\u2009~\u20091.0) grows into the high quality epitaxial phase \u03b1h\u02b9(001) with\u00a0high magnetization (MS/MS0\u2009~\u20091.47) above 450\u00a0\u00b0C. The high quality of the chemical ordering of the \u03b1h\u02b9(001) films after annealing at 500\u00a0\u00b0C and 800\u00a0\u00b0C supports the order parameter S\u2009=\u20090.96\u2009\u00b1\u20090.02, which is more than the S\u2009=\u20090.90\u2009\u00b1\u20090.02 for \u03b1l\u02b9 in 52Rh/48Fe films. This result is unexpected, since the \u03b1l\u02b9 exists in a narrow composition range of nearly equiatomic concentration and must have a more complete B2 order than the Fe-rich \u03b1h\u02b9 phase. The \u03b1h\u02b9(001) and \u03b1l\u02b9(001) films have the same orientation relationship with the substrate MgO(001) /K40 dependence  and the AFM-FM transition has a relatively low residual magnetization  \u03b1h\u02b9. Finally, we proved that even a slight Fe doping of \u03b1l\u02b9 causes a chemical reaction between Fe and \u03b1l\u02b9 and the start of the synthesis of the \u03b1h\u02b9 phase. This suggests that the high magnetization \u03b1h\u02b9 phase occurring in the 52Rh/48Fe(001) bilayer (B samples) also has more Fe content than \u03b1l\u02b9 and explains the compositional heterogeneity arising as a result of the nonequilibrium reaction processes. Thus, we show the phase evolution 45Rh/55Fe\u2009\u2192\u2009(~\u2009100\u00a0\u00b0C) nfm-B2\u2009\u2192\u2009(300\u00a0\u00b0C) \u03b1l\u02b9\u2009\u2192\u2009(450\u00a0\u00b0C) \u03b1h\u02b9 is induced by the solid-state-reaction method and the final reaction product is a highly B2-ordered phase \u03b1h\u02b9, which has a high magnetization of 1,270\u00a0emu/cm3 and in which the reversible \u03b1h\u02b9\u2009\u2194\u2009\u03b1\u02ba transition is completely suppressed.The schematic diagram in Fig.\u00a0Fig.\u00a0h\u02b900 layers ol\u02b9 phases during annealing up to 500\u00a0\u00b0C in the 68Rh/32Fe, 52Rh/48Fe  interface  layer in the Rh/\u03b1l\u02b9(001) bilayer system  surface originating from the solid-state reaction Rh\u2009+\u2009\u03b1l\u02b9\u2009\u2192\u2009(500\u00a0\u00b0C) \u03b3. As shown in Fig.\u00a0S(Ta)/MS0, and the K4(Ta)/K40 dependence presented in Fig.\u00a0l\u02b9 above 300\u00a0\u00b0C and the paramagnetic \u03b3 phases above 500\u00a0\u00b0C. As follows from Fig.\u00a0l\u02b9 phase exists and undergoes a reversible AFM-FM transition (\u03b7\u2009~\u20090.9) in the 300\u2013500\u00a0\u00b0C temperature range  nfm-B2\u2009\u2192\u2009(300\u00a0\u00b0C) \u03b1l\u02b9\u2009\u2192\u2009(500\u00a0\u00b0C)\u03b3 during thermal annealing up to 800\u00a0\u00b0C and the final reaction product contains only an epitaxial \u03b3(001) layer on the MgO(001) surface.Figure\u00a08Fe Fig.\u00a0a and 55Rl\u02b9\u2009\u2192\u2009\u03b1\u02ba transition, the synthesis kinetics of the nfm-B2 layer during isothermal aging at 110\u00a0\u00b0C was investigated. As stated above, deposition of Rh on Fe(001) at room temperature at any ratio of thicknesses between Rh and Fe leads to the formation of a thin interfacial nanocrystalline nfm-B2 layer. However, slight heating to 100\u00a0\u00b0C during sputtering cannot be excluded, therefore, aging of as-deposited samples was investigated at 110\u00a0\u00b0C. XRD data from the as-deposited Rh/Fe(001) bilayer and after aging up to 360\u00a0h shows a small broadened (001) superlattice and the fundamental (002) peaks of the nfm-B2 phase which did not change from aging time to 360\u00a0h  layer, which entered into a reaction with Rh at 110\u00a0\u00b0C, as a function of aging time. There is a large experimental error in the thickness dFe measurements and therefore the dependence dFe(t) is impossible to describe by an unambiguous kinetic equation, which suggests a possible growth mechanism. As shown in Fig.\u00a0Fe after aging for 360\u00a0h at 110\u00a0\u00b0C is\u2009~\u20098\u00a0nm, which corresponds to the thickness dnfm-B2\u2009~\u200917\u00a0nm of the nfm-B2 layer  interface at the temperature of the \u03b10\u00a0h Fig.\u00a0a. This m\u00a0nm Fig.\u00a0b. Figurel\u02b9 around 300\u00a0\u00b0C, we investigated the evolution of the temperature dependencies of the magnetization and the thickness of the interfacial hB2-FeRh layer in the 52Rh/B2-FeRh/48Fe(001) trilayer after annealing at 280\u00a0\u00b0C, 300\u00a0\u00b0C and 350\u00a0\u00b0C. Figure\u00a0nfm-B2 interlayer in the 48Rh/nfm-B2/52Fe(001) trilayer increases to a thickness around dnfm-B2 ~ 30\u00a0nm after annealing at 280\u00a0\u00b0C. \u2009~\u200920\u00a0nm of the \u03b1l\u02b9 layer in the B2-FeRh interlayer. This clearly proves that after annealing at 300\u00a0\u00b0C the B2-FeRh interlayer contains a mixture of 50% nfm-B2 and 50% \u03b1l\u02b9 phases /K40 dependence /K40 \u2009<\u2009150\u00a0\u00b0C49, Tin(Ni/Al)\u2009~\u2009180\u00a0\u00b0C50, Tin(Cd/Au)\u2009=\u200967\u00a0\u00b0C51 in Ti/Ni, Ni/Al, Cd/Au bilayers, respectively. These temperatures are close to or coincide with the reverse\u00a0martensitic transformation starting temperatures\u00a0As(B2-TiNi)\u2009~\u2009100\u00a0\u00b0C, As(B2-NiAl)\u2009~\u2009180\u00a0\u00b0C, As(B2-CdAu)\u2009=\u200967\u00a0\u00b0C. The reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transition in B2-FeRh possesses all the characteristics of a martensitic transformation , because it can pass at high speeds53, has isotropic volume changes at the transition1, can be induced by the application of stress40 and magnetic field10, has martensitic instabilities54 and the \u03b1l\u02b9 and \u03b1\u02ba lattices have a cube-on-cube orientation relationship. According to the phase diagram, the transition \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba has a minimum temperature Tk\u2009~\u2009100\u00a0\u00b0C among other structural transformations in the Fe-Rh system. From the above, we have concluded that the initiation temperature of the reaction Tin(Rh/Fe) in the Rh/Fe bilayer coincides with the martensitic-like transition temperature TK\u2009~\u2009100\u00a0\u00b0C in B2-FeRh. The coincidence of the starting temperature of the reaction between Fe and Rh and the temperature of the magnetostructural AFM-FM transition suggests common chemical mechanisms behind both phenomena, but that connection remains to be confirmed by additional experimentation.It is well established that ordered B2 alloys, such as NiTi, AuCd, NiAl have reversible low-temperature martensitic transformations, in which the high-temperature austenite B2-phase develops into a low-temperature martensitic phase through a complex process of the55 and found in the experimental study36. Competition between the \u03b1l\u02b9 and \u03b1\u02ba phases during the partial crystallization suppresses grain growth and stabilizes the nano-grained B2 structures in an amorphous matrix. The formation of an amorphous phase is a quite common phenomenon in the initial stage of solid-state reactions in bilayers and multilayers, although the nature of this phenomenon is still a subject of dispute58. It is interesting to note the general features of the initial stage of the synthesis of B2 phases in Ti/Ni and Rh/Fe thin films. In Ti/Ni multilayers the amorphous phase starts near the martensitic transition temperature (~\u2009100\u00a0\u00b0C), which turns into B2-NiTi60 at annealing temperatures above 350\u00a0\u00b0C. Similar to Ti/Ni, the reaction in the Rh/Fe(001) bilayer starts at\u2009~\u2009100\u00a0\u00b0C with the formation of the interfacial amorphous phase, which partially crystallizes. From this point the as-deposited films consist of nanocrystalline B2 grains dispersed in the amorphous matrix. This strongly suggests that both amorphous phases are amorphous martensite, which may be a universal phenomena of the solid-state synthesis of martensitic phases61. This scenario is different from the synthesis of B2-NiAl and B2-AuCd, which begin to form in Al/Ni50 and Cd/Au51 bilayers at martensitic transformation temperatures without the formation of an intermediate amorphous martensite.As mentioned above, the formation of compounds at the Rh/Fe interface starts in the temperature range 100\u2013300\u00a0\u00b0C from the synthesis of the non-ferromagnetic nfm-B2 phase. Since this phase has only (001) and (002) B2-FeRh reflections, this means that nfm-B2 is either a martensitic-like antiferromagnetic \u03b1\u02ba-phase or a non-ferromagnetic martensitic variant which is stabilized by strains resulting from the non-equilibrium synthesis of the nfm-B2 phase. B2-FeRh, similar to other B2 phases of NiTi, AuCd, NiAl alloys, experiences premartensitic instabilities with the subsequent formation of the different\u00a0structural variants of martensite. Our hypothesis is the amorphous phase appears above 100\u00a0\u00b0C at the Rh/Fe interface, which is then transformed into a\u00a0nanocrystalline state containing B2 nanograins of martensite variants with lattice parameters close to \u03b1\u02ba martensite.\u00a0This is consistent with the possible existence of various structural phases of FeRh, predicted by ab initio calculationsin(\u03b1h\u02b9)\u2009=\u2009\u2009~\u2009450\u00a0\u00b0C and Tin(\u03b3)\u2009=\u2009\u2009~\u2009500\u00a0\u00b0C of the \u03b1h\u02b9 and \u03b3 phases coincide with the phase transition temperatures in the Fe-rich and Rh-rich regions of the Fe\u2013Rh system, respectively. Such an approach is justified by us for the well-studied Fe\u2013Ni system62 and made it possible to predict phase transformations in other binary metallic systems48. Therefore, further study of solid-state reactions in Rh/Fe films, depending on the composition, will make it possible to specify the low-temperature part of the Fe\u2013Rh phase diagram, which still remains unknown63.Analysis of the general thermodynamic characteristics and features of B2-FeRh and B2-NiTi suggests the possibility of a fabrication of the B2-FeRh compound by self-propagating synthesis  samples and the \u03b1l\u02b9 reacted with Ph and formed the non-ferromagnetic \u03b3 phase in the 68Rh/32Fe(001)samples. Magnetic analysis has revealed that only the \u03b1l\u02b9 undergoes the complete reversible \u03b1l\u02b9\u2009\u2194\u2009\u03b1\u02ba transition and there\u2019s no transition in the \u03b1h\u02b9 samples. Thus, our work not only provides an idea of how phase sequences start and develop depending on the composition of the Fe/Rh bilayers, but also suggests the interesting possibility that a similar chemical mechanism may be at play behind the low-temperature reaction of Fe and Rh and the AFM-FM transition in B2-FeRh.In conclusion, we have uncovered that regardless of the Rh and Fe thicknesses the thin nonmagnetic nanocrystalline B2-FeRh layer starts to form at\u2009~\u2009100\u00a0\u00b0C and grows up to 300\u00a0\u00b0C on the Rh/Fe interface. Above 300\u00a0\u00b0C the nonmagnetic phase is converted into a low-ferromagnetic B2 \u03b14, which coincided with the value of bulk iron K1\u2009=\u20094.9\u2009\u00d7\u2009105\u00a0erg/cm3. The constant K4 in the (001) plane was determined by a torque magnetometer in a magnetic field H\u2009=\u200912 kOe. The torque curve L\u01c0\u01c0(\u03c6) in the (001) plane was determined according to the equation 2L\u01c0\u01c0(\u03c6)\u2009=\u2009K4Vsin4\u03c6\u2009+\u20092 Ku VSin(2\u03c6\u2009+\u2009\u03b3), in which, in addition to the dominant 4\u03c6-term, there is a minor 2\u03c6-term Ku term due to the surface roughness of the MgO(001) substrate and a slight misorientation of the Fe(001) grains. In the equation Ku is uniaxial anisotropy constant, V is the volume of the film, \u03c6 is the angle between the easy axis of fourfold anisotropy and the magnetization MS, \u03b3 is the angle between the easy axis of fourfold anisotropy and the axis of the uniaxial anisotropy. The K4V value was calculated from the torque curve L\u01c0\u01c0(\u03c6) at the maximum of the 4\u03c6-term: 2Lmax\u2009=\u2009K4V. High quality epitaxial Fe(001)/MgO(001) films also can be obtained by various other methods as reported in the literature.At first the epitaxial Fe(001)/MgO(001) films were grown on single-crystal MgO(001) substrates\u00a0by a\u00a0thermal\u00a0evaporation\u00a0method in a vacuum chamber at a pressure of 10\u20136\u00a0mbar. To obtain high-quality Fe(001) films, the substrates was previously outgassed at 300\u00a0\u00b0C for 1\u00a0h and the Fe layers were deposited at 250\u00a0\u00b0C. Epitaxial Fe (001) films had the orientation ratio Fe(001),[100]||MgO(001),[110] with the MgO(001) substrate and the magnetocrystalline\u00a0anisotropy constant K\u20136\u00a0mbar, and a working pressure of\u2009~\u20091 mTorr Ar was used during sputtering. To prevent a reaction between Rh and Fe, the Rh layer was deposited at room temperature. Under such deposition conditions the polycrystalline Rh layer was formed on the Fe(001) surface. Three different types of samples were prepared for the experiments, namely Rh/Fe (001) bilayers with Rh-rich, approximately 1Fe:1Rh and Fe-rich atomic ratios, each with a total thickness about 300\u00a0nm. The elemental chemical composition determined by energy dispersion X-ray (EDX) analysis showed sample compositions of Rh68Fe32, Rh52Fe48 and Rh45Fe55, respectively. The saturation magnetization MS0 and the magnetic fourfold anisotropy constants K40 were determined for the total volume of the 52Rh/48Fe, 45Rh/55Fe and 68Rh/32Fe bilayers, which turned out to be MS0\u2009=\u2009825 emu/cm3, K40\u2009=\u20092.2\u00a0\u00d7\u00a0105\u00a0erg/cm3 for the 52Rh/48Fe bilayers, MS0\u2009=\u2009875 emu/cm3, K40\u2009=\u20092.4\u00a0\u00d7\u00a0105\u00a0erg/cm3 for the 45Rh/55Fe bilayers and MS0\u2009=\u2009450 emu/cm3, K40\u2009=\u20091.25\u00a0\u00d7\u00a0105\u00a0erg/cm3 for the 68Rh/32Fe bilayers.The starting Rh/Fe(001) bilayers were obtained by the evaporation of the Rh layers on Fe(001)/MgO(001) samples using dc sputtering in a magnetron sputtering system. The base pressure of the chamber was less than\u2009~\u20091\u00a0\u00d7\u00a010S and the coercivity HC were measured with a vibration magnetometer in magnetic fields up to 22 kOe. All saturation magnetization measurements were monitored using the torque method64.The reversible AFM-FM phase transitions were checked using a superconducting quantum interference device (SQUID) magnetometer. Magnetic fields of H\u2009=\u20091.0 kOe were applied along the in-plane [100] MgO direction, which coincides with the easy axis of the Rh/Fe (001) bilayers, at all measurements in the 77\u2013400\u00a0K temperature interval. The saturation magnetization M001/I002)1/2/1.07, where I001 and I002 are experimental integrated intensities of superstructural (001) and fundamental (002) reflections65.The formed phases were identified with a DRON-4-07 diffractometer (CuKa radiation). The epitaxial relationships between MgO(001) and the B2, \u03b3 layers that formed in the reaction products were X-ray studied with a PANalytikal X'Pert PRO diffractometer with a PIXctl detector. CuKa radiation monochromatized by a secondary graphite monochromator was used in the instrument. The order parameter for the synthesized samples at temperatures in the 600\u2013800\u00a0\u00b0C range was estimated using the equation S\u2009=\u2009 at 40\u00a0kV. In order to protect the surface of interest from milling by the Ga\u2009+\u2009ion beam during sample preparation, a Ge layer was deposited onto the Fe-Rh film before cross-sectional sample preparation by FIB. TEM studies were carried out using a Hitachi HT7700 TEM  equipped with a STEM system and a Bruker Nano XFlash 6T/60 energy dispersive X-ray (EDX) spectrometer. The imaging and EDX spectroscopy line scans and mapping were carried out in STEM mode with an electron probe of diameter\u2009~\u200930\u00a0nm.\u22126\u00a0Torr for 1\u00a0h. To characterize the phase transformations the crystal structure, the magnetic moments m0(Ta) (where m0(300\u00a0K)\u2009=\u2009MS0V), the magnetic fourfold anisotropy constants K4(Ta) and the degree of the \u03b1\u02b9\u2009\u2192\u2009\u03b1\u02ba transition \u03b7(Ta) were determined for all bilayers after annealing at each temperature Ta. In order to fully characterize the phase transformations, cross-sectional SEM images and an elemental analysis of the phases of several samples using EDX were carried out.The starting 52Rh/48Fe, 45Rh/55Fe and 68Rh/32Fe bilayers were annealed at temperatures ranging from 50 to 800\u00a0\u00b0C in increments of 50\u00a0\u00b0C. The samples were held at each temperature at a pressure of 10a) of the FM-AFM phase transition was determined for all 52Rh/48Fe, 45Rh/55Fe and68Rh/32Fe samples after annealing at each temperature in the range of 100\u2013800\u00a0\u00b0C . The magnetic moments m0(Ta) were measured by the torque method64, after annealing at temperature Ta and cooling in liquid nitrogen mN(Ta), to find the value\u00a0of the degree \u03b7(Ta). The magnetic moment m(Ta) of the synthesized \u03b1l\u02b9\u2014FeRh layer in the Rh/\u03b1l\u02b9\u2014FeRh/Fe(001) trilayer after annealing at temperature Ta is equal to the difference m(Ta)\u2009=\u2009m0(Ta)\u2014K4(Ta)m0/K40 of the magnetic moments of the m0(Ta) film and the K4(Ta)m0/K40 unreacted layer of the Fe(001) layer, where K4(Ta)m0/K40 is the magnetic moments of the unreacted Fe(001) layer. After placing the sample in liquid nitrogen, only the ferromagnetic \u03b1l\u02b9\u2014FeRh phase in the Rh/\u03b1l\u02b9\u2014FeRh/Fe(001) trilayer is subjected to the transition into the antiferromagnetic \u03b1\u02ba phase and the magnetic moment m(Ta) is reduced to mN(Ta). The quantity \u03b7\u2009=\u20091\u00a0\u2212\u00a0mN(Ta)/m(Ta) is a quantitative characteristic of the degree of the \u03b1l\u02b9\u2009\u2192\u2009\u03b1\u02ba transition, where \u03b7\u2009=\u20090 and \u03b7\u2009=\u20091 mean the absence of and the complete FM\u2009\u2192\u2009AFM transition , respectively.In experiments, the degree \u03b7(TSupplementary file1 (DOCX 4798 kb)"}
{"text": "The crystal packing features N\u2014H\u22efN hydrogen bonds, which generate [101] chains.The title structure consists of [Ni(CN) 10H10N3)2[Ni(CN)4], the dihedral angle between the pyridine rings in the cation is 1.92\u2005(13)\u00b0 and the complete anion is generated by a crystallographic centre of symmetry. An intra\u00admolecular N\u2014H\u22efN hydrogen bond occurs in the cation, which closes an S(6) ring. In the crystal, the components are linked by N\u2014H\u22efN and weak C\u2014H\u22efN hydrogen bonds, which generate chains propagating in the [101] direction. Weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed. A Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contact types in the crystal packing are N\u22efH/H\u22efN, C\u22efH/H\u22efC and H\u22efH with contributions of 37.2, 28.3 and 21.9%, respectively.In the title mol\u00adecular salt, (C The C\u2014Non Fig.\u00a01. The  cyanide ligands, exhibiting a square-planar geometry. The bond lengths and angles in the anion are in good agreement with those found in other [Ni(CN)4]2\u2212 salts  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01) link (Table\u00a01H) forms a strong N3\u2014H3A\u22efN2 hydrogen bond with a cyano group acceptor and the H3A\u22efN2 distance is 2.0\u2005\u00c5. Fig.\u00a03S(6) centroids and pyridyl groups [centroid\u2013centroid distance of 3.487\u2005(2)\u2005\u00c5].Fig.\u00a03k Table\u00a01. The secet al., 2007CrystalExplorer 17.5 . Areas on the Hirshfeld surface with high curvedness  can be related to the planar packing arrangement of the cations. The most abundant inter\u00admolecular inter\u00adactions in the crystal packing \u00b7[CuCl4] . The mixture was sealed in a Teflon-lined autoclave and held at 423\u2005K for 3\u2005d, and then cooled to room temperature at a rate of 10\u2005K per hour (yield 27%). Pale-yellow plates of (I)The title compound was synthesized solvothermally under autogenous pressure using a mixture of iron(II) sulfate hepta\u00adhydrate , 2,2\u2032-di\u00adpyridyl\u00adamine  and potassium tetra\u00adcyano\u00adnickelate(II)  in mixed solvents of water/ethanol (3:1 Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902001419X/hb7948sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902001419X/hb7948Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902001419X/hb7948sup3.tifFigure S1 Hirshfeld surface of (C10H10N3)2[Ni(CN)4] mapped with shape index (a) and curvedness (b). DOI: 2040378CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) graph-set motif. Inter\u00admolecular \u03c0\u2013\u03c0 stacking and C\u2014O\u22ef\u03c0 inter\u00adactions dominate the crystal packing.A short [2.592\u2005(3)\u2005\u00c5] intra\u00admolecular N\u2014H\u22efO hydrogen bond leads to an  13H12N2O2, crystallizes in the ortho\u00adrhom\u00adbic space group Pna21 with two very similar mol\u00adecules in the asymmetric unit. An intra\u00admolecular N\u2014H\u22efO hydrogen bond leads to an S(6) graph-set motif in each of the mol\u00adecules. Inter\u00admolecular \u03c0\u2013\u03c0 stacking and C=O\u22ef\u03c0 inter\u00adactions involving the aldehyde O atoms link mol\u00adecules into stacks parallel to [100]. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing stem from H\u22efH (49.4%) and H\u22efO/O\u22efH (21.5%) inter\u00adactions. Energy framework calculations reveal a significant contribution of dispersion energy. The crystal studied was refined as a two-component inversion twin.At 100\u2005K, the title compound, C Two major aspects contribute to the inter\u00adest in modified structural analogues of quinazoline alkaloids. On the one hand, they are attractive targets for the development of methods in organic synthesis; reactions sufficiently general to target a wide range of derivatives of a given lead structure should be easy to carry out and warrant high yields. On the other hand, substituted quinazolines allow the study of structure\u2013property relationships with respect to their biological activities  was first isolated from the plant Mackinlaya subulata Philipson   may be the reason for this selectivity towards primary amines.The title compound, 6-formyl-7,8,9,11-tetra\u00adhydro-51) Fig.\u00a01, does re1) Fig.\u00a01, 2016 \u25b8,1H NMR data and quantum-chemical calculations, Zhurakulov et al. (20161) in the solid state, we studied its mol\u00adecular and crystal structure. We also report the analysis of the Hirshfeld surface and the energy framework of crystalline (1).Based on  al. 2016 confirmeA and B . In contrast to the quinazolinone moiety, the alkyl ring is not planar. The maximum deviation from the least-squares plane through each of the mol\u00adecules is encountered for the atoms C2A and C2B and amounts to 0.515\u2005(3) and 0.521\u2005(3)\u2005\u00c5, respectively. The almost coplanar arrangement of the aldehyde group and the pyrimidine ring in either mol\u00adecule A and B enables an intra\u00admolecular N\u2014H\u22efO inter\u00adaction (Table\u00a01S(6) graph-set motif.The asymmetric unit of the title compound contains two mol\u00adecules  B Fig.\u00a02. They ar B Fig.\u00a02; an overn Table\u00a01 and form1) stack into columns parallel to [100] in an equidistant series of coplanar moieties; the independent mol\u00adecules A and B segregate into different stacks  of 1.5.Mol\u00adecules of  crystallizes in the non-centrosymmetric achiral space group Pna21, and its absolute structure deserves a comment. The absolute structure is linked to the direction of the polar screw axis along [001]. In the absence of heavy atoms, resonant scattering in (1) is minor, with Friedif  were associated with rather large standard uncertainties: the Flack parameter  and benzene  rings and involve contact distances of Cg1\u22efCg3 = 3.5154\u2005(18)\u2005\u00c5 (slippage 0.954\u2005\u00c5) and of Cg7\u22efCg9 = 3.5159\u2005(19)\u2005\u00c5 (slippage 1.054\u2005\u00c5).Consecutive mol\u00adecules in each column along [100] inter\u00adact ts Fig.\u00a04. \u03c0\u2013\u03c0 stavia C=O\u22ef\u03c0 contacts; they amount to C11A=O2A\u22efCg1(x\u00a0+\u00a0y\u00a0+\u00a0z) = 3.212\u2005(2)\u2005\u00c5 and C11B=O2B\u22efCg7(x\u00a0\u2212\u00a0y\u00a0+\u00a0z) = 3.215\u2005(2)\u2005\u00c5. Perpendicular to the stacking direction, non-classical C\u2014H\u22efO hydrogen bonds , the Hirshfeld surface (HS)  or longer than the sum of the van der Waals radii, respectively.In order to visualize inter\u00admolecular inter\u00adactions in (a. H\u22efH contacts are responsible for the largest contribution (49.4%) to the Hirshfeld surface . Besides these contacts, H\u22efO/O\u22efH (21.5%), H\u22efC/C\u22efH (14.9%), C\u22efC (6.7%) and N\u22efC/C\u22efN (4.0%) inter\u00adactions contribute significantly to the total Hirshfeld surface; their decomposed fingerprint plots are shown in Fig.\u00a06c\u2013f. The contributions of further contacts are only minor and amount to N\u22efO/O\u22efN (1.4%), C\u22efO/O\u22efC (1.4%), N\u22efH/H\u22efN (0.5%) and O\u22efO (0.1%).The two-dimensional fingerprint plot for all contacts is depicted in Fig.\u00a06ce Fig.\u00a06b. BesidCrystal Explorer 17  is the sum of electrostatic (Eelec), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies -one moiety with a similar planar conformation to that in the title structure: 3-(2-methyl\u00adphen\u00adyl)-2-(2-oxo\u00adphenyl\u00adeth\u00adyl)-4(3H)-quinazol\u00adinone -quinazolinone quinazolinone -quinazolinone -quinazolinone -2-[2-oxo-2-(thio\u00adphen-2-yl)ethyl\u00adidene]-3-phenyl-2,3-di\u00adhydro\u00adquin\u00adazolin-4(1H)-one , all compounds mentioned above exist as the enamine tautomer in the crystalline state, and their intra\u00admolecular N\u2014H\u22efO hydrogen bond between the ethanone and the amine N atom results in an S(6) graph set motif.A search in the Cambridge Structural Database  was synthesized according to the method of Oripov et al. (1979Rf 0.78 (C6H6: MeOH 4:1). A detailed report on the synthesis of (1) and its characterization by 1H NMR is available in Zhurakulov et al.  = 1.2Ueq(C). The enamine H atoms H5A and H5B were refined with a common isotropic displacement parameter; N\u2014H distances were restrained to similarity.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020016059/wm5590sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020016059/wm5590Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020016059/wm5590sup3.tifFigure S1. DOI: Click here for additional data file.10.1107/S2056989020016059/wm5590Isup4.cmlSupporting information file. DOI: 2049242CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked by C\u2014H\u22efN and weak C\u2014H\u22ef\u03c0 hydrogen bonds and very weak \u03c0\u2013\u03c0 stacking inter\u00adactions. Two-dimensional fingerprint plots show that the largest contributions to the crystal stability come from H\u22efH and C\u22efH/H\u22efC inter\u00adactions. 17H16N2OS, was synthesized by a condensation reaction between 2-amino benzo\u00adthia\u00adzole and 4-N-propoxybenzaldehyde. The benzo[d]thia\u00adzole ring system is nearly planar (r.m.s. deviation 0.0088\u2005\u00c5) and makes a dihedral angle of 3.804\u2005(12)\u00b0 with the phenyl ring. The configuration about the C=N double bond is E. In the crystal structure, pairs of C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into inversion dimers with an R22(16) ring motif. These dimers are additionally linked by weak \u03c0\u2013\u03c0 stacking inter\u00adactions between the phenyl rings, leading to a layered arrangement parallel to (010). Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the packing arrangement are from H\u22efH (47.9%) and C\u22efH/H\u22efC (25.6%) inter\u00adactions.The title compound, C Benzo\u00adthia\u00adzole is a weak base, and is widely found in bioorganic and medicinal chemistry with application in drug discovery as a pharmacologically and biologically active compound \u2005\u00c5 for atom C4]. The benzo[d]thia\u00adzole ring system and the phenyl ring (C9\u2013C14) are slightly twisted with respect to each other, making a dihedral angle of 3.804\u2005(12)\u00b0. In the thia\u00adzole ring, the C6\u2014N1 [1.379\u2005(3)\u2005\u00c5] and C7\u2014N1 [1.288\u2005(3)\u2005\u00c5] distances indicate substantial electronic delocalization. The C8=N2 double bond has a length of 1.272\u2005(3)\u2005\u00c5, and thus is slightly longer than comparable bonds found in other Schiff base structures  and the centroid of the C1\u2013C6 phenyl ring (Cg2) of an adjacent mol\u00adecule : \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z) where Cg3 is the centroid of the C9\u2013C14 phenyl ring. The resulting supra\u00admolecular network is layered and expands parallel to (010).In the crystal structure, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 hydrogen bonds Table\u00a01 between le Fig.\u00a02. Pairs oif Fig.\u00a02. The dimCrystalExplorer -N-benzyl\u00adidenebenzo[d]thia\u00adzol-2-amine skeleton gave 20 hits. Of these 20, the most similar to the title compound are 2-[carbonoimido\u00adyl]phenol -2-[(6-eth\u00adoxy\u00adbenzo\u00adthia\u00adzol-2-yl)imino\u00admeth\u00adyl]-6-meth\u00adoxy\u00adphenol  was then added dropwise into the mixture under stirring, in the presence of a catalytic amount of glacial acetic acid. The reaction mixture was then placed inside an unmodified household microwave oven and was irradiated for 32\u2005min (eight pulses each of 4\u2005min) at 540\u2005W power, with short inter\u00adruptions of one minute. The progress of the reaction was monitored by thin-layer chromatography using ethyl acetate and n-hexane (3:7 v:v) as eluent (Rf = 0.69). The formed precipitate was filtered off, washed with 1-propanol, and dried. The resulting solid was further purified by recrystallization from n-hexane to give the pure imine as a crystalline solid .2-Amino benzo\u00adthia\u00adzole  was dissolved in 10\u2005ml of 1-propanol in a 50\u2005ml borosilicate glass beaker. 4-Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other C\u2013bound H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020012128/wm5582sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012128/wm5582Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012128/wm5582Isup3.cmlSupporting information file. DOI: 1979807CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Diels\u2013Alder cyclo\u00adaddition of cyclo\u00adhepta\u00adtriene and maleic anhydride produces the title carb\u00adoxy\u00adlic anhydride; reaction of this anhydride with 4-bromo\u00adphenyl\u00adaniline forms the corresponding tetra\u00adcyclic imide. The anhydride features C\u2014H\u22efO hydrogen bonds in the solid state, while the imide also features C\u2014H\u22efO hydrogen bonds as well as C\u2014H\u22ef\u03c0 and lone pair\u2013\u03c0 inter\u00adactions. 11H10O3 (I) and C17H14BrNO2 (II), both containing the bi\u00adcyclo\u00ad[2.2.2]octene ring system, are reported here octene ring system. Non-covalent inter\u00adactions present in the crystal structure of II include a number of C\u2014H\u22efO inter\u00adactions. The extended structure of II also features C\u2014H\u22efO hydrogen bonds as well as C\u2014H\u22ef\u03c0 and lone pair\u2013\u03c0 inter\u00adactions, which combine together to create supra\u00admolecular sheets.The syntheses and crystal structures of the two title compounds, C Goh 2014. Private The bond lengths of the carbonyl groups of the anhydride are shorter than the imide, as expected, with C1=O1 = 1.1943\u2005(18), C2=O2 = 1.1904\u2005(17), C1\u2014O3 = 1.3868\u2005(17) and C2\u2014O3 = 1.3978\u2005(16)\u2005\u00c5. The corresponding data for the C1a mol\u00adecule are 1.1913\u2005(17), 1.1871\u2005(18), 1.3855\u2005(17) and 1.3905\u2005(18)\u2005\u00c5, respectively. The configurations of the stereogenic centres in the arbitrarily chosen asymmetric mol\u00adecules are: C3 S, C4 R, C5 R, C8 S, C9 S, C10 R and C3a R, C4a S, C5a S, C8a R, C9a R, C10a S: crystal symmetry generates a racemic mixture in the bulk.The structure of the title anhydride II was solved in the monoclinic space group P21/n, and its atom labeling scheme is shown in Fig.\u00a04II are C3 R, C4 S, C5 S, C8 R, C9 R and C10 S; again, crystal symmetry generates a racemic mixture.The structure of the imide I is dominated by C\u2014H\u22efO hydrogen bonds  to 3.4882\u2005(17)\u2005\u00c5 with D\u2014H\u22efA angles ranging from 119 to 159\u00b0; the C9 bond is likely very weak based on its H\u22efA distance of 2.73\u2005\u00c5. Combined together, these inter\u00adactions create supra\u00admolecular sheets that lie in the ab plane.The extended structure of the anhydride II, the mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds as well as C\u2014H\u22ef\u03c0 and C\u2014Br\u22ef\u03c0 inter\u00adactions (Table\u00a02D\u22efA distance of 3.175\u2005(2)\u2005\u00c5 with a D\u2014H\u22efA angle of 139\u00b0. The C\u2014H\u22ef\u03c0 inter\u00adaction is between C3\u2014H3, which is \u03b1 to the carbonyl group C1(O1), and the aromatic ring C12\u2013C17. This inter\u00adaction has a H\u22efCg distance of 3.801\u2005(2)\u2005\u00c5 (where Cg is the centroid of the C12\u2013C17 ring), with a C\u2014H\u22efCg angle of 165\u00b0. The aromatic ring C12\u2013C17 bears an electron-withdrawing bromine atom, and accepts a lone pair(LP)\u2013\u03c0 inter\u00adaction from the bromine atom of a nearby mol\u00adecule \u2005\u00c5 with a C15\u2014Br1\u22efCg angle of 87.43\u2005(6)\u00b0. Dimers of imide II are formed via the Br\u22ef\u03c0 inter\u00adactions, and these dimers are linked into supra\u00admolecular sheets that lie along (010) by the C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions via short-path distillation and the reaction mixture was left to cool at room temperature. The round-bottom flask was fitted with a stopper and left to recrystallize for 48\u2005h to afford large, cream-colored needles. The product was recrystallized once more by dissolving in 8\u2005ml of xylene: after a week at room temperature, the pure product I was obtained in the form of large colorless crystals . 1H NMR  \u03b4 5.88 , 3.46 , 3.23 , 1.17\u20131.04 . 13C NMR  \u03b4 172.45, 128.55, 45.88, 33.65, 9.56, 5.24.Cyclo\u00adhepta\u00adtriene  and maleic anhydride  were added to an oven-dried round-bottom flask containing 10\u2005ml of xylene and the mixture was refluxed for 1.5\u2005h. Approximately half of the xylenes were distilled off Synthesis of the imide (II)I  and p-bromo\u00adaniline  were added to a vial containing 5\u2005ml of xylene and the mixture was refluxed for 5\u2005min. The mixture was then cooled to room temperature and left for 5 days in a sealed vial. The precipitate was recrystallized from ethanol solution to yield colorless needle-like crystals of II . 1H NMR  \u03b4 7.54 , 7.06 , 5.84 , 3.48 , 3.12 , 1.14 , 0.38\u20130.21 . 13C NMR  \u03b4 177.42, 132.34, 130.88, 128.11, 127.92, 122.47, 45.40, 33.90, 9.97, 4.80.Compound Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020009512/hb7931sup1.cifCrystal structure: contains datablock(s) global, II, I. DOI: 10.1107/S2056989020009512/hb7931Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020009512/hb7931IIsup4.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020009512/hb7931Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020009512/hb7931IIsup5.cmlSupporting information file. DOI: 2015807, 2015806CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "It should read as \u201cbuffer A (10 mM Tris\u2013HCl (pH 8.0), 50 mM NaCl, 1 mM NaThe authors would like to apologize for any inconvenience caused."}
{"text": "The title di-substituted thio\u00adurea has hy\u00addroxy\u00adlethyl and ethyl benzoate substituents bound to the same amine-N atom; overall the mol\u00adecule is twisted. Supra\u00admolecular layers are formed in the crystal, with the mol\u00adecules connected by O\u2014H\u22efS and N\u2014H\u22efO hydrogen bonds. 12H16N2O3S, has the hy\u00addroxy\u00adlethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine\u2014C\u2014C\u2014O torsion angles of 49.39\u2005(13) and 59.09\u2005(12)\u00b0, respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26\u2005(4)\u00b0. In the crystal, supra\u00admolecular layers propagating in the ac plane are formed via a combination of hydroxyl-O\u2014H\u22efS(thione), amine-N\u2014H\u22efO hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of \u03c0\u2013\u03c0 stacking [inter-centroid separation = 3.8722\u2005(7)\u2005\u00c5] and parallel C=O\u22ef\u03c0 inter\u00adactions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the inter\u00adactions involving the benzene residue.The title di-substituted thio\u00adurea, C In an experiment with R = CH2CH2OH and Ar = C6H5, the solution was also heated resulting in an apparent rearrangement with deprotonation of one hy\u00addroxy\u00adethyl group followed by nucleophilic attachment at the carbonyl-C atom along with protonation of the primary amine and cleavage of the original N\u2014C(=O) bond to yield (I)2NC(=S)N(CH2CH2OH)CH2CH2OC(=O)C6H5. The mol\u00adecular structure of (I)The title compound, (I)2S atoms of the thio\u00adurea core are almost planar, exhibiting a r.m.s. deviation = 0.0054\u2005\u00c5, with the appended C2 and C4 atoms lying 0.0236\u2005(18) and 0.0216\u2005(16)\u2005\u00c5 to either side of the plane. The conformation of the C2-hy\u00addroxy\u00adlethyl residue is (+)syn-clinal as indicated by the N2\u2014C2\u2014C3\u2014O1 torsion angle of 49.39\u2005(13)\u00b0. The CO2 residue is close to co-planar with the (C7\u2013C12)-benzene ring to which it is connected, forming a dihedral angle of 4.83\u2005(9)\u00b0. The dihedral angle between the least-squares planes through the CN2S core and the benzene ring is 69.26\u2005(4)\u00b0, indicating the mol\u00adecule is highly twisted. Finally, the N2\u2014C4\u2014C5\u2014O2 torsion angle of 59.09\u2005(12)\u00b0 is indicative of a (+)syn-clinal configuration about the C\u2014C bond, thereby confirming the twisted nature of the mol\u00adecule.The mol\u00adecule of (I)a-axis direction, Fig.\u00a02a). These hydrogen bonds also lead to the formation of 12-membered {\u22efHO\u22efHNCS}2 and 14-membered {\u22efOC2NCNH}2 synthons, each disposed about a centre of inversion, and linked via the edges defined by the amine-N\u2014H\u22efO(hydrox\u00adyl) hydrogen bonds. The tape has a step-ladder topology and projecting laterally to either side of the tape are the remaining amine-H and carbonyl-O atoms, which form the donors and acceptors of amine-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds to link the tapes into a layer in the ac plane, Fig.\u00a02b). The directional links between layers are twofold, namely \u03c0\u2013\u03c0 stacking between the centrosymmetrically related benzene rings  and parallel C=O\u22ef\u03c0 inter\u00adactions, Table\u00a01c). These inter\u00adactions are possible owing to the inter-digitation of the benzene rings along the b-axis direction, as highlighted in Fig.\u00a02d).As anti\u00adcipated, hydrogen bonding plays a key role in the supra\u00admolecular assembly of (I)Crystal Explorer 17  hydrogen bond with a dnorm distance of 1.92\u2005\u00c5, which is significantly shorter, by 0.69\u2005\u00c5 , the ester-C6\u22ef\u03c0(benzene), benzene-C9\u2014H9\u22efS1(thione) and benzene-C9\u2013H9\u22efC1(thione) contacts with a combined Eint of \u221248.3\u2005kJ\u2005mol\u22121 and hydroxyl-O1\u2013H1O\u22efS1(thione) [\u221228.8\u2005kJ\u2005mol\u22121]. Close in energy to latter is that due to \u03c0\u2013\u03c0 [Cg1\u22efCg1 = 3.8722\u2005(7)\u2005\u00c5] with Eint = \u221228.3\u2005kJ\u2005mol\u22121. Next most significant are the pairwise ethyl\u00adene-C2\u2014H2A\u22efS1(thione) inter\u00adactions (Eint = \u221223.1\u2005kJ\u2005mol\u22121) then methyl\u00adene-C3\u2014H3B\u22efH8(benzene) (Eint = \u22124.3\u2005kJ\u2005mol\u22121).Among all the inter\u00adactions, it is the amine-N1\u2014H2viz. amine-N1\u2014H1N\u22efO3(carbon\u00adyl) that propagates along the c axis together with amine-N1\u2014H2N\u22efO1(hydrox\u00adyl) and hydroxyl-O1\u2014H1O\u22efS1(thione), which extend along the a axis, thereby forming a step-ladder framework as shown in Fig.\u00a07a). On the other hand, significant dispersion force is also present as evidenced from the wire mesh-like dispersion energy framework predominantly governed by the \u03c0\u2013\u03c0 inter\u00adactions, with contributions from the inter\u00adactions involving the benzene-C9 atom, Fig.\u00a07b). Overall, the combination of electrostatic and dispersion forces leads to a cuboid-like framework shown in Fig.\u00a07c).The crystal of (I)R(R\u2032)NC(=S)NH2 are comparatively rare with the simplest derivative being the R = R\u2032 = Me species, the almost planar mol\u00adecule being first reported in 1994  : 3419 \u03bd(OH), 3323 \u03bd(NH2)asym, 3222 \u03bd(NH2)sym, 3058 \u03bd(CH)arom, 3002\u20132881 \u03bd(CH), 1706 \u03bd(COO), 1647 \u03bd(C=O), 1600 \u03b4(NH), 1523 \u03bd(C=C), 1270 \u03bd(CN), 1053 \u03bd(C=S), 711 \u03b4(CH).Compound (I)Uiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located from a difference-Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020006829/hb7918sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020006829/hb7918Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006829/hb7918Isup3.cmlSupporting information file. DOI: 2004940CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A study of their luminescence properties indicates that co-crystals 1 and 2 exhibit distinctly different luminescence in the solid state at room temperature.Two new co-crystals of tetra\u00adiodo\u00adethyl\u00adene with two aza\u00adphenanthrenes were successfully synthesized. In the crystals, C\u2014I\u22ef 2I4\u00b7C13H9N (1) and tetra\u00adiodo\u00adethyl\u00adene\u2013benzo[f]quinoline (1/2), 0.5C2I4\u00b7C13H9N (2), were obtained from tetra\u00adiodo\u00adethyl\u00adene and aza\u00adphenanthrenes, and characterized by IR and fluorescence spectroscopy, elemental analysis and X-ray crystallography. In the crystal structures, C\u2014I\u22ef\u03c0 and C\u2014I\u22efN halogen bonds link the independent mol\u00adecules into one-dimensional chains and two-dimensional networks with subloops. In addition, the planar aza\u00adphenanthrenes lend themselves to \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions, leading to a diversity of supra\u00admolecular three-dimensional structural motifs being formed by these inter\u00adactions. Luminescence studies show that co-crystals 1 and 2 exhibit distinctly different luminescence properties in the solid state at room temperature.Two new co-crystals, tetra\u00adiodo\u00adethyl\u00adene\u2013phenanthridine (1/2), 0.5C Halogen bonding (XB) is a powerful tool to assemble supra\u00admolecular materials and to promote chemical or biological mol\u00adecular recognition , which is expected to tune their luminescence behaviour via a change of the co-crystal structures. Single crystal X-ray diffraction (XRD) data reveal that the two co-crystals of TIE with PHN and BfQ reported here have inter\u00adesting structural properties and exhibit different luminescence behaviour from previous reports. TIE as a quadridentate XB donor allows the formation of three-dimensional halogen-bonded networks with XB acceptors, PHN and BfQ. Using the conventional solution-based method, yellow co-crystals suitable for XRD measurement were obtained. The crystal structures of the co-crystals are mainly constructed by C\u2014I\u22ef\u03c0 and C\u2014I\u22efN halogen bonds. Other multiple inter\u00admolecular inter\u00adactions, such as \u03c0\u2013\u03c0 stacking, C\u2014H\u22ef\u03c0, C\u2014H\u22efI as well as C\u2014H\u22efH\u2014C inter\u00adactions, are also observed in the co-crystals.Nitro\u00adgen heteroaromatic rings are a common type of luminescence or luminescent precursor materials. However, in general, it is difficult to use them to generate phospho\u00adrescence or delayed fluorescence. Haloperfluoro\u00adbenzenes, as XB donors, have been used in attempts to assemble luminescence co-crystals with aza\u00adphenanthrenes . The I1\u22efN1i distance is 2.864\u2005(7)\u2005\u00c5 and the corresponding C14\u2013I1\u22efN1i angle is 172.8\u2005(2)\u00b0 . The strong C14\u2014I1\u22efN1 halogen bond results in a I1\u22efC13i distance [3.553\u2005(8)\u2005\u00c5] shorter than the sum of the van der Waals radii, which indicates a C1\u2014I1\u22efC13 halogen inter\u00adaction. In addition, the C14\u2014I2\u22efC9ii/C10ii C\u2014I\u22ef\u03c0 separations  are 3.432\u2005(9) and 3.612\u2005(8)\u2005\u00c5, and the corresponding bond angles are 165.6\u2005(2) and 156.7\u2005(2)\u00b0, respectively. Furthermore, \u03c0\u2013\u03c0 stacking  and C\u2014H\u22efH\u2014C inter\u00adactions between two adjacent PHN mol\u00adecules contribute to the extension of the two-dimensional network into a three-dimensional supra\u00admolecular structure , I1\u22efC1 = 3.641\u2005(5), I2\u22efC13 = 3.436\u2005(5) and I2\u22efC8 = 3.733\u2005(4)\u2005\u00c5, respectively] in co-crystal 2 are all a little longer (0.004\u20130.121\u2005\u00c5) than in 1 . In addition, the two-dimensional network \u2005\u00c5, Cg1\u22efCg2ii = 3.963\u2005(2)\u2005\u00c5, Cg1\u22efCg3ii = 3.746\u2005(3)\u2005\u00c5, Cg2\u22efCg2ii = 3.768\u2005(2)\u2005\u00c5; Cg1, Cg2 and Cg3 are the centroids of rings N1/C1\u2013C5, C4\u2013C9 and C8\u2013C13, respectively; symmetry codes: (i) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; (ii) 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z] and C\u2014H\u22efI hydrogen bonds  in the 2\u03b8 range of 5 to 50\u00b0. As shown in Fig.\u00a061 and 2 match well with the spectra simulated from the XRD data, which confirms the purity of 1 and 2.The powder X-ray diffraction (PXRD) experiments were carried out for the title co-crystals using a Bruker D8-ADVANCE X-ray diffractometer  state to drop below that of the 3 state. It is supposed that for the singlet states the 0\u20130 transition of emitters in co-crystals is localized at 375\u2005nm and 450\u2005nm, respectively, and for triplet states the 0\u20130 transition is at about 600\u2005nm. The energy gap between S1 and T1 is largely greater than 20\u2005kJ\u2005mol\u22121, so the delayed fluorescence most likely originates from the triplet\u2013triplet annihil\u00adation process, named P-type delayed fluorescence (P-DF). Both delayed fluorescence and phospho\u00adrescence are relative to triplet states, so they should be significant for improving the exciton emission efficiency of luminescence materials  are about 10\u2005ns, while the delayed fluorescence lifetime (4.36\u2005\u00b5s for 1 and 6.45\u2005\u00b5s for 2) is less than the 10\u2005\u00b5s level because of the strong heavy-atom effect leading to a faster decay of the triplet state. Additionally, the phospho\u00adrescence is too weak to measure its decay lifetime. However, the phospho\u00adrescence lifetime can be estimated to be about 20\u2005\u00b5s based on the relationship between P-DF and the accompanying phospho\u00adrescence  measurements were obtained by slow evaporation of the solvent at room temperature after about two weeks. Elemental analysis  calculated for C14H9NI2 (445.02): C 37.78, H 2.04, N 3.15. Found: C 37.54, H 2.31, N 3.26. For co-crystal 1, and C 37.85, H 2.16, N 3.04 for co-crystal 2. IR  For 1: 3048(w), 1603(w), 1572(w), 1494(m), 1446(w), 1382(m), 1293(m), 1267(m), 1189(m), 1089(m), 948(m), 870(s), 832(s), 802(s), 749(s), 707(s), 615(m), 538(m), 487(m), 435(m). For 2: 3048(w), 1611(w), 1576(s), 1522(w), 1486(w), 1458(m), 1440(m), 1238(m), 1132(m), 1032(m), 953(m), 924(m), 889(s), 745(s), 714(s), 610(m), 552(m), 448(m), 423(m).0.1\u2005mmol of PHN/BfQ and 0.05\u2005mmol of TIE were dissolved in an acetone/chloro\u00adform (2:1) mixture in a glass vial. Well\u2013formed co-crystals Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020002182/vm2225sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989020002182/vm22251sup4.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989020002182/vm22252sup5.hklStructure factors: contains datablock(s) 2. DOI: 1899078, 1899077CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The three para-phenyl\u00adene rings bonded to the N atom are in a propeller form. All of the naphthalene ring systems are slightly bent. In the crystal, mol\u00adecules form an inversion dimer, through two pairs of C\u2014H\u22ef\u03c0 inter\u00adactions, which further inter\u00adacts with the adjacent dimer via another two pairs of C\u2014H\u22ef\u03c0 inter\u00adactions, forming a column structure along the a axis. There are no significant inter\u00adactions between these column structures.In the title mol\u00adecule, C The torsion angles C3\u2014C2\u2014N1\u2014C34, C19\u2014C18\u2014N1\u2014C2 and C35\u2014C34\u2014N1\u2014C18 are \u221235.0\u2005(2), \u221260.6\u2005(2) and \u221230.3\u2005(2)\u00b0, respectively. The para-phenyl\u00adene ring and the mean plane of the neighboring naphthalene ring system are inclined to each other by 54.66\u2005(7)\u00b0 for (C2\u2013C7)/(C8\u2013C17), 48.80\u2005(7)\u00b0 for (C18\u2013C23)/(C24\u2013C33) and 56.21\u2005(7)\u00b0 for (C34\u2013C39)/(C40\u2013C49).The mol\u00adecular structure of the title compound is shown in Fig.\u00a01via four inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions  \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a02], forming an inversion dimer  \u2212x, \u2212y, \u2212z\u00a0+\u00a02] , which included eleven hits (nine compounds) with heteroaromatic rings and eight hits (seven compounds) with phenyl rings. The seven compounds with phenyl rings at the three para-position of the tri\u00adphenyl\u00adamine skeleton include tris\u00ad(biphenyl-4-yl)amine [WEHLIE phen\u00adyl]amine , toluene (42\u2005mL) and water (10.4\u2005mL) were placed in a 100\u2005mL round-bottom flask. After the solution was purged with nitro\u00adgen for 10 minutes, it was heated at 373\u2005K under nitro\u00adgen for 24\u2005h. The reaction mixture was extracted with ethyl acetate. After drying over anhydrous Na2SO4, the organic layer was evaporated. The residue was redissolved in a small amount of ethyl acetate. The addition of a large amount of methanol gave the pure product as a white precipitate . Colorless single crystals suitable for X-ray diffraction were obtained by means of the vapor diffusion method from chloro\u00adform as a rich solvent and n-hexane as a poor solvent after standing for one week.The title compound was prepared by a modification of the previously reported Suzuki\u2013Miyaura coupling reaction (Kwon Uiso(H) = 1.2Ueq(C). One outlier (011) was omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020012529/is5556sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020012529/is5556Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012529/is5556Isup3.cmlSupporting information file. DOI: 2031765CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Biological screening showed these compounds as good inhibitors for several glycosidases. Especially  Glycosidases are involved in many important biological processes, and inhibitors of glycosidases \u20133 are diAn extended search in literature as of 2020, October, revealed there are some 30,600 structures containing the substructure of a 6-amino-6-deoxy-hexopyranose (or -pyranoside). Monofluorinated analogs, however, have scarcely been prepared  \u201337\u2014but t1 D\u2009=\u2009+39.9\u00b0 ]; R\u0192 \u2009=\u20090.53; analysis calcd for C23H26O6 (398.45): C 69.33, H 6.58; found: C 69.09, H 6.63.Data for C ; R\u0192 \u2009=\u20090.63; analysis calcd for C23H26O6 (398.45): C 69.33, H 6.58; found: C 69.17, H 6.71.Data for C (lit.:  124\u2009\u00b0C);1  in dry DCM (40.0\u2009mL) while maintaining the temperature at \u221278\u2009\u00b0C. The mixture was stirred for 2\u2009h at \u221278\u2009\u00b0C, then a solution of Et3N  in dry DCM (40.0\u2009mL) was added dropwise. The mixture was stirred at \u221278\u2009\u00b0C for another 30\u2009min and at 25\u2009\u00b0C for 12\u2009h. Usual aqueous workup followed by chromatography  gave 2  as a white solid; MP 130\u2013132\u2009\u00b0C; [\u03b1]D\u2009=\u2009\u221247.95\u00b0 ; R\u0192 \u2009=\u20090.40 (ketone); R\u0192 \u2009=\u20090.19 (hydrate); analysis calcd for C23H24O6 (396.43): C 69.68, H 6.10; found: C 69.43, H 6.27.To a solution of dry DMSO  in dry DCM (40.0\u2009mL) at \u221278\u2009\u00b0C, a solution of trifluoroacetic anhydride  in dry DCM (10.0\u2009mL) was slowly added dropwise, and the mixture was stirred at this temperature for 45\u2009min followed by adding a solution of 2  in dry DCM (6.0\u2009mL), DAST (417\u2009\u03bcL 3.03\u2009mmol) was added dropwise under argon, and the mixture was stirred at 25\u2009\u00b0C for 5 days. Methanol (1.0\u2009mL) was carefully added, and the solvents were removed under diminished pressure. The oily residue was dissolved in DCM (90\u2009mL) and washed with water (50\u2009mL). The aqueous phase was re-extracted with DCM (3\u2009\u00d7\u2009100\u2009L); the organic layers were combined, and the solvent was evaporated under reduced pressure. The remaining residue was subjected to chromatography  to afford 3  as a white solid; MP 79\u201381\u2009\u00b0C; [\u03b1]D\u2009=\u2009\u221226.10\u00b0  R\u0192 \u2009=\u20090.75; analysis calcd for C23H24O5F2 (418.43): C 66.02, H 5.78; found: C 65.85, H 5.92.To a solution of 3  in dry ether (30\u2009mL) and THF (30\u2009mL), lithium aluminum hydride  was added in several portions, and the suspension was stirred for 15\u2009min at 25\u2009\u00b0C. Then, the suspension was heated to reflux, and a solution of dry aluminum chloride  in dry ether (30\u2009mL) was added dropwise followed by stirring under reflux for another 48\u2009h. The suspension was cooled to 25\u2009\u00b0C, methanol (30\u2009mL) was carefully added, and stirring was continued for another 30\u2009min. After usual aqueous workup followed by chromatography  4  and 5  were obtained each as a colorless oil.To an ice-cold solution of 4: [\u03b1]D\u2009=\u2009\u221248.23\u00b0 ; R\u0192 \u2009=\u20090.51; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.55, H 6.40.Data for 5: [\u03b1]D\u2009=\u2009\u221218.27\u00b0 ; R\u0192 \u2009=\u20090.41; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.47, H 6.39.Data for 5  in toluene (30\u2009mL) containing triphenylphosphane  and imidazole , iodine  was added in several portions. After stirring at 90\u2009\u00b0C for 2\u2009h, the reaction mixture was decanted, and the remaining oil was washed with ether (3\u2009\u00d7\u2009100\u2009mL). The combined organic layers were evaporated, and the remaining residue was subjected to chromatography  to afford 6  as a colorless oil; [\u03b1]D\u2009=\u2009\u221225.32\u00b0 ; R\u0192 \u2009=\u20090.56; analysis calcd for C23H25O4F2I (530.34): C 52.09, H 4.75; found: C 51.84, H 4.92.To a solution of 6  in dry DMF (19\u2009mL) a solution of lithium azide  was added at 25\u2009\u00b0C, and the solution was stirred at this temperature for 4 days. The solvents were removed under diminished pressure, and the remaining residue was dissolved in DCM (100\u2009mL) and water (50\u2009mL). The aq. phase was extracted with DCM (3\u2009\u00d7\u2009100\u2009mL), and the combined organic layers were dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining residue was subjected to chromatography  to afford 7  as a colorless oil; [\u03b1]D\u2009=\u2009\u221233.01\u00b0 ; R\u0192 \u2009=\u20090.39; analysis calcd for C23H25O4F2N3 (445.44): C 62.01, H 5.66, N 9.43; found: C 61.80, H 5.81, N 9.25.To a solution of 7  in dry MeOH (20.0\u2009mL) containing palladium on charcoal  was hydrogenated . The solution was filtered through a pad of Celite; the pad was rinsed with methanol (4\u2009\u00d7\u200950\u2009mL). The combined organic layers were dried (MgSO4), the solvent was removed under reduced pressure, and the residue was subjected to chromatography  to afford 8  as a white foam; [\u03b1]D\u2009=\u2009\u221220.26\u00b0 ; R\u0192 \u2009=\u20090.14; analysis calcd for C9H17O4F2N (241.23): C 44.81, H 7.10, N 5.81; found: C 44.69, H 7.32, N 5.69.A solution of 9  in dry dichloromethane (40.0\u2009mL) was added dropwise, maintaining the temperature at \u221278\u2009\u00b0C during this addition. The mixture was stirred for 2\u2009h at \u221278\u2009\u00b0C, then a solution of Et3N  in dry DCM (40.0\u2009ml) was added. The mixture was stirred at \u221278\u2009\u00b0C for another 30\u2009min and at 25\u2009\u00b0C for 12\u2009h. Usual aqueous workup followed by chromatography  gave 10  as a white solid; MP 125\u2013127\u2009\u00b0C; [\u03b1]D\u2009=\u2009\u221264.84\u00b0 ; R\u0192 \u2009=\u20090.73; analysis calcd for C23H24O6 (396.43): C 69.68, H 6.10; found: C 69.50, H 6.37.To a mixture of dry DMSO  and dry DCM (72.0\u2009ml) at \u221278\u2009\u00b0C, a solution of trifluoroacetic anhydride  in dry DCM (18.0\u2009mL) was slowly added, and the mixture was stirred at this temperature for 45\u2009min. Then a solution of 10  in dry DCM (6.0\u2009mL) DAST  was added dropwise, and the mixture was stirred at 25\u2009\u00b0C for 5 days. Methanol (2.0\u2009mL) was carefully added, and the solvents were removed under diminished pressure. Usual aqueous workup followed by chromatography  gave 11  as a white amorphous solid; [\u03b1]D\u2009=\u2009\u221227.89\u00b0 ; R\u0192 \u2009=\u20090.67; analysis calcd for C23H24O5F2 (418.43): C 66.02, H 5.78; H 65.79, H 5.93.To a solution of 11  in dry ether (40\u2009mL) and THF (40\u2009mL) lithium aluminum hydride  was added in several portions, and the suspension was stirred for 15\u2009min at 25\u2009\u00b0C. Then, the suspension was heated under reflux, and a solution of dry aluminum chloride  in dry ether (30\u2009mL) was added followed by stirring under reflux for 72\u2009h. The suspension was cooled to 25\u2009\u00b0C, methanol (30\u2009mL) was carefully added, and stirring was continued for another 45\u2009min. Usual aqueous workup followed by chromatography  gave 12  and 13  each as a viscous oil;To an ice-cold solution of 12: [\u03b1]D\u2009=\u2009+14.57\u00b0 ; R\u0192 \u2009=\u20090.47; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.59, H 6.46.Data for 13: [\u03b1]D\u2009=\u2009\u221217.26\u00b0 ; R\u0192 \u2009=\u20090.61; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.56, H 6.41.Data for 12  in toluene (40\u2009mL) containing triphenylphosphane  and imidazole  iodine  was added in several portions. After stirring at 90\u2009\u00b0C for 1\u2009h, the reaction mixture was decanted and the remaining oil was washed with ether (4\u2009\u00d7\u2009100\u2009mL). The combined organic layers were evaporated, and the remaining residue was subjected to chromatography  to afford 14  as a colorless oil; [\u03b1]D\u2009=\u2009+23.79\u00b0 ; R\u0192 \u2009=\u20090.51; analysis calcd for C23H25O4F2I (530.34): C 52.09, H 4.75; found: C 51.84, H 4.93.To a solution of 14  in dry DMF (29\u2009mL) a solution of lithium azide  was added at 25\u2009\u00b0C, and the solution was stirred at this temperature for 4 days. The solvents were removed under diminished pressure, and the remaining residue was dissolved in DCM (100\u2009mL) and water (50\u2009mL). The aq. phase was extracted with DCM (3\u2009\u00d7\u2009100\u2009ml), and the combined organic layers were dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining residue was subjected to chromatography  to afford 15  as a colorless oil; [\u03b1]D\u2009=\u2009+33.95\u00b0 ; R\u0192 \u2009=\u20090.48; analysis calcd for C23H25O4F2N3 (445.44): C 62.01, H 5.66, N 9.43; found: C 61.86, H 5.71, N 9.21.To a solution of 15  in dry methanol (20.0\u2009mL) containing palladium on charcoal  was hydrogenated . Workup as described above followed by chromatography  gave 16  as a white foam; [\u03b1]D\u2009=\u2009\u221227.95\u00b0 ; R\u0192 \u2009=\u20090.13; analysis calcd for C9H17O4F2N (241.23): C 44.81, H 7.10, N 5.81; found: C 44.65, H 7.34, N 5.68.A solution of Supplementary Materials"}
{"text": "Scientific Reports 10.1038/srep45179, published online 23 March 2017Correction to: 3 NFs synthesized at 210\u2009\u00b0C for 12\u2009h shown in panels d-f were incorrectly given as SEM images of P(VDF-HFP) based nanocomposites with 5.0\u2009vol%, 10.0\u2009vol% and 20.0\u2009vol% BaTiO3 NFs synthesized at 210\u2009\u00b0C for 24\u2009h. The correct Figure 5 appears below as Fig.\u00a0This article contains errors in Figure 5. The SEM images of the nanocomposites with 2.5\u2009vol%, 5.0\u2009vol% and 7.5\u2009vol% BaTiO"}
{"text": "Corrections to the article, \u201cMultilabel segmentation of cancer cell culture on vascular structures with deep neural networks,\u201d by S. Rahkonen et\u00a0al. J. Med. Imag.7(2), 024001 (2020) doi: 10.1117/1.JMI.7.2.024001] was originally published online on 7 April 2020 with errors in the panel labels for Fig.\u00a06.This article [The following corrections were made to the originally published version:1.in Fig 6(h), \u201cPrediction (O)\u201d was corrected to read \u201cPrediction (S)\u201d;2.in Fig 6(i), \u201cPrediction (I)\u201d was corrected to read \u201cPrediction (IP)\u201d;3.in Fig 6(j), \u201cErrors (R)\u201d was corrected to read \u201cErrors (P)\u201d;4.in Fig 6(k), \u201cErrors (O)\u201d was corrected to read \u201cErrors (S)\u201d;5.in Fig 6(l), \u201cErrors (I)\u201d was corrected to read \u201cErrors (IP)\u201d;6.in Fig 6(m), \u201cAbs. errors (R)\u201d was corrected to read \u201cAbs. errors (P)\u201d;7.in Fig 6(n), \u201cAbs. errors (O)\u201d was corrected to read \u201cAbs. errors (S)\u201d; and8.in Fig 6(o), \u201cAbs. errors (I)\u201d was corrected to read \u201cAbs. errors (IP).\u201dThis article was corrected on 13 April 2020."}
{"text": "MF6  compounds and a related coordination polymer are reported.The crystal structures of three copper(II)-bi\u00adpyridine\u2013 2N,N\u2032)copper(II) hexa\u00adfluorido\u00adsilicate tetra\u00adhydrate, [Cu(bpy)2(H2O)][SiF6]\u00b74H2O , (I), bis\u00ad-di-\u03bc-fluorido-1:3\u03ba2F:F;2:3\u03ba2F:F-deca\u00adfluorido-1\u03ba5F,2\u03ba5F-ditantalum(V)copper(II), [Cu(bpy)2(TaF6)2], (II), tris\u00adcopper(II) bis[hexa\u00adfluorido\u00adtantalate(V)], [Cu(bpy)3][TaF6]2, (III), and catena-poly[[di\u00adaqua\u00adcopper(II)]-\u03bc-fluorido-tetra\u00adfluorido\u00adtin-\u03bc-fluorido], [Cu(bpy)(H2O)2SnF6]n, (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C2, D2, and D3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O\u2014H\u22efF and O\u2014H\u22efO hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin.We report the hydro\u00adthermal syntheses and crystal structures of aqua\u00adbis\u00ad(2,2\u2032-bi\u00adpyridine-\u03ba The structure features isolated C2-symmetric \u0394- and \u039b-[Cu(bpy)2(H2O)]2+ cations and octa\u00adhedral SiF62\u2013 anions , as described by the parameter \u03c4 = (\u03b2\u00a0\u2212\u00a0\u03b1)/60, where \u03b2 and \u03b1 are the two largest angles of the complex  2(H2O)]2+ complexes ns Fig.\u00a01. The fiv2(TaF6)2 and crystallizes in space group P2(TaF6)2 complexes with local D2 symmetry. Each CuII center is equatorially coordinated by two bpy ligands and axially coordinated by two TaF6\u2212 groups. Two independent Cu(bpy)2(TaF6)2 units with the same handedness are present within the arbitrarily chosen asymmetric unit it Fig.\u00a02. These c3][TaF6]2 and crystallizes in the enanti\u00adomorphous space group P32. The structure of (III)D3-symmetric \u039b-Cu(bpy)32+ cations with CuII in an octa\u00adhedral CuN6 coordination environment. The Cu\u2014N distances are in agreement with those of the Cu(bpy)32+ cations in [Cu(bpy)3][PF6]2 it Fig.\u00a03.2O)2SnF6 and crystallizes in space group P2/n. The structure is composed of one-dimensional coordination chains propagating in the [101] direction that can be described as alternating Cu(bpy)(H2O)22+ cations (Cu site symmetry 2) and SnF62\u2212 anions catenated through bridging Cu\u2014F\u2014Sn linkages. The Sn4+ ion occupies a crystallographic inversion center. Intra\u00admolecular hydrogen bonding is present along the chains via O1\u2014H1A\u22efF2 and O1\u2014H1B\u22efF3 contacts ts Fig.\u00a04. The Cu\u20142(H2O)2+ and SiF62\u2212 groups are linked via O\u2014H\u22efF hydrogen bonding between the apical water mol\u00adecule and two SiF62\u2212 ions (Table\u00a012(H2O)2+ units participate in displaced heterochiral \u03c0\u2013\u03c0 stacking inter\u00adactions between the N1/C1\u2013C5 and N2/C6\u2013C10 rings with an inter\u00adplanar angle of 1.11\u2005(11)\u00b0, centroid\u2013centroid distance of 3.8774\u2005(12)\u2005\u00c5, and a slippage distance of 1.490\u2005\u00c5 to form \u0394up\u2013\u039bdown\u2013\u0394up\u2013\u039bdown and \u0394down\u2013\u039bup\u2013\u0394down\u2013\u039bup chains (up/down refers to the orientation of the Cu\u2014O bond vector in the +a or \u2013a direction). The water mol\u00adecules of hydration are involved in O\u2014H\u22efF hydrogen bonding inter\u00adactions with the SiF62\u2212 anion as well as O\u2014H\u22efO bonds with other water mol\u00adecules s Table\u00a01. The \u0394/\u039bes Fig.\u00a05.2(TaF6)2 complexes in (II)a + b or b \u2013 a directions, as shown in Fig.\u00a06c-axis direction, each chain is neighbored by a chain with the opposite chirality and same orientation on one side and a chain with the same chirality and opposite orientation on the other.The neutral Cu(bpy)32+ complexes participate in displaced \u03c0\u2013\u03c0 stacking inter\u00adactions propagating along the 32 screw axes with an inter\u00adplanar angle of 13.9\u2005(2)\u00b0, centroid\u2013centroid distance of 3.933\u2005(2)\u2005\u00c5 between adjacent N1/C1\u2013C5 and N5/C21\u2013C25 pyridine rings, and a horizontal shift distance of 1.970\u2005\u00c5. Each \u039b-Cu(bpy)32+ cation is surrounded by six TaF6\u2212 anions ns Fig.\u00a07.via parallel displaced \u03c0\u2013\u03c0 stacking inter\u00adactions ns Fig.\u00a08. One of et al., 20162(H2O)]2+ complexes and fluorinated inorganic anions: [Cu(bpy)2(H2O)][BF4]2 ][PF6]2 ][MF6] MF62\u2212 anions hydrogen bonded to the [Cu(bpy)2(H2O)]2+ complex are both hydrogen bonded to the same pair of [Cu(bpy)2)(H2O)]2+ complexes in the ETM case, whereas they are bound to two different complexes in the SiF62\u2212 case. Further, while the [Cu(bpy)2(H2O)][MF6]  compounds display both face-to-face and displaced \u03c0\u2013\u03c0 stacking inter\u00adactions, (I)A survey of structures related to (I)et al., 2017a-axis direction. Additionally, these complexes participate in heterochiral \u03c0\u2013\u03c0 stacking inter\u00adactions.A search of the CSD for structures related to (II)A(bpy)3][PF6] 32+ complexes.Compound (III)2O)HfF6 (H2O)2MOxFx6\u2013 compounds , which display polar zigzag chains et al., 1993\u22121 to 150\u00b0C and held at 150\u00b0C for 24\u2005h. The autoclaves were allowed to cool to room temperature at a rate of 6\u00b0C h\u22121 and the solid products were recovered by vacuum filtration. Compound (I)3)2\u00b7H2O, 5\u2005mmol of 2,2\u2032-bi\u00adpyridine, 1.5\u2005mmol of (NH4)2SiF6 and 1ml of deionized H2O. Compound (II)2O5, 0.8\u2005ml HF(aq), and 0.3\u2005ml of deionized H2O. Compound (III)2O5, 1\u2005ml of HF(aq) and 0.1\u2005ml of deionized H2O. Compound (IV)3)2\u00b7H2O, 1.3\u2005mmol of 2,2\u2032-bi\u00adpyridine, 1.7\u2005mmol of (NH4)2SnF6 and 1\u2005ml of deionized H2O.The compounds reported here were synthesized by the hydro\u00adthermal pouch method (Harrison Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a03m1. The twinning occurs with a BASF of 0.5, suggesting that both the P31 and P32 configurations are present in equal proportions within the sample.The measured crystal of (III)10.1107/S2056989021000633/hb7957sup1.cifCrystal structure: contains datablock(s) global, II, III, IV, I. DOI: 2048914, 2048918, 2048917, 2048915CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Completion of the overall layer structure occurs through weak C\u2014H\u22efO, C\u2014H\u22ef\u03c0 (ring) and head-to-tail slipped \u03c0-stacking inter\u00adactions.The title mol\u00adecule is only a few degrees out of planarity except for the 2-hy\u00addroxy\u00adethyl substituent. In the crystal, O\u2014H\u22efN hydrogen bonds form stepped chains along the  12H13N3O2S, the benzo\u00adthia\u00adzine moiety is slightly non-planar, with the imidazolidine portion twisted only a few degrees out of the mean plane of the former. In the crystal, a layer structure parallel to the bc plane is formed by a combination of O\u2014HHydethy\u22efNThz hydrogen bonds and weak C\u2014HImdz\u22efOImdz and C\u2014HBnz\u22efOImdz  inter\u00adactions, together with C\u2014HImdz\u22ef\u03c0(ring) and head-to-tail slipped \u03c0-stacking [centroid-to-centroid distances = 3.6507\u2005(7) and 3.6866\u2005(7)\u2005\u00c5] inter\u00adactions between thia\u00adzole rings. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (47.0%), H\u22efO/O\u22efH (16.9%), H\u22efC/C\u22efH (8.0%) and H\u22efS/S\u22efH (7.6%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, C\u2014H\u22efN and C\u2014H\u22efO hydrogen-bond energies are 68.5 (for O\u2014HHydethy\u22efNThz), 60.1 (for C\u2014HBnz\u22efOImdz) and 41.8\u2005kJ\u2005mol\u22121 (for C\u2014HImdz\u22efOImdz). Density functional theory (DFT) optimized structures at the B3LYP/6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state.In the title mol\u00adecule, C A plausible mechanism for the formationof the product, 1--3-(2-hy\u00addroxy\u00adeth\u00adyl)imid\u00adazolidin-2-one (I), is given in the reaction scheme.Compounds containing the benzo\u00adthia\u00adzole backbone have been studied extensively in both academic and industrial laboratories , carried out at the B3LYP/6-311G  level, are compared with the experimentally determined mol\u00adecular structure in the solid state.I)  and B (S1/N1/C1/C6/C7)]. A puckering analysis of the conformation of the imidazolidine ring C (N2/N3/C8-C10) gave the parameters Q(2) = 0.0767\u2005(14)\u2005\u00c5 and \u03c6(2) = 66.5\u2005(10)\u00b0. The conformation is described as an \u2018envelope on C9\u2032. This ring is almost coplanar with the thia\u00adzole ring B with a dihedral angle of 3.61\u2005(4)\u00b0 between their mean planes.In the title mol\u00adecule (I) Fig.\u00a01, the benHydethy\u22efNThz (Hydethy = hy\u00addroxy\u00adethyl and Thz = thia\u00adzole) hydrogen bonds  and C\u2014HImdz\u22ef\u03c0(ring) inter\u00adactions (Table\u00a01Bnz\u22efOImdz (Bnz = benzene) inter\u00adactions. Both the layer formation and stacking are also assisted by head-to-tail slipped \u03c0-stacking inter\u00adactions  and 3.6866\u2005(7)\u2005\u00c5, respectively; symmetry codes: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (ii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a0z\u00a0+\u00a0Cg2 is the centroid of ring B].In the crystal, O\u2014Hs Table\u00a01 form steon Fig.\u00a02. These as Table\u00a01. The lays Figs. 3 and 4 \u25b8 I, a Hirshfeld surface (HS) analysis  has a symmetrical distribution of points with the edges at de + di = 2.40\u2005\u00c5. The presence of C\u2014H\u22ef\u03c0 inter\u00adactions is indicated by the characteristic wings with a spikes with the tips at de + di = 2.63\u2005\u00c5 in the fingerprint plot delineated into H\u22efC/C\u22efH contacts . The H\u22efS/S\u22efH contacts contribute 7.6% to the overall crystal packing and are seen in Fig.\u00a08e as widely scattered points with the tips at de + di = 3.03\u2005\u00c5. The pair of spikes in the fingerprint plot delineated into H\u22efN/N\u22efH contacts  has a symmetrical distribution of points with the tips at de + di = 1.88\u2005\u00c5. The C\u22efC contacts  have an arrow-shaped distribution of points with the tip at de = di = 1.70\u2005\u00c5. The N\u22efC/C\u22efN inter\u00adactions  give rise to tiny wings with the tips at de + di = 3.41\u2005\u00c5. The O\u22efC/C\u22efO contacts  give widely scattered points with the tips at de + di = 3.56\u2005\u00c5. Finally, the S\u22efC/C\u22efS and S\u22efN/N\u22efS inter\u00adactions, contributing 2.2% and 1.3% to the overall crystal packing  give rise to tiny wings with the tips at de + di = 3.63\u2005\u00c5 and de + di = 3.63\u2005\u00c5, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a08n Table\u00a02 is H\u22efH, ts Fig.\u00a08f, 5.3% ng Fig.\u00a08j and k dnorm plotted onto the surface are shown for the H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH, H \u22ef S/S\u22efH, H\u22efN/N\u22efH and C\u22efC inter\u00adactions in Fig.\u00a09a--f, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efO/O\u22efH and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be \u221267.2 (Eele), \u221218.0 (Epol), \u221235.4 (Edis), 75.7 (Erep) and \u221268.5 (Etot) for O2\u2014H2A\u22efN1, \u221221.5 (Eele), \u22126.1 (Epol), \u221282.0 (Edis), 62.3 (Erep) and \u221260.1 (Etot) for C5\u2014H5\u22efO1 and \u22121.2 (Eele), \u22126.3 (Epol), \u221273.7 (Edis), 45.7 (Erep) and \u221241.8 (Etot) for C8\u2014H8B\u22efO1.The inter\u00admolecular inter\u00adaction energies were calculated by the CE\u2013B3LYP/6\u2013311G energy model available in I in the gas phase have been computed using the B3LYP functional level of theory and the 6-31G  basis set \u00b0 while the corresponding dihedral angle in the others vary from 13.64\u00b0 in III to 0.61\u00b0 in V.A search of the Cambridge Structural Database . The mixture was stirred at 353\u2005K for 24\u2005h. The solid material was removed by filtration and the solvent evaporated in vacuo. The solid product was purified by recrystallization from ethanol to give colourless crystals (yield: 70%).To a mixture of 2-amino\u00adbenzo\u00adthia\u00adzole (2.22\u2005mmol), bis(2-chloro\u00adeth\u00adyl)amine (1.11\u2005mmol) and potassium carbonate (3.21\u2005mmol) in DMF (25\u2005mL) was added a catalytic amount of tetra-Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020001723/jj2219sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020001723/jj2219Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001723/jj2219Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020001723/jj2219Isup4.cmlSupporting information file. DOI: 1982595CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction to: BMC Public Health (2019) 19:1599https://doi.org/10.1186/s12889-019-7985-5It was highlighted that in the original article  the dataIncorrect statementEven though the prevalence rate of hypertension in male (29.1%) was mildly lower than female (32.7%), our finding showed a significantly higher PRAL in the male (25.3\u2009\u00b1\u200920.2\u2009mEq/d) comparing to the female (19.4\u2009\u00b1\u200916.7\u2009mEq/d).Correct statementPrevalence rate of hypertension in male (32.7%) was mildly higher than female (29.1%) and a significantly higher PRAL in the male (25.3\u2009\u00b1\u200920.2\u2009mEq/d) was also identified comparing to the female (19.4\u2009\u00b1\u200916.7\u2009mEq/d)."}
{"text": "Febuxostat and ethanol mol\u00adecules are linked into an O\u2014H\u22efO and O\u2014H\u22efN bonded chain structure. 16H16N2O3S\u00b7C2H6O, (I), displays inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN bonds in which the carboxyl group of the febuxostat mol\u00adecule and the hydroxyl group of the ethanol mol\u00adecule serve as hydrogen-bond donor sites. These inter\u00adactions result in a helical hydrogen-bonded chain structure. The title structure is isostructural with a previously reported methanol analogue.The title compound, 2-(3-cyano-4-iso\u00adbut\u00adoxyphen\u00adyl)-4-methyl-1,3-thia\u00adzole-5-car\u00adb\u00adoxy\u00adlic acid ethanol monosolvate, C The hy\u00addroxy group of the solvent additionally serves as a hydrogen-bond donor group for an O14\u2014H14\u22efO23 bond to a second febuxostat mol\u00adecule  typically adopts a value close to 0\u00b0. However, an opposite geometry with \u03c4 values close to 180\u00b0 has been reported for the polymorphs Q and H1, a co-crystal with 4-amino\u00adbenzoic acid and a 2-(pyridin-2-yl\u00adamino)\u00adpyridinium salt.Table\u00a02The preparation of febuxostat was carried out according to the scheme in Fig.\u00a032, 10.0\u2005g) and hexa\u00admethyl\u00adene\u00adtetra\u00admine (5.86\u2005g) were added to tri\u00adfluoro\u00adacetic acid (100\u2005ml). The reaction mixture was heated to reflux under stirring for 40\u2005h, and tri\u00adfluoro\u00adacetic acid was distilled out. The obtained residue was cooled to 298\u2005K, water (200\u2005ml) was added slowly, and the slurry was stirred for 4\u2005h. After filtration, the product was washed and dried under vacuum to give 9.60\u2005g of 3.Ethyl 2-(4-hy\u00addroxy\u00adphen\u00adyl)-4-methyl-5-thia\u00adzole carboxyl\u00adate , potassium carbonate (332\u2005g) and isobutyl bromide (330\u2005g) were added to DMF (1.75 1). The reaction mixture was heated to 383\u00b13\u2005K and stirred for 4\u2005h. The reaction mixture was cooled to 298\u2005K, and water (0.50\u2005l) was added slowly. The slurry was stirred for 2\u2005h. After filtration, the product was washed and dried under vacuum to give 389\u2005g of 4. 1H NMR (CDCl3), 400\u2005MHz): \u03b4 = 1.079\u20131.101 , 1.366\u20131.413 , 2.185\u20132.230 , 2.769 , 3.914\u20133.935 , 4.316\u20134.387 , 7.045\u20137.074 , 8.188\u20138.225 , 8.353\u20138.361 .Ethyl 2-(3-formyl-4-hy\u00addroxy\u00adphen\u00adyl)-4-methyl-5-thia\u00adzole\u00adcarboxyl\u00adate , sodium formate (123\u2005g) and hydroxyl\u00adamine hydro\u00adchloride (84\u2005g) were successively added to formic acid (1.4\u2005l). The reaction mixture was heated to reflux and stirred for 5\u2005h to complete the reaction. The reaction solution was cooled to 298\u2005K, and water (2.8\u2005l) was slowly added. After stirring for approximately 1\u2005h, the slurry was filtered, the product was washed with water and dried under vacuum to give 321\u2005g of 5. 1H NMR (CDCl3), 400\u2005MHz): \u03b4 = 1.053\u20131.104 , 1.368\u20131.463 , 2.164\u20132.225 , 2.768 , 3.890\u20133.911 , 4.324\u20134.395 , 6.998\u20137.027 , 8 8.188\u20138.225 , 8.353\u20138.361 .Ethyl 2-(3-formyl-4-iso\u00adbut\u00adoxy\u00adphen\u00adyl)-4-methyl-5-thia\u00adzole\u00adcarboxyl\u00adate  and potassium carbonate (200\u2005g) were successively added to a mixture of MeOH (7.5\u2005l) and water (250\u2005ml). To complete the reaction, the solution was heated to reflux for 3\u2005h under stirring. The clear solution was cooled, and vacuum was applied to distil out the solvent below 313\u2005K. Water (5\u2005l) was added to the residue. After stirring, EtOAc (2.5\u2005l) was added. The solution was stirred, and the layers were separated. The pH of the aqueous solution was adjusted to 2.5\u00b10.2 by adding diluted hydro\u00adchloric acid solution at 313\u2005K. After stirring for 1\u2005h, the slurry was filtered, and the product was washed with water and dried under vacuum to give 215\u2005g of 1.Ethyl 2-(3-cyano-4-iso\u00adbut\u00adoxy\u00adphen\u00adyl)-4-methyl-5-thia\u00adzole\u00adcarboxyl\u00adate (Febuxostat (1\u2005g) was dissolved in ethanol (10\u2005ml), which yielded a clear solution upon heating to 338\u2005K. After filtration, the solution was allowed to cool to room temperature, and the subsequent crystallization resulted in febuxostat ethanol solvate.Uiso parameters were set to 1.5Ueq(C) of the parent carbon atom. H atoms bonded to secondary CH2 (C\u2014H = 0.99\u2005\u00c5) or tertiary CH (C\u2014H = 0.99\u2005\u00c5) carbon atoms and H atoms bonded to C atoms in aromatic rings (C\u2014H = 0.95\u2005\u00c5) were positioned geometrically and refined with Uiso set to 1.2Ueq(C) of the parent carbon atom. H atoms in OH groups were identified in difference maps, refined with a distance restraint [O\u2014H = 0.84\u2005(2)\u2005\u00c5] and a free Uiso parameter. Two outliers  I. DOI: 10.1107/S2056989020006076/fy2145Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006076/fy2145Isup3.cmlSupporting information file. DOI: 2000973CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structures of both compounds are dominated by hydrogen bonds involving water coordination ligands, with an underlying 3.6 \u2212  8H4N4O2)(H2O)4]n, (I), and [Sr(C8H4N4O2)(H2O)3]n, (II), from the one-pot hydrolysis transformation of benzoyl chloride and the in situ self-assembled [2\u00a0+\u00a03] cyclo\u00adaddition of nitrile are presented. These coordination compounds are prepared by reacting 4-cyano\u00adbenzoyl chloride with divalent alkaline-earth salts (BaCl2 and SrCl2) in aqueous solution under hydro\u00adthermal conditions. The mononuclear coordination compounds (I) and (II) show the same mode of coordination of the organic ligands. The cohesion of the crystalline structures is provided by hydrogen bonds and \u03c0-stacking inter\u00adactions, thus forming three-dimensional supra\u00admolecular networks. The two compounds have a three-dimensional -connected topology, and the structural differences between them is in the number of water mol\u00adecules around the alkaline earth metals. Having the same emission frequencies, the compounds exhibit photoluminescence properties with a downward absorption value from (I) to (II).Two alkaline-earth coordination compounds, [Ba(C In these two coordination compounds, the asymmetric unit comprises half of a crystallographically independent alkaline-earth metal ion, half of a deprotonated 4-(tetrrazol-5-yl)benzoate anion (ttzbenz), and two halves of water mol\u00adecules in compound (I)et al., 2009et al., 2007et al., 2009Compound (I)10 sphenocorona coordination geometry . In (I)2+ ion is eightfold coordinated, being surrounded by four bridging water mol\u00adecules and by four oxygen atoms from three symmetry-related ttzbenz ligands .The crystal structures of compounds (I)ds Fig.\u00a02, thus geAe2+ ion (Ae2+ = Ba2+ and Sr2+) range between 42.49\u2005(6) and 142.50\u2005(2)\u00b0 in compound (I)et al., 2010Ae2+ one-dimensional coordination polymers: Ba\u2014O = 2.647\u20133.179\u2005\u00c5, Sr\u2014O = 2.486\u20132.843\u2005\u00c5 in [C24H28N2O13Cl2CuSr]n and [C24H28N2O13Cl2CuBa]n 6(H2O)4]n, Ba\u2014O = 2.801\u2005(2)\u20133.6143\u2005(2)\u2005\u00c5 for M = Ni, Ba\u2014O = 2.797\u2005(2)\u20132.999\u2005(2)\u2005\u00c5 for M = Zn, and Ba\u2014O = 2.801\u2005(2)\u20133.004\u2005(2)\u2005\u00c5 for M = Co \u2005\u00c5 for compound (I)The ttzbenz ligand can adopt several coordination modes by involving the tetra\u00adzole ring ed Fig.\u00a04 with a cCg1) and the phenyl rings (centroid Cg2) with centroid\u2013centroid distances Cg1\u22efCg2 = 3.622\u2005(3)\u2005\u00c5 and Cg2\u22efCg2 = 3.897\u2005(3)\u2005\u00c5 \u2005\u00c5 Fig.\u00a04.et al., 2011c net with stoichiometry (3-C)2(6-C), which can be represented by the point symbol {43}2{46.66.83}. Thus the two structures consist of planar layers running parallel to (100)  to obtain the underlying network. In such models, only metal centers and the centroids of organic ligands are considered as structural units (Alexandrov 0) Fig.\u00a05.et al., 2016et al., 2009et al., 2012et al., 2012et al., 2007et al., 2009et al., 2013et al., 2016et al., 2009et al., 2011et al., 2017et al., 2016et al., 2016et al., 2015et al., 2016N,N-di\u00admethyl\u00adacetamide  benzoate in the Cambridge Structural Database  for (I)2\u00b76H2O  for (II)Colorless crystals suitable for X-ray diffraction were obtained by hydro\u00adthermal synthesis in an aqueous solution according to a literature procedure \u22121): 3300 \u03bd(O\u2014H)water, 3100 \u03bd(C\u2014H)Ph, 1435 \u03bdsym (C\u2014C), 1523 \u03bd(N\u2014N)ring, 1603 \u03bd(C\u2014N)ring, 628\u20131050 \u03b3,\u03b4 (tetra\u00adzole).FT\u2013IR of (I)\u22121): 3600 \u03bd(O\u2014H)water, 3200 \u03bd(C\u2014H)Ph, 1408 \u03bdsym (C\u2014C), 1530 \u03bd(N\u2014N)ring, 1585 \u03bd(C\u2014N)ring, 654\u20131009 \u03b3, \u03b4 (tetra\u00adzole) .FT\u2013IR of (II)The thermogravimetric analysis (TGA) was performed in the range 25\u2013600\u00b0C under air atmosphere at a flow rate of 5\u00b0C/min Fig.\u00a06. The pyr\u22121  was performed in the range 25\u2013600\u00b0C under an air atmosphere at a flow rate of 5\u00b0C min\u22121 Fig.\u00a06. The pyreX = 322\u2005nm) on an Agilent Cary Eclipse Fluorescence Spectrophotometer at room temperature. Excitation of the two compounds after dissolution in DMSO leads to similar fluorescence emission spectra. The emission maximum of (I)supporting information), probably corresponding to \u03c0* \u2192 \u03c0 or \u03c0*\u2192n electronic transition of the aromatic ring ttzbenz ligands Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020006386/tx2021sup1.cifCrystal structure: contains datablock(s) TTZBENZ_AE, I, II. DOI: 10.1107/S2056989020006386/tx2021Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020006386/tx2021IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup4.jpgInfrared spectra. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup5.jpgPhotoluminescent spectra. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup6.docTable S1. Comparative shape analysis of two polymers. DOI: 2003538, 2003537CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule forms a centrosymmetric water-bridged hydrogen-bonding dimer with graph-set notation via two longer inter\u00admolecular hydrogen-bonding inter\u00adactions between the second hydrogen atom on the bridging water mol\u00adecule and both a pyridine nitro\u00adgen atom and carbonyl oxygen. The tri\u00adfluoro\u00admethyl groups extend out the faces of the sheet providing for F\u22efF and C\u2014H\u22efF contacts between the sheets, completing the three-dimensional packing.The title compound, [systematic name: 5-(tri\u00adfluoro\u00admeth\u00adyl)pyridine-2-carb\u00adoxy\u00adlic acid monohydrate], C 7H4F3NO2\u00b7H2O, is the acid hydrate of a pyridine with a carb\u00adoxy\u00adlic acid group and a tri\u00adfluoro\u00admethyl substituent situated para to one another on the aromatic ring. The mol\u00adecule forms a centrosymmetric water-bridged hydrogen-bonding dimer with graph-set notation R44 (12). Hydrogen-bonding distances of 2.5219\u2005(11) and 2.8213\u2005(11)\u2005\u00c5 are observed between the donor carb\u00adoxy\u00adlic acid and the bridging water acceptor, and the donor water and carbonyl oxygen acceptor, respectively. The dimers are further linked into a two-dimensional sheet via two longer inter\u00admolecular hydrogen-bonding inter\u00adactions between the second hydrogen atom on the bridging water mol\u00adecule and both a pyridine nitro\u00adgen atom and carbonyl oxygen with distances of 3.1769\u2005(11) and 2.8455\u2005(11)\u2005\u00c5, respectively. The tri\u00adfluoro\u00admethyl groups extend out the faces of the sheet providing for F\u22efF and C\u2014H\u22efF contacts between the sheets, completing the three-dimensional packing.The title compound [systematic name: 5-(tri\u00adfluoro\u00admeth\u00adyl)pyridine-2-carb\u00adoxy\u00adlic acid monohydrate], C The twoThe structure of 5-(tri\u00adfluoro\u00admeth\u00adyl)picolinic acid (I)W distance of 2.5219\u2005(11)\u2005\u00c5 characterizing the O1\u2014H1\u22efO1W hydrogen bond, while the water hydrogen atom H2W bonds to the carbonyl oxygen atom with an O1W\u22efO2i distance of 2.8213\u2005(11)\u2005\u00c5 charaterizing the O1W-\u2013H2W\u22efO2i hydrogen bond .The mol\u00adecular packing in the solid state can be characterized by the 5-(tri\u00adfluoro\u00admeth\u00adyl)picolinic acid (I)2) Fig.\u00a02. The carW, further bridge the dimer units together to form a pleated strip or tape motif that propagates along the crystallographic [010] direction  and 2.8455\u2005(11)\u2005\u00c5, respectively, characterize the O1W\u2014H1W\u22efNii and O1W\u2014H1W\u22efO2ii hydrogen bonds NO3\u00b7H2O hydrogen bonds into thick two-dimensional sheets with the tri\u00adfluoro\u00admethyl\u00adaromatic groups extending to the faces of the sheets -2-pyridine\u00adcarb\u00adoxy\u00adlic acid has been used as a monoanionic ligand in several metal complexes, including with Co5-(Tri\u00adfluoro\u00admeth\u00adyl)-2-pyridine\u00adcarb\u00adoxy\u00adlic acid  was purchased from Aldrich Chemical Company, USA, and was used as received.Uiso(H) = 1.2Ueq(C) of the aryl C-atoms. The position of the carb\u00adoxy\u00adlic acid and water hydrogen atoms were found in the difference map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a021H NMR : \u03b4 3.70 , 8.21 , 8.37 , 9.07 . 13C NMR : \u03b4 123.23 , 124.73 , 127.30 , 135.12 , 146.24 , 151.98 , 165.13 . 19F NMR : \u03b4 \u221261.35 . IR : 3469 , 3050 , 2849 (w), 2571 (w), 1961 (m), 1707 , 1606 (s), 1582 (s), 1493 (s), 1440 (s), 1392 (s), 1328 (m), 1290 (m), 1251 (s), 1163 (m), 1126 (s), 1075 (s), 1023 (s), 948 (s), 878 (m), 864 (s), 806 (s), 760 (s), 704 (s), 643 (s), 524 (s). GC\u2013MS (Agilent Technologies 7890A GC/5975C MS): +M = 191 amu, corresponding to the anhydrous form, 5-(tri\u00adfluoro\u00admeth\u00adyl)pyridine-2-carb\u00adoxy\u00adlic acid (I)10.1107/S2056989020013523/dj2015sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020013523/dj2015Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020013523/dj2015Isup3.cmlSupporting information file. DOI: 2036131CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-018-22971-w, published online 16 March 2018Correction to: In Figure 4, the panels r and s were presented as s and r respectively. The correct Figure 4 appears below as Figure\u00a0In addition, this Article contains an error in the Methods section under subheading \u2018Collagen gel preparation\u2019 where\u201cRat tail type 1 collagen gels (Merck 08\u2013115) were prepared at 1\u2009mg/ml in 10\u2009\u00d7\u2009M199 (Life Technologies 11825\u2013015) and the pH was adjusted to 7.5 with 2.2% (w/v) NaHCO3. 10\u2009\u00d7\u2009M199 and NaHCO3 were both measured at 1/10 of the final volume.\u201dshould read:\u201cRat tail type 1 collagen gels (Merck 08\u2013115) were prepared at 1\u2009mg/ml in 10\u2009\u00d7\u2009M199 (Life Technologies 11825\u2013015) and the pH was adjusted with 2.2% (w/v) NaHCO3. 10\u2009\u00d7\u2009M199 and NaHCO3 were both measured at 1/10 of the final volume.\u201d"}
{"text": "The asymmetric unit of the title compound comprises three independent mol\u00adecules of similar geometry. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds in addition to C\u2014Cl\u22ef\u03c0 inter\u00adactions. 16H14Cl3N3, comprises three mol\u00adecules of similar shape in the asymmetric unit. The crystal cohesion is ensured by inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds in addition to C\u2014Cl\u22ef\u03c0 inter\u00adactions. Hirshfeld surface analysis and two-dimensional fingerprint plots reveal that Cl\u22efH/H\u22efCl (33.6%), H\u22efH (27.9%) and C\u22efH/H\u22efC (17.6%) are the most important contributors towards the crystal packing.The title compound, C Nevertheless, they can control the reactivity of mol\u00adecules, the crystal packing, tautomerization and other properties -(4-chloro\u00adphen\u00adyl)diazen\u00adyl]ethen\u00adyl}-N,N-di\u00admethyl\u00adaniline, which features C\u2014H\u22efN, C\u2014H\u22ef\u03c0 and C\u2014Cl\u22efCl types of weak inter\u00admolecular inter\u00adactions.In a previous study we have attached resonance-assisted hydrogen-bonded synthons or chlorine atoms to dye mol\u00adecules, which leads to inter\u00admolecular weak inter\u00adactions for the resulting products with inter\u00adesting analytical and solvatochromic properties (Maharramov A (C1A\u2013C16A/N1A\u2013N3A/Cl1A\u2013Cl3A) and Mol-N1B (C1B\u2013C16B/N1B\u2013N3B/Cl1B\u2013Cl3B). The conformational differences between mol\u00adecules Mol-N1, Mol-N1A and Mol-N1B are highlighted in an overlay diagram shown in Fig.\u00a02A\u2013C6A and C8A\u2013C13A (mol\u00adecule Mol-N1A), and C1B\u2013C6B and C8B\u2013C13B (mol\u00adecule Mol-N1B)] of the 4-chloro\u00adphenyl and N,N-di\u00admethyl\u00adaniline groups are 69.94\u2005(10), 79.68\u2005(12) and 88.08\u2005(13)\u00b0, respectively. In mol\u00adecule Mol-N1, the N1\u2014N2\u2014C7\u2014C14, N2\u2014C7\u2014C14\u2014Cl2, N2\u2014C7\u2014C14\u2014Cl3 and C8\u2014C7\u2014C14\u2014Cl3 torsion angles are \u2212178.7\u2005(2), 3.1\u2005(3), \u2212176.21\u2005(16) and 4.1\u2005(3)\u00b0, respectively. The corres\u00adponding angles are 178.4\u2005(2), 3.8\u2005(3), \u2212175.1\u2005(2) and 2.5\u2005(3)\u00b0 for mol\u00adecule Mol-N1A, and \u2212175.0\u2005(2), 0.3\u2005(3), 179.71\u2005(18) and \u22120.1\u2005(4) for mol\u00adecule Mol-N1B.The asymmetric unit of the title compound Fig.\u00a01 containsIn the crystal, the mol\u00adecules are connected by inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds and C\u2014Cl\u22ef\u03c0 inter\u00adactions, which contribute to the overall packing, forming a three-dimensional network Table\u00a01.et al., 2007Crystal Explorer 17.5 . The shape-index of the Hirshfeld surface is a tool to visualize \u03c0\u2013\u03c0 stacking inter\u00adactions; Fig.\u00a04b clearly suggest that there are no \u03c0\u2013\u03c0 inter\u00adactions in the title compound. The red spots in Fig.\u00a04a correspond to the relatively strong C\u2014H\u22efN hydrogen-bonding inter\u00adactions in the crystal structure; in Mol-N1A it involves the N3A atoms of the N,N-di\u00admethyl\u00adaniline group as acceptors with the aromatic H2A donor atom of the chloro\u00adbenzene ring in Mol-N1 (C2\u2014H2A\u22efN3A).Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and inter\u00admolecular inter\u00adactions in the crystal structure. The Hirshfeld surfaces . Another significant reciprocal inter\u00adaction (H\u22efH) with a contribution of 27.9% is present as broad symmetrical spikes at diagonal axes de + di \u2243 2.2\u2005\u00c5 . The pair of characteristic wings in the fingerprint plot delineated into C\u22efH/H\u22efC contacts , have tips at de + di \u2243 2.80\u2005\u00c5. The Cl\u22efCl contacts, Fig.\u00a05e (5.7% contribution), have an arrow-shaped distribution of points with the tip at de = di = 3.50\u2005\u00c5.Two-dimensional fingerprint plots are presented in Fig.\u00a05ce Fig.\u00a05b. Anoth\u2005\u00c5 Fig.\u00a05c. The pviz. Cl\u22efC/C\u22efCl (5.4%), N\u22efH/H\u22efN (4.7%), C\u22efC (1.7%), Cl\u22efN/N\u22efCl (1.6%), N\u22efC/C\u22efN (1.0%) and N\u22efN (0.8%) contacts, show only small contributions and thus have a negligible effect on the packing.The other weak inter\u00admolecular inter\u00adactions, et al., 2016E)-1--2-phenyl\u00addiazene skeleton gave 25 hits, of which six closely resemble the title compound, viz. 1-(4-bromo\u00adphen\u00adyl)-2-diazene . Additional van der Waals inter\u00adactions consolidate the three-dimensional packing. In the crystal of HODQAV, mol\u00adecules are stacked in columns along [100] via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further stabilized by short Cl\u22efCl contacts. In XIZREG, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running along [001]. The crystal packing is further stabilized by C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In the crystal of LEQXIR, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and Cl\u22efO contacts were found, and in LEQXOX, C\u2014H\u22efN and Cl\u22efCl contacts are observed.In the crystal structures of HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9\u2005(2) and 64.1\u2005(2)\u00b0, respectively. Mol\u00adecules are linked through weak et al., 2018E)-4-[(2-(4-chloro\u00adphen\u00adyl)hydrazineyl\u00adidene]meth\u00adyl)-N,N-di\u00admethyl\u00adaniline , tetra\u00admethyl\u00adethylenedi\u00adamine (TMEDA) , CuCl  and CCl4 . After 1\u20133\u2005h , the reaction mixture was poured into a \u223c0.01 M solution of HCl  and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined organic phase was washed with water (3 x 50\u2005ml), brine (30\u2005ml), dried over anhydrous Na2SO4 and concentrated in vacuo in a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1) to give an orange solid. Yield: 72%; mp 408\u2005K. Analysis: calculated for C16H14Cl3N3: C 54.19, H 3.98, N 11.85; found: C 54.08, H 3.91, N 11.82%. 1H NMR  \u03b4 3.05 , 6.79\u20137.79 . 13C NMR  \u03b4 152.41, 151.45, 150.29, 137.26, 135.11, 131.08, 129.27, 124.50, 119.11, 111.48, 40.29. ESI\u2013MS: m/z: 355.48 [M + H]+.The title compound was synthesized according to a reported literature protocol  = 0.93\u2005\u00c5, iUso(H) = 1.2Ueq(C) for aromatic H atoms, and 0.96\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for methyl H atoms. Owing to poor agreement between observed and calculated intensities, five outliers  I. DOI: 10.1107/S2056989020007549/wm5554Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007549/wm5554Isup3.cmlSupporting information file. DOI: 2007970CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The phenol ring makes a dihedral angle of 44.77\u2005(3)\u00b0 with the benzene ring of the tri\u00adfluoro\u00admethyl group. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO inter\u00adactions, forming polymeric chain along the b-axis direction.The title compound, C 15H12F3NO, crystallizes with one mol\u00adecule in the asymmetric unit. The configuration of the C=N bond is E and there is an intra\u00admolecular O\u2014H\u22efN hydrogen bond present, forming an S(6) ring motif. The dihedral angle between the mean planes of the phenol and the 4-tri\u00adfluoro\u00admethyl\u00adphenyl rings is 44.77\u2005(3)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO inter\u00adactions, forming polymeric chains extending along the a-axis direction. The Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from C\u22efH/H\u22efC (29.2%), H\u22efH (28.6%), F\u22efH/H\u22efF (25.6%), O\u22efH/H\u22efO (5.7%) and F\u22efF (4.6%) inter\u00adactions. The density functional theory (DFT) optimized structure at the B3LYP/6-311\u2005G level is compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap. The crystal studied was refined as an inversion twin.The title compound, C These compounds show biological activities including anti\u00adbacterial, anti\u00adfungal, anti\u00adcancer and herbicidal activities  carried out at the B3LYP/6-311\u2005G level are compared with the experimentally determined mol\u00adecular structure of (I)S(6) ring motif; this is a common feature in related imine\u2013phenol compounds. The imine group displays a C9\u2014C8\u2014N1\u2014C6 torsion angle of 170.1\u2005(4)\u00b0 while the mean plane of the phenol ring (C9\u2013C14) is inclined to that of the 4-tri\u00adfluoro\u00admethyl\u00adphenyl group (C1\u2013C6) by 44.77\u2005(3)\u00b0. The configuration of the C8=N1 bond is E. The C10\u2014O1 bond length [1.357\u2005(8)\u2005\u00c5  and 1.342\u2005\u00c5 ] indicates single-bond character a-axis direction on Fig.\u00a02. The cryet al., 2007CrystalExplorer17.5  and shape-index  surfaces of (I)b) inter\u00adactions that involve C1\u2014H1A and the oxygen atom O1 of the phenol group de and di diagonal axes. The presence of C\u2014H\u22efO inter\u00adactions in the crystal is indicated by the pair of characteristic wings in the fingerprint plot delineated into C\u22efH/H\u22efC  contacts (29.2% contributions to the Hirshfeld surface). In Fig.\u00a05c, the widely scattered points in the fingerprint plot are related to H\u22efH contacts, which make a contribution of 28.6% to the Hirshfeld surface. There are also F\u22efH/H\u22efF , O\u22efH/H\u22efO  and F\u22efF  contacts, with smaller contributions from N\u22efH/H.\u00b7N (2.4%), O\u22efC/C\u22efO (2.2%), F\u22efC/C\u22efF (0.8%) and O\u22efN/N\u22efO (0.2%) contacts.In order to visualize the role of weak inter\u00admolecular inter\u00adactions in the crystal, a Hirshfeld surface (HS) analysis  using the standard B3LYP functional and the 6-311G basis-set calculations A = \u2212EHOMO), the ionization potential (I = \u2212ELUMO), the HOMO\u2013LUMO energy gap (\u0394E), the chemical hardness (\u03b7) and softness (S)  and the lowest-unoccupied mol\u00adecular orbital (LUMO) are very important aspects as many electronic, optical and chemical reactivity properties of compounds can be predicted from these frontier mol\u00adecular orbitals -2-{[(3-chloro\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-6-methyl\u00adphenol -2-[(2-hy\u00addroxy-5-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile -1-phenyl-N-imino}\u00admeth\u00adyl)phenolato]rhodium(III) chlorido\u00ad[2-({[4-(tri\u00adfluoro\u00admeth\u00adyl) phen\u00adyl]imino}\u00admeth\u00adyl)phen\u00adolato]iridium(III) sal\u00adicylaldiminato)titanium(IV) toluene solvate meth\u00adyl]amin\u00adato}copper(II) imino\u00admeth\u00adyl]phenolato}bis(tetra\u00adhydro\u00adfuran)\u00advanadium(III) imino\u00admeth\u00adyl]phenolato}(tetra\u00adhydro\u00adfuran)\u00advanadium(III) phen\u00adyl]-3-meth\u00adoxy\u00adsalicylaldimine -3-{[3-(tri\u00adfluoro\u00admeth\u00adyl)phenyl\u00adimino]\u00admeth\u00adyl}benz\u00adene-1,2-diol -5-(tri\u00adfluoro\u00admeth\u00adyl)aniline -2-meth\u00adyl-6-[3-(tri\u00adfluoro\u00admeth\u00adyl)phenyl\u00adimino\u00admeth\u00adyl]phenol -2-[(4-chloro\u00adphen\u00adyl)imino\u00admeth\u00adyl]-4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol -4-methyl-2-[3-(tri\u00adfluoro\u00admeth\u00adyl)phenyl\u00adimino\u00admeth\u00adyl]phenol  in ethanol (15\u2005mL) and 4-tri\u00adfluoro\u00admethyl\u00adphenyl\u00adamine  in ethanol (15\u2005mL) and stirring the mixture for 8\u2005h under reflux. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2\u20131.5Ueq(C). The hydrogen atom of the phenol group was located in a difference map and also included as a riding contributor with O\u2014H = 0.82\u2005\u00c5 and Uiso(H) = 1.5Ueq(O). During refinement, the twin transformation matrix , was used.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020009615/mw2164sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009615/mw2164Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009615/mw2164Isup3.cmlSupporting information file. DOI: 2016363CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Pseudomonas putida and Bacillus subtilis. Notably, the more water\u2010soluble cIPTG derivative proved to be particularly suitable for light\u2010mediated gene expression in these alternative expression hosts.Photolabile protecting groups play a significant role in controlling biological functions and cellular processes in living cells and tissues, as light offers high spatiotemporal control, is non\u2010invasive as well as easily tuneable. In the recent past, photo\u2010responsive inducer molecules such as 6\u2010nitropiperonyl\u2010caged IPTG (NP\u2010cIPTG) have been used as optochemical tools for Lac repressor\u2010controlled microbial expression systems. To further expand the applicability of the versatile optochemical on\u2010switch, we have investigated whether the modulation of cIPTG water solubility can improve the light responsiveness of appropriate expression systems in bacteria. To this end, we developed two new cIPTG derivatives with different hydrophobicity and demonstrated both an easy applicability for the light\u2010mediated control of gene expression and a simple transferability of this optochemical toolbox to the biotechnologically relevant bacteria  Extended toolbox: New photocaged IPTG derivatives with various hydrophobicities for light\u2010induced gene expression were synthesised and tested with three different expression host strains. The most water\u2010soluble compound showed superior performance, especially in Bacillus subtilis. A dean\u2010stark trap filled with molecular sieve (3\u2005\u00c5) was utilised for the constant removal of water. After the reaction was completed as indicated by TLC, it was washed with saturated NaHCO3 solution. The aqueous phase was then extracted with CH2Cl2 and the combined organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on SiO2 (petroleum ether/ethyl acetate 85\u2009:\u200915) to yield a yellow solid . Rf=0.25 (petroleum ether/ethyl acetate 80\u2009:\u200920) m.p. 62.1\u2009\u00b0C; 1H NMR : \u03b4=1.12 , 1.22 , 3.50 , 3.62 , 4.18 , 4.19 , 4.96 , 4.99 , 5.88 , 7.09 , 7.57\u2005ppm ; 13C NMR : \u03b4=14.0 (C\u201011 and C\u201011\u2032), 14.9 (C\u20102\u2032), 60.8 (C\u201010 or C\u201010\u2032), 60.9 (C\u201010 or C\u201010\u2032), 65.5 (C\u20108 or C\u20108\u2032), 65.6 (C\u20108 or C\u20108\u2032), 97.7 (C\u20107), 110.6 (C\u20103), 111.5 (C\u20106), 127.9 (C\u20101), 141.4 (C\u20102), 146.5 (C\u20104), 150.2 (C\u20105), 168.1 (C\u20109 or C\u20109\u2032), 168.1\u2005ppm (C\u20109 or C\u20109\u2032); IR (ATR\u2010film): \u1e7d=2981, 1755, 1692, 1581, 1526, 1446, 1346, 1291, 1196, 1176, 1080, 878, 796\u2005cm\u22121; HRMS (ESI): m/z calcd for C19H27NO10+: 447.1973 [M+NH4]+; found: 447.1972.Synthesis of BEC\u2010cIPTG (10\u2009a): To a solution of 4,5\u2010bis(ethoxycarbonylmethoxy)\u20102\u2010nitrobenzylaldehyde diethyl acetal (12)  in dry CH2Cl2 (6\u2005mL) IPTG  was added. After 5\u2005min p\u2010TSA  was added to the suspension and it was stirred at room temperature for 20\u2005h. After the reaction was completed as indicated by TLC, a small amount of triethylamine was added and the reaction was concentrated under reduced pressure. The residue was purified by flash column chromatography on SiO2 (petroleum ether/ethyl acetate 50\u2009:\u200950 to 20\u2009:\u200980) to yield a white solid . Rf=0.35 (petroleum ether/ethyl acetate 20\u2009:\u200980); m.p. 104.5\u2009\u00b0C; [\u03b1]= \u221268 (c=1.0 in CHCl3); 1H NMR : \u03b4=1.31 , 1.35 , 1.36 , 2.56 , 3.25 , 3.52 , 3.64\u20133.70 , 4.08 , 4.24\u20134.31 , 4.41 , 4.77 , 4.82 , 6.21 , 7.35 , 7.54\u2005ppm ; 13C NMR : \u03b4=14.3 (C\u201011 or C\u201011\u2032), 14.3 (C\u201011 or C\u201011\u2032), 24.1 (CH3\u2010a or CH3\u2010b), 24.3 (CH3\u2010a or CH3\u2010b), 35.5 (SCH), 61.8 (C\u201010 or C\u201010\u2032), 61.9 (C\u201010 or C\u201010\u2032), 66.4 (C\u20108 or C\u20108\u2032), 66.6 (C\u20108 or C\u20108\u2032), 69.8 (C\u20106\u2032\u2032), 70.1 (C\u20105\u2032\u2032), 70.3 (C\u20103\u2032\u2032), 73.9 (C\u20102\u2032\u2032), 76.2 (C\u20104\u2032\u2032), 85.7 (C\u20101\u2032\u2032), 96.6 (C\u20107), 111.5 (C\u20103), 112.8 (C\u20106), 127.7 (C\u20101), 141.3 (C\u20102), 147.6 (C\u20104), 151.7 (C\u20105), 167.9 (C\u20109 or C\u20109\u2032), 167.9\u2005ppm (C\u20109 or C\u20109\u2032); IR (ATR\u2010film): \u1e7d=3478, 2967, 2916, 2866, 1747, 1520, 1287, 1176, 1097, 1077, 1027, 989\u2005cm\u22121; UV/Vis (MeOH): \u03bbmax (\u03f5)=298 nm (8006\u2005dm3 mol\u22121 cm\u22121); HRMS (ESI): m/z calcd for C24H37N2O13S: 593.2011 [M+NH4]+; found: 593.2011.Synthesis of BC\u2010cIPTG (10\u2009b): A solution of BEC\u2010cIPTG (10a)  in MeOH (3.5\u2005mL) was cooled to 0\u2009\u00b0C and a 0.2\u2005m solution of LiOH (3.5\u2005mL) was added. The reaction mixture was stirred for 1\u2005h at room temperature. After the reaction was completed as indicated by TLC, the MeOH was evaporated under reduced pressure and the remaining solution was lyophilised overnight. The residue was suspended in THF, sonicated for 15\u2005min and filtrated. After washing with small amounts of cold THF a white solid  was obtained. m.p. 190\u2009\u00b0C (decay); [\u03b1]=\u221292 (c=1.0 in H2O); 1H NMR : \u03b4=1.29 , 1.31 , 3.26 , 3.66 , 3.71\u20133.82 , 4.18 , 4.37 , 4.60 , 4.62 , 4.67 , 6.20 , 7.32 , 7.55\u2005ppm ; 13C NMR : \u03b4=22.9 (CH3\u2010a), 23.3 (CH3\u2010b), 35.0 (SCH), 67.3(C\u20108\u2032), 67.4 (C\u20108), 69.1 (C\u20102\u2032\u2032), 69.3 (C\u20106\u2032\u2032), 69.6 (C\u20105\u2032\u2032), 72.8 (C\u20103\u2032\u2032), 76.5 (C\u20104\u2032\u2032), 84.8 (C\u20101\u2032\u2032), 96.4 (C\u20107), 109.2 (C\u20103), 110.8 (C\u20106), 126.3 (C\u20101), 140.0 (C\u20102), 147.2 (C\u20104), 151.5 (C\u20105), 175.1 (C\u20109), 175.4\u2005ppm (C\u20109\u2032); IR (ATR\u2010film): \u1e7d=3124, 3043, 1605, 1522, 1398, 1335, 1277, 1077, 1047, 1024, 824\u2005cm\u22121; UV/Vis (H2O): \u03bbmax (\u03f5)=245 (5008), 342\u2005nm (3191\u2005dm3 mol\u20101 cm\u22121); HRMS (ESI): m/z calcd for C20H29N2O13S+: 537.1385 [M+NH4]+; found: 537.1382.Determination of purity by qNMR: The purity of the photocaged IPTG derivatives 10\u2009a, 10\u2009b and 1 was determined via quantitative NMR. 3,5\u2010bis(trifluoromethyl)bromobenzene was utilised as internal standard for 10\u2009a as well as 1 and (methanesulfonyl)methane for 10\u2009b. The spectra were measured at 20\u2009\u00b0C on a Bruker Avance/DRX 600 spectrometer with 64 scans each and 30\u2005\u03bcs relaxation time between each scan. The results in Table\u2005S3 are means of triplicate measurements.Solubility analysis: The solubility of 10\u2009a, 10\u2009b and 14 was determined photometrically at 25\u2009\u00b0C using a spectrophotometer Shimadzu UV\u20101800 (CPS\u2010240A). The absorbance of a serial dilution in degassed and deionised water was measured at the absorption maximum of the respective compound. A saturated solution was measured under the same conditions. The solubility was calculated using the Beer\u2010Lambert law.Hydrolytic stability: For the determination of the hydrolytic stability, a 1 mm solution of the respective compound in methanol or sodium phosphate buffer  was stored in the dark at room temperature. Samples were removed after 0 and 24\u2005h and analysed by reversed\u2010phase HPLC.Quantification of uncaging half\u2010life times: A 1\u2005mm solution of each photocaged compound in methanol or sodium phosphate buffer  was prepared. In a cuvette 1 mL of this solution was irradiated at room temperature using the LUMOS 43 (375\u2005nm) for a certain time period. The sample was then analysed by reverse phase HPLC Jasco HPLC system [column: Hyperclone 5\u2005\u03bc ODS (C18) 120 (Phenomenex)]. For each photocaged compound, the procedure was repeated for different irradiation times. The decrease of concentration was measured by an UV detector.Determination of uncaging quantum yields: The quantum yields of 1, 10\u2009a and 10\u2009b were determined by a relative method in comparison to the quantum yield of 2\u2010nitropiperonylacetate (NPA\u2010Ac), as this substrate shows a sufficient similarity to 1, 10\u2009a and 10\u2009b. The procedure was followed as previously described in literature .[Bacterial strains and plasmids: The E.\u2005coli strain DH5\u03b1E.\u2005coli strain S17\u20101E.\u2005coli strains, the P.\u2005putida strain KT2440B.\u2005subtilis strain DB430E.\u2005coli) or 30\u2009\u00b0C . Media were supplemented either with kanamycin (50\u2005\u03bcg\u2009mL\u22121), gentamicin (25\u2005\u03bcg\u2009mL\u22121), irgasan (25\u2005\u03bcg\u2009mL\u22121) or chloramphenicol (5\u2005\u03bcg\u2009mL\u22121), when appropriate.All bacterial strains and plasmids used in this study are listed in Table\u2005S1, Supporting Information.Plasmid construction: All recombinant DNA techniques were carried out as described by Sambrook et al.B.\u2005subtilis expression vector pHT01\u2010sfGFP, the sfGFP\u2010encoding gene was synthesised with flanking NdeI and HindIII restriction sites  and subsequently cloned into pET\u201022(b) . The resulting vector pET\u201022(b)\u2010sfGFP was used as template for SLIC cloningsfgfp gene into the B.\u2005subtilis expression vector pHT01  using oligos 3\u20136 . The P.\u2005putida expression vector pVLT33\u2010GFPmut3 was constructed by restriction and ligation. To this end, the gfpmut3 gene was amplified with flanking EcoRI and XbaI restriction sites via PCR using oligos 1\u20132 (Table\u2005S1). Afterwards, the EcoRI/XbaI hydrolysed fragment was ligated into the likewise hydrolysed vector backbone pVLT33, resulting in the final expression vector pVLT33\u2010GFPmut3. Correct nucleotide sequences of all constructs were confirmed by Sanger sequencing (Eurofins Genomics).Cultivation conditions: All E.\u2005coli, P.\u2005putida and B.\u2005subtilis expression cultures were grown in 48\u2010well Flowerplates\u00ae in a BioLector microbioreactor system  , inoculated with an optical density at 580\u2005nm of 0.05. During cultivation, the cell density was measured online through the scattered light intensity at 620\u2005nm. In addition, fluorescence of eYFP and GFP variants (GFPmut3 and sfGFP) were continuously determined using a 508/532\u2005nm and 488/520\u2005nm filter, respectively. cIPTG variants 10\u2009a, 10\u2009b or NP\u2010cIPTG (1) were added prior inoculation  and expression of reporter genes was induced during the early logarithmic growth phase  via UV\u2010A light exposure  or by addition of equal amounts of conventional IPTG (14) after illumination.Determination of expression heterogeneity: For measurement of the expression heterogeneity, E.\u2005coli and B.\u2005subtilis cultures were analysed on the single\u2010cell level by flow cytometry regarding their fluorescence intensity and distribution. Expression cultures were grown as described above and were subsequently sampled as soon as they reached the late logarithmic growth phase (after 8\u2005h for E.\u2005coli and after 10\u2005h for B.\u2005subtilis). For this purpose, 40\u2005\u03bcL was taken out of the Flowerplate\u00ae cultures and added to 600\u2005\u03bcL PBS buffer (pH\u20057.4). Subsequently, the cells were harvested by centrifugation , adjusted to an optical density of 0.5 (OD580) in 100\u2005\u03bcL PBS buffer and then transferred into a 96\u2010well microtiter plate . Finally, these samples were analysed with a flow cytometer . The individual cellular fluorescence brightness was measured using a 488\u2010nm laser (15\u2009% intensity for E.\u2005coli and 5\u2009% for B.\u2005subtilis) for excitation and a 528/46\u2005nm bandpass filter for detection. To exclude cell debris and cell aggregates, the cells were also analysed regarding their size  and granularity . FSC was measured using an FSC laser (nm) with 80\u2009% of the laser power for E.\u2005coli and 50\u2009% for B.\u2005subtilis and a 456/51\u2005nm bandpass filter for detection. For determination of SSC a nm\u2010light laser with 80\u2009% of the laser power for E.\u2005coli and 50\u2009% for B.\u2005subtilis (773/56\u2005nm bandpass filter) was used. Based on the scatter plots, bacterial cells were gated from irrelevant counts for fluorescence analysis. Flow cytometric data were evaluated with the CellStreamTM Analysis Software .The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The crystal structure features both intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonds, as well as inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions, leading to the formation of sheets parallel to the ac plane.The crystal structure of a pyrrolidine-substituted  11H15NO2S, features a sulfonamide group with S=O bond lengths of 1.4357\u2005(16) and 1.4349\u2005(16)\u2005\u00c5, an S\u2014N bond length of 1.625\u2005(2)\u2005\u00c5, and an S\u2014C bond length of 1.770\u2005(2)\u2005\u00c5. When viewing the mol\u00adecule down the S\u2014N bond, both N\u2014C bonds of the pyrrolidine ring are oriented gauche to the S\u2014C bond with torsion angles of \u221265.6\u2005(2)\u00b0 and 76.2\u2005(2)\u00b0. The crystal structure features both intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonds, as well as inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions, leading to the formation of sheets parallel to the ac plane.The mol\u00adecular structure of the title compound, C Sulfonamides are of significant value in organic chemistry because of their therapeutic properties. These mol\u00adecules are referred to in the pharmaceutical industry as sulfa drugs. This class of drugs has been widely used in various pharmaceutical applications owing to their anti\u00adbacterial, anti\u00adviral, anti\u00admalarial, anti\u00adfungal, anti\u00adcancer, anti\u00addepressant, and other properties \u00b0 and C5\u2014S1\u2014N1\u2014C4 = 76.16\u2005(19)\u00b0. A conformational analysis of the five-membered pyrrolidine ring pucker gives a puckering amplitude (Q2) parameter of 0.352\u2005(3)\u2005\u00c5 and a \u03c62 parameter of 262.2\u2005(4)\u00b0. Consequently, this ring is in a half-chair conformation with a twist along the C2\u2014C3 bond. Lastly, an intra\u00admolecular C\u2014H\u22efO contact  and a symmetry-derived ring . The \u03c0\u2013\u03c0 inter\u00adaction has a centroid-to-centroid distance of 3.8162\u2005(15)\u2005\u00c5 with a slippage of 1.307\u2005\u00c5. The result of these inter\u00adactions is the formation of sheets that lie in the ac plane  to a stirring mixture of pyrrolidine  and 10\u2005ml of tetra\u00adhydro\u00adfuran. This was followed by the dropwise addition of 0.59 M aqueous potassium carbonate  and the mixture was stirred at room temperate for 6\u2005h. Upon acidification with 5 M HCl, a white precipitate was isolated by vacuum filtration to give the crude sulfonamide product. The crude product was dissolved in hot ethanol and filtered. The filtrate was transferred to a scintillation vial and crystallized upon standing for 24\u2005h to afford colorless crystals, filtered from the mother liquor .The title compound was prepared by the dropwise addition of Uiso(H) = 1.2Ueq(C) for methyl\u00adene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902000208X/wm5540sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902000208X/wm5540Isup2.hklStructure factors: contains datablock(s) I. DOI: 1983920CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Phnl\u22efNPrmdn and N\u2014HPrmdn\u22efOPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds link the mol\u00adecules into infinite chains along the b-axis direction. C\u2014H\u22ef\u03c0 inter\u00adactions may further stabilize the crystal structure.The title compound consists of perimidin and meth\u00adoxy\u00adphenol units. In the crystal, O\u2014H 18H16N2O2, consists of perimidine and meth\u00adoxy\u00adphenol units, where the tricyclic perimidine unit contains a naphthalene ring system and a non-planar C4N2 ring adopting an envelope conformation with the NCN group hinged by 47.44\u2005(7)\u00b0 with respect to the best plane of the other five atoms. In the crystal, O\u2014HPhnl\u22efNPrmdn and N\u2014HPrmdn\u22efOPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds link the mol\u00adecules into infinite chains along the b-axis direction. Weak C\u2014H\u22ef\u03c0 inter\u00adactions may further stabilize the crystal structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (49.0%), H\u22efC/C\u22efH (35.8%) and H\u22efO/O\u22efH (12.0%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, the O\u2014HPhnl\u22efNPrmdn and N\u2014HPrmdn\u22efOPhnl hydrogen-bond energies are 58.4 and 38.0\u2005kJ\u2005mol\u22121, respectively. Density functional theory (DFT) optimized structures at the B3LYP/ 6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C We report herein the synthesis, the mol\u00adecular and crystal structures along with Hirshfeld surface analysis and computational calculations of the title compound, (I)Six-membered heterocyclic compounds carrying two nitro\u00adgen atoms have been widely studied , ring gave the parameters q2 = 0.3879\u2005(12)\u2005\u00c5, q3 = \u22120.2565\u2005(12)\u2005\u00c5, QT = 0.4650\u2005(13)\u2005\u00c5, \u03b82 = 123.47\u2005(15)\u00b0 and \u03c62 = 235.98\u2005(18)\u00b0]. The ring adopts an envelope conformation, where atom C1 is at the flap position and at a distance of 0.6454\u2005(12)\u2005\u00c5 from the best plane through the other five atoms. The C4N2 ring is hinged about the N\u22efN vector with the N1\u2014C1\u2014N2 plane being inclined by 47.44\u2005(7)\u00b0 to the best plane of the other five atoms (N1/N2/C9\u2013C11). In the meth\u00adoxy\u00adphenol moiety, the C8\u2014O2\u2014C4\u2014C5 and C8\u2014O2\u2014C4\u2014C3 torsion angles are \u22122.9\u2005(2)\u00b0 and 176.72\u2005(12)\u00b0, respectively. Rings A (C2\u2013C7), C (C10\u2013C15) and D (C9/C10/C15\u2013C18) are oriented at dihedral angles of A/C = 65.39\u2005(4)\u00b0, A/D = 69.63\u2005(4)\u00b0 and C/D = 4.31\u2005(3)\u00b0.The title compound, (I)ng Fig.\u00a01. A puckePhnl\u22efNPrmdn and N\u2014HPrmdn\u22efOPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds  analysis  have a symmetrical distribution of points with the tips at de + di = 3.03\u2005\u00c5. The H\u22efN/N\u22efH contacts  have a distribution of points with the tips at de + di = 2.72\u2005\u00c5. The C\u22efC contacts  have the tip at de = di = 3.37\u2005\u00c5. Finally, the O\u22efC/C\u22efO inter\u00adactions make only a 0.5% contribution to the overall crystal packing.The overall two-dimensional fingerprint plot, Fig.\u00a06dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions in Fig.\u00a07a\u2013c, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated as \u221237.5 (Eele), \u22127.8 (Epol), \u221252.0 (Edis), 52.4 (Erep) and \u221258.4 (Etot)  of the mol\u00adecule is about 2.6162\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22123.1985 and \u22120.5823\u2005eV, respectively.The optimized structure of the title compound, (I)et al., 2011et al., 2013et al., 2013bet al., 2014et al., 2011et al., 2013bet al., 2013bet al., 2011et al., 2013et al., 2014Similar compounds of the perimidine derivative have also been reported  and 1,8- di\u00adaminona\u00adphthalene (4\u2005mmol) in ether (30\u2005ml) under agitation at room temperature. Brown single crystals were obtained by the slow evaporation of the acetone solvent after 15 days (yield: 75%).The title compound, (I)C, H15A and H15B of the allyl moiety), 0.98\u2005\u00c5 (for methine H atom) and 0.97\u2005\u00c5 (for methyl\u00adene H atoms), and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The hydroxyl H atom was placed in a calculated position with O\u2014H = 0.82\u2005\u00c5 and Uiso(H) = 1.5Ueq(O) while H atoms bonded to N atoms were refined independently with Uiso(H) = 1.2Ueq(N)Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020004284/lh5952sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020004284/lh5952Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020004284/lh5952Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020004284/lh5952Isup4.cmlSupporting information file. DOI: 1976883CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the PDF version of this Article, the abbreviations for corresponding authors have been reversed\u201cCorrespondence and requests for materials should be addressed to Y.Z. (email: jinrong@bjmu.edu.cn) or R.J. (email: zhangyu007@bjmu.edu.cn)\u201dshould read:\u201cCorrespondence and requests for materials should be addressed to R.J. (email: jinrong@bjmu.edu.cn) or Y.Z. (email: zhangyu007@bjmu.edu.cn)This is correct in the HTML version of the ArticleIn the Materials and Methods section under the subheading \u201cThymic stromal cell isolation\u201d section,+), pDCs (CD11cint/hiCD45RA+), resident conventional DCs (CD11c+CD8\u03b1+CD172\u03b1\u2212), and migratory DCs (CD11c+CD8\u03b1\u2212CD172\u03b1\u2212)\u201d\u201cTo purify thymic DCs, cells were stained with fluorescence-labeled antibodies against CD11c, CD45RA, CD8\u03b1 and CD172\u03b1 and sorted on a BD FACS Aria II into the following fractions: total DCs (CD11cshould read:+), pDCs (CD11cint/hiCD45RA+), resident conventional DCs (CD11c+CD8\u03b1+CD172\u03b1\u2212), and migratory DCs (CD11c+CD8\u03b1\u2212CD172\u03b1+)\u201d\u201cTo purify thymic DCs, cells were stained with fluorescence-labeled antibodies against CD11c, CD45RA, CD8\u03b1 and CD172\u03b1 and sorted on a BD FACS Aria II into the following fractions: total DCs ,+ and CD172\uf061+ cDC was analyzed by flow cytometry following intracellular staining with anti-IL-27\u201d.\u201c(B) IL-27 protein expression in pDC, CD8\uf061Should read+ and CD172\u03b1+ cDC was analyzed by flow cytometry following intracellular staining with anti-IL-27\u201d.\u201c(B) IL-27 protein expression in pDC, CD8\u03b1Figure 6B and 6C were inverted. The correct Figure 6 appears below as"}
{"text": "After publication, an error was noticed in the \"Cell spreading is altered by RGD mutations\" section of the Results. The error occurred in the first paragraph, and the corrected text appears below.RGE and cFN\u0394RGD allows \u03b15\u03b21 and \u03b1v-class integrin\u2013mediated adhesion maturation and spreading, we plated pKO-\u03b1v, pKO-\u03b21, and pKO-\u03b1v/\u03b21 fibroblasts in serum replacement medium (SRM) on purified cFN variants and determined cell spreading as well as morphology and distribution of FAs  and pKO-\u03b1v/\u03b21 fibroblasts (79.6 \u00b1 7.9%) spread on cFNRGE; and a neglectable percentage of pKO-\u03b21 fibroblasts spread on cFNRGE. On cFN\u0394RGD, the numbers of spread pKO-\u03b1v and pKO-\u03b1v/\u03b21 fibroblasts dropped to 22.2 \u00b1 15% and 10.4 \u00b1 7.0%, respectively, and of pKO-\u03b21 fibroblasts to <1% , similar to pKO-\u03b1v (583 \u00b1 42 \u00b5m2) and pKO-\u03b1v/\u03b21 fibroblasts (514 \u00b1 49 \u00b5m2) on cFNRGE. 2 (P < 0.05 compared to pKO-\u03b1v cells) on cFNRGE. In RGE cells from P < 0.001 to P < 0.05.The few adherent pKO-\u03b21 fibroblasts covered a reduced area of 419 \u00b1 36 \u00b5m On cFN\u0394RGD, the adherent pKO-\u03b1v, pKO-\u03b21, and pKO-\u03b1v/\u03b21 fibroblasts covered significantly smaller spreading areas  when compared with the same cell lines seeded on cFNRGD (\"To test whether full-length cFNn of FAs . At 60 ms to <1% . Moreoven cFNRGD .\"The P values in"}
{"text": "II ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two -1,2-bis\u00ad(bi\u00adnaphthyl\u00adphospho\u00adnito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octa\u00adhedral coordination geometry. Weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions occur in the crystal.In the title compound, the Fe 2,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-deca\u00aden-13-yl]ethane}\u00addichlorido\u00adiron(II) di\u00adchloro\u00admethane disolvate), [FeCl2(C42H28O4P2)2]\u00b72CH2Cl2, the FeII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two -1,2-bis\u00ad(bi\u00adnaphthyl\u00adphospho\u00adn\u00adito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octa\u00adhedral coordination geometry. In the crystal, weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into layers lying parallel to (001). A weak intra\u00admolecular C\u2014H\u22efO hydrogen bond is also observed. The asymmetric unit contains one CH2Cl2 solvent mol\u00adecule, which is disordered over two sets of site with refined occupancies in the ratio 0.700\u2005(6):0.300\u2005(6).In the title compound (systematic name: bis\u00ad{1,2-bis[12,14-dioxa-13-phospha\u00adpenta\u00adcyclo\u00ad[13.8.0.0 R,R)- or -1,2-bis\u00ad(bi\u00adnaphthyl\u00adphospho\u00adnito)ethane  prepared from either (R)- or (S)-1,1\u2032-bi(2-naphthol)  has been used extensively in asymmetric catalysis, as has the related ligand (R) or (S)-2,2\u2032-bis\u00ad(di\u00adphenyl\u00adphosphino)-1,1\u2032-binaphthyl . For example, the BINAP ligand has been coordinated to ruthenium and used for the asymmetric hydrogenation of ketones 2]. The BPE ligand and similar bidentate and monodentate phospho\u00adnite ligands have been coordinated to rhodium and iridium and used for asymmetric alkene and quinoline hydrogenation reactions, respectively 2, which crystallized as a di\u00adchloro\u00admethane solvate.As an extension of these studies, we now describe the synthesis and crystal structure of the iron(II) complex FeClII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two BPE ligands and two Cl ligands in a distorted cis-FeCl2P4 octa\u00adhedral coordination geometry. The largest distortion from ideal coordination geometry is the P2\u2014Fe\u2014P2i angle of 108.49\u2005(7)\u00b0  are the same, with values of 54.5\u2005(2)\u00b0. A weak intra\u00admolecular C\u2014H\u22efO hydrogen bond is observed :0.300\u2005(6).The mol\u00adecular structure of the title compound is shown in Fig.\u00a01d Table\u00a02. The asyCg2\u22efCg2 of 4.171\u2005(5)\u2005\u00c5 (where Cg2 is the centroid of the C4\u2013C9 benzene ring) may be a very weak \u03c0-stacking inter\u00adaction.In the crystal, weak C\u2014H\u22efO hydrogen bonds link mol\u00adecules into sheets parallel to (001) Table\u00a02. Within et al., 20162(P2)2 (P2 = a diphosphine) with P\u2014C bonds reported. The majority, 33 complexes, crystallize with the chloride ions trans to each other, while there are three examples where the chloride ions are cis, as in the title complex. The complex trans-FeCl2ethyl\u00adene)2, for example, crystallizes with the chloride ions trans 2  and 2.3423\u2005(11)\u2005\u00c5 in the title complex.A search of the Cambridge Structural Database -BINOL  was combined with -BPE  in 10\u2005ml THF and stirred in a 20\u2005ml dram vial for 24\u2005h. The THF was vacuumed off to yield a brown powder: 31P{1H} NMR : 257.72 ppm, singlet.The ligand was synthesized according to a literature procedure using  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a032Cl2 solvent mol\u00adecule was refined without restraints while the minor component was restrained to have similar geometry and anisotropic displacement parameters to the major component using the SAME and SADI instructions in SHELXL  I. DOI: 10.1107/S2056989020011160/hb7939Isup2.hklStructure factors: contains datablock(s) I. DOI: 2023248CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "An intra\u00admolecular short S\u22efO contact [3.215\u2005(2)\u2005\u00c5] is observed. The crystal packing features C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, the dihedral angle between the fused pyrazole and pyridine rings is 1.76\u2005(7)\u00b0. The benzene and meth\u00adoxy phenyl rings make dihedral angles of 44.8\u2005(5) and 63.86\u2005(5)\u00b0, respectively, with the pyrazolo\u00ad pyridine moiety. An intra\u00admolecular short S\u22efO contact [3.215\u2005(2)\u2005\u00c5] is observed. The crystal packing features C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, C The thio\u00admethyl (\u2013SCH3) group fused to the pyrazolo\u00adpyridine unit exhibits a (+)anti-periplanar conformation [C8\u2014S1\u2014C7\u2014C6 = 175.47\u2005(15)\u00b0]. The torsion angles involving the \u2013SCH3 group differ from those for NUDWOB  group. The \u2013COOC2H5 group attached to the pyrazolo\u00adpyridine moiety has a (+)anti-periplanar conformation [N3\u2014C7\u2014C6\u2014C9 = 176.44\u2005(16)\u00b0]. Further, the methyl group attached to the pyrazole subunit is (+)anti-periplanar [C1\u2014N2\u2014N1\u2014C4 = 178.78\u2005(17)\u00b0] and it is attached to the pyridine ring showing a (+)syn-periplanar conformation [C1\u2014N2\u2014C2\u2014N3 = 1.3\u2005(3)\u00b0]. The fused pyrazole and pyridine rings in the title compound are not exactly planar, as in NUDWOB \u00b0 and that between the meth\u00adoxy\u00adphenyl and pyrazolo\u00adpyridine rings is 63.86\u2005(5)\u00b0.In the title compound Fig.\u00a01, the pheCg and C23\u2014H23\u22efCg) inter\u00adactions  = 3.291\u2005(2)\u2005\u00c5] may also exist  noted by Thomas et al. methanone; Ravi et al., 2017a]pyridine; Wu et al., 2016H-pyrazolo\u00adpyridine-5-carboxyl\u00adate; Rao et al., 20202CH3 substituent in the title compound are comparable with those reported for FIZLEI and NUDWOB. The bond distances for the thio\u00admethyl and aryl moieties in the title compound are comparable with those of NUDWOB. Moreover, the bond lengths in the pyrazolopyridine unit of the title compound are comparable with those in NUDWOB, FIZLEI, ALAFID, DAWKAQ and NADPIU. The pyrazolo\u00adpyridine moiety (N1\u2013N3/C2\u2013C4/C5\u2013C7) of the title compound is approximately planar, as is also observed for NUDWOB, FIZLEI, ALAFID, DAWKAQ and NADPIU. In the title compound, a short intra\u00admolecular S\u22efO contact of 3.215\u2005(2)\u2005\u00c5 occurs, but this is not observed in FIZLEI, ALAFID, DAWKAQ, NADPIU and NUDWOB. Moreover, the inter\u00adaction distance [3.291\u2005(2)\u2005\u00c5] of the short inter\u00admolecular C\u22efO contact in the title compound is comparable with the C\u22efO inter\u00adaction [3.424\u2005(2)\u2005\u00c5] in the structure of NUDWOB. Furthermore, as in the title compound, C\u2014H\u22ef\u03c0 inter\u00adactions are observed in the crystal structures of ALAFID, DAWKAQ and NADPIU. The inter\u00adaction distance of these related structures ranges from 2.89 to 3.23\u2005\u00c5, comparable with the C\u2014H\u22ef\u03c0 inter\u00adactions observed in the title compound.A similarity search of the Cambridge Structural Database  and ethyl 2-(4-meth\u00adoxy\u00adbenzo\u00adyl)-3,3-bis\u00ad(methyl\u00adthio)\u00adacrylate  in toluene (3\u2005mL), a catalytic amount of TFA (tri\u00adfluoro\u00adacetic acid) 30\u2005mol % in toluene (3\u2005mL) was added under an N2 atmosphere. The reaction mixture was refluxed for 24\u2005h in an oil bath, the progress of the reaction being monitored by TLC using a mixture of hexane and ethyl acetate (9.9:0.1). After completion of the reaction, the mixture was loaded on a silica gel column  and eluted with increasing amounts of ethyl acetate in hexa\u00adnes (1% to 5%) to obtain 186\u2005mg (yield = 75%) of ethyl 6-(4-meth\u00adoxy\u00adphen\u00adyl)-1-methyl-4-(methyl\u00adthio)-3-phenyl-1H-pyrazolo\u00adpyridine-5-carboxyl\u00adate as a colourless crystalline solid; m.p. 406\u2005K; Rf = 0.3\u2005cm (hexa\u00adne: ethyl acetate 9.9:0.1). A sample suitable for single-crystal X-ray analysis was obtained by recrystallization from 2\u2005mL of dry methanol.To a solution of 1-methyl-3-phenyl-1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020008841/dx2029sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008841/dx2029Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008841/dx2029Isup3.cmlSupporting information file. DOI: 2005976CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Acetamino\u00adphen assists as a co-former in the crystallization of hexa\u00admethyl\u00adene\u00adtetra\u00admine carboacetamino\u00adphenborane, which may otherwise be challenging to form a crystal itself. 15H22BN5O3\u00b7C8H9NO2. In the first of these mol\u00adecules, both the borate-ester and acetyl\u00adamino groups are considerably twisted away from the plane of the inter\u00advening benzene ring . The extended structure of this co-crystal features N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, which link the components into (100) sheets and weak C\u2014H\u22efO hydrogen bonds help to consolidate the structure.Hexa\u00admethyl\u00adene\u00adtetra\u00admine carboacetamino\u00adphenborane, a mol\u00adecule with two pharmacophores attached to a central carb\u00adoxy\u00adborate moiety, was synthesized and crystals were grown with an acetamino\u00adphen co-crystal former to result in the title 1:1 co-crystal [hexa\u00admethyl\u00adene\u00adtetra\u00admine 4-acetamido\u00adphenyl 2-boranyl\u00adacetate\u20134-acet\u00adamido\u00adphenol (1/1)], C This type of bond has been previously reported in the acetamino\u00adphen co-crystal with citric acid  of this hydrogen bond is similar to the N\u2014H\u22efO\u2014H bond (2.09\u2005\u00c5) from the known acetamino\u00adphen crystal form II  is identical in length to that of acetamino\u00adphen crystal form II (1.85\u2005\u00c5). Several weak C\u2014H\u22efO hydrogen bonds may help to consolidate the structure.During crystallization, the new difunctionalized mol\u00adecule, CORCB-1-APAP, forms a co-crystal with acetamino\u00adphen at a 1:1 ratio with hydrogen-bonding inter\u00adactions Table\u00a01 between et al., 1998A mol\u00adecular packing projection of (I)et al., 1980et al., 2002et al., 2002et al., 2017et al., 2009et al., 2011et al., 2007et al., 2002The crystal structures of amine carb\u00adoxy\u00adborane have been reported as dimers  involves several steps using tri\u00admethyl\u00adamine carb\u00adoxy\u00adborane (CORCB-3) as the starting material. Tri\u00admethyl\u00adamine carb\u00adoxy\u00adborane, synthesized by the previously reported method  = 1.2Ueq or 1.2Ueq(Cmeth\u00adyl)].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020015327/hb7947sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020015327/hb7947Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020015327/hb7947sup4.pdfCheckCIF. DOI: 1828957CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules of the title compound, a potential ligand containing two 8-quinolinol and one 2-pyridine units, are linked by inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO quadruple hydrogen bonds, forming an inversion dimer with two  24H15Cl2N3O2, one quinoline ring system is essentially planar and the other is slightly bent. An intra\u00admolecular O\u2014H\u22efN hydrogen bond involving the hy\u00addroxy group and a pyridine N atom forms an S(5) ring motif. In the crystal, two mol\u00adecules are associated into an inversion dimer with two R22(7) ring motifs through inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds. The dimers are further linked by an inter\u00admolecular C\u2014H\u22efO hydrogen bond and four C\u2014H\u22ef\u03c0 inter\u00adactions, forming a two-dimensional network parallel to (001).In the title compound, C The torsion angles C8\u2014C16\u2014C17\u2014C18, C26\u2014C18\u2014C17\u2014C27, and C28\u2014C27\u2014C17\u2014C16 are \u221288.6\u2005(2), \u2212101.2\u2005(2) and \u221287.8\u2005(2)\u00b0, respectively.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01fs Fig.\u00a01. The arri and O4\u2014H4\u22efN5i; symmetry code: (i) \u2013x\u00a0+\u00a01, \u2013y\u00a0+\u00a02, \u2013z\u00a0+\u00a02], forming an inversion dimer with two et al., 1999Cg1iii and C24\u2014H24\u22efCg3v; Cg1 is the centroid of the C18\u2013C21/C25/C26 ring and Cg3 is the centroid of the N7/C27\u2013C31 ring; symmetry codes: (iii) x\u00a0+\u00a01, y\u00a0+\u00a01, z; (v) \u2013x, \u2013y\u00a0+\u00a01, \u2013z\u00a0+\u00a02], forming a ribbon structure along [110]  x \u2013 1, y, z] and a C\u2014H\u22ef\u03c0 inter\u00adaction . The chains are linked by two C\u2014H\u22ef\u03c0 inter\u00adactions , generating a two-dimensional network parallel to (001)  Fig.\u00a04.et al., 2016et al., 19992 methane  and ethanol (6\u2005mL) were placed in a 15\u2005mL capped pressure tube. It was heated at 353\u2005K for 96\u2005h. The generated pale-white precipitate was filtered to give a pale-white solid . Single crystals of title compound suitable for X-ray diffraction were grown by slow evaporation of a solution in CHCl3/n-hexane  at ambient temperature. 1H NMR  \u03b4 = 6.63 , 7.21 , 7.33 , 7.52 , 7.52 , 7.67 , 8.48 , 8.64 , 8.81 , 8.84 .The title compound was prepared by a modification of the reported KUiso(H) = 1.2Ueq (C). One outlier  global, I. DOI: 10.1107/S2056989020009317/is5545Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009317/is5545Isup3.cmlSupporting information file. DOI: 2014831CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These are connected in three-dimensions by benzene-C\u2014H\u22efO(DTBA), DTBA-C=O\u22ef\u03c0(benzene) and benzene-C\u2014H\u22ef\u03c0(benzene) inter\u00adactions.In the title 1:1 solvate, 2,2\u2032-di\u00adthiodi\u00adbenzoic acid (DTBA):di\u00admethyl\u00adformamide (DMF), the DTBA mol\u00adecule is twisted [C\u2014S\u2014S\u2014C = \u221288.57\u2005(6)\u00b0]. Four-mol\u00adecule aggregates are formed in the crystal  14H10O4S2\u00b7C3H7NO, features a twisted mol\u00adecule of 2,2\u2032-di\u00adthiodi\u00adbenzoic acid (DTBA), with the central C\u2014S\u2014S\u2014C torsion angle being \u221288.57\u2005(6)\u00b0, and a mol\u00adecule of di\u00admethyl\u00adformamide (DMF). The carb\u00adoxy\u00adlic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03\u2005(19) and 7.4\u2005(2)\u00b0. Intra\u00admolecular, hypervalent S\u2190O inter\u00adactions are noted [S\u22efO = 2.6140\u2005(9) and 2.6827\u2005(9)\u2005\u00c5]. In the crystal, four-mol\u00adecule aggregates are formed via DTBA-O\u2014H\u22efO(DMF) and DTBA-O\u2014H\u22efO(DTBA) hydrogen bonding, the latter via an eight-membered {\u22efOHCO}2 homosynthon. These are linked into supra\u00admolecular layers parallel to (011) via benzene-C\u2014H\u22efO(DTBA) and DTBA-C=O\u22ef\u03c0(benzene) inter\u00adactions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C\u2014H\u22ef\u03c0(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned inter\u00admolecular contacts, the presence of stabilizing inter\u00adactions between a benzene ring and a quasi-\u03c0-system defined by O\u2014H\u22efO hydrogen bonds between a DTBA dimer, i.e. the eight-membered {\u22efOCOH}2 ring system, and between a benzene ring and a quasi-\u03c0(OCOH\u22efOCH) system arising from the DTBA-O\u2014H\u22efO(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49\u2005\u00c5, respectively.The title 1:1 solvate, C In a recent study, it was found the anti\u00adcipated {\u22efHOCO}2 synthon was not always formed but was usurped by a DTBA-O\u2014H\u22efO(DMF) hydrogen bond for one of the carb\u00adoxy\u00adlic acids, i.e. in the 1:1:1 co-crystal solvate DTBA:2-ClBA:DMF  solution also gave the DTBA:2DMF solvate  solution yielded the mono-solvate, i.e. the title compound DTBA:DMF, (I)Co-crystal formation with 2-mercapto\u00adbenzoic acid (2-MBA) is fraught as during crystallization, this is usually oxidized to 2,2\u2032-di\u00adthiodi\u00adbenzoic acid (DTBA)  solution indicating the acid oxidized to DTBA during crystallization. The observed disparity in the C\u2014O bond lengths in the carb\u00adoxy\u00adlic acid residues  confirms the location of the acidic H atoms on the O1 and O3 atoms, respectively. A characteristic twisted conformation is evidenced in the C3\u2014S1\u2014S2\u2014C8 torsion angle of \u221288.57\u2005(6)\u00b0. The dihedral angle between the benzene rings is 87.71\u2005(3)\u00b0, consistent with an orthogonal disposition. The C1-carb\u00adoxy\u00adlic acid group is almost co-planar with the (C2\u2013C7) benzene ring to which it is connected with the dihedral angle between the least-squares planes being 1.03\u2005(19)\u00b0. By contrast, a small twist is noted for the C14-carb\u00adoxy\u00adlic acid residue where the comparable dihedral angle is 7.4\u2005(2)\u00b0. Intra\u00admolecular hypervalent S\u2190O inter\u00adactions via an eight-membered {\u22efOHCO}2 homosynthon. The result is the four-mol\u00adecule aggregate shown in Fig.\u00a02a). For the DTBA\u22efDMF inter\u00adaction, further stabilization is realized through a DMF-C15\u2014H\u22efO2(carbon\u00adyl) contact, Table\u00a01via benzene-C7\u2014H\u22efO(hydrox\u00adyl) inter\u00adactions occurring between centrosymmetrically related mol\u00adecules. The chains are connected by parallel C=O\u22ef\u03c0(benzene) inter\u00adactions as detailed in Fig.\u00a02b) and Table\u00a01c), with connections between them leading to a three-dimensional architecture being benzene-C11\u2014H\u22ef\u03c0(benzene), Fig.\u00a02d).The key feature of the supra\u00admolecular aggregation in the crystal of (I)Mercury Crystal Explorer 17  and hy\u00addroxy-O3\u2014H3O\u22efO4(carbon\u00adyl) hydrogen bonds with the corresponding dnorm contact distances being 1.62 and 1.64\u2005\u00c5, respectively, i.e. significantly shorter by almost 1\u2005\u00c5 compared to the sum of the van der Waals radii of 2.61\u2005\u00c5 , Table\u00a02To better comprehend the supra\u00admolecular features of (I)\u03c0\u2013\u03c0 inter\u00adaction formed between the C8\u2013C13 benzene ring and a quasi-\u03c0-system defined by O3\u2014H3O\u22efO4 hydrogen bonds between a DTBA dimer, i.e. the eight-membered {\u22efO4\u2013C14\u2013O3\u2013H3O}2 ring system. A similar observation is also noted for the C1\u22efC15 contact which is encapsulated within an apparent \u03c0(C2\u2013C7)\u22efquasi-\u03c0(O2\u2013C1\u2013O1\u2013H1O\u22efO5\u2013C15\u2013H15) inter\u00adaction. The separation between the ring centroids of the aforementioned \u03c0\u2013\u03c0 contacts are 3.65 and 3.49\u2005\u00c5, respectively. The stacking arrangement between the relevant aromatic and quasi-aromatic rings is supported by shape complementarity as revealed by the concave (red) and convex (blue) regions in the shape index, Fig.\u00a05a)\u2013(d), as well as curvedness mappings, Fig.\u00a05e) and (f), obtained through the Hirshfeld surface analysis.Of particular inter\u00adest among all close contacts present in (I)d,p) approach to verify the nature of the contacts present in (I)O\u22efO5 followed by H3O\u22efO4 inter\u00adactions which is consistent with their corresponding short contact distances. By contrast, for the H\u22efC and C\u22efO inter\u00adactions relatively smaller charge disparity is noted indicating weaker attractions between the participating atoms,. The exception is found for the C\u22efC contacts which exhibit positive electrostatic charge for both donor and acceptor atoms signifying the dispersive nature of the contacts.The electrostatic potential property was mapped onto the Hirshfeld surface using the DFT-B3LYP/6-31G of 2.89\u2005\u00c5, Fig.\u00a06e). Further delineation of H\u22efO/O\u22efH, H\u22efC/C\u22efH and H\u22efS/S\u22efH shows that those heterogeneous contacts are more inclined towards -X\u22efH- in DTBA, while the opposite is true for DMF indicating the complementary H-bond accepting and donating nature of DTBA and DMF, respectively. The inclination is more towards -X\u22efH- for (I)The qu\u00adanti\u00adfication of the corresponding close contacts on the Hirshfeld surface through fingerprint plot analysis for overall (I)NCIPLOT 2 and \u03c0(C2\u2013C7)\u2013quasi-\u03c0(O2\u2013C1\u2013O1\u2013H1O\u22efO5\u2013C15\u2013H15) inter\u00adactions as detected in the Hirshfeld surface analysis by calculating the electron density derivatives through wavefunction approach. The visualization of the resulting gradient isosurface supported the existence of the \u03c0\u2013quasi-\u03c0 contacts based on the corresponding large green domain sandwiched between the aromatic and quasi-aromatic rings. The overall density is in the range of \u22120.05 < sign(\u03bb2)\u03c1 < 0.03 a.u. indicating a weak but attractive inter\u00adaction  hydrogen bond, leading to the eight-membered homosynthon as well as the seven-membered heterosynthon formed between hy\u00addroxy-O1\u2014H1O\u22efO5(carbon\u00adyl) and DMF-C15\u2014H15\u22efO2(carbon\u00adyl) exhibit the greatest inter\u00adaction energies (Eint) of \u221269.8 and \u221258.9\u2005kJ\u2005mol\u22121, respectively. These are relatively stronger than the other supplementary contacts in (I)viz. electrostatic (Eele), polarization (Epol), dispersion (Edis), exchange-repulsion (Erep) together with the total energy are collated in Table\u00a04The strength of each close contact between all pairwise mol\u00adecules in (I)Crystal Explorer 17, the Eint for the pairs of \u03c0\u22efquasi-\u03c0 inter\u00adactions were modelled in Gaussian16 \u22efquasi-\u03c0(\u22efO4\u2013C14\u2013O3\u2013H3O)2 or \u03c0(C2\u2013C7)\u22efquasi-\u03c0(O2\u2013C1\u2013O1\u2013H1O\u22efO5\u2013C15\u2013H15) inter\u00adactions, i.e. \u221259.3 and \u221259.2\u2005kJ\u2005mol\u22121, respectively.Complementing the calculations with Eele topological framework as shown in Fig.\u00a08a). On the other hand, the dispersion force sustained by the specified \u03c0\u2013\u03c0 inter\u00adactions results in a boat-shape topology, Fig.\u00a08b). The combination of the electrostatic and dispersion forces supersedes the strong inter\u00adaction energy from O\u2014H\u22efO contacts and lead to a refined overall energy framework with razor-blade-like topology, Fig.\u00a08c).The crystal of (I)et al., 2006et al., 2013i.e. occupied unit-cell volume = 220.8\u2005\u00c53 = 25.4% for (I)3 and 47.5% for (II).The crystal structure of DTBA\u00b72DMF (II) is also known, being reported four times In term of contact distribution on the Hirshfeld surface for the corresponding individual DTBA mol\u00adecules and overall (I)Chemical Context, DTBA is usually generated during co-crystallization experiments with 2-mercapto\u00adbenzoic acid (2-MBA), implying oxidation of the latter. In addition to oxidation of 2-MBA, other crystallization outcomes have been observed during recent experiments suggesting chemical reactions are occurring. A less common outcome of crystallization experiments with 2-MBA was the sulfur extrusion product, 2,2\u2032-thiodi\u00adbenzoic acid methyl\u00adene]cyclo\u00adhexane-1,4-di\u00adamine, for n = 2, 3 and 4  was co-crystallized with 2-MBA, a salt of composition [DTBA_2H]\u00b7DMF\u00b7H2O was isolated  is 2-(4-ammonio\u00adcyclo\u00adhex\u00adyl)-3-(pyridin-2-yl)imidazopyridin-2-ium di-cation, isolated from the co-crystallization of 2-MBA with the n = 2 isomer of (III) C6H10N(+)H3][4-DTBA_2H]\u00b7DMSO\u00b7H2O was the crystallization product : 3072 \u03bd(C\u2014H), 1680 \u03bd(C=O), 1464 \u03bd(C=C), 1410 \u03b4(C\u2014H), 722 \u03bd(C\u2014S).The DMF monosolvate of DTBA, (I)Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from a difference-Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020008257/hb7925sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008257/hb7925Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008257/hb7925Isup3.cmlSupporting information file. DOI: 2011285CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Log10 Kw>c, values, of the complementary amino acid pairs are strongly correlated to the central (2nd) purine base of the mRNA codon and the complementary pyrimidine base of the tRNA anticodon. Clustering of amino acids is temperature independent with regard to the direction of translation (3\u2032\u202f\u2192\u202f5\u2032 or 5\u2032\u202f\u2192\u202f3\u2032). The Log10 Kw>c discriminate between artificial Hecht \u03b1- and \u03b2-protein datasets at 25\u00a0\u00b0C and 100\u00a0\u00b0C. Interpretation of this data may be found in the research article entitled \u201cDetermining amino acid scores of the genetic code table: complementarity, structure, function and evolution\u201d .We present the data concerning the clustering of sense and antisense amino acid pairs into polar, nonpolar and neutral groups, as measured using hydrophobicity parameter\u2014logarithmic equilibrium constants (Log Specifications table\u202210 Kw>c) discriminates between artificial \u03b1- and \u03b2-protein datasets at 25\u00a0\u00b0C and 100\u00a0\u00b0C.The data are useful since it is shown that the nucleobase coding of amino acid hydrophobicity, specified by the 2nd codon base, is temperature independent at 25\u00a0\u00b0C and 100\u00a0\u00b0C. The hydrophobicity parameter\u2014logarithmic equilibrium constant  nucleobases.\u2022The data presented can be used for theoretical analyses of proteins, experiments with sense and antisense peptide binding, and research of biological systems at different temperature conditions.110 Kw>c10 Kw>c are logarithmic equilibrium constants for the transfer of amino acid side-chains from neutral solution to cyclohexane at 25\u00a0\u00b0C and 100\u00a0\u00b0C The data presented here describe the analysis of temperature dependence of amino acid hydrophobicity parameter\u2014Log10 Kw>c, in a temperature independent manner.10 Kw>c values of the complementary, i.e. sense and antisense, amino acid pairs depend strongly on the central (2nd) purine base of the mRNA codon and the complementary pyrimidine of the tRNA anticodon. All calculated correlations are strong (r\u00a0\u2265\u00a00.85). With respect to the Log10 Kw>c measurements observed, temperatures of 25\u00a0\u00b0C and 100\u00a0\u00b0C do not affect the result  specify polar-nonpolar and neutral-neutral clusters for all possible complementary codon pairs irrespective of temperature value and direction of sequence translation.In 10 Kw>c) accurately predict the \u03b1- and \u03b2-artificial protein class at 25\u00a0\u00b0C and 100\u00a0\u00b0C  and Phase 2 (secondary) amino acids are clearly separated based on temperature independence of LogPART decision list (25\u00a0\u00b0C)2 AND Log10 Kw>c at 25\u00a0\u00b0C <= 2.64 AND Mean Buried Area > 113.9 \u00c52IF Mean Buried Area > 97.8 \u00c5THEN aa Prebiotic Phase 2 1: L,I,V,S,P,T,A,N,D,E,G)ELSE aa Prebiotic Phase 1 (11/\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014PART decision list (100\u00a0\u00b0C)2 AND Log10 Kw>c at 100\u00a0\u00b0C <= 2.60 AND Mean Buried Area > 113.9 \u00c52IF Mean Buried Area > 97.8 \u00c5THEN aa Prebiotic Phase 2 1: L,I,V,S,P,T,A,N,D,E,G)ELSE aa Prebiotic Phase 1 \u202f=\u202f+1,\u2022polar or hydrophilic amino acid (2nd A codon score)\u202f=\u202f-1,\u2022neutral or intermediate amino acid (2nd C or G codon score)\u202f=\u202f0.The agglomerative hierarchical clustering (HAC) method in High agglomerative coefficients of 0.96 were observed for 25\u00a0\u00b0C and 100\u00a0\u00b0C measurements.2.2k\u202f=\u202f3 clusters, Manhattan metric and standardized variables). The first variable involved the amino acid logarithmic equilibrium constants (Log10 Kw>c), and the second variable was amino acid codon scoring according to Davis Section 2.1.). The values of average silhouette widths for 25\u00a0\u00b0C (0.67) and 100\u00a0\u00b0C (0.65) confirm the validity of the model Two-variable fuzzy partitioning was produced using S-Plus 2000 software (2.310 Kw>c) for transfer of amino acid side-chains from neutral solution to cyclohexane at 25\u00a0\u00b0C and at 100\u00a0\u00b0C. The correlations are presented in https://folk.uio.no/ohammer/past/): x\u202f=\u202ffree energy ligandaa, and y\u202f=\u202f|ligandaa\u202f\u2212\u202freceptoraa| free energy absolute difference (aa\u202f=\u202famino acid).Correlations of complementary pairs of polar-nonpolar residues and neutral-neutral residues in a 3\u2032\u202f\u2192\u202f5\u2032 and 5\u2032\u202f\u2192\u202f3\u2032 translation directions, with respect to the logarithmic equilibrium constants  Primary amino acid sequences of 15 artificial Hecht \u03b1- and 17 \u03b2-protein folds were converted into a numerical series by assigning the Log2.610 Kw>c values, and Mean Buried Area parameter https://www.cs.waikato.ac.nz/ml/weka/) The prediction of Phase 1 (primary) and Phase 2 (secondary) amino acids based on temperature independence of Log"}
{"text": "This structure features C\u2014H\u22efO hydrogen bonds (both intra- and inter\u00admolecular) and inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions.The synthesis and crystal structure of a diisopropyl-substituted  13H21NO2S, is reported here along with its crystal structure. This compound crystallizes with two mol\u00adecules in the asymmetric unit. The sulfonamide functional group of this structure features S=O bond lengths ranging from 1.433\u2005(3) to 1.439\u2005(3)\u2005\u00c5, S\u2014C bond lengths of 1.777\u2005(3) and 1.773\u2005(4)\u2005\u00c5, and S\u2014N bond lengths of 1.622\u2005(3) and 1.624\u2005(3)\u2005\u00c5. When viewing the mol\u00adecules down the S\u2014N bond, the isopropyl groups are gauche to the aromatic ring. On each mol\u00adecule, two methyl hydrogen atoms of one isopropyl group are engaged in intra\u00admolecular C\u2014H\u22efO hydrogen bonds with a nearby sulfonamide oxygen atom. Inter\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions link mol\u00adecules of the title compound in the solid state.The synthesis of the title compound, C We attribute this relatively small torsion angle to the presence of intra\u00admolecular C-H\u22efO inter\u00adactions, which are described in more detail below. The torsion angles (O2\u2014S1\u2014N1\u2014C11 and O2A\u2014S1A\u2014N1A\u2014C11A) between the methine carbon atom of the other isopropyl group and the other sulfonamide oxygen are 46.7\u2005(3) and 46.8\u2005(3)\u00b0, respectively. Both sulfur atoms adopt a slightly distorted tetra\u00adhedral geometry with \u03c44 descriptors for fourfold coordination of 0.94 for both S1 and S1A , we describe them here as potential C\u2014H\u22efO hydrogen bonds. Specifically, O1 inter\u00adacts with C9(H9A) and C10(H10B), while the equivalent atom O1a inter\u00adacts with C9A(H9AC) and C10A(H10F). These inter\u00adactions have D\u22efA distances ranging from 3.039\u2005(5) to 3.157\u2005(5)\u2005\u00c5 and D\u2014H\u22efA angles ranging from 117 to 121\u00b0  x, \u22121\u00a0+\u00a0y, z] with a D\u22efA distance of 3.465\u2005(4)\u2005\u00c5 and a D\u2014H\u22efA angle of 150.8\u00b0  to a stirring mixture of diiso\u00adpropyl\u00adamine , pyridine  and 10\u2005mL of degassed di\u00adchloro\u00admethane under a nitro\u00adgen atmosphere. The reaction mixture was stirred at room temperature for 24\u2005h under a nitro\u00adgen atmosphere. After acidification with 5 M HCl and dilution with 15\u2005mL of di\u00adchloro\u00admethane, the organic layer was washed with water and brine. The aqueous layers were back extracted with 10\u2005mL of di\u00adchloro\u00admethane. The combined organic layers were then dried over anhydrous sodium sulfate and evaporated to dryness. The resulting solid was dissolved in hot ethanol and filtered. The filtrate was placed in a freezer for two days and the product was isolated via vacuum filtration to give colorless crystals .The title compound was prepared by the dropwise addition of Uiso(H) = 1.2Ueq(C) for methine groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020007185/pk2628sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020007185/pk2628Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007185/pk2628Isup3.cmlSupporting information file. DOI: 2006237CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 4-iodo\u00adbenzene ring is inclined to the phenol ring by 39.1\u2005(2)\u00b0. The configuration about the C=N bonds is E. The crystal structure features C\u2014H\u22efO hydrogen-bonding inter\u00adactions.In the title Schiff base compound, C 13H9IN2O3, was synthesized by a condensation reaction between 2-hy\u00addroxy-5-nitro\u00adbenzaldehyde and 4-iodo\u00adaniline, and crystallizes in the ortho\u00adrhom\u00adbic space group Pna21. The 4-iodo\u00adbenzene ring is inclined to the phenol ring by a dihedral angle of 39.1\u2005(2)\u00b0. The configuration about the C=N double bond is E. The crystal structure features C\u2014H\u22efO hydrogen-bonding inter\u00adactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the packing arrangement are O\u22efH/H\u22efO (26.9%) and H\u22efH (22.0%) inter\u00adactions.The title compound, C The imine group displays a C8\u2014C7\u2014N1\u2014C4 torsion angle of 174.5\u2005(6)\u00b0. The 4-iodo\u00adbenzene ring (C1\u2013C6) is inclined by a dihedral angle of 39.1\u2005(2)\u00b0 to the phenol ring (C8\u2013C13), which renders the mol\u00adecule non-planar. The configuration of the C7=N1 bond of this Schiff base is E, and the intra\u00admolecular O1\u2014H1\u22efN1 hydrogen bond forms an S(6) ring motif if Fig.\u00a01. The 4-ni  hydrogen bonds between screw-related mol\u00adecules, which form helical chains propagating along the crystallographic screw axis parallel to c  x\u00a0+\u00a0y, \u22121\u00a0+\u00a0z)], which makes a zigzag tape motif  c Fig.\u00a02. The shoif Fig.\u00a03. There aCrystal Explorer 17.5  or longer than the van der Waals radii sum, respectively rm Fig.\u00a04, white set al., 2016E)-2-{[(4-iodo\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-phenol fragment. Of these 26, the most similar to (I)p-iodo-N-(p-cyano\u00adbenzyl\u00adidene)aniline -5-(di\u00adethyl\u00adamino)-2-[(4-iodo\u00adphenyl\u00adimino)\u00admeth\u00adyl]phenol -4-iodo\u00adbenzene; imino]\u00admeth\u00adyl}-6-meth\u00adoxy\u00adphenol -4-iodo\u00adaniline  ring motif.A search of the Cambridge Structural Database  and 4-iodo\u00adaniline  in ethanol (15\u2005ml). After the mixture had refluxed for about 15\u2005h, the orange product was washed with ether and dried at room temperature . Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020008191/pk2635sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008191/pk2635Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008191/pk2635Isup3.cmlSupporting information file. DOI: 1922980CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound, containing a tetra-substituted pyrrolidine ring, has an N-bound  4-nitro\u00adphen\u00adyl)ethyl\u00adcarboxyl\u00adate group with an adjacent C-bound 4-meth\u00adoxy\u00adphenyl  and then two acet\u00adyloxy subtituents in equatorial and axial positions, respectively. The five-membered ring is twisted about the bond bearing the acet\u00adyloxy subtituents. 23H24N2O9, is a tetra-substituted pyrrolidine derivative with a twisted conformation, with the twist evident in the C\u2014C bond bearing the adjacent acet\u00adyloxy substituents. These are flanked on one side by a C-bound 4-meth\u00adoxy\u00adphen\u00adyl group and on the other by a methyl\u00adene group. The almost sp2-N atom [sum of angles = 357\u00b0] bears a 4-nitro\u00adbenzyl\u00adoxycarbonyl substituent. In the crystal, ring-methyl\u00adene-C\u2014H\u22efO(acet\u00adyloxy-carbon\u00adyl) and methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions lead to supra\u00admolecular layers lying parallel to (The title compound, C The conformation of the five-membered ring is twisted about the C2\u2014C3 bond with the C1\u2014C2\u2014C3\u2014C4 torsion angle being 39.70\u2005(16)\u00b0, consistent with a (+)syn-clinal configuration. The sum of the angles about the N1 atom is 356.7\u00b0, indicating an approximate sp2 centre. The N1-bound group occupies an equatorial position with those at the C1\u2013C3 centres being bis\u00adectional, equatorial and axial, respectively \u00b0.The mol\u00adecular structure of (I)With respect to the least-squares plane through the pyrrolidine ring, the nitro\u00adbenzene and meth\u00adoxy\u00adbenzene rings are splayed, as seen in the dihedral angles of 58.58\u2005(8) and 77.65\u2005(6)\u00b0, respectively; the dihedral angle between the benzene rings is 50.56\u2005(5)\u00b0. There is a twist in the nitro\u00adbenzene ring as seen in the value of the C11\u2014C10\u2014N2\u2014O4 torsion angle of 17.7\u2005(3)\u00b0. By contrast, the meth\u00adoxy group is co-planar with the ring to which it is connected, as shown by the C15\u2014C16\u2014O5\u2014C19 torsion angle of 176.2\u2005(2)\u00b0.b-axis direction, being propagated by 21 symmetry. The other inter\u00adactions falling within the distance criteria of PLATON . A view of the unit-cell contents is shown in Fig.\u00a02b), highlighting the stacking of layers, without directional inter\u00adactions between them.The only directional non-covalent inter\u00adactions of note in the crystal of (I)Supra\u00admolecular features were also evaluated by calculating non-covalent inter\u00adaction plots  with the green isosurface between the inter\u00adacting atoms and the distinctive blue feature in the reduced density gradient (RDG) versus sign(\u03bb2)\u03c1(r) plot in the lower view, i.e. indicating the density value is less than 0.0 a.u., suggest these inter\u00adactions are weakly attractive. The same is true for the ring-methyl\u00adene-C4\u2014H\u22efO7(acet\u00adyloxy-carbon\u00adyl) inter\u00adactions that lead to the helical chain, Fig.\u00a03b).The aforementioned weak C\u2014H\u22efO contacts identified in dnorm-surface plots, electrostatic potential  and two-dimensional fingerprint plots following literature procedures B as well as the O5 and O7 atoms  and O2\u22efO5 short contacts, being \u223c0.02\u2005\u00c5 shorter than their respective sums of the van der Waals radii, Table\u00a02The Hirshfeld surface analysis of (I)B), benzyl (C15 and H9), methyl (C21) and nitro (O4) atoms correspond to long-range intra-layer methyl\u00adene-C6\u2014H6B\u22efC15(benz\u00adyl), benzyl-C9\u2014H9\u22efC21(meth\u00adyl) inter\u00adactions and inter-layer O4\u22efO4 short contacts, Table\u00a02In the views of Fig.\u00a05a), the two-dimensional fingerprint plot for the Hirshfeld surface of (I)de and di diagonal axes, and those delineated into H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH, O\u22efO and O\u22efC/C\u22efO contacts are illustrated in Fig.\u00a07b)\u2013(f), respectively. The percentage contributions from different inter\u00adatomic contacts are summarized in Table\u00a03de = di \u223c2.4\u2005\u00c5, Fig.\u00a07b), corresponding to the H17\u22efH23B inter-layer contact listed in Table\u00a02de + di \u223c2.5\u2005\u00c5 in Fig.\u00a07c). The H\u22efC/C\u22efH contacts that match the long-range C\u2014H\u22efC inter\u00adactions discussed above are shown as a pairs of forceps-like tips at de + di \u223c2.7\u2005\u00c5 in the fingerprint plot delineated into H\u22efC/C\u22efH contacts, Fig.\u00a07d). Although both O\u22efO and O\u22efC/C\u22efO contacts appear at de + di \u223c3.0\u2005\u00c5 in the respective fingerprint plots, Fig.\u00a07e) and (f), their contributions to the overall Hirshfeld surface are only 2.1 and 1.2%, respectively. The other inter\u00adatomic contacts have a negligible effect on the mol\u00adecular packing as their accumulated contribution is about 2.2%.As illustrated in Fig.\u00a07Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies as per the literature  basis set with the B3LYP function. The individual energy components as well as the total inter\u00adaction energies are collated in Table\u00a04Hirshfeld surface analysis as well as two additional C\u2014H\u22efO inter\u00adactions, i.e. methyl\u00adene-C4\u2014H4A\u22efO4(nitro) and methyl-C21\u2014H21C\u22efO4(nitro) with H\u22efO separations of 2.63 and 2.77\u2005\u00c5, respectively.The pairwise inter\u00adaction energies between the mol\u00adecules in the crystal of (I)Edis terms associated with the H\u22efH contacts as well as the long-range C\u2014H\u22efO inter\u00adactions (\u221214.4\u2005kJ\u2005mol\u22121). For the former, the maximum energy is not found for the shortest H17\u22efH23B contact (\u22127.1\u2005kJ\u2005mol\u22121), Table\u00a02b), but rather for a pair of benzene-H\u22efH(meth\u00adyl) inter\u00adactions occurring in close proximity in a hydrogen-rich region but at longer separations (\u221234.2\u2005kJ\u2005mol\u22121). For the inter-layer O4\u22efO4 contact mentioned above, there are almost equal contributions from Eele and Edis, Table\u00a04\u22121. The magnitudes of inter\u00admolecular energies are represented graphically in Fig.\u00a08Edis in the mol\u00adecular packing.The stabilization energies in the inter-layer region are also dominated by the et al., 2016et al., 2004There are relatively few related structures having a similar substitution pattern to the tetra-substituted pyrrolidine ring of (I)S,3S,4R)-3,4-dihy\u00addroxy-2-(4-meth\u00adoxy\u00adphen\u00adyl)pyrrolidine-1-carboxyl\u00adate  in CH2Cl2 (15\u2005ml) were added pyridine , acetic anhydride  and N,N-dimethyl-4-amino\u00adpyridine . The solution was stirred for 2\u2005h at room temperature, concentrated in a rota-evaporator and the residue dissolved in EtOAc (10\u2005ml). The resulting solution was washed with a HCl 5% solution (3 \u00d7 5\u2005ml) and with saturated solutions of NaHCO3 (2 \u00d7 5\u2005ml) and of NaCl (5\u2005ml). The phases were separated and the organic phase was dried with anhydrous Na2SO4, filtered and concentrated in vacuo.To a solution of 4-nitro\u00adbenzyl (2n-hexane elution gradient (1:3 and 1:2). Yield: 716\u2005mg (98%). Colourless irregular crystals for the X-ray analysis were obtained by the slow evaporation of its n-hexane solution. M.p. 409.5\u2013410.5\u2005K. The 1H and 13C{1H} NMR reflect the presence of two conformational rotamers in solution. 1H NMR : \u03b4 = 7.75 ; 7.65 ; 7.18 ; 6.99 ; 6.76 ; 6.72 ; 6.65 ; 6.37 ; 5.42 ; 5.33 ; 5.00 ; 4.92 ; 4.74 ; 4.44 ; 3.89 ; 3.72 ; 3.29 ; 3.35\u20133.23 ; 1.61\u20131.60 . 1H NMR : \u03b4 = 8.23 ; 8.00 ; 7.53 ; 7.16 ; 6.96 ; 6.88 ; 5.45\u20135.32 ; 5.31\u20135.18 ; 5.01\u20134.87 ; 4.13 ; 4.06 ; 3.85\u20133.67 ; 2.12-2.07 . 13C{1H} NMR : \u03b4 = 169.9; 169.8; 159.4; 159.2; 154.2; 154.1; 147.6; 147.2; 143.6; 143.4; 130.6; 129.4; 128.1; 127.5; 126.8; 126.7; 123.7; 123.4; 114.2; 78.2; 69.2; 68.7; 65.7; 65.5; 64.7; 64.1; 55.3; 55.2; 49.0; 48.4; 20.8; 20.7; 20.6.The residue was purified by flash column chromatography in silica gel, using an EtOAc/Uiso(H) set to 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020007914/hb7923sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020007914/hb7923Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007914/hb7923Isup3.cmlSupporting information file. DOI: 2009242CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In a palliative situation like metastatic spinal cord compression (MSCC), overall treatment time of radiotherapy should be as short as possible. This study compared 5\u2009\u00d7\u20095\u00a0Gy in 1\u00a0week to 10\u2009\u00d7\u20093\u00a0Gy in 2\u00a0weeks in a prospective cohort.Forty patients receiving 5\u2009\u00d7\u20095\u00a0Gy in a phase II trial were matched 1:2 to 213 patients receiving 10\u2009\u00d7\u20093\u00a0Gy in two previous prospective studies for tumor type, ambulatory status, time developing motor deficits, interval between tumor diagnosis and MSCC and visceral metastases. These factors were consistent in all three patients (triple) used for each 1:2 matching. Groups were compared for local progression-free survival (LPFS), motor function, ambulatory status, and overall survival (OS).p\u2009=\u20090.36), 6-month OS-rates 43% and 35% (p\u2009=\u20090.74). Improvement of motor function was achieved in 59% and 34% of patients (p\u2009=\u20090.028); overall response rates (improvement or no further progression of motor deficits) were 94% and 89% (p\u2009=\u20090.71). Post-treatment ambulatory rates were 81% after 5\u2009\u00d7\u20095\u00a0Gy and 85% after 10\u2009\u00d7\u20093\u00a0Gy (p\u2009=\u20090.61). Of non-ambulatory patients, 50% (6/12) and 46% (11/24) regained the ability to walk (p\u2009=\u20091.00).After matching, 32 triples remained for analyses . Six-month LPFS-rates were 94% after 5\u2009\u00d7\u20095\u00a0Gy and 87% after 10\u2009\u00d7\u20093\u00a0Gy (5\u2009\u00d7\u20095\u00a0Gy in 1\u00a0week appeared similarly effective as 10\u2009\u00d7\u20093\u00a0Gy in 2\u00a0weeks. These results may not be applicable to long-term survivors and should be confirmed in a randomized trial directly comparing 5\u2009\u00d7\u20095\u00a0Gy and 10\u2009\u00d7\u20093\u00a0Gy.Trial registration clinicaltrials.gov NCT03070431. Registered 27 February 2017. Metastatic spinal cord compression (MSCC) occurs in 5\u201310% of patients with malignant diseases . Many ofPatients in the phase II trial  received precision radiotherapy with 5\u2009\u00d7\u20095\u00a0Gy in 1\u00a0week between 02/2017 and 03/2018 . ImproveSince the EQD2 of 5\u2009\u00d7\u20095\u00a0Gy (31.3\u00a0Gy) for tumor cell kill  is similar to 10\u2009\u00d7\u20093\u00a0Gy (32.5\u00a0Gy), it is assumed that both regimens are similarly effective . PatientThe 40 patients of the PRE-MODE trial were matched 1:2 to the 213 patients receiving 10\u2009\u00d7\u20093\u00a0Gy in a previous trial , 10. MatComparisons for LPFS and OS were performed using Kaplan\u2013Meier method and log-rank test. For the comparison regarding age, the Mann-Whiney U test was used. The comparisons for patient characteristics, improvement of motor function, overall response and ambulatory status were performed with the Fisher\u2019s exact test.z-score was 0.933, and distribution was considered approximately normal.After 1:2 matching, 32 triples remained for analyses, corresponding to a total of 96 patients. The distribution of the patient characteristics was not significantly different (Table p\u2009=\u20090.36), and 6-month OS-rates 43% and 35% . Improvement of motor function was achieved in 59% (19/32) and 34% (22/64) of patients (p\u2009=\u20090.028). Overall response rates were 94% (30/32) and 89% (57/64) (p\u2009=\u20090.71). Deterioration of motor deficits occurred in 6% (2/32) and 11% (7/64) of patients (p\u2009=\u20090.71). Post-treatment ambulatory rates were 81% after 5\u2009\u00d7\u20095\u00a0Gy and 85% after 10\u2009\u00d7\u20093\u00a0Gy (p\u2009=\u20090.61). Of non-ambulatory patients, 50% (6/12) after 5\u2009\u00d7\u20095\u00a0Gy and 46% (11/24) after 10\u2009\u00d7\u20093\u00a0Gy, respectively, regained walking ability (p\u2009=\u20091.00). Of ambulatory patients, 100% (20/20) and 93% (37/40), respectively, remained ambulatory (p\u2009=\u20090.54).Six-month LPFS-rates were 94% after 5\u2009\u00d7\u20095\u00a0Gy and 87% after 10\u2009\u00d7\u20093\u00a0Gy  when compared to a historical control group receiving 5\u2009\u00d7\u20094\u00a0Gy [Important endpoints of radiotherapy for MSCC include functional outcome and local control \u20133. In se5\u2009\u00d7\u20094\u00a0Gy . EQD2 fo5\u2009\u00d7\u20094\u00a0Gy . 5\u2009\u00d7\u20095\u00a0GThis study compared 5\u2009\u00d7\u20095\u00a0Gy to 10\u2009\u00d7\u20093\u00a0Gy using data of three prospective studies. Forty patients receiving 5\u2009\u00d7\u20095\u00a0Gy were matched 1:2 to 213 patients receiving 10\u2009\u00d7\u20093\u00a0Gy. Matching criteria were selected according to previous studies , 12\u201314. 5\u2009\u00d7\u20095\u00a0Gy resulted in a significantly higher rate of improvement of motor function than 10\u2009\u00d7\u20093\u00a0Gy. For the other investigated endpoints including the main objective LPFS, no significant differences were found. Thus, 5\u2009\u00d7\u20095\u00a0Gy appeared similarly effective as 10\u2009\u00d7\u20093\u00a0Gy. When interpreting these results, the limitations of the study must be considered including the non-randomized design. To minimize the risk of hidden selection biases, we used only data from prospective studies. Further limitations include the facts that follow-up MRI was not performed at pre-defined time points and that for grading of MSCC radiological criteria were not considered \u201310, 15. 5\u2009\u00d7\u20095\u00a0Gy in 1\u00a0week appeared similarly effective as 10\u2009\u00d7\u20093\u00a0Gy in 2\u00a0weeks for LPFS, functional outcome and OS. These results may not be applicable to long-term survivors and should be confirmed in a randomized trial that directly compares 5\u2009\u00d7\u20095\u00a0Gy and 10\u2009\u00d7\u20093\u00a0Gy."}
{"text": "The aim of the study was to explore genotype distribution thalassemia and G6PD deficiency in Meizhou city, China.G6PD mutations by gene chip analysis. Genotypes and allele frequencies were analyzed.A total of 16\u00a0158 individuals were involved in thalassemia genetic testing. A total of 605 subjects were screened for common Chinese SEA (65.12%), \u2010\u03b13.7 (19.05%), and \u2010\u03b14.2 (8.05%) deletion were the main mutations of \u03b1\u2010thalassemia, while IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) (40.39%), CD41\u201042(\u2010TCTT) (32.72%), \u201028(A\u00a0\u2192\u00a0G) (10.11%), and CD17(A\u00a0\u2192\u00a0T) (9.32%) mutations were the principal mutations of \u03b2\u2010thalassemia in Meizhou. There were significant differences in allele frequencies in some counties. Genetic testing for G6PD deficiency, six mutation sites, and one polymorphism were detected in our study. A total of 198 alleles with the mutation were detected among 805 alleles (24.6%). G6PD Canton (c.1376 G\u00a0\u2192\u00a0T) (45.96%), G6PD Kaiping (c.1388 G\u00a0\u2192\u00a0A) (39.39%), and G6PD Gaohe (c.95 A\u00a0\u2192\u00a0G) (9.09%) account for 94.44% mutations, followed by G6PD Chinese\u20105 (c.1024 C\u00a0\u2192\u00a0T) (4.04%), G6PD Viangchan (c.871G\u00a0\u2192\u00a0A) (1.01%), and G6PD Maewo (c.1360 C\u00a0\u2192\u00a0T) (0.51%). There were some differences of the distribution of G6PD mutations among eight counties in Meizhou.A total of 5463 cases carried thalassemia mutations were identified, including 3585 cases, 1701 cases, and 177 cases with \u03b1\u2010, \u03b2\u2010, and \u03b1\u00a0+\u00a0\u03b2\u2010thalassemia mutations, respectively. \u2010\u2010SEA, \u2010\u03b13.7, and \u2010\u03b14.2 deletion were the main mutations of \u03b1\u2010thalassemia, while IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T), CD41\u201042(\u2010TCTT), \u201028(A\u00a0\u2192\u00a0G), and CD17(A\u00a0\u2192\u00a0T) mutations were the principal mutations of \u03b2\u2010thalassemia in Meizhou. G6PD c.1376 G\u00a0\u2192\u00a0T, c.1388 G\u00a0\u2192\u00a0A, and c.95 A\u00a0\u2192\u00a0G were the main mutations of G6PD deficiency. There were some differences of the distribution of thalassemia and G6PD mutations among eight counties in Meizhou.The \u2010\u2010 As one of the commonest monogenic disorder in the world, thalassemia assumes diversity in clinical phenotypes varying from almost asymptomatic to lethal hemolytic anemia.G6PD gene is located on chromosome Xq28 which consists of 13 exons and 12 introns, encoding 515 amino acids. The deficiency is widely distributed and occurs in about 400\u00a0million people worldwide.Hereditary G6PD deficiency is one of the most common genetic enzyme deficiency diseases in the world. G6PD deficiency is an X\u2010linked incomplete dominant inherited\u00a0disease. The Meizhou is a city located in the northeast of Guangdong Province, and most of the residents living in this area are Hakka peoples. Hakka is an intriguing Han Chinese population that mainly inhabit in southern China who migrated to south originally from northern China.Population screening and genetic counseling are important to prevent the birth of children with thalassemia major. Using genetic analysis for prenatal diagnosis can diagnose thalassemia major fetuses in early pregnancy and terminate pregnancy in time, so as to avoid the birth of thalassemia major patients, which is an effective method to prevent this disease at present. Precise mutation frequencies studies in different populations will help healthcare programs to control thalassemia.22.1A total of 16\u00a0158 individuals who visited Meizhou People's Hospital  from January 2015 to May 2018 were involved in thalassemia genetic testing in this study. From February 2016 to May 2018, 605 subjects were screened for common Chinese G6PD mutations by gene chip analysis. The subjects included patients who went to cardiovascular disease center, prenatal diagnosis center, reproductive medicine center, physical examination center, pediatrics, gynecology, and other professional departments of our hospital, excluding patients with blood diseases. Figure 2.22.2.12 (<2.5%) were considered probable \u03b1\u2010thalassemia carriers, whereas with high HbA2 (>3.5%) were deemed possible \u03b2\u2010thalassemia carriers.Samples were obtained via venipuncture of an antecubital vein, and then, 2\u00a0mL of peripheral blood was collected in EDTA anticoagulant tube. Sysmex XE\u20102100 blood analyzer  was used to determine erythrocyte correlative indices following the standard operating procedures. Hemoglobin electrophoresis analysis was performed by Sebia capillary electrophoresis system  compiling with standard operating procedures. Subjects detected to low mean corpuscular volume (MCV) values (<82\u00a0fL) and (or) lower mean corpuscular hemoglobin (MCH) values (<27\u00a0pg) were thought as suspicious thalassemia carriers. Subjects with low HbA2.2.2SEA, \u2010\u03b13.7, and \u2010\u03b14.2) and non\u2010deletional mutations (Hb Constant Spring (\u03b1CS\u03b1) , Hb Quong Sze (\u03b1QS\u03b1) , and Hb Westmead (\u03b1WS\u03b1) ). Sixteen common non\u2010deletional mutations in \u03b2\u2010globin gene were detected by PCR and flow\u2010through hybridization technology : CD41\u201042(\u2010TCTT), CD43(G\u00a0\u2192\u00a0T), IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T), CD17(A\u00a0\u2192\u00a0T), CD14\u201015(+G), \u201028(A\u00a0\u2192\u00a0G), \u221229(A\u00a0\u2192\u00a0G), CD71\u201072(+A), CD26(G\u00a0\u2192\u00a0A), IVS\u2010I\u20101(G\u00a0\u2192\u00a0T), IVS\u2010I\u20101(G\u00a0\u2192\u00a0A), CD27\u201028(+C), IVS\u2010I\u20105(G\u00a0\u2192\u00a0C), Cap\u00a0+\u00a040\u201043(\u2010AAAC), initiation codon (T\u00a0\u2192\u00a0G), and CD31(\u2010C).Peripheral blood was collected with EDTA anticoagulant tube, in which genomic DNA was extracted from leukocytes. DNA concentration was quantified using NanoDrop 2000\u2122 Spectrophotometer (Thermo Fisher Scientific). Gap\u2010polymerase chain reaction (gap\u2010PCR) and flow\u2010through hybridization technology  were used to detect \u03b1\u2010thalassemia mutations, both deletional mutations (\u2010\u20102.3G6PD Gene Typing Detection Kit (gene chip assay) (Sinochips Bioscience Co.). We detected the six mutation and one polymorphism sites in G6PD gene most commonly seen in the Chinese population by gene chip assay, including G6PD Gaohe , G6PD Viangchan , G6PD Chinese\u20105 , G6PD Maewo , G6PD Canton , G6PD Kaiping , and one polymorphism .Genomic DNA was extracted from EDTA anticoagulant blood of subjects using the QIAamp DNA Blood Mini Kit (Qiagen). Amplification was performed using the 2.4P\u00a0<\u00a0.05 was considered to statistical difference.This study used SPSS statistical software version 20.0  to analyze data, and the results would be displayed with corresponding proportion. Descriptive analysis and Pearson chi\u2010square test were used to compare the frequencies of genotype and allele among different counties in Meizhou region. 3A total of 16\u00a0158 blood samples were obtained and analyzed from eight counties of Meizhou area. A total of 8701 cases with microcytosis (MCV\u00a0<\u00a082\u00a0fL and/or MCH\u00a0<\u00a027\u00a0pg) were found, and corresponding percentages of microcytosis in Xingning, Wuhua, Meixian, Meijiang, Fengshun, Jiaoling, Pingyuan, and Dabu were 56.96% (1792/3146), 56.87% (1750/3077), 51.29% (1407/2743), 55.14% (1025/1859), 48.76% (1023/2098), 48.33% (652/1349), 55.54% (536/966), and 55.98% (515/920), respectively. The corresponding abnormal\u00a0ratio\u00a0of\u00a0hemoglobin in Xingning, Wuhua, Meixian, Meijiang, Fengshun, Jiaoling, Pingyuan, and Dabu were 52.64% (1656/3146), 52.00% (1600/3077), 46.34% (1271/2743), 47.98% (892/1859), 47.47% (996/2098), 44.48% (600/1349), 48.96% (473/966), and 50.98% (469/920), respectively.P\u00a0=\u00a0.043) was lower than other counties in Meizhou area. However, the relative proportions of \u03b1\u2010 and \u03b2\u2010thalassemia did not differ greatly among eight counties. The prevalence of \u03b1\u2010thalassemia in Meijiang  was lower than other counties in Meizhou area. The prevalence of Hb H disease in Wuhua  was higher than other counties in Meizhou area, while in Jiaoling  was lower than other counties.The result of the incidence rate of \u03b1\u2010 and \u03b2\u2010thalassemia of eight counties in Meizhou area is shown in Table P\u00a0=\u00a0.032) and \u2010\u03b13.7 deletion , and higher frequencies in \u03b1WS\u03b1 allele of Xingning , in \u2010\u03b14.2 deletion of Jiaoling , in \u03b1CS\u03b1 allele of Dabu , and in IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) allele of Pingyuan  were showed compared with other counties separately. IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) mutation was found dominance in most of these counties, while Meixian and Fengshun had a higher percentage in CD41\u201042(\u2010TCTT)  allele. The \u03b2\u2010thalassemia mutations in the order of allele frequency between eight regions of Meizhou, the mutations were IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T)\u00a0>\u00a0CD41\u201042(\u2010TCTT)\u00a0>\u00a0\u201028(A\u00a0\u2192\u00a0G)\u00a0>\u00a0CD17(A\u00a0\u2192\u00a0T) in Xingning, Meijiang, Jiaoling and Pingyuan (similar to Jiangxi), IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T)\u00a0>\u00a0CD41\u201042(\u2010TCTT)\u00a0>\u00a0CD17(A\u00a0\u2192\u00a0T)\u00a0>\u00a0\u201028(A\u00a0\u2192\u00a0G) in Wuhua and Dabu (similar to Fujian), CD41\u201042(\u2010TCTT)\u00a0>\u00a0IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T)\u00a0>\u00a0CD17(A\u00a0\u2192\u00a0T)\u00a0>\u00a0\u201028(A\u00a0\u2192\u00a0G) in Meixian and Fengshun.Allele frequencies of \u03b1\u2010 and \u03b2\u2010thalassemia of eight counties in Meizhou area are exhibited in Table 4.2/\u03b1\u03b1, \u03b2N/\u03b2N of Jiaoling , in \u2010\u2010SEA/\u2010\u03b13.7, \u03b2N/\u03b2N  and \u03b1\u03b1/\u03b1\u03b1, \u03b2IVS\u2010II\u2010654/\u03b2N  of Pingyuan, in \u03b1CS\u03b1/\u03b1\u03b1, \u03b2N/\u03b2N of Meixian , and in \u2010\u2010SEA/\u03b1CS\u03b1, \u03b2N/\u03b2N of Dabu  compared with other counties. There are lower frequencies in \u03b1CS\u03b1/\u03b1\u03b1, \u03b2N/\u03b2N of Xingning  and in \u03b1\u03b1/\u03b1\u03b1, \u03b2\u201028/\u03b2N of Dabu  compared with other counties.The result of genotypes of different counties in Meizhou area is shown in Table G6PD mutations and 19 genotypes were detected, including six kinds of heterozygotes, six kinds of hemizygotes, and seven kinds of homozygotes. The result of allele frequencies of G6PD in different counties of Meizhou area is shown in Table G6PD mutations including G6PD Canton (c.1376 G\u00a0\u2192\u00a0T)(45.96%), G6PD Kaiping (c.1388 G\u00a0\u2192\u00a0A)(39.39%), and G6PD Gaohe (c.95 A\u00a0\u2192\u00a0G)(9.09%) account for 94.44% of mutations, followed by G6PD Chinese\u20105 (c.1024 C\u00a0\u2192\u00a0T)(4.04%), G6PD Viangchan (c.871G\u00a0\u2192\u00a0A)(1.01%), and G6PD Maewo (c.1360 C\u00a0\u2192\u00a0T)(0.51%). There were higher frequency in G6PD c.1376 G\u00a0\u2192\u00a0T allele of Wuhua  and lower frequency in G6PD c.1376 G\u00a0\u2192\u00a0T allele of Meijiang  compared with other counties. The mutations were c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.95 A\u00a0\u2192\u00a0G in Xingning and Dabu, c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.95 A\u00a0\u2192\u00a0G in Wuhua and Meixian, c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.1024 C\u00a0\u2192\u00a0T in Meijiang, c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.95 A\u00a0\u2192\u00a0G in Fengshun, c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.1024 C\u00a0\u2192\u00a0T in Jiaoling, and c.1376 G\u00a0\u2192\u00a0T\u00a0>\u00a0c.1388 G\u00a0\u2192\u00a0A\u00a0>\u00a0c.1360 C\u00a0\u2192\u00a0T in Pingyuan. In addition, we detected 55 patients (9.09%) with the polymorphism (c.1311 C\u00a0\u2192\u00a0T).For G6PD deficiency, there were six Among these cases, 130 cases were simultaneously performed on genetic testing for thalassemia and G6PD deficiency, among them, 70 cases with G6PD deficiency mutations, 27 cases carried thalassemia mutations were identified, and 13 cases with both thalassemia and G6PD deficiency mutations\u00a0and\u00a046 cases did not carry thalassemia and G6PD deficiency mutations. Due to the small number of cases, we cannot analyze the relationship of thalassemia and G6PD deficiency. Of course, further studies are required to reveal the relationship, which is one of our next major research goals.4Thalassemia is an inherited autosomal recessive disease that is mainly prevalent in Guangdong, Guangxi, and Hainan provinces. Thalassemia major places a heavy financial burden on some families.In this study, the total incidence of thalassemia in Meizhou region was 33.80%, of \u03b1\u2010thalassemia was 22.17%, of \u03b2\u2010thalassemia was 10.53%, and of \u03b1\u2010compound \u03b2\u2010thalassemia was 1.10%. Compared with previous studies, our research presented relatively higher prevalence of thalassemia because our subjects were hospitalized patients.SEA/\u03b1\u03b1 and 39.4% of \u03b2\u2010thalassemia with the main genotype of CD41\u201042(\u2010TCTT) and IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) (5.8%) ranked the fifth position.4.2, \u2010\u03b13.7 deletion, 3.83% of \u03b2\u2010thalassemia with lead genotype of CD41\u201042(\u2010TCTT) mutation, while the Han people in Hainan Province presented 12.16% of \u03b1\u2010thalassemia with chief genotype of \u2010\u2010SEA, \u2010\u03b13.7 deletion, 6.11% of \u03b2\u2010thalassemia with the main mutation is CD41\u201042(\u2010TCTT).SEA and \u2010\u03b13.7 deletion were the main genotypes with frequencies 46.9% and 36.5%, respectively, while the carrier rate of \u03b2\u2010thalassemia was 2.54% in which CD41\u201042(\u2010TCTT) (36.4%) and IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) (24.8%) were the principal genotypes.SEA deletion (74.85% of mutations), 1.99% of \u03b2\u2010thalassemia in which CD41\u201042(\u2010TCTT) and IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T) played a dominant role with frequencies 41.25% and 27.50%, respectively.SEA deletion was 3.44%, 3.97% of \u03b2\u2010thalassemia with chief genotype of CD41\u201042(\u2010TCTT).SEA/\u03b1\u03b1 was the most common \u03b1\u2010thalassemia genotype, accounted for 62.93% of \u03b1\u2010thalassemia. \u03b1WS\u03b1  accounted for 0.37% (120/32316) of \u03b1\u2010thalassemia and was relatively lower than the proportion of in Guangdong Province reported in the previous study. The main genotype of \u03b2\u2010thalassemia in Meizhou is IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T), whereas the counterpart in Guangdong is CD41\u201042(\u2010TCTT); however, CD41\u201042(\u2010TCTT) showed higher proportion in Fengshun and Meixian.The statistics and analysis of molecular characteristics and morbidity of thalassemia in different regions have increasingly enriched in many studies. For example, frequency of carriers for \u03b1\u2010thalassemia is 15% and \u03b2\u2010thalassemia carriers comprise 4.8% in Guangxi Province, while 46.7% of \u03b1\u2010thalassemia with the main genotype of \u2010\u2010SEA deletion is potentially at risk of begetting infants with HbH disease or the Hb Bart's hydrops fetalis syndrome, depending upon the \u03b1\u2010globin genotype of his/her partner, which would exhibit range from hypochromic anemia to hydrops fetalis. According to previous researches, most of regions indicated a similar feature with higher genotype of \u2010\u2010SEA deletion. Our results are consistent with those reported in most other regions. Nonetheless, the distributions and proportions in different areas regarding \u03b2\u2010thalassemia genotype seem to be subtly difference. Our research may not fully represent the epidemiology of thalassemia in this region related to the randomization and sample capacity of study subjects possibly as for most of our subjects were hospitalized patients.A person who is a carrier of \u2010\u2010G6PD mutations in Hakka population of Guangdong Province studied by Yu et alG6PD gene mutations in Chinese population, which generally accounts for more than 50%. In this study, c.1376 G\u00a0\u2192\u00a0T, c.1388 G\u00a0\u2192\u00a0A, and c.95 A\u00a0\u2192\u00a0G mutations accounted for 94.44% of the total mutation types, and the mutation distribution was consistent with the results in other places.G6PD deficiency gene carrying incidence rate was 5.41% in Guangdong Province.G6PD gene mutations, and next study may reveal the correlation between thalassemia and G6PD deficiency.It is reported that the G6PD enzyme activity in patients with G6PD deficiency compound thalassemia may be higher than that of G6PD deficiency patients, due to an increase in the number of newborn erythrocytes and increase in the activity of G6PD in the chronic hemolysis of the G6PD deficiency compound thalassemia patients.The genotype distribution and frequencies of thalassemia and G6PD deficiency in Meizhou area have regional characteristics, and there are also significant differences in different counties. Local governments can formulate corresponding measures and detection projects to prevent and control thalassemia major and G6PD deficiency according to the genotype distribution and frequencies, effectively saving costs and enhancing social benefits.5SEA, \u2010\u03b13.7, and \u2010\u03b14.2 deletion were the main mutations of \u03b1\u2010thalassemia, while IVS\u2010II\u2010654(C\u00a0\u2192\u00a0T), CD41\u201042(\u2010TCTT), \u201028(A\u00a0\u2192\u00a0G) and CD17(A\u00a0\u2192\u00a0T) mutations were the principal mutations of \u03b2\u2010thalassemia in Meizhou. Genetic testing for G6PD deficiency, c.1376 G\u00a0\u2192\u00a0T, c.1388 G\u00a0\u2192\u00a0A, and c.95 A\u00a0\u2192\u00a0G were the main mutations of G6PD deficiency in this region. In addition, there were some differences of the distribution of thalassemia and G6PD mutations among eight counties in Meizhou.In conclusion, \u2010\u2010"}
{"text": "N atom generating an S(6) ring motif. The 3-chloro\u00adbenzene ring is inclined to the phenol ring by 9.38\u2005(11)\u00b0. The configuration about the C=N bond is E.In the title Schiff base compound, the hy\u00addroxy group forms a intra\u00admolecular hydrogen bond to the imine  15H14ClNO, was synthesized by condensation reaction of 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde and 3-chloro-4-methyl\u00adaniline, and crystallizes in the monoclinic space group P21/c. The 3-chloro\u00adbenzene ring is inclined to the phenol ring by 9.38\u2005(11)\u00b0. The configuration about the C=N bond is E and an intra\u00admolecular O\u2014H\u22efN hydrogen bond forms an S(6) ring motif. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the packing arrangement are from H\u22efH (43.8%) and C\u22efH/H\u22efC (26.7%) inter\u00adactions. The density functional theory (DFT) optimized structure at the B3LYP/ 6\u2013311\u2005G level is compared with the experimentally determined mol\u00adecular structure and the HOMO\u2013LUMO energy gap is provided.The title compound, C RCH=N\u2013R\u2032) and are prepared by condensation reactions between amines and active carbonyl compounds. Schiff bases are employed as catalyst carriers . The imine group, which displays a C9\u2014C8\u2014 N1\u2014C5 torsion angle of \u2212177.49\u2005(18)\u00b0, contributes to the general non-planarity of the mol\u00adecule. The chloro\u00adbenzene ring (C2\u2013C7) is inclined by 9.38\u2005(11)\u00b0 to the phenol ring (C9\u2013C14). The configuration of the C7=N1 bond of this Schiff base is E, and the intra\u00admolecular O1\u2014H1\u22efN1 hydrogen bond forms an S(6) ring motif A\u22efN1 [H1A\u22efN1 = 2.86\u2005\u00c5] inter\u00adactions, forming sheets propagating along the a-axis direction . Weak C\u2014H\u22ef\u03c0 inter\u00adactions [C1\u2014H1C\u22efCg1 = 2.92\u2005\u00c5] are observed (Table\u00a01b). Notably, weak \u03c0\u2013\u03c0 stacking inter\u00adactions between chloro\u00adbenzene rings  along the a axis lead to the formation of a three-dimensional network.In the crystal packing of (I)on Fig.\u00a02a. Weak d Table\u00a01b. NotabCrystal Explorer 17.5  and shape index (e) surface mappings are shown in Fig.\u00a03dnorm surface represent O1\u22efCl1 inter\u00adactions  and C1\u2014H1C\u22efCg1 inter\u00adactions . Some additional inter\u00adactions indicated by light-red spots are corresponding to contacts around phenolic and chloro\u00adbenzene rings . The red and blue triangles are absent on the shape-index surface, which indicates there are no strong \u03c0\u2013\u03c0 stacking inter\u00adactions in the crystal structure.The inter\u00admolecular inter\u00adactions were investigated qu\u00adanti\u00adtatively and visualized with ns Fig.\u00a03b and C1ns Fig.\u00a03c. Some gs Fig.\u00a03d. The ra\u2013f) indicates that the H\u22efH (43.8%) inter\u00adactions are the major factor in the crystal packing with C\u22efH/H\u22efC (26.7%) inter\u00adactions making the next highest contribution. The percentage contributions of other weak inter\u00adactions are: Cl\u22efH/H\u22efCl (12.4%), O\u22efH/H\u22efO (6.6%) and N\u22efH/H\u22efN (3.8%).Analysis of the two-dimensional fingerprint plots Fig.\u00a04a\u2013f indivia density functional theory (DFT) using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations , hardness (\u03b7), electrophilicity (\u03c9), softness (\u03c3) and fraction of electron transferred (\u0394N). These data are recorded in Table\u00a03\u03c3 is for the evaluation of both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig.\u00a05E = ELUMO\u00a0\u2212\u00a0EHOMO] of the mol\u00adecule is 4.0023\u2005eV, the frontier mol\u00adecular orbital energies EHOMO and ELUMO being \u22125.9865\u2005eV and \u22121.9842\u2005eV, respectively. The dipole moment of (I)The optimized structure in the gas phase of compound (I)et al., 2016E)-4-meth\u00adoxy-2-{[(4-methyl\u00adphen\u00adyl)imino]\u00admeth\u00adyl}phenol -(5-chloro-2-methyl\u00adphen\u00adyl)imino\u00admeth\u00adyl]-4-methyl\u00adphenol -[(3-chloro-4-meth\u00adyl\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol  ring. In 2-{(E)-[(3-iodo-4-methyl\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol -2,4,6-tri\u00admethyl\u00adaniline  in ethanol (15\u2005ml) and 3-chloro-4-methyl\u00adaniline  in ethanol (15\u2005ml). The reaction mixture was stirred for 5\u2005h under reflux. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .H atom was located in a difference-Fourier map and its positional parameters were refined freely with Uiso(H) = 1.5Ueq(O). Other H atoms were fixed geometrically and treated as riding with C\u2014H = 0.96\u2005\u00c5 (meth\u00adyl) or 0.93\u2005\u00c5 (aromatic), and Uiso(H) = 1.2Ueq(C) for aromatic H atoms or Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020009421/vm2236sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009421/vm2236Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009421/vm2236Isup3.cmlSupporting information file. DOI: 2015356CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Ohy\u00addroxy\u2014H\u22efOwater, Ohy\u00addroxy\u2014H\u22efOhy\u00addroxy, Owater\u2014H\u22efOhy\u00addroxy, and Owater\u2014H\u22efNpyridine, result in the formation of a ribbon structure running along .In the title pyridine derivative, C In this paper, we report the crystal structure of 2,6-bis\u00ad(3-methyl\u00adbutyn-3-ol)pyridine monohydrate, 1\u00b7H2O.Pyridine derivatives with propargyl alcohol groups as substituents in the 2,6-positions are inter\u00adesting compounds that have been used as synthons of many reactive compounds  and C\u2261C\u2013C(OH) (C6\u2261C7\u2014C8 and C11\u2261C12\u2014C13) bond angles are 176.0\u2005(2), 176.4\u2005(2), 174.6\u2005(2) and 178.5\u2005(2)\u00b0, respectively. C6\u2261C7\u2014C8 is slightly distorted from a linear structure compared to the other bonds. The two OH groups are oriented in directions opposite to each other with respect to the plane of the pyridine ring, and the pyridine ring makes dihedral angles of 50.50\u2005(17) and 57.58\u2005(15)\u00b0, respectively, with the C7/C8/O1 and C12/C13/O2 planes.The mol\u00adecular structure of the title compound is depicted in Fig.\u00a011\u00b7H2O along the c axis. The water mol\u00adecules present as the crystallization solvent form inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN inter\u00adactions with the hydroxyl groups and the N atoms of the pyridine unit of mol\u00adecule 1  \u2212x\u00a0+\u00a0y\u00a0+\u00a01, z\u00a0+\u00a01  have been reported 2  as a catalyst in a THF (50\u2005mL)\u2013NEt3 (150\u2005mL) solvent for 19\u2005h at room temperature. The resulting dark-brown solution was quenched with an aqueous NH4Cl solution and the obtained solid was elimin\u00adated by celite filtration. The solution was extracted by AcOEt, and the organic phase was dried over MgSO4. After filtering off the desiccant, the filtrate was concentrated and subjected to silica-gel chromatography (eluent: AcOEt:hexane 3:2). Single crystals suitable for X-ray diffraction studies were obtained from an ethyl acetate solution via slow evaporation in air.2,6-Bis(3-methyl\u00adbutyn-3-ol)pyridine was prepared by using a modified Potts method (Potts Uiso(H) = 1.2Ueq (aromatic-C) or 1.5Ueq (methyl-C).Crystal data, data collection and refinement details are summarized in Table\u00a0210.1107/S2056989020013304/is5553sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020013304/is5553Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020013304/is5553Isup3.cmlSupporting information file. DOI: 2035321, 2035321CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The bridged bimetallic compounds adopt \u039b-shaped configurations, with the octa\u00adhedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these \u039b-shaped compounds are organized through both intra- and inter\u00admolecular hydrogen bonds and inter\u00admolecular \u03c0\u2013\u03c0 stacking. The salt compound [Cu(phen)(H2O)2F]2[HfF6]\u00b7H2O displays an isolated square-pyramidal Cu(phen)(H2O)2F+ complex linked to other cationic complexes and isolated HfF62\u2212 anions through inter\u00admolecular hydrogen-bonding inter\u00adactions.The crystal structures of three bridged bimetallic mol\u00adecular compounds, namely, tri\u00adaqua-2\u03ba Although these compounds crystallize with inversion symmetry, the novel mol\u00adecular building units are potential targets of future studies aimed to perturb their packing arrangement to form NCS structures. The salt compound [Cu(phen)(H2O)2F]2[HfF6]\u00b7H2O provides a point of comparison as an unbridged analogue of [Cu(phen)(H2O)3(HfF6)]\u00b7H2O.Lambda (\u039b)-shaped mol\u00adecules have been demonstrated as efficient building blocks in the synthesis of non-centrosymmetric (NCS) materials 2O)3(TiF6)]\u00b7H2O and crystallizes in the ortho\u00adrhom\u00adbic space group Pbca  to 1.9035\u2005(13)\u2005\u00c5. The \u039b-shape, indicated by the Cu1\u2014F1\u2014Ti1 bond angle of 134.93\u2005(6)\u00b0, is enforced by the two intra\u00admolecular O2\u2014H2B\u22efF5 and O3\u2014H3B\u22efF6 hydrogen bonds (Table\u00a01Compound (I)ca Fig.\u00a01. The strs Table\u00a01.2O)3(ZrF6)]\u00b7H2O and crystallizes in the monoclinic space group P21/n  to 2.0430\u2005(6)\u2005\u00c5. The \u039b-shape, indicated by the Cu1\u2014F1\u2014Zr1 bond angle of 132.59\u2005(3)\u00b0, is enforced by an intra\u00admolecular O2\u2014H2B\u22efF6 hydrogen bond (Table\u00a0262\u2212 group significantly relative to the TiF62\u2212 group in compound (I)Compound (II)/n Fig.\u00a02. The strd Table\u00a02. The sin2O)3(HfF6)]\u00b7H2O and crystallizes in the monoclinic space group P21/n /n Fig.\u00a03. Compoun2O)2F]2[HfF6]\u00b7H2O and crystallizes in the monoclinic space group P21/n 2F+ cations and octa\u00adhedral HfF62\u2212 anions. The free HfF62\u2212 octa\u00adhedron occupies an inversion center with three distinct bond lengths ranging between 1.9863\u2005(10) and 1.9957\u2005(9)\u2005\u00c5.Compound (IV)/n Fig.\u00a04. The strThe \u039b-shaped building units in compounds (I)\u2013(III) are arranged in head-to-tail chains via inter\u00admolecular hydrogen bonding with multiple hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 stacking contacts to adjacent chains.2O)3(TiF6)] complex in compound (I)2O)3(TiF6)] complexes and three free water mol\u00adecules 3(MF6)]  units in compound (II)2O)3(MF6)] complexes and three contacts to hydrating water mol\u00adecules 3(MF6)] complexes participate in parallel displaced \u03c0\u2013\u03c0 stacking inter\u00adactions (Table\u00a05The [Cu(phen)2F+ complexes (H2O)2F+ complexes and O1\u2014H1B\u22efF4 hydrogen bonds with HfF62\u2212 groups (Table\u00a04B\u22efF1 hydrogen bond to an adjacent Cu(phen)(H2O)2F+ complex and a O2\u2014H2A\u22efO3 hydrogen bond with a free water mol\u00adecule (Table\u00a04MF62\u2212 group forms hydrogen bonds with four free water mol\u00adecules and two Cu(phen)(H2O)2F+ complexes. The Cu(phen)(H2O)2F+ complexes pack with both face-to-face and parallel displaced \u03c0\u2013\u03c0 stacking inter\u00adactions (Table\u00a05In compound (IV)es Fig.\u00a08. The equs Table\u00a04. The apie Table\u00a04. Each MFs Table\u00a05.2O)5(VO(H2O)F4)]\u00b7H2O 5(VOF4(H2O))]\u00b7H2O contains a mol\u00adecular \u039b-shaped [Cu(H2O)5(VOF4(H2O))] mol\u00adecule that is bridged via the Cu1\u2014O8\u2014V1 linkage with a bond angle of 142.88\u00b0. The \u039b-shape of this complex is supported by a single intra\u00admolecular hydrogen bond as well as two hydrogen-bonding inter\u00adactions with a free water mol\u00adecule that serves as an inter\u00admolecular \u2018bridging mol\u00adecule\u2019. In contrast, the hydrating water mol\u00adecules in compounds (I)2O)5(VOF4(H2O))]\u00b7H2O is 88.42\u00b0, meaning that the complex has a small tilt similar to compound (I)Aside from compounds (I)2O)5(VO(H2O)F4)]\u00b7H2O are arranged in a polar NCS lattice containing head-to-head/tail-to-tail chains in which the polar moments of the \u039b-shaped complexes are partially aligned perpendicular to the chain direction, with head-to-tail orientations between chains. In contrast, the \u039b-shapes found in compounds (I)The \u039b-shapes in [Cu2, 2.56\u2005mmol of 1,10-phenanthroline, 1.0\u2005mL (27.6\u2005mmol) of HF(aq) (48%), and 0.1\u2005mL (5.5\u2005mmol) of deionized H2O. Compound (II)2, 2.56\u2005mmol of phen, 1.0\u2005mL (27.6\u2005mmol) of HF(aq) (48%), and 0.1\u2005mL (5.5\u2005mmol) of deionized H2O. Compound (III)2, 2.56\u2005mmol of phen, 1.0\u2005mL (27.6\u2005mmol) of HF(aq) (48%), and 0.1\u2005mL (5.5\u2005mmol) of deionized H2O. Compound (IV)2, 2.56\u2005mmol of phen, 0.4\u2005mL (11.03\u2005mmol) of HF(aq) (48%), and 0.7\u2005mL (38.85\u2005mmol) of deionized H2O.The compounds reported here were synthesized by the hydro\u00adthermal pouch method (Harrison Uiso(H) = 1.2Ueq(C) within OLEX2 .Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989021000645/tx2034sup1.cifCrystal structure: contains datablock(s) I, II, III, IV, I, II, III, IV. DOI: 10.1107/S2056989021000645/tx2034Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989021000645/tx2034IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989021000645/tx2034IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989021000645/tx2034IVsup5.hklStructure factors: contains datablock(s) IV. DOI: 2045776, 2045775, 2045774, 2045773CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Retinal ischemia is a medical condition associated with numerous retinal vascular disorders, such as age-related macular degeneration, glaucoma, and diabetic retinopathy. This in vitro cell and in vivo animal study investigated not only the protective effect of S-allyl L-cysteine  against retinal ischemia but also its associated protective mechanisms. \u03b1, and vascular endothelium factor (VEGF) in the proposed anti-ischemic mechanism. Lastly, the safety of drug consumption was investigated for changes in the animal's body weight, ERG waves, and blood biochemical parameters .  Retinal ischemia was mimicked by raising the intraocular pressure to 120\u2009mmHg for 1 hour in one eye. The effects of pre-/postischemic administration of vehicle vs. SAC 0.18\u2009mg vs. SAC 0.018\u2009mg vs. SAC 0.0018\u2009mg treatments on retina cells were evaluated through cellular viability (MTT assay), flash electroretinograms (ERGs), and fluorogold retrograde labelling  counting). Also, protein immunoblot was utilized to assess the role of Wnt, hypoxia inducible factor (HIF)-1\u03b1/VEGF protein was ameliorated significantly by preischemic low dose of SAC. In terms of the animal safety, no significant body weight and electrophysiological differences were observed among defined different concentrations of SAC without following ischemia. In low SAC dosage and vehicle groups, various blood biochemical parameters were normal; however, high and medium concentrations of SAC significantly lowered the levels of uric acid, Hb, and MCHC.  The characteristic ischemic changes including significant reduction in ERG b-wave ratio and RGC number were significantly counteracted by pre- and postischemic low dose of SAC. Additionally, ischemia-induced overexpression of Wnt/HIF-1\u03b1/VEGF might presently explain SAC's anti-ischemic mechanism. This study shows that preischemic administration of low SAC dosage has been proved to be safe and most effective against rat retinal ischemia electrophysiologically and/or histopathologically. Moreover, counteracting the ischemia-induced overexpression of Wnt/HIF-1 Common retinal ischemic disorders include central/branch retinal artery occlusion, central/branch retinal vein occlusion, glaucoma, diabetic retinopathy, and neovascular age-related macular degeneration. These diseases are associated with visual impairment and even blindness in more severe cases. Characteristic retinal ischemic findings are known to affect electroretinogram's b-wave amplitude and retinal ganglion cell (RGC) number . There a\u03b2-catenin expression. This is done by binding to frizzled and low-density lipoprotein receptor-related protein 5 or 6, which prevents the breakdown of \u03b2-catenin [\u03b2-catenin can work with lymphoid enhancer-binding factor 1, in order to regulate the target gene expression as vascular endothelial growth factor (VEGF) [\u03b1 (HIF-1\u03b1), which consequently also increases VEGF levels in hypoxia [The current knowledge is that the canonical Wnt pathway is said to stabilize -catenin . Liu et r (VEGF) . Other s hypoxia \u201312. Our  hypoxia .\u22128\u2009g/kg\u22483\u223c150\u2009ng of SAC has been proven to protect the human eye against retinal ischemia via its antioxidative and other neuroprotective properties [Therefore, it is important to carry out an investigation into the ischemic alterations associated with the Wnt pathway as well as provide an alternative and complementary treatment to it. Due to the limitations of current treatment , new strategies for retinal vascular disorders driven by persistent ischemia/hypoxia are needed . In thisoperties , 8. Lastoperties  makes it\u03b1, or VEGF (identified through western blotting assay). Finally, the safety of fortified SAC in animals was also evaluated through its effects on the animal's body weight (BW), electrophysiology, and biochemical alterations. Overall, it is hypothesized that SAC would be able to nullify ischemic-induced insults in the retina and with little side effects. Specifically, the addition of SAC would downregulate the level of Wnt, HIF-1\u03b1, and VEGF protein expression. Thus, it would lead to less pronounced retinal ischemia associated alterations, namely, decreased RGC number and ERG b-wave amplitude.In the following study, the effects and mechanisms of SAC against retinal ischemia-reperfusion (I/R) injury were explored, via cellular viability analysis, electroretinogram measurement along with retrograde fluorogold labelling RGC number count, and also its regulation on the defined proteins of Wnt, HIF-1\u03bcg (0.00018\u2009mg) in a 0.2\u2009kg rat and 10\u2009\u03bcg of a 70\u2009kg human. This means that the cellular concentration of the fortified (10-fold) SAC  is equivalent to 0.0018\u2009mg (1.8\u2009\u03bcg) per day in animal tests. In the present in vitro cellular viability tests, ten (1\u2009mM), hundred (10\u2009mM), and thousand folds (100\u2009mM) of the original dose were prepared. These are equivalent to 0.0018 (low dose), 0.018 (medium dose), and 0.18\u2009mg (high dose) used in the in vivo animal studies.SAC was purchased from Sigma-Aldrich  and prepared by dissolving it in distilled water. Based on our previous publication , the maxFor the animal study, defined administration by oral gavage of daily dose of SAC was carried out in these following groups, namely, a preischemic administration (SAC 0.0018\u2009mg\u2009+\u2009I/R and SAC 0.018\u2009mg\u2009+\u2009I/R) for 4 weeks or a postischemic administration (I/R\u2009+\u2009SAC 0.0018\u2009mg) for seven days. In contrast, the rats in the Vehicle\u2009+\u2009I/R group subjected to ischemia were preadministrated with the same volume of vehicle as that of the pre-/postadministrated SAC.The RGC-5 cell lines for the dosing regimen were prepared using the protocol described by Chao et al.  but with\u03bcL of experimental cells and allowed to react for a total of 3\u2009h at 37\u00b0C. Then, the reduced MTT was solubilized by the addition of 100\u2009\u03bcL of dimethyl sulfoxide [The MTT assay was carried out, in order to test the efficient concentrations of SAC. When the NAD(P) H-dependent cellular oxidoreductase enzymes reduces MTT, it forms a purple-colored substance called formazan. In this case, a more purple solution reflects a higher number of viable cells. In order to conduct this test, MTT  was placed into 96-well plate that contains 100\u2009This animal study followed the regulations, which is set by ARVO Statement for the Use of Animals in Ophthalmology and Vision Research. Also, the permission to conduct the study was obtained from institutional review board of Cheng-Hsin General Hospital . As for the animals, six-week-old Wistar rats (BioLasco) were purchased and reared in an environment set at 40\u223c60% humidity and 19\u223c23\u00b0C temperature. Throughout the experimental days, the animals were kept on a 12\u2009h light/dark setting along with 12\u223c15 air refreshment per hour and also given food and water at their own pleasure.Then, the animals were randomly placed into normal, ischemic (Vehicle\u2009+\u2009I/R), preischemic treatment groups (SAC 0.0018\u2009mg\u2009+\u2009I/R and SAC 0.018\u2009mg\u2009+\u2009I/R) and postischemic treatment group (SAC I/R\u2009+\u20090.0018\u2009mg).An intraperitoneal injection was employed to anesthetize the rats. Specifically, 100\u2009mg/kg ketamine (Pfizer) and 5\u2009mg/kg xylazine (Sigma-Aldrich) are given to the rat, which causes the effect of sedation along with analgesia. Another intraperitoneal injection of 140\u2009mg/kg sodium pentobarbital (SCI Pharmtech) was conducted to humanely kill the rat (Scientific Procedures Acts 1986).Each rat (200\u2013250\u2009g) was anesthetized using the method described above and set onto a stereotaxic frame. As described in Chao et al. , a rat mAfter the rats were euthanized, blood sample is slowly taken from the rat's left ventricle, via technique known as cardiac puncture . Then, t\u22121 was given via a strobe 2\u2009cm before the rat's eyes. In this case, fifteen continuous recordings were done at each 2\u2009s interval, which is set at 10\u2009s\u22121. Afterwards, their amplitudes were maximized and calibrated to give a mean, via usage of an amplifier P511, regulated power supply RPS107, and stimulator PS22 (Grass-Telefactor). The b-wave amplitude ratio of I/R eye to that of the normal eye was measured, in order to compare between different experimental treatments as illustrated by Chao et al. [For the flash ERG measurements, they were carried out on day 0 (nonadministered rats) along with the day after vehicle\u2009+\u2009I/R, SAC\u2009+\u2009I/R, or I/R\u2009+\u2009SAC procedure. Then, the dark adaptation was carried out for a total of 8 hours, and anesthesia was conducted for ERG recording with pupil dilation. Then, a stimulus of 0.5\u2009so et al. .\u03bcl of 5% fluorogold (Sigma-Aldrich) at 3.8, 4.0, and 4.2\u2009mm below its skull. Of note, this step was carried out 3 days prior euthanasia of rat. Then, the retina was dissected and collected, as described by Chao et al. [The anesthetic rat is placed onto the stereotaxic frame, and a 2\u2009cm deep cut is created on the rat's scalp and 2 small holes drilled into its skull . Afterwao et al. . Finallyo et al. .\u03bcg/30\u2009\u03bcl/well, and underwent separation through 12% sodium dodecyl sulfate polyacrylamide gel electrophoresis . Once that is completed, the samples were transferred from the gel onto polyvinylidene fluoride membrane. The membranes itself were soaked with 5% fat-free skimmed milk at 4\u00b0C and blocking buffer  for 16 hours. Then, the membranes were incubated with a series of primary antibodies  at 25\u00b0C for 1\u2009hour, namely, mouse anti-\u03b2-actin monoclonal antibody , rabbit anti-Wnt3a monoclonal antibody , mouse anti-HIF-1\u03b1 antibody , and rabbit polyclonal anti-VEGF antibody . The blots were then incubated with the relevant secondary antibodies, which were horseradish peroxidase-conjugated goat anti-rabbit IgG  and anti-mouse IgG  at 25\u00b0C for 1 hour. Lastly, the blots were developed through enhanced chemiluminescent analysis system (HyCell) and exposed to an X-ray film (Fujifilm), and then the proteins levels were analyzed through scanning densitometry.The samples of the retina were isolated and sonicated in lysis buffer  after the rat is euthanized. Then, they were divided to similar amount of 30\u2009t test was utilized to compare between two groups, whereas one-way analysis of variance (ANOVA) was carried out for comparison of three or more than 3 independent groups. After the ANOVA tests, Dunnet's test was selected to compare the control  versus the rest of the groups . Of note, results were presented as mean\u2009\u00b1\u2009SE, and a P value that is smaller than 0.05 was considered as significant.An unpaired To test the optimal and safe cellular concentration of fortified SAC onOGD-insulted cells, lower  and higher  concentrations of pre-OGD administration of SAC were tested and then compared against the control group .As demonstrated in P < 0.001; at 1\u2009mM) attenuation of the OGD-induced cellular injury.In contrast, as shown in Overall, the result implies that SAC with concentrations below 1\u2009mM or 0.0018\u2009mg/day should have some form of protective effect against ischemic injury. Thus, this data along with ERG's results (mentioned later) lead to the selection of SAC 0.0018\u2009mg for testing in animal studies, namely, fluorogold labelling and western blot analysis.SAC 0.0018\u2009mg\u201d, which is as follows: baseline (220.2\u2009\u00b1\u200918.1 vs. 217.0\u2009\u00b1\u200918.2 vs. 221.8\u2009\u00b1\u200916.9 vs. 224.0\u2009\u00b1\u200918.1), week 1 (258.2\u2009\u00b1\u200916.0 vs. 257.3\u2009\u00b1\u200914.5 vs. 262.2\u2009\u00b1\u200915.8 vs. 269.5\u2009\u00b1\u200918.2), week 2 (282.2\u2009\u00b1\u200913.8 vs. 280.0\u2009\u00b1\u20098.3 vs. 304.5\u2009\u00b1\u200914.7 vs. 292.0\u2009\u00b1\u200912.1), week 3 (324.0\u2009\u00b1\u200912.3 vs. 310.7\u2009\u00b1\u20096.7 vs. 325.7\u2009\u00b1\u20099.1 vs. 328.2\u2009\u00b1\u20098.2), and week 4 (321.0\u2009\u00b1\u20099.5 vs. 322.3\u2009\u00b1\u20098.7 vs. 323.3\u2009\u00b1\u200912.5 vs. 330.7\u2009\u00b1\u200917.7). Of note, these BW results were represented as mean\u2009\u00b1\u2009SE (g). From the values above, it could be implied that the animals followed a normal growth rate over time (increase of BW), which is not affected by the presence of vehicle or SAC.As shown in SAC 0.0018\u2009mg\u201d across weeks, which enables a comparison between different groups. The ERG a-wave amplitudes in 0.07\u2009\u00b1\u20090.02), week 1 (0.10\u2009\u00b1\u20090.03 vs. 0.09\u2009\u00b1\u20090.02 vs. 0.07\u2009\u00b1\u20090.02 vs. 0.05\u2009\u00b1\u20090.01), week 2 (0.09\u2009\u00b1\u20090.03 vs. 0.08\u2009\u00b1\u20090.02 vs. 0.10\u2009\u00b1\u20090.02 vs. 0.06\u2009\u00b1\u20090.02), week 3 (0.07\u2009\u00b1\u20090.02 vs. 0.07\u2009\u00b1\u20090.02 vs. 0.06\u2009\u00b1\u20090.02 vs. 0.06\u2009\u00b1\u20090.02), and week 4 (0.09\u2009\u00b1\u20090.03 vs. 0.07\u2009\u00b1\u20090.02 vs. 0.09\u2009\u00b1\u20090.02 vs. 0.06\u2009\u00b1\u20090.01). Throughout the 4 weeks of observation, there was no significant difference of a-wave amplitudes between each group and at each week.By means of ERG, preischemia daily doses of vehicle or SAC  have been proved to be safe, as shown in Tables 0.41\u2009\u00b1\u20090.07), week 1 (0.49\u2009\u00b1\u20090.05 vs. 0.44\u2009\u00b1\u20090.05 vs. 0.44\u2009\u00b1\u20090.06 vs. 0.45\u2009\u00b1\u20090.06), week 2 (0.43\u2009\u00b1\u20090.07 vs. 0.37\u2009\u00b1\u20090.06 vs. 0.46\u2009\u00b1\u20090.01 vs. 0.47\u2009\u00b1\u20090.08), week 3 (0.41\u2009\u00b1\u20090.07 vs. 0.35\u2009\u00b1\u20090.04 vs. 0.44\u2009\u00b1\u20090.06 vs. 0.40\u2009\u00b1\u20090.01), and week 4 (0.35\u2009\u00b1\u20090.04 vs. 0.38\u2009\u00b1\u20090.05 vs. 0.44\u2009\u00b1\u20090.03 vs. 0.41\u2009\u00b1\u20090.04). Similarly, these data are also not significantly different across different groups and various weeks.As for Of note, the ERG a-wave amplitudes are relatively smaller and sometimes harder to be measured than b-wave amplitudes. Thus, it is usually disregarded for the test of therapeutic properties of drugs; instead, it is presently for safety tests and evidence of retinal normality.https://pubmed.ncbi.nlm.nih.gov/31651183/ [SAC 0.0018\u2009mg\u201d for comparison.As reported in previous publication 1651183/ , blood ln\u2009=\u20094\u223c11): for glucose (136.55\u2009\u00b1\u20094.67 vs. 124.71\u2009\u00b1\u20096.83 vs. 128.76\u2009\u00b1\u20093.73 vs. 130.39\u2009\u00b1\u20098.41), blood urea nitrogen (15.89\u2009\u00b1\u20090.51 vs. 15.39\u2009\u00b1\u20090.42 vs. 15.75\u2009\u00b1\u20090.65 vs.17.14\u2009\u00b1\u20091.25), creatinine (0.41\u2009\u00b1\u20090.01 vs. 0.43\u2009\u00b1\u20090.01 vs. 0.42\u2009\u00b1\u20090.02 vs. 0.47\u2009\u00b1\u20090.02), AST (109.71\u2009\u00b1\u20095.91 vs. 104.25\u2009\u00b1\u20095.46 vs. 112.86\u2009\u00b1\u20099.12 vs. 107.71\u2009\u00b1\u20092.30), ALT (35.67\u2009\u00b1\u20091.62 vs. 31.43\u2009\u00b1\u20090.84 vs. 33.71\u2009\u00b1\u20092.16 vs. 34.86\u2009\u00b1\u20091.72), ALKP (101.40\u2009\u00b1\u20095.22 vs. 113.00\u2009\u00b1\u20094.99 vs. 113.17\u2009\u00b1\u20095.38 vs. 108.14\u2009\u00b1\u20093.94), triglyceride (39.11\u2009\u00b1\u20096.08 vs. 35.57\u2009\u00b1\u20093.47 vs. 38.00\u2009\u00b1\u20097.48 vs. 35.22\u2009\u00b1\u20093.78), cholesterol (41.89\u2009\u00b1\u20092.34 vs. 38.11\u2009\u00b1\u20093.01 vs. 36.00\u2009\u00b1\u20092.16 vs. 40.33\u2009\u00b1\u20091.35), high-density lipoprotein , low-density lipoprotein , red blood cells (8.12\u2009\u00b1\u20090.16 vs. 8.00\u2009\u00b1\u20090.11 vs. 7.79\u2009\u00b1\u20090.18 vs. 8.19\u2009\u00b1\u20090.13), hematocrit (46.03\u2009\u00b1\u20090.65 vs. 44.04\u2009\u00b1\u20090.49 vs. 44.94\u2009\u00b1\u20090.77 vs. 44.24\u2009\u00b1\u20090.60), mean corpuscular volume (MCV: 55.68\u2009\u00b1\u20090.72 vs. 55.46\u2009\u00b1\u20090.50 vs. 55.46\u2009\u00b1\u20090.85 vs. 54.51\u2009\u00b1\u20090.67), mean corpuscular hemoglobin , and platelet (1018.89\u2009\u00b1\u200933.50 vs. 1022.00\u2009\u00b1\u200936.15 vs. 1148.50\u2009\u00b1\u200946.56 vs. 1032.50\u2009\u00b1\u200969.83). In addition, there were also no significant differences among various groups (n\u2009=\u20096\u223c8) for albumin (1.51\u2009\u00b1\u20090.04 vs. 1.68\u2009\u00b1\u20090.04 vs. 1.58\u2009\u00b1\u20090.03) and WBC (6.19\u2009\u00b1\u20090.29 vs. 7.140.39 vs. 6.80\u2009\u00b1\u20090.51).After 4 weeks of treatment, there were no significant differences among various groups (P=0.005) vs. 1.12\u2009\u00b1\u20090.10 (P < 0.001) vs. 1.49\u2009\u00b1\u20090.23. As for P < 0.001) vs. 15.81\u2009\u00b1\u20090.26 vs. 15.41\u2009\u00b1\u20090.22. Finally, the mean corpuscular hemoglobin concentration found in P=0.006) vs. 34.73\u2009\u00b1\u20090.18 vs. 34.15\u2009\u00b1\u20090.35.Of note, the only significant side effects were the following parameters displayed in P < 0.001) resulted in ERG b-wave ratio reduction of 0.20\u2009\u00b1\u20090.04 (n\u2009=\u20098), relative to that of normal (control) retina . The ischemia-induced ERG b-wave reduction was either tended to be alleviated or significantly blunted by pre- or postischemia oral ingestion of SAC, namely, SAC 0.018\u2009mg\u2009+\u2009I/R , SAC 0.0018\u2009mg\u2009+\u2009I/R , and I/R\u2009+\u2009SAC 0.0018\u2009mg .As shown in Figures n\u2009=\u20094), the Vehicle\u2009+\u2009I/R treatment led to significant (P < 0.001) reductions in RGC numbers per field of 185.48\u2009\u00b1\u20097.50  elevated number of RGCs cells, namely, 329.52\u2009\u00b1\u200917.25\u2009cells/field for SAC 0.0018\u2009mg\u2009+\u2009I/R  upregulation of target proteins, namely, Wnt3a  are target genes of Wnt pathway, which largely correlated with the development of ischemic-related ocular diseases [The results show that I/R significantly affected the retina in a number of ways, via cellular viability Figures  and 4, ediseases .\u03b1 and in return increases VEGF [\u03b1  for 4 weeks was proven to be the safest and most effective, via observation of body weight changes , ERG alt\u03b1/VEGF overexpression , relative to conventional treatment methods such as anti-VEGF.Preischemia administration of fortified SAC (low dose: 0.0018\u2009mg) is proven to be experimentally safe as shown by the animal safety experiments and electrophysiological/histopathological data, in terms of the ability of SAC to alleviate retinal ischemia injury. Of medical importance and novelty to this paper, the ischemia-induced elevation of upstream protein Wnt3a and its associated downstream target HIF-1"}
{"text": "Status epilepticus (SE) is a life-threatening neurological disorder. The hippocampus, as an important area of the brain that regulates cognitive function, is usually damaged after SE, and cognitive deficits often result from hippocampal neurons lost after SE. Fyn, a non-receptor Src family of tyrosine kinases, is potentially associated with the onset of seizure. Saracatinib, a Fyn inhibitor, suppresses epileptogenesis and reduces epileptiform spikes. However, whether saracatinib inhibits cognitive deficits after SE is still unknown.In the present study, a pilocarpine-induced SE mouse model was used to answer this question by using the Morris water maze and normal object recognition behavioral tests.We found that saracatinib inhibited the loss in cognitive function following SE. Furthermore, we found that the number of hippocampal neurons in the saracatinib treatment group was increased, when compared to the SE group.These results showed that saracatinib can improve cognitive functions by reducing the loss of hippocampal neurons after SE, suggesting that Fyn dysfunction is involved in cognitive deficits after SE, and that the inhibition of Fyn is a possible treatment to improve cognitive function in SE patients. Epilepsy is a chronic neurological disorder characterized by a persistent occurrence of seizures. Status epilepticus (SE) is characterized by prolonged seizures or intermittent seizures and unconsciousness , which pA receptors and is associated with both excitatory and inhibitory ion channels, which are potentially associated with the onset of seizure .Sarscatinib  was administered (25\u00a0mg/kg) orally starting 2\u00a0h after diazepam injection and repeated twice daily for the first 3\u00a0days followed by a single dose each day for the next 11\u00a0days during the 2\u00a0weeks after SE. Same volume of saline was gave to CON mice.Mice that received continuous video-EEG monitoring were implanted with silver wire electrodes (0.125\u00a0mm in diameter) into the hippocampal dentate gyrus (DG) region after anesthesia with pentobarbital . The electrode implantation site used the following coordinates with the bregma as the reference: bregma: \u2212\u20092.3\u00a0mm, lateral: 1.8\u00a0mm and depth: 2.0\u00a0mm. The reference electrode was placed in the frontal cortex. All implanted surgery was performed at 7\u00a0days before the induced SE. EEG activity was recorded 12\u00a0h every day for up to 7\u00a0days at 14\u00a0days after induced SE using PowerLab 8/35 software  . Epileptic spikes (sharp (<\u200950\u00a0ms) positive or negative deflections with amplitudes exceeding twice the baseline EEG) were detected and scored by the Gotman spike using PowerLab software. Mice behavior was monitored using video and reviewed by an investigator who was blinded to the identity of the groups (n\u2009=\u20095 each in every group).One month after induced SE, the mice were anesthetized with pentobarbital  and transcardially perfused with phosphate-buffered saline (PBS) followed by 4% paraformaldehyde in 0.1\u00a0M PBS to sacrifice the mice. The brain was dissected and fixed in 4% paraformaldehyde overnight at 4\u00a0\u00b0C and then cryoprotected in 30% sucrose in PBS for 72\u00a0h at 4\u00a0\u00b0C. Coronary sections\u00a0(8 \u03bcm) were cut with a cryostat and mounted onto glass slides. Sections were washed in PBS and rehydrated in ethanol of decreasing concentrations. After washing with PBS, the sections were incubated with anti-NeuN antibody  overnight at 4\u00a0\u00b0C and washed with PBS. The sections were then incubated with secondary antibody and visualized using 3,3-diaminobenzidine. NeuN-positive neurons in a 100 \u03bcm line long DG of hippocampus were counted in five sections from identical levels in each mouse (n\u2009=\u20095/groups).p\u2009<\u20090.05 was considered statistically significant.Data are expressed as the mean\u2009\u00b1\u2009SEM. One-way or two-way analysis of variance was used to assess differences between two groups and the least significant difference (LSD) or Dunnett T3 post hoc test was used to compare multiple groups after normality tests. A value of Mice often exhibited hypoactivity, curling up, tremors, head bobbing, and myoclonic movement of the limbs after pilocarpine injection. SE usually began by rearing with or without falling and jumping at the onset of SE.t(8)=2.986, p\u2009=0.007). Furthermore, video-EEG showed that saracatinib injection decreased the duration =2.763, p\u2009=0.025) and frequency =3.715, p\u2009=0.006) of spontaneous seizure after SE \u2009=\u20093.68; CON vs SE: 33.59\u2009\u00b1\u20093.8 vs 50.29\u2009\u00b1\u20094.87 on 3\u00a0days, p\u2009=\u20090.13; F\u2009=\u20097.116; CON vs SE vs Sar\u2009+\u2009SE: 22.13\u2009\u00b1\u20093.4 vs 45.83\u2009\u00b1\u20095.8 vs 30.11\u2009\u00b1\u20094.18 on 4\u00a0days, p\u2009=\u20090.01 in CON vs SE, p\u2009=\u20090.025 in SE vs Sar\u2009+\u2009SE; F\u2009=\u200910.307; CON vs SE vs Sar\u2009+\u2009SE: 17.42\u2009\u00b1\u20092.88 vs 41.72\u2009\u00b1\u20093.94 vs 26.45\u2009\u00b1\u20094.69 on 5\u00a0days, p\u2009=\u20090.009 in CON vs SE; p\u2009=\u20090.012 in SE vs Sar\u2009+\u2009SE) and swimming path length from the starting position to the target platform \u2009=\u20093.02; CON vs SE: 1589.37\u2009\u00b1\u2009213.03 vs 2490.87\u2009\u00b1\u2009296.99 on 3\u00a0days, p\u2009=\u20090.23; F\u2009=\u20098.54; CON vs SE: 1138.7\u2009\u00b1\u2009166.62 vs 2381.65\u2009\u00b1\u2009258.46 on 4\u00a0days, p\u2009=\u20090.15; F\u2009=\u200913.81; CON vs SE vs Sar\u2009+\u2009SE: 802.907\u2009\u00b1\u2009103.21 vs 1786.48\u2009\u00b1\u2009155.98 vs 1070.8637\u2009\u00b1\u2009113.52 on 5\u00a0days, p\u2009=\u20090.001 CON vs SE; p\u2009=\u20090.16 SE vs Sar\u2009+\u2009SE) were decreased in Sar\u2009+\u2009SE mice, when compared with the SE mice. However, the swimming speed was similar in all groups mice \u2009=\u20090.54; CON vs SE vs Sar\u2009+\u2009SE: 62.09\u2009\u00b1\u20092.69 vs 61.72\u2009\u00b1\u20093.02 vs 57.85\u2009\u00b1\u20093.79 on 3\u00a0days, p\u2009>\u20090.05; F\u2009=\u20090.475, CON vs SE vs Sar\u2009+\u2009SE: 57.46\u2009\u00b1\u20092.87 vs 55.94\u2009\u00b1\u20093.3 vs 59.62\u2009\u00b1\u20092.6 on 4\u00a0days, p\u2009>\u20090.05; F\u2009=\u20090.11, CON vs SE vs Sar\u2009+\u2009SE: 59.01\u2009\u00b1\u20092.36 vs 57.85\u2009\u00b1\u20092.7 vs 57.43\u2009\u00b1\u20092.46 on 5\u00a0days, p\u2009>\u20090.05). There results suggested that decreased escape latency and swimming path length in the Sar\u2009+\u2009SE group mice were not due to an impaired capacity of swim. When the target platform was removed in the probe trails, the number of crossing target platform areas \u2009=\u20095.917; CON vs SE vs Sar\u2009+\u2009SE: 3.22\u2009\u00b1\u20090.43 vs 1.25\u2009\u00b1\u20090.25 vs 2.5\u2009\u00b1\u20090.5, p\u2009=\u20090.012 in CON vs SE; p\u2009=\u20090.04 in SE vs Sar\u2009+\u2009SE) and staying time in the quadrant \u2009=\u20095.202; CON vs SE vs Sar\u2009+\u2009SE: 20.8\u2009\u00b1\u20091.97 vs 12.84\u2009\u00b1\u20092.14 vs 18.237\u2009\u00b1\u20090.922, p\u2009=\u20090.01 in CON vs SE; p\u2009=\u20090.38 in SE vs Sar\u2009+\u2009SE) where the target platform was previously located were increased in the Sar\u2009+\u2009SE group, when compared with the SE group. Furthermore, when we performed the NOR test, the PI was similar in both SE group mice and Sar\u2009+\u2009SE group mice \u2009=\u20090.326; CON vs SE vs Sar\u2009+\u2009SE: 0.58\u2009\u00b1\u20090.017 vs 0.553\u2009\u00b1\u20090.02 vs 0.545\u2009\u00b1\u20090.049, p\u2009>\u20090.05), but the RI of the Sar\u2009+\u2009SE mice was increased \u2009=\u20096.944; CON vs SE vs Sar\u2009+\u2009SE: 0.64\u2009\u00b1\u20090.029 vs 0.453\u2009\u00b1\u20090.039 vs 0.578\u2009\u00b1\u20090.036, p\u2009=\u20090.015 in CON vs SE; p\u2009=\u20090.023 in SE vs Sar\u2009+\u2009SE). Together, these results showed that saracatinib inhibited deficits in cognitive function after SE.Cognitive function deficits are a common sequelae after SE, so we examined whether saracatinib inhibited deficits in cognitive function after SE. Using the MWM test, escape latency Fig.\u00a0a \u2009=\u200912.32; CON vs SE vs Sar\u2009+\u2009SE: 30.32\u2009\u00b1\u20091.65 vs 20.48\u2009\u00b1\u20091.09 vs 26.44\u2009\u00b1\u20091.42, p\u2009=\u20090.005 in CON vs SE; p\u2009=\u20090.032 in SE vs Sar\u2009+\u2009SE), suggesting that saracatinib relieved the cognitive function deficits by rescuing hippocampal neuronal loss during SE.Because hippocampal neuron loss is an important reason for the deficits in cognitive function after SE, we next determined the number of hippocampal neurons. Neurons in the DG region in the hippocampus were visualized by anti-NeuN antibody using immunohistochemical staining Fig.\u00a0a. The reSE is a neurological condition with high mortality, involving continuous seizure activity, which is often considered as one of the precipitating factors for temporal lobe epilepsy (TLE). The hippocampus and piriform cortex are brain areas commonly damaged by SE. In addition, the amygdala, thalamus, neocortex, and cerebellum are also brain areas that are usually damaged after SE . NeuronaThe Src kinase family is a family of non-receptor tyrosine kinases that plays important roles in regulating signal transduction. Fyn, as a member of the Src family kinases, plays critical roles in regulating cognitive function in AD and in frontotemporal dementia (FTD) patients , 26. FynLoss of hippocampal neurons is the most common reason for cognitive deficits. Neuronal loss frequency occurs in both patients with TLE and in animal models of SE , 22, 32.The Fyn inhibitor, saracatinib, decreased cognitive deficits by attenuating the loss of hippocampal neurons in a pilocarpine-induced SE mouse model, indicating that inhibition of Fyn activity can potentially improve cognitive deficits in patients with TLE. However, further investigation is necessary to identify the mechanism responsible for this neuroprotective effects."}
{"text": "Cyclic GMP\u2010AMP synthase (cGAS) is a cytosolic DNA sensor that catalyzes the synthesis of the cyclic GMP\u2010AMP dinucleotide 2\u20323\u2032\u2010cGAMP. 2\u20323\u2032\u2010cGAMP functions as inducer for the production of type I interferons. Derivatives of this important second messenger are highly valuable for pharmaceutical applications. However, the production of these analogues requires complex, multistep syntheses. Herein, human cGAS is shown to react with a series of unnatural nucleotides, thus leading to novel cyclic dinucleotides. Most substrate derivatives with modifications at the nucleobase, ribose, and the \u03b1\u2010thio phosphate were accepted. These results demonstrate the catalytic promiscuity of human cGAS and its utility for the biocatalytic synthesis of cyclic dinucleotide derivatives. Enzymatic shortcut: Cyclic dinucleotides, which are of great interest to study immunology and immune oncology, can be synthesized in a one\u2010step biotransformation significantly shortening the chemical synthesis route. The enzyme displays a surprisingly large substrate scope. Cyclic dinucleotides are second messengers that can be found in prokaryotes and also in eukaryotes.Vibrio cholerae.During recent years, the structure, regulation, mechanism, and kinetics of human cGAS and other homologues have been described.4b, 5 Herein, we show that the substrate promiscuity of human cGAS can be exploited to produce a series of 2\u20323\u2032\u2010cGAMP analogues in a one\u2010step reaction superior to classical synthesis routes. The substrate derivatives were chosen with modifications at different positions in the nucleobase, ribose or \u03b1\u2010phosphate Scheme\u2005. Each su2\u2010ATP (entry\u20053) and ATP\u2010\u03b1\u2010S (entry\u200516) and only minor amounts for the substrate 8\u2010Cl\u2010ATP (entry\u200513). Higher specific activities between 40 and 43\u2005mU\u2009mg\u22121 were determined for the derivatives 8\u2010Br\u2010dATP (entry\u200511), 8\u2010Br\u2010ATP (entry\u200510) and GTP\u2010\u03b1\u2010S (entry\u200517) with conversions between 56 and 93\u2009%. The specific activities are comparable to those measured for the conversion of the natural substrates ATP and GTP (74\u2005mU\u2009mg\u22121). The highest specific activity of 136\u2005mU\u2009mg\u22121 was measured for the product synthesis from 8\u2010Br\u2010GTP with a yield of 85\u2009%. Thus, the addition of a bromide at the 8\u2010position of the nucleobase seems to be preferred for both, ATP and GTP, substrates. Another interesting substrate derivative, the \u03b1\u2010thio phosphate GTP analogue (entry\u200517), was accepted for the cyclization reaction and 93\u2009% was converted within 24\u2005h. This product has relevant chemical properties and is of particular importance, because the phosphothionate diester linkages are more resistant to hydrolysis than the phosphate diesters.The specific activities and conversions within 24\u2005h were calculated for all reactions Table\u2005. No prodThe cGAS products were additionally analyzed by electrospray ionization\u2010liquid chromatography\u2010mass spectrometry (ESI\u2010LC\u2010MS) and the expected masses were compared with the detected product masses. The synthesis of nine of the 17 products was confirmed with ESI\u2010LC\u2010MS analysis  were converted into the corresponding cyclic dinucleotide derivative using cGAS within 24\u2005h. The conversion of 5\u2005\u03bcmol ATP and GTP served as a reference reaction. The reactions resulted in 65\u2009% conversion of GTP with 2\u2032\u2010F\u2010ATP, 47\u2009% GTP with 8\u2010Br\u2010ATP, 35\u2009% GTP with 8\u2010Cl\u2010ATP, 55\u2009% GTP with 8\u2010NH2\u2010ATP, and 58\u2009% GTP with 8\u2010N3\u2010ATP. These conversions were similar, but not fully comparable with the biotransformations on analytical scale, which can only be attributed to the change in the reaction scale. HPLC Purification of 2\u20323\u2032\u2010cGAMP yielded 1.1\u2005mg of product. The derivatives were purified by two\u2010step HPLC to give 0.1\u2005mg cyclic GMP\u20102\u2032\u2010F\u2010AMP, and 4.1\u2005mg cyclic GMP\u20108\u2010NH2\u2010AMP. The syntheses of cGAMP, cyclic GMP\u20102\u2032\u2010F\u2010AMP and cyclic GMP\u20108\u2010NH2\u2010AMP were successfully validated by NMR spectroscopy (see the Supporting Information for details). The products cyclic GMP\u20108\u2010Br\u2010AMP, cyclic GMP\u20108\u2010N3\u2010AMP and cyclic GMP\u20108\u2010Cl\u2010AMP were not purified in quantifiable amounts.Based on our findings mg\u2010scale biotransformations of 2\u2032\u2010F\u2010ATP, 8\u2010Br\u2010ATP, 8\u2010Cl\u2010ATP, 8\u2010NHIn summary, we have reported a short and facile enzymatic synthesis of novel unnatural cyclic dinucleotides based on the promiscuous activity of human cGAS. Remarkably, most tested ATP and GTP substrate derivatives with modifications at the nucleobases, riboses and \u03b1\u2010phosphate were converted into cyclic dinucleotides with their natural counterpart.The relevance of these cyclic dinucleotide derivatives was recently demonstrated by investigating the biological activity towards the STING receptor based on the analysis of the structure\u2010activity relationship and mouse model systems.Analytical scale biotransformation: For enzyme assays, 40\u2005mM HEPES, 10\u2005mM MgCl2, pH\u20057.2 was used with 0.1\u2005mg\u2009mL\u22121 Herring testis DNA and 40\u2005\u03bcg\u2009mL\u22121 human cGAS. The reaction was started by adding 0.5\u2005mM substrate derivative and 0.5\u2005mM substrate, either ATP or GTP. The reaction volume was 1\u2005mL. Negative controls were performed analogously without the addition of enzyme. All samples were incubated at 37\u2009\u00b0C and 300\u2005rpm in an orbital shaker for at least 24\u2005h. Reactions were stopped by heating at 95\u2009\u00b0C for 5\u2005min. The samples were analyzed with HPLC and LC\u2010MS. The activities given in Table\u2005Milligram\u2010scale biotransformation: For milligram\u2010scale biotransformation, 20\u2005mL reaction solution  was used in shaking flasks. The reaction was started by adding 40\u2005\u03bcg\u2009mL\u22121 human cGAS. The reaction mixture was incubated at 37\u2009\u00b0C and 200\u2005rpm in an orbital shaker for 24\u2005h. The reaction was stopped by heating at 95\u2009\u00b0C for 5\u2005min. The product solutions were frozen and stored at \u221220\u2009\u00b0C.Fractionation of biotransformation products by HPLC: The frozen samples were lyophilized to dryness, subsequently resolved in 1\u2005mL H2O and centrifuged at 21\u2009000\u2005g for 5\u2005min. The supernatant of the product solution was separated and collected as fractions with a LaChrome Elite HPLC system  equipped with an ISAspher 100\u20103C18AQ column, 150\u00d73\u2005mm . The column temperature was set to 30\u2009\u00b0C. The flow rate was set to 1\u2005mL min\u22121. The product solution was repetitively injected with volumes of 99.5\u2005\u03bcL. A gradient of 50\u2005mM triethylamine acetate (TEAA) with 3\u2009% v/v acetonitrile (solvent A) and 100\u2009% acetonitrile (solvent B) was used for the chromatography. The solvent gradient for all products was: 0\u201310\u2005min: 0\u2009% B, 10\u201320\u2005min: 0 to 30\u2009% B, 20\u201322\u2005min: 30\u2009% B, 22\u201325\u2005min 30 to 0\u2009% B, 25\u201330\u2005min 0\u2009% B. Fractions were taken: cGAMP: 12\u201313\u2005min; cyclic GMP\u20102\u2032\u2010F\u2010AMP: 11\u201312\u2005min and 17\u201318\u2005min; cyclic GMP\u20108\u2010Br\u2010AMP: 17\u201319\u2005min; cyclic GMP\u20108\u2010Cl\u2010AMP: 16\u201318\u2005min; cyclic GMP\u20108\u2010NH2\u2010AMP: 11\u201313\u2005min; cyclic GMP\u20108\u2010N3\u2010AMP: 16\u201317\u2005min. Elution of compounds was monitored with a UV detector at 254\u2005nm. The collected fractions were lyophilized and product purification was validated with NMR analysis.2\u2010AMP: 0\u201318\u2005min: 0\u2009% B, 18\u201328\u2005min: 0 to 30\u2009% B, 28\u201330\u2005min: 30 to 90\u2009% B, 30\u201338\u2005min: 90\u2009% B, 38\u201340\u2005min: 90 to 0\u2009% B, 40\u201350\u2005min: 0\u2009% B; Fractions were taken: 25.9\u201327.9\u2005min; cyclic GMP\u20108\u2010N3\u2010AMP: 0\u201315\u2005min: 0 to 22.5\u2009% B, 15\u201317\u2005min: 22.5 to 90\u2009% B, 17\u201325\u2005min: 90\u2009% B, 25\u201327\u2005min: 90 to 0\u2009% B, 27\u201337\u2005min: 0\u2009% B; Fractions were taken: 7.1\u20139.1\u2005min. Elution of compounds was monitored with a UV detector at 254\u2005nm. The collected fractions were lyophilized and product purification was validated with NMR analysis.For further purification of the product derivatives, a second fractionation using chromatography was performed. In the second fractionation, the solvent gradient was individually adapted for each compound: cyclic GMP\u20102\u2032\u2010F\u2010AMP: 0\u201320\u2005min: 0 to 22.5\u2009% B, 20\u201322\u2005min: 22.5 to 90\u2009% B, 22\u201330\u2005min: 90\u2009% B, 30\u201332\u2005min 90 to 0\u2009% B, 32\u201342\u2005min 0\u2009% B; Fractions were taken: 8.7\u201310.2\u2005min; cyclic GMP\u20108\u2010Br\u2010AMP: 0\u201320\u2005min: 0 to 15\u2009% B, 20\u201322\u2005min: 15 to 90\u2009% B, 22\u201330\u2005min: 90\u2009% B, 30\u201332\u2005min: 90 to 0\u2009% B, 32\u201342\u2005min: 0\u2009% B; Fractions were taken: 14.3\u201316.3\u2005min; cyclic GMP\u20108\u2010Cl\u2010AMP: 0\u20135\u2005min: 0\u2009% B, 5\u201325\u2005min: 0 to 30\u2009% B, 25\u201327\u2005min: 30 to 90\u2009% B, 27\u201335\u2005min: 90\u2009% B, 35\u201337\u2005min: 90 to 0\u2009% B, 37\u201347: 0\u2009% B; Fractions were taken:12.7\u201314.1\u2005min and 16.3\u201318.3\u2005min; cyclic GMP\u20108\u2010NHNMR analysis: NMR spectra were recorded on a Bruker AV 600 Avance III HD system  with D2O as solvent and 25\u2005\u03bcL [D4]methanol as internal standard. The solvent signals were referenced to \u03b4H 3.31\u2005ppm and \u03b4C 49.0\u2005ppm.2\u2010AMPCyclic GMP\u20108\u2010NH: 1H NMR : \u03b4=8.08 , 7.94 , 6.17 , 5.99 , 5.60 , 5.06 , 4.72 , 4.62 , 4.44 , 4.38 , 4.27 , 4.37, 4.14\u2005ppm ; 13C NMR : \u03b4=160.2 (CCO), 154.5 (CN), 153.2 (CN), 153.1 (CN), 150.1 (CH), 149.7 (CN), 142.3 (CH), 118.1 (CN), 117.1 (CN), 91.5 (CH), 86.8 (CH), 84.6 (CH), 80.6 (CH), 75.6 (CH), 74.7 (CH), 72.4 (CH), 71.7 (CH), 66.7 (CH2), 62.9\u2005ppm (CH2).Cyclic GMP\u20108\u2010F\u2019\u2010AMP: 1H NMR : \u03b4=8.30 , 8.29 , 7.87 , 6.47 , 5.96 , 5.67 , 5.56 , 5.12 , 4.60 , 4.57 , 4.40 , 4.25 , 4.16\u2005ppm ; 13C NMR : \u03b4=n.d. (CCO), n.d. (CN), 156.0 (CN), 155.1 (CH), 152.2 (CN), 148.1 (CN), 142.9 (CH), 140.7 (CH), 119.2 (CN), 118.1 (CN), 87.8 (CH), 87.6 (CH), 87.2 (CH), 84.0 (CH), 74.6 (CH), 72.2 (CH), 71.8 (CH) 69.9 (CH), n.d. (CH), 66.8\u2005ppm (CH). (n.d.=not detected)The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Developing a universal strategy to improve the specificity and sensitivity of PEGylated nanoaparticles (PEG-NPs) for assisting in the diagnosis of tumors is important in multimodality imaging. Here, we developed the anti-methoxypolyethylene glycol (mPEG) bispecific antibody , which has dual specificity for mPEG and human epidermal growth factor receptor 2 (HER2), with a diverse array of PEG-NPs to confer nanoparticles with HER2 specificity and stronger intensity.++) but not MCF7/neo1 cells (HER2+/\u2212). The \u03b1HER2/Lipo-DiR and \u03b1HER2/SPIO could enhance the sensitivity of untargeted PEG-NPs on MCF7/HER2 (HER2++). In in vivo imaging, \u03b1HER2/Lipo-DiR and \u03b1HER2/SPIO increased the specific targeting and enhanced PEG-NPs accumulation at 175% and 187% on 24\u00a0h, respectively, in HER2-overexpressing tumors.We used a one-step formulation to rapidly modify the nanoprobes with mPEG\u2009\u00d7\u2009HER2 and optimized the modified ratio of BsAbs on several PEG-NPs . The \u03b1HER2/PEG-NPs could specifically target MCF7/HER2 cells (HER2mPEG\u2009\u00d7\u2009HER2, therefore, provided a simple one-step formulation to confer HER2-specific targeting and enhanced sensitivity and contrast intensity on HER2 positive tumors for multimodality imaging.  Optical imaging (OI) is relatively inexpensive and robust for all kinds of molecular and cellular processes in small animals, but clinical applications are hindered by limited depth penetration /[\u00b5W/cm2].MCF7/HER2 (5\u2009\u00d7\u2009106\u00a0cell/well) were incubated \u03b1HER2/SPIO, \u03b1DNS/SPIO or SPIO were added to the tubes and incubated at 37\u00a0\u00b0C for 1\u00a0h. After washing with PBS three times, cells precipitated at the bottom of the Eppendorf tube and were then imaged with 7T MRI  TR/TE, 3000/65\u00a0ms; echo train length, 10; flip angle, 150o; field of view, 6\u00a0cm\u2009\u00d7\u20096\u00a0cm; slice thickness, 1\u00a0mm; interslice gap, 0.1\u00a0mm (10% of slice thickness); and matrix, 192\u2009\u00d7\u2009192. BALB/c nude mice bearing MCF7/HER2 (HER2++) and MCF7/neo1 (HER2+/\u2212) tumor (~\u2009100\u00a0mm3) were injected intravenously with \u03b1HER2/SPIO and \u03b1DNS/SPIO (10\u00a0mg/kg per mouse) in their mammary fat pad regions, respectively. Isoflurane anesthetized mice were imaged with 7T MRI at 0, 24\u00a0h after injection. TR/TE, 3000/65\u00a0ms; echo train length, 10; flip angle, 150; field of view, 4\u00a0cm; slice thickness, 1.2\u00a0mm; interslice gap, 0.12\u00a0mm (10% of slice thickness); and matrix, 256\u2009\u00d7\u2009210. The negative enhancement was calculated by [pretreated signal intensity (SI0)-treated signal intensity (SI24)]/SI0*100.MCF7/HER2 cells  and 500\u00a0units/ml recombinant human granulocyte\u2013macrophage colony-stimulating factor (R&D systems), and then seeded 4\u2009\u00d7\u2009105\u00a0cells/well in 24-well plate. On day 6, 20\u00a0ng/ml recombinant human TNF-\u03b1 (Sigma) and 10\u00a0ng/ml IL-1\u03b2 (R&D systems) were added to the cells to activate DCs for 24\u00a0h. On day\u00a07, the harvested DCs were counted and then incubated 50\u00a0\u03bcg/ml mitomycin C for 30\u00a0min at 37\u00a0\u00b0C at a density of 1\u2009\u00d7\u2009106\u00a0cells/ml, then washed extensively. Autologous CD4+ T cells were isolated on Day 7 by negative selection using CD4+ T Cell Isolation Kit II and LS columns (Miltenyi Biotech). After counting, 2\u2009\u00d7\u2009105 CD4+ T Cells were added to 2\u2009\u00d7\u2009104 mitomycin C-treated DCs and incubated with mPEG\u2009\u00d7\u2009HER2, mPEG\u2009\u00d7\u2009DNS at concentration of 350\u00a0nM in 96-well round bottom plates. Controls included dendritic cells plus CD4+ T cells alone and with concentration of 10\u00a0\u03bcg/ml phytohemagglutinin (PHA). Cells were cultured at 37\u00a0\u00b0C for 5\u00a0days. Proliferation was assessed by ATPlite Luminescence Assay kit (Perkin Elmer). Counts per minute (cpm) for each well were determined by multimode plate reader (Perkin Elmer).To prepare monocyte-derived dendritic cells (DCs), peripheral blood mononuclear cells (PBMCs) from healthy donor blood isolated by Ficoll-Paque and monocytes isolated using Miltenyi Pan Monocyte Isolation Kits and LS columns (Miltenyi Biotech). Monocytes were resuspended in RPMI1640 supplemented with 10% FCS, 2\u00a0mM\u00a0Additional file 1: Table S1. The BsAb-conjugation rate of \u03b1HER2/PEG-NPs. Table S2. The Characterization of BsAb/mPEG-NPs. Figure S1. Immunogenicity of humanized BsAbs. We cocultured dendritic cells differentiated from human PBMCs with autologous CD4+ T cells and stimulated with control medium (represented as DC+T), PHA (as positive control), PEG\u00d7HER2, PEG\u00d7DNS, respectively, for 5 days. Then, we detected the proliferation of CD4+ T cells by ATPlite assay. Bars, SD. CPM, counts per minute; PBMC, peripheral blood mononuclear cell; PHA, phytohemagglutinin."}
{"text": "Cordyceps militaris Improves Chronic Kidney Disease by Affecting TLR4/NF-\u03baB Redox Signaling Pathway\u201d [In the article titled \u201cPathway\u201d , there w2)\u201d.\u201cAll the patients were with the CKD late stage 3 or stage 4 (estimated glomerular filtration rate (eGFR) 25 to 40\u2009mL/min)\u201d should read \u201cAll the patients were with the CKD late stage 3 or stage 4 (estimated glomerular filtration rate (eGFR) 25 to 40\u2009mL/min/1.73\u2009m\u201cAll patients met the following criteria: (1) urine\u2009protein/creatinine\u2009ratio < 5\u201d should read \u201cAll patients met the following criteria: (1) urinal\u2009protein > 1\u2009g/24\u2009h.\u201dP < 0\u200905)\u201d should read \u201cAfter the three-month therapy, the values of eGFR (45.6 \u00b1 8.4\u2009mL/min/1.73\u2009m2) were increased significantly when compared with before therapy .\u201d\u201cAfter the three-month therapy, the values of eGFR (28.3 \u00b1 5.2) were reduced significantly when compared with the CG group (32.8 \u00b1 9.2,"}
{"text": "The cyclo\u00adpenta\u00addienyl rings are eclipsed in both of the title compounds and their packing is dominated by H\u22efH  contacts, as determined by Hirshfeld surface analyses. N,N-di\u00admethyl\u00adamino)\u00admeth\u00adyl]ferrocene, [Fe(C5H5)(C8H12N)], (1), is an inter\u00adesting starting material for the synthesis of planar chiral 1,2-disubstituted ferrocenes, as demonstrated by the preparation of -bis\u00ad{2-[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]ferrocen\u00adyl}di\u00admethyl\u00adsilane, [Fe2(C5H5)2(C18H18N2Si)], (2), from the li\u00adthia\u00adted derivative of 1. The configuration of the lithium compound is unchanged after the substitution reaction and the chirality is preserved in space group P212121. In both compounds, the Cp rings adopt eclipsed conformations. Hirshfeld surface analysis was used to investigate the inter\u00admolecular inter\u00adactions, and showed that H\u22efH  inter\u00adactions dominate in both structures with contact percentages of 83.9 and 88.4% for 1 and 2, respectively.The title compound [( N,N-Di\u00admethyl\u00adamino\u00admethyl\u00adferrocene  was first synthesized by Hauser & Lindsay  and can be converted by a further step using an electrophile -N,N-dimethyl-1-ferrocenyl\u00adethyl\u00adamine, or Ugi\u2019s amine with a chiral directing group -tetra\u00admethyl-1,2-cyclo\u00adhexa\u00adnedi\u00adamine (TMCDA) with yields in high stereoselectivity  and the mechanistic course of the reaction can be described by quantum-chemical calculations -meso-compound of bis\u00ad[dimeth\u00adyl(amino\u00admeth\u00adyl)ferrocen\u00adyl]di\u00admethyl\u00adsilane was characterized by Roewer and co-workers using X-ray diffraction analysis and formed during the synthesis of di\u00admethyldi\u00adchloro\u00adsilane with two equivalents of the racemic li\u00adthia\u00adted N,N-di\u00admethyl\u00adamino\u00admethyl\u00adferrocene -bis\u00ad[dimeth\u00adyl(amino\u00admeth\u00adyl)ferro\u00adcen\u00adyl]di\u00admethyl\u00adsilane (2) and analyze their inter\u00admolecular inter\u00adactions using Hirshfeld surfaces and two-dimensional fingerprint plots.In this paper, we report the crystal structures of 1 crystallizes from n-pentane at 243\u2005K as orange needles with monoclinic (P21/n) symmetry. There are no noticeable irregularities in the bond lengths or bond angles found: the amino\u00admethyl side chain is oriented above its attached cyclo\u00adpenta\u00addienyl ring, and the Cp rings are eclipsed, the dihedral angle between their mean planes being 1.53\u2005(15)\u00b0. The mol\u00adecular structure of 1 is presented in Fig.\u00a01Compound 2 is an orange\u2013red crystalline solid and occurs in enantiomerically pure form in the ortho\u00adrhom\u00adbic space group P212121. The structure is illustrated in Fig.\u00a022 can be assigned the -configuration; furthermore the cyclo\u00adpenta\u00addienyl rings are also in an eclipsed conformation for both iron atoms . The Si\u2014C bonds span the range of 1.869\u2005(3) to 1.874\u2005(3)\u2005\u00c5, which is consistent with the literature \u00b0 (C14\u2014Si1\u2014C10) as the smallest and 112.17\u2005(13)\u00b0 (C14\u2014Si1\u2014C16) as the largest. This flexibility is often observed for Si\u2014C bonds  for N2 and 3.584\u2005(3)\u2005\u00c5 for N1 are too long to be regarded as coordinate bonds to Si from the N lone pairs.Compound 1 is shown in Fig.\u00a03dnorm in the range from \u22120.072 to 1.201 (arbitrary units) and the related fingerprint plots generated by CrystalExplorer  and the C\u22efH/H\u22efC contacts (11.6%) contribute to the packing arrangement of the crystal. Inter\u00admolecular inter\u00adactions of the cyclo\u00adpenta\u00addienyl rings with neighbouring mol\u00adecules can also be visualized.The crystal packing of compound 1. Selected examples found in the Cambridge Structural Database -meso-bis\u00ad[dimeth\u00adyl(amino\u00admeth\u00adyl)ferrocen\u00adyl]di\u00admethyl\u00adsilane -meso-bis\u00ad[dimeth\u00adyl(amino\u00admeth\u00adyl)ferrocen\u00adyl]di\u00adchloro\u00adsilane -[2-(di\u00admethyl\u00adamino\u00admeth\u00adyl)ferrocen\u00adyl]lithium  in n-pentane (1\u2005ml) was made up and stored at 243\u2005K and compound 1 crystallized in the form of orange needles.2 is illustrated in Fig.\u00a07Sp)-[2-(di\u00admethyl\u00adamino\u00admeth\u00adyl)ferrocen\u00adyl]lithium (4.00\u2005mmol) , the product (46%) could be obtained as yellowish plates.The reaction scheme for the synthesis of compound 1H NMR : \u03b4 = 0.81 , 2.02 {s, 12H; [N(CH3)2]2}, 2.80, 3.64 , 4.08 , 4.12 , 4.19 , 4.35  ppm.1H}13C NMR : \u03b4 = 0.6 , 45.4 {4C; [CH2N(CH3)2]2}, 60.5 , 69.7 , 69.8 , 72.6 , 74.2 , 76.6 , 90.5  ppm.{1H}29Si NMR : \u03b4 = \u22127.07  ppm.{m/z (%): 498\u2005(20) [(M\u2013NMe2)+], 409\u2005(100) [(M\u2013NMe2\u2013CH2NMe2\u2013Me2)+], 299\u2005(50) [(M\u2013FcCH2NMe2)+], 199\u2005(50) [(M\u2013SiMe2FcCH2NMe2\u2013NMe2)+].ESI-(+)-MS: Rf:  = 0.20.Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989020010397/hb7933sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989020010397/hb79331sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989020010397/hb79332sup3.hklStructure factors: contains datablock(s) 2. DOI: 2019451, 2019450CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title mol\u00adecule contains a 16-membered macrocycle with the conformation of the C\u2014O\u2014C\u2014C\u2014O\u2014C\u2014C\u2014O\u2014C polyether chain being  27H24N2O5, is a product of the deamination reaction from aza-14-crown-4 ether containing the \u03b3-piperidone subunit. The title mol\u00adecule contains a 16-membered macrocycle with the conformation of the C\u2014O\u2014C\u2014C\u2014O\u2014C\u2014C\u2014O\u2014C polyether chain being t\u2013g(-)\u2013t\u2013t\u2013g(+)\u2013t . The dihedral angle between the planes of the benzene rings fused to the aza-14-crown-4-ether moiety is 31.11\u2005(14)\u00b0. The cavity size inside the macrocycle is 4.72\u2005\u00c5. The macrocycle is significantly flattened as a result of the extended conjugated system. Steric repulsion between the pyridyl\u00adcarboxamide fragment and the benzene ring results in a slight deviation of macrocycle from planarity. The structure also features intra\u00admolecular hydrogen bonding, which results in a deviation of the angle between the planes of amide and pyridyl groups from planarity: this angle is 16.32\u2005(18)\u00b0. In the crystal, the mol\u00adecules are linked into infinite zigzag chains via inter\u00admolecular C\u2014H\u22ef\u03c0 contacts. The chains are bound into layers parallel to (100) by weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds.The title compound, C The mol\u00adecular structure of (3) is presented in Fig.\u00a01t\u2013g(-)\u2013t\u2013t\u2013g(+)\u2013t  conformation. The dihedral angle between the mean planes of the benzene rings fused to the aza-14-crown-4-ether moiety is 31.11\u2005(14)\u00b0. The cavity size inside the macrocycle, determined as a double-mean distance between the C16, C19, O5, O8 and O11 atoms and the center of this penta\u00adgon, is 4.72\u2005\u00c5. The macrocycle is significantly flattened because of the extended conjugated system. The steric repulsion between the 17-pyridyl\u00adcarboxamide fragment and the aromatic ring (C11A/C12\u2013C15/C15A) results in a slight deviation of the macrocycle from planarity. The mol\u00adecular structure also features intra\u00admolecular hydrogen bonds  are linked into infinite zigzag chains via inter\u00admolecular C26\u2014H\u22ef\u03c0(C22) contacts  was synthesized according to the procedure described previously  and 0.44\u2005g (4.7\u2005mmol) \u03b1-amino\u00adpyridine (2) in 10\u2005ml o-xylene was refluxed with stirring for 5\u2005h (monitored by TLC until the disappearance of the starting organic compound spots). The solvent was evaporated under vacuum, then the residue was purified by column chromatography (ethyl acetate:n-hexane = 5:1) and recrystallized from ethanol to obtain 1.27\u2005g of pure compound (3) as single crystals in 58% yield. Tmlt = 482\u2013484\u2005K. Rf = 0.66 . IR, \u03bd, cm\u22121: 1687 (C=O), 1638 (HN\u2014C=O), 3317 (NH). 1H NMR : 3.89 , 4.01 , 4.33 , 6.91\u20137.75 , 7.73 , 8.18 , 8.32 , 8.36 . Mass spectrum, m/z : 456 [M]+ (4), 428\u2005(1), 309\u2005(4), 283\u2005(3), 265\u2005(3), 238\u2005(25), 221\u2005(18), 210\u2005(50), 189\u2005(10), 173\u2005(89), 159\u2005(20), 147\u2005(38), 131\u2005(100), 118\u2005(48), 115\u2005(51), 103\u2005(27), 91\u2005(81), 89\u2005(52), 78\u2005(65), 45\u2005(38). Analysis calculated for C27H24N2O5, %: C, 71.04; H, 5.30; N, 6.14. Found: C, 70.82; H, 5.34; N, 6.01.A solution of 2.0\u2005g (4.7\u2005mmol) aza-crown ether (Uiso(H) = 1.2Ueq(N)]. The other hydrogen atoms were placed in calculated positions with C\u2014H = 0.95\u20130.99\u2005\u00c5 and refined as riding with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020010968/yk2136sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020010968/yk2136Isup2.hklStructure factors: contains datablock(s) I. DOI: 2022314CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are associated into inversion dimers via short Cl\u22efCl contacts [3.3763\u2005(9)\u2005\u00c5]. A Hirshfeld surface analysis indicates that the most important contact percentages for the different types of inter\u00adactions are H\u22efH (43.9%), Cl\u22efH/H\u22efCl (22.9%), C\u22efH/H\u22efC (20.8%) and N\u22efH/H\u22efN (8.0%).In the title compound, C In order to continue our work in this direction, we now describe the synthesis and structure of the title compound, CDatabase survey.The title compound has a non-planar mol\u00adecular conformation Fig.\u00a01; the dihvia short halogen\u22efhalogen contacts  compared to the van der Waals radius sum of 3.50\u2005\u00c5. No other directional contacts could be identified and the shortest aromatic-ring-centroid separation is greater than 5.25\u2005\u00c5. The packing for (I)In the crystal, mol\u00adecules of (I)et al., 2007CrystalExplorer17 The Hirshfeld surface (McKinnon a) and those delineated into H\u22efH, Cl\u22efH/H\u22efCl and C\u22efH/H\u22efC contacts . The pair of characteristic wings in the fingerprint plot delineated into C\u22efH/H\u22efC contacts , have the tips at de + di \u2243 2.80\u2005\u00c5. The remaining contributions from the other different inter\u00adatomic contacts to the Hirshfeld surfaces are listed in Table\u00a01et al., 2015The overall two-dimensional fingerprint plot Fig.\u00a04a and thce Fig.\u00a04c. The pet al., 2016E)-1--2-phenyl\u00addiazene unit resulted in 25 hits. Six compounds are closely related to the title compound, viz. 1-(4-bromo\u00adphen\u00adyl)-2-diazene , C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets parallel to the ab plane. Additional van der Waals inter\u00adactions consolidate the three-dimensional packing. In the crystal of HODQAV, the planes of the benzene rings make a dihedral angle of 56.13\u2005(13)\u00b0. Mol\u00adecules are stacked in columns along the a-axis direction via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In XIZREG, the benzene rings form a dihedral angle of 63.29\u2005(8)\u00b0. Mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In the crystals of LEQXIR and LEQXOX, the dihedral angles between the aromatic rings are 56.18\u2005(12) and 60.31\u2005(14)\u00b0, respectively. In LEQXIR, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short Cl\u22efO contacts occur and in LEQXOX C\u2014H\u22efN and short Cl\u22efCl contacts are observed.In the crystals of HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9\u2005(2) and 64.1\u2005(2)\u00b0, respectively. Mol\u00adecules are linked through weak Z)-4-{[2-hydrazineyl\u00adidene]meth\u00adyl}-N,N-di\u00admethyl\u00adaniline , tetra\u00admethyl\u00adethylenedi\u00adamine (TMEDA) , CuCl  and CCl4 . After 1\u20133\u2005h  the reaction mixture was poured into \u223c0.01 M solution of HCl  and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined organic phase was washed with water (3 \u00d7 50\u2005ml), brine (30\u2005ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3:1\u20131:1) to form a red solid in 85% yield (m.p. 429\u2005K). Orange plates of (I)18H19Cl2N3: C 62.08, H 5.50, N 12.07; found: C 62.01, H 5.48, N 12.03%. 1H NMR  \u03b4 2.38 , 3.05 , 6.88\u20137.43 . 13C NMR  \u03b4 155.57, 153.15, 151.94, 147.03, 142.69, 138.64, 137.97, 133.14, 131.20, 127.08, 121.02, 21.20. ESI\u2013MS: m/z: 349.18 [M+H]+.A 20\u2005ml screw-neck vial was charged with DMSO (10\u2005ml), (Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C) was applied in all cases.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020009202/hb7912sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009202/hb7912Isup2.hklStructure factors: contains datablock(s) I. DOI: 2014419CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The phenol ring makes a dihedral angle of 36.56\u2005(3)\u00b0 with the nitro\u00adbenzene ring. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO inter\u00adactions, forming chains along the  15H14N2O3, was prepared by condensation of 2-hy\u00addroxy-5-methyl-benzaldehyde and 2-methyl-3-nitro-phenyl\u00adamine in ethanol. The configuration of the C=N bond is E. An intra\u00admolecular O\u2014H\u22efN hydrogen bond is present, forming an S(6) ring motif and inducing the phenol ring and the Schiff base to be nearly coplanar [C\u2014C\u2014N\u2014C torsion angle of 178.53\u2005(13)\u00b0]. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO inter\u00adactions, forming chains along the b-axis direction. The Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (37.2%), C\u22efH (30.7%) and O\u22efH (24.9%) inter\u00adactions. The gas phase density functional theory (DFT) optimized structure at the B3LYP/ 6\u2013311\u2005G level is compared to the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C Depending on the tautomers, two types of intra\u00admolecular hydrogen bonds are generally observed in ortho-hy\u00addroxy Schiff bases, namely, O\u2014H\u22efN in enol\u2013imine and N\u2014H\u22efO in keto\u2013amine tautomers  ring motif and also induces the phenol ring and the Schiff base to be nearly coplanar, as indicated by the C3\u2014C8\u2014N1\u2014C9 torsion angle of 178.53\u2005(13)\u00b0. An intra\u00admolecular C15\u2014H15B\u22efO2 inter\u00adaction is also observed. The phenol ring (C1\u2013C8/O1) is inclined to the tolyl ring (C9\u2013C14) by 37.57\u2005(3)\u00b0, and the nitro group (N2/O2/O3) is inclined to the tolyl ring (C9\u2014C14) by 35.05\u2005(2)\u00b0. The configuration of the C8=N1 bond is E. The C4\u2014O1 distance is 1.3455\u2005(18)\u2005\u00c5, which is close to normal values reported for single C\u2014O bonds in phenols and salicyl\u00adidene\u00adamines i and C7\u2014H7C\u22efO1i, resulting in the formation of an infinite chain along the b-axis direction . The two-dimensional fingerprint plots  provide information about the percentage contributions of the various inter\u00adatomic contacts. The most important are H\u22efH inter\u00adactions, which contribute 37.2% to the total Hirshfeld surface. Other contributions are from C\u22efH (30.7%), O\u22efH (24.9%), N\u22efH (2.0%) and C\u22efO (1.8%) contacts. There are also smaller contributions  using the standard B3LYP functional and 6-311G basis-set calculations , the ionization potential (I = \u2212ELUMO), HOMO\u2013LUMO energy gap (\u0394E), the chemical hardness (\u03b7) and softness (S) of the title compound were predicted based on the EHOMO and ELUMO energies. As a result of the large \u0394E and \u03b7 values (Table\u00a03E)-2-{[(3-chloro\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-6-methyl\u00adphenol -2-[(2-hy\u00addroxy-5-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile -4-methyl-2-[(2-methyl-3-nitro-phenyl\u00adimino)\u00admeth\u00adyl]phenol moiety resulted in no hits when both methyl groups were included in the search. Without the methyl groups, seven related compounds were found. Out of these, few are very similar to the title compound and some are metal complexes such as di\u00adazido-}bis\u00ad(4-methyl\u00adpheno\u00adlato)]man\u00adganese amino]-4,5-di\u00adnitro\u00adphen\u00adyl}imino)\u00admeth\u00adyl]-4,6-di-t-butyl\u00adphenolato}iron(III) meth\u00adanol solvate hemihydrate amino]-4,5-di\u00adnitro\u00adphen\u00adyl}imino)\u00admeth\u00adyl]phenolato}iron(III) bis\u00ad]nickel(II) methanol solvate -4,5-di\u00adnitro\u00adphen\u00adyl]aza\u00adnedi\u00adyl}bis\u00ad(methyl\u00adene)]bis\u00ad}meth\u00adano\u00adlcobalt(III) methanol solvate -3-nitro\u00adaniline  in ethanol (15\u2005ml) and 2-methyl-3-nitro-phenyl\u00adamine  in ethanol (15\u2005ml). The reaction mixture was stirred for 5\u2005h under reflux. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.5Ueq(O). Other H atoms were fixed geometrically and treated as riding with C\u2014H = 0.96\u2005\u00c5 (meth\u00adyl) or 0.93\u2005\u00c5 (aromatic), Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989020011652/zl2794sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020011652/zl2794Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020011652/zl2794Isup3.cmlSupporting information file. DOI: 2025323CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "CENP\u2010A\u2010containing nucleosomes. To preserve centromere identity, CENP\u2010A must be escorted to centromeres by a CENP\u2010A\u2010specific chaperone for deposition. Despite this essential requirement, many eukaryotes differ in the composition of players involved in centromere maintenance, highlighting the plasticity of this process. In humans, CENP\u2010A recognition and centromere targeting are achieved by HJURP and the Mis18 complex, respectively. Using X\u2010ray crystallography, we here show how Drosophila CAL1, an evolutionarily distinct CENP\u2010A histone chaperone, binds both CENP\u2010A and the centromere receptor CENP\u2010C without the requirement for the Mis18 complex. While an N\u2010terminal CAL1 fragment wraps around CENP\u2010A/H4 through multiple physical contacts, a C\u2010terminal CAL1 fragment directly binds a CENP\u2010C cupin domain dimer. Although divergent at the primary structure level, CAL1 thus binds CENP\u2010A/H4 using evolutionarily conserved and adaptive structural principles. The CAL1 binding site on CENP\u2010C is strategically positioned near the cupin dimerisation interface, restricting binding to just one CAL1 molecule per CENP\u2010C dimer. Overall, by demonstrating how CAL1 binds CENP\u2010A/H4 and CENP\u2010C, we provide key insights into the minimalistic principles underlying centromere maintenance.Centromeres are microtubule attachment sites on chromosomes defined by the enrichment of histone variant  CAL1 binds both pre\u2010nucleosomal CENP\u2010A/H4 histone dimers and the centromere receptor CENP\u2010C, thus combining the activities of mammalian counterparts HJURP and Mis18 complex.X\u2010ray crystallography reveals how the evolutionary distinct histone chaperone  Centromeres are specialised chromosomal regions that act as a platform for the assembly of kinetochores, the microtubule anchoring sites essential for chromosome segregation during mitosis and meiosis , but lack clear homologues of HJURP and the subunits of the Mis18 complex. Instead, fly\u2010specific CAL1 appears to combine the roles of both HJURP and the Mis18 complex: pre\u2010nucleosomal CENP\u2010A recognition and its targeting to the centromere for deposition, respectively   is sufficient to interact with CAL1 and H4. Subsequently, using CAL11\u2013160, CENP\u2010A144\u2013255 and H4, we reconstituted a truncated protein complex (His\u2010CAL11\u2013160\u2013CENP\u2010A144\u2013225\u2013H4). The molecular weights (MW) measured for His\u2010CAL11\u2013160\u2013CENP\u2010A101\u2013225\u2013H4 and His\u2010CAL11\u2013160\u2013CENP\u2010A144\u2013225\u2013H4 using size\u2010exclusion chromatography combined multi\u2010angle light scattering (SEC\u2010MALS) are 47.0\u00a0\u00b1\u00a00.9 and 43.4\u00a0\u00b1\u00a00.8\u00a0kDa, respectively  residues 1\u2013200 predicted to fold into \u03b1 helices Fig\u00a0A and B. vely Fig\u00a0C. These 1\u2013160\u2013CENP\u2010A101\u2013225\u2013H4 and CAL11\u2013160\u2013CENP\u2010A144\u2013225\u2013H4 yielded two different crystal forms: form I that diffracted X\u2010rays to about 3.5\u00a0\u00c5 and form II that diffracted anisotropically to about 4.4\u00a0\u00c5 (Table\u00a0Drosophila melanogaster (dm) H3/H4 heterodimer  . Purified recombinant CAL11\u2013160\u2013CENP\u2010A101\u2013225\u2013H4 complex was cross\u2010linked using EDC (solid lines), a zero\u2010length cross\u2010linker that covalently links carboxylate groups of Asp or Glu residues with primary amines of Lys and N\u2010terminus, or hydroxyl group of Ser, Thr and Tyr, or BS3 (dashed lines), a cross\u2010linker that covalently links amine to amine or hydroxyl group of Ser, Thr and Tyr. The cross\u2010linked peptides were analysed by mass spectrometry to identify intra\u2010 and intermolecular contacts  is very similar to human CENP\u2010A/H4 (PDB: 3NQJ)  and hydrophobic (involving CAL1\u00a0L11 and M14) interactions, the C\u2010terminal half, mainly aa W22 and F29, is sandwiched between CENP\u2010A \u03b12 and H4 \u03b13    and without \u03b1 helical elements (CAL11\u201350) to bind CENP\u2010A/H4 did not show a noticeable difference under the conditions (buffer containing at least 1M NaCl) needed for CENP\u2010A/H4 solubility. We speculate that in a cellular context post\u2010translational regulation such as phosphorylation or/and other intermolecular interaction involving the downstream helical segments of CAL1 might modulate CENP\u2010A/H4 binding dynamics required for correct CENP\u2010A recruitment at centromeres. This may be a possible explanation for why CAL11\u201350 is not sufficient for CENP\u2010A recruitment in cells  and tested their ability to interact with His\u2010CAL11\u2013160 in a nickel\u2010NTA pull\u2010down assay    and a four\u2010stranded (\u03b24\u2010\u03b29\u2010\u03b26\u2010\u03b27)  and analysed their oligomeric structure by measuring the MW using SEC\u2010MALS  , the overall fold conferring the \u03b2 barrel structure is conserved. However, two loop regions  show striking conformational variation as compared with their equivalent regions in budding yeast CENP\u2010C, Mif2p . The structure reported here and PDB: 6O2K are nearly identical and superpose well with an RMSD of 0.27\u00a0\u00c5  . Next, samples comprising a SEC purified untagged complex were analysed. Both the mass and sedimentation coefficient are consistent with a 2:1 complex, but not with a 2:2 complex . Thus, the AUC together with the crystal structure shows that CENP\u2010C cupin dimer binds just one copy of CAL1 at any given time.Although CAL1 binding by CENP\u2010C involves just a cupin monomer, only one of the two cupin monomers was observed to interact with CAL1, while the equivalent CAL1 binding site of the dimeric counterpart was empty in the crystal structure. We speculate that the other binding site might be sterically hindered by the remaining residues of CAL1 not seen in the crystal structure, thus not allowing a second monomer of CAL1 to bind. This agrees with our previous observation that CAL1AUC) Fig\u00a0C demonst101\u2013225 and H4\u00a0in a similar manner to CAL11\u2013160. The resulting folded complex was analysed by SEC on its own and mixed with 1.2 molar excess of\u00a0His\u2010CENP\u2010C1264\u20131411  compared to His\u2010CAL11\u2013160\u2010LL\u2010841\u2013979/CENP\u2010A101\u2013225/H4 (14.62\u00a0ml) and His\u2010CENP\u2010C1264\u20131411 (16.05\u00a0ml) on their own  results in genome instability, often leading to cell death. To maintain centromere identity defined by the enrichment of CENP\u2010A containing nucleosome, the CENP\u2010A\u2010specific chaperone (HJURP in humans and Scm3 in yeast) escorts CENP\u2010A until its incorporation into the centromeric chromatin  and Schizosaccharomyces pombe (Cnp3) CENP\u2010C cupin domains, with striking differences in the mode of dimerisation  and used directly in ligation\u2010independent cloning (LIC) into bacterial expression vectors. Smaller fragments were amplified using PCR and then used for LIC. CAL11\u2013160\u2010LL\u2010841\u2013979 was produced using homologous PCR.Codon optimised All mammalian expression vectors used in this study were constructed in a pN2\u2010CMV vector.101\u2013225 was generated in  Gold (Agilent) grown in 2XTY media. His\u2010CENP\u2010C1264\u20131411 was expressed in Rosetta (DE3) (Novagen) cells, using 2XTY. His\u2010SUMO\u2010CAL1841\u2013979 was expressed in BL21 (DE3) Gold in LB. After reaching O.D ~\u00a00.6 at 37\u00b0C, cultures were induced at 18\u00b0C using 0.3\u00a0mM IPTG before being purified under native and denaturing conditions. Under native conditions for all protein, pellets were resuspended in a buffer containing 20\u00a0mM Tris\u2013HCl pH 8.0, 100\u00a0mM NaCl, 35\u00a0mM imidazole and 2\u00a0mM \u03b2ME and supplemented with 1\u00a0mM PMSF and cOmplete EDTA\u2010free (Sigma) before lysing by sonication. Clarified lysates were applied onto a HisTrap\u00ae HP column. For His\u2010CAL11\u2013160, His\u2010CAL11\u201350 and His\u2010CAL11\u2013160\u2010LL\u2010841\u2013979, HisTrap\u00ae HP columns were then washed with 60 CV of lysis buffer, 20 CV of 20\u00a0mM Tris\u2013HCl pH 8.0, 1\u00a0M NaCl, 35\u00a0mM imidazole, 50\u00a0mM KCl, 10\u00a0mM MgCl2, 2\u00a0mM ATP and 2\u00a0mM \u03b2ME and then 10 CV of lysis buffer. Proteins were then eluted in 20\u00a0mM Tris\u2013HCl pH 8.0, 100\u00a0mM NaCl, 500\u00a0mM imidazole and 2\u00a0mM \u03b2ME. For His\u2010SUMO\u2010CAL1841\u2013979 and His\u2010CENP\u2010C1264\u20131411, HisTrap\u00ae HP columns were washed with 80 CV of lysis buffer. Protein was eluted using 20\u00a0mM Tris\u2013HCl pH 8.0, 100\u00a0mM NaCl, 500\u00a0mM imidazole and 2\u00a0mM \u03b2ME, and fractions containing protein were dialysed overnight against 20\u00a0mM Tris\u2013HCl pH 8.0, 500\u00a0mM NaCl and 2\u00a0mM DTT for His\u2010CENP\u2010C1264\u20131411 and 20\u00a0mM Tris\u2013HCl pH 8.0, 100\u00a0mM NaCl and 2\u00a0mM DTT for His\u2010SUMO\u2010CAL1841\u2013979. His\u2010SUMO\u2010CAL1841\u2013979 was applied to a HiTrap\u00ae Q HP column and eluted with a gradient of 20\u00a0mM Tris\u2013HCl (pH 8.0), 1\u00a0M NaCl and 2\u00a0mM DTT.His\u2010CAL1Tags were removed by incubation with 3C or TEV overnight followed by a reverse affinity step to remove His\u2010SUMO. Proteins were purified by SEC using either a Superdex 200 increase 10/300 GL, Superdex 75 10/300 GL or Superdex 75 increase 10/300 GL column .1\u2013160, His\u2010CAL11\u201350 and His\u2010CAL11\u2013160\u2010LL\u2010841\u2013979, pellets were suspended in 2\u00a0ml/g of wet pellet of 20\u00a0mM Tris\u2013HCl pH 8.0, 500\u00a0mM NaCl, 25\u00a0mM imidazole, 7\u00a0M urea and 2\u00a0mM \u03b2ME, and incubated for 1\u00a0h at 4\u00b0C with rotation. DNA was sheared by sonication before clarifying by centrifugation. Lysate was then incubated with 10\u00a0ml of HisPur\u2122 Ni\u2010NTA resin (Thermo Fisher Scientific) overnight, before washing with 60 CV of buffer, 20 CV of 20\u00a0mM Tris\u2013HCl (pH 8.0), 1\u00a0M NaCl, 25\u00a0mM imidazole, 7\u00a0M urea and 2\u00a0mM \u03b2ME, 10 CV of 500\u00a0mM NaCl buffer before eluting with 20\u00a0mM Tris\u2013HCl (pH 8.0), 500\u00a0mM NaCl, 500\u00a0mM imidazole, 7\u00a0M guanidine HCl and 2\u00a0mM \u03b2ME.For denatured His\u2010CAL1To refold histones with and without CAL1, histones were resuspended in 20\u00a0mM Tris\u2013HCl pH 7.5, 7\u00a0M guanidine HCl and 2\u00a0mM \u03b2ME and mixed with equimolar amounts of proteins needed. Proteins were then dialysed for 2\u00a0h at 4\u00b0C against 200\u00a0ml of 20\u00a0mM Tris\u2013HCl pH 7.5, 7\u00a0M guanidine HCl and 2\u00a0mM \u03b2ME; then, 2\u00a0l of 10\u00a0mM Tris\u2013HCl pH 7.5, 2\u00a0M NaCl, 1\u00a0mM EDTA and 5\u00a0mM \u03b2ME was slowly added overnight using a peristaltic pump. If needed, refolded protein was further dialysed against a lower salt concentration solvent; if not, complexes were purified by SEC using either a Superdex 200 increase 10/300 GL or Superdex 75 increase 10/300 GL column .1\u2013160\u2010CENP\u2010A101\u2013225\u2010H4, 27\u00a0mg/ml of complex in a buffer of 20\u00a0mM Tris\u2013HCl pH 8.0, 1\u00a0M NaCl and 5\u00a0mM DTT crystallised after about a year in 0.01\u00a0M Cobalt (II) chloride hexahydrate, 0.1\u00a0M MES pH 6.5 and 1.8\u00a0M ammonium sulphate at 18\u00b0C. For CAL11\u2013160\u2010CENP\u2010A144\u2013225\u2010H4, protein in 20\u00a0mM Tris\u2013HCl pH 8.0, 1\u00a0M NaCl and 2\u00a0mM DTT was concentrated to 17\u00a0mg/ml and crystallised in C11, 0.2\u00a0M lithium sulphate, 0.1\u00a0M Tris pH 8.5 and 30% PEG 4000. An optimisation screen was set up in a 24\u2010well format, using half the original concentrations of protein. Tris\u2013HCl pH 8.5 was kept at 0.1\u00a0M, while concentrations of lithium sulphate varied from 0.1 to 0.3\u00a0M and PEG 4000 varied from 24 to 34%.Crystallisation trials were performed using a nanolitre Crystal Gryphon robot (Art Robbins) and grown by vapour diffusion methods. For CAL11264\u20131411 was screened at 15\u00a0mg/ml in 20\u00a0mM Tris\u2013HCl pH 8.0, 500\u00a0mM NaCl and 2\u00a0mM DTT against several commercial and homemade screens at 18\u00b0C. Crystals were obtained in around 13% of all conditions tested. His\u2010CENP\u2010C1264\u20131411\u2010CAL1841\u2013979 complex was made in 20\u00a0mM Tris\u2013HCl pH 8.0, 100\u00a0mM NaCl and 2\u00a0mM DTT and used with Structure 1\u00a0+\u00a02 and JCSG+ (Molecular Dimensions) at 15\u00a0mg/ml at 4\u00b0C. Crystals were briefly transferred to a cryoprotectant solution (either oil or the mother liquor supplemented with 40% peg 3350) before directly flash cooled in liquid nitrogen and analysed on beamlines i03 and i04\u20101 at the Diamond Light Source .Cleaved CENP\u2010C1\u2013160\u2013CENP\u2010A/H4 form I, CENP\u2010C1264\u20131411; CENP\u2010C1264\u20131411\u2010CAL1841\u2013979) and i04\u20101 (CAL11\u2013160\u2013CENP\u2010A/H4 form II), at the Diamond Light Source . Data were processed using the software pipeline available at Diamond Light Source that relies on XDS, CCP4, CCTBX, AutoPROC and STARANISO , CENP\u2010C1264\u20131411 and CENP\u2010C1264\u20131411\u2010CAL1841\u2013979 structures were determined by molecular replacement with the program PHASER . Data collection, phasing and refinement statistics are shown in Table\u00a0Diffraction data were collected on beamlines i03  run at 180\u00a0V for 1\u00a0h in MES buffer. Gels were then stained with Coomassie Blue, and scanned gel images were analysed and quantified with ImageJ.Ni\u2010NTA pull\u2010down assays were performed using His\u2010CAL1Size\u2010exclusion chromatography  coupled to UV, static light scattering and refractive index detection  was used to determine the molecular mass of proteins and protein complexes in solution. Injections of 100\u00a0\u03bcl of 1\u20135\u00a0mg/ml material were used.1\u2013160\u2010CENP\u2010A101\u2013225\u2010H4 (\u2202A280\u00a0nm/\u2202c\u00a0=\u00a00.67 AU.ml/mg), His\u2010CAL11\u2013160\u2010CENP\u2010A144\u2013225\u2010H4 (\u2202A280\u00a0nm/\u2202c\u00a0= 0.75 AU.ml/mg) and His\u2010CAL11\u201350\u2010CENP\u2010A101\u2013225\u2010H4 (\u2202A280\u00a0nm/\u2202c\u00a0= 0.55 AU.ml/mg) were run on a Superdex 200 increase 10/300 GL size\u2010exclusion column pre\u2010equilibrated in 50\u00a0mM HEPES pH 8.0, 2\u00a0M NaCl and 1\u00a0mM TCEP at 22\u00b0C with a flow rate of 0.5\u00a0ml/min. His\u2010CENP\u2010C1264\u20131411 L1357E/M1407E (\u2202A280\u00a0nm/\u2202c\u00a0=\u00a00.75\u00a0AU.ml/mg) was run on a Superdex 200 increase 10/300 GL size\u2010exclusion column pre\u2010equilibrated in 50\u00a0mM HEPES pH 8.0, 300\u00a0mM NaCl and 1\u00a0mM TCEP at 22\u00b0C with a flow rate of 0.5\u00a0ml/min. CENP\u2010C1264\u20131411 (\u2202A280\u00a0nm/\u2202c\u00a0=\u00a00.84\u00a0AU.ml/mg) was run at 4\u00b0C on a Superdex 75 increase 10/300 GL size\u2010exclusion column pre\u2010equilibrated in 50\u00a0mM HEPES pH 8.0, 100\u00a0mM NaCl and 1\u00a0mM TCEP.For His\u2010CAL1280\u00a0nm were analysed by a homo\u2010polymer model  using the parameters stated for each protein, \u2202n/\u2202c\u00a0=\u00a00.185\u00a0ml/g and buffer RI value of 1.335. The mean standard error in the mass accuracy determined for a range of protein\u2013protein complexes spanning the mass range of 6\u2013600\u00a0kDa is \u00b1\u00a01.9%.Light scattering, refractive index (RI) and A3 was used to cross\u2010link 10\u00a0\u03bcg of protein for 2\u00a0h at RT. The reactions were quenched with final concentration 100\u00a0mM Tris\u2013HCl or 5\u00a0mM ammonium bicarbonate, respectively, before separation on Bolt\u2122 4\u201312% Bis\u2010Tris Plus gels (Invitrogen). Following previously established protocol  and 66\u00a0\u03bcg sulpho\u2010NHS (Thermo Fisher Scientific) were used to cross\u2010link 10\u00a0\u03bcg of protein for 1.5\u00a0h at RT. 30\u00a0\u03bcg of BSet\u00a0al (5 cells per well. Cells were transfected using X\u2010tremeGENE DNA Transfection Reagent (Roche) according to the manufacturer's instructions, using 200\u00a0ng of plasmid DNA. Transfected cells were analysed by immunofluorescence 72\u00a0h post\u2010transfection.Schneider S2 cells containing the LacO array (L2\u20104_LacO_LexA_Clone11) were generated as described in Mendiburo et\u00a0al . Schneidet\u00a0al, 2 incubator. Cells were seeded in 10\u00a0cm dishes, a day prior to transfection at a density of 2.5\u00a0\u00d7\u00a0106 cells per well. Transfections were performed with Lipofectamine 3000 (Life Technologies) according to the manufacturer's instructions, using 15\u00a0\u03bcg of plasmid DNA and Opti\u2010MEM I reduced serum medium (Life Technologies). Next day, cells were washed once with 1\u00d7DPBS, trypsinised, counted and re\u2010plated on poly\u2010lysine\u2010coated coverslips in 6\u2010well plates at a density of 106 cells per\u00a0well. Downstream experiments were performed 3\u00a0days post\u2010transfection.U2OS cells containing 200 copies of an array of 256 tandem repeats of the 17\u00a0bp LacO sequence on chromosome 1  overnight at 4\u00b0C in a humidified chamber and were used in 1:100 dilution unless otherwise stated: myc (Abcam\u2010ab9106), V5 (Invitrogen\u2010R96025) and HA . Secondary antibodies coupled to Alexa Fluor 555 and 647 (Invitrogen) were used at 1:100 dilutions. Counterstaining of DNA was performed with DAPI (5\u00a0\u03bcg/ml), and coverslips were mounted on the slides with 30\u00a0\u03bcl of SlowFade\u00ae Gold antifade reagent.Cells were washed once in PBS and then fixed with 3.7% formaldehyde in 0.1% Triton X\u2010100 in 1\u00d7 PBS (PBST) for 8\u00a0min at RT. Following fixation, the slides were washed once in PBST and then blocked in Image\u2010iTz\u2010stacks of 0.2\u00a0\u03bcm increments, using a 100\u00d7 oil immersion objective on a DeltaVision RT Elite Microscope and a CoolSNAP HQ Monochrome camera. All images were deconvolved using the aggressive deconvolution mode on a SoftWorx Explorer Suite (Applied Precision) and are shown as quick projections of maximum intensity. For U2OS cells, the mean fluorescence intensity of the protein of interest was measured at the LacO spot, and then the mean fluorescence intensity in the nucleus (background) was subtracted from this value. For S2 cells, the mean fluorescence intensity of the protein of interest was measured at the LacO spot, and then the mean fluorescence intensity of three spots around the LacO spot was subtracted from this value. 25\u201350 cells were analysed per biological replicate, and a minimum of three independent biological replicates were quantified per experiment.All IF images were taken as 50 et\u00a0al, et\u00a0al, Sedimentation velocity and SE experiments were performed using a Beckman Coulter XL\u2010I analytical ultracentrifuge equipped with an An\u201050 Ti eight\u2010hole rotor. Depending on their concentration, samples were loaded into 12 (low concentration) or 3\u00a0mm (high concentration) pathlength charcoal\u2010filled epon double\u2010sector centrepieces, sandwiched between two sapphire windows. For SV, samples were equilibrated at 4\u00b0C in vacuum for 6\u00a0h before running at 49\u00a0k rpm. For SE, data were recorded at 26\u00a0k rpm. The laser delay, brightness and contrast were pre\u2010adjusted at 3\u00a0k rpm to acquire the best quality interference fringes. Data were collected using Rayleigh interference and absorbance optics recording radial intensity or absorbance at 280\u00a0nm. For SV, data were recorded between radial positions of 5.65 and 7.25\u00a0cm, with a radial resolution of 0.005\u00a0cm and a time interval of 7\u00a0min, and analysed with the program SEDFIT Schuck,  using a t\u2010test or Mann\u2013Whitney test. For each statistical test, P\u2010value of <\u00a00.05 was considered significant.Data are representative of at least three independent experiments, unless otherwise stated. Statistics were performed using GraphPad Prism, version 7.0e , using an unpaired two\u2010tailed AAJ and PH conceived the project. BM\u2010P, VL, PH and AAJ designed experiments. BM\u2010P,VL, OB, MAA and JZ performed experiments. JR provided expertise and feedback. BM\u2010P and AAJ wrote the manuscript with input from all authors.The authors declare that they have no conflict of interest.AppendixClick here for additional data file.Expanded View Figures PDFClick here for additional data file.Review Process FileClick here for additional data file."}
{"text": "In the crystal structure of the title compound inter\u00admolecular hydrogen-bonding inter\u00adactions and weak C\u2014H\u22ef\u03c0 inter\u00adactions between the constituents lead to the formation of a three-dimensional network. Hirshfeld surface analysis revealed that H\u22efH inter\u00adactions dominate the crystal packing. 22H17NO2\u00b7C3H7NO, was synthesized by condensation of an aromatic aldehyde with a secondary amine and subsequent reduction. It was crystallized from a di\u00admethyl\u00adformamide solution as a monosolvate, C22H17NO2\u00b7C3H7NO. The aromatic mol\u00adecule is non-planar with a dihedral angle between the mean planes of the aniline moiety and the methyl anthracene moiety of 81.36\u2005(8)\u00b0. The torsion angle of the Car\u00adyl\u2014CH2\u2014NH\u2014Car\u00adyl backbone is 175.9\u2005(2)\u00b0. The crystal structure exhibits a three-dimensional supra\u00admolecular network, resulting from hydrogen-bonding inter\u00adactions between the carb\u00adoxy\u00adlic OH group and the solvent O atom as well as between the amine functionality and the O atom of the carb\u00adoxy\u00adlic group and additional C\u2014H\u22ef\u03c0 inter\u00adactions. Hirshfeld surface analysis was performed to qu\u00adantify the inter\u00admolecular inter\u00adactions.The title compound, C Schiff bases belong to a class of organic compounds that are formed by the condensation reaction of a carbonyl carbon with an aliphatic/aromatic amine, resulting in the formation of a characteristic imine bond (\u2013HC=N\u2013). Many Schiff bases exhibit activities of biological and pharmaceutical significance. Moreover, Schiff bases are actively used as organic linkers for building metal complexes with inter\u00adesting properties.et al., 2017et al., 2014et al., 2012), anti\u00admicrobial . The title compound crystallizes with a di\u00admethyl\u00adformamide (DMF) solvent mol\u00adecule in a 1:1: ratio. Both anthraldehyde and PABA have shown anti\u00adcancer (Pavitha ar\u00adyl\u2014CH2\u2014NH\u2014Car\u00adyl backbone (C9\u2014C8\u2014N1\u2014C5) is 175.9\u2005(2)\u00b0. The C8\u2014N1 bond length of 1.452\u2005(3)\u2005\u00c5 is in agreement with the corresponding bond length of 1.457\u2005(3)\u2005\u00c5 in the solvent-free compound \u00adisophthalic acid containing gadolinium  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020005393/wm5548sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020005393/wm5548Isup2.hklStructure factors: contains datablock(s) I. DOI: 1982147CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-heterocyclic carbene precursor, zwitterionic 3,3\u2032-bis\u00ad(propane-1-sulfonate) crystallized as its dihydrate and was characterized by single-crystal X-ray diffraction, revealing point group symmetry A known  16H26N4O6S2\u00b72H2O, a water-soluble di-N-heterocyclic carbene ligand precursor was determined using a single crystal grown by the slow cooling of a hot N,N-di\u00admethyl\u00adformamide solution of the compound. The dihydrate crystallizes in the monoclinic space group P21/c, with half of the zwitterionic mol\u00adecule and one water mol\u00adecule of crystallization in the asymmetric unit. The remaining part of the mol\u00adecule is completed by inversion symmetry. In the mol\u00adecule, the imidazole ring planes are parallel with a plane-to-plane distance of 2.741\u2005(2)\u2005\u00c5. The supra\u00admolecular network is consolidated by hydrogen bonds of medium strength between the zwitterionic mol\u00adecules and the water mol\u00adecules of crystallization, as well as by \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazole rings of neighbouring mol\u00adecules and C\u2014H\u22efO hydrogen-bonding inter\u00adactions.The crystal structure of the title compound, C To the best of our knowledge, this is the first crystal structure determination of an alkyl\u00adene-bridged di-imidazolium salt with \u03c9-propyl\u00adsulfonate wingtips. Compound 1 is known from the literature bis\u00ad. No molecules of the solvent, DMF, from which the crystals were obtained, are built into the lattice.The di-1 \u2005\u00c5, S1\u2014O1 = 1.446\u2005(2)\u2005\u00c5, S1\u2014O2 = 1.450\u2005(2)\u2005\u00c5, S1\u2014O3 = 1.453\u2005(2)\u2005\u00c5, and angles O1\u2014S1\u2014O2 = 112.16\u2005(14)\u00b0, O1\u2014S1\u2014O3 = 111.80\u2005(14)\u00b0, and O2\u2014S1\u2014O3 = 112.80\u2005(15)\u00b0. As a result of the point group symmetry The zwitterionic mol\u00adecule of 1 Fig.\u00a02 is compo\u2005\u00c5 Fig.\u00a03 from eacx, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; centroid-to-centroid distance of 3.9541\u2005(17)\u2005\u00c5, slippage 1.622\u2005\u00c5, Fig.\u00a05The water mol\u00adecules bridge adjacent zwitterionic mol\u00adecules through hydrogen bonds of medium strength with sulfonate O atoms as acceptor groups into ribbons aligned parallel to [001] Table\u00a01. \u03c0\u2013\u03c0 staet al., 2016N-heterocyclic carbene ligand precursor mol\u00adecules where two N-\u03c9-sulfonato\u00adpropyl-imidazolium units are connected through an \u03b1,\u03c9-alkyl\u00adene bridge. Crystals of similar sulfoalkyl-imidazolium di-NHC precursors containing aromatic linkers have been grown by Kohmoto et al.  were also reported.A search of the Cambridge Structural Database ], refcode: YAVROF, and [Pd(2)2], refcode: YAVXAX, crystallize in space group type PP21/c.The Pd complexes [PdCl1 was synthesized according to the method of Papini et al. . Analytical data: 13C{1H}-NMR  \u03b4 [ppm], 135.6, 122.5, 48.8, 47.8, 47.2, 26.2, 25.0; ESI\u2013MS , m/z observed 435.1359, calculated value for C16H27N4O6S2, ([M - H]+): 435.1367). For recrystallization, 1 was suspended in DMF and heated to approximately 373\u2005K, then filtered and left overnight to slowly cool down to room temperature. Single crystals, suitable for X-ray analysis, were obtained as colourless prisms after storing the solution in open glass vials in a refrigerator at 278\u2005K. A possible source of water is the employed DMF, which is hygroscopic and easily adsorbs water from a humid atmos\u00adphere. The same type of prismatic crystals were also grown from hot water, revealing a very similar unit cell. However, these crystals were of poor quality, and the best Rint value was very high, 0.19.Compound  al. 2009. 4.4\u2005mmoUiso(H) = 1.5Ueq(O).Crystal data, and details of data collection and structure refinement are summarized in Table\u00a0210.1107/S2056989020009779/wm5571sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009779/wm5571Isup3.cdxSupporting information file. DOI: 10.1107/S2056989020009779/wm5571Isup4.hklStructure factors: contains datablock(s) I. DOI: 2017141CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Nature Communications 10.1038/s41467-020-14509-4, published online 31 January 2020.Correction to: The original version of this Article contained an error in the information provided in the legend for Supplementary Fig. 4D. The text should read: 1\u2009=\u2009UA-GalNAc4S; 2\u2009=\u2009UA-GalNAc4S incubated with B.theta PBS washed cells for 1h; 3\u2009=\u2009UA-GalNAc4S incubated with B.theta PBS washed cell for 24h; 4\u2009=\u2009UA-GalNAc4S incubated with sonicated B.theta PBS washed cells for 1h; 5\u2009=\u2009UA-GalNAc4S incubated with sonicated B.theta PBS washed cell for 24h; 6\u2009=\u2009GalNAc; 7\u2009=\u2009GalNAc6S; 8\u2009=\u2009GalNAc6S incubated with B.theta PBS washed cells for 1h; 9\u2009=\u2009GalNAc6S incubated with B.theta PBS washed cells for 24h; 10\u2009=\u2009GalNAc6S incubated with sonicated B.theta PBS washed cell for 1h and 11\u2009=\u2009GalNAc6S incubated with sonicated B.theta PBS washed cells for 24.This has been corrected in both the PDF and HTML versions of the Article."}
{"text": "II\u2010mediated base pair than a rigid HgII\u2010mediated base pair within the base stack of a double helix.Oligonucleotides incorporating a central C\u2010nucleoside with either a rigid or flexible benzaldoxime base moiety have been synthesized, and the hybridization properties of their metallacyclic derivatives have been studied by UV melting experiments. In all cases, the metallated duplexes were less stable than their unmetallated counterparts, and the metallacyclic nucleobases did not show a clear preference for any of the canonical nucleobases as a base\u2010pairing partner. With palladated oligonucleotides, increased flexibility translated to less severe destabilization, whereas the opposite was true for the mercurated oligonucleotides; this reflects the greater difficulties in accommodating a rigid Pd Take the strain: A flexible PdII\u2010mediated base pair of a benzaldoxime palladacycle disrupts oligonucleotide hybridization less than its rigid analogue, whereas the opposite is true for HgII\u2010mediated base pairs. With a base pair of an incompatible geometry, increased flexibility alleviates some of the strain; with a strain\u2010free base pair it merely leads to an increased entropic penalty of hybridization. II for the canonical nucleobasesDouble\u2010helical oligonucleotides incorporating metal\u2010mediated base pairsII\u2010mediated base pairs have been reported since 1999,II\u2010mediated base pairing remained elusive for a long time and even today the most compelling results have been obtained on duplexes having the PdII\u2010mediated base pair(s) at a terminal position.II\u2010mediated base pair could stem from suboptimal geometries of the base pairs reported so far. Indeed, a thorough study of PdII\u2010mediated base pairing between terpyridine and various azoles has revealed that a planar base pair was only formed with 1\u2010methyltetrazole, having no substituents (not even hydrogens) facing the PdII\u2010terpyridine complex.II center somewhat more exposed than the PdII\u2010terpyridine complex but achieving a coplanar orientation of the palladacycle and the canonical nucleobase may still be difficult. As the steric requirements for base pairing are less strict at the termini than within the base stack, the stabilization provided by the high binding affinity of PdII is not offset by strain imposed by the unfavorable geometry of the PdII\u2010mediated base pair.Although a number of PdII ion in the same position but the former \u20103\u2010[(tert\u2010butyldimethylsilyl)oxy]\u20102,3\u2010dihydrofuran\u20102\u2010yl}methanol and 2\u2010(4\u2010bromophenyl)\u20101,3\u2010dioxane. Compound 1 was then desilylated to the ketone intermediate 2 which, in turn, was reduced to the protected C\u2010nucleoside 3. 5\u2032\u2010Dimethoxytritylation of compound 3 afforded intermediate 4 and subsequent 3\u2032\u2010phosphitylation the phosphoramidite building block 5. Synthesis of compound 5 has been described previouslySynthesis of the protected benzaldehyde C\u2010nucleoside 8 and its phosphoramidite building block 10 were synthesized following the pathway outlined in Scheme\u20057 was first prepared by a Mitsunobu reaction between 3,5\u2010di\u2010O\u2010benzyl\u2010C\u2010hydroxymethyl\u20102\u2010deoxy\u2010\u03b2\u2010d\u2010ribofuranose (6)N\u2010hydroxhphthalimide. Removal of the benzyl protections by Pd(OH)2/C\u2010catalyzed hydrogenation afforded compound 8. Preparation of compound 8 has been reported previously8 was 5\u2032\u2010dimethoxytritylated to give compound 9 which, in turn, was 3\u2032\u2010phosphitylated to give the phosphoramidite building block 10. These last two steps were carried out as described in the literature.Phthaloyl\u2010protected aminooxymethyl C\u2010nucleoside ON1x, ON1y and ON1b were assembled on an automated DNA/RNA synthesizer by the conventional phosphoramidite strategy, employing an extended coupling time for building blocks 5 and 10. Normal (ca. 99\u2009%) coupling yields were observed throughout the synthesis. The acetal and phthaloyl protections of the benzaldehyde and aminooxymethyl residues were removed on\u2010support by treatment with dichloroacetic acid in wet CH2Cl2 or hydrazine acetate in pyridine, respectively. The newly exposed aminooxy function was immediately allowed to react with either 3\u2010hydroxybenzaldehyde or benzaldehyde. Finally, oligonucleotides ON1x, ON1y and ON1b were released from the solid support and deprotected by conventional ammonolysis and purified by RP\u2010HPLC. ON1x eluted as two barely separable peaks, presumably attributable to E and Z isomers of the oxime bond. The stereoselectivity of oximation of benzaldehydes is known to be highly sensitive to the reaction conditionsortho\u2010mercuration), the oligonucleotide environment probably affects as well. Unfortunately, the isolated amounts of the putative isomers of ON1x were not sufficient for more detailed characterization.Table\u2005ON1b was treated with an aqueous solution of methoxylamine to convert the central benzaldehyde residue into an O\u2010methylbenzaldoxime residue. Oligonucleotide ON1z thus obtained was purified by RP\u2010HPLC and cyclopalladated in an aqueous solution of Li2PdCl4. The product mixture was fractioned on RP\u2010HPLC to afford the palladacyclic oligonucleotide ON1z\u2212Pd. Finally, oligonucleotides ON1b, ON1x, ON1y, ON1z and ON1z\u2212Pd were characterized by ESI\u2010TOF\u2010MS and quantified by UV spectrophotometry. Synthesis of the modified oligonucleotides ON1x\u2212Hg and ON1y\u2212Pd has been described previously.ON1x, ON1x\u2212Hg, ON1y, ON1y\u2212Pd, ON1z and ON1z\u2212Pd were studied by conventional UV melting experiments. Each modified oligonucleotide was mixed with each of the unmodified counterparts ON2a, ON2c, ON2g and ON2t, pairing the artificial residue with adenine, cytosine, guanine or thymine, respectively. The oligonucleotide concentrations of the samples were 1.0\u2005\u03bcM, the pH\u20057.4 (20\u2005mM cacodylate buffer) and the ionic strength 0.10\u2005M (adjusted with sodium perchlorate). Melting profiles for unmodified duplexes of otherwise identical sequence but with cytosine in place of the modified residue have been reported previously.Hybridization properties of the modified oligonucleotides ON1x\u2009\u22c5\u2009ON2t, ON1x\u2212Hg\u2009\u22c5\u2009ON2t, ON1y\u2009\u22c5\u2009ON2t, ON1y\u2212Pd\u2009\u22c5\u2009ON2t, ON1z\u2009\u22c5\u2009ON2t and ON1z\u2212Pd\u2009\u22c5\u2009ON2t as representative examples . With the notable exception of ON1z\u2212Pd, monophasic sigmoidal melting curves were observed in most cases. Melting temperatures of the unmetallated duplexes formed by ON1y, ON1z and the faster\u2010eluting isomer of ON1x ranged from 33 to 36\u2009\u00b0C, typical for 11\u2010mer oligodeoxynucleotides containing a single mismatch . Apparently PdII\u2010mediated base pairing by the benzaldoxime palladacycles of ON1y\u2212Pd and ON1z\u2212Pd causes strain that in the former case is to some extent relieved by the flexible structure of the palladacycle but in the latter case prevents formation of a double helix. Disruption of Watson\u2010Crick base pairing by a neighboring metal\u2010mediated base pairing has been described previously in detail with Ag(I) as the bridging metal ion.Figure\u2005ON1x remained elusive as no consistent pattern of different enthalpies and entropies emerged. The relatively low stability of the duplexes formed by the mercurated oligonucleotide ON1x\u2212Hg compared to respective duplexes incorporating a 5\u2010mercuricytosineON1x\u2212Hg (500\u2013600\u2005J\u2009mol\u22121\u2009K\u22121) than for its unmercurated counterpart ON1x (700\u2013800\u2005J\u2009mol\u22121\u2009K\u22121), it was still considerably higher than the respective value reported for those more stable mercurated duplexes (200\u2013400\u2005J\u2009mol\u22121\u2009K\u22121). HgII\u2010mediated base pairing generally leads to a reduced entropic penalty of hybridization owing to dehydration of the bridging HgII ionON1x\u2212Hg some of this effect is offset by restricted rotation of several \u03c3 bonds. The enthalpies of hybridization were similar for the duplexes formed by ON1x\u2212Hg and those containing 5\u2010mercuricytosine, approximately 200\u2005kJ\u2009mol\u22121.When applicable, thermodynamic parameters of hybridization were determined as described previouslyII\u2010mediated base pairing, detailed thermodynamic data on PdII\u2010mediated base pairing is scanty but reanalysis of UV melting profiles reported previously for octamer duplexes with an unpalladated or palladated benzylamine attached to the 5\u2032 terminus through a flexible linker revealed more negative enthalpies and entropies of hybridization for the palladated oligonucleotides.II\u2010mediated base pairing itself is an enthalpy\u2010driven process, whereas the entropic penalty is consistent with conformational restriction of the flexible linker. In the present case, however, both the enthalpies and the entropies of hybridization were less negative with ON1y\u2212Pd than with ON1y and the differences were actually considerably larger than between ON1x\u2212Hg and ON1x. This result, while in apparent conflict with the data obtained on oligonucleotides featuring terminal palladacyclic modifications, could be understood if formation of the PdII\u2010mediated base prevented formation of some (in the case of ON1y\u2212Pd) or all (in the case of ON1z\u2212Pd) of the canonical Watson\u2010Crick base pairs.Compared to the well\u2010documented HgON1x\u2212Hg and ON1y\u2212Pd were largely similar except for ON1x\u2212Hg\u2009\u22c5\u2009ON2g, in which case the signal at 250\u2005nm was hardly detectable. With ON1z\u2212Pd the spectra were much more distorted and the ellipticity lower, in line with the inability of this oligonucleotide to form a double helix with any of the unmodified counterparts at temperatures above 10\u2009\u00b0C. Gradual thermal diminution of the Cotton effects, consistent with denaturation of the double helix, was observed with all of the duplexes studied.All samples were also analyzed CD spectropolarimetrically for more detailed information on the secondary structures adopted by the oligonucleotides. The spectra were recorded between 10 and 90\u2009\u00b0C at 10\u2009\u00b0C intervals. At the low end of the temperature range, the spectra of the unmetallated duplexes were characteristic of B\u2010type double helices, with negative and positive Cotton effects of nearly equal intensity at 250 and 280\u2005nm, respectively (spectra presented in the Supporting Information). The corresponding spectra of the duplexes formed by II\u2010 or HgII\u2010mediated base pair. The oligonucleotide incorporating a flexible palladacyclic nucleoside formed more stable duplexes than its more rigid counterpart whereas comparison of the present data with those reported previously revealed the opposite to be true for oligonucleotides incorporating organomercury nucleosides. These results can be understood in terms of the different geometries of PdII\u2010 and HgII\u2010mediated base pairs. The former may be unable to assume the coplanar orientation preferred within the base stack of a double helix and in such a case a flexible structure might be able to alleviate some of the resulting strain. The latter, on the other hand, are usually nearly planar and geometrically very similar to canonical Watson\u2010Crick base pairs and in such a case increased flexibility will only result in an increased entropic penalty as the flexible structure is constrained within the base stack.Increased flexibility of the metallated nucleoside analog was found to have profoundly different effects on the melting temperatures of oligonucleotide duplexes containing a central PdGeneral methods: All experiments involving air and/or moisture sensitive compounds were performed using oven\u2010dried glassware under argon atmosphere. For preparation of HPLC elution buffers, freshly distilled triethylamine was used. Other commercially available chemicals were used without further purification unless otherwise stated. The solvents for organic synthesis were of reagent grade and dried over 4\u2005\u00c5 molecular sieves. All reactions were monitored by thin layer chromatography (TLC), performed on Merck 60 (silica gel F254) plates. Chromatographic purification of products was accomplished using flash column chromatography on silica gel (230\u2013400\u2005mesh). 1H, 13C and 31P NMR spectra were recorded in deuterated solvents on a Bruker Biospin 500 or 600\u2005MHz NMR spectrometer. Chemical shifts  are quoted relative to the residual solvent peak as internal standard. Mass spectra were recorded on a Bruker Daltonics micrOTOF\u2010Q ESI mass spectrometer.Oligonucleotide synthesis: Synthesis of the modified oligonucleotides ON1x\u2212Hg and ON1y\u2212Pd has been described previously. The other modified oligonucleotides  were assembled on an Applied Biosystems 3400 automated DNA/RNA synthesizer by conventional phosphoramidite strategy. For the acetal protected benzaldehyde and the phtahaloyl\u2010protected aminooxymethyl C\u2010nucleoside phosphoramidite building blocks 2 and 8, the coupling time was extended to 300\u2005s. Based on trityl response, all couplings proceeded with normal efficiency. Removal of the acetal protecting group of the benzaldehyde residue was carried out on\u2010support by treatment with 2\u2009% dichloroacetic acid and 1\u2009% H2O in CH2Cl2 at 25\u2009\u00b0C for 2\u2005h.2Cl2 (3.0\u2005mL) or neat benzaldehyde  to eventually afford oligonucleotides ON1x and ON1y, respectively. Finally, oligonucleotides ON1x, ON1y and ON1b were released from the solid support and the phosphate and base moieties were deprotected by incubation in 25\u2009% aqueous ammonia at 55\u2009\u00b0C for 12\u2005h and purified by RP\u2010HPLC on a Hypersil ODS C18 column  eluting with a linear gradient of MeCN (5\u201330\u2009% over 30\u2005min) in 50\u2005mM aqueous triethylammonium acetate. The flow rate was 1.0\u2005mL\u2009min\u22121 and the detection wavelength 260\u2005nm.ON1b was converted into an O\u2010methylbenzaldoxime residue by treatment with a mixture of methoxylamine hydrochloride (1.0\u2005\u03bcmol) and NaOAc (1.0\u2005\u03bcmol) in H2O (100\u2005\u03bcL) at 25\u2009\u00b0C for 12\u2005h. The crude oligonucleotide ON1z thus obtained was purified by RP\u2010HPLC as described above. For cyclopalladation, ON1z (40\u2005nmol), Li2PdCl4 (60\u2005nmol) and NaOAc (240\u2005nmol) were dissolved in H2O (10\u2005\u03bcL) and the resulting mixture was incubated at 55\u2009\u00b0C for 40\u2005h. The crude product ON1z\u2212Pd was purified by RP\u2010HPLC as described above. As reported previously for other cyclopalladated oligonucleotides,ON1z\u2212Pd eluted as a broad and convoluted peak even after purification, presumably due to the relatively slow ligand\u2010exchange of PdII giving rise to a variety of slow\u2010equilibrating structures involving intra\u2010 as well as interstrand PdII\u2010mediated base pairing. All of the newly synthesized oligonucleotides  were characterized by ESI\u2010TOF\u2010MS and quantified UV spectrophotometrically using molar absorptivities calculated by an implementation of the nearest\u2010neighbors method.The central benzaldehyde residue of oligonucleotide UV melting experiments: UV melting profiles were acquired on a PerkinElmer Lambda 35 UV\u2010Vis spectrometer equipped with a Peltier temperature control unit, using quartz glass cuvettes with 10.00\u2005mm optical path length. The samples were prepared by mixing appropriate oligonucleotides (1.0\u2005\u03bcM) in 20\u2005mM cacodylate buffer (pH\u20057.4), the ionic strength of which was adjusted to 0.10\u2005M with NaClO4. Before each experiment, the samples were annealed by heating to 90\u2009\u00b0C for 30\u2005min and then allowing to gradually cool down to room temperature. Three denaturing and renaturing ramps were performed  with each sample and absorbance at \u03bb=260\u2005nm was recorded at 0.5\u2009\u00b0C intervals. The melting temperatures were determined as inflection points on the UV melting curves.CD experiments: CD spectra were recorded on an Applied Photophysics Chirascan spectropolarimeter equipped with a Peltier temperature control unit, using quartz glass cuvettes with 10.00\u2005mm optical path length. Sample preparation was identical to the procedures used for the UV melting experiments above. Nine spectra were acquired for each sample at 10\u2009\u00b0C intervals over T=10\u201390\u2009\u00b0C and \u03bb=200\u2013400\u2005nm. Before each measurement, the samples were allowed to equilibrate at the appropriate temperature for either 120\u2005s  or 1800\u2005s .O\u2010(tert\u2010Butyldimethylsilyl)\u20102\u2010deoxy\u20102,3\u2010didehydro\u2010\u03b2\u2010d\u2010erythro\u2010pentofuranosyl]phenyl}\u20101,3\u2010dioxane (1)2\u2010{4\u2010\u20102,3\u2010dihydrofuran\u20102\u2010yl}methanol , Bu4NBr , DIPEA  and (tBu3P)2Pd(0)  were taken in a round\u2010bottomed flask and purged with argon. 1,4\u2010dioxane  was added and the mixture stirred at 70\u2009\u00b0C for 16\u2005h. The volatiles were evaporated and the residue was co\u2010evaporated twice from toluene. The crude product was purified by silica gel flash column chromatography  affording compound 1  as a colorless foam. 1H NMR : \u03b4=7.48 , 7.39 , 5.74 , 5.50 , 4.83 , 4.62 , 4.25 , 3.97 , 3.74\u20133.66 , 2.22 , 1.95 , 1.43 , 0.96 ), 0.24 , 0.21 . 13C NMR : \u03b4=151.5 (C3\u2032), 143.0 (C1), 138.8 (C4), 127.1 (C3 & C5), 126.3 (C2 & C6), 101.4 (dioxane\u2212C1), 101.3 (C2\u2032), 84.6 (C4\u2032), 83.3 (C1\u2032), 67.3 (dioxane\u2212C3 & C5), 63.0 (C5\u2032), 25.8 (dioxane\u2212C5), 25.6 (SiC(CH3)3), 18.1 (SiC(CH3)3), \u22124.9 (SiCH3), \u22125.0 (SiCH3). HRMS (ESI+): m/z: calcd for C21H32O5SiNa [M+Na]+: 415.1911; found: 415.1894.R,5R)\u20105\u2010(Hydroxymethyl)\u20104\u2010oxotetrahydrofuran\u20102\u2010yl]phenyl}\u20101,3\u2010dioxane (2)2\u2010{4\u2010+: 301.1046; found: 301.1045.d\u2010erythro\u2010pentofuranosyl)phenyl]\u20101,3\u2010dioxane (3)2\u2010+: 303.1203; found: 303.1202.O\u2010\u20102\u2010deoxy\u2010\u03b2\u2010d\u2010erythro\u2010pentofuranosyl]phenyl}\u20101,3\u2010dioxane (4)2\u2010{4\u2010+: 605.2510; found: 605.2511.O\u2010\u20105\u2010: Et3N  and 2\u2010cyanoethyl\u2010N,N\u2010diisopropylchlorophosphoramidite  were added to a stirred solution of compound 4  in dry CH2Cl2 (3.0\u2005mL) at 25\u2009\u00b0C under N2. The reaction mixture was stirred for 2\u2005h, after which it was diluted with CH2Cl2 (50\u2005mL) and washed with saturated aq. NaHCO3 (50\u2005mL). The organic layer was dried over Na2SO4 and evaporated to dryness. The residue was purified by silica gel flash column chromatography  affording compound 5  as a white foam. 1H NMR : \u03b4=7.52\u20137.43 , 7.41\u20137.37 , 7.32\u20137.29 , 7.24 , 6.86\u20136.83 , 5.52 , 5.19 , 4.52 , 4.30\u20134.26 , 4.01 , 3.82 , 3.74\u20133.69 , 3.67\u20133.61 , 3.36 , 3.28 , 2.47 , 2.33 , 2.26 , 2.01 , 1.47 , 1.21 2), 1.18 2). 13C NMR : \u03b4=158.5 (MeOPh\u2212C4), 144.9 (Ph\u2212C1), 142.5 (C1), 138.0 (C4), 136.2 (MeOPh\u2212C1), 136.1 (MeOPh\u2212C1), 130.18 (MeOPh\u2212C2 & C6), 130.15 (MeOPh\u2212C2 & C6), 128.3 (Ph\u2212C3 & C5), 127.8 (Ph\u2212C2 & C6), 126.7 (Ph\u2212C4), 126.0 (C3 & C5), 125.9 (C2 & C6), 117.5 (CN), 113.1 (MeOPh\u2212C3 & C5), 101.5 (dioxane\u2212C1), 86.1 (CAr3), 86.0 , 80.1 (C1\u2032), 75.7 , 67.4 (dioxane\u2212C3 & C5), 64.1 (C5\u2032), 58.3 , 55.2 (OCH3), 43.5 , 43.2 , 25.8 (dioxane\u2212C4), 24.6 2), 24.5 2), 20.2 . 31P : \u03b4=148.1. 1H NMR : \u03b4=7.51\u20137.43 , 7.40\u20137.36 , 7.30\u20137.27 , 7.22 , 6.85\u20136.81 , 5.52 , 5.19 , 4.52 , 4.29 , 4.24 , 4.01 , 3.87\u20133.77 , 3.80 , 3.62\u20133.53 , 3.31 , 3.26 , 2.63 , 2.40 , 2.25 , 1.99 , 1.47 , 1.19 2), 1.10 2). 13C NMR : \u03b4=158.4 (MeOPh\u2212C4), 144.9 (Ph\u2212C1), 142.5 (C1), 138.0 (C4), 136.13 (MeOPh\u2212C1), 136.11 (MeOPh\u2212C1), 130.17 (MeOPh\u2212C2 & C6), 130.13 (MeOPh\u2212C2 & C6), 128.3 (Ph\u2212C3 & C5), 127.8 (Ph\u2212C2 & C6), 126.7 (Ph\u2212C4), 126.0 (C3 & C5), 125.8 (C2 & C6), 117.5 (CN), 113.1 (MeOPh\u2212C3 & C5), 101.5 (dioxane\u2212C1), 86.0 (CAr3), 85.7 , 80.0 (C1\u2032), 76.1 , 67.4 (dioxane\u2212C3 & C5), 64.2 (C5\u2032), 58.4 , 55.2 (OCH3), 43.5 , 43.2 , 25.8 (dioxane\u2212C4), 24.6 2), 24.5 2), 20.4 . 31P : \u03b4=147.8. HRMS (ESI+): m/z: calcd for C45H55N2O8PK [M+K]+: 821.3328; found: 821.3325.O\u2010benzyl\u2010C\u2010phthalimidooxymethyl\u20102\u2010deoxy\u2010\u03b2\u2010d\u2010ribofuranose (7)3,5\u2010Di\u2010: A solution of DIAD  in dry THF (8.0\u2005mL) was added dropwise to a stirred solution of compound [613] , N\u2010hydroxyphthalimide  and PPh3  in dry THF (65.0\u2005mL) at 0\u2009\u00b0C. The resulting mixture was stirred at 0\u2009\u00b0C for 2\u2005h and then at 25\u2009\u00b0C for 12\u2005h, after which it was evaporated to dryness. The residue was suspended in H2O and extracted with EtOAc (2\u00d750\u2005mL). The combined extracts were dried over Na2SO4 and evaporated to dryness. The residue was purified by silica gel flash column chromatography  affording compound 7  as a colorless syrup. 1H NMR : \u03b4=7.83 , 7.74 , 7.37\u20137.27 , 4.58 , 4.55 , 4.52 , 4.35\u20134.29 , 4.19 , 4.11 , 3.54 , 3.47 , 2.21 , 2.04 . 13C NMR : \u03b4=163.3 (C=O), 138.2 (phenyl\u2212C1), 138.1 (phenyl\u2212C1), 134.4 , 129.0 , 128.43 (phenyl\u2212C3 & C5), 128.37 (phenyl\u2212C3 & C5), 127.70 (phenyl\u2212C4), 127.68 (phenyl\u2212C4), 127.60 (phenyl\u2212C2 & C6), 127.57 (phenyl\u2212C2 & C6), 123.5 , 84.1 (C4\u2032), 80.6 (C3\u2032), 79.6 (CH2ON), 76.4 (C1\u2032), 73.4 (PhCH2), 71.2 (PhCH2), 70.9 (C5\u2032), 34.6 (C2\u2032). HRMS (ESI+): m/z: calcd for C28H27O6NNa [M+Na]+: 496.1731; found: 496.1728.Cd\u2010ribofuranose (8)\u2010phthalimidooxymethyl\u20102\u2010deoxy\u2010\u03b2\u2010: Compound 7  was dissolved in EtOAc (50.0\u2005mL). 20\u2009% Pd(OH)2/C (190.0\u2005mg) was added, the reaction vessel was filled with H2, and the reaction mixture was stirred at 25\u2009\u00b0C under H2 atmosphere  for 1\u2005h. The mixture was filtered through celite, and the filter was washed with EtOAc (2\u00d720\u2005mL). The combined filtrates were concentrated under vacuum and the residue was purified by silica gel flash column chromatography  affording compound 8  as colorless syrup. 1H NMR  \u03b4=7.87\u20137.83 , 4.51 , 4.30\u20134.24 , 3.82 , 3.57\u20133.51 , 2.09\u20131.97 . \u03b4=163.5 (C=O), 134.4 , 128.9 , 122.9 , 87.7 (C4\u2032), 79.5 (CH2ON), 76.1 (C1\u2032), 72.1 (C3\u2032), 62.4 (C5\u2032), 36.6 (C2\u2032). m/z: calcd for C14H15O6NNa [M+Na]+: 316.0792; found: 316.0792.O\u2010\u2010C\u2010phthalimidooxymethyl\u20102\u2010deoxy\u2010\u03b2\u2010d\u2010ribofuranose (9)5\u2010: Compound 9 was prepared from compound 8 as described in the literatureO\u2010[(2\u2010Cyanoethoxy)\u2010C\u2010phthalimidooxymethyl\u20102\u2010deoxy\u2010\u03b2\u2010d\u2010ribofuranose (10)\u2010diisopropylamino)phosphinyl]\u20105\u2010: Compound 10 was prepared from compound 9 as described in the literatureThe authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "According to the literature, only small and twinned crystals of this double salt could be synthesised in a concentrated solution of MgCl2. For the crystal structure solution, single-crystal diffraction was carried out at a synchrotron radiation source. The monoclinic crystal structure (space group Cc) exhibits double chains of MgO octa\u00adhedra linked by corners, connected by carbonate units and water mol\u00adecules. The chloride ions are positioned between these double chains parallel to the (100) plane. Dry MgCO3\u00b7MgCl2\u00b77H2O decom\u00adposes in the air to chlorartinite, Mg2(OH)Cl(CO3)\u00b7nH2O (n = 2 or 3). This work includes an extensive char\u00adacterization of the title com\u00adpound by powder X-ray diffraction, thermal analysis, SEM and vibrational spectroscopy.MgCO Therefore, the system MgCl2\u2013MgCO3\u2013H2O\u2013CO2 has been investigated. The only nonbasic salt containing carbonate and chloride ions is MgCO3\u00b7MgCl2\u00b77H2O , b = 11.30\u2005(8), c = 9.22\u2005(7)\u2005\u00c5 and \u03b2\u00a0= 118.2\u2005(6)\u00b0. Due to the low scattering power and the small size of the crystals, a crystal structure analysis of single crystals was not possible until now. Our own investigations should provide a better com\u00adprehension of the synthesis of MgCO3\u00b7MgCl2\u00b77H2O and provide a more detailed characterization, including a crystal structure analysis.Schmittler 1964 conclude3\u00b7MgCl2\u00b77H2O is based on the information of Schmidt . The suspension was stirred for 30\u2005min. Afterwards, the undissolved MgO was filtered off. CO2 was bubbled through the stirred solution for 24\u2005h at room tem\u00adper\u00adature. The product was filtered off for further characterization.The synthesis of MgCOmidt 1960. MgO (1\u20053\u00b7MgCl2\u00b77H2O was recovered from a droplet of its mother liquor and mounted rapidly in the cold (150\u2005K) stream of nitro\u00adgen gas of the diffractometer.Data were collected on beamline SCD at the KIT Synchrotron Radiation Source using a Stoe IPDS diffrac\u00adtom\u00adeter with monochromated radiation of \u03bb = 0.8000\u2005\u00c5. A crystal of MgCOK\u03b11 radiation, Vantec 1 detector). The samples were prepared as flat plates and measured at room temperature.PXRD patterns were taken for phase identification with a laboratory Bruker D8 Discover powder diffractometer in Bragg\u2013Brentano set up .The thermal analysis was performed with a TG/DTA 220 instrument from Seiko Instruments (reference substance: AlThe SEM images were recorded with a TESCAN Vega 5130 SB instrument (20\u2005kV accelerating voltage). The sample was coated with gold.\u22121, 256 scans per measurement) with KBr blanks was used.For the FT\u2013IR spectrum, a Thermo Scientific Nicolet 380 FTIR spectrometer .max/\u03bb = 0.56\u2005\u00c5\u22121 could be considered for the structure refinement. The crystal structure was solved by direct methods. The resulting structure solution exhibits a chemically reasonable atomic arrangement, distances, angles and displacement parameters.Crystal data, data collection and structure refinement details are given in Table\u00a01Uiso values were set at 1.2Ueq(O) using a riding-model approximation.H atoms were placed in the positions indexed by difference Fourier maps and their The crystal exhibits nonmerohedral twinning. The matrix that relates the individual diffraction pattern was determined as . The reflections of both domains were integrated .3\u00b7MgCl2\u00b77H2O Cl(CO3)\u00b73H2O] begins within a few days 4(OH)2\u00b74H2O] and amorphous phases. At 803\u2005K the decom\u00adposition is com\u00adplete and only MgO remains in the residue. The observed mass loss of 74.3\u2005(1)% confirms the theoretical mass loss of 73.6%.The thermal decom\u00adposition of MgCOps Fig.\u00a02. H2O, COmann 1964. A preci3\u00b7MgCl2\u00b77H2O show thin needles (50 \u00d7 5\u2005\u00b5m), which are twinned or even more inter\u00adgrown Cl(CO3)\u00b73H2O  plane, are located the chloride ions Cl1 and Cl2 Fig.\u00a08. The poss Table\u00a03. As a co3\u00b7MgCl2\u00b77H2O and MgCO3\u00b73H2O Cl(CO3)\u00b72H2O (chlorartinite) and Mg2(OH)Cl(CO3)\u00b7H2O (dehydrated clorarti\u00adnite), do not exhibit such double chains  I. DOI: 10.1107/S2053229620008153/uk3196Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2053229620008153/uk3196Isup3.cmlSupporting information file. DOI: 2010753CCDC reference:"}
{"text": "In the ferrocene unit, the penta\u00addienyl (Cps) rings are in an eclipsed conformation. Strong inter\u00admolecular \u03c0\u2013\u03c0-stacking, CH(Cp)\u2014C(Cp), and O(p-nitro\u00adphen\u00adyl)\u2014HC(Cp) inter\u00adactions consolidate the crystal structure.The title ferrocene derivative including an alkyne and a  5H5)2(C8NO2)], including an alkyne bonded to a para-nitro\u00adphenyl substituent, which was synthesized from a copper-free Sonogashira cross-coupling reaction between ethynylferrocene and 4-bromo-1-nitro\u00adbenzene, crystallizes in the P21/n space group. In the ferrocene unit, the penta\u00addienyl (Cps) rings are in an eclipsed conformation. The angle of rotation between the substituted cyclo\u00adpenta\u00addienyl ring and the p-nitro\u00adphenyl group is 6.19\u2005(10)\u00b0, yielding a quasi-linear extension of the ferrocenyl substitution. Important inter\u00admolecular inter\u00adactions arise from \u03c0\u2013\u03c0 stacking between the Cp rings and the p-nitro\u00adphenyl, from corners of the Cp rings that are perpendicularly aligned, and between the O atoms from the nitro substituent and carbons at the corners of the Cp rings, propagating along all three crystallographic axes.The title ferrocene derivative, [Fe(C The distances of the Fe1 atom from the centroids of the substituted and unsubstituted Cp rings are 1.6461\u2005(8) and 1.6584\u2005(8)\u2005\u00c5, respectively. The Cg1\u2014Fe1\u2014Cg2 angle is 179.27\u00b0, where Cg1 and Cg2 are the centroids of substituted and unsubstituted Cp rings, respectively. The Cp rings in the ferrocene system are thus almost parallel, since the angle between the Cp ring planes is 1.03\u2005(13)\u00b0. In addition, the Cp rings display a nearly eclipsed conformation with a slight deviation, as demonstrated by the average C\u2014Cg1\u2014Cg2\u2014C torsion angle of 12.26\u00b0. The C\u2014C bond distances in the Cp rings range from 1.417\u2005(2) to 1.436\u2005(2)\u2005\u00c5, while the Fe\u2014C bond lengths range between 2.038\u2005(2) and 2.055\u2005(2)\u2005\u00c5.Fig.\u00a01p-nitro\u00adphenyl substituent, allowing the formation of a zigzag structure; atom pairs involved relate C6(Cp) and C7(Cp) to C17(p-nitro\u00adphen\u00adyl) and C18(p-nitro\u00adphen\u00adyl) of a neighboring mol\u00adecule, with short contacts of 3.340\u2005(2) and 3.397\u2005(2)\u2005\u00c5, respectively. This inter\u00adaction can be described as pairs of mol\u00adecules being inter\u00adrupted by two C3(Cp)\u22efH8\u2014C8(Cp) inter\u00adactions from a different inter\u00adconnected pair of perpendicularly oriented Fc moieties with short contact distances of 2.83\u2005\u00c5 each. Short contacts from neighboring mol\u00adecules establishing a distinctive inter\u00adconnected pair between a corner of the Cp ring and one of the oxygen atoms from the p-nitro\u00adphenyl substituent yield a closed arrangement of atoms. Short contacts involve H6\u2014C6(Cp)\u22efO1(p-nitro\u00adphen\u00adyl) at a distance of 3.461\u2005(2)\u2005\u00c5. Another inter\u00adconnection is found between adjacent p-nitro\u00adphenyl groups, yielding a ring arrangement involving pairs from H17\u2014C17(p-nitro\u00adphen\u00adyl)\u22efO2(p-nitro\u00adphen\u00adyl) with a distance of 2.727\u2005(2)\u2005\u00c5 and pairs from O1(p-nitro\u00adphen\u00adyl)\u22efH15\u2014C15(p-nitro\u00adphen\u00adyl) with a distance of 2.716\u2005(2)\u2005\u00c5. In addition, a chain is formed by short contacts from the C17\u2014H17(p-nitro\u00adphen\u00adyl)\u22efO1(p-nitro\u00adphen\u00adyl) inter\u00adaction belonging to the p-nitro\u00adphenyl substituent with a distance of 3.203\u2005(19)\u2005\u00c5. Numerical details of the hydrogen-bonding inter\u00adactions are given in Table\u00a01The title compound exhibits \u03c0\u2013\u03c0 stacking inter\u00adactions between one of the Cp rings from the Fc moiety and the CrystalExplorer17  and those decomposed into nine individual inter\u00adactions: H\u22efH , C\u22efH/ H\u22efC , O\u22efH/ H\u22efO , C\u22efC , C\u22efO/O\u22efC , C\u22efN/N\u22efC , N\u22efO/O\u22efN , O\u22efO  and N\u22efH/H\u22efN . The Hirshfeld surface analysis for the title compound indicates that the most significant contributions arise from H\u22efH and C\u22efH contacts 2 (0.01\u2005mmol), Et3N (2\u2005mmol) and 4-bromo-1-nitro\u00adbenzene (1.0\u2005mmol) to a 25\u2005mL round-bottom flask, followed by the addition of DMF (1.0\u2005mL) by syringe. The reaction was stirred for 1\u2005h at 353\u2005K. The reaction was stopped and crashed out with 20\u2005mL of cold distilled water, then the solid was vacuum filtrated, and chromatographed [silica (hepta\u00adne\u2013ethyl acetate/7:3)] to afford the pure compound, 70% yield. Dark-red crystals suitable for X-ray diffraction were obtained by the slow evaporation of CDCl3 solution of the title compound at room temperature. NMR analyses were performed on a Bruker AV-700 spectrometer by using CDCl3 99.9% pure as a solvent and Me4Si as external standard.1H NMR : 4.26 , 4.32 , 4.55 , 7.59 , 8.18 . 13C NMR : 63.6, 69.6, 70.1, 71.8, 84.5, 95.2, 123.6, 131.1, 131.8, 146.4. IR : 2200 (C\u2261C). Electrochemistry: .The title compound was prepared by adding ethynylferrocene (1.0\u2005mmol), PdClUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020010336/dj2003sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020010336/dj2003Isup2.hklStructure factors: contains datablock(s) I. DOI: 1991635CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Figure\u00a06 Liver control [1] appears identical to Fig.\u00a010 liver control [2]Figure\u00a06 Lung PEG-NPs [1] appears identical to Fig.\u00a010 lung PEG-CF [2]Figure\u00a06 Spleen control [1] appears identical to Fig.\u00a010 spleen control [2]Figure\u00a06 Spleen treatment [1] appears identical to Fig.\u00a010 spleen treatment [2]Figure 7A [1] appears to be identical but in a different order to Fig.\u00a06A all panels [3]Figure 7B [1] appears identical to Fig.\u00a06B [3]Figure 7D [1] appears identical to Fig.\u00a06D [3] using a different scaleFigure 7C [1] appears identical to Fig.\u00a06E [3] using a different scaleAll authors agree with this retraction.The authors have retracted their article  because"}
{"text": "Type 1 diabetes (T1D) and celiac disease (CD) share common genetic loci, mainly within the human leukocyte antigen (HLA) class II complex. Extended genotyping of HLA class II alleles and their potential risk for developing both diseases remains to be studied. The present study compared extended HLA\u2010class II gene polymorphisms in children with T1D, CD, and a subgroup diagnosed with both diseases (T1D w/CD).Next\u2010generation targeted sequencing (NGTS) of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1, DQB1, DPA1, and DPB1 alleles from DNA collected from 68 T1D, 219 CD, and seven T1D w/CD patients were compared with 636 HLA\u2010genotyped Swedish children from the general population selected as controls.DRB4*01:03:01 allele occurred more frequently in T1D w/CD (odds ratio (OR)\u2009=\u20097.84; 95% confidence interval (95% CI)\u2009=\u2009, P\u2009=\u20090.0002) and T1D , P\u2009=\u20091.07\u2009\u00d7\u200910\u221214), respectively. The DRB3*01:01:02 allele occurred more frequently in CD as compared to controls , P\u2009=\u20094.24\u2009\u00d7\u200910\u221271), but less frequently in T1D , P\u2009=\u20097.29\u2009\u00d7\u200910\u221207) and T1D w/CD , P\u2009\u2264\u20090.999). The frequency of the DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01 (DR4\u2010DQ8) haplotype was higher in T1D w/CD  P\u2009=\u20093.75\u2009\u00d7\u200910\u22129), and moderately higher in T1D  P\u2009=\u20090.01) compared with controls, but comparable in CD , P\u2009=\u20090.08) and controls.In comparison to controls, the DRB4*01:03:01, DRB3*01:01:02, and DRB3*02:02:01 of which DRB4*01:03:01 confers the strongest risk allele for developing T1D w/CD.Children with T1D and CD are associated with  HLA\u2010class II allele sequencing was performed using the ScisGo HLA v4 typing kit . Known haplotypes were used to phase the extended haplotypes and to predict the genotypes. Amplicon\u2010based 2\u2010stage polymerase chain reaction (PCR)\u2010based amplification of HLA\u2010class II alleles and sequencing\u2010by\u2010synthesis approach by using fluorescently labeled reversible terminator nucleotides with MiSeq v2 PE500  technology was performed as previously described.2.3\u03c72 tests and Fisher's exact tests (if any cell contained fewer than three observations) were used to test whether the frequencies of a given allele/haplotype differed between cases and noncases. The RPE method was used to identify the disease risk alleles, haplotypes or genotypes with the strongest predisposing or protective effects at each iteration. The selected alleles were then removed from the dataset, and the analysis was repeated until no risk or protective alleles were identified. Comparisons of DR and DQ allele frequencies were performed for both exons 2 and 3 of chromosome 6p21 by performing pairwise comparisons between all study groups and listed in order of increasing P\u2010value, followed by the extended haplotype and genotype frequencies. In the HLA\u2010DR locus, alleles of HLA\u2010DRB1 are in linkage disequilibrium with alleles of either HLA\u2010DRB3 or DRB4 or DRB5. Hence, by treating these highly dependent DR subtypes and their allelic variations as different alleles, analysis of HLA\u2010DRB1 and the secondary DRB3, DRB4 or DRB5 alleles by PRE method produces estimates of frequencies for all haplotypes provided that expectation numbers of corresponding haplotypes are five or more copies in both patients and control subjects. P\u2010values \u2264.05 were considered statistically significant, and alleles with a low frequency (\u22641%) were not shown in the analysis. The P\u2010values presented are nominal and not adjusted for multiple comparisons. Analyses were performed in R (r-project.org) version 3.6.1 and R package epiDisplay version 3.5.0.1.Allelic frequency distribution analysis of HLA\u2010class II genes was performed using the relative predispositional effects (RPE) analysis.33.1DRB345, \u2010DRB1, \u2010DQA1 and \u2010DQB1 allele frequencies in children with CD compared with controls are summarized in Table S1. The allelic distributions of the disease associated DRB alleles differed significantly between all the patient groups and the controls , P\u2009=\u20094.24\u2009\u00d7\u200910\u221271), DRB4*01:03:01 in 32% , P\u2009=\u20090.002) and DRB4*01:03:02 in only 1.4% , P\u2009=\u20090.021). Likewise, DRB3*02:02:01 occurred in 4.6% which was less frequent than in controls , P\u2009=\u20091.23\u2009\u00d7\u200910\u22129). DRB1*03:01:01 occurred in 64% of CD children which was higher than in the controls , P\u2009=\u20093.82\u2009\u00d7\u200910\u2212105). The DRB1*04:01:01 allele was found in 19%  P\u2009=\u20091.85\u2009\u00d7\u200910\u22127) and DRB1*04:04:01 found in 12% , P\u2009=\u20095.66\u2009\u00d7\u200910\u22128). The DRB1*08:01:01 allele had a protective effect in 1% , P\u2009=\u20090.0005).HLA\u2010ls Table  and 3. ADQA1*05:01:01 occurred in 64% of the CD children , P\u2009=\u20093.82\u2009\u00d7\u200910\u2212105), DQA1*03:01:01 in 31% , P\u2009=\u20092.92\u2009\u00d7\u200910\u221218) and DQA1*03:02:01 in 2.5% , P\u2009=\u20090.002). The DQB1*02:01:01 allele occurred in 54% of the CD children , P\u2009=\u20092.06\u2009\u00d7\u200910\u2212109) and DQB1*03:02:01 in 33% , P\u2009=\u20091.46\u2009\u00d7\u200910\u221222). DQB1*04:02:01 occurred in 1% , P\u2009=\u20090.0001).Among the HLA\u2010DQA1 and DQB1 alleles, DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01 (DRB3\u2010DR3\u2010DQ2.5) was found in 46% of CD children , P\u2009=\u20091.12\u2009\u00d7\u200910\u221261) and DRB3*02:02:01\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01 in 3% , P\u2009=\u20090.0496). On a genotype level, a total of 29 different haplotype combinations were found in CD children compared with 315 in controls. Being homozygous for DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01(DR3\u2010DQ2.5/DR3\u2010DQ2.5) was the most significant genotype (43) of CD group when compared to the control group , P\u2009=\u20091.42\u2009\u00d7\u200910\u221257, Data not shown).A complete list of HLA\u2010DRB\u2010DQA1\u2010DQB1 haplotypes is summarized in Table S4. Of these, only two haplotypes were observed more frequently in CD children compared with controls: 3.2DRB345, \u2010DRB1, \u2010DQA1 and \u2010DQB1 allele frequencies in T1D children and controls are summarized in Table S2. Of these alleles, DRB4*01:03:01 was found in 55% of T1D children , P\u2009=\u20091.07\u2009\u00d7\u200910\u221214), DRB3*01:01:02 in 34% , P\u2009=\u20097.29\u2009\u00d7\u200910\u221207), DRB3*02:02:01 in 4.4%, which were less frequent compared with controls , P\u2009=\u20090.0003). The DRB1*04:01:01 allele was the most frequent DRB1 allele and occurred in 39% , P\u2009=\u20094\u2009\u00d7\u200910\u221222), followed by DRB1*03:01:01 in 38% , P\u2009=\u20091.05\u2009\u00d7\u200910\u221215), and DRB1*04:04:01 in 11% , P\u2009=\u20090.002). The DQA1*03:01:01 allele occurred in 52% of T1D children , P\u2009=\u20095.38\u2009\u00d7\u200910\u22123) and DQA1*05:01:01 in 38% , P\u2009=\u20091.05\u2009\u00d7\u200910\u221215). DQB1*03:02:01 was present in 54% , P\u2009=\u20091.29\u2009\u00d7\u200910\u221235) and DQB1*02:01:01 in 37.5% , P\u2009=\u20094.43\u2009\u00d7\u200910\u221217). DPB1*04:02:01 occured in 2.2%, which was less frequent compared with controls , P\u2009=\u20090001). In contrast, DPB1*01:01:01 was associated with increased risk , P\u2009=\u20090007).HLA\u2010DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01 (DRB4\u2010DR4\u2010DQ8) was more frequently found in T1D children (11%) compared with controls , P\u2009=\u20090.01). On a genotype level, 20 different different haplotype combinations were identified. Among those, DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01(DR3\u2010DQ2.5/DR3\u2010DQ2.5) was found in 4.4% of T1D children , P\u2009=\u20090.0339, Data not shown).Haplotype frequencies in T1D children are summarized in Table S5. Only 3.3DRB4*01:03:01 was the most frequent occurring allele and found in 71.4% of T1D w/CD children , P\u2009=\u20090.0002), in comparison to 14.3% that carried either DRB3*01:01:02 or DRB3*02:02:01(P \u2264 0.999). DRB1*04:01:01 was present in 64% of T1D w/CD , P\u2009=\u20091.53\u2009\u00d7\u200910\u221206), DRB1*03:01:01 in 29% , P\u2009=\u20090.08). DQA1*03:01:01 was present in 57% of T1D w/CD children , P\u2009=\u20091.07\u2009\u00d7\u200910\u221206) and DQA1*05:01:01 in 29% . DQB1*03:02:01 occurred in 71% of T1D w/CD children , P\u2009=\u20097.95\u2009\u00d7\u200910\u221207) and DQB1*02:01:01 in 29% , P\u2009=\u20090.06). Haplotype distributions are listed in Table S6. Among those, only DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01 occurred more frequently in T1D w/CD children compared with controls and found in 42.9% , P\u2009=\u20093.75\u2009\u00d7\u200910\u22129). Four different DRB3 DRB4 DRB5\u2010DRB1\u2010DQA1\u2010DQB1 genotypes were found among T1D w/CD children, but there was no difference compared with controls.HLA class II alleles frequencies are summarized in Table S3. 3.4DRB3, \u2010DRB4, \u2010DRB5 alleles using RPE analysis (Table S1\u2010S2\u2010S3), DRB4*01:03:01 rank higher in T1D and T1D w/CD predisposition than DRB3*01:01:02, which rank higher in CD predisposition in comparison to the control group. DRB4*01:03:01 occurred in 55% of T1D children , P \u2009=\u20091.59\u2009\u00d7\u200910\u221206) and 71% of T1D w/ CD children , P\u2009=\u20090.003), which was higher compared with 32% of CD children. The opposite was true for DRB3*01:01:02, which was found in 60% of CD children compared with 33% of T1D children , P\u2009=\u20097.17\u2009\u00d7\u200910\u221209) , P\u2009=\u20096.3\u2009\u00d7\u200910\u201006) and 64% of T1D w/CD children , P\u2009=\u20090.0004) compared with only 19% of CD children, whereas DRB1*03:01:01 was found in 66% of CD children compared with 37% in T1D , P\u2009=\u20093.28\u2009\u00d7\u200910\u221209) and 28% of T1D w/CD , P\u2009=\u20090.009), respectively , P\u2009=\u20093.28\u2009\u00d7\u200910\u221209) and 28% of T1D w/CD , P\u2009=\u20090.009), respectively. In contrast, DQB1*03:02:01 was more frequently found in T1D (54%) but not compared with CD (34%) , P\u2009=\u20092.36\u2009\u00d7\u200910\u221205) compared with 71% of T1D w/CD , P\u2009=\u20090.007).By estimating the hierarchy of risk among all \u2010DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01 (DRB3\u2010DR3\u2010DQ2.5) was the most common haplotype and occurred in 45% of CD children compared with 5% in T1D (P\u2009=\u20095.89\u2009\u00d7\u200910\u221218), while DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*03:01:01\u2010DQB1*02:01:01 was the most common haplotype in T1D. The DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01 (DR4\u2010DQ8) haplotype was carried in 42% of T1D w/CD children compared with 11% in T1D , P\u2009=\u20090.001) and 7.8% in CD , P\u2009=\u20095.33\u2009\u00d7\u200910\u221206) children  was the most frequent genotype and found in 43% of CD children compared with 4.4% in T1D , P\u2009=\u20097.92\u2009\u00d7\u200910\u221211, Data not shown). In T1D, the DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*03:01:01\u2010DQB1*02:01:01/DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*05:01:01\u2010DQB1*03:02:01 (DR3\u2010DQ2/DR4\u2010DQ8) genotype was found in 38% of T1D children compared with 17% of CD children , P\u2009=\u20090.0002) and 28% of children with T1D w/CD . In T1D w/CD, being homozygous for DRB4*01:03:01\u2010DRB1*04:01:01\u2010DQA1*05:01:01\u2010DQB1*03:02:01 (DR4\u2010DQ8/DR4\u2010DQ8) was the most frequent genotype and found in 42% , P\u2009=\u20090.002) compared with 3.2% in CD and 10% in T1D , P\u2009=\u20090.04, Data not shown) children, respectively.In CD children, the 4DRB4*01:03:01, DRB3*01:01:02, and DRB3*02:02:01 alleles, were found to be associated with T1D w/CD. Of these three alleles DRB4*01:03:01 was associated with T1D only, DRB3*01:01:02 was associated with CD only, but inversely associated with T1D only. The DRB3*02:02:01 allele was associated with a low predisposition in all three groups. The novelty of the study lies in the fact that several alleles in DRB3, DRB4 and DRB5 among T1D w/CD children seem to have an extended HLA polymorphism more similar to that in children with T1D than that in children with CD.The present study aimed to fill the gap of knowledge of why some children with either T1D or CD are at an increased risk for developing both diseases (T1D w/CD) by analyzing extended HLA class II genes. The main findings were that the DRB4*01:03:01\u2010containing haplotypes conferred a positive association with T1D w/CD as well as T1D in comparison to DRB3*01:01:02\u2010containing haplotypes that were positively associated with CD. Around 50% of T1D and 70% of T1D w/CD haplotypes carry the former allele compared with 60% of CD haplotypes which carry the latter allele. Noting that all copies of chromosome 6 have a DRB1 locus, and most, but not all, have a functional second DRB locus, DRB4 was shown to be secondary for DRB1*04 haplotypes. The increase of DRB4*01:03:01 on DRB1*04:01 haplotypes in DRB1*04:01/*04:01 T1D w/CD case subjects versus DRB1*03:01/DRB1*04:01 case subjects and control subjects could reflect linkage of disequilibrium (LD) with alleles at other high\u2010risk loci. The analyses of the extended DRB1\u2010DRB3\u2010DRB4\u2010DRB5 haplotypes suggests that the risk for developing both diseases likely resembles T1D risk.Dissecting the extended DRB1\u2010DRB3\u2010DRB4\u2010DRB5 haplotypes, On a genotype level, differences between T1D w/CD and T1D children were found of whom T1D w/CD children were more likely to be homozygous for DR4\u2010DQ8/DR4\u2010DQ8 compared with T1D children. In line with other studies, the DR3\u2010DQ2 haplotype occurred in over a third of T1D children,trans, in addition to the DQ molecules encoded by alleles in cis, in linkage disequilibrium; DQA1*05, and DQB1*02, encoding the DQ2.5 molecule, and DQA1*03 and DQB1*03, encoding the DQ8 molecule.The suggested hypothesis for the increased susceptibility to CD and T1D coexistence is the putative presence of DQ heterodimers encoded by alleles in The strengths of the present study were the use of high\u2010resolution NGTS for extended HLA genotyping, which enabled examining the disease susceptibility between T1D w/CD and extended HLA\u2010DRB3, DRB4 and DRB5 alleles. The RPE analysis used to estimate the association between HLA alleles (or haplotypes) and each of the outcomes  accounts for the fact that a high frequency of a given allele \u201cinduces\u201d a lower frequency of all other alleles, as their total must remain constant.DRB4*01:03:01 and DRB3*01:01:02 of which DRB4*01:03:01 conferred the strongest risk allele for developing T1D w/CD.In conclusion, NGTS for genetic risk profiling of children with T1D and CD showed shared risk associations with The authors have declared no conflicting interests.Table S1 RPE analysis of the estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 alleles among celiac patients and population controls. (XLSX)Table S2 RPE analysis of the estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 alleles among type 1 diabetes patients and population controls. (XLSX)Table S3 RPE analysis of the estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 alleles among type 1 diabetes with celiac disease patients and population controls. (XLSX)Table S4 RPE analysis of estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 haplotypes among celiac patients and population controls. (XLSX)Table S5 RPE analysis of estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 haplotypes among type 1 diabetes and population controls. (XLSX)Table S6 RPE analysis of the estimated frequencies of HLA\u2010DRB3, DRB4, DRB5, DRB1, DQA1 and DQB1 haplotypes among type 1 diabetes with celiac disease and population controls. (XLSX)Click here for additional data file."}
{"text": "Kampert et al. express questions regarding (1) the measurement of pulmonary function, (2) listing of the data, (3) and a model of blood flow redistribution at peak exercise described by Harms et al. In addition, (4) they comment on the peak metabolic demand of the three conditions.p = 0.001, tidal volume sm \u22129.9\u2009\u00b1\u200911.3% and ffpm: \u221214.4\u2009\u00b1\u200913.0%, p = 0.016, inhalation time sm: +12\u2009\u00b1\u200915%, ffpm: +19\u2009\u00b1\u200916%, p < 0.001, compared to nm.Ad 1: During CPET, VE sm: \u221212.0\u2009\u00b1\u200912.6%, ffpm: \u221223.1\u2009\u00b1\u200913.6%, Ad 2: The complete results are listed in Tables 2 and 3.Ad 3: Harms et al. 1998) were cited describing possible changes in the distribution of total blood flow with additional work of breathing (e.g. higher breathing resistance) [998 were p\u00a0=\u00a00.596).Ad 4: At maximum load, the metabolic demands were similar in all three conditions. The respiratory exchange ratio (RER) did not differ between the tests (nm 1.13\u00a0\u00b1\u00a00.08, sm 1.15\u00a0\u00b1\u00a00.09, ffpm 1.13\u00a0\u00b1\u00a00.08, one-way ANOVA A straightforward way to get a feeling for the clear results of the study could be to personally try out the effects of sm and ffpm during exercise."}
{"text": "The structure of the title compound exhibits a folded conformation with the three arms all on the same side of the tertiary N atom. The crystal packing features \u03c0\u2013\u03c0 inter\u00adactions. 29H26N4O6, exhibits a folded conformation with the three arms all on the same side of the tertiary N atom. The two phthalimide units make a dihedral angle of 12.18\u2005(12)\u00b0 and the dihedral angles between the benzyl plane and the phthalimide units are 68.08\u2005(7) and 67.71\u2005(7)\u00b0. The crystal packing features \u03c0\u2013\u03c0 inter\u00adactions.The structure of the title compound, C There is also a longer centrosymmetric interaction of the nitro benzyl groups (N4/C24\u2013C29) with a distance of 4.694\u2005(5)\u2005\u00c5.The crystal structure consists of centrosymmetrical dimers with off-set \u03c0\u2013\u03c0 stacking between phthalimide groups (N3/C15\u2013C22) running along the on Fig.\u00a02. The cenet al., 20162CH2CH2N)3 resulted in 149 entries. Similar off-set \u03c0\u2013\u03c0 stacking was seen in another compound with two phthalimide groups . 3,3\u2032-Diphthal\u00adimido\u00addi\u00adpropyl\u00adamine , 2-nitro\u00adbenzyl\u00adchloride , and potassium carbonate  were heated at 433\u2005K for one\u2005h to give the title compound. Crystals suitable for X-ray analysis were slowly grown from chloro\u00adform.The title compound was prepared by using a previously reported method (Keypour Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989020016771/zn2003sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020016771/zn2003Isup4.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020016771/zn2003Isup3.cmlSupporting information file. DOI: 2052908CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, mol\u00adecules are linked through C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains parallel to the [010] direction. The mol\u00adecular geometry in the ground state was been calculated using DFT. Additionally, frontier mol\u00adecular orbital and mol\u00adecular electrostatic potential map analyses were performed. 14H12ClNO, the mol\u00adecules are linked through C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains parallel to the [010] direction. \u03c0\u2013\u03c0 inter\u00adactions and intra\u00admolecular hydrogen bonds are also observed. The mol\u00adecular geometry of the title compound in the ground state has been calculated using density functional theory at the B3LYP level with the 6\u2013311++G basis set. Additionally, frontier mol\u00adecular orbital and mol\u00adecular electrostatic potential map analyses were performed.In the crystal structure of the title compound, C The mol\u00adecular structure has two planar rings. The whole mol\u00adecule is approximately planar, with a maximum deviation of \u22120.0236\u2005(12)\u2005\u00c5 from planarity for the C8 atom of Schiff base. The title compound displays an E configuration with respect to the C8=N double bond. The dihedral angle between the two phenyl ring planes is 0.34\u2005(9)\u00b0 and the C5\u2014C8\u2014N1\u2014C9 torsion angle is \u2212179.81\u2005(15)\u00b0. The planar mol\u00adecular conformation is stabilized by the intra\u00admolecular O1\u2014H1\u22efN1 hydrogen bond, which forms an S(6) motif.The structure of the title compound (I)In the crystal, the mol\u00adecules are linked by C10\u2014H10\u22efO1 hydrogen bonds Table\u00a01, generaton Fig.\u00a02. C\u2014H\u22ef\u03c0 ion Fig.\u00a02. \u03c0\u2013\u03c0 staet al., 2016E)-2-{[(3-chloro\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-6-methyl\u00adphen\u00adol structure. With a value of 1.271\u2005(2)\u2005\u00c5, the N1\u2014C8 bond in the title compound (I)E)-(5-chloro-2-methyl\u00adphen\u00adyl)imino\u00admeth\u00adyl]-4-methyl\u00adphenol -imino\u00admeth\u00adyl]phenol salicylaldimine -2-[(3-chloro\u00adphenyl\u00adimino)\u00admeth\u00adyl]-4-meth\u00adoxy\u00adphenol -[imino]\u00admeth\u00adyl}benzene-1,2-diol salicylaldimine  level  and ionization potential (IP) can be defined as A = \u2212ELUMO and IP = \u2212EHOMO. Additionally, these values can also be used calculate the electronegativity (\u03c7), chemical hardness (\u03b7) and chemical softness (S)  method. In Fig.\u00a05The analysis of a three-dimensional plot of the mol\u00adecular electrostatic potential (MEP) surface is a technique for mapping the electrostatic potential onto the isoelectronic density surface, providing information about the reactive sites. The surface simultaneously displays mol\u00adecular size and shape and the electrostatic potential value. In the colour scheme adopted, red indicates an electron-rich region with a partial negative charge and blue an electron-deficient region with partial positive charge, light blue indicates a slightly electron-deficient region, yellow a slightly electron-rich region and green a neutral region  and 4-chloro\u00adaniline  was stirred with ethanol (30\u2005mL) at 377\u2005K for 4\u2005h, affording the title compound . Single crystals suitable for X-ray measurements were obtained by recrystallization from methanol at room temperature.Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019017353/mw2154sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019017353/mw2154Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019017353/mw2154Isup3.cmlSupporting information file. DOI: 1974885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Pbca. The phenol ring is inclined to the benzo\u00adnitrile ring by 25.65\u2005(3)\u00b0. The configuration about the C=N bond is E, stabilized by a strong intra\u00admolecular O\u2014H\u22efN hydrogen bond that forms an S(6) ring motif.The title compound crystallizes in the ortho\u00adrhom\u00adbic space group  15H12N2O, was synthesized by condensation reaction of 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde and 2-amino\u00adbenzo\u00adnitrile, and crystallizes in the ortho\u00adrhom\u00adbic space group Pbca. The phenol ring is inclined to the benzo\u00adnitrile ring by 25.65\u2005(3)\u00b0. The configuration about the C=N bond is E, stabilized by a strong intra\u00admolecular O\u2014H\u22efN hydrogen bond that forms an S(6) ring motif. In the crystal, C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions lead to the formation of sheets perpendicular to the a axis. C\u2014H\u22ef\u03c0 inter\u00adactions, forming polymeric chains along the a-axis direction, connect these sheets into a three-dimensional network. A Hirshfeld surface analysis indicates that the most important contributions for the packing arrangement are from H\u22efH and C\u22efH/H\u22efC inter\u00adactions. The density functional theory (DFT) optimized structure at the B3LYP/6\u2013311\u2005G level is compared with the experimentally determined mol\u00adecular structure and the HOMO\u2013LUMO energy gap is given.The title compound, C RCH=N\u2013R\u2032) are prepared by a condensation reaction between amines and reactive carbonyl compounds, such as aldehydes. Schiff bases are employed as catalyst carriers  and keto\u2013amine (NH) forms. Depending on the tautomers, two types of intra\u00admolecular hydrogen bonds are generally observed in ortho-hy\u00addroxy Schiff bases, namely O\u2014H\u22efN in enol\u2013imine and N\u2014H\u22efO in keto\u2013amine tautomers  ring motif . The C10\u2014O1 bond length [1.3503\u2005(17)\u2005\u00c5 for X-ray and 1.337\u2005\u00c5 for B3LYP] indicates single-bond character, while the imine C8=N2 bond length [1.2795\u2005(17)\u00c5 for X-ray and 1.291\u2005\u00c5 for B3LYP] indicates double-bond character. All bond lengths and bond angles are within normal ranges and are comparable with those in related Schiff base compounds . As shown in Fig.\u00a05b, the most widely scattered points in the fingerprint plot are related to H\u22efH contacts, which make a contribution of 39.2% to the Hirshfeld surface. There are also N\u22efH/H\u22efN , O\u22efH/H\u22efO  and C\u22efC  contacts, with smaller contributions from C\u22efN/N\u22efC (2.6%), C\u22efO/O\u22efC (0.4%) and N\u22efN (0.3%) contacts.In order to better visualize and analyze the role of weak inter\u00admolecular contacts in the crystal, a Hirshfeld surface (HS) analysis  calculations using the standard B3LYP functional and a 6-311G basis-set , the ionization potential (I = -ELUMO), HOMO\u2013LUMO energy gap (\u0394E), the chemical hardness (\u03b7) and softness (S) of the title compound were predicted based on the EHOMO and ELUMO energies  and the lowest-unoccupied mol\u00adecular orbital (LUMO) are very important parameters for quantum chemistry. Many electronic, optical and chemical reactivity properties of compounds can be predicted from frontier mol\u00adecular orbitals -2-{[(3-chloro\u00adphen\u00adyl)imino]\u00admeth\u00adyl}-6-methyl\u00adphenol -2-[(2-hy\u00addroxy-5-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile -2-[(5-bromo-2-hy\u00addroxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile \u00adbenzo\u00adnitrile -2-\u00adbenzo\u00adnitrile -2-(4-di\u00adethyl\u00adamino-2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00adben\u00adzo\u00adnitrile -2-[amino]\u00adbenzo\u00adnitrile  ring motif. The dihedral angles between the aromatic rings are generally smaller than the value of 25.65\u2005(3)\u00b0 observed for the title compound, with angles between 1.09\u2005(4)\u00b0 (for FOWXOF and GEJGAE) and 13.84\u2005(13)\u00b0 (for PUJDOO). Only YOVBUH features angles similar to those of (I)A search of the Cambridge Structural Database  in ethanol (15\u2005ml) and 2-amino\u00adbenzo\u00adnitrile  in ethanol (15\u2005ml) and stirring the mixture for 5\u2005h under reflux . Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.Uiso(H) = 1.2\u20131.5Ueq(C). The position of the H1 atom was obtained from a difference map; it was placed in a calculated position with a fixed C\u2014O\u2014H angle, but the O\u2014H distance and the torsion angle were allowed to freely refine.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020008907/zl2787sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008907/zl2787Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008907/zl2787Isup3.cmlSupporting information file. DOI: 2013269CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structures of the four isomeric hydrogen-bonded 1:1 co-crystals of 6-methyl\u00adquinoline with 2-chloro-4-nitro\u00adbenzoic acid, 2-chloro-5-nitro\u00adbenzoic acid, 3-chloro-2-nitro\u00adbenzoic acid and 4-chloro-2-nitro\u00adbenzoic acid have been determined at 185\u2013190\u2005K. In each crystal, the acid and base mol\u00adecules are linked by a short O\u2014H\u22efN hydrogen bond. 7H4ClNO4\u00b7C10H9N, namely, 2-chloro-4-nitro\u00adbenzoic acid\u20136-methyl\u00adquinoline (1/1), (I), 2-chloro-5-nitro\u00adbenzoic acid\u20136-methyl\u00adquinoline (1/1), (II), 3-chloro-2-nitro\u00adbenzoic acid\u20136-methyl\u00adquinoline (1/1), (III), and 4-chloro-2-nitro\u00adbenzoic acid\u20136-methyl\u00adquinoline (1/1), (IV), have been determined at 185\u2013190\u2005K. In each compound, the acid and base mol\u00adecules are linked by a short hydrogen bond between a carboxyl O atom and an N atom of the base. The O\u22efN distances are 2.5452\u2005(12), 2.6569\u2005(13), 2.5640\u2005(17) and 2.514\u2005(2)\u2005\u00c5, respectively, for compounds (I)\u2013(IV). In the hydrogen-bonded acid\u2013base units of (I), (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.65\u2005(3):0.35\u2005(3), 0.59\u2005(4):0.41\u2005(4) and 0.48\u2005(5):0.52\u2005(5), respectively, for (I), (III) and (IV). The H atom in the hydrogen-bonded unit of (II) is located at the O-atom site. In all of the crystals of (I)\u2013(IV), \u03c0\u2013\u03c0 inter\u00adactions between the quinoline ring system and the benzene ring of the acid mol\u00adecule are observed. In addition, a \u03c0\u2013\u03c0 inter\u00adaction between the benzene rings of adjacent acid mol\u00adecules and a C\u2014H\u22efO hydrogen bond are observed in the crystal of (I), and C\u2014H\u22efO hydrogen bonds and O\u22efCl contacts occur in the crystals of (III) and (IV). These inter\u00admolecular inter\u00adactions connect the acid and base mol\u00adecules, forming a layer structure parallel to the bc plane in (I), a column along the a-axis direction in (II), a layer parallel to the ab plane in (III) and a three-dimensional network in (IV). Hirshfeld surfaces for the title compounds mapped over dnorm and shape index were generated to visualize the weak inter\u00admolecular inter\u00adactions.The structures of the four isomeric compounds of 6-methyl\u00adquinoline with chloro- and nitro-substituted benzoic acids, C Ka values of the acids and bases as well as inter\u00admolecular inter\u00adactions in the crystals. In our ongoing study on crystal structures of the system of quinoline derivatives\u2013chloro- and nitro-substituted benzoic acids, we have shown that three compounds of quinoline with 3-chloro-2-nitro\u00adbenzoic acid, 4-chloro-2-nitro\u00adbenzoic acid and 5-chloro-2-nitro\u00adbenzoic acid, the \u0394pKa [pKa(base)\u00a0\u2212\u00a0pKa(acid)] values of which are 3.08, 2.93 and 3.04, respectively, have a short double-well O\u2014H\u22efN/O\u22efH\u2014N hydrogen bond between the carb\u00adoxy O atom and the aromatic N atom , 8-hy\u00addroxy\u00adquinolinium 3-chloro-2-nitro\u00adbenzoate (\u0394pKa = 3.02) and 3-chloro-2-nitro\u00adbenzoic acid\u20135-nitro\u00adquinoline (1/1) (\u0394pKa = 0.98) , 5-chloro-2-nitro\u00adbenzoic acid\u20135-nitro\u00adquinoline (1/1) (\u0394pKa = 0.94) \u2013(IV).Properties of hydrogen bonds formed between organic acids and organic bases depend on the pThe mol\u00adecular structures of compounds (I)\u2013(IV) are shown in Fig.\u00a01In the hydrogen-bonded acid\u2013base unit of compound (I)Similar to (I)P212121. In the acid\u2013base unit, the quinoline ring system and the benzene ring of the acid are slightly twisted to each other with a dihedral angle of 14.50\u2005(5)\u00b0. The quinoline ring system and the carb\u00adoxy group are also slightly twisted with a dihedral angle of 12.55\u2005(18)\u00b0. The benzene ring makes dihedral angles of 3.14\u2005(18) and 85.04\u2005(11)\u00b0, respectively, with the carb\u00adoxy group and the nitro group.Compound (III)Cc. In the acid\u2013base unit, the quinoline ring system and the benzene ring of the acid are twisted to each other with a dihedral angle of 30.39\u2005(9)\u00b0. The quinoline ring system and the carb\u00adoxy group are also twisted with a dihedral angle of 21.7\u2005(3)\u00b0. The benzene ring makes dihedral angles of 16.4\u2005(3) and 74.4\u2005(3)\u00b0, respectively, with the carb\u00adoxy group and the nitro group.Compound (IV)i; symmetry code as given in Table\u00a01c-axis direction  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01]. The dimeric units are further linked into a column structure stacked along the b-axis direction through a weak \u03c0\u2013\u03c0 inter\u00adaction between the benzene rings with Cg1\u22efCg1iv = 3.9401\u2005(6)\u2005\u00c5 . The mol\u00adecular chains are thus stacked into a layer parallel to the bc plane via these \u03c0\u2013\u03c0 inter\u00adactions.In the crystal of (I)on Fig.\u00a02. The aciit Fig.\u00a03; the cenvia \u03c0\u2013\u03c0 inter\u00adactions between the acid benzene ring and the quinoline ring system, so that the hydrogen-bonded acid\u2013base units related by an inversion center are linked into a column structure along the a-axis direction  \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (ii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01]. There are no significant inter\u00adactions between the columns.In the crystal of (II)on Fig.\u00a04. The ceni; symmetry code as in Table\u00a03b-axis direction , 3.6126\u2005(8) and 3.6393\u2005(8)\u2005\u00c5, respectively, for Cg1\u22efCg2iii, Cg1\u22efCg3iii and Cg1\u22efCg3iv, where Cg1, Cg2 and Cg3 are the centroids of the C1\u2013C6, N2/C8\u2013C11/C16 and C11\u2013C16 rings, respectively  is observed between the layers.In the crystal of (III)on Fig.\u00a05. The aciem Fig.\u00a06, and thuc-axis direction \u2005\u00c5; (ii) x, \u2212y, z\u00a0+\u00a0a-axis direction via \u03c0\u2013\u03c0 inter\u00adactions between the acid ring and the quinoline ring system  x\u00a0\u2212\u00a0y\u00a0+\u00a0z\u00a0\u2212\u00a0x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0\u2212\u00a0In the crystal of (IV)on Fig.\u00a07 via C\u2014H\u22efem Fig.\u00a08, and thudnorm and shape index \u2013(IV) mapped over et al., 2016trans-but-2-enedioic acid) \u2013(IV) were obtained by slow evaporation from aceto\u00adnitrile solutions of 6-methyl\u00adquinoline with chloro-nitro\u00adbenzoic acids in a 1:1 molar ratio at room temperature [80\u2005ml aceto\u00adnitrile solution of 6-methyl\u00adquinoline (0.20\u2005g) and chloro-nitro\u00adbenzoic acid (0.28\u2005g for each acid)].Uiso(H) = 1.5Ueq(N or O); the refined distances are given in Tables 1Uiso(H) = 1.2 or 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989020013134/hb7946sup1.cifCrystal structure: contains datablock(s) global, I, II, III, IV. DOI: 10.1107/S2056989020013134/hb7946Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020013134/hb7946IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989020013134/hb7946IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989020013134/hb7946IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989020013134/hb7946Isup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020013134/hb7946IIsup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020013134/hb7946IIIsup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020013134/hb7946IVsup9.cmlSupporting information file. DOI: 2034476, 2034475, 2034474, 2034473CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supra\u00admolecular network is consolidated by hydrogen-bonding inter\u00adactions primarily with nitro\u00adgen, sulfur and chlorine atoms, as well as parallel displaced \u03c0-stacking of the aryl rings. The UV\u2013vis, IR, and CV data are also consistent with monoanionic di\u00adthiol\u00adene ligands and an overall CoII oxidation state.The title compound, bis\u00ad(1,2-diphenyl-2-sulfanyl\u00adidene\u00adethane\u00adthiol\u00adato-\u03ba The cobalt di\u00adthiol\u00adene core is approximately planar, with angles of 89.73\u2005(2)\u00b0 for S1\u2014Co1\u2014S2, 88.93\u2005(2)\u00b0 for S1\u2014Co1\u2014S3, 88.41\u2005(2)\u00b0 for S2\u2014Co1\u2014S4, and 89.90\u2005(2)\u00b0 for S3\u2014Co1\u2014S4. The sum of the angles is 356.97\u2005(4)\u00b0, consistent with only a slight distortion from planarity. The PTA ligand occupies a 5th coordination site with angles of 101.94\u2005(2)\u00b0 for P1\u2014Co1\u2014S1, 98.12\u2005(2)\u00b0 for P1\u2014Co1\u2014S2, 90.97\u2005(2)\u00b0 for P1\u2014Co1\u2014S3, and 97.22\u2005(2)\u00b0 for P1\u2013Co1\u2014S4. Therefore, the overall geometry of [Co(pdt)2(PTA)] is approximately square pyramidal.[Co(pdt)p-anisyl-substituted analogues with PMe3 and PPh3 2(PTA)] is attributed to the small cone angle of 103\u00b0 \u2005\u00c5 for Co1\u2014S1, 2.1669\u2005(6)\u2005\u00c5 for Co1\u2014S2, 2.1685\u2005(5)\u2005\u00c5 for Co1\u2014S3, and 2.1487\u2005(5)\u2005\u00c5 for Co1\u2014S4. These are mostly within the range of Co\u2014S distances of 2.1659\u2005(9)\u20132.1765\u2005(9)\u2005\u00c5 reported for the p-anisyl-substituted analogues with PMe3 and PPh3, respectively \u2005\u00c5 for S1\u2014C7, 1.719\u2005(2)\u2005\u00c5 for S2\u2014C8, 1.729\u2005(2)\u2005\u00c5 for S3\u2014C21, and 1.731\u2005(2)\u2005\u00c5 for S4\u2014C22. These are mostly within the range of S\u2014C distances of 1.721\u2005(2)\u20131.726\u2005(3) and 1.730\u2005(3)\u20131.742\u2005(3)\u2005\u00c5 reported for the 2(PTA)] and one mol\u00adecule of 1,2-dicholorethane are present in the unit cell, as depicted in Fig.\u00a03ii distance of 2.78\u2005\u00c5 \u00c5 Figs. 3, #2 \u25b8 anb axis, parallel displaced \u03c0-stacking of the aryl rings is revealed \u2005\u00c5 apart \u00b0, while the sum of the angles is 356.97\u2005(6)\u00b0 for the PMe3 complex. Similarly, the phosphine in PPh3 is axially distorted because of the steric bulk of the phenyl groups, resulting in two more obtuse bond angles for S2\u2014Co1\u2014P1 and S3\u2014Co1\u2014P1 of 101.31\u2005(3) and 106.6\u2005(3)\u00b0, respectively. The other bond angles of 92.81\u2005(3)\u00b0 for S1\u2014Co1\u2013P1 and 97.13\u2005(3)\u00b0 for S4\u2014Co1\u2014P1 are within the range of S\u2014Co1\u2014P1 angles of 91.19\u2005(3) to 99.65\u2005(3)\u00b0 observed for the PMe3 complex.A survey of the Cambridge Structural Database ] was conducted in di\u00adchloro\u00admethane  transition, based on comparison with the related iron complex with PPh3  complex. The IR signal for [Co(pdt)2(PTA)] at 1157.61\u2005cm\u22121 is characteristic of monoanionic di\u00adthiol\u00adenes with a \u03c0-radical when coordinated to metals, and is attributed to \u03bd(C=S\u00b7) ne Fig.\u00a05 and reve2(PTA)] was collected in a solution of dichoro\u00admethane with a platinum working electrode  of [Co(pdt)de Fig.\u00a06 and a glde Fig.\u00a06. Both CV2(pdt)4]  and PTA  under an N2 atmosphere. To this mixture of solids, 20\u2005mL of CH2Cl2 were added and stirred for 4\u2005h at room temperature. The solvent was removed under reduced pressure and the resulting dark-orange solid was washed with 3 \u00d7 5\u2005mL of Et2O and dried under vacuum. The product was stable under reduced pressure and at room temperature. Yield: 92% . Crystals suitable for X-ray diffraction were grown by the vapor diffusion method with diffusion of pentane over a 1,2-di\u00adchloro\u00adethane solution of the compound. UV\u2013Vis spectra were obtained at ambient temperature with a Varian Cary 50 diode array spectrometer, while IR spectra were taken neat with an ALPHA FTIR instrument. Electrochemical measurements were performed with a CHI600E electroanalyzer workstation using an Ag/AgCl reference electrode, a platinum disk working electrode, a platinum wire auxiliary electrode, and [nBu4N][PF6] as the supporting electrolyte in CH2Cl2. Under these conditions, the [Cp2Fe]+/ Cp2Fe couple consistently occurred at +440\u2005mV. UV\u2013vis in CH2Cl2: : 301\u2005nm (17881), 877\u2005nm (6428). IR spectroscopy (cm\u22121): 3366.53 (w), 3054.34 (w), 2928.02 (w), 2869.68 (w), 1592.50 (w), 1440.63 (m), 1415.07 (s), 1275.25 (m), 1240.54 (w), 1157.61 (m), 1091.56 (s), 1012.49 (m), 969.10 (s), 940.65 (vs), 739.50 (s), 693.31 (s).A 50\u2005mL Schlenk flask containing a stir bar was charged with [Co2, respectively, and refined using a riding model with Uiso(H) = 1.2 Ueq(C) for CH and CH2.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989020005447/zl2776sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020005447/zl2776Isup2.hklStructure factors: contains datablock(s) I. DOI: 1986931CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-019-42476-4, published online 11 April 2019Correction to: The original version of this Article contained errors.In the Abstract,\u201cThe comparison of the mean load to failure of all 3 groups  did not reveal a significant difference.\u201dnow reads:\u201cThe comparison of the mean load to failure of all 3 groups  did not reveal a significant difference.\u201dIn Table 1,2\u201d.\u201cStiffness in N/mmnow reads:\u201cStiffness in N/mm\u201d2\u201d, row r7,Furthermore, in column \u201cStrength in N/mm\u201c-27.1\u201dnow reads:\u201c27.1\u201dAdditionally Table 1 contained errors in the values in columns Stiffness in N/mm, Strength in N/mm\u00b2, Cross sectional area in mm\u00b2. The original Table\u00a0As a result of this, in the Results section,2 . There was no significant difference between mean stiffness  and strength . A detailed overview is presented in Table\u00a0\u201cThe mean cross sectional area of ROI (fracture region) was 1.81 mmnow reads:2 .There was no significant difference between mean stiffness  and strength . A detailed overview is presented in Table\u00a0\u201cThe mean cross sectional area of ROI (fracture region) was 1.72 mmAnd,\u201cNo significant difference in the load to failure values between the three groups was found (p\u2009\u2009=\u2009\u20090.113). The mean load to failure in group 1 was 28.7\u2009\u2009\u00b1\u2009\u20096.1\u2009N  compared to 23.8\u2009\u2009\u00b1\u2009\u20093.8\u2009N  in group 2. The mean load to failure in group 3 was 23.7\u2009\u2009\u00b1\u2009\u20095.7\u2009N .\u201dnow reads:\u201cNo significant difference in the load to failure values between the three groups was found (p\u2009=\u20090.113). The mean load to failure in group 1 was 28.7\u2009\u00b1\u20096.4\u2009N  compared to 23.7\u2009\u00b1\u20096.0\u2009N  in group 2. The mean load to failure in group 3 was 24.0\u2009\u00b1\u20093.9\u2009N .\u201dThese errors have now been corrected in the PDF and HTML versions of the Article."}
{"text": "Hydrogen bonding of the anions is restricted to F-atom acceptors only, with particularly strong N\u2013H\u22efF inter\u00adactions [N\u22efF = 2.5072\u2005(15)\u2005\u00c5] established by axial and cis-positioned equatorial F atoms.In the structure of the title salt, second-order Jahn\u2013Teller distortion of the coordination octa\u00adhedra around V ions is reflected by coexistence of short V\u2014O bonds and  7H12N6)[VOF5], second-order Jahn\u2013Teller distortion of the coordination octa\u00adhedra around V ions is reflected by coexistence of short V\u2014O bonds [1.5767\u2005(12)\u2005\u00c5] and trans-positioned long V\u2014F bonds [2.0981\u2005(9)\u2005\u00c5], with four equatorial V\u2014F distances being inter\u00admediate in magnitude [1.7977\u2005(9)\u20131.8913\u2005(9)\u2005\u00c5]. Hydrogen bonding of the anions is restricted to F-atom acceptors only, with particularly strong N\u2013H\u22efF inter\u00adactions [N\u22efF = 2.5072\u2005(15)\u2005\u00c5] established by axial and cis-positioned equatorial F atoms. Hirshfeld surface analysis indicates that the most important inter\u00adactions are overwhelmingly H\u22efF/F\u22efH, accounting for 74.4 and 36.8% of the contacts for the individual anions and cations, respectively. Weak CH\u22efF and CH\u22efN bonds are essential for generation of three-dimensional structure.In the structure of the title salt, (C MvOF5]2\u2212 series  of ions [VOF5] [VOF5] \u00b7[VOF5]2\u2212, which gives insight into the hydrogen-bonding behaviour of [VOF5]2\u2212 anions when combined with the bitopic nitro\u00adgen-rich 4,4\u2032-bis dication. This cation provides different kinds of hydrogen-bond donor sites complemented by triazole-N acceptors, which are relevant to many types of coordination and hydrogen-bonded systems \u2005\u00c5], which define the local polar axis of the anion. Four equatorial V\u2014F bonds 2\u2212 anions in the salts with (H2bipy)2+ 2+ cations  = 103.46\u2005(12) and 104.11\u2005(12)\u00b0 \u00b0 and N3\u2014C5\u2014C6\u2014C7 of \u221263.73\u2005(17)\u00b0. A diversity of metal complexes suggest nearlys equal occurrence of trans\u2013gauche and all-trans sequences for the present moiety \u2005\u00c5 .Primary strong N\u2014H\u22efF bonding links the ionic counterparts into chains, which aggregate forming layers parallel to the ks Fig.\u00a02. The firThe packing of the layers extends the structure in the third dimension. For every next layer of the succession, the direction of the primary N\u2014H\u22efF bonded chains is inclined by 56.8\u00b0 to the direction of chains from the preceding layer Fig.\u00a03. Links bet al., 2004CrystalExplorer17  to 1.3445 (blue) a.u. indicates a number of red spots related to hydrogen-bond contacts. Particularly prominent spots are associated with the strongest N\u2014H\u22efF bonds. However, even the C\u2014H\u22efF inter\u00adaction with the weakest of the present donors  is reflected by a red spot on the surface . In addition to this very sharp spike, the plot clearly reveals the more subtle feature of anion\u22ef\u03c0 bonding, which appears as a short spike at 2.7\u2005\u00c5 , 0.84\u2005ml of 7% aqueous HF solution (3.0\u2005mmol) and 2\u2005ml of water were placed in a Teflon vessel and heated in a steel bomb at 413\u2005K for 24\u2005h. Cooling to room temperature over a period of 48\u2005h afforded colourless crystals of the title salt, in a yield of 27\u2005mg (40%). Analysis (%) calculated for C7H12F5N6OV: C 24.57, H 3.54, N 24.57; found: C 24.38, H 3.49, N 24.70.The bitriazole was prepared in a yield of 33% by the acid-catalysed condensation of 1,3-di\u00adamino\u00adpropane and 2) = 0.98\u2005\u00c5; Uiso(H) = 1.2Ueq(CH) and 1.5Ueq(NH).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902000585X/hb7908sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698902000585X/hb7908Isup2.hklStructure factors: contains datablock(s) I. DOI: 1999654CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Of these compounds, 10 and 12 form 1D or 2D coordination polymers in the solid state. (Spectro)Electrochemical studies confirmed reversible Fc/Fc+ redox events between \u2212130 and 160\u2005mV. 1,6\u2010 and 2,7\u2010Substitution in 5\u2009a (E\u00b0\u2032=\u2212130\u2005mV) and 7\u2009a (E\u00b0\u2032=50\u2005mV) influences the redox potentials, whereas the ones of 5\u2009b and 7\u2009b (E\u00b0\u2032=20\u2005mV) are independent. Compounds\u20055\u2009b, 7\u2009b, 10, and 12 show single Fc oxidation processes with redox splittings between 70 and 100\u2005mV. UV/Vis/NIR spectroelectrochemistry confirmed a weak electron transfer between FeII/FeIII in mixed\u2010valent [5\u2009b]+ and [12]+. DFT calculations showed that 5\u2009bnon\u2010covalently interacts with the single\u2010walled carbon nanotube (SWCNT) sidewalls as proven by, for example, disentangling experiments. In addition, CV studies of the as\u2010obtained dispersions confirmed exohedral attachment of 5\u2009b at the SWCNTs.The synthesis of 1\u2010Fc\u2010 (\u03b75\u2010C5H5)) is discussed. Two of these compounds form 1D or 2D coordination polymers in the solid state. (Spectro)electrochemical studies confirmed reversible Fc/Fc+ redox events between \u2212130 and 160\u2005mV. With the example of 2,5\u2010Fc2\u2010cC4H2E (Fc=Fe(\u03b75\u2010C5H4)(\u03b75\u2010C5H5); E=O, S, NR), it could be shown that similar geometries and hence comparable electrostatic interactions enable a correlation between electrochemical and spectroscopic properties.Redox\u2010active ferrocenyl\u2010functionalized five\u2010non\u2010covalent interactions, for example, \u03c0\u2013\u03c0 stacking.Furthermore, aromatics are suitable to modify carbon nanotubes (CNTs) by + (NADH=dihydronicotinamide adenine dinucleotide).Ferrocene\u2010functionalized CNT nanohybrids have attracted much attention in the fields of (bio)analytical electrochemistry,N\u2010(pyren\u20101\u2010ylmethyl)propanamide to SWCNTs and tested as glucose sensor electrode materials.6)2.II/RuIII redox potential is stable over 200 cycles. Another hybrid material is CNT/cobalt bis\u2010pentyl]butyramide).Non\u2010covalently functionalized CNTs bearing a ferrocenyl substituent were recently obtained through \u03c0\u2010stacking of 3\u2010ferrocenyl\u2010Lately, we became interested in attaching redox\u2010active Fc\u2010functionalized polyaromatic hydrocarbons to SWCNTs as a way to achieve debundeling as well as to influence the electronic properties of the thus\u2010modified carbon nanotubes and to use them as field\u2010effect sensors.2\u2010, and 2,7\u2010Fc2\u2010pyrenes, 3,6\u2010Fc2\u20109,10\u2010phenanthrenedione, and 3,6\u2010Fc2\u20109,10\u2010dimethoxyphenanthrene compounds is discussed. Their (spectro)electrochemical properties and their molecular structures in the solid state are reported. DFT calculations for 1,6\u2010Fc2\u2010pyrene and semiconducting and metallic SWCNTs are provided, as well as the use of 1,6\u2010Fc2\u2010pyrene to disentangle SWCNTs. The electrochemical properties of the as\u2010obtained dispersions are presented.Hence, within this study, the synthesis and characterization of a series of 1\u2010Fc\u2010, 1,6\u2010Fc3, 5\u2009a,b, 7\u2009a, 10) or Negishi  C\u2212C cross\u2010coupling reactions were applied (\u03b75\u2010C5H5)) was treated with the respective 1\u2010Br\u2010 (2), 1,6\u2010Br2\u2010 (4), 2,7\u2010Br2\u2010pyrene (6), or 3,6\u2010Br2\u20109,10\u2010phenanthrenedione (9) in the presence of [PdCl2(dppf)] ferrocene) as the catalyst in the molar ratio of 1:1 or 2:1 in boiling toluene. After appropriate work\u2010up, compounds\u20053, 5\u2009a,b, 7\u2009a, and 10 could be isolated as orange  or green (10) solids in a yield of 3\u201365\u2009% . For comparison, compound 9\u2010ferrocenylphenanthren was synthesized according to the Suzuki C\u2212C cross\u2010coupling protocol used within the synthesis of 3, 5\u2009a,b, 7\u2009a, and 10 .Ferrocene boronic acid FcB(OH)1 with 1,6\u2010Br2\u2010C16H8 (4) in the molar ratio of 2:1, a mixture of the respective mono\u2010 and diferrocenyl\u2010functionalized pyrenes\u20055\u2009a,b was formed .In the transmetalation reaction of 1 with 2,7\u2010Br2\u2010C16H8 (6) in a 2:1 ratio in boiling toluene solely gave the monoferrocenyl\u2010substituted species 2\u2010Br\u20107\u2010Fc\u2010pyrene (7\u2009a), which was obtained as an orange solid in a yield of 32\u2009% after column chromatography 6 in the presence of 1.0\u2005mol\u2009% [PdCl2(dppf)] as the catalyst in boiling tetrahydrofuran produced 7\u2009b, however, in a yield as low as 2\u2009% . In this reaction, other than 7\u2009b, ferrocene was formed as the main product. Compound\u20057\u2009b is a very poorly soluble species in common polar organic solvents. Once 7\u2009b was isolated in its solid form, it was almost impossible to redissolve it and hence spectroscopic and electrochemical experimental data on this organometallic compound are limited.However, diferrocenyl pyrene\u200510 and 12 were synthesized by either the Suzuki\u2013Miyaura (10) or the Negishi (12) reaction starting from 3,6\u2010dibromophenanthrene\u20109,10\u2010dione 9  in toluene in the presence of catalytic amounts of [PdCl2(dppf)] led to the formation of green 3,6\u2010diferrocenylphenanthrene\u20109,10\u2010dione (10) in a yield of 28\u2009%. However, the synthetic methodology described by Phulwale et\u2005al. for the reduction of the ketone functionalities in 10 did not lead to the formation of the respective 3,6\u2010diferrocenyl\u20109,10\u2010dimethoxyphenanthrene compound\u200512.9 was performed prior to the C\u2212C cross\u2010coupling reaction. Thus, compound\u200511 could be isolated in virtual quantitative yield. Upon treatment of 11 with two equivalents of FcZnCl (8) in tetrahydrofuran as solvent for 24\u2005h in the presence of [PdCl2(dppf)] gave orange 12 in an overall yield of 13\u2009% .Compounds\u20055\u2009a,b, 7\u2009a,b, 10, and 12 was confirmed by elemental analysis, IR, 1H and 13C{1H} NMR spectroscopy, and high\u2010resolution ESI\u2010TOF mass\u2010spectrometry , whereas the physical and analytical data  of 3 are documented in reference\u20057\u2009b).The identity of 1H, 13C{1H} NMR) data of 3, 5\u2009a,b, 7\u2009a,b, 10, and 12 are consistent with their formulations as mono\u2010 or diferrocenyl\u2010functionalized pyrene, 9,10\u2010phenanthrenedione, and 9,10\u2010dimethoxyphenanthrene compounds, showing the characteristic coupling patterns of the appropriate isomers .7\u2009b no reliable 13C{1H} NMR data could be obtained, owing to its low solubility in common polar organic solvents (see above).The spectroscopic , I2/a (5\u2009a), P21/n (5\u2009b), or P21/c  and in the orthorhombic space groups Pnn2 (12) and P212121 (9\u2010ferrocenylphenanthrene) with one  or two (10) independent molecules in the asymmetric unit. Intermolecular \u03c0\u2013\u03c0 interactions were investigated between the aromatic entities and the ferrocenyl cyclopentadienyl units .The compounds crystallize in the monoclinic space groups ipso\u2010carbon atoms and the aromatic units is similar for all investigated compounds (from 1.476(3)\u2005\u00c5 (7\u2009a) to 1.554(8)\u2005\u00c5 (10)) and agree well with literature values.The distance between the ferrocenyl cyclopentadienyl  to 1.554\u2005\u00c5 (10)) In Tables\u2005SI3 and SI4 (in the Supporting Information), the bond lengths of the different aromatic cores are summarized. The substitution pattern does not affect the position of the single and double bonds in the aromatic moieties. This observation is in good agreement with values published for other substituted pyrenyl and phenanthrenyl derivatives.3, 5\u2009a,b, 7\u2009a,b, 12, and 9\u2010ferrocenylphenanthrene. Compounds containing hydrogen atoms in position 8 with regard to the Fc group  possess increased values of 31.5(5)\u00b0 (5\u2009b) to 40.05(10)\u00b0 (5\u2009a), owing to a steric interaction with the \u03b1\u2010H atoms of the ferrocenyls. In contrast, the geometric properties of the 2\u2010 or 3\u2010substitution pattern  allow for more planar intersections between 0.1(3)\u00b0 (10) and 22.1(9)\u00b0 (12). Hence, these compounds should be preferred to achieve a high degree of electron transfer interaction between the \u03c0\u2010system of the ferrocenyls and the aromatic cores.3, 5\u2009a,b, and 9\u2010ferrocenylphenanthrene argue for a weak interaction. In addition, the rms distortions (root mean square deviations) of the condensed aromatic units were calculated and are summarized in Table\u2005SI5 (in the Supporting Information), where 5\u2009a (0.0497) and 12 (0.0680) showed exceptional high values.The rotation of the ferrocenyls out of the aromatic co\u2010planarity was examined for 5\u2009b, 7\u2009b, 10, and 12 exhibit an anti\u2010positioning of the Fc groups towards each other with regard to the aromatic planes.10) to 12.7288(8)\u2005\u00c5 (7\u2009b). Thereby, the Fe\u22c5\u22c5\u22c5Fe distances in 10 (9.0374(13)\u2005\u00c5 Fe1\u2013Fe2; 9.0390(13)\u2005\u00c5, Fe3\u2013Fe4) and 12 (10.123(6)\u2005\u00c5) point towards a better electronic coupling between the ferrocenyl groups than in 5\u2009b (11.477(2)\u2005\u00c5) and 7\u2009b (12.7288(8)\u2005\u00c5).The diferrocenyl\u2010substituted compounds\u20053, 5\u2009a,b, 7\u2009a,b, 10, 12, and 9\u2010ferrocenylphenanthrene as \u03c0\u2010surfactants on CNTs, the interaction through intermolecular \u03c0/C\u2212H\u22c5\u22c5\u22c5\u03c0 bonding was investigated for the aromatic and ferrocenyl units . Except for 7\u2009b, all compounds show intermolecular \u03c0\u2013\u03c0 interactions , of which 3, 5\u2009b, and 9\u2010ferrocenylphenanthrene show T\u2010shaped \u03c0\u2010interactions between C5H5/C5H4 units and the aromatic moieties with distances of 4.5276(14) (3)\u20134.994(6)\u2005\u00c5 (5\u2009b). The solid\u2010state structures of 5\u2009a and 7\u2009a show T\u2010shaped and parallel displaced \u03c0\u2010interactions with distances between 4.6081(17) (5\u2009a) and 4.6925(14)\u2005\u00c5 (7\u2009a) and angles from 84.68(15) (5\u2009a) to 89.24(14)\u00b0 (7\u2009a). The parallel displaced \u03c0\u2010interactions between the pyrene cores of 5\u2009a and 7\u2009a show distances of approximately 3.6\u2005\u00c5, forming dimers .With regard to the utilization of 10 and 12, the parallel displaced \u03c0\u2010interactions between the arenes led to the formation of 1D (12) and 2D coordination polymers (10) along the a\u2010 (10) or b\u2010axis (12), resulting in the formation of columns . The columnar structure of 12 is based on the parallel displaced \u03c0\u2010interactions involving C11\u2013C16 of the phenanthrene with centroid\u2013centroid distances of 5.165(12)\u2005\u00c5, exceeding the criterion for \u03c0\u2010stacking (3.3\u20133.8\u2005\u00c5).In case of 10 builds a 2D coordination polymer, whereby both molecules of the asymmetric unit are responsible for the columnar structure. Parallel displaced \u03c0\u2010interactions between the ferrocenyl's cyclopentadienyls interconnect the columns. The arrangement along the a\u2010axis is based on the interactions between the arenes of the phenanthrene backbone with distances ranging from 3.589(3) to 4.549(3)\u2005\u00c5. Furthermore, this stacking is supported by \u03c0\u2010interactions involving the Fc\u2010C5H4 units and the aromatic moieties with distances ranging from 3.466(3) to 4.800(3)\u2005\u00c5 .Compound\u2005\u1e7dmax) of compound\u200510 were measured in a set of 23 common organic solvents of different polarities and hydrogen\u2010bonding abilities =658\u2005nm =553\u2005nm). This shift corresponds to a positive solvatochromism with a solvatochromic range of \u0394\u1e7dmax (10)=2880\u2005cm\u22121.Compound\u2005The interactions of solvatochromic dyes with pure solvents or solvent mixtures arise from a combination of many effects.\u03b1, \u03b2, and \u03c0*. In addition, \u1e7dmax,0 corresponds to a standard process, referenced to a nonpolar medium. The parameters a, b, and s represent solvent\u2010independent correlation coefficients, which reflect the relative effect of each of the three parameter \u03b1, \u03b2, and \u03c0*.According to Equation\u2005(1), the effect of hydrogen\u2010bonding donor capacity (HBD),\u03b1, \u03b2, and \u03c0* used for the multiple linear regression analysis are given in Table\u2005SI6 (in the Supporting Information).10, which is qualitatively the best according to the solvent scales of Kamlet\u2013Taft, is given in Table\u2005The solvent parameters r is greater than 0.90 for the LSE relationship, indicating a high validity of the multiparameter equation, allowing significant conclusions to be drawn. Compound\u200510 shows a positive solvatochromism with increasing acidity and dipolarity/polarizability of the solvents.The correlation coefficient s indicates that the electronically excited state of 10 becomes solvated stronger and is consequently stabilized with increasing solvent dipolarity/polarizability. Owing to the strength of the higher dipole moment, the energy of the electronically excited state decreases more than the energy of the ground state. This is in good agreement with a bathochromic shift of the UV/Vis absorption maxima with increased polarity of the solvent.The negative sign of a for 10 indicates that there is a bathochromic shift of \u03bbmax with increasing hydrogen\u2010bond donor capacity of the solvent (positive solvatochromism). Owing to the solvation of the carbonyl oxygen atom by HBD solvents the push\u2013pull character becomes enhanced. This effect is on the same order of magnitude as the influence of the dipolarity/polarizability. The hydrogen\u2010bond acceptor capacity of the solvents, on the other hand, has no influence on the solvatochromic behavior of 10 (b=0).The negative sign of parameter \u1e7dmax) of 1820\u20132460\u2005cm\u22121 in contrast to 10 with 2880\u2005cm\u22121, which indicates a stronger solvatochromic behavior.A similar behavior was observed for ferrocenyl\u2010substituted maleimides.3, 5\u2009a,b, 7\u2009a,b, 10, and 12 were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), and spectroelectrochemistry (in situ UV/Vis/NIR). As supporting electrolyte, an anhydrous dichloromethane solution containing 0.1\u2005mol\u2009L\u22121 of [NnBu4][B(C6F5)4] was used.6]\u2212 or [Cl]\u2212, [B(C6F5)4]\u2212 stabilizes highly charged species in solution and minimizes ion pairing effects.+ redox couple.\u22121 are summarized in Table\u2005The redox properties of compounds\u20053  as well as 5\u2009b, 7\u2009b, 10, and 12  show one  or two  reversible redox processes. The aromatic cores are characterized by a reversible (5\u2009a) or irreversible redox event  between 950 and 1250\u2005mV, however, for 7\u2009b, 10, and 9\u2010ferrocenylphenanthrene no oxidation of the aromatic core occurred under the applied measurement conditions.The Fc groups of 9\u2010ferrocenylphenanthrene and 5\u2009a, 7\u2009a), the substitution pattern  and the nature of the aromatic core . Comparison with 3 shows that the bromo substituent has a strong impact on the electron density at Fc, shifting the potential by 160\u2005mV anodically. The Fc\u2010based redox process of 7\u2009a is further shifted to 50\u2005mV (vs. FcH/FcH+) compared with 3. Positions 2 and 7 are electron\u2010poor5\u2009a. This observation is in contrast to the investigations of Fc\u2010substituted naphthalenes, where the influence of the substitution pattern is stronger than the impact of electron\u2010withdrawing entities like bromine.3 and 9\u2010ferrocenylphenanthrene, respectively. Dhokale et\u2005al. reported that 1\u2010ferrocenylpyrene and 1\u2010ferrocenylethynylpyrene show Fc\u2010based oxidations at 50 and 70\u2005mV when using [NnBu4][PF6] as the electrolyte versus a saturated calomel electrode (SCE).nBu4][B(C6F5)4] as a weakly coordinating electrolyte.Within the series of monoferrocenyl\u2010substituted pyrenes, compound\u20055\u2009b and 7\u2009b show a single redox event for both ferrocenyl groups at 20\u2005mV  and 100\u2005mV pyrene by using [NnBu4][PF6] as the electrolyte.tert\u2010butyl\u20109\u2009H\u2010carbazol\u20109\u2010yl)pyrene) to 100\u2005mV pyrene), which is in good agreement with the results observed for 5\u2009b and 7\u2009b.5\u2010C5Me5)(dppe)RuC\u2261C)2\u2010pyrene, which showed a value of 120\u2005mV.Diferrocenyl pyrenes es Table\u2005 point to10 and 12 were synthesized to investigate the influence of electron\u2010withdrawing and \u2010donating groups on the redox potential of the ferrocenyl oxidation. The methoxy\u2010functionalized compound\u200512 shows a redox process at 30\u2005mV (vs. FcH/FcH+). In contrast to that, the electron\u2010withdrawing keto groups in positions 9 and 10 of 10 decrease the electron density of the Fc entities and therefore shift the respective potential by 130\u2005mV anodically. The redox separation of 10 and 12 is lower than for the appropriate diferrocenyl\u2010substituted pyrenes\u20055\u2009b and 7\u2009b. By deconvolution of the SW voltammograms, redox splittings of 70 (10) and 80\u2005mV (12) were found, pointing to a weak metal\u2013metal interaction based on either electrostatic interactions or electron transfer  measurements were performed. Compound\u20057\u2009b could not be investigated by this method, owing to its low solubility. Furthermore, the UV/Vis/NIR investigations of 10 revealed no intervalence charge transfer (IVCT) absorption but a MLCT  transition, which is in good agreement with the postulated resonance structures (Scheme\u2005SI2 in the Supporting Information).For the purpose of classification, the electron transfer between the Fc/Fc5\u2009b and 12) or propylene carbonate solutions (12) containing 5\u2009b or 12 (2.0\u2005mmol\u2009L\u22121) and [NnBu4][B(C6F5)4] (0.1\u2005mol\u2009L\u22121) as supporting electrolyte in an OTTLE  cell.5\u2009b and 12. During the measurements, oxidation of the neutral compounds to mixed\u2010valent [5\u2009b]+ and [12]+ and finally to the fully oxidized species [5\u2009b]2+ and [12]2+ was observed  gave mixed\u2010valent species [5\u2009b]+ and [12]+ and hence a broad absorption within this area (800\u20133000\u2005nm) was observed. A further increase in the potential resulted in a decrease of this band, which is characteristic for intervalence charge transfer excitations  and therefore the small comproportionation constants  lead, in the best case, to a mixture consisting of an equilibrium of 73\u2009% mixed\u2010valent monocationic [12]+ as well as 13.5\u2009% neutral 12 and di\u2010cationic species [12]2+ each. As the composition of this equilibrium is not determinable by using an OTTLE cell, the extinction values are associated with considerable uncertainties.For neutral 5\u2009b and 12. The NIR data of the IVCT absorptions are summarized in Table\u2005The observed spectra were deconvoluted into three Gaussian\u2010shaped bands, which represent a LF (ligand field),5\u2009b and 12 showed no absorption in the NIR region, whereas mixed\u2010valent [5\u2009b]+ and [12]+ have weak and broad absorptions between 750 and 2000\u2005nm. The IVCT bands of Fc\u2010substituted aromatics 5\u2009b and 12 exhibit different characteristics . The highest intensity of 510\u2005L\u2009mol\u22121\u2009cm\u22121 was found for 575\u2005mV (vs. Ag/Ag+). From Figure\u2005SI20 (in the Supporting Information), it can be seen that in the series of increasing potential the IVCT absorption increases until its maximum at 575\u2005mV, followed by a decrease of intensity upon further oxidation to [5\u2009b]2+ and an increase of LMCT. The determined values of the IVCT absorption of 5\u2009b are in good agreement with 2,7\u2010bispyreneNeutral cs Table\u2005. For 5\u2009b12 leads to a more intense and narrow IVCT absorption  than in Fc2\u2010substituted pyrene 5\u2009b and is further shifted hypsochromically compared with the metal\u2013metal interaction band of 5\u2009b. This statement is based on the higher electron density of the dimethoxy\u2010substituted phenanthrene moiety, which was observed in the CV measurements (Table\u200512 is oxidized more easily (1110\u2005mV vs. FcH/FcH+) than the pyrenyl connectivity of 5\u2009b .The smaller \u03c0\u2010conjugated bridge present in \u03bc=4.9\u2005D) was further chosen as an additional solvent for the spectroelectrochemical measurements of 12. Analogous investigations on 5\u2009b failed in the UV/Vis/NIR setup, owing to its insufficient solubility in propylene carbonate. In the case of [12]+, the IVCT transition could be detected at approximately 11\u2009000\u2005cm\u22121 by using the solvent with higher polarity, revealing a solvatochromic shift (\u0394\u03bdmax) of 1000\u2005cm\u22121 (Table\u2005\u03bdmax in comparison for very strongly coupled systems (\u0394\u03bdmax\u2248100\u2005cm\u22121)Within these species, the IVCT bands typically show strong solvatochromism.3, 5\u2009a,b, 7\u2009a, and 12 were investigated, except for 10, which showed a MLCT . The UV/Vis/NIR spectra are depicted in Figures\u2005SI17\u2013SI19, SI21, SI22, SI24, and SI25 in the Supporting Information). The respective LMCT data of [3]+, [5\u2009a]+, [5\u2009b]2+, [7\u2009a]+, and [12]2+ are summarized in Table\u2005To gain a deeper insight into the communication between the aromatic core and the ferrocenyl ligands, the ligand\u2010to\u2010metal charge transfer properties of E\u00b0\u2032, the transition energy \u03bdmax is increased. The only exception is 1\u2010ferrocenylpyrene\u20053, which shows an anodic shift of its redox event and its transition at 8150\u2005cm\u22121. This might be based on the fact that the plane intersection of 3 in the solid state exhibits a rms value of 0.0348, which indicates a bent aromatic core. Further, the carbon atom C11 shows the highest displacement with 0.0685(17)\u2005\u00c5, confirming a weak interaction between the Fc and the arene moieties (Table\u2005SI5 in the Supporting Information). Equivalent correlations have been reported for charge transfer complexes, for example, ferrocenyl naphthalenes,5\u2009a with 7\u2009a, it is clear that a better communication between the Fc and the pyrene building blocks is given by the substitution in positions 1 and 6 than in 2 and 7, owing to higher intensity of the transition for 5\u2009a.The energy of the LMCT absorptions is related to the redox potentials of the Fc entities, displaying that with an increase of th 0.0685\u2005\u00c5, confi5\u2009b for disentangeling and modification studies of the SWCNTs surface. Hence, DFT calculations were additionally carried out to support the respective pyrene\u2013SWCNT interactions.Based on the spectroelectrochemical properties  and that the pyrene connectivity is favored to non\u2010covalently bind to CNTs,5\u2009b and SWCNTs. Here, we have considered both semiconducting \u2010SWCNT and metallic \u2010SWCNT as representative models of SWCNTs. Figure\u20055\u2009b on \u2010SWCNT. It was found that the pyrene group of 5\u2009b tends to orient parallel to the CNT surface owing to optimized \u03c0\u2013\u03c0 interactions. The computed pyrene\u2013CNT equilibrium distance and adsorption energy are 3.2\u2005\u00c5 and \u22121.26\u2005eV by using the PBE (Perdew\u2013Burke\u2013Ernzerhof) functional with empirical dispersion corrections (PBE\u2010D). In contrast, the plain DFT\u2010PBE calculations predict a much larger pyrene\u2013CNT equilibrium distance (4.1\u2005\u00c5) and a negligible adsorption energy (\u22120.1\u2005eV). These data indicate that the van der Waals forces are the dominant interactions between 5\u2009b and SWCNTs. This conclusion was also observed for the adsorption of 5\u2009b on a \u2010SWCNT surface, suggesting that the diameter and chirality of CNTs have only a small influence on the adsorption mechanism. Additionally, Mulliken population analysis was employed to study the charge transfer in the ground state. The calculation results reveal that only a few electrons (about 0.1\u2009e) are transferred from 5\u2009b to the CNT, which further confirms their \u03c0\u2013\u03c0 interactions.Density functional theory (DFT) calculations were performed to provide mechanistic insights into the interactions between 5\u2009b to interact with SWCNTs in a non\u2010covalent fashion in solution, debundeling experiments were performed with two commercially available materials: (i)\u2005chirality\u2010enriched \u2010SWCNTs as powder  and (ii)\u2005NanoIntegris IsoSol S\u2010100\u00ae SWCNT in dispersion. \u2010SWCNTs are, owing to their low purity, not suitable for electronic components but are an appropriate model system for the disentangling. However, the NanoIntegris IsoSol S\u2010100\u00ae SWCNT dispersion, consisting of up to 99.9\u2009% semiconducting material, has proven to be an appropriate material for the scalable fabrication of CNT transistors and sensorsTo investigate the ability of 5\u2009b was used for disentangling experiments with the NanoIntegris IsoSol S\u2010100\u00ae SWCNT dispersion and the results thereof are summarized in Figure\u20055\u2009b are presented in Figure\u2005SI26 (in the Supporting Information).As indicated above, compound\u20055\u2009b by using a vacuum filtration procedure aryl\u2010based polymer)Gen1 solid, both the S22 and S33 transitions of the SWCNT mixture as well as the PFH\u2010R transition remain unchanged from a spectral point of view, the relative composition of the absorption spectrum allows us to conclude a first successful depletion step for the reference solid through the vacuum filtration procedure. For the Gen2 solid, the spectrum clearly mimics the SWCNT signature from the Gen0 and Gen1 spectra as well as the particular PFH\u2010R transition (spectrum PFH\u2010R (toluene) mathematically deconvoluted from the spill liquid and the Gen0 spectrum). Additionally, the spectrum for the Gen2 solid shows a transition at 352\u2005nm, which can be identified as an absorption feature of 5\u2009b (measured spectrum 5\u2009b (toluene)), which unambiguously indicates that 5\u2009b is present in the redispersed SWCNT solid after the vacuum filtration procedure.In spectrum 0 Figure\u2005, the S225\u2009b was further confirmed by electrochemical measurements. The redox properties of the dispersion Gen2 ({5\u2009b}{PFH\u2010R}@SWCNT) were investigated by cyclic voltammetry by using Gen2\u2010modified graphene paper\u22121 KCl. The voltammetry measurements were performed at 25\u2009\u00b0C. All potentials are referenced to the SCE using K3[Fe(CN)6] as the internal standard.The functionalization of SWCNTs with Gen2 show a ferrocenyl\u2010based redox process at 380\u2005mV .The CVs of Ep value of the respective redox processes are characteristic.\u22121; Table\u2005i\u2248vr0.62; vr=sweep rate), which is far from a linear relationship, but also does not reflect the i\u2248\u221avr of a fully dissolved redox system. The redox processes of dispersion Gen2 show \u0394Ep values between 40 and 55\u2005mV . This emphasizes that 5\u2009b is exohedrally attached to the SWCNTs. In Gen2, where 5\u2009b is \u03c0\u2010bonded to SWCNTs, but not immobilized at the electrode surface, the above criteria for surface\u2010confined redox couples are unfulfilled, whereas simultaneously the electrochemical system Gen2 does not behave accordingly to homogeneously dissolved redox\u2010active molecules.To exclude that the redox process of + event is quite stable after polymerization, as the peak current decreases only slightly after five cycles .To investigate the influence of the pyrene core towards the ferrocenyl\u2010based redox process, the potential area was extended to 900\u2005mV Figure\u2005. An irre3), 1\u2010Br\u20106\u2010Fc\u2010 (5\u2009a), 2\u2010Br\u20107\u2010Fc\u2010 (7\u2009a), 1,6\u2010Fc2\u2010pyrene (5\u2009b), and 3,6\u2010Fc2\u20109,10\u2010phenanthrenedione (10) were synthesized by reacting ferrocene boronic acid (1) with the respective bromo\u2010functionalized aromatics by applying the Pd\u2010catalyzed Suzuki C\u2212C cross\u2010coupling protocol. The Negishi C\u2212C cross\u2010coupling methodology allowed the formation of 2,7\u2010Fc2\u2010pyrene (7\u2009b) and 3,6\u2010Fc2\u20109,10\u2010dimethoxyphenanthrene (12).Compounds 1\u2010Fc\u2010  to 22.1(9)\u00b0). Parallel displaced \u03c0\u2010interactions were found for 10 and 12, and 10 and 12 exhibit a columnar stacking between the aromatic building blocks, leading to the formation of 1D (12) or 2D coordination polymers (10) along the a\u2010 (10) or b\u2010axis (12).The molecular structures of 3, 5\u2009a,b, 7\u2009a,b, 10, and 12, and 9\u2010ferrocenylphenanthrene for comparison, revealed a strong impact on the redox processes when bearing electron\u2010withdrawing or \u2010donating functionalities such as Br or OMe units. Within the series 3, 5\u2009a, and 7\u2009a, it could be shown that Br in position 1 influences the redox behavior most by shifting the potential cathodically from 50\u2005mV in 7\u2009a to \u2212130\u2005mV in 5\u2009a (vs. FcH/FcH+). The Fc group in position 1 in 3 (30\u2005mV vs. FcH/FcH+) is more easily to oxidize than the Fc in position 2 in 7\u2009a (E\u00b0\u2032=50\u2005mV). However, the 1,6\u2010 and 2,7\u2010substitution patterns of pyrenes 5\u2009b and 7\u2009b have no significant influence on the redox potentials and the redox splitting as was reported for Fc2\u2010naphthalenes,tert\u2010butyl\u20109\u2009H\u2010carbazol\u20109\u2010yl)\u2010, and 2,7\u2010((\u03b75\u2010C5Me5)(dppe)RuC\u2261C)2\u2010pyrenes.+ redox potential of 10 and 12 differ as expected for electron\u2010withdrawing (C(=O)) or \u2010donating (MeO) groups in positions 9 and 10 of the phenanthrene core. The redox splitting in the latter species is smaller than in pyrenes 5\u2009b and 7\u2009b, which is based on the closer proximity of the Fc ligands and the more electron\u2010poor \u03c0\u2010conjugated bridge in 10 and 12.Electrochemical studies of the Fc\u2010substituted aromatics 5\u2009b, 10, and 12, in situ UV/Vis/NIR studies were performed; 7\u2009b was excluded from these studies owing to its low solubility (see above). In the case of mono\u2010oxidized [10]+, the UV/Vis/NIR studies showed no IVCT absorption, which is due to the resonance structure of 10 and hence the redox separation is ascribed to electrostatic interactions. On the contrary, mixed\u2010valent [5\u2009b]+ and [12]+ showed IVCT absorptions, however, of low intensity, indicating weakly coupled systems according to the classification by Robin and Day, which is in good agreement with, for example, 2,7\u2010bispyrene.5\u2009b]+ appeared together with LMCT. Compound [12]+ showed a more intense and narrow IVCT absorption, indicating a stronger metal\u2013metal interaction than for 5\u2009b. This might originate from the higher electron density at the Fc groups, owing to the electron\u2010donating OMe functionalities in positions 9 and 10 at phenanthrene. Furthermore, the IVCT transition of [12]+ was investigated in two different solvents, exploring its solvatochromic characteristics. A \u0394\u03bdmax shift of 1000\u2005cm\u22121 was observed, confirming a class\u2005II classification according to Robin and Day.To confirm the metal\u2013metal interaction in 5\u2009a with 7\u2009a, it becomes apparent that positions 1 and 6 at pyrene are favorable over positions 2 and 7. Moreover, the higher electron density of phenanthrene 12 bearing electron\u2010donating functionalities resulted in a more intense LMCT than in Fc2\u2010pyrene 5\u2009b. These findings are in good agreement with, for example, ferrocenyl naphthalenes,In addition, within the spectroelectrochemical studies, LMCT transitions were observed that are shifted bathochromically depending on the characteristics of the substituents and the substitution pattern. Comparing the intensities of the LMCT transitions of 10 showed a complex solvation of the push\u2013pull system, reflecting the solvent properties such as hydrogen\u2010bond donor capacity, polarizability, and solvation, resulting in a bathochromic shift of \u03bbmax.Solvatochromic studies on 5\u2009b and SWCNTs was investigated by DFT calculations, which showed that the pyrene group of 5\u2009b is oriented parallel to the CNT surface based on optimized \u03c0\u2013\u03c0 interactions. The adsorption behavior of 5\u2009b is insignificantly influenced by the chirality or the diameter of the SWCNTs.The interaction between 5\u2009b to interact non\u2010covalently with different SWCNTs \u2010SWCNTs and semiconducting SWCNTs) was investigated by disentangling experiments. The debundeling with chirality\u2010enriched \u2010SWCNTs was performed for different sonication protocols (see the Supporting Information). For one parameter set, the dispersions containing SWCNTs and 5\u2009b in chloroform showed the typical S11 and the S22 transitions of disentangled SWCNTs in the UV/Vis/NIR spectra, which agree well with the reference spectra of a standard SWCNT dispersion, indicating a direct non\u2010covalent interaction between 5\u2009b and the SWCNT sidewalls.Based on the DFT calculations, the ability of 5\u2009b with semiconducting SWCNTS was studied (Gen2). As a result thereof, it was found that 5\u2009b is able to disentangle SWCNTs as evident from the appearance of the S22 and S33 transitions in the UV/Vis/NIR spectra.With regard to the possible use of functionalized SWCNTs, integrated in CNT\u2010FETs, the interaction of 5\u2009b in an exohedral fashion at the SWCNT sidewalls was proven by CV by using graphene paper as the working electrode, which showed a Fc/Fc+ redox event at 380\u2005mV. This was further strengthened by the electrochemical investigations of solely 5\u2009b, showing no ferrocenyl\u2010based redox processes. At a potential of 800\u2005mV, the irreversible oxidation of the pyrene core occurred, resulting in polymerization and subsequent formation of polypyrene oligomers.The attachment of The debundeling and functionalization of SWCNTs by redox\u2010active Fc\u2010pyrenes in a non\u2010covalent manner is conceivable when using the 1,6\u2010substitution pattern at pyrene.5\u2009b could be used in nanoelectronic application scenarios.Based on these findings, compound\u2005All synthesis procedures were performed under an atmosphere of argon with the solvents degassed prior to use. All reagents were obtained from commercial suppliers and used without further purification. The SWCNTs solid material was purchased from a commercial supplier \u2010SWCNTs, batch number #MKB76336V) and used without further treatment. A commercial SWCNT dispersion, NanoIntegris IsoSol S\u2010100\u00ae, batch SP31\u2010176, was purchased from commercial suppliers and used without any further purification. Ferrocene boronic acid was synthesized from lithioferrocene1H and 125.7\u2005MHz for 13C{1H} in the Fourier transform mode at ambient temperature. Chemical shifts are reported in \u03b4 (ppm) downfield from tetramethylsilane with the solvent as the reference signal . FTIR spectra were recorded by using a Thermo Nicolet IR 200 instrument. The melting points were determined with a Gallenkamp MFB 595 010\u2009m melting point apparatus. Elemental analyses were performed by applying a Thermos FlashAE 1112 instrument. High\u2010resolution mass spectra were recorded with a Bruker Daltonite micrOTOF\u2010QII spectrometer . UV/Vis spectra between 210 and 1010\u2005nm were recorded with a Carl Zeiss MCS 400 spectrometer utilizing CLD 300 (210\u2013600\u2005nm) and CLX 11 lamps (300\u20131010\u2005nm). UV/Vis/NIR spectra of the SWCNT dispersions between 350\u2005nm and 1300\u2005nm were recorded by using a Shimadzu UV\u20103100 PC absorption spectrometer on liquids in quartz cuvettes . For sonication, an Elmasonic P 30 H ultrasonic bath and a Bandelin KE76 tip sonotrode were used. Centrifugation of the dispersions was performed at a Sigma 3\u201330\u2005K lab centrifuge in Oak Ridge tubes  with 10\u2005mL nominal volume.NMR spectra were recorded with a Bruker Avance III 500 spectrometer operating at 500.3\u2005MHz for 3, 5\u2009a,b, 7\u2009a,b, 10, and 12 (1.0\u2005mmol\u2009L\u22121 [NnBu4][B(C6F5)4] as the supporting electrolyte) in dichloromethane were performed in a dried, argon\u2010purged cell at 25\u2009\u00b0C. For the measurements, a three\u2010electrode cell containing a Pt auxiliary electrode, a glassy\u2010carbon working electrode (3.0\u2005mm diameter), and an Ag/Ag+ (0.01\u2005mmol\u2009L\u22121 [AgNO3]) reference electrode fixed on a Luggin capillary was used. The working electrode was pretreated by polishing it with a MicroFloc first with 1\u2005\u03bcm and then with a 0.25\u2005\u03bcm diamond paste. The reference electrode was constructed from a silver wire inserted in a 0.01\u2005mmol\u2009L\u22121 [AgNO3] and a 0.1\u2005mol\u2009L\u22121 [NnBu4][B(C6F5)4] acetonitrile solution in a Luggin capillary with a Vycor tip. This Luggin capillary was inserted into a second Luggin capillary containing a 0.1\u2005mol\u2009L\u22121 [NnBu4][B(C6F5)4] dichloromethane solution and a Vycor tip. Experiments under the same conditions showed that all reduction and oxidation potentials were reproducible within \u00b15\u2005mV. Experimental potentials were referenced against an Ag/Ag+ reference electrode, but the presented results are referenced against ferrocene as an internal standard as required by IUPAC.\u22121 decamethylferrocene (Fc*). Data were processed with a Microsoft Excel worksheet to set the formal reduction potentials of the FcH/FcH+ couple to 0.0\u2005V. Under our conditions, the Fc*/Fc*+ couple appeared at \u2212619\u2005mV vs. FcH/FcH+, \u0394Ep=60\u2005mV, whereas the FcH/FcH+ couple itself was at 220\u2005mV vs. Ag/Ag+, \u0394Ep=61\u2005mV.5\u2009b@SWCNT (Gen2) nanoconjugates, a three\u2010electrode arrangement containing a Pt auxiliary electrode and an Ag/AgCl reference electrode (consisting of a silver wire covered with a thin film of AgCl) fixed in a glass tube (providing a pipetting controller for the supply of the electrolyte) at 25\u2009\u00b0C was used.3[Fe(CN)6] (5\u2005mm aqueous solution) in 1\u2009m aqueous KCl solution (0.358\u2005V).Electrochemical measurements of \u22121 solutions of 3, 5, 7\u2009a, 10, 12, or 9\u2010ferrocenylphenanthrene in anhydrous dichloromethane containing 0.1\u2005mol\u2009L\u22121 of [NnBu4][B(C6F5)4] as the supporting electrolyte were performed in an OTTLE \u03f5max \u00b1100\u2005L\u2009mol\u22121\u2009cm\u22121, \u03bdmax \u00b150\u2005cm\u22121, and \u0394\u03bd1/2 \u00b150\u2005cm\u22121.Spectroelectrochemical UV/Vis/NIR measurements of 2.0\u2005mmol\u2009LK\u03b1 radiation  or CuK\u03b1 radiation  at 110\u2005K by using oil\u2010coated shock\u2010cooled crystals. The structures were solved by direct methods and refined by full\u2010matrix least\u2010squares procedures on F2.Diffraction data were collected with an Oxford Gemini S diffractometer using graphite\u2010monochromated MoEads) of 5\u2009b on CNT is calculated by Eads=E5\u2009b/CNT\u2212E5\u2009b\u2212ECNT, where E5\u2009b/CNT, E5\u2009b, and ECNT denote the total energies of the optimized structures of 5\u2009b adsorbed on CNT, gaseous 5\u2009b, and isolated CNT, respectively.Density functional theory (DFT) calculations were performed with periodic models by using the CASTEP code.2] (1\u2005mol\u2009%), ferrocene boronic acid , K3PO4\u22c5H2O , and the respective aryl halide . Anhydrous toluene (15\u2005mL) was added. The reaction mixture was stirred for 5\u2005min at ambient temperature and then heated to reflux for 24\u2005h. After cooling to ambient temperature, the reaction mixture was filtered through a pad of silica. Afterwards, all volatiles were removed by evaporation. Purification was realized by column chromatography  by using different dichloromethane/hexane mixtures (see below).A three\u2010necked 100\u2005mL flask was charged with +; elemental analysis calcd for C26H17BrFe (465.16\u2005g\u2009mol\u22121): C 67.13, H 3.68, found: C 67.69, H 4.76. Crystal data for 5\u2009a: C26H17BrFe, Mr=465.15\u2005g\u2009mol\u22121, monoclinic, I2/a, \u03bb=0.71073\u2005\u00c5, a=18.4055(14)\u2005\u00c5, b=7.4788(6)\u2005\u00c5, c=26.788(2)\u2005\u00c5, \u03b2=96.988(7)\u00b0, V=3659.9(5)\u2005\u00c53, Z=8, \u03c1calcd=1.688\u2005mg\u2009cm\u22123, \u03bc=3.016\u2005mm\u22121, T=116.8(6)\u2005K, \u03b8 range 3.565\u201324.992\u00b0, 8764 reflections collected, 3199 independent reflections (Rint=0.0352), R1=0.0327, wR2=0.0701 (I>2\u03c3(I)).Compound\u20055\u2009b: Yield: 72.3\u2005mg . M.p.: 176\u2009\u00b0C (decomposition); 1H\u2005NMR (CDCl3): \u03b4=4.22 , 4.49 , 4.84 , 8.02 , 8.10 , 8.39 , 8.73\u2005ppm ; 13C\u2005NMR (CDCl3): \u03b4=68.7 (C5H4), 69.9 (C5H5), 71.1 (C5H4), 87.6 , 124.1 (C16H8), 125.1 (C16H8), 125.4 (C16H8), 127.0 (C16H8), 129.0 (C16H8), 129.3 (C16H8), 129.7 (C16H8), 134.0\u2005ppm (C16H8); IR (KBr): \u03bd=2964 (m), 2925 (w), 2855 (w), 1601 (w), 1496 (w), 1456 (w), 1428 (w), 1409 (w), 1373 (w), 1262 (s), 1211 (w), 1105 (s), 1074 (s), 1022 (s), 881 (m), 866 (m), 854 (m), 804 (s), 684 (m), 668\u2005cm\u22121 (m); HR\u2010MS (ESI\u2010TOF) m/z calcd for C36H26Fe2: 570.0729; found: 570.0734 [M]+; elemental analysis calcd for C36H26Fe2 (570.28\u2005g\u2009mol\u22121): C 75.82, H 4.60; found: C 75.56, H 4.52. Crystal data for 5\u2009b: C36H26Fe2, Mr=570.27\u2005g\u2009mol\u22121, monoclinic, P21/n, \u03bb=0.71073\u2005\u00c5, a=14.3748(18)\u2005\u00c5, b=8.6113(9)\u2005\u00c5, c=20.585(2)\u2005\u00c5, \u03b2=105.022(12)\u00b0, V=2461.1(5)\u2005\u00c53, Z=4, \u03c1calcd=1.539\u2005mg\u2009cm\u22123, \u03bc=1.204\u2005mm\u22121, T=116.95(10)\u2005K, \u03b8 range 3.043\u201324.996\u00b0, 5798 reflections collected, 5798 independent reflections (Rint=0.0655), R1=0.0771, wR2=0.1997 (I>2\u03c3(I)).7\u2009a was prepared according to the general synthetic methodology described above by using 2,7\u2010dibromopyrene . Compound\u20057\u2009a was separated by column chromatography by using hexane/dichloromethane mixtures (v/v) starting from 9:1  to 4:1 (7\u2009a). After evaporation of all volatiles, the received solid was recrystallized from acetone at \u221220\u2009\u00b0C. Compound\u20057\u2009a was isolated as an orange solid. Yield: 37\u2005mg . M.p.: 223\u2009\u00b0C; 1H\u2005NMR (CDCl3): \u03b4=4.08 , 4.46 , 4.96 , 7.96 , 8.07 , 8.26\u2005ppm ; 13C\u2005NMR (CDCl3): \u03b4=67.2 (C5H4), 69.7 (C5H4), 70.0 (C5H5), 85.3 , 119.7 (C16H8), 123.1 (C16H8), 123.4 (C16H8), 123.5 (C16H8), 126.7 (C16H8), 127.3 (C16H8), 128.7 (C16H8), 131.1 (C16H8), 132.6 (C16H8), 138.0\u2005ppm (C16H8); IR (KBr): \u03bd=3036 (w), 2924 (w), 2852 (w), 1597 (s), 1554 (m), 1487 (m), 1429 (m), 1409 (m), 1299 (m), 1245 (s), 1217 (w), 1152 (m), 1145 (m), 1105 (s), 1037 (m), 1030 (m), 998 (s), 929 (m), 898 (m), 878 (s), 867 (s), 858 (s), 853 (s), 846 (s), 830 (s), 820 (s), 803 (s), 762 (s), 707 (s), 669\u2005cm\u22121 (s); HR\u2010MS (ESI\u2010TOF) m/z calcd for C26H17BrFe: 463.9859; found: 463.9849 [M]+; elemental analysis calcd for C26H17BrFe (465.16\u2005g\u2009mol\u22121): C 67.13, H 3.68; found: C 67.25, H 3.71. Crystal data for 7\u2009a: C26H17BrFe, Mr=465.15\u2005g\u2009mol\u22121, monoclinic, P21/c, \u03bb=0.71073\u2005\u00c5, a=10.3922(8)\u2005\u00c5, b=13.9915(11)\u2005\u00c5, c=12.8138(11)\u2005\u00c5, \u03b2=99.217(3)\u00b0, V=1839.1(3)\u2005\u00c53, Z=4, \u03c1calcd=1.680\u2005mg\u2009cm\u22123, \u03bc=3.001\u2005mm\u22121, T=100\u2005K, \u03b8 range 3.525\u201324.997\u00b0, 26\u2009828 reflections collected, 3234 independent reflections (Rint=0.0982), R1=0.0268, wR2=0.0707 (I>2\u03c3(I)).Compound\u200510 was synthesized in accordance with the general synthesis procedure described above by using 3,6\u2010dibromophenathren\u20109,10\u2010dione . Compound\u200510 was separated by column chromatography  by using first hexane  and then dichloromethane/ethylacetate mixtures (v/v) of ratios 4:1 and 3:1 (10). After evaporation of all volatiles, compound\u200510 was obtained as a green solid. Yield: 136\u2005mg . M.p.: 123\u2009\u00b0C; 1H\u2005NMR (CDCl3): \u03b4=4.13 , 4.55 , 4.86 , 7.56 , 8.05 , 8.15\u2005ppm ; 13C\u2005NMR (CDCl3): \u03b4=67.6 (C5H4), 70.3 (C5H5), 70.9 (C5H4), 83.0 , 120.6 (C14H6), 127.1 (C14H6), 129.0 (C14H6), 130.9 (C14H6), 136.0 (C14H6), 149.5 (C14H6), 180.1\u2005ppm (CO); IR (KBr): \u03bd=2959 (m), 2925 (s), 2854 (m), 1774 (w), 1658 (m), 1590 (s), 1465 (m), 1416 (m), 1262 (s), 1105 (s), 1029 (s), 924 (m), 807 (s), 731\u2005cm\u22121 (m); elemental analysis calcd for C34H24Fe2O2 (576.25\u2005g\u2009mol\u22121): C 70.87, H 4.20; found: C 70.76, H 4.11. Crystal data for 10: C35H26Cl2Fe2O2, Mr=661.16\u2005g\u2009mol\u22121, monoclinic, P21/c, \u03bb=0.71073\u2005\u00c5, a=10.1023(5)\u2005\u00c5, b=38.6119(18)\u2005\u00c5, c=13.9755(8)\u2005\u00c5, \u03b2=93.989(5)\u00b0, V=5438.2(5)\u2005\u00c53, Z=8, \u03c1calcd=1.615\u2005mg\u2009cm\u22123, \u03bc=1.297\u2005mm\u22121, T=129.9(4)\u2005K, \u03b8 range 3.023\u201325.999\u00b0, 34\u2009953 reflections collected, 10\u2009644 independent reflections (Rint=0.0537), R1=0.0819, wR2=0.1943 (I>2\u03c3(I)).Compound\u2005m solution of tert\u2010butyllithium  in pentane was added dropwise at \u221230\u2009\u00b0C to ferrocene  and KOtBu  dissolved in tetrahydrofuran (20\u2005mL). After 1\u2005h of stirring at this temperature, anhydrous [ZnCl2 2\u2009thf]  was added in a single portion. The solution was kept for 1\u2005h at \u221230\u2009\u00b0C and an additional hour at 25\u2009\u00b0C. Afterwards, [PdCl2(dppf)]  and the respective dibromoarenes  were added in a single portion and the reaction solution was stirred for 24\u2005h at 60\u2009\u00b0C. After evaporation of all volatiles, the precipitate was dissolved in dichloromethane (200\u2005mL) and washed thrice with 100\u2005mL portions of water. The organic phase was dried over MgSO4 and the solvent was removed under oil\u2010pump vacuum. The remaining solid was purified by column chromatography  by using different dichloromethane/hexane mixtures. All volatiles were removed under reduced pressure. The title compounds were obtained as solids.A 1.9\u20097\u2009b was synthesized according to the general synthetic methodology for the Negishi C\u2212C cross\u2010coupling protocol by using 2,7\u2010dibromopyrene . Compound\u20057\u2009b was separated by column chromatography by using hexane/dichloromethane eluent mixtures (v/v) starting from 9:1  to 1:9 (7\u2009b). The obtained solid was recrystallized from acetone at \u221220\u2009\u00b0C. Compound\u20057\u2009b was isolated as a red solid. Yield: 15\u2005mg . M.p.: 265\u2009\u00b0C (decomposition); 1H\u2005NMR (CDCl3): \u03b4=4.08 , 4.45 , 4.96 , 8.04 , 8.24\u2005ppm ; IR (KBr): \u03bd=3116 (w), 3092 (w), 1606 (m), 1424 (m), 1407 (m), 1382 (m), 1103 (s), 1030 (s), 1000 (s), 932 (m), 881 (m), 829 (m), 806 (m), 714 (m), 668\u2005cm\u22121 (w); elemental analysis calcd for C36H26Fe2 (570.28\u2005g\u2009mol\u22121): C 75.82, H 4.60; found: C 76.63, H 4.43. Crystal data for 7\u2009b: C36H26Fe2, Mr=570.27\u2005g\u2009mol\u22121, monoclinic, P21/c, \u03bb=1.54184\u2005\u00c5, a=11.0921(3)\u2005\u00c5, b=7.8868(2)\u2005\u00c5, c=14.2973(4)\u2005\u00c5, \u03b2=100.294(2)\u00b0, V=1230.61(6)\u2005\u00c53, Z=2, \u03c1calcd=1.539\u2005mg\u2009cm\u22123, \u03bc=9.630\u2005mm\u22121, T=100\u2005K, \u03b8 range 4.051\u201365.912\u00b0, 11\u2009449 reflections collected, 2128 independent reflections (Rint=0.0443), R1=0.0375, wR2=0.0961 (I>2\u03c3(I)).Compound\u200511; 396\u2005mg, 0.5\u2005mmol). Compound\u200512 was separated by column chromatography by using hexane/dichloromethane eluent mixtures (v/v) starting from 9:1  to 1:9 (12). After evaporation of all volatiles, 12 was obtained as an orange solid. Yield: 100\u2005mg . M.p.: 169\u2009\u00b0C; 1H\u2005NMR (CDCl3): \u03b4=4.10 , 4.12 , 4.43 , 4.86 , 7.80 , 8.16 , 8.68\u2005ppm ; 13C\u2005NMR (CDCl3): \u03b4=61.2 (OCH3), 67.0 (C5H4), 69.4 (C5H5), 69.9 (C5H4), 86.0 , 119.4 (C14H6), 122.3 (C14H6), 126.1 (C14H6), 127.8 (C14H6), 128.5 (C14H6), 136.9\u2005ppm (C14H6); IR (KBr): \u03bd=2925 (s), 2854 (s), 1744 (m), 1700 (m), 1684 (m), 1653 (m), 1607 (s), 1559 (m), 1540 (m), 1507 (m), 1458 (s), 1446 (s), 1419 (m), 1337 (m), 1311 (s), 1189 (m), 1105 (s), 1092 (s), 1061 (s), 1027 (m), 983 (s), 885 (m), 874 (s), 707 (w), 668 (w), 661\u2005cm\u22121 (w); elemental analysis calcd for C36H30Fe2O2 (606.32\u2005g\u2009mol\u22121): C 71.31, H 4.99; found: C 70.50, H 4.89. Crystal data for 12: C36H30Fe2O2, Mr=606.30\u2005g\u2009mol\u22121, orthorhombic, Pnn2, \u03bb=1.54178\u2005\u00c5, a=19.680(2)\u2005\u00c5, b=6.3428(8)\u2005\u00c5, c=10.6327(17)\u2005\u00c5, V=1327.3(3)\u2005\u00c53, Z=2, \u03c1calcd=1.517\u2005mg\u2009cm\u22123, \u03bc=9.021\u2005mm\u22121, T=100(2)\u2005K, \u03b8 range 4.493\u201364.897\u00b0, 23\u2009836 reflections collected, 2100 independent reflections (Rint=0.1099), R1=0.1412, wR2=0.4059 (I>2\u03c3(I)).The title compound was prepared according to the general synthesis protocol for the Negishi C\u2212C cross\u2010coupling by using 3,6\u2010dibromo\u20109,10\u2010dimethoxyphenanthrene (Master5\u2009b was prepared by dissolving 5\u2009b (1.86\u2005mg) in chloroform . Afterwards, the obtained solution was treated by bath sonication  for 10\u2005min.The master solution Master5\u2009b (800\u2005\u03bcL) in chloroform .The mixture FC00 was obtained by diluting The mixture FC01 was prepared by dispersing SWCNTs solid material (0.82\u2005mg) in FC00 (6\u2005mL) and applying bath sonication  for 30\u2005min, followed by centrifugation .The mixture FC02 was prepared by dispersing SWCNTs solid material (0.75\u2005mg) in FC00 (6\u2005mL) and applying tip sonication  for 30\u2005min, followed by centrifugation .\u22121.Dispersions FC01 and FC02 were prepared with a SWCNT solid content of (0.128\u00b10.009)\u2005mg\u2009mL3) was obtained by pouring SWCNTs into CHCl3 and employing bath sonication  for 30\u2005min followed by centrifugation . The SWCNT solid content was kept to (0.128\u00b10.009)\u2005mg\u2009mL\u22121.The reference dispersion SWCNTs (CHCl2O) was obtained by adapting previously reported sonication procedures.\u22121.The reference dispersion of SWCNTs (HH\u2010fluoren\u20102\u2010yl)aryl\u2010based polymer (PFH\u2010R)5\u2009b dissolved in toluene  to attach 5\u2009b at those parts of the SWCNT sidewalls depleted from PFH\u2010R. To apply UV/Vis/NIR analysis for this step, the bucky paper obtained this way was manually delaminated from the filter by using standard lab cutlery. The slices of the SWCNT solid were then collected in a new glass vial (10\u2005mL screw\u2010cap) and re\u2010dispersed in toluene (2\u2005mL) by using a bath sonicator . The obtained liquid obtained by this procedure (Gen2) was subjected to the UV/Vis/NIR analysis and compared with basic spectra of 5\u2009b in toluene, just diluted NanoIntegris IsoSol S\u2010100\u00ae (Gen0) and a reference sample obtained directly by dissolving a bucky paper derived from NanoIntegris IsoSol S\u2010100\u00ae without the washing (toluene) and flushing (5\u2009b in toluene) steps (Gen1).The commercial SWCNT dispersion, stabilized by a 9\u2010 for all new compounds are given. This material is available free of charge via the Internet. CCDC\u2005https://www.ccdc.cam.ac.uk/services/strctures?id=doi:10.1002/chem.201904450 contain the supplementary crystallographic data for this paper. These data are provided free of charge by http://www.ccdc.cam.ac.uk/.Additional structural data, cyclic voltammograms, square wave voltammograms, and UV/Vis/NIR spectra as well as spectroscopic details  should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "In contrast, 1,7\u2010bis(1\u2010phospholano)heptane (1b) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis\u2010phospholane and halido ligands. A unique paddle wheel\u2010type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X\u2010ray crystallography.In a 2:2 reaction with silver(I) chloride or bromide, 1,5\u2010bis(1\u2010phospholano)pentane ( John Wiley & Sons, Ltd. Gr\u00fcttner and Krause. They synthesized 1\u2010phenylphospholane by reacting the di\u2010Grignard reagent of 1,4\u2010dibromobutane with dichlorophenylphosphine.Brunner et al. published the synthesis of the chiral 3,4\u2010disubstituted correspondent.Wilson et al.Burk et al.Baccolini et al.H\u2010phospholane and P\u2010substituted phospholanes can be obtained using this method. In 2009, the same group reported the successful synthesis of chiral alkylphospholanes.Phospholanes are five\u2010membered cyclic phosphines with good \u03c3\u2010donor properties, which make them especially interesting as ligands in transition metal catalysis. Their ring structure and well\u2010defined geometry are key features, which set them apart from other phosphines.Burk and co\u2010workers.Burk published a paper entitled \u201cModular Phospholane Ligands in Asymmetric Catalysis\u201d, which shows the ten\u2010year development of ligands based on the trans\u20102,5\u2010disubstituted phospholane moiety.Clark and Landis comprehensively summarized the following developments in this field.The real success story of the phospholane ligands started, however, in 1990 with the synthesis of bis\u2010phospholanoethane (BPE) and DuPhos by cis complexes with catalytically active metals.Emrich and Jolly,Oisaki et al.4 as a metal complex precursor.3CN)4]BF4.These chiral bis\u2010phospholanes are usually based on rigid spacers that allow them to act as chelate ligands forming 1a)1b)We have performed an in\u2010depth study of the coordination behavior of these flexible bis\u2010phospholane ligands in silver(I) halide complexes and report here the synthesis, characterization, and structural elucidation of complexes based on 1,5\u2010bis(1\u2010phospholano)pentane (1a)31P{1H} NMR spectrum of the crude reaction mixture showed the expected downfield shift from the free ligands (ca. \u201327 ppm)2 and 3 suitable for X\u2010ray structure analysis were obtained at room temperature by slow diffusion of n\u2010hexane into a DCM/toluene solution. The results showed two different coordination modes: A metallacycle 2 with intramolecular chlorido bridges  (Table 2 [245.5(2) and 245.7(2) pm] which are more than 8 pm longer than those in the corresponding AgBF4 complex.2Cl2 moiety forms an almost perfect square as shown by Ag\u2013Cl bond lengths of 271.1(2) and 270.9(2) pm and a Cl1\u2013Ag1\u2013Cl1' bond angle of 90.00(5)\u00b0. A similar structure was reported for the 2:2 complexes of 1,5\u2010bis(diphenylphosphanyl)pentane (dpppn) with AgX  by Effendy et al.Cassel.2, which is to be expected given the electron\u2010withdrawing effect of the phenyl groups of the triphenylphosphine.Complex 31P{1H} NMR spectrum of complex 2 in CDCl3 shows a singlet at \u03b4 = \u20135.7 ppm. Coupling with the NMR\u2010active silver isotopes 107Ag (NA = 51.84\u2009%) or 109Ag  is not observed. The lack of coupling in solution at room temperature was also observed by Streitberger et al.Effendy and co\u2010workers who carried out more thorough NMR studies on silver(I) bis(diphenyl)phosphine complexes.2 in solution is evidenced by the ESI(+) mass spectrum which showed the [M\u2013Cl]+ molecular ion at m/z = 739.1.The 3 crystallizes in the monoclinic space group C2/c with four molecules in the unit cell. The solid\u2010state structure shows two molecules of 1,5\u2010bis(1\u2010phospholano)pentane bridging two silver(I) cations forming a frame\u2010like macrocycle   and 237.02(8) pm but a significantly larger P\u2013Ag\u2013P bond angle of 176.89(1)\u00b0 for a distinct frame\u2010like structure obtained using AgBF4  cations of neighboring metallamacrocycles interact with an additional AgBr moiety, thus forming Ag3Br3 assemblies  phosphine complexes. Often they form tetrameric cubane\u2010like structures (Ag4Br4), when simple monodentate phosphine ligands are employed.Effendy et al. reported a tetranuclear 2:1 complex , which is formed when AgX and bis(diphenylphosphanyl)methane (dppm) are reacted in a 2:1 ratio. The structure of the complex includes an Ag4Br4 assembly with a \u201cstep\u201d conformation.Schubert et al. found that dppm and AgBr can also form a 3:3 complex bearing an [Ag3Br2]+ cluster, while bis(diphenylphosphanyl)methylamine (dppa) forms a dimeric 2:4 complex in which an [Ag4Br2]2+ octahedron is present.3Br3 assembly to the one found in complex 3 was assumed to bridge adjacent macrocycles in a silver(I) complex based on 2,5\u2010bis(diphenylphosphinomethyl)thiophene (dpmt). However, only the crystal structure of the iodine homologue was reported.3 shows that Ag3Br3 bicycles are bridged by a set of two 1,5\u2010bis(1\u2010phospholano)pentane ligands, building a polymeric chain along (101) .Ag31P{1H} NMR spectrum of complex 3 in CDCl3 shows a singlet at \u03b4 = \u20138.5 ppm. The ESI(+) mass spectrum showed peaks at m/z = 1590.6, 1402.8, 1158.7, and 1215.0, corresponding to the fragments [M+L+2Ag+Br]+, [M+L+Ag]+, [M+Ag]+, and [3 L+3Ag+2Br]+, respectively. The peaks at m/z = 970.9 (base peak) and 780.0 corresponding to fragments [M\u2013Br]+ and [M\u2013AgBr2]+, respectively, are proof that the frame\u2010like metallamacrocycle is stable in solution .The 1b)1a. The reaction mixtures were shielded from light. After stirring at room temperature for four hours, the 31P{1H} NMR spectra of the crude reaction mixture showed the expected downfield shift with signals around \u20137 ppm. Crystals of the final products 4a and 4b  are marginally shorter than in complex 2. One of the Ag\u2013Cl bonds (Ag1\u2013Cl2) is ca. 6 pm shorter than the one in 2, causing the Ag2Cl2 ring to slightly deviate from the ideal square arrangement, with angles ranging from 85.54(4) to 93.24(3)\u00b0 (Table Ag\u2013P bond lengths in 4a forms a (001) layer structure in which the silver(I) cations are linked in series by chlorine atoms, while the bis\u2010phospholane ligands are arranged in a zigzag fashion. The layers are formed by two distinct interwoven polymeric chains  mass spectrum showed the base peak at m/z = 795 corresponding to the fragment [L2Ag2Cl]+ (L = ligand 1b).The 4b crystallizes in the monoclinic space group P21/c. The solid\u2010state structure  layer  to 138.70(3)\u00b0, Table 3 alkane ligands when comparing open macrocycles [P\u2013Ag\u2013P 144.30(7)\u00b0] to species in which halido bridging was observed [P\u2013Ag\u2013P 131.24(9)\u00b0].4b + (L = ligand 1b). Two other peaks corresponding to species with higher m/z values were observed but could not be attributed and probably correspond to oligomeric fragments.The 1a,1b and two equivalents of AgBr were performed under similar conditions as described for the 1:1 reactions. The 31P{1H} NMR spectrum of the crude reaction mixtures showed, in each case, one downfield\u2010shifted broad singlet. Suitable crystals for X\u2010ray structure analysis were obtained at room temperature by layering a DCM/toluene (for ligand 1a) or DCM (for ligand 1b) solution of the crude product with n\u2010hexane. X\u2010ray structure analysis showed that in the case of ligand 1b the same coordination polymer 4b was formed as in the 1:1 reaction, while ligand 1a yielded the metallacryptand 5  cations are bridged by three 1,5\u2010bis(1\u2010phospholano)pentane ligands in a trigonal\u2010planar fashion forming a triangular prism (paddle wheel) with Ag\u2013P distances ranging from 241.88(9) to 251.48(9) pm and P\u2013Ag\u2013P angles ranging from 104.74(3) to 137.51(3)\u00b0  and 248.5(1) pm, respectively]. Ag\u2013Br bond lengths [278.90(4) and 281.84(5) pm] are comparable to those previously observed in 4b.Complex 31P{1H} NMR studies reported by Dean et al. (1987) and later by Peringer et al. (1988) postulated the formation of complexes [Ag2(\u03bc\u2010dppm)3](AsF6)22(\u03bc\u2010dppm)3](CF3SO3)2,Hong et al. published the structure of [Ag2(\u03bc\u2010dppm)3](NO3)2 and revealed its paddle wheel topology.5 is not only the first such example bearing bis\u2010phospholane ligands but also the first silver(I) bis\u2010phosphine paddle wheel\u2010type metallacryptand.Silver(I) complexes with an M:L ratio of 2:3 and with bridging bis(phosphanyl)alkane ligands are rare. 1a) and 1,7\u2010bis(1\u2010phospholano)heptane (1b), gave macrocycles, coordination polymers and paddle wheel\u2010type metallacryptands depending on the stoichiometry, length of alkylene spacer (C5 or C7) and counter anion. These complexes are further proof that these simple and highly flexible bis\u2010phospholane ligands have extremely versatile coordination properties.The reaction of silver(I) chloride or bromide with two highly flexible bis\u2010phospholane ligands, 1,5\u2010bis(1\u2010phospholano)pentane (1b)\u03b4) of 1H, 13C, and 31P are reported in parts per million (ppm) at 400.12, 100.63, and 162.02 MHz, respectively, with tetramethylsilane as internal standard and referencing to the unified \u039e scale.J are given in Hertz. The numbering scheme for assignment of 1H NMR spectra is given in Scheme \u20131. Wavenumbers \u03bd\u0303 are reported in cm\u20131. Mass spectra were recorded with an ESQUIRE 3000 plus spectrometer. Elemental analyses were carried out with a Heraeus VARIO EL oven. Melting points were measured in sealed capillaries by using a variable heater from Gallenkamp.All reactions and crystallization of compounds were carried out in a nitrogen atmosphere by using standard Schlenk techniquesSynthesis of Bisdisilver(I) dichloride (2): AgCl  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards, the white residue was washed with n\u2010hexane (3\u2009\u00d7\u20092 mL) to yield 2  as a white solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction were obtained from a DCM/toluene mixture layered with n\u2010hexane at room temperature. M.p. 129 \u00b0C. 1H NMR (CDCl3): \u03b4 = 2.19\u20132.03 , 1.92\u20131.72 , 1.72\u20131.59 , 1.50\u20131.48 ppm . 13C{1H} NMR (CDCl3): \u03b4 = 32.3\u201332.0 , 28.0\u201327.9 , 27.2 (s), 27.1\u201326.9 , 26.3\u201325.7 ppm . 31P{1H} NMR (CDCl3): \u03b4 = \u20135.7 ppm (s). IR: \u03bd\u0303 = 2937 , 2915 , 2855 , 1455 , 1436 , 1113 (w), 843 (w), 689 cm\u20131 (w). MS (ESI(+), DCM/acetonitrile): m/z = 739.1 [M\u2013Cl]+, 597.2 [AgL2]+, 351.1 [AgL]+; L = 1a. C26H52Ag2Cl2P4: calcd. C 40.28, H 6.76\u2009%; found C 40.29, H 6.82\u2009%.Synthesis of Poly{bistrisilver(I) tribromide} (3): AgBr  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n\u2010hexane (3\u2009\u00d7\u20092 mL) to remove excess ligand, yielding 3  as a white solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction were obtained from a DCM solution layered with n\u2010hexane at room temperature. M.p. 195 \u00b0C. 1H NMR (CDCl3): \u03b4 = 2.20\u20132.04 , 1.91\u20131.76 , 1.75\u20131.55 ppm . 13C{1H} NMR (CDCl3): \u03b4 = 27.6\u201327.3 , 27.1 (s), 26.3\u201326.0 , 26.0\u201325.8 ppm . 31P{1H} NMR (CDCl3): \u03b4 = \u20138.5 ppm (s). IR: \u03bd\u0303 = 2934 , 2919 , 2845 , 1444 , 1407 , 1112 (w), 1023 (w), 845 (w), 708 cm\u20131 (w). MS (ESI(+), DCM/MeOH): m/z = 1590.6 [M+L+2Ag+Br]+, 1402.8 [M+L+Ag]+, 1158.7 [M+Ag]+, 1215.0 [Ag3L3Br2]+, 970.9 [M\u2013Br]+, 780.0 [M\u2013AgBr2]+; M = [Ag3L2Br3], L = 1a. C26H52Ag3Br3P4: calcd. C 29.69, H 4.98\u2009%; found C 29.66, H 5.01\u2009%.Synthesis of Poly{bissilver(I) chloride} (4a): AgCl  was added as a solid to a stirred solution of 1b  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n\u2010hexane (3\u2009\u00d7\u20092 mL) to yield 4a  as a white solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction were obtained from a DCM/THF mixture layered with n\u2010hexane at room temperature. M.p. 103 \u00b0C. 1H NMR (CDCl3): \u03b4 = 2.12\u20131.99 , 1.85\u20131.66 , 1.64\u20131.53 , 1.51\u20131.14 . 13C{1H} NMR (CDCl3): \u03b4 = 31.1\u201330.5 , 29.2 (s), 28.3\u201327.8 , 27.2 (s), 27.1\u201326.8 , 26.3\u201325.8 ppm . 31P{1H} NMR (CDCl3): \u03b4 = \u20135.3 ppm (s). IR: \u03bd\u0303 = 2962 , 2927 , 2856 , 1446 , 1261 (s), 1105 (s), 1024 (s), 802 (s), 720 cm\u20131 (w). MS (ESI(+), DCM/MeOH): m/z = 795.0 [Ag2L2Cl]+, 651.0 [AgL2]+, 379.0 [AgL]+; L = 1b. C15H30AgClP2: calcd. C 43.34, H 7.27\u2009%; found C 43.30, H 7.21\u2009%.Synthesis of Poly{bissilver(I) bromide} (4b): AgBr  was added as a solid to a stirred solution of 1b  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n\u2010hexane (3\u2009\u00d7\u20092 mL) to yield 4b  as a white solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction were obtained from a DCM solution layered with n\u2010hexane at room temperature. M.p. 150 \u00b0C. 1H NMR (CDCl3): \u03b4 = 2.22\u20132.09 , 1.94\u20131.74 , 1.70\u20131.60 , 1.54\u20131.22 ppm . 13C{1H} NMR (CDCl3): \u03b4 = 31.0\u201330.2 , 29.1 (s), 28.4\u201327.7 , 27.3 (s), 27.1\u201326.7 , 26.5\u201325.8 ppm . 31P{1H} NMR (CDCl3): \u03b4 = \u20135.7 ppm (s). IR: \u03bd\u0303 = 2931 , 2852 , 1447 , 1400 , 1113 (w), 846 cm\u20131 (w). MS (ESI(+), chloroform/MeOH): m/z = 839.1 [Ag2L2Br]+, 381.1 [AgL]+; L = 1b. C15H30AgBrP2: calcd. C 39.16, H 6.57\u2009%; found C 39.23, H 6.65\u2009%.Synthesis of Trisdisilver(I) Dibromide (5): AgBr  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n\u2010hexane (3\u2009\u00d7\u20092 mL) to yield 5  as a white solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction were obtained from a DCM/toluene mixture layered with n\u2010hexane at room temperature. M.p. 139 \u00b0C. 1H NMR (CDCl3): \u03b4 = 2.18\u20132.05 , 1.94\u20131.81 , 1.79\u20131.68 , 1.60\u20131.48 , 1.45\u20131.38 ppm . 13C{1H} NMR (CDCl3): \u03b4 = 34.0\u201333.4 , 29.3 (s), 27.9 , 27.4 (s), 27.0 ppm . 31P{1H} NMR (CDCl3): \u03b4 = \u20139.1 ppm (s). IR: \u03bd\u0303 = 2921 , 2855 , 1447 , 1409 , 1109 (w), 1069 (w), 848 cm\u20131 (w). MS (ESI(+), DCM/MeOH): m/z = 783.0 [Ag2L2Br]+, 595.2 [AgL2]+; L = 1a. C39H78Ag2Br2P6: calcd. C 42.26, H 7.09\u2009%; found C 42.28, H 7.04\u2009%.Crystal Structure Determinations: The data were collected on a Gemini diffractometer (Rigaku Oxford Diffraction) using Mo\u2010K\u03b1 radiation (\u03bb = 71.073 pm) and \u03c9\u2010scan rotation. Data reduction was performed with CrysAlisPro2: SHELXS\u201097;4a: SIR\u2010923, 4b, 5: SHELXT\u201020144a, all structures are disordered to a certain extent. Mostly the five\u2010membered C4H8P ring was disordered, and for 3 and 4b some of the CnH2n chains were disordered as well. Details concerning data collection and crystallographic details are summarized in Table 2), CCDC\u20101974714 (3), CCDC\u20101974716 (4a), CCDC\u20101974717 (4b), and CCDC\u20101974715 (5) .Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository numbers CCDC\u20101974713 (Supporting Information (see footnote on the first page of this article): 1H, 13C{1H}, 31P{1H} NMR, IR and mass spectra (ESI(+)) of complexes 2, 3, 4a, 4b and 5, and 31P{1H} NMR spectrum of the reaction mixture of 1a with AgBr, ratio 3:2.https://doi.org/10.1002/zaac.202000001 or from the author.Supporting information for this article is available on the WWW under Supporting InformationClick here for additional data file."}
{"text": "A symmetrical dicarbonohydrazide was used to synthesize a centrosymmetric tetra\u00adnuclear zinc(II) complex in which two of the zinc cations are penta\u00adcoordinated and the other two are hexa\u00adcoordinated. II complex, [Zn4(C13H11N6O)2Cl6(H2O)2] or {[Zn2(HL)(H2O)(Cl2)](\u03bcCl)2[Zn2(HL)(H2O)(Cl)]}2, was synthesized by mixing an equimolar amount of a methanol solution containing ZnCl2 and a methanol solution containing the ligand H2L . In the tetra\u00adnuclear complex, each of the two ligand mol\u00adecules forms a dinuclear unit that is connected to another dinuclear unit by two bridging chloride anions. In each dinuclear unit, one ZnII cation is penta\u00adcoordinated in a N2OCl2 in a distorted square-pyramidal geometry, while the other ZnII cation is hexa\u00adcoordinated in a N3OCl2 environment with a distorted octa\u00adhedral geometry. The basal plane around the penta\u00adcoordinated ZnII cation is formed by one chloride anion, one oxygen atom, one imino nitro\u00adgen atom and one pyridine nitro\u00adgen atom with the apical position occupied by a chloride anion. The basal plane of the hexa\u00adcoordinated ZnII cation is formed by one chloride anion, one hydrazinyl nitro\u00adgen atom, one imino nitro\u00adgen atom and one pyridine nitro\u00adgen atom with the apical positions occupied by a water oxygen atom and a bridged chloro anion from another dinuclear unit, leading to a tetra\u00adnuclear complex. A series of intra\u00admolecular C\u2014H\u22efCl hydrogen bonds is observed in each tetra\u00adnuclear unit. In the crystal, the tetra\u00adnuclear units are connected by inter\u00admolecular C\u2014H\u22efCl, C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming a planar two-dimensional structure in the ac plane.A tetra\u00adnuclear Zn S-cis or S-trans, yielding different structures with the same metal cation. These ligands can coordinate to transition metals in a penta\u00addentate or hexa\u00addentate manner  complex 4](NO3)4\u00b72H2O where H2L1 is 1,5-bis\u00ad[1-(pyridin-2-yl)ethyl\u00adidene)carbonohydrazide]. The study of the fluorescence properties of the ligand H2L1 and its complex revealed that complexation increased the fluorescent properties of the ligand (H2O)(Cl2)](\u03bcCl)2[Zn2(HL)(H2O)(Cl)]}2 where H2L is 1,5-bis\u00ad(pyridin-2-yl\u00admethyl\u00adene)carbono\u00adhydrazide.The behavior of these mol\u00adecules has attracted the inter\u00adest of chemists working in coordination chemistry. The free dicarbonohydrazide exhibits biological activities /60 where \u03b2 and \u03b1 are the largest values of the bond angles around the central atom]; \u03c4 = 0 for a perfect square pyramidal geometry while \u03c4 = 1 for a perfect trigonal\u2013bipyramidal geometry. In the case of the title complex, the \u03c4 value of 0.1085 is indicative of a distorted square-pyramidal geometry around the Zn1 center. The equatorial plane is occupied by atoms N5, N6, Cl3, O2 while the apical position is occupied by Cl2. The angles N5\u2014Zn1\u2014O2 [72.76\u2005(9)\u00b0], O2\u2014Zn1\u2014Cl3 [96.00\u2005(6)\u00b0], Cl3\u2014Zn1\u2014N6 [97.10\u2005(8)\u00b0] and N6\u2014Zn1\u2014N5 [75.82\u2005(10)\u00b0] deviate from those for a regular square pyramid. The transoid angles in the basal plane O2\u2014Zn1\u2014N6 and N5\u2014Zn1\u2014Cl3 deviate severely from linearity with values of 144.87\u2005(10) and 138.36\u2005(8)\u00b0, respectively \u2013111.20\u2005(7)\u00b0 and transoid angles of 171.67\u2005(8)\u00b0 [N2\u2014Zn2\u2014Cl1] and 148.24\u2005(10)\u00b0 [N4\u2014Zn2\u2014N1]. The sum of the angles subtended by the atoms in the plane is 359.77\u00b0. The apical positions are occupied by O1 and Cl1i with O 1\u2014Zn2\u2014Cl1i = 172.20\u2005(7)\u00b0 \u00b0 is in accordance with the value reported for the complex di-\u03bc-chlorido-bis\u00ad{[2-({[2-(2-pyrid\u00adyl)eth\u00adyl](2-pyridyl\u00admeth\u00adyl)amino}\u00admeth\u00adyl)-phen\u00adol]zinc(II)} bis\u00ad(perchlorate) dihydrate  and 2.7489\u2005(10)\u2005\u00c5, respectively, agree with those for a chloride anion in a bridging position  or diprotonated (H4L2+) and additionally one Dy complex mol\u00adecule in which HL\u2212 and L2\u2212 are present as ligands. Among the diprotonated mol\u00adecules, three different counter-ions are present: I\u2212 in AVOSOV : 3439, 3204, 3198, 3055, 2936, 1684, 1582, 1610, 1582, 1532, 1467, 1360, 1274, 1131. 1H NMR : 7.6\u20138.72 ; 10.82 ; 8.03 . 13C NMR : 157.9 (C=O); 154.70 (CPy); 148.07 (CPy); 146.67 (C=N) imine; 137.60 (CPy); 123.00 (CPy); 119.09 (CPy).Carbonohydrazide  was introduced into a 100\u2005mL flask containing 20\u2005mL of methanol. To the resulting suspension was added a methano\u00adlic solution containing 2-pyridine\u00adcarbaldehyde (4.757\u2005g 44.4\u2005mmol) and two drops of glacial acetic acid. The mixture was stirred under reflux for 2\u2005h. After being kept for two days at 277\u2005K, the resulting orange solution yielded a precipitate, which was recovered by filtration. The solid was washed successively with cold methanol (2 \u00d7 10\u2005mL) and diethyl ether (2 \u00d7 10\u2005mL) before being dried under PSynthesis of the title complex2L  in 10\u2005mL of methanol and a methano\u00adlic solution of ZnCl2 . A yellow solution was obtained after stirring for 1\u2005h at room temperature. The solution was filtered, and the filtrate left for slow evaporation. After two weeks, yellow crystals suitable for X-ray diffraction were collected, yield 87.9%. Analysis calculated for [C26H26Cl6Zn4N12O4] C, 29.89; H, 2.51; N, 16.09. Found: C, 29.88; H, 2.49; N, 16.05. \u039bM (S cm2 mol\u2212): 11. IR (cm\u22121): 3428, 3116, 3043, 1585, 1553, 1497, 1461, 1377, 1313, 1226, 1143, 820.The title complex was prepared by mixing a solution of HUiso(H) = 1.2Ueq(N) or 1.5Ueq(O). C atoms were placed in calculated positions and refined as riding with C\u2014H = 0.93\u2005\u00c5 and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989020009834/ex2035sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009834/ex2035Isup2.hklStructure factors: contains datablock(s) I. DOI: 2011426CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-019-45003-7, published online 14 June 2019Correction to: The Supplementary Information file originally published with this Article contained errors.In the \u2018Detailed experimental procedures:\u2019 section,\u201c106.57 (c-2\u2019)\u201dnow reads:\u201c10657 (C-2\u2019)\u201dand\u201cmp 91\u201392\u2009\u00b0C\u201dnow reads:\u201cm.p. mp 91\u201392\u2009\u00b0C\u201d.Finally, the original file contained tracked changes.These errors have been corrected in the Supplementary Information that now accompanies the Article."}
{"text": "To the Editor,Colorectal cancer (CRC) is a malignance ranking the third cause of death in malignant tumors.P value\u00a0=\u00a07.458 \u00d7 10\u221218) and indicated a favorable prognosis in patients with CRC (P\u00a0=\u00a0.016), which was inconsistent with our general understanding in other type of cancers , \u22120.71 (P\u00a0=\u00a08 \u00d7 10\u221257), and 0.71 (P\u00a0=\u00a01 \u00d7 10\u221255), respectively    showed that CCDC80 expression level was independent predictive factor  Figure\u00a0. Kaplan\u2010) Figure\u00a0. The RNA) Figure\u00a0.To explore the relationship between the drugs sensitivity and CCDC80 expression, the Genomics of Drug Sensitivity in Cancer database was utilized to analyze the correlation coefficient of CCDC80 level and IC50 of multiple drugs Figure\u00a0. To our Next, we overexpressed CCDC80 in Lovo cells by lentivirus infection and validated by RT\u2010PCR Figure\u00a0. ConsistP\u00a0=\u00a05.32 \u00d7 10\u221202), dendritic cells (P\u00a0=\u00a07.04 \u00d7 10\u221240), macrophage cells (P\u00a0=\u00a03.52 \u00d7 10\u221256), CD4+ T cells (P\u00a0=\u00a08.64 \u00d7 10\u221229), CD8+ T cells (P\u00a0=\u00a04.14\u00a0\u00d7 10\u221208), and neutrophil cells (P\u00a0=\u00a03.34 \u00d7 10\u221228)  Figure\u00a0. Furthern Figure\u00a0. Among tThe authors declare no conflict of interest.Guangci Distinguished Young Scholars Training Program; Grant Number: GCQN\u20102019\u2010B17.Yu\u2010Jun Dai, Da\u2010Wei Wang, and Ling\u2010Ling Shu designed the concept and experiments. Wei\u2010Da Wang, Kun\u2010Hao Bai, and Guo\u2010Yan Wu performed the experiments; Wei\u2010Da Wang, Si\u2010Yuan He, Xin Huang, Qian\u2010Yi Zhang, Pei\u2010Dong Chi, and Liang Li collected the data and did the analysis. Wei\u2010Da Wang, Yu\u2010Jun Dai, and Guo\u2010Yan Wu prepared the manuscript draft. Yu\u2010Jun Dai and Da\u2010Wei Wang provided research support and revised the manuscript. All the authors approved the final proof.figureS1Click here for additional data file.figureS2Click here for additional data file.tableS1Click here for additional data file.tableS2Click here for additional data file.tableS3Click here for additional data file.tableS4Click here for additional data file.Supporting informationClick here for additional data file."}
{"text": "The structure is composed of cation\u2013oxygen bilayers, which are surrounded by hydro\u00adphobic methyl\u00adethyl chains on both sides. Stacking of these sandwiches forms the structure. The potassium cations are situated in an irregular coordination polyhedron composed of seven O atoms.The structure of poly[bis\u00ad(\u03bc 2(C4H7O2)2(H2O)]n, is composed of stacked sandwiches, which are formed by cation\u2013oxygen bilayers surrounded by methyl\u00adethyl hydro\u00adphobic chains. These sandwiches are held together by van der Waals inter\u00adactions between the methyl\u00adethyl groups. The methyl\u00adethyl groups are disordered over two positions with occupancies 0.801\u2005(3):0.199\u2005(3). The potassium cations are coordinated by seven O atoms, which form an irregular polyhedron. There is a water mol\u00adecule, the oxygen atom of which is situated in a special position on a twofold axis (Wyckoff position 4e). The water H atoms are involved in Owater\u2014H\u22efOcarbox\u00adyl hydrogen bonds of moderate strength. These hydrogen bonds are situated within the cation\u2013oxygen, i.e. hydro\u00adphilic, bilayer.The structure of the title compound, [K These sandwiches are bonded by van der Waals forces.In all of these structural types, water mol\u00adecules can occur; examples are given in Table\u00a01M+CnHn+12COO\u2212, n > 2, as follows from the known structures of Li(C3H5O2) , catena-[(\u03bc2-propano\u00adato)thallium(I)(propano\u00adato)thallium(I)]  have been reviewed. The motif of stacked layers, however, seems to be typical for simple alkali alkanoates Thus, the typical motif of separated hydro\u00adphobic and hydro\u00adphilic parts of the mol\u00adecules can be generalized for carboxyl\u00adates other than formates and acetates.nHn+12COO\u2212, n > 2, hinder possible applications of these compounds, although there are some exceptions such as lanthanide zinc butyrates or their analogues, which have been applied for the synthesis of lanthanide\u2013zinc\u2013oxygen nanoparticles  1\u00a0\u2212\u00a0x, y, z; (ii) x, \u2212y, z; (iii) x, y, z; (iv) x, \u22121\u00a0+\u00a0y, z.) It is also worth mentioning that the distances between the cation and the oxygen atoms belonging to the same carboxyl\u00adate are quite different: K1\u2014O1 = 3.1113\u2005(13)\u2005\u00c5 and K1\u2014O2 = 2.8056\u2005(13)\u2005\u00c5.The structural unit of the title compound is shown in Fig.\u00a01The prominent feature of the title structure is the presence of an oxygen\u2013metal bilayer, which is surrounded by methyl\u00adethyl chains on both sides Fig.\u00a02. This biwater\u2014H\u22efOcarboxyl\u00adate hydrogen bonds of moderate strength  and 3.01\u2005(2)\u2005\u00c5, respectively, see Fig.\u00a03v, the bond valence of which is 0.0385\u2005(1) 6  = 105.00\u2005(1)\u00b0 while Uiso(H1O3) = 1.5Ueq(O3). A trial refinement showed that the water oxygen was fully occupied. The C1\u2014C2, C1\u2014C2a bonds were restrained to be equal [1.540\u2005(1)\u2005\u00c5] as were C2\u2014C3, C2\u2014C3a and C2\u2014C4, C2\u2014C4a [1.500\u2005(1)\u2005\u00c5]. These values were found to yield the lowest R factors. Moreover, angle restraints to C3\u2014C2\u2014C4 and C3a\u2014C2a\u2014C4a were also applied. Of course, these C\u2014C distances are affected by a large thermal agitation and are less reliable, as are the geometric parameters, compared to those of atom C1.The methane\u00adtriyl hydrogens H110.1107/S2056989020012591/dj2009sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020012591/dj2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012591/dj2009Isup3.smiSupporting information file. DOI: 2032320CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We performed batch incubation experiments with an anammox-dominated biomass to investigate nitrogen (N) and oxygen (O) isotopic fractionation factors during anammox and also examined apparent isotope fractionation factors during anammox in an actual wastewater treatment plant. We conducted one incubation experiment with high \u03b418O of water to investigate the effects of water \u03b418O. The N isotopic fractionation factors estimated from incubation experiments and the wastewater treatment plant were similar to previous values. We also found that the N isotopic effect (15\u03b5NXR of \u201377.8 to \u201365.9\u2030 and 15\u0394NXR of \u201331.3 to \u201330.4\u2030) and possibly O isotopic effect (18\u03b5NXR of \u201320.6\u2030) for anaerobic nitrite oxidation to nitrate were inverse. We applied the estimated isotopic fractionation factors to the ordinary differential equation model to clarify whether anammox induces deviations in the \u03b418O vs \u03b415N of nitrate from a linear trajectory of 1, similar to heterotrophic denitrification. Although this deviation has been attributed to nitrite oxidation, the O isotopic fractionation factor for anammox is crucial for obtaining a more detailed understanding of the mechanisms controlling this deviation. In our model, anammox induced the trajectory of the \u03b418O vs \u03b415N of nitrate during denitrification to less than one, which strongly indicates that this deviation is evidence of nitrite oxidation by anammox under denitrifying conditions.Isotopic fractionation factors against  However, they lacked information on the 18O fractionation factor for anammox, and assumed that the 18O fractionation factor during NO3\u2013 production by anammox was similar to that for aerobic nitrite oxidation to NO3\u2013 by nitrifiers (nitrification). Thus, it is essential to investigate the 15N and 18O fractionation factors during anammox not only for the better use of the \u03b418O and \u03b415N of NO3\u2013 in anammox studies, but also to obtain a more detailed understanding of 15N and 18O fractionation.Studies on 18O fractionation factors during anammox. We calculated apparent 15N and 18O fractionation factors with data collected from a wastewater treatment plant (WWTP) at which anammox reactors were installed at the final stage of treatment .In the first experiment (Experiment A), the biomass in the reactor was sampled and incubated with the media used for the reactor, while the sampled biomass was re-suspended in fresh, chemically defined media in the second (Experiment B) and third (Experiment C) experiments. Difficulties were associated with performing incubation experiments with the anammox biomass for isotopic measurements, and, thus, we employed slightly different settings and operations to facilitate constant and active anammox reactions. In each experiment, 15\u200d \u200dmL of the biomass suspension in media solution was filtered with filter paper  and differences in filter weights before and after filtration were used to calculate the suspended solid (S.S.) concentration after the filter had been oven-dried (at 105\u00b0C).2 gas to remove dissolved oxygen (DO). pH, DO, and the concentrations of NH4+ and NO2\u2013 were regularly measured to confirm the anammox activity of the biofilm, and pH (8.0) was maintained by adding KH2PO4 and Na2HPO4\u00b712H2O solution. After the addition of NaNO2, (NH4)2SO4, and NaHCO3, we started the incubation and sampled 10\u200d \u200dmL of media. Sampled media were filtered with a 0.20-\u03bcm syringe filter and then split into three; one for NO3\u2013 followed by the removal of NO2\u2013 (2\u2013 with high pH by the addition of 2M 2\u2013 andNaOH solution to prevent oxygen atom exchange between NO water (4+ with low pH by the addition of 4.8 M H2SO4 to prevent NH4+ from volatilizing. These subsamples were frozen (\u201330\u00b0C) until further analyses.The biofilm and incubation media solution  were sampled from the incubation membrane in the anammox reactor (SI Text 1.1). The incubation was performed anaerobically in the glovebox at room temperature (25\u201330\u00b0C) after the purging of media by N of NO2\u2013 , another2 purged) in the glovebox. Media consisted of NaHCO3 502\u200d \u200dmg L\u20131; MgSO4\u00b77H2O 603\u200d \u200dmg L\u20131; CaCl2 180.5\u200d \u200dmg L\u20131; KH2PO4 169\u200d \u200dmg L\u20131; Na2HPO4\u00b712H2O 282\u200d \u200dmg L\u20131; trace elements of solution I  0.5\u200d \u200dmL and solution II  0.5\u200d \u200dmL. We added NaNO2 and (NH4)2SO4 to media (500\u200d \u200dmL) with the anammox granules and then started the incubation at room temperature (25\u201330\u00b0C). We monitored pH (7.9 to 8.8) and NO2\u2013 to assess the progress of anammox. Sampling was performed as described in Experiment A.The granule biomass that accumulated at the bottom of the anammox reactor was sampled. Granules were rinsed anaerobically with new media (N\u03b418O of water (\u03b418OH2O) was markedly higher (229\u2030) than that in Experiments A and B (\u20138\u2030). This \u201cheavy\u201d water was prepared by mixing 18O-labeled water (10% atom 18O) with Milli-Q water. During the incubation, media with biofilms were shaken at a constant temperature (30\u00b0C) and continuously purged with a gas mixture (95% Ar\u00a0+\u00a05% CO2) to maintain low DO levels. pH ranged between 7.1 and 7.5 and the monitoring and sampling scheme was identical to Experiment BWe incubated the biofilm collected from the incubation membrane in the anammox reactor with the same media used in Experiment B; however, the 4+ concentrations were measured during the incubation by the o-phthaldialdehyde (OPA) method    with USGS 32, 34, 35, and IAEA-2 as standards, and with the azide method  with TUAT-NO2-1 to TUAT-NO2-5  were evaluated using GC-IRMS with the denitrifier method after the conversion of NH4+ to NO3\u2013 by persulfate oxidation \u20131 and (R_SampleO/R_Oxygen)\u20131 where R_SampleN and R_SampleO are [15N/14N] and [18O/16O] of the sample, respectively, R_Nitrogen is [15N/14N] of atmospheric N2 and R_Oxygen is [18O/16O] of Vienna Standard Mean Ocean Water , residual NH4+ (\u03b415NNH4+_ANX), and the fraction of NH4+ reacting (NH4+f) in ANX reactor (15\u0394AMX (The ammonium oxidation to N reactor  at a ste15\u0394AMX = (\u03b415NNH4+_ANX \u2013 \u03b415NNH4+_NT) / NH4+f --- eq. (1)NH4+f = ([NH4+]NT \u2013 [NH4+]ANX) / [NH4+]NT4+]NT and [NH4+]ANX are the NH4+ concentrations in NT and ANX reactors, respectively.where ANX / ([NO2 \u2013 ]NT \u2013 [NO2\u2013]ANX)b = ([NO3\u2013]ANX \u2013 [NO3\u2013]NT) / ([NO2\u2013]NT \u2013 [NO2\u2013]ANX)\u03b415NNO2\u2013_NT is \u03b415NNO2\u2013 in NT reactor and the concentrations of NO2\u2013 and NO3\u2013 in NT and ANX reactors are [NO2\u2013]NT, [NO2\u2013]ANX, [NO3\u2013]NT, and [NO3\u2013]ANX, respectively.where The combination of eqs. (2) and (4) gives\u03b415NNO2\u2013_NT = (1 \u2013 a \u2013 b) \u00d7 \u03b415NN2_ANX + a \u00d7 \u03b415NNO2\u2013_ANX + b\u00d7 \u03b415NNO3\u2013_ANXa \u2013 b) \u00d7 (\u03b415NNO2\u2013_ANX \u2013 15\u0394AMXNIR) + a\u00d7 \u03b415NNO2\u2013_ANX + b \u00d7 \u03b415NNO3\u2013_ANX= (1 \u2013 \u03b415NNO2\u2013_ANX \u2013 15\u0394AMXNIR \u2013 a \u00d7 \u03b415NNO2\u2013_ANX+ a \u00d7 15\u0394AMXNIR \u2013 b \u00d7 \u03b415NNO2\u2013_ANX + b \u00d7 15\u0394AMXNIR+ a \u00d7 \u03b415NNO2\u2013_ANX + b \u00d7 \u03b415NNO3\u2013_ANX= b \u00d7 (\u03b415NNO3\u2013_ANX \u2013 \u03b415NNO2\u2013_ANX) + \u03b415NNO2\u2013_ANX+ 15\u0394AMXNIR \u00d7 (a + b \u2013 1)= b \u00d7 15\u0394NXR) + \u03b415NNO2\u2013_ANX + 15\u0394AMXNIR \u00d7 (a + b \u2013 1)= \u2013 (15\u0394AMXNIR = [\u03b415NNO2\u2013_ANX \u2013 \u03b415NNO2\u2013_NT \u2013 b \u00d7 15\u0394NXR] / (a + b \u2013 1) --- eq. (5)18O fractionation during nitrite oxidation to nitrate, we followed the approach described by 18EAMXcombined) because of the lack of detailed information on isotopic fractionation for the nitrite oxidation and oxygen atom incorporation during nitrite oxidation. Thus, we calculated 18EAMXcombined as follows:To calculate 18EAMXcombined = 2/3 \u03b418ONO2\u2013_ANX + 1/3 \u03b418OH2O \u2013 \u03b418ONO3\u2013_ANX--- eq. (6)\u03b418ONO2\u2013_ANX, \u03b418OH2O, and \u03b418ONO3\u2013_ANX are the 18O ratios of NO2\u2013, water, and NO3\u2013 in ANX reactor, respectively.where 2\u2013 were then estimated from isotopic data.We developed an ordinary differential equation model as described by Fluxes regarding the anammox process  are defikAMO14N \u00d7 [14NH4+] --- eq. (7)AMX = AMXNIR = x / (1 \u2013 x)) --- eq. (8)NXR = AMXNIR \u00d7 (14N) fluxes of ammonium oxidation, nitrite oxidation, and reduction by anammox  .where AMX, NXR, and AMXNIR are the   in the a [NO2\u2013])  and the 2\u2013;Regarding NO14NO2\u2013] = \u2013 NXR \u2013 AMXNIR --- eq. (9)d/dt [15NO2\u2013] = \u2013 (R_NitriteN \u00d7 NXR / 15\u03b5NXR)15\u03b5AMXNIR) --- eq. (10)\u2013 (R_NitriteN \u00d7 AMXNIR / d/dt [16O2\u2013] = \u2013 2NXR \u2013 2AMXNIR --- eq. (11)d/dt [N16O18O\u2013] = \u2013 (R_NitriteO \u00d7 2NXR / 18\u03b5NXR)\u2013 (R_NitriteO \u00d7 2AMXNIR / 18\u03b5AMXNIR)\u2013 N16O18O\u2013exch_OUT + N16O18O\u2013exch_INd/dt [N18\u03b5NXR)\u2013 (R_NitriteO \u00d7 2AMXNIR / 18\u03b5AMXNIR)\u2013 kexch \u00d7 [N16O18O\u2013] + kexch\u00d7R_WaterO / 18\u03b5EQ--- eq. (12)= \u2013 , N16O18O\u2013exch_OUT, and N16O18O\u2013exch_IN  as described by 2\u2013 and H2O.where R_NitriteO, R_NitrateO, R_NitriteN, and R_NitrateN are the e and pH . We appl3\u2013;Regarding NO14NO3\u2013] = NXR --- eq. (13)d/dt [15NO3\u2013] = (R_NitriteN \u00d7 NXR / 15\u03b5NXR) --- eq. (14)d/dt [16O3\u2013] = 3 NXR --- eq. (15)d/dt [N18O16O2\u2013] = (R_NitriteO \u00d7 2 NXR / 18\u03b5NXR)+ (R_WaterO \u00d7 NXR) / 18\u03b5H2ONXR) --- eq. (16)d/dt [N18\u03b5H2ONXR d/dt [15NH4+] = \u2013 (R_AmmoniumN \u00d7 AMX/ 15\u03b5AMX) --- eq. (18)d/dt [15N / 14N of [NH4+] and 15\u03b5AMX is the N isotopic fractionation factor for NH4+ consumption by anammox (where R_AmmoniumN is the  anammox .2\u2013 and NH4+ to N2 and NO3\u2013 is as follows (The approximate stoichiometry of the anammox process converting NO2\u2013 + 1NH4+ \u2192 1N2 + 0.3NO3\u2013 + 2H2O --- eq. (19)1.3NOx) together with kAMO14N with concentration data, which provided the AMX, AMXNIR, and NXR fluxes used in the calculation above . We assigned the range from 0 to 60\u2030  to estimate isotopic fractionation factors. We considered this 60\u2030 range for the curve-fitting estimate to be reasonable because isotopic fractionation factors larger than 60\u2030 are rarely observed  and consequently 18EAMXcombined , were not all successfully estimated for Experiments B and C. Based on these uncertainties in parameter estimations, we did not report these calculated values for Experiments B and C; however, we speculate that these calculated parameter sets support 18\u03b5AMXNIR as normal and 18\u03b5NXR being inverse isotope fractionation, as discussed below for Experiment A. The curve-fitting function (\u201cmultiple-fit\u201d in BM software) (\u20136. BM codes for the anammox model for curve fittings with concentrations and isotopic data are provided in the Zenodo website (https://doi.org/10.5281/zenodo.3895346) and However, this stoichiometry between nitrite removal and nitrate production has been reported to vary d/dt [15NO2\u2013] = \u2013 (R_NitriteN \u00d7 NXR / 15\u03b5NXR)+ (R_NitrateN \u00d7 NAR / 1518\u03b5NAR)\u2013 (R_NitriteN \u00d7 DENNIR / 15\u03b5DENNIR)\u2013 (R_NitriteN \u00d7 AMXNIR / 15\u03b5AMXNIR) --- eq. (21)d/dt [16O2\u2013] = \u2013 2 NXR + 2 NAR \u2013 2 DENNIR \u2013 2 AMXNIR --- eq. (22)d/dt [N1518\u03b5NAR + (R_NitrateO \u00d7 2 NAR / 1518\u03b5NAR) / 18\u03b5H2OBRNAR\u2013 (R_NitriteO \u00d7 2 DENNIR / 18\u03b5DENNIR)\u2013 (R_NitriteO \u00d7 2 AMXNIR / 18\u03b5AMXNIR) --- eq. (23a)d/dt [N18\u03b5H2OBRNAR is the 18O fractionation factor for the \u201cbranching effect\u201d  + 1]d/dt  = NXR \u2013 NAR --- eq. (24)d/dt [15NO3\u2013] = (R_NitriteN \u00d7 NXR / 15\u03b5NXR) \u2013 (R_NitrateN \u00d7 NAR / 1518\u03b5NAR) --- eq. (25)d/dt [18O16O2\u2013] = 3 NXR \u2013 3 NAR --- eq. (26)d/dt [N18O16O2\u2013] = (R_NitriteO \u00d7 2 NXR / 18\u03b5NXR)+ (R_WaterO \u00d7 NXR / 18\u03b5H2ONXR)\u2013 (R_NitrateO \u00d7 3 NAR / 1518\u03b5NAR) --- eq. (27)d/dt  and [NO2\u2013] decreased during anammox (\u03b418ONO2\u2013 and \u03b418ONO3\u2013 did not change in Experiment A (\u03b418ONO3\u2013 increased by ~2\u2030 and \u03b418ONO2\u2013 decreased by ~3\u2030 in Experiment B (\u03b418O of H2O (229\u2030), \u03b418ONO2\u2013 and \u03b418ONO3\u2013 rapidly increased  for Kuenenia stuttgartiensis in batch incubation experiments  (Candidatus Jettenia\u201d with the nirK gene ( 2 \u00b1 2\u2030) . The simirK gene .15N and 18O fractionation factors during anaerobic nitrite oxidization to NO3\u2013 of \u201377.8\u2030 for 15\u03b5NXR and \u201320.6\u2030 for 18\u03b5NXR ; defined as  \u2013 (18\u03b5 / 15\u03b5), where 18\u03b5 / 15\u03b5 is the ratio of isotopic fractionation for O and N during denitrification, respectively, and assigned as 1; see the inset in 2\u2013 was consumed. In the case of denitrification in which AMX / NAR is equal to 0 (indicating no anammox), \u03b418ONO3\u2013 vs \u03b415NNO3\u2013 was set to show a slope of 1 . To elucidate the relationship between \u0394, AMX / NAR, and isotopic fractionation factors, we simulated the \u03b418ONO3\u2013 and \u03b415NNO3\u2013 trajectories along with the different AMX / NAR ratios and 15\u03b5AMXNXR ; however, \u0394 depended on AMX / NAR, 15\u03b5AMXNXR, and 15\u03b5NXR , our simulation exercise revealed that \u0394, the offset from the 1:1 relationship between \u03b415N and \u03b418O, may be useful for detecting NXR (nitrite oxidation) in denitrifying systems in both freshwater and seawater.We developed an anammox-denitrification model with the estimated isotopic fractionation factors  denitrification with auxiliary Nap NO3\u2013 reductase may exhibit a 2:1 rather than 1:1 relationship between \u03b415N and \u03b418O, resulting in an offset from the 1:1 relationship  is not considered to be a major environmental sink for NO3\u2013  may induce an offset from the denitrification trajectory . In practice, \u0394 may be evaluated with time-course samplings or short incubation studies to investigate the occurrence of anammox, similar to denitrification. This technique will be advantageous because of its potential in evaluations of the quantitative contribution in situ of anammox versus denitrification. Although the detection and quantification of functional genes in denitrification and anammox may be readily performed, difficulties are associated with detecting the in situ occurrence of denitrification and anammox. Although the isotopic fractionation factors used also need to be considered, \u0394 is a promising parameter to complement molecular data and the results from laboratory incubation experiments in the study of anammox.We estimated Microbes Environ 35: ME20031.Kotajima, S., Koba, K., Ikeda, D., Terada, A., Isaka, K., Nishina, K., et al. (2020) Nitrogen and Oxygen Isotope Signatures of Nitrogen Compounds during Anammox in the Laboratory and a Wastewater Treatment Plant. https://doi.org/10.1264/jsme2.ME20031Supplementary Material"}
{"text": "Hypercalcemia is a frequently encountered electrolyte abnormality with a well-described differential diagnosis and classic algorithm for evaluation. The treatment for hypercalcemia is dependent on the underlying etiology. Hypervitaminosis D is an uncommon cause of hypercalcemia, but the use of vitamin D supplementation has expanded and case reports of supplemental vitamin D induced hypercalcemia have become more frequent. We present a case of hypervitaminosis D-induced altered mental status where diagnosis was delayed and additional invasive testing was performed due to an assumption regarding phosphatemia.  Vitamin D is a steroid hormone crucial for both bone health and calcium homeostasis . It can 2 95%. Physical exam revealed bilateral upper extremity tremors and obtundation. Pupils were symmetric and reactive to light, and he periodically tracked with his eyes. Neurological exam, including reflexes, was limited due to altered mental status. Cardiopulmonary exam was benign. Chest X-ray was notable for a normal cardiopulmonary silhouette. Electrocardiogram revealed normal sinus rhythm with a QTc interval of 409\u00a0ms. Computed tomography of the brain without contrast showed normal gray-white matter differentiation. A 64-year-old man with a history of chronic obstructive pulmonary disease and ethanol abuse use presented to the emergency department with altered mentation. He was obtunded on arrival, unable to provide any additional history. Presenting vitals were notable for blood pressure of 150/93, pulse of 69 beats per minute, temperature of 97.3\u00a0\u00b0F (36.3\u00a0\u00b0C), respiratory rate of 18 BPM, and SpOLaboratory evaluation revealed a sodium 143\u00a0mEq/L (135\u00a0\u2013\u00a0145\u00a0mEq/L), potassium 3.0\u00a0mEq/L (3.6\u00a0\u2013\u00a05.1\u00a0mEq/L), chloride 105 mEq/L (98\u00a0\u2013\u00a0110\u00a0mEq/L), bicarbonate 27\u00a0mEq/L (22\u00a0\u2013\u00a032 mEq/L), blood urea nitrogen 14\u00a0mg/dL (6\u00a0\u2013\u00a024\u00a0mg/dL), creatinine 1.11\u00a0mg/dL (0.64\u00a0\u2013\u00a01.27 mg/dL), undetectable blood ethanol level, blood glucose 95\u00a0mg/dL (67\u00a0\u2013\u00a099\u00a0mg/dL), calcium 12.8\u00a0mg/dL (8.5\u00a0\u2013\u00a010.5 mg/dL), ionized calcium 6.3\u00a0mg/dL (4.2\u00a0\u2013\u00a05.2\u00a0mg/dL), phosphorus of 2.2\u00a0mg/dL (2.4\u00a0\u2013\u00a04.8 mg/dL), and albumin 4.0\u00a0g/dL (3.5\u00a0\u2013\u00a05.0\u00a0g/dL). Initial management consisted of volume expansion with 3\u00a0L normal saline without improvement in mentation. Calcitonin was given on hospital day\u00a02 and zoledronic acid was given on hospital day\u00a03, but hypercalcemia persisted. Further labwork returned with intact parathyroid hormone (iPTH) 17\u00a0pg/mL (18\u00a0\u2013\u00a080\u00a0pg/mL), parathyroid hormone related peptide (PTHrP) 9\u00a0pg/mL (pg/mL 14\u00a0\u2013\u00a027), serum protein electrophoresis (SPEP) and immunofixation (IFE) without evidence of monoclonal protein, \u03ba light chains 85.4\u00a0mg/L (3.3\u00a0\u2013\u00a019.4 mg/L), \u03bb light chains 40.8 mg/L (5.7\u00a0\u2013\u00a026.3\u00a0mg/L), and \u03b2-2 microglobulin 3.75\u00a0mg/L (0.97\u00a0\u2013\u00a02.64\u00a0mg/L). The elevation of \u03ba/\u03bb ratio in the setting of a normal glomerular filtration rate prompted evaluation for a monoclonal gammopathy. Skeletal survey was negative for lytic lesions and bone marrow biopsy was negative for plasma cell dyscrasia. Finally, the following labs resulted: 25-hydroxy vitamin D >\u00a0150\u00a0ng/mL (30.0\u00a0\u2013\u00a0100.0\u00a0ng/mL), 1,25-hydroxy vitamin D 36 pg/mL (18\u00a0\u2013\u00a072\u00a0pg/mL). The patient remained agitated and confused for the first 10\u00a0days of hospitalization, but mentation improved thereafter with calcium normalizing after 18\u00a0days. Upon recovery, he reported misunderstanding medication instructions and had been consuming 4 vitamin\u00a0D 50,000 IU tablets daily. This case highlights the risks of pathophysiologic assumptions. The findings of hypercalcemia with appropriately suppressed iPTH and low PTHrP resulted in an evaluation for hypervitaminosis D. However, hypophosphatemia directed the evaluation away from hypervitaminosis D, leading to additional evaluation for paraproteinemia. The finding of an abnormal \u03ba-to-\u03bb ratio and elevated \u03b2-2 microglobulin, resulted in evaluation for plasma cell dyscrasia with a bone marrow biopsy. The patient had an elevated vitamin D 25OHD and normal calcitriol revealing the ultimate diagnosis to be hypervitaminosis D. The presentation of hypercalcemia frequently varies with the level of serum calcium. Individuals with mild hypercalcemia (<\u00a012\u00a0mg/dL) are typically asymptomatic . ModeratHypervitaminosis D classically presents as hypercalcemia with hyperphosphatemia and low PTH , 12. VitSerum phosphorus regulation is likely incompletely understood. Phosphate is regulated by PTH, fibroblast growth factor 23 (FGF23), and 1,25OHD . PhosphaThis case highlights the importance of having a broad differential for hypercalcemia. We recommend that hypervitaminosis D be considered in patients with hypercalcemia and low PTH regardless of phosphorus level. The authors did not receive support for this work. The authors declare no conflict of interest."}
{"text": "Litylenchus crenatae mccannii (Anguinidae) nematodes by systematically testing thermostable polymerases, proofreading enzymes and buffers. The combination of thermostable DreamTaq\u2122, proofreading Pfu polymerase, and PicoMaxx\u2122 buffer provided the best results. These nematodes are the subject of surveys currently active at many sites in the northeastern United States. This new, optimized PCR protocol will be useful for diagnostic labs associated with the surveys.Generating DNA markers for microscopic plant parasitic nematodes can be especially difficult if only a few valuable, tiny specimens are available. Providing a reliable maximum amount of unambiguous genetic information from single nematodes is especially important when identifying damaging, regulated nematodes of importance to trade where a few nucleotide differences in diagnostic markers are significant. There are many possible reasons for difficulty amplifying unpurified nematode DNA for long range PCR followed by direct sequencing. Specimen age, proofreading errors and reagent compatibility during PCR are among those problems. While unsuccessful direct amplification of difficult samples may sometimes be overcome by cloning, a more expensive and time-consuming process. Therefore, long segment PCR of a large 3.5\u2009kb segment of ribosomal DNA was optimized for individual difficult-to-amplify young  Fagus grandifolia) trees in Ohio, Pennsylvania, New York and Connecticut. It was discovered first in 2012 near Lake Erie in the Cleveland Metroparks, region of Ohio (Beech leaf disease (BLD) is an emerging tree disease in the Northeast for American beech . Their ribosomal DNA (rDNA) loci were amplified by PCR with the one primer set and an enhanced DNA polymerase system, and the resulting 3.5\u2009kb  rDNA amplicons were directly sequenced  and PicoMaxx\u2122 High Fidelity PCR System  were selected and tested in this study.Commonly used o 2.9\u2009kb . It has R system . As a reLitylenchus specimens were isolated from the banding lesions of American beech leaves with BLD as described in Litylenchus and the visualization, cleanup and direct DNA sequencing, including sequencing primers, of the PCR products were performed by using the procedures described in previous studies  were performed by using the procedures, including primer sets, 18S-CL-F3 and 28S-CL-R for the 3.5\u2009kb ribosomal loci, 18S-CL-F3 and 18S-CL-R7 for the 18\u2009S locus (1.7\u2009kb) and ITS-CL-F2 and 28S-CL-R for the ITS-28S (D1D2D3) loci (1.9\u2009kb) described in the previous study   was carried out in a 25\u2009\u03bcl of mixture containing Platinum\u2122 Taq (10 units/\u03bcl) 0.125\u2009\u03bcl, 10X PCR Buffer Mg 2.5\u2009\u03bcl, MgCl2 (50\u2009mM) 1\u2009\u03bcl, dNTP (2.0\u2009mM each) 2.5\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer (10\u2009\u03bcm) 0.75\u2009\u03bcl and reverse primer (10\u2009\u03bcm) 0.75\u2009\u03bcl for either primer set 18S-CL-F3 and 28S-CL-R or ITS-CL-F2 and 28S-CL-R, and molecular biology grade water  15.375\u2009\u03bcl. The thermal cycling program was one cycle of 95\u00b0C for 3\u2009min; 36 cycles of 95\u00b0C for 30\u2009sec, 50\u00b0C for 45\u2009sec, 72\u00b0C for 3\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with Platinum\u2122 Taq2000\u2122 DNA Polymerase  was carried out in a 25\u2009\u03bcl mixture containing Taq2000\u2122 (5 units/\u03bcl) 0.25\u2009\u03bcl, 10X PCR Buffer 2.5\u2009\u03bcl, MgCl2 (50\u2009mM) 0.25\u2009\u03bcl, dNTP (2.0\u2009mM each) 2.5\u2009\u03bcl, Template DNA 2\u2009\u03bcl, both forward primer (10\u2009\u03bcm) 0.75\u2009\u03bcl and reverse primer (10\u2009\u03bcm) 0.75\u2009\u03bcl for either primer set 18S-CL-F3 and 28S-CL-R or ITS-CL-F2 and 28S-CL-R, and molecular biology grade water  16\u2009\u03bcl. The thermal cycling program was one cycle of 95\u00b0C for 3\u2009min; 36 cycles of 95\u00b0C for 30\u2009sec, 50\u00b0C for 45\u2009sec, 72\u00b0C for 3\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with Taq\u2122 DNA Polymerase  alone or combined with DreamTaq\u2122 was carried out in a 25\u2009\u03bcl of mixture containing TaKaRa Ex Taq\u2122 (5 units/\u03bcl) 0.125\u2009\u03bcl (or plus DreamTaq\u2122 (5 units/\u03bcl) 0.125\u2009\u03bcl), 10X Ex Taq Buffer 2.5\u2009\u03bcl, dNTP (2.5\u2009mM each) 2\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10 \u03bcm) 1.25\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 1.25\u2009\u03bcl, and molecular biology grade water  15.875\u2009\u03bcl (or 15.75\u2009\u03bcl). The thermal cycling program was: one cycle of 98\u00b0C for 30\u2009sec; 36 cycles of 98\u00b0C for 10\u2009sec, 68\u00b0C for 5\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with TaKaRa Ex Taq\u2122 was carried out in a 25\u2009\u03bcl of mixture containing PicoMaxx\u2122 high fidelity PCR system (PicoMaxx\u2122 (5 units/\u03bcl)) 0.5\u2009\u03bcl (or plus DreamTaq\u2122 (5 units/\u03bcl) 0.125\u2009\u03bcl), 10\u00d7 PicoMaxx\u2122 reaction buffer (PicoMaxx\u2122 buffer) 2.5\u2009\u03bcl, dNTP (25\u2009mM each) 0.2\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10\u2009\u03bcm) 1.25\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 1.25\u2009\u03bcl, and molecular biology grade water  17.3\u2009\u03bcl (or 17.175\u2009\u03bcl). The thermal cycling program was one cycle of 95\u00b0C for 2\u2009min; 36 cycles of 95\u00b0C for 30\u2009sec, 55\u00b0C for 45\u2009sec, 72\u00b0C for 5\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with PicoMaxx\u2122 High Fidelity PCR System (PicoMaxx\u2122 System)  alone or combined with Dreampfu DNA polymerase  alone or combined with DreamTaq\u2122 was carried out in a 25\u2009\u03bcl of mixture containing pfu (2.5 units/\u03bcl) 0.75\u2009\u03bcl (or plus DreamTaq\u2122 (5 units/\u03bcl) 0.125\u2009\u03bcl), 10\u00d7 Pfu reaction buffer, 10\u00d7 PicoMaxx\u2122 buffer, or 10\u00d7 DreamTaq\u2122 buffer 2.5\u2009\u03bcl, dNTP (25\u2009mM each) 0.2\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10\u2009\u03bcm) 1.25\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 1.25\u2009\u03bcl, and molecular biology grade water  16.85\u2009\u03bcl (or 16.725\u2009\u03bcl). The thermal cycling program was one cycle of 95\u00b0C for 2\u2009min; 36 cycles of 95\u00b0C for 30\u2009sec, 55\u00b0C for 45\u2009sec, 72\u00b0C for 5\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with Pwo DNA polymerase  alone or combined with DreamTaq\u2122 was carried out in a 25\u2009\u03bcl final volume consisting of two mixtures: 12.5\u2009\u03bcl of mixture A containing Pwo (5 units/\u03bcl) 0.125\u2009\u03bcl (or plus DreamTaq (5 units/\u03bcl) 0.125\u2009\u03bcl), 10\u00d7 Pwo reaction buffer or 10\u00d7 PicoMaxx\u2122 buffer 2.5\u2009\u03bcl, and molecular biology grade water  9.875\u2009\u03bcl (or 9.75\u2009\u03bcl); 12.5\u2009\u03bcl of mixture B containing dNTP (25\u2009mM each) 0.4\u2009\u03bcl, template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10\u2009\u03bcm) 1.25\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 1.25\u2009\u03bcl. The thermal cycling program was one cycle of 95\u00b0C for 2\u2009min; 36 cycles of 95\u00b0C for 30\u2009sec, 57\u00b0C for 45\u2009sec, 72\u00b0C for 5\u2009min; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with Each PCR amplification with Herculase\u00ae II Fusion DNA polymerase  was carried out in a 25\u2009\u03bcl of mixture containing Herculase\u00ae II Fusion DNA polymerase 0.5\u2009\u03bcl, 5\u00d7 reaction buffer 5\u2009\u03bcl, dNTP (25\u2009mM each) 0.25\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10\u2009\u03bcm) 0.625\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 0.625\u2009\u03bcl, and molecular biology grade water  16\u2009\u03bcl. The thermal cycling program was: one cycle of 95\u00b0C for 2\u2009min; 36 cycles of 95\u00b0C for 20\u2009sec, 55\u00b0C for 20\u2009sec, 72\u00b0C for 2\u2009min 15\u2009sec; and final extension at 72\u00b0C for 7\u2009min.Each PCR amplification with Phusion\u2122 High-Fidelity DNA Polymerase  was carried out in a 25\u2009\u03bcl of mixture containing Phusion\u2122 High-Fidelity DNA Polymerase (2 units/\u03bcl) 0.25\u2009\u03bcl, 5\u00d7 reaction buffer 5\u2009\u03bcl, dNTP (2.5\u2009mM each) 0.5\u2009\u03bcl, Template DNA 2\u2009\u03bcl, forward primer 18S-CL-F3 (10\u2009\u03bcm) 1.25\u2009\u03bcl, reverse primer 28S-CL-R (10\u2009\u03bcm) 1.25\u2009\u03bcl, DMSO 0.25\u2009\u03bcl, and molecular biology grade water  14.5\u2009\u03bcl. The thermal cycling program was: one cycle of 95\u00b0C for 2\u2009min; 36 cycles of 95\u00b0C for 20\u2009sec, 55\u00b0C for 20\u2009sec, 72\u00b0C for 2\u2009min 15\u2009sec; and final extension at 72\u00b0C for 7\u2009min.Taq\u2122 system were carried out in 10 out of 11 Fall specimens. The direct sequencing for the three loci (3.5\u2009kb) was also conducted successfully in all specimens, except for 104H89 and 104H90 with low PCR yields that were good for sequencing only one or two loci. The 3.5\u2009kb rDNA sequences generated for the specimens, 104H82 ( MN525396) and 104H83 (MN525397) were submitted to GenBank. This result shows that DreamTaq\u2122 had the ability to amplify the 3.5\u2009kb target in most Fall specimens within the size limit by Taq DNA polymerase up to 3 to 4\u2009kb on amplicon , and ITS and 28\u2009S loci (1.9\u2009kb) within the 3.5\u2009kb target, respectively. The amplifications showed that DreamTaq\u2122 can amplify both medium 1.7\u2009kb and 1.9\u2009kb fragments with high yield  seen in Both TaKaRa  compare  with 3B.pecimens , the Drebination . This suPwo (derived from Pyrococcus woesei), another proofreading DNA polymerase, was tested in line with the Pfu in PicoMaxx\u2122 buffer. Pwo or DreamTaq\u2122 alone . No significant amplifications of the 3.5\u2009kb target were seen in the presence of either buffer (data not shown). This confirms again that PCR buffer is another key to the success of the DreamTaq\u2122 and Pfu or Pwo combination.with Pwo . The preTaq\u00ae system and PicoMaxx\u2122 system was also performed. Taq\u00ae systems failed to amplify the 3.5\u2009kb target, but the PicoMaxx\u2122 system gave DreamTaq\u2122 dramatic leverage over the TaKaRa Ex Taq\u00ae system  and ability to amplify long target (>20\u2009kb) (both Agilent and Thermo Fisher Scientific web sites). Herculase\u00ae II Fusion DNA polymerase and Phusion\u2122 High-Fidelity DNA Polymerase were tested. Fusion DNA polymerase is an engineered fusion of a proofreading polymerase and a processivity-enhancing domain  and offeTaq2000\u2122, which is one of the components of the PicoMaxx\u2122 system, Platinum\u2122 Taq and DreamTaq\u2122 were also compared in Spring specimens. In the presence of their own buffers, both the long segment PCR for the 3.5\u2009kb target and the medium range PCR for the 1.9\u2009kb target were carried out. In the long segment PCR amplifications, all of the three Taqs failed to amplify the 3.5\u2009kb target  and DreamTaq\u2122 can successfully amplify the 3.5\u2009kb target in the specimens where both DreamTaq\u2122 and PicoMaxx\u2122 systems failed separately.The PCR performances of b target . In the Taq-based blend systems, TaKaRa Ex Taq\u00ae DNA Polymerase in the specimen 104J58 (OH), PicoMaxx\u2122 High Fidelity PCR System in the Summer Specimen 104K17 (OH); by the combination of DreamTaq\u2122 and PicoMaxx\u2122 High Fidelity PCR System in the Summer specimens, 104K25  and 104K37  were sequenced and the resulting rDNA sequences (ITS and 28\u2009S loci) were deposited in GenBank with the accession numbers, 104H82, MN525396; 104H83, MN525397; 104J58 MN525398; 104K17, MN525399; 104k25, MN525400; 104K37, MN525401, respectively. Multiple alignments of these sequences above with the 3.5\u2009kb rDNA (MK292137 and MK292138) of the Ohio Litylenchus specimens in the previous study  in these Summer specimens . DreamTaq\u2122 also demonstrated its higher sensitivity than either Taq2000\u2122 or Platinum\u2122 Taq , Pristionchus sp. (Rhabditida) and Prodorylaimus sp. (Dorylaimida) when their specimens were difficult to amplify with the one primer set and DreamTaq\u2122 (data not shown). This improvement provides high fidelity, sensitivity and yield with minimum optimization of reaction and cycling conditions. It should not be limited to long segment PCR amplification only, and could be considered for short range PCR with forensic or ancient DNA, single copy nuclear gene PCR or where improved proofreading can rescue mismatches that take place between the 3\u2019 primer termini and its target templates.Taken together, the size limit to the 3.5\u2009kb target by"}
{"text": "The title compound exhibits exceptionally weak inter\u00admolecular C\u2014H\u22ef\u03c0 hydrogen bonding of the ethynyl groups, with the corresponding H\u22ef\u03c0 separations [2.91\u2005(2) and 3.12\u2005(2)\u2005\u00c5] exceeding normal vdW distances. This bonding compliments distal contacts of the CH \u22ef\u03c0 type [H\u22ef\u03c0 = 3.12\u2005(2)\u20133.14\u2005(2)\u2005\u00c5] to sustain supra\u00admolecular layers. 14H16, exhibits exceptionally weak inter\u00admolecular C\u2014H\u22ef\u03c0 hydrogen bonding of the ethynyl groups, with the corresponding H\u22ef\u03c0 separations [2.91\u2005(2) and 3.12\u2005(2)\u2005\u00c5] exceeding normal vdW distances. This bonding complements distal contacts of the CH \u22ef\u03c0 type [H\u22ef\u03c0 = 3.12\u2005(2)\u20133.14\u2005(2)\u2005\u00c5] to sustain supra\u00admolecular layers. Hirshfeld surface analysis of the title compound suggests a relatively limited significance of the C\u22efH/H\u22efC contacts to the crystal packing (24.6%) and a major contribution from H\u22efH contacts accounting 74.9% to the entire surface.The title compound, C The shortest contacts between successive layers concern inter\u00adactions involving the methyl\u00adene groups C10H\u22efCg(C1C2)iv  . The Hirshfeld surface of the mol\u00adecule, mapped over dnorm in the color range 0.0957 to 1.3378 a.u., indicates only a set of normal vdW contacts (white regions) corresponding to the closest inter\u00adactions  are by far the major contributors (74.9%) to the entire surface, while the fraction of C\u22efH/H\u22efC contacts accounts for only 24.6%. The latter value may be compared with contributions of 40.0 and 32.4% calculated for \u03b1,\u03c9-octa- and deca\u00addiynes  global, I. DOI: 10.1107/S2056989020005964/lh5958Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020005964/lh5958Isup3.cmlSupporting information file. DOI: 2000259CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the mol\u00adecular packing, O\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds lead to supra\u00admolecular layers propagating in the ab plane.In the title tri-substituted thio\u00adurea mol\u00adecule, a substantial twist is evident as seen in the dihedral angle of 65.92\u2005(12)\u00b0 between the planes through the CN 12H15N3O5S, a tris\u00adubstituted thio\u00adurea derivative, the central CN2S chromophore is almost planar (r.m.s. deviation = 0.018\u2005\u00c5) and the pendant hy\u00addroxy\u00adethyl groups lie to either side of this plane. While to a first approximation the thione-S and carbonyl-O atoms lie to the same side of the mol\u00adecule, the S\u2014C\u2014N\u2014C torsion angle of \u221247.8\u2005(2)\u00b0 indicates a considerable twist. As one of the hy\u00addroxy\u00adethyl groups is orientated towards the thio\u00adamide residue, an intra\u00admolecular N\u2014H\u22efO hydrogen bond is formed which leads to an S(7) loop. A further twist in the mol\u00adecule is indicated by the dihedral angle of 65.87\u2005(7)\u00b0 between the planes through the CN2S chromophore and the 4-nitro\u00adbenzene ring. There is a close match between the experimental and gas-phase, geometry-optimized (DFT) mol\u00adecular structures. In the crystal, O\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds give rise to supra\u00admolecular layers propagating in the ab plane. The connections between layers to consolidate the three-dimensional architecture are of the type C\u2014H\u22efO, C\u2014H\u22efS and nitro-O\u22ef\u03c0. The nature of the supra\u00admolecular association has been further analysed by a study of the calculated Hirshfeld surfaces, non-covalent inter\u00adaction plots and computational chemistry, all of which point to the significant influence and energy of stabilization provided by the conventional hydrogen bonds.In the title compound, C Such N,N\u2032-di-N\u2032-benz\u00adoyl\u00adthio\u00adurea derivatives have a carbonyl group connected to the thio\u00adurea framework and offer opportunities for rich coordination chemistry as these mol\u00adecules feature both hard (oxygen) and soft (sulfur) donor atoms along with nitro\u00adgen donors and indeed, a variety of coordination modes have been observed. The neutral mol\u00adecule has been observed to coordinate in a monodentate-S mode  inter\u00adactions \u00b0 is consistent with a significant twist in the mol\u00adecule about the C1\u2014N2 bond; the O3\u2014C6\u2014N2\u2014C1 torsion angle is \u22123.6\u2005(2)\u00b0.Selected geometrical data for (I)2S plane (r.m.s. deviation = 0.017\u2005\u00c5). Crucially, the O1-hydroxy\u00adethyl group is folded towards the thio\u00adamide residue, which allows for the formation of an intra\u00admolecular N2\u2014H\u22efO1 hydrogen bond and an S(7) loop, Table\u00a022S atoms and the terminal C7\u2013C12 aryl ring. From Table\u00a01The hy\u00addroxy\u00adethyl groups lie to either side of the CNd,p) basis set \u00b0 (X-ray) versus \u221216.5\u00b0 , indicating a greater deviation from the anti-disposition in the optimized structure. Also, the N1\u2014C2\u2014C3\u2014O1 and N1\u2014C4\u2014C5\u2014O2 torsion angles are close to symmetric in the optimized structure cf. the experimental structure. Similar trends were noted in analogous calculations performed on the 4-methyl analogue . The layers are connected into a three-dimensional architecture by methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl), methyl\u00adene-C\u2014H\u22efS(thione) and comparatively rare nitro-O\u22ef\u03c0(ar\u00adyl) contacts, Fig.\u00a03b).In the crystal of (I)s Table\u00a02 lead to Crystal Explorer 17  reflects the relative likelihood of the formation of X-to-Y inter\u00adactions in a crystal, i.e. the ratio between the proportion of actual contacts in a crystal to the theoretical proportion of random contacts. Data for (I)The enrichment ratio (ER) descriptor, which is derived from the analysis of the Hirshfeld surface (Jelsch a)\u2013(f), respectively, with a summary of the percentage contributions from the various contacts given in Table\u00a05de + di \u223c1.8\u2005\u00c5 in Fig.\u00a07c). The prominent features in Fig.\u00a07d) reflect the significant C\u22efH/H\u22efC contacts evident in the packing, Tables 2de + di \u223c2.1\u2005\u00c5 in the fingerprint plot of Fig.\u00a07e). The 5.8% contribution from C\u22efO/O\u22efC contacts and the aforementioned ER value of 1.66 clearly indicate the significance of the nitro-N\u2014O\u22ef\u03c0 inter\u00adaction upon the packing; this inter\u00adaction is reflected in the pair of short spikes de + di \u223c3.0\u2005\u00c5, Fig.\u00a07f).The overall fingerprint plots for (I)EBSSEint) are listed in Table\u00a06et al., 2019The energy calculations were performed using DFT-wB97XD/aug-cc-pVTZ  of all pairwise inter\u00adactions sums to \u221245.89 kcal/mol, while the total dispersion energy term (Edispersion) computes to \u221251.51 kcal/mol.From the aforementioned, the mol\u00adecular packing is clearly governed by directional hydrogen bonding between mol\u00adecules. The simulated energy frameworks N(H)C(=S)N(CH2CH2OH)2, namely Y = H, which has been reported twice , 68.96\u2005(12), 69.51\u2005(8) and 72.15\u2005(10)\u00b0 for (I)Y = H, F and Me, respectively.There are three literature precedents to (I)The mol\u00adecular packing in the crystals is also very similar with the formation of the intra\u00admolecular thio\u00adamide-N\u2014H\u22efO(hy\u00addroxy) hydrogen bond as well as the inter\u00admolecular hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen and hy\u00addroxy-O\u2014H\u22efS(thione) hydrogen bonding, leading to a supra\u00admolecular layer in each case.\u22121): 3277 , 3170 , 3077 , 2973\u20132882 , 1692 , 1538 , 1524 , 1343 , 1270 , 1053 , 734 . UV : \u03bbmax nm (log \u220a) 366.4 (4.16), 301.6 (4.88), 271.2 (5.00), 205.8 (5.14).Synthesis of (I)2, equivalent a 15% weight loss, in the first stage in the range 194 and 222\u00b0C. This was followed by the liberation of a benzene mol\u00adecule, corresponding to 29% weight loss, between 222 and 282\u00b0C, whereas the subsequent stages involve the pyrolysis of CO (282 to 360\u00b0C) and OH (360 to 496\u00b0C) corresponding to 15 and 11% weight loss, respectively. Gradual weight loss continued beyond 800\u00b0C.The pyrolytic process  for (I)Uiso(H) set to 1.2Ueq(C). The O- and N-bound H atoms were located from a difference map and refined with O\u2014H and N\u2014H = 0.84\u00b10.01 and 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989019017328/hb7880sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019017328/hb7880Isup2.hklStructure factors: contains datablock(s) I. DOI: 1919879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title morpholino\u00adchlorin adopts a ruffled conformation of its porphyrinic \u03c0-system chromophore inducing a red-shift of its optical spectrum compared to its chlorin analog. 46H16F20N4O3, was crystallized from hexa\u00adne/methyl\u00adene chloride as its 0.44 methyl\u00adene chloride solvate, C46H16F20N4O3\u00b70.44CH2Cl2. The morpholino\u00adchlorin was synthesized by stepwise oxygen insertion into a porphyrin using a \u2018breaking and mending strategy\u2019: NaIO4-induced diol cleavage of the corresponding 2,3-di\u00adhydroxy\u00adchlorin with in situ methanol-induced, acid-catalyzed intra\u00admolecular ring closure of the inter\u00admediate secochlorins bis\u00adaldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-di\u00admeth\u00adoxy\u00admorpholine moiety. Like other morpholino\u00adchlorins, the macrocycle of the title compound adopts a ruffled conformation, and the modulation of the porphyrinic \u03c0-system chromophore induces a red-shift of its optical spectrum compared to its corresponding chlorin analog. Packing in the crystal is governed by inter\u00adactions involving the fluorine atoms of the penta\u00adfluoro\u00adphenyl substituents, dominated by C\u2014H\u22efF inter\u00adactions, and augmented by short fluorine\u22effluorine contacts, C\u2014F\u22ef\u03c0 inter\u00adactions, and one severely slipped \u03c0-stacking inter\u00adaction between two penta\u00adfluoro\u00adphenyl rings. The solvate methyl\u00adene chloride mol\u00adecule is disordered over two independent positions around an inversion center with occupancies of two \u00d7 0.241\u2005(5) and two \u00d7 0.199\u2005(4), for a total site occupancy of 88%.The title morpholino\u00adchlorin, C Those adjacent to the morpholine moiety (C6F5 rings of C21 and C39) are more sterically encumbered and are about 10\u00b0 closer to perpendicular to the macrocycle plane, with values of 82.70\u2005(3) and 81.44\u2005(2)\u00b0. The corresponding values for compound 1b are very similar, with values of 71.89 and 73.73\u00b0, and 89.55 and 86.32\u00b0, respectively.Similar to other 1b and 1d allows us to investigate how minor conformational changes might affect the optical properties of the morpholino\u00adchlorins. The torsion angles between the two C\u2014C bonds in the morpholine units  in the two morpholino\u00adchlorins 1b and 1d vary slightly, with this angle being smaller in the title compound [35.2\u00b0 in 1b and 25.5\u2005(4)\u00b0 1d]. This angle is important as it strongly affects the \u03bbmax of the morpholino\u00adchlorins .The close structural relationship between the 2,3-disubstituted derivatives 1d in the crystal. Dominant are C\u2014H\u22efF hydrogen-bond-like inter\u00adactions, involving both methyl as well as pyrrole moieties as the hydrogen-atom donor. Weak C\u2014H\u22efF inter\u00adactions involving the solvent are also present. The most prominent of these inter\u00adactions are given in Table\u00a01Inter\u00adactions involving fluorine atoms play a dominant role in facilitating the arrangement of mol\u00adecules of et al., 2019a). Both meth\u00adoxy substituents are engaged in several of these inter\u00adactions: C45 exhibits inter\u00adactions with fluorine atoms from three different penta\u00adfluoro\u00adphenyl groups: with meta fluorine atoms F12iii and F19iv , and one intra\u00admolecular inter\u00adaction with F20, an ortho-fluorine atom. Angular and H\u22efF distance values for this intra\u00admolecular inter\u00adaction appear quite unfavorable: the C\u2014H\u22efF angle is only 103\u00b0, and the H\u22efF distance is 2.82\u2005\u00c5. However, only a slight rotation of the methyl H atoms is required to create a much more favorable geometry, and the C\u22efF distance between C45 and F20 is at 3.184\u2005(3) quite short . Inter\u00adactions involving the meth\u00adoxy group of C46 involve F10v and F1vi, two ortho-fluorine atoms . Two C\u2014H\u22efF inter\u00adactions originate from pyrrole moieties, involving H atoms at the pyrrole moieties flanking the morpholine unit: H8 towards F18i, and H18 towards F8ii, with both F8 and F18 being para-fluorine atoms . These two inter\u00adactions work in tandem with each other and with a severely slipped \u03c0\u2013\u03c0 stacking inter\u00adaction, between the rings of F6\u2013F10 and F16i\u2013F20i, connecting two opposite ends of the morpholino\u00adchlorin mol\u00adecule with its neighbors to create infinite chains connected via C\u2014H\u22efF and slipped \u03c0\u2013\u03c0 stacking inter\u00adactions . The centroid-to-centroid distance of the \u03c0-stacking inter\u00adaction is 4.3551\u2005(15)\u2005\u00c5, with a ring slippage of 2.795\u2005\u00c5 and a centroid-to-mean-plane distance of 3.1661\u2005(12)\u2005\u00c5. The last C\u2014H\u22efF inter\u00adaction involves the methyl\u00adene group of the minor moiety solvate methyl\u00adene chloride mol\u00adecule. Given the degree of disorder of the solvate mol\u00adecules (see Refinement section), this inter\u00adaction is probably vaguely defined at best and will not be discussed in detail.The most prominent C\u2014H\u22efF inter\u00adactions , inter\u00adactions between two fluorine atoms are different and much weaker in nature \u2005\u00c5 (F5\u22efF7vii) and 2.828\u2005(3)\u2005\u00c5 (F5\u22efF8vii) . With the intra\u00admolecular distance between F7 and F8 being 2.726\u2005(2)\u2005\u00c5, this leads to the formation of a nearly equilateral triangle of F atoms . It should be noted that atom F8 of this F3-triangle also acts as the acceptor of the C18\u2014H18\u22efF8ii contact and the backside of the aromatic ring of F8 is involved in the slipped \u03c0\u2013\u03c0 stacking inter\u00adaction (see discussion above). Fluorine atom F11 features a close contact with a symmetry-created copy of itself, created by a twofold axis. The F\u22efFiii distance here is 2.783\u2005(3)\u2005\u00c5, and the C\u2014F\u22efFiii angle is 125.5\u2005(2)\u00b0 .Besides C\u2014H\u22efF inter\u00adactions, which are generally considered as directional inter\u00adactions similar in strength to the better investigated C\u2014H\u22efO inter\u00adactions, ms Fig.\u00a06a. It shns Fig.\u00a07a. The ler Fig.\u00a06b. The Fvi and C42vi) of another penta\u00adfluoro\u00adphenyl ring [symmetry code: (vi) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01]. The F\u22efC distances are 3.034\u2005(3) and 2.978\u2005(3)\u2005\u00c5 for F2 and F3, respectively. There are two inter\u00adactions of this kind per mol\u00adecule, one as the C\u2014F donor and one as the \u03c0-density moiety accepting the C\u2014F\u22ef\u03c0 bond, connecting mol\u00adecules into centrosymmetric dimers. One of the methyl C\u2014H\u22efF contacts (towards F1) is also involved in the formation of these dimers .Besides F11, F2 and F3 are also involved in inter\u00admolecular C\u2014F\u22ef\u03c0 inter\u00adactions, pointing nearly perpendicularly towards C atoms , fifteen morpholino\u00adchlorins, two thio\u00admorpholines . Disorder with hexane, the other type of solvent used during crystallization, was excluded as a possibility due to the limited size of the solvate pocket, and it is thus assumed that 12% of void spaces in the crystal structure remained unoccupied during the crystallization process.The solvate methyl\u00adene chloride mol\u00adecule is disordered over four positions around an inversion center . The C\u2014Cl and Cl\u22efCl distances were restrained to target values and 2 and CH3 moieties, respectively. Methyl CH3 groups were allowed to rotate but not to tip to best fit the experimental electron density. Uiso(H) values were set to a multiple of Ueq(C) with 1.5 for CH3, and 1.2 for CH and CH2 units, respectively.N-bound H atoms were located in a difference electron-density map and were freely refined. H atoms attached to carbon atoms were positioned geometrically and constrained to ride on their parent atoms. C\u2014H bond distances were constrained to 0.95\u2005\u00c5 for pyrrole CH moieties, and to 1.00, 0.99 and 0.98\u2005\u00c5 for aliphatic CH, CH10.1107/S2056989020009093/is5543sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020009093/is5543Isup2.hklStructure factors: contains datablock(s) I. DOI: 2013871CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Phormidium ambiguum and Microcystis aeruginosa) were exposed to diurnal light-intensity variation to investigate their favorable and stressed phases during a single day. The photosynthetically active radiation (PAR) started at 0 \u00b5mol\u00b7m\u22122\u00b7s\u22121 (06:00 h), increased by ~25 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or ~50 \u00b5mol\u00b7m\u22122\u00b7s\u22121 every 30 min, peaking at 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 (12:00 h), and then decreased to 0 \u00b5mol\u00b7m\u22122\u00b7s\u22121 (by 18:00 h). The H2O2 and antioxidant activities were paralleled to light intensity. Higher H2O2 and antioxidant levels , and superoxidase dismutase) were observed at 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 rather than at 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121. Changes in antioxidant levels under each light condition differed between the species. Significant correlations were observed between antioxidant activities and H2O2 contents for both species, except for the CAT activity of P. ambiguum at 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121. Under each of the conditions, both species responded proportionately to oxidative stress. Even under maximum light intensities (300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 PAR intensity), neither species was stressed. Studies using extended exposure durations are warranted to better understand the growth performance and long-term physiological responses of both species.Two harmful cyanobacteria species ( The growth and spread of cyanobacteria have increased, thus threatening today\u2032s water bodies and supplies worldwide ,2. GlobaDuring cyanobacteria control efforts, chemical control measures are discouraged due to their potentially harmful secondary effects on ecosystems ,13,14, wBiological, chemical, and physical factors collectively determine the occurrence and distribution of cyanobacteria in the environment ,25,26. PThe photosynthetic species produce reactive oxygen species (ROS) as a byproduct of the photosynthesis process, which is harmful when accumulated in cells . Therefo2O2) and antioxidant (guaiacol peroxidase (GPX), catalase (CAT), ascorbic peroxidase (APX), and superoxidase dismutase (SOD)) responses of cyanobacteria to diurnal changes in the light intensity were studied. Two photosynthetically active radiation (PAR) levels, 300 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121, were selected as maximum light intensities, and the responses of two cyanobacterial species, Phormidium ambiguum and Microcystis aeruginosa, were tested for gradually varying light conditions. P. ambiguum is a non-heterocystous filamentous cyanobacterial species, categorized as a benthic cyanobacterium [M. aeruginosa is a floating (buoyant) and colony foaming type cyanobacterium [In this study, the oxidative stress  and M. aeruginosa (strain NIES 111) were obtained from the National Institute for Environmental Studies, Tsukuba, Japan. Both species were cultured for 14 days at 20 \u00b0C under a 12 h:12 h light:dark cycle inside an incubator . Light was provided with cool white fluorescent lamps and the intensity was maintained at 20\u201330 \u00b5mol\u00b7m\u22122\u00b7s\u22121 PAR. The nutrient medium was 100% BG-11 [0% BG-11 . During P. ambiguum and M. aeruginosa cyanobacteria cultures were made, maintaining the 0.6 \u00b1 0.02 optical density measured at 730 nm (OD730) using a spectrophotometer . The dilution of the cyanobacteria culture was accomplished with BG11 nutrient medium. In all experiments, the temperature was maintained at 20 \u00b0C in an incubator, whereas the lighting conditions changed from 0 \u00b5mol\u00b7m\u22122\u00b7s\u22121 (at 06:00 h) to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 (at 12:00 h) by changing the lighting intensity by ~25 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or ~50 \u00b5mol\u00b7m\u22122\u00b7s\u22121 every 30 min with a VBP-L24-C2 light . The light intensity was then decreased at the same rate (until 18:00 h). The lighting condition was controlled with warm light-emitting diode panel lights, and the light intensity was measured using a quantum flux meter . Cyanobacteria samples from each flask were collected for analysis every 3 h, at 06:00 h, 09:00 h, 12:00 h, 15:00 h, 18:00 h, and 21:00 h. To facilitate mixing, each flask was manually shaken at the time of sampling.Following the 14-day incubation, 3 replicate conical flasks  from each of the 2O2 contents were estimated according to standard methods [g for 10 min at 4 \u00b0C. The cell pellets were washed once with ultrapure water . To extract cellular H2O2, cell pellets were homogenized in 1 mL of 0.1 M pH 6.5 phosphate buffer and centrifuged at 10,000\u00d7 g for 10 min at 4 \u00b0C. A total of 750 \u03bcL of 1% titanium chloride in 20% H2SO4 (v/v) was then added to initiate the reaction. The optical absorption was measured at 410 nm using a spectrophotometer (UVmini-1240), following centrifugation  at room temperature (25 \u00b1 2 \u00b0C). The H2O2 concentration was determined using a standard curve, prepared using a series of samples with known H2O2 concentration.Cellular H methods . Brieflyg at 4 \u00b0C for 10 min and removing the supernatant and cell pellets, which were homogenized in 1 mL potassium phosphate buffer . A total of 65 \u00b5l of enzyme extract was then mixed with 920 \u03bcL of potassium phosphate buffer  containing 20 mM guaiacol. With the addition of 15 \u03bcL of 0.6% H2O2, the reaction was then started, and the absorbance change was recorded at 470 nm every 10 s for 3 min using UV mini-1240. GPX activity was calculated using an extinction coefficient of 26.6 mM/cm.The GPX activity was assayed as described by Hoda et al.  and MacAg at 4 \u00b0C for 10 min. The supernatant was removed, and the cell pellets were homogenized in 1 mL potassium phosphate buffer , containing 0.1 mM EDTA. After centrifuging again , the supernatant was collected as the enzyme extract. The CAT activity was measured by reacting 15 \u00b5L of 750 mM H2O2, 920 \u00b5L of potassium phosphate buffer, and 65 \u00b5L of extract supernatant. Optical absorption was measured at 240 nm using UV mini-1240. The measurements were recorded every 10 s for 3 min, and the CAT activity was calculated using an extinction coefficient of 39.4 mM/cm.CAT activity was measured using the method described by Aebi . A total2O2. Calculations were performed using a molar extinction coefficient for ascorbate of 2.8 mM/cm.APX activity was assayed, as described by Nakano and Asada . The decSOD activities were determined by performing nitro blue tetrazolium (NBT) assays, as described by Ewing and Janero . Each saP. ambiguum and M. aeruginosa were evaluated using a Student\u2019s t-test, assuming equality of variance. Pearson\u2019s correlation analysis was used to evaluate correlations between parameters. Statistical analyses were performed by using IBM SPSS Statistics for Windows, Version 25.0. .One-way analysis of variance (ANOVA), followed by Tukey\u2019s post-hoc test, was performed to test the statistical significance of variations among the means of sample groups. Data were normalized relative to the starting group (06:00 h), by dividing the results of each group by the corresponding 06:00 h group for each replicate. Significant differences between experimental groups of 2O2 contents of P. ambiguum and M. aeruginosa increased with increasing light intensity and peaked between 12:00 h and 15:00 h. The H2O2 content decreased thereafter in parallel with decreasing light intensity. The cyanobacteria were exposed to dark at 18:00 h; however, even at 21:00 h, the H2O2 contents did not reach the initial level measured at 06:00 h . ANOVA testing of P. ambiguum exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped H2O2 contents at 06:00 h, 09:00 h, and 18:00 h, and 12:00 h, 15:00 h, and 21:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing grouped H2O2 contents at 06:00 h, 09:00 h, and 21:00 h, 12:00 h and 15:00 h, and 18:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped H2O2 contents at each time point . Comparing the H2O2 contents of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121, max PAR intensity groups showed that the H2O2 contents of both P. ambiguum and M. aeruginosa differed significantly at each time point (p < 0.01 for each time point).The H 06:00 h . For P. P. ambiguum and M. aeruginosa increased over time and reached the maximum at 12:00 h when the maximum PAR intensity was reached (300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121). With decreasing light intensity, the GPX activities of both species were decreased. However, with the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity group, at 18:00 h and 21:00 h, the GPX activities decreased even further than the starting GPX activity (06:00 h). With the 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR-intensity, the GPX activity of both species decreased with decreasing light, but the GPX activity of P. ambiguum remained higher than the starting GPX activity, even at 21:00 h. For M. aeruginosa, GPX activity of 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity reached the starting GPX activity (06:00 h) at 21:00 h . ANOVA testing of the P. ambiguum exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped GPX activities at 06:00 h and 09:00 h; 12:00 h and 15:00 h; 18:00 h; and 21:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing groped GPX activities at 06:00 h, 18:00 h, and 21:00 h; 12:00 h; and 09:00 h and 15:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped GPX activities at 06:00 h and 21:00 h; 06:00 h, 09:00 h, and 18:00 h; 09:00 h, 15:00 h, and 18:00 h; and 12:00 h . A comparison between 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups showed that the GPX activities of P. ambiguum and M. aeruginosa differed significantly at each time point (p < 0.01 for each time point).The GPX activities of both  21:00 h . For P. P. ambiguum and M. aeruginosa increased over time but showed a delayed response, as the maximum CAT activities were reached at 15:00 h (which was 3 h after the maximum light intensities of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 PAR was reached). Decreasing light intensities were paralleled by reduced CAT activities, although the CAT activity did not reach the initial CAT level, even at 21:00 h . ANOVA testing of P. ambiguum exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped CAT activities at 06:00 h and 21:00 h; 09:00 h, 12:00 h, and 18:00 h; and 15:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing groped CAT activities at 06:00 h and 21:00 h; 9:00 h; 21:00 h, 09:00 h, and 18:00 h; and 12:00 h and 15:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped CAT activities at 06:00 h and 21:00 h; 09:00 h and 18:00 h; 12:00 h; and 15:00 h . Comparisons between the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups showed that the CAT activities of P. ambiguum differed significantly at 09:00 h, 12:00 h, 15:00 h, and 18:00 h (p < 0.01), although the CAT activities at 06:00 h and 21:00 h were not different (p > 0.05). The CAT activities of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups of M. aeruginosa also differed at 09:00 h, 15:00 h, and 21:00 h (p < 0.05).The CAT activities of both  21:00 h . For P. P. ambiguum and M. aeruginosa increased with increasing light intensity, but a delayed response was observed, where the maximum APX activity was reached at 15:00 h (3 h after the maximum light intensities were reached). With subsequent decreasing light intensity, the APX activities of both species decreased and reached the initial APX activity (06:00 h) at 21:00 h . ANOVA testing of P. ambiguum exposed 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped APX activities at 06:00 h, 18:00 h, and 21:00 h; 09:00 h, 18:00 h, and 21:00 h; and 12:00 h and 15:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing grouped APX activities at 06:00 h, 18:00 h, and 21:00 h; 06:00 h, 09:00 h, and 15:00 h; and 12:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped APX activities at 06:00 h and 21:00 h; 06:00 h, 09:00 h, and 18:00 h; 09:00 h, 15:00 h, and 18:00 h; and 12:00 h . Comparisons between the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups showed that the differences in APX activities for both species were significantly higher in the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups, from 09:00 h to 18:00 h (p < 0.01 for each light condition for both species). The 21:00 APX activities of P. ambiguum were significantly lower in the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity group than in the 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity group (p < 0.01), although no differences were observed for M. aeruginosa.The APX activities of both  21:00 h . For P. P. ambiguum and M. aeruginosa increased with the light intensity. With decreasing light, SOD activity decreased for both species and approached the starting level at 21:00 h, for both 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR conditions . ANOVA testing of P. ambiguum exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped SOD activities at 06:00 h, 18:00 h, and 21:00 h; 09:00 h, 18:00 h, and 21:00 h; 12:00 h; and 15:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing grouped SOD activities at 06:00 h and 21:00 h; 06:00 h and 09:00 h; 09:00 h, 15:00 h, and 18:00 h; and 12:00 h, 15:00 h, and 18:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped SOD activities at 06:00 h and 21:00 h; 06:00 h, 09:00 h, 15:00 h, and 18:00 h; and 09:00 h and 12:00 h . Comparisons between the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity groups indicated that the SOD activities of P. ambiguum differed at 12:00 h and 15:00 h (p < 0.01) and that M. aeruginosa showed no significant differences between 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity conditions (p > 0.05).The SOD activities of both nditions . For P. P. ambiguum and M. aeruginosa increased with the light intensity. With decreasing light, the AOX activity decreased, and, for both species, the AOX activity approached the starting level at 21:00 h, under both the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 PAR conditions . ANOVA testing of P. ambiguum exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped AOX activities at 06:00 h, 18:00 h, and 21:00 h; 09:00 h, 18:00 h, and 21:00 h; 15:00 h; and 12:00 h . For M. aeruginosa exposed to 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity, ANOVA testing grouped AOX activities at 06:00 h and 21:00 h; 09:00 h and 18:00 h; and 12:00 h and 15:00 h . ANOVA testing of M. aeruginosa exposed to 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity grouped AOX activities at 06:00 h and 21:00 h; 06:00 h and 18:00 h; 09:00 h, 15:00 h, and 18:00 h; and 12:00 h and 15:00 h . The AOX activities of 300 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensities differed significantly at 12:00 h and 15:00 h, with P. ambiguum (p < 0.01), while those for M. aeruginosa only exhibited a significant difference at 09:00 h (p < 0.01). In other cases, no significant differences were observed.The total antioxidant (AOX) activities of both nditions . For P. 2O2 levels and those of the antioxidants  and the AOX levels were significantly linearly correlated, except for the GPX activity of P. ambiguum under the 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 max PAR intensity , confirming that less variance occurred. When the AOX values were considered, the 2R showed relatively higher values (>0.72).The relationships between the Hntensity . Pearson2O2 contents and the antioxidant activities of P. ambiguum and M. aeruginosa were highly responsive to the diurnal variations in light intensity. In this study, the only variable factor was the light intensity, where H2O2 levels were high during times of higher light intensities and decreased at lower light intensities. When cellular H2O2 level increases, the antioxidant activities correspondingly increase to prevent damage induced by oxidative stress [2O2 levels, the antioxidant activities also varied during the same time frame and followed the H2O2 levels, which increased at higher light intensities and decreased at lower light intensities. The antioxidant activities of both species were correlated linearly with the H2O2 contents. Although the H2O2-antioxidant relationships were varied from strong to weak (depending on the antioxidant species), overall, our findings suggest that the antioxidant levels of both species responded to the cellular H2O2 level accordingly.The He stress ,50. As o2O2 and antioxidant responses followed the same trends for both maximum light intensity conditions (PAR intensities of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121 or 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121). Under the maximum PAR intensity of 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121, the cyanobacteria received approximately twice the photon energy of the group with a maximum PAR of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121. Therefore, it can be anticipated that the experiment groups, which receive higher photon energy, undergo an enhanced rate of photosynthesis. This is evidenced by the increased H2O2 formed after exposure to a higher light intensity [2O2 production is reduced with higher light exposure [2O2 contents correlated directly with light intensity, even at higher intensities, PAR intensities under 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121 did not subject either cyanobacterial species to photo stress. However, this study only involved a single day diurnal variation, and the H2O2 levels of the cells did not reach the starting H2O2 conditions at 06:00 h (even at 21:00 h) for either species. The antioxidant activities almost decreased to the initial conditions by 21:00 h. Therefore, cells may undergo oxidative stress during dark conditions due to the lack of antioxidant activities. If the H2O2 was continued to be presence in cells, the protein synthesis of photosystems will be inhibited [2O2 and adaptation responses.The Hntensity ,52. Howentensity ,54, duriexposure ,56,57. Anhibited  and, in nhibited . TherefoM. aeruginosa than P. ambiguum, except for GPX. Under high H2O2 contents, the AOX activity was highly elevated in P. ambiguum, but in the dark, both species reached the starting AOX activity level at 21:00 h. This finding suggests that M. aeruginosa is less tolerant to oxidative stress than P. ambiguum [2O2 contents, both species demonstrated significant linear relationships (with the only exception being for GPX of P. ambiguum under a maximum PAR of 300 \u00b5mol\u00b7m\u22122\u00b7s\u22121). Therefore, despite the high AOX content of the P. ambiguum, both species were able to maintain balanced antioxidant activity under every light condition of the single day exposure.The antioxidant levels differed between the two species, where the response level was lower for ambiguum ,59. ConcM. aeruginosa is a buoyant species that floats in a range of depths and might have higher tolerance to oxidative stress [P. ambiguum. However, in the present study, both species experienced same light intensity variance as the cultures were mixed periodically. The non-different H2O2 contents between the two species suggested that both species experienced similar levels of oxidative stress. Therefore, less oxidative stress tolerance of P. ambiguum triggered the antioxidant activity at a relatively higher rate. Conversely, nonenzymatic antioxidants, primarily carotenoids, protect against ROS in phototrophs, including cyanobacteria [P. ambiguum than M. aeruginosa [M. aeruginosa is due to involvement of nonenzymic antioxidant over the P. ambiguum.The difference in antioxidant levels of the two species can be related to their behavioral characteristics. The e stress ,61 than bacteria ,62. The ruginosa ,64,65; t\u22122\u00b7s\u22121 and 600 \u00b5mol\u00b7m\u22122\u00b7s\u22121) confirmed that the OD730 and chlorophyll-a contents of cyanobacteria  were significantly reduced, which was associated with oxidative stress [Our previous study on the effects of 8 days of exposure to non-varying, high-light intensities (300 \u00b5mol\u00b7me stress . In futu"}
{"text": "V\u03b39V\u03b42 T\u00a0cells respond in a TCR-dependent fashion to both microbial and host-derived pyrophosphate compounds . Butyrophilin-3A1 (BTN3A1), a protein structurally related to the B7 family of costimulatory molecules, is necessary but insufficient for this process. We performed radiation hybrid screens to uncover direct TCR ligands and cofactors that\u00a0potentiate BTN3A1\u2019s P-Ag sensing function. These experiments identified butyrophilin-2A1 (BTN2A1) as essential to V\u03b39V\u03b42 T cell recognition. BTN2A1 synergised with BTN3A1 in sensitizing P-Ag-exposed cells for V\u03b39V\u03b42 TCR-mediated responses. Surface plasmon resonance experiments established V\u03b39V\u03b42 TCRs used germline-encoded V\u03b39 regions to directly bind the BTN2A1 CFG-IgV domain surface.\u00a0Notably, somatically recombined CDR3 loops implicated in P-Ag recognition were uninvolved. Immunoprecipitations demonstrated close cell-surface BTN2A1-BTN3A1 association independent of P-Ag stimulation. Thus, BTN2A1 is a BTN3A1-linked co-factor critical to V\u03b39V\u03b42 TCR recognition. Furthermore, these results suggest a composite-ligand model of P-Ag sensing wherein the V\u03b39V\u03b42 TCR directly interacts with both BTN2A1 and an additional ligand recognized in a CDR3-dependent manner.  \u2022Radiation hybrids identify BTN2A1 as crucial for V\u03b39V\u03b42 phosphoantigen (P-Ag) sensing\u2022BTN2A1 binds directly to the T\u00a0cell receptor via germline-encoded regions of V\u03b39\u2022Cell-surface BTN2A1 associates directly with BTN3A1 independent of P-Ag stimulation\u2022The V\u03b39-BTN2A1 interaction modality suggests an additional CDR3-dependent TCR ligand Karunakaran et\u00a0al. find that butyrophilin 2A1 (BTN2A1) associates with BTN3A1 on the cell surface and binds directly to germline-encoded regions of the V\u03b39 chain of the V\u03b39V\u03b42 TCR. Thus, BTN2A1 collaborates with BTN3A1 to potentiate V\u03b39V\u03b42 T\u00a0cell recognition, playing an essential role in phosphoantigen sensing. Human peripheral blood \u03b3\u03b4 T\u00a0cells are dominated from an early age by V\u03b39V\u03b42 lymphocytes , an innaV\u03b39V\u03b42-mediated P-Ag sensing requires cell-cell contact  and depeTursiops truncatus) and alpaca (Vicugna pacos)  . Of notea pacos) . In conta pacos) . Consista pacos) . Furthera pacos)  and canca pacos) . From thOur previous studies have established that BTN3A1 is necessary but not sufficient for P-Ag sensing and indicated the existence of an additional putative Chr-6-encoded factor that synergized with BTN3A1 to stimulate P-Ag-mediated responses , which wWe showed previously that a T\u00a0cell hybridoma expressing the\u00a0V\u03b39V\u03b42 MOP TCR produced interleukin (IL)-2 in co-culture with BTN3A1-transduced Chinese hamster ovary (CHO) cells incubated with the anti-BTN3A1 monoclonal antibody (mAb) 20.1 but exhibited a complete lack of response to HMBPP or Zol . In contTo identify Factor X, we used an unbiased genome-based approach involving generation of radiation hybrids between CHO-Chr 6 cells and BTN3A1-transduced hypoxanthine-aminopterin-thymidine (HAT)-sensitive rodent fusion partners and subsequent analysis of their capacity to stimulate P-Ag sensing by V\u03b39V\u03b42 T\u00a0cells A. We posWe fused CHO-Chr6 cells separately with two HAT-sensitive fusion partners\u2014first BTN3A1-transduced A23 hamster cells and second BTN3A1-transduced mouse BW cells  Sanders; resultiHFE, the BTN3A1 gene already transduced into rodent fusion partners, BTN3A2, BTN3A3, and BTN2A1 and BTN2A2. Since we knew that expression of all three BTN3 genes was insufficient for reconstitution of the P-Ag response , BTN2A1 and BTN2A2, which to date have been discussed mainly for their immunomodulatory properties  or BTN2A1 (BTN2A1\u2212/\u2212) or BTN2A2 alone (BTN2A2\u2212/\u2212). Inactivation of both BTN2 genes completely abolished interferon (IFN)\u03b3 production by polyclonal V\u03b39V\u03b42 T\u00a0cell lines in response to Zol\u00a0pulsed cells (BTN2\u2212/\u2212 and BTN2A1\u2212/\u2212 exhibited a complete loss of IL-2 production by TCR-MOP cells in response to either HMBPP (BTN2A2\u2212/\u2212 were similar to wild-type (WT) 293T cells  and 49.9\u00a0\u03bcM (n\u00a0= 8), respectively . Injection of BTN2A1 IgV produced substantially enhanced signals over surfaces with immobilized V\u03b39V\u03b42 TCR relative to V\u03b34V\u03b45 and V\u03b32V\u03b41 TCRs or control streptavidin surfaces, indicating specific binding A. Equiliectively B.Figure\u00a0+ T\u00a0cell subset (d 46.6\u03bcM [n\u00a0= 8]) of the BTN2A1-V\u03b39V\u03b41 TCR interaction  (d 39\u201350\u00a0\u03bcM [n\u00a0= 3]).An initial homology model suggested strong feasibility of a similar interaction mode and highlighted seven amino acids on the face of the BTN2A1 IgV domain incorporating the C, C', F and G \u03b2 strands (CFG face), equivalent to the region of BTNL3 IgV domain involved in binding V\u03b34, as candidates for alanine mutation C. Indivi0\u201315\u00a0\u03bcM) D and S3B0\u201315\u00a0\u03bcM) . Based o0\u201315\u00a0\u03bcM) D and a B0\u201315\u00a0\u03bcM) E in the 0\u201315\u00a0\u03bcM) F and S3G0\u201315\u00a0\u03bcM) G and S3H+ TCR binding  and assessed effects on V\u03b39V\u03b42-mediated P-Ag response. Although permissive for cell-surface BTN2A1 expression  and CDR2  loops of the V\u03b39 IgV domain in BTN2A1 interaction, regions also critical for BTNL3-V\u03b34 interaction  Figure\u00a0F. ConsisCollectively, these findings established that V\u03b39V\u03b42 TCR binds BTN2A1 IgV via a binding mode that closely mimics that of V\u03b34 TCR for BTNL3 and that this binding is essential for P-Ag sensing but occurs alongside parallel and essential V\u03b42 CDR-mediated binding events.BTN and BTNL molecules have been shown to form either homo- or heterodimers . To inveInterestingly, the BTN2A1 IgV-C model also highlighted close proximity of extracellular membrane-proximal cysteine residue (C247) with its equivalent residue in the opposing monomer B, suggesFinally, by combining our HADDOCK-derived model of V\u03b39V\u03b42/BTN2A1 interaction B with ouTo assess whether BTN2A1 and BTN3A1 were associated with each other at the cell surface either before or after P-Ag exposure, a membrane-impermeable amine-reactive cross-linker incorporating a 16\u00c5 spacer was used to cross-link proteins on the surface of CHO transductants co-expressing C-terminally HA-tagged BTN2A1 (BTN2A1-HA) and a N-terminally FLAG-tagged BTN3A1 (FLAG-BTN3A1). Immunoprecipitation (IP) using anti-HA beads or 20.1 mAb and subsequent anti-FLAG western blot (WB) was used to detect cross-linked BTN2A1-BTN3A1 species .Figure\u00a05Following IP of BTN2A1-HA using anti-HA beads and subsequent WB detection of FLAG-BTN3A1 under reducing conditions using an anti-FLAG antibody, two discrete bands were detected that considerably exceeded the size of either BTN2A1 or BTN3A1 monomers  A; each w1H-15N-labeled BTN3A1 IgV in E.\u00a0coli and performed 1H-15N heteronuclear single quantum coherence (HSQC) spectroscopy in the absence and presence of an equimolar amount of naturally labeled E.\u00a0coli-expressed BTN2A1 IgV . Reagents generated in this study are available on request from the Lead Contact with a completed Materials Transfer Agreement.Further information and requests for resources and reagents should be directed to and will be fulfilled by the Lead Contact, Benjamin E. Willcox  were cultured with RPMI (GIBCO) supplemented with 10% FCS, 1\u00a0mM sodium pyruvate, 2.05\u00a0mM glutamine, 0.1\u00a0mM nonessential amino acids, 50\u00a0\u03bcM \u03b2-mercaptoethanol, penicillin (100\u00a0U/mL) and streptomycin (100\u00a0U/mL). Peripheral blood mononuclear cells isolated from healthy volunteers were also maintained as above with or without rhIL-2 (Novartis Pharma). 293T cells were maintained in DMEM (GIBCO) supplemented with 10% FCS.6 or 107 cells) were irradiated at Faxitron CP160 . The irradiated cells and fusion partner (BW or A23) were mixed at 1:1 or 1:3 ratio (irradiated cell:fusion partner) and centrifuged at 461\u00a0g for 5\u00a0min at RT. The cell pellet was gently tapped and 1\u00a0mL PEG1500 was added slowly over a minute with gentle mixing in a prewarmed water-bath. After addition of PEG, cells were resuspended in 50\u00a0mL warm serum free RPMI and incubated for 30\u00a0min, followed by centrifugation at 461\u00a0g for 5\u00a0min and careful resuspension in RPMI supplemented with 10% FCS at 104 cells/mL. The cell suspension was seeded in 96 well plate flat bottom (A23 fused) or round bottom (BW fused) plates in 100\u00a0\u03bcl per well. On the following day, 100\u00a0\u03bcl of 2X HAT was added and cells were selected for two weeks. The selected clones were supplemented with HT medium and further seeded at limiting dilutions to obtain single cell clones which were tested for P-Ag mediated activation of our V\u03b39V\u03b42 TCR (MOP) transductants. P-Ag presentation capable and incapable clones were PCR characterized for human Chr 6 regions with primers listed in CHO Chr 6  using STAR and the corresponding Gene Transfer Format (gtf) file (version 87). Unmapped reads and those exhibiting more than two mismatches were selected and mapped against the Chinese hamster genome . The corresponding gtf-file was downloaded from the pre-Ensembl ftp site (Cricetulus_griseus.CriGri_1.pre.gtf). Afterward, all unmapped reads and those containing more than two mismatches were again selected to finally map against the human genome . Only reads showing maximally one mismatch were considered as true. With the help of featureCounts, mapped reads were assigned to genomic features using the above mentioned gtf-files. The results were summarized within an Excel-file. Further gene information were extracted from BioMart  and total RNA was extracted. Sequencing libraries were produced with an Illumina Truseq RNA preparation kit as described by the supplier\u2019s protocol and were sequenced with an Illumina HiSeq4000. Sequence reads were mapped to the human genome (hg38) with STAR (version STAR_2.50a) and read counts of gene transcripts were determined using gtf file Homo_sapiens.GRCH38.84.gtf and featureCount (v1.5.0-p1). Cell lines were then compared for presence, i.e., expression, of human Chr 6 genes. To filter out reads descending from mouse or hamster cells, all fastq-files were initially mapped against the mouse genome  as per manufacturer\u2019s protocol.For 6 cells/mL density in a 96 well U bottom plate for 10\u00a0days with 100\u00a0\u03bcL per well. After 10\u00a0days, cells were pooled and washed twice and cultivated to rest without rhIL- 2 at 106 cells/mL density in a 6-well plate. After three days, rested cells were subjected for further experiments.Fresh peripheral blood mononuclear cells (PBMCs) were isolated from healthy volunteers after obtained written informed consent in accordance with the Declaration of Helsinki and approval by the University of W\u00fcrzburg institutional review board. Whole blood was layered over the Histopaque-1077 in a 50\u00a0mL falcon tube and centrifuged at 400\u00a0g for 30\u00a0min at room temperature (RT) with no acceleration and brakes. After centrifugation, the opaque interface containing PBMCs were aspirated and washed twice at 461\u00a0g for 5\u00a0min at RT. V\u03b39V\u03b42 T\u00a0cells were expanded by cultivation of PBMCs with RPMI containing 10% FACS, 1\u00a0\u03bcM BrHPP and recombinant human IL-2 100 IU/mL (Novartis Pharma) in 10BTN2A1 and BTN2A2 genes were disrupted in 293T cells using CRISPR. The CRISPR sequencing targeting functional BTN2A genes were designed with the help of online tools mentioned in the table (software section) and sequences were cloned into GeneArt CRISPR Nuclease vector as per manufacturer\u2019s instructions. On day1, 1.5\u00a0\u00d7 106 293T cells were seeded in a 6\u00a0cm cell culture plate with DMEM medium without pyruvate (10% FCS). On day 2, cells were transfected with 5\u00a0\u03bcg of BTN2A-IgV_CRISPR cloned GeneArt CRISPR Nuclease (CD4 enrichment) Vector or BTN2A1_49FCRISPR cloned GeneArt CRISPR Nuclease (OFP Reporter) Vector or BTN2A2_343CRISPR cloned GeneArt CRISPR Nuclease (CD4 enrichment) Vector in a calcium-phosphate dependent method  BTN2A1 IgV CRISPR target site2A1IgV \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0GCAGTGTTTGTGTATAAAGGTGGCAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a0552A1allele1 \u00a0GCAGTGTTT\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014-GTGGCAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a0452A1allele2 \u00a0GCA\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014-GTGGCAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a039\u2217\u2217\u2217 \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0BTN2A2 IgV CRISPR target site1b) 2A2IgV \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0GCAGTGTTTGTGTATAAGGGTGGGAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a0552A2allele1 \u00a0GCAGTGTTTGTGTATA-GGGTGGGAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a0542A2allele2 \u00a0GCAGTGTTTG\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014TGGGAGAGAGAGAACAGAGGAGCAGATGGAGGAGT \u00a045\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0BTN2A1\u2212/\u2212 allelic phenotype2) 2A1-49F \u00a0\u00a0\u00a0\u00a0\u00a0GGACTAGGCTCTAAGCCCCTCATTTCAATGAGGGGCCATGAA-GACGGGGGCATCCGGC \u00a059Allele1 \u00a0\u00a0\u00a0\u00a0\u00a0GGACTAGGCTCTAAGCCCCTCATTTCAATGAGGGGCCATGAAGGACGGGGGCATCCGGC \u00a059Allele2 \u00a0\u00a0\u00a0\u00a0\u00a0GGACTAGGCTCTAAGCCCCTCATTTCAATGAGGGG\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014GGCATCCGGC \u00a045\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0BTN2A2\u2212/\u2212 allelic phenotype3) 2A2 \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0CAAGAAGGCAGGTCCTACGATGAGGCCATCCTACGCC-TCGTGGTGGCA \u00a048Allele \u00a0\u00a0\u00a0\u00a0\u00a0CAAGAAGGCAGGTCCTACGATGAGGCCATCCTACGCCCTCGTGGTGGCA \u00a049\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u2217\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0BTN2\u2212/\u2212 cells were seeded overnight in triplicates at 2\u00a0\u00d7 104 cells/well in 100\u00a0\u03bcL DMEM containing 10% FCS in a 96 well flat bottom cell culture plate with or without 25\u00a0\u03bcM Zol. Next day, DMEM with/without Zol was aspirated and cells were washed twice with PBS at RT and 2\u00a0\u00d7 104 expanded V\u03b39V\u03b42 T\u00a0cells/well in 100\u03bcL RPMI was added and cocultured for 4 h. After 4 h, supernatants were collected and frozen at \u221220\u00b0C, until cytokine assay was performed with human IFN\u03b3 ELISA kit (Invitrogen) was used according to the manufacturer\u2019s instructions.293T or 293T BTN2A1 and BTN2A2 were amplified from the cDNA obtained from 293T cells with the help of pMIM-BTN2A1/2Fwd and pMIM-BTN2A1/2Rev primers , V\u03b42-R51A and V\u03b42-CDR3 deletion mutant (\u0394CDR3: CDR3\u03b4 sequence CACD\u2014\u2014\u2013YTDKLIF) TCR chains were generated as reported earlier . V\u03b39-E70Drosophila S2 cells and purified by nickel chromatography as previously described (cDNA encoding wild type BTN2A1 (S27 to V142) or BTN2A2 IgV domains (S31 to V146), or BTN2A1 IgV incorporating the described\u00a0mutations, were generated as gblocks (Integrated DNA Technologies) including the sequence for a C-terminal 6x Histidine\u00a0tag and cloned into the pET23a expression vector (Novagen). Proteins were overexpressed, purified and refolded as described . BTN2A1 escribed . TCRs we5 cells at 4\u00b0C.Flow cytometry staining of the samples were performed with the below mentioned antibodies and samples were measured on FACSCalibur or LSRII flow cytometer (BD). The expression of BTN3A1 and BTN2A1 were detected with anti-huBTN3 (CD277) clone 103.2 (gift from David Olive) and anti-huBTN2A1 clone 1C7D (MBL), followed by secondary antibody F(ab\u2019) Donkey anti mouse IgG\u00a0(H+L) R-PE (Jackson Immunoresearch). mIgG1,\u03ba isotype clone p3.6.2.81 (eBiosciences) and mIgG2a,\u03ba isotype clone-eBM2a (eBiosciences) were used a isotype controls and were detected by above mentioned secondary antibody. N-terminal HA-tagged BTN2A1 or BTN2A2 were detected using anti-HA-FITC (Biolegend). PBMC expanded human V\u03b39V\u03b42 T\u00a0cells were detected with FITC- conjugated anti-human V\u03b42 (BD Biosciences). Biotinylated soluble V\u03b39V\u03b42 TCRs were tetramerized by the addition of Streptavidin-PE conjugate (ThermoFisher Scientific) at room temperature, and 1-2\u03bcg of tetramer used to stain 10SPR was performed as previously described  on a BIABTN2A1 and BTN2A2 loci have been functionally inactivated (293T BTN2\u2212/\u2212 cells), or CHO CD80+ cells, were transduced to overexpress HA-tagged BTN2A1 or BTN2A2, or BTN3A1, as indicated. Cells were surface biotinylated using EZ-Link Sulfo NHS-LC-biotin  for 30\u00a0min on ice, quenched with 20mM Tris pH 7.5 for 5\u00a0min, washed in TBS, and lysed in lysis buffer containing 1% NP40 in 20mM Tris pH 7.5, 150mM NaCl\u00a0\u00b1 10mM iodoacetamide (Sigma). HA-tagged BTN2A1 or BTN2A2 was immunoprecipitated using anti-HA resin (BioLegend). Immunoprecipitations were washed in lysis buffer and eluted in nonreducing (NR) or reducing (R) SDS sample buffer and boiled, or incubated at 37C for 5\u00a0min before separation on 4%\u201320% SDS-PAGE gels (BioRad). Proteins were transferred to PVDF using the BioRad TransBlot Turbo system, blocked in 3% BSA, then incubated with streptavidin-HRP (Thermo). To investigate potential association of BTN2A1 and BTN3A1 at the cell surface, CHO cells overexpressing BTN2A1-HA, FLAG-BTN3A1, or both, were treated with the soluble, membrane-impermeable crosslinker sulfo-EGS (ThermoFisher) at 0.5mM in PBS, at 4\u00b0C for 2 h. Following this, the reaction was quenched by addition of Tris pH 7.5 to 20mM. Cells were washed in TBS and lysed in 1% NP40 lysis buffer. After centrifugation to remove insoluble material, immunoprecipitation was carried out using anti-HA resin or 20.1 antibody bound to protein A Sepharose . Immunoprecipitates were run on duplicate 4%\u201320% gels (BioRad) and blotted with anti-BTN2A1 or anti-FLAG antibodies.293T cells in which the The ectodomain structures of BTN2A1 (residues Q29-A248) and BTN2A2 (residues Q33-M265), were generated using the I-TASSER (Iterative Threading ASSEmbly Refinement) server . BrieflyThe BTN2A1-IgV/V\u03b39 complex was modeled with HADDOCK . BTN2A1 R65 (located in the IgV domain of BTN2A1) forms a salt bridge interaction with E76 (in the V\u03b39 TCR chain). This interaction is likely to be abolished by introducing Ala at this position in BTN2A1 IgV domain (R65A), consistent with abrogation of binding by the R65A mutant. The hydroxyl group of S72 (BTN2A1) is in close proximity to V58 (TCR). Juxtaposition of this polar residue (S72) with a hydrophobic residue (V58) is likely to be energetically unfavorable for binding in this region. By substituting an Ala (ie a non-polar residue) at this position, the S72A mutation is likely to introduce hydrophobic interactions with V58, consistent with enhanced binding compared to wild-type (11-15\u03bcM (S72A) versus 50\u03bcM (Wild-type)).K79A leads to reduced binding to TCR (100\u03bcM). K79 forms a salt bridge interaction with E76 (TCR). Change to Ala will result in loss of this interaction consistent with a reduction in binding affinity. The fact that binding is not totally abolished suggests that this interaction is a not a major contributor to the binding energy. Note however that E76 also contacts R65 (see above).R124A mutation in BTN2A1 abolishes binding to TCR. The HADDOCK model suggests that R124 forms a salt bridge interaction with E70 (V\u03b39-IgV TCR) and a hydrogen bonding interaction with the hydroxyl group of T83. These interactions will be lost when introducing an Ala at this position.Y126A abolishes binding to TCR. Y126 forms multiple hydrophobic stacking interactions with I74 (HV4 region of Vg9-IgV). In addition, the hydroxyl group of Y126 forms a hydrogen bonding interaction with T77. These will be lost upon alanine substitution.Although Y133A is located at the interface with V\u03b39, it does not mediate interactions with V\u03b39 TCR residues and hence it is unsurprising that substitution to alanine does not affect binding affinity. E135 forms a salt bridge interaction with R20 (TCR). Substitution to Ala will result in a loss of this interaction, and consistent with this, E135A mutation abolishes binding to the TCR.1H-15N-labeled BTN3A1. Experiments were processed using Topspin 3.2 (Bruker). All analysis was performed using CCPN Analysis . SPR data was analyzed in BIAevaluation  and Origin 2015 (OriginLab).Stimulation data and transcript visualization in https://doi.org/10.17632/ny6bxn4y9s.1The RNaseq data of radiation hybrid clones filtered for transcribed human genes are available at Mendeley data"}
{"text": "However, in the context of human breast cancer, there is a lack of information for potential phenotypic alterations of this crucial immune cell subset. This is partly due to V\u03b42+ \u03b3\u03b4 T cells scarcity in surgical specimens. To break this deadlock, we assessed V\u03b42+ \u03b3\u03b4 T cell phenotypes using untreated breast cancer patients\u2019 peripheral blood, so-called minimally invasive \u201cliquid biopsy\u201d. We show that circulating V\u03b42+ \u03b3\u03b4 T cell phenotypic alterations are already established at diagnosis and related to tumor progression. Notably, terminally differentiated V\u03b42+ \u03b3\u03b4 T cells expressing canonical markers of replicative senescence and exhaustion were significantly associated with tumor-draining lymph node invasion. Our results shed light on the interest of using liquid biopsy to monitor rare events and support V\u03b42+ \u03b3\u03b4 T cell involvement in breast cancer pathogenesis and progression.V\u03b42+ \u03b3\u03b4 T cells in breast cancer is strongly supported by in vitro and murine preclinical investigations, characterizing them as potent breast tumor cell killers and source of Th1-related cytokines, backing cytotoxic \u03b1\u03b2 T cells. Nonetheless, insights regarding V\u03b42+ \u03b3\u03b4 T cell phenotypic alterations in human breast cancers are still lacking. This paucity of information is partly due to the challenging scarcity of these cells in surgical specimens. \u03b1\u03b2 T cell phenotypic alterations occurring in the tumor bed are detectable in the periphery and correlate with adverse clinical outcomes. Thus, we sought to determine through an exploratory study whether V\u03b42+ \u03b3\u03b4 T cells phenotypic changes can be detected within breast cancer patients\u2019 peripheral blood, along with association with tumor progression. By using mass cytometry, we quantified 130 immune variables from untreated breast cancer patients\u2019 peripheral blood. Supervised analyses and dimensionality reduction algorithms evidenced circulating V\u03b42+ \u03b3\u03b4 T cell phenotypic alterations already established at diagnosis. Foremost, terminally differentiated V\u03b42+ \u03b3\u03b4 T cells displaying phenotypes of exhausted senescent T cells associated with lymph node involvement. Thereby, our results support V\u03b42+ \u03b3\u03b4 T cells implication in breast cancer pathogenesis and progression, besides shedding light on liquid biopsies to monitor surrogate markers of tumor-infiltrating V\u03b42+ \u03b3\u03b4 T cell antitumor activity.The rationale for therapeutic targeting of V\u03b42 Breast cancer (BC) remains the most diagnosed and leading cause of cancer death among women worldwide . AlongsiHowever, exploring antitumor immunity patterns in the tumor bed using resected or biopsied primary or metastatic tumors shows multiple constraints. First, apart from being invasive, tumor biopsies are not always repeatedly feasible and are therefore poorly suitable for longitudinal studies or transfer in clinical routine. Second, genetic and immunological heterogeneity exists between and within each metastasis and the primary tumor, which contributes to the complexity of antitumor immunity pattern study using solid biopsies ,16. Thos+ T cells, \u03b3\u03b4 T cells display pro-inflammatory cytokine production and cytotoxic effector function. As for \u03b1\u03b2 CD8+ T cells, \u03b3\u03b4 T cells can be divided into four functionally distinct subsets reflecting their maturation stages, using a combination of canonical markers known to be differentially expressed during the course of T cell maturation. That is, following antigenic stimulation, CD45RA+ CCR7+ CD27+ CD28+ na\u00efve \u03b3\u03b4 T cells mature to CD45RA\u2212 CCR7+ central memory (CM) \u03b3\u03b4 T cells with low effector function and strong proliferative potential. Still, upon antigenic stimulation, CM \u03b3\u03b4 T cells can further mature to CD45RA\u2212 CCR7\u2212 CD27+/\u2212 CD28+/\u2212 effector memory (EM) \u03b3\u03b4 T cells, producing pro-inflammatory cytokines  and cytolytic protein . EM \u03b3\u03b4 T cells finally mature to CD45RA+ CCR7\u2212 CD27\u2212 CD28\u2212 re-expressing CD45RA terminally differentiated effector memory (TEMRA) \u03b3\u03b4 T cells with low proliferative potential and strong cytotoxic function [Human \u03b3\u03b4 T cells represent a unique conserved lineage of T cells, which are responsive against viral/microbial pathogens and transformed cells . Similarfunction ,31,32. W+ \u03b3\u03b4 T cells since they are the predominant subtype of \u03b3\u03b4 T cells in breast tissues. Yet V\u03b41+ \u03b3\u03b4 T cell functions remain controversial, either affiliated with a Th1 or regulatory polarization [+ \u03b3\u03b4 T cells are a potent pro-inflammatory mediator and cytotoxic effectors towards breast tumor cells and have been observed in direct contact with the latter in breast tumors [+ \u03b3\u03b4 T cells are the major subtype of \u03b3\u03b4 T cells in the peripheral blood [+ \u03b3\u03b4 T cells [+ \u03b3\u03b4 T cells phenotypic alterations in human breast cancers and their impact on disease progression is needed.Contrasting from their counterpart \u03b1\u03b2 T cells, \u03b3\u03b4 T cells display a major histocompatibility complex (MHC)-unrestricted antigen presentation and TCR activation, driving their maturation and the expression of natural killer cells (NK) associated cytotoxic receptors. Indeed, \u03b3\u03b4 T cells also differ from \u03b1\u03b2 T cells by expressing natural killer cell receptors such as the NKG2 receptors family. Hence, \u03b3\u03b4 T cells carry hallmarks of innate as well as adaptive immune responses . In brearization ,38,39. Ot tumors ,41,42. Wal blood . Of note T cells ,44,45. H+ \u03b3\u03b4 T cells phenotypic alteration detectable at diagnosis of early-stage breast cancer. Notably, peripheral PD-1+ or CD57+ EMRA V\u03b42+ \u03b3\u03b4 T cells are associated with the pathological involvement of tumor-draining axillary lymph nodes.To this end, we used mass cytometry to quantify up to 130 immune variables from the peripheral blood of untreated breast cancer patients. We evidenced peripheral V\u03b42A total of 122 immune variables were quantified from peripheral blood mononuclear cells (PBMCs) of 13 newly diagnosed BC patients and four healthy volunteers (HV) using two mass cytometry panels Table S1Because there are only two groups, BGA output is a single dimension discriminating axis, where each sample is positioned according to the coexpression of the 122 variables used as input . Still, in the HV group, T cell populations displayed poorly differentiated and non-activated profiles. Indeed, the frequency of Na\u00efve (CD45RA+ CCR7+ CD27+ CD28+) V\u03b42+ \u03b3\u03b4 T cells, Na\u00efve \u03b1\u03b2CD8+ T cells, Na\u00efve \u03b1\u03b2CD4+ conventional T cells, central memory  V\u03b42+ \u03b3\u03b4 T cells, resting (CD45RA+ CCR7+ CTLA-4low ICOSlow) Tregs and Tregs expressing a marker associated with a disrupted immunosuppressive activity (DNAM1+), were increased in HV samples compared to BC samples. On the opposite, T cells displaying a differentiated and polarized phenotype were associated with the BC group. Indeed, the frequency of effector memory T cells re-expressing CD45RA  V\u03b42+ \u03b3\u03b4 T cells, TEMRA \u03b1\u03b2CD8+, late effector memory  \u03b1\u03b2CD8+ T cells and early effector memory  \u03b1\u03b2CD4+ conventional T cells were increased in BC samples compared to HV samples. Additionally, an increased frequency of highly cytotoxic (CD8+) NK cells was also detected in BC samples. Importantly, frequencies of V\u03b42+ \u03b3\u03b4 T, \u03b1\u03b2CD8+ T and NK cells expressing inhibitory receptors  were also increased in BC samples.In the group of HV, we detected an increased frequency of NK cells expressing NK triggering receptors , 7% (NK NKG2C+), 6.3% (V\u03b42+ \u03b3\u03b4 CD4+), 4.7% (V\u03b42+ \u03b3\u03b4 CM), 4.1% (\u03b1\u03b2CD8+ Naive), 4% (NK IL7R+), 3.5% (Tregs DNAM1+), 3.1%(Tregs resting) and 3%  of contribution to the discrimination of groups (+ \u03b3\u03b4 KIR2DL1/DS1+), 6.1% (\u03b1\u03b2CD8+ KIR2DL1/DS1+), 4.5% (V\u03b42+ \u03b3\u03b4 KIR2DL2/DL3+), 4.2% (\u03b1\u03b2CD8+ LEM), 4% , 3.7% (\u03b1\u03b2CD8+ TEMRA), 3.5% (\u03b1\u03b2CD8+ LAG3+) and 3.2% (NK CD8+) of contribution to the discrimination of groups  and six BC patients harboring invaded tumor-draining lymph nodes (BC N+). Among the 130 immune variables, 32, 31, 20, 19 and 28 variables were, respectively expressed by V\u03b42ications A.+) highly cytotoxic (CD56+) V\u03b42+ \u03b3\u03b4 T cells profiles. Of note, TEMRA V\u03b42+ \u03b3\u03b4 T cells were the unique population harboring a significantly increased frequency in BC N+ patients compared to BC N\u2212 patients  and a canonical marker of T cell functional replicative senescence (CD57+) tends to increase in some patients harboring lymph node invasion, although the difference was not significant. The frequency of NK cells and \u03b1\u03b2CD4+ T cells expressing inhibitory immune checkpoint receptors  also tended to increase in some patients harboring lymph node invasion.Interestingly, BC N+ patients displayed fully differentiated (TEMRA), activated (ICOSpatients . However+ \u03b3\u03b4 TEMRA), 7% (V\u03b42+ \u03b3\u03b4 CD57+), 4.5% , 4.1% (V\u03b42+ \u03b3\u03b4 TIM3+), 3.6% , 3.4% (V\u03b42+ \u03b3\u03b4 KIR2DL1/DS1+), 3% (V\u03b42+ \u03b3\u03b4 ICOS+) and 2.7%  of contribution to the discrimination of groups (+ \u03b3\u03b4 KIR2DL1/DS1+), 6% (\u03b1\u03b2CD8+ KIR2DL1/DS1+), 5% (V\u03b42+ \u03b3\u03b4 KIR2DL2/DL3+), 4% (\u03b1\u03b2CD8+ LEM) and 3% , 3.7% (\u03b1\u03b2CD8+ TEMRA), 3.5% (\u03b1\u03b2CD8+ LAG3+) of contribution to the discrimination of groups  , cytotoxic potential , activation state , replicative senescence (CD57), inhibitory signaling and tumor-promoting tolerance , susceptibility to apoptosis (Fas), tumor cell recognition and costimulatory signaling (DNAM-1)  A. Twenty(DNAM-1) . Echoing+ \u03b3\u03b4 T cell clusters that coexpressed inhibitory checkpoint receptors and T cells replicative senescence markers were found to be associated with lymph node involvement (+ PD-L1+ BTLA+ EEM (cluster 2), TIGIT+ CTLA-4+ PD-1+ EEM (cluster 12), CD16+ CD56+ CD57+ PD-1\u2212/+ TIGIT+/\u2212 PD-L1\u2212/+ TEMRA  V\u03b42+ \u03b3\u03b4 T cells were exclusively found in patients with lymph node involvement  approved by the institutional review board (Comit\u00e9 d\u2019Orientation Strat\u00e9gique (COS), Marseille, France) of the Paoli-Calmettes Institute. Written informed consent was obtained from all patients in concordance with the Declaration of Helsinki. Age-matched healthy subjects were recruited from the Etablissement Fran\u00e7ais du Sang (EFS Alpes-M\u00e9diterran\u00e9e).Breast cancer patients treated at the Institut Paoli-Calmettes were prospectively enrolled between February 2018 and June 2018. Fresh EDTA-anticoagulated blood samples were obtained from patients at diagnosis (n = 13) and healthy volunteers (N = 4). Blood samples were processed extemporaneously. After analysis of morphological tumor characteristics by pathologists, patients were classified as summarized in \u00ae instrument, Fluidigm), at an acquisition rate of approximately 500 events per second. Following the manufacturer\u2019s instructions, settings were on default.PBMCs were obtained using Ficoll-Paque density-gradient centrifugation. Cells were consecutively centrifuged and incubated with cisplatin 0.1 M to stain dead cells. Aspecific epitope binding was blocked with 0.5 mg/mL human Fc Block . The two mass cytometry panels used are provided in + T cells, \u03b1\u03b2CD8+ T cells, \u03b1\u03b2CD4+ conventional T cells, Tregs and NK cells were manually gated according to the gating strategy displayed in TCR\u03b3\u03b42+ \u03b3\u03b4 T cells were exported using FlowJo V10.6.2. Prior to t-SNE analyses using Cytosplore V2.2.1 [+ \u03b3\u03b4 T cells for each file. The t-SNE analysis was carried out with the default setting (perplexity of 30 and 1000 iterations), and V\u03b42+ \u03b3\u03b4 T cell subpopulations were automatically defined by cell density gradient. The results of the t-SNE analysis for each panel are provided in Manually gated V\u03b42e V2.2.1 , consensp-value < 0.05 was considered as significant.Statistical analyses were generated using GraphPad Prism V5.00. Data are expressed as mean \u00b1 standard error of the mean (SEM). Statistical significance between two groups was calculated using the nonparametric Mann\u2013Whitney test. A + \u03b3\u03b4 T cells, phenotypic alterations were evidenced in newly diagnosed breast cancer patients. PD-1+ or CD57+ EMRA V\u03b42+ \u03b3\u03b4 T cells associated with lymph node invasion. These findings evidenced in the context of an exploratory study require confirmation in a larger cohort. However, they open new perspectives for the development of V\u03b42+ \u03b3\u03b4 T cell immunotherapy in breast cancer.Circulating V\u03b42"}
{"text": "Scientific Reports 10.1038/s41598-020-62990-0, published online 20 April 2020Correction to: This Article contains errors in Table 1 where two column headings are incorrect.d13C (\u2030)\u201d and \u201cd15N (\u2030)\u201d.\u201cshould read:\u03b413C (\u2030)\u201d and \u201c\u03b415N (\u2030)\u201d, respectively.\u201c"}
{"text": "RDPBR\u2019 Pd0 and PdII complexes (RDPBR\u2019=(o\u2010PR2C6H4)2BR\u2019, diphosphinoborane) was analyzed using XRD, 11B\u2005NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state PdII and Pd0, stabilizing the latter. Reaction of lithium amides with [(RDPBR\u2019)PdII(4\u2010NO2C6H4)I] chemoselectively yields the C\u2212N coupling product. DFT modelling indicates no significant impact of PdII\u2192B coordination on the inner\u2010sphere reductive elimination rate.The dative Pd\u2192B interaction in a series of  Ligand effects: The borane acceptor in diphosphinoborane ligands discriminates between the oxidation state PdII and Pd0, stabilizing the latter. The impact of the Pd\u2192B interaction on inner\u2010sphere C\u2212N bond reductive elimination of N,N\u2010dimethyl\u20104\u2010nitroaniline was investigated (see scheme). We determine how the oxidation state of Pd and co\u2010ligands affect the strength of the Pd\u2192B interaction in DPB complexes. NBO/NLMO calculations and solid\u2010state structures are used to assess the strength of Pd\u2192B interactions. The value of the 11B\u2005NMR chemical shift as a probe is discussed. The reductive elimination of N,N\u2010dimethyl\u20104\u2010nitroaniline from [(PhDPBPh)PdII(4\u2010NO2\u2010C6H4)NMe2] (5) was studied and modelled with DFT calculations to investigate the assumed influence of the borane acceptor.We speculated that the electron\u2010withdrawing properties of the borane functionality in diphosphinoborane (DPB) ligands enhances the rate of inner\u2010sphere reductive elimination from Pd complexes due to 1)\u2005overall reduced electron density at the PdPhDPBPh)PdII] complexes was synthesized to examine a possible correlation between the nature of ligands at Pd and the strength of the PdII\u2192B interaction (Scheme\u2005A series of [(n Scheme\u2005.PhDPBPh)PdIICl2] (7) was produced by reaction of PhDPBPh ligand with [(cod)PdCl2] in DCM and was isolated in 74\u2009% yield \u2005\u00c5 is shorter than the sum of the van der Waals radii (3.28\u2005\u00c5),2\u2010 type coordination to the PdII center. A slightly increased pyramidalization at the boron atom is observed (\u03a3B\u03b1=355.4\u00b0) compared to complex [(iPrDPBPh)PdCl2] (\u03a3B\u03b1=359.9\u00b0).Complex  and was isolated in 67\u2009% yield. The 31P\u2005NMR spectrum displays two broad resonances of equal intensity at \u03b4=45.2 and 38.1\u2005ppm (CD2Cl2), suggesting a similar dynamic process as in 7. Due to the poor solubility of both 7 and 8, no 11B\u2005NMR spectra could be obtained.Complex\u2005PhDPBPh)PdIICl]SbF6 (9) was produced in 51\u2009% isolated yield by halide abstraction from 7 with AgSbF6 PdII(\u03bc\u2010Cl)]2(SbF6)2 is observed with an inversion center between the two PdII centers. Within the dimer, the PdII center is coordinated in a square\u2010pyramidal fashion with the borane located in the apical position. The Pd, B distance in complex\u20059 is 2.721(5)\u2005\u00c5, which is slightly shorter than in [(PhDPBPh)PdIICl2] 7 (2.762(3)\u2005\u00c5). However, pyramidalization of the borane is almost identical (\u03a3B\u03b1=355.8\u00b0). The absence of a relevant \u03b72\u2192PdII interaction is suggested by the long Pd1,C1 distance of 3.338(4) \u00c5. The Pd,B distance and lack of significant pyramidalization at the borane suggest a weak PdII\u2192B interaction, which is in line with a broad resonance in the 11B\u2005NMR spectrum at \u03b4=65\u2005ppm (\u03c91/2=1900\u00b1500\u2005Hz).Cationic complex SbF6 (10) was synthesized by reaction of AgSbF6 with zwitterionic allyl complex [{(o\u2010PPh2C6H4)2B(OAc)Ph}PdII(C3H5)] (4) \u2005\u00c5, which is in line with a minor pyramidalization at the borane center (\u03a3B\u03b1=354.7\u00b0) and a broad 11B\u2005NMR resonance at \u03b4=62\u2005ppm (\u03c91/2=1200\u00b1100\u2005Hz). A large Pd,C22 distance of 3.066(6)\u2005\u00c5 eliminates the possibility of a strong \u03b72\u2192PdII interaction. The \u03b73\u2010coordinated C3H5\u2010ligand is disordered. Using the borane as a reference point, a 39:61 mixture of the exo\u2010 and endo\u2010isomers is observed. A wider P\u2010Pd\u2010P angle of 102.86(5)\u00b0 is realized by a decrease in the twisting of the ligand backbone . The observed disorder of the C3H5\u2010ligand is in good agreement with the observed NMR spectra. In the 31P\u2005NMR spectrum (CD2Cl2), two singlet resonances are observed in a 40:60 ratio (\u03b4=28.1 and 26.9\u2005ppm) and two sets of C3H5\u2010units are detected in the 1H\u2005NMR spectrum. DFT calculations (BP86/def\u2010SV(P)) based on the solid\u2010state structures of endo10\u2010 and exo10\u2010 indicate a small Gibbs free energy preference of \u0394G=0.74\u2005kcal\u2009mol\u22121 for endo10\u2010, predicting a 29:71 ratio at 298\u2005K.Cationic allyl complex [(H5)]SbF6 0 was syno\u2010PPh2C6H2B(OAc)PhII\u2192B interaction on reductive elimination proceeding via an inner\u2010sphere mechanism, complex [(PhDPBPh)PdII(4\u2010NO2\u2010C6H4)I] (5) was reacted with lithium amides. Complex\u20055 was reacted with LiNMe2 (1.1\u2005equiv) at room temperature in [D8]THF  and 38.3\u2005ppm (14\u2009%). After a total of 4.5\u2005h, all resonances in the 31P\u2005NMR spectrum disappeared in favor of the singlet at \u03b4=31.1\u2005ppm. 11B\u2005NMR spectroscopy suggested formation of a zero\u2010valent palladium complex by a broad resonance at \u03b4=19\u2005ppm (\u03c91/2=400\u00b1100\u2005Hz). The concurrent formation of the expected reductive elimination product N,N\u2010dimethyl\u20104\u2010nitroaniline was confirmed by GC/MS analysis, using an independently prepared sample as a reference. The absence of an intermediate complex cis\u2010[(PhDPBPh)PdII(4\u2010NO2\u2010C6H4)NMe2] suggests that transmetalation is rate\u2010limiting in this transformation. The intermediate occurrence of the 31P\u2005NMR resonance at \u03b4=38.3\u2005ppm is possibly due to a reversible reaction of LiNMe2 with complex\u20056. In a control experiment complex [(PhDPBPh)Pd0(pyridine)] (1) was reacted with LiNCy2 and LiNMe2 in [D8]THF. In both cases ca. 7\u2009% of a new complex at \u03b4=38.5 (s) and 37.7\u2005ppm (s) were observed.A conversion of 84\u2009% was observed 6 decomposed within hours with simultaneous precipitation of palladium black. Addition of PMe3 as a stabilizing co\u2010ligand led to the formation of complex [(PhDPBPh)Pd0(PMe3)] 11. The 31P\u2005NMR spectrum of 11 showed a doublet at \u03b4=35.3 and a triplet at \u221240.1\u2005ppm (J=15.1\u2005Hz) in a 2:1 ratio, which is consistent with the expected \u03ba3P\u2010coordination. The broad resonance in the 11B\u2005NMR spectrum at \u03b4=25\u2005ppm (\u03c91/2=400\u00b1100\u2005Hz) suggested a strong Pd0\u2192B interaction. Complex\u200511 could also be synthesized independently by reaction of PBP pincer 12 with PhLi and PMe3, or reaction of 1 with PMe3, thus confirming unambiguously the identity of 11 (Scheme\u2005Complex\u20055 reacted in a similar fashion with LiNCy2 (26\u2009% 6 after 3\u2005h) and LiNHtBu (14\u2009% 6 after 5.5\u2005h). However, the reaction proceeded slower with these sterically more demanding substrates. The reaction of complex\u20055 with LiNHtBu was monitored for 96\u2005h by 31P\u2005NMR spectroscopy (46\u2009% conversion towards 6) without any side products being observed (cf. Table\u2005S1). This is in line with the assumption of a rate\u2010determining transmetalation followed by a quick reductive elimination.Complex\u20050/II DPB complexes were analyzed to identify factors which affect the strength of Pd\u2192B interactions. In addition to the new Pd complexes presented in this work (6\u201310), the structurally characterized DPB complexes cis\u2010[(PhDPBPh)PdII(4\u2010NO2\u2010C6H4)I] (5),PhDPBPh)Pd0(pyridine)] (1),PhDPBMe)Pd0(PMe3)] (13)CyDPBPh)Pd0] (3)0/II center. The shorter Pd,B distances and higher degree of borane pyramidalization =2.194(3) \u22122.243(2)\u2005\u00c5 vs. PdII: \u03a3B\u03b1=354\u2013356\u00b0, d=2.676(5) \u22122.762(2)\u2005\u00c5). Remarkably, even the generation of cationic PdII complexes (9 and 10) has no significant impact on the strength of PdII\u2192B interactions. The oxidation state at Pd is unambiguously the dominant factor for the strength of the Pd,B bond.The solid\u2010state structures of PdPBPh)PdII\u2010NO2\u2010C6H4s work 6\u20130, the st1, 3, 5\u201311 and 13 were geometrically optimized using Turbomole 7.0.1 (BP86/def\u2010SV(P)). A good agreement was observed between the optimized structures and their corresponding solid\u2010state structures \u2010coordination was found in the NBO calculations. The Wiberg bond index for Pd,Cipso was below 0.02, with the exception of Pd0 complexes\u20051 (0.0697) and 6 (0.0325). Reactivity studies of [(DPB)Pd]\u2010complexes presented in this paper thus appear to be unaffected from significant \u03b72\u2010coordination.The Pd\u2192B interactions were further analyzed using QM calculations. Complexes\u2005II\u2192B interactions, a narrow range of NBO stabilizing energies between 8.04 and 11.46\u2005kcal\u2009mol\u22121 was observed. Surprisingly, generation of cationic complexes , exchange of chloro\u2010ligands by bromide (8) or iodide/aryl (5) had very little effect. In the case of Pd0\u2192B interactions, significantly higher NBO stabilizing energies of 19.53\u201346.83\u2005kcal\u2009mol\u22121 were found. Regardless of the oxidation state at Pd an approximately linear correlation between the Pd,B distance and the NBO stabilizing energy (E2) associated with the Pd,B interaction was observed  by PCy2\u2010groups (3) had only a minor effect. The E2 values for the Pd0\u2192B interaction in the 14 VE complexes\u20053  and 6  significantly deviate from this correlation and are almost twice as much as for 16\u2005VE complexes\u20051  and 13 . Neither the 11B\u2005NMR chemical shift, Pd,B distance or pyramidalization at B indicate a change of the Pd0\u2192B interaction strength in this magnitude between the 14\u2005VE and the 16\u2005VE complexes Pd0(PPh3)] (2) reported by Kameo and Bourissou\u03b4(11B) 27\u2005ppm). In contrast, the 11B\u2005NMR resonance shifts linearly towards lower field with an increasing Pd,B distance in case of PdII complexes. 11B\u2005NMR spectroscopy therefore can be used as a tool to assess the strength of Pd\u2192B interactions within a given ligand system, provided that the oxidation state at the Pd center is taken into account. However, given the difficulty to determine the precise \u03b4(11B) of [(DPB)PdII] complexes (poor solubility and \u03c91/2 >1000\u2005Hz ), a certain error for weak PdII\u2192B interactions needs to be factored in.The r Figure\u2005. ComplexN,N\u2010dimethyl\u20104\u2010nitroaniline from complex\u200514\u2010B , yielding Pd0 complex\u20056 and N,N\u2010dimethyl\u20104\u2010nitroaniline . In order to understand how the PdII\u2192B interaction affects the reductive elimination, the reaction was also modeled for bis[(2\u2010diphenylphosphino)phenyl]ether (DPEphos) complex\u200514\u2010O and diphosphinoamine complex\u200514\u2010N. DPEphos is well established as an effective ligand in palladium catalyzed Buchwald\u2013Hartwig\u2010type coupling reactions,PhDPBPh (Table\u2005o\u2010PPh2C6H4)2NPhN\u2010Ph bridgehead gives a good model of the B\u2010Ph group in 14\u2010B. Elimination of N,N\u2010dimethyl\u20104\u2010nitroaniline from complexes\u200514\u2010O and 14\u2010N gave very similar Gibbs free reaction energies of \u0394G=\u221238.52\u2005kcal\u2009mol\u22121 and \u0394G=\u221238.63\u2005kcal\u2009mol\u22121, respectively. No Pd0/II\u2192E interactions were observed in complexes featuring DPEphos and the diphosphinoamine ligand \u2005an electronic effect by Pd\u2192B coordination and 2)\u2005increased steric bulk of the DPB ligand imposed by the B\u2010Ph group. In case of diphosphinoamine complex 14\u2010N the reductive elimination barrier decreased to \u0394G\u2260=5.54\u2005kcal\u2009mol\u22121 , possibly as a result of the increased steric pressure imposed by the N\u2010Ph group  proceeds via structurally early transition\u2010state 15\u2010E  were used to model the inner\u2010sphere reductive elimination of 15\u2010B, compared to starting complex\u200514\u2010B, as indicated by a slightly elongated Pd,B distance (2.947\u2005\u00c5) in 15\u2010B compared to 14\u2010B (2.906\u2005\u00c5). Similarly, the Wiberg bond index for the Pd\u2192B interaction is reduced to 0.162 in 15\u2010B (14\u2010B: 0.176), and the NPA charge at the borane remains unchanged (14\u2010B: +0.737 vs. 15\u2010B: +0.735). The increase of the Pd\u2192B interaction strength occurs after the reductive elimination, explaining why the inner\u2010sphere reductive elimination of the C\u2212N bond does not kinetically profit from the substantial increase of the Pd\u2192B strength in the course of the reaction.Unexpectedly, the Pd\u2192B interaction is slightly weakened in transition\u2010state N,N\u2010dimethyl\u20104\u2010nitroaniline was also modeled using cis\u2010[(PMe3)2PdII(4\u2010NO2C6H4)NMe2]  and its BH3 adduct [(PMe3)2(BH3)PdII(4\u2010NO2C6H4)NMe2]  as substrates (cf. Scheme\u2005S1). Again, a more favorable transition state was found for the acceptor free complex 17 , than for the borane adduct 17\u2010B .To rule out effects originating from restraints imposed by a chelating ligand frame work, the reductive elimination of 11B\u2005NMR spectroscopy has been established as a useful tool to assess the strength of Pd\u2192B interactions in solution. Reaction of lithium amides with [(PhDPBPh)PdII(4\u2010NO2C6H4)I] (5) chemoselectively yields the C\u2010N coupling product and [(PhDPBPh)Pd0] (6). Inner\u2010sphere reductive C\u2212N bond elimination was modelled with DFT methods for the PhDPBPh ligand. In contrast to reports on acceptor promoted outer\u2010sphere reductive C\u2212N bond elimination,The strength of Pd\u2192B interactions in [(DPB)Pd] complexes depends primarily on the oxidation state of Pd. In contrast, modifications of the DPB ligand or co\u2010ligands have only a minor effect. n\u2010hexane were dried over sodium, distilled under argon prior to use and stored over activated molecular sieves (4\u2005\u00c5).All manipulations were performed under an argon atmosphere using standard Schlenk line and glovebox techniques. Glassware was oven dried at 120\u2009\u00b0C overnight and dried with a heat gun under vacuum prior to use. Tetrahydrofuran was dried by an MBraun solvent purification system. Benzene and 2Cl2 and C6D6 were degassed employing the freeze\u2010pump\u2010thaw technique and stored over activated molecular sieves (4\u2005\u00c5). [D8]THF was dried over activated molecular sieves (3\u2005\u00c5), distilled under an argon atmosphere and degassed employing the freeze\u2010pump\u2010thaw technique. PhDPBPh, [(PhDPBPhOAc)Pd(C3H5)] (4), [(PhDPBPh)Pd(4\u2010NO2C6H4)I] (5) and [{(o\u2010PPh2C6H4)2BPh}PdI] (12) were synthesized according to published procedures.CD\u00ae quick pressure valve NMR tubes. 1H, 11B{1H}, 13C{1H}, 19F{1H}, and 31P{1H} NMR spectra were recorded on a Bruker Avance II  or a Bruker Avance  spectrometer. 1H and 13C{1H} NMR spectra were referenced to residual solvent resonances as implemented in MesReNova 10.0.2. Infrared spectra were recorded on an Avatar 360 FT\u2010IR E.S.P. device by Nicolet. CHN combustion analysis were carried out on an Elementar EL device by Elementar Analysesysteme GmbH.NMR\u2010experiments were performed in Wilmad7), 1987625 (9) and 1987626 (10) Deposition Number(s) 1987620 ( contain(s) the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures.8]THF (0.25\u2005mL) was added dropwise over a period of 4\u2005min to a stirred solution of nitroarene complex\u20055  in [D8]THF (0.25\u2005mL). The resulting mixture was stirred for another 5\u2005min and then transferred into an NMR tube. Reductive elimination was monitored by 31P\u2005NMR spectroscopy.A solution of the respective lithium amide  in [D2Cl2 (8\u2005mL) was added to a mixture of PhDPBPh  and [(cod)PdCl2] . The mixture was stirred for 30\u2005min at room temperature. Yellow crystals  were formed by overlaying the solution n\u2010pentane (16\u2005mL). Single crystals suitable for X\u2010ray diffraction were grown from a solution of [(cod)PdCl2]  and PhDPBPh  in CD2Cl2 (0.7\u2005mL) overlaid with benzene (0.3\u2005mL). 11B and 13C\u2005NMR data have not been collected due to poor solubility. 1H\u2005NMR : \u03b4 7.81\u20137.76 , 7.55 , 7.50\u20137.46 , 7.46\u20137.38 , 7.35\u20137.14 , 6.97\u20136.78 , 5.32 . 31P{1H} NMR : \u03b4 44.5 . IR (KBr): \u03bd\u02dc=3643\u20103284 (w), 3049 (w), 1587 (w), 1497 (m), 1433 , 1223 (s), 1158 (vw), 1128 (w), 1093 (vs.), 987 (w), 889 (vw), 864 (vw), 754 (s), 744 (s), 733 (m), 688 (vs.), 667 (w), 611 (m), 600 (s), 542 (m), 523 (vs.), 505 (m) cm\u22121. Elemental analysis calcd (%) for C42H33BCl2P2Pd\u22c5CH2Cl2: C 59.18, H 4.04, found: C 59.61, H 4.33.CHPhDPBPh ligand  and [(cod)PdBr2]  were solved in DCM (10\u2005mL) and stirred at r.t. for 30\u2005min. The solution was overlaid with n\u2010hexane (20\u2005mL) yielding title compound\u20058 as orange crystals . 11B and 13C\u2005NMR data have not been collected due to poor solubility. 1H\u2005NMR : \u03b4 7.85\u20137.76 , 7.59\u20137.19 . 31P{1H} NMR : \u03b4 45.2 , 38.1 . IR (KBr): \u03bd\u02dc=3424 (s), 3048 (m), 1621 (w), 1587 (w), 1478 (m), 1455 (w), 1432 (s), 1311 (w), 1237 (w), 1220 (s), 1205 (m), 1187 (m), 1153 (w), 1126 (m), 1092 (s), 1027 (w), 1000 (m), 887 (w), 863 (w), 753 (s), 741 (s), 713 (m), 699 (s), 690 (s), 667 (m), 610 (s), 600 (s), 539 (s), 522 (s), 505 (s), 465 (m) cm\u22121. Elemental analysis calcd (%) for C42H33BBr2P2Pd\u22c50.25CH2Cl2: C 56.51; H 3.76, found: C 56.72, H 3.83.The 7  and AgSbF6  were stirred in DCM (15\u2005mL) for 40 minutes. The suspension was filtered through a syringe filter . The clear solution was overlaid with n\u2010hexane (30\u2005mL) yielding the title compound\u20059 as long colorless needles . 1H\u2005NMR : \u03b4 7.97\u20137.92 , 7.80 , 7.69 , 7.65 , 7.55 , 7.47\u20137.34 , 7.27\u20137.16 , 7.00 , 6.83 . 11B{1H} NMR : \u03b4=65 . 13C{1H} NMR : \u03b4=\u03b4 141.79, 135.43 , 134.88 , 134.25, 133.69 , 133.22 , 132.49 , 129.67 , 129.33\u2013128.82 (m), 128.10, 127.13, 126.74, 126.16. 31P{1H} NMR : \u03b4 49.9 . IR (KBr): \u03bd\u02dc=3441 (s), 3058 (w), 1588 (w), 1482 (w), 1435 (s), 1230 (m), 1200 (w), 1125 (w), 1034 (m), 1001 (w), 867 (vw), 752 (s), 702 (s), 692 (s), 659 (vs.), 614 (m), 538 (s), 517 (s), 697 (w) cm\u22121. Elemental analysis calcd (%) for C42H33BClF6P2PdSb\u22c50.25 C6H14: C 51.75, H 3.64, found: C 51.77, H 3.785.Complex\u20054  and AgSbF6  were solved in CH2Cl2 (7\u2005mL) and stirred at r.t. for 20\u2005min. The suspension was filtered through a syringe filter . The clear solution was overlaid with n\u2010hexane (10\u2005mL). The obtained crystals showed insufficient purity and were crystallized again under the same conditions yielding 10 as slightly yellow crystals . 1H\u2005NMR : \u03b4 7.72\u20137.59 , 7.58\u20137.53 , 7.53\u20137.44 , 7.43\u20137.29 , 7.23\u20137.15 , 7.05\u20136.87 , 6.78\u20136.67 , 5.88\u20135.70 , 3.77\u20133.61 , 3.59\u20133.33 , 3.03\u20132.85 , 2.49\u20132.29  . 11B{1H} NMR : \u03b4 64 . 13C{1H} NMR : \u03b4 141.1, 140.2, 136.1, 135.5, 135.3, 135.0, 134.4, 134.3, 134.0, 133.2 , 132.3, 132.2, 132.1, 131.6, 131.5, 131.2, 131.0, 129.6 , 129.3, 128.9, 123.1, 80.4, 80.2. 31P{1H} NMR : \u03b4 28.1 , 26.9 . IR (KBr): \u03bd\u02dc=3430 (s), 3000 (m), 1588 (m), 1480 (m), 1458 (w), 1434 (s), 1268 (m), 1227 (s), 1127 (m), 1095 (m), 1031 (w), 999 (w), 950 (vw), 875 (w), 772 (w), 754 (m), 742 (m), 733 (m), 695 (s), 659 (vs.), 609 (s), 537 (m), 521 (s), 478 (w), 430 (w) cm\u22121. Elemental analysis calcd (%) for C46H40BCl2F6P2PdSb: C 51.22, H 3.74, found: C 51.04, H, 3.86.Allyl complex\u20052\u22c5THF  in [D8]THF (0.25\u2005mL) was added over a period of 3\u2005min to a solution of complex\u20055  in [D8]THF (0.25\u2005mL). The combined solutions were transferred to an NMR tube and NMR spectra were recorded after 1.5 and 4.5\u2005h. 11B{1H} NMR : \u03b4 19 . 31P{1H} NMR : \u03b4 30.93 (s).A solution of LiNMe12  in THF (0.5\u2005mL). After stirring for 10\u2005min at r.t. a solution of PMe3 in toluene  was added. The precipitate was removed by filtration and the solution was concentrated in vacuo. The resulting solid was washed with pentane and dried in vacuo . 1H\u2005NMR : \u03b4 8.34 , 7.69\u20137.58 , 7.44\u20137.37 , 7.36\u20137.28 , 7.12 , 7.09\u20137.05 , 6.85 , 6.68 , 0.64 . 11B{1H} NMR : \u03b4 25 . 13C{1H} NMR : \u03b4 168.7 (bs), 143.2 , 143.0 , 141.5 , 138.9 , 135.8 , 135.7 , 133.5 , 133.0 , 132.3 (s), 132.3 (s), 132.4 , 129.5 (s), 129.0 (s), 128.6 (s), 127.2 (s), 126.1 , 125.2 (s), 18.1 . 31P{1H} NMR : \u03b4 35.44 , \u221240.13 .A solution of PhLi  in THF (0.5\u2005mL) was slowly added to a solution of complex\u2005The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The title hydrazine carbodi\u00adthio\u00adate chloro\u00adform hemi-solvate features approximately planar mol\u00adecules with splayed phenyl groups. Supra\u00admolecular tapes are formed in the crystal through a combination of N\u2014H\u22efS, hydroxyl-O\u2014H\u22efO(hydrox\u00adyl) and hydroxyl-O\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions. 15H14N2O2S2\u00b7CHCl3, comprises two independent hydrazine carbodi\u00adthio\u00adate mol\u00adecules, A and B, and a chloro\u00adform mol\u00adecule; the latter is statistically disordered about its mol\u00adecular threefold axis. The common features of the organic mol\u00adecules include an almost planar, central CN2S2 chromophore [r.m.s. deviation = 0.0203\u2005\u00c5 (A) and 0.0080\u2005\u00c5 (B)], an E configuration about the imine bond and an intra\u00admolecular hydroxyl-O\u2014H\u22efN(imine) hydrogen bond. The major conformational difference between the mol\u00adecules is seen in the relative dispositions of the phenyl rings as indicated by the values of the dihedral angles between the central plane and phenyl ring of 71.21\u2005(6)\u00b0 (A) and 54.73\u2005(7)\u00b0 (B). Finally, a difference is seen in the disposition of the outer hydroxyl-H atoms, having opposite relative orientations. In the calculated gas-phase structure, the entire mol\u00adecule is planar with the exception of the perpendicular phenyl ring. In the mol\u00adecular packing, the A and B mol\u00adecules assemble into a two-mol\u00adecule aggregate via N\u2014H\u22efS hydrogen bonds and eight-membered {\u22efHNCS}2 synthons. The dimeric assemblies are connected into supra\u00admolecular chains via hydroxyl-O\u2014H\u22efO(hydrox\u00adyl) hydrogen bonds and these are linked into a double-chain through hy\u00addroxy-O\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions. The double-chains are connected into a three-dimensional architecture through phenyl-C\u2014H\u22efO(hydrox\u00adyl) and phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions. The overall assembly defines columns along the a-axis direction in which reside the chloro\u00adform mol\u00adecules, which are stabilized by chloro\u00adform\u2013methine-C\u2014H\u22efS(thione) and phenyl-C\u2014H\u22efCl contacts. The analysis of the calculated Hirshfeld surfaces, non-covalent inter\u00adaction plots and inter\u00adaction energies confirm the importance of the above-mentioned inter\u00adactions, but also of cooperative, non-standard inter\u00adactions such as \u03c0(benzene)\u22ef\u03c0(hydrogen-bond-mediated-ring) contacts.The title hydrazine carbodi\u00adthio\u00adate chloro\u00adform hemisolvate, 2C Di\u00adthio\u00adcarbazato Schiff bases have received considerable attention because of the presence of both soft sulfur and hard nitro\u00adgen atoms As part of on-going studies in this area \u2005\u00c5, for the N2 atom, and 0.0319\u2005(16)\u2005\u00c5 for N1; the C2 and C9 atoms lie, respectively, 0.161\u2005(3) and 0.096\u2005(4)\u2005\u00c5 out of the plane, in the direction of the N2 atom. The comparable plane for the S3-mol\u00adecule is significantly more planar with an r.m.s. deviation = 0.0080\u2005\u00c5 with maximum deviations of 0.0131\u2005(16)\u2005\u00c5 for the N3 atom and 0.0104\u2005(12)\u2005\u00c5 for atom N4; the C17 atom lies 0.018\u2005(3)\u2005\u00c5 out of the central plane in the direction of the N3 atom, and the C24 lies 0.123\u2005(3)\u2005\u00c5 out of the plane in the direction of the N4 atom. The small difference in planarity is reflected in the C1\u2014N1\u2014N2\u2014C2 and C16\u2014N3\u2014N4\u2014C17 torsion angles of 171.8\u2005(2) and 179.3\u2005(2)\u00b0, respectively. More significant conformational differences are apparent in rest of the mol\u00adecules: for the S1-mol\u00adecule, the dihedral angles between the central residue and terminal hy\u00addroxy\u00adbenzene and phenyl rings are 6.18\u2005(13) and 77.21\u2005(6)\u00b0, respectively, indicating close to co-planar and perpendicular relationships; the dihedral angle between the terminal rings is 71.22\u2005(8)\u00b0. The equivalent dihedral angles for the S3-mol\u00adecule are 6.07\u2005(13), 54.53\u2005(6) and 54.73\u2005(7)\u00b0, respectively. The other notable difference between the mol\u00adecules relates to the relative orientation of the hy\u00addroxy-H atoms in the 4-position, no doubt arising owing to the dictates of the mol\u00adecular packing.The crystallographic asymmetric unit of (I)E in each case. The comparison of geometric parameters in Table\u00a01The relatively co-planar relationship between the central residue and the appended hy\u00addroxy\u00adbenzene ring allows for the formation of an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(imine) hydrogen bond in each mol\u00adecule, Table\u00a02Gaussian16 An overlay diagram for the experimental and theoretical, gas-phase structures is shown in Fig.\u00a02via O4-hy\u00addroxy-O\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions as illustrated in Fig.\u00a03a). The assembly lies parallel to  more than \u22120.18 a.u., Fig.\u00a06b) and (c). The intra\u00admolecular O\u2014H\u22efN contacts reveal similar attractive inter\u00adactions.Among all close contacts present in (I)NCIPLOT results, the strength of inter\u00adaction for each close contact was qu\u00adanti\u00adfied by calculation of the inter\u00adaction energy in Gaussian16 , the combination of \u03c0(C3\u2013C8)\u2013quasi-\u03c0, quasi-\u03c0\u2013quasi-\u03c0, C24\u2014H24A\u22efS2, C14\u2014H14\u22ef \u03c0(C25\u2013C30) and C15\u2014H15\u22ef\u03c0(C25\u2013C30) between S1- and S3-mol\u00adecules exhibits the greatest inter\u00adaction energy among all close contacts with an E of \u221265.73\u2005kJ\u2005mol\u22121, Table\u00a052 synthon, being the second strongest inter\u00adaction with E = \u221259.79\u2005kJ\u2005mol\u22121. The strength of the N1\u2014H1N\u22efS3/N3\u2013H3N\u22efS1 inter\u00adaction is consistent with the energy range of \u221254.06 to \u221257.99\u2005kJ\u2005mol\u22121 displayed by the equivalent contacts in the cinnamaldehyde Schiff base of S-(4-methyl\u00adbenz\u00adyl) di\u00adthio\u00adcarbaza\u00adtes calculated through wB97XD/6-31G C=NN(H)C(=S)SR, five of which have the hydroxyl substituent in the 2-position enabling the formation of an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(imine) hydrogen bond. In the most closely related compounds, i.e. with 2-OH substituents, the R group in the ester substituent is methyl  and 2,4-di\u00adhydroxy\u00adbenzaldehyde  were mixed and heated until the initial volume was reduced by half. The yellow precipitate formed after cooling the mixture to room temperature was collected and washed with cold ethanol. It was recrystallized from ethanol solution and dried over silica gel for three days. Light-yellow prisms were obtained from its 1:1 diethyl ether/chloro\u00adform solution by slow evaporation.Two solutions, \u22121): 3310 , 3094 , 1604 , 1100 , 1024 , 948 . 1H NMR : \u03b4 13.19 , 10.21 , 10.07 , 8.35 , 7.45 , 7.36 , 7.21 , 6.29 , 6.26 , 4.44 . 13C{1H}-NMR : \u03b4 ppm. 194.4 (C=S), 162.1, 159.6 (C\u2014OH), 146.5 (N=C), 129.7\u2013127.8 (Ph & benzene), 38.0 (CH2); GCMS (DI): m/z calculated for C15H14N2O2S2+ [M+]: 318, found 318.Yield: 4.98\u2005g, 62%; m.p. 463\u2013465\u2005K. FT\u2013IR UATR (solid), \u03bb (cmUiso(H) set to 1.2Ueq(C). The O- and N-bound H atoms were located in a difference-Fourier map but, were refined with O\u2014H (0.84\u00b10.01\u2005\u00c5) and N\u2014H (0.88\u00b10.01\u2005\u00c5) distance restraints, and with Uiso(H) set to 1.5Ueq(O) and to 1.2Ueq(N), respectively. The CHCl3 solvent mol\u00adecule is statistically disordered about the mol\u00adecular threefold axis. The C31 atom is common to both conformations and the individual Cl atoms were refined anisotropically. A loose distance restraint for C\u2014Cl was applied, i.e. C\u2014Cl = 1.76\u00b10.02\u2005\u00c5. The maximum and minimum residual electron density peaks of 1.04 and 1.22\u2005e\u2005\u00c5\u22123, respectively, are located 1.03 and 0.90\u2005\u00c5 from the Cl3\u2032 atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989020007070/hb7919sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989020007070/hb7919Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007070/hb7919Isup3.cmlSupporting information file. DOI: 2005815CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cation and anion are linked together by supra\u00admolecular inter\u00adactions [graph-set notation of hydrogen bonding a-axis direction]. Additionally, there is \u03c0\u2013\u03c0 stacking involving the salicylate anion and the piperazinium cation in adjacent asymmetric units as well as a C\u2014H\u22ef\u03c0 inter\u00adaction between a hydrogen atom on the piperazine ring and the phenyl ring within the salicyclate anion. In bis\u00ad[4-(4-nitro\u00adphen\u00adyl)piperazin-1-ium] bis\u00ad(4-fluoro\u00adbenzoate) trihydrate (2C10H14N3O2+\u00b72C7H4FO2\u2212\u00b73H2O), there are two cations, two anions, and three water mol\u00adecules of solvation in the asymmetric unit, all linked by hydrogen bonds [graph-set notation of hydrogen bonding R22(20) between adjacent cations and R33(9) between a cation and its adjacent anion]. In the anion, the 4-nitro\u00adphenyl ring occupies an axial substitution position in the piperazinium ring, which is relatively rare. Within the asymmetric unit, the phenyl groups in the cations show an offset \u03c0\u2013\u03c0 inter\u00adaction. Additionally, there is a C\u2014H\u22ef\u03c0 inter\u00adaction between a hydrogen atom on the phenyl ring within a cation and the phenyl ring within an anion. In 4-(4-nitro\u00adphen\u00adyl)piperazin-1-ium 3,5-di\u00adnitro\u00adbenzoate (C10H14N3O2+\u00b7C7H4N2O6\u2212), there is a strong N\u2014H\u22efO hydrogen bond linking the cation and anion and the 4-nitro\u00adphenyl ring occupies an axial substitution position in the piperazinium ring, as seen in the previous structure. In the crystal, the cation and the anion form a complex three-dimensional hydrogen-bonded array involving R22(8), R44(12) and R44(20) rings propogating in the a-axis direction. The nitro\u00adphenyl group is disordered with occupancies of 0.806\u2005(10) and 0.194\u2005(10).The structures and Hirshfeld surface analysis of three salts of 1-(4-nitro\u00adphenyl)\u00adpiperazine are discussed. In 4-(4-nitro\u00adphen\u00adyl)piperazin-1-ium salicylate (C Additionally, ring B\u2032s piperazine substituent forms a weak C\u2014H\u22efO inter\u00adaction with an oxygen atom in ring C\u2032s terminal nitro group . Ring C\u2032s piperazine substituent forms a similar inter\u00adaction with ring B\u2032s terminal nitro group . In the conformation of rings A\u2013D, the dihedral angles between the 4-nitro\u00adphenyl rings in rings B and C, the 4-nitro\u00adphenyl ring and nitro group in ring B, the 4-nitro\u00adphenyl ring and nitro group in ring C, the piperazine ring and the 4-nitro\u00adphenyl ring in ring B, the piperazine ring and 4-nitro\u00adphenyl ring in ring C, the fluoro\u00adbenzene ring in ring D and the phenyl ring in ring C, and the fluoro\u00adbenzene ring in A and the phenyl ring in C are 11.4\u2005(4), 1.1\u2005(2), 0.2\u2005(2), 141.72\u2005(16), 145.17\u2005(17), 101.47\u2005(17) and 103.32\u2005(17)\u00b0, respectively. The third and fourth angles listed indicate that the 4-nitro\u00adphenyl ring occupies an axial position in both cations, which is relatively rare. In a previous paper containing eleven analogous structures, only one had this substitution pattern , crystallizes in the monoclinic space group C2/c with eight formula units in the unit cell. The structure consists of a 4-nitro\u00adphenyl\u00adpiperazinium cation and a 3,5-di\u00adnitro\u00adbenzoate anion linked by a strong N\u2014H\u22efO hydrogen bond . Additionally, there is a C\u2014H\u22ef\u03c0 inter\u00adaction between a hydrogen atom in the piperazine ring and the phenyl ring within the salicyclate anion  x, y, z).In discussing the supra\u00admolecular features of the three structures, the direct hydrogen bonding involving the linking of the 4-nitro\u00adphenyl\u00adpiperazinium cations and organic acid anions is omitted since it has already been discussed in the previous section. For 2, there are two anions and two cations as well as three water mol\u00adecules of solvation in the asymmetric unit. This leads to a complex three-dimensional array of hydrogen bonding involving both B and C, and R33(9) motifs between rings C and D as well as one water mol\u00adecule, as seen in Fig.\u00a06x, y, \u2212z; see Table\u00a02B forms an offset \u03c0\u2013\u03c0 inter\u00adaction with the phenyl ring in C . Additionally, there is a C\u2013H\u22ef\u03c0 inter\u00adaction between a hydrogen atom on the phenyl ring in C and the phenyl ring in D .For 3, the cation and the anion form a complex three-dimensional array of hydrogen bonding involving a-axis direction between the 4-nitro\u00adphenyl group of one cation with the piperazinium ring of an adjacent cation , two cations and two anions in adjacent asymmetric units , two cations and two anions in adjacent asymmetric units , respectively, as seen in Fig.\u00a09Cg2\u22efCg2i distance, 4.4132\u2005(9)\u2005\u00c5; perpendicular distance: 3.5596\u2005(9)\u2005\u00c5; slippage of 2.609\u2005\u00c5, symmetry code: (i) x, y, 1\u00a0\u2212\u00a0z; Cg2 is the centroid of the C1\u2013C6D ring].For 4.et al., 1997et al., 2014et al., 2019Related structures containing 1-phenyl\u00adpiperazine or the 1-phenyl\u00adpiperazinium cation include racemic perhydro\u00adtri\u00adphenyl\u00adene (PHTP), which has been shown to form a polar inclusion compound with 1-(4-nitro\u00adphen\u00adyl)piperazine (NPP) as a guest mol\u00adecule -4-(4-nitro\u00adphen\u00adyl)piperazine (BIQYIM), 1-(4-bromo\u00adbenzo\u00adyl)-4-(4-nitro\u00adphen\u00adyl)piperazine (BIRHES), 1-(3-bromo\u00adbenzo\u00adyl)-4-(4-nitro\u00adphen\u00adyl)piperazine (BIRHIW) and bis\u00ad[(4-fluoro\u00adphen\u00adyl)methanone] (BIRGOB) have been reported  4-nitro\u00adphenyl\u00adpiperazine  in methanol (10\u2005ml) was mixed with equimolar solutions of the appropriate acids in methanol (10\u2005ml) and ethyl acetate (10\u2005ml) viz., salicylic acid (67\u2005mg) for 1, 4-fluoro\u00adbenzoic acid (68\u2005mg) for 2 and 3,5-di\u00adnitro\u00adbenzoic acid (102\u2005mg) for 3  for a week. For 3, DMF (3\u2005ml) was used for crystallization. The corresponding melting points were 453\u2013458\u2005K (1), 373\u2013378\u2005K (2) and 445\u2013447\u2005K (3).For the synthesis of salts 6.Uiso(H) = 1.2Ueq(C) while the N\u2013H and water O\u2013H hydrogen atoms were refined isotropically. In 3 the nitro\u00adphenyl group is disordered with occupancies of 0.806\u2005(10)/0.194\u2005(10) and constrained to have similar metrical parameters.Crystal data, data collection and structure refinement details for the three structures are summarized in Table\u00a0410.1107/S2056989023002517/vm2276sup1.cifCrystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S2056989023002517/vm22761sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989023002517/vm22762sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989023002517/vm22763sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989023002517/vm22761sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023002517/vm22762sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023002517/vm22763sup7.cmlSupporting information file. DOI: 2248697, 2248696, 2248695CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Blood Cancer Journal (2023) 13:111 10.1038/s41408-023-00883-x, published online 20 July 2023Correction to: N\u2009=\u20093111)\u201d and \u201cNon-ASCT (N\u2009=\u20092437)\u201d were assigned in incorrect lines. Correct Table\u00a0In Table\u00a0ASCT N\u2009=\u2009437\u201d wereThe original article has been corrected."}
{"text": "In the published article, there was an error in the name and abbreviation of the measure \u201cmean corpuscular hemoglobin concentration\u201d abbreviated to \u201cMCHC\u201d. It should be \u201cmean corpuscular hemoglobin\u201d and abbreviated to \u201cMCH\u201d. Throughout the text of the article, \u201cmean corpuscular hemoglobin concentration\u201d has been corrected to \u201cmean corpuscular hemoglobin\u201d and the abbreviation \u201cMCHC\u201d has been corrected to \u201cMCH\u201d.In the published article, there was an error in the header, title and legend for The corrected In the published article, there was an error in the legend for In the published article, there was an error. A correction has been made to the section Results, subsection \u201cAnalysis of anemia prevalence and hematological phenotype indexes in pregnant women with various thalassemia genotypes\u201d, paragraph 1. This sentence previously stated:SEA, \u2013\u03b13.7/\u2013\u03b13.7, \u2013\u03b13.7/\u2013\u03b14.2, and \u2013\u03b14.2/\u2013\u03b14.2 ranged from 35.96 to 37.82% (P < 0.05).\u201d\u201cThe anemia rates of \u03b1\u03b1/\u2013The corrected sentence appears below:SEA, \u2013\u03b13.7/\u2013\u03b13.7, \u2013\u03b13.7/\u2013\u03b14.2, and \u2013\u03b14.2/\u2013\u03b14.2 ranged from 35.96 to 37.82% (P > 0.05).\u201d\u201cThe anemia rates of \u03b1\u03b1/\u2013A correction has been made to the section Discussion, subsection \u201cAnalysis of anemia prevalence and hematological phenotype indexes of pregnant women with various thalassemia genotypes\u201d, paragraph 1. This sentence previously stated:SEA, \u2013\u03b13.7/\u2013\u03b13.7, \u2013\u03b14.2/\u2013\u03b14.2, and \u2013\u03b13.7/\u2013\u03b14.2 ranged from 35.96 to 37.82% (P < 0.05), and no significant differences were observed in Hb levels among those genotypes.\u201d\u201cThe anemia rate among carriers of \u03b1\u03b1/\u2013The corrected sentence appears below:SEA, \u2013\u03b13.7/\u2013\u03b13.7, \u2013\u03b14.2/\u2013\u03b14.2, and \u2013\u03b13.7/\u2013\u03b14.2 ranged from 35.96 to 37.82% (P > 0.05), and no significant differences were observed in Hb levels among those genotypes.\u201d\u201cThe anemia rate among carriers of \u03b1\u03b1/\u2013A correction has been made to the section Discussion, subsection \u201cPrevalence of iron deficiency in anemic pregnant women with various genotypes of thalassemia\u201d, paragraph 1. This sentence previously stated:\u201cAlthough there is no large sample, multicenter randomized controlled study that has yet confirmed the need for routine iron supplementation in PW with thalassemia minor genotypes, we suggest that the iron load of APW with \u03b2- thalassemia minor genotypes should be monitored dynamically during iron supplementation\u201dThe corrected sentence appears below:\u201cAlthough there is no large sample, multicenter randomized controlled study that has yet confirmed the need for routine iron supplementation in PW with thalassemia minor genotypes, we suggest that the ferritin levels of APW with \u03b2- thalassemia minor genotypes should be monitored dynamically during iron supplementation\u201dThe authors apologize for these errors and state that this does not change the scientific conclusions of the article in any way. The original article has been updated."}
{"text": "Wu et al. show that the mitotic kinesin CENP-E promotes full expansion of the outer layer of the kinetochore known as the fibrous corona. This new function of CENP-E is independent of its motor activity. The findings expand the roles of CENP-E in spindle assembly and chromosome congression in mitosis. Correct chromosome segregation during cell division depends on proper connections between spindle microtubules and kinetochores. During prometaphase, kinetochores are temporarily covered with a dense protein meshwork known as the fibrous corona. Formed by oligomerization of ROD/ZW10/ZWILCH-SPINDLY (RZZ-S) complexes, the fibrous corona promotes spindle assembly, chromosome orientation, and spindle checkpoint signaling. The molecular requirements for formation of the fibrous corona are not fully understood. Here, we show that the fibrous corona depends on the mitotic kinesin CENP-E and that poorly expanded fibrous coronas after CENP-E depletion are functionally compromised. This previously unrecognized role for CENP-E does not require its motor activity but instead is driven by farnesyl modification of its C-terminal kinetochore- and microtubule-binding domain. We show that in cells, CENP-E binds Spindly and recruits RZZ-S complexes to ectopic locations in a farnesyl-dependent manner. CENP-E is recruited to kinetochores following RZZ-S, and\u2014while not required for RZZ-S oligomerization per se\u2014promotes subsequent fibrous corona expansion. Our comparative genomics analyses suggest that the farnesylation motif in CENP-E orthologs emerged alongside the full RZZ-S module in an ancestral lineage close to the fungi\u2013animal split (Obazoa), revealing potential conservation of the mechanisms for fibrous corona formation. Our results show that proper spindle assembly has a potentially conserved non-motor contribution from the kinesin CENP-E through stabilization of the fibrous corona meshwork during its formation. The cell division cycle culminates in the segregation of duplicated sister chromatids to nascent daughter cells. Segregation is driven by the microtubule-based spindle apparatus . MicrotuThe fibrous corona houses over two dozen proteins to perform its various roles in spindle assembly and chromosome segregation . It is fcomet, the Cyclin B1\u2013CDK1 kinase complex, the CLASP1/2 microtubule dynamics regulators, and the microtubule-binding protein centromere protein F  was fully sufficient to restore fibrous corona formation after CENP-E loss, we next attempted to further narrow down the essential region. Expression in HeLa cells of a series of MT-binding domain mutants of CENP-E 2111-C  revealedC2698A delayed chromosome congression  have sm ZWINT-1 . The kin ZWINT-1 . In cont ZWINT-1 . Further ZWINT-1 , showing ZWINT-1  or expre ZWINT-1  abolisheOur data thus far showed that farnesylated CENP-E is important for fibrous corona formation and that CENP-E can quite robustly recruit RZZ-S to ectopic locations in a manner dependent on its farnesylation. To understand more about how CENP-E promotes fibrous corona formation, we asked when and how CENP-E localizes to kinetochores, relative to RZZ-S. Again we made use of the monopolar spindle assay, in which fibrous corona proteins are depleted from kinetochores and accumulate at the spindle pole upon chemical inhibition of CENP-E. Subsequent addition of nocodazole to these cells to deplete microtubules caused detectable relocalization of ZW10 back to the kinetochores within \u223c1 min, followed by CENP-E after \u223c8 min . Importa\u0394N) bypasses the need for regulatory mechanisms of fibrous corona formation and does not bind dynein/dynactin, resulting in persistent fibrous coronas  should be able to bypass this step in the absence of CENP-E. This is not so, showing CENP-E contributes to a parallel or downstream event. An alternative hypothesis is that CENP-E is an integral component of the RZZ-S meshwork. However, RZZ-S can oligomerize in vitro without CENP-E . Our current analysis pinpoints emergence of SPINDLY one branch earlier than the cysteine in CENP-E, but we note that the CENP-E ortholog sequences in Breviata are incomplete. Better sampling of genomes from Breviata species might therefore reveal FL CENP-E ORF sequences with a cysteine at \u22124 from the carboxy terminus, which would indicate near-simultaneous emergence of SPINDLY and the potential for CENP-E farnesylation. Beyond SPINDLY, the RZZ-S complex and the potential for CENP-E farnesylation show strongly cohesive presence/absence in Obazoa, with notable coherent losses close in the species tree. Interestingly, kinetochores in colchicine-treated Drosophila S2 cells do not appear to form clear fibrous coronas  supplemented with 9% tetracycline-free fetal bovine serum and 100 \u03bcg/ml penicillin-streptomycin .\u0394N, and LAP-SPINDLY\u0394N/C602A in pCDNA5 vector were previously cloned by PCR-based strategy; SPINDLY\u0394N: SPINDLY 65-605; SPINDLY\u0394N/C602A: SPINDLY 65-605 with C602A  to the C-terminal CENP-E 2111-C (comprising KT-binding domain and MT-binding domain). LAP-tagged CENP-E 2,111\u20132,697^CAAXLAP-ROD in pCDNA5 vector was cloned based on the ROD cDNA, which was a kind gift from Reto Gassmann , TagRFP-CENP-E 2111-C and H2B-mScarlet were cloned into the pLVX-IRES-Puro vector (Clontech) by PCR-based Gibson assembly method.CENP-E-1aa-XhoI-GA-F: 5\u2032-CGG\u200bAGG\u200bTGG\u200bATC\u200bCAC\u200bTAG\u200bTCT\u200bCGA\u200bGAT\u200bGGC\u200bGGA\u200bGGA\u200bAGG\u200bAGC\u200bCGT-3\u2032CENP-E-2,701aa-NotI-GA-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTC-3\u2032CENP-E-1,301-BamHI-F: 5\u2032-GCA\u200bCAT\u200bGGA\u200bCAG\u200bCGG\u200bAGG\u200bTGG\u200bATC\u200bCAC\u200bTCA\u200bGGA\u200bAAC\u200bAAT\u200bGAA\u200bTGA\u200bACT\u200bGGA\u200bGT-3\u2032CENP-E-2,111-BamHI-F: 5\u2032-GCA\u200bCAT\u200bGGA\u200bCAG\u200bCGG\u200bAGG\u200bTGG\u200bATC\u200bCGA\u200bTGA\u200bTCA\u200bTTA\u200bTGA\u200bGTG\u200bCTT\u200bGAA\u200bTAG\u200bATT\u200bGTC\u200bTCT-3\u2032CENP-E 2,599-NotI-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAT\u200bTGT\u200bTTG\u200bTGA\u200bGCC\u200bTCT\u200bCTT\u200bTTA\u200bAGG\u200bGTT-3\u2032CENP-E 2,643-NotI-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAA\u200bCAA\u200bGAT\u200bTTT\u200bGGT\u200bGAT\u200bTCC\u200bTTT\u200bGGC\u200bACA-3\u2032CENP-E-2,600-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bTTG\u200bTTT\u200bGTG\u200bAGC\u200bCTC\u200bTCT\u200bTTT\u200bAAG\u200bGGT\u200bT-3\u2032CENP-E-2,609-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bAAA\u200bGTG\u200bACT\u200bGGA\u200bACA\u200bGCT\u200bTCT\u200bAAA\u200bAAG\u200bAAA\u200bC-3\u2032CENP-E-2,610-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bAGG\u200bAGA\u200bCTT\u200bTGG\u200bAGA\u200bATT\u200bCTC\u200bACA\u200bAG-3\u2032CENP-E-2,619-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bCAA\u200bATT\u200bACA\u200bCCC\u200bTCT\u200bCAA\u200bTGC\u200bAAG\u200bGAA\u200bC-3\u2032CENP-E-2,620-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bTTT\u200bCTT\u200bTTT\u200bAGA\u200bAGC\u200bTGT\u200bTCC\u200bAGT\u200bCAC-3\u2032CENP-E-2,629-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bAAT\u200bTTA\u200bCAA\u200bGAT\u200bCCT\u200bGTG\u200bCCA\u200bAAG\u200bGAA\u200bTC-3\u2032CENP-E-2,630-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bCCG\u200bTTC\u200bCTT\u200bGCA\u200bTTG\u200bAGA\u200bGGG\u200bTG-3\u2032CENP-E-2,639-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bCCA\u200bAAA\u200bTCT\u200bTGT\u200bTTT\u200bTTT\u200bGAT\u200bAGC\u200bCGA\u200bTC-3\u2032CENP-E-2,640-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bTGA\u200bTTC\u200bCTT\u200bTGG\u200bCAC\u200bAGG\u200bATC\u200bTTG-3\u2032CENP-E-2,649-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bAAG\u200bTCT\u200bTTA\u200bCCA\u200bTCA\u200bCCT\u200bCAT\u200bCCA\u200bG-3\u2032CENP-E-2,650-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bTGA\u200bTCG\u200bGCT\u200bATC\u200bAAA\u200bAAA\u200bACA\u200bAGA\u200bTTT\u200bTG-3\u2032CENP-E-2,659-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bTAT\u200bTTT\u200bGAT\u200bAAC\u200bTCA\u200bAGT\u200bTTA\u200bGGC\u200bCTT\u200bTGT\u200bC-3\u2032CENP-E-2,660-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bGCG\u200bAAC\u200bTGG\u200bATG\u200bAGG\u200bTGA\u200bTGG\u200bTAA-3\u2032CENP-E-2,669-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bCCA\u200bGAG\u200bGTG\u200bCAA\u200bAAT\u200bGCA\u200bGGA\u200bG-3\u2032CENP-E-2,670-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bACA\u200bAAG\u200bGCC\u200bTAA\u200bACT\u200bTGA\u200bGTT\u200bATC\u200bAAA\u200bAT-3\u2032CENP-E-2,679-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bGTG\u200bGAT\u200bTCT\u200bCAG\u200bCCA\u200bGGT\u200bCCT\u200bTG-3\u2032CENP-E-2,680-mutation10AA-GA-R: 5\u2032-TGC\u200bAGC\u200bCGC\u200bTGC\u200bAGC\u200bTGC\u200bCGC\u200bTGC\u200bGGC\u200bAGC\u200bACT\u200bCTC\u200bTGC\u200bTCC\u200bTGC\u200bATT\u200bTTG\u200bC-3\u2032CENP-E-2,689-mutation10AA-GA-F: 5\u2032-GCG\u200bGCA\u200bGCT\u200bGCA\u200bGCG\u200bGCT\u200bGCA\u200bTCC\u200bTCA\u200bGGC\u200bAAG\u200bGAT\u200bGTG\u200bCCT\u200bG-3\u2032CENP-E-2,689-NotI-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAG\u200bGCG\u200bTGC\u200bCAA\u200bGGA\u200bCCT\u200bGGC\u200bTGA\u200bG-3\u2032CENP-E-2,701-NotI-S2690A-R2: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAA\u200bGCG\u200bGCG\u200bTGC\u200bCAA\u200bGGA\u200bCCT\u200bG-3\u2032CENP-E-2,701-NotI-S2691A-R2: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCA\u200bGCG\u200bGAG\u200bGCG\u200bTGC\u200bCAA\u200bGGA\u200bC-3\u2032CENP-E-2,701-NotI-K2693A-R2: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCA\u200bGCG\u200bCCT\u200bGAG\u200bGAG\u200bGCG\u200bTGC\u200bCAA\u200bGGA\u200bC-3\u2032CENP-E-2,701-NotI-D2694A-R2: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bGCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGCG\u200bTGC\u200bCAA\u200bGGA\u200bC-3\u2032CENP-E-2,701-NotI-V2695A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGA\u200bGCA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGCG\u200bTG-3\u2032CENP-E-2,701-NotI-P2696A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGCC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGC-3\u2032CENP-E-2,701-NotI-E2697A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTG\u200bCAA\u200bGCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG-3\u2032CENP-E-C-C2698A-R2: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTA\u200bGCC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGC-3\u2032CENP-E-2,701-NotI-K2699A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTA\u200bGCG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCC-3\u2032CENP-E-2,701-NotI-T2700A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGCT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bC-3\u2032CENP-E-2,701-NotI-Q2701A-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAA\u200bGCA\u200bGTT\u200bTTG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bT-3\u2032CENP-E-2,701-NotI-C2698S-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bTGA\u200bGTT\u200bTTT\u200bGAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGCG\u200bTG-3\u2032CENP-E^KRAS_caax_R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCC\u200bTAC\u200bATT\u200bATA\u200bATG\u200bCAC\u200bTCA\u200bGGC\u200bACA\u200bTCC\u200bTTG\u200bCCT\u200bGAG\u200bGAG\u200bGCG\u200bTG-3\u2032TagRFP-kozak-EcoR1-F: 5\u2032-CTA\u200bCTA\u200bGAG\u200bGAT\u200bCTA\u200bTTT\u200bCCG\u200bGTG\u200bAAT\u200bTCG\u200bCCA\u200bCCA\u200bTGG\u200bTGT\u200bCTA\u200bAGG\u200bGCG\u200bAAG\u200bAGC\u200bTGA\u200bTTA\u200bAG-3\u2032TagRFP-C-toCENP-E2111-R: 5\u2032-TCT\u200bATT\u200bCAA\u200bGCA\u200bCTC\u200bATA\u200bATG\u200bATC\u200bATC\u200bGGA\u200bTCC\u200bACC\u200bTCC\u200bGCT\u200bATT\u200bAAG\u200bTTT\u200bGTG\u200bCCC\u200bCAG\u200bTTT\u200bGCT-3\u2032ROD-1aa-XhoI-GA-F: 5\u2032-CGG\u200bAGG\u200bTGG\u200bATC\u200bCAC\u200bTAG\u200bTCT\u200bCGA\u200bGAT\u200bGTG\u200bGAA\u200bTGA\u200bTAT\u200bTGA\u200bGCT\u200bGCT\u200bAAC\u200bAAA\u200bTG-3\u2032ROD-1,100aa-overlap-GA-R: 5\u2032-AAT\u200bAGC\u200bAAT\u200bTTC\u200bCCA\u200bGTG\u200bTCA\u200bGCA\u200bTT-3\u2032ROD-1,100aa-overlap-GA-F: 5\u2032-AAT\u200bGCT\u200bGAC\u200bACT\u200bGGG\u200bAAA\u200bTTG\u200bCTA\u200bTT-3\u2032ROD-2,209aa-NotI-GA-R: 5\u2032-GCG\u200bGGT\u200bTTA\u200bAAC\u200bGGG\u200bCCC\u200bGCG\u200bGCC\u200bGCT\u200bTAC\u200bGAT\u200bAAT\u200bCCA\u200bCTA\u200bAGA\u200bAAC\u200bATC\u200bTTC\u200bAGA\u200bAT-3\u2032TurboID-N-BamHI-F: 5\u2032-GCA\u200bCAT\u200bGGA\u200bCAG\u200bCGG\u200bAGG\u200bTGG\u200bATC\u200bCAA\u200bAGA\u200bCAA\u200bTAC\u200bTGT\u200bGCC\u200bTCT\u200bGAA\u200bGCT-3\u2032TurboID-C-BamHI-R: 5\u2032-TCA\u200bAGC\u200bACT\u200bCAT\u200bAAT\u200bGAT\u200bCAT\u200bCGG\u200bATC\u200bCGC\u200bTGA\u200bATT\u200bCCT\u200bTTT\u200bCGG\u200bCAG\u200bACC\u200bGCA\u200bGAC\u200bT-3\u2032CENP-E-1aa-BamHI-cut-GA-F: 5\u2032-GCA\u200bCAT\u200bGGA\u200bCAG\u200bCGG\u200bAGG\u200bTGG\u200bATC\u200bCAT\u200bGGC\u200bGGA\u200bGGA\u200bAGG\u200bAGC\u200bCGT\u200bG-3\u2032CENP-E-426aa-BamHI-cut-GA-R: 5\u2032-ATT\u200bCAA\u200bGCA\u200bCTC\u200bATA\u200bATG\u200bATC\u200bATC\u200bGGA\u200bTCC\u200bGCC\u200bAAG\u200bGCA\u200bCCA\u200bAGT\u200bAAC\u200bTCT\u200bTC-3\u2032Lentiviruses were produced by cotransfection of HEK 293T cells with the lentiviral vector containing TagRFP-CENP-E 2111-C or H2B-mScarlet and separate plasmids that express Tat, vesicular stomatitis virus G glycoprotein, Rev, and Gag-Pol, with the transfection reagent of Fugene HD . 72 h after transfection, cell culture supernatant was harvested and filtered.RPE1 FlpIn cell line stably expressing EB3-TagRFPT-ires-GFP-ZWILCH was made previously by transduction of viruses that were produced by cotransfection of HEK 293T cells with the lentiviral vector containing gene of EB3-TagRFPT-ires-GFP-Zwilch, which was cloned into the pLVX-IRES-Puro vector .\u0394N were made previously by cotransfection of pCDNA5-constructs with gene of interest and construct of pOG44 recombinase in a 1:2 ratio with electroporation machine (Amaxa Nucleofector II) using protocol U-017. 3 d after transfection, RPE1 cells were selected with 100 \u03bcM hygromycin  for about 3 wk (RPE1 FlpIn cell line inducible expressing LAP-SPINDLY FL and LAP- SPINDLYout 3 wk .RPE1 FlpIn cell lines were cotransfected with pCDNA5-constructs with gene of interest and construct of pOG44 recombinase in a 1:2 ratio with an electroporation machine (Amaxa Nucleofector II) using protocol U-017. 3 d after transfection, RPE1 cells were selected with 100 \u03bcM hygromycin  for about 3 wk.HeLa FlpIn were cotransfected with pCDNA5 constructs with the gene of interest and construct of pOG44 recombinase in a 1:9 ratio with Fugene HD  under the manufacturer\u2019s instructions. 1 d after transfection, HeLa cells were selected with 200 \u03bcM hygromycin  for about 3 wk.To generate HeLa FlpIn cells stably expressing TagRFP-CENP-E 2111-C and inducible expressing LAP-ROD, HeLa FlpIn cells inducible expressing LAP-ROD were infected with lentiviruses and selected with 1 \u03bcg/ml puromycin for 1 wk.To generate HeLa FlpIn cell stably expressing H2B-mScarlet, HeLa FlpIn were infected with lentiviruses and selected with 1 \u03bcg/ml puromycin for 1 wk.To generate HeLa FlpIn cells inducible expressing CENP-E FL WT or CENP-E FL C2698A and stably expressing H2B-mScarlet, HeLa FlpIn cells inducible expressing CENP-E FL WT or CENP-E FL C2698A were infected with lentiviruses and selected with 1 \u03bcg/ml puromycin for 1 wk.The siRNAs targeting GAPDH , CENP-E  for 15 h (overnight) for fibrous corona formation before the fixation. HeLa FlpIn cells were treated with 6.6 \u03bcM nocodazole for 6\u223c8 h before the fixation. For cells transfected with siRNA, nocodazole was added 48 h after siRNA transfection. For the rescue experiments, 1 \u03bcg/ml doxycycline  was added to cells 40 h after siRNA transfection to induce the expression of protein mutants. For nocodazole washout assay, 6.6 \u03bcM nocodazole was added to the culture medium for 15 h before washout. For CENP-E inhibition, cells were treated with 250 nM GSK923295  for 15 h (overnight). For farnesyl transferase inhibition, cells were treated with 5 \u00b5m lonafarnib  for 15 h (overnight). For the fast disassembly of microtubules, cells were treated with 13.2 \u03bcM nocodazole for 4 h. Cells were treated with 10 mM STLC  for 15 h (overnight). For the experiments in which translocated fibrous corona proteins were released from spindle poles, cells were cotreated with STLC and GSK923295 for 15 h (overnight) and were further treated with 13.2 \u03bcM nocodazole for indicated time before fixation. In the TurboID pulldown experiment, HeLa cells were treated with 1 \u03bcg/ml doxycycline for 24 and 1 h of 250 \u03bcM biotin  before harvest. For spindle end-on attachment experiments, HeLa cells were cotreated with STLC and ZM447439  for 6 h before fixation.Glued . We used the following secondary antibodies: Goat anti-guinea pig Alexa Fluor 647 , Goat anti-rabbit Alexa Fluor 488 , Goat anti-rabbit Alexa Fluor 568 , Goat anti-rabbit Alexa Fluor 405 , Goat anti-mouse Alexa Fluor 568 , Goat anti-mouse Alexa Fluor 647 , and GFP-Booster Atto 488 .We used guinea pig polyclonal antibody against CENPC , and rabbit polyclonal antibodies against CENP-E , ZW10 , and were blocked with 2% BSA diluted in PBST for 30 min. After blocking, cells were incubated with primary antibodies diluted in PBST containing 2% BSA for 1 h at room temperature in humid conditions. Subsequently, cells were washed three times with PBST and incubated with secondary antibodies diluted in PBST together with or without DAPI for 1 h at room temperature. Then, cells were washed three times with PBST. In the end, coverslips were sequentially rinsed in 70% and 100% ethanol, air-dried, and mounted on glass slides with Prolong Gold antifade.n = 1.5160  using SoftWorx 6.0 software . Images were acquired as z-stacks at 0.2-\u03bcm intervals for 32 stacks using Photometrics Coolsnap HQ2 cameral (Roper Scientific) and deconvolved using SoftWoRx. The images are maximum-intensity projections of deconvoluted stacks.All images were acquired on a deconvolution system  with a 100\u00d7/1.40 NA UPlanSApo objective (Olympus) and imaging medium with https://fiji.sc). For quantification of protein levels, all images of immunostaining experiments were acquired with identical illumination settings. Protein levels near the kinetochores were determined on maximum projections of z-stacks images using an ImageJ macro . 488 and 561 nm lasers were used for sample excitation and images were acquired using an Andor iXon-888 EMCCD camera. Nocodazole washout was done during the imaging with a warm culture medium. Before and after nocodazole washout, cells were kept at 37\u00b0C and 5% CO2 using a cage incubator and Boldline temperature/CO2 controller (OKO-Lab).For imaging of RPE1 cells coexpressing EB3-TagRFPT and GFP-Zwilch in nocodazole washout assay, RPE1 cells were cultured in a 24-well glass bottom plate . Live-cell imaging was performed on a Nikon TiE microscope, controlled by NIS Elements software , by acquiring images every 20 or 30 s with z-stacks at 1-\u03bcm intervals for 15 stacks at 1 \u2009\u00d7 \u20091 binning on an Andor CSU-W1 spinning disk (50 \u03bcm disk) with Nikon 100\u00d7 1.45 NA oil objective and immersion oil with n = 1.406 . 488 and 561 nm lasers were used for sample excitation and images were acquired using an Andor iXon-888 EMCCD camera. Cells were kept at 37\u00b0C and 5% CO2 using a cage incubator and Boldline temperature/CO2 controller (OKO-Lab).Imaging of HeLa FlpIn cells expressing H2B-mScarlet and HeLa FlpIn cells coexpressing LAP-CENP-E FL WT or LAP-CENP-E FL C2698A with H2B-mScarlet that were cultured in 8-well plates  was performed on a Nikon TiE microscope, controlled by NIS Elements software , by acquiring images every 3 min with z-stacks at 2-\u03bcm intervals for eight stacks at 1\u2009 \u00d7 \u20091 binning on an Andor CSU-W1 spinning disk (50-\u03bcm disk) with Nikon 30\u00d7 silicon objective and silicon immersion oil with In the TurboID-based proteins pulldown experiments, HeLa cells inducible expressing LAP-TurboID-CENP-E 2111-C mutants were treated with 1 \u03bcg/ml doxycycline for 24 h to induce the expression of LAP-TurboID-CENP-E 2111-C mutants and 1 h of 250 \u03bcM biotin before harvest. The cells were harvested by trypsinization and centrifuge. The cells were washed once with ice-cold PBS and lysated with lysis buffer  on ice for 10 min. After lysis, the samples were centrifuged at 14,000 rpm for 20 min at 4\u00b0C. The supernatants of the centrifuged samples were incubated with the streptavidin magnetic beads  for 1 h in a 4\u00b0C cold room. The beads were washed with wash buffer  three times. The wash buffer was removed after the final wash and the beads were stored in a \u221280\u00b0C freezer.2 Fold Change and \u2212log10 P value higher than 2. The program used for the analyses was R (version 4.0.4) through RStudio (version 1.5.64).Precipitated proteins were denatured and alkylated in 50 \u00b5l 8 M urea, 1 M ammonium bicarbonate (ABC) containing 10 mM tris (2-carboxyethyl) phosphine hydrochloride and 40 mM 2-chloro-acetamide for 30 min. After fourfold dilution with 1 M ABC and digestion with trypsin (20 \u00b5g/200 \u00b5l), peptides were separated from the beads and desalted with homemade C-18 stage tips (3 M), eluted with 80% acetonitrile (ACN) and, after evaporation of the solvent in the speedvac, redissolved in buffer A (0.1% formic acid [FA]). After separation on a 30-cm pico-tip column  in-house packed with C-18 material  using a 140 min gradient , delivered by an easy-nLC 1,000 (Thermo Fisher Scientific), peptides were electrosprayed directly into a Orbitrap Fusion Tribrid Mass Spectrometer (Thermo Fisher Scientific). The latter was set in data-dependent top speed mode with a cycle time of 1 s, in which the full scan over the 400\u20131,500 mass range was performed at a resolution of 240,000. Most intense ions  were isolated by the quadrupole, where after they were fragmented with a higher-energy collisional dissociation collision energy of 30%. The maximum injection time of the ion trap was set to 50 ms with injection of ions for all available parallelizable time. Raw data were analyzed with MaxQuant (version 1.6.3.4) using the Homo Sapiens (taxonomy ID: 9606) fasta file, extracted from UniprotKB. To determine proteins of interest, the protein group output file was used to perform a differential enrichment analysis. Proteins with less than one unique peptide and proteins that have not been identified in at least two out of three of the replicates of one condition were filtered out. Then, a background correction and normalization of the data were performed by variance stabilizing transformation, shifting and scaling the protein intensities by sample group. A left-shifted Gaussian distribution randomization was used to impute since the data presented a pattern of missingness not at random. Finally, a differential enrichment analysis was performed to identify those proteins that were differentially enriched and selected those falling inside the threshold for logThe mass spectrometry proteomics data have been deposited to the ProteomeXchange Consortium via the PRIDE  partner Preprint), with some minor adjustments detailed in The eukaryotic sequence database used for the evolutionary analysis consisted of 177 predicted proteomes derived from genomes or transcriptomes and spans a representative set of species across the eukaryotic tree of life. This dataset is derived from earlier work  and Prism 9 . Data distribution was assumed to be normal but this was not formally tested. The results of The data generated are available in the published article and its online supplemental material. The mass spectrometry proteomics data have been deposited to the ProteomeXchange Consortium via the PRIDE partner repository with the dataset identifier PXD040338."}
{"text": "In the title compound, which is related to the herbicide flufenacet, the amide group and fluoro\u00adbenzene ring are almost perpendicular. A short O\u22ef\u03c0 contact is observed in the crystal. 12H16FNO3S, which is related to the herbicide flufenacet, are presented. The dihedral angle between the amide group and the fluorinated benzene ring is 87.30\u2005(5)\u00b0 and the N\u2014C\u2014C\u2014S torsion angle defining the orientation of the methyl\u00adsulfonyl substituent relative to the amide group is 106.91\u2005(11)\u00b0. In the crystal, inversion-related mol\u00adecules form dimers as a result of pairwise C\u2014H\u22efO hydrogen bonds, which appear to be reinforced by short O\u22ef\u03c0 contacts [O\u22efCg = 3.0643\u2005(11)\u2005\u00c5]. A Hirshfeld surface analysis was used to qu\u00adantify the various types of inter\u00admolecular contacts, which are dominated by H atoms.The synthesis and crystal structure of the title compound, C For example, substituted phenyl\u00adacetamides and their use as protease inhibitors was reported by Kreutter et al. -yl]acetamides was given by Ahmad et al. (2013N4-substituted sulfonamide\u2013acetamide derivatives as di\u00adhydro\u00adfolate reductase (DHFR) inhibitors was reported by Hussein et al. (2019N-(substituted phen\u00adyl)-N-(substituted)acetamide derivatives as potent analgesic agents was described by Verma et al. -2-phenyl\u00adacetamide derivatives as potential anti\u00admycobacterial agents was reported by G\u00fczel-Akdemir et al. , systematic name N-(4-fluoro\u00adphen\u00adyl)-N-propan-2-yl-2-{\u00adoxy}acetamide, is an herbi\u00adcide, xenobiotic and environmental contaminant   Fig.\u00a01.2.I, the nitro\u00adgen atom of the amide group is close to planar, the sum of bond angles about N1 being 358.92\u2005(19)\u00b0, which places N1 0.0862\u2005(14)\u2005\u00c5 from the plane passing through C1, C4, and C7. The amide group is also almost planar, having an r.m.s. deviation from the mean plane of N1, C1, O1, C2 of 0.0095\u2005\u00c5 [maximum = 0.0165\u2005(11)\u2005\u00c5 for C1], and is almost perpendicular to the fluoro\u00adbenzene ring (C7\u2013C12), subtending a dihedral angle of 87.30\u2005(5)\u00b0. The overall conformation of the mol\u00adecule is defined by the torsion angles C7\u2014N1\u2014C1\u2014C2 [14.68\u2005(17)\u00b0], N1\u2014C1\u2014C2\u2014S1 [106.91\u2005(11)\u00b0], C1\u2014C2\u2014S1\u2014C3 [74.53\u2005(10)\u00b0] and by the orientation of the ipropyl group, e.g., C1\u2014N1\u2014C4\u2014C6 [139.85\u2005(13)\u00b0]. Otherwise, all bond lengths and angles lie within the expected ranges.In the crystal structure of 3.I  1 \u2013 x, 1 \u2013 y, 1 \u2013 z]. These dimers also feature close contacts between the sulfone O3 atom and the inversion-related benzene ring to give an O3\u22efCg(C7\u2013C12)i distance of 3.0643\u2005(11)\u2005\u00c5 . The other weak C\u2014H\u22efO inter\u00adactions involve inversion, translation, and c-glide related mol\u00adecules (Table\u00a01a). A Hirshfeld surface analysis using CrystalExplorer .There are no strong hydrogen bonds in the crystal structure of I Fig.\u00a02, but thes Table\u00a01a. A Hir4.et al., 2016N-phenyl\u00adacetamide with \u2018any non-H group\u2019 attached at the nitro\u00adgen atom, the 4-position of the benzene ring, and replacing one hydrogen of the methyl group, yielded 259 hits. A similar fragment, but with \u2018any halogen\u2019 at the 4-position on the ring, gave 92 hits. With the halogen restricted to fluorine, twelve hits were returned, and with an isopropyl group attached to the nitro\u00adgen atom, only one match was found: CSD refcode QEMHOG  was presented by Gung et al. (2008A search of the CSD for non-bonded close contacts (up to 3.1\u00c5) between S=O oxygen atoms and a benzene-ring centroid (with \u2018any substituent\u2019) returned 154 hits, none of which have much else in common with  al. 2008.d-threo-2,2-di\u00adchloro-N-{2-hy\u00addroxy-1-(hy\u00addroxy\u00admeth\u00adyl)-2-[4-(methyl\u00adsulfon\u00adyl)phen\u00adyl]eth\u00adyl}acet\u00ada\u00ad\u00admide -2-hy\u00addroxy-2-[4- (methyl\u00adsulfon\u00adyl)phen\u00adyl]eth\u00adyl}acetamide -2-(2-{3-[4-(methyl\u00adsulfon\u00adyl)phen\u00adyl]-1,2,4-oxa\u00addiazol-5-yl}phen\u00adoxy)acetamide -N-(methyl\u00adsulfon\u00adyl)acetamide -N-(methyl\u00adsulfon\u00adyl)acetamide phen\u00adyl)acetamide -4-nitro\u00adphen\u00adyl]-N-methyl\u00adacetamide acetamide \u00adacetyl chloride were added. The mixture was stirred at room temperature for 5\u2005h. After this, 100\u2005ml of water were added and the mixture was extracted three times, each with 100\u2005ml of methyl tert-butyl ether (MTBE). The combined organic phases were dried over MgSO4 and the solvent was evaporated under reduced pressure. The crude product, N-(4-fluoro\u00adphen\u00adyl)-N-isopropyl-2-(methyl\u00adthio)\u00adacetamide, was used for the next stage with purification (7.5\u2005g).In a 250\u2005ml flask (with a nitro\u00adgen inlet and a septum) was placed 5\u2005g of 4-fluoro-N-(4-fluoro\u00adphen\u00adyl)-N-isopropyl-2-(methyl\u00adthio)\u00adacetamide dissolved in 150\u2005ml of di\u00adchloro\u00admethane. After cooling to 263\u2013273\u2005K, 13.37\u2005g of meta-chloro\u00adperbenzoic acid in 100\u2005ml di\u00adchloro\u00admethane was added slowly at the same temperature. The mixture was stirred at room temperature for 5\u2005h. After this, 200\u2005ml of water were added and the organic layer was separated, and washed with 100\u2005ml of 10% sodium bicarbonate twice. The organic phases were dried over MgSO4 and the solvent was evaporated under reduced pressure. The crude product was purified by chromatography over SiO2 (hexa\u00adne:ethyl acetate 9:1 v/v). The title compound was recrystallized from diethyl ether solution in the form of colorless plates. The overall reaction scheme is shown in Fig.\u00a04To a 250\u2005ml round-bottomed flask (with a nitro\u00adgen inlet and a septum) was added 7.5\u2005g of 1H NMR: CDCl3 : 1.097\u20131.08 ; 3.198 ; 3.664 ; 5.006\u20134.938 ; 7.273\u20137.132 . MS m/z: 273.45 (M)+.6.sp2H), 0.98\u2005\u00c5 (RCH3), 0.99\u2005\u00c5 (R2CH2) and 1.00\u2005\u00c5 (R3CH). Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq (RCH3 only) of the attached atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023003675/hb8062sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023003675/hb8062Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023003675/hb8062Isup3.cmlSupporting information file. DOI: 2258160CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The capsid p24 (CA-p24) antigen is a component of the viral capsid of human immunodeficiency virus (HIV) that has been commonly used for clinical diagnosis and monitoring of HIV infections in Enzyme-linked Immunosorbent Assays (ELISAs). Commercial CA-p24 ELISAs are widely used in research settings, but these kits are costly and have limited breadth for detecting diverse HIV isolates.Commercial CA-p24 antibodies were used as capture and detection antibodies. Specific CA-p24 ELISAs were established with these antibodies and tested for the detection of HIV-1 isolates with the aim of developing in-house protocols to recognize HIV-1 infections in vitro for research purposes.Here we present four protocols for in-house ELISAs to detect HIV CA-p24 using commercial antibodies. The assays were able to detect the CA-p24 antigen of different HIV-1 isolates tested. Comparison between the protocols showed that these in-house ELISAs exhibit high specificity, sensitivity, and reproducibility for CA-p24 quantitation but their reactivity varied per HIV-1 isolate and subtype.These optimized ELISA protocols represent valuable tools to investigate HIV-1 infections in research facilities at a lower price than commercial CA-p24 kits.The online version contains supplementary material available at 10.1186/s12985-023-02242-5. HIV infections are prevalent worldwide. If left untreated, HIV can progress to AIDS (Acquired Immunodeficiency Syndrome) and cause more than 600,000 deaths every year . The curCurrent research approaches include viral genome editing through CRISPR-Cas systems, stem cell transplants, and mRNA vaccines \u20137. SucceIn this study, we aimed to optimize and compare four in-house CA-p24 ELISA systems to detect and quantitate distinct HIV-1 isolates. We determined the reproducibility and sensitivity of the ELISA systems and described their characteristics for testing CA-p24 antigen.q\u2009=\u20090.0065, Kruskal\u2013Wallis\u2019 test), and 45\u2009\u00d7\u2009lower than very high-cost commercial kits (q\u2009=\u20090.0048) , Anogen (ANG), Sino Biological (SB), and R&D Systems (RND). The costs per each in-house assay range between \u20ac25 and \u20ac30 per one 96-well plate, which is 15\u2009\u00d7\u2009lower than medium-cost commercial kits, 25\u2009\u00d7\u2009lower than high-cost commercial kits , possibly due to the use of the same detection antibody. Similarly, SB-CA-p24 ELISA showed a significantly high correlation with ABR-CA-p24 ELISA . RND-CA-p24 ELISA also exhibited a significant high correlation with ABR-CA-p24 ELISA  , suggesting a similar sensitivity between both assays, possibly due to their similar reactivity for HIV-1 B subtypes. The lowest correlations were observed between RND- and SB-CA-p24 ELISAs  and between ANG- and SB-CA-p24 ELISAs  , suggesting a high between-assay reproducibility for the ELISA systems.We then assessed the reproducibility of the ELISA systems, examining both their consistency within individual assays and their reliability between different assays. In order to assess within-assay reproducibility, we employed the NL4-3 HIV-1 isolate as a test model. We quantified its concentration in each assay by utilizing technical replicates and applying different inactivation treatments, including heat and/or detergent. We observed that the concentration of the NL4-3 isolate remained consistent between the replicates within the tested conditions  guidelines classify HIV-1 as a Risk Group 3 agent. Research involving HIV-1 was approved by the institutional biosafety office and carried out according to laboratory biosafety 3 guidelines.Twenty-two different HIV-1 isolates were produced according to standard protocols . The HIVVirus stocks were generated on CD8\u2009+\u2009-depleted human peripheral blood mononuclear cells (PBMCs) for each isolate, including the lab-adapted strains, and virus production was measured by CA-p24 ELISA (in-house assays). The HIV stocks were inactivated with 0.1% Empigen  followed by incubation at 56\u00a0\u00b0C for 30\u00a0min.Aalto Bio Reagents (ABR) system2O. Adjust pH to 7.4 with HCl and add ddH2O up to a volume of 1,000\u00a0mL. Store at room temperature (20\u201325\u00a0\u00b0C). Dilute 1:10 with ddH2O for 1\u2009\u00d7\u2009TBS buffer.10\u2009\u00d7\u2009Tris buffered saline (TBS) buffer: 1.37\u00a0M NaCl (80\u00a0g)\u2009+\u200927\u00a0mM KCl (2\u00a0g)\u2009+\u20092.4\u00a0g of Tris in a volume of 950\u00a0ml of ddHFirst wash buffer solution and dilution buffer:1\u2009\u00d7\u2009TBS\u2009+\u20090.05% Empigen: Add 83\u00a0ml of 30% Empigen into 500\u00a0ml of 1\u2009\u00d7\u2009TBS buffer (Table 2O. Adjust pH to 7.4 with HCl up to 1000\u00a0mL and purify with a 0.2\u00a0\u00b5m filter and store at room temperature (20\u201325\u00a0\u00b0C). Dilute 1:10 with ddH2O for 1\u2009\u00d7\u2009PBS buffer.10\u2009\u00d7\u2009phosphate-buffered saline (PBS): 20 PBS tablets and up to 950\u00a0mL of ddHSecond wash buffer solution:2O for 1\u2009\u00d7\u2009PBS buffer\u2009+\u20090.1% Tween.10\u2009\u00d7\u2009PBS buffer\u2009+\u20091% Tween. Add 10\u00a0ml of Tween 20 into 990\u00a0ml of 10\u2009\u00d7\u2009PBS buffer. Store at room temperature (20\u201325\u00a0\u00b0C). Dilute 1:10 with ddH3: 4.2\u00a0g NaHCO3 and up to 450\u00a0mL of ddH2O. Adjust pH to 8.5 and add ddH2O up to a volume of 500\u00a0mL. Store at room temperature (20\u201325\u00a0\u00b0C).0.05\u00a0M NaHCOCoating buffer and antibody:3 (10\u00a0\u00b5g/mL) and dispense 25\u00a0\u00b5l of capture antibody solution into each well.Anti-HIV Gag CA-p24: reconstitute according to manufacturer\u2019s instructions. Make 100\u00a0\u00b5l aliquots and store at \u2212\u00a020\u00a0\u00b0C until use. To coat one 96-well plate, add 25\u00a0\u00b5l of aliquoted capture antibody into 2,475\u00a0\u00b5l of 0.05\u00a0M NaHCOCA-p24 protein: reconstitute with 1\u2009\u00d7\u2009TBS, 20% Sheep serum, and 1% Empigen to a concentration of 10\u00a0\u00b5g/mL. Dilute 1:10 with 1\u2009\u00d7\u2009TBS\u2009+\u20091% Empigen to a concentration of 1\u00a0\u00b5g/mL. Make 30\u00a0\u00b5l aliquots and store at -80\u00a0\u00b0C until use.CA-p24 standard curve: add 25\u00a0\u00b5l of aliquoted CA-p24 standard into 225\u00a0\u00b5l of dilution buffer (1\u2009\u00d7\u2009TBS\u2009+\u20090.05% Empigen) (working stock). Prepare standard curve dilutions as specified in Additional File CA-p24 standard protein and curve:ABR, ANG):HIV-CA-p24, Alkaline Phosphatase Conjugate monoclonal antibody (AP-mAb): reconstitute and dilute 1:5 by adding 20\u00a0\u00b5l of antibody into 80\u00a0\u00b5l triethanolamine. Store at 4\u00a0\u00b0C until use.Prepare the conjugate for one 96-well plate as followed: 2\u00a0mL of 1\u2009\u00d7\u2009TBS\u2009+\u20090.5\u00a0mL of sheep serum\u2009+\u20092.5\u00a0\u00b5l of Tween 20\u2009+\u20090.05\u00a0g of skim milk (2%)\u2009+\u20090.31\u00a0\u00b5l of the reconstituted conjugated . Dispense 25\u00a0\u00b5l of conjugate solution into each well.Detection antibody, conjugate, and substrate  into each well Table .2.Sino Biological (SB) and Anogen (ANG) systemsABR protocol). Store at room temperature (20\u201325\u00a0\u00b0C). Dilute 1:10 with ddH2O for 1\u2009\u00d7\u2009PBS buffer\u2009+\u20090.05% Tween : to prepare the blocking buffer needed for one 96-well plate, add 0.2\u00a0g of BSA into 10\u00a0ml of 1\u2009\u00d7\u2009PBS buffer\u2009+\u20090.05% Tween.1\u2009\u00d7\u2009PBS\u2009+\u20090.05% Tween\u2009+\u20090.1% BSA: to prepare the dilution buffer needed for one 96-well plate, dilute 1:20 the blocking buffer into new 1\u2009\u00d7\u2009PBS buffer\u2009+\u20090.05% Tween as needed.SB): reconstitute according to manufacturer\u2019s instructions. To coat one 96-well plate, add 5.6\u00a0\u00b5l of coating antibody into 2.8\u00a0mL of 1\u2009\u00d7\u2009PBS (2\u00a0\u00b5g/mL) and dispense 25\u00a0\u00b5l of coating antibody solution into each well (Table Mouse Anti-HIV-CA-p24 (Coating antibodies:ANG): reconstitute according to manufacturer\u2019s instructions. To coat one 96-well plate, add 25\u00a0\u00b5l of aliquoted coating antibody into 2,475\u00a0\u00b5l of 1\u2009\u00d7\u2009PBS (10\u00a0\u00b5g/mL) and dispense 25\u00a0\u00b5l of coating antibody solution into each well  into 225\u00a0\u00b5l of dilution buffer (1\u2009\u00d7\u2009PBS\u2009+\u20090.05% Tween\u2009+\u20090.1% BSA) (working stock). Prepare standard curve dilutions as specified in Additional File CA-p24 standard curve:SB): reconstitute according to manufacturer\u2019s instructions. Dilute 1:1,000 in HRP stabilizer (Table Mouse Anti-HIV-CA-p24 horseradish peroxidase (HRP) antibody (SB): to prepare the conjugate for one 96-well plate, dilute 1:1,000 aliquoted detection antibody by adding 3\u00a0\u00b5l of antibody into 3,000\u00a0\u00b5l of dilution buffer (100\u00a0ng/mL) and dispense 25\u00a0\u00b5l of conjugate solution into each well.Conjugate (SB): dilute 1:10 Lumiphos A and B solutions by adding 150\u00a0\u00b5l of solution A and 150\u00a0\u00b5l of solution B into 2.7\u00a0ml of ddH2O. Dispense 25\u00a0\u00b5l of LumiPhos A\u2009+\u2009B solution into each well SB/ANG protocols) with ddH2O.1\u2009\u00d7\u2009PBS buffer\u2009+\u20090.05% Tween: dilute 1:10 10\u2009\u00d7\u2009PBS buffer\u2009+\u20090.5% Tween  into 45\u00a0\u00b5l of dilution buffer (1\u2009\u00d7\u2009PBS\u2009+\u20090.2% TritonX-100\u2009+\u20091% BSA) (working stock). Prepare standard curve dilutions as specified in Additional File CA-p24 standard curve: add 5\u00a0\u00b5l of aliquoted CA-p24 standard (CA-p24 standard curve:Biotinylated Mouse Anti-HIV-1 Gag CA-p24 Detection Antibody: reconstitute according to manufacturer\u2019s instructions with 1.0\u00a0ml of dilution buffer (1\u2009\u00d7\u2009PBS\u2009+\u20090.2% TritonX-100\u2009+\u20091% BSA). Make 45\u00a0\u00b5l aliquots and store at \u2212\u00a020\u00a0\u00b0C until use. To prepare the antibody solution for one 96-well plate, add 41.8\u00a0\u00b5l of aliquoted detection antibody into 5\u00a0mL of 1\u2009\u00d7\u2009PBS\u2009+\u20090.2% TritonX-100\u2009+\u20091% BSA buffer (125\u00a0ng/mL) and dispense 50\u00a0\u00b5l of detection antibody solution into each well.Conjugate: to conjugate the detection antibody in one 96-well plate, dilute 1:80 Streptavidin-HRP solution by adding 62.5\u00a0\u00b5l of antibody into 5\u00a0ml of 1\u2009\u00d7\u2009PBS\u2009+\u20090.2% TritonX-100\u2009+\u20091% BSA buffer and dispense 50\u00a0\u00b5l of solution into each well.2O  was used to analyze datasets and determine the sensitivity of the assays and Pearson\u2019s Additional file 1: Supplementary Figs.\u00a01\u20134. (.pdf). Fig. S1. Comparison of costs between in-house and commercial ELISA kits. Fig. S2. Standard curves generated by ABR-, ANG-, SB-, and RND-CA-p24 ELISAs. Fig. S3. Effect of viral inactivation on assay performance and within-assay reproducibility of ELISA systems. Fig. S4. Between-assay reproducibility of the ELISA systems.Additional file 2: Supplementary Tables 1\u20134 (.pdf). Table S1. List of commercial ELISA kits and their costs. Tables S2\u2013S4. Four tables with the volumes and details needed to prepare the standard curves for the ABR-, ANG-, SB-, and RND-CA-p24 ELISAs."}
{"text": "A short and directional tetrel bond between tin and oxygen is identified in the title compound. 6H5)3]\u00b7C18H21OP, is reported. The 1:1 cocrystal features a short and directional tetrel bond between tin and oxygen. The tin\u2013oxygen distance is 2.346\u2005(4)\u2005\u00c5, representing 62% of the sum of the van der Waals radii of Sn and O. The Cl\u2014Sn\u22efO angle is 174.0\u2005(1)\u00b0 and this nearly linear arrangement is consistent with a tetrel bond formed via a \u03c3-hole opposite the tin\u2013chlorine covalent bond. Some weak C\u2014H\u22efCl inter\u00adactions are noted between adjacent mol\u00adecules.The single-crystal X-ray diffraction structure of the title compound, [SnCl(C The asymmetric unit consists of one complete mol\u00adecule of each type. The tin\u2013oxygen distance is 2.346\u2005(4)\u2005\u00c5 and the Cl\u2014Sn\u22efO TB angle is 174.0\u2005(1)\u00b0 \u2005\u00c5 and the Cl\u2014Sn\u22efO TB angle is 177.57\u2005(7)\u00b0 (p-tol\u00adyl)tin]-\u03bc-1,2-bis\u00ad(di\u00adphenyl\u00adphosphor\u00adyl)ethane-\u03ba2O:O\u2032-[bromido\u00adbis\u00ad(p-chloro\u00adphen\u00adyl)(p-tol\u00adyl)tin] 2\u00b7(Me2N)2PO tin\u2013hexa\u00admethyl\u00adphospho\u00adr\u00adamide , a moderately strong and directional noncovalent inter\u00adaction, has received renewed inter\u00adest in recent years as a useful structure-directing element and crystal engineering tool \u00b0 Fig.\u00a01. This divia slow evaporation of the solvent in a fume hood over a period of 5\u2005d. Evidently, during the synthesis, the phosphane was oxidized to give the phosphane oxide, as the process was not carried out under an inert atmosphere.In a typical procedure, triphenyltin(IV) chloride (0.0614\u2005g) and cyclo\u00adhexyl\u00addiphenyl\u00adphosphane (0.0894\u2005g) were added to hexane (60\u2005ml) in a beaker. The mixture was heated and stirred until the solids were completely dissolved. Cocrystals grew The crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623006375/bv4048sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623006375/bv4048Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623006375/bv4048Isup3.cmlSupporting information file. DOI: 2267964CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Hirshfeld surface analysis indicates that H\u22efH and H\u22efC/C\u22efH contacts are the most important inter\u00adactions.A new copper(II) complex with 3-methyl\u00adbenzoate and 2,2\u2032-bi\u00adpyridine synthesized displays chains of hydrogen-bonded complex units along the  2N,N\u2032)bis\u00ad(3-methyl\u00adbenzoato)-\u03ba2O,O\u2032;\u03baO-copper(II) 0.68-hydrate, [Cu(C8H7O2)2(C10H8N2)(H2O)]\u00b70.68H2O or [Cu(3-mb)2(bipy)(H2O)]\u00b70.68H2O. The coord\u00adination environment of CuII is a distorted octa\u00adhedron. The metal atom is attached to two 3-mb moieties, which bind in monodentate and bidentate fashions. One of the 3-mb units is disordered. The coordination environment is completed by one bipy ligand and a water mol\u00adecule. A second water mol\u00adecule is outside the coordination sphere of the CuII atom and its occupancy refined to 0.68. The structure consists of chains along the b-axis direction formed by complex units joined via hydrogen bonds between the coordinated water mol\u00adecule and an O atom of a coordinated 3-mb unit. Hirshfeld surface analysis indicates that the most abundant contacts are H\u22efH (56.8%), H\u22efC/C\u22efH (21.7%) and H\u22efO/O\u22efH (13.7%).3-Methyl\u00adbenzoic acid (3-mbH) and 2,2\u2032-bi\u00adpyridine (bipy) reacted with a cop\u00adper(II) salt forming a new mixed ligand complex, aqua\u00ad(2,2\u2032-bi\u00adpyridine-\u03ba The complex was octa\u00adhedral with 3-mb acting as monodentate  complexes continues to be of inter\u00adest. Copper is an important part of various metalloenzymes. It takes part in many metabolic processes such as iron metabolism, mitochondrial oxidative phospho\u00adrylation and catecholamine production  to 2.0131\u2005(18)\u2005\u00c5 and the N1\u2014Cu1\u2014N2 angle is 80.58\u2005(7)\u00b0 (Table\u00a01carboxyl\u00adate distances are 1.842\u2005(17)\u20132.2988\u2005(18)\u2005\u00c5. The Cu\u2014O and Cu\u2014N values are very close to those reported for copper(II) complexes involving benzoate (BZA) as a ligand, for example [Cu(BZA)2(bipy)(H2O)] [Cu\u2014O = 1.9951\u2005(12)\u20131.9633\u2005(12)\u2005\u00c5 and Cu\u2014N = 2.0064\u2005(14)\u20132.0111\u2005(13)\u2005\u00c5; Devereux et al., 2007Complex 1 Fig.\u00a01 crystall\u00b0 Table\u00a01. The Cu13.B\u22efO4) leads to the formation of a linear chain in the b-axis direction  refined to 0.68, which seems to be due to water escaping the crystal through the channels that run along the b-axis direction.In the crystal, hydrogen bonding between H atoms of the coord\u00adin\u00adated water mol\u00adecule and the O atoms of the coordinated 3-mb , H\u22efC/C\u22efH  and H\u22efO/O\u22efH  contacts are 56.8, 21.7 and 13.7%, respectively.\u22efH Fig.\u00a04c and H\u22ef\u22efH Fig.\u00a04d contac6.3)2\u00b73H2O  in water (20\u2005ml) under stirring. A solution of 2,2\u2032-bi\u00adpyridine  in EtOH (25\u2005ml) was added and the color changed from greenish blue to blue. The precipitate was filtered off, washed with water and dried. Blue single crystals of the title complex suitable for X-ray diffraction studies were obtained after evaporation of an ethanol solution after several days.3-Methyl\u00adbenzoic acid  and sodium hydroxide  in water (20\u2005ml) were added to a solution of Cu(NO7.A\u2013O6\u2013H6B refined to 0.680\u2005(10). The coordinates of the ordered water atom were refined with Uiso(H) = 1.5Ueq(O). All other H atoms were positioned geometrically and refined as riding with Uiso(H) = 1.2\u20131.5Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023006904/dj2063sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023006904/dj2063Isup2.hklStructure factors: contains datablock(s) I. DOI: 2117143CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The formation of a co-crystal sustained by \u03c0-type halogen bonds involving 1,4-di\u00adiodo\u00adperchloro\u00adbenzene and naphthalene is reported. 6I2Cl4) as the halogen-bond donor along with naphthalene (nap) as the acceptor is reported. The co-crystal  generates a chevron-like structure that is held together primarily by \u03c0-type halogen bonds (i.e. C\u2014I\u22ef\u03c0 contacts) between the components. In addition, C6I2Cl4 also inter\u00adacts with the acceptor via C\u2014Cl\u22ef\u03c0 contacts that help stabilize the co-crystal. Within the solid, both aromatic components are found to engage in offset and homogeneous face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. Lastly, the halogen-bond donor C6I2Cl4 is found to engage with neighboring donors by both Type I chlorine\u2013chlorine and Type II iodine\u2013chlorine contacts, which generates an extended structure.The formation and crystal structure of a co-crystal based upon 1,4-di\u00adiodo\u00adperchloro\u00adbenzene (C Recently, we reported the formation of photoreactive co-crystals based upon C6I2Cl4 along with trans-1,2-bis\u00ad(pyridine-4-yl)ethyl\u00adene  resulting in a chevron-like structure. In addition to the \u03c0-type halogen bond, the co-crystal (C6I2Cl4)\u00b7(nap) is also held together by the combination of C\u2014Cl\u22ef\u03c0 contacts, homogeneous face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions, Type I chlorine\u2013chlorine contacts, and Type II iodine\u2013chlorine contacts.A continued goal within our research groups has been in the design and formation of halogen-bonded co-crystals based upon 1,4-di\u00adiodo\u00adperchloro\u00adbenzene (C2.6I2Cl4)\u00b7(nap) crystallizes in the centrosymmetric triclinic space group P\u012b. The asymmetric unit contains half a mol\u00adecule of both C6I2Cl4 and nap where inversion symmetry generates the remainder of each mol\u00adecule \u00b7(nap), the donor C6I2Cl4 is found to engage in Type I chlorine\u2013chlorine contacts  1\u00a0\u2212\u00a0x, -y, 1 \u2212 z], with a distance of 3.499\u2005(1)\u2005\u00c5 and a C\u2014Cl\u22efCl bond angle of \u03b81 = \u03b82 = 132.16\u2005(6)\u00b0  1\u00a0\u2212\u00a0x, -y, 1 \u2212 z], with a distance of 3.808\u2005(1)\u2005\u00c5 and a C\u2014I\u22efCl bond angle of 111.83\u2005(4)\u00b0. Both the aromatic halogen-bond donor and acceptor are found to engage in an offset and homogeneous face-to-face \u03c0\u2013\u03c0 stacking arrangement that stabilizes the co-crystal \u2005\u00c5 measured for Cl1\u22efC5.In addition to \u03c0-type halogen bond within \u00b7(nap). This Hirshfeld surface analysis along with the observed bond lengths confirms the ability of C6I2Cl4 to engage in \u03c0-type halogen bonds to a polycyclic aromatic hydro\u00adcarbon, namely nap.These various non-covalent inter\u00adactions were also investigated and visualized by utilizing a Hirshfeld surface analysis  in which the I atom is within the van der Waals radius of an aromatic surface revealed only one structure, refcode HONBIY \u00b7(nap).A search of the Cambridge Crystallographic Database  was synthesized utilizing a previously published method  were both purchased from Sigma-Aldrich Chemical  and used without any additional purification. The halogen-bond donor 1,4-di\u00adiodo\u00adperchloro\u00adbenzene \u00b7(nap) was achieved by dissolving 50.0\u2005mg of C6I2Cl4 in 2.0\u2005mL of toluene and then combined with a 2.0\u2005mL toluene solution containing 13.7\u2005mg of nap . Within two days, single crystals suitable for X-ray diffraction were formed upon loss of some of the solvent by slow evaporation.The formation of  I. DOI: 10.1107/S2056989023008356/jy2037Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023008356/jy2037Isup3.cmlSupporting information file. DOI: 2291675CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title com\u00adplex, bis\u00ad{\u03bc-1,1\u2032-(o-xylylene)bis\u00ad[4-(pyridin-2-yl)triazole]-\u03baN3:N3\u2032}dipalladi\u00adum(II) tetra\u00adkis\u00ad(tetrafluoridoborate)\u2013di\u00admethyl\u00adformamide\u2013diethyl ether (1/2/1), as the BF4 salt, and including di\u00admethyl\u00adformamide and diethyl ether solvent mol\u00adecules, with stoichiometry [Pd2(C22H18N8)2](BF4)4\u00b72C3H7NO\u00b7C4H10O, the Pd complex and the disordered diethyl ether mol\u00adecule lie on inversion centers. The ligand coordinates to the PdII centers with square-planar geometry, forming a dimeric macrocycle. The Pd\u22efPd separation in the complex [Pd2(o-xpt)2]4+ cation is 3.6184\u2005(4)\u2005\u00c5. In the crystal, the complex mol\u00adecules are stacked along the b axis, with \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl\u00adtriazole ligands of two mol\u00adecules.A tetra\u00addentate ligand, namely,  Herein, we report the synthesis and crystal structure of the title compound.The self-assembly of polydentate ligands with transition-metal ions to create functional metal\u2013organic supra\u00admolecules has been of great inter\u00adest in recent years. In particular, the complexation of 2-pyridyl-1,2,3-triazole chelating pockets with transition-metal ions has intensified due to the ease of synthesis of the ligands through the copper-catalyzed azide\u2013alkyne cyclo\u00adaddition (CuAAC) reaction 2]4+ lying on an inversion center, two BF4\u2212 anions in general positions, a di\u00admethyl\u00adformamide solvent mol\u00adecule in a general position and a diethyl ether solvent mol\u00adecule disordered about an inversion center  atoms of two pyridyl\u00adtriazole moieties. The N\u2014Pd\u2014N chelating angles are N1\u2014Pd1\u2014N2 = 79.46\u2005(8)\u00b0 and N7\u2014Pd1\u2014N8 = 79.75\u2005(8)\u00b0. The N(py)\u2014Pd bonds  are slightly longer than N(trz)\u2014Pd bonds , suggesting the triazolium N atom coordinates more strongly to the Pd center than the pyridyl N atom of the ligand. These values are typical for the reported mononuclear PdII complex of pyridyl\u00adtriazole ligands  with an average interplanar distance of 3.364\u2005\u00c5, indicating \u03c0\u2013\u03c0 interaction between the mol\u00adecules; this is shown along the 3CN)4]BF4  in aceto\u00adnitrile (5\u2005ml), o-xpt  in aceto\u00adnitrile (5\u2005ml) was added dropwise. The solution was stirred for 1\u2005h at room temperature. The volatiles were removed in vacuo. The residue was washed with di\u00adchloro\u00admethane (2\u2005ml), followed by methanol (2\u2005ml), and dried under vacuum to give [Pd2(o-xpt)2](BF4)4  as a pale-yellow solid. Crystals suitable for X-ray analysis were obtained by slow vapor diffusion of diethyl ether into a di\u00admethyl\u00adformamide (DMF) solution of the complex at room tem\u00adper\u00adature. Our attempts to obtain a clean 1H NMR spectrum in DMSO-d6 were not successful, possibly due to the labile nature of the complex in solution. High resolution ESI\u2013MS analysis showed a monocationic signal at m/z 1255.1478 {calculated 1255.1540 for [Pd2(o-xpt)2(BF4)4]+}.To a stirred solution of [Pd values were assigned as 1.2Ueq for the attached atom (1.5 for meth\u00adyl). A torsional parameter was refined for each methyl group, except for those of the diethyl ether mol\u00adecule, which were staggered with respect to CH2. The diethyl ether solvent mol\u00adecule is disordered about an inversion center with two half-populated sites. A number of distance and displacement parameter restraints were necessary to model the disorder.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314623003620/xu4050sup1.cifCrystal structure: contains datablock(s) I, glonal. DOI: 10.1107/S2414314623003620/xu4050Isup2.hklStructure factors: contains datablock(s) I. DOI: 2257865CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angles between the A and B rings and their attached phenyl rings are 49.15\u2005(8) and 80.78\u2005(8)\u00b0, respectively. In the extended structure, the mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions, which variously generate C(11) chains and Edis at \u2212428.6\u2005kJ\u2005mol\u22121 being the major contributor.In the title compound, C 38H28O6, the dihedral angles between the naphthalene ring system and its pendant benz\u00adyloxy rings A and B are 88.05\u2005(7) and 80.84\u2005(7)\u00b0, respectively. The dihedral angles between the A and B rings and their attached phenyl rings are 49.15\u2005(8) and 80.78\u2005(8)\u00b0, respectively. In the extended structure, the mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 hydrogen bonds, and \u03c0\u2013\u03c0 stacking inter\u00adactions, which variously generate C(11) chains and R22(12) loops as part of a three-dimensional network. The Hirshfeld surface  and inter\u00admolecular inter\u00adaction energies are reported, with dispersion (Edis = \u2212428.6\u2005kJ\u2005mol\u22121) being the major contributor.In the title compound, C A variety of banana-shaped, bow-shaped or bent-core ferroelectric liquid crystals were developed by incorporating a benzene ring as a rigid core  and its pendant C26\u2013C31 (A) and C12\u2013C17 (B) benz\u00adyloxy rings are 88.05\u2005(7) and 80.84\u2005(7)\u00b0, respectively. The dihedral angles between the A and B rings and their attached C33\u2013C38 and C19\u2013C24 phenyl rings are 49.15\u2005(8) and 80.78\u2005(8)\u00b0, respectively. Key torsion angles include C1\u2014O4\u2014C25\u2014C26 [\u2212160.98\u2005(13)\u00b0], C28\u2014O2\u2014C32\u2014C33 [\u2212172.04\u2005(14)\u00b0], C10\u2014O1\u2014C11\u2014C12 [\u2212168.94\u2005(14)\u00b0] and C14\u2014O3\u2014C18\u2014C19 [172.84\u2005(14)\u00b0]. Otherwise, the geometrical data for the title compound may be regarded as normal.The title compound crystallizes with one mol\u00adecule in the asym\u00admetric unit Fig.\u00a01 in the s3.C(11) chain (arising from the C21\u2014H21\u22efO2ii hydrogen bond), which runs along [010], and centrosymmetric i hydrogen bond) between the mol\u00adecules as shown in Fig.\u00a02In the crystal, the mol\u00adecules are linked by numerous C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions Table\u00a01. Promine4.et al., 2007CrystalExplorer17  are electrostatic (Eele), polarization (Epol), dispersion (Edisp) and exchange\u2013repulsion (Erep), and the cylinder-shaped energy frameworks represent the relative strengths of the inter\u00adaction energies in individual directions, as well as the topologies of pairwise inter\u00admolecular inter\u00adaction energies within the crystal  in DCM (20\u2005ml). Filtration was used to remove the precipitated N,N-di\u00adcyclo\u00adhexyl\u00adurea and the solvent was evaporated. To obtain the pure product, the solid residue was purified using column chromatography on silica gel with DCM as an eluent, followed by recrystallization from ethyl alcohol solution.Under an inert atmosphere, 1,2-di\u00adhydroxy\u00adnaphthalene (1.00\u2005mmol), a catalytic amount of 4-di\u00admethyl\u00adamino\u00adpyridine and 3-benzyl\u00adoxybenzoic acid (2.00\u2005mmol) were dissolved in 50\u2005ml of dry di\u00adchloro\u00admethane (DCM). The above mixture was stirred for 2\u2005h at room temperature with a solution of 7.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023005571/hb8069sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023005571/hb8069Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023005571/hb8069sup3.docxSupplementary Figures showing C--H...pi interactions. DOI: 2271880CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Compounds (I)\u2013(III) are constructed from vertex-sharing ZnO3N tetra\u00adhedra (the organic mol\u00adecule acting as a ligand) and HPO3 pseudo pyramids in a 1:1 ratio to generate the same motif of infinite 4-ring \u2018ladder\u2019 chains propagating in the [010], [101] and [100] directions, respectively, whereas (IV) consists of (010) layers of vertex-sharing ZnO4 and HPO3 units in a 3:4 ratio with the protonated organic mol\u00adecule acting as a template. When an excess of HCl is used in the synthesis, the simple hydrated mol\u00adecular salt, bis\u00ad(2-amino-3-methyl\u00adpyridinium) tetra\u00adchloro\u00adzincate monohydrate, (C6H8N2)2[ZnCl4]\u00b7H2O, (V), arises. Com\u00adpounds (I)\u2013(V) feature extensive networks of hydrogen bonds, both classical  and non-classical  in nature, which help to consolidate the extended structures.The syntheses and crystal structures of four hydro\u00adthermally prepared organo\u2013zinc phosphites,  Each O atom is bonded to one Zn and one P atom [mean Zn\u2014O\u2014P = 130.2\u00b0], thus there are no \u2018dangling\u2019 The asymmetric unit of (I)C2/c, consists of two Zn2+ ions, two [HPO3]2\u2013 hydrogen phosphite anions, and two C6H7N2 2-amino-4-methyl\u00adpyridine mol\u00adecules acting as ligands, i.e., Z\u2032 = 2. Unlike (I)3N tetra\u00adhedra and [HPO3]2\u2013 dianions \u2013 and the major structural features of (II)4\u2032 = 0.97; comparable data for Zn2 = 1.940\u2005\u00c5, 100.10\u2005(5)\u2013121.28\u2005(5)\u00b0 and 0.91, respectively; mean P1\u2014O = 1.525\u2005\u00c5; spread of O\u2014P1\u2014O bond angles = 110.64\u2005(6)\u2013113.78\u2005(6)\u00b0; P1 displacement from its attached O atoms = 0.4278\u2005(7)\u2005\u00c5; comparable data for P2 = 1.520\u2005\u00c5, 111.44\u2005(6)\u2013113.14\u2005(7)\u00b0 and \u22120.4269\u2005(8)\u2005\u00c5, respectively. All six O atoms are bridging between Zn and P atoms with a mean bond angle of 131.3\u00b0 [range = 123.26\u2005(6)\u2013144.09\u2005(8)\u00b0]. The extended structure of (II)The asymmetric unit of (II)P212121 with a well-defined absolute structure and its asymmetric unit  and 115.09\u2005(8)\u00b0, respectively, \u03c44\u2032 = 0.96] and [HPO3]2\u2013 units . The three O atoms bridge adjacent zinc and phospho\u00adrus atoms with a mean Zn\u2014O\u2014P bond angle of 126.7\u00b0. For the extended structure of (III)Compound (III)it Fig.\u00a03 consistsP4 tetra\u00adhedra and four [HPO32\u2013] pseudo pyramids as well as two protonated 2-amino-4-methyl\u00adpyridinium cations, which therefore act as templates rather than ligands; a water mol\u00adecule of crystallization (O13) completes the structure. Geometrical data for the zinc polyhedra are as follows: mean Zn1\u2014O = 1.941\u2005\u00c5, spread of bond angles = 100.42\u2005(8)\u2013122.18\u2005(9)\u00b0, \u03c44\u2019 = 0.90; equivalent data for Zn2: 1.936\u2005\u00c5, 98.33\u2005(8)\u2013115.30\u2005(9)\u00b0 and 0.98, respectively; equivalent data for Zn3: 1.945\u2005\u00c5, 99.70\u2005(8)\u2013117.10\u2005(8)\u00b0 and 0.96, respectively. The four [HPO3]2\u2013 anions adopt their normal geometries: mean P1\u2014O = 1.519\u2005\u00c5, minimum and maximum O\u2014P1\u2014O = 111.00\u2005(11) and 112.70\u2005(11)\u00b0, respectively, deviation of P1 from its attached O atoms = 0.4498\u2005(13)\u2005\u00c5; equivalent data for P2: 1.522\u2005\u00c5, 110.08\u2005(10)\u00b0, 115.33\u2005(11)\u00b0 and \u22120.4122\u2005(12)\u2005\u00c5, respectively; equivalent data for P3: 1.516\u2005\u00c5, 110.19\u2005(11)\u00b0, 114.49\u2005(12)\u00b0 and \u22120.4123\u2005(13)\u2005\u00c5, respectively; equivalent data for P4: 1.516\u2005\u00c5, 112.68\u2005(12)\u00b0, 114.13\u2005(12)\u00b0 and 0.3903\u2005(13)\u2005\u00c5, respectively. The twelve unique O atoms all bridge Zn and P atoms , maximum = 146.90\u2005(13), spread = 21.5\u00b0). For the extended structure of (IV)In (IV)it Fig.\u00a04 reveals P6H8N2+ cations protonated at their pyridine N atoms, a [ZnCl4]2\u2013 anion and a water mol\u00adecule of crystallisation. The tetra\u00adchloro\u00adzincate ion has a mean Zn\u2014Cl separation of 2.2704\u2005\u00c5 [range = 2.2536\u2005(13)\u20132.2867\u2005(13)\u2005\u00c5] and smallest and largest Cl\u2014Zn\u2014Cl bond angles of 104.48\u2005(5) and 113.75\u2005(5)\u00b0, respectively. The synthetic intent here was to lower the pH with HCl and establish if a di\u00adhydrogen phosphite (H2PO3\u2212) anion containing a terminal P\u2014OH moiety could be incorporated into the structure 3.3N and HPO3 polyhedra are linked by Zn\u2014O\u2014P bonds into [010] polyhedral 4-ring (two Zn and two P nodes) \u2018ladder\u2019 chains in which the zinc and phospho\u00adrus nodes strictly alternate  to adjacent P atoms (and a fourth bond to the organic species) and that the P atom forms three links to zinc atoms (and a fourth P\u2014H vertex), the 1:1 Zn:P stoichiometry is to be expected and hence no charge compensating, protonated template is needed. In (II)Z\u2032 = 2, every other 4-ring is generated by inversion symmetry and translation in the [101] direction leads to the extended array. In (III)motif is again apparent te Fig.\u00a06: the chant Fig.\u00a06, althougns Fig.\u00a06.4 and HPO3 polyhedra sharing corners. One way to visualize this rather complex arrangement  is in terms of contorted chains of 4-rings featuring atoms Zn1, Zn2, Zn3, P2, P3 and P4 as the nodes propagating in the [001] direction. One out of every three 4-rings in a chain is generated by inversion symmetry. These chains are cross-linked in the a-axis direction by the P1-centred hydrogen phosphite groups to form the (010) layers, which encapsulate 8-ring voids built up from four Zn and four P nodes although there is no suggestion of \u2018zeolitic\u2019 porosity. So far as stoichiometry is concerned, in this case the zinc nodes forming four bonds  to nearby phospho\u00adrus atoms and the P nodes forming three bonds to Zn atoms leads to the 3:4 ratio of zinc and phospho\u00adrus, which is the proportion most commonly seen in this family of phases 4] unit, hence the two protonated template mol\u00adecules. The template cations and water mol\u00adecules of crystallisation occupy the inter-layer regions.The extended structure of (IV)Various classical  and non-classical (C\u2014H\u22efO and C\u2014H\u22efCl) hydrogen bonds occur in these structures. As is normal, the hydrogen phosphite P\u2014H unit does not participate in hydrogen bonding  and inter-chain (via H1N and H3N) links, with the latter serving to cross-link the [101] chains into a three-dimensional network (Table\u00a02B\u22efO2 bond (Table\u00a03A) of the amine grouping does not participate in a hydrogen bond, the closest acceptor O atom being some 2.77\u2005\u00c5 distant. There are no significant \u03c0\u2013\u03c0 stacking inter\u00adactions in (III)In (II)k Table\u00a02. The arok Table\u00a02, the sind Table\u00a03 cross-livia two O\u2014H\u22efO hydrogen bonds. The N\u2014H\u22efO hydrogen bonds originating from the protonated pyridine N atoms and the \u2013NH2 groups of the organic species all link to the same sheet for each template cation, i.e., there are no inter-sheet hydrogen bonds associated with the templates. Significant aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions occur between centrosymmetric pairs of each template cation, as indicated by the centroid\u2013centroid separation of 3.6167\u2005(15)\u2005\u00c5 (slippage = 1.196\u2005\u00c5) for the C1 species and 3.4695\u2005(17)\u2005\u00c5 (0.146\u2005\u00c5) for the C7 cation.In (IV)w (w = water) and O\u2014H\u22efCl inter\u00adactions to generate [001] chains; within these chains, centrosymmetric assemblages of two C6H8N2+ cations, two [ZnCl4]2\u2013 anions and two water mol\u00adecules are apparent t Fig.\u00a012.4.et al., 20165H6N2\u00b7Zn(HPO3)]n, catena-[(\u03bc3-hydrogenphosphito)(2-amino\u00adpyridine)\u00adzinc] (CSD refcode LUZYOU)  layers of 4- and 8-rings.A survey of the Cambridge Structural Database (Groom 3 units in (I)motif in the wider ZnPO phase space: two other examples with very different ligating mol\u00adecules to those in (I)\u2013(III) are [C4H8N2O3\u00b7Zn(HPO3)]n (C4H8N2O3 = l-asparagine) ]n  \u2013(III).The fact that the N-bonded zinc ions and HPO6H8N2 organic mol\u00adecule acts as a ligand (a Zn\u2014N bond and a 1:1 Zn:P ratio) and (IV)6H9N2+ template (N\u2014H\u22efO hydrogen bonds and a 3:4 Zn:P ratio) arose from similar syntheses, with the only difference being the source of zinc ions . Assuming that hydro\u00adthermal synthesis is not just an impenetrable \u2018black box\u2019 5.3PO3 and 1.14\u2005g of 2-amino-3-methyl\u00adpyridine (Zn:P:template ratio \u2243 1:1:1), which were placed in a 50\u2005ml polypropyl\u00adene bottle with 20\u2005ml of water and shaken well to result in a white slurry. The bottle was placed in an 353\u2005K oven for 24\u2005h and then removed and allowed to cool to room temperature. The solids were recovered by vacuum filtration to result in a mass of needle-like transparent crystals. IR: 2383\u2005cm\u22121 (P\u2014H stretch). Increasing the heating time to one week led to the same product, with a slight improvement in crystallinity, as indicated by sharper peaks in its IR spectrum and X-ray powder diffraction pattern.Compound (I)3PO3 and 1.10\u2005g of 2-amino-4-methyl\u00adpyridine (Zn:P:template ratio \u2243 1:1:1); otherwise following the same procedure as for (I)\u22121 (P\u2014H stretch). Two peaks may arise because of the two different P\u2014H groups in the asymmetric unit 2, 0.86\u2005g of H3PO3 and 1.09\u2005g of 2-amino-5-methyl\u00adpyridine (Zn:P:template ratio \u2243 1:1:1) and 20\u2005ml of water were placed in a 50 ml polypropyl\u00adene bottle and heated to 353\u2005K for three days. Upon cooling, the product consisted of a mass of colourless blocks. IR: 2406\u2005cm\u22121 (P\u2014H stretch).To prepare compound (III)2, 0.77\u2005g of H3PO3 and 1.03\u2005g of 2-amino-4-methyl\u00adpyridine (Zn:P:template ratio \u2243 1:1:1) and 20\u2005ml of water. These components were placed in a 50-ml polypropyl\u00adene bottle and heated to 353\u2005K for 24\u2005h. Upon cooling, the product consisted of a mass of colourless blocks. IR: 3000\u20133600 (broad) (O\u2014H stretch), 2391, 2381\u2005cm\u22121 (P\u2014H stretch). The same product arises if the mixture is heated for one week.Compound (IV)M HCl.Compound (V)6.Uiso(H) = 1.2Ueq(N or O). The phosphite H atoms were geometrically placed (P\u2014H = 1.32\u2005\u00c5) and refined as riding atoms with Uiso(H) = 1.2Ueq(P). All the C-bound H atoms were located geometrically (C\u2014H = 0.95\u20130.98\u2005\u00c5) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density. Two peaks greater than 1\u2005e\u2005\u00c5\u22123 were found in the final difference map for (IV)Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989023002062/pk2681sup1.cifCrystal structure: contains datablock(s) I, II, III, IV, V, global. DOI: 10.1107/S2056989023002062/pk2681Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023002062/pk2681IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989023002062/pk2681IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989023002062/pk2681IVsup5.hklStructure factors: contains datablock(s) IV. DOI: 10.1107/S2056989023002062/pk2681Vsup6.hklStructure factors: contains datablock(s) V. DOI: 2246111, 2246110, 2246109, 2246108, 2246107CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Speciation, mechanism and polymer chain growth studies support a step\u2010growth process where reversible chain transfer occurs, i.e. H3B\u2009\u22c5\u2009PRH2/oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H2BPPhH]110\u2010b\u2010[H2BP(n\u2010hexyl)H]11 can be synthesized and self\u2010assembles in solution to form either rod\u2010like micelles or vesicles depending on solvent polarity.An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism\u2010led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H 2BPPhH]110\u2010b\u2010[H2BP(n\u2010hexyl)H]11, have been prepared by a mechanism\u2010led strategy of the catalytic reversible chain transfer dehydropolymerization of precursor monomers, H3B\u2009\u22c5\u2009PRH2 . These self\u2010assemble in THF:hexane solutions to form nanostructured rod\u2010like micelles, the morphology of which can be controlled by solvent polarity.Amphiphilic block copolymers of polyphosphinoboranes, [H Organic block copolymers (BCPs), in which chemically\u2010distinct segments of monomer units are linked together in a polymer chain, have played an important role in the development of macromolecular science.3, 4 T2BPRH]n (ClCH2Cl)][BArF4], I,2OTf, II.[I.II a non\u2010living chain\u2010growth mechanism is proposed.2PCH2CH2PPh2)2]Cl, 1, and harnessing a step\u2010growth like mechanism in which reversible chain transfer also occurs,Polyphosphinoborane homopolymers are generally (\u03b76\u2010FC6H5)[BArF4] (L1=Ph2PCH2CH2CH2PPh2) will dehydropolymerize H3B\u2009\u22c5\u2009PPhH2 under melt conditions to form [H2BPPhH]n, while solution conditions produced shorter\u2010chain oligomers.III complex with a chelating P\u2212H activated diboraphosphine is a plausible intermediate, e.g. [Rh(L1)H][BArF4], III 2C6H3);[F4]\u2212 anion we explored the use of air\u2010stable [Rh(Ph2PCH2CH2PPh2)2]Cl, 1, in the anticipation that the chelating phosphine may become labile under the conditions of catalysis (\u2248100\u2009\u00b0C). Optimization of conditions showed that 1\u2005mol% 1, 1.25\u2005M H3B\u2009\u22c5\u2009PPhH2, heated at 100\u2009\u00b0C in toluene for 19\u2005hours in a sealed thick\u2010walled NMR tube, followed by precipitation into hexanes, afforded [H2BPPhH]n as a white solid in 86\u2009% isolated yield.Mn=26\u2009500\u2005g\u2009mol\u22121, \u00d0=1.6 =355\u2005Hz. Under these conditions no significant amounts of shorter chain, or cyclic, oligomers are observed.[1 will also dehydropolymerize relatively electron\u2010poor H3B\u2009\u22c5\u2009P2C6H3)H2 to form higher molecular weight polyphosphinoborane [H2BP2C6H3)H]n, Mn=127\u2009500\u2005g\u2009mol\u22121, \u00d0=1.2 in the same reaction time .31P NMR spectrum by a statistical distribution of proposed rr,  or mm triads, \u03b4(31P{1H}) \u221245.6, \u221246.9, \u221248.3 (1\u2009:\u20092\u2009:\u20091 respectively), as noted previously.[1 to form [H2BP(n\u2010hexyl)H]n as a colorless, hexane\u2010soluble, oil, Mn=33\u2009000\u2005g\u2009mol\u22121, \u00d0=1.3;,[2PCH2CH2PPh2)H]Cl, 2, Scheme\u20052, and a similar mixture of diastereoisomers, can also be formed by direct addition of a slight excess of H3B\u2009\u22c5\u2009PPhHBH2\u2009\u22c5\u2009PPhH22PCH2CH2PPh2)(\u03b76\u2010C6H5F)][BArF4]8\u2010toluene. ESI\u2010MS analysism/z=747.2  with the correct isotopologue pattern. Irrespective of the method of synthesis, accompanying 2 are unidentified minor hydride signals observed between \u221215 to \u221216\u2005ppm, that become dominant as catalysis reaches completion. These are currently unidentified,3B\u2009\u22c5\u2009PPhH2 they are not deactivation products. Complex 2, at least at the early stages of catalysis, is thus identified as a likely resting state.In situ catalyst speciation studies , using the distinctive P\u2212H resonances between 5.5 and 3.5\u2005ppm, reveals a first order decay of H3B\u2009\u22c5\u2009PPhH2 \u00d710\u22124\u2005s\u22121), linear diboraphosphine H3B\u2009\u22c5\u2009PPhHBH2\u2009\u22c5\u2009PPhH2 as an intermediate and the growth in of oligomeric/polymeric [H2BPPhH]n, Scheme\u20053B\u2009\u22c5\u2009PPhH2 restarts catalysis (kobs=1.5(1)\u00d710\u22124\u2005s\u22121). In a separate experiment (3\u2005mol% 1) using H3B\u2009\u22c5\u2009PPhHBH2\u2009\u22c5\u2009PPhH2 (0.14\u2005M) as the precursor resulted in its clean first order consumption (kobs=1.0(1)\u00d710\u22124\u2005s\u22121) to form [H2BPPhH]n . Combined these observations on the resting state and the temporal evolution of substrates and products lead us to propose a simplified mechanism, Scheme\u2005(i)\u2005the P/B dehydrocoupling of \u2212PPhH2 and \u2212BH3 end groups at the metal center to form 2 (R\u2032=H), or a close analog thereof, i.e. R\u2032=[PPhHBH2]nPPhH\u2009\u22c5\u2009BH3; (ii)\u2005a reversible chain transfer between bound and free phosphine\u2013boranes; (iii)\u2005a turnover limiting step that involves substitution of the newly coupled oligomer with another phosphine\u2013borane (monomer/oligomer/polymer), that leads to the observed first\u2010order decay of monomers H3B\u2009\u22c5\u2009PPhH2 or H3B\u2009\u22c5\u2009PPhHBH2\u2009\u22c5\u2009PPhH2; (iv)\u2005an overall step\u2010growth like mechanism that supports the observation of H3B\u2009\u22c5\u2009PPhHBH2\u2009\u22c5\u2009PPhH2 as a persistent intermediate.Following reaction progress by t 100\u2009\u00b0C \u2005mol% 1, t 100\u2009\u00b0C \u2005mol% 1, Mn of isolated polymer using higher loadings, but incomplete conversions with higher dispersities at lower loadings using the same reaction time  clearly demonstrates step growth propagation (Scheme\u2005Mn=77\u2009000\u2005g\u2009mol\u22121) is only formed after 5\u2005days reaction time. In contrast, for a chain growth process, high molecular weight polymer would be expected to be observed at low conversions of monomer.n, Mn(MALS)=7\u2009000\u2005g\u2009mol\u22121, with H3B\u2009\u22c5\u2009P(n\u2010hexyl)H2 monomer (1.25\u2005M in toluene), catalyst 1 (3\u2005mol%), and heating for 66\u2005hrs at 100\u2009\u00b0C resulted in a mixture of products by 31P{1H} NMR spectroscopy, including homopolymer [H2BP(n\u2010hexyl)H]n and related short\u2010chain oligomers. Using the noted solubility difference between Ph\u2010 and n\u2010hexyl substituted polyphosphinoboranes, extraction into hexanes selectivity removed polymers/oligomers containing only n\u2010hexyl groups. Importantly the hexane insoluble portion displayed both phenyl and hexyl resonances in the corresponding 1H and 31P spectra, an initial indication that a block copolymer had been formed, Scheme\u200531P NMR spectrum a signal at \u03b4 \u221249.5 [J(PH)=350\u2005Hz] is assigned to [H2BPPhH]n segments, while a cluster of signals centered at \u221263.4 is assigned to [H2BP(n\u2010hexyl)H]n, interestingly in which the atacticity can now be observed,1H NMR spectrum in the P\u2212H region indicates a similar ratio of Ph to n\u2010hexyl units. Additional smaller signals are observed in the 31P NMR spectrum at \u03b4 \u221255.8 as an apparent triplet, that simplifies to a singlet on decoupling 1H, and \u03b4 \u221248 . These could reflect connecting units between block segments, P(n\u2010hexyl)H2 end groups110\u2010b\u2010[H2BP(n\u2010hexyl)H]11, BCP1. A small amount of low molecular weight oligomer (\u2248500\u2005g\u2009mol\u22121) is also observed in the GPC spectrum. As pre\u2010formed [H2BPPhH]n contained no such species, we assign this to short oligomers of [H2BP(n\u2010hexyl)H]n.With this calibration in hand, taking pre\u2010formed n and [H2BP(n\u2010hexyl)H]n have very different diffusion coefficients (1.5(2) and 3.9(8) \u00d710\u221210\u2005m2\u2009s\u22121, respectively, Figure S42). However, BCP1 also has a different diffusion coefficient, that is the same for both phenyl and hexyl regions of the 1H NMR spectrum (1.99(3) and 1.95(5) \u00d710\u221210\u2005m2\u2009s\u22121), indicating both segments are in the same macromolecule. A two\u2010component model is needed to best fit the data in the alkyl region, with a minor, faster diffusing, component required (9.6(2)\u00d710\u221210\u2005m2\u2009s\u22121). This is fully consistent with the shorter, oligomeric, material observed by GPC. Dynamic Light Scattering  experiments place the apparent hydrodynamic radius of BCP1 as 2.7\u00b12.0\u2005nm in CHCl3 , a reasonable fit with that from DOSY (2.1\u00b10.2\u2005nm), and supports the formation of non\u2010aggregated polymer chains in CHCl3 solution.BCP1, the ability to reversibly bind and activate different terminus P\u2212H/B\u2212H groups is no doubt important to the formation of a block copolymer. As it is well established that P\u2212H activation occurs more quickly with PPhH2 than with P(n\u2010hexyl)H2 H2 or equivalent short chain oligomers.While we currently cannot comment on the precise order of events to form r Scheme\u2005, we suggs Scheme\u2005C, followBCP1 self\u2010assembled micellar nanostructures should be formed in solution. Molecularly dissolved BCP unimers were observed in pure THF and CHCl3, or in an equal volume mixture of THF and hexane by dynamic light scattering (DLS) . When the volume fraction of hexane was increased to 37.5\u2009%:62.5\u2009% v/v THF:hexane, to enhance the selectivity for the \u2212[H2BP(n\u2010hexyl)H]11 segment of BCP1, DLS provided evidence for the formation of self\u2010assembled aggregates with Rh=132\u00b112\u2005nm .\u2005Decreasing the solvent polarity further to 25\u2009%:75\u2009% THF:hexane resulted in larger aggregates being formed . The solvent composition and DLS data indicate that micelles are formed with a core of the more polar \u2212[H2BPPhH]110 block and a corona of the less polar \u2212[H2BP(n\u2010hexyl)H]11 segment. The core:corona block ratio ca. 10\u2009:\u20091 classifies these systems as crew\u2010cut micelles and non\u2010spherical morphologies, rather than star\u2010like micelles, would be anticipated based on packing\u2010parameter considerations.BCP1 in 37.5\u2009%:62.5\u2009% v/v THF:hexane solution revealed the formation of rod\u2010like micelles  should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the crystal structure of the title compound, the packing is driven by C\u2014H\u22efF, N\u2014H\u22efO and C\u2014H\u22ef\u03c0 contacts. Hirshfeld surface analysis showed that the largest contribution to the surface contacts arise from F\u22efH/H\u22efF inter\u00adactions. 11H10F4N2O2, the conformation about the N\u2014C\u2014C\u2014O bond is gauche [torsion angle = 61.84\u2005(13)\u00b0]. In the crystal, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into [010] chains, which are cross-linked by C\u2014H\u22efF and C\u2014H\u22ef\u03c0 contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing. This analysis showed that the largest contribution to the surface contacts arises from F\u22efH/H\u22efF inter\u00adactions (35.6%), followed by O\u22efH/H\u22efO (17.8%) and H\u22efH (12.7%).In the title compound, C The amine nitro\u00adgen atom (N2) and ester oxygen atom (O1) are gauche to one another, with N2\u2014C6\u2014C7\u2014O1 = 61.84\u2005(13)\u00b0. The C10 methyl group is oriented in such a fashion as to enable a weak C\u2014H\u22ef\u03c0 inter\u00adaction with the aromatic ring of an adjacent mol\u00adecule  linker unit between the amine nitro\u00adgen atom and the ester, and F3 as acceptor. One of these inter\u00adactions is intra\u00admolecular (C6\u2014H6A\u22efF3) with the other being inter\u00admolecular (C7\u2014H7A\u22efF3). A hydrogen-bonding inter\u00adaction occurs between the secondary amine and the carbonyl oxygen atom (N2\u2014H1N2\u22efO2). Finally, a weak C\u2014H\u22ef\u03c0 inter\u00adaction is observed between H7B and the pyridine ring \u03c0 system.The main directional inter\u00adactions in the crystal structure of the title compound are of the type C\u2014H\u22efF, N\u2014H\u22efO and C\u2014H\u22ef\u03c0 Table\u00a01. The N\u2014HCrystalExplorer17.5  to 1.38 (blue) a.u.; the pale-red spots symbolize short contacts and negative dnorm values on the corresponding surface plots shown in Fig.\u00a02Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and inter\u00admolecular inter\u00adactions in the crystal structure. The Hirshfeld surface analysis  < 1.15\u2005\u00c5. The H\u22efH and C\u22efH/H\u22efC contacts have the second and third largest contributions, at 17.8 and 12.7%, respectively. Smaller spikes on the shoulder of the fingerprint plot, appearing at 1.15\u2005\u00c5 < (id + ed) < 1.160\u2005\u00c5, correspond to the N\u22efH/H\u22efN contacts.The largest contribution to the overall crystal packing is from F\u22efH/H\u22efF inter\u00adactions (35.6%) Table\u00a02. However4.et al., 2016ConQuest amino]\u00adethan-1-ol was synthesized using a known method and used without further purification : \u03b4 6.01 , 5.61 , 4.90 , 4.38 , 3.86 , 1.93 \u2013, 3H); 19F NMR : \u03b4 \u221293.6 , \u2212163.4 ; 13C NMR : \u03b4 167.8 (C=O), 135.8 (CH2=C(CH3)-), 126.4 [CH2=C(CH3)\u2013], 63.7 (\u2013OCH2CH2NH\u2013), 44.1 (\u2013OCH2CH2NH\u2013), 18.3 [CH2=C(CH3)\u2013].A 500\u2005ml round-bottom flask equipped with an addition funnel was charged with 2-[(perfluoro\u00adpyridin-4-yl)amino]\u00adethan-1-ol , tri\u00admethyl\u00adamine  and diethyl ether (300\u2005ml). The solution was stirred under nitro\u00adgen at 273\u2013278\u2005K for 15 minutes. Next, a solution of methacrylol chloride  in ether (10\u2005ml) was added dropwise to the round-bottom flask using an addition funnel. The solution was allowed to gradually warm to room temperature and was stirred for 96\u2005h under nitro\u00adgen. Precipitated salts were removed by vacuum filtration and the filtrate was concentrated under reduced pressure. Crystals of the title compound in the form of colorless needles were obtained by recrystallization from a solution in warm (\u223c328\u2005K) hexa\u00adnes : m.p. 335\u2013336\u2005K; 6.Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023004334/hb8066sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004334/hb8066Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023004334/hb8066Isup3.cmlSupporting information file. DOI: 2263932CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Details of correction: correct footnotes to tables\u00a01, 2 and 3; please correct each oneExisting text: in the footnotes of tables\u00a01,2 and 3:\u00b5g Vit D31 \u00b5g = 40 Corrected text should read:IU Vit D31 \u00b5g = 40"}
{"text": "The crystal structure of the bromo\u00adbenzene\u00adsulfonamide derivative of the type 2 diabetes drug metformin is presented. 10H14BrN5O2S, is the bromo\u00adbenzene\u00adsulfonamide derivative of the type 2 diabetes drug metformin. The asymmetric unit contains two mol\u00adecules with almost identical conformations but a different orientation of the bromo\u00adphenyl moiety. Both mol\u00adecules exhibit intra\u00admolecular N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds. The mol\u00adecular packing features chain formation in the a-axis direction by alternating N\u2014H\u22efN and N\u2014H\u22efO inter\u00adactions. In addition, ring motifs consisting of four mol\u00adecules and \u03c0\u2013\u03c0 inter\u00adactions between the phenyl rings contribute to the three-dimensional architecture. A Hirshfeld surface analysis shows that the largest contributions to surface contacts arise from contacts in which H atoms are involved.The title compound, C Metformin works by decreasing gluconeogenesis in the liver, increasing insulin sensitivity and preventing insulin resistance  in the asymmetric unit  and N30\u22efN34 (mol\u00adecule B) are shared by the two nitro\u00adgen atoms with an occupancy of 0.85\u2005(4) at atoms N15 and N34, and 0.15\u2005(4) at atoms N11 and N30. The dihedral angles between the phenyl ring  and the best plane through the N-containing moiety (N11\u2013C19 in A and N30\u2013C38 in B) are 87.12\u2005(12) and 96.05\u2005(12)\u00b0 in A and B, respectively. Next to the intra\u00admolecular hydrogen bonds N15\u2014H15B\u22efN11 and N34\u2014H34B\u22efN30, a short inter\u00adaction is present between atoms H16B and O9 in A, and H35B and O9 in B  inter\u00adaction, while mol\u00adecule B forms an N34\u2014H34A\u22efO10 hydrogen-bond inter\u00adaction (Table\u00a01D11(2); Etter & MacDonald, 1990a-axis direction is formed by subsequent N16\u22efN32 and N34\u22efO10 inter\u00adactions  distance is 3.686\u2005(3)\u2005\u00c5 and the slippage is 0.650\u2005\u00c5, while for mol\u00adecule B the Cg2\u22efCg2 distance is 4.1086\u2005(3)\u2005\u00c5 and the slippage is 1.936\u2005\u00c5 .Further dimer formation is obtained through \u03c0\u2013\u03c0 stacking between the phenyl rings Fig.\u00a06. For molCrystal Explorer21.3 , H16A\u22efN32 [2.54\u2005(5)\u2005\u00c5] and Br\u22efBr [3.4165\u2005(10)\u2005\u00c5] inter\u00adactions present in the crystal packing. The bright-red spots in Fig.\u00a08A and H35B refer to the N16\u2014H16A\u22efN32, N34\u2014H34A\u22efO10 and N35\u2014H35B\u22efO9 hydrogen bonds, while the additional faint-red spots illustrate weaker H15A\u22efN30 [2.70\u2005(5)\u2005\u00c5] and C14\u22efH23 (2.66\u2005\u00c5) inter\u00adactions present in the crystal packing. The relative distributions from the different inter\u00adatomic contacts to the Hirshfeld surfaces are presented in Table\u00a02A and B, respectively).A Hirshfeld surface analysis was performed, and two-dimensional fingerprint plots were created with 4.et al., 2016a resulted in 17 hits [DEXBUF and DEXBUF01 . For the title compound, this torsion angle is \u2212177.5\u2005(4) and \u2212171.8\u2005(4)\u00b0 in A and B, respectively.A search of the Cambridge Structural Database . The mixture was stirred for 30\u2005min at room temperature. After the reaction was complete, water was removed under reduced pressure and the residue was dissolved in cold anhydrous methanol. The sodium chloride was filtered off and the filtrate was evaporated under reduced pressure to obtain basic metformin.Metformin hydro\u00adchloride  was dissolved in 12Cl2 = 1:10) to obtain the title compound as a colourless solid.The basic metformin  and 3-bromo\u00adbenzene\u00adsulfonyl chloride  were dissolved in 6\u2005mL of anhydrous di\u00adchloro\u00admethane and stirred under a nitro\u00adgen atmosphere for 3\u2005h at room temperature. The solvent was removed on a rotary evaporator and the residue was purified by column chromatography  and sodium gliclazide  were dissolved in 5\u2005mL of acetone and stirred overnight at room temperature. The solvent was removed under reduced pressure and a light-yellow solid was obtained, which was expected to be the sulfonyl\u00adurea salt of the title compound.Cuboid-shaped colourless crystals were grown in an NMR tube by slow evaporation over two weeks using deuterated chloro\u00adform as solvent. However, the grown crystals consist of the title compound and not of its sulfonyl\u00adurea salt.1H NMR  \u03b4 8.03 , 7.90\u20137.76 , 7.64\u20137.57 , 7.56\u20137.22 , 7.06 , 5.19 , 2.99 . 13C NMR  \u03b4 160.29 (s), 158.59 (s), 145.65 (s), 134.41 (s), 130.20 (s), 129.13 (s), 124.70 (s), 122.54 (s), 37.00 (s).NMR spectra of the title compound were recorded on a 400\u2005MHz NMR spectrometer: 6.Uiso(H) values assigned as 1.2Ueq or 1.5Ueq (methyl only) of the parent atoms, with C\u2014H distances of 0.93 (aromatic) and 0.96\u2005\u00c5 (meth\u00adyl). The hydrogen atoms bound to nitro\u00adgen were located in a difference-Fourier map and refined freely with Uiso(H) values assigned as 1.2Ueq of the parent atoms. The occupancy factors of hydrogen atoms H11 and H15B (mol\u00adecule A), and H30 and H34B (mol\u00adecule B) involved in intra\u00admolecular hydrogen bonds converged during refinement to 0.85\u2005(4) for H15B and H34B, and 0.15\u2005(4) for H11 and H30.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023002165/pk2683sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023002165/pk2683Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023002165/pk2683sup3.pdfCSD survey results. DOI: Click here for additional data file.10.1107/S2056989023002165/pk2683Isup4.cmlSupporting information file. DOI: 2246792CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom is coordinated by the S and N atoms of two N\u2032-[(Z)-(furan-2-yl)methyl\u00adidene]carbamohydrazono\u00adthioic acid ligands in a distorted square-planar geometry.In the title complex, the Ni 6H6N3OS)2]\u00b72CH3OH, the NiII atom is coordinated by the S and N atoms of two N\u2032-[(Z)-(furan-2-yl)methyl\u00adidene]carbamohydrazono\u00adthioic acid ligands in a distorted square-planar geometry. The two mutual ligands bound to NiII are also connected by C\u2014H\u22efS inter\u00adactions, while the H atoms of the NH2 group of the ligands form R44(8) motifs with the O atoms of the solvent ethyl alcohol mol\u00adecules. At the same time, the OH groups of the solvent ethyl alcohol mol\u00adecules form parallel layers to the (011) plane by the O\u2014H\u22efN inter\u00adactions with the ligand N atom that is not bonded to the NiII atom.. The layers are connected by van der Waals inter\u00adactions. A Hirshfeld surface analysis indicates that the most important contacts are H\u22efH (37.7%), C\u22efH/H\u22efC (14.6%), O\u22efH/H\u22efO (11.5%) and S\u22efH/H\u22efS (10.6%).In the title complex, [Ni(C The ligands assume a trans arrangement with respect to each other around the NiII ion, which lies on a crystallographic inversion centre at . The Ni\u2014S [2.1818\u2005(6)\u2005\u00c5] and Ni\u2014N [1.9055\u2005(17)\u2005\u00c5] bond lengths lie within the range of those found in related structures.Fig.\u00a013.II are also linked by C\u2014H\u22efS inter\u00adactions, while the H atoms of the NH2 group of the ligands form et al., 1995II atom  is shown in Fig.\u00a05A Hirshfeld surface analysis was carried out using b; 37.7%) contacts to be the most common, followed by C\u22efH/H\u22efC , O\u22efH/H\u22efO  and S\u22efH/H\u22efS  contacts. The N\u22efH/H\u22efN (8.5%), O\u22efC/C\u22efO (4.9%), Ni\u22efH/H\u22efNi (3.2%), O\u22efN/N\u22efO (2.2%), N\u22efC/C\u22efN (1.9%), C\u22efC (1.8%), S\u22efC/C\u22efS (1.1%), S\u22efS (0.7%), O\u22efO (0.7%),S\u22efO/O\u22efS (0.5%) and Ni\u22efC/C\u22efNi (0.2%) contacts have little directional influence on the mol\u00adecular packing.The two-dimensional fingerprint plots show the H\u22efH Fig.\u00a06b; 37.7%\u22efC Fig.\u00a06c; 14.6%\u22efO Fig.\u00a06d; 11.5%\u22efS Fig.\u00a06e; 10.6%4.et al., 2016et al., 1987et al., 2009A search of the Cambridge Structural Database \u2005\u00c5 and Ni\u2014N(2) = 1.921\u2005(2)\u2005\u00c5. The coordination around Ni is trans planar with respect to the two S and two N atoms. The furan ring plane is at an angle of 3(1)\u00b0 to the coordination plane. In the crystal of NOQCUS, the coordination environment around the nickel(II) ion is totally planar, as the NiN2S2 chromophore lies on its least-squares calculated plane and the four angles formed by the metal centre with the four donor atoms add up to exactly 360\u00b0. The Ni\u2014N and Ni\u2014S distances are within the usual range. This plane forms a 18\u00b0 angle with the uncoordinated furan ring, which is also highly planar.In the crystal of FUTRAN, Ni 5.E)-2-(furan-2-yl\u00admethyl\u00adene)hydrazine-1-carbo\u00adthio\u00adamide were dissolved in 30\u2005mL of methanol then 13\u2005mg (0.05\u2005mmol) of Ni(OOCCH3)2\u00b74H2O were added. The reaction mixture was kept in air at room temperature for slow evaporation. After ca 2\u20133\u2005d, orange crystals, suitable for X-ray analysis, were formed.17\u2005mg (0.1\u2005mmol) of (14H20N6NiO4S2 (M = 459.17); C 36.61 ; H 4.35 (4.39); N 18.26 (18.30) %. IR (KBr): 3372 \u03bd(OH), 2965 and 2854 \u03bd(NH), 1643 \u03bd(C=N) cm\u22121.Yield 81%, soluble in DMSO, ethanol and di\u00admethyl\u00adformamide and insoluble in non-polar solvents. Elemental analysis: C6.Uiso(H) = 1.2 or 1.5Ueq(C). O- and N-bound H atoms were located in difference Fourier maps  and refined with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O), with their positions fixed. Two reflections (001) and (010), affected by the beam stop, were omitted in the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023005182/jy2031sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023005182/jy2031Isup2.hklStructure factors: contains datablock(s) I. DOI: 2269284CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In all three title crystals, the cations are linked by O\u2014H\u22efO and/or C\u2014H\u22efO hydrogen bonds. The three-dimensional packing is further consolidated by strong halogen\u2013hydrogen and weak van der Waals inter\u00adactions. N,N-di\u00admethyl\u00adacetamide\u20131-(dimethyl-\u03bb4-aza\u00adnyl\u00adidene)ethan-1-ol tribromide (1/1), C4H9NO\u00b7C4H10NO+\u00b7Br3\u2212 or [(C4H9NO)\u00b7(C4H10NO)](Br3), (I), N,N-di\u00admethyl\u00adacetamide\u20131-(dimethyl-\u03bb4-aza\u00adnyl\u00adidene)ethan-1-ol di\u00adbromido\u00adiodate (1/1), C4H9NO\u00b7C4H10NO+\u00b7Br2I\u2212 or [(C4H9NO)\u00b7(C4H10NO)](Br2I), (II), and N,N-di\u00admethyl\u00adacetamide\u20131-(dimethyl-\u03bb4-aza\u00adnyl\u00adidene)ethan-1-ol di\u00adchlorido\u00adiodate (1/1), C4H9NO\u00b7C4H10NO+\u00b7Cl2I\u2212 or [(C4H9NO)\u00b7(C4H10NO)]\u00b7(Cl2I), (III), all the anions are almost linear in geometry and all the cations, except for the methyl H atoms, are essentially planar. In the crystal structure of (I), the cations are linked by pairs of C\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(8) ring motif. These dimers also exhibit O\u2014H\u22efO hydrogen bonding. Dimerized cation pairs and anions are arranged in columns along the a axis. In the crystal of (II), the cations are linked by pairs of O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming an R44(14) ring motif. These groups of cations and the anions form individual columns along the a axis and jointly reside in planes roughly parallel to (011). In the crystal of (III), cations and anions also form columns parallel to the a axis, resulting in layers parallel to the (020) plane. Furthermore, the crystal structures of (I), (II) and (III) are consolidated by strong halogen (Br and/or I and/or Cl)\u22efH and weak van der Waals inter\u00adactions. In addition to the structural evaluation, a Hirshfeld surface analysis was carried out.In the title compounds,  The cations, except for their methyl H atoms, are essentially planar [r.m.s. deviation = 0.041\u2005(1)\u2005\u00c5 for O1]. For (II), the angles and distances of the anion are Br1\u2014I1\u2014Br2 = 177.942\u2005(5)\u00b0, I1\u2014Br1 = 2.7244\u2005(2)\u2005\u00c5 and I1\u2014Br2 = 2.68597\u2005(19)\u2005\u00c5. These values are in agreement with data reported in the literature , I1 resides in the centre of inversion symmetry [Cl1\u2014I1\u2014Cl1\u00a0= 180.0\u00b0], with distances of I1\u2014Cl1 = 2.53973\u2005(18)\u2005\u00c5. The cations, except for their methyl H atoms, are planar and all reside on mirror planes.In the title compounds  Figs. 1 and 3 \u25b8,I), (II) and (III), the O\u2014C and N\u2014C bond distances of the cation all fall between single and double bond values, with C1\u2014N1 = 1.3134\u2005(17)\u2005\u00c5 and C1\u2014O1 = 1.2786\u2005(16)\u2005\u00c5 for (I), C1\u2014N1 = 1.3168\u2005(16)\u2005\u00c5, C5\u2014N2 = 1.3121\u2005(16)\u2005\u00c5, C1\u2014O1 = 1.2771\u2005(15)\u2005\u00c5 and C5\u2014O2 = 1.2794\u2005(15)\u2005\u00c5 for (II), and C1\u2014N1 = 1.3161\u2005(8)\u2005\u00c5 and C1\u2014O1 = 1.2750\u2005(8)\u2005\u00c5 for (III). The corresponding bond lengths of the three compounds are in good agreement with each other and with the literature.In (3.I), the cations are linked by pairs of C\u2014H\u22efO hydrogen bonds , forming inversion dimers with an et al., 1995x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a02). Dimerized cation pairs and anions are arranged in columns along the a axis , two cations are refined in the asymmetric unit. These cations are linked by pairs of O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming an a axis and reside in planes parallel to (011) , cations and anions are arranged in columns parallel to the a axis, forming layers parallel to the (020) plane (Table\u00a03I), (II) and (III) are consolidated by strong halogen (Br and/or I and/or Cl)\u22efH bonding inter\u00adactions, Coulombic attraction and weak van der Waals inter\u00adactions , (II) and (III) are 2.4224\u2005(15), 2.4278\u2005(14) and 2.4261\u2005(9)\u2005\u00c5, respectivly, and are thereby within the range (2.31\u20132.63\u2005\u00c5) found for short/strong classical hydrogen bonds , (II) and (III) were carried out and created with CrystalExplorer17.5 , (II) and (III) is given in Table\u00a04I), (II) and (III) are shown in Fig.\u00a010b)\u2013(d) and Table\u00a05I); 60.3% for (II); 88.9% for (III)], Br\u22efH/H\u22efBr , O\u22efH/H\u22efO [6.5% for (III)] and O\u22efH/H\u22efO  and C\u22efH/H\u22efC [2.0% for (III)] contacts.The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots over the cations of (I): space group, monoclinic P21/n, Z = 2; (II): space group, triclinic PZ = 2; (III): space group, monoclinic C2/m, Z = 2], may be the result of small deviations in the inter\u00adactions arising from the different crystal systems and packing, as well as from the variations in the anions of the compounds.The respective differences in the crystal structures of the three title compounds [aluminium(III)] bis\u00ad\u00adium hepta\u00adkis\u00ad(perchlorate)  tetra\u00adchloro\u00adgold(III) , the Al3+ ion is surrounded by dma mol\u00adecules (dma = di\u00admethyl\u00adacetamide) in an octa\u00adhedral arrangement. The dma mol\u00adecules are essentially planar. Three Al\u2014O\u2014C\u2014N torsion angles [138.8\u2005(8)\u2013149.3\u2005(4)\u00b0] are found to deviate significantly from 180\u00b0. The centrosymmetric cation has the bridging H atom at the centre of inversion. The planar structure is essentially the same as those reported for [H(dma)2]+ cations; the O\u22efO distance [2.386\u2005(8)\u2005\u00c5] is within the range (2.31\u20132.63\u2005\u00c5) found for short hydrogen bonds , the structure consists of distinct [AuCl4]\u2212 anions and [H(dma)2]+ cations, with the gold and the bridging H atoms located at centres of symmetry. The hydrogen bond is \u2018symmetrical\u2019 as a result of crystallographic requirements. The O\u22efO distance is 2.430\u2005(16)\u2005\u00c5. Thermal motion analysis indicates that methyl groups attached to nitro\u00adgen have higher rotational amplitudes, resulting in short apparent C\u2014H bond lengths [average 0.96\u2005(4)\u2005\u00c5] compared with the methyl group attached to a carbonyl C atom which has an average C\u2014H bond length of 1.02\u2005(2)\u2005\u00c5.In the crystal of HDMAAU , two N,N-di\u00admethyl\u00adacetamide mol\u00adecules in the asymmetric unit are connected to each other by an O\u2014H\u22efO hydrogen bond, essentially sharing the central H atom. These mol\u00adecules and the Br\u2014Br\u2014Br groups are arranged in columns parallel to the a axis. The arrangement is consolidated in the crystal packing by van der Waals inter\u00adactions between these columns.In the crystal of SEGMOG , the unit-cell parameters and the arrangement of the mol\u00adecules are relatively similar to the older structure (SEGMOG), while the H atom bridging the the two acetamides was not refined.In the crystal of SEGMOG01  hydrogen halides as orange colored solids. Single crystals of bis\u00ad hydrogen halides were obtained by slow crystallization from methanol.To a solution of di\u00admethyl\u00adacetamide  in 0.09\u2005mol of 38% hydro\u00adchloric or 40% hydro\u00adbromic acid under stirring and cooling in an ice\u2013water bath, 0.05\u2005mol iodine monochloride , iodine monobromide  or bromine  was added gradually. The mixture was stirred for 1\u2005h and the crystals were filtered off, dried and recrystallized from methanol to give the target bis\u00ad: 1664 (NCO). 1H NMR : \u03b4  12.51 , 3.28 , 3.19 , 2.45 ; 13C{1H} NMR : \u03b4 174.5, 39.7, 37.5, 19.9.Bright orange crystals (Rodygin 5.3.\u22121): 1606 (NCO). 1H NMR : \u03b4  10.72 , 3.28 , 3.19 , 2.46 ; 13C{1H} NMR : \u03b4 174.6, 39.6, 37.5, 20.1.Bright-orange crystals, yield 44% (10.2\u2005g), m.p. 343\u2013344\u2005K. IR (KBr), \u03bd (cm5.4.\u22121): 1611 (NCO). 1H NMR : \u03b4  9.98 , 3.25 , 3.17 , 2.41 ; 13C{1H} NMR : \u03b4 174.2, 39.4, 37.2, 19.8.Bright orange crystals, yield 75% (14\u2005g), m.p. 364\u2013365\u2005K. IR (KBr), \u03bd (cm6.I), (II) and (III), the C-bound H atoms were positioned geometrically, with C\u2014H = 0.98\u2005\u00c5 (for methyl H atoms), and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C). The hy\u00addroxy H atoms were found in the difference Fourier maps and their coordinates were refined freely, with Uiso(H) = 1.5Ueq(O). In (I), the H atom of the OH group is located in a special position  with an occupancy of 0.5 for the rrefined atom. In (II), the H atoms of the OH groups are disordered over two positions, with occupancies of 0.49 and 0.51. In (III), the H atom of the OH group was refined with an occupancy of 0.25 for its position close to an inversion centre in between the O atoms of two acetamides and simultaneously residing on a mirror plane.Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989023005509/yz2034sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989023005509/yz2034Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023005509/yz2034IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989023005509/yz2034IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 2271693, 2271692, 2271691CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Thus, we highlight thesections where these changes apply.In a recent Letter,Abstract: The DO\u2013Dbond dissociation energy has been reportedto be 5.41 \u00b1 0.10 eV, while considering EA(O) in the originalmanuscript. However, EA(OD) should be used instead, thus leading toa bond dissociation energy of 5.28 \u00b1 0.20 eV.Page 5365,left column, second paragraph; \u201cFrom the appearance...\u201dis reorganized and reads as follows:Table S4 togetherwith the BDE, the enthalpy of reaction can be obtained from \u0394Hr(OH\u2013) = D(H\u2013OH) \u2013 EA(OH) = 3.34 eV. In the charge transfer process,if we add the potassium ionization energy, OH\u2013 isexpected at 7.68 eV. The reactions threshold was obtained assumingno excess energy (E#), yet momentum conservationof the dissociating partners may impact on the lighter fragment kineticenergy, thus shifting the energy to a higher value. We note a differenceof \u223c1.1 eV for the energy loss data, which is certainly plausiblegiven the kinetic-energy release distribution of H\u2013 in Figure S3. Thus, from the appearanceenergy (AE) in the H2O energy loss spectrum at \u0394E \u2248 8.8 eV, one can obtain the HO\u2013Hbond dissociation energy (BDE) by taking the potassium ionizationenergy and the data from Table S4,2 i.e., D(HO\u2013H) = AE(OH\u2013) \u2013 IE(K) + EA(OH) \u2013 E#, yielding therefore D(HO\u2013H)= 5.19 \u00b1 0.20 eV which is in good agreement with the values 5.15eV 3 and 5.17eV.4 Following the same approach for D2O, the energy loss spectrum shows a threshold feature at \u0394E \u2248 9.0 eV. We obtain for the first time the DO\u2013Dbond dissociation energy to be D(DO\u2013D) = 5.28\u00b1 0.20 eV. In D2O the DO\u2013D energy value isslightly higher than the O\u2013D bond dissociation energy (5.176eV5), which is in agreement with its analogueH2O.Taking the values in Page 5366, right column, last paragraph; \u201cElectronicstatespectroscopy...\u201d reads as follows:2O/D2O was thoroughly discussedfrom the experimental K+ energyloss spectra obtained, from which the DO\u2013D bond dissociationenergy has been obtained for the first time to be 5.28 \u00b1 0.20eV.The electronic statespectroscopy of HfHg\u00b0) in reactions 2a.1\u20132b.2and 4a.1\u20134b.2are actually enthalpies of reaction (\u0394Hr). Table S2 decimal places forO\u2013 and OH\u2013 from H2Ohave been corrected; they now read 12.08 \u00b1 0.20 and 7.80 \u00b10.20.Enthalpies of formation (\u0394"}
{"text": "However, the difficulty in expanding cytotoxic \u03b3\u03b4T cells to an adequate number has been a major limitation to the efficacy of treatment in most cases. We successfully re-generated \u03b3\u03b4T cells from \u03b3\u03b4T cell-derived human induced pluripotent stem cells (iPSCs). The iPSC-derived \u03b3\u03b4T cells (i\u03b3\u03b4Ts) killed several cancer types in a major histocompatibility complex (MHC)-unrestricted manner. Single-cell RNA sequencing (scRNA-seq) revealed that the i\u03b3\u03b4Ts were identical to a minor subset of PB\u03b3\u03b4Ts. Compared with a major subset of PB\u03b3\u03b4Ts, the i\u03b3\u03b4Ts showed a distinctive gene expression pattern: lower CD2, CD5, and antigen-presenting genes; higher CD7, KIT, and natural killer (NK) cell markers. The i\u03b3\u03b4Ts expressed granzyme B and perforin but not interferon gamma (IFN\u03b3). Our data provide a new source for \u03b3\u03b4T cell-based immunotherapy without quantitative limitation.For a long time,   \u2022We successfully re-generated \u03b3\u03b4T cells from \u03b3\u03b4T cell-derived human iPSCs\u2022The re-generated \u03b3\u03b4T cells showed cytotoxicity against cancer cell lines\u2022Distinctive signatures of the re-generated \u03b3\u03b4T cells were identified ex vivo-expanded peripheral-blood-derived \u03b3\u03b4T cells. Cytotoxicity of i\u03b3\u03b4Ts against several cancer cell lines was exhibited in an MHC-unrestricted manner. The novel cell resource will advance off-the-shelf \u03b3\u03b4T cell-based immunotherapy.Murai et\u00a0al. successfully re-generated \u03b3\u03b4T cells from \u03b3\u03b4T cell-derived human iPS cells. Molecular signatures of the re-generated \u03b3\u03b4T cells (i\u03b3\u03b4Ts) were identical to those of a minor subset of  Therefoical use . Howeverical use . Furtherex\u00a0vivo expansion rate of PBMC-derived \u03b3\u03b4T cells varies widely from donor individual to individual; thus, ex\u00a0vivo-expanded autologous PB\u03b3\u03b4T cell therapy cannot be applied to all patients; (2) patients have to wait for the expansion of autologous cells but not for off-the shelf allogenic cells; and (3) an autologous approach would be associated with high costs. iPSCs have infinite proliferation ability: they show logarithmic growth for at least 100\u00a0days and \u223c1,028-fold expansion during 100\u00a0days  (Induced pluripotent stem cell (iPSC) technology may be able to overcome these limitations and enable us to realize off-the-self allogenic \u03b3\u03b4T cell-based therapy, which has several advantages over autologous \u03b3\u03b4T cells therapy: (1) the 2\u00a0weeks) . To gene2\u00a0weeks) , and re-2\u00a0weeks) .bona fide lymphocyte, including \u03b3\u03b4T cells, and should be categorized as cells resulting from an aberrant characteristic of lymphocytes derived from iPSCs, or abnormal cells. Previous studies have demonstrated that such abnormal cells can be derived from pre-rearranged TCR-carrying pluripotent stem cells or hematopoietic progenitors, and such iPSCs reportedly gave rise to abnormal T\u00a0cells expressing TCR, an NK cell marker NK1.1, and CD8\u03b1\u03b1  exhibited cytotoxicity against several cancer cell lines in an MHC-unrestricted manner. We identified distinctive molecular signatures of i\u03b3\u03b4Ts and clarified that the i\u03b3\u03b4Ts were identical to a minor subset of in\u00a0vitro embryoid body (EB)-mediated differentiation experiment showed that they could differentiate into three germ layers  stimulated with HMBPP for 1\u00a0week being composed of both \u03b3\u03b4TCR-positive and \u03b1\u03b2TCR-positive cells, CD3-positive i\u03b3\u03b4Ts contained no \u03b1\u03b2TCR-positive cells A. Genomiin i\u03b3\u03b4Ts B. Furthein i\u03b3\u03b4Ts , whereasin i\u03b3\u03b4Ts ).Figure\u00a0These data indicated that we successfully re-generated monoclonal \u03b39\u03b42 T\u00a0cells via \u03b3\u03b4T-iPSCs.A key advantage of \u03b3\u03b4T cells for cancer immunotherapy is that one type of \u03b3\u03b4T cell is applicable for various types of cancer in a human leukocyte antigen (HLA)-unrestricted manner . We therFirst, we labeled Jurkat cells with carboxyfluorescein diacetate succinimidyl ester (CFSE) as target cells, co-cultured with the i\u03b3\u03b4Ts as effector cells at an effector (E):target (T)\u00a0ratio of 2:1 and stained these cells with 7-aminoactinomycin-D (7-AAD) to identify dead cells, followed by flow cytometry (FCM). The no-effector condition showed that only approximately 5% of Jurkat cells were dead B, althouTo assess the cytotoxicity of i\u03b3\u03b4Ts toward solid tumor cells, we observed the co-culture of 62B3 \u03b3\u03b4T-iPSC line-derived i\u03b3\u03b4Ts with GFP-Huh-7 cells by time-lapse imaging. After 12\u00a0h of co-culture, the areas of GFP-Huh-7 cells decreased to 28.7%, 30.1%, and 64.5% of those in no-effector control culture in three independent experiments C and 3D.This video displays the continuous imaging of i\u03b3\u03b4Ts co-cultured with GFP-labeled Huh-7 cells at an E:T ratio of 2:1 from 0 to 6 h. The scale bar (upper left) indicates 100\u00a0\u03bcm.Next, to confirm the cytotoxicity of purified-i\u03b3\u03b4Ts, we co-cultured CD3-MACS-purified i\u03b3\u03b4T cells and tumor cells and quantified the tumor toxicity at an E:T ratio of 2:1 at 12\u00a0h using xCELLigence. Against Huh-7 cells, the purified i\u03b3\u03b4T and PB\u03b3\u03b4T cells showed no significant difference in cytotoxicity G. MoreovThese data demonstrated that the i\u03b3\u03b4Ts have cytotoxicity for at least four different types of cancer cells in an HLA-unrestricted manner. Moreover, we were able to catch i\u03b3\u03b4Ts coming into contact with GFP-Huh-7 cells and peeling off as time went on .We next performed several experiments to obtain insight into the mode of action of the i\u03b3\u03b4Ts. The co-culture of i\u03b3\u03b4Ts and Jurkat cells at various E:T ratios showed the dose-dependent cytotoxic effects of i\u03b3\u03b4Ts A and S3ENext, we investigated the mechanism by which i\u03b3\u03b4Ts exhibit cytotoxicity. Both blocking antibodies for \u03b3\u03b4TCR and NKG2D reduced the cytotoxicity of the purified i\u03b3\u03b4Ts,\u00a0suggesting that the i\u03b3\u03b4Ts recognize tumor cells by both\u00a0\u03b3\u03b4TCR and NKG2D C. PerforNotably, no i\u03b3\u03b4Ts were positive for IFN\u03b3. In contrast, most granzyme B-positive cells in PB\u03b3\u03b4T cells were positive for IFN\u03b3 D. This fWe compared the cell surface markers of i\u03b3\u03b4Ts with PB\u03b3\u03b4T cells by FCM E. Both dIn general, T\u00a0cells are divided into four subsets of naive or memory phenotypes corresponding to the CD45RA and CD27 expression patterns . Despitein\u00a0vitro for 7\u00a0days and CD3(+) \u03b3\u03b4TCR(+) cells were sorted. (iii) i\u03b3\u03b4Ts; differentiated cells from \u03b3\u03b4T-iPSC clone 62B3 (according to the protocol shown in \u03b3\u03b4T cells have been reported to have various subtypes  and it wTRDC(+), CD3E(+), CD4(\u2212), CD8A(+), and CD8B(\u2212) (TRDC(+), CD3E(+), CD4(\u2212) CD8A(\u2212), and CD8B(\u2212)  B and S4A CD8B(\u2212) B and S4Ased SELL B. Cells onocytes C. Cells and CD3E B, but diclusters D. We catThe t-SNE distribution of each sample and the fraction of clusters in each sample are shown in To examine the expression of major immune-related genes in each \u03b3\u03b4T subset, we created dot plots for T\u00a0cell-differentiation marker genes , cytokinCTSW, FCER1G, KLRC3, CD244, NKG7, as well as the cytotoxic marker perforin coding gene [PRF1]). Cells in \u03b3\u03b4T subset 2, the dominant population of in\u00a0vitro-expanded PB\u03b3\u03b4Ts stimulated with HMBPP, expressed immune checkpoint inhibitory receptors   and IFN\u03b3 and IFN\u03b3-inducing genes  . Cells in \u03b3\u03b4T subset 1, the main population of i\u03b3\u03b4Ts, were enriched for NK cell-related genes  E. The doB, IRF4)  were exp\u03b4T cells , was notectively C. The ex 1 and 3 A and 6C. 1 and 3 A and 6C.In order to investigate the reproducibility of the i\u03b3\u03b4T data, the expression of these marker genes in scRNA-seq data of i\u03b3\u03b4Ts prepared three times independently was shown by a heatmap. The similar expression patterns indicated that the gene expression of i\u03b3\u03b4Ts was reproducible E.Taken together, we successfully re-generated MHC-unrestricted cytotoxic \u03b3\u03b4T cells from iPSCs and clarified the\u00a0distinctive molecular signatures of iPSC-derived \u03b3\u03b4T cells.in\u00a0vivo.In the present study, we successfully re-generated CD3(+)\u03b3\u03b4TCR(+) cells from \u03b3\u03b4T cell-derived iPSCs. Although there have been reports of the re-generation of \u03b1\u03b2T cells from \u03b1\u03b2T cell-derived iPSCs , it was ex\u00a0vivo-expanded PB\u03b3\u03b4Ts, indicating that the cells resembling the major population of i\u03b3\u03b4Ts exist in adult PBMCs in nature but are not expandable with HMBPP stimulation, at least under the culture condition used in this study. Previously there have been many studies concerning the classification of human peripheral \u03b3\u03b4T cells. For example, the functions of \u03b3\u03b4T cells were reportedly separated into five subsets: IFN-\u03b3-producing, antigen-presenting, follicular B helper, regulatory \u03b3\u03b4T, and IL-17-producing cells , and CD5(\u2212) \u03b3\u03b4T cells were reported to be more cytotoxic than CD5(+) \u03b3\u03b4T cells . In addiNK cell-related markers were expressed in i\u03b3\u03b4Ts. A subset of authentic \u03b3\u03b4T cells reportedly expressed NK cell-related genes and recognize target cells by a similar mechanism to NK cells. In addition, it is reported that mimetic-\u03b3\u03b4 NKT cells, which expressed low T\u00a0cell-related genes and high NK cell-related genes, were induced from iPSCs . The shaWe herein demonstrated that our i\u03b3\u03b4Ts were completely negative for \u03b1\u03b2TCR and that they killed tumor cells in an MHC-independent manner. The negative expression of \u03b1\u03b2TCR may reduce the risk of graft-versus-host disease . For thiSeveral limitations of the present study should be addressed in our future studies. First, the induction efficiency of i\u03b3\u03b4Ts was not satisfactory, and we have not clarified what CD3(\u2212) cells existing after i\u03b3\u03b4Ts induction were. Second, it should be evaluated whether or not the i\u03b3\u03b4Ts attack non-cancer cells of KIR-ligand mismatch recipients. Third, the i\u03b3\u03b4T induction protocol established in this study used xenogenic serum and feeder cells, which are difficult for clinical applications. We are currently trying to generate i\u03b3\u03b4Ts under feeder-free and serum-free conditions (data not shown). Our technologies will advance off-the-shelf \u03b3\u03b4T cell-based immune therapy.This study did not generate new unique reagents.3 cells and cultured in StemFit medium .Seven days before induction, human \u03b3\u03b4T-iPSCs were seeded onto a six-well plate at a density of 2.0\u00a0\u00d7\u00a010On day 0, the medium was completely replaced by StemFit medium supplemented with 4\u00a0\u03bcM CHIR99021 , 80\u00a0ng/mL BMP4 , and 80\u00a0ng/mL vascular endothelial growth factor (VEGF) . On day 2, the medium was replaced by Essential 6 medium  supplemented with 2\u00a0\u03bcM SB431542 , 50\u00a0ng/mL bFGF , 50\u00a0ng/mL SCF , and\u00a080\u00a0ng/mL VEGF. On day 4, the medium was replaced by StemPRO-34 SFM  supplemented with 2\u00a0mM L-glutamine, 50\u00a0ng/mL IL-3 , 50\u00a0ng/mL IL-6 , 50\u00a0ng/mL FLT3L , 50\u00a0ng/mL SCF, 20\u00a0ng/mL VEGF, and 10 IU/mL EPO .On days 6 and 8, the medium was replaced with StemPRO-34 SFM supplemented with 2\u00a0mM L-glutamine, 50\u00a0ng/mL IL-6, 50\u00a0ng/mL SCF, and 10 IU/mL EPO.On day 10, hematopoietic cells were transferred into wells co-cultured with feeder cells. Floating cells and supernatant were collected in the tube. Adhesive cells were dissociated with Accutase , and incubated at 37\u00b0C for 10\u00a0min. Supernatant was returned to the well, pipetted, and filtered using a 35-\u03bcm cell strainer. After centrifugation at 1,200\u00a0rpm for 4\u00a0min, cells were suspended in OP9 medium supplemented with 10\u00a0ng/mL SCF, 10\u00a0ng/mL TPO , 5\u00a0ng/mL IL-7 , 5\u00a0ng/mL FLT3L, and 100\u00a0\u03bcg/mL L-ascorbic acid . Cells were reseeded to the same well and incubated at 37\u00b0C for 30\u00a0min. Without pipetting, supernatant and floating cells were transferred into a new well confluent with pre-seeded OP9/N-DLL1 cells.On day 12, half of the medium was changed and cells were transferred into new wells with fresh OP9/N-DLL1 cells by vigorous pipetting. Then, half of the medium was changed every other day and cells were transferred onto fresh OP9/N-DLL1 cells every 6\u00a0days.On day 30, we collected cells with Accutase, similarly to day 10. Cells were suspended with RPMI1640 medium supplemented with 10% FBS, 1\u00a0nM HMBPP , 100 IU/mL IL-2 , and 10\u00a0\u03bcM 2-mercaptoethanol and seeded onto new plates in a feeder-free condition. Half of the medium was changed every other day. After more than a week of stimulation, cytotoxicity was analyzed.The day before the targeted scRNA-seq analysis, CD3(+)\u03b3\u03b4TCR(+) cells were sorted on a BD FACS Aria III from PB\u03b3\u03b4Ts and i\u03b3\u03b4Ts that were stimulated with HMBPP for the indicated days as described above. To infer the origin of the sample, all cells were labeled with multiplex sample tags. Single-cell capture and cDNA library preparation were performed using a BD Rhapsody Single-Cell Analysis System with a BD Human Single-Cell Multiplexing Kit  and BD Human Immune Response Targeted Panel for Human , which contains 399 primer pairs, targeting 397 different genes, according to the manufacturer\u2019s recommendations. The concentration, size, and integrity of the resulting PCR products were assessed using a Qubit High-Sensitivity dsDNA Kit.Sequencing was performed using an Illumina HiSeq X  in Macrogen . Fastq files were uploaded to the Seven Bridges Genomics online platform. The obtained counts were adjusted by distribution-based error correction (DBEC), an error correction algorithm developed by BD Biosciences. DBEC data were then loaded into Seurat (version 4.0.4.). Cells were then clustered using a resolution of 0.03 and visualized by t-SNE. The Seurat functions FeaturePlot, DotPlot, DoHeatmap, and Vlnplot were used to visualize the gene expression with feature plot, dot plot, heatmap, and violin plot, respectively. Markers for a specific cluster against all remaining cells were found by using the Seurat function FindAllMarkers.GSE194072.ScRNA-seq data have been deposited in GEO under accession number Data are expressed as the mean\u00a0\u00b1 SD. Differences between two groups were analyzed using a paired t test. Statistical analyses were performed using Microsoft Excel 2013 and EZR. p values of <0.05 were considered statistically significant.Conceptualization, T.A; methodology, N.M; software, T.A. and M.K.-A; validation, M.K.-A.; formal analysis M.K.-A.; investigation, N.M.; resources, N.M.; writing\u00a0\u2013 original draft, N.M.; writing\u00a0\u2013 review\u00a0& editing, T.A., M.K.-A.; supervision, T.A. and H.T.; project administration, T.A."}
{"text": "The quinoxaline unit in the title mol\u00adecule is slightly puckered [dihedral angle between the rings = 2.07\u2005(12)\u00b0] while the whole mol\u00adecule adopts an L-shaped conformation. The packing in the crystal is governed by C\u2014H\u22efO hydrogen bonds and slipped \u03c0-stacking inter\u00adactions. 18H16N4O5, is slightly puckered [dihedral angle between the rings = 2.07\u2005(12)\u00b0] while the whole mol\u00adecule adopts an L-shaped conformation. Intra\u00admolecular hydrogen bonding determines the orientation of the substituted phenyl ring and the amide nitro\u00adgen atom is almost planar. The packing in the crystal is governed by C\u2014H\u22efO hydrogen bonds and slipped \u03c0-stacking inter\u00adactions.The quinoxaline unit in the title mol\u00adecule, C The oris Table\u00a01. H3A mayn Table\u00a01. The quic-axis direction \u2005\u00c5, dihedral angle = 2.07\u2005(10)\u00b0, slippage alternates between 1.40 and 1.28\u2005\u00c5 along the stack]. The \u03c0-stacking is reinforced by C8=O1\u22efCg1 inter\u00adactions, where Cg1 is the centroid of the C1/C6/N1/C7/C8/N2 ring: O1\u22efCg1 = 3.3333\u2005(16)\u2005\u00c5, C8\u22efCg1 = 3.689\u2005(2)\u2005\u00c5, C8=O1\u22efCg1 = 96.89\u2005(2)\u00b0. The stacks are linked by C10\u2014H10A\u22efO2 and C16\u2014H16\u22efO4 hydrogen bonds -one was dissolved in 25\u2005ml of di\u00admethyl\u00adformamide, then 1.53\u2005g (6.24\u2005mmol) of 2-chloro-N-(4-meth\u00adoxy-2-nitro\u00adphen\u00adyl)acetamide were added followed by 1.0\u2005g (7.5\u2005mmol) of potassium bicarbonate, and a spatula tip of BTBA [2-benzyl\u00adsulfanyl-5-(tri\u00adfluoro\u00admeth\u00adyl)benzoic acid] was used for the phase-transfer catalysis. The reaction was stirred for 2\u2005h under reflux at 80\u00b0C. When the starting reagents had completely reacted, 500\u2005ml of distilled water were added and a few minutes later the product precipitated. This was filtered, dried and recrystallized from hot ethanol solution to yield light-yellow plate-like crystals of the title compound.A mass of 1.00\u2005g (6.24\u2005mmol) of 3-methyl\u00adquinoxalin-2 global, I. DOI: 10.1107/S2414314623001918/hb4426Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623001918/hb4426Isup3.cmlSupporting information file. DOI: 2245645CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this DFT mechanistic work, a novel substrate\u2010dependent catalytic mechanism is disclosed involving cooperative Ca\u2212H\u2212Ca bridges for H2 isotope exchange, competitive Ca\u2212H\u2212Ca bridges and terminal Ca\u2212H bonds for anti\u2010Markovnikov addition of unactivated 1\u2010alkenes, and terminal Ca\u2212H bonds for Markovnikov addition of conjugation\u2010activated styrene. THF\u2010coordination plays a key role in favoring the anti\u2010Markovnikov addition while strong cation\u2010\u03c0 interactions direct the Markovnikov addition to terminal Ca\u2212H bonds.Recently, it was shown that the double Ca\u2212H\u2212Ca bridged calcium hydride cation dimer complex [LCaH Calcium hydride cation dimer catalysis: Dispersion\u2010corrected DFT calculations reveal that the same double Ca\u2212H\u2212Ca bridged calcium hydride cation dimer catalyst [LCaH2CaL]2+\u22c5THF shows a novel substrate\u2010dependent catalytic activity, involving cooperative Ca\u2212H\u2212Ca bridges for efficient H2 isotope exchange, terminal Ca\u2212H bond for the Markovnikov addition of conjugation\u2010activated styrene, and competitive Ca\u2212H\u2212Ca bridges and terminal Ca\u2212H bonds for the anti\u2010Markovnikov addition of unactivated 1\u2010alkenes. In THF solution, the weakly (or non\u2010) coordinating counter\u2010anions BAr4\u2212 should be solvated into separated ions, and thus not considered further. Consistent with experiment,2+1 is indeed \u22122.8\u2005kcal/mol exergonic, with a decisive stabilizing dispersion contribution of \u22127.6\u2005kcal/mol otherwise the coordination should be 4.8\u2005kcal/mol endergonic and thus thermodynamically unstable. For comparison, the THF coordination to the cation monomer +1\u2009m is only \u22121.5\u2005kcal/mol exergonic with a smaller dispersion contribution of \u22124.2\u2005kcal/mol. The formation of double Ca\u2212H\u2212Ca bridged 2+1 from two +1\u2009m monomers is \u221218.4\u2005kcal/mol exergonic again with a sizable dispersion contribution of \u22126.2\u2005kcal/mol. The THF coordination to 2+1\u22c5THF smoothly leads to two +1\u2009m\u22c5THF cation monomers that is 15.3\u2005kcal/mol endergonic, indicating a rapid dimer\u2010to\u2010monomer equilibrium even at room temperature (see Supporting Information Table\u2005S1).To gain deep mechanistic insight into the cation dimer 22Ca(BDI)]2 is about 7.7\u2005kcal/mol higher in free energy than two (THF)(BDI)CaH monomers in benzene solution,2Ca(BDI)] is 40.4\u2005kcal/mol lower in enthalpy than two (BDI)CaH monomers in gas\u2010phase,In two related mechanistic studies on 1\u2010alkene hydrogenation reactions, the THF\u2010coordinated [(THF)(BDI)CaH]2+1\u22c5THF, the anti\u2010Markovnikov addition of unactivated 1\u2010alkene CH2=CHR (R=3\u2010cyclohexenyl) to a Ca\u2212H\u2212Ca bridge of 2+1 after THF\u2010elimination is 3.6\u2005kcal/mol endergonic over a sizable free energy barrier of 23.8\u2005kcal/mol (via transition state 2+TS1) to selectively form the dinuclear complex 2+A [LCaHR'CaL]2+ containing both a Ca\u2212H\u2212Ca and a Ca\u2212R\u2019\u2212Ca  bridge. The alternative Markovnikov addition with the hydride added to the terminal alkene carbon is kinetically 7.6\u2005kcal/mol less favorable . The subsequent H2 addition over the Ca\u2212R\u2019\u2212Ca bridge of 2+A is highly exergonic and kinetically 5.8\u2005kcal/mol more favorable (via 2+TS2) to form the hydrogenated product CH3CH2R along with regenerated 2+1\u22c5THF after THF coordination. Such a catalytic 1\u2010alkene hydrogenation is thus \u221223.7\u2005kcal/mol exergonic over a sizable barrier of 23.8\u2005kcal/mol involving anti\u2010Markovnikov alkene addition to cooperative Ca\u2212H\u2212Ca bridges.As shown in Figure\u2005+1\u2009m\u22c5THF that is 7.8\u2005kcal/mol higher in free energy than 2+1\u22c5THF, the anti\u2010Markovnikov addition of unactivated CH2=CHR to the terminal Ca\u2212H bond is still 4.0\u2005kcal/mol endergonic but over nearly the same free energy barrier of 23.8\u2005kcal/mol (via +mTS1) to selectively form the calcium alkyl complex +mA [LCaHR\u2019\u22c5THF]+, with the alternative Markovnikov addition being kinetically 6.0\u2005kcal/mol less favorable . The subsequent hydrogenolysis of the Ca\u2212C bond of +mA with H2 is highly exergonic and kinetically 2.9\u2005kcal/mol more favorable (via +mTS2) to form the hydrogenated product CH3CH2R along with regenerated +1\u2009m\u22c5THF. When cyclohexene is used as an internal alkene substrate in +1\u2009m\u22c5THF catalyzed hydrogenation, a 3.3\u2005kcal/mol higher barrier  is found for the anti\u2010Markovnikov addition to the terminal Ca\u2212H bond, consistent with the experimentally observed selective hydrogenation of terminal alkene.On the other hand, via the THF\u2010coordinated cation monomer +1\u2009m is kinetically 0.7\u2005kcal/mol less reactive  than that of +1\u2009m\u22c5THF towards CH2=CHR addition, mainly due to a less Lewis\u2010basic hydride (Mulliken atomic charges: \u22120.16 e in +1\u2009m vs. \u22120.53 e in +1\u2009m\u22c5THF). Together with the positive THF affinity of +1\u2009m, this leads to a 2.1\u2005kcal/mol higher barrier of 25.9\u2005kcal/mol for CH2=CHR addition without the coordinating THF. Interestingly, despite nearly the same free energy barriers  at 298\u2005K for the competitive mechanisms via 2+TS1 and +mTS1, our DFT calculations show that the former via the solvent\u2010free dimer 2+1 becomes kinetically 1.4\u2005kcal/mol more favorable than the latter via the THF\u2010coordinated +1\u2009m\u22c5THF  upon heating at 60\u2009\u00b0C (333\u2005K) in experiment,2+1\u22c5THF to reach the solvent\u2010free 2+TS1. In contrary to the usual intuition that the dimer\u2010to\u2010monomer conversion should be favored upon heating due to favorable entropy effects, our DFT calculations show that the equilibrium of 2+1\u22c5THF+THF\u2192+1\u2009m\u22c5THF++1\u2009m\u22c5THF in solution is hardly affected by such temperature change due to negligible entropy difference with an unchanged number of molecules on both sides (see Supporting Information Table\u2005S1).Interestingly, after THF elimination, the terminal Ca\u2212H bond of solvent\u2010free 2 isotope exchange may occur via one of two cooperative Ca\u2212H\u2212Ca bridges of the solvent\u2010free cation dimer 2+1 over a low barrier of 16.9\u2005kcal/mol (via 2+TS3) after THF\u2010elimination from stable 2+1\u22c5THF catalyst. Interestingly, three exchanging hydrogen atoms are placed evenly between two calcium ions and perpendicular to the remaining Ca\u2212H\u2212Ca bridge, suggesting potentially strong cooperative effects. With the coordinating THF within 2+1\u22c5THF, similar H2 isotope exchange (via 2+TS3a) becomes kinetically 4.5\u2005kcal/mol less favorable. On the other hand, facile H2 isotope exchange may also occur via terminal Ca\u2212H bonds that are more reactive but higher in free energy than Ca\u2212H\u2212Ca bridges. Indeed, the THF\u2010coordinated cation monomer +1\u2009m\u22c5THF is intrinsically 3.9\u2005kcal/mol (via +mTS3) more reactive than 2+1 for H2 isotope exchange but 7.8\u2005kcal/mol higher in free energy, eventually leading to a 3.9\u2005kcal/mol higher barrier. Interestingly, the solvent\u2010free cation monomer +1\u2009m with a less Lewis\u2010basic hydride turns out to be intrinsically 3.9\u2005kcal/mol less reactive than +1\u2009m\u22c5THF in mediating H2 isotope exchange, which is further disfavored by its positive THF affinity of 1.4\u2005kcal/mol. It is thus clear that very efficient H2 isotope exchange observed at room temperature2+1 over a low barrier of 16.9\u2005kcal/mol (via 2+TS3) rather than recently proposed terminal Ca\u2212H bonds.As seen in Figure\u20052+1\u22c5THF, the Markovnikov addition of styrene (CH2=CHPh) as a typical \u03c0\u2010conjugation\u2010activated 1\u2010alkene to a cooperative Ca\u2212H\u2212Ca bridge of 2+1 after THF\u2010elimination is 0.2\u2005kcal/mol endergonic over a sizable barrier of 24.3\u2005kcal/mol (via 2+TS4), selectively leading to the dinuclear calcium\u2010complex 2+B [LCaHR\u201cCaL]2+ containing both a Ca\u2212H\u2212Ca and a Ca\u2212R\u201d\u2212Ca Ph) bridge. Note that the hydride is now added to the terminal rather than the inner alkene carbon as directed by strong Ca+\u2026Ph cation\u2010\u03c0 interactions; the anti\u2010Markovnikov addition encounters a 2.7\u2005kcal/mol higher barrier  and thus is kinetically disfavored. The subsequent hydrogenolysis of the Ca\u2212R\u201d\u2212Ca bridge of 2+B with H2 is highly exergonic and kinetically 7.7\u2005kcal/mol more favorable (via 2+TS5) to form the hydrogenated product CH3CH2Ph along with regenerated catalyst 2+1\u22c5THF after THF\u2010coordination. Such dimeric catalytic mechanism is \u221222.3\u2005kcal/mol exergonic over a sizable barrier of 24.3\u2005kcal/mol involving Markovnikov 1\u2010alkene addition to cooperative Ca\u2212H\u2212Ca bridges.As shown in Figure\u20052+1\u22c5THF, the Markovnikov styrene addition to the terminal Ca\u2212H bond of the solvent\u2010free cation monomer +1\u2009m (via +mTS4) is now kinetically very efficient and again directed by strong Ca+\u2026Ph ion\u2010\u03c0 interaction, which is now \u22127.7\u2005kcal/mol exergonic over a moderate barrier of 20.6\u2005kcal/mol to selectively form the calcium benzyl complex +mB LCaR\u201c+. The alternative anti\u2010Markovnikov styrene addition is 6.4\u2005kcal/mol less favorable  and is kinetically highly disfavored. The subsequent H2 hydrogenolysis of the Ca\u2212C bond of +mB is \u221214.6\u2005kcal/mol exergonic over a moderate barrier of 19.0\u2005kcal/mol (via +mTS5) to form the hydrogenated product CH3CH2Ph along with regenerated catalyst 2+1\u22c5THF after +1\u2009m dimerization and THF\u2010coordination, which is kinetically 1.6\u2005kcal/mol more favorable than the preceding Markovnikov styrene addition. It is thus clear that the catalytic styrene hydrogenation via the terminal Ca\u2212H bond of the solvent\u2010free cation monomer +1\u2009m encounters only a moderate barrier of 20.6\u2005kcal/mol, which is kinetically 3.7\u2005kcal/mol more favorable than that via cooperative Ca\u2212H\u2212Ca bridges of the solvent\u2010free cation dimer 2+1 and reasonably accounts for the efficient styrene hydrogenation observed at room temperature.Interestingly, starting from the stable complex 2 isotope exchange reactions with the same calcium hydride cation dimer catalyst 2+1\u22c5THF. It is shown that cooperative Ca\u2212H\u2212Ca bridges of solvent\u2010free dimer 2+1 are favored for H2 isotope exchange, competitive Ca\u2212H\u2212Ca bridges of 2+1 and the terminal Ca\u2212H bond of cation monomer +1\u22c5THF are involved in the anti\u2010Markovnikov addition of unactivated 1\u2010alkenes, while the terminal Ca\u2212H bond of solvent\u2010free monomer +1 is preferred for the Markovnikov addition of conjugation\u2010activated styrene as directed by strong cation\u2010\u03c0 interactions. The novel mechanism can reasonably explain the known experimental observations and may be a useful guide for rational catalyst design.Extensive dispersion\u2010corrected DFT calculations disclose a novel substrate\u2010dependent catalytic mechanism of 1\u2010alkene hydrogenation and Hsolv=3.18\u2005\u00c5). The density\u2010fitting RI\u2212J approachAll DFT calculations were performed with the TURBOMOLE 7.4 suite of programs.More accurate solvation free energies in THF solution were computed with the COSMO\u2010RS modelThe authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "P21/c symmetry with four mol\u00adecules in the unit cell. The imidazole ring is rotated 80.7\u2005(1)\u00b0 relative to the phenyl ring. Inter\u00admolecular stabilization primarily results from close contacts between the N-atom at the 3-position on the imidazole ring and the C\u2014H bond at the 4-position on the neighboring DippIm.At 106\u2005(2)\u2005K, the title mol\u00adecule has monoclinic  15H20N2 or DippIm, is reported. At 106\u2005(2)\u2005K, the mol\u00adecule has monoclinic P21/c symmetry with four mol\u00adecules in the unit cell. The imidazole ring is rotated 80.7\u2005(1)\u00b0 relative to the phenyl ring. Inter\u00admolecular stabilization primarily results from close contacts between the N atom at the 3-position on the imidazole ring and the C\u2014H bond at the 4-position on the neighboring DippIm, with ar\u00adyl\u2013aryl distances outside of the accepted distance of 5\u2005\u00c5 for \u03c0-stacking.The crystal structure of the title compound, C They are precursors in many synthetic processes and find use in pharmaceuticals and agrochemicals to create anti\u00adfungal agents and fungicides  in H2O, followed by addition of H2NCH2CH(OEt2), and acidic workup with HCl and HNO3  ligands, which are a common ligand class for organometallic chemistry and catalysis  or potassium bis\u00ad(tri\u00admethyl\u00adsil\u00adyl)amide (KHMDS) to form the free carbene ligands  reported by our group  is reported.Few aryl\u00adimidazoles have been structurally characterized, with 1--12.DippIm crystallizes as depicted in Fig.\u00a01MesIm of 106.44\u2005(16), 105.65\u2005(17), 110.89\u2005(18), 104.54\u2005(17), and 112.48\u2005(17)\u00b0, respectively  and 1.3759\u2005(16)\u2005\u00c5, respectively \u2005\u00c5, C1\u2014N2 = 1.316\u2005(3)\u2005\u00c5, C2\u2014C3 = 1.356\u2005(3)\u2005\u00c5, N1\u2014C3 = 1.384\u2005(2)\u2005\u00c5, and N2\u2014C2 = 1.382\u2005(3)\u2005\u00c5 \u2005\u00c5 between N1\u2014C1 and a longer bond of 1.3153\u2005(16)\u2005\u00c5 between C1\u2014N2, likely due to steric effects of the aryl group. The backbone imidazole C2\u2014C3 bond distance of 1.3578\u2005(16)\u2005\u00c5 is consistent with a C3.Mercury program\u2019s centroid algorithm -1H-imidazole. A SciFinder search  of colorless crystals. The product was characterized with 1H NMR and the results were consistent with reported literature values  I. DOI: 10.1107/S2056989023009179/oi2001Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023009179/oi2001Isup3.cmlSupporting information file. DOI: 2302037CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: Neural Dev 18, 1 (2023)10.1186/s13064-022-00169-1The authors would like to correct errors and update two figures in the original publication of the article .1. Page 2, \u201cAll mouse lines were backcrossed for at least 6 generations\u201d corrected to \u201cAll mouse lines were backcrossed for at least 4 generations\u201d.2. Page 4, \u201c0.1\u00a0M boric acid pH 8\u201d corrected to \u201c0.1\u00a0M sodium borate pH 8\u201d.3. Page 4, after \u201cRFP goat polyclonal Rockland Immunochemicals 200-101-379 1:500\u201d and before \u201cRFP rabbit polyclonal Rockland Immunochemicals 600-401-379 1:500\u201d, addition of \u201cRFP guinea pig polyclonal Frontier Institute MSFR105900 1:500\u201d.4. Page 4, \u201cTo our knowledge, this mouse line was not previously characterized.\u201d corrected to \u201cTo our knowledge, this mouse line was not previously characterized in detail.\u201d.2\u201d corrected to \u201cEGFP\u2009+\u2009KI-67\u2009+\u2009ASCL1\u2009+\u2009cells, 3373\u2009\u00b1\u2009532 cells per mm2\u201d.5. Page 6, \u201cKI-67\u2009+\u2009ASCL1\u2009+\u2009EGFP\u2009+\u2009cells, 3373\u2009\u00b1\u2009532 cells per mm6. Page 6, \u201cConsistent with the notion that the EGFP\u2009+\u2009KI-67- ASCL1- cells are quiescent B1 type stem cells\u201d corrected to \u201cConsistent with the notion that at least some of the EGFP\u2009+\u2009KI-67- ASCL1- cells are quiescent B1 type stem cells\u201d.7. Page 12, \u201call of the RFP\u2009+\u2009postnatal radial glial cells had cell body under the ventricular wall and contacted the ventricle with an apical extension .\u201d corrected to \u201calmost all of the RFP\u2009+\u2009postnatal radial glial cells had cell body under the ventricular wall and contacted the ventricle with an apical extension .\u201d8. Figure\u00a09. Figure"}
{"text": "This novel combination of a stereochemical probe and isotopic labeling in a silicon\u2010stereogenic compound opens new analytic possibilities to study stereochemical courses of reactions with the aid of chiral silanols mechanistically.A silicon\u2010stereogenic aminosilanol was isolated in excellent diastereomeric ratio and the absolute configuration was determined. The silanol is configurative and condensation stable in solution and shows stereoselective transformations with a clean stereospecific pathway in follow\u2010up reactions, which leads to the isolation of a silicon\u2010stereogenic zinc complex and siloxane compounds. Investigations with  Silanols are important industrial building blocks for the functionalization of surfaces. In this research, one silicon\u2010stereogenic silanol was selectively synthesized and analyzed. By using an innovative combination of this stereochemical probe and isotope labeling, a configurationally stable chiral silanol was studied, providing new insights into mechanistic studies. Silanols are a central class of compounds in silicon chemistry and are widely used in synthesis,4, 5 cHowever, the preparation of Si\u2010chiral compounds has proven challenging in the past due to limited access to suitable prochiral or chiral precursors.24, 25Despite these initial findings on the limited configurational stability of silanols in solution, this aspect was not investigated further. Questions arise here, whose answers are essential in order to maximize the potential applications of chiral silanols. How stable is the configuration of chiral silanols in solution? Which subsequent reactions can be realized without loss of stereo information to make further functional components accessible?1  like siloxides and siloxanes.Thus, it can be used as an efficient mechanistic probe whose potential can be extended by 1 was synthesized by the acid\u2010catalyzed hydrolysis of the corresponding methoxysilane . Silanol 1 crystallizes in the space group P21. The quality of the crystal structure allowed the localization and free refinement of all protons. Two silanol molecules were observed in the asymmetric unit. These pack with the molecules generated by symmetry operations along the a\u2010axis to form long, chain\u2010like structures and are connected by intermolecular hydrogen bonds between the hydroxyl group of silanol 1 and the amine function of the next silanol.After hydrolysis, silanol 1 would be configurationally stable. Moreover, silanol 1 does not show condensation to the siloxane to provide the conditions for clean conversion reactions. For this purpose, the silanol was dissolved in different solvents and 1H\u2010 and 29Si\u2005NMR spectra of the compound were recorded over a period of several days  and THF (8\u2005days) also showed high stability of silanol 1 in the time periods studied.In the following, conditions were sought in which silanol 1 under the conditions was confirmed, it was converted in first transformation reactions. The focus was on the selective synthesis of chiral siloxanes and siloxides. In this case, access to Si\u2010chiral representatives is of great interest, especially for the development of new materials. In addition, the metallated siloxides often show outstanding catalytic activity and access to Si\u2010stereogenic ligands could open the development of new components for chiral catalysis. to be able to detect the minor diastereomer as well. To ensure constant experimental conditions, the solution was stored in the refrigerator (T=4\u2009\u00b0C) for the duration of the experiment.For this purpose, a THF solution of silanol r Scheme\u2005. The comSSi/RSi) were determined after derivatization to siloxane 5. In parallel, the most intense oxygenated molecule fragments were used to determine the respective proportions of 18O in the corresponding diastereomers by GC/EI\u2010MS. The evaluation of the experiments shows an unexpectedly long stability of the configuration at the silicon center, which at first glance suggests no exchange with water. However, at the same time, the incorporation of large amounts of 18O into the diastereomers of silanol 1 is observed, making the labeled species the major components in solution at the end of the experimental period. Since this exchange occurs without loss of stereochemical information, it can be concluded that the reaction proceeds cleanly with retention of the configuration.During the experiment, samples were taken at regular intervals and the corresponding ratios of the diastereomers \u2010isomer exchanges with water faster than the (RSi)\u2010isomer of 1. It is possible that the amino substituent influences the exchange process through the formation of hydrogen bonds.These show that a stable configuration is not necessarily associated with frozen reactivity, since initial experiments of chiral silanol 1 that proceed in THF with retention of the configuration, thus ensuring long term stability of the configuration in the aqueous environment. The combination of a stereochemical probe and isotopic labeling experiments opens the possibility for large\u2010scale mechanistic studies of the central processes of silanols, which could provide access to new synthesis opportunities for silanol\u2010based materials.In summary, we were able to demonstrate access to a Si\u2010chiral silanol that is stable to configurational changes and to condensation reactions in solution, which can be transformed in clean stereochemical transformations to siloxanes and siloxides. In addition, an isotope labeling experiment revealed hidden exchange processes of water with silanol General remarks: All reactions with oxygen\u2010 and moisture\u2010sensitive compounds were performed under an atmosphere of argon with Schlenk\u2010techniques in dried solvents. The solvents were purified and dried by distillation over sodium and storage under argon atmosphere. Commercially available reagents were used without further purification except for phenylmethyldimethoxysilane, which was distilled and stored over molsieve (4\u2005\u00c5) in argon atmosphere. The NMR spectra were measured on a Bruker Avance III HD NanoBay \u2013 400\u2005MHz, 500\u2005MHz Bruker Avance NEO, 600\u2005MHz Bruker Avance III HD and 500\u2005MHz Agilent Technologies DD2 spectrometer at 25\u2009\u00b0C. Chemical shifts (\u03b4 in ppm) are referred to tetramethylsilane (TMS), with the deuterium signal of the solvent serving as internal lock and the residual solvent signal as additional reference 1H\u2005NMR \u03b4 (C6D5H)=7.16\u2005ppm). Signals were assigned with the help of HSQC experiments. For the multiplicities following abbreviations were used: s=singlet, br=broad signal, d=doublet, q=quartet. In diastereomeric associations, diastereomeric signals were assigned to the major diastereomer (Dmaj) and the minor diastereomer (Dmin) if distinguishable. For spectra measured in non\u2010deutered solvents, a capillary with C6D6 was added and served as an internal standard. 13C\u2005NMR Spectra were measured with broadband decoupling and referred to the signal of the solvent [{1H}13C\u2005NMR \u03b4 (C6D6)=128.39\u2005ppm]. {1H}29Si\u2005NMR spectra were as inverted gated with TMS as external standard. Single crystal X\u2010ray diffraction for compounds 1 and 6 were conducted on a Bruker D8 Venture four\u2010circle diffractometer by Bruker AXS GmbH using a PHOTON II CPAD detector by Bruker AXS GmbH. X\u2010ray radiation was generated by a microfocus source I\u03bcS Mo by Incoatec GmbH with HELIOS mirror optics and a single\u2010hole collimator by Bruker AXS GmbH. For the data collection, the programs APEX 4 Suite (v.2020.10\u20100) with the integrated programs SAINT (integration) and SADABS (absorption correction) by Bruker AXS GmbH were used.MiTeGen were used for mounting. For mass spectrometric evaluation a GC/EI\u2010MS system with a nominal\u2010resolution ISQ mass spectrometer coupled to a Thermo Trace GC Ultra oven and a direct probe controller from Thermo Fischer Scientific was used. The capillary column used was an OPTIMA  from Macherey\u2010Nagel. Helium was used as the carrier gas. For high resolution mass spectrometry data a LTQ\u2010Orbitrap (Linear Trap Quadrupole Orbitrap) from Thermo Fischer Scientific coupled to a Shimadzu HPLC consisting of a CBM\u201020A communication module, a SPD\u2010M30A UV detector, a CTO\u201020AC column oven, a SIL\u201030AC autosampler, a LC\u201020ADXR pump system, and a DGU\u201020A5R degasser unit were used. Elemental analyses were performed with the elemental analyzer vario MICRO cube from the company Elementar and the weighing of the substance quantities was done with the microbalance Cubis MSE3.6P from the company Sartorius. Optical rotations were measured with an A. Kr\u00fcss Optical polarimeter operating on the sodium D\u2010line (589\u2005nm) using a quartz glass cuvette (1\u2005mL) and are reported as: [\u03b1]DT. The melting point for compound 1 was obtained using a B\u00fcchni M\u2010560 melting point apparatus and the resulting value is non\u2010corrected.Using Olex2, the structures were solved with the ShelXT structure solution program using Intrinsic Phasing and refined with the ShelXL refinement package using Least Squares minimization. MicroGrippers from Compound (S)\u20102: (S)\u20107  was suspended portion wise in 95\u2009% formic acid  under ice cooling and 37\u2009% formaldehyde solution  was subsequently added portion wise. The reaction solution was then stirred for 6\u2005h under reflux and then for 12\u2005h at room temperature. Subsequently, the reaction solution was adjusted to a pH of 13 by adding 2\u2005M sodium hydroxide solution. The aqueous phase was extracted with Et2O (3\u00d750\u2005ml) and the combined organic phases were dried over Na2SO4. After removal of the solvent, the residue was purified by \u201cKugelrohr\u201d\u2010distillation . The desired product (S)\u20102 was obtained as a colorless oil . 1H\u2005NMR : \u03b4=1.23 , 2.08 , 3.07 , 7.08\u20137.12 , 7.18\u20137.21 , 7.31\u20137.33 . 1H}13C\u2005NMR{ : \u03b4 =21.1 , 43.7 , 66.6 , 127.4 , 128.1 , 128.9 , 145.9 . GC/EI\u2010MS: tR=6.04\u2005min [80\u2009\u00b0C (1\u2005min)\u20137\u2009\u00b0C/min\u2013170\u2009\u00b0C (2.5\u2005min)\u201050\u2009\u00b0C/min\u2013250\u2009\u00b0C (1\u2005min)]; m/z (%): 149 (24.5) [M+], 134 (100) [(M\u2212Me)+], 105 (47) [(M\u2212NMe2)+], 91 (23), 77 (36) [(Ph)+], 72 (79) [(M\u2212Ph)+]. Specific rotation: [\u03b1]D20=\u221265.02\u00b0\u2005mL\u2009g\u22121\u2009dm\u22121 .Compound \u20103: (S)\u20102  was dissolved in Et2O (80\u2005ml). The solution was cooled to 0\u2009\u00b0C and t\u2010Butyllithium  was dropped into solution. The yellowish solution was stirred for 1.5\u2005h at 0\u2009\u00b0C. Phenylmethyldimethoxysilane  was then added to the solution and the solution was slowly thawed to room temperature with stirring and stirred for 24\u2005h in total. The solids were separated and the solvent was removed in vacuum. After purification by \u201cKugelrohr\u201d\u2010distillation at reduced pressure , the product \u20103 was isolated as a colorless oil . 1H\u2005NMR : \u03b4=Dmaj 0.63, Dmin 0.66 , Dmin 1.04, Dmaj 1.08 , Dmaj 1.76, Dmin 1.81 , Dmin 3.34, Dmaj 3.36 , Dmin 3.52, Dmaj 3.57 , 7.16\u20137.18 , 7.21\u20137.33 , 7.54\u20137.59 , 7.63 , 8.04\u20138.11 . 1H}13C\u2005NMR{ : \u03b4=Dmaj \u22123.0, Dmin \u22121.9 , Dmin 17.4, Dmaj 18.9 , Dmin 42.5, Dmaj 42.8 , Dmaj 50.8, Dmin 50.9 , Dmin 63.7, Dmaj 64.2 , 126.7 , 128.3 , 129.8 , 130.9 , 134.6 , 136.9 , 138.0 , 138.6 , 153.3 . 1H}29Si\u2005NMR{ : \u03b4=Dmin \u22126.3, Dmaj \u22125.4 (1Si). GC/EI\u2010MS: tR=5.99\u2005min [80\u2009\u00b0C (1\u2005min)\u201310\u2009\u00b0C\u2005min\u22121\u20131\u2013250\u2009\u00b0C (5.5\u2005min)]; m/z (%): 299 (1) [(M+)], 284 (17) [(M\u2212CH3)+], 268 (3) [(M\u2212OCH3)+], 252 (9) [(M\u2212OCH3\u2212CH3)+], 223 (7) [(M\u2212Ph)+], 206 (100) [(M\u2212Ph\u2212CH3\u2212H)+]. Elemental analysis: Calc.: C: 72.19\u2009%, H: 8.41\u2009%, N: 4.68\u2009%. Found: C: 72.0\u2009%, H: 8.4\u2009%, N: 4.4\u2009%.Compound \u20101: \u20103  was dissolved in Et2O (80\u2005ml). 2\u2005M HCl  was added to the solution and the emulsion was intensively stirred for 2\u2005h. After that the reaction mixture was then cooled to 0\u2009\u00b0C and adjusted to pH\u200513 with KOH. The phases were separated and the aqueous phase was extracted with Et2O (3\u00d715\u2005mL). The combined organic phases were dried with MgSO4 and the volume of the solution was concentrated to 30\u2005ml. After storage at \u221230\u2009\u00b0C for 12\u2005h, the product \u20101 was obtained in the form of colorless crystals . 1H\u2005NMR : \u03b4=Dmaj 0.63, Dmin 0.66 , Dmin 1.04, Dmaj 1.08 , Dmaj 1.76, Dmin 1.81 , Dmin 3.34, Dmaj 3.36 , Dmin 3.52, Dmaj 3.57 , 7.16\u20137.18 , 7.21\u20137.33 , 7.54\u20137.59 , 7.63 , 8.04\u20138.11 . 1H}13C\u2005NMR{ : \u03b4=Dmaj \u22123.0, Dmin \u22121.9 , Dmin 17.4, Dmaj 18.9 , Dmin 42.5, Dmaj 42.8 , Dmaj 50.8, Dmin 50.9 , Dmin 63.7, Dmaj 64.2 , 126.7 , 128.3 , 129.8 , 130.9 , 134.6 , 136.9 , 138.0 , 138.6 , 153.3 . 1H}29Si\u2005NMR{ : \u03b4 =Dmin \u22126.3, Dmaj \u22125.4 (1Si). GC/EI\u2010MS: tR=5.99\u2005min [80\u2009\u00b0C (1\u2005min)\u201310\u2009\u00b0C\u2005min\u22121\u20101\u2013250\u2009\u00b0C (5.5\u2005min)]; m/z (%): 299 (1) [(M+)], 284 (17) [(M\u2212CH3)+], 268 (3) [(M\u2212OCH3)+], 252 (9) [(M\u2212OCH3\u2212CH3)+], 223 (7) [(M\u2212Ph)+], 206 (100) [(M\u2212Ph\u2212CH3\u2212H)+].Elemental analysis: Calc.: C: 72.19\u2009%, H: 8.41\u2009%, N: 4.68\u2009%. Found: C: 72.0\u2009%, H: 8.4\u2009%, N: 4.4\u2009%.Compound (S)\u20105: \u20101  was dissolved in Et2O (3.0\u2005mL). Hexamethyldisilazane  was then added to the reaction solution. The solution was then stirred for 20\u2005h. The solvent and volatiles were removed under vacuum and the siloxane (S)\u20105 was obtained as a colorless oil . 1H\u2005NMR : \u03b4=0.13 , 0.69 , 1.14 , 1.86 , 3.50 , 7.15\u20137.17 , 7.22 , 7.32 , 7.54\u20137.57 , 7.74 , 7.95 . 1H}13C\u2005NMR{ : \u03b4=1.0 , 2.5 , 21.0 , 43.4 , 64.8 , 126.7 , 127.0 , 128.3 , 128.5  129.8 , 130.9 , 134.3 , 136.0 , 136.2 , 140.6 , 153.3 . 1H}29Si\u2005NMR{ : \u03b4 =Dmin\u201014.8, Dmaj \u221213.6 , Dmin \u22128.4, Dmaj \u22128.9 . GC/EI\u2010MStR=6.00\u2005min [80\u2009\u00b0C (1\u2005min)\u201320\u2009\u00b0C/min\u2013290\u2009\u00b0C (2\u2005min)]; m/z: 342 (10) [(M\u2212Me)+], 297 (14) {[M\u2212H3CHN(CH3)2]+}, 264 (100) [(M\u2212Ph\u2212Me)+], 209 (21) {[PhMeSiOSi(CH3)3]+}, 72 (41) {[Si(CH3)3]+}, 59 (1) {[CH2N(CH3)2]+}. m/z: 344 (10) [(18M\u2212Me)+], 299 (14) {[18M\u2212H3CHN(CH3)2]+}, 266 (100) [(18M\u2212Ph\u2212Me)+], 211 (4) {[PhMeSi18OSi(CH3)3]+}, 72 (40) {[Si(CH3)3]+}, 59 (1) {[CH2N(CH3)2]+}. LC/HR\u2010MS: tR=6.23\u2005min [0.3\u2005mL/min H2O/MeCN (+ 0.1\u2009% MeCOOH): 95\u2009:\u20095 (2\u2005min)\u201380\u2009:\u200920 \u20130\u2009:\u2009100 \u201395\u2009:\u20095 ]; 358.20225\u2005m/z {C20H32ONSi2 [M+H]+, (\u0394=1.552\u2005ppm)} 360.20618\u2005m/z {C20H3218ONSi2 [M+H]+, (\u0394=0.666\u2005ppm)} Specific rotation: [\u03b1]D20=+7.338\u00b0\u2005mL\u2009g\u22121\u2009dm\u22121 .Elemental analysis: Calc: C: 67.17\u2009%, H: 8.74\u2009%, N: 3.92\u2009%. Found: C: 67.3\u2009%, H: 8.7\u2009%, N: 4.0\u2009%.Compound \u20106: \u20101  was dissolved in 1\u2005mL acetone. ZnBr2  was dissolved in 1\u2005mL acetone and added to the silanol solution. After a few days, the product \u20106 crystallized from acetone in the form of colorless blocks in space group P212121 . Yield: 0.06\u2005g, 0.07\u2005mmol  Elemental analysis: Calc.: C: 52.03\u2009%, H: 6.14\u2009%, N: 3.28\u2009%. Found: C: 52.3\u2009%, H: 6.2\u2009%, N: 3.4\u2009%.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The triazole ring in the title mol\u00adecule is not quite coplanar with the six-membered ring to which it is fused, the dihedral angle between the two least-squares planes being 2.52\u2005(6)\u00b0. In the crystal, a layer structure is formed by N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds plus slipped \u03c0-stacking inter\u00adactions, with the fused cyclo\u00adhexene rings projecting to either side. 9H10N4O, is not quite coplanar with the six-membered ring to which it is fused, the dihedral angle between the two least-squares planes being 2.52\u2005(6)\u00b0. In the crystal, a layered structure is formed by N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds plus slipped \u03c0-stacking inter\u00adactions, with the fused cyclo\u00adhexene rings projecting to either side.The triazole ring in the title mol\u00adecule, C Karan et al., 2021e.g. Zhao et al., 2021e.g. El-Shershaby et al., 2021e.g. Zhang et al., 2020e.g. Ibrahim et al., 2021Compounds containing nitro\u00adgen heterocycles make up a significant portion (approximately 60%) of small drug mol\u00adecules that have been approved by the FDA \u2005\u00c5, \u03b8 = 129.71\u2005(14)\u00b0 and \u03c6 = 326.36\u2005(18)\u00b0. This conformation is quite similar to a half-chair form. The C8/N2/C9/N3/N4 ring is closer to planarity than is the C1/C2/C7/N1/C8/N4 ring  and the dihedral angle between their mean planes is 2.52\u2005(6)\u00b0. In the crystal, N1\u2014H1\u22efN3 hydrogen bonds  and ethyl 2-oxo-cyclo\u00adhexa\u00adnecarboxyl\u00adate  were combined and heated under reflux in 10\u2005ml of acetic acid for 1\u2005h. The solid product obtained was recrystallized from ethanol solution to afford colorless crystals.1Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623004091/tk4091sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623004091/tk4091Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623004091/tk4091Isup3.cmlSupporting information file. DOI: 2259950CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The distorted coordination octa\u00adhedra around Li+ involve four short bonds with two pyrazolate N atoms and two aqua ligands and two longer contacts with nitro-O atoms. When combined with \u03bc4-{TNBPz}2\u2212, this generates a mono-periodic polymeric structure incorporating discrete centrosymmeric [(H2O)2Li\u2013(di\u00adnitro\u00adpyrazolato)2\u2013Li(H2O)2] units. The three-dimensional stack of mutually orthogonal coordination chains is reminiscent of a Lincoln log pattern.In the title salt, the 3,3\u2032,5,5\u2032-tetra\u00adnitro-4,4\u2032-bi\u00adpyrazole-1,1\u2032-diide dianion [{TNBPz} 2(C6N8O8)(H2O)4]n, the 3,3\u2032,5,5\u2032-tetra\u00adnitro-4,4\u2032-bi\u00adpyrazole-1,1\u2032-diide dianion [{TNBPz}2\u2212] is situated across the twofold axis. The distorted coordination octa\u00adhedra around Li+ involve four short bonds with two pyrazolate N atoms and two aqua ligands [Li\u2014N(O) = 1.999\u2005(3)\u20132.090\u2005(2)\u2005\u00c5] and two longer contacts with nitro-O atoms . When combined with \u03bc4-{TNBPz}2\u2212, this generates a mono-periodic polymeric structure incorporating discrete centrosymmeric [(H2O)2Li\u2013(di\u00adnitro\u00adpyrazolato)2\u2013Li(H2O)2] units. The three-dimensional stack of mutually orthogonal coordination chains is reminiscent of a Lincoln log pattern. It is influenced by conventional hydrogen bonding [O\u22efO = 2.8555\u2005(17)\u20133.0010\u2005(15)\u2005\u00c5] and multiple lone pair\u2013\u03c0 hole inter\u00adactions of the nitro groups [N\u22efO = 3.0349\u2005(15) and 3.0887\u2005(15)\u2005\u00c5]. The Hirshfeld surface and two-dimensional fingerprint plots also support the significance of non-covalent bonding. Coordinative saturation and a favorable geometry at the Li+ ions, dense packing of the polymeric subconnectivities and particularly extensive inter\u00adanion inter\u00adactions may be involved in the stabilization of the structure. The title salt is a rare example of an energetic Li nitro\u00adazolate, which nicely crystallizes from aqueous solution and is neither hygroscopic nor efflorescent. The TG/DTA data reveal total dehydration in the range of 330\u2013430\u2005K and stability of the anhydrous material up to 633\u2013653\u2005K.In the structure of the title salt, [Li The nitro\u00adpyrazolates crystallize with difficulty  and 2.090\u2005(2)\u2005\u00c5], two aqua-O atoms [1.999\u2005(3) and 2.027\u2005(3)\u2005\u00c5] and two elongated bonds with nitro-O atoms [2.550\u2005(2) and 2.636\u2005(2)\u2005\u00c5] Li]n\u2013  \u2005\u00c5 [symmetry code: (ii) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z], are likely attractive, as a kind of lone pair\u2013\u03c0 hole bonding \u2005\u00c5 vs 1.4644\u2005(15) and 1.462\u2005(2)\u2005\u00c5 for H2(TNBPz) and Rb{H(TNBPz)}, respectively], which indicates a lack of essential conjugation between two pyrazolate rings. Shortening of the C-NO2 bonds upon deprotonation is also minor [mean 1.4308\u2005(16)\u2005\u00c5 vs 1.439\u2005(2)\u2005\u00c5 for H2(TNBPz)], while a certain increase in conjugation is reflected rather by a perceptible flattening of the di\u00adnitro\u00adpyrazole fragments. For the latter, the NO2 groups are nearly coplanar with the ring, the two dihedral angles are 1.35\u2005(8) and 11.66\u2005(8)\u00b0, for N4O3O4 and N3O1O2 groups, respectively. In the case of H2(TNBPz), the twist comes to 22.8\u2005(2)\u00b0. The most appreciable consequence of the dianionic structure is similarity of bond angles at the ring-N atoms: N2\u2014N1\u2014C1 = 107.11\u2005(9)\u00b0 and N1\u2014N2\u2014C3 = 106.93\u2005(9)\u00b0. For the neutral di\u00adnitro\u00adpyrazole rings, the parameters for N- [103.9\u2005(2)\u00b0] and NH-sites [112.0\u2005(2)\u00b0] are clearly different 2 cycles (pz is pyrazole).The title compound adopts a mono-periodic polymeric structure with the {TNBPz}rn Fig.\u00a02, which iA\u22efO6vii  are important for the connection of the chains into layers, which are parallel to the ab plane, whereas the second aqua/aqua bond O5\u2014H\u22efO6v  is readily available by nitration of 4,4\u2032-bi\u00adpyrazole in mixed acids (yield 92%) and subsequent crystallization from water  of solid H2(TNBPz)\u00b7H2O was added with stirring. The mixture was stirred for 30\u2005min and the resulting clear deep-yellow solution was cooled to r.t. Slow evaporation to a minimum volume over 8\u201310\u2005d led to crystallization of the product as well-developed large lemon-yellow prisms. The crystals were removed and dried on a filter paper in air. The yield was 1.25\u2005g (90%). The material shows neither signs of hygroscopy nor efflorescence when exposed to ambient air for months.For the preparation of the title compound, 0.294\u2005g (7.0\u2005mmol) of LiOH\u00b7H6H8Li2N8O12: C 18.10, H 2.03, N 28.15; found: C 18.45, H 1.99, N 28.42. IR : 564 m, 636 m, 698 m, 716 m, 773 w, 853 s, 1006 m, 1021 s, 1189 w, 1284 w, 1308 s, 1321 s, 1353 s, 1381 s, 1410 s, 1484 s, 1540 s, 1641 m, 1658 m, 3460 br, 3580 br.Analysis (%) calculated for C\u22121 (O\u2014H stretching), 1641, 1658\u2005cm\u22121 (bend) and 564\u2005cm\u22121 (libration). The peaks for symmetric and asymmetric NO2 stretching  are very similar to the spectra of comparable 3,5-di\u00adnitro\u00adpyrazole , and its shift, with respect to the band for H2(TNBPz)\u00b7H2O . The anhydrous material is stable up to 633\u2005K, with the very minor exothermic event at 597\u2005K possibly indicating a phase transition. Exothermic decomposition proceeds above 653\u2005K, with instantaneous loss of any remaining weight and a sharp exothermic effect at ca 700\u2005K suggesting an explosion. For comparison, typical onset temperatures for decomposition of energetic Li nitro\u00adpyrazolates are 400\u2013500\u2005K, and only 3,5-di\u00adnitro\u00adpyrazolate is stable up to 600\u2005K . There are two partially separated stages for nearly identical weight losses in the temperature range of 330\u2013430\u2005K Fig.\u00a07, which c6.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023005339/pk2688sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989023005339/pk2688Isup2.hklStructure factors: contains datablock(s) I. DOI: 2269963CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The caffeinium cations form a double layer via hydrogen bonds and \u03c0-stacking inter\u00adactions. The Hirshfeld surface analysis showed that the largest contribution to the crystal packing is made by H\u22efH (31.2%), H\u22efCl/Cl\u22efH (22.6%), O\u22efH/H\u22efO (21.9%) contacts for the cation and H\u22efCl/Cl\u22efH (79.3%) contacts for the anion.The mol\u00adecular and crystal structure of the title compound, (C Studies on the inter\u00adaction of hexa\u00adchloro\u00adplatinates with various biological organic compounds have been performed before, for example by Novikov et al.  hexa\u00adchloro\u00adplatinum RECJAO  crystallizes in the triclinic space group Pb) contains two caffeinium cations and one centrosymmetric hexa\u00adchloro\u00adplatinate anion with a platinum atom in a special position 1a. In the imidazole ring of the caffeine mol\u00adecule, the nitro\u00adgen N1 atom is protonated. The cation, including the methyl groups, has a flat geometry (maximum deviation for non-hydrogen atoms 0.030\u2005\u00c5). The [PtCl6]2\u2212 anion has a slightly distorted octa\u00adhedral geometry with similar Pt\u2014Cl bond distances \u2005\u00c5 .Hydrogen bonds and \u03c0-stacking play a significant role in the formation of inter\u00admolecular inter\u00adactions in the crystal structure of \u2005\u00c5 Fig.\u00a01b.et al., 2016et al., 2018et al., 2011et al., 2022Cz) and chlorine atoms Cl1 and Cl2, with Cz \u22ef Cl distances of 3.8643\u2005(11) and 3.7170\u2005(11)\u2005\u00c5, respectively, and \u03b1 angles between the ring plane and the Cz\u22efCl vector of 61.82\u2005(7) and 62.28\u2005(7)\u00b0, respectively. It is uncertain whether such an inter\u00adaction exists with Cl3 .Similarly, \u03c0\u2013halogen inter\u00adactions  plane  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z] inter\u00adaction being the strongest.The crystal packing in ne Fig.\u00a02. The cafne Fig.\u00a02, the N1\u20144.Crystal Explorer 21 was used to calculate the Hirshfeld surfaces (HS) and two-dimensional fingerprint plots  to 1.063 (blue) for cation and \u22120.402 to 0.934 a.u. for anion, as illus\u00adtrated in Fig.\u00a03b).s Figs. 3 and 4 \u25b8.c,d,i. The structures of II and III show distributions of contacts .Analysis of inter\u00admolecular contacts shows that for the caffeinum cation, the largest contributions are made by H\u22efH, Cl\u22efH/H\u22efCl and O\u22efH/H\u22efO contacts Fig.\u00a05, and fors Figs. 5 and 6 \u25b8 5.et al., 20166 type. The closest analogues of I found were II and III (see above), the former containing N-protonated 3-carb\u00adoxy\u00adpyridine (nicotinic acid) as the cation and [PtCl6]2\u2212 as the anion, the latter containing a caffeinium cation with a methyl\u00adated (rather than protonated) N1 atom and a PF6\u2212 anion.A search of the Cambridge Structural Database  refined], C4H3 as rotationally disordered between two orientations with occupancies of 0.62\u2005(4) and 0.38\u2005(4) [Uiso(H) = 1.2Ueq(C)], with C\u2014H 0.96\u2005\u00c5 in each case. The H atoms at N1 and C3 were refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023005157/zv2027sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023005157/zv2027Isup2.hklStructure factors: contains datablock(s) I. DOI: 2268577CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cinnamaldehyde 4-thio\u00adsemicarbazone homoleptic complex is reported. As a result of H\u22efS intra\u00admolecular inter\u00adactions, graph-set motif S(5), the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the mol\u00adecules are linked by H\u22efS inter\u00adactions, with graph-set motifs The synthesis, crystal structure and Hirshfeld surface analysis of a new Pd E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-yl\u00adidene]hydra\u00adzine\u00adcarbo\u00adthio\u00adamide  deprotonated with NaOH in ethanol with an ethano\u00adlic suspension of PdII chloride in a 2:1 molar ratio yielded the title compound, [Pd(C16H14N3S)2]. The anionic ligands act as metal chelators, \u03ba2N1S-donors, forming five-membered rings with a trans-configuration. The PdII ion is fourfold coordinated in a slightly distorted square-planar geometry. For each ligand, one H\u22efS and one H\u22efN intra\u00admolecular inter\u00adactions are observed, with S(5) and S(6) graph-set motifs. Concerning the H\u22efS inter\u00adactions, the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the complexes are linked via pairs of H\u22efS inter\u00adactions, with graph-set motif R22(8), and building a mono-periodic hydrogen-bonded ribbon along [001]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: H\u22efH (45.3%), H\u22efC/C\u22efH (28.0%), H\u22efS/S\u22efH (8.0%) and H\u22efN/N\u22efH (7.4%).The reaction of (2 It was pointed out that the main product of the characterization reaction was a thio\u00adsemicarbazone derivative, R3R4C=N\u2014N(H)C(=S)NR1R2 \u2014C(=S) fragment can be easily deprotonated and the negative charge is then delocalized over the N\u2014N\u2014C\u2014S entity, which enables chemical bonding with many different metal centers, with different Lewis acidity, and a diversity of coordination modes, II heteroleptic complexes with a cinnamaldehyde-thio\u00adsemicarbazone deriv\u00adative turned out to be very active on in vitro Human Topo\u00adisomerase II\u03b1 inhibition, a biological target of prime importance for cancer research , cervix (HeLa), hepatocellular (HepG2), breast (MCF-7) and prostate (PC-3)  and lung (A549) 2 homo- and heteroleptic complexes results in the formation of ZnS nanocrystallites  2 and CdI2(LH)2 were used as starting materials to obtain CdS nanoparticles 2 homo- and heteroleptic complexes  and 177.57\u2005(2)\u00b0, respectively. The metal ion is fourfold coordinated in a slightly distorted square-planar geometry. The maximum deviation from the mean plane through the Pd1/N1/N4/S1/S2 fragment is 0.0227\u2005(5)\u2005\u00c5 for Pd1 and the r.m.s. for the selected atoms is 0.0151\u2005\u00c5. Concerning the geometry of the N\u2014N\u2014C\u2014S entities, the N1\u2014N2\u2014C10\u2014S1 torsion angle is 0.6\u2005(3)\u00b0, while N4\u2014N5\u2014C26\u2014S2 is \u22120.4\u2005(3)\u00b0. Both of the ligands are non-planar, with the angle between the mean planes through the C4\u2013C9 and the C11\u2013C16 aromatic rings being 15.7\u2005(1)\u00b0, while that between the C20\u2013C25 and the C27\u2013C32 rings is 45.5\u2005(8)\u00b0.The asymmetric unit comprises one mol\u00adecule of the title compound, with all atoms being located in general positions Fig.\u00a01. The comS(5), and C16\u2014H13\u22efN2 and C32\u2014H26\u22efN5, with graph-set motif S(6). Considering the S(5) rings, a hydrogen-bonded macrocyclic coordination environment-type can be suggested for the PdII metal center, while the S(6) rings contribute to the stabilization of the mol\u00adecular structure.Four intra\u00admolecular hydrogen-bonding inter\u00adactions are observed Fig.\u00a02: C1\u2014H1\u22efSi.e., non-coordinating thio\u00adsemicarbazones, the N\u2014N and C\u2014S bonds have lengths of double-bond character, while the N\u2014C bond shows lengths of single-bond type, which can be written as a N=N(H)\u2014C=S fragment. When the acidic H atom of the hydrazinic fragment is removed, the negative charge is delocalized over the N\u2014N\u2014C\u2014S chain and the bond lengths change to inter\u00admediate values. Thus, the N\u2014N and the C\u2014S bond lengths assume single-bond character, being longer, and the N\u2014C bond lengths assume double-bond character, being shorter. Information about the bond lengths of the N\u2014N\u2014C\u2014S entities for the cinnamaldehyde-4-phenyl\u00adthio\u00adsemicarbazone mol\u00adecule, C16H15N3S, and the Ni(C16H14N3S)2 2 complexes, this work, are summarized in Table\u00a02et al., 2014Finally, the anionic form of the ligands was assigned because of the absence of hydrazinic H atoms and the change in the bond lengths of the N\u2014N\u2014C\u2014S entities. For the neutral or free, 3.via pairs of N\u2014H\u22efS inter\u00adactions with graph-set motif In the crystal, the mol\u00adecules are connected 1] Fig.\u00a03.Crystal Explorer  x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0a) H\u22efH (45.3%), (b) H\u22efC/C\u22efH (28.0%), (c) H\u22efS/S\u22efH (8.0%) and (d) H\u22efN/N\u22efH (7.4%). The contributions to the crystal packing are shown as two-dimensional Hirshfeld surface fingerprint plots with cyan dots  and the de (y-axis) values are the closest inter\u00adnal and external distances from given points on the Hirshfeld surface (in \u00c5).The Hirshfeld surface analysis  and as a ligand, viz. in the homoleptic [Ni(C16H14N3S)2] complex  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01]. The negative charge of the ligand was assigned by the absence of a hydrazinic H atom and the bond distances in the N\u2014N\u2014C\u2014S chain , the metal center is fourfold coordinated in a square-planar geometry and the N\u2014N\u2014C\u2014S entity torsion angle is 1.5\u2005(6)\u00b0.To the best of our knowledge and using database tools such as ry Fig.\u00a06  Fig.\u00a06. The H\u22efC] Fig.\u00a06 and theyII coordination compound was also performed with CrystalExplorer  H\u22efH (47.4%), (b) H\u22efC/C\u22efH (27.6%), (c) H\u22efN/N\u22efH (7.0%) and (d) H\u22efS/S\u22efH (6.5%). The di (x-axis) and the de (y-axis) values are the closest inter\u00adnal and external distances from given points on the Hirshfeld surface contacts (in \u00c5). While for the PdII title compound and the NiII reference compound the most important inter\u00admolecular contacts are H\u22efH and the H\u22efC/C\u22efH, the order of importance changes for the H\u22efS/S\u22efH and H\u22efN/N\u22efH contacts. For the crystal packing of the PdII complex, the H\u22efS/S\u22efH contacts are more important then H\u22efN/N\u22efH contacts, while for the NiII complex this order is the opposite.The Hirshfeld surface analysis  = 1.2 Ueq, and with C\u2014H = 0.93\u2005\u00c5 and N\u2014H = 0.86\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023008654/zn2032sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989023008654/zn2032Isup2.hklStructure factors: contains datablock(s) I. DOI: 2163054CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, pairs of mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds, forming  6H8N2OS, all atoms except for the methyl H atoms are coplanar, with a maximum deviation of 0.026\u2005(4)\u2005\u00c5. In the crystal, pairs of mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds, forming R22(8) ring motifs. Dimers are connected by N\u2014H\u22efO hydrogen bonds, forming layers parallel to the (102) plane. Consolidating the mol\u00adecular packing, these layers are connected by C\u2014H\u22ef\u03c0 inter\u00adactions between the center of the 1,3-thia\u00adzole ring and the H atom of the methyl group attached to it, as well as C=O\u22ef\u03c0 inter\u00adactions between the center of the 1,3-thia\u00adzole ring and the O atom of the carboxyl group. According to a Hirshfeld surface study, H\u22efH (37.6%), O\u22efH/H\u22efO (16.8%), S\u22efH/H\u22efS (15.4%), N\u22efH/H\u22efN (13.0%) and C\u22efH/H\u22efC (7.6%) inter\u00adactions are the most significant contributors to the crystal packing.In the title compound, C Other major contributors are O\u22efH/H\u22efO , S\u22efH/H\u22efS , N\u22efH/H\u22efN  and C\u22efH/H\u22efC  inter\u00adactions. Other, smaller contributions are made by S\u22efC/C\u22efS (2.7%), C\u22efO/O\u22efC (2.6%), C\u22efC (1.8%), N\u22efC/C\u22efN (1.5%), S\u22efO/O\u22efS (0.8%), S\u22efN/N\u22efS (0.1%) and O\u22efN/N\u22efO (0.1%) inter\u00adactions.u. Fig.\u00a07. The intu. Fig.\u00a07b. Other4.et al., 20161,3-thia\u00adzole yielded five compounds related to the title compound, viz. CSD refcodes IXAMAV via weak C\u2014H\u22efO hydrogen bonds into a two-dimensional supra\u00admolecular framework. The crystal structure of DUTZEY involves inter\u00admolecular N\u2014H\u22efN hydrogen bonds. In the crystal of LAMQOJ, weak C\u2014H\u22efN hydrogen bonds build up a wavy layer of mol\u00adecules in the (011) plane. The layers are stacked in the [100] direction by weak \u03c0\u2013\u03c0 stacking inter\u00adactions between the 1,3-thia\u00adzole rings.In the crystal of IXAMAV, the supra\u00admolecular network is based upon N\u2014H\u22efN hydrogen-bonded centrosymmetric dimers linked by N\u2014H\u22efO contacts. ABEGAQ forms a supra\u00admolecular network based on N\u2014H\u22efN hydrogen-bonded centrosymmetric dimers that are linked in turn by N\u2014H\u22efO contacts. In the crystal of FEFKUY, an inter\u00adplay of O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds connects the mol\u00adecules to form 5.et al., 2012The title compound was synthesized using a reported procedure  = 1.2Ueq(N) for the NH2 group and 1.5Ueq(C) for CH3 groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023007181/vm2288sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023007181/vm2288Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007181/vm2288Isup3.cmlSupporting information file. DOI: 2288949CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing involves three borderline C\u2014H\u22efN contacts and a pairing of the triazole rings across an inversion centre.In the crystal structure of the title compound, the triazole ring exhibits inter\u00adplanar angles of  17H14N4O2, the triazole ring exhibits inter\u00adplanar angles of 63.86\u2005(2) and 76.96\u2005(2)\u00b0 with the phenyl and benzo\u00adthia\u00adzole planes, respectively. The C\u2014C\u2014C angle at the methyl\u00adene group is rather wide at 114.28\u2005(4)\u00b0. The packing involves three borderline C\u2014H\u22efN contacts, two of which combine to form layers parallel to ac, and a pairing of the triazole rings across an inversion centre [inter\u00adplanar distance of 3.1852\u2005(2)\u2005\u00c5].In the structure of the title compound, C A selection, mostly involving the heteroatoms, is presented in Table\u00a01imine contact in N-[3-(benzo[d]thia\u00adzol-2-yl)-6-bromo-2H-chromen-2-yl\u00adidene]-4-methyl\u00adbenzenamine , 3.1852\u2005(2) and 0.94\u2005\u00c5, respectively. This feature is reinforced by the other C\u2014H\u22efN inter\u00adaction, which involves the same operator.The mol\u00adecular packing displays few significant features. There are three borderline C\u2014H\u22efN inter\u00adactions Table\u00a02, two of ne Fig.\u00a03. The tri4.et al., 2002et al., 2016The searches employed the routine ConQuest -1,3-benzo\u00adthia\u00adzole  to 445 values in the range 106\u2013122\u00b0, with a mean value of 114\u2005(5)\u00b0. However, restricting one ring to be a C2-substituted thia\u00adzole gave only three hits, with four values of 109.6\u2013112.9\u00b0 for the angle at the methyl\u00adene groups. These all involved two planar ring systems of the benzo[d]thia\u00adzole type, but with different heteroatoms in some cases  and phenyl iso\u00adthio\u00adcyanate 2 (0.01\u2005mol) was stirred for 30\u2005min in ethanol (25\u2005mL) in the presence of sodium ethoxide (0.01\u2005mol). After cooling, methyl iodide (0.015\u2005mol) was added. The reaction mixture was stirred for 30\u2005min at room temperature, then refluxed for 1\u2005h. The resulting precipitate was filtered off, washed with water, dried, and recrystallized from ethanol. The title compound was isolated as a white solid; yield 75%; m.p. 429\u2005K; IR : \u03bd 3053 (Ar\u2014CH), 2928 , 1594 (C=N); 1H NMR : \u03b4 2.60 , 4.57 , 7.36\u20137.50 , 7.89 , 8.01 ; Analysis calculated for C17H14N4S2 (338.45): C 60.33, H 4.17, N 16.55, S 18.95. Found C 60.66; H 4.15; N 16.40; S 18.90%.A mixture of 2-benzo\u00adthia\u00adzolyl acetohydrazide 6.aromatic = 0.95\u2005\u00c5, C\u2014Hmethyl\u00adene = 0.99\u2005\u00c5). The U(H) values were fixed at 1.5 \u00d7 Ueq of the parent carbon atoms for the methyl group and 1.2 \u00d7 Ueq for other hydrogens.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023007041/yz2038sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023007041/yz2038Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007041/yz2038Isup3.cmlSupporting information file. DOI: 2287438CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title bis-urea derivative, the host mol\u00adecules are linked by N\u2014H\u22efO=C hydrogen bonds and C\u2014H\u22efO contacts with  26H26N4O6\u00b72C4H8O, representing a bis-urea with terminal phenyl\u00adalanine units, crystallized with two tetra\u00adhydro\u00adfuran (THF) mol\u00adecules. The main mol\u00adecule is located on a crystallographic twofold axis, while the solvent mol\u00adecule is disordered over two positions, with occupancies of 0.571\u2005(15) and 0.429\u2005(15). The host mol\u00adecules are linked by N\u2014H\u22efO=C hydrogen bonds and C\u2014H\u22efO contacts with R21(6) and R21(7) ring motifs. The THF mol\u00adecules enclosed in the crystal are connected to the bis-urea compound via O\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions.The title compound, C The angle between the planes of adjacent urea moieties is 83.7\u2005(1)\u00b0, thus they are nearly perpendicular to one other. Such a motif is also well known in the literature  and 2.32\u2005(3)\u2005\u00c5; Table\u00a013 (corresponding to about 29% of the unit-cell volume). The cavities are bounded by the nonpolar phenyl\u00adene and arene units of the title compound. In addition, the carb\u00adoxy groups point into the inter\u00adior of these cavities and form O\u2014H\u22efO hydrogen bonds with the THF O atom [H\u22efO = 1.73\u2005(3)\u2005\u00c5]. Further stabilization of the mol\u00adecular network, each involving the THF mol\u00adecules, is realized by C\u2014H\u22efO contacts with the carb\u00adoxy group of an adjacent mol\u00adecule (H\u22efO = 2.78\u2005\u00c5) and weak C\u2014H\u22ef\u03c0 contacts (H\u22efCg = 2.61\u20133.00\u2005\u00c5) with the central benzene core or peripheral arene substituents.The crystal structure exhibits cavities which are occupied by THF mol\u00adecules requiring about 961\u2005\u00c5et al., 2012The synthetic and spectroscopic details for the title compound have been reported previously (Stapf Uiso(H) values were fixed at 1.2 times the equivalent Ueq value of the parent C atoms. The THF solvent mol\u00adecule is disordered over at least two positions [refined occupancies 0.571\u2005(15) and 0.429\u2005(15)]. Therefore, the solvent mol\u00adecule was refined using ISOR for C16A, C16B, C17A and C17B (approximate isotropic behaviour) and SADI (same distances over pairs of bonded atoms) restraints  I. DOI: 10.1107/S2414314623007435/bh4077Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623007435/bh4077Isup3.cmlSupporting information file. DOI: 2290568CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The first high-quality crystal structure of unmodified 2\u2032-de\u00adoxy\u00adguanosine is reported. The isolated crystals are the dimethyl sulfoxide disolvate. 10H13N5O4\u00b72C2H6OS, which is of inter\u00adest with respect to its biological activity, at 183\u2005K has ortho\u00adrhom\u00adbic (P212121) crystal symmetry. The structure displays a network of inter\u00admolecular N\u2014H\u22efN, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds. 2\u2032-De\u00adoxy\u00adguanosine mol\u00adecules are linked to each other and to the two dimethyl sulfoxide solvent mol\u00adecules by hydrogen bonding.The title com\u00adpound, C Understanding the properties of DNA is crucial for our knowledge of its reactivity in cellular processes of replication and transcription to yield transfer RNA  crystallized in the ortho\u00adrhom\u00adbic Sohnke space group P212121, with four formula units per unit cell and one per asymmetric unit .Nucleobase -one. The cocrystal structures of (actinomycin D)\u00b72(2\u2032-de\u00adoxy\u00adguanosine)\u00b712H2O (ACTDGU) and (7-bromo\u00adac\u00adtino\u00admycin)\u00b72(2\u2032-de\u00adoxy\u00adguanosine)\u00b711H2O (BRAXGU) at room temperature were also reported , is the only purine nucleoside solvate in the CSD  were obtained upon slow evaporation of 2\u2032-de\u00adoxy\u00adguanosine  from DMSO.Single crystals of  values were set at 1.2 times  or 1.5 times (for methyl and OH groups) the Ueq value of the parent atom. The Flack parameter x was \u22120.00\u2005(6) by classical fit to all intensities and 0.022\u2005(14) by Parsons\u2019 method  I, global. DOI: 10.1107/S2056989023007405/zv2028Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023007405/zv2028sup3.pdfFigures S1 and S2. DOI: 2290127CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular conformation is stabilized by two intra\u00admolecular N\u2014H\u22efN inter\u00adactions. In the crystal, mol\u00adecules are also linked via C\u2014H\u22ef\u03c0 inter\u00adactions forming a three-dimensional network.In the title compound, [24]di\u00adthia\u00adamethyrin(1.0.0.1.0.0); C 50H44Cl4N4S2 were obtained from the reaction of 2,5-bis\u00ad(4-propyl-1H-pyrrol-2-yl)thio\u00adphene and 3,5-di\u00adchloro\u00adbenzaldehyde in the presence of tri\u00adfluoro\u00adacetic acid for 3\u2005h and subsequent addition of p-chloranil. The macrocycle in the title compound can be described as a highly planar structure wthe the average deviation of the 32 macrocyclic atoms from the least-squares plane being 0.0416\u2005\u00c5. Its mol\u00adecular conformation is stabilized by two intra\u00admolecular N\u2014H\u22efN bonds and a three-dimensional network is formed by C\u2014H\u22ef\u03c0 inter\u00adactions.Purple crystals of the title compound, C Neighboring mol\u00adecules form dimers via inter\u00admolecular C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions owing to the H6\u22efCl1 (2.93\u2005\u00c5), H17A\u22efCl2 (3.34\u2005\u00c5), and C3\u2014C11 (3.36\u2005\u00c5) distances, as shown in Fig.\u00a02The mol\u00adecular structures and electronic properties of hexa\u00adpyrrolic expanded porphyrins with different numbers of \u03c0-electrons and et al. (20152Cl2 (ca 300\u2005mL) under an Ar atmosphere, to which 3,5-di\u00adchloro\u00adbenzaldehyde (68.4\u2005\u00b5L) and tri\u00adfluoro\u00adacetic acid (160\u2005\u00b5L) were added. The reaction mixture was stirred for 3\u2005h, p-chloranil (544\u2005mg) was added to it, and the mixture was stirred overnight at ambient temperature. Then, the mixture was neutralized with an aqueous NaHCO3 solution, and the crude products were passed through an alumina column. Finally, the products were purified by chromatography on a silica gel column using chloro\u00adform as elute. The third blue (2%) fraction afforded the title compound. The compound was recrystallized from a mixture of hexane and chloro\u00adform. Purple plates of suitable quality for diffraction were obtained by slow-diffusing hexane into chloro\u00adform. 1H NMR : \u03b4 (ppm) 24.0 , 7.20\u2013 6.87 , 5.05 , 4.61 , 0.76 , 0.52 , 0.32 ; MALDI\u2013TOF MS found = 904.254, monoisotopic mass = 904.176 calculated for C50H44Cl4N4S2. UV\u2013vis (CH2Cl2): \u03bb = 387, 500\u2005nm.The title compound was prepared by a modified previously reported method by Ishimaru  al. 2015. 2,5-BisCrystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2414314623007666/xu4052sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623007666/xu4052Isup2.hklStructure factors: contains datablock(s) I. DOI: 2292415CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, chains of mol\u00adecules extending along the  28H34ClN3O9S, is disordered over two closely spaced sets of sites; the site occupancy of the major component = 0.542\u2005(3). The conformation of each component is approximately U-shaped with the chloro\u00adbenzene ring forming the base and the indolinyl and sulfamoyl groups the sides; an intra\u00admolecular C\u2014H\u22efCl hydrogen bond possibly contributes to the stabilization of the conformation. In the crystal, a corrugated layer structure parallel to the ab plane is formed by C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) inter\u00adactions.The majority of the title mol\u00adecule, C Missioui et al., 2022Indapamide, is a di\u00adhydro-indole-based thia\u00adzide-like diuretic used to manage heart failure and treat hypertension. Various activities are associated with indole derivatives, including anti\u00adviral  = 0.247\u2005(8)\u2005\u00c5 and \u03c6(2) = 327\u2005(2)\u00b0 for the major component and Q(2) = 0.399\u2005(9)\u2005\u00c5 and \u03c6(2) = 329.6\u2005(16)\u00b0 for the other. The dihedral angle between the mean planes of the C1\u2013C6 and C15\u2013C20 rings is 86.2\u2005(4)\u00b0 while that between the two disordered components of the C1\u2013C6 ring is 3.8\u2005(5)\u00b0 and that between the two disordered components of the C15\u2014C20 ring is 5.68\u2005(6)\u00b0.The mol\u00adecule adopts an approximate U-shaped conformation Fig.\u00a01 with thed Table\u00a01 may helpd Table\u00a01 of the tA\u22efCl1 hydrogen bonds  and potassium bicarbonate  were dissolved in di\u00admethyl\u00adformamide (10\u2005mL), to which was added ethyl 2-bromo\u00adacetate . Under reflux, the reaction was stirred for 3\u2005h at 80\u00b0C. When the starting reagents had reacted completely, distilled water (100\u2005ml) was added. The product precipitated in solid form, was filtered, dried and recrystallized from ethanol solution to afford colorless blocks.N-(2-methyl\u00adindolin-1-yl)glycinate portion of the mol\u00adecule is disordered over two partially resolved sets of sites in a 0.542\u2005(3):0.458\u2005(3) ratio. In addition, the C23\u2014C24 ethyl group is disordered over two sets of sites in a 0.526\u2005(12):0.474\u2005(12) ratio. The two components of each disorder were refined with restraints that their geometries be comparable.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623006995/tk4094sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623006995/tk4094Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623006995/tk4094Isup3.cmlSupporting information file. DOI: 2280340CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title hydrated salt features a dense array of hydrogen bonds, forming a three-dimensional network. 5H5Cl2N2+\u00b7C6H4NO3\u2212\u00b7H2O, the pyridine N atom of the cation is protonated and an intra\u00admolecular O\u2014H\u22efO hydrogen bond is observed in the anion, which generates an S(6) ring. The crystal packing features N\u2014H\u22efN, O\u2014H\u22efO, N\u2014H\u22efO, C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds, which generate a three-dimensional network.In the title hydrated salt, C In the extended structure, the cations, anions and water mol\u00adecules are connected by N\u2014H\u22efN, O\u2014H\u22efO, C\u2014H\u22efCl, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds  was mixed with a hot aqueous solution of 4-amino 3,5-di\u00adchloro pyridine (34\u2005mg). The mixture was cooled slowly and kept at room temperature. After a few days, colourless block shaped crystals were obtained.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623008210/hb4452sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623008210/hb4452Isup2.hklStructure factors: contains datablock(s) I. DOI: 2294939CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "To provide the correct values of UCCR, the UCCR was calculated again by converting cortisol and creatinine in the same measurement unit (nmol/L).Section 3 Analytical Procedures, first paragraph, last sentence, should be as follows. \u201cThe UCCR was calculated by dividing the urine cortisol concentration (nmol/L) by the urine creatinine concentration (mmol/L).\u201dReference 29 is removed from the References list.\u22126 (1.04\u20103.81\u2009\u00d7\u200910\u22126), 32.09\u2009\u00d7\u200910\u22126 (7.68\u2010245.5\u2009\u00d7\u200910\u22126), and 10.55\u2009\u00d7\u200910\u22126 (3.47\u201054.05\u2009\u00d7\u200910\u22126) in dogs with HA, dogs with DMHA and healthy dogs, respectively.\u201dSection 4 Results, UCCR subsection, first sentence should be as follows. \u201cThe median UCCR was 2.03\u2009\u00d7\u200910\u22126 (7.68\u2010245.46\u2009\u00d7\u200910\u22126).Section 4 Results, UCCR subsection, fifth sentence should be as follows. \u201cThe median UCCR in dogs with DMHA and BSC \u22642\u2009\u03bcg/dL (\u226455\u2009nmol/L) was 27.14\u2009\u00d7\u200910Section 4 Results, UCCR subsection, last sentence should be as follows. \u201cA cut\u2010off value of UCCR <4.4 revealed 100% sensitivity (95% CI: 69.1\u2010100) and 97.3% specificity (95% CI: 85.8\u201099.9) in diagnosing HA.\u201dFigure 1, to be replaced with this new Figure 1.FIGURE 1 Scatter scale plot comparing urinary corticoid: creatinine ratio (UCCR) of dogs with hypoadrenocorticism , dogs with disease mimicking hypoadrenocorticism  and healthy dogs . The horizontal bars represent the median, the maximum, and the minimum value of each group."}
{"text": "The crystal structures of two benzo\u00adthio\u00adphene derivatives are described along with an analysis of the inter\u00admolecular contacts in the crystals performed using Hirshfeld surface analysis and two-dimensional fingerprint plots. 26H19NO2S2, (I), and C25H19NO2S2, (II), the benzo\u00adthio\u00adphene rings are essentially planar with maximum deviations of 0.026\u2005(1) and \u22120.016\u2005(1)\u2005\u00c5 for the carbon and sulfur atoms in compounds (I) and (II), respectively. In (I), the thio\u00adphene ring system is almost orthogonal to the phenyl ring attached to the sulfonyl group, subtending a dihedral angle of 88.1\u2005(1)\u00b0, and the di\u00adhydro\u00adpyridine ring adopts a screw\u2013boat conformation. In both compounds, the mol\u00adecular structure is consolidated by weak C\u2014H\u22efO intra\u00admolecular inter\u00adactions formed by the sulfone oxygen atoms, which generate S(5) ring motifs. In the crystal of II, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, generating C(7) chains running along the [100] direction. No significant inter\u00admolecular inter\u00adactions are observed in I.In both of the title compounds, C Thio\u00adphene derivatives possess pharmacological and biological activities including anti\u00adbacterial  attached to an N--N-prop-2-yn-1-yl benzene\u00adsulfonamide group (C9\u2013C15/N1/S2/O1/O2) , 19.0\u2005(1) and 33.9\u2005(1), respectively, in compound I and 0.7\u2005(2), 38.1\u2005(2) and 87.6\u2005(2)\u00b0, respectively, in compound II with the C1\u2013C6, C11\u2013C16 and C17\u2013C22 phenyl rings. The benzo\u00adthio\u00adphene ring system is almost orthogonal to the C17\u2013C22 phenyl ring attached to the sulfonyl group in I, subtending a dihedral angle of 88.1\u2005(1)\u00b0, while the di\u00adhydro\u00adpyridine ring (C10/C11/C16/C23/C24) adopts a screw\u2013boat conformation, as is evident from the Cremer\u2013Pople puckering analysis of the six-membered heterocyclic ring The mol\u00adecular structure of compound I Fig.\u00a01 comprise2) Fig.\u00a02. In bothI and 119.9\u2005(2)\u00b0 in II], with a simultaneous decrease in the N1\u2014S2\u2014C17 angle [108.5\u2005(1)\u00b0 in I and 107.6\u2005(1)\u00b0 in II] from the ideal tetra\u00adhedral value (109.5\u00b0) are attributed to the Thorpe\u2013Ingold effect \u2005\u00c5 in II] and N1\u2014C16 . No significant inter\u00admolecular inter\u00adactions or C\u2014H\u22ef\u03c0 inter\u00adactions with centroid distances of less than 4\u2005\u00c5 are observed in the structure.In the crystal of II, mol\u00adecules are linked via C25\u2014H25\u22efO1 hydrogen bonding, generating C(7) chains \u2005\u00c5 where Cg3 is the centroid of the S1/C1/C6\u2013C8 ring; symmetry code: (ii) \u2212x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] and C\u2014H\u22ef\u03c0 inter\u00adactions . are also present. Packing view of the title compound are shown in Figs. 3In the crystal of 4.et al., 2019et al., 2007dnorm, curvedness and shape index and 2D fingerprint plots) were performed with CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of \u22120.085 (red) to 1.564 (blue) for compound I and \u22120.286 (red) to 1.374 (blue) for compound II. The red spots indicate inter\u00admolecular contacts involved in hydrogen bonding.The Hirshfeld surfaces of compounds I, they reveal that the principal inter\u00admolecular contacts are H\u22efH , H\u22efC/C\u22efH , O\u22efH/H\u22efO , C\u22efC , S\u22efH/H\u22efS , S\u22efC/C\u22efS  and N\u22efH/H\u22efN . For compound II, they reveal a similar trend, with the principal inter\u00admolecular contacts being H\u22efH/H\u22efH , H\u22efC/C\u22efH , O\u22efH/H\u22efO , C\u22efC , S\u22efH/H\u22efS , S\u22efC/C\u22efS , C\u22efO/O\u22efC  and S\u22efO/O\u22efS . In both compounds, the H\u22efH inter\u00admolecular contacts predominate, followed by C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts.The fingerprint plots are illustrated in Figs. 65.I: A solution of N-propargyl\u00adbenzene\u00adsulfonamide (0.50\u2005g) in xylenes (20\u2005mL), MnO2 (0.50\u2005g) was added and the reaction mixture was refluxed for 24\u2005h. It was then filtered through a celite pad and washed with hot xylenes (2 \u00d7 10\u2005mL). The combined filtrate was concentrated under vacuum and then triturated with MeOH to afford dibenzo[b]thio\u00adphene  as a dull white solid. Finally, compound I was crystallized using ethanol.Compound II: To a solution of (E)-N-{2-[2-(benzo[b]thio\u00adphen-2-yl)ethenyl]phen\u00adyl}benzenesulfonamide  in CH3CN (10\u2005mL), K2CO3  and propargyl bromide  were added and the mixture was stirred at room temperature for 12\u2005h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (50\u2005g) containing conc. HCl (5\u2005mL), extracted with ethyl acetate (2 \u00d7 20\u2005mL) then washed with water (2 \u00d7 20\u2005mL) and dried (Na2SO4). Removal of the solvent in vacuo followed by crystallization from methanol (4\u2005mL) afforded compound II as a white solid.Compound 6.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023003821/zn2028sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989023003821/zn2028Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023003821/zn2028IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989023003821/zn2028Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023003821/zn2028IIsup5.cmlSupporting information file. DOI: 2259716, 2259715CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We previously reported that diacylglycerol (DG) kinase (DGK) \u03b4 interacts with DG\u2010generating sphingomyelin synthase (SMS)\u2010related protein (SMSr), but not SMS1 or SMS2, via their sterile \u03b1 motif domains (SAMDs). However, it remains unclear whether other DGK isozymes interact with SMSs. Here, we found that DGK\u03b6, which does not contain SAMD, interacts with SMSr and SMS1, but not SMS2. Deletion mutant analyses demonstrated that SAMD in the N\u2010terminal cytosolic region of SMSr binds to the N\u2010terminal half catalytic domain of DGK\u03b6. However, the C\u2010terminal cytosolic region of SMS1 interacts with the catalytic domain of DGK\u03b6. Taken together, these results indicate that DGK\u03b6 associates with SMSr and SMS1 in different manners and suggest that they compose new DG signaling pathways. The sterile \u03b1 motif domain (SAMD) of sphingomyelin synthase (SMS)\u2010related protein (SMSr) binds to the C\u2010terminal half catalytic domain of diacylglycerol kinase (DGK) \u03b6. Moreover, the C\u2010terminal cytosolic region of SMS1 interacts with the catalytic domain of DGK\u03b6. SMSr\u2010SAMD associates with DGK\u03b4\u2010SAMD and activates DGK\u03b4. However, SMSr\u2010SAMD moderately suppresses the activity of DGK\u03b6 in contrast to DGK\u03b4. CPESceramide phosphoethanolamine synthaseDGdiacylglycerolDGKdiacylglycerol kinaseFLfull lengthHRPhorseradish peroxidasePAphosphatidic acidPAPphosphatidic acid phosphatasePCphosphatidylcholinePEphosphatidylethanolaminePIphosphatidylinositolPLCphospholipase CPSphosphatidylserineSAMDsterile \u03b1 motif domainSMSsphingomyelin synthaseSMSrsphingomyelin synthase\u2010related proteinTEVtobacco etch virusTMDtransmembrane domainTSTwin\u2010Strepl\u2010lactate dehydrogenase A, and creatine kinase muscle type [Diacylglycerol kinase (DGK) phosphorylates diacylglycerol (DG) to convert it to phosphatidic acid (PA) , 3, 4, 5cle type , 15, 16.Diacylglycerol kinase isozymes function in a wide variety of physiological events, including immunity, cell proliferation, and the central nervous system , 18. ForThere are three isoforms of sphingomyelin synthase (SMS) , 37, SMSWe recently searched for an upstream enzyme (a DG supply enzyme) of DGK\u03b4. Consequently, we found that DGK\u03b4 interacts with SMSr , which sIn the present study, we comprehensively searched for interactions between DGK isozymes and SMS isozymes. We found that DGK\u03b6 binds to SMS1 and SMSr but not SMS2. Moreover, DGK\u03b6 interacts with SMSr and SMS1 in different manners. These results suggest that, beyond our expectations, DGK isozymes and SMS isozymes form a complex network.Mouse monoclonal anti\u2010V5 antibody  was obtained from Thermo Fisher Scientific . Rabbit polyclonal anti\u2010GFP antibody (#598) was purchased from Medical and Biological Laboratories . Mouse monoclonal anti\u2010FLAG\u2013tag antibody (F1804) was obtained from Sigma\u2013Aldrich . Mouse monoclonal anti\u2010GFP antibody (sc\u20109996) was purchased from Santa Cruz Biotechnology . Mouse monoclonal anti\u2010Strep II (M211\u20103) and rabbit polyclonal anti\u2010GST (PM013) were obtained from Medical and Biological Laboratories . A horseradish peroxidase (HRP)\u2010conjugated goat anti\u2010mouse IgG antibody was obtained from Bethyl Laboratories . Goat anti\u2010rabbit IgG\u2010HRP was purchased from Jackson ImmunoResearch .Plasmids for expressing N\u2010terminal 3\u00d7FLAG\u2010tagged human or rat DGK isozymes  and for We used the following nomenclature for epitope\u2010tagged proteins: TagX\u2010(protein) and (protein)\u2010TagY means that TagX and TagY are located at the N and C termini of the protein, respectively.EcoRI/SalI sites. The amplicons were generated using the following primers: SMS1\u2010NT (aa 1\u2013134) using 5\u2032\u2010CTCAAGCTTCGAATTATGAAGGAAGTGGTTTATTG\u20103\u2032 (forward) and 5\u2032\u2010CCGCGGTACCGTCGATCACTTGCCCCACTCCATG\u20103\u2032 (reverse); SMS1\u2010CT (aa 348\u2013413) using 5\u2032\u2010CTCAAGCTTCGAATTCACACTATGGCCAATCAGC\u20103\u2032 (forward) and 5\u2032\u2010CCGCGGTACCGTCGATTATGTGTCATTCACCAGCC\u20103\u2032 (reverse); SMSr\u2010NT (aa 1\u2013151), 5\u2032\u2010CTCAAGCTTCGAATTATGGCAGGTCCTAATC\u20103\u2032 (forward) and 5\u2032\u2010CCGCGGTACCGTCGATCACTTCCAGTATTCTGGGTC\u20103\u2032 (reverse); SMSr\u2010CT (aa 364\u2013415), 5\u2032\u2010CTCAAGCTTCGAATTCATACTCTGGCCAATACC\u20103\u2032 (forward) and 5\u2032\u2010 CCGCGGTACCGTCGATCATCCAATTAGTCTTTTC\u20103\u2032 (reverse).The N\u2010terminal (NT) or C\u2010terminal (CT) cytosolic regions of SMS1 and SMSr were subcloned into the pAcGFP\u2010C1 vector  via In\u2010Fusion cloning (Clontech\u2010Takara Bio) at the S\u2010transferase (GST)\u2010tagged SMS1\u2010CT and SMSr\u2010NT were generated by in\u2010fusion cloning. The pGEX\u20106P\u20101 vector  was linearized at the EcoRI and SalI sites, and amplified gene with 15\u2009bp extensions homologous to vector ends. We generated SMS1\u2010CT using 5\u2032\u2010GGGATCCCCGGAATTCCACACTATGGCCAATCAGC\u20103\u2032 (forward) and 5\u2032\u2010GTCGACCCGGGAATTCTATGTGTCATTCACCAGCC\u20103\u2032 (reverse) and SMSr\u2010NT using 5\u2032\u2010GAATTCCCGGGTCGAATGGCAGGTCCTAATCAAC\u20103\u2032 (forward) and 5\u2032\u2010GGCCGCTCGAGTCGATCACTTCCAGTATTCTGGGTCC\u20103\u2032 (reverse).Glutathione The cDNAs encoding DGK isozymes  that were subcloned into the expression plasmid, p3\u00d7FLAG\u2010CMV (Sigma\u2013Aldrich), for expression in mammalian cells were generated as described .EcoRI/SalI sites of the 3\u00d7FLAG CMV 7.1 vector. The following DGK\u03b6 mutants were generated using the following primers: DGK\u03b6\u2010NT (aa 1\u2013283), 5\u2032\u2010GGTGGTGAATTCAATGGAGCCGCGGGACGG\u20103\u2032 (forward) and 5\u2032\u2010ACGCGTCGACCTAGAAGGGTCTCCAGCGGCC\u20103\u2032 (reverse); DGK\u03b6\u2010CD (aa 284\u2013640), 5\u2032\u2010CCGGAATTCAATCATCAGGCCCACCCCC\u20103\u2032 (forward) and 5\u2032\u2010ACGCGTCGACCTACACCGGCTGCTGGTCG\u20103\u2032 (reverse); DGK\u03b6\u2010CD\u2010a (aa 284\u2013641), 5\u2032\u2010CCGGAATTCAATCATCAGGCCCACCCCC\u20103\u2032 (forward) and 5\u2032\u2010ACGCGTCGACCTACTCAGGCCCTGCCTCGG\u20103\u2032 (reverse); DGK\u03b6\u2010CD\u2010b (aa 433\u2013640), 5\u2032\u2010CCGGAATTCAGACCGAGATGAAGGCGCC\u20103\u2032 (forward) and 5\u2032\u2010ACGCGTCGACCTACACCGGCTGCTGGTCG\u20103\u2032 (reverse); DGK\u03b6\u2010CT (aa 641\u2013928) using the primers 5\u2032\u2010CCGGAATTCACCAGAGCAGTTGCGCATCC\u20103\u2032 (forward) and 5\u2032\u2010ACGCGTCGACCTACACAGCCGTCTCCTGGTC\u20103\u2032 (reverse).N\u2010terminal 3\u00d7FLAG\u2010tagged human DGK\u03b6 mutants were generated by PCR and inserted into the 2\u2010GGSA\u2010WSHPQFEK) was cloned into the XhoI/BglII site of the pCAGGS vector [BglII site of pCAGGS\u2010C\u2010TEV\u2010Twin\u2010Strep via In\u2010Fusion cloning. The following primers were used to amplify FL DGK\u03b6: forward, 5\u2032\u2010TTTTCAAGGCAGATCTATGGAGCCGCGGGACG\u20103\u2032; reverse, 5\u2032\u2010AGAGGGAAAAAGATCTCTACACAGCCGTCTCCTGG\u20103\u2032. N\u2010terminal Twin\u2010Strep\u2010tagged DGK\u03b6 was subcloned into pOET3 vector . The following primers were used, forward, 5\u2032\u2010TTTTCAAGGCAGATCTATGGAGCCGCGGGACG\u20103\u2032; reverse, 5\u2032\u2010TTATTAATTAAGATCTCTACACAGCCGTCTCCTGG\u20103\u2032.The plasmid expressing N\u2010terminal Tobacco Etch Virus (TEV) protease cleavable Twin\u2010Strep\u2010tag (ENLYFQGS\u2010WSHPQFEK\u2010(GGGS)S vector  to gener\u22121 penicillin/100\u2009\u03bcg\u00b7mL\u22121 streptomycin  at 37\u2009\u00b0C in an atmosphere containing 5% CO2. The plasmids were transiently transfected using PolyFect  according to the manufacturer's instructions or using polyethylenimine Max  [\u22121, pH 8.0) were preincubated for 10\u2009min at a 1\u2009:\u20093 ratio (20\u2009\u03bcg DNA: 60\u2009\u03bcL polyethylenimine Max) in 750\u2009\u03bcL of Opti\u2010MEM before transfection. The cells overexpressing recombinant proteins were harvested after 24\u2009h and the pellets were resuspended in 40% (v/v) glycerol diluted in phosphate\u2010buffered saline. The cell samples were flash\u2010frozen in liquid nitrogen and stored at \u221280\u2009\u00b0C until use.HEK293 cells  were maintained in Dulbecco's modified Eagle's medium  supplemented with 5% FBS (Thermo Fisher Scientific) and 100\u2009U\u00b7mLPA, USA) . The exp2 in the dark. Volume of the medium was kept at 20\u201330% of flask volume. To generate recombinant baculovirus was generated using pOET3 vector and the flashBAC system (Oxford Expression Technologies) as described previously [Sf9 cells were maintained in Sf\u2010900 II serum\u2010free medium  in sterile Erlenmeyer flask at 120\u2009r.p.m. and 28\u2009\u00b0C without COeviously .HEK293 cell lysates expressing V5\u2010tagged SMS1, SMS2, SMSr, or their AcGFP\u2010tagged mutants and 3\u00d7FLAG\u2010tagged DGKs  or their mutants were subjected to immunoprecipitation with anti\u2010V5 (MA5\u201015253) or anti\u2010GFP (#598) antibody and Protein A/G PLUS\u2010agarose beads (Santa Cruz Biotechnology) as described previously .S\u2010transferase\u2010fused SMS1\u2010CT and SMSr\u2010NT were bacterially expressed and highly purified using glutathione\u2010Sepharose beads . Twin\u2010Strep (TS)\u2010tagged DGK\u03b6 (TS\u2010DGK\u03b6) was expressed by mammalian cells and highly purified using Strep\u2010Tactin XT beads .Glutathione S\u2010transferase pull\u2010down assays were performed as previously [m Tris\u2013HCl, pH 7.5, 150\u2009mm NaCl, 1\u2009mm EDTA, 0.1% (v/v) Triton X\u2010100, and 1\u2009mm phenylmethylsulfonyl fluoride. Purified Twin\u2010strep tagged DGK\u03b6 was incubated with the beads for 2\u2009h at 4\u2009\u00b0C with constant rocking. Then, the beads were washed five times with buffer. The washed beads washed were then boiled in SDS sample buffer, and the extracts were analyzed by western blotting.Glutathione eviously . Purifiem Tris\u2013HCl, pH 7.4, containing 150\u2009mm NaCl, 10% (v/v) glycerol, 1\u2009mm PMSF, 0.1\u2009mm DTT, 20\u2009\u03bcg\u00b7mL\u22121 aprotinin, 20\u2009\u03bcg\u00b7mL\u22121 leupeptin, 20\u2009\u03bcg\u00b7mL\u22121 pepstatin, and 20\u2009\u03bcg\u00b7mL\u22121 soybean trypsin inhibitor) containing detergents (1% (w/v) n\u2010dodecyl\u2010\u03b2\u2010d\u2010maltoside (DDM) and 0.2% (w/v) cholesteryl hemisuccinate (CHS)). The supernatant (1% DDM soluble fraction) was isolated by ultracentrifugation at 100\u2009000\u2009g for 30\u2009min at 4\u2009\u00b0C and then purified using Strep\u2010Tactin XT beads. The beads were washed with the lysis buffer containing 0.05% DDM and 0.01% CHS. Subsequently, the bound proteins were eluted with the lysis buffer containing 0.05% DDM, 0.01% CHS, and 2.5\u2009mm d\u2010desthiobiotin (Sigma\u2013Aldrich). TS\u2010tagged DGK\u03b6 was purified using Strep\u2010Tactin XT beads without detergents.C\u2010terminally TS\u2010tagged human SMS1 and SMSr (SMS1\u2010TS and SMSr\u2010TS), and N\u2010terminally TS\u2010tagged DGK\u03b6 (TS\u2010DGK\u03b6) were expressed in HEK293 cells. SMS1\u2010TS and SMSr\u2010TS were lysed via lysed via homogenization on ice with ice\u2010cold lysis buffer (20\u2009mDiacylglycerol kinase activity was measured using liquid chromatography\u2013tandem mass spectrometry (LC\u2013MS/MS) as previously described .Western blotting was carried out as previously described . Equal qt test for the comparison of two groups or one\u2010way ANOVA followed by Tukey's or Dunnett's post hoc test for multiple comparisons using graphpad prism 8  to determine any significant differences. P\u2009<\u20090.05 was considered significant.Data are represented as the means\u2009\u00b1\u2009SDs and were analyzed by the Student's We first examined the interaction of all DGK isozymes with SMSr Fig.\u00a0. We confNext, we determined the interaction between 10 DGK isozymes and SMS1 Fig.\u00a0. As prevWe next examined the interaction between 10 DGK isozymes and SMS2 Fig.\u00a0. As prevWe next attempted to determine a DGK\u03b6\u2010interaction region in SMSr. AcGFP\u2010tagged N\u2010terminal (AcGFP\u2010SMSr\u2010NT) and C\u2010terminal (AcGFP\u2010SMSr\u2010CT) cytosolic regions of SMSr were generated Fig.\u00a0, and theA DGK\u03b6\u2010interaction region in SMS1 was also identified. For this purpose, AcGFP\u2010tagged N\u2010terminal (AcGFP\u2010SMS1\u2010NT) and C\u2010terminal (AcGFP\u2010SMS1\u2010CT) cytosolic regions of SMS1 were made Fig.\u00a0. InteresTo narrow the DGK\u03b6\u2010interaction area in the N\u2010terminal cytosolic region of SMSr, the DGK\u03b6\u2010interaction activity of SAMD alone of SMSr was tested. Figure To determine an SMSr\u2010interaction region in DGK\u03b6, we divided the protein into three parts, DGK\u03b6\u2010NT, DGK\u03b6\u2010CD, and DGK\u03b6\u2010CT Fig.\u00a0, and detNext, the interaction of DGK\u03b6\u2010NT, DGK\u03b6\u2010CD, and DGK\u03b6\u2010CT with SMS1\u2010CT was examined. Among them, 3\u00d7FLAG\u2010DGK\u03b6\u2010CD most strongly interacted with AcGFP\u2010SMS1\u2010CT Fig.\u00a0. AlthougWe further divided the catalytic domain of DGK\u03b6 into CD\u2010a and CD\u2010b Fig.\u00a0 and deteWe next examined whether DGK\u03b6 directly binds to SMSr and SMS1. GST\u2010fused SMSr\u2010NT and SMS1\u2010CT Fig.\u00a0 were bacin\u2009vitro [in\u2009vitro in the presence of 34:1 (16:0/18:1)\u2010DG. Intriguingly, SMSr, but not SMS1, moderately inhibited DGK\u03b6 activity  in\u2009vitro . Moreoveity Fig.\u00a0. Moreoveity Fig.\u00a0 also attity Fig.\u00a0. These rIn the present study, we demonstrated for the first time that DGK\u03b6 interacts with SMS1 and SMSr but not SMS2 Figs\u00a0. DGK\u03b41 aWe previously reported that DGK\u03b4 associates with SMSr via the interaction between DGK\u03b4\u2010SAMD and SMSr\u2010SAMD . AlthougSMSr, but not SMS1, inhibited DGK\u03b6 activity Fig.\u00a0. TherefoIn the case of the SMSr\u2013DGK\u03b6 interaction, SAMD in the N\u2010terminal cytosolic region of SMSr binds to DGK\u03b6 Fig.\u00a0. In contSMSr\u2010SAMD interacted with DGK\u03b6\u2010CD\u2010a Fig.\u00a0. Howeverhttps://www.proteinatlas.org/ENSG00000149091\u2010DGKZ/tissue), SMSr (https://www.proteinatlas.org/ENSG00000156671\u2010SAMD8/tissue), and SMS1 (https://www.proteinatlas.org/ENSG00000198964\u2010SGMS1/tissue) are ubiquitously expressed in a variety of tissues [Although SMSr is a DG\u2010generating enzyme, its CPES activity is very low . We rece tissues . These rIn summary, in the present study, we demonstrated for the first time that DGK\u03b6 interacts with SMS1 and SMSr but not SMS2 Fig.\u00a0. DGK\u03b4 alThe authors declare no conflict of interest.https://www.webofscience.com/api/gateway/wos/peer\u2010review/10.1002/2211\u20105463.13628.The peer review history for this article is available at MF primarily designed and conducted the experiments and analyzed the data. CM, YN, and RS designed and conducted the experiments and analyzed the data. CM, FS, and MF wrote the manuscript. CM and FS conceived the research. All authors revised the manuscript and approved its final version.Fig. S1. Sequence alignment of SMSr\u2010SAMD and SMS1\u2010SAMD. (A) Sequence alignment of SMSr\u2010SAMD (aa 12\u201378) and SMS1\u2010SAMD (aa 7\u201370). Sequence alignment was created using Clustal Omega provided by EMBL's European Bioinformatics Institute (EMBL\u2010EBI). Compared with SMSr\u2010SAMD, white letters on a black background indicate fully conserved residues, and black letters on a gray background indicate strongly similar residues. (B) Amino acid identities between the SAMDs of SMSr and SMS1. Amino acid identity and similarity were determined using Pairwise Sequence Alignment provided by the European Molecular Biology Open Software Suite (EMBOSS).Fig. S2. Multiple sequence alignment of the C\u2010terminal regions of SMS1, SMS2, and SMSr. (A) Multiple sequence alignment of the C\u2010terminal regions of SMS1\u2010CT (aa 348\u2013413), SMS2\u2010CT (aa 292\u2013365), and SMSr\u2010CT (aa 364\u2013415). Multiple sequence alignment was created using Clustal Omega provided by EMBL's European Bioinformatics Institute (EMBLEBI). Compared with SMS1\u2010CT, white letters on a black background indicate fully conserved residues, and black letters on a gray background indicate strongly similar residues. (B) Amino acid identities between the C\u2010terminal regions of SMS1, SMS2, and SMSr. Amino acid identity and similarity were determined using Pairwise Sequence Alignment provided by the European Molecular Biology Open Software Suite (EMBOSS).Fig. S3. Sequence alignment of DGK\u03b6\u2010CD and DGK\u03b9\u2010CD. (A) Sequence alignment of DGK\u03b6\u2010CD (aa 293\u2013622) and DGK\u03b9\u2010CD (aa 374\u2013702). Sequence alignment was created using Clustal Omega provided by EMBL's European Bioinformatics Institute (EMBL\u2010EBI). Compared with DGK\u03b6\u2010CD, white letters on a black background indicate fully conserved residues, and black letters on a gray background indicate strongly similar residues. (B) Amino acid identities between DGK\u03b6\u2010CD and DGK\u03b9\u2010CD. Amino acid identity and similarity were determined using Pairwise Sequence Alignment provided by the European Molecular Biology Open Software Suite (EMBOSS).Click here for additional data file."}
{"text": "The crystal structure of bucetin, an analgesic and anti\u00adpyric similar to phenacetin, is presented. N-(4-eth\u00adoxy\u00adphen\u00adyl)-3-hydroxy\u00adbutanamide], C12H17NO3, the mol\u00adecule is in an extended conformation as illustrated by the C\u2014O\u2014C\u2014C torsion angle [170.14\u2005(15)\u00b0] in the eth\u00adoxy group and the subsequent C\u2014N\u2014C\u2014C [\u2212177.24\u2005(16)\u00b0], N\u2014C\u2014C\u2014C [170.08\u2005(15)\u00b0] and C\u2014C\u2014C\u2014C [171.41\u2005(15)\u00b0] torsion angles in the butanamide chain. In the crystal, the O\u2014H group donates an inter\u00admolecular O\u2014H\u22efO hydrogen bond to the amide carbonyl oxygen atom and also accepts an inter\u00admolecular N\u2014H\u22efO hydrogen bond from an adjacent N\u2014H group. The former forms 12-membered dimeric rings about inversion centers, and the latter form chains in the [001] direction. The overall hydrogen-bonded network is two-dimensional, with no propagation in the [100] direction.In the title compound, racemic bucetin [systematic name:  N-(4-Eth\u00adoxy\u00adphen\u00adyl)-3-hydro\u00adbutanamide, popularly known as bucetin, is an analgesic and anti\u00adpyric that is similar in structure to phenacetin [N-(4-eth\u00adoxy\u00adphen\u00adyl)acetamide]. Once thought to be a better substitute for phenacetin hydroxyl\u00adamine and 1-eth\u00adoxy-4-nitroso\u00adbenzene) on PGE2 synthesis and a possible reduction of COX-2 expression acetamide  and 2.8611\u2005(19)\u2005\u00c5 for N\u2014H\u22efO was obtained from Sigma-Aldrich, St. Louis, MO and was used without further purification. Single crystals of racemic bucetin were prepared by slow cooling of a nearly saturated solution of bucetin in boiling deionized water.The title compound, CCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623002316/vm4059sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623002316/vm4059Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623002316/vm4059Isup3.cmlSupporting information file. DOI: 2247342CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure, the Th atom (site symmetry 3\u221e[ThBr4/2Br4/2]. In comparison with the previous crystal structure refinement , the current rerefinement resulted in much higher preciscion of the lattice parameters and the atomic coordinates.Single crystals of \u03b1-ThBr al. 1974. J. Less A comparison of the structural parameters of the original crystal structure refinement and of the current rerefinement is given in Table\u00a01The crystal structure of \u03b1-ThBra, site symmetry f, site symmetry 1) in the asymmetric unit. The Th atom is surrounded by eight Br atoms to form a tetra\u00adgonal-disphenoidal coordination polyhedron. The Th\u2014Br bond lengths of 4\u00a0\u00d7 2.9100\u2005(4)\u2005\u00c5 and 4\u00a0\u00d7 3.0107\u2005(4)\u2005\u00c5 are in good agreement with previously reported values of 2.909 and 3.020\u2005\u00c5 , with values of 2.85 and 3.12\u2005\u00c5 \u2005\u00c5 in \u03b1-ThBr4 is shorter compared to \u03b2-ThBr4, with a value of 4.8774\u2005\u00c5 \u2005\u00c5 and 4\u00a0\u00d7 6.70680\u2005(19)\u2005\u00c5.Fig.\u00a01\u22123\u2005mbar; 1\u2005bar = 105\u2005Pa) at least three times before use. Aluminium bromide  was sublimed in vacuo before use; \u03b2-ThBr4 was prepared according to a literature protocol  using a fine-vacuum line and a glove-box (MBraun). Silica ampoules were flame-dried under dynamic fine vacuum  and CuBr , and sealed under vacuum. The ampoule was heated in a furnace to 753\u2005K at a rate of 1\u2005K\u2005min\u22121 and kept at this temperature for 480\u2005h for the reaction to take place. Afterwards, it was cooled to 330\u2005K at a rate of 50\u2005K\u2005d\u22121. Several colourless crystals of \u03b1-ThBr4 were obtained.A silica glass ampoule was loaded with \u03b2-ThBrCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623008908/wm4200sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314623008908/wm4200Isup2.hklStructure factors: contains datablock(s) I. DOI: 2300477CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The carbamate group has key bond lengths of 1.404\u2005(6)\u2005\u00c5 (N\u2014C), 1.330\u2005(5)\u2005\u00c5 (O\u2014C), and 1.201\u2005(6)\u2005\u00c5 (C=O). The crystal contains inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions, as well as both type I and type II inter\u00admolecular I\u22efI inter\u00adactions.The mol\u00adecular structure of  These inter\u00adactions have Cg\u22efCg distances of 3.484\u2005(3) and 3.589\u2005(3)\u2005\u00c5 with slippages of 1.028 and 1.376\u2005\u00c5 and angles of 0.00\u2005(3)\u00b0 . The supra\u00admolecular pillars are held together via both type I and type II inter\u00admolecular I\u22efI inter\u00adactions  with an angle of 147.68\u2005(13)\u00b0 and an I\u22efI distance of 3.6630\u2005(5)\u2005\u00c5. The type II inter\u00adaction is found between atoms C11\u2014I2\u22efI1 with an I\u22efI distance of 3.8332\u2005(5)\u2005\u00c5 and an angle of 46.69\u2005(13)\u00b0.In the crystal, mol\u00adecules of the title compound form pillars 4.et al., 2016et al., 2015I with iodine atoms at the C5 and C11 positions, but where the nitro\u00adgen atom has been alkyl\u00adated with either a butyl or benzyl group. Structure ECUNUM bears bromine atoms at the C5 and C11 positions with a phenyl\u00adcarbamate group on the nitro\u00adgen atom  = 1.2Ueq(C) for aromatic hydrogen atoms and Uiso(H) = 1.5Ueq(C) for the hydrogen atoms of the methyl group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S205698902300230X/wm5676sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902300230X/wm5676Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902300230X/wm5676Isup3.cmlSupporting information file. DOI: 2247288CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-chromen-4-yl\u00adamino)\u00adbenzoate, has been synthesized and characterized.A new coumarin derivative, methyl 2-(2-oxo-2 H-chromen-4-yl\u00adamino)\u00adbenzoate, C17H13NO4 (1), was pre\u00adpared by condensation between 4-hy\u00addroxy\u00adcoumarin and methyl 2-amino\u00adbenzoate. It crystallizes in the ortho\u00adrhom\u00adbic space group Pca21 at 300\u2005K. The mol\u00adecule of compound 1 consists of the 2H-chromen-2-one part connected by an amine moiety (\u2013NH\u2013) to the methyl benzoate ring. The supra\u00admolecular array is formed by hydrogen bonds between the aromatic ring and the O atoms of the lactone and ester portions. The structural details match the spectroscopic data acquired from NMR and IR spectroscopy.Methyl 2-(2-oxo-2 These sDipteryx odorata Wild; Fabaceae family) by Vogel in 1820. Since then, more than 1300 coumarins have been identified from natural sources \u00adbenzoate, 1 \u00adbenzoate mol\u00adecule , although the C4\u2014N1\u2014C9 angle at 130.9\u2005(4)\u00b0 is about 7\u00b0 larger than in those mol\u00adecules, presumably due to the intra\u00admolecular N1\u2014H1\u22efO2 hydrogen bond (Table\u00a01The average C\u2014C bond distance in the aromatic portion of the coumarin is 1.374\u2005(7)\u2005\u00c5, while the C9\u2014C13, C9\u2014C10 and C10\u2014C11 bond lengths in the lactone portion are 1.450\u2005(7), 1.353\u2005(7) and 1.412\u2005(7)\u2005\u00c5, respectively, because of the partial localization of \u03c0-bonding within the ring. The C11\u2014O3 and C12\u2014O3 bond lengths are equivalent at 1.374\u2005(7) and 1.373\u2005(7)\u2005\u00c5, respectively, while the C11=O4 distance is 1.204\u2005(7)\u2005\u00c5. The sum of the angles about N1 is 359\u2005(3)\u00b0, implicating involvement of its lone pair in N\u2014C \u03c0-bonding. This is supported by the N1\u2014C9 and N1\u2014C4 distances of 1.351\u2005(6) and 1.391\u2005(6)\u2005\u00c5, respectively. Similar geometrical parameters are found in closely related structures \u00b0.1H and 13C NMR confirms the product as methyl 2-(2-oxo-2H-chromen-4-yl\u00adamino)\u00adbenzoate. In the 1H NMR spectrum, there is a singlet at \u03b4 3.74 ppm attributable to the meth\u00adoxy group of the ester, the coumarin vinylic H atom appears at \u03b4 5.31 ppm and a singlet is seen at \u03b4 9.67 which can be assigned to N\u2014H. In addition, there are eight aromatic H atoms between \u03b4 7.44 and 8.14 ppm. In the 13C NMR spectrum, the meth\u00adoxy group appears at \u03b4 52.47 ppm, the two carbonyl C atoms at \u03b4 166.50 and 161.40, and the vinylic and aromatic C atoms between \u03b4 114 and 154 ppm.The NMR spectra are shown in Figs. 43.B\u22efO4i) and the H atom from the aromatic ring (C7\u2014H7\u22efO4ii)  Table\u00a01. These bon Fig.\u00a06. The cryon Fig.\u00a06 involves4.et al., 2016H-chromen-2-one -2H-chromen-2-one  was heated in a 50\u2005ml Becher at 453\u2005K for 1\u2005h. A solution comprised of 30\u2005ml of hot methanol and 30\u2005ml of aqueous NaOH (1\u2005mol\u2005l\u22121) was then added to the solid. This mixture was stirred for 30\u2005min at 333\u2005K and then filtered. The solid was washed with water, dried and used without further purification.The reaction was carried out according to the literature  I. DOI: 10.1107/S2056989023007351/mw2198Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007351/mw2198Isup3.cmlSupporting information file. DOI: 2289922CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure features C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, which link the mol\u00adecules into layers parallel to the (100) plane. IC\u2014H\u22ef\u03c0 inter\u00adactions and weak van der Waals inter\u00adactions occur between the layers. 25H17N3O5S2, intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid-to-centroid distance = 3.5640\u2005(9)\u2005\u00c5] are observed between the furan and benzene rings of the 4-cyano\u00adphenyl group. In the crystal, mol\u00adecules are connected via C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming layers parallel to the (100) plane. These layers are inter\u00adconnected by C\u2014H\u22ef\u03c0 inter\u00adactions and weak van der Waals inter\u00adactions. Hirshfeld surface analysis indicates that H\u22efH (30.2%), N\u22efH/H\u22efN (22.3%), C\u22efH/H\u22efC (17.9%) and O\u22efH/H\u22efO (15.4%) inter\u00adactions make the most significant contributions to the crystal packing.In the title compound, C Reactions with ammonia, and primary and secondary amines are the most widespread. A primary amine will form a soluble sulfonamide salt in the presence of aqueous alkali (either KOH or NaOH). A secondary amine in the same reaction forms an insoluble sulfonamide. The most widely used sulfonyl\u00adamide is sulfanil\u00adamide, an anti\u00adbacterial drug that was first obtained in 1908 by the Austrian chemist Paul Josef Jakob Gelmo while he was trying to synthesize a dye for textile materials .In the title compound Fig.\u00a02, the angCg1\u22efCg4 = 3.5640\u2005(9)\u2005\u00c5; Cg1 and Cg4 are the centroids of the furan (O1/C7\u2013C10) and benzene rings (C19\u2013C24), respectively, of one of the two 4-cyano\u00adphen\u00adyl)sulfonyl groups, respectively; slippage = 0.793\u2005\u00c5], ensures the stability of the mol\u00adecular configuration.Intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions  between the furan and a phenyl ring of one of the two (3-nitro\u00adphen\u00adyl)sulfonyl groups result in chains parallel to the a axis. In JOBTIF (space group P21/n), mol\u00adecules are linked by pairs of C\u2014H\u22efO hydrogen bonds, forming inversion dimers. In CEGMIM (space group Pbca), mol\u00adecules are connected by C\u2014H\u22efO inter\u00adactions into sheets in the ab plane. In the crystal of CEGSUE , mol\u00adecules associate via N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, forming extended hydrogen-bonded sheets that lie parallel to the bc plane. The N\u2014H\u22efN hydrogen bonds propagate along the b-axis direction, while the N\u2014H\u22efO hydrogen bonds propagate along the c-axis direction. The crystal structure of OCABUR (space group P21/c) features C\u2014H\u22efO hydrogen bonds. In the crystal structure of AYUPUG (space group P21/c), weak C\u2014H\u22efO inter\u00adactions connect the mol\u00adecules in a zigzag manner along the a-axis direction. In the crystal of PONZIC (space group Pa axis by inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions. In ROGJON (space group Pbca), the crystal structure features weak inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions.In PIMGUR  was added gradually to a solution of 2-(5-methyl-2-fur\u00adyl)aniline  in pyridine (7\u2005mL) under stirring and cooling in an ice\u2013water bath. The mixture was stirred for 7\u2005h at r.t. and after completion of the reaction , the mixture was poured into hydro\u00adchloric acid . The separated oil was washed with water until its crystallization. The obtained crystals were filtered off, dried, and recrystallized from an ethanol/di\u00admethyl\u00adformamide (DMF) mixture to give the target disulfonamide as a colourless solid. Single crystals were obtained by slow crystallization from an EtOH/DMF mixture . IR (KBr), \u03bd (cm\u22121): 1156 (\u03bds SO2), 1329 (\u03bdas SO2), 2237 (CN). 1H NMR  : \u03b4 8.08 , 7.90 , 7.72 , 7.56 , 7.36 , 7.04 , 6.61 , 5.93 , 1.96 ; 13C{1H} NMR : \u03b4 153.2, 147.9 (2C), 142.9, 134.0 (4C), 133.7, 132.2, 132.0, 129.6 (4C), 128.8, 128.7, 128.6, 117.9 (2C), 117.4 (2C), 112.0, 108.6, 13.4; MS (ESI) m/z: [M + H]+ 504. Elemental analysis calculated (%) for C25H17N3O5S2 %: C 59.63, H 3.40, N 8.34, S 12.74; found: C 60.00, H 3.27, N 8.56, S 13.03.6.Ueq(C) (1.5 for methyl groups). The hydrogen atoms of the methyl group containing the C11 atom were disordered over two positions with equal occupancies.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023006254/tx2071sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023006254/tx2071Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023006254/tx2071Isup3.cmlSupporting information file. DOI: 2282070CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, N\u2014H\u22efO and C\u2014H\u22efO hydro\u00adgen bonds form chains extending along the b-axis direction. Due to the disorder of the p-tolyl rings, short C\u22efC distances are observed between adjacent chains.The quinoxaline moiety in the title mol\u00adecule, C Lgaz et al., 2015e.g. Abad et al., 2021Among the various classes of nitro\u00adgen heterocyclic compounds, quinoxaline derivatives display a broad spectrum of biological and pharmacological activities \u00b0 apart in a 0.503\u2005(2):0.497\u2005(2) ratio. In the crystal, N3\u2014H3A\u22efO2 and C10\u2014H10B\u22efO2 hydro\u00adgen bonds (Table\u00a01b-axis direction. Pairs of inversion-related chains show C16\u22efC17i and C17\u22efC16i  distances of 2.695\u2005(4)\u2005\u00c5, which is 0.71\u2005\u00c5 less than the sum of the van der Waals radii and is likely due to the disorder involving this ring. The chains stack along the c-axis direction \u00b0 between the mean planes through the constituent rings. The s Table\u00a01 form chan Figs.\u00a02 and\u00a03 \u25b8.H)-one was dissolved in 25\u2005ml of di\u00admethyl\u00adformamide and 1.15\u2005g (6.24\u2005mmol) of 2-chloro-N-(p-tol\u00adyl)acetamide were added, followed by 1.0\u2005g (7.5\u2005mmol) of potassium bicarbonate, and a spatula tip of BTBA (benzyl\u00adtri\u00adbutyl\u00adammonium chloride) was used as a phase-transfer catalyst. The reaction was stirred for 2\u2005h under reflux at 353\u2005K. When the starting reagents had completely reacted, 500\u2005ml of distilled water were added and a few minutes later the product precipitated. This was filtered off, dried and recrystallized from hot ethanol solution to yield light-yellow plate-like crystals of the title compound.1.00\u2005g (6.24\u2005mmol) of 3-methyl\u00adquinoxalin-2(1I/\u03c3(I) > 20 and chosen from the full data set with CELL_NOW :0.497\u2005(2) ratio] of the disordered C12\u2013C17 ring were refined as rigid hexa\u00adgons.Crystal, data collection and refinement details are presented in Table\u00a0210.1107/S2414314623003577/vm4060sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623003577/vm4060Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623003577/vm4060Isup3.cmlSupporting information file. DOI: 2254194CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: BMC Ophthalmol\u00a023, 279 (2023)https://doi.org/10.1186/s12886\u2013023-03012-1After publication of the original article , the autThe original article has been updated and the correct values are also given below in bold.The second paragraph in page 4 should read:28.6\u00a0mg/dL, and apolipoprotein A1\u00a0131.6\u00a0mg/dL. A total of 782 patients in the alirocumab group had\u2009\u2265\u20092 consecutive LDL-C values\u2009<\u200915\u00a0mg/dL (0.39\u00a0mmol/L) and were matched to 2346 patients from the placebo group with similar baseline characteristics (Tables 4 and 5). Baseline characteristics of these patients included mean age 59\u00a0years, male sex (81%), diabetes (33%); and mean body mass index 27.3\u00a0kg/m2, LDL-C 2.0\u00a0mmol/L, lipoprotein (a) 18.8\u00a0mg/dL, and apolipoprotein A1\u00a0129.9\u00a0mg/dL.A total of 4305 patients in the alirocumab group had\u2009\u2265\u20092 consecutive LDL-C values\u2009<\u200925\u00a0mg/dL (0.65\u00a0mmol/L) and were matched to 4305 patients from the placebo group with similar baseline characteristics (Tables 2 and 3). Baseline characteristics of these patients included mean age 59\u00a0years, male sex (81%), diabetes (33%); and mean body mass index 28.3\u00a0kg/m2, LDL-C 2.1\u00a0mmol/L, lipoprotein (a)"}
{"text": "The layers are connected by additional C\u2014H\u22efO hydrogen bonds and \u03c0-stacking inter\u00adactions.In the title compound, the thia\u00adzine ring exhibits a screw-boat conformation. In the crystal, corrugated layers of mol\u00adecules parallel to the  8H7NO3S, the nitro\u00adgen atom has a planar environment, and the thia\u00adzine ring exhibits a screw-boat conformation. In the crystal, corrugated layers of mol\u00adecules parallel to the ab plane are formed by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) and S=O\u22ef\u03c0(ring) inter\u00adactions. The layers are connected by additional C\u2014H\u22efO hydrogen bonds and \u03c0-stacking inter\u00adactions. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H\u22efO/O\u22efH (49.4%), H\u22efH (23.0%) and H\u22efC/C\u22efH (14.1%) inter\u00adactions. The volume of the crystal voids and the percentage of free space were calculated as 75.4\u2005\u00c53 and 9.3%. Density functional theory (DFT) computations revealed N\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding energies of 43.3, 34.7 and 34.4\u2005kJ\u2005mol\u22121, respectively. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via the electrostatic energy contribution. Moreover, the DFT-optimized structure at the B3LYP/ 6\u2013311\u2005G level is compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.In the title mol\u00adecule, C The distorted screw-boat conformation places O2 in an axial position and O3 in a pseudo-equatorial position \u2005\u00c5, S1\u22efCg2 = 4.1655\u2005(5)\u2005\u00c5, S1=O2\u22efCg2i = 101.77\u2005(3)\u00b0; symmetry code: (i) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0Cg2\u22efCg2 = 3.7353\u2005(5)\u2005\u00c5, slippage = 1.55\u2005\u00c5] into a tri-periodic network structure  with 4.9% contribution to the HS is viewed at de + di = 3.30\u2005\u00c5. The C\u22efC contacts  appearing as a bullet-shaped distribution of points make a contribution of 3.7% to the HS with the tip at de = di = 1.70\u2005\u00c5. The spikes of H\u22efN/N\u22efH contacts  with 3.2% contribution to the HS are viewed at de + di = 2.75\u2005\u00c5. Finally, the O\u22efO  and C\u22efN/N\u22efC  contacts contribute 1.3% and 0.4%, respectively, to the HS. The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H\u22efO/O\u22efH, H\u22efH and H\u22efC/C\u22efH inter\u00adactions in Fig.\u00a08a\u2013c, respectively. The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efO/O\u22efH, H\u22efH and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions play the major role in the crystal packing u. Fig.\u00a04, the whits Fig.\u00a07e with 4ts Fig.\u00a07f appearts Fig.\u00a07g with 3\u22efO Fig.\u00a07h and C\u22ef\u22efC Fig.\u00a07i contacet al., 2011a,b) and the percentage of free space in the unit cell are calculated as 75.4\u2005\u00c53 and 9.3%, respectively. Thus, the crystal packing appears compact and the mechanical stability should be substantial.The strength of the crystal packing is important for determining the response to an applied mechanical force. If the crystal packing results in significant voids, then the mol\u00adecules are not tightly packed and a small amount of applied external mechanical force may easily break the crystal. To check the mechanical stability of the crystal, a void analysis was performed by adding up the electron densities of the spherically symmetric atoms contained in the asymmetric unit  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be  for N1\u2014H1\u22efO3,  for C8\u2014H8B\u22efO2 and  for C5\u2014H5\u22efO1.The inter\u00admolecular inter\u00adaction energies were calculated using the CEB3LYP/631G energy model available in et al., 2015Eele Energy frameworks combine the calculation of inter\u00admolecular inter\u00adaction energies with a graphical representation of their magnitude EHOMO and ELUMO, electronegativity (\u03c7), hardness (\u03b7), dipole moment (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are compiled in Table\u00a03\u03b7 and \u03c3 are essential for assessing reactivity and stability. The electron transition from HOMO to LUMO energy levels is depicted in Fig.\u00a011b]thia\u00adzin-3(4H)-one 1,1-dioxide ring. The energy band gap [\u0394E = ELUMO\u00a0\u2212\u00a0EHOMO] for the mol\u00adecule is 11.7261\u2005eV, and the energies of the frontier mol\u00adecular orbitals, EHOMO and ELUMO, are \u22129.6740\u2005eV and 2.0522\u2005eV, respectively.The highest-occupied mol\u00adecular orbital (HOMO), functioning as an electron donor, and the lowest-unoccupied mol\u00adecular orbital (LUMO), acting as an electron acceptor, serve as vital parameters in quantum chemistry. A small energy gap signifies high mol\u00adecular polarizability and enhanced chemical reactivity. The DFT calculations provided crucial insights into the reactivity and site selectivity of the mol\u00adecular framework. Parameters such as 7.et al., 2016II was dissolved in 3\u2005ml of acetic acid and added dropwise into a solution of potassium permanganate (1.81\u2005mmol) in 6\u2005ml of water. After stirring for one\u2005h at room temperature, a solution of sodium thio\u00adsulfate penta\u00adhydrate (20%wt) was added to react with excessive potassium permanganate. The precipitate obtained was filtered and recrystallized from ethanol to yield single-crystals suitable for X-ray structure analysis..3,4-Di\u00adhydro-29.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698902300868X/wm5698sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698902300868X/wm5698Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902300868X/wm5698Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698902300868X/wm5698Isup4.cmlSupporting information file. DOI: 2298958CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The various inter\u00admolecular inter\u00adactions, such as N\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22efO, were investigated using Hirshfeld surface analysis and the three-dimensional inter\u00adaction energies were calculated. 29H27F2N3O6, which crystallizes in the monoclinic space group P21/c, the cyclo\u00adhexenone ring is puckered and adopts an envelope conformation. The crystal structure features various inter\u00admolecular inter\u00adactions, such as N\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22efO. These inter\u00adactions were investigated using Hirshfeld surface analysis and the three-dimensional inter\u00adaction energies were calculated using the B3LYP/6\u201331\u2005G energy density model.In the title compound, C The orientation of other two carboxyl\u00adate groups at the C4 and C5 positions are described by the torsion angles C1\u2014C6\u2014C27\u2014O6 = \u221215.4\u2005(5)\u00b0 (\u2013syn-periplanar), C1\u2014C6\u2014C27\u2014O5 = 167.2\u2005(4)\u00b0 (+anti-periplanar), C5\u2014C6\u2014C27\u2014O5 = \u221217.2\u2005(6)\u00b0 (\u2013anti-periplanar), C5\u2014C6\u2014C27\u2014O6 = 160.1\u2005(3)\u00b0 (+anti-periplanar) and C3\u2014C4\u2014C23\u2014O3 = 44.9\u2005(5)\u00b0 , C3\u2014C4\u2014C23\u2014O4 = \u2212136.4\u2005(3)\u00b0 , C5\u2014C4\u2014C23\u2014O3 = \u221275.8\u2005(4)\u00b0 , C5\u2014C4\u2014C23\u2014O4 = 102.9\u2005(3)\u00b0 . The orientation is due to the inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions.In the title compound Fig.\u00a01, the cyc3.N\u22efO1, C14\u2014H14B\u22efN3, and C24\u2014H24B\u22efO3 propane-1,2,3-tri\u00adcarboxyl\u00adate  was computed using two-dimensional fingerprint calculations  mapped over ns Fig.\u00a05. The res6.CrystalExplorer 17.5 software calculates inter\u00adaction energies between crystal mol\u00adecular pairs. Energy calculations were carried out using the B3LYP/6-31G basis set within a default radius of 3.8\u2005\u00c5  is associated with a pair of yellow mol\u00adecules with the short centroid distance R = 9.29\u2005\u00c5 with rotational symmetry \u2212x, y\u00a0+\u00a0z\u00a0+\u00a0Etot = \u221217.6\u2005kJ\u2005mol\u22121) was observed for a pair of green mol\u00adecules inter\u00adacting at the longer centroid distance R = 12.86\u2005\u00c5; this is in accordance with the classical laws of electrostatics. In each of the energy terms, the dispersion component is dominant over the others.7.2SO4, then concentrated under reduced pressure to get the crude product. This was purified by silica gel column chromatography using n-hepta\u00adne/ethyl acetate as eluent. The mixture was quenched in cold water and the organic layer was extracted with ethyl acetate, washed with 5% sodium bicarbonate solution, and dried over anhydrous sodium sulfate. Slow evaporation of the solvent lead to crystals of the title compound, which were recrystallized from ethanol solution.Piperidine (6\u2005mmol) was added to ethyl cyano\u00adacetate (30\u2005mmol) and the mixture was stirred for 10\u2005min. Then 4-fluoro\u00adbenzaldehyde (20\u2005mmol) was added dropwise and during the addition, the temperature of the reaction mass rose to 333\u2005K (it should not be cooled), and the mass was stirred for 30\u2005min. The temperature slowly came down to 293\u2013298\u2005K over 30\u2005min. The progress of the reaction was monitored by TLC and found to be complete. Methyl\u00adene chloride (30\u2005ml) and water (20\u2005ml) were added and the mixture was stirred for 10\u2005min. The organic layer was separated and washed with sat. aq. NaCl solution and dried over anhydrous Na8.Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023003134/ex2065sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989023003134/ex2065Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023003134/ex2065Isup3.cmlSupporting information file. DOI: 2202315CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "However, it remains largely unclear how those cells develop. Here we show that transforming growth factor beta (TGF-\u03b2) signaling controls the development of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. Deletion of TGF-\u03b2 receptors or Smad3 and Smad2 in bone marrow stem cells caused a deficiency of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in mixed bone marrow chimeric mice. Mechanistically, TGF-\u03b2 is required for the development of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs thymic precursors (CD44\u2013CD25\u2013 \u03b3\u03b4 thymocytes). In addition, TGF-\u03b2 signaling induced CD8\u03b1 in thymic \u03b3\u03b4T cells and maintained CD8\u03b1 expression and survival in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. Moreover, TGF-\u03b2 also indirectly controls TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs by modulating the function of intestinal epithelial cells (IECs). Importantly, TGF-\u03b2 signaling in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs safeguarded the integrity of the intestinal barrier in dextran sulfate sodium (DSS)-induced colitis.\u03b3\u03b4 intestinal intraepithelial lymphocytes (IELs) constitute the majority of IELs with unique CD8\u03b1\u03b1 T cell receptor (TCR)+ IELs, which express either TCR\u03b3\u03b4+ or TCR\u03b1\u03b2+ are usually classified into conventional and unconventional IELs according to their distinct phenotype and developmental pathways. \u03b3\u03b4 IELs are thought to be homed to the intestine immediately after their generation from \u03b3\u03b4T precursors in the thymus2. They comprise the vast majority of IELs in the small intestine and are essential to maintaining immune homeostasis in the intestinal territory, such as keeping the integrity of the gut barrier, limiting translocation of microbiomes, responding to antigens invasion, and healing tissue damage. Accumulated studies have shown that the function of \u03b3\u03b4 IELs is tightly related to their crosstalk with IECs; the dynamic movement of \u03b3\u03b4 IELs surrounding IECs results in more efficient immune surveillance and higher expression of antimicrobial or antiviral genes5.Intestinal intraepithelial lymphocytes (IELs) localize within the intestinal epithelium and predominate in the mucosal immune system; they are typically surrounded by intestinal epithelial cells (IECs) with a ratio of ~1:10 (IELs:IECs) in the small intestine+ homodimers that are considered the main cell resource for the production of cytokines like IFN-\u03b3, IL-10, and IL-13 from \u03b3\u03b4 IELs1. However, it remains uncertain which factors determine the development of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. The development of \u03b3\u03b4T cells in the thymus undergoes several stages from DN1 to DN4 that can be classified by CD44 and CD25 expression, namely CD44+CD25\u2013 (DN1), CD44+CD25+ (DN2), CD44\u2013CD25+ (DN3), and CD44\u2013CD25\u2013 (DN4)8. However, it has been recently suggested that the V\u03b37+ subset of IELs were generated in an extrathymic way, which relies on Butyrophilin-like (Btnl) molecules on IECs9, but this remains to be verified.Unlike systemic \u03b3\u03b4T cells settled in other sites, roughly 90% of \u03b3\u03b4 IELs have a specific phenotype of CD8\u03b1\u03b112. TGF-\u03b2 is enriched in the intestinal environment and represents one of the most important regulators in gut immune system as both IECs and immune cells, including IELs, contribute to TGF-\u03b2 production14. Additionally, we and others have previously found that TGF-\u03b2 signaling is crucial for the development of TCR\u03b1\u03b2+CD8\u03b1\u03b1+ IELs and the generation of TCR\u03b1\u03b2+CD8\u03b1+CD4+ IELs16. However, it remains unknown whether TGF-\u03b2 plays a role in the development of TCR\u03b3\u03b4+ CD8\u03b1\u03b1+ IELs.TGF-\u03b2 signaling is involved in the development of various immune cells in the thymus and periphery, such as \u03b1\u03b2T cells, T regulatory cells (Tregs), and Th17 cells+CD8\u03b1\u03b1+ IELs in a Smad2 and Smad3 (Smad2/3)-dependent manner. Mice lacking TGF-\u03b2 receptors or Smad2/3 have fewer TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs and thymic \u03b3\u03b4 precursors capable of migrating to the intestine. We discovered that TGF-\u03b2 induces CD8\u03b1 but not CD8\u03b2 expression in DN \u03b3\u03b4 thymic precursors of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs through the upregulation of RUNX family transcription factor 3 (Runx3) and downregulation of Th-inducing POZ-Kruppel factor (Th-Pok), two transcriptional factors important for CD8+T cell commitment in the thymus. Moreover, TGF-\u03b2 directly regulates the maintenance of CD8\u03b1 expression, proliferation, and apoptosis of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs or indirectly influences these \u03b3\u03b4 IELs by modulating the function of IECs. Finally, we found that mice with TGF-\u03b2 signaling deficiency in \u03b3\u03b4T cells were more vulnerable to bacterial attacks and had a worse response to DSS-induced IBD.We here show that TGF-\u03b2 controls the development of TCR\u03b3\u03b418. The number of \u03b3\u03b4 IELs gradually increases from the day of mouse birth and remains stable in 1 month19. We generated mixed BM chimeric mice to investigate the role of TGF-\u03b2 in the development of \u03b3\u03b4 IELs. BM cells from CD45.1 wild-type (WT) mice (CD45.1) were mixed with BM cells from CD45.2 Tgfbr1f/fEsr1-cre mice that had been pretreated with tamoxifen (R1 KO) or oil (R1 WT) for 5 days in a ratio 1:6 (CD45.2:CD45.1). The mixed BM cells were then transferred into irradiated recombination-activation gene 1-deficient (Rag1\u2212/\u2212) mice. The Rag1\u2212/\u2212 mice were sacrificed to examine IELs populations 4\u20135 weeks later  cells and reside in the intestine after development in the thymusced Fig. , while tsed Fig. . The fresed Fig.  and totased Fig.  were alssed Fig.  and lympsed Fig.  showed nTgfbr2f/fEsr1-cre mice (pretreated with tamoxifen (R2 KO) or oil (R2 WT) for 5 days) and obtained similar results. Specifically, the frequency and total cell number of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs from R2 KO BM-transferred mice were decreased compared to other control mice  or WT control  BM cells and found that TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs were significantly reduced in Smad2/3dko mice 20. We next examined subsets of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs from Smad2/3dko BM chimeric mice and found that their CD8\u03b1\u03b1+ V\u03b31  \u03b3\u03b4T cell population were all diminished in R1 KO BM-derived thymocytes  had no difference between R1 WT and R1 KO mice  and \u03b1E\u03b27 integrin , and \u03b3\u03b4T cells in the thymus express a high level of CCR9 that is downregulated when they arrive in the intestine accompanied by CD103 upregulation in mice22. We examined CCR9 on thymic DN4 \u03b3\u03b4T cells from CD45.1\u2009+\u2009R1 WT and CD45.1\u2009+\u2009R1 KO mixed BM chimeric mice. Both the frequency of CCR9+ cells and MFI of CCR9 expression in DN4 thymic \u03b3\u03b4T cell precursors  analysis of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs isolated from the mixed BM chimeric mice 4\u20135 weeks post-BM transplantation as shown in Fig. https://www.ncbi.nlm.nih.gov/sra/?term=PRJNA739380). Consistent with our flow cytometry analysis, the gene expression of CD103 (Itgae) was substantially downregulated in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs from R1 KO BM chimeric mice, while the gene of CCR9 (Ccr9) was comparable  is another factor that potentially impacts the migration of \u03b3\u03b4 IELs, and RNA-seq revealed no difference of Itga4 in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs  was downregulated in thymic \u03b3\u03b4T cells by TGF-\u03b21 , Aatk (apoptosis-associated tyrosine kinase), and Bcl2l14  were all upregulated in R1 KO TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs according to our RNA-seq data  or tamoxifen (R1 KO)-treated Tgfbr1f/fEsr1-cre mice for 5 days and examined the mRNA expression of Butyrophilin-like (Btnl1), IL-15 and Myd88 in IECs. These genes are expressed on IECs and suggested to be important for TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs generation28. In R1 KO IECs, the expression of Btnl1  or Smad3\u2212/\u2212 mice with IECs from WT or Smad3\u2212/\u2212 mice with a ratio 1:10  and RegIII\u03b2 , such as Il17a, Il23a, and Ifng31 were all upregulated in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in TGF-\u03b2 receptor I-deficient mice  approach. The intestinal structure of Smad3\u2212/\u2212 mice exhibited more damage with heavier bacteria located within or under the epithelial layer than WT mice  that contained fewer TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs  was diminished in the absence of TGF-\u03b2 signaling, but CD44\u2212CD25+TCR\u03b3\u03b4+ thymocytes (DN3-\u03b3\u03b4T) were not much altered. This suggests that TGF-\u03b2 might start working in the stage when \u03b3\u03b4T cells are developing from DN3 to DN4. Intriguingly, we found more CD44+CD25\u2212TCR\u03b3\u03b4+ thymocytes, which exhibit DN1-like phenotype, in TGF-\u03b2 receptor I-deficient mice, suggesting that TGF-\u03b2 signaling controls this subset of CD44+CD25\u2212TCR\u03b3\u03b4+ thymocytes37. However, the mechanism underlying this abnormal increase in this unique type of CD44+CD25\u2212TCR\u03b3\u03b4+ thymocytes remains unknown. As TCR\u03b3\u03b4+ thymocytes are presented as either DN3 or DN4 by surface staining38, these CD44+CD25\u2212TCR\u03b3\u03b4+ cells are likely recirculated peripheral \u03b3\u03b4T cells, which are activated in the absence of TGF-\u03b2 or are converted from DN4 CD44\u2212CD25\u2212 \u03b3\u03b4T cells by regaining expression of CD44 due to the Tgfbr1 deficiency. Nevertheless, the decrease in CD44\u2212CD25\u2212TCR\u03b3\u03b4+ DN4 thymocyte should contribute to the deficiency of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in the absence of TGF-\u03b2 signaling.Consistent with the crucial role of TGF-\u03b2 in the thymic environment+CD8\u03b1\u03b1+ IELs was not affected by TGF-\u03b2 because their expression of the essential chemokine CCR9 and integrin \u03b14\u03b27 for homing to the gut intraepithelial layer was comparable between WT and TGF-\u03b2-deficient mice. However, the ability of \u03b3\u03b4 IELs to reside in the gut could be degraded due to CD103 low expression on TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IEL in TGF-\u03b2 signaling-deficient mice. As \u03b3\u03b4 IELs normally express CD103 rather than CCR9 in the gut, CD103 is more important for \u03b3\u03b4T cells to settle down in the gut. This notion is further supported by the evidence that TGF-\u03b2 induces more expression of CD103 in normal thymic \u03b3\u03b4T cells and gut T cells23. Collectively, TGF-\u03b2 promotes the development of the thymic precursor CD25\u2212CD44\u2212TCR\u03b3\u03b4+ cells of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs and increases the expression of their gut-resident integrin CD103, which together provide a crucial step to fulfill a sufficient number of \u03b3\u03b4 IELs.The migration ability of thymic \u03b3\u03b4 precursors of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in the gut. Therefore, we have revealed that TGF-\u03b2 induces expression of CD8\u03b1 in thymic \u03b3\u03b4T cells and maintains CD8\u03b1 expression in mature TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. For thymic \u03b3\u03b4T cells, TGF-\u03b2 induces CD8\u03b1 by regulating the balance of Runx3 and Th-Pok expression, i.e., via upregulation of Runx3 and downregulation of Th-Pok, although the detailed molecular mechanism by which TGF-\u03b2 regulates these two transcriptional factors remains to be elucidated. Strikingly, we believe that the role of TGF-\u03b2 in thymic \u03b3\u03b4T cells also includes facilitating those cells to maintain the potential to develop into CD8\u03b1\u03b1+ homodimers, instead of CD8\u03b1\u03b2+ heterodimers, based on our data that CD8\u03b2 on thymic \u03b3\u03b4T cells tends to be inhibited by TGF-\u03b2 treatment. In splenic \u03b3\u03b4T cells, however, TGF-\u03b2 is capable of driving both CD8\u03b1 and CD8\u03b2 upregulation, suggesting that splenic \u03b3\u03b4T cells are unlikely the precursors of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. For \u03b3\u03b4 IELs, TGF-\u03b2 upregulates or maintains CD8\u03b1 expression on TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs but does not induce it in TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs. This indicates that TGF-\u03b2 promotes the development of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs not through the conversion of TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs into TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs.However, the aforementioned function of TGF-\u03b2 in the thymic \u03b3\u03b4T precursors clearly cannot explain the unique phenotype of TCR\u03b3\u03b4\u2212CD8\u2212\u03b3\u03b4T cells in the thymus, spleen, and IEL have the distinct potential to be CD8\u03b1+ under stimulation of TGF-\u03b21. In this regard, TGF-\u03b21 increases CD8\u03b1 but decreases CD8\u03b2 in thymic \u03b3\u03b4T cells, upregulates both CD8\u03b1 and CD8\u03b2 in splenic \u03b3\u03b4T cells, and fails to induce CD8\u03b1 and CD8\u03b2 in TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs. Though the underlying mechanisms remain unknown, it could be due to the developing stage and tissue-specific imprint. Thymic \u03b3\u03b4T cells are less developed compared to splenic \u03b3\u03b4T cells or \u03b3\u03b4 IELs and, therefore, have a higher potential to be induced to express CD8\u03b1+. Splenic \u03b3\u03b4T cells, however, tend to express CD8\u03b1\u03b2+ rather than CD8\u03b1\u03b1+ in response to sufficient TGF-\u03b2 stimulation. The biological significance of this feature remains unknown, but it suggests that splenic \u03b3\u03b4T cells are unlikely to be the precursors of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs should go through a similar developmental process to TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs but cannot express CD8\u03b1\u03b1, suggesting that they are stable in the CD8\u03b1\u2212\u03b2\u2212 phenotype and might be terminally differentiated and, thus, less likely convert to be CD8\u03b1+ when encountering stimuli such as TGF-\u03b2. As expected39, we showed that the decrease in TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in the absence of TGF-\u03b2 signaling was not due to the suppression of proliferation but can be contributed by the increase in the apoptosis of the knockout TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs.Intriguingly, CD4+ phenotype that is distinct from \u03b3\u03b4T cells in other tissues4. As a crucial cytokine produced by IECs, TGF-\u03b2 also indirectly modulates the maintenance and proliferation of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs by regulating the expression of several genes on IECs, which are known to tightly influence the development of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs40. Btnl is expressed on IECs and determines the maturation and expansion of V\u03b37+ IELs extrathymically regardless of food antigen and microbiomes;19 IL-15 and IL-15R\u03b1 complexes are abundant in IECs and critical for proliferation and survival of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs; MyD88-deficient mice also have less TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs due to IL-15 shortage42. We showed that the expression of Btnl, IL-15, and MyD88 on IECs are all downregulated in TGF-\u03b2 signaling-deficient mice. Reduction of the expression of these genes led Smad3\u2212/\u2212 IECs unable to maintain CD8\u03b1\u03b1+ on TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs in an IECs\u2013IELs coculture system. However, TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs were rarely to be CD8\u03b1+ even co-cultured with WT IECs, further confirming their inability to become TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs. Both TCR\u03b3\u03b4+CD8\u03b1\u03b1+ and TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs showed greater proliferation when co-cultured with Smad3\u2212/\u2212 IECs, suggesting that factors promoting \u03b3\u03b4 IELs proliferation were released more from Smad3\u2212/\u2212 IECs, although this remains to be fully understood. \u03b3\u03b4 IELs developed in an intestinal environment lacking Smad3 show a lower frequency of CD8\u03b1\u03b1+, V\u03b37, and V\u03b34 populations, indicating that the interaction between IECs and IELs is also important for the development and/or function of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs.In addition, IECs provide an organ-specific environment for \u03b3\u03b4 IELs to obtain a special CD8\u03b1\u03b120. As shown previously44, TGF-\u03b2 signaling in \u03b3\u03b4 IELs is crucial for intestinal homeostasis and the control of DSS-induced IBD. Supporting this conclusion is the observation that depletion of TGF-\u03b2 signaling in \u03b3\u03b4T IELs leads to increased susceptibility to and exacerbation of DSS-induced colitis, as evidenced in both Smad3\u2212/\u2212 mice and \u03b3\u03b4T cell-specific TGF-\u03b2 receptor I-deficient mice, due to enhanced bacterial invasion and damage to the epithelial barrier resulting from the reduction of \u03b3\u03b4 IELs in these knockout mice. Furthermore, TGF-\u03b2-deficient TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs exhibit upregulation of pro-inflammation cytokines IFN-\u03b3, IL-6, IL-21, IL-23\u03b1, and IL-12\u03b1, as well as downregulation of antimicrobial proteins such as RegIII\u03b3 and RegIII\u03b231. In addition to its importance in maintaining the integrity of the murine intestinal barrier, TGF-\u03b2 has been shown to be effective in enhancing the cytotoxicity of expanded human V\u03b42 cells in combination with IL-15, likely through the upregulation of CD103 and IL-9 expression in the presence of TGF-\u03b246.Due to their special localization, rapid activation, and broad antigen recognition spectrum, \u03b3\u03b4 IELs serve as the first line of the intestinal immune system to detect bacteria invasion and maintain the integrity of the epithelial barrier+CD8\u03b1\u03b1+ IELs are CD8\u03b1\u03b1+V\u03b37+ and CD8\u03b1\u03b1+V\u03b31+, suggesting that TGF-\u03b2 has the potential to alter the TCR repertoire and modulate the differentiation of \u03b3\u03b4 IELs. This hypothesis is further supported by the weaker ability of \u03b3\u03b4 IELs lacking TGF-\u03b2 signaling to maintain the integrity and homeostasis of the intestinal barrier, indicating that the remaining \u03b3\u03b4 IELs without TGF-\u03b2 exhibit distinct characteristics that may be caused by differences in TCR repertoire. However, we have yet to determine the detailed TCR repertoire specificity of \u03b3\u03b4 IELs lacking TGF-\u03b2 signaling compared to cells from WT mice. We plan to investigate this issue in future studies.According to our results, the main diminished populations of TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs, which play a crucial role in maintaining immune homeostasis and resisting DSS-induced inflammation in the gut.In summary, we have elucidated a previously unrecognized mechanism in which TGF-\u03b2 is a key factor in the formation and development of TCR\u03b3\u03b4Rag1\u2212/\u2212, CD45.1, TCR\u03b4 ER Cre mice used in this study were purchased from The Jackson Laboratory. Tgfbr1f/fEsr1-cre, Tgfbr2f/fEsr1-cre, Smad2f/fER Cre, Smad3\u2212/\u2212, Smad2/Smad3 double KO mice , and Tgfbr1f/fTCR\u03b4ERCre (Tgfbr1f/fcrossed with TCR\u03b4 ER Cre) mice were housed and bred in the animal facility in National Institute of Dental and Craniofacial Research. All mice were housed in specific pathogen-free conditions with adequate food and water supply, with 12\u2009h light/dark cycle, 50% humidity, and room temperature between 25 to 27\u2009\u00b0C, and the maximum number of mice in each cage is 5. All procedure of animal studies was performed under the National Institutes of Health guidelines for the use and care of live animals and were approved by the Animal Care & Use Committee (ACUC) of the National Institute of Dental and Craniofacial Research (NIDCR).6- to 8-week-old C57BL/6, TM Foxp3/Transcription Factor Staining Buffer Set (Cat# 00-5523-00) were from eBioscience. Mouse TCR \u03b3/\u03b4 T cell Isolation Kit (130-092-125) was from Miltenyi Biotec.Anti-mouse CD45.1 (A20), anti-mouse CD45.2 (104), anti-mouse CD45 (30-F11), anti-mouse TCR \u03b3/\u03b4 (GL3), anti-mouse TCR \u03b2 (H57-597), anti-mouse CD8\u03b1 (53-6.7), anti-mouse CD8\u03b2 (YTS156.7.7), anti-mouse V\u03b31.1 (2.22), anti-mouse V\u03b31.2 (4B2.9), anti-mouse V\u03b37 (F2.67), anti-mouse Ki67 (16\u2009A8), anti-mouse CD25 (PC61), anti-mouse CD44 (IM7), anti-mouse CD45RB (C363-16A), anti-mouse CD103 (2E7), anti-mouse CCR9 (9B1), anti-mouse IFN-\u03b3 (XMG1.2), anti-mouse TNF-\u03b1 (MP6-XT22), anti-mouse IL-17A (TC11-18H10.1), anti-mouse CD4 (GK1.5), and anti-mouse CD326 (G8.8) were purchased from Biolegend. Purified anti-mouse CD3 (145-2C11) was purchased from Bio X Cell. Recombinant mouse IL-2 (402-ML) and human TGF-\u03b21 (240-B) were purchased from R&D Systems. SB431542 was obtained from Selleckchem (Cat# S1067). Cell Proliferation Dye eFluor\u2122 450 (Cat# 65-0842-90), eBioscience Cells were collected and adjusted into appropriate density for antibody staining. For cell surface marker staining, cells were incubated with antibodies for 20\u2009min at 4\u2009\u00b0C in the dark. Intracellular staining for cytokines detection, cells were treated with PMA (10\u2009ng/mL), ionomycin (250\u2009ng/mL), and Golgi-Plug (diluted by 1:1000) for 4\u2009h at 37\u2009\u00b0C incubator. After being stained with surface markers, cells were fixed with the fixation/permeabilization buffer solution according to the manufacturer\u2019s instructions. Apoptosis of cells was investigated by staining Annexin V and 7-AAD solution diluted with Annexin binding buffer for 30\u2009min at room temperature. Intranuclear staining were performed by using fixation/permeabilization buffer solution according to the manufacturer\u2019s instructions.15. Small intestines were removed from Peyer patches, opened, and washed with 1\u00d7 PBS several times to clean gut content, then cut into four to six pieces and incubated in IEL buffer  for 20\u2009min in 37\u2009\u00b0C incubator with shaking. Suspensions were filtered by 70\u2009\u03bcm and 40\u2009\u03bcm strainer, centrifuged on a 44 and 70% percoll density gradient at 1800 rpm for 20\u2009min with brake 0. IELs can be obtained on the layer between 44% and 70% percoll.IELs from mouse small intestines were obtained as described previously19. Mouse small intestines were opened and washed with cold PBS to remove bacteria and gut content. Clean intestines were cut into small pieces and incubated in DMEM supplemented with 5% FBS, 5\u2009mM EDTA and 0.145\u2009mg/mL dithiothreitol for 20\u2009min on a turning wheel. Tissue pieces were transferred into a new tube with 5\u201310\u2009mL medium, with a vortex of 15\u2009s three times to get more epithelial cells; all the media were collected into a container with suspensions, filtered by 70 and 40\u2009\u03bcm strainer, centrifuged 1000 rpm for 10\u2009min at 4\u2009\u00b0C; cells were suspended by lysis buffer for 3\u2009min and washed once by PBS. Stained by flow antibodies for FACS sorting, CD45\u2212CD326+ cells from above were gated and collected for experiments.IECs were isolated in a way as described in the previous publication+Tgfbr1f/fEsr1-cre or Tgfbr2f/fEsr1-cre mice (treated with tamoxifen for 5 days) and CD45.1+ C57BL/6 mice. CD45.2+ and CD45.1+ BM were mixed with a ratio of 1:6, then injected into irradiated (450 rads) Rag1\u2212/\u2212 mice intravenously. Four to five weeks later, mice were sacrificed and cell populations were isolated for staining. Age-matched littermates of Smad3+/+ or Smad3\u2212/\u2212 recipients were irradiated (450 rads) 6\u2009h before BM cell transfer. BM cells were isolated from C56BL/6\u2009J mice and injected intravenously into Smad3+/+ or Smad3\u2212/\u2212 recipients. One month after transfer, IELs were isolated and analyzed by flow cytometry.BM cells were isolated from CD45.2+CD45+TCR\u03b3\u03b4+ cells, and cultured in 96 round plate in the RPMI-1640 complete medium, supplemented with anti-CD3 , IL-2 (10\u2009ng/mL), with or without TGF-\u03b21 , and SB431542 (5\u2009uM). TCR\u03b3\u03b4+CD8\u03b1\u03b1+ IELs and TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs were sorted from IELs by FACSAria Sorter with gating live+CD45+TCR\u03b3\u03b4+CD8\u03b1+\u03b2\u2212 or live+CD45+TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 specifically and cultured in RPMI-1640 complete medium supplemented with anti-CD3, IL-2 (100\u2009U/mL), IL-3 (10\u2009ng/mL), IL-4 (10\u2009ng/mL), and IL-15 (10\u2009ng/mL) as previously described in ref. 19, treated with or without TGF-\u03b21 , or SB431542 (5\u2009uM).Pure mouse \u03b3\u03b4T cells were sorted from mouse splenocytes or thymocytes by FACSAria Sorter with staining live+CD8\u03b1\u03b1+ IELs or TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212 IELs were sorted from IELs by FACSAria Sorter with gating live+CD45+TCR\u03b3\u03b4+CD8\u03b1+\u03b2\u2212 or live+CD45+TCR\u03b3\u03b4+CD8\u03b1\u2212\u03b2\u2212, and were mixed with pure intestinal epithelial cells (sorted by gating live+CD45+CD326+ from IECs) as a ratio 1:10 (IELs:IECs), which is the ratio of IELs to IECs in mice gut according to the published studies1. Cells were cultured in 96 round plates in RPMI-1640 medium, which was supplemented with anti-CD3, IL-2, IL-3, and IL-4 for 3 days before being prepared for flow cytometry.TCR\u03b3\u03b4Tgfbr1f/fTCR\u03b4 ER Cre mice at 7\u201312 days of age were cut and incubated in lysis buffer at 50\u2009\u00b0C overnight, then diluted with dH2O for PCR cocktail preparation. The primers used for Tgfbr1f/f mouse strain are F: TTCTGCTAATCCTGCAGTAAAC; R: ACCCTCTCACTCTTCCTGAGT. And the primers for the TCR\u03b4 ER Cre mouse strain are WT R: GCTTCCAAAACACTTGCACA; Common F: GGAGAGTTTTCCTAGCAGCA; Mutant R: ACACCGGCCTTATTCCAAG. PCR products were separated on 2% agarose gel with EtBr staining to distinguish bands of genes.Tails of Hprt (Mm00446968_m1), CD8\u03b1 (Mm01182197_g1), CD8\u03b21 (Mm00438116m1), Runx3 (Mm00490666), Zbtb7b (Mm00784709_s1), Btnl1 (Mm01281669_m1), Il-15 (Mm00434210), MyD88 (Mm00440338), CCL25 (Mm00436443), or Cdh1 (Mm01247357).Total RNA of isolated IECs or 18-h cultured \u03b3\u03b4T cells were extracted by using RNeasy Mini Kit (QIAGEN) according to the instruction of the manufacturer and reversed transcribed by High-Capacity cDNA Reverse Transcription Kit (Applied Biosystems). Quantitative real-time PCR was performed using TaqMan assays with primers of Smad3\u2212/\u2212 or age- and gender-matched Smad3+/+ mice were given 3% DSS drinking water continuously for 7 days; body weight and disease activity index were monitored during treatment. Tgfbr1f/fTCR\u03b4 ER Cre and Tgfbr1+/+TCR\u03b4 ER Cre littermates were treated with tamoxifen (10\u2009mg/mL) five times to deplete T\u03b2R1 specifically on \u03b3\u03b4T cells before 3% DSS water treatment. Body weight and disease activity index were monitored during treatment.47. Small intestinal tissues were taken from mice, fixed, and embedded into paraffin before being cut into 5-\u03bcm sections; then they were deparaffinized in two changes of xylene, rehydrated in 95% and 90% ethanol for 10\u2009min respectively; 16\u2009S rRNA bacteria probe: (AminoC6\u2009+\u2009Alexa488) GCTGCCTCCCGTAGGAGT (Eurofins MWG Operon) was diluted to the concentrations of 100\u2009nM to 1\u2009\u03bcM by hybridization buffer and incubated at 50\u2009\u00b0C for 3\u2009h. DAPI was stained for microscope detection.FISH experiments for bacteria invasion in the intestinal barrier were conducted based on the procedures described in the previous publicationt-test was used for the comparison of two independent experimental groups; the comparison of more than two groups was conducted by one-way ANOVA. RNA-seq data were analyzed by DeSeq2 for gene expression and normalization. P value threshold for the statistical difference was 0.05.Statistical analysis was conducted by GraphPad Prism 9 and shown in figure legends. Unpaired two-tailed Student\u2019s Supplementary InformationSupplementary Dataset S1"}
{"text": "The title compound is a phthalimide-protected polyamine with a protonated central nitro\u00adgen atom. The crystal packing features a hydrogen-bond network, a two-coordinated chloride ion, and off-set \u03c0\u2013\u03c0 stacking. 20H18N3O4+\u00b7Cl\u2212\u00b72H2O, is a phthalimide-protected polyamine that was synthesized by a previous method. It was characterized by ESI\u2013MS, 1H NMR, and FT\u2013IR. Crystals were grown from a solution of H2O and 0.1 M HCl. The central nitro\u00adgen atom is protonated and forms hydrogen bonds with the chloride ion and a water mol\u00adecule. The two phthalimide units make a dihedral angle of 22.07\u2005(3)\u00b0. The crystal packing features a hydrogen-bond network, two-coordinated chloride, and off-set \u03c0\u2013\u03c0 stacking.The title compound {systematic name: bis\u00ad[2-eth\u00adyl]aza\u00adnium chloride dihydrate}, C These units point in opposite directions to each other from the perspective of the central nitro\u00adgen atom. The central tetra\u00adhedral nitro\u00adgen atom (NH2) forms hydrogen bonds with a water mol\u00adecule and the chloride ion.The mol\u00adecular structure of the title compound is shown in Fig.\u00a013.b-axis direction \u22efCg (N3/C13\u2013C20) centroid\u2013centroid distance is 4.0143\u2005(7)\u2005\u00c5. A hydrogen-bond network (Table\u00a01A), a water mol\u00adecule (O1W), and a second water mol\u00adecule (O2W). Both water mol\u00adecules  also form hydrogen bonds with phthalimide oxygen atoms . The chloride ions form two hydrogen bonds with the protonated amine and a water mol\u00adecule.The crystal structure features off-set \u03c0\u2013\u03c0 stacking between phthalimide groups running along the on Fig.\u00a02. The Cg k Table\u00a01 exists b4.et al., 20162CH2NH2)2 resulted in 1707 hits, while the structure with protonated amines +HN(CH2CH2NH3+)2 resulted in 182 hits. One of these structures is the triprotonated di\u00adethyl\u00adenetri\u00adamine trichloride , 386.1 (M + Na+). 1H NMR  \u03b4 ppm 7.75 , 3.75 , 3.0 , 1.60 . FTIR (cm\u22121) = 3326 \u03bd(N\u2014H), 1698 \u03bd(C=O). Crystals suitable for X-ray crystallography were grown by evaporation, with the compound dissolved in a solution of H2O and 0.1 M HCl.Following a previous protocol (Utz 6.Uiso(H) = 1.2Ueq(N). C-bound and water H atoms were positioned geometrically  and refined as riding with Uiso(H) = 1.2\u20131.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023004565/ex2070sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004565/ex2070Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023004565/ex2070Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023004565/ex2070Isup4.cmlSupporting information file. DOI: 2264952CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The aim of the present study was to compare the surface morphology alterations, mineral content, and surface roughness of eroded enamel surface versus eroded enamel surface which was preceded by Bioactive Glass 45S5 (BAG45S5) application in both primary and permanent human dentitions.Fifty-two primary teeth and fifty-two permanent teeth were selected. Teeth were randomly divided into 4 groups of twenty-six teeth each. Groups A1 and B1 underwent erosion with 1% citric acid, while groups A2 and B2 were subjected to application of BAG45S5 powder followed by the same erosive conditions as A1 and B1. Measurements were performed by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and surface profilometry. They were used to examine the surface morphology alterations, mineral content, and surface roughness, respectively.p\u2009<\u20090.005) in both human dentitions. Erosion-only groups showed significantly less surface roughness in permanent teeth (p\u2009<\u20090.045). A marked decrease in surface roughness was observed in surfaces receiving BAG45S5, primary teeth (p\u2009<\u20090.001), and permanent teeth (p\u2009<\u20090.001).SEM of enamel which received BAG45S5 showed smoother surface in primary teeth post erosion. EDX analysis showed that enamel exhibited crucial resistance to mineral loss in the group which received BAG45S5 prior to inducing erosion as compared to the induced erosion-only group. This was significant (Bioactive Glass 45S5 proved successful against erosive conditions in both primary and permanent teeth with better performance in the permanent teeth so it can be regarded as a means of prevention.Bioactive Glass 45S5 powder could be used not only to remove stains but also as a prophylactic preventive measure against the multiple episodes of acidic food and beverage consumption in children. Dental erosion is the chronic and progressive, irreversible loss of dental hard tissues caused by a chemical process without any bacterial involvement. It has become a significant clinical challenge in the recent years. This is due to the major lifestyle changes that have led to an increase in the amount and frequency of consumption of acid-containing foods and beverages . Owing tErosion could have dramatic effect on the dental tissues and would result in alterations in surface roughness, changes in surface morphology, and even mineral loss of dental tissues \u20137. TheseBioactive glasses are biocompatible silicate-based materials, containing calcium and phosphate in an amorphous matrix. They undergo a unique biological reaction at the interface stimulating the formation of a chemical bond between living structures and the material itself . These sA study by Dionysopoulos et al. revealed that surface pre-treatment using air abrasion with BAG45S5 may help to prevent enamel surface erosion induced by an acidic drink in bovine teeth . In addiThe current study is a cross-sectional in vitro study, which was conducted in the Pediatric Dentistry and the Oral Biology Departments, Faculty of Dentistry, Pharos University in Alexandria, Alexandria, Egypt. Ethical approval was obtained from the Research Ethics Committee\u2014Pharos University in Alexandria in adherence to the tenets of the Declaration of Helsinki 1964 and its later amendments (# PUA02202207243036) . ParticiSample size was based on 95% confidence level to detect differences in surface roughness and mineral content between eroded enamel surface as opposed to eroded enamel surface preceded by BAG45S5 application. Dionysopoulos et al. reported mean\u2009\u00b1\u2009SD difference in surface roughness of eroded enamel pre-treated with Bioactive Glass\u2009=\u20090.002\u2009\u00b1\u20090.001, whereas it was 0.006\u2009\u00b1\u20090.01 for eroded enamel . The calAge group 6\u201320\u00a0years; normally shed or serially extracted teeth ; sound labial/buccal enamel surface.Labial/buccal enamel surface with cracks; developmental defects; caries; erosion; fillings.Group A1: twenty-six primary teeth undergoing erosion induction only. Subgroups: two teeth assigned for scanning electron microscopy (SEM) (A1-SEM); twelve teeth for energy-dispersive X-ray spectroscopy (EDX) (A1-EDX); twelve teeth for profilometry (A1-Pro)Group A2: twenty-six primary teeth receiving BAG45S5 followed by erosion induction. Subgroups: two teeth assigned for SEM (A2-SEM); twelve teeth for EDX (A2-EDX); twelve teeth for profilometry (A2-Pro)Group B1: twenty-six permanent teeth undergoing erosion induction only. Subgroups: two teeth assigned for SEM (B1-SEM); twelve teeth for EDX (B1-EDX); twelve teeth for profilometry (B1-Pro)Group B2: twenty-six permanent teeth receiving BAG45S5 followed by erosion induction. Subgroups: two teeth assigned for SEM (B2-SEM); twelve teeth for EDX (B2-EDX); twelve teeth for profilometry (B2-Pro)  Fig.\u00a0Fifty-two primary teeth were randomly and equally divided into 2 groups A1 and A2. Fifty-two permanent teeth were also randomly and equally divided into the other 2 groups B1, B2. Randomization was completed using a computer-generated list of random numbers using RAND and RANK functions-Excel (MS Office 365). A serial number was given to each tooth indicating its allocation.Collected teeth were kept in 10% formaldehyde solution at 4\u00a0\u00b0C for 7\u00a0days for sterilization . Teeth w(BAG45S5) in the form of Sylc\u00ae powder  with particle size ranging from 25 to 120\u00a0\u00b5m  for 3\u00a0min, rinsed with distilled water, and stored in artificial saliva (storage medium) for 65\u201380\u00a0min between the 6 cycles for remineralization iii.Surface roughnessThe outcomes of the current study included:Assessment of outcomes was performed at baseline and post erosion for all groups.Scanning electron microscopy (SEM) JSM-IT200 InTouchScope\u2122 Scanning Electron Microscope  was used for this purpose. Two teeth from each group were sectioned into buccal and lingual specimens using a double-sided fine grit water-cooled diamond disc yielding 4 specimens. One specimen of each tooth was randomly selected for baseline assessment of ultra-structure surface morphology alterations, while the other one was used for post erosion assessment. All specimens were dehydrated at the time of evaluation by passed through series of 50%, 70%, and 95% ethyl alcohol for 10\u00a0min each and then in absolute alcohol for two changes of 1-h period each. This was followed by drying in vacuum desiccator for 1\u00a0h . The assEnergy-dispersive X-ray spectroscopy (EDX) JSM-IT200 InTouchScope\u2122 Scanning Electron Microscope  was used for this purpose. Assigned teeth were well-polished using diamond paste (1-\u03bcm size). Then, they were washed out under running water, dehydrated, and air dried . After dProfilometry using linear scanning stylus; MarSurf PS 10  ISO 16610\u201321, Lt\u2009=\u20091.5\u00a0mm (0.25\u2009\u00d7\u20095), parameters Ra and Rz was used for this purpose. Twelve teeth from each group were assessed for their surface roughness at baseline and then post erosion. Teeth were firstly polished using 1200-grit abrasive sandpaper to smoothen out any irregularities on the enamel surface. Then, they were stored in artificial saliva for 1\u00a0h. For each tooth, three measurements were taken, and an average reading for those three measurements was obtained.. . Qualitative data were described using number and percent. The Kolmogorov\u2013Smirnov test was used to verify the normality of distribution. Quantitative data were described using range mean, standard deviation. Significance of the obtained results was judged at the 5% level. The used tests: Student t-test for normally distributed quantitative variables to compare between two groups and paired t-test for normally distributed quantitative variables to compare between two periods.Data were analysed using IBM SPSS software package version 20.0Group A1-SEM micrograph demonstrated generalized smooth surface architecture of the enamel surface (\u00d7\u2009500) Fig.\u00a0. Group BGroup A2-SEM micrograph was showing microscopic roughness and irregularities in some areas on the enamel surface (\u00d7\u20091500) Fig.\u00a0. Group Bp\u2009<\u20090.001). Carbon (C) (mean\u2009\u00b1\u2009SD) showed an increase post erosion\u2009=\u200951.48\u2009\u00b1\u20092.38\u00a0than baseline\u2009=\u200912.15\u2009\u00b1\u20092.65 which was statistically significant (p\u2009<\u20090.001). Oxygen (O2) (mean\u2009\u00b1\u2009SD) showed a decrease post erosion\u2009=\u200943.47\u2009\u00b1\u20091.54\u00a0than baseline\u2009=\u200948.60\u2009\u00b1\u20091.75\u00a0which was statistically significant (p\u2009<\u20090.001). Fluoride (F) (mean\u2009\u00b1\u2009SD) showed a negligible amount at baseline and post erosion with no significant difference (p\u2009=\u20090.275).The (mean\u2009\u00b1\u2009SD) was at baseline for calcium (Ca) and phosphorus (P)\u2009=\u200924.29\u2009\u00b1\u20091.24 and 14.30\u2009\u00b1\u20090.81\u00a0respectively which decreased post erosion to\u2009=\u20093.20\u2009\u00b1\u20091.99\u00a0and 1.43\u2009\u00b1\u20090.88\u00a0for Ca and P, respectively. This was statistically significant (p\u2009<\u20090.001). C (mean\u2009\u00b1\u2009SD) showed an increase post erosion\u2009=\u200910.85\u2009\u00b1\u20091.26\u00a0than baseline\u2009=\u20099.59\u2009\u00b1\u20092.50\u00a0which was statistically non-significant (p\u2009=\u20090.182). O2 (mean\u2009\u00b1\u2009SD) showed an increase post erosion\u2009=\u200953.01\u2009\u00b1\u20091.68\u00a0than baseline\u2009=\u200948.96\u2009\u00b1\u20092.97\u00a0which was statistically significant (p\u2009<\u20090.001). Fluoride (F) (mean\u2009\u00b1\u2009SD) showed a negligible amount at baseline and post erosion with no significant difference (p\u2009=\u20090.156) (Table The (mean\u2009\u00b1\u2009SD) was at baseline for Ca and P\u2009=\u200926.09\u2009\u00b1\u20091.57\u00a0and 14.82\u2009\u00b1\u20090.77\u00a0respectively which decreased post erosion to\u2009=\u200922.45\u2009\u00b1\u20091.27 and 12.95\u2009\u00b1\u20090.57\u00a0for Ca and P, respectively. This was statistically significant (p\u2009=\u20090.335). Also, for P, (mean\u2009\u00b1\u2009SD) was comparable between baseline and post erosion\u2009=\u200916.36\u2009\u00b1\u20090.56\u00a0and 16.15\u2009\u00b1\u20090.72,\u00a0respectively. This was non-significant (p\u2009=\u20090.520). C (mean\u2009\u00b1\u2009SD) showed a decrease post erosion\u2009=\u200910.27\u2009\u00b1\u20093.56\u00a0than baseline\u2009=\u200913.18\u2009\u00b1\u20091.92 which was non-significant (p\u2009=\u20090.085). O2 (mean\u2009\u00b1\u2009SD) showed an increase post erosion\u2009=\u200935.23\u2009\u00b1\u20094.30\u00a0than baseline\u2009=\u200932.69\u2009\u00b1\u20093.17\u00a0which was non-significant (p\u2009=\u20090.067). F (mean\u2009\u00b1\u2009SD) showed an increase post erosion than baseline\u2009=\u20090.61\u2009\u00b1\u20090.26\u00a0and\u2009=\u20090.37\u2009\u00b1\u20090.22,\u00a0respectively. This was statistically significant (p\u2009=\u20090.004).The (mean\u2009\u00b1\u2009SD) was comparable for Ca between baseline and post erosion\u2009=\u200937.32\u2009\u00b1\u20092.65\u00a0and 37.92\u2009\u00b1\u20094.48,\u00a0respectively. This was non-significant (p\u2009=\u20090.255). Also, for P, (mean\u2009\u00b1\u2009SD) was comparable between baseline and post erosion\u2009=\u200916.78\u2009\u00b1\u20090.61\u00a0and 17.29\u2009\u00b1\u20090.70,\u00a0respectively. This was non-significant (p\u2009=\u20090.064). C (mean\u2009\u00b1\u2009SD) showed a decrease post erosion\u2009=\u20095.83\u2009\u00b1\u20091.68\u00a0than baseline\u2009=\u200910.55\u2009\u00b1\u20091.63\u00a0which was statistically significant (p\u2009<\u20090.001). O2 (mean\u2009\u00b1\u2009SD) showed an increase post erosion\u2009=\u200936.59\u2009\u00b1\u20095.24\u00a0than baseline\u2009=\u200933.93\u2009\u00b1\u20092.94\u00a0which was statistically significant (p\u2009=\u20090.049). F (mean\u2009\u00b1\u2009SD) showed a negligible amount at baseline and post erosion with no significant difference (p\u2009=\u20090.352) (Table The (mean\u2009\u00b1\u2009SD) was comparable for Ca between baseline and post erosion\u2009=\u200938.19\u2009\u00b1\u20092.99\u00a0and 39.49\u2009\u00b1\u20095.26,\u00a0respectively. This was non-significant (p\u2009<\u20090.001). The (mean\u2009\u00b1\u2009SD) of P content change decreased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u200912.87\u2009\u00b1\u20090.47\u00a0and\u2009\u2212\u20091.87\u2009\u00b1\u20090.53,\u00a0respectively. This change was statistically significant (p\u2009<\u20090.001). The (mean\u2009\u00b1\u2009SD) of O2 content change decreased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u20095.13\u2009\u00b1\u20092.01\u00a0and 4.06\u2009\u00b1\u20092.94,\u00a0respectively. This change was statistically significant (p\u2009<\u20090.001). The (mean\u2009\u00b1\u2009SD) of F content change decreased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u20090.11\u2009\u00b1\u20090.34\u00a0and 0.20\u2009\u00b1\u20090.45,\u00a0respectively. This change was non-significant (p\u2009=\u20090.115). The (mean\u2009\u00b1\u2009SD) of C content change increased in A1-EDX than that of B1-EDX\u2009=\u200939.33\u2009\u00b1\u20092.17\u00a0and 1.25\u2009\u00b1\u20093.05,\u00a0respectively. This change was statistically significant (p\u2009<\u20090.001).Post erosion, the (mean\u2009\u00b1\u2009SD) of Ca content change decreased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u200921.09\u2009\u00b1\u20091.15\u00a0and\u2009\u2212\u20093.64\u2009\u00b1\u20090.98, respectively. This change was statistically significant (p\u2009=\u20090.476). The (mean\u2009\u00b1\u2009SD) of P content change decreased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u20090.22\u2009\u00b1\u20091.14\u00a0and 0.51\u2009\u00b1\u20090.86,\u00a0respectively. This change was non-significant (p\u2009=\u20090.159). The (mean\u2009\u00b1\u2009SD) of O2 content change showed comparable change in A1-EDX and B1-EDX\u2009=\u20092.55\u2009\u00b1\u20094.35\u00a0and 2.66\u2009\u00b1\u20094.18,\u00a0respectively. This change was non-significant (p\u2009=\u20090.947). The (mean\u2009\u00b1\u2009SD) of F content showed comparable change in A1-EDX and B1-EDX\u2009=\u20090.24\u2009\u00b1\u20090.23\u00a0and 0.16\u2009\u00b1\u20090.59,\u00a0respectively. This change was non-significant (p\u2009=\u20090.716). The (mean\u2009\u00b1\u2009SD) of C content change increased in A1-EDX than that of B1-EDX\u2009=\u2009\u2009\u2212\u20092.90\u2009\u00b1\u20095.31\u00a0and\u2009\u2212\u20094.72\u2009\u00b1\u20092.04,\u00a0respectively. This change was non-significant (p\u2009=\u20090.340)  of Ca content change decreased in A2-EDX than that of B2-EDX\u2009=\u20090.60\u2009\u00b1\u20092.06\u00a0and 1.31\u2009\u00b1\u20093.76,\u00a0respectively. This change was non-significant p\u2009=\u20090.76. The (P\u2009=\u200916.15\u2009\u00b1\u20090.72 and 1.43\u2009\u00b1\u20090.88 respectively (p\u2009<\u20090.001). The mineral content change of C and O2 significantly decreased in A2-EDX than A1-EDX as C\u2009=\u200910.27\u2009\u00b1\u20093.56 and 51.48\u2009\u00b1\u20092.38 respectively (p\u2009<\u20090.001) and O2\u2009=\u200935.23\u2009\u00b1\u20094.30 and 43.47\u2009\u00b1\u20091.54 respectively (p\u2009<\u20090.001). F content change was comparable between groups A2-EDX and A1-EDX\u2009=\u20090.61\u2009\u00b1\u20090.26 and 0.54\u2009\u00b1\u20090.18 respectively which was non-significant (p\u2009=\u20090.454).The mineral content change of Ca and P significantly increased in A2-EDX than A1-EDX as Ca\u2009=\u200937.92\u2009\u00b1\u20094.48 and 3.20\u2009\u00b1\u20091.99 respectively (p\u2009<\u20090.001) and p\u2009<\u20090.001), and P\u2009=\u200917.29\u2009\u00b1\u20090.70 and 12.95\u2009\u00b1\u20090.57 respectively (p\u2009<\u20090.001).The mineral content change of Ca and P significantly increased in B2-EDX than B1-EDX as Ca\u2009=\u200939.49\u2009\u00b1\u20095.26 and 22.45\u2009\u00b1\u20091.27 respectively (2 significantly decreased in B2-EDX than B1-EDX as C\u2009=\u20095.83\u2009\u00b1\u20091.68 and 10.85\u2009\u00b1\u20091.26 respectively (p\u2009<\u20090.001) and O2\u2009=\u200936.59\u2009\u00b1\u20095.24 and 53.01\u2009\u00b1\u20091.68 respectively (p\u2009<\u20090.001). F content change was comparable between groups B2-EDX and B1-EDX\u2009=\u20090.67\u2009\u00b1\u20090.45 and 0.79\u2009\u00b1\u20090.48 respectively which was non-significant (p\u2009=\u20090.537) . (Mean\u2009\u00b1\u2009SD) of B1-Pro readings at baseline was\u2009=\u20090.56\u2009\u00b1\u20090.16, while for post erosion, it was decreased to\u2009=\u20090.28\u2009\u00b1\u20090.06, and this was statistically significant (p0\u2009<\u20090.001). (Mean\u2009\u00b1\u2009SD) of A2-Pro readings at baseline was\u2009=\u20090.58\u2009\u00b1\u20090.07, while for post erosion, it was decreased to\u2009=\u20090.27\u2009\u00b1\u20090.09, and this was statistically significant (p0\u2009<\u20090.001). (Mean\u2009\u00b1\u2009SD) of B2-Pro readings at baseline was\u2009=\u20090.61\u2009\u00b1\u20090.12, while for post erosion, it was decreased to\u2009=\u20090.28\u2009\u00b1\u20090.10, and this was statistically significant (p0\u2009<\u20090.001). The change in surface roughness from baseline to post erosion significantly decreased in B1-Pro than that of A1-Pro\u2009=\u20090.56\u2009\u00b1\u20090.16/0.28\u2009\u00b1\u20090.06 and\u2009=\u20090.58\u2009\u00b1\u20090.16/0.57\u2009\u00b1\u20090.42 respectively (p1\u2009=\u20090.045). The change in surface roughness from baseline to post erosion was similarly decreased in A2-Pro and B2-Pro\u2009=\u20090.58\u2009\u00b1\u20090.07/0.27\u2009\u00b1\u20090.09 and\u2009=\u20090.61\u2009\u00b1\u20090.12/0.28\u2009\u00b1\u20090.10 respectively (p1\u2009=\u20090.563). The change in surface roughness, post erosion, between group A1-Pro\u2009=\u20090.57\u2009\u00b1\u20090.42, and A2-Pro\u2009=\u20090.27\u2009\u00b1\u20090.09 was significantly less in group A2-Pro (p\u2009=\u20090.026). The change in surface roughness, post erosion, between group B1-Pro\u2009=\u20090.28\u2009\u00b1\u20090.06, and B2-Pro\u2009=\u20090.28\u2009\u00b1\u20090.10 was not significant (p\u2009=\u20090.960) (Table (Mean\u2009\u00b1\u2009SD) of A1-Pro readings at baseline was\u2009=\u20090.58\u2009\u00b1\u20090.16, while for post erosion, it was\u2009=\u20090.57\u2009\u00b1\u20090.42 which was not statistically significant p0\u2009=\u20090.55.  on both human primary and permanent dentitions.\u00a0To overcome the lack of reliability in the use of bovine teeth instead of human ones, teeth were used from both human dentitions instead of bovine teeth for more favourable clinically applicable results. In a review of literature conducted by Yassen et al.  and baseDissolution of the enamel usually occurs when it is exposed to undersaturated solutions at a pH less than the critical pH, which is thought to be 5.5 . TherefoBAG45S5 has been widely studied for its effectiveness on enamel remineralization. It improved the microhardness of the subsurface-eroded enamel surface . A fluorChanges in surface roughness commonly occur after the interaction of acidic solutions with tooth structures. While the effect of erosive solutions on the surface roughness depends on the thickness of the aprismatic layer, the non-treated permanent enamel with its thin aprismatic surface layer demonstrated a notable roughness after exposure to the erosive acid, whereas the non-treated primary enamel with its generally uniform and thicker aprismatic layer presenting a more stable surface texture was not as affected by the erosive agent . On the Moreover, the results of the current study revealed that both human dentitions were showing significant loss of calcium and phosphate ions post the erosive challenge. The dissolution was expected to occur due to the weak constitution of the calcium-deficient carbonated hydroxyapatite crystals present in the enamel layer causing a distorted lattice conformation that is\u202fmore soluble in acidic environments.\u00a0The primary dentition presented greater mineral loss and surface distortion, because of the higher number of carbonate molecules in the hydroxyapatite crystals in the primary enamel as well as the presence of copious organic content specific to primary enamel . This isOn the contrary, enamel surface that was pre-treated by BAG45S5 before the erosive challenge showed decreased rates of carbon ions when compared to the baseline. Moreover, there was no significant change in calcium or phosphate content after erosion also compared to baseline. The effect of BAG45S5 on enamel lessened the effect of erosion on either primary or permanent enamel compared to enamel of erosion-only surfaces. BAG45S5 was suggested to be able to restore early erosive enamel lesions with complete loss of hydroxyapatite crystal content . In the On demineralized enamel surface, BAG45S5 acted in some way differently as suggested by several studies. Abbassy et al. , in theiThroughout the comparison between both dentitions, the permanent dentition which received BAG45S5 showed slightly better response following exposure to induced erosive challenge. Permanent enamel has better consolidation with particles of BAG45S5 due to the intrinsically higher inorganic content as well as morphological differences, indicating that the permanent enamel\u202fallows better integration of Bioactive Glass with the inherent calcium and phosphate ions to form more hydroxycarbonate apatite crystals . Since tIt can be concluded that applying Bioactive Glass 45S5 (BAG45S5) to the enamel surface prior to inducing erosion showed better results than inducing erosion alone in both primary and permanent dentitions. Consequently, BAG45S5 can limit or even prevent dental erosion in both primary and permanent dentitions by protecting the enamel surface from acid dissolution, with better performance on the permanent enamel. This means that BAG45S5 could be considered a promising method of erosion prevention. It could be implemented as a part of the preventive program tailored to children who show high consumption of juice and acidic beverages. Further clinical trials on children are needed to assess the effect on teeth sensitivity of using BAG45S5 prior to the repeated episodes of acidic food and beverage intake.Being dependant on collecting human teeth, difficulty was encountered in collecting the required number of teeth which led to compensating this through teeth sectioning."}
{"text": "Correction to: Acta Neuropathologica (2019) 138:251\u2013273 10.1007/s00401-019-02013-zIn this article author would like to make few changes in the article text. The corrections are given below.1. In Materials and methods section for Immunofluorescence of human sections:In the sentence:goat serum blocking with 0.1\u00a0M KPBS and 0.025% Triton-X) for at least 1\u00a0h with gentle agitation.\u201d\u201cThe sections were then washed (3\u2009\u00d7\u200915\u00a0min) in 0.1\u00a0M KPBS, after which they were incubated in blocking buffer  and TNF-\u03b1 (627\u20130.153\u00a0pg/mL). The A\u03b240 detection range was 15,100\u20133.69\u00a0pg/mL, and the A\u03b242 detection range was 2280\u20130.557\u00a0pg/mL. ELISA plates from R&D (DY008 and DY1197-05) were used to measure the levels of gal3 (detection range 1000\u201315.6\u00a0pg/mL) in culture media.\u201d\u201cThe detection ranges of the different cytokines measured were as follows: IL1\u03b2 (1670\u20130.408\u00a0pg/mL), IL4 (1660\u20130.405\u00a0pg/mL), IL12 , IL10 (3410\u20130.833\u00a0pg/mL), IFN-\u03b3 (938\u20130.229\u00a0pg/mL), IL2 (2630\u20130.642\u00a0pg/mL), IL5 (967\u20130.236\u00a0pg/mL), IL6 (5720\u20131.40\u00a0pg/mL), Action: Write \u201cIL8 regarded as human functional homolog to rodent KC\u201d\u00a0between brackets next to KC/GRO."}
{"text": "Analysis of the Hirshfeld surface shows structure-defining inter\u00adactions for bromo\u00admethyl\u00adalcohol 1, resulting in inter\u00admolecular hydrogen bonds between the hydroxyl groups along the a-axis direction.Trimeth\u00adyl({tris\u00ad[(phenyl\u00adsulfan\u00adyl)meth\u00adyl]sil\u00adyl}meth\u00adoxy)silane ( 3), C26H32OS3Si, is a new ligand for transition-metal coordination chemistry derived from 3-bromo-2,2-bis\u00ad(bromo\u00admeth\u00adyl)propan-1-ol (1), C5H9Br3O, through silylation and following exchange of bromine groups with NaSPh. Silylated thio\u00adether ligand 3 crystallizes in the centrosymmetric space group C2/c. Bromo\u00admethyl\u00adalcohol 1 crystallizes in the space group P1, resulting in inter\u00admolecular hydrogen bonds between the hydroxyl groups along the a-axis direction.Trimeth\u00adyl({tris\u00ad[(phenyl\u00adsulfan\u00adyl)meth\u00adyl]sil\u00adyl}meth\u00adoxy)silane ( As a result of the soft property of thio\u00adethers, they coordinate to transition metals . The mol\u00adecular structure of bromo\u00admethyl\u00adalcohol 1 is shown in Fig.\u00a01Bromo\u00admethyl\u00adalcohol et al., 1987The bond lengths to be expected for a C\u2013Br bond are in the range 1.880\u20131.940\u2005\u00c5 % for O1/Si1/C24\u2013C26 and 49.1\u2005(3)% for O1\u2032/Si1\u2032/C24\u2032\u2013C26\u2032. The disorder at the TMSO group also shows a shorter O1\u2014C23 [1.384\u2005(15)\u2005\u00c5] bond length than O1\u2032\u2014C23 [1.479\u2005(14)\u2005\u00c5]. The expected bond length for a C\u2014O\u2014Si bond is between 1.365 and 1.467\u2005\u00c5  bonds are of comparable lengths to each other and correspond to the expected bond lengths for alk\u00adyl\u2013sulfur bonds \u2005\u00c5]. Moreover, the angles are approximately linear at 175\u2005(4)\u00b0 (O3\u2014H3\u22efO4) and 168\u2005(4)\u00b0 (O1\u2014H1\u22efO2). These hydrogen bonds can be assigned the graph-set symbol D11(2). This means that a hydrogen bond between two adjacent hydroxyl groups, O1\u2014H1\u22efO2, is established. The contact between O4\u2014H4\u22efO1 is created via the symmetry operation (i) x\u00a0\u2212\u00a01, y, z.The crystal packing of bromo\u00admethyl\u00adalcohol CrystalExplorer21 , which is due to the spatial arrangement of the bromine substituents in relation to the hydroxyl group.To gain further insight into the supra\u00admolecular packing inter\u00adactions, a Hirshfeld surface analysis was performed prop\u00adoxy]benzene-1,2-dicarbo\u00adnitrile silane]di\u00adbromo\u00admercury(II)] silane-S,S\u2032]mercury(II) -2-[(phenyl\u00adthio)\u00admeth\u00adyl]propan-2-ol yielded no hits in the WebCSD. By replacing the quaternary carbon with a silicon atom, the comparable structural motif of 2I2 rhomboids  was dropped into diethyl ether (50\u2005mL) at 273.15\u2005K to 1 (15.39\u2005mmol). The solution was stirred for 1\u2005h at room temperature and then chloro\u00adtri\u00admethyl\u00adsilane (16.93\u2005mmol) was added at 273.15\u2005K. It was stirred again for 1\u2005h at room temperature, then the reaction solution was quenched with water. The aqueous phase was extracted three times with di\u00adchloro\u00admethane and the combined organic layers were dried over magnesium sulfate. The volatiles were removed to give compound 2 crude.Methyl\u00adlithium  \u03b4 = 3.33 , 3.18 , 0.03 3) ppm.1H}13C NMR  \u03b4 = 61.6 , 44.3 , 34.6 , \u22120.7  ppm.{2 in DMF (10\u2005mL) at 273.15\u2005K and stirred for 10 minutes. The reaction solution was irradiated with microwaves  and then quenched with water. The aqueous phase was extracted three times with di\u00adchloro\u00admethane, the combined organic layers were dried over magnesium sulfate and the volatiles were removed. The residue was separated by fractional distillation under reduced pressure. Crystallization from diethyl ether at 243.15\u2005K provided silylated thio\u00adether ligand 3 as clear and colourless blocks.Thio\u00adphenol (5.83\u2005mmol) was then added to sodium hydride (5.83\u2005mmol) in DMF (5\u2005mL) at 273.15\u2005K and stirred for 10 minutes. The NaSPh solution was added to 1H NMR  \u03b4 = 7.38\u20137.34 , 7.30\u20137.23 , 7.19\u20137.15 , 3.60 , 3.22 , 0.04  ppm.1H}13C NMR  \u03b4 = 137.2 , 129.8 , 128.9 , 126.2 , 64.1 , 46.0 4), 38.7 , \u22120.6  ppm.{6.Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms. Hydrogen atoms H1, H2, H3 and H4 for compound 1 were refined independently. The TMSO group in 3 is disordered with occupancies converging to 50.9\u2005(3)% for O1/Si1/C24\u2013C26 and 49.1\u2005(3)% for O1\u2032/Si1\u2032/C24\u2032\u2013C26\u2032.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698902300227X/vm2278sup1.cifCrystal structure: contains datablock(s) 1, 3, global. DOI: 10.1107/S205698902300227X/vm22781sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698902300227X/vm22783sup3.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S205698902300227X/vm22781sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698902300227X/vm22783sup5.cmlSupporting information file. DOI: 2247226, 2247225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title carbazole derivative, the dihedral angle between the carbazole ring system and the pendant phenyl ring is 56.78\u2005(8)\u00b0. 19H15NO, the dihedral angle between the benzene rings of the carbazole moiety is 1.73\u2005(12)\u00b0 and the meth\u00adoxy-substituted phenyl ring deviates from the mean plane of the carbazole grouping (r.m.s. deviation = 0.020\u2005\u00c5) by 56.78\u2005(8)\u00b0. In the crystal, weak C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules. The two-dimensional fingerprint plots derived from the Hirshfeld surface indicate that H\u22efH (51.2%) and C\u22efH/H\u22efC (39.9%) contacts dominate the packing.In the title compound, C The crystal structure is consolidated by weak C\u2014H\u22ef\u03c0 inter\u00adactions  = 2.71\u2005\u00c5; symmetry code: 1\u00a0\u2212\u00a0x, \u2212y, z; C17\u2014H17\u22efCg(C7\u2013C12) = 2.92\u2005\u00c5; symmetry code: x, 1\u00a0+\u00a0y, z]. The crystal packing viewed along the a-axis direction is shown in Fig.\u00a03The title compound crystallizes in the ortho\u00adrhom\u00adbic space group it Fig.\u00a01. As expens Fig.\u00a02 [C9\u2014H9\u22efCet al., 2017dnorm within the range \u22120.05 to 1.63 a.u. shows a few red spots in the locales of D\u22efA  inter\u00adactions, consistent with the presence of weak C\u2014H\u22ef\u03c0 inter\u00adactions , which were uniformly dispersed in 35\u2005ml of di\u00admethyl\u00adformamide (DMF) and the mixture was dissolved homogeneously under an N2 atm. To the mixture, K2CO3 , CuI  and 1,10-phenanthroline  was added and the mixture was refluxed for 12\u2005h under N2. The progress of the reaction was monitored by TLC. After the completion of the reaction, the reaction was quenched in ice\u2013water and the solid product was dissolved in ethyl acetate and washed with brine solution. The obtained solvent was removed under reduced pressure and the obtained residue was further purified using column chromatography (100\u2013200 mesh silica gel) to afford the title compound as shown in Fig.\u00a06A 100\u2005ml round-bottom flask was charged with 4-iodo\u00adanisole 1.78\u2005g , 9Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314623006740/hb4441sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623006740/hb4441Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623006740/hb4441Isup3.cmlSupporting information file. DOI: 2280833CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two benzo\u00adthio\u00adphene derivatives are described and the inter\u00admolecular contacts in the crystals analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots. 22H16FNO2S2 (I) and C26H20FNO2S2 (II), the benzo\u00adthio\u00adphene rings are essentially planar with maximum deviations of 0.009\u2005(1) and 0.001\u2005(1)\u2005\u00c5 for the carbon and sulfur atom in compounds I and II, respectively. In I, the thio\u00adphene ring system is almost orthogonal to the phenyl ring attached to the sulfonyl group, with a dihedral angle of 77.7\u2005(1)\u00b0. In compound I, the mol\u00adecular structure is stabilized by weak C\u2014H\u22efO intra\u00admolecular inter\u00adactions formed by the sulfone oxygen atoms, which generate two S(5) ring motifs. In the crystal of I, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into R22(8) rings, which are connected into a C(10) chain via C\u2014H\u22efF hydrogen bonds. Inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are also observed. In compound II, the mol\u00adecules are linked via C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonding, generating infinite C(11) and C(13) chains running parallel to [010].In the title compounds, C Thio\u00adphene derivatives possess pharmacological and biological activities including anti\u00adbacterial benzene\u00adsulfonamide (C7\u2013C22/N1/S2/O1/O2/F1) while compound II, C26H20FNO2S2 benzene\u00adsulfonamide (C9\u2013C15/N1/S2/O1/O2). In both compounds, the benzo\u00adthio\u00adphene ring systems (S1/C1\u2013C8) are essentially planar with maximum deviations of 0.009\u2005(1) and 0.001\u2005(1)\u2005\u00c5 for atom C8 and S1 in compounds I and II, respectively. The mean planes of the thio\u00adphene ring system in I make dihedral angles of 1.2\u2005(2), 2.3\u2005(2), 77.7\u2005(2)\u00b0 with the C1\u2013C6, C11\u2013C16 and C17\u2013C22 phenyl rings. The mean planes of the thio\u00adphene ring system in II make dihedral angles of 0.3\u2005(2), 33.3\u2005(2), 25.2\u2005(2)\u00b0, respectively, with the C1\u2013C6, C11\u2013C16 and C17\u2013C22 phenyl rings, The benzo\u00adthio\u00adphene ring system in I is almost orthogonal to the C17\u2013C22 ring attached to sulfonyl group with dihedral angle of 77.7\u2005(1)\u00b0 in I. For both compounds, the bond lengths and angles are close to those observed for similar structures \u00b0 in II], with a simultaneous decrease in the N1\u2014S2\u2014C17 angle [106.35\u2005(9) in I and 108.3\u2005(2)\u00b0 in II] from the ideal tetra\u00adhedral value (109.5\u00b0) are attributed to the Thorpe\u2013Ingold effect  and N1\u2014C16 = 1.450\u2005(5)\u2005\u00c5 bond lengths in the mol\u00adecule are longer than the mean Nsp2\u2014Csp2 bond-length value of 1.355\u2005(14)\u2005\u00c5   inter\u00adactions, where the Cg1 is the centroid of the C1\u2013C6 ring  were performed with CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of \u22120.434 (red) to 1.449 (blue) for compound I and \u22120.119 (red) to 1.765 (blue) for compound II, where the red spots indicate the inter\u00admolecular contacts involved in the hydrogen bonding. The electrostatic potential was also mapped on the Hirshfeld surface using a STO-3G basis set and the Hartee\u2013Fock level of theory . Areas on the Hirshfeld surface with high curvedness tend to divide the surface into contact patches with each neighbouring mol\u00adecule. The coordination number in the crystal is defined by the curvedness of the Hirshfeld surface . The nearest neighbour coordination environment of a mol\u00adecule is identified from the colour patches on the Hirshfeld surface depending on their closeness to adjacent mol\u00adecules .The Hirshfeld surfaces of compounds I, they reveal that the principal inter\u00admolecular contacts are H\u22efH contacts at 36.9% , H\u22efC/C\u22efH contacts at 26.1% , O\u22efH/H\u22efO at 15.1% , F\u22efH/H\u22efF at 9.2% , C\u22efC at 6.7% , S\u22efC/C\u22efS at 2.2% , S\u22efH/H\u22efS contacts at 0.9% , F\u22efC/C\u22efF at 0.8% , N\u22efC/C\u22efN at 0.7%  and N\u22efH/H\u22efN contacts at 0.3% .The fingerprint plots are given in Figs. 89% Fig.\u00a08b, H\u22efC/C1% Fig.\u00a08c, O\u22efH/H1% Fig.\u00a08d, F\u22efH/H2% Fig.\u00a08e, C\u22efC a7% Fig.\u00a08f, S\u22efC/C2% Fig.\u00a08g, S\u22efH/H9% Fig.\u00a08i, F\u22efC/C8% Fig.\u00a08j, N\u22efC/C7% Fig.\u00a08k and N\u22ef3% Fig.\u00a08l.II, they reveal a similar trend, with the principal inter\u00admolecular contacts being H\u22efH/H\u22efH at 41.4% , H\u22efC/C\u22efH contacts at 25.1% , O\u22efH/H\u22efO at 12.1% , F\u22efH/H\u22efF at 8.1% C\u22efC at 4.6% , C\u22ef\u00b7C at 4.7% , S\u22efH/H\u22efS contacts at 4.5% , S\u22efC/C\u22efS contacts at 2.1% , C\u22efO/O\u22efC contacts at 1.0% , F\u22efS/S\u22efF at 0.9%  and O\u22efO contacts at 0.3 . In both compounds, the H\u22efH inter\u00admolecular contacts predominate, followed by the C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts.For compound 4% Fig.\u00a09b, H\u22efC/C1% Fig.\u00a09c, O\u22efH/H6% Fig.\u00a09e, C\u22ef\u00b7C 7% Fig.\u00a09f, S\u22efH/H5% Fig.\u00a09g, S\u22efC/C1% Fig.\u00a09h, C\u22efO/O0% Fig.\u00a09i, F\u22efS/S9% Fig.\u00a09j and O\u22ef.3 Fig.\u00a09k. In bo5.I: To a solution of (E)-2-(2-(benzo[b]thio\u00adphen-2-yl)vin\u00adyl)-5-fluoro\u00adbenzenaminium chloride  in dry DCM (10\u2005mL), pyridine  and PhSO2Cl  were added and stirred at room temperature for 12\u2005h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (50\u2005g) containing conc. HCl (5\u2005mL), extracted with DCM (2 \u00d7 20\u2005mL) then washed with water (2 \u00d7 20\u2005mL) and dried (Na2SO4). Removal of solvent in vacuo followed by crystallization from di\u00adethyl\u00adether (4\u2005mL) afforded (E)-N-{2-[2-(benzo[b]thio\u00adphen-2-yl)ethen\u00adyl]-5-fluoro\u00adphen\u00adyl}benzene\u00adsulf\u00adonamide as a white solid.Compound II: To a solution of (E)-N-{2-[2-(benzo[b]thio\u00adphen-2-yl)vin\u00adyl]-5-fluoro\u00adphen\u00adyl}benzene\u00adsulfonamide  in CH3CN (10\u2005mL), K2CO3  and 1-bromo\u00adbut-2-yne  were added and stirred at room temperature for 12\u2005h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (50\u2005g) containing conc. HCl (5\u2005mL), extracted with ethyl acetate (2 \u00d7 20\u2005mL) then washed with water (2 \u00d7 20\u2005mL) and dried (Na2SO4). Removal of solvent in vacuo followed by crystallization from methanol (4\u2005mL) afforded (E)-N-{2-[2-(benzo[b]thio\u00adphen-2-yl)ethen\u00adyl]-5-fluoro\u00adphen\u00adyl}-N-(but-2-yn-1-yl)benzene\u00adsulfonamide as a white solid.Compound 6.I, the NH H atoms were located in difference-Fourier maps and freely refined. For compound II, they were included in calculated positions and refined as riding: N\u2014H = 0.93\u2005\u00c5 with Uiso(H) = 1.2Ueq(N). All C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms: C\u2013H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. In compound I, the thio\u00adphene ring is disordered over two positions with a refined occupancy ratio of 0.756\u2005(4):0.244\u2005(3). The geometries were regularized using soft restraints.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023006096/zn2029sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989023006096/zn2029Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023006096/zn2029IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989023006096/zn2029Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023006096/zn2029IIsup5.cmlSupporting information file. DOI: 2280606, 2280605CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "It crystallizes isotypically with H-La2[Si2O7]. The four crystallographically distinct CeIII cations form distorted square anti\u00adprisms, capped square anti\u00adprisms, and bicapped square anti\u00adprisms as coordination polyhedra consisting of oxygen atoms. Four crystallographically different silicon atoms recruit the centers of two different isolated [Si2O7]6\u2013 units.The title compound, dicerium(III) oxidodisilicate, Ce H-type Ce2[Si2O7], like H-La2[Si2O7]  cover an inter\u00adval from 2.366\u2005(4) to 2.817\u2005(4)\u2005\u00c5 (Table\u00a01plus 3.11\u2005(4)\u20133.34\u2005(4)\u2005\u00c5 to most caps. All oxygen atoms belong to pyroanionic oxidodisilicate anions [Si2O7]6\u2013  = 1.588\u2005(4)\u20131.676\u2005(4)\u2005\u00c5   as reaction vessel at a temperature of 1023\u2005K, taking advantage of the presumed mineralizers Sb2O3 and CeCl3. The transparent, colorless crystals exhibit a platelet-like habit.Single crystals of Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623005916/wm4192sup1.cifCrystal structure: contains datablock(s) I, 1R. DOI: 10.1107/S2414314623005916/wm4192Isup2.hklStructure factors: contains datablock(s) I. DOI: 2222660CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Araucaria araucana is an ancient conifer, native to the mountain ranges in Chile and Argentina. These trees host a large number of organisms, mainly insects, strongly or even exclusively associated with them. The recent emergence of a novel canker disease on A. araucana has emphasised the importance of fungi associated with these iconic trees and has resulted in the discovery of various new species. In this study, we considered the identity of an unknown calicioid fungus consistently found on resin on the branches of A. araucana. Preliminary phylogenetic analyses placed isolates in the recently described sub-class Cryptocaliciomycetidae, closest to Cryptocalicium blascoi. However, the morphology of the ascomata and its occurrence in a unique niche suggested that the closest relative could be Resinogalea humboldtensis , a fungus with similar sporing structures found on resin of Araucaria humboldtensis in New Caledonia. There are no living cultures or sequence data available for either R. humboldtensis or its supposed closest relative, Bruceomyces castoris, precluding sequence-based comparisons. Morphological comparisons of the sporing structures on A. araucana confirmed that the ascomatal morphology of our unknown calicioid fungus and R. humboldtensis are almost identical and resemble each other more so than B. castoris or Cr. blascoi. A phylogenetic analysis based on the small subunit (SSU), internal transcribed spacer (ITS) and large subunit (LSU) rDNA regions resolved our strains into two clades with Cr. blascoi as its closest relative. Further analyses applying the Genealogical Concordance Phylogenetic Species Recognition (GCPSR) based on ITS, mini chromosome maintenance protein complex (MCM7), RNA polymerase II second largest subunit (RPB2) and translation elongation factor 1-alpha (TEF) gene regions, confirmed that strains represent two new species. Based on our morphological observations and phylogenetic analyses, we introduce two new Resinogalea species, R. araucana and R. tapulicola, and reclassify the genus in the subclass Cryptocaliciomycetidae.The online version contains supplementary material available at 10.1186/s43008-023-00122-9. Araucaria araucana (Araucariaceae), commonly known as Araucaria, pew\u00e9n or the monkey puzzle tree, is an ancient species native to the mountain ranges of Chile and Argentina. The species is one of only two in the genus and family found in South America, with the remainder distributed in the Southeast Asia\u2013Oceania region     to accommodate both genera, Resinogalea and Bruceomyces, each containing a single species  or 2% malt extract agar  in Petri dishes. Plates were incubated for 14 d at 20\u201325\u00a0\u00b0C. Fungal colonies of interest were transferred to new MEA plates in order to produce pure cultures. Isolates were further purified by transferring them to 2% water-agar  and allowing these to grow for 2\u20134 d before transferring single hyphal tips to new MEA plates. Direct isolations from ascomata were made by collecting ascospores with a sterile needle, spreading these onto WA and after 2\u20134\u00a0days, transferring germinating single spores to new MEA plates.All relevant isolates used in this study were deposited into the culture collection (CMW) housed at the Forestry and Agricultural Biotechnology Institute . Representative strains for each species were subsequently deposited into the CMW-IA culture collection  and to the culture collection (CBS) of the Westerdijk Fungal Biodiversity Institute . Specimens were deposited in the PREM fungarium of the South African National Collections of Fungi housed at the Agricultural Research Council .DNA extractions were performed using the Prepman\u00ae Ultra Sample Preparation Reagent kit  following the manufacturer\u2019s protocols. For some strains, DNA was extracted using a phenol\u2013chloroform method. For the latter approach, strains were grown on MEA for 21 d, after which mycelium was collected in 2\u00a0mL Eppendorf tubes and freeze dried overnight. Mycelia was ground by adding metal beads and shaking this in a mixer mill  and then following the protocol described by Barnes et al.  and modiRPB2) with primers RPB2-5f2 & RPB2-7cR  with primers Cer-MCM7F & Cer-MCM7R  large intron with primers EF1-782F & EF-2  of each primer (10\u00a0\u00b5M), 0.3 \u00b5L MyTaq\u2122 DNA Polymerase and 17.7 \u00b5L (16.7 \u00b5L for MCM7) sterile deionized water. The thermal cycling conditions included an initial denaturation step of 95 \u02daC for 3\u00a0min, followed by 35 cycles of denaturing at 95 \u02daC for 30\u00a0s, annealing at 56 \u02daC (52 \u02daC for TEF1 and MCM7) for 30\u00a0s and elongation at 72 \u02daC for 45\u00a0s, followed by a final elongation step at 72 \u02daC for 4\u00a0min. Successful amplifications were confirmed by staining PCR amplicons with GelRed\u00ae (2 \u00b5L per 4 \u00b5L of PCR product) and electrophoresing the product on a 1% agarose gel for 12\u00a0min at 110\u00a0V.Six gene regions were amplified through PCR, which included: (i) the internal transcribed spacer 5.8S rDNA (ITS) with primers ITS1 & ITS4 .PCR amplicons were cleaned from excess primers and unincorporated nucleotides either by sodium acetate precipitation  approach  and edited using Affinity Designer v.1.10.5.1342 (Serif (Europe), Nottingham, UK). Aligned datasets and IQ-TREE outputs were uploaded to the University of Pretoria\u2019s research data repository hosted on Figshare and can be accessed at https://doi.org/10.25403/UPresearchdata.21640298.Each dataset was aligned using the MAFFT v.7 online service selecting the L-INS-i algorithm . Microscopic slides were prepared from 28 d old colonies using 10% lactic acid as mountant. Structures collected directly from samples were first sectioned using a Leica CM1520 cryostat  before a microscope specimen was prepared. Characters were observed and photographed using a Zeiss AXIO Zoom.V16 dissection and AXIO Imager.A2 compound microscopes both equipped with a Zeiss AxioCaM 512 colour camera driven by Zen Blue v.3.2 software . For dissection microscope images, extended depth of field analyses were performed using Helicon Focus v.7.5.4 . Up to 50 measurements were made for each character where available, and boxplot graphs were constructed with measurements of each character to visualize data distribution. Photographic plates were prepared in Affinity Designer v.1.10.5.1342 (Serif (Europe) Ltd, Nottingham, UK). Attempts were made at the time of the study to obtain specimens for R. humboldtensis but these were unsuccessful. Morphological comparisons were thus based on the description published in Rikkinen et al.  using a micropipette and allowed to dry for 10\u00a0min before plates were sealed with Parafilm\u00ae and incubated upside down. Plates were incubated at temperature gradient of 5\u00a0\u00b0C intervals from 5\u201335\u00a0\u00b0C for 21 d and colony diameters measured every 3\u20134 d. The colony area was measured from images taken on day 21 using ImageJ v.1.52  and Trongol Alto .Isolations made from surface disinfested n\u2009=\u200923), and from single spore isolates from five fruiting bodies (n\u2009=\u20095). A preliminary phylogenetic analysis , 39 gaps (6%)), followed by Penicillium scabrosum , 35 gaps (5%)), P. hirayamae , 28 gaps (4%)), P. copticola\u00a0, 16 gaps (3%)), and P. terrigenum , 27 gaps (4%)). Six strains were selected from each of the two ITS clades and five additional gene regions sequenced for them to continue further analyses.DNA extraction and ITS sequencing was performed for all strains originating from plant tissue , ITS  and LSU  were concatenated resulting in a matrix containing 62 taxa that was 5770\u00a0bp long. The most suitable nucleotide substitution models according to the Bayesian information criterion (BIC) for SSU, ITS and LSU were TNe\u2009+\u2009I\u2009+\u2009G4, GTR\u2009+\u2009F\u2009+\u2009I\u2009+\u2009G4, and TN\u2009+\u2009F\u2009+\u2009I\u2009+\u2009G4 respectively. ML and BI analyses resolved strains, with high bootstrap support, into two clades in the subclass Cryptocaliciomycetidae with Cr. blascoi as its closest relative  in Cr. blascoi and the outgroup Caliciopsis pinea. Substitution models for the aligned ITS , MCM7 , RPB2 , and TEF1 , datasets were, respectively, TNe\u2009+\u2009G4, K2P\u2009+\u2009I, TNe\u2009+\u2009I and TNe\u2009+\u2009G4. All gene regions resolved the strains in two concordant well-supported clades, and with the exception of SSU, all regions resolved them in a clade separate from Cr. blascoi. Similarities between isolates from the two clades containing our isolates were low; the SSU differed by three or more substitutions, the LSU differed by eight or more substitutions, the ITS differed by 20 or more substitutions, the MCM7 differed by 99 or more substitutions, the TEF1 differed by 102 or more substitutions, and the RPB2 differed by 99 or more\u00a0substitutions.Single gene phylogenies were subsequently calculated to assess the phylogenetic relationships between our strains by applying GCPSR Fig.\u00a0. For theR. humboldtensis  and distinctive characters such as the shape of the ascomata and ascospore ornamentation  were observed only on branch samples, never in culture, and all strains obtained from them resided in a single clade based on DNA sequence comparisons. The ascomata on the samples emerged directly from resin or the plant tissue that surrounded it Fig.\u00a0. Ascomaties Fig.\u00a0a, b. TheRikkinen ; Table 2Cryptocalicium blascoi, the closest phylogenetic relative to our species, shares broad morphological and niche features with our fungus and R. humboldtensis . Furthermore, morphological characteristics, colony growth rate and optimal growth temperature data revealed minor but consistent differences between two species which we describe below : Conguill\u00edo National Park sector Los Paraguas: -38.697836\u00b0, -71.817216\u00b0, from ascomata on branches of A. araucana, 02 May 2018, F. Balocchi .Description: In nature \u2014 Ascomata emerging from dry resin patches in branches of A. araucana, stipitate, capitate, (556\u2013)766\u20131070(\u20131540) \u00b5m tall (excluding mazaedium); stipe cylindrical, subulate or rarely dumbbell-shaped, bent wholly or at the base, rarely straight, black, rugose, covered with a granular orange to reddish-brown mineral pruina, (257\u2013)364\u2013598(\u20131069)\u2009\u00d7\u2009(70\u2013)92\u2013214(\u2013275) \u00b5m; stipe medulla composed of textura intricata-porrecta, brownish pigmentation; stipe outermost layer composed of 15\u201320 layers of textura prismatica-porrecta, long parallel hyphae, cylindrical, septate, slightly thick walled, hyaline inner layers becoming dematiaceous towards outer layers, hyphae 2\u20133\u00a0\u00b5m wide; strongly melanized mycelium emerging from the base of the stipe, hyphae darkly pigmentated and thick walled, (3\u2013)6\u20139(\u201313.5)\u2009\u00d7\u20093\u20135(\u20137.5) \u00b5m; capitulum spherical when immature, ampulliform or urceolate when mature, (204\u2013)293\u2013394(\u2013467) \u00b5m wide, (121\u2013)230\u2013344(\u2013500) \u00b5m tall (not including mazaedium), black, rugose, sometimes covered with white to yellowish white resin; margins at the apical opening discrete, irregular, sometimes crenate-like, light brown; mazaedium well-developed in mature ascomata, reddish-brown, irregularly shaped or in some cases columnar, up to 290\u00a0\u00b5m in length; ectal excipulum poorly differentiated from the medullary excipulum, both combined consisting of 8\u201314 layers of textura prismatica\u2013porrecta, hyphae periclinally arranged, darkly pigmented in the outer layers and becoming hyaline in the inner, (8\u2013)11\u201317(\u201332)\u2009\u00d7\u20093\u20136(\u20139) \u00b5m; subhymenium hyaline or with very slight yellowish pigmentation, composed of textura angularis-intricata. Asci clavate, hyaline, pedicellate, bitunicate, evanescent, eight-spored, often with biseriately arranged spores, sporiferous part (15.5\u2013)19\u201323(\u201330)\u2009\u00d7\u20094\u20136\u00a0\u00b5m, pedicel 6\u201318.5(\u201332)\u2009\u00d7\u20091.5\u20133\u00a0\u00b5m. Ascospores non-septate, hyaline when immature, becoming brownish with age, smooth to finely roughened, broadly ellipsoidal, some globose or ellipsoidal, some erythrocyte-like, 4\u20135.5(\u20136.5)\u2009\u00d7\u2009(3.5\u2013)4\u20135.5\u00a0\u00b5m, (x\u0305\u2009=\u20095.25\u2009\u00b1\u20090.6\u2009\u00d7\u20094.34\u2009\u00b1\u20090.49), average length/width 1.22\u2009\u00b1\u20090.12 (n\u2009=\u200950). Paraphyses hyaline, filiform, obtuse, non-branched, 1\u20135 septate, 64\u2013121(\u2013172)\u2009\u00d7\u20092\u20133\u00a0\u00b5m. Phialide-like structures sporadically found inside the capitulum, potentially emerging from walls, hyaline, single-celled, subglobose, ellipsoidal or ampulliform, guttulate, (3\u2013)4.5\u20137.5(\u20138.5)\u2009\u00d7\u20092\u20133(\u20134) \u00b5m, bearing single conidia-like structures, globose to obovoid, sometimes lobsided, hyaline when immature, becoming brownish with age, smooth or finely roughened, 4\u20136(\u20137)\u2009\u00d7\u20093.5\u20135.5\u00a0\u00b5m (x\u0305\u2009=\u20095.54\u2009\u00b1\u20090.67\u2009\u00d7\u20094.47\u2009\u00b1\u20090.59), average length/width\u2009=\u20091.25\u2009\u00b1\u20090.19 (n\u2009=\u200937).In culture \u2014 colony diameters: (mm after 14 d (after 21 d)): MEA at 5\u00a0\u00b0C microcolonies (3\u20135), at 10\u00a0\u00b0C 6\u20139 (13\u201315), at 15\u00a0\u00b0C 13\u201321 (17\u201328), at 20\u00a0\u00b0C 19\u201326 (29\u201335), at 25\u00a0\u00b0C 18\u201324 (29\u201337); PDA at 5\u00a0\u00b0C microcolonies (3\u20134), at 10\u00a0\u00b0C 8\u201311 (13\u201317), at 15\u00a0\u00b0C 15\u201318 (21\u201326), at 20\u00a0\u00b0C 20\u201324 (28\u201335), at 25\u00a0\u00b0C 19\u201327 (27\u201340), at 30\u00a0\u00b0C 6\u201315 (8\u201321), at 35\u00a0\u00b0C no growth; WA at 5\u00a0\u00b0C microcolonies (2\u20135), at 10\u00a0\u00b0C 5\u20138 (10\u201313), at 15\u00a0\u00b0C 10\u201314 (15\u201320), at 20\u00a0\u00b0C 14\u201319 (22\u201327), at 25\u00a0\u00b0C 14\u201323 (25\u201336); OA at 20\u00a0\u00b0C 18\u201324 (30\u201336).Colony characters: MEA 25\u00a0\u00b0C 21 d: Colonies velvety, concentric darkening or without pattern, umbonate, margins entire to slightly irregular, subsurface, obverse greyish yellow to dark yellow (4B4\u2013C8), aerial mycelium yellowish white to orange white (4A2\u20135A2) at margins, pale to light yellow (4A3\u20135) centrally, reverse beige to blond (4C3\u20134) orange yellow to dark yellow (4B8\u2013C7) centrally. MEA 20\u00a0\u00b0C 21 d: Colonies slimy, glabrous and sulcate, rarely dry and fluffy, umbonate, with full or slightly crenate margins, obverse greyish yellow to dark yellow (4B3\u2013C8), aerial mycelium yellowish white to orange white (4A2\u20135A2) at margins, yellowish white to light yellow (4A2\u20135) centrally, reverse beige to blond (4C3\u20134) at margins, orange yellow to dark yellow (4B8\u2013C7) centrally. MEA 20\u201325\u00a0\u00b0C 6 wks or older: Colonies slimy, glabrous, sulcate, irregular margins, producing sporodochia as mucilaginous spore masses on the surface, in concentric halos or with no pattern, dark brown to brownish black (6F4\u2013H8). PDA 25\u00a0\u00b0C 21 d: Colonies velvety, glabrous, some cultures slimy only at centres, concentric or slightly petaloid pattern, umbonate, with full or slightly crenate margins, obverse yellowish grey to orange white (4B2\u20135A2), margins sunken in the medium, aerial mycelium greyish yellow to pale orange (4B4\u20135A3) at margins, becoming slightly darker or sometimes grey (4B1\u2013D1) towards the centre, reverse yellowish white to yellowish grey (4A2\u2013B2) at margins, pale yellow to olive (2D4\u20134A3) at centre, sometimes olive (2F7).Microscopic characters: Somatic hyphae at colony periphery hyaline, smooth, thin-walled, branched, transversely septate, 1.5\u20134.5\u00a0\u00b5m diam, anastomosing and developing coils, becoming inflated and melanized with age. Conidiomata most commonly absent, sporodochial with age, composed of pseudostromatic thick-walled melanized hyphae, setae absent. Conidiophores reduced, unbranched, rarely single branched or stromatic. Conidiogenous cells monophialidic or undifferentiated, then acropleurogenous; denticles sometimes present, up to 3\u00a0\u00b5m in length; terminal conidiogenous loci 13.5\u201325 (\u201335) \u00b5m in length from septa; phialides ampulliform, curved or straight and tapering towards the apex, collarette distinct, (5.5\u2013)7\u201310(\u201315)\u2009\u00d7\u20092.5\u20133(\u20134) \u00b5m. Conidia produced in slimy heads, hyaline, sometimes dematiaceous with age, aseptate, smooth walled, distinct hilum mostly present, globose to broadly ellipsoidal, larger conidia on PDA and WA typically ellipsoidal to ovoid, variable in size, from MEA (3\u2013)3.5\u20134.5(\u20136.5)\u2009\u00d7\u20093\u20133.5(\u20134) \u00b5m (x\u0305\u2009=\u20093.83\u2009\u00b1\u20090.46\u2009\u00d7\u20093.41\u2009\u00b1\u20090.26), average length/width\u2009=\u20091.13\u2009\u00b1\u20090.17 (n\u2009=\u2009228), from PDA 3.5\u20136(\u20138)\u2009\u00d7\u2009(3\u2013)3.5\u20135\u00a0\u00b5m, (x\u0305\u2009=\u20095.06\u2009\u00b1\u20091.11\u2009\u00d7\u20093.82\u2009\u00b1\u20090.46), average length/width\u2009=\u20091.32\u2009\u00b1\u20090.26 (n\u2009=\u200956), from WA (3\u2013)3.5\u20135(\u20136.5)\u2009\u00d7\u2009(2.5\u2013)3\u20133.5 (\u20134.5) \u00b5m (x\u0305\u2009=\u20094.39\u2009\u00b1\u20090.82\u2009\u00d7\u20093.3\u2009\u00b1\u20090.38), average length/width\u2009=\u20091.34\u2009\u00b1\u20090.26 (n\u2009=\u200962).Habitat/host: Resinogalea araucana produces ascomata on dry resin patches on damaged tissues in A. araucana branches. It was isolated directly from resin or plant tissues covered with resin. The type of damage inducing the exudated resin in which this fungus was found varied between samples, and included cankers caused by pathogenic fungi or insect feeding. This suggests that the presence of this fungus is merely associated with the presence of dry resin and has no role in causing resin to be produced. Strains originated from all collection sites in the Andes and Coastal range, suggesting that its distribution overlaps that of A. araucana.Material examined:Chile:Araucan\u00eda (IX): Conguill\u00edo National Park (sector Los Paraguas), -38.697836\u00b0, -71.817216\u00b0, from branches of A. araucana, 2 May 2018, F. Balocchi ; ibid, -38.697836\u00b0, -71.817216\u00b0, from branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, (culture CMW 53536\u2009=\u2009AR023); \u2014 Villarrica National Park sector Puesco, -39.572706\u00b0, -71.499235\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 13 Dec. 2017, F. Balocchi . \u2014 Biob\u00edo (VIII), Ralco Natural Reserve, -37.962620\u00b0, -71.327679\u00b0, cankers on branches on A. araucana (isolates from plant tissue covered in resin), 27 Dec. 2017, F. Balocchi (culture CMW 53543\u2009=\u2009AR224); \u2014 Nahuelbuta mountain range, Trongol Alto, -37.564893\u00b0, -73.205764\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 21 Dec. 2017, F. Balocchi ; \u2014 -37.553434\u00b0, -73.188438\u00b0, ascomata on branches of A. araucana, 5 Dec. 2019, F. Balocchi .Distinguishing characters: See below.MycoBank: MB 846746.Etymology: Latin, \u2018tapulicola\u2019, named after the Mapudungun (indigenous Chilean and Argentinian Mapuche language) word \u2018tap\u00fcl\u2019 meaning the leaves of a tree, and the Latin '-cola' meaning an inhabitant, inhabitant of leaves of a tree.Diagnosis: ITS barcode: OP508126. Alternative identification markers: LSU\u2009=\u2009OP508138, MCM7\u2009=\u2009OP524462, RPB2\u2009=\u2009OP524476, SSU\u2009=\u2009OP508114, TEF1\u2009=\u2009OP524488.Type:Chile:Araucan\u00eda (IX): Conguill\u00edo National Park sector Los Paraguas, -38.697836\u00b0, -71.817216\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, F. Balocchi .Description: Only known in culture. Colony diameters: (mm after 14 d (after 21 d)): MEA at 5\u00a0\u00b0C microcolonies (3\u20134), at 10\u00a0\u00b0C 9\u201310 (15\u201317), at 15\u00a0\u00b0C 15\u201318 (24\u201326), at 20\u00a0\u00b0C 22\u201327 (33\u201339), at 25\u00a0\u00b0C 23\u201331 (33\u201347); PDA at 5\u00a0\u00b0C microcolonies (3\u20135), 10\u00a0\u00b0C 9\u201312 (16\u201319), 15\u00a0\u00b0C 17\u201320 (25\u201330), 20\u00a0\u00b0C 21\u201329 (32\u201344), at 25\u00a0\u00b0C 27\u201334 (39\u201349), 30\u00a0\u00b0C 11\u201319 (15\u201327), 35\u00a0\u00b0C no growth; WA at 5\u00a0\u00b0C microcolonies (3\u20135), at 10\u00a0\u00b0C 7\u20139 (10\u201316), at 15\u00a0\u00b0C 13\u201316 (17\u201324), at 20\u00a0\u00b0C 15\u201323 (22\u201334), at 25\u00a0\u00b0C 17\u201324 (29\u201336); OA at 20\u00a0\u00b0C 20\u201324 (29\u201337).Colony characters: MEA 25\u00a0\u00b0C 21 d: Colonies velvety to tomentose, mycelium growth in a rosaceous and/or concentric pattern, umbonate, margins irregular, obverse dark yellow to greyish yellow (4B4\u2013C8) at margins, aerial mycelium yellowish white to orange grey (4A2\u20135B2) at margins, pale to light yellow (4A3\u20135) centrally, reverse greyish yellow to blond (4B3\u2013C4) at margins, becoming dark yellow to brownish yellow (4B8\u20135C7) centrally. MEA 20\u201325\u00a0\u00b0C 6 wks or older: slimy, glabrous, rarely velvety, umbonate, mycelium growing in a rosaceous and/or concentric pattern, margins irregular, soluble pigments golden brown to reddish brown (5D7\u20138E6), obverse orange grey to light brown (6B2\u2013D4), aerial mycelium sometimes present, white to greyish red (3A1\u20137B4), reverse brownish orange to brown (5C3\u2013F6), sporodochia appear as mucilaginous spore masses on the surface, in concentric halos or with no pattern, light brown to dark brown (6D6\u2013F8). PDA 25\u00a0\u00b0C 21 d: slimy, glabrous to tomentose, mycelium growing in a rosaceous or stellate pattern, margins irregular, obverse edges sunken in the medium, yellowish grey (2B2\u20134B2), aerial mycelium white to pale yellow (3A1\u20133) at margins, becoming olive to dark grey (1F1\u20133E8) centrally, reverse pale grey to yellowish grey (3B1\u20133) at margins, becoming dull yellow to olive (3B4\u2013E5) centrally, sometimes darker (3F7).Microscopic characters: Somatic hyphae at colony periphery hyaline, smooth, thin-walled, branched, transversely septate, 1.5\u20134\u00a0\u00b5m diam, anastomosing, often developing coils, becoming inflated and melanized with age. Conidiomata most commonly absent, sporodochial with age, composed of interwoven thick-walled melanized hyphae, setae absent. Conidiophores reduced, unbranched, single branched, becoming monoverticillate to richly branched. Conidiogenous cells monophialidic or undifferentiated, then acropleurogenous; denticles sometimes present, up to 4.5\u00a0\u00b5m in length; terminal conidiogenous loci (10.5\u2013)19\u201328(\u201352) \u00b5m in length from septa; phialides ampulliform, sometimes constricted at the middle, curved or straight and tapering towards the apex, with distinct collarette, (6\u2013)8\u201312(\u201316)\u2009\u00d7\u2009(2\u2013)2.5\u20133.5(\u20134) \u00b5m. Conidia produced in slimy heads, hyaline and thin-walled when young or on nutrient poor media, thick-walled and/or dematiaceous with age, aseptate, smooth walled, distinct hilum mostly present, on MEA globose to broadly ellipsoidal, rarely ellipsoidal, 3.5\u20134.5(\u20136)\u2009\u00d7\u20093\u20134.5\u00a0\u00b5m (x\u0305\u2009=\u20094.28\u2009\u00b1\u20090.49\u2009\u00d7\u20093.91\u2009\u00b1\u20090.32), average length/width\u2009=\u20091.09\u2009\u00b1\u20090.09 (n\u2009=\u2009114), on PDA and WA subglobose to ellipsoidal, rarely globose, on PDA (3.5\u2013)4\u20135(\u20136)\u2009\u00d7\u20093\u20134(\u20134.5) (x\u0305\u2009=\u20094.66\u2009\u00b1\u20090.66\u2009\u00d7\u20093.55\u2009\u00b1\u20090.38), average length/width\u2009=\u20091.32\u2009\u00b1\u20090.21 (n\u2009=\u200958), on WA (3\u2013)4\u20135(\u20137.5)\u2009\u00d7\u2009(3\u2013)3.5\u20134(\u20134.5) (x\u0305\u2009=\u20094.31\u2009\u00b1\u20090.93\u2009\u00d7\u20093.62\u2009\u00b1\u20090.38), average length/width\u2009=\u20091.19\u2009\u00b1\u20090.19 (n\u2009=\u200950).Habitat /host: A sexual morph of this fungus has not been observed, and is only known from cultures isolated from plant tissues that had resin on them. Strains originate from collection sites in the Andes and Coastal range suggesting that its distribution overlaps that of A. araucana. Its occurrence on other tree species has not been explored and a broader geographical distribution may thus exist.Material examined:Chile:Araucan\u00eda (IX): Conguill\u00edo National Park sector Los Paraguas, -38.697836\u00b0, -71.817216\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, F. Balocchi . \u2014 Villarrica National Park sector Puesco, -39.575582\u00b0, -71.493489\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 13 Dec. 2017, F. Balocchi ; \u2014 Biob\u00edo (VIII), Nahuelbuta mountain range, Trongol Alto, -37.564893\u00b0, -73.205764\u00b0, branches of A. araucana (isolates from plant tissue covered in resin), 15 Jan. 2019, F. Balocchi .Distinguishing characters: The general morphology of the ascomata produced by R. araucana closely resembles those of R. humboldtensis, and to a lesser extent Cr. blascoi. Ascomata were not observed for R. tapulicola. Comparing ascomata of R. araucana with those reported for R. humboldtensis 92\u2013214(\u2013275) \u00b5m vs 80\u2013140\u00a0\u00b5m), and the mineral pruina covering it was orange to darker red as oppose to yellowish brown. Ascospores of R. araucana were on average slightly larger (4\u20135.5(\u20136.5)\u2009\u00d7\u2009(3.5\u2013)4\u20135.5\u00a0\u00b5m vs (3\u2013)3.6\u20134.7(\u20135.8)\u2009\u00d7\u2009(2.7\u2013)3.3\u20134.3(\u20134.6) \u00b5m) and asci were thinner (4\u20136\u00a0\u00b5m vs 6\u20139\u00a0\u00b5m) with commonly shorter pedicels (6\u201318.5(\u201332) \u00b5m vs 22\u201343\u00a0\u00b5m). Cryptocalicium blascoi produces smaller ascomata (150\u2013360\u00a0\u00b5m vs (556\u2013)766\u20131070(\u20131540) \u00b5m), generally smaller microscopic features, and is characterized by a greenish mazaedium, contrasting with the reddish brown mazaedium of R. araucana.R. araucana and R. tapulicola resemble each other and could easily be confused. Resinogalea tapulicola grows faster than R. araucana  originating from them was confirmed by sequencing. This difference in results between isolates from R. araucana and R. humboldtensis may be an outcome of different ages and/or preservation status of the specimens at their time of collection and/or processing. The erythrocyte-like shape of ascospores in R. humboldtensis observed by Rikkinen et al.  alongside B. castoris  with Cryptocalicium, the only other genus in the family. However, we consider Bruceomyces (B. castoris) to be morphologically sufficiently distinct from Resinogalea and Cryptocalicium to merit retention as the monotypic genus of Bruceomycetaceae. Furthermore, we emphasise that DNA sequence data will be needed to determine its relationship with other fungi.The results of our analyses using DNA sequence data generated from Cryptocalicium, Prieto et al. . As a consequence, R. humboldtensis has remained taxonomically obscure and its relationship to the specimen we found on A. araucana was initially only suspected based on the hosts and substrate. This situation has been highlighted by numerous authors who note that a large number of old fungal names remain unsequenced , had no reference DNA sequence data available and had not been classified within the ascomycetes (incertae sedis). Morphological and ecological data supports our conclusions that the fungi collected in this study on A. araucana are most closely related to R. humboldtensis,\u00a0and phylogenetic analyses showed that they reside in the recently described subclass Cryptocaliciomycetidae. The genus Resinogalea has consequently been re-classified in the Cryptocaliciaceae  together with the two new species R. araucana and R. tapulicola described here from A. araucana in Chile.This study combines morphological, ecological, and phylogenetic data to describe two novel Additional file 1.\u00a0Maximum likelihood tree for the ITS gene region for 28 isolates obtained from branches of Araucaria araucana."}
{"text": "DFT analysis at M06/6-311G  level was accomplished to explore the photonic behavior of PCMD1\u2013D9 compounds. Various kind of analysis like; UV\u2013Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8\u2009<\u2009PCMD5\u2009=\u2009PCMD9\u2009<\u2009PCMD6\u2009<\u2009PCMD7\u2009<\u2009PCMD4\u2009<\u2009PCMD3\u2009<\u2009PCMD2\u2009<\u2009PCMD1 with the least band gap of 2.048\u00a0eV in PCMD8 among all the compounds. The UV\u2013Visible spectrum of the entitled chromophores manifested high values of \u03bbmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization  for PCMD8 chromophore. The highest linear polarizability (<\u03b1>) and dipole moment (\u00b5tot) values were exhibited by PCMD5 at 2.712\u2009\u00d7\u200910\u201322. and 1.995\u2009\u00d7\u200910\u201317 esu, respectively. PCMD8 push\u2013pull configured molecular entity exhibited highest first hyper-polarizability (\u03b2tot) at 4.747\u2009\u00d7\u200910\u201327 esu and second hyper-polarizability at 6.867\u2009\u00d7\u200910\u201332 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1\u2013D9) with D-\u03c0 One particularly fascinating aspect of NLO is Second Harmonic Generation (SHG), a process that transforms incoming light waves into waves with double their initial frequency. This phenomenon has garnered extensive attention for its practical applications, particularly in advanced technologies like photovoltaics and optoelectronics2.In the past few decades, non-linear optics (NLO) has emerged as a rapidly expanding field of scientific exploration. It delves into the intricate relationship between light interacts with matter, especially when subjected to external electric fields, this phenomenon referred to as \u2018nonlinear optical phenomena\u2019 due to the non-trivial relationship between the response of matter and the strength of the applied electric field3. Each material possesses unique attributes that may make it well-suited for one application while less relevant for others. The performance of materials becomes notably significant when they exhibit a high degree of nonlinearity, demonstrates promising potential for crystal growth, and possesses a high damage threshold, among other qualities. The continuous development of novel materials with exceptional characteristics plays a pivotal role in advancing leading-edge technologies6. The strength of optical parallelism and fast speed will progressively generate optoelectronic systems where more functions could be executed optically. Nevertheless, the technological evolution of photonics dependent on formulating novel compounds with enhanced performance7.When an electric field interacts with dielectric materials, it induces a rearrangement of the spatial distribution of electrons around the nucleus. This distortion leads to the establishment of electric dipoles within the material, resulting from these electron\u2013nucleus distortions. The choice of a suitable crystal for a specific application in nonlinear optics depends on several factors, including the nonlinear phenomenon being employed, the characteristics of the pump laser, and the desired properties of the device8. Due to D\u2013\u03c0\u2013A architecture increased conjugation and these are utilized in number of fields causing organic compound having excellent NLO properties9. Conjugated polymers are considered the most comprehensive researched materials for nonlinear optics and among the organics. Having a quality of existence of a delocalized \u03c0-electron system making it quick response giving and substantial third-order nonlinear optical characteristics11. They can also be created in many geometries, such as waveguides, films, fibers, and single crystals and they can be utilized by molecular engineering. So, polymers with the \u03c0-conjugated structures are considered as top applicants for succeeding optical photonic technologies.Different NLO substances have been attained by many scientific efforts during current years to bring out synthetic resins, molecular dyes, organic and inorganic semiconductor diodes. Low dielectric constants, low cost, high photoelectric coefficients, accessibility, the contribution of \u03c0-bonding system and electronic displacement besides facile formulation made the organic compounds should be selected in preferences. Intra-molecular charge transfer (ICT) is an important phenomenon in NLO response. The NLO substances demonstrating \u201cpush\u2013pull\u201d system due to donor-\u03c0-acceptor framework is the reason for development of ICT13, reduced ground state dipole interaction, chirality15, and organometallic complex18, however physical and chemical methods have been successful in attaining non-centro symmetric organic compounds.Due to electronic delocalization, particularly conjugation present in organic materials, they exhibit distinctive optoelectronic characteristics such as photocatalytic, photovoltaic and photoconductive behavior. High second order nonlinear optical response is present in organic compounds demonstrating intramolecular charge transfer (ICT). Charge spread asymmetrically in the p electron structure in organic materials having electron deficient (acceptor) and rich (donor) motifs and hence exhibit enhanced NLO behavior. The conditions of chemical and mechanical stability, large damage threshold, and high phase matchable NLO coefficient must be present in NLO crystals. Molecular properties based on a few of the above conditions can be fulfilled through molecular formulation. By choosing appropriate acceptor and donor combinations, the molecular ICT can be regulated. Various approaches have been presented to develop organic compounds with non-centro symmetric structures like hydrogen bonding\u03b2 values) and high nonlinear optical coefficients. Due to their expanded aromatic rings in structure, they have an extremely conjugated \u03c0-electron system. This conjugation gives rise to efficient electron delocalization and charge transfer, which are important for generating nonlinear optical responses. Having highly linear planar structure and having strong molecular packing makes the octacyclic naphthalene-based organic scaffolds (NITT) selection as \u03c0-spacer for current study. Yang et al. inserted a terminal end group i.e., IC-2F with NITT core, namely NITTBF to further explore nonlinear properties19. NITT-BF compound showed red shifted absorption along with higher electron mobility because of enhanced intermolecular \u03c0\u2013\u03c0 stacking. Its blend film gives increased exciton dissociation and charge collection properties. NITT-BF delivers higher electron mobility and stronger intermolecular \u03c0\u2013\u03c0 stacking, which account for the higher exciton dissociation and charge collection efficiency in NITT-BF-based device. In addition, NITT-BF has an optical energy gap of 1.25 eV which corresponds to higher nonlinearity.A large and delocalized \u03c0-electron system of octacyclic naphthalene-based organic compounds which leads to exceptional hyperpolarizabilities  configured PCMD1\u2013D9 organic chromophores by substituting acceptor motif in the reference PCMR having acceptor\u2013\u03c0\u2013acceptor (A\u2013\u03c0\u2013A) configuration from parent NITT-BF. The reference compound has been obtained by substituting R1 (3-ethylheptane) and R2 (1-hexyl-4-methylbenzene) with methyl group to reduce computational cost and time of investigation. However, in PCMD9 the one side acceptor is replaced with donor motif which remained constant in the rest of the compounds. But from PCMD1\u2013D9 the end capped acceptor group was substituted by variant acceptor groups to study their molecular nonlinearity and impact on ICT. The analyses were performed at M06/6-311G functional. The TD-DFT and DFT calculations would be executed to interpret the effect of variant acceptors on intramolecular charge transmission, band gap, nonlinear response and absorption spectra. Therefore, various analysis such as FMO, NLO, NBO, UV\u2013Vis, TDM and DOS were performed. We hope these theoretically engineered molecules will lead to more advancements in leading optical technology.20. Complete investigation of the present research were accomplished utilizing M0621/6-311G22 theory level. Transition density matrix (TDM) as well as natural bond orbital (NBO) analyzed charge transition interactions through Multiwfn 3.723 and NBO package 3.124. The energies of frontier molecular orbitals (FMOs) and orbital diagrams were obtained through Avogadro25. The Ultraviolet\u2013Visible (UV\u2013Vis) study was executed utilizing GaussSum26 and the spectral diagram was depicted via Origin 8.027. However, the density of states illustrations were obtained through PyMOlyze28. The dipole moment (\u00b5tot)29 and nonlinear optical parameters like linear polarizability (<\u03b1>)30 as well as nonlinear hyperpolarizability (\u03b2tot and \u03b3tot)31 were also computed at the same level M06/6-311G through Eqs.\u00a0 and PCMD1\u2013D9 having donor-\u03c0-acceptor (D\u2013\u03c0\u2013A) system) were calculated employing density functional theory (DFT) via Gaussian 09 program\u03c3), chemical potential (\u03bc)32, ionization potential (IP)33, electronegativity (X)34, global hardness (\u03b7)35, electron affinity (EA) and global electrophilicity index (\u03c9)36.Equations\u00a0\u201311) wer wer11) w19 was utilized. The structural modification of NITT-BF into three parts; 2- malononitrile two acceptor groups on either side and NITT core. The R1 (3-ethylheptane) and R2 (1-hexyl-4-methylbenzene) groups in NITT core were replaced by methyl groups to convert NITT-BF to reference PCMR with A\u2013\u03c0\u2013A configuration  energy gap is directly influenced by above mentioned factors. These orbitals determine intra-molecular charge transference efficiency42. However, their energy difference (\u0394E) is efficient to know molecular chemical reactivity as well as dynamic stability Less \u0394E value corresponds to high polarizability which in turn lead to exceptional NLO behavior43. On the other hand, high \u0394E value corresponds to molecular stability and hardness leading to less reactivity and chemical alteration. Table NLO characteristics of molecule\u2019s electronic structure is determine by frontier molecular investigationFrom the above table, the reference organic molecule (PCMR) possesses\u2009\u2212\u20095.941 and\u2009\u2212\u20093.505\u00a0eV of HOMO and LUMO energies, which are comparable to the experimental values of\u2009\u2212\u20095.75 and\u2009\u2212\u20094.15\u00a0eV, respectively, indicating the accurateness in the selection of functional group for the present analysis. The achieved values of HOMO for all the derivatives (PCMD1\u2013D9) are higher than the reference compound at\u2009\u2212\u20095.658,\u2009\u2212\u20095.637,\u2009\u2212\u20095.649,\u2009\u2212\u20095.657,\u2009\u2212\u20095.697,\u2009\u2212\u20095.682,\u2009\u2212\u20095.659,\u2009\u2212\u20095.696 and\u2009\u2212\u20095.693\u00a0eV, respectively. However, the obtained LUMO values for PCMD1\u2013D4 and PCMD7 are higher than the reference i.e.,\u2009\u2212\u20093.362,\u2009\u2212\u20093.352,\u2009\u2212\u20093.402,\u2009\u2212\u20093.445 and\u2009\u2212\u20093.459\u00a0eV, correspondingly but on the other hand PCMD5, PCMD6, PCMD8 and PCMD9 exhibit less values than PCMR at\u2009\u2212\u20093.623,\u2009\u2212\u20093.525, 3.648 and\u2009\u2212\u20093.619\u00a0eV, respectively. Hence, the high HOMO and less LUMO values result in less band gap in PCMD5, PCMD6, PCMD8 and PCMD9 showing high charge transmission probability in these molecules.The highest band gap is exhibited by PCMR at 2.436\u00a0eV. This largest energy difference is attributed to the presence of 2-malononitrile as a acceptor motifs with A\u2013\u03c0\u2013A configuration. Because moving from PCMR to PCMD1 the one end capped acceptor group is substituted with 9-phenyl-9H-carbazole which significantly reduces the band gap to 2.296\u00a0eV in PCMD1.Conversely, the least band gap value of 2.048\u00a0eV is present in PCMD8, that might be owing to the presence of high electronegative nitro functional groups at 6 and 7 positioning of 1-(dicyanomethylene)-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalene (DMP) acceptor group. The second lowest energy gap value is exhibited by PCMD5 and PCMD9 at 2.074\u00a0eV because of the presence of sulfonic acid groups and cyano groups at 6 and 7 positioning of DMP acceptor moiety rendering high electron withdrawing tendency. However, PCMD6 possess 2.157\u00a0eV energy gap resulted from the 6, 7 positioning of trifluoromethyl functional group in DMP. The presence of acetate, chloro and fluoro groups at 6, 7 positioning of DMP acceptor group in PCMD7, PCMD4 and PCMD3 corresponds to band gap of 2.200, 2.212 and 2.247\u00a0eV, respectively. 2.285\u00a0eV of energy gap is present in PCMD2 in relation to the absence of any electron withdrawing functional groups in DMP. The ascending order of energy difference (HOMO/LUMO) for the derivatives is PCMD8\u2009<\u2009PCMD5\u2009=\u2009PCMD9\u2009<\u2009PCMD6\u2009<\u2009PCMD7\u2009<\u2009PCMD4\u2009<\u2009PCMD3\u2009<\u2009PCMD2\u2009<\u2009PCMD1. Figure\u00a044. In DOS pictographs, the HOMO signifies valence band showing negative values while the positive values are represented by the conduction band (LUMO)45. The analysis was performed at the same DFT functional for\u00a0PCMR and PCMD1\u2013D9. DOS indicates the contribution of each fragment of molecule in charge transfer. For determining the density of states (DOS), we split our studied molecules into se98parate fragments. The\u00a0PCMR1 was divided into two fragments\u00a0i.e., donor (D) and acceptor (A) while, the derivatives (PCMD1\u2013D9) were divided into three segments\u00a0i.e., donor, \u03c0-spacer, and acceptor. From Fig.\u00a0The DOS analysis verify the results shown by the FMOs diagrams and explain the electronic distribution in frontier molecular orbitals47. Franck\u2013Condon principle relates spectral highest absorption maxima (\u03bbmax) to vertical excitation. The information about oscillator strength (fos), absorption maxima (\u03bbmax), excitation energy (E), along with molecular orbital (MO) contribution in transition are given in Table \u03bbmax) in ultraviolet visible region for PCMR and PCMD1\u2013D9 is presented in Fig.\u00a0The ultraviolet visible computation in gaseous form for PCMR and PCMD1\u2013D9 were performed at M06/6-311G to apprehend oscillator strength as well as excitation energy with relation to important electronic transitions\u03bbmax) value for reference (PCMR) i.e., 606.899\u00a0nm is lowest among all the compounds with transition energy of 2.043\u00a0eV, 2.956 oscillator strength and molecular orbital contribution from HOMO to LUMO of 95%, however, from HOMO-1 to LUMO-1 it is 3%. Hence, it is observed that absorption maxima are significantly impacted by highly electron rich donor and electron withdrawing acceptor end capped groups as well as molecular configuration (reference (A\u2013\u03c0\u2013A)\u03bbmax value of reference compound resulted from two electron withdrawing acceptor groups on either side of the \u03c0-linker. However, the highest \u03bbmax value of 701.541\u00a0nm is exhibited by PCMD8 among all the chromophores because of high electronegative nitro functional groups present in DMP acceptor group, results in 1.767\u00a0eV energy of transition and oscillator strength of 1.299. The molecular orbital contribution exhibited by PCMD8 compound is 96% from HOMO to LUMO and 3% HOMO-1 to LUMO. The second highest \u03bbmax of 696.849\u00a0nm is present in PCMD5 due to the presence of sulfonic acid groups in DMP with 1.779\u00a0eV of transition energy, 1.779 fos and MO contribution of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. However, the third highest \u03bbmax of 695.442\u00a0nm is shown by PCMD9 because of cyano groups presence in DMP with transition energy and fos values of 1.783\u00a0eV and 1.362, respectively. However, the molecular orbital contributions in PCMD9 corresponds to 95% from HOMO to LUMO and 3% from HOMO-1 to LUMO. Owing to the presence of trifluoromethyl groups in PCMD6, the \u03bbmax reduces to 663.580\u00a0nm with E 1.868\u00a0eV, 1.504 fos and MO contributions of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. Substituting trifluoromethyl groups by chloro groups result in \u03bbmax of 641.238\u00a0nm in PCMD4 with E 1.934\u00a0eV, 1.687 fos and MO contributions of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. The overall decreasing trend for PCMD1\u2013D9 as; PCMD8\u2009>\u2009PCMD5\u2009>\u2009PCMD9\u2009>\u2009PCMD6\u2009>\u2009PCMD4\u2009>\u2009\u2009>\u2009PCMD3\u2009>\u2009PCMD1\u2009>\u2009PCMD2 with chief molecular orbital contribution is from HOMO to LUMO of 94\u201396%. The compounds with lower Eg showed wider absorption spectrum as the decreasing trend of \u03bbmax is almost similar with the increasing trend of energy gap. All fabricated molecules showed bathochromic shift 49. \u03c3\u2009\u2192\u2009\u03c3*, \u03c0\u2009\u2192\u2009\u03c0*, LP\u2009\u2192\u2009\u03c3* and LP\u2009\u2192\u2009\u03c0* orbital overlapping lead to hyper conjugation. The \u03c0-conjugation present in the computed derivatives having D\u2013\u03c0\u2013A configuration lead to \u03c0\u2009\u2192\u2009\u03c0* transitions, hence result in efficient nonlinear optical substances. Weak \u03c3\u2009\u2192\u2009\u03c3* transitions are also present because of poor donor and acceptor interactions. Table Here, Molecular orbitals for PCMR and PCMD1\u2013D9 involve in consistent \u03c0\u2009\u2192\u2009\u03c0* transitions are \u03c0(C18\u2013C19)\u2009\u2192\u2009\u03c0*(C22\u2013C23) corresponds to stabilization energies of 31.57, 32.39, 31.82, 32.24, 32.6, 34.13, 33.46, 32.84, 34.31 and 34.06\u00a0kcal/mol, respectively. The lowest \u03c0\u2009\u2192\u2009\u03c0* transitions exhibited by PCMR and PCMD1\u2013D9 corresponds to \u03c0(C61\u2013C62)\u2009\u2192\u2009\u03c0*(C61\u2013C62), \u03c0(C34\u2013O35)\u2009\u2192\u2009\u03c0*(C28\u2013C29), \u03c0(C107\u2013C108)\u2009\u2192\u2009\u03c0*(C107\u2013C108), \u03c0(C80\u2013C83)\u2009\u2192\u2009\u03c0*(C80\u2013C83), \u03c0(C105\u2013C106)\u2009\u2192\u2009\u03c0*(C105\u2013C106), \u03c0(C39\u2013N40)\u2009\u2192\u2009\u03c0*(C37\u2013N38), \u03c0(C95\u2013C96)\u2009\u2192\u2009\u03c0*(C95\u2013C96), \u03c0(C95\u2013C96)\u2009\u2192\u2009\u03c0*(C95\u2013C96), \u03c0(C39\u2013N40)\u2009\u2192\u2009\u03c0*(C37\u2013N38) and \u03c0(C37\u2013N38)\u2009\u2192\u2009\u03c0*(C39\u2013N40) at 0.65, 4.16, 0.67, 0.51, 0.67, 0.8, 0.67, 0.67, 0.81 and 0.79\u00a0kcal/mol stabilization energy, respectively.Likewise, orbitals involved in \u03c3\u2009\u2192\u2009\u03c3* transitions in PCMR and PCMD1\u2013D9 are \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C12\u2013C13)\u2009\u2192\u2009\u03c3*(C13\u2013C19), \u03c3(C3\u2013C4)\u2009\u2192\u2009\u03c3*(C4\u2013C5), \u03c3(C22\u2013H24)\u2009\u2192\u2009\u03c3*(C18\u2013S20), \u03c3(C3\u2013C4)\u2009\u2192\u2009\u03c3*(C4\u2013C5) and \u03c3(C62\u2013C64)\u2009\u2192\u2009\u03c3*(C66\u2013C84) at highest energy of stabilization of 10.27, 10.36, 10.42, 10.43, 10.48, 4.92, 4.99, 10.54, 4.99 and 4.99\u00a0kcal/mol, respectively. Whereas, the lowest stabilization energy for \u03c3\u2009\u2192\u2009\u03c3* transitions involve \u03c3(C37\u2013N38)\u2009\u2192\u2009\u03c3*(C33\u2013C36), \u03c3(C65\u2013C66)\u2009\u2192\u2009\u03c3*(C6\u2013C15), \u03c3(C62\u2013C64)\u2009\u2192\u2009\u03c3*(C62\u2013S63), \u03c3(C61\u2013C62)\u2009\u2192\u2009\u03c3*(C6\u2013C59), \u03c3(C61\u2013C62)\u2009\u2192\u2009\u03c3*(C6\u2013C59), \u03c3(C62\u2013C64)\u2009\u2192\u2009\u03c3*(C62\u2013S63), \u03c3(C62\u2013C64)\u2009\u2192\u2009\u03c3*(C62\u2013S63), \u03c3(C61\u2013C62)\u2009\u2192\u2009\u03c3*(C6\u2013C59), \u03c3(C37\u2013N38)\u2009\u2192\u2009\u03c3*(C33\u2013C36) and \u03c3(C61\u2013C62)\u2009\u2192\u2009\u03c3*(C6\u2013C59) at 0.51\u00a0kcal/mol in PCMR and 0.5\u00a0kcal/mol in PCMD1\u2013D9 chromophores.LP\u2009\u2192\u2009\u03c0* and LP\u2009\u2192\u2009\u03c3* transitions are also observed conforming to resonance. LP\u2009\u2192\u2009\u03c0* transitions involve LP(1)(C68)\u2009\u2192\u2009\u03c0*(C64\u2013C66), LP(1)(N82)\u2009\u2192\u2009\u03c0*(C83\u2013C85), LP(1)(N96)\u2009\u2192\u2009\u03c0*(C107\u2013C108), LP(2)(S20)\u2009\u2192\u2009\u03c0*(C12\u2013C13), LP(2)(S20)\u2009\u2192\u2009\u03c0*(C12\u2013C13), LP(1)(C3)\u2009\u2192\u2009\u03c0*(C9\u2013C57), LP(1)(N94)\u2009\u2192\u2009\u03c0*(C95\u2013C96), LP(2)(O120)\u2009\u2192\u2009\u03c0*(C118\u2013O119), LP(3)(O117)\u2009\u2192\u2009\u03c0*(N115\u2013O116) and LP(1)(N94)\u2009\u2192\u2009\u03c0*(C105\u2013C106) orbitals having 72.81, 35.44, 35.42, 29.54, 29.56, 69.77, 35.34, 47.48, 194.76 and 35.4\u00a0kcal/mol in PCMR and PCMD1\u2013D9 chromophores, correspondingly. All the same, LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34), LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34), LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34), LP(1)(O35)\u2009\u2192\u2009\u03c3*(C23\u2013C34), LP(3)(O119)\u2009\u2192\u2009\u03c3*(S118\u2013O122), LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34), LP(1)(O116)\u2009\u2192\u2009\u03c3*(C115\u2013O117), LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34) and LP(1)(O35)\u2009\u2192\u2009\u03c3*(C29\u2013C34) at 21.25, 21.3, 20.67, 20.8, 18.57, 29.05, 21.11, 33.38, 21.35 and 21.24\u00a0kcal/mol in PCMR and PCMD1\u2013D9 chromophores, correspondingly. Hence, this analysis reveals that their stabilization is significantly influenced by extended hyperconjugation and strong intramolecular charge transfer. These factors underscore the importance of their charge transfer properties, which are pivotal for their nonlinear optical (NLO) characteristics.\u03c3), chemical potential (\u03bc)32, ionization potential (IP)33, electronegativity (X)34, global hardness (\u03b7)35, electron affinity (EA) and global electrophilicity index (\u03c9)36 that impart knowledge about molecular stability and its reactivity. Ionization potential (IP) is the principal parameter which defines energy needed to eliminate electron out of MO. From Table IP value is present in PCMD1 i.e. 5.64\u00a0eV. The trend for IP value is; PCMD9\u2009>\u2009PCMD4\u2009=\u2009PCMD7\u2009>\u2009PCMD8\u2009>\u2009PCMD5\u2009>\u2009PCMD3\u2009=\u2009PCMR\u2009>\u2009PCMD2\u2009>\u2009PCMD1. Conversely, energy liberates on electronic insertion in valence shell is termed as electron affinity (EA). The highest EA is exhibited by PCMD7 at 3.65\u00a0eV while 3.35\u00a0eV is the least energy released upon electronic addition in PCMD1. Knowledge about polarization of electronic cloud is collected from global softness (\u03c3) and global hardness (\u03b7) values. High polarization of electronic cloud is demonstrated by softer molecules while least is associated with harder compounds. The highest \u03b7 value is present in PCMD9 at 1.22\u00a0eV that reduces to 1.02\u00a0eV in PCMD7. The values of global softness (\u03c3) are lesser than their respective global hardness (\u03b7) and global electrophilicity index (\u03c9) values. PCMD7 manifests highest softness at 4.88\u00a0eV\u22121 with 0.436\u00a0eV\u22121 being the least softness among all compounds present in PCMD1. Hence all the fabricated chromophores exhibited the higher value of softness which supported the greater charge transference in them than reference chromophore which in result would express good NLO response. The highest value of global electrophilicity index (\u03c9) is possessed by PCMD4 at 10.47\u00a0eV. While the lowest of 8.86\u00a0eV is present in PCMR. Chemical potential (\u03bc) is inversely related to Electronegativity (X) value. Where, chemical potential describes affinity of electron removal while electronegativity reveals affinity to accept electrons. PCMD9 with highest electronegativity and lowest chemical potential at 4.72 and\u2009\u2212\u20094.72\u00a0eV, correspondingly, manifests highest electron transmission in turn possess highest nonlinearity.Global reactivity parameters (GRPs) encompass multiple descriptors i.e. global softness  demonstrate density of transition which is the estimation of excitations involving charge transmission. Whereas, local excitations corresponds to transition density demonstrated by equivalent basis functions (correspondent to same atomic centers)51.Transition density matrices (TDMs) is employed for visualizing and investigating optical nature of each electronic transition in a molecular system during excited state charge dispersion and electron\u2013hole mobilityThe current inquiry of PCMR and PCMD1\u2013D9 has been executed at M06/6-311G via Multiwfn 3.7 . While atomic and molecular nonlinearity subject to extensive nonlinear optical phenomenon is hyperpolarizability . The first order hyperpolarizability (\u03b2tot), second order hyperpolarizability (\u03b3tot), linear polarizability (<\u03b1>) and dipole moment (\u00b5tot) values including tensors for PCMR and PCMD1\u2013D9 are presented in Tables NLO is an eminent discipline of current investigations due to its importance in managing primary tasks of optical memory, telecommunications, signal processing, frequency shifting, optical interconnections, optical logic, optical switching and optical modulation\u00b5) is greatly affected by difference of electronegativity that could be categorically the product of charge magnitude and distance among them, where high electronegativity corresponds to large \u00b555. Besides, molecular \u00b5, polarity is crucial in improving molecular nonlinearity. The \u00b5tot characterize average dipole moment, whereas, tensors contributes to \u00b5tot along x, y and z-orientations are \u00b5x, \u00b5y and \u00b5z56. The highest \u00b5tot values are detected in all the derivatives (PCMD1\u2013D9) in 0.981\u20131.995\u2009\u00d7\u200910\u201317 esu range contrary to reference (PCMR) at 0.308\u2009\u00d7\u200910\u201317esu. The descending order of \u00b5tot is; PCMD5\u2009>\u2009PCMD8\u2009=\u2009PCMD9\u2009>\u2009PCMD6\u2009>\u2009PCMD7\u2009>\u2009PCMD4\u2009>\u2009PCMD1\u2009>\u2009PCMD3\u2009>\u2009PCMD2\u2009>\u2009PCMR. The findings indicate major contribution by x-axis in the overall \u00b5tot 57, a standard molecule for investigating the NLO properties, these compounds exhibit 0.06, 0.23, 0.20, 0.22, 0.24, 0.40, 0.29, 0.24, and 0.37 times greater \u00b5 values. Similarly, when compared to CPTR158, similar analog to our compounds, 0.8, 3.0, 2.6, 3.0, 3.2, 5.4, 3.8, 3.2, and 5.0 the times greater values are found in our fabricated chromophores.The dipole polarizability (ot Table . The PCM\u03b1>) values of PCMR and PCMD1\u2013D9 along with polarizability contributing tensors and their values. The\u2009<\u03b1>\u2009value of 2.712\u2009\u00d7\u200910\u201322 esu is the highest polarizability value among all the chromophores exhibited by PCMD5. However, the least\u2009<\u03b1>\u2009value of 2.310\u2009\u00d7\u200910\u201322 esu corresponds to PCMD1. The\u2009<\u03b1>\u2009values for the rest of the compounds PCMR, PCMD2-D4, PCMD6-D9 are 2.499, 2.495, 2.506, 2.608, 2.588, 2.670, 2.686 and 2.695\u2009\u00d7\u200910\u201322 esu, respectively. The investigation extends to the realm of linear polarizability, where a comparison is drawn between our computed compounds (PCMR and PCMD1\u2013D9) and the standard pNA57 and CPTR158. Notably, the linear polarizability values of pNA57 and CPTR158 stand at 1.178\u2009\u00d7\u200910\u201323 and 1.370\u2009\u00d7\u200910\u201322 esu, respectively. In contrast, our designed derivatives exhibit intriguing linear polarizability values in relation to pNA and CPTR1. Correspondingly, the comprehensive analysis of their contributing tensors indicates major contribution by \u03b1xx towards the overall\u2009<\u03b1>\u2009in all the compounds. The formulated chromophores have shown comparable\u2009<\u03b1>\u2009values with given descending order; PCMD5\u2009>\u2009PCMD9\u2009>\u2009PCMD8\u2009>\u2009PCMD7\u2009>\u2009PCMD4\u2009>\u2009PCMD6\u2009>\u2009PCMD3\u2009>\u2009PCMR\u2009>\u2009PCMD2\u2009>\u2009PCMD1.Table \u03b2tot) value which increases in strongly push\u2013pull configured molecular systems because of extended conjugation. The nine tensors i.e., \u03b2xxx,\u00a0\u03b2xxy,\u00a0\u03b2xyy,\u00a0\u03b2yyy,\u00a0\u03b2xxz,\u00a0\u03b2yyz,\u00a0\u03b2xzz,\u00a0\u03b2yzz,\u00a0\u03b2zzz are used to determine hyperpolarizability values. Table \u03b2tot) values are tabulated in Table \u03b2tot highest of 4.747\u2009\u00d7\u200910\u201327 esu is exhibited by PCMD8, whereas the least hyperpolarizability is present in PCMR at 0.099\u2009\u00d7\u200910\u201327 esu. The same trend for second hyperpolarizability values has been observed, where the highest \u03b3tot of 6.867\u2009\u00d7\u200910\u201332 esu is exhibited by PCMD8, but the least \u03b3tot is present in PCMD1 at 3.517\u2009\u00d7\u200910\u201332 esu. Where the major contribution towards \u03b2tot is exhibited by \u03b2xxx tensor and \u03b3tot in is by \u03b3x tensor. Comparative analysis with pNA and CPTR1 our compounds illustrated higher values for \u03b2 and \u03b3tot50. In conclusion, the changing configuration from A-D-A to D\u2013\u03c0\u2013A and variant acceptor groups indicates substantial ICT besides bathochromic shift which in turn enhances the optical nonlinearity in all the designed chromophores. The high values of hyperpolarizability and polarizability manifest designed compounds as potential candidate for technologically advanced optical devices.Compound\u2019s nonlinearity is calculated by first hyper-polarizability  with greater red shift (701.541\u00a0nm) is examined in PCMD8 than that of other molecules. From all the devised NLO compounds, PCMD8 demonstrated relatively high first hyperpolarizability and second hyperpolarizability of 4.747\u2009\u00d7\u200910\u201327 esu and 6.867\u2009\u00d7\u200910\u201332 esu, respectively. Nevertheless, PCMD5 manifested high dipole moment and linear polarizability value of 1.995\u2009\u00d7\u200910\u201317 esu and 2.712\u2009\u00d7\u200910\u201322 esu, respectively. So, PCMD8 and PCMD5 possessed high optoelectronic (linear and nonlinear) behavior resulted from the induction of nitro and sulfonic acid groups in the acceptor moiety. However, all the formulated compounds have shown higher nonlinearity on comparison with pNA as a standard molecule from the literature. Subsequently, PCMD8 chromophores is approved to be proficient NLO candidates for technologically advanced nonlinear optical devices.In current report, we devised novel octacyclic naphthalene-based PCMD1\u2013D9 nonlinear organic compounds by substituting one end acceptor moiety in PCMR with donor (9-phenyl-9H-carbazole) in derivatives and altering acceptor group in each successive derivative. Quantum chemical calculation were applied to investigate the NLO behavior of fabricated chromophores. The NBO study revealed a hyper conjugative interaction played significant role in stabilizing the molecule. An efficient charge transference from donor to acceptor through spacer has been studied by FMO findings which were further also supported by DOS and TDM analysis. A lower band gap (2.048\u00a0eVSupplementary Information."}
{"text": "N,N\u2032-bidentate ligands [4-(2-amino\u00adeth\u00adyl)morpholine] and two trans-located acetate mol\u00adecules. The Cd atom is located on a centre of inversion, whereas the morpholine and four water mol\u00adecules are adjacent to the acetate moieties. In the crystal, neighboring metal complexes and uncoordinated water mol\u00adecules are linked via N\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding inter\u00adactions.In the title coordination compound, the Cd atom is octa\u00adhedrally coordinated by two  2H3O2)2(C6H14N2O)2]\u00b74H2O, was synthesized by mixing 2 moles of 4-(2-amino\u00adeth\u00adyl)morpholine and 1 mole of cadmium acetate in double-distilled water. The Cd atom is octa\u00adhedrally coord\u00adinated by two N,N\u2032-bidentate ligands [4-(2-amino\u00adeth\u00adyl)morpholine] and two trans-located acetate mol\u00adecules. The Cd atom is located on a center of inversion, whereas the 4-(2-amino\u00adeth\u00adyl)morpholine and four water mol\u00adecules are adjacent to the acetate mol\u00adecules. The chair conformation of the morpholine mol\u00adecules is confirmed. In the crystal, adjacent metal complexes and uncoord\u00adinated water mol\u00adecules are linked via N\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding inter\u00adactions, generating R22(6), R66(16), R66(20) and S11(6) motifs and forming a three-dimensional network. A Hirshfeld surface analysis indicated the contributions of various contacts: H\u22efH (71.8%), O\u22efH/H\u22efO (27.1%), and C\u22efH/H\u22efC (1.0%).The title coordination compound, [Cd(C The coordination polyhedron around the metal atom may be best described as a distorted octa\u00adhedron. The four nitro\u00adgen atoms of the di\u00adamine ligands define the equatorial plane, and two oxygen atoms from the acetate anions coordinate in the trans-axial positions. The coordination of the morpholine ligands creates two five-membered chelate rings  by varying the M\u2014N distances and N\u2014M\u2014N angles. Many articles and reviews have reported that an important factor for metal-ion selection is the chelate ring size, in which five-membered chelate rings promote selectivity for large metal ions with an ionic radius (r+) close to 1.0\u2005\u00c5. Theoretical calculations show that for five-membered N\u2013C\u2013C\u2013N\u2013M chelate rings, the ideal values for the N\u2014M distance and N\u2014M\u2014N angle are 2.5\u2005\u00c5 and 69\u00b0, respectively  and 2.2788\u2005(15)\u2005\u00c5 (Cd\u2014N2 and Cd\u2014N2i), are in good agreement with the values reported in the literature  \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a01] and the cis-angles of the octa\u00adhedron involving O2 and O2i are close to the ideal value of 90\u00b0. The morpholine rings adopt a chair conformation. The acetate group is disordered over two positions of equal occupancy and in both of the crystallographically independent water mol\u00adecules, one of the protons is equally disordered over two positions. Finally, water atom O5 from the water mol\u00adecules is disordered over two positions in a 75\u2005(3):25\u2005(3) ratio.The title compound Fig.\u00a01 crystallgs Fig.\u00a02. Upon co3.et al., 1995et al., 2000a-axis direction indicated by cyan dashed lines. In the crystal, the mol\u00adecules are linked by numerous N\u2014H\u22efO and O\u2014H\u22efO inter\u00adactions  are the most significant, contributing 71.8% to the total crystal packing. This major contribution may be due to van der Waals inter\u00adactions . Fig.\u00a09d shows the C\u22efH/H\u22efC inter\u00adactions, which contribute 1.0% to the Hirshfeld surface.A Hirshfeld surface analysis was performed for the complex alone (excluding the water molecules) and the two-dimensional (2D) fingerprint plots were created with 4.et al., 2016catena-[bis\u00ad-[4-(2-amino\u00adeth\u00adyl)morpholine]]\u00adnickel(II) morpholine]\u00adbis\u00ad(nitrito)nickel(II) bis\u00adnickel(II) copper(II) monohydrate bis\u00ad[4-(2-amino\u00adeth\u00adyl)morpholine]\u00addi\u00adcop\u00adper(II) morpholine-2\u03ba-N,N\u2032]nickel(II) dichloride morpholine.A search in the Cambridge Structural Database : 3301 , 2887 , 1549 , 1411 , 1342 , 1192 , 960 , 653  and 594 .As shown in the reaction scheme Fig.\u00a010, the tit6.Uiso(H) = 1.2\u20131.5Ueq(C), while the N\u2014H and O\u2014H protons were located in residual electron-density maps and refined with distance restraints (DFIX and SADI) and with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O). The acetate group was refined as disordered over two positions (ratio 50:50%) with distance, geometry and ijU restraints . H4 and H6 are disordered over two positions in a 50:50 ratio due to symmetry-related hydrogen bonds. O5 is disordered over two positions in a 75\u2005(3):25\u2005(3) ratio. As both positions have the same distance to H5, H6 and H6\u2032, only one set of the hydrogen atoms was refined for both O5 and O5B.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023008782/jq2030sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023008782/jq2030Isup4.hklStructure factors: contains datablock(s) I. DOI: 2299387CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O\u2014H\u22efO hydrogen bonds between the hy\u00addroxy substituent and the carbonyl O atom of the adjacent mol\u00adecule.The title compound,which is produced by the oxidation of 1-(4- 5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butyl\u00adphen\u00adyl)-2-ethyl-3-ferrocenyl\u00adpyrrole, crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7\u2005(2)\u00b0 with respect to the attached cyclo\u00adpenta\u00addienyl ring and of 43.6\u2005(7)\u00b0 with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butyl\u00adphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589\u2005(16) and 0.411\u2005(16), respectively. In the crystal, mol\u00adecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O\u2014H\u22efO hydrogen bonds between the hy\u00addroxy substituent and the carbonyl O atom of the adjacent mol\u00adecule.The title compound, [Fe(C Therefore, a new centre of chirality is created at C1, which used to be an sp2 carbon atom in the starting compound. Since no chiral reaction conditions were applied, a racemate of the title compound is produced. The title compound also crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The mol\u00adecular structure of the S-enanti\u00adomer is shown in Fig.\u00a01tert-butyl\u00adphenyl group, as well as the non-substituted Cp ring, are disordered with s.o.f. values of 0.589\u2005(16) and 0.411\u2005(16). Bond lengths and angles are of expected values with the C2\u2014C3 bond length of 1.336\u2005(5)\u2005\u00c5, clearly indicating a double bond. In addition, the N1\u2014C4 bond [1.366\u2005(5)\u2005\u00c5] is shortened with respect to the other nitro\u00adgen carbon bonds, as is typical for amides.The title compound, 3.b-axis direction by O\u2014H\u22efO hydrogen bonds of the C(6) type -one CSD -2-ethyl-3-ferrocenyl\u00adpyrrole were treated with 5\u2005mol% p-toluene sulfonic acid and were dissolved in 1.0\u2005mL of anhydrous ethanol. The solution was placed in a 10\u2005mL screw-cap vessel closed with parafilm. The process of the oxidation reaction was followed by thin layer chromatography and it could be observed that the reaction was finished after approximately 8 days. The reaction mixture was transferred to a Schlenk tube, the solvent was removed in vacuo and the remaining oily residue was purified by column chromatography  using CH2Cl2 as the eluent. Slow evaporation of the solvent at ambient temperature led to the formation of crystalline material of the title compound . 1H NMR : (ppm) = 0.55 ; 1.31 ; 1.92 ; 2.84 ; 4.17 ; 4.44\u20134.50 ; 4.72\u20134.73 ; 6.24 ; 7.37\u20137.43 ; 7.48\u20137.52 . 13C NMR : (ppm) = 7.80 (CH3); 26.37 (CH2); 31.32 (CH3); 34.50 (C); 68.03 (CpR); 68.85 (CpR); 70.03 (Cp); 72.96 (CpR); 95.55 (C); 118.48 (=CH); 125.44 (CHPh); 125.86 (CHPh); 135.19 (CPh); 149.21 (CPh); 160.63 (C); 169.10 (C=O). MS (DEI): m/z (%) = 443\u2005(96) [M+]; 427\u2005(76) [M+\u00a0\u2212\u00a0O]; 426\u2005(40) [M+\u00a0\u2212\u00a0OH]; 425\u2005(75) [M+\u00a0\u2212\u00a0H2O]; 398\u2005(22) [M+ \u2212 3CH3]; 360\u2005(98) [M+\u00a0\u2212\u00a0C5H5\u00a0\u2212\u00a0H2O]; 322\u2005(48) [M+\u00a0\u2212\u00a0C5H5Fe]; 305\u2005(58) [M+\u00a0\u2212\u00a0C5H5Fe\u00a0\u2212\u00a0OH]; 294\u2005(64) [M+\u00a0\u2212\u00a0C5H5Fe\u00a0\u2212\u00a0CO].0.5\u2005mmol (200\u2005mg) of 1-(4-6.O2) was located in a difference-Fourier map and refined freely. All carbon-bound hydrogen atoms were placed in idealized positions and refined using a riding model with isotropic displacement parameters Uiso(H) = 1.2eqU(C) for methyl\u00adene and aromatic hydrogen atoms and H3 and Uiso(H) = 1.5eqU(C) for methyl groups. The p-tBuC6H4 and Cp groups are disordered over two positions and were found to refine well with only one free variable. The proportion of the two positions is 58.94:41.06%. SIMU, RIGU, SAME, SADI and FLAT instructions were used to restrain the geometry and displacement parameters of the disordered moieties.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023001858/jq2026sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023001858/jq2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 961575CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-1,3-benzo\u00addiazol-2(3H)-one (I and II) exhibit identical bond distances and angles except for the C\u2014N\u2014C\u2014C torsion angle between the benzimidazolone backbone and the phenyl substituent, which has an effect on the crystal packing and supra\u00admolecular features. The structure of I contains a stronger C=O\u22efH\u2014N hydrogen-bonding inter\u00adaction and a weaker \u03c0\u2013\u03c0 inter\u00adaction between adjacent bezimidazolone moieties in comparison to II.The two polymorphic structures of 3-phenyl-1 I and II) of 3-phenyl-1H-1,3-benzo\u00addiazol-2(3H)-one, C13H10N2O, acquired from pentane diffusion into the solution in THF, are reported. The structures show negligible differences in bond distances and angles, but the C\u2014N\u2014C\u2014C torsion angles between the backbone and the phenyl substituent, 123.02\u2005(15)\u00b0 for I and 137.18\u2005(11)\u00b0 for II, are different. Compound I features a stronger C=O\u22efH\u2014N hydrogen bond than that in II, while the structure of II exhibits a stronger \u03c0\u2013\u03c0 inter\u00adaction than in I, as confirmed by the shorter inter\u00adcentroid distance [3.3257\u2005(8)\u2005\u00c5 in II in comparison to 3.6862\u2005(7)\u2005\u00c5 in I]. Overall, the supra\u00admolecular inter\u00adactions of I and II are distinct, presumably originating from the variation in the dihedral angle.The polymorphic structures ( The compound was prepared following the reported procedure using 1,1\u2032-carbonyl\u00addiimidazole and N1-phenyl\u00adbenzene-1,2-di\u00adamine in CH2Cl2  and blocks (II).Here we report two polymorphic structures of 3-phenyl-12.I) and blocks (II) in space groups C2/c and Pbca, respectively. The two polymorphic structures exhibit identical bond distances and angles, except for the dihedral angle of the phenyl substituent  and \u2212137.18\u2005(12)\u00b0 for I and II, respectively. No additional differences are observed from an analysis of bond distances and angles.The title compounds crystallized as colorless needles \u2005\u00c5, while the corres\u00adponding distance in I is more elongated at 3.6862\u2005(7)\u2005\u00c5.Initial investigations of supra\u00admolecular features for y Figs. 2 and 3 \u25b8.I indicate the inter\u00admolecular inter\u00adactions of C4\u22efC2/C2\u22efC4, C3A\u22efC3A and C7\u2014H7/H7\u2014C7, whereas those in II correspond to C2\u22efC5/C5\u22efC2, C4\u2014H4\u22efC12/ C12\u22efH4\u2014C4, C7A\u22efH6\u2014C6/C6\u2014H6\u22efC7A, C3A\u22efH6\u2014C6/C6-H6\u22efC3A and C3A\u22efC6/C6\u22efC3A contacts. The largest contributions to the Hirshfeld surface of I arises from H\u22efH (44.4%), C\u22efH/H\u22efC (31.9%), and O\u22efH/H\u22efO (13.5%) contacts, whereas the contributions for II are H\u22efH (45.8%), C\u22efH/H\u22efC (27.5%) and O\u22efH/H\u22efO (15.5%). Minor contributions include N\u22efH/H\u22efN (3.6%), C\u22efC (3.2%), C\u22efN/N\u22efC (2.1%), C\u22efO/O\u22efC (1.4%) for I and C\u22efC (5.4%), C\u22efN/N\u22efC (3.4%), N\u22efH/H\u22efN (3.2%), C\u22efO/O\u22efC (0.2%) for II.Minor inter\u00admolecular inter\u00adactions are observed as faint red spots on the surface. The spots in 4.et al., 2016et al., 2013tert-butyl  chains. The distances between a nitro\u00adgen donor and an oxygen acceptor range from 2.79\u20132.84\u2005\u00c5, comparable to the values for I and II of 2.7786\u2005(14) and 2.8453\u2005(14)\u2005\u00c5, respectively.A search for the title compound in the Cambridge Structural Database -one was prepared following a reported procedure  was stirred at room temperature overnight. The resulting white precipitate was filtered. An additional white precipitate was acquired by adding Et2O (10\u2005mL) into the filtrate. Combined yield: 0.30\u2005g (46%). 1H NMR : \u03b4 10.75 , 7.58 , 7.45 , 7.17 , 7.10 , 7.06 . Pentane vapor diffusion into a solution of the compound in THF formed colorless needles and blocks.3-Phenyl-16.Crystal data, data collection, and refinement statistics are summarized in Table\u00a0310.1107/S2056989023003961/vm2281sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989023003961/vm2281Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023003961/vm2281IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989023003961/vm2281Isup4.cmlSupporting information file. DOI: 2260424, 2260423CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Reducing the necessary time to restore primary teeth improves the cooperation of paediatric patients. This study aimed to investigate the marginal integrity of restorations prepared with a bulk-fill resin-based composite (RBC) containing additional fragmentation chain transfer (AFCT) compared to a conventional RBC when light cured with a rapid high-irradiance (3\u00a0s) and a regular (10\u00a0s) curing mode.2 or high-irradiance: 3\u00a0s @ 3000 mW/cm2) and the used restorative material . After thermo-mechanical loading, the marginal integrity was analysed using scanning electron microscopy. A beta regression model and pairwise comparisons were used to statistically analyse the data.Forty class-II cavities were prepared in 40 primary molars. The molars were randomly divided into four groups based on the applied light-curing modes (regular: 10\u00a0s @ 1200 mW/cmp\u2009\u2264\u20090.05). The difference between the light-curing modes for the same RBC was not statistically significant (p \u02c3 0.5).The mean marginal integrity (% \u00b1 SD) of the restorations for each group was as follows: Power Fill (10\u00a0s: 79.7\u2009\u00b1\u200915.6) (3\u00a0s: 77.6\u2009\u00b1\u200911.3), Prime (10\u00a0s: 69.7\u2009\u00b1\u200911.1) (3\u00a0s: 75.0\u2009\u00b1\u20099.7). The difference between the RBCs for the same light-curing mode was statistically significant (AFCT-containing bulk-fill RBC \u201cPower Fill\u201d achieves similar marginal integrity when light-cured with either high-irradiance or regular light-curing modes. \u201cPower Fill\u201d achieves better marginal integrity than the conventional RBC \u201cPrime\u201d regardless of the applied light-curing mode. Resin-based composites have become a solid restorative material option in both permanent and primary teeth \u20133. Some 2), and the incorporation of an \u03b2-allyl sulfone addition fragmentation chain transfer (AFCT) reagent in the matrix of the bulk-fill composite [Two major developments led to the possibility of such short polymerisation time: the introduction of high-power light emitting diode (LED) polymerisation units that can produce high radiant exitance  and the authorisation from the ethics committee was waived . Roots of the extracted molars were embedded in acrylic resin  3\u00a0mm below the cemento-enamel junction and mounted on custom-made holders. One standardised mesial or distal proximal cavity  was prepared in each primary molar. Proximal cavities were prepared with 80-\u00b5m cylindrical burs  rotating at 40,000\u00a0rpm in a high-speed contra-angle handpiece . The bur was exchanged after preparing four cavities. The molars were then randomised into four groups  based on the RBC they would be restored with and the light-curing mode they would be subjected to. The sample size was determined based on recent similar research [2 . The cavities were restored based on their experimental group as shown in Fig.\u00a02, curing time\u2009=\u200910\u00a0s). In groups 3 and 4, each layer of both materials was subjected to high-irradiance light-curing . The composition of the used RBCs is shown in Table\u00a0The molars were mounted and restored in a custom-made adjacent-tooth simulator with two plastic molars on each side on a laboratory desk. A stainless-steel matrix band  was inserted and fixed with a wooden wedge placed 1\u00a0mm below the gingival margin of the cavity. A universal adhesive  was scrubbed for 20\u00a0s on all cavity walls in self-etch mode, thinned with a gentle blow of air in order to evaporate the solvent, and then light-cured for 10\u00a0s at 1200 mW/cmAfter the storage time, impressions were taken for each restoration with an A-silicon material . The impressions were poured out , fixed on aluminium holders  and the formed replicas were sputter-coated with gold . After sputter coating, each replica was examined under a stereo microscope . The cemento-enamel junction buccally and lingually from the restoration was accentuated inside the epoxy resin using a fine scalpel. The replicas were quantitatively analysed for marginal integrity using scanning electron microscopy (SEM) at 20\u00a0kV and 200 \u00d7 magnification . The marginal integrity for each restoration was expressed as a percentage of continuous margins in relation to the entire length of assessable margins. After this initial marginal analysis, all restorations underwent a thermo-mechanical loading (TML) inside an electronic masticator . The restorations were loaded on their occlusal part using a metal ball (diameter\u2009=\u20093\u00a0mm) for 400 000 loading cycles at 49\u00a0N . SimultaA-silicon impressions were taken again after TML and a final quantitative margin analysis using the same aforementioned protocol was carried out. The margin analysis was conducted by one calibrated and experienced operator (MZ) who was blinded to the groups and had only access to the SEM images. Figure\u00a02 and 3\u00a0s @ 3000 mW/cm2). A beta regression model was set to analyse the data. Post-hoc pairwise comparisons between the groups of the same material with different light-curing modes \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d and \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d and between the groups of the same light-curing mode with different materials \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d and \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d were computed using the emmeans package [www.R-project.org).The marginal integrity  was set as the target variable. This variable was analysed with respect to the restoration type  and the light-curing modes (10\u00a0s @ 1200 mW/cm package . The sigp \u02c3 0.1).Before TML, the achieved marginal integrity (% \u00b1 standard deviation SD) of each tested RBC  with each tested light-curing mode (regular \u201c10 s\u201d and high-irradiance \u201c3 s\u201d) was as follows: Power Fill (10\u00a0s: 92.1\u2009\u00b1\u200910.2) (3\u00a0s: 90.1\u2009\u00b1\u20095.4), Prime (10\u00a0s: 90.1\u2009\u00b1\u20096.9) (3\u00a0s: 90.3\u2009\u00b1\u20097.3). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d and \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d and between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d and \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was not statistically significant (p\u2009\u2264\u20090.05). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d, and between \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d was not statistically significant (p \u02c3 0.5). Figure\u00a0After TML, the achieved marginal integrity (% \u00b1 SD) of each tested RBC with each tested light-curing mode was as follows: Power Fill (10\u00a0s: 79.7\u2009\u00b1\u200915.6) (3\u00a0s: 77.6\u2009\u00b1\u200911.3), Prime (10\u00a0s: 69.7\u2009\u00b1\u200911.1) (3\u00a0s: 75.0\u2009\u00b1\u20099.7). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d, and between \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was statistically significant (p \u02c3 0.1).Before TML, the achieved marginal integrity (% \u00b1 SD) of each tested RBC with each tested light-curing mode was as follows: Power Fill (10\u00a0s: 93.3\u2009\u00b1\u200910.6) (3\u00a0s: 89.5\u2009\u00b1\u20095.3), Prime (10\u00a0s: 89.3\u2009\u00b1\u20098.3) (3\u00a0s: 91.3\u2009\u00b1\u20096.7). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d and \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d, and between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d and \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was not statistically significant (p \u02c3 0.1). Figure\u00a0After TML, the achieved marginal integrity (% \u00b1 SD) of each tested RBC with each tested light-curing mode was as follows: Power Fill 10\u00a0s: 83.4\u2009\u00b1\u200916.1) (3\u00a0s: 77.0\u2009\u00b1\u200911.9), Prime (10\u00a0s: 75.8\u2009\u00b1\u200914.1) (3\u00a0s: 76.9\u2009\u00b1\u20099.4). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d and \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d, and between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d and \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was not statistically significant (\u2009\u00b1\u200916.1 (p \u02c3 0.5).Before TML, the achieved marginal integrity (% \u00b1 SD) of each tested RBC with each tested light-curing mode was as follows: Power Fill (10\u00a0s: 88.9\u2009\u00b1\u200914.2) (3\u00a0s: 91.3\u2009\u00b1\u20097.0), Prime (10\u00a0s: 92.0\u2009\u00b1\u20094.7) (3\u00a0s: 88.2\u2009\u00b1\u200913.6). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d and \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d, and between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d and \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was not statistically significant (p\u2009\u2264\u20090.05). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPower Fill (3 s)\u201d, and between \u201cPrime (10 s)\u201d vs. \u201cPrime (3 s)\u201d was also statistically significant (p\u2009\u2264\u20090.05). Figure\u00a0After TML, the achieved marginal integrity (% \u00b1 SD) of each tested RBC with each tested light-curing mode was as follows: Power Fill (10\u00a0s: 71.0\u2009\u00b1\u200918.1) (3\u00a0s: 78.8\u2009\u00b1\u200914.0), Prime (10\u00a0s: 57.7\u2009\u00b1\u200915.4) (3\u00a0s: 71.2\u2009\u00b1\u200915.0). The difference between \u201cPower Fill (10 s)\u201d vs. \u201cPrime (10 s)\u201d, and between \u201cPower Fill (3 s)\u201d vs. \u201cPrime (3 s)\u201d was statistically significant (2) on the marginal integrity of an AFCT-containing bulk-fill RBC  and a conventional RBC in standardised deep class-II cavities in primary molars. The marginal integrity in this study was not affected by the different light-curing modes (the first null-hypothesis cannot be rejected), but indeed affected by the tested RBC (the second null-hypothesis must be rejected).This in-vitro study investigated the effect of a high-irradiance light curing  in the present study. The first attempts to evaluate dental restorative materials with regard to their marginal integrity date back to the 1970s . Some stThe here used loading force and frequency  is reported to be most frequently used to simulate the mechanical degradation of resin composite restorations in vitro . HoweverTaking the margins of the whole restoration (enamel and dentine) into consideration, employing the high-irradiance light-curing mode resulted in similar marginal integrities as the regular 10-s light-curing mode, regardless of the tested RBC. As for Power Fill, this result could be attributed to the presence of the AFCT reagent, which allows a step-like progression of the polymer chain and enhances the thermal and mechanical properties of RBCs, and to the fact that this RBC was actually developed to be compatible with high-irradiance light curing . Par et The bulk-fill RBC \u201cPower Fill\u201d showed better marginal integrity than the conventional RBC \u201cPrime\u201d regardless of the used light-curing mode. This is in contrast to the results of a recent study, which compared the same RBCs and concluded that both achieve similar marginal integrity in primary molars . This co2) does not actually help explain the observed similar marginal integrity. Nevertheless, Steffen et al. [2) or high-irradiance (3\u00a0s @ 2850 mW/cm2) modes. Similar findings (regarding shrinkage stress and degree of conversion) for AFCT-free RBCs were also reported by Par et al. [The conventional RBC \u201cPrime\u201d was not especially developed for high-irradiance light curing and does not contain an AFCT reagent. This makes the observed similar marginal integrity between both applied light-curing modes rather interesting. The fact that the radiant exposure in case of the high-irradiance light-curing mode is less than the regular light-curing mode  or regular light-curing modes (10\u00a0s @ 1200 mW/cm2).AFCT-containing high-viscous bulk-fill RBC \u201cPower Fill\u201d achieves similar performance with regard to marginal integrity of deep class-II cavities in primary molars when light-cured with high-irradiance (3\u00a0s @ 3000 mW/cmAFCT-containing high-viscous bulk-fill RBC \u201cPower Fill\u201d achieves better performance than the conventional RBC \u201cPrime\u201d with regard to marginal integrity in deep class-II cavities in primary molars regardless of the used light-curing mode."}
{"text": "Plasmodium falciparum, is driven by specific transcriptional programs, but it is unclear how most genes are activated or silenced at specific times. There is an association between transcription and spatial organization; however, the molecular mechanisms behind genome organization are unclear. While P.\u2009falciparum lacks key genome\u2010organizing proteins found in metazoans, it has all core components of the cohesin complex. To investigate the role of cohesin in P.\u2009falciparum, we functionally characterize the cohesin subunit Structural Maintenance of Chromosomes protein 3 (SMC3). SMC3 knockdown during early stages of the intraerythrocytic developmental cycle (IDC) upregulates a subset of genes involved in erythrocyte egress and invasion, which are normally expressed at later stages. ChIP\u2010seq analyses reveal that during the IDC, SMC3 enrichment at the promoter regions of these genes inversely correlates with gene expression and chromatin accessibility. These data suggest that SMC3 binding contributes to the repression of specific genes until their appropriate time of expression, revealing a new mode of stage\u2010specific gene repression in P.\u2009falciparum.The complex life cycle of the human malaria parasite,  Plasmodium falciparum, the cohesin subunit SMC3 plays a role in stage\u2010specific gene repression that is distinct from heterochromatin\u2010mediated repression of genes involved in antigenic variation and gametocytogenesis.In the human malaria parasite  Plasmodium falciparum, has a significant impact on human health in endemic regions  was found to play a role in the nuclear organization of centromeres, and knockdown led to defects in var gene transcription \u2014key genome organizing proteins in metazoans , SMC3 (PF3D7_0414000), and a protein with the N\u2010terminal Rad21/Rec8 domain  is present in the P. falciparum cohesin complex  and stag , 24 (trophozoite), and 36 (schizont) hours post invasion (hpi). Using the macs2 peak calling algorithm  between significant peaks called in both clones for each time point, and we used this cohort of shared peaks for further analysis  of SMC3\u20103HA\u2010 Dataset\u00a0. No signet\u00a0al,\u00a0et\u00a0al\u00a0, \u201ccell\u2013cell adhesion\u201d , \u201cresponse to host\u201d , and \u201cantigenic variation\u201d , \u201cmovement in host environment\u201d (q\u2009=\u20093.3\u2009\u00d7\u200910\u22123), \u201cexit from host\u201d (q\u2009=\u20090.026), and \u201centry into host\u201d (q\u2009=\u20090.05). These categories include genes that are involved in invasion of or egress from the red blood cell such as ralp1 , as knockdown at the protein level could not be achieved after a single cell cycle , 69% at 24 hpi (Dataset\u00a0q\u2009=\u20091.3\u2009\u00d7\u200910\u221239), and 48% at 36 hpi  and ribonucleoprotein complex biogenesis (1.82\u2009\u00d7\u200910\u221215), subunit organization (2.47\u2009\u00d7\u200910\u221213), and assembly , glideosome\u2010associated protein 45 , merozoite surface protein 1 , and merozoite surface protein 9  does not inhibit parasite growth agrees with reports in S. cerevisiae and D. melanogaster in which normal growth and sister chromatid cohesion were achieved despite an 87 and 80% decrease, respectively, in Rad21, a core component of the cohesin complex  datasets do not provide evidence of typical enhancer\u2010promoter interactions found in other eukaryotes  is involved in transcription of invasion\u2010related genes via binding to the GTGCA motif, likely by interaction with the bromodomain protein 1  lysis during ring stage followed by a plasmagel  enrichment for late blood stages 24\u2009h later. Another sorbitol treatment 6\u2009h afterward places the 0\u2009h time point 3\u2009h after the plasmagel enrichment. Thus, the window of synchronicity for cultures is \u00b1\u20093\u2009h. Parasite development was monitored by Giemsa staining. Parasites were harvested at 1\u20135% parasitemia.Blood stage 3D7 io et\u00a0al\u00a0. Brieflyglms strain was generated using a two\u2010plasmid system (pUF1 and pL7) based on the CRISPR/Cas9 system previously described in Ghorbal et\u00a0al\u00a0(PfSMC3\u20103HA\u2010glmS containing the single guide RNA (sgRNA) \u2010encoding sequence 5\u2032\u2010CCTAGAAAATTAGAACAATT\u20103\u2032 targeting the 3\u2032 UTR of PF3D7_0414000. The pL7\u2010PfSMC3\u20103HA\u2010glmS plasmid also contained the homology repair construct 5\u2032\u2010AGATAGAGAGAGTTATATATCTAAAGGAACAAAGAATGAGGCCTACGAAATTATTAGCATTGTATAAAAAAAAAAAGAAAAAAAAAAGAAAAAAAAAAAAGATTATATATATAATATATGTTGACAATTAATAAATATATTTGTATATATCTGTTAACTAATTATGAAAATTTTTGAATCAATAAATTTTTTAAATAACAAAAAAAAAAAAAAATATATATATTATATATATATTTTATATTTTATATTTTCTTGTAATTTTTGTTTTTTTAGGAGGAAAAACATGCCCTAGAAAATggcggtggaTACCCTTACGATGTGCCTGATTACGCGTAtCCcTAtGAcGTaCCaGAcTAtGCGTACCCtTAtGAcGTtCCgGATTAtGCtcacggggtgTAAGCGGCCGCGGTCTTGTTCTTATTTTCTCAATAGGAAAAGAAGACGGGATTATTGCTTTACCTATAATTATAGCGCCCGAACTAAGCGCCCGGAAAAAGGCTTAGTTGACGAGGATGGAGGTTATCGAATTTTCGGCGGATGCCTCCCGGCTGAGTGTGCAGATCACAGCCGTAAGGATTTCTTCAAACCAAGGGGGTGACTCCTTGAACAAAGAGAAATCACATGATCTTCCAAAAAACATGTAGGAGGGGACAACAATTTGGTTTTGTTTTTTTCTTTAGGTTTTGAGAAAAACAAATAGGAAATACAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAATGTATTTTTACATATGCACTTGGATTATTTTATTTTTATTATTTTTCTTTATATAAAGTAAAAATATACATAAGTATGCTTATTTATTACATAAGAGTTTATTTAAGAAAGGTTTCTTTTTCATAATATTGTGTGCATGAGTTTTTTTTTATTTTATTTTTTTTTTTTATTTCTGTAACGAAAAGGATATTAAAAAAAATAATAAAA\u20103\u2032 . This homology repair construct comprises a 3\u2009\u00d7\u2009Hemaglutinin (3HA) \u2013 encoding sequence followed by a glmS ribozyme\u2010encoding sequence  and 1.5\u2009\u03bcM DSM1 (MR4/BEI Resources). Parasites reappeared approximately 3\u2009weeks after transfection, and 5\u2010fluorocytosine was used to negatively select the pL7 plasmid.The SMC3\u20103HA\u2010al et\u00a0al\u00a0. A 3D7 wet\u00a0al\u00a0(smc1 (PF3D7_1130700) and stag (PF3D7_1456500), respectively, were amplified using either SMC1\u2010HR\u2010FW/RV or STAG\u2010HR\u2010FW/RV (Dataset\u00a0The SMC1\u20103HA\u2010dd and STAG\u20103HA\u2010dd strains were generated\u00a0using the method of selection\u2010linked integration (SLI) previously\u00a0described in Birnbaum et\u00a0al\u00a0. Homolog Dataset\u00a0. The obt Dataset\u00a0, followeE. coli (Agilent Technologies 200315). All the parasite lines were cloned by limiting dilution, and integration at the targeted genomic locus was confirmed by PCR (Dataset\u00a0All cloning was performed using KAPA HiFi DNA Polymerase (Roche 07958846001), In\u2010Fusion HD Cloning Kit (Clontech 639649), and XL10\u2010Gold Ultracompetent  Dataset\u00a0 and Sangglms clone  and WT culture , as a negative control, were synchronized. Late stage parasites (1.5\u2009\u00d7\u2009109 parasites) were enriched using Percoll density gradient separation and then cross\u2010linked with 1\u2009ml 0.5\u2009mM dithiobissuccinimidyl propionate  in DPBS for 60\u2009min at 37\u00b0C  containing protease and phosphatase inhibitor cocktail (Thermo Fisher 78440) and 1\u2009U/\u03bcl of Benzonase (Merck 71206). The lysates were cleared by centrifugation at 16,000\u2009g for 10\u2009min at 4\u00b0C. Supernatants were incubated with 25\u2009\u03bcl of anti\u2010HA Dynabeads (Thermo Fisher 88836) overnight with rotation at 4\u00b0C. Beads were collected with a magnet and washed five times with 1\u2009ml RIPA buffer, then five times with 1\u2009ml DPBS, and then once with 1\u2009ml 25\u2009mM NH4HCO3 (Sigma 09830). The beads were reduced with 100\u2009mM dithiothreitol (Sigma D9779), alkylated with 55\u2009mM iodoacetamide (Sigma I1149), and subjected to on\u2010bead digestion using 1\u2009\u03bcg of trypsin (Thermo Fisher 90059). The resulting peptides were desalted using C18 ziptips (Merck ZTC04S096) and sent for MS analysis.An SMC3\u20103HA\u2010m/z, AGC 1e5  using an EASY\u2010Spray column, 50\u2009cm\u2009\u00d7\u200975\u2009\u03bcm ID, PepMap RSLC C18, 2\u2009\u03bcm (Thermo Fisher ES803A) over a 70\u2010min gradient before nanoelectrospray using a Q Exactive HF\u2010X mass spectrometer (Thermo Fisher). The mass spectrometer was operated in a data\u2010dependent mode. The parameters for the full scan MS were as follows: resolution of 60,000 across 350\u20131,500\u20092, 1% IGEPAL CA\u2010630, and 1\u00d7 protease inhibitor cocktail ) at 4\u00b0C and incubated on ice for 30\u2009min. The cytoplasmic lysate was cleared with centrifugation . The pellet (containing the nuclei) was resuspended in 3.3 times less volume of nuclear extraction buffer  than cytoplasmic lysis buffer at 4\u00b0C, transferred to 1.5\u2009ml sonication tubes , and sonicated for 5\u2009min total (10\u2009cycles of 30\u2009s on/off) in a Diagenode Pico Bioruptor at 4\u00b0C. This nuclear lysate was cleared with centrifugation . Protein samples were supplemented with NuPage Sample Buffer (Thermo Fisher NP0008) and NuPage Reducing Agent (Thermo Fisher NP0004) and denatured for 10\u2009min at 70\u00b0C. Proteins were separated on a 4\u201312% Bis\u2010Tris NuPage gel (Thermo Fisher NP0321) and transferred to a PVDF membrane with a Trans\u2010Blot Turbo Transfer system (Bio\u2010Rad). The membrane was blocked for 1\u2009h with 1% milk in PBST  at 25\u00b0C. HA\u2010tagged proteins and histone H3 were detected with anti\u2010HA  and anti\u2010H3  primary antibodies, respectively, followed by donkey anti\u2010rabbit secondary antibody conjugated to horseradish peroxidase . SMC3 was detected with an in\u2010house\u2010generated anti\u2010SMC3 antibody , followed by sheep HRP anti\u2010mouse secondary antibody .\u00a0HRP signal was developed with SuperSignal West Pico Plus or Femto chemiluminescent substrate  and imaged with a ChemiDoc XRS+ (Bio\u2010Rad).Parasites were washed once with Dulbecco's phosphate\u2010buffered saline , then resuspended in cytoplasmic lysis buffer  was amplified from cDNA of 3D7 wild\u2010type parasites and inserted into the pGEX expression vector. The plasmid was verified by sequencing and used to transform SHuffle T7 expression bacteria (New England BioLabs C3026J). Recombinant protein expression was induced with 100\u2009\u03bcM IPTG overnight with shaking at 16\u00b0C, and the pellet was frozen at \u221280\u00b0C until use. Soluble GST\u2010tagged recombinant protein was purified using Glutathione Sepharose 4 Fast Flow (Cytiva GE17\u20105132\u201003), according to manufacturer's instructions. Briefly, the bacterial pellet was resuspended in cold lysis buffer . The lysate was sonicated on ice with a probe sonicator . The sample was centrifuged at 18,000\u2009g for 1\u2009h at 4\u00b0C, and the soluble lysate was incubated with Glutathione Sepharose beads (Cytiva GE17\u20105132\u201003) overnight with gentle tumbling at 4\u00b0C. The next day, the lysate with beads was loaded onto chromatography columns , and the beads were washed with cold PBS containing 5\u2009mM EDTA. Recombinant protein was eluted with elution buffer , buffer exchanged into PBS , and stored at \u221220\u00b0C until use. Final protein concentration was obtained using Protein Assay (BioRad).The coding sequence for the N\u2010terminal region (amino acids 1\u2010253) of th, 2013). All experiments were approved by the Ethics Committee CETEA Institute Pasteur and registered under the reference Permit Number dap180040, issued in 2018. The PfSMC3 antibody was purified from pooled mouse serum using rProtein G Agarose (Invitrogen 15920) according to manufacturer's instructions. The final purified antibody was dialyzed in PBS using a Float\u2010A\u2010Lyzer (Repligen). Purified antibodies were stored at \u221220\u00b0C in 50% Glycerol.Purified recombinant protein was used to immunize C57BL/6 mice. Ten micrograms were used for the first immunization in Freund's Complete Adjuvant (Sigma F5881) and three subsequent boosters in Freund's Incomplete Adjuvant (Sigma F5506). Animals were housed in the Institute Pasteur animal facilities, accredited by the French Ministry of Agriculture for performing experiments on live rodents. Work on animals was performed in compliance with French and European regulations on care and protection of laboratory animals . Parasite cultures were centrifuged at 800\u2009g for 3\u2009min at 25\u00b0C. Medium was removed and the RBCs were lysed with 10\u2009ml 0.075% saponin (Sigma S7900) in DPBS at 37\u00b0C. The parasites were centrifuged at 3,250\u2009g for 3\u2009min at 25\u00b0C and washed twice with 10\u2009ml DPBS at 4\u00b0C. The supernatant was removed, and the parasite pellet was resuspended in 1\u2009ml 0.5\u2009mM dithiobissuccinimidyl propionate  in DPBS for 30\u2009min at 25\u00b0C  were washed twice with ChIP dilution buffer  using a DynaMag magnet (Thermo Fisher 12321D). The beads were resuspended in 200\u2009\u03bcl 0.02% Tween\u201020 in DPBS with 1\u2009\u03bcg of anti\u2010HA antibody (Abcam ab9110) or IgG (Diagenode C15410206) and incubated with rotation at 4\u00b0C for 6\u2009h.g and the supernatant was removed. The pellet was resuspended in 1\u2009ml cytoplasmic wash buffer  and rotated for 10\u2009min. The lysates were centrifuged for 5\u2009min at 5,000\u2009g, and the supernatant was removed. The pellet was resuspended in 200\u2009\u03bcl nuclear lysis buffer , transferred to 1.5\u2009ml sonication tubes (Diagenode C30010016), and sonicated for 2.5\u2009min total (5\u2009cycles of 30\u2009s on/off) in a Diagenode Pico Bioruptor. The sonicated extracts were centrifuged at 13,500\u2009g for 10\u2009min. The supernatant was diluted with 400\u2009\u03bcl dilution buffer 2 .All further steps were performed at 4\u00b0C. The cross\u2010linked parasites were resuspended in 900\u2009\u03bcl of cytoplasmic lysis buffer  and rotated for 30\u2009min. The lysates were centrifuged for 5\u2009min at 2,000\u2009PfSMC3 antibody (1:500 in 1% milk\u2010PBST) followed by sheep HRP anti\u2010mouse secondary antibody . Histone H3 was detected with Anti\u2010H3 , followed by donkey HRP anti\u2010rabbit secondary antibody . HRP signal was developed with SuperSignal West Pico Plus or West Femto chemiluminescent substrate  and imaged with a ChemiDoc XRS+ (Bio\u2010Rad).Using a DynaMag magnet, the antibody\u2010conjugated Dynabeads were washed once with 200\u2009\u03bcl of dilution buffer 1  and resuspended in 200\u2009\u03bcl dilution buffer 2 . The washed antibody\u2010conjugated Dynabeads were added to the diluted nuclear lysate and incubated overnight with rotation at 4\u00b0C. The beads were collected on a DynaMag magnet and the supernatant was removed and kept as flow through. The beads were washed three times with 200\u2009\u03bcl of wash buffer . The beads were resuspended in 30\u2009\u03bcl of 2\u00d7 NuPage Sample Buffer (Thermo Fisher NP0008) and 3.4\u2009\u03bcl of NuPage Reducing Agent (Thermo Fisher NP0004) and denatured for 5\u2009min at 95\u00b0C. The eluate was separated from the beads with the DynaMag magnet. Lysates and the bead eluate were separated on a 3\u20108% Tris\u2010Acetate NuPage gel (Thermo Fisher EA0375) and transferred to a PVDF membrane with a Trans\u2010Blot Turbo Transfer system (Bio\u2010Rad). Membranes were blocked with 1% milk\u2010PBST . HA\u2010tagged SMC1 and STAG proteins were detected with anti\u2010HA conjugated to HRP . SMC3 was detected with anti\u2010et\u00a0al,\u00a0et\u00a0al\u00a0 in PBS for 30\u2009min. Cells were incubated with anti\u2010HA  and/or anti\u2010HP1 [from  with DAPI  for 45\u2009min followed by three 10\u2009min washes with 0.5% Tween\u00ae20/PBS. Cells were washed once more with PBS and placed onto polyethyleneimine\u2010coated slides (Thermo Scientific 30\u201042H\u2010RED\u2010CE24). Once adhered to the slide, cells were washed twice with PBS and mounted with VectaShield\u00ae (Vector Laboratories). Images were acquired using a Deltavision Elite imaging system , and Fiji (http://fiji.sc) was used for analysis using the least manipulation possible.iRBCs were washed once with DPBS (Thermo Fisher 14190) at 37\u00b0C and fixed in suspension in 4% paraformaldehyde (EMS 15714) with 0.0075% glutaraldehyde (EMS 16220) in PBS for 20\u2009min at 25\u00b0C, as described previously , 24  and 36 hpi . Parasite culture was centrifuged at 800\u2009g for 3\u2009min at 25\u00b0C. Medium was removed and the RBCs were lysed with 10\u2009ml 0.075% saponin (Sigma S7900) in DPBS at 37\u00b0C. The parasites were centrifuged at 3,250\u2009g for 3\u2009min at 25\u00b0C and washed with 10\u2009ml DPBS at 37\u00b0C. The supernatant was removed, and the parasite pellet was resuspended in 10\u2009ml of PBS at 25\u00b0C. The parasites were cross\u2010linked by adding methanol\u2010free formaldehyde  and incubating with gentle agitation for 10\u2009min at 25\u00b0C. The cross\u2010linking reaction was quenched by adding glycine  and incubating with gentle agitation for 5\u2009min at 25\u00b0C. Parasites were centrifuged at 3,250\u2009g for 5\u2009min at 4\u00b0C and the supernatant removed. The pellet was washed with DPBS and centrifuged at 3,250\u2009g for 5\u2009min at 4\u00b0C. The supernatant was removed, and the cross\u2010linked parasite pellets were snap\u2010frozen.Two clonal populations (clone A and B) of SMC3\u20103HA\u2010For each time\u2010point, 200\u2009\u03bcl of Protein G Dynabeads (Invitrogen 10004D) were washed twice with 1\u2009ml ChIP dilution buffer  using a DynaMag magnet (Thermo Fisher 12321D). The beads were resuspended in 1\u2009ml ChIP dilution buffer with 8\u2009\u03bcg of anti\u2010HA antibody (Abcam ab9110) and incubated on a rotator at 4\u00b0C for 6\u2009h.g at 4\u00b0C, the supernatant was removed, and the pellet was resuspended in SDS lysis buffer  at 4\u00b0C (3.6\u2009ml for the 12 hpi sample and 1.8\u2009ml for the 24 ad 36 hpi samples). The liquid was distributed into 1.5\u2009ml sonication tubes  and sonicated for 12\u2009min total (24\u2009cycles of 30\u2009s on/off) in a Diagenode Pico Bioruptor at 4\u00b0C. The sonicated extracts were centrifuged at 13,500\u2009g for 10\u2009min at 4\u00b0C and the supernatant, corresponding to the chromatin fraction, was kept. The DNA concentration for each time point was determined using the Qubit dsDNA High Sensitivity Assay Kit (Thermo Fisher Scientific Q32851) with a Qubit 3.0 Fluorometer (Thermo Fisher Scientific). For each time point, chromatin lysate corresponding to 100\u2009ng of DNA was diluted in SDS lysis buffer  and kept as \u201cinput\u201d at \u221220\u00b0C. For clones A and B, chromatin lysate corresponding to 19 and 18\u2009\u03bcg (12 hpi), 2 and 1.4\u2009\u03bcg (24 hpi) and 3 and 5.2\u2009\u03bcg (36 hpi) of DNA, respectively,\u00a0was diluted 1:10 in ChIP dilution buffer at 4\u00b0C.The cross\u2010linked parasites were resuspended in 4\u2009ml of lysis buffer  at 4\u00b0C, and 10% Nonidet\u2010P40 was added . The parasites were lysed in a prechilled dounce homogenizer (200 strokes for 12 hpi parasites and 100 strokes for 24 and 36 hpi parasites). The lysates were centrifuged for 10\u2009min at 13,500\u2009Low salt wash buffer  at 4\u00b0C.High salt wash buffer  at 4\u00b0C.LiCl wash buffer  at 4\u00b0C.TE wash buffer  at 25\u00b0C.Using a DynaMag magnet, the antibody\u2010conjugated Dynabeads were washed twice with 1\u2009ml ChIP dilution buffer and resuspend in 100\u2009\u03bcl of ChIP dilution buffer at 4\u00b0C. Then the washed antibody\u2010conjugated Dynabeads were added to the diluted chromatin sample and incubated overnight with rotation at 4\u00b0C. The beads were collected on a DynaMag into eight different tubes per sample, the supernatant was removed, and the beads in each tube were washed for 5\u2009min with gentle rotation with 1\u2009ml of the following buffers, sequentially:After the washes, the beads were collected on a DynaMag, the supernatant was removed, and the beads for each time point were resuspended in 800\u2009\u03bcl of elution buffer and incubated at 65\u00b0C for 30\u2009min with agitation . The beads were collected on a DynaMag and the eluate, corresponding to the \u201cChIP\u201d samples, was transferred to a different tube.g at 4\u00b0C to separate phases. The aqueous top layer was transferred to another tube and mixed with 30\u2009\u03bcg glycogen (Thermo Fisher 10814) and 5\u2009M NaCl . Eight hundred microliters 100% EtOH at 4\u00b0C were added to each sample, which was then incubated at \u221220\u00b0C for 30\u2009min. The DNA was pelleted by centrifugation for 10\u2009min at 13,500\u2009g at 4\u00b0C, washed with 500\u2009\u03bcl 80% EtOH at 4\u00b0C, and centrifuged for 5\u2009min at 13,500\u2009g at 4\u00b0C. After removing the EtOH, the pellet was dried at 25\u00b0C and all DNA for each sample was resuspended in 30\u2009\u03bcl 10\u2009mM Tris\u2013HCl, pH 8 total. The DNA concentration and average size of the sonicated fragments was determined using a DNA high sensitivity kit (Agilent 5067\u20104626) and the Agilent 2100 Bioanalyzer. Libraries for Illumina Next Generation Sequencing were prepared with the MicroPlex library preparation kit (Diagenode C05010014), with KAPA HiFi polymerase (KAPA biosystems) substituted for the PCR amplification. Libraries were sequenced on the NextSeq 500 platform (Illumina).For purification of the DNA, both \u201cChIP\u201d and \u201cInput\u201d samples were incubated for approximately 10\u2009h at 65\u00b0C to reverse the crosslinking. Two hundred microliters of TE buffer followed by 8\u2009\u03bcl of RNaseA  were added to each sample, which was then incubated for 2\u2009h at 37\u00b0C. Four microliters Proteinase K  were added to each sample, which was then incubated for 2\u2009h at 55\u00b0C. Four hundered microliters phenol:chloroform:isoamyl alcohol  were added to each sample, which was then mixed with vortexing and centrifuged for 10\u2009min at 13,500\u2009P.\u00a0falciparum genome  were mapped to the P. falciparum reference genome feature file  was added to one half of the culture for two rounds of parasite replication (approximately 96\u2009h). Parasites were then re\u2010synchronized and three technical replicates (with and without glucosamine) were harvested at 12, 24, and 36 hpi. RBCs were lysed in 0.075% saponin (Sigma S7900) in PBS at 37\u00b0C, centrifuged at 3,250\u2009g for 5\u2009min, washed in PBS, centrifuged at 3,250\u2009g for 5\u2009min, and resuspended in 700\u2009\u03bcl QIAzol reagent (Qiagen 79306). RNA was extracted using an miRNeasy Mini kit (Qiagen 1038703) with the recommended on\u2010column DNase treatment. Total RNA was poly (A) selected using the Dynabeads mRNA Purification Kit (Thermo Fischer Scientific 61006). Library preparation was performed with the NEBNext\u00ae Ultra\u2122 II Directional RNA Library Prep Kit for Illumina\u00ae (New England Biolabs E7760S) and paired end sequencing was performed on the Nextseq 550 platform (Illumina). Sequenced reads were mapped to the P. falciparum genome  using the built\u2010in tool at PlasmoDB.org .A WT and SMC3\u20103HA\u2010et\u00a0al,\u00a0et\u00a0al,\u00a0et\u00a0al\u00a0 of each sample to the microarray data from  was added to one half for approximately 96\u2009h before starting the growth curve. The parasites were tightly re\u2010synchronized and diluted to ~0.2% parasitemia (5% hematocrit) at ring stage. The growth curve was performed in a 96\u2010well plate (200\u2009\u03bcl culture per well) with three technical replicates per condition per blood. Every 24\u2009h, 5\u2009\u03bcl of the culture were fixed in 45\u2009\u03bcl of 0.025% glutaraldehyde in PBS for 1\u2009h at 4\u00b0C. After centrifuging at 800\u2009g for 5\u2009min, free aldehyde groups were quenched by re\u2010suspending the iRBC pellet in 200\u2009\u03bcl of 15\u2009mM NH4Cl in PBS. A 1:10 dilution of the quenched iRBC suspension was incubated with Sybr Green I (Sigma S9430) to stain the parasite nuclei. Quantification of the iRBCs was performed in a CytoFLEX S cytometer (Beckman Coulter), and analysis with was done with FlowJo Software. Growth rate was calculated and expressed as the parasitemia at Day X divided by the starting average parasitemia (Day 1) of the correspondent culture.Parasite growth was measured as described previously (Vembar BioRender.com.The synopsis image for this manuscript was created with Catarina Rosa: Conceptualization; investigation; visualization; writing \u2013 original draft; writing \u2013 review and editing. Parul Singh: Conceptualization; data curation; formal analysis; validation; visualization; writing \u2013 original draft; writing \u2013 review and editing. Patty Chen: Investigation; visualization. Ameya Sinha: Investigation. Aur\u00e9lie Cla\u00ebs: Investigation. Peter R Preiser: Supervision; funding acquisition. Peter C Dedon: Supervision; funding acquisition. Sebastian Baumgarten: Conceptualization; formal analysis; supervision; validation; visualization; writing \u2013 original draft; writing \u2013 review and editing. Artur Scherf: Supervision; funding acquisition. Jessica M Bryant: Conceptualization; formal analysis; supervision; funding acquisition; visualization; writing \u2013 original draft; project administration; writing \u2013 review and editing.The authors declare that they have no conflict of interest.Expanded View Figures PDFClick here for additional data file.Dataset EV1Click here for additional data file.Dataset EV2Click here for additional data file.Dataset EV3Click here for additional data file.Dataset EV4Click here for additional data file.Dataset EV5Click here for additional data file.Dataset EV6Click here for additional data file.Dataset EV7Click here for additional data file.Dataset EV8Click here for additional data file.Dataset EV9Click here for additional data file.Dataset EV10Click here for additional data file.Dataset EV11Click here for additional data file.Dataset EV12Click here for additional data file.Dataset EV13Click here for additional data file.Dataset EV14Click here for additional data file.Dataset EV15Click here for additional data file.Dataset EV16Click here for additional data file.Dataset EV17Click here for additional data file.Dataset EV18Click here for additional data file.Dataset EV19Click here for additional data file.Dataset EV20Click here for additional data file.Dataset EV21Click here for additional data file.Dataset EV22Click here for additional data file.PDF+Click here for additional data file.Source Data for Figure 1Click here for additional data file.Source Data for Figure 2Click here for additional data file.Source Data for Figure 4Click here for additional data file."}
{"text": "The crystal structures of a di\u00adhydro\u00adfurylsilane and a di\u00adhydro\u00adfurylgermane are reported. Hirshfeld surface analyses were performed to investigate the inter\u00admolecular inter\u00adactions. 4H5O)4 (1) and Ge(C4H5O)4 (2) are di\u00adhydro\u00adfuryl compounds of silicon and germanium and are useful building blocks for the functionalization of these elements. Both structures crystallize in space group P21/n in the monoclinic crystal system with two mol\u00adecules in the asymmetric unit: the Si and Ge atoms adopt slightly distorted tetra\u00adhedral geometries, while the C4H5O moieties exhibit shallow envelope conformations. Through a Hirshfeld surface analysis of the structures, inter\u00adactions within the crystal packing could be elucidated: compound 1 features a polymeric chain in the (101) plane via C\u2014H\u22efO hydrogen bonds whereas in 2 C\u2014H\u22efO hydrogen bonds create a polymeric chain in the (010) plane.The title compounds Si(C The two compounds are already known in the literature  were prepared by Lukevits and co-workers in the 1980s  \u2212x, \u2212y, \u2212z] with a distance of 2.22\u2005(4)\u2005\u00c5 was identified by the red spots on the Hirshfeld surface. However, these red spots show only a small proportion of the inter\u00adactions indicated in the fingerprint. Furthermore, a C30\u22efH24Bii  van der Waals inter\u00adaction with a separation of 2.796\u2005(16)\u2005\u00c5 was also identified. The contribution of the C\u22efH inter\u00adactions is 10.7%, which is a low contribution to the crystal packing. Besides these inter\u00adactions, H\u22efO inter\u00adactions could be identified and contribute 19.2% of the structure in the solid state. Hydrogen bonds between C\u2014H\u22efO, which are indicated by red spots on the Hirshfeld surface are listed in Table\u00a05A\u22efO5ii, C27\u2014H27B\u22efO3iii and C31\u2014H31A\u22efO4 can be described as having a D11(2) graph-set motif. C23\u2014H23B\u22efO5i is described by et al., 1990B\u22efO3iii and C31\u2014H31A\u22efO4, a part of the crystal packing is defined along the [101] direction \u2005\u00c5 and H7B\u22efH7Bi  at 2.20\u2005(4)\u2005\u00c5 are visible as red spots and could be identified as close inter\u00adactions by the Hirshfeld surface. The contribution of the van der Waals inter\u00adactions is slightly lower at 10.0%. The inter\u00adaction C32\u22efH4Aii  at 2.79\u2005(2)\u2005\u00c5 could also be detected on the Hirshfeld surface. As in the case of 1, inter\u00adactions of the form H\u22efO could be determined, which contribute 18.3% to the crystal packing. These hydrogen bonds were detected by red spots on the Hirshfeld surface and are shown in Table\u00a06A\u22efO7i and C23\u2013H23A\u22efO4ii can be described by the graph-set motif D11(2). In contrast, the hydrogen bond C31\u2014H31A\u22efO7iii is described by the graph-set motif et al., 1990A\u22efO7iii and C31\u2014H31A\u22efO7i, a part of the crystal packing, which forms a plane in the [010] direction, can be seen in Fig.\u00a08For the Hirshfeld surface analysis of ed Fig.\u00a06. The dised Fig.\u00a06. The dis4.et al., 2016et al., 2022et al., 20201 and 2. They also display similar (DHF)C\u2014Si\u2014C(DHF) bond angles and also a slightly distorted tetra\u00adhedron. In addition, a deviation in the planarity of the di\u00adhydro\u00adfuryl rings was found there. An extended search for 3-silanes revealed the compounds (trimeth\u00adyl)silane -5-methyl-4-(t-butyl\u00addiphenyl\u00adsil\u00adyl)-2,3-di\u00adhydro-furan-2-carb\u00adoxy\u00adlic acid (1\u2032-phenyl\u00adeth\u00adyl)amide -furan\u00adone silane was also found in the database when searching for (2-furan\u00adyl)silane germane and an extended search for 3-germane found no hits.5.1 and 2 have already been described by Lukevits and Ertschak , tert-butyl\u00adlithium  was added at 228\u2005K to a solution of 2,3-di\u00adhydro\u00adfuran  in diethyl ether (approx. 100\u2005ml). The reaction solution was stirred for 1\u2005h at room temperature. Then, tetra\u00adchloro\u00adsilane  was added at 243\u2005K and the reaction solution was stirred for 1\u2005h. The resulting solid was separated by inert filtration. The obtained solution was concentrated in vacuo and crystallized at 243\u2005K. The solvent was removed and the solid was washed with cold diethyl ether. The product tetra\u00adkis\u00adsilane (1)  was obtained as colourless blocks.Compound 1H NMR: : \u03b4 = 2.25 , 4.06 , 5.88  ppm. {1H}13C NMR: : \u03b4 = 31.4 , 71.0 , 117.8 , 155.1  ppm. {1H}29Si NMR: : \u03b4 = \u221251.40  ppm.2), tert-butyl\u00adlithium  was added at 228\u2005K to a solution of 2,3-di\u00adhydro\u00adfuran  in diethyl ether (approx. 100\u2005ml). The reaction solution was stirred for 1\u2005h at rt. Tetra\u00adchloro\u00adgermane  was added at 213\u2005K and the reaction solution was stirred for 1\u2005h. The resulting solid was separated by inert filtration. The obtained solution was concentrated in vacuo and crystallized at 243\u2005K. The solvent was removed, and the solid was washed with cold diethyl ether. The product tetra\u00adkis\u00adgermane (2)  was obtained as colourless blocks.For the synthesis of tetra\u00adkis\u00adgermane : \u03b4 = 2.26 , 4.05 , 5.62  ppm. {1H}13C NMR: : \u03b4 = 30.8 , 71.0 , 113.8 , 155.7  ppm.6.A,B, H23A,B, H24A,B, H27A,B and H31A,B for compound 1 and all H atoms for compound 2 were refined independently. Other H atoms were positioned geometrically (C\u2014H = 0.95\u20131.00\u2005\u00c5) and were refined using a riding model, with Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen.Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989023003158/hb8058sup1.cifCrystal structure: contains datablock(s) 1. DOI: 10.1107/S2056989023003158/hb80581sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989023003158/hb80581sup4.cmlSupporting information file. DOI: 10.1107/S2056989023003158/hb80582sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989023003158/hb80582sup5.cmlSupporting information file. DOI: 2254180CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound exhibits I\u22ef\u03c0 halogen bonding and \u03c0-stacking in its extended structure. 18H8I2, is an ethynyl-substituted anthracene. The C\u2014C\u2014I bond angles deviate from 180\u00b0, being affected by inter\u00admolecular I\u22ef\u03c0 inter\u00adactions. These inter\u00adactions form a two-dimensional supra\u00admolecular structure further supported by offset \u03c0\u2013\u03c0 stacking of neighboring anthracene moieties.The title compound, C Two-dimensional crystals can have unique properties with applications in electronics, biomedicine, and sensors \u2014I moieties and the \u03c0-electrons of the adjacent anthracene rings  [I1\u22efCg1 = 3.528\u2005(4)\u2005\u00c5 and C16\u2014I1\u22efCg1 = 151.2\u2005(3)\u00b0] and I2 has a short contact to the centroid of the C9\u2013C14 ring (Cg2) [I2\u22efCg2 = 3.767\u2005(4)\u2005\u00c5 and C18\u2014I2\u22efCg2 = 150.1\u2005(3)\u00b0]. The bent nature of the C\u2014I\u22efcentroid inter\u00adactions leads to short I\u22efC contacts ranging from 3.352\u2005(4) to 3.655\u2005(4)\u2005\u00c5. The shorter contact between I1 and Cg1 appears to influence more significantly the bending of the entire alkynyl substituent [C1\u2014C15\u2014I1 = 173.8\u2005(3)\u00b0 versus C8\u2014C17\u2014I2 = 178.7\u2005(3)\u00b0], notably pulling the I1 atom away from the central ring of the neighboring anthracene mol\u00adecule and toward its C2\u2013C7 centroid.The crystal stucture represents the first example of an ethynyl\u2013anthracene halogenated with iodine Fig.\u00a01. The C\u2014Igs Fig.\u00a02, where Iet al., 2008et al., 2014et al., 2015tert-but\u00adyl)[4-(iodo\u00adethyn\u00adyl)phen\u00adyl]carbamate  plane Fig.\u00a03. Inter\u00adeet al., 2021N-iodo\u00adsuc\u00adcinimide  and AgNO3  were added to dry di\u00admethyl\u00adformamide (5\u2005ml), and the resulting mixture was stirred under nitro\u00adgen. After 5\u2005h, the reaction mixture was diluted with EtOAc (30\u2005ml) and washed with H2O (5 \u00d7 30\u2005ml). The organic layer was dried in vacuo, resulting in an orange solid. The product was crystallized from the orange solid using vapor\u2013vapor diffusion (CH2Cl2/hexa\u00adnes).The procedure was modeled after an analogous functionalization of an alkynylsilane : \u03b4 8.33 , 7.82 .Crystal data, data collection, and structural refinement details are summarized in Table\u00a0110.1107/S2414314623005539/hb4433sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314623005539/hb4433Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623005539/hb4433Isup3.cmlSupporting information file. DOI: 2191397CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E-configuration with respect to the double bond of the hydrazone bridge and with an ac\u00adyl\u2013hydrazone (\u2014CH=N\u2014NH\u2014CO\u2014) torsion angle of 166.0\u2005(3)\u00b0. The mol\u00adecule exhibits a non-planar conformation, likely induced by packing requirements.The title aroylhydrazone ether exists in an  22H19N3O4, shows a non-coplanar conformation, with dihedral angles between the phenyl rings of 73.3\u2005(1) and 80.9\u2005(1)\u00b0. These deformations are induced by the crystal packing that is mainly governed by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming a mono-periodic arrangement parallel to the b axis.The mol\u00adecular structure of the title compound, C The active pharmacophore group, \u2014CH=N\u2014NH\u2014C=O\u2014, present in a hydrazone is primarily responsible for its broad spectrum of biological aspects \u2005\u00c5 is slightly shorter than that of 1.397\u2005(4)\u2005\u00c5 determined in the corresponding derivative having a thienyl ring replacing the p-nitro\u00adphenyl group , 3315 \u03bd(N\u2014H), 1606 \u03bd(C=Nazomethine). LC\u2013MS (FAB) m/z: [M + H]+ calculated for C22H19N3O4; 390.1446; found 390.1448.Yield: 0.29\u2005g, 79%; melting point (m.p.): 531\u2013533\u2005K; FT\u2013IR: 1636 \u03bd I, global. DOI: 10.1107/S2056989023003948/wm5682Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023003948/wm5682Isup3.cmlSupporting information file. DOI: 2232132CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E)-1-(4-bromo\u00adphen\u00adyl)-3-(2-methyl\u00adphen\u00adyl)prop-2-en-1-one, the mol\u00adecules are linked into chains by weak C\u2014H\u22efO inter\u00adactions along the b axis. Successive chains form a zigzag structure along the c axis, and these chains are connected to each other by face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions along the a axis, forming layers parallel to the (001) plane. The crystal structure maintains its stability via van der Waals inter\u00adactions between the layers.In the crystal of \u00b0, and the configuration about the C=C bond is E. In the crystal, the mol\u00adecules are linked into chains by weak C\u2014H\u22efO inter\u00adactions along the b axis. Successive chains form a zigzag structure along the c axis, and these chains are connected to each other by face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions along the a axis. These layers, parallel to the (001) plane, are linked by van der Waals inter\u00adactions, thus consolidating the crystal structure. Hirshfeld surface analysis showed that the most significant contacts in the structure are H\u22efH (43.1%), C\u22efH/H\u22efC (17.4%), Br\u22efH/H\u22efBr (14.9%), C\u22efC (11.9%) and O\u22efH/H\u22efO (9.8%).In the title com\u00adpound, C The mol\u00adecule is approximately planar, as indicated by the torsion angles C10\u2014C5\u2014C4\u2014C3 = 1.9\u2005(5)\u00b0, C9\u2014C4\u2014C3\u2014C2 = \u22124.4\u2005(5)\u00b0, C4\u2014C3\u2014C2\u2014C1 = \u2212176.3\u2005(3)\u00b0, C3\u2014C2\u2014C1\u2014C11 = \u2212168.2\u2005(3)\u00b0, C2\u2014C1\u2014C11\u2014C12 = 15.9\u2005(4)\u00b0 and Br1\u2014C14\u2014C15\u2014C16 = 178.5\u2005(2)\u00b0. The dihedral angle between the planes of the 2-methyl\u00adphenyl and 4-bromo\u00adphenyl rings is 23.49\u2005(15)\u00b0.The title com\u00adpound Fig.\u00a01 is com\u00adp3.C(5) chains \u2005\u00c5, slippage = 1.890\u2005\u00c5; Cg2\u22efCg2a = 3.9420\u2005(18)\u2005\u00c5, slippage = 1.942\u2005\u00c5; symmetry code: (a) x\u00a0\u2212\u00a01, y, z; Cg1 and Cg2 are the centroids of the 2-methyl\u00adphenyl (C4\u2014C9) and 4-bromo\u00adphenyl (C11\u2013C16) rings, respectively]. They form layers parallel to the (001) plane through van der Waals inter\u00adactions, thus consolidating the crystal structure.In the crystal, the mol\u00adecules are linked into is Fig.\u00a03 and thesCrystalExplorer17.5 ; 43.1%], C\u22efH/H\u22efC , Br\u22efH/H\u22efBr , C\u22efC  and O\u22efH/H\u22efO  inter\u00adactions contribute the most to the surface contacts. The crystal packing is additionally influenced by Br\u22efC/C\u22efBr (2.0%), Br\u22efBr (0.8%), N\u22efN (2.6%) and O\u22efC/C\u22efO (0.2%) contacts. The Hirshfeld surface study confirms the significance of H-atom inter\u00adactions in the packing formation. The large number of H\u22efH, C\u22efH/H\u22efC, Br\u22efH/H\u22efBr, C\u22efC and O\u22efH/H\u22efO inter\u00adactions indicates that van der Waals inter\u00adactions and hydrogen bonding are important in the crystal packing -1,3-di\u00adphenyl\u00adprop-2-en-1-one\u2019 unit in the Cambridge Structural Database \u2005\u00c5], forming layers lying parallel to the ab plane. In the crystal of RUCKIM, the mol\u00adecules are linked through type II halogen bonds, forming a sheet structure parallel to the bc plane. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are observed between the sheets. In the crystal of XOLLOC, mol\u00adecules are linked via pairs of C\u2014H\u22efO inter\u00adactions with an via C\u2014H\u22ef\u03c0 inter\u00adactions. In the crystal of OBIYUW01, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions between the bromo\u00adphenyl and fluoro\u00adphenyl rings, resulting in a two-dimensional layered structure parallel to the ab plane. The mol\u00adecular packing is consolidated by weak Br\u22efH and F\u22efH contacts.In the crystal of KOCZUA, the shortest inter\u00admolecular contacts are Cl\u22efO [3.173\u2005(3)\u2005\u00c5]; these link the mol\u00adecules to form a 25.et al., 2021v/v) solution at room temperature.The title com\u00adpound was synthesized using a reported procedure (Chithiraikumar 6.Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and C\u2014H = 0.98\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023007387/tx2073sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023007387/tx2073Isup2.hklStructure factors: contains datablock(s) I. DOI: 2290092CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This salt consists of a complex [Ni(OPD)2(H2O)2]2+ cation with two bidentate OPD ligands and trans aqua ligands, and a non-coordinating NDS2\u2013 anion, which is the double-deprotonated form of H2NDS. The NiII atom is situated at a center of inversion and exhibits a slightly tetra\u00adgonally distorted {O2N4} octa\u00adhedral coordination environment, with four shorter equatorial Ni\u2014N bonds [2.0775\u2005(17) and 2.0924\u2005(18)\u2005\u00c5] and a longer axial Ni\u2014O bond [2.1381\u2005(17)\u2005\u00c5]. The OPD ligand is located about an inversion center and is nearly coplanar with the NiN4 plane [dihedral angle 0.95\u2005(9)\u00b0]. In the crystal, the cations and anions are connected by charge-assisted inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding inter\u00adactions into the tri-periodic network structure. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (44.1%), O\u22efH/H\u22efO (34.3%), C\u22efH/H\u22efC (14.8%) C\u22efC (6.5%) (involving the cations) and O\u22efH/H\u22efO (50%), H\u22efH (25%), C\u22efH/H\u22efC (15.3%), C\u22efC (8.2%) (involving the anions) inter\u00adactions.The reaction of  Its reactions with carb\u00adoxy\u00adlic acids and their derivatives produce the important class of benzimidazoles  or its deprotonated form (sulfonates) are of inter\u00adest in supra\u00admolecular chemistry 2]\u00b7NDS, where the NDS2\u2013 anion is not part of the metal coordination sphere.In this work, we focus on the synthesis, crystal structure, and Hirshfeld surface analysis of a nickel(II) complex,  and a pair of longer axial Ni\u2014O bonds [2.1381\u2005(17)\u2005\u00c5]. The OPD ligand, likewise located over a crystallographic inversion center at the middle of the central C11\u2014C11 bond, is almost coplanar with the NiN4 plane, with a dihedral angle of 0.95\u2005(9)\u00b0. The deviation of the ideal octa\u00adhedral coordination sphere around nickel might be explained as follows: The inflexible nature of the OPDA ring system with an N\u22efN distance between the amino groups of 2.770\u2005(2)\u2005\u00c5 determines the N2\u2014Ni1\u2014N1 and N2\u2014Ni1\u2014N1 bite angles of 83.26\u2005(7) and 96.74\u2005(7) \u00b0, respectively.The structures of the mol\u00adecular entities of the title compound are shown in Fig.\u00a013.2(H2O)2]2+ cation and the NDS2\u2013 anion are associated via charge-assisted inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds (Table\u00a012(H2O)2]2+ cation forms N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds with six neighboring organic anions whereby the two aqua and two OPD ligands act solely as hydrogen-bonding donor groups . Additionally, cations and neighboring dianions are linked through O1W\u2014H1WA\u22efO3iv and N2\u2014H2B\u22efO3i hydrogen bonds. The mol\u00adecules stack along [001], thereby forming a consolidated tri-periodic supra\u00admolecular network s Table\u00a01. Each 2+ cation and the NDS2\u2013 dianion. The dnorm surface has twelve bright-red spots on the Hirshfeld surface for the cation and anion each 2]2+ cation and NDS2\u2013 anion, respectively; Fig.\u00a06b and 6f). O\u22efH/H\u22efO and C\u22efH/H\u22efC, inter\u00adactions in the cation, and H\u22efH and C\u22efH/H\u22efC inter\u00adactions in the dianion follow with contributions of 34.3, 14.8, 25 and 15.3%, respectively . Other minor contributions are from C\u22efC (6.5%) and C\u22efO (0.3%) contacts in the cation, and from C\u22efC (8.2%), C\u22efO (0.3%), O\u22efO (0.1%) and S\u22efH (0.1%) contacts in the dianion. The O\u22efH/H\u22efO contacts are visible as a spike with a sharp tip on the side of the corresponding two-dimensional fingerprint plot, which is indicative of strong inter\u00admolecular inter\u00adactions between atoms. On the other hand, the C\u22efH/H\u22efC contacts form less pronounced spikes, suggesting that these inter\u00adactions are much weaker.The supra\u00admolecular inter\u00adactions discussed above were qu\u00adanti\u00adtatively investigated and visualized using Hirshfeld surface analysis performed with ch Fig.\u00a05, resultily Fig.\u00a06c,d,g,h.4.et al., 2016o-phenyl\u00adenedi\u00adamine moiety were identified. Out of these, 129 compounds were metal complexes, while 78 compounds were organic salts. One organic salt comprising protonated o-phenyl\u00adenedi\u00adamine and 1,5-naphthalene\u00addisulfonate has been studied  sulfate hepta\u00adhydrate  and disodium naphthalene-1,5-di\u00adsulfonate  in 10\u2005ml of the same mixed ethanol/water solvent. The resulting mixture was heated under reflux and stirred for 40\u2005min. After 5\u2005d of slow solvent evaporation at room temperature, a light-green crystalline product was obtained with a yield of 65% (based on Ni). Elemental analysis calculated (%) for C22H26N4NiO8S2: C 44.24, H 4.39, N 9.38; found: C 44.18, H 4.34, N 9.31.The starting materials are commercially available and were used without further purification. The ligand OPDA  was dissolved in 10\u2005ml of a 1:1 6.Uiso(H) = 1.2Ueq(C) and C\u2014H = 0.93\u2005\u00c5 for aromatic H atoms. Hydrogen atoms of the amino groups and of the water mol\u00adecule were located using a difference-Fourier map and refined with bond-length restraints of 0.89\u2005(1) and 0.85\u2005(1)\u2005\u00c5, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023009350/wm5701sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023009350/wm5701Isup2.hklStructure factors: contains datablock(s) I. DOI: 2303464CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Bombina maxima. Here, we reported that B.\u00a0maxima cells secreted \u03b2\u03b3-CAT under glucose, glutamine, and pyruvate deficiency to scavenge extracellular proteins for their nutrient supply and survival. AMPK signaling positively regulated the expression and secretion of \u03b2\u03b3-CAT. The PFP complex selectively bound extracellular proteins and promoted proteins uptake through endolysosomal pathways. Elevated intracellular amino acids, enhanced ATP production, and eventually prolonged cell survival were observed in the presence of \u03b2\u03b3-CAT and extracellular proteins. Liposome assays indicated that high concentration of ATP negatively regulated the opening of \u03b2\u03b3-CAT channels. Collectively, these results uncovered that \u03b2\u03b3-CAT is an essential element in cell nutrient scavenging under cell nutrient deficiency by driving vesicular uptake of extracellular proteins, providing a new paradigm for PFPs in cell nutrient acquisition and metabolic flexibility.Nutrient acquisition is essential for animal cells. \u03b2\u03b3-CAT is a pore-forming protein (PFP) and trefoil factor complex assembled under tight regulation identified in toad   \u2022The PFP \u03b2\u03b3-CAT is expressed and secreted by toad cells under nutrient deficiency\u2022AMPK signaling positively regulates the expression and secretion of \u03b2\u03b3-CAT\u2022The secreted \u03b2\u03b3-CAT selectively binds and scavenges extracellular nutrients\u2022The high concentrations of ATP may negatively regulate \u03b2\u03b3-CAT channel opening Cell biology The former operates in uptake of small nutrient, such as glucose and amino acids, and the latter is the main pathway through which cells obtain insoluble nutrients, such as cholesterol and iron.,,Bombina maxima. It forms membrane pores (channels) with a functional diameter 1.5\u20132.0\u00a0nm.,,,,,Numerous pore-forming proteins (PFPs) with a membrane insertion domain similar to bacterial toxin aerolysin, namely aerolysin family PFPs , have been found in plants and animals.,,,,,This PFP complex firstly targets cell surface acidic glycosphingolipids in lipid rafts via a double-receptor binding model, corresponding to BmALP1 subunit and BmTFF3 subunit binding gangliosides and sulfatides, respectively.B.\u00a0maxima cells to further investigate the role of SELC protein \u03b2\u03b3-CAT in cell nutrient acquisition and metabolic flexibility under cell nutrient deficiency. Interestingly, toad liver and gastrointestinal cells secreted \u03b2\u03b3-CAT to scavenge extracellular protein nutrients, such as albumin and ovalbumin, through endolysosomal pathways in the absence of glucose, glutamine and pyruvate, which elevated intracellular amino acids and ATP levels and supported cell survival under nutrient deficiency. The expression and secretion of \u03b2\u03b3-CAT were largely attenuated by inhibition of AMP-activated kinase (AMPK) signaling. Furthermore, in a liposome model, ATP, but not AMP inhibited \u03b2\u03b3-CAT channel opening. These results revealed the essential role of a secretory PFP in extracellular nutrient scavenging by cells through endolysosomal pathways under cell nutrient deficiency.Here, we used the nutrient deficiency model of toad ,,,,+/Gln+/Pyr+), glucose/glutamine/pyruvate-depleted medium (Glc\u02c9/Gln\u02c9/Pyr\u02c9), and glucose-containing but glutamine/pyruvate-depleted medium (Glc+/Gln\u02c9/Pyr\u02c9). In the isolated toad liver cell population, there were 62.4% hepatocytes  on the basis of toad skin transcriptomeT172 and pACC1S80 in human, respectively) were evolutionarily conserved from toad B.\u00a0maxima to human  in culture supernatants of toad liver cells under Glc\u02c9/Gln\u02c9/Pyr\u02c9 conditions , and dextran (70\u00a0kDa), an indicator of macropinocytosisKD values of \u03b2\u03b3-CAT with OVA and Bm-SA was approximately 2.33\u00a0\u00d7\u00a010\u22128\u00a0M and 2.47\u00a0\u00d7\u00a010\u22128\u00a0M, respectively. Ovalbumin-DQ (OVA-DQ) is a fluorescent indicator that fluoresces on proteolytic degradation.\u02c9/Gln\u02c9/Pyr\u02c9 conditions was observed by scanning confocal microscopy  under Glc\u02c9/Gln\u02c9/Pyr\u02c9 conditions , toad croscopy B and flocroscopy C. \u03b2\u03b3-CATs at 3\u00a0h A, a leves \u03b2\u03b3-CAT B and 3C.nditions B. Furthenditions D. Ethyl-nditions C and mamnditions D in the nditions E. Collec\u02c9/Gln\u02c9/Pyr\u02c9 conditions for 7\u00a0h by LC/MS and LC-MS/MS. The levels of amino acids, including asparagine and glutamine, in toad liver cells treated with bovine serum albumin (BSA) and \u03b2\u03b3-CAT were augmented compared with those in cells treated with BSA only  staining.nditions A. Notablnditions A. Howevenditions A or ovalnditions B. Additinditions C and 4D.\u02c9/Gln\u02c9/Pyr\u02c9 conditions  on liposomes, which induces dye release from lipid vesicles, an advantageous model without ATP receptors.nditions C. Notablnditions D. This rnditions E. Collec,,B.\u00a0maxima PFP protein complex \u03b2\u03b3-CAT in cell nutrient scavenging and energy supply under the deprivation of glucose and glutamine, essential nutrient components in cell metabolism.B.\u00a0maxima \u03b2\u03b3-CAT indeed acts as a novel system driven cell vesicular delivery that should play a physiological role in cell nutrient acquisition by mediating cellular nutrient import through endolysosomal pathways.,,PFPs are widely distributed in all kingdoms of life, which have long been recognized as either pore-forming toxin for microbial infection or host immune executors.+/Gln+/Pyr+) from 1 to 5\u00a0h  and intracellular nutrient sensors, which survey the abundance of energy and major metabolites, play an important role in metabolic homeostasis and cell survival.,,,,in\u00a0vivo and in\u00a0vitro in toad osmoregulatory organs to facilitate toad water maintaining.in\u00a0vivo. Indeed, the secreted \u03b2\u03b3-CAT could bind to ovalbumin and toad B.\u00a0maxima serum albumin (nutrients) directly. Furthermore, the colocalization of \u03b2\u03b3-CAT and OVA-DQ was readily observed under cell nutrient deficiency. These results were suggested that the pathway of \u03b2\u03b3-CAT importing and enriching nutrients might be selective, which was different from classical pinocytosis/macropinocytosis-like endocytosis.Diverse endocytic pathways are available at the surface of metazoan cells.,,,The functional diameter of bacterial toxin aerolysin channels is approximately 1.5\u00a0nm, which is large enough for translocation of oligonucleotides, peptides, and unfolded proteins.,,,,The physiological concentrations of ATP in cells are estimated to be 5\u201310\u00a0mM.,\u03b2\u03b3-CAT is a complex of BmALP1 and BmTFF3, in which BmTFF3 acts as a chaperon and regulatory unit of BmALP1 to stabilize the PFP monomer and deliver it to proper targets.,,,It is well documented that autophagy is a cellular process to sequester and degrade intracellular components under nutrient deficiency, which is the last defense for cells under nutrient deficiency and excess autophagy may lead to cell death.B.\u00a0maxima cells secrete \u03b2\u03b3-CAT to scavenge extracellular nutrients under nutrient deficiency at the cellular level (present study). Second, \u03b2\u03b3-CAT in toad B.\u00a0maxima blood circulation is an immediate and active responsive element under toad fasting in\u00a0vivo, which trans cellularly deliver and transport albumin-bound fatty acids to tissue parenchymal cells for their nutrient supply.B.\u00a0maxima physiology for adaptation to various nutrient environments. Rationally, similar strategies and executive pathways should be conserved in vertebrates, in which various families of PFPs including af-PFPs are widely distributed. Knowledge from \u03b2\u03b3-CAT can provide clues to understand novel PFP-driven cell vesicular delivery systems in nutrient acquisition and metabolic flexibility. Although af-PFPs have not been clearly observed in Eutherian mammals, other PFP family members can readily compensate for the role of af-PFPs.SELC protein \u03b2\u03b3-CAT works in cell nutrient acquisition at least at two levels. First, toad B.\u00a0maxima cells secrete \u03b2\u03b3-CAT, a PFP and trefoil factor (TFF) complex assembled depending on environmental cues under glucose, glutamine, and pyruvate deficiency. This PFP complex supports cell survival by driving the cellular import of extracellular proteins through endolysosomal pathways. The imported proteins serve as nutrients in nutrient-deprived cells for energy supply. AMPK signaling positively regulates the expression and secretion of \u03b2\u03b3-CAT, whereas high concentrations of ATP (> 1\u00a0mM) bind to and negatively regulate \u03b2\u03b3-CAT channels. Our findings define the essential role of toad B.\u00a0maxima PFP complex \u03b2\u03b3-CAT in cell macromolecular nutrient scavenging, providing a new paradigm for PFPs in cell nutrient acquisition and metabolic flexibility.In conclusion, the present study elucidated that toad in\u00a0vitro cell experiments. Consequently, it is necessary to study whether the secretory PFP \u03b2\u03b3-CAT contribute to the nutrient acquisition in\u00a0vivo under starvation, which revealed that the PFP \u03b2\u03b3-CAT was secreted into toad blood in response to toad fasting,,,,Our work was restricted zhangy@mail.kiz.ac.cn).Further information and requests for resources and reagents should be directed to and will be fulfilled by the lead contact, Yun Zhang (All unique/stable reagents generated in this study are available from the B.\u00a0maxima) was performed as described previously and the males with a mean body weight of 25\u00a0\u00b1 5\u00a0g were used for this study . All procedures and the care and handing of animals were approved by the Ethics Committee of the Kunming Institute of Zoology, Chinese Academy of Sciences .Feeding of toads  containing 10% fetal bovine serum  and 1% Penicillin-Streptomycin Solution  at 37\u00b0C with 5% CO+/Gln+/Pyr+ medium, Biological Industries, Cat 01-172-1A), glucose, pyruvate and glutamine-free medium , or added 3.151\u00a0g/L glucose to Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium (Glc+/Gln\u02c9/Pyr\u02c9 medium). For macropinocytosis inhibition, cells were first incubated with 100\u00a0\u03bcM EIPA (5-(N-ethyl-N-isopropyl)-Amiloride), a Na+/H+-exchanger inhibitor used for macropinocytosis inhibition)  in Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium for 1\u00a0h at 26\u00b0C (toad cells) or 37\u00b0C (HepG2 cells), respectively. For AMPK signaling inhibition, cells were treated with 0\u201310\u00a0\u03bcM compound C or 0\u201320\u00a0\u03bcM SBI-0206965  in Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium for 3\u00a0h at 26\u00b0C. To deplete endogenous \u03b2\u03b3-CAT, toad cells were incubated with 100\u00a0\u03bcg/mL anti-\u03b2\u03b3-CAT rabbit polyclonal antibodies or 100\u00a0\u03bcg/mL rabbit IgG  as the isotype control in Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium at 26\u00b0C.Cells were cultured in basal medium containing 3.151\u00a0g/L glucose, 1\u00a0mM pyruvate and 2.5\u00a0mM glutamine  according to the manufacturer\u2019s instructions.Total 2\u00d7106 isolated toad liver cells were cultured at 26\u00b0C in various media for 0, 3, 5 and then up to 11\u00a0h at 2-h intervals. The treatments were as follows: Glc+/Gln+/Pyr+ medium, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing 100\u00a0nM \u03b2\u03b3-CAT, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing 500\u00a0\u03bcg/mL ovalbumin  or BSA , Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing 100\u00a0nM \u03b2\u03b3-CAT and 500\u00a0\u03bcg/mL OVA or BSA, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing 100\u00a0\u03bcg/mL anti-\u03b2\u03b3-CAT antibodies in the presence of 500\u00a0\u03bcg/mL OVA or BSA, and Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing 100\u00a0\u03bcg/mL rabbit IgG in the presence of 500\u00a0\u03bcg/mL OVA or BSA. To assess the viability of toad stomach cells, 5\u00d7106 isolated toad stomach cells were subjected to various treatments  for 7\u00a0h at 26\u00b0C. To assess cytotoxicity of compound C and SBI-0206965, 5\u00d7106 isolated toad liver cells were cultured in Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium plus compound C (0\u201310\u00a0\u03bcM) or SBI-0206965 (0\u201320\u00a0\u03bcM) for 3\u00a0h at 26\u00b0C. After treatments, toad cells were stained with 500\u00a0ng/mL PI  for 4\u00a0min at 26\u00b0C. Fluorescence was recorded using an LSR Fortessa cell analyzer .Cell viability of toad cells was measured using propidium iodide (PI) stain assay as described previously.6 toad liver cells were cultured in Glc+/Gln+/Pyr+ medium or Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium containing various concentration of \u03b2\u03b3-CAT (0\u20131000\u00a0nM) for 3\u00a0h, then the supernatant of toad cells was collected, and LDH release was detected by LDH cytotoxicity assay kit  according to the manufacturer\u2019s instructions.To assess the cytotoxicity of \u03b2\u03b3-CAT in toad liver cells, the total 1\u00d7104 cells were seeded into each well of a 96-well culture plate. After overnight culture, the cells were washed thrice with PBS and incubated in Glc+/Gln+/Pyr+ medium, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium, Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium plus various concentrations of \u03b2\u03b3-CAT (0\u2013160\u00a0nM), or Glc\u02c9/Gln\u02c9/Pyr\u02c9 medium plus 5\u00a0mg/mL OVA in the presence or absence of 40\u00a0nM \u03b2\u03b3-CAT for 36\u00a0h. Then, the cells were incubated with MTS reagent  for 2\u00a0h in the dark at 37\u00b0C with 5% CO2. Absorbance was read at 490\u00a0nm with an Infinite 200 Pro microplate reader .To assess viability of mammalian HepG2 cells, 1\u00d7107 toad liver, intestinal, or stomach cells was collected and then washed twice with 30\u00a0mL Ringer\u2019s solution. Toad liver cells were cultured in Glc+/Gln+/Pyr+, Glc\u02c9/Gln\u02c9/Pyr\u02c9, or Glc+/Gln\u02c9/Pyr\u02c9 medium for 1\u20135\u00a0h at 26\u00b0C, and intestinal or stomach cells was cultured for 1\u00a0h at 26\u00b0C. Then, culture supernatants were collected and prepared for the hemolytic activity assay as described previously.A total of 1\u00d710in\u00a0vitro, and the detail methods were performed as described previouslyKD were determined using Octet Analysis Studio Software using a 1:1 model.The BLI assay was used for the interaction between \u03b2\u03b3-CAT and the extracellular nutrients 6 isolated toad liver cells were treated as described in the \u201cB.\u00a0maxima serum albumin ) or 20\u00a0\u03bcg/mL Ovalbumin-DQ  in the dark at 26\u00b0C for 15\u00a0min. Fluorescence was detected by the LSR Fortessa cell analyzer using the FITC channel. In each sample, 1\u00d7104 single cells were analyzed.A total of 5\u00d710For immunofluorescence, cells were incubated with 100\u00a0\u03bcg/mL Ovalbumin-DQ in the dark at 26\u00b0C for 15\u00a0min. To stain \u03b2\u03b3-CAT, cells were washed and incubated with 20\u00a0\u03bcg/mL anti-\u03b2\u03b3-CAT primary antibodies overnight at 4\u00b0C in the dark. After washing with PBS three times, the cells were incubated with 10\u00a0\u03bcg/mL cy3-conjugated anti-rabbit IgG for 1\u00a0h at 37\u00b0C in the dark. Then, the samples were sealed with an anti-fluorescent quench agent containing DAPI. Images were acquired by a Zeiss LSM 880 microscope system .7 isolated toad liver cells were treated in various media as described in the \u201c2O and MeOH solution (1:4) at\u00a0\u221280\u00b0C, and then the samples were incubated for 15\u00a0min at \u221280\u00b0C. Then, the supernatants were collected by centrifuging at 17,000\u00a0g for 10\u00a0min 10\u00a0\u03bcL of these supernatants were injected per analysis. Samples were run on a Vanquish (Thermo Fisher Scientific) UHPLC system with mobile phase A  and mobile phase B (ACN) at a flow rate of 200\u00a0\u03bcL/min on an Accucore-150-Amide-HILIC column 2.6\u00a0\u03bcm (100\u00a0\u00d7\u00a02.1\u00a0mm)  at 40\u00b0C at a gradient from 45% to 90% A in 15\u00a0min followed by a 10-min isocratic step. The UHPLC was coupled to a Q-Exactive (Thermo Fisher Scientific) mass analyzer running in polarity switching mode at 3.5\u00a0kV for positive change scanning and 3.0\u00a0kV for negative change scanning at an MS1 resolution of 70,000. Metabolites were identified by exact mass (MS1), retention time, and in some cases, by their fragmentation patterns (MS2) at normalized collision energy. Quantification was performed by area under the curve integration of MS1 ion chromatograms with the Thermo Scientific Xcalibur software package. Area values were normalized to cell count averages from triplicate wells treated in parallel for each condition.A total of 1\u00d710Intracellular ATP was extracted and measured by an ATP detection kit  in accordance with the manufacturer\u2019s protocol. Briefly, toad liver cells were treated same as described in the \u201cTo assess the effect of adenosine phosphate on \u03b2\u03b3-CAT channel formation-induced liposome dye release, liposomes were incubated with 600\u00a0nM \u03b2\u03b3-CAT in the presence or absence of adenosine phosphate  (Sigma), and then dye release assays were performed as described previously.The purification of \u03b2\u03b3-CAT were performed as described previously.KD) was determined using BIA evaluation 4.1 software and its equation for 1:1 Langmuir binding.A direct interaction was assessed as described previously.+/Gln+/Pyr+, Glc\u02c9/Gln\u02c9/Pyr\u02c9, or Glc+/Gln\u02c9/Pyr\u02c9 medium, respectively. Then, the cells were lysed and prepared for Western blotting. The cell supernatant was concentrated to one-10th of the original volume by a vacuum lyophilizer for Western blotting as described previously.To assess protein level of \u03b2\u03b3-CAT in toad liver cell lysate and supernatant, cells were cultured in GlcTo assess AMP-activated protein kinase (AMPK) signaling, cells were treated as described in the \u201cThe mRNA levels of BmALP1 (\u03b2\u03b3-CAT-\u03b1) and BmTFF3 (\u03b2\u03b3-CAT-\u03b2) in toad liver cells were measured by quantitative real-time PCR (qRT-PCR) using a ChamQ Universal SYBR qPCR Master Mix kit . The cycle counts of target genes were normalized to those of \u03b2-actin. Primer sequences of \u03b2\u03b3-CAT and \u03b2-actin used were the same as report previously.2, and 1\u00a0mM EDTA, pH 7.5) for 30\u00a0min at 26\u00b0C. Cell lysates from HepG2 cells were used as a positive control. Absorbance was read at 620\u00a0nm, and the free phosphate concentration was calculated by a standard curve (0\u201350\u00a0\u03bcM free phosphate).The ATPase activity of \u03b2\u03b3-CAT was measured by an ATPase activity assay kit  according to the manufacturer\u2019s protocol. Briefly, various concentrations \u03b2\u03b3-CAT was incubated with 4\u00a0mM ATP in assay buffer (40\u00a0mM Tris, 80\u00a0mM NaCl, 8\u00a0mM MgAcB.\u00a0maxima with other species was conducted by Clustal Omega6.Sequence alignment analysis of AMPK\u03b1 and ACC1 in t-test. Multiple comparisons were performed by one-way ANOVA with post-hoc contrasts by Dunnett\u2019s multiple comparisons test. Multi-group comparisons were made by two-way ANOVA with Sidak\u2019s multiple comparisons test. p < 0.05 was considered statistically significant. the statistical details of experiments can be found in the figure legends.All experimental values are expressed as means\u00a0\u00b1 SD. Each experiment was repeated at least twice. All data were analyzed using GraphPad Prism 8.0 software. Two comparisons were performed using the standard unpaired"}
{"text": "The low-temperature (90\u2005K) crystal structure of 4-(di\u00admethyl\u00adaza\u00adnium\u00adyl)-2-hy\u00addroxy\u00adanilinium dichloride monohydrate is presented along with a Hirshfeld surface analysis of the organic cation. 8H14N2O+\u00b72Cl\u2212\u00b7H2O, at low temperature (90\u2005K) are presented. The organic cation is essentially planar: the r.m.s. deviation of its non-hydrogen atoms (aside from the two methyl groups) is 0.0045\u2005\u00c5. The methyl carbons are 1.3125\u2005(12)\u2005\u00c5 and 1.1278\u2005(12)\u2005\u00c5 either side of the mean plane. The crystal packing involves extensive hydrogen bonding of types O\u2014H\u22efCl, N\u2014H\u22efCl, N\u2014H\u22efOW, and OW\u2014HW\u22efCl (where W = water), which arrange into chains of R24(12) motifs that combine to form corrugated layers parallel to -2-hy\u00addroxy\u00adanilinium dichloride monohydrate, C Perkin, 1896aka, acetamino\u00adphen/Tylenol) and the fenamate family of NSAIDs (anthranilic acid deriv\u00adatives). Within this context, a concise review of aniline and its derivatives was presented by Anjalin et al. , at 90\u2005K.Given the industrial and pharmaceutical significance of anilinium salts, this paper presents the crystal structure and Hirshfeld-surface analysis of 4-(di\u00admethyl\u00adaza\u00adnium\u00adyl)-2-hy\u00addroxy\u00adanilinium dichloride monohydrate  and N2\u2014H2N\u22efCl2 [D\u2013Ad = 3.0467\u2005(9)\u2005\u00c5] hydrogen bonds with the chloride anions, which in turn act as acceptors for O1W\u2014H1W1\u22efCl1vi [D\u2013Ad = 3.1493\u2005(9)\u2005\u00c5] and O1W\u2014H2W1\u22efCl2vi [D\u2013Ad = 3.1036\u2005(9)\u2005\u00c5] hydrogen bonds with the water mol\u00adecule (symmetry codes as per Table\u00a01via N1\u2014H3N1\u22efO1W [D\u2013Ad = 2.7093\u2005(12)\u2005\u00c5] hydrogen bonds, forming chains that extend parallel to [101] \u2005\u00c5] and N1\u2014H1N1\u22efCl2i [D\u2013Ad = 3.1299\u2005(9)\u2005\u00c5] hydrogen bonds, forming corrugated layers parallel to  Fig.\u00a03.normd for the cation in I were obtained using CrystalExplorer 4+\u00b74Cl\u2212\u00b74H2O; Stylianou et al., 2017I. Two other anilinium salts not returned in the above search but that share similar features to I are POMXUL  and PAXXIX -(hy\u00addroxy\u00adimino)\u00admeth\u00adyl]-N,N-dimethyl anilinium chloride (C9H13N2O+\u00b7Cl\u2212).A search of the Cambridge Structural Database  and 0.98\u2005\u00c5 (RCH3) and Uiso(H) parameters set to either 1.2Ueq (R2CH) or 1.5Ueq (RCH3) of the attached carbon. Nitro\u00adgen and oxygen-bound hydrogens were fully refined .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023007223/vm2289sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023007223/vm2289Isup2.hklStructure factors: contains datablock(s) I. DOI: 2289098CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "IO2\u00a0=\u00a00.209; HIGH FIO2\u00a0=\u00a00.155; VHIGH FIO2\u00a0=\u00a00.125) on glycaemic control, insulin sensitivity, and oxidative stress during a subsequent oral glucose tolerance test (OGTT) in males with overweight (mean (SD) BMI\u00a0=\u00a027.6 (1.3) kg/m2; n\u00a0=\u00a012). Feasibility was defined by exceeding predefined withdrawal criteria for peripheral blood oxygen saturation (SpO2), partial pressure of end\u2010tidal oxygen or carbon dioxide and acute mountain sickness (AMS), and dyspnoea symptomology. Hypoxia reduced SpO2 in a stepwise manner (CON\u00a0=\u00a097(1)%; HIGH\u00a0=\u00a091(1)%; VHIGH\u00a0=\u00a081(3)%, p\u2009<\u20090.001), but did not affect peak plasma glucose concentration (CON\u00a0=\u00a07.5(1.8) mmol\u2219L\u22121; HIGH\u00a0=\u00a07.7(1.1) mmol\u2219L\u22121; VHIGH\u00a0=\u00a07.7(1.1) mmol\u2219L\u22121; p\u00a0=\u00a00.777; \u03b72\u00a0=\u00a00.013), plasma glucose area under the curve, insulin sensitivity, or metabolic clearance rate of glucose (p\u2009>\u20090.05). We observed no between\u2010conditions differences in oxidative stress (p\u2009>\u20090.05), but dyspnoea and AMS symptoms increased in VHIGH (p\u2009<\u20090.05), with one participant meeting the withdrawal criteria. Acute HIGH or VHIGH exposure prior to an OGTT does not influence glucose homeostasis in males with overweight, but VHIGH is associated with adverse symptomology and reduced feasibility.Previous research has shown that \u226460\u2009min hypoxic exposure improves subsequent glycaemic control, but the optimal level of hypoxia is unknown and data are lacking from individuals with overweight. We undertook a cross\u2010over pilot feasibility study investigating the effect of 60\u2010min prior resting exposure to different inspired oxygen fractions (CON F Likewise, Mackenzie et al.\u00a0 were reduced, and insulin sensitivity improved, during a subsequent intravenous glucose tolerance test. In men with obesity (mean(SD) body mass index (BMI)\u00a0=\u00a032.7(1.3) kg/m2), a more prolonged intervention consisting of ten nights of moderate normobaric hypoxia (FIO2\u00a0=\u00a00.15) reduced fasting blood [glucose] and improved insulin sensitivity  and two normobaric\u2010hypoxic conditions equivalent to a simulated altitude of ~2500\u2009m, i.e., \u2018high\u2019 altitude , and\u2009~\u20094000\u2009m, i.e., \u2018very\u2010high\u2019 altitude   was recruited from the host university (mean (SD) age\u00a0=\u00a032(7) years; height\u00a0=\u00a01.82(0.08) m; mass\u00a0=\u00a091.8(10.1) kg; BMI\u00a0=\u00a027.6(1.3) kg/m2). Although intended as a pilot feasibility\u2010study, our sample size was in keeping with similar previous work that informed the study  of 0.14 for a given outcome variable using repeated measures ANOVA . All participants were free from metabolic disease including T2DM (glycated hemoglobin (HbA1c)\u00a0=\u00a034(4) mmol/mol), thalassemia, and haemoglobinopathies, were not taking any medications and had normal resting lung function , ECG, and blood pressure.To balance the three conditions, a convenience sample of 12 males with overweight  and connected to a metabolic cart  calibrated using known concentrations of O2, CO2, and N2 gas, and a 3\u2010L air syringe . Participants were blind to the FIO2 on each occasion with CON serving as a sham control condition. Pulmonary gas exchange and ventilation were averaged into 60\u2010s time bins. Peripheral oxygen saturation was measured by fingertip pulse oximetry  interfaced with a data acquisition system  and heart rate using short range telemetry . Participants were withdrawn if their peripheral blood oxygen saturation (SpO2) fell below 65% for 15 continuous seconds, or if the partial pressure of end\u2010tidal oxygen (PETO2) fell below 45\u2009mmHg, or the partial pressure of end\u2010tidal carbon dioxide (PETCO2) fell below 25\u2009mmHg, for three consecutive breaths. Preliminary data collection indicated that, for most participants, the lower FIO2 would approximate the exposure limits permitted within our laboratory.Participants reported to the laboratory at 0730\u2009hours on test days following a 12\u2010h overnight fast and in a hydrated state, having only consumed water and having abstained from alcohol and strenuous exercise in the previous 24\u2009h. Participants rested in a semi\u2010recumbent position and a venous cannula was inserted into a forearm vein. Thereafter, following a 15\u2010min rest period, baseline measurements were obtained and the participant donned an oronasal mask delivering the required FInformed by previous studies showing beneficial effects of acute hypoxia on subsequent glycaemic control  were removed. Energy expenditure and substrate utilization were calculated during the OGTT using indirect respiratory calorimetry, and hunger scores were summed over the OGTT period to create a single hunger score. Criteria for feasibility were (i) withdrawal from the study due to physiological perturbation exceeding any of the study withdrawal criteria for SpO2, PETO2, or PETCO2 or (ii) symptoms attributable to acute hypoxia (AMS and dyspnoea). Between\u2010conditions differences were examined using one\u2010way RM\u2010ANOVA, with the exception of AMS symptoms and perceived dyspnoea, which were analyzed using Friedman's test; if the RM\u2010ANOVA violated the assumption of sphericity, the Greenhouse\u2013Geisser statistic was employed. The effect size for RM ANOVA is reported as \u03b72, and post\u2010hoc analysis of significant RM\u2010ANOVA and Friedman's test effects were undertaken using (least significant difference) pairwise comparisons and Wilcoxon's signed ranks test, respectively.Statistical analyses were undertaken using SPSS Version 28 , and significance was set a priori at P\u2009\u2264\u20090.05. Data are presented mean (SD), with the exception of the Lake Louise questionnaire and dyspnoea scale data, which are presented as median(range). Peak and AUC (trapezoid method) were calculated for [glucose] and AOPP to provide an index of glucose homeostasis and a marker of oxidative stress, respectively, following the hypoxic exposure. Post\u2010prandial insulin sensitivity and metabolic clearance rate of glucose (a maker of insulin sensitivity) were calculated according to validated equations incorporating demographic data (age and BMI) and on the basis of [glucose] and [insulin] samples at 0, 60, and 120\u2009min of the OGTT  and 0.126(0.05) for the HIGH and VHIGH trials, respectively. SpO2 differed between all conditions (CON\u00a0=\u00a097(1)%; HIGH\u00a0=\u00a091(1)%; VHIGH\u00a0=\u00a081(3)%; p\u2009<\u20090.001, \u03b72\u00a0=\u00a00.957) being highest in CON and lowest in VHIGH .One participant was unable to complete the experimental trials due to reaching the study P\u22121; HIGH\u00a0=\u00a07.7(1.1) mmol\u2219L\u22121; VHIGH\u00a0=\u00a07.7(1.1) mmol\u2219L\u22121; p\u00a0=\u00a00.777, \u03b72\u00a0=\u00a00.013) during the OGTT nor the area under the curve (CON\u00a0=\u00a011.5(2.9) mmol\u2219h\u22121/L; HIGH\u00a0=\u00a012.3(1.6) mmol\u2219h\u22121/L; VHIGH\u00a0=\u00a012.5(2.0) mmol\u2219h\u22121/L; p\u00a0=\u00a00.241, \u03b72\u00a0=\u00a00.146) differed between conditions  \u03bcmol\u2219kg\u22121\u2219min\u22121\u2219pmol/L; VHIGH\u00a0=\u00a00.11(0.01) \u03bcmol\u2219kg\u22121\u2219min\u22121\u2219pmol/L; p\u00a0=\u00a00.351, \u03b72\u00a0=\u00a00.099)  mL\u2219kg\u22121\u2219min\u22121; VHIGH\u00a0=\u00a09.6(0.7) mL\u2219kg\u22121\u2219min\u22121; p\u00a0=\u00a00.256, \u03b72\u00a0=\u00a00.142) were unaffected by the FIO2. Oxidative stress (plasma [AOPP]) before and after the hypoxic intervention period, and during the subsequent OGTT, is shown in Figure\u00a0p\u00a0=\u00a00.621, \u03b72\u00a0=\u00a00.051) and accumulated oxidative stress (AUC [AOPP]: CON\u00a0=\u00a0526(202) pmol\u2219h\u22121/L; HIGH\u00a0=\u00a0532(176) pmol\u2219h\u22121/L; VHIGH 567(203) pmol\u2219h\u22121/L; p\u00a0=\u00a00.606, \u03b72\u00a0=\u00a00.054) did not differ between the conditions, whereas IL\u20106 remained below the detectable limits of the assay (9.4\u00a0pg\u2219mL\u22121).Plasma [glucose] and [insulin] before and after the hypoxic intervention period, and during the subsequent OGTT, are shown in Figure\u00a0p\u00a0=\u00a00.011, \u03b72\u00a0=\u00a00.394), being lower in HIGH than VHIGH or CON (p\u2009<\u20090.05), although at an individual substrate level neither the total energy from fat (CON\u00a0=\u00a0104(72) kcal; HIGH\u00a0=\u00a0104(54) kcal; VHIGH\u00a0=\u00a0126(46) kcal; p\u00a0=\u00a00.220, \u03b72\u00a0=\u00a00.155) nor the total energy from carbohydrates (CON\u00a0=\u00a0152(39) kcal; HIGH\u00a0=\u00a0130(46) kcal; VHIGH\u00a0=\u00a0121(30) kcal; p\u00a0=\u00a00.113, \u03b72\u00a0=\u00a00.215) differed between conditions. Similarly, the average RER during the OGTT did not differ between conditions (CON\u00a0=\u00a00.90(0.08); HIGH\u00a0=\u00a00.87(0.06); VHIGH\u00a0=\u00a00.85(0.04); p\u00a0=\u00a00.092, \u03b72\u00a0=\u00a00.233). Hunger score was unaffected by the hypoxic intervention (CON\u00a0=\u00a0220(155) A.U; HIGH\u00a0=\u00a0253(146) A.U; VHIGH\u00a0=\u00a0240(123) A.U; p\u00a0=\u00a00.331, \u03b72\u00a0=\u00a00.116).Total energy expenditure during the OGTT differed between conditions (CON\u00a0=\u00a0256(39) kcal; HIGH\u00a0=\u00a0235(38) kcal; VHIGH\u00a0=\u00a0247(32) kcal; \u22121; HIGH\u00a0=\u00a064(6) b\u2219min\u22121; VHIGH\u00a0=\u00a073(10) b\u2219min\u22121; p\u00a0=\u00a00.008, \u03b72\u00a0=\u00a00.629 (n\u00a0=\u00a08)), being higher in both HIGH and VHIGH than CON (both p\u2009<\u20090.01), and higher in VHIGH than HIGH (p\u2009<\u20090.05), but neither systolic blood pressure (CON\u00a0=\u00a0129(10) mmHg; HIGH\u00a0=\u00a0122(9) mmHg; VHIGH\u00a0=\u00a0124(9) mmHg; p\u00a0=\u00a00.194, \u03b72\u00a0=\u00a00.167), diastolic blood pressure (CON\u00a0=\u00a080(8) mmHg; HIGH\u00a0=\u00a077(6) mmHg; VHIGH\u00a0=\u00a078(8) mmHg; p\u00a0=\u00a00.574, \u03b72\u00a0=\u00a00.060), nor mean arterial pressure (CON\u00a0=\u00a096(8) mmHg; HIGH\u00a0=\u00a092(7) mmHg; VHIGH\u00a0=\u00a093(6) mmHg; p\u00a0=\u00a00.263, \u03b72\u00a0=\u00a00.138) differed.Heart rate over the normobaric\u2010hypoxic exposure period differed between conditions (CON\u00a0=\u00a061(5) b\u2219minp\u00a0=\u00a00.009), which were greater in VHIGH compared to HIGH and CON (p\u2009<\u20090.05), with two participants meeting the criteria for AMS , being higher in VHIGH than HIGH or CON (p\u2009<\u20090.05).There was a between\u2010conditions difference in AMS symptoms following the normobaric\u2010hypoxic exposures (CON\u00a0=\u00a00(0\u20132); HIGH\u00a0=\u00a00(0\u20131); VHIGH\u00a0=\u00a01(0\u20137); 4IO2 (VHIGH).The aim of the present study was to assess the short\u2010term effects of different levels of acute hypoxia on subsequent glucose tolerance, insulin sensitivity, markers of inflammation and oxidative stress, and feasibility in males with overweight. Our main findings were that, following 60\u2009min of breathing either of two hypoxic gas mixtures: (1) neither glucose tolerance, as assessed by peak [glucose] and [glucose] AUC, insulin sensitivity, nor metabolic clearance rate of glucose significantly differed across conditions; (2) markers of oxidative stress and inflammation were not elevated by the acute hypoxic exposures; and (3) feasibility was reduced at the lowest FIO2 of 0.148 did not differ from a normoxic control, and Morishima and Goto\u00a0(IO2\u00a0=\u00a00.155) on resting postprandial glucose regulation. They differ, however, from those showing beneficial effects of acute hypoxia on subsequent glycaemic control in metabolically compromised individuals  indicates that detection of a between\u2010conditions difference would have been possible with 17 participants .Hypoxia has been shown to increase muscle glucose uptake through effects on insulin\u2010independent  the highest level of hypoxia that is reliably tolerated without adverse symptoms in individuals with overweight, (ii) the minimal effective exposure duration to this level of hypoxia in this cohort, and (iii) the recruitment of individuals with overweight with overtly compromised glycaemic control.Written informed consent was obtained before participation. The study was approved by the University's Faculty of Science and Health, Research Ethics Committee and conformed to the Declaration of Helsinki, except for registration in a database."}
{"text": "II\u2013di\u00adthio\u00adether complex. It crystallizes in the monoclinic space group P21/c. Additional Hirshfeld analyses indicate a C\u2014H\u22ef\u03c0 inter\u00adaction along the [010] axis to be the most important packing factor.The title complex represents a further example of a square-planar Pt 2(C7H8I2)2], represents a further example of a square-planar PtII\u2013di\u00adthio\u00adether complex. It crystallizes in the monoclinic space group P21/c. Additional Hirshfeld analyses indicate a C\u2014H\u22ef\u03c0 inter\u00adaction along the [010] axis to be the most important packing factor.The title complex, [PtI Alternatively, this air-stable complex could be prepared in a much improved yield of 80% by reaction of bis\u00ad(benzo\u00adnitrile)\u00addiiodo\u00adplatinum with 2 equivalents of methyl phenyl sulfide (thio\u00adanisol) MeSPh using di\u00adchloro\u00admethane as solvent. This compound was characterized by NMR spectroscopy in solution and exhibits a singlet resonance for the two magnetically equivalent methyl groups at \u03b4 3.01 ppm, flanked by 195Pt satellites due to a 3JPtH coupling of 48\u2005Hz. Furthermore, we report herein on the solid-state structure and structural analysis of trans-di\u00adiodido\u00adbis\u00ad[(methyl\u00adsulfan\u00adyl)benzene-\u03baS]platinum(II) (1). In addition, the results of a Hirshfeld analysis of the inter\u00admolecular inter\u00adactions are presented.In the past, our groups have investigated the coordination of chelating di\u00adthio\u00adethers such as the vinylic ferrocenyl-di\u00adthio\u00adether 2.trans-Di\u00adiodido\u00adbis\u00ad[(methyl\u00adsulfan\u00adyl)benzene-\u03baS]platinum(II) (1) crystallizes from di\u00adchloro\u00admethane in the monoclinic crystal system, space group P21/c. The mol\u00adecular structure of 1 is presented in Figs.\u00a021, which shows Ch2 symmetry. The distance from the coordinating iodine center I1 to Pt1 is 2.61205\u2005(15)\u2005\u00c5, showing a slight elongation with respect to its educt structure trans-[PtI2(NCPh)2] (2) (2.6052\u2005(8)\u2005\u00c5; Viola et al., 2018trans-[PtCl2(SMePh)2] (3) reported by Ahlgr\u00e9n 2] (4) 2] (5) \u2005\u00c5 in 5]. The chelate complexes cis-di\u00adiodo-\u00adplatinum(II) di\u00adiodoplatinum(II) \u00b0, C2\u2014S1\u2014Pt1 = 104.52\u2005(7)\u00b0 and C2\u2014S1\u2014C1 = 103.46\u2005(11)\u00b0.All further bonds have characteristic dimensions  x, y, \u2212z] with a distance between the phenyl ring and H1Bi of 2.5377\u2005(10)\u2005\u00c5 benzene] ligand and its oxidized derivative are focused on now. The already compared structure trans-di\u00adchloro-bis\u00ad[meth\u00adyl(phen\u00adyl)sulfan\u00adyl]platinum \u00adpalladium has been published independently by two different research groups [JISWUD platinum(II) platinum(II) 2SiPh2}] 2SiPh2}]\u00b7DCM 2Si2Me4}] 2Si2Me4}]\u00b7DCM benzene]\u00adplatinum (1) was synthesized by adding methyl\u00adphenyl sulfide  dissolved in 0.5\u2005mL of di\u00adchloro\u00admethane via a microsyringe to a solution of bis\u00ad(benzo\u00adnitrile)\u00addiiodo\u00adplatinum  in di\u00adchloro\u00admethane (3\u2005mL) and stirring overnight at room temperature. trans-Di\u00adiodo\u00adbis\u00ad[(methyl\u00adsulfan\u00adyl)benzene]\u00adplatinum  was isolated as red crystals after layering with heptane.14H16I2PtS2 (697.30\u2005g\u2005mol\u22121): C, 24.11; H, 2.32; S, 9.20. Found: C, 23.92; H, 2.21; S, 9.05%.Calculated for C1H NMR : \u03b4 = 3.01 , 7.05\u20137.73  ppm.6.Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso (H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023003717/jy2030sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023003717/jy2030Isup2.hklStructure factors: contains datablock(s) I. DOI: 2258409CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The salts were characterized by the multinuclear NMR and IR spectroscopy as well as X\u2010ray diffraction. Hirshfeld surface analysis and solid state structures reveal various intermolecular anion\u2010\u03c0 and \u03c3\u2010hole interactions between the corresponding halogenated pyridinium cations and the anion [Al(OTeF5)4]\u2212.The synthesis and the first structural characterization of the halogenated pyridinium salts [C 5F5NH]+ and [C5F4ClNH]+ and the dimeric cations [(C5F5N)2H]+ and [(C5Cl5N)2H]+ as [Al(OTeF5)4]\u2212 salts are presented. These cations show noncovalent interactions with the weakly coordinating anion [Al(OTeF5)4]\u2212 such as strong fluorine specific interactions as well as \u03c3\u2010hole and anion\u2010\u03c0 interactions.The synthesis and structural characterization of the perhalogenated pyridinium cations [C While non fluorinated pyridine can be protonated by HCl or HBr, pentafluoropyridine can only be protonated by Br\u00f8nsted superacids such as HF/AsF5 and HF/SbF5.o\u2010C6H4F2\u2010H][Al(OTeF5)4] is known for the protonation of weak bases like benzene and white phosphorus, resulting in [C6H7]+ and [P4H]+, respectively.6F6, which can result in anion\u2010\u03c0 interactions.4]\u2212 and [PF6]\u2212[6] or between perfluoroarenes, like C5F5N, C6F6 and C10F8 with different halide anions.5F5N, C5F4ClN, and C5Cl5N by [o\u2010C6H4F2\u2010H][Al(OTeF5)4] (1\u2009a) and studied hydrogen bonding, halogen bonding and anion\u2010\u03c0 interactions between pentafluororopyridinium [C5F5NH]+ (2), 4\u2010chloro\u20102,3,5,6\u2010tetrafluoropyridinium [C5F4ClNH]+ (3), pentachlororopyridinium [C5Cl5NH]+ (4) and the fluorinated WCA [Al(OTeF5)4]\u2212 (a).In contrast to pyridine, the perfluorinated pyridine C5F5N<C5F4ClN<C5Cl5N  of the pyridinium cations illustrate that in all cases, their strongest interaction with an anion will be observed via the N\u2212H moiety Figure\u2005. Beside 5F5N, C5F4ClN or C5Cl5N with the Br\u00f8nsted superacid 1\u2009a in ortho\u2010difluorobenzene (oDFB) \u00b0. These moieties are symmetry related by an inversion center. As short fluorine/fluorine (F4\u22c5\u22c5\u22c5F3) contacts of 276.8(21)\u2005pm are observed between the two cations we further inspected the fluorine\u2010specific interaction in an isolated [C5F5NH]+\u2010dimer by means of atoms in molecules (AIM) analysis. At the bond critical points (CP) between F3 and F4 the electron density is very low (\u03c1CP=0.045\u2005e\u2009A\u22123) and the Laplacian is small and positive (\u25bf2\u03c1CP=0.035\u2005e\u2009A\u22125). Together with a value of the electron localization function (ELF) close to zero (0.01) and a ratio of the absolute potential (|V|) and the kinetic energy density (G) below 1 (0.74), this indicates a non\u2010shared interaction such as a van\u2010der\u2010Waals interaction. An ionic interaction appears to be unlikely for this dimer of two cations.Figure\u2005The Hirshfeld surface analysis Figure\u2005 reveals 1\u2009a with an excess of C5F5N the salt [(C5F5N)2H][Al(OTeF5)4] (5\u2009a) was obtained. It crystallizes in the monoclinic space group Cc \u2005pm which is about 35\u2005pm shorter than the sum of the van der Waals radii of 310\u2005pm.5 moiety above and below the plane of the pentafluoropyridines are stabilizing the planar arrangement . For 4\u2010halotetrafluoropyridines, the halogen bond donor strength weakens in the order I, Br, Cl.5)4]\u2212 in the solid state.1\u2009a 4] (3\u2009a) crystallizes in the monoclinic space group C2/c . The reaction of two equivalents of pentachloropyridine with 1\u2009a yielded single crystals of [(C5Cl5N)2H][Al(OTeF5)4]\u22c5C6H4F2 (6\u2009a\u22c5C6H4F2). The compound crystallizes in the monoclinic space group P21/c \u2005pm which is 20\u2005pm below the sum of the van der Waals radii. Multiple short Fc Figure\u2005.5\u2009a the pyridine rings form a pyridinium\u2010pyridine dimer. The N\u2212N distances in dimers 5\u2009a and 6\u2009a are indistinguishable within the experimental error. Moreover, the two pentachloropyridine rings in 6 are staggered with an angle between the planes of 95.8(1)\u00b0, in contrast to the fluorinated analogue 5 which is arranged coplanar \u2005pm which indicates a rather strong interaction.6 . Additionally, a number of halogen interactions are observed beween the chlorine atoms in 2,6\u2010 and 4\u2010positions of 6 and a) fluorine atoms (d(Cl6\u2010F20)=307.47(18)\u2005pm, d(Cl3\u2010F14)=312.3(2)\u2005pm, d(Cl15\u2010F13)=317.93(19)\u2005pm), b) oxygen atoms (d(Cl8\u2010O4)=301.71(18)\u2005pm) of the WCA, and c) fluorine atoms of the co\u2010crystalized oDFB (d(Cl10\u2010F22)=307.43(19)\u2005pm, d(Cl10\u2010F21)=300.34(19)\u2005pm).As for the fluorine analogue r Figure\u2005. Single 2\u2009a and 3\u2009a several broad bands for the N\u2212H stretch are observed. The N\u2212H band for 2\u2009a exhibits two maxima at 3104\u2005cm\u22121 and 2953\u2005cm\u22121, respectively. The N\u2212H band for 3\u2009a shows three maxima at 3301\u2005cm\u22121, 3204\u2005cm\u22121 and 2953\u2005cm\u22121, respectively. In contrast to the spectra of the monomeric cations the spectra of the pyridinum\u2010pyridine dimers show very broad bands in the region from 3000 to 1750\u2005cm\u22121 for 5\u2009a and from 3500 to 2000\u2005cm\u22121 for 6\u2009a attributed to the N\u2212H stretching vibration. This is well combarable to the reported spectrum of the nonhalogenated pyridinum\u2010pyridine dimer.In the IR spectra of o\u2010C6H4F2\u2010H][Al(OTeF5)4] is able to protonate a series of the very weakly basic perhalogenated pyridines. The cations [C5F5NH]+, [C5F4ClNH]+, [(C5Cl5N)2H]+, and [(C5F5N)2H]+ were structurally characterized for the first time. In the solid state rather strong noncovalent interactions between these electron deficient aromatic cations and the weakly coordinating anion [Al(OTeF5)4]\u2212 are observed. Due to the protonation of the halogenated pyridines, their ability to form halogen bonds as well as anion\u2010\u03c0 interactions is increased compared to the neutral species.The Br\u00f8nsted superacid \u2010acetone was flame sealed in a glass capillary and the lock oscillator frequency was adjusted to give \u03b4(1H)=7.26\u2005ppm for a CHCl3 sample locked on the capillary. Chemical shifts and coupling constants of strongly coupled spin systems are given as simulated in gNMR.8 Venture diffractometer with a PHOTON 100 CMOS area detector using Mo\u2212K\u03b1 radiation. Single crystals were coated with a perfluoroether oil at \u221225\u2009\u00b0C and selected under nitrogen atmosphere. Using Olex2,For detailed experimental data, see electronic Supporting Information. All reactions were carried out under inert conditions using standard Schlenk techniques. Glass vessels were greased with Triboflon III. All solid materials and triethylaluminium (Al(C2\u2009a), 2074488 (for 5\u2009a), 2082692 (for 3\u2009a), 2074489 (for 6\u2009a)2082701 (for  contain(s) the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.Deposition Number (s) 5\u2009a, the 3\u2010D dnorm surfaces were mapped using a fixed color scale of \u22120.4727 (red) to 0.5303 (blue), using an isovalue of 0.5. For 2\u2009a, 3\u2009a and 6\u2009a\u22c5o\u2010C6H4F2, the 3\u2010D dnorm surfaces were mapped using a fixed color scale of \u22120.0964 (red) to 0.9305 (blue), using an isovalue of 0.5. Red contours indicated a contact less than the sum of the van der Waals radii of the respective elements. Blue and white contours indicate that the nearest external atom is at a distance greater or equal to the sum of the van der Waals radii respectively from atomic coordinates. Atoms in Molecules (AIM) analysis of an isolated [C5F5NH]+\u2010dimer based on calculations at B3LYP\u2010D3/cc\u2010pVTZAll calculations were performed using a general\u2010purpose High\u2010Performance Computer at ZEDAT (CURTA),5F5NH][Al(OTeF5)4] (2Synthesis of [C\u2009a): A sample of Al(C2H5)3  was dissolved in 3\u2005mL of ortho\u2010difluorobenzene (oDFB). The solution was degassed and HOTeF5  was condensed onto it at \u2212196\u2009\u00b0C. The reaction mixture was warmed up to \u221230\u2009\u00b0C. Afterwards a gas bubbler was added and the reaction mixture was stirred for 30\u2005min. A yellow solution was obtained indicating the formation of the corresponding Br\u00f8nsted superacid. C5F5N  was condensed into a Schlenk tube with a PTFE cap and dissolved in 2\u2005mL of oDFB. This solution was added to reaction vessel via syringe under an argon stream. The gas bubbler was exchanged with a stopper and the mixture was stirred for another 30\u2005min at \u221230\u2009\u00b0C. The pressure in the reaction vessel was reduced and the flask was placed in a \u221224\u2009\u00b0C fridge for crystallization. [C5F5NH][Al(OTeF5)4] was obtained as colourless crystals. 1H\u2005NMR : \u03b4=12.1  ppm; 19F\u2005NMR : \u03b4=\u221240.5 , \u221247.6 , \u221295.2 , \u2212100.1 , \u2212153.1  ppm; 27Al\u2005NMR : \u03b4=49.9 \u2212, d, 22.5\u2009% [Al(OTeF5)3(O125TeF5)]\u2212, 2J=72\u2005Hz; t, 2.5\u2009% [Al(OTeF5)2(O125TeF5)2]\u2212, 2J=69\u2005Hz] ppm. IR : v\u02dc=3103 (w), 2953 (w), 1691 (m), 1610 (m), 1535 (w), 1466 (w), 1325 (w), 1122 (m), 988 (w), 927 , 799 , 684 , 606 , 553  cm\u22121. 5F5NH][Al(OTeF5)4]Crystal Data for [Al(OTeF5)4] (3Synthesis of [C\u2009a): The synthesis was analogous to the one of [C5F5NH][Al(OTeF5)4] using C5F4ClN  that was previously dissolved in 2\u2005mL of oDFB. After the reaction was complete, all volatile parts were removed in vacuo. The flask with the remaining solution was put into a \u221224\u2009\u00b0C fridge for crystallization. [C5F4ClNH][Al(OTeF5)4] was obtained as colourless crystals. 1H\u2005NMR : \u03b4=12.2  ppm. 19F\u2005NMR : \u03b4=\u221238.8 , \u221245.7 , \u221299.1 , \u2212133.3  ppm. 27Al\u2005NMR : \u03b4=50.1 \u2212; d, 22.5\u2009% [Al(OTeF5)3(O125TeF5)]\u2212, 2J=72\u2005Hz; t, 2.5\u2009% [Al(OTeF5)2(O125TeF5)2]\u2212, 2J=73\u2005Hz] ppm. IR : v\u02dc=3301 (w), 3204 (m), 2953 (vw), 1671 (w), 1649 (w), 1570 (m), 1471 (w), 1445 (w), 1305 (m), 928 , 687 , 636 , 633 (m), 618 (m), 553 , 246 (w) cm\u22121. 5F4ClNH][Al(OTeF5)4]Crystal Data for [Al(OTeFSynthesis of [(C5)4] (5\u2009a): The synthesis was analogous to the one of [C5F5NH][Al(OTeF5)4] using 10\u2005equivalents of C5F5N  that were previously dissolved in 3\u2005mL of oDFB. [(C5F5N)2H][Al(OTeF5)4] was obtained as a colourless crystals. 1H\u2005NMR : \u03b4=11.5  ppm; 19F\u2005NMR : \u03b4=\u221238.7 , \u221245.8 , \u221289.7 , \u2212132.2 , \u2212161.8  ppm; 27Al\u2005NMR : \u03b4=50.1 \u2212, d, 22.5\u2009% [Al(OTeF5)3(O125TeF5)]\u2212, 2J=73\u2005Hz; t, 2.5\u2009% [Al(OTeF5)2(O125TeF5)2]\u2212, 2J=73.2\u2005Hz] ppm. IR : v\u02dc=2323 (w), 1848 (w), 1666 (m), 1610 (m), 1442 (s), 1394 (w), 1307 (m), 1213 (vw), 1104 (m), 1092 (m), 930 , 685 , 641 , 627 (m), 553 , 431 (w) cm\u22121. 5F5N)2H][Al(OTeF5)4]Crystal Data for [Al(OTeFSynthesis of [(C5)46H4F2 (6]\u22c5C\u20096H4F2)a\u22c5C: The synthesis was analogous to the one of [C5Cl5NH][Al(OTeF5)4] using 2\u2005equivalents of C5Cl5N  that were previously dissolved in 3\u2005mL of oDFB. [(C5Cl5N)2H][Al(OTeF5)4] was obtained as colourless crystals. 1H\u2005NMR : \u03b4=17.5  ppm; 19F\u2005NMR : \u03b4=\u221238.6 , \u221245.7  ppm; 27Al\u2005NMR : \u03b4=50.0 \u2212, d, 22.5\u2009% [Al(OTeF5)3(O125TeF5)]\u2212, 2J=73.0\u2005Hz; t, 2.5\u2009% [Al(OTeF5)2(O125TeF5)2]\u2212, 2J=73.0\u2005Hz] ppm. IR : v\u02dc=3555 (m), 3001 (vw), 2953 (vw), 1619 (w), 1541 (w), 1491 (w), 1449 (w), 1403 (w), 1143 (m), 1120 (m), 1088 (m), 1085 (m), 1007 (m), 922 , 859 (m), 693 , 633 (m), 618 (m), 555 , 420 (s) cm\u22121. 5Cl5N)2H][Al(OTeF5)4]\u22c5C6H4F2Crystal Data for [(C (M=1599.10\u2005g/mol): monoclinic, space group P21/c (no. 14), a=12.978(3)\u2005\u00c5, b=22.529(5)\u2005\u00c5, c=14.071(3)\u2005\u00c5, \u03b2=96.167(8)\u00b0, V=4090.4(15)\u2005\u00c53, Z=4, T=100.1\u2005K, \u03bc(MoK\u03b1)=3.632\u2005mm\u22121, Dcalc=2.597\u2005g/cm3, 173293 reflections measured (4.442\u00b0\u22642\u0398\u226456.616\u00b0), 10174 unique  which were used in all calculations. The final R1 was 0.0208 (I>2\u03c3(I)) and wR2 was 0.0484 .The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The crystal structures and Hirshfeld surface analyses of three salts of 1-(4-nitro\u00adphenyl)\u00adpiperazine with 2-chloro\u00adbenzoic acid, 2-bromo\u00adbenzoic acid and 2-iodo\u00adbenzoic acid are reported. 10H14N3O2+\u00b7C7H4ClO2\u2212, contains whole-ion-disordered cations and anions, which were modeled with two equivalent conformations with occupancies of 0.745\u2005(10)/0.255\u2005(10) and 0.563\u2005(13)/0.437\u2005(13), respectively. The bromo\u00adbenzoate and iodo\u00adbenzoate derivatives are isomorphous and crystallize as hemihydrates, viz. C10H14N3O2+\u00b7C7H4BrO2\u2212\u00b70.5H2O and C10H14N3O2+\u00b7C7H4IO2\u2212\u00b70.5H2O, respectively [the water mol\u00adecule is disordered over two locations with occupancies of 0.276\u2005(3)/0.223\u2005(3) for the iodo\u00adbenzoate derivative]. In the extended structures, all three salts feature an R44(12) loop of two anions and two cations linked by N\u2014H\u22efO hydrogen bonds.The crystal structures and Hirshfeld surface analyses of three salts of 1-(4-nitro\u00adphenyl)\u00adpiperazine with 2-chloro\u00adbenzoic acid, 2-bromo\u00adbenzoic acid and 2-iodo\u00adbenzoic acid are reported. The chloro\u00adbenzoate salt, C When discussing the conformations of the anion and cation, only the major components will be used. In the chloro\u00adbenzoate anion, the carboxyl\u00adate group is significantly twisted with respect to the 2-chloro\u00adphenyl ring with a dihedral angle of 76.7\u2005(4)\u00b0, which is likely due to the steric inter\u00adaction between the ortho-chloro substituent and the carboxyl\u00adate group. Structures 2 and 3 exhibit similar cation conformations, with equivalent dihedral angles of 65.5\u2005(3) and 67.1\u2005(5)\u00b0, respectively. Additionally, in all three structures, the 4-nitro\u00adphenyl group occupies an equatorial position in its attachment to the piperazinium ring.Structure ds Fig.\u00a01, which w2 and 3 are isostructural, only 2 will be discussed in detail. This structure consists of a 4-(4-nitrophenyl)piperazin-1-ium cation linked to a 2-bromo\u00adbenzoate anion by two N\u2014H\u22efO hydrogen bonds /0.223\u2005(3) for the iodo\u00adbenzoate derivative]. Additionally, there is a weak C\u2014H\u22efBr inter\u00adaction accepted by the bromine atom in the 2-bromo\u00adbezoate anion and a carbon atom in the piperazinium ring, as well as a pair of weak C\u2014H\u22efO inter\u00adactions between adjacent 4-nitro\u00adphenyl rings in the 4-(4-nitrophenyl)piperazin-1-ium cation.Since s Figs. 2 and 3 \u25b8.3.1, which contains both a disordered cation and anion as well as disordered water of solvation, the discussion will focus solely on the major component. The cation forms an x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; x, 1\u00a0+\u00a0y, z; 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; see Fig.\u00a04x, \u2212y, \u2212z; Y\u22efCg distance = 3.488\u2005(18)\u2005\u00c5; X\u2014Y\u22efCg: 85.8\u2005(12)\u00b0].In the packing of 2, two cations and two anions form an et al., 1990x, \u2212y, \u2212z; see Fig.\u00a06x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z) that form an x, y, z). The phenyl rings in adjacent cations form \u03c0\u2013\u03c0 inter\u00adactions with a perpendicular distance between centroids of 3.5332\u2005(11)\u2005\u00c5 . These are all clearly seen in the fingerprint plot generated by CrystalExplorer  that form an Refinement). This species is likely to be involved in hydrogen bonding with an adjacent oxygen atom in the anion  and with the piperazine ring in the cation, forming an x, 1\u00a0\u2212\u00a0y, \u2212z; slippage = 0.379\u2005\u00c5).In the packing of 4.et al., 2014et al., 2022aet al., 2022et al., 2022aRelated structures containing the 4-(4-nitrophenyl)piperazin-1-ium cation include 4-(4-nitrophenyl)piperazin-1-ium chloride monohydrate \u2013(3), a solution of commercially available (from Sigma-Aldrich) 1-(4-nitro\u00adphenyl)\u00adpiperazine  in methanol (10\u2005ml) was mixed with equimolar solutions of the appropriate acids in methanol (10\u2005ml) and ethyl acetate (10\u2005ml), viz., 2-chloro\u00adbenzoic acid  for (1), 2-bromo\u00adbenzoic acid  for (2), and 2-iodo\u00adbenzoic acid  for (3), The resulting solutions were stirred for 15 minutes at room temperature and allowed to stand at the same temperature. X-ray quality crystals were formed on slow evaporation after one week for all compounds, where ethanol:ethyl\u00adacetate (1:1) was used for crystallization. The melting points are 439\u2013441\u2005K (1), 443\u2013445\u2005K (2) and 451\u2013453\u2005K (3).For the synthesis of salts (6.Uiso(H) = 1.2Ueq(C) while the N\u2014H hydrogen atoms were refined isotropically. For 1, in which both the cation and the anion exhibit whole-ion disorder, two equivalent conformations were modeled with occupancies of 0.745\u2005(10)/0.255\u2005(10) and 0.563\u2005(13)/ 0.437\u2005(13) respectively. The water hydrogen atoms were refined isotropically with idealized geometries.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698902300302X/hb8051sup1.cifCrystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S205698902300302X/hb80511sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698902300302X/hb80512sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S205698902300302X/hb80513sup4.hklStructure factors: contains datablock(s) 3. DOI: 2253382, 2253381, 2253380CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "After the introduction of a pyridine\u2010containing auxiliary, which provided access to challenging junctions (proline or \u03b2\u2010branched amino acids), we herein probe the role of the pyridine\u2010ring nitrogen. We observed side reactions leading to preliminary auxiliary loss. We describe a new easy to attach \u03b2\u2010mercapto\u2010\u03b2\u2010(4\u2010methoxy\u20102\u2010pyridinyl)\u2010ethyl (MMPyE) auxiliary, which 1) has increased stability; 2) enables NCL at sterically encumbered junctions ; and 3) allows removal under mildly basic (pH\u20058.5) conditions was introduced. The synthesis of a 120 aa long peptide containing eight MUC5AC tandem repeats via ligation of two 60mers demonstrates the usefulness. Making use of hitherto unexplored NCL to tyrosine, the MMPyE auxiliary provided access to a head\u2010to\u2010tail\u2010cyclized 21\u2010mer peptide and a His A properly positioned pyridine ring can speed up auxiliary\u2010mediated native chemical ligation. A methoxy substituent increases auxiliary stability and facilitates rapid syntheses of long and multiphosphorylated multirepeat proteins and of head\u2010to\u2010tail cyclized peptides. N\u2010terminal cysteine for reactions with peptide thioesters. The ligation\u2010desulfurization involves thiolated amino acids, which mimic the 1,2\u2010aminothiol structure of cysteine. After ligation, the thiol group is removed by a radical reaction.The native chemical ligation (NCL) reaction is a cornerstone of protein total synthesis.N\u2010terminus.N\u2010terminal alkylation reduces the reactivity of the amino group. Exemplary for this problem are the early N\u2010benzyl type auxiliaries  will become challenging if not impossible at amino acids with larger steric demand than glycine. A solution to the problem became apparent when we, while working on alternative auxiliary scaffolds, became aware of a radical fragmentation reaction (see below) that allows removal of non\u2010benzyl auxiliaries.8 ethyl (MPyE) scaffold 9 is the first auxiliary enabling ligations at sterically demanding junctions such as Leu\u2010Arg, Leu\u2010Val or Pro\u2010Ala.S,N\u2010acyl transfer by base catalysis . While shifting the nitrogen from the ortho to the para position should have little effect on its basicity, the intramolecular proton abstraction  should be impossible. For the para isomer of the MPyE auxiliary, we therefore expected a ligation speed comparable to that of the MPE auxiliary 8.The recently introduced MPyE auxiliary enables NCL reactions at ligation junctions inaccessible to previous ligation auxiliaries. For example, we established Ala\u2010Val, Leu\u2010Val, Pro\u2010Ala and Pro\u2010Arg bonds.17 . Under these conditions, the original ortho isomer of the MPyE auxiliary remained stable. Nevertheless, with quick and careful handling we succeeded in the isolation of product (53\u2009%) and subsequently analyzed reactions of the para\u2010MPyE peptide with the peptide thioester 19A. The attempted Ala\u2010Asn ligation was slow . The decrease of ligation rates upon para positioning illustrates the role of the ring nitrogen, which must be in the ortho position to allow acceleration of the S,N\u2010acyl transfer by intramolecular base catalysis.The aldehyde precursor 7 Figure\u2005A requirepara\u2010MPyE group from peptide 18N prompted us to also critically analyze the stability of the ortho\u2010MPyE auxiliary. In a published example23LV  and iminium ion 31. The latter would undergo rapid hydrolysis. Alternatively, the ethylpyridine structures may undergo a Hoffman elimination facilitated by anchimeric assistance from a deprotonated thiol group, which would be considerably acidified by pyridine protonation =4.88; pKA (pyridine)=5.17)The considerations on the stability and reactivity of the MPyE auxiliary indicate an important role of the ring nitrogen. We examined methoxy substitution in meta position to the nitrogen. Methoxy substitution decreases the basicity of pyridine nitrogen (pK\u03b1\u2010methyl carbon with lithium diisopropylamide and subjected to a nucleophilic acylation with diethyl carbonate to yield methyl (5\u2010methoxy\u20102\u2010pyridinyl)acetate (37). Treatment with lithium bis(trimethylsilyl)amide afforded an ester enolate which was converted to the \u03b1\u2010mercapto ester 39 in an electrophilic thiolation. Reduction of 39 with diisobutylaluminium hydride (DIBALH) furnished 40 as a suitable precursor for auxiliary introduction by reductive alkylation. Compound 40 is present in its enole form and shelf\u2010stable.For the introduction of the MMPyE auxiliary, a suitable precursor was synthesized in 4 steps  in presence of 2\u2009% acetic acid, the peptides were treated with a mixture of TFA/H2O/TIS (95/2.5/2.5 v/v/v) for final deprotection and cleavage of the peptides from resin. The crude peptides were obtained in high purity, indicative of efficient reductive alkylation .We next attached the MMPyE auxiliary to the unprotected N\u2010terminus of asparagine and valine test peptides Figure\u2005B. After 41X with the peptide thioesters 19Z the compounds were dissolved in a mixture prepared by adding 3\u2005vol.% thiophenol to a phosphate buffer containing 6\u2005M guanidinium hydrochloride with an apparent pH\u20057.5. The ligations proceeded smoothly. Compared to reactions at the non\u2010substituted MPyE peptide we observed the expected decrease in the reaction rate , we observed a rapid auxiliary cleavage within 3 to 6\u2005h .52 was prepared by microwave\u2010assisted solid phase peptide synthesis (MW\u2010SPPS) and used in crude form in the reaction with mercaptopropionate (MPA). The conversion to the MPA ester 53 proceeded smoothly . For an approach to a peptide thioester, we first synthesized the peptide hydrazide by microwave\u2010assisted solid\u2010phase synthesis. Dawson's acetoacetone method was applied to establish the peptide thioester 59 without detriment to the three phospho sites .59 and 57 was discontinued by treatment with hydrazine. Though our aim was to develop a method providing rapid access of product without isolation of intermediates, we also analyzed the ligation mixture . We observed an unexpected by\u2010product resulting from cleavage of the N\u2010terminal tyrosine from peptide 57. This side reaction was less pronounced in ligations with non\u2010phosphorylated peptides  and did not occur at all with a test peptide . At current, we cannot explain this unusual side reaction. Other ligations at tyrosine 6 peptide 60 in pure form.Due to our interest in post\u2010translationally modified multirepeat proteins, we tested the auxiliary in the rapid synthesis of a hexaphosphorylated peptide comprising 6 heptapeptide repeat units from the C\u2010terminal domain of the large RNA polymerase II subunit.In a further exploration of application scenarios, we studied a cyclopeptide. The chemical synthesis of cyclopeptides is an active area in medicinal peptide chemistry and NCL is powerful method to achieve cyclization of unprotected linear peptide precursors.Previously we have shown that cysteine residues should be protected during auxiliary removal.\u03b2\u2010mercapto\u2010\u03b2\u2010(2\u2010pyridinyl)\u2010ethyl auxiliaries proceed in high rate and enable joining of peptide fragments at junctions, such as the Leu\u2010Val bond inaccessible to previous ligation auxiliaries. In this work, we probed the role of the ortho\u2010positioned ring nitrogen. A comparison with the para isomer (\u03b2\u2010mercapto\u2010\u03b2\u2010(4\u2010pyridinyl)\u2010ethyl) scaffold revealed the superior reactivity of the ortho pyridine derivatives. We attribute the high reactivity to the ortho ring nitrogen abstracting a proton from an ammonium ion formed when the amino group intramolecularly attacks the thioester bond. Without deprotonation the S,N\u2010acyl shift cannot proceed and the reaction stops at the thioester intermediate stage. Our investigations also uncovered a peculiar lability of peptides modified with the \u03b2\u2010mercapto\u2010\u03b2\u2010(4\u2010pyridinyl)\u2010ethyl) group at the N\u2010terminus. While the para\u2010pyridine auxiliary\u2010peptide bond was stable during TFA cleavage, rapid cleavage occurred at moderately acidic pH\u20052. This reaction only occurs prior to ligation indicating a role of the amino terminus\u2019 lone pair. Though at a slower rate, premature auxiliary loss was also observed with the ortho\u2010system (\u03b2\u2010mercapto\u2010\u03b2\u2010(2\u2010pyridinyl)\u2010ethyl). Importantly, our studies show that the auxiliary gains stability when a methoxy substituent is added at the 4\u2010position of the ortho\u2010pyridine ring (i.\u2009e. meta to the ring nitrogen).Native chemical ligation reactions on \u03b2\u2010mercapto\u2010\u03b2\u2010(4\u2010methoxy\u20102\u2010pyridinyl)\u2010ethyl) auxiliary is conveniently attached to the peptide N\u2010terminus in the last step of solid\u2010phase synthesis by reductive alkylation. Despite slightly lowered ligation rates, the MMPyE auxiliary is better suited for NCL at challenging junctions than the MPyE auxiliary becausethe increased stability is a significant advantage when reactions such as the selenoester\u2010NCLs are performed at slightly acidic conditions. Reactions proceed cleanly also when long reaction times are needed in ligations of large peptides. Furthermore, the increased stability enables ligations at elevated temperature. The usefulness of the MMPyE auxiliary was demonstrated in three applications. The synthesis of a 120 aa long peptide containing 8 MUC5AC tandem repeats and two \u201csticky\u201d coiled coil peptides involved the smooth ligation of two 60mers via a Ser\u2010Ala junction. Using a hitherto unexplored ligation site in NCL chemistry and demonstrating the potential for the preparation of post\u2010translationally modified peptides, we applied the MMPyE auxiliary in a Ser\u2010Tyr ligation for the synthesis of a His6\u2010tagged hexaphosphorylated peptide spanning 6 tandem repeats of the RNA polymerase II C\u2010terminal domain. The rapid synthesis of a Phe\u2010Tyr\u2010cyclized 21 aa peptides comprising the primary sequence of microcin J25 illustrates an application of the auxiliary in head\u2010to\u2010tail cyclization reactions.The new MMPyE  are stable over a wide pH range, 2) enable native chemical ligations at sterically encumbered junctions, 3) allow removal under mildly basic (pH\u20058.5) conditions and 4) provide options for attaching further handles by means of 4\u2010alkoxy substituents. The last option offers prospects for the introduction of functional units such as oligoethylene glycol or oligoarginine units that enhance the solubility of unfolded peptide segments.Ethyl 2\u2010(pyridin\u20104\u2010yl)\u20102\u2010thio)acetate (S4): Under argon atmosphere, lithium hexamethyldisilazide  was added to a stirred solution of ethyl 2\u2010(pyridin\u20104\u2010yl)acetate  in 75\u2005mL anhydrous THF over the course of 25\u2005min at \u221278\u2009\u00b0C. After 30\u2005min of stirring, thiosulfonate 38  in 40\u2005mL anhydrous THF was added at \u221278\u2009\u00b0C over 100\u2005min. The reaction mixture was allowed to gradually warm to room temperature over the course of 30\u2005min and a saturated solution of NH4Cl was added. The resultant mixture was extracted with EtOAc (3x) and the combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (EtOAc) to afford desired product  in 82\u2009% yield as a white solid. 1H NMR : \u03b4 [ppm]=8.52 , 7.38 , 6.16 , 4.66 , 4.12 , 3.78 , 3.75 , 3.75 \u2010 3.72 , 1.19 . 13C NMR : \u03b4 [ppm]=170.94, 161.94, 159.85, 150.77, 147.17, 124.38, 107.02, 91.64, 62.74, 56.44, 56.06, 52.28, 25.19, 14.32.2\u2010(Pyridin\u20104\u2010yl)\u20102\u2010thio)acetaldehyde (17): Under argon atmosphere ester S4  was dissolved in 5\u2005mL anhydrous DCM and cooled to \u201094\u2009\u00b0C. Diisobutylaluminium hydride  was added carefully over the vessel wall over the course of 1\u2005h. The reaction mixture was stirred for an additional 15\u2005min at \u221294\u2009\u00b0C. Subsequently, a mixture of DCM/MeOH  was added via the vessel wall over the course of 30\u2005min at \u221294\u2009\u00b0C. The reaction mixture was stirred at room temperature for 10\u2005min and a saturated solution of potassium sodium tartrate and DCM (20\u2005ml each) was added. The resulting mixture was stirred at room temperature for 1\u2005h and then extracted with DCM (3x). The combined organic layers were dried over MgSO4, filtered and concentrated. The residue was purified by flash column chromatography on silica gel (EtOAc) to afford the aldehyde 17 (247\u2005mg) as yellow oil. The material was used for reductive alkylation despite impurities from remaining solvents and partial decomposition. 1H NMR : \u03b4 [ppm]=9.52 , 8.52 , 7.27 , 6.10 , 4.62 , 3.78 , 3.77 , 3.75 .Ethyl 2\u2010(5\u2010methoxypyridin\u20102\u2010yl)acetate (37): nBuLi  was added dropwise to a stirred solution of diisopropylamine  in 20\u2005ml anhydrous THF at \u221278\u2009\u00b0C under argon. The resulting solution was slowly warmed to room temperature and was added dropwise over 1\u2005h to a stirred solution of 5\u2010methoxy\u20102\u2010methylpyridine  and anhydrous diethylcarbonate  in 26\u2005ml anhydrous THF at \u221278\u2009\u00b0C. After 2\u2005h of reaction, the solution was slowly warmed to room temperature and a saturated solution of NH4Cl was added. The resultant mixture was extracted with EtOAc (3x), and the combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (cyclohexane/EtOAc=6\u2009:\u20094 v/v) to afford 37  as a light\u2010yellow oil. 1H NMR : \u03b4 [ppm]=8.25 , 7.28\u20137.20 , 4.18 , 3.86 , 3.82 , 1.26 . 13C NMR : \u03b4 [ppm]=170.91, 154.88, 146.23, 136.13, 124.52, 122.22, 61.17, 55.83, 42.59, 14.28. HRMS: m/z=196.0967 (C10H14NO3 (M+H)+, calcd.: 196.0968).Ethyl 2\u2010(5\u2010methoxypyridin\u20102\u2010yl)\u20102\u2010thio) acetate (39): Under argon atmosphere, lithium hexamethyldisilazide  was added to a stirred solution of ethyl 2\u2010(5\u2010methoxypyridin\u20102\u2010yl)acetate  in 40\u2005mL anhydrous THF over the course of 25\u2005min at \u221278\u2009\u00b0C. After 30\u2005min of stirring, thiosulfonate 38  in 37\u2005mL anhydrous THF was added at \u221278\u2009\u00b0C within 100\u2005min. The reaction mixture was allowed to gradually warm to room temperature over the course of 30\u2005min and a saturated solution of NH4Cl was added. The resultant mixture was extracted with EtOAc (3x) and the combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (cyclohexane/EtOAc=1\u2009:\u20091 v/v) to afford 39  as a white solid. 1H NMR : \u03b4 [ppm]=8.15 , 7.43 , 7.27 , 6.17 , 4.75 , 4.12 , 3.83 , 3.78 , 3.76 , 1.19 . 13C NMR : \u03b4 [ppm]=171.39, 161.69, 159.74, 155.98, 149.63, 137.36, 124.05, 122.02, 107.32, 91.52, 62.23, 56.37, 56.33, 55.95, 54.59, 25.03, 14.33. HRMS: m/z=408.1455 (C20H26NO6S (M+H)+, calcd.: 408.1475).E)\u20102\u2010(5\u2010methoxypyridin\u20102\u2010yl)\u20102\u2010thio)ethenol (40) was dissolved in 2.1\u2005mL anhydrous DCM and cooled to \u201094\u2009\u00b0C. Diisobutylaluminium hydride  was added carefully via the vessel wall over the course of 1\u2005h. The reaction mixture was stirred for an additional 15\u2005min at \u221294\u2009\u00b0C. Subsequently, a mixture of DCM/MeOH  was added via the vessel wall over the course of 30\u2005min at \u221294\u2009\u00b0C. The reaction mixture was stirred at room temperature for 10\u2005min and a saturated solution of potassium sodium tartrate and DCM (20\u2005ml each) was added. The resulting mixture was stirred at room temperature for 1\u2005h and then extracted with DCM (3x). The combined organic layers were dried over MgSO4, filtered and concentrated. The residue was purified by recrystallization (MeOH/H2O) to afford the enol 40  as bright yellow crystals. 1H NMR : \u03b4 [ppm]=14.83 , 8.07 , 7.79 , 7.45 , 7.15 , 6.11 , 3.86 , 3.76 , 3.70 , 3.61 . 13C NMR : \u03b4 [ppm]=162.21, 161.52, 159.95, 154.14, 153.60, 132.01, 124.77, 122.72, 107.40, 102.62, 91.34, 56.68, 56.29, 55.97, 28.49. HRMS: m/z=364.1201 (C18H22NO5S (M+H)+, calcd.: 364.1213).Peptide Purification: The desired peptides were purified by preparative HPLC on a C18\u2010column with a binary mixture of A  and B  as mobile phase (flow=6.0\u2005mL/min). For model peptides a linear gradient from 3\u201330\u2009% B was used. For other peptides a linear gradient was used as indicated. All products were isolated as white solids after lyophilization. Yields were determined by measurements of UV absorption as described in chapter 5.3. of the Suppl. Inf. or by weighing.2)2(CO)\u2010Gly\u2010NH2 (19A)LYRAA\u2010S(CH: Thioester 19A was synthesized according to the published procedure.R=1.39\u2005min (3\u201330\u2009% B in 4\u2005min); m/z=737.5 (C32H53N10O8S (M+H)+, calcd.: 737.4), 369.3 (C32H54N10O8S (M+2H)2+, calcd.: 369.2); C32H52N10O8S (MW=736.4\u2005g\u2009mol\u22121).2)2(CO)\u2010Gly\u2010NH2 (19L)LYRAL\u2010S(CH: Thioester 19L was synthesized according to the published procedure.R=3.57\u2005min (3\u201335\u2009% B in 6\u2005min); m/z=779.7 (C35H59N10O8S (M+H)+, calcd.: 779.4), 390.4 (C35H60N10O8S (M+2H)2+, calcd.: 390.2); C35H58N10O8S (MW=778.4\u2005g\u2009mol\u22121).LYRAA\u2010SePh (22A): Selenoester 22A was synthesized according to the published procedure.R=5.31\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=733.4 (C33H49N8O6Se (M+H)+, calcd.: 733.3), 367.4 (C33H50N8O6Se (M+2H)2+, calcd.: 367.1); C33H48N8O6Se (MW=732.3\u2005g\u2009mol\u22121).LYRAL\u2010SePh (22L): Selenoester 22L was synthesized according to the published procedure.R=2.31\u2005min (3\u201060\u2009% B in 4\u2005min); m/z=775.4 (C36H55N8O6Se (M+H)+, calcd.: 775.3), 388.3 (C36H56N8O6Se (M+2H)2+, calcd.: 388.2); C36H54N8O6Se (MW=774.3\u2005g\u2009mol\u22121).General Procedure for Introduction of MMPyE Auxiliary: The peptidyl\u2010resin was allowed to swell in MeOH/NMP/AcOH (6\u2009:\u20094\u2009:\u20090.02 v/v/v) for 15\u2005min and then treated with a mixture of the enol 40 and NaCNBH3  in MeOH/NMP/AcOH (3\u2009:\u20091\u2009:\u20090.02 v/v/v) over night at room temperature . Afterwards the resin was washed with DCM (5x), MeOH (5x) and DCM (5x) and dried under vacuum. Finally, the peptide was deprotected and cleaved of the resin by addition of a mixture of TFA\u2009:\u2009TIS\u2009:\u2009H2O . After 18\u201324\u2005h the cleavage cocktail was collected by filtration and the resin was washed with TFA (3\u00d70.5\u2005mL). The combined filtrates were concentrated and ice cold Et2O (\u223c8\u201310\u2010fold volume) was added. The suspension was centrifuged  and the ether phase was decanted. For HPLC purification, the peptide pellet was dissolved in H2O\u2009:\u2009ACN\u2009:\u2009TFA (1\u2009:\u20091\u2009:\u20090.001 v/v/v).pMPyE\u2010NRAEYSGLG (18N): Synthesis of 16N was achieved by microwave\u2010assisted solid phase peptide synthesis . The auxiliary was introduced according to the published procedure for the MPyE auxiliary2O/TIS (95\u2009:\u20092.5\u2009:\u20092.5 v/v/v) for 18\u2005h. After analyzing the resulting fractions with UPLC\u2010MS, the auxiliary peptide containing solutions were swiftly frozen for lyophilization to avoid decomposition of the product. Yield: 7.69\u2005mg, 53\u2009%. Note: 18N was stored as dry lyophilizate at \u221280\u2009\u00b0C to avoid auxiliary cleavage . UPLC\u2010MS: tR=2.87\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=1102.6 (C47H72N15O14S (M+H)+, calcd.: 1102.5), 552.1 (C47H73N15O14S (M+2H)2+, calcd.: 551.8); C47H71N15O14S (MW=1102.2\u2005g\u2009mol\u22121).MMPyE\u2010NRAEYSGLG (41N): Yield: 6.55\u2005\u03bcmol, 66\u2009%. UPLC\u2010MS: tR=3.71\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=1132.6 (C48H74N15O15S (M+H)+, calcd.: 1132.5), 566.9 (C48H75N15O15S (M+2H)2+, calcd.: 566.8); C48H73N15O15S (MW=1132.3\u2005g\u2009mol\u22121).MMPyE\u2010VRAEYSGLG (41V): Yield: 6.15\u2005\u03bcmol, 41\u2009%. UPLC\u2010MS: tR=4.33\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=1117.7 (C49H77N14O14S (M+H)+, calcd.: 1117.6), 559.4 (C49H78N14O14S (M+2H)2+, calcd.: 559.3); C48H74N14O13S (MW=1117.3\u2005g\u2009mol\u22121).Ligation of Model Peptides with Peptide Thioester: To the ligation buffer  3\u2005vol.% thiophenol was added and the mixture was transferred to a lyophilized mixture of auxiliary peptide (1\u2005equiv) and peptide thioester (1.5\u2005equiv) to a final concentration of 5\u2005mM auxiliary peptide. An argon atmosphere was applied to the reaction vessel. To monitor the progress of the reaction, aliquots were withdrawn from the ligation mixture, quenched with an aqueous solution of 0.1\u2009% TFA or 0.1\u2009% TFA, 2.5\u2009% hydrazine, 30\u2005mM TCEP and analyzed by UPLC\u2010MS. The progress of the ligation reaction was assessed by integration of the corresponding peak areas. After completion of the ligation, hydrazine and TCEP were added to the ligation solution. Ligated peptides showed partial rearrangement back to the thioester intermediate via N\u2192S acyl transfer due to the acidic conditions used during and shortly after purification. Swift lyophilization after purification minimizes rearrangement. Alternatively, peptide solutions containing high amounts of rearranged thioesters can be treated with a solution of NH4Ac  to a final pH of 5 to retrieve the amide.Ala\u2010Asn Ligation on pMPyE (20AN): 2\u2005\u03bcmol of para\u2010MPyE peptide 18N and 3\u2005\u03bcmol of peptide thioester 19A were allowed to react. The mixture was analyzed via UPLC\u2010MS after t=5\u2005min and t=24\u2005h : 2\u2005\u03bcmol of MMPyE\u2010peptide 41N and 3\u2005\u03bcmol of peptide thioester 19A were allowed to react for 72\u2005h. Yield: 1.02\u2005\u03bcmol, 51\u2009%. UPLC\u2010MS: tR=4.04\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=854.0 (C75H118N24O20S (M+2H)2+, calcd.: 853.4), 569.9 (C75H118N24O20S (M+3H)3+, calcd.: 569.3); C75H116N24O20S (MW=1705.9\u2005g\u2009mol\u22121).Leu\u2010Asn Ligation on MMPyE (42LN): 2\u2005\u03bcmol of MMPyE\u2010peptide 41N and 3\u2005\u03bcmol of peptide thioester 19L were allowed to react for 72\u2005h. Yield: 1.14\u2005\u03bcmol, 57\u2009%. UPLC\u2010MS: tR = 5.00\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=875.0 (C78H124N24O20S (M+2H)2+, calcd.: 874.5), 583.9 (C78H125N24O20S (M+3H)3+, calcd.: 583.3); C78H122N24O20S (MW=1748.0\u2005g\u22c5mol\u22121).Ala\u2010Val Ligation on MMPyE (42AV): 2\u2005\u03bcmol of MMPyE\u2010peptide 41V and 3\u2005\u03bcmol of peptide thioester 19A were allowed to react for 72\u2005h. Yield: 1.20\u2005\u03bcmol, 60\u2009%. UPLC\u2010MS: tR=6.07\u2005min (3\u201330\u2009% B in 8\u2005min); m/z=846.7 (C76H121N23O19S (M+2H)2+, calcd.: 845.9), 565.1 (C76H122N23O19S (M+3H)3+, calcd.: 564.3); C76H119N23O19S (MW=1691.0\u2005g\u2009mol\u22121).Leu\u2010Val Ligation on MMPyE (42LV): 2\u2005\u03bcmol of MMPyE\u2010peptide 41V and 3\u2005\u03bcmol of peptide thioester 19L were allowed to react for 120\u2005h. Yield: 0.58\u2005\u03bcmol, 29\u2009%. UPLC\u2010MS: tR=5.86\u2005min (3\u201335\u2009% B in 6\u2005min); m/z=867.5 (C76H127N23O19S (M+2H)2+, calcd.: 866.9), 578.9 (C76H128N23O19S (M+3H)3+, calcd.: 578.3); C76H125N23O19S (MW=1733.0\u2005g\u2009mol\u22121).Ligation with Model Peptide Selenoester: A lyophilized mixture of MMPyE peptide (1\u2005equiv) and peptide selenoester (2\u2005equiv) was dissolved in the ligation buffer , pH=6.2) to a final concentration of 5\u2005mM auxiliary peptide. An argon atmosphere was applied to the reaction vessel. To monitor the progress of the reaction, aliquots were withdrawn from the ligation mixture, quenched with an aqueous solution of 0.1\u2009% TFA or 0.1\u2009% TFA, 2.5\u2009% hydrazine, 30\u2005mM TCEP and analyzed by UPLC\u2010MS. The progress of the ligation reaction was assessed by integration of the corresponding peak areas. After completion of the ligation, hydrazine and TCEP were added to the ligation solution.Ala\u2010Asn Ligation on MMPyE (\u219242AN) with Selenoester 22A: 1\u2005\u03bcmol of MMPyE\u2010peptide 41N and 2\u2005\u03bcmol of peptide selenoester 22A allowed to react for 24\u2005h. Yield: 0.73\u2005\u03bcmol, 73\u2009%. UPLC\u2010MS: tR=4.05\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=854.4 (C75H118N24O20S (M+2H)2+, calcd.: 853.4), 570.1 (C75H119N24O20S (M+3H)3+, calcd.: 569.3); C75H116N24O20S (MW=1705.9\u2005g\u2009mol\u22121).Leu\u2010Val Ligation on MMPyE (\u219242LV) with Selenoester 22A: 0.5\u2005\u03bcmol of MMPyE\u2010peptide 41V and 1.0\u2005\u03bcmol of peptide selenoester 22L were allowed to react for 72\u2005h. Yield: 0.24\u2005\u03bcmol, 48\u2009%. UPLC\u2010MS: tR=5.01\u2005min (3\u201340\u2009% B in 6\u2005min); m/z=867.9 (C76H127N23O19S (M+2H)2+, calcd.: 866.9), 579.1 (C76H128N23O19S (M+3H)3+, calcd.: 578.3); C76H125N23O19S (MW=1733.0\u2005g\u2009mol\u22121).Auxiliary Cleavage from Model Ligation Products: Lyophilized ligation products were dissolved in the auxiliary cleavage mixture  to a final concentration of 1\u2005mM in plastic tubes. The closed lid was punctured to allow supply of oxygen. Note: Hydrazine is a known oxygen scavenger and auxiliary removal does not tolerate the presence of hydrazine.Removal of Auxiliary from Ligation Product AN (51AN): 500\u2005nmol of ligated peptide 42AN was incubated in the cleavage mixture for 3\u2005h. Yield: 250\u2005nmol, 50\u2009%. UPLC\u2010MS: tR=4.44\u2005min ; m/z=770.7 (C67H108N22O20 (M+2H)2+, calcd.: 770.4), 514.2 (C67H109N22O20 (M+3H)3+, calcd.: 513.9); C67H106N22O20 (MW=1538.8\u2005g\u2009mol\u22121).Removal of Auxiliary from Ligation Product AV (51AV): 500\u2005nmol of ligated peptide 42AV was incubated in the cleavage mixture for 6\u2005h. Yield: 180\u2005nmol, 36\u2009%. UPLC\u2010MS: tR=3.85\u2005min (then 3\u201330\u2009% B in 6\u2005min); m/z=763.2 (C68H111N21O19 (M+2H)2+, calcd.: 762.9), 509.2 (C68H112N21O19 (M+3H)3+, calcd.: 508.9); C68H109\u2005N21O19 (MW=1523.8\u2005g\u2009mol\u22121).Removal of Auxiliary from Ligation Product LN (51LN): 260\u2005nmol of ligated peptide 42LN was incubated in the cleavage mixture for 3\u2005h. Yield: 104\u2005nmol, 40\u2009%. UPLC\u2010MS: tR=5.16\u2005min ; m/z=791.7 (C70H114N22O20 (M+2H)2+, calcd.: 791.4), 528.1 (C70H115N22O20 (M+3H)3+, calcd.: 527.9); C70H112N22O20 (MW=1580.8\u2005g\u2009mol\u22121).Removal of Auxiliary from Ligation Product LV (51LV): 300\u2005nmol of ligated peptide 42AN was incubated in the cleavage mixture for 6\u2005h. Yield: 109\u2005nmol, 36\u2009%. UPLC\u2010MS: tR=4.14\u2005min (3\u201330\u2009% B in 6\u2005min); m/z=784.5 (C71H117N21O19 (M+2H)2+, calcd.: 783.9), 523.1 (C71H118N21O19 (M+3H)3+, calcd.: 523.0); C71H115N21O19 (MW=1566.8\u2005g\u2009mol\u22121).4 Thioester EIQALEEENAQLEQENAALEEEIAQLEY\u2010(APTTSTTS): The peptide was synthesized on a rink amide resin pre\u2010loaded with Hnb\u2010(StBu)Cys\u2010Gly via automated microwave assisted peptide\u2010synthesis . The peptide resin was treated with H2N\u2212OH\u2009\u22c5\u2009HCl , washed and deprotected with TFA\u2009:\u2009phenol\u2009:\u2009H2O\u2009:\u2009TIS (88\u2009:\u20095\u2009:\u20095\u2009:\u20092 v/v/v/v) for 2\u2005h. The precipitated crude peptide was shaken at 37\u2009\u00b0C in an aqueous buffer  containing 10\u2005vol.% MPA. The reactions was quenched with 10\u2005vol.% TFA. Preparative HPLC: 15\u201335\u2009% B in 40\u2005min. Yield: 0.43\u2005\u03bcmol, 31\u2009%, UPLC: tR=5.95\u2005min (15\u201335\u2009% B in 8\u2005min). The product was submitted to ligation without further characterization.4\u2010KIAQLKQKIQALKQENQQLEEENAALEY MMPyE\u2010(APTTSTTS): Synthesis was performed on a rink amide resin via automated microwave assisted peptide\u2010synthesis . For reductive alkylation 10\u2005equiv 40 and 30\u2005equiv NaCNBH3 were allowed to react for 24\u2005h. Preparative HPLC: 15\u201335\u2009% B in 40\u2005min. Yield: 771\u2005nmol, 57\u2009%. UPLC: tR=4.27\u2005min (15\u201335\u2009% B in 8\u2005min). The product was submitted to the ligation without further characterization.Ligation of 53 and 54 (\u219255): Peptide thioester 53 (315\u2005nmol) and auxiliary peptide 54 (210\u2005nmol) were dissolved in ligation buffer  and allowed to react for 120\u2005h. Yield: 53\u2005nmol, 25\u2009%. UPLC: tR=5.87\u2005min (15\u201335\u2009% B in 8\u2005min). The product was submitted to auxiliary cleavage without further characterization.8\u2010P4 (56)P1\u2010Muc5AC: Ligation product 55 (18\u2005nmol) was incubated in the cleavage mixture for 4\u2005h. Preparative HPLC: 15\u201335\u2009% B in 40\u2005min. Yield: 9.5\u2005nmol, 53\u2009%. UPLC: tR=6.6\u2005min (15\u201335\u2009% B in 8\u2005min); HRMS: m/z=1786.9876 (C522H862N139O214 (M+11H)7+, calcd.: 1786.7282), 1563.5361 (C522H863N139O214 (M+11H)8+, calcd.: 1563.5131), 1389.9659 (C522H864N139O214 (M+11H)9+, calcd.: 1389.9013), 1251.0593 (C522H865N139O214 (M+11H)10+, calcd.: 1251.0119), 1137.4254 (C522H866N139O214 (M+11H)11+, calcd.: 1137.3751), 1042.6994 (C522H867N139O214 (M+12H)12+, calcd.: 1042.6778).Synthesis of phosphorylated MMPyE\u2010CTD Peptide 57: Synthesis was performed on a Rink amide resin via MW\u2010SPPS . For reductive alkylation 7\u2005equiv 40 and 16\u2005equiv NaCNBH3 were allowed to react for 18\u2005h. The peptide was cleaved for 6\u2005h with TFA:H2O:phenol:EDT  protecting group to avoid formation of cleavage side\u2010product). Preparative HPLC: 3\u201340\u2009% B in 40\u2005min. Yield: 3.46\u2005\u03bcmol, 35\u2009%. UPLC\u2010MS: tR=3.45\u2005min (3\u201330\u2009% B in 4\u2005min); m/z=1172.4, (C104H148N23O37S (M+3H)3+, calcd.: 1172.5), m/z=783.3, (C104H148N23O37S (M+4H)4+, calcd.: 783), C104H150N23O46P3S (MW=2343.01\u2005g\u2009mol\u22121). UPLC\u2010MS: tR=2.53\u2005min (3\u201330\u2009% B in 4\u2005min); m/z=862.0, (C104H150N23O46P3S (M+3H)3+, calcd.: 861.6), C104H150N23O46P3S (MW=2581.9\u2005g\u2009mol\u22121).6\u2010[(CH2)2O]6CH2CO\u2010(YpSPTSPS)3 Hydrazide (58)His: The peptide was assembled on a chlorotriyl resin pre\u2010loaded with Fmoc\u2010hydrazine via automated solid\u2010phase peptide synthesis . After introduction of the PEG6\u2010chain (Fmoc\u2010HN\u2010[(CH2)2O]6\u2010COOH (5\u2005equiv), HATU  and DIPEA (15\u2005equiv) in DMF), capping and coupling of six histidines, the peptide was cleaved with TFA:H2O:phenol:EDT  for 3\u2005h. Preparative HPLC 3\u201340\u2009% B in 40\u2005min. Yield: 1.86\u2005\u03bcmol, 19\u2009%; 58: 2.15\u2005\u03bcmol, 22\u2009%. UPLC\u2010MS (58): tR=2.08\u2005min (3\u201050\u2009% B in 4\u2005min); m/z=1197.3, (C147H213N42O58P3 (M+3H)3+, calcd.: 1196.8), 898.8 (C147H210N42O49 (M+4H)4+, calcd.: 897.9), 719.2 (C147H210N42O49 (M+5H)5+, calcd.: 718.5).Formation of Thioester 59, Ligation with 57\u2009and Removal of MMPyE Group (60): Peptide hydrazide 58  was dissolved in H2O containing 200\u2005mM MPAA and 6\u2005M Gdn HCl (pH=3) and acetylacetone  was added. After 1\u2005h reaction at room temperature, the solution was transferred to a mixture of auxiliary peptide 57  in 100\u2005mM TCEP, 200\u2005mM Na2HPO4 and 6\u2005M Gdn HCl (pH=8.5). NaOH (5\u2005M) was added carefully by alternating addition over the vessel cap followed by vortexing to adjust the pH to 6.3. After 120\u2005h, the ligation was quenched by the addition of 5\u2005\u03bcl hydrazine solution (81\u2009% in H2O) and 10\u2005\u03bcl of TCEP (1\u2005M in H2O) and the resulting mixture was subjected to an Amicon Ultra Mass Filter from Merck Millipore  and washed twice. After lyophilization, the crude peptide mixture was dissolved in 100\u2005\u03bcl phosphate buffer  and purified via a His\u2010Tag kit using Ni2+ Agarose\u2010NTA beads. The resulting peptide solution was lyophilized and used i without further purification. The peptide mixture obtained after lyophilization was dissolved in 200\u2005\u03bcL of the auxiliary removal mixture  for 24\u2005h. Preparative HPLC: 3\u201340\u2009% B in 40\u2005min. Yield: 18\u2005nmol, 4\u2009% over 3 steps. UPLC\u2010MS: tR=5.47\u2005min (5\u201030\u2009% B in 8\u2005min); m/z=1195.1 (C243H350N62O103P6 (M+5H)5+, calcd.: 1195.1), 996.9 (C243H350N62O103P6 (M+6H)6+, calcd.: 996.0), m/z=854.1 (C243H350N62O103P6 (M+7H)7+, calcd.: 853.9) m/z=745.9 (C243H350N62O103P6 (M+8H)8+, calcd.: 747.3) m/z=664.3 (C243H350N62O103P6 (M+9H)9+, calcd.: 664.4), (C243H350N62O103P6 (MW=5970.3).Synthesis of MMPyE\u2010peptide 62, Formation of Thioester 63\u2009and Cyclization (64): Microwave assisted peptide\u2010synthesis was performed on a pre\u2010loaded chlorotrityl\u2010tentagel resin . For reductive alkylation 7\u2005equiv of 40 and 16\u2005equiv of NaCNBH3 were allowed to react for 18\u2005h. Approx, 1.0\u2005\u03bcmol MMPyE\u2010peptide 62 was cleaved from the resin with hexafluoroisopropanol/DCM (7\u2009:\u20093 v/v) and thioester 63 was formed according to the general procedure . The peptide was cleaved for 18\u2005h with TFA, H2O, phenol, thioanisole, EDT (82\u2009:\u20095\u2009:\u20095\u2009:\u20095\u2009:\u20093 v/v/v/v/v) and incubated in ligation buffer at 37\u2009\u00b0C for 2\u2005h. Preparative HPLC: 20\u201350\u2009% B in 40\u2005min. Yield: 89\u2005nmol, 9\u2009%. UPLC\u2010MS: tR=4.88\u2005min (20\u201350\u2009% B in 8\u2005min); m/z=1138.2, (C109H150N24O28S (M+2H)2+, calcd.: 1138.0), 758.9 (C109H151N24O28S (M+3H)3+, calcd.: 759.0), C109H148N24O28S (MW=2274.55\u2005g\u22c5mol\u22121).Cyclopeptide 65: 55\u2005nmol of ligation product 64 was incubated in the cleavage mixture for 12\u2005h. Preparative HPLC: 20\u201350\u2009% B in 40\u2005min. Yield: 24\u2005nmol, 44\u2009%. UPLC\u2010MS: tR=3.93\u2005min (20\u201350\u2009% B in 8\u2005min); m/z=1054.42 (C101H141N23O27 (M+2H)2+, calcd.: 1054.02), 703.01 (C101H142N23O27 (M+3H)3+, calcd.: 703.35), C101H139N23O27 (MW=2107.32). MALDI\u2010MS: m/z=2104 (C101H140N23O27 (M+H)+, calcd.: 2108).More detailed procedures and characterization data is provided in the Supporting Information.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the crystal, these components are organized in infinite zigzag chains via inter\u00admolecular hydrogen bonds. Weak inter\u00adactions between the chains lead to a three-dimensional network.The title salt consists of three components, comprising one di\u00adbenzyl\u00adammonium cation, [(C 14H16N+\u00b7C6H7AsNO3\u2212\u00b7H2O or [(C6H5CH2)2NH2][H2NC6H4As(OH)O2]\u00b7H2O, (I), was synthesized by mixing an aqueous solution of (4-amino\u00adphenyl)\u00adarsonic acid with an ethano\u00adlic solution of di\u00adbenzyl\u00adamine at room temperature. Compound I crystallizes in the monoclinic P21/c space group. The three components forming I are linked via N\u2014H\u22efO and O\u2014H\u22efO inter\u00admolecular hydrogen bonds, resulting in the propagation of an infinite zigzag chain. Additional weak inter\u00adactions between neighbouring chains, such as \u03c0\u2013\u03c0 and N\u2014H\u22efO contacts, involving phenyl rings, \u2013NH2 and \u2013As(OH)O3 functions, and H2O, respectively, lead to a three-dimensional network.The title salt, C This compound was employed for pharmaceutical applications, in particular against trypanosomal infection. Subsequently, in the early 20th century, Paul Ehrlich was inspired by this work to develop a new organoarsenic derivative, called Arsphenamine or Salvarsan  has been determined 2NH2][H2NC6H4As(OH)O2]\u00b7H2O (I).From a structural point of view, the crystal structure of phenyl\u00adarsonic acid was first solved in the early 1960s 2NH2]+, one hydrogen (4-amino\u00adphen\u00adyl)arsonate anion [H2NC6H5As(OH)O2]\u2212 and one water mol\u00adecule of solvation. The three components of I are linked together through inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds. The As atom of the anion is bonded to three O atoms and one carbon atom of the phenyl ring, describing a slightly distorted tetra\u00adhedral geometry . The As\u2014O bonds exhibit two distinct lengths: As\u2014O1 = 1.7267\u2005(10)\u2005\u00c5, and As\u2014O2 = 1.6730\u2005(10)\u2005\u00c5 and As\u2014O3 =1.6699\u2005(10)\u2005\u00c5, which can be considered to be identical. The As\u2014O1 distance is consistent with the presence of a hydroxyl group \u2005\u00c5; symmetry code: (iv) \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01, Table\u00a01et al., 2002para position to the arsonate function. Both functional groups are contained in the plane of the phenyl ring. The negative charge of [H2NC6H4As(OH)O2]\u2212 is compensated by the presence of one di\u00adbenzyl\u00adammonium cation, [(C6H5CH2)2NH2]+, whose NH2+ group is hydrogen bonded to the oxygen atom O3 of the arsonate function . Moreover, the di\u00adbenzyl\u00adammonium cation shows a syn\u2013anti conformation, displaying C\u2014C\u2014N\u2014C torsion angles of 57.65\u2005(16)\u00b0 and \u2212178.14\u2005(11)\u00b0, which are in the range of previous examples of X-ray structures involving [(C6H5CH2)2NH2]+ \u2005\u00c5; symmetry code: (v) 1\u00a0+\u00a0x, y, z] completes the composition of salt I. From a spectroscopic point of view, the infrared spectrum of I (ATR mode) highlights \u03bd(As\u2014C) and \u03bd(As\u2014O) absorption bands, which are characteristic of the arsonate function .The asymmetric unit of the title salt, which is depicted in Fig.\u00a013.I:At the supra\u00admolecular stage, two levels of organization can be observed in the crystal structure of a-axis direction resulting from the hydrogen-bonding inter\u00adactions \u00b0], with the oxygen atoms O3 of two arsonate moieties  and the O1 oxygen atom of an adjacent \u2013As(OH)O2 function [N2\u2014H2B\u22efO1ii = 3.0769\u2005(17)\u2005\u00c5] (symmetry codes as in Table\u00a01(ii) The association of chains leading to a three-dimensional network and resulting from a combination of weak inter\u00adactions Fig.\u00a04. Two typ4.et al., 20166H5As(OH)O2\u2212. To our knowledge, eleven examples including this fragment have already been identified: ammonium 4-nitro\u00adphenyl\u00adarsonate 2NH2]+, 117 hits incorporating such an entity were found in the Cambridge Structural Database.A search of the Cambridge Structural Database 2O] was prepared according to a previous work  and arsenic acid (As(OH)3O). The title salt was obtained by neutralization of an aqueous solution (20\u2005mL) of (4-amino\u00adphen\u00adyl)arsonic acid  with di\u00adbenzyl\u00adamine ((C6H5CH2)2NH)  dissolved in 20\u2005mL of ethanol. The mixture was stirred for about two\u2005h at room temperature (301\u2005K). After three days of slow solvent evaporation, colourless prism-shaped crystals of [(C6H5CH2)2NH2][H2NC6H4As(OH)O2]\u00b7H2O , suitable for an X-ray crystallographic analysis, were collected from the solvent (m.p. 393\u2005K). FT\u2013IR : 3447, 3304, 3187, 1595, 1501, 1454, 1096, 923, 878, 825,752, 735, 695. Elemental analysis  \u2013 analysis calculated for C20H23N2O3As\u00b70.25H2O (418.83), salt I partially dehydrated: C, 57.35; H, 5.66; N, 6.69; O, 12.41; found: C, 57.82; H, 5.61; N, 6.62; O, 12.37%.All chemicals were purchased from Sigma-Aldrich (Germany) and used without any further purification. (4-Amino\u00adphen\u00adyl)arsonic acid [H6.Uiso(H) = 1.5Ueq(O). C-bound hydrogen atoms were placed at calculated positions [C\u2014H = 0.95\u2005\u00c5 (aromatic) or 0.99\u2005\u00c5 (methyl\u00adene group)] and H atoms of the NH2 and OH terminal groups were placed geometrically  and refined as riding with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902300837X/dj2065sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698902300837X/dj2065Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902300837X/dj2065Isup3.cmlSupporting information file. DOI: 2297206CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The magnesium cation exhibits a distorted octa\u00adhedral coordination with two bidentate di\u00admeth\u00adoxy\u00adethane mol\u00adecules and a dinuclear aluminate anion, coordinated to Mg2+via oxido and hydroxido units. The anion is an oxido-bridged species, [HOAl(hfip)2(\u03bc-O)Al(hfip)3]2\u2013, with one Al3+ cation tetra\u00adhedrally coordinated by an oxido (O2\u2013) anion, a hydroxido anion, and two hfip groups, whereas the second Al3+ cation is coordinated by the oxido anion and three hfip groups.Partial hydrolysis of a sample of [Mg(dme) The nearly right angle involves the oxido and hydroxido groups (O\u2014Al1\u2014OH). The anion coordinates to the magnesium cation via hydroxido and oxido units, thus making these ligands \u03bc- and \u03bc3-bridges, respectively, resulting in an Mg1\u22efAl1 distance of 2.8074\u2005(3)\u2005\u00c5. The angles at the hydroxido and oxido bridges between Al1 and Mg1 are similar , whereas the angles involving \u03bc3-oxido and Al2 are more obtuse . The Mg2+ cation has a distorted octa\u00adhedral coordination with cis-O\u2014Mg\u2014O angles ranging from 76.40\u00b0 (2) to 101.00\u2005(2)\u00b0 and trans-O\u2014Mg\u2014O angles in the range 164.77\u2005(3)\u2013168.38\u2005(3)\u00b0. The O\u2014Mg\u2014O bite angles of the dme ligands [76.40\u2005(3) and 77.08\u2005(3)\u00b0] and the anion [76.99\u2005(2)\u00b0] are nearly identical.The title compound crystallizes in the monoclinic space group ly Fig.\u00a01. In the \u00c5] Fig.\u00a01. The tet2(CF3SO3)2] 2 \u20131.7444\u2005(10)\u2005\u00c5 in NMe4[Al(hfip)4] 4] , 2.1146\u2005(12)\u2005\u00c5, 77.49\u2005(5)\u00b0 in  sample 3][Al(hfip)4]2 + 2H2O \u2192 [Mg(dme)2{HOAl(hfip)2OAl(hfip)3}] + dme + 3hfipH.[Mg(dme)et al., 2010The crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2414314623007162/hb4443sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623007162/hb4443Isup2.hklStructure factors: contains datablock(s) I. DOI: 2156683CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two compounds have a structural overlap r.m.s. deviation of 0.27\u2005\u00c5. The pyran and seven-membered cyclo\u00adheptene rings in both structures adopt boat and boat-sofa conformations, respectively. Intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonds are responsible for the consolidation of the crystal packing of both mol\u00adecules. In addition to this, weak C\u2014H\u22ef\u03c0 inter\u00adactions are also observed. The inter\u00admolecular inter\u00adactions were qu\u00adanti\u00adfied and analysed using Hirshfeld surface analysis.The title compounds, C It is the fundamental component of many beneficial alkaloids, including atropine, scopolamine, and cocaine, whose derivatives are important in the treatment of neurological and psychiatric conditions such depression and panic disorder q2 = 1.021\u2005(2) and q3 = 0.391\u2005(2)\u2005\u00c5 in (I)q2 = 1.053\u2005(2) and q3 = 0.374\u2005(2)\u2005\u00c5 in (II)q2 = QT = 0.185\u2005(2)\u2005\u00c5 and \u03c6 = 43.9\u2005(1)\u00b0 [in (I)] and q2 = QT = 0.087\u2005(1)\u2005\u00c5 and \u03c6 = 47.1\u2005(1)\u00b0 [in (II)]. The cyclo\u00adhexene ring (C15\u2013C20) has a distorted sofa conformation in both (I)sC(C17) asymmetry parameters  in both compounds has a boat-sofa conformation, with puckering parameters , see Fig.\u00a04In the crystal of (I)via C\u2014H\u22efO inter\u00admolecular inter\u00adaction , see Fig.\u00a04In the crystal of (II)if Fig.\u00a05. The dim4.Crystal Explorer 21 et al., 2021To further characterize the inter\u00admolecular inter\u00adactions in the title compound, we carried out a Hirshfeld surface (HS) analysis Compound (II)6.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902300275X/zn2026sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S205698902300275X/zn2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698902300275X/zn2026IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2251053, 2251052CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The layers are further connected by \u03c0\u2013\u03c0 stacking inter\u00adactions.In the crystal of the title com\u00adpound, C\u2014H\u22efO hydro\u00adgen bonds link the mol\u00adecules, enclosing  14H11NO3, the di\u00adhydro\u00adquinoline core deviates slightly from planarity, indicated by the dihedral angle of 1.07\u2005(3)\u00b0 between the two six-membered rings. In the crystal, layers of mol\u00adecules almost parallel to the bc plane are formed by C\u2014H\u22efO hydro\u00adgen bonds. These are joined by \u03c0\u2013\u03c0 stacking inter\u00adactions. A Hirshfeld surface analysis revealed that the most important contributions to the crystal packing are from H\u22efH (36.0%), H\u22efC/C\u22efH (28.9%) and H\u22efO/O\u22efH (23.5%) inter\u00adactions. The evaluation of the electrostatic, dispersion and total energy frameworks indicates that the stabilization is dominated by the dispersion energy contribution. Moreover, the mol\u00adecular structure optimized by density functional theory (DFT) at the B3LYP/6-311G level is com\u00adpared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.In the title mol\u00adecule, C Moreover, a Hirshfeld surface analysis and inter\u00adaction energy and energy framework calculations were performed. The mol\u00adecular structure optimized by density functional theory (DFT) at the B3LYP/6-311G level is com\u00adpared with the experimentally determined mol\u00adecular structure in the solid state.2.A (C1\u2013C5/N1) and B (C4\u2013C9) rings. Atoms O1, O2, O3, C10, C13 and C14 are \u22120.1294\u2005(11), 0.1907\u2005(12), \u22120.2708\u2005(15), 0.0177\u2005(14), \u22120.0267\u2005(13) and 0.0953\u2005(23)\u2005\u00c5 from the least-squares plane of the A ring. The O2\u2014C13 [1.3123\u2005(17)\u2005\u00c5] and O3\u2014C13 [1.1955\u2005(16)\u2005\u00c5] distances in the ester group indicate localized single and double bonds, rather than delocalized bonding arrangements. The O2\u2014C13\u2014O3 bond angle [122.55\u2005(12)\u00b0] seems to be slightly increased with respect to that present in a free acid bis\u00ad(nicotinamide-\u03baN1)zinc(II)  rings  to form a triperiodic network.In the crystal, C\u2014H\u22efO hydro\u00adgen bonds Table\u00a01 link thene Fig.\u00a02. These l4.CrystalExplorer ] and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efC, C\u22efO/O\u22efC, H\u22efN/N\u22efH, C\u22efN/N\u22efC and N\u22efO/O\u22efN contacts \u2013(i), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH, contributing 36.0% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydro\u00adgen content of the mol\u00adecule with the tip at de = di = 1.22\u2005\u00c5. In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions, the pair of characteristic wings resulting in the fingerprint plot delineated into H\u22efC/C\u22efH contacts [Fig.\u00a06c)] have a 28.9% contribution to the HS, with the tips at de + di = 2.68\u2005\u00c5. The pair of the scattered points of spikes resulting in the fingerprint plot delineated into H\u22efO/O\u22efH contacts [Fig.\u00a06d)], with a 23.5% contribution to the HS, has an almost symmetric distribution of points, with the tips at de + di = 2.44\u2005\u00c5. The C\u22efC contacts [Fig.\u00a06e)] appear as an arrow-shaped distribution of points and have a contribution of 7.0% to the HS with the tip at de = di = 1.69\u2005\u00c5. The tiny spikes of C\u22efO/O\u22efC contacts [Fig.\u00a06f)], with a 2.5% contribution to the HS, are visible at de + di = 3.58\u2005\u00c5. Finally, the H\u22efN/N\u22efH [Fig.\u00a06g)], C\u22efN/N\u22efC [Fig.\u00a06h)] and N\u22efO/O\u22efN [Fig.\u00a06i)] contacts contribute 1.4, 0.4 and 0.4%, respectively, to the HS.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title com\u00adpound, a Hirshfeld surface (HS) analysis \u2013(c), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions play the major role in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange\u2013repulsion (Erep) energies , Edis (green cylinders) and Etot (blue cylinders), and are shown in Figs.\u00a08a)\u2013(c). The evaluation of the electrostatic, dispersion and total energy frameworks indicates that in the title com\u00adpound the stabilization is dominated by the dispersion energy contribution.Using 6.GAUSSIAN09  using the standard B3LYP functional and the 6311G basis set  derived from the conceptual DFT calculations are given in Table\u00a03E = ELUMO \u2212 EHOMO] , with layer-by-layer connections approximately parallel to  and tetra-n-butyl\u00adammonium bromide . The reaction mixture was stirred at room tem\u00adper\u00ada\u00adture in DMF for 6\u2005h. After removal of the formed salts, the solvent was evaporated under reduced pressure and the residue obtained was dissolved in di\u00adchloro\u00admethane. The organic phase was dried over Na2SO4 and then concentrated in vacuo. A pure com\u00adpound was obtained after recrystallization from di\u00adchloro\u00admethane/hexane (2:3 v/v).To a solution of methyl 2-oxo-1,2-di\u00adhydro\u00adquinoline-4-car\u00adbox\u00adyl\u00adate (4.47\u2005mmol) in 10\u2005ml of di\u00admethyl\u00adformamide (DMF) were added propargyl bromide (9.83\u2005mmol), K10.1107/S2056989023007557/wm5688sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023007557/wm5688Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007557/wm5688Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023007557/wm5688Isup4.cdxSupporting information file. DOI: 2291603CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "G\u03b3- and A\u03b3-globin genes were examined by DNA analysis and rapid diagnosis of HPFH mutations were developed by PCR-based methods. Twenty subjects with five different mutations were identified including three known mutations, \u2212\u00a0202 A\u03b3 (C>T) (n\u2009=\u20093), \u2212\u00a0196 A\u03b3 (C>T) (n\u2009=\u20093), and \u2212\u00a0158 A\u03b3 (C>T) (n\u2009=\u200912), and two novel mutations, \u2212\u00a0117 A\u03b3 (G>C) (n\u2009=\u20091) and \u2212\u00a0530 G\u03b3 (A>G) (n\u2009=\u20091). Interaction of the \u2212\u00a0117 A\u03b3 (G>C) and Hb E (HBB:c.79G>A) resulted in elevation of Hb F to the level of 13.5%. Two plain heterozygous subjects with \u2212\u00a0530 G\u03b3 (A>G) had marginally elevated Hb F with 1.9% and 3.0%, whereas the proband with homozygous \u2212\u00a0530 G\u03b3 (A>G) had elevated Hb F of 11.5%. Functional prediction indicated that the \u2212\u00a0117 A\u03b3 (G>C) and \u2212\u00a0530 G\u03b3 (A>G) mutations dramatically alter the binding of transcription factors to respective \u03b3-globin gene promotors, especially the CCAAT and GATA-1 transcription factors. Diverse heterogeneity of non-deletional HFPH with both known and new mutations, and complex interactions of them with other forms of thalassemia are encountered in Thai population.High Hb F determinants are genetic defects associated with increased expression of hemoglobin F in adult life, classified as deletional and non-deletional forms. We report the first description of non-deletional hereditary persistence of fetal hemoglobin (HFPH) in Thailand. Study was done on 388 subjects suspected of non-deletional HPFH with elevated Hb F expression. Mutations in the  In Thailand, high prevalence of hemoglobinopathies has been documented including 20\u201330% of \u03b1-thalassemia, 3\u20139% of \u03b2-thalassemia, 20\u201330% of Hb E (HBB:c.79G>A), 1\u20138% of Hb Constant Spring (HBA2:c.427T>C) and Hb Pakse\u2032 (HBA2:c.429A>T), and other structural Hb variants and high Hb F determinants. These lead to diverse heterogeneity and complex thalassemia syndromes in the country5. Accurate diagnosis of these hemoglobinopathies is important for promoting appropriate management, genetic counseling, and a prevention and control program of thalassemia in the region.The inherited disorders of hemoglobin (Hb) or hemoglobinopathies are the commonest human monogenic diseases, found in about 7% of the world population. These can be broadly classified into 3 groups, structural Hb variants, thalassemia and hereditary persistence of fetal hemoglobin (HPFH)7. Since co-inheritance of these high Hb F determinants in \u03b2-thalassemia disease has an ameliorating effect on the disease severity, identification of them in routine practice is important. At the molecular level, they could be classified into deletional and non-deletional high Hb F determinants. While the former involves several large DNA deletions removing \u03b4- and \u03b2-globin genes, the latter is usually caused by point mutations on G\u03b3- or A\u03b3-globin gene promoters affecting the binding of related transcription factors5.During early childhood, the level of Hb F normally declines to less than 1\u20132% of total Hb. The level of Hb F is therefore less than 1\u20132% in normal adult. High Hb F determinants are a group of genetic defects associated with increased expression of Hb F in adult life. The conditions include \u03b4\u03b2-thalassemia, \u03b3\u03b4\u03b2-thalassemia and hereditary persistence of fetal hemoglobin (HPFH). While \u03b4\u03b2-thalassemia and \u03b3\u03b4\u03b2-thalassemia are usually associated with elevated Hb F and hypochromic microcytic red blood cell indices, HPFH is associated with higher Hb F expression with normal red blood cells. Homozygous or compound heterozygous for \u03b4\u03b2-thalassemia and \u03b2-thalassemia may have clinical phenotype of non-transfusion-dependent thalassemia or transfusion-dependent thalassemia. In contrast, homozygous HPFH or compound heterozygous HPFH and \u03b2-thalassemia usually have no clinical symptom. However, these clinical phenotypes are generally overlapped which renders their differentiation in routine setting difficult unless DNA analysis is performed0-thalassemia (12.6\u00a0kb deletion) (NG_000007.3:g.64383_76994), Indian deletion-inversion G\u03b3(A\u03b3\u03b4\u03b2)0-thalassemia , Chinese A\u03b3\u03b4\u03b20-thalassemia (78.9\u00a0kb deletion) (NG_000007.3:g.48795_127698del), \u03b4\u03b20-thalassemia (11.3\u00a0kb deletion) (NG_000007.3:g.60045_71313delinsTACATTAAGAGATACCTTAATG), Siriraj A\u03b3\u03b4\u03b20-thalassemia (~\u2009118\u00a0kb deletion) (AC104389.8:g.52507_165744), Thai deletion-inversion-insertion A\u03b3\u03b4\u03b20-thalassemia  and Vietnamese/SEA HPFH (27\u00a0kb deletion) (NG_000007.3:g.64384_76993del)10. However, non-deletional form of HFPH has rarely been described. This study provides for the first time the molecular description of non-deletional HFPH in Thailand including known and novel mutations affecting the CCAAT and GATA-1 transcription factors binding.In Thailand, several deletional forms of \u03b4\u03b2-thalassemia and HPFH have been documented. These included HPFH-6 (79.3\u00a0kb deletion) (NG_000007.3:g.45595_124872), \u03b4\u03b210. These included subjects with normal \u03b2-globin gene but Hb F\u2009\u2265\u20091.0% (n\u2009=\u200981), Hb E heterozygotes with Hb F\u2009\u2265\u20091.0% (n\u2009=\u2009287), \u03b2-thalassemia carriers with Hb F>10% (n\u2009=\u20096), and homozygous Hb E with Hb F>20% (n\u2009=\u200914). For comparison, normal individuals with Hb F\u2009<\u20091.0% (n\u2009=\u200960) were also analyzed. Hematological data is routinely recorded on standard automated blood cell counter. Hb analysis is performed using automated capillary electrophoresis system  or automated high-performance liquid chromatography (HPLC) .This study was conducted in accordance with the Declaration of Helsinki and ethical approval of this study protocol was obtained from the Institutional Review Board of Khon Kaen University, Thailand (HE652154). Left-over blood specimens of 388 subjects suspected of non-deletional HPFH were selectively recruited at our routine thalassemia diagnostic service at Khon Kaen University, Thailand. They were all negative for deletional forms of high Hb F determinants previously found in ThailandSEA, --THAI, -\u03b13.7, -\u03b14.2, Hb Constant Spring, and Hb Pakse\u2032), \u03b2-thalassemia, deletional high Hb F determinants, and Kr\u00fcppel-like factor 1 (KLF1) mutations found in Thai population were identified by PCR-based methods as described previously14. G\u03b3- and A\u03b3-globin promoter mutations were examined by DNA sequencing on ABI PRISM\u2122 3730 XL analyzer  using primers F35 and \u03b3515, and F229 and \u03b33516. Sequences of all primers used in this study are listed in the Supplementary Table Common \u03b1-thalassemia (--G\u03b3- globin promoter (C>T) (HBG2:c.\u2212\u00a0211C>T) and \u2212\u00a0158 A\u03b3-globin promoter (C>T) (HBG1:c.\u2212\u00a0211C>T) was developed as shown in Supplementary Fig. G\u03b3- and A\u03b3-globin gene promoters was done using primers \u03b3415 and \u03b35 (577\u00a0bp in length), and F22 & \u03b35 (639\u00a0bp in length), respectively. With this assay, the amplified product was digested to completion with XmnI restriction enzyme (5\u2032-GAANN\u25bcNNTTC-3\u2032) . After digestion, the 577\u00a0bp of \u2212\u00a0158 G\u03b3-globin promoter with T allele [XmnI (+)] was digested into two fragments with 402\u00a0bp and 175\u00a0bp in lengths, and the 639\u00a0bp fragment for the \u2212\u00a0158 A\u03b3- globin promoter with T allele [XmnI (+)] was digested into two fragments with 464\u00a0bp and 175\u00a0bp in lengths. The \u2212\u00a0158 G\u03b3- and A\u03b3-globin promoters with C allele [XmnI (\u2212)] remain undigested16.The PCR-restriction fragment length polymorphism (PCR\u2013RFLP) assay for detection of \u2212\u00a0158 A\u03b3-globin (C>T) (HBG1:c.\u2212\u00a0255C>T)  (HBG1:c.\u2212\u00a0249C>T)  (HBG1:c.\u2212\u00a0170G>C)  (HBG2:c \u2212\u00a0583A>G) , \u2212\u00a0196 A\u03b3-globin (C>T), and \u2212\u00a0117 A\u03b3-globin (G>C) mutations. Similarly, primers (F40 & \u03b35) were used to produce the 795\u00a0bp internal control fragment for \u2212\u00a0530 G\u03b3-globin (A>G) mutation. Specific primer pairs (F38 & F22), (F39 & F22), (G211 & \u03b35), and (F41 & F40) were used to generate specific fragments of 444, 450, 150, and 276 bps in length for the \u2212\u00a0202 A\u03b3-globin (C>T), \u2212\u00a0196 A\u03b3-globin (C>T), \u2212\u00a0117 A\u03b3-globin (G>C), and \u2212\u00a0530 G\u03b3-globin (A>G), respectively. The PCR mixture (50\u00a0\u03bcl) contains 50\u2013200\u00a0ng genomic DNA, 30\u00a0pmol each primer, 200\u00a0\u03bcM dNTPs and 1 unit Taq DNA polymerase  in 10 mM\u00a0Tris-HCl (pH 8.3), 50 mM\u00a0KCl, 0.01% gelatin and 3 mM\u00a0MgCl2. The amplification reaction was carried out on a T-Personal Thermocycler . A total of 30 cycles after initial heating at 94\u00a0\u00b0C for 3\u00a0min was performed under the following PCR condition: 93\u00a0\u00b0C 30\u00a0s, 62\u00a0\u00b0C 30\u00a0s, and 72\u00a0\u00b0C for 1\u00a0min. The amplified PCR product was separated on 2.0% agarose gel electrophoresis and visualized under UV light after ethidium bromide staining.Allele-specific PCR assays were developed for rapid identification of four non-deletional HPFH mutations including \u2212\u00a0202 HincII, G\u03b3-HindIII, A\u03b3-HindIII, \u03c8\u03b2-HincII, 3\u2032\u03c8\u03b2-HincII, \u03b2-AvaII and 3\u2032\u03b2-BamHI were determined using PCR\u2013RFLP assays as described previously17.Seven polymorphic restriction sites on \u03b2-globin gene cluster including \u03b5-https://tfbind.hgc.jp/)18 was used to compare the binding affinity of transcription factors to the promoters of \u03b3-globin genes with wild-type sequences and their mutant counterparts including \u2212\u00a0117 A\u03b3 (G>A), \u2212\u00a0117 A\u03b3 (G>C), \u2212\u00a0114 A\u03b3 (C>T), \u2212\u00a0530 G\u03b3 (A>G), and \u2212\u00a0533 to \u2212\u00a0529 (-ATAAG) mutations.The online TFBIND software (G\u03b3- and A\u03b3-globin genes was selectively carried out in 177 subjects with Hb F>5.0%. Fourteen subjects (7.9%) with five mutations in the \u03b3-globin gene promoters were identified including three known mutations, \u2212\u00a0202 A\u03b3 (C>T) (n\u2009=\u20093), \u2212\u00a0196 A\u03b3 (C>T) (n\u2009=\u20093), and \u2212\u00a0158 A\u03b3 (C>T) (n\u2009=\u20096), and two novel mutations, \u2212\u00a0117 A\u03b3 (G>C) (n\u2009=\u20091) and \u2212\u00a0530 G\u03b3 (A>G) (n\u2009=\u20091). All mutations but the \u2212\u00a0530 G\u03b3 (A>G) were identified in heterozygotic form. Rapid PCR diagnosis based on PCR\u2013RFLP assays  mutation on PCR\u2013RFLP based assay. No mutation was detected in 60 normal subjects with Hb F\u2009<\u20091.0%. Therefore, a total of 20 of 388 (5.1%) recruited subjects were found to carry HPFH mutations. These included in total \u2212\u00a0202 A\u03b3 (C>T) (n\u2009=\u20093), \u2212\u00a0196 A\u03b3 (C>T) (n\u2009=\u20093), \u2212\u00a0158 A\u03b3 (C>T) (n\u2009=\u200912), \u2212\u00a0117 A\u03b3 (G>C) (n\u2009=\u20091) and \u2212\u00a0530 G\u03b3 (A>G) (n\u2009=\u20091). As shown in Table A\u03b3 (C>T) HPFH mutation and Hb F 27.1% was a boy (2-yr-old) who was found to be a carrier of \u03b20-thalassemia (\u03b217(AAG>TAG), HBB:c.52A>T) and \u03b1+-thalassemia (3.7\u00a0kb deletion). This boy was therefore a triple heterozygote for A\u03b3-HPFH, \u03b20-thalassemia and \u03b1+-thalassemia, a hitherto undescribed complex condition. Extended family analysis indicated that the \u2212\u00a0158 A\u03b3 (C>T) mutation was detected in trans to the \u03b20-thalassemia gene. He had Hb A2 of 4.3%, still within diagnostic range for a \u03b2-thalassemia trait.Among 388 subjects recruited DNA sequencing of +-Thalassemia was detected in 8 of 20 HPFH subjects with relatively decreased Hb F levels as compared to those with the same HPFH mutations but without \u03b1-thalassemia. The overall hematological parameters, Hb analysis results as well as \u03b1- and \u03b2-globin genotypes of these 20 non-deletional HPFH were summarized in Table No mutation in both \u03b3-globin genes was identified in subjects with homozygous Hb E with unusually high Hb F level. Further screening for the KLF1 mutations previously described in Thai population showed that 3 of these 20 subjects with HPFH  carried the KLF1 mutations i.e., H299D (NG_013087.1:g.6869C>G) (n\u2009=\u20091), T334R (NG_013087.1:g.7231C>G) (n\u2009=\u20091) and G176Afs*179 (NG_013087.1:g.6493_6499dupCGGCGCC) (n\u2009=\u20091). \u03b1G\u03b3 (A>G) novel mutation is located at the GATA-1 transcription factor binding motif of G\u03b3-globin gene promoter and is identified in homozygotic form, further family analysis was carried out as shown in Fig.\u00a0G\u03b3 (A>G) mutation. Apparently, heterozygosity for the \u2212\u00a0530 G\u03b3 (A>G) mutation is associated with normal hematological features and marginally elevated Hb F (1.9% in the mother and 3.0% in the sister). The father had alternatively reduced Hb F (0.3%) due to a co-inheritance of \u03b1+-thalassemia (3.7\u00a0kb deletion) since he was a double heterozygote for G\u03b3-HPFH and \u03b1+-thalassemia. In all members, the levels of Hb A2 were within normal range (2.4\u20132.6%). The proband\u2019s wife (27-year-old) was a patient with Hb E-\u03b2+-thalassemia with mild hypochromic microcytic anemia with Hb 10.1\u00a0g/dL, MCV 52.7 fL and MCH 18.6\u00a0pg. Therefore, they were at risk of having a child with compound G\u03b3-HPFH/\u03b2+-thalassemia or G\u03b3-HPFH/Hb E syndrome. In addition, screening for KLF1 mutations previously described in Thai population14 yielded negative results in all members. \u03b2-Globin gene haplotype analysis on 7 polymorphic restriction sites within \u03b2-globin gene cluster as described in the \u201cG\u03b3 (A>G) mutation was linked to the \u03b2-globin gene haplotype (-\u2009++-+-+) in this Thai family and pointed to the same origin of this G\u03b3-HPFH in the father and the mother. Appropriate genetic counselling was provided to the family members.Since the \u2212\u00a0530 0-thalassemia and A\u03b3\u03b4\u03b20-thalassemia. At least 7 different deletional forms of HPFH and \u03b4\u03b20-thalassemia have been characterized in Thailand10. In contrast, the molecular basis of non-deletional HPFH in Thailand has not been investigated. This study represents the first extensive study of non-deletional HPFH among Thai population. At present, around 30 non-deletional HFPH mutations on both G\u03b3- and A\u03b3-globin genes have been characterized worldwide. These include 15 mutations each on G\u03b3-globin and A\u03b3-globin genes 19. We have now reported for the first time in Thai population, five different HPFH mutations found in 20 subjects including four A\u03b3-HPFH and a G\u03b3-HPFH. Of these five HPFH mutations, three known mutations were \u2212\u00a0202 A\u03b3 (C>T) (n\u2009=\u20093), \u2212\u00a0196 A\u03b3 (C>T) (n\u2009=\u20093) and \u2212\u00a0158 A\u03b3 (C>T) (n\u2009=\u200912). Two novel mutations namely \u2212\u00a0117 A\u03b3 (G>C) and \u2212\u00a0530 G\u03b3 (A>G) were unexpectedly detected. As shown in Table In Thailand, we have extensively investigated the molecular basis of deletional form of HPFH and other high Hb F determinants including \u03b4\u03b2A\u03b3 (C>T) and the Italian/Chinese \u2212\u00a0196 A\u03b3 (C>T), are located within the G-rich area upstream of the \u2212\u00a0195 to \u2212\u00a0202 of \u03b3-globin gene. This DNA region is known to be the binding site of a ubiquitous transcription factor Sp1. As compared to the wild-type sequence, these two mutations decreased the binding of Sp1 on gel-shift experiment22. It has also been suggested that mutations in this G-rich sequence disrupt an intramolecular triplex proposed to be the binding site of a repressor, thereby increasing expression of \u03b3-globin gene23. Carriers of the \u2212\u00a0202 A\u03b3 (C>T) and \u2212\u00a0196 A\u03b3 (C>T) reported previously had Hb F in the ranges of 1.6\u20133.9% and 12\u201321%, respectively23. In our study, the three carriers of the \u2212\u00a0196 A\u03b3 (C>T) had as expected the average Hb F of 14.3\u2009\u00b1\u20091.9% (Table A\u03b3 (C>T) demonstrated higher Hb F levels with the average of 9.9\u2009\u00b1\u20091.6% as compared to the previously reported cases, possibly due to the presence of Hb E and the \u2212\u00a0158 G\u03b3 XmnI (\u2009+) in all Thai subjects. In addition, two of them also carried the KLF1 mutations (H299D & T334R) (case no. 2 & 3), known to be associated with increased Hb F expression in Hb E syndrome14.The Black \u2212\u00a0202 A\u03b3 (C>T) or the Cretan HPFH was originally described in three unrelated Greek adults with slightly increased Hb F level (2.9\u20135.1%) and normal hematological parameters. The \u2212\u00a0158 A\u03b3 (C>T) mutation has presumably resulted from a gene conversion event24. It is noteworthy that this form of HPFH was the most common one in Thai population, being detected in 12 of 20 Thai non-deletional HPFH subjects in this study (Table A\u03b3 (C>T) mutation on Hb F production can be raised. We found that this mutation is associated in cis with the \u2212\u00a0158 G\u03b3 XmnI (\u2009+) polymorphism in Thai population. It has been noted that a 240-kDa activator protein, a member of the CAAT/enhancer-binding proteins family, binds to \u2212\u00a0158 to -\u2212\u00a0161 nucleotides of \u03b3-globin gene promoter and induces expression of \u03b3-globin gene. This may explain the effect of \u2212\u00a0158 G\u03b3 XmnI (+) (C>T) and \u2212\u00a0158 A\u03b3 (C>T) to elevated \u03b3-globin gene expression25. While the \u2212\u00a0158 G\u03b3 XmnI (+) (C>T) polymorphism is associated with marginally elevated Hb F during erythropoietic stress, the \u2212\u00a0158 A\u03b3 (C>T) mutation is associated with higher Hb F expression with average of 7.8\u2009\u00b1\u20096.8% (Table A\u03b3-globin gene is more effective in competition with G\u03b3-globin gene for the Locus Control Region (LCR) in the adult stage25. The combined action of \u2212\u00a0158 A\u03b3 (C>T) in cis with \u2212\u00a0158 G\u03b3 (C>T) may lead further to higher Hb F production than having \u2212\u00a0158 G\u03b3 (C>T) alone24. In addition, study in Chinese and Thai subjects has identified that the \u2212\u00a0158 G\u03b3 XmnI (+) (C>T) was linked to the\u2009+\u200925 (G>A) polymorphism of A\u03b3-globin promoter (rs368698783), the binding motif of Ly-1 antibody reactive (LYAR) transcription factor. This polymorphism decreased the binding efficiency of the repressor of \u03b3-globin genes leading to increased Hb F production26. We found that all Thai subjects with \u2212\u00a0158 A\u03b3 (C>T) HPFH mutation also carried the \u2212\u00a0158 XmnI G\u03b3 (+) and the\u2009+\u200925 A\u03b3 (G>A) polymorphism. This should explain the higher Hb F production in these Thai subjects  found with the HPFH mutation alone or in combinations several common hemoglobinopathies including Hb E, \u03b2-thalassemia, \u03b1-thalassemia, and KLF1 mutation (G176Afs*179). The lowest Hb F of 2.1% was found in a heterozygous subject with the \u2212\u00a0158 A\u03b3 (C>T) in combination with Hb E and \u03b1+-thalassemia (3.7\u00a0kb deletion). This is not unexpected since it has been known that co-inheritance of \u03b1-thalassemia can lead to the reduced Hb F level in several hemoglobinopathies29. Of interest is the finding of subject with complex interaction of the \u2212\u00a0158 A\u03b3 (C>T), \u03b1+-thalassemia (3.7\u00a0kb deletion), and \u03b20-thalassemia (\u03b217(AAG>TAG)) (Table 2 (4.3%) and as high as 27.1% Hb F 30. This is in contrast with the deletional form of high Hb F determinants in which co-inheritance with \u03b2-thalassemia is associated with normal Hb A2 level5. Although diagnosis of a \u03b2-thalassemia heterozygote with this complex interaction seen in the case no. 17 is not altered due to elevated Hb A2, an unusually increased Hb F (27.1%) in heterozygous \u03b2-thalassemia, as seen in Thai subject, might be a good marker for a co-inheritance of HPFH in \u03b2-thalassemia, requiring further investigation. We recommend therefore to investigate all cases of heterozygous \u03b2-thalassemia with Hb F higher than 2% for further investigation of a possible co-inheritance of HPFH. This is a very important and useful information at genetic counselling since co-inheritance of HPFH can ameliorate the severity of \u03b2-thalassemia disease3. The last case in this group of HPFH with \u2212\u00a0158 A\u03b3 (C>T) mutation is an adult male encountered with a homozygous for this mutation who had 7.6% Hb F. He also carried the heterozygosity for KLF1 mutation (p.G176Afs*179), and \u03b1+-thalassemia (3.7\u00a0kb deletion). Homozygosity for a \u2212\u00a0158 XmnI G\u03b3 (+) was not unexpectedly noted due to the linkage of these two mutations. Again, high Hb F with normal level of Hb A2 and other hematological parameters , CCAAT displacement protein (CDP), and an erythroid specific protein NFE132. It has been shown that the Greek/Black/Sardinian \u2212\u00a0117 A\u03b3 (G>A) and Japanese \u2212\u00a0114 G\u03b3 (C>T) HPFH mutations slightly increased the binding of CP1 and CDP but reduced the binding of NFE1 to the distal CCAAT motif32. A novel mutation at the same region, [\u2212\u00a0117 A\u03b3 (G>C)] identified in Thai subject with Hb E heterozygote in this study was associated with 13.5% Hb F. It is conceivable that this Thai \u2212\u00a0117 A\u03b3 (G>C) HPFH mutation should behave similar mechanism with that of the Greek/Black/Sardinian \u2212\u00a0117 A\u03b3 (G>A) HPFH mutation. Prediction of transcription factors binding to the region using the TFBIND program18 in comparison between the wild-type promoter, \u2212\u00a0117 A\u03b3 (G>A) Greek/Black/Sardinian HPFH, \u2212\u00a0117 A\u03b3 (G>C) Thai HPFH and \u2212\u00a0114 G\u03b3 (C>T) Japanese HPFH was carried out as shown in Table RRCCAATSA) for the CCAAT box as shown in Table A\u03b3 (G>A) with score of 0.922056. The Thai \u2212\u00a0117 A\u03b3 (G>C) and the Japanese \u2212\u00a0114 G\u03b3 (C>T) had decreased scores of 0.824343 and 0.797797, respectively.Unlike other globin genes which contain only one CCAAT motif, \u03b3-globin gene has duplicated CCAAT sequences. The proximal CCAAT motif is located at -88 nucleotide and the distal one is found at \u2212\u00a0115 regions. The proximal CCAAT motif is corresponding to the CCAAT motif of \u03b2-globin gene in which mutations in this motif result in reduced \u03b2-globin gene expression and \u03b2-thalassemia pursue. In contrast, mutations in the distal CCAAT motif of \u03b3-globin gene results in higher \u03b3-globin expression and HPFH phenotypeG\u03b3-globin gene has been proposed as a negative regulatory element based on study in transiently transfected K562 cell33. The Iranian \u2212\u00a0567 G\u03b3 (T>G) HPFH mutation (HBG2:c.\u2212\u00a0620\u00a0T>G) which changed a GATA-1 binding motif to GAGA sequence (AGATAA>AGAGAA) was associated with increased Hb F of 5.9% and 10.2% in two Iranian subjects33. The five bp deletion between \u2212\u00a0533 to \u2212\u00a0529 (-ATAAG) of G\u03b3 globin gene (HBG2:c.\u2212\u00a0582_\u2212\u00a0586del ATAAG), located at the GATA-1 binding site was also associated with HPFH phenotype in an Indian family34. Therefore, alteration of GATA-1 and related repressor proteins bindings to the motif should result in up-regulation of \u03b3-globin gene expression. In contrast, the Thai \u2212\u00a0530 G\u03b3 (A>G) HPFH mutation which is located at the same region of GATA-1 binding motif (AGATAA>AGATAG) may have less effect on G\u03b3-globin gene expression since it does not modify the GATA-1 binding site (A/T)GATA(A/G) at this position significantly. Therefore, as shown in Table silico analysis of GATA-1 related transcription factors binding of the Thai \u2212\u00a0530 G\u03b3-HPFH using the online TFBIND program showed less changes on the similarity scores as compared to the wild-type sequence which contrasts with the \u2212\u00a0533 to \u2212\u00a0529 (-ATAAG) Indian HPFH mutation which reduced binding of all GATA-1 isoforms. As shown in the table, we found that the Thai HPFH mutation had slight increased binding scores of two GATA-1 isoforms and decreased binding scores for another two GATA-1 isoforms. The mechanisms underlying up-regulation of \u03b3-globin gene in these HPFH mutations may be difference. Accordingly, the effect of the \u2212\u00a0530 G\u03b3 (A>G) Thai HPFH mutation on the G\u03b3-globin gene expression could be minimal. This might explain the marginal elevation of Hb F (1.9% and 3.0%) observed in pure heterozygotic form of the mother and the sister of the proband and indicated that two copies of the \u2212\u00a0530 G\u03b3 (A>G) mutation in homozygote state is required for dramatically increased in Hb F (11.5%) as seen in the proband  and \u2212\u00a0158 XmnI G\u03b3 (\u2212) had normal Hb F level (0.3%) due to a co-inheritance of \u03b1+-thalassemia. It is evidenced from the Indian and Thai HPFH families that subjects with combined non-deletional HPFH mutation and \u03b2-thalassemia mutation in trans had elevated Hb A2 for \u03b2-thalassemia trait i.e., 3.6\u20133.9% in Indians34 and 4.3% in Thai (Table 25.Nucleotides between \u2212\u00a0675 to \u2212\u00a0526 of 0-thalassemia, A\u03b3\u03b4\u03b20-thalassemia, and HPFH described before10. Complex interactions between these non-deletional HPFH in both heterozygote and homozygote with other hemoglobinopathies commonly found in the region can lead to various hematological phenotypes and Hb F productions which could render diagnosis difficult. Identification of these non-deletional HPFH using rapid PCR diagnostic assays developed should improve this diagnosis in routine practice in the regions.In summary, three known and two novel HPFH mutations were identified for the first time in Thai population. This result indicates a diverse molecular heterogeneity of non-deletional HPFH in Thai population in addition to the deletional forms of \u03b4\u03b2Supplementary Information."}
{"text": "These chains are linked to each other by N\u2014H\u22efN hydrogen bonds, N\u2013H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions, forming a three-dimensional network.In the crystal, the mol\u00adecules are connected by N\u2014H\u22efN hydrogen bonds into dimers with an  19H15N5S, the thio\u00adphene ring is disordered in a 0.6:0.4 ratio by an approximate 180\u00b0 rotation of the ring around the C\u2014C bond linking it to the pyridine ring. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds into dimers with an R22(12) motif, forming chains along the b-axis direction. These chains are connected to each other by further N\u2014H\u22efN hydrogen bonds, forming a three-dimensional network. Furthermore, N\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid separations = 3.899\u2005(8) and 3.7938\u2005(12)\u2005\u00c5] inter\u00adactions also contribute to the crystal cohesion. A Hirshfeld surface analysis indicated that the most important contributions to the surface contacts are from H\u22efH (46.1%), N\u22efH/H\u22efN (20.4%) and C\u22efH/H\u22efC (17.4%) inter\u00adactions.In the title compound, C The dihedral angle between the phenyl (C7\u2013C12) and pyridine (N1/C2\u2013C6) rings is 64.42\u2005(11) \u00b0.The pyridine ring (N1/C2\u2013C6) of the title compound Fig.\u00a01 is large3.et al., 1995b-axis direction. These chains are connected to each other by further N\u2014H\u22efN hydrogen bonds, forming a three-dimensional network (Tables 1Cg1\u22efCg1i = 3.899\u2005(8)\u2005\u00c5; slippage = 1.899\u2005\u00c5; Cg3\u22efCg3ii = 3.7938\u2005(12)\u2005\u00c5; slippage = 1.383\u2005\u00c5; symmetry codes: (i) \u2212x, 1\u00a0\u2212\u00a0y, z; (ii) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, z; Cg1 and Cg3 are the centroids of the major component of the disordered thio\u00adphene ring and of the pyridine ring, respectively] also contribute to crystal cohesion . Fig.\u00a08u. Fig.\u00a07a,b. Fig4.et al., 2016et al., 2019et al., 2014aet al., 2014bet al., 2014cThe four related compounds found as a result of the search for \u20182,6-di\u00adamino-4-(thio\u00adphen-2-yl)pyridine-3,5-dicarbo\u00adnitrile\u2019 in the Cambridge Structure Database , chains running along the b-axis direction are formed through N\u2014H\u22efO inter\u00adactions between the 1,4-di\u00adhydro\u00adpyridine N atom and one of the O atoms of the ester groups. Neighbouring chains are linked by C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. In the crystal of WOJCIJ (space group P21/c), inversion dimers linked by pairs of N\u2014H\u22efN hydrogen bonds generate P21/n), inversion dimers linked by pairs of N\u2014H\u22efNc (c = cyanide) hydrogen bonds generate Pbca), inversion dimers linked by pairs of N\u2014H\u22efNn (n = nitrile) hydrogen bonds generate In the crystal of MUCLAA (space group 5.To a solution of 2-(thio\u00adphen-2-yl\u00admethyl\u00adene)malono\u00adnitrile  and malono\u00adnitrile  in methanol (25\u2005mL), phenyl\u00adethyl\u00adamine  was added and the mixture was stirred at room temperature for 48\u2005h. Then 15\u2005mL of methanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from ethanol/water (1:1) solution .1H NMR : 1.55 ; 5.45 ; 7.21\u20137.88 ; 13C NMR : 21.69 (CH3), 50.00 (CH\u2014Ar), 79.77 (=Ctert), 80.92 (=Ctert), 116.85 (CN), 116.97 (CN), 127.14 (2CHarom), 127.22 (CHarom), 128.11 (CHthien\u00adyl), 128.63 (2CHarom), 130.14 (CHthien\u00adyl), 130.75 (CHthien\u00adyl), 134.53 (Car), 144.53 (Cthien\u00adyl), 152.30 (=Ctert), 158.70 (N=Ctert), 161.38 (=Ctert).6.SHELXL were used for the Uij values of equivalent atom pairs  and DFIX commands were used to restrain the nearest-neighbour and next-nearest-neighbour bond distances in the two disorder components to be equal with a standard deviation of 0.03\u2005\u00c5. All C-bound H atoms were placed in calculated positions (0.95\u20131.00\u2005\u00c5) and refined as riding with Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atoms were located in a difference map and refined with Uiso(H) = 1.2Ueq(N) .Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023003845/vm2282sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023003845/vm2282Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023003845/vm2282Isup3.cmlSupporting information file. DOI: 2260011CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These ribbons are connected by N\u2014H\u22efO, N\u2014H\u22efN hydrogen bonds and van der Waals inter\u00adactions.In the crystal, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds into ribbons parallel to (022) along the  11H7N5OS, contains two independent mol\u00adecules (1 and 2). The thio\u00adphene ring in mol\u00adecule 2 is rotationally disordered (flip disorder) by ca 180\u00b0  over two sites with the site-occupation factors of 0.9 and 0.1. These two orientations of the thio\u00adphene ring in mol\u00adecule 2 are not equivalent. In the crystal, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds into ribbons parallel to (022) along the a axis. Within the (022) planes, these ribbons are connected by van der Waals inter\u00adactions and between the (022) planes by N\u2014H\u22efO hydrogen bonds. In mol\u00adecule 1, Hirshfeld surface analysis showed that the most important contributions to the crystal packing are from N\u22efH/H\u22efN (27.1%), H\u22efH (17.6%), C\u22efH/H\u22efC (13.6%) and O\u22efH/H\u22efO (9.3%) inter\u00adactions, while in mol\u00adecule 2, H\u22efH (25.4%) inter\u00adactions are the most significant contributors to the crystal packing.The asymmetric unit of the title compound, C These two orientations of the thio\u00adphene ring in mol\u00adecule 2 are not equivalent.As seen in Fig.\u00a01Database survey section.In mol\u00adecule 1, the angle between the thio\u00adphene (S1/C8\u2013C11) and pyridine (N1/C2\u2013C6) rings is 50.72\u2005(9)\u00b0. In mol\u00adecule 2, the angle between the two disordered thio\u00adphene rings (S2/C19\u2013C22 and S2\u2032/C19/C20\u2032\u2013C22\u2032) is 6.2\u2005(5)\u00b0, and they make an angle with the pyridine ring (N6/C13-C17) of 40.3\u2005(1) and 34.8\u2005(5)\u00b0, respectively. Mol\u00adecules 1 and 2 (r.m.s. deviation = 0.126\u2005A) are almost identical and the geometric parameters are normal and comparable to those of related compounds listed in the B\u22efN2 and N10\u2014H10A\u22efN7 hydrogen bonds, forming S(5) motifs  along the s Table\u00a01. Within s Table\u00a01 and 4 \u25b8.CrystalExplorer17.5  represent N\u2014H\u22efO inter\u00adaction zones (Table\u00a01b) inter\u00adactions provide the highest contribution (Table\u00a02c), C\u22efH/H\u22efC  and O\u22efH/H\u22efO  contacts are also significant. Table\u00a02dnorm mappings were performed in the range \u22120.5165 to +1.1535 a.u. The locations of N\u2014H\u22efO inter\u00adactions are shown by bright-red circles on the dnorm surfaces , Table\u00a01c; 25.4%) are the major factor in the crystal packing with N\u22efH/H\u22efN , O\u22efH/H\u22efO  and C\u22efH/H\u22efC  inter\u00adactions representing the next highest contributions. The percentage contributions of comparatively weaker inter\u00adactions in mol\u00adecules 1 and 2 are given in Table\u00a02es Fig.\u00a05a,b reprs Table\u00a01. The fins Table\u00a01 show thas Table\u00a01b inter\u00adn Table\u00a02, as wouln Table\u00a02c, C\u22efH/Hes Fig.\u00a05c,d, Tab\u22efN Fig.\u00a06b; 24.3%\u22efO Fig.\u00a06e; 11.7%\u22efC Fig.\u00a06d; 11.4%4.et al., 2016viz. CSD refcodes BEFFOL , pairs of mol\u00adecules are linked by pairs of N\u2014H\u22efN hydrogen bonds, forming dimers with an II crystallizes in the triclinic space group PIIA and IIB) in the asymmetric unit. In the crystal of II, mol\u00adecules IIA and IIB are linked by inter\u00admolecular N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds into layers parallel to (001). These layers are connected along the c-axis direction by weak C\u2014H\u22efN contacts. C\u2014H\u22ef\u03c0 and C\u2014N\u22ef\u03c0 inter\u00adactions connect adjacent mol\u00adecules, forming chains along the a-axis direction. In III (space group: Pc), the two mol\u00adecules in the asymmetric unit are joined together by N\u2014H\u22efO hydrogen bonds, forming a dimer with an c-axis direction, which are connected by C\u2014Br\u22ef\u03c0 inter\u00adactions. In IV (space group: Pc), inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, as well as N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions, connect the mol\u00adecules in the crystal, generating a 3D network. In both V (space group: PVI (space group: PVII (space group: P21/n), the crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions, and in VIII (space group: P21/c), by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. In IX (space group: Cc), inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds form mol\u00adecular sheets parallel to the (110) and (110) planes, crossing each other. Adjacent mol\u00adecules are further linked by C\u2014H\u22ef\u03c0 inter\u00adactions, which form zigzag chains propagating parallel to [100]. The compound X (space group: Pca21) crystallizes with two independent mol\u00adecules in the asymmetric unit. In the crystal, the A and B mol\u00adecules are linked by N\u2014H\u22efS, N\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds, forming a three-dimensional network. In XI (space group: P21/c), mol\u00adecules are linked into a chain along the b-axis direction via C\u2014H\u22efO inter\u00adactions. In XII (space group: PXIII (space group: P21/c), the mol\u00adecules form centrosymmetric dimers via N\u2014H\u22efS hydrogen bonds.In the crystal of 5.et al., 2020The title compound was synthesized using a recently reported procedure (Babaee 6.Uiso(H) = 1.2Ueq(C). The N-bound H atoms were found in a difference-Fourier map, and refined freely , with Uiso(H) = 1.2Ueq(N). The thio\u00adphene ring (S2/C19\u2013C22) in mol\u00adecule 2 is rotationally disordered (flip disorder) by ca 180\u00b0  over two sites with the site-occupation factors of 0.9 and 0.1 (fixed after refinement cycles). A DFIX instruction was applied to constrain the distances in the thio\u00adphene rings of disordered mol\u00adecule 2. For these rings, FLAT and EADP instructions were also used.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023003237/tx2066sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023003237/tx2066Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023003237/tx2066Isup3.cmlSupporting information file. DOI: 2255359CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A co-crystal of quabodepistat and 2,5-di\u00adhydroxy\u00adbenzoic acid was obtained and the crystal structure was solved from microcrystal electron diffraction (MicroED) data. R,4R)-1--3,4-di\u00adhydroxy\u00adpiperidin-4-yl]meth\u00adoxy}-8-fluoro-3,4-di\u00adhydro\u00adquinolin-2(1H)-one); C21H20ClF3N2O4] and 2,5-di\u00adhydroxy\u00adbenzoic acid  were successfully co-crystallized. Given the small size of the crystals (1 \u00d7 0.2 \u00d7 0.2\u2005\u00b5m) the structure was solved via microcrystal electron diffraction (MicroED). The C\u2014O and C=O bond-length ratio of the carb\u00adoxy\u00adlic group in 2,5DHBA is 1.08 (1.34\u2005\u00c5/1.24\u2005\u00c5), suggesting that 2,5DHBA remains protonated. Therefore, the material is a co-crystal rather than a salt. The amide group of quabodepistat participates in a cyclic hydrogen bond with the carb\u00adoxy\u00adlic group of the 2,5DHBA. Additional hydrogen bonds involving the quabodepistat amide and hydroxyl groups result in a three-dimensional network.Quabodepistat [(5-{[(3 The angles O21\u2014C16\u2014C17, F30\u2014C28\u2014C23, C6\u2014N7\u2014C8, C9\u2014C10\u2014C11, O1\u2014C14\u2014C15, and C6\u2014C11\u2014C2 also have z-score values greater than 3.Quabodepistat and 2,5DHBA co-crystallize in a 1:1 stoichiometric ratio in the monoclinic system, space group 2 values  exhibit \u03c73.via hydrogen bonds are observed between quabodepistat and 2,5DHBA. One of the inter\u00adactions is between a carb\u00adoxy\u00adlic group and an amide. As shown in Fig.\u00a01et al., 2020Inter\u00admolecular inter\u00adactions 4.et al., 2016A search for co-crystals with 2,5-di\u00adhydroxy\u00adbenzoic acid (or gentisic acid) in the Cambridge Structural Database . Tetra\u00adhydro\u00adfuran (THF) and hexane were purchased from FUJIFILM Wako Pure Chemical Corporation . 2,5DHBA was purchased from Tokyo Kasei Kogyo Co., Ltd. . Quabodepistat (5\u2005g) and 2,5DHBA  were dissolved in 100\u2005mL of THF. 250\u2005mL of hexane were added while stirring. Precipitation occurred as soon as hexane was added. The THF/hexane was stirred at room temperature (approximately 298\u2005K) for three days. After filtration, it was dried at room temperature for 24\u2005h, then heated at 383\u2005K for 20\u2005h.6.\u2212\u00c5\u22122 s\u22121. Contiguous diffraction frames were collected every 0.5\u00b0 from each crystal by continuously rotating the sample stage at a goniometer rotation speed of 1\u00b0 s\u22121; the sample stage was rotated from \u221240\u00b0 to 40\u00b0 for the first crystal  and from \u221260\u00b0 to 60\u00b0 for the second crystal . The structure was refined kinematically. Refinement with SHELXL was carried out using the scattering factors for electron diffraction  global, I. DOI: Click here for additional data file.10.1107/S2056989023006047/dj2052Isup2.cmlSupporting information file. DOI: https://doi.org/10.5281/zenodo.7156704Deposit the raw data into Zenodo: https://dx.doi.org/10.5517/ccdc.csd.cc2d19zrDeposit the raw data into CCDC: 2205804CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound consists of two independent mol\u00adecules differing slightly in conformation and in their inter\u00admolecular inter\u00adactions in the solid. 8H7NO3, consists of two mol\u00adecules differing slightly in conformation and in their inter\u00admolecular inter\u00adactions in the solid. The dihedral angle between the benzene and dioxolane rings is 0.20\u2005(7)\u00b0 in one mol\u00adecule and 0.31\u2005(7)\u00b0 in the other. In the crystal, the two mol\u00adecules are linked into dimers through pairwise O\u2014H\u22efN hydrogen bonds, with these units being formed into stacks by two different sets of aromatic \u03c0-stacking inter\u00adactions. The stacks are connected by C\u2014H\u22efO hydrogen bonds. A Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are H\u22efO/O\u22efH (36.7%), H\u22efH (32.2%) and C\u22efH/H\u22efC (12.7%).The asymmetric unit of the title mol\u00adecule, C For the C1\u2013C6 rings, the centroid\u2013centroid distance is 3.6024\u2005(11)\u2005\u00c5 with a slippage of 1.185\u2005\u00c5 between mol\u00adecules at x, y, z and \u2212x, \u2212y\u00a0+\u00a01, \u2212z. These paired mol\u00adecules make weak, slipped \u03c0-stacking inter\u00adactions with corresponding pairs at \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01 with a centroid\u2013centroid distance of 3.8479\u2005(11)\u2005\u00c5 and a slippage of 1.947\u2005\u00c5. The C9\u2013C14 ring has slipped \u03c0-stacking inter\u00adactions with its counterparts in mol\u00adecules at x\u00a0\u2212\u00a0y\u00a0+\u00a0z\u00a0\u2212\u00a0x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0B\u22efO4, C8\u2014H8\u22efO6, C15\u2014H15A\u22efO1 and C16\u2014H16\u22efO3 hydrogen bonds -2-(1H-imidazol-1-yl)ethyl\u00adidene]hydroxyl\u00adamine N-hy\u00addroxy-3-(1H-imidazol-1-yl)propan-1-imine iso\u00adpropanol solvate  form and (Z)-3,4-methyl\u00adene\u00addioxy\u00adbenzaldehyde oximium 4-toluene\u00adsulfonate A search using CCDC ConQuest of the Cambridge Structural Database  and 5(b), respectively. Fig.\u00a06a)] and delineated into C\u22efH/H\u22efC [Fig.\u00a06c)], and H\u22efO/O\u22efH [Fig.\u00a06h)] inter\u00adactions. For completeness, the H\u22efH inter\u00adactions constitute 32.2% of the surface [Fig.\u00a06b)]. The other inter\u00adactions contribute small amounts, viz., C\u22efN/N\u22efC (1.0%), C\u22efO/O\u22efC (2.4%), C\u22efC (9.5%), H\u22efN/N\u22efH (4.1%), N\u22efO/O\u22efN (1.1%), N\u22efN (0.0%) and O\u22efO (0.4%).The Hirshfeld surface analysis was performed with 6.d]dioxole-5-carbaldehyde dissolved in 50\u2005ml of ethanol was added to the mixture. After 5\u2005h of stirring at 273\u2005K, the product was allowed to precipitate and then filtered with a yield of 90%. Single crystals were recrystallized from ethanol solution.A solution of 5.0\u2005g of sodium hydroxide dissolved in 20\u2005ml of water was mixed with 8.0\u2005g of hydroxyl\u00adamine hydro\u00adchloride dissolved in 15\u2005ml of water, then 8.0\u2005g of benzo[7.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989023004139/hb8064sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004139/hb8064Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023004139/hb8064Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023004139/hb8064Isup4.cmlSupporting information file. DOI: 2262070CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E)-1-[(carbamo\u00adthioyl\u00adamino)\u00adimino]\u00adeth\u00adyl}-4-methyl-1,3-thia\u00adzol-3-ium cations are linked by O\u2014H\u22efCl, N\u2014H\u22efCl, N\u2014H\u22efO, N\u2014H\u22efS and C\u2014H\u22efS hydrogen bonds, forming a tri-periodic network.In the crystal, the 2-amino-5-{-1-[(carbamo\u00adthioyl\u00adamino)\u00adimino]\u00adeth\u00adyl}-4-methyl-1,3-thia\u00adzol-3-ium cation, one chloride anion and one water mol\u00adecule of crystallization. The cation is nearly flat (r.m.s. deviation of non-H atoms is 0.0814\u2005\u00c5), with the largest deviation of 0.1484\u2005(14)\u2005\u00c5 observed for one of the methyl C atoms. In the crystal, the cations are linked by O\u2014H\u22efCl, N\u2014H\u22efCl, N\u2014H\u22efO, N\u2014H\u22efS and C\u2014H\u22efS hydrogen bonds, forming a tri-periodic network. The most important contributions to the crystal packing are from H\u22efH (35.4%), S\u22efH/H\u22efS (24.4%), N\u22efH/H\u22efN (8.7%), Cl\u22efH/H\u22efCl (8.2%) and C\u22efH/H\u22efC (7.7%) inter\u00adactions.In the hydrated title salt, C In the 1,3-thia\u00adzol-3-ium ring, as expected, the C1\u2014N2 distance of 1.3309\u2005(16)\u2005\u00c5 indicates double-bond character, while the C2\u2014N2 distance of 1.3885\u2005(14)\u2005\u00c5 has more single-bond character.The asymmetric unit of (I)N\u2032-[(1Z)-ethyl\u00adidene]ethane\u00adthio\u00adhydrazide group, the S2\u2014C7\u2014N4\u2014N3, N5\u2014C7\u2014N4\u2014N3, C7\u2014N4\u2014N3\u2014C5 and N4\u2014N3\u2014C5\u2014C6 torsion angles are 178.17\u2005(8), \u22120.63\u2005(16), 174.48\u2005(10) and 0.16\u2005(18)\u00b0, respectively. The title compound shows bond lengths and angles that are typical and are in agreement with those reported for the related compounds discussed in the Database survey section.In the amino-The cation is nearly flat (r.m.s. deviation of the 14 non-H atoms is 0.0814\u2005\u00c5), with the largest deviations observed for C6 [0.1484\u2005(14)\u2005\u00c5], N1 [0.1357\u2005(10)\u2005\u00c5], and S2 [0.1399\u2005(6)\u2005\u00c5].3.In the crystal of (I)Crystal Explorer 17.5 , ds Fig.\u00a06.The two-dimensional fingerprint plots of the most abundant contacts are presented in Fig.\u00a074.et al., 2016et al., 2012et al., 2003et al., 1996et al., 2011A search of the Cambridge Crystallographic Database , the mol\u00adecular packing is determined by inter\u00adionic N\u2014H\u22efCl contacts. In the crystal of (V), the mol\u00adecules of substituted urea are connected by O\u2014H\u22efO hydrogen bonds into sheets. In turn, these sheets are connected to each other via N\u2014H\u22efO hydrogen bonds with hydrogen phosphate anions, forming a tri-periodic network.In the crystal of (II), mol\u00adecules are linked by O\u2014H\u22efCl and N\u2014H\u22efCl hydrogen bonds, forming zigzag chains along [001]. There is also a C\u2014H\u22efCl inter\u00adaction present. The crystal structure of (III) comprises a substituted thia\u00adzolium ring that is connected to a nitrate ion 5.et al., 2016v:v) solution at room temperatureThe title compound was synthesized using a reported procedure (Gomha 6.Uiso(H) = 1.5Ueq(C). The H atoms attached to the N atom and the H atoms of the water mol\u00adecule were found in a difference-Fourier map. Their positional parameters were refined freely while setting Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023007090/wm5691sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023007090/wm5691Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007090/wm5691Isup3.cmlSupporting information file. DOI: 2288159CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Single-crystal X-ray crystallographic analysis of 1 confirmed the presence of the first known (arene)cuprate. Also, unlike all previously known homoleptic (anthracene)metallates of d-block elements, which con\u00adtain metals coordinated only to terminal rings, the organocuprate unit in 1 con\u00adtains copper bound to the 9,10-carbons of the central ring of anthracene. No other d- or f-block metal is known to afford an anthracene or other aromatic hydro\u00adcarbon com\u00adplex having the architecture of organodicuprate 1.Reactions of (tri\u00adcyclo\u00adhexyl\u00adphosphane)copper(I) chloride with two equivalents of potassium anthracene (KAn) in tetra\u00adhydro\u00adfuran (THF) at 200\u2005K provides air-sensitive but thermally stable (at 293\u2005K) solutions from which yellow crystalline blocks of bis\u00ad[bis\u00ad(tetra\u00adhydro\u00adfuran-\u03ba Although the cuprate was originally speculated to be a copper analog of the mono\u00adatomic gold anion, Au1\u2212, established to be present in cesium auride, CsAu , which have been proposed to exist in solid neon at 4\u201310\u2005K \u00admetallates , in THF. Also, because stoichiometrically analogous naph\u00adtha\u00adlene and anthracene com\u00adplexes of a given d-block element may possess very similar mol\u00adecular structures, particularly in the solid state ]n  ]2 (Cy\u00a0= cyclo\u00adhex\u00adyl)  adducts of copper(I) halides due to the ease with which coordinated or free PPh3 and mixed tertiary ar\u00adyl\u2013alkyl phosphanes undergo reductive cleavage of P\u2014C(ar\u00adyl) bonds, unlike tri\u00adalkyl\u00adphosphanes ]2 with four equivalents of MAn  in THF appear by NMR spectra to afford similar products in solution, owing to the facile isolation and crystallization of the potassium salt, only the latter will be described now. Thus, the addition of a colorless solution of [CuCl(PCy3)]2 in THF to a dark-blue solution of KAn (molar ratio: 2 KAn/Cu) in THF at 200\u2005K, led to the formation of an air-sensitive but thermally stable (at 293\u2005K) yellow\u2013brown solution, from which yellow crystalline blocks of [K(THF)2]2[{Cu}2], 1, were isolated  halides, 2\u2212 , with X\u00a0= Cl \u2005\u00c5] is long  to 3.98\u2005(1)\u2005\u00c5.To the best of our knowledge, only the long-known dimeric organoalanate com\u00adplexes  is well within the range of 1.83\u20132.05\u2005\u00c5 observed previously for homoleptic diorganocuprates \u2005\u00c5. Prior studies suggest that d10Cu\u2013d10Cu inter\u00adactions are very weak to non-existent when the Cu\u22efCu separation is greater than \u223c2.50\u2005\u00c5 in mol\u00adecular entities con\u00adtaining CuI com\u00adplexes dicuprate(2\u2212) com\u00adplex, relative to unknown monomeric monoanions, i.e. [{Cu(THF)x}]1\u2212 (x\u00a0= 0\u20132), which would likely be strained metallacycles, vide infra. In the case of the structurally related organoaluminium com\u00adplexes 2 and 3, it was proposed that the dimeric, rather than plausible monomeric structures, \u2018are favored by smaller deviations from tetra\u00adhedral angles about the aluminum atoms in the dianions rather than about the aluminum atom in the hypothetical monoanions.\u2019 However, surprisingly, the possible importance of contact ion-pairing in contributing to the stabilization of the dimers in the solid state, and possibly also in solution, was not considered ]1\u2212 (Np\u00a0= naph\u00adtha\u00adlene), based only on a proton NMR spectrum in THF and identification of 1,4-di\u00adhydro\u00adnaph\u00adtha\u00adlene as a key hydrolysis product anthracene)], 4, strongly suggests that the natures of 2 and 3 in solution merit reinvestigation. It should also be emphasized that presently we cannot rule out the possibility that monomeric forms of 1 could be present in THF or other solvents  distance of 2.057\u2005(4)\u2005\u00c5, which is significantly longer than the normal Al\u2014C(Et) distance of 1.966\u2005(4)\u2005\u00c5 present in 4 ], 5, possessing a C9\u2014Mg\u2014C10 angle of 71.4\u00b0. This angle is significantly sharper than the corresponding angle in 4, likely owing in part to the higher coordination number of Mg in 5. The latter also con\u00adtains a rather long Mg\u2014C distance of 2.30\u2005(2)\u2005\u00c5 \u2005\u00c5 metal com\u00adplex to be recognized as a strained metallacycle ], 6, or 2,3:5,6-dibenzo-7-di\u00admethyl\u00adger\u00admano\u00adrbor\u00adna\u00addiene. X-ray structure characterization of 6, Me2GeAn, revealed a sharp C9\u2014Ge\u2014C10 angle of 77.72\u2005(5)\u00b0, and Ge\u2014C distances [average 2.030\u2005(1)\u2005\u00c5] which are significantly longer than the Ge\u2014C(Me) distance [average 1.943\u2005(4)\u2005\u00c5] \u2005\u00c5; Hencher & Mustoe, 19756 suffers thermal loss of anthracene at 373\u2005K in toluene to produce in good yield an intriguing di\u00admethyl\u00adgermylene, Me2Ge, adduct [{Ge2Me4}], 7, which may arise via insertion of highly reactive Me2Ge into a strained Ge\u2014C(bridgehead) bond of 6. However, also possible is an initial dimerization of Me2Ge to the digermene, Me4Ge2, followed by its facile [4\u00a0+\u00a02] cyclo\u00adaddition to free anthracene, which was established previously to afford 7  of ca \u221237\u2005kcal\u2005mol\u22121 of 7 Mg solvate in crystalline 1\u2212, the monomer of structurally characterized dimeric 3 ]z (z\u00a0= 0 or \u22121), are presently known to form dimers (or oligomers) related to 1, 2, or 3. Calculations on the structures and relative stabilities of the monomeric forms of 1, 2, and 3, com\u00adpared to the respective dimers, would be of considerable inter\u00adest. Inclu\u00adsion of contact ion-pairing could be of key importance in such a study, but might prove to be a nontrivial extension.Of particular relevance to our discussion is that neutral 1, which con\u00adtains only Cu\u2014C \u03c3-bonds, all prior (arene)copper com\u00adpounds have been characterized as \u03c0-com\u00adplexes, including the homoleptic cationic species, [Cu(arene)2]1+ [(\u03bc-Cl)3AlCl] (PR3)]PF6 (R\u00a0= phenyl or phenoxide) were described am\u00adino\u00admeth\u00adyl)anthracene}]1+ com\u00adplex, in which CuI is con\u00adstrained via chelation with di\u00adphenyl\u00adphosphanyl groups to lie over the central ring of nearly planar anthracene  and 2.414\u2005(6)\u2005\u00c5] for asymmetric \u03c0-bonding of the 1-naph\u00adthyl group, the Cu\u2014C distances in the copper\u2013\u03b76-anthracene com\u00adplex are in the range 2.773\u20133.021\u2005\u00c5. These are much longer than usual in (arene)copper com\u00adplexes, indicative, at best, of a very weak copper\u2013anthracene inter\u00adaction (PR3)]PF6, the Cu\u2014C distances are in the range 2.253\u20132.300\u2005\u00c5 ]2 (Cy\u00a0= cyclo\u00adhex\u00adyl) was prepared as described previously  colorless solution of [CuCl(PCy3)]2  in THF (50\u2005ml) and stirring continued for 12\u2005h at 200\u2005K. The resulting yellow\u2013brown solution was warmed over a ca 6\u2005h period to near 290\u2005K (room tem\u00adper\u00ada\u00adture) and filtered (medium or P4 porosity frit) to remove KCl. After careful evaporation of all but about 20\u2005ml of solvent in vacuo at 273\u2013293\u2005K, pentane (100\u2005ml) was added with stirring. The resulting slurry was filtered, washed vigorously with pentane (2 \u00d7 10\u2005ml) and dried in vacuo to afford 0.59\u2005g  of homogeneous yellow solid [K(THF)2]2[{Cu(C14H10)}2], 1. No elemental analysis was con\u00adducted on the bulk solid 1, so its com\u00adposition is based exclusively on the SCXRD study and NMR spectra. X-ray-quality yellow blocks of 1 were grown from a pentane-layered saturated solution in THF at 240\u2005K over a 6\u2005d period.Sublimed anthracene  and shiny pieces of potassium metal  were transferred in an argon-filled glove-box to a round-bottomed Schlenk flask, along with a glass-enclosed magnetic stirrer bar. Subsequently, THF (100\u2005ml) was added and the mixture was stirred vigorously in the dark for 6\u2005h at 293\u2005K to afford a deep-blue solution of potassium anthracene (KAn), which is susceptible to photo-oxidation by visible light. This solution/slurry was cooled to 200\u2005K with stirring and to it was transferred 1H NMR : 1.77 , 3.52 , 3.63 , 6.24 , 6.35 . 13C{1H} NMR : 24.2 , 52.4 , 66.3 , 117.7 , 117.9 , 145.2 .3}], 5 : 3.51 , 5.95 , 6.01 ; 13C{1H} NMR : 57.7 , 114.1 , 118.1 , 145.9   monomeric (anthracene)metal com\u00adplex, 2[{Cu}2], con\u00adtains one copper center and one anthracene ligand in contact with one [K(THF)2]1+ counter-ion. A crystallographic inversion center generates full well-resolved 1 (\u03b76-Np)]2\u2212 metal dimer com\u00adplex present in [Na(THF)2]2[{(AlMe2)}2], 3,  is greater than the corresponding sum for Na and Al (2.87\u2005\u00c5) \u2005\u00c5, K1\u22efCu1A\u00a0= 3.3762\u2005(9)\u2005\u00c5, K1\u22efK1A\u00a0= 6.542\u2005(2)\u2005\u00c5 and Cu1\u22efCu1A\u00a0= 2.6171\u2005(7)\u2005\u00c5 , than the corresponding distances in 3, i.e. Na1\u22efAl1\u00a0= 4.348\u2005(6)\u2005\u00c5, Na1\u22efAl1A\u00a0= 4.455\u2005(7)\u2005\u00c5, Na1\u22efNa1A\u00a0= 7.28\u2005(1)\u2005\u00c5 and Al1\u22efAl1A\u00a0= 4.95\u2005\u00c5. As described in Section\u00a011 arises from the essentially linear C9\u2014Cu\u2014C10A angle, expected for two-coordinated d10 CuI \u00b0], resulting from the distorted tetra\u00adhedral geometry of four-coordinated AlIII, causes the Al\u22efAl distance to be much longer \u2005\u00c5] and, as a result, its mol\u00adecular structure, without the THF groups, is fairly symmetrical and deviates only slightly from Dh2 symmetry \u2005\u00c5  and 3.57\u2005(1)\u2005\u00c5, respectively], which show that the two formal 9,10-coordinated anthracene dianion units are slightly further apart in 1 than they are in 3, owing also to the different coordination numbers of copper and aluminium in these remarkable com\u00adpounds, both of which are worthy of additional study.However, in er Fig.\u00a02. Of part\u2005\u00c5 Fig.\u00a01, with on1 and 3 are similar. Thus, for 1, the bridgehead angles C11\u2014C10\u2014C14 [113.3\u2005(2)\u00b0] and C12\u2014C9\u2014C13 [113.1\u2005(2)\u00b0] (Table\u00a023 , which are both close to the value of 1.51\u2005(5)\u2005\u00c5 observed previously for C(sp2)\u2014C(sp3) distances 2}]1\u2212, is structurally nearly identical, without the metal, to those observed in the dianions of 1 and 3, with an average bridgehead C\u2014C distance of 1.485\u2005(9)\u2005\u00c5. The lutetium anion also has an average bridgehead C\u2014C\u2014C angle of 111.8\u2005(5)\u2005\u00c5, which is very close to the corresponding angles of 1 and 3. A key structural difference in the lutetium anion is the sharp C9\u2014Lu\u2014C10 angle of 67.1\u2005(2)\u00b0, owing to the metalla\u00adcyclo\u00adpropane character of the com\u00adplex and, likely also the large bulk of the bis\u00ad(cyclo\u00adpenta\u00addien\u00adyl)lutetium moiety, which may well be responsible for its stability towards dimerization or oligomerization in solution (THF) and in the solid state as a crystalline [Na(diglyme)2]1+ salt (diglyme\u00a0= di\u00adethyl\u00adene glycol dimethyl ether) at ca 293\u2005K  having the shortest distances [average 3.14\u2005(13)\u2005\u00c5], whereas the K\u22efC distances for the six C atoms closest to the long K\u22efCu contact  are longer [average 3.38\u2005(5)\u2005\u00c5]  to 3.24\u2005(1)\u2005\u00c5, but the Na\u2014C distances of the four more crowded ring-junction C atoms are mostly longer  and C\u2014C\u2014C angles [average 119.9\u2005(2)\u00b0] that are quite similar to those found in uncharged free benzene dicuprate(2\u2212) with relatively weakly inter\u00adacting cations, such as [K([2.2.2.]cryptand)]1+, tetra\u00adalkyl\u00adammonium\u00ad(1+), etc., would be of considerable inter\u00adest. As our laboratory will be irreversibly shuttered in 2023, others are encouraged to examine these possibilities and related issues, vide infra.Inter\u00adactions of the alkali metal cations with the 4-naph\u00adtha\u00adlene)\u00adzir\u00adco\u00adnate(2\u2212), the first confirmed homoleptic (polyarene)metallate of a d-block metal 6]2\u2212, our research group has been inter\u00adested in discovering what other d-block elements, throughout the periodic table, would afford related and hopefully labile com\u00adplexes. Thus began our exploration in a systematic fashion of the synthesis and reactivity patterns of transition-metal com\u00adpounds con\u00adtaining metals in formal negative oxidation states 3, and particularly organic isocyanides, to determine whether the anthracenes would be displaced to produce new formal Cu com\u00adplexes. Noteworthy is that although isolable Cu1\u2212 com\u00adplexes remain unknown, very recently, the first unambiguous Cu0 com\u00adplex was isolated, thoroughly characterized, and structurally authenticated  I, global. DOI: 10.1107/S2053229623008367/eq3012Isup2.hklStructure factors: contains datablock(s) I. DOI: 2296812CCDC reference:"}
{"text": "N-butylamine (DBM). The aromatic compounds chosen were 2-aminopyridine (A2MP), 2-amino-4-methylpyridine (A24MP), 2-amino-6-methylpyridine (A26MP) and 4-dimethylaminopyridine (DMAP). The salts were characterised using single-crystal X-ray diffraction, thermal analysis, FTIR spectroscopy and Hirshfeld surface analysis. For all the crystal structures, N-H\u00b7\u00b7\u00b7O and C-H\u00b7\u00b7\u00b7Cl contacts were present. O-H\u00b7\u00b7\u00b7O contacts were found in all the crystal structures except for (3-chloro-4-hydroxyphenylacetic acid (CHPAA) is a fungal metabolite. It is a small molecule that is useful in crystal engineering studies due to the functional groups present. Six amines were selected to form salts with CHPAA. Linear derivatives included diethylamine (DEA) and di- N-butylamine (DBM), 2-aminopyridine (A2MP), 2-amino-4-methylpyridine (A24MP), 2-amino-6-methylpyridine (A26MP) and 4,4-dimethylaminopyridine (DMAP). These are depicted in Ka [Ka values of the amines are DEA (10.58), DBM (10.75), A2MP (6.84), A24MP (7.62), A26MP (7.60) DMAP (8.78). Thus, the \u2206pKa values ranged from 3.78 to 7.69. Salt formation is expected when \u2206pKa > 4. If <\u22121 \u2206pKa < 4, then either salt or co-crystal can form [Multicomponent crystals are important in the pharmaceutical industry as the formation of new solid forms can improve the physicochemical properties of active pharmaceutical ingredients ,2. The ced in Ka  of CHPAAcan form . In thisP\u012a, Z = 2 (d(C11\u00b7\u00b7\u00b7O2) of 3.4706(18) \u00c5 as well as contacts to the chlorine atom; C-H\u00b7\u00b7\u00b7Cl (d(C11\u00b7\u00b7\u00b7Cl1) = 3.821(2) \u00c5) and N-H\u00b7\u00b7\u00b7Cl (d(N1\u00b7\u00b7\u00b7Cl1) = 3.4818(16) \u00c5). The hydrogen bond metrics are summarised in 2\u2212 anions point directly towards each other, forming a type I halogen bond with d(Cl\u00b7\u00b7\u00b7Cl) = 3.517(2) \u00c5 and an angle of 174\u00b0  . Two mod(1.76 \u00c5) ,24 and W(1.76 \u00c5) . Subsequ(1.76 \u00c5) ,27,28. Tivatives . The DEAchannels c within C2/c with Z = 8 .th Z = 8 a. Both Nchannels b. The voP\u012a, Z = 2 (\u2212 anions (3.639(1) \u00c5) and between 2+AMP cations (3.835(1) \u00c5).\u012a, Z = 2 a. There am below b, the ca1/cP2 and its asymmetric unit contains one anti-oriented (H13A) on the primary amine forms an additional hydrogen bond, allowing the structure to generate an extended network system described as chains oftructure a, the acd anions b are arrP\u012a and its asymmetric unit contains two a-axis. The \u03c0-\u03c0 stacking interactions between synthons a consist diagram b shows cPbca and its asymmetric unit contains one 2 group in DMAP. There are \u03c0\u2013\u03c0 stacking interactions between adjacent b-axis.The salt of 4-dimethylaminopyridinium-3-chloro-4-hydroxyphenylacetate, ractions a. The st\u2212)(DBM+) displayed C-H\u00b7\u00b7\u00b7O interactions. The O-H\u00b7\u00b7\u00b7O and N-H\u00b7\u00b7\u00b7O hydrogen bonds gave contact distances with average values for d(H\u00b7\u00b7\u00b7O) = 1.79 \u00c5, d(H\u00b7\u00b7\u00b7N) = 1.89 \u00c5, d(O\u00b7\u00b7\u00b7O) = 2.62 \u00c5 and d(N\u00b7\u00b7\u00b7O) = 2.78 \u00c5. These were followed by the C-H\u00b7\u00b7\u00b7O and C-H\u00b7\u00b7\u00b7Cl contacts which gave average values of d(H\u00b7\u00b7\u00b7O) = 2.55 \u00c5, d(H\u00b7\u00b7\u00b7 Cl) = 3.01 \u00c5, d(C\u00b7\u00b7\u00b7O) = 3.44 \u00c5 and d(C\u00b7\u00b7\u00b7Cl) = 3.72 \u00c5.In summary,  and Cl\u00b7\u00b7\u00b7H (15.8\u201318.8%) contacts. There are prominent wings on the fingerprint plots for\u2212 anions in these structures. Only . Thus, salt formation with the aromatic amines resulted in increased thermal stability with the highest melting point observed for Differential scanning calorimetry (DSC) results are presented for all the salts, and thermogravimetric analysis (TGA) was completed for , A24MP (3429 cm\u22121) and A26MP (3461 cm\u22121) either disappeared or diminished in the IR spectra of the resulting salts. This can be attributed to the \u2212NH2 group\u2019s involvement in hydrogen bonding in the A2MP, A24MP and A26MP salts. The FTIR spectra are given in FTIR spectroscopy is often used in screening new solid forms to distinguish between co-crystal and salt formation ,33. It iPXRD analyses of all compounds obtained from the grinding and slurry experiments were performed to determine whether the salts obtained by the slow evaporation technique can also be prepared using other techniques. The calculated PXRD patterns obtained from LAZYPULVERIX  were comAll chemicals were purchased from Sigma Aldrich  and were used as received. K. Diffraction data for all compounds were collected on a Bruker APEX II diffractometer . SADABS  was usedA D2 PHASER Bruker diffractometer with Cu-K\u03b1 radiation (1.54184 \u00c5) was used for PXRD. The voltage tube and current were at 30 kV and 10 mA max, respectively, with a scintillation counter 1-dim LYNXEYE detector. The scanning process of each sample was between 4\u201350\u00b0 2\u03b8.\u22121.Spectra were obtained from the universal attenuated total reflectance (UTAR) infrared spectrometer Perkin Elmer spectrum two. Sample spectra were measured over the range of 4000\u2013400 cm\u22121. These analyses were conducted from 303\u2013573 K with a heating rate of 10 K min\u22121.DSC analyses were performed on a Perkin-Elmer 6 system with a purge of nitrogen at 20 mL minSamples of 2\u20135 mg were removed from the mother liquor, dried with filter paper, then crushed to a fine powder and placed in a vented pan for the DSC analysis.\u2212)(DBM+). The Cl\u00b7\u00b7\u00b7Cl halogen bond was only found in (Salts of CHPAA with selected linear and aromatic amines were successfully prepared. The formation of the new solid forms was validated using DSC analysis, and in the case of the aromatic amines, the resulting salts demonstrated enhanced thermal stability compared to the starting materials. FTIR spectroscopy confirmed salt formation. The salt structures of CHPAA, except for ("}
{"text": "The dihedral angles between the indole ring system and pendant nitro\u00adbenzodioxolane rings system and phenyl\u00adsulfonyl ring are 4.81\u2005(14) and 72.24\u2005(19)\u00b0, respectively. In the crystal, the indole mol\u00adecules are linked to each other and to the chloro\u00adform mol\u00adecule by weak C\u2014H\u22efO, C\u2014H\u22efCl, C\u2014H\u22ef\u03c0, C\u2014Br\u22ef\u03c0 and C\u2014Cl\u22ef\u03c0 and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions.The title indole derivative crystallizes with a partial occupancy [0.585\u2005(4)] CHCl 24H17Br3N2O6S, crystallizes with a partial occupancy [0.585\u2005(4)] CHCl3 solvent mol\u00adecule. The dihedral angles between the indole ring system and pendant nitro\u00adbenzodioxolane rings system and phenyl\u00adsulfonyl ring are 4.81\u2005(14) and 72.24\u2005(19)\u00b0, respectively. In the crystal, the indole mol\u00adecules are linked to each other and to the chloro\u00adform mol\u00adecule by weak C\u2014H\u22efO, C\u2014H\u22efCl, C\u2014H\u22ef\u03c0, C\u2014Br\u22ef\u03c0 and C\u2014Cl\u22ef\u03c0 and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions. A Hirshfeld surface analysis was carried out and the inter\u00admolecular contacts with the most significant contributions are H\u22efO/O\u22efH (24.3%), H\u22efH (18.4%), Br\u22efH/H\u22efBr (16.8%) and C\u22efH/H\u22efC (8.4%).The title indole derivative, C The C1\u2014N1 and C4\u2014N1 bond lengths are 1.423\u2005(5) and 1.427\u2005(5)\u2005\u00c5, respectively, while in the case of N atoms in planar configurations, the reported mean value is 1.355\u2005(14)\u2005\u00c5 vinyl moiety occurs due to an addition reaction with Br2. The Br1\u2014C16\u2014C15\u2014Br2 grouping is in a trans configuration and the torsion angle has a value of 178.14\u2005(17)\u00b0. Intra\u00admolecular C5\u2014H5\u22efO1, C15\u2014H15\u22efO2, C16\u2014H16\u22efO6 and C24\u2014H24B\u22efBr2 inter\u00adactions \u00b0 with the C1\u2013C8/N1 indole ring system Fig.\u00a01. The C1\u2014ns Fig.\u00a01 are obse3.Cg2i cyclo\u00adhex-3-en-1-yl}vin\u00adyl)-3-methyl-1-(phenyl\u00adsulfon\u00adyl)-1H-indole tetra\u00adhydrate , H\u22efH (18.4%), Br\u22efH/H\u22efBr (16.8%) and C\u22efH/H\u22efC (8.4%).The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were determined using the 6.E)-3-methyl-2-[2-vin\u00adyl]-1-(phenyl\u00adsulfon\u00adyl)-1H-indole  and N-bromo\u00adsuccinimide  in dry CCl4 (100\u2005ml) containing a catalytic amount of azobisisobutyro\u00adnitrile  was refluxed for 2\u2005h. The reaction mixture was cooled to room temperature. Then, the suspended succinimide was filtered off and the filtrate was concentrated in vacuo to obtain the crude product, which upon trituration with methanol (10\u2005ml) gave the title compound as a bright-yellow solid. Yield: 800\u2005mg (88%) m.p. 431\u2013433\u2005K. The synthesized compound was crystallized by slow evaporation using chloro\u00adform as solvent.A solution of  I. DOI: 10.1107/S2056989023007120/hb8071Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007120/hb8071Isup3.cmlSupporting information file. DOI: 2279852CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: BMC Cancer 23, 540 (2023)https://doi.org/10.1186/s12885-023-10997-xFollowing publication of the original article , the autThe incorrect author name is: \u00c1d\u00e1ny R\u00f3zaThe correct author name is: R\u00f3za \u00c1d\u00e1nyThe author group has been updated above and the original article  has been"}
{"text": "Inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds connect individual mol\u00adecules into layers extending parallel to (100). These layers are connected by C\u2014H\u22ef\u03c0 inter\u00adactions. 32H29N5O2\u00b7C3H7NO, the bi\u00adcyclo[3.3.1]nonane ring sys\u00adtem adopts a half-chair/twist-boat conformation, with the phenyl rings in equatorial orientations with respect to the piperidine ring. The two oxane rings of the 2-oxabi\u00adcyclo\u00ad[2.2.2]octane ring system exhibit a distorted boat conformation. Inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds connect the mol\u00adecules in the crystal, generating layers extending parallel to (100). These layers are connected by C\u2014H\u22ef\u03c0 inter\u00adactions. A Hirshfeld surface analysis was per\u00adformed to qu\u00adantify the contributions of the different inter\u00admolecular inter\u00adactions, indicating that the most important contributions to the crystal packing are from H\u22efH (52.5%), N\u22efH/H\u22efN (19.2%), C\u22efH/H\u22efC (18.8%) and O\u22efH/H\u22efO (8.3%) inter\u00adactions.In the title compound, C The phenyl rings  are in equatorial orientations with respect to the piperidine ring (C1/C2/N3/C4/C5/C9). The two oxane rings (O9/C9/C1/C8/C7/C10 and O9/C9/C5/C6/C7/C10) of the 2-oxabi\u00adcyclo\u00ad[2.2.2]octane ring system (C10/O9/C9/C1/C8/C7/C6/C5) exhibit a distorted boat conformation with puckering parameters QT = 0.799\u2005(2)\u2005\u00c5, \u03b8 = 91.88\u2005(14)\u00b0, \u03c6 = 247.89\u2005(15)\u00b0 for the O9/C9/C1/C8C7/C10 ring, and QT = 0.826\u2005(2)\u2005\u00c5, \u03b8 = 96.04\u2005(14)\u00b0, \u03c6 = 50.59\u2005(15)\u00b0 for the O9/C9/C5/C6/C7/C10 ring.The mol\u00adecular structure of the title compound is displayed in Fig.\u00a02le Fig.\u00a02. As showle Fig.\u00a02 are QT 3.In the crystal, inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds Table\u00a01 link indCrystalExplorer17  to 1.4361 (blue) a.u. is shown in Fig.\u00a06dnorm surface represent the aforementioned C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions  points from all the contacts contributing to the Hirshfeld surface analysis in normal mode for all atoms. The most important inter\u00admolecular inter\u00adactions are H\u22efH contacts, contributing 52.5% to the overall crystal packing. Other inter\u00adactions and their respective contributions are N\u22efH/H\u22efN (19.2%), C\u22efH/H\u22efC (18.8%), O\u22efH/H\u22efO (8.3%), N\u22efN (0.6%), C\u22efN/N\u22efC (0.3%), C\u22efC (0.2%) and C\u22efO/O\u22efC (0.1%), respectively.Fig.\u00a07et al., 2015The Hirshfeld surface study verifies the significance of H-atom inter\u00adactions in the packing formation. The contributions of H\u22efH and N\u22efH/H\u22efN inter\u00adactions imply that van der Waals inter\u00adactions are important in the crystal packing   -3-aza\u00adbicyclo\u00ad[3.3.1]nonan-9-ol (III)    and (III) crystallize in monoclinic space groups , whereas (II) is ortho\u00adrhom\u00adbic . In each of the three structures, the bicyclic ring system adopts a chair/chair conformation and the phenyl rings are in equatorial orientations with respect to the piperidine ring. In (II), apart from van der Waals forces, only weak inter\u00admolecular C\u2014H\u22efO-type inter\u00adactions are involved in the packing.Compounds (IV) has monoclinic symmetry  and has two mol\u00adecules in the asymmetric unit. A et al., 1995via N\u2014H\u22efO hydrogen bonds.The structure of (V), which likewise is monoclinic , the bicyclic ring system adopts a twin-chair conformation. The two methyl groups attached to the bicycle are in an equatorial orientation for both rings. In the crystal, very long N\u2014H\u22efO hydrogen bonds connect the mol\u00adecules into a chain perpendicular to [010].In  solution.The title compound was synthesized using a previously reported procedure (Mamedov 6.Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atoms were located from difference-Fourier maps and refined with free atomic coordinates and Uiso = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989023001718/wm5672sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023001718/wm5672Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023001718/wm5672Isup3.cmlSupporting information file. DOI: 2244417CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S is established as a function of several basic geometric parameters to well characterize the noncovalent interaction energy, which exhibits a good inverse correlation with the reorganization energies of the photo-excited states or electron-pumped charged states in organic/polymeric semiconductors. In particular, the experimental 1H, 77Se, and 125Te NMR, the optical absorption and emission spectra, and single crystal structures of eight compounds fully confirm the theoretical predictions. This work provides a simple descriptor to characterize the strength of noncovalent intramolecular interactions, which is significant for molecular design and property prediction.In recent years, intramolecular noncovalent interaction has become an important means to modulate the optoelectronic performances of organic/polymeric semiconductors. However, it lacks a deep understanding and a direct quantitative relationship among the molecular geometric structure, strength of noncovalent interaction, and optoelectronic properties in organic/polymeric semiconductors. Herein, upon systematical theoretical calculations on 56 molecules with and without noncovalent interactions , we reveal the essence of the interactions and the dependence of its strength on the molecular geometry. Importantly, a descriptor  Intramolecular noncovalent interactions can block molecules in a given conformation enhancing performance of organic semiconductors. Here, the authors report a molecular descriptor to weigh them that strongly correlates with the reorganization energy of excited or charged states. Many experimental and theoretical works focus on intermolecular noncovalent interactions since they are directly responsible for the formation of molecular crystals, large clusters, folding of proteins, and binding of DNA and drugs14. However, intramolecular noncovalent interactions are less investigated, although they are also important to determine the structure of basic units for building larger aggregates17. It is noteworthy that the intramolecular interactions significantly influence the conformation of the organic/polymeric semiconductors, which is critical to determine their physicochemical properties, such as optical properties and charge transport mobilities20. Many groups have adopted the noncovalent intramolecular interactions as an important strategy for designing high-performance organic/polymeric semiconductors for different applications, including organic solar cells (OSCs)28, thin film transistors (OTFTs)32, photodetectors (OPDs)33 and light-emitting diodes (OLEDs)37, since Huang, Marks, Facchetti, and coworkers termed this intramolecular noncovalent interaction as \u201cNoncovalent Conformational Locks (NoCLs)\u201d owing to their conformation-locking feature in enhancing the planarity and rigidity of organic semiconductors38. For example, the noncovalent fused ring electron acceptors (NFREAs) have been developed using the NoCLs strategy, which greatly improved the power conversion efficiencies (PCEs) to reach over 15%, similar to those of the fused ring electron acceptors (FREAs), while significantly decreased the synthetic complexity28. Moreover, various NoCLs  have been used to enhance the charge transport mobilities of organic/polymeric semiconductors for OTFTs29, affording the record mobility as high as 14.9 cm2\u00a0V\u22121\u00a0s\u22121\u200931. Also, the OLED based on the thermally activated delayed fluorescence (TADF) obtained by the NoCLs strategy showed a high external quantum efficiency of 23.2%39. Although these investigations presented the efficacy of NoCLs in designing high-performance organic/polymeric semiconductors, they lack direct correlation between chemical structures, the strengths of NoCLs, and the optoelectronic properties of organic/polymeric semiconductors. Furthermore, the nature of intramolecular NoCLs in organic/polymeric semiconductors, whether they arise from orbital overlap or electrostatic interactions, remains controversial47.Noncovalent interactions play important roles in chemistry, biology, catalysis, and material sciences49, which dramatically increased the difficulty of experimental characterization. Moreover, due to various chemical elements or groups, there is a wide variety of noncovalent intramolecular interaction, such as cation-\u03c0, anion-\u03c0, chalcogen-\u03c0, carbonyl-\u03c0, hydrogen bonding, halogen bonding, and chalcogen-bonding in organic molecules53. Thus, the theoretical study of these interactions became very complicated and challenging.Although many efforts have been made, it is very challenging to deeply investigate the fundamentals of NoCLs. First, noncovalent interactions are very weak forces, usually one to two orders of magnitude smaller than covalent interactions1H, 77Se, and 125Te NMR, the optical absorption and emission spectra, and the single crystal structures of eight synthesized compounds fully confirmed the theoretical predictions.In this work, 56 molecules Fig.\u00a0 with varM(S\u00b7\u00b7\u00b7O) and PhM/PhM-H(S\u00b7\u00b7\u00b7O) were selected as representatives to investigate the feature of X\u00b7\u00b7\u00b7Y NoCLs. The relaxed potential energy (E) surface (PES) scans were performed along the dihedral angle \u03b8  analysis54 was performed to obtain the variation of energy (E(2)), and took atomic dipole moment-corrected Hirshfeld (ADCH) charge55 , and Eelec, as well as the distances between the atoms. From Fig.\u00a0M(S\u00b7\u00b7\u00b7O) appeared at \u03b8\u2009=\u20090.01o, whose E was set to zero on the PES. At equilibrium geometry, the S\u00b7\u00b7\u00b7O distance d(S\u00b7\u00b7\u00b7O) of 2.85\u2009\u00c5 is much shorter than the sum of van der Waals radii (dv) of S and O atoms dv(S\u00b7\u00b7\u00b7O) of 3.32\u2009\u00c5; the Eelec is a small negative value due to few charges on S (qS) and O (qO) atoms  is a large negative value owing to large overlap between the n-orbital (lone pair electron of the oxygen atom) and the \u03c3*-orbital of the S-C bond (n(O)\u2009\u2192\u2009\u03c3*(S-C))  are formed by the orbital interactions. Differently, the two minima on the PES of type II are very close in energy with a large energy barrier  with 0o\u2009\u2264\u2009\u03b8\u2009\u2264\u200990o, and the H\u00b7\u00b7\u00b7O interaction is detected in PhM-H(S\u00b7\u00b7\u00b7O) with 90o\u2009<\u2009\u03b8\u2009\u2264\u2009180o. As shown in Fig.\u00a0PhM(S\u00b7\u00b7\u00b7O) (\u03b8\u2009=\u200918.92o and d(S\u00b7\u00b7\u00b7O)\u2009=\u20092.76\u2009\u00c5), and both the orbital interactions and the electrostatic interactions are weak at the minimal of PhM-H(S\u00b7\u00b7\u00b7O) (\u03b8\u2009=\u2009157.34o and d(H\u00b7\u00b7\u00b7O)\u2009=\u20092.31\u2009\u00c5). The orbital interaction in PhM(S\u00b7\u00b7\u00b7O) comes from n(O)\u2192\u03c3*(S-C) and that in PhM-H(S\u00b7\u00b7\u00b7O) stems from n(O)\u2192\u03c3*(H-C).The molecules 5 Figure\u00a0 to calcuenergy (E), and toenergy (E), and tos Figure\u00a0; and the) Figure\u00a0. These iier Fig.\u00a0. Hence, 56 for the studied systems. For type II systems, the energy differences between two minima (PhM-H(O\u00b7\u00b7\u00b7Y) is more stable than PhM(O\u00b7\u00b7\u00b7Y), while PhM(X\u00b7\u00b7\u00b7O) (X\u2009=\u2009S and Se) and PhM(Te\u00b7\u00b7\u00b7Y)  are more stable than their corresponding PhM-H. The differences in energies between two conformations are small for the others. The potential energy surfaces of the systems were further scanned at the same level and plotted in Figure\u00a0PhM(X\u00b7\u00b7\u00b7C) and PhM-H(X\u00b7\u00b7\u00b7C) , owing to a low energy barrier  of mutual transformation between them, and the others have only one conformation due to large energy barrier.The nature of NoCLs was examined at the equilibrium geometry of the studied systems. The equilibrium geometries were optimized and the frequencies were calculated at the B3LYP(D3)/6-31\u2009+\u2009G(d) levelsee Fig.\u00a0. It is oM(X\u00b7\u00b7\u00b7Y) ones, 9 PhM(X\u00b7\u00b7\u00b7Y) ones, and 11 PhM-H(X\u00b7\u00b7\u00b7Y) ones). It is generally believed that the NoCLs are effectively formed between two atoms if the distance between them is less than dv. According to the \u0394d\u2009=\u2009dv-d results given in Fig.\u00a0d (>0.10\u2009\u00c5), being conducive to the formation of NoCL. The nature of NoCLs is either electronic interaction or orbital interaction45. From Fig.\u00a0\u22121, which is impossible to be responsible for the NoCLs. The orbital interaction varies greatly with E(2) ranging from \u22125.27 to 0.00\u2009kcal\u2009mol\u22121  for the systems with and without NoCLs, which is likely to be the main contributor to form NoCLs. Of 36 compounds, 15 with E(2)<\u22121.00\u2009kcal\u2009mol\u22121 are considered to have significant NoCLs, and the strength of NoCL exhibits the order of S\u00b7\u00b7\u00b7F\u2009<\u2009Se\u00b7\u00b7\u00b7F\u2009<\u2009Te\u00b7\u00b7\u00b7F, S\u00b7\u00b7\u00b7O\u2009<\u2009Se\u00b7\u00b7\u00b7O\u2009<\u2009Te\u00b7\u00b7\u00b7O, and X\u00b7\u00b7\u00b7F\u2009<\u2009X\u00b7\u00b7\u00b7O . The orbital interaction is determined by the type, shape, and orientation of orbitals and bonds. As shown in Fig.\u00a02), n(p)\u2192\u03c3*(sp2), and n(sp)\u2192\u03c3*(sp2) for M and PhM molecules, and n(s)\u2192\u03c3*(s), n(p)\u2192\u03c3*(s) and n(sp2)\u2192\u03c3*(s) for PhM-H molecules. The n(sp2)\u2192\u03c3*(sp2) shows the strongest interaction when p-orbital component dominates in the hybrid sp2-orbital, because the shape and orientation of the sp2-orbital are favorable for overlap, such as Te\u00b7\u00b7\u00b7O NoCL. While the participation of s-orbital weakens the interaction due to its very small electronic density distribution area, like H\u00b7\u00b7\u00b7Y NoCL. Hence, the H\u00b7\u00b7\u00b7Y NoCLs in PhM-H molecules are always weaker than X\u00b7\u00b7\u00b7Y NoCLs in M and PhM molecules. Overall, 15 of 36 molecules were predicted to have significant NoCLs, namely, X\u00b7\u00b7\u00b7Y  and Te\u00b7\u00b7\u00b7S in M and PhM, and H\u00b7\u00b7\u00b7S and H\u00b7\u00b7\u00b7Cl in PhM-H  and the length of NoCL d(S\u00b7\u00b7\u00b7O), the angle between S\u00b7\u00b7\u00b7O NoCL and S-C bond (\u03b1), and the dihedral angle between two thiophene rings (\u03b8) which is closely related to molecular structural planarity and disorder57. It is found the E(2) as an exponential function of the distance, and the cosine function of the angle \u03b1 or \u03b8. Based on this, we proposed a simple descriptor that contains several geometrical parameters  versus S, which are calculated based on the optimized equilibrium geometries for 36 isolated systems in Fig.\u00a0R2 is as high as 0.927, which indicates a very strong positive correlation between E(2) and S. Moreover, the S value varies in the order of S\u00b7\u00b7\u00b7O\u2009<\u2009Se\u00b7\u00b7\u00b7O\u2009<\u2009Te\u00b7\u00b7\u00b7O and S\u00b7\u00b7\u00b7F\u2009<\u2009Se\u00b7\u00b7\u00b7F\u2009<\u2009Te\u00b7\u00b7\u00b7F, which is in good agreement with the order of strength of NoCLs obtained above by E(2). This is mainly because from S to Te the atomic radius gradually increases while the distances of X\u00b7\u00b7\u00b7Y and other factors are almost unchanged, which results in the increase of \u0394d, corresponding to the strengthening of NoCLs in this order. In addition, as it is described above that the orbital interactions of hydrogen bond in PhM-H compounds happen between s-orbital of H atom and p- or sp2-orbital of Y atoms, and it is almost independent of the orientation of C-H bond because s-orbital is spherical. And if removing cos\u03b1 from the S for PhM-H systems, the results would become better  and S were further calculated for 11 compounds of 36 with strong NoCLs at B3LYP(D3)/def2-TZVP, \u03c9B97XD/def2-TZVP and CCSD(T)/def2-TZVP levels  and S becomes stronger at large basis set and higher theory levels. Based on the optimized geometries by B3LYP(D3)/def2-TZVP, the linear fitting coefficient is improved from R2\u2009=\u20090.974 at B3LYP(D3)/def2-TZVP level to R2\u2009=\u20090.991 at CCSD(T)/def2-TZVP level. Based on the optimized geometries by \u03c9B97XD/def2-TZVP  and S with R2\u2009=\u20090.992  and S of 56 compounds is still strong with R2\u2009=\u20090.907  less than ca. \u22121.00\u2009kcal\u2009mol\u22121).Considering the effect of the basis set and method on the results, the els Fig.\u00a0c, d. TheP Figure\u00a0, the CCS992 Fig.\u00a0. In addi7 Figure\u00a0. Therefoa) absorbs a phonon to form an excited state (b), the excited molecule firstly experiences a relaxation of geometrical structure to a new equilibrium point (c) by releasing reorganization energy (\u03bbES) and then decays to the ground state (d) by radiative and nonradiative processes, finally relax to the initial ground-state equilibrium point (a) by giving out reorganization energy (\u03bbGS). The reorganization energy decides the shape and width of the optical spectra. Under the framework of the linear coupling model, the sum of the two reorganization energies can be crudely considered as the Stokes shift between the absorption and emission spectra, \u03ba\u2009=\u2009\u03bbGS\u2009+\u2009\u03bbES59. Moreover, there is a positive relationship between the nonradiative decay rate and the excited reorganization energy, in which the excitation energy is always much larger than the reorganization energy61. Consequently, small reorganization energy can effectively block the nonradiative decay process. For electron-pumped charge transfer processes, the charge transfer rates between molecule dimers can be calculated by Marcus rate equation in the high temperature and short time limits, +\u2192M+\u2009+\u2009M), \u0394G can be approximately zero, and there is an inverse relationship between the rate constant of charge transfer and the charge reorganization energy \u03bbcharge. As a result, the molecules with small reorganization energy usually are designed to exhibit excellent charge transport property62. The \u03bbcharge can be calculated by the sum of \u03bbNS and \u03bbCS between the neutral (ground) state (NS) and the charged states (CS) in organic molecules, as shown in Fig.\u00a0As it is well known that reorganization energy or relaxation energy is an important physical parameter to character the optoelectronic properties. Reorganization energy is defined as the energy dissipated from the equilibrium geometry in the initial state to the relaxed equilibrium geometry in the final state for an isolated molecule  and PhM(X\u00b7\u00b7\u00b7C) with X\u2009=\u2009O, S, Se, and Te were calculated as shown in Fig.\u00a0S behaves good negative relationship with \u03bbopt (Stokes shift \u03ba). The Stokes shifts of the systems with strong NoCLs are far smaller than those of the corresponding systems without NoCLs. Moreover, the larger S is, the larger the difference of Stokes shift is. For example, the Stokes shift from PhM(Se\u2009\u2219\u2009\u2219\u2219C)  to PhM(Se\u2009\u2219\u2009\u2219\u2219O)  is decreased by 75\u2009nm, while that from PhM(Te\u2009\u2219\u2009\u2219\u2219C)  to PhM(Te\u2009\u2219\u2009\u2219\u2219O)  decreased by 118\u2009nm. The linear correlation between \u0394\u03bbopt and S is very good with R2\u2009=\u20090.801 for 6 pairs of compounds of type II molecules with apparent noncovalent interactions  of X\u2009=\u2009O, S, Se, and Te, and Y\u2009=\u2009O and C were synthesized ,PhM(S\u00b7\u00b7\u00b7O) PhM(Se\u00b7\u00b7\u00b7O), and PhM(Te\u00b7\u00b7\u00b7O). In these compounds, the d values are 2.38(9) \u00c5 for H\u00b7\u00b7\u00b7O, 2.68(2) \u00c5 for S\u00b7\u00b7\u00b7O, 2.69(1) \u00c5 for Se\u00b7\u00b7\u00b7O, and 2.76(0) \u00c5 for Te\u00b7\u00b7\u00b7O, respectively, which are much shorter than the corresponding dv, confirming the existence of strong NoCLs. Differently, both PhM/PhM-H (S\u00b7\u00b7\u00b7C) and PhM/PhM-H (Se\u00b7\u00b7\u00b7C) possess two conformations, which fully prove the theoretical predictions above. Moreover, the torsion angles between chalcogenide and phenyl rings in PhM(S\u00b7\u00b7\u00b7O)  and PhM(Se\u00b7\u00b7\u00b7O)  are much smaller than those in PhM(S\u00b7\u00b7\u00b7C)  and PhM(Se\u00b7\u00b7\u00b7C) , illustrating the \u201clock of planarity\u201d function of NoCLs.To confirm the theoretical prediction, eight compounds d Figure\u00a0\u2013S18, andd Figure\u00a0. The con1H-1H NOESY NMR of eight compounds was measured in d2-tetrachloroethane solution, which is always used to certify conformational preferences through spatial interactions between different 1H signals  is more stable than PhM(O\u00b7\u00b7\u00b7O) in d2-tetrachloroethane and the O\u00b7\u00b7\u00b7H NoCL is stronger than O\u00b7\u00b7\u00b7O one. Similarly, the cross-peak between H1 and H2 in Fig.\u00a0PhM(Te\u00b7\u00b7\u00b7O) conformation with strong Te\u00b7\u00b7\u00b7O NoCLs. Both the cross-peaks between H5 and H2, and between H1 and H2 are observed in Fig.\u00a0PhM(O\u00b7\u00b7\u00b7C) and PhM-H(O\u00b7\u00b7\u00b7C), and PhM(Te\u00b7\u00b7\u00b7C) and PhM-H(Te\u00b7\u00b7\u00b7C) coexist owing to freely rotatable aromatic rings without NoCLs, suggesting no effective NoCLs in these compounds. These NMR observations are consistent with the experimental results that no single conformation was observed for PhM-H(S\u00b7\u00b7\u00b7C) and PhM-H(Se\u00b7\u00b7\u00b7C) in their respective crystals as shown in Figure\u00a0PhM(S\u00b7\u00b7\u00b7O) seems to be inconsistent with its crystal structure since it exhibits no cross-peaks neither between H6 and H2, nor between H1 and H2  calculated in Table\u00a0\u03b8 of isolated PhM(S\u00b7\u00b7\u00b7O) is calculated to be 17.29o, which is larger than that of 4.68o/5.59o in crystal, implying a more twisted conformation in solution. Since the strengths of NoCLs decrease sharply from \u03b8\u2009=\u20090o to 20o  may become very weak in solution, causing the alienation of H1 and H2. Thus, these experimental observations reinforce the reliability of theoretical predictions. In addition, The 77Se and 125Te NMR of PhM(Se\u00b7\u00b7\u00b7O), PhM(Se\u00b7\u00b7\u00b7C), PhM(Te\u00b7\u00b7\u00b7O), and PhM(Te\u00b7\u00b7\u00b7C) are further measured and the results were shown in Figure\u00a077Se NMR of PhM(Se\u00b7\u00b7\u00b7O) displays one single peak of symmetric Se nucleus located at 645.70 ppm, with a downfield shift of 9.15 ppm compared to the signal of PhM(Se\u00b7\u00b7\u00b7C) at 636.55 ppm. Since the inductive effect of the O atom generally decays along chemical bonds and disappears after three \u03b4 bonds, this phenomenon can only be triggered by Se\u00b7\u00b7\u00b7O interaction. Note that this trend is in accordance with that in literature reported by Tomita64. Similarly, the downfield shift phenomenon is observed in PhM(Te\u00b7\u00b7\u00b7O) (851.62 ppm) in comparison to that of PhM(Te\u00b7\u00b7\u00b7C) (841.78 ppm) in 125Te NMR, which reveals the existence of Te\u00b7\u00b7\u00b7O interactions. Overall, the reflected results by 1H-1H NOESY NMR tell us that the Te\u00b7\u00b7\u00b7O, O\u00b7\u00b7\u00b7H, and S\u00b7\u00b7\u00b7O are significant NoCLs while the O\u00b7\u00b7\u00b7C, Te\u00b7\u00b7\u00b7C, and H\u00b7\u00b7\u00b7C are not effective NoCLs in these compounds, which are consistent with the theoretically predicted results.The als Fig.\u00a063. As sh2 Figure\u00a0. AccordiPhM(Te\u00b7\u00b7\u00b7O) with strong NoCLs as an example, the 1H-1H NOESY NMR is further measured in d2-dichloromethane (d2-DCM) and d6-dimethylsulfoxide (d6-DMSO) shown in Figure\u00a01 and H2 appears in the three solvents. The position of the cross-peak hardly shifts with the increase of the polarity of the solvent, which implies these NoCLs are not controlled by the electrostatic interactions47.In order to reveal the nature of NoCLs, the effect of solvents on NoCLs was investigated. Taking PhM(X\u00b7\u00b7\u00b7C) , there display immense redshifts of the absorption peaks in PhM(X\u00b7\u00b7\u00b7O) , which accounts for the introduction of NoCLs for higher molecular planarity65. The resultant Stokes shift sharply decreased from PhM(X\u00b7\u00b7\u00b7O) to PhM(X\u00b7\u00b7\u00b7C) , which depicts the enhancement of rigidity brought by NoCLs. Specific \u0394\u03ba values are rendered to estimate the relative ability of NoCLs in altering rigidity with 61 (63) nm for S\u00b7\u00b7\u00b7O interaction, 75 (66) nm for Se\u00b7\u00b7\u00b7O interaction, and 118 (91) nm for Te\u00b7\u00b7\u00b7O interaction. This implies the stronger the NoCLs, the more its ability in enhancing rigidity. Moreover, the intensity order of S\u00b7\u00b7\u00b7O\u2009<\u2009Se\u00b7\u00b7\u00b7O\u2009<\u2009Te\u00b7\u00b7\u00b7O of the NoCLs is perfectly reflected by the \u0394\u03ba values, which are in good agreement with the theoretically calculated results above. The same experiments are carried out in tolune and THF solvents with different polarity, and the Stokes shifts and their changes exhibit extremely small changes  based on the theoretical equilibrium structures in the gas (solid) phase and the experimental S (SExp) based on the experimental crystal structures for the six compounds , which demonstrates that the SExp based on the crystal structure is also very reliable. To confirm the assumption, we arbitrarily select a series of compounds from the CCDC crystal database to calculate E(2) and the SExp based on experimental crystal structures and plot them in Fig.\u00a0R2 is very high with a value of 0.972, which reveals that the S can be applied widely. Thus far, it is safe to conclude that S is a suitable descriptor for evaluating the strength of NoCLs, which would be used for further machine-learning-based molecular screening studies.To extend the application of this descriptor, twelve compounds were selected to be investigated Fig.\u00a0. First, nds Fig.\u00a0. Excitin1H, 77Se, and 125Te NMR, and UV-vis spectra of the eight new synthesized systems fully confirmed the theoretical predictions. This work provides an in-depth understanding and simple description of noncovalent interaction, which is important for the rational molecule design of high-performance organic/polymeric semiconductors.Herein, 56 organic semiconductors with and without noncovalent interactions  were investigated to show that the interactions are mainly derived from orbital interactions based on the theoretical calculations and experimental results. The strength of interactions followed the order of S\u00b7\u00b7\u00b7F\u2009<\u2009Se\u00b7\u00b7\u00b7F\u2009<\u2009Te\u00b7\u00b7\u00b7F, S\u00b7\u00b7\u00b7O\u2009<\u2009Se\u00b7\u00b7\u00b7O\u2009<\u2009Te\u00b7\u00b7\u00b7O, and X\u00b7\u00b7\u00b7F\u2009<\u2009X\u00b7\u00b7\u00b7O . In contrast, O\u00b7\u00b7\u00b7Y , X\u00b7\u00b7\u00b7C , and Se\u00b7\u00b7\u00b7Y  cannot form effective noncovalent interactions in the systems. Furthermore, it is disclosed that the strength of noncovalent interactions is closely related to the structural parameters, including the molecular planarity, the angle between two relevant orbitals, and the distance between the two related atoms. Significantly, a descriptor 66 of theory using the basis set 6-31\u2009+\u2009G(d)  and LANL2DZ for Se and Te or def2-TZVP in Guassian16 Program67, including geometrical parameters, energy, atomic dipole moment-corrected Hirshfeld population (ADCH) charge analyses68, natural bond orbital (NBO) analysis54. NBO analysis have been carried out using Multiwfn software69. The CCSD/def2-TZVP method was used to calculate the orbital interaction. As for the solid phase, the initial structure is obtained from the X-ray crystal structure, and geometrical structures in the ground state are calculated based on QM/MM model through Gaussian16 Program. The centered molecule is treated as a high layer and calculated at B3LYP(D3)/def2-TZVP level for QM, and the surrounding molecules are treated as a low layer and computed by MM with UFF forces field. The reorganization energy is calculated using the adiabatic potential energy surface method in MOMAP72.All the geometrical and electronic structures of the investigated system in the ground state were calculated at B3LYP(D3) or \u03c9B97XD level3)4 (5% equiv) were added under nitrogen in anhydrous toluene (20.0\u2009mL). The mixture was stirred and refluxed at 120\u2009\u00b0C for 12\u2009h. Afterwards, an aqueous potassium fluoride solution  was added to the mixture. After quenching the reaction, the organic phase was extracted with dichloromethane (3\u2009\u00d7\u2009100\u2009mL). The combined organic portion was collected, washed with water and brine, and dried over MgSO4. After filtration, the solution was filtered through a short silica gel column (petroleum ether), concentrated to afford the crude product, which is subjected to the recrystallization in hexane. Finally, the crystals were dried in vacuo to afford PhM(X\u00b7\u00b7\u00b7O)/PhM(X\u00b7\u00b7\u00b7C). The detailed synthesis is described in Supplementary Information, and the final products were characterized by 1H-NMR, 13C-NMR, 77Se-NMR, and 125Te-NMR. (Supplementary Section 13).Preparations of 1,4-dihexyl-2,5-diiodobenzene, 1,4-dihexyloxy-2,5-diiodobenzene, 2-tributylstannyl-derivatives are illustrated thoroughly in Supplementary Information. To a round-bottom flask (100\u2009mL), 1,4-dihexyl-2,5-diiodobenzene  (1.0 equiv), 2-tributylstannyl-derivatives (2.5 equiv) and Pd(PPhUV-Vis absorption spectra were measured on a Gary 60 UV-Vis Spectrophotometer. Photoluminescence spectra were measured on a FLS 1000 (EDINBURGH INSTRUMENTS) with an Xenon Lamp. All liquid samples were well dissolved in chloroform. All film samples were spin-coated on glass substrates.A glass vial (5\u2009mL) containing a chloroform or toluene solution of the compounds (2\u2009mg) was placed inside a vial (20\u2009mL) containing methanol. After 2\u20137 days, white (yellow) solid single crystals were collected.Supplementary InformationPeer Review FileDescription of Additional Supplementary FilesSupplementary Data 1Supplementary Data 2Supplementary Data 3Supplementary Data 4Supplementary Data 5Supplementary Data 6Supplementary Data 7"}
{"text": "The PdII atom displays a slightly distorted square-planar PdP2S2 geometry with a bidentately coordinated pyridin-2-ylcarbonimidodithio\u00adate ligand and two triphenyl\u00adphosphine mol\u00adecules, coordinated in cis positions. The crystal structure features weak \u03c0\u2013\u03c0 [centroid\u2013centroid distance =3.7327(15)\u2005\u00c5] and C\u2013H\u22ef\u03c0 inter\u00adactions and contains an almost spherically shaped void of 50.4\u2005\u00c53 per unit cell.The title compound, [Pd(C DOI: 10.1107/S1600536810050518/im2253Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Adjacent Zn atoms are bridged by the bidentate carboxyl\u00adate groups into a cationic chain extending along [010]. N\u2014H\u22efN, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds link the cationic chains, nitrate anions and uncoordinated water mol\u00adecules into a supra\u00admolecular network. \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings and between the pyridine and benzene rings [centroid\u2013centroid distances = 3.615\u2005(4) and 3.636\u2005(4)\u2005\u00c5] are present.In the title compound, {[Zn(C DOI: 10.1107/S1600536811021088/hg5047Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ru0 atom adopts a distorted trigonal\u2013bipyramidal coordination geometry, with the C\u00a0O ligand and the ketone O atom occupying the axial positions. The two triphenyl\u00adphosphane ligands are cis to each other. The olefinic C=C bond is almost coplanar with the Ru0 atom and the two P atoms (maximum deviation of 0.0516\u2005\u00c5 from the mean plane defined by the five constituent atoms). The coordinated C=C bond has a length of 1.449\u2005(3)\u2005\u00c5, which is significantly longer than that of a free C=C bond (1.34\u2005\u00c5). There are two C\u2014H\u22ef\u03c0 inter\u00adactions involving neighbouring phenyl rings in the mol\u00adecule. In the crystal, mol\u00adecules are linked via two further C\u2014H\u22ef\u03c0 inter\u00adactions.The 1-vinyl\u00adpyrrolidin-2-one ligand in the title compound, [Ru(C For C=C al. 1989. For str al. 1998; Jazzar  al. 2001.6H9NO)(C18H15P)2(CO)] = 0.025wR(F2) = 0.084S = 1.157113 reflections442 parametersH-atom parameters constrainedmax = 0.66 e \u00c5\u22123\u0394\u03c1min = \u22120.80 e \u00c5\u22123\u0394\u03c1CrystalClear  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812014766/su2399Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The ZnII ions are bridged by the ligands, forming a helical chain along [001]. C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the imidazole rings [centroid\u2013centroid distance = 3.4244\u2005(10)\u2005\u00c5] assemble the chains into a three-dimensional supra\u00admolecular network.In the title complex, [Zn(C DOI: 10.1107/S1600536812012706/hy2526Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One of the CuII ions has a square-pyramidal arrangement, which is defined by a water mol\u00adecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2\u2032-bipyridine mol\u00adecule, one carboxyl\u00adate O atom from a terephthalate ligand and one O atom from a water mol\u00adecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water mol\u00adecule. An O\u2014H\u22efO and O\u2014H\u22efCl hydrogen-bonded three-dimensional network is formed between the components.In the binuclear title compound, [Cu Cl(C10H8N2)2(H2O)3]NO3\u00b7H2O = 0.052wR(F2) = 0.172S = 1.046973 reflections412 parametersH-atom parameters constrainedmax = 0.71 e \u00c5\u22123\u0394\u03c1min = \u22120.64 e \u00c5\u22123\u0394\u03c1RAPID-AUTO  I, global. DOI: 10.1107/S1600536812019848/fj2542Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Intra- and inter\u00admolecular \u03c0\u2013\u03c0 stacking is present in the crystal structure, and the centroid\u2013centroid distances between the benzene and pyridine rings of adjacent dmphen ligands are 3.492\u2005(3) and 3.592\u2005(3)\u2005\u00c5, respectively. Inter\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions help to stabilize the crystal structure.In the title complex, [Pb(NO DOI: 10.1107/S1600536810022312/xu2779Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two CdII atoms are bridged by two chloride anions, forming an inversion-related Cd2Cl2 unit; these units are further linked through thio\u00adcyanate anions, leading to a chain structure extending parallel to [010]. Weak \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances of 3.430\u2005(4)\u2005\u00c5 and an inter\u00adplanar separation of 3.390\u2005(3)\u2005\u00c5 between the pyridine and benzene rings link the chains into a two-dimensional network parallel to (C DOI: 10.1107/S1600536811051373/wm2567Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The silver ion is surrounded by two tryptanthrin ligands, each coordinating through the N atoms, with Ag\u2014N bond lengths of 2.247\u2005(3) and 2.264\u2005(3)\u2005\u00c5, and an anionic nitrate ligand coordinating through two O atoms, with Ag\u2014O bond lengths of 2.499\u2005(3) and 2.591\u2005(3)\u2005\u00c5. The N\u2014Ag\u2014N plane and the O\u2014Ag\u2014O plane are roughly perpendicular, making a dihedral angle of 81.6\u2005(2)\u00b0. In the crystal, C\u2014H\u22efO inter\u00adactions between aromatic H atoms and keto and nitrate O atoms as well as \u03c0\u2013\u03c0 inter\u00adactions [centroid-centroid distance = 3.706\u2005(4)\u2005\u00c5] give rise to a three-dimensional network.In the crystal structure of the title compound, [Ag(NO DOI: 10.1107/S1600536812001821/rn2096Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The benzene ring of the 4-carb\u00adoxy-2-sulfonato\u00adbenzoate anion is twisted with respect to the two phen ring systems at dihedral angles of 66.38\u2005(9) and 53.56\u2005(9)\u00b0. In the crystal, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonding links the mol\u00adecules into chains running parallel to [100]. Inter\u00admolecular \u03c0\u2013\u03c0 stacking is also observed between parallel phen ring systems, the face-to-face distance being 3.432\u2005(6)\u2005\u00c5.In the title complex, [Mn(C DOI: 10.1107/S1600536810023743/xu2781Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 23.00\u2005(10)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 85.34\u2005(4)\u00b0. An intra\u00admolecular O\u2014H\u22efO hydrogen bond occurs between coordinating water mol\u00adecule and the carboxyl\u00adate group. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. A weak C\u2014H\u22ef\u03c0 inter\u00adaction also occurs in the crystal.In the title complex, [Cu(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.025wR(F2) = 0.066S = 1.093482 reflections216 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.40 e \u00c5\u22123\u0394\u03c1min = \u22120.39 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812028814/xu5579Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The complex shows several inter\u00adesting features: (i) the polyoxygenated loop of C4 effectively chelates a sodium cation in the form of a distorted octahedron and separates it from the iodide counter-ion, the shortest Na+\u22efI\u2212 distance being greater than 6.5\u2005\u00c5; (ii) the cavity of C4 is filled by a methanol mol\u00adecule; (iii) a second methanol mol\u00adecule is hydrogen-bonded to the N atom of a pyridinyl substituent pendant of C4 and halogen-bonded to the I atom of a tFdIB mol\u00adecule; (iv) the two I atoms of another tFdIB mol\u00adecule are halogen-bonded to two iodide anions, which act as monodentate halogen-bond acceptorss; (v) one of the two tFdIB molecules is located about a centre of inversion.The title compound, [Na(C When ca62H76N2O6)]I\u00b71.5C6F4I2\u00b72CH4O = 0.045wR(F2) = 0.095S = 1.1333353 reflections847 parametersH-atom parameters constrainedmax = 2.33 e \u00c5\u22123\u0394\u03c1min = \u22121.52 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SIR2002  global, I. DOI: Click here for additional data file.10.1107/S1600536813007757/bg2501Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal packing is stabilized by inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.4669\u2005(19) and 3.764\u2005(2)\u2005\u00c5].In the title compound, (C DOI: 10.1107/S1600536810054371/bt5430Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Partial hydrolysis led to the title compound, the hydro\u00adchloric acid adduct of the dichloride, having a penta\u00adcoordinated Sn atom with a trigonal\u2013bipyramidal C2SnCl3 core. The N atom of the 2-[(diisopropyl\u00adammonio)\u00admeth\u00adyl]phenyl ligand forms a strong intra\u00admolecular N\u2014H\u22efCl hydrogen bond, resulting in a zwitterionic species, [2-(iPr2HN+CH2)C6H4]SnBuCl3               \u2212\u00b7CH2Cl2. Disorder was found in the n-butyl group, which was refined as disordered over three positions, with site occupancies of 0.22\u2005(1), 0.51\u2005(1) and 0.27\u2005(2).The title compound, [Sn(C DOI: 10.1107/S1600536810050713/zl2332Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the polymeric title compound, {[Pb(C13H11N4O)(CH3OH)2]ClO4}n, is coordinated by an N\u2032-[1-(pyridin-2-yl-\u03baN)ethyl\u00adidene]isonicotinohydrazidate ligand via O,N,N\u2032-donors and simultaneously bridged by a neighbouring ligand via the isonicotinoyl N atom; two additional sites are occupied by methanol O atoms. The resultant supra\u00admolecular chain is a zigzag along the c axis. The PbII atom is seven-coordinated within an N3O3 donor set and a lone pair of electrons, which defines a \u03a8-pentagonal\u2013bipyramidal coordination geometry with the pyridine N and lone pair in axial positions. The supra\u00admolecular chains are linked into the two-dimensional array via inter\u00admolecular Pb\u22efN [3.020\u2005(4)\u2005\u00c5] inter\u00adactions. Layers stack along the a axis, being connected by O\u2014H\u22efO hydrogen bonds formed between the coordinated methanol mol\u00adecules and perchlorate anions.The Pb N\u2032-[1-(2-pyrid\u00adyl)ethyl\u00adidene]isonicotinohydrazide ligand, see: Maurya et al. (CH4O)2]ClO4                         = 0.024                           wR(F                           2) = 0.066                           S = 1.05                           3492 reflections255 parametersH-atom parameters constrainedmax = 0.97 e \u00c5\u22123                        \u0394\u03c1min = \u22120.98 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811046769/hg5133Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The equatorial plane is formed by two trans-related N,O-bidentate pyridazine-3-carboxyl\u00adate ligands and the axial positions are occupied by two water mol\u00adecules. The CoII complex mol\u00adecules are stacked in a column along the a-axis direction by an O\u2014H\u22efN hydrogen bond between the non-coordinating pyridazine N atom and the coordinating water mol\u00adecule. These columns are further connected into a layer parallel to the ac plane by additional hydrogen bonds involving the coordinating and non-coordinating water mol\u00adecules, and the non-coordinating carboxyl\u00adate O atom. The crystal packing is completed by inter\u00adlayer weak C\u2014H\u22efO inter\u00adactions.The title compound, [Co(C For a r al. 2004.5H3N2O2)2(H2O)2]\u00b72H2O = 0.026wR(F2) = 0.058S = 1.081369 reflections122 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.28 e \u00c5\u22123\u0394\u03c1min = \u22120.31 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: OLEX2  I, global. DOI: 10.1107/S1600536813017340/is5284Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One of the two quniolinium ions forms an N\u2014H\u22efOp  hydrogen bond and the other an N\u2014H\u22efOw (w = water) hydrogen bond. The water mol\u00adecules further link the components by O\u2014H\u22efOp and O\u2014H\u22efOw hydrogen bonds. A number of C\u2014H\u22efO inter\u00adactions and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid separation = 3.541\u2005(7)\u2005\u00c5] are also observed. Together, these generate a three-dimensional network.In the title compound, (C DOI: 10.1107/S1600536813027347/hb7146Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, [Cd(C6H12NS2)2(C10H8N2)], is hexa\u00adcoordinated by two dithio\u00adcarbamate ligands and the N atoms from a bidentate 2,2\u2032-bipyridyl mol\u00adecule. The coordination geometry is based on a distorted trigonal\u2013prismatic arrangement of the N2S4 donor set. Supra\u00admolecular chains, aligned along the a-axis direction, are mediated by C\u2014H\u22efS inter\u00adactions and these are connected into layers that stack along the c axis via \u03c0\u2013\u03c0 inter\u00adactions [Cg(pyrid\u00adyl)\u22efCg(pyrid\u00adyl) = 3.6587\u2005(13)\u2005\u00c5].The Cd DOI: 10.1107/S1600536811006878/pk2304Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between the phen and DHB ligands [centroid\u2013centroid distances = 3.542\u2005(4) and 3.879\u2005(4)\u2005\u00c5] and between the pyridine and benzene rings of adjacent phen ligands [centroid\u2013centroid distance = 3.751\u2005(4)\u2005\u00c5] stabilize the crystal structure. Intra\u00admolecular O\u2013H\u22efO hydrogen bonds are observed in the DHB ligands.In the mononuclear title complex, [Dy(C DOI: 10.1107/S1600536810048348/hy2381Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are two acridine mol\u00adecules  and one and a half water mol\u00adecules in the asymmetric unit. The half-mol\u00adecule of water is located on a crystallographic twofold axis. The crystal structure is built up from two threads of mol\u00adecule II sewn together with water mol\u00adecules through O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds from one side and with \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.640\u2005(3) and 3.7431\u2005(3)\u2005\u00c5] between overlapping mol\u00adecules II on the other side. Mol\u00adecule I is attached to this thread from both sides by C\u2014H\u22efO hydrogen bonds. The threads are connected to each other by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.582\u2005(3) and 3.582\u2005(3)\u2005\u00c5] between the inner side of mol\u00adecule I and stabilized by a C\u2014H\u22ef\u03c0 inter\u00adaction on the other side of mol\u00adecule I. This thread with rows of mol\u00adecule I hanging on its sides is generated by translation perpendicular to the a axis.The title compound, C \u00c5                           b = 8.893 (5) \u00c5                           c = 17.492 (5) \u00c5                           V = 4107 (3) \u00c53                                                   Z = 16                           K\u03b1 radiationMo \u22121                        \u03bc = 0.08 mmT = 197 K                           0.3 \u00d7 0.3 \u00d7 0.3 mm                                 Bruker SMART 6000 diffractometer14504 measured reflections3606 independent reflectionsI > 2\u03c3(I)1733 reflections with R                           int = 0.068                                                            R[F                           2 > 2\u03c3(F                           2)] = 0.058                           wR(F                           2) = 0.197                           S = 1.00                           3606 reflections272 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.35 e \u00c5\u22123                        \u0394\u03c1min = \u22120.29 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXTL  I, global. DOI: 10.1107/S1600536811038220/ez2255Isup2.hkl            Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038220/ez2255Isup3.cml            Supplementary material file. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two imidazole rings are oriented to each other with a dihedral angle of 75.1\u2005(2)\u00b0. Strong O\u2014H\u22efO hydrogen bonds between protonated and deprotonated carboxyl\u00adate groups occur in the mol\u00adecular structure. In the crystal structure extensive O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds help to stabilize the three-dimensional supra\u00admolecular framework. The propyl groups of anions are disordered over two sites with refined occupancies of 0.768\u2005(6):0.232\u2005(6) and 0.642\u2005(8):0.358\u2005(8).In the title complex, [Cd(C DOI: 10.1107/S1600536810031466/xu5001Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the CuII ions is coordinated in a distorted square-planar environment and the other is coordinated in a distorted square-pyramidal environment. The long apical Cu\u2014O bond of the square-pyramidal coordinated CuII ion is formed by a symmetry-related O atom, creating a one-dimensional polymer along [010]. In addition, short inter\u00admolecular Cl\u22efCl distances [3.444\u2005(2)\u2005\u00c5] and weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.736\u2005(2)\u20133.875\u2005(3)\u2005\u00c5] are observed. The crystal studied was an inversion twin with a refined twin component ratio of 0.60\u2005(1):0.40\u2005(1).The asymmetric unit of the title compound, [Cu DOI: 10.1107/S1600536812028462/lh5494Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II complex, [Cu(C7H4BrO2)2(C6H6N2O)2(H2O)2], contains one half-mol\u00adecule, the CuII atom being located on an inversion center. The unit cell contains two nicotinamide (NA), two 4-bromo\u00adbenzoate (PBB) ligands and two coordinated water mol\u00adecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 22.17\u2005(16)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.80\u2005(6)\u00b0. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. A weak C\u2014H\u22ef\u03c0 inter\u00adaction is also observed.The asymmetric unit of the title mononuclear Cu N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.039                           wR(F                           2) = 0.108                           S = 1.13                           3515 reflections203 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.86 e \u00c5\u22123                        \u0394\u03c1min = \u22121.29 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811021696/su2279Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex lies on an inversion center. The metal atom is surrounded by two chelating isobidentate O-propan-2-yl (4-eth\u00adoxy\u00adphen\u00adyl)dithio\u00adphospho\u00adnate ligands in a trans configuration binding through the S-donor atoms. The Ni\u2014S bond lengths are 2.2328\u2005(5) and 2.2369\u2005(5)\u2005\u00c5, an insignificant difference to be considered anisobidentate. The Ni\u22efP separation is 2.8224\u2005(5)\u2005\u00c5 and the S\u2014P bond lengths are 2.0035\u2005(7) and 2.0053\u2005(7)\u2005\u00c5. The S\u2014Ni\u2014S (chelating) and S\u2014Ni\u2014S (trans) bond angles are 88.321\u2005(18) and 180\u00b0. The Ni\u2014S\u2014P bond angles are 83.26\u2005(2) and 83.33\u2005(2)\u00b0, indicating a very minor distortion from ideal square-planar geometry for the Ni atom. The P atom, however, is distorted quite significantly from an ideal tetra\u00adhedral geometry, as reflected by the S\u2014P\u2014S and O\u2014P\u2014C bond angles of 101.93\u2005(3) and 100.70\u2005(7)\u00b0, respectively. The title compound, [Ni(C DOI: Click here for additional data file.10.1107/S1600536812045114/bh2460Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The ErIII ion has a distorted dodeca\u00adhedral coordination with six coordinating O atoms derived from the ferrocene\u00adcarboxyl\u00adate ligands and two coordinated O atoms from one water mol\u00adecule and one methanol mol\u00adecule. The asymmetric unit comprises a half of the complex mol\u00adecule and a methanol solvent mol\u00adecule. Intra\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions occur. In the crystal, mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and C\u2014H\u22efO as well as C\u2014H\u22ef\u03c0 inter\u00adactions.In the centrosymmetric title coordination compound, [Er DOI: 10.1107/S1600536811051245/kp2371Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The phenyl rings of biphenyl are twisted from each other by dihedral angles of 50.5\u2005(2), 44.5\u2005(2) and 27.8\u2005(2)\u00b0. The arsine-substituted phenyl rings make dihedral angles of 61.56\u2005(18), 89.36\u2005(18) and 83.27\u2005(18)\u00b0 with each other. The dihedral angles between the two benzene rings are 87.5\u2005(2) and 81.95\u2005(19)\u00b0 for the two diphenyl\u00adarsanyl groups. In the crystal, mol\u00adecules are linked into dimers by inter\u00admolecular C\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.601\u2005(3)\u2005\u00c5] inter\u00adactions stabilize the crystal structure.In the title  DOI: 10.1107/S1600536811000237/ng5094Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds link the mol\u00adecules into columns in [001]. The porous crystal packing is further stabilized via \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.746\u2005(3)\u2005\u00c5] with voids of 270\u2005\u00c53.In the title compound, [Ni(C DOI: 10.1107/S1600536812014109/cv5274Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The distorted tetrahedral coordination sphere is defined by chelating N atoms that define an acute angle [69.6\u2005(3)\u00b0] and two I atoms that form a wide angle [142.80\u2005(4)\u00b0]. The linearly coordinated HgII atom [177.0\u2005(4)\u00b0] exists with a donor set defined by C and Cl atoms. Secondary inter\u00adactions are apparent in the crystal packing with the tetra\u00adhedrally and linearly coordinated HgII atoms expanding their coordination environments by forming weak Hg\u22efI [3.772\u2005(7)\u2005\u00c5] and Hg\u22efO [2.921\u2005(12)\u2005\u00c5] inter\u00adactions, respectively. Mercury-containing mol\u00adecules stack along the a axis, are connected by \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distance between pyridine and benzene rings = 3.772\u2005(7)\u2005\u00c5] and define channels in which the dimethyl sulfoxide mol\u00adecules reside. The latter are connected by the aforementioned Hg\u22efO inter\u00adactions as well as C\u2014H\u22efI and C\u2014H\u22efO inter\u00adactions, resulting in a three-dimensional architecture.The title dimethyl sulfoxide solvate, [Hg E)-N-(pyridin-2-yl\u00admethyl\u00adidene)aryl\u00adamine-type ligands, see: Basu Baul, Kundu, H\u00f6pfl et al. I2]\u00b7C2H6OS = 0.053wR(F2) = 0.143S = 1.034848 reflections208 parametersH-atom parameters constrainedmax = 4.40 e \u00c5\u22123\u0394\u03c1min = \u22121.45 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  general, I. DOI: 10.1107/S1600536813029693/hg5358Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The SnIV ion is coordinated by two N atoms [Sn\u2014N = 2.266\u2005(2) and 2.274\u2005(2)\u2005\u00c5] from the bis\u00ad(2-pyrid\u00adyl)selenide ligand and four chloride anions [Sn\u2014Cl = 2.3717\u2005(6)\u20132.3939\u2005(6)\u2005\u00c5] in a distorted octa\u00adhedral geometry. The central six-membered chelate ring has a boat conformation with the Se and Sn atoms deviating by 0.692\u2005(3) and 0.855\u2005(3)\u2005\u00c5, respectively, from the mean plane through the remaining four ring atoms. The pyridine rings are inclined to each other by a dihedral angle of 49.62\u2005(8)\u00b0. The crystal packing exhibits short inter\u00admolecular Se\u22efCl contacts [3.5417\u2005(7) and 3.5648\u2005(7)\u2005\u00c5], weak C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings with a centroid\u2013centroid distance of 3.683\u2005(3)\u2005\u00c5.The title compound, [SnCl DOI: 10.1107/S160053681202586X/cv5309Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal structure, the complex mol\u00adecules and the uncoodinated water mol\u00adecules are connected by O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds into a three-dimensional network. A \u03c0\u2013\u03c0 stacking inter\u00adaction between the pyridyl ring of the ip ligand and the benzene ring of the neighboring ligand [centroid\u2013centroid distance = 3.579\u2005(2)\u2005\u00c5] is also observed.In the title centrosymmetric dinuclear compound, [Mn DOI: 10.1107/S1600536810031909/hy2338Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are significant differences in the chemically equivalent Cd\u2014O bond lengths [2.618\u2005(2)\u2005\u00c5 and 2.561\u2005(2)\u2005\u00c5].In the title compound, [Cd(C DOI: 10.1107/S1600536811038712/lh5332Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the ZnII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 2.96\u2005(11)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 79.26\u2005(4)\u00b0. The coordinating water mol\u00adecule links with the carboxyl\u00adate group via an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. A \u03c0\u2013\u03c0 contact between the parallel pyridine rings of adjacent mol\u00adecules may further stabilize the crystal structure [centroid\u2013centroid distance = 3.5654\u2005(8)\u2005\u00c5].In the title complex, [Zn(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.025wR(F2) = 0.081S = 1.164409 reflections246 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.46 e \u00c5\u22123\u0394\u03c1min = \u22120.33 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812031200/xu5586Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the 1-benzyl-3-methyl\u00adimidazolium units, the dihedral angles between imidazolium and phenyl rings are 80.47\u2005(15) and 76.53\u2005(14)\u00b0. The F atoms of the general-position hexa\u00adfluoro\u00adphosphate anion are disordered over two sets of sites in a 0.767\u2005(17):0.233\u2005(17) ratio. In the crystal, the hexa\u00adfluoro\u00adphosphate anions link the cations into three-dimensional networks via inter\u00admolecular C\u2014H\u22efF hydrogen bonds and are further consolidated by \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distances = 3.5518\u2005(15)\u2005\u00c5] inter\u00adactions.In the title compound, K[Ag(C DOI: 10.1107/S1600536810051925/hb5767Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two independent mol\u00adecules do not differ substanti\u00adally and a mol\u00adecule of water completes the asymmetric unit. The synthesis of the title compound does not modify the stereochemical center, as shown by the absolute configuration found in this crystal structure. Comparison with the non-bromo starting material differs mainly by rotation features. For instance the H(methine)\u2014C\u2014C(methyl\u00adene)\u2014C(ipso) is 173.0\u2005(2)\u00b0 torsion angle in one mol\u00adecule and 177.3\u2005(2)\u00b0 in the other, indicating a trans arrangement. This is in contrast with approximately 50\u00b0 in the starting material. A short inter\u00admolecular Br\u22efBr separation is observed [3.2938\u2005(3)\u2005\u00c5]. The molecules in the crystal are connected via a network of hydrogen bonds through an N\u2014H\u22efO hydrogen bond between the hydroxy group of the phenol of the tyrosine and the N\u2014H of the amide of the other molecule and an O\u2014H\u22efO hydrogen bond between the hydroxy group of the carboxylic acid and the oxygen of the carbonyl of the amide.The title compound, C N-Acetyl-3,5-dibromo-l-tyrosine is a substrate of biological inter\u00adest, for instance it is involved in the synthesis of isodityrosine unit, which has been found in numerous biologically active natural products that include K-13, OF4949 and vancomycin family of glycopeptide anti\u00adbiotics. For the synthesis and specific optical activity of the title compound, see: Bovonsombat et al.  \u00c5b = 22.5186 (9) \u00c5c = 8.6486 (4) \u00c5\u03b2 = 105.946 (1)\u00b0V = 1331.3 (1) \u00c53Z = 4K\u03b1 radiationMo \u22121\u03bc = 6.10 mmT = 125 K0.23 \u00d7 0.17 \u00d7 0.05 mmBruker SMART CCD area-detector diffractometerSADABS; Bruker 2007Tmin = 0.334, Tmax = 0.750Absorption correction: multi-scan (18331 measured reflections7067 independent reflectionsI > 2\u03c3(I)6449 reflections with Rint = 0.030R[F2 > 2\u03c3(F2)] = 0.022wR(F2) = 0.048S = 0.927067 reflections361 parameters17 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.41 e \u00c5\u22123\u0394\u03c1min = \u22120.34 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 3399 FrFlack parameter: 0.005 (5)SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812032928/bg2470Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032928/bg2470Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.745\u2005(3)\u2005\u00c5] are present in the crystal.In the title compound, [CoCl DOI: Click here for additional data file.10.1107/S1600536812041116/hy2591Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The bridging function of the Br atoms leads to a chain structure along [100]. Inter\u00adchain C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 contacts between the thia\u00adzole rings [centroid\u2013centroid distances = 3.810\u2005(5) and 3.679\u2005(5)\u2005\u00c5] are observed.In the title coordination polymer, [CdBr DOI: 10.1107/S1600536811020861/hy2437Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.763\u2005(5)\u2005\u00c5] are present.In the title compound, [CdBr DOI: 10.1107/S1600536812033648/hy2576Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 32.12\u2005(14)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.02\u2005(5)\u00b0. The coordinating water mol\u00adecule links with the carboxyl\u00adate group via an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network.In the title complex, [Cu(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.021wR(F2) = 0.058S = 1.133531 reflections203 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.97 e \u00c5\u22123\u0394\u03c1min = \u22120.50 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812034587/xu5599Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atom is located on an inversion centre and has an overall octa\u00adhedral coordination environment. Two N and two O atoms from (pyzdc)2\u2212 ligands define the equatorial plane and two water mol\u00adecules are in axial positions, resulting in a typical tetra\u00adgonally Jahn\u2013Teller-distorted environment. Extensive classical O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO and non-classical C\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between aromatic rings of the cations [centroid\u2013centroid distance = 3.58\u2005(9)\u2005\u00c5], lead to the formation of a three-dimensional supra\u00admolecular structure.The title compound, (C DOI: 10.1107/S1600536811008981/wm2462Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordin\u00adation sphere about one CoII atom comprises four O-atom donors from two bidentate chelate (Ophenolate and Ocarbox\u00adyl) and bridging dianionic ligands and two water mol\u00adecules [Co\u2014O range = 2.0249\u2005(11)\u20132.1386\u2005(14)\u2005\u00c5], while that about the second CoII atom has four water mol\u00adecules and two bridging carboxyl\u00adate O-donor atoms [Co\u2014O range = 2.0690\u2005(14)\u20132.1364\u2005(11)\u2005\u00c5]. The coordinated water mol\u00adecules as well as the water mol\u00adecules of solvation give O\u2014H\u22efO water\u2013water and water\u2013carboxyl hydrogen-bonding inter\u00adactions in the three-dimensional framework structure.In polymeric title compound, {[Co II, see: Deng et al. 2(H2O)6]\u00b72H2O = 0.023                           wR(F                           2) = 0.061                           S = 1.07                           2560 reflections225 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.32 e \u00c5\u22123                        \u0394\u03c1min = \u22120.47 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SIR92 (Altomare et al., 1994SHELXL97 (Sheldrick, 2008PLATON (Spek, 2009PLATON.Data collection: 10.1107/S1600536810052694/rn2077sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810052694/rn2077Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The MnII ion exhibits a centrosymmetric octa\u00adhedral geometry involving two carboxyl\u00adate O atoms of two different pztmb ligands and four O atoms of four coordinated water mol\u00adecules. The packing shows a three-dimensional supra\u00admolecular network via O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.884\u2005(8) and 4.034\u2005(8)\u2005\u00c5] between the benzene ring of one pztmb anion and the pyrazine ring of an adjacent anion.The title compound, [Mn(C DOI: 10.1107/S160053681004506X/pk2282Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The full dimer is generated by an inversion center. In the dimer, the two IrIII atoms and two bridging Cl atoms form a perfectly planar ring. The two IrIII atoms and the two terminal Cl atoms also form a rigorous plane that is orthogonal [89.48\u2005(3)\u00b0] to the Ir2Cl2 ring. The plane of the cyclo\u00adpenta\u00addienyl ligand forms a dihedral angle of 54.06\u2005(7)\u00b0 with respect to the Ir2Cl2 ring.The asymmetric unit of the title complex, [Ir For the al. 2011.2Cl4(C12H19)2] = 0.019wR(F2) = 0.040S = 1.064440 reflections141 parametersH-atom parameters constrainedmax = 1.02 e \u00c5\u22123\u0394\u03c1min = \u22121.18 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813005072/pk2466Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813005072/pk2466Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, [RuCl2(C15H10)(C18H15P)2]\u00b72C4H8O, has a distorted square-pyramidal conformation. The P and Cl atoms are at the base of the pyramid and the Ru\u2014Cindenyl\u00adidene bond is in the axial position. The two Cl ligands and the two phosphane ligands are in trans positions. The Cl\u2014Ru\u2014Cl and P\u2014Ru\u2014P angles are 157.71\u2005(2) and 166.83\u2005(2)\u00b0, respectively. The two independent tetra\u00adhydro\u00adfuran (THF) solvent mol\u00adecules are disordered. One THF mol\u00adecule was refined using a split-atom model. The second THF mol\u00adecule was accounted for by using program PLATON/SQUEEZE . The molecular conformation shows three intramolecular C\u2014H\u22efCl contacts and two C\u2014H\u22ef\u03c0 interactions while the crystal packing features an intermolecular C\u2014H\u22efCl contact and two very weak intermolecular C\u2014H\u22ef\u03c0 contacts.The RuSpek 2009. Acta Cr DOI: 10.1107/S1600536811016692/si2353Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Si2Cp centroid\u2013titanium distance is 2.0763\u2005(10)\u2005\u00c5 and the SiCp centroid\u2013titanium distance is 2.0793\u2005(10)\u2005\u00c5. The angle subtended at the Ti atom by the centroids of both cyclo\u00adpenta\u00addienyl rings is 131.22\u2005(4)\u00b0 and the Cl\u2014Ti\u2014Cl angle is 94.14\u2005(2)\u00b0.In the title compound, [Ti(C DOI: 10.1107/S1600536811046228/fj2469Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two heterocyclic rings of the 5-(2-pyridin-2-\u00adyl)pyrazine-2-carbonitrile ligand are almost coplanar [dihedral angle = 5.63\u2005(8)\u00b0], and the two chelating ligands are in an anti relationship. The mononuclear units are inter\u00adconnected along [010] through C\u2014H\u22efO(nitrate) and C\u2014H\u22efN(cyano) inter\u00adactions, forming an infinite chain. The mononuclear units are stacked along the a axis and inter\u00adconnected via inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent pyridine and pyrazine rings [centroid\u2013centroid distances = 3.984\u2005(2) and 3.595\u2005(3)\u2005\u00c5], thus forming a three-dimensional supra\u00admolecular structure.In the mononuclear title complex, [Ag(NO DOI: 10.1107/S1600536811049221/zq2135Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A significant Jahn\u2013Teller distortion is observed with two axial Cu\u2014O distances significantly longer than those in the equatorial CuO2N2 plane. In the crystal, \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances of 3.547\u2005(3) or 3.728\u2005(3)\u2005\u00c5 between the phenanthroline rings, form layers parallel to (011).In the title compound, [Cu(C DOI: 10.1107/S1600536811018162/sj5144Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the N-bound H atoms is involved in an intra\u00admolecular N\u2014H\u22efCl hydrogen bond, while another one inter\u00adacts with the solvent methanol mol\u00adecule via an N\u2014H\u22efO hydrogen bond. Inter\u00admolecular O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds link two further complex mol\u00adecules and four solvent mol\u00adecules into a centrosymmetric structural unit. The short distance of 3.624\u2005(4)\u2005\u00c5 between the centroids of the five- and the six-membered rings of two benzimidazole fragments indicates the presence of \u03c0\u2013\u03c0 inter\u00adactions.In the title complex, [CuCl(C I complexes with triphenlyphosphine ligands, see: Gennari et al. -thione ligand, see: Schneider et al. (C18H15P)2]\u00b72CH4O = 0.086wR(F2) = 0.217S = 1.077835 reflections510 parametersH-atom parameters constrainedmax = 1.53 e \u00c5\u22123\u0394\u03c1min = \u22120.57 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536814001251/cv5442Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814001251/cv5442Isup3.cdxSupporting information file. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the complex mol\u00adecules are connected by O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 interactions between the benzene rings [centroid\u2013centroid distance = 3.8924\u2005(17)\u2005\u00c5] into a chain along [010]. Between adjacent chains, \u03c0\u2013\u03c0 inter\u00adactions occur between the pyridine rings [centroid\u2013centroid distance = 3.898\u2005(2)\u2005\u00c5], giving an overall two-dimensional architecture.In the title compound, [Co(C DOI: Click here for additional data file.10.1107/S1600536813006752/hy2620Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dipic and acr ligands are nearly planar [maximum deviation = 0.069\u2005(3)\u2005\u00c5 in dipic and 0.091\u2005(4)\u2005\u00c5 in acr] and the dihedral angle between their mean planes is 58.67\u2005(7)\u00b0. The Pd\u2014O bond lengths are nearly equal, but the Pd\u2014N bond lengths are slightly different. There is a short C\u2014H\u22efO inter\u00adaction in the mol\u00adecule involving the two ligands. In the crystal, complex mol\u00adecules are linked through C\u2014H\u22efO inter\u00adactions, forming a three-dimensional network. There are also a number of inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions present, the shortest ring centroid\u2013centroid distance being 3.622\u2005(3)\u2005\u00c5.In the title complex, [Pd(C II complex [Pt(C7H3NO4)(C13H9N)], see: Ha (C13H9N)] = 0.041wR(F2) = 0.100S = 0.993152 reflections244 parametersH-atom parameters constrainedmax = 1.21 e \u00c5\u22123\u0394\u03c1min = \u22121.14 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812011385/su2392Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One of the Cp rings is substituted by a nitro\u00adbenzenamine group, which is essentially perpendicular to the substituted cyclo\u00adpenta\u00addienyl ring, with an N\u2014C(H2)\u2014C\u2014C torsion angle of 89.8\u2005(2)\u00b0. Intra\u00admolecular N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds occur. In the crystal, weak C\u2014H\u22efO hydrogen bonds link adjacent mol\u00adecules. In the title compound, [Fe(C DOI: 10.1107/S1600536812039177/zq2180Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mononuclear units are inter\u00adconnected through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.801\u2005(2) and 3.979\u2005(3)\u2005\u00c5] and the hexa\u00adfluoridophosphate anions are embedded within the inter\u00adstices. C\u00a0N\u22ef\u03c0 inter\u00adactions [N\u22efcentroid = 3.519\u2005(2)\u2005\u00c5] and C\u2014H.\u22efN hydrogen-bonding inter\u00adactions also occur.In the mononuclear title complex, [Ag(C DOI: 10.1107/S1600536811051403/bt5734Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the mol\u00adecules inter\u00adact through inter\u00admolecular N\u2014H\u22efO hydrogen bonds between the amino and meth\u00adoxy groups on the naphthalene ring systems and N\u2014H\u22ef\u03c0 inter\u00adactions between the amino groups and the naphthalene rings. Furthermore, weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the benzene rings are observed. The centroid\u2013centroid and inter\u00adplanar distances between the benzene rings of the aroyl group and the naphthalene ring systems of adjacent mol\u00adecules are 3.6954\u2005(8) and 3.2375\u2005(5)\u2005\u00c5, respectively. The dihedral angle between the mean planes of the benzene ring and the naphthalene ring system is 83.59\u2005(5)\u00b0. The benzene ring and the carbonyl group in the benzoyl unit are almost coplanar [C\u2014C\u2014C\u2014O torsion angle = 175.91\u2005(10)\u00b0].The title compound {systematic name: (4-aminophenyl)methanone}, C DOI: 10.1107/S1600536810041346/rz2496Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The O atom, the aldehyde H atom and the benzene ring of one of the FB anions are disordered over two positions. The O atoms were freely refined [refined occupancy ratio 0.79\u2005(2):0.21\u2005(2)], while the aldehyde H atoms and the benzene ring atoms were refined with fixed occupancy ratios of 0.8:0.2 and 0.5:0.5, respectively. In the ordered FB anion, the carboxyl\u00adate group is twisted away from the attached benzene ring (A) by 22.7\u2005(8)\u00b0. In the disordered FB anion, the corresponding angles are 15.6\u2005(10) and 11.4\u2005(11)\u00b0 for rings B and B\u2032, respectively. Benzene rings A and B are oriented at a dihedral angle of 24.2\u2005(7), A and B\u2032 at 43.0\u2005(8)\u00b0. The pyrazine ring makes dihedral angles of 67.5\u2005(4), 89.6\u2005(7) and 86.2\u2005(7)\u00b0, respectively, with benzene rings A, B and B\u2032. The pyrazine ligands bridge the CdII cations, forming polymeric chains running along the b-axis direction. In the crystal, O\u2014Hwater \u22ef Ocarboxyl\u00adate hydrogen bonds link adjacent chains into layers parallel to the bc plane. These layers are linked via C\u2014Hpyrazine \u22ef Oform\u00adyl hydrogen bonds, forming a three-dimensional network. \u03c0\u2013\u03c0 interactions [centroid\u2013centroid distances = 3.870\u2005(11)\u20133.951\u2005(5)\u2005\u00c5] further stabilize the crystal structure. There is also a weak C\u2014H\u22ef\u03c0 inter\u00adaction present.The polymeric title compound, [Cd(C DOI: 10.1107/S1600536813035010/su2679Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal packing features \u03c0\u2013\u03c0 contacts between the pyridine rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.773\u2005(5)\u2005\u00c5] and also between a pyridine ring of one mol\u00adecule and the five-membered chelate ring of an adjacent mol\u00adecule [centroid\u2013centroid distance = 3.668\u2005(4)\u2005\u00c5].In the title complex, [HgI DOI: 10.1107/S1600536811004041/ya2136Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometry of the resulting CuN2O4 coordination can be described as distorted octa\u00adhedral. In the crystal, there are several inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. An intra\u00admolecular N\u2014H\u22efO hydrogen bond occurs in one of the cations. Considerable \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed between the aromatic rings of the cations, with centroid\u2013centroid distances of 3.4567\u2005(13), 3.5342\u2005(14), 3.6941\u2005(14) and 3.4568\u2005(13)\u2005\u00c5. These non-covalent inter\u00adactions connect the components, forming a three-dimensional supra\u00admolecular structure.The title compound, (C DOI: 10.1107/S160053681100674X/vm2078Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The PMe3 ligand is coordinated in the basal position, roughly cis to the Fe\u2014Fe bond. The Fe\u2014Fe distance of 2.4970\u2005(6)\u2005\u00c5 is relatively short compared to those (ca 2.53\u2005\u00c5) found in another monosubstituted diiron compound. A rigid planar dithiol\u00adate bridge is featured, with an angle of 2.78\u2005(1)\u00b0 between the Fe\u2014Fe bond and the normal to the pyrazine-2,3-dithiol\u00adate plane.In the title compound, [Fe DOI: 10.1107/S1600536811046770/hy2484Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, C\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efS inter\u00adactions link adjacent mol\u00adecules into layers parallel to the ac plane. A weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction occurs between the aromatic rings with a centroid\u2013centroid distance of 3.9412\u2005(9)\u2005\u00c5.In the title compound, [Cu(NCS) DOI: 10.1107/S1600536810050889/is2639Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atom exhibits a distorted octa\u00adhedral N3O3 environment. O\u2014H\u22efO hydrogen bonding between coordinated water and carboxyl\u00adate O atoms, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions [inter\u00adplanar distances between phen rings = 3.293\u2005(2)\u2005\u00c5] lead to a supermolecular assembly.The title compound, [Ni(C DOI: 10.1107/S1600536811026055/pv2419Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Characteristic features of the Cu6S6 skeleton are a total of six chemically identical \u03bc3-thiol\u00adate bridges and almost planar Cu2S2 units with a maximum deviation of 0.110\u2005(1)\u2005\u00c5 from the best plane. Each Cu2S2 unit then shares common Cu\u2013S edges with a neighbouring unit; the enclosed dihedral angle is 60.14\u2005(2)\u00b0. The geometric centre of the Cu6S6 cation lies on a crystallographic inversion centre. Cu\u2014S bond lengths range from 2.294\u2005(1) to 2.457\u2005(1)\u2005\u00c5, Cu\u2014N bond lengths from 2.005\u2005(3) to 2.018\u2005(3)\u2005\u00c5 and the non-bonding Cu\u22efCu distances from 2.5743\u2005(7) to 2.5892\u2005(6)\u2005\u00c5. C\u2014H\u22efF hydrogen-bond inter\u00adactions occur between the PF6\u2212 anion and the complex mol\u00adecule and between the PF6\u2212 anion and the acetonitrile solvent mol\u00adecule.The mol\u00adecular structure of the title compound, [Cu DOI: Click here for additional data file.10.1107/S1600536812050428/nr2037Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, dinuclear units with a Cd\u22efCd separation of 3.8208\u2005(7)\u2005\u00c5 are observed. Each of these dinuclear units is bridged via 3,3\u2032-bpda in a chelating/chelating and bridging fashion, generating a zigzag chain along the c axis. Neighboring chains are further packed via weak \u03c0\u2013\u03c0 inter\u00adactions between inter\u00adchain parallel 1,10-phen rings [centroid\u2013centroid distance = 3.5197\u2005(9)\u2005\u00c5] into a three-dimensional supra\u00admolecular architecture.In the title compound, [Cd(C DOI: 10.1107/S1600536811042085/im2322Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Of the two water H atoms, one is engaged in an intra\u00admolecular hydrogen bond with a free oxygen of the dianion whereas the second is engaged in an inter\u00admolecular hydrogen bond, building a corrugated layer parallel to (100). These layers are further connected through \u03c0\u2013\u03c0 stacking inter\u00adactions involving symmetry-related phenanthroline rings [centroid\u2013centroid distance = 3.5599\u2005(17) and 3.5617\u2005(18)\u2005\u00c5], building a three dimensionnal network. C\u2014H\u22ef\u03c0 inter\u00adactions involving the phenanthroline ring system are also observed.In the centrosymmetric dinuclear title complex, [Cu DOI: 10.1107/S1600536811007938/dn2661Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "I atom in the title centrosymmetric dinuclear compound, [Ag2(C11H10N3O)2(C11H11N3O)2]\u00b72H2O, shows a T-shaped coordination arising from bonding to the N atom of a neutral 2-[(pyrimidin-2-yl)amino\u00admeth\u00adyl]phenol ligand, the N atom of the 2-[(pyrimidin-2-yl)amino\u00admeth\u00adyl]phenolate anion [N\u2014Ag\u2014N = 171.8\u2005(1)\u00b0] and the terminal O atom of the other anion [Ag\u2014O = 2.606\u2005(3)\u2005\u00c5]. A pair of 2-[(pyrimidin-2-yl)amino\u00admeth\u00adyl]phenolate anions link the two AgI atoms to form the dinuclear compound. In the crystal, adjacent dinuclear mol\u00adecules are linked to the lattice water mol\u00adecules, generating an O\u2014H\u22efO- and N\u2014H\u22efO-connected three-dimensional network. In the crystal, the hy\u00addroxy H atom is disordered over two positions in a 1:1 ratio; one half-occupancy H atom is connected to one hy\u00addroxy group, whereas the other half-occupancy H atom is connected to another hy\u00addroxy group. The Ag DOI: Click here for additional data file.10.1107/S1600536812045783/xu5644Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal packing is dominated by inter\u00admolecular C\u2014H\u22efF hydrogen bonds, C\u2014F\u22ef\u03c0 inter\u00adactions between the penta\u00adfluoro\u00adbenzene groups [F\u22efcentroid distances = 3.882\u2005(2) and 3.884\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions between the penta\u00adfluoro\u00adbenzene and cyclo\u00adpenta\u00addienyl rings [centroid\u2013centroid distance = 3.741\u2005(1)\u2005\u00c5].The mol\u00adecular structure of the title compound, [Fe(C DOI: 10.1107/S1600536810026772/hy2327Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the packing of the mol\u00adecules is controlled by C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions  and weak Br\u22efBr halogen bonds [3.508\u2005(4)\u2005\u00c5], linking the mol\u00adecules into an infinite three-dimensional supra\u00admolecular network.In the title complex, [Cu(C DOI: Click here for additional data file.10.1107/S1600536813009847/zl2543Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the cation, the pyridinium rings attached to the central 1-aza\u00adniumyl-2-hy\u00addroxy\u00adethane fragment have an anti conformation, as indicated by the central C\u2014C\u2014C\u2014C torsion angle of \u2212166.5\u2005(6)\u00b0, and they are inclined to one another by 63.5\u2005(4)\u00b0. In the crystal, the cations and anions are linked through N\u2014H\u22efCl and O\u2014H\u22efCl hydrogen bonds. There are also \u03c0\u2013\u03c0 contacts [centroid\u2013centroid distances = 3.671\u2005(4) and 3.851\u2005(4)\u2005\u00c5] and a number of C\u2014H\u22efCl inter\u00adactions present, consolidating the formation of a three-dimensional supra\u00admolecular structure.The title compound, (C DOI: Click here for additional data file.10.1107/S160053681300425X/su2560Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The PbN2S4 coordination geometry approximates to a penta\u00adgonal bipyramid with one equatorial site vacant. The N atoms occupy the axial sites. One of the pyridine mol\u00adecules is disordered over two sets of sites in a 0.907\u2005(7):0.093\u2005(7) ratio and one of the tert-butyl groups is disordered over two sets of sites in a 0.534\u2005(6):0.466\u2005(6) ratio. An intra\u00admolecular C\u2014H\u22efO inter\u00adaction occurs in one of the ligands. In the crystal, pairs of short Pb\u22efS contacts [3.4018\u2005(11)\u2005\u00c5] generate a centrosymmetric dimeric assembly with the distant S atom lying in the region of the vacant coordination site of the metal atom. No directional packing inter\u00adactions occur.In the title compound, [Pb(C For the preparation of the ligand, see: Li & Xie 1997. For van20H26O2PS2)2(C5H5N)2] = 0.033wR(F2) = 0.068S = 1.0210953 reflections663 parameters572 restraintsH-atom parameters constrainedmax = 0.80 e \u00c5\u22123\u0394\u03c1min = \u22120.69 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I. DOI: 10.1107/S1600536813023945/hb7129Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mol\u00adecular structure exhibits an S(6) ring motif, owing to an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, weak C\u2014H\u22efO contacts generate an infinite chain along the c axis. There are also \u03c0\u2013\u03c0 stacking inter\u00adactions between neighbouring isochromanedione benzene rings, with a centroid\u2013centroid distance of 3.755\u2005(1)\u2005\u00c5, and C\u2014O\u22ef\u03c0 inter\u00adactions with an O\u22efcentroid distance of 3.964\u2005(2)\u2005\u00c5.In the title compound, C DOI: 10.1107/S1600536811050975/fj2488Isup2.hkl            Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050975/fj2488Isup3.cml            Supplementary material file. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "I cations, three p-toluene\u00adsulfonate (pts) anions, three hexa\u00admethyl\u00adene\u00adtetra\u00admine (hmt) mol\u00adecules and four water mol\u00adecules in the asymmetric unit of the title coordination polymer, {[Ag3(C7H7O3S)3(C6H12N4)3(H2O)]\u00b73H2O}n. Two of the pts anions show positional disorder of their O atoms in 0.60:0.40 and 0.50:0.50 ratios. The AgI ion is coordinated by three hmt mol\u00adecules in an approximate trigonal\u2013planar AgN3 arrangement. In each case, longer Ag\u2014O bonds to a water mol\u00adecule and a pts anion complete a distorted trigonal\u2013bipyramidal AgN3O2 geometry for the metal ion. In the crystal, the bridging hmt mol\u00adecules and pts ions generate a wave-like layer parallel to (001) and O\u2014H\u22efO hydrogen-bonding inter\u00adactions consolidate the packing.There are three Ag DOI: 10.1107/S1600536810048567/hb5739Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The central Cu2N2 core is a rhombus as the \u03bc2-azide ligands bridge in an asymmetric fashion. Each CuII atom is also coordinated by a monoanionic tridentate Schiff base ligand via the anti\u00adcipated oxide O, imine N and amine N atoms. The resulting N4O coordination geometry is based on a square pyramid. No specific inter\u00admolecular inter\u00adactions are noted in the crystal packing, but the amine H atoms form intra\u00admolecular N\u2014H\u22efO(oxide)/N(azide) hydrogen bonds.The complete mol\u00adecule of the title complex, [Cu For a r al. 2012. For add al. 1984.2(C13H19N2O2)2(N3)2] = 0.039wR(F2) = 0.105S = 1.063314 reflections198 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.54 e \u00c5\u22123\u0394\u03c1min = \u22120.52 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812028954/sj5249Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The guanidinium cation (the C atom has site symmetry 3) and the octa\u00adhedral hexa\u00adaqua\u00adzinc(II) dication (the Zn2+ cation has site symmetry -3) are occupationally disordered in a 1.30:0.35 ratio. In the crystal, the components are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds to generate infinite (001) sheets. Weak aromatic \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distance = 3.797\u2005(8)\u2005\u00c5] is also observed in the crystal.In the title mol\u00adecular salt, (CH DOI: 10.1107/S160053681202987X/hb6768Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the nearly planar PtI2NS unit [maximum deviation = 0.083\u2005(2)\u2005\u00c5] and the acridine ligand [maximum deviation = 0.038\u2005(6)\u2005\u00c5] is 89.29\u2005(7)\u00b0. In the crystal structure, the complex mol\u00adecules are arranged in a V-shaped packing pattern along the c axis and linked by inter\u00admolecular C\u2014H\u22efO contacts into supra\u00admolecular chains. There are also several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings, with a shortest ring centroid\u2013centroid distance of 3.804\u2005(5)\u2005\u00c5.In the title complex, [PtI DOI: 10.1107/S1600536810031387/tk2697Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In complex A, [Cd(C7H5O3)2(C6H6NO)2(H2O)2], the CdII cation is located on an inversion center and is coordinated by two salicylate anions, two nicotinamide (NA) ligands and two water mol\u00adecules in a slightly distorted octa\u00adhedral geometry. In complex B, [Cd(C7H5O3)2(C6H6NO)(H2O)2], the CdII cation is coordinated by two salicylate anions, one nicotinamide (NA) ligand and two water mol\u00adecules in an irregular seven-coordinate geometry. There are extensive intra\u00admolecular O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds as well as extensive inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding in the crystal structure. \u03c0\u2013\u03c0 stacking between the pyridine and benzene rings, between the benzene rings, between the benzene and pyridine rings and between the pyridine rings  further stabilize the crystal structure. A weak N\u2014H\u22ef\u03c0 inter\u00adaction also occurs. One of the lattice water mol\u00adecules is disordered over two positions with an occupancy ratio of 0.70:0.30.The crystal structure of the title compound, [Cd(C DOI: Click here for additional data file.10.1107/S1600536813006168/xu5682Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The chain in (I) extends parallel to [100] and is severely puckered, with a Zn\u22efZn distance of 8.3599\u2005(3)\u2005\u00c5 and a Zn\u22efZn\u22efZn angle of 107.516\u2005(3)\u00b0, as a result of hydrogen-bonding inter\u00adactions of the types O\u2014H\u22efO and C\u2014H\u22efO. There is no evidence for \u03c0\u2013\u03c0 inter\u00adactions in (I). The differences between the solvent-free and solvent-containing structures can be accounted for by the absence of the ethanol solvent mol\u00adecule and the use of the converging pair of O atoms in the bis-monodentate bridging HBTC2\u2212 ligand in (I).The title one-dimensional coordination polymer, [Zn(C al. 1997. Chem. M For a r al. 2009. 9H4O6)(C5H5N)2] = 0.028wR(F2) = 0.075S = 1.034402 reflections257 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.32 e \u00c5\u22123\u0394\u03c1min = \u22120.27 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813014347/cq2004Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II complex, [Cu(C7H4BrO2)2(C10H14N2O)2(H2O)2], contains two 4-bromo\u00adbenzoate (PBB), two diethyl\u00adnicotinamide (DENA) monodentate ligands and two water mol\u00adecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by two N atoms of the DENA ligands in the axial positions. Intra\u00admolecular O\u2014H\u22efO hydrogen bonds link the water mol\u00adecules to the carboxyl\u00adate groups. The dihedral angles between the carboxyl\u00adate groups and the adjacent benzene rings are 3.1\u2005(3) and 3.74\u2005(17)\u00b0, while the pyridine rings and the benzene rings are oriented at dihedral angles of 6.81\u2005(10) and 3.38\u2005(12)\u00b0. In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into double chains along the b axis. C\u2014H\u22efO inter\u00adactions are also observed. \u03c0\u2013\u03c0 contacts between pyridine rings [centroid\u2013centroid distance = 3.485\u2005(2)\u2005\u00c5] may further stabilize the crystal structure.The title Cu N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.035                           wR(F                           2) = 0.079                           S = 1.03                           7011 reflections463 parameters5 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 1.08 e \u00c5\u22123                        \u0394\u03c1min = \u22120.59 e \u00c5\u22123                        \u0394\u03c1Absolute structure: Flack 1983, 2353 FrFlack parameter: 0.412 (7)                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811034787/su2303Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NH2CH2CHBrCH2Br ligand contains a chiral carbon atom. The Fe\u2014N bond length is 2.011\u2005(3)\u2005\u00c5 and the Fe\u2014Cp centroid distance is 1.7189\u2005(5)\u2005\u00c5. In the crystal, the ions are linked via two N\u2014H\u22efF inter\u00adactions and a weak N\u2014H\u22efBr inter\u00adaction.The title compound, [Fe(\u03b7 DOI: 10.1107/S1600536812025925/fj2567Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The water mol\u00adecule at the apical position shows a long bond [Cu\u2014O = 2.276\u2005(2)\u2005\u00c5]. The basal plane is formed by two N atoms of the 2,2\u2032-bipyridine ligand and two carboxyl\u00adate O atoms from a malonate group. The five-membered chelate ring is almost planar [maximum deviation = \u22120.006\u2005(2)\u2005\u00c5], while the six-membered chelate ring defined by the malonate ligand adopts a distorted boat conformation. In the crystal, CuII complex mol\u00adecules and lattice water mol\u00adecules are connected by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. The crystal packing is further stabilized by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.563\u2005(2)\u20133.828\u2005(2)\u2005\u00c5].In the title compound, [Cu(C For rel al. 1998; Cui et  al. 2005. For rin al. 2005.4H4O4)(C10H8N2)(H2O)]\u00b72H2O = 0.049wR(F2) = 0.119S = 1.053782 reflections242 parameters6 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.97 e \u00c5\u22123\u0394\u03c1min = \u22120.52 e \u00c5\u22123\u0394\u03c1CrysAlis CCD  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812024889/bt5931Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mean bond lengths of the two Ru complexes are Ru\u2014C = 2.276\u2005\u00c5, Ru\u2014P\u00a0= 2.3816\u2005\u00c5, and Ru\u2014Cl = 2.3924\u2005\u00c5. Both chloride ligands form only intra\u00admolecular C\u2014H\u22efCl inter\u00adactions. Seven weak inter\u00admolecular C\u2014H\u22efF inter\u00adactions involving mainly arene H atoms consolidate the crystal packing, which reveals an approximate c/2 pseudo-translation relating the two independent Ru complex mol\u00adecules.The asymmetric unit of the title compound, [FeRuCl(C DOI: 10.1107/S1600536811036506/kp2346Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and partly overlapping \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 4.017\u2005(2)\u2005\u00c5] into a three-dimensional supra\u00admolecular network.In the title compound, [Zn(C DOI: 10.1107/S1600536811019519/hy2433Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.576\u2005(5)\u2005\u00c5].The title salt, (C DOI: 10.1107/S1600536811024792/aa2014Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, O\u2014H\u22efCl, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distances = 3.7236\u2005(17) and 3.6026\u2005(19)\u2005\u00c5] stabilize the structure. Intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds are also present.In the title compound, [VClO(C DOI: 10.1107/S1600536812040251/hy2588Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The ZnII ion shows a distorted octa\u00adhedral coordination geometry and is coordin\u00adated by two N atoms from two SCN\u2212 anions and four N atoms from two organic ligands. The L ligands act as bridging bis-chelating ligands with cis coordination modes at the ZnII ion. One-dimensional coordination polymers are arranged into layers by \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazole rings of adjacent chains, with an inter\u00adplanar distance of 3.46\u2005(1)\u2005\u00c5 and centroid\u2013centroid distances of 3.8775\u2005(16)\u2005\u00c5. One of the thio\u00adcyanate ligands is disordered over two positions with an occupancy factor of 0.564\u2005(3) for the major component. The partially occupied water mol\u00adecule forms an O\u2014H\u22efS hydrogen bond with the disordered thio\u00adcyanate group.The title one-dimensional coordination polymer, {[Zn(NCS) For coo al. 2004. For sim al. 2002; Luan et al. 2006. For the al. 2008.       2(C24H20N6)2]\u00b70.28H2O = 0.038                           wR(F                           2) = 0.102                           S = 1.04                           4707 reflections362 parameters30 restraintsH-atom parameters constrainedmax = 0.38 e \u00c5\u22123                        \u0394\u03c1min = \u22120.33 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008DIAMOND (Brandenburg & Putz, 2008SHELXL97.Data collection: 10.1107/S1600536810027571/gk2287sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810027571/gk2287Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Intra\u00admolecular C\u2014H\u22efO hydrogen bonds and inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.637\u2005(4) and 3.818\u2005(4)\u2005\u00c5] are present in the crystal structure.In the title compound, [ZnI DOI: 10.1107/S1600536810046763/hy2375Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One AgI atom is coordinated by two pyridine N atoms from two symmetry-related A ligands in a geometry slightly distorted from linear [N\u2014Ag\u2014N = 173.2\u2005(3)\u00b0], forming a left-handed helical chain, while the other AgI atom is coordinated by two pyridine N atoms from two symmetry-related B ligands in a bent arrangement [N\u2014Ag\u2014N = 157.1\u2005(3)\u00b0], forming a right-handed helical chain. Both helical chains have the same pitch length [10.4007\u2005(7)\u2005\u00c5], propagate along the b-axis direction and are alternately arranged via Ag\u22efAg [3.0897\u2005(12)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.564\u2005(7) and 3.518\u2005(6)\u2005\u00c5], resulting in the formation of a two-dimensional supra\u00admolecular network extending parallel to the ab plane. Inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efF hydrogen-bonding inter\u00adactions occur between the helical chains and the anions.In the asymmetric unit of the title polymeric complex, {[Ag(C I coordination polymers with dipyridyl ligands, see: Leong & Vittal ](CF3O3S) = 0.088wR(F2) = 0.238S = 1.095797 reflections415 parameters6 restraintsH-atom parameters constrainedmax = 2.70 e \u00c5\u22123\u0394\u03c1min = \u22121.89 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536813016309/sj5332Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "I ions resulted in the formation of the polymeric title compound, {[Ag(C10H8N2)](C17H9F6O4)}n, in which the metal atoms are bridged by the 4,4\u2032-bipyridine ligands, generating cationic chains extending along [010]. The dihedral angles between the benzene rings in the anion and the pyridine rings in the cation are 72.42\u2005(9) and 9.36\u2005(10)\u00b0, respectively. The mol\u00adecular conformation of the anion is stabilized by intra\u00admolecular C\u2014H\u22efF hydrogen bonds. In the crystal, the anions inter\u00adact with the cationic chains via C\u2014H\u22efO hydrogen bonds, forming layers parallel to (001), in which weak \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.975\u2005(3)\u20134.047\u2005(3)\u2005\u00c5] involving the pyridine rings of adjacent 4,4\u2032-bipyridine ligands are present. The planes are further assembled into a three-dimensional network by O\u2014H\u22efO hydrogen bonds.Assembly of the flexible dicarb\u00adoxy\u00adlic ligand 4-benzoate and 4,4\u2032-bipyridine as co-ligand with Ag DOI: 10.1107/S1600536812015322/rz2731Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II(C2H8N2)3]Cl2, was obtained unexpectedly as the product of an attempted solvothermal synthesis of cobalt selenide from the elements in the presence of NH4Cl in ethyl\u00adenedi\u00adamine solvent. The three chelate rings of the distorted octa\u00adhedral [Co(C2H8N2)3]2+ complex cation adopt twisted conformations about their C\u2014C bonds. The spread of cis-N\u2014Co\u2014N bond angles [80.17\u2005(6)\u201398.10\u2005(6)\u00b0] in the title compound is considerably greater than the equivalent data for [CoIII(C2H8N2)3]Cl3 . In the crystal, the components are linked by numerous N\u2014H\u22efCl hydrogen bonds, generating a three-dimensional network in which the cationic complexes are stacked in columns along [010] and separated by columns of chloride anions.The title compound, [Co al. 2008. Angew.  III\u2013tris-ethyl\u00adenedi\u00adamine complex with chloride counter-anions has been reported by Takamizawa et al. 3]Cl2 = 0.024wR(F2) = 0.059S = 1.062700 reflections232 parametersAll H-atom parameters refinedmax = 0.26 e \u00c5\u22123\u0394\u03c1min = \u22120.37 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813013135/hb7079Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The cyano-bound 4-cyano\u00adpyridine mol\u00adecule also is disordered across the inversion centre. The four N atoms of the pyrrole rings of the dianionic 5,10,15,20-tetra\u00adphenyl\u00adporphyrin ligand occupy the equatorial sites of the octa\u00adhedron [Mg\u2014N = 2.0552\u2005(10) and 2.0678\u2005(11)\u2005\u00c5] and the axial Mg\u2014 bond length is 2.3798\u2005(12)\u2005\u00c5. The crystal packing is stabilized by weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions.In the title complex, [Mg(C DOI: Click here for additional data file.10.1107/S1600536812049434/zs2246Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "It is built up from discrete [Zn{(CH3)2SO}6]2+ units connected through non-classical hydrogen bonds to linear I42\u2212 polyiodide anions (C\u2014H\u22efI = 3.168\u2005\u00c5). The ZnII ion in the cation has an octa\u00adhedral coordination geometry, with all six Zn\u2014O bond lengths being equivalent, at 2.111\u2005(4)\u2005\u00c5. The linear polyiodide anion contains a neutral I2 mol\u00adecule weakly coordinated to two iodide ions.The title compound, [Zn{(CH DOI: 10.1107/S1600536813028377/fj2643Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each Mo2               4+ unit is equatorially coordinated by four pentafluoro\u00adbenzoate groups, while the axial positions are occupied by two 4,4\u2032-bipyridine mol\u00adecules. The Mo\u2014Mo bond length of 2.1227\u2005(4)\u2005\u00c5 is representative of a dimolybdenum quadruple bond. An infinite linear chain parallel to [110] is formed by the Mo2               4+ unit coordinating axially to the two N atoms of the 4,4\u2032-bipyridine ligand [Mo\u2014N = 2.594\u2005(2)\u2005\u00c5]. The crystal packing shows mol\u00adecules linked together into a three-dimensional network via Mo\u2014N coordination inter\u00adactions and weak \u03c0\u2013\u03c0 stacking inter\u00adactions between perfluoro\u00adphenyl rings [centroid\u2013centroid distance = 3.7280\u2005(3)\u2005\u00c5 and centroid-to-plane distance = 3.6103\u2005(12)\u2005\u00c5 between two penta\u00adfluoro\u00adphenyl rings]. In the title compound, [Mo DOI: 10.1107/S1600536811031734/jj2094Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The water mol\u00adecules and 3,5-bis\u00ad(trifluoro\u00admeth\u00adyl)pyrazolide anions act as bridges between the potassium cations. Each potassium cation is surrounded by four O atoms [K\u2014O = 2.705\u2005(3)\u20132.767\u2005(3)\u2005\u00c5] and four F atoms [K\u2014F = 2.870\u2005(7)\u20133.215\u2005(13)\u2005\u00c5]. The water mol\u00adecules and the 3,5-bis\u00ad(trifluoro\u00admeth\u00adyl)pyrazolide anions are connected by O\u2014H\u22efN hydrogen bonds, forming layers in the ab plane. All \u2013CF3 groups show rotational disorder between two orientations each.The asymmetric unit of the title compound, [K(C DOI: 10.1107/S1600536810027133/cv2744Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ReI atom is facially surrounded by three carbonyl ligands and a tridentate bis\u00ad(pyridin-2-ylmeth\u00adyl)amine ligand in a distorted octahedral environment. N\u2014H\u22efBr, O\u2014H\u22efBr, C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds are present in the crystal structure and \u03c0\u2013\u03c0 stacking is also observed [centroid\u2013centroid distances = 3.669\u2005(1)\u2005\u00c5 and 4.054\u2005(1)\u2005\u00c5], giving rise to a three-dimentional network. The mol\u00adecules pack in a head-to-head fashion along the ac plane.The title compound,  DOI: 10.1107/S1600536812019654/ru2033Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "All of the CuII atoms in the trinuclear centrosymmetric title complex are six-coordinated in a distorted octa\u00adhedral geometry with N2O4 and N4O2 environments for the outer and central CuII atoms, respectively. Various inter\u00adactions, including numerous O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014O\u22ef\u03c0 stacking of the pyridine and carboxyl\u00adate groups [O\u22efcentroid distances = 3.669\u2005(2) and 3.668\u2005(2)\u2005\u00c5] are observed in the crystal structure. The title compound, [Cu DOI: 10.1107/S1600536812022039/qm2066Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Weak C\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds between the 1-ethyl-4,4\u2032-bipyridin-1-ium cations and mnt anions and weak \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of the cations [centroid\u2013centroid distances = 3.808\u2005(3) and 3.972\u2005(3)\u2005\u00c5] lead to a two-dimensional network parallel to (010).In the anion of the title compound, (C DOI: 10.1107/S1600536813015493/hy2630Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the benzene rings is 36.86\u2005(14)\u00b0. In the crystal, mol\u00adecules are linked into inversion dimers by pairs of weak C\u2014H\u22efO hydrogen bonds. In addition, \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.7279\u2005(16)\u2005\u00c5] and weak C\u2014H\u22ef\u03c0 inter\u00adactions are observed.In the title Schiff base complex, [Cu(C DOI: 10.1107/S1600536812033491/lh5504Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The angles between the mean planes of the pyrrolo-indole ring and the phenyl\u00adsulfonyl and p-toluene\u00adsulfonyl rings are 73.7\u2005(6) and 80.6\u2005(0)\u00b0, respectively. The dihedral angle between the mean planes of the two benzene rings is 78.7\u2005(4)\u00b0. In the crystal, both classical N\u2014H\u22efO and non-classical C\u2014H\u22efO inter\u00admolecular hydrogen-bonding inter\u00adactions are observed, as well as weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.6258\u2005(8) and 3.9298\u2005(8)\u2005\u00c5], which contribute to the stability of the packing.The title compound, C DOI: 10.1107/S1600536810039425/fl2319Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the solid state, the second acidic proton of isophthalic acid is partially transferred to the imidazole N atom of the adeninium cation [refined O\u2014H versus N\u2014H ratio = 0.70\u2005(11):0.30\u2005(11)]. Through the partially transferred proton, the adeninium cation is strongly hydrogen bonded (N\u2014H\u22efO/O\u2014H\u22efN) to the isophthalate anion. This strong inter\u00adaction is assisted by another N\u2014H\u22efO hydrogen bond originating from the adeninium NH2 group towards the isophthalate keto O atom, with an R22(8) graph-set motif. This arrangement is linked via N\u2014H\u22efO hydrogen bonds to the O atoms of the carboxyl\u00adate group of an isophthalate anion. Together, these hydrogen bonds lead to the formation criss-cross zigzag isophthalate\u22efadeninium chains lying parallel to (501) and (50-1). The adeninium cations and the isophthalate anions are arranged in infinite \u03c0 stacks that extend along the c-axis direction [inter\u00adplanar distance = 3.305\u2005(3)\u2005\u00c5]. Mol\u00adecules are inclined with respect to this direction and within the stacks they are offset by ca. half a mol\u00adecule each. Combination of the N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds with the \u03c0\u2013\u03c0 inter\u00adactions forms infinitely stacked isophthalate\u22efadeninium chains, thus leading to a two-dimensional supra\u00admolecular structure with parallel inter\u00addigitating layers formed by the \u03c0 stacked isophthalate\u22efadeninium chains. The DMF mol\u00adecules of crystallization are bonded to the adeninium cations through strong N\u2014H\u22efO hydrogen bonds and project into the lattice space in between the anions and cations. There are also C\u2014H\u22efO hydrogen bonds present which, combined with the other inter\u00adactions, form a three-dimensional network. The crystal under investigation was found to be split and was handled as if non-merohedrally twinned.In the title proton-transfer organic salt, C \u00c5b = 46.05 (2) \u00c5c = 3.7832 (18) \u00c5V = 6674 (5) \u00c53Z = 16K\u03b1 radiationMo \u22121\u03bc = 0.11 mmT = 100 K0.55 \u00d7 0.15 \u00d7 0.04 mmBruker SMART APEX CCD diffractometerTmin = 0.730, Tmax = 1.000Absorption correction: multi-scan 2703 reflections with R[F2 > 2\u03c3(F2)] = 0.088wR(F2) = 0.233S = 1.053888 reflections251 parameters2 restraintsH atoms treated my a mixture of independent and constrained refinementmax = 0.58 e \u00c5\u22123\u0394\u03c1min = \u22120.50 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536813034971/su2677Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813034971/su2677Isup3.cmlSupporting information file. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Four water O atoms in the equatorial plane around the ZnII ion [Zn\u2014O = 2.089\u2005(2) and 2.128\u2005(2)\u2005\u00c5] form a slightly distorted square-planar arrangement and the distorted octa\u00adhedral geometry is completed by the two N atoms [Zn\u2014N = 2.117\u2005(2)\u2005\u00c5] from two isonicotinamide ligands. In the anion, the carboxyl\u00adate group is twisted from the attached benzene ring at 9.0\u2005(2)\u00b0. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O\u2014H\u22efO and N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds, consolidates the crystal packing, which exhibits \u03c0\u2013\u03c0 stacking between the benzene and pyridine rings, with centroid\u2013centroid distances of 3.458\u2005(2) and 3.609\u2005(2)\u2005\u00c5. One of the two H atoms of each uncoordinating water mol\u00adecule is disordered over two orientations with an occupancy ratio of 0.60:0.40.The asymmetric unit of the title compound, [Zn(C DOI: Click here for additional data file.10.1107/S1600536813006466/xu5683Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, the components are linked by O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and weak aromatic \u03c0\u2013\u03c0 stacking [shortest centroid\u2013centroid separation = 3.778\u2005(2)\u2005\u00c5] inter\u00adactions. (001) layers of alternating organic cations and complex inorganic anions are apparent.In the title compound, (C DOI: 10.1107/S1600536814002530/hb7194Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Fe atom and the phenolate ligand are disordered across the porphyrin ring with the two phenolates appearing to be roughly related by a center of symmetry. The occupancies of the two phenolate groups refined to 0.788\u2005(3) for the major component and 0.212\u2005(3) for the minor component. The structure shows extraordinary Fe displacements of 0.488\u2005(4) (major) and 0.673\u2005(4)\u2005\u00c5 (minor) from the 24-atom mean plane of the porphyrin. The Fe\u2014Np distances range from 2.063\u2005(4) to 2.187\u2005(6)\u2005\u00c5 and the Fe\u2014O distances are 1.903\u2005(5)\u2005\u00c5 for major component and 1.87\u2005(2)\u2005\u00c5 for minor component. The four phenyl groups attached to the porphyrin ring form dihedral angles of 63.4\u2005(4), 49.6\u2005(4), 62.4\u2005(4), and 63.3\u2005(4)\u00b0  with the three nearest C atoms of the porphyrin ring. The major and minor component phenolate groups form dihedral angles of 24.9\u2005(4)\u00b0 and 24.8\u2005(4)\u00b0, respectively, with the four porphyrin N atoms. The Fe\u22efFe distance between the two iron(III) atoms of adjacent porphyrin mol\u00adecules is 6.677\u2005(3)\u2005\u00c5. No close inter\u00admolecular inter\u00adaction was observed. The crystal studied was twinned by inversion, with a major\u2013minor component ratio of 0.53\u2005(3):0.47\u2005(3).The title compound, [Fe(C DOI: 10.1107/S160053681302607X/pk2492Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The structure is isotypic with [CdBr2(C4H5N3O)2] . There are two inter\u00adligand N\u2014H\u22efBr hydrogen bonds, generating two hydrogen-bonded rings stabilizing the coordination sphere. The complex aggregates, forming supra\u00admolecular chains, sheets and staircases through N\u2014H\u22efO and N\u2014H\u22efBr hydrogen bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.616\u2005(2)\u2005\u00c5].In the title complex, [ZnBr DOI: 10.1107/S1600536810049305/hg2756Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, O\u2014H\u22efO, N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds link the complex cations and nitrate anions into a three-dimensional network. \u03c0\u2013\u03c0 inter\u00adactions between the thia\u00adzole and imidazole rings and between the thia\u00adzole and benzene rings are observed [centroid\u2013centroid distances = 3.592\u2005(3) and 3.735\u2005(3)\u2005\u00c5].In the title compound, [NiCl(C DOI: 10.1107/S1600536812029728/hy2553Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, the complexes are linked into a three-dimensional supra\u00admolecular network by both O\u2014H\u22efO hydrogen-bonding inter\u00adactions between water mol\u00adecules and the uncoordinated carboxyl\u00adate O atoms of neighboring mol\u00adecules, and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions between neighboring phenanthroline rings with centroid\u2013centroid distances of 3.4654\u2005(17) and 3.697\u2005(2)\u2005\u00c5.In the title complex, [Zn(C DOI: 10.1107/S1600536810049573/vm2055Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the L ligand, the dihedral angle between benzoimidazole and benzotriazole ring systems is 10.8\u2005(3)\u00b0. In the crystal, the complex mol\u00adecules are connected by O\u2014H\u22efN hydrogen bonds; inter\u00admolecular \u03c0\u2013\u03c0 stacking is also observed [centroid\u2013centroid distances of 3.668\u2005(5)\u2005\u00c5 between triazole and benzene rings and 3.780\u2005(5)\u2005\u00c5 between imidazole rings].In the title complex, [Cd(C DOI: Click here for additional data file.10.1107/S1600536813001827/xu5670Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dimethyl sulfoxide solvent mol\u00adecules and CuII complex mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonding. In addition, C\u2014H\u22efO contacts and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.590\u2005(1)\u2005\u00c5] occur.In the title complex, [Cu(C DOI: 10.1107/S1600536811003424/bt5466Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two essentially planar 2,1,3-benzoselenadiazole ligands [maximum deviations = 0.012\u2005(2) and 0.030\u2005(2)\u2005\u00c5] are approximately coplanar [dihedral angle = 6.14\u2005(6)\u00b0]. In the crystal, short inter\u00admolecular Se\u22efBr, Se\u22efN and N\u22efN inter\u00adactions are observed. These short inter\u00adactions and inter\u00admolecular C\u2014H\u22efBr hydrogen bonds link the complex mol\u00adecules into two-dimensional arrays parallel to the ac plane.In the title complex, [CuBr DOI: 10.1107/S160053681005422X/sj5081Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The anion is an eight-coordinate complex with a square-anti\u00adprismatic geometry around the BiIII atom. In the crystal, extensive O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, as well as ion pairing, C=O\u22ef\u03c0 inter\u00adactions [O\u22efcentroid distance = 3.583\u2005(5)\u2005\u00c5], \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distance = 3.864\u2005(3)\u2005\u00c5], and C\u2014H\u22ef\u03c0 and C\u2014H\u22efO inter\u00adactions, play an important role in the formation and stabilization of the three-dimensional supra\u00admolecular structure.The asymmetric unit of the ionic title compound, (C DOI: 10.1107/S160053681202630X/su2401Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "An intra\u00admolecular C\u2014H\u22efO hydrogen bond occurs. The crystal structure is stabilized by C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distances = 3.582\u2005(5) and 3.582\u2005(5)\u2005\u00c5].In the title compound, [CdBr DOI: 10.1107/S1600536812033168/hy2573Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The metal atom is in a distorted tetra\u00adhedral coordination environment with the two S atoms from two thio\u00adurea ligands and two O atoms from two acetate anions as the coordinating atoms. All H atoms of the thio\u00adurea ligands are involved in N\u2014H\u22efO and N\u2014H\u22efS hydrogen bonds, leading to a three-dimensional network.The title compound, [Co(CH II compound, see: Cavalca et al. 2(CH4N2S)2] = 0.016wR(F2) = 0.041S = 1.043087 reflections190 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.35 e \u00c5\u22123\u0394\u03c1min = \u22120.19 e \u00c5\u22123\u0394\u03c1APEX2  I, global. DOI: 10.1107/S1600536814002074/sj5387Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The NiII atom exhibits a slightly distorted square-planar coordination geometry. In the crystal, the water mol\u00adecule links anions and cations into a three-dimensional network via O\u2014H\u22efN, O\u2014H\u22efS and O\u2014H\u22efO hydrogen bonds. The structure is further stabilized by weak S\u22ef\u03c0 contacts [S\u22efcentroid = 3.8047\u2005(9)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions [centriod\u2013centroid distance = 3.8653\u2005(7)\u2005\u00c5].In the title ion-pair complex, (C DOI: 10.1107/S1600536811045430/rz2659Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title complex, [Cd(NO3)(C18H40N4)]NO3\u00b70.5H2O, is coordinated within a cis-N4O2 donor set provided by the tetra\u00addentate macrocyclic ligand and two O atoms of a nitrate anion; the coordination geometry is distorted octa\u00adhedral. The lattice water mol\u00adecule is located on a twofold rotation axis. N\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efO inter\u00adactions link the complex cations into a supra\u00admolecular layer in the bc plane. Layers are connected by O\u2014H\u22efO hydrogen bonds between the lattice water mol\u00adecule and the non-coordinating nitrate anion, as well as by weak C\u2014H\u22efO contacts.The Cd DOI: 10.1107/S160053681201238X/xu5483Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex and the PdN2Cl2 unit is exactly planar. The dihedral angle between the PdN2Cl2 unit and the acridine ligand is 84.66\u2005(6)\u00b0. In the crystal, the complex mol\u00adecules are stacked in columns along the a axis connected by C\u2014H\u22efCl hydrogen bonds, forming chains along [110]. In the columns, numerous inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings are present, the shortest ring centroid\u2013centroid distance being 3.722\u2005(4)\u2005\u00c5.In the title complex, [PdCl X            2(acr)2] , see: Ha 2] = 0.059                           wR(F                           2) = 0.107                           S = 0.98                           2124 reflections142 parametersH-atom parameters constrainedmax = 0.83 e \u00c5\u22123                        \u0394\u03c1min = \u22120.66 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811053335/bq2326Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The equatorial positions are occupied by two N atoms from two 2,2\u2032-bipyridyl ligands [Fe\u2014N = 2.121\u2005(5) and 2.147\u2005(5)\u2005\u00c5] and two Cl atoms [Fe\u2014Cl = 2.220\u2005(2) and 2.2074\u2005(18)\u2005\u00c5]. Weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions consolidate the crystal packing.In the crystal structure of the title compound, [FeCl DOI: 10.1107/S1600536811016035/zq2098Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The resulting CdN3O4 coordination polyhedron approximates to a very distorted penta\u00adgonal bipramid with one O and one N atom in axial positions. One of the ABTC ligands is bridging to an adjacent metal atom, generating an infinite chain propagating in [100]. A three-dimensional network is constructed from N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separations = 3.641\u2005(2) and 3.682\u2005(3)\u2005\u00c5].In the title coordination polymer, [Cd(C DOI: 10.1107/S160053681201642X/hb6715Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each CuI cation is in a distorted tetra\u00adhedral coordination environment defined by two iodide anions and two nitro\u00adgen atoms from two individual HIPy ligands. Two CuI atoms are connected by two HIPy ligands to form a dimer and these dimers are further bridged through the iodide atoms, leading to a chain structure extending parallel to [100]. Moreover, inter\u00admolecular N\u2014H\u22efI hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions  between pyridyl rings link the chains into a two-dimensional supra\u00admolecular network in the ac plane.The title polymeric compound, [Cu N-heterocyclic carb\u00adoxy\u00adlic acid ligands, see: Chen & Tong 2] = 0.031                           wR(F                           2) = 0.080                           S = 1.06                           1682 reflections118 parametersH-atom parameters constrainedmax = 0.86 e \u00c5\u22123                        \u0394\u03c1min = \u22120.69 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811033605/zl2401Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the triazole and pyridine rings is 23.15\u2005(12)\u00b0. In the crystal, mol\u00adecules are linked by N\u2014H\u22efN and O\u2014H\u22efS hydrogen bonds. Offset \u03c0\u2013\u03c0 stacking between parallel pyridine rings of adjacent mol\u00adecules is also observed, the centroid\u2013centroid distance being 3.6319\u2005(14)\u2005\u00c5.In the title compound, [Cd(NCS) DOI: 10.1107/S1600536812032473/xu5596Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The anion bears two nine-coordinate CeIII ions, each with a distorted tricapped trigonal\u2013prismatic geometry. In the crystal, inter\u00admolecular C\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of 3.514\u2005(3)\u2005\u00c5 connect the various components into a supra\u00admolecular structure.The title compound, {(C DOI: 10.1107/S1600536811004995/hy2405Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The O\u2014Al\u2014N bite angle of the chelating ligand is 94.14\u2005(9)\u00b0. The O\u2014C\u2014C\u2014C\u2014N backbone of the ligand is nearly coplanar (r.m.s. deviation = 0.029\u2005\u00c5) and the Al atom deviates significantly from the mean plane by 0.525\u2005(3)\u2005\u00c5. In the crystal, weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions are observed.The mol\u00adecular structure of the title compound, [Al(CH DOI: 10.1107/S1600536812005880/zq2142Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005880/zq2142Isup4.cdxSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II complex, [Mn(C7H4BrO2)2(C10H14N2O)2(H2O)2], the MnII cation is located on an inversion center and coordinated by two diethyl\u00adnicotinamide (DENA) ligands, two 4-bromo\u00adbenzoate (PBB) anions and two water mol\u00adecules in a distorted octa\u00adhedral geometry. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 3.25\u2005(14)\u00b0. In the mol\u00adecule, the pyridine ring and the benzene ring are oriented at a dihedral angle of 77.24\u2005(5)\u00b0. In the crystal, inter\u00admolecular C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a two-dimensional network. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.537\u2005(1)\u2005\u00c5] further consolidate the crystal packing. In the crystal structure of the title Mn N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.026                           wR(F                           2) = 0.073                           S = 1.09                           4616 reflections233 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.42 e \u00c5\u22123                        \u0394\u03c1min = \u22120.39 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811031412/xu5285Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The six Ag atoms form a distorted octa\u00adhedron, with Ag\u22efAg distances in the range 2.933\u2005(1)\u20133.401\u2005(1)\u2005\u00c5. Each Ag atom is surrounded by one N atom and two thiol\u00adate S atoms from two deprotonated 2-hy\u00addroxy-1-naphthaldehyde thio\u00adsemi\u00adcarb\u00ada\u00adzone ligands. Each ligand coordinates three Ag atoms via a bridging thiol\u00adate S atom and a monodentate N atom, thus two Ag3S3 hexa\u00adgonal rings are linked together. Two dimethyl\u00adformamide solvent mol\u00adecules are located in four sets of sites with half-occupancy and form O\u22efH\u2014N hydrogen bonds to the complex mol\u00adecule. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds are also present. The discrete hexa\u00adnuclear clusters are further linked through \u03c0\u2013\u03c0 inter\u00adactions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698\u2005(2)\u2005\u00c5.In the title compound, [Ag DOI: Click here for additional data file.10.1107/S1600536812050155/yk2079Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The four nearest O atoms around each CuII ion form a distorted square-planar arrangement, the distorted square-pyramidal coordination being completed by the O atom of the water mol\u00adecule at a distance of 2.1525\u2005(16)\u2005\u00c5. The dihedral angle between the benzene ring and the carboxyl\u00adate group is 25.67\u2005(13)\u00b0 in one of the independent IB ligands and 6.44\u2005(11)\u00b0 in the other. The benzene rings of the two independent IB ligands are oriented at a dihedral angle of 86.61\u2005(7)\u00b0. In the crystal, O\u2014H\u22efO inter\u00adactions link the mol\u00adecules into a two-dimensional network. \u03c0\u2013\u03c0 contacts between the benzene rings [centroid\u2013centroid distances = 3.810\u2005(2) and 3.838\u2005(2)\u2005\u00c5] may further stabilize the structure.In the centrosymmetric binuclear title complex, [Cu N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 4(H2O)2] = 0.019wR(F2) = 0.045S = 1.163987 reflections207 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.61 e \u00c5\u22123\u0394\u03c1min = \u22120.66 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812010367/bq2345Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "IIMnIII               2(C11H13NO4)2(CH3CO2)4(H2O)2]\u00b72CH3CN\u00b72H2O, there are two MnIII and one MnII atoms. The MnII atom lies on an inversion center and the MnIII\u2014MnII\u2014MnIII angle is therefore 180\u00b0, as required by crystallographic symmetry. The MnIII and MnII atoms are six-coordinated in a distorted octa\u00adhedral geometry. In the crystal, complex mol\u00adecules and solvent mol\u00adecules are linked into a three-dimensional network by O\u2014H\u22efO and O\u2014H\u22efN hydrogen-bonding inter\u00adactions. In the title complex, [Mn DOI: 10.1107/S1600536811027899/pv2425Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex, the MnII ion is six-coordinated in a considerably distorted octa\u00adhedral environment defined by four N atoms of the two chelating 2,2\u2032-bipyrimidine (bpym) ligands, one I\u2212 anion and one O atom of a water ligand. As a result of the different trans effects of the I and O atoms, the Mn\u2014N bond trans to the I atom is slightly longer than the Mn\u2014N bond trans to the O atom. The dihedral angle between the least-squares planes of the two bpym ligands [maximum deviation = 0.088\u2005(4)\u2005\u00c5] is 76.48\u2005(6)\u00b0. In the crystal, the complex cation, the anion and the solvent water mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efI and O\u2014H\u22efN hydrogen bonds.The asymmetric unit of the title compound, [MnI(C II complexes, see: Hong et al. 2(H2O)]I\u00b72H2O = 0.037                           wR(F                           2) = 0.096                           S = 1.05                           5707 reflections271 parametersH-atom parameters constrainedmax = 0.97 e \u00c5\u22123                        \u0394\u03c1min = \u22121.15 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811037810/aa2026Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "As a result of the different trans effects of Br, N and O atoms, the Mn\u2014N bond trans to the Br atom is slightly longer than the Mn\u2014N bond trans to the N or O atoms. In the crystal, the dpa ligands are not planar, the dihedral angles between the two pyridine rings being 29.2\u2005(4) and 28.2\u2005(3)\u00b0. The complex cations and the Br\u2212 anions are linked by inter\u00admolecular O\u2014H\u22efBr and N\u2014H\u22efBr hydrogen bonds. Inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are present between the pyridine rings, with a centroid\u2013centroid distance of 3.793\u2005(4)\u2005\u00c5.In the title compound, [MnBr(C II complexes with a di-2-pyridyl\u00adamine ligand, see: Bose et al. 2(H2O)]Br = 0.057                           wR(F                           2) = 0.174                           S = 0.96                           4215 reflections271 parametersH-atom parameters constrainedmax = 1.02 e \u00c5\u22123                        \u0394\u03c1min = \u22121.02 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811048100/hy2487Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination about each Rb atom is completed by a monodentate water mol\u00adecule and a phenolic O-atom donor which gives a bridging extension [Rb\u2014O range = 3.116\u2005(7)\u20133.135\u2005(5)\u2005\u00c5]. The polymeric structure is stabilized by inter\u00admolecular water O\u2014H\u22efOcarboxyl\u00adate hydrogen bonds and weak inter-ring \u03c0\u2013\u03c0 inter\u00adactions [minimum ring centroid separation = 3.620\u2005(4)\u2005\u00c5]. An intramolecular O\u2014H\u22efO hydrogen bond between phenol and carboxylate groups is also present.In the structure of title compound, [Rb(C DOI: 10.1107/S1600536811037561/nk2111Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "These chains are further extended into a three-dimensional network via O\u2014H\u22efO hydrogen-bonding inter\u00adactions and inter\u00adchain \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.662\u2005(2)\u2005\u00c5].In the title compound, [Co DOI: 10.1107/S1600536811019970/sj5153Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The central five-membered ring (Pro2) of the peptide mol\u00adecule has a disordered envelope conformation [occupancy ratio 0.879\u2005(2):0.121\u2005(2)] with the envelope flap atom, the central C atom of the three ring methylene groups, lying on alternate sides of the mean ring plane. The terminal five-membered ring (Pro4) also adopts an envelope conformation with the C atom of the methylene group closest to the carboxylic acid function as the envelope flap, and the six-membered tetra\u00adhydro\u00adpyrane ring shows a chair conformation. The tetra\u00adpeptide exists in a helical conformation, stabilized by an intra\u00admolecular hydrogen bond between the amide N\u2014H group of the heterocyclic \u03b1-amino acid Thp and the amide O atom of the 4-meth\u00adoxy\u00adbenzoyl group. This inter\u00adaction has a graph set motif of S(10) and serves to maintain a fairly rigid \u03b2-turn structure. In the crystal, the terminal hy\u00addroxy group forms a hydrogen bond with the amide O atom of Thp of a neighbouring mol\u00adecule, and the amide N\u2014H group at the opposite end of the mol\u00adecule forms a hydrogen bond with the amide O atom of Thp of another neighbouring mol\u00adecule. The combination of both inter\u00admolecular inter\u00adactions links the mol\u00adecules into an extended three-dimensional framework.The asymmetric unit of the title compound, C \u00c5b = 13.7414 (2) \u00c5c = 21.1929 (3) \u00c5V = 3162.48 (7) \u00c53Z = 4K\u03b1 radiationMo \u22121\u03bc = 0.16 mmT = 160 K0.28 \u00d7 0.20 \u00d7 0.18 mmNonius KappaCCD area-detector diffractometer53400 measured reflections9238 independent reflectionsI > 2\u03c3(I)7711 reflections with Rint = 0.044R[F2 > 2\u03c3(F2)] = 0.042wR(F2) = 0.103S = 1.029231 reflections433 parameters21 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.28 e \u00c5\u22123\u0394\u03c1min = \u22120.33 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack & Bernardinelli 1999, 2000 \u25b6,Flack parameter: \u22120.02 (8)COLLECT  I, global. DOI: Click here for additional data file.10.1107/S1600536813004546/nc2305Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813004546/nc2305Isup3.cdxSupplementary material file. DOI: Click here for additional data file.10.1107/S1600536813004546/nc2305Isup4.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal structure, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into centrosymmetric dimers, and \u03c0\u2013\u03c0 inter\u00adactions  link these dimers into layers parallel to the ac plane. Weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions further consolidate the crystal packing.In the title mol\u00adecule, C DOI: 10.1107/S1600536810028394/cv2747Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bis\u00ad(diphenyl\u00adphosphan\u00adyl)ethane ligand bridges an Ru\u2014Ru bond and the monodentate stibine ligand bonds to the third Ru atom. Both the stibine and phosphine ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three stibine-substituted benzene rings make dihedral angles of 38.7\u2005(3), 71.5\u2005(3) and 70.0\u2005(3)\u00b0 with each other in mol\u00adecule A whereas these angles are 83.9\u2005(3), 88.2\u2005(3) and 56.8\u2005(3)\u00b0 in mol\u00adecule B. Similarly, the dihedral angles between the two benzene rings are 80.7\u2005(3) and 87.6\u2005(3)\u00b0 for the two diphenyl\u00adphosphanyl groups in mol\u00adecule A and 84.0\u2005(3) and 72.6\u2005(4)\u00b0 in mol\u00adecule B. In the crystal, mol\u00adecules are linked into tetra\u00admers via inter\u00admolecular C\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions further stabilize the crystal structure.The asymmetric unit of the title  DOI: 10.1107/S1600536810054218/sj5087Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Sn\u2014Cl bond [2.366\u2005(2)\u2005\u00c5] trans to nitro\u00adgen is shorter than the others [2.438\u2005(2) and 2.414\u2005(2)\u2005\u00c5]. The N\u2014Sn\u2014N angle [76.19\u2005(11)\u00b0] is smaller than the O\u2014Sn\u2014N angle [87.89\u2005(10)\u00b0] in the Schiff base ligand. No classical inter\u00admolecular hydrogen-bonding inter\u00adactions are observed. The crystal packing exhibits \u03c0\u2013\u03c0 stacking inter\u00adactions, with a distance of 3.595\u2005(2)\u2005\u00c5 between the centroids of the phenolate ring and the benzene ring of the quinoline group of inversion-related mol\u00adecules.In the title compound, [Sn(C For a related structure, see: Takano & Shibahara 2008.20H19N2O3)Cl3] = 0.042wR(F2) = 0.101S = 1.045989 reflections292 parametersH-atom parameters constrainedmax = 1.51 e \u00c5\u22123\u0394\u03c1min = \u22121.24 e \u00c5\u22123\u0394\u03c1CrystalClear CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004  global, I. DOI: 10.1107/S1600536812002528/pk2385Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II title complex, [Ni(C7H4FO2)2(C6H6N2O)2(H2O)2], the NiII atom, located on an inversion center, is coordinated by two nicotinamide and two 4-fluoro\u00adbenzoate ligands and two water mol\u00adecules in a distorted N2O4 octa\u00adhedral geometry. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 8.95\u2005(8)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 75.01\u2005(7)\u00b0. The water mol\u00adecule links the adjacent carboxyl\u00adate O atom via an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, O\u2014H\u22efO, N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 stacking between parallel pyridine rings [centroid\u2013centroid distance = 3.7287\u2005(11)\u2005\u00c5] is also observed.In the mononuclear Ni N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.030                           wR(F                           2) = 0.077                           S = 1.04                           3220 reflections203 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.46 e \u00c5\u22123                        \u0394\u03c1min = \u22120.57 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811044771/xu5359Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The AgI ion lies on a twofold rotation axis. The primary structure consists of a one-dimensional coordination polymer formed by the AgI ions and the bipyridyl azine ligand in which there is an inversion center at the mid-point of the N\u2014N bond. The nitrite anion inter\u00adacts with the AgI ion through a chelating \u03bc2 inter\u00adaction involving both O atoms. In the crystal, the coordination chains are parallel and inter\u00adact through Ag\u22ef\u03c0 [3.220\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 [3.489\u2005(3)\u2005\u00c5] inter\u00adactions.The asymmetric unit of the title compound, [Ag(NO For the al. 2005. For nit al. 2005; Blake e al. 1999; Cingola al. 1999; Fl\u00f6rke  al. 1998; Tong et al. 2002.       2)(C14H14N4)] = 0.023                           wR(F                           2) = 0.048                           S = 1.05                           1693 reflections102 parametersH-atom parameters constrainedmax = 0.44 e \u00c5\u22123                        \u0394\u03c1min = \u22120.44 e \u00c5\u22123                        \u0394\u03c1                                 DENZO  used to solve structure: SIR92  global, I. DOI: 10.1107/S1600536811028546/lh5278Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The PdII cations are bridged by the S atoms of two benzene\u00adthiol\u00adate ligands with different Pd\u2014S distances [2.2970\u2005(11) and 2.3676\u2005(11)\u2005\u00c5]. The coordination of the metal atom is completed by a chloride anion [2.3383\u2005(11)\u2005\u00c5] and a tri\u00adphenyl\u00adphosphane ligand [2.2787\u2005(11)\u2005\u00c5]. Weak C\u2014H\u22efCl inter\u00adactions are present between complex mol\u00adecules and the CHCl3 solvent mol\u00adecule. The latter is disordered over two positions in a 0.792\u2005(8):0.208\u2005(8) ratio. The crystal under investigation was found to be twinned by nonmerohedry, with a fraction of 73.4\u2005(1)% for the major twin component.The title compound, [Pd DOI: 10.1107/S1600536813019806/wm2753Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "V compound, [Nb2(C44H28N4)2O3], each Nb atom is seven-coordinated with three bridging O atoms and four N atoms from a chelating tetra\u00adphenyl\u00adporphyrinate anion. The Nb\u2014O bond lengths range from 1.757\u2005(6) to 2.331\u2005(6)\u2005\u00c5, and the average (niobium\u2013pyrrole N atom) distance is 2.239\u2005\u00c5. In the dinuclear mol\u00adecule, the Nb\u22efNb separation is 2.8200\u2005(8)\u2005\u00c5, and the dihedral angle between the two porphyrinate mean planes is 5.4\u2005(1)\u00b0. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are present in the crystal structure.In the title dinuclear Nb DOI: 10.1107/S1600536811020538/xu5216Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The methoxide ligands form an asymmetric bridge between the two TiIV atoms [Ti\u2014O bond lengths of 1.9794\u2005(12) and 2.0603\u2005(12)\u2005\u00c5] with the two phenolato ligands occupying the remaining basal sites [Ti\u2014O 1.8218\u2005(11) and 1.8135\u2005(11)\u2005\u00c5]. The Ti\u2014O\u2014C phenolato bond angles are similar at 161.24\u2005(10) and 160.66\u2005(11)\u00b0. The methyl ligand attached to the metal atom has a Ti\u2014C bond length of 2.0878\u2005(17)\u2005\u00c5.The molecule of the title compound, [Ti DOI: 10.1107/S1600536813025634/gg2122Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The EuIII ion is eight-coordinated by two O atoms from two Hbdc ligands, three O atoms from two H2bdc ligands and three water mol\u00adecules, showing a distorted square-anti\u00adprismatic geometry. The EuIII ions are bridged by the carboxyl\u00adate groups of the Hbdc and H2bdc ligands, forming a chain along [110], with an Eu\u22efEu separation of 5.4594\u2005(3)\u2005\u00c5. These chains are further connected by inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions between the imidazole and benzene rings , into a three-dimensional supra\u00admolecular network.In the title one-dimensional coordination polymer, {[Eu(C H-benzimidazole-5,6-dicarboxyl\u00adate complexes, see: Fu et al. (C9H5N2O4)(H2O)3]\u00b72H2O = 0.024                           wR(F                           2) = 0.057                           S = 1.04                           3711 reflections328 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.63 e \u00c5\u22123                        \u0394\u03c1min = \u22120.67 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, glogal. DOI: 10.1107/S1600536811033496/hy2459Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.838\u2005(1)\u2005\u00c5] and C\u2014H\u22efCl hydrogen bonds link adjacent mol\u00adecules into a chain structure along [101].In the title compound, [CuCl DOI: 10.1107/S160053681101333X/ng5145Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The apical PbII atom of each pyramid is 1.33059\u2005(3)\u2005\u00c5 above the basal S4 plane. The metal atom is surrounded by two chelating dithio\u00adphospho\u00adnate ligands binding through the S-donor atoms. The ligands are anisobidentate as the pyramid is comprised of Pb\u2014S bond lengths that vary substanti\u00adally , clearly indicating two short and two longer bond lengths. The P\u2014S bond lengths are also paired as shorter [1.9959\u2005(9) and 1.9877\u2005(8)\u2005\u00c5] and slightly longer [2.0115\u2005(9) and 2.0245\u2005(9)\u2005\u00c5], indicating an anisobidentate nature of the ligand whereby the shorter P\u2014S bond has more double-bond character than the other. The S\u2014Pb\u2014S (chelating) bond angles range from 71.841\u2005(18) to 72.692\u2005(19)\u00b0, whilst the Pb\u2014S\u2014P bond angles range from 84.70\u2005(3) to 90.51\u2005(3)\u00b0.The title compound, [Pb(C DOI: Click here for additional data file.10.1107/S1600536812046818/gk2529Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Fe atom is slightly closer to the substituted cyclo\u00adpenta\u00addienyl ring, with an Fe\u2013centroid distance of 1.6374\u2005(3)\u2005\u00c5 [1.6494\u2005(3)\u2005\u00c5 for the unsubstituted ring]. The amide group is essentially coplanar with the substituted cyclo\u00adpenta\u00addienyl ring, with an N\u2014C(O)\u2014C\u2014C torsion angle of 2.3\u2005(3)\u00b0.In the title compound, [Fe(C DOI: 10.1107/S1600536811026341/fj2441Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four Fe\u2014N bond lengths range from 1.9142\u2005(12) to 1.9579\u2005(11)\u2005\u00c5, while the Fe\u2014P bonds are 2.2452\u2005(4) and 2.2506\u2005(4)\u2005\u00c5 [P\u2014Fe\u2014P = 165.523\u2005(14)\u00b0], consistent with FeII in a low-spin state. Unlike related Fe PNP complexes based on 2,6-diamino\u00adpyridine, the BF4 anions are not hydrogen bonded to the two NH groups of the pincer ligand but show instead anion\u2013\u03c0 inter\u00adactions with the triazine ring and acetonitrile mol\u00adecules in addition to ten C\u2014H\u22efF inter\u00adactions. Most remarkable among these is an anion\u2013\u03c0(triazine) inter\u00adaction with a short distance of 2.788\u2005(2)\u2005\u00c5 between one F and the centroid of the \u03c0-acidic triazine ring. The corresponding shortest distance between this F atom and a triazine carbon atom is 2.750\u2005(2)\u2005\u00c5. The two NH groups of the pincer ligand donate N\u2014H\u22efN hydrogen bonds to the triazine N atom of a neighbouring complex and to an uncoordinated acetonitrile mol\u00adecule. This last mol\u00adecule is in a side-on head-to-tail association with the second uncoordinated acetonitrile at C\u22efN distances of 3.467\u2005(2) and 3.569\u2005(2)\u2005\u00c5. In contrast to several related compounds with diamino\u00adpyridine- instead of diamino\u00adtriazine-based PNP ligands, the title crystal structure is remarkably well ordered. This suggests that the diamino\u00adtriazine moiety exerts notable crystal structure stabilizing effects.In the title compound, [Fe(CH DOI: 10.1107/S1600536811049804/gk2437Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The HfIV and Si atoms lie on the rotation axis with all other atoms being in general positions. The HfIV atom is six-coordinated by two N atoms from the N2,N2\u2032-(di\u00admethyl\u00adsilanedi\u00adyl)bis\u00ad(N-tert-butyl-3-methyl\u00adbenz\u00adimid\u00adamidate) ligand and four Cl\u2212 ions in a slightly distorted octa\u00adhedral geometry. The two amidinate moieties are connected through the central Si atom with Si\u2014N bond length of 1.762\u2005(3)\u2005\u00c5, generating the characteristic N\u2014C\u2014N\u2014Si\u2014N\u2014C\u2014N skeleton of a silyl-linked ansa-bis\u00ad(amidine) species.The symmetric title mol\u00adecule, [Hf(C Cl4] = 0.028wR(F2) = 0.061S = 1.022920 reflections169 parametersH-atom parameters constrainedmax = 0.53 e \u00c5\u22123\u0394\u03c1min = \u22120.29 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536813030328/sj5366Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the cation, the pyridinium rings attached to the central 1-aza\u00adniumyl-2-hy\u00addroxy\u00adethane fragment show an anti conformation, as indicated by the central C\u2014C\u2014C\u2014C torsion angle of \u2212178.1\u2005(4)\u00b0, and they are inclined to one another by 25.7\u2005(2)\u00b0. In the crystal, the cations and anions are linked through N\u2014H\u22efCl and O\u2014H\u22efCl hydrogen bonds. There are also \u03c0\u2013\u03c0 contacts [centroid\u2013centroid distance = 3.788\u2005(3)\u2005\u00c5] and a number of C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions are present, consolidating the formation of a three-dimensional structure.The asymmetric unit of the title compound, (C DOI: Click here for additional data file.10.1107/S1600536812050817/su2540Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, [Zn(C5H10NS2)2(C12H8N2)], exists in a distorted cis-octa\u00adhedral N2S4 donor set defined by two chelating dithio\u00adcarbamate anions as well as a 1,10-phenanthroline ligand. Each of the ligands coordinates in a symmetric mode. The crystal packing is stabilized by weak C\u2014H\u22efS, C\u2014H\u22ef\u03c0(ZnS2C) and \u03c0\u2013\u03c0 [ring centroid distance between centrosymmetrically related pyridyl rings = 3.5955\u2005(13)\u2005\u00c5] inter\u00adactions.The Zn DOI: 10.1107/S1600536811012499/hb5835Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A zigzag chain structure is formed, extending along (001). Each chain is surrounded by three others which are inter\u00adconnected through weak C=O\u22ef\u03c0pyrid\u00adyl [O\u22efcentroid = 2.999\u2005(3)\u2005\u00c5] and \u03c0pyrid\u00adyl\u2013\u03c0pyrid\u00adyl inter\u00adactions [minimum ring centroid separation = 4.014\u2005(2)\u2005\u00c5], giving a three-dimensional framework. In the title polymer, [ZnCl DOI: 10.1107/S160053681104671X/zs2159Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII atom is coordinated by three O atoms from two 1-naphthyl\u00adacetate ligands, one monodentate and the other asymmetric bidentate chelate, and two N atoms from a 5,5\u2032-dimethyl-2,2\u2032-bipyridine ligand, giving an irregular environment. In the crystal, the complex mol\u00adecules are inter\u00adlinked through the water mol\u00adecule by O\u2014H\u22efOcarboxyl\u00adate hydrogen bonds, together with weak C\u2014H\u22efO and bipyridine ring \u03c0\u2013\u03c0 stacking inter\u00adactions [ring centroid separation = 3.761\u2005(2)\u2005\u00c5], giving a two-dimensional network structure.In the title compound, [Zn(C DOI: 10.1107/S1600536811013353/zs2105Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the cluster, the CaII atom is connected to two S atoms of an Fe2S2 core [Ca\u2014S = 2.7463\u2005(8) and 2.7523\u2005(8)\u2005\u00c5]. No Fe\u2014Ca bonds are formed [Fe\u22efCa = 3.6708\u2005(6) and 3.5802\u2005(6)\u2005\u00c5]. There are five close C\u2013H\u22efO\u2013C contacts in the crystal structure.Reaction between [Fe DOI: Click here for additional data file.10.1107/S1600536812048039/zl2517Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Z\u2032 = 2) in the asymmmetric unit of the title compound, [CuBr(C16H32N4)]Br\u00b72H2O. The title crystal consists of two [Cu(C16H32N4)]2+ cations, two Br\u2212 anions and four uncoordinated water mol\u00adecules. The metal atom is five-coordinate square pyramidal, with a long apical Cu\u2014Br bond [2.9734\u2005(11) and 2.9229\u2005(11)\u2005\u00c5 in the two cations]. The two cations form a loosely associated dimer through the formation of hydrogen bonds between both N\u2014H and O\u2014H and Br\u2212. In addition, there is a network of N\u2014H\u22efBr, O\u2014H\u22efBr and N\u2014H\u22efO hydrogen bonds, leading to the formation of a chain structure.There are two formula units ( DOI: 10.1107/S1600536811012852/bv2173Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ligands form a slightly distorted square-planar coordination environment for the Rh(I) atom. An intra\u00admolecular P\u2013Rh\u2013P bite angle of 83.91\u2005(2)\u00b0 is observed. The dihedral angle between the P\u2014Rh\u2014P and the X\u2014Rh\u2014X planes (X is the centroid of a double bond) is 14.0\u2005(1)\u00b0. The BF4 anion is disordered over two positions in a 0.515\u2005(7):0.485\u2005(7) ratio.The title compound, [Rh(C DOI: 10.1107/S1600536810039577/si2281Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The monodentate-coordinated carboxyl\u00adate group is involved in an intra\u00admolecular O\u2014H\u22efO hydrogen bond with the coordinated water mol\u00adecule. In the crystal structure, inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into layers parallel to the ab plane. The crystal packing is further stabilized by weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions indicated by the short distance of 3.6181\u2005(8)\u2005\u00c5 between the centroids of the benzene and pyridine rings of neighbouring mol\u00adecules.In the title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Krishnamachari 2(C6H6N2O)(H2O)2] = 0.022                           wR(F                           2) = 0.050                           S = 1.01                           4838 reflections333 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.29 e \u00c5\u22123                        \u0394\u03c1min = \u22120.24 e \u00c5\u22123                        \u0394\u03c1Absolute structure: Flack 1983, 1761 FrFlack parameter: 0.015 (7)                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S160053681002194X/cv2727sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002194X/cv2727Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the cation, the CuII atom shows a slightly distorted square-pyramidal coordination geometry provided by a pair of \u03bc-OH\u2212 anions and by the N atoms of a chelate tmen ligand in the basal plane. The apical position is statistically occupied by the O atom of a half-occupancy water mol\u00adecule. The F atoms of the anion are disordered over three sets of sites with occupancies of 0.598\u2005(9):0.269\u2005(6):0.134\u2005(8). The crystal packing is governed by ionic forces as well as by O\u2014H\u22efF hydrogen bonds.The title compound, [Cu For add al. 1984.2(OH)2(C6H16N2)2(H2O)](BF4)2 = 0.046wR(F2) = 0.143S = 1.122118 reflections168 parameters1 restraintH-atom parameters constrainedmax = 1.01 e \u00c5\u22123\u0394\u03c1min = \u22120.61 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global, New_Global_Publ_Block. DOI: 10.1107/S1600536812021836/rz2749Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Cl\u2014Cu\u2014N angles of 90.55\u2005(9) and 89.45\u2005(9)\u00b0 are close to ideal values. In the crystal, weak \u03c0\u2013\u03c0 stacking inter\u00adactions are observed between inversion-related benzene rings [centroid\u2013centroid distance = 4.0028\u2005(6)\u2005\u00c5].In the title compound, [CuCl DOI: 10.1107/S1600536812015486/bh2425Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Eucranium Brull\u00e9\u00e9 has been revised and now includes six species: E. arachnoides Brull\u00e9\u00e9, E. belenae Ocampo new species, E. cyclosoma Burmeister, E. dentifrons Gu\u00e9\u00e9rin-M\u00e9\u00e9neville, E. planicolle Burmeister, and E. simplicifrons Fairmaire. Eucranium pulvinatum Burmeister is a new junior synonym of Eucranium arachnoides Brull\u00e9\u00e9, and Eucranium lepidum Burmeister is a new junior synonym of E. dentifrons Gu\u00e9\u00e9rin-M\u00e9\u00e9neville. The following lectotypes and neotypes are designated: Eucranium pulvinatum Burmeister, lectotype; Eucranium planicolle Burmeister, lectotype; Psammotrupes dentifrons Gu\u00e9\u00e9rin-M\u00e9\u00e9neville, neotype; and Eucranium lepidum Burmeister, neotype. Description of the genus and new species, diagnosis and illustrations, and distribution maps are provided for all species. A key to the species of this genus is provided, and the biology and conservation status of the species are discussed.The South American genus  Anomiopsoides Blackwelder, Ennearabdus van Lansberge, Eucranium Brull\u00e9\u00e9, and Glyphoderus Westwood (Eucranium consists of six species. The genus is endemic to Argentina and distributed in the Monte and Chacoan biogeographic provinces (based on The tribe Eucraniini (Scarabaeidae: Scarabaeinae) constitutes a monophyletic group and includes four genera, Westwood . This wobased on  schema; based on .Eucranium was originally described by Brull\u00e9\u00e9 (1834) for one species, E. arachnoides Brull\u00e9\u00e9 (1834). The name was originally proposed by Dejean . Gu\u00e9\u00e9rin-M\u00e9\u00e9neville . Laporte (1840) described Pachysoma (Cyclodema) lacordairei (= E. arachnoides) and indicated that this was the only species of Pachysoma in America. Blanchard (Anomiopsis aelianus (= E. arachnoides). In 1845 Blanchard redescribed A. aelianus and referred to E. arachnoides and A. dioscorides with indication of their similarity to A. aelianus. Also Blanchard . Lacordaire (Eucranium to Brull\u00e9\u00e9 (1834) and provided a synonymy list . Burmeister . Mouth parts and male genitalia were dissected and cleaned in a dilute solution (\u223c?10%) of potassium hydroxide and neutralized in a dilute solution (\u223c? 10%) of acetic acid. The male genitalia were placed in a glycerin-filled vial pinned under the specimen.Body measurements, puncture density, puncture size, and density of setae were based on the following standards: Body length was measured from the middle of the anterior margin of the pronotum (at the middle) to the apex of the elytra, plus head length from the apex of clypeal process to the base of the head . Body width was measured across mid-pronotum. Puncture density was considered \u201c\u201cdense\u201d\u201d if punctures were nearly confluent to less than 2 puncture diameters apart, \u201c\u201cmoderately dense\u201d\u201d if punctures were 2\u20136 diameters apart, and \u201c\u201csparse\u201d\u201d if punctures were separated by more than 6 diameters. Puncture size was defined as \u201c\u201csmall\u201d\u201d if punctures were 0.02 mm or smaller, \u201c\u201cmoderate\u201d\u201d if 0.02\u20130.07 mm, and \u201c\u201clarge\u201d\u201d if 0.07 mm or larger. Setae were defined as \u201c\u201csparse\u201d\u201d if there were few setae, \u201c\u201cmoderately dense\u201d\u201d if the surface was visible but with many setae, and \u201c\u201cdense\u201d\u201d if the surface was not visible through the setae. Elytral carinae were counted from the elytral suture. Specimen labels were copied literally using \u201c\u201c/\u201d\u201d between lines and \u201c\u201c;\u201d\u201d between labels.Neotypes and Lectotypes were designated to provide the nomenclatural stability of the taxon studied, according to the Article 72 of the International Code of Zoological Nomenclature (1999).CMNC: Canadian Museum of Nature, Ottawa, Canada .HECO: Hope Entomological Museum, Oxford, England (Mann D).IAZA: Instituto Argentino de Investigaciones de las Zonas \u00c1\u00c1ridas, Mendoza, Argentina (F Ocampo).IMLA: Fundaci\u00f3\u00f3n e Instituto Miguel Lillo, Universidad Nacional de Tucum\u00e1\u00e1n, Tucum\u00e1\u00e1n, Argentina (MV Colomo).LEMQ: Lyman Entomological Museum, Mc Gill University, Quebec, Canada (S Boucher).MACN: Museo Argentino de Ciencias Naturales, Buenos Aires, Argentina (A Roig).MNHN: Mus\u00e9\u00e9um National d'Histoire Naturelle, Paris, France (O Montreuil).MLPA: Museo de La Plata, La Plata, Argentina (A Lanteri).UNSM: University of Nebraska State Museum, Lincoln, NE, USA (BC Ratcliffe).USNM: United States National Museum, Washington D.C. USA (D Furth).Specimens for this research were collected or borrowed from and deposited in the following institutions and collections:Eucranium genus were described and recognized based mostly on the shape and length of the clypeal processes, and the pronotal and elytral sculptures. These characters rendered variable within species and were not reliable for species identification or description. In this work, new characters were explored and used to define species. Among these are Elytral pseudoepipleuron, pseudoepipleural angle with respect to elytral disc, elytral 8th striae (shape and sculpture), and shape and development of mesotibial spurs. Species male genitalia were studied in order to find species-specific patterns in the shape of the paremares, but the findings were not informative at this level. Internal sacs of paremeres were extracted and studied and these structures provided highly valuable information for phylogenetic analysis, however, they are impractical for species identification. Nevertheless, the information from the paremeres internal sacs is currently being used in a separate project on Eucraniini evolutionary biology .Traditionally species in the Eucranium Brull\u00e9\u00e9 1834: 286.EucraniumNomen nudum).EucraniumAnomiopsisnecA. dioscoridesAnomiopsis Westwood 1838: 159, PsammotrupesP. dentifronsPsammotrupesCyclodema Laporte 1840: 68, (as subgenus of Pachysoma Mac Leay), junior synonym. Type species Pachysoma lacordairei Laporte 1840: 68.Anomiopsis Westwood 1838; Eucranium).Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium Brull\u00e9\u00e9; Eucranium arachnoides Brull\u00e9\u00e9 1834, by monotypy.Type species: DiagnosisThe Eucraniini genus thacan be distinguished from other members of the New World Scarabaeinae by the following combination of characters: Body relatively large (13\u201330 mm), black , 22, 24;RedescriptionHead . Venter: Surface smooth, glabrous or sparsely setose, prosternum pentagonal, anterior margins slightly concave. Mesosternum wider than long, mesometasternum suture visible or not. Metasternum flat, strongly narrowed in middle (metacoxae contiguous). Metepisternum 2.5\u20133 times longer than wide (at base). Ventrites narrower at middle. Pygidium with base grooved medially; disc slightly convex, sparsely punctate, punctures variable. Legs . These differences are not consistent among individuals of the same population. Based on the species concept used in this work to recognize Eucranium species, all these differences are attributed to intraspecific variation. Molecular information is needed to elucidate weather isolated populations ; Argerich (1); Bah\u00ed\u00eda Blanca (4); Bah\u00ed\u00eda San Blas (1); Bajo Hondo (4); Carmen de Patagones (2); Estancia Barrau (6); Felipe Sol\u00e1\u00e1 (7); La Colina (1); Maza (3); Villa Iris (1). C\u00f3\u00f3rdoba: no data (6); \u201c\u201cSur de C\u00f3\u00f3rdoba\u201d\u201d (1); San Javier (2); Las Rosas (3); Potrero de G\u00f3\u00f3mez (1); Yacanto de San Javier (1). La Pampa: no more data (1); Gaviotas (1); Santa Rosa (1); Victorica (4). Mendoza: no more data (1); Agua Escondida (2); Aguada de los Ciegos (1); Arroyo el Rosario, Puesto las Gateadas (1); Arroyo La Rinconada (1); Base del Volc\u00e1\u00e1n Diamante (1); Blanco Encalada (1); Caverna de los Tigres (1); Confluencia r\u00ed\u00edo Diamante and r\u00ed\u00edo Salado (1); Costa de Araujo (1); Dique Agua del Toro (4); Dique Agua del Toro (20 km S) (3); Dique El Carrizal (3); Divisadero (2); El Mollar (2); El Nihuil, M\u00e9\u00e9danos (1); Embalse El Nihuil (4); Fort\u00ed\u00edn Malarg\u00fc\u00fce (1); Huayquer\u00ed\u00edas (1); From RN 40 to Puesto Alvarado (2); Malarg\u00fc\u00fce (no more data) (4); Malarg\u00fc\u00fce, Los Corrales (5); Monte Com\u00e1\u00e1n (1); \u00d1\u00d1acu\u00f1\u00f1\u00e1\u00e1n (9); Pareditas (2); Reserva de la Bi\u00f3\u00f3sfera \u00d1\u00d1acu\u00f1\u00f1\u00e1\u00e1n (11); Reserva Natural Laguna del Diamante (15 km SE) (19); Reserva Natural La Payunia, Puesto La Senillosa (1); Reserva Natural La Payunia, Los Relinchos (11); Reserva Natural La Payunia, Valle del Saino (1); RN 40 and Arroyo Yaucha (3); RN 40 (km 143) (1); RN 40 (S of Pareditas) (2); Road to Paso de Los Tigres (1); Salar del Nihuil (2); San Rafael (10). R\u00ed\u00edo Negro: Coronel G\u00f3\u00f3mez (2); R\u00ed\u00edo Colorado (3). San Luis: no more data (1); Arizona (19); Balde (2); San Luis, Departamento Capital (7); El Volc\u00e1\u00e1n (1); San Ger\u00f3\u00f3nimo (1). \u201c\u201cPatagonia\u201d\u201d no more data (1).ARGENTINA . Buenos Temporal distributionJanuary (79); February (12); March (12); April (5); May (1); July (2); August (4); September (7); October (4); November (15); December (51); no data (41).Biology and conservationEucranium species. Populations of this species generally have a small, patchy distribution and consequently susceptibly to local extinction if changes in the environmental conditions occur. The only known populations of E. arachnoides that are currently in a protected area are those from Reserva Natural \u00d1\u00d1acu\u00f1\u00f1\u00e1\u00e1n and Reserva Natural La Payunia in the Mendoza province.Biology and behavior of this species were recently discussed by Zunino et al. , MontereType materialEucranium belenae Ocampo holotype male at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / R.N 142 km 107. N. Rva. / Telteca / 510m. 32\u00b0\u00b015\u2032?12\u2033?S / 67\u00b0\u00b049\u2032?13\u2033?W. 30/III/2009/ F. C. Ocampo\u201d\u201d; \u201c\u201cEucranium / belenae / HOLOTYPE / F. C. Ocampo\u201d\u201d, Allotype female labeled as holotype except: \u201c\u201cEucranium / belenae / ALLOTYPE / F. C. Ocampo.\u201d\u201d Twenty eight male and twenty female paratypes at IAZA: labeled as holotype. Eleven male and six female paratypes at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / Reserva Telteca. 32\u00b0\u00b022\u2248?59.58\u2033? S, / 68\u00b0\u00b003\u2032?14.16\u2033? W. 548m. / 11-IV-2008. Col. L. Mu\u00f1\u00f1oz.\u201d\u201d Fourteen male and nine female paratypes at IAZA labeled as previous except: \u201c\u201c12-IV-2008\u201d\u201d. Three male paratypes at IAZA labeled as previous except: \u201c\u201c13-IV-2008\u201d\u201d. Three male paratypes at IAZA labeled as previous except: \u201c\u201c14-IV-2008\u201d\u201d. One male paratype at IAZA labeled as previous except: \u201c\u201c15-IV-2008\u201d\u201d. Three male and two female paratypes at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / R.N. 142 Km 107, N Rva. / Telteca. 510m. 32\u00b0\u00b015\u2032?12\u2033?S / 67\u00b0\u00b049\u2032?13\u2033?W. 1-III-2009. / KS Sheldon, FC Ocampo.\u201d\u201d Four male and eight female paratype at IAZA labeled as previous except: \u201c\u201c1/III/2009\u201d\u201d. Four male and Four female paratype at IAZA labeled as previous except: \u201c\u201cFC Ocampo, K Sheldon\u201d\u201d and \u201c\u201c17/III/2009\u201d\u201d. Seven male and three female paratypes at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / Lavalle. Telteca. 32\u00b0\u00b022\u2032?59.58\u2033?S. / 68\u00b0\u00b003\u2032?14.16\u2033?W. 548m. 05-II-2008. / Col. F. Ocampo, E. Ruiz, G. San Blas.\u201d\u201d One paratype at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / Lavalle. Telteca. 32\u00b0\u00b022\u2032?59.58\u2033?S. / 68\u00b0\u00b003\u2032?14.16\u2033?W. 548m. 27-XI-2007. / Col. F. Ocampo\u201d\u201d. One male and one female paratypes at IAZA labeled: \u201c\u201cARGENTINA: Lavalle / Puente R\u00ed\u00edo Mendoza. 21 Feb. 2006. E. Ruiz.\u201d\u201d One male and one female paratypes at IAZA labeled: \u201c\u201cARGENTINA: Mendoza / Reserva Telteca. 563m. S32\u00b0\u00b023\u2032?33\u2033? W68\u00b0\u00b003\u2032?00\u2033? / Jan-3-2002. F. C. Ocampo.\u201d\u201d Four female paratypes at IAZA labeled: \u201c\u201cR.A. Mza. Lavalle / Telteca / 3/2-14/3 /1995 / S. Roig / G. Flores.\u201d\u201d Four female paratypes at IAZA labeled: \u201c\u201cRA. Mza. Lavalle / Telteca /2/11 \u2013 1/12 /1994 / G. Flores.\u201d\u201d One male and two female paratypes at IAZA labeled: \u201c\u201cRa. Mendoza Tel- / teca 17/VIII-24/IX / 1996. Flores/Roig.\u201d\u201d One male and one female paratypes at IAZA labeled: \u201c\u201cRa. Mendoza Tel- / teca 25/XI-25/XII / 1995. Flores/Roig.\u201d\u201d One male and one female paratypes at IAZA labeled: \u201c\u201cRa. Mendoza Tel- / teca 25/IX-5/XI / 1996. Flores/Roig\u201d\u201d. One male paratype at IAZA labeled: \u201c\u201cRa. Mendoza Tel- / teca 14/8 -24/9/ / 1995 Flores/Roig.\u201d\u201d Two female paratype at IAZA labeled: \u201c\u201cMendoza, Lavalle / Telteca 15-2 al 25-3-96. Col. G. Flores / IADIZA.\u201d\u201d One female paratype at IAZA labeled as previous except: \u201c\u201c15-4-95\u201d\u201d. One male and three female paratypes at IAZA labeled: \u201c\u201cRa. Mendoza Tel- / teca 3/II -14/III / 1995. Flores/Roig.\u201d\u201d One male and two female paratype at IAZA labeled: Mendoza, Lavalle / Telteca 1 al 15/12/ 94 Flores/Roig / IADIZA.\u201d\u201d One female paratype at IAZA labeled: \u201c\u201cMendoza, Lavalle / Telteca 10/10 al 3/12/96 / Col. Gonzalez / IADIZA.\u201d\u201d Three male paratypes at IAZA labeled: \u201c\u201cRA. Mza. Lavalle / Telteca / 01.III.94 / G. Flores / IADIZA.\u201d\u201d One male paratype at IAZA labeled: \u201c\u201cMendoza. Lavalle / Parque Telteca / 10.5.93 / M. Gonz\u00e1\u00e1lez / IADIZA\u201d\u201d One female paratype at IAZA labeled: \u201c\u201cMendoza Lavalle Telteca 3-XII-96 / 6-I-97 Flores-Roig.\u201d\u201d One female paratype at IAZA labeled: \u201c\u201cMendoza Lavalle Telteca 25/9-31/10 / 1995 Flores/Roig.\u201d\u201d One female paratype at IAZA labeled: \u201c\u201cMendoza Lavalle Telteca 2/V-14/6 / 96 Flores/Roig / IADIZA.\u201d\u201d One male paratype at IAZA labeled: \u201c\u201cRA. Mza. Lavalle / El Enc\u00f3\u00f3n 12-IV-84 / IADIZA\u201d\u201d; \u201c\u201cCE.000131 / IADIZA\u201d\u201d. One male paratype at IAZA labeled: \u201c\u201cRA.Mza. Lavalle / Rva. Telteca / 15/X/03 / col. G. Debandi.\u201d\u201d One female paratype at IAZA labeled: \u201c\u201cRA. Mza. Lavalle / Telteca 01.III.94. / G. Flores / IADIZA.\u201d\u201d Three male and one female paratypes at IAZA with no data. All paratypes with a yellow paratype label: \u201c\u201cEucranium / belenae / PARATYPE / F. C. Ocampo.\u201d\u201dType localityArgentina, Mendoza, RN 142, km 107, 32\u00b0\u00b0 15\u2032? 12\u2033? S - 67\u00b0\u00b0 49\u2032? 13\u2033? W.DiagnosisE. belenae can be distinguished from other Eucranium species by the following combination of characters: Elytron with pseudoepipleuron not developed; elytral disc with interstriae becoming slightly convex toward margin, 8th stria slightly sulcate; apex of mesotarsus reaching apex of outer mesotibial spur or not   ; outer mal axis)  ; RN 142 Km 107 (114); RN 142 and R\u00ed\u00edo Mendoza (2); Reserva Natural Telteca (27); Telteca (94).ARGENTINA . MendozaTemporal distributionJan (11); Feb (27); March (59); April (66); May (2); June (1); August (4); September (7); October (2); November (14); December (15).Biology and conservationE. belenae were observed carrying goat pellets and small pieces of dry horse dung at daylight hours ; Andalgal\u00e1\u00e1 (2); Barranca Larga (4); Bel\u00e9\u00e9n (3); Capillitas (3); Corral Quemado (3); El Arenal (1); RP 47 N of Capillitas (9); El Ingenio (1); Hualf\u00ed\u00edn (3); Isla de Sauce (1); Loma Negra (2); Pipanaco (1); Punta de Balasto, 12 Km W. Campo El Arenal (3); Punta de Balasto (S. of Santa Maria) (28); RN 40 KM 892 (3). La Rioja: no more data (4); Aimogasta (1); Aminga (1); Anillaco (6); Anillaco (2 km N) (12); RN 40 E of Guandacol (1); La Rioja (1). Salta: La Caldera, Campo Alegre (1). Tucum\u00e1\u00e1n: Taf\u00ed\u00ed del Valle (1).ARGENTINA . CatamarTemporal distributionJanuary (21); February (52); March (7); November (23); December (4).Biology and conservationE. cyclosoma were observed carrying small pieces of dry horse dung at daylight hours over sand dunes in Catamarca province (Specimens of province . ConservEucranium dentifrons (Psammotrupes)ntifrons : 46  and so these species are placed in synonymy.Based on morphological evidence it was concluded that there are no differences between Eucranium dentifrons presents considerable variation in pronotal and elytral sculpture. Variation in puncture size and density on the pronotum and elytra is found among specimens of the same population and among populations. Variation is also found in rugosity on elytral interval seven, been in most specimens obvious and in some specimens slightly evident . These differences are more obvious among specimens from Neuqu\u00e9\u00e9n and western R\u00ed\u00edio Negro province.DistributionChubut: no data (1); Gaiman (1); Puerto Madryn (CENPAT) (5); Telsen (2); Pen\u00ed\u00ednsula Valdez, Estancia la Irma (5); Pen\u00ed\u00ednsula Valdez, Estancia Los M\u00e9\u00e9danos (5); Pen\u00ed\u00ednsula Valdez, Estancia San Pablo (23); Pen\u00ed\u00ednsula Valdez (no more data) (8); Pen\u00ed\u00ednsula Valdez, Playa Fracaso (1); Pen\u00ed\u00ednsula Valdez, Puerto Pir\u00e1\u00e1mides (1); Pen\u00ed\u00ednsula Valdez, Punta Delgada (5). Neuqu\u00e9\u00e9n: Aguada Florencia (2); Arroyo Pic\u00fa\u00fan Leuf\u00fa\u00fa (1); Colonia Centenario (1); Las Lajas (19 Km S) (4); Las Lajas, Cerro de la Cuchilla (4); Neuqu\u00e9\u00e9n (1); Pic\u00fa\u00fan Leuf\u00fa\u00fa (11); Piedra del \u00c1\u00c1guila (6); Plaza Huincul (16); R\u00ed\u00edo Agrio  (7); RN 40 Km 2396, S of Las Lajas (14); RN 40, Bajada del Agrio (1); RN 40, El Marucho (1); Villa El Choc\u00f3\u00f3n(2 km W) (3); Zapala (4). R\u00ed\u00edo Negro: Barrancas del Gualicho (1); Cipolletti (1); Coronel Juan Jos\u00e9\u00e9 G\u00f3\u00f3mez (2); General Roca (1); San Antonio Oeste, Las Grutas (8).ARGENTINA . Chubut:Temporal distributionJanuary (38); February (62); March (16); April (8); September (1); October (6); November (2); December (12).Biology and conservationE. dentifrons have been observed caring and provisioning their borrows with guanaco dung pellets and small pieces of dry horse dung at daylight over sand dunes in Pen\u00ed\u00ednsula Valdez, Chubut, and in Choc\u00f3\u00f3n and near Las Lajas, Neuqu\u00e9\u00e9n  (Specimens of rvation) .E. dentifrons is known to occur is Pen\u00ed\u00ednsula Vald\u00e9\u00e9z in Chubut province.Conservation status of this species has not been assessed. The only protected area where Eucranium planicolleType materialEucranium planicolle Burmeister lectotype male at MACN labeled: \u201c\u201cPampa / occid.\u201d\u201d; \u201c\u201cEucranium / planicolle / planicolle 6\u201d\u201d; \u201c\u201cEucranium / planicolle / Burm. / LECTOTYPE / F. C. Ocampo det. 2009\u201d\u201d. Lectotype here designated. One paralectotype male at MACN labeled as lactotype except: \u201c\u201cplanicolle 5\u201d\u201d.DiagnosisE. planicolle can be distinguished from other Eucranium species by the following combination of characters: Elytron with well defined pseudoepipleuron, pseudoepipleuron forming an \u223c?45\u201360\u00b0\u00b0 angle with elytral disc ; Bah\u00ed\u00eda Blanca (3); Bah\u00ed\u00eda San Blas (1); Bajo Hondo (6); Coronel Pringles (1); Estaci\u00f3\u00f3n Delta near Monte Hermoso (13); Estancia Barrau (30 Km SW Villa Iris) (8); Monte Hermoso (3); Villa Iris (7). La Pampa: no more data (1); Anguil (1). Mendoza: no more data (6); 25 de Mayo (1); Agua Escondida (1); Dique Agua del Toro (2); Dique Agua del Toro (20 Km S.) (2); Monte Com\u00e1\u00e1n (1); RP 143, Km 33 (1); Pareditas (3 Km S) (1); Pareditas (10 Km S) (1); Pareditas (22 Km S.) (1); Piedra P\u00f3\u00f3mez (1); Reserva Natural Laguna del Diamante, 10 Km E. (1); RN 40, Puesto Alvarado (1); RN 40 and Arroyo Yaucha (1); RN 40, S of Pareditas (4); RP 150 (1). R\u00ed\u00edo Negro: no more data (2); R\u00ed\u00edo Colorado (8); RP 4  (2). San Luis: Departamento Capital (5).ARGENTINA . No dataTemporal distributionJanuary (3); February (15); March (2); April (1); October (2); November (16); December (31).Biology and conservationE. planicolle are known to be diurnal and have been observed caring and provisioning their borrows with goat dung pellets in Mendoza province  . Conservation status of this species has not been assessed.Specimens of Eucranium simplicifrons Fairmaire 1873: 608.DiagnosisE. simplicifrons can be distinguished from other Eucranium species by the following combination of characters: Elytron with or without pseudoepipleuron, if present, pseudoepipleuron forming an <65\u00b0\u00b0 angle with elytral disc ; Choya (8); El Charco (4); Fern\u00e1\u00e1ndez (1); Guasay\u00e1\u00e1n (1); Ram\u00ed\u00edrez deVelezco (1 Km N) (2).ARGENTINA . SantiagTemporal distributionFebruary (1); April (1); August (4); October (9); November (2).Biology and conservationE. simplicifrons. Conservation status of this species has not been assessed; the species does not occur in any protected area.With the exception that the species is diurnal  nothing is known about the biology of th striae carinated, carina sharp and reflexed or rounded and reflexed1. Elytron with well defined pseudoepipleuron, pseudoepipleura forming a 45\u201360\u00b0\u00b0 angle with elytral disc , 23; ely2th stria not carinated, or if carinated, carinae poorly defined and never reflexed1\u2032?. Elytron with or without pseudoepipleuron, if present pseudoepipleuron forming a <65\u00b0\u00b0 angle with elytral disc , 15, 25;3th stria carinated, carina sharp 2. Elytron with outer margin of 8na sharp , 23; elyEucranium planicolle Burmeister  (neville) 3. Elytron with pseudoepipleuron absent43\u2032?. Elytron with pseudoepipleuron present, sometimes poorly developedEucranium arachnoides Brull\u00e9\u00e9 ; outer mesotibial spur distinctively broad at apical 1/2, obviously asymmetrical  ; mesotibial outer spur slightly broad on apical 1/3, nearly symmetrical . SantiagEucranium simplicifrons Lacordaireth stria slightly sulcate; west central Argentina (northeastern Mendoza province)5. Elytral disc with interstriae becoming slightly convex toward apical margin, 8Eucranium belenae Ocampo sp. nov. 5\u2032?. Elytral disc with interstriae smooth, evenly flat, 8Eucranium cyclosoma Burmeister . Thus, the Monte and Chacoan biota have multiple origins with most genera being from Neotropical origin followed by groups with Patagonian or Andean affinities.Morphological divergence of n biotas . South An biotas . In the Eucranium are distributed across a \u223c?2000 km long (North-South) and 500 km wide (East West) range. Nevertheless, species in this genus show little sympatry, E. arachnoides and E. planicolle partially share they distributional range, while the rest of the species, E. belenae, E. cyclosoma, E. dentifrons, and E. simplicifrons are isolated from other species in the genus or only share a few localities (ex. E. arachnoides and E. dentifrons in R\u00ed\u00edo Negro province). Eucranium species have high endemicity and populations have patchy distributions that make them susceptibly to local extinction if changes in the environmental conditions occur. Nothing is known for Eucranium species' population dynamics or habitat conservation status. Only two species, E. belenae and E. dentifrons are distributed within natural reserves or protected areas. It is well documented that there are genetic implications for small population size, among these it is a decline of genomic variation resulting from allelic loss (and Carrol (1997) for the long term viability of a population it is important for it to maintain genetic variability which would enable the population to adaptively tolerate changes in environmental conditions. Further more, Keller et al. , in order to preserve these species it is critical to understand their population dynamics and their habitat conservation status. Eucranium is characterized by its unusual morphology and unique biology and behavior, and it constitutes an old evolutionary lineage. Vane-Wright et al. (Eucranium of high conservation value.Species of lic loss . Accordir et al. , based ot et al.  proposed"}
{"text": "Each of the two independent AuIII ions lies on an inversion center and has a distorted square-planar geometry. In the crystal, inter\u00admolecular C\u2014H\u22efCl hydrogen bonds, \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.5548\u2005(16) and 3.7507\u2005(16)\u2005\u00c5] and Au\u22ef\u03c0 inter\u00adactions [Au\u22efcentroid distance = 3.6424\u2005(10)\u2005\u00c5] are effective in the stabilization of the structure, resulting in the formation of a supra\u00admolecular structure. Intra\u00admolecular N\u2014H\u22efN hydrogen bonds are present in the cation.In the title compound, (C DOI: 10.1107/S1600536811036208/hy2466Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II ion in the title complex, [PtCl2(C14H10N4)], is four-coordinated in a distorted square-planar environment by two N atoms of a chelating 2,3-di-2-pyridyl\u00adpyrazine ligand and two chloride anions. The pyridyl ring coordinated to the PtII atom is inclined slightly to its carrier pyrazine ring [dihedral angle = 13.5\u2005(1)\u00b0], whereas the uncoordinated pyridyl ring is inclined considerably to the pyrazine ring [dihedral angle = 54.3\u2005(2)\u00b0]. The dihedral angle between the two pyridyl rings is 59.2\u2005(2)\u00b0. In the crystal, the complexes are assembled through inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds, forming a three-dimensional network. Intra\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds are also present.The Pt DOI: 10.1107/S1600536811038906/tk2794Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NO5 donor set is based on a distorted octa\u00adhedron. Helical supra\u00admolecular chains along [010] are found in the crystal structure mediated by O\u2014H\u22efO hydrogen bonds formed between the coordinating methanol mol\u00adecule and the phenolate O atom of the chloro\u00adbenzene residue.The title Schiff base complex, [V(C E)-2-(2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00adphenolates containing halide atoms on the aromatic ring(s), see: Yeni\u015fehirli et al. (CH3O)O(CH4O)] = 0.046wR(F2) = 0.131S = 1.043453 reflections221 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 1.37 e \u00c5\u22123\u0394\u03c1min = \u22120.93 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S160053681200311X/hg5167Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atoms in the title complex, [Ni2(CN)4(C16H36N4)]\u00b7C3H7NO\u00b70.5H2O, are bridged by a cyanide ion. The macrocycle folds around one NiII atom, which is five-coordinated in an NiN5 square-pyramidal geometry. The other NiII atom is surrounded by the cyanide ions in an NiN4 square-planar geometry. The dimethyl\u00adformamide solvent mol\u00adecule is disordered over two positions in a 0.62\u2005(1):0.38\u2005(1) ratio and the water mol\u00adecule is disordered about a center of inversion. The dinuclear mol\u00adecule and solvent mol\u00adecules are linked by N\u2014H\u22efO, N\u2013H\u22efN and O\u2014H\u22efO hydrogen bonds, forming a three-dimensional network.The two Ni DOI: 10.1107/S1600536810042625/bt5382Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Activation of the \u03b1-secretase processing pathway of amyloid precursor protein (APP) is recognized as an important mechanism which diverts APP processing from production of beta-amyloid (A\u03b2) to non toxic sAPP\u03b1, decreasing Alzheimer\u2019s disease (AD) plaque formation and AD-associated cognitive deficits. Two potent classes of PKC modulators can activate the \u03b1-secretase pathway, the benzo/indolactams and bryostatin/bryologues. While both modulate PKC-dependent APP processing, no direct comparisons of their relative pharmacological potencies have been accomplished which could assist in the development of AD therapies. In this study, we measured the activation of \u03b1-secretase APP processing and PKC-\u03b1, -\u03b4, and -\u03b5 induced by the benzolactam-APP modulator TPPB and bryostatin-1 in the neuroblastoma cell line SH-SY5Y which expresses APP and \u03b1- and \u03b2-secretase processing mechanisms. Bryostatin-1 produced a more rapid, potent, and sustained activation of \u03b1-secretase APP processing than TPPB and selectively activated PKC-\u03b4 and PKC-\u03b5. Although TPPB also activated \u03b1-secretase, its potency was approximately 10- to 100-fold lower, possibly reflecting lower PKC-\u03b4 and -\u03b5 activation. Because bryostatin-1 is a highly potent PKC-\u03b4 and -\u03b5 activator which activates \u03b1-secretase APP processing, further characterization of bryostatin-1/bryologues may help refine their use as important tools for the clinical management of AD. N-methyl-d-aspartate receptor antagonist, which reduces glutamate-dependent excitotoxicity, Ca2+ influx, and oxidant stress in neurons , few effective treatment options have been developed  and \u201cstatins,\u201d inhibitors of HMG-coA reductase, may also reduce formation and persistence of A\u03b2 and have been suggested as potential adjuvant therapies for AD  include diphenylurea, derivatives of hydroxyethylamine, and celastol, all of which at least partly block conversion of APP to A\u03b2. \u03a4hese drugs have been extensively studied in AD therapy , a disintegrin and metalloprotease (\u2018ADAM\u2019)-17  activation. Several drugs which modulate PKC isoenzyme activity, particularly the PKC-\u03b4 and PKC-\u03b5 isoforms, potently activate \u03b1-secretase processing of APP, generating the non toxic sAPP\u03b1 and preventing A\u03b2 formation. Currently, PKC activators may represent the most important, novel, and specific treatments for AD. At least two important classes of agents can activate PKC-dependent APP processing at relatively low (\u03bcM to nM) doses: (1) the benzolactam/indolactams and (2) bryostatin-1 and related bryologues.Ki\u2009=\u200911.9\u00a0nM for inhibition of phorbol 12,13 dibutryrate binding to PKC-\u03b1) which enhances sAPP\u03b1 secretion in fibroblasts and PC12 neuronal cells --8-(5-(4-(trifluoromethyl) phenyl)-2,4-pentadienoylamino) benzolactam] (CAS#497259-23-1) was purchased from Reagent 4 Research LLC  and was diluted in ethanol. All ethanol concentrations in this study were below 0.1\u00a0% in cellular assays.Bryostatin-1 in ethanol stock solutions was provided by Aphios Corporation . The benzolactam APP modulator TPPB , -\u03b4 , and -\u03b5  antibodies . H-7 antibody is a mouse monoclonal antibody raised against amino acids 645\u2013672 on human PKC-\u03b1 which recognizes a single 80-kDA PKC-\u03b1 isoform. G-9 antibody is a mouse monoclonal antibody raised against amino acids 647\u2013673 of rat PKC-\u03b4 which recognizes a single 78-kDA band, and E-5 antibody is a mouse monoclonal antibody which was raised against amino acids 705\u2013737 of human PKC-\u03b5 and recognizes a single 90-kDA PKC-\u03b5 band. PKC isoform bands were visualized using HRP-conjugated 2\u00b0 antibody  with ECL plus  with SRX101 film. Band intensities were quantified by densitometric analysis using an HP Scanjet 3970 Densitometer and Image-J image analysis system software .Measurements of cytosolic and membrane-associated levels of PKC-\u03b1, -\u03b4, and -\u03b5 isoenzymes were used to assess PKC translocation in response to bryostatin-1 or TPPB as described by Racchi et al.  with modp\u2009<\u20090.05 was considered as statistically significant.All data are presented as mean \u00b1 standard deviation and were analyzed by one-way ANOVA with Dunnett\u2019s post-testing . A value of \u22127\u00a0M (**p\u2009<\u20090.01), 10\u22128\u00a0M (**p\u2009<\u20090.01), 10\u22129\u00a0M (*p\u2009<\u20090.05), and 10\u221210\u00a0M (*p\u2009<\u20090.05). TPPB also induced sAPP\u03b1 release, but to a lesser extent and only at 10\u22127\u00a0M (p\u2009<\u20090.05) and 10\u22128\u00a0M (p\u2009<\u20090.05) ; TPPB was able to significantly increase sAPP\u03b1 at 6\u00a0h (*p\u2009<\u20090.05) , 6\u00a0h (**p\u2009<\u20090.01), and 12\u00a0h (*p\u2009<\u20090.05). At this dose, TPPB only significantly increased the release of sAPP\u03b1 at 6\u00a0h (*p\u2009<\u20090.05) , which persisted at 1\u00a0h (**p\u2009<\u20090.01) and 3\u00a0h time points (**p\u2009<\u20090.01). By comparison, TPPB only induced the significant release of sAPP\u03b1 at 3\u00a0h (*p\u2009<\u20090.05) ; however, TPPB at 10\u221210\u00a0M did not significantly increase the release of sAPP\u03b1 at any of the time points tested  Fig.\u00a0. At 10\u2212805) Fig.\u00a0. Bryosta05) Fig.\u00a0. Bryostated Fig.\u00a0.Fig. 2a\u22128, 10\u22129, and 10\u221210\u00a0M bryostatin-1 significantly increased the activation of PKC-\u03b1 in SH-SY5Y cells (**p\u2009<\u20090.01)   ; 10\u221210\u00a0M TPPB did not activate PKC-\u03b1 at any time point tested. A dose-dependent comparison of bryostatin-1 and TPPB showed that, at 3\u00a0h, PKC-\u03b4 was activated by 10\u22128\u00a0M bryostatin-1 (**p\u2009<\u20090.01), 10\u22129\u00a0M bryostatin-1 (*p\u2009<\u20090.05), and 10\u221210\u00a0M bryostatin-1 (*p\u2009<\u20090.05) , 1\u00a0h (**p\u2009<\u20090.01), and 3\u00a0h (**p\u2009<\u20090.01); by comparison, 10\u22129\u00a0M TPPB did not activate PKC-\u03b4 at any time point tested  and 3\u00a0h (**p\u2009<\u20090.01); by comparison, 10\u221210\u00a0M TPPB did not activate PKC-\u03b4 at any time point , 10\u22129\u00a0M bryostatin-1 (**p\u2009<\u20090.01), and 10\u221210\u00a0M bryostatin-1 (*p\u2009<\u20090.05) , 1\u00a0h (**p\u2009<\u20090.01), and 3\u00a0h (**p\u2009<\u20090.01) , 1\u00a0h (*p\u2009<\u20090.01), and 3\u00a0h (**p\u2009<\u20090.01)  following treatment with bryostatin-1 or TPPB. Confluent cultures of SH-SY5Y neuroblastoma cells were treated with different concentrations of either bryostatin-1 or TPPB for time points up to 3\u00a0h, when membrane and cytosolic pools of PKCs were isolated by differential detergent extraction, and Western-blotted for each individual isoform. Actin was also Western-blotted in each fraction to ensure equal loading. At 3\u00a0h, 1001) Fig.\u00a0; 10\u22128, 1C-\u03b1 Fig.\u00a0. A time 01) Fig.\u00a0; 10\u22129\u00a0M 01) Fig.\u00a0. Bryosta05) Fig.\u00a0; TPPB di05) Fig.\u00a0. A time ted Fig.\u00a0. A time int Fig.\u00a0. A dose-05) Fig.\u00a0; TPPB di05) Fig.\u00a0. A time 01) Fig.\u00a0; by compted Fig.\u00a0. A time 01) Fig.\u00a0; by compted Fig.\u00a0.Fig. 3aThe presence of A\u03b2-laden cerebral plaques in AD, a central feature of Alzheimer\u2019s disease (AD), is thought to contribute to the disturbances in nerve structure, function, and memory which characterize AD dementia  GABA(A)R-regulated post-synaptic currents, and (3) cholinergic signaling  activates \u03b1-secretase via PKC-\u03b1  and \u201cnovel\u201d PKC isoforms to stimulate sAPP\u03b1 processing  to enhance non-amyloidogenic processing of APP to sAPP\u03b1. Currently, the toxicological properties of TPPB are not fully known. An important goal in PKC\u2013APP modulator drug design must be to overcome the potential carcinogenic properties of benzolactams/indolactams because TPPB, like TPA and other phorbol esters, may still retain tumor-promoting activity  of TPPB needed to reach equivalent \u03b1-secretase activation as bryostatin-1 which may hamper its use in human AD therapy. There are, of course, relative factors of availability and cost of bryostatin-1 versus reduced potency and higher toxicity of TPPB which can ultimately determine clinical use.By comparison, TPPB is a novel, synthetic cell-permeable benzolactam PKC activator which has been used as a standard APP modulator . Bryostatin-1 also appears to be a more active, rapid, and persistent APP modulator which reflects its greater specificity toward PKC-\u03b4 or PKC-\u03b5 isoform activation at low doses.Novel PKC activators are important candidate treatments for AD because they activate beneficial APP processing through \u03b1-secretase. We compared how PKC-\u03b1 , -\u03b4, and -\u03b5 (novel PKC isoforms) were activated in neuroblastoma cells by bryostatin-1 and TPPB as a function of time and concentration. Bryostatin-1 significantly induced PKC-\u03b1, -\u03b4, and -\u03b5 activation at 10Here, we found that bryostatin-1 exerted a more rapid, potent, and sustained activation of APP processing , which was associated with its more potent and specific activation of PKC-\u03b4 and PKC-\u03b5 at low doses. The further refinement of bryostatin-1 pharmacology in PKC mobilization and \u03b1-secretase activation may help move this drug class more rapidly into clinical treatment for AD."}
{"text": "The pyridyl N atom of the Schiff base and the imino N atom of the 4-methyl-pyridine-2-yl\u00adimino ligand are not involved in the coordination. There is an intra\u00admolecular N\u2014H\u22efN hydrogen bond involving the pyridine N atom and the amino group of the 2-amino\u00adpyridine ligand. In the crystal, mol\u00adecules are linked via N\u2014H\u22efCl hydrogen bonds, forming chains propagating along [001].In the title complex, [Cu(C Cl(C6H8N2) = 0.055wR(F2) = 0.114S = 0.943339 reflections243 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.40 e \u00c5\u22123\u0394\u03c1min = \u22120.45 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812047198/su2518Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The carboxyl\u00adate groups of the HB ions are slightly twisted away from the attached benzene rings by 2.84\u2005(15) and 4.8\u2005(2)\u00b0. The planes of the two benzene rings of the HB ions are oriented with respect to each other at a dihedral angle of 84.41\u2005(8)\u00b0. In the crystal, adjacent polymeric chains inter\u00adact via O\u2014H\u22efO, N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds. The solvent water mol\u00adecule links with the polymeric chains via O\u2014H\u22efO hydrogen bonding. \u03c0\u2013\u03c0 stacking between the benzene and pyridine rings and between the benzene rings [centroid\u2013centroid distances = 3.731\u2005(2) and 3.353\u2005(2)\u2005\u00c5] are present in the crystal.In the crystal of the title polymeric compound, {[Pb(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)]\u00b7H2O = 0.017wR(F2) = 0.050S = 1.194783 reflections304 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.94 e \u00c5\u22123\u0394\u03c1min = \u22121.27 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812004357/xu5463Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the polymeric title compound, {[Pb(C13H11N4O)]ClO4}n, is coordinated by the N\u2032-[1-(pyridin-2-yl-\u03baN)ethyl\u00adidene]isonicotinohydrazidate ligand via its O,N,N\u2032-donors and simultaneously bridged by a neighbouring ligand via the pyridin-2-yl N atom. The resultant supra\u00admolecular chain is a zigzag along the a axis. The stereochemistry of the PbII atom is defined by an N3OE donor set (E = lone pair of electrons), which results in a \u03a8-trigonal\u2013bipyramidal coordination with the O and pyridin-2-yl N atoms in axial positions. The dihedral angle between the pyridine rings of the ligand is 6.3\u2005(3)\u00b0. The supra\u00admolecular cationic chains are linked into a three-dimensional array via secondary Pb\u22efO [3.133\u2005(6) and 3.28\u2005(7)\u2005\u00c5] and Pb\u22efN [3.028\u2005(4)\u2005\u00c5] inter\u00adactions. Weak C\u2014H\u22efO inter\u00adactions and aromatic \u03c0\u2013\u03c0 stacking [centroid\u2013centroid separation = 3.693\u2005(2)\u2005\u00c5] also occur in the crystal.The Pb N\u2032-[1-(2-pyrid\u00adyl)ethyl\u00adidene]isonicotinohydrazide ligand, see: Maurya et al. ]ClO4                         = 0.022                           wR(F                           2) = 0.056                           S = 1.07                           2811 reflections218 parametersH-atom parameters constrainedmax = 0.55 e \u00c5\u22123                        \u0394\u03c1min = \u22120.45 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811046691/hb6465Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecules are linked by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds. Two types of \u03c0\u2013\u03c0 stacking inter\u00adactions occur between the TPTZ ligands of adjacent complexes [centroid-to-centroid distances = 3.760\u2005(4) and 3.870\u2005(3)\u2005\u00c5].In the title compound, [Nd(NO DOI: 10.1107/S1600536811014589/ff2007Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the CuII ions is coordinated in a distorted square-planar geometry, whereas the other is coordinated in a distorted square-pyramidal geometry, the long apical Cu\u2014O bond [2.885\u2005(4)\u2005\u00c5] of the square-pyramidal coordination being provided by a symmetry-related O atom creating a one-dimensional polymer along [010]. \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.783\u2005(4)\u2005\u00c5] and short inter\u00adchain Br\u22efBr inter\u00adactions [3.6142\u2005(12)\u20133.6797\u2005(12)\u2005\u00c5] are observed.The asymmetric unit of the title coordination polymer consists of a dinuclear neutral complex mol\u00adecule of formula [Cu DOI: 10.1107/S1600536812029285/rz2776Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Adjacent complex mol\u00adecules are stacked through aromatic \u03c0\u2013\u03c0 inter\u00adactions; the closest distance between adjacent aromatic rings is 3.598\u2005(2)\u2005\u00c5.In the mononuclear title compound, [ZnCl DOI: 10.1107/S1600536812022313/rk2337Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the CoII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 23.91\u2005(9)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 88.84\u2005(4)\u00b0. The coordinating water mol\u00adecule links with the carboxyl\u00adate group via an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 stacking between the parallel benzene rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.8505\u2005(8)\u2005\u00c5] may further stabilize the structure. A weak C\u2014H\u22ef\u03c0 inter\u00adaction also occurs in the crystal.In the title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.026wR(F2) = 0.069S = 1.053527 reflections216 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.42 e \u00c5\u22123\u0394\u03c1min = \u22120.36 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812032205/xu5597Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "This is only possible as the mol\u00adecule has a hinged cis arrangement about the Pd2+ coordination spheres. For this hinged dimeric structure, the angles between the two coordination planes in each mol\u00adecule are 21.59\u2005(4) and 22.10\u2005(4)\u00b0. This hinged cis arrangement also allows the two mol\u00adecules to form pairs linked by secondary inter\u00adactions between the Pd and Te atoms of an adjoining mol\u00adecule, leading to a tetra\u00admeric overall structure. C\u2014H\u22efCl inter\u00adactions consolidate the crystal packing.The asymmetric unit of the title compound, [Pd For related structures of bridged dimers of palladium mediated by Se, see: Brown & Corrigan 2004; Chakrab al. 2011; Dey et  al. 2006; Ford et al. 2004; Kaur et al. 2009; Morley  al. 2006; Nakata  al. 2009; Oilunka al. 1999, 2001 \u25b6.2(C9H12NTe)2Cl2]\u00b70.5CH2Cl2 = 0.039wR(F2) = 0.102S = 1.065506 reflections254 parametersH-atom parameters constrainedmax = 2.12 e \u00c5\u22123\u0394\u03c1min = \u22120.90 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 2355 FrFlack parameter: 0.06 (4)APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812000104/jj2116Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atom lies 0.065\u2005(1)\u2005\u00c5 above the N2O2 plane and the Cu\u2014O [2 \u00d7 1.945\u2005(2)\u2005\u00c5] and Cu\u2014N bond lengths [1.968\u2005(3) and 1.962\u2005(3)\u2005\u00c5] lie in expected ranges. The two aromatic ring planes make a dihedral angle of 85.48\u2005(1)\u00b0.The mol\u00adecular structure of the title compound, [Cu(C DOI: Click here for additional data file.10.1107/S1600536812046387/aa2076Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The metal-coordinated pyridine rings are almost coplanar, making a dihedral angle of 1.5\u2005(2)\u00b0, while the two pendent pyrazine rings are arranged on the same side of the N\u2014Ag\u2014N line. Along the a axis, the mononuclear coordination units are stacked with \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.569\u2005(4)\u2005\u00c5], leading to infinite chains. The chains are inter\u00adconnected through inter\u00admolecular N(pyrazine)\u22ef\u03c0(pyrazine) inter\u00adactions forming layers parallel to the ab plane [N\u22efcentroid = 3.268\u2005(5)\u2005\u00c5]. These layers are further stacked along the c-axis direction, furnishing a three-dimensional supra\u00admolecular framework with the tetra\u00adfluoridoborate anions embedded within the inter\u00adstices.In the title mononuclear complex, [Ag(C DOI: 10.1107/S1600536811051270/zq2141Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the complex cations and the monodeprotonated 2-carb\u00adoxy\u00adbenzoate anions are connected by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming a tape along [100]. Adjacent tapes are further linked into a three-dimensional arrangement via \u03c0\u2013\u03c0 stacking inter\u00adactions between the triazole and benzene rings and between the pyridine and benzene rings [centroid\u2013centroid distances = 3.6734\u2005(14)/3.9430\u2005(16) and 3.8221\u2005(14)\u2005\u00c5]. Intra\u00admolecular N\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds are also observed.In the complex cation of the title salt, [Cu(C DOI: 10.1107/S1600536812000128/hy2503Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The coordination geometry around the CuII atom is square-pyramidal, comprising two N atoms from a symmetrically chelating 1,10-phenanthroline ligand, one O atom from a trichloro\u00adacetate ligand and two Cl\u2212 anions. In addition, there is a weak intra\u00admolecular Cu\u22efO inter\u00adaction of 2.9403\u2005(14)\u2005\u00c5 involving the carbonyl O atom of the trichloro\u00adacetate ligand. The central Cu2Cl2 core takes the form of a rhombus, owing to the disparate Cu\u2014Cl bond lengths. Mol\u00adecules are connected in the crystal structure by C\u2014H\u22efCl and C\u2014H\u22efO inter\u00adactions.The title compound, [Cu II 1,10-phenanthroline complexes, see: De Burgomaster et al. 2Cl2(C12H8N2)2] = 0.026wR(F2) = 0.070S = 1.053233 reflections208 parametersH-atom parameters constrainedmax = 0.52 e \u00c5\u22123\u0394\u03c1min = \u22120.46 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812003947/bt5807Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, each palladium dimer is accompanied by a dichloro\u00admethane solvent mol\u00adecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd\u2014P(av.) = 2.2135\u2005(4)\u2005\u00c5, Pd\u2014C(av.) = 1.9648\u2005(16)\u2005\u00c5 and P\u2014Pd\u2014C = 84.05\u2005(5) and 87.98\u2005(5)\u00b0, and O\u2014Pd\u2014O\u2032 = 60.56\u2005(4) and 61.13\u2005(4)\u00b0. Bonding with the carbonate O atoms shows values of 2.1616\u2005(11) and 2.1452\u2005(11)\u2005\u00c5 for the Pd\u2014O\u2014Pd bridge, whereas other Pd\u2014O distances are slightly longer at 2.2136\u2005(11) and 2.1946\u2005(11)\u2005\u00c5. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723\u2005(6):0.277\u2005(6). Weak C\u2014H\u22efO interactions are observed propagating the molecules along the [100] direction. The title compound, [(\u03bc DOI: Click here for additional data file.10.1107/S1600536812048702/yk2080Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "A chain along the c axis is formed by C\u2014H\u22efN hydrogen-bonding inter\u00adactions and a weak \u03c0\u2013\u03c0 inter\u00adaction is observed between the pyrimidine rings of two adjacent parallel chains [centroid\u2013centroid distance = 3.722\u2005(2)\u2005\u00c5]. N\u2014H\u22efCl, CN\u2014H\u22efCl and N\u2014H\u22efO interactions also occur. In the title compound, (C DOI: 10.1107/S1600536811045995/vn2019Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The water mol\u00adecules are involved in intra- and inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonding. Inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds are formed between ligands. In addition, weak \u03c0\u2013\u03c0 inter\u00adactions are observed between the benzene rings of the ligands [centroid\u2013centroid distance = 3.580\u2005(3)\u2005\u00c5]. The inter\u00admolecular hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions lead to the formation of a three-dimensional supra\u00admolecular network.In the title complex, [NiCl H)-one, see: Turgunov & Englert (2010H)-one, see: Turgunov et al. (2010For a Cd(II) coordination polymer with quinazolin-42(H2O)2] = 0.052wR(F2) = 0.139S = 0.941686 reflections132 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.75 e \u00c5\u22123\u0394\u03c1min = \u22120.51 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812019381/hg5221Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Extensive inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds lead to the stability of the crystal structure. Inter\u00adactions between one C\u2014H group of the 2,3-diamino\u00adpyridinium [+] cation and the aromatic ring of the pyridine-2,6-dicarboxyl\u00adate (pydc) ligand (C\u2014H\u22efcentroid distance = 2.78\u2005\u00c5) and \u03c0\u2013\u03c0 inter\u00adactions between the + cations and between the + cation and the pydc ligand [centroid\u2013centroid distances = 3.489\u2005(5) and 3.694\u2005(5)\u2005\u00c5] are observed.In the centrosymmetric dinuclear complex anion of the title compound, (C DOI: 10.1107/S1600536811005629/hy2406Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine and benzene rings of adjacent mol\u00adecules, with a centroid\u2013centroid distance of 3.829\u2005(2)\u2005\u00c5.In the title centrosymmetric dinuclear complex, [Eu DOI: 10.1107/S1600536810046131/hy2358Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "III cations in the polymeric title compound, {[La2(C7H3NO4)3(H2O)4]\u00b72H2O}n. One is nine-coordinated in an LaN2O7 tricapped trigonal\u2013prismatic geometry formed by three pyridine-2,6-dicarboxyl\u00adate anions and two water mol\u00adecules, while the other is ten-coordinated in an LaNO9 bicapped square-anti\u00adprismatic geometry formed by four pyridine-2,6-dicarboxyl\u00adate anions and two water mol\u00adecules. The two LaIII cations are separated by a non-bonding distance of 5.026\u2005(3)\u2005\u00c5. The pyridine-2,6-dicarboxyl\u00adate anions bridge the LaIII cations, forming a three-dimensional polymeric complex. The crystal structure contains extensive classical O\u2014H\u22efO hydrogen bonds and weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The crystal structure is further consolidated by \u03c0\u2013\u03c0 stacking between pyridine rings, the shortest centroid\u2013centroid distance between parallel pyridine rings being 3.700\u2005(5)\u2005\u00c5.There are two independent La DOI: 10.1107/S1600536811030807/xu5269Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It is coordinated by two water mol\u00adecules in the apical directions and four 4-fluoro\u00adbenzoate (PFB) anions, bridging the symmetry related Mn atoms in the basal plane to form an infinite two-dimensional polymeric structure parallel to (100). The four O atoms of the PFB anions around the MnII atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two O atoms of the water mol\u00adecules. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 27.29\u2005(16)\u00b0. The O\u2014H\u22efO hydrogen bonds further connect the manganese-carboxyl\u00adate units. \u03c0\u2013\u03c0 contacts between the benzene rings [centroid-centroid distance = 3.6894\u2005(15)\u2005\u00c5] further stabilize the crystal structure.In the crystal structure of the title complex, [Mn(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(H2O)2] = 0.039                           wR(F                           2) = 0.111                           S = 1.28                           1758 reflections114 parametersH atoms treated by a mixture of independent and constrained refinementmax = 1.24 e \u00c5\u22123                        \u0394\u03c1min = \u22120.45 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811021921/su2282Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination network can be described as an uninodal 4-connected net with the sql topology. The HgII ion lies on a site of -1 symmetry and the apym ligand lies on sites of m symmetry with the mirror plane perpendicular to the pyrimidine plane and passing through the NH2 group N atom. This polymeric structure is stabilized by N\u2014H\u22efCl hydrogen bonds and columnar \u03c0\u2013\u03c0 stacking of pyrimidine rings, with a centroid\u2013centroid distance of 3.832\u2005(2)\u2005\u00c5.The title compound, [HgCl For mer al. 2007. For the al. 2007; Xie & W al. 2007. For top al. 2007. For an  al. 2011. For our al. 2009, 2011 \u25b6.2(C4H5N3)] = 0.020wR(F2) = 0.049S = 1.12992 reflections52 parametersH-atom parameters constrainedmax = 0.84 e \u00c5\u22123\u0394\u03c1min = \u22121.01 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812008793/gk2458Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II ion in the title compound, [Mn(CH3CO2)2(C15H11N3)]\u00b72H2O, is seven-coordinated in a considerably distorted penta\u00adgonal\u2013bipyramidal geometry by three N atoms of the tridentate 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine ligand and four O atoms from two acetate anions which chelate the Mn atom via two O atoms. The lateral pyridine rings are slightly inclined to the central pyridine ring, making dihedral angles of 13.6\u2005(2) and 5.7\u2005(2)\u00b0. The complex and solvent water mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds into a three-dimensional network.The Mn For rel al. 2004; Rich et al. 2010.2H3O2)2(C15H11N3)]\u00b72H2O = 0.055wR(F2) = 0.146S = 0.934936 reflections276 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.69 e \u00c5\u22123\u0394\u03c1min = \u22120.52 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The IrIII atom is coordinated by an \u03b75-C5Me5 ligand, a chloride and a Ph2P(CH2)3SPh-\u03baP,\u03baS ligand, leading to a three-legged piano-stool geometry. In the crystal, two water molecules and two chloride anions are linked by weak O\u2014H\u22efCl hydrogen bonding into tetra\u00admers that are located on centers of inversion. The H atoms of one of the methyl groups are disordered and were refined using a split model.The crystal structure of the title compound, [Ir(C For an  al. 2012.10H15)Cl(C21H21PS)]Cl\u00b7H2O = 0.041wR(F2) = 0.088S = 1.255513 reflections337 parameters147 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 1.68 e \u00c5\u22123\u0394\u03c1min = \u22121.50 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812021964/nc2278Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "An intra\u00admolecular N\u2014H\u22efO(carbon\u00adyl) hydrogen bond closes an S(6) ring. Supra\u00admolecular chains along [01-1] mediated by O\u2014H\u22efN(pyridine) hydrogen bonds feature in the crystal. A three-dimensional architecture is completed by \u03c0\u2013\u03c0 inter\u00adactions occurring between the benzene ring and the two rings of the thienopyridine residue [centroid\u2013centroid distances = 3.6963\u2005(13) and 3.3812\u2005(13)\u2005\u00c5]. The F atom is disordered over the two meta sites in a near statistical ratio [0.545\u2005(5):0.455\u2005(5)].In the title compound, C DOI: 10.1107/S1600536812027195/hb6844Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027195/hb6844Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the Me\u2013salen ligand, the benzene rings are almost parallel, making a dihedral angle of 0.48\u2005(13)\u00b0, but the torsion angle along the central C\u2014C bond is 41.1\u2005(2)\u00b0\u00b7The pyrrolidine rings are in slightly distorted chair conformations. The N atoms of the pyrrolidine axial ligands are involved in N\u2014H\u22efO hydrogen bonds with the perchlorate anions, and these hydrogen bonds connect the ionic species into infinite chains along the b axis. Some relatively short C\u2014H\u22ef\u03c0 inter\u00adactions are also present in the crystal structure and C\u2014H\u22efO inter\u00adactions occur. The guest solvent p-xylene mol\u00adecule lies on a special position at the inversion centre.In the mononuclear title complex, [Co(C For rel al. 2003. For thebach 1969.       18H18N2O2)(C4H9N)2]ClO4\u00b70.5C8H10                         = 0.040                           wR(F                           2) = 0.084                           S = 0.99                           7081 reflections502 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.67 e \u00c5\u22123                        \u0394\u03c1min = \u22120.51 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SIR92 (Altomare et al., 1993SHELXL97 (Sheldrick, 2008Stereochemical Workstation Operation Manual (Siemens, 1989SHELXL97.Data collection: 10.1107/S160053681004660X/jh2227sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004660X/jh2227Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CeIII atom is coordinated by eight O atoms from six INAIP ligands and a water mol\u00adecule in a distorted tricapped trigonal\u2013prismatic geometry, while the AgI atom has a distorted trigonal\u2013planar AgN2O geometry. O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine and benzene rings [centroid\u2013centroid distances = 3.642\u2005(4) and 3.624\u2005(3)\u2005\u00c5] stabilize the crystal structure.The 4 DOI: 10.1107/S1600536811027668/hy2446Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The equatorial Cu\u2014N and Cu\u2014O bond lengths are in the range 1.979\u2005(2)-1.998\u2005(3)\u2005\u00c5. The axial Cu\u2014O bond distances are 2.365\u2005(2) and 2.394\u2005(2)\u2005\u00c5. In the crystal, the complex cations and perchlorate anions are connected by numerous C\u2014H\u22efO hydrogen bonds, which leads to additional stabilization of the structure. The perchlorate anion is disordered over two sets of sites with a 0.716\u2005(3):0.284\u2005(3) occupancy ratio.The title compound, [Cu(C DOI: 10.1107/S1600536813018485/nr2046Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Ag\u2014C and Ag\u2014Cl single-bond lengths are 2.087\u2005(3) and 2.3267\u2005(9)\u2005\u00c5. The C\u2014Ag\u2014Cl bond angle is 172.84\u2005(7)\u00b0. C\u2014H\u22ef\u03c0 inter\u00adactions contribute to the stabilization of the crystal structure. A very weak \u03c0\u2013\u03c0 stacking inter\u00adaction between adjacent tetra\u00admethyl\u00adbenzene rings [centroid\u2013centroid distance = 4.0610\u2005(18)\u2005\u00c5] is also observed.In the title compound, [AgCl(C DOI: 10.1107/S1600536812012998/sj5223Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each AgI ion is bicoordinated in a slightly distorted linear coordination geometry by the N atoms of two ligands, resulting in the formation of a 22-membered metallamacrocycle. In the dication, \u03c0\u2013\u03c0 inter\u00adactions are observed between the imidazole rings, with centroid\u2013centroid distances of 3.528\u2005(3)\u2005\u00c5 and dihedral angles of 9.92\u2005(9)\u00b0. The crystal structure is stabilized by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions involving the benzene rings of adjacent dications, with centroid\u2013centroid distances of 3.651\u2005(2)\u2005\u00c5.In the title compound, [Ag DOI: 10.1107/S1600536811018691/rz2589Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII atom is situated on a crystallographic center of inversion and is octa\u00adhedrally coordinated by two O atoms from two anions, two N atoms of two 1,2-bis\u00ad(pyridin-4-yl)ethane mol\u00adecules and two O atoms from two water mol\u00adecules. A three-dimensional network is established by inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.The asymmetric unit of the title compound, [Co(C For general background to the design of metal-organic supra\u00admolecular solids with potential functionality, see: Moulton & Zaworotko 2001; Janiak 9H7O4)2(C12H10N2)2(H2O)2] = 0.055                           wR(F                           2) = 0.105                           S = 1.06                           3635 reflections268 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.71 e \u00c5\u22123                        \u0394\u03c1min = \u22120.36 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811024755/im2300Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom lies on a crystallographic twofold rotation axis and shows a significantly distorted tetra\u00adhedral coordination geometry. The dihedral angle between the phenyl rings is 74.3\u2005(2)\u00b0. The crystal structure is stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.635\u2005(2)\u20133.803\u2005(3)\u2005\u00c5].The asymmetric unit of the title compound, [CuCl DOI: 10.1107/S1600536811050690/rz2665Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distance = 3.510\u2005(3)\u2005\u00c5] are present in the crystal.In the title compound, [InCl DOI: 10.1107/S1600536812038147/hy2584Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One AgI ion is coordinated by one O atom from a 3-carboxyl\u00adato-4-hy\u00addroxy\u00adbenzene\u00adsulfonate (L) ligand, two N atoms from two pyrazine ligands and a water mol\u00adecule. The other AgI ion is coordinated by two O atoms from two L ligands and one N atom from a pyrazine ligand. One of the pyrazine ligands lies on an inversion center. The L and pyrazine ligands link the AgI ions into polymeric layers parallel to the ac plane. The layers are connected by inter\u00admolecular O\u2014H\u22efO hydrogen bonds. An intra\u00admolecular O\u2014H\u22efO hydrogen bond is also present in the L ligand.The title coordination polymer, {[Ag For a related structure, see: Nie & Qu 2011.       4(C7H4O6S)2(C4H4N2)3(H2O)2]\u00b72H2O = 0.033                           wR(F                           2) = 0.073                           S = 0.88                           3387 reflections256 parameters5 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.70 e \u00c5\u22123                        \u0394\u03c1min = \u22121.09 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811041626/hy2474Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination environment of each ReI atom is distorted octahedral. Four intra\u00admolecular O\u2014H\u22efN and four inter\u00admolecular C\u2014H\u22efO hydrogen-bond inter\u00adactions are observed. Relatively strong hydrogen bonds are found between the hydrogen-bond donor (\u03bc3-OH) and acceptor (basic N atom of pyridine), with N\u22efO distances between 2.586\u2005(10) and 2.628\u2005(10)\u2005\u00c5. Inter\u00adcube distances of 9.873\u2005(2) and 12.376\u2005(3)\u2005\u00c5 are observed.The title compound, [Re DOI: 10.1107/S1600536812036033/hg5243Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each RhI atom is coordinated by one O atom [Rh\u2014O = 2.044\u2005(2) and 2.026\u2005(2)\u2005\u00c5], one N atom [Rh\u2014N = 2.083\u2005(2) and 2.090\u2005(2)\u2005\u00c5], and one COD ligand via two \u03b72-bonds, each directed toward the mid-point of a C=C bond (Cg): Rh\u2014Cg = 2.007\u2005(2), 2.013\u2005(2), 2.000\u2005(2) and 2.021\u2005(2)\u2005\u00c5. Each RhI atom has a quasi-square-planar coordination geometry, with average r.m.s. deviations of 0.159\u2005(1) and 0.204\u2005(1)\u2005\u00c5 from the mean planes defined by Rh and the termini of its four coordinating bonds. The two COD ligands have quasi-C2 symmetry, twisted from ideal Cv2 symmetry by 30.0\u2005(3) and \u221233.1\u2005(3)\u00b0, and are quasi-enanti\u00adomers of one another. The intra\u00admolecular Rh\u22efRh distance of 5.9432\u2005(3)\u2005\u00c5 suggests that there is no direct metal\u2013metal inter\u00adaction.In the title solvate, [Rh DOI: 10.1107/S1600536812040603/cv5334Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The water ligands of the core are involved in hydrogen bonds with the triazole N atoms of the organic mol\u00adecules, which generates a layer motif in the ab plane. There are \u03c0\u2013\u03c0 stacking inter\u00adactions between benzene rings of 3.490\u2005(6)\u2005\u00c5, and between triazole rings of 3.543\u2005(8) and 3.734\u2005(7)\u2005\u00c5 in neighboring layers, forming a three-dimensional network.The title complex, [Fe DOI: 10.1107/S160053681202613X/pk2413Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title salt, [Cu(C10H24N4)(H2O)2](C8H7O2)2\u00b7H2O, is chelated by the four N atoms of the 1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane (cyclam) ligand and is coordinated by two water mol\u00adecules in a Jahn\u2013Teller-type of tetra\u00adgonally distorted octa\u00adhedral geometry. The cations, anions and lattice water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds to form a layer structure parallel to (001).The Cu DOI: 10.1107/S1600536810026012/bt5288Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each mol\u00adecule, the fused six-membered rings have chair\u2013chair\u2013chair\u2013chair conformations and the cyclo\u00adpentane ring adopts an envelope conformation with the C atom bearing the hy\u00addroxy\u00admethyl group as the flap. All ring junctions are trans-fused. With the exception of one of the methyl groups adjacent to the C=O group, all the methyl groups are in axial positions. The isopropenyl group is equatorial and the hy\u00addroxy\u00admethyl group is in an axial orientation. In the crystal, weak C\u2014H\u22efO inter\u00adactions link the mol\u00adecules into chains along [010]. Weak intra\u00admolecular C\u2014H\u22efO hydrogen bonds are also observed but the hy\u00addroxy groups are not involved in hydrogen bonds.The asymmetric unit of the title compound, C \u00c5b = 19.1818 (6) \u00c5c = 28.1141 (7) \u00c5V = 5093.3 (3) \u00c53Z = 8K\u03b1 radiationMo \u22121\u03bc = 0.07 mmT = 100 K0.60 \u00d7 0.56 \u00d7 0.20 mmOxford Diffraction diffractometer with a Sapphire3 detectorCrysAlis RED; Oxford Diffraction, 2008Tmin = 0.960, Tmax = 0.986Absorption correction: multi-scan (61473 measured reflections5036 independent reflectionsI > 2\u03c3(I)4401 reflections with Rint = 0.055R[F2 > 2\u03c3(F2)] = 0.051wR(F2) = 0.141S = 1.035036 reflections609 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.55 e \u00c5\u22123\u0394\u03c1min = \u22120.50 e \u00c5\u22123\u0394\u03c1CrysAlis CCD  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813011008/lh5603Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The pyridinium rings are almost planar [maximum deviations = 0.004\u2005(4) and 0.003\u2005(4)\u2005\u00c5]. The ethyl groups are approximately perpendicular to the corresponding pyridinium ring planes [N\u2014C\u2014C\u2014C = 88.8\u2005(4)\u00b0 in each ligand]. The packing of the mol\u00adecules is controlled by \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.625\u2005(3) and 3.711\u2005(2)\u2005\u00c5, forming chains approximately parallel to (102). The crystal studied was non-merohedrally twinned .In the bioactive title compound, [ZnBr DOI: 10.1107/S1600536810052190/sj5050Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two O,O\u2032-bis\u00ad(4-methyl\u00adphen\u00adyl)dithio\u00adphosphate anions occupy the axial positions with long Cu\u22efS distances of 3.0090\u2005(8)\u2005\u00c5. Inter\u00admolecular N\u2014H\u22efS and C\u2014H\u22efS hydrogen bonding is present between the anions and the cation.In the title compound, [Cu(C DOI: 10.1107/S1600536810046672/xu5079Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Four symmetry-equivalent mesitylacetamidate ligands bridge the Rh\u2014Rh unit. Thus, each RhII atom has an approximately octa\u00adhedral coordination by one Rh [Rh\u2014Rh = 2.4290\u2005(6)\u2005\u00c5], two acetamidate O atoms trans to each other [Rh\u2014O = 2.044\u2005(3)\u2005\u00c5], two acetamidate N atoms trans to each other [Rh\u2014N = 2.091\u2005(4)\u2005\u00c5], and a benzonitrile N atom trans to Rh [Rh\u2014N = 2.222\u2005(3)\u2005\u00c5]. The structure is held together by weak van der Waals forces.The title structure, [Rh DOI: 10.1107/S1600536812024518/qk2033Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, generating [001] C               2               2(4) chains such that mol\u00adecules A and B alternate. There is no aromatic \u03c0\u2013\u03c0 stacking in the crystal as the shortest centroid\u2013centroid distance is greater than 4.74\u2005\u00c5.The previous structure determination [Gillier-Pandraud  al. 1972. C. R. A DOI: 10.1107/S1600536811013547/hb5838Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II(TpivPP) {TpivPP is the dianion of 5,10,15,20-tetra\u00adkis\u00ad[2-\u00adphen\u00adyl]por\u00adph\u00adyrin} with an excess of KCN salts and an excess of the 18-crown-6 in chloro\u00adbenzene leads to the polymeric title compound catena-polyporphyrinato-1\u03baO5:2\u03ba4N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2032:1\u2032\u03baO15}cobalt(III)potassium] dihydrate], {[CoK(CN)2(C12H24O6)(CN)2]\u2212 ion complex and one half of a . In the crystal, the polymeric chains and the lattice water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, as well as weak C\u2014H\u22efO, O\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions into a three-dimensional supra\u00admolecular architecture.The reaction of Co DOI: 10.1107/S1600536814003596/xu5770Isup2.hklStructure factors: contains datablock(s) I. DOI: 987431CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains one half of the [Mg(TPP)(H2O)2] complex and one half of an 18-crown-6 mol\u00adecule. The average equatorial magnesium\u2013pyrrole N atom distance (Mg\u2014Np) is 2.071\u2005(1)\u2005\u00c5 and the axial Mg\u2014O(H2O) bond length is 2.213\u2005(1)\u2005\u00c5. The crystal packing is stabilized by two O\u2014H\u22efO hydrogen bonds between coordinating water mol\u00adecules and adjacent 18-crown-6 mol\u00adecules, and exhibits a one-dimensional supramolecular structure along the a axis. The supramolecular architecture is futher stabilized by weak C\u2014H\u22ef\u03c0 inter\u00adactions. The 18-crown-6 mol\u00adecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.In the title compound, [Mg(C DOI: Click here for additional data file.10.1107/S1600536813001219/xu5669Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazole rings [centroid\u2013centroid distances = 3.4914\u2005(15) and 3.6167\u2005(15)\u2005\u00c5] further stabilize the crystal structure. In the title compound, [Co(C DOI: 10.1107/S1600536812037579/hy2579Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuI atom has a distorted tetra\u00adhedral coordination. The O\u2014Cu\u2014O angle is 80.07\u2005(8)\u00b0 and the P\u2014Cu\u2014P angle is 123.49\u2005(3)\u00b0. The crystal packing is stablized by intra\u00admolecular C\u2014H\u22efO inter\u00adactions and inter\u00admolecular C\u2014H\u22efO and O\u2014H\u22efO inter\u00adactions.In the title compound, [Cu(C DOI: 10.1107/S1600536811011470/fi2105Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ligator atoms comprise the two pyridine N atoms of the chelating di-2-pyridyl\u00adamine (dpa) ligand and two N atoms from two azide anions. The dpa ligand coordinates the Pd atom in a boat conformation, the dihedral angle between the pyridine rings being 24.4\u2005(1)\u00b0. The pyridine rings are somewhat inclined to the least-squares plane of the PdN4 unit, making dihedral angles of 29.02\u2005(9) and 26.47\u2005(9)\u00b0. The azide ligands are slightly bent, with N\u2014N\u2014N angles of 173.0\u2005(4) and 174.2\u2005(4)\u00b0. In the crystal, mol\u00adecules are connected by N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, forming chains along the c axis. When viewed down the b axis, successive chains are stacked in opposite directions. Intra\u00admolecular C\u2014H\u22efN hydrogen bonds are also observed.In the title complex, [Pd(N II complexes [PdX2(dpa)] (X = Cl or Br), see: Rauterkus et al. 2(C10H9N3)] = 0.029wR(F2) = 0.073S = 1.062322 reflections181 parametersH-atom parameters constrainedmax = 0.71 e \u00c5\u22123\u0394\u03c1min = \u22120.41 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "These two constituents are linked by a remarkably short inter\u00adaction between the Br atom of the imidazolium cation [C\u2014Br = 1.85\u2005(3)\u2005\u00c5] and one N atom of the cyanidoargentate anion [Br\u22efN = 2.96\u2005(2)\u2005\u00c5], which is much less than the sum of the van der Waals radii (3.40\u2005\u00c5). The crystal studied was twinned by merohedry.The title structure, (C DOI: 10.1107/S1600536811051828/qk2020Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoIII atom exhibits an octa\u00adhedral geometry, coordinated by four N atoms from the tris\u00ad(2-pyridyl\u00admeth\u00adyl)amine ligand with an average Co\u2014N distance of 1.953\u2005(2)\u2005\u00c5, and two cyanide C atoms with an average Co\u2014C distance of 1.895\u2005(2)\u2005\u00c5. The crystal packing is stabilized by inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efF inter\u00adactions.In the title complex, [Co(CN) DOI: 10.1107/S1600536811012001/vm2083Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the central Ti2(\u03bc2-O)2 fragment, the metal\u2013oxygen distances are significantly different [1.7962\u2005(19) and 1.9292\u2005(19)\u2005\u00c5]. In the crystal, the chloro\u00adform mol\u00adecule is anchored via an N\u2014H\u22efCl and a bifurcated C\u2014H\u22ef hydrogen bond. Slipped \u03c0\u2013\u03c0 stacking [shortest C\u22efC distance = 3.585\u2005(4)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions contribute to the coherence of the structure.In the title structure, [Ti DOI: 10.1107/S1600536813029656/qk2062Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813029656/qk2062Isup3.molSupplementary material file. DOI: 969061 crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two LaIII metal ions are linked by two bidentate bridging carboxyl\u00adate groups with a \u03ba2               O:O\u2032 coordination mode and two bidentate chelating bridging carboxyl\u00adate groups with a \u03ba3               O:O,O\u2032 coordination mode. The coordination sphere of lanthanum, completed by a terminal chloride and three water mol\u00adecules, adopts a distorted tricapped trigonal\u2013prismatic arrangement. N\u2014H\u22efCl, N\u2014H\u22efO and O\u2014Hwater\u22efCl hydrogen bonds, and slipped \u03c0\u2013\u03c0 inter\u00adactions between parallel benzene rings [centroid\u2013centroid distance of 3.647\u2005(3)\u2005\u00c5] are observed in the structure. These combine to stabilize a three-dimensional network.The tiltle complex, [La DOI: 10.1107/S1600536810052864/su2239Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ru\u2014Ru distance and Ru\u2014O\u2014Ru angle are 3.2838\u2005(3)\u2005\u00c5 and 121.79\u2005(7)\u00b0, respectively, and the average Ru\u2014N(pyridine) bond length is 2.164\u2005(8)\u2005\u00c5. Several C\u2014H\u22efF, C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions generate a three-dimensional network in the crystal structure. \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.6389\u2005(3)\u2005\u00c5] between inversion-related 2,2\u2032-bipyridine rings are also observed.The hemerythrin-type dinuclear title complex, [Ru DOI: Click here for additional data file.10.1107/S1600536813003334/gg2109Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angles between the oxazole rings and their pendant rings are 2.0\u2005(3) and 24.3\u2005(2)\u00b0. The F atoms are disordered over two sites with occupancies of 0.627\u2005(3) and 0.373\u2005(3) in the phenyl\u00adene\u2013oxazol\u00adyl\u2013phenyl and in oxazol\u00adyl\u2013phenyl fragments, respectively. In the crystal structure, mol\u00adecules are linked through a network of C\u2014H\u22efF and weak \u03c0\u2013\u03c0 stacking inter\u00adactions.In the title compound, C DOI: 10.1107/S1600536810031235/fb2208Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The cation has a distorted octa\u00adhedral coordination environment and is surrounded by two N and two Cl atoms in the equatorial plane, while the coordinating water O atoms occupy the axial positions. The crystal exhibits nonmerohedral twinning with two domain states, the volume fractions of which were refined to 0.883\u2005(2) and 0.117\u2005(3). The crystal packing is stabilized by O\u2014H\u22efCl hydrogen-bond inter\u00adactions, forming two-dimensional networks lying parallel to (001). The crystal packing also features \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings, with centroid\u2013centroid separations of 3.493\u2005(3) and 3.545\u2005(3)\u2005\u00c5.The title mol\u00adecule, [CoCl For related structures, see: Li et al. 2(H2O)2] = 0.047wR(F2) = 0.149S = 1.162211 reflections88 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.71 e \u00c5\u22123\u0394\u03c1min = \u22120.99 e \u00c5\u22123\u0394\u03c1CrysAlis CCD  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536813022484/fb2288Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In each mol\u00adecule, the four-coordinated SnIV atom exists in a distorted tetra\u00adhedral geometry and two intra\u00admolecular N\u2014H\u22efO hydrogen bonds with S(6) ring motifs are present. In one mol\u00adecule, the benzene ring of the 2-amino-3-nitro\u00adbenzoate ligand makes dihedral angles of 42.74\u2005(11), 89.66\u2005(13) and 53.04\u2005(10)\u00b0 with the three phenyl rings. The corresponding dihedral angles for the other mol\u00adecule are 6.29\u2005(11), 66.55\u2005(11) and 62.33\u2005(10)\u00b0. In the crystal, a weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction and a \u03c0\u2013\u03c0 stacking inter\u00adaction with a centroid\u2013centroid distance of 3.5877\u2005(12)\u2005\u00c5 are observed.The asymmetric unit of the title compound, [Sn(C DOI: 10.1107/S160053681101244X/is2696Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each PdII ion has a distorted square-planar coordination sphere, defined by three N atoms of the macrocyclic ligand and a chloride ion. The PdII complex cations and the methanol mol\u00adecules are linked through N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a zigzag chain along [101]. An intra\u00admolecular N\u2014H\u22efCl hydrogen bond is also observed.In the crystal structure of the title compound, [Pd For dipters 2010; Goforth al. 2013. For pal al. 2013; Parker  al. 1985. For a s al. 2003. For a s al. 2010.2(C36H42N6)Cl2](ClO4)2\u00b72C3H7NO\u00b72CH4O = 0.038wR(F2) = 0.097S = 1.085826 reflections324 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.80 e \u00c5\u22123\u0394\u03c1min = \u22120.81 e \u00c5\u22123\u0394\u03c1CrystalClear  used to solve structure: SIR92  global, I. DOI: 10.1107/S1600536813022666/is5294Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The compound is a tetra\u00adnuclear ZnII complex centered about a fourfold roto-inversion axis, with the ligand coordinating in the doubly deprotonated form. The ZnII atom has a distorted square-pyramidal geometry being coordinated by one N and two O-atom donors from the doubly deprotonated L2\u2212 ligand, and by one N atom and one O-atom donor from a symmetry-related L2\u2212 ligand. In the crystal, four symmetry-related lattice water mol\u00adecules, centred about a fourfold roto-inversion axis, form a cyclic tetra\u00admer through O\u2014H\u22efO hydrogen bonds. These tetra\u00admers connect to the complex mol\u00adecules through O\u2014H\u22efN hydrogen bonds, forming a chain propagating along [100]. Neighbouring mol\u00adecules are linked by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.660\u2005(2)\u2005\u00c5] involving the quinolidine rings.In the title compound, [Zn N-donor ligands, see: Palacios et al. 4]\u00b74H2O = 0.036wR(F2) = 0.087S = 1.032900 reflections217 parametersH-atom parameters constrainedmax = 0.27 e \u00c5\u22123\u0394\u03c1min = \u22120.23 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812018995/su2415Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One RhII atom is five-coordinate, in a distorted pyramidal geometry, while the other is six-coord\u00adin\u00adate, with a disorted octa\u00adhedral geometry. For the six-coord\u00adinate RhII atom, the axial nitrile ligand shows a non-linear Rh\u2013nitrile coordination with an Rh\u2014N\u2014C bond angle of 166.4\u2005(4)\u00b0 and a nitrile N\u2014C bond length of 1.138\u2005(6)\u2005\u00c5. Each unique RhII atom is coordinated by a trans pair of N atoms and a trans pair of O atoms from the four acetamide ligands. The Neq\u2014Rh\u2014Rh\u2014Oeq torsion angles on the acetamide bridge varies between 12.55\u2005(11) and 14.04\u2005(8)\u00b0. In the crystal, the 3-methyl\u00adbenzo\u00adnitrile ring shows a \u03c0\u2013\u03c0 inter\u00adaction with an inversion-related equivalent [inter\u00adplanar spacing = 3.360\u2005(6)\u2005\u00c5]. A phenyl ring on one of the acetamide ligands also has a face-to-face \u03c0\u2013\u03c0 inter\u00adaction with an inversion-related equivalent [inter\u00adplanar spacing = 3.416\u2005(5)\u2005\u00c5].In the title compound, [Rh DOI: 10.1107/S1600536813029838/pk2497Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Am. Mineral.54, 19\u201330], all non-H atoms were refined with anisotropic displacement parameters and H-atoms were located by difference Fourier methods and refined from X-ray diffraction data. The structure is built up from nearly regular [Al(H2O)6]3+ octa\u00adhedra and infinite double-stranded chains [Na(SO4)2]3\u2212 that extend parallel to [001]. The Na+ cation has a strongly distorted octa\u00adhedral coordination by sulfate O atoms [Na\u2014O = 2.2709\u2005(11) \u2013 2.5117\u2005(12)\u2005\u00c5], of which five are furnished by the chain-building sulfate group S2O4 and one by the non-bridging sulfate group S1O4. The [Na(SO4)2]3\u2212 chain features an unusual centrosymmetric group formed by two NaO6 octa\u00adhedra and two S2O4 tetra\u00adhedra sharing five adjacent edges, one between two NaO6 octa\u00adhedra and two each between the resulting double octa\u00adhedron and two S2O4 tetra\u00adhedra. These groups are then linked into a double-stranded chain via corner-sharing between NaO6 octa\u00adhedra and S2O4 tetra\u00adhedra. The S1O4 group, attached to Na in the terminal position, completes the chains. The [Al(H2O)6]3+ octa\u00adhedron (\u2329Al\u2014O\u232a = 1.885\u2005(11)\u2005\u00c5) donates 12 comparatively strong hydrogen bonds (O\u22efO = 2.6665\u2005(14) \u2013 2.7971\u2005(15)\u2005\u00c5) to the sulfate O atoms of three neighbouring [Na(SO4)2]3\u2212 chains, helping to connect them in three dimensions, but with a prevalence parallel to (010), the cleavage plane of the mineral. Compared with the previous work on tamarugite, the bond precision of Al\u2014O bond lengths as an example improved from 0.024 to 0.001\u2005\u00c5.The crystal structure of tamarugite [sodium aluminium bis\u00ad(sulfate) hexa\u00adhydrate] was redetermined from a single crystal from Mina Alcaparossa, near Cerritos Bayos, southwest of Calama, Chile. In contrast to the previous work [Robinson & Fang 1969. Am. Min DOI: 10.1107/S1600536813025154/pj2005Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is stabilized by weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0(arene) inter\u00adactions. The Ru\u2014\u03b75-cyclopentadienyl centroid bond length is 1.946\u2005(11)\u2005\u00c5In the title mol\u00adecule, [Ru(C DOI: 10.1107/S1600536810033180/lh5113Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal atom is further chelated by a carboxyl\u00adate group and is covalently bonded to a monodentate carboxyl\u00adate group as well as to a monodentate sulfonate group in a distorted square anti\u00adprismatic geometry. The coordinating water molecules and the lattice water molecules, one of which is disordered over two positions [major component 65\u2005(3)%], are hydrogen bonded to the network.The 4-sulfophthalate trianion in the polymeric complex, {[Er(C III derivative, see: Xiao et al. Eu al. 2010.8H3O7S)(C12H8N2)(H2O)2]\u00b72H2O = 0.037wR(F2) = 0.095S = 1.094014 reflections353 parameters33 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.97 e \u00c5\u22123\u0394\u03c1min = \u22121.21 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812003467/xu5455Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, {[Pb2(C7H6NO2)4]}n, is chelated by two 3-aminobenzoato ligands in a distorted pentagonal-bipyramidal coordination geometry with five oxygen donors in the equatorial positions, one nitro\u00adgen donor and one oxygen donor in the axial positions. Two mol\u00adecules are linked through a centre of inversion, forming a dinuclear entity. These entities are linked in a \u03bc3-bridging mode through the amino N atom and two carboxyl\u00adate O atoms into a chain along the b axis. Classical inter\u00admolecular N\u2014H\u22efO hydrogen bonding is observed in the structure. The supra\u00admolecular structure is consolidated by \u03c0\u2013\u03c0 stacking inter\u00adactions with  centroid\u2013centroid distances between benzene rings of 3.837\u2005(8)\u2005\u00c5.The Pb DOI: 10.1107/S1600536810041322/rk2229Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the trigonal\u2013pyramidal Ru3P core, one RuII atom is coordinated by a triphenyl\u00adphosphane ligand in a terminal fashion. Two hydride ligands bridge over two Ru\u2014Ru bonds. These Ru\u2014Ru bonds [2.9400\u2005(4) and 2.9432\u2005(4)\u2005\u00c5] are slightly longer than the nonhydride-bridged Ru\u2014Ru bond [2.8146\u2005(4)\u2005\u00c5]. The terminal triphenyl\u00adphosphane ligand coordinates to the RuII atom, which is involved in two hydride bridges.In the crystal structure of the title compound, [Ru H2(C18H15P)(CO)8] = 0.030wR(F2) = 0.118S = 1.238304 reflections444 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.74 e \u00c5\u22123\u0394\u03c1min = \u22121.79 e \u00c5\u22123\u0394\u03c1PROCESS-AUTO  I, global. DOI: 10.1107/S1600536812039499/nc2293Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The carbonyl and chloride ligands in the cation adopt a mutually cis arrangement and these are disordered over two sets of sites with site occupancies of 0.721\u2005(6) and 0.279\u2005(6). The Ru\u2014N bond length [2.117\u2005(2)\u2005\u00c5] trans to the carbonyl ligand is slightly longer than the average of the other Ru\u2014N bond lengths (2.08\u2005\u00c5), which can be explained by the expected trans influence of the carbonyl group. In the crystal, weak C\u2014H\u22efF inter\u00adactions are observed between the complex cation and the PF6\u2212 anion, leading to the formation of a three-dimensional supramolecular structure. The crystal studied was an inversion twin with twin fractions of 0.78\u2005(4) and 0.22\u2005(4).In the title compound, [RuCl(C Cl]+, see: Ishida et al. 2(CO)]\u00b7PF6 = 0.032wR(F2) = 0.062S = 1.085177 reflections330 parametersH-atom parameters constrainedmax = 1.37 e \u00c5\u22123\u0394\u03c1min = \u22121.28 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 2249 FrFlack parameter: 0.22 (4)CrystalClear-SM  used to solve structure: SIR97  global, I. DOI: Click here for additional data file.10.1107/S1600536812048246/is5220Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mol\u00adecular structure is stabilized by weak C\u2014H\u22efO and C\u2014H\u22efF hydrogen-bond inter\u00adactions. The crystal structure is stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions (centroid\u2013centroid distance = 3.951\u2005\u00c5).The title compound, [Ir(C DOI: 10.1107/S1600536813026160/bx2449Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, pairs of mol\u00adecules form inversion dimers via N\u2014H\u22efCl hydrogen bonds. In addition, intra\u00admolecular N\u2014H\u22efCl and weak C\u2014H\u22efCl, C\u2014H\u22efN, N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 hydrogen bonds are observed. One of the Cl atoms of the solvent mol\u00adecule is disordered over two sites with refined occupancies of 0.62\u2005(1) and 0.38\u2005(1).In the title compound, [RuCl DOI: 10.1107/S1600536812014080/lh5442Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Within the pcp ligands, the dihedral angles between the polycyclic skeletons and pendant pyridine rings are 6.2\u2005(2) and 8.3\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked by O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds. Several aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid separation = 3.516\u2005(3)\u2005\u00c5] are also observed.In the title compound, [Mn(C DOI: 10.1107/S1600536811004569/hb5800Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atom is in a distorted octa\u00adhedral coordination by two N atoms in a cis disposition [Ni\u2014N = 2.0753\u2005(16) and 2.1048\u2005(16)\u2005\u00c5] and by four water O atoms [Ni\u2014O = 2.0500\u2005(15)\u20132.0822\u2005(15)\u2005\u00c5]. The crystal structure is completed by four further non-coordinating water mol\u00adecules and all constituents are linked in a three-dimensional manner by an extensive system of 16 O\u2014H\u22efO hydrogen bonds.The title structure, [Ni(C DOI: 10.1107/S1600536812027122/qk2036Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The 4-(dimethyl\u00adamino)\u00adpyridinium cations are protonated at the pyridine N atoms and form N\u2014H\u22efCl hydrogen bonds with Cl\u2212 counter-ions. The dimethyl\u00adamino groups (C/N/C) lie close to the plane of the pyridinium rings, making dihedral angles of 1.6\u2005(6)\u00b0 and 6.5\u2005(3)\u00b0. In the crystal, the [Nd2Cl4(H2O)10]2+ dications are linked via O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds, forming sheets lying parallel to the bc plane. These sheets are linked via O\u2014H\u22efCl hydrogen bonds, forming a three-dimensional network. The 4-(dimethyl\u00adamino)\u00adpyridinium cations are located in the cavities and linked to the framework by C\u2014H\u22efCl interactions.The title compound, (C DOI: Click here for additional data file.10.1107/S1600536812041724/su2506Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II complex, [Cu(C7H3NO4)(C6H5NO2)(H2O)]\u00b7H2O, the environment of the Cu2+ ion is a distorted square pyramid with the axial site occupied by the O atom from the coordinated water mol\u00adecule and the square base formed by two O and two N atoms from the tridentate anion and the neutral monodentate pyridine-3-carboxylic acid ligand. O\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.945\u2005(3)\u2005\u00c5] contribute to the stabilization of this structure.In the title Cu DOI: 10.1107/S160053681101926X/yk2006Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 stacking between the pyridine rings in the bc plane [centroid\u2013centroid distance = 3.725\u2005(3)\u2005\u00c5] are present in the crystal structure.In the title compound, [CoBr DOI: Click here for additional data file.10.1107/S1600536812041980/xu5630Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal packing exhibits a short O\u22efBr inter\u00adaction [Br\u22efO = 3.185\u2005(3)\u2005\u00c5] and a weak inter\u00admolecular C\u2014H\u22efO contact.The title compound, C DOI: 10.1107/S1600536811010051/fy2003Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The octa\u00adhedral environment around niobium is slightly distorted with Nb\u2014O distances in the range 1.8603\u2005(15)\u20132.1083\u2005(15)\u2005\u00c5 and an Nb\u2014Cl distance of 2.4693\u2005(9)\u2005\u00c5. The O\u2014Nb\u2014O angles vary between 80.74\u2005(6) and 100.82\u2005(7)\u00b0, while the trans Cl\u2014Nb\u2014O angle is 167.60\u2005(5)\u00b0. There are no hydrogen bonds observed, only an inter\u00admolecular C\u2014H\u22efO inter\u00adaction.In the title compound, [Nb(CH DOI: 10.1107/S1600536810021719/pv2289Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the components are linked into a three-dimensional framework by inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and N\u2014H\u22efN and weak C\u2014H\u22efO hydrogen bonds. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances in the range 3.4809\u2005(7)\u20133.8145\u2005(6)\u2005\u00c5 are observed.The asymmetric unit of the title complex, (C DOI: 10.1107/S1600536811027917/lh5282Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds connect mol\u00adecules into chains along [100] and there are \u03c0\u2013\u03c0 stacking inter\u00adactions between pairs of chains with a centroid\u2013centroid distance of 3.5485\u2005(15)\u2005\u00c5.In the title compound, C DOI: 10.1107/S160053681002979X/lh5093Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CdII atom is seven-coordinated in a distorted penta\u00adgonal\u2013bipyramidal configuration, defined by five O atoms from the carboxyl\u00adate groups of three 7-oxabicyclo\u00ad[2.2.1]heptane-2,3-dicarboxyl\u00adato ligands and two N atoms from the 2,2\u2032-bipyridine ligand. Two O atoms link two CdII atoms, forming a dinuclear center: the Cd\u2014O\u2014Cd bridging angle is 110.19\u2005(6)\u00b0. The polymeric structure extends along [100] and is linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds involving the solvent water molecule. Extensive \u03c0\u2013\u03c0 stacking exists between 2,2-bypiridine ligands along [010] with centroid-centroid distance of 3.650\u2005(2)\u2005\u00c5The title compound, {[Cd(C DOI: 10.1107/S1600536811036634/zb2016Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the components are linked via inter\u00admolecular O\u2014H\u22efO hydrogen bonds, forming layers parallel to (001). Additional stabilization within these layers is provided by \u03c0\u2013\u03c0 [centroid\u2013centroid distances of 3.7848\u2005(9)\u20134.4231\u2005(9)\u2005\u00c5] stacking inter\u00adactions.The central CuN DOI: 10.1107/S1600536811013808/bq2292Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The range of Ag\u2014O bond lengths is 2.169\u2005(2)\u20132.433\u2005(2)\u2005\u00c5, whereas the Ag\u22efAg separations are in the range 2.8674\u2005(4)\u20133.6256\u2005(5)\u2005\u00c5. The 2-methyl\u00adbenzoate groups are oriented at a dihedral angle of 60.7\u2005(1)\u00b0 with respect to each other.The crystal structure of the title compound, [Ag DOI: 10.1107/S1600536811016801/ez2241Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the dinuclear complex mol\u00adecules are linked into one-dimensional supra\u00admolecular columns parallel to the b axis by O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.7259\u2005(11)\u2005\u00c5].The title complex, [Cu DOI: 10.1107/S1600536812039839/rz5004Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Intra\u00admolecular O\u2014H\u22efN hydrogen bonds between the hy\u00addroxy O atoms and the imine N atoms, with O\u22efN distances in the range 2.607\u2005(3)\u20132.665\u2005(3)\u2005\u00c5, form nearly planar six-membered rings. In the crystal, weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds occur and several intra- and inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are present between adjacent benzene rings, with a shortest centroid\u2013centroid distance of 3.507\u2005(2)\u2005\u00c5.In the title compound, C DOI: 10.1107/S1600536810047185/is2631Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The HgII atom is four-coordinated in a distorted tetra\u00adhedral geometry by one terminal Cl atom, two bridging Cl atoms, and one C atom from the ylidic ligand, resulting in a polymeric chain parallel to [010]. The terminal Cl atom is more strongly bound to the HgII ion [2.3916\u2005(9)\u2005\u00c5] than the bridging Cl atoms. The bridge is asymmetric, as indicated by the two different Hg\u2014Cl(bridging) bond lengths [2.5840\u2005(8) and 2.7876\u2005(8)\u2005\u00c5]. Intra\u00admolecular C\u2014H\u22efO and weak C\u2014H\u22efCl contacts stabilize the polymeric chain. In the crystal, adjacent chains inter\u00adact via C\u2014H\u22efO hydrogen bonds. In the title organometallic polymer, [HgCl II complex, see: Ebrahim et al. ] = 0.025wR(F2) = 0.067S = 1.036143 reflections307 parametersH-atom parameters constrainedmax = 0.96 e \u00c5\u22123\u0394\u03c1min = \u22120.45 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812043073/bh2457Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II title compound, [Cd2(C9H10NO2)4(C6H6N2O)2(H2O)2], each seven-coordin\u00adated CdII atom is chelated by the carboxyl\u00adate groups of the two 4-(dimethyl\u00adamino)\u00adbenzoate (DMAB) anions; the two monomeric units are bridged through the two O atoms of the two carboxyl groups. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distance = 3.974\u2005(1)\u2005\u00c5] may further stabilize the structure. Weak C\u2014H\u22ef\u03c0 inter\u00adactions are also observed.In the centrosymmetric dimeric Cd DOI: 10.1107/S160053681002163X/xu2771Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Zn\u2014Br bond lengths range from 2.3901\u2005(19) to 2.449\u2005(2)\u2005\u00c5 and the Br\u2014Zn\u2014Br angles range from 107.09\u2005(8) to 112.48\u2005(8)\u00b0. In the crystal, each [ZnBr4]2\u2212 anion is connected to four cations through two N\u2014H\u22efBr and two C\u2014H\u22efBr hydrogen bonds, forming two-dimensional \u22ef(cation)2\u22efanion\u22ef(cation2)\u22ef sheets parallel to the bc plane. Within each sheet, the anions are arranged in stacks with no significant inter-anion Br\u22efBr inter\u00adactions [the shortest being > 4.3\u2005\u00c5], while the cations are in chains, with weak \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.991\u2005\u00c5] between cations inter\u00adacting with the same anion.In the title compound, (C DOI: Click here for additional data file.10.1107/S1600536812040925/pv2593Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The uncoordinating phen mol\u00adecule is approximately parallel to the 1,10-phenanthrolin-1-ium (Hphen) anion [dihedral angle = 3.3\u2005(4)\u00b0]. The centroid\u2013centroid distance of 3.801\u2005(5)\u2005\u00c5 between pyridine rings suggests the existence of \u03c0\u2013\u03c0 stacking. The crystal structure contains an extensive network of classical O\u2014H\u22efO and N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds. C\u2014H\u22ef\u03c0 inter\u00adactions between phen and 4-hy\u00addroxy\u00adbenzoate is also present in the crystal structure. In the crystal, the uncoordinating phen is equally disordered over two sites about an inversion center.In the title compound, C DOI: 10.1107/S1600536810051767/xu5103Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the benzimidazole and benzene rings is 9.57\u2005(1)\u00b0. In the crystal, mol\u00adecules are linked by weak N\u2014H\u22efCl hydrogen bonds into layers parallel to the bc plane. \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances in the range 3.4452\u2005(8)\u20133.8074\u2005(8)\u2005\u00c5 are also observed.In the title benzimidazole mononuclear complex, [ZnCl DOI: 10.1107/S1600536811026572/rz2622Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII ion is coordinated in a distorted square-planar geometry by the tetra\u00addentate ligand. The dihedral angle between the two symmetry-related benzene rings is 47.12\u2005(8)\u00b0. In the crystal, pairs of symmetry-related O\u2014H\u22efO hydrogen bonds form R               2               2(6) ring motifs. In addition, there are weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds, and \u03c0\u2013\u03c0 stacking inter\u00adactions with a centroid\u2013centroid distance of 3.4760\u2005(8)\u2005\u00c5.In the title compound, [Ni(C DOI: 10.1107/S1600536811054262/lh5396Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The L\u2212 ligands link the CdII atoms into a plane parallel to (100), with one ligand being tridentate, coordinating via the N atom and chelating a second Cd atom, and the other being bidentate, bridging two Cd atoms via the N and one O atom.. This two-dimensional network extends into a double-layer network by \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.680\u2005(2) and 3.752\u2005(2)\u2005\u00c5. Another type of \u03c0\u2013\u03c0 inter\u00adaction between pyridine rings [centroid\u2013centroid distance = 3.527\u2005(2)\u2005\u00c5] leads to a three-dimensional supra\u00admolecular architecture.In the title compound, [Cd(C DOI: 10.1107/S1600536812001031/vn2029Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, [Cd(C5H10NS2)2(C10H8N2)], exists in an N2S4 donor set defined by two chelating dithio\u00adcarbamate anions as well as a 2,2\u2032-bipyridine ligand. The coordination geometry approximates a trigonal prism. The crystal packing features weak C\u2014H\u22efS inter\u00adactions, leading to linear supra\u00admolecular chains along the a axis. The primary connections between these are by \u03c0\u2013\u03c0 stacking inter\u00adactions [ring centroid distance between centrosymmetrically related pyridyl rings = 3.7455\u2005(10)\u2005\u00c5]. Overall, the crystal structure may be described as comprising double layers of mol\u00adecules that stack along the b axis.The Cd DOI: 10.1107/S1600536811012414/hb5834Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The calcium ion is six-coordinated and is bonded to all phen\u00adoxy O atoms from both zwitterionic saltren mol\u00adecules. There are strong intra\u00admolecular N\u2014H\u22efO hydrogen bonds. The cations are linked into chains via weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.306\u2005(3) and 3.415\u2005(3)\u2005\u00c5].The title complex, [Ca(C DOI: 10.1107/S1600536810053961/pv2371Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An intra\u00admolecular O\u2014H\u22efO hydrogen bond occurs. In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 inter\u00adactions between the imidazole and benzene rings [centroid\u2013centroid distance = 3.9031\u2005(17)\u2005\u00c5] consolidate the crystal packing.In the title compound, [Co(C DOI: 10.1107/S1600536811029059/hy2449Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each PtII ion is four-coordinated in an essentially square-planar environment by four pyridine N atoms derived from the two chelating di-2-pyridyl\u00adamine (dpa) ligands, and the PtN4 unit is exactly planar. The chelate ring formed by the dpa ligand displays a boat conformation, with dihedral angles between the pyridine rings of 35.9\u2005(2) and 41.0\u2005(2)\u00b0. The complex cations, Br\u2212 anions and solvent water mol\u00adecules are linked by O\u2014H\u22efBr, N\u2014H\u22efBr, C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds, forming a three-dimensional network.The asymmetric unit of the title compound, [Pt(C II and PtII complexes, see: \u017divkovi\u0107 et al. 2]Br2\u00b7H2O = 0.029wR(F2) = 0.069S = 1.054109 reflections274 parametersH-atom parameters constrainedmax = 1.43 e \u00c5\u22123\u0394\u03c1min = \u22121.21 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CdII ion is coordinated in a disorted square-pyramidal CdBr2N2S environment with one of the Br atoms in the apical site. In the crystal structure, the benzimidazole ring systems are involved in weak inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.606\u2005(2) and 3.753\u2005(2)\u2005\u00c5]. Further stabilization is provided by weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The methyl H atoms of the dimethyl\u00adformamide solvent mol\u00adecule are disordered about a mirror plane.In the title compound, [CdBr DOI: 10.1107/S1600536810028448/lh5084Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title compound, [Zn(C2H3O2)2(C14H13N3)], is coordinated by an N2O3 donor set defined by the quinolinyl- and pyrazolyl-N atoms of the chelating heterocyclic ligand, and three carboxyl\u00adate-O atoms derived from the monodentate and bidentate carboxyl\u00adate ligands. Distortions from the ideal square-pyramidal coordination geometry relate to the restricted bite angle of the chelating ligands, i.e. O\u2014Zn\u2014O = 59.65\u2005(5) and N\u2014Zn\u2014N = 76.50\u2005(6)\u00b0, and the close approach of the non-coordinating carbonyl atom [Zn\u22efO = 2.858\u2005(2)\u2005\u00c5]. In the crystal, mol\u00adecules are consolidated into a three-dimensional architecture by C\u2014H\u22efO inter\u00adactionsThe Zn DOI: 10.1107/S1600536812025664/hb6839Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Both Na atoms exhibit a distorted octa\u00adhedral coordination geometry and are coordinated by five water O atoms and the terminal O atom from a 7-hy\u00addroxy\u00adcoumarin ligand. Four of the water mol\u00adecules are bridging, whereas the fifth is terminal. Na\u2014O bond distances are in the range 2.288\u2005(2)\u20132.539\u2005(2)\u2005\u00c5. In the chains, extending parallel to [100], adjacent Na atoms are separated by 3.60613\u2005(7)\u2005\u00c5. The uncoordinated water mol\u00adecules and 7-hy\u00addroxy\u00adcoumarin phenolate anions are located between the chains and are hydrogen bonded to the chains.The asymmetric unit of the title compound, {[Na(C HOC), see: Toyama et al. (H2O)3](C9H5O3)\u00b7H2O = 0.056                           wR(F                           2) = 0.153                           S = 1.13                           7251 reflections573 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.32 e \u00c5\u22123                        \u0394\u03c1min = \u22120.31 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL (Sheldrick, 2008SHELXTL.Data collection: 10.1107/S160053681002341X/rk2209sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002341X/rk2209Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Fe\u2014N bond length is 1.924\u2005(3)\u2005\u00c5 and the Fe\u2014Cp* centroid distance is 1.722\u2005\u00c5.In the structure of the title compound, [Fe{\u03b7 DOI: 10.1107/S1600536811021350/hg5040Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The hy\u00addroxy group of the hy\u00addroxy\u00adacetate ligand links with the counter NO3               \u2212 anion via a pair of bifurcated O\u2014H\u22efO hydrogen bonds. The centroid\u2013centroid distance of 3.5676\u2005(14)\u2005\u00c5 between benzene rings of parallel phen ligands of adjacent mol\u00adecules suggests the existence of \u03c0\u2013\u03c0 stacking. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonding is also present in the crystal structure.In the title compound, [Cu(C DOI: 10.1107/S1600536811013110/xu5175Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atom is located on a twofold rotation axis and is bonded to four N atoms at distances of 2.037\u2005(8) and 2.109\u2005(9)\u2005\u00c5, and to two S atoms at a distance of 2.406\u2005(3)\u2005\u00c5, leading to a distorted octa\u00adhedral coordination. The angle between the mean planes of the coordinating moieties of the two symmetry-related tridentate ligands is 83.3\u2005(2)\u00b0. In the crystal, complex mol\u00adecules are linked by weak C\u2014H\u22efS hydrogen bonds, \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.775\u2005(9)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions. The hydrogen-bonding inter\u00adactions lead to the formation of layers parallel to (010); \u03c0\u2013\u03c0 inter\u00adactions link these layers into a three-dimensional network.The title compound, [Ni(C DOI: Click here for additional data file.10.1107/S1600536813013032/wm2742Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813013032/wm2742Isup3.molSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The pyridyl N atom of the pydc2\u2212 anion and one pyridyl N atom of bpy occupy the axial positions. O\u2014H\u22efO hydrogen bonds involving the ethanol solvent mol\u00adecule as donor and a carboxyl\u00adate O atom as acceptor atoms, as well as C\u2014H\u22efO hydrogen bonds, together with \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent aromatic rings (average centroid\u2013centroid distance = 3.577\u2005\u00c5), seem to be effective in the stabilization of the crystal packing, resulting in the formation of a three-dimensional structure.In the title compound, [V(C O(C10H8N2)]\u00b7C2H6O = 0.058                           wR(F                           2) = 0.144                           S = 1.03                           2959 reflections263 parameters18 restraintsH-atom parameters constrainedmax = 0.40 e \u00c5\u22123                        \u0394\u03c1min = \u22120.47 e \u00c5\u22123                        \u0394\u03c1                                 X-AREA  used to solve structure: SHELXTL (Sheldrick, 2008SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009Data collection: 10.1107/S1600536811002376/wm2448sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002376/wm2448Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The quaternary C atoms of the complexed arene ring are located at the longest distance from the Fe atom, with Fe\u2014C distances of 2.112\u2005(4) and 2.105\u2005(3)\u2005\u00c5, which are slightly longer than the average Fe\u2014C distance for this ring (2.083\u2005\u00c5). The Fe ion is located 1.660\u2005(1) and 1.543\u2005(1)\u2005\u00c5, respectively, from the cyclo\u00adpenta\u00addienyl and the complexed arene ring.At 296\u2005(2)\u2005K, both complexed rings in the iron(II) complex cation of the title salt, [Fe(C DOI: 10.1107/S1600536810033179/si2288Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2-phenyl\u00adpyridine ligands are not planar, the dihedral angles between the pyridine and benzene rings being 50.1\u2005(2) and 45.7\u2005(2)\u00b0. An inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction between the six-membered rings is present, the ring centroid\u2013centroid distance being 3.898\u2005(4)\u2005\u00c5.In the title complex, [PdI DOI: 10.1107/S1600536811055425/is5038Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The central CuII atom exhibits a distorted square-planar coordination geometry, defined by two O atoms, one N atom from the ligand and one pyridine N atom with Cu\u2014N distances of 1.874\u2005(4) and 1.963\u2005(4)\u2005\u00c5, while the Cu\u2014O distances are 1.857\u2005(3) and 1.890\u2005(3)\u2005\u00c5. An intra\u00admolecular O\u2014H\u22efN inter\u00adaction occurs.The mononuclear title complex, [Cu(C DOI: 10.1107/S1600536810047719/bx2325Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom shows a distorted square-planar geometry. The dihedral angle between the two aromatic rings is 48.16\u2005(13)\u00b0. The crystal structure is stabilized by inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances in the range 3.485\u2005(2)\u20133.845\u2005(3)\u2005\u00c5.The asymmetric unit of the title compound, [Cu(C DOI: 10.1107/S1600536810053183/jh2247Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Of the two independent dimethyl\u00adformamide mol\u00adecules, one is hydrogen bonded to a single \u2013COOH group, while one links two adjacent \u2013COOH groups via a strong accepted O\u2014H\u22efO and a weak donated C(O)\u2014H\u22efO hydrogen bond. Two of these last mol\u00adecules and the two \u2013COOH groups form a centrosymmetric hydrogen-bonded ring in which the CH=O and the \u2013COOH groups by disorder adopt two alternate orientations in a 0.44:0.56 ratio. These hydrogen bonds link the CuII complex mol\u00adecules and the dimethyl\u00adformamide solvent mol\u00adecules into infinite chains along [-111]. Slipped \u03c0\u2013\u03c0 stacking inter\u00adactions between two centrosymmetric pyridine rings (centroid\u2013centroid distance = 3.63\u2005\u00c5) contribute to the coherence of the structure along [0-11].In the title compound, [Cu DOI: Click here for additional data file.10.1107/S1600536812051422/qk2049Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Four water O atoms in the equatorial plane around the NiII ion [Ni\u2014O = 2.052\u2005(2) and 2.079\u2005(2)\u2005\u00c5] form a slightly distorted square-planar arrangement, which is completed up to a distorted octa\u00adhedron by the two N atoms [Ni\u2014N = 2.075\u2005(3)\u2005\u00c5] from two isonicotinamide ligands. In the anion, the carboxyl\u00adate group is twisted from the attached benzene ring by 8.8\u2005(3)\u00b0. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, consolidates the crystal packing, which also exhibits \u03c0\u2013\u03c0 inter\u00adactions between the benzene and pyridine rings, with centroid\u2013centroid distances of 3.455\u2005(2) and 3.621\u2005(2)\u2005\u00c5, respectively.The asymmetric unit of the title compound, [Ni(C DOI: 10.1107/S1600536812002218/cv5237Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Neighbouring units inter\u00adact through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.380\u2005(3) and 3.283\u2005(4)\u2005\u00c5]. Finally, three types of O\u2014H\u22efO hydrogen bonds exist between coordinated dissociative water mol\u00adecules and hybridization water mol\u00adecules and carboxyl\u00adate O atoms, resulting in a two-dimensional network parallel to (010).In the title compound, [Cd(C DOI: 10.1107/S1600536810045551/nk2061Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination environments around the MoVI atoms are distorted octa\u00adhedral, defined by two oxide ligands and an N2O2 donor set of the tetra\u00addentate Schiff base in each mol\u00adecule. The dihedral angles between the benzene rings in the mol\u00adecules are 76.2\u2005(3) and 77.7\u2005(3)\u00b0. An inter\u00adesting feature of the crystal structure is the presence of Br\u22efBr contacts , which are shorter than the sum of the van der Waals radius of Br atoms (3.70\u2005\u00c5). The crystal structure is further stabilized by inter\u00admolcular C\u2014H\u22efBr and C\u2014H\u22ef\u03c0 inter\u00adactions. The crystal under investigation was twinned by nonmerohedry in a 0.053\u2005(1):0.947\u2005(1) ratio.The asymmetric unit of the title compound, [Mo(C O2] = 0.048wR(F2) = 0.101S = 1.0111292 reflections546 parametersH-atom parameters constrainedmax = 1.28 e \u00c5\u22123\u0394\u03c1min = \u22121.11 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXTL  global, I. DOI: 10.1107/S1600536812039785/wm2668Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The inter\u00adnal cohesion of the mol\u00adecule is enhanced by an intra\u00admolecular O\u2014H\u22efO hydrogen bond. Inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 contacts [centroid\u2013centroid distance = 3.6549\u2005(2)\u2005\u00c5] define two-dimensional networks parallel to (001), which are further connected by weaker C\u2014H\u22efO inter\u00adactions into a weakly connected three-dimensional supra\u00admolecular framework.In the centrosymmetric title compound, [Cd(C DOI: 10.1107/S1600536812033739/bg2473Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings of the pydc ligands [centroid\u2013centroid distance = 3.4714\u2005(14)\u2005\u00c5] are present. C=O\u22ef\u03c0 inter\u00adactions between the carbonyl groups and pyridine rings [O\u22efcentroid distances = 3.150\u2005(2) and 3.2233\u2005(19)\u2005\u00c5] are also observed.In the title compound, (C DOI: 10.1107/S1600536811024378/hy2413Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.5469\u2005(16)\u2005\u00c5] between the pyridyl and benzene rings. The shortest Ag\u22efAg distance is 3.2574\u2005(5)\u2005\u00c5.In the title compound, [Ag(C DOI: 10.1107/S1600536810025511/zl2286Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "They are inclined to one another at an angle of 1.95\u2005(2)\u00b0 and lie 3.309\u2005(2)\u00c5 away from each other. The ethyl\u00adidene\u00adthio\u00adcarbonohydrazide fragment is planar, with an r.m.s. deviation of 0.0347\u2005(2)\u2005\u00c5 from the mean plane of its eight non-H atoms, and makes dihedral angles of 21.78\u2005(1) and 19.97\u2005(1)\u00b0 with respect to the two Cp rings. The mol\u00adecule adopts a trans geometry about the C=N double bond. In the crystal, N\u2014H\u22ef(N/S) and C\u2014H\u22efS inter\u00adactions stack the mol\u00adecules in an inverse fashion along the b axis.In the title compound, [Fe(C DOI: Click here for additional data file.10.1107/S1600536812044078/sj5273Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In each mol\u00adecule, the SnIV atom is coordinated by O, N and S atoms from a \u00adthio\u00adsemicarbazonato ligand and two C atoms from phenyl rings in a distorted trigonal\u2013bipyramidal geometry. Weak inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efS hydrogen bonds link four mol\u00adecules into a centrosymmetric tetra\u00admer. The crystal packing exhibits short inter\u00admolecular S\u22efS contacts of 3.335\u2005(3)\u2005\u00c5.The asymmetric unit of the title compound, [Sn(C DOI: 10.1107/S1600536810054024/cv5008Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu atoms are bridged by two O atoms of the monodentate phenyl\u00adacetate groups [Cu\u2014O = 1.9808\u2005(14) and 2.3668\u2005(14)\u2005\u00c5]. The longer of the two bridging Cu\u2014O bonds takes the apical position of the distorted square-pyramidal environment of the Cu atom, which is completed by two N atoms of the chelate 2,2\u2032-bipyridine ligand [Cu\u2014N = 2.0107\u2005(17) and 2.0234\u2005(16)\u2005\u00c5]. The mol\u00adecules are assembled into stacks along [100] through \u03c0\u2013\u03c0 inter\u00adactions with inter\u00adplanar distances of 3.630\u2005(4) and 3.407\u2005(3)\u2005\u00c5; the resulting stacks are further connected into a three-dimensional supra\u00admolecular architecture by O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions.The mol\u00adecule of the binuclear title complex, [Cu DOI: 10.1107/S1600536811035483/ya2144Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu(4-methyl\u00adpyridine)4 units are, in turn, connected with each other via bridging sulfate anions, leading to the formation of infinite [Cu{H3C(C5H4N)}4SO4]n zigzag chains along [001]. The completed coordination spheres of the Cu2+ ions are slightly distorted octa\u00adhedral. The axial Cu\u2014O bonds are elongated [average length = 2.42\u2005(4)\u2005\u00c5] compared to the equatorial Cu\u2014N bonds [average length = 2.043\u2005(2)\u2005\u00c5]. The inter\u00adstitial space between the chains is filled with uncoordinated water mol\u00adecules that consolidate the structure through O\u2014H\u22efO hydrogen bonding. One of the five crystallographically independent solvent water mol\u00adecules is partially occupied with an occupancy factor of 0.396\u2005(4). Due to hydrogen bonding between symmetry-equivalent water mol\u00adecules across inversion centers, several of the water H atoms are disordered in 1:1 ratios over mutually exclusive positions. The crystal under investigation was found to be non-merohedrally twinned in a 0.789\u2005(1):0.211\u2005(1) ratio by a 180\u00b0 rotation around the reciprocal b axis.The structure of the title compound, {[Cu(SO DOI: 10.1107/S1600536811006325/wm2458Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cd\u2014S and Cd\u2014O bond lengths around the Cd atoms in the bis\u00ad(thio\u00adurea) cations are in the ranges 2.580\u2005(4)\u20132.599\u2005(4) and 2.323\u2005(8)\u20132.421\u2005(9)\u2005\u00c5, respectively, and the S atoms are in a cis orientation. In the tris\u00ad(thio\u00adurea) cations, the corresponding bond lengths around the Cd atoms are slightly longer and are in the ranges 2.559\u2005(4)\u20132.706\u2005(3) and 2.303\u2005(7)\u20132.480\u2005(10)\u2005\u00c5, respectively, and the S atoms are in a fac disposition. The crystal structure features numerous N\u2014H\u22efO, N\u2014H\u22efN, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds. Two O atoms of a sulfate anion were found to be disordered over two orientations in a 0.620\u2005(9):0.380\u2005(9) ratio. The crystal studied was a racemic twin with BASF = 0.17\u2005(5)The title compound, [Cd(CH DOI: 10.1107/S1600536812026682/hb6807Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The [ZnCl4]2\u2212 anions have a distorted tetra\u00adhedral geometry. Weak inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions exist between neighbouring aromatic rings of the cations with a centroid\u2013centroid distance of 3.712\u2005(7)\u2005\u00c5.The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536811005691/cv5049Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ni\u2014O bond lengths range from 2.004\u2005(2) to 2.106\u2005(2)\u2005\u00c5, while the Ni\u2014N bond lengths are 2.038\u2005(2) and 2.0465\u2005(19)\u2005\u00c5. The cis bond angles range from 78.64\u2005(8) to 97.30\u2005(8)\u00b0, with the former being due to the small bite of the amino\u00adalcohol ligand, while the trans bond angles range from 167.86\u2005(8) to 171.23\u2005(8)\u00b0. One of the alcohol H atoms forms a hydrogen bond with the dimethyl\u00adformamide (DMF) solvent mol\u00adecule, while the other links mol\u00adecules into chains along the b axis through inter\u00admolecular O\u2014H\u22efO hydrogen bonds. There are bifurcated C\u2014H\u22efO inter\u00adactions involving one of the nitro groups between parallel stacks of mol\u00adecules in the b-axis direction.In the title compound, [Ni(C DOI: 10.1107/S1600536811031229/jj2096Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "O\u2014H\u22efO hydrogen bonds connect adjacent complex mol\u00adecules into dimers. C\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings [centroid\u2013centroid distances = 3.700\u2005(2) and 3.845\u2005(2)\u2005\u00c5] are also present.In the title complex, [Co(C DOI: 10.1107/S1600536811029461/hy2451Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The RuII atom has a distorted octa\u00adhedral geometry due to the restricted bite angle [157.7\u2005(3)\u00b0] of the two mer-arranged N,N\u2032,N\u2032\u2032-tridendate ligands, viz. 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine (tpy) and 4\u2032-ethynyl-2,2\u2032:6\u2032,2\u2032\u2032-terpyridine (tpy\u2032), which are essentially perpendicular to each other, with a dihedral angle of 87.75\u2005(12)\u00b0 between their terpyridyl planes. The rod-like acetyl\u00adene group lies in the same plane as its adjacent terpyridyl moiety, with a maximum deviation of only 0.071\u2005(11)\u2005\u00c5 from coplanarity with the pyridine rings. The mean Ru\u2014N bond length involving the outer N atoms trans to each other is 2.069\u2005(6)\u2005\u00c5 at tpy and 2.070\u2005(6)\u2005\u00c5 at tpy\u2032. The Ru\u2014N bond length involving the central N atom is 1.964\u2005(6)\u2005\u00c5 at tpy and 1.967\u2005(6)\u2005\u00c5 at tpy\u2032. Two of the three counter anions were refined as half-occupied.The title heteroleptic  II\u2013terpyridine complex containing the {Ru(tpy\u2013C\u00a0C)} fragment, see: Ruben et al. (C17H11N3)](PF6)2\u00b72C2H3N = 0.084wR(F2) = 0.228S = 1.257496 reflections596 parametersH-atom parameters constrainedmax = 1.75 e \u00c5\u22123\u0394\u03c1min = \u22120.94 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812051227/sj5287Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The compound exhibits a three-dimensional supra\u00admolecular structure composed of the complex mol\u00adecules and lattice water mol\u00adecules, which are linked together by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and partly overlapping \u03c0\u2013\u03c0 inter\u00adactions between the pyridine and benzene rings [centroid\u2013centroid distances = 3.922\u2005(2) and 3.921\u2005(2)\u2005\u00c5]. One of the lattice water mol\u00adecules is disordered over two positions in an occupancy ratio of 0.521\u2005(6):0.479\u2005(6).In the title compound, [Ni(C DOI: 10.1107/S1600536811032090/hy2454Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the pyridine rings is 6.3\u2005(2)\u00b0. The N\u2014C\u2014C\u2014N torsion angle is 177.5\u2005(2)\u00b0. In the dianion, the CrVI ions are in a slightly distorted tetra\u00adhedral coordination environment and the bond angles at the independent CrVI ions are in the ranges 105.93\u2005(10)\u2013110.60\u2005(11) and 107.35\u2005(11)\u2013111.07\u2005(12)\u00b0. The Cr\u2014O\u2014Cr angle is 127.96\u2005(12)\u00b0. The crystal used was an inversion twin with refined components of 0.510\u2005(19) and 0.490\u2005(19).In the cation of the title salt, (C DOI: 10.1107/S1600536812005430/lh5410Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atom is five-coordinated in a distorted square-pyramidal environment by two phenolate O atoms and two imine N atoms of the tetra\u00addentate Schiff base anion in the basal plane and one water mol\u00adecule in the apical position. Because of symmetry, the pyridine N atom and the corresponding C atom at the 4-position of the pyridine ring are disordered. The crystal packing can be described as being composed of alternating layers stacked along [001]. Intra\u00admolecular C\u2014H\u22efN and inter\u00admolecular C\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding inter\u00adactions, as well as C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid distance = 3.799\u2005(8)\u2005\u00c5 and inter\u00adplanar distance = 3.469\u2005(2)\u2005\u00c5] are observed.Mol\u00adecules of the title compound, [Cu(C DOI: 10.1107/S1600536812031273/wm2656Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two pyridine rings coordinating to the AgI atom are almost perpendicular to each other [dihedral angle = 87.73\u2005(10)\u00b0]. Inter\u00admolecular Ag\u22efO inter\u00adactions [3.149\u2005(3) and 2.686\u2005(3)\u2005\u00c5], N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions between the cyclic dimers and the anions or the solvent mol\u00adecules lead to the formation of a three-dimensional supra\u00admolecular network.In the binuclear title compound, [Ag I coordination polymers with symmetrical dipyridyl ligands, see: Lee et al. 2](ClO4)2\u00b72C2H6OS = 0.033wR(F2) = 0.086S = 1.023367 reflections217 parametersH-atom parameters constrainedmax = 0.61 e \u00c5\u22123\u0394\u03c1min = \u22120.65 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026585/sj5353Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the anion, the two pyridine rings are inclined to one another by 87.75\u2005(13)\u00b0. Two types of robust O\u2014H\u22efO hydrogen bond synthons, viz. R               2               2(16) and R               6               6(42), link the anions to form a two-dimensional network parallel to the bc plane. Furthermore, O\u2014H\u22efO, N\u2014H\u22efO, N\u2014H\u22efN and weak C\u2014H\u22efO hydrogen bonds connect the two dimensional networks, forming a three-dimensional structure. In the crystal, there are also C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances of 3.5554\u2005(18) and 3.7681\u2005(18)\u2005\u00c5], and C=O\u22ef\u03c0 inter\u00adactions [O\u22efcentroid distance = 3.117\u2005(2)\u2005\u00c5] present. One of the three crystal water molecules shows an occupancy of 0.35.In the title compound, (C DOI: 10.1107/S1600536811052445/lh5386Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII ion is six coordinate, with distorted octa\u00adhedral geometry, ligated by two N atoms and two O atoms from a 2,2\u2032-bis\u00ad(5-carboxy-1H-imidazole-4-carboxyl\u00adate) dianion, one N atom from a pyridine mol\u00adecule and one coordinating water mol\u00adecule. The Co\u2014O bond lengths range from 2.076\u2005(2) to 2.1441\u2005(15)\u2005\u00c5, while the Co\u2014N bond lengths are 2.138\u2005(3) and 2.1515\u2005(17)\u2005\u00c5. A two-dimensional network of N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds stabilizes the crystal packing. There are \u03c0\u2013\u03c0 inter\u00adactions between the bipyridine and imidazole rings [centroid\u2013centroid distance = 3.7694\u2005(4)\u2005\u00c5]. The propane-1,3-diyl group is disordered over two conformations, with refined occupancies of 0.755\u2005(8) and 0.245\u2005(8).In the title compound, [Co(C DOI: 10.1107/S1600536812029856/pk2422Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CoII ion is situated on an inversion centre and is coordinated by two O and two N atoms of two symmetry-related 1,4-pyrazine-2,3-dicarboxyl\u00adate ligands and two water mol\u00adecules and has a disorted octa\u00adhedral coordination environment. The asymmetric unit also contains four water mol\u00adecules. In the crystal, extensive inter\u00admolecular classical N\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.490\u2005(1)\u2005\u00c5] connect the various components, forming a three-dimensional network.The title compound, (C DOI: 10.1107/S1600536811001127/bt5444Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Fe atom is slightly closer to the substituted cyclo\u00adpenta\u00addienyl ring, with an Fe\u22efcentroid distance of 1.639\u2005(2)\u2005\u00c5, compared with 1.645\u2005(2)\u2005\u00c5 for the unsubstituted ring. The C=N double bond is essentially coplanar with the substituted cyclo\u00adpenta\u00addienyl ring with a deviation of 10.3\u2005(1)\u00b0. The angle formed by the C=N double bond and the naphthal\u00adene ring system is 47.1\u2005(1)\u00b0. The C\u2014N=C\u2014C torsion angle is 177.32\u2005(5)\u00b0.In the title mol\u00adecule, [Fe(C DOI: 10.1107/S1600536808026330/lh2673Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title compound, [ZnCl2(C14H13N3)], is coordinated by a Cl2N2 donor set defined by quinoline and pyrazole N atoms of the chelating ligand and two Cl atoms. Distortions from the ideal tetra\u00adhedral geometry relate to the restricted bite angle of the chelating ligand [N\u2014Zn\u2014N = 78.54\u2005(12)\u00b0]. In the crystal, mol\u00adecules are connected into a three-dimensional structure by C\u2014H\u22efCl inter\u00adactions, involving both Cl atoms, and \u03c0\u2013\u03c0 inter\u00adactions that occur between the pyrazole ring and each of the pyridine and benzene rings of the quinoline residue [inter\u00adcentroid distances = 3.655\u2005(2) and 3.676\u2005(2)\u2005\u00c5].The Zn DOI: 10.1107/S1600536812014390/hg5206Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angles between the imidazole and triazole rings in the cations are 44.7\u2005(3) and 89.4\u2005(3)\u00b0. The BiIII ion is coordinated by six chloride ligands in a slightly distorted octa\u00adhedral geometry. In each cation, an intra\u00admolecular N\u2014H\u22efS hydrogen bond is observed. In the crystal, N\u2014H\u22efCl, N\u2014H\u22efS, N\u2014H\u22efO, O\u2014H\u22efCl, O\u2014H\u22efS and O\u2014H\u22efO hydrogen bonds connect the components into a three-dimensional network. In addtion, \u03c0\u2013\u03c0 stacking inter\u00adactions between inversion-related triazole rings are observed, with a centroid\u2013centroid distance of 3.322\u2005(3)\u2005\u00c5The asymmetric unit of the title hydrated salt, (C DOI: 10.1107/S1600536813016449/lh5614Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the mean planes of the coordination rings is 9.15\u2005(12)\u00b0 while the dihedral angle between the mean planes of the two aromatic rings is 3.48\u2005(16)\u00b0. In the crystal, pairs of inter\u00admolecular C\u2014H\u22efO hydrogen bonds link neighboring mol\u00adecules into a chain along the a axis. The crystal structure is further stabilized by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.883\u2005(2)\u2005\u00c5].In the title compound, [Ni(C DOI: 10.1107/S1600536811022732/kj2181Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each mol\u00adecule, the metal atom is coordinated by an N,N\u2032,N\u2032\u2032-tridenate Schiff base and two Cl atoms in a distorted square-pyramidal geometry. The two mol\u00adecules differ little in their geometry, but more in their inter\u00admolecular inter\u00adactions. In the crystal, adjacent mol\u00adecules are connected via C\u2014H\u22efCl inter\u00adactions into a three-dimensional supra\u00admolecular structure. The network is supplemented by \u03c0\u2013\u03c0 inter\u00adactions formed between the aromatic rings of pairs of the symmetry-related mol\u00adecules [centroid\u2013centroid distances = 3.6255\u2005(10) and 3.7073\u2005(10)\u2005\u00c5]. The crystal lattice contains void spaces with a size of 52\u2005\u00c53.The asymmetric unit of the title compound, [ZnCl For the al. 1999; Sun ] = 0.021                           wR(F                           2) = 0.052                           S = 1.04                           6294 reflections313 parametersH-atom parameters constrainedmax = 0.36 e \u00c5\u22123                        \u0394\u03c1min = \u22120.28 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811025669/om2444Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu\u2014O distances involving the four O atoms in the square plane are in the range 1.9501\u2005(11)\u20131.9677\u2005(11)\u2005\u00c5, with the Cu atom lying nearly in the plane [deviation = 0.0726\u2005(2)\u2005\u00c5]. The axial O atom occupies the peak position with a Cu\u2014O distance of 2.885\u2005(12)\u2005\u00c5, which is significantly longer than the rest of the Cu\u2014O distances. Each 1,8-nap ligand acts as bridge, linking two CuII atoms into a dinuclear structure. Inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions consolidate the structure.In the centrosymmetric dinuclear title complex, [Cu DOI: 10.1107/S1600536810028497/pv2300Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both macrocycles exhibit a planar conformation with average deviation from the least-squares-plane of the 24 macrocycle atoms of \u039424 = 0.043\u2005\u00c5 for the first mol\u00adecule and 0.026\u2005\u00c5 for the mol\u00adecule located on an inversion center. The average Ni\u2014N bond lengths are 1.955\u2005(2) and 1.956\u2005(2)\u2005\u00c5 in the two mol\u00adecules. The mol\u00adecules form \u03c0\u2013\u03c0 dimers of inter\u00admediary strength with a mean plane separation of 3.36\u2005(2)\u2005\u00c5.The title compound, [Ni(C DOI: 10.1107/S1600536812035726/rn2107Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The MnII ion and two coordinated water mol\u00adecules lie on a twofold rotation axis. The water mol\u00adecules are involved in O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds with the triazole N atoms and carboxyl\u00adate O atoms, yielding a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings [centroid\u2013centroid distance = 3.836\u2005(9)\u2005\u00c5] are observed.In the title compound, [Mn(C DOI: 10.1107/S1600536811025335/hy2445Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distance = 3.5419\u2005(19)\u2005\u00c5] result in the formation of a supra\u00admolecular structure.In the anion of the title compound, (C DOI: 10.1107/S160053681202853X/hy2560Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "For example, the torsion angles N\u2014C\u2014C\u2014C involving the N-benzyl moieties are 57.3\u2005(7) and 11.6\u2005(8)\u00b0 in one mol\u00adecule and 76.5\u2005(7) and 97.4\u2005(7)\u00b0 in the other. In each mol\u00adecule, the P atom exhibits a distorted tetra\u00adhedral conformation [the bond angles at P are in the ranges 104.7\u2005(2)\u2013115.2\u2005(2) and 105.1\u2005(2)\u2013115.1\u2005(2)\u00b0 in the two molecules], and the phosphoryl group and the N\u2014H group adopt an anti orientation with respect to one another. In the crystal, mol\u00adecules are linked via N\u2014H\u22efO(P) hydrogen bonds, forming a chain parallel to the a axis.The asymmetric unit of the title compound, C DOI: 10.1107/S1600536811046046/nc2247Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the aromatic rings of pyridine-2,5-dicarb\u00adoxy\u00adlate with centroid\u2013centroid distances of 3.6166\u2005(13)\u2005\u00c5.In the polymeric title compound, [Ca(C DOI: 10.1107/S1600536810054334/bt5441Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The porphyrin N atoms occupy the equatorial positions while the axial positions are occupied by the O atoms of the methane\u00adsulfonate anions. The phenyl rings make dihedral angles of 77.02\u2005(13) and 87.89\u2005(14)\u00b0 with the porphyrin ring. Of the three solvent chloro\u00adform mol\u00adecules, one is disordered over a twofold rotation axis. In the crystal a three-dimensional assembly is accomplished via C\u2014H\u22efO hydrogen bonds between the H atoms of the phenyl groups in the porphyrin ring and the O atoms of the methane\u00adsulfonate ligands.In the crystal structure of the title compound, [Sn(C For the al. 2004, 2009 \u25b6.44H28N4)(CH3O3S)2]\u00b73CHCl3 = 0.033wR(F2) = 0.088S = 1.045192 reflections331 parametersH-atom parameters constrainedmax = 0.91 e \u00c5\u22123\u0394\u03c1min = \u22120.86 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812015875/wm2606Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the phenyl ring and the metal-bound pyridine ring is 50.3\u2005(4)\u00b0 for each 2-phenyl\u00adpyridine ligand. This arranges the phenyl ring from one ligand in the complex above the pyridine ring of the other resulting in an intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction, with a centroid\u2013centroid distance of 3.6796\u2005(17)\u2005\u00c5. Weak C\u2014H\u22efCl hydrogen bonds stabilize the crystal packing, linking mol\u00adecules into chains along the c axis.In the title compound, [ZnCl DOI: 10.1107/S1600536812010616/sj5207Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "III atom of the title compound, [Ir(C11H8N)2Cl(CH3CN)], displays a distorted octa\u00adhedral coordination. The pyridyl groups are in trans positions [N\u2014Ir\u2014N = 173.07\u2005(10)\u00b0], while the phenyl groups are trans with respect to the acetonitrile and chloride groups [C\u2014Ir\u2014N = 178.13\u2005(11) and C\u2014Ir\u2014Cl = 176.22\u2005(9)\u00b0]. The pyridyl\u00adphenyl groups only show a small deviation from planarity, with the dihedral angle between the planes of the two six-membered rings in each pyridyl\u00adphenyl group being 5.6\u2005(2) and 5.8\u2005(1)\u00b0. The crystal packing shows inter\u00admolecular C\u2014H\u22efCl, C\u2014H\u22ef\u03c0(acetonitrile) and C\u2014H\u22ef\u03c0(pyridyl\u00adphen\u00adyl) contacts.The Ir DOI: 10.1107/S1600536811049373/tk5023Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Mn\u2014O distances range from 2.151\u2005(2) to 2.5093\u2005(19)\u2005\u00c5, while the Mn\u2014N distances are 2.226\u2005(2) and 2.248\u2005(2)\u2005\u00c5. Each 5-ferrocenyl\u00adbenzene-1,5-dicarboxyl\u00adate anion links to two MnII ions, resulting in a chain along the b axis. A three-dimensional network of N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds helps to stabilize the crystal packing.In the title coordination polymer, {[FeMn(C DOI: 10.1107/S1600536811022781/fj2428Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, the mol\u00adecules are linked via weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds [3.334\u2005(5)\u2005\u00c5] and there are also short inversion-related intermolecular Br\u22efBr contacts [3.4263\u2005(6)\u2005\u00c5]In the title complex, [Co(C DOI: 10.1107/S1600536810032162/zs2053Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII ion is situated on an inversion centre. The Ni\u2014N distances range from 2.0589\u2005(19) to 2.0757\u2005(19)\u2005\u00c5, intra-ligand N\u2014Ni\u2014N angles range from 84.50\u2005(8) to 85.15\u2005(8)\u00b0, and adjacent inter-ligand N\u2014Ni\u2014N angles range between 94.85\u2005(8) and 95.50\u2005(8)\u00b0. In the crystal, O\u2014H\u22efO hydrogen bonds between methanol solvent mol\u00adecules and tri\u00adfluoro\u00admethane\u00adsulfonate anions are observed.In the title salt, [Ni(C DOI: 10.1107/S1600536813024653/lh5647Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The EuIII ion is coordinated by nine O atoms from two H2bdc ligands, two sulfate anions and three water mol\u00adecules, displaying a bicapped trigonal prismatic geometry. The carboxyl\u00adate groups of the H2bdc ligands and the sulfate anions link the EuIII ions, forming a chain along [010]. These chains are further connected by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the imidazole and benzene rings  into a three-dimensional supra\u00admolecular network.In the title coordination polymer,  H-benzimidazole-5,6-dicarboxyl\u00adate complexes, see: Wang et al. 2(SO4)2(H2O)6]\u00b76H2O = 0.036                           wR(F                           2) = 0.097                           S = 1.02                           2841 reflections248 parametersH atoms treated by a mixture of independent and constrained refinementmax = 1.82 e \u00c5\u22123                        \u0394\u03c1min = \u22122.51 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The angles around the CuII atom vary between 85.32\u2005(6) and 94.68\u2005(6)\u00b0. The Cu\u2014O bond distances between the CuII atom and the O atoms vary between 1.9424\u2005(14) and 2.3229\u2005(15)\u2005\u00c5. The layers inter\u00addigitate via face-to-face aromatic inter\u00adactions [3.6490\u2005(8)\u2005\u00c5] between coumarin moieties such that the inter\u00adlayer separation is 10.460\u2005(2)\u2005\u00c5, i.e. the length of the c axis. O\u2014H\u22efO hydrogen bonds between the H atoms of coordinated water mol\u00adecules and the O atoms of carboxyl\u00adate groups link the complex mol\u00adecules into layers parallel to the ab plane.In the title compound, [Cu(C DOI: 10.1107/S1600536811018708/zk2008Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions and short inter\u00admolecular I\u22efO contacts [3.142\u2005(2)\u2005\u00c5] are observed.In the title compound, C DOI: 10.1107/S1600536810033581/nc2194Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The average Ru\u2014C distance to the penta\u00admethyl\u00adcyclo\u00adpenta\u00addienyl (Cp*) group is 2.19\u2005(3)\u2005\u00c5, and 2.21\u2005(1)\u2005\u00c5 to the ortho, meta and para C atoms of the arene ring. The Ru\u2014Cipso bond length of 2.272\u2005(3)\u2005\u00c5 is significantly longer, reflecting movement of the Ru atom away from the C atoms with electronegative substituents attached. The amide H atom in the cation forms an inter\u00admolecular N\u2014H\u22efO hydrogen bond with the carbonyl O atom of the acetone solvent mol\u00adecule. A C\u2014H\u22efO inter\u00adaction also occurs.The title complex, [Ru(C DOI: 10.1107/S1600536811031655/ng5208Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds result in a supra\u00admolecular layer parallel to (101). These layers are connected by \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings [centroid\u2013centroid distance = 3.891\u2005(2)\u2005\u00c5].In the title complex, [Cu(NO DOI: 10.1107/S160053681103529X/hy2463Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the substituted benzene rings is 29.95\u2005(16)\u00b0. In the crystal, mol\u00adecules are linked along the b axis, forming individual dimers through C\u2014H\u22efO inter\u00adactions. The crystal structure is further stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6131\u2005(17)\u2005\u00c5].In the title Schiff base complex, [Cu(C DOI: 10.1107/S160053681200195X/hp2025Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The geometry around the ZnII atoms is distorted trigonal\u2013bipyramidal, supported by the N2O2 donor atoms of the tetradentate Schiff base and a coordinating water mol\u00adecule. The dihedral angles between the benzene rings in the two mol\u00adecules are 34.10\u2005(15)\u2005\u00c5 and 30.61\u2005(15)\u2005\u00c5. In the crystal, neighbouring independent mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming dimers with R22(6) ring motifs, and by O\u2014H\u22efCl hydrogen bonds. There are short Cl\u22efCl  contacts present, and mol\u00adecules are also linked by C\u2014H\u22efO and \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.671\u2005(2)\u2005\u00c5] inter\u00adactions.The asymmetric unit of the title compound, [Zn(C DOI: 10.1107/S1600536812025986/su2451Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Two PbII atoms are bridged by the Hbtc ligands, forming a discrete centrosymmetric dinuclear complex. Inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine and imidazole rings, and between the pyridyl rings of the L ligands [centroid\u2013centroid distances = 3.600\u2005(6) and 3.732\u2005(6)\u2005\u00c5] lead to a three-dimensional supra\u00admolecular structure.In the title compound, [Pb DOI: 10.1107/S1600536810045812/hy2360Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title salt, [Cu(C10H24N4)(H2O)2][CH3(CH2)8CO2]2\u00b72H2O, is chelated by the four N atoms of the 1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane (cyclam) ligand and is coordinated by two water mol\u00adecules in a Jahn\u2013Teller-type tetra\u00adgonally distorted octa\u00adhedral geometry. The CuII atom lies on a center of inversion. The cations, anions and uncoordinated water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a layer structure parallel to (001).The Cu DOI: 10.1107/S1600536810025699/bt5286Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "I atom in the title compund, [Cu(C7H2Br3O2)(C19H17P)2], is located on a twofold rotation axis; the 3,5,7-tribromo\u00adtropolonate anion coordinates as a bidentate ligand with a bite angle of 76.42\u2005(9)\u00b0. An intra\u00admolecular C\u2014H\u22efO inter\u00adaction occurs. Within the crystal, extensive weak C\u2014H\u22ef\u03c0 inter\u00adactions contribute to the herringbone pattern observed in the packing of the mol\u00adecules.The Cu DOI: Click here for additional data file.10.1107/S1600536812042286/ng5299Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The coordination sphere about the Na atom in each complex unit comprises five bonds to O atoms of the crown ether [Na\u2014O = 2.390\u2005(7)\u20132.466\u2005(6)\u2005\u00c5] and one to a thio\u00adsulfate O atom [Na\u2014O = 2.305\u2005(4) and 2.447\u2005(3)\u2005\u00c5].In the title complex, [Na(C DOI: 10.1107/S1600536811022252/zs2116Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials: interactive version of Fig. 1            Enhanced figure:"}
{"text": "In the crystal, O\u2014H\u22efCl and N\u2014H\u22efCl hydrogen bonds link the complex mol\u00adecules into a layer parallel to (100). \u03c0\u2013\u03c0 inter\u00adactions between the thia\u00adzole rings are observed [centroid\u2013centroid distance = 3.749\u2005(3)\u2005\u00c5].In the title complex, [CuCl DOI: 10.1107/S1600536812013037/hy2524Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angles between the central benzene ring and the two outer rings are 4.79\u2005(15) and 7.54\u2005(15)\u00b0. In the crystal, mol\u00adecules are connected through inter\u00admolecular C\u2014H\u22efO hydrogen bond, resulting in chains extending along the c axis. The crystal structure is further stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances in the range 3.3760\u2005(15)\u20133.7196\u2005(17)\u2005\u00c5.In the title Schiff base complex, [Ni(C DOI: 10.1107/S1600536810051834/pv2367Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The chelate ring including the CuII atom is essentially planar, with a maximum deviation of 0.0181\u2005(17)\u2005\u00c5 for one of the coordinated N atoms. This plane forms a dihedral angle of 30.75\u2005(6)\u00b0 with the CuCl2 plane. In the crystal, each pair of adjacent mol\u00adecules is linked into a centrosymmetric dimer by N\u2014H\u22efCl hydrogen bonds. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efCl hydrogen bonds and weak slipped \u03c0\u2013\u03c0 stacking inter\u00adactions between symmetry-related mol\u00adecules, with an inter\u00adplanar separation of 3.439\u2005(19)\u2005\u00c5 and a centroid\u2013centroid distance of 3.581\u2005(19)\u2005\u00c5.In the title complex, [CuCl DOI: 10.1107/S1600536811004375/fj2386Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid distance = 3.5537\u2005(18)\u2005\u00c5].In the title complex, [Cd(NO DOI: 10.1107/S160053681002550X/tk2681Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Besides two pyridine-2,5-dicarboxyl\u00adate anions, one bidentate 2,2\u2032-bipyridine and one water mol\u00adecule coordinate to the Co cation, completing a distorted octa\u00adhedral coordination geometry. Within the dinuclear mol\u00adecule, \u03c0\u2013\u03c0 stacking occurs between parallel pyridine rings with centroid\u2013centroid distances of 3.802\u2005(2)\u2005\u00c5. The crystal structure contains extensive O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions.In the centrosymmetric title compound, [Co DOI: 10.1107/S1600536811003059/xu5145Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Zn(TPP) complex exhibits a nearly planar conformation of the porphyrin core [maximum deviation = 0.106\u2005(2)\u2005\u00c5] with an average Zn\u2014N distance of 2.047\u2005(2)\u2005\u00c5. The title compound is considered as a one-dimensional polymer along [010], in which the Zn(TPP) moiety is linked to the closest O atoms of two symmetry-related 18-crown-6 mol\u00adecules with a Zn\u2014O distance of 2.582\u2005(1)\u2005\u00c5, completing a distorted octahedral coordination environment of the metal ion. The chains are mainly sustained by weak C\u2014H\u22ef\u03c0 inter\u00adactions. An ethyl\u00adene group of the 18-crown-6 mol\u00adecule is disordered over three sites with occupancies of 0.50, 0.25 and 0.25.In the title compound, [Zn(C DOI: 10.1107/S1600536813018126/hy2633Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The N atoms are cis to each other, while the water O atoms and ligand O atoms are mutually trans. The crystal structure is stabilized by a network of O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.730\u2005(3) and 3.652\u2005(3)\u2005\u00c5] between the 5-methyl\u00adpyrazine-2-carboxyl\u00adate ligands. The structure is isotypic with the manganese analog.In the title compound, [Cd(C DOI: 10.1107/S1600536811035045/bt5630Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit is composed of six TPPI mol\u00adecules, eight TFTIB mol\u00adecules and two methanol mol\u00adecules, overall 16 constituents. The formation of the architecture is essentially guided by a number of C\u2014I\u22efI\u2212 halogen bonds (XB), whose lengths are in the range 3.276\u2005(1)\u20133.625\u2005(1)\u2005\u00c5. Layers of supra\u00admolecular polyanions are formed parallel to (10-1) wherein iodide anions function as penta-, tetra- or bidentate XB acceptors. The structure is not far from being P21/n, but the centrosymmetry is lost due to a different conformation of a single couple of cations and the small asymmetry in the formed supra\u00admolecular anion. One methanol mol\u00adecule is hydrogen bonded to an iodide anion, while the second is linked to the first one via an O\u2014H\u22efO contact. This second methanol mol\u00adecule is more loosely pinned in its position than the first and presents very high anisotropic displacement parameters and a seeming shortening of the C\u2014O bond length. The crystal studied was refined as a perfect inversion twin.The crystallization of a 1:1 molar solution of 1,3,5-tri\u00adfluoro-2,4,6-di\u00adiodo\u00adbenzene (TFTIB) and tetra\u00adphenyl\u00adphosponium iodide (TPPI) from methanol produced tetra\u00adgonal needles of pure TPPI and tabular pseudo-hexa\u00adgonal truncated bipyramids of the title compound, 3C \u00c5b = 22.001 (4) \u00c5c = 28.260 (5) \u00c5\u03b2 = 92.49 (2)\u00b0V = 10704 (3) \u00c53Z = 4K\u03b1 radiationMo \u22121\u03bc = 4.45 mmT = 90 K0.34 \u00d7 0.20 \u00d7 0.12 mmBruker SMART APEX diffractometerSADABS; Bruker, 1998)Tmin = 0.614, Tmax = 1.000Absorption correction: multi-scan (105822 measured reflections28547 independent reflectionsI > 2\u03c3(I)26385 reflections with Rint = 0.047R[F2 > 2\u03c3(F2)] = 0.040wR(F2) = 0.081S = 1.0928547 reflections2304 parameters13 restraintsH-atom parameters constrainedmax = 2.46 e \u00c5\u22123\u0394\u03c1min = \u22120.89 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SIR2002 ORTEP-3 for Windows  global, I. DOI: Click here for additional data file.10.1107/S1600536813012397/im2426Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mol\u00adecules are stabilized by C\u2014H\u22efCl hydrogen bonds. In the crystal, inter\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efS hydrogen bonds with R               2               2(8), R               4               2(8) and R               2               2(6) ring motifs generate a polymeric network.In the centrosymmetric title compound, [Co DOI: 10.1107/S1600536811013067/si2349Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are hydrogen-bonding inter\u00adactions between the secondary amine H atom and the phenolate O atom, as well as C\u2014H\u22efO inter\u00adactions, which result in the dihedral angle between the aromatic phenyl ring of the 2-formyl\u00adphenolate moiety and the pyridine ring being 80.23\u2005(4)\u00b0. In the packing, there are both C\u2014H\u22ef\u03c0 inter\u00adactions, which link the mol\u00adecules into chains along the b axis, and offset \u03c0\u2013\u03c0 inter\u00adactions involving both the pyridine and phenyl rings of the 2-BAP ligands [centroid\u2013centroid distances = 4.0100\u2005(8)\u2005\u00c5 for the pyridine rings and 3.6601\u2005(8) and 4.8561\u2005(8)\u2005\u00c5 for the phenyl rings].In the title complex, [Ni(C DOI: 10.1107/S1600536811001425/zl2338Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazole rings [centroid\u2013centroid distances = 3.5188\u2005(15) and 3.6687\u2005(15)\u2005\u00c5] further stabilize the structure.In the title compound, [Mn(C DOI: Click here for additional data file.10.1107/S1600536813004091/hy2616Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two complex cations have similar conformations with the butterfly-like Fe4S4 core surrounded by two penta\u00admethyl\u00adcyclo\u00adpenta\u00addienyl ligands and the S atoms of two dithiol\u00adate ligands. In each Fe4S4 core, there are four short Fe\u2014Fe and two long Fe\u22efFe contacts, suggesting bonding and non-bonding inter\u00adactions, respectively. The Fe\u2014S distances range from 2.1287\u2005(13) to 2.2706\u2005(16)\u2005\u00c5 for one and from 2.1233\u2005(13) to 2.2650\u2005(16)\u2005\u00c5 for the other Fe4S4 core. The Fe\u2014S distances involving the dithiol\u00adate ligands are in a more narrow range [2.1764\u2005(16)\u20132.1874\u2005(13)\u2005\u00c5 for one and 2.1743\u2005(14)\u20132.1779\u2005(16)\u2005\u00c5 for the other cation]. There are no significant inter\u00adactions between cations and anions.The asymmetric unit of the title compound, [Fe DOI: Click here for additional data file.10.1107/S1600536813007514/wm2732Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The metal atoms are bridged by 1,2-bis\u00ad[4-(pyridin-3-yl)pyrimidin-2-ylsulfan\u00adyl]ethane ligands, giving a polymeric chain extending along the b axis. Adjacent chains related by an inversion center are further bridged by Cd\u2014O bonds formed between the O atom of one of the acetate ligands and the metal atom. The five Cd\u2014O bond lengths are in the range 2.329\u2005(3)\u20132.485\u2005(3)\u2005\u00c5. There are \u03c0\u2013\u03c0 stacking inter\u00adactions between the aromatic rings of adjacent polymeric chains, the centroid\u2013centroid distances being 3.556\u2005(3) and 3.698\u2005(3)\u2005\u00c5, organizing the chains into a three-dimensional framework. This framework is additionally stabilized by extensive O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonding between water mol\u00adecules and the ligands.The title compound, {[Cd(CH DOI: 10.1107/S1600536811046794/gk2423Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII ion is displaced by 0.586\u2005\u00c5 in the direction of the chloride ligand from the atoms forming the square plane. In the crystal, the components are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds, generating chains along the b axis.In the title compound, [Zn(C Cl(C9H7NO)]\u00b7CH4O = 0.034                           wR(F                           2) = 0.082                           S = 1.05                           3806 reflections244 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.47 e \u00c5\u22123                        \u0394\u03c1min = \u22120.42 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S160053681103337X/lh5311Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dicationic complexes are arranged in a staggered configuration. The torsion angle subtended by the 1-methyl\u00adimidazole ring relative to the terpyridine ring is 114.9\u2005(5)\u00b0. Inter\u00admolecular C\u2014H\u22efO inter\u00adactions between the perchlorate anions and the H atoms of the terpy ligand are observed. Consideration of related phenyl\u00adbipyridyl complexes of platinum(II), which are monocationic, leads to the conclusion that the electrostatic repulsion between the dicationic chelates prevents the formation of Pt\u22efPt inter\u00adactions. These inter\u00adactions are a common feature associated with the monocationic species.The reaction between [Pt(terpy)Cl]\u00b72H For the al. 1996 and for  al. 2007. For stu al. 2007. For a c al. 2008. For Pt\u22ef al. 1997; Field e al. 2003; Jaganyi al. 2003.       15H11N3)(C4H6N2)](ClO4)2\u00b7CH3NO2                         = 0.045                           wR(F                           2) = 0.118                           S = 0.98                           5102 reflections354 parametersH-atom parameters constrainedmax = 1.59 e \u00c5\u22123                        \u0394\u03c1min = \u22122.64 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis CCD  I, global. DOI: 10.1107/S1600536811025475/fi2109Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The inter\u00adnal benzene rings, A and B, make dihedral angles of 86.72\u2005(5) and 79.22\u2005(5)\u00b0 with the naphthalene ring system. The two terminal benzene rings, C and D, of the 4-phen\u00adoxy\u00adbenzoyl groups are twisted with respect to benzene rings A and B, with dihedral angles of A/C = 62.72\u2005(8) and B/D\u00a0= 87.61\u2005(6)\u00b0. In the crystal, H atoms in the naphthalene system make two types of inter\u00admolecular C\u2014H\u22efO inter\u00adactions with the carbonyl O atom and the phenyl etheral O atom of neighbouring mol\u00adecules. Mol\u00adecules are further linked by C\u2014H\u22ef\u03c0 inter\u00adactions involving a H atom of terminal benzene ring D and the \u03c0-system of the inter\u00adnal benzene ring A, forming dimers centered about an inversion center.In the title mol\u00adecule {systematic name: (4-phenoxyphenyl)methan\u00adone}, C DOI: 10.1107/S1600536810042170/su2217Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometry around the NiII atom in each mol\u00adecule is distorted square planar. The dihedral angles between the two phen\u00adoxy rings in each mol\u00adecule are 17.8\u2005(4) and 36.5\u2005(4)\u00b0. The crystal packing is stabilized by weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.758\u2005(5)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions.The asymmetric unit of the title complex, [Ni(C DOI: 10.1107/S1600536811029813/su2297Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the cation, the average Sb\u2014N distance is 2.066\u2005(2)\u2005\u00c5, while the Sb\u2014Cl distances are 2.3410\u2005(11) and 2.3639\u2005(12)\u2005\u00c5. The central unit of the cation, SbN4C20, is far from being planar, with deviations of atoms from the least-squares plane ranging from \u22120.110\u2005(4) to 0.124\u2005(4)\u2005\u00c5. The Sb\u2014Cl distances in the anion, which is located about an inversion center, lie in the wide range 2.3715\u2005(13)\u20132.7489\u2005(13)\u2005\u00c5, the longest distances being between the Sb and bridging Cl atoms. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efCl inter\u00adactions involving the cations, the anions and the solvent mol\u00adecules. The solvent mol\u00adecule is disordered over two orientations in a 0.901\u2005(13):0.099\u2005(13) ratio.The asymmetric unit of the title complex, [Sb(C Cl2][Sb2Cl8]0.5\u00b7CH2Cl2 = 0.052wR(F2) = 0.114S = 1.1112918 reflections539 parameters2 restraintsH-atom parameters constrainedmax = 1.36 e \u00c5\u22123\u0394\u03c1min = \u22120.88 e \u00c5\u22123\u0394\u03c1COLLECT  global, I. DOI: 10.1107/S1600536812018351/gk2479Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One Cl atom and one water mol\u00adecule in trans positions complete a distorted octa\u00adhedral geometry around the metal atom. In the crystal, the complex mol\u00adecules and the uncoordinated water mol\u00adecules are connected via O\u2014H\u22efN, O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds into layers parallel to the ac plane and these are consolidated by C\u2014H\u22ef\u03c0 inter\u00adactions. The layers are further linked into a three-dimensional network through C\u2014H\u22efO inter\u00adactions.In the title compound, [Mn(C II complex of the same Schiff base, see: Ikmal Hisham et al. 2Cl(H2O)]\u00b7H2O = 0.039                           wR(F                           2) = 0.093                           S = 0.99                           6393 reflections373 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.43 e \u00c5\u22123                        \u0394\u03c1min = \u22120.32 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811026493/is2745Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit consists of one half of the mol\u00adecular unit, the remainder generated by a twofold rotation axis located along the Cl\u2014Sn\u2014Cl bonds. The SnIV atom is coordinated by two phenyl groups, two Cl atoms and two thio\u00adurea ligands in an all trans octa\u00adhedral C2Cl2S2 environment. Individual mol\u00adecules are connected through N\u2014H\u22efCl hydrogen bonds, leading to a three-dimensional network structure. Intra\u00admolecular N\u2014H\u22efCl hydrogen bonds are also present.The title compound, [Sn(C For org al. 2001; Pelleri al. 2001. For chl al. 2002; M\u00fcller  al. 2008. For tin al. 1984; Sow et  al. 2012; Wirth e al. 1998.6H5)2Cl2(CH4N2S)2] = 0.019wR(F2) = 0.051S = 1.062183 reflections123 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.40 e \u00c5\u22123\u0394\u03c1min = \u22120.72 e \u00c5\u22123\u0394\u03c1COLLECT  used to solve structure: SIR97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024343/wm2764Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Pt atom is located on an inversion centre and thus the asymmetric unit contains one half of the complex; the PtN2Cl2 unit is exactly planar. The dihedral angle between the PtN2Cl2 unit and the quinoline ligand is 85.1\u2005(1)\u00b0. In the crystal, the complex mol\u00adecules are stacked into columns along the b axis. In the columns, several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings are present, the shortest ring centroid\u2013centroid distance being 3.733\u2005(5)\u2005\u00c5 between pyridine rings.In the title complex,  Ha 2012a. For the al. 2001; Ha (201l. 2001b.2(C9H7N)2] = 0.034wR(F2) = 0.080S = 0.971569 reflections106 parametersH-atom parameters constrainedmax = 1.74 e \u00c5\u22123\u0394\u03c1min = \u22120.97 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812013608/ng5260Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuI ion is coordinated in a distorted tetra\u00adhedral geometry by two bridging Br atoms in addition to an N and an S atom from the 2-[disulfan\u00adyl]-4,6-dimethyl\u00adpyrimidine ligand. In the crystal, \u03c0\u2013\u03c0 stacking inter\u00adactions are observed with a centroid\u2013centroid distance of 3.590\u2005(2)\u2005\u00c5.The title dinuclear complex, [Cu DOI: 10.1107/S1600536812016315/lh5449Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The PdII atom is in a distorted quadratic coordination by two P and two Cl atoms with bond lengths of 2.2414\u2005(3) and 2.2438\u2005(3)\u2005\u00c5 for Pd\u2014P, and 2.3452\u2005(3) and 2.3565\u2005(3)\u2005\u00c5 for Pd\u2014Cl. The conformation of the Pd complex is controlled by an intra\u00admolecular slipped \u03c0\u2013\u03c0 stacking inter\u00adaction between a phenyl and a cyclo\u00adpenta\u00addienyl ring with corresponding C\u22efC distances starting at 3.300\u2005(2)\u2005\u00c5 and the distance between ring centroids being 3.674\u2005(2)\u2005\u00c5. The crystal structure is stabilized by C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds. The (CH3)2SO solvent mol\u00adecules are arranged in layers parallel to (101) and are linked in pairs by C\u2014H\u22efO inter\u00adactions. One (CH3)2SO mol\u00adecule is orientationally disordered [occupancy ratio 0.8766\u2005(17):0.1234\u2005(17)] with sulfur in two positions at both sides of its C2O triangle.The racemic title compound, [FePdCl DOI: 10.1107/S160053681103618X/gk2404Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The correct text is \"C\u03b1-model\" \"C"}
{"text": "Two N and two O atoms of the tetra\u00addentate ligand and an O atom of an ethanol ligand form the equatorial plane. The dihedral angle between the mean planes of the two benzene rings is 34.8\u2005(3)\u00b0. In the crystal, relatively strong O\u2014H\u22efO hydrogen bonds connect the complex and ethanol solvent mol\u00adecules into alternating centrosymmetric R               2               2(8) and R               4               4(16) ring motifs, forming chains along [100]. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds are also present.In the title compound, [U(C S-alkyl-thio\u00adsemicarbazone compounds, see: Gerbeleu & Revenko O2(C2H6O)]\u00b7C2H6O = 0.041                           wR(F                           2) = 0.120                           S = 1.01                           5467 reflections309 parameters1 restraintH-atom parameters constrainedmax = 2.48 e \u00c5\u22123                        \u0394\u03c1min = \u22121.18 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SIR92  global. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains two Na+ cations located on a centre of symmetry and on a mirror plane, respectively, one half of a bis-phospho\u00adnate anion (the entire anion is completed by mirror symmetry), one chloride anion on a mirror plane and one water mol\u00adecule in general positions. The two Na+ cations exhibit distorted octa\u00adhedral NaCl2O4 coordination polyhedra, each consisting of two deprotonated O atoms of the bis-phospho\u00adnate anion, of two water mol\u00adecules and of two chloride anions. Strong O\u2014H\u22efO hydrogen bonds between the \u2013OH group and one of the free O atoms of the bis-phospho\u00adnate anion connect adjacent layers along [100], supported by N\u2014H\u22efCl inter\u00adactions. Intra\u00adlayer O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds are also observed.The title compound, [Na Cl(H2O)2][NaMr = 321.50Monoclinic, a = 5.53806 (4) \u00c5b = 10.50365 (8) \u00c5c = 10.2096 (1) \u00c5\u03b2 = 104.0764 (7)\u00b0V = 576.06 (1) \u00c53Z = 2K\u03b11 radiationCu \u03bb = 1.5406 \u00c5\u22121\u03bc = 6.62 mmT = 298 KFlat sheet, 8 \u00d7 8 mmSTOE Transmission STADI P diffractometerSpecimen mounting: powder loaded between two Mylar foilsData collection mode: transmissionScan method: stepGSAS  = 0.02572 = 1.769\u03c74250 data points109 parameters10 restraintsH atoms treated by a mixture of independent and constrained refinementWinXPOW  used to solve structure: EXPO2009  global, I. DOI: 10.1107/S1600536812018077/wm2620Isup2.rtvRietveld powder data: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The resulting SmN2O6 coordination polyhedron is a distorted square anti\u00adprism. In the crystal, C\u2014H\u22efO inter\u00adactions connect mol\u00adecules into chains along the b-axis direction. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions are observed with centroid\u2013centroid distances in the range 3.6422\u2005(13)\u20133.7329\u2005(13)\u2005\u00c5.In the title compound, [Sm(C DOI: 10.1107/S1600536813016139/ff2109Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The asymmetric unit is completed by one 4-methyl\u00adbenzoate anion, one isonicotinamide (INA) ligand and one uncoordinated water mol\u00adecule; all the ligands are monodentate. The two O and the two N atoms around the CuII ion form a slightly distorted square-planar arrangement. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 13.86\u2005(9)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 86.08\u2005(5)\u00b0. The uncoordinated water mol\u00adecules are linked to the INA ligands by O\u2014H\u22efO hydrogen bonds. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network.In the centrosymmetric title compound, [Cu(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2]\u00b72H2O = 0.035                           wR(F                           2) = 0.080                           S = 1.08                           3199 reflections204 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.63 e \u00c5\u22123                        \u0394\u03c1min = \u22120.51 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999Data collection: 10.1107/S1600536810028060/su2197sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028060/su2197Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the three components are assembled into a tape structure along the a axis by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. Between the tapes, a \u03c0\u2013\u03c0 inter\u00adaction with a centroid\u2013centroid distance of 3.569\u2005(3)\u2005\u00c5 and a weak C\u2014H\u22efF hydrogen bond are observed.In the title compound, [Mn(C DOI: 10.1107/S1600536811049968/is2782Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II polymeric complex, [Cd(C7H4ClO2)2(C10H14N2O)(H2O)]n, the CdII cation is chelated by two chloro\u00adbenzoate anions and coordinated by two N,N-di\u00ad\u00adethyl\u00adnicotinamide (DENA) ligands and one water mol\u00adecule in a distorted NO6 penta\u00adgonal\u2013bipyramidal geometry. The CdII cations are bridged by the pyridine N atom and carbonyl O atom of the DENA ligand to form a polymeric chain running along the b axis. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds between coordinating water mol\u00adecules and carboxyl\u00adate groups link adjacent chains into layers parallel to the bc plane. \u03c0\u2013\u03c0 contacts between benzene rings [shortest centroid\u2013centroid distance = 3.912\u2005(2)\u2005\u00c5] further stabilizes the crystal structure. In the mol\u00adecule, weak C\u2014H\u22efO hydrogen bonds occur between the pyridine ring and carboxyl\u00adate groups; the dihedral angles between the carboxyl\u00adate groups and adjacent benzene rings are 4.6\u2005(3) and 12.8\u2005(3)\u00b0, while the benzene rings are oriented at a dihedral angle of 1.89\u2005(13)\u00b0.In the crystal of the title Cd N,N-di\u00adethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)(H2O)] = 0.046wR(F2) = 0.093S = 1.356531 reflections326 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.77 e \u00c5\u22123\u0394\u03c1min = \u22121.02 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S160053681301965X/xu5721Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The acesulfamate ligand is N-bound to Pd [Pd\u2014N = 2.127\u2005(2)\u2005\u00c5] with a dihedral angle of 76.35\u2005(6)\u00b0 relative to the square plane. Relatively long phen\u00adyl\u2013acesulfamate C\u2014H\u22efO and phen\u00adyl\u2013fluorine C\u2014H\u22efF inter\u00adactions consolidate the crystal packing.The title acesulfamate complex, [Pd(C DOI: 10.1107/S1600536811002911/gw2097Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the cation, the CoII atom is six-coordinated in a distorted octa\u00adhedral geometry. It bonds to two O atoms of two water mol\u00adecules, and two pairs of N atoms from two 4-amino-3,5-bis\u00ad(2-pyrid\u00adyl)-4H-1,2,4-triazole mol\u00adecules, which behave as bidentate chelating ligands. There are intra\u00admolecular N\u2014H\u22efN hydrogen bonds in the cation. In the crystal, there are a number of inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, as well as inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.657\u2005(2) and 3.847\u2005(2)\u2005\u00c5], that link the mol\u00adecules into two-dimensional networks lying parallel to the ab plane. The presence of C\u2014H\u22efO inter\u00adactions leads to the formation of a three-dimensional network.The title complex, [Co(C DOI: 10.1107/S1600536811035446/su2310Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The FeIII atom is displaced by 0.40\u2005(1)\u2005\u00c5 towards the trifluoro\u00admethane\u00adsulfonate anion from the 24-atom mean plane of the porphyrin. The average Fe\u2014Np distance is 2.044\u2005(2)\u2005\u00c5 and the Fe\u2014O distance is 2.001\u2005(2)\u2005\u00c5.The title compound, [Fe(CF DOI: 10.1107/S1600536811001395/bv2171Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bond lengths lie within the range 2.3000\u2005(2)\u20132.326\u2005(2)\u2005\u00c5 for the Tb\u2014O bonds and 2.543\u2005(3)\u20132.553\u2005(3)\u2005\u00c5 for the Tb\u2014N bonds. The NaI atom is five-coordinated by two water O atoms and three carboxyl\u00adate O atoms in a distorted square-pyramidal geometry. In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network.In the title compound, {[NaTb(C DOI: 10.1107/S1600536810038456/is2603Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Cu(C7H4FO2)2(C10H14N2O)2(H2O)2], contains one-half of the mol\u00adecule. The CuII ion is located on an inversion centre, and is coordinated by two N atoms from two diethyl\u00adnicotinamide ligands, two O atoms from two 4-fluoro\u00adbenzoate (PFB) ligands and two water mol\u00adecules in a distorted octa\u00adhedral geometry. In the PFB ligand, the carboxyl\u00adate group is twisted at an angle of 2.10\u2005(14)\u00b0 from the attached benzene ring. In the crystal structure, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link mol\u00adecules related by translation along the a axis into chains. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of neighbouring mol\u00adecules [centroid-to-centroid distance = 3.571\u2005(2)\u2005\u00c5] further consolidate the crystal packing.The asymmetric unit of the title mononuclear Cu N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.033                           wR(F                           2) = 0.099                           S = 1.15                           4109 reflections233 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.57 e \u00c5\u22123                        \u0394\u03c1min = \u22120.45 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811029941/cv6646Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, C\u2014H\u22ef\u03c0 inter\u00adactions [C\u2014H\u22efcentroid distances = 3.443\u2005(3) and 3.788\u2005(3)\u2005\u00c5] and N\u2014H\u22efS hydrogen bonds form layers parallel to (100). An intra\u00admolecular N\u2014H\u22efI hydrogen bond is also observed.In the mononuclear title complex, [CuI(C DOI: Click here for additional data file.10.1107/S1600536812044066/zb2025Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each CuII atom is four-coordinated by two phenolate O and two imine N atoms from two symmetry-related Schiff base 2-{[2-(isopropyl\u00adaza\u00adnium\u00adyl)eth\u00adyl]imino\u00admeth\u00adyl}-6-meth\u00adoxy\u00adphenolate (L) ligands in a distorted square-planar geometry. The ammonium groups are involved in the formation of N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, which link one dication and two anions into an electroneutral cluster. When very weak Cu\u2014N interactions with a distance of 2.910\u2005(5)\u2005\u00c5 between the metal and the thiocyanate anions in apical positions are considered, the secondary coordination polyhedron is a very elongated CuN4O2 octahedron. The asymmetric unit of the title compound, [Cu(C For rel al. 2010; Cai 2](NCS)2                         = 0.078                           wR(F                           2) = 0.143                           S = 1.15                           2406 reflections190 parameters6 restraintsH-atom parameters constrainedmax = 0.38 e \u00c5\u22123                        \u0394\u03c1min = \u22120.36 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL (Sheldrick, 2008SHELXL97.Data collection: 10.1107/S1600536811001322/cv5037sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001322/cv5037Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "As a consequence, the Cl and Br atoms are not well ordered but distributed over the three possible positions such that the overall stiochiometry is two Br atoms and one Cl atom. The scrambling of the Br and Cl atoms indicates a small energy barrier for the exchange process between the apical and equatorial positions. Overall, the Te atom geometry is slightly distorted square pyramidal (\u03c4 = 0.052 for the major component). However, there is a weak secondary inter\u00adaction between the Te atoms and the disordered Br/Cl atoms of a nearby mol\u00adecule. The Te\u2014Br and Te\u2014Cl distances in both disorder components fall into two groups; a longer distance for the Br/Cl involved in this secondary inter\u00adaction [2.6945\u2005(17)\u2005\u00c5 for Br and 2.601\u2005(9)\u00c5 for Cl] and shorter bond distances to the remaining halogen atoms, indicating that this inter\u00adaction has slightly weakened the Te\u2014X bond, as is the case in the previously reported tribromido structure [Singh et al. (1990). J. Chem. Soc. Dalton Trans. pp. 907\u2013913]. Otherwise, the metrical parameters in the two structures are not significantly different. An intermolecular C\u2014H\u22efBr interaction occurs.The title compound, C \u00c5                           b = 12.4785 (5) \u00c5                           c = 14.4098 (6) \u00c5                           \u03b2 = 98.200 (4)\u00b0V = 1296.61 (9) \u00c53                                                   Z = 4                           K\u03b1 radiationMo \u22121                        \u03bc = 8.63 mmT = 123 K                           0.63 \u00d7 0.50 \u00d7 0.10 mm                                 Oxford Diffraction Xcalibur Ruby Gemini diffractometerCrysAlis PRO 2981 reflections with R                           int = 0.044                                                            R[F                           2 > 2\u03c3(F                           2)] = 0.038                           wR(F                           2) = 0.056                           S = 0.96                           4241 reflections141 parameters1 restraintH-atom parameters constrainedmax = 0.91 e \u00c5\u22123                        \u0394\u03c1min = \u22120.92 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811054560/jj2114Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The TiIV atom displays a distorted tetra\u00adhedral geometry, with Ti\u2014O bond lengths ranging from 1.805\u2005(3) to 1.830\u2005(3)\u2005\u00c5 and O\u2014Ti\u2014O ligand bite angles of 100.16\u2005(12) and 101.36\u2005(12)\u00b0. The short Ti\u2014N bond distances, ranging from 1.877\u2005(4) to 1.905\u2005(4)\u2005\u00c5, indicate strong bonding between the TiIV atom and the dimethyl\u00adamide ligands.In the title four-coordinate complex, [Ti(C DOI: 10.1107/S1600536812002929/yk2040Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Pd\u2014P and Pd\u2014Cl bond lengths are 2.3550\u2005(7) and 2.2906\u2005(7)\u2005\u00c5, respectively. Some weak inter\u00adactions are observed between the aromatic rings of adjacent mol\u00adecules, with an inter\u00adplanar distance between two \u03c0-stacked rings of 3.505\u2005(3)\u2005\u00c5. Intra- and intermolecular C\u2014H\u22efCl hydrogen bonds also occur.The title compound,  DOI: 10.1107/S1600536810042595/pk2275Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The oral administration of vitamin B12 offers a potentially simpler and cheaper alternative to parenteral administration, but its effectiveness has not been definitively demonstrated. The following protocol was designed to compare the effectiveness of orally and intramuscularly administered vitamin B12 in the treatment of patients \u00e2\u2030\u00a565\u00e2\u20ac\u2030years of age with vitamin B12 deficiency.The proposed study involves a controlled, randomised, multicentre, parallel, non-inferiority clinical trial lasting one year, involving 23 primary healthcare centres in the Madrid region (Spain), and patients \u00e2\u2030\u00a565\u00e2\u20ac\u2030years of age. The minimum number of patients required for the study was calculated as 320 (160 in each arm). Bearing in mind an estimated 8-10% prevalence of vitamin B12 deficiency among the population of this age group, an initial sample of 3556 patients will need to be recruited.Eligible patients will be randomly assigned to one of the two treatment arms. In the intramuscular treatment arm, vitamin B12 will be administered as follows: 1\u00e2\u20ac\u2030mg on alternate days in weeks 1 and 2, 1\u00e2\u20ac\u2030mg/week in weeks 3\u00e2\u20ac\u201c8,and 1\u00e2\u20ac\u2030mg/month in weeks 9\u00e2\u20ac\u201c52. In the oral arm, the vitamin will be administered as: 1\u00e2\u20ac\u2030mg/day in weeks 1\u00e2\u20ac\u201c8 and 1\u00e2\u20ac\u2030mg/week in weeks 9\u00e2\u20ac\u201c52. The main outcome variable to be monitored in both treatment arms is the normalisation of the serum vitamin B12 concentration at weeks 8, 26 and 52; the secondary outcome variables include the serum concentration of vitamin B12 (in pg/ml), adherence to treatment, quality of life (EuroQoL-5D questionnaire), patient 3satisfaction and patient preferences. All statistical tests will be performed with intention to treat and per protocol. Logistic regression with random effects will be used to adjust for prognostic factors. Confounding factors or factors that might alter the effect recorded will be taken into account in analyses.The results of this study should help establish, taking quality of life into account, whether the oral administration of vitamin B12 is an effective alternative to its intramuscular administration. If this administration route is effective, it should provide a cheaper means of treating vitamin B12 deficiency while inducing fewer adverse effects. Having such an alternative would also allow patient preferences to be taken into consideration at the time of prescribing treatment.This trial has been registered with ClinicalTrials.gov, number NCT 01476007, and under EUDRACT number 2010-024129-20. Vitamin B12 , along with other derivatives of folic acid, is a nutrient essential for the synthesis of DNA. Its deficiency is manifested through changes in the number and morphology of erythrocytes, leucocytes and platelets, and by neurological alterations owed to the progressive demineralisation of the nervous system (a consequence of defective myelin synthesis). Vitamin B12 is found mostly in food of animal origin. It is separated from ingested food through the action of the gastric acid, and in the duodenum the vast majority binds to intrinsic factor (IF). The vitamin B12/IF complex formed, which is very resistant to digestion, is then absorbed by endocytosis in the terminal ileum. Only 1-2% of vitamin B12 absorption occurs independent of IF .In the primary healthcare setting, the most commonly seen causes of vitamin B12 deficiency are related to abnormalities of digestion  or absorption , and, to a lesser extent, a lack of exogenous supply. The exact prevalence of vitamin B12 deficiency in industrialised countries is unknown; indeed, different studies using different definitions have reported it as between 5% and 60% . ResultsIn the elderly, the symptoms of vitamin B12 deficiency caused by deficient diets and/or digestive and/or absorption problems can be nonspecific, making a diagnosis of deficiency more difficult. For example, up to 40% of elderly people show no haematological alterations. Further, neurological symptoms may appear before those of anaemia; indeed, only about 60% of elderly people with vitamin B12 deficiency are anaemic .The trial protocol was approved by the Madrid Region Clinical Research Ethics Committee  in the last five years for vitamin B12 deficiency\u00c2\u00b7 serious neurological or psychiatric symptoms, including psychotic problems\u00c2\u00b7 dementia preventing the giving of informed consent to take part\u00c2\u00b7 atrophy of the optic nerve\u00c2\u00b7 serum folic acid concentration of <2.3\u00e2\u20ac\u2030ng/ml\u00c2\u00b7 stage 4 kidney disease 4 (estimated glomerular filtration rate [GFR] 15\u00e2\u20ac\u201c29\u00e2\u20ac\u2030ml/min)\u00c2\u00b7 having received/suffering malabsorption-related:\u00e2\u2014\u2039 surgery or diseases affecting the jejunum-ileum\u00e2\u2014\u2039 inflammatory-intestinal disease, e.g., Crohn\u00e2\u20ac\u2122s disease, ulcerative colitis\u00e2\u2014\u2039 celiac disease\u00c2\u00b7 chronic pancreatitis\u00c2\u00b7 myelodisplasia or malignant blood disease\u00c2\u00b7 haemophilia or other coagulation problems contraindicating parenteral administration\u00c2\u00b7 severe systemic disease\u00c2\u00b7 having been involved in any other trial involving the administration of any experimental treatment in the 28\u00e2\u20ac\u2030days prior to the start of the present study\u00c2\u00b7 being treated for HIV, HVB or HVC infection\u00c2\u00b7 hypersensitivity to vitamin B12, or any of the vitamin preparation\u00e2\u20ac\u2122s excipients\u00c2\u00b7 receiving anticoagulation treatment\u00c2\u00b7 being away from home and with no intention of residing for the following year in the health district where consultation was made\u00c2\u00b7 failing to meet any inclusion criterion\u00c2\u00b7 limitations regarding oral treatmentParticipants will be enrolled consecutively by their general practitioners when attending a primary healthcare centre in the study area Figure . All patThe sample size required was determined bearing in mind the results of Kuzminski et al. . In the Assuming that the percentage of patients showing an increase in serum vitamin B12 concentration to above 179\u00e2\u20ac\u2030pg/ml in both groups is 70%, means the study requires at least 304 patients (152 in each arm) for a threshold of non-inferiority of 10% and a statistical power of 60% with significance set at p\u00e2\u20ac\u2030<\u00e2\u20ac\u20300.05. Given the type of patients to be studied, i.e., patients who have come to the health centres for consultation, plus the fact that their own family doctors are members of the research team, a loss to follow-up of under 5% is expected. The minimum starting sample size for each arm was therefore deemed to be n\u00e2\u20ac\u2030=\u00e2\u20ac\u2030160. With an expected prevalence of vitamin B12 deficiency of 8-10% , the original number of patients to be enrolled so that 320 with a vitamin B12 deficiency can be guaranteed is 3556.In studies with the present design it is impossible to blind the patient to the treatment received. However, this limitation is compensated for by the objective measurement of the main outcome variable (the serum vitamin B12 concentration) and the randomisation of the patients to the treatment groups. Further, the persons charged with the statistical analysis of the data will be blind to the identity of the patients in each treatment arm.The pharmaceutical formulations to be used in the study are commercially available in Spain. The treatments will involve:\u00c2\u00b7 Intramuscular route: 1\u00e2\u20ac\u2030mg of vitamin B12 on alternate days during weeks 1 and 2; 1\u00e2\u20ac\u2030mg/week over weeks 3\u00e2\u20ac\u201c8 ; and 1\u00e2\u20ac\u2030mg/month from weeks 9\u00e2\u20ac\u201c52\u00c2\u00b7 Oral route: 1\u00e2\u20ac\u2030mg/day of vitamin B12 for 8\u00e2\u20ac\u2030weeks; 1\u00e2\u20ac\u2030mg/week from weeks 9\u00e2\u20ac\u201c52Patients in both arms will undergo analytical monitoring in weeks 8, 26 and 52. They will receive appointments for the appropriate dates. The response to treatment will be recorded alongside adherence to treatment and the appearance of any adverse effects.Before work begins, the project will be presented to all the research team members in a special meeting. Training sessions lasting 2\u00e2\u20ac\u201c3\u00e2\u20ac\u2030h will also be held at each participating health centre. These will involve a review of the inclusion and exclusion criteria, provide instructions regarding the intervention, and examine the ethical requirements to be met for the trial to be held.The procedures to be followed and information to be recorded at each of a patient\u00e2\u20ac\u2122s visits to a participating health centre is as follows:Selection Visit\u00c2\u00b7 Signing of informed consentAssessment of inclusion/exclusion criteriaRecording of demographic data (age and sex)Analysis: serum vitamin B12. If concentration is <179 pg/ml the following analyses are to be requested: haemogram, biochemical analysis , ferritin, folic acid, anti-IF antibody level. If serum vitamin B12 concentration is >179 pg/ml: patient preference questionnaireRandomisation of patients to treatment groupVisit 1 (start of treatment)\u00c2\u00b7 Anamnesis: record whether the patient lives alone or with others, lifestyle habits, use of alcohol, whether a vegan diet is followed, whether the patient has undergone gastrectomySymptoms: record paresthesia, asthenia, loss or reduction of appetite, sadness or change in state of mind, concomitant pharmacological treatmentPhysical examination: for Hunter\u00e2\u20ac\u2122s glositis, positional and vibrational sensitivityQuestionnaires: Lobo cognitive mini-exam, EuroQoL-5DRecord concomitant treatmentRequest analyses to be performed one week before next visit: haemogram and serum vitamin B12Therapeutic plan: patient in oral arm \u00e2\u20ac\u201c provision of medication; patient in intramuscular arm \u00e2\u20ac\u201c provide appointments for injectionsVisit 2 (week 8)\u00c2\u00b7 Anamnesis: record lifestyle habits and use of alcoholSymptoms: if pathological at the first visit, record paresthesia, asthenia, loss or reduction of appetite, sadness or change in level of happiness, and concomitant pharmacological treatmentPhysical examination: if pathological at the first visit examine for Hunter\u00e2\u20ac\u2122s glositis, positional and vibrational sensitivityRecord concomitant treatmentRequest analyses to be performed one week before next visit: haemogram and serum vitamin B12Questionnaires: EuroQoL-5DAssessment of adverse effectsTherapeutic plan: patient in oral arm \u00e2\u20ac\u201c provision of medication; patient in intramuscular arm \u00e2\u20ac\u201c provide appointments for injectionsAssess adherence to treatment: oral route \u00e2\u20ac\u201c count number of vials used; intramuscular route: count injections givenVisit 3 (week 26)\u00c2\u00b7 Anamnesis: record lifestyle habits and use of alcoholSymptoms: if pathological at the first visit, record paresthesia, asthenia, loss or reduction of appetite, sadness or change in level of happiness, and concomitant pharmacological treatmentPhysical examination: if pathological at the first visit examine for Hunter\u00e2\u20ac\u2122s glositis, positional and vibrational sensitivityRecord concomitant treatmentRequest analyses to be performed one week before next visit: haemogram and serum vitamin B12Questionnaire: EuroQoL-5DAssessment of adverse effectsTherapeutic plan: patient in oral arm \u00e2\u20ac\u201c provision of medication; patient in intramuscular arm \u00e2\u20ac\u201c provide appointments for injectionsAssess adherence to treatment: oral route \u00e2\u20ac\u201c count number of vials used; intramuscular route: count injections givenVisit 4 (week 52)\u00c2\u00b7 Anamnesis: record lifestyle habits and use of alcoholSymptoms: record paresthesia, asthenia, loss or reduction of appetite, sadness or change in level of happiness, and concomitant pharmacological treatmentPhysical examination: for Hunter\u00e2\u20ac\u2122s glositis, positional and vibrational sensitivityRecord concomitant treatmentQuestionnaires: EuroQoL-5D, satisfaction and preferencesAssessment of haemogram and serum vitamin B12 concentrationAssessment of adverse effectsAssess adherence to treatment: oral route \u00e2\u20ac\u201c count number of vials used; intramuscular route: count injections givenThe main outcome to be measured is the normalisation of the serum vitamin B12 concentration (>179\u00e2\u20ac\u2030pg/ml) at 8, 26 and 52\u00e2\u20ac\u2030weeks. The secondary outcomes will be the serum vitamin B12 concentration (pg/ml), adverse events , adherence to treatment , quality of life (measured using the EuroQoL-5D questionnaire), and patient satisfaction and preferences.Including age, sex, whether the patient lives alone or with others, whether a vegan diet is followed, and the use of alcohol (g/week).Symptoms such as paresthesia, asthenia, loss or reduction of appetite, sadness or change in state of mind (anamnesis), Hunter\u00e2\u20ac\u2122s glositis, positional and vibrational sensitivity , and cognitive decline (Lobo test).Haemogram (complete blood cell and platelet count) and biochemical analysis . Blood analyses will be performed in plasma or serum as required and under standard conditions.Recording of the taking of protein pump inhibitors, H2 receptor antagonists, antacids, potassium, metformin, colchicine, neomycin, p-aminosalicylic acid, parenteral chloramphenicol, Fe, vitamin C and other vitamin supplements.Patients will be removed from the trial if any of the following conditions are met:\u00c2\u00b7 Serum vitamin B12 concentration still <179\u00e2\u20ac\u2030pg/ml after 8\u00e2\u20ac\u2030weeks of treatment. Treatment will be deemed to have failed in these patients, and they will be further studied and treated outside the trial according to normal clinical practice.\u00c2\u00b7 Serious adverse events.\u00c2\u00b7 Voluntary withdrawal or violation of the protocol.At least two attempts will be made to contact by telephone those patients who do not come for their scheduled visits. All patients will be informed that they can abandon the study at any time without this affecting their future medical treatment in any way.The trial will involve a descriptive statistical analysis of the baseline characteristics of patients in both treatment arms. Quantitative variables will be described in terms of their measure of central tendency, mean or median (for those showing asymmetric distributions), and the corresponding dispersion, standard deviation or interquartile range. Qualitative variables will be described in terms of proportions and their corresponding confidence intervals.The Student t test or Mann\u00e2\u20ac\u201cWhitney U test  will be used to determine whether the two treatment arms are comparable based on their quantitative baseline characteristics and known prognostic factors. Comparisons on qualitative variables will be undertaken using the Pearson Chi-squared test or Fisher\u00e2\u20ac\u2122s Exact test as required. If cases of inequality are detected, the confounding factors will be defined and appropriate adjustments made.Intention-to-treat and per-protocol analyses will both be performed, as is recommended for non-inferiority studies .The effectiveness of treatment will be analysed by examining the therapeutic success achieved in each arm at 8, 26 and 52\u00e2\u20ac\u2030weeks, determining the 95% confidence interval for the percentage of patients in each treatment arm whose serum vitamin B12 concentrations become normalised. If the confidence intervals do not fall outside the non-inferiority limit (10%), it can be concluded that the oral treatment is not inferior to the intramuscular treatment. The within-patient percentage change in serum vitamin B12 concentration at each monitoring point will be determined, and the confidence intervals for the difference in the mean values for each arm calculated.If the distribution of confounding factors differs in the two arms, explicative regression analysis will be performed in which the dependent variable will be the normalisation of the serum vitamin B12 concentration, and the independent variable will be the treatment group.Repeated measures ANOVA will be used to examine the change in serum vitamin B12 concentration in each group at each monitoring point.The incidence of adverse events in the two arms will be compared using the Pearson Chi-squared test or Fisher\u00e2\u20ac\u2122s Exact test as required.-based quality of life values.The perception of quality of life by the patients of each arm will be assessed by comparing the EuroQol 5D scores  and the transformation of these scores into utilityAdherence to treatment will be examined via the counting of oral doses taken in the oral arm, and the number of injections given in the intramuscular arm. An operative indicator variable will then be defined to describe the degree of adherence.th 2011). It will be performed by qualified medical and scientific staff. The rights and welfare of the patients will be respected at all times. All patients will be adequately informed, both verbally and in writing, of the nature of the trial, its aim, and its risks and possible benefits. Given that the study is a non-inferiority trial, all patients will be informed that the oral treatment is expected to be as effective as the standard intramuscular treatment. Signed, dated consent to be included will be required from each patient.The trial has been approved by the Madrid Region Clinical Research Ethics Committee (February 8Convenio de Oviedo) (1997).Spanish law regarding the use of human subjects in clinical trials will be adhered to. The trial will respect all basic ethical principles of autonomy, justice, goodness of intent and absence of malintent according to the standards of good clinical practice enshrined in the Declaration of Helsinki  and the Oviedo Agreement  that quality scientific information supports the effectiveness of the therapeutic options on offer, and 2) that heterogeneous groups of patients have recorded their satisfaction with these options. The present trial provides for information in this respect to be gathered  and therThe trial is also designed to provide information on the effect of the normalisation of serum vitamin B12 concentrations by both treatments on patient-perceived quality of life. Physicians commonly assume that taking oral supplements will be associated with a feeling of greater well-being, although this has never been proven . The preThe trial suffers from the practical limitation of having to enrol a large number of patients to meet its sample size requirements. However, a high degree of motivation is expected of the research team since its clinical assistance members are those involved in the enrolment process. Further, the fact that the patients to be enrolled will be seeking medical help  suggests few will be lost to follow-up. A further possible limitation is the low statistical power used in the calculation of the sample size. The 60% power contemplated requires a sample size of 304 patients (152 in each arm) \u00e2\u20ac\u201c higher powers would increase the sample size required and the enrolment of such numbers cannot be guaranteed. However, given the results reported in previous studies  that used moderate/high doses of vitamin B12, it should be possible to demonstrate the non-inferiority of the oral treatment with this power level. If the 95% confidence interval were to cross the non-inferiority threshold, i.e., showing the results to be inconclusive, the intramuscular treatment would remain the treatment of choice. To determine the degree of adherence to treatment (and thus avoid outcome dilution effects) , the numThe decision not to take serum methylnalonic acid and homocysteine concentrations into account as diagnostic markers and outcome variables was made bearing in mind that these are not normally determined, either at diagnosis or during follow-up, in patients with a vitamin B12 deficiency.Finally, given the pragmatic nature of the proposed trial, the decision was taken to include consecutive patients seeking medical help at the participating centres, thus ensuring the enrolment of subjects similar to those that would be seen in normal clinical practice.Fe: Ferrum; g: Gram; GFR: Glomerular filtration rate; GGT: Gamma-glutamyl transpeptidase; GOT: Glutamic oxaloacetic transaminase; GP: General practitioner; GPT: Glutamic-pyruvic transaminase; HIV: Human immunodeficiency virus; HVB: Hepatitis B virus; HVC: Hepatitis C virus; IF: Intrinsic factor; \u00ce\u00bcg: Microgram; MMA: Methylmalonic acid; mg: Milligrams; ng: Nanograms; pg: Picograms.The authors declare that they have no competing interests.PGE y RRF conceived of the study and participated in its design. TSC; RRF; SGE; IdCG; JMF; EEM; participated in the design and coordination of the study. FRS; MGS; RGG; MAMS; COL; MLSP; CMR; BMB; AVP; FGBG; JEMS; RRB; GAC; LMCB; EPC; MRB; MTRM; SSD; SMI; RRG; IBL; MVN; JSD; TGG; MDC; AAB participated in different phases of the design. TSC; RRF; SGE; IdCG; JMF; EEM directed the writing of the manuscript. All authors OB12 Group read and approved the final manuscript.Healthcare Centre (HC) Barajasx: Germ\u00c3\u00a1n Reviriego Ja\u00c3\u00a9n, Cristina Montero Garc\u00c3\u00ada, Ana Isabel Sanz Lorente, Ma del Pilar Serrano Simarro, Juli\u00c3\u00a1n D\u00c3\u00adaz S\u00c3\u00a1nchez, Irma Ma Ramos Guti\u00c3\u00a9rrez, Josefa Ma San Vicente Rodr\u00c3\u00adguez, Pilar Huelin Mart\u00c3\u00adn, Ma Inmaculada Gonz\u00c3\u00a1lez Garc\u00c3\u00ada, Margarita Camarero Shelly, Clarisa Reinares Mart\u00c3\u00adnez, Laura Villanova Cuadra, Rosa Ma\u00e2\u20ac\u2030G\u00c3\u00b3mez del Forcallo. HC Doctor Cirajas: Francisco Endrino G\u00c3\u00b3mez, Ma Rosario Ferreras Eleta, Luis De Vicente Aymat, Mar\u00c3\u00ada Santos Santander Guti\u00c3\u00a9rrez, Alicia Mateo Madurga. HC Juncal: Nuria Caballero Ram\u00c3\u00adrez, Ana Mor\u00c3\u00a1n Escudero, Mercedes Rodr\u00c3\u00adguez Franco, M\u00c2\u00aa Luz Meiri\u00c3\u00b1o P\u00c3\u00a9rez, M\u00c2\u00aa Mar Zamora G\u00c3\u00b3mez, Francisco Vivas Rubio, Mar\u00c3\u00ada Mart\u00c3\u00adn Mart\u00c3\u00adn. HC Miguel de Cervantes: Rafael P\u00c3\u00a9rez Quero, M\u00c2\u00aa Isabel Manzano Mart\u00c3\u00adn, Raimundo Pastor S\u00c3\u00a1nchez, Alicia Herrero de Dios, Cesar Redondo Luci\u00c3\u00a1\u00c3\u00b1ez. HC Reyes Magos: Cristina Casado Rodr\u00c3\u00adguez, Luisa Mar\u00c3\u00ada Andr\u00c3\u00a9s Arreaza, Pilar Hombrados Gonzalo, Soledad Escolar Llamazares, Francisco L\u00c3\u00b3pez Ortiz, Luz M\u00c2\u00aa del Rey Moya, Isabel Rodr\u00c3\u00adguez L\u00c3\u00b3pez. HC Calesas: Diego Mart\u00c3\u00adn Acicoya, Pilar Kloppe Villegas, Isabel Garc\u00c3\u00ada Amor, Magdalena Canals Aracil, Jos\u00c3\u00a9 Javier G\u00c3\u00b3mez Marco, Alberto Gonz\u00c3\u00a1lez \u00c3\ufffdlvaro, Fco Javier San Andr\u00c3\u00a9s Rebollo, In\u00c3\u00a9s Gonz\u00c3\u00a1lez L\u00c3\u00b3pez, Isabel Herreros Hernanz, Antonio Revuelta Alonso, Nieves Calvo Arrabal, M\u00c2\u00aa Milagros Jimeno Gal\u00c3\u00a1n, Rosa Garc\u00c3\u00ada Hern\u00c3\u00a1ndez. HC Guayaba: Tom\u00c3\u00a1s G\u00c3\u00b3mez Gasc\u00c3\u00b3n, Concepci\u00c3\u00b3n Vargas-Machuca Caba\u00c3\u00b1ero, M\u00c2\u00aa Isabel Guti\u00c3\u00a9rrez S\u00c3\u00a1nchez, M\u00c2\u00aa Angeles Fern\u00c3\u00a1ndez Abad, Margarita Beltejar Rodr\u00c3\u00adguez, Javier Mart\u00c3\u00adnez Suberviola, Miguel Angel Real P\u00c3\u00a9rez, Carmen Coello Alarc\u00c3\u00b3n, Carlos San Andr\u00c3\u00a9s Pascua, Jos\u00c3\u00a9 Antonio Granados Garrido. HC General Ricardos: Santiago Mach\u00c3\u00adn Hamalainen, Raquel Mateo Fern\u00c3\u00a1ndez, Cristina de la C\u00c3\u00a1mara Gonzalez, Jos\u00c3\u00a9 D.Garc\u00c3\u00a9s Ranz, Asunci\u00c3\u00b3n Prieto Orzanco, M\u00c2\u00aa Teresa Mar\u00c3\u00adn Becerra, Paulino Cubero Gonz\u00c3\u00a1lez, Francisco R. Abell\u00c3\u00a1n L\u00c3\u00b3pez, Olga \u00c3\ufffdlvarez Montes, Mercedes Canellas Manrique, M\u00c2\u00aa Jos\u00c3\u00a9 San Telesforo Navarro, M\u00c2\u00aa Mercedes Parrilla Laso, M\u00c2\u00aa \u00c3\ufffdngeles Aragoneses Ca\u00c3\u00b1as, Angela Au\u00c3\u00b1\u00c3\u00b3n Muelas HC Los Y\u00c3\u00a9benes, Esther Vald\u00c3\u00a9s Cruz, Consuelo Mayoral Lopez, Teresa Gijon Seco, Francisca Martinez Vallejo. HC Valle Incl\u00c3\u00a1n: Ana Isabel Men\u00c3\u00a9ndez Fern\u00c3\u00a1ndez, M\u00c2\u00aa del Mar De la Pe\u00c3\u00b1a Gonz\u00c3\u00a1lez, M\u00c2\u00aa \u00c3\ufffdngeles Maroto Garc\u00c3\u00ada, Mar\u00c3\u00ada S\u00c3\u00a1nchez Crist\u00c3\u00b3bal. HC Lavapi\u00c3\u00a9s: M\u00c2\u00aa Carmen \u00c3\ufffdlvarez Orviz, Jes\u00c3\u00bas Herrero Hern\u00c3\u00a1ndez, M\u00c2\u00aa Veredas Gonz\u00c3\u00a1lez M\u00c3\u00a1rquez, M\u00c2\u00aa Jes\u00c3\u00bas L\u00c3\u00b3pez Rodr\u00c3\u00adguez, M\u00c2\u00aa de las Maravillas Almarza Garc\u00c3\u00ada, M\u00c2\u00aa Teresa San Clemente Pastor, M\u00c2\u00aa \u00c3\ufffdmparo Corral Rubio. HC Colmenar Viejo Norte: Gonzalo Ruiz Zurita, \u00c3\ufffdngela Allue Bergua, Marta Cabrera Orozco, M\u00c2\u00aa del Puerto De Antonio Garc\u00c3\u00ada, Ana Isabel Cerezo Diviu, Inmaculada Solsons Roig, Pilar G\u00c3\u00b3mez de Abia. HC Fuentelarreina: Mar\u00c3\u00ada Concepci\u00c3\u00b3n D\u00c3\u00adaz Laso, M\u00c2\u00aa Luisa Asensio Ruiz, Carmen Siguero P\u00c3\u00a9rez. HC Presentaci\u00c3\u00b3n Sabio: Antonio Molina Siguero, Inmaculada Cerrada Puri, Paloma Rodr\u00c3\u00adguez Almagro, Rosa Rosanes Gonz\u00c3\u00a1lez, M\u00c2\u00aa Carmen P\u00c3\u00a9rez Garc\u00c3\u00ada. HC Cuzco: Mar Noguerol \u00c3\ufffdlvarez, M\u00c2\u00aa \u00c3\ufffdngeles de Miguel Abanto, M\u00c2\u00aa Lourdes Reyes Mart\u00c3\u00adnez, Pilar Guti\u00c3\u00a9rrez Valent\u00c3\u00adn, Jorge G\u00c3\u00b3mez Ciriano, Raquel Calzada Benito, Carolina Torrijos Bravo, David Ferreiro Gonz\u00c3\u00a1lez, Judit Le\u00c3\u00b3n Gonz\u00c3\u00a1lez. HC San Mart\u00c3\u00adn de Valdeiglesias: Nuria Tom\u00c3\u00a1s Garc\u00c3\u00ada, Alberto Alcal\u00c3\u00a1 Fa\u00c3\u00bandez, Eva Fern\u00c3\u00a1ndez L\u00c3\u00b3pez, In\u00c3\u00a9s Melero Redondo, Ricardo Gonz\u00c3\u00a1lez Gasc\u00c3\u00b3n. HC Pedroches: Jeannet S\u00c3\u00a1nchez Y\u00c3\u00a9pez, Mercedes del Pilar Fern\u00c3\u00a1ndez Gir\u00c3\u00b3n, Beatriz L\u00c3\u00b3pez Serrano, M\u00c2\u00aa Teresa Rodr\u00c3\u00adguez Monje, Paloma Morso Pelaez, Mar\u00c3\u00ada Cortes Duran, Carolina L\u00c3\u00b3pez Olmeda, Almudena Garc\u00c3\u00ada- Uceda Sevilla, Dolores Serrano Gonz\u00c3\u00a1lez, Inmaculada Santamar\u00c3\u00ada L\u00c3\u00b3pez. HC Mendiguch\u00c3\u00ada Carriche: Francisca Garc\u00c3\u00ada De Blas Gonz\u00c3\u00a1lez, Alberto L\u00c3\u00b3pez Garc\u00c3\u00ada-Franco, Amaya Azcoaga Lorenzo, Mar \u00c3\ufffdlvarez Villalba, Bel\u00c3\u00a9n Pose Garc\u00c3\u00ada. HC Santa Isabel: Rosa Fern\u00c3\u00a1ndez Garc\u00c3\u00ada, Francisco de Alba G\u00c3\u00b3mez, Antonio Redondo Horcajo, Beatriz Pajuelo M\u00c3\u00a1rquez, Jos\u00c3\u00a9 Luis Gala Paniagua, Encarnaci\u00c3\u00b3n Cidoncha Calder\u00c3\u00b3n, \u00c3\ufffdngel Delgado Delgado, M\u00c2\u00aa Jes\u00c3\u00bas G\u00c3\u00b3mez Mart\u00c3\u00adn, Jos\u00c3\u00a9 Francisco \u00c3\ufffdvila Tomas. HC El Greco: Jos\u00c3\u00a9 Enrique Mari\u00c3\u00b1o Su\u00c3\u00a1rez, Jos\u00c3\u00a9 Luis Quintana G\u00c3\u00b3mez, Jos\u00c3\u00a9 Antonio Gonz\u00c3\u00a1lez-Posada Delgado, Enrique Revilla Pascual, Esperanza Duralde Rodr\u00c3\u00adguez, Milagros Beamud Lagos. HC Arroyo de la Media Legua: Leonor Gonz\u00c3\u00a1lez Gal\u00c3\u00a1n, Mar\u00c3\u00ada Verdugo Rosado, Luis Nistal Mart\u00c3\u00adn de Serranos, M\u00c2\u00aa Jes\u00c3\u00bas L\u00c3\u00b3pez Barroso, Mariano Rivera Moreno, Margarita Torres Parras, M\u00c2\u00aa Reyes Delgado Pulpon, Elena Alcal\u00c3\u00a1 Llorente. HC Federica Montseny: Sonsoles Mu\u00c3\u00b1oz Moreno, Ana Mar\u00c3\u00ada Ribao Verdugo, Mar\u00c3\u00ada Jes\u00c3\u00bas Fidalgo Baz, Isabel Vaquero Turi\u00c3\u00b1o, Ana Mar\u00c3\u00ada Je\u00c3\u00ba Fidalgo Baz, Clementa Sanz Sanchez, Ana Mar\u00c3\u00ada S\u00c3\u00a1nchez Sempere, Javier Mart\u00c3\u00adnez Sanz, Mar\u00c3\u00ada Isabel Arratibel Elizondo. HC Buenos Aires: Paloma Gonz\u00c3\u00a1lez Escobar, Javier Mu\u00c3\u00b1oz Guti\u00c3\u00a9rrez, Raquel Ba\u00c3\u00b1os Morras, Carmen Molins Santos, Ana Mar\u00c3\u00ada Ibarra S\u00c3\u00a1nchez, Cecilio G\u00c3\u00b3mez Almod\u00c3\u00b3var, Cristina Cassinello Espinosa.Ministerio de Sanidad, Pol\u00c3\u00adtica Social e Igualdad, Spain  and by CAIBER - Spanish Clinical Research Network. The authors thank the following persons for their contributions to this work: Dolores Otero-Criado, Carlos Carvajales Fern\u00c3\u00a1ndez, Rosa Zurdo-Baz and Raisa Gonz\u00c3\u00a1lez-P\u00c3\u00a9rez.This study was funded by the The pre-publication history for this paper can be accessed here:http://www.biomedcentral.com/1471-2458/12/394/prepub"}
{"text": "The asymmetric unit further contains one 4-meth\u00adoxy\u00adbenzoate anion, one nicotinamide (NA) ligand and one coordinated and one uncoordinated water mol\u00adecule; all ligands are monodentate. The four O atoms in the equatorial plane around the NiII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 7.2\u2005(1)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 72.80\u2005(4)\u00b0. An intra\u00admolecular O\u2014H\u22efO hydrogen bond links the uncoordinated water mol\u00adecule to one of the carboxyl\u00adate groups. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network.In the mononuclear title compound, [Ni(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2]\u00b72H2O = 0.026                           wR(F                           2) = 0.067                           S = 1.04                           3740 reflections228 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.41 e \u00c5\u22123                        \u0394\u03c1min = \u22120.32 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810025985/ci5126sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025985/ci5126Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two pyridine rings in L form a dihedral angle of 50.0\u2005(2)\u00b0. L ligands bridge adjacent HgCl2 units into polymeric chains propagating in [010]. The crystal packing is further stabilized by weak inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings, with a centroid\u2013centroid separation of 3.529\u2005(9)\u2005\u00c5.In the title coordination polymer, [HgCl DOI: 10.1107/S1600536812035775/cv5327Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The small deviations from the ideal tetra\u00adhedral geometry around the P atoms are illustrated by C\u2014P\u2014C angles ranging from 104.08\u2005(9) to 106.46\u2005(9)\u00b0. In the crystal, the mol\u00adecules are linked by weak C\u2014H\u22efF, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Ir(C DOI: 10.1107/S1600536812035593/hb6932Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "IV atom in the centrosymmetric title complex, [Sn2(CH3)4(NCS)2(OH)2], adopts a distorted trigonal\u2013bipyramidal coordination environment defined by two methyl C atoms and one bridging hydroxide group in the equatorial plane while the other bridging hydroxide group and the N atom of the thio\u00adcyanate anion are in the apical >positions. The dinuclear species are linked through O\u2014H\u22efS and C\u2014H\u22ef S hydrogen-bonding inter\u00adactions into a three-dimensional network.The Sn For str al. 2007; Ng 4(NCS)2(OH)2] = 0.026wR(F2) = 0.056S = 1.111603 reflections71 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 1.06 e \u00c5\u22123\u0394\u03c1min = \u22120.64 e \u00c5\u22123\u0394\u03c1COLLECT  used to solve structure: SIR97  I, global. DOI: Click here for additional data file.10.1107/S1600536812043462/wm2689Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II ion in the title complex, [Pd(NCS)2(C14H10N4)], is four-coordinated in a distorted square-planar environment by the two pyridine N atoms of the chelating 2,3-di-2-pyridyl\u00adpyrazine (dpp) ligand and two S atoms from two thio\u00adcyanate anions. The pyridine rings are considerably inclined to the least-squares plane of the PdS2N2 unit [maximum deviation = 0.027\u2005(1)\u2005\u00c5], making dihedral angles of 70.3\u2005(2) and 69.2\u2005(1)\u00b0. The pyrazine ring is almost perpendicular to the PdS2N2 plane, with a dihedral angle of 86.3\u2005(1)\u00b0. The thio\u00adcyanate ligands are located on opposite sides of the PdS2N2 unit plane and are almost linear [N\u2014C\u2014S angles = 177.8\u2005(6) and 178.9\u2005(6)\u00b0]. The complex mol\u00adecules are stacked in columns along the b axis and are connected by inter\u00admolecular C\u2014H\u22efN hydrogen bonds, forming chains along the a axis.The Pd X2(dpp)] , see: Ha ] = 0.046wR(F2) = 0.100S = 1.003247 reflections226 parametersH-atom parameters constrainedmax = 0.89 e \u00c5\u22123\u0394\u03c1min = \u22120.66 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II complex, [Cd2(C7H5O4)4(C12H8N2)2(H2O)2], the CdII cation is coord\u00adinated by a bidentate phenanthroline (phen) ligand, three dihy\u00addroxy\u00adbenzoate (dhba) anions and one water mol\u00adecule in a distorted CdN2O4 octa\u00adhedral geometry. Among the dhba anions, two anions bridge two CdII cations to form the dimeric complex with significant different Cd\u2014O bond distances of 2.2215\u2005(19) and 2.406\u2005(2)\u2005\u00c5. The centroid\u2013centroid distance of 3.4615\u2005(19)\u2005\u00c5 between two nearly parallel benzene rings of the dhba and phen ligands coordinating to the same CdII cation indicates the existence of intra\u00admolecular \u03c0\u2013\u03c0 stacking in the complex. Extensive O\u2014H\u22efO hydrogen bonding and inter\u00admolecular weak C\u2014H\u22efO hydrogen bonding help to stabilize the crystal structure. One hy\u00addroxy group of the monodentate dhba ligand is disordered over two sites with a site-occupancy ratio of 0.9:0.1.In the title centrosymmetric dimeric Cd DOI: 10.1107/S1600536810021252/ng2775Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The \u2013C\u00a0CH and the chlorine ligands are disordered over two equivalent positions (0.5 occupancy each). The coordination geometry is distorted octa\u00adhedral, with the \u2013C\u00a0CH fragment and the Cl ligand in trans positions. The four P atoms occupy the equatorial plane of the octa\u00adhedron and the chloride and acetyl\u00adide ligands the axial positions.The mol\u00adecular structure of the title compound,  Cl(C26H24P2)2] = 0.030wR(F2) = 0.072S = 1.096470 reflections293 parametersH-atom parameters constrainedmax = 0.49 e \u00c5\u22123\u0394\u03c1min = \u22120.48 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: Click here for additional data file.10.1107/S1600536812044558/bg2483Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The asymmetric unit contains two complex cations, two hexa\u00adfluoridophosphate anions and one uncoordinated water mol\u00adecule. In one of the hexa\u00adfluoridophosphate anions, four of the F aroms are disordered over two sets of sites in a 0.632\u2005(11):0.368\u2005(11) ratio. In the crystal, the cations, anions and water mol\u00adecules are connected by O\u2014H\u22efO and O\u2014H\u22efF hydrogen bonds. \u03c0\u2013\u03c0 inter\u00adactions are present between the pyridine rings [centroid\u2013centroid distance = 3.814\u2005(1)\u2005\u00c5].In the title complex, [Co(C DOI: 10.1107/S1600536811023270/hy2438Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing exhibits weak inter\u00admolecular Cl\u22efCl contacts of 3.279\u2005(4)\u2005\u00c5, \u03c0\u2013\u03c0 inter\u00adactions between the substituted Cp rings of two neighbouring 2-chloro-1-ferrocenyl\u00adethanone mol\u00adecules [centroid\u2013centroid distance = 3.534\u2005(3)\u2005\u00c5], and weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds. In the title co-crystal, [Fe(C DOI: 10.1107/S1600536811038244/cv5144Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each paddle-wheel unit is joined to four such neighbours through bridging dicarboxyl\u00adate ligands, producing a two-dimensional undulating layer parallel to (-101). Adjacent sheets are stacked in a parallel fashion to form a three-dimensional supra\u00admolecular structure which is stabilized by inter\u00adlayer \u03c0\u2013\u03c0 inter\u00adactions between benzene rings, with a centroid\u2013centroid distance of 3.722\u2005\u00c5. The range of Zn\u2014O bond lengths is 2.0440\u2005(17)\u20132.1256\u2005(15)\u2005\u00c5 and the Zn\u2014Cl bond length is 2.2622\u2005(6)\u2005\u00c5.The title compound, [Zn(C Cl] = 0.027wR(F2) = 0.078S = 1.072640 reflections181 parametersH-atom parameters constrainedmax = 0.45 e \u00c5\u22123\u0394\u03c1min = \u22120.45 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812020077/bg2452Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The thiophene rings form different dihedral angles [40.15\u2005(9) and 15.43\u2005(10)\u00b0] with the pyrazine ring. A strong \u03c0\u2013\u03c0 stacking inter\u00adaction occurs between adjacent pyrazine\u00adphenanthroline units with an inter\u00adplanar distance of 3.4352\u2005(16)\u2005\u00c5.The mol\u00adecule of the title compound, C DOI: 10.1107/S160053681201522X/aa2049Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The MnII atom is coordinated by four N atoms [Mn\u2014N = 2.2168\u2005(14) and 2.2407\u2005(14)\u2005\u00c5] from two 2,2\u2032-biimidazole ligands and two water mol\u00adecules [Mn\u2014O = 2.2521\u2005(14)\u2005\u00c5] in a distorted octa\u00adhedral geometry. Inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds consol\u00adidate the crystal packing, which also exhibits \u03c0\u2013\u03c0 inter\u00adactions between five-membered rings, with a centroid\u2013centroid distance of 3.409\u2005(2)\u2005\u00c5.The asymmetric unit of the title compound, [Mn(C DOI: 10.1107/S160053681202199X/cv5293Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The 2,2\u2032-bipyridine mol\u00adecule is slightly twisted with a dihedral angle between the pyridine rings of 7.35\u2005(12)\u00b0. Intra\u00admolecular C\u2014H\u22efS hydrogen bonds are present. In the crystal, mol\u00adecules are stacked along the c axis by \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.6021\u2005(15) and 3.6401\u2005(16)\u2005\u00c5. The crystal structure also features weak C\u2014H\u22ef\u03c0 inter\u00adactions.In the title benzene-solvated heteroleptic lithium complex, [Li(C DOI: Click here for additional data file.10.1107/S160053681300456X/rz5044Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atoms are linked by the bridging ligands into a layer parallel to (101). The presence of intra\u00adlayer O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine and benzene rings [centroid\u2013centroid distances = 3.808\u2005(2) and 3.927\u2005(2)\u2005\u00c5] stabilizes the layer. Further O\u2014H\u22efO hydrogen bonds link the layers and the dimethyl\u00adformamide solvent mol\u00adecules.In the title compound, {[Cu(C DOI: Click here for additional data file.10.1107/S1600536813006430/hy2619Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The product contains an unusual six-membered thiol\u00adate\u2013carboxyl\u00adate chelate ring. This slightly distorted octa\u00adhedral complex exhibits cis angles ranging from 77.55\u2005(11) to 97.30\u2005(8)\u00b0 due to the presence of the thiol\u00adate\u2013carboxyl\u00adate chelate ring and the constrained bipyridine group. The crystal packing appears to be controlled by a combination of \u03c0-stacking [centroid\u2013centroid distance = 3.611\u2005(2)\u2005\u00c5] and C\u2014H\u22efO inter\u00adactions.The title complex, [Pt(CH DOI: 10.1107/S1600536811013626/tk2735Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds into chains along [100]. These chains are further linked by weak \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances in the range of 3.609\u2005(2)\u20133.758\u2005(1)\u2005\u00c5, forming a three-dimensional supra\u00admolecular network.In the title centrosymmetric tetra\u00adnuclear complex, [Mn DOI: 10.1107/S1600536810049433/lh5168Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The AgI ion exhibits a slightly distorted tetra\u00adhedral coordination geometry formed by a P atom from a triphenyl\u00adphosphane ligand, two metal-bridging S atoms from thio\u00adsemicabazide ligands and one chloride ion. The S atoms bridge two symmetry-related AgI ions, forming a strictly planar Ag2S2 core with an Ag\u22efAg separation of 2.7802\u2005(7)\u2005\u00c5. There is an intra\u00admolecular N\u2014H\u22efCl hydrogen bond. In the crystal, N\u2014H\u22efCl and N\u2014H\u22efS hydrogen bonds link complex mol\u00adecules, forming layers parallel to (001). These layers are connected through \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.665\u2005(2)\u2005\u00c5], leading to the formation of a three-dimensional network.The dinuclear title complex, [Ag For pot al. 1999; Wujec e al. 2009; Mohareb al. 2009; He et a al. 2012. For exa al. 2012; Lobana  al. 2008.2Cl2(CH5N3S)2(C18H15P)2] = 0.026wR(F2) = 0.069S = 1.065026 reflections251 parameters5 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.38 e \u00c5\u22123\u0394\u03c1min = \u22120.55 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812051562/lh5573Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the central benzene ring and each of the two symmetry-related outer benzene rings is 5.1\u2005(2)\u00b0. The crystal structure is stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances in the range 3.466\u2005(2)\u20133.6431\u2005(16)\u2005\u00c5.In the title complex, [Cu(C DOI: 10.1107/S1600536810042789/lh5150Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Within the mononuclear complex mol\u00adecule, intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions are observed, the first between a coordinated phen mol\u00adecule and a DHB ligand [centroid\u2013centroid distance = 3.7291\u2005(16)\u2005\u00c5], and the second between a coordinated phen mol\u00adecule and an uncoordinated phen ligand [centroid\u2013centroid distance = 3.933\u2005(2)\u2005\u00c5]. Inter\u00admolecular \u03c0\u2013\u03c0 stacking is observed between adjacent complexes [inter\u00adplanar distance = 3.461\u2005(3)\u2005\u00c5]. Intra- and inter\u00admolecular O\u2014H\u22efO hydrogen bonds are observed in the DHB ligands and between a water mol\u00adecule and DHB ligands, respectively. O\u2014H\u22efN hydrogen bonds are also observed in the DHB ligands and between uncoordinated phen mol\u00adecules and aqua ligands.In the title compound, [La(C DOI: 10.1107/S1600536810047318/vm2058Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Bi\u2014O bond lengths are 2.283\u2005(3) and 2.309\u2005(2)\u2005\u00c5, but as a result of additional long Bi\u22efO inter\u00adactions [2.787\u2005(3) and 2.734\u2005(3)\u2005\u00c5], one of the C\u2014Bi\u2014C angles is 148.62\u2005(13)\u00b0. In the crystal, weak C\u2014H\u22efO hydrogen bonds connect pairs of mol\u00adecules into inversion dimers. These dimers are further connected by weak C\u2014H\u22ef\u03c0 inter\u00adactions into chains along [100] .In the title mol\u00adecule, [Bi(C DOI: Click here for additional data file.10.1107/S1600536813013317/lh5612Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The independent Fe2S2 fragment [Fe\u2014Fe = 2.527\u2005(1)\u2005\u00c5] is in a butterfly conformation, and each Fe atom displays a pseudo-square-pyramidal coordination geometry. The phosphane group occupies an apical position [Fe\u2014P = 2.2670\u2005(14)\u2005\u00c5]. In the crystal, weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into chains along [110]. In the title compound, [Fe DOI: 10.1107/S160053681105584X/cv5221Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII ion and the water O atom lie on a twofold axis. The CuII ion exhibits a six-coordinate distorted octa\u00adhedral geometry, with two N atoms from the bipy ligand [Cu\u2014N = 1.9996\u2005(16)\u2005\u00c5] and four O atoms from two 3-meth\u00adoxy\u00adbenzoate ligands [Cu\u2014O = 1.9551\u2005(15) and 2.6016\u2005(16)\u2005\u00c5]. The mol\u00adecules are linked by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming a three-dimensional network.The title compound, [Cu(C DOI: 10.1107/S1600536811005563/rn2078Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It has an E conformation with respect to the azomethine double bond and a Z conformation about the amide C=N bond. The CuII atom has a slightly distorted square-pyramidal coordination geometry. The crystal packing involves inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22ef\u03c0 and two types of \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.9958\u2005(10) and 3.7016\u2005(13)\u2005\u00c5.The binuclear molecule of the title compound, [Cu DOI: 10.1107/S1600536812031467/fj2577Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The [Co(CN)6]3\u2212 anion exhibits an octa\u00adhedral geometry. In the structure, cations and anions are linked alternatively through O\u2014H\u22efO, O\u2014H\u22efN, N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.523\u2005(2)\u20134.099\u2005(2)\u2005\u00c5] and van der Waals forces, forming a three-dimensional supra\u00admolecular network.The structure of the title compound, (C DOI: Click here for additional data file.10.1107/S1600536813003632/rz5042Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "III compound, {[Sm(C9H7O3)3(H2O)]\u00b7H2O}n, was obtained under hydrothermal conditions. Its structure is isotypic with the analogous Eu complex. The latter was reported incorrectly in space group P1 by Yan et al. . This was corrected by Marsh  to P-1. The SmIII ion is nine-coordinated by O atoms from one coordinating water molecule and the remaining ones from the 3-(3-hy\u00addroxy\u00adphen\u00adyl)prop-2-enoatate anions , leading to a distorted tricapped trigonal\u2013prismatic coordination polyhedron surrounded by solvent water mol\u00adecules. In the crystal, extensive intermolecular O\u2014H\u22efO hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid separation = 3.9393\u2005(1)\u2005\u00c5] lead to the formation of a three-dimensional supra\u00admolecular network.The title Sm DOI: 10.1107/S1600536812013724/zj2052Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "N. The proposed method has an O(N3 \u00b7 Multiplication(N) + N4) preprocessing time, after which a binomial coefficient C with 0 \u2264 Q \u2264 P \u2264 2N \u2212 1 can be computed modulo 2N in O(N2 \u00b7 log(N) \u00b7 Multiplication(N)) time. Multiplication(N) denotes the time complexity of multiplying two N-bit numbers, which can range from O(N2) to O(N \u00b7 log(N) \u00b7 log(log(N))) or better. Thus, theoverall time complexity for evaluating M binomial coefficients C modulo 2N with 0 \u2264 Q \u2264 P \u2264 2N \u2212 1 is O((N3 + M \u00b7 N2 \u00b7 log(N)) \u00b7 Multiplication(N) + N4). After preprocessing, we can actually compute binomial coefficients modulo any 2R with R \u2264 N. For larger values of P and Q, variationsof Lucas' theorem must be used first in order to reduce the computation tothe evaluation of multiple (O(log\u2061(P))) binomial coefficients C  modulo 2N with 0 \u2264 Q\u2032 \u2264 P\u2032 \u2264 2N \u2212 1.I present a new algorithm for computing binomial coefficients modulo 2 N\u2009\u2009(N \u2265 1). The definition of the binomial coefficient C is the usual one:In this paper I present a novel efficient algorithm for computing binomial coefficients modulo 2P \u2264 2N \u2212 1, and after fully handling this case, we will discuss how to compute C modulo 2N for P \u2265 2N.We will mainly consider the case where O(N3 \u00b7 Multiplication(N) + N4) time, where Multiplication(N) is the time complexity for multiplying two N-bit numbers. Multiplication(N) can range from O(N2)  to O(N \u00b7 log\u2061\u2061(N) \u00b7 log\u2061\u2061(log\u2061\u2061(N))) or slightly better . FFODD will be equal to the product (modulo\u2009\u20092N) of all the odd numbers from the interval . Thus, we will haveWe will first evaluate FODD is easy to compute. If Q(1) = 0, then FFODD = 1; otherwise it is equal to SOSP(Q(1), 0).FFODD(i > 1. Let X(i) be equal to 2Q(1) + \u22ef+2Q(i\u22121). If Q(i) = 0, then FFODD = (X(i) + 1)\u2009mod\u2061\u20092N. Otherwise we can write FFODD asLet us consider now the case By using Newton's binomial theorem, we can rewrite  as(27)\u2211j up to min\u2061{2Q(i)\u22121, N \u2212 1}, because for j \u2265 N, the corresponding term of the sum is zero modulo 2N. We should also notice that SSP(Q(i) \u2212 1, j) is multiplied by 2j. Since its precision is larger than N \u2212 j, the multiplication of SSP(Q(i) \u2212 1, j) and 2j is exact modulo 2N. Then we iterate with j in descending order. For the initial value of j, we compute XP(i) = (X(i)\u22121)j; for the other values, we only multiply XP(i) by (X(i)\u22121)\u22121 in order to obtain XP(i) as (X(i)\u22121)j. We now have an algorithm performing O(N) multiplications of N-bit numbers for computing FFODD. Overall, we have an algorithm performing O(N2) multiplications of N-bit numbers for computing FODD(P) (O(N) multiplications for each of the O(N) bits of P). However, we can do better by rewriting  is even. In fact, it is a multiple of 2Q(i\u22121), meaning that it is at least a multiple of 2Q(i)+1. For j > (N/(Q(i) + 1)), each term of the sum will be zero modulo 2N. Thus, we only need to consider at most N/(Q(i) + 1) + 1 terms (from j = 0 to j = N/(Q(i) + 1)). We will start with XP(i) = 1 when j = 0, and then for each subsequent value of j, we will multiply XP(i) by X(i) in order to have XP(i) = X(i)j at each iteration.Note that O(N \u00b7 log\u2061(N)) terms for computing FODD(P)(O(N + N/(Q(2) + 1) + N/(Q(3) + 1)+\u22ef+N/(Q(K) + 1))); for each such term, an N-bit multiplication needs to be performed.Overall we only need to consider P), we can use it in order to write F2(P > 1) asNow that we have a method of efficiently computing FODD(F2(0 \u2264 P \u2264 1) is equal to 1. Since P is of the order of magnitude of 2N and FODD(P) can be evaluated with O(N \u00b7 log\u2061(N))\u2009\u2009N-bit multiplications, computing F2(P) will require O(N2 \u00b7 log\u2061(N))\u2009\u2009N-bit multiplications, obtaining an O(N2 \u00b7 log\u2061(N) \u00b7 Multiplication\u2009(N)) time complexity.C with 0 \u2264 Q \u2264 P \u2264 2N \u2212 1. In order to evaluate it modulo 2N we will first need to compute F2(P), F2(Q), and F2(P \u2212 Q). Then, we will need to find the largest exponent exp\u2061(X) such that 2X)exp\u2061\u2009\u2009N-bit multiplications. Computing exp\u2061(X) where X \u2264 2N \u2212 1 can be performed in O(N2) time (O(N) bit shifts to the right and O(N)\u2009\u2009N-bit number additions). Thus, the time complexity for computing the binomial coefficient modulo 2N is dominated by the computation of F2(P), F2(Q), and F2(P \u2212 Q).As discussed earlier, the multiplicative inverse of an odd number by using , using OC modulo 2N for P \u2265 2N (and 0 \u2264 Q \u2264 P), we need to make use of some variations of Lucas' theorem [P = P1 \u00b7 2N + P0 and Q = Q1 \u00b7 2N + Q0, then, according to [In order to compute a binomial coefficient  theorem . If P = rding to , we haveC modulo 2N, we will need to evaluate O(log\u2061(P)) binomial coefficients C, where 0 \u2264 Q\u2032, P\u2032 \u2264 2N \u2212 1. After the O(N3 \u00b7 Multiplication(N)) preprocessing stage, evaluating C modulo 2N will take only O(N2 \u00b7 log\u2061(N) \u00b7 log\u2061(P) \u00b7 Multiplication(N) + log\u20612\u2061(P)) time (the log2(P) factor appears when P \u2265 2N because we need to perform O(log\u2061(P)) divisions, each of which takes O(log\u2061(P)) time because they can be implemented by shifting bits to the right, in order to obtain the O(log\u2061(P)) binomial coefficients or factorials which are needed in order to compute C modulo 2N).Thus, in order to compute C modulo 2N (for P \u2265 2N) to the computation of multiple (O(log\u2061(P))) factorials P\u2032! (of a restricted type) with P\u2032 \u2264 2N \u2212 1 were presented in [Other methods for reducing the computation of ented in .C modulo R, where R is a prime number. The computation of C is reduced to the computation of multiple (O(log\u2061(P))) binomial coefficients C modulo R, with 0 \u2264 Q\u2032 \u2264 P\u2032 \u2264 R \u2212 1. In [M is to evaluate them modulo the  prime powers which are divisors of M and then use the Chinese Remained Theorem [M , but inerved in  a more derved in .O(log\u20612\u2061(P) + v4 \u00b7 log\u2061(P) \u00b7 log\u2061(u) + v4 \u00b7 u \u00b7 log\u20613\u2061(u)) time for computing C modulo uv, where u is a prime number  + N4 \u00b7 log\u2061(P) + N4). If we consider Multiplication(N) = O(N2), our algorithm takes O(N5) time for preprocessing and O(N4 \u00b7 log\u2061(N) \u00b7 log\u2061(P) + log\u20612\u2061(P)) in order to compute C in the general case. These time complexities are slightly worse than the ones obtained in [N) = O(N \u00b7 log\u2061(N) \u00b7 log\u2061(log\u2061(N))) [O(N4 \u00b7 log\u2061(N) \u00b7 log\u2061(log\u2061(N))) time complexity for the preprocessing stage and an O(N3 \u00b7 log\u20612\u2061(N) \u00b7 log\u2061\u2061(log\u2061(N)) \u00b7 log\u2061(P) + log\u20612\u2061(P)) time complexity for actually computing the binomial coefficient modulo 2N. In this case our time complexities are slightly better than the ones presented in [P) > log\u2061(N) \u00b7 log\u2061\u2061(log\u2061(N))). However, it is not clear which time complexity for the multiplication of two N-bit numbers was considered in [An algorithm for computing binomial coefficients modulo prime powers (for any prime) was presented in . The algtated in , but a sained in . Howeverog\u2061(N))) , 2, we oented in  .In this paper I presented a novel efficient algorithm for computing binomial coefficients modulo 2The time complexity of the presented algorithm is comparable with that of state-of-the-art algorithms for computing binomial coefficients modulo prime powers . In factN . If the values SSP defined in P, Q) values in a more efficient manner.When computing a small number of binomial coefficients , the bottleneck of the algorithm (in the preprocessing stage) consists of the computation of sums of products of elements of subsets having sizes 0 to"}
{"text": "The dimethyl\u00adamino groups are orientated at 41.80\u2005(7) and 36.43\u2005(7)\u00b0 with respect to the borazine ring. The nitro\u00adoxy group is almost normal to the borazine ring [dihedral angle = 85.33\u2005(14)\u00b0]. The methyl C atom trans to the NO3 group is displaced by \u22120.512\u2005(3)\u2005\u00c5 from the ring plane, whereas the two ortho-methyl C atoms are displaced by 0.239\u2005(3) and 0.178\u2005(3)\u2005\u00c5.In the title compound, C DOI: Click here for additional data file.10.1107/S1600536813007484/hb7055Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813007484/hb7055Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mean bond lengths in the biferrocene unit are Fe\u2014C = 2.048\u2005(10)\u2005\u00c5 and C\u2014C = 1.427\u2005(8)\u2005\u00c5 within the cyclo\u00adpenta\u00addienyl rings. The B\u2014N bond lengths of the BH3 protected amine is 1.631\u2005(3)\u2005\u00c5. The inter\u00adplanar angle between the two connected cyclo\u00adpenta\u00addienyl rings is 54.29\u2005(8)\u00b0 and the corresponding Fe\u2014Cg\u2014Cg\u2014Fe torsion angle is \u221252.5\u00b0. The conformation of the mol\u00adecule is stabilized by an intra\u00admolecular C\u2014H\u22efBr inter\u00adaction.The title structure, [Fe DOI: 10.1107/S1600536811049270/bq2322Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is controlled by C\u2014H\u22efO hydrogen bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions involving the benzene rings, with a centroid\u2013centroid distance of 3.4220\u2005(1)\u2005\u00c5.In the title compound, (C DOI: 10.1107/S160053681002893X/pv2307Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The amide group is almost perpendicular to the plane of the substituted Cp ring, with a C\u2014N\u2014C\u2014C torsion angle of 101.3\u2005(2)\u00b0, and the N and O atoms in the ethanoyl group are coplanar, with a C\u2014N\u2014C\u2014O torsion angle of \u22120.7\u2005(3)\u00b0. Weak C\u2014H\u22efO hydrogen bonds link adjacent mol\u00adecules.In the title compound, [Fe(C DOI: 10.1107/S1600536812016303/hy2528Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the NiII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 23.67\u2005(8)\u00b0, while the pyridine and benzene rings are oriented at an angle of 89.04\u2005(4)\u00b0. The coordinating water mol\u00adecule links with the carboxyl\u00adate group via an O\u2014H\u22efO hydrogen bond. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 contacts between benzene rings [centroid\u2013centroid distance = 3.8414\u2005(7)\u2005\u00c5] may further stabilize the structure. A weak C\u2014H\u22ef\u03c0 inter\u00adaction also occurs.In the title complex, [Ni(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.023wR(F2) = 0.063S = 1.073492 reflections216 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.40 e \u00c5\u22123\u0394\u03c1min = \u22120.42 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812026943/xu5564Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, there are no hydrogen bonds  present, and only very weak \u03c0\u2013\u03c0 inter\u00adactions  are observed [centroid\u2013centroid distance = 3.985\u2005(4)\u2005\u00c5], which connect neighbouring tetra\u00adnuclear units into a chain motif along the b axis.In the title centrosymmetric tetra\u00adnuclear complex, [Cu DOI: 10.1107/S1600536811026468/su2284Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title salt, [Cu(C10H24N4)(H2O)2][CH3(CH2)5CO2]2\u00b72H2O, is chelated by the four N atoms of the 1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane (cyclam) ligand and is coordinated by two water mol\u00adecules in a tetra\u00adgonally Jahn\u2013Teller-distorted octa\u00adhedral geometry. The CuII atom lies on a center of inversion. The cations, anions and uncoordinated water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a layer structure parallel to (100). The alkyl chain of the anion is disordered over two positions in a 0.82\u2005(1):0.18\u2005(1) ratio.The Cu DOI: 10.1107/S1600536810025687/bt5285Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each complex mol\u00adecule, the Cu atom is O,N,O\u2032-chelated by the tridentate Schiff base ligand and N,N\u2032-chelated by the 1,10-phenanthroline ligand in a distorted square-pyramidal geometry. The Cu\u2014N bond distances in the apical directions are 2.298\u2005(4) and 2.268\u2005(4)\u2005\u00c5. In the crystal, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds together with C\u2014H\u22ef\u03c0 inter\u00adactions result in a three-dimensional supra\u00admolecular structure.The asymmetric unit of the title complex, [Cu(C DOI: 10.1107/S160053681004554X/xu5077Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom is located about an inversion centre. The mol\u00adecule consists of three planar units , adopting a staircase-like structure. The six-membered metallocycles have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triaza\u00adpenta\u00addienyl ligands by 0.246\u2005(5)\u2005\u00c5. The ipso-C atoms of the CCl3 substituents are slightly out of the 1,3,5-triaza\u00adpenta\u00addienyl planes by 0.149\u2005(6) and \u22120.106\u2005(6)\u2005\u00c5. The CCl3 groups of each 1,3,5-triaza\u00adpenta\u00addienyl ligand are practically in the energetic\u00adally favourable mutually eclipsed conformation. In the crystal, the mol\u00adecules are packed in stacks along the a axis. The mol\u00adecules in the stacks are held together by two additional axial Cu\u22efCl inter\u00adactions of 3.354\u2005(2)\u2005\u00c5. Taking the axial Cu\u22efCl inter\u00adactions into account, the CuII atom exhibits a distorted [4\u00a0+\u00a02]-octa\u00adhedral coordination environment. The stacks are bound to each other by weak inter\u00admolecular attractive Cl\u22efCl [3.505\u2005(2)\u20133.592\u2005(3)\u2005\u00c5] inter\u00adactions.The title compound, [Cu(C DOI: 10.1107/S1600536812036124/aa2069Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The mol\u00adecule is located about a twofold rotation axis. The coordination environment of the SnIV atom is a distorted octa\u00adhedron, with two bidentate 2-pyridine\u00adseleno\u00adlate ligands inclined to each other at an angle of 83.96\u2005(7)\u00b0. The two Sn\u2014Cl and two Sn\u2014N bonds are in cis configurations, while the two Sn\u2014Se bonds of 2.5917\u2005(3)\u2005\u00c5 are in a trans configuration, with an Se\u2014Sn\u2014Se angle of 157.988\u2005(15)\u00b0. In the crystal, \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid-to-centroid distance of 3.758\u2005(3)\u2005\u00c5] and weak inter\u00admolecular C\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into chains along the c axis.The title compound, [SnCl DOI: 10.1107/S1600536813014657/cv5413Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Each AgI ion is coordinated by two N atoms from two bridging bipy ligands, forming chains along [101]. \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.638\u2005(8) and 3.688\u2005(8)\u2005\u00c5] connect the chains. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the uncoord\u00adinated water mol\u00adecules and the perchlorate anions.In the title compound, {[Ag DOI: 10.1107/S1600536811040153/hy2472Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the two I\u2212 anions is disordered over two sets of sites, with refined occupancies of 0.66\u2005(5) and 0.34\u2005(5). The CdII ions are bridged by bmi ligands, leading to the formation of a chain along [001]. Dimethyl\u00adformamide solvent mol\u00adecules are located between these chains. Classical N\u2014H\u22efO hydrogen bonding between the bmi ligands and the solvent mol\u00adecules leads to a consolidation of the structure.In the title complex, {[CdI N-heterocyclic ligands, see: Meng et al. ]\u00b7C3H7NO = 0.035                           wR(F                           2) = 0.071                           S = 1.15                           3950 reflections218 parametersH-atom parameters constrainedmax = 0.42 e \u00c5\u22123                        \u0394\u03c1min = \u22120.77 e \u00c5\u22123                        \u0394\u03c1                                 CrystalClear  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811050823/wm2569Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bond lengths  and angles (C\u2014Fe\u2014Fe and Fe\u2014S\u2014Fe) are within expected ranges. The S\u22efS distance [2.9069\u2005(12)\u2005\u00c5] and the dihedral angle between two Fe\u2014S\u2014Fe planes [78.5\u2005(3)\u00b0] of the butterfly-shaped Fe2S2 core are enlarged compared with related bridged dithiol\u00adate diiron analogues. The calculated 4-benzothia\u00adzolebenzyl best planes are almost parallel [dihedral angle = 3.7\u2005(7)\u00b0].The title compound, [Fe DOI: 10.1107/S1600536812007581/vm2158Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "A short Cd\u22efN contact [2.890\u2005(3)\u2005\u00c5] to the monodentate sulfadiazinate ion also occurs. The dihedral angles between the planes of the aromatic rings of the anions are 86.81\u2005(14) and 68.65\u2005(14)\u00b0. The crystal structure features inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.In the title compound, [Cd(C DOI: 10.1107/S1600536811019635/hb5888Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The employed \u03b1-diimine opens up, forming a highly asymmetric ammonium that has its protons at one of the N atoms [N\u2014C= 1.264\u2005(4) and 1.516\u2005(4)\u2005\u00c5]. One of the C=N double bonds was oxidized to C\u2014N, which is consistent with the bond length of 1.516\u2005(4)\u2005\u00c5. Meanwhile SnIV was reduced to SnII. The (SnCl)3\u2212 anion is trigonal\u2013pyramidal. In the crystal, mol\u00adecules are linked by C\u2014H\u22efCl, N\u2014H\u22efCl, N\u2014H\u22efN and C\u2014H\u22efN bonds. The crystal studied was twinned by pseudo-merohedry.In the title compound, (C DOI: 10.1107/S1600536812014729/hp2032Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The NiII ion is six-coordinated in a distorted octa\u00adhedral geometry by two N, two O and two S atoms. An intra\u00admolecular C\u2014H\u22efS hydrogen bond generates an S(6) ring motif. In the crystal, mol\u00adecules are linked through inter\u00admolecular N\u2014H\u22efS, N\u2014H\u22efO, C\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds into infinite two-dimensional network parallel to the ab plane. The structure is further stablized by weak C\u2014H\u22ef\u03c0 inter\u00adactions. The dimethylformamide solvent molecule is disordered over two sets of sites in a 0.514\u2005(15):0.486\u2005(15) ratio.The asymmetric unit of the title compound, [Ni(C DOI: 10.1107/S1600536812012834/zj2062Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Two O atoms of one bidentate 2-meth\u00adoxy\u00adbenzoate ligand are each disordered over two positions, with site-occupancy factors of 0.579\u2005(4) and 0.421\u2005(4). In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming a two-dimensional network lieing parallel to the bc plane. The crystal packing is further stablized by \u03c0\u2013\u03c0 stacking inter\u00adactions between the dmphen rings of neighboring mol\u00adecules, with distances between their parallel dmphen ring planes of 3.517\u2005(3) and 3.610\u2005(3)\u2005\u00c5.In the title compound, [Cd(C DOI: 10.1107/S1600536812010835/bg2438Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The asymmetric unit consists of half a Lindquist anion and one [Cu(phen)(PPh3)2]+ cationic complex. In the cation, there are intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.617\u2005(2) and 3.7272\u2005(18)\u2005\u00c5]. This inorganic\u2013organic adduct is connected by C\u2014H\u22efO hydrogen bonds, forming a two dimensional network lying in the ab plane. These networks are connected by C\u2014H\u22ef\u03c0 inter\u00adactions into a three-dimensional structure.The title compound, [Cu(C DOI: 10.1107/S1600536812036367/hg5234Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Extensive inter\u00admolecular N\u2014H\u22efO, N\u2014H\u22efN, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, as well as weak inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efO inter\u00adactions occur in the crystal. \u03c0\u2013\u03c0 stacking between between pyrazine rings of coordinating ligands and lattice molecules [centroid\u2013centroid distance = 3.5669\u2005(14)\u2005\u00c5] may further stabilize the structure.In the title compound, [Cd(NO DOI: 10.1107/S1600536812028577/xu5577Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Fe\u2014O bond lengths are in the range 1.9818\u2005(18)\u20131.9957\u2005(18)\u2005\u00c5. The trans O\u2014Fe\u2014O angles are 169.06\u2005(13) and 171.54\u2005(8)\u00b0, whereas the corresponding cis angles are in the range 84.81\u2005(10)\u2013100.68\u2005(12)\u00b0. In the crystal, mol\u00adecules are linked via C\u2014H\u22efCl inter\u00adactions.In the title compound, [Fe(C DOI: 10.1107/S1600536812023215/im2375Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Cu\u2014N bond lengths in the base of the resulting CuN5 pyramid are in the range 2.016\u2005(3)\u20132.024\u2005(3)\u2005\u00c5 and the apical Cu\u2014N(\u00a0C) distance is 2.385\u2005(4)\u2005\u00c5. Based on the \u03c4 parameter, the shape of the coordination polyhedron is tetra\u00adgonal\u2013pyramidal (\u03c4 = 0). All atoms of the square-planar tetracyanidopalladate(II) moiety and the CuII ion are located on a mirror plane. The electroneutral mol\u00adecules inter\u00adact by N\u2014H\u22efN hydrogen bonds, resulting in the formation of a three-dimensional network.The title compound, [Cu(NH II complexes see: Escorihuela et al. 4] = 0.025wR(F2) = 0.061S = 1.001051 reflections81 parametersH-atom parameters constrainedmax = 0.54 e \u00c5\u22123\u0394\u03c1min = \u22121.26 e \u00c5\u22123\u0394\u03c1X-AREA  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813011033/ff2104Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The anions are disordered each over two sets of sites, with an occupancy ratio of 0.617\u2005(6):0.383\u2005(6). The distances from the Fe atoms to the centroids of the unsubstituted and substituted cyclo\u00adpenta\u00addienyl (Cp) rings are 1.645\u2005(1)/1.657\u2005(1) and 1.644\u2005(1)/1.647\u2005(1)\u2005\u00c5. The dihedral angles between the two Cp rings are 2.49\u2005(3) and 1.45\u2005(4)\u00b0 in the two ferrocenyl groups of the cations.The asymmetric unit of the title complex, [Fe(C DOI: 10.1107/S1600536812001766/hy2506Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In each mol\u00adecule, four penta\u00adfluoro\u00adbenzoate anions bridge the quadruply bonded Mo2               4+ unit that is, in addition, axially coordinated by two O atoms of tetra\u00adhydro\u00adfuran (THF) mol\u00adecules. In the two independent mol\u00adecules, the mean Mo\u2014Mo bond length is 2.110\u2005\u00c5. Since the THF mol\u00adecules are equally disordered over two sets of sites, there are four different Mo\u2014O distances in both half-mol\u00adecules with an overall mean of 2.542\u2005\u00c5. A zigzag chain is formed by \u03c0\u2013\u03c0 stacking inter\u00adactions between penta\u00adfluoro\u00adphenyl rings, indicated by a centroid\u2013centroid distance of 3.7054\u2005(11)\u2005\u00c5 and a centroid-to-plane distance of 3.4169\u2005(3)\u2005\u00c5. The extension of the unit gives a three-dimensional network structure with the THF mol\u00adecules located in the voids.In the asymmetric unit of the title compound, [Mo DOI: 10.1107/S1600536811033411/wm2516Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the CoII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 22.3\u2005(3)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 84.59\u2005(13)\u00b0. Intra\u00admolecular O\u2014H\u22efO hydrogen bonding occurs between the carboxyl\u00adate group and coordinated water mol\u00adecule. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network.In the title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.046wR(F2) = 0.110S = 1.163618 reflections203 parameters6 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 2.60 e \u00c5\u22123\u0394\u03c1min = \u22122.03 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S160053681201330X/xu5493Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The FeIII cation has an approximate octa\u00adhedral geometry, defined by six N atoms from two bpca\u2212 anions. The nearly parallel [dihedral angle = 1.50\u2005(1)\u00b0] bpca\u2212 anions form two-dimensional supermolecules along the a axis by the way of weak \u03c0\u2013\u03c0 stacking inteactirons . Intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonding occurs. The water mol\u00adecule [occupancies 0.520\u2005(5) and 0.480\u2005(5)], two carbonyl O atoms [occupancies 0.622\u2005(7) and 0.378\u2005(7)] and the four perchlorate O atoms [occupancies 0.887\u2005(4) and 0.113\u2005(4)] are each disordered over two positions.The structure of the title salt complex, [Fe(C DOI: 10.1107/S1600536811047684/jj2105Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds lead to a three-dimensional supra\u00admolecular network. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings and between the benzene and triazole rings [centroid\u2013centroid distances = 3.657\u2005(1) and 3.752\u2005(1)\u2005\u00c5] are observed.In the title compound, [Cu(C DOI: 10.1107/S1600536811018356/hy2429Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The average Ru\u2014S bond length is 2.41\u2005(1)\u2005\u00c5 and the average S\u2014Ru\u2014S bite angle is 81.13\u2005(19)\u00b0.In the title complex, [Ru(C DOI: Click here for additional data file.10.1107/S1600536813014141/hy2626Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The packing of the structure involves weak \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl and benzene rings of neighbouring ppaBr ligands [centroid\u2013centroid distance = 3.928\u2005(2)\u2005\u00c5] and inter\u00adactions between the Br atom on the ppaBr ligand and the hfac ligand [Br\u22efC = 3.531\u2005(2)\u2005\u00c5].In the title complex, [Co(C DOI: 10.1107/S1600536810032757/zs2056Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Co2+ ion, coordinated by three O atoms from two different carboxyl\u00adate groups and three water mol\u00adecules, displays a distorted octa\u00adhedral environment. In the crystal, \u03c0\u2013\u03c0 inter\u00adchain inter\u00adactions, with centroid\u2013centroid distances of 3.656\u2005(2) and 3.669\u2005(2)\u2005\u00c5 between the benzene rings of the ligands, assemble the chains into sheets parallel to (100). O\u2014H\u22efO hydrogen-bonding inter\u00adactions between the coordinating water mol\u00adecules and carboxyl\u00adate O atoms link the sheets into a three-dimensional network.The polymeric title compound, {[Co(C DOI: 10.1107/S1600536812009580/wm2597Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is made up of \u221e               1[Nb2PS10] chains expanding along [010]. These chains are built up from bicapped trigonal-prismatic [Nb2S12] units and tetra\u00adhedral [PS4] groups and are linked through a linear S\u2014Ag\u2014S bridge, forming a two-dimensional layer. These layers then stack on top of each other, completing the three-dimensional structure with an undulating van der Waals gap. The disordered Cs+ ions reside on sites with half-occupation in the voids of this arrangement. Short [2.8843\u2005(5)\u2005\u00c5] and long [3.7316\u2005(4)\u2005\u00c5] Nb\u2014Nb distances alternate along the chains, and anionic S2               2\u2212 and S2\u2212 species are observed. The charge balance of the com\u00adpound can be represented by the formula [Cs+]0.5[Ag+]0.5[Nb4+]2[PS4               3\u2212][S2               2\u2212]3.The quinter\u00adnary thio\u00adphosphate Cs DOI: 10.1107/S1600536810021768/wm2357Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the coordination cation, the CuII atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms from a bridging\u2013chelating carboxyl\u00adate group of the pyridine-2,6-dicarboxyl\u00adate anion, completing a distorted N4O2 octa\u00adhedral coordination environment. The TbIII atom, located on a twofold rotation axis, is nine-coordinated by three tridentate pyridine-2,6-dicarboxyl\u00adate anions forming an N3O6 donor set. The intra\u00admolecular Cu\u22efTb distance of 5.0592\u2005(11)\u2005\u00c5 indicates weak inter\u00adactions between the CuII and TbIII atoms. The coordination cations, nitrate anions and water mol\u00adecules are connected via O\u2014H\u22efO hydrogen bonds into layers parallel to the (001) plane. Moreover, there are extensive \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 4.332\u2005(7) and 3.878\u2005(5)\u2005\u00c5] between the phenanthroline ligands and between phenanthroline and pyridine-2,6-dicarboxyl\u00adate ligands.The asymmetric unit of the title compound, [Cu For the al. 2010; Yang et al. 2006.2Tb(C7H3NO4)3(C12H8N2)4]NO3\u00b74H2O = 0.041wR(F2) = 0.134S = 1.046454 reflections479 parameters27 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.88 e \u00c5\u22123\u0394\u03c1min = \u22121.09 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812031686/gk2483Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The central ion is coordinated by the thia\u00adzole N atom, the thio\u00adureido N and the S atom of the deprotonated thio\u00adsemicarbazone ligand. The other ligand is linked with the central ion through the C=S group. The deprotonated ligand intra\u00admolecularly hydrogen bonds to the thia\u00adzole ring N atom, while the ligand forms an inter\u00admolecular hydrogen bond to the thiol\u00adate S atom of the second ligand. The deprotonation of the tridentate ligand and its coordination to the CdII ion via the S atom strikingly affects the C\u2014S bond lengths. The C\u2014S bond lengths in the neutral and deprotonated ligands in the metal complex are 1.709\u2005(3) and 1.748\u2005(2)\u2005\u00c5, respectively, whereas it is 1.671\u2005(3)\u2005\u00c5 in the free ligand. In the metal complex, the Cd\u2014S distances are 2.6449\u2005(6) and 2.5510\u2005(6)\u2005\u00c5. The Cd\u2014I bond length is 2.7860\u2005(2)\u2005\u00c5.In the title complex, [Cd(C I(C12H12N4S2)] = 0.027wR(F2) = 0.060S = 1.028142 reflections354 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.92 e \u00c5\u22123\u0394\u03c1min = \u22120.60 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  global, I. DOI: Click here for additional data file.10.1107/S160053681300915X/bv2219Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The distorted trans square-planar environment is completed by two P atoms [Rh\u2014P = 2.3251\u2005(4)\u2005\u00c5] from two diphen\u00adyl(4-vinyl\u00adphen\u00adyl)phosphane ligands. The vinyl group is disordered over two sets of sites in a 0.668\u2005(10):0.332\u2005(10) ratio. The crystal packing exhibits weak C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the phenyl rings of neighbouring mol\u00adecules, with a centroid\u2013centroid distance of 3.682\u2005(2)\u2005\u00c5.In the title compound,  DOI: 10.1107/S1600536812013669/cv5270Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CdII ion is in a strongly distorted CdN2O5 penta\u00adgonal-bipyramidal geometry, defined by two N atoms from one 2,2\u2032-bipyridine ligand and five O atoms from three 2-phenyl\u00adquinoline-4-carboxyl\u00adate ligands, one monodentate, two bidentate. Weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.712\u2005(3)\u2005\u00c5] help to establish the packing of the structure.The neutral binuclear title complex, [Cd DOI: 10.1107/S1600536810049640/bh2323Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the components are linked into a three dimensional network by O\u2014H\u22efO, N\u2014H\u22efO, N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and a \u03c0\u2013\u03c0 inter\u00adaction with a centroid\u2013centroid distance of 3.6080\u2005(8)\u2005\u00c5.In the complex anion of the title compound, (C DOI: 10.1107/S1600536811011147/is2693Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, noncovalent inter\u00adactions play an important role in the stabilization of the structure, involving O\u2014H\u22efO, N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings of the pyridine-2,6-dicarboxyl\u00adate ligands [centroid\u2013centroid distance = 3.7138\u2005(15)\u2005\u00c5] and between the 8-hy\u00addroxy-2-methyl\u00adquinolinium cations .In the title compound, (C DOI: 10.1107/S1600536811021015/hy2430Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ni\u2014N distances range from 2.0594\u2005(12) to 2.0664\u2005(12)\u2005\u00c5, intra-ligand N\u2014Ni\u2014N angles range from 84.59\u2005(5) to 86.06\u2005(5)\u00b0, and adjacent inter-ligand N\u2014Ni\u2014N angles range between 93.94\u2005(5) and 95.41\u2005(5)\u00b0. In the crystal, inversion-related pyrazole rings are \u03c0\u2013\u03c0 stacked, with an inter\u00adplanar spacing of 3.4494\u2005(18)\u2005\u00c5, forming chains that propagate parallel to the a-axis direction. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds are present between water mol\u00adecules and tri\u00adfluoro\u00admethane\u00adsulfonate anions.In the title salt, [Ni(C DOI: 10.1107/S1600536813024252/tk5252Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atom is in a square-pyramidal coordination environment formed by four O atoms of four carboxyl\u00adate groups and one water mol\u00adecule, which is located in the apical position. The carboxyl\u00adate groups are twisted relative to the benzene rings by 11.09\u2005(16) and 45.55\u2005(19)\u00b0. The nitro groups are not coplanar with the parent aromatic rings [dihedral angles = 16.2\u2005(3)\u201351.45\u2005(14)\u00b0]. O\u2014H\u22efO hydrogen bonds between the coordinated water mol\u00adecules and one of the nitro groups, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.5764\u2005(12)\u2005\u00c5] between the benzene rings, assemble the complex mol\u00adecules into a one-dimensional polymeric structure which is further extended into a three-dimensional polymeric network via O\u2014H\u22efO hydrogen bonds involving the water molecules of crystallization.The title compound, [Cu DOI: 10.1107/S1600536811000547/gk2339Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The first reported polymorph of this complex was triclinic . The present polymorph crystallized in the monoclinic space group P21/c. The CuII ion is in a square planar environment and is coordinated by one phenolate O, one imine N and one pyridine N atom of the tridentate Schiff base ligand and by one water O atom. In the crystal, mol\u00adecules are linked through inter\u00admolecular O\u2014H\u22efO hydrogen bonds to form chains along the a axis.The title complex, [Cu(C al. 2010. Acta Cr For the al. 2010.13H10ClN2O)(H2O)]NO3\u00b7H2O = 0.037wR(F2) = 0.089S = 1.063410 reflections233 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.39 e \u00c5\u22123\u0394\u03c1min = \u22120.48 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXTL  I, global. DOI: 10.1107/S1600536812004564/qm2051Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The B atom deviates by 0.202\u2005(1)\u2005\u00c5 from the least-squares plane of the mesityl ring. All of the meth\u00adoxy groups are approximately coplanar with the 2,4,6-trimeth\u00adoxy\u00adphenyl ring, whereas the BOH group is twisted with respect to it by 19.5\u00b0. The borinic OH group is engaged in an intra\u00admolecular O\u2014H\u22efO hydrogen bond with one of ortho-meth\u00adoxy groups. The mol\u00adecular structure is stabilized by weak C\u2014H\u22efO contacts. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, generating a three-dimensional network.In the title mol\u00adecule, C DOI: 10.1107/S160053681002297X/pv2296Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One CdII ion is six-coordinated and exhibits a distorted octa\u00adhedral geometry, while the other two CdII ions are seven-coordinated, displaying a distorted penta\u00adgonal\u2013bipyramidal geometry. The CdII ions are bridged by two types of sulfate anions, producing inorganic chains along [100]. These chains are further connected by the H2bic ligands, leading to a three-dimensional framework. N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the imidazole and benzene rings  further stabilize the crystal structure. The asymmetric unit of the title compound, [Cd H-benzimidazole-5-carboxyl\u00adate com\u00adplexes, see: Gao et al. 2(SO4)2(H2O)3] = 0.025                           wR(F                           2) = 0.067                           S = 1.06                           3935 reflections361 parameters1 restraintH-atom parameters constrainedmax = 0.56 e \u00c5\u22123                        \u0394\u03c1min = \u22120.71 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811034477/hy2460Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ir=Ccarbene bond is strong and short and exerts a notable effect on the trans-Ir\u2014N bond, which is about 0.10\u2005\u00c5 longer than the two other Ir\u2014N bonds. The chloro\u00adform solvent mol\u00adecule is anchored via a weak C\u2014H\u22efCl hydrogen bond to the Cl atom of the Ir complex mol\u00adecule. In the crystal, the constituents adopt a layer-like arrangement parallel to (010) and are held together by weak inter\u00admolecular C\u2014H\u22efCl hydrogen bonds, as well as weak Cl\u22efCl [3.498\u2005(2)\u2005\u00c5] and Cl\u22ef\u03c0 [3.360\u2005(4)\u2005\u00c5] inter\u00adactions. A weak intra\u00admolecular C\u2014H\u22efO hydrogen bond is also observed.In the title compound, [Ir(C N,N\u2032,N\u2032\u2032)-iridium moiety Ir[TpMe2]. Its formation from [(TpMe2)Ir(C6H5)2(k1-N2)]  and eth\u00adoxy\u00adbenzene involved multiple C\u2014C,H,O,Cl bond transformations by the outstanding activity of the Ir[TpMe2] moiety. For general information on C\u2014H and C\u2014C activation, see: Lin & Yamamoto borate-moto 1999; Dyker (C8H7O)Cl]\u00b7CHCl3 = 0.028wR(F2) = 0.071S = 1.028053 reflections341 parametersH-atom parameters constrainedmax = 1.29 e \u00c5\u22123\u0394\u03c1min = \u22121.43 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813007344/lh5594Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. In each biphenyl unit, the phenyl rings are twisted from each other, making dihedral angles of 51.22\u2005(18), 42.94\u2005(16) and 26.95\u2005(16)\u00b0. The arsine-substituted phenyl rings make dihedral angles of 61.22\u2005(15), 87.17\u2005(15) and 83.32\u2005(15)\u00b0 with each other. The dihedral angles between the two benzene rings are 85.52\u2005(18) and 81.77\u2005(15)\u00b0 for the two diphenyl\u00adphosphanyl groups, respectively. In the crystal, mol\u00adecules are linked into dimers by inter\u00admolecular C\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.6981\u2005(18)\u2005\u00c5] inter\u00adactions stabilize the crystal structure.In the title  DOI: 10.1107/S160053681100078X/ng5095Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The structure of the dinuclear tetracation exhibits significant distortion from planarity in the bridging 2,3,5,6-tetra\u00adkis\u00ad(pyridin-2-yl)pyrazine (tppz) ligand, which has a saddle-like geometry with an average dihedral angle of 42.96\u2005(18)\u00b0 between adjacent pyridine rings. The metal\u2013ligand coordination environment is nearly equivalent for the two RuII atoms, which have a distorted octa\u00adhedral geometry due to the restricted bite angle [157.57\u2005(13)\u2013159.28\u2005(12)\u00b0] of their two mer-arranged tridendate ligands  orthogonal to each other. At the peripheral tpy ligands, the average Ru\u2014N bond distance is 2.072\u2005(4)\u2005\u00c5 for the outer N atoms trans to each other (Nouter) and 1.984\u2005(1)\u2005\u00c5 for the central N atoms . At the bridging tppz ligand, the average metal\u2013ligand distances are significantly shorter [2.058\u2005(4)\u2005\u00c5 for Ru\u2014Nouter and 1.965\u2005(1)\u2005\u00c5 for Ru\u2014Ncentral] as a result of both the geometric constraints and the stronger \u03c0-acceptor ability of the pyrazine-centered bridge. The dihedral angle between the two tpy planes is 27.11\u2005(6)\u00b0. The intra\u00admolecular linear distance between the two Ru atoms is 6.6102\u2005(7)\u2005\u00c5.In the title compound [Ru DOI: Click here for additional data file.10.1107/S1600536812051215/zl2523Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The binuclear complex mol\u00adecules are linked together by inter\u00admolecular O\u2014H\u22efO hydrogen bonds into a layer parallel to (100). The layers are connected by C\u2014H\u22efCl hydrogen bonds. Intra\u00admolecular O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.5958\u2005(16)\u2005\u00c5] are also present.In the centrosymmetric binuclear title compound, [Cu DOI: 10.1107/S1600536811035112/hy2462Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, weak N\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into layers, while weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 4.2758\u2005(18)\u2005\u00c5] also help to stabilize the packing.In the title compound, (C DOI: 10.1107/S1600536810046817/jh2229Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.6113\u2005(11)\u2005\u00c5] between two of the 4-fluoro\u00adphenyl groups is complemented by both C\u2014H\u22efF and C\u2014H\u22efO inter\u00adactions with distances in the range 2.51\u20132.60\u2005\u00c5, resulting in a tight head-to-tail packing. In the title complex, [Cu(NO DOI: Click here for additional data file.10.1107/S1600536812043346/mw2090Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The sixth coordination site of molybdenum is occupied by the O atom of a methanol mol\u00adecule. In this complex, the NO5 coordination sphere adopts a distorted octa\u00adhedral coordination geometry. The metal atom is shifted by 0.335\u2005(1)\u2005\u00c5 from the square plane defined by the three donor atoms of the Schiff base ligand and one oxide group towards the second oxide group in the cis position. In the crystal, the complex forms inversion dimers through a pair of O\u2014H\u22efN hydrogen bonds involving the methanol \u2013OH group and the pyridine N atom. Additional C\u2014H\u22efO contacts stack the mol\u00adecules along the b axis.In the title complex, [Mo(C O2(CH4O)] = 0.026wR(F2) = 0.070S = 1.073474 reflections239 parameters13 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.31 e \u00c5\u22123\u0394\u03c1min = \u22120.60 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXTL  I, global. DOI: 10.1107/S1600536813019077/sj5344Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The bridging carbonyl C\u2014C(=O)\u2014C plane makes dihedral angles of 47.07\u2005(6)\u00b0 with the naphthalene ring system and 24.20\u2005(10)\u00b0 with the benzene ring. A weak inter\u00admolecular C\u2014H\u22efO hydrogen bond exists between the H atom of one meth\u00adoxy group and the O atom of the other meth\u00adoxy group in an adjacent mol\u00adecule. The crystal packing is additionally stabilized by two types of weak inter\u00admolecular inter\u00adactions involving the Br atom, C\u2014H\u22efBr and Br\u22efO [3.2802\u2005(14)\u2005\u00c5].In the title compound, C DOI: 10.1107/S160053681004016X/vm2049Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The central PbII ion has a (4\u00a0+\u00a02) coordination by four O atoms of the two ABTC ligands and two weaker Pb\u2014S bonding inter\u00adactions (Pb\u2014S secondary bonds) from S atoms of other two neighbouring ABTC ligands. These bonds link the metal ions into zigzag chains along the c axis, which, in turn, aggregate through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.7436\u2005\u00c5] between ABTC rings and N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds.The title complex, [Pb(C DOI: 10.1107/S1600536810049330/bg2378Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.319\u2005(1)\u2005\u00c5] in the crystal structure.In the title compound, [Cd(NO DOI: 10.1107/S1600536811039687/jh2323Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The anion is a six-coordinated complex with a distorted CuN2O4 octa\u00adhedral geometry around the CuII ion. N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds along with \u03c0\u2013\u03c0 contacts between the pyridine rings of the (2a4mpH)+ cations [centroid\u2013centroid distance = 3.573\u2005(2)\u2005\u00c5] stabilize the crystal structure.The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536811001139/bt5449Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecular complex has no crystallographically imposed symmetry. The coordination geometry around the metal atom is distorted square-pyramidal. The equatorial coordination around copper involves donor atoms of the bidentate chelating 2-(dimethyl\u00adamino)\u00adethanol ligand and the 2-(dimethyl\u00adamino)\u00adethano\u00adlate group, which are mutually trans to each other, with four approximately equal short Cu\u2014O/N bond distances. The axial Cu\u2014I bond is substanti\u00adally elongated. Inter\u00admolecular hydrogen-bonding inter\u00adactions involving the \u2013OH group of the neutral 2-(dimethyl\u00adamino)\u00adethanol ligand to the O atom of the monodeprotonated 2-(dimethyl\u00adamino)\u00adethano\u00adlate group of the mol\u00adecule related by the n-glide plane, as indicated by the O\u22efO distance of 2.482\u2005(12)\u2005\u00c5, form chains of mol\u00adecules propagating along [101].The title compound, [Cu(C I(C4H11NO)] = 0.058wR(F2) = 0.204S = 1.002471 reflections133 parametersH-atom parameters constrainedmax = 1.80 e \u00c5\u22123\u0394\u03c1min = \u22120.83 e \u00c5\u22123\u0394\u03c1AFC6S Diffractometer Control Software AFC6S Diffractometer Control Software; data reduction: TEXSAN  I, global. DOI: 10.1107/S1600536812010215/ds2178Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "An intra\u00admolecular O\u2014H\u22efO hydrogen bond in the ligand generates an S(6) ring. The dihedral angle between the aromatic rings joined to the acetyl\u00adacetonate unit is 6.4\u2005(2)\u00b0. The ethanol mol\u00adecule is disordered over two orientations in a 0.65\u2005(3):0.35\u2005(3) ratio. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO bonds.In the title complex, [Co(C DOI: 10.1107/S1600536810029776/hb5579Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the ferrocenyl moiety, the unsubstituted cyclo\u00adpenta\u00addienyl ring is disordered over two orientations with site occupancies of 0.64\u2005(2) and 0.36\u2005(2). In the pyrrolizine ring, one C atom is disordered over two positions, with site occupancies of 0.71\u2005(1) and 0.29\u2005(1). Intra\u00admolecular C\u2014H\u22efO inter\u00adactions occur. The crystal packing is established through weak inter\u00admolecular C\u2014H\u22efO and N\u2014H\u22efO inter\u00adactions.In the title compound, [Fe(C DOI: 10.1107/S1600536810045459/im2240Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four acetamide ligands bridging the dirhodium core are arranged in a 2,2-cis manner, with two N atoms and two O atoms coordinating to the unique RhII atom cis to one another. The Neq\u2014Rh\u2014Rh\u2014Oeq torsion angles on the acetamide bridges vary between 1.62\u2005(4) and 1.78\u2005(4)\u00b0. The Rh\u2014Rh bond length is 2.4319\u2005(3)\u2005\u00c5. The axial nitrile ligand completes the distorted octahedral coordination sphere and shows a non-linear coordination with an Rh\u2014N\u2014C bond angle of 167.14\u2005(15)\u00b0, while the N\u2014C bond length is 1.135\u2005(3)\u2005\u00c5.The complex molecule of the title compound, [Rh DOI: Click here for additional data file.10.1107/S1600536813012828/mw2103Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The AuI atom is in a trigonal\u2013planar geometry within an IP2 donor set with the greatest distortion seen in the P\u2014Au\u2014P angle [128.49\u2005(3) \u00b0]. Close intra\u00admolecular Au\u22efO inter\u00adactions [3.172\u2005(3)\u2005\u00c5] are observed. No specific inter\u00admolecular inter\u00adactions are noted in the crystal packing.In the title compound, [AuI(C DOI: 10.1107/S1600536812011609/su2394Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The average of the four Ru\u2014Cl bond lengths is 2.355\u2005(15)\u2005\u00c5, and the Ru\u2014S and Ru\u2014N bond lengths are 2.2853\u2005(3) and 2.1165\u2005(11)\u2005\u00c5, respectively. The complex forms a chain, with a six-coordinate sodium ion bridging the ruthenium(III) units. The sodium cation is coordinated by cis-chloride ligands on ruthenium [Na\u2014Cl = 2.9576\u2005(7) and 2.6988\u2005(7)\u2005\u00c5], chloride and DMSO ligands from the ruthenium complexes related by inversion , a nitro\u00adgen ligand from the pyrimidine of the tetrachlorido\u00adruthenium(III) complex related by the twofold rotation axis [Na\u2014N = 2.5224\u2005(14)\u2005\u00c5] and an oxygen-bound DMSO [Na\u2014O = 2.3165\u2005(12)\u2005\u00c5]. The title complex, [NaRuCl DOI: 10.1107/S1600536811017211/om2427Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Danio rerio ; (ii) the African clawed toad Xenopus laevis ; and iii) the pond snail Radix balthica . Image sequences were analysed using Sparse Optic Flow and the resultant frame-to-frame motion parameters were analysed using Discrete Fourier Transform to quantify the distribution of energy at different frequencies. This spectral frequency dataset was then used to construct a Bray-Curtis similarity matrix and differences in movement patterns between embryos in this matrix were tested for using ANOSIM.Motion analysis is one of the tools available to biologists to extract biologically relevant information from image datasets and has been applied to a diverse range of organisms. The application of motion analysis during early development presents a challenge, as embryos often exhibit complex, subtle and diverse movement patterns. A method of motion analysis able to holistically quantify complex embryonic movements could be a powerful tool for fields such as toxicology and developmental biology to investigate whole organism stress responses. Here we assessed whether motion analysis could be used to distinguish the effects of stressors on three early developmental stages of each of three species: (i) the zebrafish Xenopus laevis at stages 24, 32 and 34 exposed to a salinity of 20, Danio rerio at 33\u2009hpf exposed to 1.5% ethanol, and Radix balthica at stages E4, E9 and E11 exposed to salinities of 5, 10 and 15. This technique was better able to distinguish embryos exposed to stressors than analysis of manual quantification of movement and within species distinguished most of the developmental stages studied in the control treatments.Spectral frequency analysis of these motion parameters was able to distinguish stage-specific effects of environmental stressors in most cases, including This innovative use of motion analysis incorporates data quantifying embryonic movements at a range of frequencies and so provides an holistic analysis of an embryo\u2019s movement patterns. This technique has potential applications for quantifying embryonic responses to environmental stressors such as exposure to pharmaceuticals or pollutants, and also as an automated tool for developmental staging of embryos. The development of imaging technology over the past two decades has enabled significant advances in biology and resulted in an exponential increase in the size and complexity of the data sets generated ,2. HowevAmong the many methods of automated image analysis available to biologists is motion analysis, a technique that has been used for quantifying the behavior of mammals , fish 88, sperm Danio rerio embryos at stages 19\u2009h, 21.5\u2009h and 33\u2009h , and a salinity of 5 : 598 \u2013 298\u2009s; [2]: 200 \u2013 149\u2009s; [3]: 120 \u2013 99\u2009s; [4]: 85 \u2013 54\u2009s; [5]: 49 \u2013 33\u2009s; [6]: 29 \u2013 20.5\u2009s; [7]: 21 \u2013 17\u2009s; [8]: 16 \u2013 15\u2009s; [9]: 14 \u2013 13\u2009s; [10]: 12 \u2013 11\u2009s; [11]: 10 \u2013 5\u2009s; [12]: 4.9 \u2013 3.5\u2009s; [13]: 3.3 \u2013 2.5\u2009s; [14]: 2.4 \u2013 1.7\u2009s; [15]: 1.6 \u2013 1\u2009s; [16]: 0.9 \u2013 0.33\u2009s; [17]: 0.3 \u2013 0.25\u2009s; [18]: 0.24 \u2013 0.1\u2009s. Analysis of Radix balthica\u2019s frame-to-frame motion analysis output was performed using 18 frequency bins for developmental stage comparisons - [1]: 598 \u2013 299\u2009s; [2]: 291 \u2013 145\u2009s; [3]: 120 \u2013 100\u2009s; [4]: 85 \u2013 75\u2009s; [5]: 66 \u2013 60\u2009s; [6]: 54 \u2013 50\u2009s; [7]: 46 \u2013 43\u2009s; [8]: 40 \u2013 37\u2009s; [9]: 35 \u2013 30\u2009s; [10]: 29 \u2013 24\u2009s; [11]: 20 \u2013 17\u2009s; [12]: 15 \u2013 12.5\u2009s; [13]: 12.2 \u2013 10\u2009s; [14]: 9.5 \u2013 5\u2009s; [15]: 2 \u2013 1.1\u2009s; [16]: 1 \u2013 0.68\u2009s; [17]: 0.66 \u2013 0.5\u2009s; [18]: 0.3 \u2013 0.26\u2009s, and 30 frequency bins for environmental stressor analysis - [1]: 300 \u2013 150\u2009s; [2]: 100 \u2013 75\u2009s; [3]: 60 \u2013 50\u2009s; [4]: 43 \u2013 37.5\u2009s; [5]: 33.5 \u2013 30\u2009s; [6]: 27.5 \u2013 25\u2009s; [7]: 23 \u2013 21.5\u2009s; [8]: 20 \u2013 19\u2009s; [9]: 17.5 \u2013 16.5\u2009s; [10]: 16 \u2013 14.5\u2009s; [11]: 13.5 \u2013 12.5\u2009s; [12]: 12 \u2013 11\u2009s; [13]: 10.5 \u2013 9.5\u2009s; [14]: 9 \u2013 6.5\u2009s; [15]: 6.3 \u2013 5\u2009s; [16]: 4.9 \u2013 3.5\u2009s; [17]: 3.3 \u2013 2.5\u2009s; [18]: 2.4 \u2013 2\u2009s; [19]: 1.9 \u2013 1.5\u2009s; [20]: 1.4 \u2013 1\u2009s; [21]: 0.9 \u2013 0.8\u2009s; [22]: 0.7 \u2013 0.65\u2009s; [23]: 0.6 \u2013 0.5\u2009s; [24]: 0.49 \u2013 0.4\u2009s; [25]: 0.39 \u2013 0.34\u2009s; [26]: 0.33 \u2013 0.28\u2009s; [27]: 0.27 \u2013 0.22\u2009s; [28]: 0.21 \u2013 0.18\u2009s; [29]: 0.17 \u2013 0.15\u2009s; [30]: 0.14 \u2013 0.13\u2009s. Radix balthica during its development performs movement types ranging from ciliary driven rotation to muscular driven crawling. As a result, to discern treatments more frequency bins were required for analysis of Radix balthica than for Danio rerio or Xenopus laevis, as movement differences fell within rather than between frequency bins. These extra frequency bins enhanced the frequency discrimination and therefore the detection of subtle changes to these complex movement behaviours.Frame-to-frame motion analysis data were analysed for spectral content using the Discrete Fourier Transform (DFT) . This reThe data resulting from the DFT comprises 72 parameters  for each individual. These data were transformed (Log X\u2009+\u20091) and for each species a Bray-Curtis similarity matrix was calculated. This matrix was used to generate Multidimensional Scaling (MDS) plots and ANOSIM  was usedThe authors have a patent pending, entitled: Method and system for determining characteristics of an embryo and uses thereof .This work was funded by the Marine Institute at Plymouth University through the HEIF4 programme.TB and OT carried out experimental work and bioimaging. PC carried out programming required for motion analysis and frequency analysis. TB, OT, SDR and JIS participated in the data analysis. All authors read and approved the final manuscript."}
{"text": "Two SnIV atoms are coordin\u00adated by two butyl groups, one benzoate O atom and two bridging O atoms, whereas the other two SnIV atoms are coordinated by two butyl groups, two benzoate O atoms and a bridging O atom. All the butyl groups are equatorial with respect to the SnO3 trigonal plane. In the crystal, mol\u00adecules are linked into a two-dimensional layer parallel to the ab plane by inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and further stabilized by a \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.6489\u2005(11)\u2005\u00c5]. Intra\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds stabilize the mol\u00adecular structure. Two of the butyl groups are each disordered over two sets of sites with site-occupancy ratios of 0.510\u2005(4):0.490\u2005(4) and 0.860\u2005(5):0.140\u2005(5).In the title complex, [Sn DOI: 10.1107/S1600536811028212/is2746Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination geometry around the CuII atom can be described as distorted elongated octa\u00adhedral with Rout = 2.277\u2005(2)\u2005\u00c5, Rin = 2.052\u2005(2)\u2005\u00c5 and a tetra\u00adgonality of 0.9011, acquiring a \u2018static\u2019 stereochemistry. In the supra\u00admolecular network, there are inter\u00admolecular C\u2014H\u22efF and C\u2014H\u22efN inter\u00adactions with R33(16), R22(7), R12(4), R33(16) and C32(7) motifs that lead to an infinite three-dimensional network.In the title compound, [Cu(C DOI: 10.1107/S1600536812028267/ru2037Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The RhI atom is displaced from the plane through these surrounding atoms by 0.0085\u2005(2)\u2005\u00c5. The dihedral angle between the benzene ring and the N\u2014C\u2014C\u2014C\u2014O plane is 89.82\u2005(6)\u00b0, and the N\u2014Rh\u2014O bite angle for the bidentate ligand is 90.53\u2005(6)\u00b0. An inter\u00admolecular C\u2014H\u22efO inter\u00adaction is observed between a methyl group of the benzene ring and a carbonyl O atom.In the title compound, [Rh(C DOI: 10.1107/S1600536812017175/hy2537Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "There are C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.487 \u2005(3)\u2005\u00c5] in the crystal structure. The perchlorate anion is disordered over two positions with an occupancy ratio of 0.628\u2005(9):0.372\u2005(9). In the crystal structure of the title compound, [Cu(HCO DOI: 10.1107/S1600536811039675/jh2326Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atom is bonded by two O atoms of the bidentate chelating sulfate ligand and the four N atoms of two chelating 2,2\u2032-bi\u00adpyridine ligands. The Ni\u2014N bond lengths range from 2.059\u2005(3) to 2.075\u2005(3)\u2005\u00c5 and the Ni\u2014O bond lengths are 2.098\u2005(3) and 2.123\u2005(3)\u2005\u00c5. The bipyridyl ligands are both close to planar (r.m.s. deviations of 0.254 and 0.0572\u2005\u00c5) and are almost orthogonal, making a dihedral angle of 82.77\u2005(1)\u00b0. In the crystal, the complex and water mol\u00adecules are connected by O\u2014H\u22efO hydrogen bonds. Inter\u00adestingly, six water mol\u00adecules form a chain linking two complex mol\u00adecules via sulfate O atoms. There are also stacking inter\u00adactions between the aromatic rings of neighbouring 2,2\u2032-bi\u00adpyridine ligands with shortest non-covalent contacts of 3.268\u2005(6), 3.393\u2005(6) and 3.435\u2005(5)\u2005\u00c5. One of the three unique water molecules shows half-occupation.The title compound, [Ni(SO DOI: Click here for additional data file.10.1107/S1600536813014219/sj5321Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The negatively charged N atom of the group binds to the terminal SnIV atom at a shorter distance [Sn\u2014N = 2.240\u2005(3)\u2005\u00c5] compared with the neutral N atom that binds to the central SnIV atom [Sn\u2190 N = 2.641\u2005(3)\u2005\u00c5]. The terminal SnIV atom is five-coordinate in a cis-C2SnNO2 trigonal\u2013bipyramidal geometry [C\u2014Sn\u2014C = 127.5\u2005(2)\u00b0], whereas the central SnIV atom is six-coordinate in a C2SnNO3 skew-trazepoidal bipyramidal geometry [C\u2014Sn\u2014C = 145.0\u2005(2)\u00b0].The tetra\u00adnuclear title compound, [Sn DOI: Click here for additional data file.10.1107/S1600536812047708/bt6863Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The RuII atom has a classical three-legged piano-stool environment being coordinated by an \u03b76-benzene ligand [Ru\u2014centroid = 1.6964\u2005(6)\u2005\u00c5], two chloride ligands with an average Ru\u2014Cl bond length of 2.4138\u2005(3)\u2005\u00c5 and a dicyclo\u00adhexyl\u00adphenyl\u00adphosphane ligand [Ru\u2014P = 2.3786\u2005(3)\u2005\u00c5]. The effective cone angle for the phosphane was calculated to be 158\u00b0. In the crystal, weak C\u2014H\u22efCl hydrogen bonds link the RuII complexes into centrosymmetric dimers. The crystal packing exhibits intra- and inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions resulting in a zigzag pattern in the [101] direction.The asymmetric unit of the title compound, [RuCl II\u2013arene complexes, see: Chen et al. (C18H27P)]\u00b71.5C6H6 = 0.018wR(F2) = 0.048S = 1.037589 reflections334 parametersH-atom parameters constrainedmax = 0.54 e \u00c5\u22123\u0394\u03c1min = \u22120.43 e \u00c5\u22123\u0394\u03c1APEX2  global, I. DOI: Click here for additional data file.10.1107/S1600536812044674/cv5349Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the L ligand, the two benzene rings are nearly parallel, forming a dihedral angle of 2.0\u2005(1)\u00b0. In the crystal, inter\u00admolecular O\u2014H\u22efN hydrogen bonds link pairs of mol\u00adecules into centrosymmetric dimers which exhibit \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings [centroid\u2013centroid distance = 3.677\u2005(5)\u2005\u00c5].In the title mol\u00adecule, [V(C DOI: 10.1107/S1600536811010385/cv5063Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CaII atom is octa\u00adcoordinated by two O atoms from two water mol\u00adecules and six O atoms from four acetate ligands. Each acetate acts as a tridentate ligand bridging two CaII atoms, resulting in a chain running along the c axis. O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds connect the chains into a two-dimensional network parallel to [011]. \u03c0\u2013\u03c0 inter\u00adactions between adjacent isoindoline-1,3-dione rings [centroid\u2013centroid distance = 3.4096\u2005(11)\u2005\u00c5] further consolidate the structure. One of the carboxylate O atoms is disordered over two sites in a 0.879\u2005(12):0.121\u2005(12) ratio.In the title complex, [Ca(C N-phthaloylglycine, see: Khan & Ismail 2(H2O)2] = 0.036                           wR(F                           2) = 0.102                           S = 1.04                           2339 reflections160 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.28 e \u00c5\u22123                        \u0394\u03c1min = \u22120.23 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811027851/pv2422Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efO hydrogen bonds into a chain along [010]. \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings and between the pyrazole rings [centroid\u2013centroid distances = 3.772\u2005(2) and 3.546\u2005(2)\u2005\u00c5] connect the chains.In the title complex, [Mn(CH DOI: 10.1107/S1600536811010506/hy2414Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The five Cl atoms bound to Sb [Sb\u2014Cl = 2.4043\u2005(9)\u20132.6262\u2005(11)\u2005\u00c5] form a square-pyramidal coordination environment. In addition, two [SbCl5]2\u2212 anions related by an inversion center are joined by Sb\u22efCl inter\u00adactions [Sb\u22efCl = 3.7273\u2005(14)\u2005\u00c5] into an [Sb2Cl10]4\u2212 dimer with two bridging Cl atoms. The anions, water mol\u00adecules and ammonium groups of the cations are linked by N\u2014H\u22efCl, N\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds, forming layers parallel to the ac plane. The benzene rings of the 4-methyl\u00adanilinium cations are packed between these layers.The title compound, (C DOI: 10.1107/S1600536812009427/yk2046Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In comparison with the original determination based on photographic data , the current study allows the location of reliable postions for the H atoms and thus leads to better understanding of the inter\u00adionic and inter\u00admolecular inter\u00adactions. The crystal structure consists of an octa\u00adhedrally coordinated cationic CoIII complex ion, an octa\u00adhedrally coordinated anionic CoIII complex ion and a lattice water mol\u00adecule. The complex cation, complex anion and lattice water mol\u00adecule are connected by an intricate network of O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming a three-dimensional structure.The structure of the title compound, [Co(NO al. 1976. Inorg.  III complexes, see: Angelici 2(C2H8N2)2][Co(NO2)4(C2H8N2)]\u00b7H2O = 0.035wR(F2) = 0.087S = 1.076280 reflections340 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.72 e \u00c5\u22123\u0394\u03c1min = \u22120.84 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  global, I. DOI: Click here for additional data file.10.1107/S1600536812050325/wm2706Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One iodo\u00adbenzoate anion and one water mol\u00adecule bridge adjacent Co cations, forming a polymeric chain running along the a axis, while the other iodo\u00adbenzoate anion and water mol\u00adecule coordinate in a monodentate manner to the CoII cation, completing the slightly distorted octa\u00adhedral geometry. In the two independent anionic ligands, the carboxyl\u00adate groups are twisted away from the attached benzene rings by 51.38\u2005(18) and 39.89\u2005(11)\u00b0, and the two benzene rings are nearly perpendicular to each other with a dihedral angle of 86.09\u2005(10)\u00b0. Intra\u00admolecular O\u2014H\u22efO hydrogen bonds between coordinating water mol\u00adecules and adjacent carboxyl\u00adate O atoms help to stabilize the mol\u00adecular structure. In the crystal, weak C\u2014H\u22efO hydrogen bonds link the polymeric chains into a three-dimentional supra\u00admolecular network.The asymmetric unit of the polymeric title compound, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(H2O)2] = 0.020wR(F2) = 0.051S = 1.204313 reflections224 parameters8 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.60 e \u00c5\u22123\u0394\u03c1min = \u22121.03 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 1835 FrFlack parameter: 0.016 (19)APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812015115/xu5504Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "A distorted octahedral coordination geometry of the CoII atom results from ligation of an H atom, which is part of an agostic B\u2014H\u22efCo inter\u00adaction [H\u22efCo = 2.12\u2005(3)\u2005\u00c5], and by five imine N atoms, two from a Bp ligand and three from a Tp ligand. Weak intra- and inter\u00admolecular C\u2014F\u22ef\u03c0 inter\u00adactions with F\u22efcentroid distances ranging from 3.025\u2005(4) to 3.605\u2005(4)\u2005\u00c5 are observed.The title compound, [Co(Cenza 2010. Acta Cr DOI: 10.1107/S1600536811021994/rz2601Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efO hydrogen bonds lead to the formation of a two-dimensional layer structure parallel to (001). The layers are connected by \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl and benzene rings of the phenanthroline ligands [centroid\u2013centroid distances = 3.591\u2005(1) and 3.610\u2005(1)\u2005\u00c5].In the title mononuclear complex, [Cd(C DOI: 10.1107/S1600536810028175/hy2328Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In both ligands, the benzyl and benzimidazole rings are nearly perpendicular [dihedral angles = 81.7\u2005(2) and 81.5\u2005(2)\u00b0]. The two benzimidazole systems are essentially planar [maximum deviations = 0.015\u2005(3) and 0.020\u2005(2)\u2005\u00c5] and form a dihedral angle of 78.09\u2005(8)\u00b0. In the crystal, centrosymmetrically related mol\u00adecules are linked by pairs of C\u2014H\u22efCl hydrogen bonds into chains parallel to the a axis.In the title compound, [ZnCl DOI: 10.1107/S1600536814002840/rz5104Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The hydrazine carbothio\u00adamide moiety and one of the pyridyl rings together adopt an almost planar arrangement, with a maximum deviation of 0.052\u2005(4)\u2005\u00c5 for the C atom of the thio\u00adurea moiety. There are two mol\u00adecules of methanol solvent per complex in the asymmetric unit. The nonconventional intra\u00admolecular C\u2014H\u22efBr hydrogen bonds make the mol\u00adecule more rigid, whereas the conventional N\u2014H\u22efN and O\u2014H\u22efBr inter\u00admolecular hydrogen-bonding inter\u00adactions, supported with N\u2014H\u22ef\u03c0 inter\u00adactions, establish a supra\u00admolecular linkage among the mol\u00adecules in the crystal. An intermolecular C\u2014H\u22efO inter\u00adaction is also present.In the centrosymmetric binuclear title compound, [Cu DOI: 10.1107/S1600536812005934/fj2511Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Within the complex, the carb\u00adoxy\u00adlic acid forms intra\u00admolecular O\u2014H\u22efO hydrogen bonds, while the mol\u00adecules are assembled through N\u2014H\u22efO(carbox\u00adyl) hydrogen bonds into chains extending along the a-axis direction. These chains are further linked by weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid separation = 3.930\u2005(2)\u2005\u00c5].The structure of the title compound, [Cu(C DOI: 10.1107/S160053681102839X/zs2128Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the benzene rings is 12.27\u2005(11)\u00b0. Adjacent complex mol\u00adecules are linked into dimers by O\u2014H\u22efO hydrogen bonds, generating rings of R               1               2(6) and R               1               2(5) graph-set motifs, and by aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions, with a centroid\u2013centroid distance of 3.812\u2005(2)\u2005\u00c5. The crystal packing is further stabilized by inter\u00admolecular C\u2014H\u22efN hydrogen bonds. The C and N atoms of the acetonitrile solvent mol\u00adecule are located on a crystallographic twofold axis.In the mononuclear complex mol\u00adecule of the title compound, [Cr(C DOI: 10.1107/S1600536811037275/rz2636Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efI hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.790\u2005(2)\u2005\u00c5] are present in the crystal structure.In the centrosymmetric dinuclear title compound, [Cd DOI: 10.1107/S1600536810041681/hy2362Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The benzene and pyridine rings are oriented at a dihedral angle of 56.7\u2005(6)\u00b0. The crystal packing is stabilized by C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.796\u2005(6)\u2005\u00c5].In the centrosymmetric binuclear molecule of the title complex, [Hg DOI: 10.1107/S1600536812039050/hy2585Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In addition, there is a Zn\u22efS contact involving a symmetry-related S atom which, when considered, forms a pseudo-square-pyramidal coordination with respect to the ZnII ion. Three of the ethyl groups are disordered over two sites with occupancy ratios of 0.841\u2005(10):0.159\u2005(10), 0.802\u2005(10):0.198\u2005(10) and 0.457\u2005(13):0.543\u2005(13). Weak intra\u00admolecular C\u2014H\u22efN and C\u2014H\u22efS inter\u00adactions contribute to the stability of the mol\u00adecular conformation. Inter\u00admolecular C\u2014H\u22efS contacts, weak C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centriod distances = 3.832\u2005(4) and 3.850\u2005(5)\u2005\u00c5] contribute to the stabilization of the crystal structure.In the title compound, [Zn(C DOI: 10.1107/S1600536810028588/lh5086Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitro\u00adgen and the other CuII atom are located in apical positions. The whole mol\u00adecule looks like a paddle-wheel. In the crystal, chains are assembled along the b axis through C\u2014H\u22efO hydrogen bonds and slipped \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.6929\u2005(3)\u2005\u00c5 and slippage = 0.641\u2005(1)\u2005\u00c5].In the binuclear copper(II) title complex, [Cu II carboxyl\u00adato compounds with subnormal magnetic moments, see: Kato et al. 4(C2H3N)2] = 0.037wR(F2) = 0.105S = 1.073466 reflections271 parametersH-atom parameters constrainedmax = 0.55 e \u00c5\u22123\u0394\u03c1min = \u22120.32 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812049410/lr2089Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, the complex anions and cations are linked via N\u2014H\u22efCl hydrogen bonds into layers parallel to (101). Short Br\u22efCl contacts of 3.4239\u2005(11) and 3.4503\u2005(12)\u2005\u00c5 are observed, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine and pyridinium rings, with alternating centroid-to-centroid distances of 3.653\u2005(2) and 3.845\u2005(2)\u2005\u00c5.The structure of the title salt, (C DOI: Click here for additional data file.10.1107/S1600536813011884/wm2739Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The structure contains two uncoordinated water mol\u00adecules. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings of the pydc ligands, with a centroid\u2013centroid distance of 3.4582\u2005(18)\u2005\u00c5, stabilize the structure.In the title compound, (C DOI: 10.1107/S1600536811024366/hy2434Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angles formed between the mean planes of the pyrazole rings and the phenanthroline system are 15.74\u2005(15) and 16.30\u2005(13)\u00b0. In the crystal, there is a \u03c0\u2013\u03c0 stacking inter\u00adaction involving two symmetry-related pyrazole rings, with a centroid\u2013centroid distance of 3.664\u2005(3)\u2005\u00c5. In addition, there is a relatively short inter\u00admolecular contact between C atoms [C\u22efC = 3.399\u2005(6)\u2005\u00c5] involving symmetry-related pyridine rings along the a axis.In the title complex, [Cd(NCS) DOI: 10.1107/S1600536810051275/lh5181Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The o-nitro\u00adsotoluene ligand is N-bound to iron(II) [Fe\u2014N = 1.8406\u2005(18)\u00c5 and Fe\u2014N\u2014O = 122.54\u2005(14)\u00b0]. The axial N\u2014Fe\u2014N linkage is almost linear, with a bond angle of 177.15\u2005(7)\u00b0. One phenyl group of the porphyrin ligand is disordered over two orientations in a 0.710\u2005(3):0.290\u2005(3) ratio. The di\u00adchloro\u00admethane solvent mol\u00adecule was severely disordered and its contribution to the scattering was removed with the SQUEEZE routine .The solvated title compound, [Fe(CSpek 1990. Acta Cr DOI: 10.1107/S160053681400083X/hb7178Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion in the title complex, [PtBr2(C10H9N3)], is four-coordinated in an essentially square-planar environment by two N atoms from a chelating di-2-pyridyl\u00adamine (dpa) ligand and two Br\u2212 anions. The dpa ligand is not planar, with the dihedral angle between the pyridine rings being 40.8\u2005(2)\u00b0. The complex mol\u00adecules are stacked in columns along [001] through \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.437\u2005(3) and 3.520\u2005(3)\u2005\u00c5]. Inter\u00admolecular N\u2014H\u22efBr hydrogen bonds connect the mol\u00adecules into chains running along [010]. Intra\u00admolecular C\u2014H\u22efBr interactions are also observed.The Pt II complex [PtCl2(dpa)], see: Li & Liu ] = 0.029wR(F2) = 0.079S = 1.102973 reflections145 parametersH-atom parameters constrainedmax = 1.41 e \u00c5\u22123\u0394\u03c1min = \u22122.22 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The amine N\u2014H group and pyridine N atom are syn allowing for the formation of centrosymmetric eight-membered {\u22efHNCN}2 synthons via N\u2014H\u22efN hydrogen bonds. The two-mol\u00adecule aggregates are sustained in the three-dimensional crystal packing via C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance for pyridyl rings = 3.7535\u2005(12)\u2005\u00c5]The title amine, C DOI: 10.1107/S1600536811044059/hg5117Isup2.hkl            Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044059/hg5117Isup3.cml            Supplementary material file. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each mol\u00adecule, the CuII ion is five-coordinated in a distorted square-pyramidal geometry wherein the basal plane is defined by the N,N\u2032,N\"-tridentate Schiff base and one N-bound thio\u00adcyanate ligand. The second N-donor thio\u00adcyanate group, located at the apical site, completes the coordination environment. In the crystal, inter\u00admolecular C\u2014H\u22efS and C\u2014H\u22efN hydrogen bonds link adjacent mol\u00adecules into infinite layers parallel to the ac plane. Intra\u00admolecular C\u2014H\u22efN inter\u00adactions are also observed.The asymmetric unit of the title compound, [Cu(NCS) For the al. 2011. For a d al. 1984.       2(C11H17N3)] = 0.045                           wR(F                           2) = 0.128                           S = 1.00                           7159 reflections385 parametersH-atom parameters constrainedmax = 1.04 e \u00c5\u22123                        \u0394\u03c1min = \u22120.81 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811022057/is2717Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In complex A, [Zn2(C8H7O2)4(H2O)2], each Zn cation is chelated by a 4-methyl\u00adbenzoate (PMB) anion and coordinated by a water mol\u00adecule, and is further bridged by two PMB anions in a trigonal-bipyramidal geometry. In complex B, [Zn2(C8H7O2)4(C6H6N2O)2], each ZnII cation is coordinated by a monodentate PMB anion and one nicotinamide (NA) ligand, and is further bridged by two PMB anions in a tetra\u00adhedral geometry. Weak intra-mol\u00adecular \u03c0\u2013\u03c0 stacking between adjacent benzene rings is observed in complex B, the centroid\u2013centroid distance being 3.710\u2005(2)\u2005\u00c5. Extensive O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding and weak C\u2014H\u22efO hydrogen bonding is present in the crystal structure. The crystal studied was a racemic twin; the minor twin component refined to 38%.The crystal structure of the title compound, [Zn DOI: 10.1107/S1600536810022476/xu2762Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "AbstractHarpapion safranumsp. n. and Harpapion borisisp. n. are described and figured. Harpapion vietnamense  is recorded as new for China. The genitalia andterminalia of H. considerandum, H. coelebs andH. vietnamense are redescribed and redrawn. The diagnostic characters of Harpapion are defined. A key to the known species of the genus Harpapion from China is provided. Affinities with the genus Flavopodapion Korotyaev, 1987 are discussed. Harpapion was erected and initially placed as a subgenus of Apiotherium Beguin-Billecocq, 1905 by Apioninaeincertae sedis by Aspidapiini Alonso-Zarazaga, 1990 based on its elongate-triangular scutellum and the genitalia with apparently primitive traits  and Harpapion vietnamense , respectively from China and Vietnam were identified as new records of Harpapion in Southeast Asia , and then Harpapion compared with Pseudaspidapion Wanat, 1990.The apionid genus e traits . Moreovee traits  until twast Asia . Wanat , Harpapion coelebs andHarpapion vietnamense.Recently, we obtained two more specimens of the monotypic species Institute of Zoology, Chinese Academy of Sciences, Beijing (IZCAS) and the Biological Museum, Sun Yat-Sen University, Guangdong (BMSYU). Type and identified specimens were obtained from BMSYU, Natural History Museum (NHM), Zoological Institute (ZIN) on loan or belong to IZCAS.Materials examined of the new species for this study are to be deposited in the Descriptions were made and photographs were taken with a Canon EOS 5D mounted on a Nikon SMZ1500. Extended focus images were generated with CombineZM and edited with Adobe Photoshop CS 5.0 when required. Microscopic slides were studied under a Leica DM 2500 microscope and photos were taken with a Nikon CoolPix P7100. Drawings were made from the original photographs by using the software Adobe Illustrator CS5.0, or directly by using a drawing tube attached to the microscope.Scanning Electron Microscope (SEM) photos were taken with a FEI ESEM Quanta 450 device and the software xT microscope control. Specimens were cleaned by hair pencil and mounted on the mounting card directly.Nomenclature of the rostral parts follows The dissecting method used follows After description, the genitalia and other parts of each specimen were placed in DMHF on an acetate card for long term conservation .Labels are described as they are (in Chinese or Cyrillic), with pinyin romanization for Chinese and ISO 9:1995 for Russian, and translations in square brackets; labels are separated by semicolons and lines by slashes. Alternative modern pinyin romanizations are also given in some cases where labels are written using other romanization systems, like Wade-Giles.Harpapion could be defined as follows: 1) scutellum triangular, distinctly elongate and basally projecting, apically raised (Pseudaspidapion)  the pygidium is of the aspidapionine type, subsemicircular in dorsal view, with the apical flange strongly raised, the transverse sulcus deep but not cutting the sides; 8) the ninth sternite  is Y-shaped, slender and subsymmetrical, not winged; 9) the apex of the penis is moderately to distinctly curved in lateral view, sometimes the pedon is recurved at apex; 10) the tegminal plate is articulated with the free ring, laterally developed, enveloping; the parameroid lobes present a usually well developed apical membranous area with a small apical notch, the basal sclerotized area has a medial sinuation in its front margin and bears 4-7 macrochaetae on each side; the fenestrae are present and variable; the prostegium is bidentate with two lateral projections (absent in Harpapion coelebs).According to species examined, the diagnostic characters of y raised ; 2) the idapion) , 16; 3) http://species-id.net/wiki/Harpapion_considerandumPygidium subsemicircular in dorsal view, 0.83\u00d7 as long as wide, apical flange strongly raised, transverse sulcus deep  Y-shaped, slender and nearly symmetrical, not winged, manubrium about 1.21\u00d7 as long as arms . Penis i1\u2642: : Magila / E. Africa / A. V. Legros / 98-190; : Wagner det. \u2642 / considerandum F\u00e5hr.; 1\u2640: : X. 1983 / in clove tree / CIEA15888; : Tanzania / Zanjibar / Kitunda; : pres by: Comm Inst Ent B. M. 1984-1. Specimens in the NHM.Harpapion considerandum s. str. has been recorded from the following African countries: Guinea, Cameroon, Republic of the Congo, Democratic Republic of the Congo (ex Zaire), Chad, Ethiopia, Kenya, Tanzania, Uganda, Angola, Zimbabwe and South Africa   from Senegal, Guinea, Mali, Nigeria and Tanzania  from Tanzania and Angola  . Two subTanzania ; and sspd Angola .http://species-id.net/wiki/Harpapion_coelebsPygidium subsemicircular in dorsal view, 0.83\u00d7 as long as wide, apical flange strongly raised, transverse sulcus distinctly depressed and wide, disc with 2\u20133 rows of punctures between disc and sulcus, pubescent sparse and minute : \u4e91\u5357\u666f\u4e1c\u8463\u5bb6\u575f [Y\u00fann\u00e1n J\u01d0ngD\u014dng D\u01d2ngji\u0101f\u00e9n] / 1956.V.28/1250m / leg. \u514b\u96f7\u8ba9\u8bfa\u592b\u65af\u57fa [Kryzhanovsky]; : \u042e\u043d\u044c\u043d\u0430\u043d\u044c, 10 \u043a\u043c. N \u0426\u0437\u0438\u043d-  / \u0434\u0443\u043d\u0430 [-D\u014dng], 1250 \u043c, 28. V. 1956 / \u041a\u0440\u044b\u0436\u0430\u043d\u043e\u0432\u0441\u043a\u0438\u0439 [Kryzhanovsky].Yunnan.http://species-id.net/wiki/Harpapion_vietnamensePygidium subsemicircular in dorsal view, 0.89\u00d7 as long as wide, apical flange strongly raised, transverse sulcus deep and narrow, disc nearly smooth, without visible punctures or pubescence ] / \u91c7\u96c6\u4eba\uff1a\u5b5f\u4ee4\u66fe [C\u01ceij\u00edr\u00e9n (leg.): M\u00e8ng L\u00ecngz\u0113ng]; Guomenshan, VI/1D / 06.05.2009/ leg. L. Z. Meng; IOZ(E)1369311; 1\u2642: \u4e91\u78a7\u5927\u5f00\u6cb3 [Y\u00fan B\u00ec D\u00e0k\u0101ih\u00e9] / 1957.IV.23 / \u6731\u589e\u6d69 [leg. Zh\u016b Z\u0113ngh\u00e0o]; IOZ(E)1639312.Holotype. \u2642 : \u0412\u044c\u0435\u0442\u043d\u0430\u043c, \u043f\u0440\u043e\u0432. \u0425\u0430\u0448\u043e\u043d\u0431\u0438\u043d\u044c   / 7 \u043a\u043c \u044e.-\u0432. \u0425\u043e\u0430\u0431\u0438\u043d\u044f, \u0432\u0442\u043e\u0440\u0438\u0447\u043d\u044b\u0439 \u0442\u0440\u043e\u043f\u0438\u0447\u0435\u0441\u043a\u0438\u0439 \u043b\u0435\u0441 \u0438 \u043a\u0443\u0441\u0442\u0430\u0440\u043d\u0438\u043a \u043d\u0430 \u0441\u043a\u043b\u043e\u043d\u0435   / 17. X 1976 / leg. \u041b. \u041d. \u041c\u0435\u0434\u0432\u0435\u0434\u0435\u0432 [L. N. Medvedev]; 1\u2642: \u4e91\u5357\u666f\u6d2a\u52d0\u6d77\u53bf\u7eb3\u677f\u6cb3 [Y\u00fann\u00e1n J\u01d0ngh\u00f3ng M\u011bngh\u01ceixi\u00e0n N\u00e0b\u01cenh\u00e9] / \u4fdd\u62a4\u533a\u8fc7\u95e8\u5c71\uff08\u68ee\u6797\uff09 [b\u01ceoh\u00f9q\u016b Gu\u00f2m\u00e9nsh\u0101n (s\u0113n l\u00edn [forest]) / 2009.V.06, 1114m; Yunnan (new record for China), Vietnam.Wang & Alonso-Zarazagasp. n.http://zoobank.org/887BB3CE-2FF2-4337-A439-88763EA93AE1http://species-id.net/wiki/Harpapion_safranumMeasurements (in mm): Standard length: 1.84. Rostrum: length: 0.77, maximum width: 0.16. Pronotum: median length: 0.53, maximum width: 0.57. Elytra: median length: 1.33, maximum width: 0.92.(holotype). Integument  and grayish acute hairs on antennae, tibiae and tarsomeres. Pronotal vestiture centripetal, scales on apex parallel to margin, but on base perpendicular to margin, pronotal disc with scales distinctly longer and thicker than on legs, reaching base of anterior scales. Elytral scales in one row per interstriae, two irregular rows on disc, scales on striae 1/2-2/3 as long as scales on interstriae. One specialized seta on apical region of 9th interstria.Rostrum cylindrical and moderately robust, in dorsal view 8.25\u00d7 as long as apical width, 1.45\u00d7 as long as pronotum in midline, widest at mesorostrum, prorostrum constricted apicad, metarostrum with sides almost parallel, metarostrum with median dorsal area impunctate, dorsal submedial sulci and dorsal submedial keels weak, minutely punctate and pubescent, lateral area of metarostrum and prorostrum with weak oblong confluent punctures, weakly microreticulate, apical third of prorostrum almost impunctate, smooth and shining; in lateral view moderately curved, sides converging to apex, carinae and sulci weak, ventral medial keel fine and complete, ventral sublateral keels with dense line of scales under mesorostrum.Head transverse, frons very weakly convex, as wide as metarostrum, constricted behind eyes, medial area impunctate and glabrous, lateral areas with irregular rows of punctures and scales, subocular keel not reaching middle of eyes, area between subocular keel flat, microreticulate and impunctate. Eyes round, moderately convex.Antennae inserted at basal 0.23 of rostral length, scape 3.20\u00d7 as long as wide, about as long as mesorostral width. Pedicel 2.00\u00d7 as long as wide, as long as desmomeres 2+3, desmomeres 2\u20133 1.33\u00d7 as long as wide, desmomeres 4\u20135 and 7 1.00\u00d7 as long as wide, desmomere 6 0.75\u00d7 as long as wide. Club oval, slightly flattened, 1.88\u00d7 as long as wide, as long as last 5.5 desmomeres, sutures obsolete.Pronotum campaniform, 0.93\u00d7 as long as wide, apical constriction relatively strong, little wider at base than at middle, base 1.39\u00d7 as wide as apex, bisinuate with rounded medial projection towards scutellum, basal flange developed. Prescutellar fovea shallow, very short, about as broad as diameter of one puncture, as long as 2\u20133 diameters, reaching 1/4 of pronotum. Discal punctures relatively deep, ca. 0.5\u20131\u00d7 diameter apart, interspaces moderately convex, microreticulate.Scutellum elongate, triangular, ca. 2.00\u00d7 as long as wide, 2 basal tubercles fused at base in front view, apical tubercle rounded, slightly prominent and hardly visible in lateral view : Standard length: 1.62\u20131.90. Rostrum: length: 0.61\u20130.75, maximum width: 0.14\u20130.16. Pronotum: median length: 0.47\u20130.57, maximum width: 0.51\u20130.60. Elytra: median length: 1.26\u20131.46, maximum width: 0.72\u20130.92. Female paratypes 1639313; Paratypes: 3\u2642: Kwangtung [Gu\u01cengd\u014dng] S. China / Loh Fau Shan, [Lu\u00f3f\u00fash\u0101n], / Poh-lo [B\u00f3lu\u00f3] District / April 6\u20138, 1934 / K. C. Yeung; En-071380~En-071382; 1\u2642: Hong Kong: Un-long [Yu\u00e1nl\u00e1ng], / New Territories / September 19. 1940 / J. Linsley Gressitt; En-071403; 1\u2642: Hainan I. South China / Ta-hian [probably D\u00e0oxi\u01ceng], Alt. 300 met. / N. side, 5- Finger Mts. [W\u00fazh\u012dsh\u0101n] / VI-12-1935 / L. Gressitt / En-071423; 1\u2640: Kwangtung [Gu\u01cengd\u014dng], S. China / Ho-y\u00fcn [Heyun] to Wui-lung [probably W\u00e9il\u00f3ng] / Ho-yuen [H\u00e9yu\u00e1n] District / Apr. 7, 1940. J. L. / Gressitt & F. K. To; En-071409; 1\u2640: Kwangtung [Gu\u01cengd\u014dng], S. China. / Sin-fung [X\u012bnf\u0113ng] to Lung-kai [Longgai (probably L\u00f3ngj\u012be which can be found on the modern maps)]. / Sin-fung [X\u012bnf\u0113ng] & Lien-p\u2019ing [Li\u00e1np\u00edng] / Dist\u2019s, Apr. 12, 1940 / L. Gressitt & F. E. To; En-071367.Guangdong, Hong Kong, Hainan.Holotype will be deposited in IZCAS, while all paratypes in BMSYU.Harpapion safranum sp. n., can be easily recognized from other species from China by its external characters  However, it is extremely similar to Harpapion considerandum which can be distinguished from the former by genitalia which were described above and illustrated in safranum after its testaceous legs. This is a Medieval Latin name of the plant now called Crocus sativus L. (saffron) which yields a yellowish-orange dye. It is considered a noun in apposition.This species is named Wang & Alonso-Zarazagasp. n.http://zoobank.org/03462889-EF2B-418A-BAE5-394758F1E2DBhttp://species-id.net/wiki/Harpapion_borisiMeasurements (in mm). Standard length: 1.22. Rostrum: length: 0.44, maximum width: 0.08. Pronotum: median length: 0.36, maximum width: 0.41. Elytra: length: 0.94, maximum width: 0.54.(holotype). Integument generally piceous, tibiae and tarsi relatively paler and antennae pale reddish brown ] / \u91c7\u96c6\u4eba\uff1a\u5b5f\u4ee4\u66fe [C\u01ceij\u00edr\u00e9n (leg.): M\u00e8ng L\u00ecngz\u0113ng]; Guomenshan VI/1D / 16.03.2009 / leg. L. Z. Meng; IOZ(E)1639309; Paratype: 1\u2642, : \u4e91\u5357\u666f\u6d2a\u52d0\u6d77\u53bf\u7eb3\u677f\u6cb3 [Y\u00fann\u00e1n J\u01d0ngh\u00f3ng M\u011bngh\u01ceixi\u00e0n N\u00e0b\u01cenh\u00e9] / \u4fdd\u62a4\u533a\u8fc7\u95e8\u5c71\uff08\u68ee\u6797\uff09 [b\u01ceoh\u00f9q\u016b Gu\u00f2m\u00e9nsh\u0101n (s\u0113n l\u00edn [forest])] / 2009.VI.26 1114m; 22.24644\u00b0N, 100.60610\u00b0E\u98de\u963b [F\u0113iz\u016d (flight intercept)] / \u91c7\u96c6\u4eba\uff1a\u5b5f\u4ee4\u66fe [C\u01ceij\u00edr\u00e9n (leg.): M\u00e8ng L\u00ecngz\u0113ng]; Guomenshan VI/1D / 26.06.2009 / leg. L. Z. Meng; IOZ(E)1639310.Holotype: 1\u2642: : \u4e91\u5357\u666f\u6d2a\u52d0\u6d77\u53bf\u7eb3\u677f\u6cb3 [Y\u00fann\u00e1n J\u01d0ngh\u00f3ng M\u011bngh\u01ceixi\u00e0n N\u00e0b\u01cenh\u00e9] / \u4fdd\u62a4\u533a\u8fc7\u95e8\u5c71\uff08\u68ee\u6797\uff09 [b\u01ceoh\u00f9q\u016b Gu\u00f2m\u00e9nsh\u0101n (s\u0113n l\u00edn [forest])] / 2009.III.16 1114m; Yunnan.Both holotype and paratype will be deposited in IZCAS.Harpapion borisi sp. n. can be distinguished from other congeners by the following traits: 1) body standard length 1.22\u20131.24 mm (the others more than 1.5 mm); 2) elytral scales with similar size, in one regular row per interstria; 3) rostral pubescence not surpassing middle of prorostrum, nearly entire prorostrum glabrous; 4) prostegial teeth short and narrow; 5) tegminal median unsclerotized strip absent; 6) spiculum gastrale with manubrium about as long as arms.Apionidae from South China and helped us in many ways.This species is named after the Russian curculionidologist Boris A. Korotyaev, who has much improved the taxonomy of Harpapion considerandum is short and medially sinuate, and the apical membranous area  is wellFlavopodapion Korotyaev, 1987 )  with the manubrium distinctly shorter than the arms )  resemblender SEM . On the arpapion . Other carpapion  coincidethe arms , the parthe arms . However"}
{"text": "In the crystal, mol\u00adecules are assembled by C\u2014H\u22efO hydrogen bonding and \u03c0\u2013\u03c0 inter\u00adactions between bipy groups [centroid\u2013centroid distances = 3.7686\u2005(16) and 3.7002\u2005(16)\u2005\u00c5] into a three-dimensional network. The nitrite anion is equally disordered over two sets of sites.In the title compound, [Cu(NO DOI: 10.1107/S1600536811002571/kp2303Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII ion is coordinated by two N and four O atoms from one bis\u00ad{[bis\u00ad(carboxyl\u00adatometh\u00adyl)amino]\u00admeth\u00adyl}phosphinate ligand in a distorted octa\u00adhedral coordination geometry. The two crystallographically independent potassium ions exhibit different coordination environments. The potassium ion in a general position is hepta\u00adcoordinated by five carboxyl\u00adate O atoms, one phosphinate O atom and one water mol\u00adecule [K\u2014O = 2.718\u2005(3)\u20133.040\u2005(3)\u2005\u00c5], and the potassium ion situated on the twofold rotation axis is hexa\u00adcoordinated by four carboxyl\u00adate O atoms and two water mol\u00adecules [K\u2014O = 2.618\u2005(3)\u20132.771\u2005(3)\u2005\u00c5]. The water mol\u00adecules are also involved in formation of inter\u00admolecular O\u2014H\u22efO hydrogen bonds.In the title compound, K DOI: 10.1107/S1600536811053608/cv5214Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "O\u2014H\u22efO hydrogen bonding between \u2013COOH and \u2013COO\u2212 groups of adjacent mol\u00adecules and between carboxyl\u00adate groups and coordinated and uncoordin\u00adated water mol\u00adecules leads to a three-dimensional structure which is further stabilized by weak \u03c0\u2013\u03c0 inter\u00adactions of adjacent phen ligands with centroid\u2013centroid separations of 4.2932\u2005(1)\u2005\u00c5.In the title complex, [Mn(C DOI: 10.1107/S1600536810048142/wm2428Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The thia\u00adzolidine ring mean plane makes a dihedral angle of 59.08\u2005(11)\u00b0 with the pyrrolidine ring mean plane, which in turn makes a dihedral angle of 83.40\u2005(10)\u00b0 with the cyclo\u00adpentane ring, indicating that the latter two rings are almost orthogonal to one another. In the crystal, a pair of C\u2014H\u22efO hydrogen bonds link the mol\u00adecules forming inversion dimers. The dimers are linked via \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.7764\u2005(10)\u2005\u00c5] involving the quinoxaline moieties forming chains propagating along [1-10].In the title compound, [Fe(C DOI: 10.1107/S1600536813022605/su2630Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Cl atom of the mol\u00adecule with the smaller C\u2014Sn\u2014C angle inter\u00adacts weakly with the SnIV atom of the mol\u00adecule with the wider C\u2014Sn\u2014C angle at an Sn\u22efCl distance of 3.595\u2005(1)\u2005\u00c5. Weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonding is present in the crystal structure.The asymmetric unit of the title complex, [Sn(CH DOI: 10.1107/S1600536810027790/xu2800Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination number of copper is six with four basal O atoms, one axial N atom and one axial Cu atom. Four acetate ligands act as bidentate linker and connect two Cu atoms, with a crystallographic inversion center located at the mid-point of the Cu\u2014Cu bond. The acetate ligands form slightly distorted square planes around each metal ion, while the copper ions are displaced by 0.2089\u2005(4)\u2005\u00c5 from these planes towards the N atoms. Thus, the Cu\u2014Cu distance is elongated to 2.6378\u2005(7)\u2005\u00c5, compared with the 2.2180\u2005(7)\u2005\u00c5 distance between the two basal planes. The angle between the basal plane and the Cu\u2014N bond is 4.84\u2005(6)\u00b0.The title compound, [Cu LCu)2(\u03bc-O2CCH3)4 complexes is the crystal structure of cupric acetate monohydrate (L = water), see: Van Niekerk & Schoening L = 2-amino-benzothia\u00adzole, see: Sun et al. L = benzothia\u00adzole, see: Ford et al. 4(C7H5NS)2] = 0.032                           wR(F                           2) = 0.075                           S = 0.97                           2784 reflections165 parametersH-atom parameters constrainedmax = 0.45 e \u00c5\u22123                        \u0394\u03c1min = \u22120.45 e \u00c5\u22123                        \u0394\u03c1                                 X-AREA  used to solve structure: SIR92  I, global. DOI: 10.1107/S1600536811027140/hg5042Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the title complex, [HgI2(C12H6N2O2)], is tetra\u00adhedrally coordinated by the N atoms of the chelating 1,10-phenanthroline-5,6-dione ligand and two I atoms. The range of tetra\u00adhedral angles is broad, viz. 68.94\u2005(17)\u00b0 for the chelate angle to a wide 132.627\u2005(15)\u00b0 for the I\u2014Hg\u2014I angle. The ligand mol\u00adecule is non-planar with the O atoms lying 0.422\u2005(5) and \u22120.325\u2005(5)\u2005\u00c5 out of the plane through the remaining atoms [r.m.s. deviation = 0.068\u2005\u00c5]. Mol\u00adecules are consolidated in the crystal packing by C\u2014H\u22efO inter\u00adactions.The Hg DOI: 10.1107/S1600536811038748/hg5098Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A twofold rotation axis passes through the Fe4S4 core, completing the coordination of the four Fe atoms with two penta\u00admethyl\u00adcyclo\u00adpenta\u00addienyl ligands and two chelating dithiol\u00adate ligands. There are three short Fe\u2014Fe and three long Fe\u22efFe contacts in the Fe4S4 core, suggesting bonding and non-bonding inter\u00adactions, respectively. The Fe\u2014S bonds in the Fe4S4 core range from 2.1523\u2005(5) to 2.2667\u2005(6)\u2005\u00c5 and are somewhat longer than the Fe\u2014S bonds involving the dithiol\u00adate ligand.The title compound, [Fe DOI: Click here for additional data file.10.1107/S1600536813005564/wm2725Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The SnIV atom is displaced out of the C3Sn girdle of the trans-C3SnO2 trigonal-bipyramidal polyhedron in the direction of the covalently-bonded O atom [Sn\u2014O\u2014C = 137.63\u2005(11)\u00b0] by 0.247\u2005(1)\u2005\u00c5; the geometry is distorted towards an octa\u00adhedron by a remote O atom of the meth\u00adoxy subsituent [Sn\u22efO = 3.019\u2005(1)\u2005\u00c5]The formyl\u00admeth\u00adoxy\u00adnitro\u00adphenoxide ions in the polymeric title compound, [Sn(C DOI: 10.1107/S1600536811016436/jh2283Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII atoms are bridged by two carboxyl\u00adate O atoms from two DNSA ligands, forming a centrosymmetric dinuclear structure. Neighbouring dinuclear units inter\u00adact with each other through two types of \u03c0\u2013\u03c0 inter\u00adactions between the L ligands [shortest centroid\u2013centroid distance = 3.646\u2005(3)\u2005\u00c5] and between the L and DNSA ligands [shortest atom-to-centroid distance = 3.794\u2005(3)\u2005\u00c5]. N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds are observed, which lead to a three-dimensional structure.In the title compound, [Co DOI: 10.1107/S1600536810017629/hy2303Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The SnIV atom shows cis-C2SnCl2O trigonal\u2013bipyramidal coordination [C\u2014Sn\u2014C = 157.0\u2005(1)\u00b0]; however, two [Me2SnCl2(H2O)] units are linked by a tin\u2013chlorine bridge [Sn\u2190Cl = 3.247\u2005(1)\u2005\u00c5] across a center of inversion, generating a dinuclear species, so that the geometry is better regarded as a mer-C2SnCl3O octa\u00adhedron. The crown ether inter\u00adacts through O\u2014H\u22efO hydrogen with the metal atom through the coordinated water mol\u00adecules in an outer-sphere manner, generating a hydrogen-bonded chain running along [101]. The 15-crown-5 mol\u00adecule is disordered over the 2/m site.The Sn, Cl and water O atoms of the title compound, [Sn DOI: 10.1107/S1600536812008781/xu5444Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The conformation of the aliphatic C\u2014C\u2014C\u2014C chain is gauche [torsion angle = \u221267.7\u2005(8)\u00b0]. A weak C\u2014H\u22efBr inter\u00adaction helps to establish the conformation. In the crystal, there is a weak secondary bonding inter\u00adaction [Te\u22efN = 3.456\u2005(11)\u2005\u00c5] between the Te atom and the N atom of the solvent mol\u00adecule, which completes a distorted TeNCBr4 octa\u00adhedron. Inversion dimers linked by pairs of C\u2014H\u22efBr inter\u00adactions are also observed.In the title compound, [TeBr DOI: Click here for additional data file.10.1107/S1600536812051707/hb7012Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The [SbBr6]3\u2212 and [SbBr4]\u2212 anions are linked together by two long Sb\u2014Br bonds of 3.2709\u2005(8) and 3.5447\u2005(7)\u2005\u00c5 into {[Sb2Br10]4\u2212}n chains along [001]. One of the three tetra\u00admethyl\u00adethylendi\u00adammonium cations is disordered and was refined using a split model (occupancy ratio 0.58:0.42). The cations and the water mol\u00adecule are connected to the {[Sb2Br10]4\u2212}n polymeric anions by weak N\u2014H \u22efBr and O(water)\u2014H \u22efBr hydrogen bonding.The asymmetric unit of the title compound {(C DOI: 10.1107/S1600536813028894/nc2318Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The azotetra\u00adzolate ligand displays a bridging coordination mode, forming an infinite zigzag chain. Inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonding and offset face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.4738\u2005(13)\u2005\u00c5] lead to a three-dimensional network.In the title compound, {[Fe(C DOI: 10.1107/S1600536810039632/ng5036Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex cation [Mn2(C2O4)(C10N2H8)4]2+, two MnII atoms are bridged by a bis\u00ad(bidentate) oxalate ligand, each MnII atom being further coordinated by two bpy ligands in a distorted octa\u00adhedral geometry. The distance between the two six-coordinated metal atoms is 5.583\u2005(1)\u2005\u00c5. \u03c0\u2013\u03c0 stacking inter\u00adactions [inter\u00adplanar distances between bpy rings = 3.739\u2005(1)\u2005\u00c5] are essential to the supramolecular assembly. There are extensive inter\u00adionic C\u2014H\u22efO inter\u00adactions between the cations and between the cation and anion. Three of the four perchlorate O atoms are disordered over two sets of sites with occupancy ratios of 0.852\u2005(6):0.148\u2005(6).The unit cell of the title compound, [Mn DOI: 10.1107/S1600536811038475/bv2191Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex, there is an intra\u00admolecular N\u2014H\u22efN hydrogen bond. In the crystal, the binuclear units are connected by inter\u00admolecular N\u2014H\u22efCl hydrogen bonds, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.526\u2005(2) and 3.696\u2005(2)\u2005\u00c5], forming a two-dimensional layered structure parallel to (010).In the centrosymmetric binuclear title complex, [Hg DOI: 10.1107/S1600536811029886/su2294Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dimeric aggregates thus formed are arranged in rows with their terminal NH2 groups forming N\u2014H\u22efO hydrogen bonds with neighbouring aggregates to form a two-dimensional array in the ac plane with an overall T-shaped topology. Layers inter\u00addigitate along the b axis being connected by C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.6316\u2005(19)\u2005\u00c5] inter\u00adactions.The constituents of the title co-crystal, C DOI: 10.1107/S1600536810034094/hg2707Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom in the cation of the title salt, [Zn(C2H3O2)(C18H40N4)]ClO4, is five-coordinated by the four N atoms of the macrocycle and the O atom of the monodentate acetate ligand. The N4O donor set is based on a trigonal bipyramid with two N atoms occupying axial positions [N\u2014Zn\u2014N = 170.89\u2005(16)\u00b0]. The perchlorate anions are associated with the cations via N\u2014H\u22efO hydrogen bonds; intra\u00admolecular N\u2014H\u22efO(acetate) inter\u00adactions are also observed. The neutral aggregates are connected into an helical chain along the b axis via N\u2014H\u22efO(acetate) hydrogen bonds. The perchlorate anion was found to be disordered about a pseudo-threefold axis: the major component of the disorder had a site occupancy factor of 0.692\u2005(11).The Zn N-substituted derivatives and their metal complexes, see: Bembi et al. (C18H40N4)]ClO4                         = 0.080                           wR(F                           2) = 0.183                           S = 1.29                           4534 reflections320 parameters22 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.63 e \u00c5\u22123                        \u0394\u03c1min = \u22120.48 e \u00c5\u22123                        \u0394\u03c1                                 CrystalClear  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811045582/hb6470Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each, two \u03ba2N:N-chelating 5-(pyridin-2-yl)pyrazine-2-carbonitrile ligands surround the AgI atom, giving an N4O square-pyramidal coordination geometry with one trifluoro\u00adacetate O atom at the apex. The difference between the two lies in the Ag\u2014N bond lengths: in one complex, three normal [range 2.272\u2005(5)\u20132.552\u2005(5)\u2005\u00c5] and one long [2.706\u2005(4)\u2005\u00c5] and in the second, two normal [2.254\u2005(5) and 2.290\u2005(5)\u2005\u00c5] and two long [2.647\u2005(5) and 2.675\u2005(5)\u2005\u00c5] are present. Short inter\u00admolecular F\u22efF contacts [2.586\u2005(4)\u2005\u00c5] and weak \u03c0\u2013\u03c0 stacking inter\u00adactions [minimum ring centroid separation 3.836\u2005(5)\u2005\u00c5] between pyridyl and pyrazinyl rings connect the complex units, forming columns which extend along the b-axis direction.In the asymmetric unit of the title compound, [Ag(C DOI: Click here for additional data file.10.1107/S1600536812040846/zs2235Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII ion has a square-pyramidal coordination sphere, the basal plane being occupied by four N atoms  in a nearly planar array [mean deviation = 0.048\u2005(6)\u2005\u00c5] with the CuII ion displaced slightly from the plane [0.167\u2005(5)\u2005\u00c5] toward the fifth ligand. The apical position is occupied by a coordinating water mol\u00adecule [Cu\u2014O = 2.319\u2005(4)\u2005\u00c5]. The crystal structure is stabilized by hydrogen-bonding inter\u00adactions between the water mol\u00adecules and carbonyl O atoms. The inversion-related square-pyramidal complex molecules pack base-to-base with long Cu\u22efNpy contact distances of 3.537\u2005(9)\u2005\u00c5, preventing coordination of a sixth ligand.The title compound, [Cu(C II complexes, see: Landee & Turnbull (N3)(H2O)] = 0.063wR(F2) = 0.105S = 1.172258 reflections205 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.50 e \u00c5\u22123\u0394\u03c1min = \u22120.69 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027499/sj5358Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The central Fe2S2 core is in a butterfly conformation and each FeI atom has a pseudo-square-pyramidal coordination by three O atoms and two S atoms. The Fe\u2014Fe distance is 2.471\u2005(2)\u2005\u00c5 and the dihedral angle between the two Fe\u2014S\u2014Fe planes is 78.96\u2005(7)\u00b0. The least-squares plane through the \u2013S(C7H6S)S\u2013 bridge nearly bis\u00adects the mol\u00adecular structure: except for the two Fe(CO)3 units, all atoms are in this plane with an average deviation from the plane of 0.028\u2005(3)\u2005\u00c5. In the crystal, the mol\u00adecules are linked into chains along [001] by C\u2014H\u22ef\u03c0(arene) inter\u00adactions.The title compound, [Fe DOI: Click here for additional data file.10.1107/S1600536813009860/vn2067Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The organic ligand is bidentate, coordinating the ZnII atom via the two N atoms. The benzene and pyridine rings are oriented at a dihedral angle of 11.67\u2005(9)\u00b0. In the crystal, weak C\u2014H\u22efI and C\u2014H\u22efO hydrogen bonds are observed, in addition to \u03c0\u2013\u03c0 stacking inter\u00adactions, with a centroid\u2013centroid distance of 3.72\u2005(5)\u2005\u00c5.In the title complex, [ZnI DOI: 10.1107/S1600536812030486/br2207Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal packing can be described as ClO4 tetra\u00adhedra and CuN4O2 octa\u00adhedra alternating in a zigzag fashion along the c axis. The structure is stabilized by intermolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 interactions [centroid\u2013centroid distance = 3.7179\u2005(15)\u2005\u00c5].In the title compound, [Cu(ClO DOI: 10.1107/S1600536812029868/zj2084Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The ZnII atoms are connected by the bridging ligands into a layer parallel to (101). O\u2014H\u22efO hydrogen bonds link the layers and the dimethyl\u00adformamide solvent mol\u00adecules. \u03c0\u2013\u03c0 inter\u00adactions between the pyridine and benzene rings [centroid\u2013centroid distances = 3.7428\u2005(17) and 3.7619\u2005(17)\u2005\u00c5] and intra\u00adlayer O\u2014H\u22efO hydrogen bonds are also present.In the title compound, {[Zn(C DOI: Click here for additional data file.10.1107/S1600536812043838/hy2597Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The 4,4\u2032-bpy ligand has an inversion center at the mid-point of the central C\u2014C bond. The empty side of the metal ion is capped by two carboxyl\u00adate O atoms from a neighboring mol\u00adecule, with weak Pb\u22efO contacts [Pb\u22efO = 3.069\u2005(2) and 3.071\u2005(3)\u2005\u00c5]. The crystal structure is stabilized by C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the benzene and pyridine rings [centroid\u2013centroid distance = 3.749\u2005(3)\u2005\u00c5].In the title dinuclear complex, [Pb DOI: 10.1107/S1600536811022422/hy2436Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Its structure is isotypic with the CoII analogue. The crystal structure is built up from centrosymmetric dinuclear complex mol\u00adecules and the structure is reinforced by a net of inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. One water mol\u00adecule is bound to the NiII atom in the octahedral coordination sphere, while the second is part of the inter\u00admolecular hydrogen-bond system.The title compound {sys\u00adtematic name: bis(\u03bc II compound, see: Man et al. 4(H2O)2]\u00b72H2O = 0.046wR(F2) = 0.124S = 1.073522 reflections298 parameters6 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 2.44 e \u00c5\u22123\u0394\u03c1min = \u22120.67 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812022532/zj2074Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, the complex mol\u00adecules and uncoordinated water mol\u00adecules are linked via inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds, forming a three-dimensional supra\u00admolecular network. \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings provide additional stability of the crystal packing [centroid\u2013centroid distance = 3.792\u2005(2)\u2005\u00c5].In the title compound, [Ni(C DOI: 10.1107/S1600536811051063/hy2491Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each Ni2+ cation is coordinated in a cis-mode by two tridentate N,N\u2032,S-chelating Schiff base ligands, creating a distorted octa\u00adhedron . The dihedral angle between the mean coordination planes of the two ligands is 86.76\u2005(7)\u00b0 for one and 89.99\u2005(7)\u00b0 for the second mol\u00adecule. \u03c0\u2013\u03c0 inter\u00adactions between neighbouring pyridine rings with plane-to-plane distances of 3.540\u2005(1) and 3.704\u2005(1)\u2005\u00c5 are observed.The asymmetric unit of the title compound, [Ni(C DOI: 10.1107/S1600536812017333/wm2622Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Cu atom binds to four O atoms, resulting in a four-coordinate square-planar complex. The asymmetric unit contains half of the complex, the other half being completed by inversion symmetry. The Cu\u2014O bond lengths have similar distances, viz. 1.9153\u2005(10)\u2005\u00c5 for the pair opposite (trans) each other and 1.9373\u2005(10)\u2005\u00c5 for the other (trans) pair. The P\u2014O bond lengths are 1.5250\u2005(11)\u2005\u00c5, indicating significant electron delocalization across the O\u2014P\u2014C\u2014P\u2014O atoms in the chelate ring, resulting in a longer P\u2014O bond length when compared to a formal double-bond P=O character (much shorter at approximately 1.47\u2005\u00c5). The two inter\u00adsecting O\u2014Cu\u2014O angles are both linear at 180\u00b0, whilst the remaining L-shaped O\u2014Cu\u2014O bond angles are 88.26\u2005(5) and 91.74\u2005(5)\u00b0. The C\u2014C\u00a0N fragment is slightly distorted from linearity at 177.44\u2005(19)\u00b0 and the C\u00a0N bond length of 1.151\u2005(2)\u2005\u00c5 indicates predominantly triple-bond character.The title complex, [Cu(C For a b al. 2011 and for  al. 2008. For bac al. 2008        26H20NO2P2)2] = 0.033                           wR(F                           2) = 0.086                           S = 1.03                           5640 reflections286 parametersH-atom parameters constrainedmax = 0.49 e \u00c5\u22123                        \u0394\u03c1min = \u22120.32 e \u00c5\u22123                        \u0394\u03c1                                 COSMO  I, global. DOI: 10.1107/S1600536811031564/ff2023Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two axial coordination sites are occupied by carbonyl O atoms of neighbouring glycine mol\u00adecules. The Cu\u2014O distances for the axial O atoms [2.648\u2005(2) and 2.837\u2005(2)\u2005\u00c5] are considerably longer than both the Cu\u2014O [1.9475\u2005(17) and 1.9483\u2005(18)\u2005\u00c5] and Cu\u2014N [1.988\u2005(2) and 1.948\u2005(2)\u2005\u00c5] distances in the equatorial plane, which indicates a strong Jahn\u2013Teller effect. In the crystal, the two-dimensional networks are arranged parallel to (001) and are linked via N\u2014H\u22efO hydrogen bonds, forming a three-dimensional arrangement.The title coordination polymer, [Cu(C DOI: 10.1107/S1600536811031503/su2280Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the CoII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 29.7\u2005(4)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 83.17\u2005(15)\u00b0. Intra\u00admolecular O\u2014H\u22efO hydrogen bonding occurs between the carboxyl\u00adate group and coordinating water mol\u00adecule. In the crystal, inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network.In the title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.088wR(F2) = 0.237S = 1.233285 reflections202 parametersH atoms treated by a mixture of independent and constrained refinementmax = 1.42 e \u00c5\u22123\u0394\u03c1min = \u22121.61 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813004984/xu5678Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the benzene rings is 24.8\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked into chains along the b axis by weak C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions. An inter\u00admolecular Cl\u22efCl [3.4564\u2005(19)\u2005\u00c5] inter\u00adaction is present which is shorter than the sum of the van der Waals radii of Cl atoms (3.50\u2005\u00c5).In the title compound, [Ni(C DOI: 10.1107/S1600536812002085/lh5404Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The bpbd mol\u00adecules bridge the Ag atoms into a chain. Two adjacent chains are further connected by Ag\u22efAg inter\u00adactions [3.1631\u2005(8)\u2005\u00c5], forming a double-chain structure. A \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.758\u2005(3)\u2005\u00c5] occurs between the double chains. Inter\u00adchain C\u2014H\u22efO hydrogen bonds are observed.In the title compound, [Ag(NO DOI: 10.1107/S1600536810025997/hy2324Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The stereochemistry about each FeCl3O centre is distorted tetra\u00adhedral [Fe\u2014Cl = 2.2176\u2005(5)\u20132.2427\u2005(5)\u2005\u00c5 and Fe\u2014O = 1.7545\u2005(2)\u2005\u00c5]. The Cl atoms are involved in weak anion\u2013cation C\u2014H\u22efCl inter\u00adactions, giving a network structure.In the title compound (C DOI: 10.1107/S1600536810024098/zs2046Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex mol\u00adecule and the solvent water mol\u00adecule are located on a twofold rotation axis. In the complex, the MnII ion has a distorted cis-N4O2 octa\u00adhedral coordination geometry defined by four N atoms of the two chelating 2,2\u2032-bipyrimidine ligands and two O atoms of water mol\u00adecules. In the crystal, the complex cations, anions and solvent mol\u00adecules are linked by inter\u00admolecular O\u2014H\u22efN, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds. The ClO4               \u2212 anion is disordered over two sites with a site-occupancy factor of 0.512\u2005(12) for the major component.The asymmetric unit of the title compound, [Mn(C II complexes, see: Hong et al. 2(H2O)2](ClO4)2\u00b72CH3NO2\u00b7H2O = 0.059                           wR(F                           2) = 0.199                           S = 1.06                           3617 reflections208 parametersH-atom parameters constrainedmax = 1.05 e \u00c5\u22123                        \u0394\u03c1min = \u22120.69 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811045612/xu5372Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecule belongs to the symmetry point group Ch2. The CuII ion is located on a twofold rotation axis and the hydroxide and perchlorate ligands are located on a mirror plane. Within the dinuclear mol\u00adecule, the Cu\u22efCu separation is 2.8614\u2005(7)\u2005\u00c5. The crystal structure exhibits O\u2014H\u22efO, C\u2014H\u22efO and \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.5374\u2005(13)\u2005\u00c5] inter\u00adactions.In the title binuclear copper(II) complex, [Cu DOI: 10.1107/S1600536813027852/bt6938Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is stablized by weak inter\u00admolecuar C\u2014H\u22ef\u03c0 and N\u2014H\u22ef\u03c0 inter\u00adactions.In the title mol\u00adecule, C DOI: 10.1107/S1600536810029788/lh5094Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The correct Equation should be j = \u03c3 E. An error occurred in Equation 6, j ="}
{"text": "The asymmetric unit contains two independent complex mol\u00adecules as well as two independent benzoic acid solvent mol\u00adecules, one of which is disordered over two positions with almost equal occupancies [0.504\u2005(5) and 0.496\u2005(5)]. The two complex mol\u00adecules have similar configurations with the hexa\u00adcoordinated environment of the PbII atom formed by four carboxyl\u00adate O atoms of two chelate benzoate ligands and two N atoms of the bipy ligand. The Pb\u2014O bonds involving one of the benzoate ligands are almost coplanar with Pb\u2014N bonds to the bipy ligand [dihedral angles of 12.67\u2005(11) and 14.73\u2005(11)\u00b0] ; if the second benzoate ligand is treated as one coordination site, the overall coordination may be represented as a distorted pseudo-square pyramid. Weak inter\u00admolecular Pb\u22efO inter\u00adactions [3.046\u2005(3) and 3.359\u2005(3)\u2005\u00c5] link each of the complex mol\u00adecules into two symmetry-independent centrosymmetric dimers. Hydrogen bonds involving the carboxyl H atoms of solvent benzoic acid mol\u00adecules and metal-coordinated carboxyl\u00adate O atoms link complex mol\u00adecules and benzoic acid solvent mol\u00adecules into insular aggregates.The reaction of lead acetate, benzoic acid and 2,2\u2032-bipyridine (bipy) in aqueous solution yielded the title complex, [Pb(C For the al. 2006; Masaoka al. 2001.       7H5O2)2(C10H8N2)]\u00b7C7H6O2                         = 0.035                           wR(F                           2) = 0.081                           S = 1.01                           14302 reflections773 parametersH-atom parameters constrainedmax = 1.17 e \u00c5\u22123                        \u0394\u03c1min = \u22121.13 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL (Sheldrick, 2008SHELXTL.Data collection: 10.1107/S1600536810046489/ya2132sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810046489/ya2132Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both amine H atoms are involved in N\u2014H\u22efS hydrogen bonding, resulting in the formation of layers of inter\u00adlinked mol\u00adecules parallel to the ab plane, which are further held together by weak \u03c0\u2013\u03c0 inter\u00adactions between adjacent complexes, involving one ring of each dipyridyl\u00adamine unit [centroid\u2013centroid distance = 3.777\u2005(4)\u2005\u00c5], forming a three-dimensional assembly.The mononuclear neutral title complex, [Ni(NCS) II, CuII and ZnII complexes with amine ligands, see: Wrzeszcz et al. 2(NCS)2] complexes, see: Wang et al. 2] = 0.066                           wR(F                           2) = 0.161                           S = 1.03                           4107 reflections304 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.77 e \u00c5\u22123                        \u0394\u03c1min = \u22120.84 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811050197/pk2364Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecular conformation is stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid distance = 3.600\u2005(1)\u2005\u00c5] between substituted benzene rings of different ligands. The crystal packing is characterized by C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions involving the chloro\u00adform solvent mol\u00adecules.In the title compound, [PdCl DOI: Click here for additional data file.10.1107/S1600536812045801/zq2184Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The effective cone angles for the two phosphane ligands are 160 and 169\u00b0. C\u2014H\u22efCl inter\u00adactions generate infinite long chains along [01-1]. Additional C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking interactions [centroid\u2013centroid distance = 4.2499\u2005(15)\u2005\u00c5 and ring slippage = 2.386\u2005\u00c5] are observed.In the mononuclear title compound,  DOI: Click here for additional data file.10.1107/S160053681204696X/ng5305Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, weak C\u2014H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between parallel pyridine rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.653\u2005(3)\u2005\u00c5] link the mol\u00adecules into a two-dimensional supra\u00admolecular architecture. The structure contains voids of 124\u2005(9)\u2005\u00c53, which are free of solvent molecules.In the title complex, [Fe(NCS) For rel al. 2008; Min et  al. 2008; Phan et al. 2012; Wei et  al. 2011.2(C18H18N4)] = 0.069wR(F2) = 0.203S = 1.114456 reflections283 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.42 e \u00c5\u22123\u0394\u03c1min = \u22120.47 e \u00c5\u22123\u0394\u03c1CrystalClear  used to solve structure: SHELXTL  I, global. DOI: 10.1107/S1600536813034818/xu5762Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The CuII atom occupies a four-coordinate pseudo-tetra\u00adhedral environment bound to one S atom, one imine N atom and one pyridine N atom from the N1,N2-bis\u00ad(pyridin-2-yl)hydrazine-1,2-dicarbo\u00adthio\u00adamidate ligand, and one Cl\u2212 anion. The metal atoms are connected via the bis-tridentate ligand into a binuclear structure. The mol\u00adecule is bow-shaped with the pyridine rings inclined to one another by 51.56\u2005(14)\u00b0. In the crystal, N\u2014H\u22efCl hydrogen bonds lead to the formation of ribbons propagating along [001]. These ribbons are connected via C\u2014H\u22efCl, C\u2014H\u22efS and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6146\u2005(19)\u2005\u00c5], leading to the formation of a three-dimensional structure.The binuclear title compound, [Cu Cl2] = 0.024wR(F2) = 0.068S = 1.071561 reflections110 parametersH-atom parameters constrainedmax = 0.73 e \u00c5\u22123\u0394\u03c1min = \u22120.34 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: Click here for additional data file.10.1107/S1600536812048659/su2393Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two pyridyl planes are inclined with dihedral angles of 59.1\u2005(2) and 61.84\u2005(19)\u00b0 with respect to the PtCl2N2 plane. In the crystal, the complex mol\u00adecules display inter- and intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid-centroid distances of 3.806\u2005(5)\u20133.845\u2005(5)\u2005\u00c5, which form a one-dimensional column structure along the a axis.In the title complex,  DOI: 10.1107/S160053681004393X/is2622Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The environment of Cu2+ ion is a distorted octa\u00adhedron. The axial bond lengths between the CuII ion and the N atoms are considerably longer than the equatorial bond distances between the CuII ion and the N atoms of the ethyl\u00adenediamine ligand as a consequence of the Jahn\u2013Teller effect. The mol\u00adecular conformation is stabilized by intra\u00admolecular N\u2014H\u22efO hydrogen bonds. In the crystal, mol\u00adecules are connected by inter\u00admolecular N\u2014H\u22efO hydrogen bonds into chains running along the a axis.In the crystal structure of the title compound, [Cu(C H)-one 2,2-dioxide], see: Clauss & Jensen 2(C2H8N2)2] = 0.024                           wR(F                           2) = 0.065                           S = 1.09                           2023 reflections150 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.23 e \u00c5\u22123                        \u0394\u03c1min = \u22120.25 e \u00c5\u22123                        \u0394\u03c1                                 X-AREA  I, global. DOI: 10.1107/S1600536811051658/bt5731Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The HgII atoms are four-coordinated in a distorted tetra\u00adhedral geometry by two N atoms from a 2,2\u2032-dimethyl-4,4\u2032-bi-1,3-thia\u00adzole ligand and two Br atoms. In the crystal structure, inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 contacts between the thia\u00adzole rings [centroid\u2013centroid distances = 3.670\u2005(3) and 3.614\u2005(2)\u2005\u00c5] stabilize the structure.The asymmetric unit of the title compound, [HgBr DOI: 10.1107/S1600536810051494/hy2386Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II ion in the title complex, [PtI2(C10H9N3)], is four-coordinated in a distorted square-planar environment defined by the two pyridine N atoms of the chelating di-2-pyridyl\u00adamine (dpa) ligand and by two I\u2212 anions. The dpa ligand is not planar, the dihedral angle between the pyridine rings being 52.8\u2005(3)\u00b0. Pairs of complex mol\u00adecules are assembled through inter\u00admolecular N\u2014H\u22efI hydrogen bonds, forming a dimer-type species. The complexes are stacked in columns along the b axis and display several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings, with a shortest ring centroid\u2013centroid distance of 3.997\u2005(5)\u2005\u00c5.The Pt II complex [PtCl2(dpa)], see: Li & Liu ] = 0.031wR(F2) = 0.077S = 1.072527 reflections145 parametersH-atom parameters constrainedmax = 1.47 e \u00c5\u22123\u0394\u03c1min = \u22121.31 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812011907/wm2603Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the ligand, the hy\u00addroxy group is involved in an intra\u00admolecular O\u2014H\u22efN hydrogen bond and the two aromatic rings form a dihedral angle of 5.5\u2005(1)\u00b0. In the crystal, weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings [centroid\u2013centroid distance = 3.816\u2005(3)\u2005\u00c5] link the mol\u00adecules into centrosymmetric dimers.In the title compound, [Sn(CH DOI: 10.1107/S1600536811025621/cv5115Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "IV atom in the title complex, [V(C19H17N3O2S)O], is coordinated by two N and two O atoms of the dianionic tetra\u00addentate Schiff base ligand and the terminal oxide O atom. The N2O3 donor set defines a square-pyramidal coordination geometry with the oxide O atom in the apical site. Some buckling in the tetra\u00addentate ligand is indicated by the dihedral angle of 17.92\u2005(19)\u00b0 between the six-membered chelate rings. Supra\u00admolecular chains are formed along the b axis via C\u2014H\u22efO contacts in the crystal. The chains are connected into a layer in the ab plane via C\u2014H\u22ef\u03c0 inter\u00adactions. The atoms comprising the \u2013SCH2\u2014CH=CH2 and methyl substituents were found to be disordered in a 0.916\u2005(2):0.088\u2005(2) ratio. The crystal studied was found to be twinned by nonmerohedry with a 28.1\u2005(4)% minor twin component.The V O] = 0.076wR(F2) = 0.191S = 1.204134 reflections257 parameters3 restraintsH-atom parameters constrainedmax = 0.98 e \u00c5\u22123\u0394\u03c1min = \u22120.94 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812029819/hb6874Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Two dppm ligands, two dpp ligands and two trifluoro\u00adacetate anions bridge four metal atoms, forming a centrosymmetric tetra\u00adnuclear complex. Intra\u00admolecular C\u2014H\u22efO hydrogen bonds and a weak \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.9804\u2005(13)\u2005\u00c5] are also observed.In the cation of the title compound, [Ag DOI: 10.1107/S1600536811045466/rz2658Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It is chelated by four N atoms of two different 5,5\u2032-dimethyl-2,2\u2032-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water mol\u00adecules are disordered and their H atoms were not located, there are typical O\u22efO distances between 2.8 and 3.0\u2005\u00c5, indicating O\u2014H\u22efO hydrogen bonding. The crystal packing is consolidated by C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent pyridine rings of the dmbpy ligands, with centroid\u2013centroid distances of 3.694\u2005(3) and 3.7053\u2005(3)\u2005\u00c5.In the title complex, [Co(CO DOI: 10.1107/S160053681200894X/wm2590Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The organic cation is essentially planar, with a maximum deviation of 0.013\u2005(1)\u2005\u00c5. In the crystal structure, the ions and mol\u00adecules are linked into a pseudo-layered three-dimensional supra\u00admolecular network via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions further stabilize the crystal structure [centroid\u2013centroid distance = 3.5231\u2005(4)\u2005\u00c5].In the title compound, (C DOI: 10.1107/S1600536810026693/hb5536Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the mol\u00adecules are packed via \u03c0\u2013\u03c0 stacking inter\u00adactions alternating between imidazole and benzene rings [mean inter\u00adplanar distances = 3.754\u2005(3) and 3.624\u2005(3)\u2005\u00c5]. An inter\u00admolecular N\u2014H\u22efO hydrogen bond links the dimers together. The two-coordinate CuI atom displays an O\u2014Cu\u2014N bond angle of 176.3\u2005(2)\u00b0. The Cu\u22efCu distance within the dimer is 5.100\u2005(2)\u2005\u00c5.The dimeric title complex, [Cu DOI: 10.1107/S1600536810046040/om2365Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the water mol\u00adecules is coordinated with the ZnII ion and this mol\u00adecule forms an O\u2014H\u22efO inter\u00adaction with the lattice water mol\u00adecule. The pyridine-2,6-dicarboxyl\u00adate ligand is almost planar (r.m.s. deviation = 0.0242\u2005\u00c5). In the crystal, C\u2014H\u22efO, C\u2014H\u22efN, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds are present.In the title compound, [Zn(C DOI: 10.1107/S1600536811015571/zj2009Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal atom is surrounded by the two dimethyl sulfoxide (DMSO) ligands, each coordinating through the O atom, and two anionic saccharinate  ligands coordinating through the N atom. The tetra\u00adhedral geometry is slightly distorted as is evident from the N\u2014Zn\u2014N bond angle of 113.85\u2005(6)\u00b0, the O\u2014Zn\u2014O bond angle of 98.92\u2005(6)\u00b0 and O\u2014Zn\u2014N bond angles of 116.96\u2005(6) and 103.93\u2005(6)\u00b0. The Zn\u2014N bond lengths are 1.9742\u2005(15) and 2.0025\u2005(16)\u2005\u00c5. The Zn\u2014O bond lengths are 1.9806\u2005(14)\u2005\u00c5 and 1.9468\u2005(14)\u2005\u00c5. The DMSO ligand coordinates through the lone pair of electrons on the O atom, as can be seen from the Zn\u2014O\u2014S bond angle of 131.30\u2005(8)\u00b0.The title compound, [Zn(C DOI: 10.1107/S1600536811045703/fj2470Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One uncoordinated dmphen mol\u00adecule is situated on a crystallographic twofold axis and the asymmetric unit is completed by one water mol\u00adecule. In the crystal, mol\u00adecules form a one-dimensional framework in the [001] direction through O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds. The crystal packing is further stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions between the dmphen rings of neighboring mol\u00adecules, with a centroid\u2013centroid separation of 3.5641\u2005(8)\u2005\u00c5 and a partially overlapped arrangement of parallel dmphen rings with a distance of 3.407\u2005(2)\u2005\u00c5.In the title compound, 2[Co(C DOI: 10.1107/S1600536811035148/bh2369Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex mol\u00adecules are connected into a one-dimensional structure along [001] via N\u2014H\u22efN hydrogen bonds and further into a three-dimensional structure via N\u2014H\u22efCl hydrogen bonds. \u03c0\u2013\u03c0 inter\u00adactions between the pyrazine and benzene rings and between the benzene rings [centroid\u2013centroid distances = 3.5635\u2005(15) and 3.9128\u2005(16)\u2005\u00c5] are present.In the title complex, [CuCl(C DOI: 10.1107/S1600536812005582/hy2514Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The distorted octa\u00adhedral trans-N2S4 donor set for the Cd2+ ion is defined by two symmetrically S,S\u2032-chelating dithio\u00adcarbamate anions and two pyridine N atoms derived from two monodentate 4-pyridine\u00adaldazine (or 4-{[(pyridin-4-yl\u00admethyl\u00adidene)hydrazinyl\u00adidene}meth\u00adyl]pyridine) mol\u00adecules [dihedral angle between the aromatic rings = 17.33\u2005(8)\u00b0]. In the crystal, mol\u00adecules are connected into a supra\u00admolecular chain via O\u2014H\u22efN hydrogen bonds involving the 4-pyridine\u00adaldazine N atoms not involved in coordination to cadmium. Weak C\u2014H\u22efO and C\u2014H\u22efN links consolidate the packing.The complete mol\u00adecule of the title compound, [Cd(C DOI: 10.1107/S1600536811004508/hb5795Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atoms are bridged by the 3-amino\u00adpyridine ligands [Ni\u22efN = 6.7048\u2005(3)\u2005\u00c5] and Cl\u2212 atoms [Ni\u22efN = 3.5698\u2005(3)\u2005\u00c5], forming  two-dimensional nets. The DMF solvent mol\u00adecule and the non-bridged Cl\u2212 ions participate in N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds with the amino groups. The title compound, {[NiCl DOI: 10.1107/S1600536812036215/xu5609Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title salt, [Cu(C10H24N4)(H2O)2](C6F5CO2)2\u00b72H2O, is chelated by the four N atoms of the 1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane (cyclam) ligand and is coordinated by two water mol\u00adecules in a Jahn\u2013Teller-type tetra\u00adgonally distorted octa\u00adhedral geometry. The CuII atom lies on a center of inversion. The cations, anions and uncoordinated water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a layer structure parallel to (001).The Cu DOI: 10.1107/S1600536810025705/bt5287Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Co atom is 0.0187\u2005(8)\u2005\u00c5 out of the mean plane of the four equatorial N atoms. The structure has an O\u22efH\u22efO bridge, which is very common in cobaloxime derivatives, with O\u22efH distances of 1.24\u2005(2) and 1.25\u2005(2)\u2005\u00c5. In the title compound, [Co(C DOI: 10.1107/S1600536811051397/vn2023Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II ion in the title complex, [PdI2(C10H9N3)], is four-coordinated in a distorted square-planar environment defined by the two pyridine N atoms of the chelating di-2-pyridyl\u00adamine (dpa) ligand and two I\u2212 anions. The dpa ligand is not planar, the dihedral angle between the pyridine rings being 51.2\u2005(2)\u00b0. In the crystal, pairs of complex mol\u00adecules are assembled through inter\u00admolecular N\u2014H\u22efI hydrogen bonds into dimeric species. The complexes are stacked in columns along the b axis and display several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings, with a shortest ring centroid\u2013centroid distance of 3.957\u2005(3)\u2005\u00c5.The Pd II complex [PtI2(dpa)], see: Ha ] = 0.028wR(F2) = 0.065S = 1.013152 reflections145 parametersH-atom parameters constrainedmax = 1.17 e \u00c5\u22123\u0394\u03c1min = \u22120.78 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812033946/tk5137Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 9.14\u2005(9)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 82.18\u2005(8)\u00b0. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a two-dimensional network lying parallel to (101). \u03c0\u2013\u03c0 stacking between parallel pyridine rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.7765\u2005(8)\u2005\u00c5] further stabilizes the crystal structure.In the title complex, [Co(C N,N-di\u00adethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.027wR(F2) = 0.074S = 1.112797 reflections204 parameters52 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.32 e \u00c5\u22123\u0394\u03c1min = \u22120.33 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S160053681301458X/su2606Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title complex, [Ni(C8H5N5O3)(C2H8N2)(H2O)]\u00b72H2O, is six-coordinated in a distorted octa\u00adhedral geometry by a tridentate 2-amino-7-methyl-4-oxidopteridine-6-carboxyl\u00adate (pterin) ligand, a bidentate ancillary ethane-1,2-diamine (en) ligand and a water mol\u00adecule. The pterin ligand forms two chelate rings. The en and pterin ligands are arranged nearly orthogonally [dihedral angle between the mean plane of the en mol\u00adecule and the pterin ring = 77.1\u2005(1)\u00b0]. N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds link the complex mol\u00adecules and lattice water mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 inter\u00adactions are observed between the pyrazine and pyrimidine rings [centroid\u2013centroid distance = 3.437\u2005(2)\u2005\u00c5].The Ni DOI: Click here for additional data file.10.1107/S160053681300069X/hy2612Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the cations, the ZnII ions have distorted trigonal\u2013bipyramidal environments formed by four N atoms from two 2-chloro-1,10-phenanthroline (cphen) ligands and one N atom from a thio\u00adcyanate ligand. The ZnII atoms in the complex anions also have distorted trigonal\u2013bipyramidal environments, formed by two N atoms from a cphen ligand and three N atoms from three thio\u00adcyanato ligands. The crystal packing exhibits \u03c0\u2013\u03c0 inter\u00adactions between the rings of the cphen ligands [shortest centroid\u2013centroid distance = 3.586\u2005(5)\u2005\u00c5] and short inter\u00admolecular S\u22efCl [3.395\u2005(5)\u2005\u00c5] and S\u22efS [3.440\u2005(4)\u2005\u00c5] contacts.The asymmetric unit of the title compound, [Zn(NCS)(C DOI: 10.1107/S1600536812002280/cv5234Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the complex, the MnII ion is six-coordinated in a distorted octa\u00adhedral environment defined by four N atoms of the two chelating 2,2\u2032-bipyrimidine (bpym) ligands, one I\u2212 anion and one O atom of a water ligand. The dihedral angle between the least-squares planes of the two bpym ligands [maximum deviation = 0.092\u2005(7)\u2005\u00c5] is 79.9\u2005(1)\u00b0. In the crystal, the complex, anion and solvent water mol\u00adecule are linked by inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efI and O\u2014H\u22efN hydrogen bonds.The asymmetric unit of the title compound, [MnI(C II complexes, see: Hong et al. 2(H2O)]I\u00b7H2O = 0.052                           wR(F                           2) = 0.126                           S = 1.07                           5309 reflections262 parametersH-atom parameters constrainedmax = 1.69 e \u00c5\u22123                        \u0394\u03c1min = \u22121.98 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97  I. DOI: 10.1107/S160053681103875X/bv2192Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two NdIII atoms are linked by two bridging bidentate carboxyl\u00adate groups and two bidentate chelating bridging carboxyl\u00adate groups, with an Nd\u22efNd separation of 4.1259\u2005(4)\u2005\u00c5. Each NdIII atom is nine-coordin\u00adated by five O atoms from the carboxyl\u00adate groups of the zwitterionic azaniumylbenzoate ligands and four from water mol\u00adecules. They adopt a distorted tricapped trigonal\u2013prismatic arrangement. The dihedral angle between the mean planes of the benzene ring and the carboxlate groups are 7.7\u2005(6) and 24.4\u2005(5)\u00b0. The two carboxyl\u00adate groups are almost perpendicular to one another with a dihedral angle of 84.0\u2005(7)\u00b0, while the two benzene rings are inclined to one another by 81.8\u2005(2)\u00b0. The mol\u00adecular packing is stabilized by O\u2014Hwater\u22efCl, O\u2014Hwater\u22efN, N\u2014H\u22efCl, N\u2014H\u22efO, and O\u2014Hwater\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.500\u2005(3)\u2005\u00c5] between symmetry-related benzene rings. All of the Cl\u2212 anions and the uncoordinated water molecules are disordered over two sets of sites with different occupancy ratios.The structure of the title compound, [Nd DOI: 10.1107/S1600536811012700/su2265Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the mol\u00adecules are linked by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the triazole and benzene rings [centroid\u2013centroid distance = 3.794\u2005(3)\u2005\u00c5] into a band extending in [010]. These bands are further connected by C\u2014H\u22efN hydrogen bonds into a two-dimensional network parallel to (100).In the title complex, [HgI DOI: 10.1107/S160053681302518X/hy2634Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The asymmetric unit is completed by one 4-meth\u00adoxy\u00adbenzoate anion, one nicotinamide (NA) ligand and one coordinated and one uncoordinated water mol\u00adecule. All ligands act in a monodentate mode. The four O atoms in the equatorial plane around the CoII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 6.47\u2005(7)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 72.80\u2005(4)\u00b0. An O\u2014H\u22efO hydrogen bond links the uncoordinated water mol\u00adecule to one of the carboxyl\u00adate groups. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network.In the mononuclear title compound, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2]\u00b72H2O = 0.027                           wR(F                           2) = 0.074                           S = 1.07                           3776 reflections230 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.55 e \u00c5\u22123                        \u0394\u03c1min = \u22120.31 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810026462/cv2740sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026462/cv2740Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Three Cl atoms of the [ZnCl4]2\u2212 tetra\u00adhedron act as acceptors in N\u2014H\u22efCl hydrogen bonds. The hydrogen bonds, both of which are bifurcated, lead to the formation of a three-dimensional network. Within the network, inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions with a centroid\u2013centroid distance of 3.5911\u2005(7)\u2005\u00c5 arrange the 4-(dimethyl\u00adamino)\u00adpyridinium cations into anti\u00adparallel dimers.In the title compound, (C DOI: 10.1107/S1600536811005010/rk2262Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ppy ligands are not planar, the dihedral angles between the pyridine and benzene rings being 49.0\u2005(3) and 47.3\u2005(3)\u00b0. In the crystal, the complex mol\u00adecules are stacked in columns along the a axis. In the columns, there are numerous intra- and inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings, the shortest ring centroid\u2013centroid distance being 3.774\u2005(6)\u2005\u00c5.In the title complex, [PtBr II and PdII complexes, cis-[PtCl2(ppy)2] and trans-[PdX2(ppy)2] (X = Cl or I), see: Yoshinari et al. 2] = 0.028wR(F2) = 0.068S = 1.042931 reflections244 parameters2 restraintsH-atom parameters constrainedmax = 1.73 e \u00c5\u22123\u0394\u03c1min = \u22120.93 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 856 FriFlack parameter: \u22120.037 (13)SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Two NdIII ions are bridged by four carboxyl\u00adate groups in bi- and tridentate modes, forming a centrosymmetric dinuclear unit, with an Nd\u22efNd distance of 4.0021\u2005(5)\u2005\u00c5, and intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.960\u2005(2)\u2005\u00c5]. Inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.820\u2005(2) and 3.804\u2005(2)\u2005\u00c5] and O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds connect the dinuclear mol\u00adecules into a three-dimensional supra\u00admolecular network.In the title compound, [Nd DOI: 10.1107/S1600536811023798/hy2440Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The axial Cu\u2014O distances are significantly longer [2.512\u2005(2)\u2005\u00c5], than the Cu\u2014N [2.022\u2005(2)\u2005\u00c5] and Cu\u2014Cl [2.3232\u2005(4)\u2005\u00c5] distances as a result of Jahn\u2013Teller distortion. Aqua ligands are involved in intra- and inter\u00admolecular hydrogen bonding, and N\u2014H\u22efO inter\u00admolecular hydrogen bonds are formed between the organic ligands. In addition, weak \u03c0\u2013\u03c0 inter\u00adactions are observed between the benzene rings of the ligand [centroid\u2013centroid distance = 3.678\u2005(1)\u2005\u00c5].In the title complex, [CuCl H)-one was reported by Vaillancourt et al. (1998H)-one, see: Turgunov & Englert 2(H2O)2] = 0.032                           wR(F                           2) = 0.089                           S = 1.10                           1725 reflections137 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.37 e \u00c5\u22123                        \u0394\u03c1min = \u22120.46 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis PRO  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008XP (Bruker, 1998publCIF (Westrip, 2010Data collection: 10.1107/S1600536810048890/nk2075sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048890/nk2075Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Hf\u2014O bond lengths vary from 2.073\u2005(2) to 2.244\u2005(2)\u2005\u00c5 and the O\u2014Hf\u2014O bite angles vary from 73.49\u2005(9) to 75.60\u2005(9)\u00b0. Weak O\u2014H\u22efO hydrogen-bonding inter\u00adactions are observed between the bridging hy\u00addroxy groups and the dimethylformamide solvent mol\u00adecules. The unit cell contains solvent-accessible voids of 131\u2005\u00c53, but the residual electron density in the difference Fourier map suggests no solvent mol\u00adecule occupies this void.The binuclear molecule of the title compound, [Hf O,O\u2032-and N,O-bidentate ligands with hafnium(IV) and zirconium(IV) to exploit possible separation techniques and for the crystal structures of hafnium(IV) and zirconium(IV) complexes, see: Viljoen et al. 6(OH)2]\u00b72C3H7NO = 0.030                           wR(F                           2) = 0.072                           S = 1.03                           8726 reflections475 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 1.33 e \u00c5\u22123                        \u0394\u03c1min = \u22120.97 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SIR92  I, global. DOI: 10.1107/S1600536811049543/pv2484Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "As a result of this difference in the coordination modes, the C\u2014S bond lengths are different, viz. 1.687\u2005(2) and 1.692\u2005(2)\u2005\u00c5 in the bidentate ligand and 1.723\u2005(2)\u2005\u00c5 in the monodentate ligand, whereas the non-coordinating S atom has a C\u2014S distance of 1.649\u2005(2)\u2005\u00c5. The crystal packing is stabilized by C\u2014H\u22efO inter\u00adactions.The title compound, [Pd(C DOI: 10.1107/S1600536811040487/bt5655Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the 2-trifluoro\u00admethyl-1H-benzimidazolium cations link to the [HgCl4]2\u2212 complex anions and lattice water mol\u00adecules via N\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds, and the lattice water mol\u00adecules further link to the Hg complex anion and the organic cations via O\u2014H\u22efCl and O\u2014H\u22efF hydrogen bonding. One of the trifluoro\u00admethyl groups is disordered over two orientations in a 0.59\u2005(4):0.41\u2005(4) ratio.In the title compound, (C DOI: 10.1107/S1600536812018855/xu5519Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The NiII atom is coordinated by four PzMe3 mol\u00adecules and two thio\u00adcyanate anions to define a trans N4S2 distorted octa\u00adhedral geometry. A number of intra\u00admolecular N\u2014H\u22efN, N\u2014H\u22efS and C\u2014H\u22efN inter\u00adactions contribute to the stability of the complex. The crystal structure is stabilized by inter\u00admolecular N\u2014H\u22efS inter\u00adactions, which link neighbouring mol\u00adecules into chains along the a axis.In the title compound, [Ni(NCS) DOI: 10.1107/S1600536811041419/tk2796Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dpa ligand coordinates the PdII atom in a boat conformation of the resulting chelate ring; the dihedral angle between the pyridine rings is 39.3\u2005(2)\u00b0. The two acetate anions coordinate the PdII atom as monodentate ligands and are located on the same sides of the PdN2O2 unit plane. The carboxyl\u00adate groups of the anionic ligands appear to be delocalized on the basis of the C\u2014O bond lengths. Two complex mol\u00adecules are assembled through inter\u00admolecular N\u2014H\u22efO hydrogen bonds, forming a dimer-type species. Inter\u00admolecular C\u2014H\u22efO hydrogen bonds further stabilize the crystal structure.In the title complex, [Pd(CH II complexes [PdX2(dpa)] (X = Cl or Br), see: Rauterkus et al. 2(C10H9N3)] = 0.049wR(F2) = 0.116S = 0.922925 reflections205 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.99 e \u00c5\u22123\u0394\u03c1min = \u22120.81 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Intra\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions stabilize the mol\u00adecular conformation. The dihedral angles formed by the central benzene ring with the outer benzene rings of the terphenyl groups are 47.92\u2005(8), 59.38\u2005(8), 48.24\u2005(8) and 52.37\u2005(8)\u00b0. The dichloro\u00admethane solvent mol\u00adecule inter\u00adacts with the complex mol\u00adecule via a C\u2014H\u22efO hydrogen bond. In the crystal, centrosymmetrically related complex mol\u00adecules are linked into dimers through pairs of C\u2014H\u22efO hydrogen bonds.In the title compound, [Fe(C DOI: 10.1107/S1600536812015553/rz2736Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The NH group of the hydrazone moiety does not form a hydrogen bond, due to a steric crowding. In the crystal, the thio\u00adphene ring takes part in weak \u03c0\u2013\u03c0 stacking inter\u00adactions with the pyridine ring [centroid-to-centroid separation = 3.7553\u2005(19)\u2005\u00c5 and inter\u00adplanar angle = 5.48\u2005(12)\u00b0] and the benzene ring [3.7927\u2005(19)\u2005\u00c5 and 4.58\u2005(12)\u00b0]. Together, these lead to [100] stacks of mol\u00adecules in an alternating head-to-tail arrangement, with two \u03c0\u2013\u03c0 stacking contacts between each adjacent pair.In the title compound, C DOI: 10.1107/S1600536812005673/kp2384Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005673/kp2384Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II atom in the title compound, [Cu(C16H10ClN2O)2], is located on an inversion center and is tetra\u00adcoordinated by two N and two O atoms from two bidentate 1-[(E)-(2-chloro\u00adphen\u00adyl)diazen\u00adyl]naphthalen-2-olate ligands, forming a square-planar complex. In the crystal, mol\u00adecules are linked via weak C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds, forming chains propagating along [010]. There are also \u03c0\u2013\u03c0 inter\u00adactions present involving adjacent naphthalene rings [centroid\u2013centroid distance = 3.661\u2005(13)\u2005\u00c5].The Cu DOI: 10.1107/S1600536813016681/su2613Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "An intra\u00admolecular O\u2014H\u22efO hydrogen bond occurs. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds link pairs of mol\u00adecules into centrosymmetric dimers. Weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings [shortest centroid\u2013centroid distance = 3.4962\u2005(2)\u2005\u00c5] further stabilize the crystal packing.In the title compound, [Co(C DOI: 10.1107/S1600536811051804/cv5209Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 1,10-phenanthroline ligand is slightly folded for one complex, the dihedral angle between the pyridine planes being 5.3\u2005(1)\u00b0. In contrast it is nearly planar [0.5\u2005(1)\u00b0] as it complexes with the other HgII atom. The thio\u00adcyanate ligands are virtually linear and the S atom is bonded to HgII with N\u22efS\u2014Hg angles ranging from 99.3\u2005(1) to 103.5\u2005(1)\u00b0. Despite the presence of six aromatic rings in the asymmetric unit, there are no significant inter\u00admolecular \u03c0\u2013\u03c0 contacts between phenanthroline ligands as the centroid\u2013centroid distance of the closest contact between six-membered rings is 4.11\u2005(1) A\u00b0.The asymmetric unit of the title compound, [Hg(SCN) DOI: 10.1107/S1600536812038160/vn2049Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, the anions and cations are linked by N\u2014H\u22efO inter\u00adactions along the b axis and a short N\u2014O\u22ef\u03c0 contact [3.2899\u2005(5)\u2005\u00c5] also occurs.In the title compound, C DOI: 10.1107/S1600536810032629/bx2300Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds. There are also \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of the pydc ligands and between the pydc ligands and the benzene-1,3-diammonium cations, with centroid\u2013centroid distances of 3.4575\u2005(15) and 3.7521\u2005(15)\u2005\u00c5.In the title compound, (C DOI: 10.1107/S1600536811009858/hy2407Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The carboxyl\u00adate groups of the PEB ions are twisted away from the attached benzene rings by 4.0\u2005(6) and 13.3\u2005(5)\u00b0. The two benzene rings of the PEB ions bonded to the same metal ion are oriented at a dihedral angle of 87.4\u2005(3)\u00b0. In the polymeric chain, the NA ligand is linked to one of the carboxyl\u00adate groups via N\u2014H\u22efO hydrogen bonding. In the crystal, adjacent polymeric chains inter\u00adact via N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds; and the lattice water mol\u00adecule links with the polymeric chains via N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonding. \u03c0\u2013\u03c0 stacking between the benzene and the pyridine rings [centroid\u2013centroid distance = 3.805\u2005(5)\u2005\u00c5] and weak C\u2014H\u22ef\u03c0 inter\u00adactions are also observed in the crystal structure.In the crystal structure of the polymeric title compound, {[Pb(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)]\u00b7H2O = 0.043                           wR(F                           2) = 0.099                           S = 1.06                           5076 reflections314 parameters5 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 1.11 e \u00c5\u22123                        \u0394\u03c1min = \u22120.96 e \u00c5\u22123                        \u0394\u03c1                                 CrystalClear  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811026535/xu5254Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two Bi atoms and two of the C atoms directly bonded to bis\u00admuth are quasi-planar  with the carbonate group. The remaining two ligands are in a trans arrangement relative to the quasi-planar (CBi)2CO3 system. The metal atom is strongly coordinated by the N atom of one pendant arm [Bi\u2014N = 2.739\u2005(6)\u2005\u00c5], almost trans to the O atom, while the N atom of the other pendant arm exhibits a weaker intra\u00admolecular inter\u00adaction [Bi\u22efN = 3.659\u2005(7)\u2005\u00c5] almost trans to a C atom. If both these intra\u00admolecular N\u2192Bi inter\u00adactions per metal atom are considered, the overall coordination geometry at bis\u00admuth becomes distorted square-pyramidal [2BiO cores] and the compound can be described as a hypervalent 12-Bi-5 species. Additional quite short intra\u00admolecular Bi\u22efO inter\u00adactions are also present [3.796\u2005(8)\u20134.020\u2005(9)\u2005\u00c5]. Inter\u00admolecular associations through weak \u03b76\u22efBi inter\u00adactions [Bi\u22efcentroid of benzene ring = 3.659\u2005(1)\u2005\u00c5] lead to a ribbon-like supra\u00admolecular association.The mol\u00adecular structure of the title compound, [Bi DOI: 10.1107/S160053681005453X/rk2252Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex cation, the FeII atom is coordinated by six N atoms from three chelating dimephen ligands at an average Fe\u2014N distance of 1.963\u2005(4)\u2005\u00c5 giving a distorted octa\u00adhedral geometry. The crystal structure is stabilized by weak C\u2014H\u22efN hydrogen bonds and C\u00a0N\u22ef\u03c0 inter\u00adactions between planar [maximum deviations of 0.024\u2005(3) and 0.015\u2005(3)\u2005\u00c5] tcm anions and pyridine rings of dimephen .The title compound, [Fe(C DOI: Click here for additional data file.10.1107/S1600536812046880/bx2428Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The deprotonated ligand intra\u00admolecularly hydrogen bonds to the thia\u00adzole ring N atom, while the deprotonated ligand forms an inter\u00admolecular hydrogen bond to the thiol\u00adate S atom. The deprotonation of the tridentate ligand and its coordination to Hg via the S atom strikingly affects the C\u2014S bond lengths. In the free ligand, the C\u2014S bond distance is 1.685\u2005(7)\u2005\u00c5, whereas it is 1.749\u2005(7)\u2005\u00c5 in the deprotonated ligand. Similarly, the Hg\u2014S bond distance is slightly longer to the neutral ligand [2.6682\u2005(18)\u2005\u00c5] than to the deprotonated ligand [2.5202\u2005(19)\u2005\u00c5]. The Hg\u2014I distance is 2.7505\u2005(8)\u2005\u00c5.In the title compound, [Hg(C I(C12H12N4S2)] = 0.042                           wR(F                           2) = 0.085                           S = 1.02                           5837 reflections346 parametersH-atom parameters constrainedmax = 1.36 e \u00c5\u22123                        \u0394\u03c1min = \u22121.27 e \u00c5\u22123                        \u0394\u03c1                                 COLLECT  used to solve structure: SIR97 (Altomare et al., 1999SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997SHELXL97.Data collection: 10.1107/S160053681101974X/vm2089sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101974X/vm2089Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The isobutyl group is disordered over two sets of sites in a 0.899\u2005(9):0.101\u2005(9) ratio. In the crystal, weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions involving the imidazole and thia\u00addiazole rings with a centroid\u2013centroid distance of 3.8067\u2005(7)\u2005\u00c5 occur.In the title compound, C DOI: 10.1107/S1600536810053201/hb5776Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the ZnII cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 24.13\u2005(8)\u00b0, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 88.52\u2005(4)\u00b0. The coordinating water mol\u00adecule links with the carboxyl\u00adate group via an O\u2014H\u22efO hydrogen bond. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, and a weak C\u2014H\u22ef\u03c0 inter\u00adaction link the mol\u00adecules into a two-dimensional network parallel to (010). These networks are linked via C\u2014H\u22efO and \u03c0\u2013\u03c0 inter\u00adactions between inversion-related benzene rings [centroid\u2013centroid distance = 3.8483\u2005(7)\u2005\u00c5], forming a three-dimensional supra\u00admolecular structure.In the title complex, [Zn(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.022wR(F2) = 0.060S = 1.063475 reflections216 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.43 e \u00c5\u22123\u0394\u03c1min = \u22120.31 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S160053681203320X/su2483Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two phen ligands exhibit nearly perfect coplanarity (r.m.s. deviations = 0.027 and 0.031\u2005\u00c5), making a dihedral angle of 85.7\u2005(1)\u00b0. The mean inter\u00adplanar distances of 3.36\u2005(2) and 3.41\u2005(3)\u2005\u00c5 between adjacent phen ligands indicate \u03c0\u2013\u03c0 stacking inter\u00adactions. The uncoordinated water mol\u00adecules are partly occupied. One carboxyl\u00adate O atom and two Br atoms are each disordered over two sites, with occupancy factors of 0.60 and 0.40. In the crystal structure, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions link the complex cations, uncoordinated 4-bromo\u00adbenzoate anions and water mol\u00adecules into a three-dimensional supra\u00admolecular network. An intra\u00admolecular O\u2014H\u22ef\u00b7O hydrogen bond is observed in the cation.In the title compound, [Zn(C DOI: 10.1107/S160053681003864X/hy2357Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The N atoms occupy one axial and one equatorial site and the terminal chloride ion occupies an equatorial site. The dihedral angle between the pyridine and pyrazole rings is 12.8\u2005(2)\u00b0. In the crystal, aromatic \u03c0\u2013\u03c0 stacking [centroid\u2013centroid separations = 3.812\u2005(3) and 3.848\u2005(3)\u2005\u00c5] and C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions help to establish the packing.In the centrosymmetric binuclear title compound, [Zn DOI: 10.1107/S1600536810026127/hb5500Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Adjacent chains are linked by Owater\u2014H\u22efO hydrogen-bonding inter\u00adactions. The Cu(OH2)3O4 cluster displays a penta\u00adgonal bipyrimadal geometry with two weak coordinations [Cu\u2014Ofuran = 2.790\u2005(2)\u2005\u00c5) and Cu\u2014Ocarboxyl\u00adate = 2.684\u2005(2)\u2005\u00c5] and two water mol\u00adecules located in axial positions. In the title compound, [Cu(C DOI: 10.1107/S1600536812010161/zj2064Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Ca\u2014O bond lengths are in the range 2.354\u2005(3)\u20132.453\u2005(2)\u2005\u00c5, while the Ca\u2014N bond lengths are in the range 2.523\u2005(2)\u20132.548\u2005(2)\u2005\u00c5. An intra\u00admolecular O\u2014H\u22efO hydrogen bond between the carb\u00adoxy and carboxyl\u00adate groups stabilizes the mol\u00adecular configuration. A three-dimensional network of N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds help to stabilize the crystal packing.In the title compound, [Ca(C DOI: 10.1107/S1600536812035544/ff2078Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One of the nearly planar quinoline ligands [maximum deviations = 0.042\u2005(6) and 0.018\u2005(7)\u2005\u00c5] is almost perpendicular to the PtCl2N2 unit [maximum deviation = 0.024\u2005(3)\u2005\u00c5], making a dihedral angle of 89.6\u2005(1)\u00b0, whereas the other is slightly inclined to the central plane with a dihedral angle of 74.1\u2005(1)\u00b0. The dihedral angle between the quinoline ligands is 88.3\u2005(2)\u00b0. In the crystal, each solvent mol\u00adecule is linked to the metal complex by weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds.In the title compound, [PtCl DOI: 10.1107/S1600536812012469/xu5489Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The geometry around the CuII ion is highly distorted with the range of Cl\u2014Cu\u2014Cl angles being 94.94\u2005(1)\u2013141.03\u2005(1)\u00b0. The crystal structure is stabilized by N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds. In the three-dimensional network, cations and anions pack in the lattice so as to generate chains of [CuCl4]2\u2212 anions separated by two orientations of cation layers, which are inter\u00adlocked through \u03c0\u2013\u03c0 stacking contacts between pairs of pyridine rings, with centroid\u2013centroid distances of 3.7874\u2005(7)\u2005\u00c5.The asymmetric unit of the title salt, (C DOI: 10.1107/S1600536813028006/bq2389Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is stabilized by inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title complex, [Ag(C DOI: 10.1107/S1600536811017776/jh2288Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The negatively charged N atom of the group binds to the terminal SnIV atom at a shorter distance [Sn\u2014N = 2.236\u2005(2)\u2005\u00c5] compared with the neutral N atom that binds to the central SnIV atom [Sn\u2190 N = 2.805\u2005(2)\u2005\u00c5]. The terminal SnIV atom is five-coordinate in a cis-C2SnNO2 trigonal\u2013bipyramidal geometry [C\u2014Sn\u2014C = 136.4\u2005(1)\u00b0], whereas the central SnIV atom is six-coordinate in a C2SnNO3 skew-trazepoidal bipyramidal geometry [C\u2014Sn\u2014C = 145.4\u2005(1)\u00b0]. The C atoms of the isopropoxy group are disordered over two positions in a 0.591\u2005(7):0.409\u2005(7) ratio.The tetra\u00adnuclear title compound, [Sn DOI: Click here for additional data file.10.1107/S160053681204771X/bt6864Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The supra\u00admolecular structure is based on inter\u00adactions involving the meth\u00adoxy groups , \u03c0\u2013\u03c0 stacking of the electron-rich meth\u00adoxy-substituted rings [centroid\u2013centroid distances of 3.6454\u2005(9)\u20133.738\u2005(1)\u2005\u00c5] and C\u2014H\u22ef\u03c0 contacts .The title compound, C DOI: 10.1107/S1600536811012888/vm2079Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II\u2013LuIII salen-type complex, [CuLu(C22H24N2O4)(NO3)3], with the ligand 6,6\u2032-dimeth\u00adoxy-2,2\u2032-diphenolate, the irregular nine-coordinate LuIII coordination sphere comprises four O atoms from the ligand and five O atoms from three nitrate groups, two bidentate and one monodentate [Lu\u2014O = 2.230\u2005(3)\u20132.621\u2005(4)\u2005\u00c5]. The slightly distorted square-planar four-coordinate CuII atom comprises two imine N atoms [Cu\u2014N = 1.903\u2005(4) and 1.912\u2005(4)\u2005\u00c5] and two phenolate O atoms from the ligand mol\u00adecule [Cu\u2014O = 1.897\u2005(3) and 1.906\u2005(3)\u2005\u00c5]. All atoms of the cyclo\u00adhexane ring of the ligand mol\u00adecule are disordered over two sets of sites with equal occupancy.In the title dinuclear Cu DOI: 10.1107/S1600536810048245/zs2074Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "This disorder is correlated with the disorder of one of the H atoms of the water mol\u00adecule. The carboxyl group is twisted relative to the attached benzene ring by 75.1\u2005(4)\u00b0. The intra\u00admolecular I\u22efO distance is 2.112\u2005(6)\u2005\u00c5. Mol\u00adecules are linked via O\u2014H\u22efO hydrogen bonding, C\u2014I\u22efO halogen bonding, with I\u22efO distances in the range 3.156\u2005(5)\u20133.274\u2005(6)\u2005\u00c5, and dipolar C=O\u22efC=O inter\u00adactions between the carboxyl and carboxyl\u00adate groups, with an O\u22efC distance of 2.944\u2005(10)\u2005\u00c5.In the title compound, C DOI: 10.1107/S1600536812005351/gk2447Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005351/gk2447Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The oxide O atoms adopt a cis conformation: one is trans to the methanol O atom and the other is trans to the ligand N atom. The dihedral angle between the two benzene rings in the hydrazone ligand is 4.0\u2005(3)\u00b0. In the crystal, mol\u00adecules are linked by O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds.In the title dioxidomolybdenum(VI) complex, [Mo(C O2(CH4O)] = 0.044wR(F2) = 0.093S = 1.034300 reflections269 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 0.62 e \u00c5\u22123\u0394\u03c1min = \u22120.69 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812008549/hb6656Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the pyridine rings is 1.92\u2005(11)\u00b0. In the crystal, \u03c0\u2013\u03c0 stacking between parallel pyridine rings of adjacent complex mol\u00adecules is observed, the centroid\u2013centroid distance being 3.6788\u2005(19)\u2005\u00c5. Weak C\u2014H\u22efO hydrogen bonds further link the mol\u00adecules into a three-dimensional supra\u00admolecular architecture.In the title complex, [Cu(NO DOI: 10.1107/S1600536813028201/xu5745Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Li+ ion is N,N\u2032-chelated by the N-silylated amido ligand, with Li\u2014N = 2.015\u2005(5) and 2.074\u2005(5)\u2005\u00c5. The two amido ligands are arranged cis to each other. The mol\u00adecule exhibits a twofold rotational symmetry operation along the Li\u2013Na axis. The Na+ ion is coordinated by two N atoms from the tetra\u00admethyl\u00adethylenediamine ligand [Na\u2014N = 2.553\u2005(4)\u2005\u00c5] and shares two amido N atoms from the N-silylated amido ligands with the Li+ ion. Although the crystal structure contains voids with an approximate volume of 50\u2005\u00c53 there is no inclusion of solvent mol\u00adecules.In the heterometallic title bulky amido complex, [LiNa(C N-silylated quinolyl amido ligands, see: Engelhardt et al. 2(C6H16N2)] = 0.062wR(F2) = 0.195S = 0.974001 reflections209 parameters1 restraintH-atom parameters constrainedmax = 0.32 e \u00c5\u22123\u0394\u03c1min = \u22120.26 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S160053681204576X/rk2385Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The complex mol\u00adecules are connected via water O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions between the benzene rings [minimum ring centroid separation = 3.750\u2005(6)\u2005\u00c5] into a three-dimensional polymeric structure. The imidazolyl group of the ligand is partially disordered over two sets of sites with refined occupancies of 0.531\u2005(7):0.469\u2005(7).In the title compound, [Mn(C DOI: 10.1107/S1600536812010446/zs2182Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridyl rings [centroid\u2013centroid distance = 3.7337\u2005(18)\u2005\u00c5] are present in the crystal structure.In the title compound, [CdCl DOI: 10.1107/S1600536810029399/hy2335Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal atom is further chelated by a carboxyl\u00adate group and is covalently bonded to a monodentate carboxyl\u00adate group and to a monodentate sulfonate group in a distorted square-anti\u00adprismatic geometry. The coordinating and the solvent water mol\u00adecules are hydrogen bonded to the network. In the crystal, one solvent water mol\u00adecule is disordered over two positions [major component = 59\u2005(3)%].The 4-sulfophthalate trianion in the polymeric title complex, {[Dy(C III complex, see: Zhang et al. (C12H8N2)(H2O)2]\u00b72H2O = 0.037wR(F2) = 0.093S = 1.204022 reflections353 parameters33 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.97 e \u00c5\u22123\u0394\u03c1min = \u22121.85 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812003613/xu5457Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The benzene rings of the anions are involved in \u03c0\u2013\u03c0 stacking. The centroid\u2013centroid distance between parallel benzene rings of adjacent mol\u00adecules is 3.9017\u2005(17)\u2005\u00c5, and the centroid\u2013centroid distance between benzene and pyridine rings of adjacent mol\u00adecules is 3.584\u2005(2)\u2005\u00c5. Intra\u00admolecular O\u2014H\u22efO hydrogen bonding is present.In the title compound, [Zn(C DOI: 10.1107/S1600536811020435/ng5174Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II ion in the title centrosymmetric dinuclear complex, [Hg2Cl4(C13H12N2)2]\u00b7[HgCl2], adopts a distorted square-pyramidal geometry, being coordinated by the bis-chelating N-heterocyclic ligand, two bridging Cl atoms and one terminal Cl atom. One of the bridging Hg\u2014Cl bonds [2.8428\u2005(11)\u2005\u00c5] is significantly longer than the other [2.5327\u2005(10)\u2005\u00c5]. In the crystal, there are weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.630\u2005(3)\u2005\u00c5] between the aromatic rings of the discrete units. The HgCl2 adduct molecule is located on an inversion centre and has an Hg\u2014Cl bond length of 2.2875\u2005(11)\u2005\u00c5.The Hg DOI: 10.1107/S1600536810050725/jh2236Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are linked into sheets parallel to the bc plane by C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.669\u2005(1)\u2005\u00c5].In the title compound, [ZnCl DOI: 10.1107/S160053681004119X/ci5172Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are connected by C\u2014H\u22efBr and C\u2014H\u22efO hydrogen bonds, and \u03c0\u2013\u03c0 inter\u00adactions between the oxazole and benzene rings [centroid\u2013centroid distance = 3.7344\u2005(19)\u2005\u00c5], resulting in a three-dimensional supra\u00admolecular structure.In the title compound, [PdBr(C DOI: Click here for additional data file.10.1107/S1600536812049197/hy2606Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Four water O atoms in the equatorial plane around the CoII ion [Co\u2014O = 2.0593\u2005(16) and 2.1118\u2005(16)\u2005\u00c5] form a slightly distorted square-planar arrangement, and the distorted octahedral geometry is completed by the two N atoms [Co\u2014N = 2.1306\u2005(18)\u2005\u00c5] from two isonicotinamide ligands. In the anion, the carboxyl\u00adate group is twisted from the attached benzene ring at 8.84\u2005(17)\u00b0. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, consolidates the crystal packing, which exhibits \u03c0\u2013\u03c0 inter\u00adactions between the benzene and pyridine rings, with centroid\u2013centroid distances of 3.458\u2005(1) and 3.606\u2005(1)\u2005\u00c5, respectively.The asymmetric unit of the title compound, [Co(C DOI: 10.1107/S1600536812003911/cv5239Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the aromatic ring and the pyridyl ring is 71.7\u2005(1)\u00b0. In the crystal, the mol\u00adecules are stacked in columns along the c axis and several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are present between the six-membered rings, with a shortest centroid\u2013centroid distance of 3.707\u2005(2)\u2005\u00c5.The title compound, C DOI: 10.1107/S1600536811003011/ng5109Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, adjacent mol\u00adecules are connected by \u03c0\u2013\u03c0 contacts between the thia\u00adzole rings [centroid\u2013centroid distance = 3.591\u2005(3)\u2005\u00c5].In the title compound, [HgI DOI: 10.1107/S1600536810029302/hy2334Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the components are linked by O\u2014H\u22efO, C\u2014H\u22efO and aromatic \u03c0\u2013\u03c0 stacking [shortest centroid\u2013centroid separation = 3.659\u2005(5)\u2005\u00c5] inter\u00adactions.In the title compound, [Co(C DOI: 10.1107/S1600536810022750/hb5497Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 5-hy\u00addroxy\u00adnicotinate ligand is protonated at the N atom and deprotonated at the hy\u00addroxy group. The HoIII atoms are bridged by the carboxyl\u00adate and phenolate O atoms, forming a three-dimensional framework. N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.794\u2005(2)\u2005\u00c5], are observed.In the title compound, {[Ho DOI: 10.1107/S1600536812032916/hy2567Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "One of the Cp ligands is additionally substituted by a dimethyl\u00adamino\u00admethyl group causing the chirality of the mol\u00adecule. Surprisingly, although the synthetic procedure yielded the title compound as a racemic mixture, the reported crystal is enanti\u00adomerically pure with the R absolute configuration. The dimethyl\u00adamino group is exo with respect to the Cp ring. Both diphenyl\u00adthio\u00adphosphine groups are trans with respect to the centroid\u2013Fe\u2013centroid direction. Weak intra\u00admolecular C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions between symmetry-related mol\u00adecules are observed. The contribution of the disordered solvent was removed from the refinement using SQUEEZE in PLATON . In the title compound, [Fe(CSpek 2009. Acta Cr For the al. 2010; Debono  al. 2010; Diab et al. 2008; Le Roux al. 2007; Malaceal. 2006a,b \u25b6; Ro20H21NPS)(C17H14PS)]\u00b7CH2Cl2 = 0.042wR(F2) = 0.102S = 1.097854 reflections393 parametersH-atom parameters constrainedmax = 0.63 e \u00c5\u22123\u0394\u03c1min = \u22120.36 e \u00c5\u22123\u0394\u03c1Absolute structure: Flack 1983, 3441 FrFlack parameter: 0.043 (16)APEX2  used to solve structure: SIR97  I, global. DOI: 10.1107/S1600536812022301/im2377Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The resulting N2O3 donor set defines a distorted square-pyramidal geometry with the coordinated water mol\u00adecule in the apical position. In the crystal, the presence of O\u2014Hw\u22efOc (w = water and c = carbon\u00adyl) hydrogen bonding leads to the formation of a supra\u00admolecular chain propagating along the c axis, which associates into a double chain via C\u2014H\u22ef O and \u03c0\u2013\u03c0 contacts between pyridyl rings [centroid\u2013centroid distance = 3.527\u2005(3)\u2005\u00c5]. The solvent mol\u00adecules, which are disordered over two orientations in a 0.678\u2005(11):0.322\u2005(11) ratio, occupy voids defined by the complex mol\u00adecules and are held in place via C\u2014H\u22efO inter\u00adactions.The title complex, [Cu(C DOI: 10.1107/S1600536810030436/hb5590Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "IV atom in the title compound, [Sn(C6H5)2Cl2(C13H12OS)], displays a distorted C2Cl2O trigonal\u2013bipyramidal coordination environment, with a mean Sn\u2014C distance of 2.121\u2005(9)\u2005\u00c5 and with Sn\u2014O = 2.331\u2005(2)\u2005\u00c5. The SnIV atom is displaced by 0.169\u2005(2)\u2005\u00c5 from the equatorial C2Cl plane towards the direction of the second axially bonded Cl atom.The Sn DOI: 10.1107/S1600536811014474/wm2481Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom is tetra\u00adcoordinated, displaying a slightly distorted square-planar geometry. The main deviation from the ideal geometry is seen in the differences in the Cu\u2014O [1.8833\u2005(10)\u2005\u00c5] and Cu\u2014N [1.9405\u2005(13)\u2005\u00c5] bond lengths, while angular deviations are less than 3\u00b0. Intra\u00admolecular O\u2014H\u22efO and inter\u00admolecular C2sp\u2014H\u22efO hydrogen bonds form S(5) and R22(8) ring motifs, respectively. The latter inter\u00adaction results in chains of mol\u00adecules along [100].In the title compound, [Cu(C DOI: 10.1107/S1600536812032187/lr2071Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Three RuCp+ (Cp is cyclo\u00adpenta\u00addien\u00adyl) groups are bonded to the three aromatic rings of the ligand. Surprisingly, the pyramidalized N atom of the heterocycle (\u03a3 C\u2014N\u2014C = 329.0\u00b0) points towards the anthracenyl group, so losing its coordinative ability. There is an inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction involving an acetone mol\u00adecule and the adjacent benzyl ring of the ligand. In the crystal, mol\u00adecules are linked via a number of C\u2014H\u22efO and C\u2014H\u22efF inter\u00adactions and a C\u2014H\u22ef\u03c0 inter\u00adaction, leading to the formation of a three-dimensional supra\u00admolecular structure. One of the Cp groups is disordered over two positions, with refined occupancies of 0.695\u2005(14):0.305\u2005(14). Two of the three hexa\u00adfluoro\u00adphospate anions are disordered, with refined occupancies of 0.630\u2005(6):0.370\u2005(6) and 0.771\u2005(8):0.229\u2005(8). One of the two solvent acetone mol\u00adecules is also disordered, with refined occupancies of 0.82\u2005(2):0.18\u2005(2).In the title compound, [Ru DOI: 10.1107/S1600536812040652/su2499Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CdII ions are connected by two bridging benzoate anions and each ion is seven-coordinated by five O atoms from three benzoate ligands and by two N atoms from 1,10-phenanthroline. The benzoate ligands adopt two different coordination modes, acting as bidentate and bridging tridentate ligands. The discrete neutral mol\u00adecules further extend their structure into a three-dimensional supra\u00admolecular framework by inter\u00admolecular \u03c0\u2013\u03c0 [inter\u00adplanar distances of 3.392\u2005(4)\u2005\u00c5] and C\u2014H\u22ef\u03c0 stacking inter\u00adactions [H\u2013mean plane = 2.567\u2005(4) and 2.781\u2005(4)\u2005\u00c5].The dinuclear title compound, [Cd DOI: 10.1107/S1600536811022185/zq2105Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII ion is coordinated by two N atoms from one mol\u00adecule of the aromatic base and four O atoms from two bidentate, symmetry-related acetate anions, which coordinate asym\u00admetrically [Zn\u2014O distances of 2.058\u2005(2) and 2.362\u2005(3)\u2005\u00c5], while the two Zn\u2014N bond distances are equal as imposed by symmetry [2.079\u2005(2)\u2005\u00c5]. The crystal structure is supported by a number of weak C\u2014H\u22efO inter\u00adactions and C\u2014H\u22ef\u03c0 contacts, with no \u03c0\u2013\u03c0 inter\u00adactions present, mainly hindered by the substituent methyl groups and the relative mol\u00adecular orientation. The result is a three-dimensional structure in which each mol\u00adecule is linked to eight different neighbors.The mol\u00adecular structure of the title compound, [Zn(CH DOI: Click here for additional data file.10.1107/S1600536812042699/br2212Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "It should be noted, that a solvent-masking procedure as implemented in OLEX2 [Dolomanov et al. (2009). J. Appl. Cryst.42, 339\u2013341II ion is five-coordinated by two phenanthroline ligands and one chloride ion in a distorted trigonal\u2013bipyramidal geometry. The dihedral angle between the phen ligands is 65.21\u2005(5)\u00b0. The MnII ion is six-coordinated by one Cl atom, two N atoms from a phen ligand, as well one N atom and two O atoms from pydc in a distorted octa\u00adhedral coordination geometry, with cis angles ranging from 72.00\u2005(8) to 122.07\u2005(8)\u00b0 and trans angles ranging from 143.98\u2005(8) to 163.15\u2005(6)\u00b0. In the crystal, C\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds, cation\u2013anion \u03c0\u2013\u03c0 inter\u00adactions between the phen ring systems with centroid\u2013centroid distances in the range 3.881\u2005(34)\u20134.123\u2005(36)\u2005\u00c5, as well as cation\u2013cation, anion\u2013anion \u03c0\u2013\u03c0 inter\u00adactions between the phen rings with centroid\u2013centroid distances in the range 3.763\u2005(4)\u20133.99\u2005(5)\u2005\u00c5 and pydc rings with centroid\u2013centroid distances 3.52\u2005(5)\u2005\u00c5 link the various components. The title complex, [CuCl(C DOI: 10.1107/S1600536814006369/br2237Isup2.hklStructure factors: contains datablock(s) I. DOI: 993053CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angles between the mean planes of the central phenolate rings and the peripheral phenyl rings are 46.62\u2005(10)/87.06\u2005(9), 60.44\u2005(8)/23.13\u2005(8) and 46.49\u2005(6)/65.29\u2005(6)\u00b0. The crystal packing is stabilized by weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions. Mol\u00adecules are further linked by two \u03c0\u2013\u03c0 [centroid\u2013centroid distances = 3.8612\u2005(14) and 3.9479\u2005(14)\u2005\u00c5] and four C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network.In the title compound, [Co(C DOI: 10.1107/S1600536814001664/hg5379Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The slightly distorted square-planar coordination sphere of the CuII atom comprises two phenolate O atoms and two oxime N atoms from two bidentate\u2013chelate 2-[1-(eth\u00adoxy\u00adimino)\u00adeth\u00adyl]-1-naphtho\u00adlate O-ethyl oxime (L               \u2212) ligands [Cu\u2014O = 1.8919\u2005(17)\u2005\u00c5 and Cu\u2014N = 1.988\u2005(2)\u2005\u00c5]. The two naphthalene ring systems in the mol\u00adecule are parallel, with a perpendicular inter\u00adplanar spacing of 1.473\u2005(2)\u2005\u00c5, while each complex unit forms links to four other mol\u00adecules via inter\u00admolecular methyl C\u2014H\u22ef\u03c0 inter\u00adactions, giving an infinite cross-linked layered supra\u00admolecular structureIn the title complex, [Cu(C DOI: 10.1107/S1600536810047574/zs2078Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ligands are mutually transoid with respect to the metal atom. Weak inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.8452\u2005(14) and 3.9932\u2005(14)\u2005\u00c5, are found in the crystal packing.In the title complex, [ZnCl DOI: 10.1107/S1600536811022884/fj2423Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In each mol\u00adecule, the geometry around the Pd atom is distorted square-planar, with the Pd atom displaced by 0.0549\u2005(12) and 0.0734\u2005(13)\u2005\u00c5 from the least-squares plane of the I\u2014P\u2014P\u2014C atoms. The PPh3 ligands are in trans positions, with P\u2014Pd\u2014P angles of 173.12\u2005(4) and 170.29\u2005(4)\u00b0, while the pyrazinyl ligands and I atoms, also trans to each other, form C\u2014Pd\u2014I angles of 179.38\u2005(12) and 178.44\u2005(12)\u00b0. In the crystal, C\u2014H\u22ef\u03c0 inter\u00adactions occur, resulting in a three-dimensional supramolecular architecture.There are two independent mol\u00adecules with similar configurations in the asymmetric unit of the title complex, [Pd(C I(C18H15P)2] = 0.048wR(F2) = 0.101S = 1.0415924 reflections829 parametersH-atom parameters constrainedmax = 1.35 e \u00c5\u22123\u0394\u03c1min = \u22120.55 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812043589/bg2480Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The pyrimidine\u00adthiol\u00adate anion acts both as a bridging and a chelating ligand. The AgI ions are linked via two \u03bc2-S donor atoms, which generate a strictly planar Ag2S2 core with an Ag\u22efAg separation of 2.9569\u2005(4)\u2005\u00c5. The AgI ion presents a distorted tetra\u00adhedral coordination geometry. In the crystal, weak C\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds link the complex mol\u00adecules into a two-dimensional network parallel to (010).The dinuclear title complex, [Ag For rel al. 2000; Lobana  al. 2008; Isab et al. 2010.2(C6H7N2S)2(C18H15P)2] = 0.032wR(F2) = 0.088S = 1.045568 reflections266 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.54 e \u00c5\u22123\u0394\u03c1min = \u22120.29 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536812048210/bh2464Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "A weak intra\u00admolecular C\u2014H\u22efO hydrogen bond occurs between the DMBP and DMSO ligands. \u03c0\u2013\u03c0 stacking between pyridine rings [centroid\u2013centroid distances = 3.682\u2005(3) and 3.598\u2005(3)\u2005\u00c5] is observed in the crystal.In the title compound, [CdBr DOI: 10.1107/S1600536812028553/xu5571Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex; the PdN2Cl2 unit is exactly planar. The dihedral angle between the PdN2Cl2 unit and quinoline ligand is 85.63\u2005(8)\u00b0. In the crystal, the complex mol\u00adecules are stacked into columns along the b axis. In the columns, several inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings are present, the shortest ring centroid\u2013centroid distance being 3.764\u2005(3)\u2005\u00c5 between pyridine rings.In the title complex, [PdCl II complex cis-[PtCl2(quinoline)2]\u00b70.25DMF, see: Davies et al. 2] = 0.040wR(F2) = 0.095S = 1.051577 reflections106 parametersH-atom parameters constrainedmax = 1.30 e \u00c5\u22123\u0394\u03c1min = \u22120.40 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  global. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal, there are aromatic \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distances = 3.9577\u2005(13)\u2005\u00c5] and inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds.In the title compound, [Zn(NO DOI: 10.1107/S1600536811050227/bt5709Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometry around the RuII atom is pseudo-octa\u00adhedral, with two cis-binding PPh3 ligands and one chelating bidentate [Fc(O)PS2]2\u2212 ligand via two S atoms. The average Ru\u2014S and Ru\u2014P bond lengths are 2.434\u2005(1) and 2.398\u2005(1)\u2005\u00c5, and the Ru\u2014O and Ru\u2014C bond lengths are 2.157\u2005(3) and 1.826\u2005(4)\u2005\u00c5, respectively. In the crystal, pairs of O\u2014H\u22efO hydrogen bonds link adjacent mol\u00adecules into dimers.The structure of the title complex, [FeRu(C DOI: Click here for additional data file.10.1107/S1600536813014311/ds2231Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The whole repeating mol\u00adecular unit is generated by inversion symmetry. This leads to the formation of a looped-chain one-dimensional coordination polymer propagating along [110]. The dimethyl\u00adformamide (DMF) mol\u00adecules are linked to the chains via O\u2014H\u22efO hydrogen bonds. The chains are linked via N\u2014H\u22efO hydrogen bonds, forming two-dimensional networks parallel to (001). There are also a number of C\u2014H\u22efO inter\u00adactions present and a parallel slipped \u03c0\u2013\u03c0 inter\u00adaction. The latter involves inversion-related pyridine rings with a centroid\u2013centroid distance of 3.594\u2005(2)\u2005\u00c5 [normal distance = 3.3338\u2005(13) and slippage = 1.341\u2005\u00c5]. These inter\u00adactions lead to the formation of a three-dimensional structure.In the title coordination polymer, {[Cu(SO N,N\u2032-bis-(4-pyrid\u00adyl)isophthalamide ligand, see: Adarsh et al. (C18H14N4O2)(H2O)]\u00b7C3H7NO = 0.052wR(F2) = 0.124S = 1.075581 reflections339 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.44 e \u00c5\u22123\u0394\u03c1min = \u22120.48 e \u00c5\u22123\u0394\u03c1CrystalClear  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813003413/su2555Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Two symmetry-related azide ligands bridge in \u03bc2-modes giving a Cu\u22efCu distance of 3.533\u2005(2)\u2005\u00c5. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the components into a three-dimensional network. In addition, there are weak inter\u00admolecular C\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances ranging from 3.562\u2005(2) to 3.974\u2005(2)\u2005\u00c5. In the centrosymmetric dinuclear title complex, [Cu DOI: 10.1107/S1600536811045909/lh5362Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The SnIV atom of the one-dimensional coordination polymer is located on a mirror plane and is coordinated by two chelating oxalate ions with two rather different Sn\u2014O bond lengths of 2.150\u2005(1) and 2.425\u2005(1)\u2005\u00c5, and two t-butyl groups with Sn\u2014C bond lengths of 2.186\u2005(2) and 2.190\u2005(2)\u2005\u00c5. The coordination polyhedron around the SnIV atom is a distorted tetra\u00adgonal disphenoid. The centrosymmetric oxalate ion also has an asymmetric coordination geometry, as reflected by the two slightly different C\u2014O bond lengths of 1.242\u2005(2) and 1.269\u2005(2)\u2005\u00c5. The chains of the polymer propagate along the b-axis direction. Only van der Waals inter\u00adactions are observed between the chains.The title compound, [Sn(C For 2(C2O4)] = 0.015wR(F2) = 0.038S = 1.101548 reflections83 parametersH-atom parameters constrainedmax = 0.53 e \u00c5\u22123\u0394\u03c1min = \u22120.37 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I. DOI: 10.1107/S160053681400539X/cq2010Isup2.hklStructure factors: contains datablock(s) I. DOI: 990826CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "IV ion in the title complex, [PtBr4(C10H9N3)], is six-coordinated in a slightly distorted octa\u00adhedral environment by two pyridine N atoms from a chelating di-2-pyridyl\u00adamine (dpa) ligand and four Br\u2212 anions. The complex mol\u00adecule has mirror symmetry, with the PtIV atom, two Br atoms and the central N atom of the dpa ligand lying on the mirror plane. The dpa ligand is not planar, showing a dihedral angle of 34.7\u2005(2)\u00b0 between the pyridine rings. The complex mol\u00adecules are connected by inter\u00admolecular N\u2014H\u22efBr hydrogen bonds, forming chains along [001]. Inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.667\u2005(4)\u2005\u00c5] are also observed.The Pt DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The geometry around the MoVI atom is distorted octa\u00adhedral in each complex mol\u00adecule, supported by two oxide O atoms and the N2O2 donor atoms of the coordinating ligand. The dihedral angle between the benzene rings is 74.96\u2005(11)\u2005\u00c5 for mol\u00adecule A and 76.05\u2005(11)\u2005\u00c5 for mol\u00adecule B. In the crystal, the B mol\u00adecules are linked by pairs of C\u2014H\u22efCl hydrogen bonds, forming inversion dimers. The crystal structure is further stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions. An inter\u00adesting feature of the crystal structure is a Cl\u22efCl contact [3.3748\u2005(18)\u2005\u00c5], which is shorter than the sum of the van der Waals radii of Cl atoms (3.50\u2005\u00c5).The asymmetric unit of the title compound, [Mo(C O2] = 0.027wR(F2) = 0.079S = 1.078626 reflections541 parametersH-atom parameters constrainedmax = 0.69 e \u00c5\u22123\u0394\u03c1min = \u22120.71 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SIR92  global, I. DOI: 10.1107/S160053681203807X/su2496Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The MnII atom is six-coordinated by 2\u2212 anions in a tridentate fashion and is at the centre of a distorted octa\u00adhedron formed by the MnO4N2 bonding set. In the crystal, various inter\u00admolecular inter\u00adactions between different moieties can be found, such as different kinds of hydrogen bonds, offset or slipped \u03c0\u2013\u03c0 [centroid\u2013centroid distances in the range 3.3704\u2005(12) to 3.8674\u2005(13)\u00c5] and C=O\u22ef\u03c0 [3.563\u2005\u00c5] inter\u00adactions, which lead to the formation of a three-dimensional supra\u00admolecular network. The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536811036981/om2447Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "N,N\u2032-(o-phenyl\u00adene)bis\u00ad(pyridine-2-carboxamidato)]manganese(II)} ethanol hepta\u00adsolvate 3.5-hydrate, [Mn(C18H12N4O2)(C7H10N2)(NO)]8\u00b77C2H5OH\u00b73.5H2O, or 8[Mn(bpb)(DMAP)(NO)]\u00b77EtOH\u00b73.5H2O, is an unusual example of a structure with Z\u2032 = 8. The tetra\u00addentate bpb ligand, together with the nitrosyl and dimethyl\u00adamino\u00adpyridine ligands, gives rise to a distorted octa\u00adhedral coordination environment for the Mn(II) ion. The average Mn\u2014N(N=O) bond length is 1.631\u2005(13)\u2005\u00c5. The eight mol\u00adecules in the asymmetric unit differ mainly in the rotation of the DMAP pyridine plane with respect to a reference plane of the Mn and three N atoms, one of which is the N atom of the NO group. The dihedral angles between the normals to these planes range from a minimum of 28.0\u2005(2)\u00b0 to a maximum of 64.2\u2005(2)\u00b0. There are also some differences in O\u2014H\u22efO hydrogen bonding inter\u00adactions. For example, of the sixteen C=O acceptors, there are seven different inter\u00adactions with EtOH donors and two inter\u00adactions with H2O donors. The crystal studied was found to be a two-component twin, with a 179.9\u00b0 rotation about the real axis . Due to the presence of a superlattice and, consequently, the large number of weak reflections, the refinement utilized rigid solvate groups and isotropic displacement parameters for all except the Mn atoms. H atoms were not located for hydrate molecules.The structure of the title compound octa\u00adkis\u00ad{[4-(dimethyl\u00adamino)\u00adpyridine](nitros\u00adyl)[ DOI: 10.1107/S1600536811038669/wm2529Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The previous structure report [Spofford & Amma  and 0.001\u2005\u00c5 (new)]. The asymmetric unit contains two formula units, with both CuI atoms coordinated by one terminal S atom and two bridging S atoms of thio\u00adurea ligands. This connectivity leads to polymeric [100] chains in the crystal. If very long contacts to nearby chloride ions [2.8687\u2005(9) and 3.1394\u2005(12)\u2005\u00c5] are considered to be bonding, then very distorted CuS3Cl tetra\u00adhedral coordination polyhedra arise. The crystal structure is consolidated by weak intra- and inter-chain N\u2014H\u22efS and N\u2014H\u22efCl hydrogen bonds.The structure of the polymeric title compound, [CuCl(CHAmma 1970. Acta Cr For the structure of a related thio\u00adurea salt, see: Zouihri 2012. For the4N2S)2] = 0.043wR(F2) = 0.081S = 1.154089 reflections245 parameters16 restraintsAll H-atom parameters refinedmax = 0.58 e \u00c5\u22123\u0394\u03c1min = \u22120.85 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812004448/hb6598Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "It is built up by association of (2-(diphenyl\u00adphosphino)ferrocen\u00adyl)meth\u00adyl)dimethyl\u00adammonium cations and diphenyl\u00adphosphino dithio\u00adate anions. N\u2014H\u22efS, C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions link the anions and cations. Each anion\u2013cation pair is linked two by two through C\u2014H\u22ef\u03c0 inter\u00adactions, forming pseudo dimers.2-(Diphenyl\u00adthio\u00adphosphino)dimethyl\u00adamino\u00admethyl\u00adferrocene is a key inter\u00admediate in the synthesis of various ferrocenyl ligands. During one such synthesis, the title compound, [Fe(C DOI: 10.1107/S1600536812009129/hp2031Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "VI atom in the title compound, [Mo(C16H14N2O4)O2(C2H6OS)], is distorted octa\u00adhedral. The phenolate O, imino N, oxide O from the enolized carbonyl group and one of the terminal O atoms form the equatorial plane; the axial positions are occupied by the other terminal O atom of the dioxidomolybdenum group and the donor O atom of DMSO. The O=Mo=O angle is 105.31\u2005(6)\u00b0. An intra\u00admolecular O\u2014H\u22efN hydrogen bond and weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds are present in the structure.The coordination geometry at the Mo O2(C2H6OS)] = 0.024                           wR(F                           2) = 0.120                           S = 1.15                           4556 reflections266 parametersH-atom parameters constrainedmax = 0.47 e \u00c5\u22123                        \u0394\u03c1min = \u22121.68 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811020290/xu5215Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecules form an inversion dimer via a pair of weak C\u2014H\u22efO hydrogen bonds and a \u03c0\u2013\u03c0 stacking inter\u00adaction with a centroid\u2013centroid distance of 3.7401\u2005(12)\u2005\u00c5. Weak intra\u00admolecular C\u2014H\u22efBr inter\u00adactions and an intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adaction with a centroid\u2013centroid distance of 3.8118\u2005(15)\u2005\u00c5 are also observed.In the title compound, [MoBr DOI: 10.1107/S1600536811015881/is2705Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The benzimidazole ring system forms dihedral angles of 26.68\u2005(9) and 56.16\u2005(9)\u00b0 with the adjacent benzene ring and the methyl\u00adphenolate group benzene ring, respectively. In the crystal, mol\u00adecules are linked by N\u2014H\u22efCl hydrogen bonds into chains along [100]. Furthermore, weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, in addition to \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances in the range 3.5826\u2005(13)\u20133.9681\u2005(13)\u2005\u00c5, are also observed.In the title mononuclear complex, [Zn(C Cl] = 0.042                           wR(F                           2) = 0.088                           S = 1.03                           5678 reflections249 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.64 e \u00c5\u22123                        \u0394\u03c1min = \u22120.39 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXTL  global, I. DOI: 10.1107/S1600536811030170/lh6598Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The SnIV ion is five-coordinated in a distorted trigonal\u2013bipyramidal geometry by two monodentate carboxyl\u00adate groups and three phenyl rings. The axial sites are occupied by the O atoms of two symmetry-related carboxyl\u00adate groups [O\u2014Sn\u2014O = 170.88\u2005(3)\u00b0]. The benzene ring of the 5-amino-2-nitro\u00adbenzoate ligand forms dihedral angles of 82.92\u2005(6), 81.10\u2005(6) and 83.54\u2005(6)\u00b0 with respect to the three phenyl rings. In the crystal, the chains are linked by inter\u00admolecular N\u2014H\u22efO and weak C\u2014H\u22efO inter\u00adactions into a three-dimensional network. The crystal structure is further stabilized by weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions.The title compound, [Sn(C For the al. 1987.       6H5)3(C7H5N2O4)] = 0.018                           wR(F                           2) = 0.046                           S = 1.07                           7981 reflections297 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.51 e \u00c5\u22123                        \u0394\u03c1min = \u22120.54 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXTL  global, I. DOI: 10.1107/S1600536811033332/lh5316Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the [FeBr4]\u2212 anion, the FeIII atom (3 symmetry) is four-coordinated in a distorted tetra\u00adhedral geometry. In the crystal, inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and Br\u22ef\u03c0 inter\u00adactions [Br\u22efcentroid distances = 3.562\u2005(3) and 3.765\u2005(2)\u2005\u00c5] link the cations and anions, stabilizing the structure.In the [Fe DOI: 10.1107/S1600536811004181/hy2404Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, C\u2014H\u22efO and \u03c0\u2013\u03c0 inter\u00adactions connect the mol\u00adecules, forming double layers that stack along the  30H28N2O6, the pyran ring adopts a slightly distorted half-chair conformation and the pyrone ring adopts an envelope conformation, with the C atom bearing the carboxyl\u00adate group as the flap. The pyrazole ring [maximum deviation = 0.002\u2005(2)\u2005\u00c5] forms a dihedral angle of 13.2\u2005(1)\u00b0 with the attached benzene ring. The near-planar atoms of the pyran ring and the pyrazole ring are close to coplanar, the dihedral angles between their mean planes being 6.4\u2005(1)\u00b0. The dihedral angle between the pyrone ring and the benzene ring of the chromene unit is 10.7\u2005(1)\u00b0. The mol\u00adecular conformation is stabilized by an intra\u00admolecular C\u2014H\u22efO hydrogen bond, which generates an S(6) ring motif. In the crystal, C\u2014H\u22efO inter\u00adactions generate supra\u00admolecular chains propagating in [100] and these are connected into double layers that stack along the c-axis direction by weak \u03c0\u2013\u03c0 inter\u00adactions between pyrazole rings [centroid\u2013centroid distance = 3.801\u2005(1)\u2005\u00c5].In the title compound, C The pyrazole ring is approximately planar, with a maximum deviation of 0.002\u2005(2)\u2005\u00c5 for atom C2, and forms a dihedral angle of 13.2\u2005(1)\u00b0 with the attached benzene ring. The planar atoms of the pyran ring and the pyrazole ring are close to coplanar, the dihedral angles between their mean planes being 6.4\u2005(1)\u00b0. Moreover, the planar atoms of the pyrone ring and the benzene ring of the chromene unit are also almost coplanar, the dihedral angle between their mean planes being 10.7\u2005(1)\u00b0. The geometric parameters of the title mol\u00adecule agree well with those reported for similar structures  ring motif. The crystal packing features C17\u2014H17\u22efO3 hydrogen bonds, which form a supra\u00admolecular chain along the a axis. This chain is connected into double layer that stacks along the c axis (Table\u00a01Cg is the centroid of the pyrazole N1/N2/C3/C1/C2 ring) by \u03c0\u2013\u03c0 inter\u00adactions, with Cg\u22efCgii = 3.801\u2005(1)\u2005\u00c5 .The mol\u00adecular conformation is stabilized by an intra\u00admolecular C19\u2014H19\u22efO1 hydrogen bond, which generates an et al., 2013a2,7.013,17]hepta\u00addeca-2(7),3,5,13\u2005(17),15-penta\u00adene-10-carboxyl\u00adate, (III) E)-methyl 2-[(2-formyl-6-meth\u00adoxy\u00adphen\u00adoxy)meth\u00adyl]-3-(4-meth\u00adoxy\u00adphen\u00adyl)acrylate  and 3-methyl-1-phenyl-1H-pyrazol-5-one  was placed in a round-bottomed flask and melted at 453\u2005K for 1\u2005h. After completion of the reaction as indicated by thin-layer chromatography, the crude product was washed with 5\u2005ml of an ethyl acetate and hexane mixture (1:49 ratio), which successfully provided the title compound as a colourless solid in 93% yield. Colourless blocks were obtained by slow evaporation of an ethyl acetate solution at room temperature.A mixture of (Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Owing to poor agreement, the reflections 100, 011 and 100 were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814017929/hb7257sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814017929/hb7257Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814017929/hb7257Isup3.cmlSupporting information file. DOI: 962784CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Figure legend 1 is incorrect. The correct figure legend is:Figure 1. Effect of maggot secretions on the tPA-induced lysis of plasma clots (representative example). No secretions \u2014; 12.5 \u00b5g of secretions/mL \u2014 \u2014 \u2014; 25 \u00b5g of secretions/mL \u2013 \u2014 \u2013 \u2014; 50 \u00b5g of secretions/mL \u2013 \u2013 \u2013."}
{"text": "The title compound crystallized with two independent mol\u00adecules in the asymmetric unit. In the crystal, they are linked to one another, forming chains enclosing  22H17NO4, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. Each mol\u00adecule exists as an E isomer with C\u2014C=C\u2014C torsion angles of \u2212175.69\u2005(17) and \u2212178.41\u2005(17)\u00b0 in A and B, respectively. In mol\u00adecule A, the planes of the terminal benzene rings are twisted by an angle of 26.67\u2005(10)\u00b0, while the biphenyl unit is non-planar, the dihedral angle between the rings being 30.81\u2005(10)\u00b0. The dihedral angle between the nitro\u00adphenyl ring and the inner phenyl ring is 6.50\u2005(9)\u00b0. The corresponding values in mol\u00adecule B are 60.61\u2005(9), 31.07\u2005(8) and 31.05\u2005(9)\u00b0. In the crystal, mol\u00adecules are arranged in a head-to-head manner, with the 3-nitro\u00adphenyl groups nearly parallel to one another. The A and B mol\u00adecules are linked to one another via C\u2014H\u22efO hydrogen bonds, forming chains lying parallel to (-320) and enclosing R22(10) and R22(12) ring motifs. The meth\u00adoxy group in both mol\u00adecules is positionally disordered with a refined occupancy ratio of 0.979\u2005(4):0.021\u2005(4) for mol\u00adecule A and 0.55\u2005(4):0.45\u2005(4) for mol\u00adecule B.The title compound, C Each mol\u00adecule exists as an E isomer with the C17\u2014C16\u2014C15\u2014C14 and C39\u2014C38\u2014C37\u2014C36 torsion angles being \u2212175.69\u2005(17) and \u2212178.41\u2005(17)\u00b0, respectively. In mol\u00adecule A, the terminal benzene rings (C2\u2013C7) and (C17\u2013C22) are twisted by an angle of 26.67\u2005(10)\u00b0, while the biphenyl rings (C2\u2013C7 and C8\u2013C13) are non-planar, the dihedral angle being 30.81\u2005(10)\u00b0. The dihedral angle between rings (C8\u2013C13) and (C17\u2013C22) is 6.50\u2005(9)\u00b0. The corresponding dihedral angles in mol\u00adecule B are (C24\u2013C29 and C39\u2013C44) 60.61\u2005(9), (C30\u2014C35 and C24\u2013C29) 31.07\u2005(8) and (C30\u2013C35 and C39\u2013C44) 31.05\u2005(9)\u00b0.The title compound, Fig.\u00a01A and B lie head-to head almost parallel to one another. They are linked via C\u2014H\u22efO hydrogen bonds, forming chains lying parallel to -3-(biphenyl-4-yl)-1-prop-2-en-1-one -1--3-(2-methyl\u00adphen\u00adyl)prop-2-en-1-one -3-(3-nitro\u00adphen\u00adyl)prop-2-en-1-one  and 6.50\u2005(9)\u00b0, respectively.A search of the Cambridge Structural Database  and 3-nitro benzaldehyde  in ethanol (25\u2005ml) in the presence of NaOH (10\u2005ml 30%) was heated in a water bath for 30\u2005min. and then allowed to cool. The solid that separated was filtered and recrystallized from ethanol. The yellow-coloured crystals of the title compound used for the X-ray diffraction study were grown by slow evaporation from acetone .Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. The refined occupancy ratios for the disordered meth\u00adoxy groups are 0.979\u2005(4):0.021\u2005(4) for atoms O1A/O1B and C1A/C1B in mol\u00adecule A and 0.55\u2005(4):0.45\u2005(4) for atoms O5A/O5B and C23A/C23B in mol\u00adecule B.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989014025110/su5021sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014025110/su5021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014025110/su5021Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989014025110/su5021Isup4.cmlSupporting information file. DOI: 1034620CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The amide group is twisted by 31.30\u2005(16)\u00b0 with respect to the pyridine ring. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO, O\u2014H\u22efS and N\u2014H\u22efS hydrogen bonds into a three-dimensional supra\u00admolecular network. Weak \u03c0\u2013\u03c0 stacking is observed between parallel pyridine rings of adjacent mol\u00adecules, the centroid\u2013centroid distance being 3.8270\u2005(19)\u2005\u00c5.In the title compound, [Co(NCS) DOI: 10.1107/S1600536814011453/xu5790Isup2.hklStructure factors: contains datablock(s) I. DOI: 850080CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the structure of the naphtho\u00adquinone derivative 2-hy\u00addroxy-3-(2-methyl\u00adprop-1-en-1-yl)naphthalene-1,4-dione, the mol\u00adecules form a centrosymmetric cyclic dimer through inter\u00admolecular O\u2014H\u22efO hydrogen bonds which, together with inter\u00admolecular C\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 ring inter\u00adactions, give rise to an overall two-dimensional structure. 14H12O3, the substituent side chain, in which the H atoms of both methyl groups are disordered over six equivalent sites, lies outside of the plane of the naphthalene\u00addione ring. The ring-to-chain C\u2014C\u2014C\u2014C torsion angles are 50.7\u2005(3), \u2212176.6\u2005(2) and 4.9\u2005(4)\u00b0. An intra\u00admolecular meth\u00adyl\u2013hy\u00addroxy C\u2014H\u22efO hydrogen bond is present. In the crystal, mol\u00adecules are primarily connected by inter\u00admolecular O\u2014H\u22efO hydrogen bonds, forming a centrosymmetric cyclic dimer motif [graph set R22(10)]. Also present is a weak inter\u00admolecular C\u2014H\u22efO hydrogen bond linking the dimers and a weak \u03c0\u2013\u03c0 ring inter\u00adaction [ring centroid separation = 3.7862\u2005(13)\u2005\u00c5], giving layers parallel to (10-3).In the structure of the title compound, C Also present in the structure is a weak inter\u00admolecular C7\u2014H\u22efO2ii hydrogen bond [3.339\u2005(3)\u2005\u00c5], linking the dimers and a weak \u03c0\u2013\u03c0 ring inter\u00adaction between the benzene and quinone ring moieties of the parent ring system , giving layers parallel to  = 1.2Ueq(C). Rotational disorder was identified in the hydrogen atoms of the methyl carbon atoms C12 and C22 and these were included in the refinement over six equivalent 60\u00b0 sites with 50% occupation, with C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015024755/zs2357sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015024755/zs2357Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024755/zs2357Isup3.cmlSupporting information file. DOI: 1444109CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ligand selection of bidentate \u03b2\u2010diketonates is shown to be key to isolating a cyclic trimer. Additional reaction of \u03b2\u2010diketonates with diethyl zinc were spectroscopically characterized as compounds of the type [{Zn(Et)(\u03b2\u2010diketonate)}n] (\u03b2\u2010diketonate=OC(Me)CHC(Me)O, 2, OC(OtBu)CHC(Me)O, 3). Further studies have shown that selective oxidation of these species produces cubanes of the general formula [{Zn(OC(R)CHC(Me)O)2Zn(Et)OEt}2] , allowing a high oxygen content whilst remaining structurally suitable for use as precursors. The successful deposition of thin films of zinc oxide through aerosol\u2010assisted chemical vapor deposition (AACVD), using a novel precursor, is described and fully characterized.A conventional solution\u2010based route to a cyclic trimeric organozinc compound [{Zn(Et)( Studies involving zinc alkoxides were first reported by Frankland in 18492Zn compounds through the contributions of Lewi\u0144ski et\u2005al. and a handful of other groups.azol)]2[EtZn(azol)]2,  bridged by peroxide groups. Interestingly, this work was the first to \u2018suggest the presence of a trimer as the predominate species in solution\u2019 of the precursor aggregate, namely, [EtZn(azol)]n.The widely accepted belief that the oxidation of zinc alkyls is so fast, selectivity is not possible, was first dispelled by the structural characterization of a novel zinc alkylperoxide.It is known that the structure of organozinc compounds can be enormously varied, including multinuclear rings3 \u20102\u2010(dimethylaminomethyl)\u2010iso\u2010propoxide), whilst not crystallographically characterized, has a cyclic, not a roof\u2010like, trimeric structure (thf)}2] under mild conditions to give [{tBuZnOtBu}3]. This cluster was reported to have two distinct types of organozinc centers: two four\u2010coordinate zinc centers linked by two \u03bc3\u2010 and one \u03bc2\u2010oxygen atoms, and one three\u2010coordinate zinc center binding to two \u03bc2\u2010oxygen atoms. It was found to be a metastable product, as solution\u2010based attempts to form the compound resulted solely in the tetramer. Later in 2012, it was shown that by using a more rigid quinoline ligand, thus moving from a ZnCO3 coordination environment to ZnCNO2, a trimer could be isolated and was structurally characterized as [tBuZn(q)]3 (q=8\u2010hydroxyquinoline).In 2010, the first crystallographically characterized organozinc \u2018dimeric aggregate\u2019 with a Zn3 , in which the use of bidentate \u03b2\u2010diketonate ligands facilitated crystallization. Similar reactions of diethyl zinc with \u03b2\u2010diketonates yielded compounds of the type [{Zn(Et)(\u03b2\u2010diketonate)}n], which were spectroscopically characterized. In addition, selective reaction of these compounds with oxygen yields distorted cubanes of the general formula [{Zn(\u03b2\u2010diketonate)2Zn(Et)OEt}2]. These compounds exhibit a similar central motif to that reported previously.Herein, we report the first instance of a conventional solution\u2010based synthetic route to a structurally characterized cyclic trimeric organozinc compound with the coordination environment ZnCO3 Figure\u2005\u2009a, [{Zn(\u03b2\u2010diketonate [{Zn(Et)(OC(OMe)CHC(Me)O)}3]\u2005(1) was isolated and structurally characterized; furthermore, compounds of stoichiometry [{Zn(Et)(OC(R)CHC(Me)O)}n], where R=Me\u2005(2) and OtBu\u2005(3) (Scheme\u20051\u20133 were isolated from the equimolar reaction of Et2Zn with the respective carbonyl in high yield (>90\u2009%) and characterized by using spectroscopic techniques. Although 2 and 3 formed crystalline solids, none were of suitable quality for crystallographic analysis.The trimeric Me)O)}3]\u2005 was isol1 crystallizes in the monoclinic space group P21/n with three zinc centers, all exhibiting a distorted tetrahedral coordination \u2013O(O(1):2.0489(9)\u2005\u00c5, Zn(2)\u2013O(4):2.0247(9)\u2005\u00c5, Zn(3)\u2013O(7):2.0367(9)\u2005\u00c5] and the longer bridging Zn\u2212O lengths , which is comparable to similar structures found in the literature.1 results largely from the constraints of the central Zn3O3 ring and the three outer ZnO2C3 rings formed from coordination to the bidentate ligands.Compound\u2005tBuZnOtBu}3] \u2013O(7), 3.042\u2005\u00c5, which is considerably larger than the comparable distance in [{tBuZnOtBu}3] (2.164\u2005\u00c5),1.For comparison with the previously reported \u2018dimeric aggregate\u2019 [{] Figure\u2005\u2009c, the ctBu}3] 2.4\u2005\u00c5,16 pr\u03b2\u2010diketonate ligand facilitates the isolation of a novel type of cyclic trimeric organozinc complex\u2005(1) with a coordination environment of ZnCO3, as confirmed by crystallographic characterization. The monodentate tBu groups used by Lewi\u0144ski resulted in a metastable roof\u2010like trimer (or aggregated dimer), whereas the flexible amino alcoholates utilized by Molloy and co\u2010workers yielded oils, not solids, although NMR studies did suggest a cyclic trimeric center.The above data indicate that the use of a rigid bidentate 1\u20133 were explored.The rationale behind this ligand choice firstly lies in the successful isolation of a novel structural type, but also in increasing the oxygen loading of the compounds (as zinc precursors can lead to oxygen\u2010deficient thin films).2Zn(Et)OEt}2] (R=OMe\u2005(4), Me\u2005(5), OtBu\u2005(6)) were synthesized through the controlled addition of O2 to solutions of 1\u20133 (Scheme\u2005\u03bc2\u2010OEt group in accordance with previous reports.4\u20136 were isolated in high yields (>80\u2009%) and characterized by using spectroscopic techniques. Compounds\u20055 and 6 both crystallized out of concentrated solutions held at \u221218\u2009\u00b0C as centrosymmetric clusters in the triclinic P\u03041 space group with four zinc centers; two of which are unique and two are symmetrically generated about an inversion center .\u2005(2 and 3). Through selective oxidation, we have subsequently shown the synthesis of [{Zn(OC(R)CHC(Me)O)2Zn(Et)OEt}2]\u2005(4\u20136). X\u2010ray crystallography of 5 and 6 revealed these complexes to have a face\u2010shared, corner\u2010removed, inversion\u2010related, bis\u2010heterocubane central motif. Of additional importance is that these materials can be used as precursors to thin films of zinc oxide; as exemplified in the successful deposition of hexagonal wurtzite zinc oxide thin films. We believe these results provide a new route, through careful ligand selection, to cyclic organozinc trimers, whose rarity was commented on by Power and co\u2010workers back in 1991.In summary, we have demonstrated the solution\u2010based synthesis of the first structurally characterized cyclic trimer with a Zn1, 5, and 6 can be found in the Supporting Information.Crystallographic/refinement data for compounds\u2005m in hexanes) was obtained from Sigma Aldrich and used as supplied. Acetylacetone, methyl acetoacetate, and tert\u2010butyl acetoacetate were obtained from Sigma Aldrich, degassed, and stored over activated molecular sieves.All manipulations were performed under a dry dinitrogen atmosphere by using standard Schlenk techniques. Hexane was stored in an alumina column and dried with anhydrous engineering equipment. Diethylzinc solution . Mass spectroscopy was performed on a Thermo Finnigan MAT900 XP operating in electron impact and chemical ionization modes. Single\u2010crystal X\u2010ray diffraction datasets were collected on a SuperNova  Atlas diffractometer by using either monochromated Cu K\u03b1 radiation (\u03bb=1.54184\u2005\u00c5) or monochromated Mo K\u03b1 (\u03bb=0.71073\u2005\u00c5).m solution in hexanes, 9.76\u2005mmol) was added to dry hexane (5\u2005mL) at \u221278\u2009\u00b0C. Dry methyl acetoacetate  was added dropwise to the solution and stirred at RT for 48\u2005h. Hexane was fully removed in\u2005vacuo, resulting in an off\u2010white solid. Off\u2010white crystals grew from a concentrated solution held at \u221218\u2009\u00b0C. Yield: 1.86\u2005g, 91\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.55 , 1.47 , 1.90 , 3.27 , and 4.95\u2005ppm ; 13C{1H} NMR (600\u2005MHz) \u03b4 (C6D6): 1.0 (CH2CH3), 12.5 (CH2CH3), 27.5 (CCH3), 51.1 (OCH3), 89.3 (CCHC), 174.0 (COCH3), and 184.4\u2005ppm (CCH3); anal. calcd. for C21H36O9Zn3: C 40.12, H 5.77; found: C 40.21, H 5.89.Diethylzinc  was added to dry hexane (5\u2005mL) at \u221278\u2009\u00b0C. Dry acetylacetone  was added dropwise to the solution and stirred at RT for 48\u2005h. Hexane was fully removed in\u2005vacuo, resulting in an off\u2010white solid. Yield: 1.71\u2005g, 90\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.57 , 1.48 , 1.79 , and 5.03\u2005ppm ; 13C{1H} NMR (600\u2005MHz) \u03b4 (C6D6): 1.0 (CH2CH3), 12.4 (CH2CH3), 28.3 (CCH3), 102.0 (CCHC), and 193.1\u2005ppm (CCH3); anal. calcd. for C21H36O6Zn3: C 43.44, H 6.25; found: C 43.09, H 6.77.Diethylzinc  was added to dry hexane (5\u2005mL) at \u221278\u2009\u00b0C. Dry tert\u2010butyl acetoacetate  was added dropwise to the solution and stirred at RT for 48\u2005h. Hexane was fully removed in\u2005vacuo, resulting in an off\u2010white solid. Yield: 2.25\u2005g, 91\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.37 , 1.31 3), 1.33 , 1.94 , and 4.90\u2005ppm ; 13C{1H} NMR \u03b4 (600\u2005MHz) (C6D6): 3.4 (CH2CH3), 11.7 (CH2CH3), 27.6 (CCH3), 28.4 (C(CH3)3), 80.9 C(CH3)3, 91.0 (CCHC), 173.8 (COC(CH3)3), and 183.2\u2005ppm (CCH3); anal. calcd. for C30H54O9Zn3: C 47.73, H 7.21; found: C 46.93; H 6.97.Diethylzinc  was added to a solution of 1 and stirred for 15\u2005min at \u221278\u2009\u00b0C. The flask was purged with N2 and stirred at room temperature for 24\u2005h. Off\u2010white crystals formed from a concentrated solution held at \u221218\u2009\u00b0C. Yield: 1.85\u2005g, 87\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.62 , 1.33 , 1.60 , 1.90 , 3.33 , 3.87 , and 4.99\u2005ppm ; 13C{1H} NMR (600\u2005MHz) \u03b4 (C6D6): 2.2 (ZnCH2CH3), 12.6 (ZnCH2CH3), 19.7 (OCH2CH3), 27.3 (CCH3), 50.6 (OCH3), 61.3 (OCH2CH3), 87.0 (CCHC), 173.6 (COCH3), and 183.3\u2005ppm (CCH3); anal. calcd. for C28H48O14Zn4: C 38.64, H 5.56; found: C 38.45, H 5.64. MS: m/z [M\u2212Zn2O5C13H27]+\u22c5: 474.87; [M\u2212Zn3O8C18H34]+\u22c5: 294.97.O2 (5\u2005mL) was added to a solution of 2 and stirred for 15\u2005min at \u221278\u2009\u00b0C. The flask was purged with N2 and stirred at room temperature for 24\u2005h. Off\u2010white crystals formed from a concentrated solution held at \u221218\u2009\u00b0C. Yield: 1.66\u2005g, 84\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.69 , 1.42 , 1.61 , 1.79 , 3.80 , and 5.06\u2005ppm ; 13C{1H} NMR (600\u2005MHz) \u03b4 (C6D6): 2.7 (ZnCH2CH3), 12.9 (ZnCH2CH3), 20.1 (OCH2CH3), 28.1 (CCH3), 61.1 (OCH2CH3), 100.6 (CCHC), and 193.1\u2005ppm (CCH3); anal. calcd. for C28H48O10Zn4: C 41.71, H 6.00; found: C 42.06, H 5.92. MS: m/z [M+C3H5]+\u22c5: 847.04; [M\u2212C8H20]+\u22c5: 691.11; [M\u2212Zn2O4C13H27]+\u22c5: 426.91; [M\u2212Zn3O6C18H34]+\u22c5: 263.00.O2 (5\u2005mL) was added to a solution of 3 and stirred for 15\u2005min at \u221278\u2009\u00b0C. The flask was purged with N2 and stirred at room temperature for 24\u2005h. Off\u2010white crystals formed from a concentrated solution held at \u221218\u2009\u00b0C. Yield: 2.09\u2005g, 83\u2009%; 1H\u2005NMR (600\u2005MHz) \u03b4 (C6D6): 0.58 (q (br), 4\u2009H, ZnCH2CH3), 1.44 3), 1.51 (t (br), 6\u2009H, OCH2CH3), 1.66 , 1.92 , 4.02 , and 4.96\u2005ppm ; 13C{1H} NMR (600\u2005MHz) \u03b4 (C6D6): 1.8 (ZnCH2CH3), 13.1 (ZnCH2CH3), 19.8 (OCH2CH3), 27.4 (CCH3), 28.7 (C(CH3)3), 61.4 (OCH2CH3), 79.7 (C(CH3)3), 88.7 (CCHC), 173.4 (COC(CH3)3), and 182.1\u2005ppm (CCH3); anal. calcd. for C40H72O14Zn4: C 46.26, H 6.99; found: C 46.43, H 7.27. MS: m/z [M\u2212Zn2O5C16H33]+\u22c5: 601.05; [M\u2212Zn3O8C24H46]+\u22c5: 379.04.O2. [(Zn(OC(Me)CHC(Me)O)2Zn(Et)O(Et))2]\u2005(5)  was dissolved in dry toluene (30\u2005mL) under N2 and stirred for 10\u2005min. Thin films were deposited by using optimal conditions of a N2 flow rate of 1.2\u2005L\u2009min\u22121, a substrate temperature of 450\u2009\u00b0C, and annealing in air for 5\u2005h at 600\u2009\u00b0C. XRD was performed using a Bruker D8 Discover X\u2010ray diffractometer by using monochromatic Cu K\u03b11 and Cu K\u03b12 radiation of wavelengths 1.54056 and 1.54439\u2005\u00c5, respectively, emitted in an intensity ratio of 2:1 with a voltage of 40\u2005kV and a current of 40\u2005mA. SEM was performed by using a Philips XL30 FEG operating in plan and cross\u2010section mode with an electron beam accelerating energy of 30\u2005kV. XPS surface and depth profiling was performed by using a Thermo Scientific K\u2010Alpha XPS system with monochromatic Al K\u03b1 radiation at 1486.6\u2005eV as the X\u2010ray source. Etching was achieved by using an Ar\u2010ion etch beam at 1\u2005KeV with a current of 1.51\u2005\u03bcA. CasaXPS software was used to analyze the data with binding energies referenced to an adventitious C\u20091s peak at 284.8\u2005eV. UV/Vis/NIR transmission spectra were recorded by using a PerkinElmer Lambda 950 spectrometer in the range of 300\u20131400\u2005nm with an air background.Films were deposited onto float\u2010glass substrates with a 25\u2005nm barrier layer of crystalline SiOAs a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "E,E)-2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone azine mol\u00adecule is located on an inversion centre and linked with di\u00admethyl\u00adformamide solvent mol\u00adecules via O\u2014H\u22efO hydrogen bonds.The approximately planar -2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone azine mol\u00adecule is centrosymmetric, the mid-point of the N\u2014N bond being located on an inversion centre. All the non-H atoms of the azine mol\u00adecule are approximately coplanar, the maximum deviation being 0.017\u2005(2)\u2005\u00c5. An intra\u00admolecular O\u2014H\u22efN hydrogen bond occurs between the azine N atom and the hy\u00addroxy group. In the crystal, azine and di\u00admethyl\u00adformamide solvent mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds.In the title compound {systematic name: 4,4\u2032-bis\u00ad}, C Fluorescence properties of hydrazones have been reported -2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone azine di\u00admethyl\u00adformamide disolvate, (I)Although 2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone azine has been pre\u00adpared and studied as a fluorescent probe, its structure has not been reported. As a part of our studies on synthesis and structural peculiarities of Schiff base ligands derived from 2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone and hydrazine, we determined the structure of the title compound, -2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone azine and one dimethylformamide (DMF) mol\u00adecule. The complete azine mol\u00adecule is centrosymmetric and exists in an E,E configuration with respect to the two C=N bonds. The N1\u2014C2 bond length of 1.301\u2005(3)\u2005\u00c5 shows double-bond character. The C\u2014O bond lengths [1.349\u2005(3) and 1.358\u2005(3)\u2005\u00c5] are comparable with similar bonds in related structures  are essentially planar, with a mean deviation of 0.0024\u2005\u00c5. Each hy\u00addroxy group is nearly coplanar with its attached benzene ring; the r.m.s. deviation is 0.0045\u2005\u00c5 for the seven non-H atoms. Intra\u00admolecular O\u2014H\u22efN hydrogen bonds exist in the azine mol\u00adecule , inter\u00admolecular O\u2014H\u22efO hydrogen bonds exist between azine mol\u00adecules and DMF mol\u00adecules Table\u00a01.E,E)-2,2\u2032-di\u00adphenol -4,4\u2032-di\u00adchloro-2,2\u2032-diphenol -3,3\u2032-dieth\u00adoxy-2,2\u2032-diphenol -4,4\u2032-dimeth\u00adoxy-2,2\u2032-diphenol : \u03b4 13.59 , 10.14 , 7.58\u20137.61 , 6.37\u20136.41 , 6.30\u20136.31 , 3.34 .A mixture of 2\u2032,4\u2032-di\u00adhydroxy\u00adaceto\u00adphenone , hydrazine sulfate  and tri\u00adethyl\u00adamine  in ethanol (40\u2005ml) was heated under reflux for 24\u2005h. After cooling, the precipitate was filtrated and washed with water to afford a yellow solid. Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in DMF at room temperature for 5\u2005d . Uiso(H) = 1.2Ueq(C) for aromatic H atoms or 1.5Ueq for methyl and hy\u00addroxy groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016003686/xu5885sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016003686/xu5885Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016003686/xu5885Isup3.cmlSupporting information file. DOI: 1457201CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Pd\u2014N bond distances are 2.022\u2005(2) and 2.027\u2005(2)\u2005\u00c5, the Pd\u2014Cl bond distances are 2.2880\u2005(7) and 2.2833\u2005(7)\u2005\u00c5, and the ligand bite angle is 80.07\u2005(9)\u00b0. The dimethyl sulfoxide and water mol\u00adecules form linear chains along [100] by O\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds, generating eight- and 12-membered rings. C\u2014H\u22efCl inter\u00adactions link the chains, forming a three-dimensional arrangement. In addition, the 4,4-di-tert-butyl-2,2\u2032-bi\u00adpyridine ligand exhibits \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.8741\u2005(15) and 3.8353\u2005(15)\u2005\u00c5]. The DMSO solvent is disordered and was refined with an occupancy ratio of 0.866\u2005(3):0.134\u2005(3).The title compound, [PdCl DOI: 10.1107/S1600536814009453/pj2010Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming chains propagating along the  23H20BrNO3S, the \u2013(CH2)4\u2013 atoms are positionally disordered [occupancy ratio = 0.753\u2005(6):0.247\u2005(6)]. The ring has a half-chair conformation for both the major and minor components. The dihedral angles between the mean plane of the thio\u00adphene ring and those of the benzene and phenyl rings are 35.2\u2005(4) and 57.7\u2005(3)\u00b0, respectively. The planes of the two aryl rings are twisted with respect to each other by 86.4\u2005(6)\u00b0. In the mol\u00adecule, there is an O\u2014H\u22efN hydrogen bond forming an S(6) ring motif. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, forming chains parallel to [100].In the cyclo\u00adhexene ring of the title compound, C Reviews on the synthesis and properties of these compounds have been reported (Sabnis A/C4\u2013C7/C7A) and (C3A/C44\u2013C47/C7A) adopt a half-chair conformation. The mean plane of the major component (C3A/C4\u2013C7/C7A) is slightly twisted from the mean plane of the thio\u00adphene ring (S1/C2/C3/C3A/C7A) by 5.18\u2005(14)\u00b0. The dihedral angles between the mean plane of the thio\u00adphene ring and the benzene (C21\u2013C26) and phenyl (C31\u2013C36) rings are 35.2\u2005(4) and 57.7\u2005(3)\u00b0, respectively. The two aryl rings are normal to each other, making a dihedral angle of 86.4\u2005(6)\u00b0. In the mol\u00adecule there is an O\u2014H\u22efN hydrogen bond forming an S(6) ring motif methanone derivatives gave eight hits, which include five structures closely related to the title compound. These include [2-[(2-hy\u00addroxy\u00adbenzyl\u00adidene)amino](phen\u00adyl)methanone (I)et al., 2014aet al., 2014bb]thio\u00adphen-3\u00adyl](phen\u00adyl)methanone (III) -4,5,6,7-tetra\u00adhydro\u00adbenzo[b]thio\u00adphen-3-yl](phen\u00ad\u00adyl)methanone (IV) thio\u00adphene-3-yl](phen\u00adyl)methanone (V) thiophen-3-yl)-phenyl\u00admethanone  in 10\u2005ml of methanol an equimolar amount of 5-bromo-2-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde  was added with constant stirring. The mixture was refluxed for 6\u2005h. A yellowish brown precipitate was obtained. Completion of the reaction was confirmed by thin layer chromatography. The precipitate obtained was filtered and dried at room temperature overnight. The solid was then recrystallized using a 1:1 solution of aceto\u00adnitrile and di\u00adchloro\u00admethane, giving colourless block-like crystals.To a solution of  = 1.5Ueq for the hydroxyl and methyl H atoms, and = 1.2Ueq(C) for other H atoms. A single weak outlier reflection  I. DOI: 10.1107/S2056989015000195/su5055Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015000195/su5055Isup3.cmlSupporting information file. DOI: 1042320CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These inter\u00adactions exhibit a parallel displaced \u03c0\u2013\u03c0 stacking mode. Additional weak C\u2014H\u22ef\u03c0-ring and C\u2014H\u22efN and C\u2014H\u22efF inter\u00adactions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octa\u00adhedral geometry. The counter-charge is provided by two hexa\u00adfluorido\u00adphosphate anions and the asymmetric unit is completed by three aceto\u00adnitrile solvent mol\u00adecules of crystallization. Four F atoms of one PF6\u2212 anion are disordered over three sets of sites with occupancies of 0.517\u2005(3):0.244\u2005(3):0.239\u2005(3). Two aceto\u00adnitrile solvent mol\u00adecules are highly disordered and their estimated scattering contribution was subtracted from the observed diffraction data using the SQUEEZE option in PLATON .In the title compound, Spek 2009. Acta Cr II complexes with tape and bpy-type ligands, see: Brietzke et al. 2(C16H8N4)](PF6)2\u00b73C2H3N = 0.047wR(F2) = 0.124S = 0.948918 reflections743 parameters363 restraintsH-atom parameters constrainedmax = 0.51 e \u00c5\u22123\u0394\u03c1min = \u22120.54 e \u00c5\u22123\u0394\u03c1X-AREA  global, I. DOI: 10.1107/S1600536814011969/tk5315Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004679CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked  25H25N3O, comprises a 2-amino\u00adpyridine ring fused with a cyclo\u00adheptane ring, which adopts a chair conformation. The central pyridine ring (r.m.s. deviation = 0.013\u2005\u00c5) carries three substituents, viz. a benzyl\u00adamino group, a meth\u00adoxy\u00adphenyl ring and a carbo\u00adnitrile group. The N atom of the carbo\u00adnitrile group is significantly displaced [by 0.2247\u2005(1)\u2005\u00c5] from the plane of the pyridine ring, probably due to steric crowding involving the adjacent substituents. The phenyl and benzene rings are inclined to one another by 58.91\u2005(7)\u00b0 and to the pyridine ring by 76.68\u2005(7) and 49.80\u2005(6)\u00b0, respectively. In the crystal, inversion dimers linked by pairs of N\u2014H\u22efNnitrile hydrogen bonds generate R22(14) loops. The dimers are linked by C\u2014H\u22ef\u03c0 and slipped parallel \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6532\u2005(3)\u2005\u00c5] into a three-dimensional structure.The title compound, C The cyclo\u00adheptane ring adopts a chair conformation with puckering parameters Q2 = 0.4634\u2005(15)\u2005\u00c5, \u03d52 = 304.24\u2005(18)\u00b0 and Q3 = 0.6481\u2005(16)\u2005\u00c5 and \u03d53 = 284.37\u2005(12)\u00b0. The phenyl (C22\u2013C27) and benzene (C31\u2013C36) rings are inclined to one another by 58.91\u2005(7)\u00b0 and to the pyridine (N3/C2\u2013C6) ring by 76.68\u2005(7) and 49.80\u2005(6)\u00b0, respectively. The N atom of the carbo\u00adnitrile group, N1, is significantly displaced by 0.2247\u2005(1)\u2005\u00c5 from the plane of the pyridine ring, perhaps due to steric crowding. The shortening of the C\u2014N distance [C5\u2014N3 = 1.3390\u2005(14)\u2005\u00c5] and the opening of the N3\u2014C5\u2014C4 angle to 124.47\u2005(10)\u00b0 may be attributed to the size of the substituent at C1, and correlates well with the values observed in a similar structure \u2005\u00c5 is shorter than the average conjugated C\u2014N single bond, 1.370\u2005(1)\u2005\u00c5, found in the Cambridge Structural Database \u2005\u00c5 is significantly shorter than the O1\u2014C37 distance of 1.410\u2005(2)\u2005\u00c5. An enlarge\u00adment of bond angle [C33\u2014C34\u2014O1 = 124.34\u2005(13)\u00b0] on one side and a narrowing of bond angle [C35\u2014C34\u2014O1 = 116.29\u2005(12)\u00b0] on the other side of the benzene ring may be due to the steric repulsion between the aromatic rings and the methyl group, as found in a similar structure , normal distance = 3.5920\u2005(5), slippage = 0.667\u2005\u00c5; Cg1 is the centroid of the N3/C2\u2013C6 ring; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01], as shown in Fig.\u00a02In the crystal, mol\u00adecules are linked r Table\u00a01. They arH-cyclohepta\u00ad[b]pyridine -4-(4-meth\u00adoxy\u00adphen\u00adyl)-6,7,8,9-tetra\u00adhydro-5p-TSA (1.0\u2005mmol) was added. The reaction mixture was heated under reflux for 2\u20133\u2005h. On completion of the reaction, checked by thin-layer chromatography (TLC), the mixture was poured into crushed ice and extracted with ethyl acetate. The excess solvent was removed under vacuum and the residue was subjected to column chromatography using petroleum ether/ethyl acetate mixture (97:3 v/v) as eluent to afford pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of the title compound. .A mixture of cyclo\u00adhepta\u00adnone (1\u2005mmol), 4-meth\u00adoxy aldehyde (1\u2005mmol) and malono\u00adnitrile (1\u2005mmol) and benzyl\u00adamine (1mmol) was taken in ethanol (10\u2005ml) to which Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq for other H atoms. The DELU restraint was applied.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814024878/su5014sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814024878/su5014Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814024878/su5014Isup3.cmlSupporting information file. DOI: 1033842CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The naphthyl moieties are close to perpendicular [dihedral angle = 72.08\u2005(5)\u00b0]. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, generating layers which surround channels occupied by disordered guest mol\u00adecules.In the solid-state, bis- 44H44N2O8, iminium\u00adyl]meth\u00adyl}-3,3\u2032-dimethyl-2,2\u2032-bi\u00adnaphthalene-7,7\u2032-diolate) has been obtained by the addition of p-anizidine to gossypol dissolved in di\u00adchloro\u00admethane. In the solid state, the title compound exists in the enamine or quinoid form. The two naphthyl moieties are inclined to one another by 72.08\u2005(5)\u00b0. The pendant phenyl rings are inclined at 22.26\u2005(14) and 23.86\u2005(13)\u00b0 to the corresponding naphthyl rings. In the crystal, mol\u00adecules are incorporated into layers through inversion-related pairs of O\u2014H\u22efO inter\u00adactions [graph sets R22(20) and R22(10)] and translation-related O\u2014H\u22efO inter\u00adactions [graph set C(15)]. The packing of these layers in the crystal structure gives rise to channels in the [011] direction, with hydro\u00adphobic inter\u00adactions occurring between adjacent layers. The channels are 5\u20137\u2005\u00c5 wide, and the void volume of each cell is 655\u2005\u00c53, corresponding to 26.6% of the cell volume. Disordered guest mol\u00adecules, probably solvent and water mol\u00adecules, occupy these voids of the crystal; their contribution to the scattering was removed with the SQUEEZE routine  of PLATON .The title compound, CSpek 2015. Acta CrSpek 2009. Acta Cr However, bis-p-anizidinegossypol crystallizes in a triclinic  and 1.476\u2005(4)\u2005\u00c5. In addition, the N1\u2014C22 [1.332\u2005(4)\u2005\u00c5] and N2\u2014C27 [1.319\u2005(4)\u2005\u00c5] bonds are shorter than N1\u2014C31 [1.433\u2005(4)\u2005\u00c5] and N2\u2014C38 [1.441\u2005(4)\u2005\u00c5], respectively. Contrarily, C7=O3 [1.289\u2005(3)\u2005\u00c5] and C17=O7 [1.275\u2005(3)\u2005\u00c5] bonds are longer than typical standard values.The mol\u00adecule consists of four ring systems, two of which are naphthalene ring systems, and the other two are phenyl rings. The C1\u2013C10 naphthyl unit is more planar then C11\u2013C20 naphthyl one in which atoms C12, C16, C17, C18 and C19 deviate by 0.051\u2005(3), 0.070\u2005(3), 0.059\u2005(3), 0.082\u2005(3) and 0.054\u2005(3)\u2005\u00c5, respectively, from the mean plane. The two naphthyl moieties are inclined to one another by 72.08\u2005(5)\u00b0. The phenyl rings are inclined at 22.26\u2005(14) and 23.86\u2005(13)\u00b0 to the corresponding naphthyl rings. The bond lengths and angles are mostly in good agreement with those observed in the analogous fragments of the gossypol and dianilinegossypol mol\u00adecules (Gdaniec A\u22efO3 (and N2\u2014H2\u22efO7) bond closes a six-membered ring C7\u2014C8\u2014C22\u2014N1\u2014H1A\u22efO3 (and C17\u2014C18\u2014C27\u2014N2\u2014H3\u22efO7), while the other type of hydrogen bond O4\u2014H4\u22efO3 (and O8\u2014H8\u22efO7) forms a five-membered ring C6\u2014C7\u2014O3\u22efH4\u2014O4 (and C16\u2014C17\u2014O7\u22efH8\u2014O8) (Table\u00a01There are two intra\u00admolecular hydrogen bonds in the mol\u00adecule. The N1\u2014H1) Table\u00a01.p-anizidinegossypol mol\u00adecules are incorporated into centrosymmetric dimers typical for gossypol and dianilinogossypol crystal structures by means of a pair of inversion-related hydrogen bonds O5\u2014H5\u22efO3  and a very weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adaction with a Cg\u22efCg distance of 4.182\u2005(2)\u2005\u00c5 where Cg is the centroid of the C31\u2013C36 ring. The packing of these layers in the crystal structure gives rise to wide ragged channels in the [011] direction. The stabilization of the crystal structure is supported by hydro\u00adphobic inter\u00adactions between adjacent layers. The channels in the structure are 5-7\u2005\u00c5 wide and the void volume of each cell is 655\u2005\u00c53, corresponding to 26.6% of the cell volume. Disordered solvated mol\u00adecules, probably solvent and water mol\u00adecules, occupy these voids of the crystal; their contribution to the scattering was removed with the SQUEEZE routine . C-bound H atoms were positioned geometrically and refined using a riding model, with d(C\u2014H) = 0.93\u2005\u00c5 and Uiso = 1.2Ueq(C) for aromatic, d(C\u2014H) = 0.98\u2005\u00c5 and Uiso = 1.2Ueq (C) for methine, d(C\u2014H) = 0.96\u2005\u00c5 and Uiso = 1.5Ueq (C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015020393/hb7516sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020393/hb7516Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020393/hb7516Isup3.cmlSupporting information file. DOI: 1433643CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I complex, a discrete binuclear AgI complex, acetate anions, aceto\u00adnitrile solvent mol\u00adecules and water mol\u00adecules. The mol\u00adecular components are linked through O\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds, forming a chain structure along [100].The title compound consists of a mononuclear Ag 2(C3H6N2S)4(C18H15P)2](C2H3O2)2\u00b7[Ag(C2H3O2)(C3H6N2S)(C18H15P)2]2\u00b72C2H3N\u00b74H2O, the AgI ion in the mononuclear neutral complex exhibits a distorted tetra\u00adhedral environment with coordination by two P atoms from tri\u00adphenyl\u00adphosphane (PPh3) ligands, one S atom of an imidazolidine-2-thione (etu) ligand and one O atom of an acetate anion. The binuclear cationic complex comprises two inversion-related [Ag(C3H6N2S)2(C18H15P)] units with AgI ions bridged by two S atoms from etu ligands forming a four-membered Ag\u2013S\u2013Ag\u2013S ring. Each AgI ion is coordinated by a P atom of a PPh3 ligand, two S atoms of bridging etu ligands and the terminal S atom of an etu ligand in a distorted tetra\u00adhedral environment. In the crystal, the mononuclear complex is linked to lattice water mol\u00adecules through O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming a chain along [100]. In addition, the binuclear complex mol\u00adecules are connected to acetate anions and lattice water mol\u00adecules via O\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds, also along [100].In the title compound, [Ag The mol\u00adecule of the binuclear complex lies across a crystallographic inversion center which is at the center of the Ag2S2 core. The two AgI ions are bridged by two S atoms of etu ligands forming a four-membered Ag\u2013S\u2013Ag\u2013S ring. Each AgI ion is in a distorted tetra\u00adhedral coordination geometry formed by a P atom of a PPh3 ligand, the S atoms of two bridging etu ligands and a terminal S atom of an etu ligand.The structures of the mol\u00adecular components of the title compound are shown in Fig.\u00a01A\u22efO6, O7\u2014H7B\u22efO6iv, N6\u2014H6\u22efO4 and N5\u2014H5\u22efO7iii hydrogen bonds   was added and the mixture was stirred for 3\u2005h. Ethyl\u00adene\u00adthio\u00adurea  was added and the new reaction mixture was heated under reflux for 5\u2005h. The resulting clear solution was filtered off and left to evaporate at room temperature. Crystals suitable for X-ray diffraction, which were deposited upon standing for a week, were filtered off and dried under reduced pressure.Tri\u00adphenyl\u00adphosphane  was dissolved in 30\u2005cmUiso(H) = 1.2Ueq(C); 0.99\u2005\u00c5 (CH2) and Uiso(H) = 1.2Ueq(C); 0.98\u2005\u00c5 (CH3) and Uiso(H) = 1.5Ueq(C); 0.88\u2005\u00c5 (NH) and Uiso(H) = 1.2Ueq(N). Water hydrogen atoms were located from a difference Fourier map and were refined with an O\u2014H distance restraint of 0.84\u2005(2)\u2005\u00c5 and Uiso(H) = 1.2Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901600308X/wm5275sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901600308X/wm5275Isup2.hklStructure factors: contains datablock(s) I. DOI: 1452047CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound contains two crystallographically independent mol\u00adecules with the similar conformation, the piperidine rings in both mol\u00adecules adopt a similar distorted chair conformation and have pseudo mirror planes passing through the N\u2014O bond. 22H25F2N4O2, contains two crystallographically independent mol\u00adecules. In one mol\u00adecule, the two benzene rings are oriented at a dihedral angle of 1.93\u2005(10)\u00b0 and in the other mol\u00adecule the corresponding dihedral angle is 7.19\u2005(9)\u00b0. The piperidine rings in the two mol\u00adecules adopt a similar distorted chair conformation, and both have pseudo-mirror planes passing through the N\u2014O bonds. An intra\u00admolecular O\u2014H\u22efN hydrogen bond between the hy\u00addroxy group and the imine N atom is observed in both mol\u00adecules. In the crystal, weak C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds, enclosing R22(6) ring motifs, and weak \u03c0\u2013\u03c0 stacking inter\u00adactions link the mol\u00adecules into a three-dimensional supra\u00admolecular network, with centroid-to-centroid distances between the nearly parallel phenyl and benzene rings of adjacent mol\u00adecules of 3.975\u2005(2) and 3.782\u2005(2)\u2005\u00c5.The asymmetric unit of the title compound, C The six-membered rings (O1/H1/N3/C10/C11/C13) and (O3/H3/N7/C31/C32/C35) are almost planar, and they are oriented at dihedral angles of 0.83\u2005(10) and 0.92\u2005(9)\u00b0, respectively, to the adjacent benzene (B and E) rings.The phenyl [C (N4/C14\u2013C18) and F (N8/C36\u2013C40)] rings are in distorted chair conformations  having total puckering amplitudes QT of 0.491\u2005(3)\u2005\u00c5 (for ring C) and 0.509\u2005(3)\u2005\u00c5 (for ring F), and they have pseudo mirror planes passing through the N4\u2014O2 (for ring C) and N8\u2014O4 (for ring F) bonds.The piperidine , with centroid\u2013centroid distances of 3.975\u2005(2) and 3.782\u2005(2)\u2005\u00c5, respectively, may further stabilize the structure.In the crystal, strong intra\u00admolecular O\u2014H\u22efN and weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds Table\u00a02 link the3 (1:1) solution (70\u2005ml) of 5-[diazen\u00adyl]-2-hy\u00addroxy\u00adbenzaldehyde , and heated at 333\u2005K for 2\u2005h. Then, the reaction mixture was left to slowly cool to room temperature. After one day, orange microcrystals were obtained . Orange block-shaped crystals, suitable for X-ray analysis, were obtained by recrystallization from methanol/CHCl3 (1:1) solution by slow evaporation at room temperature after several days (m.p. 473\u2013475\u2005K).The title compound was synthesized by the reaction of 5-[diazen\u00adyl]-2-hy\u00addroxy\u00adbenzaldehyde , 0.97\u2005\u00c5 (for CH2) and 0.98\u2005\u00c5 (for CH), and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and x = 1.2 for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015012049/xu5856sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015012049/xu5856Isup2.hklStructure factors: contains datablock(s) I. DOI: 1408338CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E conformation. An intra\u00admolecular C\u2014H\u22efF hydrogen bond generates an S(6) ring motif. In the crystal, mol\u00adecules are arranged into centrosymmetric dimers via pairs of C\u2014H\u22efF hydrogen bonds. The crystal structure also features C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions. Hirshfeld surface analysis was used to confirm the existence of inter\u00admolecular inter\u00adactions.In the title compund, the enone moiety adopts an  23H14ClFO, the enone moiety adopts an E conformation. The dihedral angle between the benzene and anthracene ring is 63.42\u2005(8)\u00b0 and an intra\u00admolecular C\u2014H\u22efF hydrogen bond generates an S(6) ring motif. In the crystal, mol\u00adecules are arranged into centrosymmetric dimers via pairs of C\u2014H\u22efF hydrogen bonds. The crystal structure also features C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions. Hirshfeld surface analysis was used to confirm the existence of inter\u00admolecular inter\u00adactions.In the title compound, C The anthracene ring system (C10\u2013C23) is twisted at the C9\u2013C10 bond from the (E)-3-(2-chloro-6-fluoro\u00adphen\u00adyl)acryl\u00adaldehyde moiety [maximum deviation = 0.193\u2005(16)\u2005\u00c5 for atom O1] with a C8\u2014C9\u2014C10\u2014C23 torsion angle of \u221261.4\u2005(2)\u00b0. The terminal benzene and anthracene ring systems  form a dihedral angle of 63.42\u2005(8)\u00b0. The least-squares plane through the enone moiety [O1/C7\u2013C9) with a maximum deviation of 0.033\u2005(2)\u2005\u00c5 for atom C9] makes dihedral angles of 5.62\u2005(13) and 59.18\u2005(12)\u00b0 with the benzene (C1\u2013C6) and anthracene (C10\u2013C23) rings, respectively. An intra\u00admolecular C8\u2014H8A\u22efF1 hydrogen bond is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with those in previously reported structures  inter\u00adactions .In the crystal Fig.\u00a02, the mol1 Table\u00a01 hydrogeng1 Fig.\u00a03 and Cg1\u22efet al., 2012dnorm are shown in Fig.\u00a04The inter\u00admolecular inter\u00adactions of the title compound can be visualized using Hirshfeld surface analysis .The C17\u2014H17ed + id \u223c2.6\u2005\u00c5 on the fingerprint plot. The presence of \u03c0\u2013\u03c0 inter\u00adactions is shown as C\u22efC contacts, which contribute 8.9% of the Hirshfeld surfaces. The presence of these inter\u00adactions can also be shown by the Hirshfeld surfaces mapped by shape index  can be also be seen, indicated by the wings of ex Fig.\u00a06 and the ex Fig.\u00a06.A mixture of 9-acetyl\u00adanthracene  and 2-chloro-6-fluoro\u00adbenzaldehyde  was dissolved in methanol (20\u2005ml). A catalytic amount of NaOH  was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5\u20136\u2005h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50\u2005ml) and the resulting crude solid was collected by filtration. The compound was dried and purified by repeated recrystallization from acetone solution, forming yellow plates.Uiso(H) = 1.2Ueq(C). The most disagreeable reflections (\u22121\u00a0\u2212\u00a02 4 and \u22121 1 0) were omitted from the final refinement.Crystal data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016005028/hb7569sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016005028/hb7569Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016005028/hb7569Isup3.cmlSupporting information file. DOI: 1470351CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "P21/n, the methyl acrylate and nitro\u00advinyl units are relatively planar with an E conformation about the C=C bonds. The two aromatic rings are inclined to one another by 74.87\u2005(9) and 75.65\u2005(2)\u00b0 for compounds (I) and (II), respectively. In the crystal of (I), chains along the b axis are formed via C\u2014H\u22efO hydrogen bonds. In the crystal of (II), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming sheets parallel to the ac plane.In the title compounds, (I) and (II), both of which crystallize in the monoclinic space group  19H16ClNO5, (I), and C19H15Cl2NO5, (II), both crystallize in the monoclinic space group P21/n. They differ essentially in the orientation of the methyl acetate group, with the C=O bond directed towards the NO2 group in (I) but away from it in (II). In compound (I), the mean plane of the methyl acrylate unit is planar, with a maximum deviation of 0.0044\u2005(2)\u2005\u00c5 for the methyl C atom, while in (II) this deviation is 0.0147\u2005\u00c5. The inter\u00adplanar angles between the two aromatic rings are 74.87\u2005(9) and 75.65\u2005(2)\u00b0 for compounds (I) and (II), respectively. In both compounds, the methyl acrylate and nitro\u00advinyl groups each adopt an E conformation about the C=C bond. In the crystal of (I), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds forming chains along the b axis. The chains are linked via C\u2014H\u22efCl hydrogen bonds, forming sheets parallel to the ab plane. The sheets are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional structure. In the crystal of (II), mol\u00adecules are linked by pairs of C\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(30) ring motif. The dimers are linked via C\u2014H\u22efO hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs. The sheets are linked via parallel slipped \u03c0\u2013\u03c0 inter\u00adactions (inter\u00adcentroid distances are both ca 3.86\u2005\u00c5), forming a three-dimensional structure.The title compounds, C In (I)In both compounds, the nitro\u00advinyl groups [C2=C1\u2014N1], have an b-axis direction n Table\u00a01. The chane Fig.\u00a04. The shee Table\u00a01.ac plane and enclosing via slipped parallel \u03c0\u2013\u03c0 inter\u00adactions, forming a three-dimensional structure, Fig.\u00a06Cg1\u22efCg1i = 3.863\u2005(2)\u2005\u00c5, inter-planar distance = 3.487\u2005(1)\u2005\u00c5, slippage 1.662\u2005\u00c5; Cg1 is the centroid of ring C3\u2013C8; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y, z\u00a0+\u00a01, and Cg2\u22efCg2ii = 3.861\u2005(2)\u2005\u00c5, inter-planar distance = 3.506\u2005(2)\u2005\u00c5, slippage = 1.617\u2005\u00c5; Cg2 is the centroid of ring C14\u2013C19; symmetry code: (ii) \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a02].In compound (II)f Table\u00a02. The dims Table\u00a02. The sheE)-2-(phen\u00adoxy\u00admeth\u00adyl)-3-phenyl\u00adacrylate gave 12 hits. There is a great variety in the dihedral angle involving the two aromatic rings; from a minimum of ca 47.2\u00b0 in (E)-methyl 2-({2-eth\u00adoxy-6-[(E)-(hy\u00addroxy\u00adimino)\u00admeth\u00adyl]phen\u00adoxy}meth\u00adyl)-3-phenyl\u00adacrylate -2-[(2-nitro\u00adphen\u00adoxy)meth\u00adyl]-3-phenyl\u00adacrylate -3-(2-chloro\u00adphen\u00adyl)-2-{[2-phen\u00adoxy]meth\u00adyl}acrylate (1\u2005mmol) for compound (I)E)-2-{[4-chloro-2-phen\u00adoxy]meth\u00adyl}-3-(2-chloro\u00adphen\u00adyl)acrylate (1\u2005mol) for compound (II)tert-butyl dicarbonate (1.2 equiv) were added and the solutions of the corresponding crude products were stirred at 318\u2013323\u2005K for 2\u2005h, followed by TLC (20% EtOAc and petroleum ether). The solvents were removed under reduced pressure and the residues purified by column chromatography on silica gel  to afford pure products. The purified compounds were recrystallized from ethanol, by slow evaporation of the solvent, yielding block-like crystals of compounds (I)The title compounds were prepared in a similar manner using a mixture of methyl (Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016001493/su5265sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989016001493/su5265Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016001493/su5265IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016001493/su5265Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016001493/su5265IIsup5.cmlSupporting information file. DOI: 1449405, 1449404CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing features supra\u00admolecular layers sustained by O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonding.A distorted octa\u00adhedral  2(C12H10N2)3(C6H12NOS2)4]\u00b74C2H3N, comprises a CdII atom, two di\u00adthio\u00adcarbamate (dtc) anions, one and a half trans-1,2-dipyridin-4-yl\u00adethyl\u00adene (bpe) mol\u00adecules and two aceto\u00adnitrile solvent mol\u00adecules. The full binuclear complex is generated by the application of a centre of inversion. The dtc ligands are chelating, one bpe mol\u00adecule coordinates in a monodentate mode while the other is bidentate bridging. The resulting cis-N2S4 coordination geometry is based on an octa\u00adhedron. Supra\u00admolecular layers, sustained by hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) and hy\u00addroxy-O\u2014H\u22efN(bpe) hydrogen bonding, inter\u00adpenetrate to form a three-dimensional architecture; voids in this arrangement are occupied by the aceto\u00adnitrile solvent mol\u00adecules. Additional inter\u00admolecular inter\u00adactions falling within the specified framework have been analysed by Hirshfeld surface analysis, including \u03c0\u2013\u03c0 inter\u00adactions.The asymmetric unit of the title compound, [Cd The di\u00adthio\u00adcarbamate ligands coordinate with significant differences in their Cd\u2014S bond lengths, Table\u00a01d(Cd\u2014Slong) \u2013 d(Cd\u2014Sshort) = 0.15\u2005\u00c5 for the S1-di\u00adthio\u00adcarbamate ligand cf. 0.10\u2005\u00c5 for the S3-ligand. Nevertheless, there is considerable delocalization of \u03c0-electron density in the CdS2C chelate rings as evidenced by the equivalence of the associated C\u2014S bond lengths, Table\u00a01trans [178.06\u2005(3)\u00b0] and the less tightly bound sulfur atoms are trans to nitro\u00adgen atoms, Table\u00a01cis. The distortions from the ideal geometry are readily related to the restricted bite angles of the chelating ligands, Table\u00a01i and C22\u2014C21\u2014C24\u2014C25 torsion angles of \u221212.2\u2005(6) and 13.9\u2005(5)\u00b0 for the bi- and mono-dentate ligands, respectively; symmetry code: (i) 2\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z.The mol\u00adecular structure of the binuclear title compound, {Cdn TONTO  inter\u00adactions  and pyridyl-C\u2014H\u22efN(acetonitrile) inter\u00adactions. The presence of short inter\u00admolecular C\u22efC and C\u22efH contacts, Table\u00a03A atoms in Fig.\u00a03i link of the bridging bpe ligand can be viewed as a bright-red region around the C18 atom in the dnorm mapped surface, Fig.\u00a03b; this arises as it is the asymmetric unit that has been investigated not the entire binuclear mol\u00adecule. With respect to the aceto\u00adnitrile molecule the dnorm mapped surfaces show only the aceto\u00adnitrile-N7 to be involved in a significant inter\u00admolecular C\u2014H\u22efN inter\u00adaction \u2005\u00c5, symmetry code: 3\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z] is reflected through the appearance of green points around de = di \u223c1.8\u2005\u00c5, the red and blue triangle pairs on the Hirshfeld surface mapped with shape-index property identified with arrows in the image of Fig.\u00a07g, with the tips at de + di \u223c2.95\u2005\u00c5 arising from the short inter\u00adatomic S\u22efH/H\u22efS contacts listed in Table\u00a03In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into C\u22efH/H\u22efC contacts with 15.9% contribution to the Hirshfeld surface, Fig.\u00a06et al., 2014i.e. 0.97, is in accord with expectation , may be calculated on the basis of Hirshfeld surface analysis 2(\u03bc-bpe)]n, which is a linear coordination polymer with a trans-N2S4 donor set  zinc atoms 2]2(\u03bc-bpe) species still forms with non-coordinating bpe included in the structure 2]2(\u03bc-bpe) and one-dimensional [Zn(S2COEt)2(\u03bc-bpe)]n are formed with the dimensionality correlated with the steric bulk of the xanthate-bound R groups 2]2(\u03bc-bpe)}n, R = iPr and Cy (\u03bc2-NO3)(\u03bc-bpe)(bpe)(OH2)]n 2(\u03bc-bpe)(bpe)2(OH2)4]n (\u03bc-bpe)(bpe)2(OH2)2]NO3(bpe)(H2O)4.45 i.e. 2:1, 1:1 or 1:2, between the precursor mol\u00adecules. In a typical experiment, Cd[S2CN(iPr)CH2CH2OH]2  was dissolved in boiling aceto\u00adnitrile (30\u2005ml). trans-1,2-Dipyridin-4-yl\u00adethyl\u00adene  was added to this solution, which was allowed to slowly cool to room temperature. Yellow prisms precipitated within an hour. The yield was not measured but was close to qu\u00adanti\u00adtative based on Cd. M.p. = 463\u2013465\u2005K (uncorrected). IR : 1607 m, 1449 ms, 1407 s, 1170 s, 1037 s, 968 s, 954 s, 824 s. NMR: 1H \u03b4 (p.p.m.): 8.6 , 7.6 , 7.54 , 5.21 , 4.82 , 3.76-3.67 , 1.18 . TGA: one sharp step  followed by a protracted mass loss totalling 71.5%, assigned to decomposition to CdS .The title compound was isolated regardless of the ratio, Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989016010768/hb7594sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016010768/hb7594Isup2.hklStructure factors: contains datablock(s) I. DOI: 1489732CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the two independent mol\u00adecules stack head-to-tail probably due to the presence of the dipole moment of the  11H12N6O2, a \u03c0-conjugated triazene, crystallized with two independent mol\u00adecules (A and B) in the asymmetric unit. Both mol\u00adecules have an E conformation about the \u2013N=N\u2013 bond and have slightly twisted overall conformations. In mol\u00adecule A, the imidazole ring is inclined to the benzene ring by 8.12\u2005(4)\u00b0, while in mol\u00adecule B the two rings are inclined to one another by 7.73\u2005(4)\u00b0. In the crystal, the independent mol\u00adecules are linked to each other by C\u2014H\u22efO hydrogen bonds, forming \u2013A\u2013A\u2013A\u2013 and \u2013B\u2013B\u2013B\u2013 chains along [100]. The chains are linked by C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming sheets lying parallel to (001). The sheets are linked by further C\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions , forming a three-dimensional framework structure.The title compound, C The structure of the triazene moiety is influenced by the resonance arising from delocalization of the electron lone-pair on the third N atom, towards the double bond. Triazenes are relatively old compounds from the organic chemist\u2019s viewpoint. It was as early as 1862 that Griess described a suitable method for the synthesis of 1,3-di\u00adphenyl\u00adtriazene  of the title compound are illustrated in Fig.\u00a01E conformation about the \u2013N5=N4\u2013 and \u2013N11=N10\u2013 bonds and the bond lengths and angles of the \u03c0-conjugated triazene unit  are inclined to one another by 7.73\u2005(4)\u00b0.The mol\u00adecular structures of the two independent mol\u00adecules ; see Fig.\u00a02Cg1\u22efCg4i = 3.5243\u2005(5)\u2005\u00c5; Cg1 and Cg4 are the centroids of the imidazole ring of mol\u00adecule A and the benzene ring of mol\u00adecule B; symmetry code: (i) x, y, z\u00a0\u2212\u00a01], forming a three-dimensional framework structure : \u03b4 7.99 , 7.85\u20137.83 , 7.70\u20137.69 , 7.55\u20137.52 , 7.06  3.60 . 13C NMR : \u03b4 154.4, 151.1, 149.0, 130.6, 126.9, 118.8, 118.3, 114.4, 35.7. UV/Vis : \u03bb (\u220a) = 455\u2005nm. HRMS : m/z calculated for C11H13N6O2 [M + H]+ 261.1095, found 261.1094.1-Azido-3-nitro\u00adbenzene was prepared according to the literature procedure  = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814020698/su2778sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814020698/su2778Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814020698/su2778Isup3.cmlSupporting information file. DOI: 977732CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Supra\u00admolecular layers sustained by N\u2014H\u22efN and N\u2014H\u22ef\u03c0 inter\u00adactions are found in the crystal packing; these are connected by \u03c0\u2013\u03c0 contacts.A penta\u00adcoordinated Zn 32H16N8)(C7H9N)]\u00b73C7H9N, comprises two independent complex mol\u00adecules and three benzyl\u00adamine solvent mol\u00adecules. Each complex mol\u00adecule features a penta\u00adcoordinated Zn2+ ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl\u00adamine mol\u00adecule; it is the relative orientations of the latter that differentiate between the independent complex mol\u00adecules. The uncoordinated benzyl\u00adamine mol\u00adecules display different conformations in the structure, with syn-Car\u2014Car\u2014Cm\u2014N  torsion angles spanning the range \u221228.7\u2005(10) to 35.1\u2005(14)\u00b0. In the crystal, N\u2014H\u22efN and N\u2014H\u22ef\u03c0 inter\u00adactions lead to supra\u00admolecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl\u00adamine mol\u00adecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593\u2005(2)\u2005\u00c5] so that a three-dimensional architecture is formed.The asymmetric unit of the title compound, 2[Zn(C Recent inter\u00adest has centered on their electronic, photoelectronic and catalytic properties for a diverse array of applications including photodynamic therapy  is still less than 7\u2005mM Zinc phthalocyanine (ZnPC) is one of the more soluble members of the transition metal phthalocyanines, although a saturated solution in NMP (i.e. 2.025\u2005(3)\u2005\u00c5 [Zn1\u2014N6] to 2.045\u2005(3) [Zn1\u2014N4] \u00c5, suggesting extensive delocalization of \u03c0-electron density over the PC chromophore. Further, the Zn\u2014N(PC) bond lengths are systematically shorter than the Zn\u2014N(amino) bonds. The N5 donor set defines an approximately square-pyramidal geometry with the benzyl\u00adamino-N atoms occupying the axial position. In this description, Zn1 lies 0.4670\u2005(16)\u2005\u00c5 above the least-squares plane defined by the four PC-N atoms (r.m.s. deviation = 0.0104\u2005\u00c5) in the direction of the benzyl\u00adamino-N atom [2.570\u2005(4)\u2005\u00c5 above the plane]; the comparable values for the Zn2-containing mol\u00adecule are 0.4365\u2005(16), 0.0076 and 2.549\u2005(4)\u2005\u00c5, respectively. That the N5 donor set defines a square pyramid is qu\u00adanti\u00adfied by the value of \u03c4 = 0.02 for each of the Zn1- and Zn2-containing mol\u00adecules, which compares to the \u03c4 values of 0.0 and 1.0 for ideal square-pyramidal and trigonal\u2013bipyramidal geometries, respectively  angles collated in Table\u00a01The asymmetric unit of (I)As seen from the overlay diagram in Fig.\u00a02Database survey.A discussion of the uncoordinated benzyl\u00adamine mol\u00adecules is found below in the PLATON  inter\u00adaction. The second amine-H atom of the coordinating benzyl\u00adamine mol\u00adecule forms an N\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adaction with a non-coordinating N21-benzyl\u00adamine mol\u00adecule. For the Zn2-containing mol\u00adecule, the coordinating N18-benzyl\u00adamine forms a donor N\u2014H\u22efN hydrogen bond to a non-coordinating N20-benzyl\u00adamine mol\u00adecule which is folded to enable a donor N\u2014H\u22efN hydrogen bond to an exocyclic-N atom of the PC dianion. As seen from the lower view of Fig.\u00a03ab plane. These have a zigzag topology and present the flat PC residues to the outside with the benzyl\u00adamine mol\u00adecules, both coordinating and non-coordinating, in the inter-layer region. The layers stack along the c axis being connected by \u03c0\u2013\u03c0 inter\u00adactions between pyrrolyl and fused-phenyl rings [inter-centroid \u22ef(C57\u2013C62) distance = 3.593\u2005(2)\u2005\u00c5 with an angle of inclination = 6.1\u2005(2)\u00b0]. A view of the unit cell contents is shown in Fig.\u00a04Based on the standard criteria incorporated within i.e. with 4-methyl\u00adpridine 2L2 , syn and anti-C(phen\u00adyl)\u2014C(phen\u00adyl)\u2014C(benz\u00adyl)\u2014N(amine) torsion-angle data collated in Table\u00a04et al., 2010Finally, a few comments on the benzyl\u00adamine mol\u00adecule which has now been characterized in its uncoordinated form in five crystal structures. From the et al., 2007\u22121) \u03bd 1608 s (C=N), 1584 w (C=C), 1377 m, 1334 m, 1285 m, 1164 w, 1118 m, 1088 m, 1060 m, 888 w, 878 w, 752 m, 728 s. Crystals of (I)Zinc phthalocyanine was prepared by a modification of a literature procedure (Bayo Uiso(H) set to 1.2Ueq(C). The N-bound H atoms were treated similarly with N\u2014H = 0.88\u2005\u00c5, and with Uiso(H) = 1.2Ueq(N). Each of three solvent benzyl\u00adamine mol\u00adecules suffered from high thermal motion. In the final refinement the benzene rings were constrained to be regular hexa\u00adgons (C\u2014C = 1.39\u2005\u00c5) and their ADP\u2019s restrained to be nearly isotropic using the ISOR command. Owing to poor agreement, two reflections, i.e. (0 3 2) and (4 0 14), were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989015014280/hb7468sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015014280/hb7468Isup2.hklStructure factors: contains datablock(s) I. DOI: 1415614CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Weak C\u2014H\u22efCl inter\u00admolecular inter\u00adactions result in a two-dimensional extended sheet structure normal to the b axis.The mol\u00adecular structure of [Fe 4(C5H7O2)4(CH3O)6Cl2] or [Fe4(acac)4(\u03bc2-OMe)4(\u03bc3-OMe)2Cl2] (acac = acetyl\u00adacetonate), crystallizes in the ortho\u00adrhom\u00adbic Pbca space group with one half of the mol\u00adecule per asymmetric unit, the other half being completed by inversion symmetry. The core structure consists of a face-sharing double pseudo-cubane entity with two opposite corners missing. Weak C\u2014H\u22efCl inter\u00admolecular inter\u00adactions result in a two-dimensional layered structure parallel to the ac plane.The title complex, [Fe In line with this observation, we now report that the addition of NaOSi(OMe)2Me to Fe(acac)2Cl results in the formation of a tetra\u00adnuclear iron(III) methano\u00adlate compound, Fe4(acac)4(\u03bc2-OMe)4(\u03bc3-OMe)2Cl2, (I)We have investigated the syntheses of metal meth\u00adoxy\u00adsilanolates III metal atoms. Both cations are in approximately octa\u00adhedral coordination environments. The coordination sphere of Fe1 is filled by the O atoms of one \u03ba2-acac ligand [Fe1\u2014O1 = 1.9971\u2005(13)\u2005\u00c5 and Fe1\u2014O2 = 1.9934\u2005(13)\u2005\u00c5], two \u03bc2-methano\u00adlate groups , one \u03bc3-methano\u00adlate group [Fe1\u2014O4 = 2.2135\u2005(12)\u2005\u00c5], and one terminal chloride ligand [Fe1\u2014Cl1 = 2.2776\u2005(5)\u2005\u00c5]. The coordination sphere of Fe2 is filled by the O atoms of one \u03ba2-acac ligand [Fe2\u2014O6 = 1.9717\u2005(13)\u2005\u00c5 and Fe2\u2014O7 = 1.9692\u2005(12)\u2005\u00c5], two \u03bc2-methano\u00adlate groups [Fe2\u2014O3 = 1.9755\u2005(12)\u2005\u00c5 and Fe2\u2014O5 = 1.9823\u2005(12)\u2005\u00c5], and two \u03bc3-methano\u00adlate groups [Fe2\u2014O4 = 2.0815\u2005(12)\u2005\u00c5 and Fe2\u2014O4i = 2.0809\u2005(12)\u2005\u00c5]. The angles around both Fe1 and Fe2 distort significantly from the ideal values of 90 and 180\u00b0 of a perfect octa\u00adhedron. For Fe1, the cis angles range from 75.69\u2005(5) to 98.40\u2005(4)\u00b0, while the trans angles range from 164.47\u2005(5) to 170.40\u2005(3)\u00b0. The angles around Fe2 have narrower ranges, with cis being 78.95\u2005(5)\u201396.48\u2005(5)\u00b0 and trans being 170.08\u2005(5)\u2013170.16\u2005(5)\u00b0.The structure of (I)4(OMe)6] face-sharing double pseudo-cubane entity with two opposite corners missing. The outside of the cluster is decorated by one acac ligand per metal and the Fe atoms at either end of the cluster are coordinated by one chloride ion. Neighboring Fe\u22efFe distances range from 3.1997\u2005(4) to 3.2175\u2005(6)\u2005\u00c5, while the Fe1\u22efFe1i distance is 5.5702\u2005(6)\u2005\u00c5.The mol\u00adecular structure of (I)\u2212 ion and an acac ligand on neighboring mol\u00adecules s Table\u00a01. Taking is Fig.\u00a02.4(acac)4(OMe)6(N3)2], has previously been reported 4(OMe)6] face-sharing double cubane cluster with two opposite corners missing. The average Fe\u2014Oacac distance of 1.978\u2005\u00c5 is quite close to the average Fe\u2014Oacac distance of 1.982\u2005\u00c5 in (I)2-OMe: 1.977\u2005\u00c5; \u03bc3-OMe: 2.124\u2005\u00c5) are also comparable to those in (I)2-OMe: 1.983\u2005\u00c5; \u03bc3-OMe: 2.125\u2005\u00c5).One closely related complex, [Fe4(OR)6] cluster core similar to (I)et al., 2009et al., 20094(OR)6] motif is present is 63 additional materials as part of a higher-order cluster complex  in THF (3\u2005ml) was added to a solution of Fe(acac)2Cl  in THF (see Scheme). The mixture was stirred rapidly at room temperature, and a slight color change from a dark-red to a lighter red was observed. Removal of the solvent under vacuum resulted in the precipitation of an orange solid, which upon washing with dry Et2O (2 \u00d7 10\u2005ml) left a yellow solid. The yellow solid was extracted into dry CH2Cl2 and filtered through Celite. The CH2Cl\u00ad2 was then removed under vacuum, leaving a yellow solid . Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a CH2Cl2 solution of the yellow solid.A solution of NaOSi(OMe)RCH3, were optimized by rotation about R\u2014C bonds, with idealized C\u2014H, R\u2014H and H\u22efH distances (C\u2014H = 0.98\u2005\u00c5). The remaining H atoms were included as riding idealized contributors (C\u2014H = 0.95\u2005\u00c5). H atoms were assigned Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) otherwise. The 102 reflection was omitted from the final refinement because it was partially obscured by the shadow of the beam stop.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015013535/cv5491sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015013535/cv5491Isup2.hklStructure factors: contains datablock(s) I. DOI: 1412851CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in the title compound shows a slightly distorted octa\u00adhedral coordination environment to four N atoms of the aza\u00admacrocylic ligand in the equatorial plane and two isonicotinate O atoms in axial positions. Inter\u00admolecular N\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions consolidate the crystal packing.The Ni 6H4NO2)2(C16H38N6)], was prepared through self-assembly of a nickel(II) aza\u00admacrocyclic complex with isonicotinic acid. The NiII atom is located on an inversion center and exhibits a distorted octa\u00adhedral N4O2 coordination environment, with the four secondary N atoms of the aza\u00admacrocyclic ligand in the equatorial plane [average Ni\u2014Neq = 2.064\u2005(11)\u2005\u00c5] and two O atoms of monodentate isonicotinate anions in axial positions [Ni\u2014Oax = 2.137\u2005(1)\u2005\u00c5]. Intra\u00admolecular N\u2014H\u22efO hydrogen bonds between one of the secondary amine N atoms of the aza\u00admacrocyclic ligand and the non-coordinating carboxyl\u00adate O atom of the anion stabilize the mol\u00adecular structure. Inter\u00admolecular N\u2014H\u22efN hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions between neighbouring pyridine rings, give rise to the formations of supra\u00admolecular ribbons extending parallel to [001].The title compound, [Ni(C The longer axial bonds can be attributed to a ring contraction of the aza\u00admacrocyclic ligand  adopts the expected chair conformation, whereas the five-membered NiC2N2 ring (Ni1\u2013N1\u2013C1\u2013C4\u2013N2) has a gauche conformation (ClO4)2], was prepared in a slightly modified procedure with respect to the reported method (ClO4)2]  was slowly added an aceto\u00adnitrile solution (8\u2005mL) containing isonicotinic acid  and excess tri\u00adethyl\u00adamine  at room temperature. The purple precipitate was filtered off, washed with aceto\u00adnitrile and diethyl ether, and dried in air. Single crystals of compound (l)16H38N6)(ClO4)2] for several days. Yield: 0.167\u2005g (52%). FT\u2013IR : 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.The starting complex, [Ni values of 1.2 or 1.5Ueq of the parent atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016001031/wm5263sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016001031/wm5263Isup2.hklStructure factors: contains datablock(s) I. DOI: 1447865CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the cations, anions, 4-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde and water mol\u00adecules of crystallization are linked by classical O\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds into a three-dimensional supra\u00admolecular architecture. The crystal packing is further stabilized by weak C\u2014H\u22ef\u03c0 inter\u00adactions involving pyrrole and benzene rings. \u03c0\u2013\u03c0 stacking between parallel benzene rings of adjacent 4-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde mol\u00adecules is also observed, the centroid\u2013centroid distance being 3.8003\u2005(13)\u2005\u00c5. The three F atoms of the anion are disordered over two sets of sites, with a refined occupancy ratio 0.527\u2005(12):0.473\u2005(12). The O atom of one water mol\u00adecule of crystallization is also disordered over two positions in an occupancy ratio of 0.68\u2005(5):0.32\u2005(5).In the title compound, [Fe(C DOI: 10.1107/S1600536814015335/xu5800Isup2.hklStructure factors: contains datablock(s) I. DOI: 975656CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, weak N\u2014H\u22efS hydrogen bonds between the amino groups and the thio\u00adcyanate anions form an R42(8) motif. The complex mol\u00adecules are linked by O\u2014H\u22efO, O\u2014H\u22efS, and N\u2014H\u22efS hydrogen bonds into a three-dimensional supra\u00admolecular structure. Weak \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings is also found [centroid\u2013centroid distance = 3.8578\u2005(14)\u2005\u00c5].In the title complex, [Ni(NCS) DOI: 10.1107/S1600536814006771/hy2643Isup2.hklStructure factors: contains datablock(s) I. DOI: 993930CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked via pairs of N\u2014H\u22efO hydrogen bonds, forming inversion dimers which are linked by O\u2014H\u22efO hydrogen bonds, involving the crystal water mol\u00adecule, forming chains propagating along the a-axis direction.The title compound is twisted in such a way that the almost planar  segments are inclined to on another by 77.36\u2005(8)\u00b0, while the benzene rings are normal to one another, making a dihedral angle of 89.69\u2005(9)\u00b0. In the crystal, the water mol\u00adecule links three mol\u00adecules through two O\u2014H\u22efO and one N\u2014H\u22efO hydrogen bonds. The mol\u00adecules are linked via pairs of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(14) ring motif. The dimers are linked by O\u2014H\u22efO hydrogen bonds, involving two mol\u00adecules of water, forming chains along [100], enclosing R22(14) and R22(18) ring motifs. The chains are linked through C\u2014H\u22efO inter\u00adactions, forming sheets parallel to (010). Within the sheets, there are C\u2014H\u22ef\u03c0 and parallel slipped \u03c0\u2013\u03c0 stacking inter\u00adactions present [inter-centroid distance = 3.6458\u2005(12)\u2005\u00c5].The title compound, C N-Acyl\u00adhydrazones have been reported to be promising in terms of their future potential as anti\u00adbacterial drugs  and the C\u2014H(imine) bonds. The C9\u2014O2 bond length of 1.2251\u2005(19)\u2005\u00c5 indicates that the mol\u00adecule exists in the keto form in the solid state, and the C10\u2014N3 bond length of 1.271\u2005(2)\u2005\u00c5 confirms its significant double-bond character. The C9\u2014N2 and N2\u2014N3 bond distances of 1.351\u2005(2) and 1.3771\u2005(18)\u2005\u00c5, respectively, indicate a significant delocalization of the \u03c0-electron density over the hydrazone portion of the mol\u00adecule. Variations in the C\u2014N bond lengths of 1.330\u2005(2), 1.442\u2005(2) and 1.351\u2005(2)\u2005\u00c5 for C7\u2014N1, C8\u2014N1 and C9\u2014N2, respectively, characterize mobility of the bridge and the integral flexibility of the \u2013C(=O)\u2013NH\u2013CH2C(=O)\u2013NH\u2013N=CH\u2013 group connecting the two benzene rings. The mol\u00adecule is twisted at atom C8, the C7\u2014N1\u2014C8\u2014C9 torsion angle being 79.8\u2005(2)\u00b0. The hydrazone part of the mol\u00adecule is almost planar, with C9\u2014N2\u2014N3\u2014C10 and N2\u2014N3\u2014C10\u2014C11 torsion angles of \u2212177.07\u2005(15) and 179.38\u2005(14)\u00b0, respectively. Further, the dihedral angle between the almost planar hydrazone segment \u2005\u00c5 for atom N2) and the attached benzene ring (C11\u2013C16) is 8.17\u2005(6)\u00b0. The two benzene rings (C1\u2013C6 and C11\u2013C16) are orthogonal to each other, making a dihedral angle of 89.69\u2005(9)\u00b0. The planar amide segment  is inclined to the attached toluene ring (C1\u2013C6) by 8.06\u2005(9)\u2005\u00c5.The title compound crystallizes as a monohydrate Fig.\u00a01. The conN\u22efO3). A pair of N2\u2014H2N\u22efO1 inter\u00admolecular hydrogen bonds link the mol\u00adecules, forming inversion dimers, with an via hydrogen bonds involving the water mol\u00adecule generating N\u22efO1 and N1\u2014H1N\u22efO3 hydrogen bonds between the mol\u00adecules of the main compound and water mol\u00adecules translate into a-axis direction (Table\u00a01Cg2\u22efCg2i = 3.6458\u2005(12)\u2005\u00c5; inter-planar distance = 3.4135\u2005(8)\u2005\u00c5, slippage = 1.281\u2005\u00c5; Cg2 is the centroid of ring C11\u2013C16; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01] involving inversion-related chloro\u00adbenzene rings; see Fig.\u00a03In the crystal of (I)n Table\u00a01 The chai2\u2013C(=O)\u2013NH\u2013N=CH\u2013, yielded only one hit, namely N-(2-hy\u00addroxy-1-naphthyl\u00admethyl\u00adene)-N\u2032-(N-phenyl\u00adglyc\u00adyl)hydrazine -N-{2-[2-(3-chlorobenzyl\u00adidene)hydrazin\u00adyl]-2-oxoeth\u00adyl}-4-methyl\u00adbenzene\u00adsulf\u00adonamide monohydrate (II) N1) and hydrazone segment (N2\u2013N3=C10\u2013C11) with respect to the glycinyl C8\u2014C9 bond in (I)cis orientation of the sulfonamide and hydrazone segments, with respect to the glycinyl C\u2014C bond, observed in compound (II). In the structure of (I)A search of the Cambridge Structural Database  was added slowly. The organic phase was separated and washed with water (30\u2005ml), dried with anhydrous Na2SO4 and evaporated to yield the corresponding ester, N-(4-methyl\u00adbenzo\u00adyl)glycine ethyl ester (L1). L1 (0.01\u2005mol) was added in small portions to a stirred solution of 99% hydrazine hydrate (10\u2005ml) in 30\u2005ml ethanol. The mixture was refluxed for 6\u2005h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(4-methyl\u00adbenzo\u00adyl)-glycinyl hydrazide (L2). 2-Chloro\u00adbenzaldehyde (0.01\u2005mol) and two drops of glacial acetic acid were added to L2 (0.01\u2005mol) in anhydrous methanol (30\u2005ml). The reaction mixture was refluxed for 8\u2005h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (479\u2013480\u2005K). Prism-like colourless single crystals of the title compound were grown from a solution in DMF by slow evaporation of the solvent.Tri\u00adethyl\u00adamine (0.03\u2005mol) and 4-methyl\u00adbenzoyl chloride (0.01\u2005mol) were added to a stirred suspension of glycine ethyl\u00adester hydro\u00adchloride (0.01\u2005mol) in di\u00adchloro\u00admethane (50\u2005ml) in an ice bath. The reaction mixture was stirred at room temperature for 20\u2005h. After completion of the reaction, 2\u22121 for the stretching bands of N\u2014H (amide I), N\u2014H (amide II), C=O(hydrazone), C=O(amide) and C=N, respectively. The characteristic 1H and 13C NMR spectra of the title compound are as follows: 1H NMR : 2.36 , 4.01, 4.45 , 7.25 , 7.33\u20137.40 , 7.42\u20137.45 , 7.81 , 7.97\u20137.99 , 8.39, 8.63 , 8.54, 8.76 , 11.65, 11.73 . 13C NMR : 20.97, 40.74, 42.04, 126.60, 126.83, 127.28, 128.64, 129.66, 130.85, 131.35, 133.10, 139.45, 141.06, 142.70, 165.98, 166.54, 170.48.The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3323.3, 3203.8, 1685.8, 1620.2 and 1566.2\u2005cmUiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined as riding atoms: C\u2014H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015011147/su5148sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015011147/su5148Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011147/su5148Isup3.cmlSupporting information file. DOI: 1405614CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) graph-set motif. In the crystal, pairs of C\u2014H\u22efCl hydrogen bonds link mol\u00adecules into inversion dimers with an R22(26) motif. Weak C\u2014H\u22efO inter\u00adactions further link these dimers into ribbons propagating in [100].The hy\u00addroxy group in this carbazole derivative is involved in an intra\u00admolecular O\u2014H\u22efO hydrogen bond, which generates an  25H15Cl2NO4S, the di\u00adchloro\u00adphenyl ring is twisted by 68.69\u2005(11)\u00b0 from the mean plane of the carbazole ring system [r.m.s. deviation = 0.084\u2005(2)\u00b0]. The hy\u00addroxy group is involved in an intra\u00admolecular O\u2014H\u22efO hydrogen bond, which generates an S(6) graph-set motif. In the crystal, pairs of C\u2014H\u22efCl hydrogen bonds link mol\u00adecules into inversion dimers with an R22(26) motif. Weak C\u2014H\u22efO inter\u00adactions further link these dimers into ribbons propagating in [100].In the title compound, C The widening of angle O1\u2014S1\u2014O2 [120.49\u2005(11)\u00b0] and narrowing of angle N1\u2014S1\u2014C1 [105.36\u2005(10)\u00b0] from the ideal tetra\u00adhedral values are attributed to the Thorpe\u2013Ingold effect  graph-set motif. In the crystal, pairs of C\u2014H\u22efCl hydrogen bonds link mol\u00adecules into inversion dimers with an et al., 1995The hy\u00addroxy group is involved in an intra\u00admolecular O\u2014H\u22efO hydrogen bond Table\u00a01, which g2  in dry DMF (20\u2005ml) at reflux for 1\u2005h under N2. The reaction mass was poured over crushed ice (50\u2005ml) containing concentrated HCl (1\u2005ml). The precipitated solid was filtered, washed with water and air-dried to obtain the crude compound, which was purified by flash column chromatography on silica gel  to afford 17\u2005g as pale-yellow crystals suitable for X-ray analysis. Yield: 368\u2005mg (78%); m.p.: 461\u2013463\u2005K.Enamine 16\u2005g  was reacted with CuBrUiso(H) = 1.2Ueq(C). The components of the anisotropic displacement parameters in the direction of the bond between O4 and C19 were restrained to be equal within an effective standard deviation of 0.001 using the DELU command in SHELXL97  global, I. DOI: 10.1107/S1600536814024064/cv5474Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814024064/cv5474Isup3.cmlSupporting information file. DOI: 1032055CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex coordinated by hepta\u00adfluoro\u00adbutanoic acid, 1,10-phenanthroline and a water mol\u00adecule is described.The mol\u00adecular structure of a mononuclear Cu 4F7O2)2(C12H8N2)(H2O)], is mononuclear and contains a penta\u00adcoordinated CuII ion. The geometry of CuII ion can be described as distorted square-pyramidal with two O atoms of two butano\u00adate anions and two N atoms of the o-phenanthroline ligand occupying the basal plane, and a water O atom located at the axial position. In the crystal, C\u2014H\u22ef and O\u2014H\u22ef hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid-to-centroid distance 3.533\u2005(2)\u2005\u00c5] link the mol\u00adecules into a three-dimensional supra\u00admolecular structure.The title compound, [Cu(C For perfect tetra\u00adgonal symmetry, \u03c4 is zero, and for perfect trigonal\u2013bipyramidal geometry, \u03c4 becomes 1.0  and 1.980\u2005(3)\u2005\u00c5] in the quadrilateral plane are shorter than the apical position [2.173\u2005(3)\u2005\u00c5]. The mean Cu\u2014N(phen) distance of 2.043\u2005\u00c5 and the bite angle N1\u2014Cu1\u2014N2 of 81.75\u2005(12)\u00b0 are close to the corresponding values observed in related copper\u2013via atoms H5A and H5B, to oxygen atom O3 of one coordinating carboxyl\u00adate group (\u2212x\u00a0+\u00a0y\u00a0+\u00a0z) and to the dangling oxygen atom O2 of the other coordinating carboxyl\u00adate group (\u2212x\u00a0+\u00a0y\u00a0+\u00a0z), thus enclosing centrosymmetric et al., 1995b-axis direction \u2005\u00c5.  was added to a solution of o-phenanthroline  and hepta\u00adfluoro\u00adbutanoic acid  in methanol (7\u2005ml). Afterwards the obtained transparent blue solution was left to evaporate slowly in the air at ambient temperature and after two weeks, X-ray quality crystals appeared as blue plates. They were filtered off, washed with diethyl ether and dried in the air. Yield: 46\u2005mg, 86%.Cu(ClO4)\u00b76HUiso(H) = 1.2Ueq(C). The coordinates of the water H atoms were refined, and Uiso(H) was set to be 2Ueq(O). One of the hepta\u00adfluoro\u00adbutano\u00adate groups is disordered over two sets of sites in a 0.705\u2005(9):0.955\u2005(9) ratio. Atoms associated with the disorder were refined with isotropic displacement parameters.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015022720/pj2026sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015022720/pj2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 1434356CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The hydrogen-bonded structures of both a (1:1) mol\u00adecular adduct and a salt of 5-(4-bromo\u00adphen\u00adyl)-1,3,4-thia\u00addiazol-2-amine with 4-nitro\u00adbenzoic acid and 3,5-di\u00adnitro\u00adsalicylic acid, respectively, have been determined. 8H6BrN3S\u00b7C7H5NO4, (I), and the salt C8H7BrN3S+\u00b7C7H3N2O7\u2212, (II), obtained from the inter\u00adaction of 5-(4-bromo\u00adphen\u00adyl)-1,3,4-thia\u00addiazol-2-amine with 4-nitro\u00adbenzoic acid and 3,5-di\u00adnitro\u00adsalicylic acid, respectively, have been determined. The primary inter-species association in both (I) and (II) is through duplex R22(8) (N\u2014H\u22efO/O\u2014H\u22efO) or (N\u2014H\u22efO/N\u2014H\u22efO) hydrogen bonds, respectively, giving heterodimers. In (II), these are close to planar [the dihedral angles between the thia\u00addiazole ring and the two phenyl rings are 2.1\u2005(3) (intra) and 9.8\u2005(2)\u00b0 (inter)], while in (I) these angles are 22.11\u2005(15) and 26.08\u2005(18)\u00b0, respectively. In the crystal of (I), the heterodimers are extended into a chain along b through an amine N\u2014H\u22efNthia\u00addiazole hydrogen bond but in (II), a centrosymmetric cyclic hetero\u00adtetra\u00admer structure is generated through N\u2014H\u22efO hydrogen bonds to phenol and nitro O-atom acceptors and features, together with the primary R22(8) inter\u00adaction, conjoined R46(12), R21(6) and S(6) ring motifs. Also present in (I) are \u03c0\u2013\u03c0 inter\u00adactions between thia\u00addiazole rings [minimum ring-centroid separation = 3.4624\u2005(16)\u2005\u00c5], as well as short Br\u22efOnitro inter\u00adactions in both (I) and (II) .The structures of the 1:1 co-crystalline adduct C This \u2018planar\u2019 conformation is found in the parent acid \u00adbenzoic acid  PNBA adduct with BATZ, (I)ed Fig.\u00a01, in whicanti-related carb\u00adoxy\u00adlic acid H atom forming the common intra\u00admolecular S(6) hydrogen bond which is found in ca. 70% of DNSA salt structures \u00b0] whereas the second nitro group and the carboxyl\u00adate group lie essentially in the plane [torsion angles: C6A\u2014C5A\u2014 N5A\u2014O51A = 179.5\u2005(4) and C2A\u2014C1A\u2014 C11A\u2014O11A = \u2212178.0\u2005(4)\u00b0].In the DNSA salt (II)B\u2014H21B\u22efN4Bi hydrogen bonds s Table\u00a01 forming 1b Fig.\u00a03. This is1b Fig.\u00a03 and the  Fig.\u00a03b. A weak B) and the adjacent nitro-O atom (O31A) (Table\u00a02S(6) motifs \u2005\u00c5]. However, unlike in the structure of (I)With (II)) Table\u00a02 gives anfs Fig.\u00a04. The hetnitro contacts are found: for (I)B\u22efO42Aiii = 3.314\u2005(4)\u2005\u00c5, and for (II)B\u22ef O52Aiv = 3.104\u2005(3)\u2005\u00c5 .In both (I)The title compounds were prepared by the reaction of 1\u2005mmol (260\u2005mg) of 5-(4-bromo\u00adphen\u00adyl)-1,3,4-thia\u00addiazol-2-amine with 1\u2005mmol of either 4-nitro\u00adbenzoic acid (167\u2005mg) [for (I)] or 3,5-di\u00adnitro\u00adsalicylic acid (228\u2005mg) [for (II)] in 20\u2005mL of 50% ethanol\u2013water, with 10\u2005min refluxing. Partial evaporation of the solvent gave colourless needles of (I)Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included at calculated positions [C\u2014H = 0.95\u2005\u00c5] and also treated as riding, with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814021138/lh5731sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S1600536814021138/lh5731Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536814021138/lh5731IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S1600536814021138/lh5731Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814021138/lh5731IIsup5.cmlSupporting information file. DOI: 1025540, 1025541CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N6-benzoyl\u00adadenine-adipic acid (1/0.5) is reported. The typical C=O\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions are also present in this structure.The supra\u00admolecular architecture in a co-crystal of N(7)\u2014H tautomeric form of  12H9N5O\u00b70.5C6H10O4, consists of one mol\u00adecule of N6-benzoyl\u00adadenine (BA) and one half-mol\u00adecule of adipic acid (AA), the other half being generated by inversion symmetry. The dihedral angle between the adenine and phenyl ring planes is 26.71\u2005(7)\u00b0. The N6-benzoyl\u00adadenine mol\u00adecule crystallizes in the N(7)\u2014H tautomeric form with three non-protonated N atoms. This tautomeric form is stabilized by intra\u00admolecular N\u2014H\u22efO hydrogen bonding between the carbonyl (C=O) group and the N(7)\u2014H hydrogen atom on the Hoogsteen face of the purine ring, forming an S(7) ring motif. The two carboxyl groups of adipic acid inter\u00adact with the Watson\u2013Crick face of the BA mol\u00adecules through O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, generating an R22(8) ring motif. The latter units are linked by N\u2014H\u22efN hydrogen bonds, forming layers parallel to (10-5). A weak C\u2014H\u22efO hydrogen bond is also present, linking adipic acid mol\u00adecules in neighbouring layers, enclosing R22(10) ring motifs and forming a three-dimensional structure. C=O\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions are also present in the structure.The asymmetric unit of the title co-crystal, C As evident from the angles at N7 [C8\u2014N7\u2014C5 = 106.82\u2005(11)\u00b0] and N9 [C8\u2014N9\u2014C4 = 103.90\u2005(11)\u00b0], the N6-benzoyl\u00adadenine moiety exists in the N(7)\u2014H tautomeric form with non-protonated N1, N3 and N9 atoms. In addition, the C8\u2014N7 bond [1.3415\u2005(17)\u2005\u00c5)] is longer than C8\u2014N9 [1.3175\u2005(19)\u2005\u00c5]. These values are similar to those in neutral N6-benzoyl\u00adadenine  ring motif. The dihedral angle between the adenine and phenyl ring plane is 26.71\u2005(7)\u00b0 and the C6\u2014N6\u2014C10\u2014C11 torsion angle is 173.08\u2005(14)\u00b0. The bond lengths and bond angles of AA are in the range of values reported N6-benzyl\u00adadenine , N6-benz\u00adoyl\u00adadenine-dl-tartaric acid (1:1)  is also present (Table\u00a01A functions as a bifurcated hydrogen-bond acceptor whereas N7\u2014H is a bifurcated hydrogen-bond donor.Each of the two carboxyl groups of adipic acid inter\u00adacts with the Watson\u2013Crick face (atoms N1 and N6) of the corres\u00adponding BA through O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, generating an if Fig.\u00a01. Thus eas Table\u00a01 forming t Table\u00a01, linkinga) and C10=O1B\u22ef\u03c0 inter\u00adactions between the carbonyl oxygen O1B and the centroid of the (N1/C2/N3/C4/C5/C6) pyrimidine ring  , N6-benzoyl\u00adadenine-dl-tartaric acid (1:1)  and adipic acid (19\u2005mg) . The mixture was warmed in a water bath for 20 min. After cooling to room temperature, colourless plate-like crystals were collected from the mother liquor after a few days (m.p. 438\u2005K).The title co-crystal was synthesized by mixing a DMF solution of Uiso(H) = kUeq, where k = 1.5 for hy\u00addroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016007581/hg5474sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016007581/hg5474Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016007581/hg5474Isup3.cmlSupporting information file. DOI: 1478504CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Zn\u2014Cl bond lengths differ sligthly at 2.2310\u2005(10) and 2.2396\u2005(11)\u2005\u00c5 while the Zn\u2014S bond lengths are equal at 2.3663\u2005(9) and 2.3701\u2005(10)\u2005\u00c5. The Cl\u2014Zn\u2014Cl angle is 116.04\u2005(4) and S\u2014Zn\u2014S is 101.98\u2005(3)\u00b0. All other angles at the central Zn atom range from 108.108\u2005(3) to 110.21\u2005(4)\u00b0. The C\u2014S\u2014Zn angles are 100.75\u2005(10) and 103.68\u2005(11)\u00b0, the difference most probably resulting from packing effects, as both the C\u2014S and both the S\u2014Zn bonds are equal in each case. The two imidazole ring planes make a dihedral angle of 67.9\u2005(1)\u00b0. The CH3 groups of one isopropyl moiety are disordered over two sets of sites with occupation factors of 0.567\u2005(15) and 0.433\u2005(15). It may be noteworthy that the isomolecular Cu complex shows a different crystal packing (group\u2013subgroup relation) with the Cu atom lying on a twofold rotation axis. In the crystal, the shortest non-bonding contact is a C\u2014H\u22efCl inter\u00adaction. This leads to the formation of centrosymmetric dimers that are stacked along the c-axis.The mol\u00adecular structure of the title compound, [ZnCl DOI: 10.1107/S1600536814023642/hp2069Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814023642/hp2069fig1.tif. DOI: Mol\u00adecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level. Both orientations of disordered isopropyl group at C13 shown.1031227CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked through weak C\u2014H\u22efCl hydrogen bonds into a tape structure.In the title compound, [Pd(C 2(C11H9N)(C13H14N2)], represents a new class of palladium-based polymerizable monomer which could give a potentially catalytically active polymer. It was synthesized via transmetallation from the corresponding silver complex. The PdII ion coordinates two Cl anions, one C atom from the N-heterocyclic carbene (NHC) ligand and one N atom from the 4-phenyl\u00adpyridine ligand, displaying a slightly distorted square-planar geometry. The dihedral angle between the imidazole ring and the pyridine ring is 34.53\u2005(8)\u00b0. The Pd\u2014C bond length between the NHC ligand and the PdII ion is 1.9532\u2005(16)\u2005\u00c5. In the crystal, weak non-classical C\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into a tape structure along [101]. A weak \u03c0\u2013\u03c0 inter\u00adaction is also observed [centroid\u2013centroid distance = 3.9117\u2005(11)\u2005\u00c5]. The title compound, [PdCl The two mutually trans Cl ions fulfil the coordination sphere  and 65.78\u2005(7)\u00b0, respectively. The C12\u2014C13 bond length of the vinyl group is 1.299\u2005(3)\u2005\u00c5, corroborating the double-bond character. The same goes for the C2\u2014C3 distance which is 1.330\u2005(3)\u2005\u00c5. The N2\u2014C4\u2014Pd1\u2014N3, N1\u2014C4\u2014Pd1\u2014Cl2, C18\u2014N3\u2014Pd1\u2014Cl2 and C17\u2014C16\u2014C19\u2014C24 torsion angles are \u221230\u2005(7), 81.15\u2005(15), \u221249.40\u2005(15) and 32.42\u2005(3)\u00b0, respectively. A Cambridge Structural Database (CSD) search to validate the Pd\u2014Cl and Pd\u2014N bonding was performed over 47 entries. The Cl\u2014Pd\u2014Cl and N\u2014C\u2014N angles range from 170 to 180\u00b0 and from 104.8 to 106.2\u00b0, respectively; the Pd\u2014Cl bond lengths are in the range 2.286\u20132.318\u2005\u00c5. The bond lengths and angles of the title compound 4 shows a \u03c0\u2013\u03c0 inter\u00adaction between the C19\u2013C24 phenyl rings of neighbouring mol\u00adecules with a centroid\u2013centroid distance of 3.9117\u2005(11)\u2005\u00c5  route, as shown in Fig.\u00a042 gave the chlorido-bridged palladium dimer 3. Cleavage of the dimer with phenyl\u00adpyridine afforded complex 4 in excellent yield. With its vinyl groups it can serve as a precursor in co-polymerization reactions with e.g. styrene to form polymeric materials with catalytic properties.2(bmim)]2[PdCl (4). 4-Phenyl\u00adpyridine  was added to a 40\u2005ml solution of 3  in dry CH3CN and stirred at ambient temperature for 24\u2005h, during which time the solution changed colour to clear yellow. The mixture was filtered through Celite and all solvents were evaporated. The solids were dissolved in CH2Cl2 and, upon addition of n-hexane, a yellow solid was formed, which was collected on a frit and dried under vacuum to give 0.153\u2005g (93%) of 4.4 suitable for X-ray diffraction were obtained by slow diffusion of n-hexane into a saturated CH2Cl2 solution of the compound.Single crystals of Uiso(H) = 1.2Ueq(C).Crystal data and structure refinement details are summarized in Table\u00a0210.1107/S2056989016004394/is5447sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989016004394/is5447Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016004394/is5447sup3.tifNumbering for the assignment of NMR spectra. DOI: 1468135CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II, four aqua and two N-bound 2-chloro\u00adpyrazine ligands, weak O\u2014H\u22efO as well as \u03c0\u2013\u03c0 inter\u00adactions play important roles in the mol\u00adecular self-assembly, resulting in the formation of a three-dimensional structure.Between the tosyl\u00adate anions and the octa\u00adhedral complex cations consisting of Fe II(C4H3ClN2)2(H2O)4](C7H7O3S)2, contains a complex cation with point group symmetry 2/m. The high-spin FeII cation is hexa\u00adcoordinated by four symmetry-related water and two N-bound 2-chloro\u00adpyrazine mol\u00adecules in a trans arrangement, forming a distorted FeN2O4 octa\u00adhedron. The three-dimensional supra\u00admolecular structure is supported by inter\u00admolecular O\u2014H\u22efO hydrogen bonds between the complex cations and tosyl\u00adate anions, and additional \u03c0\u2013\u03c0 inter\u00adactions between benzene and pyrazine rings. The methyl H atoms of the tosyl\u00adate anion are equally disordered over two positions.The title salt, [Fe Series of thio\u00adcyanato coordination polymers [M(NCS)2L2]\u221e  in which the small-sized thiocyanate anions are terminally N-bound and therefore not involved in any magnetic exchange interactions are also known 2(H2O)4](C7H7O3S)2 containing a cationic iron(II) complex with 2-chloro\u00adpyrazine and aqua ligands, and tosyl\u00adate as an anion.In this paper, we report on the crystal structure of [Fe2(H2O)4]2+ and two tosyl\u00adate anions. The FeII atom, located on a special position with site symmetry 2/m, is sixfold coordinated by two N atoms of two symmetry-related 2-chloro\u00adpyrazine ligands occupying the axial positions and four O atoms of four H2O mol\u00adecules forming the equatorial plane \u2005\u00c5] of the H2O mol\u00adecules are significantly shorter than those between FeII and N [2.200\u2005(2)\u2005\u00c5] atoms of the two 2-chloro\u00adpyrazine ligands, hence the resulting FeO4N2 octa\u00adhedron is distorted. The metal-to-ligand distances clearly signalize the high-spin nature of the complex described in here \u00b0; for symmetry codes see caption to Fig.\u00a01ii\u2014Fe1\u2014N1 = 90.68\u2005(5)\u00b0] indicate only a small angular distortion.The structure of the title compound consists of a complex cation [Fe(2-chloro\u00adpyrazine)ne Fig.\u00a01. The disA\u22efO2 and O1\u2014H1B\u22efO3i hydrogen bonds  (OTs = p-toluene\u00adsulfonate) and ascorbic acid (0.001\u2005g) in water (5\u2005ml). After seven days this yielded colourless blocks of the title compound that were collected, washed with water and dried in air. Yield 0.090\u2005g (64%).Crystals of the title compound were obtained by adding 2-chloro\u00adpyrazine  to Fe(OTs)d(C\u2014H) = 0.95\u2005\u00c5 for aromatic and 0.98\u2005\u00c5 for CH3 hydrogen atoms. Because of the symmetry of the complete complex cation, methyl H atoms were modelled as equally disordered over two sets of sites. The H atoms of the water mol\u00adecule were located from a difference Fourier map and were modelled with a common isotropic displacement parameter fixed at 0.08\u2005\u00c52. The O\u2014H bonds lengths were constrained to 0.82\u2005\u00c5. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015010713/wm5168sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015010713/wm5168Isup2.hklStructure factors: contains datablock(s) I. DOI: 1404715CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure consists of discrete tetra\u00adhedral complexes, that are linked by inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding. 2(C6H6N2O)2], consists of one Zn2+ cation located on a twofold rotation axis, as well as of one thio\u00adcyanate anion and one neutral isonicotinamide ligand, both occupying general positions. The Zn2+ cation is tetra\u00adhedrally coordinated into a discrete complex by the N atoms of two symmetry-related thio\u00adcyanate anions and by the pyridine N atoms of two isonicotinamide ligands. The complexes are linked by inter\u00admolecular C\u2014H\u22efO and N\u2014H\u22efO, and weak inter\u00admolecular N\u2014H\u22efS hydrogen-bonding inter\u00adactions into a three-dimensional network.The asymmetric unit of the title complex, [Zn(SCN) The synthesis and crystal structure of the resulting compound, [Zn(NCS)2(C6H6N2O)2], are reported here.The synthesis of magnetic materials is still a major field in coordination chemistry  to 123.6\u2005(2)\u00b0.The asymmetric unit of the title compound consists of one Znex Fig.\u00a01. As expeex Fig.\u00a01. The angc axis and are linked by inter\u00admolecular N\u2014H\u22efO hydrogen bonding between one of the two amide H atoms and the amide O atom of a neighboring complex 2 was synthesized by stirring 3.076\u2005g Ba(NCS)2\u00b73H2O (10\u2005mmol) with 1.795\u2005g ZnSO4\u00b7H2O (10\u2005mmol) in 350\u2005ml water. The white residue was filtered off and the filtrate was dried using a rotary evaporator. The homogenity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-Ray diffraction were obtained by the reaction of 27.2\u2005mg Zn(NCS)2 (0.15\u2005mmol) with 36.64\u2005mg isonicotinamide (0.3\u2005mmol) in methyl\u00adcyanide (1.5\u2005ml) within a few days.Ba(NCS)Uiso(H) = 1.2Ueq using a riding model with C\u2014H = 0.95\u2005\u00c5 for aromatic and N\u2014H = 0.88\u2005\u00c5 for the amide H atoms. The absolute structure was determined and is in agreement with the selected setting [Flack x parameter: 0.005\u2005(19) by classical fit to all intensities  I. DOI: 10.1107/S2056989016008963/wm5297Isup2.hklStructure factors: contains datablock(s) I. DOI: 1483379CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III atoms, the title compound, [Re2Cl2{O2C(CH2)2CH3}4], exhibits a paddle-wheel or lantern-type structure with four n-butyrate groups bridging two ReIII atoms in a syn\u2013syn fashion. The axial chloride ligands together with the Re\u2014Re quadruple bond [2.2330\u2005(3)\u2005\u00c5] complete an essentially octa\u00adhedral geometry around each ReIII atom. There is little distortion, with an Re\u2014Re\u2014Cl bond angle of 176.18\u2005(3)\u00b0 and typical cis-O\u2014Re\u2014O bond angles ranging from 89.39\u2005(11) to 90.68\u2005(11)\u00b0. There are two mol\u00adecules in the unit cell, and no significant inter\u00admolecular inter\u00adactions were noticed between mol\u00adecules in the crystal.With an inversion center at the mid-point of the two Re DOI: 10.1107/S1600536814020273/wm5055Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814020273/wm5055fig1.tifx y z . DOI: x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a02.]The mol\u00adecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are drawn as small spheres of arbitrary radius. [Symmetry code i) \u2212Click here for additional data file.10.1107/S1600536814020273/wm5055fig2.tif. DOI: The packing diagram for the title compound viewed along [100].1023523CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both complexes, crystallized from aceto\u00adnitrile and diethyl ether, exhibit paddlewheel conformations with quadruple bonds between the Re atoms.The structures of [Re 2Br2(O2CC3H7)4], (1), and [Re2(O2CC3H7)4Cl2]\u00b72CH3CN, (2), both exhibit paddlewheel structures with four carboxyl\u00adate ligands bridging two ReIII atoms. The Re\u2014Re distances are 2.2325\u2005(2) and 2.2299\u2005(3)\u2005\u00c5, indicating quadruple bonds between the ReIII atoms in each complex. Both complexes contain an inversion center at the mid-point of the Re\u2014Re bond. The Re\u2014Br bond [2.6712\u2005(3)\u2005\u00c5] in (1) is 0.1656\u2005(6)\u2005\u00c5 longer than the Re\u2014Cl distance [2.5056\u2005(5)\u2005\u00c5] of (2). In (2), the N atom of each co-crystallized aceto\u00adnitrile solvent mol\u00adecule is nearly equidistant between and in close contact with two carboxyl\u00adate C atoms.The title complexes, [Re The first compound discovered to contain a metal\u2013metal quadruple bond was K al. 1966 and in s al. 2001, Cotton  al. 1997, and Veg al. 2002. This co1) and (2), respectively, are indicative of quadruple bonds  and 2.2299\u2005(3)\u2005\u00c5, in ( Tables 1 and 2 \u25b8.2) also contains one co-crystallized aceto\u00adnitrile solvent mol\u00adecule in a general position, thus giving rise to twice that in the formula unit. The asymmetric unit of (X\u2014Re\u2014Re\u2014X bonds in (1) and (2) are nearly linear, as can be seen in the Re\u2014Re\u2014Br [175.018\u2005(7)\u00b0] and Re\u2014Re\u2014Cl [178.254\u2005(11)\u00b0] bond angles, and are comparable to those observed in similar compounds  is similar to those of the previously published analog without co-crystallized aceto\u00adnitrile 3)4], and [Re2Cl2(O2CC6H5)4]\u00b72CHCl3  is slightly longer than the Re\u2014Br bond [2.603\u2005(1)\u2005\u00c5] found in [Re2Br2(O2CC(CH3)3)4]  and (2) differ by 0.1656\u2005(6)\u2005\u00c5 and those of Cotton and coworkers differ by 0.126\u2005(3), both of which are consistent with the difference in covalent radii of Cl and Br (0.15\u2005\u00c5).The 1) is isotypic with the chlorido analog published by Thomson et al. (20142Cl2(O2CC3H7)4]. In compound (2), the C1\u2014C2\u2014C3\u2014C4 torsion angle is \u221270.2\u2005(2)\u00b0, comparable to \u221267.9\u2005(2)\u00b0 for C5\u2014C6\u2014C7\u2014C8 4] without co-crystallizing solvent, the torsion angles vary more    Table\u00a01.2) nitro\u00adgen atom N1 of the co-crystallized aceto\u00adnitrile solvent mol\u00adecule is located at distances of 3.197\u2005(3) and 3.216\u2005(3)\u2005\u00c5 from the carboxyl\u00adate carbon atoms C1 and C5, respectively. This is just within the sum of the van der Waals radii of 3.25\u2005\u00c5  = 1.2Ueq(C) and methyl, C\u2014H = 0.98\u2005\u00c5, with Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015020563/pj2025sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989015020563/pj20251sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989015020563/pj20252sup3.hklStructure factors: contains datablock(s) 2. DOI: 1434257, 1434256CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the acetate anion is connected to the complex mol\u00adecule via a pair of N\u2014H\u22efO hydrogen bonds [graph-set motif R22(8)] and the solvent methanol mol\u00adecule is connected to the anion via an O\u2014H\u22efO hydrogen bond. This aggregate is further connected through a weak C\u2014H\u22efO hydrogen bond, forming a chain along [100]. In addition, sixfold phenyl embraces with inter\u00admolecular distances of 6.6463\u2005(13)\u20136.667\u2005(2)\u2005\u00c5 are arranged in a chain along [001]. The combination of hydrogen bonding and phen\u00adyl\u22efphenyl inter\u00adactions leads to the formation of a two-dimensional network parallel to (010).In the mononuclear title complex, [Ag(C For pot al. 2007; Isab et al. 2010. For det al. 2010; Scudder al. 2010. For hyd al. 1990. 5H12N2S)(C18H15P)3](C2H3O2)\u00b7CH4O = 0.053wR(F2) = 0.120S = 1.0016670 reflections653 parametersH-atom parameters constrainedmax = 1.23 e \u00c5\u22123\u0394\u03c1min = \u22121.13 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I. DOI: 10.1107/S1600536814010824/lh5701Isup2.hklStructure factors: contains datablock(s) I. DOI: 1002206CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecules associate through an inter\u00admolecular O\u2014H\u22efNnitrile hydrogen bond and are inter\u00adlinked through very weak C\u2014H\u22efN hydrogen bonds.In the crystal of the title substituted hemibi\u00adquinone derivative, the ring systems inter\u00adact through an intra\u00admolecular O\u2014H\u22efO 16H11BrN2O4 or [BrHBQH2(CN)2], the substituted benzene rings are rotated about the central C\u2014C bond, forming a dihedral angle of 53.59\u2005(7)\u00b0. The ring systems inter\u00adact through an intra\u00admolecular O\u2014H\u22efOmeth\u00adoxy hydrogen bond, which induces a geometry quite different from those in previously reported hemibi\u00adquinone structures. In the crystal, the mol\u00adecules associate through an inter\u00admolecular O\u2014H\u22efNnitrile hydrogen bond, forming chains which extend along [100] and are inter\u00adlinked through very weak C\u2014H\u22efN hydrogen bonds, giving a overall two-dimensional structure lying parallel to (010).In the crystal of the title substituted hemibi\u00adquinone derivative, C This bending of the mol\u00adecule about its long axis may also be due to hydrogen bonding as it causes the meth\u00adoxy group to approach the OH group more closely. The aromatic C\u2014C bonds of both rings have a narrow range of distances [from 1.387\u2005(2) to 1.412\u2005(2)\u2005\u00c5]. The C\u2014C, C\u2014O, C\u2014N, and C\u00a0N distances for the mol\u00adecule are similar to the corresponding distances in 2,3,5,6-tetra\u00adcyano\u00adhydro\u00adquinone \u00b0. As a result of the influence of other short contacts and supra\u00admolecular inter\u00adactions (see below), the phenolic C\u2014O\u2014H bond angles deviate when compared to the meth\u00adoxy C\u2014O\u2014C bond angles: C8\u2014O3\u2014H is 108\u2005(2)\u00b0, C11\u2014O4\u2014H is 112.3\u2005(2)\u00b0, C3\u2014O2\u2014C14 is 117.9\u2005(1)\u00b0, and C6\u2014O1\u2014C13 is 117.2\u2005(1)\u00b0. As in other structures, the meth\u00adoxy groups are aligned mostly in-plane with the benzene ring, C5\u2014 C6\u2014O1\u2014C13 being bent out of plane by \u22124.5\u2005(2)\u00b0 and C2\u2014C3\u2014O2\u2014C14 bent out of plane by \u22121.3\u2005(2)\u00b0. The C12\u2014C11\u2014O4\u2014H phenol group is also nearly planar, being bent out of plane by 1.3\u00b0. However, the hydrogen-bonded phenol is unsurprisingly bent out of plane, C7\u2014C8\u2014O3\u2014H = 38\u2005(2)\u00b0. The meth\u00adoxy methyl groups point away from the sterically restricting groups a-axis direction. Both nitrile groups are involved in inter\u00admolecular hydrogen-bonding inter\u00adactions, the first one (O4\u2014H\u22efN1) strong, the second one (C2\u2014H\u22efN2) weaker but still highly directional. For details, see Table\u00a01a- and b-axis directions, respectively, forming sheets parallel to (010)  contacts to six neighboring mol\u00adecules Fig.\u00a03. As in p0) Fig.\u00a04. The quib and stacking along c can be seen in Fig.\u00a05ac plane.The remaining two mol\u00adecules in the unit cell are oriented orthogonally to the central mol\u00adecules. These mol\u00adecules are anti\u00adparallel to each other, where the di\u00admeth\u00adoxy\u00adbenzene rings stack with those of the central pair. Slightly repulsive \u03c0-inter\u00adactions between mol\u00adecules along 2O. Upon pouring the aqueous solution into the organic solution, the mixture immediately changed from a vibrant red to a deep purple. After stirring for 1\u2005h, 50\u2005\u00b5L of concentrated HCl solution was added, changing the color of the mixture from purple to bright orange. The mixture was diluted with 50\u2005mL of water and the aceto\u00adnitrile was removed by rotary evaporation. A tan\u2005powder precipitated, which was recovered by filtration and washed with water to yield the crude product. This material was recrystallized from acetone giving 0.196\u2005g (70.4%) of pure material as yellow\u2013orange prisms. 1H NMR  \u03b4 = 10.02 , 8.75 , 7.34 , 7.24 , 7.05 , 3.88 , 3.82 .2-Bromo-5-cyclo\u00adhexa-2,5-diene-1,4-dione, BrHBQBr,  was dissolved in 350\u2005mL of aceto\u00adnitrile. In a separate beaker, potassium cyanide  was dissolved in 50\u2005mL of HUiso = 1.5Ueq(O). Hydrogen atoms bonded to carbon were placed in calculated positions with C\u2014H = 0.93\u2005\u00c5 (aromatic) or 0.96\u2005\u00c5 (meth\u00adyl) and their coordin\u00adates and thermal parameters were constrained to ride on the carrier atom, with Uiso = 1.5Ueq(aromatic C) or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016005715/zs2361sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005715/zs2361Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016005715/zs2361Isup3.cmlSupporting information file. DOI: 1472611CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(4-methyl\u00adphen\u00adyl)benzene\u00adsulfonamide and N-(4-fluoro\u00adphen\u00adyl)-4-meth\u00adoxy\u00adbenzene\u00adsulfonamide, the supra\u00admolecular architecture of the former is controlled by C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions, forming a two-dimensional architecture, while in the latter, a pair of C\u2014H\u22efO inter\u00admolecular inter\u00adactions lead to the formation of a three-dimensional architecture.In the crystal structures of 4-meth\u00adoxy- N-(ar\u00adyl)aryl\u00adsulfonamides, namely, 4-meth\u00adoxy-N-(4-methyl\u00adphen\u00adyl)benzene\u00adsulfonamide, C14H15NO3S, (I), and N-(4-fluoro\u00adphen\u00adyl)-4-meth\u00adoxy\u00adbenzene\u00adsulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzene\u00adsulfonamide ring is disordered over two orientations, in a 0.516\u2005(7):0.484\u2005(7) ratio, which are inclined to each other at 28.0\u2005(1)\u00b0. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36\u2005(19)\u00b0, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26\u2005(13)\u00b0. In the crystal structure of (I), N\u2014H\u22efO hydrogen bonds form infinite C(4) chains extended in [010], and inter\u00admolecular C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N\u2014H\u22efO hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C\u2014H\u22efO inter\u00admolecular inter\u00adactions consolidate the crystal packing of (II) into a three-dimensional supra\u00admolecular architecture.Crystal structures of two  The dihedral angle between the two parts of disordered benzene ring, i.e. C1/C2A/C3A/C4/C5A/C6A and C1/C2B/C3B/C4/C5B/C6B, is 28.0\u2005(1)\u00b0. The dihedral angle between the sulfonyl benzene ring (considering the major component) and the aniline ring is 63.36\u2005(19)\u00b0, and the N\u2014C bond in the C\u2014SO2\u2014NH\u2014C segment has a gauche torsion with respect to the S=O bonds. Further, the mol\u00adecule is twisted at the S\u2014N bond, with a C1\u2014S1\u2014N1\u2014C7 torsion angle of 66.33\u2005(19)\u00b0. The meth\u00adoxy group in the sulfonyl\u00adbenzene ring is in the same plane as that of the major component of the disordered sulfonyl\u00adbenzene ring, the torsion angle C5A\u2014C4\u2014O3\u2014C14 being \u2212176.2\u2005(4)\u00b0, while it deviates slightly from planarity with respect to the minor component, the C5B\u2014C4\u2014O3\u2014C14 torsion angle being 165.9\u2005(4)\u00b0.In (I)2\u2014NH\u2014C segment has a gauche torsion with respect to the S=O bonds. Further, the mol\u00adecule is twisted at the S\u2014N bond, with a C1\u2014S1\u2014N1\u2014C7 torsion angle of 68.4\u2005(2)\u00b0. Similar to (I)In (II)C(4) chains along [010]. Neighbouring C(4) chains are inter\u00adconnected via C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions s Table\u00a01 into lays Table\u00a01 parallelC(4) chains along [001]. Further, weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions s Table\u00a02 consolids Table\u00a02.N-(4-substituted-phen\u00adyl)-4-meth\u00adoxy\u00adbenzene\u00adsul\u00adfon\u00adam\u00adides benzene\u00adsulfonamide, (III), 4-meth\u00adoxy-N-(4-meth\u00adoxy\u00adphen\u00adyl)benzene\u00adsulfonamide, (IV), and N-(4-chloro\u00adphen\u00adyl)-4-meth\u00adoxy\u00adbenzene\u00adsulfonamide, (V), have been reported previously. Compounds (IV) and (V) crystallize in monoclinic syngony, while compound (III) crystallizes in ortho\u00adrhom\u00adbic syngony. The dihedral angles between the two benzene rings in (III), (IV) and (V) are 55.1\u2005(1), 56.3\u2005(1) and 42.6\u2005(1)\u00b0, respectively. Comparison of the dihedral angles between the two benzene rings in (I)\u2013(V) shows that, when an electron-donating substituent is introduced into the para position of the aniline ring of (I)Three para position of the aniline ring of (I)C(4) chains, and thus, the supra\u00admolecular architecture is one-dimensional. In (IV), one N\u2014H\u22efO hydrogen bond and two alternating C\u2014H\u22ef\u03c0ar\u00adyl (centroid of aniline ring) inter\u00adactions direct a two-dimensional architecture. This is quite similar to the crystal structure of (I)C(4) chains. Further, (V) does not feature any structuredirecting inter\u00admolecular inter\u00adactions, and thus, the structure is one-dimensional. In contrast to this, the crystal structure of (II)Comparison of the crystal structures (I)et al. (2015Compounds (I) al. 2015. The purR1, wR2, and S (goodness-of-fit), a partially obscured reflection (i.e. 100) was omitted from the final refinement of (I)A and B) of the disordered benzene\u00adsulfonyl ring in (I)A) and 0.054\u2005(1)\u2005\u00c5 (minor-component ring B). The disordered atoms  in both components were isotropically refined, and the C\u2014C bond lengths were restrained to 1.391\u2005(1)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015019787/cv5497sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989015019787/cv5497Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015019787/cv5497Isup4.cmlSupporting information file. DOI: 10.1107/S2056989015019787/cv5497IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989015019787/cv5497IIsup5.cmlSupporting information file. DOI: 1432501CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The SrII ion, situated on a C2 axis, is coordinated by four O atoms from four pydc2\u2212 ligands and four water mol\u00adecules. The coordination geometry of the SrII atom can be best described as a distorted dodeca\u00adhedron. Each SrII ion bridges four [Co(pydc)2(H2O)2]2\u2212 units by four COO\u2212 groups of four pydc2\u2212 ligands to form a three-dimensional network structure. Two additional solvent water mol\u00adecules are observed in the crystal structure and are connected to the three-dimensional coordination polymer by O\u2014H\u22efO hydrogen bonds. Further intra- and intermolecular O\u2014H\u22efO hydrogen bonds consolidate the overall structure.In the title polymeric complex, {[CoSr(C DOI: 10.1107/S2056989015014942/im2469Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015014942/im2469fig1.tifx y z x y z x y z x y z x y z . DOI: x,-y\u00a0+\u00a01,-z\u00a0+\u00a01; B: \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01; C: x\u00a0\u2212\u00a0y\u00a0+\u00a01/2,z; G: \u2212x,y,-z\u00a0+\u00a0x\u00a0\u2212\u00a0y,z\u00a0\u2212\u00a01/2.The mol\u00adecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: A: \u2212Click here for additional data file.10.1107/S2056989015014942/im2469fig2.tifb . DOI: b-axis, with hydrogen bonds drawn as dashed lines.The packing diagram for the title compound, viewed down the 761895CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali\u2013H groups. An X-ray structure of imidazolium-based scaffolds using Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions (A\u2212\u2009=\u2009anion) shows that a halide anion is directly interacting with fifteen Cali\u2013H groups . Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.Since the aliphatic C\u2013H\u00b7\u00b7\u00b7anion interaction is relatively weak, anion binding using hydrophobic aliphatic C\u2013H (C Because the Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interaction is weak, anion binding by the Cali\u2013H groups is generally enhanced through the incorporation of additional binding sites to the anion. Indeed, though C\u2013H\u00b7\u00b7\u00b7A\u2212 type interactionsali\u2013H groups are rarely used as H-bond donors in synthetic receptors. Nevertheless, such interactions are essential to the overall stability of complexes of proteins and DNA as well as various organic transformations and the transition states of diverse catalytic cycles2ali\u2013H donors constitutes a useful opportunity to tailor molecular recognition phenomena4ali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions due to relatively low binding strengths, although there are some reports about interactions between anions and multi Cali\u2013H donors67910\u2212 interactions. In comparison, the C\u2013H bonds found in nonpolar alkanes are relatively less acidic, though the corresponding interactions with anions may be increased through the incorporation of electron-withdrawing groups.The structure of an anion that is surrounded exclusively by multiple Cali\u2013H\u00b7\u00b7\u00b7A\u2212 H-bondsali\u2013H\u00b7\u00b7\u00b7A\u2212 hydrogen bonding was reported for adducts of anions and a resorcinarene cavitand, which was shown to adopt a bowl-shaped cavity that provided up to four convergent C\u2013H groups activated by adjacent oxygen atomsali\u2013H hydrogen bonding appear to be limited to a palladium complexali\u2013H groups1516\u2212 interaction sites towards an anion.The first charge-neutral systems of highly fluorinated receptors with aliphatic methylene groups were polarized by neighboring electronegative O and F atomsali\u2013H groups. The methyl and methylene moieties in this host form Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions with various anions. In particular, we report that bisimidazolium and tetraalkylammonium based hosts drive the formation of multideca to pentadeca binding sites with halide anions exclusively through Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions.Herein, we disclose the synthesis and study of a bis-imidazolium host bearing acidic C1](PF6)2 was synthesized and characterized using NMR spectroscopy  were grown under anhydrous conditions. Single crystal X-ray diffraction analysis \u2009=\u20091.2U. The Cl\u2212 anion appeared to be surrounded by multiple Cali\u2013H groups  di-hexafluorophosphate (Cl)2 are not small .Then, in our crystal structures, we find that these H\u2009\u2265\u2009100\u00b0) . It shou\u2212 in bis-tetramethylimidazolium complexes, we were pleasantly surprised to find that one of two kinds of Cl\u2212 has 15 binding sites via H-bonds and H-bonding-like interactions, ten strong H-donors ), 1 moderate H-donor (#13), and four weak H-donors  (\u2212\u00b7\u00b7\u00b7C distances (dCl\u00b7\u00b7\u00b7C), twelve C atoms were within H-bond distance from Cl\u2212 (4.01\u20134.08\u2009\u00c5), in consideration that rvdWCl\u00b7\u00b7\u00b7(H)C: 4.01\u20134.08\u2009\u00c5 , while additional two C atoms  were positioned at relatively long distances . The Cali\u2013H\u00b7\u00b7\u00b7Cl\u2212 angles (\u03b8) were measured to be in all circumstances greater than 148\u00b0 except for the bidentate case (129/124\u00b0 and 100/100\u00b0 in X-ray/DFT) by the two H atoms  attached on the same C atom at dCl\u00b7\u00b7\u00b7C\u2009=\u20094.05\u2009\u00c5. Namely, eleven C atoms involved in strong bidentate H-bonds were in agreement with the formation of bona fide H-bonds. In addition, one C atom involved in bidentate Cali\u2013H\u00b7\u00b7\u00b7Cl\u2212 interactions with its two H atoms was considered to have weak H-bonding-like interactions (\u03b8: 129\u00b0 and 100\u00b0) because the dCl\u00b7\u00b7\u00b7H  distances are somewhat long even though dCl\u00b7\u00b7\u00b7C (=\u20094.05\u2009\u00c5) \u2248 rvdWCl\u00b7\u00b7\u00b7(H) (=\u20094.01\u20134.08\u2009\u00c5). Nevertheless, these bidentate H-bonding-like interactions could be considered as bidentate H-bonds or at least bidentate H-bonding-like bindings. Further, two weak uni-dentate H bonding-like interactions at relatively long distances (dCl\u00b7\u00b7\u00b7C\u2009=\u20094.71/4.83\u2009\u00c5) but with favorable angles (\u03b8: 153\u00b0/177\u00b0) can also be taken into account as direct binding sites. Then, Cl shows fifteen binding sites (thirteen uni-dentate and one bidentate H-bonding or H-bonding-like interaction sites) by the Cali\u2013H groups in seven molecules of [1] surrounding the Cl\u2212 anion. Furthermore, each Cali\u2013H\u00b7\u00b7\u00b7Cl\u2212 binding for the given dCl\u00b7\u00b7\u00b7H and \u03b8 shows adequate BEs  for all the fifteen cases due to the strong electrostatic interactions between negatively charged Cl\u2212 and positively charged H3C-NH3+. In all the above cases of fifteen H atoms, no other atom exists within the sphere having the diameter from each H atom to Cl\u2212, and thus, the fifteen H atoms directly bind Cl\u2212 as Voronoi nearest neighbors.From the analysis of binding sites for Cl 14, 15) . In term\u2212\u00b7\u00b7\u00b7H-Cali is mainly an electrostatic interaction between positive and negative charges where the positive charge of H is enhanced due to the polarization through the H-Cali bond. In the model system of Cl\u2212\u00b7\u00b7\u00b7H-CH3, the induction and electrostatic energies based on DFT  are dominant for the binding in the fully optimized structure . Even with a highly increased distance between H and Cl, the induction energy gives significant contribution for binding: \u2206Etotal\u2009=\u2009\u22122.33; \u2206Eelst\u2009=\u2009\u22120.36; \u2206Eind\u2009=\u2009\u22120.95; \u2206Eexch\u2009=\u2009\u22120.36\u2009kcal/mol for dCl\u00b7\u00b7\u00b7H\u2009=\u20093.871\u2009\u00c5  than in the methane model (+0.218). All of the Cl\u2212\u00b7\u00b7\u00b7H-Cali angles deviate slightly from 180\u00b0 but, by considering flexibility of the range of H-bond angles, the angles in the 15 H atoms cases are in favor of significant interaction energies. In addition, if the angle reduces from 180\u00b0 to 100\u00b0, the Hx-C (Hx: hydrogen interacting with Cl\u2212) bond distance decreases from 1.108 to 1.102\u2009\u00c5, while Cl\u2212\u00b7\u00b7\u00b7Hx distance increases from 2.705 to 3.5\u2009\u00c5. Namely, as the angle is close to 180\u00b0, the Cl\u2212\u00b7\u00b7\u00b7Hx interaction energy becomes stronger, showing the significant angle-dependence of the H-bonding characteristics.Although we classified the above binding interaction as the H-bonding and H-bonding-like interactions, even the latter show most features of H-bond addressed in the IUPAC provisional recommendation (criteria and characteristics)20\u2212\u00b7\u00b7\u00b7H\u2013Cali interactions in the CH4\u2013Cl\u2212 and NH3CH3+\u00b7\u00b7\u00b7Cl\u2212 models as well as the crystal structure of [1](Cl)2 have H-bond-like characteristics based on both the IUPAC recommendation and the Koch-Popelier definition (\u03c1(r)\u2009=\u20090.002\u20130.040 au and 1](Cl)2 crystal structure highlights that Cl\u2212 is stabilized by strong H-bonds as well as strong ionic electrostatic interactions (dCl\u00b7\u00b7\u00b7Hx\u2009\u2264\u20093.15\u2009\u00c5 in X-ray structure) and weak H-bonding-like interactions  critical pointractions . Overallali-H groups is conceptually similar to the cation recognition of hydrophobic aromatic rings, but the origin of noncovalent interactions are quite different   for such high number of binding sites similar to those described herein. Therein, we indeed found 14 binding sites for anions in the tetraalkylammouniun complexes (BUXTOD)actions) , and SI,3 groups that were bonded to the N atoms, where the C atom was slightly positively charged due to the ammonium group. Thus, weakly positively charged H atoms surround the anion nearly spherically, and then the weakly negatively charged C atoms surround the region of positively charged H atoms. The nearly concentric structures showing alternating +/\u2212 electrostatic potential shells are formed 13dCl\u00b7\u00b7\u00b7H\u2009=\u20092.88\u20133.13\u2009\u00c5, dCl\u00b7\u00b7\u00b7C\u2009=\u20093.65\u20133.75\u2009\u00c5, \u03b8Cl\u00b7\u00b7\u00b7H\u2013C\u2009=\u2009121\u2013132\u00b0; dI\u00b7\u00b7\u00b7H\u2009=\u20093.35\u20133.30\u2009\u00c5, dI\u00b7\u00b7\u00b7C\u2009=\u20093.88\u2009\u00c5, \u03b8I\u00b7\u00b7\u00b7H\u2013C\u2009=\u2009117\u2013120\u00b0]. In consideration of small angles, this dodeca coordination somewhat reflects a caged structure, i.e., strained coordination, instead of H-bonding. However, it may still be labeled as a dodeca-coordination complex, with centrospherical shells that feature Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions and contain alternating regions of +/\u2212 electrostatic potential.Such nearly centrospherical shell structures containing multiple C\u2013H\u00b7\u00b7\u00b7A\u2212 anions in the bisimidazolium complex have pentadeca binding sites exclusively by Cali\u2013H groups. The electrostatic potential maps feature nearly concentro-spherical shells with alternating +/\u2212 electrostatic interactions, quite different in structure from many well-known H-bond complexes for anions. These intriguing Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions have not been properly recognized previously. The positively charged hosts render the aliphatic C\u2013H moieties relatively acidic and thus increase their binding affinities for anions. Collectively, the results described herein may give rise to new classes of aliphatic hosts that display selectivity toward anions via tight control of cavity geometry and acidity of their respective H-bond donors. We also note that complexes of tetradeca binding sites and other multiple binding sites show nearly concentro-spherical shells depicting alternating +/\u2212 electrostatic potential for the Cali\u2013H\u00b7\u00b7\u00b7A\u2212 interactions.Our study finds that the ClHere, we discuss the number of binding sites as compared with the coordination number (CN) which are well defined in inorganic chemistry. In solid and liquid states materials, the CN is also often used, differently from the terminology used in inorganic chemistry. Indeed, the CN has been a widely used terminology in various branches of science. The definition of CN originates from mathematics, where it means the number of equivalent hyperspheres in n dimensions that can touch an equivalent hypersphere without any intersections45Though the definition might not be clear in certain cases, it is assumed that each binding event needs to show significant positive  BE associated with noncovalent interaction, noncovalent bonding, or electrostatic interaction. The van der Waals (vdW) interactions are generally not considered in counting CNs. Coordination phenomena often include cation-anion interactions, hydrogen bonding, and \u03c0 interactions4748\u03b8 between two vectors constructed from any other atom to the coordinating site and the coordinated site. If any other atom has the angle \u03b8\u2009>\u200990\u00b0, the assumed coordinating atom/site should be removed from the direct coordination. If all angles \u03b8 obtained for all other atoms are less than 90\u00b0, it means that all of them are out of the sphere, and so this case is considered to be directly coordinated. In this way, the obtained CN is equivalent to the Voronoi-based CN nearest neighborsWhen the local coordination does not have high symmetry, the direct coordination can be considered as a case where a given coordinating atom (or site) does not have any other atoms in the sphere centered on the midpoint between the given site and the coordinated atom. This can be analyzed by measuring the angle 4)4]152+, which has a large metal cation and many small ligands3BNMe2BH3)4]4)4, its derivatives 52544 groups.Although examples of complexes that feature multiple coordination numbers have been widely observed, cases of very high coordination are rare. Structures with very high coordination numbers have been found with actinide-based cations, such as + 905.500, found 905.070; m/z calcd. for [M \u2013 I]+ 389.298, found 388.914.1,2,4,5-Tetramethylimidazole  and diiodomethane  were heated at 110\u2009\u00b0C in a sealed tube overnight. The resulting mixture was filtered and washed with dichloromethane several times to afford [1](I)2  was added a saturated aqueous solution of NH4PF6  at room temperature. A precipitate formed which was subsequently collected by filtration and washed with water to afford [1](PF6)2 as a light brown solid. Yield: 2.16\u2009g, 83%. 1H NMR , \u03b4 6.15 , 3.61 , 2.53 , 2.20 , 2.04 . 13CNMR , \u03b4 145.83 (N\u2009=\u2009CCH3N), 129.44 (H3CN-CCH3\u2009=\u2009C), 126.87 (-CH2N-CCH3\u2009=\u2009C), 56.41 (CH2), 33.77 (NCH3), 11.88 (N\u2009=\u2009CCH3N), 9.50 (-CH2N-CCH3\u2009=\u2009C), 9.12 (H3CN-CCH3\u2009=\u2009C). HRMS , m/z calcd. for [2M \u2013 PF6]+ 959.3240, found 959.3247; m/z calcd. for [M \u2013 PF6]+ 407.1799, found 407.1828; m/z calcd. for [M \u2013 2PF6]2+ 131.1078, found 131.1071.To an aqueous solution of [How to cite this article: Shi, G. et al. Halides with Fifteen Aliphatic C-H\u00b7\u00b7\u00b7Anion Interaction Sites. Sci. Rep.6, 30123; doi: 10.1038/srep30123 (2016)."}
{"text": "III(N**)3] . Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three-coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N\u201c)3] (N\u201d=N(SiMe3)2\u2212), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N\u201c)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single-molecule magnets.We report the synthesis and characterization of the uranium(III) triamide complex [U Both covalent[19] and electrostaticIII(N\u201c)3],III(N**)3] 2\u2212), which adopts an unprecedented trigonal planar geometry for an actinide triamide complex. Complex 1 is closely related to [UIII(N\u201d)3], allowing the contributions to pyramidalization to be assessed, together with the impact of geometry on magnetic (including dynamic) and electronic properties of UIII complexes, for the future rational design of useful An materials.f-Block metal centers favor high CNs, because Ln and An cations have relatively large ionic radii and bonding regimes that are dominated by electrostatic contributions.1 was prepared by a modification of the revised synthesis of [UIII(N\u201c)3].III(I)3(THF)4]2tBu)2}]2 in THF, followed by work-up and recrystallization from hexane to give 1 as dark purple needles in 62\u2009% yield (1 at \u22121 are attributed to the UNSi2 stretching modes of the silylamide ligand. The asymmetric stretch (950\u2005cm\u22121) is 40\u2005cm\u22121 lower than that observed for [UIII(N\u201d)3] (990\u2005cm\u22121),3] MNSi2 asymmetric stretches (ca. 50\u2005cm\u22121).6aComplex \u2009% yield .21 Absor1H\u2005NMR spectrum of 1 exhibits two resonances at \u03b4=3.8 (\u03bd\u00bd=206\u2005Hz) and \u221247.0\u2005ppm (\u03bd\u00bd=4597\u2005Hz) in a 54:36 ratio that are assigned to the tBuSi and Me2Si protons, respectively. The Me2Si resonance of 1 is much broader than the analogous resonance for [UIII(N\u201c)3] ,\u03b4=\u221232.9\u2005ppm, \u03bd\u00bd=266\u2005Hz).13C\u2005NMR spectrum of 1 exhibited two resonances for the Me2Si (\u03b4=\u22122.1 and 1.5\u2005ppm) and tBuSi quaternary carbons (\u03b4=18.2 and 32.0\u2005ppm), but only one for the tBuSi primary carbons (\u03b4=26.4\u2005ppm). In contrast, in the 13C\u2005NMR spectrum of [UIII{N(SiPhMe2)2}3], the Me2Si group resonates at \u03b4=\u221257.1\u2005ppm.29Si\u2005NMR spectrum of 1 at \u03b4 \u2212296.0\u2005ppm (\u03bd\u00bd=73\u2005Hz), which has not been reported for similar systems,III complex.23The 13\u21925f26d1 transitions at 20\u2009000 (\u03b5=776\u2009m\u22121\u2009cm\u22121) and 22\u2009500\u2005cm\u22121 (\u03b5=770\u2009m\u22121\u2009cm\u22121) that are typical of UIII[24] and comparable to a broad absorption observed for [UIII{N(SiPhMe2)2}3] at 21\u2009500\u2005cm\u22121 (\u03b5=430\u2009m\u22121\u2009cm\u22121).\u22121 region, weak Laporte forbidden 5f\u21925f transitions were observed (\u03b5=15\u201364\u2009m\u22121\u2009cm\u22121).III complexes, such as [U(I)3(THF)4]III{N(SiPhMe2)2}3],[27]The electronic absorption spectrum of 1 was determined and is depicted in Figure 1 crystallizes in the C2/c space group, with a twofold axis bisecting the U(1)\u2013N(1) bond. This contrasts to [Fe(N\u201c)3],III(N\u201d)3],III(N\u201c)3],III(N\u201d)3],P31c space group, and [UIII{N(SiPhMe2)2}3], which crystallizes in R3.1 is almost ideally trigonal planar, with U\u2013N bonds that are statistically identical within experimental uncertainty [U-N range 2.403(3)\u20132.415(6)\u2005\u00c5]. These distances are longer than those observed in [UIII(N\u201c)3] [2.320(4)\u2005\u00c5]III{N(SiPhMe2)2}3] [2.34(2)\u2005\u00c5],1 arising from the sterically demanding tBu groups. The U centroid/N(1)-N(2)-N(2A) mean plane distance in 1 is 0.008(2)\u2005\u00c5, and the N-U-N bond angles (range 119.1(2)\u2013120.47(9)\u00b0) sum to 360\u00b0; in contrast, [UIII(N\u201d)3] and [UIII{N(SiPhMe2)2}3] exhibit U centroids 0.456(1) and 0.874\u2005\u00c5 from the N3 planes, and the N-U-N angles average 116.24(7) (\u03a3 angles 348.72(7)\u00b0) and 106.88\u00b0 (\u03a3 angles 320.64\u00b0), respectively.2 fragments of 1 are essentially planar and all bisect the UN3 plane (range 53.23\u201361.35\u00b0) to form a molecular propeller.The crystal structure of III(N\u201c)3] and [UIII{N(SiPhMe2)2}3] are predicted by the polarized-ion model, whereby net stabilization was achieved by dipole formation.III(N\u201d)3] exhibits unequal U-N-Si angles (108.50(7) and 125.25(7)\u00b0), because one Si\u2013C bond for each N\u201c ligand is relatively close to the U center .\u22c5\u22c5\u22c5Si\u2013C\u03b3 interactions, as have been discussed for [UIII{CH(SiMe3)2}3]III(N\u201d)3].[31] The shortest U\u22c5\u22c5\u22c5C\u03b3 and U\u22c5\u22c5\u22c5Si distances in 1 are 3.119\u20133.301\u2005\u00c5 and 3.433\u20133.510\u2005\u00c5, respectively, and they are not correctly orientated to interact with the U center. Although there is no evidence for agostic U\u22c5\u22c5\u22c5Si\u2013C\u03b3 interactions in 1, stabilizing U\u22c5\u22c5\u22c5C\u2013H contacts cannot be discounted.The pyramidal geometries of [U1 and [UIII(N\u201c)3].1 , providing qualitative models 3] 0.393\u2005\u00c5). In both models, the HOMO, HOMO\u22121 and HOMO\u22122 represent the three unpaired UIII 5f electrons 3] 86.81, 86.32, 84.17\u2009% U 5f, respectively). Both models exhibit essentially insignificant degrees of U 6d/5f orbital contributions to the U\u2013N bonds, with the HOMO\u22123, HOMO\u22124. and HOMO\u22125, representing the \u03c0 components 3] 4.29/0, 0/2.06, 1.63/1.39\u2009% U 5f/6d, respectively) and the HOMO\u22126, HOMO\u22127, and HOMO\u22128 the \u03c3 components 3] 0/5.04, 0/5.26, 2.14/0\u2009% U 5f/6d, respectively). This concurs with gas-phase photoelectron spectroscopy (PES) studies of [U(N\u201d)3], which have shown that \u03c0 bonding between the ligand and U center is insignificant in this complex.1=\u22123.26; [UIII(N\u2032\u2032)3]=\u22123.26) are identical, which also supports similar bonding patterns for 1 and [UIII(N\u201c)3].Unrestricted DFT calculations were carried out on full models of III(CH3)3] III(NH2)3] 1 and [UIII(N\u201c)3] together with the small U 6d/5f contributions to the U\u2013N \u03c3 and \u03c0 components, we suggest that the experimentally determined trigonal planar geometry of 1 results from steric interactions involving the large N** ligands. These interactions could predominate over crystal packing forces, which are often only approximately 10\u2005kJ\u2009mol\u22121.1 and [UIII(N\u201d)3], therefore, the planar geometry of 1 derives principally from steric effects involving the ligands.Ab initio calculations on [An1 was calculated to be 2.59\u2005\u03bcB in [D6]benzene at 298\u2005K by using the Evans method.[36] Magnetometry measurements on a powdered sample of 1 suspended in eicosane gave a magnetic susceptibility temperature product, \u03c7T, of 1.07\u2005cm3\u2009Kmol\u22121 (2.92\u2005\u03bcB) at 298\u2005K,3 4I9/2 ground state (3.69\u2005\u03bcB), because not all crystal field levels are thermally occupied,III complexes described in the literature (range 2.13\u20134.63\u2005\u03bcB).[38] The \u03c7T value of 1 decreases to 0.41\u2005cm3\u2009Kmol\u22121 at 2\u2005K; ac measurements give a low-temperature plateau in the in-phase \u03c7\u2032T at 0.48\u2005cm3\u2009Kmol\u22121[21] consistent with thermal depopulation into a Kramers doublet ground state.1 are consistent with UIII,[27] and simulation gives geff=3.55, 2.97, and 0.553 for the ground Kramers doublet 3] is an SMM,1 to probe differences in the dynamic magnetic behavior as a result of the higher symmetry. Compound 1 is also an SMM, with clear frequency-dependent behavior 3], and maxima in the out-of-phase susceptibility \u03c7\u2032\u2032(T) are seen to significantly higher temperatures for 1 than for [UIII(N\u201c)3] at equivalent frequencies . An Arrhenius treatmentUeff=21.4\u00b10.2\u2005K for 1. Although this is lower than that reported for [UIII(N\u201d)3] (31\u2005K), the latter value was derived from an extremely limited temperature range\u03c4) at 2\u2005K is 2.6\u2005ms for 1; from the previously reported dataIII(N\u201c)3] at 2\u2005K, an order of magnitude quicker. The pre-factor \u03c40 for 1 is greater by four orders of magnitude (3.1\u00d710\u22127 cf. 10\u221211\u2005s for [UIII(N\u201d)3]).\u03c7\u2032 and \u03c7\u201c at 1.8\u2005K for 1\u03b1=0.001\u20130.03 from Cole\u2013Cole analysis), an order of magnitude lower than in [UIII(N\u201d)3] (\u03b1=0.09\u20130.34).1 at 1.8\u2005K on a conventional superconducting quantum interference device (SQUID) magnetometer 3].Compound  from optical studies.1 and [UIII(N\u201d)3] are SMMs despite their easy-plane anisotropy: this highlights the complexity of interpreting f-block relaxation data,1 compared with [UIII(N\u201c)3] on flattening the geometry is because of quenched mixing. In Dh3 |zJ|=1/2 cannot mix with any other doublet within the 4I9/2 term, whereas in Cv3, it can mix with both |zJ|=5/2 and 7/2.In the trigonal planar geometry of 1 and [UIII(N\u201c)3] can be attributed to differences in symmetry that may be useful to consider in the future design of UIII SMMs with greater relaxation times. Computational analyses of 1 and [UIII(N\u201d)3] have shown only minor differences in their calculated bonding schemes, therefore, the energy gained by pyramidalization, which leads to favorable agostic M\u22c5\u22c5\u22c5Si\u2013C\u03b3 interactions in [UIII(N\u201c)3],To conclude, we have prepared and fully characterized an unprecedented trigonal planar actinide triamide complex. Differences in the spectroscopic and magnetic data between Synthesis of 1: THF (20\u2005mL) was added to a precooled (\u221278\u2009\u00b0C) mixture of [K{N(SiMe2tBu)2}]2  and [U(I)3(THF)4] . The reaction mixture was allowed to warm to RT slowly with stirring over 48\u2005h, with precipitation of a pale solid. Volatiles were removed in vacuo, and the dark purple solid was extracted with hexanes (3\u00d710\u2005mL). Recrystallization from hexanes (5\u2005mL) at \u221230\u2009\u00b0C gave 1 as dark purple needles .1H\u2005NMR : \u03b4=\u221247.04 2), 3.79\u2005ppm 3); 13C{1H}\u2005NMR : \u03b4=\u22122.13 (Si(CH3)2), 1.45 (Si(CH3)2), 18.22 (SiC(CH3)3), 26.40 (SiC(CH3)3), 31.98\u2005ppm (SiC(CH3)3); 29Si{1H}\u2005NMR : \u03b4=\u2212296.04\u2005ppm ; FTIR (Nujol); 2), 825 , 761 , 655 (m), 604 (s) cm\u22121; \u03bceff=2.59\u2005\u03bcB (Evans method); elemental analysis calcd for C36H90Si6N3U (971.67\u2005g\u2009mol\u22121): C 44.5, H 9.34, N 4.33; found: C 38.29, H 9.10, N 4.22. Low carbon values were obtained upon repeating the analysis multiple times on different batches and is ascribed to 1 being a silicon-rich molecule, as was observed previously.42"}
{"text": "H-1,2,4-triazol-3-yl-\u03baN4)acetato-\u03baO]di\u00adaqua)\u00adnickel(II) dihydrate, is the first transition metal complex of 2-acetic acid (ATAA).The title compound, bis\u00ad[(5-amino-1 4H5N4O2)2(H2O)2]\u00b72H2O, represents the first transition metal complex of the novel chelating triazole ligand, 2-acetic acid (ATAA), to be structurally characterized. In the mol\u00adecule of the title complex, the nickel(II) cation is located on an inversion centre and is coordinated by two water mol\u00adecules in axial positions and two O and two N atoms from two trans-oriented chelating anions of the deprotonated ATAA ligand, forming a slightly distorted octa\u00adhedron. The trans angles of the octa\u00adhedron are all 180\u00b0 due to the inversion symmetry of the mol\u00adecule. The cis-angles are in the range 87.25\u2005(8)\u201392.75\u2005(8)\u00b0. The six-membered chelate ring adopts a slightly twisted boat conformation with puckering parameters Q = 0.542\u2005(2)\u2005\u00c5, \u0398 = 88.5\u2005(2) and \u03d5 = 15.4\u2005(3)\u00b0. The mol\u00adecular conformation is stabilized by intra\u00admolecular N\u2014H\u22efO hydrogen bonds between the amino group and the chelating carboxyl\u00adate O atom of two trans-oriented ligands. In the crystal, the complex mol\u00adecules and lattice water mol\u00adecules are linked into a three-dimensional framework by an extensive network of N\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.The title compound, [Ni(C C-amino-1,2,4-triazoles are employed as polydentate ligands for the synthesis of coordination compounds with various metals that demonstrate useful spectroscopic, magnetic, biological and catalytic properties  can act as chelating polydentate ligands acetic acid 2(H2O)2]\u00b72H2O (1).In a continuation of our work on the synthesis and reactivity of amino\u00adtriazole carb\u00adoxy\u00adlic acids \u201392.75\u2005(8)\u00b0. The third water mol\u00adecule is not involved in coordination. The anions of ATAA coordinate the NiII cation through the nitro\u00adgen atom N1 of the triazole ring and the oxygen atom O53 of the carboxyl\u00adate group \u2005\u00c5, \u0398 = 88.5\u2005(2), \u03d5 = 15.4\u2005(3)\u00b0. The Ni\u2014N1 bond length is 2.051\u2005(2)\u2005\u00c5, and the Ni\u2014O1 and Ni\u2014O53 bond lengths are 2.083\u2005(2) and 2.059\u2005(2)\u2005\u00c5, respectively, within the normal ranges for other reported NiII complexes , the Nion Fig.\u00a02. The traup Fig.\u00a02, similards Fig.\u00a02.In the crystal, mol\u00adecules of the complex and lattice water mol\u00adecules are linked into a three\u2013dimensional framework by extensive N\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds Table\u00a01.et al., 2010H-1,2,4-triazole-3-carb\u00adoxy\u00adlic acid (ATCA) with various metals acetate (2) in an aqueous solution of nickel nitrate 2\u00b76H2O in water (5\u2005ml). After standing at room temperature for two weeks, the formed crystals were collected by filtration yielding the target compound (1).All attempts to prepare crystals of complex (1) suitable for X-ray investigation by mixing solutions of te Fig.\u00a04. A solut2 group and refined as riding, with Uiso(H) = 1.2Ueq(C). The N,O-bound H atoms that are involved in hydrogen bonds were found from difference Fourier maps. Their distances to the parent atoms were refined to be equal, with a common Uiso(H) value for pairs of related H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814021436/wm5066sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814021436/wm5066Isup2.hklStructure factors: contains datablock(s) I. DOI: 1026535CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Each AgI ion is bridged by the ligands, forming a helical chain propagating along the b-axis direction. The right- and left-handed helical chains are alternately arranged via Ag\u22efAg [3.2639\u2005(5)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.523\u2005(1)\u2005\u00c5], resulting in the formation of a two-dimensional supra\u00admolecular network extending parallel to (101). Weak Ag\u22efF inter\u00adactions [longest Ag\u22efF inter\u00adaction = 3.153\u2005(2)\u2005\u00c5], as well as N\u2014H\u22efF and C\u2014H\u22efF hydrogen-bonding inter\u00adactions, occur between the helical chains and the anions.In the title polymeric complex, {[Ag(C I coordination polymers with symmetrical dipyridyl ligands, see: Lee et al. ]PF6 = 0.027wR(F2) = 0.071S = 1.052740 reflections199 parametersH-atom parameters constrainedmax = 0.86 e \u00c5\u22123\u0394\u03c1min = \u22120.44 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011465/sj5402Isup2.hklStructure factors: contains datablock(s) I. DOI: 1003661CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The coordinating water mol\u00adecules are hydrogen bonded to the carboxyl O atoms [O \u22ef O = 2.6230\u2005(17)\u2005\u00c5], enclosing an S(6) hydrogen-bonding motif, while inter\u00admolecular O\u2014H\u22efO hydrogen bonds link two of the non-coordinating water mol\u00adecules to the coordinating water mol\u00adecules and NA anions. In the crystal, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules, enclosing The asymmetric unit of the monomeric cobalt complex, [Co(C 11H13O2)2(C6H6N2O)2(H2O)2]\u00b72H2O, contains one half of the complex mol\u00adecule, one coordinating and one non-coordinating water mol\u00adecule, one 4-tert-butyl\u00adbenzoate (TBB) ligand and one nicotinamide (NA) ligand; the Co atom lies on an inversion centre. All ligands coordinating to the Co atom are monodentate. The four nearest O atoms around the Co atom form a slightly distorted square-planar arrangement, with the distorted octa\u00adhedral coordination completed by the two pyridine N atoms of the NA ligands at distances of 2.1638\u2005(11)\u2005\u00c5. The coordinating water mol\u00adecules are hydrogen bonded to the carboxyl O atoms [O \u22ef O = 2.6230\u2005(17)\u2005\u00c5], enclosing an S(6) hydrogen-bonding motif, while inter\u00admolecular O\u2014H\u22efO hydrogen bonds link two of the non-coordinating water mol\u00adecules to the coordinating water mol\u00adecules and NA anions. The dihedral angle between the planar carboxyl\u00adate group and the adjacent benzene ring is 29.09\u2005(10)\u00b0, while the benzene and pyridine rings are oriented at a dihedral angle of 88.53\u2005(4)\u00b0. In the crystal, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules, enclosing R22(8), R22(10) and R44(12) ring motifs, forming layers parallel to (001). The C and H atoms of the tert-butyl group of the TBB ligand are disordered over two sets of sites with an occupancy ratio of 0.631\u2005(5):0.369\u2005(5). The asymmetric unit of the mononuclear cobalt complex, [Co(C The Co\u2014O bond lengths are 2.1104\u2005(11)\u2005\u00c5 (for water oxygens) and 2.1252\u2005(9)\u2005\u00c5 (for benzoate oxygens) and the Co\u2014N bond length is 2.1638\u2005(11)\u2005\u00c5, close to standard values. The Co1\u2014O2\u2014C1\u2014C2 torsion angle [\u2212163.00\u2005(9)\u00b0] causes a slight downward tilt of the ligand.The dihedral angle between the planar carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene (C2\u2013C7) ring is 29.09\u2005(10)\u00b0, while the benzene and pyridine (N1/C9\u2013C13) rings are oriented at a dihedral angle of 88.53\u2005(4)\u00b0.w\u22efOc  hydrogen bonds (Table\u00a01S(6) hydrogen-bonding motifs, while inter\u00admolecular O\u2014Hw\u22efOw and O\u2014Hw\u22efOna (na = nicotinamide) hydrogen bonds link two of the non-coordinating water mol\u00adecules to the coordinating water mol\u00adecules and NA anions  in water (75\u2005ml) and nicotinamide  in water (25\u2005ml) with sodium 4-tert-butyl\u00adbenzoate  in water (250\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for five days, giving pink single crystals.The title compound was prepared by the reaction of CoSO2), H41, H42, H51 and H52 (for H2O) were located in a difference Fourier map and were refined freely. The C-bound H atoms were positioned geometrically, with C\u2014H = 0.93 and 0.96\u2005\u00c5 for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic H atoms. During the refinement process the disordered t-butyl group atoms were refined with major:minor occupancy ratios of 0.631\u2005(5):0.369\u2005(5).Experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016008689/pk2579sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016008689/pk2579Isup2.hklStructure factors: contains datablock(s) I. DOI: 1482507CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One of these P atoms belongs to a bridging dppb ligand [Cu\u2014P = 2.2381\u2005(5)\u2005\u00c5] and two belong to a chelating dppb ligand [Cu\u2014P = 2.2450\u2005(6) and 2.2628\u2005(5)\u2005\u00c5]. The bridging dppb ligand lies on an inversion centre. In the crystal, the cation and the PF6\u2212 anion are linked by C\u2014H\u22efF inter\u00adactions, forming a tape along [110]. The cation and the diethyl ether solvent mol\u00adecule are also linked by a C\u2014H\u22efO inter\u00adaction.In the centrosymmetric dinuclear copper(I) complex cation of the title compound, [Cu For cop al. 1999; Kitagaw al. 1995. For our al. 2006.2(C28H28P2)3](PF6)2\u00b72C4H10O = 0.036wR(F2) = 0.090S = 1.069436 reflections523 parametersH-atom parameters constrainedmax = 0.41 e \u00c5\u22123\u0394\u03c1min = \u22120.35 e \u00c5\u22123\u0394\u03c1CrystalClear  used to solve structure: SIR92  global, I. DOI: 10.1107/S1600536814009763/is5355Isup2.hklStructure factors: contains datablock(s) I. DOI: 1000315CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two copper(II) complexes, a dinuclear and a hexa\u00adnuclear complex with bridging hydroxyl and nitrate ligands, were obtained from reaction of copper nitrate with di\u00adhydroxy\u00adbipyridine at neutral and slightly acidic pH. Formation of multi-nuclear complexes contrasts with the equivalent sulfate compounds which formed discrete mononuclear complexes. The complexes feature intra\u00admolecular and inter\u00admolecular hydrogen bonding. 3)2 and 6,6\u2032-di\u00adhydroxy\u00adbipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (\u03bc-hydroxido-1:2\u03ba2O:O\u2032)(\u03bc-nitrato-1:2\u03ba2O:O\u2032)(nitrato-1\u03baO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6\u2032-O-bpy)(NO3)(\u03bc-OH)(\u03bc-NO3)Cu], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water\u2013ethanol mixture at neutral pH. The hexa\u00adnuclear complex bis\u00adtetra\u00adkis\u00adtetra\u00adkis\u00ad(\u03bc-hydroxido-\u03ba2O:O\u2032)bis\u00ad(methanol-\u03baO)tetra\u00adkis\u00ad(\u03bc-nitrato-\u03ba2O:O\u2032)hexa\u00adcopper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(\u03bc-NO3)2(\u03bc-OH)Cu(\u03bc-OH)Cu(CH3OH)]2, (II), with a 1:1 NO3\u2013OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intra\u00admolecular O\u2014H\u22efO hydrogen bonding. Inter\u00admolecular O\u2014H\u22efO hydrogen bonding links symmetry-related mol\u00adecules forming chains along [100] for complex (I) with \u03c0-stacking along [010] and [001]. Complex (II) forms inter\u00admolecular O\u2014H\u22efO hydrogen-bonded chains along [010] with \u03c0-stacking along [100] and [001].Two multinuclear complexes synthesized from Cu(NO A new coordination mode is observed for the mono-deprotonated (6-O-6\u2032-OH-bpy) ligand in which it bridges two metals, through  coordination of N1,N2 to Cu1 and through bridging to Cu2 via the pyridino\u00adlate oxygen O2 [1.946\u2005(3)\u2005\u00c5]. The C\u2014O bond lengths (\u00c5) for the dhbp ligands are 1.335\u2005(5) (C1\u2014O1), 1.322\u2005(5) (C11\u2014O3), and 1.316\u2005(4) (C20\u2014O4) for the protonated hydroxyl groups and slightly shorter at 1.310\u2005(4) (C10\u2014O2) for the pyridino\u00adlate, reflecting double-bond character. Both copper atoms have a distorted square-pyramidal geometry with \u03c4 = 0.394 at Cu1 and \u03c4 = 0.119 at Cu2 \u2005\u00c5 hydrogen bond from O5 to O11 (hydroxyl to nitrate) with a bond angle of 164\u2005(4)\u00b0. Numerical details of the hydrogen bonds are given in Table\u00a01The dinuclear copper(II) dhbp complex (I)et al., 1984N,N bound), one bridging hydroxide to Cu2 (O14), one bridging nitrate to Cu2 (O11), and one bridging nitrate (O7) which tethers the two asymmetric units. The coordination of Cu2 entails one deprotonated dhbp , one bridg\u00ading nitrate to Cu1 (O12), and two bridging hydroxides to Cu1 and Cu3 . The remaining coord\u00adination sphere of Cu3 entails one dhbp , one methanol (O15), one bridging hydroxide (O13), and one bridging nitrate (O8) which tethers the two asymmetric units. Each deprotonated oxygen of dhbp acts as an acceptor for intra\u00admolecular hydrogen bonds from the two protonated dhbp ligands, O2 to O3 at 2.499\u2005(3)\u2005\u00c5 (O\u2014H\u22efO bond angle of 172\u00b0), and O6 to O4 at 2.495\u2005(3)\u2005\u00c5 (O\u2014H\u22efO bond angle of 168\u00b0) shown in Fig.\u00a04The hexa\u00adnuclear copper(II)Comparison of complex (I)II ions is charge balanced with one terminal and one bridging nitrate each with a single negative charge, one deprotonated hydroxyl group of dhbp, and one bridging hydroxide. The bond lengths to the bridging hydroxide from Cu1 to O5 is 1.964\u2005(3)\u2005\u00c5 and Cu2 to O5 is 1.939\u2005(3)\u2005\u00c5 where the proton of O5 hydrogen bonds to one acceptor. A comparable bond length is 1.946\u2005(3)\u2005\u00c5 from Cu2 to O2 of the deprotonated dhbp ligand. The remaining oxygen atoms of the dhbp ligands are each protonated and engaged in hydrogen bonding as described above. The asymmetric unit of complex (II)The bridging oxygen species for both complexes (I)vide supra. The dinuclear complex (I)x, \u2212y, \u2212z at a distance of 3.894\u2005(3)\u2005\u00c5 between the centroids of the rings. The pyridine ring containing N1 inter\u00adacts with its symmetry-equivalent ring across the symmetry operation 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z with a centroid-to-centroid distance of 3.969\u2005(3)\u2005\u00c5. The dhbp ligand coordinating to Cu2 also shows \u03c0-stacking via two alternating inversion-symmetry operations, forming chains along [100]. The pyridine rings containing N3 and N4 inter\u00adcross by the symmetry operation 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z where the centroid of the ring defined by N3 is at a distance of 3.604\u2005(2)\u2005\u00c5 from the centroid of the ring defined as N4 on side of the dhbp plane with the bridging hydroxide. These rings also \u03c0-stack on the opposite face of the plane at a distance of 3.768\u2005(2)\u2005\u00c5 from the centroid of the ring defined by N3 to N4 through the symmetry operation \u2212x, \u2212y, 1\u00a0\u2212\u00a0z. Inter\u00admolecular hydrogen bonding from the bridging hydroxide ligand to the terminal oxygen of the bridging nitrate ligand inter\u00adlinks neighboring mol\u00adecules primarily along [100]. See Fig.\u00a06Some inter\u00admolecular hydrogen-bonding inter\u00adactions in both complexes have already been discussed, ac plane and exhibit \u03c0-stacking but in a less regular fashion than for complex (I)x, \u2212y, \u2212z with a centroid-to-centroid distance of 3.784\u2005(2)\u2005\u00c5 of the pyridine rings containing N1 to the ring containing N2 and vice versa. A single ring of each dhbp ligand bound to Cu2 and Cu3 \u03c0-stack via translation at a distance of 3.551\u2005(2)\u2005\u00c5 between the centroids of the pyridine rings defined by N3 and N5, respectively. Additionally, the Cu3 dhbp ligand \u03c0-stacks via the symmetry-equivalent ring defined by N5 of a neighboring mol\u00adecule across the symmetry operation \u2212x, \u2212y, 1\u00a0\u2212\u00a0z at a centroid-to-centroid distance of 3.887\u2005(2)\u2005\u00c5. Close proximity occurs in plane between the pyridine ring containing N4 of the dhbp ligand bound to Cu2 at a distance of 3.818\u2005(2)\u2005\u00c5 between C18 to C19 and vice versa across the symmetry operation 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z.The hexa\u00adnuclear complex (II)et al., 2007et al., 2013et al., 2009et al., 2013et al., 2006et al., 2006et al., 2002Although many structures have been reported featuring a hydroxide anion bridging two copper(II) ions each bound by 2,2\u2032-bi\u00adpyridine, no analogous structure has been reported with a 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine ligand. A search of the Cambridge Structural Database  Copper(II)The neutral copper hexanuclear complex (II) Copper(II)Crystal data, data collection, and structure refinement details are summarized in Table\u00a03Cell Now  involve domain 2 only, mean I/\u03c3 8.2, 34813 data (9811 unique) involve 2 domains, mean I/sigma 9.5, 11 data (11 unique) involve 3 domains, mean I/\u03c3 8.7 and 4 data (2 unique) involve 4 domains, mean I/\u03c3 57.6 The exact correlation matrix as identified by the integration program was found to be 1.00336 0.02923 \u22120.02720, \u22120.01894 1.02272 \u22120.04903, 0.02520 0.05747 0.97055. The data were corrected for absorption using TWINABS arom = 0.95\u2005\u00c5 with Uiso(H) = 1.2Ueq(C), C\u2014Hmeth\u00adyl = 0.98\u2005\u00c5 with Uiso(H) = 1.5Ueq(C). O\u2014H were refined for complex (I)Uiso(HOH) were set to 1.5Ueq(O).C- and O-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms: aromatic C\u2014H10.1107/S205698901502037X/lh5780sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S205698901502037X/lh5780Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901502037X/lh5780IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1433678, 1000450CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The coordination geometry of the metal ion is distorted trigonal bipyramidal, with the ligand O atoms in the axial sites. Two of the carboxyl\u00adate groups of the ligand remain protonated and form short symmetric O\u2014H\u22efO hydrogen bonds. In the crystal, the ribbons inter\u00adact via a network of O\u2014H\u22efO hydrogen bonds in which coordinating water mol\u00adecules act as donors and carboxyl\u00adate O atoms within adjacent ribbons act as acceptors, giving rise to a three-dimensional framework. O\u2014H\u22efN inter\u00adactions are also observed. The asymmetric unit contains quarter of the ligand and the complete ligand has 2/m symmetry; the Li+ ion lies on a special position with m.. site symmetry. Both bridging water mol\u00adecules have m2m site symmetry and both lattice water mol\u00adecules have m.. site symmetry; one of the latter was modelled with a site occupancy of 0.25.The title coordination polymer, {[Li For the structures of related lithium complexes with pyrazine-2,3,5,6-tetra\u00adcarboxyl\u00adate and water ligands, see: Starosta & Leciejewicz 2010, 2014 \u25b6.2(C8H2N2O8)(H2O)2]\u00b72.5H2O = 0.042wR(F2) = 0.122S = 1.071151 reflections85 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.25 e \u00c5\u22123\u0394\u03c1min = \u22120.29 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S160053681401174X/hb7224Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004410CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(aryl\u00adsulfon\u00adyl)-4-fluoro\u00adbenzamides, namely 4-fluoro-N-(2-methyl\u00adphenyl\u00adsulfon\u00adyl)\u00adbenzamide, (I), N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-fluoro\u00adbenzamide, (II), and N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-fluoro\u00adbenzamide monohydrate, (III), are described and compared with related structures. The conformation of the three mol\u00adecules is very similar with the aromatic rings being inclined to one another by 82.83\u2005(11) and 85.01\u2005(10)\u00b0 in the two independent mol\u00adecules of (I), 89.91\u2005(10)\u00b0 in (II) and 81.82\u2005(11)\u00b0 in (III).The crystal structures of three  N-aryl\u00adsulfonyl-4-fluoro\u00adbenzamides, namely 4-fluoro-N-(2-methyl\u00adphenyl\u00adsulfon\u00adyl)benzamide, C14H12FNO3S, (I), N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-fluorobenzamide, C13H9ClFNO3S, (II), and N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-fluoro\u00adbenzamide monohydrate, C13H9ClFNO3S\u00b7H2O, (III), are described and compared with related structures. The asymmetric unit of (I) contains two independent mol\u00adecules (A and B), while that of (II) contains just one mol\u00adecule, and that of (III) contains a mol\u00adecule of water in addition to one main mol\u00adecule. The dihedral angle between the benzene rings is 82.83\u2005(11)\u00b0 in mol\u00adecule A and 85.01\u2005(10)\u00b0 in mol\u00adecule B of (I), compared to 89.91\u2005(10)\u00b0 in (II) and 81.82\u2005(11)\u00b0 in (III). The crystal structure of (I) features strong N\u2014H\u22efO hydrogen bonds between the A and B mol\u00adecules, resulting in an R44(16) tetra\u00admeric unit. These tetra\u00admeric units are connected into sheets in the bc plane by various C\u2014H\u22efO inter\u00adactions, and adjacent sheets are further inter\u00adlinked via C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions, forming a three-dimensional architecture. The crystal structure is further stabilized by \u03c0ar\u00adyl\u2013\u03c0ar\u00adyl and S=O\u22ef\u03c0ar\u00adyl inter\u00adactions. In the crystal of (II), mol\u00adecules are connected into R22(8) and R22(14) dimers via N\u2014H\u22efO hydrogen bonds and C\u2014H\u22efO inter\u00adactions, respectively; the dimers are further inter\u00adconnected via a weak C=O\u22ef\u03c0ar\u00adyl inter\u00adaction, leading to the formation of chains along [1-10]. In the crystal of (III), N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds involving both the main mol\u00adecule and the solvent water mol\u00adecule results in the formation of sheets parallel to the bc plane. The sheets are further connected by C\u2014H\u22efO inter\u00adactions and weak C\u2014Cl\u22ef\u03c0ar\u00adyl, C\u2014F\u22ef\u03c0ar\u00adyl and S=O\u22ef\u03c0ar\u00adyl inter\u00adactions, forming a three-dimensional architecture.The crystal structures of three  An intra\u00admolecular C14B\u2013-H14B\u22efO2B hydrogen bond S(6) ring motif.The asymmetric unit of compound (I)B) Fig.\u00a01, that diB) Fig.\u00a01 containsB) Fig.\u00a01 crystallnt Fig.\u00a01. This isA\u2014H1A\u22efO1B and N1B\u2014H1B\u22efO1A hydrogen bonds , while in the second level the tetra\u00admeric unit has a graph-set motif of R44(16). Adjacent tetra\u00admers are connected into sheets in the bc plane  ar\u00adyl\u2013\u03c0ar\u00adyl inter\u00adactions \u2005\u00c5; Cg1 and Cg2 are the centroids of the fluoro\u00adbenzoyl rings of mol\u00adecules A and B, respectively] and also by weak S1A=O2A\u22ef\u03c0ar\u00adyl inter\u00adactions .The crystal structure of (I)s Table\u00a01 between it Fig.\u00a04. The unine Fig.\u00a04 via C6A\u2014s Table\u00a01. AdjacenB) Fig.\u00a05 to form ns Fig.\u00a06  connect these dimers, thus forming a one-dimensional architecture .In the crystal of (II)re Fig.\u00a07b.via bridging water mol\u00adecules, through strong N1\u2014H1\u22efO4, O4\u2014H1O4\u22efO1, O4\u2014H2O4\u22efO2 and O4\u2014H2O4\u22efO3 hydrogen bonds \u2005\u00c5], C11\u2014F1\u22efCg2 [F1\u22efCg2 = 3.8674\u2005(17)\u2005\u00c5] and S1=O2\u22efCg1 inter\u00adactions [O2\u22efCg1 = 3.2039\u2005(17)\u2005\u00c5] , forming a complex three-dimensional architecture s Table\u00a03, resultie Figs. 8 and 9 \u25b8.viz N-(aryl\u00adsulfon\u00adyl)-4-(substituted)benzamides, gave 14 hits. These fourteen compounds along with the three title compounds, (I)\u2013(III), are grouped into three series; series 1: N-(2-methyl\u00adphenyl\u00adsulfon\u00adyl)benzamide, N-(2-methyl\u00adphen\u00adyl\u00adsulfon\u00adyl)-4-(chloro/meth\u00adyl/nitro/meth\u00adoxy)benzamides and (I)series 2: N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)benzamide, N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-(chloro/meth\u00adyl/nitro/meth\u00adoxy)benzamides and (II)series 3: N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)benzamide, N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-(chloro/meth\u00adyl/nitro)benzamides and (III)A search of the Cambridge Structural Database benzamide -4-nitro\u00adbenzamide -4-meth\u00adoxy\u00adbenzamide -4-chloro\u00adbenzamide -4-methyl\u00adbenzamide -4-fluoro\u00adbenzamide (I)ortho-methyl group on the benzene\u00adsulfonyl ring is syn to the N\u2014H bond in the central \u2013C\u2013SO2--N\u2013C(O)\u2013 segment. The values of the dihedral angle between the two aromatic rings in the mol\u00adecules of series 1 fall in the range 73.9\u2005(1)\u2013 89.4\u2005(1)\u00b0, the smallest dihedral angle being in N-(2-methyl\u00adphenyl\u00adsulfon\u00adyl)benzamide and the largest in N-(2-methyl\u00adphenyl\u00adsulfon\u00adyl)-4-chloro\u00adbenzamide  hydrogen bonds. However, except for compound (I)1 Table\u00a04, the asye Table\u00a04. CompariSeries 2: The asymmetric units of all of the compounds in series 2 \u2013 segment. The values of the dihedral angle between the two aromatic rings in the mol\u00adecules fall in the range 73.3\u2005(1)\u201389.91\u2005(10)\u00b0, which is almost the same as in series 1, the smallest being in N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)benzamide -4-fluoro\u00adbenzamide (II)N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-benzamide, N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-chloro\u00adbenzamide -4-methyl\u00adbenzamide  hydrogen bonds, while strong N\u2014H\u22efO(S) hydrogen bonds in N-(2-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-nitro\u00adbenzamide -4-meth\u00adoxy\u00adbenzamide -4-fluoro\u00adbenzamide (II)via C=O\u22ef\u03c0ar\u00adyl inter\u00adactions, forming a one-dimensional architecture.2 Table\u00a05 contain Series 3: In series 3, the parent compound N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)benzamide -4-chloro\u00adbenzamide -4-methyl\u00adbenzamide -4-nitro\u00adbenzamide -4-fluoro\u00adbenzamide (III)N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)benzamide and the largest for N-(4-chloro\u00adphenyl\u00adsulfon\u00adyl)-4-methyl\u00adbenzamide (Table\u00a06e Table\u00a06. Except Compounds (I)\u2013(III) were prepared by refluxing a mixture of 4-fluoro\u00adbenzoic acid, the corresponding substituted benzene\u00adsulfonamides and phospho\u00adrousoxychloride for 3\u2005h on a water bath. The resultant mixtures were cooled and poured into ice-cold water. The solids obtained were filtered, washed thoroughly with water and then dissolved in sodium bicarbonate solutions. The compounds were later re-precipitated by acidifying the filtered solutions with dilute HCl. They were filtered, dried and recrystallized. [Melting point (m.p.) of (I)Uiso = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. In the final cycles of refinement, reflections (0 1 1), (0 0 2) and  I, II, III, global. DOI: 1470505, 1470504, 1470503CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compounds, (I), (II) and (III), are indole derivatives. Compounds (I) and (II) present two independent moieties in the asymmetric unit, and their packing is led by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. In compound (III), the C\u2014H\u22efO hydrogen bonds form  17H13NO2S, (I), C17H13NO3S, (II), and C24H17ClN2O5S\u00b7CHCl3, (III), are indole derivatives. Compounds (I) and (II) crystalize with two independent mol\u00adecules in the asymmetric unit. The indole ring systems in all three structures deviate only slightly from planarity, with dihedral angles between the planes of the pyrrole and benzene rings spanning the tight range 0.20\u2005(9)\u20131.65\u2005(9)\u00b0. These indole ring systems, in turn, are almost orthogonal to the phenyl\u00adsulfonyl rings [range of dihedral angles between mean planes = 77.21\u2005(8)\u201389.26\u2005(8)\u00b0]. In the three compounds, the mol\u00adecular structure is stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds, generating S(6) ring motifs with the sulfone O atom. In compounds (I) and (II), the two independent mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, while in compound (III), the mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, generating R22(22) inversion dimers.The title compounds, C The corresponding bond lengths and bond angles of mol\u00adecules A and B [in compounds (I)A and B of compound (I)], 0.20\u2005(9) and 0.86\u2005(9) [mol\u00adecules A and B of compound (II)], and 1.34\u2005(14)\u00b0 [compound (III)].The mol\u00adecular structures of title compounds (I)The indole ring systems are almost orthogonal to the phenyl\u00adsulfonyl rings [dihedral angles = 77.21\u2005(8) and 89.26\u2005(8)\u00b0 in (I)sp2 bond lengths are longer than the mean value of 1.355\u2005(14)\u00c5 for the N\u2014C bond length  ring motifs with the sulfone O atom (Tables 1The sums of the bond angles around atoms N1 are 351.55 and 356.16\u00b0 in (I) Tables 1 and 3 \u25b8.via inter\u00admolecular C16B\u2014H16B\u22efO2A hydrogen bonds running parallel to the [101] direction. The crystal packing is further stabilized by inter\u00admolecular C10A\u2014H10A\u22efCg1, C11A\u2014H11A\u22efCg2 and C16A\u2014H16A\u22efCg3 inter\u00adactions, with separations of 3.727\u2005(2), 3.546\u2005(2) and 3.699\u2005(3)\u2005\u00c5 at  and , respectively. Cg2 is the centre of gravity of pyrrole ring N1B/C1B/C6B/C7B/C8B, and Cg1 and Cg3 are the centres of gravity of benzene rings C1B\u2013C6B and C1A\u2013C6A, respectively. C\u2014H\u22ef\u03c0 inter\u00adactions run parallel to the [210] direction n Table\u00a01.A and B) are linked by inter\u00admolecular C12B\u2014H12B\u22efO2A hydrogen bonds and are further connected by C5A\u2014H5A\u22efCg1 and C17B\u2014H17C\u22efCg2 inter\u00adactions, with separations of 3.550\u2005(2) and 3.729\u2005(2)\u2005\u00c5 at  (1 and Cg2 are the centres of gravity of benzene rings C9A\u2013C14A and C1A\u2013C6A), respectively). The C12B\u2014H12B\u22efO2A and C17B\u2014H17C\u22efCg2 inter\u00adactions run parallel to the [101] direction and C5A\u2014H5A\u22efCg1 inter\u00adactions run along the tri\u00adphenyl\u00adphospho\u00adnium ylide  in dry toluene (20\u2005ml) was refluxed for 12\u2005h under an N2 atmosphere. After consumption of the starting material [monitered by thin-layer chromatography (TLC)], removal of the solvent in vacuo followed by column chromatographic purification  gave (I)A solution of tri\u00adphenyl\u00adphosphonium ylide  and 5-chloro\u00adnitro\u00adbenzaldehyde  in dry chloro\u00adform (50\u2005ml) was refluxed for 10\u2005h under an N2 atmosphere. Removal of the solvent in vacuo followed by titration of the crude product with methonal (10\u2005ml), gave (III)A solution of [(3-acetyl-1-phenyl\u00adsufanyl-1Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(nonmethyl C). The rotation angles for methyl groups were optimized by least squares.Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989015014917/bg2558sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989015014917/bg2558Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014917/bg2558IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015014917/bg2558IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989015014917/bg2558IIsup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015014917/bg2558IIIsup6.cmlSupporting information file. DOI: 1417660, 1417659, 1417658CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the hydrogen phosphate anions are linked by O\u2014H\u22efO hydrogen bonds into chains parallel to [100]. The inorganic anionic chains and the organic cations are linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming a two-dimensional supra\u00admolecular network extending parallel to (001). 6H9N2+\u00b7HPO42\u2212, comprises two 2-amino\u00adanilinium cations and one hydrogen phosphate dianion. In the crystal, the HPO42\u2212 dianions are linked by O\u2014H\u22efO hydrogen bonds into chains along [100]. The inorganic anionic chains and organic cations are linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming a two-dimensional supra\u00admolecular network extending parallel to (001).The asymmetric unit of the title compound, 2C Organic mono\u00adhydrogen (HPO42\u2212) and di\u00adhydrogen phosphate (H2PO4\u2212) compounds provide a class of materials with numerous practical and potential uses in various fields such as biomolecular sciences, catalysis, liquid-crystal-material development, ferroelectrics, non-linear optical and supra\u00admolecular studies \u00b0].The asymmetric unit of the title compound comprises two 2-amino\u00adanilinium cations and one hydrogen phosphate dianion Fig.\u00a01. The exiviz. O\u2014H\u22efO, N\u2014H\u22efO and N\u2014H\u22efN (Table\u00a01D\u22efO2i hydrogen bond  connects adjacent hydrogen phosphate anions, forming anionic chains extending along [100]. The oxygen atom O3 acts as a trifurcated hydrogen-bond acceptor for the donor nitro\u00adgen atom N1 at ,  and , forming a one-dimensional supra\u00admolecular ladder extending along [100] as shown in Fig.\u00a02C\u22efO3, N3\u2014H3A\u22efO3i and N3\u2014H3B\u22efO3iv  hydrogen bonds, forming two types of fused rings of B\u22efO2, N1\u2014H1A\u22efO4ii and N1\u2014H1C\u22efO4iii  hydrogen bonds, resulting in the formation of a two-dimensional organic\u2013inorganic supra\u00admolecular layered network parallel to (001)  \u2212x, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a02; (v) x, \u22121\u00a0+\u00a0y, z] hydrogen bonds stabilize the (001) network. In the crystal structure  Fig.\u00a03. In the re Fig.\u00a04, adjacenConQuest 1.17; Groom & Allen, 2014et al., 2002et al., 2012et al., 2010et al., 1998et al., 2005A CSD database search  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016004709/rz5186sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016004709/rz5186Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016004709/rz5186Isup3.cmlSupporting information file. DOI: 1469440CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two symmetry-related tetra\u00adbromo\u00adphthalate anions bridge the two CuII cations, forming a centrosymmetric dinuclear complex in which the Cu\u22efCu separation is 5.054\u2005(2)\u2005\u00c5. Intra\u00admolecular classic O\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efO hydrogen bonds occur in the dinuclear mol\u00adecule. In the crystal, the mol\u00adecules are linked by weak C\u2014H\u22efBr and C\u2014H\u22efO inter\u00adactions into supra\u00admolecular chains propagating along the b-axis direction.In the title complex, [Cu For the al. 2004; Colacio al. 2009; Rodpun  al. 2015; Yang et al. 2002. For the al. 2009; Kozlev\u010d al. 2004. For sup al. 2013; Stibran al. 2009; Aaker\u00f6y al. 2003; Vald\u00e9s- al. 1993; Julve e al. 1984. For mol al. 1984; Mendy e al. 2010.2(C8Br4O4)2(C6H16N2)2(H2O)2] = 0.016wR(F2) = 0.039S = 1.073739 reflections245 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.80 e \u00c5\u22123\u0394\u03c1min = \u22120.41 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015015194/xu5866Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015194/xu5866fig1.tif. DOI: The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.Click here for additional data file.10.1107/S2056989015015194/xu5866fig2.tif. DOI: View of inter\u00adactions in the crystal.1418832CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atoms in the dication of the title structure, [(C6H5)2PCH2P(C6H5)2Au2]Cl2\u00b7(CH3)2C=O\u00b7H2O, show an aurophilic inter\u00adaction of 2.9743\u2005(2)\u2005\u00c5.The Au 2{(C6H5)2PCH2P(C6H5)2}]Cl2\u00b7(CH3)2C=O\u00b7H2O, the dication forms an eight-membered {\u2014PCPAu}2 ring with a transannular aurophilic inter\u00adaction [Au\u22efAu = 2.9743\u2005(2)\u2005\u00c5]. The ring approximates a flattened boat conformation, with the two methyl\u00adene C atoms lying ca 0.58\u20130.59\u2005\u00c5 above the least-squares plane defined by the Au2P4 atoms (r.m.s. deviation = 0.0849\u2005\u00c5). One Cl\u2212 anion functions as a weak bridge between the AuI atoms [Au\u22efCl = 2.9492\u2005(13) and 2.9776\u2005(12)\u2005\u00c5]. The second Cl\u2212 anion forms two (water)O\u2014H\u22efCl hydrogen bonds about a centre of inversion, forming a centrosymmetric eight-membered {\u22efHOH\u22efCl}2 supra\u00admolecular square. Globally, the dications and loosely associated Cl\u2212 anions assemble into layers lying parallel to the ac plane, being connected by C\u2014H\u22efCl,\u03c0(phen\u00adyl) inter\u00adactions. The supra\u00admolecular squares and solvent acetone mol\u00adecules are sandwiched in the inter-layer region, being connected to the layers on either side by C\u2014H\u22efCl,O(acetone) inter\u00adactions.In the title complex salt, [Au These compounds are cytotoxic and kill cancer cells by initiating apoptotic pathways  carbonimido\u00adthio\u00adates, 2C6H4} ]Cl2, was isolated as an acetone monosolvate monohydrate, (I)2(Ph2PCH2PPh2)]Cl2 salts characterized as an acetone solvate  thiol\u00adates, reactions with the bipodal mol\u00adecule, {1,4-[MeOC(=S)N(H)]2(Ph2PCH2PPh2)]2+ dication, two Cl\u2212 anions, and a solvent mol\u00adecule each of acetone and water; all species are in general positions. The mol\u00adecular structure of the dication is shown in Fig.\u00a01I atoms are bridged by two Ph2PCH2PPh2 ligands, forming an eight-membered {\u2014PCPAu}2 ring. The ring has the form of a boat with the methyl\u00adene-C1 and C2 atoms lying to one side of the ring and 0.589\u2005(5) and 0.581\u2005(5)\u2005\u00c5, respectively, above the least-squares plane through the Au2P4 atoms which have a r.m.s. deviation of 0.0849\u2005\u00c5. There is a transannular Au1\u22efAu2 (aurophilic) inter\u00adaction of 2.9743\u2005(2)\u2005\u00c5. This inter\u00adaction is partly responsible for the deviations of the P1\u2014Au1\u2014P3 and P2\u2014Au2\u2014P4 angles from the ideal 180\u00b0, i.e. 173.24\u2005(4) and 170.04\u2005(4)\u00b0, respectively. The Au\u2014P bond lengths are almost equivalent, ranging from a short Au1\u2014P1 2.3061\u2005(12) to a long Au2\u2014P4 2.3130\u2005(12)\u2005\u00c5. The Cl1\u2212 anion forms a weak bridge between the two AuI atoms with Au1\u22efCl1 and Au2\u22efCl2 separations of 2.9492\u2005(13) and 2.9776\u2005(12)\u2005\u00c5, respectively. The second Cl\u2212 anion participates in hydrogen bonding as described below in Supra\u00admolecular features.The asymmetric unit of (I)2 supra\u00admolecular squares with edge lengths of 3.217\u2005(5) and 3.200\u2005(5)\u2005\u00c5, Table\u00a01ac plane, corresponding to the inter-layer region between layers of dications and Cl1\u2212 anions, Fig.\u00a02\u2212 anion forms a single (phen\u00adyl)C\u2014H\u22efCl contact, a reduced propensity reflecting its close association with the AuI atoms (see above). By contrast, the Cl2\u2212 anion forms four independent C\u2014H\u22efCl2 inter\u00adactions, i.e. a (methyl\u00adene)C\u2014H\u22efCl2 and three (phen\u00adyl)C\u2014H\u22efCl2 inter\u00adactions, providing links between the {\u22efHOH\u22efCl}2 rings and the cations. The acetone solvent mol\u00adecule accepts a (methyl\u00adene)- and a (phen\u00adyl)C\u2014H\u22efO contact.The most notable feature of the crystal packing of (I)2(Ph2PCH2PPh2)]Cl2 salt has been characterized twice previously, originally as an acetone solvate 2(Ph2PCH2PPh2)]Cl2 salts relates to the mode of association between the complex Au cations and Cl\u2212 anions. As noted above and shown in Fig.\u00a04a, the Cl1\u2212 anion in (I)I atoms. In the acetone solvate \u2005\u00c5. A similar pattern is noted in the aceto\u00adnitrile solvate ]Cl2 salts with loosely associated Cl\u2212 anions having greater distortions from linearity, in particular for the acetone solvate (AuCl)2  in aceto\u00adnitrile (50\u2005ml) was added NaOH  and {1,4-[MeOC(=S)N(H)]2C6H4}  in aceto\u00adnitrile (50\u2005ml). The resulting mixture was stirred at 323\u2005K for 2\u2005h. The final product was extracted with di\u00adchloro\u00admethane (100\u2005ml) and the solution was left for evaporation at room temperature. After 3 weeks a slurry formed. This was redissolved in a solvent mixture of acetone/aceto\u00adnitrile  and left for slow evaporation. Colourless crystals were obtained after 10 days. Yield: 0.213\u2005g (43%). M.p. 477\u2013479\u2005K. 1H NMR : \u03b4 7.96 , 7.49 , 7.41 , 4.84 , 2.82 . Analysis calculated for C53H52Au2Cl2O2P4: C, 48.61; H, 4.00. Found: C, 48.64; H, 3.99. IR (cm\u22121): 3044 (m) \u03bd(C\u2014H), 1484 (s) \u03bd(C\u2014C).The title compound is an unexpected product from the reaction of bis\u00ad[chlorido\u00adgold(I)] bis\u00ad(di\u00adphenyl\u00adphosphane)methane with an equimolar amount of {1,4-[MeOC(=S)N(H)]Uiso(H) set to 1.2\u20131.5Uequiv(C). The water-bound H atoms were refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) = 1.5Uequiv(O). The U33 parameter was elongated for the C93 atom. In the final refinement this was restrained to be nearly isotropic using the ISOR command in SHELXL  I, global. DOI: 10.1107/S2056989015013341/wm5185Isup2.hklStructure factors: contains datablock(s) I. DOI: 1412185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title platinum(II) complex shows a trigonal\u2013bipyramidal coordination and inter\u00admolecular C\u2014H\u22efCl, C\u2014H\u22ef\u03c0 and (C/O)\u2014H\u22efO hydrogen bonds. 11H13O2)Cl(C5H11N)]\u00b7C2H5OH, the PtII cation is penta\u00adcoordinated in a distorted square-planar geometry. In the crystal, inversion dimers showing C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions are further stacked in columns along the a axis via C\u2014H\u22ef\u03c0 inter\u00adactions. The ethanol solvate mol\u00adecule inter\u00adacts with neighbouring meth\u00adoxy groups of methyl\u00adeugenol through O\u2014H\u22efO hydrogen bonds.In the title compound, [Pt(C In order to avoid steric hindrance between Cl1 and the two ring systems, especially atoms C2 and C12, both rings rotate along their bond with Pt1. This is easier for the piperidine ring [resulting in a C12\u2014N1\u2014Pt1\u2014Cl1 torsion angle of 70.7\u2005(2)\u00b0] than for the phenyl ring [C2\u2014C1\u2014Pt1\u2014Cl1 torsion angle of only \u221225.0\u2005(4)\u00b0]. As a consequence the H12B\u22efCl1 distance (2.831\u2005\u00c5) is larger than the H2\u22efCl1 distance (2.789\u2005\u00c5).In [PtCl(Meug-1H)(piperidine)], the Ptom Fig.\u00a01. The twoA\u22efCg1 inter\u00adactions, Cg1 is the centroid of the C1\u2013C6 aromatic ring, see Table\u00a01A\u22efCg1 inter\u00adactions. The ethanol mol\u00adecule inter\u00adacts by bifurcated O\u2014H\u22efO hydrogen bonds with both meth\u00adoxy groups of methyl\u00adeugenol and further on by C\u2014H\u22efO inter\u00adactions to a neighboring meth\u00adoxy group. No voids are present in the crystal packing.In the crystal packing Fig.\u00a02, the com3 torsion angles vary between \u221228 and +32\u00b0 (only 11 torsion angles are outside this region).The Cambridge Structural Database 2] was prepared from K[PtCl3(Meug)] in high yield (85%) according to Da et al. 2] and 6ml of acetone. The reaction mixture was stirred at room temperature for 30\u2005min. The obtained solution was cooled to 255\u2005K after which the precipitate was collected and washed with Et2O. The yield was 320\u2005mg (65%). The powder was dissolved in an acetone\u2013ethanol mixture. Colourless plate-like crystals were harvested after slow evaporation of acetone at room temperature.The title compound was synthesized by adding a solution of 1\u2005mmol of piperidine in 3\u2005ml of acetone to a mixture of 408\u2005mg (0.5\u2005mmol) of : C16H24ClNO2Pt, M = 491\u2013495 au; found : 490\u2013494 ([M\u2212H]+).IR  with C\u2014H distances of 0.95 (aromatic), 0.98 (meth\u00adyl) and 0.99\u2005\u00c5 (methyl\u00adene), N\u2014H distance of 0.93 (NH) and O\u2014H distance of 0.84\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814023575/rz5134sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023575/rz5134Isup2.hklStructure factors: contains datablock(s) I. DOI: 1031185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the brightly green fluorescent Zn-complex of the hardly luminescent dipyrrin, the metal ion is bound by two dipyrrin ligands, as revealed first by its mass spectra. The crystal structure of this Zn-complex of the dipyrrin confirmed a regular 2:1 composition of the bidentate dipyrrin ligand and the metal ion. The latter was coordinated in a distorted tetrahedral fashion, as found in other dipyrrin Zn-complexes. The here studied Zn-complex of a designed dipyrrin ligand provides insights into the coordination properties of the proposed (2:1)- and (2:2)-complexes of phylloxanthobilin and bilirubin, respectively, which are two abundant natural bilin-type tetrapyrroles.A high yield preparation, spectroscopic and crystallographic investigation of the crystalline Zn-complex of a di( Dipyrrins (or dipyrromethenes) feature two conjugated pyrrole rings and represent  dipyrrolic building blocks for the construction of porphyrins and related tetrapyrrolic macrocycles . The com\u03b2,\u03b2\u2032-sulfoleno)pyrrin 2.In the context of our recent interest in the metal coordination properties of yellow chlorophyll catabolites (phylloxanthobilins) , and of \u03b2,\u03b2\u2032-sulfoleno)pyrrin 2 relied on the earlier made corresponding dipyrromethane (1), available, in turn, from condensation of 3,5-di-tert-butylbenzaldehyde and \u03b2,\u03b2\u2032-sulfolenopyrrole + at m/z\u00a0=\u00a01087.2. Corresponding significant fragments occurred at m/z\u00a0=\u00a01023.3, 894.4, and 830.4, due to consecutive loss of the one, three, and four SO2-groups, respectively. The derived molecular formula of the Zn-complex 3 suggested the presence of two dipyrrin ligands 2 and one Zn(II)-ion, i.e. to represent Zn-(2)2 (see Scheme\u00a0The molecular formula of the dipyrrin Zn-complex 3 displayed a UV/Vis-spectrum in CH2Cl2 that featured a maximum at 487\u00a0nm (and a shoulder at 463\u00a0nm), corresponding to a 51\u00a0nm bathochromic shift, when compared with the spectrum of the dipyrrin 2 (see above). Similar bathochromic shifts of the absorption spectrum upon coordination of a Zn(II) ion were observed in Zn-complexes of bilirubin , a signal of an HN was lacking (which was found at 12.76\u00a0ppm in the spectrum of the dipyrrin 2), consistent with bidentate binding of the dipyrrin ligand 2 to the coordinated Zn(II) ion. Signals of aryl-o hydrogens and aryl-p hydrogen are slightly shifted to lower field while signals of \u03b2-methylene groups and pyrrole-\u03b1 hydrogens are slightly moved to higher field.In the 3 grew from a solution of 3 in CH2Cl2 when n-C6H14 was mixed in slowly at 4\u00a0\u00b0C. The Zn-complex 3 crystalized in the triclinic system with space group P-1 (no. 2). A unit-cell contained four molecules of 3. The crystal structure of 3 showed two bidentate dipyrrin moieties wrapped around one Zn(II) center leading to coordination in a distorted tetrahedral fashion with N\u2013Zn\u2013N angles of about 94, 113, and 121\u00b0  Zn-complexes -cycloaddition reactions. As was recently developed with porphyrinoids, such as tetra-sulfolenoporphyrins  were reagent grade commercial chemicals from Fluka and were used as received; EtOAc, dichloromethane, methanol (MeOH), and n-C6H14 were from Acros and were distilled before use. Column chromatography (CC): Fluka silica gel 60 (230\u2013400 mesh). Thin layer chromatography (TLC): Merck 0.25\u00a0mm silica gel 60 plates. Equipment: UV/Vis: Agilent Cary 60 UV\u2013Visible, \u03bbmax in nm (log \u03b5). Fluorescence (FL): Varian Cary Eclipse, \u03bb in nm (rel. intensity); Nuclear magnetic resonance (1H) spectra: Bruker 300 at 298K, chemical shifts (\u03b4) in ppm, with \u03b4 (CHCl3)\u00a0=\u00a07.26\u00a0ppm, signal assignment follows the X-ray numbering scheme. FAB-MS: Finnigan MAT-95, positive ion mode, NOBA matrix; X-ray analyses: data collection on a Nonius Kappa CCD, equipped with graphite mono-chromatized Mo-K\u03b1-radiation (\u03bb\u00a0=\u00a00.71073\u00a0\u00c5) at 233K. Melting point: B\u00fcchi 535.Dichlorodicyano-1 (3.8\u00a0\u03bcmol) +), 894.4 ([M\u20133SO2]+), 830.4 ([M\u20134SO2]+).Dipyrrin 54H62N4O8S4Zn\u00a0\u00d7\u00a0CH2Cl2\u00a0\u00d7\u00a00.75 C6H14, formula weight: 1238.24; temperature 233(2)\u00a0K; radiation wavelength 0.71073\u00a0\u00c5; crystal system triclinic; space group P-1 (no. 2); unit cell dimensions a\u00a0=\u00a018.5998(4)\u00a0\u00c5, b\u00a0=\u00a018.9173(3)\u00a0\u00c5, c\u00a0=\u00a021.6741(5)\u00a0\u00c5, \u03b1\u00a0=\u00a098.771(1)\u00b0, \u03b2\u00a0=\u00a0104.394(1)\u00b0, \u03b3\u00a0=\u00a0109.204(1)\u00b0; volume 6743.1(2) \u00c53; Z\u00a0=\u00a04; density  1.220\u00a0g/cm3; absorption coefficient 0.618\u00a0mm\u22121; crystal size 0.45\u00a0\u00d7\u00a00.25\u00a0\u00d7\u00a00.03\u00a0mm3; F(000) 2606; theta range for data collection 1.335\u00b0\u201324.145\u00b0; index ranges \u221221\u00a0\u2264\u00a0h\u00a0\u2264\u00a021, \u221221\u00a0\u2264\u00a0k\u00a0\u2264\u00a021, \u221224\u00a0\u2264\u00a0l\u00a0\u2264\u00a024; reflections collected 36397; independent reflections 21231 [R(int)\u00a0=\u00a00.0379]; completeness to theta (24.145\u00b0) 98.5\u00a0%; absorption correction none; refinement method Full-matrix least-squares on F2; data/restraints/parameters 21231/29/1489; goodness-of-fit on F2 1.032; final R indices [I\u00a0>2\u03c3(I)] R1\u00a0=\u00a00.0769, wR2\u00a0=\u00a00.1998; R indices  R1\u00a0=\u00a00.1148, wR2\u00a0=\u00a00.2209. Crystallographic data of 3 (Zn-(2)2) (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC no. 1453954. Copies of the data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://summary.ccdc.cam.ac.uk/structure-summary-form.Crystallographic data: C"}
{"text": "S(6) ring and therefore establishes a syn relationship for the N atoms. In the crystal, mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds, generating [100] chains containing alternating A and B mol\u00adecules.The two mol\u00adecules of 2-(2-amino\u00adphen\u00adyl)-1,3-benzoxazole in the asymmetric unit feature an intra\u00admolecular N\u2014H\u22efN hydrogen bond, which closes an  13H10N2O, were grown from a di\u00adchloro\u00admethane/ketone/methanol solvent mixture. It crystallizes with two mol\u00adecules, A and B, in the asymmetric unit with very similar almost planar conformations . Each mol\u00adecule features an intra\u00admolecular N\u2014H\u22efN hydrogen bond, which closes an S(6) ring and therefore establishes a syn relationship for the N atoms. In the crystal, mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds, generating [100] chains containing alternating A and B mol\u00adecules. Weak aromatic \u03c0\u2013\u03c0 stacking [minimum centroid\u2013centroid separation = 3.6212\u2005(9)\u2005\u00c5] links the chains into a three-dimensional network.Crystals of the title compound, C The oriA and B, respectively. The dihedral angles between the benzene ring and the fused ring system are 0.74\u2005(8) and 0.67\u2005(6)\u00b0 for mol\u00adecules A and B, respectively. The two independent mol\u00adecules are very similar, with an r.m.s. overlay fit of 0.019\u2005\u00c5.The skeleton of each mol\u00adecule is practically planar: to analyse the planarity of the mol\u00adecule we use the torsion angle N3\u2014C2\u2014C8\u2014C9, indicating the rotation of the aromatic ring C8\u2014C13: these angles are \u22121.2\u2005(2) and 0.9\u2005(2)\u00b0 for mol\u00adecules 2 group forms an intra\u00admolecular hydrogen bond of the type N2\u2014H2B\u22efN3 (Table\u00a01A and 2.146\u2005(18)\u2005\u00c5 in mol\u00adecule B, and an inter\u00admolecular N2\u2014H2A\u22efN2 hydrogen bond with a distance of 2.289\u2005(15)\u2005\u00c5 for N2\u2014H2A\u22efN2\u2032 and 2.522\u2005(16)\u2005\u00c5 for N2\u2032\u2014H2A\u2032\u22efN2, forming zigzag chains propagating in the [100] direction and containing alternating A and B mol\u00adecules  of o-amino\u00adphenol were added followed by the addition of 0.30\u2005ml (10% mol) of a solution of ZnCl2 (1 M). The mixture was then stirred and heated slowly to reflux temperature during 18\u2005h. The crude reaction product was concentrated on a rotary evaporator with an azeotropic mixture of AcOEt/xylene to obtain a reddish brown solid which was dissolved in EtOAc and washed with 10% aq. NaCl solution. The crude reaction product was purified by column chromatography to give 356\u2005mg (55%) of the amine (I)\u03b3max cm\u22121: 3408 NH2, 3051 C\u2014H(arom), 1624 C=N; : \u03b4 = 6.20 , 6.79 , 7.29 , 7.33 , 757 , 7.72 , 8.09 ; 13C NMR  \u03b4 = 108.7, 110.4, 116.3, 116.8, 119.4, 124.3, 124.8, 128.8, 132.5, 141.9, 147.9, 149.3, 163.2 . Analysis calculated for C13H10N2O: C, 74.27; H, 4.79%; Found: C, 74.43; H, 5.05%.500\u2005mg (3.00\u2005mmol) of isatoic anhydride were dissolved in 50\u2005mL of sage 2003; 1H NMR The single crystal used in the experiment was obtained by the method of liquid\u2013liquid diffusion by slow evaporation. The pure compound was dissolved in the minimum amount of di\u00adchloro\u00admethane to be added by the walls of the tube the same amount of acetone followed by methanol. The tube was sealed to leave the solution in a vibration-free environment at room temperature. After a few days, the solution had evaporated, leaving colourless blocks of the title compound.isoU(H) = 1.2eqU(C). Hydrogen atoms of the amine group were found in a difference map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015000481/hb7320sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015000481/hb7320Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015000481/hb7320Isup3.cmlSupporting information file. DOI: 1042858CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, the sulfonamide N\u2014H group forms an inter\u00admolecular hydrogen bond to the amine N atom. 15H24N2O2S, was synthesized via a substitution reaction between the enanti\u00adopure -(+)-1,2-di\u00adamino\u00adcyclo\u00adhexane and 2,4,6-tri\u00admethyl\u00adbenzene-1-sulfonyl chloride. The cyclo\u00adhexyl and phenyl substituents are oriented gauche around the sulfonamide S\u2014N bond. In the crystal, mol\u00adecules are linked via N\u2014H\u22efN hydrogen bonds, forming chains propagating along [100].The title compound, C A weak intra\u00admolecular inter\u00adaction is present between the amine H2A atom and the sp2-hybridized sulfonamide N1 atom  inter\u00adactions with an H2B\u22efO1 distance of 2.72\u2005\u00c5 between the donor amine N2\u2014H2B and the acceptor sulfonamide O1 atoms can also be noticed within this chain.Mol\u00adecules of the title compound are held together in the solid state by inter\u00admolecular hydrogen-bonding inter\u00adactions between the donor sulfonamide N1\u2014H1 and the acceptor amine N2 atoms Table\u00a01. These hD\u22efH = 0.860\u2005(7)\u2005\u00c5; H\u22efA = 2.160\u2005(8)\u2005\u00c5; D\u22efA = 3.011\u2005(8)\u2005\u00c5; D\u2014H\u22efA = 169.9\u2005(5)\u00b0].As for the racemic crystal FAVHEP, in the model deposited in the CSD there is one inter\u00admolecular hydrogen bond present between a donor sulfonamide N1\u2014H1 and a nearby amine acceptor N atom [et al., 2012et al., 2014et al., 2010trans-1,2-di\u00adamino\u00adcyclo\u00adhexane ring are bonded to a mesitylsulfonamide group. Structure FAVHEP -(+)-1,2-di\u00adamino\u00adcyclo\u00adhexane  in 5\u2005ml of CH2Cl2 at 273\u2005K was added a solution of 2,4,6-tri\u00admethyl\u00adbenzene-1-sulfonyl chloride  in 5\u2005ml CH2Cl2. After the addition was complete (20\u2005min), the mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was washed with H2O (3 \u00d7 25\u2005ml) and the aqueous layer was back-extracted with CH2Cl2 (20\u2005ml). The combined organic extracts were dried over Na2SO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography over silica gel (CH2Cl2/EtOAc 1:1 v/v) to afford a pale-yellow\u2013white solid . Part of the purified product was redissolved in CH2Cl2 and after slow evaporation for several days, white large chunky crystals (stained yellow) were formed that were suitable for analysis by X-ray diffraction (m.p. 406\u2013407\u2005K).To a stirred solution of (1Uiso(H) = 1.2Ueq(C) for methine, methyl\u00adene and aryl groups, and Uiso(H) = 1.5Ueq(C) for methyl groups. H atoms bonded directly to N atoms  were located in difference-Fourier maps and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901502191X/gk2646sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901502191X/gk2646Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502191X/gk2646Isup3.cmlSupporting information file. DOI: 1437453CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "L2(H2O)4]\u00b72H2O , the CdII ion is situated on an inversion centre being coordinated by four aqua mol\u00adecules in the equatorial plane and two deprotonated phospho\u00adnate O atoms from two L ligands in the axial positions in a distorted octa\u00adhedral geometry. Each ligand L exists in a zwitterionic form, and with an intra\u00admolecular O\u2014H\u22efO inter\u00adaction forming an S(6) ring motif and two intra\u00admolecular N\u2014H\u22efO inter\u00adactions each generating an S(5) ring motif. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link complex mol\u00adecules into a three-dimensional network with voids of 38\u2005\u00c53 filled with ordered lattice water mol\u00adecules, which are also involved in O\u2014H\u22efO hydrogen bonding.In the compound [Cd L2(H2O)4]\u00b72H2O , the CdII ion is situated on an inversion centre being coordinated by four aqua mol\u00adecules in the equatorial plane and two phosphonate O atoms from two deprotonated L ligands in the axial positions in a distorted octa\u00adhedral geometry. The asymmetric unit contains one-half of the complex mol\u00adecule and one lattice water mol\u00adecule. The ligand L exists in a zwitterionic form, with a positive charge on the NH3 group and a negative charge on the O atom of the non-coordinating phospho\u00adnate group, and with an intra\u00admolecular O\u2014H\u22efO inter\u00adaction forming an S(6) ring motif and two intra\u00admolecular N\u2014H\u22efO inter\u00adactions each generating an S(5) ring motif. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the complex mol\u00adecules into a three-dimensional network in which the voids of 38\u2005\u00c53 are filled with ordered lattice water mol\u00adecules, which are also involved in O\u2014H\u22efO hydrogen bonding.In the title compound, [Cd All bond lengths and angles in (I)et al., 1991et al., 1997et al., 2005et al., 2006et al., 2007et al., 2007et al., 2009et al., 2010et al., 2010II atom occupies a special position on an inversion centre and shows a slightly distorted octa\u00adhedral coordination environment formed by two phospho\u00adnic O atoms in trans positions and four aqua O atoms in the equatorial plane. The distorted octa\u00adhedral coordination polyhedron is slightly compressed in the axial direction; the Cd1\u2014O2 bond length is 0.1\u2005\u00c5 shorter than the Cd1\u2014O1W and Cd1\u2014O2W bonds. The values of the axial O\u2014Cd\u2014O angles are in the range 80.1\u2005(4)\u201399.9\u2005(4)\u00b0, indicating a significant deviation from ideal values. The ligand L exists in a zwitterionic form, with a positive charge on the NH3 group and a negative charge on the O atom of the non-coordinating phosphonate group, and with an intra\u00admolecular O\u2014H\u22efO inter\u00adaction forming an S(6) ring motif and two intra\u00admolecular N\u2014H\u22efO inter\u00adactions each generating an S(5) ring motif f Table\u00a01.b axis. Inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds  at 273\u2005K to produce the title compound (I)1H and 13C{1H} NMR spectra were recorded on a Bruker Bio spin 400 spectrometer.All reactions and manipulations were carried out in air with reagent grade solvents. 1-Amino\u00adethane-1,1-diyldi\u00adphospho\u00adnic acid was prepared according to the literature method of Rukiah & Assaad 2013. The titSpectroscopic data for (I)1H NMR : \u03b4 1.67 . 13C{1H} NMR : \u03b4 20.5 , 54.7 . 31P{1H} NMR : \u03b4 13.61. IR : 3446.2 (NH3), 2351.5 (POH), 1605.0 (O=P\u2014O\u2014H).\u03b11 radiation (\u03bb= 1.54060\u2005\u00c5) selected with an incident-beam curved-crystal Ge(111) monochromator with a linear position-sensitive detector (PSD). The pattern was scanned over the angular range 6.0\u201390.0\u00b0 (2\u03b8). For pattern indexing, extraction of the peak positions was carried out with the program WinPLOTR  = 37.1, F(20) = 78.5]. The best estimated monoclinic space group was P21/c.Crystal data, data collection and structure refinement details are summarized in Table\u00a02et al., 1988FULLPROF . These \u03bc\u00b7d values were determined experimentally. The preferred orientation was modelled with 12 coefficients using a spherical harmonics correction  = 0.011009 and \u03c72 = 8.940) indicate that the preferred orientation improvement of the refinement is considerable.The powder pattern was subsequently refined with cell and resolution constraints  on bond lengths were applied to normal values for these bonds. The final refinement cycles were performed varying isotropic displacement parameters for Cd and water O atoms, and fixed isotropic displacement parameters for P, C, N,O and H atoms. The final Rietveld plot is shown in Fig.\u00a03Before the final refinement, the H atoms of the CH10.1107/S2056989015004028/cv5484sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004028/cv5484Isup2.rtvRietveld powder data: contains datablock(s) I. DOI: 1051338CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Nature Communications7: Article number: 10269 10.1038/ncomms10269 (2016); Published: 01052015; Updated: 05112016x axis in Supplementary Figure 3 (lower panel). The x axis in this panel should have been labelled \u201822\u2009\u00b0C Mock; 22\u2009\u00b0C GDA; 29\u2009\u00b0C Mock; 29\u2009\u00b0C GDA'. The correct version of this figure appears below.This Article contains errors in the labelling of the Supplementary Figure 3"}
{"text": "The cyclo\u00adhexene ring adopts an envelope conformation in both mol\u00adecules, with the C atom to which is attached the central benzene ring as the flap. The crystal packing, is stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions. 27H26O3, crystallized with two independent mol\u00adecules (A and B) in the asymmetric unit. In mol\u00adecule A, the plane of the central benzene ring forms dihedral angles of 75.78\u2005(14) and 52.75\u2005(16)\u00b0 with that of the terminal benzene rings, and the dihedral angle between the planes of the terminal benzene rings is 51.49\u2005(17)\u00b0. The corresponding values for mol\u00adecule B are 75.18\u2005(14), 58.11\u2005(16) and 47.91\u2005(16)\u00b0, respectively. The cyclo\u00adhexene ring adopts an envelope conformation in both mol\u00adecules, with the C atom to which is attached the central benzene ring as the flap. The crystal packing, is stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions.The title compound, C Cyclo\u00adhexenone and cyclo\u00adhexenone derivatives are known for anti-inflammatory and analgesic activities  in the asymmetric unit  and 1.224\u2005(3)\u2005\u00c5, respectively, indicate double-bond character. In both mol\u00adecules, the C\u2014O bond lengths are in the range 1.362\u2005(3)\u20131.414\u2005(4)\u2005\u00c5 and represent single-bond character. In mol\u00adecule A, the torsion angles C5\u2014C4\u2014C7\u2014C8 = 69.2\u2005(4)\u00b0 and C24\u2014C9\u2014C10\u2014C11 = \u221216.0\u2005(4)\u00b0 show that the benzyl\u00adoxyphenyl and meth\u00adoxy\u00adphenyl groups have a +sc and -sp orientation with respect to the cyclo\u00adhexene moiety. The arrangement in mol\u00adecule B is slightly different, with torsion angles C5A\u2014C4A\u2014C7A\u2014C8A = 111.5\u2005(3)\u00b0 and C24A\u2014C9A\u2014C10A\u2014C11A = 20.8\u2005(4)\u00b0. The cyclo\u00adhexene ring in both mol\u00adecules adopts an envelope conformation with atoms C7 and C7A as the flaps in mol\u00adecules A and B, respectively.The title compound crystallized with two mol\u00adecules -3-(4-Benzyl\u00adoxyphen\u00adyl)-1-(4-meth\u00adoxy\u00adphen\u00adyl)prop-2-en-1-one was synthesized following the literature procedure of Ezhilarasi et al. -3-(4-benzyl\u00adoxyphen\u00adyl)-1-(4-meth\u00adoxy\u00adphen\u00adyl)prop-2-en-1-one (0.01\u2005mol) and ethyl methyl ketone (0.01\u2005mol) were refluxed in absolute alcohol (50\u2005ml) in the presence of 10% sodium hydroxide solution (10\u2005ml) for 1\u2005h in an oil bath. The reaction mixture was then cooled and the precipitate obtained filtered, washed with distilled water and dried. The crude product was recrystallized twice from absolute alcohol (yield 80%), giving yellow block-like crystals. = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989014025390/su5016sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989014025390/su5016Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014025390/su5016Isup3.cmlSupporting information file. DOI: 1035112CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The sulfonate group is disordered over two positions with occupancy factors of 0.655\u2005(5) and 0.345\u2005(5). The hexa\u00adaqua\u00adnickel(II) cation inter\u00adacts through hydrogen bonding with eight QOH mol\u00adecules and two water mol\u00adecules. The six-membered rings of quinoline show \u03c0\u2013\u03c0 stacking [centroid-to-centroid distances of 3.679\u2005(2)\u2005\u00c5 and 3.714\u2005(2)\u2005\u00c5].The asymmetric unit of the title compound, [Ni(H Quinine, cinchonine, chloro\u00adquine, plasmoquine and acriquine, for instance, are known to be able to cure malaria  has been synthesized from eugenol and its anti\u00adbacterial activities have been reported . As quinoline rings are known to complex with metal ions, the formation of a complex between QOH and NiII was studied. The reaction product, however, could not be characterized unambiguously by IR or 1H NMR spectroscopic methods. The spectroscopic data are different from those obtained for free QOH and in favour of a deprotonated carb\u00adoxy\u00adlic acid group, but give no indication about a possible complex formation. X-ray diffraction now shows that QOH is not complexing directly with NiII.Recently, the new quinoline derivative 6-hy\u00addroxy-3-sulfoquinolin-7-yloxyacetic 6]2+ is located about an inversion center and has an octa\u00adhedral volume of 11.629\u2005\u00c53 with Ni\u2014O bond lengths between 2.034\u2005(3) and 2.106\u2005(2)\u2005\u00c5.The structure determination shows that the carboxyl group of rm Fig.\u00a01, which wQOH moieties and two water mol\u00adecules through O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding (Table\u00a01The hexa\u00adaqua\u00adnickel(II) cation plays the role of glue in the crystal packing. In total, it inter\u00adacts with eight g Table\u00a01.Cg1\u22efCg1ix = 3.679\u2005(2)\u2005\u00c5, Cg1\u22efCg2ix = 3.714\u2005(2)\u2005\u00c5; Cg1 and Cg2 are the centroids of the rings C12/C13/N14/C15\u2013C17 and C15/C16/C18\u2013C21, respectively; symmetry code: (ix) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01; Fig.\u00a03Furthermore, \u03c0\u2013\u03c0 stacking between the quinoline rings results in the formation of inversion dimers [QOH mol\u00adecule and furthermore with the sulfonate group (O7) of a second QOH mol\u00adecule and the hexa\u00adaqua complex (O2). Whereas hydroxyl group O23\u2014H23 only inter\u00adacts with water mol\u00adecule O29, the second hydroxyl group O22\u2014H22 is involved in the formation of another type of inversion dimers through C\u2014H\u22efO hydrogen bonding and inter\u00adacts with a sulfonate group (O8) (Table\u00a01Lattice water mol\u00adecule O29 inter\u00adacts with the carboxyl\u00adate (O27) and hydroxyl (O23) groups of a neighboring ) Table\u00a01.A search of the Cambridge Structural Database  was synthesized and further transformed to 5,6-dihy\u00addroxy-3-sulfoquinolin-7-yloxyacetic acid (QOH) according to a procedure described by Dinh et al.  in ethanol\u2013water  was added dropwise to a solution of QOH  in ethanol\u2013water . The obtained solution was stirred for three hours, at 313\u2013323\u2005K, during reflux. A few days later, the green\u2013yellow precipitate was collected by filtration, washed consecutively with ethanol and diethyl ether and dried in vacuo. The obtained crystals are soluble in water and DMSO, but only slightly soluble in ethanol, acetone and chloro\u00adform. The yield was 65%. Single crystals suitable for X-ray investigation were obtained by slow evaporation from a ethanol\u2013water (1:1 v/v) solution at room temperature. IR : 3420 (\u03bdOH); 3080, 2918 (\u03bdC-H); 1620 (\u03bdCOOas); 1426(\u03bdCOOs); 1528 (\u03bdC=Cring or \u03bdC=N); 466 (\u03bdNi-O). 1H NMR : \u03b4 8.74 , 8.17 , 7.2 , 4.64 ; : \u03b4 9.26 , 9.01 , 7.01 , 4.80 .A solution containing NiClB, H3B, H4B, H14, H29A and H29B were located in difference Fourier maps. All other H atoms were placed at idealized positions and refined in riding mode, with C\u2014H distances of 0.95 (aromatic) and 0.99\u2005\u00c5 (methyl\u00adene), and O\u2014H distances of 0.84\u2005\u00c5. The H atoms of water mol\u00adecule O29 were refined with an O\u2014H distance restraint of 0.85\u2005\u00c5 and H\u22efH distance restraint of 1.39\u2005\u00c5. For all H atoms, Uiso(H) values were assigned as 1.2Ueq of the parent atoms (1.5Ueq for H22 and H23). The SO3 group is disordered over two positions, the occupancy ratio refines to 0.655\u2005(5):0.345\u2005(5) for part 1  and part 2 , respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015662/vn2096sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015662/vn2096Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419884CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports5 Article number: 14289; 10.1038/srep14289 published online: 09232015; updated: 12182015.In Supplementary Figure 1a, the Linzizong volcanic rock samples \u201812LZ14-1\u2019 and \u201812LZ13-1\u2019 should read \u201813LZ14-1\u2019 and \u201813LZ13-1\u2019 respectively. The correct Supplementary Figure 1a appears below as In Table S1, samples \u201812LZ13-1@02\u2019 and \u201812LZ14-1@02\u2019 should read \u201813LZ13-1@02\u2019 and \u201813LZ14-1@02\u2019 respectively."}
{"text": "The angles at the NiII cation, which lies on a twofold rotation axis, are Cl\u2014Ni\u2014Cl = 115.58\u2005(3)\u00b0 and S\u2014Ni\u2014S = 94.55\u2005(3)\u00b0. All other angles at the central NiII atom range from 109.46\u2005(2) to 112.96\u2005(2)\u00b0. The C\u2014S\u2014Ni angle is 99.91\u2005(6)\u00b0. The planes of two imidazolium rings make a dihedral angle of 70.56\u2005(6)\u00b0.In the mol\u00adecular structure of the title compound, [NiCl DOI: 10.1107/S2056989015012281/hp2071Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015012281/hp2071fig1.tif. DOI: Mol\u00adecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level.1408996CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit consists of one Cd2+ cation, two thio\u00adcyanate anions and two 4-(hy\u00addroxy\u00admeth\u00adyl)pyridine ligands in general positions. Two Cd2+ cations are linked by two \u03bc-1,3 N- and S-bonding thio\u00adycanate anions into dimers which are further linked into branched chains along [100] by two \u03bc-1,6 N- and O-bonding 4-(hy\u00addroxy\u00admeth\u00adyl)pyridine ligands. One additional N-bonded 4-(hy\u00addroxy\u00admeth\u00adyl)pyridine ligand and one additional N-bonded thio\u00adcyanate anion are only terminally bonded to the metal cation. Inter\u00adchain O\u2014H\u22efS hydrogen bonds between the hy\u00addroxy H atoms and one of the thio\u00adcyanate S atoms connect the chains into a three-dimensional network.The crystal structure of the title compound, [Cd(NCS) DOI: 10.1107/S2056989015008890/wm5156Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008890/wm5156fig1.tifx y z x y z . DOI: x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (ii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01.]Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) \u2212Click here for additional data file.10.1107/S2056989015008890/wm5156fig2.tif. DOI: Crystal structure of the title compound in a view approximately along [001]. Inter\u00admolecular O\u2014H\u22efS hydrogen bonding is shown as dashed lines; the disordered pyridine rings are omitted for clarity.1063786CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Solvent-dependent outcomes are noted in co-crystallization experiments between DABCO and 4-nitrobenzoic acid with mono- and diprotonated forms of DABCO are isolated. 6H13N2+\u00b7C7H4NO4\u2212\u00b72H2O, (1), whereas from methanol, the salt C6H14N22+\u00b72C7H4NO4\u2212, (2), was isolated. In (1), the cation and anion are linked by a strong N\u2014H\u22efO hydrogen bond, and the carboxyl\u00adate anion is close to planar [dihedral angle between terminal residues = 6.83\u2005(9)\u00b0]. In (2), a three-ion aggregate is assembled by two N\u2014H\u22efO hydrogen bonds, and the carboxyl\u00adate anions are again close to planar [dihedral angles between terminal residues = 1.7\u2005(3) and 5.9\u2005(3)\u00b0]. Through the inter\u00advention of solvent water mol\u00adecules, which self-assemble into helical supra\u00admolecular chains along the b axis, the three-dimensional architecture in (1) is stabilized by water\u2013DABCO O\u2014H\u22efN and water\u2013carboxyl\u00adate O\u2014H\u22efO hydrogen bonds, with additional stability afforded by C\u2014H\u22efO inter\u00adactions. The global crystal structure comprises alternating layers of water mol\u00adecules and ion pairs stacked along the c axis. In the crystal of (2), the three-ion aggregates are assembled into a three-dimensional architecture by a large number of methyl\u00adene\u2013carboxyl\u00adate/nitro C\u2014H\u22efO inter\u00adactions as well as \u03c0\u2013\u03c0 contacts between inversion-related benzene rings [inter-centroid distances = 3.5644\u2005(16) and 3.6527\u2005(16)\u2005\u00c5]. The cations and anions assemble into alternating layers along the c axis.The 1:1 co-crystallization of 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octane (DABCO) with 4-nitro\u00adbenzoic acid in ethanol\u2013water (3/1) gave the salt dihydrate C In this context, it is not surprising that a search of the Cambridge Structural Database  comprises a 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octan-1-ium mono-cation, a 4-nitro\u00adbenzoate anion and two water mol\u00adecules of hydration Fig.\u00a01. The mosi.e. 1.281\u2005(3) and 1.228\u2005(3)\u2005\u00c5, is slightly greater than that in C8\u2014O5, O6 of 1.273\u2005(3) and 1.231\u2005(3)\u2005\u00c5, respectively. In each case the longer bond forms a strong N\u2014H\u22efO hydrogen bond  and 8.7\u2005(2)\u00b0, respectively, and the dihedral angle between the terminal groups is 1.7\u2005(3)\u00b0. The comparable angles for the O5-containing anion are 2.2\u2005(3), 7.4\u2005(2) and 5.9\u2005(3)\u00b0, respectively. As discussed below in Supra\u00admolecular features, the ions participate in strong N\u2014H\u22efO hydrogen bonds, forming a three-ion aggregate  comprises a 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octane-1,4-diium di-cation and two 4-nitro\u00adbenzoate anions Fig.\u00a02. In the d Table\u00a02. In ordete Fig.\u00a02 in whichb axis. Adjacent columns stack along the a axis to form layers in the ab plane. The layers are inter\u00adspersed by layers of water mol\u00adecules which self-assemble into helical chains along the b axis, where each independent water mol\u00adecule donates and accepts a water-O\u2014H\u22efO(water) hydrogen bond (Table\u00a01In (1), the cation and anion are linked by a strong N2\u2014H\u22efO1 hydrogen bond Fig.\u00a01. The twod Table\u00a01. This led Table\u00a01.W\u2014H\u22efN3 and water-OW2\u2014H\u22efO2(carboxyl\u00adate). Additional stability to the supra\u00admolecular assembly is afforded by methyl\u00adene-C\u2014H\u22efO2(carboxyl\u00adate) and O2W(water) inter\u00adactions; it is noteworthy that both of the former inter\u00adactions involve hydrogen atoms derived from the same methyl\u00adene-C12 atom \u2005\u00c5 for inter\u00adactions between the C2\u2013C8 rings  and 3.6527\u2005(16)\u2005\u00c5 between C9\u2013C14 rings . An alternate description of the global crystal packing is based on alternating of layers of cations and layers of anions along the c axis , the di-cation is linked to two anions ds Fig.\u00a04. Globall\u00c5 Table\u00a02. All int\u00c5 Table\u00a02. Additiois Fig.\u00a05.Chemical context, there are 57 species in the crystallographic literature containing DABCO or its mono- or diprotonated forms and a carb\u00adoxy\u00adlic acid or carboxyl\u00adate anion. In fact, co-crystals are rare, being around 10% of all structures. Co-crystals are formed with several di\u00adcarb\u00adoxy\u00adlic acids where the functional groups are separated by long chains of over four carbon atoms , was mixed with 4-nitro\u00adbenzoic acid  in a solution containing ethanol (30\u2005ml) and water (10\u2005ml). The solution was heated for 2\u2005h at 350\u2005K. The mixture was then left for slow evaporation and colourless crystals of (1) formed after 4 days. In a similar experiment, 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octane  was mixed with 4-nitro\u00adbenzoic acid  in a solution of methanol (50\u2005ml). The solution was heated for 2\u2005h at 345\u2005K. The mixture was then left for slow evaporation and colourless crystals of (2) formed after 4 days.Uiso(H) = 1.2Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint: N\u2014H = 0.88\u2005(1)\u2005\u00c5 with Uiso(H) = 1.2Ueq(N). For (1), the water-bound H atoms were refined with distance restraints: O\u2014H = 0.84\u2005(1) and H\u22efH = 1.39\u2005(2)\u2005\u00c5 with Uiso(H) =1.5Ueq(O). For (2), the maximum and minimum residual electron density peaks of 0.60 and 0.58\u2005e\u2005\u00c5\u22123, respectively, were located 0.81 and 0.10\u2005\u00c5 from atoms O5 and H4N, respectively. In order to confirm the location of the N-bound H atoms, in a separate refinement these were refined without distance restraints. For (1), the N2\u2014H2N bond length was 0.948\u2005(17)\u2005\u00c5. For (2), the N3\u2014H3N and N4\u2014H4N bond lengths were 0.93\u2005(4) and 1.08\u2005(3)\u2005\u00c5, respectively. In the refinement of (1), one reflection, i.e. (180), was omitted from the refinement owing to poor agreement. For the same reasons, the following reflections were omitted from the final refinement of (2): (550),  1, 2, global. DOI: 10.1107/S1600536814011532/su00051sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814011532/su00052sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S1600536814011532/su00051sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814011532/su00052sup5.cmlSupporting information file. DOI: 1004283, 1004284CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III ion has a distorted O5Cl octa\u00adhedral coordination environment defined by two bidentate 2-eth\u00adoxy-6-formyl\u00adphenolato ligands, one Cl atom and one water mol\u00adecule. In the crystal, O\u2014H\u22efO hydrogen bonds link the two independent mol\u00adecules to form a dimer while the solvent mol\u00adecule is linked to the complex mol\u00adecule by a weak C\u2014H\u22efO hydrogen bond. Further weak C\u2014H\u22efO inter\u00adactions along with weak C\u2014H\u22efCl hydrogen bonds link the components into chains parallel to [001].In both complex mol\u00adecules in the asymmetric unit, the Fe L)2Cl(H2O)]\u00b70.5CH3CN, , there are two independent complex mol\u00adecules and one aceto\u00adnitrile solvent mol\u00adecule in the asymmetric unit. In each complex mol\u00adecule, the FeIII ion has a distorted O5Cl octa\u00adhedral coordination environment defined by two bidentate 2-eth\u00adoxy-6-formyl\u00adphenolato ligands, one Cl atom and one water mol\u00adecule. In the crystal, O\u2014H\u22efO hydrogen bonds link the two independent mol\u00adecules to form a dimer. The solvent mol\u00adecule is linked to the complex mol\u00adecule by a weak C\u2014H\u22efO hydrogen bond. Further weak C\u2014H\u22efO inter\u00adactions along with weak C\u2014H\u22efCl hydrogen bonds link the components into chains parallel to [001].In the title compound, [Fe( Those complexes display dominant ferromagnetic inter\u00adactions between metal ions.Recently, we have investigated the coordination behavior of the tridentate 2-hy\u00addroxy-benzaldehyde ramification ligand 3-eth\u00adoxy-2-hy\u00addroxy-benzaldehyde and reported two heterometallic polymers [ZnNa(ehbd)L)2Cl(H2O)]\u00b70.5CH3CN (HL = C9H10O3), was prepared similarly to the cubane cluster [Ni4(\u03bc3-OMe)4(heb)4(MeOH)1.05(H2O)2.95] \u00b76H2O was replaced by FeCl3\u00b76H2O in an attempt to prepare a cubane-type iron cluster. The crystals obtained, however, were those of the title mononuclear FeIII complex.The title compound, [Fe(L)2Cl(H2O)] mol\u00adecules and a aceto\u00adnitrile solvent mol\u00adecule. One of the independent mol\u00adecules is shown in Fig.\u00a01III ion is coordinated by four O atoms from two different \u2212L ligands, one Cl\u2212 ion and one terminal water mol\u00adecule, forming a distorted octa\u00adhedral geometry. The Fe\u2014O bond lengths are in the range 1.909\u2005(2)\u20132.157\u2005(2)\u2005\u00c5 (Table\u00a01trans-angles at the FeIII atom lie in the range 169.4\u2005(1)\u2013171.4\u2005(1)\u00b0, the cis-angles vary from 81.6\u2005(1) to 99.9\u2005(1)\u00b0. The \u2212L ligand displays a \u03bc1:\u03ba1:\u03ba1 coordination mode, which is the same as that of [Ni4(\u03bc3-OMe)4(heb)4(MeOH)1.05(H2O)2.95] 2(N3)6]n \u00c5 is observed, where Cg1 and Cg2 are the centroids defined by ring atoms C1\u2013C6 and C19\u2013C24, respectively. The solvent mol\u00adecule is linked to the complex mol\u00adecule by a weak C\u2014H\u22efO hydrogen bond. Further weak C\u2014H\u22efO inter\u00adaction along with weak C\u2014H\u22efCl hydrogen bonds link the components into chains parallel to [001] , 3-eth\u00adoxy-2-hy\u00addroxy-benzaldehyde , methanol (5\u2005mL) and aceto\u00adnitrile (5\u2005mL), with a pH adjusted to 7.5 by addition of tri\u00adethyl\u00adamine, was poured into a Teflon-lined autoclave (15\u2005mL) and then heated at 413K for 3 days. Black crystals of the title compound were collected by filtration, washed with methanol and dried in air. Phase pure crystals were obtained by manual separation .A mixture of FeCl2) or 0.97\u2005\u00c5 (CH3) with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl). H atoms bonded to O atoms were included with O\u2014H = 0.84\u20130.85\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814021205/lh5728sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814021205/lh5728Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814021205/lh5728Isup3.cdxSupporting information file. DOI: 1025672CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Hypoxia inducible factor 1\u03b1 (HIF-1\u03b1) is a stress-responsive transcription factor to hypoxia and its expression is correlated to tumor progression and angiogenesis. Several single nucleotide polymorphisms (SNPs) of HIF-1\u03b1 gene in the oxygen-dependent degradation (ODD) domain was reportedly associated with increased HIF-1\u03b1 activity.In this study, we focused on the relationship between SNP 1772 C\u2009>\u2009T (rs11549465) of HIF-1\u03b1 gene and its breast cancer risk, as well as its correlation with HIF-1\u03b1 expression and tumor angiogenesis. Ninety six breast cancer patients and 120 age-matched controls were enrolled. We found that 1772\u00a0T allele of HIF-1\u03b1 gene was associated with increased breast cancer risk . This SNP was not associated with clinicopathologic features of angiogenesis such as VEGF activity and the micro-vessel density and survival of breast cancer patients.Taken together, the 1772 C\u2009>\u2009T of HIF-1\u03b1 gene is a potential biomarker for breast cancer susceptibility. Single nucleotide polymorphisms (SNPs), the most common variants in human genome , are popTumor hypoxia is common in tumorigenesis. Hypoxia inducible factor-1 (HIF-1) is a crucial transcription factor in cellular response to tumor hypoxia and is considered as an adverse prognostic factor in breast cancers -14. AddiRecent studies demonstrated that another SNP located in ODD of HIF-1\u03b1, 1772 C\u2009>\u2009T (rs11549465), may lead to an amino acid change from proline 582 to serine (P582S) and are reportedly associated with renal ,19, headThe purpose of this study is to investigate the association between SNP 1772 C\u2009>\u2009T of the HIF-1\u03b1 gene in breast cancer patients and healthy control subjects. Furthermore, HIF-1 has been reported to transactivate many oxygen responsive genes such as vascular endothelial growth factor (VEGF) . TherefoBetween 1991 and 2001, a total of 96 randomly-selected female patients with breast cancer at Kaohsiung Medical University Hospital, Kaohsiung, Taiwan, were enrolled in this study. All patients underwent a standard modified radical mastectomy. Ninety-four patients  received adjuvant systemic chemotherapy with 6\u00a0cycles of 5-fluorourcil, doxorubicin and cyclophosphamide. After completion of chemotherapy, all patients received hormone therapy with tamoxifen and 92 patients  received radiation therapy. The principle of treatment was followed as described previously . We coll2, 0.2\u00a0\u03bcl of 10\u00a0mM dNTP each, 0.6\u00a0\u03bcl DMSO, 0.14\u00a0\u03bcl of Taq enzyme, 0.12\u00a0\u03bcl of 350\u00a0\u03bcg/ml primers mix (1:1), 2\u00a0\u03bcl DNA extracts and 5.64\u00a0\u03bcl distilled water. PCR was performed with the following protocol: 94\u00b0C (1\u00a0min); 4\u00a0cycles of 94\u00b0C (15\u00a0s), 64\u00b0C (15\u00a0s), 70\u00b0C (8\u00a0s); 4\u00a0cycles of 94\u00b0C (15\u00a0s), 61\u00b0C (15\u00a0s), 70\u00b0C (8\u00a0s); 4\u00a0cycles of 94\u00b0C (15\u00a0s), 58\u00b0C (15\u00a0s), 70\u00b0C (8\u00a0s); 60\u00a0cycles of 94\u00b0C for (15\u00a0s), 55\u00b0C (15\u00a0s), 70\u00b0C (8\u00a0s); 94\u00b0C (1\u00a0min) and 60\u00b0C (5\u00a0min). The available restriction enzyme for HIF-1\u03b1 1772 C\u2009>\u2009T (rs11549465) was retrieved from the SNP-RFLP freeware [Hph I restriction enzyme (NEB) at 37\u00b0C for overnight and then they were subjected to 3% agarose electrophoresis and stained with SYBR Safe\u2122 DNA gel stain (Invitrogen) for visualization of the PCR-restriction fragment length polymorphism (PCR-RFLP) patterns.Genomic DNA was isolated from paraffin-embedded tumor tissues of surgical specimens and peripheral blood of 120 normal controls as described ,28. The freeware -31. PCR Typical patterns of genotyping by PCR-RFLP have confirmed by sequencing. DNA amplicon from PCR reaction was purified using a MiniElute PCR purification kit (Qiagen)  for commStreptoavidin-biotin based immunohistochemical staining (IHC) was performed to detect HIF-1\u03b1 and VEGF protein levels as previously described . ImmunorMicrovessel density (MVD) represents tumor angiogenesis by using immunostaining of endothelial cells with monocloncal antibody, recognizing the CD31 endothelial glycoprotein. Each slide was scanned at low magnification (\u00d7 100) to identify the four areas of high density of microvessels (hotspots). The number of stained vessels per in each hotspot was counted at high power fields (\u00d7 400). Any stained endothelia cell was considered as a countable single microvessel. Large vessels with thick muscular walls were excluded. MVD was classified as either low (\u226635.0) or high (>35.0/high power field (HPF)); 35.0 was the median value.p values smaller than 0.05 are regarded as significance.Statistical significance was evaluated by the chi-square test and Fisher exact test. Overall survival curves were analyzed by the Kaplan-Meier method, and differences between the curves were analyzed by log-rank test. The p\u2009=\u20090. 22).In Table\u00a0In Figure\u00a0p\u2009<\u20090.001). The allele frequencies in controls and cancer patients were 232 C (97%)/8\u00a0T (3%) and 127 C (66%)/65\u00a0T (34%), respectively. The T-allele distribution in breast cancer patients differed significantly from that of controls .Based on PCR-RFLP analysis, the genotype distribution of control group was 116 CC (97%), 0 CT (0%) and 4 TT (3%). In contrast, the genotype distributions of breast cancer patients were 53 CC (55%), 21 CT (22%), and 22 TT (23%). The genotype distribution in breast cancer patients differed significantly from that of controls , T-stage (p\u2009=\u20090.303), N-stage (p\u2009=\u20090.936), local recurrence (p\u2009=\u20090.817), distant metastasis (p\u2009=\u20090.572), HIF-1\u03b1 expression (p\u2009=\u20090.311), VEGF expression (p\u2009=\u20090.375) and microvessel density (p\u2009=\u20090.211).When connecting the results of these stainings with HIF-1\u03b1 genotypes with clinicopathological analysis Table\u00a0, there wp\u2009<\u20090.001) and microvessel density (Exp. (B)\u2009=\u20092.6082, p\u2009<\u20090.05) were the most influential factors  and overall survival  by multi-variable analyses. Similarly, Kaplan-Meier analysis  and overall survival curves , respectively.In Table\u00a0rs Table\u00a0. HoweverThe SNP 1772 C\u2009>\u2009T of HIF-1\u03b1 gene chosen in current study are located within ODD of the HIF-1\u03b1. We found that T allele of the SNP 1772 C\u2009>\u2009T (P582S) of HIF-1\u03b1 gene was significantly higher in 96 breast cancer patients than in 120 controls. In contrast, the association results of SNP 1772 C\u2009>\u2009T of HIF-1\u03b1 gene with different kinds of cancers were not consistent in literature review. For example, the SNP 1772 C\u2009>\u2009T of HIF-1\u03b1 gene was detected in several cancers -21,23 buWithin ODD of the HIF-1\u03b1, proline residues 402 and 564 were reported to independently determine tightly binding to the von Hippel-Lindau (VHL) protein for HIF-1\u03b1 ubiquitination and degradation under nonhypoxia condition ,36-39. IFurthermore, the genotypes of SNP 1772 C\u2009>\u2009T of HIF-1\u03b1 gene are not significantly associated with clinicopathologic characteristics and clinical outcome of breast cancer (Table\u00a0p\u2009=\u20090.059) and disease-free survival (p\u2009=\u20090.110) [p\u2009=\u20090.0732) but weak association with overall survival (p\u2009=\u20090.3225)  . SimilarThe phenomena mentioned above may be partly explained by the multigene theory for carcinogenesis . FurtherTaken together, SNP 1772 C\u2009>\u2009T (P582S) of HIF-1\u03b1 gene confers significant association with breast cancer risk but it show no association with the clinicopathologic features and survival of breast cancer patients."}
{"text": "In the title salt, the cations and anions are linked through O\u2014H\u22efO,N\u2014H\u22efO, N\u2014H\u22efN and \u03c0\u2013\u03c0 stacking inter\u00adactions, forming double layers parallel to (101). Weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds connect the double layers into a three-dimensional network. 6H9ClN3+\u00b7C6H3O4S\u2212, the cations and anions are linked via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming R66(37) ring motifs that are inter\u00adconnected with each other, producing sheets. Separate parallel inversion-related sheets are linked through N\u2014H\u22efN and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.5414\u2005(13)\u2005\u00c5], forming double layers parallel to (101). Weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, as well as C\u2014H\u22ef\u03c0 inter\u00adactions, connect the double layers into a three-dimensional network.In the title salt, C The mixture was cooled slowly and kept at room temperature. After a few days colourless plate-like crystals were obtained.3). Isotropic displacement parameters for these atoms were set to 1.2 (CH) or 1.5 (CH3) times Ueq of the parent atom. Idealized Me H atoms were refined as rotating groups. There are larger than expected residual density peaks close to the Cl and S atoms but these are not chemically sensible and are assumed to be related to the quality of the crystal.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016010148/lh5814sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010148/lh5814Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016010148/lh5814Isup3.cmlSupporting information file. DOI: 1486940CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of (I), pairs of [Fe(CN)4]\u2212 units  are linked together through \u03c0\u2013\u03c0 stacking between the pyridyl rings of the 2,2\u2032-bipy ligands to form a graphite-like structure parallel to the ab plane. The three independent water mol\u00adecules are hydrogen-bonded alternately with each other, forming a ladder chain structure with R44(8) and R66(12) graph-set ring motifs, while the disordered [N(CH3)4]+ cations lie above and below the water chains, and the packing is stabilized by weak C\u2014H\u22efO hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional network via O\u2014H\u22efO hydrogen bonds involving the lattice water mol\u00adecules and the N atoms of terminal cyanide groups of the [Fe(CN)4]\u2212 building blocks, forming an R44(12) ring motif. Compound (II) features a two-dimensional {[Fe(CN)4Cd(en)2]}n layer structure (en is ethyl\u00adenedi\u00adamine) extending parallel to (010) and constructed from {[Fe(CN)4Cd(en)]}n chains inter\u00adlinked by bridging en ligands at the Cd atoms. Classical O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds involving the lattice water mol\u00adecule and N atoms of terminal cyanide groups and the N\u2014H groups of the en ligands are observed within the layers. The layers are further connected via \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent pyridine rings of the 2,2\u2032-bipy ligands, completing a three-dimensional supra\u00admolecular structure.The crystal structures of the building block tetra\u00admethyl\u00adammonium (2,2\u2032-bi\u00adpyridine-\u03ba M(CN)6]n\u2212 (n = 2\u20134), have been used extensively as building blocks for the design and construction of a large number of high-dimensional cyanide-bridged bimetallic coordination polymers because of their ability to act as multidentate ligands to link numerous metal atoms through all six cyanide groups 6]3\u2013 with octa\u00adhedrally coordinated transition metal ions  such as 2,2\u2032-bi\u00adpyridine  or 1,10-phenanthroline  in cyanide-containing building blocks of general formula [M(L)(CN)4]n\u2212  instead of [M(CN)6]n\u2212 has been a recent development in the field of low-dimensionality cyanide-bridged bimetallic coordination compounds 4][Fe(CN)4(C10H8N2)]\u00b73H2O (I)4)(C10H8N2)(C2H8N2)2]\u00b7H2O (II)As part of our search for novel cyanide-bridged bimetallic coordination polymers, we herein describe the synthesis and crystal structure of [N4]+ and three water mol\u00adecules, as displayed in Fig.\u00a01III ion is coordinated by two nitro\u00adgen atoms from one 2,2\u2032-bipy ligand and four cyanide carbon atoms in a distorted octa\u00adhedral geometry. This distortion around the metal atom is defined by the sum of the octa\u00adhedral angular deviations from 90\u00b0 (\u03a3), in which the trigonal distortion angle = 0 for a perfect octa\u00adhedron \u00b0. The three trans angles  are bent slightly from the ideal value of 180\u00b0. The iron atom and terminal cyanido groups, viz. [Fe1\u2014C3\u2261N3 = 178.7\u2005(3) and Fe1\u2014C4\u2261N4 = 179.8\u2005(4)\u00b0] are almost linear compared to the iron atom and the corresponding equatorial cyano groups [viz. Fe1\u2014C1\u2014N1 = 175.8\u2005(4) and Fe1\u2014C2\u2014N2 = 176.6\u2005(4)\u00b0]. This difference is probably caused by hydrogen bonding (see below). The Fe\u2014C bond lengths range from 1.917\u2005(4) to 1.969\u2005(4)\u2005\u00c5, whereas the Fe\u2014N bond lengths are 1.981\u2005(3) and 1.985\u2005(3)\u2005\u00c5. The whole mol\u00adecule of 2,2\u2032-bipy ligand is planar with an r.m.s. deviation of 0.016\u2005\u00c5; the dihedral angle between the two pyridyl rings is 1.57\u2005(18)\u00b0. Bond lengths and angles within the [Fe(CN)4]\u2212 anion in (I)4]\u00b7H2O (CN)4]\u00b7H2O (CN)4]\u00b7CH3CN  consists of one [Fe(CN)III precursor was reduced to FeII under the crystallization conditions. The asymmetric unit contains half each of an [Fe(CN)4]\u2212 anion and a [Cd(en)2]2+ cation, with the mol\u00adecules lying across twofold rotation axes, Fig.\u00a02II ion is a distorted octa\u00adhedron with a \u03a3 of 28.90\u00b0. The Fe\u2014C\u2014N angles for both bridging [Fe1\u2014C1\u2014N1 = 178.15\u2005(14)\u00b0] and terminal [Fe1\u2014C2\u2014N2 = 176.85\u2005(16)\u00b0] cyanide groups deviate slightly from strict linearity. The Fe\u2014Ccyanide bond lengths at 1.8950\u2005(16) and 1.9363\u2005(17)\u2005\u00c5 are slightly shorter than the Fe\u2014N2,2\u2032-bipy bond length, 1.9976\u2005(14)\u2005\u00c5. The CdII ion is six-coordinated by two N atoms from two cyanide groups, two N atoms from a chelating en ligand and two N atoms from two different bridging en ligands in a highly distorted octa\u00adhedral geometry with a \u03a3 of 108.08\u00b0. The Cd\u2014N bond lengths and the N\u2014Cd\u2014N bond angles in (II)4N)[{Fe(CN)6}3{Cd(en)}4] 2] }3]\u00b74H2O ]2+cations, forming a chain of [Fe(CN)4Cd(en)] units running parallel to the a axis. Along the b axis, adjacent chains are then inter\u00adconnected through the N atoms of the bridging en ligands at the Cd atoms into a two-dimensional layer of [Fe(CN)4Cd(en)2], as shown in Fig.\u00a032}2{Cd(en)}2] units with an Fe\u22efCd distance through the cyanide bridge and a Cd\u22efCd distance through the en bridge of 5.1292\u2005(7) and 7.6692\u2005(12)\u2005\u00c5, respectively. The M\u22efM distances across the cyclic windows vary from 5.5614\u2005(10) to 14.0061\u2005(10)\u2005\u00c5.Compound (II)4]\u2212 mol\u00adecules are linked together through the parallel pyridyl rings of the 2,2\u2032-bipy ligands to generate a graphite-like layers parallel to the ab plane. Within the sheets, the neighbouring pyridyl moieties related by an inversion centre are in a head-to-head arrangement with centroid (Cg) to centroid distances of 4.005\u2005(3)\u2005\u00c5 [inter\u00adplanar angle = 0.0\u2005(4)\u00b0] and 3.903\u2005(3)\u2005\u00c5 [inter\u00adplanar angle = 0.0\u2005(3)\u00b0] for rings A\u22efAi and B\u22efBii , respectively. The FeIII\u22efFeIII separations along the \u03c0\u2013\u03c0 stacking of parallel rings A\u22efAi and rings B\u22efBii are 8.2821\u2005(12) and 8.4572\u2005(13)\u2005\u00c5, respectively. The adjacent pyridyl rings A and Biii  related by translation parallel to the a axis are arranged alternately in a head-to-tail manner with a Cg\u22efCg distance of 3.865\u2005(2)\u2005\u00c5 [inter\u00adplanar angle = 1.51\u2005(12)\u00b0] and an FeIII\u22efFeIII separation of 6.8690\u2005(9)\u2005\u00c5.The three-dimensional supra\u00admolecular structure in (I)2O)4 and hexa\u00admeric (H2O)6 subunits into (H2O)10 units [the dihedral angle between the best plane of the (H2O)4 and (H2O)6 subunits is 55.2\u2005(2)\u00b0]; neighbouring units are further joined together, giving rise to ladder-like water chains running parallel to the a axis. As can be seen from Fig.\u00a05i, O2, and O2i (for symmetry code see Table\u00a012O)4 3(DMF)4(H2O)2]\u00b74DMF\u00b74H2O i, O1ii, O2, O2iii, O3, and O3iii ]+ cations lie above and below the water chains and take part in the formation of weak C\u2014H\u22efO hydrogen bonds with the water mol\u00adecule.The hexa\u00admeric water unit has crystallographically imposed inversion symmetry. The six water mol\u00adecules O1via \u03c0\u2013\u03c0 stacking between adjacent pyridyl rings with Cg\u22efCg distances of 4.2925\u2005(18) [inter\u00adplanar angle = 1.55\u2005(18)\u00b0] and 4.0642\u2005(18)\u2005\u00c5 [inter\u00adplanar angle = 0.0\u2005(3)\u00b0] for rings C\u22efCiv and C\u22efCv , respectively, Fig.\u00a06For (II)3)4[Fe(CN)4]\u00b73H2O (I)4[Fe(CN)4]\u00b7H2O . Analysis calculated for C18H26FeN7O: C, 48.66; H, 5.90; N, 22.07%. Found: C, 48.66; H, 5.90; N, 22.07%.The building block N(CH3)2\u00b74H2O  and ethyl\u00adenedi\u00adamine  were dissolved in distilled H2O (4\u2005ml), and this was pipetted into one side of an H-tube. N(CH3)4[Fe(CN)4]\u00b73H2O  was dissolved in distilled H2O (4\u2005ml), and this was pipetted into the other side arm of the H-tube. The H-tube (15\u2005ml capacity) was then carefully filled with distilled H2O. Slow diffusion in the dark for three weeks yielded dark-yellow plate-shaped crystals of (II)18H26CdFeN10O: C, 38.15; H, 4.62; N, 24.72%. Found: C, 38.18; H, 4.60; N, 24.68%.For the synthesis of (II)Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq otherwise. For (I)Uiso(H) = 1.5Ueq(O). For (II)Uiso(H) = 1.5Ueq(O). The tetra\u00admetyl\u00adammonium cation in (I)A, C17A and C18A, and 0.560\u2005(6) for atoms C16B, C17B, and C18B. Anisotropic displacement parameters of all atoms were restrained using enhanced rigid-bond restraints  I, II. DOI: 10.1107/S2056989016006848/bg2584Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016006848/bg2584IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1476008, 1476007CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two bromo\u2013hy\u00addroxy\u2013benzoic acid derivatives, namely, methyl 4-bromo-2-(meth\u00adoxy\u00admeth\u00adoxy)benzoate, (I), and 4-bromo-3-(meth\u00adoxy\u00admeth\u00adoxy)benzoic acid, (II), are compared. Compound (II) crystallizes with two independent mol\u00adecules in the asymmetric unit. In the crystal structures of both compounds, two-dimensional architectures are formed principally by C\u2014H\u22efO hydrogen bonds, and by Br\u22efO inter\u00adactions in (I) and by \u03c0\u2013\u03c0 inter\u00adactions in (II). 10H11BrO4, (I), and C9H9BrO4, (II), are derivatives of bromo\u2013hy\u00addroxy\u2013benzoic acids. Compound (II) crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. In both (I) and (II), the O\u2014CH2\u2014O\u2014CH3 side chain is not in its fully extended conformation; the O\u2014C\u2014O\u2014C torsion angle is 67.3\u2005(3) \u00b0 in (I), and \u221265.8\u2005(3) and \u221274.1\u2005(3)\u00b0 in mol\u00adecules A and B, respectively, in compound (II). In the crystal of (I), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming C(5) chains along [010]. The chains are linked by short Br\u22efO contacts [3.047\u2005(2)\u2005\u00c5], forming sheets parallel to the bc plane. The sheets are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional architecture. In the crystal of (II), mol\u00adecules A and B are linked to form R22(8) dimers via two strong O\u2014H\u22efO hydrogen bonds. These dimers are linked into \u22efA\u2013B\u22efA\u2013B\u22efA\u2013B\u22ef [C22(15)] chains along [011] by C\u2014H\u22efO hydrogen bonds. The chains are linked by slipped parallel \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distances = 3.6787\u2005(18) and 3.8431\u2005(17)\u2005\u00c5], leading to the formation of slabs parallel to the bc plane.The title compounds, C The dihedral angle between the benzene ring and the ester segment (O1/C7/O2/C8) is 14.5\u2005(2)\u00b0, while the plane through atoms C10/O4/C9 of the meth\u00adoxy\u00admeth\u00adoxy side chain is inclined to the benzene ring by 82.5\u2005(3)\u00b0.The mol\u00adecular structure of compound (I)A and B) in the asymmetric unit. The conformations of the two mol\u00adecules differ in the torsion angles of the \u2013O\u2013CH2\u2013O\u2013CH3 side chains and the orientation of the \u2013COO\u2013 group with respect to the benzene ring, as shown in the AutoMolFit diagram \u00b0, and torsion angle O3B\u2014C8B\u2014O4B\u2013-C9B in mol\u00adecule B is \u221274.1\u2005(3)\u00b0. The dihedral angle between the benzene ring and the plane through atoms C8A/O4A/C9A of the meth\u00adoxy\u00admeth\u00adoxy side chain in mol\u00adecule A is 79.2\u2005(3)\u00b0, while the corresponding dihedral angle in mol\u00adecule B, between the benzene ring and plane C9B/O4B/O8B is 67.1\u2005(3)\u00b0. This is less than in compound (I)A and 9.1\u2005(4)\u00b0 in B; also less than observed in compound (I)viz. 14.5\u2005(2)\u00b0.The mol\u00adecular structure of compound (II)am Fig.\u00a03. The \u2013O\u2013A\u22efO1 hydrogen bonds (Table\u00a01C(5) chains along the b axis. Adjacent chains are linked by short Br1\u22efO4i contacts  leading to the formation of sheets parallel to plane (100). The sheets are linked by C5\u2014H5\u22ef\u03c0 inter\u00adactions (centroid of the benzene ring C1\u2013C6) along the a-axis direction, forming a three-dimensional structure s Table\u00a01, forminge Table\u00a01.A and B are linked via two strong O\u2014H\u22efO hydrogen bonds, namely, O2A\u2013-H2A\u22efO1B and O2B\u2013-H2B\u22efO1A, forming dimers with an B\u2014H8B2\u22ef\u00b7O3A hydrogen bonds \u2005\u00c5; Cg2 is the centroid of ring C1B\u2013C6B; inter-planar distance = 3.3691\u2005(12)\u2005\u00c5; slippage = 1.477\u2005\u00c5; symmetry code (ii): \u2212x, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01], and between A and B mol\u00adecules , thus forming slabs lying parallel to the bc plane f Table\u00a02. Adjacens Table\u00a02, formingne Fig.\u00a07.Synthesis of methyl 4-bromo-2-(meth\u00adoxy\u00admeth\u00adoxy) benzoate (I)N,N-diiso\u00adpropyl\u00adethyl\u00adamine  (DIPEA), followed by chloro\u00admethyl methyl ether  (MOM-Cl), at 273\u2005K and the reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with water (50\u2005ml) and the organic layer was extracted with ethyl acetate (2 \u00d7 50\u2005ml). The combined organic layers were washed successively with water, brine, dried over anhydrous magnesium sulfate (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate:hexane (1:9) as eluent to afford (I)1H NMR : \u03b4 = 3.39 , 3.79 , 5.29  7.29 , 7.44 , 7.60 .To a stirred solution of methyl 4-bromo-2-hy\u00addroxy-benzoate  in di\u00adchloro\u00admethane (15\u2005ml) (DCM) was added Synthesis of 4-bromo-3-(meth\u00adoxy\u00admeth\u00adoxy)benzoic acid (II)N hydro\u00adchloric acid. The precipitated solid was filtered, dried under vacuum to afford (II)1H NMR : \u03b4 = 3.39 , 5.28 , 7.26 , 7.40 , 7.59 , 12.90 .A mixture of methyl 4-bromo-3-(meth\u00adoxy\u00admeth\u00adoxy) benzoate , 10% aqueous potassium hydroxide , tetra\u00adhydro\u00adfuran (5\u2005ml) and methanol (20\u2005ml) was stirred at room temperature for 2\u2005h. The mixture was then concentrated to remove organic solvents and the aqueous layer was acidified with 6\u2005Single crystals of compounds (I)Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. In the final cycles of refinement reflection (0 0 2) in (I)F2obs and F2calc, considerably improving the values of R1, wR2, and GOF.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016003777/su5284sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: Click here for additional data file.10.1107/S2056989016003777/su5284Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016003777/su5284IIsup3.cmlSupporting information file. DOI: 1457944, 1457943CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The triflate ligand was found to be disordered over two sets of sites, with a site-occupancy ratio of 0.622\u2005(16):0.378\u2005(16). Weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efF hydrogen-bonding inter\u00adactions generate a two-dimensional supra\u00admolecular structure lying parallel to (100). This is only the second crystal structure reported of a mononuclear bis\u00ad(acetyl\u00adacetonato)iron(III) complex.The mononuclear title complex, [Fe(CF The dinuclear alkoxides, [Fe(acac)2(\u03bc-OR)] are also known iron(III) complex, [Fe(acac)2(OTf)(THF)], the title compound (I)Because of its ease-of-handling, relative stability and good solubility in most organic solvents, tris\u00ad(acetyl\u00adacetonato)iron(III) [Fe(acac)3+ atom in an slightly distorted octa\u00adhedral FeO6 environment. The coordination sphere of the metal comprises four oxygen atoms from two \u03ba2-acac ligands [Fe\u2014Oacac range = 1.9517\u2005(11)\u20131.9762\u2005(11)\u2005\u00c5], one oxygen atom of a THF solvate mol\u00adecule [Fe1\u2014O8 = 2.0781\u2005(11)\u2005\u00c5] and one oxygen atom of a disordered triflate anion [Fe1\u2014O5 = 2.063\u2005(4)\u2005\u00c5 or Fe1\u2014O5B = 2.066\u2005(6)\u2005\u00c5] (Table\u00a01cis angles range from 84.63\u2005(5)\u00b0 to 98.09\u2005(5)\u00b0 and the trans angles range from 172.60\u2005(5)\u00b0 to 174.9\u2005(6)\u00b0.The mol\u00adecular structure of the mononuclear complex (I)] Table\u00a01. The disa,b). A series of Cmeth\u00adyl\u2014H\u22efOacac, Cmeth\u00adyl\u2014H\u22efOtriflate, Cmeth\u00adyl\u2014H\u22efFtriflate, CTHF\u2014H\u22efOtriflate, and CTHF\u2014H\u22efFtriflate inter\u00adactions make up the layers, the details of these inter\u00adactions are presented in Table\u00a02c,d.There are no significant supra\u00admolecular features to discuss in the extended structure of (I)2Cl] acac range of 1.945\u20132.062\u2005\u00c5.Only one other mononuclear bis\u00ad(acetyl\u00adacetonato)iron(III) complex has been characterized crystallographically, [Fe(acac)2(C6H5)(OTf)] (THF)] -triflate complex, [Os(acac)3]  in dry THF (5\u2005mL). The resulting purple\u2013red solution was stirred at room temperature for 1\u2005h. The reaction mixture was then concentrated under vacuum to a volume of approximately 2\u2005mL, and 20\u2005mL of pentane was added. A dark purple\u2013red microcrystalline solid precipitated. The mixture was filtered through a glass-frit and the microcrystalline solid was dried under vacuum . Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a THF solution of the purple\u2013red solid. CH analysis calculated for C15H22F3FeO8S (MW: 475.235): C 37.91%; H 4.67%. Found: C 37.69%; H, 4.45%.Triflic acid  was added to a solution of . Remaining H atoms were also included as riding idealized contributors .Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015016849/zs2341sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015016849/zs2341Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015016849/zs2341Isup3.tifSupporting information file. DOI: 1423096CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 2427810.1038/srep24278; published online: 04072016; updated: 06102016.This Article contains an error in Figure S3; where the labels \u20180\u2009\u00b0C\u2019 and \u201825\u2009\u00b0C\u2019 are inverted. The correct Figure S3 appears below as"}
{"text": "In the crystal, mol\u00adecules are linked  12H13N2+\u00b7Cl\u2212, the chloride salt of 1,1\u2032-di\u00adphenyl\u00adhydrazine, the phenyl rings are inclined to one another by 78.63\u2005(17)\u00b0. The N\u2014+NH3 bond lengths is 1.445\u2005(3)\u2005\u00c5, and the N\u2014Cphen\u00adyl bond lengths are 1.435\u2005(3) and 1.447\u2005(4)\u2005\u00c5. In the crystal, mol\u00adecules are linked via N\u2014H\u22efCl hydrogen bonds, forming chains along [10-1], which enclose two adjacent R42(6) ring motifs. The chains are reinforced by C\u2014H\u22efCl hydrogen bonds.In the title compound, C It has been used as a starting reagent for the preparation of Schiff bases as fluorescent sensors for fluoride . The latter compound is one of a series that has been used to prepare bis\u00ad(imino)\u00adpyridyl iron and cobalt complexes to study the effect of nitro\u00adgen substituents on ethyl\u00adene oligomerization and polymerization via N\u2014H\u22efCl hydrogen bonds, forming chains along . There are no \u03c0\u2013\u03c0 inter\u00adactions present in the crystal structures of any of the three compounds.In the crystal of compound (II), mol\u00adecules are linked by N\u2014H\u22efN, N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, forming two-dimensional networks parallel to (001). These sheets are linked N,N-di\u00adphenyl\u00adhydrazone) by a condensation reaction involving 1,1\u2032-di\u00adphenyl\u00adhydrazinium hydro\u00adchloride and 2,6-di\u00adacetyl\u00adpyridine in methanol.Brown block-like crystals of the title compound were obtained during an attempt to prepare the ligand 2,6-di\u00adacetyl\u00adpyridine bis\u00ad(Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814022879/lh5735sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814022879/lh5735Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814022879/lh5735Isup3.cmlSupporting information file. DOI: 1029761CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "However, the crystal structure exhibits pseudosymmetry as the two independent mol\u00adecules are related by an approximate but non-crystallographic inversion located close to  in the selected asymmetric unit, and the structure exhibits partial inversion twinning. The approximate inversion relationship between the two mol\u00adecules in the selected asymmetric unit is clearly shown by comparison of the relevant torsion angle in the two mol\u00adecules; the corresponding torsion angles have similar, although not identical magnitudes but with opposite signs. The mean planes of the quinoline rings in the two independent mol\u00adecules are almost parallel, with a dihedral angle of only 0.16\u2005(3)\u00b0 between them, and the mutual orientation of these rings permits significant \u03c0\u2013\u03c0 stacking inter\u00adactions between them [centroid\u2013centroid distances = 3.7579\u2005(15) and 3.7923\u2005(15)\u2005\u00c5]. In addition, the bimolecular aggregates which are related by translation along [010] are linked by a further \u03c0\u2013\u03c0 stacking inter\u00adaction [centroid\u2013centroid distance = 3.7898\u2005(15)\u2005\u00c5], so forming a \u03c0-stacked chain running parallel to [010]. However, there are no C\u2014H\u22efN hydrogen bonds in the structure nor, despite the number of independent aromatic rings, are there any C\u2014H\u22ef\u03c0 hydrogen bonds; hence there are no direction-specific inter\u00adactions between adjacent \u03c0-stacked chains.The title compound, C \u00c5b = 7.1401 (3) \u00c5c = 13.0804 (5) \u00c5V = 2532.47 (17) \u00c53Z = 8K\u03b1 radiationMo \u22121\u03bc = 0.30 mmT = 173 K0.48 \u00d7 0.32 \u00d7 0.22 mmAgilent Eos Gemini diffractometerCrysAlis RED; Agilent, 2012Tmin = 0.808, Tmax = 0.936Absorption correction: multi-scan (29727 measured reflections5975 independent reflectionsI > 2\u03c3(I)5204 reflections with Rint = 0.037R[F2 > 2\u03c3(F2)] = 0.040wR(F2) = 0.097S = 1.085975 reflections331 parameters1 restraintH-atom parameters constrainedmax = 0.25 e \u00c5\u22123\u0394\u03c1min = \u22120.22 e \u00c5\u22123\u0394\u03c1x determined using 1610 quotients [(I+)\u2212(I\u2212)]/[(I+)+(I\u2212)] CrysAlis PRO  global, I. DOI: 10.1107/S205698901500804X/hg5440Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500804X/hg5440Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901500804X/hg5440fig1.tif. DOI: The two independent mol\u00adecules in the title compound showing the atom-labelling scheme. Displacement ellipsoids are shown at the 30% probability level.Click here for additional data file.10.1107/S205698901500804X/hg5440fig2.tif. DOI: The two mol\u00adecules in the selected asymmetric unit, viewed normal to the planes of the quinolone units, showing the ring overlap which leads to a \u03c0..\u03c0 sktacking inter\u00adaction. For the sake of clarity, the H atoms have been omitted.Click here for additional data file.10.1107/S205698901500804X/hg5440fig3.tif. DOI: A stereoview of part of the crystal structure of the title compound showing the formation of a \u03c0-stacked chain parallel to [010]. For the sake of clarity, the H atoms have been omitted.1061227CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The bond lengths and angles of the cyclo\u00adpenta\u00addienyl and phosphane ligands are very similar to that of the unsolvated complex [Taqui Khan et al.  and 1.156\u2005(3)\u2005\u00c5 and has an N\u2014N\u2014Ru angle of 119.20\u2005(15)\u00b0, indicating a greater contribution of the canonical form Ru\u2014N=N(+)=N(-) for the bonding situation. An intra\u00admolecular C\u2014H\u22efN hydrogen-bonding inter\u00adaction between one ortho H atom of a phosphane ligand and the N atom coordinating to the metal is observed. A similar inter\u00admolecular inter\u00adaction is observed between a meta H atom of a phosphane ligand and the terminal azide N atom of a neighbouring complex. Finally, two C\u2014H\u22efN inter\u00adactions exists between the H atoms of the di\u00adchloro\u00admethane solvent mol\u00adecule and the terminal N atom of two azide anions. The solvent mol\u00adecule is located about a twofold rotation axis and shows disorder of the Cl atoms with an occupancy ratio of 0.62\u2005(3):0.38\u2005(3).The title solvated complex, [Ru(\u03b7 al. 1994. Acta Cr For oth al. 1999; Govinda al. 2005. For met al. 2005; Seok &  al. 2005. Non-cla al. 2005 of respe al. 2002.5H5)(N3)(C18H15P)2]\u00b70.5CH2Cl2[Ru \u00c5b = 12.4559 (3) \u00c5c = 28.6781 (6) \u00c5\u03b2 = 94.213 (2)\u00b0V = 7189.7 (3) \u00c53Z = 8K\u03b1 radiationMo \u22121\u03bc = 0.63 mmT = 293 K0.72 \u00d7 0.51 \u00d7 0.20 mmAgilent Xcalibur Atlas Gemini diffractometerCrysAlis PRO 6038 reflections with Rint = 0.032R[F2 > 2\u03c3(F2)] = 0.027wR(F2) = 0.065S = 1.067106 reflections449 parametersH-atom parameters constrainedmax = 0.33 e \u00c5\u22123\u0394\u03c1min = \u22120.49 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019187/wm5050Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814019187/wm5050fig1.tif. DOI: Mol\u00adecular structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major component of the disordered di\u00adchloro\u00admethane solvate is shown. Hydrogen atoms of the metal complex have been removed for clarity.Click here for additional data file.10.1107/S1600536814019187/wm5050fig2.tif. DOI: View of the mol\u00adecular arrangement in the title structure viewed along [010]. Hydrogen bonds are denoted by dashed lines.1021189CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom with a distorted octa\u00adhedral coordination environment defined by six N atoms from three bidentate phenanthroline ligands. The non-coordinating N,N\u2032-diglycine ligand links the cationic building blocks via C\u2014H\u22efO contacts and through lone-pair\u22ef\u03c0 inter\u00adactions. Further observed non-covalent inter\u00adactions contribute to the consolidation of the supra\u00admolecular network.The complex cation of the title compound includes one Co 12H8N2)3]2(NO3)4\u00b7C12H12N2O6\u00b78H2O, contains a CoII atom with a distorted octa\u00adhedral coordination environment defined by six N atoms from three bidentate 1,10-phenanthroline ligands. The asymmetric unit of the title compound is completed by one-half of the N,N\u2032-diglycine solvent mol\u00adecule, which is located on a centre of inversion, by two nitrate counter-anions and four solvent water mol\u00adecules. Two [Co(C12H8N2)3]2+ cations are connected through C\u2014H\u22efO contacts and through lone-pair\u22ef\u03c0 inter\u00adactions involving the non-coordinating N,N\u2032-diglycine and phenanthroline mol\u00adecules. The different aromatic ring systems are involved in \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions, with centroid-to-centroid distances in the range 3.7094\u2005(8)\u20133.9973\u2005(9)\u2005\u00c5. The crystal structure is stabilized by further anion\u22ef\u03c0 inter\u00adactions and C\u2014H\u22efO contacts, as well as O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds between water mol\u00adecules, the non-coordinating nitrate anions, N,N\u2032-diglycine and phenanthroline mol\u00adecules. These non-covalent inter\u00adactions give rise to a three-dimensional supra\u00admolecular network.The complex cation of the title compound, [Co(C Application fields for these materials are in catalysis, in gas storage diglycine as metal-linking ligand, zigzag chains are formed, constructing inter\u00adpenetrating networks (see Database survey). In our synthetic approach, we offer such systems another electron-deficient bidentate aromatic ring system like phenanthroline or bi\u00adpyridine in order to block parts of the coordination sphere of the metal atoms so that these zigzag chains are truncated or not formed at all. Thus, an alternative route for the resultant system lies in the use of the offered \u03c0-inter\u00adaction possibilities as well as in stacking inter\u00adactions as a new linking mode. Recently, we have described the inter\u00adactions of a cobalt(III) bi\u00adpyridine complex with supra\u00admolecular synthons diglycine. The chosen ligand N,N\u2032-diglycine is a relatively rigid mol\u00adecule with one sp3-hybridized methyl\u00adene carbon atom that allows the acid moiety to rotate. Moreover, this ligand simultaneously possesses several coordination sites through the carb\u00adoxy\u00adlic group and the oxygen atom of the amide group. These functional groups can also be involved in hydrogen bonding and D\u2014H\u22ef\u03c0 inter\u00adactions.In previously synthesized transition metal complexes with N,N\u2032-diglycine solvent molecule linking two tris\u00ad(phenanthroline)cobalt(II) cationic building blocks via the mentioned non-classical inter\u00adactions.In the present contribution we have determined the structure of a novel cobalt(II) coordination polymer with a non-coordinating II complex cation in which three bidentate phenanthroline ligands define a distorted octa\u00adhedral coordination sphere. Distances and angles of this rather common cationic species, [Co(C12H8N2)3]2+, are well within expected ranges and are comparable to those found in the literature diglycine molecule. The asymmetric unit is completed by two non-coordinating nitrate counter-anions and four solvent water mol\u00adecules. The N,N\u2032-diglycine mol\u00adecule links two complex tris\u00adcobalt(II) cations via lone-pair\u22ef\u03c0 inter\u00adactions involving the carb\u00adoxy\u00adlic acid function and the phenanthroline aromatic system as well as C\u2014H\u22efO contacts between the oxygen atom of the amide group and one phenanthroline ligand. Moreover, \u03c0\u2013\u03c0 stacking inter\u00adactions between different aromatic ring systems and C\u2014H\u22ef\u03c0 as well as O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding are observed and consolidate an extensive three-dimensional supra\u00admolecular network.The mol\u00adecular entities Fig.\u00a01 of the tvia O\u2014H\u22efO, C\u2014H\u22efO and partly via N\u2014H\u22efO hydrogen bonds with water, phenanthroline and N,N\u2032-diglycine mol\u00adecules diglycine solvent mol\u00adecules stack these components along the c axis \u2005\u00c5 and between Cg7\u22efCg7 is 3.9973\u2005(9)\u2005\u00c5 \u22efCg8 of 3.037\u2005(1)\u2005\u00c5, where Cg8 is the centroid defined by the ring atoms N5/C25\u2013C28/C36. Moreover, a relatively short N\u2014H\u22ef\u03c0 distance of 4.08\u2005(6)\u2005\u00c5 is observed diglycine solvent and the Cg2 centroid of a phenanthroline ligand are associated with a distance of 3.400\u2005(5)\u2005\u00c5. Similar distances of 3.461\u2005(5)\u2005\u00c5 prevail between the O10 atom of a water mol\u00adecule and the Cg3 centroid of a phenanthroline ligand, where Cg2 and Cg3 are the centroids defined by the ring atoms N1/C1\u2013C4/C12 and C4\u2013C7/C11/C12, respectively. The values are similar to those found in the literature \u2005\u00c5 that is comparable to previously reported structures diglycine resulted in six metal-organic compounds diglycine and shows a number of non-classical inter\u00adactions diglycine, was prepared by the method of Cleaver & Pratt (1955v/v) mixture of water and methanol (50\u2005ml) and refluxed for 30 minutes. The mixture was allowed to cool to room temperature, and a previously prepared aqueous solution of cobalt nitrate (1\u2005mmol) was slowly added under continuous stirring. Deep dark-orange block-shaped crystals of the title compound were obtained by slow evaporation at room temperature.The starting material, ratt 1955. Cesium Uiso(H) = 1.2 Ueq(C) and C\u2014H(aromatic) = 0.94\u2005\u00c5 and C\u2014H(methyl\u00adene) = 0.98\u2005\u00c5 using a riding model. The water H atoms were located in a different Fourier map and were refined with O\u2014H distances restrained to 0.82\u20130.87\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015013006/wm5178sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015013006/wm5178Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015013006/wm5178Isup4.cdxSupporting information file. DOI: 1410901CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I with the pyridyl\u00adimidazol ligand 4--1H-imidazol-2-yl)pyridine, afforded a nitrate-free one-dimensional looped-chain polymeric structure. The AgI cation adopts a highly distorted tetra\u00adhedral geometry coordinated by two pyridine N atoms and two imidazole N atoms from four individual ligands.The reaction of Ag 29H25N3)2]NO3\u00b7CH3OH\u00b7H2O}n, the AgI cation is four-coordinated by two pyridine N atoms and two imidazole N atoms from four individual 4--1H-imidazol-2-yl)pyridine (i-pro-pyim) ligands. This gives rise to a highly distorted tetra\u00adhedral geometry with bond angles falling in the range 100.33\u2005(19)\u2013122.76\u2005(19)\u00b0. Two crystallographically independent i-pro-pyim ligands (A and B) adopt very similar conformations to one another, such that the dihedral angles between the pyridyl and imidazolyl rings in the two ligands are 40.7\u2005(3) and 42.2\u2005(3)\u00b0, respectively. Each i-pro-pyim ligand binds two symmetry-related Ag+ cations, leading to the formation of 14-membered cyclic dimers, in which the AgI atoms are separated by 6.963\u2005(2)\u2005\u00c5 for the Ag\u2013A2\u2013Ag dimer and 7.020\u2005(2)\u2005\u00c5 for Ag\u2013B2\u2013Ag. These cyclic dimers are alternately connected to each other by sharing AgI atoms, resulting in the formation of a looped-chain structure extending along the [100] direction. Moreover, adjacent looped chains are connected by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid-to-centroid distance = 3.689\u2005(4)\u2005\u00c5], giving rise to the formation of a two-dimensional supra\u00admolecular network propagating parallel to (110). Several inter\u00admolecular C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds further contribute to the stabilization of the crystal structure.In the title compound, {[Ag(C The coordination polymer is obtained by addition of the ligand to AgNO3 in methanol/aceto\u00adnitrile. The title nitrate salt is closely related to the perchlorate salt  because of their high efficiency and long-term stability , one nitrate anion, one methanol solvent mol\u00adecule, and two water solvent mol\u00adecules, each with an occupancy factor of 0.5, in the asymmetric unit. As shown in Fig.\u00a01I atom is coordinated by two pyridine N atoms and two imidazole N atoms from four individual i-pro-pyim ligands, giving rise to a highly distorted tetra\u00adhedral geometry with bond angles falling in the range of 100.33\u2005(19)\u2013122.76\u2005(19)\u00b0  and 42.2\u2005(3)\u00b0, respectively. Moreover, there are intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl and phenyl rings of both ligand types, N3,C4\u2013C8 and C21\u2013C26 [centroid-to-centroid distance = 3.760\u2005(4)\u2005\u00c5] for A and N6,C33\u2013C37 and C51\u2013C56 [centroid-to-centroid distance = 3.716\u2005(4)\u2005\u00c5] for B.In the title compound there are two crystallographically independent ligands, A ligands link two AgI atoms, resulting in the formation of a 14-membered cyclic dimer with an Ag\u22efAg distance of 6.963\u2005(2)\u2005\u00c5 and a \u03c0\u2013\u03c0 inter\u00adaction [centroid-to-centroid distance = 3.890\u2005(4)\u2005\u00c5] between N3-containing pyridine rings \u2005\u00c5 and a \u03c0\u2013\u03c0 inter\u00adaction [centroid-to-centroid distance = 3.922\u2005(4)\u2005\u00c5] between N6-containing pyridine rings. The two cyclic dimers are connected alternately by sharing AgI atoms, leading to the formation of a looped-chain structure extending along the a axis  \u2212x\u00a0+\u00a02, \u2212y, \u2212z\u00a0+\u00a01], resulting in the formation of a two-dimensional supra\u00admolecular network propagating parallel to (110) \u2005\u00c5] between the C50\u2013C55 and C500) Fig.\u00a03. No nota0) Fig.\u00a03.i-pro-pyim ligand was synthesized according to literature procedures  and allowing the solution to evaporate slowly at room temperature.The W and O2W) were refined with site-occupancy factors of 0.5, and their H atoms were not included in the model. All H atoms except those of the water mol\u00adecules were positioned geometrically and refined using a riding model, with d(C\u2014H) = 0.95\u2005\u00c5 for Csp2\u2014H, 1.00\u2005\u00c5 for methine, C\u2014H, 0.98\u2005\u00c5 for methyl, and O\u2014H 0.84\u2005\u00c5 for hydroxyl H atoms. For all H atoms, Uiso(H) = 1.2\u20131.5Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901600949X/sj5501sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901600949X/sj5501Isup2.hklStructure factors: contains datablock(s) I. DOI: 1484735CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title salt, crystalline water mol\u00adecules serve as donors for the weak inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efBr hydrogen bonds which link adjacent polymeric chains. 2(C5H9NO2)]\u00b7H2O}n, the CdII ion is coordinated by four bromido ligands and two carboxyl\u00adate oxygen atoms of two symmetry-related proline ligands, which exist in a zwitterionic form, in a distorted octa\u00adhedral geometry. There is an intra\u00admolecular N\u2014H\u22efO hydrogen bond between the amino group and the carboxyl\u00adate fragment. Each coordinating ligand bridges two CdII atoms, thus forming polymeric chains running along the c-axis direction. The water mol\u00adecules of crystallization serve as donors for the weak inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efBr hydrogen bonds that link adjacent polymeric chains, thus forming a three-dimensional structure. N\u2014H\u22efO and N\u2014H\u22efBr hydrogen bonds also occur.In the title coordination polymer, {[CdBr It is known that the chiral amino acids and their complexes are potential materials for NLO applications \u20132.7737\u2005(12)\u2005\u00c5] and two carboxyl\u00adate oxygen atoms [Cd\u2014O = 2.312\u2005(8) and 2.318\u2005(8)\u2005\u00c5] of two proline ligands in a slightly distorted octa\u00adhedral geometry. The title complex is extended as a polymeric chain which runs parallel to the c axis. Within one chain, adjacent CdII ions are separated by 3.727\u2005(1)\u2005\u00c5. The closest Cd\u22efCd distance between neighbouring polymeric chains is 8.579\u2005(2)\u2005\u00c5. The five endocyclic torsion angles of the pyrrolidine ring of the proline residue are N1\u2014C2\u2014C3\u2014C4 = 31.8\u2005(13)\u00b0, C2\u2014C3\u2014C4\u2014C5 = \u221239.1\u2005(15)\u00b0, C3\u2014C4\u2014C5\u2014N1 = 29.9\u2005(14)\u00b0, C2\u2014N1\u2014C5\u2014C4 = \u22129.7\u2005(12)\u00b0 and C5\u2014N1\u2014C2\u2014C3 = \u221213.1\u2005(11)\u00b0. The pyrrolidine ring exhibits twisted conformation on the C3\u2014C4 bond with a pseudo-rotation angle \u0394 = 249.3\u2005(12)\u00b0 and a maximum torsion angle \u03d5m = 38.5\u2005(8)\u00b0 et al., 1983A\u22efO2 hydrogen bond between the amino group and the carboxyl\u00adate fragment.In (I)The crystal structure of (I)viz. catena-[di\u00adchlorido-(4-hy\u00addroxy-l-proline)cadmium] (\u03bc2-l-pro\u00adline)cadmium monohydrate] manganese(II) monohydrate], has been structurally determined three times and has similar cell parameters and the same space group as the title compound  and cadmium bromide tetra\u00adhydrate (Loba) in an equimolar ratio were dissolved in double-distilled water. The obtained solution of the homogeneous mixture was evaporated at room temperature to afford the white crystalline title compound, which was then recrystallized by slow evaporation from an aqueous solution.To prepare the title compound, et al., 1983W\u22efH2W distances of the water mol\u00adecules were restrained to 0.85\u2005(2) and 1.38\u2005(2)\u2005\u00c5, respectively, using the DFIX option and included in the structure-factor calculations with Uiso(H1W/H2W) = 1.1Ueq(O1W). The remaining hydrogen atoms were placed in geometrically idealized positions (C\u2014H = 0.97\u20130.98\u2005\u00c5 and N\u2014H = 0.89\u2005\u00c5) with Uiso(H) = 1.2Ueq(C/N) and were constrained to ride on their parent atoms. Reflections 110 and 020 were partially obscured by the beam stop and were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015001176/cv5483sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015001176/cv5483Isup2.hklStructure factors: contains datablock(s) I. DOI: 1044327CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Stevens classification of levels of measurement involves four types of scale: \u201cNominal\u201d, \u201cOrdinal\u201d, \u201cInterval\u201d and \u201cRatio\u201d. This classification has been used widely in medical fields and has accomplished an important role in composition and interpretation of scale. With this classification, levels of measurements appear organized and validated. However, a group theory-like systematization beckons as an alternative because of its logical consistency and unexceptional applicability in the natural sciences but which may offer great advantages in clinical medicine. According to this viewpoint, the Stevens classification is reformulated within an abstract algebra-like scheme; \u2018Abelian modulo additive group\u2019 for \u201cOrdinal scale\u201d accompanied with \u2018zero\u2019, \u2018Abelian additive group\u2019 for \u201cInterval scale\u201d, and \u2018field\u2019 for \u201cRatio scale\u201d. Furthermore, a vector-like display arranges a mixture of schemes describing the assessment of patient states. With this vector-like notation, data-mining and data-set combination is possible on a higher abstract structure level based upon a hierarchical-cluster form. Using simple examples, we show that operations acting on the corresponding mixed schemes of this display allow for a sophisticated means of classifying, updating, monitoring, and prognosis, where better data mining/data usage and efficacy is expected. In 1946, S. S. Stevens devised his classification of \u201clevels of measurement\u201d ,3.Thus, in the following, we re-interpret Stevens classification, and endeavour to give it meaning in some abstract algebra-like modelling. There, the most preferred construct is a vector-like structure of various sets of scores based on individual scales and operators that permit changes of score within the set. Additionally, classical datasets that are classified in terms of the Stevens scales of measurement can be mined and combined on a higher abstract structure level based upon a hierarchical-cluster form. To explore this possibility, we provide simple examples to help readers understand this modelling tool.Stevens classified the scales of measurement into four scale types ; \u0406) \u201cNomFor \u0406), the \u201cNominal scale\u201d, there seems to be little room where group theoretical operations apply because within that scale only a labelling scheme is permissible. Although some non-cyclic group might be definable, it seems that little meaning can be attached to operations for this sort of scale.N\u2009=\u2009{0, 1, 2, 3,\u2026, N \u2013 2, N \u2013 1}, where modulo N addition is postulated. With this assumption, given two elements \u2018Xj\u2019 and \u2018Xk\u2019  corresponding for example to the severity of a clinical symptom and/or finding, then composition (denoted by \u2018*\u2019) is taken to be modulo N addition; \u2018Xj*X(j\u2192k)\u2009=\u2009Xk\u2019 (with X(j\u2192k) \u2208 ZN). Here \u2018X(j\u2192k)\u2019 is an operator that produces the change in score, \u2018Xj\u2009\u2192\u2009Xk\u2019 \u2009=\u2009Xj-1*Xk\u2009=\u2009Xk \u2013 Xj\u2019). Then, all scores \u2018Xj\u2019s and operators \u2018X(j\u2192k)\u2019 are composable within a single Abelian modulo additive group \u2018ZN\u2019, where \u2018Xj*Xk\u2009=\u2009Xk*Xj\u2019 holds, at least, in terms of operation \u2018*\u2019. Thus a patient\u2019s state corresponding to a certain illness or disease can be changed through the application of a single operation determined by the two elements belonging to \u2018ZN\u2019 , the combination of all scores being \u20180\u2019 and represented by the identity element for group Y\u2009=\u2009{ZN\u00d7n, *}. Here, Y is the n-fold Cartesian product of \u2018ZN\u2019 (n: the number of components) that comprises all possible assessments related to each state of a given disease, for instance, \u2018hypertension\u2019, \u2018hyperglycaemia\u2019, \u2018diabetes mellitus\u2019, \u2018acute pancreatitis\u2019, \u2018systemic lupus erythematosus\u2019, and \u2018cerebral artery stroke\u2019. If in addition composition is given by modulo \u2018N\u2019 arithmetic, prime numbers  are preferable , cj\u2009=\u2009Xj\u2009-\u2009[Xj], \u20180\u2009\u2264\u2009cj\u2009<\u20091\u2019; \u2018[X]\u2019 is the floor function meaning the highest integer below \u2018X\u2019). Similarly,\u2009-\u2009(v) can be redefined using the unit length \u20181\u2019 as an interval scale,0\u2019 (=0) that satisfies \u2018Xj \u25e6X0\u2009=\u2009X0 \u25e6Xj (=Xj\u2009+\u2009X0\u2009=\u2009Xj\u2009+\u20090)\u2009=\u2009Xj\u2019. Additionally, the inverse element is \u2018Xj-1\u2009=\u2009-Xj\u2019 satisfying \u2018Xj-1\u25e6Xj\u2009=\u2009Xj \u25e6Xj-1\u2009=\u2009Xj\u2009+\u2009Xj-1\u2009=\u2009Xj\u2009-\u2009Xj\u2009=\u2009X0 (=0)\u2019.There exists an identity element \u2018Xj\u2019s, i.e., U\u2009\u2261\u2009{Xj | Xj \u2208 R}. Because \u2018Xj , Xk, Xj \u2208 set U, the closure law holds. Therefore, this operation defines a group U\u2009=\u2009{Xj, \u25e6}  (mEq/l), sodium: [Na+] (mEq/l), calcium: [Ca++] (mg/dl), chloride: [Cl-] (mEq/l) and bicarbonate: [HCO3-] (mEq/l)\u2019. Also, there are clinical scales whose ranges are the open interval like \u2018-\u221e\u2009<\u2009X\u2009<\u2009+\u221e\u2019 ; \u2018Anion gap [AG]\u2009=\u2009[Na+]\u2009-\u2009([Cl-]\u2009+\u2009[HCO3-]) (reference range for blood tests: 12\u2009\u00b1\u20092\u00a0mEq/l)\u2019 and \u2018Base excess [BE] (reference range for blood tests: 0\u2009\u00b1\u20092\u00a0mmol/l)\u2019. However, both can be treated using the notion of \u2018field\u2019 because those values are real numbers where all four arithmetic operations are included, with the exception of division by zero. Thus, the above clinical values could be definable over a \u2018field\u2019. In this regard, we assume a rule that each unit like \u2018mEq/l\u2019 accompanies the value automatically with the results of operations regardless of types of operation among the four arithmetic operations (Note that there are cases when units vanish as when ratios are taken \u2018mEq/mEq (unitless)\u2019 or displayed in reciprocal form like \u2018l/mEq\u2019). Examples for \u2018[WBC] (/mm3)\u2019, \u2018[Na+] (mEq/l)\u2019 are presented in Appendix C.Nevertheless, other clinical scales range over a semi-open continuous interval like \u20180\u2009\u2264\u2009X\u2009<\u2009+\u221e\u2019 , such as \u2018blood concentration of white blood cells: [WBC] (/mmj # Xk\u2009=\u2009Xl (\u2208V), where ordinal arithmetic calculations are performed excluding of course division by zero.In this case, we consider a set V and assume that \u2018#\u2019 means one of \u2018addition, subtraction, multiplication, and division\u2019 collectively; thus, \u2018Xj\u2009+\u2009Xk\u2009=\u2009Xk\u2009+\u2009Xj, and associative: (Xj\u2009+\u2009Xk)\u2009+\u2009Xl\u2009=\u2009Xj\u2009+\u2009(Xk\u2009+\u2009Xl). As for multiplication, set V meets the conditions of a \u2018monoid\u2019  (/mm3)\u201d, field V2\u2009\u2261\u2009{X2j | X2j \u2208 R (mEq/l)} and V2\u2009=\u2009{X2j, #} for \u201cadministration of a certain drug like lithium carbonate: [Li+] (mEq/l)\u201d, field V3\u2009\u2261\u2009{X3j | X3j \u2208 R (mEq/l)} and V3\u2009=\u2009{X3j, #} for \u201csodium: [Na+] (mEq/l)\u201d, field V4\u2009\u2261\u2009{X4j, #} for calcium: [Ca++] (mg/dl), field V5 for chloride: [Cl-] (mEq/l), field V6 for \u2018Anion gap [AG] (mEq/l)\u2019, field V7 for \u2018Base excess [BE] (mmol/l)\u2019,\u2026, VN,\u2026, . For each, an independent abstract algebraic treatment is possible as for ordinal abstract algebra.Furthermore, different fields based on different sets of clinical values can be described as follows: field Vj\u2019, j\u2009=\u20091, 2, 3,\u2026: number of sessions), where the mixed expression and its totality of operations that could be performed belong to a single set R. Because of the possible variety of operation rules, the genuine use of this set may be unwieldy at this stage.By making use of all types of scales of measurement, we propose a vector-like expression of a patient\u2019s state  | clock time for the onset of sleep (/24\u00a0hrs) | blood concentration of white blood cell [WBC] (/mm3) | blood concentration of [Na+] (mEq/l)| a certain value ],Rj\u2019 changes to \u2018Rj+1\u2019 effected by operator \u2018R(j\u2192j+1)\u2019; we denote by \u2018\u25ca\u2019 the binary composition composed of the product of compositions for each component. Three possible states are:Next, suppose the patient\u2019s state \u2018R(1)1\u2019,\u2018X(2)1\u2019, and \u2018X(3)1\u2019, modulo 7 arithmetic (addition) is used. For the 2nd components, \u2018X(1)2, X(2)2, X(3)2\u2019, operations of Abelian addition are used. For the 3rd component, \u2018X(1)3, X(2)3, X(3)3\u2019, 4th \u2018X(1)4, X(2)4, X(3)4\u2019, the four arithmetic operators (those operations denoted by \u2018#\u2019) are required, and for the 5th, \u2018X(1)5, X(2)5, X(3)5\u2019, a certain operational unit is postulated. In the following examples, only addition/subtraction is presented; naturally, multiplication/division is also considered permissible.For the 1st component, \u2018X(1\u2192\u20092)\u2009=\u2009[X(1\u2192\u20092)1(mod\u20097)\u00a0|\u00a0X(1\u2192\u20092)2(/24\u00a0hrs)|\u00a0X(1\u2192\u20092)3(/mm3)|\u00a0X(1\u2192\u20092)4(mEq/l)|X(1\u2192\u20092)5(\u2026)], and R(2\u2192\u20093)\u2009=\u2009[X(2\u2192\u20093)1(mod\u20097)\u00a0|\u00a0X(2\u2192\u20093)2(/24\u00a0hrs)|\u00a0X(2\u2192\u20093)3(/mm3)|\u00a0X(2\u2192\u20093)4(mEq/l)|X(2\u2192\u20093)5(\u2026)]With related operators R(1\u21922)\u2019 and \u2018R(2\u21923)\u2019 from the three states given above are as follows:Then, using results in Appendix D, \u2018RThus, we confirm the relationDetails are illustrated in Appendix E.0)\u2009=\u2009[0 (mod 7)| 0 (/24\u00a0hrs)| 0 (/mm3)| 0 (mEq/l) | X0 (\u2026)]\u2019 such that \u2018Rj\u25caE\u2009=\u2009E\u25caRj\u2009=\u2009Rj\u2019. Additionally, there exists an inverse for any \u2018Rj\u2019, \u2018Rj-\u20091\u2009=\u2009[X(j)1-\u20091(mod\u20097)\u00a0|\u00a0X(j)2-\u20091(/24\u00a0hrs)|\u00a0X(j)3-\u20091(/mm3)|\u00a0X(j)4-\u20091(mEq/l)|X(j)5-\u20091(\u2026)] =\u2009[7\u2013X(j)1(mod\u20097)\u00a0|\u00a024\u2009-\u2009X(j)2(/24\u00a0hrs)|\u2009-\u2009X(j)3(/mm3)|\u2009-\u2009X(j)4(mEq/l)|X(j)5-\u20091(\u2026)]\u2019 that satisfies \u2018Rj-1\u25caRj\u2009=\u2009Rj\u25caRj-1\u2009=\u2009E\u2019. However, commutativity, \u2018Rj\u25caRk\u2009=\u2009Rk\u25caRj\u2019 and associativity, \u2018(Rj\u25caRk)\u25caRl\u2009=\u2009Rj\u25ca(Rk\u25caRl)\u2019 are not satisfied. Here, we assume that operators acting on \u2018Rj\u2019s should be performed from left to right, that is, from R1 to Rm . They should not be applied between \u2018Rj\u2019s. For any assortment of \u2018Rj\u2019s with scales of measurement among types I)\u2013IV), a single set R\u2009=\u2009{Rj| X(j)1\u2009\u00d7\u2009X(j)2\u2009\u00d7\u2009X(j)3\u2009\u00d7\u2009X(j)4\u2009\u00d7\u2009X(j)5} (\u2018\u00d7\u2019 means products among groups and fields) using a vector-like notation for the scoring of patient states can be structured where all possible assessments and/or clinical findings of the patient and treatment are included. The general form is the n-fold product; set R\u2009=\u2009{Rj| X(j)1\u2009\u00d7\u2009X(j)2\u2009\u00d7\u2009X(j)3\u2009\u00d7\u2009X(j)4\u2009\u00d7\u2009\u2026\u00d7X(j)(n-2)\u2009\u00d7\u2009X(j)(n-1)\u2009\u00d7\u2009X(j)n} .Note that, in general, there exists an identity \u2018E  each with four component (\u2018n\u2009=\u20095\u2019) and arrows (only symbols) that indicate the possible changes among the \u2018Rj\u2019s, as displayed in Figure\u00a0j\u2019s, are not combined directly with each other in the sense of operations. Then, the arrows could be re-displayed according to our concepts as operators \u2018R(j\u2192k) that can be regarded as elements \u2018Rj\u2019 belonging to a set R as in Figure\u00a0j\u2019s are merely a collection of values and the arrows in Figure\u00a0j\u2019s and \u2018R(j\u2192k)\u2019s are elements of a single set R subject to axioms of an abstract algebra as indicated using composition symbol \u2018\u25ca\u2019 in Figure\u00a0j to Rk\u2019 can be traced at each session. Displayed in this way, Figure\u00a0As for the possible application to better data mining or data usage from the viewpoint of our reinterpretation, we provide a simple example that may help readers to follow an outline of the argument. Consider an example of 17 states \u201cR1\u2019 there are four outcomes \u2018R6\u2019, \u2018R9\u2019, \u2018R16\u2019, and \u2018R17\u2019 containing nodes at \u2018R2\u2019 \u2018R4\u2019 \u2018R10\u2019 \u2018R12\u2019 and \u2018R13\u2019. By making use of our previous examples \u2018R1\u2009-\u2009R3\u2019, the next simplest examples with \u2018n (component number)\u2009=\u20095\u2019 can be confirmed easily:Here, consider the scenario of Figure\u00a0Following these results, the next relations, according to the tree in Figure\u00a0The operator expressions are evaluated in Appendix F.Similarly, the next sequences are definable in principle,a to Rb (=Ra\u25caR(a\u2192b)\u2009=\u2009Rb)\u2019 and \u2018Ra to Rc (=Ra\u25caR(a\u2192c)\u2009=\u2009Rc)\u2019 as \u2018Ra[(\u25caR(a\u2192b))(\u25caR(a\u2192c))]\u2019 ; here \u2018\u2026\u2019 meaning simple juxtaposition. All paths belonging to the operational tree of Figure\u00a0In general, we denote a node divergence \u2018R6, R9, R16, and R17\u2019 and divergence point \u2018R4\u2019 a notation \u2018(=R6), (=R9), (=R16) and (=R17)\u2019 might be considered. Hence,To display for easy recognition, for example, end states like \u2018R(3\u2009\u2192\u20094)[(\u25caR(4\u2009\u2192\u20095)\u2009\u25ca\u2009R(5\u2009\u2192\u20096))(\u25caR(4\u2009\u2192\u20098)\u2009\u25ca\u2009R(8\u2009\u2192\u20099)\u2009\u25ca\u2009R(9\u2009\u2192\u200910))(\u25caR(4\u2009\u2192\u200915)\u2009\u25ca\u2009R(15\u2009\u2192\u200916))\u2009\u2026] from the left-hand side by \u2018R3\u2019. The subsequent result can be expressed in accordance with the single scheme presented in Figure\u00a0Moreover, composition with an operator as in operating on \u2018R\u2009\u2192\u20094, \u20182Rj1 = 21Rj2 \u222a 22Rj2\u2019 = [X(j)3 (/mm3) | X(j)4 (mEq/l)|X(j)5 (\u2026)], whereas at the third level, \u201822Rj2 = 221Rj3 \u222a 222Rj3\u2019 = [X(j)4 (mEq/l)|X(j)5 (\u2026)], 221Rj3 = [X(j)4 (mEq/l)], 222Rj3 = [X(j)5 (\u2026)] 1, X(j)2, X(j)3, X(j)4, X(j)5} = [X(j)1 (mod 7) | X(j)2 (/24 hrs) | X(j)3 (/mm3) | X(j)4 (mEq/l) | X(j)5 (\u2026)]. A hierarchy has additional levels as necessary to reach single units at its base \u2019 and \u2018R1 = [X(1)1| X(1)2 |\u2026| X(1)b]\u2019, \u2018{Rk, R1} =Rj [X(j)1| X(j)2 |\u2026| X(j)a | X(j)a+1| X(j)a+2 |\u2026| X(j)a+b] \u2019 . In this way, classical datasets that are classified in the Stevens scales of measurement could be mined and combined on a higher abstract structure level. To help better understand the concept, a sequence of schemes illustrating the principles of our model is presented in Figure\u00a0Additionally, we can include data mining in a more symbolic/abstract way as follows. For an arbitrary j , a hierarchical-cluster-like expression can be defined . For ins X(j)2 /2 hrs], \u20182Subject to future improvements, we envisage that this compact description is versatile to provide better data mining/data usage than from existing methods, although a final version is far from complete at this early stage.11\u2019 arises as a natural modular scale. In contrast, similar approaches might be difficult for a \u201cvisual analogue scale\u201d  changes in the following manner: \u20185000 (/mm1 = 145 (mEq/l)\u2019 changes into \u2018[Na]2 = 128 (mEq/l)\u2019, because \u2018[Na]1 # [Na](1\u21922) = [Na]2\u2019, the operator for addition is obtain from \u2018[Na](1\u21922) = [Na]2 - [Na]1 = 128 - 145 = - 17 (mEq/l)\u2019. Collectively, the operator for division is \u2018[Na](1\u21922) = [Na]2/[Na]1 = 128/145 (mEq/l)\u2019.For an another example, if \u2018[Na](1\u21922) = R2 - R1R3) | 128 (mEq/l) | X(2)5 (\u2026)] - [2 (mod 7) | 21 (/24 hrs) | 5000 (/mm3) | 145 (mEq/l) | X(1)5 (\u2026)],= [5 (mod 7) | 19.5 (/24 hrs) | 18000 (/mm3) | 128 - 145 (mEq/l) | X(1\u21922)5 (\u2026)],= [5 - 2 (mod 7) | 19.5 - 21 (/24 hrs) | 18000 - 5000 (/mm3) | - 17 (mEq/l) | X(1\u21922)5 (\u2026)].= [3 (mod 7) | - 1.5 (/24 hrs) | 13000 (/mm(2\u21923) = R3 - R2R3) | 158 (mEq/l)] | X(3)5 (\u2026)] - [5 (mod 7) | 19.5 (/24 hrs) | 18000 (/mm3) | 128 (mEq/l) | X(2)5 (\u2026)],= [3 (mod 7) | 22 (/24 hrs) | 7000 (/mm3) | 158 - 128 (mEq/l) | X(2\u21923)5 (\u2026)],= [3 - 5 (mod 7) | 22 - 19.5 (/24 hrs) | 7000 - 18000 (/mm3) | 30 (mEq/l) | X(2\u21923)5 (\u2026)],= [- 2 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm3) | 30 (mEq/l) | X(2\u21923)5 (\u2026)].= [5 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm1\u25caR(1\u21922)\u25caR(2\u21923) = [2 (mod 7) | 21 (/24 hrs) | 5000 (/mm3) | 145 (mEq/l) | X(1)5 (\u2026)]\u25ca[3 (mod 7) | - 1.5 (/24 hrs) | 13000 (/mm3) | - 17 (mEq/l) | X(1\u21922)5 (\u2026)]\u25ca[5 (mod 7) | 2.5 (/24 hrs) | - 11000 (/mm3) | 30 (mEq/l) | X(2\u21923)5 (\u2026)],R3) | 145 - 17 +30 (mEq/l) | X(3)5 (\u2026)],= [2 + 3 + 5 (mod 7) | 21 - 1.5 + 2.5 (/24 hrs) | 5000 + 13000 - 11000 (/mm3) | 158 (mEq/l) | X(3)5 (\u2026)],= [10 (mod 7) | 22 (/24 hrs) | 7000 (/mm3) | 158 (mEq/l) | X(3)5 (\u2026)].= [3 (mod 7) | 22 (/24 hrs) | 7000  = R10 - R2 = [0 - 5 (mod 7) | 17 - 19.5 (/24 hrs) | 9000 - 18000 (/mm3) | 130 - 128 (mEq/l) | X(2\u219210)5 (\u2026)] = [- 5 (mod 7) | - 2.5 (/24 hrs) | - 9000 (/mm3) | 2 (mEq/l) | X(2\u219210)5 (\u2026)],R(10\u219211) = R11 - R10 = [6 - 0 (mod 7) | 20 - 17 (/24 hrs) | 20000 - 9000 (/mm3) | 149 - 130 (mEq/l) | X(10\u219211)5 (\u2026)] = [6 (mod 7) | 3 (/24 hrs) | 11000 (/mm3) | 19 (mEq/l) | X(10\u219211)5 (\u2026)],R(11\u219212) = R12 - R11 = [4 - 6 (mod 7) | 23 - 20 (/24 hrs) | 6000 - 20000 (/mm3) | 140 - 149 (mEq/l) | X(11\u219212)5 (\u2026)] = [- 2 (mod 7) | 3 (/24 hrs) | - 14000 (/mm3) | - 9 (mEq/l) | X(11\u219212)5 (\u2026)],R(10\u219213) = R13 - R10 = [1 - 0 (mod 7) | 18 - 17 (/24 hrs) | 5000 - 9000 (/mm3) | 135 - 130 (mEq/l) | X(10\u219213)5 (\u2026)] = [1 (mod 7) | 1 (/24 hrs) | - 4000 (/mm3) | 5 (mEq/l) | X(10\u219213)5 (\u2026)],R(13\u219217) = R17 - R13 = [2 - 1 (mod 7) | 23.5 - 18 (/24 hrs) | 3000 - 5000 (/mm3) | 150 - 135 (mEq/l) | X(13\u219217)5 (\u2026)] = [1 (mod 7) | 5.5 (/24 hrs) | - 2000 (/mm3) | 15 (mEq/l) | X(13\u219217)5 (\u2026)].RThe authors declare that they have no competing interests.JS conceived the main concept of this article and wrote the manuscript. SM revised the manuscript. JI gave advice on the potential validity from the viewpoint of clinical research and treatment. Additionally, all authors read and approved the final manuscript."}
{"text": "The aromatic substituents on the sulfonate group are oriented gauche to one another with a C\u2014O\u2014S\u2014C torsion angle of \u221262.0\u2005(3)\u00b0. The supra\u00admolecular features that contribute to the crystal lattice are offset \u03c0-\u03c0 and multiple C\u2014H\u22efO inter\u00adactions.The title compound, C 13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-di\u00adnitro\u00adphenol and p-toluene\u00adsulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH . The aromatic substituents on the sulfonate group are oriented gauche to one another with a C\u2014O\u2014S\u2014C torsion angle of \u221262.0\u2005(3)\u00b0. The supra\u00admolecular features that contribute to the crystal stability are offset \u03c0\u2013\u03c0 [centroid\u2013centroid distance = 3.729\u2005(2)\u2005\u00c5] and multiple C\u2014H\u22efO inter\u00adactions.The title compound, C Analogous to the carbonyl group, nucleophilic substitution reactions of sulfonyl derivatives have also been reported  reactions similar to those reported by others . The bond angle between the S=O groups (O1\u2014S1\u2014O2) is 121.20\u2005(17)\u00b0, while that of the aromatic substituents (O3\u2014S1\u2014C5) is 103.27\u2005(15)\u00b0. The two aromatic rings are in a gauche orientation about the O3\u2014S1 bond with a torsion angle (C8\u2014O3\u2014S1\u2014C5) of \u221262.0\u2005(3)\u00b0.The central sulfur atom (S1) is tetra\u00adhedral with S=O bond lengths of 1.415\u2005(3) and 1.414\u2005(3)\u2005\u00c5, and an S\u2014O bond length of 1.634\u2005(3)\u2005\u00c5 Fig.\u00a02a. The bet al., 2003ab). While the bond lengths of the two polymorphs agree within 0.01\u2005\u00c5 of each other, there are some differences between bond angles. The aromatic rings in WUVYUH are in an anti orientation along the S\u2014O bond, with a torsion angle of 141.02\u2005(9)\u00b0. The bond angle between the S=O groups (O1\u2014S1\u2014O2) is 119.80\u2005(6)\u00b0, while that of the aromatic substituents (O3\u2014S1\u2014C5) is 98.17\u2005(5)\u00b0.For comparison, the polymorph WUVYUH  = 3.379\u2005(4)\u2005\u00c5, and O7(nitro)\u22efS1v(sulfonic ester) = 3.877\u2005(3)\u2005\u00c5. The relatively short inter\u00admolecular distance between N2 and O17 suggests the presence of favorable N\u22efO inter\u00adactions in the crystal  is in proximity to the sulfonic ester of the C2\u2013C7et al., 2008ortho-substit\u00aduent is a nitro group and the para-position bears a second tosyl\u00adate group. The remaining entries have various electron-rich groups in the ortho-position including meth\u00adoxy .The CSD contains three additional structures where the position p-toluene\u00adsulfonyl chloride (5\u2005mmol) and pyridine (3\u2005mmol) in 10\u2005mL of di\u00adchloro\u00admethane for 30 minutes at room temperature. The reaction was heated to 353\u2005K for 30 minutes in a microwave reactor, then cooled to room temperature and stirred overnight in a fume hood. The reaction mixture was transferred to a scintillation vial where the pale yellow product crystallized upon standing after several days and was filtered from the mother liquor (m.p. 393.4\u2013394.7\u2005K).The title compound was prepared by stirring 2,4-di\u00adnitro\u00adphenol (5\u2005mmol), Uiso(H) = 1.2Ueq(C) for CH groups and Uiso(H) = 1.5 Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015650/pk2562sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015650/pk2562Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015650/pk2562Isup3.cmlSupporting information file. DOI: 1419864CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-tosyl\u00adacryl\u00adamide compounds, (I) and (II), the conformation about the C=C bond is E. In (I), the furan, phenyl and 4-methyl\u00adbenzene rings are inclined to the acryl\u00adamide mean plane [\u2013NH\u2014C(= O)\u2014C=C\u2013] by 26.47\u2005(11), 69.01\u2005(8) and 82.49\u2005(9)\u00b0, respectively. In (II), the phenyl, and 3-methyl and 4-methyl\u00adbenzene rings are inclined to the acryl\u00adamide mean plane by 11.61\u2005(10), 78.44\u2005(10) and 78.24\u2005(10)\u00b0, respectively. In the crystals of both compounds, mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with In the title  N-tosyl\u00adacryl\u00adamide compounds, C20H17NO4S, (I), and C23H21NO3S, (II), the conformation about the C=C bond is E. The acryl\u00adamide groups, [\u2013NH\u2014C(=O)\u2014C=C\u2013], are almost planar, with the N\u2014C\u2014C=C torsion angle being \u2212170.18\u2005(14)\u00b0 in (I) and \u2212168.01\u2005(17)\u00b0 in (II). In (I), the furan, phenyl and 4-methyl\u00adbenzene rings are inclined to the acryl\u00adamide mean plane by 26.47\u2005(11), 69.01\u2005(8) and 82.49\u2005(9)\u00b0, respectively. In (II), the phenyl, 3-methyl\u00adbenzene and 4-methyl\u00adbenzene rings are inclined to the acryl\u00adamide mean plane by 11.61\u2005(10), 78.44\u2005(10) and 78.24\u2005(10)\u00b0, respectively. There is an intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction present in compound (II). In the crystals of both compounds, mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(8) ring motif. In (I), the dimers are reinforced by C\u2014H\u22efO hydrogen bonds and linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains along [011]. In the crystal of (II), the dimers are linked via C\u2014H\u22efO hydrogen bonds, forming chains along [100]. The chains are further linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to (010).In the title  There is also a C\u2014H\u22ef\u03c0 inter\u00adaction present, linking the chains to form layers lying parallel to (010).In the crystal of both compounds, mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds Tables 1 and 2 \u25b8,et al., 2016N-(phenyl\u00adsulfon\u00adyl)acryl\u00adamide yielded five hits. Four of these compounds involve the 4-methyl\u00adbenzene\u00adsulfonyl group and one compound involves a phenyl\u00adsulfonyl group. This later compound, 2-(4-chloro\u00adphen\u00adyl)-3-(2-fur\u00adyl)-N-(phenyl\u00adsulfon\u00adyl)acryl\u00adamide : 4-methyl\u00adbenzene\u00adsulfonyl azide (4.5\u2005mmol), CuI , Et4NI , ethynyl\u00adbenzene (4.5\u2005mmol), and furan-2-carbaldehyde (3\u2005mmol) were suspended in CH2Cl2 (5\u2005ml) in a 10\u2005mL Schlenk tube under nitro\u00adgen at rt. LiOH  was then added, and the resulting solution was stirred at this temperature. Upon full consumption of furan-2-carbaldehyde, the reaction was quenched by saturated aqueous NH4Cl (5\u2005ml) and extracted with CH2Cl2 (10\u2005ml \u00d7 3). The combined organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude residue was purified by column chroma\u00adtography on silica gel (n-hexa\u00adne/EtOAc 5:1 v/v) to afford compound (I)n-hexa\u00adne/EtOAc and after slow evaporation over several days, colourless crystals suitable for analysis by X-ray diffraction were formed.Compound (II): 4-methyl\u00adbenzene\u00adsulfonyl azide (4.5\u2005mmol), CuI , Et4NI , 1-eth\u00adyn\u00adyl-3-methyl\u00adbenzene (4.5\u2005mmol), and benzaldehyde (3\u2005mmol) were suspended in CH2Cl2 (5\u2005ml) in a 10\u2005mL Schlenk tube under nitro\u00adgen at rt. LiOH  was then added, and the resulting solution was stirred at this temperature. Upon full consumption of benzaldehyde, the reaction was quenched by saturated aqueous NH4Cl (5\u2005ml) and extracted with CH2Cl2 (3 \u00d7 10\u2005ml). The combined organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The crude residue was purified by column chroma\u00adtography on silica gel (n-hexa\u00adne/EtOAc 5:1 v/v) to afford compound (II)n-hexa\u00adne/EtOAc and after slow evaporation over several days, colourless block-like crystals were obtained.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016007611/su5296sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: Click here for additional data file.10.1107/S2056989016007611/su5296Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007611/su5296IIsup3.cmlSupporting information file. DOI: 1478730, 1478729CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, supra\u00admolecular chains are formed  13H10N2O2 , features an almost planar (r.m.s. deviation = 0.0095\u2005\u00c5) central C3O2 core consolidated by an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bond. Twists are evident in the mol\u00adecule, as seen in the dihedral angles between the central core and the 2- and pyridin-3-yl rings of 8.91\u2005(7) and 15.88\u2005(6)\u00b0, respectively. The conformation about the C=C bond [1.3931\u2005(17)\u2005\u00c5] is Z, and the N atoms lie to the same side of the mol\u00adecule. In the mol\u00adecular packing, supra\u00admolecular chains along the a axis are mediated by \u03c0(pyridin-2-yl)\u2013\u03c0(pyridin-3-yl) inter\u00adactions [inter-centroid distance = 3.7662\u2005(9)\u2005\u00c5]. The observation that chains pack with no directional inter\u00adactions between them is consistent with the calculated electrostatic potential, which indicates that repulsive inter\u00adactions dominate.The title compound, C III and GaIII octa\u00adhedral building blocks for network structures linked by AgI ions -2,4-penta\u00adnedione as well as the mixed-MOF with AgNO3 in a two-dimensional honeycomb structure while at higher AgI concentrations, a one-dimensional ladder motif was formed versus hy\u00addroxy-O atoms is not readily confirmed by a great disparity in the C1\u2014O1 [1.2871\u2005(14)\u2005\u00c5] and C3\u2014O2 [1.3041\u2005(14)\u2005\u00c5] bond lengths. The assignment was based on an unrestrained refinement of the H1O atom which resulted in a O2\u2014H1O bond length of 1.090\u2005(18)\u2005\u00c5. More certainty is associated with the assignment of the nitro\u00adgen atoms in the pyridyl rings. Thus, the short C5\u2014N1 and C4\u2014N1 [1.3325\u2005(17) and 1.3484\u2005(15)\u2005\u00c5] and C10\u2014N2 and C11\u2014N2 [1.3371\u2005(17) and 1.3397\u2005(18)\u2005\u00c5] bond lengths cf. the C\u2014C bonds in the rings confirm their assignment. The central C3O2 residual in (I)syn arrangement of the oxygen atoms enables the formation of an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bond, Table\u00a01Z, and, to a first approximation, the N1 and N2 atoms lie to the same side of the mol\u00adecule.In (I)Cg(N1-pyridin\u00adyl)\u22efCg(N2-pyridin\u00adyl) = 3.7662\u2005(9)\u2005\u00c5, angle of inclination = 7.45\u2005(6)\u00b0 for symmetry operation 1\u00a0+\u00a0x, y, z]. The result is the formation of a linear supra\u00admolecular chain, Fig.\u00a02a. The chains pack with no directional inter\u00adactions between them in accord with the distance criteria in PLATON , is viewed as bright-red spots near these atoms on the Hirshfeld surface mapped over dnorm, Fig.\u00a04From the Hirshfeld surface mapped over electrostatic potential, Fig.\u00a03gs Fig.\u00a02a, is via, and those delin\u00adeated into H\u22efH, C\u22efC, O\u22efH/H\u22efO, C\u22efH/H\u22efC and N\u22efH/H\u22efN contacts are illustrated in Fig.\u00a05b\u2013f, respectively; their relative contributions to the surface are qu\u00adanti\u00adfied in Table\u00a02et al., 2007b, with a single peak at  less than the van der Waals separation corresponding to a short H13\u22efH13 contact of 2.33\u2005\u00c5 . The short inter\u00adatomic C5\u22efC10 contact and \u03c0\u2013\u03c0 stacking inter\u00adactions appear as an arrow-like distribution of points with the tip at de + di \u223c 3.3\u2005\u00c5 . The presence of \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridyl rings is also apparent from the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with shape-index property identified with arrows in the image of Fig.\u00a06The overall 2D fingerprint plot, Fig.\u00a05\u2005\u00c5 Fig.\u00a05c. The pd\u2013f. However, the points are distributed at  distances greater than their respective van der Waals separations. This is consistent with the repulsion between the atoms having electrostatic negative potential dominating the mol\u00adecular packing, hence the lack of specific inter\u00admolecular inter\u00adactions between supra\u00admolecular chains.The two-dimensional fingerprint plots delineated into O\u22efH/H\u22efO, C\u22efH/H\u22efC and N\u22efH/H\u22efN inter\u00adactions exhibit their usual characteristic features in their respective plots; Fig.\u00a04et al., 2016et al.  solution afforded colourless crystals. Yield: 4.03\u2005g (70.7%). M.p: 377\u2013378\u2005K. IR (KBr pellet) \u03bdmax/cm\u22121: 3121 (m), 3053 (m), 2922 (m), 2853 (m), 1611 (s), 1595 (s), 1539 (m), 1458 (m), 1418 (m), 1221 (m), 1188 (m), 1146 (m), 1115 (m), 1067 (m), 1018 (m), 989 (m), 926 (m), 775 (s), 739 (m), 679 (s), 611 (m). Analysis calculated for C13H10N2O2: C, 69.03; H, 4.42; N, 12.19. Found: C, 68.73; H, 4.54; N, 12.16. MS: m/z 226. 1H NMR  \u03b4 9.22 , 8.82 , 8.44 , 8.17 , 8.09 , 7.70 , 7.63 .2-Acetyl\u00adpyridine  was added to a suspension of NaH  in anhydrous THF (10\u2005ml) at room temperature with stirring. Ethyl nicotinate  in anhydrous THF (10ml) was added dropwise to the mixture over 3\u2005min. The yellow mixture was refluxed under a nitro\u00adgen atmosphere for 1.3\u2005h and then quenched with ice\u2013water (50\u2005ml). Glacial acetic acid was added to adjust the pH to 6\u20137. The resulting yellow precipitate was collected by filtration, washed with cold water and dried under vacuum. Recrystallization from di\u00adchloro\u00admethane\u2013hexane (1:1 Uiso(H) set to 1.2Ueq(C). The hy\u00addroxy-H atom was located in a difference map and refined with O\u2014H = 0.82\u00b10.01\u00c5, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698901600832X/hb7587sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901600832X/hb7587Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600832X/hb7587Isup3.cmlSupporting information file. DOI: 1481225CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A and B) in the asymmetric unit. In the crystal, individual mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming A\u2013A and B\u2013B inversion dimers with The title compound, crystallized with two conformationally similar mol\u00adecules  in the asymmetric unit. The two mol\u00adecules have the same conformation; the mol\u00adecular overlap gives weighted and unit-weight r.m.s. fits of 0.047 and 0.043\u2005\u00c5, respectively. The conformation of the N-(hydroxeth\u00adyl)formamide chains are very similar, as indicated by the C\u2014N(H)\u2014C=O and C\u2014N(H)\u2014C\u2014O(H) torsion angles, which are, respectively, \u22121.8\u2005(3) and \u221291.5\u2005(2)\u00b0 for mol\u00adecule A, and \u22122.1\u2005(3) and \u221295.7\u2005(2)\u00b0 for mol\u00adecule B. In the crystal, individual mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming A\u2013A and B\u2013B inversion dimers with R22(12) ring motifs. The dimers are linked via N\u2014H\u22efO hydrogen bonds, forming alternating layers of A and B mol\u00adecules parallel to the bc plane. Within the layers of B mol\u00adecules, there are weak C\u2014H\u22efCl hydrogen bonds present.The title compound, C This has led to the use of formamides as key inter\u00admediates in numerous organic synthetic endeavours (Kobayashi A and B) in the asymmetric unit. The arbitrarily chosen chirality of atoms C2 in mol\u00adecule A and C5 in mol\u00adecule B is the same. The backbones of the two mol\u00adecules  have almost identical conformations with weighted and unit-weight r.m.s. overlay fits of 0.047 and 0.043\u2005\u00c5, respectively, for the six atoms in each mol\u00adecule formamide, yielded 25 hits. The majority concern metal complexes of the ligand N-(hy\u00addroxy\u00admeth\u00adyl)nicotinamide. Only one compound, N,N\u2032-diformamide formamide chain as indicated by the C\u2014N(H)\u2014C\u2014O(H) and C\u2014N(H)\u2014C=O torsion angles: 1.6\u2005(2) and \u221299.09\u2005(14)\u00b0 for the above mentioned compound compared to \u22121.8\u2005(3) and \u221291.5\u2005(2)\u00b0 for mol\u00adecule A and \u22122.1\u2005(3) and \u221295.7\u2005(2)\u00b0 for mol\u00adecule B of the title compound formamide was dissolved in hot ethanol, followed by treatment with charcoal. The filtered solution was left to crystallize by slow evaporation, forming colourless block-like crystals (m.p. 393\u2005K).The title compound can be synthesized following a literature procedure  I. DOI: 10.1107/S2056989015020459/hg5462Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020459/hg5462Isup3.cmlSupporting information file. DOI: 1009715CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two aromatic rings present in the mol\u00adecule are almost coplanar, forming a dihedral angle of 1.4\u2005(2)\u00b0. The five-membered ring involving the metal atom is puckered, with an amplitude Q = 0.358\u2005(2)\u2005\u00c5 and \u03d5 = 204.1\u2005(6)\u00b0. In the crystal, pairs of inversion-related mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds. An O\u2014H\u22efO hydrogen bond connects the water ligand to the di\u00admethyl\u00adformamide solvent mol\u00adecule. The crystal packing also features \u03c0\u2013\u03c0 [centroid\u2013centroid distance of 3.688\u2005(2)\u2005\u00c5] and C\u2014H\u22efO inter\u00adactions.The title compound, [Mo(C The complex adopts a distorted octa\u00adhedral geometry around the Mo atom \u2005\u00c5] is close to the reported C\u2014O single bond length  and \u22121.4\u2005(4)\u00b0, respectively]. This configuration is similar to that of the metal-free ligand \u00c5 and \u03d5 = 204.1\u2005(6)\u00b0.The ligand adopts D\u22efA distances 2.891\u2005(4) and 2.701\u2005(4)\u2005\u00c5 respectively, and a non-classical C\u2014H\u22efO inter\u00adaction with a D\u22efA distance of 3.421\u2005(5)\u2005\u00c5. These inter\u00adactions connect pairs of mol\u00adecules along with the solvent di\u00admethyl\u00adformamide. The complex mol\u00adecule is stacked along the b axis through two different types of O\u2014H\u22ef\u03c0 inter\u00adaction  with a centroid-centroid distance of 3.688\u2005(2)\u2005\u00c5  for 3\u2005h. The brown precipitate obtained was filtered, washed with methanol, dried and recrystallized from di\u00admethyl\u00adformamide . FT\u2013IR  \u03bdmax: 3400, 3194, 1657, 1546, 1345, 937, 810.The complex was synthesized by refluxing a methano\u00adlic solution of benzoyl hydrazone  and MoClUiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C). The O\u2014H distances were restrained with 1,2 and 1,3 distance restraints of 0.86\u2005(1) and 1.36\u2005(2)\u2005\u00c5. Reflections (0 0 2), (1 0 1) and  I. DOI: 10.1107/S2056989015009639/pk2550Isup2.hklStructure factors: contains datablock(s) I. DOI: 1401828CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Weak C\u2014H\u22efCl and C\u2014H\u22efS hydrogen-bonding inter\u00adactions consolidate the packing of the structure.The title cobalt(II) complex consists of a CoCl 3CS)2C=NC\u00a0 N}2CoCl2], consists of a CoII atom coordinated in a distorted tetra\u00adhedral manner by two Cl\u2212 ligands and the terminal N atoms of two dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate ligands. The two organic ligands are almost coplanar, with a dihedral angle of 5.99\u2005(6)\u00b0 between their least-squares planes. The crystal packing features pairs of inversion-related complexes that are held together through C\u2014H\u22efCl and C\u2014H\u22efS inter\u00adactions and \u03c0\u2013\u03c0 stacking [centroid-to-centroid distance = 3.515 (su?) \u00c5]. Additional C\u2014H\u22efCl and C\u2014H\u22efS inter\u00adactions, as well as Cl\u22efS contacts < 3.6\u2005\u00c5, consolidate the crystal packing.The structure of the mononuclear title complex, [{(H N-cyano\u00addithio\u00adimino\u00adcarbonate with its two N and two S atoms has four possible coordination sites and hence should present a high coordination ability. The behaviour of N and S atoms according to Pearson\u2019s concept as hard and soft donors, respectively, may allow coordination to both hard and soft Lewis acids. Despite this coordination property, the ligand has scarcely been studied. Only one crystalline compound with dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate as a ligand has been reported previously  chloride hexa\u00adhydrate and dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate which has yielded the title complex, [{(H3CS)2C=NC\u00a0 N}2CoCl2].Dimethyl II atom coordinated in a distorted tetra\u00adhedral manner by two Cl\u2212 ligands and the cyanide N atoms of two dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate ligands \u00b0]. The CoII atom lies 0.437\u2005(2) and 0.557\u2005(2)\u2005\u00c5 from the mean planes of the two ligands.The structure of the title complex consists of a Cods Fig.\u00a01. Co\u2014Cl ads Fig.\u00a01. The Cl\u2014t Table\u00a01. Despite3C\u2014S groups of the adjacent mol\u00adecule, presumably reducing steric inter\u00adactions. Apart from C\u2014H\u22efCl and C\u2014H\u22efS inter\u00adactions (Table\u00a02(su?) \u00c5 prevails within a pair of complex mol\u00adecules. In the crystal, these pairs are arranged parallel to (110)  Fig.\u00a02. Additio0) Fig.\u00a02.2\u00b76H2O  in aceto\u00adnitrile (30\u2005ml) and dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate  in aceto\u00adnitrile (20\u2005ml) at room temperature. The resulting blue solution was stirred for about 2\u2005h. Blue crystals suitable for single-crystal X-ray diffraction were obtained after six days of slow solvent evaporation at room temperature (300\u2005K).All chemicals were purchased from Aldrich (Germany) and were used as received. The title compound was prepared by mixing of CoCl\u03bd(C\u00a0N) 2224\u2005cm\u22121, \u03bd(C=N) 1458\u2005cm\u22121, \u03bd(CS2) + rocking CH3 1024 and 962\u2005cm\u22121. Melting point 398\u2005K. Elemental analyses of C8H12Cl2CoN4S4: calculated (found): C 22.75 (21.91), H 2.86 (3.43), N 13.27 (12.63), S 30.37 (29.40).Infra-red bands: Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989015023439/wm5249sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023439/wm5249Isup2.hklStructure factors: contains datablock(s) I. DOI: 1440755CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex, the MnII atom is coordinated by two 4-nitro\u00adbenzoate (NB) anions, two nicotinamide (NA) ligands and two water mol\u00adecules; the NB and NA ligands act as monodentate ligands. The resulting MnN2O4 coordination polyhedron is a distorted octa\u00adhedron.In the title centrosymmetric Mn 7H4NO4)2(C6H6N2O)2(H2O)2], contains one MnII atom, one 4-nitro\u00adbenzoate (NB) anion, one nicotinamide (NA) ligand and one water mol\u00adecule; NA and NB each act as a monodentate ligand. The MnII atom, lying on an inversion centre, is coordinated by four O atoms and two pyridine N atoms in a distorted octa\u00adhedral geometry. The water mol\u00adecules are hydrogen bonded to the carboxyl\u00adate O atoms. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 24.4\u2005(3)\u00b0, while the benzene and pyridine rings are oriented at a dihedral angle of 86.63\u2005(11)\u00b0. In the crystal, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules, forming a layer parallel to the ab plane. The layers are further linked via weak C\u2014H\u22efO hydrogen bonds, a \u03c0\u2013\u03c0 stacking inter\u00adaction [centroid\u2013centroid distance = 3.868\u2005(2)\u2005\u00c5] and a weak C\u2014H\u22ef\u03c0 inter\u00adaction, resulting in a three-dimensional network.The asymmetric unit of the title compound, [Mn(C A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. The NA ring is the reactive part of nicotinamide adenine dinucleotide (NAD) and its phosphate (NADP), which are the major electron carriers in many biological oxidation\u2013reduction reactions \u00admanganese \u00adbis\u00ad(4-nitro\u00adbenzoato)manganese  of the two symmetry-related monodentate NB anions and the two symmetry-related water O atoms (O6 and O6iii) around the MnII atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two pyridine N atoms (N2 and N2iii) of the two symmetry-related monodentate NA ligands in the axial positions  in the carboxyl\u00adate group indicates delocalized bonds rather than localized single and double bonds. The Mn\u2014O bond lengths [2.156\u2005(2) and 2.115\u2005(2)\u2005\u00c5] and the Mn\u2014N bond length [2.134\u2005(3)\u2005\u00c5] are close to the standard values. Atom Mn1 lies 0.4172\u2005(1)\u2005\u00c5 above the O1/O2/C1 plane of the carboxyl\u00adate group. The O\u2014Mn\u2014O and O\u2014Mn\u2014N bond angles deviate slightly from the ideal value of 90\u00b0. The dihedral angle between the carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene (C2\u2013C7) ring is 24.4\u2005(3)\u00b0, while the benzene ring and the pyridine (N2/C8\u2013C12) ring are oriented at a dihedral angle of 86.63\u2005(11)\u00b0.na\u22efOna (na = nicotinamide), N\u2014Hna\u22efOc (c = carboxyl\u00adate group) and O\u2014Hw\u22efOna (w = water) hydrogen bonds \u2005\u00c5; symmetry code: (ix) 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z, where Cg1 is the centroid of the C2\u2013C7 ring].In the crystal, inter\u00admolecular N\u2014Hs Table\u00a01 link thene Fig.\u00a02. In the n Table\u00a01 and a \u03c0\u20134\u00b7H2O  in H2O (25\u2005ml) and nicotinamide  in H2O (25\u2005ml) with sodium 4-nitro\u00adbenzoate  in H2O (150\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colourless single crystals.The title compound was prepared by the reaction of MnSOA and H3B of the NH2 group were located in a difference Fourier map, and their coordinates were refined with distance restraints of O\u2014H = 0.85\u2005(2)\u2005\u00c5 and N\u2014H = 0.86\u2005(2)\u2005\u00c5, and with Uiso(H) = 1.5Ueq. The C-bound H atoms were positioned geometrically with C\u2014H = 0.93\u2005\u00c5 and were constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016005612/is5449sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016005612/is5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 1472331CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III atom in the title mol\u00adecule adopts a distorted octa\u00adhedral coordination sphere, being C,N-chelated by two 2-(pyridin-2-yl)phenyl ligands and N,O-chelated by one ancillary 2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolate ligand. The crystal packing is stabilized by inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions.The Ir 11H8N)2(C13H10NO)]\u00b7CH2Cl2, the IrIII ion is six-coordinated by two C,N-bidentate 2-(pyridin-2-yl)phenyl ligands and one N,O-bidentate 2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolate anion, giving rise to a distorted octa\u00adhedral environment. The C,N-bidentate ligands, in which the C and N atoms are statistically disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other, are almost perpendicular to each other [the dihedral angle between the least-square planes is 87.00\u2005(4)\u00b0]. An intra\u00admolecular C\u2014H\u22efO hydrogen bond, as well as inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions, contribute to the stabilization of the mol\u00adecular and crystal structure.In the title compound, [Ir(C III complexes are of great inter\u00adest due to their excellent phospho\u00adrescent properties and electroluminescence applications. In particular, heteroleptic IrIII complexes with imine-based ancillary ligands exhibit aggregation-induced phospho\u00adrescent emission (AIPE), resulting in enhanced phospho\u00adrescence phenomena in the solid state 2(C13H10NO)]\u00b7CH2Cl2, a heteroleptic IrIII complex with an ancillary salicyl\u00adimine ligand.Cyclo\u00admetallated IrIII ion, two 2-(pyridin-2-yl)phenyl ligands, and one 2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolate anion. The IrIII ion adopts a distorted octa\u00adhedral coordination geometry, being N,O-chelated by the 2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolate ligand and C,N-chelated by two 2-(pyridin-2-yl)phenyl ligands, in which the C and N atoms are equally disordered over two sites and therefore both pairs of C and N atoms are trans and cis relative to each other. The equatorial plane is formed by N1/O1/N2/C12 atoms, the mean deviation from the least-squares plane being 0.002\u2005\u00c5. The IrIII ion is displaced by 0.0481\u2005(9)\u2005\u00c5 from the equatorial plane towards the axial imino N3 atom. The C,N-bidentate ligands are nearly perpendicular to each other, with a dihedral angle between the least-squares planes of 87.00\u2005(4)\u00b0. Within the C,N-bidentate ligands, the dihedral angles between the aromatic rings are 3.70\u2005(10) (between rings C1\u2013C6 and N1/C7\u2013C11) and 7.67\u2005(16)\u00b0 (between rings C12\u2013C17 and N2/C18\u2013C22). As shown in Table\u00a01III compounds, e.g. {(E)-2-[\u00admeth\u00adyl]phenolato-\u03ba2N,O}bis\u00adiridium(III) -2-[\u00admeth\u00adyl]phenolato-\u03ba2N,O}bis\u00adiridium(III) -2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolato-\u03ba2N,O}bis\u00adiridium(III) \u2005\u00c5 and Cg3\u22efCg4 = 3.8873\u2005(17)\u2005\u00c5; Cg1, Cg3 and Cg4 are the centroids of the N1/C7\u2013C11, C12\u2013C17 and C30\u2013C35 rings, respectively; symmetry code: (ii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01] contribute to the stabilization of the crystal structure  = 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016008100/wm5290sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016008100/wm5290Isup2.hklStructure factors: contains datablock(s) I. DOI: 1480710CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation while a water mol\u00adecule further coordinates to the CuII cation to complete the elongated distorted octa\u00adhedral coordination geometry.In a hydrated copper(II) complex, 2-amino-7-methyl-4-oxidopteridine-6-carboxyl\u00adate and 1,10-phenanthroline ligands chelate the Cu 8H5N5O3)(C12H8N2)(H2O)]\u00b73H2O, the CuII cation is O,N,O\u2032-chelated by the 2-amino-7-methyl-4-oxidopteridine-6-carboxyl\u00adate anion and N,N\u2032-chelated by the 1,10-phenanthroline (phen) ligand. A water mol\u00adecule further coordinates to the CuII cation to complete the elongated distorted octa\u00adhedral coordination geometry. In the mol\u00adecule, the pteridine ring system is essentially planar [maximum deviation = 0.055\u2005(4)\u2005\u00c5], and its mean plane is nearly perpendicular to the phen ring system [dihedral angle = 85.97\u2005(3)\u00b0]. In the crystal, N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22ef\u00b7O hydrogen bonds, as well as weak C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, link the complex mol\u00adecules and lattice water mol\u00adecules into a three-dimensional supra\u00admolecular architecture. Extensive \u03c0\u2013\u03c0 stacking between nearly parallel aromatic rings of adjacent mol\u00adecules are also observed, the centroid-to-centroid distances being 3.352\u2005(2), 3.546\u2005(3), 3.706\u2005(3) and 3.744\u2005(3)\u2005\u00c5.In the title compound, [Cu(C Location of the pyrazine ring N atom (N6) in the equatorial plane is in agreement with earlier observations on related copper and cobalt complexes \u2005\u00c5] may be elucidated in the light of Joule\u2019s hypothesis  complexes chelated by the pterin-6-carboxyl\u00adate anion have been reported by Kohzuma  al. 1989 and Funa al. 1999. In both8H7N5O3\u00b71.5H2O) was obtained by a published procedure  containing Cu(NO3)2\u00b73H2O , 1,10-phenanthroline monohydrate  and pterin  dissolved in NaOH  for 60\u2005h at 310\u2013312\u2005K under subdued light; additional NaOH solution was added for adjusting the initial pH at 10.5. Within a short while the initial bright-green solution turned hazy blue due to the presence of a fine white precipitate which gradually disappeared substanti\u00adally. The final blue solution was slightly hazy. Upon storage under aerobic conditions for one week the clear blue solution yielded green crystals, suitable for X-ray structure determination. Analysis calculated for C20H21CuN7O7: C 44.90, H 3.93, N 18.33%; found: C 44.38, H 4.06, N 17.65%. ESIMS data: the mol\u00adecular ion peak [M + 2H]+ appeared at 536.4 (relative abundance = 41.2%); the [M \u2212 4H2O \u2212 3H]+ peak was observed at 459.2 (relative abundance = 100%), indicating stability of the desolvated ternary species arising from the title complex.Method B. Using NaBH4 reduction in equimolar proportion of the original complex (obtained by Method A) and subsequent aerial reoxidation of the reduced complex to the present crystals merits attention due to the involvement of intricate redox chemistry. The NaBH4 treatment  to be Na2[Cu2I(L\u2032)2(phen)(H2O)4]\u00b72H2O, where L\u2032 is the 7,8-di\u00adhydro form of the present pterin ligand anion (C8H5N5O3) .Method B, represent better accuracy [R = 0.057 and wR(F2)= 0.135] as compared to the other one [R = 0.113 and wR(F2) = 0.279].Although the title compound could be obtained by two alternative methods, the present structural data obtained using the crystals from E\u00b0\u2032 value of \u22120.68\u2005V; now using an E\u00b0\u2032 value of \u22120.80\u2005V for NaBH4 in neutral medium  for the FeIII\u2013tetra\u00adhydro\u00adbiopterin reduction in phenyl\u00adalanine hy\u00addroxy\u00adlase ; using an E\u00b0\u2032 value of 0.70\u2005V for the O2/H2O2 couple, an Ecell value of 1.37\u2005V is obtained, indicating facile aerial oxidation. Now using an E\u00b0\u2032 value of 0.19\u2005V for the chelated pterin ligand  = 1.2\u20131.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814022302/xu5822sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022302/xu5822Isup2.hklStructure factors: contains datablock(s) I. DOI: 1028413CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The highlighted ruthenium complex forms discrete dimers by \u03c0\u2013\u03c0 stacking inter\u00adactions and hydrogen bonds. This combination of inter\u00adactions results in an unusual nearly face-to-face \u03c0\u2013\u03c0 stacking mode. 14H16N4)(C16H8N4)](PF6)2\u00b71.422CH3CN, discrete dimers of complex cations, [Ru(L\u2013N4H2)tape]2+ are formed {L\u2013N4H2 = 2,11-di\u00adaza\u00ad[3.3]pyridino\u00adphane; tape = 1,6,7,12-tetra\u00adaza\u00adperylene}, held together by \u03c0\u2013\u03c0 stacking inter\u00adactions via the tape ligand moieties with a centroid\u2013centroid distance of 3.49\u2005(2)\u2005\u00c5, assisted by hydrogen bonds between the non-coordinating tape ligand \u03b1,\u03b1\u2032-di\u00adimine unit and the amine proton of a 2,11-di\u00adaza\u00ad[3.3]-pyridino\u00adphane ligand of the opposite complex cation. The combination of these inter\u00adactions leads to an unusual nearly face-to-face \u03c0\u2013\u03c0 stacking mode. Additional weak C\u2014H\u22efN, C\u2014H\u22efF, N\u2014H\u22efF and P\u2014F\u22ef\u03c0-ring  (with F\u22efcentroid distances of 2.925\u20133.984\u2005\u00c5) inter\u00adactions are found, leading to a three-dimensional architecture. The RuII atom is coordinated in a distorted octa\u00adhedral geometry, particularly manifested by the Namine\u2014Ru\u2014Namine angle of 153.79\u2005(10)\u00b0. The counter-charge is provided by two hexa\u00adfluorido\u00adphosphate anions and the asymmetric unit is completed by aceto\u00adnitrile solvent mol\u00adecules of crystallization. Disorder was observed for both the hexa\u00adfluorido\u00adphosphate anions as well as the aceto\u00adnitrile solvate mol\u00adecules, with occupancies for the major moieties of 0.801\u2005(6) for one of the PF6 anions, and a shared occupancy of 0.9215\u2005(17) for the second PF6 anion and a partially occupied aceto\u00adnitrile mol\u00adecule. A second CH3CN mol\u00adecule is fully occupied, but 1:1 disordered across a crystallographic inversion center.In the title compound, [Ru(C The microwave-assisted synthesis of the precursor [Ru(L\u2013N4Me2)]2+, starting from [Ru(DMSO)4Cl2] and L\u2013N4Me2, in an ethano\u00adlic solution finished within 30\u2005min. It is not only fast, but also reproducible with only few byproducts, and hence requires no labor-intensive workup. Moreover, using the C2v symmetric macrocycle rather than bi\u00adpyridine-type ligands avoids the formation of mono- and dinuclear complexes with multiple stereoisomeric forms -pyridino\u00adphane (L\u2013N4H2) as a new ligand for RuII. Herein, we present the structure of the complex [Ru(L\u2013N4H2)tape](PF6)2, , obtained as its aceto\u00adnitrile solvate.Heteroaromatic ligands with more than three fused rings are commonly called large-surface ligands. Such ligands have attracted attention due to their use as connecting building blocks for supra\u00admolecular assemblies. If large-surface ligands feature more than one ligand donor site, connection between neighboring complexes can be realized through normal metal coordination (Ishow 4H2)tape]2+ in [Ru(C14H16N4)(C16H8N4](PF6)2\u00b71.422CH3CN. The Ru\u2014N bond lengths formed by the tape ligand (Table\u00a014Me2)tape]2+ \u00b0] from the idealized value of 180\u00b0 is slightly larger than for analogous ruthenium L\u2013N4Me2 complexes 2+, the dimers are also connected through bifurcated hydrogen bonds between one of the two L\u2013N4H2 ligand amine protons and both nitro\u00adgen atoms of the non-coordin\u00adating tape ligand \u03b1,\u03b1\u2032-di\u00adimine unit of the second complex cation of the dimer. In the crystal structure, these additional hydrogen bonds result in a short Ru\u22efRu distance of 8.8306\u2005(2)\u2005\u00c5, a tape ligand centroid\u2013centroid distance of 3.49\u2005(2)\u2005\u00c5 and an angle of 13.7 (1.4)\u00b0 between the ring normal and the centroid-to-centroid vector. Therefore, the \u03c0\u2013\u03c0 stacking motif can be described as parallel-displaced, but near to face-to-face -pyridino\u00adphane, see Brietzke, Mickler, Kelling, Schilde et al. tape](PF6)2 was synthesized as reported for [Ru(L\u2013N4Me2)tape](PF6)2  instead of L\u2013N4Me2. A yield of 44%  was obtained; m.p. > 573\u2005K. 1H NMR = (MeCN\u2013d3): \u03b4 = 8.69 , 8.56 , 8.01 , 7.77 , 7.72 , 7.65 , 5.6 , 4.83 , 4.47  p.p.m. 13C NMR = (MeCN-d3): \u03b4 = 160.0 (C2 + C6), 152.4 (Ce), 150.28 (Cd), 150.24 (Ca), 145.7 (Cf), 138.9 (C4), 136.7 (Cb\u2032), 123.5 (Cb), 122.7 (C3 + C5), 122.0 (Cc), 119.3 (Ce\u2032), 64.8 (CH2) p.p.m. ESI=-MS: calculated for [M\u2013PF6]+ 743.0809; found 743.0778.The syntheses of the ligands L\u2013N4H2)tape](PF6)2. The solution was filled into a test tube, which was placed into a diethyl ether-containing bottle. Dark-green crystals began to form at ambient temperature within a few days.Crystals suitable for X-ray structure analysis were obtained by vapor diffusion of diethyl ether into a saturated aceto\u00adnitrile solution of [Ru(L\u2013N6 anions were refined as disordered over one major and one minor moiety each. The geometry of the minor moieties were each restrained to be similar to that of the major moieties (within an estimated standard deviation of 0.02\u2005\u00c5). The minor moieties were subjected to a rigid bond restraint , and the anisotropic displacement parameters of the major and minor phospho\u00adrus atoms were each constrained to be identical. Associated with the major moiety of the PF6 anion of P1 is an aceto\u00adnitrile mol\u00adecule that is absent for the minor moiety. Subject to the restraints and constraints used, the occupancy ratios refined to 0.9215\u2005(17) to 0.0785\u2005(17) for the PF6 units of P1A and P1B, and to 0.801\u2005(6) and 0.199\u2005(6) for those of P2A and P2B.Disorder was observed for both the hexa\u00adfluorido\u00adphosphate anions as well as the aceto\u00adnitrile solvate mol\u00adecules. Both PFUij components to their neighbors closer than 2\u2005\u00c5, including those of symmetry-related atoms .A second aceto\u00adnitrile mol\u00adecule is disordered across a crystallographic inversion center, with substantial overlap for the two carbon atoms of symmetry-related mol\u00adecules. The geometry of the mol\u00adecule was restrained to be similar to that of the first aceto\u00adnitrile mol\u00adecule, and the ADPs of its C and N atoms were restrained to be have similar 3), 0.99 (CH2), 0.95 (Carom), N\u2014H = 1.0\u2005\u00c5, and with Uiso(H) = 1.2Ueq(C) with the exception of methyl hydrogen atoms, which were refined with Uiso(H) = 1.5Ueq(C).All hydrogen atoms connected to C and N atoms were placed in their expected calculated positions and refined as riding with C\u2014H = 0.98  global, I. DOI: 10.1107/S1600536814021060/zl2602Isup2.hklStructure factors: contains datablock(s) I. DOI: 1025408CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Water mol\u00adecules play an important role in the structure connectivity.In a novel one-dimensional hybrid compound, the inorganic part contains zigzag chains formed by corner-sharing [SbCl catena-poly[[[bis\u00ad [tetra\u00adachlorido\u00adanti\u00admonate(III)]-\u03bc-chlorido-[tetra\u00adchlorido\u00adanti\u00admonate(III)]-\u03bc-chlorido]] monohydrate], {(C6H14N2)2[Sb2Cl10]\u00b7H2O}n, is self-assembled into alternating organic and inorganic layers parallel to the bc plane. The anionic inorganic layer consists of infinite zigzag chains of corner-sharing [SbCl6]3\u2212 octa\u00adhedra running along the b axis. The organic part is made up of 1,4-diazo\u00adniabi\u00adcyclo\u00ad[2.2.2]octane dications (dabcoH22+). The water mol\u00adecules in the structure connect inorganic and organic layers. Hydrogen-bonding inter\u00adactions between the ammonium groups, water mol\u00adecules and Cl atoms ensure the structure cohesion.The hybrid title compound,  Ra)n+MbX3b+na}  are able to combine desirable characteristics from both types of constituents into a mol\u00adecular scale composite. These hybrids have been extensively studied for their excitonic and magneto-optical properties. In recent years, a significant number of organic\u2013inorganic hybrid materials based on anti\u00admony\u2013halide units have been studied. Six-coordinate anti\u00admony halides can arrange themselves in three-, two- or one-dimensional networks through sharing halides in the SbX6 octa\u00adhedra, separated by organic cations 2[Sb2Cl10]\u00b7H2O, (I)2)2+ dications, a corner sharing bi-octa\u00adhedron deca\u00adchlorido\u00addianti\u00admonate(III) anion and one crystallization water mol\u00adecule. The cations are labeled Cat1 (containing atoms N1 and N2) and Cat2 (containing N3 and N4) and the atomic numbering scheme is shown in Fig.\u00a01The asymmetric unit of the new chlorido\u00adanti\u00admonate(III) compound, 2)2+ cations located in the holes around the corner-sharing octa\u00adhedra. The layers are stacked along the a axis and water mol\u00adecules connect the organic and inorganic components ts Fig.\u00a02.6]3\u2212 and [Sb2Cl6]3\u2212) joined by the Cl2 ion. Both octa\u00adhedra are severely distorted with Sb\u2014Cl bond lengths lying in the range of 2.5233\u2005(18)\u20133.073\u2005(2)\u2005\u00c5 for the bridging ones and 2.4277\u2005(15)\u20132.8233\u2005(17)\u2005\u00c5 for the terminal ones. The two bridging halides (Cl2 and Cl4) connecting the central octa\u00adhedron to its neighbours are related cis, leading to zigzag chain of corner-sharing [SbCl6]3\u2212 octa\u00adhedra running along the b axis is Fig.\u00a03.P63/m) 2+ cations exhibit deviations from ideal Dh3 symmetry. The observed lowering symmetry  is probably due to the distortion of the (dabcoH2)2+ cation and can be related to the complex hydrogen-bond network linking the mol\u00adecular components .It is worth noting that at room temperature the DABCO mol\u00adecule crystallizes in the hexa\u00adgonal system (Pna21). These are two indispensable conditions making this phase a potential promising candidate for non-linear optical (NLO) behaviour as is the case for the well-known KTiOPO4 (KTP) and equivalent efficient NLO materials.The studied compound crystals are transparent and the structure is noncentrosymmetric (2)2+ cations and two water mol\u00adecules via hydrogen bonds  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0\u2212\u00a0x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0\u2212\u00a0via Cl1\u22efH2iii\u2014N2iii, Cl3\u22efH2iii\u2014N2iii and Cat2 by Cl3\u22efH4ii\u2014N4ii 3\u2212 octa\u00adhedra via O\u2014H13A\u22efCl5 and O\u2014H13B\u22efCl9iii \u00b72H2O containing isolated [Sb2Cl10]4\u2212 double octa\u00adhedra, (dabcoH2)2+ cations and water mol\u00adecules 2NH(CH2)2NH3]2+, see: Bujack & Angel  and DABCO (0.5\u2005mmol) was dissolved in a hydro\u00adchloric aqueous solution and stirred for several minutes at 353\u2005K. Colourless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature after two weeks.A mixture of SbClSHELXL  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015007379/vn2091Isup2.hklStructure factors: contains datablock(s) I. DOI: 943047CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of 2,2\u2032\u2032-bis\u00ad-1,1\u2032:4\u2032,1\u2032\u2032-terphenyl as the tris\u00ad(tri\u00adethyl\u00adamine) solvate, the diol host mol\u00adecule possesses a \u2018folded\u2019 mol\u00adecular conformation with inversion symmetry. Two of the three solvent mol\u00adecules form O\u2014H\u22efN hydrogen bonds and the third one forms C\u2014H\u22efN hydrogen bonds with the host compound. 44H26Cl4O2\u00b73C6H15N, the asymmetric part of the unit cell comprises two halves of the diol mol\u00adecules, 2,2\u2032\u2032-bis\u00ad-1,1\u2032:4\u2032,1\u2032\u2032-terphenyl, and three mol\u00adecules of tri\u00adethyl\u00adamine, i. e. the diol mol\u00adecules are located on crystallographic symmetry centres. Two of the solvent mol\u00adecules are disordered over two positions [occupancy ratios of 0.567\u2005(3):0.433\u2005(3) and 0.503\u2005(3):0.497\u2005(3)]. In the diol mol\u00adecules, the outer rings of the 1,1\u2032:4\u2032,1\u2032\u2032-terphenyl elements are twisted with reference to their central arene ring and the mean planes of the fluorenyl moieties are inclined with respect to the terphenyl ring to which they are connected, the latter making dihedral angles of 82.05\u2005(8) and 82.28\u2005(8)\u00b0. The presence of two 9-fluoren-9-ol units attached at positions 2 and 2\u2032\u2032 of the terphenyl moiety induces a \u2018folded\u2019 geometry which is stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions, the latter formed between the fluorenyl units and the central ring of the terphenyl unit [centroid\u2013centroid distances = 3.559\u2005(1) and 3.562\u2005(1)\u2005\u00c5]. The crystal is composed of 1:2 complex units, in which the solvent mol\u00adecules are associated with the diol mol\u00adecules via O\u2014H\u22efN hydrogen bonds, while the remaining solvent mol\u00adecule is linked to the host by a C\u2014H\u22efN hydrogen bond. The given pattern of inter\u00admolecular inter\u00adactions results in formation of chain structures extending along [010].In the title solvate, C Moreover, the location of the central ring of the terphenyl unit between the fluorenyl units [ring centroid distances = 3.559\u2005(1) and 3.562\u2005(1)\u2005\u00c5] indicate the presence of \u03c0\u2013\u03c0 stacking inter\u00adactions  with respect to the inner ring (A or A\u2032)  Fig.\u00a02 of the td(H\u22efN) 1.91\u20131.95\u2005\u00c5] (Table\u00a01via C\u2014H\u22efO hydrogen bonding , giving an overall chain structure extending along [010] -1,1\u2032:2\u2032,1\u2032\u2032:4\u2032\u2032,1\u2032\u2032\u2032:2\u2032\u2032\u2032,1\u2032\u2032\u2032\u2019-quinquephenyl  bis\u00ad(di\u00adethyl\u00adamine) clathrate  bis\u00ad(propan-1-ol) clathrate  bis\u00ad(but\u00adan-1-ol) clathrate  bis\u00ad(ethanol) clathrate  bis\u00ad(propan-1-ol) clathrate  bis\u00ad(di\u00adethyl\u00adamine) clathrate  bis\u00ad(butan-1-ol) clathrate  to a cold solution (195\u2005K) of 2,2\u2032\u2032-di\u00adiodo-1,1\u2032:4\u2032,1\u2032\u2032-terphenyl  in 20\u2005ml of dry THF. After 45\u2005min of stirring, 4,4\u2032-di\u00adchloro\u00adbenzo\u00adphenone , dissolved in 4\u2005ml benzene and 15\u2005ml THF, was added. The colourless reaction mixture was warmed to room temperature and stirred for 4\u2005h. The solution was extracted twice with diethyl ether. The combined organic extracts were washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. Colourless crystals were isolated by recrystallization from hexane (yield: 7.0%). M.p. 543\u2013546\u2005K; ESI\u2013MS [M + H]\u2212m/z 731.3. IR (KBr) \u03bd (cm\u22121) 3547, 3056, 3025, 1913, 1641, 1591, 1575, 1489, 1331, 1182, 1157, 1097, 1014, 919, 903, 840, 761. 1H NMR : \u03b4 = 2.84 , 6.75 , 7.09 , 7.11 , 7.22 , 7.26 , 7.32 . 13C NMR : \u03b4 = 82.68 (C-OH), 126.89, 127.43, 128.10, 129.11, 129.33, 129.83, 133.40, 140.24, 141.01, 144.06, 145.58 (Ar-C). EA calculated for C44H30O2Cl4: C 72.1, H 4.1%; found: C 72.2, H 4.4%. Crystals of (IIa) suitable for X-ray diffraction were obtained from a solution of (II) in tri\u00adethyl\u00adamine upon slow evaporation of the solvent at room temperature.The unsolvated compound (II) was prepared by addition of a solution of Uiso(H) = 1.2Ueq(C) for aromatic and methyl\u00adene, with C\u2014H = 0.98 and O\u2014H = 0.84\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl and hy\u00addroxy groups, respectively. Two mol\u00adecules of tri\u00adethyl\u00adamine are each disordered over two positions with occupancy ratios of 0.567\u2005(3):0.433\u2005(3) and 0.503\u2005(3):0.497\u2005(3). They were modelled with restrained bond lengths based on average values of 1.47\u2005(1)\u2005\u00c5 for N\u2014C and 1.53\u2005(1)\u2005\u00c5 for C\u2014C bonds.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015018824/zs2345sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015018824/zs2345Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015018824/zs2345Isup3.cmlSupporting information file. DOI: 1430018CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Cations and anions are linked through C\u2014H\u22efO hydrogen bonds.The asymmetric unit of the title compound consists of one [Eu(C 3H7NO)8][PMo12O40], the asymmetric unit comprises one \u03b1-Keggin-type [PMo12O40]3\u2212 polyoxidometalate anion and one distorted dodeca\u00adhedral [Eu(C3H7NO)8]3+ complex cation. In the crystal, the isolated polyoxidometalate anions are packed into hexa\u00adgonally arranged rows extending parallel to [001]. The complex cations are situated between the rows and are linked to the neighbouring anions through weak C\u2014H\u22efO hydrogen-bonding inter\u00adactions, leading to the formation of a three-dimensional network structure.In the title salt, [Eu(C The latter species are fused together by sharing corner atoms (Ob) and consist of three MoO6 octa\u00adhedra condensed in a triangular arrangement by sharing edges (Oc). There is also a terminal oxygen atom (Od) in every MoO6 octa\u00adhedron. The P\u2014O bond lengths range from 1.521\u2005(5)\u2005\u00c5 to 1.536\u2005(4)\u2005\u00c5 and the Mo\u2014O bond lengths from 1.690\u2005(5)\u2005\u00c5 to 2.438\u2005(4)\u2005\u00c5. The O\u2014P\u2014O angles [109.1\u2005(2)\u2013109.8\u2005(3)\u00b0] indicate only a slight distortion of the central PO4 tetra\u00adhedron. The EuIII cation is coordinated by eight di\u00admethyl\u00adformamide ligands through their oxygen atoms with Eu\u2014O distances from 2.369\u2005(5) to 2.416\u2005(6)\u2005\u00c5. These values are comparable to those of related oxido-europium(III) species, e.g for the [Eu(thd)3(DMF)2] complex  with Eu\u2014O = 2.494\u2005(5)\u20132.442\u2005(5)\u2005\u00c5 8]3+ cation is linked to four neighbouring \u03b1-Keggin-type [PMo12O40]3\u2212 anions through C\u2014H\u22efO hydrogen-bonding inter\u00adactions between the methyl groups of the DMF ligands and the terminal-oxygen (Od) and the bridging-oxygen atoms  of the [PMo12O40]3\u2212 anions  distances are between 3.174\u2005(10) and 3.541\u2005(11)\u2005\u00c5 while the C\u22efO distances are between 3.289\u2005(11) and 3.473\u2005(12)\u2005\u00c5. In the crystal packing, the POM anions are packed into hexa\u00adgonally arranged rows extending parallel to [001] with the [Eu(DMF)8]3+ cations located between the rows 4N)4H3][PMo11O39] was prepared using a literature method  and isonicotinic acid (C6H5NO2)  were dissolved in 10\u2005ml of di\u00admethyl\u00adformamide. This solution was added dropwise to a yellow di\u00admethyl\u00adformamide solution of [(C4H9)4N)4H3][PMo11O39] (0.33\u2005mmol in 10\u2005ml). The mixture was heated under stirring for 1\u2005h at 333\u2005K. Single crystals of the title compounds were obtained by slow diffusion of 2-propanol through the di\u00admethyl\u00adformamide solution. UV\u2013vis spectrum in di\u00admethyl\u00adformamide: \u03bbmax (nm) 315 and 205.The starting material [, \u03bdas(Mo=Od), \u03bdas(Mo\u2014Ob\u2014Mo) and \u03bdas(Mo\u2014Oc\u2014Mo) appear at 1065, 951, 885 and 974\u2005cm\u22121, respectively  (rocking vibration), \u03b4a(CH3), \u03b4s(CH3) and \u03bd(C-H) of the di\u00admethyl\u00adformamide ligand Uiso(H) = 1.2Ueq(C) for methine groups and C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl groups. The refined Flack parameter  I. DOI: 10.1107/S2056989016003546/wm5274Isup2.hklStructure factors: contains datablock(s) I. DOI: 1456619CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Molecules in both polymorphs of the title compound display deviations from planarity owing to crystal packing effects. 12H11N3O2, is a second monoclinic polymorph  of the previously reported monoclinic  form [Akhmad Aznan et al.  to 26.24\u2005(19)\u00b0. The geometry-optimized structure [B3LYP level of theory and 6\u2013311\u2005g+ basis set] has the same features except that the entire mol\u00adecule is planar. In the crystal, the three-dimensional architecture is consolidated by a combination of C\u2014H\u22efO, C\u2014H\u22ef\u03c0, nitro-N\u2014O\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distances = 3.649\u2005(2)\u20133.916\u2005(2)\u2005\u00c5].The title compound, C al. 2010. Acta Cr Similar conformations were observed for the two independent mol\u00adecules in the previously reported P21/c polymorph  inter\u00adaction to close the 10-membered {\u22efHC2NO}2 synthon is a little longer that the standard distance criteria incorporated in PLATON  inter\u00adactions ], and toluene C18\u2013C23 and N8-pyridine rings . As summarized in Table\u00a01via meth\u00adyl\u2013toluene C\u2014H\u22ef\u03c0 inter\u00adactions, and layers are connected into a three-dimensional architecture \u22ef(C18\u2013C23) = 3.916\u2005(2)\u2005\u00c5, with an angle of inclination of 11.04\u2005(19)\u00b0, and inter\u00adcentroid distance for (C6\u2013C11)\u22ef(N5/C13\u2013C17) = 3.913\u2005(2)\u2005\u00c5, with an angle of inclination of 13.44\u2005(19)\u00b0 and symmetry operation .Globally, the crystal packing features alternating layers of mol\u00adecules that stack along the s Table\u00a01. Ten-memns Fig.\u00a03. These cns Fig.\u00a04. The \u03c0\u2013\u03c0re Fig.\u00a05 via weakN-(3-chloro\u00adphen\u00adyl)-3-nitro\u00adpyridin-2-amine  hydrogen bond, the coplanarity of the nitro group and pyridine ring, and a conrotatory twist of the two rings, i.e. dihedral angles of 9.88\u2005(5) and 84.77\u2005(10)\u00b0, respectively. Finally, the structure of the all-phenyl analogue, 2-nitro\u00addiphenyl\u00adamine, has been reported -3-nitro\u00adpyridin-2-amine , prepared according to the literature procedure of Akhmad Aznan et al.  set at 1.2Ueq(C). N-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5 and with Uiso(H) set at 1.2Ueq(N). In the absence of significant anomalous scattering effects, 4208 Friedel pairs were averaged in the final refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814012227/hb0011sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814012227/hb0011Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814012227/hb0011Isup3.cmlSupporting information file. DOI: 1004278CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The furan and one of the phenanthrene groups are fused in an almost coplanar arrangement [dihedral angle = 5.14\u2005(8)\u00b0] and the furan unit makes dihedral angles of 70.27\u2005(11) and 57.58\u2005(8)\u00b0 with the planes of the phenyl and the second phenanthrene group, respectively. In the crystal, neighbouring mol\u00adecules are connected via two inter\u00admolecular hydrogen-bonding inter\u00adactions (O\u2014H\u22efO and C\u2014H\u22efO) towards the carbonyl O atom with donor\u2013acceptor distances of 2.824\u2005(2) and 3.277\u2005(3)\u2005\u00c5, creating an inversion dimer. A non-classical C\u2014H\u22efCl inter\u00adaction [3.564\u2005(2)\u2005\u00c5] and three C\u2014H\u22ef\u03c0 inter\u00adactions, with C\u22ef\u03c0 distances of 3.709\u2005(3), 3.745\u2005(2) and 3.628\u2005(3)\u2005\u00c5, connect the mol\u00adecules, forming a three-dimensional supra\u00admolecular architecture in the solid state.In the title compound, C The cenb-axis direction -furan\u00adone [2-(4-chloro\u00adphen\u00adyl)-2-hy\u00addroxy-1-oxa\u00adcyclo\u00adpenta\u00ad[l]phenanthren-3-one] (4) (65%), which was purified by recrystallization from a mixture of methanol and di\u00adchloro\u00admethane (2:1 v/v). The title compound (3) was the minor product formed along with (4) during the reaction . Diffraction-quality single crystals were generated by slow evaporation from methanol. Yield 1.90\u2005g (14%); m.p. 459\u2005K; IR : 3374 (OH), 1591 (C=O) cm\u22121; 1H NMR (CDCl3): \u03b4 8.79\u20137.26 , 8.69 ; MS: m/z 548 (M+). Analysis calculated for C37H21ClO3: C 80.94, H 3.86%; found: C 80.82, H 3.66%.A mixture of phenanthrene\u00adquinone (1) , 4-chloro\u00adaceto\u00adphenone (2)  and powdered potassium hydroxide (1\u2005g) in methanol (30\u2005ml) was stirred at 333\u2005K for 4\u2005h and then kept in a refrigerator for 48\u2005h. The main product obtained was a 3 = 1.2Ueq(C). The phenanthroline atom H3 was located from a difference Fourier map and refined with a distance restraint of O\u2014H = 0.86\u2005(1)\u2005\u00c5. The reflection 101 was omitted owing to bad agreement. Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814022338/zl2597sup1.cifCrystal structure: contains datablock(s) 3. DOI: 10.1107/S1600536814022338/zl25973sup2.hklStructure factors: contains datablock(s) 3. DOI: 1024475CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Page 1: In the Acknowledgements: \u201cproject ID RFMEFI57614X0061\u201d should read \u201cproject ID RFMEFI60414X0022.\u201dVolume 2, no. 6,"}
{"text": "The torsion angles indicate a non-helical conformation of the mol\u00adecule.In a de\u00adhydro\u00adamino acid with a C=C bond between the \u03b1- and \u03b2-C atoms, the amino acid residues are linked  11H17BrN2O5, is a de\u00adhydro\u00adamino acid with a C=C bond between the \u03b1- and \u03b2-C atoms. The amino acid residues are linked trans to each other and there are no strong intra\u00admolecular hydrogen bonds. The torsion angles indicate a non-helical conformation of the mol\u00adecule. The dipeptide folding is influenced by an inter\u00admolecular N\u2014H\u22efO hydrogen bond and also minimizes steric repulsion. In the crystal, mol\u00adecules are linked by strong N\u2014H\u22efO hydrogen bonds, generating (001) sheets. The sheets are linked by weak C\u2014H\u22efO and C\u2014H\u22efBr bonds and short Br\u22efBr [3.4149\u2005(3)\u2005\u00c5] inter\u00adactions.The title compound, C This reaction proceeds in two steps, namely by halogenation of de\u00adhydro\u00adamino acids, which gives \u03b1-bromo-imines, followed by tautomerization to the desired products upon treatment with an amine  is 175.79\u2005(16)\u00b0, while \u03c93 (O5\u2014C6\u2014N8\u2014C9) is 176.12\u2005(15)\u00b0. There are no strong intra\u00admolecular hydrogen bonds. The values of the \u03d52,3 and \u03c82,3 angles corresponds to a non-helical conformation \u00b0], which may correspond to the presence of the bromine atom in the structure. The other angles are normal, as the backbone of the mol\u00adecule is folded to minimize steric repulsion. The Boc group features two short intra\u00admolecular C\u2014H\u22efO contactsThe mol\u00adecular structure of the title compound, (I)A\u22efO17i and N12\u2014H12A\u22efO7ii) and one weak accompanying C9\u2014H9A\u22efO11i hydrogen bonds  \u2212x\u00a0+\u00a03, \u2212y, \u2212z\u00a0+\u00a01]. The sheets are connected to each other by weak C14\u2014H14A\u22efO11iii and C19\u2014H19B\u22efBr15iii hydrogen bonds and one Br\u22efBriv [3.4149\u2005(3)\u2005\u00c5] halogen bond  \u2212x\u00a0+\u00a03, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].In the crystal, mol\u00adecules form two strong twin N\u2014H\u22efO  of Boc\u2013Gly\u2013\u0394Ala\u2013OMe was dissolved in 2.5\u2005ml of di\u00adchloro\u00admethane and cooled to 193\u2005K. Then, bromine 0.027\u2005ml (0.5\u2005mM) was added. The solution was stirred over 10 minutes followed by addition of tri\u00adethyl\u00adamine 0.210\u2005ml (1.5\u2005mM). After 15 minutes, the mixture was quenched with 20\u2005ml of saturated aqueous NaHCO3 and warmed to room temperature. The product was extracted by di\u00adchloro\u00admethane (3 \u00d7 15\u2005ml). The organic layer was washed with brine (3 \u00d7 10\u2005ml) and dried over anhydrous Na2SO4. Evaporation of the solvent at reduced pressure gave 0.119\u2005g (0.35\u2005mM) of crude product (70% yield). Recrystal\u00adlization was performed from mixtures of diethyl ether/ethyl acetate\u00ad(2:1)/hexane solvents, yielding irregular colourless crystals. It is worth noting that in the case of our study, the formation of only the Z isomer was observed while in the preceding paper, the bromination of de\u00adhydro\u00adalanine-containing compound gave the E isomer. 1H NMR  \u03b4 1.38 , 3.67 , 3.69 , 7.05 , 7.30 , 9.63 . 13C NMR  \u03b4 28.21, 42.79, 52.54, 78.12, 113.26, 132.88, 155.80, 162.63, 168.80. Melting point = 386\u2013388\u2005K.Boc\u2013Gly\u2013\u0394Ala and its methyl ester were prepared according to the methodology described by Makowski  al. 1985 and Coss al. 2008. The \u03b2-bUiso (H) = 1.5Ueq(C); for N atoms, N\u2014H = 0.86\u2005\u00c5 and Uiso (H) = 1.2Ueq(C); for secondary C atoms, C\u2014H = 0.97\u2005\u00c5 and Uiso (H) = 1.2Ueq(C), with no refinement of their parameters.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814025677/hb7312sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814025677/hb7312Isup2.hklStructure factors: contains datablock(s) I. DOI: 1035539CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the complex cation, the SbV atom lies on an inversion center and is octa\u00adhedrally coordinated by four N atoms from a macrocyclic tetra\u00adphenyl\u00adporphyrinate ligand and two chloride ions. The complex cation has approximately a planar core with a maximum deviation of 0.018\u2005(5)\u2005\u00c5 from the porphyrin mean plane. The average Sb\u2014N distance is 2.062\u2005(11)\u2005\u00c5, while the Sb\u2014Cl distance is 2.355\u2005(1)\u2005\u00c5. The SbV atom of the anion is also located on an inversion center. The [SbCl6]\u2212 octa\u00adhedron exhibits rhombic distortion characterized by the Sb\u2014Cl bond lengths . In the crystal, the cations and anions are linked C\u2014H\u22ef Cl hydrogen bonds, forming a layer parallel to (211).The asymmetric unit of the title compound, [Sb(C Cl2][SbCl6] = 0.065wR(F2) = 0.173S = 1.134749 reflections266 parametersH-atom parameters constrainedmax = 2.55 e \u00c5\u22123\u0394\u03c1min = \u22121.45 e \u00c5\u22123\u0394\u03c1COLLECT  used to solve structure: SIR2004  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814012653/is5356Isup2.hklStructure factors: contains datablock(s) I. DOI: 1006075CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III ion in the title cationic complex is coordinated by four N atoms from the macrocyclic ligand, one water mol\u00adecule and one chloride in a cis geometry, displaying a distorted octa\u00adhedral environment. The crystal packing is stabilized by N\u2014H\u22efCl, O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds.The Cr cis-[CrCl(cycb)(H2O)][ZnCl4]\u00b73H2O , has been determined from synchrotron data. In the complex cation, the CrIII ion is bound by four N atoms from the tetra\u00addentate cycb ligand, a chloride ion and one water mol\u00adecule in a cis arrangement, displaying a distorted octa\u00adhedral coordination geometry. The distorted tetra\u00adhedral [ZnCl4]2\u2212 anion and three additional water mol\u00adecules remain outside the coordination sphere. The Cr\u2014N(cycb) bond lengths are in the range of 2.0837\u2005(14) to 2.1399\u2005(12)\u2005\u00c5 while the Cr\u2014Cl and Cr\u2014(OH2) bond lengths are 2.2940\u2005(8) and 2.0082\u2005(13)\u2005\u00c5, respectively. The crystal packing is stabilized by hydrogen-bonding inter\u00adactions between the N\u2014H groups of the macrocyclic ligand, the O\u2014H groups of the water mol\u00adecules and the Cl atoms of the tetra\u00adchlorido\u00adzincate anion, leading to the formation of a three-dimensional network.The structure of the title compound,  C-meso or racemic-5,5,7,12,12,14-hexa\u00admethyl-1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane (cyca and cycb) ligands are known to exist in trans or cis octa\u00adhedral coordination geometries when combined with two auxiliary ligands (OH2)]ZnCl4\u00b73H2O, (I)Chromium(III) complexes containing III ion with an O1A\u2014Cr1A\u2014Cl1A bond angle of 85.74\u2005(4)\u00b0. The rest of the coordination sites are occupied by four nitro\u00adgen atoms of the tetra\u00addentate macrocyclic cycb ligand, giving rise to a distorted octa\u00adhedral coordination sphere.In the mol\u00adecular structure of the complex cation, there is one chlorine atom and one water mol\u00adecule coordinating the Crb ligand is folded about the N2A\u2014Cr1A\u2014N4A line and is in its most stable cis-V conformation  bond lengths are in the range 2.0837\u2005(14) to 2.1399\u2005(12)\u2005\u00c5, in good agreement with those observed in cis-[Cr(OH)2(cycb)]ClO4\u00b72H2O ClO4\u00b7H2O Br\u00b7H2O Cl ClO4\u00b70.5H2O (NO3)2 Cl (NO3)2 (OH2)](ClO4)2\u00b7H2O  and 172.43\u2005(5)\u00b0, respectively. The angles N1A\u2014Cr1A\u2014N2A and N3A\u2014Cr1A\u2014N4A are 87.01\u2005(5) and 87.77\u2005(5)\u00b0, reflecting the distorted octa\u00adhedral coordination sphere. The tetra\u00adhedral [ZnCl4]2\u2212 anion and three additional water mol\u00adecules remain outside the coordination sphere of CrIII. The complex anion is distorted due to its involvement in hydrogen-bonding inter\u00adactions. Zn\u2014Cl bonds in the anion span a range from 2.2569\u2005(7) to 2.3131\u2005(8)\u2005\u00c5, and the Cl\u2014Zn\u2014Cl angles from 106.02\u2005(4) to 111.49\u2005(3)\u00b0.The cycon Fig.\u00a01. The Cr\u2014Extensive hydrogen-bonding inter\u00adactions occur in the crystal structure Table\u00a01. The supIII complexes involving the macrocyclic rac-5,5,7,12,12,14-hexa\u00admethyl-1,4,8,11-tetra\u00adaza\u00adcyclo\u00adtetra\u00addecane ligand. The crystal structures of cis-[Cr(OH)2(cycb)]ClO4\u00b72H2O 2(cycb)]ClO4\u00b7H2O (cycb)]Br\u00b7H2O 2(cycb)]Cl (cycb)]ClO4\u00b70.5H2O (OH2)](NO3)2 (cyca)(OH2)](ClO4)2\u00b7H2O (OH2)]2+ cationic complex with any anion was found, although the preparation of cis-[CrCl(cycb)(OH2)](ClO4)2\u00b70.4HClO4\u00b73H2O has been reported ]Cl\u00b7H2O was prepared according to literature procedures ]Cl\u00b7H2O (0.07\u2005g) was dissolved in 4\u2005mL of 0.01 M HCl at 353\u2005K and the 1\u2005mL of 6 M HCl containing 0.15\u2005g of solid ZnCl2 were added to this solution. The mixture was refluxed for 30\u2005min and then cooled to room temperature. The resulting solution was filtered and the filtrate was allowed to stand at room temperature for one day to afford purple crystals of compound (I)All chemicals were reagent grade materials and used without further purification. The starting material, Uiso(H) values of 1.2 or 1.5 \u00d7 Ueq of the parent atoms. The hydrogen atoms of water mol\u00adecules were located in difference maps restrained with O\u2014H = 0.84\u2005\u00c5 using DFIX and DANG commands.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015212/wm5196sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015212/wm5196Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419197CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structures of two isomeric compounds of iso\u00adquinoline with 3-chloro-2-nitro\u00adbenzoic acid and 4-chloro-2-nitro\u00adbenzoic acid have been determined at 190\u2005K. In each compound, the acid and base mol\u00adecules are held together by a short hydrogen bond between a carb\u00adoxy O atom and a base N atom. In the hydrogen-bonded unit of the former, the H atom is disordered over two positions, while in the latter, an acid\u2013base inter\u00adaction involving H-atom transfer occurs and the H atom is located at the N site. 9H7.3N\u00b7C7H3.7ClNO4, (I), and C9H8N\u00b7C7H3ClNO4, (II), of iso\u00adquinoline with 3-chloro-2-nitro\u00adbenzoic acid and 4-chloro-2-nitro\u00adbenzoic acid, the two components are linked by a short hydrogen bond between a base N atom and a carb\u00adoxy O atom. In the hydrogen-bonded unit of (I), the H atom is disordered over two positions with N and O site occupancies of 0.30\u2005(3) and 0.70\u2005(3), respectively, while in (II), an acid\u2013base inter\u00adaction involving H-atom transfer occurs and the H atom is located at the N site. In the crystal of (I), the acid\u2013base units are connected through C\u2014H\u22efO hydrogen bonds into a tape structure along the b-axis direction. Inversion-related adjacent tapes are further linked through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.6389\u2005(7)\u20133.7501\u2005(7)\u2005\u00c5], forming a layer parallel to (001). In the crystal of (II), the acid\u2013base units are connected through C\u2014H\u22efO hydrogen bonds into a ladder structure along the a-axis direction. The ladders are further linked by another C\u2014H\u22efO hydrogen bond into a layer parallel to (001).In each of the title isomeric compounds, C In the hydrogen-bonded unit, the iso\u00adquinoline ring system make dihedral angles of 54.12\u2005(15) and 71.89\u2005(5)\u00b0, respectively, with the carb\u00adoxy group and the benzene ring of the acid. In the acid mol\u00adecule, the benzene ring makes dihedral angles of 26.59\u2005(15) and 67.69\u2005(15)\u00b0, respectively, with the carb\u00adoxy and nitro groups.The mol\u00adecular structure of (II)i; Table\u00a01b-axis direction , Cg1\u22efCg2iv = 3.6674\u2005(7), Cg1\u22efCg3iii = 3.6637\u2005(7) and Cg1\u22efCg3iv = 3.6389\u2005(7)\u2005\u00c5, where Cg1, Cg2 and Cg3 are the centroids of the C1\u2013C6 benzene ring of the acid, and the N2/C8\u2013C10/C15/C16 rings of the base, respectively. Symmetry codes: (iii) \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (iv) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01.]In the crystal of (I)on Fig.\u00a03. Adjacenon Fig.\u00a03, formingi and C13\u2014H13\u22efO3ii; Table\u00a02a-axis direction on Fig.\u00a05. AdjacenA search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(N or O). The positional parameters were refined with bond restraints of O\u2014H = 0.84\u2005(2)\u2005\u00c5 and N\u2014H = 0.88\u2005(2)\u2005\u00c5. Atom H2 in (II)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989014026152/lh5740sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989014026152/lh5740IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1036583, 1036582CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the components are linked by N\u2014H\u22efCl, N\u2014H\u22efO, O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds, generating double layers propagating in (100).In the cation of the title hydrated mol\u00adecular salt, C As long ago as 1887, it was demonstrated -N--5-[amino]-2-hy\u00addroxy-4-oxo\u00adcyclo\u00adhexa-2,5-dien-1-iminium chloride, 4, which generates the zwitterion 5 when treated with base.In the course of our ongoing studies ] in the form of purple needles. This reaction must proceed via the elusive inter\u00admediate 6 which spontaneously hydrolyses. The first hydrolysis product should be inter\u00admediate 7. This contains a conjugated iminium salt and a vinyl\u00adogous amide, which must hydrolyse rapidly, possibly because of the stability of the acidic enol formed. It appears to be a rapid hydrolysis for an amide under mild conditions and so stabilization of a tetra\u00adhedral inter\u00admediate by the positive iminium salt might occur.By careful oxidation of the tetra\u00adhydro\u00adchloride salt of amine 6H7N2O2+ cation (r.m.s. deviation for the non-hydrogen atoms = 0.028\u2005\u00c5), a chloride counter-ion and a water mol\u00adecule of crystallization on Fig.\u00a01. Despitevia the C\u2014N and C\u2014C bonds between them. In terms of the \u2018oxygen side\u2019 of the cation, the C6\u2014O2 bond [1.320\u2005(4)\u2005\u00c5] is short for a C\u2014O single bond whereas C2\u2014O1 [1.227\u2005(4)\u2005\u00c5] is slightly lengthened for a nominal C=O double bond. This in combination with the C1\u2014C2 and C1\u2014C6 bond lengths again implies a degree of delocalization over these five atoms. However, the long C2\u2014C3 and C5\u2014C6 bonds imply little, if any, conjugation between the two delocalized components (O2/C6/C1/C2/O1 and N2/C5/C4/C3/N1) of the cation.The short C3\u2014C4 and C4\u2014C5 bonds correlate with the approximately equal C3\u2014N1 [1.320\u2005(4)] and C5\u2014N2 [1.306\u2005(4)\u2005\u00c5] bond lengths, which imply equal delocalization of the positive charge of the cation over atoms N1 and N2, mediated viz. N1\u2014H2n\u22efO1 and N2\u2014H4n\u22efO2 (Table\u00a01S(5) rings.The cation features two intra\u00admolecular N\u2014H\u22efO hydrogen bonds, 2 Table\u00a01, which bc-glide symmetry. Each link in the chain comprises two cations and two anions and In the crystal, the components are linked by N\u2014H\u22efCl, N\u2014H\u22efO, O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds Table\u00a01. If the via the intra\u00admolecular N1\u2014H2n\u22efO1 hydrogen bond).When the cation and water mol\u00adecule are considered together, an [001] chain also arises Fig.\u00a03. The watw\u22efCl1 hydrogen bond providing the key link between the sheets. Overall, the chloride ion accepts four hydrogen bonds (three N\u2014H\u22efCl and one O\u2014H\u22efCl inter\u00adactions) in an irregular geometry.When all components are considered together, (100) double sheets result Fig.\u00a04, with thE)-N--5-[amino]-2-hy\u00addroxy-4-\u03bfxo\u00adcyclo\u00adhexa-2,5-dien-1-iminium chloride chloro\u00adform monosolvate  and stirred at room temperature for 24\u2005h. The brown mixture was neutralized with NaHCO3 giving a brown or red precipitate, which was then extracted with CH2Cl2 (10 \u00d7 50\u2005ml). The yellow extracts were combined, deca\u00adnted, then stirred with methanol (50\u2005ml) containing five drops of conc. HCl(aq). The yellow solution turned purple. This was evaporated to dryness, then the product was dissolved in methanol (50\u2005ml) to yield a red solution and recrystallized by slow evaporation to leave the title compound  as purple needles: m.p. > 473\u2005K; \u03bbmax (ethanol)/nm 503 (log \u220a 2.90) and 325(3.99); \u03bd (diamond anvil)/cm\u22121 2953br, 1688s, 1547vs, 1401vs, 1310vs, 1251vs, 1141vs, 871vs, 853s, 711vs, 654vs, 579vs, 454s and 420s; m/z (orbitrap ASAP) 139.0498 , C6H7N2O2 requires 139.0502. The UV/visible spectrum of (I)1,2,4,5-Benzene\u00adtetra\u00adamine tetra\u00adhydro\u00adchloride  in distilled water (75\u2005ml) was treated with an excess of KUiso(H) = 1.2Ueq(carrier) was applied in all cases. The crystal studied was found to be a twin with the components related by a 180\u00b0 rotation about [001].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016005107/sj5497sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005107/sj5497Isup2.hklStructure factors: contains datablock(s) I. DOI: 1470620CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A 1:1.4 molar equivalent of benzene-1,3,5-tri\u00adcarb\u00adoxy\u00adlic acid cocrystallized with 4-hy\u00addroxy\u00adpyridine yields the 4-hy\u00addroxy\u00adpyridin-1-ium 3,5-di\u00adcarb\u00adoxy\u00adbenzoate salt. 5H6NO+\u00b7C9H5O6\u2212, (I), shows that 4-hy\u00addroxy\u00adpyridine has abstracted an H atom from benzene-1,3,5-tri\u00adcarb\u00adoxy\u00adlic acid, yielding a pyridinium cation and carboxyl\u00adate anion. The two ions form an extensive three-dimensional hydrogen-bonded network throughout the crystal. The hydrogen bonds that comprise the core of the network are considered strong, with O\u2014H\u22efO and N\u2014H\u22efO donor-to-acceptor distances ranging from 2.533\u2005(2) to 2.700\u2005(2)\u2005\u00c5. Packing is further enhanced by \u03c0-stacking of the cations and anions with like species [centroid\u2013centroid distance = 3.6206\u2005(13)\u2005\u00c5].The structure of the title salt, C This result allows for the hy\u00addroxy O and pyridine N atom to both act as hydrogen-bond donors, rather than the donor/acceptor situation of the 4-pyridone species. These two mol\u00adecules have been incorporated as linker species in metal\u2013organic frameworks  shows that the 4-hy\u00addroxy\u00adpyridine has abstracted an H atom from the benzene\u00adtri\u00adcarb\u00adoxy\u00adlic acid, yielding a pyridinium cation and a carboxyl\u00adate anion  and 1.348\u2005(3)\u2005\u00c5, respectively]. The remaining bonds within the ring display typical aromatic distances [C2\u2014C3 = 1.405\u2005(3)\u2005\u00c5 and C3\u2014C4 = 1.402\u2005(3)\u2005\u00c5]. The C3\u2014O1 distance of 1.326\u2005(2)\u2005\u00c5 is typical for a hy\u00addroxy O atom bound to an aromatic ring. Bond angles within the pyridine ring are unexceptional.The structure of \u2005\u00c5 and C14\u2014O7 = 1.332\u2005(3)\u2005\u00c5; C12\u2014O2 = 1.224\u2005(2)\u2005\u00c5 and C14\u2014O6 = 1.204\u2005(3)\u2005\u00c5]. The remaining carboxyl\u00adate group displays C\u2014O bond distances that are similar to each other and indicate delocalization of the C\u2014O bonds , supporting the proposed single negative charge on the benzene\u00adtri\u00adcarb\u00adoxy\u00adlic acid mol\u00adecule. This is further supported by the presence of H atoms, located in a difference Fourier map, on atoms O3 and O7. Bond distances and angles within the benzene ring are as expected.i [symmetry code: (i) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0\u2212\u00a0ii and O2iii, respectively [symmetry codes: (ii) \u2212x, \u2212y, z\u00a0\u2212\u00a0x, \u2212y\u00a0+\u00a01, z\u00a0+\u00a0The local inter\u00admolecular contacts consist of the pyridinium cation forming a hydrogen bond from the hy\u00addroxy group to the anionic carboxyl\u00adate group \u2005\u00c5, i.e. the c-axis spacing. The centroid-to-perpendicular distances are 3.3629\u2005(9)\u2005\u00c5 for the cation and 3.4372\u2005(9)\u2005\u00c5 for the anion. Both measurements are within accepted \u03c0\u2013\u03c0 contact ranges -one  in MeOH (3\u2005ml) in a 20\u2005ml vial was added a solution of 4-hy\u00addroxy\u00adpyridine  in MeOH (3\u2005ml). The mixture was shaken vigorously, covered with perforated Parafilm and allowed to evaporate slowly over a period of 5\u2005d, yielding colorless rod-like crystals.Uiso(H) = 1.2 Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a03x parameter refined to 0.20\u2005(8), which suggests the possibility of a small amount of inversion twinnning  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011780/pk2555Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011780/pk2555Isup3.cmlSupporting information file. DOI: 1407819CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Additional \u03c0\u2013\u03c0 inter\u00adactions between pyridinium rings stabilize this arrangement.In the crystal structure of the title compound, the mol\u00adecular components,  7H11N2)3[Cr(C2O4)3]\u00b74H2O, the central CrIII ion of the complex anion (point group symmetry 2) is coordinated by six O atoms from three chelating oxalate(2\u2212) ligands in a slightly distorted octa\u00adhedral coordination sphere. The Cr\u2014O bond lengths vary from 1.9577\u2005(11) to 1.9804\u2005(11)\u2005\u00c5, while the chelate O\u2014Cr\u2014O angles range from 82.11\u2005(6) to 93.41\u2005(5)\u00b0. The 4-(di\u00admethyl\u00adamino)\u00adpyridinium cations  are protonated at the pyridine N atoms. In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the cations and anions into a three-dimensional network. \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of adjacent cations provide additional stabilization of the crystal packing, with the closest centroid-to-centroid distances being 3.541\u2005(1) and 3.575\u2005(1)\u2005\u00c5.In the title hybrid salt, (C The chelate O\u2014Cr\u2014O angles range from 82.11\u2005(6) to 93.41\u2005(5)\u00b0. The Cr\u2014O bond lengths vary from 1.9577\u2005(11) to 1.9804\u2005(11)\u2005\u00c5 and are similar to those found in the guanidinium tris\u00adchromate(III) salt \u00adpyridinium cations and lattice water mol\u00adecules Table\u00a01. In addi6(H2O)17[Cr(C2O4)3]4}\u00b77H2O , with an aqueous solution of 4-(di\u00admethyl\u00adamino)\u00adpyridine  and oxalic acid . The mixture was stirred at 333\u2005K for about 30 minutes and then cooled to room temperature and filtered. The title compound crystallized by slow evaporation of the solvent at room temperature in form of light-violet crystals with dimensions up to 3\u2005mm within a few weeks.The title compound was obtained by reaction of an aqueous solution of the freshly prepared barium-oxalatochromate(III) salt {BaUiso(H) = 1.2Ueq(C) for aromatic and 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl H atoms. H atoms of water mol\u00adecules as well as those bonded to N atoms were located from a difference Fourier map. Water H atoms were refined with soft restraints on O\u2014H and H\u22efH distances [O\u2014H = 0.82\u2005(1)\u2005\u00c5 and H\u22efH = 1.30\u2005(2)\u2005\u00c5] and Uiso(H) = 1.5Ueq(O) whereas H atoms bonded to N atoms were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015020113/wm5230sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020113/wm5230Isup2.hklStructure factors: contains datablock(s) I. DOI: 1400490CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports5: Article number: 17676; 10.1038/srep17676 Published online: 12032015; Updated: 04072016This Article contains an error in Supplementary Figure 1 where the value of the male chemotaxis index towards ascr#9 \u20180.26\u2009\u00b1\u20090.07\u2019 was incorrectly depicted as \u20180.38\u2009\u00b1\u20090.07\u2019. The correct Supplementary Figure 1 appears below as"}
{"text": "N-[2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]benzamides are reported. The 3-fluoro\u00adbenzamide crystallized with two independent mol\u00adecules in the asymmetric unit; the dihedral angles between the two benzene rings are 43.94\u2005(8) and 55.66\u2005(7)\u00b0. In the 3-bromo\u00adbenzamide and the 3-iodo\u00adbenzamide, this dihedral angle is much smaller, viz. 10.40\u2005(12) and 12.5\u2005(2)\u00b0, respectively.The crystal structures of three  14H9F4NO, (I), C14H9BrF3NO, (II), and C14H9F3INO, (III), the two benzene rings are inclined to one another by 43.94\u2005(8)\u00b0 in mol\u00adecule A and 55.66\u2005(7)\u00b0 in mol\u00adecule B of compound (I), which crystallizes with two independent mol\u00adecules in the asymmetric unit, but by only 10.40\u2005(12)\u00b0 in compound (II) and 12.5\u2005(2)\u00b0 in compound (III). In the crystals of all three compounds, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules to form chains propagating along the a-axis direction for (I), and along the b-axis direction for (II) and (III). In the crystal of (I), \u2013A\u2013B\u2013A\u2013B\u2013 chains are linked by C\u2014H\u22efO hydrogen bonds, forming layers parallel to (010). Within the layers there are weak offset \u03c0\u2013\u03c0 inter\u00adactions present [inter\u00adcentroid distances = 3.868\u2005(1) and 3.855\u2005(1)\u2005\u00c5]. In the crystals of (II) and (III), the chains are linked via short halogen\u2013halogen contacts [Br\u22efBr = 3.6141\u2005(4)\u2005\u00c5 in (II) and I\u22efI = 3.7797\u2005(5)\u2005\u00c5 in (III)], resulting in the formation of ribbons propagating along the b-axis direction.In the title compounds, C The dihedral angle between the two benzene rings is 43.94\u2005(8)\u00b0 in mol\u00adecule A, while in mol\u00adecule B it is larger, being 55.66\u2005(7)\u00b0. The torsion angle of the central \u2013Car\u2014C(=O)\u2014N\u2014Car\u2013 segment is 176.74\u2005(12)\u00b0 in mol\u00adecule A and \u2212179.58\u2005(12)\u00b0 in mol\u00adecule B.The mol\u00adecular structure of compound (I)am Fig.\u00a02. In both3 substitution on the aniline ring are anti to one another, and the 3-bromo and 3-iodo substituents are anti to the N\u2014H bond in the central \u2013Car\u2014C(=O)\u2014N\u2014Car\u2013 segment of the mol\u00adecules, similar to situation observed in (I)A and B of compound (I)ar\u2014C(=O)\u2014N\u2014Car\u2013 segment is \u2212175.5\u2005(2)\u00b0 in (II)A and B of compound (I)The mol\u00adecular structures of compounds (II)A\u2013B\u2013A\u2013B\u2013 C(4) chains running along the a-axis direction \u2005\u00c5 and Cg2\u22efCg3i = 3.8553\u2005(9)\u2005\u00c5; Cg1 and Cg3 are the centroids of the aniline rings C1\u2013C6 and C15\u2013C20, respectively; Cg2 and Cg4 are the centroids of the benzoic acid rings C8\u2013C13 and C22\u2013C27, respectively; symmetry code (i) x\u00a0\u2212\u00a01, y, z]. The crystal structure does not feature any C\u2014H\u22efF or F\u22efF inter\u00adactions n Table\u00a01. Neighbos Table\u00a01, formingne Fig.\u00a06. Within ns Fig.\u00a06.C(4) chains running parallel to the b axis \u2005\u00c5], forming ribbons along [010]; see Fig.\u00a07The crystal structure of (II)is Fig.\u00a07. AdjacenC(4) chains running parallel to the b axis (Table\u00a03via short I\u22efI contacts [3.7797\u2005(5)\u2005\u00c5], forming ribbons along [010]; see Fig.\u00a08The crystal structure of (III)s Table\u00a03. Adjacenmeta position of the benzoic acid ring have a similar effect on the mol\u00adecular conformations and the supra\u00admolecular architectures exhibited by this class of compounds, whereas the fluoro substitution has a very different influence. For instance, there are two mol\u00adecules in the asymmetric unit of (I)A and B) of (I)From the above observations, it can be concluded that the bromo and iodo substitutions on the et al., 2016viz. N-(2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl)aryl\u00adamides, gave four hits. They include N-(2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl)benzamide, for which there are three reports: JOZFUB and JOZFUB01 in space group P43 phen\u00adyl)benzamide \u2014Car\u2013 segment is 175.1\u2005(5)\u00b0, which is very close to the values observed for the two independent mol\u00adecules in compound (I)meta position of the benzoyl ring, as in compound (I)A search of the Cambridge Structural Database  were dissolved in phospho\u00adrous oxychloride taken in a 250\u2005ml round-bottomed flask. The mixtures were refluxed for an hour and later cooled to 273\u2005K. An equimolar amount of 2-(tri\u00adfluoro\u00admeth\u00adyl)aniline was added dropwise to these mixtures with continuous stirring. After completion of the addition, the reaction mixtures were brought to room temperature and stirring was continued for 1\u2005h. The reaction mixtures were poured into ice-cold water. The solids that separated were washed thoroughly with water, followed by washing with dilute hydro\u00adchloric acid, water, aqueous sodium hydrogen carbonate solution and again with water. The compounds were filtered under suction, dried and recrystallized from aqueous ethanol to constant melting points. Prismatic colourless single crystals of all three compounds were obtained by slow evaporation of solutions in methanol, with a few drops of water.Uiso = 1.2Ueq(C). In the final cycles of refinement of compound (III)R1, wR2, and GOF.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989016007866/su5298sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989016007866/su5298Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016007866/su5298IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989016007866/su5298IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298IIIsup7.cmlSupporting information file. DOI: 1479657, 1479656, 1479655CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the title compound, a supra\u00admolecular sheet structure is formed through N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. 19H19NO5, the amide carbonyl O atom is positioned anti to the other two carbonyl O atoms. The 4-hy\u00addroxy\u00adhydro\u00adcinnamate fragment is disordered over two positions with an occupancy ratio of 0.729\u2005(12):0.271\u2005(12). The N\u2014(C=O)\u2014C plane of the acetamide group and the acetate O\u2014(C=O)\u2014C plane are almost co-planar; the acetamide plane makes dihedral angles of 1.9\u2005(6) and 16.0\u2005(19)\u00b0, respectively, with the acetate planes of the major and minor occupancy components. In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a supra\u00admolecular sheet structure parallel to (102).In the title compound, C The carbonyl O1 and O16 atoms are positioned anti with respect to the carbonyl O12 atom. These C=O bond lengths are in the range 1.176\u2005(12)\u20131.226\u2005(6)\u2005\u00c5.The fragment O1/O12/N10/C2\u2013C9/C11/C13 including the acetamide group is almost planar with an r.m.s. deviation of 0.034\u2005(11)\u2005\u00c5. The 4-hy\u00addroxy\u00adhydro\u00adcinnamate fragment is disordered over two positions with occupancy ratio of 0.729\u2005(12):0.271\u2005(12). The acetamide plane O12/N10/C11/C12 makes dihedral angles of 1.9\u2005(6) and 16.0\u2005(19)\u00b0, respectively, with the disordered acetate planes O14/O16/C15/C17 and O14via N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds -2-chloro\u00adacetamide in the presence of dimethyl formamide (DMF) solvent and tri\u00adethyl\u00adamine base  as eluent. The single crystals were obtained from a solvent mixture of ethyl acetate/n-hexane (3:1) upon slow evaporation at room temperature . FTIR \u03bdmax cm\u22121: 3428 (N\u2014H), 3354 (O\u2014H), 2971 (sp2 C\u2014H), 2887 (sp3 C\u2014H), 1735 (C=O ester), 1646 (C=O amide), 1601 (C=C aromatic), 1154 .The title compound was synthesized by direct condensation of 4-hy\u00addroxy\u00adphenyl propanoic acid with se Fig.\u00a04. The reaA, O25A and C15A\u2013C24A of the minor component were refined isotropically. Planarity restraints were applied for atoms C18\u2013C24, O25, C18A\u2013C24A and O25A. Bond-distance restraints were also applied for C20, C22, C23, O16A and C15A\u2013C24A. H10 and H25 of the NH and OH groups, respectively, were located in a difference Fourier map and the coordinates were refined with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O) [N\u2014H = 0.86\u2005(5)\u2005\u00c5 and O\u2014H = 0.95\u2005(12)\u2005\u00c5]. H25A of the minor occupancy OH group was refined with a restraint of O\u2014H = 0.90\u2005(2)\u2005\u00c5, and with Uiso(H) = 1.5Ueq(O). All other H atoms were included as riding atoms, with C\u2014H = 0.93\u20130.97\u2005\u00c5 and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901600894X/is5453sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901600894X/is5453Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600894X/is5453Isup3.cmlSupporting information file. DOI: 1483293CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-cyano\u00adpyridine axial ligand in a distorted square-pyramidal geometry. The non-coordinating 4-cyano\u00adpyridine mol\u00adecule is disordered over two positions in the supra\u00admolecular channel formed by complex mol\u00adecules.In the crystal, the Zn 72H44N4O8)(C6H4N2)]\u00b7C6H4N2 or [Zn(TPBP)(4-CNpy]\u00b7(4-CNpy) , the ZnII cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-CNpy axial ligand in a distorted square-pyramidal geometry. The average Zn\u2014N(pyrrole) bond length is 2.060\u2005(6)\u2005\u00c5 and the Zn\u2014N(4-CNpy) bond length is 2.159\u2005(2)\u2005\u00c5. The zinc cation is displaced by 0.319\u2005(1)\u2005\u00c5 from the N4C20 mean plane of the porphyrinate anion toward the 4-cyano\u00adpyridine axial ligand. This porphyrinate macrocycle exhibits major saddle and moderate ruffling and doming deformations. In the crystal, the [Zn(TPBP)(4-CNpy)] complex mol\u00adecules are linked together via weak C\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, forming supra\u00admolecular channels parallel to the c axis. The non-coordinating 4-cyano\u00adpyridine mol\u00adecules are located in the channels and linked with the complex mol\u00adecules, via weak C\u2014H\u22efN inter\u00adactions and \u03c0-\u03c0 stacking or via weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. The non-coordinating 4-cyano\u00adpyridine mol\u00adecule is disordered over two positions with an occupancy ratio of 0.666\u2005(4):0.334\u2005(4).In the title compound, [Zn(C However, only three structures of zinc\u20134-NCpy non-porphyrinic species [CSD refcodes CYPYZN (4-CNpy)]\u00b7(4-CNpy) (I)During the last two decades, renewed attention to zinc metalloporphyrins has been noted for their applications in different fields II cation of the [Zn(TPBP)(4-CNpy)] complex has a distorted square-pyramidal coordination geometry  bond length [2.159\u2005(2)\u2005\u00c5] is in the range (2.055\u20132.248\u2005\u00c5) of those of the zinc\u20134-CNpy complexes reported in the literature [CSD refcodes LIMWUZ ]  [CSD refcodes ATUSOX . This value is close to those of the related five-coordinated zinc metalloporphyrins [Zn(TPP)(DMSO)]  nearly bis\u00adects the \u2018cis\u2019 Np\u2014Fe\u2014Np angle, which is also the case for the title zinc\u20134-CNpy deriv\u00adative (I)The via weak non-classical C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and by C\u2014H\u22ef\u03c0 inter\u00adactions \u2005\u00c5 and 3.457\u2005(4)\u2005\u00c5, respectively.Within the crystal structure of (I)s Table\u00a01. The nitc axis  atom C82A of the free 4-NCpy mol\u00adecule and atom O8 of a TPBP porphyrin [C82A\u2014H82A\u22efO8 distance = 3.226\u2005(5)\u2005\u00c5], (ii) the centroid (Cg18) of the C80A\u2013C81A\u2013C82A\u2013N8A\u2013C83A\u2013C84A ring of the disordered free 4-CNpy mol\u00adecule and the carbon atom C49 of an adjacent TPBR porphyrinato ligand with a C49\u2014H49\u22efCg18 contact length of 3.448\u2005(4)\u2005\u00c5, (iii) by aromatic \u03c0\u2013\u03c0 inter\u00adactions between the centroid (Cg19) of the C80A\u2013C81B\u2013C82B\u2013N8B\u2013C83B\u2013C84B ring of a free disordered 4-CNpy mol\u00adecule and the centroid (Cg11) of the phenyl porphyrin ring C28\u2013C33  and the N8B nitro\u00adgen atom of this second 4-CNpy mol\u00adecule is weakly bonded to the carbon atom C72 of a phenyl ring of a nearby TPBR porphyrinato ligand [C72__H72\u22efN8B distance = 3.226\u2005(15)\u2005\u00c5] (4-CNpy)] complexes parallel to the is Fig.\u00a04. Each fr\u00c5] Fig.\u00a05.2TPBP) and the starting [Zn(TPBP)] complex were synthesized using modified reported methods  dissolved in 33\u2005mL of di\u00adchloro\u00admethane was added dropwise and stirred at 273\u2005K and then at room temperature for 12\u2005h. Upon completion, the reaction mixture was filtered and the solvent was evaporated to dryness, to afford 9.3\u2005g of a pale-yellow solid (yield 86%), m.p. = 356\u2013358\u2005K, C14H10O3: C 74.33, H 4.46%; found: C 73.98, H 4.35%. Spectroscopic analysis: 1H NMR  \u03b4H (p.p.m.) 10.04 , 8.17 , 8.04 , 7.80 , 7.64 , 7.56 . 13C NMR  \u03b4C (p.p.m.) 192.09, 164.12, 155.21, 134.31, 134, 131.13, 129.91, 129.03, 128.47, 122.90.Benzoic acid , 4-hy\u00addroxy\u00adbenzaldehyde  and di\u00admethyl\u00adamino\u00adpyridin DMAP  were dissolved at 273\u2005K in 20\u2005mL of di\u00adchloro\u00admethane. To this solution, 10.12\u2005g of v/v as an eluent). A purple solid was obtained and dried under vacuum .4.5\u2005mg of 4-formyl\u00adphenyl\u00adbenzoate (19.9\u2005mmol) were dissolved in 50\u2005mL of propionic acid. The solution was heated under reflex at 413\u2005K. Freshly distilled pyrrole  was then added dropwise and the mixture was stirred for another 40\u2005min. The mixture was cooled overnight at 277\u2005K and filtered under vacuum. The crude product was purified using column chromatography  \u03b4 (p.p.m.) 8.94 , 8.39 , 8.29 , 7.71 , 7.62 , \u22122.80 . UV/Vis (CHCl3): \u03bbmax  420 (512.7), 516 (16.7), 552 (7.4), 591 (4.8), 646 (4.0).Spectroscopic analysis: 2TPBP porphyrin  and [Zn(OAc)2]\u00b72H2O  in CHCl3 (30\u2005mL) and CH3OH (5\u2005mL) was stirred at room temperature overnight. The solvent was evaporated and a light-purple solid of the [Zn(TPBP)] complex was obtained .A mixture of the H1H NMR  \u03b4(p.p.m. ) 9.04 , 8.40 , 8.30 , 7.85 , 7.64 , \u22122.80 . UV/Vis (CHCl3):\u03bbmax  (10\u22123 \u220a) 425 (613.5), 554 (23.0), 596 (6.9).Spectroscopic analysis: To a solution of [Zn(TPBP)]  in di\u00adchloro\u00admethane (5\u2005mL) was added an excess of 4-cyano\u00adpyridine . The reaction mixture was stirred at room temperature for 2\u2005h. Single crystals of the title complex were obtained by diffusion of hexa\u00adnes through the di\u00adchloro\u00admethane solution.1H NMR  \u03b4(p.p.m. ) 9.04 , 8.40 , 8.30 , 7.67 , 7.53 . UV/Vis (CHCl3): \u03bbmax  425 (613.5), 554 (23.0), 596 (6.9).Spectroscopic analysis: \u22121 domain using a Perkin\u2013Elmer Spectrum Two FTIR spectrometer. The spectrum presents characteristic IR bands of the TPBP porphyrinato moiety. The C\u2014H stretching frequencies of the porphyrin are in the range 3060\u20132860\u2005cm\u22121, the ester group of the meso-substituents of this porphyrin are identified by a strong band at 1736\u2005cm\u22121, \u03bd(C=O) stretch and by two strong bands at 1264 and 1061 corresponding to the \u03bd(C\u2014O) stretching vibration. The IR spectrum of (I)\u22121 attributed to the nitrile stretching frequency \u03bd(C\u00a0N). The value of this band is almost identical to the one of the free 4-cyano\u00adpyridine (2236\u2005cm\u22121) which could be attributed both to the 4-CNpy ligand or the free 4-CNpy mol\u00adecule in (I)et al., 2000\u22121 (vw: very weak), 1523\u2005cm\u22121 (vw), 1505\u2005cm\u22121(w: weak), 1406\u2005cm\u22121 (m: medium), 996\u2005cm\u22121 (s: strong), 707\u2005cm\u22121 (m), 685\u2005cm\u22121 (m) and 538\u2005cm\u22121 (w) attributed to the pyridyl group of the coordinating and the free 4-cyano\u00adpyridine species (4-CNpy)]\u00b7(4-CNpy) (I)Uiso(H) = 1.2 Ueq(C). The non-coordinating 4-cyano\u00adpyridine mol\u00adecule is disordered over two positions A and B with refined occupancies of 0.666\u2005(4) and 0.334\u2005(4), respectively. The bond lengths and angles of this mol\u00adecule were restrained to ensure proper geometry using DFIX and DANG instructions of SHELXL2014  I, global. DOI: 10.1107/S2056989016000062/xu5882Isup2.hklStructure factors: contains datablock(s) I. DOI: 1445100CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The central C4N2O2 group of atoms in the dication are almost planar (r.m.s. deviation = 0.009\u2005\u00c5), and the carbonyl groups lie in an anti disposition to enable the formation of intra\u00admolecular amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds. To a first approximation, the pyridinium and amide N atoms lie to the same side of the mol\u00adecule [Npy\u2014C\u2014C\u2014Namide torsion angle = 34.8\u2005(2)\u00b0], and the anti pyridinium rings are approximately perpendicular to the central part of the mol\u00adecule [dihedral angle = 68.21\u2005(8)\u00b0]. In the anion, one carboxyl\u00adate group is almost coplanar with the ring to which it is connected [Cben\u2014Cben\u2014Cq\u2014O torsion angle = 2.0\u2005(3)\u00b0], whereas the other carboxyl\u00adate and carb\u00adoxy\u00adlic acid groups are twisted out of the plane . In the crystal, anions assemble into layers parallel to (10-4) via hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) and charge-assisted hy\u00addroxy-O\u2014H\u22efO(carboxyl\u00adate) hydrogen bonds. The dications are linked into supra\u00admolecular tapes by amide-N\u2014H\u22efO(amide) hydrogen bonds, and thread through the voids in the anionic layers, being connected by charge-assisted pyridinium-N\u2014O(carboxyl\u00adate) hydrogen bonds, so that a three-dimensional architecture ensues. An analysis of the Hirshfeld surface points to the importance of O\u2014H\u22efO hydrogen bonding in the crystal structure.The asymmetric unit of the title salt, C N,N\u2032-bis\u00ad(pyridin-n-ylmeth\u00adyl)ethanedi\u00adamides, n = 2, 3 or 4, the mol\u00adecule with n = 2 appears to have attracted the least attention in co-crystallization studies; for the chemical structure of the diprotonated form of the n = 2 isomer see Scheme 1. By contrast, the n = 3 and 4 mol\u00adecules have attracted inter\u00adest from the crystal engineering community in terms of their ability to form co-crystals with iodo-containing species leading to aggregates featuring N\u22efI halogen bonding ethanedi\u00adamide conducted in ethanol. The harvested crystals were shown by crystallography to comprise (2-pyridinium)CH2N(H)C(=O)C(=O)CH2N(H)(2\u2013pyridinium) dications and 3,5-di\u00adcarb\u00adoxy\u00adbenzoate anions in the ratio 1:2; as the dication is located about a centre of inversion, one anion is found in the asymmetric unit. The confirmation for the transfer of protons during the co-crystallization experiment is found in (i) the pattern of hydrogen-bonding inter\u00adactions as discussed in Supra\u00admolecular features, and (ii) the geometric characteristics of the ions. Thus, the C\u2014N\u2014C angle in the pyridyl ring has expanded by over 3\u00b0 cf. that found in the only neutral form of N,N\u2032-bis\u00ad(pyridin-2-ylmeth\u00adyl)ethanedi\u00adamide characterized crystallographically in an all-organic mol\u00adecule, i.e. in a 1:2 co-crystal with 2-amino\u00adbenzoic acid  and 1.250\u2005(2)\u2005\u00c5 is consistent with deprotonation and the formation of a carboxyl\u00adate group, and contrasts the great disparity in the C15\u2014O4, O5 [1.206\u2005(2) and 1.320\u2005(2)\u2005\u00c5] and C16\u2014O6, O7 [1.229\u2005(2) and 1.315\u2005(2)\u2005\u00c5] bond lengths.The title salt, Fig.\u00a014N2O2 chromophore is almost planar, having an r.m.s. deviation of 0.009\u2005\u00c5 and, from symmetry, the carbonyl groups are anti. An intra\u00admolecular amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bond is noted, Table\u00a02syn as seen in the value of the N1\u2014C1\u2014C6\u2014N2 torsion angle of 34.8\u2005(2)\u00b0. This planarity does not extend to the terminal pyridinium rings which are approximately perpendicular to and lying to either side of the central chromophore, forming dihedral angles of 68.21\u2005(8)\u00b0. The central C7\u2014C7i bond length of 1.538\u2005(4)\u2005\u00c5 is considered long for a C\u2014C bond involving sp2-hybridized atoms \u2005\u00c5, and almost perpendicular in the salt, with N1\u2014C1\u2014C6\u2014N2 being 73.84\u2005(15)\u00b0. These differences are highlighted in the overlay diagram shown in Fig.\u00a02In the dication, the central Cet al., 2009et al., 2015et al., 1998i.e. C_IV \u00b0, and for one of the carb\u00adoxy\u00adlic acid groups, i.e. 22.50\u2005(10)\u00b0.In the anion, the C13\u2014C8\u2014C14\u2014O2 and C9\u2014C10\u2014C15\u2014O4 torsion angles of 15.3\u2005(3) and 16.4\u2005(3)\u00b0, respectively, indicate twisted conformations between these residues and the ring to which they are attached whereas the C11\u2014C12\u2014C16\u2014O6 torsion angle of 2.0\u2005(3)\u00b0 shows this carb\u00adoxy\u00adlic acid group to be co-planar with the ring. The conformational flexibility in 3,5-di\u00adcarb\u00adoxy\u00adbenzoate anions is well illustrated in arguably the four most closely related structures in the crystallographic literature  hydrogen bonds to form a familiar eight-membered {\u22efHOCO}2 synthon. These are connected by charge-assisted hy\u00addroxy-O\u2014H\u22efO(carboxyl\u00adate) hydrogen bonds that form C(8) chains. The result is a network of anions lying parallel to  chains featuring pairs of amide-N\u2014H\u22efO(amide) hydrogen bonds and 10-membered {\u22efHNC2O}2 synthons, Fig.\u00a03b. The tapes are aligned along the a axis and, in essence, thread through the voids in the anionic layers to form a three-dimensional architecture, Fig.\u00a03c. The links between the anionic layers and cationic tapes are hydrogen bonds of the type charge-assisted pyridinium-N\u2014O(carboxyl\u00adate). In this scheme, no apparent role for the carbonyl-O4 atom is evident. However, this atoms accepts two C\u2014H\u22efO inter\u00adactions from pyridyl- and methyl\u00adene-H to consolidate the mol\u00adecular packing. Additional stabilization is afforded by pyridyl-C\u2014H\u22efO inter\u00adactions, Table\u00a02The mol\u00adecular packing may be conveniently described in terms of O\u2014H\u22efO hydrogen bonding to define an anionic network which is connected into a three-dimensional architecture by N\u2014H\u22efO hydrogen bonds; Table\u00a02Crystal Explorer 3.1  region between 1.7 and 2.7\u2005\u00c5. A small but significant contribution to the Hirshfeld surface of the dication due to N\u22efO/O\u22efN contacts is the result of inter\u00admolecular amide-N\u2014H\u22efO(amide) inter\u00adactions.The overall two-dimensional fingerprint plot (FP) of the salt together with those of the dication and anion, and FP\u2019s delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC and C\u22efO/O\u22efC contacts are illustrated in Fig.\u00a07et al., 2014i.e. 0.8, due to a 23.7% contribution from the 54.5% available Hirshfeld surface and anti\u00adcipated 29.7% random contacts. The ER value of 1.4 corresponding to O\u22efH/H\u22efO contacts results from a relatively high 43.2% contribution by O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions. The carbon and oxygen atoms involved in the inter\u00admolecular C\u2014H\u22efO inter\u00adactions and short inter C\u22efO/O\u22efC contacts are at distances shorter than the sum of their respective van der Waals radii, hence they also have a high formation propensity, so the ER value is > 1. The C\u22efH/H\u22efC contacts in the crystal are enriched due to the poor nitro\u00adgen content and the presence of short inter\u00adatomic C\u22efH/H\u22efC contacts so the ratio is close to unity, i.e. 0.99. Finally, the ER value of 1.68 corresponding to N\u22efO/O\u22efN contacts for the surface of dication is the result of the charge-assisted N\u2014H\u22efO inter\u00adactions consistent with their high propensity to form.The inter\u00admolecular inter\u00adactions were further analysed using a recently reported descriptor, the enrichment ratio, ER ethanedi\u00adamide (LH2), has not been as well studied as the n = 3 and 4 isomers. This notwithstanding, the coordin\u00adation chemistry of LH2 is more advanced and diverse. Thus, co-crystals have been reported with a metal complex, i.e. [Mn3][ClO4]2\u00b7(LH2) 2 Pt}22+ \u00b7H2O}n 2(LH2)3}n  chemistry, as in the aforementioned [CuL(LH2)(OH2)]2 , prepared in accord with the literature procedure (Schauer Uiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located in a difference Fourier map but were refined with distance restraints of O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989016000980/hb7560sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016000980/hb7560Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016000980/hb7560Isup3.cmlSupporting information file. DOI: 1447965CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Refinement of the site-occupancy factors of the three disordered bromide ions converges with occupancies 0.701\u2005(2), 0.831\u2005(2) and 0.456\u2005(2) summing to approximately two bromide ions per formula unit. The structure was refined as a two-component inversion twin with volume fractions 0.109\u2005(8):0.891\u2005(8) for the two domains. The central C3N unit of the bis\u00adamidinium ion is linked to the aliphatic propyl chain by a C\u2014N single bond. The other two bonds in this unit have double-bond character as have the four C\u2014N bonds to the outer NMe2 groups. In contrast, the three C\u2014N bonds to the central N atom of the (di\u00admethyl\u00adaza\u00adnium\u00adyl)propyl group have single-bond character. Delocalization of the two positive charges occurs in the N/C/N and C/N/C planes, while the third positive charge is localized on the di\u00admethyl\u00adammonium group. The crystal structure is stabilized by O\u2014H\u22efO, N\u2014H\u22efBr, O\u2014H\u22efBr and C\u2014H\u22efBr hydrogen bonds, forming a three-dimensional network.The asymmetric unit of the title hydrated salt, C N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adchloro\u00adformamidinium chloride, see: Tiritiris & Kantlehner (2008N-[3-(di\u00admethyl\u00adamino)\u00adprop\u00adyl]-N--N\u2032,N\u2032,N\u2032\u2032,N\u2032\u2032-tetra\u00admethyl\u00adguanidinium bis\u00ad(tetra\u00adphenyl\u00adborate), see: Tiritiris & Kantlehner (2015N\u2032\u2032-[3-(di\u00admethyl\u00adamino)\u00adprop\u00adyl]-N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adguanidine, see: Tiritiris & Kantlehner  \u00c5b = 12.2932 (7) \u00c5c = 10.6633 (6) \u00c5\u03b2 = 97.454 (3)\u00b0V = 1190.39 (12) \u00c53Z = 2K\u03b1 radiationMo \u22121\u03bc = 3.40 mmT = 100 K0.41 \u00d7 0.29 \u00d7 0.25 mmBruker Kappa APEXII DUO diffractometerTmin = 0.334, Tmax = 0.481Absorption correction: multi-scan 6391 reflections with Rint = 0.033R[F2 > 2\u03c3(F2)] = 0.031wR(F2) = 0.069S = 0.997244 reflections265 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 0.37 e \u00c5\u22123\u0394\u03c1min = \u22120.23 e \u00c5\u22123\u0394\u03c1Absolute structure: refined as an inversion twinAbsolute structure parameter: 0.109 (8)APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015024305/sj5490Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024305/sj5490fig1.tif. DOI: The structure of the title compound with displacement ellipsoids at the 50% probability level. All carbon-bonded hydrogen atoms are omitted for the sake of clarity.Click here for additional data file.10.1107/S2056989015024305/sj5490fig2.tifac . DOI: ac view).N\u2014H\u22efBr, O\u2014H\u22efBr and O\u2014H\u22efO hydrogen bonds (black dashed lines) in the crystal structure of the title compound . The N\u2014H\u22efBr, O\u2014H\u22efBr, O\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds are depicted by black dashed lines.Mol\u00adecular packing of the title compound (1443022CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Vortioxetine, a new drug used to treat patients with major depressive disorder, has been crystallized as the free base and its methanol monosolvate. In both structures, the vortioxetine mol\u00adecules have similar conformations. 18H22N2S, (1), systematic name 1-{2-[sulfan\u00adyl]phen\u00adyl}piperazine, a new drug used to treat patients with major depressive disorder, has been crystallized as the free base and its methanol monosolvate, C18H22N2S\u00b7CH3OH, (2). In both structures, the vortioxetine mol\u00adecules have similar conformations: in (1), the dihedral angle between the aromatic rings is 80.04\u2005(16)\u00b0 and in (2) it is 84.94\u2005(13)\u00b0. The C\u2014S\u2014C bond angle in (1) is 102.76\u2005(14)\u00b0 and the corresponding angle in (2) is 103.41\u2005(11)\u00b0. The piperazine ring adopts a chair conformation with the exocyclic N\u2014C bond in a pseudo-equatorial orientation in both structures. No directional inter\u00adactions beyond normal van der Waals contacts could be identified in the crystal of (1), whereas in (2), the vortioxetine and methanol mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, generating [001] chains.Vortioxetine, C Views of the asymmetric units of (1) and (2), with atom labelling, are presented in Figs. 1A\u22efO1i [symmetry code: (i) x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0c-axis direction (Table\u00a01There are no hydrogen bonds or \u03c0\u2013\u03c0 stacking inter\u00adactions linking the mol\u00adecules in (1), while in (2) the presence of the additional methanol solvent mol\u00adecule results in the formation of zigzag chains mediated by alternating O1\u2014H1\u22efN2 and N2\u2014H2n Table\u00a01. a packiVortioxetine was supplied by Zhejiang Jingxin Pharmaceutical Co., Ltd. Crystals of (1) and (2) suitable for X-ray diffraction were recrystallized by slow evaporation from aceto\u00adnitrile and methanol\u2013water solutions, respectively, at room temperature over a few days.Uiso(H) = 1.2Ueq or 1.5Ueq(carrier atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015012256/hb7395sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989015012256/hb73951sup3.hklStructure factors: contains datablock(s) 1, 2. DOI: 10.1107/S2056989015012256/hb73952sup4.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989015012256/hb73951sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015012256/hb73952sup5.cmlSupporting information file. DOI: 1408949, 1408948CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A and B) in the asymmetric unit, the A and B mol\u00adecules are linked via pairs of N\u2014H\u22efS hydrogen bonds, forming dimers with an via pairs of C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming ribbons propagating along [100].In the crystal of the title compound, which crystallized with two independent mol\u00adecules  in the asymmetric unit. Both mol\u00adecules have an L-shape but differ in the orientation of the benzyl ring with respect to the 3,4-di\u00admeth\u00adoxy\u00adbenzyl\u00adidine ring, this dihedral angle is 65.59\u2005(8)\u00b0 in mol\u00adecule A and 73.10\u2005(8)\u00b0 in mol\u00adecule B. In the crystal, the A and B mol\u00adecules are linked via pairs of N\u2014H\u22efS hydrogen bonds, forming dimers with an R22(8) ring motif. The dimers are linked via pairs of C\u2014H\u22efO hydrogen bonds, giving inversion dimers of dimers. These units are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming ribbons propagating in the [100] direction.The title compound, C S-benzyl\u00addithio\u00adcarbazate (SBDTC) whose derivatives have shown promising biological activities  in the asymmetric unit. Both mol\u00adecules have an l-shape but differ in the orientation of the benzyl ring with respect to the 3,4-di\u00admeth\u00adoxy\u00adbenzyl\u00adidine ring, this dihedral angle being 65.59\u2005(8) \u00b0 in mol\u00adecule A and 73.10\u2005(8) \u00b0 in mol\u00adecule B  are 1.331\u2005(2) and 1.282\u2005(2)\u2005\u00c5, respectively, in mol\u00adecule A, and 1.336\u2005(2) and 1.280\u2005(2)\u2005\u00c5, respectively, in mol\u00adecule B. The shorter length of the C\u2014N bond suggests the existence of a double bond which belongs to the imine group. Similarly, the shorter C\u2014S bond length  relative to that of  suggests that the former possesses double-bond character, indicating that the mol\u00adecule exists in its thione form in the solid state. The functional group identities proposed from these bond lengths are further supported by data obtained from the IR analysis reported below. Furthermore, the bond distances in the title compound are similar to those found for other carbodi\u00adthio\u00adate-derived Schiff bases \u2014C bond lengths (C1\u2014N1 and N2\u2014C9 in A and B) crystallizes in the conformer in which the two aromatic rings of the compound are cis with respect to each other across the C=N bonds, while the thione sulfur atom is trans with respect to the same bond.Both mol\u00adecules  ring motif -2-benzyl\u00adidenehydrazine-1-carbodi\u00adthio\u00adates gave 13 hits. One of these concerns a structure very similar to the title compound, namely benzyl (E)-2-(4-meth\u00adoxy\u00adbenzyl\u00adidene)hydrazine-1-carbodi\u00adthio\u00adate \u00b0 in mol\u00adecule A and 73.10\u2005(8)\u00b0 in mol\u00adecule B of the title compound.A search of the Cambridge Structural Database . IR : 3360, 3122, 1602, 1069, 1023, 950, 788, 695. LCMS (ESI+): 347.1 [M+H]+.1.98\u2005g (0.01\u2005mol) of Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901500095X/su5044sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500095X/su5044Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500095X/su5044Isup3.cmlSupporting information file. DOI: 1043887CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in this one-dimensional coordination polymer, with aqua, 4-formyl\u00adbenzoate and bridging pyrazine ligands, is located on a twofold rotation axis and has a slightly distorted octa\u00adhedral coordination sphere. Strong intra\u00admolecular O\u2014H\u22efO hydrogen bonds link the water mol\u00adecules to the carboxyl\u00adate O atoms.The Co 8H5O3)2(C4H4N2)(H2O)2]n, the CoII atom is located on a twofold rotation axis and has a slightly distorted octa\u00adhedral coordination sphere. In the equatorial plane, it is coordinated by two carboxyl\u00adate O atoms of two symmetry-related monodentate formyl\u00adbenzoate anions and by two N atoms of two bridging pyrazine ligands. The latter are bis\u00adected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water mol\u00adecules. In the formyl\u00adbenzoate anion, the carboxyl\u00adate group is twisted away from the attached benzene ring by 7.50\u2005(8)\u00b0, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90\u2005(4)\u00b0. The pyrazine ligands bridge the CoII cations, forming linear chains running along the b-axis direction. Strong intra\u00admolecular O\u2014H\u22efO hydrogen bonds link the water mol\u00adecules to the carboxyl\u00adate O atoms. In the crystal, weak O\u2014Hwater\u22efOwater hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via C\u2014Hpyrazine\u22efOform\u00adyl hydrogen bonds, forming a three-dimensional network. There are also weak C\u2014H\u22ef\u03c0 inter\u00adactions present.In the title polymeric compound, [Co(C Atoms N1 and N2 of the pyrazine ligand and Co1 are located on a twofold rotation axis  x, y\u00a0+\u00a01, z] is 7.1193\u2005(4)\u2005\u00c5.The asymmetric unit of the title compound contains a Cois Fig.\u00a01. The pyron Fig.\u00a02. The disIIO4N2 coordination sphere is composed of two carboxyl\u00adate O atoms  of two symmetry-related monodentate formyl\u00adbenzoate anions and two N atoms  of two bridging pyrazine ligands, which are bis\u00adected by the twofold rotation axis. The axial positions are occupied by two O atoms (O4 and O4i) of the coordinating water mol\u00adecules.The equatorial plane of the CoA (C2\u2013C7) is 7.50\u2005(8)\u00b0, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90\u2005(4)\u00b0.The near equality of the C1\u2014O1 [1.272\u2005(2)\u2005\u00c5] and C1\u2014O2 [1.245\u2005(2)\u2005\u00c5] bonds in the carboxyl\u00adate group indicates a delocalized bonding arrangement, rather than localized single and double bonds. The Co\u2014N bond length is 2.165\u2005(9)\u2005\u00c5, while the Co\u2014O bond lengths are 2.0551\u2005(9)\u2005\u00c5 (for benzoate oxygen) and 2.1491\u2005(11)\u2005\u00c5 (for water oxygen), close to standard values. The Co1 atom is displaced by 0.1034\u2005(2)\u2005\u00c5 from the mean plane of the carboxyl\u00adate group (O1/C1/O2). The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring water\u22efOwater hydrogen bonds  were located in a difference Fourier map and were refined freely. The methine H atom was also located in a difference Fourier map and the C\u2014H distance restrained to 0.984\u2005(13)\u2005\u00c5. The aromatic C-bound H atoms were positioned geometrically with C\u2014H = 0.93\u2005\u00c5, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a024\u00b77H2O  in H2O (25\u2005ml) and pyrazine  in H2O (25\u2005ml) with sodium 4-formyl\u00adbenzoate  in H2O (70\u2005ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving orange single crystals.The title compound was prepared by the reaction of CoSO10.1107/S205698901500403X/wm5129sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500403X/wm5129Isup2.hklStructure factors: contains datablock(s) I. DOI: 1051344CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Compound (I) was the expected product and compound (II) was the oxidation product from air exposure.The title compounds C 17H14BrNO2, (I), and C17H15NO3, (II), were obtained from the reaction of 6-meth\u00adoxy-3,4-di\u00adhydro-2H-naphthalen-1-one and 2-bromo\u00adnicotinaldehyde in ethanol. Compound (I) was the expected product and compound (II) was the oxidation product from air exposure. In the crystal structure of compound (I), there are no short contacts or hydrogen bonds. The structure does display \u03c0\u2013\u03c0 inter\u00adactions between adjacent benzene rings and adjacent pyridyl rings. Compound (II) contains two independent mol\u00adecules, A and B, in the asymmetric unit; both are non-planar, the dihedral angles between the meth\u00adoxy\u00adbenzene and 1H-pyridin-2-one mean planes being 35.07\u2005(9)\u00b0 in A and 35.28\u2005(9)\u00b0in B. In each mol\u00adecule, the 1H-pyridin-2-one unit participates in inter\u00admolecular N\u2014H\u22efO hydrogen bonding to another mol\u00adecule of the same type (A to A or B to B). The structure also displays \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl and the benzene rings of non-equivalent mol\u00adecules .The title compounds C Our research strategy to synthesize novel compounds considered analogs of the natural product chalcone, which contains two aromatic rings and an \u03b1-\u03b2-unsaturated ketone. Chalcones, bioactive defense mol\u00adecules found in plants and used in traditional Chinese medicine, have demonstrated anti\u00adcancer, anti\u00adbacterial, anti\u00adfungal, and anti-inflammatory properties  and O1B\u2014C1B = 1.257\u2005(3)\u2005\u00c5. The mol\u00adecules are also non-planar, the benzene\u2013pyridyl angle being 36.18\u2005(10)\u00b0 in A and 35.91\u2005(10)\u00b0 in B.Compound (I)Cg1i distance is 3.635\u2005(3)\u2005\u00c5  and has a \u2018face-on\u2019 geometry. There are two \u03c0\u2013\u03c0 inter\u00adactions in the crystal between adjacent benzene rings, Cg1\u22efCg1ii = 3.944\u2005(4)\u2005\u00c5  and between adjacent pyridyl rings, Cg2\u22efCg2iii = 3.639\u2005(4)\u2005\u00c5 . The \u03c0\u2013\u03c0 inter\u00adactions form ribbons in the ne Fig.\u00a03, which ane Fig.\u00a03.H-pyridin-2-one unit participates in inter\u00admolecular N\u2014H\u22efO hydrogen bonding, with a classical A to A or B to B), see Fig.\u00a05A\u2013B or B\u2013A inter\u00adactions)  and Cg5\u22efCg6ii = 3.857\u2005(4)\u2005\u00c5 .In each one of the independent mol\u00adecules in (II)s) Fig.\u00a06; Cg3\u22efCg4et al., 2016et al., 2002et al., 2005et al., 2002A search of the Cambridge Structural Database  and 2-bromo\u00adnicotinaldehyde (1\u2005mmol) were dissolved in ethanol (5\u2005mL). An NaOH solution  was added and the reaction was stirred until a precipitate formed. The reaction mixture was cooled in an ice bath for 20 minutes. The solids were filtered off and recrystallized from MeOH/H2O. Slow evaporation of a methano\u00adlic solution gave dark purple/brown crystals, which proved to be 3-[(E)-meth\u00adyl]pyridin-2(1H)-one, (II), and lighter purple crystals which proved to be (E)-2-[(2-bromopyridin-3-yl)methyl\u00adidene]-6-meth\u00adoxy-3,4-di\u00adhydro\u00adnaph\u00adthalen-1(2H)-one, (I).6-Meth\u00adoxy-3,4-di\u00adhydro-2Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016009300/bg2587sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989016009300/bg2587Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016009300/bg2587IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1484124, 1484123CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this model CD8+ T cells mediate biliary ductular damage, whereas CD4+ T cells mediate induction of colon-specific autoimmunity. Importantly, IL-2R\u03b1\u2212/\u2212 mice have high levels of interferon \u03b3 (IFN-\u03b3), and interleukin-17A (IL-17A). We produced unique double deletions of mice that were either IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 or IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 to specifically address the precise role of these two cytokines in the natural history of autoimmune cholangitis and colitis. Of note, deletion of IL-17A in IL-2R\u03b1\u2212/\u2212 mice led to more severe liver inflammation, but ameliorated colitis. In contrast, there were no significant changes in the immunopathology of double knock-out IFN-\u03b3\u2212/\u2212 IL-2R\u03b1\u2212/\u2212 mice, compared to single knock-out IL-2R\u03b1\u2212/\u2212 mice with respect to cholangitis or colitis. Furthermore, there was a significant increase in pathogenetic CD8+ T cells in the liver of IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice. Our data suggest that while IL-17A plays a protective role in autoimmune cholangitis, it has a pro-inflammatory role in inflammatory bowel disease. These data take on particular significance in the potential use of anti-IL-17A therapy in humans with primary biliary cirrhosis.IFN-\u03b3 is a signature Th1 cell associated cytokine critical for the inflammatory response in autoimmunity with both pro-inflammatory and potentially protective functions. IL-17A is the hallmark of T helper 17 (Th17) cell subsets, produced by \u03b3\u03b4T, CD8+ T, NK and NKT cells. We have taken advantage of our colony of IL-2R\u03b1 We report herein that deletion of IL-17A in IL-2R\u03b1\u2212/\u2212 mice aggravated cholangitis but ameliorated colitis. In contrast, there was no significant effect of the deletion of IFN-\u03b3 on the immunopathology of either autoimmune cholangitis or colitis. Importantly, T cells, particularly CD8+ T cells, were significantly increased in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice. Our data suggests that IL-17A plays a protective role in autoimmune cholangitis but a proinflammatory role in colitis in IL-2R\u03b1\u2212/\u2212 mice.To examine in specific detail the role of IFN-\u03b3 versus IL-17A in autoimmune cholangitis and colitis, we took advantage of IL-17A\u2212/\u2212  and IFN-\u03b3\u2212/\u2212 (B6.129S7-IFN-\u03b3tm1Ts) mice on a C57B/6J background were initially obtained from the Jackson Laboratory . IL-17A\u2212/\u2212 mice were donated by Dr. Yoichiro Iwakura . All genetically modified mice studied herein have been backcrossed to C57BL/6 background for at least 10 generations. IL-2R\u03b1\u2212/\u2212 were bred to heterozygosity to these strains. To generate IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 and IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice, IL-17A\u2212/\u2212 or IFN-\u03b3\u2212/\u2212 mice were mated with IL-2R\u03b1+/\u2212 mice to obtain IL-17A+/\u2212IL-2R\u03b1+/\u2212 or IFN-\u03b3+/\u2212IL-2R\u03b1+/\u2212 mice, which were subsequently backcrossed with IL-17A\u2212/\u2212 or IFN-\u03b3\u2212/\u2212 mice to obtain IL-17A\u2212/\u2212IL-2R\u03b1+/\u2212 or IFN-\u03b3\u2212/\u2212IL-2R\u03b1+/\u2212 mice; IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 or IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice were obtained by inter-breeding. The IL-2R\u03b1 gene was identified by flow cytometric analysis based on mean fluorescent intensity of CD25. All mice were studied between 12 and 16 weeks of age and animals were individually housed in ventilated cages under the specific pathogen-free conditions. All animal experimental protocols were approved by the Institutional Animal Care and Use Committee of the School of Life Sciences, University of Science and Technology of China, Hefei, China. Animals were anesthetized for blood collection with Xylazine (5 mg/kg)/Ketamine (25 mg/kg) administered subcutaneously. Euthanasia was performed by an overdose of CO2 by inhalation, consistent with the recommendations on the Panel on Euthanasia of the American Veterinary Medical Association. There was no surgery performed and any animals exhibiting discomfort or distress by the veterinary staff were euthanized.IL-2R\u03b12. Cells were then stained for surface markers using anti-CD4 PerCP/CY5.5, anti-NK1.1 PE/CY7, anti-CD3 Pacific Blue and anti-CD8\u03b2 FITC (Biolegend), then intracellular stained with anti-IFN-\u03b3 PE and anti-IL-17A APC (Biolegend) after fixation and permeabilization with Fixation Buffer and Permeabilization Wash Buffer (Biolegend), Rat IgG1, \u03ba PE and Rat IgG1, \u03ba APC were used as isotype controls for anti-IFN-\u03b3 PE and anti-IL-17A APC respectively. Finally, samples were subjected to multiple-color analysis by BD FACSVerse flow cytometer (BD Biosciences). Acquired data were analyzed with FlowJo Software .Lymphocytes from spleen and liver were isolated using 40%/70% percoll  Liver and colon were fixed in 4% paraformaldehyde, embedded in paraffin and cut into 4 and 6 \u00b5m sections respectively, then deparaffinized, stained with hematoxylin and eosin (H&E), and evaluated using light microscopy. The quantitation of tissue damage was performed by a \u201cblinded\u201d pathologist. Firstly, the degree of portal inflammation was evaluated and scored according to the most severe lesions as follows: 0, no change; 1, minimal inflammation; 2, mild inflammation; 3, moderate inflammation; 4, severe inflammation. In addition, the degree of inflammatory frequency in a specimen was determined by the percentage of affected tissue within the total hepatic lobules per specimen and coded as follows: 0, none, 1, 1%\u201310%; 2, 11\u201320%; 3, 21\u201350%; 4, more than 50%. Finally, a summary score that includes severity and frequency analysis was generated as the sum of these scores. We note that lobular inflammation was scored in the same fashion as portal inflammation. Second, bile duct damage was evaluated firstly by the degree of severity in the most severe lesions as follows: 0, no change; 1, epithelial damage (only cytoplasmic change); 2, epithelial damage with cytoplasmic and nuclear change; 3, non-suppurative destructive cholangitis (CNSDC); 4, bile duct loss. The frequency of bile duct damage was then scored as follows: 0, none; 1, 1%\u201310%; 2, 11\u201320%; 3, 21\u201350%; 4, more than 50%. To evaluate bile duct loss, bile duct epithelium was highlighted by immunostaining using rabbit anti-keratin wide antibody . To obtain an integrative evaluation, the scores of severity and frequency were added together. Third, colon histopathology was scored as follows: 0, no significant changes; 1, minimal scattered mucosal inflammatory cell infiltrates, with or without minimal epithelial hyperplasia; 2, mild scattered to diffuse inflammatory cell infiltrates, sometimes extending into the submucosa and associated with erosions, with mild to moderate epithelial hyperplasia and mild to moderate mucin depletion from goblet cells; 3, moderate inflammatory cell infiltrates that were sometimes transmural, with moderate to severe epithelial hyperplasia and mucin depletion; and 4, marked inflammatory cell infiltrates that were often transmural and associated with crypt abscesses and occasional ulceration, with marked epithelial hyperplasia, mucin depletion, and loss of intestinal glands \u2212\u0394\u0394Ct method Total RNA from liver and colon was extracted with RNeasy Mini Kit , and cDNA synthesized with the PrimeScript RT reagent Kit . Quantitative PCR was performed using a SYBR Premix Ex TaqTM II . Data were collected by an ABI StepOne real-time PCR system . The PCR primers used in this study are listed in The levels of IFN-\u03b3, tumor necrosis factor \u03b1 (TNF-\u03b1), IL-2, IL-4, IL-6 and IL-10 from serum were measured simultaneously with a cytometric bead array kit , using a FACSVerse flow cytometer with CBA software (BD Biosciences).Data are presented as the mean \u00b1 standard error. The histological scores of liver inflammation and colitis were compared using one-way analysis of variance (ANOVA) followed by Kruskal-Wallis multiple comparisons. The two-tailed unpaired Mann-Whitney test was used in other comparisons. A value of p<0.05 was considered statistically significant; a value of 0.05<p<0.1 was noted as only a trend.\u2212/\u2212 mice. CD8+ T cells from IL-2R\u03b1\u2212/\u2212 mice produced a greater quantity of IFN-\u03b3 compared to IL-2R\u03b1+/\u2212 in liver (P\u200a=\u200a0.0159), but almost no IL-17A. In contrast, IL-2R\u03b1\u2212/\u2212 CD4+T cells produced more IL-17A than IL-2R\u03b1+/\u2212 CD4+ T cells (P\u200a=\u200a0.0159), while CD4+T cells also produced some IFN-\u03b3 but at levels lower than CD8+T cells (P\u200a=\u200a0.0286) (P\u200a=\u200a0.0190) and CD8+T cells expressing intracellular IFN-\u03b3 (P\u200a=\u200a0.0095) comparing IL-2R\u03b1\u2212/\u2212 mice to IL-2R\u03b1+/\u2212 mice (We determined the cellular source of IL-17A and IFN-\u03b3 in IL-2R\u03b1\u200a0.0286) . Similar+/\u2212 mice .\u2212/\u2212 mice respectively to generate IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice and IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice. Histological examination of the liver tissue sections from 12-16-week-old mice demonstrated that IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice had more lymphocytes infiltrating around portal tracts compared to IL-2R\u03b1\u2212/\u2212 mice (P<0.05), and more severe lobular inflammation (P<0.05). IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice also had more severe bile duct damage compared to IL-2R\u03b1\u2212/\u2212 mice (P<0.05). In contrast, there was no significant difference between IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice and IL-2R\u03b1\u2212/\u2212 mice (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0058), but no significant difference between IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice and IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.6720)  . All res\u2212/\u2212 mice developed massive enlargement of lymph nodes and spleen \u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice. There was also a greater frequency of splenomegaly in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice (8/22) compared to IL-2R\u03b1\u2212/\u2212 mice (0/17) and IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice (0/11) (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice positively correlated with liver mononuclear cells (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 compared to IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0005), due to the remarkable expansion of CD8+T cells (P\u200a=\u200a0.0011). There were no differences between IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 and IL-2R\u03b1\u2212/\u2212 mice. The absolute number of total hepatic T cells (P\u200a=\u200a0.0524) and CD8+T cells (P\u200a=\u200a0.0630) trended toward an increase in total hepatic CD4+T cells (P\u200a=\u200a0.0375) in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice, but there were no differences noted in IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 or IL-2R\u03b1\u2212/\u2212 mice (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0355). The absolute number of splenic CD8+T cell was also increased in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared with IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0039) (It has been reported that IL-2Rae (0/11) . The splar cells . The per\u2212/\u2212 mice . The fre\u200a0.0039) .\u2212/\u2212IL-2R\u03b1\u2212/\u2212 and IL-2R\u03b1\u2212/\u2212, but not IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice frequently suffered from rectal prolapse and diarrhea. Therefore we examined these strains for colitis. There was no significant difference between IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice and IL-2R\u03b1\u2212/\u2212 mice. Colitis, however, was improved in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice (P<0.05), although minimal colitis still occurred in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0034), but no significant difference was found in IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.2723) (IFN-\u03b3\u2212/\u2212 mice . Colon w\u200a0.2723) .P\u200a=\u200a0.0055) , CD4+T cells (P\u200a=\u200a0.0185) and CD8+T cells (P\u200a=\u200a0.0039) (P\u200a=\u200a0.0463) (\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice (P\u200a=\u200a0.0050) (Mesenteric lymphocytes were significantly decreased (\u200a0.0055)  in IL-17\u200a0.0039) . The fre\u200a0.0463)  and the \u200a0.0050) .\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared with IL-2R\u03b1\u2212/\u2212 mice contained significantly higher levels of IFN-\u03b3 (P\u200a=\u200a0.0168) and IL-10 (P\u200a=\u200a0.0444), but lower levels of IL-6 (P\u200a=\u200a0.0221), and no changes in IL-2 (P\u200a=\u200a0.3969) or TNF-\u03b1 (P\u200a=\u200a0.6019). Meanwhile serum from IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared with IL-2R\u03b1\u2212/\u2212 mice contained lower levels of IL-6 (P\u200a=\u200a0.0111), and no changes in IL-2 (P\u200a=\u200a0.5350), IL-10 (P\u200a=\u200a0.4295) and TNF-\u03b1 (P\u200a=\u200a0.2769) , IL-27 (IL-27p28 and Ebi3), IL-6, TNF\u03b1 and IFN-\u03b3. As shown in P\u200a=\u200a0.0012), TNF-\u03b1 (P\u200a=\u200a0.0023) and Ebi3 (P\u200a=\u200a0.0012), but decreased the level of IL-6 (P\u200a=\u200a0.0379) in the liver. There were no detectable changes of these cytokines in the colon. And after deletion of IFN-\u03b3 in IL-2R\u03b1\u2212/\u2212 mice there were lower levels of TNF-\u03b1 (P\u200a=\u200a0.0111) and IL-6 (P\u200a=\u200a0.0006), but no change in Ebi3 (P\u200a=\u200a0.8048) in the liver. In the colon tissue of IL-2R\u03b1\u2212/\u2212 mice, the mRNA levels of TNF-\u03b1 (P\u200a=\u200a0.0003) and Ebi3 (P\u200a=\u200a0.0002) were decreased, whereas that of IL-6 (P\u200a=\u200a0.2345) reflected no change. There was no change of mRNA levels of IL-17 expression in colon and liver after deletion of IFN-\u03b3 in IL-2R\u03b1\u2212/\u2212 mice (data not shown). We stimulated hepatic mononuclear cells and stained the cells for intracellular cytokines IFN-\u03b3, IL-4 and IL-17F. The frequency of IFN-\u03b3+ cells was significantly increased both in CD4+T (P\u200a=\u200a0.0186) cells and CD8+T (P\u200a=\u200a0.0759) cells from IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice, although there is only a trend toward significance in CD8+T cells (Serum from IL-17A\u200a0.2769) . Further+T cells . Little \u2212/\u2212 mice, IL-17A levels appear to peak at 8 weeks to 13 weeks of age and then steadily decline, indicating that IL-17 may be involved in earlier disease development \u2212/\u2212 mice, autoimmune cholangitis is more severe. IL-2R\u03b1\u2212/\u2212 mice spontaneously develop clinically apparent autoimmune cholangitis at 8 weeks; the appearance of increased IL-17A, at that time, may serve an anti-inflammatory role.IL-17A is mainly produced by Th17 cells, also by \u03b3\u03b4T cells, CD8+T cells, natural killer (NK) cells and NKT cells. The functions of IL-17 are mediated via binding to IL-17RA and IL-17RC, two isoforms of the IL-17 receptor \u2212/\u2212 hosts transferred with IL-17A\u2212/\u2212 CD4+ CD45RBhigh T cells show more severe colitis compared to Rag1\u2212/\u2212 mice received corresponding wild type CD4+ T cells, accompanying by increased IFN-\u03b3 level in colon reg cell\u2013depleted CD4+ CD45RBlow cells into Rag\u2212/\u2212 mice could also induce colitis, but with a slower onset than with CD4+ CD45RBhigh T cells. Colitis mediated by CD4+ CD45RBhigh T cells is characterized by increased Th1 cytokines and Treg cell\u2013depleted CD4+ CD45RBlow cells are characterized by an increase in Th17 cytokines \u2212/\u2212 mice, the ratio of effector/memory CD4+ T cells significantly increased. Hence, the colitis in IL-2R\u03b1\u2212/\u2212 mice may be mediated by CD4+ CD45RBlow T cells. The percentage of memory CD4+T cell in mesenteric lymph nodes decreased in IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice compared to IL-2R\u03b1\u2212/\u2212 mice, while there was no change in IFN-\u03b3\u2212/\u2212IL-2R\u03b1\u2212/\u2212 mice. Previous studies have identified that CD8+T cells mediate intrahepatic damage in IL-2R\u03b1\u2212/\u2212 mice. Herein we demonstrate that deletion of IL-17A in IL-2R\u03b1\u2212/\u2212 mice is associated with significantly increased intrahepatic CD8+T cells and increased intracellular expression of IFN-\u03b3 by CD8+T cells. We examined the IL-7 and IL-15 expression in liver (data not shown), which could promote CD8+T proliferation, but there were no significant differences in mRNA levels for these genes between IL-17A\u2212/\u2212IL-2R\u03b1\u2212/\u2212 and IL-2R\u03b1\u2212/\u2212 mice. These data take on particular significance in the possible use of cytokine blocking reagents to treat either autoimmune cholangitis or colitis. Our data suggest that IL-17A plays a different role in autoimmune cholangitis and colitis and raises concerns and caution regarding the therapeutic use of anti-IL-17A.The role of IL-17 in IBD is controversial. IL-17A plays a proinflammatory role in acute TNBS (Trinitro-Benzene-Sulfonic Acid)-induced colitis \u2212/\u2212 mice develop simultaneous cholangitis and colitis. We also suggest that future work explore treatment of mice with established disease using antibodies against IL-17. Our data would further imply the potential of modulating IL-17A in patients with PBC, but also caution against such usage in inflammatory bowel disease. It is likely that the immunopathology in each of these human diseases will be different during different stages of immunopathology and it seems important that any clinical trials include a rigorous analysis of the patient's immune response, including monitoring cytokines. Finally, we should emphasize that this is the first report of the use of this combination of double knockouts as a model to explore autoimmune cholangitis and inflammatory bowel disease. The data, as with any animal model, should be interpreted with caution before any direct extrapolation to human therapy.IL-17 has pleiotropic effects and the data herein reflect the immunopathology in our unique model. Clearly, further work can potentially explore these relationships between IL-17A and IFN-\u03b3. We emphasize that IL-2R\u03b1"}
{"text": "Scientific Reports6: Article number: 19829; 10.1038/srep19829 published online: 01292016; updated: 05202016.This Article contains typographical errors.In the Results section under subheading \u2018Quantitative comparison of WNS on bats\u2019,\u201cThe fungal load on qPCR-positive bats ranged from 0.21 pg to 3.41\u2009\u03bcg across the surface of the left wing \u201d.should read:\u201cThe fungal load on qPCR-positive bats ranged from 0.21 fg to 3.41\u2009ng across the surface of the left wing \u201d.\u22125\u2009\u03bcg) overlapped that from UV-positive individuals \u201d.\u201cThe fungal load from UV-negative individuals (median\u2009=\u20093.78\u2009\u00d7\u200910should read:\u22125\u2009ng) overlapped that from UV-positive individuals \u201d.\u201cThe fungal load from UV-negative individuals (median\u2009=\u20093.78\u2009\u00d7\u2009102 (log10(ng))\u2019 was incorrectly given as \u2018Fungal load per cm2 (log10(\u03bcg))\u2019In the upper panel of Figure 4, the y-axis \u2018Fungal load per cmP. destructans load per cm2 (log10(ng))\u2019 was incorrectly given as \u2018P. destructans load per cm2 (log10(\u03bcg))\u2019In the upper panel of Figure 5, the y-axis \u2018P. destructans load per cm2 (log10(ng))\u2019 was incorrectly given as \u2018P. destructans load per cm2 (log10(\u03bcg))\u2019In Figure 6, the x-axis \u20182 (log10(ng))\u2019 was incorrectly given as \u2018Fungal load per cm2 (log10(\u03bcg))\u2019In Figure 8, the x-axis \u2018Fungal load per cmIn the legend of Figure 8,n\u2009=\u2009255) and negative  using UV trans-illumination\u201d.\u201cBats were identified as positive  and negative  using UV trans-illumination\u201d.\u201cBats were identified as positive (orange; The correct Figures 4, 5, 6 and 8 appear below as"}
{"text": "The title mol\u00adecular salt, obtained by the reaction of sulfamic acid with 2-amino-5-nitro\u00adpyridine, is the result of a proton transfer from sulfamic acid to the N atom of the pyridine ring. In the crystal, the cations and anions are linked by a number of N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming sheets lying parallel to (100). 5H6N3O2+ \u00b7H2NO3S\u2212, was obtained from the reaction of sulfamic acid with 2-amino-5-nitro\u00adpyridine. A proton transfer from sulfamic acid to the pyridine N atom occurred, resulting in the formation of a salt. As expected, this protonation leads to the widening of the C\u2014N\u2014C angle of the pyridine ring, to 122.9\u2005(3)\u00b0, with the pyridinium ring being essentially planar (r.m.s. deviation = 0.025\u2005\u00c5). In the crystal, the ion pairs are joined by three N\u2014H\u22efO and one N\u2014H\u22efN hydrogen bonds in which the pyridinium N atom and the amino N atom act as donors, and are hydrogen bonded to the carboxyl\u00adate O atoms and the N atom of the sulfamate anion, thus generating an R33(22) ring motif. These motifs are linked by further N\u2014H\u22efO hydrogen bonds enclosing R33(8) loops, forming sheets parallel to (100). The sheets are linked via weak C\u2014H\u22efO hydrogen bonds, forming a three-dimensional structure. The O atoms of the nitro group are disordered over two sets of sites with a refined occupancy ratio of 0.737\u2005(19):0.263\u2005(19).The title mol\u00adecular salt, C Some pyridine derivatives possess non-linear optical (NLO) properties  bond is clearly longer than that in the ring \u2005\u00c5] bond is shorter than the N3\u2014C1 [1.357\u2005(4)\u2005\u00c5] and N3\u2014C5 [1.340\u2005(5)\u2005\u00c5] bonds, and the C1\u2014C2 [1.411\u2005(5)\u2005\u00c5] and C3\u2014C4 [1.402\u2005(6)\u2005\u00c5] bonds lengths are significantly longer than bonds C2\u2014C3 [1.348\u2005(5)\u2005\u00c5] and C4\u2014C5 [1.338\u2005(6)\u2005\u00c5], similar to those observed previously for the amino\u00adpyridinium cation (Babu 2 [1.317\u2005(5)\u2005\u00c5] and C\u2014NO2 [1.449\u2005(6)\u2005\u00c5] distances in the cations are, respectively, shortened and lengthened with respect to the same bond lengths [1.337\u2005(4) and 1.429\u2005(4)\u2005\u00c5] observed for 2-amino-nitro\u00adpyridine , which induces the aggregation of the independent organic cation 2-amino-5-nitro\u00adpyridinium. This kind of arrangement is also observed in the related structure of 2-amino-5-nitro\u00adpyridinium hydrogen selenate  hydrogen bonds  and C\u2014N(O2) bond lengths are ca 1.32 and 1.45\u2005\u00c5, respectively. A search for the anion amino\u00adsulfamate gave 23 hits but only 17 contained atomic coordinates. Here the S\u2014O bond lengths vary from ca 1.399 to 1.469\u2005\u00c5, while the N\u2014S bond length varies from ca 1.63 to 1.80\u2005\u00c5. The bond lengths and angles in the title salt are very similar to those reported for the various structures in the CSD.A search of the Cambridge Structural Database  = 1.2Ueq(C). The O atoms of the nitro group are disordered over two sets of sites (O1/O1\u2032 and O2/O2\u2032) with a refined occupancy ratio of 0.737\u2005(19):0.263\u2005(19).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015000365/su5048sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015000365/su5048Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015000365/su5048Isup3.cmlSupporting information file. DOI: 1042506CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Macrocycle A and mol\u00adecule B both occupy special positions on a twofold rotation axis and the inversion centre, respectively. The supra\u00admolecular unit [A\u2022B] is built by the simultaneous coordination of one of the nitrile N atoms of B to the three mercury atoms of the macrocycle A. The Hg\u22efN distances range from 2.990\u2005(4) to 3.030\u2005(4)\u2005\u00c5 and are very close to those observed in the related adducts of the macrocycle A with other nitrile derivatives. The mol\u00adecule of B is almost perpendicular to the mean plane of the macrocycle A at the dihedral angle of 88.20\u2005(5)\u00b0. The donor\u2013acceptor Hg\u22efN inter\u00adactions do not affect the C\u00a0N bond lengths [1.136\u2005(6) and 1.140\u2005(6)\u2005\u00c5]. The trans nitrile group of B coordinates to another macrocycle A, forming an infinite mixed-stack [A\u2022B]\u221e architecture toward [101]. The remaining N atoms of two nitrile groups of B are not engaged in any donor\u2013acceptor inter\u00adactions. In the crystal, the mixed stacks are held together by inter\u00admolecular C\u2014F\u22efC\u00a0N secondary inter\u00adactions [2.846\u2005(5)\u20132.925\u2005(5)\u2005\u00c5].The title compound, [Hg Both macrocycle A and the mol\u00adecule of B occupy special positions on a twofold rotation axis and inversion centre, respectively. The supra\u00admolecular unit of (I) is built by the simultaneous coordination of the nitrile N1 nitro\u00adgen atom of B to the three mercury atoms of the macrocycle A \u20132.99\u2005(1)\u2005\u00c5], acrylo\u00adnitrile [2.87\u2005(1)\u20132.96\u2005(1)\u2005\u00c5] and benzo\u00adnitrile [2.97\u2005(1)\u20133.13\u2005(1)\u2005\u00c5]  [3.102\u2005(11)\u20133.134\u2005(11)\u2005\u00c5] \u00b0. It is very important to point out that the donor\u2013acceptor Hg\u22efN inter\u00adactions do not affect the C\u00a0N bond lengths [1.136\u2005(6) and 1.140\u2005(6)\u2005\u00c5].Complex , F5\u22efC12iv 2.846\u2005(5) and F6\u22efC11v 2.925\u2005(5)\u2005\u00c5; symmetry codes: (iii) \u2212x, y, z; (iv) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; (v) \u2212x, \u2212y, z]  and (II) are very similar. In both complexes, the guest mol\u00adecules of tetra\u00adcyano\u00adethyl\u00adene B and tetra\u00adcyano\u00adquinodi\u00admethane C are arranged perpendicularly to macrocycle A, with the same coordination mode of the trans nitrile groups to the three mercury atoms  is A\u2022B (a 1:1 ratio), whereas that in (II) is A\u2022C\u2022A (a 2:1 ratio)  includes the additional solvate CS2 (D) mol\u00adecules. The mol\u00adecules of D participate in the construction of the supra\u00admolecular architecture of (II), resulting in infinite mixed stacks [A\u2022C\u2022A\u20221.5D]\u221e  and (II) is equal .It is inter\u00adesting to note that the crystal structures of  Fig.\u00a04. Beside \u221e Fig.\u00a04. RemarkaI) and (II) being structural analogs, they are substanti\u00adally different in their chemical stability. The crystalline complex (II) decomposes over a few days, while complex (I) is stable in the solid state for several months under ambient conditions. As free B decomposes rapidly upon reaction with moisture to produce toxic hydrogen cyanide, the high chemical stability of complex (I) is surprising. Moreover, the thermal stability of complex (I) has been studied by thermogravimetric analysis (TGA) which revealed that, upon complexation, tetra\u00adcyano\u00adethyl\u00adene is stable to higher temperatures , B is stable up to 393\u2005K. Complex (I) decomposes in two different steps. The first step of a 18.3% weight loss is attributed to molecule B because the much lower decomposition temperature of this molecule compared to macrocycle A. Consequently, the second weight loss of 81.7% is attributed to decomposition of macrocycle A. The complete decomposition of the free B is complete at 445\u2005K; however, its final decomposition temperature is equal to 467\u2005K within the supra\u00admolecular complex (I). Final decomposition of complex (I) occurs at 573\u2005K, and is likely due decomposition of macrocycle A.Despite complexes .Trimeric per\u00adfluoro-o-phenyl\u00adene mercury  and tetra\u00adcyano\u00adethyl\u00adene  were dissolved in di\u00adchloro\u00admethane in separate tubes using ultrasonication. The contents of the tubes were mixed carefully, and then left for slow evaporation of the solvents. Complex (I) was obtained as yellow prismatic crystals, m.p. = 499\u2013500\u2005K.Stoichiometric amounts of trimeric per\u00adfluoro-\u22123 near the Hg1 and Hg2 atoms due to considerable absorption effects which could not be completely corrected.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989015019350/ru2064sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019350/ru2064Isup2.hklStructure factors: contains datablock(s) I. DOI: 1430883CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(quinolin-6-yl)-2H-chromene-3-carboxamide coumarin derivative displays intra\u00admolecular N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds, which probably contribute to the approximate planarity of the mol\u00adecule [dihedral angle between the coumarin and quinoline ring systems = 6.08\u2005(6)\u00b0]. The supra\u00admolecular structures feature C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions, as confirmed by Hirshfeld surface analyses.The 6-methyl-2-oxo- 20H14N2O3, displays intra\u00admolecular N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds, which probably contribute to the approximate planarity of the mol\u00adecule [dihedral angle between the coumarin and quinoline ring systems = 6.08\u2005(6)\u00b0]. The supra\u00admolecular structures feature C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions, as confirmed by Hirshfeld surface analyses.The title coumarin derivative, C In fact, the mol\u00adecule is roughly planar, as may be evaluated by the set of values for the dihedral angles which are less than 7\u00b0 (Table\u00a02The C\u2014N rotamer of the amide group governs the conformation of the mol\u00adecule: the \u2212p Table\u00a01. Both th\u00b0 Table\u00a02.i hydrogen bond to form a C(8) chain, which runs parallel to the a axis , mol\u00adecules are linked by a weak C314\u2014H314\u22efO31is Fig.\u00a02. There aet al., 2008Crystal Explorer  plots  is built up by several \u03c0\u2013\u03c0 inter\u00adactions Table\u00a04. The redng Fig.\u00a04. The molis Fig.\u00a05. The molet al.  = 1.2Ueq(C), and methyl C\u2014H = 0.98\u2005\u00c5, with Uiso(H) = 1.5Ueq(C). The amino H atoms were freely refined. Crystal data, data collection and structure refinement details are summarized in Table\u00a05H atoms were treated as riding atoms, with aromatic C\u2014H = 0.95\u2005\u00c5, with 10.1107/S2056989016011026/hb7596sup1.cifCrystal structure: contains datablock(s) 1, general. DOI: 10.1107/S2056989016011026/hb7596Isup2.hklStructure factors: contains datablock(s) I. DOI: 1491340CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the silver atom is coordinated by two 1,3-bis\u00adimidazol-2-yl\u00adidene ligands, with the imidazole rings inclined to one another by 46.69\u2005(13)\u00b0. In the crystal, mol\u00adecules are linked by trifurcated C\u2014H\u22ef hydrogen bonds, forming two-dimensional networks parallel to (010). 27H36N2)2]Cl\u00b7C4H8O, the AgI atom is coordinated by two 1,3-bis\u00adimidazol-2-yl\u00adidene ligands. The imidazole rings are inclined to one another by 46.69\u2005(13)\u00b0 and the benzene rings in each ligand are almost normal to the imdazole ring to which they are attached, with dihedral angles varying from 82.39\u2005(13) to 88.27\u2005(12)\u00b0. There are C\u2014H\u22ef\u03c0 inter\u00adactions present in the cation, involving the two ligands, and the solvent mol\u00adecule is linked to the cation via a C\u2014H\u22efO hydrogen bond. In the crystal, mol\u00adecules are linked by trifurcated C\u2014H\u22ef hydrogen bonds, forming slabs parallel to (101). One isopropyl group is disordered over two sets of sites with an occupancy ratio of 0.447\u2005(17):0.553\u2005(17) and the THF mol\u00adecule is disordered over two positions with an occupancy ratio of 0.589\u2005(6):0.411\u2005(6).In the title salt, [Ag(C Herein, the crystal structure of one of the two products of this reaction, [Ag(NHC)2]Cl\u00b7THF, (I) Recently, we have shown that the penta\u00adphosphenide NaH-imidazol-2-ylidene)silver(I) cations, chloride anions and a THF solvent mol\u00adecule in a 1:1:1 ratio. The Ag atom is bonded to two C atoms with bond lengths Ag1\u2014C4 = 2.103\u2005(2) and Ag1\u2014C1 = 2.1058\u2005(19)\u2005\u00c5. The C1\u2014Ag1\u2014C4 bond angle is almost perfectly linear at 179.36\u2005(7)\u00b0. The dihedral angle between the two heterocycles is 46.70\u2005(11)\u00b0. The two 2,6-di-iso\u00adpropyl\u00adphenyl rings (C11\u2013C16 and C21\u2013C26) are inclined to the imdazole ring (N1/N2/C1\u2013C3) by 86.64\u2005(12) and 88.27\u2005(12)\u00b0, respectively. In the second ligand, the two 2,6-di-iso\u00adpropyl\u00adphenl rings (C31\u2013C36 and C41\u2013C46) are inclined to the imidazole ring (N3/N4/C4\u2013C6) by 82.39\u2005(13) and 83.41\u2005(13)\u00b0, respectively. There are also C\u2014H\u22ef\u03c0 inter\u00adactions present involving the two ligands ; Table\u00a01viz. bis\u00adsilver(I) tetra\u00adchlorido\u00adgallate(III) (Ia)   and 2.128 and 2.129\u2005\u00c5 in (Ib)]. However, while the dihedral angle between the two heterocycles is 46.70\u2005(11)\u00b0 in the title compound, it is significantly smaller in (Ia) (32.4\u00b0) and (Ib) (37.8\u00b0).The structures of the same cation but with different anions have been reported, viz. Ag1\u2014C1 = 2.1058\u2005(19) and Ag1\u2014C4 = 2.103\u2005(2)\u2005\u00c5.A database search 3] (0.1\u2005mmol) in 1\u2005mL THF was treated with a solution of [Ag(NHC)Cl]  2\u2005mL THF. The reaction mixture was stirred for 18\u2005h at room temperature. After overlaying the THF solution with cyclo\u00adhexane (6\u2005mL), colourless block-like crystals of the title compound were obtained after 10 days at room temperature (yield: 41%).A solution of NaUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. One isopropyl group (atoms C481/C482 and C483/C484) is disordered over two sets of sites with an occupancy ratio of 0.447\u2005(17):0.553\u2005(17) while the THF mol\u00adecule is disordered over two positions with an occupancy ratio of 0.589\u2005(6):0.411\u2005(6). Symmetry-equivalent bond lengths and angles in the two THF sites were restrained to be equal, distance C73\u2032\u22efC75\u2032 was restrained to 2.30\u2005(1)\u2005\u00c5, and the displacement parameters of the C atoms were restrained to an isotropic behaviour.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015007525/su5115sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015007525/su5115Isup2.hklStructure factors: contains datablock(s) I. DOI: 1060013CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One of the methyl groups and the 4-meth\u00adoxy\u00adphenyl substituent are in axial positions and the chloro\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)methyl substituent is in the equatorial position of the cyclo\u00adhexane ring which adopts a chair conformation. The packing features inversion-symmetric dimeric units and strands along [100] and [010] established by weak C\u2014H\u22efO and C\u2014H\u22efCl contacts. 23H25ClO4, the cyclo\u00adhexane ring adopts a chair conformation with the 4-meth\u00adoxy\u00adphenyl substituent in an axial position and the chloro\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)methyl substituent in an equatorial position. The packing features inversion dimers formed by pairs of C\u2014H\u22efO contacts and strands along [100] and [010] established by further C\u2014H\u22efO and C\u2014H\u22efCl contacts, respectively.In the title compound, C The crude product was recrystallized from diethyl ether/pentane (1:1 v/v) affording the title compound .Zinc chloride , tetra\u00adbutyl\u00adammonium chloride , diethyl ether (0.10\u2005ml) and phenyl\u00adiodo\u00adnium-4,4-di\u00admethyl\u00adcyclo\u00adhexane-2,6-dione  were dissolved in di\u00adchloro\u00admethane (6\u2005ml) and cooled to 195\u2005K. Then 4,4\u2032-di\u00admeth\u00adoxy\u00adbenzhydryl chloride  in di\u00adchloro\u00admethane (4\u2005ml) was added dropwise. The reaction solution was stirred at 195\u2005K for 2\u2005h. The resulting mixture was quenched with 2 2, 1.00\u2005\u00c5 for aliphatic C\u2014H, 0.95\u2005\u00c5 for aromatic H) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The methyl groups were allowed to rotate along the C\u2014C bonds to best fit the experimental electron density.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016002085/rz5184sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016002085/rz5184Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016002085/rz5184Isup3.cmlSupporting information file. DOI: 1451618CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the anions are linked  7H11N2+\u00b72C7H4NO4\u2212\u00b73H2O, crystallized with two anions and two cations in the asymmetric unit, together with three water mol\u00adecules. Both 4-di\u00admethyl\u00adamino\u00adpyridinium cations are protonated at their pyridine N atoms with the plane of the N(CH3)2 hetero atoms inclined to the pyridine ring by 4.5\u2005(2) and 1.4\u2005(2)\u00b0. In the 2-nitro\u00adbenzoate anions, the carboxyl and nitro groups are inclined to their respective benzene rings by 77.1\u2005(3) and 20.0\u2005(3)\u00b0, and 75.8\u2005(2) and 20.9\u2005(3)\u00b0. In the crystal, the anions are linked via O\u2014H\u22efO hydrogen bonds involving the water mol\u00adecules, forming chains along [100]. The cations are linked to these chains by N\u2014H\u22efO hydrogen bonds. The chains are linked via C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distances range from 3.617\u2005(1) to 3.851\u2005(1)\u2005\u00c5], forming a three-dimensional structure.The title salt, 2C In the 2-nitro\u00adbenzoate anions the carboxyl groups (O3/O4/C15 and O5/O6/C28) are inclined to the respective benzene rings (C16\u2013C21 and C22\u2013C27) by 77.1\u2005(3) and 75.8\u2005(2)\u00b0. The nitro groups (O1/O2/N5 and O7/O8/N6) are inclined to their respective benzene rings by 20.0\u2005(3) and 20.9\u2005(3)\u00b0.The asymmetric unit of the title salt consists of two 4-di\u00admethyl\u00adamino\u00adpyrdinium cations and two 2-nitro\u00adbenzoate anions, together with three water mol\u00adecules Fig.\u00a01. The geovia O\u2014H\u22efO hydrogen bonds involving the water mol\u00adecules, forming chains along [100]; Table\u00a01via C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions, forming a three-dimensional structure .In the crystal, the dihedral angle between the two pyridine rings (N1/C1\u2013C5 and N2/C8\u2013C12) is 5.16\u2005(9)\u00b0, while the benzene rings (C16\u2013C21 and C22\u2013C27) form a dihedral angle of 19.56\u2005(9)\u00b0. The anions are linked et al., 2000A search of the Cambridge Structural Database  and 2-nitro\u00adbenzoic acid  were dissolved in 50\u2005ml of hot ethanol as a solvent. The mixture was stirred well for 8\u2005h to give a homogeneous solution and is was then allowed to evaporate in air at room temperature. Within a few days, small colourless block-like crystals of the title salt were formed.Uiso(H) = 1.5Ueq(O) for the water H atoms. The C-bound H atoms were positioned geometrically and refined using a riding model: C\u2014H = 0.93\u20130.96\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814020583/su2777sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814020583/su2777Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814020583/su2777Isup3.cmlSupporting information file. DOI: 1024182CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-phenyl ring being inclined to the central p-phenyl\u00adenedi\u00adamine ring by 29.34\u2005(4) and 43.43\u2005(7)\u00b0, respectively. In the crystal, mol\u00adecules are linked by a number of weak N\u2014H\u22ef\u03c0, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distances = 3.5569\u2005(11)\u20133.708\u2005(1)\u2005\u00c5], forming slabs lying parallel to  and the terminal N-phenyl ring are 29.34\u2005(4) and 43.43\u2005(7)\u00b0, respectively. The conformation about the C=N bond is E. In the crystal, mol\u00adecules are linked by N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions forming chains propagating along the [10-2] direction. These chains are linked via \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distances are in the range 3.5569\u2005(11)\u20133.708\u2005(1)\u2005\u00c5], forming slabs lying parallel to (30-4).In the title compound, C Inter\u00adaction Cg6\u22efCg6ii is a slipped parallel \u03c0\u2013\u03c0 inter\u00adaction with an inter\u00adplanar distance of 3.3614\u2005(7)\u2005\u00c5 and a slippage of 1.163\u2005\u00c5.In the crystal, mol\u00adecules are connected N-phenyl-p-phenyl\u00adenedi\u00adamine gave three hits. Of these three compounds, N1-phenyl-N4-(quinolin-2-yl\u00admethyl\u00adene)benzene-1,4-di\u00adamine {synonym: N-phenyl-4-[(quinolin-2-yl\u00admethyl\u00adene)amino]aniline; WOJJIQ; Faizi et al., 2014A search of the Cambridge Structural Database  of pyrene-1-carbaldehyde in 5\u2005ml of absolute ethanol was added dropwise under stirring. The mixture was stirred for 10\u2005min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2h. The resulting yellow precipitate was recovered by filtration, washed several times with small portions of ice-cold ethanol and then with diethyl ether to give 150\u2005mg (87%) of the title compound. Yellow block-like crystals suitable for X-ray analysis were obtained within 3 days by slow evaporation of a solution in MeOH.80\u2005mg (0.435\u2005mmol) of Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015001814/su5072sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001814/su5072Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015001814/su5072Isup3.cmlSupporting information file. DOI: 1045835CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The thio\u00adphene and hy\u00addroxy-substitiuted rings form dihedral angles of 23.43\u2005(9) and 35.45\u2005(9)\u00b0, respectively, with the benzo\u00adthia\u00addiazole ring system. An intra\u00admolecular O\u2014H\u22efN hydrogen bond is observed. In the crystal, weak C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.880\u2005(3)\u2005\u00c5] link mol\u00adecules into chains along [100]. In addition, there are short S\u22efS contacts [3.532\u2005(3)\u2005\u00c5] which link these chains, forming a two-dimensional network parallel to (010).In the title mol\u00adecule, C DOI: 10.1107/S1600536814014883/lh5710Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814014883/lh5710Isup3.cmlSupporting information file. DOI: 1010080CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by weak intra- and inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains along the  50H46N2O4)], crystallizes in the triclinic space group P-1, with two mol\u00adecules in the asymmetric unit (Z\u2032 = 2). Each NiII atom has a slightly distorted square-planar geometry [\u03c9 = 3.91\u2005(5)\u00b0 and 2.04\u2005(7)\u00b0] defined by the two phenolate O and two imine N atoms of the tetra\u00addentate Schiff base ligand. The dihedral angles between the central phenolate ring and peripheral phenyl rings are 60.5\u2005(2)/70.0\u2005(2) and 86.4\u2005(2)/56.1\u2005(2)\u00b0 in mol\u00adecule A, and 89.43\u2005(19)/18.0\u2005(2) and 63.87\u2005(19)/68.2\u2005(2)\u00b0 in mol\u00adecule B. The two central phenolate rings are twisted by angles of 19.37\u2005(19) and 19.36\u2005(18)\u00b0 in the two mol\u00adecules. The packing is stabilized through intra- and inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains parallel to the b axis. The tert-butyl groups in one of the two mol\u00adecules are positionally disordered with a refined occupancy ratio of 0.707\u2005(13):0.293\u2005(13).The mononuclear title complex, [Ni(C The mol\u00adecular structure of one of the independent mol\u00adecules is shown in Fig.\u00a01II atom is coordinated by a tetra\u00addentate dianionic ligand involving two phenolato O and two imine N atoms. The coordination geometry around the metal atom is slightly distorted square planar [\u03b2 = 88.44\u2005(16) and 88.55\u2005(15)\u00b0  and \u03c9 = 3.8\u2005(4) and 2.2\u2005(4)\u00b0 (the angle between the coordination planes Ni1\u2013N1A\u2013O1A and Ni1\u2013N2A\u2013O2A in A and Ni2\u2013N1B\u2013O1B and Ni2\u2013N2B\u2013O2B in B) for Ni1 and Ni2, respectively  and 0.006\u2005(3)\u2005\u00c5, respectively. Atoms C25 and C26 in A and B are significantly out of plane, as indicated by the N\u2014C\u2014C\u2014N torsion angles, \u221232.9\u2005(7)\u00b0 in A and \u221240.5\u2005(3)\u00b0 in B. The dihedral angles between the central phenolato ring  and the peripheral phenyl rings  are 60.5\u2005(2) & 70.0\u2005(2)\u00b0 and 86.4\u2005(2) & 56.1\u2005(2)\u00b0 in mol\u00adecule A and 89.43\u2005(19) & 18.0\u2005(2)\u00b0 and 63.87\u2005(19) & 68.2\u2005(2)\u00b0 in mol\u00adecule B. The two central phenolato rings (C1A\u2013C6A & C34A\u2013C39A and C1B\u2013C6B & C34B\u2013C39B) are twisted by angles of 19.37\u2005(19) and 19.36\u2005(18)\u00b0, respectively, in the two mol\u00adecules.The mononuclear title complex crystallizes in the triclinic space group b axis by weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions  was added dropwise to the stirred hot solution of the tetra\u00addentate Schiff base, LH2  in ethanol under argon. The resulting wine-red solution was heated to reflux at 343\u2013353\u2005K. The clear solution thus obtained was filtered and allowed to cool to ambient temperature. Slow evaporation of the solvent resulted in red\u2013brown irregular plate-shaped crystals within a few days . Analysis calculated for C50H46N2O4Ni (%): C 75.29, H 5.81. Found: C 75.40, H 5.60.An ethano\u00adlic solution of NiClUiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. The refined occupancy ratios for the disordered t-butyl groups are 0.707\u2005(13):0.293\u2005(13) for atoms C8A/C9A/C10A and C8C/C9C/C10C in mol\u00adecule A. The ISOR restraint and EADP constraint commands in the SHELXL2014 software were used for the disordered atoms. There are voids in the structure of 348\u2005\u00c53 due to the packing of the mol\u00adecules but when these were checked using the SQUEEZE routine  I. DOI: 10.1107/S2056989015021052/zl2639Isup2.hklStructure factors: contains datablock(s) I. DOI: 1435344CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A. reticulata, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. The two mol\u00adecules differ essentially in the orientation of the propenyl group at the 2-position with respect to the mean plane of the furan\u00adocoumarin moiety. In the crystal, the two mol\u00adecules are linked via O\u2014H\u22efO hydrogen bonds forming zigzag \u2013A\u2013B\u2013A\u2013B\u2013 chains propagating along [001].The title furan\u00adocoumarin, isolated from the Indian herb  14H12O4 chromen-7-one], crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. The two mol\u00adecules differ essentially in the orientation of the propenyl group with respect to the mean plane of the furan\u00adocoumarin moiety; the O\u2014C(H)\u2014C=C torsion angle is 122.2\u2005(7)\u00b0 in mol\u00adecule A and \u221210.8\u2005(11)\u00b0 in mol\u00adecule B. In the crystal, the A and B mol\u00adecules are linked via O\u2014H\u22efO hydrogen bonds, forming zigzag \u2013A\u2013B\u2013A\u2013B\u2013 chains propagating along [001]. The chains are reinforced by bifurcated C\u2014H\u22ef hydrogen bonds, forming ribbons which are linked via C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.602\u2005(2)\u2005\u00c5], forming a three-dimensional structure.The title furan\u00adocoumarin, C A. reticulata, by column chromatography over silica gel with a mixture of binary solvent hexane and ethyl acetate by gradient elution. Furan\u00adocoumarins, such as oroselone chromen-2-one], whose atomic connectivity has been established by spectrometric and spectroscopic analyses  in the asymmetric unit. The compound is composed of three fused rings  with hydroxyl and propenyl substituents at positions 9 and 2, respectively. The furan\u00adocoumarin moieties are essentially planar with r.m.s. deviations of 0.05\u2005\u00c5 for mol\u00adecule A (O1/O2/C1\u2013C11) and 0.079\u2005\u00c5 for mol\u00adecule B (O5/O6/C16\u2013C25). The furan ring in mol\u00adecule A has an envelope conformation with atom C2 as the flap, deviating by 0.120\u2005(4)\u2005\u00c5 from the mean plane of the furan\u00adocoumarin moiety. In mol\u00adecule B, the furan ring has a twisted conformation on bond C17\u2013C16 with atoms C16 and C17 deviating by \u22120.232\u2005(6) and 0.076\u2005(6)\u2005\u00c5, respectively, from the other atoms of the twisted five-membered ring. The two mol\u00adecules differ essentially in the orientation of the propenyl group with respect to the mean plane of the furan\u00adocoumarin moiety, as shown by AutoMolFit analysis  \u00b0 in mol\u00adecule B. The bond distances and bond angles in the propenyl side chains  also differ in the two mol\u00adecules , the circular dichroism (CD) spectrum was measured in a solution of chloro\u00adform at concentration of 1\u2005mg/ml using a cell with path length 1\u2005cm. This CD measurement revealed that the absolute configuration of atom C2  is S.The absolute structure of the mol\u00adecule in the crystal could not be determined by resonant scattering. In order to determine the chirality at atom C2 \u2005\u00c5, inter\u00adplanar distance = 3.4168\u2005(2)\u2005\u00c5, slippage 1.284\u2005\u00c5, where Cg2 and Cg9 are the centroids of rings C1/C4\u2013C8 and C15/C18\u2013C22, respectively; symmetry code: (i) \u2212 x\u00a0+\u00a01, y\u00a0+\u00a0z].In the crystal, the viz. 2,3-di\u00adhydro-9-hy\u00addroxy-2-(1-hy\u00addroxy-1-methyl\u00adeth\u00adyl)-7H-furo(1) benzo\u00adpyran-7-one monohydrate  at room temperature by slow evaporation of the solvents (m.p. 498\u2005K). 1H NMR data  7.60 , 6.85 , 6.20 , 5.35 , 5.11 , 4.94 , 3.47\u20133.34 ,3.16\u20133.04 , 1.78 . EIMS (70 ev) data: m/z (%) 244(15.9) [M+], 226 (68.6) , 185\u2005(30),171 (16.8), 155 (30.1), 140 (16.4), 127 (13.5), 115 , 75 (22.3), 63 (26.5), 41 (16.0).The title compound was isolated as a colourless solid from the methanol extract of Uiso(H) = 1.2Ueq(O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C\u2014H = 0.93\u20130.98\u2005\u00c5 with Uiso(H) = 1.2Ueq(C). The limited number of Friedel pairs measured were merged for refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016003303/su5279sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016003303/su5279Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016003303/su5279Isup3.cmlSupporting information file. DOI: 1422810CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of tris\u00ad(di\u00admethyl\u00adamido)\u00adbis\u00ad(di\u00admethyl\u00adamine) zirconium(IV) iodide is reported. 2H6N)3(C2H7N)2]I. The bond lengths and bond angles are consistent with a slightly distorted trigonal\u2013bipyramidal coordination geometry around the metal atom. N\u22efI contacts of 3.6153\u2005(15) and 3.5922\u2005(14)\u2005\u00c5 are consistent with the presence of N\u2014H\u22efI inter\u00adactions. These N\u2014H\u22efI inter\u00adactions link the complex cations and iodide anions into extended chains that propagate parallel to the a axis.Zirconium amides have become increasingly popular and useful due to their widespread use as precursors to other zirconium complexes and their use in the production of solid oxide fuel cells (SOFCs). Herein we report the mol\u00adecular structure of tris\u00ad(di\u00admethyl\u00adamido)\u00adbis\u00ad(di\u00admethyl\u00adamine)\u00adzirconium(IV) iodide, [Zr(C Additionally, many zirconium amide complexes are precatalysts for hydro\u00adamination/cyclization of unactivated amino\u00adalkenes  and 3.5922\u2005(14)\u2005\u00c5 are consistent with the presence of N\u2014H\u22efI inter\u00adactions Table\u00a01. The \u2018twet al., 1988The synthesis or crystal structure of tris\u00ad(di\u00admethyl\u00adamido)\u00adbis(di\u00admethyl\u00adamine)\u00adzirconium(IV) iodide has not been reported as of 22 April 2015 based on a comprehensive WebCSD and Scifinder Scholar search. Similar compounds have been characterized crystallographically, for example tetra\u00adkis\u00ad(di\u00admethyl\u00adamido)\u00adzirconium(IV) and its lithium di\u00admethyl\u00adamido adduct phenyl\u00adene](di\u00admethyl\u00adamido)\u00addiiodidozirconium(IV) and 2-bis\u00ad(di\u00admethyl\u00adamido)iodidozirconium(IV) had crystallized in the form of needles, which were not suitable for single-crystal X-ray diffraction. However, a suitable tablet-shaped crystal of tris\u00ad(di\u00admethyl\u00adamido)\u00adbis\u00ad(di\u00admethyl\u00adammine)zirconium(IV) iodide was selected, mounted, and analyzed.1,3-Bis(3\u2032-hexyl\u00adimidazol-1\u2032-yl)benzene diiodide , tetra\u00adkis\u00ad(di\u00admethyl\u00adamido)\u00adzirconium(IV)  and dry toluene (2.8\u2005mL) were combined in an inert atmosphere of Ar and heated at 383\u2005K for 5\u2005min in a sealed screw-cap vial. While heating, the reaction mixture became homogeneous. Upon cooling to room temperature, an oil formed. The top layer was removed and the oil was washed with toluene (3 \u00d7 3\u2005mL). The toluene washings were combined and allowed to sit at room temperature. Colorless crystals formed after 2 months. The mother liquor was deca\u00adnted and the crystals were covered with paratone oil after using a few crystals for Uiso(H) = 1.5Ueq(C) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015023919/pk2563sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023919/pk2563Isup2.hklStructure factors: contains datablock(s) I. DOI: 1037746CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound compound, the phenyl and pyrimidine rings are inclined to one another at 31.72\u2005(6)\u00b0. The residues are associated into ribbons parallel to [110] by three classical hydrogen bonds. Adjacent ribbons are connected by translation parallel to the  12H10BrN5O3S2\u00b7C3H7NO, displays an almost planar amine group. The inter\u00adplanar angle between the rings is 31.72\u2005(6)\u00b0. The residues are associated into ribbons parallel to [110] by three classical hydrogen bonds; one from each amine Hamine to ODMF and one from NHamide to Ooxo. Adjacent ribbons are connected by translation parallel to the c axis by a \u2018weak\u2019 hydrogen bond Hmeth\u00adyl\u22efOsulfon\u00adyl to form a layer structure parallel to (1-10), while a further contact Hbromo\u00adphen\u00adyl\u22efOsulfon\u00adyl connects the residues in the third dimension.The title compound, C N-cyano\u00adimido-S,S-dimethyl-di\u00adthio\u00adcarbonate and other ketene di\u00adthio\u00adacetals for synthesizing new classes of anti\u00admetabolites -6-oxopyrimidin-1(6H)-yl)-4-bromo\u00adbenzene\u00adsulfonamide (I)N-cyano\u00addithio\u00adimino\u00adcarbonate with N\u2032-(4-bromo\u00adphen\u00adyl)sulfonyl-2-cyano\u00adethane\u00adhydrazide. The chemical nature was proposed on the basis of elemental analysis and spectroscopic data and its X-ray structure determination was undertaken to confirm the nature of the product. We have recently presented the structure of a related pyrimidine \u00b7DMF, is shown in Fig.\u00a01x, \u2212y, 1\u00a0\u2212\u00a0z) and H03\u22efO4, involve the di\u00admethyl\u00adformamide oxygen atom and lead to the formation of inversion-symmetric rings of graph set x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z), also forms inversion-symmetric rings, but of graph set The components are associated into ribbons parallel to [110] Fig.\u00a02 by threeB\u22efO3 connects neighbouring ribbons by translation parallel to the c axis, thus completing a layer structure parallel to .There are two short and acceptably linear C\u2014H\u22efO contacts that may be assumed to represent \u2018weak\u2019 hydrogen bonds; H7x, 2\u00a0\u2212\u00a0y,1\u00a0\u2212\u00a0z) and a weak hydrogen bond of 3.05\u2005\u00c5 from H17, with an angle of 124\u00b0 at hydrogen. These inter\u00adactions also connect the residues in the third dimension.The bromine atom is involved in two secondary contacts: a halogen bond of 3.4582\u2005(10)\u2005\u00c5 with O1 was added to a stirred solution of N\u2032-(4-bromo\u00adphen\u00adyl)sulfonyl-2-cyano\u00adethane\u00adhydrazide (0.01\u2005mol) in dry dioxane (50\u2005mL) containing potassium hydroxide (0.01\u2005mol) at room temperature. The reaction mixture was stirred for 30\u2005min at room temperature; the precipitated solid was collected by filtration and crystallized from dimethyl formamide to give pale yellow crystals, m.p. 483\u2013485\u2005K, yield 85%.Dimethyl Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015018903/lh5790sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015018903/lh5790Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015018903/lh5790Isup3.cmlSupporting information file. DOI: 1430044CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "O\u2014H\u22efO hydrogen bonds between water mol\u00adecules and ClO4 units lead to the formation of a three-dimensional network in each of the structures.The crystal structures of the tri-, tetra- and nona\u00adhydrate phases of Sr(ClO 4)2(H2O)3]n}, strontium perchlorate tetra\u00adhydrate {di-\u03bc-aqua-bis\u00ad(tri\u00adaqua\u00addiperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona\u00adhydrate {hepta\u00adaqua\u00addiperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]\u00b72H2O}, were crystallized at low temperatures according to the solid\u2013liquid phase diagram. The structures of the tri- and tetra\u00adhydrate consist of Sr2+ cations coordinated by five water mol\u00adecules and four O atoms of four perchlorate tetra\u00adhedra in a distorted tricapped trigonal\u2013prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol\u00adecules and thus forming chains parallel to [100]. In the tetra\u00adhydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol\u00adecules are formed. The structure of the nona\u00adhydrate contains one Sr2+ cation coordinated by seven water mol\u00adecules and by two O atoms of two perchlorate tetra\u00adhedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol\u00adecules, which are located on twofold rotation axes. O\u2014H\u22efO hydrogen bonds between the water mol\u00adecules as donor and ClO4 tetra\u00adhedra and water mol\u00adecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures.The title compounds, strontium perchlorate trihydrate {di-\u03bc-aqua-aquadi-\u03bc-perchlorato-strontium, [Sr(ClO Thereby, the trigonal base planes are chosen such that each oxygen atom of the perchlorate anions represents a capping atom. The third cap is provided by a water oxygen atom.The crystal structure of strontium perchlorate trihydrate contains two crystallographically distinct Srra Fig.\u00a01. Four of0] Fig.\u00a02. The cry0] Fig.\u00a02 or mercunt Fig.\u00a03b. There2+ cations 7] coordination polyhedra and two towards perchlorate tetra\u00adhedra 7] polyhedra additionally are linked via other O\u2014H\u22efO hydrogen bonds. The resulting arrangement can be seen in a larger section of the structure . O\u2014H\u22efO hydrogen bonds also dominate the crystal packing in the two other structures, in each case leading to the formation of a three-dimensional network 2\u00b73H2O phases, see: Gallucci & Gerkin (1988M = Ba); Hennings et al. (2014aM(ClO4)2\u00b74H2O phases, see: Robertson & Bish 2\u00b73H2O were used as purchased . The isolated crystals were stored in a freezer separated and embedded in perfluorinated ether to avoid contact with humidity. Sr(ClO4)2\u00b74H2O crystallized from an aqueous solution of 75.08 wt% Sr(ClO4)2 at 273\u2005K after two days and Sr(ClO4)2\u00b79H2O from an aqueous solution of 60.12 wt% Sr(ClO4)2 at 238\u2005K after one week. For preparing these aqueous solutions, strontium perchlorate trihydrate was used. The Sr2+ content was analyzed per complexometric titration with EDTA. The crystals are stable in the saturated aqueous solutions over a range of at least four weeks. The samples were stored in a freezer or a cryostat at low temperatures and were separated and embedded in perfluorinated ether for X-ray analysis.Crystals of Sr(ClO4)2\u00b73H2O and Sr(ClO4)2\u00b74H2O distance restraints were applied for all water mol\u00adecules, with O\u2014H and H\u2014H distance restraints of 0.84\u2005(1) and 1.4\u2005(1)\u2005\u00c5, respectively. For Sr(ClO4)2\u00b79H2O Uiso values were set at 1.2Ueq(O) using a riding model approximation. Distance restraints were applied for that structure for all water mol\u00adecules, with O\u2014H and H\u2014H distance restraints of 0.84\u2005(1) and 1.4\u2005(1)\u2005\u00c5, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S1600536814024726/wm5080sup1.cifCrystal structure: contains datablock(s) SrClO4_3H2O_100K, SrClO4_4H2O_150K, SrClO4_9H2O_100K. DOI: 10.1107/S1600536814024726/wm5080SrClO4_3H2O_100Ksup2.hklStructure factors: contains datablock(s) SrClO4_3H2O_100K. DOI: 10.1107/S1600536814024726/wm5080SrClO4_4H2O_150Ksup3.hklStructure factors: contains datablock(s) SrClO4_4H2O_150K. DOI: 10.1107/S1600536814024726/wm5080SrClO4_9H2O_100Ksup4.hklStructure factors: contains datablock(s) SrClO4_9H2O_100K. DOI: Click here for additional data file.10.1107/S1600536814024726/wm5080SrClO4_3H2O_100Ksup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814024726/wm5080SrClO4_4H2O_150Ksup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814024726/wm5080SrClO4_9H2O_100Ksup7.cmlSupporting information file. DOI: 1033590, 1033589, 1033588CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit comprises two independent mol\u00adecules. In the crystal, the two independent mol\u00adecules are linked by bifurcated N\u2014H\u22efO hydrogen bonds, forming a supra\u00admolecular chain with a  16H17N3O2S, there are two independent mol\u00adecules (A and B), which show an E conformation with respect to the C=N bond. An intra\u00admolecular O\u2014H\u22efN hydrogen bond with an S(6) motif stabilizes the mol\u00adecular structure. The terminal phenyl and benzene rings are almost orthogonal to each other, the dihedral angle being 87.47\u2005(13)\u00b0 for mol\u00adecule A and 89.86\u2005(17)\u00b0 for mol\u00adecule B. In the crystal, weak bifurcated N\u2014H\u22ef hydrogen bonds link the two independent mol\u00adecules, forming a supra\u00admolecular chain with a C21(14)[R21(5)] motif along the b axis. A weak C\u2014H\u22efO inter\u00adaction is also observed in the chain.In the asymmetric unit of the title compound, C The hydrazine carbo\u00adthio\u00adamide backbone is nearly planar with a maximum deviation of 0.023\u2005(2)\u2005\u00c5 at atom N2 for mol\u00adecule A and of 0.054\u2005(2)\u2005\u00c5 at atom N2\u2032 for B. The closeness of the C=S bond lengths [C9\u2014S1 = 1.666\u2005(2)\u2005\u00c5 and C9\u2032\u2014S1\u2032 = 1.657\u2005(2)\u2005\u00c5] to the expected distance  and longer than corresponding double bonds \u00b0 for B. In each mol\u00adecule (A and B), an intra\u00admolecular O\u2014H\u22efN inter\u00adaction (Table\u00a01S(6) ring motif stabilizes the mol\u00adecular structure  x, \u22121\u00a0+\u00a0y, z] with b axis. An inter\u00admolecular C\u2014H\u22efO inter\u00adaction is also observed within the chain -4-methyl-4-phenyl-1-(2-pyridyl\u00admethyl\u00adene)-3-thio\u00adsemicarbazide  indicate some degree of delocalization in the compounds. The C=S bond lengths in all compared compounds lie in the range 1.66\u20131.67\u2005\u00c5, inter\u00admediate between S\u2014Csp2 and S=Csp2 bond lengths , showing a partial double-bond character. Similar bond lengths for the C=S bond have also been observed in hydrazine carbo\u00adthio\u00adamide derivatives  of 2-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde in 10\u2005ml of ethanol over a period of 10\u2005min with continuous stirring. The reaction mixture was refluxed for 2\u2005h and allowed to cool whereby a shining yellow compound began to separate. This was filtered and washed thoroughly with ethanol and then dried in vacuum. The compound was recrystallized from a hot ethanol solution, giving colourless block-like crystals (yield 91%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of an ethanol solution at room temperature.1.81\u2005g (0.01\u2005mol) of Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl groups. The rotation angles for methyl groups were optimized.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016005326/is5446sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016005326/is5446Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016005326/is5446Isup3.cmlSupporting information file. DOI: 1435114CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation is located on a centre of inversion and exhibits a slightly distorted octa\u00adhedral arrangement of water mol\u00adecules. The noncoordinating water mol\u00adecules and di\u00admethyl\u00adammonium cations connect the sulfate and [Ni(H2O)6]2+ octa\u00adhedra via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds into a three-dimensional framework.In the salt bis\u00ad(di\u00admethyl\u00adammonium) hexa\u00adaqua\u00adnickelate(II) bis\u00ad(sulfate) dihydrate, the Ni 2H8N)2[Ni(H2O)6)](SO4)2\u00b72H2O, the NiII cation is located on a centre of inversion and exhibits a slightly distorted octa\u00adhedral arrangement of water mol\u00adecules. The Ni\u2014O bond lengths in the complex [Ni(H2O)6]2+ cation show a distribution as in the related Tutton salt (NH4)2[Ni(H2O)6](SO4)2, but are longer in average [2.056\u2005(13) versus 2.037\u2005(12)\u2005\u00c5]. The noncoordinating water mol\u00adecules and di\u00admethyl\u00adammonium cations connect the sulfate and [Ni(H2O)6]2+ octa\u00adhedra via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds from weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel (001).In the title salt, (C The NiII cation reaches an overall bond valence sum 6]2+ octa\u00adhedra. Together with relatively weaker N\u2014H\u22efO hydrogen bonds of the ammonium H atoms to sulfate anions, a three-dimensional framework is formed with pronounced formation of sheets of complex metal cations and sulfate anions parallel (001) (Table\u00a01Hydrogen bonds of weak up to medium strength involving coordinating and noncoordinating water mol\u00adecules as donor groups and O atoms of the sulfate anions as acceptor groups inter\u00adconnect neighbouring [Ni(H) Table\u00a01.\u22121) in a stoichiometric ratio of 1:2:1. The resulting solution was kept at room temperature by cooling. The title compound crystallized by slow evaporation of the solvent at room temperature in form of light-green crystals with dimensions up to 4\u2005mm within 12 weeks.The title compound was obtained by reaction of an aqueous solution of nickel(II) sulfate with di\u00admethyl\u00adamine and sulfuric acid (18\u2005mol\u2005lUiso(H) = 1.5Ueq(C) for methyl H atoms, and N\u2014H = 0.90\u2005\u00c5 and Uiso(H) = 1.2Ueq(N) for ammonium H atoms. The H atoms of water mol\u00adecules were refined with a distance restraint of O\u2014H = 0.98\u2005\u00c5 and individual Uiso values for each H atom.Details of structure refinement are given in Table\u00a0210.1107/S160053681402234X/wm5074sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681402234X/wm5074Isup2.hklStructure factors: contains datablock(s) I. DOI: 1028557CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are connected by N\u2014H\u22efO hydrogen bonds generating \u2013A\u2013B\u2013A\u2013B\u2013 zigzag chains extending along [010]. The chains are linked via C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions [with a centroid\u2013centroid distance of 3.444\u2005(3)\u2005\u00c5)] between the benzene ring and the imino group of symmetry-related mol\u00adecules, forming slabs lying parallel to (100).The title compound, C 23H25N3O, crystallized with one single mol\u00adecule in the asymmetric unit and is present in the zwitterionic form. There is an intra\u00admolecular N\u2014H\u22efO hydrogen bond in the mol\u00adecule with the phenol ring being inclined to the central benzene ring by 20.67\u2005(14)\u00b0. The terminal amino\u00adphenyl ring forms a dihedral angle of 54.21\u2005(14)\u00b0 with the central benzene ring. The two outer aromatic rings are inclined to one another by 74.54\u2005(14)\u00b0. In the crystal, the mol\u00adecules are connected by N\u2014H\u22efO hydrogen bonds, with adjacent molecules related by a 21 screw axis, generating \u2013A\u2013B\u2013A\u2013B\u2013 zigzag chains extending along [010]. The chains are linked via C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [with a centroid\u2013centroid distance of 3.444\u2005(3)\u2005\u00c5] between the benzene ring and the imino group of symmetry-related mol\u00adecules, forming slabs lying parallel to (100).The title compound, C It is well known that Schiff bases of salicyl\u00adaldehyde derivative may exhibit thermochromism or photochromism, depending on the planarity or non-planarity of the mol\u00adecule, respectively  with respect to the central benzene ring (C12\u2013C17); the dihedral angle between them is 54.21\u2005(14)\u00b0. The two outer aromatic rings (C18\u2013C23 and C1\u2013C6) are inclined to one another by 74.54\u2005(14)\u00b0. The C\u2014N, C=N and C\u2014C bond lengths are normal and close to the values observed in related structures ; see Table\u00a01Cg1\u22efCg2i = 3.444\u2005(3)\u2005\u00c5, where Cg1 and Cg2 are the centroids of atoms C1\u2013C6 and the midpoint of atoms N2/C11, respectively -N\u2032-phenyl\u00adbenzene-1,4-di\u00adamine  of 4-di\u00adethyl\u00adamino-2-hy\u00addroxy\u00adbenzaldehyde in 5\u2005ml of absolute ethanol was dropwisely added under stirring. This mixture was stirred for 10\u2005min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2\u2005h. The resulting yellow precipitate was recovered by filtration, washed several times with a small portions of EtOH and then with diethyl ether to give 150\u2005mg (88%) of 5-di\u00adethyl\u00adamino-2-[(E)-{[4-(phenyl\u00adamino)\u00adphen\u00adyl]imino\u00admeth\u00adyl}phenol] (DPIM). Crystals of the title compound suitable for X-ray analysis were obtained within three days by slow evaporation of the DMF solvent.100\u2005mg (1\u2005mmol) of Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015019490/lh5793sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019490/lh5793Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015019490/lh5793Isup3.cmlSupporting information file. DOI: 1431311CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Three closely related methyl\u00adated hydrazine carbamates show different hydrogen-bonding patterns, although they all result in chains. l-serine are presented, namely benzyl N-{(E)-1-[2-(4-cyanobenzylidene)-1-methylhydrazinyl]-3-hydroxy-1-oxopro\u00adpan-2-yl}carbamate, C20H20N4O4, tert-butyl N-{(E)-1-[2-(4-cyanobenzylidene)-1-methylhydrazinyl]-3-hydroxy-1-oxopropan-2-yl}carbamate, C17H22N4O4, and tert-butyl N-[(E)-1-(2-benzylidene-1-methylhydrazinyl)-3-hydroxy-1-oxopro\u00adpan-2-yl]carbamate, C16H23N3O4. One of them shows that an unexpected racemization has occurred during the mild-condition methyl\u00adation reaction. In each crystal structure, the mol\u00adecules are linked into chains by O\u2014H\u22efO hydrogen bonds, but with significant differences between them.The crystal structures of three methyl\u00adated hydrazine carbamate derivatives prepared by multi-step syntheses from  The C9\u2014N2 bond length of 1.358\u2005(6)\u00c5 is typical of an amide and the N1\u2014N2 bond length of 1.374\u2005(5) is shorter than the reference value of 1.40\u2005\u00c5 for a nominal N(sp2)\u2014N(sp2) single bond. This suggests at least some electronic conjugation over the almost planar C7/N1/N2/C9/O1 grouping (r.m.s. deviation = 0.010\u2005\u00c5): the C1 benzene ring is twisted by 6.1\u2005(2)\u00b0 with respect to these atoms. The C7\u2014N1\u2014N2\u2014C8 torsion angle of \u22121.9\u2005(6)\u00b0 shows that the carbon atoms are almost eclipsed with respect to the N\u2014N bond whereas the C9\u2014C10\u2014C11\u2014O2 torsion angle of \u221250.9\u2005(5)\u00b0 indicates a gauche conformation about the C10\u2014C11 bond. The C9\u2014C10\u2014N3\u2014H3A torsion angle is 38\u00b0 and the separation between H2A (bonded to O2) and H3A is 2.5\u2005\u00c5.The mol\u00adecular structure of (I)S) was assumed to be the same as that of the corresponding atom in the l-serine starting material. In terms of the C7/N1/N2/C9/O1 grouping in (II)A and H3 is 2.7\u2005\u00c5. These values are evidently sufficiently different from the corresponding data for (I)The mol\u00adecular structure of (II)S configuration. The O2\u2014H2 hy\u00addroxy group is disordered over two orientations in a 0.802\u2005(7):0.198\u2005(7) ratio. The geometric parameters for (III)A (major disorder component) torsion angle is \u221254.9\u2005(4)\u00b0. The C9\u2014C10\u2014C11\u2014O2B torsion angle for the minor disorder component is \u2212156.7\u2005(8)\u00b0, which has a significant role to play in the hydrogen-bonding pattern in the crystal of (III)Compound (III)A\u22efO4i  and much longer N3\u2014H3A\u22efO4i hydrogen bonds (Table\u00a01C(7) O\u2014H\u22efO and C(4) N\u2014H\u22efO chains. A pair of weak C\u2014H\u22ef\u03c0 inter\u00adactions are also observed but there is no aromatic \u03c0\u2013\u03c0 stacking (shortest centroid\u2013centroid separation > 4.7\u2005\u00c5).In the extended structure of (I)s Table\u00a01 to the sC(7) O2\u2014H2A\u22efO4i  hydrogen bonds (Table\u00a02i to not form an inter\u00admolecular hydrogen bond (H3\u22efO4i = 3.2\u2005\u00c5), but instead forms an intra\u00admolecular link to O1. A very long inter\u00admolecular C\u2014H\u22efN inter\u00adaction is observed but there is no \u03c0\u2013\u03c0 stacking in (II)The extended structure of (II)s Table\u00a02 with alm1 screw axis, so that the C1-benzene ring is \u2018flipped\u2019 from one side of the chain to the other in adjacent mol\u00adecules. As noted above, the hydroxyl group is disordered over two orientations. The hydrogen bond from the major orientation of O2A\u2014H2A is still a bond to O4i  forms an O\u2014H\u22efO hydrogen bond in the opposite chain direction to O1ii : O1 also accepts an intra\u00admolecular N\u2014H\u22efO hydrogen bond, as seen in (II)The packing in the centrosymmetric structure of (III)i Table\u00a03, where i2OH)CON(CH3)N=CH\u2013 fragments reported in Version 5.36 of the Cambridge Structural Database CONHN=CH\u2013 groupings with different substituents at each end of the fragment, all of which have been reported by us in the last few years -(S)-ROCONHCH(CH2OH)CONHN=CH-benzene compound  was added to a solution of the appropriate , b = 13.003\u2005(19), c = 22.94\u2005(3)\u2005\u00c5, \u03b1 = 92.93\u2005(2), \u03b2 = 91.48\u2005(3), \u03b3 = 98.13\u2005(3)\u00b0, V = 2804\u2005(7)\u2005\u00c53]. An atomic model could be developed in space group P1 with Z = 6, but a PLATON ]. The C-bound H atoms were placed geometrically (C\u2014H = 0.95\u20131.00\u2005\u00c5) and refined as riding atoms. The constraint Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied in all cases. The H atoms of the hydroxyl groups were allowed to rotate about their C\u2014O bond (SHELXL HFIX 83 instruction with O\u2014H = 0.84\u2005\u00c5 and C\u2014O\u2014H = 109.5\u00b0) to best fit the electron density. The methyl groups were allowed to rotate, but not to tip, to best fit the electron density (AFIX 137 instruction).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989015010440/hg5443sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989015010440/hg5443Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010440/hg5443IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015010440/hg5443IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989015010440/hg5443Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015010440/hg5443IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015010440/hg5443IIIsup7.cmlSupporting information file. DOI: 1404006, 1404005, 1404004CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These represent the chiral atropoisomers distinguished by the mutual arrangement of the two acet\u00adyl\u2013hydrazone groups with a cis conformation of the C=N bonds. The two cyclo\u00adpenta\u00addienyl (Cp) rings are planar and nearly parallel, the tilt between the two rings being 3.16\u2005(16)\u00b0 [4.40\u2005(18)\u00b0 for the second independent mol\u00adecule]. The conformation of the Cp rings is close to eclipsed, the twist angle being 0.1\u2005(2)\u00b0 [3.3\u2005(2)\u00b0]. The two acet\u00adyl\u2013hydrazone substituents are also planar and are inclined at 13.99\u2005(15)/9.17\u2005(16)\u00b0 [6.83\u2005(17)/14.59\u2005(15)\u00b0] relative to the Cp rings. The Fe\u2014C bond lengths range from 2.035\u2005(3) to 2.065\u2005(2)\u2005\u00c5, with an average of 2.050\u2005(3)\u2005\u00c5 , which agrees well with those reported for most ferrocene derivatives. In the crystal, the mol\u00adecules form dimers via two strong N\u2014H\u22efN hydrogen bonds. The dimers are linked into a three-dimensional framework by weak N\u2014H\u22efN hydrogen bonds.The title compound, [Fe(C DOI: 10.1107/S1600536814014366/rk2429Isup2.hklStructure factors: contains datablock(s) I. DOI: 1009066CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The CoII atoms are linked by the oxalate anions into a chain running parallel to [100]. The chains are linked by the BPMO ligands into a three-dimensional architecture. In addition, N\u2014H\u22efO hydrogen bonds stabilize the crystal packing.In the polymeric title compound, [Co(C DOI: 10.1107/S1600536814015608/bt6986Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814015608/bt6986fig1.tifx y z x y z x y z x y z . DOI: x\u00a0+\u00a01, \u2212y, \u2212 z\u00a0+\u00a01; (ii) \u2212x, \u2212y, \u2212 z\u00a0+\u00a01; (iii) x, \u2212 y\u00a0+\u00a0z\u00a0+\u00a0x\u00a0+\u00a01, \u2212 y\u00a0+\u00a0z\u00a0\u2212\u00a0A view of the mol\u00adecule of (I). Displacement ellipsoids are drawn at the 30% probability level. (i) \u2212 Click here for additional data file.10.1107/S1600536814015608/bt6986fig2.tif. DOI: View of the three-dimensional structure of (I).1012047CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cations that are linked by thio\u00adcyanato anions into chains which are further connected into layers by inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efS hydrogen bonding via additional methanol mol\u00adecules.The crystal structure of the title compound consists of Cd 2(C6H6N2S)]\u00b72CH3OH}n, consists of one cadmium(II) cation that is located on a centre of inversion as well as one thio\u00adcyanate anion, one pyridine-4-carbo\u00adthio\u00adamide ligand and one methanol mol\u00adecule in general positions. The CdII cations are octa\u00adhedrally coordinated by the pyridine N atom of two pyridine-4-carbo\u00adthio\u00adamide ligands and by the S and N atoms of four thio\u00adcyanate anions and are linked into chains along [010] by pairs of anionic ligands. These chains are further linked into layers extending along (201) by inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds. One of the amino H atoms of the pyridine-4-carbo\u00adthio\u00adamide ligand is hydrogen-bonded to the O atom of a methanol mol\u00adecule, and a symmetry-related methanol mol\u00adecule is the donor group to the S atom of another pyridine-4-carbo\u00adthio\u00adamide ligand whereby each of the pyridine-4-carbo\u00adthio\u00adamide ligands forms two pairs of centrosymmetric N\u2014H\u22efS and O\u2014H\u22efS hydrogen bonds. The methanol mol\u00adecules are equally disordered over two orientations.The asymmetric unit of the polymeric title compound, {[Cd(NCS) The CdII cation is sixfold coordinated by two N-bonding pyridine\u00adthio\u00adamide ligands as well as two N- and two S-coordinating thio\u00adcyanate anions in an all trans distorted octa\u00adhedral environment nt Fig.\u00a01. As expent Fig.\u00a01. The CdI0] Fig.\u00a02. The metvia the methanol solvent mol\u00adecules  by inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efS hydrogen bonding es Fig.\u00a03. Each pyes Fig.\u00a03. The hydes Fig.\u00a03. This aret al., 2014According to the Cambridge Structural Database 2\u00b73H2O were purchased from Alfa Aesar. Cd(NCS)2 was synthesized by stirring 17.5\u2005g (57.0\u2005mmol) Ba(NCS)2\u00b73H2O and 14.6\u2005g (57.0\u2005mmol) CdSO4\u00b73/8H2O in 300\u2005ml water at room temperature for 3\u2005h. The white residue of BaSO4 was filtered off and the resulting solution dried at 353\u2005K. The homogeneity of the product was checked by X-ray powder diffraction and elemental analysis. The title compound was obtained by reaction of 11.4\u2005mg Cd(NCS)2 (0.05\u2005mmol) with 27.6\u2005mg pyridine-4-carbo\u00adthio\u00adamide (0.2\u2005mmol) in boiling methanol (2\u2005ml). Crystals suitable for single-crystal x-ray diffraction formed after cooling.CdSOUiso(H) = 1.2Ueq (1.5 for methyl and O\u2014H hydrogen atoms) using a riding model with C\u2014H = 0.95\u2005\u00c5 for aromatic, C\u2014H = 0.98\u2005\u00c5 for methyl, N\u2014H = 0.88\u2005\u00c5 and O\u2014H = 0.84\u2005\u00c5, respectively. The methanol mol\u00adecule is equally disordered over two orientations and was refined using a split model using SAME restraints  I, New_Global_Publ_Block. DOI: 10.1107/S2056989016002632/wm5271Isup2.hklStructure factors: contains datablock(s) I. DOI: 1453442CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S-benzyl-\u03b2-N-(2-hy\u00addroxy\u00adphenyl\u00adethyl\u00adidene)di\u00adthio\u00adcarbazate groups, connected through an S\u2014S single bond. The two moieties are twisted with a dihedral angle of 87.88\u2005(4)\u00b0 between the S2C=N planes.The title mol\u00adecule consists of two Schiff base moieties, namely two  32H30N4O2S4, consists of two Schiff base moieties, namely two S-benzyl-\u03b2-N-(2-hy\u00addroxy\u00adphenyl\u00adethyl\u00adidene)di\u00adthio\u00adcarbazate groups, which are connected through an S\u2014S single bond. These two moieties are twisted with respect to each other, with a dihedral angle of 87.88\u2005(4)\u00b0 between the S2C=N planes. A bifurcated intra\u00admolecular O\u2014H\u22ef hydrogen bond is observed in each moiety. In the crystal, mol\u00adecules are linked by pairs of C\u2014H\u22efO hydrogen bonds into inversion dimers. The dimers are further stacked in a column along the b axis through weak C\u2014H\u22ef\u03c0 inter\u00adactions.The title compound, C S-benzyl\u00addithio\u00adcarbazate (SBDTC) . The (imino\u00adeth\u00adyl)phenol fragments (C1\u2013C8/O1/N1 and C25\u2013C32/O2/N4) are essentially planar with maximum deviations of 0.0559\u2005(12)\u2005\u00c5 for N1 and 0.0200\u2005(11)\u2005\u00c5 for N4 and make dihedral angles of 18.17\u2005(4) and 17.49\u2005(4)\u00b0 with the N2/S1/S2/C9 and N3/S3/S4/C17 planes, respectively. The C\u2014S distances  of 1.7461\u2005(12)\u20131.8220\u2005(13)\u2005\u00c5 are comparable to the values for the most similar di\u00adthio\u00adcarbazate derivatives di\u00adthio\u00adcarbazate was prepared by Pramanik et al. , was prepared according to the literature method . The prepared compound (0.17\u2005g) was dissolved in aceto\u00adnitrile (20\u2005ml) on warming and mixed with ethanol (10\u2005ml). Light-yellow platelet single crystals of the title compound (m.p. 386\u2013387\u2005K) suitable for X-ray study were obtained after 17 days along with colorless needle-shaped crystalline solids (m.p. 413\u2013418\u2005K).The ligand precursor, Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016002371/is5440sup1.cifCrystal structure: contains datablock(s) General, I. DOI: 10.1107/S2056989016002371/is5440Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016002371/is5440Isup3.cmlSupporting information file. DOI: 1452193CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R stereochemical configuration. No head-to-tail hydrogen bonding is observed in the crystal packing, as is the case in estrone and other derivatives.A new ferrocene complex, 16-ferrocenylmethyl-3\u03b2-hy\u00addroxy\u00adestra-1,3,5(10)-trien-17-one, has been synthesized and structurally characterized by single-crystal X-ray diffraction techniques. The ferrocenylmethyl group is positioned at the \u03b2 face of the estrone moiety; as a result, a new stereogenic center is formed leading to an  5H5)(C24H27O2)]\u00b7C2H6OS, has been synthesized and structurally characterized by single-crystal X-ray diffraction techniques. The mol\u00adecule crystallizes in the space group P21 with one mol\u00adecule of dimethyl sulfoxide. A hydrogen bond links the phenol group and the dimethyl sulfoxide O atom, with an O\u22efO distance of 2.655\u2005(5)\u2005\u00c5. The ferrocene group is positioned in the \u03b2 face of the estrone moiety, with an O\u2014C\u2014C\u2014C torsion angle of 44.1\u2005(5)\u00b0, and the carbonyl bond length of the hormone moiety is 1.216\u2005(5)\u2005\u00c5, typical of a C=O double bond. The average Fe\u2014C bond length of the substituted Cp ring [Fe\u2014C(Cp*)] is similar to that of the unsubstituted one [Fe\u2014C(Cp)], i.e. 2.048\u2005(3) versus 2.040\u2005(12)\u2005\u00c5. The structure of the complex is compared with those of estrone and eth\u00adoxy\u00admethyl\u00adestrone.A new ferrocene complex, 16-ferrocenylmethyl-3\u03b2-hy\u00addroxy\u00adestra-1,3,5(10)-trien-17-one dimethyl sulfoxide monosolvate, [Fe(C In this context, we present herein the synthesis and crystal structure of 16-ferrocenylmethyl-3\u03b2-hy\u00addroxy\u00adestra-1,3,5(10)-trien-17-one dimethyl sulfoxide monosolvate (2) and compare it with the structure of estrogen (1) and 16\u03b2-eth\u00adoxy\u00admethyl\u00adestrone (3) \u2005\u00c5, which is very similar to in estrogen and 16\u03b2-eth\u00adoxy\u00admethyl\u00adestrone , corresponding to a carbon\u2013oxygen double (C=O) bond. However, the substitution at C16 of the steroid in 2 and 3, ferrocenylmethyl and eth\u00adoxy\u00admethyl groups, respectively, makes torsion angles and bond angles at the 16-position slightly different. Both substituents are located on the beta face but, the torsion angle (between C19 and carbonyl group) defined as C19\u2013C16\u2014C17\u2014O2 in 2 is smaller than in 3 (between the carbonyl and the meth\u00adoxy groups), 44.1\u2005(5) and 49.7\u2005(2)\u00b0, respectively. The ferrocene moiety is positioned at 112.6\u2005(3)\u00b0 from C16 (\u2220C20\u2014C19\u2014C16) while the eth\u00adoxy\u00admethyl group is at 108.4\u2005(1)\u00b0 (\u2220C16\u2014C1\u2014O3). The average Fe\u2014C bond length of the substituted Cp ring [Fe\u2014C vs 2.040\u2005(12)\u2005\u00c5  as mobile phase, affording 67% of 2 as a yellow solid. Yellow rod-shaped crystals were obtained after dissolving the solid 16-ferro\u00adcenyl\u00admethyl-3\u03b2-hy\u00addroxy\u00adestra-1,3,5(10)-trien-17-one in a solution of CH2Cl2 with a few drops of dimethyl sulfoxide, to assure a concentrate solution, layered in hexane.In a 500\u2005mL Parr bottle, 16-ferrocenyl\u00adidene-3\u03b2-hy\u00addroxy\u00adestra-1,3,5(10)-trien-17-one complex was dissolved in a mixture of tetra\u00adhydro\u00adfuran (THF) and ethanol (1:1) and Pd/C . The system was purged three times with Hd(C\u2014H) = 0.95\u2005\u00c5, Uiso(H) = 1.2Ueq(C); d(C\u2014H2) = 0.99\u2005\u00c5,Uiso(H) = 1.2 Ueq (C); d(C\u2014H3) = 0.98\u2005\u00c5, Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016008446/bg2586sup1.cifCrystal structure: contains datablock(s) I. DOI: 1479699CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 5-fluoro\u00adcytosine and melamine mol\u00adecules inter\u00adact via N\u2014H\u22efO, N\u2014H\u22efN and N\u2014H\u22efO, N\u2014H\u22efN, C\u2014H\u22efF hydrogen bonds.The asymmetric unit of the title compound comprises two independent 5-fluoro\u00adcytosine mol\u00adecules and one half-mol\u00adecule of melamine. The 5-fluoro\u00adcytosine mol\u00adecules are linked through two different homosynthons; one is formed  4H4FN3O\u00b7C3H6N6, comprises of two independent 5-fluoro\u00adcytosine (5FC) mol\u00adecules (A and B) and one half-mol\u00adecule of melamine (M). The other half of the melamine mol\u00adecule is generated by a twofold axis. 5FC mol\u00adecules A and B are linked through two different homosynthons [R22(8) ring motif]; one is formed via a pair of N\u2014H\u22efO hydrogen bonds and the second via a pair of N\u2014H\u22efN hydrogen bonds. In addition to this pairing, the O atoms of 5FC mol\u00adecules A and B inter\u00adact with the N2 amino group on both sides of the melamine mol\u00adecule, forming a DDAA array of quadruple hydrogen bonds and generating a supra\u00admolecular pattern. The 5FC (mol\u00adecules A and B) and two melamine mol\u00adecules inter\u00adact via N\u2014H\u22efO, N\u2014H\u22efN and N\u2014H\u22efO, N\u2014H\u22efN, C\u2014H\u22efF hydrogen bonds forming R66(24) and R44(15) ring motifs. The crystal structure is further strengthened by C\u2014H\u22efF, C\u2014F\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions.The asymmetric unit of the title compound, 4C The twofold axis of melamine coincides with the crystallographic twofold axis. An ORTEP view of the crystal structure is shown in Fig.\u00a01A and 1.3492\u2005(18)\u2005\u00c5 in 5FC B and the corresponding internal angles at the carbon-carrying fluorine atom [C2A\u2014N3A\u2014C4A = 119.96\u2005(13) in 5FC A and C2B\u2014N3B\u2014C4B = 119.92\u2005(13)\u00b0 in 5FC B] agree with those reported in the literature  mol\u00adecules  are involved in the generation of a quadruple hydrogen-bonded DDAA array having a fused-ring sequence of via N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds. These quadruple arrays are further linked by three large ring motifs: A mol\u00adecules, two 5FC B mol\u00adecules and two melamine mol\u00adecules through several N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, generating a hexa\u00admeric supermolecule. The A mol\u00adecule, two 5FC B mol\u00adecules and one melamine mol\u00adecule through N\u2014H\u22efO, N\u2014H\u22efN and C\u2014H\u22efF hydrogen bonds, generating a tetra\u00admeric supermolecule. Similarly, the A mol\u00adecules, one 5FC B mol\u00adecule and one melamine mol\u00adecule through N\u2014H\u22efO, N\u2014H\u22efN and C\u2014H\u22efF hydrogen bonds, generating another tetra\u00admeric supermolecule. The association of these DDAA array and A and B mol\u00adecules with an inter\u00adplanar distance of 3.475\u2005(6)\u2005\u00c5, centroid-to-centroid distance of 3.6875\u2005(11)\u2005\u00c5, and slip angle of 19.52\u00b0. The crystal structure is further strengthened by a C\u2014F\u22ef\u03c0 inter\u00adaction [3.4541\u2005(14)\u2005\u00c5] between 5-fluoro\u00adcytosinium mol\u00adecule A and the melamine mol\u00adecule  while the melamine mol\u00adecule inter\u00adacts with them via N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, generating the supra\u00admolecular architecture.In this co-crystal, 5FC mol\u00adecules et al., 1982et al., 2009et al., 2013abet al., 2012et al., 2013et al., 2001et al., 2014abet al., 2005et al., 2007The crystal structure of 5-fluoro\u00adcytosine monohydrate (Louis Hot aqueous solutions of 5-fluoro\u00adcytosine (32\u2005mg) and melamine (31\u2005mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed to 353\u2005K using a water bath for half an hour and kept at room temperature for crystallization. After one week, colourless crystals were obtained.A, N4B) groups were located in a difference Fourier map and refined freely. The other hydrogen atoms were positioned geometrically  and were refined using a riding model with Uiso(H) = 1.2Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901600476X/hg5470sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901600476X/hg5470Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600476X/hg5470Isup3.cmlSupporting information file. DOI: 1469709CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit is completed by one-half of the 2-({4-[(carboxyl\u00adatometh\u00adyl)carbamo\u00adyl]phen\u00adyl}formamido)\u00adacetate dianion, which is located on a centre of inversion, and by three water mol\u00adecules. Two [Co(CO3)(C10H8N2)2]+ cations are connected through C\u2014H\u22efO contacts by the uncoordinating anions. The aromatic rings of the 2,2\u2032-bi\u00adpyridine ligands and di\u00adacetate anions are involved in \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions. The centroid\u2013centroid distances are in the range 3.4898\u2005(4)\u20133.6384\u2005(5)\u2005\u00c5. The crystal structure is stabilized by further O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, which give rise to a three-dimensional supra\u00admolecular network.The complex cation of the title compound, [Co(CO DOI: 10.1107/S160053681400631X/wm5010Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S160053681400631X/wm5010Isup3.cdxSupporting information file. DOI: 992984CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Its geometry is different from saturated peptides but is in excellent agreement with other de\u00adhydro\u00adalanine compounds. In the crystal, an N\u2014H\u22efO hydrogen bond links the mol\u00adecules in a herringbone packing arrangement.In the crystal structure of the de\u00adhydro\u00addipeptide (Boc-Phe-\u0394Ala-OiPr), the mol\u00adecule has a  20H28N2O5), the mol\u00adecule has a trans conformation of the N-methyl\u00adamide group. The geometry of the de\u00adhydro\u00adalanine moiety is to some extent different from those usually found in simple peptides, indicating conjugation between the H2C=C group and the peptide bond. The bond angles around de\u00adhydro\u00adalanine have unusually high values due to the steric hindrance, the same inter\u00adaction influencing the slight distortion from planarity of the de\u00adhydro\u00adalanine. The mol\u00adecule is stabilized by intra\u00admolecular inter\u00adactions between the isopropyl group and the N atoms of the peptide main chain. In the crystal, an N\u2014H\u22efO hydrogen bond links the mol\u00adecules into ribbons, giving a herringbone head-to-head packing arrangement extending along the [100] direction. In the stacks, the mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen-bonding associations.In the title compound, the de\u00adhydro\u00addipeptide (Boc\u2013Phe\u2013\u0394Ala\u2013OiPr, C The unsaturated amino acid is introduced into the structure of these polycyclic peptides by post-translational modification of selected serine and threonine residues -phenyl\u00adalanylde\u00adhydro\u00adalanine isopropyl ester and its structure determination by single-crystal X-ray crystallographic methods are presented.De\u00adhydro\u00adpeptides are a class of compounds containing at least one residue of an \u03b1,\u03b2-de\u00adhydro\u00adamino acid. These compounds are of inter\u00adest in many fields of science because of their structural and chemical properties. De\u00adhydro\u00adamino acids are found in natural products (Bonauer N-(tert-but\u00adoxy\u00adcarbon\u00adyl)phenyl\u00adalanylde\u00adhydro\u00adalanine isopropyl ester  is shown in Fig.\u00a01trans-conformation of the N-methyl\u00adamide group. The geometry of the de\u00adhydro\u00adalanine is to some extent different from those usually found in simple peptides glycine , C17\u2014N19\u2014C20 = 126.8\u2005(2) and O18\u2014C17\u2014N19 = 123.5\u2005(2)\u00b0] due to the steric hindrance between atoms C21 and O18. The same inter\u00adaction influences the slight distortion from planarity of the de\u00adhydro\u00adalanine moiety. The \u03c9, \u03d5 and \u03c8 torsion angles  of the de\u00adhydro\u00adalanine residue are \u2212166.9\u2005(2), 175.1\u2005(2) and 178.0\u2005(2)\u00b0. The geom\u00adetries of the phenyl\u00adaniline and the protecting groups are normal. There are four intra\u00admolecular C\u2014H\u22efO close contacts but three of them have a D\u2014H\u22efA angle of less than 120\u00b0.The mol\u00adecular structure of i hydrogen bonds  of Boc\u2013Phe\u2013\u0394Ala was dissolved in 5\u2005ml of methanol and calcium carbonate 0.329\u2005g (1\u2005mM) was added. The mixture was stirred for one\u2005h at room temperature, after which the solvent was evaporated. The residue was dissolved in 7\u2005ml of DMF and isopropyl iodide  was added in portions to the stirred mixture at room temperature during the reaction, the progress of which was monitored by thin-layer chromatography, using 5% methanol in chloro\u00adform as eluent. After completion of the reaction, the solvent was evaporated and the oily residue was dissolved in ethyl acetate and washed consecutively with: 1 M HCl, saturated KHCO3, 0.1 M Na2S2O3 and brine. The organic layer was dried over anhydrous MgSO4 and the title compound was obtained in 81% yield (m.p. = 367\u2013369\u2005K). Recrystallization was performed using mixture of diethyl ether and hexane.The de\u00adhydro\u00addipeptide was obtained by condensation of  al. 2008. For thi1H NMR  \u03b4 1.26 , 1.30 , 2.76 , 3.02 , 4.27\u20134.39 , 5.01 , 5.70 , 6.23 , 7.15\u20137.36 , \u03b4 9.30 . 13C NMR  \u03b4 21.43, 28.10, 36.63, 56.34, 69.40, 78.41, 108.65, 126.29, 128.07, 129.25, 132.71, 138.03, 155.53, 162.81, 171.53. IR  3600\u20132800 broad (H-bonding), 1715 (C=Oester), 1700 (C=Ourethane), 1690 IAB (C=Oamide), 1632 (C=C), 1526 IIAB (C\u2013N and N\u2013H), 1317 (CO\u2013N\u2013C=and N\u2013(C=C)\u2013CO), 1196 and 1166 (C\u2013O\u2013C), 896 (=CH2).Uiso (H) = 1.2Ueq(N), C\u2014Haromatic = 0.95\u2005\u00c5 and Uiso (H) = 1.2Ueq(C), C\u2014Hmeth\u00adyl = 0.98\u2005\u00c5 and Uiso (H) = 1.5Ueq(C); C\u2014Hmethyl\u00adene = 0.99\u2005\u00c5 or C\u2014Hmethine = 0.95\u2005\u00c5 and Uiso (H) = 1.2Ueq(C). Although not definitive, the absolute structure factor  configuration, was \u22120.1\u2005(6) for 1095 Friedel pairs.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814025197/zs2321sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814025197/zs2321Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814025197/zs2321Isup3.cmlSupporting information file. DOI: 1034604CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Packing in the title keto ester compound is dominated by the formation of inversion dimers by both non-classical hydrogen bonds and offset \u03c0\u2013\u03c0 stacking inter\u00adactions. 15H10BrClO3, was synthesized in a single-step reaction by condensation of 3-bromo\u00adbenzoic acid with 2-bromo-1-(4-chloro\u00adphen\u00adyl)ethanone in di\u00admethyl\u00adformamide in the presence of tri\u00adethyl\u00adamine as a catalyst. The structure consists of an aryl ketone moiety linked to an aryl ester unit by a methyl\u00adene group. Both units are reasonably planar  and are almost orthogonal, with an angle of 88.60\u2005(3)\u00b0 between them. In the crystal, mol\u00adecules form five separate sets of inversion dimers. Three of these are generated by two C\u2014H\u22efO inter\u00adactions and a C\u2014H\u22efBr contact, and form chains along c and along the ab cell diagonal. In addition, two inversion-related \u03c0\u2013\u03c0 stacking inter\u00adactions between like aryl rings again form chains of mol\u00adecules but in this instance along the bc diagonal. These contacts generate infinite layers of mol\u00adecules parallel to (011) and stack the mol\u00adecules along the a-axis direction.2-(4-Chloro\u00adphen\u00adyl)-2-oxoethyl 3-bromo\u00adbenzoate, C There is an r.m.s. deviation of 0.119\u2005\u00c5 from the best-fit plane through atoms Br1, C1\u2013C8, O1, O2 [maximum deviation 0.2477\u2005(11)\u2005\u00c5 for O1] while the plane of the carboxyl\u00adate unit subtends an angle of 15.5\u2005(2)\u00b0 to that of the bromo\u00adbenzene ring. In addition, the plane of the aryl ketone unit C8\u2013C15, O3, Cl1 has an r.m.s. deviation of 0.010\u2005\u00c5 [maximum deviation 0.0171\u2005(15)\u2005\u00c5 for C15]. The aryl ketone and aryl ester planes are almost orthogonal with an angle of 88.61\u2005(3)\u00b0 between them. Bond lengths and angles in the mol\u00adecule are normal and are generally similar to those found in closely related mol\u00adecules \u2005\u00c5, and neighbouring 4-chloro\u00adphenyl rings Cg2\u22efCg2v = 3.8585\u2005(11)\u2005\u00c5, in this case along the bc diagonal, Fig.\u00a03Cg1 and Cg2 are the centroids of the C1\u2013C6 and C10\u2013C15 rings, respectively; symmetry codes (iv) \u2212x, 2\u00a0\u2212\u00a0y, \u2212z; (v) 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. These contacts combine to generate extended layers of mol\u00adecules parallel to (011), Fig.\u00a04a-axis direction, Fig.\u00a05In the crystal structure, each mol\u00adecule forms five separate inversion dimers. C8\u2014H8et al., 2011aet al., 2011b Chidan Kumar et al., 2014abet al., 2014cA search of the Cambridge Crystallographic Database , followed by a solution of 2-bromo-1-(4-chloro\u00adphen\u00adyl)ethanone (1.0\u2005mmol). The reaction mixture was stirred for 2\u2005h. Progress of the reaction was monitored by TLC. After completion, the mixture was poured into water and the precipitated solid was filtered, dried and recrystallized (EtOAc/hexa\u00adne) to afford 2-(4-chloro\u00adphen\u00adyl)-2-oxoethyl 3-bromo\u00adbenzoate (1). The formation of keto ester (3) was indicated by the appearance of two typical stretching vibrations \u03bd(C=O) ester (1724) and \u03bd(C=O) keto (1698)\u2005cm\u22121, respectively and the disappearance of characteristic IR stretching absorptions ascribable to the carb\u00adoxy\u00adlic acid group in the region of 3400\u20132400\u2005cm\u22121. In the 1H NMR spectrum, the signals for the aromatic protons appeared in their respective regions and the disappearance of a characteristic signal for the COOH proton confirmed the formation of the title compound (1). The 13C NMR spectrum displayed two characteristic signals for the keto and ester carbonyl carbon atoms at 190.7 and 165.3 p.p.m., respectively. Yield: 88%; m.p. 372\u2013373\u2005K; Rf: 0.72 (10% EtOAc/hexa\u00adne); IR : 3089 (Csp2-H), 2933, 2856 (Csp3-H), 1724 (C=O ester), 1698 (C=O ketone), 1585, 1479 (C=C Ar), 1225 (C\u2014O); 1H NMR : \u03b4 8.06\u20138.03 , 7.94\u20137.90 , 7.73\u20137.70 , 7.52\u20137.48 , 7.46\u20137.36 , 5.57 ; 13C NMR : \u03b4 190.7, 165.3, 140.6, 134.5, 133.1, 132.4, 132.0, 131.0, 129.3, 129.3, 127.3, 122.1, 66.5.The preparation followed a procedure developed for the preparation of a related compound (Khan Uiso(H) = 1.2Ueq(C) for aromatic, and C\u2014H = 0.99\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for the methyl\u00adene H atoms.All H atoms were refined using a riding model, with C\u2014H = 0.95\u2005\u00c5 and 10.1107/S1600536814021643/hg5410sup1.cifCrystal structure: contains datablock(s) global, 1. DOI: 10.1107/S1600536814021643/hg54101sup2.hklStructure factors: contains datablock(s) 1. DOI: 864789CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compounds, N\u2014H\u22efO hydrogen bonds lead to dimers; the dimers are linked by weak inter\u00adactions into a three-dimensional network in one case and chains in the other. N-(aryl\u00adsulfon\u00adyl)aryl\u00adamides, namely N-(3-fluoro\u00adbenzo\u00adyl)benzene\u00adsulfonamide, C13H10FNO3S, (I), and N-(3-fluoro\u00adbenzo\u00adyl)-4-methyl\u00adbenzene\u00adsulfonamide, C14H12FNO3S, (II), are described and compared with related structures. The dihedral angle between the benzene rings is 82.73\u2005(10)\u00b0 in (I) compared to 72.60\u2005(12)\u00b0 in (II). In the crystal of (I), the mol\u00adecules are linked by C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in a three-dimensional grid-like architecture, while C\u2014H\u22efO inter\u00adactions lead to one-dimensional ribbons in (II). The crystals of both (I) and (II) feature strong but non-structure-directing N\u2014H\u22efO hydrogen bonds with R22(8) ring motifs. The structure of (I) also features \u03c0\u2013\u03c0 stacking inter\u00adactions.The crystal structures of two  N-(Aryl\u00adsulfon\u00adyl)aryl\u00adamides have received much attention as they constitute an important class of drugs for Alzheimers disease aryl\u00adamides are known to be potent anti\u00adtumour agents against a broad spectrum of human tumour xenografts  in nude mice syn to the N\u2014H bond in the central \u2013C\u2014SO2\u2014N\u2014C(=O)\u2013 segment. By contrast, in (II)anti with respect to the meta-fluoro substitution on the benzoyl ring. The dihedral angle between the benzene rings is 82.73\u2005(10)\u00b0 in (I)The C7 chains, forming columns propagating along the b-axis direction  inter\u00adactions link the mol\u00adecules into chains along the c axis. These chains are inter\u00adconnected via C2\u2014H2\u22ef\u03c0ar\u00adyl (\u03c0 system of the sulfonyl\u00adbenzene ring) and C11\u2014H11\u22ef\u03c0ar\u00adyl (\u03c0 system of the sulfonyl\u00adbenzene ring) inter\u00adactions, forming a three-dimensional grid-like structure rs Fig.\u00a03. These don Fig.\u00a03. In addire Fig.\u00a04. The cryvia C13\u2014H13\u22efO1 inter\u00adactions, as observed in (I)via C5\u2014H5\u22efO3 inter\u00adactions into ac plane rs Fig.\u00a05. The molne Fig.\u00a05. The oveN-(aryl\u00adsulfon\u00adyl)aryl\u00adamides, namely N-(benzo\u00adyl)benzene\u00adsulfonamide (III), N-(3-chloro\u00adbenzo\u00adyl)benzene\u00adsulfonamide (IV), N-(3-methyl\u00adbenzo\u00adyl)benzene\u00adsulfonamide (V), N-(benzo\u00adyl)-4-methyl\u00adbenzene\u00adsulfon\u00adamide (VI) and N-(3-methyl\u00adbenzo\u00adyl)-4-meth\u00adylbenzene\u00adsulfonamide (VII) have previously been reported. A comparison of the dihedral angle between the two benzene rings in these closely related structures indicates that introducing a methyl substituent into the para position of the benzene\u00adsulfonyl ring lowers the dihedral angle with compound (VII) being an exception. The dihedral angle values are 80.3\u2005(1)\u00b0 in (III) C(4) chains via strong structure-directing N\u2014H\u22efO hydrogen bonds. The structures do not feature any other type of inter\u00adactions. However, in (I)ar\u00adyl. Furthermore, introducing the methyl substit\u00aduent into the benzene\u00adsulfonyl ring of (I)The crystal structures of five related Compounds (I)Uiso = 1.2 or 1.5Ueq(parent atom). To improve considerably the values of R1, wR2 and GOOF, reflections with very bad agreement (\u221220 0 0), (\u221220 0 10) and (\u221219 1 15) in (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016003248/hb7565sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016003248/hb7565Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016003248/hb7565IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016003248/hb7565Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016003248/hb7565IIsup5.cmlSupporting information file. DOI: 1418689, 1418688CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A and B) in the asymmetric unit, which differ essentially in the orientation of the terminal amino\u00adphenyl ring with respect to the central benzene ring. In the crystal, mol\u00adecules are linked via N\u2014H\u22efO hydrogen bonds forming \u2013A-B\u2013A\u2013B\u2013 zigzag chains propagating along [010].The title compound crystallized with two independent mol\u00adecules  in the asymmetric unit. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond in each mol\u00adecule with the phenol ring being inclined to the central benzene ring by 4.93\u2005(14) and 7.12\u2005(14)\u00b0 in mol\u00adecules A and B, respectively. The conformation of the two mol\u00adecules differs essentially in the orientation of the terminal amino\u00adphenyl ring with respect to the central benzene ring; this dihedral angle is 50.51\u2005(4)\u00b0 in mol\u00adecule A and 54.61\u2005(14)\u00b0 in mol\u00adecule B. The two outer aromatic rings are inclined to one another by 51.39\u2005(14) and 49.88\u2005(14)\u00b0 in mol\u00adecules A and B, respectively. In the crystal, mol\u00adecules are connected by N\u2014H\u22efO hydrogen bonds generating \u2013A-B\u2013A\u2013B\u2013 zigzag chains extending along [010]. The chains are linked via C\u2014H\u22ef\u03c0 inter\u00adactions involving neighbouring A mol\u00adecules, forming slabs lying parallel to (100).The title compound, C In mol\u00adecules A and B the phenol rings (C1\u2013C6 and C20\u2013C25) are inclined to the central benzene rings (C8\u2013C13 and C27\u2013C32) by 4.93\u2005(14) and 7.12\u2005(14)\u00b0, respectively.The title compound crystallized with two independent mol\u00adecules \u00b0 in mol\u00adecule B. The two outer aromatic rings  are inclined to one another by 51.39\u2005(14) and 49.88\u2005(14)\u00b0 in mol\u00adecules A and B, respectively. The C\u2014N, C\u00a0N and C\u2014C bond lengths are normal and close to the values observed in related structures  with respect to the central benzene rings (C8\u2013C13 and C27\u2013C32); this dihedral angle is 50.51\u2005(4)\u00b0 in mol\u00adecule A-B\u2013A\u2013B\u2013 zigzag chains extending along [010]; Table\u00a01via C\u2014H\u22ef\u03c0 inter\u00adactions involving neighbouring A mol\u00adecules, forming slabs lying parallel to (100); see Table\u00a01In the crystal, mol\u00adecules are connected by N\u2014H\u22efO hydrogen bonds, generating \u2013et al., 2013et al., 2012viz. N-[(E)-4-chloro\u00adbenzyl\u00adidene]-N\u2032-phenyl\u00adbenzene-1,4-di\u00adamine (II) \u00b0 in mol\u00adecule B, owing to the presence of the intra\u00admolecular O\u2014H\u22efN hydrogen bond. The outer phenyl ring is inclined to the central six-membered ring by 44.18\u2005(11)\u00b0 in (II), compared to 50.51\u2005(4) and 54.61\u2005(14)\u00b0 in mol\u00adecules A and B, respectively, of the title compound.There are very few examples of similar compounds in the literature although some metal complexes of similar ligands have been reported on  of salicyladehyde in 5\u2005ml of absolute ethanol was added dropwise with stirring. The mixture was stirred for 10\u2005min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2\u2005h. The resulting reddish yellow precipitate was recovered by filtration, washed several times with a small portions of EtOH and then with diethyl ether to give 120\u2005mg (75%) of the title compound. Crystals suitable for X-ray analysis was obtained within 3 days by slow evaporation of a solution in methanol.100\u2005mg (1\u2005mmol) of Uiso(H) = 1.2Ueq(N) and = 1.5Ueq(O). All C-bound H atoms were positioned geometrically and refined using a riding model with C\u2014H = 0.93\u2005\u00c5 and with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989014026309/su5028sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026309/su5028Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014026309/su5028Isup3.cmlSupporting information file. DOI: 1036844CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom is located on a center of symmetry with an overall octa\u00adhedral coordination environment. Both intra- and inter\u00admolecular inter\u00adactions occur between the amino and acetate groups, leading to a layered structure.In a cadmium complex incorporating 1,3-di\u00adamino\u00adpropane and nitro\u00adphenyl\u00adacetate ligands, the Cd 8H6NO4)2(C3H10N2)2], the CdII atom is located on a center of symmetry with one independent Cd\u2014O distance of 2.3547\u2005(17)\u2005\u00c5 and two Cd\u2014N distances of 2.3265\u2005(18) and 2.3449\u2005(19)\u2005\u00c5. The CdII atom has an overall octa\u00adhedral coordination environment. Several types of hydrogen-bonding inter\u00adactions are evident. Both intra- and inter\u00admolecular inter\u00adactions occur between the amino groups and the O atoms of the acetate group. These N\u2014H\u22efO hydrogen bonds lead to a layered structure extending parallel to the bc plane. In addition, weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions involving the nitro groups exist, leading to the formation of a three-dimensional network structure.In the structure of the title compound, [Cd(C Several other weak inter\u00admolecular hydrogen-bonding inter\u00adactions of the C\u2014H\u22efO type also exist in the structure involving the O atoms of nitro groups and neighboring C\u2014H groups.Somewhat weaker inter\u00admolecular N\u2014H\u22efO inter\u00adactions involving the same types of donor and acceptor groups occur between neighboring mol\u00adecules Table\u00a01 and leadne Fig.\u00a02. It shou2, 0.4\u2005mmol (29.7\u2005mg) of 1,3-di\u00adamino\u00adpropane, and 0.4\u2005mmol (72.5\u2005mg) of 4-nitro\u00adphenyl\u00adacetic acid were added to 2\u2005ml of methanol in a 5\u2005ml beaker. The sample was covered with aluminum foil containing several small vent holes and left for a week to evaporate. The slow evaporation method was used to crystallize a colorless mononuclear species and crystals were gathered for X-ray crystallographic analysis.0.2\u2005mmol (36.7\u2005mg) of anhydrous CdClUiso(H) = 1.2Ueq(C) and C\u2014H distances of 0.93\u2005\u00c5 for aromatic hydrogen atoms, Uiso(H) = 1.2Ueq(C) and C\u2014H distances of 0.97\u2005\u00c5 for methylene hydrogen atoms, and Uiso(H) = 1.2Ueq(N) and N\u2014H distances of 0.90\u2005\u00c5 for amino hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016000943/wm5258sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016000943/wm5258Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016000943/wm5258Isup3.cdxSupporting information file. DOI: 1447705CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, pairs of inversion-related mol\u00adecules are linked into inversion dimers  23H19NO2, an oxazine Mannich base derivative, the oxazine ring has a half-chair conformation. The 2-hy\u00addroxy\u00adnaphthalen-1-yl substituent is placed in an axial position. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond, forming an S(6) graph-set motif. In the crystal, mol\u00adecules are connected by a pair of C\u2014H\u22ef\u03c0 inter\u00adactions into an inversion dimer, which is reinforced by another pair of weak C\u2014H\u22ef\u03c0 inter\u00adactions. The dimers are linked by a \u03c0\u2013\u03c0 inter\u00adaction [centroid-centroid distance = 3.6268\u2005(17)\u2005\u00c5], consolidating a column along the a axis. Furthermore, the columns inter\u00adact with each other by a weak C\u2014H\u22ef\u03c0 inter\u00adaction, generating a three-dimensional network.In the title compound, C Recently, we synthesized the title compound by a reaction between the cyclic aminal 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00adundecane (TATU) with 2-naphthol solvent-free at low temperature. Because a wide range of cured properties can be obtained \u2005\u00c5, \u03b8 = 50.0\u2005(3)\u00b0 and \u03c6 = 98.3\u2005(4)\u00b0 for the ring O1/C1/N1/C2/C12/C11. The methyl group bonded to atom N1 of the oxazine ring is placed in an axial position. The pendant naphthyl group (C21\u2013C30) makes a dihedral angle of 59.94\u2005(4)\u00b0 with the oxazine ring plane defined by atoms C11, C12 and O1. The bond lengths, N1\u2014C1 and O1\u2014C1, are normal and comparable to the corresponding values observed in the related structure of 6-bromo-2,4-bis\u00ad(3-meth\u00adoxy-phen\u00adyl)-3,4-di\u00adhydro-2H-1,3-naphthoxazine  graph-set motif, where the N\u22efO distance is longer by about 0.04 and 0.03\u2005\u00c5, respectively, than the observed values in related structures of 1-(piperidin-1-ylmeth\u00adyl)-2-naphthol \u2005\u00c5 . Neighboring columns are connected by a weak C\u2014H\u22ef\u03c0 inter\u00adaction   were manually ground together, heated to 313\u2005K and stirred for 12\u2005h under solvent-free conditions. Progress of the reaction was determined by TLC monitoring. After completion of the reaction, the mixture was cooled to room temperature and the solid residue was purified by silica gel column chromatography with benzene\u2013ethyl acetate (4:1) as the eluent to give 1-{oxazin-2(3H)-yl]meth\u00adyl}naphthalen-2-ol as a brown solid in 28% yield. This compound was obtained in its crystalline form by recrystallization from an absolute ethanol solution (m.p. 443\u2005K).2-Naphthol  and 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00ad[4.3.1.1Uiso(H) value and the C\u2014C\u2014O\u2014H torsion angle were refined. C-bound H atoms were fixed geometrically (C\u2014H = 0.95 or 0.99\u2005\u00c5) and treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015583/is5412sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015015583/is5412Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015583/is5412Isup3.cmlSupporting information file. DOI: 1419687CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this complex, all CuII atoms have a square-pyramidal coordination sphere, with long axial and short basal Cu\u2014O distances.The dinuclear title compound crystallizes as a dimer forming a tetra\u00adnuclear copper(II) complex, [Cu 4(CH3O)4(C11H13O2)4], consists of dimeric dinuclear copper(II) complexes oriented around a centre of inversion. Within each dinuclear fragment, the two CuII atoms are in a distorted square-planar coordination sphere. Two neighbouring fragments are linked by four apical Cu\u2014O contacts, yielding an overall square-pyramidal coordination environment for each of the four CuII atoms. The mol\u00adecules are arranged in layers parallel to (101). Non-classical C\u2014H\u22efO hydrogen-bonding inter\u00adactions are observed between the layers.The structure of the title compound, [Cu The distances and coordination modes between CuII atoms vary and thus, the compound is a suitable study case for investigating different spin-coupling paths. This knowledge is deemed important for the design of tailor-made magnetic compounds.The title compound was obtained as a by-product in the synthesis of an unsymmetrically substituted copper(II) salophene complex  ions Cu1 and Cu2 within the binuclear fragment is 2.9938\u2005(2)\u2005\u00c5  title compound consists of two dinuclear complex fragments oriented around a centre of inversion. Within each fragment the two Cu\u2005\u00c5 Fig.\u00a01 which isi  bond to the methoxido ligand of the neighbouring fragment. For the Cu2 atom, the situation is comparable, with slightly shorter Cu\u2014O distances in comparison with Cu1: Cu2\u2014O3 1.8939\u2005(8)\u2005\u00c5, Cu2\u2014O4 1.9473\u2005(9)\u2005\u00c5, Cu2\u2014O5 1.9455\u2005(8)\u2005\u00c5 and Cu2\u2014O6 1.9081\u2005(8)\u2005\u00c5. The longer distance Cu2\u2014O1i of 2.4994\u2005(9)\u2005\u00c5 to the phenoxido ligand atom of the neighbouring fragment causes less sterical congestions at the Cu2 atom and thus, appears to be the cause for the shorter basal Cu\u2014O distances.Short distances Cu1\u2014O1 of 1.9166\u2005(8)\u2005\u00c5, Cu1\u2014O2 of 1.9557\u2005(9)\u2005\u00c5, Cu1\u2014O5 of 1.9522\u2005(8)\u2005\u00c5 and Cu1\u2014O6 of 1.9154\u2005(9)\u2005\u00c5 are found for the Cu1 atom to the basal O atoms within the binuclear fragment. A substanti\u00adally longer distance of 2.3703\u2005(9)\u2005\u00c5 is observed for the apical Cu1\u2014O52versus \u03bc3) of the two methoxido ligands in each fragment can be distinguished by the angles C24\u2014O5\u2014O6  versus C23\u2014O6\u2014O5  , resulting in a more pyramidal-like geometry. This differs to the more trigonal-planar geometry of O6 (see Table\u00a01versus 1.2963\u2005(13)\u2005\u00c5].The binding modes \u00b0 due to repulsion of the In the crystal, the tetra\u00adnuclear mol\u00adecules arrange in layers parallel to (101) Fig.\u00a02. Weak notert-butyl\u00adsalicyl\u00adaldehyde in 10\u2005ml THF, the mixture was stirred for 22\u2005h at room temperature. Addition of hexane yielded the title compound as a dark crystalline material from the reaction mixture .After treatment of 102\u2005mg (0.35\u2005mmol) 4-Br-salicyl-2-(2-amino)\u00adphenyl\u00adimine with 113\u2005mg of copper(II)acetate monohydrate (0.445\u2005mmol), 1\u2005ml tri\u00adethyl\u00adamine in 10\u2005ml THF, and 65.5\u2005mg (0.368\u2005mmol) 4-Uiso(H) = 1.5Ueq(C) for sp2 C atoms and of 0.98\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for sp3 C atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901500376X/wm5122sup1.cifCrystal structure: contains datablock(s) general, I. DOI: 10.1107/S205698901500376X/wm5122Isup2.hklStructure factors: contains datablock(s) I. DOI: 1050914CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Single crystals of the ligand have been grown and analyzed.Hydrazones and their metal complexes were heavily studied due to their pharmacological applications such as antimicrobial, anticonvulsant analgesic, anti-inflammatory and anti-cancer agents. This work aims to synthesize and characterize novel complexes of VO2+, Co2+, Ni2+, Cu2+, Zn2+, Zr4+ and Pd2+ complexes have the formulas: [VO(OBH\u2013H)2]\u00b7H2O, [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH, [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH, [Cu(OBH)2Cl2]\u00b72H2O, [Zn(OBH\u2013H)2], [Zr(OBH)Cl4]\u00b72H2O, and [Pd2(OBH)(H2O)2Cl4]\u00b72H2O. All complexes are nonelectrolytes except [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH. OBH ligates as: neutral tetradentate (NNOO) in the Ni2+ and Pd2+ complexes; neutral bidentate (OO) in [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH, [Zr(OBH)Cl4]\u00b72H2O and [Cu(OBH)2Cl2]\u00b72H2O and monobasic bidentate (OO) in the Zn2+ and VO2+ complexes. The NMR (1H and 13C) spectra support these data. The results proved a tetrahedral for the Zn2+ complex; square-planar for Pd2+; mixed stereochemistry for Ni2+; square-pyramid for Co2+ and VO2+ and octahedral for Cu2+ and Zr4+ complexes. The TGA revealed the outer and inner solvents as well as the residual part. The molecular modeling of [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH and [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH are drawn and their molecular parameters proved that the presence of two metals stabilized the complex more than the mono metal. The complexes have variable activities against some bacteria and fungi. [Zr(OBH)Cl4]\u00b72H2O has the highest activity. [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH has more activity against Fusarium.Oxalo bis [OBH] has a monoclinic crystal with P 1 21/n 1 space group. The VO2+ and Co2+ complexes have square-pyramid structure. [Cu(OBH)2Cl2]\u00b72H2O and [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH decomposed to their oxides while [VO(OBH\u2013H)2]\u00b7H2O to vanadium. The energies obtained from molecular modeling calculation for [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH are less than those for [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH indicating the two metals stabilized the complex more than mono metal. The Co(II) complex is polar molecule while the Ni(II) is non-polar.Oxalo bis structure was proved by X-ray crystallography. It coordinates with some transition metal ions as neutral bidentate; mononegative bidentate and neutral tetradentate. The complexes have tetrahedral, square-planar and/or octahedral structures. The VOThe online version of this article (doi:10.1186/s13065-015-0135-y) contains supplementary material, which is available to authorized users. In the preparation of VO\u22123\u00a0mol\u00a0L\u22121 DMSO solution of the compounds was measured on Orion 3 STAB Conductivity Bridge. The IR spectra were recorded as KBr discs on a FT/IR-6300 type A (400\u20134000\u00a0cm\u22121). The electronic spectra of the complexes were recorded on a Cary 5 UV\u2013vis spectrophotometer, varian (200\u2013900\u00a0nm). The 1H NMR spectra of the ligand and the diamagnetic complexes were recorded in DMSO-d6, on a Bruker WP 200 SY Spectrometer (400\u00a0MHz) at room temperature using tetramethylsilane (TMS) as an external standard. The magnetic measurements were carried out on a Johnson-Matthey magnetic balance, UK. The TGA thermograms were recorded (25\u2013800\u00a0\u00b0C) on a Shimadzu TGA-60; the nitrogen flow and heating rate were 50\u00a0ml/min and 10\u00a0\u00b0C min\u22121, respectively. The X-ray single crystal diffraction data were collected on a Rigaku R-Axis Rapid diffractometer using filtered Mo-K \u03b1-radiation. The structure was solved by the direct methods and expanded using Fourier techniques at Kuwait University. The ligand and its complexes were investigated for antimicrobial activity against Bacillus, Aspergillus, Escherichia coli, Pennicillium and Fusarium as reported earlier \u00b7H2O, [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH, [Cu(OBH)2Cl2]\u00b72H2O, [Zn(OBH\u2013H)2], [Zr(OBH)Cl4]\u00b72H2O and binuclear complexes: [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH and [Pd2(OBH)(H2O)2Cl4]\u00b72H2O. All complexes are colored, solid and stable towards air and moisture at room temperature. They have high melting points and are insoluble in most common organic solvents and completely soluble in DMSO. The molar conductance values  complex supports the formation of [Co(OBH)2Cl]+Cl\u2212\u00b7\u00bdEtOH  and \u03bd(C=N) vibrations at 3325, 1701 and 1605, respectively in its IR spectrum Cl4]\u00b72H2O coordinating through the two amidic carbonyl groups based on the following observations: the \u03c5(C=O) band observed at 1701\u00a0cm\u22121 in ligand spectrum was shifted to 1686\u20131699\u00a0cm\u22121 in complexes having little intensity indicating that the two amidic carbonyl groups (C=Oamidic) participated in bonding while the other two carbonyl (C=Oketonic) still at the same position. The new band at 464\u2013495\u00a0cm\u22121 is due to \u03c5(M\u2013O) vibration  showed splitting of NH signal as a result of conversion of one of NHC=O to N=C\u2013OH and the existence of the others without participation ketonic, (C=O)amidic free, (C=O)amidic bonded, (C=N), (C=N)*, (C\u2013O) and CH3, respectively. The appearance of (C=N)* (due to conversion of NHC=O to N*=C\u2013O) and (C\u2013O) peaks confirm enolization process   and \u03c5(M\u2013ed water  and abse2(OBH)Cl4]\u00b7H2O\u00b7EtOH (Structure\u00a02(OBH)(H2O)2Cl4]\u00b72H2O amidic to 1644 in the Pd(II) complex and to 1552 and 1676 in the Ni(II) complex together with appearance of \u03c5(M\u2013N) \u00b7H2O\u00b7EtOH has a value of 371.7 (the base peak) corresponding to Ni(OBH)Cl\u00b7\u00bdEtOH meaning that this species is highly stable. Multi peaks were observed ending with one at 128.9 (intensity 65\u00a0%) due to ZrO2.Moreover, the mass spectrum of \u00b7H2O\u00b7EtOH is 1.36 BM which is less than the normal values reported for tetrahedral or octahedral coordination containing two unpaired electrons. Its electronic spectrum showed a broad band at 19,050\u00a0cm\u22121 (\u025b\u00a0=\u00a0180\u00a0mol\u22121\u00a0L) typical of a square-planar structure with some distortion [2(OBH)(H2O)2Cl4]\u00b72H2O proved the square-pyramid structure in which the metal is surrounded by NO donors, two chloro and one coordinated water. The bands at 37,540 and 28,470\u00a0cm\u22121 are attributed to charge transfer transitions, probably O\u00a0\u2192\u00a0Pd transition \u00b7H2O exhibits one band with maximum at 20080\u00a0cm\u22121 assigned to the 2E2g\u00a0\u2192\u00a02T2g transition in an octahedral geometry [g level. The magnetic moment value (1.45 BM) was found lower than the values reported for the d9\u2013system containing one unpaired electron (1.73\u20132.25\u00a0BM) suggesting interactions between the copper centers.The electronic spectrum of [Cu(OBH)geometry . The ban2Cl]Cl\u00b7\u00bdEtOH showed three decomposition steps at mid- points of 60, 319 and 500\u00a0\u00b0C corresponding to the removal of \u00bdCl2\u00a0+\u00a0\u00bdEtOH ; C16H24N4O6Cl  and C4H4N2  leaving [CoO4N2] moiety .The decomposition steps, the DTG maximum temperature and the removing species are shown in Table\u00a02]\u00b7H2O showed also three steps; the first (mid. point 56\u00a0\u00b0C) represents the removal of the outside water molecule ; the second (mid. point 289\u00a0\u00b0C) represents the loss of C16H24N4O6  and the third for the repulsion of C4H4N4O2 . The residue is vanadium metal .The TG curve of [VO(OBH-H)2Cl2]\u00b72H2O thermogram showed decomposition steps ending with copper oxide at Temp. >400\u00a0\u00b0C. The decomposition showed the removal of the two hydrated water in the first step at mid. point of 59\u00a0\u00b0C. The other two steps were observed at 291 and 374\u00a0\u00b0C corresponding to the removal of C16H24N4O6 and C4H4N4O3, respectively, leaving CuO as a residue.[Cu(OBH)2(OBH)Cl4]\u00b7H2O\u00b7EtOH showed four steps. The first at 72\u00a0\u00b0C is due to the removal of the outside water and EtOH . The second step (368\u00a0\u00b0C) represents the loss of Cl2\u00a0+\u00a0C8H12N2O2 . The third step represents the repulsion of Cl2 . The fourth step  corresponding to the removal of C2H2N2. The residue is 2NiO  . The first three steps observed at mid. points of 76, 313 and 449\u00a0\u00b0C are corresponding to the removal of (Cl2\u00a0+\u00a0H2O); (H2O\u00a0+\u00a0C8H12N2O2) and Cl2, respectively Cl2(OBH)(H2O)2Cl4]\u00b72H2O showed two main steps at 75 and 322\u00a0\u00b0C due to the liberation of the outside water and 2H2O\u00a0+\u00a02Cl2\u00a0+\u00a0C4H12, respectively. High residue \u00a0% was found over 500\u00a0\u00b0C.The thermogram of [Pd2Cl]Cl\u00b7\u00bdEtOH and [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH (Structure\u00a02(OBH)Cl4]\u00b7H2O\u00b7EtOH are less than those of [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH indicating that the presence of two metals stabilized the complex more than the mono metal lowering the energy. The dipole moment calculated for the Co(II) complex is 4.949\u00a0D proving the polar nature of the complex. The value of Ni(II) complex is 0.413\u00a0D indicating its non-polarity.Trials to grow single crystals for the investigated complexes were failed. In order to calculate the molecular parameters, \u00b72H2O has higher activity against all tested microorganisms except E. coli. The activity is highest and more with Penicillium (9\u00a0mm zone inhibition). The higher activity may be due the presence of non-ionizable chlorine and to the less planarity of the complex making it more lipophilic. Most compounds have high activity against Fusarium. [Cu(OBH)2Cl2]\u00b72H2O has higher value against Fusarium (15\u00a0mm). Comparing these data with that of ampicillin and those obtained for different hydrazone complexes showed more or less activity \u00b72H2O and [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH decomposed to their oxides while [VO(OBH\u2013H)2]\u00b7H2O to the metal. The energies from molecular modeling calculation is less in [Ni2(OBH)Cl4]\u00b7H2O\u00b7EtOH than those for [Co(OBH)2Cl]Cl\u00b7\u00bdEtOH indicating that the presence of two metals stabilized the complex more than the mono metal. The Co(II) complex is polar molecule while the Ni(II) is non-polar.Oxalo bis has been prepared and characterized by x-ray crystallography. It coordinates as neutral bidentate; mononegative bidentate and neutral tetradentate. The complexes have tetrahedral, square-planar and/or octahedral structures. The VOCrystallographic data for the structure reported in this paper have been deposited with Cambridge Crystallographic Data Center as supplementary publication CCDC-985982."}
{"text": "This article describes data related to the research article titled \u201cFunctional characterization of importin \u03b18 as a classical nuclear localization signal receptor\u201d  Specifications TableValue of the data\u2022These data are valuable to researchers interested in the molecular mechanisms by which the importin \u03b1-cNLS substrate complex dissociates in the nucleus.\u2022These data show that importin \u03b11 and \u03b18 have substantial differences in dimer-forming ability, despite both proteins belonging to the same subfamily.\u2022These data provide a new insight into the function of nuclear-localized importin \u03b1s.1To examine whether importin \u03b1s can directly bind with other importin \u03b1 subtypes, FLAG-tagged importin \u03b16, \u03b17, or \u03b18 recombinant proteins were incubated with either GST-importin \u03b18, or GST-importin \u03b11, and analyzed by western blotting A. To inv22.1EcoRI and NotI, and then subcloned into the pGEX6P3 plasmid . The construct integrity of pGEX6P3/FLAG-h-importin \u03b16 and pGEX6P3/FLAG-h-importin \u03b17 was confirmed by DNA sequencing using the following primers: pGEX 5\u2032 sequencing primer: 5\u2032-GGGCTGGCAAGCCACGTTTGGTG-3\u2032, pGEX 3\u2032 sequencing primer: 5\u2032-CCGGGAGCTGCATGTGTCAGAGG-3\u2032, importin \u03b16 sequencing primer: 5\u2032-GCATCTGGAACTTTTCTGCATACC-3\u2032, or importin \u03b17 sequencing primer: 5\u2032-GTACATTACAGTTTGAAGCTGCCT-3\u2032.The N-terminus FLAG-tagged cDNAs encoding full-length human importin \u03b16  or full-length human-importin \u03b17  were amplified from either HEK293 cells or MRK-nu-1 cells  by PCR using the following primers: importin \u03b16 Forward: 5\u2032-CCCGAATTCCGCCATGGACTACAAGGACGACGACGACAAGATGGATGCCATGGCTAGTCC-3\u2032 and importin \u03b16 Reverse: 5\u2032-CCCGCGGCCGCCTCGAGTTAAAGTTGAAATCCATCC-3\u2032 or importin \u03b17 Forward: 5\u2032-CCCGAATTCCGCCATGGACTACAAGGACGACGACGACAAGATGGAGACCATGGCGAGC-3\u2032 and importin \u03b17 Reverse: 5\u2032-CCCGCGGCCGCCTCGAGTTATAGCTGGAAGCCCTCC-3\u2032. The PCR program was as follows: 2\u00a0min at 94\u00a0\u00b0C followed by 40 cycles of 30\u00a0s at 98\u00a0\u00b0C and 15\u00a0min at 68\u00a0\u00b0C. The PCR products were digested with EcoRI and NotI sites of pGEX6P3, and then sequenced using either the pGEX 5\u2032 or pGEX 3\u2032 sequencing primer and the importin \u03b18 sequencing primer: 5\u2032-CAACATCGCTTCAGGGACTTCG-3\u2032.The human-importin \u03b18  cDNA with the FLAG-tag at the N-terminus was amplified by PCR from the pcDNA5/3xFLAG-h-importin \u03b18 plasmid The construct encoding SV40 large T antigen NLS  was subcloned from pGEX2T-SV40TNLS-GFP BamHI and XhoI sites of pGEX6P1, and then verified by sequencing.The human cDNA encoding the tumor protein p53 (NM_000546) was amplified from MCF7 cells by PCR performed using the following primers: p53 Forward: 5\u2032-CACGGATCCATGGAGGAGCCGCAGTCAGATC-3\u2032 and p53 Reverse: 5\u2032-GGACTCGAGTCAGTCTGAGTCAGGCCCTTCTG-3\u2032. The PCR program was as follows: one cycle of 2\u00a0min at 94\u00a0\u00b0C; 40 cycles of 15\u00a0s at 94\u00a0\u00b0C, 30\u00a0sec at 64\u00a0\u00b0C, and 1\u00a0min 20\u00a0s at 68\u00a0\u00b0C; and one cycle of 10\u00a0min at 68\u00a0\u00b0C. The PCR product was subcloned into the 2.2Escherichia coli Rosetta, and then the cells were grown at 37\u00a0\u00b0C in LB medium containing 50\u00a0\u03bcg/mL ampicillin. Expression was induced by addition of 1\u00a0mM isopropyl-\u03b2-d-thiogalactopyranoside (IPTG), followed by incubation at 20\u00a0\u00b0C for 12\u00a0h. The bacteria were lysed in lysis buffer , 0.2\u00a0mM phenylmethylsulfonyl fluoride (PMSF), 1\u00a0\u03bcg/mL aprotinin , 1\u00a0\u03bcg/mL pepstatin , and 1\u00a0\u03bcg/mL leupeptin (Peptide Institute)) by freeze\u2013thawing twice and passing through a French press . The cell lysates were sonicated using a Sonifier 250 , and centrifuged at 20,400g at 4\u00a0\u00b0C for 30\u00a0min. The resultant supernatant was incubated with glutathione-Sepharose 4B beads  at 4\u00a0\u00b0C for 12\u00a0h. After the GSH beads were washed five times with lysis buffer, GST-tagged proteins were eluted with elution buffer . Cleavage of GST from the GST-fused protein was performed using PreScission protease  with 10\u00a0units/mg of fusion protein at 4\u00a0\u00b0C for 12\u00a0h in cleavage buffer . Finally, the purified proteins were dialyzed against dialysis buffer  and concentrated by ultrafiltration using Amicon Ultra centrifugal filter units .Recombinant proteins fused to GST were purified as follows: The expression vectors were transformed into 2.32.4The following antibodies were used for western blotting: anti-FLAG M2 antibody , anti-GST antibody , anti-GFP antibody , anti-p53 (FL-393) antibody , and horseradish peroxidase (HRP)-conjugated anti-mouse or anti-rabbit IgG secondary antibodies 2.5http://rsbweb.nih.gov/ij/).Samples were loaded on a 10% SDS-PAGE gel, and the separated proteins in the gel were transferred onto an Immobilon-P membrane  using a semi-dry transfer blotting system . The membrane was blocked with blocking buffer consisting of 3% skim milk in Tris-buffered saline  with 0.05% Tween (TBS-T) for 1\u00a0h. The membrane was probed with primary antibodies diluted in Can Get Signal Immunoreaction Enhancer Solution 1  at 4\u00a0\u00b0C overnight, and then incubated with the HRP-conjugated secondary antibody diluted in Can Get Signal Immunoreaction Enhancer Solution 2 (TOYOBO) at room temperature (RT) for 1\u00a0h. After the membrane was washed with TBS-T, it was developed with Chemi-Lumi One L or Super . The intensity of each western blot signal was quantified by Image J software ("}
{"text": "I with the unsymmetrical ligand N-(pyridine-2-ylmeth\u00adyl)pyridine-3-amine afforded right- and left-handed helical chains. The AgI atom of the right-handed helical chain adopts a slightly distorted linear coordination geometry, while that of the left-handed helical chain displays a bent geometry.The reaction of Ag 11H11N3)]CF3SO3}n, there are two AgI atoms, two N-(pyridine-2-ylmeth\u00adyl)pyridine-3-amine ligands (A and B) and two CF3SO3\u2212 anions. Both AgI atoms are bridged by two pyridine N atoms from two symmetry-related A or B ligands, forming right- or left-handed helical chains, respectively. The AgI atom of the right-handed helical chain adopts a slightly distorted linear coordination geometry [N\u2014Ag\u2014N = 170.69\u2005(14)\u00b0], while that of the left-handed helical chain adopts a bent geometry [N\u2014Ag\u2014N = 149.42\u2005(14)\u00b0]. Both helical chains have the same pitch length [10.8437\u2005(5)\u2005\u00c5], propagate along the b-axial direction and are alternately arranged via Ag\u22efAg [3.0814\u2005(5)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.514\u2005(3) and 3.487\u2005(3)\u2005\u00c5], resulting in the formation of a two-dimensional supra\u00admolecular network extending parallel to the ab plane. Weak Ag\u22efO  and Ag\u22efF [3.017\u2005(3)\u2005\u00c5] inter\u00adactions as well as N\u2014H\u22efO and C\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22efF hydrogen-bonding inter\u00adactions occur between the helical chains and the anions.In the asymmetric unit of the title compound, {[Ag(C The structure of title compound is related to that of the perchlorate salt , two N-(pyridine-2-ylmeth\u00adyl)pyridine-3-amine  and two tri\u00adfluoro\u00admethane\u00adsulfonate anions. The Ag1 atom is coordinated by two pyridine N atoms from two symmetry-related A ligands giving a geometry which is slightly distorted from linear [N1\u2014Ag1\u2014N2 = 170.69\u2005(14)\u00b0], forming a right-handed helical chain, while the Ag2 atom is coordinated by two pyridine N atoms from two symmetry-related B ligands in a bent arrangement [N4\u2014Ag2\u2014N5 = 149.42\u2005(14)\u00b0], forming a left-handed helical chain. Two pyridine rings coordinating to the Ag1 and Ag2 atoms are tilted by 14.1\u2005(3) and 28.9\u2005(2)\u00b0, respectively, with respect to each other.The molecular components of the title structure are shown in Fig.\u00a01b-axial direction and are alternately arranged via Ag1\u22efAg2 inter\u00adactions [3.0814\u2005(5)\u2005\u00c5], resulting in the formation of a two-dimensional supra\u00admolecular network extending parallel to the ab plane \u2005\u00c5; symmetry code: (iv) \u2212x, y\u00a0\u2212\u00a0z\u00a0+\u00a03SO3\u2212 anions.Both helical chains in the structure have the same pitch length [10.8437\u2005(5)\u2005\u00c5], propagate along the ne Fig.\u00a02. Further] Figs. 1 and 2 \u25b6 N-(pyridin-2-ylmeth\u00adyl)pyridine-3-amine) was prepared according to a procedure described by Lee et al.  = 0.95\u2005\u00c5 for Csp2\u2014H, 0.88\u2005\u00c5 for amine N\u2014H and 0.99\u2005\u00c5 for methyl\u00adene C\u2014H. For all H atoms Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814022922/zs2318sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022922/zs2318Isup2.hklStructure factors: contains datablock(s) I. DOI: 1029928CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A near-perfect octa\u00adhedral zinc(II) complex coordinated to two coumarin fluoro\u00adphores. 14H14NO4)2(H2O)2]\u00b72C2H6OS, shows that the ZnII cation adopts an octa\u00adhedral geometry and lies on an inversion center. Two organic ligands occupy the equatorial positions of the coordination sphere, forming a chelate ring motif via the O atom on the formyl group and another O atom of the carbonyl group (a pseudo-\u03b2-diketone motif). Two water mol\u00adecules occupy the remaining coordination sites of the ZnII cation in the axial positions. The water mol\u00adecules are each hydrogen bonded to a single dimethyl sulfoxide mol\u00adecule that has been entrapped in the crystal lattice. The structure of the title coordination complex, [Zn(C This is indicated by the short C=O bond of the dione (O3\u2014C4) and the C=O bond length of the formyl moiety (O4\u2014C9), with values of 1.2686\u2005(10) and 1.2603\u2005(10)\u2005\u00c5, respectively. The Zn\u2014O bonds complete the stable six-membered chelating motif, which is favorable for smaller metal ions  distance is 2.09\u2005\u00c5  to 93.18\u2005(3)\u00b0. A single DMSO solvent mol\u00adecule completes the asymmetric unit.The mol\u00adecular structure of (1) is shown in Fig.\u00a01II ion S1\u2014O6\u22efH52\u2014O5 [1.983\u2005(9)\u2005\u00c5]. Inter\u00adestingly, there are also two C\u2014H\u22efO hydrogen-bonding inter\u00adactions from the methyl moiety of DMSO; one with the O atom on the formyl functional group in the equatorial position (H13A\u22efO4 = 2.52\u2005\u00c5) and an additional hydrogen-bonding inter\u00adaction from the carbonyl\u00addione group occupying another equatorial position (H12B\u22efO3 = 2.62\u2005\u00c5). Together these two inter\u00adactions form three C\u22efO6 (2.29\u2005\u00c5), forming an infinite chain.The crystal structure of the title compound shows an extensive array of hydrogen-bonding inter\u00adactions Table\u00a01 forming et al., 2013A) and the electron-rich region of the second coumarin ring system (C4A\u2013C8A) of an adjacent compound, whereby the centroids are 3.734\u2005\u00c5 apart  and 5(b); however, these did not yield any results. Therefore a modification of the search by specifically searching structures that have a bidentate chelating \u03b2-diketone motif coordinated to the zinc(II) in the equatorial position, with two water mol\u00adecules in the axial position, as shown in Fig.\u00a05c) was carried out. This refined search yielded two similar structures with ZnII octahedrally coordinated, the first by Solans et al., whereby two 1,3-bis\u00ad(2-hy\u00addroxy\u00adphen\u00adyl)propane-1,3-dionate ligands coordinate to the ZnII ion, with the remaining two coordination sites occupied by two ethanol mol\u00adecules  was then added to the solution. After stirring for 20\u2005min, a yellow solid formed, which was collected by filtration and dried. A small amount of the solid (20\u2005mg) was redissolved in a 1:1 mixture of MeOH and DMSO to form a saturated solution (1\u2005mL) which was was allowed to stand for several weeks to form the title compound as colorless needles suitable for X-ray analysis. 1H NMR : \u03b4 9.68 , 7.91 , 6.53 , 6.33 , 3.41 , 1.23 ; 13C NMR  \u03b4 192.2, 169.1, 165.8, 159.5, 157.7, 153.3, 128.3, 108.4, 108.0, 102.8, 96.9, 44.9, 40.6, 29.7, 12.5; LRMS\u2013ESI (negative mode), NaCl was added as a charging agent [M \u2212 2H2O + Cl]\u2212 = 619 m/z, [M \u2212 H2O \u2212 C14H15NO4 + 2Cl]\u2212 = 396 m/z, CID 396 yields [C14H15NO4]\u2212 = 261 m/z; IR (ATR solid); 3364  \u03bdOH, 2972, 2926 (m) \u03bdCH, 1722 (m) \u03bdCO (\u03b4-lactone), 1689 \u03bdCO (ketone), 1590 \u03bdCO (form\u00adyl), 564 \u03bdCO (Zn\u2014O) cm\u22121.7-(Di\u00adethyl\u00adamino)-4-hy\u00addroxy\u00adcoumarin  was dissolved in 2-propanol (20\u2005mL), tri\u00adethyl \u00adorthoformate  and 2-amino\u00adpyriimidine  were added and the solution was heated to reflux for 4\u2005h. Upon cooling, the solid was collected and used without further purification. This compound  was then dissolved in methanol (10\u2005mL), to which Zn(OAc)sp2, 0.99\u2005\u00c5 for CH2, and 0.98\u2005\u00c5 for methyl groups. Those on O atoms were assigned from difference maps, and their positions refined, with O\u2014H distances restrained to 0.86\u2005(1)\u2005\u00c5. Uiso values for H atoms were assigned as 1.2 times Ueq of the attached atoms (1.5 for methyl and water groups).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016009853/zl2668sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016009853/zl2668Isup2.hklStructure factors: contains datablock(s) I. DOI: 1486125CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the title purine derivative, mol\u00adecules are linked by O\u2014H\u22efN, N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming a three-dimensional framework. 7H7N5O3, is an adduct of guanine with glyoxal. In the mol\u00adecule, the di\u00adhydro\u00adimidazole ring adopts a twisted conformation on the C\u2014C bond, and the two hydroxyl groups lie on opposite sides of the mean plane of the ring. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efN hydrogen bonds forming a three-dimensional framework. The crystal packing is reinforced by C\u2014H\u22efO hydrogen bonds and by offset \u03c0\u2013\u03c0 stacking of the purine ring systems of inversion related mol\u00adecules [inter\u00adcentroid distance = 3.4839\u2005(12)\u2005\u00c5].The title purine derivative, C Purine derivatives have been developed as inhibitors of cyclin-dependent kinase \u2005\u00c5, inter\u00adplanar distance = 3.311\u2005(1)\u2005\u00c5, slippage = 1.112\u2005\u00c5; Cg2 and Cg3 are the centroids of the N3/C4/C3/N4/C5 and N1/C1/C4/C3/N2/C2 rings, respectively; symmetry code: (i) \u2212x, \u2212y, \u2212z\u00a0+\u00a02].In the crystal, mol\u00adecules are also linked e Table\u00a01. The laye Table\u00a01. Within e Table\u00a01, and invet al., 2016H-6-one as substructure, gave 61 hits. Many of these compounds concern guanine and guaninium and some metal complexes, but none involve a fused third ring. The structure of the title compound has not been reported previously.A search of the Cambridge Structural Database  medium.The title compound was synthesized according to a literature method  = 1.2Ueq(C) and 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016009087/xu5887sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016009087/xu5887Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016009087/xu5887Isup3.cmlSupporting information file. DOI: 1469976CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III compounds with 4-amino\u00adbenzoic acid and 4-chloro-3-nitro\u00adbenzoic acid, discrete centrosymmetric bridged dinuclear complex units are present giving an overall three-dimensional hydrogen-bonded structure in the first complex and a one-dimensional coordination polymer in the second.In the structures of two Er 2-4-amino\u00adbenzoato-\u03ba2O:O\u2032)bis\u00ad[bisdi\u00adaqua\u00aderbium(III)] dihydrate, [Er2(C7H6NO2)6(H2O)4]\u00b72H2O, (I), and 4-chloro-3-nitro\u00adbenzoic acid (CLNBAH), namely poly[hexa\u00adkis\u00ad(\u03bc2-4-chloro-3-nitro\u00adbenzoato-\u03ba2O:O\u2032)bis\u00ad(dimethyl sulfoxide-\u03baO)dierbium(III)], [Er2(C7H3ClNO4)6(C2H6OS)2]n, (II), have been determined. In the structure of solvatomorphic compound (I), the symmetry-related irregular ErO8 coordination polyhedra in the discrete centrosymmetric dinuclear complex comprise two monodentate water mol\u00adecules and six carboxyl\u00adate O-atom donors, four from two bidentate carboxyl\u00adate O,O\u2032-chelate groups and two from the bis-monodentate O:O\u2032-bridging group of the third 4-ABA anion. The Er\u2014O bond-length range is 2.232\u2005(3)\u20132.478\u2005(3)\u2005\u00c5 and the Er\u22efEr separation in the dinuclear complex unit is 4.7527\u2005(4)\u2005\u00c5. One of the coordinating water mol\u00adecules is involved in an intra-unit O\u2014H\u22efO hydrogen-bonding association with an inversion-related carboxyl\u00adate O-atom acceptor. In contrast, the anhydrous compound (II) is polymeric, based on centrosymmetric dinuclear repeat units comprising ErO7 coordination polyhedra which involve four O-atom donors from two bidentate O:O\u2032-bridging carboxyl\u00adate groups, one O-atom donor from the monodentate dimethyl sulfoxide ligand and two O-atom donors from the third bridging CLNBA anion. The latter provides the inter-unit link in the one-dimensional coordination polymer extending along [100]. The Er\u2014O bond-length range in (II) is 2.239\u2005(6)\u20132.348\u2005(6)\u2005\u00c5 and the Er\u22efEr separation within the dinuclear unit is 4.4620\u2005(6)\u2005\u00c5. In the crystal of (I), extensive inter-dimer O\u2014H\u22efO and N\u2014H\u22efO hydrogen-bonding inter\u00adactions involving both the coordinating water mol\u00adecules and the solvent water mol\u00adecules, as well as the amine groups of the 4-ABA anions, give an overall three-dimensional network structure. Within this structure are also weak \u03c0\u2013\u03c0 ring inter\u00adactions between two of the coordinating ligands [ring-centroid separations = 3.676\u2005(3) and 3.711\u2005(2)\u2005\u00c5]. With (II), only weak intra-polymer C\u2014H\u22efO, C\u2014H\u22efCl and C\u2014H\u22efS inter\u00adactions are present.The crystal structures of two erbium(III) complexes with 4-amino\u00adbenzoic acid (4-ABAH), namely bis\u00ad(\u03bc RE) metals has been investigated extensively and the structures of a large number of complexes with various ligand types are known  series of complexes  (La\u2013Tb as well as Dy and Er), in which the structures are two-dimensional, the second triclinic (P2(4-ABA)6(H2O)2]; triclinic [[Tb2(4-ABA)6(H2O)2]\u00b72H2O]} is of inter\u00adest and its occurrence was indicated as being dependent on pH control in the preparation.The coordination chemistry of the rare earth (RE series (predominantly triclinic) might also show the same effect so this was tested with Er in a reaction of erbium(III) acetate with 4-ABA in aqueous ethanol under mild reaction conditions, with no additional pH control. The title triclinic complex [Er2(C7H6NO2)6(H2O)4]\u00b72H2O, (I)3+ complex with 4-ABA , b = 11.0117\u2005(1), c = 12.7430\u2005(2)\u2005\u00c5, \u03b1 = 89.372\u2005(5), \u03b2 = 72.0360\u2005(6), \u03b3 = 75.0730\u2005(7)\u00b0, V = 1169.97\u2005(2)\u2005\u00c53, confirming that the two are isotypic.It was considered that some of the other later members of the 2(C7H3ClNO4)6(C2H6OS)2]n, was obtained in a similar reaction to (I)Complex (II)8 complex units  , four O-atom donors from two slightly asymmetric bidentate O,O\u2019 chelate carboxyl\u00adate groups (the A and B 4-ABA ligands) and two bridging O-atom donors from two symmetry-related ligands (C). The Er\u22efEri separation in the dinuclear unit is 4.7527\u2005(4)\u2005\u00c5. Unlike the polymeric solvatomorphic ErIII complex [Er2(4-ABA)6(H2O)2]n\u00b7nH2O carboxyl\u00adate hydrogen bond is present between one of the the coordinating water mol\u00adecules (O1W) and an inversion-related carboxyl\u00adate O-atom (O11Ai) ] Table\u00a01, compris) Table\u00a02. This stO,O\u2032-chelate ligands (A) and the bridging ligand (C), the groups are essentially coplanar with the benzene ring , while in the second bidentate chelate ligand (B) the group is rotated out of the plane [corresponding torsion angle = 155.9\u2005(4)\u00b0]. Such a \u2019planar\u2019 conformation is also found in the structure of the parent acid III atoms , a monodentate DMSO O-atom and O-donors (O12Ci) and O11Ci from the C ligand which extends the dinuclear unit into a one-dimensional coordination polymer lying along [100] \u2005\u00c5. Also present within the repeat unit are a C2B\u2014H\u22efO11 hydrogen bond [3.298\u2005(13)\u2005\u00c5] and a C2A\u2014H\u22efS1 inter\u00adaction [3.743\u2005(10)\u2005\u00c5] ms Fig.\u00a02 being se0] Fig.\u00a03. The Er\u20140] Fig.\u00a03 and the ] Table\u00a04.A/B/C\u2014C1A/B/C\u2014C11A/B/C\u2014O11A/B/C = 158.7\u2005(9), 177.2\u2005(9) and 160.3\u2005(8)\u00b0, respectively. The torsion angles of the nitro groups C2A/B/C\u2014C3A/B/C\u2014N3A/B/C\u2014O32A/B/C are \u2212150.4\u2005(12), 174.1\u2005(16) and 120.3\u2005(13)\u00b0, respectively. In the structure of the parent CLNBAH acid water and Ocarbox\u00adyl hydrogen bonds give a three-dimensional network structure \u2005\u00c5] and C ligands [C\u22efCviii = 3.676\u2005(3)\u2005\u00c5] 6(H2O)4]2\u00b76H2O e Figs. 4 and 5 \u25b8.With (II)The title compounds were synthesized by warming together for 10\u2005min, a solution obtained by mixing 5\u2005ml of ethano\u00adlic 4-amino\u00adbenzoic acid (1\u2005mmol: 135\u2005mg) [for (I)] or 4-chloro-3-nitro\u00adbenzoic acid (1\u2005mmol: 200\u2005mg) [for (II)], with 10\u2005ml of aqueous erbium(III) acetate hexa\u00adhydrate (0.3\u2005mmol: 216\u2005mg). Partial room-temperature evaporation of these solutions provided pale-pink block-like single crystals of (I)Uiso(H) = 1.5Ueq(O) or 1.2Ueq(N). Other H atoms were included in the refinement at calculated positions , using a riding-model approximation. In the refinement of (II)\u22123) located within 1.0\u2005\u00c5 of the Er1 site were present. These are possibly due to poor crystal quality coupled to effects of an insufficient absorption correction.Crystal data, data collection and structure refinements for (I)10.1107/S2056989015020319/wm5228sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015020319/wm5228Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015020319/wm5228IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1433543, 1433542CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-[3-(di\u00admethyl\u00adamino)\u00adprop\u00adyl]-N\u2032-(2-hy\u00addroxy\u00adphen\u00adyl)oxamide trianion bridges two CuII cations to form the binuclear complex, in which the CuII cations have distorted square-planar and square-pyramidal coordination geometries.The  2(C13H16N3O3)(C12H6N2O2)(H2O)]ClO4\u00b70.5H2O, consists of a cis-oxamide-bridged binuclear CuII complex cation, a perchlorate anion and half a solvent water mol\u00adecule. One CuII cation is N,N\u2032,N\",O-chelated by an N-[3-(di\u00admethyl\u00adamino)\u00adprop\u00adyl]-N\u2032-(2-hy\u00addroxy\u00adphen\u00adyl)oxamide trianion in a distorted square-planar geometry, whereas the other CuII cation is O,O\u2032-chelated by the oxamide moiety of the anion and N,N\u2032-chelated by a 1,10-phenanthroline-5,6-dione mol\u00adecule, and a water mol\u00adecule further coordinates the second CuII cation, completing a distorted square-pyramidal coordination geometry. In the crystal, classical O\u2014H\u22efO hydrogen bonds, weak C\u2014H\u22efO hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions link the complex cations, anions and solvent water mol\u00adecules into a three-dimensional supra\u00admolecular architecture. In the crystal, the di\u00admethyl\u00adamino\u00adpropyl unit of the oxamide anion is disordered over two positions with an occupancy ratio of 0.561\u2005(11):0.439\u2005(11); the solvent water mol\u00adecule is also disordered over two positions, the occupancy ratio being 0.207\u2005(10):0.293\u2005(10).The title compound, [Cu Its crystal structure and supra\u00admolecular structure are reported here. 1,10-Phenanthroline-5,6-dione (Phdo) is a multifaceted ligand since the structure and electronic properties thereof incorporate the features of the di\u00adimine and quinone functionalities \u2005\u00c5, which is consistent with structures reported previously \u2005\u00c5 for N4], and a water mol\u00adecule (O4) occupies the apical position, completing a distorted square-pyramidal coordination geometry with a \u03c4 value of 0.06  cations with three planar five-membered chelate rings and one six-membered ring, the latter being disordered over two positions. The puckering parameters of the first component (containing atoms C10A and C11A) are Q = 0.554\u2005(8)\u2005\u00c5, \u03b8 = 47.6\u2005(6)\u00b0 and \u03d5 = 206.0\u2005(7)\u00b0, and those of the other are Q = 0.565\u2005(11)\u2005\u00c5, \u03b8 = 123.4\u2005(8)\u00b0 and \u03d5 = 38.8\u2005(9)\u00b0; both suggest an approximate half-chair conformation.The hexa\u00addentate oxamide anion, Dmapoxx, 1\u00a0\u2212\u00a0y, \u2212z [symmetry code (iv)], and vice versa , 3.211\u2005(4) (C3iv) and 3.252\u2005(4)\u2005\u00c5 (C19iv).Besides classical O\u2014H\u22efO hydrogen bonds, weak C\u2014H\u22efO hydrogen bonds and aromatic stacking inter\u00adactions are important to the supra\u00admolecular structure. As illustrated in Fig.\u00a02sa Fig.\u00a03. The sepII complexes of 1,10-phenanthroline-5,6-dione have been reported previously, for example, Chetana et al. \u00adprop\u00adyl]-N\u2032-2-(oxidophen\u00adyl)oxamide 2\u00b76H2O  in methanol (5\u2005ml) was added dropwise to a solution of H3Dmapox  and piperidine  in methanol (5\u2005ml). The solution was stirred continuously for 0.5\u2005h. Then a solution of Phdo  in methanol (5\u2005ml) was added dropwise, and the mixture was stirred continuously at 313\u2005K for 6\u2005h and then filtered. Dark-blue crystals of the title compound suitable for X-ray analysis were obtained from the filtrate by slow evaporation at room temperature for 7\u2005d. Yield: 0.026\u2005g (71.62%). Analysis calculated for Cu2C25H25ClN5O10.5: C 41.44, H 3.48, N 9.67%; found: C 42.57, H 3.15, N 9.19%.A\u2013C13A, with occupancies of 0.561\u2005(11); C10B\u2013C13B, 0.439\u2005(11)], three oxygen atoms of the perchlorate ion  and the solvent water mol\u00adecule ; O7B, 0.293\u2005(10)]. The occupancies were refined freely except for the sum of atoms O7A and O7B which was fixed at 0.5. Some restraints on distances (DFIX) and anisotropic displacement parameters (SIMU) were applied to the disordered atoms to avoid unreasonable geometries. The hydrogen atoms of the water mol\u00adecules were found in a difference Fourier map and then refined as riding. Other H atoms were placed in calculated positions, with C\u2014H = 0.96 (meth\u00adyl), 0.97 (methyl\u00adene) and 0.93\u2005\u00c5 (aromatic), and refined using a riding model, with Uiso(H) = 1.2 Ueq(C) or 1.5 for methyl groups.Crystal data, data collection, and refinement details are summarized in Table\u00a0310.1107/S2056989015009391/xu5850sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015009391/xu5850Isup2.hklStructure factors: contains datablock(s) I. DOI: 1401557CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The latter is coordinated by two Cl atoms and two N,N\u2032-di\u00admethyl\u00adthio\u00adurea (Dmtu) ligands through their S atoms, defining a distorted tetra\u00adhedral coordination sphere with bond angles in the range 102.47\u2005(4)\u2013118.32\u2005(4)\u00b0. Intra- and inter\u00admolecular hydrogen bonds of the type N\u2014H\u22efCl with S(6) and R22(12) ring motifs are present. The inter\u00admolecular contacts make up polymeric chains extending parallel to [101].The mol\u00adecular structure of the title compound, [HgCl L) or derivatives thereof have shown that in combination with a halide or pseudohalide X, some of the complexes exist as mononuclear species [HgX2L2] 2 complexes with methyl\u00adthio\u00adurea as an auxiliary ligand  complexes with thio\u00adurea ligands (2 with di\u00admethyl\u00adthio\u00adurea (Dmtu) as an additional ligand, [HgCl2(C3H8N2S)2], (I)In this article, we report on synthesis and crystal structure of HgCl2L2] complexes et al., 1995S(6) loop motifs 2] 2] 2] 2Cl2] and [Hg(tetra\u00admethyl\u00adthio\u00adurea)2Cl2] 2] and [CdBr2(Dmtu)2], the coordination spheres around Cd deviate only slightly from ideal tetra\u00adhedral values. On the other hand in [Hg(Dmtu)2(CN)2], the HgII atom exhibits a severely distorted tetra\u00adhedral coordination sphere with bond angles in the range 94.31\u2005(2) to 148.83\u2005(13)\u00b0  HgClUiso(H) = 1.5Ueq(C) and Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015015406/wm5202sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015015406/wm5202Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419298CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In both dimers, the platinum(II) complexes are arranged anti\u00adparallel to each other. Each complex exhibits a slightly distorted square-planar coordination environment around the central Pt(II) atom. The dihedral angles between two chelate rings including the PtII atom in these complexes are 0.08\u2005(12) and 1.54\u2005(9)\u00b0.The title cyclo\u00admetalated platinum(II) complex with 2-(4-bromo\u00adphen\u00adyl)pyridinato and acetyl\u00adacetonato ligands, [Pt(C Although these complexes afford luminescence in the solid state, their crystal structures have not been sufficiently explored. We report herein the crystal structure of the cyclo\u00admetalated platinum(II) complex with 2-(4-bromo\u00adphen\u00adyl)pyridinato  and acetyl\u00adacetonato  ligands, [Pt(Brppy)(acac)].Square-planar cyclo\u00admetalated platinum(II) complexes with luminescent properties have recently attracted attention because of their potential applications  are slightly distorted from an ideal square-planar configuration, with angles around Pt1 in the range 81.89\u2005(18)\u201393.04\u2005(17)\u00b0 and around Pt2 in the range 81.73\u2005(18)\u201393.57\u2005(16)\u00b0. The Pt\u2014C bond lengths [Pt1\u2014C11 = 1.970\u2005(5) and Pt2\u2014C27 = 1.969\u2005(5)\u2005\u00c5] are slightly shorter than the Pt\u2014N bond lengths [Pt1\u2014N1 = 1.995\u2005(4) and Pt2\u2014N2 = 1.999\u2005(4)\u2005\u00c5] due to the stronger electron-donating ability of a C atom compared to that of an N atom. Pt\u2014O bond lengths are compiled in Table\u00a01The asymmetric unit of the title compound contains two complex mol\u00adecules with very similar configurations (r.m.s. deviation of fit of two molecules = 0.07\u2005\u00c5). The structure of one of the complex mol\u00adecules of the title compound is shown in Fig.\u00a01II complex (Pt1) is directed to the b axis, on the other hand, that of the other complex (Pt2) is directed to the a axis. The shortest inter\u00admolecular contacts are C4\u22efC15i = 3.406\u2005(7) and C22\u22efO3ii = 3.402\u2005(6)\u2005\u00c5 . Weak C\u2014H\u22efO and C\u2014H\u22efBr inter\u00adactions might also help to consolidate the crystal packing  and Pt2\u22efPt2ii = 3.723\u2005(1)\u2005\u00c5] are longer than the van der Waals diameter of the Pt atom (\u03bc-Cl)]2 ([Pt(C\u03bc2:-Cl)] A mixture of 2-(4-bromo\u00adphen\u00adyl)pyridine  and K2PtCl4  in a 2-eth\u00adoxy\u00adethanol\u2013water mixture (45\u2005ml/15\u2005ml) was stirred for 6\u2005h at 333\u2005K under an Ar atmosphere. After cooling to room temperature, the yellow\u2013green precipitate was filtered off, washed with di\u00adchloro\u00admethane, and dried in vacuo. Yield: 0.535\u2005g, (48.2%).11H7BrN)(C5H7O2)]:: 262\u2005(29800), 280\u2005(27500), 317 , 330 , 363\u2005(6400), 389\u2005(4200). 1H NMR ; 8.97 , 7.81 , 7.71 , 7.57 , 7.31-7.45 , 7.14 , 5.48 , 2.03 , 2.01 .Analysis found  = 1.2Ueq(C) for Csp2\u2013H, and Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015017478/wm5214sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015017478/wm5214Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015017478/wm5214Isup3.tifSupporting information file. DOI: 1425736CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(11-hy\u00addroxy\u00adundec\u00adyl)isoxazole-3-carboxamide hemihydrate, a derivative of anti\u00adviral \u2018WIN compounds\u2019, are reported.The crystal structure and supra\u00admolecular features of 5-{3-prop\u00adyl}- 29H42N4O5\u00b70.5H2O, comprises four structural units. A flexible prop\u00adyloxy unit in a gauche conformation, with a \u2013C(H2)\u2014C(H2)\u2014C(H2)\u2014O\u2013 torsion angle of \u221264.32\u2005(18)\u00b0, connects an isoxazole ring and an approximately planar phenyl\u00adoxa\u00addiazole ring system [with a maxixmum devation of 0.061\u2005(2)\u2005\u00c5], which are oriented almost parallel to one another with a dihedral angle of 10.75\u2005(7)\u00b0. Furthermore, a C11-alkyl chain with a terminal hy\u00addroxy group links to the 3-position of the isoxazole ring via an amide bond. In the crystal, a half-occupancy solvent water mol\u00adecule connects to a neighbouring mol\u00adecule via an inter\u00admolecular O\u2014H\u22efO(water) hydrogen bond to the C11-alkyl chain hy\u00addroxy group.The title compound, C The three heterocyclic rings are approximately coplanar to one another, having dihedral angles between the rings of 11.57\u2005(8) (C19\u2013C21/N22/O23 and C7\u2013C12), 10.68\u2005(9) (C19\u2013C21/N22/O23 and C2/O3/N4/C5/N6) and 4.81\u2005(9)\u00b0 (C7\u2013C12 and C2/O3/N4/C5/N6), maintaining the WIN framework in a linear conformation. The dihedral angle between the isoxazole ring (C19\u2013C21/N22/O23) and the approximately planar phenyl\u00adoxa\u00addiazole ring system  is 10.75\u2005(7)\u00b0. The isoxazole and phenyl\u00adoxa\u00addiazole ring systems are connected by a prop\u00adyloxy unit (O15\u2013C18), which is in a gauche conformation, with a C18\u2014C17\u2014C16\u2014O15 torsion angle of \u221264.32\u2005(18)\u00b0. The amide group (N26\u2013C24) at the 3-position of the isoxazole ring which joins the C11-alkyl chain (C27\u2013O38) and the WIN framework is likewise almost coplanar with the isoxazole ring, with a dihedral angle of 10.92\u2005(9)\u00b0 between the amide (H26/N26/C24/O25) and isoxazole planes. The amide hydrogen (H26) and the acidic isoxazole hydrogen (H20) are on opposite sides, with a torsion angle (N26\u2014C24\u2014C21\u2014C20) of 172.31\u2005(15)\u00b0. The C11-alkyl chain (C27\u2013C37) is in an all-anti conformation, with an average torsion angle of 178.80\u00b0. The WIN framework and the C11-linker arm structural units are aligned roughly in a 160\u00b0 angle and the total length of the title mol\u00adecule measures up to 3.4\u2005nm.The mol\u00adecular structure of the title compound is shown in Fig.\u00a0111-alkyl chain hy\u00addroxy [O\u2014H\u22efO = 1.90\u2005(1)\u2005\u00c5], solvent water [O\u2014H\u22efO = 1.87\u2005(1)\u2005\u00c5], amide carbonyl and isoxazole hydrogen (C\u2014H\u22efO = 2.56\u2005\u00c5) groups of two parallel neighbouring mol\u00adecules  and The title compound packs in the crystal lattice in layers, in which the mol\u00adecules are held together by solvent-mediated O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds (motif 1), as well as C\u2014H\u22efN and C\u2014H\u22efO inter\u00admolecular inter\u00adactions between the heterocyclic isoxazole and phenyl\u00adoxa\u00addiazole units of neighbouring mol\u00adecules (motif 2) Table\u00a01. In the es Fig.\u00a02. In a sips Fig.\u00a02.et al., 2014et al., 2014et al., 2014et al., 2004et al., 2014et al., 2004et al., 2014et al., 2014ca 60.8\u00b0. In all of the structures, the prop\u00adyloxy unit is in a gauche conformation, with torsion angles in the range 62.4\u201369.2\u00b0.A search of the Cambridge Structural Database \u00adprop\u00adyl]-N-ethyl\u00adcarbodi\u00adimide (0.19\u2005mmol) and a catalytic amount of 1-hy\u00addroxy\u00adbenzotriazole at 273\u2005K gave the title compound in 68% yield after subsequent chromatographic purification in silica with a di\u00adchloro\u00admethane\u2013methanol mixture (95:5 v/v). Needle-like crystals of the title compound were obtained from an ethanol solution by vapor diffusion with water.An amide coupling reaction of 5-{3-prop\u00adyl}isoxazole-3-carb\u00adoxy\u00adlic acid  = 1.5Ueq(C) for methyl and 1.2Ueq(C) for other H atoms, and N\u2014H = 0.88\u2005\u00c5 and Uiso(H) = 1.2Ueq(N). The positions of the O-bound H atoms were located in a difference Fourier map and refined as riding atoms with Uiso(H) = 1.5Ueq(O). The O\u2014H distance of the half-occupied water molecule was restrained to 0.84\u2005(1)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015007367/lh5758sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015007367/lh5758Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015007367/lh5758Isup3.cmlSupporting information file. DOI: 1059505CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: interactive version of Fig. 3Enhanced figure:"}
{"text": "The basal plane consists of two N atoms [Cu\u2014N = 2.008\u2005(3) and 2.032\u2005(3)\u2005\u00c5] from the phenanthroline ligand, and of two carboxyl\u00adate O atoms [Cu\u2014O = 1.942\u2005(3) and 1.948\u2005(3)\u2005\u00c5] from two 2,3,4,5-tetra\u00adfluoro\u00adbenzoate anions. Another 2,3,4,5-tetra\u00adfluoro\u00adbenzoate anion provides the apical carboxyl\u00adate O atom [Cu\u2014O = 2.262\u2005(3)\u2005\u00c5] and bridges two CuII ions into a binuclear centrosymmetric dimer. Intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between one of the tetra\u00adfluoro\u00adbenzene rings and the middle of the phenenanthroline rings [3.617\u2005(3)\u2005\u00c5] stabilize the mol\u00adecular configuration. O\u2014H\u22efO hydrogen bonds between the lattice water mol\u00adecules and the unbound carboxyl\u00adate O atoms of the metal complexes leads to the formation of a chain structure parallel to [100].In the title compound, [Cu DOI: 10.1107/S1600536814022065/wm5062Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814022065/wm5062fig1.tifx y z . DOI: x\u00a0+\u00a01, \u2013y\u00a0+\u00a01, \u2013z\u00a0+\u00a02.The mol\u00adecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms. The non-labelled atoms are generated by symmetry code \u2013Click here for additional data file.10.1107/S1600536814022065/wm5062fig2.tif. DOI: The packing of the mol\u00adecular entities of the title compound. O\u2014H\u22efO hydrogen-bonding inter\u00adactions are indicated by dashed lines.1027857CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion atom is octa\u00adhedrally coordinated in di\u00adaqua\u00adtris\u00ad(1-ethyl-1H-imidazole)\u00adsulfato\u00adnickel(II). There are three organic ligands, two water and the sulfate anion coordinated around the NiII centre. Two complex mol\u00adecules form an inversion dimer via two pairs of O\u2014H\u22efO hydrogen bonds between the coordinating sulfate anion and a water mol\u00adecule in the unit cell.The Ni 4)(C5H8N2)3(H2O)2], the NiII ion is coordinated by three facial 1-ethyl-1H-imidazole ligands, one monodentate sulfate ligand and two water mol\u00adecules in a slightly distorted octa\u00adhedral coordination environment. In the crystal, two pairs of O\u2014H\u22efO hydrogen bonds link complex mol\u00adecules, forming inversion dimers incorporating R24(8), R22(8) and R22(12) rings. The dimeric unit also contains two symmetry-unique intra\u00admolecular O\u2014H\u22efO hydrogen bonds. In addition, weak C\u2014H\u22efO hydrogen bonds, weak C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions with a centroid\u2013centroid distance of 3.560\u2005(2)\u2005\u00c5 combine to form a three-dimensional network. One of the ethyl groups is disordered over two sets of sites with occupancies in the ratio 0.586\u2005(7):0.414\u2005(7).In the title complex, [Ni(SO H-imidazole mol\u00adecules as ligands. The title compound was prepared by the reaction of NiSO4\u00b76H2O and 1-ethyl-1H-imidazole. The crystal structure of the title compound is presented herein.In spite of efforts in the past decades to synthesize structurally highly varying metal-organic complexes, no structures up to this point have been reported which contain the combination of a hydro\u00adphilic sulfate anion, water mol\u00adecules and hydro\u00adphobic 1-ethyl-1II ion is coordinated in a slightly distorted octa\u00adhedral geometry by three facially arranged 1-ethyl-1H-imidazole ligands, one monodentate sulfate ligand and two water mol\u00adecules. The Ni\u2014N bond lengths are in the range 2.0630\u2005(16)\u20132.0817\u2005(17)\u00c5 and the Ni\u2014O bond lengths are in the range 2.1195\u2005(15)\u20132.1502\u2005(14). The Niii ion is displaced by 0.1038\u2005(3)\u2005\u00c5 from the O1/O2/N11/N13 plane. The distances of two water O atoms O1 and O2 from the S1/O3/Ni1/N12 plane are the same within experimental error, with values of 1.520\u2005(2) and \u22121.504\u2005(2)\u2005\u00c5, respectively. The sulfate atom O6 is displaced by only 0.144\u2005(2)\u2005\u00c5 from the S1/O3/Ni1/N12 plane, while atoms O4 and O5 are displaced by 1.114\u2005(2) and \u22121.298\u2005(2)\u2005\u00c5, respectively, from this plane .In the crystal, two pairs of O\u2014H\u22efO hydrogen bonds Table\u00a01 link comds Fig.\u00a03. In addiet al., 2004et al., 2003et al., 2009et al., 2006et al., 1995et al., 2011et al., 2002et al., 2000A search of the Cambridge Structural Database  I. DOI: 10.1107/S2056989016002863/lh5802Isup2.hklStructure factors: contains datablock(s) I. DOI: 1454040CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the complex cation, two MnII atoms are bridged by two O atoms of two different 2-benzoyl\u00adbenzoate ligands, each MnII atom being further coordinated by two 2,2\u2032-bi\u00adpyridine (bipy) ligands in a distorted octa\u00adhedral environment. Within the binuclear mol\u00adecule, the Mn\u22efMn separation is 4.513\u2005(7)\u2005\u00c5. Inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef \u03c0 inter\u00adactions link the mol\u00adecules into a three-dimensional network. The title compound, [Mn DOI: 10.1107/S2056989015023671/bg2577Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015023671/bg2577fig1.tifx y z . DOI: x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a02.The mol\u00adecular structure of the title compound, (displacement ellipsoids are shown at 50% probability levels). Symmetry code: (i) \u2212Click here for additional data file.10.1107/S2056989015023671/bg2577fig2.tifc . DOI: c axis, showing O\u2014H\u22efO, C\u2014H\u22efC hydrogen bonds and C\u2014H\u22ef \u03c0, and \u03c0\u2013\u03c0 stacking inter\u00adactions drawn as dotted lines.Packing view drawn along the 1014518CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, weak C\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions connect mol\u00adecules forming a three-dimensional network.In the title mol\u00adecule, C 21H20ClF2NO2, the piperidine ring adopts a slightly distorted boat conformation. The two benzene rings form a dihedral angle of 87.43\u2005(1)\u00b0. A weak intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction is observed. In the crystal, weak C\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions connect the mol\u00adecules, forming a three-dimensional network.In the title mol\u00adecule, C The N1\u2014C14 [1.356\u2005(2)\u2005\u00c5] and C14\u2014O1 [1.221\u2005(2)\u2005\u00c5] bond distances indicate the presence electron delocalization in this part of the mol\u00adecule. The six-membered piperidine ring adopts a slightly distorted boat conformation. The benzene rings form a dihedral angle of 87.43\u2005(1)\u00b0. The equatorial and axial orientation of the methyl substituents bonded to atom C2 are described by the N1\u2014C1\u2014C2\u2014C6 and N1\u2014C1\u2014C2\u2014C7 torsion angles of \u2212117.45\u2005(16)\u00b0 and \u221257.2\u2005(2)\u00b0, respectively. A weak intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction is observed, which involves the C8\u2013C13 benzene ring -t-3,t-5-di\u00admethyl\u00adpiperidin-4-one [50.4\u2005(1)\u00b0] -c-3,t-3-di\u00admethyl\u00adpiperidin-4-one [77.23\u2005(7)\u00b0] -t-3-isopropyl-1-nitro\u00adsopiperidin-4-one [21.56\u00b0] -t-3-iso\u00adpropyl\u00adpiperidin-4-one [52.4\u2005(1)\u00b0]  piperidin-4-one , and tri\u00adethyl\u00adamine  in benzene (20\u2005ml), di\u00adchloro\u00adacetyl\u00adchloride  in benzene (20\u2005ml) was added dropwise for about half an hour. Stirring was continued with mild heating using a magnetic stirrer for 7\u2005h. The progress of the reaction was monitored by TLC. After the completion of reaction, it was poured into water and extracted with ether. The collected ether extracts were then washed well with 3% sodium bicarbonate solution and dried over anhydrous Na2SO4. The pasty mass obtained was purified by crystallization from a benzene\u2013petroleum ether solution (333\u2013353\u2005K) in the ratio of 95:5. X-ray quality crystals were grown by slow evaporation of an ethanol solution of the title compound at ambient temperature.The synthesis followed the procedure of Aridoss  al. 2007. To a stUiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814021278/lh5727sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814021278/lh5727Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814021278/lh5727Isup3.tifSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814021278/lh5727Isup4.cmlSupporting information file. DOI: 1026047CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ligand adopts an E conformation and the gold(I) atom displays the expected linear geometry with a Cl atom also bonded to the metal ion [Cl\u2014Au\u2014S = 174.23\u2005(5)\u00b0]. One of the pyridyl rings is protonated, giving the gold complex an overall positive charge. Two solvent water mol\u00adecules, one of which is located on a twofold rotation axis, and a non-coordinating chloride ion complete the structural assembly. The mol\u00adecular structure is stabilized by intra\u00admolecular and inter\u00admolecular N\u2014H\u22efCl, N\u2014H\u22efN, O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonding.The title complex, [AuCl(C They are compounds that can coordinate to transition metals and exhibit keto\u2013enol tautomerism  of the starting material [HPy][AuClsp hybridization of the metal.The gold(I) atom displays the expected linear geometry, with a Cl\u2014Au\u2014S coordination angle of 174.23\u2005(5)\u00b0, close to the ideal angle of 180\u00b0 expected for et al., 2006The C12\u2014S1 bond length reported for di-2-pyridyl ketone phenyl\u00adthio\u00adsemicarbazone is 1.676\u2005(2)\u2005\u00c5 and it is lengthened to 1.713\u2005(4)\u2005\u00c5 on coordination to gold; this is typical of the ketone form with a concomitant shortening of the N3\u2014N4 bond  in 5\u2005ml of CH3CN. A clear yellow solution was formed after heating the mixture to reflux for three\u2005h. Orange crystals deposited upon slow cooling of the solvent. Yield: 69%, m.p. 491\u2005K. Elemental analysis, found: C, 33.71; H, 3.15; N, 10.04%; calculated for C36H38Au2Cl4N10O3S2: C, 33.87; H, 3.16; N, 10.97%. IR (\u03bdmax cm\u22121): 3421 (O\u2014H), 3281 (N\u2014H), 2927 (N\u2014H+), 1694 (C=N), 1150 (N\u2014N), 765 (C=S).Di-2-pyridyl ketone phenyl\u00adthio\u00adsemicarbazone (1\u2005mmol) was dissolved in about 5\u2005ml of CHUiso = 1.5Ueq(O). Other H atoms were included in the refinement at calculated positions and treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015480/zl2637sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015480/zl2637Isup3.hklStructure factors: contains datablock(s) I. DOI: 1419509CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains a [1-NaMePy]+ cation and one half of an Ni(imnt)22\u2212 anion. The NiII ion lies on an inversion centre and adopts a square-planar configuration with Ni\u2014S bond lengths of 2.200\u2005(1) and 2.216\u2005(1)\u2005\u00c5. In the [1-NaMePy]+ cation, the naphthyl ringsystem and the pyridinium ring make a dihedral angle of 90.0\u2005(2)\u00b0. In the crystal, C\u2014H\u22efN and C\u2014H\u22efNi hydrogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions between the chelate ring and the pyridinium ring [centroid\u2013centroid distance = 3.675\u2005(2)\u2005\u00c5] link the ions into a three-dimensional network.A new ion-pair complex, (C Transition metal complexes with di\u00adthiol\u00adate ligands such as 2,2-di\u00adcyano\u00adethene-1,1-di\u00adthiol\u00adate (imnt) or 1,2-di\u00adcyano\u00adethene-1,2-di\u00adthiol\u00adate (mnt) are important mol\u00adecular materials with inter\u00adesting electrical conductivity, superconductivity, optical and magnetic properties 22\u2212 anion located about an inversion center. The NiS4 core exhibits a square-planar configuration, with Ni\u2014S bond lengths of 2.200\u2005(1) and 2.216\u2005(1)\u2005\u00c5. The S1\u2014Ni1\u2014S2 bond angle within the four-membered ring (Ni1/S1/C1/S2) is 78.91\u2005(3)\u00b0. The N1 and N2 atoms of the C\u00a0N groups deviate from the Ni1/S1/C1/S2 plane by 0.078\u2005(3) and 0.169\u2005(3)\u2005\u00c5, respectively. The [1-NaMePy]+ cation adopts a conformation in which both the naphthyl ring system and the pyridinium ring are twisted with respect to the N3/C11/C10 reference plane, making dihedral angles of 10.5\u2005(2)\u00b0 and 87.3\u2005(3)\u00b0, respectively. The naphthyl ring system and the pyridinium ring make a dihedral angle of 90.0\u2005(2)\u00b0.The asymmetric unit of the title compound consists of one [1-NaMePy]22\u2212 anion and [1-NaMePy]+ cation. The first is a \u03c0\u2013\u03c0 contact between the chelate ring  of the anion and the pyridinium ring of the cation on Fig.\u00a02 with a don Fig.\u00a02. The comon Fig.\u00a02.22\u2212 anion have been reported, typical examples being [TBA]2[Ni(imnt)2] and [4NO2BzPy]2[Ni(imnt)2]  2] [4FBzPy is 1-(4-fluoro\u00adbenz\u00adyl)pyrid\u00adin\u00adium] 2] (Bz2NH2Py is 1-benzyl-2-amino\u00adpyridinium) 2] [BzDMAP is 1-benzyl-4-(di\u00admethyl\u00adamino)\u00adpyridinium] 2] and [2-NaMe-4-MePy]2[Ni(imnt)2]  2] and [Bz-4-MeQl]2[Ni(imnt)2]  al., 2009. For a d al. 2013.2\u00b76H2O, K2imnt and 1-(4-naphthyl\u00admethyl\u00adene)pyridinium bromide in water  = 0.93\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for aromatic and d(C\u2014H) = 0.97\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for CH2 atoms. Crystal data, data collection and structure refinement details are summarized in Table\u00a02All H-atoms were positioned geometrically and refined using a riding model with 10.1107/S1600536814017012/kp2472sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814017012/kp2472Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814017012/kp2472Isup3.cmlSupporting information file. DOI: 1015644CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In both cases, the Pd2+ cations are coordinated by the Se and N atoms of the chelating bidentate 2-[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]benzene\u00adseleno\u00adlate ligand. The chloride ligand lies trans to selenium and the tri\u00adphenyl\u00adphosphane ligand is trans to nitro\u00adgen. The Pd\u2014Se bond lengths in the two independent coordination environments of Pd are 2.3801\u2005(4) and 2.3852\u2005(4)\u2005\u00c5, the Pd\u2014P bond lengths are 2.2562\u2005(8) and 2.2471\u2005(8)\u2005\u00c5, the Pd\u2014N bond lengths are 2.172\u2005(2) and 2.158\u2005(2)\u2005\u00c5, and the Pd\u2014Cl bond lengths are 2.3816\u2005(8) and 2.3801\u2005(8)\u2005\u00c5. The square-planar coordination around one Pd2+ cation is less distorted than that around the other.The asymmetric unit of the title compound, [PdCl(C DOI: 10.1107/S1600536814010678/nk2221Isup2.hklStructure factors: contains datablock(s) I. DOI: 1002116CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The backbone torsion angles  for \u03b23,3-Ac6c-OH are restricted to gauche conformations in all the derivatives, with a chair conformation of the cyclo\u00adhexane ring. In the crystal structure of (I), the packing of mol\u00adecules shows both carb\u00adoxy\u00adlic acid R22(8) O\u2014H\u22efO and centrosymmetric R22(14) N\u2014H\u22efO hydrogen-bonding inter\u00adactions, giving rise to chains along the c-axis direction. In (II), centrosymmetric carb\u00adoxy\u00adlic acid R22(8) O\u2014H\u22efO dimers are extended through N\u2014H\u22efO hydrogen bonds and together with inter-ring \u03c0\u2013\u03c0 inter\u00adactions between Fmoc groups [ring centroid distance = 3.786\u2005(2)\u2005\u00c5], generate a layered structure lying parallel to (010). In the case of compound (III), carb\u00adoxy\u00adlic acid O\u2014H\u22efNpyrazine hydrogen bonds give rise to zigzag ribbon structures extending along the c-axis direction.N-Protected derivatives of 1-amino\u00adcyclo\u00adhexa\u00adneacetic acid (\u03b2 Valeroyl-\u03b23,3-Ac6c-OH (I)3,3-Ac6c-OH (II)3,3-Ac6c-OH (III)In order to investigate the effect of protecting groups and disubstitution on the conformation of \u03b2-amino acids, N-protected derivatives of 1-amino\u00adcyclo\u00adhexa\u00adneacetic acid 3,3-Ac6c-OH (II)3,3-Ac6c-OH (III)B \u2014C1A and N1\u2014C1B\u2014C1A\u2014C1\u2032) adopt a gauche conformation in all three compounds . In a 3,3-disubstituted \u03b2-amino acid residue, \u03b23,3-Ac6c-OH, the cyclo\u00adhexane ring imposes a restriction on the torsion angles \u03d5 and \u03b8. The protecting groups at the N-terminus of (I)trans geometry [\u03c90 (C4\u2014C0\u2032\u2014N1\u2014C1B) = 177.4\u2005(2) for (I)0 (O\u2014C0\u2032\u2014N1\u2014C1B) = \u2212175.64\u2005(19) for (II)0 (C6\u2014C0\u2014N1\u2014 C1A) = \u2212170.04\u2005(17)\u00b0 for (III)]. In the case of the N-protected tert-butyl\u00adoxycarbonyl (Boc) group, the protecting group adopts a cis geometry with \u03c90 = 14.50\u00b0 3,3-Ac6c-OH residue and N3 of the pyrazine ring as shown in Fig.\u00a03c. There are no intra\u00admolecular hydrogen bonding inter\u00adactions observed in the crystal structures of derivatives (I)The mol\u00adecular conformations of Valeroyl-\u03b2ii bond pairs . In (II)c). Also present in the structure are \u03c0\u2013\u03c0 inter\u00adactions between the Fmoc groups with an inter\u00adcentroid distance of 3.786\u2005(2)\u2005\u00c5. Fig.\u00a04c shows the aromatic rings of Fmoc groups stacked in a face-to-face and edge-to-face manner, together with inter-plane distances that are within the range for stabilizing \u03c0\u2013\u03c0 inter\u00adactions s Table\u00a01 give a cif Fig.\u00a04a. In 3,3Ac6c-OH  was dissolved in 5\u2005ml of a 2M NaOH solution and a solution of 5\u2005mmol of valeric anhydride (931\u2005mg) dissolved in 1,4-dioxane was added, after which the mixture was stirred for 4\u2005h at room temperature. On completion of the reaction, the 1,4-dioxane was evaporated and the product was extracted with diethyl ether (3 \u00d7 5\u2005ml). The aqueous layer was acidified with 2M HCl and extracted with ethyl acetate (3 \u00d7 10ml) and the combined organic layer was washed with brine solution. The organic layer was passed over anhydrous Na2SO4 and evaporated to give Valeroyl-\u03b23Ac6c-OH . Single crystals were grown by slow evaporation from a solution in methanol/water.Preparation of Valeroyl-\u03b23,3Ac6c-OH (II)3,3Ac6c-OH  was dissolved in 1M Na2CO3 solution and Fmoc-OSu  dissolved in CH3CN was added. The reaction mixture was stirred at room temperature for 6\u2005h. After completion of the reaction, the CH3CN was evaporated and the residue was extracted with diethyl ether (3 \u00d7 10\u2005ml). The aqueous layer was acidified with 2M HCl and extracted with ethyl acetate (3 \u00d7 15\u2005ml). The combined organic layer was washed with brine solution. The ethyl acetate layer was passed over anhydrous Na2SO4 and evaporated. The residue was purified by crystallization in ethyl acetate/n-hexane, affording Fmoc-\u03b23,3Ac6c-OH . Single crystals were obtained by slow evaporation from an ethyl acetate/n-hexane solution.Preparation of Fmoc-\u03b23,3Ac6c-OH (III)2Cl2 and then 200\u2005\u00b5l of N-methyl\u00admorpholine was added, followed by \u03b23,3Ac6c-OMe. HCl  and EDCI. HCl  at 273\u2005K. The reaction mixture was stirred at room temperature for 12\u2005h. After completion of the reaction, water was added and the reaction mixture was extracted with CH2Cl2 (3 \u00d7 5ml). The combined organic layer was washed with 2M HCl (2 \u00d7 5ml), Na2CO3 (2 \u00d7 5ml) and brine solution (2 \u00d7 5ml). The organic layer was passed over anhydrous Na2SO4 and evaporated to give Pyr-\u03b23,3Ac6c-OMe . Pyr-\u03b23,3Ac6c-OMe  was dissolved in 2\u2005ml of methanol and 1\u2005ml of 2M NaOH, and the reaction mixture was stirred at room temperature for 4\u2005h. Methanol was evaporated and the residue was extracted with diethyl ether (2 \u00d7 5ml). The aqueous layer was acidified with 2M HCl and extracted with ethyl acetate (3 \u00d7 5ml). The combined organic layer was washed with brine solution (1 \u00d7 5ml). The ethyl acetate layer was passed over anhydrous Na2SO4 and evaporated to give Pyr-\u03b23,3Ac6c-OH . Single crystals were grown from an ethanol/water solution.Preparation of Pyr-\u03b2Uiso values were refined. The remaining H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C\u2014H distances of 0.96\u20130.98\u2005\u00c5 and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). For derivatives (II)Uiso values were refined. In (II)Pca21, the structure was inverted in the final cycles of refinement as the Flack parameter was 0.8\u2005(14). The inverted structure gave a value of 0.2\u2005(14) for 1585 Friedel pairs.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S1600536814020777/zs2313sup1.cifCrystal structure: contains datablock(s) I, II, III, New_Global_Publ_Block. DOI: 10.1107/S1600536814020777/zs2313Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536814020777/zs2313IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S1600536814020777/zs2313IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S1600536814020777/zs2313Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814020777/zs2313IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814020777/zs2313IIIsup7.cmlSupporting information file. DOI: 1024488, 1024489, 1024490CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "By contrast to this almost  17H14PS)2], is a second monoclinic polymorph  of the previously reported monoclinic  form [Fang et al. \u00b0. By contrast to this almost syn disposition, in the C2/c polymorph, the Fe atom lies on a centre of inversion so that the S atoms are strictly anti, with a pseudo-S\u2014P\u22efP\u2014S torsion angle of 180\u00b0. The significant difference in mol\u00adecular conformation between the two forms does not result in major perturbations in the P=S bond lengths nor in the distorted tetra\u00adhedral geometries about the P atoms. The crystal packing of the new monoclinic polymorph features weak Cp\u2014C\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions consolidating linear supra\u00admolecular chains along the a axis. These pack with no directional inter\u00adactions between them.The title compound, [Fe(C al. 1995. Polyhed R3PAu(S2CNR\u20322), attract on-going inter\u00adest owing to impressive biological activities against both cancer ferrocene (dppf), were isolated as orange needles, being a side-product of a reaction, see Synthesis and crystallization for details. Crystallography shows the title compound to be a new monoclinic polymorph of a previously described C2/c form  di\u00adthio\u00adcarbamates, 2 is shown in Fig.\u00a012P=S units linked via the P atoms through a C5H4FeC5H4 link. The S atoms lie to the same side of the mol\u00adecule and might be described as having a syn conformation. When viewed down the P\u22efP axis, the S atoms are gauche with the pseudo S\u2014P\u22efP\u2014S torsion angle being \u221253.09\u2005(3)\u00b0. This represents the major difference between dppfS2 and its C2/c\u2013dppfS2 polymorph  and Cg(C6\u2013C10) are 1.6487\u2005(8) and 1.6451\u2005(8)\u2005\u00c5, respectively, and the Cg(C1\u2013C5)\u22efFe\u22efCg(C6\u2013C10) angle is 178.92\u2005(5)\u00b0. The comparable parameters for the C2/c\u2013dppfS2 polymorph are 1.650\u2005(3)\u2005\u00c5 and 180\u00b0, and the Cp rings are strictly staggered when viewed down the Cg(C1\u2013C5)\u22efFe\u22efCg(C1\u2013C5)i axis. In dppfS2, the P=S bond lengths are experimentally distinct, i.e. P1=S1 of 1.9449\u2005(6)\u2005\u00c5 is shorter than P2=S2 of 1.9530\u2005(6)\u2005\u00c5, with the former being equivalent to P1=S1 of 1.9384\u2005(18)\u2005\u00c5 in C2/c\u2013dppfS2. Finally, the P1 and P2 atoms have distorted tetra\u00adhedral environments with the range of angles subtended at P1 of 103.94\u2005(7)\u2013113.78\u2005(6)\u00b0 being comparable to those subtended at P2, i.e. 105.55\u2005(7)\u2013114.92\u2005(5)\u00b0; the equivalent range of angles in C2/c\u2013dppfS2 is 104.8\u2005(2)\u2013114.28\u2005(15)\u00b0. In each case, the angles involving the S atom are wider than those involving C atoms only, and the narrowest angle always involves the two ipso-C atoms.The conformational differences in the polymorphs are highlighted in the overlay diagram shown in Fig.\u00a02a axis. Based on the distance criteria employed in PLATON C5H4FeC5H4P(=Y)Ph2, Y = 0, O, S and Se, have been described in the crystallographic literature. The parent compound, i.e. with Y = lone pair, has the Fe atom situated on a centre of inversion C5H4FeC5H4P(=Y)Ph2, Y = 0, O, S and Se, compounds suggesting a low energy barrier for the inter\u00adchange from one conformation to another. The structural data for Ph2P(=Y)C5H4FeC5H4P(=Y)Ph2 are summarized in Table\u00a02The structures of several oxidation products of dppf, Ph2 mol\u00adecule can function as a ligand in metal complexes, often forming zero-dimensional mononuclear species  and CS2 (84.6\u2005\u00b5l) were added. Chloro\u00adform (150\u2005ml) was then added and the reaction mixture was stirred for 2\u2005h. A second solution containing bis\u00ad[chlorido\u00adgold(I)] (1.4\u2005mmol) was prepared by dissolving potassium tetra\u00adchlorido\u00adaurate(III) (1.06\u2005g) in a solvent mixture of acetone and water . Drop-wise addition of sodium sulfite (0.71\u2005g) in water (10\u2005ml) followed. Upon discolouration, bis\u00ad(di\u00adphenyl\u00adphos\u00adphane)ferrocene  in chloro\u00adform (25\u2005ml) was added. After stirring for 15 mins, the resulting gold precursor was extracted with chloro\u00adform (150\u2005ml). Aceto\u00adnitrile (50\u2005ml) was added to this to form solvent mixture of chloro\u00adform and aceto\u00adnitrile (3:1). The solution containing the di\u00adthio\u00adcarbamate was added to that containing the gold precursor. The resulting mixture was stirred for 3\u2005h. and then filtered. After three weeks, orange needles appeared, along with the precipitate, and these were subjected to the crystallographic study. Yield: 0.0890\u2005g, 10.3% (based on dppf). M.p.: 519.5\u2013519.9\u2005K. IR: \u03bd(P=S) 628 (m).Two solutions were prepared. Firstly, a solution sodium salt of piperazine di\u00adthio\u00adcarbamate (0.7\u2005mmol) was prepared by dissolving piperazine (0.0582\u2005g) in aceto\u00adnitrile (50\u2005ml). NaOH (112\u2005\u00b5l of 50% Uiso(H) set to 1.2Uequiv(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015012682/hg5450sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015012682/hg5450Isup2.hklStructure factors: contains datablock(s) I. DOI: 1409866CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the canagliflozin mol\u00adecules and lattice water mol\u00adecules are connected  A and B) and one water mol\u00adecule in the asymmetric unit of the title compound, C24H25FO5S\u00b70.5H2O [systematic name: -2-(3-{[5-(4-fluoro\u00adphen\u00adyl)thio\u00adphen-2-yl]meth\u00adyl}-4-methylphen\u00adyl)-6-(hy\u00addroxy\u00admeth\u00adyl)-3,4,5,6-tetra\u00adhydro-2H-pyran-3,4,5-triol hemihydrate]. The dihedral angles between the methyl\u00adbenzene and thio\u00adphene rings are 115.7\u2005(4) and 111.7\u2005(4)\u00b0, while the dihedral angles between the fluoro\u00adbenzene and thio\u00adphene rings are 24.2\u2005(6) and 20.5\u2005(9)\u00b0 in mol\u00adecules A and B, respectively. The hydro\u00adpyran ring exhibits a chair conformation in both canagliflozin mol\u00adecules. In the crystal, the canagliflozin mol\u00adecules and lattice water mol\u00adecules are connected via O\u2014H\u22efO hydrogen bonds into a three-dimensional supra\u00admolecular architecture.There are two canagliflozin mol\u00adecules ( The conformational difference is also shown by the angle C10\u2014C11\u2014C12, which is 115.7\u2005(4)\u00b0 in mol\u00adecule A and 111.7\u2005(4)\u00b0 in mol\u00adecule B. The terminal aromatic rings (C1\u2013C6) are inclined to the thio\u00adphene rings, forming dihedral angles of 24.2\u2005(6) and 20.5\u2005(9)\u00b0 in mol\u00adecules A and B, respectively. The tetra\u00adhydro\u00adpyran rings exhibit a distorted chair conformation in both mol\u00adecules A and B.The conformations of the two canagliflozin mol\u00adecules are somewhat different with regard to the orientation of the central benzene ring (C12\u2013C17) with respect to the thio\u00adphene ring, as indicated by torsion angles C9B\u2014H3B1\u22efO4Bi, O2B\u2013H2B1\u22efO4Aiii, and O5B\u2014H5B1\u22efO3Biv  link canagliflozin mol\u00adecules, generating a ring of graph-set motif B\u2014H4B\u22efO6, O6\u2014H61\u22efO2A and O4A\u2014H4A\u22efO5Bii  hydrogen bonds propagating along the a axis; the chains are stacked along the c axis by further hydrogen-bonding inter\u00adactions, O3A\u2014H3A1\u22efO2Bi and O2A\u2013-H2A1\u22efO2Bi  = 1.2Ueq or 1.5Ueq(carrier atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016006769/xu5886sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016006769/xu5886Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016006769/xu5886Isup3.cmlSupporting information file. DOI: 1475516CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title complex is composed of saddle-shaped mol\u00adecules which closely inter\u00adact in a pairwise fashion through \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 contacts to form \u2018dimers\u2019. These \u2018dimers\u2019 further inter\u00adact through C\u2014H\u22efS and C\u2014H\u22ef\u03c0 contacts to construct a complex three-dimensional extended structure. 20H12S4, (I), also known as exTTF, is reported. The mol\u00adecular structure of (I) consists of a di\u00adhydro\u00adanthracene moiety with two 1,3-di\u00adthiol-2-yl\u00adidene substituents. This is a saddle-shaped mol\u00adecule, which inter\u00adacts with a close neighbor through various \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 contacts to form a \u2018dimer\u2019. These \u2018dimers\u2019 inter\u00adact through a series of C\u2014H\u22efS and C\u2014H\u22ef\u03c0 contacts to construct a complex three-dimensional extended structure.The crystal structure of the well-studied 9,10-bis\u00ad-9,10-di\u00adhydro\u00adanthracene mol\u00adecule, C The mol\u00adecule is saddle shaped in that the 1,3-di\u00adthiol-2-yl\u00adidene groups bend significantly up out of the plane of the central ring and the two benzene rings of di\u00adhydro\u00adanthracene moiety bend down out of the plane, Fig.\u00a01b. The central six-membered ring (C4\u2013C5\u2013C10\u2013C11\u2013C12\u2013C17) is in a boat conformation in which the 1,3-di\u00adthiol-2-yl\u00adidene-substituted carbon atoms [C4 and C11] are bent out of the plane defined by C5, C10, C12, and C17. The torsion angles C10\u2014C12\u2014C17\u2014C4 = 17.97\u2005(12)\u00b0 and C17\u2014C5\u2014C10\u2014C11 = 17.22\u2005(16)\u00b0 for these two carbon atoms are quite similar.The mol\u00adecular structure of (I)The benzene rings bend out of the C5\u2013C10\u2013C12\u2013C17 plane; the dihedral angle between this plane and the plane of the C5\u2013C6\u2013C7\u2013C8\u2013C9\u2013C10 ring is 17.72\u2005(15)\u00b0 while the dihedral angle for the C12\u2013C13\u2013C14\u2013C15\u2013C16\u2013C17 ring is 20.14\u2005(13)\u00b0. The 1,3-di\u00adthiol-2-yl\u00adidene groups are bent more sharply out of the C5-C10-C12-C17 plane as evidenced by the torsion angles C3\u2014C4\u2014C5\u2014C10 \u03c4 = 138.06\u2005(15)\u00b0 and C18\u2014C11\u2014C12\u2014C17 \u03c4 = 139.23\u2005(15)\u00b0. The five-membered rings both adopt an envelope conformation with the carbon atom bonded to the di\u00adhydro\u00adanthracene [C3 and C18] being the one puckered out of the plane. The torsion angles C3\u2014S1\u2014C1\u2014C2 \u03c4 = \u22128.09\u2005(14)\u00b0 and C18\u2014S4\u2014C20\u2014C19 \u03c4 = \u22126.65\u2005(15)\u00b0 show that the bend in each ring is fairly similar.The average C\u2014C bond length within the benzene rings  is 1.391\u2005\u00c5 as is typical of phenyl rings. The length of the edges shared with the central ring are slightly longer C5\u2014C10 = 1.419\u2005(2)\u2005\u00c5 and C12\u2014C17 = 1.412\u2005(2)\u2005\u00c5. The remaining C\u2014C distances making up the central ring are longer still with an average of 1.477\u2005\u00c5. Since the distances within the central ring are in between those of typical C\u2014C single and double bonds; this supports the idea of a highly delocalized bonding motif throughout the di\u00adhydro\u00adanthracene ring system. The bond distances between the di\u00adhydro\u00adanthracene and the 1,3-di\u00adthiol-2-yl\u00adidene groups are on the order of typical C=C bonds, C3=C4 = 1.360\u2005(2)\u2005\u00c5 and C11=C18 = 1.361\u2005(2)\u2005\u00c5.i\u2013C2i\u2013S2i\u2013C3i\u2013S1i ring  and is rather long at 4.068\u2005(15)\u2005\u00c5. There are five C\u2014H\u22ef\u03c0 inter\u00adactions between the two mol\u00adecules in which atoms H1 and H2 of one mol\u00adecule inter\u00adact with various \u03c0 systems of the neighbor. The shortest contact is between H1 and the C11i=C18i double bond at 2.606\u2005(12)\u2005\u00c5 . There is another short contact between H1 and the central ring of the di\u00adhydro\u00adanthracene, H1\u22efcentroid (C4i\u2013C5i\u2013C10i\u2013C11i\u2013C12i\u2013C17i) 2.852\u2005(11)\u2005\u00c5. Two other C\u2014H\u22ef\u03c0 inter\u00adactions involve H1; H1\u22efcentroid (C18i\u2013S3i\u2013C19i\u2013C20i\u2013S4i) 3.167\u2005(11)\u2005\u00c5, and H1\u22efcentroid (C5i\u2013C6i\u2013C7i\u2013C8i\u2013C9i\u2013C10i) 3.553\u2005(15)\u2005\u00c5. The fifth inter\u00adaction between the \u2018dimer\u2019 mol\u00adecules is H2\u22efcentroid (C5i\u2013C6i\u2013C7i\u2013C8i\u2013C9i\u2013C10i) 3.222\u2005(12)\u2005\u00c5.Through a series of C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions, each mol\u00adecule of (I)ii 2.922\u2005(12)\u2005\u00c5 and one C\u2014H\u22ef\u03c0 contact H14\u22efcentroid (C5ii\u2013C6ii\u2013C7ii\u2013C8ii\u2013C9ii\u2013C10ii) 3.779\u2005(17)\u2005\u00c5 . H15 also inter\u00adacts with two groups on a neighboring mol\u00adecule through two C\u2014H\u22ef\u03c0 contacts; H15\u22efcentroid (C12iii\u2013C13iii\u2013C14iii\u2013C15iii\u2013C16iii\u2013C17iii) 3.385\u2005(17)\u2005\u00c5 and H15\u22efcentroid (C4iii\u2013C5iii\u2013C10iii\u2013C11iii\u2013C12iii\u2013C17iii) 3.543\u2005(14)\u2005\u00c5 . It should be noted that the mol\u00adecules generated by symmetry operations (ii) and (iii) form a \u2018dimer\u2019. The final inter\u00adaction involving a CH group on the di\u00adhydro\u00adanthracene is H6\u22efcentroid (S1iv\u2013C1iv\u2013C2iv\u2013S2iv\u2013C3iv) 2.865\u2005(11)\u2005\u00c5 . Taking these inter\u00adactions into account, a two-dimensional layered structure is formed ed Fig.\u00a03 in whichv\u2013C6v\u2013C7v\u2013C8v\u2013C9v\u2013C10v) 2.829\u2005(18)\u2005\u00c5, H19\u22efcentroid (C4v\u2013C5v\u2013C10v\u2013C11v\u2013C12v\u2013C17v) 3.301\u2005(11)\u2005\u00c5, and H20\u22efcentroid (C12v\u2013C13v\u2013C14v\u2013C15v\u2013C16v\u2013C17v) 2.767\u2005(11)\u2005\u00c5 . These hydrogen atoms also inter\u00adact with another mol\u00adecule via C\u2014H\u22efS contacts; H19\u22efS4vi 3.367\u2005(12)\u2005\u00c5 and H20\u22efS3vi 3.288\u2005(14)\u2005\u00c5 [symmetry operation: (vi) \u2212x, y\u00a0+\u00a00.5, \u2212z\u00a0+\u00a0a axis to form a three-dimensional extended structure, Fig.\u00a04There are also five C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions in which the CH group involved resides on the 1,3-di\u00adthiol-2-yl\u00adidene portion of (I)et al., 1990P21/c) and has a similar saddle shape. It also appears to form similar \u2018dimers\u2019 in which there are both C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions between the two mol\u00adecules.Many derivatives of (I)\u22121 less stable than the predicted favorite. The study details \u03c0\u2013\u03c0 stacking between two of the di\u00adthiol rings, C\u2014H\u22ef\u03c0 contacts between the di\u00adthiol H atoms and the anthracene rings, \u03c0\u2013\u03c0 stacking between anthracene units, as well as an inter\u00adaction between the partial positive charge of the S atoms and the anthracene rings for the preferred computational \u2018dimer\u2019. The study briefly describes the C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions found in (I)A recent computational study focused on predicting the most energetically favored \u2018dimers\u2019 of (I)et al., 1989The title complex, 9,10-bis\u00ad-9,10-di\u00adhydro\u00adanthracene (I)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989015020800/bg2573sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020800/bg2573Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020800/bg2573Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015020800/bg2573Isup4.cmlSupporting information file. DOI: 1434765CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The components of the 2:1 co-crystal are linked by hy\u00addroxy-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds into a three-mol\u00adecule aggregate having the shape of the letter Z. These are connected into a supra\u00admolecular ladder by tight amide-N\u2014H\u22efO(nitro) hydrogen bonds. 7H5NO4\u00b7C14H14N4O2, in which the complete di\u00adamide mol\u00adecule is generated by crystallographic inversion symmetry, features a three-mol\u00adecule aggregate sustained by hydroxyl-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds. The p-nitro\u00adbenzoic acid mol\u00adecule is non-planar, exhibiting twists of both the carb\u00adoxy\u00adlic acid and nitro groups, which form dihedral angles of 10.16\u2005(9) and 4.24\u2005(4)\u00b0, respectively, with the benzene ring. The di\u00adamide mol\u00adecule has a conformation approximating to a Z shape, with the pyridyl rings lying to either side of the central, almost planar di\u00adamide residue (r.m.s. deviation of the eight atoms being 0.025\u2005\u00c5), and forming dihedral angles of 77.22\u2005(6)\u00b0 with it. In the crystal, three-mol\u00adecule aggregates are linked into a linear supra\u00admolecular ladder sustained by amide-N\u2014H\u22efO(nitro) hydrogen bonds and orientated along [10-4]. The ladders are connected into a double layer via pyridyl- and benzene-C\u2014H\u22efO(amide) inter\u00adactions, which, in turn, are connected into a three-dimensional architecture via \u03c0\u2013\u03c0 stacking inter\u00adactions between pyridyl and benzene rings [inter-centroid distance = 3.6947\u2005(8)\u2005\u00c5]. An evaluation of the Hirshfeld surfaces confirm the importance of inter\u00admolecular inter\u00adactions involving oxygen atoms as well as the \u03c0\u2013\u03c0 inter\u00adactions.The title 2:1 co-crystal, 2C The results of this investigation are reported herein.Arguably, the most prominent motivation for the study of co-crystals relates to their potential applications in the pharmaceutical industry whereby co-crystals of active pharmaceutical ingredients (APIs) formed with generally regarded as safe (GRAS) co-crystal coformers might provide drugs with enhanced useful properties, p-nitro\u00adbenzoic acid mol\u00adecule  in a general position, and a N,N\u2032-bis\u00ad(pyridin-3-ylmeth\u00adyl)ethanedi\u00adamide mol\u00adecule  situated about a centre of inversion. This results in the 2:1 co-crystal stoichiometry.The title co-crystal, Fig.\u00a01A2/a: Tonogaki et al., 1993P21/m: Bolte, 2009Twists are noted in the acid mol\u00adecule so that the dihedral angle between the benzene ring and the non-hydrogen atoms of the carb\u00adoxy\u00adlic acid group is 10.16\u2005(9)\u00b0. The comparable angle involving the nitro group is 4.24\u2005(4)\u00b0, consistent with a smaller twist. The substituents have a conrotatory disposition forming a dihedral angle of 13.50\u2005(8)\u00b0. The crystal structure of the free acid was first reported almost fifty years ago \u2005\u00c5 in the title co-crystal.The di\u00adamide features an essentially flat central residue with the r.m.s. deviation for the eight non-hydrogen atoms  being 0.025\u2005\u00c5. This planar arrangement allows for the formation of intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bonds Table\u00a02. The pyret al., 20085NO\u22efHNC2NC3N}2 supra\u00admolecular rings, Fig.\u00a02i.e. Cg(pyrid\u00adyl)\u22efCg(benzene)i = 3.7214\u2005(8)\u2005\u00c5, with an angle of 4.69\u2005(7)\u00b0 between the rings; symmetry operation: (i) 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. The connections between the layers to consolidate the three-dimensional architecture, Fig.\u00a04i.e. Cg(pyrid\u00adyl)\u22efCg(benzene)ii = 3.6947\u2005(8)\u2005\u00c5 with an angle of inclination = 4.69\u2005(7)\u00b0; symmetry operation: (ii) 2\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z.In the packing, the anti\u00adcipated  inter\u00adaction and the similar long spike at the same ed + id distance in the lower right region indicates the contribution of the amide-N\u2014H\u22efO(nitro) inter\u00adaction. The donor\u2013acceptor contributions of these co-crystal constituents are highlighted with the label \u2018d\u2032 in the fingerprint plot, Fig.\u00a07i.e. 32.3%, to the Hirshfeld surface of the acid, a smaller contribution, i.e. 8.3%, is provided by the di\u00adamide; the reverse is true for for the O\u22efH contacts, i.e. 8.5 and 30.4%, respectively. The overall fingerprint plot for the co-crystal when delineated into O\u22efH/H\u22efO contacts leads to the pair of spikes corresponding to donors and acceptors with a 37.1% contribution to surface  and amide-N\u2014H\u22efO(nitro) inter\u00adactions between the pair of acid mol\u00adecules and a di\u00adamide mol\u00adecule can be observed through their corresponding Hirshfeld surfaces mapped over the electrostatic potential, Fig.\u00a05i.e. the enrichment ratio, ER  hydrogen bonding was observed  hydrogen bonding is seen along with hy\u00addroxy-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding 2C6H3CO2\u2212 anion , prepared in accord with the literature procedure (Schauer Uiso(H) set to 1.2Uequiv(C). The oxygen- and nitro\u00adgen-bound H-atoms were located in a difference Fourier map but were refined with distance restraints of O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989015024068/hb7557sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015024068/hb7557Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024068/hb7557Isup3.cmlSupporting information file. DOI: 1442547CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title chalcone derivative, mol\u00adecules are linked into a three-dimensional network by C\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed. The inter\u00admolecular inter\u00adactions in the crystal structure were qu\u00adanti\u00adfied and analysed using Hirshfeld surface analysis. 16H11ClF2O2, the enone group adopts an E conformation. The dihedral angle between the benzene rings is 0.47\u2005(9)\u00b0 and an intra\u00admolecular C\u2014H\u22efF hydrogen bond closes an S(6) ring. In the crystal, mol\u00adecules are linked into a three-dimensional network by C\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed [centroid\u2013centroid separation = 3.5629\u2005(18)\u2005\u00c5]. The inter\u00admolecular inter\u00adactions in the crystal structure were qu\u00adanti\u00adfied and analysed using Hirshfeld surface analysis.In the title chalcone derivative, C The mol\u00adecule is slightly twisted at the C9\u2014-C10 bond with a C8\u2014C9\u2014C10\u2014C15 torsion angle of \u22122.2\u2005(4)\u00b0 and a maximum deviation of 0.193\u2005(16)\u2005\u00c5 for atom O1. The dihedral angle between the terminal benzene rings (C1\u2013C6 and C10\u2013C15) is 0.47\u2005(9)\u00b0. The least-squares plane through the enone moiety (O1/C7\u2013C9) makes dihedral angles of 2.87\u2005(14) and 3.33\u2005(14)\u00b0 with the C1\u2013C6 and C10\u2013C15 benzene rings, respectively. An intra\u00admolecular C8\u2014H8A\u22efF1 hydrogen bond (Table\u00a01S(6) ring motif. The bond lengths and angles are comparable with the equivalent data for previously reported structures; d Table\u00a01 is observia C2\u2014H2A\u22efO1 , centroid-to-centroid distance = 3.5629\u2005(18)\u2005\u00c5, where Cg1 and Cg2 are the centroids of the C1\u2013C6 and C10\u2013C15 rings, respectively].In the crystal, mol\u00adecules are linked into a three-dimensional network s Table\u00a01, as showCrystal Explorer 3.1 with neighbouring mol\u00adecules connected by C2\u2014H2A\u22efO1 and C3\u2014H3A\u22efO2 hydrogen bonds. This finding is corroborated by Hirshfeld surfaces mapped over the electrostatic potential  showing the negative potential around the oxygen atoms as light-red clouds and the positive potential around hydrogen atoms as light-blue clouds.The strong C\u2014H\u22efO inter\u00adactions are visualized as bright-red spots between the respective donor and acceptor atoms on the Hirshfeld surfaces mapped over rm Fig.\u00a03a with nal Fig.\u00a03b showined = id \u223c1.4\u2005\u00c5  with overall Hirshfeld surfaces of 27.5%. The contribution from the O\u22efH/H\u22efO contacts, corresponding to C\u2014H\u22efO inter\u00adactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond inter\u00adaction having almost the same ed + id \u223c2.3\u2005\u00c5 .Significant inter\u00admolecular inter\u00adactions are plotted in Fig.\u00a04\u2005\u00c5 Fig.\u00a04a with o\u2005\u00c5 Fig.\u00a04b.ed = id \u223c1.8\u2005\u00c5 . The presence of the \u03c0\u2013\u03c0 stacking inter\u00adactions is also indicated by the appearance of red and blue triangles on the shape-indexed surfaces, identified with black arrows in Fig.\u00a05The C\u22efC contacts, which refer to \u03c0\u2013\u00b7\u03c0 stacking inter\u00adactions, contribute 13.7% of the Hirshfeld surfaces. This appears as a distinct triangle at around \u2005\u00c5 Fig.\u00a04c. The pA mixture of 3-fluoro-4-meth\u00adoxy\u00adaceto\u00adphenone  and 2-chloro-6-fluoro\u00adbenzaldehyde  was dissolved in methanol (20\u2005ml). A catalytic amount of NaOH  was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5\u20136\u2005h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50\u2005ml) and the resulting crude solid was collected by filtration. Brownish blocks of (I)Uiso(H) = 1.2Ueq(C). In the final refinement, the most disagreeable reflection (020) was omitted.Crystal data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016006526/hb7578sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016006526/hb7578Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016006526/hb7578Isup3.cmlSupporting information file. DOI: 1474605CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In [Cu(Hspar)2](bdc)\u00b72H2O,the Cu2+ ion lies on a crystallographic inversion centre and a CuO4 square-planar geometry arises from its coordination by two O,O\u2032-bidentate Hspar mol\u00adecules. The bdc dianion acts as a counter-ion to the cationic complex and does not bond to the metal ion.The Mn 2O,O\u2032)bis\u00admanganese(II) dihydrate, [Mn(C8H4O4)(C19H22F2N4O3)2(H2O)0.25]\u00b72H2O or [Mn(bdc)(Hspar)2(H2O)0.25]\u00b72H2O, (I), and bis\u00adcopper(II) benzene-1,4-di\u00adcarboxyl\u00adate dihydrate, [Cu(C19H22F2N4O3)2](C8H4O4)\u00b72H2O or [Cu(Hspar)2](bdc)\u00b72H2O, (II), are reported . The Mn2+ ion in (I) is coordinated by two O,O\u2032-bidentate Hspar neutral mol\u00adecules (which exist as zwitterions) and an O,O\u2032-bidentate bdc dianion to generate a distorted MnO6 trigonal prism. A very long bond [2.580\u2005(12)\u2005\u00c5] from the Mn2+ ion to a 0.25-occupied water mol\u00adecule projects through a square face of the prism. In (II), the Cu2+ ion lies on a crystallographic inversion centre and a CuO4 square-planar geometry arises from its coordination by two O,O\u2032-bidentate Hspar mol\u00adecules. The bdc dianion acts as a counter-ion to the cationic complex and does not bond to the metal ion. The Hspar ligands in both (I) and (II) feature intra\u00admolecular N\u2014H\u22efO hydrogen bonds, which close S(6) rings. In the crystals of both (I) and (II), the components are linked by N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, generating three-dimensional networks.The syntheses and crystal structures of 0.25-aqua\u00ad(benzene-1,4-di\u00adcarboxyl\u00adato-\u03ba As well as their biological significance, this class of compounds is of inter\u00adest in coordination chemistry due to their potential to act as multi-dentate and bridging ligands in the construction of mononuclear and dinuclear complexes  complexes with nickel  with BF4\u2212 0.25]\u00b72H2O (I)2](bdc)\u00b72H2O (II)8H4O42\u2212).As a continuation of these studies, we now describe the syntheses and crystal structures of the title mixed-ligand complexes  Mn\u2014O bond to the partly occupied O13 water mol\u00adecule. Together, these lead to a distorted MnO6+1 trigonal\u2013prismatic polyhedron n Table\u00a01 with theds Fig.\u00a02. The meads Fig.\u00a02 for the 2 groups mutually syn.The conformation of the \u2013O2\u2013C1\u2013C2\u2013C3\u2013O3\u2013Mn1\u2013 chelate ring approximates to a shallow envelope with the metal atom as the flap, displaced by \u22120.222\u2005(4)\u2005\u00c5 from the mean plane of the ligand atoms (r.m.s. deviation = 0.022\u2005\u00c5). The \u2013O5\u2013C20\u2013C21\u2013C22\u2013O6\u2013Mn1\u2013 ring can be described in the same way, with Mn1 displaced by 0.128\u2005(4)\u2005\u00c5 from the other atoms (r.m.s. deviation = 0.019\u2005\u00c5). The dihedral angle between the near-planar segments of the chelate rings is 29.74\u2005(13)\u00b0. Both Hspar mol\u00adecules are orientated in the same sense with respect to the metal ion, with the NH6+1 grouping is unusual and calls for some further comment: the dihedral angle between the top (O3/O6/O8) and bottom (O2/O5/O7) triangular faces of the prism is 14.40\u2005(11)\u00b0, which is largely due to the O7\u22efO8 edge of the prism (the two O atoms of the bdc dianion) being much shorter [2.174\u2005(3)\u2005\u00c5] than the O2\u22efO3 [2.799\u2005(3)\u2005\u00c5] and O5\u22efO6 [2.802\u2005(3)\u2005\u00c5] edges, which correspond to the C1- and C-20 Hspar mol\u00adecules, respectively. The metal atom is displaced from the top and bottom faces of the prism by \u22121.2513\u2005(14) and 1.3670\u2005(12)\u2005\u00c5, respectively. The degree of twist of the prism may be estimated from the pseudo torsion angles involving the centroids of the triangular faces (denoted X1 for the O3/O6/O8 face and X2 for the O2/O5/O7 face) and the pairs of atoms forming the edges of the prism: values of X1\u22efO7\u22efO8\u22efX2 (\u201314.6), X1\u22efO5\u22efO6\u22efX2 (\u201311.2) and X1\u22efO2\u22efO3\u22efX2 (\u20138.5\u00b0) arise. These angles would be zero for a perfect triangular prism.The capped trigonal\u2013prismatic geometry of the MnOsp2 hybridization for this atom. The dihedral angle between the N2 ring and the C5 ring (r.m.s. deviation = 0.028\u2005\u00c5), which are fused at the C4\u2014C9 bond, is 7.9\u2005(2)\u00b0, indicating a substantial puckering to the quinolone system. The piperazinium ring adopts a typical chair conformation with the exocyclic N\u2014Cq (q = quinolone) bond in an equatorial orientation. The dihedral angle between the four C atoms that form the \u2018seat\u2019 of the chair and the C5 ring is 60.3\u2005(2)\u00b0. There was some suggestion that atoms C14 and C17 of this ring are positionally disordered, but refinements that attempted to model this effect were inconclusive.The most important geometrical features of the first Hspar mol\u00adecule (containing C1) are as follows: the C1\u2014O1 and C1\u2014O2 bond lengths of 1.251\u2005(4) and 1.256\u2005(4)\u2005\u00c5, respectively, are typical for a delocalized carboxyl\u00adate group and the dihedral angle between C1/O1/O2 and the adjacent N2-containing ring (r.m.s. deviation = 0.045\u2005\u00c5) is 8.6\u2005(8)\u00b0. The dihedral angle between the cyclo\u00adpropane ring and the N2 ring is 67.5\u2005(3)\u00b0. The N2 bond-angle sum of 359.8\u00b0 is consistent with a bonding model of S(6) ring. The C45/O7/O8 and C46/O9/O10 carboxyl\u00adate groups of the bdc dianion are rotated by 3.90\u2005(7) and 25.28\u2005(14)\u00b0, respectively with respect to the central ring plane. The O7\u2014Mn1\u2014O8 bite angle is 56.58\u2005(8)\u00b0.The second Hspar mol\u00adecule (containing C20) has a broadly similar geometry: the C20\u2014O4 and C20\u2014O5 bond lengths are 1.254\u2005(4) and 1.257\u2005(4)\u2005\u00c5, respectively, and the dihedral angle between C20/O4/O5 and the N6 ring (r.m.s. deviation = 0.050\u2005\u00c5) is 8.8\u2005(7)\u00b0. The dihedral angle between the N6 (bond-angle sum = 359.7\u00b0) ring and the pendent three-membered ring is 69.8\u2005(2)\u00b0. The N6 and C24 rings (r.m.s. deviation for the latter = 0.020\u2005\u00c5), fused at the C23\u2014C28 bond, are tilted by 8.1\u2005(2)\u00b0. The piperazine ring adopts a chair conformation and the dihedral angle between the chair seat and the C24 ring is 58.71\u2005(9)\u00b0. Each Hspar mol\u00adecule features an intra\u00admolecular N\u2014H\u22efO hydrogen bond Table\u00a02, which c2+ cation lying on a crystallographic inversion centre, a neutral, zwitterionic, Hspar mol\u00adecule, half a bdc dianion and a water mol\u00adecule of crystallization on Fig.\u00a03.O,O-bidentate Hspar mol\u00adecules in the usual bonding mode of quinoline O atom + syn-carboxyl\u00adate O atom  with a bite angle of 93.24\u2005(8)\u00b0, which generates a six-membered chelate ring. The result is a CuO4 square-planar coordination polyhedron (Table\u00a03The copper ion in (II)n Table\u00a03 with a mIn the Hspar mol\u00adecule, the C1\u2014O1 and C1\u2014O2 bond lengths are distinctly different at 1.226\u2005(4)\u2005\u00c5 and 1.283\u2005(4)\u2005\u00c5, respectively, unlike the situation in (I)In the bdc dianion, the C23/O4/O5 carboxyl\u00adate group is rotated by 2.7\u2005(6)\u00b0 with respect to the aromatic ring plane. The C23\u2014O4 and C23\u2014O5 bond lengths of 1.244\u2005(4) and 1.253\u2005(4)\u2005\u00c5, respectively, are consistent with the approximately equal delocalization of the negative charge over both C\u2014O bonds.In the crystal of (I)In (II)2+ ions and Hspar mol\u00adecules. The O,O-chelating mode of the Hspar mol\u00adecules is normal for other divalent transition metals ] : as these authors note, the high-spin d5 electronic configuration of Mn2+ is the \u2018least unexpected\u2019 to show a trigonal\u2013prismatic geometry because it has no crystal-field stabilization energy, which normally favours octa\u00adhedral over trigonal\u2013prismatic geometry ] have almost the same energy and the trigonal\u2013prismatic geometry is adopted in the crystal because of favourable packing inter\u00adactions 2]2+ cations seen here. In [Cu(H2spar)(H2O)(phen)]BF4\u00b73H2O  and the N,N-bidentate phen ligand in a square-planar arrangement; the water mol\u00adecule completes the square-based pyramidal coordination polyhedron in the apical site. Finally, in the novel bimetallic complex [Cu2(spar)4]\u00b74H2O \u2005\u00c5] arising from the \u2013NH2 group of an adjacent spar\u2212 anion generating a centrosymmetric, bimetallic assembly. It is thus notable that sparfloxacin can bind to Cu2+ ions in its anionic, neutral and cationic forms and we are continuing our explorations of these systems.Compound (II)3CO2)2\u00b74H2O (0.25\u2005mmol), sparfloxacin (0.5\u2005mmol), 1,4-benzene\u00addicarb\u00adoxy\u00adlic acid (0.25\u2005mmol), sodium hydroxide (1\u2005mmol) and water (15\u2005ml) was stirred for 30 minutes in air. The mixture was placed in a sealed 25\u2005ml Teflon-lined hydro\u00adthermal reactor and heated to 423\u2005K for 72\u2005h under autogenous pressure. Upon cooling, colourless prisms of (I)46H52.5MnF4N8O12.25: C 52.90 (52.63), H 5.07 (4.91), N 10.73 (10.58). IR : br3420, br3300, s1633 (C=O pyridone), s1562 (CO2asym), s1443, s1375 (CO2symm), s1292, w1184, m819, m756, m686, m517 [IR assignments following Llin\u00e0s et al. (2008To prepare (I) al. 2008].3CO2)2]\u00b7H2O (0.25\u2005mmol) used in place of the manganese acetate tetra\u00adhydrate and the vessel heated to 413\u2005K for 72\u2005h. Upon cooling, green blocks of (II)46H50CuF4N8O12: C 52.80 (52.70), H 4.82 (4.72), N 10.71 (10.64). IR : br3427, br3304, s1633 (C=O pyridone), s1556 (CO2asym), s1435, s1358 (CO2symm), s1294, w1182, w1012, w928, w814, m748, m527.Compound (II)Both (I)Uiso(H) = 1.2\u20131.5Ueq(C) applied. The N- and O-bound H atoms were located in difference maps and refined as riding atoms in their as-found relative positions.Crystal data, data collection and structure refinement details for (I)10.1107/S205698901502424X/sj5492sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S205698901502424X/sj5492Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901502424X/sj5492IIsup3.hklStructure factors: contains datablock(s) II. DOI: 932077, 932078CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The central cyclo\u00adhexane ring has a chair conformation. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to (100). 28H22O5S3, the central cyclo\u00adhexane ring adopts a chair conformation. The atoms of the furan ring attached to the 6-position of the central cyclo\u00adhexane ring are disordered over two sets of sites with occupancies of 0.832\u2005(5) and 0.168\u2005(5). The hy\u00addroxy group is disordered over two positions (at the 4- and 6-positions of the cyclo\u00adhexane ring) in the ratio 0.832\u2005(5):0.168\u2005(5). In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to (100).In the title compound, C The resulting product is a racemate crystallizing in a centrosymmetric space group.Domino or cascade reactions have many applications in organic chemistry (Tietze QT = 0.586\u2005(3)\u2005\u00c5, \u03b8 = 0.0\u2005(3)\u00b0 and \u03c6 = 169\u2005(17)\u00b0]. The mean plane of this ring makes dihedral angles of 80.42\u2005(14), 59.57\u2005(17), 85.65\u2005(17), 66.82\u2005(19), 84.88\u2005(18) and 83.1\u2005(8)\u00b0, respectively, with the five associated five-membered rings .In the title compound, Fig.\u00a01a- and b-axis directions, Figs. and 3. Short S3\u22efS3ii contacts  at 3.5210\u2005(12)\u2005\u00c5 may also contribute to the crystal packing  method -2,6-bis\u00ad(furan-2-yl)-4-hy\u00addroxy-4-(thio\u00adphen-2-yl)cyclo\u00adhexane-1,3-di\u00adyl]bis\u00ad(thio\u00adphen-2-yl\u00admethanone) was synthesized according to a literature method  were found from a difference Fourier map and their positions were constrained to the expected geometries [C\u2014H = 0.95\u00b10.02\u2005\u00c5] with a fixed U value of 0.05\u2005\u00c52. All other H atoms were placed in calculated positions  and refined using a riding model with Uiso(H) = 1.2Ueq(carrier).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016009452/sj5500sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016009452/sj5500Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016009452/sj5500Isup3.cmlSupporting information file. DOI: 1484675CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this article we report a synthetic procedure and structure of the novel dinuclear copper(II) complex, with a bridging oxalodi\u00adhydroxamate ligand and terminal 2,2\u2032-bi\u00adpyridine and DMSO ligands completing the square pyramidal coordination spheres of the Cu(II) centres.. 2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2, contains two copper(II) ions, connected through an N-deprotonated oxalodi\u00adhydroxamic acid dianion, two terminal 2,2\u2032-bi\u00adpyridine ligands, and two apically coordinating dimethylsulfoxide mol\u00adecules. Two non-coordinating perchlorate anions assure electrical neutrality. The copper(II) ions in the complex dication [Cu2(C10H8N2)2(\u03bc-C2H2N2O4)(C2H6SO)2]2+ are in an O2N3 square-pyramidal donor environment, the Cu\u2013Cu separation being 5.2949\u2005(4)\u2005\u00c5. Two hydroxamate groups in the deprotonated oxalodi\u00adhydroxamic acid are located trans to one each other. In the crystal, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the complex cations to the perchlorate anions. Further C\u2014H\u22efO hydrogen bonds combine with \u03c0\u2013\u03c0 contacts with a centroid-to-centroid separation of 3.6371\u2005(12)\u2005\u00c5 to stack the mol\u00adecules along the a-axis direction.The centrosymmetric binuclear complex, [Cu The twoet al., 2000et al., 2003et al., 2004et al., 2000et al., 1999The C\u2014N and C\u2014C bond lengths in the 2,2\u2032-bi\u00adpyridine ligands are also normal for 2-substituted pyridine derivatives \u2005\u00c5 to stack the cations along the a-axis direction, Fig.\u00a02In the crystal structure, O5\u2014H5trans-form. The bond lengths in oxalodi\u00adhydroxamic acid itself and in its ammonium and thallium salts do not differ significantly [C\u2014C bonds are in the range 1.51\u2005(2)\u20131.528\u2005(3)\u2005\u00c5, C=O 1.231\u2005(3)\u20131.248\u2005(3)\u2005\u00c5, C\u2014N 1.310\u2005(4)\u20131.33\u2005(2)\u2005\u00c5 while the N\u2014O bond lengths vary from 1.36\u2005(2) to 1.388\u2005(1)\u2005\u00c5; Lowe-Ma & Decker, 1986et al., 1987et al., 1991II complexes with ligands derived from doubly or triply deprotonated oxalodi\u00adhydroxamic acid. In one of these complexes 2\u00b76H2O in 10\u2005ml of DMSO the solution of 2,2\u2032-bi\u00adpyridine  in 10\u2005ml of methanol was added upon stirring. The resulted solution was stirred for 1\u2005h and then left for slow evaporation.To the warm mixture containing 0.060\u2005g (0.5\u2005mmol) of oxalodi\u00adhydroxamic acid and 0.370\u2005g (1\u2005mmol) of Cu of the title compound.Uiso = 1.2\u20131.5 Ueq(parent atom). The highest peak is located 0.99\u2005\u00c5 from atom Cu1 and the deepest hole is located 0.82\u2005\u00c5 from atom Cu1.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016000050/sj5487sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016000050/sj5487Isup2.hklStructure factors: contains datablock(s) I. DOI: 1445115CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III ion in the title compound is coordinated by six N atoms of three chelating 1,2-cyclo\u00adhexa\u00adnedi\u00adamine (chxn) ligands, displaying a distorted octa\u00adhedral environment. The crystal packing is stabilized by extensive hydrogen-bonding inter\u00adactions between the N\u2014H groups of the chxn ligands, O\u2014H groups or O atoms of the water mol\u00adecules, chloride ions and Cl atoms of the disordered [ZnCl4]2\u2212 anions.The Cr rac-chxn)3][ZnCl4]Cl\u00b73H2O , has been determined from synchrotron data. The CrIII ion is coordinated by six N atoms of three chelating chxn ligands, displaying a slightly distorted octa\u00adhedral coordination environment. The distorted tetra\u00adhedral [ZnCl4]2\u2212 anion, the isolated Cl\u2212 anion and three lattice water mol\u00adecules remain outside the coordination sphere. The Cr\u2014N(chxn) bond lengths are in a narrow range between 2.0737\u2005(12) and 2.0928\u2005(12)\u2005\u00c5; the mean N\u2014Cr\u2014N bite angle is 82.1\u2005(4)\u00b0. The crystal packing is stabilized by hydrogen-bonding inter\u00adactions between the amino groups of the chxn ligands and the water mol\u00adecules as donor groups, and O atoms of the water mol\u00adecules, chloride anions and Cl atoms of the [ZnCl4]2\u2212 anions as acceptor groups, leading to the formation of a three-dimensional network. The [ZnCl4]2\u2212 anion is disordered over two sets of sites with an occupancy ratio of 0.94:0.06.The structure of the title double salt, [Cr( The synthetic procedures, crystal structures and detailed spectroscopic properties of such [Cr(chxn)3]3+ complexes with chloride or nitrate anions have been reported previously 6][ZnCl4]Cl 2(cyclam)][ZnCl4]Cl\u00b7H2O 3][ZnCl4]Cl\u00b73H2O, (I)3]Cl3\u00b72H2O with 98\u2005K synchrotron data to determine the exact composition and coordination geometry of the CrIII ion. The complex crystallizes in the space group Id with eight formula units in a cell of dimensions a = 18.893\u2005(3) and c = 14.069\u2005(3)\u2005\u00c5. The Cr\u2014N(chxn) bond lengths are in the range 2.0723\u2005(19) to 2.0937\u2005(19)\u2005\u00c5, and the N\u2014Cr\u2014N bite angles are in the range 82.53\u2005(7) to 82.69\u2005(10)\u00b0. In comparison with the bond lengths and angles of the structure of this complex determined with 223\u2005K data rac-chxn)3]3+, three lattice water mol\u00adecules, together with one tetra\u00adhedral [ZnCl4]2\u2212 and one isolated Cl\u2212 counter-ion. The nitro\u00adgen atoms of the three 1,2-cyclo\u00adhexa\u00adnedi\u00adamine ligands define a distorted octa\u00adhedral coordination environment around the Cr(III) ion with a mean N\u2014Cr\u2014N bite angle of 82.1\u2005(4)\u00b0. The resulting five-membered chelate rings of chxn ligands have the expected stable gauche conformation. The Cr\u2014N(chxn) bond lengths are in the range 2.0737\u2005(12) to 2.0928\u2005(12)\u2005\u00c5, in good agreement with those determined in [Cr(RR-chxn)3](NO3)3\u00b73H2O 3]Cl3\u00b72H2O 3](NO3)3\u00b73H2O 3]Cl3\u00b72H2O 3][Co(SS-chxn)3]Cl6\u00b74H2O 3]Cl3\u00b72H2O was prepared according to the literature  chloride salt suitable for X-ray structural analysis.Commercially available (Aldrich) Uiso(H) values of 1.2 or 1.5Ueq of the parent atoms. The hydrogen atoms of water mol\u00adecules were restrained using DFIX and DANG commands during the least-squares refinement  I. DOI: 10.1107/S2056989016005788/wm5284Isup2.hklStructure factors: contains datablock(s) I. DOI: 1472901CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "All complexes adopt the expected square-planar coordination geometry, and the benzo\u00adthia\u00adzole is engaged in bonding to the metal atom through the imine N atom (Pt\u2014N).Four new platinum(II) complexes, [PtBr3(C8H7NS)] (1), tetra\u00adethyl\u00adammonium tri\u00adbromido\u00adplatinate(II), [NEt4][PtBr3(C9H9NOS)] (2), tetra\u00adethyl\u00adammonium tri\u00adbromido\u00adplatinate(II), [NEt4][PtBr3(C10H11NS)] (3), and tetra\u00adethyl\u00adammonium tri\u00adbromido\u00adplatinate(II), [NEt4][PtBr3(C8H6N2O2S)] (4), have been synthesized and structurally characterized by single-crystal X-ray diffraction techniques. These species are precursors of compounds with potential application in cancer chemotherapy. All four platinum(II) complexes adopt the expected square-planar coordination geometry, and the benzo\u00adthia\u00adzole ligand is engaged in bonding to the metal atom through the imine N atom (Pt\u2014N). The Pt\u2014N bond lengths are normal: 2.035\u2005(5), 2.025\u2005(4), 2.027\u2005(5) and 2.041\u2005(4)\u2005\u00c5 for complexes 1, 2, 3 and 4, respectively. The benzo\u00adthia\u00adzole ligands are positioned out of the square plane, with dihedral angles ranging from 76.4\u2005(4) to 88.1\u2005(4)\u00b0. The NEt4 cation in 3 is disordered with 0.57/0.43 occupancies.Four new platinum(II) complexes, namely tetra\u00adethyl\u00adammonium tri\u00adbromido\u00ad(2-methyl-1,3-benzo\u00adthia\u00adzole-\u03ba All complexes showed the benzo\u00adthia\u00adzoles to coordinate the PtII atom through the imino nitro\u00adgen atom. Also, the benzo\u00adthia\u00adzole is positioned out of the square plane with dihedral angles between 76.4\u2005(4) and 88.1\u2005(4)\u00b0, as previously reported in other platinum\u2013benzo\u00adthia\u00adzole complexes. Given that benzo\u00adthia\u00adzoles have anti\u00adcancer properties, these platinum complexes may have enhanced properties as a result of potential synergism between the ligand and PtII. This deserves further studies as suggested by Noolvi et al.  complexes with benzo\u00adthia\u00adzole ligands of general formula  (1) crystallizes in an ortho\u00adrhom\u00adbic unit cell with eight formula units. It is a square-planar complex with Pt\u2014N and average Pt\u2014Br bond lengths of 2.035\u2005(5) and 2.433\u2005(6)\u2005\u00c5, respectively, which are within the expected range for PtII complexes. There is no trans-influence observed in the Pt\u2014Br bond trans to the Pt\u2014N bond. The benzo\u00adthia\u00adzole ligand is planar and the methyl group resides in the ligand plane. The dihedral angle between the PtBr3N unit and the benzo\u00adthia\u00adzole ring is 88.1\u2005(4)\u00b0, similar to those observed in other PtII\u2013benzo\u00adthia\u00adzole complexes, as a result of reducing the steric strain between PtBr3 and the benzo\u00adthia\u00adzole ligand ] (2), [NEt4][PtBr3] (3) and [NEt4][PtBr3(5-NO2-2-Me-benzo\u00adthia\u00adzole)] (4) crystallize in the same type of unit cell and space group, monoclinic P21/n, containing four formula units. The Pt\u2014N and average Pt\u2014Br bond lengths for 2, 3, and 4 are 2.025\u2005(4)/2.430\u2005(6)\u2005\u00c5, 2.027\u2005(5)/2.425\u2005(6)\u2005\u00c5 and 2.041\u2005(4)/2.431\u2005(8)\u2005\u00c5, respectively, which are within the expected range. The dihedral angle between PtBr3N and the benzo\u00adthia\u00adzole in 2 is 86.7\u2005(3)\u00b0 and the torsion angle between the aromatic ring and the OCH3 group is 11.9\u2005(7)\u00b0. The C\u2014O (OCH3) bond length is 1.427\u2005(7)\u2005\u00c5, and the C\u2014O\u2014CH3 angle is 116.3\u2005(5)\u00b0. In contrast to 1 and 2, [NEt4][PtBr3] and [NEt4][PtBr3(5-NO2-2-Me-benzo\u00adthia\u00adzole)] have lower dihedral angles between the PtBr3N unit and the benzo\u00adthia\u00adzole ring, 78.6\u2005(4) and 76.(4)\u00b0, respectively. The methyl groups on 3 and 4 are almost co-planar with the benzo\u00adthia\u00adzole plane with deviations \u2264 1.60\u00b0 but in 4, the NO2 group is out of the benzo\u00adthia\u00adzole plane with a torsion angle of 7.5\u2005(7)\u00b0. The C\u2014NO2 bond length is 1.476\u2005(7)\u2005\u00c5, and the O\u2014N\u2014O angle is 117.4\u2005(5)\u00b0. The C\u2014NO2 bond length and O\u2014N\u2014O angle in 4 are smaller than those observed in nitro\u00adbenzene [C\u2014NO2 = 1.486\u2005(2)\u2005\u00c5 and O\u2014N\u2014O = 123.9\u2005(5)\u00b0], which suggests higher electron delocal\u00adization between the nitro group and the aromatic ring in 4 ]\u2212 anions. The [NEt4][PtBr3(2-Me-benzo\u00adthia\u00adzole)] and [NEt4][PtBr3(6-OMe-2-Me-benzo\u00adthia\u00adzole)] complexes showed partial \u03c0-stacking between the phenyl and the thia\u00adzole rings  and the corresponding amount of ligand was added with stirring. For 2-methyl-1,3-benzo\u00adthia\u00adzole (99%) 18\u2005\u03bcL  were added; for 2-methyl-5-nitro-1,3-benzo\u00adthia\u00adzole (98%)  were added, and for 2-methyl-6-meth\u00adoxy-1,3-benzo\u00adthia\u00adzole (97%)  were added. The reaction mixtures were stirred without heating until the volume reduced considerably; then the samples were placed in desiccators containing CaCl2 at room temperature to evaporate slowly, leading to the formation of X-ray quality single crystals. For the synthesis with 2,5,6-trimethyl-1,3-benzo\u00adthia\u00adzole (99%), the ligand  was added to 20\u2005mL of an acetone solution  of [NEt4]2[Pt2Br6] with stirring, and a portion of the reaction mixture was slowly evaporated at 277\u2005K in a small beaker in a secondary container which also contained CaCl2 to form X-ray quality single crystals.Acetone solutions of [NEtd(C\u2014H) = 0.95\u2005\u00c5, Uiso(H) = 1.2Ueq(C); d(C\u2014H2) = 0.99\u2005\u00c5, Uiso(H) = 1.2Ueq(C); d(C\u2014H3) = 0.98\u2005\u00c5, Uiso(H) = 1.5Ueq(C). The NEt4 cation in 3 presented disorder with 0.57/0.43 occupancies.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016002826/bg2580sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, 4. DOI: 10.1107/S2056989016002826/bg25801sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989016002826/bg25802sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989016002826/bg25803sup4.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S2056989016002826/bg25804sup5.hklStructure factors: contains datablock(s) 4. DOI: 1441324, 1441327, 1441326, 1441325CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I complex, the AgI atom is coordinated by two S atoms of thio\u00adurea and two P atoms of tri\u00adphenyl\u00adphosphane in a distorted tetra\u00adhedral geometry. In the crystal, the component ions are linked by C\u2014H\u22efO, C\u2014H\u22efS, N\u2014H\u22efO and N\u2014H\u22efS hydrogen bonds, generating (10-1) sheets.In the nitrate salt of this Ag 4N2S)2(PPh3)2]NO3, the AgI atom is coordinated by two thio\u00adurea S atoms and two tri\u00adphenyl\u00adphosphane P atoms in a distorted tetra\u00adhedral geometry, with bond angles in the range 102.90\u2005(4)\u2013123.29\u2005(4)\u00b0. The Ag\u2014S=C bond angles are 101.75\u2005(19) and 111.29\u2005(18)\u00b0. In the crystal, the component ions are linked by C\u2014H\u22efO, C\u2014H\u22efS, N\u2014H\u22efO and N\u2014H\u22efS hydrogen bonds, generating (10-1) sheets.In the title salt, [Ag(CH In the cationic complex, [Ag(PPh3)2(tu)2]+, the silver(I) atom is bound to two P atoms of PPh3 and two sulfur atoms of thio\u00adurea, assuming a slightly distorted tetra\u00adhedral geometry , B (C7\u2013C12), C (C13\u2013C18), D (C19\u2013C24), E (C25\u2013C30) and F (C31\u2013C36) are as follows: A/B, A/C, B/C, D/E, D/F and E/F = 82.67\u2005(15), 62.77\u2005(17), 86.59\u2005(14), 73.72\u2005(14), 85.01\u2005(16) and 84.06\u2005(17)\u00b0, respectively. The thio\u00adurea units G (S1/C37/N1/N2) and H (S2/C38/N3/N4) are almost planar with r.m.s. deviations of 0.0031 and 0.0007\u2005\u00c5, respectively, and are oriented at a dihedral angle of 76.82\u2005(11)\u00b0 to each other.In (I)S(6) and In the asymmetric unit, strong N\u2014H\u22efS, N\u2014H\u22efO hydrogen bonds complete distorted s Table\u00a02 and lead3 and PPh3 in a methanol\u2013aceto\u00adnitrile medium . Mixing resulted in the formation of a white precipitate. After stirring for half an hour, the mixture was filtered and the filtrate was left for crystallization. Colorless crystals of (I)et al., 2010The title complex was prepared by adding one equivalent of thio\u00adurea dissolved in 10\u2005ml methanol to a 1:1 mixture of AgNOUiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015001395/hb7352sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001395/hb7352Isup2.hklStructure factors: contains datablock(s) I. DOI: 1044766CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(9) ring motif. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds forming inversion dimers with an R44(10) ring motif. The dimers are linked by C\u2014H\u22efN hydrogen bonds, forming ribbons along [01-1].In the title compound, there is an intra\u00admolecular O\u2014H\u22efN hydrogen bond forming an  22H19ClN4O, the quinolinol moiety is almost planar [r.m.s. deviation = 0.012\u2005\u00c5]. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond involving the hy\u00addroxy group and a pyridine N atom forming an S(9) ring motif. The dihedral angles between the planes of the quinolinol moiety and the pyridine rings are 44.15\u2005(9) and 36.85\u2005(9)\u00b0. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds forming inversion dimers with an R44(10) ring motif. The dimers are linked by C\u2014H\u22efN hydrogen bonds, forming ribbons along [01-1]. The ribbons are linked by C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distance = 3.7109\u2005(11)\u2005\u00c5], forming layers parallel to (01-1).In the title compound, C Analysis calculated for C22H19ClN4O: C 67.60, H 4.90, N 14.33%; found: C 67.50, H 5.01, N 14.37%.A suspension of paraformaldehyde  and bis\u00ad(2-pyridyl\u00admeth\u00adyl)amine  in 100\u2005ml of MeOH was stirred for 18\u2005h at room temperature. The solvent was removed under vacuum. To the product obtained was added 100\u2005ml of toluene and 5-chloro-8-quinolinol , and the mixture was heated for 24\u2005h at 353\u2005K. The solvent was removed under vacuum to give an oily product, which was crystallized from hexa\u00adne\u2013di\u00adchloro\u00admethane. The crude solid was recrystallized from aceto\u00adnitrile to obtain yellow crystals of the title compound . HRMS (Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015022410/su5241sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015022410/su5241Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015022410/su5241Isup3.cmlSupporting information file. DOI: 1438483CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II coordination polymer has been prepared via solvothermal synthesis using dimethyl sulfoxide as solvent. The coordination polymer forms double-chains along [010] and exhibits \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions forming the inter\u00adior of the double-chains, separated from a C\u2014H\u22ef\u03c0 hydrogen-bonding network in the space between the double-chains.A one-dimensional Ni 7H3NO4)(C4H4N2)(C2H6OS)]n, consists of [010] chains composed of NiII ions linked by bis-monodentate-bridging pyrazine mol\u00adecules. Each of the two crystallographically distinct NiII ions is located on a mirror plane and is additionally coordinated by a dimethyl sulfoxide (DMSO) ligand through the oxygen atom and by a tridentate 2,6-pyridine-di\u00adcarb\u00adoxy\u00adlic acid dianion through one of each of the carboxyl\u00adate oxygen atoms and the pyridine nitro\u00adgen atom, leading to a distorted octa\u00adhedral coordination environment. The title structure exhibits an inter\u00adesting complementarity between coordinative bonding and \u03c0\u2013\u03c0 stacking where the Ni\u2014Ni distance of 7.0296\u2005(4)\u2005\u00c5 across bridging pyrazine ligands allows the pyridine moieties on two adjacent chains to inter\u00addigitate at halfway of the Ni\u2014Ni distance, resulting in \u03c0\u2013\u03c0 stacking between pyridine moieties with a centroid-to-plane distance of 3.5148\u2005(2)\u2005\u00c5. The double-chain thus formed also exhibits C\u2014H\u22ef\u03c0 inter\u00adactions between pyridine C\u2014H groups on one chain and pyrazine mol\u00adecules on the other chain. As a result, the inter\u00adior of the double-chain structure is dominated by \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef \u03c0 inter\u00adactions, while the space between the double-chains is occupied by a C\u2014H\u22efO hydrogen-bonding network involving DMSO ligands and carboxyl\u00adate groups located on the exterior of the double-chains. This separation of dissimilar inter\u00adactions in the inter\u00adior and exterior of the double-chains further stabilizes the crystal structure.The title coordination polymer, [Ni(C II complex obtained by reacting 2,6-pyridine di\u00adcarb\u00adoxy\u00adlic acid and nickel carbonate using water as solvent , where each of the NiII atoms is coordinated by a 2,6-pyridine-di\u00adcarb\u00adoxy\u00adlic acid dianion, a pyrazine mol\u00adecule, and a DMSO ligand \u2005\u00c5, i.e. the length of the b axis.The asymmetric unit contains two half Nind Fig.\u00a01. The triII chains form a double-chain structure via \u03c0\u2013\u03c0 stacking between their pyridine moieties . Double-chains of mol\u00adecule A are linked by C21A\u2014H21E\u22efO2Ai/iv, C12A\u2014H12A\u22efO1Ai, C21A\u2014H21D\u22efO4Aiii, and C22A\u2014H22D\u22efO4Aiii hydrogen bonds to form sheets extending along the same direction. Thus, alternating sheets with an ABAB pattern can be observed. Two neighboring sheets are connected via C11A\u2014H11A\u22efO5B and C11B\u2014H11B\u22efO5A hydrogen bonds to form a three-dimensional network. The hydrogen-bond lengths and angles are summarized in Table\u00a01In contrast to the \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions forming the inter\u00adior of the double-chains, the exterior of the double-chains is mainly occupied by polar DMSO mol\u00adecules and carboxyl\u00adate groups. As a result, a network of C\u2014H\u22efO hydrogen bonds exists in the space between the double-chains Fig.\u00a03, linkingIn summary, a separation of dissimilar inter\u00adactions can be observed between the non-covalent lipophilic \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef\u03c0 inter\u00adactions in the inter\u00adior of the double-chains and the polar hydrogen bonds in the exterior of the double-chains, further stabilizing the crystal structure.3 , 2,6-pyridine di\u00adcarb\u00adoxy\u00adlic acid , and pyrazine  were dissolved in 10\u2005ml dimethyl sulfoxide. The resulting mixture was transferred into a stainless steel autoclave which was heated at 373\u2005K for 24\u2005h and cooled to room temperature at a cooling rate of 0.1\u2005K per minute. Green needle-like crystals of the title compound were collected by filtration. Selected IR bands : 1640.6 (C=O), 1367.9 (C\u2014O), 950.9 (S=O), 480.6 (bridging pyrazine).Anhydrous NiCOUiso(H)= 1.2/1.5Ueq(C). Methyl H atoms were allowed to rotate around the corresponding C\u2014C bond. There are two disordered parts, both of which are in mol\u00adecule A. The carboxyl\u00adate atom O2A sits just outside of the mirror plane (occupancy 0.5) and one of the DMSO methyl groups is disordered over two positions in a ratio of 0.54\u2005(2):0.46\u2005(2). The C atom of this group was refined with isotropic displacement parameters.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016007064/wm5288sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016007064/wm5288Isup2.hklStructure factors: contains datablock(s) I. DOI: 1476677CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We have evaluated the efficacy of dapagliflozin in patients with type 1 diabetes mellitus (DM1) without adequate control. We expected that adding dapagliflozin to this population on top of their base treatment would lower their HbA1c levels.We conducted a pragmatic, open, 24-week study of treatment with 10\u00a0mg of oral dapagliflozin in patients with DM1 and chronic hyperglycemia. We evaluated glycemic control, lipid profile, weight, and insulin dose. Safety was assessed by adverse event reporting.p\u2009=\u20090.08). The hemoglobin A1C (HbA1C) level decreased from 9.18\u2009\u00b1\u20091.02 (77\u2009\u00b1\u200911.1\u00a0mmol/mol) to 8.05\u2009\u00b1\u20091.09\u00a0% (64\u2009\u00b1\u200911.9\u00a0mmol/mol) (p\u2009=\u20090.0156); total cholesterol decreased from 299\u2009\u00b1\u200912 to 199\u2009\u00b1\u20097\u00a0mg/dL (p\u2009=\u20090.02); triglycerides decreased from 184\u2009\u00b1\u200915 to 160\u2009\u00b1\u200911\u00a0mg/dL (p\u2009=\u20090.0002), HDL-C decreased from 40\u2009\u00b1\u200917 to 42\u2009\u00b1\u20099\u00a0mg/dL (p\u2009=\u20090.54); and LDL-C decreased from 187\u2009\u00b1\u200919 to 170\u2009\u00b1\u200921\u00a0mg/dL (p\u2009=\u20090.049). No adverse events were reported.Fasting glucose levels decreased from 176.42\u2009\u00b1\u200945.33\u00a0mg/dL to 139.67\u2009\u00b1\u200944.42\u00a0mg/dL (p\u2009=\u20090.05); although no significant valued was reached, postprandial glucose showed a decreased tendency from 230.25\u2009\u00b1\u200952.06\u00a0mg/dL to 193.83\u2009\u00b1\u200945.43\u00a0mg/dL (The beneficial effects of SGLT2 inhibitors on metabolic control and their safety after a 24-week open study demonstrate their potential indication as an adjunctive treatment with insulin in patients with DM1; however, long-term clinical trials should be considered. Treatment of Type 1 diabetes mellitus (DM1) is presently restricted to insulin and in selected cases, pramlintide and islet or pancreas transplantation .In contrast the management of DM1 with oral drugs is limited. Sodium/glucose cotransporter 2 inhibitors (SGLT2I), as initial or in combination therapy have recently been used to treat type 2 diabetes mellitus (DM2) . These dThe aim of this study was to evaluate the efficacy of dapagliflozin in a group of patients with poorly controlled DM1. We expected that adding dapagliflozin to this population\u2019s insulin regimen, would improve their glycemic control.We performed an open, 24-week, pragmatic clinical trial in a group of patients with poorly controlled DM1 in a private clinic in Monterrey, Nuevo Leon, M\u00e9xico from 2013\u20132014. Twelve patients met the following inclusion criteria: DM1 according to the American Diabetes Association classification ; both geChanges in fasting and postprandial glucose  and HbA1C were considered to be the primary outcomes. Appearance of hypoglycemia, genitourinary or micotic infections and ketonuria were routinely revised.The study protocol was approved by the local research ethics committee.2.Twelve patients were included  with a mean age of 27\u2009\u00b1\u200911\u00a0years and a mean duration of disease of 9.17\u2009\u00b1\u20097.41\u00a0years. All were overweight with a body mass index (BMI) of 27.98\u2009\u00b1\u20091.97\u00a0kg/mp\u2009=\u20090.05). The postprandial glucose decreased from 230.25\u2009\u00b1\u200952.06\u00a0mg/dL to 193.83\u2009\u00b1\u200945.43\u00a0mg/dL; however, it did not reach a significant value (p\u2009=\u20090.08). HbA1C significally decreased from 9.18\u2009\u00b1\u20091.02\u00a0% (77\u2009\u00b1\u200911.1\u00a0mmol/mol) to 8.05\u2009\u00b1\u20091.09\u00a0% (64\u2009\u00b1\u200911.9\u00a0mmol/mol) (p\u2009=\u20090.0156). The lipid profile was modified favorably, with total cholesterol decreasing from 299\u2009\u00b1\u200912 to 199\u2009\u00b1\u20097\u00a0mg/dL (p\u2009=\u20090.02), LDL-C from 187\u2009\u00b1\u200919 to 170\u2009\u00b1\u200921\u00a0mg/dL (p\u2009=\u20090.049) and triglycerides from 184\u2009\u00b1\u200915 to 160\u2009\u00b1\u200911\u00a0mg/dL (p\u2009=\u20090.0002). HDL-C was unchanged at 40\u2009\u00b1\u200917 and 42\u2009\u00b1\u20099\u00a0mg/dL (p\u2009=\u20090.54)  [\u00a0weeks [8The lipid profile also improved following treatment, with reductions in total cholesterol, c-LDL cholesterol and triglycerides . This is inconsistent with previous SGLT-2 studies and may have resulted from improved glycemic control, weight loss, or other causes , 9.An unattained metabolic control of DM1 has prompted a search for other therapeutic options, like pramlintide or islets transplantation , 10\u201312.Evidence of efficacy of SGLT2I in DM1 is limited ; howeverWe believe that dapagliflozin is safe and well tolerated with no clinically documented adverse effects. In addition, our study had the strength of a pragmatic design with a relatively long treatment period.However, recently the U.S. Food and Drug Administration (FDA) issued a Drug Safety Communication warning of an increased risk of diabetic ketoacidosis associated with the used of all the approved SGLT2I. This potential complication related is predictable, detectable, and preventable, with the full picture still favoring the use of SGLT2I DM1 patient .Nevertheless, we recognize that the data should be cautiously considered because the study was performed in a specialized care center with educated patients and a small sample size of overweight individuals. Also, we do not have information regarding the follow up of the patients.Dapagliflozin as an adjunct therapy to insulin caused significant changes in the HbA1C level, fasting and postprandial glucose and atherogenic lipid in patients with DM1. Thus, dapagliflozin may represent a new therapeutic approach, although long-term controlled clinical trials with a greater number of patients are needed to confirm our data."}
{"text": "N-{4-[(6-chloro\u00adpyridin-3-yl)meth\u00adoxy]phen\u00adyl}-2,6-di\u00adfluoro\u00adbenzamide is reported. The crystal packing is stabilized by N\u2014H\u22efN, C\u2014H\u22efO, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 hydrogen bonds supplemented by offset \u03c0\u2013\u03c0 stacking inter\u00adactions.The mol\u00adecular and crystal structure of  19H13ClF2N2O2, the conformation of the N\u2014H bond in the amide segment is anti to the C=O bond. The mol\u00adecule is not planar, with dihedral angles between the central benzene ring and the outer benzene and pyridyl rings of 73.35\u2005(7) and 81.26\u2005(6)\u00b0, respectively. A weak intra\u00admolecular C\u2014H\u22efO hydrogen bond occurs. In the crystal, N\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds lead to the formation of dimers. The N\u2014H\u22efN inversion dimers are linked by \u03c0\u2013\u03c0 contacts between adjacent pyridine rings [centroid\u2013centroid = 3.8541\u2005(12)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions. These contacts combine to stack the mol\u00adecules along the a axis.In the title compound, C The mixture was stirred at 283\u2013288\u2005K for 2\u2005h, then washed with 0.5% hydro\u00adchloric acid solution, and a saturated aqueous solution of sodium hydrogen carbonate, dried and evaporated. The residue was recrystallized from di\u00adchloro\u00admethane, giving colourless blocks of the title compound after three weeks.N-(4-(pyridin-3-ylmeth\u00adoxy)phen\u00adyl)benzamide or its substituted derivatives gave no hits. However, structures of eight substituted 2,6-di\u00adfluoro-N-phenyl\u00adbenzamide derivatives were found, see for example Cockroft et al.   = 0.93\u20130.97\u2005\u00c5 and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015023701/sj5486sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015023701/sj5486Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015023701/sj5486Isup3.cmlSupporting information file. DOI: 1441555CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The position of the second non-linking cage C atom was established unambiguously by geometric and crystallographic methods and there is no evidence of C/B disorder.In 1,1\u2032-bis[1,7-dicarba- 4H22B20, the two {1,7-closo-C2B10H11} cages are linked across a centre of inversion, with C\u2014C = 1.5401\u2005(16)\u2005\u00c5. The position of the second non-linking cage C atom was established unambiguously by geometric and crystallographic methods and there is no evidence of C/B disorder.In the title compound, C There are several isomeric possibilities for bis\u00ad(carboranes) composed of two C2B10 icosa\u00adhedra. Bis(ortho-carborane), 1,1\u2032-bis\u00ad , 1,1\u2032-bis, the subject of this study is, however, less well known. It was first prepared by Zakharkin & Kovredov ], (I)Whilst the chemistry of single-cage carboranes is well developed  linked across a crystallographic inversion centre by the C1\u2014C1A bond  \u00b0, and the facing penta\u00adgons B2/B3/B4/B5/B6 and B2A/B3A/B4A/B5A/B6A are staggered. The five C1\u2014B distances span the range 1.7107\u2005(12)\u20131.7385\u2005(12)\u2005\u00c5, whilst C7\u2014B connectivities lie between 1.6967\u2005(13) and 1.7180\u2005(13)\u2005\u00c5, with, in both cases, the two shortest distances being to the B atoms (B2 and B3) that lie between the C atoms. The B2\u2014B3 connectivity, 1.7947\u2005(13)\u2005\u00c5, is the longest B\u2014B link, with all (19) others lying between 1.7709\u2005(13) and 1.7891\u2005(15)\u2005\u00c5. In general terms these C\u2014B and B\u2014B distances are fully consistent with the averages recently calculated, 1.705\u2005(14) and 1.772\u2005(11)\u2005\u00c5, respectively z] Fig.\u00a01. The twoB at 2.39\u2005\u00c5 . Although CH units and BH units in carboranes are protonic and hydridic, respectively, there is no evidence of di\u00adhydrogen bonding, the shortest such contact being H7\u22efH12C at 2.61\u2005\u00c5 [symmetry code: (C) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0The only H\u22efH contact less than 2.40\u2005\u00c5 is H6\u22efH6closo-C2B10 fragment using Conquest (Version 1.16) returned 132 hits of which only two involve the 1,1\u2032-bis\u00ad unit. In DUWJAH 2} groups attached to C7 and C7\u2032 whilst in DUWJEL (OMe)} units. Of the remaining 130 hits there are five cases of the parent mol\u00adecule 1,7-closo-C2B10H12 co-crystallized with other mol\u00adecules, the first of these to be reported being the hexa\u00admethyl\u00adphospho\u00adr\u00adamide adduct TOKGOP  was refined and then analysed by both the Vertex-to-Centroid Distance  = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S1600536814022132/hb7290sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814022132/hb7290Isup2.hklStructure factors: contains datablock(s) I. DOI: 1027936CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H = (1\u20133/Nr)In the Methods section, Equation 2b is incorrect. The correct equation is: \u03b8"}
{"text": "I ions complexed by ferrocenediyl-1,1\u2032-dicarbo\u00adnitrile forming a paddle-wheel with two acetone mol\u00adecules, with one coordinating on top of one trigonal\u2013planar-coordinated copper ion, and the other as a packing solvent.The first ferrocenylcarbo\u00adnitrile copper complex is reported. The structure consists of two Cu O)tris\u00addicopper(I) bis\u00ad(tetra\u00adfluorido\u00adborate) acetone monosolvate, [Cu2Fe3(C6H4N)6(C3H6O)](BF4)2\u00b7C3H6O, consists of two CuI ions bridged by a ferrocene-1,1\u2032-dicarbo\u00adnitrile moiety in a paddle-wheel-architectured sandwich complex with two BF4\u2212 units as counter-ions. One of the latter is equally disordered over two sets of sites. The two CuI ions are complexed in a trigonal\u2013planar manner by three nitrile N-donor atoms. Further inter\u00adactions by the O atom of an acetone mol\u00adecule to one of the CuI atoms and a weak \u03b72,\u03c0-inter\u00adaction of two atoms of a cyclo\u00adpenta\u00addienyl ring to the other CuI atom complete a distorted trigonal\u2013pyramidal environment for each of the metal ions. A further acetone mol\u00adecule is also present as a solvent mol\u00adecule. The crystal packing is consolidated by several \u03c0\u2013\u03c0 inter\u00adactions.The mol\u00adecular structure of (acetone-\u03ba M\u2014C\u00a0C\u2014 , showing moderate electron communication between two redox-active metallocenyl termini in the mixed-valence species \u2013phenyl\u00adene bridge shows a moderate delocalization. In contrast, a weak electron transfer by generation of the mixed-valence species [Ru(N\u00a0CFc)(NH3)5]3+ [Fc = Fe(\u03b75-C5H4)(\u03b75-C5H5)] has been described  bridging unit between two redox-active ferrocenyl moieties 2CO}{\u03bc-Fe(\u03b75-C5H4C\u00a0N)2}3](BF4)2\u00b7(CH3)2CO, (I)The electron-transfer properties of the acetyl\u00adide function have been investigated intensively by using bridging units of the type \u2014C\u00a0C\u2014 al. 2011 describe2Fe3 complex mol\u00adecule in the asymmetric unit consisting of two CuI ions bridged by three 1,1\u2032-ferrocenediyl dicarbo\u00adnitrile ligands that form a triangular paddle-wheel sandwich-type complex with iron\u22efiron distances ranging from 9.1739\u2005(13) (Fe2\u22efFe3) to 10.0385\u2005(12)\u2005\u00c5 . The complex crystallizes with two BF4\u2212 counter-ions and two mol\u00adecules of acetone. One acetone mol\u00adecule coordinates with its oxygen atom to Cu1 [Cu1\u2014O1 2.375\u2005(2)\u2005\u00c5], leading to an 18 VE complex and an overall distorted trigonal\u2013pyramidal environment. The Cu2 ion exhibits a weak inter\u00admolecular \u03b72, \u03c0 inter\u00adaction  as compared to Cu2 [0.0602\u2005(16)\u2005\u00c5] due to a stronger inter\u00adaction with the axial moiety. The Cu\u22efCu distance [3.3818\u2005(7)\u2005\u00c5] exceeds the sum of the van der Waals radii  \u00b0; \u03b1 C5\u22efCu2, 93.23\u2005(1) \u00b0; Table\u00a01Besides the already noted inter\u00admolecular inter\u00adaction between Cu2 and the mid-point of the C26\u2014C27 bond, \u03c0\u2013\u03c0 inter\u00adactions are present in the crystal packing between the C23 atom and its symmetry-generated equivalent (BF4)2\u00b7(CH3)2CO: Copper powder , Cu(BF4)2\u00b75H2O  and ferrocene-1,1\u2032-dicarbo\u00adnitrile  were stirred in 5\u2005ml of di\u00adchloro\u00admethane at room temperature overnight. The resulting orange precipitate was filtered off using zeolite and washed several times with 20\u2005ml of di\u00adchloro\u00admethane until the filtrate was colorless. The residue was taken up in acetone and this solution was evaporated to dryness using a rotary evaporator affording (I)4]2\u00b75H2O). IR : \u03bd = 2248 (CN). 1H NMR  = 5.12 , 4.82 . 13C{1H} NMR: Data not available due to low solubility. HRMS (ESI\u2013TOF): M+ C12H8N2CuFe (C24H16N4CuFe2): m/z = 534.9342 ; M+ C24H16N4CuFe2 (C12H8N2CuFe): m/z = 298.9342 .Ferrocene-1,1\u2032-dicarbo\u00adnitrile was prepared according to a published procedure (Strehler Uiso(H) = 1.2Ueq(C) and a C\u2014H distance of 0.93\u2005\u00c5 for aromatic and Uiso(H) = 1.5Ueq(C) and a C\u2014H distance of 0.96\u2005\u00c5 for methyl H atoms. The F atoms of one of the two BF4\u2212 ions were refined as equally disordered over two sets of sites using DFIX [B\u2014F 1.38\u2005(2)\u2005\u00c5] and DANG [F\u2014F 2.25\u2005(4)\u2005\u00c5] instructions. Since some anisotropic displacement ellipsoids were rather elongated, DELU/SIMU/ISOR restraints were also applied  I. DOI: 10.1107/S2056989015001760/wm5104Isup2.hklStructure factors: contains datablock(s) I. DOI: 1045804CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "AbstractParaplonobia Wainstein and Neopetrobia Wainstein (Trombidiformes: Tetranychidae) are reported for the first time from Saudi Arabia. Three new species Paraplonobia (Anaplonobia) arabica Mirza & Alatawi, sp. n., Paraplonobia (Anaplonobia) haloxylonia Alatawi & Mirza, sp. n. and Paraplonobia (Anaplonobia) tabukensis Kamran & Alatawi, sp. n. are described and illustrated based on adult females, collected from Prosopisjuliflora (SW.) Dc. (Fabaceae) and Haloxylonsalicornicum Bunge (Amaranthaceae) from two different regions of Saudi Arabia. Neopetrobiamcgregori (Pritchard and Baker) is redescribed and illustrated based on female collected from Cynodondactylon L. (Poaceae).The diagnostic morphological features including leg chaetotaxy of all known species of the subgenus Anaplonobia is tabulated. A key to the world species of the genus Paraplonobia is also provided.The two tetranychid genera  Paraplonobia Wainstein belongs to the tribe Hystrichonychini Pritchard and Baker of the subfamily Bryobiinae (Acari: Prostigmata: Tetranychidae). Anaplonobia and Paraplonobia as subgenera of Aplonobia Womersley. Later, Anaplonobia and Paraplonobia as two valid genera. After that, Paraplonobia into three subgenera: Anaplonobia Wainstein, Brachynychus Mitrofanov & Strunkova and Paraplonobia Wainstein on the basis of coxal setal count and the aspect of peritremes and considered the genus Anaplonobia as subgenus of Paraplonobia , Eutetranychuspalmatus Attiah, Oligonychusafrasciaticus (McGregor), Oligonychuspratensis (Banks), Tetranychuscinnabarinus , Tetranychusturkrestzni (Ugarov & Nikolskii), and Tetranychusurticae (Koch)  harteni Meyer and Paraplonobia (Paraplonobia) dactyloni Smiley & Baker were reported from Yemen (A few tetranychid species have been reported from Saudi Arabia (SA): e (Koch) . The genom Yemen .Paraplonobia and Neopetrobia, are reported upon for the first time from Saudi Arabia with three new species: Paraplonobia (Anaplonobia) arabica sp. n., Paraplonobia (Anaplonobia) haloxylonia sp. n. and Paraplonobia (Anaplonobia) tabukensis sp. n. which are described and illustrated based on adult females. The male of Paraplonobia (Anaplonobia) haloxylonia sp. n. is also described and illustrated. Neopetrobiamcgregori (Pritchard & Baker) is redescribed and illustrated based on female.Two genera, Anaplonobia are provided including body morphological features, leg I length in comparison to body length, and leg chaetotaxy  haloxylonia sp. n., female paratype each of Paraplonobia (Anaplonobia) arabica sp. n., and Paraplonobia (Anaplonobia) tabukensis sp. n., with Accession numbers, OSAL 0115769, OSAL 00115768, OSAL 0110333 and OSAL 0110332 respectively, that were deposited at UniversityOhio State  Acarology Laboratory(OSAL), USA.The mite specimens were collected by shaking the plant parts, especially leaves, onto a white sheet of paper. Mites found moving on paper were collected with the help of a camel hairbrush and preserved in small vials containing 70% ethanol. Preserved mite specimens were observed under a stereomicroscope  and mounted on glass slides in Hoyer\u2019s medium. The mounted specimens were examined under phase contrast microscope . Different body parts were pictured using an auto montage software system , then drawn with Adobe Illustrator . All measurements are in micrometers. The terminology used in this paper follows that of Taxon classificationAnimaliaProstigmataTetranychidaeGenusWainstein, 1960Aplonobia (Paraplonobia) Wainstein, 1960: 140.Paraplonobia : Aplonobia (Paraplonobia) echinopsili Wainstein, 1960 by original designation.Based on Baker and Tuttle 1968, Gutierrez 1955, 1 normal in position, coxal setal formula variable, most species with 2\u20132\u20131\u20131 except one species of the subgenus Brachynychus having 4\u20133\u20132\u20132 setae on coxae I\u2013IV respectively; anal setae three pairs; peritremes simple/anastomosing; tarsus I with two sets of duplex setae, present close to distal end of tarsus; claws and empodium pad-like each with tenant hairs  Eight species with dorsal body setae slightly shorter/as long as or longer than distances to the bases of consecutive setae (Tables Paraplonobia (Anaplonobia) arabica sp. n., Paraplonobia (Anaplonobia) haloxylonia sp. n., and Paraplonobia (Anaplonobia) tabukensis sp. n.) reported in this study , comparative length of setae with respect to the distance of setae next behind, shape of peritremes , propodosomal shield , hysterosoma , comparative length of leg I with respect to body length (shorter/longer) and leg chaetotaxy are the major diagnostic characters vary among/within the species of subgenus ia Table , 2.Anaplonobia have been reported from USA, Mexico, South Africa and Pakistan and collected mostly from three host plants families Asteraceaea, Fabaceae and Poaceae (Most species of the subgenus  Poaceae  (Table 1Paraplonobia (Anaplonobia) arabica sp. n., collected from Prosopisjuliflora from three different regions  of Saudi Arabia, are morphologically similar except for some variations in setal counts on Tibia II and Tarsus I\u2013II\u2013III. (Table Paraplonobia (Anaplonobia) prosopis had been found also in the description made by Anaplonobia, setal variations on genua, tibiae and tarsi have been found among the different specimens collected from the same host and location within the same species. i.e. genua I (8\u20139) in Paraplonobia (Anaplonobia) candicans, tibia I (12\u201313) and tarsus II (12\u201313) of Paraplonobia (Anaplonobia) glebulanta, and tarsus III (12\u201313) of Paraplonobia (Anaplonobia) theroni . Measurement of holotype followed by 8 paratypes (in parenthesis) Figs \u20138.Dorsum , sc1 40 (38\u201341), sc2 41 (40\u201343), c1 45 (44\u201348), c2 42 (40\u201344), c3 40 (39\u201344), d1 34 (32\u201338), d2 44 (43\u201346), e1 45 (44\u201348), e2 44 (43\u201345), f1 45 (44\u201345), f2 44 (42\u201345), h1 46 (45\u201348). Distance between dorsal setae: v2\u2013v2 53 (51\u201355), v2\u2013sc1 97 PageBreak(95\u201398), sc1\u2013sc2 56 (54\u201357), sc1\u2013sc1 166 (162\u2013167), sc2\u2013sc2 263 (260\u2013266), c1\u2013c1 94 (92\u201396), c1\u2013c2 82 (80\u201385), c2\u2013c3 41 (39\u201344), c2\u2013c2 261 (260\u2013264), c3\u2013c3 345 (340\u2013346), d1\u2013d1 82 (80\u201384), d1\u2013d2 81 (80\u201382), d2\u2013d2 226 (224\u2013228), c1\u2013d1 75 (74\u201378), c3\u2013d2 97 (95\u201399), e1\u2013e1 63 (61\u201365), e1\u2013e2 78 (74\u201379), e2\u2013d2 85 (83\u201386), e2\u2013e2 79 (75\u201379), f1\u2013f1 63 (60\u201365), f2\u2013f2 107 (105\u2013108), f1\u2013f2 53 (50\u201354), f1\u2013d1 69 (66\u201370), h1\u2013h1 57 (55\u201359).sum Fig. . Body ovVenter , g2 40 (38\u201342), g1\u2013g1 40 (39\u201344), g2\u2013g2 56 (52\u201357), g1\u2013g2 12 (10\u201314); anal setae three pairs, ps1 21 (18\u201324), ps2 37 (35\u201339), ps3 58 (54\u201360), ps1\u2013ps1 33 (30\u201334), ps2\u2013ps2 26 (24\u201327), ps3\u2013ps3 19 (18\u201322); para-anal setae two pairs, h2 33 (31\u201334), h2\u2013 h2 17 (16\u201318), h3 38(35\u201340), h3\u2013h3 46 (45\u201348).ter Fig. . IdiosomGnathosoma , Deesa Valley, Dessa, Tabuk, SA, 27\u00b036.048'N, 036\u00b025.592'E, October, 18, 2015, coll. J.H. Mirza.; seven paratype females, Prosopisjuliflora (Fabaceae), Sharma, Near Red Sea, Tabuk, SA, 28\u00b003.479'N, 035\u00b017.186'E, October, 19, 2015, coll. M. Kamran.Holotype and one paratype female, Paraplonobia (Anaplonobia) arabica sp. n. relates to Paraplonobia (Anaplonobia) prosopis , Paraplonobia (Anaplonobia) algarrobicola  and Paraplonobia (Anaplonobia) boutelouae Tuttle & Baker, 1968 because of sharing following similar characters: dorsal body setae spatulate and distinctly shorter to the distances of setae next behind and widely spaced dorsal hysterosomal striations. Also, the new species closely resembles Paraplonobia (Anaplonobia) prosopis by setae c1 at least reaching half distance to the bases of setae d1. However, the new species differs PageBreakfrom all related species by having stylophore anteriorly with slight incision (notch). The new species is also distinguished from Paraplonobia (Anaplonobia) prosopis by setae c1 reaching to the distance of setae d1 (2/3 vs.1/2), setae c1\u2013c1 almost 1.5 times widely spaced than setae f1\u2013f1 vs. almost sub/equally spaced in Paraplonobia (Anaplonobia) prosopis. The new species can be separated from other related species Paraplonobia (Anaplonobia) algarrobicola and Paraplonobia (Anaplonobia) boutelouae by the setae c1 reaching 2/3 to the distance of d1 vs. less than half as long as distances to the bases setae next behind in later speciesThe Taxon classificationAnimaliaProstigmataTetranychidaehttp://zoobank.org/09E8353-E635-4C38-B277-8D6DDC56C31ADorsal setae lanceolate, densely serrate, not set on tubercles and distinctly shorter to the distances of setae next behind, dorsocentral setae  almost 1/3 to the distance of setae next behind, propodosoma medially with weak, longitudinal irregular striations, hysterosoma with transverse and closely spacedstriations medially, stylophore slightly notched anteriorly, peritremes anastomosed distally, with few long thread like branches, and hysterosomal striations closely spaced, leg I shorter than body.n = 39). Measurements of holotype followed by 38 paratypes (in parenthesis) , sc1 24 (23\u201325), sc2 22 (21\u201324), c1 19 (18\u201321), c2 22 (21\u201323), c3 25 (24\u201328), d1 15 (12\u201316), d2 18 (17\u201319), e1 16 (15\u201317), e2 20 (19\u201320), f1 25 (24\u201328), f2 31 (29\u201332), h1 34 (32\u201335). Distance between dorsal setae: v2\u2013v2 72 (70\u201373), v2\u2013sc1 75 (72\u201378), sc1\u2013sc2 66 (63\u201367), sc1\u2013sc1 167 (163\u2013172), sc2\u2013sc2 254 (250\u2013259), c1\u2013c1 90 (88\u201392), c1\u2013c2 75 (71\u201378), c2\u2013c3 81 (78\u201385), c2\u2013c2 231 (229\u2013234), c3\u2013c3 373 (372\u2013375), d1\u2013d1 91 (89\u201392), d1\u2013d2 65 (62\u201369), d2\u2013d2 204 (201\u2013206), c1\u2013d1 103 (100\u2013104), c3\u2013d2 160 (158\u2013161), e1\u2013e1 55 (53\u201357), e1\u2013e2 53 (50\u201354), e2\u2013d2 85 (82\u201386), e2\u2013e2 150 (148\u2013152), f1\u2013f1 60 (59\u201362), f2\u2013f2 80 (78\u201383), f1\u2013f2 28 (25\u201329), f1\u2013d1 93 (91\u201394), h1\u2013h1 31 (28\u201332).sum Fig. . Body ovVenter , g2 20 (19\u201321), g1\u2013g1 32 (31\u201333), g2\u2013g2 35 (34\u201336), g1\u2013g2 10 (10\u201312); anal setae three pairs, ps1 11 (10\u201312), ps2PageBreakPageBreakPageBreak16 (15\u201317), ps3 17(16\u201318), ps1\u2013ps1 16 (15\u201318), ps2\u2013ps2 22 (20\u201323), ps3\u2013ps3 26 (25\u201326); para\u2013anal setae two pairs, h2 16 (15\u201317), h2\u2013 h2 14 (13\u201316), h3 17 (15\u201317), h3\u2013h3 31 (30\u201332)  Fig. .Gnathosoma \u20139\u20139\u20139; tarsi I with 15 tactile setae, two sets of duplex setae at distal end, 11 tactile setae and two solenidia well proximal to duplex setae, two eupathidia; tarsi II with 10 tactile setae, one set of duplex setae, two eupathidia and one solenidion; tarsi III with 12 tactile setae and one solenidion; tarsi IV with 12 tactile setae and one solenidion. True claws pad like each with one pair of tenant hair; empodium pad-like with two rows of small tenant hairs.egs Figs . Length Male (n = 11)  Figs \u201328. Dorssum Fig. . Body alVenter , anal setae three pairs ; para-anal setae two pairs ; aedeagus up turned, broadly sigmoid, sharply tapering distally , Salbookh Road, Dariyah, Riyadh, SA, 24\u00b030.649'N, 46\u00b046.615'E, September, 18, 2012, coll. M. Kamran; four males and 22 female paratypes, Hilaria sp. (Poaceae), Tashlia, Heyer Road, Riyadh, SA, 24\u00b029.000'N, 46\u00b047.890'E, January, 17, 2015, coll. J.H. Mirza; five males and four females paratypes, Hilaria spp. (Poaceae), Sanabal Farm, Kharaj, Riyadh, SA, 24\u00b016.999'N, 47\u00b011.854'E, January, 23, 2015, coll. M. Kamran.Holotype female, one male and two female paratypes, Remarks. The Paraplonobia (Anaplonobia) haloxylonia sp. n. closely resembles Paraplonobia (Anaplonobia) contiguus (Paraplonobia (Anaplonobia) contiguus by comparative length of leg I (shorter than body vs. longer than body), dorsocentral setae  almost 1/3 to the distance of setae next behind vs. more than half, number of setae on genu I (5 vs. 4) in Paraplonobia (Anaplonobia) contiguus.ontiguus  because Taxon classificationAnimaliaProstigmataTetranychidaehttp://zoobank.org/57BF2D3A-80B0-4C7E-90CD-FACB4543B5FFDorsal setae slightly lanceolate, densely serrate, not present on tubercles and distinctly shorter to the distances of setae next behind, prodorsum entirely with longitudinal striaitons, hysterosomal striations closely spaced, peritremes complex anastomosed distally, stylophore slightly rounded anteriorly, leg I shorter than body length, number of setae on femur I\u2013IV 8\u20136\u20133\u20133, number of setae on genu I\u2013IV 4\u20135\u20133\u20133.(n = 3). Measurements of holotype followed by 2 paratypes (in parenthesis) Figs \u201336.Dorsum , sc1 29 (28\u201331), sc2 30 (28\u201332), c1 28 (26\u201330), c2 26 (24\u201328), c3 29 (28\u201332), d1 23 (21\u201325), d2 22 (21\u201324), e1 21 (20\u201323), e2 22 (21\u201324), f1 23 (21\u201324), f2 26 (24\u201327), h1 27 (25\u201329). Distance between dorsal setae: v2\u2013v2 89 (85\u201390), v2\u2013sc1 68 (65\u2013690), sc1\u2013sc2 68 (67\u201370), sc1\u2013sc1 204 (202\u2013206), sc2\u2013sc2 301 298\u2013302), c1\u2013c1 138 (135\u2013140), c1\u2013c2 91 (89\u201392), c2\u2013c3 79 (75\u201380), c2\u2013c2 327 (325\u2013328), c3\u2013c3 424 (422\u2013426), d1\u2013d1 119 (118\u2013120), d1\u2013d2 91 (89\u201392), d2\u2013d2 295 (292\u2013298), c1\u2013d1 88 (86\u201389), c3\u2013d2 110 (109\u2013112), e1\u2013e1 27 (25\u201328), e1\u2013e2 85 (84\u201386), e2\u2013d2 85 (84\u201386), e2\u2013e2 229 (228\u2013231), f1\u2013f1 78 (76\u201380), f2\u2013f2 113 (110\u2013114), f1\u2013f2 35 (33\u201336), f1\u2013d1 82 (81\u201384), h1\u2013h1 53 (52\u201356).sum Fig. . Body roVenter , g2 39 (35\u201340), g1\u2013g1 52 (50\u201355), g2\u2013g2 60 (58\u201364), g1\u2013g2 12 (10\u201313); anal setae three pairs, ps1 20 (18\u201321), ps2 26 (24\u201327), ps3 28 (27\u201329), ps1\u2013ps1 23 (20\u201324), ps2\u2013ps2 32 (31\u201335), ps3\u2013ps3 23 (21\u201326); para-anal setae two pairs, h2 27 (26\u201328), h2\u2013 h2 11 (10\u201313), h3 32 (31\u201334), h3\u2013h3 28 (27\u201329).ter Fig. . IdiosomGnathosoma , 30 km Tabuk road, Sharma, Tabuk region, SA, 28\u00b003.479'N, 035\u00b017.186'E, October, 19, 2015, coll. M. Kamran and J.H. Mirza.Holotype female, two paratype females, Paraplonobia (Anaplonobia) tabukensis sp. n. closely resembles Paraplonobia (Anaplonobia) theroni (Paraplonobia (Anaplonobia) theroni by shape of stylophore anteriorly (rounded vs. slightly indented), number of setae on femur I\u2013IV (8\u20136\u20133\u20133 vs. 9\u20136\u20134\u20134), number of setae on genu I\u2013IV (4\u20135\u20133\u20133 vs. 5\u20135\u20136\u20136), number of setae on tibia III (8 vs. 6) and on tarsi I\u2013II excluding duplex setae and solenidia (10\u20137 vs. 18\u201314) in Paraplonobia (Anaplonobia) theroni.The  theroni  because  theroni , 1987. TPageBreakTaxon classificationAnimaliaProstigmataTetranychidaeGenusWainstein, 1956Monoceronychus : Neopetrobia : Wainstein 1956: 151, Neopetrobiadubinini Wainstein, 1956.Based on Baker and Tuttle 1968, Gutierrez 1955, 1) widely spaced, not normal as c1; peritremes anastomosing distally.True claws pad like, each bearing a pair of tenant hairs; empodial pad longer than true claws, bearing a row of tenant hairs, distally not coalescent; dorsum with 3 pairs of prodorsal setae which are short and spindle shaped or spatulate; setal tubercles small or nonexistent; fourth pair of dorsocentral setae Monoceronychusmcgregori Pritchard & Baker, 1955.Neopetrobiamcgregori (Pritchard & Baker) Meyer, 1987. Female (n=9). Body oval; length of idiosoma 369\u2013372, maximum width 238\u2013241, length of body (gnathosoma + idiosoma) 430\u2013433.Dorsum . Length of intercoxal and coxal setae: 1a 18\u201319, 3a 19\u201320, 4a 15\u201316, 1b 30\u201331, 1c 13\u201314, 2b 16\u201317, 2c 10\u201313, 3b 15\u201317, 4b 11\u201312; aggenital setae (ag) 26\u201327, ag\u2013ag 38\u201339; genital setae two pairs, g1 17\u201318, g2 21\u201322, g1\u2013g1 41\u201342, g2\u2013g2 76\u201378, g1\u2013g2 21\u201322; anal setae three pairs, ps1 11\u201312, ps2 10\u201311, ps3 12\u201313, ps1\u2013ps1 11\u201313, ps2\u2013ps2 16\u201318, ps3\u2013ps3 11\u201313; para-anal setae two pairs, h2 11\u201313, h2\u2013 h2 7\u20139, h3 7\u20138, h3\u2013h3 17\u201319.ter Fig. . IdiosomGnathosoma , near exit10, King Abdullah Road, Riyadh, SA, 24\u00b045.826'N, 46\u00b045.470'E, September 07, 2015, coll. M. Kamran and E. M. Khan.12 females, Neopetrobiamcgregori was originally described very briefly under the genus Monoceronychus and has been only reported from Miami shores of Florida, USA   . WorldwiPageBreak"}
{"text": "II complex with a -N-phenyl-carbamohydrazino\u00adthio\u00adate ligand is reported. The crystal structure shows DMSO mol\u00adecules bridging the complex units, building an one-dimensional H-bonded polymer.The synthesis and crystal structure of a Zn N-phenyl-2-hy\u00addra\u00adzine\u00adcar\u00adbo\u00adthio\u00adamide ligand with zinc acetate dihydrate in a 2:1 molar ratio yielded a yellow solid, which was crystallized from DMSO to obtain the title compound, [Zn(C17H16N3S)2]\u00b7C2H6OS. The ZnII ion is four-coordinated in a distorted tetra\u00adhedral environment by two deprotonated ligands. Each ligand acts as an N,S-donor, forming a five-membered metallacycle. The maximum deviation from the mean plane of the N\u2013N\u2013C\u2013S chelate group is 0.0029\u2005(14)\u2005\u00c5 for the N-donor atom of one ligand and 0.0044\u2005(14)\u2005\u00c5 for the non-coordinating N atom of the second. The dihedral angle between the planes of the two chelate groups is 72.80\u2005(07)\u00b0. Bond lengths in the ligands are compared with those in the crystal structure of the free ligand. In the crystal, complex mol\u00adecules are connected by dimethyl sulfoxide solvate mol\u00adecules via N\u2014H\u22efO hydrogen-bonding inter\u00adactions, building a one-dimensional hydrogen-bonded polymer along the a-axis direction. The S atom and one C atom of the dimethyl sulfoxide solvate mol\u00adecules are disordered over two sets of sites with an occupancy ratio of 0.6:0.4.The reaction of the  II complex with the N-phenyl-2-hy\u00addra\u00adzine\u00adcar\u00adbo\u00adthio\u00adamidate ligand. Thio\u00adsemicarbazone derivatives are N,S-donors with a wide range of coordination modes and a variety of applications in biological inorganic chemistry /N21\u2014N22 = 1.393\u2005(3)\u2005\u00c5, N2\u2014C11 = 1.303\u2005(3)/N22\u2014C31 = 1.304\u2005(3)\u2005\u00c5 and C11\u2014S1 = 1.755\u2005(2)/C31\u2014S21 = 1.749\u2005(2)\u2005\u00c5.The acidic hydrogen of the hydrazine fragment is lost by the reaction with the acetate anion. The negative charge of the deprotonated ligand is delocalized over the N\u2014N\u2014C\u2014S entity, as indicated by their inter\u00admediate bond lengths. The bond lengths in the ligand are also affected by the coordination with the metal atom, especially the C\u2014S bond length, which is consistent with increased single-bond character. In the crystal structure of the free ligand  is 58.25\u2005(11)\u00b0. In the second ligand, the corresponding angle is 49.99\u2005(11)\u00b0 between the C25\u2013C30 and C32\u2013C37 rings. In addition, the aliphatic rings are also not planar. The maximum deviation from the mean plane for the C1\u2013C5/C10 ring is 0.355\u2005(3)\u2005\u00c5 for C3 and for the C21\u2013C25/C30 ring the maximum deviation is 0.359\u2005(3)\u2005\u00c5 for C23, with both of the aliphatic rings having an envelope conformationII complex mol\u00adecules and the DMSO solvent mol\u00adecules build a monomeric entity. The DMSO mol\u00adecule bridges two complex mol\u00adecules via inter\u00admolecular N\u2014H\u22efO hydrogen-bonding inter\u00adactions, building a one-dimensional hydrogen-bonded polymer along the a-axis direction hy\u00addra\u00adzine\u00adcar\u00adbo\u00adthio\u00adamide dissolved in THF (2\u2005mmol/40\u2005mL) with zinc acetate dihydrate dissolved in ethanol (1\u2005mmol/30\u2005mL) was refluxed for 4\u2005h under continuous stirring. An orange solid was obtained, filtered and washed with ethanol. Suitable crystals for X-ray diffraction were obtained in DMSO by slow evaporation of the solvent.Starting materials were commercially available and used without further purification. The ligand synthesis was adapted from a procedure reported previously  = 1.2 Ueq(C) (1.5 for methyl H atoms) using a riding model with C\u2014H = 0.95\u2005\u00c5 for aromatic, C\u2014H = 0.99\u2005\u00c5 for methyl\u00adene, C\u2014H = 0.98\u2005\u00c5 for methyl and N\u2014H = 0.88\u2005\u00c5. In the DMSO solvate mol\u00adecule, the S atom and methyl\u00adene C atom C42 and attached H atoms are disordered and were refined using a split model with an occupancy ratio of 0.4:0.6.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901500612X/im2462sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S205698901500612X/im2462Isup2.hklStructure factors: contains datablock(s) I. DOI: 1056177CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "All four phenyl rings in the two independent mol\u00adecules are arranged in a propeller-like conformation. The two mol\u00adecules exhibit S,R- and R,S- chirality and are connected via C\u2014H\u22efO inter\u00admolecular inter\u00adactions.In the title compound, C 34H28O4, the cyclo\u00adhexa\u00addiene ring has a screw-boat conformation with a torsion angle between the double bonds being on average ca 15\u00b0 [15.2\u2005(3) and \u221215.3\u2005(3) in the two independent mol\u00adecules]. All four phenyl rings in both mol\u00adecules are arranged in a propeller-like conformation. The two mol\u00adecules exhibit S,R- and R,S- chirality, respectively, and are connected via C\u2014H\u22efO inter\u00admolecular inter\u00adactions. In turn, these weakly bound dimers form the mol\u00adecular crystal.In the title compound, C Addition reactions of tetra\u00adphenyl\u00adcyclo\u00adpenta\u00addienone, often abbreviated to \u2018tetra\u00adcyclone\u2019, were reviewed by Allen 1945, 1962 \u25b8.This study provides an opportunity to investigate the geometry of 1,3-cyclo\u00adhexa\u00addiene rings surrounded by bulky substituents with no strong inter\u00admolecular inter\u00adactions.s-gauche \u2005\u00c5, \u03b8 = 115.8\u2005(3)\u00b0 and \u03c6 = 213.1\u2005(3); (C101\u2013C106) Q = 0.463\u2005(2)\u2005\u00c5, \u03b8 = 63.7\u2005(2)\u00b0 and \u03c6 = 33.5\u2005(3)\u00b0.The cyclo\u00adhexa\u00addiene rings  and \u221215.3\u2005(3) for the two independent mol\u00adecules  form short contacts  with di\u00admethyl\u00admaleate following Allen & Sheps 1934. GC\u2013MS aUiso = 1.2iUso(C). All aromatic hydrogen atoms were refined with riding coordinates with C\u2014H = 0.95\u20130.98\u2005\u00c5 and Uiso = 1.2Uiso(C). Idealized methyl groups were refined as rotating groups with Uiso = 1.5Uiso(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016009403/zl2665sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016009403/zl2665Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016009403/zl2665Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016009403/zl2665Isup4.cmlSupporting information file. DOI: 1484412CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds link complex mol\u00adecules, forming a three-dimensional network incorporating The title complex, [Mg(C 7H7N4O2)2(H2O)4], lies across an inversion centre and the MgII atom is coordinated in a slightly distorted octa\u00adhedral environment by four aqua ligands in the equatorial sites and two 1,3-dimethyl-2,6-dioxo-3,7-di\u00adhydro-1H-purin-9-ide ligands, through imidazole ring N atoms, in the axial sites. An intra\u00admolecular O\u2014H\u22efO hydrogen bond forms an S(7) graph-set motif. In the crystal, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds link complex mol\u00adecules forming a three-dimensional network incorporating R42(8) and R22(18) graph-set motifs.The title complex, [Mg(C II ion in a basic solution to give rise to a tetra\u00adaqua mononuclear MgII complex, (I)Co-crystallization represents a crystal engineering approach for modifying properties of active pharmaceutical ingredients (APIs) Sun, 2013. Metal cII atom is coordin\u00adated in a slightly distorted octa\u00adhedral environment ], in the axial sites. The symmetry-unique purine ring system is essentially planar, with a maximum deviation of 0.030\u2005(2)\u2005\u00c5 for N3 and the bonded methyl C atoms C4 and C5 deviate from this mean plane by \u22120.118\u2005(3) and 0.136\u2005(2)\u2005\u00c5, respectively.The mol\u00adecular structure of (I)t Table\u00a01 by four et al., 1995iii = 2.829\u2005(3)\u2005\u00c5 and O4\u22efO1iv = 2.780\u2005(2)\u2005\u00c5; symmetry codes: (iii) \u2212x, \u2212y, \u2212z; (iv) x, y, z\u00a0+\u00a01] between a coordinating water mol\u00adecule and a carbonyl group of a symmetry-related theophylline group. The mononuclear units are connected into a layer parallel to (010) \u2005\u00c5; symmetry code: (ii) x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0In the crystal, the coordinating water mol\u00adecules are involved in various hydrogen-bonding inter\u00adactions Table\u00a02. A (8) g0) Fig.\u00a02, which i0) Fig.\u00a02 by hydroA search of the Cambridge Structural Database  in water (15\u2005ml) was then added. The resulting solution was kept in air and, after several days, colourless block-shaped crystals were obtained.Theophylline  was dissolved in water (20\u2005ml). An aqueous solution (15\u2005ml) of NaOH  was added slowly. MgClUiso(H) = 1.2Ueq(C) or 1.5Ueq(C). H atoms bonded to O atoms were located in difference Fourier maps and were refined with a distance restraint of O\u2014H = 0.87\u2005(1)\u2005\u00c5. The isotropic displacement parameters were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015003758/lh5752sup1.cifCrystal structure: contains datablock(s) I, LOU. DOI: 10.1107/S2056989015003758/lh5752Isup2.hklStructure factors: contains datablock(s) I. DOI: 1050901CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two \u03bc3-bridging I\u2212 anions are linked by three AgI ions, leading to the formation of a dicapped triangular motif with Ag\u22efAg separations in the range 3.0823\u2005(5)\u20133.2999\u2005(5)\u2005\u00c5. Each AgI atom exhibits a distorted tetra\u00adhedral geometry, with coordination to two I atoms and two P atoms from bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane ligands. In the crystal, the I\u2212 anion is linked to the ptu mol\u00adecule through two N\u2014H\u22efI hydrogen bonds [graph-set motif R21(6)]. These N\u2014H\u22efI hydrogen bonds, in addition to weak C\u2014H\u22efS and C\u2014H\u22efI hydrogen bonds, form zigzag chains along [010]. Two of the phenyl rings of two dppm ligands are disordered over two sets of sites with refined occupancies of 0.557\u2005(16) and 0.443\u2005(16).The title complex, [Ag For the al. 2015.3I2(C25H22P2)3]I\u00b7C7H8N2S = 0.039wR(F2) = 0.104S = 1.0814160 reflections983 parameters216 restraintsH-atom parameters constrainedmax = 1.16 e \u00c5\u22123\u0394\u03c1min = \u22121.04 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I. DOI: 10.1107/S2056989015017120/lh5785Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015017120/lh5785fig1.tif. DOI: The mol\u00adecular structure with displacement ellipsoids drawn at the 50% probability level. All H atoms and the minor component of disorder are omitted for clarity.Click here for additional data file.10.1107/S2056989015017120/lh5785fig2.tif. DOI: Part of the crystal structure showing inter\u00admolecular N\u2014H\u22efI, C\u2014H\u22efS and C\u2014H\u22efI hydrogen bonds as dashed lines, forming a chain along [010].1424053CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 2086410.1038/srep20864; Published online: 02122016; Updated: 04292016This Article contains typographical errors.In the Results section under subheading \u2018Impact of ZLD1039 on breast cancer cell growth\u2019,50 values of 0.99\u2009\u00b1\u20090.23 and 0.089\u2009\u00b1\u20090.019\u2009\u03bcM, respectively\u201d.\u201cAmong the cell lines, MCF-7 and ZR-75-1 were the most sensitive to ZLD1039 with ICshould read:50 values of 0.99\u2009\u00b1\u20090.23 and 1.089\u2009\u00b1\u20090.019\u2009\u03bcM, respectively\u201d.\u201cAmong the cell lines, MCF-7 and ZR-75-1 were the most sensitive to ZLD1039 with ICIn Figure 3d, the x-axis \u20181\u20138 days of treatment\u2019 was incorrectly given as \u20180\u20137 days of treatment\u2019. The correct Figure 3d appears below as Fig.\u00a01"}
{"text": "Z\u2032 = 2) oriented almost perpendicular to each other [dihedral angle between the central core of each mol\u00adecule = 77.95\u2005(3)\u00b0]. The two mol\u00adecules exhibit similar conformations with an extended structure and are linked by bifurcated hydrogen bonds into a ribbon along the a-axis direction.The title compound crystallizes with the two mol\u00adecules in the asymmetric unit  oriented almost perpendicular to each other [dihedral angle between the central core of each mol\u00adecule = 77.95\u2005(3)\u00b0]. The two mol\u00adecules exhibit similar conformations with an extended structure. An intra\u00admolecular C\u2014H\u22efN hydrogen bond occurs in each mol\u00adecule. The two mol\u00adecules are linked by a bifurcated N\u2014H\u22ef hydrogen bond involving the NH group in mol\u00adecule A as donor. They are further linked into a ribbon along the a-axis direction by further bifurcated N\u2014H\u22ef hydrogen bonds involving the NH group in mol\u00adecule B as donor. C\u2014H\u22efO inter\u00adactions are also observed.The title compound, C E)-(meth\u00adoxy\u00adimino){2-[(2-methyl\u00adphen\u00adoxy)meth\u00adyl]phen\u00adyl}acetate] derivatives are broad spectrum fungicides  labeled A and B and shown in Fig.\u00a01A, the nitro group is coplanar with the p-nitro\u00adphenyl ring . The central ethane hydrazide moiety (N2A/N3A/C8A/O3A) is strictly planar with an r.m.s. deviation of 0.000\u2005\u00c5 for the fitted atoms. The dihedral angles between this moiety and the adjacent aromatic are 18.99\u2005(4)\u00b0 for the nitro\u00adbenzylidene ring (C1A\u2013C6A) and 62.20\u2005(4)\u00b0 for the benzene ring (C11A\u2013C16A).The title compound crystallizes with two mol\u00adecules in the asymmetric unit , 0.043\u2005(2) and 0.127\u2005(2)\u2005\u00c5, respectively]. The central ethane hydrazide moiety (N2B/N3B/C8B/O3B) is planar (r.m.s. deviation = 0.002\u2005\u00c5). The dihedral angles between this moiety and the adjacent aromatic rings are 12.43\u2005(4)\u00b0 for the nitrobenzylidene ring (C1B\u2013C6B) and 57.99\u2005(4)\u00b0 for the benzene ring (C11B\u2013C16B).In mol\u00adecule A and B are oriented almost perpendicular to each other, the dihedral angle between their central cores (atoms C7 N2 N3 and C8) being 77.95\u2005(3)\u00b0.Mol\u00adecules For both mol\u00adecules, bond lengths and angles are all within the normal ranges; however, comparisons with similar mol\u00adecules cannot be made as there are no similar overall structures although, of course, their fragments exist.A\u2014H17B\u22efN4A and C17B\u2014H17C\u22efN4B; Table\u00a01An intra\u00admolecular hydrogen bond . The mol\u00adecules are further linked into a ribbon along the a-axis direction a bifurcated N3B\u2014H3B\u22ef hydrogen bond involving the corresponding NH group in the other independent mol\u00adecule, as shown in Fig.\u00a02The two independent mol\u00adecules are linked by a bifurcated hydrogen bond Table\u00a01 between A search of the Cambridge Structural Database -2-Meth\u00adoxy\u00adimino-2-{2-[(2-methyl\u00adphen\u00adoxy)meth\u00adyl]phenyl}ethane\u00adhydrazide  was refluxed with p-nitro\u00adbenzaldehyde  in the presence of 5 drops of glacial acetic acid in 20\u2005ml absolute ethanol for about 10\u2005h to get a white-colored product. This was dissolved in methanol and white crystals were obtained by slow evaporation.(2isoU(H) = 1.5Ueq(C) for methyl H atoms and = 1.2eqU(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015004569/hg5434sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004569/hg5434Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015004569/hg5434Isup3.cmlSupporting information file. DOI: 1052231CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cations also form base pairs via N\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds.The N 12H10N5O+\u00b7NO3\u2212, the adenine unit has an N9-protonated N(7)\u2014H tautomeric form with non-protonated N1 and N3 atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10\u2005(10)\u00b0. The typical intra\u00admolecular N7\u2014H\u22efO hydrogen bond with an S(7) graph-set motif is also present. The benzoyl\u00adadeninium cations also form base pairs through N\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds involving the Watson\u2013Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra\u00admolecular ribbon with R22(9) rings. Benzoyl\u00adadeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N\u2014H\u22efO hydrogen bonds to generate a second ribbon motif. These ribbons together with \u03c0\u2013\u03c0 stacking inter\u00adactions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol\u00adecules generate a three-dimensional supra\u00admolecular architecture.In the title molecular salt, C N6-substituted adenine compounds continue to attract inter\u00adest due to their biological activity as they can act as plant hormones and have anti-allergenic, anti\u00adbacterial, anti\u00adviral and anti\u00adfungal properties et al., 1997et al., 2003et al., 2005et al., 2011Non-covalent inter\u00adactions, such as hydrogen bonding, halogen bonding and \u03c0\u2013\u03c0 inter\u00adactions play major roles in mol\u00adecular recognition and pharmaceutical drug design processes \u2014H tautomeric form with N9 protonated and N1, N3 non-proton\u00adated. The inter\u00adnal angles at N7 [C8\u2014N7\u2014C5 = 108.9\u2005(2)\u00b0] and N9 [C8\u2014N9\u2014C4 = 107.9\u2005(2)\u00b0] are similar as both carry hydrogen atoms  ring motif. A similar bond was found in the crystal structure of the neutral N6-benzoyl adenine via N\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds \u2005\u00c5 . The other face of the phenyl ring makes offset \u03c0\u2013\u03c0 contacts with both the imidazole [Cg1\u22efCg3ii = 3.7213\u2005(17)\u2005\u00c5] and the pyrimidine rings , Fig.\u00a03Cg1, Cg2 and Cg3 are the centroids of the imidazole, pyrimidine and phenyl rings, respectively. Similar contacts are found in related structures s Table\u00a01 involvinN6-substituted adenines, adeninium salts and their metal complexes have been investigated in a variety of crystalline environments. Neutral mol\u00adecules include N6-benzyl\u00adadenine  and N6-benzoyl\u00adadenine\u2013dl-tartaric acid (1:1). In these, the benzoyl\u00adadenine mol\u00adecule has a conformation similar to that reported for the neutral benzoyl\u00adadenine crystal structure , a few drops of nitric acid were added. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week colourless prismatic crystals of (I)To a hot methanol solution of Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015024871/sj5489sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015024871/sj5489Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024871/sj5489Isup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015024871/sj5489Isup4.cmlSupporting information file. DOI: 1444600CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The free 2,4-D anions are linked to the complex units through duplex water\u2013carboxyl\u00adate O\u2014H\u22efO hydrogen bonds through the coordinating water mol\u00adecules. In the crystal, inter-unit O\u2014H\u22efO hydrogen-bonding inter\u00adactions involving coordinating water mol\u00adecules as well as the solvent water mol\u00adecule (occupancy 0.5) with carboxyl\u00adate O-atom acceptors, give a layered structure lying parallel to (001), in which \u03c0\u2013\u03c0 ligand\u2013cation inter\u00adactions [minimum ring centroid separation = 3.6405\u2005(17)\u2005\u00c5] and a short O\u2014H\u22efCl inter\u00adaction are also found.In the crystal structure of the title magnesium salt of the phen\u00adoxy herbicide acetic acid , [Mg(C These include discrete monomeric {[MgL2(H2O)4] [L = 2-(2-fluoro\u00adphen\u00adoxy)acetate 5]\u00b7L }n  (H2O)5](C8H5Cl2O3)\u00b70.5H2O, was obtained from the reaction of 2,4-D with MgCO3 in aqueous ethanol and its crystal structure is reported herein.The phen\u00adoxy\u00adacetic acids comprise an important group of chemicals which has among its members those ring-substituted representatives having selective herbicidal activity, 6 complex units have, as expected, essentially octa\u00adhedral stereochemistry [Mg\u2014O bond length range = 2.031\u2005(2)\u20132.094\u2005(2)\u2005\u00c5], comprising a carboxyl\u00adate O-donor from a monodentate 2,4-D\u2212 ligand and five water mol\u00adecules. The free 2,4-D\u2212 counter-anion is linked to the complex unit through an unusual duplex water\u2013carboxyl\u00adate O\u2014H\u22efO hydrogen-bonding association involving the coordinating water mol\u00adecules O1W and O2W  being 179.0\u2005(2) and 174.8\u2005(2)\u00b0 (ligand A), and 175.7\u2005(2) and 178.7\u2005(2)\u00b0 (anion B), respectively]. This contrasts with the parent acid 2,4-D \u2005\u00c5] is also observed [for symmetry codes (i) and (iii), see: Table\u00a01In the crystal of the title compound, inter-unit O\u2014H\u22efO hydrogen-bonding inter\u00adactions Table\u00a01 involvin3 to 15\u2005ml of a hot aqueous solution of acetic acid (0.1\u2005mmol) in ethanol\u2013water (1:10 v/v). After completion of the reaction, excess MgCO3 was removed by filtration and the solution was allowed to evaporate at room temperature, providing colourless prisms of the title compound from which a specimen was cleaved for the X-ray analysis.The title compound was synthesized by the addition of excess MgCOUiso(H) = 1.5Ueq(O). Other H atoms were included in the refinement at calculated positions (aromatic C\u2014H = 0.95\u2005\u00c5 or methyl\u00adene 0.99\u2005\u00c5), with Uiso(H) = 1.2Ueq(C), using a riding-model approximation. The site-occupancy factor for the water mol\u00adecule of solvation was determined as 0.502\u2005(4) and was subsequently fixed at 0.50.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814019357/wm5045sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814019357/wm5045Isup2.hklStructure factors: contains datablock(s) I. DOI: 1021287CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Within the complex cation, the CrIII atom is coordinated by six O atoms of six urea ligands, displaying a slightly distorted octa\u00adhedral coordination environment. The Cr\u2014O bond lengths involving the urea ligands are in the range 1.9534\u2005(13)\u20131.9776\u2005(12)\u2005\u00c5. The Cr2O72\u2212 anion has a nearly staggered conformation, with a bridging angle of 130.26\u2005(10)\u00b0. The individual components are arranged in rows extending parallel to [100]. The Br\u2212 anion links the complex cation, as well as the solvent water mol\u00adecule, through N\u2014H\u22efBr and O\u2014H\u22efBr hydrogen-bonding inter\u00adactions. The supra\u00admolecular architecture also includes N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonding between urea N\u2014H and water O\u2014H donor groups and the O atoms of the Cr2O72\u2212 anion as acceptor atoms, leading to a three-dimensional network structure.The title bromide salt, [Cr{CO(NH On the other hand, CrVI is toxic and recognized as a carcinogen to humans and wildlife. The dichromate ion is environmentally important due to its high toxicity  in aqueous solution have been investigated. It was found that [Cr(urea)6]3+ is suitable to target these oxoanions Cl\u00b7H2O has been reported , b = 10.393\u2005(1), c = 17.794\u2005(3)\u2005\u00c5 and \u03b2 = 94. 86\u2005(2)\u00b0. Within our broader study of CrIII complexes as industrial materials Br\u00b7H2O, (I)Counter-ionic species in coordination compounds play important roles in chemistry, pharmacy, mol\u00adecular assembly, biology and catalysis, as well as contributing significantly to environmental pollution; however, their binding characteristics have not received much recognition Cl\u00b7H2O investigated previously In order to check if compound (I)III ion is coordinated by six urea ligands through oxygen atoms with CrA\u2014OA bond lengths ranging from 1.9534\u2005(13) to 1.9776\u2005(12)\u2005\u00c5, and with OA\u2014CrA\u2014OA bond angles in the range 85.10\u2005(5)\u201392.95\u2005(5)\u00b0. The CrA\u2014OA bond lengths involving the urea ligand are in good agreement with the value of 1.9630\u2005(17)\u2005\u00c5 for [Cr(urea)6](BF4)3 2(cyclam)]ClO4 (cyclam)]ClO4 (cyclam)](ClO4)2\u00b70.5H2O 2(cyclam)]NO2 (acac)] \u00b0, 173.94\u2005(5)\u00b0, and 175.89\u2005(5)\u00b0, respectively. The bond lengths within the urea ligand are in the ranges of 1.263\u2005(2)\u20131.276\u2005(2) and 1.316\u2005(2)\u20131.328\u2005(2)\u2005\u00c5 for C=O and C\u2014N bonds, respectively. The C=O bonds are slightly longer than that in free non-coordinating urea 2Cr2O7, the tetra\u00adhedral CrO4 groups are in an almost eclipsed conformation  and 1.8011\u2005(17)\u2005\u00c5 are longer than the terminal CrB\u2014OB bonds that are in the range of 1.6014\u2005(16)\u20131.6299\u2005(14)\u2005\u00c5. The Cr1B\u2014O7B\u2014Cr2B bridging angle in the complex anion is 130.26\u2005(10)\u00b0. The OB\u2014CrB\u2014OB bond angles in the two tetra\u00adhedral CrO4 groups are between 105.21\u2005(8) and 110.98\u2005(10)\u00b0, indicating slight angular distortions.It is of inter\u00adest to compare the conformation of Cr6]3+ moiety in compound (I)2O72\u2212 anions due to its high positive charge and the large number of hydrogen-bond donor groups of its six urea ligands.It is confirmed that the Br3\u00b73H2O was used as the starting material and was prepared according to literature procedures , dissolved in 10\u2005mL of water, was added to this solution. The mixture was refluxed at 353\u2005K for 10\u2005min and then cooled to room temperature. Green crystals of (I)2)2}6](Cr2O7)Br\u00b7H2O: C, 9.92; H, 3.61; N, 23.14%; found: C, 10.32; H, 3.08; N, 23.38%.All chemicals were reagent-grade materials and used without further purification. Chromium(III) tribromide hexa\u00adhydrate was obtained from Aldrich Chemical Co. and used as supplied. [Cr(urea)Uiso(H) = 1.2Ueq(N). H atoms of the solvent water mol\u00adecule were found from difference maps and refined with Uiso(H) = 1.2Ueq(O) and restrained to O\u2014H = 0.84\u2005(1) and H\u22efH = 1.36\u2005(2)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015019258/wm5225sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015019258/wm5225Isup2.hklStructure factors: contains datablock(s) I. DOI: 1430688CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked  33H26F2N2O2, both pyrrolidine rings of the pyrrolizidine moiety adopt an envelope conformation. The di\u00adfluoro\u00adphenyl group is oriented at an angle of 54.3\u2005(1)\u00b0 with respect to the oxindole moiety. The crystal packing features an N\u2014H\u22efO hydrogen bond, which forms an R22(8) motif, and a C\u2014H\u22efO inter\u00adaction, which generates a C(8) chain along [010]. In addition, this chain structure is stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions. In one of the pyrrolidine rings, the methyl\u00adene group forming the flap of an envelope and the H atoms of the adjacent methyl\u00adene groups are disordered over two sets of sites, with site-occupancy factors of 0.571\u2005(4) and 0.429\u2005(4)In the title pyrrolizidine derivative, C H-indole-2,3-dione) has been exploited extensively as a key inter\u00admediate in organic multicomponent reactions due to its anti\u00adbacterial   -1\u2032,2,2\u2032,3,5\u2032,6\u2032,7\u2032,7a\u2032-octa\u00adhydro-1H-indan-2-spiro-3\u2032-(3\u2032H- pyrrolizine)-1\u2032-spiro-3\u2032\u2032-1H-indoline-1,2\u2032\u2032,3-trione (IV) sp3 hybridization. The fluorine atoms, F1 and F2, deviate by 0.006\u2005(2) and \u22120.010\u2005(2)\u2005\u00c5, respectively, from the plane of the benzene ring (C1\u2013C6) to which they are attached. The oxindole group system is planar with maximum deviations from its plane for the carbonyl C30 [\u22120.048\u2005(2)\u2005\u00c5] and O2 atoms [\u22120.122\u2005(1)\u2005\u00c5]. The di\u00adfluoro\u00adphenyl group is oriented at an angle of 54.3\u2005(1)\u00b0 with respect to the oxindole moiety. The benzene rings C7\u2013C12 and C21\u2013C26 are oriented at a dihedral angle of 52.7\u2005(1)\u00b0. The dihedral angles subtended by these two benzene rings with respect to the oxindole moiety are 21.2\u2005(1) and 31.6\u2005(1)\u00b0, respectively. The dihedral angle between the benzene rings of the biphenyl group is 44.3\u2005(1)\u00b0. Atom C18 of the pyrrolizidine ring system, and the adjacent methyl\u00adene group H atoms, are disordered over two sets of sites, with the site-occupancy factors of 0.571\u2005(4) and 0.429\u2005(4).The sum of the angles at N1 of the pyrrolizidine ring system (340\u00b0) is in accordance with q2 = 0.393\u2005(2)\u2005\u00c5 and \u03d5 = \u2212167.8\u2005(2)\u00b0 for N1/C20/C14\u2013C16 ring, and q2 = 0.280\u2005(3)\u2005\u00c5 and \u03d5 = 104.8\u2005(4)\u00b0 for N1/C16\u2013C19. In the N1/C20/C14\u2013C16 ring, atom C14 deviates by 0.594\u2005(2)\u2005\u00c5 from the least-squares plane through the remaining four atoms, whereas in the N1/C16-C19 ring, atoms C18 and C18\u2032 deviate by \u22120.401\u2005(5) and 0.434\u2005(4)\u2005\u00c5, respectively, from the plane through the remaining four atoms.In the pyrrolizidine ring system, both pyrrolidine rings adopt envelope conformations; the puckering parameters are: via N\u2014H\u22efO hydrogen bonds into inversion dimers, generating an C(8) chains propagating along [010]; see Fig.\u00a04C(8) chains propagating along [010]; see Fig.\u00a05The geometry of inter\u00adactions observed in this structure are given in Table\u00a01To a solution of isatin (1\u2005mmol) and L-proline (1\u2005mmol) in methanol (25\u2005ml), 1-[4-phen\u00adyl]3-phenyl\u00adprop-2-en-1-one (1\u2005mmol) was added and the solution was refluxed for 6\u20138\u2005h. The completion of reaction was monitored by thin layer chromatography. After completion, the reaction mixture was poured onto crushed ice. The precipitate obtained was filtered and dried at room temperature. Suitable crystals were obtained by slow evaporation of a solution of the title compound in aceto\u00adnitrile at room temperature.Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Atom C18 is disordered over two positions, with the major component having 0.571\u2005(4) occupancy. Pairs of C\u2014C distances were restrained to 1.54\u2005(1)\u2005\u00c5. The temperature factor of C18\u2032 was set to that of C18 with the EADP instruction of SHELXL2014/7  I, global. DOI: 10.1107/S2056989015012931/gk2637Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015012931/gk2637Isup3.cmlSupporting information file. DOI: 1410535CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The platinum(II) complex with notable antitumor activity shows a slightly distorted square-planar coordination and intramolecular C\u2014H\u22efCl and intermolecular N\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds. 10H6NO2)Cl(C5H11N)], crystallizes with one mol\u00adecule in the asymmetric unit. The PtII cation has a slightly distorted square-planar coordination environment defined by a chloride anion, the quinoline N atom and a carboxyl\u00adate O atom of the bidentate quinaldate ligand and a piperidine N atom. An intra\u00admolecular C\u2014H\u22efCl hydrogen bond occurs. In the crystal, mol\u00adecules are stacked into columns along the c axis by the formation of N\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds.The title compound, [Pt(C The Cl\u2212 and the PtII atoms are displaced from the least-squares plane of the quinoline ring and all other coord\u00adinating atoms by 0.2936\u2005(7) and 0.0052\u2005(1)\u2005\u00c5, respectively. The piperidine ring adopts a chair conformation and is almost perpendicular to the coordination plane of the PtII cation [dihedral angle between the best plane through the piperidine ring and the four atoms coordinating to the PtII cation = 79.66\u2005(13)\u00b0]. Bond lengths are normal and agree well with related platinum compounds ] , prepared according to the synthetic protocol of Da et al. (2001v/v) was added gradually while stirring at room temperature for 1\u2005h. The reaction mixture was stirred further for 4\u2005h. The precipitated yellow substance was filtered off and washed consecutively with a 0.1 M HCl solution (2 \u00d7 2\u2005ml), warm water (3 \u00d7 2\u2005ml) and cold ethanol (2\u2005ml). The product was then dried in a vacuum at 323\u2005K for 4\u2005h. The yield was 80%. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation from an ethanol\u2013water (1:1 v/v) solution at room temperature. Positive ESI\u2013MS: m/z 1973 [4M + Na]+, 1483 [3M + Na]+, 998 [2M + Na]+, 510 [M + Na]+, 977 [2M + H]+, 489 [M + H]+; IR (KBr) cm\u22121: 3192 (\u03bdNH); 3080, 2930, 2866 (\u03bdCH); 1678 (\u03bdC=O); 1592, 1459 (\u03bdC=C arom); 1334 (\u03bdC\u2014O); 1H NMR : 9.50 , 8.51 , 8.06 , 7.91\u20137.88 , 7.71 , 3.52 , 3.27  = 12.5\u2005Hz, C510HNH), 1.76\u20131.61 , 4.00 .The starting complex K[PtCl al. 2001, was dis2 and N\u2014H = 0.93\u2005\u00c5 for amino H atoms, with Uiso = 1.2Ueq.All H atoms were refined using a riding model, with C\u2014H = 0.95\u2005\u00c5 for aromatic, C\u2014H = 0.99\u2005\u00c5 for CH10.1107/S160053681401191X/wm0005sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401191X/wm0005Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004305CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Cu\u2014Cl bond measures 2.2287\u2005(9)\u2005\u00c5, and the two Cu\u2014S bonds are significantly different from each other, with values of 2.2270\u2005(10) and 2.2662\u2005(10)\u2005\u00c5. Also, the S\u2014Cu\u2014Cl angles differ, with values of 113.80\u2005(4) and 124.42\u2005(4)\u00b0, while the S\u2014Cu\u2014S angle is 121.51\u2005(4)\u00b0. The two imidazole rings are almost parallel, making a dihedral angle of 2.1\u2005(2)\u00b0. In the crystal, the shortest C\u2014H\u22efCl interactions stabilize a three-dimensional network with molecules linked into centrosymmetric dimers that are stacked along the b-axis direction.The mol\u00adecular structure of the title compound, [CuCl(C DOI: 10.1107/S1600536814024404/zq2228Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814024404/zq2228fig1.tif. DOI: Mol\u00adecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level.1032971CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound comprises a 2-imino\u00adpyridine ring fused with a cyclo\u00adoctane ring, which adopts a twist boat\u2013chair conformation. Inter\u00admolecular C\u2014H\u22efN inter\u00adactions form  25H24ClN3, comprises a 2-imino\u00adpyridine ring fused with a cyclo\u00adoctane ring, which adopts a twist boat\u2013chair conformation. In the crystal, C\u2014H\u22efN inter\u00adactions form R22(14) ring motifs and mol\u00adecules are further connected by weak C\u2014H\u22ef\u03c0 inter\u00adactions. The resulting supra\u00admolecular structure is a two-dimensional framework parallel to the ab plane.The title compound, C They have gained importance in the medicinal and pharmaceutical fields due to their broad spectrum of biological activity, including anti-inflammatory, analgesic, anti\u00admicrobial, anti\u00adconvulsant, anti\u00adtubercular \u00b0 shows the linearity of the cyano group, a feature systematically observed in carbo\u00adnitrile compounds. Nitrile atoms C38 and N2 are displaced from the mean plane of the pyridine ring by 0.0258\u2005(1) and 0.0363\u2005(1)\u2005\u00c5, respectively. The imino C1=N1 bond length is 1.286\u2005(2)\u2005\u00c5. The imino group is nearly coplanar with the pyridine ring, as indicated by the N1=C1\u2014N3\u2014C5 torsion angle of \u2212178.89\u2005(14)\u00b0. The chloro\u00adbenzene ring is attached to the pyridine ring with a C2=C3\u2014C31\u00a0C36 torsion angle of 100.99\u2005(19)\u00b0, indicating a (+)anti\u00adclinal conformation. The C33\u00a0C34\u00a0C35 bond angle of 121.11\u2005(15)\u00b0 deviates from 120\u00b0 due to the presence of the chlorine substituent. The chlorine atom bonded to C34 deviates by 0.0446\u2005(1)\u2005\u00c5 from the mean plane of the phenyl ring. The chlorine is attached to the benzene ring with a C32\u00a0C33\u00a0C34\u2014Cl1 torsion angle of 178.95\u2005(13)\u00b0. In the pyridine ring, the formal double bonds [C4=C5 = 1.375\u2005(2) and C2=C3 = 1.369\u2005(2)\u2005\u00c5] are longer than standard C=C bonds (1.34\u2005\u00c5), while the other bond lengths are slightly shorter than standard C\u2014C and C\u2014N bond lengths, evidencing that there is a homo-conjugation effect for this ring.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01et al., 1995ab plane.In the crystal, pairs of C\u2014H\u22efN inter\u00adactions form b]pyrid\u00adine-3-carbo\u00adnitrile -5,6,7,8,9,10-hexa\u00adhydro\u00adcyclo\u00adocta\u00ad[p-toluene\u00adsulfonic acid (0.5\u2005mmol) was added. The reaction mixture was refluxed for 2\u20133\u2005h. After completion of the reaction (followed by thin-layer chromatography), the mixture was poured into crushed ice and extracted with ethyl acetate. The excess of solvent was removed under reduced pressure and the residue was chromatographed using a petroleum ether/ethyl acetate mixture (97:3 v/v) as eluent, to afford the pure product. The product was recrystallized from ethyl acetate, affording colourless crystals .Cyclo\u00adocta\u00adnone (1\u2005mmol), 4-chloro\u00adbenzaldehyde (1\u2005mmol) and malono\u00adnitrile (1\u2005mmol) were mixed in ethanol (10\u2005ml), and 2). Imine atom H1 was found in a difference map and refined freely, with the N\u2014H distance restrained to 0.84\u2005(2)\u2005\u00c5. Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.2Ueq(C) for CH and CH2 groups, while the Uiso factor for H1 was refined. Crystal data, data collection and structure refinement details are summarized in Table\u00a02.C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C\u2014H = 0.93 (aromatic CH) or 0.97\u2005\u00c5  global, I. DOI: 10.1107/S160053681401962X/bh2503Isup2.hklStructure factors: contains datablock(s) I. DOI: 1021949CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We used Sca1154Q/2Q mice, an established knock-in mouse model of the polyglutamine disease spinocerebellar ataxia type 1 (SCA1), which replicates human SCA1 features including ataxia, cognitive impairment, and neuronal death. We found that Sca1154Q/2Q mice exhibited greater synaptic instability than controls, without synaptic loss, in the cerebral cortex, where obvious neuronal death is not observed, even before the onset of distinct symptoms. Interestingly, this abnormal synaptic instability was evident in Sca1154Q/2Q mice from the synaptic developmental stage, and persisted into adulthood. Expression of synaptic scaffolding proteins was also lower in Sca1154Q/2Q mice than controls before synaptic maturation. As symptoms progressed, synaptic loss became evident. These results indicate that aberrant synaptic instability, accompanied by decreased expression of scaffolding proteins during synaptic development, is a very early pathology that precedes distinct neurological symptoms and neuronal cell death in SCA1.Late-onset neurodegenerative diseases are characterized by neurological symptoms and progressive neuronal death. Accumulating evidence suggests that neuronal dysfunction, rather than neuronal death, causes the symptoms of neurodegenerative diseases. However, the mechanisms underlying the dysfunction that occurs prior to cell death remain unclear. To investigate the synaptic basis of this dysfunction, we employed  Many late-onset neurodegenerative diseases, including Alzheimer\u2019s, Parkinson\u2019s, and prion and polyglutamine diseases, share common features, such as the aggregation of toxic proteins in neurons, and progressive neuronal cell death1ATXN1 geneSca1154Q/2Q knock-in mouse model, harbouring 154 CAG repeats within the endogenous ATXN1 locus, closely reproduces the features of human SCA16Sca1154Q/2Q mice is much higher than that in human patients, another knock-in SCA1 mouse model harbouring 78 CAG repeats, similar to the number in patients, displays only mild behavioural deficits late in lifeSca1154Q/2Q mice are suitable for studying symptom progression. Sca1154Q/2Q mice develop motor learning impairment before any obvious Purkinje cell death occurs or nuclear inclusions form in the cerebellumSca1154Q/2Q mice show nuclear inclusions in pyramidal neurons, and cognitive deficits are observed without evident neuronal lossMany neurodegenerative diseases are attributed to multiple factors, including genetic and environmental predispositions. On the other hand, spinocerebellar ataxia type 1 (SCA1), a polyglutamine disease, is a monogenic disorder caused by the expansion of an unstable CAG trinucleotide repeat tract encoding a polyglutamine stretch in the Sca1154Q/2Q knock-in mice to elucidate the synaptic basis of neuronal dysfunction. We analysed the dynamics, morphology, and density of dendritic protrusions, which are excitatory postsynaptic structures classified into mature \u2018spines\u2019 and immature \u2018filopodia\u2019. These features are strongly associated with synaptic developmentSca1154Q/2Q knock-in mice in vivo, maintaining contributions from peripheral tissues and non-neuronal cells expressing mutant ataxin-1, as well as neurons. To evaluate neuronal dysfunction while excluding the effects of neuronal death, we focused on the cerebral cortex and hippocampus, in which apparent neuronal death does not occur despite the presence of cognitive dysfunction in both Sca1154Q/2Q mice and human SCA1 patients5In the present study, we focused on SCA1 as a genetic model of neurodegenerative disease, and used Sca1154Q/2Q mice are observed by 5 weeks of age, and spatial and fear memory deficits by 8 weeks. Although nuclear inclusions of mutant ataxin-1 are observed by 6 weeks, there is no neuronal death in the limbic area during such early stages of the diseaseSca1154Q/2Q mice as a possible early SCA1 phenotype. We performed in vivo two-photon imaging in layer 1 dendrites of the primary somatosensory cortex in Sca1154Q/2Q and control Sca12Q/2Q mice, and analysed the morphology, formation, and elimination of dendritic protrusions over a 1\u2009h period under anaesthesia  vs Sca1154Q/2Q (0.33\u2009\u00b1\u20090.05/\u03bcm), p\u2009=\u20090.4532; spines: Sca12Q/2Q (0.31\u2009\u00b1\u20090.02/\u03bcm) vs Sca1154Q/2Q (0.24\u2009\u00b1\u20090.03/\u03bcm), p\u2009=\u20090.0909; filopodia: Sca12Q/2Q (0.070\u2009\u00b1\u20090.005/\u03bcm) vs Sca1154Q/2Q (0.09\u2009\u00b1\u20090.02/\u03bcm), p\u2009=\u20090.4159; unpaired t-test]. There were also no significant differences between 4-week-old Sca12Q/2Q and Sca1154Q/2Q mice in the number of spines or filopodia as a percentage of the total protrusions (Sca12Q/2Q (81\u2009\u00b1\u20091%) vs Sca1154Q/2Q (76\u2009\u00b1\u20092%), p\u2009=\u20090.0747; filopodia: Sca12Q/2Q (19\u2009\u00b1\u20091%) vs Sca1154Q/2Q (24\u2009\u00b1\u20092%), p\u2009=\u20090.0747; unpaired t-test]. Next, we analysed the dynamics of the protrusions in order to estimate synaptic stability. Notably, we found that the rates of formation and elimination of spines over 1\u2009h were significantly higher in Sca1154Q/2Q mice than in Sca12Q/2Q mice (Sca12Q/2Q (3.6\u2009\u00b1\u20090.9%) vs Sca1154Q/2Q (9\u2009\u00b1\u20092%), p\u2009=\u20090.0101; elimination rate: Sca12Q/2Q (4.5\u2009\u00b1\u20090.8%) vs Sca1154Q/2Q (12\u2009\u00b1\u20092%), p\u2009=\u20090.0017; unpaired t-test]. The elimination rate of filopodia over 1\u2009h was also significantly higher in Sca1154Q/2Q mice, but the difference in their formation rate did not reach statistical significance (Sca12Q/2Q (27\u2009\u00b1\u20096%) vs Sca1154Q/2Q (35\u2009\u00b1\u20094%), p\u2009=\u20090.2711; elimination rate: Sca12Q/2Q (23\u2009\u00b1\u20094%) vs Sca1154Q/2Q (42\u2009\u00b1\u20097%), p\u2009=\u20090.0341; unpaired t-test]. Anaesthetics can increase the formation of filopodia within a 1\u2009h periodin vivo imaging over 48\u2009h, during which time the mice were allowed to recover from the anaesthesia after the first imaging session and were returned to their home cages until the next session. We confirmed that both formation and elimination rates of spines in Sca1154Q/2Q mice were also significantly higher than those in Sca12Q/2Q mice over a 48\u2009h period (Sca12Q/2Q (8\u2009\u00b1\u20091%) vs Sca1154Q/2Q (23\u2009\u00b1\u20093%), p\u2009<\u20090.0001; elimination rate: Sca12Q/2Q (10\u2009\u00b1\u20091%) vs Sca1154Q/2Q (28\u2009\u00b1\u20094%), p\u2009=\u20090.0003; unpaired t-test]. Neither the formation nor elimination rates of filopodia over 48\u2009h were significantly different between groups, probably owing to the very high rates measured over 48\u2009h even in control mice (Sca12Q/2Q (59\u2009\u00b1\u20099%) vs Sca1154Q/2Q (52\u2009\u00b1\u20099%), p\u2009=\u20090.5763; elimination rate: Sca12Q/2Q (70\u2009\u00b1\u200910%) vs Sca1154Q/2Q (72\u2009\u00b1\u20097%), p\u2009=\u20090.8919; unpaired t-test]. These data indicate that Sca1154Q/2Q mice show abnormal synaptic instability during synaptic development, before the onset of obvious symptoms, and that these altered dynamics are detectable by imaging under anaesthesia during a 1\u2009h period.Motor learning impairments in esthesia . Dendrits of age  . The number of spines as a percentage of total protrusions was significantly lower in Sca1154Q/2Q mice than in Sca12Q/2Q mice at 6 weeks (Sca12Q/2Q (88\u2009\u00b1\u20092%) vs Sca1154Q/2Q (81\u2009\u00b1\u20092%), p\u2009=\u20090.0284; unpaired t-test], whereas that of filopodia was higher (Sca12Q/2Q (12\u2009\u00b1\u20092% vs Sca1154Q/2Q (19\u2009\u00b1\u20092%), p\u2009=\u20090.0284; unpaired t-test]. Spine dynamics were significantly greater in Sca1154Q/2Q mice than in Sca12Q/2Q mice at 6 weeks of age (Sca12Q/2Q (2.3\u2009\u00b1\u20090.5%) vs Sca1154Q/2Q (9\u2009\u00b1\u20092%), p\u2009=\u20090.0018; elimination rate: Sca12Q/2Q (2.1\u2009\u00b1\u20090.6%) vs Sca1154Q/2Q (13\u2009\u00b1\u20092%), p\u2009<\u20090.0001; unpaired t-test]. Regarding the filopodium dynamics of 6-week-old Sca1154Q/2Q mice, the elimination rate was significantly higher, but the formation rate was not different from that in Sca12Q/2Q mice (Sca12Q/2Q (18\u2009\u00b1\u20097%) vs Sca1154Q/2Q (36\u2009\u00b1\u20096%), p\u2009=\u20090.0785; elimination rate: Sca12Q/2Q (14\u2009\u00b1\u20093%) vs Sca1154Q/2Q (35\u2009\u00b1\u20097%), p\u2009=\u20090.0100; unpaired t-test]. In 8-week-old Sca1154Q/2Q mice, total protrusion and spine densities were significantly lower than those in age-matched Sca12Q/2Q mice, whereas filopodium density was not different between the two groups (Sca12Q/2Q (0.36\u2009\u00b1\u20090.02/\u03bcm) vs Sca1154Q/2Q (0.30\u2009\u00b1\u20090.02/\u03bcm), p\u2009=\u20090.0343; spines: Sca12Q/2Q (0.33\u2009\u00b1\u20090.02/\u03bcm) vs Sca1154Q/2Q (0.25\u2009\u00b1\u20090.01/\u03bcm), p\u2009=\u20090.0175; filopodia: Sca12Q/2Q (0.033\u2009\u00b1\u20090.004/\u03bcm) vs Sca1154Q/2Q (0.044\u2009\u00b1\u20090.006/\u03bcm), p\u2009=\u20090.1621; unpaired t-test]. The number of spines as a percentage of the total protrusions was significantly lower in 8-week-old Sca1154Q/2Q mice than in Sca12Q/2Q mice (Sca12Q/2Q (90\u2009\u00b1\u20091%) vs Sca1154Q/2Q (85\u2009\u00b1\u20092%), p\u2009=\u20090.0403; unpaired t-test], whereas that of filopodia was higher in 8-week-old Sca1154Q/2Q mice than in Sca12Q/2Q mice (Sca12Q/2Q (10\u2009\u00b1\u20091%) vs Sca1154Q/2Q (15\u2009\u00b1\u20092%), p\u2009=\u20090.0403; unpaired t-test]. Both formation and elimination rates of spines in 8-week-old Sca1154Q/2Q mice were significantly higher than those in Sca12Q/2Q mice (Sca12Q/2Q (2.7\u2009\u00b1\u20090.7%) vs Sca1154Q/2Q (13\u2009\u00b1\u20092%), p\u2009<\u20090.0001; elimination rate: Sca12Q/2Q (2.0\u2009\u00b1\u20090.8%) vs Sca1154Q/2Q (12\u2009\u00b1\u20094%), p\u2009=\u20090.0176; unpaired t-test]. The formation rate of filopodia in 8-week-old Sca1154Q/2Q mice was higher than that in Sca12Q/2Q, whereas the elimination rate was not significantly different (Sca12Q/2Q (5\u2009\u00b1\u20093%) vs Sca1154Q/2Q (25\u2009\u00b1\u20098%), p\u2009=\u20090.0134; elimination rate: Sca12Q/2Q (21\u2009\u00b1\u20098% vs Sca1154Q/2Q (42\u2009\u00b1\u200911%), p\u2009=\u20090.1166; unpaired t-test]. These data indicate that SCA1 mice have immature dendritic morphology and a loss of dendritic protrusions associated with persisting synaptic instability and the progression of SCA1 symptoms.We demonstrated that synaptic instability occurs in SCA1 mice before the onset of distinct symptoms at 4 weeks of age. Next, we evaluated the progression of synaptic pathology in SCA1 mice until 8 weeks of age, by which time dendritic spines have normally stabilised and the density of filopodia has reached a minimumice at 6  and 8 weice at 6 . In 6-wee groups  , whereas at 12 weeks, dendritic protrusion density was significantly lower in Sca1154Q/2Q mice than in Sca12Q/2Q mice (Sca12Q/2Q (1.53\u2009\u00b1\u20090.06/\u03bcm) vs Sca1154Q/2Q (1.28\u2009\u00b1\u20090.04/\u03bcm), p\u2009=\u20090.0011; unpaired t-test]. An abnormal frequency distribution of dendritic protrusion width was observed in Sca1154Q/2Q mice, particularly at 12 weeks of age, when the distribution curve shifted to the left . The mean dendritic protrusion width in 12-week-old Sca1154Q/2Q mice was lower than that in Sca12Q/2Q mice . These results show that the dendritic protrusion width in Sca1154Q/2Q mice decreased as SCA1 symptoms developed. An abnormal frequency distribution of protrusion length in Sca1154Q/2Q mice was evident at 5 weeks of age, and the frequency distribution curve was shifted to the right . No difference was observed in the mean length of dendritic protrusions between Sca1154Q/2Q and Sca12Q/2Q mice at either age . These results indicate that the protrusion lengths in Sca1154Q/2Q mice differ little from those in Sca12Q/2Q mice from early life through to adulthood. In summary, SCA1 mice demonstrated progressive deficits in dendritic protrusions in the hippocampus from adult ages./2Q mice . We choss of age   with EDTA-free complete protease inhibitors and PhosSTOP (Roche Applied Science). Immunoblotting was performed using the following antibodies: anti-Homer1b/c , anti-pan-Shank , anti-PSD95 , anti-mGluR5 , anti-NR2B , anti-GluR1 , anti-Bassoon , and anti-\u03b2-actin . Total protein (10\u2009\u03bcg/lane) was separated on sodium dodecyl sulphate-polyacrylamide gels, transferred to immunoblot polyvinylidene difluoride membranes , incubated with 3% BSA in TBST  for 1\u2009h at room temperature, and incubated with each primary antibody overnight at 4\u2009\u00b0C. The membranes were washed in TBST and further incubated with anti-mouse/rabbit IgG-horseradish peroxidase conjugate . After washing in TBST, the membranes were developed with Super Signal West Dura or Femto extended duration substrate (Pierce) and analysed using a ChemiImager . Proteins were identified by band position relative to a molecular weight marker.t-test, one-way ANOVA followed by Tukey multiple-comparison test, two-way ANOVA followed by Bonferroni multiple-comparison test, or the Kolmogorov\u2013Smirnov test. All statistical analyses were performed with GraphPad Prism . All data are presented as the mean\u2009\u00b1\u2009SEM.To determine statistical significance, we used the Student How to cite this article: Hatanaka, Y. et al. Abnormalities in synaptic dynamics during development in a mouse model of spinocerebellar ataxia type 1. Sci. Rep.5, 16102; doi: 10.1038/srep16102 (2015)."}
{"text": "In the title compound, the ring conformations of the tricycles are in an envelope, a half-chair and a chair. In the crystal, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into a three-dimensional architecture. 36H44O10\u00b7C6H6, the dioxolane ring adopts an envelope conformation with the C atom bonded to the H atom as the flap, while the cyclo\u00adhexene and cyclo\u00adhexane rings are in half-chair and chair conformations, respectively. In the crystal, a pair of O\u2014H\u22efO hydrogen bonds with an R22(26) graph-set motif connect the benzoate mol\u00adecules into an inversion dimer. The dimers are linked by a weak C\u2014H\u22efO inter\u00adaction into a tape structure along [01-1]. The benzene mol\u00adecule links the tapes through C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a sheet parallel to (100).In the title compound, C The title compound has been obtained in our synthetic study of paclitaxel as a cyclization precursor to build the taxane skeleton  = 0.165\u2005(2)\u2005\u00c5 and \u03d5(2) = 114.5\u2005(6)\u00b0. The flap atom C4 deviates from the mean plane of other atoms by 0.270\u2005(3)\u2005\u00c5. The cyclo\u00adhexene ring (C5\u2013C10), which is spiro-fused to the dioxolane ring, is in a half-chair conformation with puckering parameters of Q = 0.469\u2005(2)\u2005\u00c5, \u03b8 = 127.5\u2005(2)\u00b0, \u03d5(2) = 197.2\u2005(3)\u00b0, Q(2) = 0.372\u2005(2)\u2005\u00c5 and Q(3) = \u22120.285\u2005(2)\u2005\u00c5. Atoms C5 and C6 deviate from the mean plane of the other atoms by \u22120.493\u2005(4) and 0.212\u2005(4)\u2005\u00c5, respectively. The cyclo\u00adhexane ring (C24\u2013C29) is in a chair conformation with puckering parameters Q = 0.587\u2005(2)\u2005\u00c5, \u03b8 = 4.6\u2005(2)\u00b0, \u03d5 = 246\u2005(3)\u00b0, Q(2) = 0.042\u2005(2)\u2005\u00c5 and Q(3) = 0.585\u2005(2)\u2005\u00c5. The large substituents  are in the equatorial positions. The meth\u00adoxy\u00admeth\u00adoxy group (O42/C43/O44/C45) shows a helical form with torsion angles of 76.5\u2005(3)\u00b0 for C29\u2014O42\u2014C43\u2014O44 and 64.8\u2005(3)\u00b0 for O42\u2014C43\u2014O44\u2014C45 held by weak intra\u00admolecular C\u2014H\u22efO inter\u00adactions  was provided according to the reported procedure (Nicolaou Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The H atom of hy\u00addroxy group (O41) was placed guided by difference maps and then treated as riding, with O\u2014H = 0.84\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O). 13 problematic reflections were omitted from the final refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989014026048/is5382sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014026048/is5382Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014026048/is5382Isup3.cmlSupporting information file. DOI: 1036428CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains two Co2+ ions, one L3\u2212 anion originating from 5-(4-carb\u00adoxy\u00adphen\u00adoxy)isophthalic acid (H3L), one OH\u2212 ligand, one 1,4-bis\u00ad[(1H-imidazol-l-yl)meth\u00adyl]benzene (bix) ligand and one disordered lattice water mol\u00adecule (occupancy 0.25). The two Co2+ ions have different environments. One has an octa\u00adhedral O4N2 coordin\u00adation sphere, defined by four O atoms from three carboxyl\u00adate groups and one OH\u2212 ligand, and two N atoms from two symmetry-related bix ligands. The other has a trigonal-bipyramidal O5 coordination sphere resulting from three carboxyl\u00adate groups and two OH\u2212 ligands. The dihedral angles between the two benzene rings in the L3\u2212 ligand and between the benzene ring and the two imidazole rings in the bix ligand are 67.05\u2005(15), 75.27\u2005(17) and 82.05\u2005(17)\u00b0, respectively. Four neighbouring Co2+ ions are linked by six carboxyl\u00adate groups and two \u03bc3-OH ligands, forming a butterfly-shaped secondary building unit (SBU). These SBUs are connected by L3\u2212 anions into layers parallel to (1-10). Adjacent layers are cross-linked by the bix ligands, forming a three-dimensional framework that has a bimodal -connected tfz-d topology. The disordered lattice water mol\u00adecule is located in the voids of the framework and has O\u22efO and O\u22efN contacts of 2.81\u2005(2) and 2.95\u2005(2)\u2005\u00c5, suggesting medium-strength hydrogen bonds. The title compound may be a good candidate for artificial eye lenses.The title coordination polymer, {[Co For top al. 2010.2(C15H7O7)(OH)(C14H14N4)]\u00b70.25H2O = 0.037wR(F2) = 0.086S = 1.045314 reflections396 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 0.37 e \u00c5\u22123\u0394\u03c1min = \u22120.37 e \u00c5\u22123\u0394\u03c1APEX2  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022806/wm5040Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814022806/wm5040fig1.tifx y z x y z x y z x y z x y z . DOI: x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; ii) 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; iii) \u22121\u00a0+\u00a0x, \u22121\u00a0+\u00a0y, z; iv) 2\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, \u2212z; v) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, z.]The extended asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The disordered lattice water mol\u00adecule has been omitted for clarity. The tetra\u00adnuclear SBU in the structure of the title compound. [Symmetry code: A) 1\u00a0\u2212\u00a0Click here for additional data file.10.1107/S1600536814022806/wm5040fig3.tifL 3\u2212 . DOI: L3\u2212 anions.View of the layered network formed by the SBUs and the 1029647CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The geometry of the title hemibi\u00adquinone is different from previous examples and may be correlated with the weak inter\u00adactions in the crystal. 16H9BrN2O4\u00b70.5C6H6, the mol\u00adecules stack in a centrosymmetric unit cell in a 2:1 stoichiometry with co-crystallized benzene solvent mol\u00adecules and inter\u00adact via various weak inter\u00adactions. This induces a geometry different from that predicted by theory, and is unique among the hemibi\u00adquinones heretofore reported.In the crystal of the title compound, C Biphenyl derivatives have garnered great attention to themselves as conductors of electricity  mol\u00adecule, 4\u2032-bromo-2\u2032,5\u2032-dimeth\u00adoxy-2,5-dioxo--3,4-dicarbo\u00adnitrile 1 Fig.\u00a01, has beenter 1974, where aet al., 20152(CN)2], Fig.\u00a021 is comparable to that in the hydro\u00adquinone [1.481\u2005(2)\u2005\u00c5]. In this mol\u00adecule, the C5\u2014C4\u2014C7\u2014C8 torsion is 125.3\u2005(2)\u00b0, compared to the hydro\u00adquinone torsion angle of \u2212126.50\u00b0, \u00b0 and C5\u2014C6\u2014O1\u2014C14 bent out of plane by \u22127.0\u2005(3)\u00b0. The meth\u00adoxy group bond angle C3\u2014O2\u2014C13 is measured at 117.4\u2005(1)\u00b0, and C6\u2014O1\u2014C14 is measured at 117.3\u2005(1)\u00b0. The methyl portions of each of these groups point away from the sterically restricting groups 1 [1.346\u2005(2)\u2005\u00c5] is shorter than than the corresponding hydro\u00adquinone C9\u2014C10 bond [1.408\u2005(2)\u2005\u00c5] and the C1\u2014C6 bond [1.334\u2005(6)\u2005\u00c5] of BrHBQBr \u2005\u00c5] compared to the same bond in the hydro\u00adquinone precursor [1.885\u2005(1)\u2005\u00c5], but is still shorter than that of the starting material BrHBQBr . Additionally, there is a short contact between C10 and C8, at 3.486\u2005(3)\u2005\u00c5. The N2 nitrile atom possibly accepts a very weak inter\u00adaction from the meth\u00adoxy C13 and H13A pair (2.82\u2005\u00c5 and 97\u00b0). There is a long C13\u22efN2 [(3.101\u2005(3)\u2005\u00c5] inter\u00adaction as well. Even longer than those inter\u00adactions, H13 also has a weak H\u22ef\u03c0 inter\u00adaction with the di\u00admeth\u00adoxy\u00adbenzene ring on an adjacent mol\u00adecule (H\u22ef\u03c0 = 2.88\u2005\u00c5). The packing is shown in Fig.\u00a05Each HBQ mol\u00adecule inter\u00adacts with a total of three benzene mol\u00adecules by short contacts. As mentioned above, one mol\u00adecule of benzene is sandwiched between two quinone rings. Additionally, the 3-substituted nitrile group accepts a C\u2014H\u22efN hydrogen bond from a solvent mol\u00adecule . The third benzene mol\u00adecule exhibits short contacts to the 4\u2032-bromine atom on the opposite end of the mol\u00adecule, where H17 and H18 link to Br1 almost symmetrically . Since the benzene mol\u00adecule \u03c0-stacks parallel to the quinones, the benzene mol\u00adecule is oriented in the same direction relative to the di\u00admeth\u00adoxy\u00adbenzene ring. Although, in previous HBQ crystals the 4 and 4\u2032 groups show evidence of inter\u00admolecular halogen bonding, due to the excess electron density around the aryl bromine atoms and the nitrile groups, an attractive inter\u00adaction is not possible, rather a slightly repulsive inter\u00adaction is favored. Instead, the protons on C17 and C18 bifurcate to Br1 as an acceptor, forming slightly asymmetric hydrogen bonds between the di\u00admeth\u00adoxy\u00adbenzene ring and the benzene solvent mol\u00adecule. As discussed above, the quinone carbonyl groups are deflected from perfect planarity. In previous structures, meth\u00adoxy oxygen atoms tended to deflect the carbonyl groups through repulsive effects. However, this structure contains some attractive inter\u00admolecular hydrogen bonding character, including the C14\u2014H142O and 100\u2005mL of benzene. FeCl3  was added in one portion. The resulting mixture was capped and stirred overnight. The resulting phases were separated, and the organic phase was washed with water and dried over anhydrous Na2SO4. Evaporation of the solvent produced a crude product. The pure product was precipitated from a chloro\u00adform solution by addition of hexane, yielding 0.0460\u2005g (36.7%). Black, block-shaped crystals of 1 were grown from chloro\u00adform solution with residual benzene at 296\u2005K. 1H NMR  \u03b4 = 7.22 , 7.12 , 6.71 , 3.87 , 3.76 .4\u2032-Bromo-2,5-dihy\u00addroxy-2\u2032,5\u2032-dimeth\u00adoxy--3,4-dicarbo\u00adnitrile  was suspended in a mixture of 100\u2005mL of H3, 0.88\u2005\u00c5. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Uiso(H) values were set to a multiple of Ueq(C) with 1.5 for CH3. Crystal data, data collection and structure refinement details are summarized in Table\u00a01H atoms attached to carbon atoms were positioned geometrically and constrained to ride on their parent atoms, with C\u2014H-bond distances of 0.95\u2005\u00c5 for aromatic C\u2014H, 1.00, 0.99 and 0.98\u2005\u00c5 for aliphatic CH10.1107/S2056989016005120/hb7567sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005120/hb7567Isup2.hklStructure factors: contains datablock(s) I. DOI: 1470649CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two 2,2-di\u00adallyl\u00admalonate anions bridge four AgI ions in a \u03bc4- mode, setting up an Ag4O8P4 core (point group symmetry -4..) of corner-sharing tetra\u00adhedra. The shortest intra\u00admolecular Ag\u22efAg distance of 3.9510\u2005(3)\u2005\u00c5 reveals that no direct d10\u22efd10 inter\u00adactions are present. Four weak intra\u00admolecular C\u2014H\u22efO hydrogen bonds are observed in the crystal structure of the title compound, which most likely stabilize the tetra\u00adnuclear silver core.In the tetra\u00adnuclear mol\u00adecule of the title compound, [Ag On a mol\u00adecular level this is typically achieved by designing low aggregated metal compounds. In the case of silver, this can be realized by the use of phosphanes as a Lewis base; however, the concomitant increase of the mol\u00adecular weight of the transition metal complex may decrease its vapour pressure. Circumventing this difficulty, we have investigated the use of olefines as ligands for silver(I) carboxyl\u00adates, in which the olefin is covalently bonded to the carboxyl\u00adate. In the context of this approach, the title compound [{ mode \u2005\u00c5], which is supported by the respective bond angles around Ag1 (Table\u00a01The asymmetric unit of (I)de Fig.\u00a01. There i1 Table\u00a01 summing 1 Table\u00a01. However3P tetra\u00adhedra gives the tetra\u00adnuclear structure of (I)4O4 heterocubanes O,O\u2032)-, - or -chelation Ag}4{(O2C)2C(CH2CH=CH2)2}2] was prepared by the addition of PPh3  to a suspension of [(AgO2C)2C(CH2CH=CH2)2]  in di\u00adchloro\u00admethane (30\u2005ml) at 273\u2005K. After stirring for 2\u2005h at this temperature, the reaction mixture was filtered through a pad of celite. Afterwards, all volatiles were removed in oil-pump vacuum, and (I)2C)2C(CH2CH=CH2)2]).Complex [{(Ph90H80Ag4O8P4 (1844.96): C 58.59, H 4.37. Found: C 58.53, H 4.34. 1H NMR : \u03b4 = 2.79 , 4.97 , 5.03 , 5.90 , 7.30\u20137.51 . 31P{1H} NMR : \u03b4 = 15.7 . IR : \u03bd = 1637 , 1559 , 1440 , 692 (vs), 521 (vs).Analysis calculated for CUiso(H) = 1.2Ueq(C) and a C\u2014H distance of 0.93\u2005\u00c5 for aromatic and vinylic as well as 0.97\u2005\u00c5 for methyl\u00adene protons. The unit cell contains two voids of 34(1.4)\u2005\u00c53. Void volume calculation using the SQUEEZE routine in PLATON ; however, this ambiguity is resolved as the Flack parameter of the inverted structure is calculated to 1.052\u2005(9). This indicates that the original absolute structure has been assigned correctly.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814019394/wm5047sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814019394/wm5047Isup2.hklStructure factors: contains datablock(s) I. DOI: 1021407CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The chloride ion occupies an equatorial site and the dihedral angle between the 2,2\u2032-bpy ring systems is 72.02\u2005(6)\u00b0. In the crystal, the components are linked by C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid separation = 3.635\u2005(2)\u2005\u00c5], generating a three-dimensional network.In the title hydrated salt, [NiCl(C DOI: 10.1107/S1600536814009064/hb7220Isup2.hklStructure factors: contains datablock(s) I. DOI: 998760CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the structure of bis\u00ad(2-amino-5-chloro\u00adpyridinium) tetra\u00adchlorido\u00adcobaltate(II), the essentially planar cations are connected through N\u2014H\u22efCl hydrogen bonds to the tetra\u00adhedral anion. 5H6ClN2)2[CoCl4], was synthesized by slow evaporation of an aqueous solution at room temperature. The asymmetric unit consists of two essentially planar (C5H6ClN2)+ cations [maximum deviations = 0.010\u2005(3) and 0.014\u2005(3)\u2005\u00c5] that are nearly perpendicular to each other [dihedral angle = 84.12\u2005(7)\u00b0]. They are bonded through N\u2014H\u22efCl hydrogen bonds to distorted [CoCl4]2\u2212 tetra\u00adhedra, leading to the formation of undulating layers parallel to (100). The structure is isotypic with the Zn analogue The title salt, (C The bond angles C4\u2014N2\u2014C5 [123.6\u2005(3)\u00b0] and C9\u2014N3\u2014C10 [123.3\u2005(3)\u00b0] in the rings of cat1 and cat2, respectively, confirm the presence of pyridinium cations. Previous studies  to 2.2934\u2005(12)\u2005\u00c5 and the Cl\u2014Co\u2014Cl angles range from 104.84\u2005(5) to 118.58\u2005(5)\u00b0, revealing considerable distortions from the ideal tetra\u00adhedral geometry. These values are in agreement with those observed in similar compounds  by hydrogen bonds  with a second symmetry-related cat1 cation. The hydrogen-bonding environments of the two cations are similar. Both are linked to two CoCl4 tetra\u00adhedra by three hydrogen bonds 2[ZnCl4]\u00b7H2O 2[ZnCl4] 2[CdCl4]\u00b7H2O 2[CuCl4] 2[CuBr4] 2[ZnCl4]  chloride and 2-amino-5-chloro\u00adpyridine (molar ratio 1:1) was dissolved in an aqueous solution of hydro\u00adchloric acid with 5\u2005ml of ethanol. The mixture was stirred and then kept at room temperature. Blue crystals of the title compound were obtained after two weeks.Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015007707/wm5146sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015007707/wm5146Isup2.hklStructure factors: contains datablock(s) I. DOI: 990478CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ReI ion is coordinated by two N atoms from the 1,10-phenanthroline ligand and one N atom from the 1,2-bis\u00ad(pyridin-4-yl)ethane ligand [mean Re\u2014N = 2.191\u2005(15)\u2005\u00c5] and by three carbonyl ligands [mean Re\u2014C = 1.926\u2005(3)\u2005\u00c5] in a distorted octa\u00adhedral geometry. The electrostatic forces and weak C\u2014H\u22efF(O) hydrogen bonds pack cations and anions into the crystal with voids of 82\u2005\u00c53, which are filled by solvent mol\u00adecules. The crystal packing exhibits short inter\u00admolecular O\u22efO distance of 2.795\u2005(5)\u2005\u00c5 between two cations related by inversion.The asymmetric unit of the title compound, [Re(C DOI: 10.1107/S1600536814014135/cv5465Isup2.hklStructure factors: contains datablock(s) I. DOI: 1008626CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The equatorial plane is formed by two N,O-bidentate 1H-pyrazole-3-carboxyl\u00adate ligands in a trans configuration. The axial positions are occupied by two water mol\u00adecules. The mononuclear complex mol\u00adecules are arranged in layers parallel to the ab plane. Each complex mol\u00adecule is linked to four adjacent species through inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds that are established between the coordinating water mol\u00adecules and carboxyl\u00adate O atoms or protonated N atoms of the organic ligands. These layers are further connected into a three-dimensional network by additional hydrogen bonds involving solvent water mol\u00adecules and non-coordinating carboxyl\u00adate O atoms.In the title compound, [Cu(C H-pyrazole-3-carboxyl\u00adate ligand, see: Artetxe et al. , nickel(II) and zinc complexes of the 1 al. 2015; L\u00f3pez-V al. 2014.4H3N2O2)2(H2O)2]\u00b72H2O = 0.028wR(F2) = 0.074S = 1.091216 reflections109 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.36 e \u00c5\u22123\u0394\u03c1min = \u22120.35 e \u00c5\u22123\u0394\u03c1CrysAlis PRO  used to solve structure: OLEX2  I, global. DOI: 10.1107/S2056989015021593/im2473Isup2.hklStructure factors: contains datablock(s) global, a2013072_cupyc. DOI: Click here for additional data file.10.1107/S2056989015021593/im2473fig1.tif4 3 2 2 2 2 2 2 . DOI: 4H3N2O2)2(H2O)2] \u00b72H2O showing the atom labelling for the asymmetric unit and 50% probability displacement ellipsoids.Mol\u00adecular structure of [Cu. Projection of a layer of [Cu(C4H3N2O2)2(H2O)2] complexes along the [010] direction (below). Cu(II) centres are represented as translucent octa\u00adhedra and the O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds are depicted as dashed red lines.View of the crystal packing along the crystallographic 1437048CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "X is said to be End-completely-regular  if its endomorphism monoid End(X) is completely regular . In this paper, we will show that if X[Y] is End-completely-regular , then both X and Y are End-completely-regular . We give several approaches to construct new End-completely-regular graphs by means of the lexicographic products of two graphs with certain conditions. In particular, we determine the End-completely-regular and End-inverse lexicographic products of bipartite graphs.A graph  Endomorphism monoids of graphs are generalizations of automorphism groups of graphs. In recent years, much attention has been paid to endomorphism monoids of graphs and many interesting results concerning graphs and their endomorphism monoids have been obtained. The aim of this research is to develop further relationship between graph theory and algebraic theory of semigroups and to apply the theory of semigroups to graph theory. The bipartite graph is a class of famous graphs. Their endomorphism monoids are studied by several authors. In , the conX considered in this paper are undirected finite simple graphs. The vertex set of X is denoted by V(X) and the edge set of X is denoted by E(X). If two vertices x1 and x2 are adjacent in X, the edge connecting x1 and x2 is denoted by {x1, x2} and we write {x1, x2} \u2208 E(X). A subgraph H is called an induced subgraph of X if for any a, b \u2208 V(H), {a, b} \u2208 E(H) if and only if {a, b} \u2208 E(X). A graph X is called bipartite if X has no odd cycle. It is known that if a graph X is a bipartite graph, then its vertex set can be partitioned into two disjoint nonempty subsets such that no edge joins two vertices in the same set.The graphs X and Y be two graphs. The join of X and Y, denoted by X + Y, is a graph such that V(X + Y) = V(X) \u222a V(Y) and E(X + Y) = E(X) \u222a E(Y)\u222a{{x1, x2} | x1 \u2208 V(X), x2 \u2208 V(Y)}. The lexicographic product of X and Y, denoted by X[Y], is a graph with vertex set V(X[Y]) = V(X) \u00d7 V(Y), and with edge set E(X[Y]) = {{, }\u2223{x, x1} \u2208 E(X), or x = x1 and {y, y1} \u2208 E(Y)}. Denote Yx = { | y \u2208 V(Y)} for any x \u2208 V(X).Let X and Y be graphs. A mapping f from V(X) to V(Y) is called a homomorphism (from X to Y) if {x1, x2} \u2208 E(X) implies that {f(x1), f(x2)} \u2208 E(Y). A homomorphism f is called an isomorphism if f is bijective and f\u22121 is a homomorphism. A homomorphism  f from X to itself is called an endomorphism  of X (see \u03c1f the equivalence class containing a \u2208 V(X) with respect to \u03c1f.Aa of a semigroup S is called regular if there exists x \u2208 S such that axa = a. An element a of a semigroup S is called completely regular if a = axa and xa = ax hold for some x \u2208 S. A semigroup S is called regular  if all its elements are regular . An inverse semigroup is a regular semigroup in which the idempotents commute. A graph X is said to be End-regular  if its endomorphism monoid End(X) is regular . Clearly, End-completely-regular graphs as well as End-inverse graphs are End-regular.An element For undefined notation and terminology in this paper, the reader is referred to \u201314. We lX[Y] is End-regular, then both X and Y are End-regular.If G be a graph and let f \u2208 End(G). Then f is completely regular if and only if f|If \u2208 Aut(If).Let X be a bipartite graph. Then X is End-completely-regular if and only if X is one of K1, K2, P2, 2K1, 2K2, and K1 \u22c3 K2.Let X and Y be two bipartite graphs. Then X + Y is End-completely-regular if and only if one of them is End-completely-regular and the other is K1 or K2.Let G be a graph and f \u2208 End(G). Then f is completely regular if and only if there exists g \u2208 Idpt(G) such that \u03c1g = \u03c1f and Ig = If.Let X be a bipartite graph. Then X is End-inverse if and only if X = K1 or X = K2.Let X and Y be two graphs. Then End(X[Y]) = End(X)[End(Y)] if and only if for any f \u2208 End(X[Y]) and x \u2208 V(X), there exists x\u2032 \u2208 V(X) such that f(Yx)\u2286Yx\u2032.Let X[Y] is End-completely-regular, then both X and Y are End-completely-regular.In this section, we will characterize the End-completely-regular and End-inverse lexicographic products of two graphs. We first show that if X and Y be two graphs. If X[Y] is End-completely-regular, then both X and Y are End-completely-regular.Let X is End-completely-regular, it is only necessary to verify that f|If is an automorphism of If for each f \u2208 End(X). Define a mapping F from V(X[Y]) to itself byF \u2208 End(X[Y]). Since X[Y] is End-completely-regular, by F|IF is an automorphism of IF. It is easy to see that IF = If[Y]. For any distinct x1, x2 \u2208 V(If) and y \u2208 V(Y), F) = (f(x1), y) and F) = (f(x2), y) hold. Since F|IF is an automorphism of IF, (f(x1), y)\u2260(f(x2), y). Hence f(x1) \u2260 f(x2) and so f|If is an automorphism of If.By g \u2208 End(Y). Define a mapping G from V(X[Y]) to itself byG \u2208 End(X[Y]). Since X[Y] is End-completely-regular, by G|IG is an automorphism of IG. It is easy to see that IG = X[Ig]. For any x \u2208 V(X) and y1, y2 \u2208 V(Ig), G) = ) and G) = ). Since G|IG is an automorphism of IG, )\u2260), we get that g(y1) \u2260 g(y2) and so g|Ig is an automorphism of Ig, as required.Let X and Y being End-completely-regular does not yield that X[Y] is End-completely-regular.The following example shows that X and Y be two graphs with V(X) = {x1, x2}, V(Y) = {y1, y2}, E(X) = {{x1, x2}}, and E(Y) = \u03d5. By X and Y are End-completely-regular. It is easy to see that X[Y]\u2245C4. Also by Let X[Y] to be End-completely-regular. To this aim, we need the following result due to Fan ) = End(X)[End(Y)], where End(X)[End(Y)] is the wreath product of the monoids End(X) and End(Y).Let X and Y be two K3-free connected graphs such that girth(X) or girth(Y) is odd. In  is End-regular. Here we prove that if X is an End-completely-regular graph and Y is an unretractive graph, then X[Y] is End-completely-regular.Let  odd. In , Fan proX and Y be two K3-free connected graphs with girth(X) or girth(Y) being odd, and assume thatX\u2009\u2009is End-completely-regular,Y is unretractive.Then X[Y] is End-completely-regular.Let X and Y be two graphs satisfying the assumptions. To show that X[Y] is End-completely-regular, we prove that for any F \u2208 End(X[Y]), there exists an idempotent endomorphism G \u2208 End(X[Y]) such that \u03c1F = \u03c1G and IF = IG.Let F \u2208 End(X)[End(Y)]. Since End(X[Y]) = End(X)[End(Y)], F =  for some s \u2208 End(X) and f \u2208 End(Y)V(X). Thus, for any u \u2208 V(X), there exists fu = f(u) \u2208 End(Y). Let X and Y be K3-free connected graphs with girth(X) or girth(Y) being odd. By u \u2208 V(X), F(Yu)\u2286Yv for some v \u2208 V(X). Note that Y is unretractive. Then F(Yu) = Yv. Since X is End-completely-regular and s \u2208 End(X), by t \u2208 Idpt(X) such that \u03c1t = \u03c1s and It = Is. Clearly, Is is an induced subgraph of X. Hence IF = Is[Y] is an induced subgraph of X[Y].Let X is End-completely-regular, s|Is is an automorphism of Is. Thus for any u \u2208 Is, there exists only one vertex u1 \u2208 Is such that s(u1) = u. Then F(Yu1) = Yu. Now for any  \u2208 IF, there exists only one vertex  \u2208 IF such that F) = . Define a mapping G from V(X[Y]) to itself in the following way. If  \u2208 V(IF), then G) = ; if  \u2209 V(IF), then F) =  for some  \u2208 V(IF). Now let G) = , where  is the only vertex in V(IF) such that F) = . Then it is easy to see that G is well-defined. Let  \u2208 V(X[Y]). If  \u2208 V(IF), then x \u2208 Is. Thus t(x) = x. Hence G) =  \u2208 Yt(x). If  \u2209 V(IF), then t(x) = u1. Hence G) =  \u2208 Yt(x). Therefore, G) \u2208 Yt(x) for any  \u2208 V(X[Y]).Since x1, y1),  \u2208 V(X[Y]) be such that {, } \u2208 E(X[Y]). If ,  \u2208 V(IF), then {G), G)} = {, } \u2208 E(X[Y]). If  \u2208 V(IF) and  \u2209 V(IF), then x1 \u2260 x2 and {x1, x2} \u2208 E(X). Thus G) \u2208 Yt(x1) and G) \u2208 Yt(x2). Since t \u2208 Idpt(X) and {x1, x2} \u2208 E(X), {t(x1), t(x2)} \u2208 E(X). Hence {G), G)} \u2208 E(X[Y]). If  \u2209 V(IF) and  \u2209 V(IF), there are two cases.Let . Then G) \u2208 Yt(x1) and G) \u2208 Yt(x2). Since t \u2208 Idpt(X) and {x1, x2} \u2208 E(X), {t(x1), t(x2)} \u2208 E(X). Hence we have {G), G)} \u2208 E(X[Y]).Case 2. Assume that x1 = x2 and {y1, y2} \u2208 E(Y). Then we have ,  \u2208 Yx1 and G), G) \u2208 Yt(x1). Since G|Yx1 is an isomorphism from Yx1 to Yt(x1), {G), G)} \u2208 E(X[Y]). Therefore, G \u2208 End(X[Y]).x, y) \u2208 V(IF), then G2) = G) = . If  \u2209 V(IF), then G) \u2208 V(IF). Thus G2) = G)) = G). Hence G \u2208 Idpt(X[Y]). Clearly, IG = IF.If ]\u03c1F = {, ,\u2026, } for some , ,\u2026,  \u2208 V(X[Y]). In fact, it is easy to prove that \u03c1F\u2286\u03c1G\u2286\u03c1F. Let \u03c1F. Then, by the definition of G, we have G) = G) =  for some  \u2208 V(IF) with F) = F = F). So \u03c1G and thus \u03c1F\u2286\u03c1G\u2286\u03c1F. Hence \u03c1F = \u03c1G.Suppose [ such that If = R. Let g \u2208 End(R[Y]). Since R[Y] is not End-completely-regular, there exists g \u2208 End(R[Y]) such that g is not completely regular. By g|Ig is not an automorphism of Ig. Thus there exist x1, x2 \u2208 Ig with x1 \u2260 x2 such that g(x1) = g(x2). Define a mapping F from V(X[Y]) to itself byF \u2208 End(X[Y]) and IF = R[Y]. Now it is easy to see that gF \u2208 End(X[Y]) and IgF = Ig. It follows from (gF)(x1) = (gF)(x2) that (gF)|IgF is not an automorphism of IgF. Hence X[Y] is not End-completely-regular.Let X and Y be two graphs. If at least one of X and Y is not End-completely-regular, then X \u222a Y is not End-completely-regular (where X \u222a Y is the disjoint union of X and Y).Let X is not End-completely-regular. By f \u2208 End(X) such that f|If is not an automorphism of If. Define a mapping F from V(X \u222a Y) to itself byF \u2208 End(X \u222a Y). Now it is easy to see that IF = If \u222a Y and F(x) = f(x) for any x \u2208 V(X). Since f|If is not an automorphism of If, F|IF is not an automorphism of IF. Hence X \u222a Y is not End-completely-regular.Without loss of generality, we may suppose that X and Y be two bipartite graphs. Then X[Y] is End-completely-regular if and only ifX = K1 and Y is End-completely-regular orX is End-completely-regular and Y = K1 or K2.Let Sufficiency. Since K1[Y] = Y and X[K1] = X, we have immediately that K1[Y](X[K1]) is End-completely-regular if and only if Y(X) is End-completely-regular. If X = Y = K2, then X[Y] = K4. Thus End(X[Y]) is a group. Since any group is a completely regular semigroup, X[Y] is End-completely-regular. If X = 2K1 and Y = K2, then X[Y] = 2K2. By X[Y] is End-completely-regular for the following cases (see ases see .Case 1. X = P2 and Y = K2. Let f \u2208 End(X[Y]). If [x1]\u03c1f = {x1}, then [x2]\u03c1f = {x2}. Otherwise, f(x2) = f(z1) or f(x2) = f(z2). Without loss of generality, we can suppose f(x2) = f(z1). Since z1 is adjacent to every vertex of {z2, y1, y2} and {x1, x2} \u2208 E(X[Y]), f(z1) is adjacent to every vertex of {f(z2), f(y1), f(y2), f(x1)}. Note that there is no vertex in X[Y] adjacent to 4 vertices. This is a contradiction. Hence f \u2208 Aut(X[Y]) and so f is completely regular. If [x1]\u03c1f \u2260 {x1}, then f(x1) = f(z1) or f(x1) = f(z2). Without loss of generality, we can suppose f(x1) = f(z1). Then f(x2) = f(z2). Otherwise, a similar argument as above will show that f(x1) is adjacent to every vertex of {f(x2), f(y1), f(y2), f(z2)}, which yield a contradiction. Thus If\u2245K4. Since any endomorphism f maps a clique to a clique of the same size, f(If) = If. By f is completely regular. Hence P2[K2] is End-completely-regular.Case 2. X = K1 \u222a K2 and Y = K2. Let f \u2208 End(X[Y]). If [c1]\u03c1f = {c1}, then [c2]\u03c1f = {c2}. Otherwise, f(c2)\u2208{f(a1), f(a2), f(b1), f(b2)}. Without loss of generality, we can suppose f(c2) = f(a1). Since any endomorphism f maps a clique to a clique of the same size and there is only one clique of size 4 in X[Y], {f(a1), f(a2), f(b1), f(b2)} = {a1, a2, b1, b2}. Note that {c1, c2} \u2208 E(X[Y]). Then {f(c1), f(c2)} = {f(c1), f(a1)}\u2208\u2009E(X[Y]). Thus f(c1)\u2208{f(a1), f(a2), f(b1), f(b2)}, which is a contradiction. Clearly, [x]\u03c1f = {x} for any x \u2208 {a1, a2, b1, b2}. Hence f \u2208 Aut(X[Y]) and so f is completely regular. If [c1]\u03c1f \u2260 {c1}, then f(c1) = f(t) for some t \u2208 {a1, a2, b1, b2}. Without loss of generality, we can suppose f(c1) = f(a1). Then f(c2)\u2208{f(a2), f(b1), f(b2)}. Thus If\u2245K4. Hence f(If) = If and f is completely regular. Consequently, (K1 \u222a K2)[K2] is End-completely-regular.Case 3. X = 2K2 and Y = K2. Let f \u2208 End(X[Y]). If [x]\u03c1f = {x} for any x \u2208 V(X[Y]), then f \u2208 Aut(X[Y]) and so f is completely regular. If f(x) = f(y) for some x, y \u2208 V(X[Y]) with x \u2260 y, without loss of generality, we can suppose f(a1) = f(c1). Since b1, b2, c1, c2 is a clique of size 4 in X[Y], f(b1), f(b2), f(c1), f(c2) is also a clique of size 4 in X[Y]. Note that a2, d1, d2 are adjacent to a1. Then f(a2), f(d1), f(d2) are adjacent to f(a1) = f(c1). Thus f(a2), f(d1), f(d2)\u2208{f(b1), f(b2), f(c2)} and If\u2245K4. Hence f(If) = If and f is completely regular. Consequently, (2K2)[K2] is End-completely-regular. Necessity. We only need to show that X[Y] is not End-completely-regular in the following cases.Case 1\u2009\u2009(X = K2). Then X[Y] = Y + Y. By K2[Y] is not End-completely-regular for the corresponding Y.Case 2\u2009\u2009(X = P2). Then K2 is a retract of X. Since K2[Y] is not End-completely-regular for Y = P2, 2K1, 2K2, K1 \u222a K2, by P2[Y] is not End-completely-regular for the corresponding Y.Case 3\u2009\u2009(X = 2K1). Then X[Y] = 2Y. If Y is bipartite, then X[Y] is also bipartite. By K1)[Y] is not End-completely-regular for the corresponding Y.Case 4\u2009\u2009(X = 2K2). Then X[Y] = 2(Y + Y). Since Y + Y is not End-completely-regular for Y = P2, 2K1, 2K2, K1 \u222a K2, by K2)[Y] is not End-completely-regular for the corresponding Y.Case 5\u2009\u2009(X = K1 \u222a K2). Then X[Y] = Y \u222a (Y + Y). Since Y + Y is not End-completely-regular for Y = P2, 2K1, 2K2, K1 \u222a K2, by K1 \u222a K2)[Y] is not End-completely-regular for the corresponding Y.X and Y under which X[Y] is End-inverse.Next we start to seek the conditions for a lexicographic product of bipartite graphs X and Y be two graphs. If X[Y] is End-inverse, then both X and Y are End-inverse.Let X[Y] is End-inverse, X[Y] is End-regular. By X and Y are End-regular. To show that X is End-inverse, we only need to prove that the idempotents of End(X) commute.Since f1 and f2 be two idempotents in End(X). Define two mappings g1 and g2 from V(X[Y]) to itself byg1 and g2 are two idempotents of End(X[Y]) and so g1g2 = g2g1, since X[Y] is End-inverse. For any  \u2208 V(X[Y]), we havef1f2 = f2f1. Hence X is End-inverse.Let f3 and f4 be two idempotents in End(Y). Define two mappings g3 and g4 from V(X[Y]) to itself byg3 and g4 are two idempotents of End(X[Y]) and so g3g4 = g4g3, since X[Y] is End-inverse. For any  \u2208 V(X[Y]), we havef3f4 = f4f3. Hence Y is End-inverse, as required.Similarly, let The next theorem characterizes the End-inverse lexicographic products of bipartite graphs.X and Y be two bipartite graphs. Then X[Y] is End-inverse if and only if X[Y] is one of K1[K1], K1[K2], K2[K1], and K2[K2].Let Necessity. This follows directly from Sufficiency. It is easy to see that K1[K1] = K1, K1[K2] = K2[K1] = K2, and K2[K2] = K4 are End-inverse, since they are unretractive."}
{"text": "The aromatic rings attached to the SO 14H13NO5S, was synthesized via a nucleophilic substitution reaction between 3,5-di\u00admethyl\u00adphenol and 2-nitro\u00adbenzene\u00adsulfonyl chloride. The aromatic rings attached to the SO3 group are oriented in a gauche fashion around the ester S\u2014O bond, with a C\u2014S\u2014O\u2014C torsion angle of 84.68\u2005(11)\u00b0. The mol\u00adecules form centrosymmetric dimers via \u03c0\u2013\u03c0 stacking inter\u00adactions between 3,5-di\u00admethyl\u00adphenyl groups (centroid\u2013centroid distance = 3.709\u2005\u00c5). An inter\u00admolecular S=O\u22efN inter\u00adaction between the sulfonyl and nitro groups, with an O\u22efN distance of 2.9840\u2005(18)\u2005\u00c5, organizes the dimers into columns extending along [011]. These columns are further assembled into (111) layers through C\u2014H\u22efO inter\u00adactions.The title compound, C Owing to steric hindrance between the ortho substituents of the benzene ring, the nitro group is twisted relative to the benzene best plane by 39.91\u2005(2)\u00b0, so that the shortest contact of 2.7941\u2005(16)\u2005\u00c5 between the O atoms of these groups is close to the sum of the van der Waals radii.In the title mol\u00adecule Fig.\u00a02, the O1=via inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between the relatively electron-rich C7\u2013C12 benzene rings  layers. The geometry of these inter\u00adactions is given in Table\u00a01o-nitro\u00adaryl\u00adsulfonyl moiety bonded to an aromatic ring through an ester linkage. These are CSD refcodes FEMQUK \u2013103.43\u2005(13)\u00b0. In each of these structures there are either intra- or inter\u00admolecular S=O\u22efN inter\u00adactions between the sulfonate and o-nitro groups.The Cambridge Structural Database  portion-wise. The mixture was stirred at 273\u2005K for 30 mins and then at room temperature for 24\u2005h. The product precipitated from the reaction mixture after sitting at 277\u2005K for two weeks. The product was redissolved in di\u00adchloro\u00admethane, and the solvent was allowed to evaporate slowly to give large block-shaped crystals that were suitable for analysis by X-ray diffraction (m.p. 374\u2013378\u2005K).3,5-Di\u00admethyl\u00adphenol  was dissolved in chilled di\u00adchloro\u00admethane (25\u2005ml). This was followed by the addition of pyridine . The resulting solution was cooled in an ice bath under an NUiso(H) = 1.2Ueq(C) for CH groups and 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015078/gk2639sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015078/gk2639Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015078/gk2639Isup3.cmlSupporting information file. DOI: 1418463CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of a binuclear mono\u00adcarboxyl\u00adato dirhenium(III) complex with a fulvalene derivative is reported. This compound represents a radical cation salt containing a cluster unit with rhenium\u2013rhenium quadruple bond. 10H8S8)[Re2Br6(CH3COO)]\u00b70.5C2H3Cl3, contains one bis\u00ad(ethyl\u00adenedi\u00adthio)\u00adtetra\u00adthia\u00adfulvalene (ET) radical cation, one \u03bc2-acetato-bis\u00ad[tri\u00adbromido\u00adrhenate(III)] anion and a 1,1,2-tri\u00adchloro\u00adethane mol\u00adecule with half-occupancy disordered about a twofold rotation axis. The tetra\u00adthia\u00adfulvalene fragment adopts an almost planar configuration typical of the ET radical cation. The C atoms of both ethyl\u00adenedi\u00adthio fragments in the cation are disordered over two orientations with occupancy factors 0.65:0.35 and 0.77:0.23. In the anion, six Br atoms and a \u03bc2-acetate ligand form a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 dinuclear centre. In the crystal, centrosymmetrically related ET cations and Re2O2Br6 anions are linked into dimers by \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.826\u2005(8)\u2005\u00c5] and by pairs of additional Re\u22efBr contacts [3.131\u2005(3)\u2005\u00c5], respectively. The dimers are further packed into a three-dimensional network by non-directional inter\u00adionic electrostatic forces and by C\u2014H\u22efBr and C\u2014H\u22efS hydrogen bonds. The disordered 1,1,2-tri\u00adchloro\u00adethane mol\u00adecules occupy solvent-accessible channels along the b axis.The asymmetric unit of the title salt, (C Neither acetic acid nor acetate was used in the synthesis of this radical cation salt. Evidently, the acetate ligand arose by hydrolysis of CH3CN ] anions and 1,1,2-tri\u00adchloro\u00adethane mol\u00adecules in the stoichiometric molar ratio of 1:1:0.5. The solvent mol\u00adecule is disordered over two orientations of equal occupancy about a twofold rotation axis inter\u00adsecting the mid-point of the C\u2014C ethane bond. The tetra\u00adthia\u00adfulvalene fragment adopts an almost planar configuration (r.m.s. deviation = 0.033\u2005\u00c5) that is typical for ET radical cations. The dihedral angle between the five-membered rings is 0.3\u2005(6)\u00b0. The carbon atoms of both ethyl\u00adenedi\u00adthio fragments (C4/C5 and C9/C10) are disordered over two sets of sites with occupancy ratios of 0.65:0.35 and 0.77:0.23, respectively.The title compound Fig.\u00a01 consistsIII atom is coordinated by three Br atoms forming ReBr3 units which are linked by a Re\u2014Re multiple bond [2.2174\u2005(10)\u2005\u00c5] and a bridging \u03bc2-acetate ligand, forming a strongly distorted cubic O2Br6 coordination polyhedron around the Re2 core. The length of the Re\u2014Re bond is very close to the mean value of 2.222\u2005\u00c5 for quadruple bonds \u20132.2731\u2005(9)\u2005\u00c5 for compounds with no bridging ligands and in the range 2.2168\u2005(8)\u20132.2532\u2005(2)\u2005\u00c5 for compounds with O,O-bridging ligands \u2005\u00c5]. Cationic and anionic dimers are packed into a three-dimensional network by non-directional inter\u00admolecular electrostatic forces and by C\u2014H\u22efBr and C\u2014H\u22efS hydrogen bonds -hexa\u00adchlorido\u00addirhenate anion exhibiting the same structure of the title compound  anion  in a two-electrode U-shaped glass cell with platinum electrodes. The initial current intensity of 0.1\u2005\u00b5A was increased by 0.05\u2005\u00b5A per day to a final value of 0.45\u2005\u00b5A. A mixture of 1,1,2-tri\u00adchloro\u00adethane/aceto\u00adnitrile (12:1 v/v) was used as solvent. [(C4H9)4N]2[Re2Br8] (0.008\u2005mol\u2005l\u22121) was used as electrolyte. After a period of 6\u20137 weeks, black shiny plate-shaped crystals of the title salt suitable for X-ray analysis were formed.The synthesis of the radical cation title salt was performed by galvanostatic anodic oxidation of ET (0.002\u2005mol\u2005lUiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. The 1,1,2-tri\u00adchloro\u00adethane mol\u00adecule is disordered over two sets of sites about a twofold rotation axis with equal occupancy. The C4\u2013C5 and C9\u2013C10 groups of the ET cations are disordered over two orientations with occupancy factors of 0.65/0.35 and 0.77/0.23, respectively. These occupancies were initially obtained as free variables by the full-matrix refinement, and were then fixed in the final refinement cycles. The C\u2014C and C\u2014Cl bond lengths in the solvent mol\u00adecule were constrained to be 1.52\u2005(1) and 1.80\u2005(1)\u2005\u00c5, respectively, and the C\u2014Cl bonds of the solvent mol\u00adecule were restrained to have the same lengths to within 0.01\u2005\u00c5. The C\u2014S and C\u2014C bonds of the disordered fragments of the ET cation were also restrained to have the same lengths to within 0.005\u2005\u00c5. The atoms of each disordered fragment, including the solvent mol\u00adecule, were restrained to have approximately the same displacement parameters to within 0.02\u20130.04\u2005\u00c52. DELU restraints to within 0.01\u2005\u00c52 were applied to atoms C4B, C5B, C9B, C10B, C1S and Cl2S. In addition, all non-hydrogen atoms of the solvent mol\u00adecule were restrained to be approximately isotropic to within 0.03\u20130.06\u2005\u00c52. Several outlier reflections (67) that were believed to be affected by the contribution of several unresolved minor twin domains were omitted from the final cycles of refinement, reducing the R factor from 0.061 to 0.052. Attempts to refine the structure using a two-component twin model were unsuccessful. Moreover, the crystals of the title compound are stable but show a strong tendency to splicing. The poor quality of the available crystal may account for the rather low bond precision of the C\u2014C bonds and the presence of several large residual density peaks.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016006058/rz5188sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016006058/rz5188Isup2.hklStructure factors: contains datablock(s) I. DOI: 1473493CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One O atom from the adjacent hy\u00addroxy\u00adimino-tosyl\u00adhydrazone ligand bridges the CuII cation, forming the centrosymmetric dimeric complex. The cation is in an overall distorted N2O3 square-pyramidal coordination environment. The methyl\u00adbenzene ring is twisted with respect to the hydrazine fragment, with a dihedral angle of 89.54\u2005(9)\u00b0 between the planes. An intra\u00admolecular C\u2014H\u22efO hydrogen bond occurs. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efS inter\u00adactions. Weak \u03c0\u2013\u03c0 stacking is also observed between parallel benzene rings of adjacent mol\u00adecules, the centroid\u2013centroid distance being 3.9592\u2005(17)\u2005\u00c5.In the title compound, [Cu DOI: 10.1107/S1600536814016651/xu5805Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814016651/xu5805fig1.tifx y z . DOI: x\u00a0+\u00a01,-y\u00a0+\u00a01,-z\u00a0+\u00a01The mol\u00adecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level showing the dimeric structure. Symmetry code: (i)-Click here for additional data file.10.1107/S1600536814016651/xu5805fig2.tifb . DOI: b-axis showing the column of the aromatic rings with very weak \u03c0\u2013\u03c0 inter\u00adactions.Mol\u00adecules of the title compound arranged along 1014769CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ions through eight- and 12-membered rings, respectively, forming polymeric chains running along the a-axis direction.The asymmetric unit of the title zinc(II) coordination polymer contains two 4-nitro\u00adbenzoate (NB) anions and two nicotinamide (NA) ligands. Only one of the two NB anions and one of the two NA ligands bridge adjacent Zn 7H4NO4)2(C6H6N2O)2]n, contains two 4-nitro\u00adbenzoate (NB) anions and two nicotinamide (NA) ligands. The ZnII atom has a slightly distorted octa\u00adhedral coordination sphere. In the equatorial plane, it is coordinated by three carboxyl\u00adate O atoms of the NB anions and one O atom of one of the two NA ligands. The axial positions are occupied by the pyridine N atoms of the two NA ligands. In the two NB anions, the carboxyl\u00adate groups are twisted away from the attached benzene rings by 13.8\u2005(2) and 13.4\u2005(2)\u00b0, while the benzene rings are oriented at a dihedral angle of 11.5\u2005(2)\u00b0. The dihedral angle between the NA rings is 10.3\u2005(1)\u00b0. Only one of the two NB anions and one of the two NA ligands bridge adjacent ZnII ions through eight- and twelve-membered rings, respectively, forming polymeric chains running along the a-axis direction. In the crystal, N\u2014H \u22ef O hydrogen bonds link adjacent chains, enclosing R(16), R22(20) and R66(16) ring motifs, forming layers parallel to (01-1). The layers are linked via a number of C\u2014H\u22efO hydrogen bonds, forming a three-dimensional network.The asymmetric unit of the title coordination polymer, [Zn(C N,N-di\u00adethyl\u00adnicotinamide (DENA) is an important respiratory stimulant  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels , 5.855\u2005(4), 4.480\u2005(3)\u2005\u00c5 and 4.67\u2005(6), 3.668\u2005(4), 4.256\u2005(4)\u2005\u00c5, respectively ; see Fig.\u00a03The asymmetric unit of the title polymeric compound contains two 4-nitro\u00adbenzoate (NB) anions and two nicotinamide (NA) ligands; the NB anions act as monodentate ligands Fig.\u00a01. Only onon Fig.\u00a02. In the II cation form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms (N3 and N5) of the two NA ligands in the axial positions  of the three NB anions and one O atom (O10) of one of the two NA ligands in the equatorial plane around the Zns Table\u00a01.carboxyl\u00adate and Zn\u2014N distances are 2.147\u2005(2)\u2005\u00c5 and 2.285\u2005(3)\u2005\u00c5, respectively, while Zn1\u2014O10 distance is 2.280\u2005(2)\u2005\u00c5. The Zn1 atom lies 1.4330\u2005(4)\u2005\u00c5 and 0.1897\u2005(4)\u2005\u00c5 above the planar (O1/O2/C1) and (O5/O6/C8) carboxyl\u00adate groups, respectively. The average O\u2014Zn\u2014O and O\u2014Zn\u2014N bond angles are 89.93\u2005(10) and 89.99\u2005(10)\u00b0, respectively.The near equality of the C1\u2014O1 [1.247\u2005(4)\u2005\u00c5], C1\u2014O2 [1.261\u2005(4)\u2005\u00c5], C8\u2014O5 [1.248\u2005(4)\u2005\u00c5] and C8\u2014O6 [1.255\u2005(4)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn\u2014OA (C2\u2014C7) and B (C9\u2014C14)] are 13.8\u2005(2) and 13.4\u2005(2)\u00b0, respectively, while the benzene rings are oriented at a dihedral angle of 11.5\u2005(2)\u00b0. The dihedral angle between the nicotin\u00adamide rings [C (N3/C15\u2014C19) and D (N5/C21\u2014C25)] is 10.3\u2005(1)\u00b0, and they are oriented with respect to benzene rings A and B at dihedral angles of A/C = 17.3\u2005(1), A/D = 7.7\u2005(1), B/C = 28.8\u2005(1) and B/D = 18.9\u2005(1)\u00b0.The dihedral angles between the planar carboxyl\u00adate groups [(O1/O2/C1) and (O5/O6/C8)] and the adjacent benzene rings [c (c = carboxylate) and N\u2014H\u22efOn (n = nicotinamide) hydrogen bonds (Table\u00a02R(16), et al., 1995n\u22efOc and inter\u00admol\u00adec\u00adular C\u2014Hn\u22efOnb (nb = nitro\u00adbenzoate) and C\u2014Hn\u22efOn hydrogen bonds  Fig.\u00a04. Weak ins Table\u00a01 link the4\u00b7H2O  in H2O (25\u2005ml) and nicotinamide  in H2O (25\u2005ml) with sodium 4-nitro\u00adbenzoate  in H2O (150\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving yellow block-like crystals.The title compound was prepared by the reaction of ZnSOUiso(H) = 1.2Ueq. The highest residual electron density and the deepest hole were found 0.29\u2005\u00c5 and 0.48\u2005\u00c5 from atoms N6 and Zn1, respectively.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0310.1107/S2056989015006490/su5099sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015006490/su5099Isup2.hklStructure factors: contains datablock(s) I. DOI: 1057121CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H,3H,5H)-trione, which crystallized with two mol\u00adecules in its asymmetric unit along with two solvent water mol\u00adecules. A hydrogen-bonded sheet is formed by a combination of N\u2014H\u22efO and Owater\u2014H\u22efO hydrogen bonds, which are further inter\u00adconnected by C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions, leading to a three-dimensional supra\u00admolecular architecture.Reaction of 4-methyl benzyl chloride with barbituric acid gave 5,5-bis\u00ad(4-methyl\u00adbenz\u00adyl)pyrimidine-2,4,6, with similar conformations and two independent water mol\u00adecules. In the crystal, N\u2014H\u22efO and Owater\u2014H\u22efO hydrogen bonds link all moieties into two crystallographically independent kinds of sheets parallel to the ac plane. These independent sheets, each containing either A or B mol\u00adecules, are further alternately stacked along the b axis and inter\u00adconnected via C\u2014H\u22ef\u03c0ar\u00adyl inter\u00adactions.The asymmetric unit of the title compound, C In B, the corresponding angles are 50.44\u2005(18), 69.90\u2005(19) and 59.8\u2005(2)\u00b0, respectively. In the related compound 5,5-di\u00adbenzyl\u00adbarbituric acid monohydrate (II) via strong N2\u2014HN2\u22efO4 (A) and N3\u2014HN3\u22efO7 (B) hydrogen bonds C(6). Six chains pass through the unit cell. These chains are linked via water mol\u00adecules through N1\u2014H1\u22efO1 and O1\u2014H1B\u22efO5 (for A) and N4\u2014HN4\u22efO2 and O2\u2014H2A\u22efO8 (for B) hydrogen bonds (Table\u00a01D(2). In addition, the symmetry-dependent parallel chains are inter\u00adconnected via bridging water mol\u00adecules through O\u2014H\u22efO3 and O1\u2014HIB\u22efO5 (for A) and O2\u2014H2B\u22efO6 and O2\u2014H2A\u22efO8 (for B) hydrogen bonds  crystallizes in the monoclinic space group P21/n. Secondly, (I)There are several inter\u00adesting differences between the two chemically closely related structures (I)To an ice-cooled stirring solution of acetonitrile (5\u2005ml), 4-methyl benzyl chloride , 1,8-diazabicycloundec-7-ene (DBU)  and barbituric acid  were added. The reaction mixture was stirred to the room temperature and then refluxed for 8\u2005h. Thin-layer chromatography showed the absence of any starting material. The reaction mixture was cooled and poured into ice-cold water. The solid obtained was extracted with ethyl acetate and the organic layer was washed with saturated ammonium chloride solution and dried over anhydrous sodium sulphate. The solvent was removed under reduced pressure to give the title compound as a white solid .Colourless prisms of the title compound suitable for diffraction studies were grown from an ethyl acetate\u2013petroleum ether solvent system in the ratio 2.5:7.5, by the solvent evaporation technique.Ueq(C) for methyl H atoms and = 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901402619X/cv5478sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901402619X/cv5478Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901402619X/cv5478Isup3.cmlSupporting information file. DOI: 1036677CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecular components, enclosing In the title salt, [Zn(C 8H4NO2)(C6H6N2O)(H2O)3](C8H4NO2), contains one complex cation and one 4-cyano\u00adbenzoate (CNB) counter-anion. The ZnII atom in the cation is coordinated by one 4-cyano\u00adbenzoate ligand, one nicotinamide (NA) ligand and three water mol\u00adecules, the CNB anion thereby coordinating in a bidentate O,O\u2032-mode through the carboxyl\u00adate group. The latter, together with one water O atom and the N atom of the NA ligand, form a distorted square-planar arrangement, while the considerably distorted octa\u00adhedral coordination sphere of the ZnII atom is completed by the two O atoms of additional water mol\u00adecules in the axial positions. The dihedral angles between the planar carboxyl\u00adate groups and the adjacent benzene rings in the two anions are 10.25\u2005(10) and 5.89\u2005(14)\u00b0. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds link two of the coordinating water mol\u00adecules to two free CNB anions. In the crystal, further hydrogen-bonding inter\u00adactions are present, namely N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds that link the mol\u00adecular components, enclosing R22(12), R33(8) and R33(9) ring motifs and forming layers parallel to (001). \u03c0\u2013\u03c0 contacts between benzene rings [centroid-to-centroid distances = 3.791\u2005(1) and 3.882\u2005(1)\u2005\u00c5] may further stabilize the crystal structure.The asymmetric unit of the title salt, [Zn(C N,N-di\u00adethyl\u00adnicotinamide (DENA), an important respiratory stimulant , one form of niacin (C6H6ON2)(H2O)3](C8H4O2N), is composed of one complex cation and one 4-cyano\u00adbenzoate (CNB) counter-anion. The ZnII atom is coordinated by one 4-cyano\u00adbenzoate (CNB) anion, one nicotinamide (NA) ligand and three water mol\u00adecules, the CNB anion and NA ligand coordinating in bidentate and monodentate modes, respectively  in the axial positions  around the Zn1 atom show a distorted square-planar arrangement, while the considerably distorted octa\u00adhedral coordination environment of Zns Table\u00a01.9H10NO2)(C6H6N2O)\u00b72H2O] (C6H6N2O)]\u00b7H2O 2(C6H6N2O)] \u2005\u00c5], C1\u2014O2 [1.2591\u2005(19)\u2005\u00c5] and C15\u2014O7 [1.266\u2005(2)\u2005\u00c5], C15\u2014O8 [1.237\u2005(2)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn\u2014O bond lengths are 2.19\u2005(11)\u2005\u00c5 for benzoate oxygen atoms and 2.10\u2005(9)\u2005\u00c5 for water oxygen atoms; the Zn\u2014N bond length is 2.0545\u2005(12)\u2005\u00c5, close to the values in related structures. The Zn1 atom lies 0.0093\u2005(2)\u2005\u00c5 above the planar (O1/O2/C1) carboxyl\u00adate group, with a bite angle of 59.48\u2005(4)\u00b0. Corresponding O\u2014Zn\u2014O angles are 60.03\u2005(6)\u00b0 in [Zn(CA (C2\u2013C7) and C (C16\u2013C21)] are 10.25\u2005(10) and 5.89\u2005(14)\u00b0, respectively, while the benzene rings and benzene and pyridine [B (N2/C9\u201413)] rings are oriented at dihedral angles of A/C = 77.84\u2005(6), A/B = 8.97\u2005(5) and B/C = 71.43\u2005(5)\u00b0.The dihedral angles between the planar carboxyl\u00adate groups [(O1/O2/C1) and (O7/O8/C15)] and the adjacent benzene rings , may further stabilize the structure, with centroid-to-centroid distances of 3.791\u2005(1)\u2005\u00c5 and 3.882\u2005(1)\u2005\u00c5, respectively.In the crystal, N\u2014H\u22efOs Table\u00a02 link the4\u00b77H2O  in H2O (30\u2005ml) and nicotinamide  in H2O (50\u2005ml) with sodium 4-cyano\u00adbenzoate  in H2O (100\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.The title compound was prepared by the reaction of ZnSO2 group) and H41, H42, H51, H52, H61 and H62 (as part of the water mol\u00adecules) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C\u2014H = 0.93\u2005\u00c5, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0310.1107/S2056989015009743/wm5158sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015009743/wm5158Isup2.hklStructure factors: contains datablock(s) I. DOI: 1401948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 2019910.1038/srep20199; published online: 02012016; updated: 04202016.This Article contains typographical errors in in the Methods section.K\u03b1 radiation was used with the X-ray source that was run at 14.5\u2009kV. The energy analyzer operated at a constant pass energy of 50\u2009eV. Since the XPS detectable depth for Fe 2p and Pt 4f electrons are only 5.19\u2009nm and 4.17\u2009nm43, the NiTi(Nb)-SMA/L10-FePt(3\u2009nm)/Ta(5\u2009nm) samples with different elastic strain treatments were designed for the XPS tests.\u201d\u201cMg should read:K\u03b1 radiation was used with the X-ray source that was run at 14.5\u2009kV. The energy analyzer operated at a constant pass energy of 50\u2009eV. Since the XPS detectable depth for Fe 2p and Pt 4f electrons are only 3.9\u2009nm and 3.2\u2009nm43, the NiTi(Nb)-SMA/L10-FePt(3\u2009nm)/Ta(5\u2009nm) samples with different elastic strain treatments were designed for the XPS tests.\u201d\u201cAl"}
{"text": "The supra\u00admolecular inter\u00adactions between cations and anions lead to a two-dimensional network structure parallel to (001).The complex cation of the title salt, (C9H6NO3S)2. In its crystal structure, the complex cation [Cd(TEA)2]2+ and two independent NBTA\u2212 units with essentially similar geometries and conformations are present. In the complex cation, each TEA mol\u00adecule behaves as an N,O,O\u2032,O\u2032\u2032-tetra\u00addentate ligand, giving rise to an eight-coordinate CdII ion with a bicapped trigonal\u2013prismatic configuration. All ethanol groups of each TEA mol\u00adecule form three five-membered chelate rings around the CdII ion. The Cd\u2014O and Cd\u2014N distances are in the ranges 2.392\u2005(2)\u20132.478\u2005(2) and 2.465\u2005(2)\u20132.475\u2005(3)\u2005\u00c5, respectively. O\u2014H\u22efO hydrogen bonds between the TEA hy\u00addroxy groups and carboxyl\u00adate O atoms connect cationic and anionic moieties into chains parallel to [110]. Each NBTA\u2212 anion is additionally linked to a symmetry-related anion through \u03c0\u2013\u03c0 stacking inter\u00adactions between the benzene and thia\u00adzoline rings [minimum centroid-to-centroid separation = 3.604\u2005(2)\u2005\u00c5]. Together with additional C\u2014H\u22efO inter\u00adactions, these establish a double-layer polymeric network parallel to (001).The reaction of 2-acetic acid (NBTA) and tri\u00adethano\u00adlamine (TEA) with Cd(CH The N\u2014Cd\u2014O bond angles range from 68.58\u2005(8) to 122.59\u2005(10)\u00b0 and the O\u2014Cd\u2014O angles are in an inter\u00adval of 72.54\u2005(9) to 162.13\u2005(11)\u00b0. Both thia\u00adzoline rings (C1/C6/N1/C7/S1 and C1A/C6A/N1A/C7A/S1A) and bicyclic benzo\u00adthia\u00adzole units (N1/S1/C1\u2013C7 and (N1A/S1A/C1A\u2013C7A) are close to planar, the largest deviations from the least-squares planes being 0.002\u2005(2), 0.004\u2005(2) and 0.008\u2005(3), 0.005\u2005(3)\u2005\u00c5, respectively. The dihedral angles between the plane of the carboxyl\u00adate group and the attached benzo\u00adthia\u00adzole ring system are 77.895\u2005(3) and 71.408\u2005(3)\u00b0 in the two anions.The structure of the mol\u00adecular entities of (I)\u2212 anions into a chain structure extending parallel to [110], whereby each cation is surrounded by four NBTA\u2212 anions. The H atoms of all hydroxyl groups of the TEA ligands form a hydrogen bond with a carboxyl\u00adate O atom of the NBTA\u2212 ions. In addition, there is weak hydrogen bond between one \u2013CH2 group and the O1 atom of the NBTA anion, with a C\u22efO distance of 3.282\u2005(6)\u00c5  and thia\u00adzoline rings (centroid Cg2) of adjacent inversion-related mol\u00adecules [Cg1\u22efCg2  = 3.604\u2005(2)\u2005\u00c5] \u00c5 Table\u00a01. The abofs Fig.\u00a02. The NBT\u00c5] Fig.\u00a03. Togethes-, d-, p-, and f-block elements have been reported. Structures containing the [Cd(TEA)2]2+ cation are deposited in the CSD with reference codes EYIPAD, MEVQIN and YOVBIU.A survey of the Cambridge Structural Database 2  was slowly added an ethano\u00adlic solution (5\u2005ml) containing TEA (132\u2005\u00b5l) and NBT  under constant stirring. A bright-yellow crystalline product was obtained at room temperature by solvent evaporation after four weeks. Yield: 75%; calculated for C30H42CdN4O12S2: C, 43.56; H, 5.12; N, 6.77, found: C, 43.61; H, 5.15; N, 6.69To an aqueous solution (2.5\u2005ml) of Cd(CHUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016004515/wm5280sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016004515/wm5280Isup2.hklStructure factors: contains datablock(s) I. DOI: 1468939CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd\u2014Cl distances in the range 2.4829\u2005(4)\u20132.6402\u2005(4)\u2005\u00c5. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetra\u00admethyl\u00adguanidinium cations are situated between the polyanionic chains and are linked to them through N\u2014H\u22efCl hydrogen bonds, forming a layered network parallel to (010).In the structure of the title salt, {(C Several cationic complexes of Pd, Ga and Pt have been reported with tetra\u00admethyl\u00adguanidine acting as a ligand  x, y, 1\u00a0\u2212\u00a0z] are in axial positions with a Cl3\u2014Cd1\u2014Cl4i angle of 166.347\u2005(10)\u00b0. The equatorial Cd\u2014Cl bond lengths range from 2.4829\u2005(4)\u2005\u00c5 to 2.5829\u2005(4)\u2005\u00c5 while the axial bond lengths Cd1\u2014Cl3 and Cd1\u2014Cl4i are 2.5854\u2005(4)\u2005\u00c5 and 2.6403\u2005(4)\u2005\u00c5, respectively. The CdCl4 moieties of the asymmetric unit are related by an inversion center, generating an extended zigzag chain of edge-sharing trigonal bipyramids running parallel to [101]. These 1\u221e[CdCl4/2Cl1/1]\u2212 chains are formed by the bridging atoms Cl2, Cl3, Cl4 and Cl4i with a Cd\u2014Cd\u2014Cd angle of 137.893\u2005(6)\u00b0. The corrugation of the chains results in rather short Cd\u22efCd distances of 3.8720\u2005(3) and 3.8026\u2005(3)\u2005\u00c5. The same kind of zigzag chain is found, for example, in the [CdCl3]\u2212 salt obtained with benzyl\u00adtri\u00adethyl\u00adammonium as counter-cation \u00b0 in the structure of the benzyl\u00adtri\u00adethyl\u00adammonium compound compared with 129.859\u2005(2)\u00b0 for the present structure. The tetra\u00admethyl\u00adguanidinium cation has the central atom C1 in an almost trigonal\u2013planar configuration. The three N\u2014C\u2014N angles range from 119.26\u2005(14) to 121.14\u2005(14)\u00b0 and the r.m.s deviation from the least-squares plane calculated with atoms C1, N1, N2 and N3 is only 0.005\u2005\u00c5. The corresponding C\u2014N bond lengths of 1.330\u2005(2), 1.3360\u2005(19), and 1.3441\u2005(19)\u2005\u00c5 indicate a partial double-bond character. Hence the positive charge may be considered as delocalized in the CN3 plane 1\u221e[CdCl4/2Cl1/1]\u2212 chains are inter\u00adconnected through N\u2014H\u22ef\u00b7Cl hydrogen bonds by pairs of tetra\u00admethyl\u00adguanidinium cations linked to symmetry-related Cl1 atoms  = 1.5Ueq(C). H atoms bonded to the N atoms were located from a Fourier difference map and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015020836/wm5207sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020836/wm5207Isup2.hklStructure factors: contains datablock(s) I. DOI: 1434977CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked via pairs of O\u2014H\u22efO hydrogen bonds, involving the boronic acid OH groups, forming inversion dimers. The dimers are linked via O\u2014H\u22efO hydrogen bonds, involving a boronic acid OH group and the carbonyl O atom, forming undulating sheets parallel to (10-2). Within the sheets there are also C\u2014H\u22efO hydrogen bonds present, also involving the carbonyl O atom. The sheets are linked via C\u2014H\u22ef\u03c0 and offset face-to-face \u03c0-inter\u00adactions between inversion-related mol\u00adecules , forming a three-dimensional structure.In the title compound, C The unit cell consists of four mol\u00adecular units which form \u03c0-aggregated pairs in a head-to-tail fashion and are stabilized through offset face-to-face \u03c0-inter\u00adactions ; see Fig.\u00a04A of the boronic acid is in an inversion-related hydrogen-bonded network with the oxygen O2 of the boronic acid at a distance of 2.762\u2005(1)\u2005\u00c5, forming a head-to-head hydrogen-bonded network with adjacent mol\u00adecules (2-methyl\u00adimidazol\u00adyl)boronate monohydrate, tris\u00ad(4-(di\u00admethyl\u00adamino)\u00adpyridinium) bis\u00ad(4-(di\u00admethyl\u00adamino)\u00adpyridine) tris\u00ad(4-carb\u00adoxy\u00adbenzene\u00adboronate) trihydrate and 4-acetyl\u00adpyridine oxime 4-carb\u00adoxy\u00adbenzene\u00adboronate dihydrate which presented out-of-plane tilt angles of ca 10.45\u201327.74\u00b0 and O\u2014B\u2014O bond angles of ca 114.23\u2013124.94\u00b0  bis\u00ad(4-carboxyl\u00adato\u00adphenyl\u00adboronic acid) tetra\u00adhydrate, where M is nickel, manganese or cobalt. These structures where similar to the title compound and exhibited similar characteristics for the O\u2014B\u2014O bond angle and the out-of-plane tilt of the carboxyl acid group compared to the title compound. The carb\u00adoxy\u00adlic group deviated from the plane with an angle of ca 3.40\u20134.53\u00b0 and the O\u2014B\u2014O bond angles were in the range of ca 121.43\u2013122.18\u00b0  4-(di\u00adhydroxy\u00adbor\u00adyl)benzoic acid monohydrate exhibited a tilt angle of ca 2.14\u00b0 for the carb\u00adoxy\u00adlic group and an O\u2014B\u2014O bond angle of ca 126.53\u00b0 . The compound was then crystallized from a solution of 1% MeOH in CH2Cl2 layered with hexane to give a single crystal suitable for X-ray diffraction.The compound was purchased from Alfa Aesar and was purified with silica gel column chromatography using CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Uiso(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015015923/su5188sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989015015923/su5188Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015923/su5188Isup3.cmlSupporting information file. DOI: 1416885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The grid layers are held together by hydrogen bonds between the organic guest mol\u00adecules and the host framework and gives rise to a three-dimensional supra\u00admolecular architecture.{[Fe(H 2Fe(CN)4(H2O)2]\u00b72C12H10N2}n, the asymmetric unit contains one FeII cation, two water mol\u00adecules, two di\u00adcyanido\u00adargentate(I) anions and two uncoordinating 1,2-bis\u00ad(pyridin-2-yl)ethyl\u00adene  mol\u00adecules. Each FeII atom is six-coordinated in a nearly regular octa\u00adhedral geometry by four N atoms from di\u00adcyanido\u00adargentate(I) bridges and two coordinating water mol\u00adecules. The FeII atoms are bridged by di\u00adcyanido\u00adargentate(I) units to give a two-dimensional layer with square-grid spaces. The inter\u00adgrid spaces with inter\u00adlayer distance of 6.550\u2005(2)\u2005\u00c5 are occupied by 2,2\u2032-bpe guest mol\u00adecules which form O\u2014H\u22efN hydrogen bonds to the host layers. This leads to an extended three-dimensional supra\u00admolecular architecture. The structure of the title compound is compared with some related compounds containing di\u00adcyanido\u00adargentate(I) ligands and N-donor organic co-ligands.In the title compound, {[Ag These structural properties lead to potential inter\u00adesting applications in the filed of magnetism, sensing, porous mater\u00adials and catalysis 4(H2O)2]\u00b72C12H10N2}n, (I)One-, two- and three-dimensional frameworks containing di\u00adcyanido\u00adargentate(I) and N-donor linkers such as pyrazine, 4,4\u2032-bpy and 4,4\u2032-bpe  ligands have been studied  ligands, two water mol\u00adecules and two uncoord\u00adinating 2,2\u2032-bpe mol\u00adecules  ligands and two water mol\u00adecules.The asymmetric unit consists of one Fees Fig.\u00a01. Ag1 and\u00c52 Fig.\u00a02. The FeIW\u22efN5 = 2.07\u2005\u00c5 and O2\u2013H4W\u22efN6 = 2.09\u2005\u00c5) , while the other two arrange themselves across the host layer to form also hydrogen bonds (O1\u2014H1W\u22efN7 = 2.14\u2005\u00c5 and O2\u2014H3W\u22efN8 = 2.15\u2005\u00c5)  to the host layers. These hydrogen bonds generate an extended three-dimensional supra\u00admolecular framework.Four independent 2,2\u2032-bpe mol\u00adecules are located between adjacent grid layers of which two are parallel (blue) to the grid layers and two non-parallel (red) Fig.\u00a03. The int\u00c5) Fig.\u00a04a, while\u00c5) Fig.\u00a04b to the4[Ag(CN)2]2]n (imH = imidazole), a one-dimensional chain via bridging di\u00adcyanido\u00adargentate(I) is found, while all imidazole mol\u00adecules act as a terminal ligand 2]2]n (3-Fpy = 3-fluoro\u00adpyridine) consists of four cyanide moieties occupying the equatorial positions generating a square grid-type structure similar to that of the title compound, while the axial positions are occupied by two terminal 3-Fpy ligands instead of two water mol\u00adecules in (I)et al., 20072]2].pz}n (pz = pyrazine), [Mn2[Ag(CN)2]2]n, [Fe2[Ag(CN)2]2]n and [Fe(bpe)2[Ag(CN)2]2]n 2]  was added dropwise to an MeOH\u2013H2O mixed solution  of (NH4)2[Fe(SO4)2]\u00b76H2O  and 2,2\u2032-bpe  at room temperature. After filtration and slow evaporation for 1\u2005d, yellow crystals were obtained.An aqueous solution (5\u2005ml) of K[Ag(CN)isoU(H) = 1.2eqU(C). Water H atoms were located in difference Fourier maps and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S1600536814016250/vn2085sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814016250/vn2085Isup2.hklStructure factors: contains datablock(s) I. DOI: 1013775CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this manuscript the mol\u00adecular and supra\u00admolecular structure of 2\u2032,3,6\u2032-tri\u00adchloro\u00adbiphenyl-2-ylboronic acid tetra\u00adhydro\u00adfuran monosolvate is presented 12H8BCl3O2\u00b7C4H8O, crystallizes as a tetra\u00adhydro\u00adfuran monosolvate. The boronic acid group adopts a syn\u2013anti conformation and is significantly twisted along the carbon\u2013boron bond by 69.2\u2005(1)\u00b0, due to considerable steric hindrance from the 2\u2032,6\u2032-di\u00adchloro\u00adphenyl group that is located ortho to the boronic acid substituent. The phenyl rings of the biphenyl are almost perpendicular to one another, with a dihedral angle of 87.9\u2005(1)\u00b0 between them. In the crystal, adjacent mol\u00adecules are linked via O\u2014H\u22efO inter\u00adactions to form centrosymmetric dimers with R22(8) motifs, which have recently been shown to be energetically very favourable. The hy\u00addroxy groups are in an anti conformation and are also engaged in hydrogen-bonding inter\u00adactions with the O atom of the tetra\u00adhydro\u00adfuran solvent mol\u00adecule. Cl\u22efCl halogen-bonding inter\u00adactions [Cl\u22efCl = 3.464\u2005(1)\u2005\u00c5] link neigbouring dimers into chains running along [010]. Further aggregation occurs due to an additional Cl\u22efCl halogen bond [Cl\u22efCl = 3.387\u2005(1)\u2005\u00c5].The title compound, C In the structure of the related (2-bi\u00adphenyl\u00adyl)boronic acid \u00b0], whereas in (2-bi\u00adphenyl\u00adyl)boronic acid they are rotated by only 48.4 or 45.4\u00b0 for the two unique mol\u00adecules in the asymmetric unit.The B\u2014C [1.5907\u2005(16)\u2005\u00c5] and B\u2014O  bonds in the title compound (I)on Fig.\u00a01. The boranti-oriented OH group is engaged in an inter\u00admolecular O\u2014H\u22efO hydrogen bond \u2005\u00c5; the sum of the van der Waals radii for Cl is 3.50\u2005\u00c5]. In terms of geometry of this contact, it can be classified as a type I halogen bond , \u2005\u00c5] .In the crystal, centrosymmetric O\u2014H\u22efO hydrogen-bonded dimers are formed. The d Table\u00a01 with thend Fig.\u00a02a,  A solution of 2-iodo-2\u2032,3,6\u2032-tri\u00adchloro\u00adbiphenyl  in THF (50\u2005mL) was added to a stirred solution of n-BuLi (10\u2005mmol) in THF (30\u2005mL) at 195\u2005K. The resulting colorless solution was stirred for 1\u2005h to give a colorless precipitate. The electrophile, B(OMe)3  was then added to the stirred mixture to give a colorless solution which was stirred for 1\u2005h and then hydrolyzed with H2O (100\u2005mL). Dilute aq. H2SO4 was added until the pH was slightly acidic. Et2O (50\u2005mL) was next added and the mixture stirred for 10\u2005min. The organic phase was separ\u00adated and the aqueous phase was extracted with Et2O (20\u2005mL). The combined organic solutions were dried over MgSO4 and evaporated to give a colorless precipitate, yield 2.0\u2005g (66%). 1H NMR : \u03b4 = 8.00 , 7.51 , 7.39 , 7.05 ;13C{1H} NMR : \u03b4 = 141.49, 139.62, 139 (br), 136.17, 134.84, 130.49, 129.99, 128.24, 128.14, 127.53.Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a THF solution.Uiso(phenyl H) = 1.2Ueq(C). The positions of the OH hydrogen atoms were first found in a difference map. Then their bond lengths were restrained in the last least-squares cycles, with an O\u2014H distance of 0.85\u2005\u00c5 and their coordinates refined with Uiso(hydroxyl H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901502054X/sj5482sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901502054X/sj5482Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup4.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901502054X/sj5482Isup5.cmlSupporting information file. DOI: 1434205CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Eight O\u2014H\u22efO hydrogen bonds [d(O\u22efH) < 2.00\u2005\u00c5], form a two-dimensional network parallel to the ab plane.In the crystal structure of the title compound, [Fe(dmbpy)(H 12H12N2)(H2O)4]SO4, the central FeII ion is coordinated by two N atoms from the 5,5\u2032-dimethyl-2,2\u2032-bi\u00adpyridine ligand and four water O atoms in a distorted octa\u00adhedral geometry. The Fe\u2014O coordination bond lengths vary from 2.080\u2005(3) to 2.110\u2005(3)\u2005\u00c5, while the two Fe\u2014N coordination bonds have practically identical lengths [2.175\u2005(3) and 2.177\u2005(3)\u2005\u00c5]. The chelating N\u2014Fe\u2014N angle of 75.6\u2005(1)\u00b0 shows the largest deviation from an ideal octa\u00adhedral geometry; the other coordination angles deviate from ideal values by 0.1\u2005(1) to 9.1\u2005(1)\u00b0. O\u2014H\u22efO hydrogen bonding between the four aqua ligands of the cationic complex and four O-atom acceptors of the anion leads to the formation of layers parallel to the ab plane. Neighbouring layers further inter\u00adact by means of C\u2014H\u22efO and \u03c0\u2013\u03c0 inter\u00adactions involving the laterally positioned bi\u00adpyridine rings. The perpen\u00addicular distance between \u03c0\u2013\u03c0 inter\u00adacting rings is 3.365\u2005(2)\u2005\u00c5, with a centroid\u2013centroid distance of 3.702\u2005(3)\u2005\u00c5.In the title compound, [Fe(C The FeII atom is in a distorted octa\u00adhedral coordination environment and the equatorial plane of the octa\u00adhedron is formed by a pair of nitro\u00adgen donors from the 5,5\u2032-dimethyl-2,2\u2032-bipyridyl ligand and two mol\u00adecules of water, while the axial sites are occupied by two other water mol\u00adecules. The equatorial donor atoms are nearly coplanar (r.m.s. deviation = 0.0062\u2005\u00c5), while the deviation of the Fe atom from the least-squares plane is somewhat larger [0.021\u2005(2)\u2005\u00c5]. The bi\u00adpyridine chelating angle N1\u2014Fe\u2014N2 of 75.6\u2005(1)\u00b0 shows the most significant deviation from an ideal octa\u00adhedral geometry. The other angular distortions from an ideal octa\u00adhedral geometry are in the range 0.1\u2005(1) to 9.1\u2005(1)\u00b0. The S\u2014O bond lengths [1.466\u2005(3)\u20131.480\u2005(3)\u2005\u00c5] and O\u2014S\u2014O angles [108.8\u2005(2)\u2013109.9\u2005(2)\u00b0] indicate a nearly ideal tetra\u00adhedral geometry for the anion.A mol\u00adecular view of complex (I)2O)4]2+ cations engages all four coordinating water mol\u00adecules in hydrogen bonding to four [SO4]2\u2212 anions . The anions surrounding the cationic unit are positioned at similar Fe\u22efS distance of 4]2\u2212 anions appears surrounded with four cationic units, where its four O atoms engage as acceptors in bifurcated O\u2014H\u22efO hydrogen bonds towards neighbouring cations . Such a mutual arrangement leads to the formation of a two-dimensional hydrogen-bonded network parallel to the ab plane . Laterally arranged aromatic rings of the 5,5\u2032-dimethyl-2,2\u2032-bi\u00adpyridine ligand in neighbouring layers inter\u00adact by means of weak C\u2014H\u22efO and \u03c0\u2013\u03c0 inter\u00adactions, forming the three-dimensional crystal packing  in water\u2013ethanol . The mixture was transferred to a Teflon-lined autoclave and heated at 410\u2005K for 3\u2005d. The autoclave was then allowed to cool to ambient temperature. Red crystals of (I)The title compound, (I)Uiso(H) values were equal to 1.2 and 1.5 times Ueq of the corresponding C(sp2) and C(sp3) atoms. The H atoms of the four water mol\u00adecules were initially located in a difference Fourier map. During the refinement, these H atoms were allowed to ride on their parent O atoms and also to rotate about the corresponding Fe\u2014O bonds. The Uiso(H) values were set equal to 1.2 times Ueq of the parent O atom. The reflections (100) and (002) were excluded from the refinement because they were nearly completely obscured by the beamstop.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814024982/vn2087sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814024982/vn2087Isup2.hklStructure factors: contains datablock(s) I. DOI: 1034106CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The core is decorated by four tri\u00adphenyl\u00adphosphine ligands bonded to the AgI cations. Ag\u22efAg distances as short as 3.133\u2005(9)\u2005\u00c5 suggest the presence of argentophilic (d10\u22efd10) inter\u00adactions.In the title compound a distorted Ag 6H5)3P]Ag}4{NCO}4], a distorted Ag4N4-heterocubane core is set up by four AgI ions being coordinated by the N atoms of the cyanato anions in a \u03bc3-bridging mode. In addition, a tri\u00adphenyl\u00adphosphine ligand is datively bonded to each of the AgI ions. Intra\u00admolecular Ag\u22efAg distances as short as 3.133\u2005(9)\u2005\u00c5 suggest the presence of argentophilic (d10\u22efd10) inter\u00adactions. Five moderate-to-weak C\u2014H\u22efO hydrogen-bonding inter\u00adactions are observed in the crystal structure, spanning a three-dimensional network. A region of electron density was treated with the SQUEEZE procedure in PLATON  following unsuccessful attempts to model it as being part of disordered tetra\u00adhydro\u00adfuran solvent mol\u00adecules. The given chemical formula and other crystal data do not take into account these solvent mol\u00adecules.In the title compound, [{[(C The characterization of the crystals obtained by X-ray diffraction, NMR and IR spectroscopy is in accordance with the formation of the title compound, [{((C6H5)3P)Ag}4{NCO}4], (I)To get access to a large range of metal allophanates 3 moieties. However, the respective components of both disordered Ag(PPh3) units share one phenyl ring (C41\u2013C46 and C59\u2013C64). The Ag4N4-heterocubane is distorted which is reflected by the variation of the Ag\u2014N distances in the range 2.273\u2005(13)\u20132.605\u2005(12)\u2005\u00c5. Likewise, the Ag\u2014N\u2014Ag [78.7\u2005(3) \u2013 98.5\u2005(3)\u00b0] and N\u2014Ag\u2014N [80.9\u2005(3) \u2013 98.5\u2005(3)\u00b0] angles significantly deviate from 90\u00b0. The Ag2N2-faces of the Ag4N4-core are not planar [r.m.s. deviations in the range 0.0293  to 0.1947\u2005\u00c5 ], however, the opposing least-squares planes are almost parallel [angles between planes: 0.40\u2005(3) and 3.2\u2005(3)\u00b0]. Opposing planes are twisted by some degrees relative to each other, which is reflected by the Ag\u2014N\u2014Ag\u2014N and N\u2014Ag\u2014N\u2014Ag torsion angles ranging from 2.8\u2005(3)\u201319.4\u2005(3)\u00b0. As a result of the distortion of the Ag4N4-core, the Ag\u22efAg and N\u22efN separations differ significantly. The shortest distances are observed between Ag1 and Ag2 as well as Ag3/Ag3\u2032 and Ag4/Ag4\u2032 (Table\u00a01I(PPh3) fragment. The scattering contributions of two severely disordered THF solvent mol\u00adecules were treated with the SQUEEZE procedure in PLATON \u00b70.25THF. This discrepancy may be due to a facile evaporation of the co-crystallized solvent under reduced pressure.The title compound consists of a Agde Fig.\u00a01. Each Ag\u2032 Table\u00a01. Conside\u2032 Table\u00a01 a weak a\u2032 Table\u00a01. The Ag\u2014Five moderate-to-weak C\u2014H\u22efO hydrogen bonds  in the CSD database \u03bc3-\u03baN coordination of the cyanate anions towards AgI has been described for five compounds only  in anhydrous ethanol (40\u2005ml), was added at 273\u2005K ethyl allophanate . The reaction was heated to reflux overnight. The colourless precipitate formed was filtered off, washed thrice with ethanol (each 20\u2005ml) and dried under vacuum (yield: 850\u2005mg). The resulting solid material (407\u2005mg) was dissolved in water (20\u2005ml) and was added dropwise to a solution of silver nitrate  in water (15\u2005ml). The suspension obtained was stirred at ambient temperature overnight. Filtration afforded a colourless solid, which was washed with cold water (20\u2005ml) and dried under vacuum (yield: 250\u2005mg). A suspension of this solid (120\u2005mg) in anhydrous THF (20\u2005ml) was treated with PPh3  at 273\u2005K. After stirring overnight at this temperature, the reaction mixture was filtered through a pad of celite. Removal of all volatiles under reduced pressure afforded a pale purple solid . Colourless crystals of (I)To a solution of sodium ethano\u00adlate in ethanol, generated 1H NMR : \u03b4 = 7.40\u20137.28 . 13C{1H} NMR : \u03b4 = 134.0 , 132.1 , 130.4 , 129.1 . The resonance signal of the cyanate carbon atom is not observed under the measurement conditions applied. 31P{1H} NMR : \u03b4 = 9.0 (s). IR : \u03bd = 3449 (w), 3356 (w), 2170 , 1603 (w), 1429 (w), 1388 (w), 1300 (m), 1206 (m), 638 (m).M.p. 458\u2005K (decomp.). viz. (240), (Uiso(H) = 1.2Ueq(C) and a C\u2014H distance of 0.93\u2005\u00c5. Atoms Ag3 and Ag4 and two of the four P atoms of the PPh3 moieties with attached phenyl rings are disordered over two sets of sites, with occupancy ratios of 0.54\u2005(4):0.46\u2005(4) and 0.55\u2005(2):0.45\u2005(2), respectively. A phenyl ring of another PPh3 moiety is likewise disordered over two sets of sites in a 0.67\u2005(5):0.33\u2005(5) ratio. The disordered phenyl rings were treated by rigid-group refinements. If necessary, the respective C\u2014P distances were restrained to 1.85\u2005(2)\u2005\u00c5. Anisotropic displacement parameters of all atoms were restrained using enhanced rigid-bond restraints  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017636/wm5201Isup2.hklStructure factors: contains datablock(s) I. DOI: 1426238CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Fdd2 space group. Instead, there are two mol\u00adecules in the asymmetric unit, and both of them display a pseudo-trans conformation.The title compound was obtained in crystalline form after preparative HPLC. Conformation of the proposed mol\u00adecular structure was obtained by single-crystal X-ray analysis at 173\u2005K. The mol\u00adecules do not take advantage of the twofold axis provided as an available symmetry option by the  14H16N2S3, crystallized with two independent mol\u00adecules [(1a) and (1b)] in the asymmetric unit. Both mol\u00adecules display a pseudo-trans conformation. The two consecutive S\u2014S bond lengths of the tris\u00adulfane unit of mol\u00adecule (1a) are 2.06\u2005(3) and 2.08\u2005(3)\u2005\u00c5, and 2.08\u2005(3) and 2.07\u2005(2)\u2005\u00c5 for mol\u00adecule (1b). Torsion angles about each of the two S\u2014S bonds are 86.6\u2005(2) and 87.0\u2005(2)\u00b0 for (1a), and \u221284.6\u2005(2) and \u221285.9\u2005(2)\u00b0 for (1b). The core atoms, viz. the N\u2014S\u2014S\u2014S\u2014N moiety, of the two mol\u00adecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti\u00adomers. In mol\u00adecule (1a), the two phenyl rings are inclined to one another by 86.7\u2005(3)\u00b0, and in mol\u00adecule (1b), by 81.1\u2005(3)\u00b0. In the crystal, mol\u00adecules are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming sheets lying parallel to (010).The title compound, C The mol\u00adecules do not take advantage of the twofold axis provided as an available symmetry option by the Fdd2 space group. Instead, there are two mol\u00adecules, (1a) and (1b), in the asymmetric unit . All bond distances and angles in both mol\u00adecules are within expected ranges. Selected geometric parameters for compound (1) are given in Table\u00a011a) are 2.064\u2005(3) and 2.078\u2005(3)\u2005\u00c5, and for mol\u00adecule (1b) are 2.076\u2005(3) and 2.067\u2005(2)\u2005\u00c5. These values are similar to the value of 2.07\u2005\u00c5 reported for the S\u2014S bond length in elemental sulfur (S8). Torsion angles about each of the two S\u2014S bonds (comprising the tris\u00adulfane) are, respectively, 86.6\u2005(2) and 87.0\u2005(2)\u00b0 for (1a), and \u221284.6\u2005(2) and \u221285.9\u2005(2)\u00b0 for (1b). The core atoms, viz. the N\u2014S\u2014S\u2014S\u2014N moiety, of the two units superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti\u00adomers. Moreover, with respect to the four measured torsion angles, which range in absolute value from 84.6\u2005(2) to 87.0\u2005(2)\u00b0, these are slightly smaller than the theoretical optimum of 90.0\u00b0 . The theoretically possible pseudo-cis  conformation , mol\u00adecules are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming sheets lying parallel to (010) \u00adtris\u00adulfane, (2) amino]\u00adtris\u00adulfane, (3) , compounds (2) and (3) each have a unique conformation in the unit cell (Z\u2032 = 1). Selected geometric parameters of (1) and the comparison compounds, (2) and (3), are given in Table\u00a01ca 2.07\u2005\u00c5, the corresponding value is longer (2.09\u2005\u00c5) in (3) and shorter (2.04\u2005\u00c5) in (2). The absolute value of the average torsion angle of the title compound (1) is ca 86.0\u00b0, while the corresponding value is larger (93.2 and \u221289.5\u00b0) and closer to the theoretical optimum in (2), and significantly larger (109.7 and 95.9\u00b0) in (3).A search of the Cambridge Structural Database \u00adtris\u00adulfan, (2) amino]\u00adtris\u00adulfan, (3) , was synthesized and obtained in crystalline form after preparative HPLC, as described by Schroll & Barany (198637) in that publication.The title compound, (rany 1986: compounUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015011342/su5144sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015011342/su5144Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011342/su5144Isup3.cmlSupporting information file. DOI: 1406065CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystals of both compounds, mol\u00adecules are linked  13H8ClN3O6, (I), and C13H9N3O6, (II), differ in the orientation of the two aromatic rings. In (I), they are essentially coplanar, making a dihedral angle of 8.2\u2005(1)\u00b0, while in (II), they are inclined to one another by 76.2\u2005(1)\u00b0. The two nitro groups are essentially coplanar with the attached benzene rings, as indicated by the dihedral angles of 1.4\u2005(2) and 2.3\u2005(2)\u00b0 in (I), and 4.96\u2005(18) and 5.4\u2005(2)\u00b0 in (II). The carbamate group is twisted slightly from the attached benzene ring, with a C\u2014N\u2014C\u2014O torsion angle of \u2212170.17\u2005(15)\u00b0 for (I) and 168.91\u2005(13)\u00b0 for (II). In the crystals of of both compounds, mol\u00adecules are linked via N\u2014H\u22efO hydrogen bonds, forming chains propagating along [010]. In (I), C\u2014H\u22efO hydrogen bonds also link mol\u00adecules within the chains. The crystal packing in (I) also features a very weak \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.7519\u2005(9)\u2005\u00c5].The title compounds, C Within via N\u2014H\u22efO hydrogen bonds, this time involving the carbonyl O atom O5, forming chains propagating along the b axis; see Table\u00a02In the crystal of (II)N-phenyl\u00adcarbamate gave 16 hits for similar compounds, including two ortho\u00adrhom\u00adbic poylmorphs of phenyl N-phenyl\u00adcarbamate itself \u00b0 in (I)A search of the Cambridge Structural Database  dissolved in 100\u2005ml of dry THF, and to it was added the calculated amount (with 5% excess) of 4-chloro\u00adphenyl\u00adchloro\u00adformate for compound (I)Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015010245/su5141sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015010245/su5141Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010245/su5141IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989015010245/su5141Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015010245/su5141IIsup5.cmlSupporting information file. DOI: 1403525, 1403524CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the former, mol\u00adecules are linked  25H29BrN5O7, (I) dioxola-1-benzena\u00adcyclo\u00adnona\u00adphane], and C24H29N5O7S, (II) thia\u00adzola-6-triazola-3-furodioxola-1-benzena\u00adcyclo\u00adnona\u00adphane], the triazole rings adopt almost planar conformations. In (I), the fused pyrrolidine rings adopt envelope conformations with the C atoms opposite the fused N\u2014C bond as the flap in each ring, and their mean planes are inclined to one another by 52.8\u2005(3)\u00b0. In (II), the pyrrolidine and thia\u00adzole rings are both twisted on the fused N\u2014C bond, and their mean planes are inclined to one another by 70.8\u2005(2)\u00b0. In both (I) and (II), the furan ring adopts an envelope conformation with the adjacent C atom of the macrocycle as the flap. In the crystal of (I), mol\u00adecules are linked via C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming sheets parallel to (10-1), while in (II), mol\u00adecules are linked via C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming helical chains propagating along [010], which are linked via C\u2014H\u22efS hydrogen bonds, forming slabs parallel to (001).In the title compounds, C In compound (I)D = N1/C11\u2013C13/C7 and E = N1/C8\u2013C11) and the furan ring (B = O3/C15/C19/C20/C14) have envelope conformations with the maximum deviations from the respective mean planes of 0.465\u2005(5)\u2005\u00c5 for atom C13, 0.490\u2005(7)\u2005\u00c5 for C9 and 0.500\u2005(4)\u2005\u00c5 for C14. The dioxalane ring (C = O4/C15/C19/O5/C16) has a twisted conformation on bond O5\u2014C15. The mean planes of rings B and C are inclined to one another by 70.0\u2005(3)\u00b0, and the mean planes of rings D and E are inclined to one another by 52.8\u2005(3)\u00b0. The molecular structures of compounds (I) and (II) are illustrated in Figs. 1D) and thia\u00adzole rings (E = N1/C8/S9/C10/C11) have twist conformations on bond N1\u2014C11. The furan and dioxolane rings (B and C) adopt envelope conformations with maximum deviations from the mean planes of 0.631\u2005(3)\u2005\u00c5 for atom C14 and 0.319\u2005(4)\u2005\u00c5 for C16. The mean planes of rings B and C are inclined to one another by 68.5\u2005(2)\u00b0 and the mean planes of rings D and E are inclined to one another by 70.8\u2005(2)\u00b0. This latter dihedral angle is much larger than that in compound (I)cf. 52.8\u2005(3)\u00b0.In compound (II)A) makes dihedral angles of 74.0\u2005(3), 65.8\u2005(3) and 65.8\u2005(3)\u00b0 with the mean planes of rings B and D and the benzene ring (C1\u2013C6), respectively. The corresponding dihedral angles in compound (II)A/B and A/D; 74.0\u2005(3) and 65.8\u2005(3), respectively, for (IIn compound (I)via C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming sheets parallel to ; Table\u00a02In the crystal of (I)Compound (I): A solution of 5-bromo-2--2,2-dimethyl-5-[(Z)-2-nitro\u00advin\u00adyl]tetra\u00adhydro\u00adfurodi\u00adoxol-6-yl}\u00adoxy)meth\u00adyl]-1H-1,2,3-triazol-1-yl}eth\u00adoxy)benzalde\u00adhyde (1\u2005mmol) and proline (1.5\u2005mmol) was refluxed in dry aceto\u00adnitrile (50\u2005ml) under a nitro\u00adgen atmosphere for 9\u2005h. After completion of the reaction, as indicated by TLC, the aceto\u00adnitrile was evaporated under reduced pressure. The crude product was purified by column chromatography using hexa\u00adne/EtOAc (3:7) as eluent (yield 75%). After purification the compound was recrystallized in CHCl3 by slow evaporation yielding colourless block-like crystals.Compound (II): A solution of 5-bromo-2--2,2-dimethyl-5-[(Z)-2-nitro\u00advin\u00adyl]tetra\u00adhydro\u00adfurodioxol-6-yl}\u00adoxy)meth\u00adyl]-1H-1,2,3-triazol-1-yl}eth\u00adoxy)benzalde\u00adhyde (1\u2005mmol) and thia\u00adzolidine-4-carb\u00adoxy\u00adlic acid (1.5\u2005m\u2005mol) was refluxed in dry aceto\u00adnitrile (50\u2005ml) under a nitro\u00adgen atmosphere for 9\u2005h. After completion of reaction, as indicated by TLC,the aceto\u00adnitrile was evaporated under reduced pressure. The crude product was purified by column chromatography using hexa\u00adne/EtOAc (4:6) as eluent (yield 75%). After purification the compound was recrystallized in CHCl3 by slow evaporation yielding colourless block-like crystals.Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Compound (I) was refined using the instructions TWIN/BASF  global, I, II. DOI: 10.1107/S205698901501141X/su5103Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901501141X/su5103IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1023614, 1023839CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom is located on an inversion centre and is coordinated by two 4-cyano\u00adbenzoate (CNB) anions, two nicotinamide (NA) ligands and two water mol\u00adecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two N atoms of the NA ligands in the axial positions.In the title complex, the Co 8H4NO2)2(C6H6N2O)2(H2O)2], the CoII atom is located on an inversion centre and is coordinated by two 4-cyano\u00adbenzoate (CNB) anions, two nicotinamide (NA) ligands and two water mol\u00adecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 22.11\u2005(15)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 89.98\u2005(5)\u00b0. In the crystal, inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the mol\u00adecules, enclosing R22(8) and R44(8) ring motifs, forming layers parallel to (100). The layers are linked via C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, resulting in a three-dimensional network. A weak C\u2014H\u22ef\u03c0 inter\u00adaction is also observed.In the title complex, [Co(C N,N-di\u00adethyl\u00adnicotinamide (DENA) is an important respiratory stimulant  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels bis\u00ad(nico\u00adtinamide-\u03baN1)cobalt(II), [Co(C8H4O2N)2(C6H6N2O)2(H2O)2], and report herein its crystal structure.The structure\u2013function\u2013coordination relationships of the aryl\u00adcarboxyl\u00adate ion in ZnII atom is located on an inversion centre and is coordinated by two 4-cyano\u00adbenzoate (CNB) anions, two nicotinamide (NA) ligands and two water mol\u00adecules, with all ligands coordinating in a monodentate manner  and the two symmetry-related water O atoms (O4 and O4i) form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two symmetry-related N atoms (N2 and N2i) of the two NA ligands in the axial positions  \u2005\u00c5] and C1\u2014O2 [1.256\u2005(2)\u2005\u00c5], bond lengths of the carboxyl\u00adate group indicate delocalized bonding arrangements, rather than localized single and double bonds. The Co\u2014O bond lengths are 2.0835\u2005(12)\u2005\u00c5 (for benzoate oxygen atoms) and 2.1350\u2005(13)\u2005\u00c5 (for water oxygen atoms), and the Co\u2014N bond length is 2.1390\u2005(15)\u2005\u00c5, close to standard values. The Co1 atom lies 0.3921\u2005(1)\u2005\u00c5 above the planar (O1/O2/C1) carboxyl\u00adate group. The O\u2014Co\u2014O and O\u2014Co\u2014N bond angles deviate only slightly from ideal values, with average values of 90\u2005(3)\u00b0 and 90\u2005(2)\u00b0, respectively.A (C2\u2013C7)] is 22.11\u2005(15)\u00b0, while the benzene and pyridine [B (N2/C9\u2013C13)] rings are oriented at a dihedral angle of 89.98\u2005(5)\u00b0.The dihedral angle between the planar carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene ring [c (c = carboxyl\u00adate), N\u2014H\u22efOn (n = nicotinamide), O\u2014Hw\u22efOc (w = water) and O\u2014Hw\u22efOn hydrogen bonds  and C\u2014Hn\u22efNcnb hydrogen bonds  in H2O (50\u2005ml) and nicotinamide  in H2O (50\u2005ml) with sodium 4-cyano\u00adbenzoate  in H2O (100\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving pink-coloured single crystals.The title compound was prepared by the reaction of CoSO2) and H41 and H42 (for H2O) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C\u2014H = 0.93\u2005\u00c5, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The highest electron density and the deepest hole were found 0.80\u2005\u00c5 and 0.83\u2005\u00c5, respectively, from Co1.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989015008270/wm5151sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015008270/wm5151Isup2.hklStructure factors: contains datablock(s) I. DOI: 1061935CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III ion in the title compound shows a slightly distorted FeCl2N2O2 octa\u00adhedral coordination geometry. In the crystal, two complex mol\u00adecules are linked by duplex O\u2014H\u22efO hydrogen bonds. Additional hydrogen-bonding inter\u00adactions lead to the formation of undulating sheets parallel to (010).The Fe 10H15N2O2)Cl2]\u00b72H2O, the FeIII ion is coordinated by two N and two O atoms of the tetra\u00addentate 2-{(2-hy\u00addroxy\u00adeth\u00adyl)(pyridin-2-ylmeth\u00adyl)amino}\u00adethano\u00adlate ligand and by two chloride anions, resulting in a distorted octa\u00adhedral coordination sphere. The average Fe\u2014X (X = ligand N and O atoms) and Fe\u2014Cl bond lengths are 2.10 and 2.32\u2005\u00c5, respectively. In the crystal, duplex O\u2014H\u22efO hydrogen bonds between the hydroxyl and eth\u00adoxy groups of two neighbouring complexes give rise to a dimeric unit. The dimers are connected to the lattice water mol\u00adecules  through O\u2014H\u22efCl hydrogen bonds, forming undulating sheets parallel to (010). Weak C\u2014H\u22efCl hydrogen bonds are also observed.In the title compound, [Fe(C The chloride anions are trans to the deprotonated eth\u00adoxy O atom and the N atom of the pyridine group of the Hpmide ligand, respectively, and coordinate in cis position to each other. The average Fe\u2014XHpmide  bond length is 2.10\u2005\u00c5 and the Fe\u2014Cl bond lengths are 2.2773\u2005(5)  and 2.3581\u2005(7)  \u00c5. Both the average Fe\u2014N (2.182\u2005\u00c5) and Fe\u2014O (2.010\u2005\u00c5) distances in (I)2O2-chelated high-spin FeIII complexes The hydroxyl substituent of the Hpmide ligand forms a strong hydrogen bond with the O atom of the deprotonated eth\u00adoxy group of a neighbouring mol\u00adecule. These duplex inter\u00adactions lead to a dinuclear dimeric unit. The dimers are linked through O\u2014H\u22efCl inter\u00adactions to the lattice water mol\u00adecules, that are likewise connected to each other through O\u2014H\u22efO hydrogen bonds. All these hydrogen-bonding inter\u00adactions  was added dropwise a MeOH solution (3\u2005ml) of H2pmide . The colour became yellow, and then the solution was stirred for 30\u2005min at room temperature. Yellow crystals of (I)10H15Cl2FeN2O2: C 37.30, H 4.70, N 8.70%; found: C 37.19, H 4.58, N 8.78%.The HUiso(H) values of 1.2Ueq(C) of the parent atoms. One lattice water mol\u00adecule (OW1) was found to be equally disordered over two positions. The H atoms of this disordered water mol\u00adecule (H1W1 and H1W2) were located from difference Fourier maps and refined with restraints and a fixed O\u2014H distances of 0.84\u2005\u00c5, with Uiso(H) values of 1.2Ueq(O). Moreover, the second water mol\u00adecule (O2W) was modelled without hydrogen atoms because difference Fourier maps did not suggest suitable H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814022089/wm5071sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814022089/wm5071Isup2.hklStructure factors: contains datablock(s) I. DOI: 1027864CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Supra\u00admolecular chains about a 4 10H7N3O4S, the dihedral angle between the terminal five-membered rings is 27.4\u2005(2)\u00b0, with these lying to the same side of the plane through the central CN2C(=O) atoms (r.m.s. deviation = 0.0403\u2005\u00c5), leading to a curved mol\u00adecule. The conformation about the C=N imine bond [1.281\u2005(5)\u2005\u00c5] is E, and the carbonyl O and amide H atoms are anti. In the crystal, N\u2014H\u22efO hydrogen bonds lead to supra\u00admolecular chains, generated by a 41 screw-axis along the c direction. A three-dimensional architecture is consolidated by thienyl-C\u2014H\u22efO(nitro) and furanyl-C\u2014H\u22efO(nitro) inter\u00adactions, as well as \u03c0\u2013\u03c0 inter\u00adactions between the thienyl and furanyl rings [inter-centroid distance = 3.515\u2005(2)\u2005\u00c5]. These, and other, weak inter\u00admolecular inter\u00adactions, e.g. nitro-N\u2014O\u22ef\u03c0(thien\u00adyl), have been investigated by Hirshfeld surface analysis, which confirms the dominance of the conventional N\u2014H\u22efO hydrogen bonding to the overall mol\u00adecular packing.In the title carbohydrazide, C The thienyl ring is also planar within experimental error [r.m.s. deviation = 0.005\u2005\u00c5] and orientated so that the sulfur atom is syn to the carbonyl-O1 atom. Overall, the mol\u00adecule is curved with the rings lying to the same side of the plane through the bridging CN2C(=O) atoms, r.m.s. deviation = 0.0403\u2005\u00c5, with twists noted in both the S1\u2014C1\u2014C5\u2014O1 and N2\u2014C6\u2014C7\u2014O2 torsion angles of \u22129.8\u2005(5) and 5.4\u2005(6)\u00b0, respectively; the dihedral angle between the five-membered rings is 27.4\u2005(2)\u00b0.In (I)anti relationship between the carbonyl-O and amide-H atoms enables the formation of directional N\u2014H\u22efO hydrogen bonds leading to supra\u00admolecular chains, generated by a 41 screw-axis propagating along the c-axis direction, Fig.\u00a02a and Table\u00a01y, x, \u2212z. A view of the unit-cell contents is shown in Fig.\u00a02b.The Crystal Explorer 3.1 Cg = 3.506\u2005(4)\u2005\u00c5, O4\u22efCg = 3.639\u2005(4)\u2005\u00c5 and N3\u2014O4\u22efCg = 74.0\u2005(2)\u00b0] is also evident from the light-blue and red regions corresponding to their respective potentials on the Hirshfeld surface mapped over electrostatic potential in Fig.\u00a04The presence of a short inter\u00admolecular C\u22efC contact between thienyl-C2 and furanyl-C10 atoms, Table\u00a02a and those delineated into O\u22efH/H\u22efO, H\u22efH, N\u22efH/H\u22efN, C\u22efH/H\u22efC, C\u22efC, C\u22efO/O\u22efC and S\u22efH/H\u22efS contacts  distances greater than their van der Waals separations with the comparatively low contribution, i.e. 13.6%, due to the relatively low hydrogen-atom content in the mol\u00adecule. The absence of characteristic wings in the fingerprint plot delineated into C\u22efH/H\u22efC and the low contribution to the Hirshfeld surface, Fig.\u00a06e and Table\u00a03de + di \u223c2.9\u2005\u00c5 belong to short inter\u00adatomic C\u22efH contacts, Table\u00a02de + di \u223c2.7\u2005\u00c5 in the fingerprint plot corresponding to N\u22efH/H\u22efN contacts, Fig.\u00a06e, with a 7.5% contribution to the Hirshfeld surface is the result of short inter\u00adatomic N\u22efH/H\u22efN contacts, Table\u00a02de = di \u223c1.7\u2005\u00c5, Fig.\u00a06f. The presence of \u03c0\u2013\u03c0 stacking inter\u00adactions between the symmetry-related thienyl and furanyl rings is also indicated by the appearance of red and blue triangle pairs on the Hirshfeld surface mapped with the shape-index property identified with arrows in the images of Fig.\u00a07h, they do not have a significant influence on the mol\u00adecular packing as they are separated at distances greater than the sum of their van der Waals radii.The overall two-dimensional fingerprint plot is shown in Fig.\u00a06et al., 2014i.e. 0.99, corresponding to the C\u22efO/O\u22efC contacts. The high propensity to form \u03c0\u2013\u03c0 stacking inter\u00adactions between the thienyl and furanyl rings is reflected from the high enrichment ratio 2.66 for C\u22efC contacts. The ER value of 1.26 resulting from 6.75% of the surface occupied by nitro\u00adgen atoms and a 7.5% contribution to the Hirshfeld surface from N\u22efH/H\u22efN contacts is due to the presence of short N\u22efH contacts in the structure, Table\u00a02The final analysis based on the Hirshfeld surfaces is an evaluation of enrichment ratios (ER) methyl\u00adene]thio\u00adphene-2-carbohydrazide +;  = 1.2Ueq(C). The N-bound H atom was located from a difference map and refined with (N\u2014H = 0.88\u00b10.01\u2005\u00c5), and with Uiso(H) = 1.2Ueq(C). The slightly elongated displacement ellipsoid for the C2 atom in the thienyl ring is likely due to unresolved disorder in the ring where the second, co-planar orientation related by 180\u00b0 to that modelled is present. However, this was not modelled as the maximum residual electron density peak was only 0.46\u2005e\u2005\u00c5\u22123, 0.61\u2005\u00c5 from the C2 atom. It is also noted that the relevant S\u2014C and C\u2014C bond lengths show the expected values.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016009968/hb7593sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016009968/hb7593Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016009968/hb7593Isup3.cmlSupporting information file. DOI: 1486459CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure consists of hydrogen-bonded planar arrays held by X\u2014H\u22efO  and X\u2014O\u22ef\u03c0(ring)  inter\u00adactions, leaving inter\u00adstitial columnar voids.A dinuclear Cd 3-carb\u00adoxy-6-methyl\u00adpyridine-2-carboxyl\u00adate complex is reported, in which the anionic ligand displays an unusual \u03bc 3N,O2:O2;\u03ba3O2:N,O2-bis\u00ad[(nitrato-\u03baO)cadmium] methanol monosolvate, [Cd2(C8H6NO4)2(NO3)2(C10H8N2)2]\u00b7CH3OH, was isolated as colourless crystals from the reaction of Cd(NO3)2\u00b74H2O, 6-methyl\u00adpyridine-2,3-di\u00adcarb\u00adoxy\u00adlic acid (mepydcH2) and 2,2\u2032-bi\u00adpyridine in methanol. The asymmetric unit consists of a CdII cation bound to a \u03bc-\u03ba3N,O2:O2-mepydcH\u2212 anion, an N,N\u2032-bidentate 2,2\u2032-bi\u00adpyridine group and an O-mono\u00addentate nitrate anion, and is completed with a methanol solvent mol\u00adecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH\u2212 carboxyl\u00adate O atom to complete the dinuclear complex mol\u00adecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octa\u00adhedral coordination geometry about the CdII atom, the Cd\u2014O and Cd\u2014N distances in this complex are surprisingly similar. The crystal structure consists of O\u2014H\u22efO hydrogen-bonded chains parallel to a, further bound by C\u2014H\u22efO contacts along b to form planar two-dimensional arrays parallel to (001). The juxtaposed planes form inter\u00adstitial columnar voids that are filled by the methanol solvent mol\u00adecules. These in turn inter\u00adact with the complex mol\u00adecules to further stabilize the structure. A search in the literature showed that complexes with the mepydcH\u2212 ligand are rare and complexes reported previously with this ligand do not adopt the \u03bc-\u03ba3 coordination mode found in the title compound.The centrosymmetric dinuclear complex bis\u00ad(\u03bc-3-carb\u00adoxy-6-methyl\u00adpyridine-2-carboxyl\u00adato)-\u03ba The two deprotonated forms pydcH\u2212 and 2\u2212pydc have been shown to adopt a wide range of coordination modes through their carboxyl\u00adate oxygen and pyridyl nitro\u00adgen atoms , only a single structure was found involving the monoanionic mepydcH\u2212 ligand similar to that reported here  complexes [M(bpee)2(mepydcH)2] ethyl\u00adene) with octa\u00adhedral geometry around MII. Both mepydcH\u2212 fragments act in a simple \u03ba22N,O-chelating mode binding to a single nucleus while the two N-bound bpee ligands are trans-monodentate. The formation of these mononuclear complexes is unusual considering the obvious bridging potential of the bpee ligands. Mixed-ligand complexes based on non-methyl\u00adated 2,3-pyridinedi\u00adcarboxyl\u00adate and 4,4\u2032-bi\u00adpyridine-like ligands usually generate stable polymeric structures with the exo-bidentate ligands adopting a bridging role 2(mepydcH)2(NO3)2]\u00b7MeOH (I)2- coordination behaviour and the fact that the ligand is only singly deprotonated has no counterpart in complexes of the non-methyl\u00adated ligands and makes this a genuinely novel structure. The closest relatives with 2,2\u2032-bi\u00adpyridine as the auxiliary ligand are found with di-anionic 2\u2212pydc ligands, but these are either mononuclear  chelates through the pyridine N and carboxyl\u00adate O atoms. A chelating 2,2\u2032-bi\u00adpyridine that binds through both nitro\u00adgen atoms and a unidentate nitrate anion complete the coordination sphere; the asymmetric unit also contains a non-coordinating half-occupancy methanol solvate. This five coordinate CdII unit, in turn, binds to its centrosymmetric image through the carboxyl\u00adate oxygen atom of the mepydcH\u2212 ligand, forming a pair of Cd\u2013O\u2013Cd bridges. As a result, a dimeric unit forms  distances are reasonable, spanning the range 2.304\u2005(2)\u20132.332\u2005(3)\u2005\u00c5. However, the coordination angles vary widely ; the result is a rather distorted octa\u00adhedral geometry around Cd1. Selected geometric parameters are shown in Table\u00a01The complex consists of a Cdms Fig.\u00a01 with eacviz., hydrogen bonds  Contacts #1  when a lone pair provided by a carbonyl oxygen points toward the centroid of an aromatic ring  Strong inter\u00admolecular O\u2014H\u22efO contacts #2  C\u2014H\u22efO inter\u00adactions #3, #4 and #5  . These planes juxtapose along [001] with rather weak direct inter\u00adactions. In the process, however, significant columnar voids parallel to the chains are formed  in which the partial occupancy methanol solvate mol\u00adecules reside. These are not free, but enter instead into a number of weak C\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22ef\u03c0 interactions  Fig.\u00a03a. ThesemepydcH2, 2.2\u2032-bi\u00adpyridine and (I)Resolutions Pro software, using a Diamond ATR accessory. The FT\u2013IR spectrum of (I)\u22121 range, and confirms the structural data indicating the presence of the coordinating nitrate and mepydcH\u2212 anions. Bands due to the unidentate NO3\u2212 group were found at 1478 and 1298\u2005cm\u22121 and appear due to the \u03bdasym(ONO) and \u03bdsym(ONO) vibrations, with a shoulder at 1010\u2005cm\u22121 due to the \u03bd(NO) stretching modes of nitrate groups \u22121, \u03bd(OH) stretching for a hydrogen-bonded system  stretch. The deprotonated carboxyl\u00adate (COO\u2212) is characterized by the asymmetric and symmetric stretching modes \u03bdas at 1593\u2005cm\u22121 and \u03bds at 1322\u2005cm\u22121. This confirms the unidentate coordination of the carboxyl\u00adate O atom, with the difference between these frequencies being > 200\u2005cm\u22121(\u0394 = \u03bdas \u2212 \u03bds = 271\u2005cm\u22121)  of almost equal intensity due to the \u03bd(C=C) + \u03bd(C=N) vibrations from the coordinating 2,2\u2032-bi\u00adpyridine ligand \u00b74H2O  and mepydcH2  in MeOH (4.0\u2005mL). The mixture was stirred to dissolve the 2,2\u2032-bi\u00adpyridine and was then allowed to stand undisturbed at room temperature in an uncovered 10\u2005mL beaker. Colourless single crystals of compound (I)Solid 2,2\u2032-bi\u00adpyridine  was added to a solution prepared by disolving Cd = 1.2Ueq(C); C\u2014Hmeth\u00adyl: 0.97\u2005\u00c5, Ueq(H) = 1.5Ueq(C). The O\u2014H hydrogen atom was refined with a restrained O\u2014H distance [0.85\u2005(1)\u00c5], and with U(H) = 1.2Ueq(O). The methanol solvate was refined at half occupancy.Relevant crystallographic data for (I)10.1107/S2056989015012384/sj5468sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015012384/sj5468Isup2.hklStructure factors: contains datablock(s) I. DOI: 1409269CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is an example of a \u2018false conglomerate\u2019 with two mol\u00adecules of opposite handedness in the asymmetric unit. Each mol\u00adecule exists as a zwitterion, with proton transfer from the amino acid carb\u00adoxy\u00adlic acid group to the amine group. In the crystal, the components are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, generating (100) sheets. 6H9NO4\u00b7H2O [systematic name: -rel-\u03b1-amino-2-carb\u00adoxy\u00adcyclo\u00adpropane\u00adacetic acid monohydrate], crystallizes with two organic mol\u00adecules and two water mol\u00adecules in the asymmetric unit. The space group is P21 and the organic mol\u00adecules are enanti\u00adomers, thus this is an example of a \u2018false conglomerate\u2019 with two mol\u00adecules of opposite handedness in the asymmetric unit (r.m.s. overlay fit = 0.056\u2005\u00c5 for one mol\u00adecule and its inverted partner). Each mol\u00adecule exists as a zwitterion, with proton transfer from the amino acid carb\u00adoxy\u00adlic acid group to the amine group. In the crystal, the components are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, generating (100) sheets. Conformationally restricted glutamate analogs are of inter\u00adest due to their selective activation of different glutamate receptors, and the naturally occurring (+)-CCG-III is an inhibitor of glutamate uptake and the key geometrical parameters are discussed.The title compound, C CCG-I, CCG-III and CCG-IV glycines IV Fig.\u00a01 are natuII Fig.\u00a01 have beeThe racemic title compound Fig.\u00a02 crystallX = \u22124.3\u00b0 and O3A\u2014C6A\u2014C2A\u2014X = \u221211.1\u00b0  indicate that the carb\u00adoxy\u00adlic acid attached to the cyclpropane ring adopts a bis\u00adected conform\u00adation ; C2A\u2014C3A = 1.516\u2005(2)\u2005\u00c5] and are longer than the cyclo\u00adpropane bonds distal to the C2 carb\u00adoxy\u00adlic acid . These distances and torsion angles are consistent with other cyclo\u00adpropane carb\u00adoxy\u00adlic acids , between the \u03b1- and \u03b3-carboxyl\u00adate carbon atoms (2d), and their sum (1d + 2d). The classifications \u2018folded\u2019, \u2018semi-folded\u2019, \u2018semi-extended\u2019, and \u2018extended\u2019 are defined by (1d + d2) \u2264 7.5\u2005\u00c5, 7.5\u2005\u00c5 \u2264 (1d + d2) \u2264 8.0\u2005\u00c5, 8.0\u2005\u00c5 \u2264 (1d + d2) \u2264 8.5\u2005\u00c5, and (1d + d2) \u2265 8.5\u2005\u00c5, respectively , 8.24 and 8.30\u2005\u00c5, respectively. From these values, these conformers of CCG-III can be considered to be in the \u2018semi-extended\u2019 class.Conformationally restricted glutamic acid analogs can be classified into one of four categories, which are characterized by the distances between the nitro\u00adgen atom of the amino group and the \u03b3-carboxyl\u00adate carbon atom ; Table\u00a01The racemic title compound was prepared according to the literature procedure  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011500/hb7407Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011500/hb7407Isup3.cmlSupporting information file. DOI: 1406594CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III irida\u00adbenzenes that contain an open coordination site.Treatment of an irida\u00adbenzene with either bromine or iodine generates high-oxidation-state Ir 3)2], with either bromine or iodine produced di\u00adbromido\u00ad(tri\u00adphenyl\u00adphosphine)iridium(III), [IrBr2{\u2014C(Ph)=C(Ph)\u2014CH=CH\u2014CH=}(PPh3)], (I), and di\u00adiodido\u00ad(tri\u00adphenyl\u00adphosphane)iridium(III), [IrI2{\u2014C(Ph)=C(Ph)\u2014CH=CH\u2014CH=}(PPh3)], (II), respectively, which are two rare examples of 16-electron metalla\u00adbenzenes. Structural elucidation of (I) and (II) reveals that these isotypic irida\u00adbenzenes are unusual, not only in their electron count, but also in their coordination sphere of the IrIII atom where they contain an apparent open coordination site. The crystal structures of (I) and (II) confirm that the mol\u00adecules are complexes containing five-coordinated IrIII with only one tri\u00adphenyl\u00adphosphine group bound to the iridium atom, unambiguously proving that the mol\u00adecules are indeed 16-electron, high-oxidation-state irida\u00adbenzenes. The coordination geometry of the IrIII atom in both structures can be best described as a distorted square pyramid with the P, two Br (or I) and one C atom in the basal plane and another C atom in the apical position.Treatment of carbon\u00adylbis\u00ad(tri\u00adphenyl\u00adphosphane)iridium, [IrCO(\u2014C(Ph)=C(Ph)\u2014CH=CH\u2014CH=)(PPh The mol\u00adecular structures of (I)III is five-coordinated in these complexes with only one tri\u00adphenyl\u00adphosphine group bound to the iridium atom, unambiguously proving that the mol\u00adecules are indeed 16-electron, high-oxidation-state irida\u00adbenzenes. The coordination geometry of the IrIII atom in both structures can be best described as a distorted square pyramid with the P1, Br1(I1), Br2(I2) and C1 atoms in the basal plane and the C5 atom in the apical position. The Br1(I1), Br2(I2), P1, C1 fragments are planar within 0.17\u2005\u00c5 (Br) and 0.21\u2005\u00c5 (I)I irida\u00adbenzenes (2.01\u20132.05\u2005\u00c5), reflecting the higher IrIII oxidation state et al., 2007cf, Br1(I1)\u2014Ir\u2014C5, 110.5\u2005(2) [113.6\u2005(4)\u00b0]}. This site is typically occupied by CO in all of our previous irida\u00adbenzene studies, such as (III)  in (I)ca 3.18\u2005\u00c5. This H29A atom is on the opposite side from the C5 atom (the C5\u2014Ir1\u22efH29A angle is 147\u00b0). If present, the Ir\u2014H distance would be around 1.5\u20131.6\u2005\u00c5. In such a case, the distance between this H atom and the H29A atom from the phenyl ring should be 1.6\u20131.7\u2005\u00c5. This distance is too short as a typical H\u22efH contact is 2.4\u2005\u00c5. It follows then that if one H atom does not fit, H2 will not either. The displacement parameters of most C atoms in the phenyl rings are elongated perpendicular to the average plane of the Ph rings showing their flexibility or statistical disorder.Additionally, the irida\u00adbenzene ring in both structures significantly deviates from planarity (Zhu I) Fig.\u00a03. The steX  inter\u00adactions with C\u22efX distances in the ranges of 3.533\u2005(7)\u2013 3.717\u2005(5) and 3.699\u2005(17)\u20133.707\u2005(12)\u2005\u00c5, respectively, for Br and I (Tables 1Compounds (I) Tables 1 and 2 \u25b8.et al., 1999Reaction of irida\u00adbenzene (Gilbertson Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015018952/wm5215sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989015018952/wm5215Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018952/wm5215IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1430096, 1430095CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III(C48H36N4O2)(H2O)2][K(C12H24O6)(H2O)2](SO3CF3)2\u00b72C12H24O6, the FeIII atom is situated on an inversion centre and is octa\u00adhedrally coordin\u00adated by four pyrrole N atoms of the deprotenated 5,10,15,20-tetra\u00adkis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)porphyrinate ligand and two water mol\u00adecules. The average equatorial Fe\u2014N(pyrrole) bond length [2.043\u2005(6)\u2005\u00c5] is consistent with a high-spin (S = 5/2) iron(III) metalloporphyrin derivative. The K+ cation, which also lies on an inversion centre, is chelated by the six O atoms of one 18-crown-6 mol\u00adecule and is additionally coordinated by two water mol\u00adecules in a distorted hexa\u00adgonal\u2013bipyramidal geometry. In the crystal, the cations, anions and one non-coordinating 18-crown-6 mol\u00adecule are linked by classical O\u2014H\u22efO hydrogen bonds and non-conventional C\u2014H\u22efO hydrogen bonds, leading to a one-dimensional supra\u00admolecular architecture along [10-1]. The crystal packing is further stabilized by weak C\u2014H\u22ef\u03c0 inter\u00adactions involving pyrrole and phenyl rings of the porphyrins, as well as weak C\u2014H\u22efF contacts involving the (SO3CF3)\u2212 counter-ion and the 18-crown-6 mol\u00adecules.In the title compound, [Fe DOI: 10.1107/S2056989015021039/im2471Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021039/im2471fig1.tifORTEP III 2 2 + 2 2 + 3 3 \u2212 x y z . DOI: ORTEP view of the [FeIII(TMPP)(H2O)2]+ and [K(18-crown-6)(H2O)2]+ cations, the (SO3CF3)\u2212 anion and the 18-crown-6 mol\u00adecule. Displacement ellipsoids are drawn at 50% probability level. H atoms have been omitted for clarity. .An Click here for additional data file.10.1107/S2056989015021039/im2471fig2.tifb Cg . DOI: b axis. The O\u2014H\u22efO classic H bonds are drawn as dashed light blue lines, the C\u2014H\u22efO contacts as dashed dark red lines while the C\u2014H\u22efCg inter\u00admolecular inter\u00adactions are shown as dashed green lines.A drawing showing the one-dimensional supra\u00admolecular structure of the title compound viewed down the 976053CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two novel G3P[4] rotavirus strains were detected from children with acute diarrhea in Sendai, Japan, identified as a G3\u2013P[4]\u2013I2\u2013R2\u2013C2\u2013M2\u2013A2\u2013N2\u2013T2\u2013E2\u2013H2 genotype constellation by whole-genome sequence analysis. The VP7 gene of the two strains displayed the highest nucleotide sequence identity (91\u00a0%) and showed a close genetic relationship  to an equine rotavirus reported in India. The other gene segments were related to human group A rotaviruses. This report suggests a possible reassortment event between human and equine rotaviruses.The online version of this article (doi:10.1007/s11262-014-1135-z) contains supplementary material, which is available to authorized users. Rotaviruses are a leading cause of acute diarrhea in young children and cause approximately 453,000 deaths per year worldwide . In JapaReoviridae, genus Rotavirus. Its double-stranded RNA genome consists of 11 gene segments that encode six structural viral proteins  and six non-structural proteins (NSP1\u20136). The genes of the two antigenically distinct outer capsid proteins, VP7 (G type) and VP4 (P type), are used for genotyping [x\u2013P[x]\u2013Ix\u2013Rx\u2013Cx\u2013Mx\u2013Ax\u2013Nx\u2013Tx\u2013Ex\u2013Hx (where \u201cx\u201d depicts the number of the genotype) for symbolizing the VP7\u2013VP4\u2013VP6\u2013VP1\u2013VP2\u2013VP3\u2013NSP1\u2013NSP2\u2013NSP3\u2013NSP4\u2013NSP5 genes  followed by G3P[8], G9P[8], and G2P[4] . Rotavir\u00b0C for 5\u00a0min, and cooled on ice. Then 2\u00a0\u03bcl of 5\u00d7\u00a0first strand buffer (F.C: 1\u00d7), 0.5\u00a0\u03bcl of 0.1\u00a0M DTT (F.C: 5\u00a0mM), 0.25\u00a0\u03bcl of 40U/\u03bcl RNaseOUT (F.C: 1U/\u03bcl), and 0.25\u00a0\u03bcl of 200\u00a0U/\u03bcl superscript III RT (F.C: 5\u00a0U/\u03bcl) were added into the mixture. The reverse transcription step was carried out at 25\u00a0\u00b0C for 10\u00a0min, 50\u00a0\u00b0C for 50\u00a0min, followed by heating at 70\u00a0\u00b0C for 15\u00a0min to inactivate the enzyme, and cooling at 4\u00a0\u00b0C immediately. For screening of RVA, real-time PCR was performed , and 0.5\u00a0\u03bcl of 300\u00a0ng/\u03bcl random hexamer primers  (F.C: 15\u00a0ng/\u03bcl) and 0.5\u00a0\u03bcl of 10\u00a0mM dNTP (F.C: 0.5\u00a0mM), heated at 98\u00a0erformed  and for erformed . Nucleothttp://rotac.regatools.be/)  . Interestingly, two samples were of the G3P[4] genotype. One of the samples (S13\u201330) was collected from a 4-year-old boy in the last week of February 2013 and the other (S13\u201345) was collected from a 1-year-old infant girl in the middle of March 2013. Both children did not receive rotavirus vaccines.In Table\u00a0Phylogenetic trees of all 11 segments were constructed based on complete nucleotide sequences of each gene  Below is the link to the electronic supplementary material."}
{"text": "Acridine\u2013acridine stacking, thio\u00adphene\u2013thio\u00adphene stacking and acridine\u2013thio\u00adphene C\u2014H\u22ef\u03c0 inter\u00adactions also occur in the crystal.In the title co-crystal, C The inter\u00adnal angle at N1 [C6\u2014N1\u2014C18 = 119.30\u2005(15)\u00b0] and bond lengths [C18\u2014N1 = 1.346\u2005(2) and C6\u2014N1 = 1.354\u2005(2)\u2005\u00c5] agree with those reported for neutral acridine structures , Cg1\u22efCg1ii = 3.7526\u2005(9), Cg1\u22efCg2ii = 3.7293\u2005(12), Cg2\u22efCg3i = 3.6748\u2005(12) and Cg2\u22efCg3ii = 3.7298\u2005(12)\u2005\u00c5 where Cg1 is the centroid of the N1/C6/C11/C12/C13/C18 ring, Cg2 is the centroid of the C6\u2013C11 ring and Cg3 is the centroid of the C13\u2013C18 ring; symmetry codes: (i) \u2212x, 2\u00a0\u2212\u00a0y,1\u00a0\u2212\u00a0z; (ii) 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y,1\u00a0\u2212\u00a0z] and between the thio\u00adphene rings . The crystal structure also features C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular architecture (Table\u00a01The 3TPC and acridine moieties are linked by an O\u2014H\u22efN hydrogen-bonding inter\u00adaction between (O1\u2014H1) of the carboxyl group and the acridine nitro\u00adgen atom (N1) Table\u00a01. This O\u2014e Table\u00a01.et al., 2001aet al., 2014et al., 2011et al., 2001bet al., 2011The crystal structures of a number of acridine co-crystals, acridinium salts and their metal complexes have been investigated in a variety of crystalline environments such as diphenic acid\u2013acridine (1:1) (Shaameri 1) were obtained.To 10\u2005ml of a hot methanol solution of 3TPC  were added 10\u2005ml of a hot methano\u00adlic solution of acridine . The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week yellow plate-like crystals of (Uiso(H) = kUeq, where k = 1.5 for hy\u00addroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016005685/hg5473sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005685/hg5473Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016005685/hg5473Isup3.cmlSupporting information file. DOI: 1472507CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure is formed by an alternating packing of organic and inorganic layers along [001] and contains isolated (Bi2Cl10)4\u2212 bi\u00adocta\u00adhedra.The title salt, (C 6H14N2)2[Bi2Cl10]\u00b72H2O, was ob\u00adtain\u00aded by slow evaporation at room temperature of a hydro\u00adchloric aqueous solution (pH = 1) containing bis\u00admuth(III) nitrate and 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi2Cl10]4\u2212 bi\u00adocta\u00adhedra (site symmetry -1) separated by layers of organic 1,4-diazo\u00adniabi\u00adcyclo\u00ad[2.2.2]octane dications [(DABCOH2)2+] and water mol\u00adecules. O\u2014H\u22efCl, N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds lead to additional cohesion of the structure.The title compound bis\u00ad di-\u03bc-chlorido-bis\u00ad[tetra\u00adchlorido\u00adbis\u00admuthate(III)] dihydrate, (C These components are linked by strong hydrogen bonds. The inorganic moiety is an edge-sharing di\u00adocta\u00adhedron located site with symmetry 2)2+ dications  to 176.64\u2005(15)\u00b0 for the trans arrangement. Using Shannon\u2019s method 2[Bi2Cl10]\u00b72H2O structure is very close to that of (C6H14N2)2[Sb2Cl10]\u00b72H2O  in the Pnnm anti\u00admony unit cell to be comparable to the bis\u00admuth one  \u00d7 10\u22123] . It is worth noting that the water mol\u00adecule plays a more efficient role in the bis\u00admuth based compound. In (C6H14N2)2[Sb2Cl10]\u00b72H2O, the H2O mol\u00adecules are only linked to (DABCOH2)2+ and in the (C6H14N2)2[Bi2Cl10]\u00b72H2O structure they are directly hydrogen bonded to both the organic and inorganic parts \u2005\u00c5] because the metallic coordination polyhedra are aligned along this axis. On the other hand, a roughly equivalent decrease of the b parameter is observed causing the unit-cell volume of the two compounds approximately to be the same. A general comparison of the two structures reveals that they have a similar 3D pattern, built up by isolated bi\u00adocta\u00adhedra, (DABCOH2)2+ cations and water mol\u00adecules leaving empty the same voids. On the other hand, the water mol\u00adecule immediate environment is more regular in the Sb structure  and the (DABCOH2)2+ cation is more distorted in the Bi structure  explaining the lowering of the symmetry in the title compound.The  x, \u2212y\u00a0+\u00a00.5, z\u00a0+\u00a00.5] and O\u2014HW2\u22efCl5 inter\u00adactions. The DABCO cations are hydrogen bonded to water mol\u00adecules, leading to chains composed of organic moieties, inorganic clusters and H2O mol\u00adecules running along the b direction 2[Bi2Cl10]\u00b72H2O crystals were obtained at ambient conditions by dissolving Bi(NO3)3\u00b75H2O and DABCO (C6H12N2) in water in a 1:2 molar ratio. The pH of the solution was adjusted to 1 with HCl. The mixture was stirred and kept for several days. Colourless crystals were obtained after a few weeks. I. DOI: 10.1107/S2056989015019933/vn2102Isup2.hklStructure factors: contains datablock(s) I. DOI: 971956CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "B-Spline curves. Since modal intervals are used in many fields, we introduce a new sequence space h(gI) called the Hahn sequence space of modal intervals. We have given some new definitions and theorems. Some inclusion relation and some topological properties of this space are investigated. Also dual spaces of this space are computed.The history of modal intervals goes back to the very first publications on the topic of interval calculus. The modal interval analysis is used in Computer graphics and Computer Aided Design (CAD), namely, the computation of narrow bounds on Bezier and  Goes and S. Goes \u03b2\u03b2.(ii)E(gI)]\u03b2\u03b2\u03b2 = [E(gI)]\u03b2.[(iii)E1(gI)\u2283E(gI) then [E1(gI)]\u03b2 \u2282 [E(gI)]\u03b2.If Let The same results hold for dual also.Let (i) Suppose E(gI). Hence E(gI)\u2282[E(gI)]\u03b2\u03b2. The proof for (ii) follows similarly.This means that E1(gI)\u2283E(gI), E1(gI)]\u03b2 \u2282 [E(gI)]\u03b2.(iii) Suppose B-transform of a sequence Define the sequence l\u221e(gI) is the set of all sequences such that the B-transforms of them are in l\u221e(gI). That is, That is, \u03c3(l\u221e(gI)) is a complete metric space with the metric \u03c3(l\u221e(gI)).\u03c3(l\u221e(gI)) where \u03b5 > 0, there exists a positive integer n0(\u03b5) such that k \u2208 N from  that i \u2265 n0(\u03b5), taking limit j \u2192 \u221e first and letting m \u2192 \u221e in (\u03c3(l\u221e(gI)), we have Consider the sequence ave from  for eachm \u2192 \u221e in , we obtaNow, \u03c3(l\u221e(gI)) is complete.Since \u03b2-dual and \u03b3-dual of h(gI) are \u03c3(l\u221e(gI)).The \u03b5 > 0, there exists n0 such that Let k and n.Since M > 0 such that k and n.Hence there exists an M-test.Now, k \u2208 N.Thus h(gI)]\u03b2 = \u03c3(l\u221e(gI)). This completes the proof.Hence gI. From  and 31)(31)v~k\u2208\u03c3Considerh(gI) \u2282 l1(gI)\u2229\u222bc0(gI).(i) h(gI) = l1(gI)\u2229\u222bbv(gI) = l1(gI)\u2229\u222bbv0(gI).(ii) (i) Let Consider And also since h(gI) \u2282 l1(gI)\u2229\u222bc0(gI).Therefore, k = 1,2,\u2026, (ii) For h(gI) \u2282 l1(gI). Hence also h(gI) \u2282 \u222bbv(gI).The last series is convergent since Hence versely,  implies h(gI) = l1(gI)\u2229\u222bbv(gI).Therefore, nce from  and 36)(36)l1gI\u2229Similarly, we can prove other equalities."}
{"text": "II atom coordinated by two Cl atoms and two dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate ligands bonded through the terminal N atom in a distorted tetra\u00adhedral manner. The complex mol\u00adecules inter\u00adact through C\u2014H\u22efCl and Cl\u22efS inter\u00adactions to give a layered structure in the crystal.The title complex consists of a Zn II atom in the title complex, [ZnCl2(C4H6N2S2)2], is coordinated in a distorted tetra\u00adhedral manner by two Cl atoms and two terminal N atoms of two dimethyl N-cyano\u00addithio\u00adimino\u00adcarbonate ligands. In the crystal, the complex mol\u00adecules are connected through C\u2014H\u22efCl hydrogen bonds and Cl\u22efS contacts, leading to a two-dimensional structure extending parallel to the ab plane.The Zn N-cyano\u00addithio\u00adimino\u00adcarbonate (DMCDIC), which are expected to act as hard and soft donors, respectively, according to Pearson\u2019s concept, give an inter\u00adesting coordination potential to this mol\u00adecule. However, only one structure of a metal complex with DMCDIC acting as a ligand has been reported 2] ; \u03c44 = [360 - (\u03b1 + \u03b2)]/141, where \u03b1 and \u03b2 are the two largest tetra\u00adhedral angles.The structure of the title compound Fig.\u00a01 is isotyB\u22efCl1ii and C7\u2014H7B\u22efCl1ii; Table\u00a01B\u22efCl2i hydrogen bond (Table\u00a01i short contact [3.3812\u2005(7)\u2005\u00c5], giving infinite chains along , leading to a layer parallel to the ab plane .All chemicals are purchased from Aldrich Company, Germany and used as received. Dimethyl cyano\u00adcarbonimidodi\u00adthio\u00adate was mixed in aceto\u00adnitrile with ZnCl2CNCN)2Cl2]  = 1.5Ueq(C), and were allowed to rotate to minimize their contribution to the electron density.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016002607/is5443sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016002607/is5443Isup2.hklStructure factors: contains datablock(s) I. DOI: 1453191CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound, an aryl\u00adsulfonyl glycinyl aryl hydrazone Schiff base, crystallizes with two independent mol\u00adecules in the asymmetric unit. In the crystal, a series of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 and slipped parallel \u03c0\u2013\u03c0 inter\u00adactions link the mol\u00adecules, forming a three-dimensional structure. 17H19N3O3S, containing an amino acid moiety and electron-donating substituents attached to both the phenyl rings, crystallized with two independent mol\u00adecules (A and B) in the asymmetric unit. The mol\u00adecules are bent at the S atom, with C\u2014SO2\u2014NH\u2014CH2 torsion angles of \u221267.3\u2005(2) and 67.7\u2005(3)\u00b0 in mol\u00adecules A and B, respectively. Further, the dihedral angles between the sulfonyl\u00adglycine segments and the p-toluene\u00adsulfonyl rings are 76.1\u2005(1) and 85.8\u2005(1)\u00b0 in mol\u00adecules A and B, respectively. The central hydrazone segments and the toluene rings attached to them are almost co-planar with their mean planes being inclined to one another by 5.2\u2005(2) (mol\u00adecule A) and 2.9\u2005(2)\u00b0 (mol\u00adecule B). The dihedral angles between the benzene rings are 86.83\u2005(12) (mol\u00adecule A) and 74.00\u2005(14)\u00b0 (mol\u00adecule B). In the crystal, the A mol\u00adecules are linked by a pair of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked via three N\u2014H\u22efO hydrogen bonds involving the B mol\u00adecules, forming chains along [100] and enclosing R22(12) and R44(16) ring motifs. The chains are linked via C\u2014H\u22efO hydrogen bonds and a C\u2014H\u22ef\u03c0 inter\u00adaction, forming sheets parallel to (010). There is a further C\u2014H\u22ef\u03c0 inter\u00adaction and a slipped parallel \u03c0\u2013\u03c0 inter\u00adaction [inter-centroid distance = 3.8773\u2005(16)\u2005\u00c5] between the sheets, leading to the formation of a three-dimensional framework.The title acyl\u00adhydrazone derivative, C N-acyl\u00adhydrazones containing a glycine residue have been investigated extensively for their biological and medical activities  due to the presence of the C=O group, an additional donor site. N-(ar\u00adyl)-amides  of the title compound are shown in Fig.\u00a01A has an extended conformation while mol\u00adecule B is U-shaped. In mol\u00adecule A, the conformations of the hydrazide N\u2014H and C\u2014H bonds are syn to each other, while the N\u2014H and C=O bonds are anti to each other. On the sulfonamide side, the conformations of the sulfonamide N\u2014H and C=O bonds are syn to each other. In mol\u00adecule B, the conformations of the hydrazide N\u2014H and C\u2014H bonds, the hydrazide N\u2014H and C=O, and the C=O and sulfonamide N\u2014H bonds are all syn to each other.The mol\u00adecular structures of the two independent mol\u00adecules \u00b0. The mean plane through atoms C9/N3/N2/C8/O3/C7 [maximum deviation of 0.043\u2005(2)\u2005\u00c5 for N2], the central section of the mol\u00adecule, is inclined to the two benzene rings, C1\u2013C6 and C10\u2013C15, by 86.38\u2005(12) and 7.22\u2005(12)\u00b0, respectively. In mol\u00adecule B, the benzene rings (C18\u2013C23 and C27\u2013C32) are inclined to one another by 74.00\u2005(14)\u00b0, and by 76.85\u2005(13) and 2.91\u2005(12)\u00b0, respectively, to the mean plane through atoms C26/N6/N5/C25/O6/C24 [maximum deviation of 0.061\u2005(2)\u2005\u00c5 for C26]. The different conformations of mol\u00adecules A and B are further demonstrated by the differences in the equivalent torsion angles; N1\u2014C7\u2014C8\u2014N2 = 29.3\u2005(3) \u00b0 in A, compared to N4\u2014C24\u2014C25\u2014N5 = 177.2\u2005(2)\u00b0 in B, and C1\u2014S1\u2014N1\u2014C7 = \u221267.3\u2005(2)\u00b0 in A, compared to C18\u2014S2\u2014N4\u2014C24 = 67.7\u2005(3)\u00b0 in B.In mol\u00adecule A and C25\u2014O6 in B, are 1.214\u2005(3) and 1.229\u2005(3)\u2005\u00c5, respectively, indicating that the mol\u00adecules exist in the keto form in the solid state. The C9=N3 and C26=N6 bond lengths, both 1.272\u2005(3)\u2005\u00c5 in mol\u00adecules A and B, respectively, confirm their significant double-bond character. The N2\u2014N3 and N5\u2014N6 bond distances are 1.383\u2005(3) and 1.379\u2005(3)\u2005\u00c5, respectively, and the C8\u2014N2 and C25\u2014N5 bond distances are 1.339\u2005(3) and 1.334\u2005(3)\u2005\u00c5, respectively, which indicates significant delocalization of \u03c0-electron density over the hydrazone portions of the mol\u00adecules.The carbonyl bonds lengths, C8\u2014O3 in A mol\u00adecules are linked by a pair of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with an via three N\u2014H\u22efO hydrogen bonds involving the B mol\u00adecules, forming chains along [100] that enclose via C\u2014H\u22efO hydrogen bonds and a C\u2014H\u22ef\u03c0 inter\u00adaction, forming sheets parallel to (010). The is a C\u2014H\u22ef\u03c0 inter\u00adaction and a slipped parallel \u03c0\u2013\u03c0 inter\u00adaction , between the sheets, leading to the formation of a three-dimensional framework \u2013NH\u2013N=CH\u2013 yielded only one hit, namely N-(2-hy\u00addroxy-1-naphthyl\u00admethyl\u00adene)-N\u2032-(N-phenyl\u00adglyc\u00adyl)hydrazine -N-{2-[2-(3-chloro\u00adbenzyl\u00adidene) hydrazin\u00adyl]-2-oxoeth\u00adyl}-4-methyl\u00adbenzene\u00adsulfonamide monohydrate  was added to glycine (0.02\u2005mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373\u2005K for 6\u2005h, left overnight at room temperature, then filtered and treated with dilute hydro\u00adchloric acid. The solid N-(p-toluene\u00adsulfon\u00adyl)glycine (L1) obtained was crystallized from aqueous ethanol.L1 (0.02\u2005mol) dissolved in ethanol (30\u2005ml) and the mixture was refluxed. The reaction was monitored by TLC at regular inter\u00advals. After completion of the reaction, the reaction mixture was concentrated to remove the excess ethanol. The product, N-(p-toluene\u00adsulfon\u00adyl)glycine ethyl ester (L2) was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone.Sulfuric acid (0.5\u2005ml) was added to L2 (0.01\u2005mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10\u2005ml) in 30\u2005ml ethanol and the mixture was refluxed for 6\u2005h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(p-toluene\u00adsulfon\u00adyl)glycinyl hydrazide (L3).The pure L3 (0.01\u2005mol) and p-methyl\u00adbenzaldehyde (0.01\u2005mol) in anhydrous methanol (30\u2005ml) and two drops of glacial acetic acid was refluxed for 8\u2005h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (455\u2013457\u2005K). Prism-like colourless single crystals were grown from a DMF solution by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3286.7, 1678.1, 1606.7, 1323.2 and 1157.3\u2005cm\u22121 for the stretching bands of N\u2014H, C\u2014O, C\u2014N, S\u2014O asymmetric and S\u2014O symmetric, respectively.A mixture of Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined using a riding model: C\u2014H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015009330/su5131sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015009330/su5131Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015009330/su5131Isup3.cmlSupporting information file. DOI: 1401257CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Deionised water (negative) and Solcoseryl (positive) were applied on the control groups. Histochemical and biochemical assays were used to evaluate cellular and bio-molecular changes in the wound.Excision wounds were created on the dorsum of Sprague Dawley rats and treated topically twice/day with 20\u00a0\u03bcL of PE and WE (5\u00a0mg extract/mL), 0.5 \u03bcgSe2+) only increased significantly (p\u2009<\u20090.05) wound total protein content  on day 10 post wounding. PES increased significantly (p\u2009<\u20090.05) the number of fibroblasts/high power field (HPF) (75.60\u2009\u00b1\u20099.66) but decreased significantly (p\u2009<\u20090.05) the number of polymorphonuclear leukocytes/HPF (59.20\u2009\u00b1\u200912.64) in the wound compared to positive control  on day 4. Similar results were recorded for WES. PES demonstrated increased neovascularization, TGF-\u03b21 and VEGFA expressions at day 4 and increased collagen at day 10.PES (PE\u2009+\u20090.5\u00a0\u03bcg Se2+ addition.Papaya extract improved wound repair by increasing fibroblasts recruitment and reducing polymorphonuclear leukocytes infiltration through early transient expressions of TGF-\u03b21 and VEGFA at the wound area. The processes were amplified with SeThe online version of this article (doi:10.1186/s12906-015-0900-4) contains supplementary material, which is available to authorized users. Carica papaya L (papaya) has been attributed to its high content of cystein endopeptidase, mineral nutrients and vitamins .2O); gently shaken at 37\u00a0\u00b0C for 8\u00a0h, centrifuged at 200\u2009\u00d7\u2009g for 30\u00a0min at 4\u00a0\u00b0C and finally freeze-dried . Glucosamine hydrochloride (0.05\u00a0mg) was used as a standard. Values were corrected to the initial wound tissue dry weight.Wound tissue samples were completely dried in oven at 60\u00a0\u00b0C and ground to powder. The HAM content was determined at 530\u00a0nm following the established protocol . A correp\u2009<\u20090.05.Data were analyzed using the statistical software SPSS . Data were expressed as mean\u2009\u00b1\u2009standard error of mean (SEM). One way-Anova was used to analyse all data and Tukey\u2019s post-hoc test was used to find the mean differences within the groups at different time interval. Data were considered statistically significant at p\u2009<\u20090.05) increase in the total protein content of the wound tissue (95.14\u2009\u00b1\u20091.15\u00a0mg/g tissue) as compared to the treatment with PC (80.42\u2009\u00b1\u20090.86\u00a0mg/g tissue). In contrast, Zn added extracts did not show any significant changes in the wound total protein content on day 4 and day 10 post wounding as compared to NC   increase in HOP content (20.07\u2009\u00b1\u20093.19\u00a0\u03bcg/mg tissue and 19.80\u2009\u00b1\u20092.51\u00a0\u03bcg/mg tissue respectively) on day 4 compared to NC (8.47\u2009\u00b1\u20091.50\u00a0\u03bcg/mg tissue) and significantly (p\u2009<\u20090.05) increase HOP content (55.15\u2009\u00b1\u20091.06\u00a0\u03bcg/mg tissue and 52.61\u2009\u00b1\u20091.02\u00a0\u03bcg/mg tissue respectively) on day 10 compared to NC (25.35\u2009\u00b1\u20091.04\u00a0\u03bcg/mg tissue), PC (40.62\u2009\u00b1\u20090.60\u00a0\u03bcg/mg tissue), PE (37.74\u2009\u00b1\u20091.24\u00a0\u03bcg/mg tissue) and WE (27.25\u2009\u00b1\u20091.03\u00a0\u03bcg/mg tissue). Treatment with PEZ and WEZ also resulted in significant (p\u2009<\u20090.05) increase in HOP content (30.52\u2009\u00b1\u20091.23\u00a0\u03bcg/mg tissue and 31.32\u2009\u00b1\u20091.34\u00a0\u03bcg/mg tissue respectively) on day 10 compared to NC (25.35\u2009\u00b1\u20091.04\u00a0\u03bcg/mg tissue) (Table\u00a0p\u2009<\u20090.05) after treatment with PE (53.41\u2009\u00b1\u20096.21\u00a0mg/g tissue), PES (60.84\u2009\u00b1\u20096.08\u00a0mg/g tissue) and WES (53.81\u2009\u00b1\u20097.36\u00a0mg/g tissue) compared to NC (20.71\u2009\u00b1\u20094.36\u00a0mg/g tissue) and WE (25.45\u2009\u00b1\u20095.32\u00a0mg/g tissue) on day 4 and only after treatment with PES (18.12\u2009\u00b1\u20093.32\u00a0mg/g tissue) compared to NC (5.82\u2009\u00b1\u20091.28\u00a0mg/g tissue) on day 10. Treatment with only PES resulted in significantly increased (p\u2009<\u20090.05) HAM content (35.23\u2009\u00b1\u20094.95\u00a0mg/g tissue and 18.21\u2009\u00b1\u20093.03\u00a0mg/g tissue) both on day 4 and day 10 respectively compared to NC (12.54\u2009\u00b1\u20094.53\u00a0mg/g tissue day 4 and 4.59\u2009\u00b1\u20091.57\u00a0mg/g tissue day 10) (Table\u00a0Treatment with PES and WES resulted in significant (p\u2009<\u20090.05) lower both on day 4  of the mean number of PMNL/HPF compared to NC (164.40\u2009\u00b1\u200925.93), PC (101.00\u2009\u00b1\u200927.99) and WE (126.00\u2009\u00b1\u200923.53) on day 4  higher on day 4 in all treatment groups compared to NC (5.60\u2009\u00b1\u20093.21). However, significantly increased (p\u2009<\u20090.05) number of fibroblasts/HPF was observed on day 4 in PES (75.60\u2009\u00b1\u20099.66) treated only group compared to that of PC, PE and WE groups   when treated with PES (69.60\u2009\u00b1\u200913.07) as compared to NC (40.80\u2009\u00b1\u20099.09)  Fig.\u00a0. On day 09) Fig.\u00a0.On day 4, wound tissue sections from all groups exhibited disrupted wound-dermis interface, with the absence of overlying epithelia  which are affected due to injury [2+ supplementation was shown to improve healing of the wound caused by surgical incision, trauma, and burns [2+ added unripe C. papaya improves healing of excision wound through enhanced anti-inflammatory and antioxidant effect [Sentiation , 21. Whiferation . Both Seo injury . In reland burns . Earliert effect .The present study used female rats for the experimentation. Female rats are known to exhibit shorter period for complete wound healing and this has been linked to the circulating oestrogen level \u201326. Thou2+ added papaya mediates improved wound healing by reducing inflammation associated oxidative damage apparently via cyclooxygenase specific inhibition, arginine metabolism and up-regulation of antioxidant enzymes. These could be linked to the added Se2+ [Depending on the type and aetiology of wound, wound healing involves inflammation (day 1\u20134 or more), proliferative/repair day 5\u201310 or 11), and remodelling phases (day 11\u201321 or more) , 10. Pro or 11, aded Se2+ .2+ added PE/WE treated groups albeit the reduction was not as significant as Se2+ added PE/WE treated groups  and biochemical events , a model is proposed Fig.\u00a0 to descrPE through mechanisms associated with cyclooxygenase and prostaglanding E2 inhibition  reduced Consistently, PE induced a transient up-regulation of TGF-\u03b21 and VEGFA on day 4 which in turn enhanced cellular activity  as evidenced in the increased fibroblasts recruitment and early appearance of new blood vessels  in PE treatment. These effect was more pronounced in Se added PE.In addition, the establishment of new blood vessels enhanced nutrient delivery to the fibroblasts and enhanced fibroblastic synthesis of provisional matrix, primary molecules in the extracellular matrix and collagen. In line with this, Se added PE exclusively enhanced the synthesis of primary molecules of ground substances i.e. HUA and HAM. PE alone showed little effect in these regard. However, hydroxyproline an index for collagen turnover was found to be markedly increased, later on day 10, with PE treatment. Concurrently, well aligned collagen fibres and reconstructed dermis and epidermis were observed later on day 10 after treatment with PE and PES especially. Collectively, the increased recruitment of fibroblasts and their bio-molcular products resulted in the significant increase in wound total protein content later on day 10 in PE treated group.2+\u00a0added papaya extracts might (i) reduce PMNL infiltration to speed up the inflammatory phase as well as (ii) induced transient up-regulation of TGF-\u03b21 and VEGFA expression to enhance angiogenesis and fibroblast recruitment thereby enhanced cutaneous wound repair.Se"}
{"text": "III ion in the title complex is coordinated by two 1,10-phenanthroline (phen) ligands, one water mol\u00adecule and a chloride in a cis geometry, displaying a distorted octa\u00adhedral environment. The [ZnCl4]2\u2212 anion has a slightly distorted tetra\u00adhedral coordination geometry.The Cr 12H8N2)2(H2O)][ZnCl4]\u00b7H2O, has been determined from synchrotron data. The CrIII ion is bonded to four N atoms from two 1,10-phenanthroline (phen) ligands, one water mol\u00adecule and a Cl atom in a cis arrangement, displaying an overall distorted octa\u00adhedral coordination environment. The Cr\u2014N(phen) bond lengths are in the range of 2.0495\u2005(18) to 2.0831\u2005(18)\u2005\u00c5, while the Cr\u2014Cl and Cr\u2014(OH2) bond lengths are 2.2734\u2005(7) and 1.9986\u2005(17)\u2005\u00c5, respectively. The tetra\u00adhedral [ZnCl4]2\u2212 anion is slightly distorted owing to its involvement in O\u2014H\u22efCl hydrogen bonding with coordinating and non-coordinating water mol\u00adecules. The two types of water mol\u00adecules also inter\u00adact through O\u2014H\u22efO hydrogen bonds. The observed hydrogen-bonding pattern leads to the formation of a three-dimensional network structure.The structure of the title compound, [CrCl(C These complexes are promising materials for the development of new mol\u00adecule-based magnets, solar energy storage media or tunable solid state lasers ][ZnCl4]\u00b7H2O , (I)We report here on the synthesis and crystal structure of the title compound, (ClO4)3\u00b7H2O 2]ClO4\u00b7H2O 2]Cl  bond lengths in (I)2) bond length is comparable to those of 1.947\u2005(4), 1.9579\u2005(10) and 1.996\u2005(4)\u2005\u00c5 found in cis-[Cr(dpp)(phen)2(H2O)](NO3)2\u00b7H2O\u00b7CH3CN [Hdpp = (C6H5O)2\u00b7PO2H] 2(H2O)](ClO4)2\u00b72H2O (H2O)](ClO4)2\u00b7H2O  2]Cl 2Cl2]Cl  A\u2014Cr1A\u2014N2A and N3A\u2014Cr1A\u2014N4A are 79.76\u2005(5) and 80.23\u2005(7)\u00b0.The Cr\u2014N(phen) bond lengths are in the range of 2.0495\u2005(18) to 2.0831\u2005(18)\u2005\u00c5 and are in good agreement with those observed in 2\u2212 anion and the second water mol\u00adecule remain outside the coordination sphere. The ZnII atom in the complex anion exhibits a slightly distorted tetra\u00adhedral coordination sphere caused by the influence of hydrogen bonding on the Zn\u2014Cl bond lengths and the Cl\u2014Zn\u2014Cl angles. The Zn\u2014Cl bond lengths range from 2.2443\u2005(7) to 2.2854\u2005(7)\u2005\u00c5 and the Cl\u2014Zn\u2014Cl angles from 107.54\u2005(4) to 111.57\u2005(3)\u00b0.The [ZnClB of the [ZnCl4]2\u2212 anion and the Cl1A ligand atom are not involved in hydrogen bonding. An extensive array of O\u2014H\u2014O and O\u2014H\u22efCl contacts (phen)2(H2O)](NO3)2\u00b7H2O\u00b7CH3CN 3\u00b7H2O 2]ClO4 2]Cl ]2+ with any anions have been deposited.A search of the Cambridge Structural Database 2]ClO4\u00b7H2O was prepared according to a literature procedure 2]ClO4\u00b7H2O (0.2\u2005g) was dissolved in 10\u2005mL of 0.01\u2005M HCl at 313\u2005K, and 5\u2005mL of 1\u2005M HCl containing 1.2\u2005g of solid ZnCl2 were added to this solution. The mixture was refluxed at 328\u2005K for 30\u2005min and then cooled to room temperature. The resulting solution was filtered and allowed to stand at room temperature for 3\u20135 days, giving purple crystals of (I)All chemicals were reagent-grade materials and used without further purification. The starting material, Uiso(H) set to 1.2Ueq(C). The H atoms of water mol\u00adecules  were located from difference Fourier maps and refined with restraints and an O\u2014H distance of 0.84\u2005(1)\u2005\u00c5, with Uiso(H) values of 1.2 Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015003266/wm5123sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015003266/wm5123Isup2.hklStructure factors: contains datablock(s) I. DOI: 1049598CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound consists of discrete octa\u00adhedral cobalt(II) complexes that are linked by a variety of hydrogen-bonding inter\u00adactions into a three-dimensional network. 2(C6H6N2O)4]\u00b72C6H6N2O\u00b7C2H5OH, comprises one CoII cation, two thio\u00adcyanate anions, four coordinating and two solvent isonicotinamide molecules and one ethanol solvent mol\u00adecule. The CoII cations are octa\u00adhedrally coordinated by four N-coordinating isonicotinamide ligands and two terminally N-bonded thio\u00adcyanate anions. These discrete complexes are linked by inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efS hydrogen-bonding inter\u00adactions into a three-dimensional network. The two isonicotinamide and the ethanol solvent mol\u00adecules are embedded in channels of this network and are linked through further N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds to the network. The ethanol solvent mol\u00adecule is disordered over two sets of sites (occupancy ratio 0.6:0.4).The asymmetric unit of the title compound, [Co(NCS) However, instead of the expected chain compound, a discrete complex with additional solvate mol\u00adecules of composition [Co(NCS)2(C6H6N2O)4]\u00b72C6H6N2O\u00b7C2H5OH was obtained in the current study and characterized by single-crystal X-ray diffraction.There is an increasing inter\u00adest in compounds showing cooperative magnetic properties, such as ferromagnetism, anti\u00adferromagnetism and metamagnetism or a slow relaxation of the magnetization, indicative of single-mol\u00adecule or single-chain magnetism  and one positionally disordered ethanol solvent mol\u00adecule. The CoII cation is coordinated by two terminal N-bonded thio\u00adcyanate anions and four N-coordinating isonicotinamide ligands, forming a slightly distorted octa\u00adhedron \u2013178.32\u2005(11)\u00b0 for trans angles] are indicative for a slight distortion and are comparable with those in similar coordination compounds with CoII, thio\u00adcyanate anions and N-bound co-ligands.The asymmetric unit of the title compound consists of one Coon Fig.\u00a01. Bond lea axis by inter\u00admolecular N\u2014H\u22efO hydrogen-bonding inter\u00adactions  with 73.3\u2005mg isonicotinamide (0.6\u2005mmol) in ethanol (1.5\u2005ml) after being allowed to stand for a few days at room temperature.Cobalt(II) thio\u00adcyanate and isonicotinamide were obtained from Alfa Aesar and were used without further purification. Single crystals suitable for structure analysis were obtained by the reaction of 26.3\u2005mg Co(NCS)Uiso(H) = 1.2Ueq (1.5 for methyl and O\u2014H hydrogen atoms) using a riding model with C\u2014H = 0.95\u2005\u00c5 for aromatic, C\u2014H = 0.98\u2005\u00c5 for methyl, N\u2014H = 0.88\u2005\u00c5 and O\u2014 H = 0.84\u2005\u00c5, respectively. The ethanol mol\u00adecule was found to be disordered over two sets of sites and was refined with fixed occupation factors of 0.6 and 0.4, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016010951/wm5305sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010951/wm5305Isup2.hklStructure factors: contains datablock(s) I. DOI: 1491089CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Within the complex, intra\u00admolecular C\u2014H\u22efS, C\u2014H\u22ef\u03c0, N\u2014H\u22efBr and \u03c0\u2013\u03c0 stacking inter\u00adactions are observed. In the crystal, the components are linked by N\u2014H\u22efBr and C\u2014H\u22efN hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions, generating chains propagating in the [100] direction.In the solvated dinuclear complex \u00b72C2H3N or [Cu2Br2(ATU)(dppm)2]\u00b72CH3CN. Both Cu+ ions adopt distorted tetra\u00adhedral geometries, being coordinated by one terminal Br atom, one \u03bc2-S atom of the bridging ATU ligand and two P atoms of the bridging dppm ligands. Within the complex, intra\u00admolecular C\u2014H\u22efS, C\u2014H\u22ef\u03c0, N\u2014H\u22efBr and \u03c0\u2013\u03c0 stacking inter\u00adactions are observed. In the crystal, the components are linked by N\u2014H\u22efBr and C\u2014H\u22efN hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions, generating chains propagating in the [100] direction.The reaction of cuprous bromide with a mixture of 1,1-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane (dppm: C Both CuI atoms share a tetra\u00adhedral corner via an S-atom bridge.The title complex [Cu2I2(C3H8N2S)(C25H22P2)2]\u00b71.5CH3CN 3]\u00b7CH3CN 2P2 plane of the Cu1\u2013S1\u2013Cu2\u2013P3\u2013C38\u2013P4 chair conformation by an angle [72.59\u2005(3)\u00b0] that is significantly larger than that for the Cu1\u2013S1\u2013Cu2\u2013P1\u2013C13\u2013P2 plane [45.68\u2005(2)\u00b0]. Thus, the C\u2014H\u22efS effect might be the influence that leads to the longer distance between the centroids  of the phenyl rings, Cg8\u22efCg9 [4.0356\u2005(17)\u2005\u00c5] compared with the Cg4\u22efCg5 distance [3.6097\u2005(19)\u2005\u00c5]. The intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction (C31\u2014H31\u22efCg6) also imposes a contact, of 3.476\u2005(3)\u2005\u00c5, between the Csp2 atom of the phenyl ring and another phenyl ring centroid (C20\u2013C25) of the other dppm ligand. An inter\u00adaction (C12\u2014H12\u22efN2) between Cg5 and the NH2 group is also observed. In addition, two intra\u00admolecular N\u2014H\u22efBr inter\u00adactions are found between the NH2 group of ATU and Br atoms. A perspective view of all the intra\u00admolecular inter\u00adactions in (I)The intra\u00admolecular inter\u00adaction C44\u2014H44\u22efS1 Table\u00a02 has an ex, 2\u00a0\u2212\u00a0y, \u2212z), which generates Cg8\u22efCg8iii rings  generating a chain of alternating N\u2014H\u22efBr links and \u03c0\u2013\u03c0 stacking running along [100], as shown in Fig.\u00a03ii and C50\u2014H50\u22efN3i; symmetry codes: (i) \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a0x, y\u00a0\u2212\u00a0z\u00a0+\u00a0In the crystal, neighbouring dinuclear mol\u00adecules form a hydrogen-bonded dimer held together by two N\u2014H\u22efBr bonds as a cyclic pattern with its symmetry\u2013equivalent partner, generated by a crystallographic inversion center (symmetry code: \u22122I2(C3H8N2S)(dppm)2]\u00b71.5CH3CN, studied by Nimthong et al.  was added and further refluxed for four\u2005h and the precipitate slowly disappeared. Colorless crystals were obtained after the clear solution was left to evaporate at room temperature for a few days. The yield was 33% based on CuBr. Calculated for C58H58Br2Cu2N4P4S: C 55.55, H 4.66, N 4.47 and S 2.56%. Found: C 55.28, H 4.28, N 3.68 and S 2.54%. The main IR bands : 3282 [\u03bd(NH2)], 3168 [\u03bd(NH2)], 3058 [\u03bd(=C\u2014H)ph], 1580 [\u03bd(C=S)] and 1110 [\u03bd(P\u2014Cph)].Copper(I) bromide  was added to a solution of 1,1-bis\u00ad(di\u00adphenyl\u00adphosphino)methane  in 30\u2005ml aceto\u00adnitrile at 338\u2005K. The mixture was refluxed for two\u2005h and a white precipitate was formed. After that, Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The N\u2014H atoms were located in a difference map and the coordinates were refined with an N\u2014H distance restraint of 0.86\u2005\u00c5 and with Uiso(H) = 1.2eqU(N). Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015015637/hb7479sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015637/hb7479Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419827CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 2482310.1038/srep24823; published online: 04212016; updated: 05312016This Article contains a typographical error in the Results section under subheading \u20185G2\u2009mAb recognized sugar chain epitopes\u2019,a GlcNAc), Lec , core1 , core2 GalNAc), and Sia\u03b12-6core1 GalNAc) structures .\u201d\u201cThe 5G2\u2009mAb recognized the Leshould read:a GlcNAc), Lec , core1 , core2 GalNAc), and Sia\u03b12-6core1 GalNAc) structures .\u201d\u201cThe 5G2\u2009mAb recognized the Le"}
{"text": "H)-one compound that has been designed and synthesized to explore a new electron-donor (D) and -acceptor (A) conjugated complex, the two cyclo\u00adpenta\u00addienyl rings adopt an eclipsed conformation. The anthracene tricycle is distorted towards a butterfly conformation.In a ferrocen\u00adyl\u2013anthracen-9(10 5H5)(C27H16NO)], designed and synthesized to explore a new electron-donor (D) and -acceptor (A) conjugated complex, the two cyclo\u00adpenta\u00addienyl rings adopt an eclipsed conformation. The anthracene tricycle is distorted towards a butterfly conformation and the mean planes of the outer benzene rings are inclined each to other at 22.7\u2005(3)\u00b0. In the crystal, mol\u00adecules are paired into inversion dimers via \u03c0\u2013\u03c0 inter\u00adactions. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions link further these dimers into one-dimensional columns along the b axis, with the ferrocenylethynyl arms arranged between the stacks to fill the voids.In the title compound, [Fe(C D) and -acceptor (A) mol\u00adecules have attracted much attention owing to their unique structures and various characteristic properties  demonstrate guest-mol\u00adecule absorption and valence tautomerization etc. We have synthesized the title compound 1-(ferrocenylethyn\u00adyl)-10-(phenyl\u00adimino)\u00adanthracen-9(10H)-one [1-(Fc)AqPHI] and herein we report its crystal structure, determined by synchrotron radiation (SR) X-ray powder diffraction.Compounds containing a mixture of electron-donor 2Aq. Distances between the ring centroids cover the range from 4.09\u2005\u00c5 in 1,4 Fc2Aq down to 3.68\u2005\u00c5 in 1,2-(FcPh)2Aq. The smallest perpendicular distance for all the materials was close to 3.45\u2005\u00c5 . C\u2014H\u22ef\u03c0 inter\u00adactions are also found in 1,4-Fc2Aq, 1,5-Fc2Aq and 1,2-(FcPh)2Aq. Two kinds of C\u2014H\u22ef\u03c0 inter\u00adactions in 1,4-Fc2Aq connect the CP rings and the rings of the Aq groups of neighbouring mol\u00adecules. A C\u2014H\u22ef\u03c0 inter\u00adaction in 1,5-Fc2Aq links a CH\u2013 group from the Aq unit and a CP ring of Fc fragment. There are three C\u2014H\u22ef\u03c0 inter\u00adactions in 1,2-(FcPh)2Aq.In the reported examples compiled in the Cambridge Structural Database -one , ethynylferrocene , Pd(PPh3)2Cl2 (3.1\u2005mg), and CuI (5\u2005mg) were suspended in Et3N (15\u2005ml). After refluxing for 5\u2005h, Et3N was removed in vacuo, and the resultant residue was dissolved in CH2Cl2. The solution was washed with water (150\u2005ml), and dried over Na2SO4. After evaporation of the solvent, the crude product was purified with alumina column chromatography (activity II\u2013III) with a mixture of di\u00adchloro\u00admethane and hexane (1:2 v/v) as eluent. The third fraction was collected, and produced a red\u2013brown solid of the title compound . Very small single crystals unsuitable for conventional X-ray structure analysis were obtained by recrystallization from di\u00adchloro\u00admethane\u2013hexane. 1H NMR : \u03b4 8.1\u20138.5 , 7.0\u20137.9 , 6.80 , 4.1\u20134.8 . IR (KBr pellet): 2208 (\u03bd C=C/ cm\u22121), 1668 (\u03bd C=O/ cm\u22121), 1483 (\u03bd C=N/ cm\u22121). MALDI\u2013TOF\u2013MS: m/z = 490.1.Under a nitro\u00adgen atmosphere, 1-bromo-10-(phenyl\u00adimino)\u00adanthracen-9 standard powder sample was used for wavelength calibration. The calibrated wavelength was 0.80200\u2005(1)\u2005\u00c5. The powder profile was measured at 100\u2005K with 120\u2005min X-ray exposure time.The size of 1-(Fc)AqPHI crystals was small, less than 1\u2005\u00b5m. SR powder-diffraction techniques were employed for the structure determination. The powder crystallites were installed in a 0.4\u2005mm glass capillary. The X-ray powder diffraction data were measured using a large Debye\u2013Scherrer camera with an imaging-plate (IP) as a detector installed at SPring-8 BL02B2  was 63.2. The space group P21/n was assigned on the basis of systematic extinctions.Indexing was carried out using the program SP . Uiso for H atoms connected to the Aq and Ph parts were fixed at 0.05\u2005\u00c52. isoU for H atoms connected to the C25\u2013C29 and C30\u2013C34 CP rings were fixed at 0.09\u2005\u00c52 and 0.04\u2005\u00c52, respectively. A split-type pseudo-Voigt profile function  global, I, 1FcAqPHI-100K_powder_data. DOI: 10.1107/S1600536814025252/cv5475Isup2.rtvRietveld powder data: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814025252/cv5475Isup3.molSupporting information file. DOI: 1034683CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two compounds are isotypic and the two-dimensional polymeric structure is based on centrosymmetric dinuclear bridged complex units. Within the layers, which lie parallel to (100), the coordinating water mol\u00adecule forms an O\u2014H\u22efO hydrogen bond to the single bridging carboxyl\u00adate O atom. 3-2-acetato]\u00addipotassium], [K2(C8H5Cl2O3)2(H2O)]n, and poly[\u03bc-aqua-bis\u00ad[\u03bc3-2-acetato]\u00addirubidium], [Rb2(C8H5Cl2O3)2(H2O)]n, respectively, have been determined and are described. The two compounds are isotypic and the polymeric structure is based on centrosymmetric dinuclear bridged complex units. The irregular six-coordination about the alkali cations comprises a bridging water mol\u00adecule lying on a twofold rotation axis, the phen\u00adoxy O-atom donor and a triple bridging carboxyl\u00adate O atom of the oxo\u00adacetate side chain of the 3,5-D ligand, and the second carb\u00adoxy\u00adate O-atom donor also bridging. The K\u2014O and Rb\u2014O bond-length ranges are 2.7238\u2005(15)\u20132.9459\u2005(14) and 2.832\u2005(2)\u20133.050\u2005(2)\u2005\u00c5, respectively, and the K\u22efK and Rb\u22efRb separations in the dinuclear units are 4.0214\u2005(7) and 4.1289\u2005(6)\u2005\u00c5, respectively. Within the layers which lie parallel to (100), the coordinating water mol\u00adecule forms an O\u2014H\u22efO hydrogen bond to the single bridging carboxyl\u00adate O atom.The two-dimensional coordination polymeric structures of the hydrated potassium and rubidium salts of acetic acid , namely, poly[\u03bc-aqua-bis\u00ad[\u03bc The comparative M\u2014O bond length range for the two metals (Tables 1O:O1)-chelate inter\u00adaction .The hydrated complexes (I)on Fig.\u00a02, three b Tables 1 and 2 \u25b8 M\u2014O complex network with the aromatic rings of the ligands peripherally located between the layers. Within the layers there are a number of short metal\u22efmetal contacts, the shortest being across an inversion centre [K\u22efKii = 4.0214\u2005(7)\u2005\u00c5 and Rb\u22efRbii = 4.1289\u2005(6)\u2005\u00c5], the longest being K\u22efKvi = 4.3327\u2005(5)\u2005\u00c5 and Rb\u22efRbvi = 4.5483\u2005(5)\u2005\u00c5  or Rb2CO3 (115\u2005mg) (for (II)] to a hot solution of acetic acid  (220\u2005mg) in 10\u2005ml of 50% (v/v) ethanol/water. After heating for 5\u2005min, partial room temperature evaporation of the solutions gave in all two cases, colourless needles from which specimens were cleaved for the X-ray analyses.Compounds (I)aromatic = 0.95\u2005\u00c5 or C\u2014Hmethyl\u00adene = 0.99\u2005\u00c5] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The water H-atom in both structures was located in a difference Fourier map and was allowed to ride in the refinements with an O\u2014H distance restraint of 0.90\u00b10.02\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details for (I)10.1107/S2056989015016722/wm5206sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015016722/wm5206Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016722/wm5206IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989015016722/wm5206Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015016722/wm5206IIsup5.cmlSupporting information file. DOI: 1422835, 1422834CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "O\u2014H\u22efO hydrogen bonds between water mol\u00adecules and ClO4 units lead to the formation of a three-dimensional network in the structures.The crystal structures of the tetra- and hexa\u00adhydrate phases of Ca6(ClO4)]2 dimers by sharing two ClO4 tetra\u00adhedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra\u00adhedra. O\u2014H\u22efO hydrogen bonds between the water mol\u00adecules as donor and ClO4 tetra\u00adhedra and water mol\u00adecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2\u00b76H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures.The title compounds, calcium perchlorate tetra\u00adhydrate and calcium perchlorate hexa\u00adhydrate, were crystallized at low temperatures according to the solid\u2013liquid phase diagram. The structure of the tetra\u00adhydrate consists of one Ca The resulting coordination polyhedron is a distorted square anti-prism . The Ca\u2014O bond lengths involving the water mol\u00adecules range from 2.3284\u2005(17) to 2.4153\u2005(16)\u2005\u00c5 and are considerably shorter than the Ca\u2014O bond lengths involving the perchlorate O atoms [2.5417\u2005(16) to 2.5695\u2005(17)\u2005\u00c5].The Casm Fig.\u00a01b. The C2+ cations in Ca(ClO4)\u00b76H2O are each coordinated by six water mol\u00adecules and two perchlorate tetra\u00adhedra . Nevertheless, according to the bond-valence model 6(ClO4)]2 dimers oriented in layers parallel to (001).The two different Cara Fig.\u00a02. Again, 4)\u00b74H2O are shared between two adjacent Ca2+ ions, forming chains extending parallel to 2 sheets along [001] 2\u00b74H2O phases, see: Robertson & Bish (2010M = Mg); Hennings et al. (2014M(ClO4)2\u00b76H2O phases, see: Ghosh et al. ; Ghosh & Ray 2\u00b74H2O was crystallized from an aqueous solution of 62.96 wt% Ca(ClO4)2 at 273\u2005K after one day and Ca(ClO4)2\u00b76H2O from an aqueous solution of 57.55 wt% Ca(ClO4)2 at 238\u2005K after one week. For the preparation of these aqueous solutions, Ca(ClO4)2\u00b74H2O  was used. The Ca2+ content was analysed via complexometric titration with EDTA. The crystals remain stable in the saturated aqueous solution over at least four weeks.Ca2\u00b74H2O, distance restraints were applied for all water mol\u00adecules, with O\u2014H and H\u2014H distance restraints of 0.82\u2005(1) and 1.32\u2005(1)\u2005\u00c5, respectively. For Ca(ClO4)2\u00b76H2O, Uiso values were set at 1.2Ueq(O) using a riding-model approximation. Distance restraints were applied for that structure for all water mol\u00adecules, with O\u2014H and H\u2014H distance restraints of 0.84\u2005(2) and 1.4\u2005(2)\u2005\u00c5, respectively. Ca(ClO4)2\u00b76H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S1600536814024532/wm5079sup1.cifCrystal structure: contains datablock(s) CaClO4_4H2O_200K, CaClO4_6H2O_180K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup2.hklStructure factors: contains datablock(s) CaClO4_4H2O_200K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup3.hklStructure factors: contains datablock(s) CaClO4_6H2O_180K. DOI: Click here for additional data file.10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup5.cmlSupporting information file. DOI: 1033323, 1033324CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Crystal structures of morpholinium hydrogen bromanilate have been determined at 130, 145 and 180\u2005K. The asymmetric unit comprises one morpholinium cation and two halves of crystallographically independent bromanilate monoanions. The conformations of the two independent bromanilate anions are different from each other with respect to the O\u2014H orientation. The two different anions are linked alternately into a chain though a short O\u2014H\u22efO hydrogen bond, in which the H atom is disordered over two positions. 4H10NO+\u00b7C6HBr2O4\u2212, were determined at three temperatures, viz. 130, 145 and 180\u2005K. The asymmetric unit comprises one morpholinium cation and two halves of crystallographically independent bromanilate monoanions, which are located on inversion centres. The conformations of the two independent bromanilate anions are different from each other with respect to the O\u2014H orientation. In the crystal, the two different anions are linked alternately into a chain along [211] through a short O\u2014H\u22efO hydrogen bond, in which the H atom is disordered over two positions. The refined site-occupancy ratios, which are almost constant in the temperature range studied, are 0.49\u2005(3):0.51\u2005(3), 0.52\u2005(3):0.48\u2005(3) and 0.50\u2005(3):0.50\u2005(3), respectively, at 130, 145 and 180\u2005K, and no significant difference in the mol\u00adecular geometry and the mol\u00adecular packing is observed at the three temperatures. The morpholinium cation links adjacent chains of anions via N\u2014H\u22efO hydrogen bonds, forming a sheet structure parallel to (-111).Crystal structures of the title compound , C The anomalous behavior was ascribed to a drastic temperature variation of the disordered O\u2014H\u22efO hydrogen bond, as revealed by multi-temperature X-ray diffraction \u2005\u00c5 at 114\u2005K to 1.2951\u2005(10)\u2005\u00c5 at 180\u2005K; C6\u2014O4: from 1.290\u2005(10)\u2005\u00c5 at 114\u2005K to 1.2946\u2005(10) at 180\u2005K], which corresponds to population changes of the two disordered proton sites in the hydrogen bond (Tobu i: 3.1698\u2005(13)\u2005\u00c5 (130\u2005K), 3.1725\u2005(13)\u2005\u00c5 (145\u2005K) and 3.1763\u2005(13)\u2005\u00c5 (180\u2005K); Br2\u22efC1i: 3.2673\u2005(15)\u2005\u00c5 (130\u2005K), 3.2716\u2005(15)\u2005\u00c5 (145\u2005K) and 3.2808\u2005(15)\u2005\u00c5 (180\u2005K); symmetry code: (i) x- 1, y\u00a0\u2212\u00a01, z] are observed. A weak C\u2014H\u22efBr inter\u00adaction is also observed between the sheets.In the crystal, the two independent bromanilate anions with different conformations are linked alternately by short O\u2014H\u22efO hydrogen bonds Tables 1 and 3 \u25b8,A form  of bromanilic acid (200\u2005mg) with morpholine (60\u2005mg) at room temperature.Uiso(H) = 1.2Ueq(C). The N-bound H atom was located in a difference Fourier map and refined freely [refined N\u2014H = 0.85\u2005(3)\u20130.89\u2005(3)\u2005\u00c5]. Two disordered positions of the H atom in the O\u2014H\u22efO hydrogen bond were located in a difference Fourier map. Since site occupancy factors and isotropic displacement parameters are correlated and bonding effects also make the site-occupancy factors less reliable, the positional parameters and the occupancies of the H atom were refined, with Uiso(H) = 1.5Ueq(O), and with distance restraints of O\u2014H = 0.84\u2005(2)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989015017272/lh5788sup1.cifCrystal structure: contains datablock(s) General, 1, 2, 3. DOI: 10.1107/S2056989015017272/lh57881sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989015017272/lh57882sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989015017272/lh57883sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989015017272/lh57881sup5.cmlSupporting information file. DOI: 1424714, 1424713, 1424712CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal packing features \u03c0\u2013\u03c0 stacking inter\u00adactions between tpy\u2013tpy ligands.In this first crystal structure of an Ru complex with 6\u2032,6\"-bis\u00ad(pyridin-2-yl)-2,2\u2032:4\u2032,4\":2\",2\"\u2019-quaterpyridine, a \u2018half\u2019 of the ligand (one of the two terpyridyl units) is N^N^N  10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2\u2032-bi\u00adpyridine (bpy) and the tridendate ligand 6\u2032,6\u2032\u2032-bis\u00ad(pyridin-2-yl)-2,2\u2032:4\u2032,4\u2032\u2032:2\u2032\u2032,2\u2032\u2032\u2032-quaterpyridine (tpy\u2013tpy). The [RuCl(bpy)(tpy\u2013tpy)]+ monocation has a distorted octa\u00adhedral geometry at the central RuII ion due to the restricted bite angle [159.32\u2005(16)\u00b0] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78\u2005(11)\u00b0 between the least-squares planes. The lengths of the two Ru\u2014N bonds for bpy are 2.028\u2005(4) and 2.075\u2005(4)\u2005\u00c5, with the shorter bond being opposite to Ru\u2014Cl. For tpy\u2013tpy, the mean Ru\u2014N distance involving the outer N atoms trans to each other is 2.053\u2005(8)\u2005\u00c5, whereas the length of the much shorter bond involving the central N atom is 1.936\u2005(4)\u2005\u00c5. The Ru\u2014Cl distance is 2.3982\u2005(16)\u2005\u00c5. The free uncoordinated moiety of tpy\u2013tpy adopts a trans,trans conformation about the inter\u00adannular C\u2014C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant \u03c0\u2013\u03c0 stacking inter\u00adactions based on tpy\u2013tpy. The crystal structure reported here is the first for a tpy\u2013tpy complex of ruthenium. We report the structural characterization of \u00adchlorido\u00adruthenium(II) hexa\u00adfluorido\u00adphosphate, [RuCl(C In this and other related photocatalysts containing the {(tpy)Ru(bpy)(L)} moiety (L = H2O or Cl\u2212), the aqua species is typically formed by easy ligand substitution from its chlorido precursor in water Ru(tpy\u2013tpy)Ru(bpy)(Cl)]3+  crystallizes in the triclinic \u00b0 in agreement with those found in similar chlorido RuII-bpy complexes \u00b0]. The RuII atom and atoms N2, N4, N5, and Cl1 form an equatorial plane with a maximum deviation of 0.032\u2005(4)\u2005\u00c5. The Ru-bound tpy moiety and bpy are approximately planar  and their mean planes are essentially perpendicular to each other with a dihedral angle of 89.78\u2005(11)\u00b0 between planes. For the tridentate ligand, the mean Ru\u2014N distance involving the outer N1 and N3 atoms trans to each other is 2.053\u2005(8)\u2005\u00c5, whereas the bond distance involving the central N2 is much shorter [1.936\u2005(4)\u2005\u00c5] as a result of the structural constraint imposed by these mer-arranged ligands  and plane\u2013plane dihedral angles (\u03b1) are respectively: 3.723\u2005(3)\u2005\u00c5 and 2.8\u2005(2)\u00b0 for \u22ef ; 3.812\u2005(4)\u2005\u00c5 and 3.2\u2005(2)\u00b0 for \u22ef ; 3.826\u2005(4)\u2005\u00c5 and 5.6\u2005(3)\u00b0 for \u22ef ; and 3.630\u2005(4)\u2005\u00c5 and 15.5\u2005(3)\u00b0 for \u22ef . In all these \u03c0\u2013\u03c0 stacking inter\u00adactions, the slip angles from the parallel displacement  are smaller than 30\u00b0.The intra\u00admolecular Cl\u22efH contact of 2.70\u2005\u00c5 involving the hydrogen of the nearest C atom at bpy (H25) is similar to that observed earlier for complexes containing the {RuCl(bpy)} moiety -2,2\u2032:4\u2032,4\u2032\u2032:2\u2032\u2032,2\u2032\u2032\u2032-quaterpyridine. Other than one structure for the metal-free ligand itself (DMSO)2Cl2 into a solution of the tpy\u2013tpy ligand  at reflux. The reaction solution was refluxed for another 2.5\u2005h and then cooled down to room temperature. After evaporation of the solvent on a rotavap, water was added to dissolve the solid and excess NH4PF6 was added to form the precipitate, which was filtered off and dried under vacuum. Further purification was performed by column chromatography using alumina and a mixture of aceto\u00adnitrile/toluene (1:2) as the eluant. The product was collected from the first band. The solvent was evaporated and the dark-red solid was collected and dried under vacuum (yield: 30%). Analysis calculated for C40H28N8F6PClRu: C, 53.25; H, 3.13; N, 12.42. Found: C, 52.71; H, 3.12; N, 11.86. Single crystals for X-ray structural analysis were grown by slow diffusion of diethyl ether into aceto\u00adnitrile solutions of the complexes in long thin tubes.Compound + was also characterized in MeCN solutions by other techniques. Mass spectra (ESI\u2013MS: m/z 757) are in agreement with the formulation for the cation, i.e. [1(-PF6)]+ . 1H-NMR : \u03b4 10.27\u201310.26 , 9.07 , 8.89 , 8.73\u20136.95 . Electrochemical measurements by cyclic voltammetry gave a redox potential of 0.83\u2005V vs SCE for the reversible RuII/RuIII couple. This potential is anodically shifted by only 20\u2005mV relative to the [Ru(Cl)(bpy)(tpy)]+ complex (bpy)(tpy\u2013tpy)]Uiso(H) = 1.2Ueq(C). Each atom in the anion was modeled in two positions, with site occupancies tied to 1.0. A total of 48 temperature-factor restraints were used to force convergence. The SQUEEZE routine in PLATON  I. DOI: 10.1107/S2056989015014632/pk2553Isup2.hklStructure factors: contains datablock(s) I. DOI: 1416756CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by N\u2013H\u22efN 11H9N5OS2, a 1-thio\u00adphen-2-yl\u00admethyl\u00adene\u00adamino\u00adpyrimidine derivative, displays an essentially planar C\u2014NH2 group. The conformation across the N=C bond linking the pyrimidine and thienyl groups is E. The pyrimidine and thienyl ring systems subtend an inter-planar angle of 42.72\u2005(5)\u00b0. In the crystal, mol\u00adecules are linked by N\u2013H\u22efNnitrile and N\u2013H\u22efO=C hydrogen bonds, forming chains parallel to the b axis.The title compound, C Many drugs, such as 5-fluoro\u00aduracil, containing a pyrimidine moiety have been developed and used as anti\u00adcancer agents. It is difficult to find a general method for the introduction of specific substituents into the pyrimidine nucleus directly, and thus many synthetic methods have been developed for the construction of pyrimidine rings bearing potential functional groups \u2005\u00c5. Both ring systems are, as expected, planar (r.m.s. deviations are 0.017\u2005\u00c5 for the pyrimidine and 0.001\u2005\u00c5 for the thienyl ring). Atom N2 lies 0.189\u2005(2)\u2005\u00c5 out of the pyrimidine plane; all other immediate substituent atoms lie effectively in the ring plane. Carbon atom C7 of the thio\u00admethyl group is rotated slightly out of the ring plane, with torsion angle N3\u2014C4\u2014S1\u2014C7 being \u22126.30\u2005(10)\u00b0. The inter-planar angle between the rings is 42.72\u2005(5)\u00b0; the relative orientation is influenced by the torsion angles C6\u2014N1\u2014N2\u2014C10 = \u221251.78\u2005(13), N1\u2014N2\u2014C10\u2014C11 = 174.68\u2005(9) and N2\u2014C10\u2014C11\u2014S12 = 5.22\u2005(15)\u00b0. The NH2 group is planar; the nitro\u00adgen atom lies only 0.048\u2005(9)\u2005\u00c5 out of the plane of its substituents. The intra\u00admolecular contact H041\u22efN2 = 2.22\u2005(2)\u2005\u00c5 may be construed as a hydrogen bond, although the angle at the H atom is necessarily narrow at 108.4\u2005(14) \u00b0 \u2005\u00c5 and H042\u22efO1 2.14\u2005(2)\u2005\u00c5  Table\u00a01.A search of the Cambridge Structural Database  was added to a stirred solution of 1-cyano\u00adacetyl-4-thio\u00adphene\u00admethyl\u00adidenesemicarbazide (0.01\u2005mol) in dry dioxane (50\u2005ml), containing potassium hydroxide (0.01\u2005mol), at room temperature. The solution was stirred overnight at room temperature, after which a colourless solid product was collected by filtration and crystallized from ethanol (m.p. 541\u2013542\u2005K), giving colourless block-like crystals.Dimethyl Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The methyl group was refined as an idealized rigid group, allowed to rotate but not to tip.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901501885X/su5217sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901501885X/su5217Isup2.hklStructure factors: contains datablock(s) I. DOI: 1430030CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the mean plane of the benzene and piperidine rings is 89.03\u2005(3)\u00b0. In the crystal structure, inversion dimers are formed via N\u2014H\u22efCl hydrogen-bond inter\u00adactions, resulting in chains parallel to the [001] direction. The benzene rings within the chains show \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distances of 3.801\u2005(3)\u2005\u00c5] and neighbouring chains inter\u00adact via N\u2014H\u22efO hydrogen bonds.In the title complex, [PtCl Then, in the reaction solution, the cis complex converts into the trans complex and the thermodynamics of this conversion are currently under investigation by us.To explain this we suppose that et al. \u00b0]. The piperidine ring adopts the usual chair conformation, with the N2\u2014Pt1 bond in the equatorial position. The piperidine ring is oriented nearly perpendicular to the coordination plane of the PtII atom, thereby reducing the van der Waals repulsion; the dihedral angle between the least-squares mean planes through the piperdine ring and the four atoms coordinated to the Pt atom is 89.6\u2005(2)\u00b0. One short intra\u00admolecular contact is observed, i.e. H7B\u22efCl8 = 2.83\u2005\u00c5. The mean planes through the piperidine ring and the benzene ring make a dihedral angle of 89.0\u2005(3)\u00b0. The dihedral angle between the mean planes of the nitro substituent and the benzene ring is 16.6\u2005(3)\u00b0.The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01via N\u2014H\u22efCl inter\u00adactions between the aniline N atom and both Cl atoms, resulting in chains of mol\u00adecules along the [001] direction \u2005\u00c5; Cg is the centroid of the C11\u2013C16 ring; symmetry code: (iv) \u2212x, y, \u2212z\u00a0+\u00a0via N\u2014H\u22efO hydrogen bonds between the piperidine N atom and a nitro O atom , with the remaining 239 structures showing a trans coordination. There is no difference in the Pt\u2014Cl distances between both configurations. The average Pt\u2014Cl distances are 2.300\u2005(15) and 2.299\u2005(12)\u2005\u00c5 for the cis and trans arrangements, respectively, and correspond to the observed distances of 2.3039\u2005(11) and 2.2917\u2005(12)\u2005\u00c5 for Pt1\u2014Cl8 and Pt1\u2014Cl9, respectively.A search of the Cambridge Structural Database ] , prepared according to the synthetic procedure of Da et al. (2001p-nitro\u00adaniline (1\u2005mmol) in ethanol (10\u2005ml) was added gradually while stirring at 413\u2013318\u2005K. After 1\u2005h, a brown powder appeared and the reaction mixture was then stirred further for 24\u2005h until all the precipitate was completely dissolved. The solvent was removed in vacuo to give a brown\u2013yellow product. The product was washed consecutively with a 0.1 M HCl solution (2 \u00d7 2\u2005ml), warm water (2 \u00d7 2\u2005ml) and diethyl ether (2 \u00d7 2\u2005ml). The yield was 80%. Single crystals suitable for X-ray determination were obtained by slow evaporation within 12\u2005h from an acetone solution at room temperature. IR : 3199, 3113 (\u03bdNH); 3070, 2927, 2862 (\u03bdCH); 1596, 1525, 1479 (\u03bdC=C arom); 1342, 1325 (\u03bdNO); 1H NMR : \u03b4 8.21 , 7.47 , 5.49 , 3.66 , 3.26 , 2.99  = 13.0\u2005Hz, C510HNH), 1.69\u20131.43 . 13C{1H} NMR : \u03b4\u00a0149.6, 125.1, 124.2 (O2N6CH4NH2), 54.0, 27.2, 24.3 (5CH10NH).The starting complex K[PtCl al. 2001 with sliUiso(H) values assigned as 1.2Ueq of the parent atoms, with C\u2014H distances of 0.95 (aromatic) and 0.99\u2005\u00c5 (methyl\u00adene), and N\u2014H distances of 0.93 (NH) and 0.92\u2005\u00c5 (NH2).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015009196/rz5159sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009196/rz5159Isup2.hklStructure factors: contains datablock(s) I. DOI: 1400786CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(ar\u00adyl)-2,2,2-tri\u00adbromo\u00adacetamides show different weak inter\u00adactions in their crystal structures.Three  N-ar\u00adyl-2,2,2-tri\u00adbromo\u00adacetamides, namely, 2,2,2-tri\u00adbromo-N-(2-fluoro\u00adphen\u00adyl)\u00adacetamide, C8H5Br3FNO, (I), 2,2,2-tri\u00adbromo-N-[3-(tri\u00adfluoro\u00admethyl)\u00adphen\u00adyl]\u00adacetamide, C9H5Br3F3NO, (II) and 2,2,2-tri\u00adbromo-N-(4-fluoro\u00adphen\u00adyl)\u00adacetamide, C8H5Br3FNO, (III) were synthesized and their crystal structures were analysed. In the crystal structure of (I), C\u2014Br\u22ef\u03c0ar\u00adyl inter\u00adactions connect the mol\u00adecules into dimers, which in turn are connected via Br\u22efBr contacts [3.6519\u2005(12)\u2005\u00c5], leading to the formation of a one-dimensional ladder-type architecture. The crystal structure of (II) features chains linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. Two such chains are inter\u00adlinked to form ribbons through Br\u22efBr [3.6589\u2005(1)\u2005\u00c5] and Br\u22efF [3.0290\u2005(1)\u2005\u00c5] inter\u00adactions. C\u2014Br\u22ef\u03c0ar\u00adyl and C\u2014F\u22ef\u03c0ar\u00adyl inter\u00adactions between the ribbons extend the supra\u00admolecular architecture of (II) from one dimension to two. In (III), the mol\u00adecules are connected into R22(8) dimers via pairs of C\u2014H\u22efF inter\u00adactions and these dimers form ribbons through Br\u22efBr [3.5253\u2005(1)\u2005\u00c5] contacts. The ribbons are further inter\u00adlinked into columns via C\u2014Br\u22efO=C contacts, forming a two-dimensional architecture.Three  N-Ar\u00adyl-halo\u00adamides show a broad spectrum of pharmacological properties, including anti\u00adbacterial \u00adacetamide, (I)N-[3-(tri\u00adfluoro\u00admethyl)\u00adphen\u00adyl]\u00adacetamide, (II)N-(4-fluoro\u00adphen\u00adyl)\u00adacetamide, (III)The mol\u00adecular structures of (I)syn to the 2-fluoro substituent in the benzene ring, similar to that observed in the crystal structures of other ortho substituted compounds (see database survey). Contrast to the above, in (II)anti to the 3-CF3 substituent.In (I)In (I)The dihedral angle between the benzene ring and the C1\u2013N1\u2013C7(O)\u2013C8 segment in (II)The dihedral angle between the benzene ring and the C1\u2013N1\u2013C7(O)\u2013C8 segment in (III)ar\u00adyl inter\u00adactions \u00b0. The crystal structure of (I)In the crystal structure of (I)s Table\u00a04 connect re Fig.\u00a04. The Br1ar\u00adyl and C9\u2014F2\u22ef\u03c0ar\u00adyl inter\u00adactions between the ribbons extend the supra\u00admolecular architecture of (II)et al., 2012cis contact.The crystal structure of (II)via pairs of C3\u2014H3\u22efF1 inter\u00adactions ns Fig.\u00a07, formings Table\u00a06, formings Table\u00a06. The pacN-ar\u00adyl-2,2,2-tri\u00adbromo\u00adacetamides, namely, 2,2,2-tri\u00adbromo-N-phen\u00adyl\u00adacetamide, 2,2,2-tri\u00adbromo-N-(2/3/4-chloro\u00adphen\u00adyl)\u00adacetamides and 2,2,2-tri\u00adbromo-N-(2/3/4-methyl\u00adphen\u00adyl)\u00adacetamides have been previously reported. Comparison of the crystal systems of these series of compounds show that all the chloro-substituted compounds crystallize in the ortho\u00adrhom\u00adbic crystal system, while the methyl-substituted compounds crystallize in the monoclinic system (Table\u00a07i.e. (I)Seven m Table\u00a07. Howeversyn to the 2-fluoro substituent in the benzene ring, similar to that observed in the crystal structures of 2,2,2-tri\u00adbromo-N-(2-chloro\u00adphen\u00adyl)\u00adacetamide (Ia) \u00adacetamide (Ib) \u00adacetamide (Ia) \u00adacetamide (Ib)  intra\u00admolecular hydrogen bonds. Further, compounds (I)In (I)i.e. unsubstituted) compound is closer to those of chloro-substituted ones, thus the order is F < Cl(=H) < CH3.A comparison of the dihedral angle between the benzene ring and the C1\u2013N1\u2013C7(O)\u2013C8 segment in all of the compounds shows that the dihedral angles in the fluoro-substituted compounds are smaller than those observed in chloro-substituted ones, which in turn have smaller values than the methyl-substituted tri\u00adbromo\u00adacetamides Table\u00a07. The diha)] reported in the literature feature strong N\u2014H\u22efO hydrogen bonds leading into C(4) chains forming a one-dimensional architecture. Compound (Ia) (2-chloro derivative) does not exhibit any conventional inter\u00admolecular inter\u00adactions and therefore exhibits a zero-dimensional supra\u00admolecular architecture. However, the packing of mol\u00adecules in the three structures reported here are very different and are controlled by inter\u00adactions mainly involving the halogen atoms.The crystal structures of all of the seven compounds [except  = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0810.1107/S2056989015015248/hb7472sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989015015248/hb7472Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015248/hb7472IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015015248/hb7472IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1064065, 1419188, 1419189CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In membrane proteins, proline-mediated helix kinks are indispensable for the tight packing of transmembrane (TM) helices. However, kinks invariably affect numerous interhelical interactions, questioning the acceptance of proline substitutions and evolutionary origin of kinks. Here, we present the structural and thermodynamic basis of proline-induced integrin \u03b1IIb\u03b23 TM complex stabilization to understand the introduction of proline kinks in membrane proteins. In phospholipid bicelles, the A711P substitution in the center of the \u03b23 TM helix changes the direction of adjacent helix segments to form a 35\u2009\u00b1\u20092\u00b0 angle and predominantly repacks the segment in the inner membrane leaflet due to a swivel movement. This swivel repacks hydrophobic and electrostatic interhelical contacts within intracellular lipids, resulting in an overall TM complex stabilization of \u22120.82\u2009\u00b1\u20090.01\u2009kcal/mol. Thus, proline substitutions can directly stabilize membrane proteins and such substitutions are proposed to follow the structural template of integrin \u03b1IIb\u03b23(A711P). In the evolution of globular proteins, structural complexity and functionality can be increased by combining independently folding protein domains13456Indirect support for this hypothesis is abundant. Inspection of membrane protein structures reveals that helix kinks are frequently centered around proline residues 4689. Eve468TM, of \u22124.84\u2009\u00b1\u20090.01\u2009kcal/mol  and \u03b23(W715), which are located at the N- and C-helix termini, and by detecting NOEs to the aromatic ring of \u03b1IIb(F993) in fractionally deuterated samples (21To understand the basis of \u03b23(A711P), we determined the structure of the \u03b1IIb\u03b23(A711P) TM complex in isotropic phospholipid bicelles by multidimensional heteronuclear NMR spectroscopy. In the structure determination of the wild-type \u03b1IIb\u03b23 TM complex, we had used selectively methyl-labeled protein and deuterated lipids to obtain interhelical NOE distance restraintsH\u03b1 pairs , albeit  samples . Membranamples 21.15N chemical shift differences between \u03b1IIb when complexed with either \u03b23 or \u03b23(A711P) illustrated that structural changes predominantly took place for IMC residues and residues that pack near the mutation site  \u2212 (\u0394G\u00b0\u03b1IIb\u03b23(A711P),mutant \u2212\u0394G\u00b0\u03b1IIb\u03b23(A711P)) was quantified to compare the disturbance created by a mutation relative to its respective \u03b1IIb\u03b23 and \u03b1IIb\u03b23(A711P) reference structure. In accordance with largely invariant OMC interactions, \u0394\u0394G\u00b0,\u2032 was small for \u03b1IIb(G972A) with 0.16\u2009\u00b1\u20090.03\u2009kcal/mol  and \u03b1IIb\u03b23 TM complexes. Specifically, \u0394\u0394G\u00b0,\u2032\u2009=\u2009, prolines in membrane protein structures are frequently encountered near the center of TM helices422TM must be balanced with the affinity of intra- and extracellular receptor agonists and with the stability of the inactive versus the active ectodomains15\u03a4\u039c came at the expense of \u03b1IIb(R995)-\u03b23(D723) destabilization. This interaction is disrupted during talin-mediated integrin activationThe alternative to maintaining interhelical contacts near the proline kink would be to preserve interactions at the TM helix termini. When inspecting this possibility for \u03b1IIb\u03b23(A711P), it is apparent that mostly \u03b1IIb(R995)-\u03b23(D723) benefits whereas packing on \u03b23(G708) and \u03b1IIb(G976) would be less intimate . This mo7-glucose, 99% 15ND4Cl and 99% D2O. A fractionally deuterated 2H/13C/15N-\u03b1IIb(A963C)\u2013\u03b23(G690C/A711P) sample was prepared by growing E. coli cells in 60% D2O using protonated precursors. Freeze-dried peptide was reconstituted in 320 \u03bcL of 350\u2009mM 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC), 105\u2009mM 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 6% D2O, 0.02% w/v NaN3 buffered by either 25\u2009mM NaH2PO4/Na2HPO4, pH 7.4 or 25\u2009mM HEPES\u00b7NaOH, pH 7.4 for a final concentration of 0.8\u2009mM and bicelle q-factor of 0.3.The disulfide-linked \u03b1IIb(A963C)\u2013\u03b23(G690C/A711P) dimer was prepared applying published protocols1HN, 15N, 13C\u03b1, 13C\u03b2, and 13C\u2032 assignment of the \u03b1IIb\u03b23 TM complex and the \u03b23(A711P/K716A) TM segment152H/13C/15N-\u03b1IIb(A963C)\u20132H/13C/15N-\u03b23(G690C/A711P) were achieved employing HNCA, HNCO, HNCACB and NOESY-TROSY experiments. 15N-edited NOESY-TROSY experiments using 2H/15N-\u03b1IIb(A963C)\u2013\u03b23(G690C/A711P) or \u03b1IIb(A963C)\u20132H/15N-\u03b23(G690C/A711P) dimers were acquired with mixing times of 120, 150 and 175\u2009ms. Using [60% 2H]/13C/15N-\u03b1IIb(A963C)\u2013\u03b23(G690C/A711P), an aromatic 13C-edited NOESY-HSQC experiment (mixing time 150\u2009ms) was recorded. Sidechain assignments started again from the \u03b1IIb\u03b23 TM complex and were similar to the aforementioned NOESY spectra. In a general case, NOESY experiments for 2H/14N-\u03b1\u20131H/15-\u03b2 and 1H/15N-\u03b1\u20132H/14-\u03b2 can establish sidechain assignments in combination with standard experiments. Sidechain and NOE assignments were carried out manually using the program CARA. H-N residual dipolar couplings (RDC) were measured twice in compressed polyacrylamide gels  using 2H/15N-\u03b1IIb(A963C)\u20132H/15N-\u03b23(G690C/A711P) dimerStarting from the 15N, 13C\u03b1, 13C\u03b2, and 13C\u2032 chemical shift patterns\u03b1-C\u2032, N-C\u2032 RDCs measured for these monomers to further restrict the individual \u03b1IIb and \u03b23(A711P) backbone conformations. An employed torsion angle potential of mean force1 angles detected in the monomeric \u03b1IIb and \u03b23(A711P/K716A) TM segments, which mostly corresponded to their default values. Moreover, the sidechains of \u03b1IIb(Phe992) and \u03b23(Lys716) were adjusted to snorkel. Aside from standard force field terms for covalent geometry  and nonbonded contacts , dihedral angle restraints were implemented using quadratic square-well potentials. In addition, a backbone-backbone hydrogen-bonding potential was employed1D). The final values for the force constants of the different terms in the simulated annealing target function were as previously describedStructure calculations were carried out by simulated annealing, starting at 3000\u2009K using the program XPLOR-NIHsn-glycero-3-phosphocholine (DHPC), 17\u2009mM 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), 25\u2009mM NaH2PO4/Na2HPO4 pH 7.4 at 28\u2009\u00b0C. Prior to data analysis, the measurements were corrected for the heat of dilutions of the \u03b1IIb and \u03b23 peptides. The \u03b1IIb\u03b23 complex stoichiometry was fixed at 1:1XY were calculated from the measured heat changes, \u03b4Hi, as described previouslyITC measurements of the peptides listed in How to cite this article: Schmidt, T. et al. Structural and thermodynamic basis of proline-induced transmembrane complex stabilization. Sci. Rep.6, 29809; doi: 10.1038/srep29809 (2016)."}
{"text": "E conformation about the azo\u00adbenzene linkage and the benzene rings are almost coplanar to one another [dihedral angle = 1.36\u2005(7)\u00b0]. In the crystal, a combination of O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions leads to the formation of slabs parallel to (001).The title compound has an  16H14N2O3, has an E conformation about the azo\u00adbenzene [\u2014N=N\u2013 = 1.2481\u2005(16)\u2005\u00c5] linkage. The benzene rings are almost coplanar [dihedral angle = 1.36\u2005(7)\u00b0]. The O atoms of the carb\u00adoxy\u00adlic acid group are disordered over two sets of sites and were refined with an occupancy ratio of 0.5:0.5. The two disordered components of the carb\u00adoxy\u00adlic acid group make dihedral angles of 1.5\u2005(14) and 3.8\u2005(12)\u00b0 with the benzene ring to which they are attached. In the crystal, mol\u00adecules are linked via pairs of O\u2014H\u22efO hydrogen bonds, forming inversion dimers. The dimers are connected via C\u2014H\u22efO hydrogen bonds, forming ribbons lying parallel to [120]. These ribbons are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming slabs parallel to (001).The title compound, C Hence, liquid crystallinity may be induced by the formation of hydrogen-bonded dimers. A number of liquid crystal (LC) systems containing hydrogen bonds that function between identical mol\u00adecules have been reported  linkage, the length of the N1\u2014N2 bond is 1.2481\u2005(16)\u2005\u00c5 and the torsion angle for the azo unit (C7\u2014N1=N2\u2014C10) is 179.99\u2005(10)\u00b0, which is comparable with the values of ca \u00b1180\u00b0 observed in 4,4-azinodi\u00adbenzoic acid -ethyl-4-{[4-(deca\u00adnoxl\u00adoxy)phen\u00adyl]diazenly} benzoate -2-[4-(but-3-en-1-yl\u00adoxy)phen\u00adyl]-diazen-1-yl}benzoic acid, , as shown in Fig.\u00a03In the crystal, mol\u00adecules are linked s Table\u00a01. The dimet al., 2012. The terminal double bonds-containing azo\u00adbenzene compound was hydrolysed under basic conditions to yield the title compound. Red plate-like crystals were obtained by crystallization from an ethanol\u2013ethyl acetate mixture (1:1); m.p. 494\u2005K. 1H NMR (CDCl3): \u03b4 8.18 , 7.94 , 7.93 , 7.05 , 6.04 , 5.45 , 5.31 , 4.60 .The title compound was synthesized by a literature procedure (Rahman Uiso(H) = 1.5 Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model: C\u2014H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.2Ueq(C). Two outlier reflections, 341 and 309, were omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814023745/su2790sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023745/su2790Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814023745/su2790Isup3.cmlSupporting information file. DOI: 1031374CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 contacts, resulting in a three-dimensional supra\u00admolecular structure.The title spiro-compound bears  17H18O3, the two non-spiro C atoms of the cyclo\u00adpropane ring bear a formyl and a phenyl substituent which are trans-oriented. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 contacts resulting in a three-dimensional supra\u00admolecular structure.In the title compound, C The angles in the three-membered ring range from 58.80\u2005(13)\u00b0 (C2\u2014C4\u2014C3) to 61.67\u2005(13)\u00b0 (C3\u2014C2\u2014C4) being close to the ideal value of 60\u00b0 for such a ring. The six-membered ring containing the spiro atom C4 and ring atoms C5\u2013C9 adopts a chair conformation with a puckering amplitude Q of 0.491\u2005(2)\u2005\u00c5 and \u03b8 = 16.8\u2005(2)\u00b0, which indicates a slight deviation from an ideal chair conformation with \u03b8 = 0\u00b0. The plane of the central cyclo\u00adpropane ring forms dihedral angles of 66.89\u2005(16) and 89.33\u2005(16)\u00b0, respectively, with the plane of the phenyl ring and the mean plane of the cyclo\u00adhexane ring [maximum deviation from this plane is 0.272\u2005(2)\u2005\u00c5 for atom C7]. The latter two planes form a dihedral angle of 64.15\u2005(10)\u00b0. The plane of the formyl group, consisting of atoms C1, H1 and O1, is almost normal to the cyclo\u00adpropane ring with a dihedral angle of 81.3\u2005(3)\u00b0.The mol\u00adecular structure of the title compound is depicted in Fig.\u00a01B\u22efO2 contacts (red dotted lines) which are further linked to double strands along the 21-screw axes along [100] by C3\u2014H3\u22efO1 contacts (blue dotted lines). The remaining C\u2014H\u22efO as well as the C\u2014H\u22ef\u03c0 inter\u00adactions are displayed in Fig.\u00a03B\u22efO3 contacts (green dotted lines). These strands are linked by two different C\u2014H\u22ef\u03c0 contacts (Table\u00a01Cg is the centroid of this ring). Along [100] the strands are linked by C12\u2014H12\u22efiCgv contacts (orange dotted lines) while along [001] the links are established by C17\u2014H17B\u22efCgv inter\u00adactions (violet dotted lines) enclosing angles between the C\u2014H bond and the plane of the \u03c0-system of ca 39\u00b0 and 75\u00b0 respectively. As a result of these inter\u00adactions, a three-dimensional supra\u00admolecular structure is formed.The crystal packing of the title compound shows weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions Table\u00a01 and 3 \u25b8.et al., 1998trans-1,2-bis\u00ad(meth\u00adoxy\u00adcarbon\u00adyl)-6,6-di\u00admethyl\u00adspiro\u00ad(2.5)octane-4,8-dione -1,1-dichloro-6,6-dimethyl-2-[(1\u2032S*)-1\u2032-nitro\u00adeth\u00adyl]spiro\u00ad[2.5]octane-4,8-dione octane 1,4-dioxane solvate -5-benzyl-2,2,3-trimethyl-4-oxo-1-[(E)-3-phenyl\u00adallyl\u00adidene]-imidazolidin-1-ium hexa\u00adfluoro\u00adphosphate  and phenyl\u00adiodo\u00adnium-4,4-di\u00admethyl\u00adcyclo\u00adhexane-2,6-dione  in aceto\u00adnitrile (5\u2005ml). After 24\u2005h stirring at ambient temperature, water (10\u2005ml) was added. The aqueous phase was extracted with CH2Cl2 (15\u2005ml). The organic layers were combined, washed with brine, and dried over MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by column chromatography (n-penta\u00adne/Et2O: 7/3 and 6/4) to give the title compound  as colourless crystals (m.p. 397\u2013399\u2005K).A 10\u2005ml round-bottomed flask equipped with a magnetic stirring bar was charged with a solution of the (Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate along the C\u2014C bonds to best fit the experimental electron density. As a result of the absence of anomalous scatterers and high angle data, the Flack test results can be considered meaningless. The synthesis resulted in a racemic mixture, hence the structure was refined as an inversion twin.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901600164X/su5275sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901600164X/su5275Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600164X/su5275Isup3.cmlSupporting information file. DOI: 1450224CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "If Mo\u2014Mo bonds are ignored, each Mo atom can be considered as six-coordinated in a distorted octa\u00adhedral geometry. The Mo\u2014Mo distance of 2.6880\u2005(5)\u2005\u00c5 for two the Mo atoms bridged by the acetate ligand is shorter than the other two Mo\u2014Mo distances [2.7490\u2005(5) and 2.7566\u2005(5)\u2005\u00c5]. One ethyl group is disordered between two conformations in a 0.65\u2005(3):0.35\u2005(3) ratio. In the crystal, weak C\u2014H\u22efO inter\u00adactions link the trinuclear mol\u00adecules related by translation in [100] into chains. The crystal packing exhibits short inter\u00admolecular S\u22efS contacts of 3.1886\u2005(13)\u2005\u00c5. In other words, in this crystal packing, a supramolecular structure is constructed by the C\u2014H\u22efO and S\u22efS interactions.In the title compound, [Mo DOI: 10.1107/S1600536814012501/cv5459Isup2.hklStructure factors: contains datablock(s) I. DOI: 1005735CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The least-squares planes through the two aromatic ring systems make an angle of 47.3\u2005(3)\u00b0 for (I) and 38.6\u2005(2)\u00b0 for (II). Both structures show disorder for the PtCl2 fragment, in the case of (I) even further extended towards the CH2\u2014CH=CH2 ligand. An intra\u00admolecular C\u2014H\u22efCl hydrogen bond occurs in (I). In the crystal packing of (I), which is dominated by N\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions, a partially occupied water mol\u00adecule is observed on a twofold rotation axis with a refined site occupancy of 0.10\u2005(1). A C\u2014H\u22ef\u03c0 inter\u00adaction is also present. In (II), inversion dimers form chains along the b-axis direction by N\u2014H\u22efO hydrogen bonds.In the title complexes,  In both complexes, the Cl atoms are trans with respect to each other 2CH2=CH\u2014CH2 fragment is disordered over two positions [population parameters 0.679\u2005(8) and 0.321\u2005(8)], while in (II)2 fragment is disordered over two positions [population parameters 0.872\u2005(6) and 0.128\u2005(6)]. The angles between the best planes through the two aromatic rings are 47.3\u2005(3) and 38.6\u2005(2)\u00b0 for (I)A\u22efCl9 distance of 2.73\u2005\u00c5. In (I)A\u22efCl9.The complexes crystallize in different space groups, er Fig.\u00a01. The eugThe crystal packing of (I)AB\u22efO28i hydrogen bonds are further linked into chains in the b-axis direction by N2\u2014H2AA\u22ef hydrogen bonds .The crystal packing of (II)B\u22efCg1iii, H27B\u22efCg1iii = 2.72\u2005\u00c5; Cg1 is the centroid of the C20-C25 ring; symmetry code: (iii) \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0No \u03c0\u2013\u03c0 inter\u00adactions are observed in the packing of either structure. For (I)B) due to the disorder from the average Pt\u2014N distance of 2.09\u2005(5)\u2005\u00c5 for Pt\u2014NH2\u2014phenyl fragments present in the Cambridge Structural Database  and 2.305\u2005(2)\u2005\u00c5 and agree well with the average Pt\u2014Cl distance of 2.32\u2005(3)\u2005\u00c5 for trans complexes present in the CSD. One Pt1B\u2014Cl distance [2.151\u2005(2)\u2005\u00c5] deviates significantly from this average.The Pt\u2014N distances in (I)2 and C=C shows 11 hits. As fourth ligand we notice an additional Cl atom  or C atom (two hits) or O atom (one hit). In the complex [PtCl(methyl\u00adeugenol)(o-toluidine)] A search in the CSD for Pt complexes with Pt coordinated by Cl, NH3]:Synthesis of K[Pt(Alkeug)Cl3]  were synthesized following the protocol of Da and coworkers Cl2(Alkeug)(C6H6NCl)]:Synthesis of trans-[PtClv/v) was added to a mixture of 1.0\u2005mmol [K[Pt(Alkeug)Cl3] and 10\u2005mL acetone/ethanol (1:1 v/v). After two\u2005h stirring, a white precipitate of KCl was separated out. The remaining solution was stirred for two\u2005h at room temperature to obtain a yellow precipitate, which was collected by filtration, washed with ethanol and diethyl ether and dried in vacuum. The obtained crystals are soluble in chloro\u00adform and acetone, slightly soluble in ethanol and insoluble in water. The yield was 70\u201380%. Single crystals suitable for X-ray investigation were obtained by slow evaporation from a chloro\u00adform/ethanol (1:2 v/v) solution at room temperature.A solution of 127.0\u2005mg (1.0\u2005mmol) p-chloro\u00adaniline in 10\u2005mL acetone/ethanol (1:1 2(Meteug)(C6H6NCl)] (I)Data for  (II)Data for  and refined with constraints for the bond lengths present in this fragment. Refinement of the population parameter of oxygen atom O34  converged to 0.10\u2005(1). Water H atoms were not located.In (I)2 fragment is disordered over two positions [population parameters 0.872\u2005(6) and 0.128\u2005(6)].In (II)Uiso(H) values assigned as 1.2Ueq of the parent atoms (1.5 times for methyl groups), with C\u2014H distances of 0.95 (aromatic and =CH2), 0.98 (CH3), 0.99 (CH2) and 1.00\u2005\u00c5 (CH), and N\u2014H distances of 0.91\u2005\u00c5 (NH2). Enhanced rigid bond restraints were used for the anisotropic temperature factors of the non-H atoms. In the final cycles of refinement, 7 and 15 outliers were omitted for (I)All H atoms were placed in idealized positions and refined in riding mode, with 10.1107/S2056989016008872/rz5189sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989016008872/rz5189Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016008872/rz5189IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1483067, 1483066CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The complexes each form tetrahedral C 2(C8H11BrO3)(CO)6], (1), and [Co2(C12H16Br2O4)(CO)6], (2), result from the replacement of two carbonyl ligands from dicobalt octa\u00adcarbonyl by the alkynes 4-hy\u00addroxy\u00adbut-2-ynyl 2-bromo-2-methyl\u00adpropano\u00adate and but-2-yne-1,4-diyl bis\u00ad(2-bromo-2-methyl\u00adpropano\u00adate), respectively. Both mol\u00adecules have classic tetra\u00adhedral C2Co2 cluster cores with the CoII atoms in a highly distorted octa\u00adhedral coordination geometry. The alkyne ligands both adopt a cis-bent conformation on coordination. In the crystal structure of (1), classical O\u2014H\u22efO and non-classical C\u2014H\u22efO contacts form inversion dimers. These combine with weak O\u22efO and Br\u22efO contacts to stack the mol\u00adecules into inter\u00adconnected columns along the b-axis direction. C\u2014H\u22efO and C\u2014H\u22efBr contacts stabilize the packing for (2), and a weak Br\u22efO contact is also observed. Inter\u00adconnected columns of mol\u00adecules again form along the b-axis direction.The title compounds, [Co The two carbonyl groups in (2) each lie on the same side of the mol\u00adecule, with the 2-bromo-2-methyl\u00adpropano\u00adate units arranged symmetrically with respect to the central Cet al., 1995A\u22efO1 and C8\u2014H8A\u22efO12 hydrogen bonds  and Br1\u22efO1  contacts stack the mol\u00adecules into inter\u00adconnected columns along the b-axis direction , classical O1\u2014H1\u22efO3 hydrogen bonds Table\u00a03 are augmds Fig.\u00a03. These con Fig.\u00a04.B\u22efO2 and C8\u2013H8A\u22efO2 contacts \u2005\u00c5, symmetry operation x, \u22121\u00a0+\u00a0y, z], form b-axis direction , although in this mol\u00adecule no classical hydrogen bonds are possible. Bifurcated C3\u2014H3s Table\u00a04 produce gs Fig.\u00a05. The oth0] Fig.\u00a06. The neton Fig.\u00a07.et al., 2002The first structure, of dicobalt hexa\u00adcarbonyl di\u00adphenyl\u00adacetyl\u00adene, was reported using film data Sly, 1959. The cur2(CO)8 were allowed to react at room temperature for 1\u2005h in CH2Cl2 under nitro\u00adgen. The reaction mixtures were filtered through silica gel to remove any insol\u00aduble impurities and the filtrates taken to dryness in vacuo. The complexes were then purified by recrystallization from hexane at 273\u2005K. Yields were in the range 70\u201380%. Complexation was confirmed by the absence of a band at 1860\u2005cm\u22121 in the infrared spectrum, attributable to the \u03bc2 (bridging) carbonyl groups of the dicobalt octa\u00adcarbonyl starting material. In addition, a hypsochromic shift of approximately 30\u2005cm\u22121 of the remaining carbonyl stretching frequencies is seen, due to the decrease in electron density at the metal atoms upon coordination of these alkynes. Characteristic IR spectra were recorded for both products as follows: IR : (1): 3300 , \u03bd(C\u2261O) 2099, 2062, 2032, \u03bd(C=O) 1735; (2): \u03bd(C\u2261O) 2096, 2058, 2031, \u03bd(C=O) 1734.In typical preparations, 1:1 molar qu\u00adanti\u00adties of 4-hy\u00addroxy\u00adbut-2-ynyl 2-bromo-2-methyl\u00adpropano\u00adate for (1) or a 2:1 molar ratio of but-2-yne-1,4-diyl bis\u00ad(2-bromo-2-methyl\u00adpropano\u00adate) for (2) with Cod(C\u2014H) = 0.99\u2005\u00c5, Uiso = 1.2Ueq (C) for CH2, 0.98\u2005\u00c5, Uiso = 1.5Ueq (C) for CH3 atoms. In the final refinement, two reflections from the data for (2) with Fo << Fc were omitted from the refinement.All H atoms bound to carbon were refined using a riding model with 10.1107/S1600536814009659/hb0001sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S1600536814009659/hb00011sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814009659/hb00012sup3.hklStructure factors: contains datablock(s) 2. DOI: 1004257, 1004258CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The benzyl\u00adidine and benzoate rings are inclined to one another by 24.58\u2005(8)\u00b0, and the conformation about the C=N bond is E.The title  p-hy\u00addroxy Schiff base, C17H17NO4, was synthesized via the condensation reaction of benzocaine with vanillin. The benzyl\u00adidine and benzoate rings are inclined to one another by 24.58\u2005(8)\u00b0, and the conformation about the C=N bond is E. In the crystal, mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds, forming zigzag chains propagating along [010]. Adjacent chains are linked by C\u2014H\u22ef\u03c0 and weak offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.819\u2005(1)\u2005\u00c5], forming sheets parallel to (10-2).The title  The m-meth\u00adoxy group (O1/C13/C16) is slightly out of the plane of the benzene ring (C11\u2013C14/C20/C21) to which it is attached by 5.37\u2005(18)\u00b0, while the mean plane of the ethyl\u00adacetate group (O3/O17/C1/C2/C4) is inclined to the benzene ring (C5\u2013C8/C18/C19) to which it is attached by 10.23\u2005(11)\u00b0. This non-linearity is consistent for Schiff bases.The title Schiff base, (I)Cg1\u22efCg1i = 3.819\u2005(1)\u2005\u00c5, inter\u00adplanar distance = 3.672\u2005(2)\u2005\u00c5, slippage = 1.05\u2005\u00c5, Cg1 is the centroid of ring C5\u2013C8/C18/C19; symmetry code: (i) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01],In the crystal, mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds, forming zigzag chains propagating along [010]; see Table\u00a01para rather than the ortho position, this Schiff base cannot form the intra\u00admolecular C=N\u22efO\u2014H hydrogen bond responsible for keto\u2013enol tautomerism. However, the close proximity of the C=N and O\u2014H groups gives rise to the possibility that external stimulation of the material by heat or light may lead to the zwitterionic form. The potential for compound (I)The crystal structure analysis of compound (I)et al., 2016et al., 2010et al., 2012In the Cambridge Structural Database Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016008999/su5304sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989016008999/su5304Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016008999/su5304sup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016008999/su5304Isup4.cmlSupporting information file. DOI: 1483394CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angles between the benzo\u00adthia\u00adzole ring systems and the phenol rings are 4.1\u2005(4) and 5.8\u2005(4)\u00b0, indicating an almost planar geometry. Weak intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonds are observed. In the crystal, weak \u03c0\u2013\u03c0 inter\u00adactions between aromatic and thia\u00adzole rings [centroid\u2013centroid distances = 3.626\u2005(3) and 3.873\u2005(3)\u2005\u00c5] link the mol\u00adecules into a two-dimensional supra\u00admolecular network along the bc plane.In the title complex, [Cu(C DOI: 10.1107/S2056989015015303/bq2400Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015303/bq2400fig1.tif. DOI: Mol\u00adecular structure of the title complex, showing the atom-numbering scheme and 30% probability ellipsoids.Click here for additional data file.10.1107/S2056989015015303/bq2400fig2.tifvia . DOI: via C\u2014H\u22efO (black dashed lines) and \u03c0-\u03c0 (red) inter\u00adactions.Dimeric formation Click here for additional data file.10.1107/S2056989015015303/bq2400fig3.tif. DOI: Part of the crystal structure of the title complex, showing the 2-D network of mol\u00adecules linked by inter\u00admolecular C\u2014H\u22efO hydrogen bonds (black dashed lines) and \u03c0-\u03c0 inter\u00adactions (red).1419096CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing is stabilized  42H42N2P22+\u00b72Br\u2212\u00b72CH2Cl2, lies on a crystallographic twofold rotation axis. The 1,2-di\u00adamino\u00adcyclo\u00adhexane fragment has a chair conformation with two N atoms in a transoid conformation [N\u2014C\u2014C\u2014N = 163.4\u2005(2)\u00b0]. In the crystal, the cations are linked to the anions by N\u2014H\u22efBr and C\u2014H\u22efBr hydrogen bonds, forming a chain structure along the c axis. The di\u00adchloro\u00admethane mol\u00adecule takes part in the hydrogen-bond network through C\u2014H\u22ef\u03c0 and C\u2014H\u22efBr inter\u00adactions.The cation of the title solvated salt, C P,P,P-triaryl-P-amino\u00adphospho\u00adnium salts bearing a primary amino group are isolable inter\u00admediates in the Horner & Oediger \u00b0; symmetry code: (i) \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0The cation is situated on a crystallographic twofold rotation axis Fig.\u00a01. The 1,2trans-1,2-di\u00adamino\u00adcyclo\u00adhexane mol\u00adecule and the last is donated by the solvent di\u00adchloro\u00admethane mol\u00adecule  in 100\u2005ml of the same solvent. After four\u2005h of stirring at room temperature and the formation of white precipitate, a mixture of half an equivalent of (\u00b1)-trans-1,2-di\u00adamino\u00adcyclo\u00adhexane  and one equivalent of tri\u00adethyl\u00adamine  in 10\u2005ml of CH2Cl2 was added dropwise under stirring at 273\u2005K. The suspension was left under continuous stirring for 12\u2005h at room temperature. Then the reactant was extracted twice with 25\u2005ml of distilled water, and the organic phase was dried over MgSO4. All volatiles were eliminated under vacuum, and the resulting light-yellow solid was stirred with Et2O overnight. After filtration, 6.0\u2005g of the title compound was obtained as a white powder . Single crystals suitable for X-ray diffraction were grown by slow evaporation of a di\u00adchloro\u00admethane solution at room temperature.Under an NUiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically (C\u2014H = 0.93 or 0.97\u2005\u00c5) and constrained using the riding-model approximation with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016004576/is5441sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989016004576/is5441Isup2.hklStructure factors: contains datablock(s) I. DOI: 1469040CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ruthenocenecarbo\u00adnitrile mol\u00adecule exhibits mirror symmetry in the solid state. 5-C5H4C\u00a0N)(\u03b75-C5H5)], exhibits point group symmetry m, with the mirror plane bis\u00adecting the mol\u00adecule through the C\u00a0N substituent. The RuII atom is slightly shifted from the \u03b75-C5H4 centroid towards the C\u00a0N substituent. In the crystal, mol\u00adecules are arranged in columns parallel to [100]. One-dimensional inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [3.363\u2005(3)\u2005\u00c5] between the C\u00a0N carbon atom and one carbon of the cyclo\u00adpenta\u00addienyl ring of the overlaying mol\u00adecule are present.The mol\u00adecular structure of ruthenocenecarbo\u00adnitrile, [Ru(\u03b7 A synthesis for ferrocenecarbo\u00adnitrile has already been described in 1957 \u2005\u00c5]. Both cyclo\u00adpenta\u00addienyl rings adopt an ideally eclipsed conformation and are virtually oriented parallel towards each other, which is expressed by the bond angle at the RuII between the two centroids (= D), with D(C5H4)\u2014Ru1\u2014D(C5H5) = 178.87\u2005(1)\u00b0. However, the RuII atom is slightly shifted from the centre of the C5 ring to the nitrile-bonded C2 atom, which can be explained best by the significantly different Ru\u2014C bond lengths sp (ethyn\u00adyl)  as compared to (I)et al., 2008The ruthenocene backbone is hardly described in the literature. Reported derivatives contain et al., 2008et al., 2010et al., 1996et al., 2007et al., 2007Comparison of the C\u2014C [1.431\u2005(3)\u2005\u00c5] and the C\u00a0N distances [1.148\u2005(3)\u2005\u00c5] with the respective ferrocene carbo\u00adnitrile derivatives  solution were added in a single portion, and stirring was continued for additional 20\u2005min. Solid particles were removed by filtration and the filtrate was extracted with ethyl acetate (3 \u00d7 50\u2005ml). The combined organic layers were dried over MgSO4. All volatiles were removed under reduced pressure and the crude product was purified by flash chromatography on aluminum oxide using di\u00adchloro\u00admethane as eluent. Greenish crystals of (I)\u22121): \u03bd = 2226 , 2854 (s), 2925 (s), 3082 . 1H NMR : \u03b4 4.69 , 4.70 , 4.70 . 13C{1H} NMR : \u03b4 = 55.3 (Ci-C5H4), 72.4 (C5H4), 72.9 (C5H5), 73.5 (C5H4), 119.4 (CN). HRMS : C11H9NRu: m/z = 256.9792 .Formyl\u00adruthenocene was prepared according to a published procedure (Mueller-Westerhoff isoU(H) = 1.2Ueq(C) and a C\u2014H distance of 0.93\u2005\u00c5. Crystal data, data collection and structure refinement details are summarized in Table\u00a02C-bonded H atoms were placed in calculated positions and constrained to ride on their parent atoms, with 10.1107/S205698901500540X/wm5119sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901500540X/wm5119Isup2.hklStructure factors: contains datablock(s) I. DOI: 1054219CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Zn\u22efZn separation is 11.3893\u2005(14)\u2005\u00c5 and the ligands wrap around the two ZnII atoms, forming a triple helix as defined by the Zn\u2014N\u2014N\u2014Zn torsion angles of 104.05\u2005(18), 99.06\u2005(19) and 101.40\u2005(19)\u00b0. The Zn\u2014N(pyrid\u00adyl) distances in the octahedral ZnN6 coordination sphere are in the range 2.128\u2005(5)\u20132.190\u2005(5)\u2005\u00c5 and the Zn\u2014N(imine) distances are in the range 2.157\u2005(5)\u20132.277\u2005(5)\u2005\u00c5.The asymmetric unit of the title compound, [Zn DOI: 10.1107/S205698901502455X/fk2093Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502455X/fk2093fig1.tif. DOI: Mol\u00adecular structure of the title compound. Anisotropic displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.1443648CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The [Re6Se8]2+ cluster core displays a non-crystallographic center of symmetry and is bonded through the ReIII atoms to five tri\u00adethyl\u00adphosphane ligands and one p-toluene\u00adsulfonate ligand. One p-toluene\u00adsulfonate counter-ion and two di\u00adchloro\u00admethane solvent mol\u00adecules are also present in the asymmetric unit. One of the ethyl chains of one triethylphos\u00adphane ligand and one of the CH2Cl2 solvent molecules are disordered over two sets of sites . The Re\u2014O(sulfon\u00adate) bond length of 2.123\u2005(5)\u2005\u00c5 is similar to other Re\u2014O bond lengths of hexa\u00adnuclear rhenium chalcogenide clusters containing other O-donor ligands such as dimethyl sulfoxide (DMSO), di\u00admethyl\u00adformamide (DMF) and hydroxide.The title compound, [Re Later, Eremenko et al. (1993iPr)3)2(CO)(NO)(OTs)2] (OTs\u2212 = p-toluene\u00adsulfonate anion) which represented the first structural report of a rhenium complex containing tosyl\u00adate ligands. In the synthesis of octa\u00adhedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes  cluster complexes (C6H15P)5](C7H7O3S)\u00b72CH2Cl2 = 0.036wR(F2) = 0.097S = 1.0216405 reflections693 parametersH-atom parameters constrainedmax = 2.67 e \u00c5\u22123\u0394\u03c1min = \u22121.26 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: DIRDIF99  I, isu0804. DOI: 10.1107/S2056989015014334/pj2021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015014334/pj2021fig1.tif6 8 3 5 3 6 4 + . DOI: 6Se8(PEt3)5(O3SC6H4Me)]+ ion showing the atom labelling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 30% probability level. Hydrogen atoms omitted for clarity.Perspective view of the [Re1010097CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Each water mol\u00adecule is disordered over three sets of sites, with a refined occupancy ratio of 0.310\u2005(9):0.275\u2005(9):0.415\u2005(9) for one mol\u00adecule and 0.335\u2005(9):0.288\u2005(9):0.377\u2005(9) for the other mol\u00adecule. The MnII atoms exhibit a distorted octa\u00adhedral geometry, while the WV atoms adopt a distorted square-anti\u00adprismatic geometry. The MnII and WV atoms are linked alternatively through cyanide groups, forming a tetra\u00adnuclear 12-atom rhombic metallacycle. Adjacent metallacycles are further connected by \u03bc2-bridging cyanide anions, generating a 3,2-chain structure running parallel to [101]. Inter\u00adchain \u03c0\u2013\u03c0 inter\u00adactions are observed [centroid\u2013centroid distances = 3.763\u2005(3) and 3.620\u2005(2)\u2005\u00c5].The asymmetric unit of the title compound, {[Mn DOI: 10.1107/S1600536814007235/rz5113Isup2.hklStructure factors: contains datablock(s) I. DOI: 994877CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N2-amino group of the guanine residue exists in the cyclic amino\u00adglycoside form.Crystallographic analysis of a nucleoside analog of the 2\u2032-de\u00adoxy\u00adguanosine/abasic site cross-link is presented. This structure corroborates an earlier two-dimensional NMR analysis, concluding that the 2-de\u00adoxy\u00adribose unit attached at the exocyclic  R,4S,5R)-4-hy\u00addroxy-5-(hy\u00addroxy\u00admeth\u00adyl)tetra\u00adhydro\u00adfuran-2-yl]-2-{[-4-meth\u00adoxy-5-(meth\u00adoxy\u00admeth\u00adyl)tetra\u00adhydro\u00adfuran-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of mol\u00adecules A and B are linked by N\u2014H\u22efN and O\u2014H\u22efN hydrogen-bonding inter\u00adactions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O\u2014H\u22efO hydrogen bonds between the ribose moieties and numerous C\u2014H\u22efO inter\u00adactions to complete the three-dimensional structure.The title compound, 9-[(2 The disposition of these furan\u00adose rings relative to the purine rings can be described by the torsion angle C2\u2014N4\u2014C6\u2014O2, which is 70.9\u2005(3)\u00b0 in mol\u00adecule A and 61.7\u2005(3)\u00b0 in mol\u00adecule B. The furan\u00adose ring attached to the N5 position in mol\u00adecule A is again a half-chair, with the maximum deviation from planarity between C11A and C12A , while this furan\u00adose ring in mol\u00adecule B is an envelope with C11B at the flap . The disposition of these furan\u00adose rings relative to the purine rings can be described by the angle C1\u2014N5\u2014C11\u2014O5, which is \u221287.4\u2005(2)\u00b0 in mol\u00adecule A and \u221293.7\u2005(2)\u00b0 in mol\u00adecule B.The two independent mol\u00adecules  were dissolved in 0.8\u2005ml of a 3:1 mixture of DMSO and 25\u2005mM sodium phosphate buffer (pH 7.0) in a round-bottom flask. The flask was heated to 333\u2005K and the mixture stirred for 22\u2005h. The solvent removed in vacuo and the product purified by column chromatography on silica gel eluted with 0\u201315% methanol in di\u00adchloro\u00admethane  to yield 36\u2005mg (12% yield) of the title compound as a colorless oil. The precursor 3,5-bis-O-methyl-2-de\u00adoxy-d-ribo\u00adfuran\u00adose was synthesized according to previously reported procedures  and 3,5-bis-Uiso(H) = 1.2Ueq(C). Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901600517X/hb7568sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901600517X/hb7568Isup2.hklStructure factors: contains datablock(s) I. DOI: 1448235CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A stable oxopiperidinium trication salt was synthesized. In the crystal, N\u2014H\u22efCl, C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds link cations and anions into a three-dimensional network. 28H40N3O3+\u00b73Cl\u2212\u00b72H2O, the central heterocyclic ring adopts a sofa conformation, with the exocyclic N\u2014C bond in an equatorial orientation. The dihedral angles between the planar part of this heterocyclic ring and the two almost flat side-chain fragments, which include the aromatic ring and bridging atoms, are 28.8\u2005(1) and 41.1\u2005(1)\u00b0. Both di\u00adethyl\u00adaza\u00adniumyl substituents have a tetra\u00adhedral geometry, while the dihedral angles between the above-mentioned flat part of the aryl fragments and the imaginary planes drawn through atoms C\u2014N\u2014C of the di\u00adethyl\u00adaza\u00adniumyl substituents are 86.3\u2005(2) and 80.4\u2005(1)\u00b0, respectively. In the crystal, N\u2014H\u22efCl hydrogen bonds link the cations and anions into [100] chains. The chains are cross-linked by numerous C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions, generating a three-dimensional network. One of the chloride ions is disordered over two adjacent positions in a 0.895\u2005(4):0.105\u2005(4) ratio.In the trication of the title hydrated mol\u00adecular salt, C The dihedral angles between the flat part of the heterocycle  and the two almost planar fragments that include the phenyl-ring and the bridging atoms are 28.7\u2005(1) and 41.1\u2005(1)\u00b0 for (C7\u2013C13) and (C18\u2013C24), respectively. Such non-planarity might partly be caused by the presence of short intra\u00admolecular contacts H2AB\u22efH24A and H6AB\u22efH13A with distances 2.18 and 2.14\u2005\u00c5, respectively, which are shorter than the doubled van der Waals radius of the H atom -3,5-bis\u00ad[4-(di\u00adethyl\u00adamino)\u00adbenzyl\u00adidene[\u22121-methyl-4-piperidone was obtained according to a literature procedure  = k \u00d7 Ueq(C), where k = 1.2 for CH and CH2 and 1.5 for CH3 H atoms. All N-bound H atoms were located using difference Fourier maps, but in the final refinement their distances were constrained at 0.90\u2005\u00c5 (DFIX). H atoms of the two water mol\u00adecules were not localized properly, since they appeared to be disordered over several positions. These H atoms were therefore removed from the refinement, but they were still included in the resulting chemical formula. Atom Cl3 is disordered over two positions in a 0.895\u2005(4):0.105\u2005(4) ratio.Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989015020952/hb7503sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015020952/hb7503Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020952/hb7503Isup3.cmlSupporting information file. DOI: 1435161CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title aryl\u00adsulfonyl glycinyl hydrazone Schiff base compound crystallizes as a monohydrate. In the crystal, a series of O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds leads to the formation of corrugated sheets lying parallel to (100). 16H16ClN3O3S\u00b7H2O, is L-shaped being bent at the S atom; the S\u2014N\u2014C\u2014C torsion angle is 132.0\u2005(3)\u00b0. The central part of the mol\u00adecule, C\u2014C\u2014N\u2014N=C, is almost linear, with the C\u2014C\u2014N\u2014N and C\u2014N\u2014N=C torsion angles being \u2212174.1\u2005(2) and 176.0\u2005(2)\u00b0, respectively. The dihedral angle between the p-toluene\u00adsulfonyl ring and the S\u2014N\u2014C\u2014C(=O) segment is 67.5\u2005(4)\u00b0, while that between the two aromatic rings is 52.17\u2005(11)\u00b0. In the crystal, the water H atom is involved in O\u2014H\u22efO hydrogen bonds with a sulfonamide O atom and the carbonyl O atom. The water O atom is itself hydrogen bonded to both NH hydrogen atoms. These four hydrogen bonds lead to the formation of corrugated sheets lying parallel to (100). There are also weak C\u2014H\u22efO contacts present within the sheets.The mol\u00adecule of the title compound, C N-Acyl\u00adhydrazones containing a glycine residue have been investigated extensively in recent years for their biological and medical activities -amides \u2005\u00c5 indicates that the mol\u00adecule exists in the keto form in the solid state. The C9\u2014N3 bond length of 1.266\u2005(3)\u2005\u00c5 confirms its significant double-bond character. The N2\u2014N3 and C8\u2014N2 bond distances are 1.384\u2005(3) and 1.337\u2005(3)\u2005\u00c5, respectively, which indicate significant delocalization of the \u03c0-electron density over the hydrazone portion of the mol\u00adecule. The mol\u00adecule is bent at the S-atom with a S1\u2014N1\u2014C7\u2014C8 torsion angle of 132.0\u2005(2)\u00b0. The other central part of the mol\u00adecule is almost linear with the C7\u2014C8\u2014N2\u2014N3, C8\u2014N2\u2014N3\u2014C9 and N2\u2014N3\u2014C9\u2014C10 torsion angles being \u2212174.1\u2005(2), 176.0\u2005(2) and \u2212176.7\u2005(2)\u00b0, respectively. The orientation of the sulfonamide group with respect to the attached p-toluene\u00adsulfonyl ring (C1\u2013C6) is given by torsion angles C2\u2014C1\u2014S1\u2014N1 = \u221299.8\u2005(2)\u00b0 and C6\u2014C1\u2014S1\u2014N1 = 76.6\u2005(2)\u00b0, while that of the hydrazone group with the attached benzene ring (C10-C15) is given by torsion angles C11\u2014C10\u2014C9\u2014N3 = 9.9\u2005(4)\u00b0 and C15\u2014C10\u2014C9\u2014N3 = \u2212172.1\u2005(2)\u00b0. The dihedral angles between the mean plane of the central segment  and the benzene rings (C1\u2013C6 and C10\u2013C15) are 65.22\u2005(15) and 13.06\u2005(14)\u00b0, respectively. The two benzene rings are inclined to one another by 52.16\u2005(14)\u00b0.The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01In the crystal, the water O-atom, O4, shows bifurcated hydrogen bonding with the amino-H atom of the hydrazide segment (N2) and the sulfonamide-H atom (N1); see Table\u00a01viz. \u2013NH\u2013CH2\u2013C(=O)\u2013NH\u2013N=CH\u2013, yielded only one hit, namely N-(2-hy\u00addroxy-1-naphthyl\u00admethyl\u00adene)-N\u2032-(N-phenyl\u00adglyc\u00adyl)hydrazine  was added to glycine (0.02\u2005mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373\u2005K for 6\u2005h, then left overnight at room temperature, filtered and then treated with dilute hydro\u00adchloric acid. The solid N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycine (L1) obtained was crystallized from aqueous ethanol.The title compound was synthesized in a number of steps. Firstly L1 (0.02\u2005mol) dissolved in ethanol (30\u2005ml) and the mixture was refluxed. The reaction was monitored by TLC at regular inter\u00advals. After completion of the reaction, the reaction mixture was concentrated to remove excess ethanol. The product, N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycine ethyl ester (L2) obtained was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone.Sulfuric acid (0.5\u2005ml) was added to L2 (0.01\u2005mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10\u2005ml) in 30\u2005ml ethanol and the mixture was refluxed for 6\u2005h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycinyl hydrazide (L3).The pure L3 (0.01\u2005mol) and 3-chloro\u00adbenzaldehyde (0.01\u2005mol) in anhydrous methanol (30\u2005ml) and two drops of glacial acetic acid was refluxed for 8\u2005h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (457\u2013458\u2005K). The purity of the title compound was checked and characterized by its IR spectrum. The characteristic absorptions observed are 3253.9, 1680.0, 1597.1, 1334.7 and 1161.2\u2005cm\u22121 for the stretching bands of N\u2014H, C\u2014O, C\u2014N, S\u2014O asymmetric and S\u2014O symmetric, respectively.A mixture of Prism-like colourless single crystals of the title compound were grown from a DMF solution by slow evaporation of the solvent.Uiso(H) = 1.5Ueq(O). The Ueq of atoms O1 and O2 were restrained to approximate isotropic behaviour. The NH H atoms were also located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined using a riding model: C\u2014H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015008506/su5128sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015008506/su5128Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008506/su5128Isup3.cmlSupporting information file. DOI: 1062518CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound exists in the keto\u2013amine tautomeric form. In the crystal, supra\u00admolecular layers are formed by O\u2014H\u22efO hydrogen bonding. 12H16BrNO5 iminium\u00adyl}meth\u00adyl)-6-meth\u00adoxy\u00adbenzen-1-olate], C12H16BrNO5, is found in the keto\u2013amine tautomeric form, with an intra\u00admolecular iminium-N\u2014H\u22efO(phenolate) hydrogen bond and an E conformation about the C=N bond. Both gauche (two) and anti relationships are found for the methyl\u00adhydroxy groups. In the crystal, a supra\u00admolecular layer in the bc plane is formed via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) and charge-assisted hy\u00addroxy-O\u2014H\u22efO(phenolate) hydrogen-bonding inter\u00adactions; various C\u2014H\u22efO inter\u00adactions provide additional cohesion to the layers, which stack along the a axis with no directional inter\u00adactions between them. A Hirshfeld surface analysis confirms the lack of specific inter\u00adactions in the inter-layer region.In the solid state, the title compound, C Thus, various species have been studied for their anticancer potential, Database survey. The conformation about the iminium bond [1.295\u2005(4)\u2005\u00c5] is E and this residue is almost coplanar with the benzene ring, forming a C2\u2014C1\u2014C7\u2014N1 torsion angle of 1.9\u2005(4)\u00b0. This arrangement allows for the formation of a tight charge-assisted iminium-N\u2014H\u22efO(phenolate) hydrogen bond (Table\u00a01gauche relationships about the C8\u2014C9 and C8\u2014C11 bonds , and an anti relationship about the C8\u2014C10 bond . The meth\u00adoxy group is almost coplanar with the ring it is connected to, as seen in the value of the C12\u2014O5\u2014C3\u2014C2 torsion angle of 177.7\u2005(2)\u00b0.The mol\u00adecular structure of (I)d Table\u00a01. The cona). Within this framework are a number of C\u2014H\u22efO inter\u00adactions, i.e. imine-C7\u2014H\u22efO(phenolate), methyl\u00adene-C11\u2014H\u22efO(phenolate) and methyl\u00adene-C9\u2014H\u22efO(hy\u00addroxy) . In accord with the distance criteria in PLATON As anti\u00adcipated from the chemical composition of (I)y) Fig.\u00a02b. In acdnorm contact distance within the range of \u22120.67 to 1.31\u2005\u00c5 through calculation of the inter\u00adnal (di) and external (de) Hirshfeld surface distances to the nearest nucleus  over the range of \u22120.122 to 0.189 au. All Hirshfeld surface and fingerprints plots were generated using Crystal Explorer a), there are several red spots observed on the Hirshfeld surface of (I)deversus di , with the sum of contact distances being approximately 1.74\u2005\u00c5, signifying a strong inter\u00admolecular inter\u00adaction. Such strong inter\u00adactions constitute the second major contribution to the Hirshfeld surface, i.e. 25.4%, between the most prominent H\u22efH (38.2%) and other major contacts, like C\u22efH/H\u22efC (15.2%) and Br\u22efH/H\u22efBr (14.3%)  and 3(d), C\u22efH and Br\u22efH contacts are at distances greater than their respective van der Waals radii. Fig.\u00a05The Hirshfeld surface map provides a visual summary of any close contacts (shown as red) in contrast to relatively long contacts (shown as white and blue). As displayed in Fig.\u00a03i Fig.\u00a03b, with %) Fig.\u00a04. Their ca), shows that the electronegative sites are predominantly converged on O atoms and that, upon crystallization, the electronegative and electropositive sites are connected . It is noteworthy that despite bromine being an electrophilic element, it did not form a significant non-covalent inter\u00adaction with neighbouring mol\u00adecules in the inter-layer region where these atoms are directed. The closest contact in this region occurs with methyl-C\u22efH12Ci, at 3.12\u2005\u00c5, i.e beyond the sum of the respective van der Waals radii , exists in the keto\u2013amine tautomeric form and has been the subject of several investigations \u00b0 in (I)There are several closely related structures to (I)12H16BrNO5: C 44.48, H 3.70, N 1.99%; found: C 44.81, H 3.42, N 1.64%. IR (cm\u22121): 3330 (b) \u03bd, 1640 (s) \u03bd(C=N), 1528 (m) \u03bd(\u2014O\u2014C=C\u2014), 1066 (m) \u03bd(C\u2014O\u2014C). 1H NMR : \u03b4 8.35 , 7.01\u20137.10 , 6.83\u20136.89 , 5.06 , 3.95 , 3.37\u20133.75 .A solution of tris\u00ad(hy\u00addroxy\u00admeth\u00adyl)amino\u00admethane  was added to an ethano\u00adlic solution of 5-bromo-3-meth\u00adoxy-2-hy\u00addroxy\u00adbenzaldehyde  and refluxed for 2\u2005h. The solution was allowed to stand at room temperature, during which an orange solid formed. This was recrystallized by slow evaporation of its ethanol solution. Yield: 2.67 (80%). Yellow crystals. M.p. 465\u2013466\u2005K. Analysis calculated for CUiso(H) set at 1.2\u20131.5Ueq(C). The O- and N-bound H atoms were located from difference Fourier maps and refined with distance restraints O\u2014H = 0.82\u00b10.01\u2005\u00c5 and N\u2014H = 0.86\u00b10.01\u2005\u00c5, and with Uiso(H) set at 1.5Ueq(O) and Uiso(H) set at 1.2Ueq(N), respectively. Owing to poor agreement, several reflections, i.e. (\u22129 7 7), (\u221212 4 6), (\u221210 5 6) and (\u22123 3 2), were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016012159/hb7605sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016012159/hb7605Isup2.hklStructure factors: contains datablock(s) I. DOI: 1496206CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The complex exhibits twofold rotation symmetry, with the rotation axis bis\u00adecting the zinc cation. The structure is stabilized by weak inter\u00admolecular C\u2014H\u22efCl inter\u00adactions [C\u22efCl = 3.411\u2005(2) and 3.675\u2005(2)\u2005\u00c5], connecting neighbouring mol\u00adecules into layers perpendicular to the c axis.The structure of the title complex, [ZnCl DOI: 10.1107/S2056989015019143/zl2646Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015019143/zl2646fig1.tif11 9 3 2 2 x y -z . DOI: 11H9N3)2Cl2] with thermal ellipsoids plotted at the 30% probability level. Non-labelled atoms are created by the twofold symmetry axis .Mol\u00adecular structure of [Zn2Cl2] plotted down c, formed through weak C\u2013H\u22efCl inter\u00adactions.Two\u2013dimensional inter\u00adaction sheet of [Zn2Cl2] plotted down b axis, formed through weak C\u2013H\u22efCl inter\u00adactions.Two\u2013dimensional inter\u00adaction sheet of [Zn. H atoms are omitted for clarity.The arrangement of two-dimensional layers plotted down the 1430587CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Fe\u2014Fe), [Fe2(C8H8O)(CO)6], the diiron hexa\u00adcarbonyl moiety has a sawhorse arrangement, with the OC\u2014Fe\u2014Fe\u2014CO fragment forming the horizontal bar of the horse, and the other four carbonyl groups the legs. The Fe\u2014Fe distance is 2.795\u2005(2)\u2005\u00c5. Each Fe atom is also bonded to three C atoms of the cyclo\u00adocta\u00adtrienone ring. One Fe atom forms a \u03c3-bond with one ring C atom, with Fe\u2014C = 2.109\u2005(2)\u2005\u00c5, and also a metal\u2013olefin \u03c0-bond with two C atoms on the other side of the ring, with Fe\u2014C distances of 2.238\u2005(2) and 2.236\u2005(3)\u2005\u00c5. The second Fe atom forms a \u03b73-allyl bond with three other ring atoms, with Fe\u2014C bond lengths of 2.158\u2005(2), 2.062\u2005(2), and 2.123\u2005(3)\u2005\u00c5. Counting the \u03c0- and \u03c0-allyl inter\u00adactions as one bond, the coordinations of the Fe atoms can, respectively, be approximated as octa\u00adhedral and trigonal bipyramidal.In the title compound, bis\u00ad(tri\u00adcarbonyl\u00adiron)( I. DOI: 10.1107/S1600536814012690/pk2527Isup2.hklStructure factors: contains datablock(s) I. DOI: 1006076CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Ni\u2014N bond lengths to the pyridine rings are 2.1189\u2005(17) and 2.1241\u2005(17)\u2005\u00c5, whereas those to the thiocyanate anions are 2.0299\u2005(18) and 2.0359\u2005\u00c5. The Ni\u2014S bond lengths are 2.5357\u2005(6) and 2.5568\u2005(6)\u2005\u00c5. The Ni2+ cations are linked by N:S-bridging thio\u00adcyanate ligands into chains extending along [010]. The Ni\u22efNi distance within the chains is 5.5820\u2005(5)\u2005\u00c5. The asymmetric unit contains two Ni2+ cations of which one is located on a centre of inversion, whereas the second is located on a general position.In the title compound, [Ni(NCS) DOI: 10.1107/S1600536814009611/fk2081Isup2.hklStructure factors: contains datablock(s) I. DOI: 1000026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "However, their intrinsic differences remain unclear. In this study, we analyzed gene expression profiles of the two subsets using Illumina HiSeq 2000 Sequencer. We identified 1995 transcripts related to the activation of V\u03b31+ \u03b3\u03b4 T cells, and 2158 transcripts related to the activation of V\u03b34+ \u03b3\u03b4 T cells. We identified 24 transcripts differentially expressed between the two subsets in resting condition, and 20 after PMA/Ionomycin treatment. We found that both cell types maintained phenotypes producing IFN-\u03b3, TNF-\u03b1, TGF-\u03b2 and IL-10. However, V\u03b31+ \u03b3\u03b4 T cells produced more Th2 type cytokines, such as IL-4 and IL-5, while V\u03b34+ \u03b3\u03b4 T cells preferentially produced IL-17. Our study provides a comprehensive gene expression profile of mouse peripheral V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells that describes the inherent differences between them.Peripheral \u03b3\u03b4 T cells in mice are classified into two major subpopulations, V\u03b31 Although considerable progress has been made in characterizing their biological significance, much remains unknown. \u03b3\u03b4 T cells arise earlier than \u03b1\u03b2 T cells during thymic ontogeny, predominately at the early stage of fetal development + and V\u03b34+ \u03b3\u03b4 T cells, depending on their TCR expression + and V\u03b34+ \u03b3\u03b4 T cells perform distinct functions in many disease models. For example, V\u03b31+ \u03b3\u03b4 T cells produce IL-4 and IFN-\u03b3 in the liver + \u03b3\u03b4 T cells produce IFN-\u03b3 or IL-17 depending on the studied models + and V\u03b34+ \u03b3\u03b4 T cells function as oppositional pairs in diseases including coxsackievirus B3 infection + and V\u03b34+ \u03b3\u03b4 T cells remains unresolved, partly due to a lack of comprehensive analysis and comparison of gene expression. Although, gene-expression profiles of emergent \u03b3\u03b4TCR+ thymocytes have been reported + and V\u03b34+ \u03b3\u03b4 T cells functional differences has not been reported. This is likely due to the limited number of cells that can be obtained from healthy mice.\u03b3\u03b4 T cells exert diverse functions, however, individual subsets within the population appear to be biased toward specialized functions + and V\u03b34+ \u03b3\u03b4 T cells simultaneously from the same pool of mouse splenocytes. We comprehensively analyzed gene expression profiles using Illumina\u2019s sequencing technology. We identified 1995 transcripts related to the activation of V\u03b31+ \u03b3\u03b4 T cells, and 2158 transcripts were related to the activation of V\u03b34+ \u03b3\u03b4 T cells. Interestingly, only 24 transcripts were differentially expressed between two subsets in resting condition, and 20 transcripts after PMA/Ionomycin-induced activation. Both cells produced high levels of IFN-\u03b3, TNF-\u03b1, TGF-\u03b2 and IL-10. However, V\u03b31+ \u03b3\u03b4 T cells produced more Th2 type cytokines, while V\u03b34+ \u03b3\u03b4 T cells tended to produce more IL-17. These findings describe the inherent differences between V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells.In this study, we expanded V\u03b31Male C57BL/6J mice aged 6\u20138 weeks were purchased from the National Institute for Food and Drug Control. All mice were maintained under specific pathogen-free conditions in the Experimental Animal Center, Institute of Basic Medical Sciences, Chinese Academy of Medical Sciences. All animal experiments were approved by and performed in accordance with the guidelines of the international Agency for Research on Cancer\u2019s Animal Care and Use Committee and IBMS/PUMC\u2019s Animal Care and Use Committee.+ and V\u03b34+ \u03b3\u03b4 T cells were expanded from splenocytes as described previously 7 cells were eluted and added to the Ab-coated wells (4\u00d7106 cells/well) and cultured in RPMI 1640 medium (Gibco BRL) supplemented with 10% fetal calf serum and IL-2 (200 IU/ml). After 8 days of expansion, the proportion of \u03b3\u03b4 T cells reached approximately 80% as determined by Flow Cytometry.V\u03b317 V\u03b31+ and 1.2\u00d7107 V\u03b34+ \u03b3\u03b4 T cells were sorted by Flow Cytometric Cell Sorting (FACS) with PE conjugated anti-mouse TCR V\u03b31.1/Cr4 antibody  and APC conjugated anti-mouse TCR V\u03b32 antibody . The purity of sorted cells was more than 99%. 5\u00d7106 cells per well were seeded into 6-well culture plates at a concentration of 1\u00d7106/ml and rested overnight at 37\u00b0C in 5% CO2 in RPMI with 10% FCS. Cells were stimulated for 4 h with PBS or 20 ng/ml of PMA (Sigma) and 0.5\u00b5g/ml of Ionomycin (Sigma). Cells were washed with PBS and pelleted by centrifugation. Total RNA from each sample was extracted by Trizol reagent (Invitrogen) according to the manufacturer\u2019s instructions. The quality of total RNA from each sample was confirmed and comparable, based on results of Agilent Technologies 2100 Bioanalyzer.1.0\u00d710We prepared the Illumina libraries according to the manufacturer\u2019s instructions. Briefly, mRNAs were extracted from total RNA by mRNA enrichment kit  followed by fragmentation of mRNA into 250\u2013350 bp sizes. The first strand cDNAs were synthesized using reverse transcriptase and random primers. Second strand cDNAs were synthesized using DNA Polymerase I followed by the addition of a single A base at the ends for the ligation to the adapters. After purification, the final cDNA library was created by PCR. Finally, 400\u2013500 bp products were used for cluster generation, 36 bp single-end sequencing was performed using Illumina HiSeq 2000 Sequencer according to the manufacturer\u2019s instructions (Beijing Berry Genomics Co. Ltd. China). The RNA-Seq raw data files have been deposited in NCBI\u2019s Sequence Read Archive (SRA) and are accessible through SRA Series accession number SRP042029.We performed base calling using CASAVA 1.7 software (Illumina). Low quality and polluted adapter reads were filtered; clean reads were stored on fastq files. The sequence reads were aligned to the mouse genome (mm9), and gene expression was calculated by RPKM value. Differentially expressed transcripts were identified using General Chi-square test analysis. Q values were obtained by the \u201cBH\u201d method + and V\u03b34+ \u03b3\u03b4 T cells were selected for verification from biological replicates with real-time quantitative PCR. RNA was extracted as described above. 500 ng of total RNA was reverse transcribed using PrimeScript RT reagent Kit with gDNA Eraser (Takara Bio). Gene-specific primers are listed in  as described previously + and V\u03b34+ \u03b3\u03b4 T cells comprised approximately 35% and 25% respectively . \u03b3\u03b4 T cells were not screwed to one preferential subset after in vitro expansion, suggesting that in vitro expanded \u03b3\u03b4 T cells with anti-mouse TCR\u03b3\u03b4 antibodies plus IL-2 were still representative of in vivo subsets of \u03b3\u03b4 T cells. Expanded V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells were then sorted by FACS with PE-conjugated anti-mouse TCR V\u03b31.1/Cr4 antibody and APC conjugated anti-mouse TCR V\u03b32 antibody. We found the purities of sorted V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells were more than 99%  or 20 ng/ml of PMA+0.5 \u00b5g/ml of Ionomycin (activated) before mRNA extraction and fragmentation. After cDNA synthesis, adapter ligation and PCR amplification, four cDNA libraries were constructed for the resting and activated \u03b3\u03b4 T cell subsets. 400\u2013500 bp-sized products were used for cluster generation and 36 bp single-end sequencing was performed by using Illumina HiSeq 2000 Sequencer. Approximately 28 million clean reads were obtained from each sample. More than 88% of reads were mapped to the mouse genome using the default setting in TopHat, suggesting high quality of RNA-seq . Cufflin+ and V\u03b34+ \u03b3\u03b4 T cells share similar transcript profiles in both the resting and activated subsets. We identified 24 transcripts with differential expression between the resting V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells   (PMA/Ionomycin treatment induces a robust non-TCR mediated response in \u03b3\u03b4 T cells (q<0.05) . 2,158 t(q<0.05) . For a g(q<0.05) .+ \u03b3\u03b4 T cells were enriched for 32 KEGG pathways (p<0.05) (+ \u03b3\u03b4 T cells were enriched for 29 KEGG pathways (p<0.05)  . 2,158 t(p<0.05) . Our com+ and V\u03b34+ \u03b3\u03b4 T cells , Itgb2 (Cd18), Itgal (Cd11a), Itgae (Cd103) and Itgb1 (Cd29) (Resting V\u03b31 subsets . Interes1 (Cd29) . However+ and V\u03b34+ \u03b3\u03b4 T cells, upregulating T cell activation markers CD25, CD69 and CD44 along with several cytokines. Therefore, we analyzed the expression of these representative markers in activated V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells. As expected, PMA/Ionomycin treatment induced expression of XCL1, CCL3, CCL4, CCL1, IFN-\u03b3, Lta, Csf2, TNF-\u03b1, IL-2, Gzmb and Gzmc  technology. They concluded inherent gene expression differences in subsets defined their distinct functional responses Phylogenetic analysis suggests \u03b3\u03b4 T cells are precursors to modern B and \u03b1\u03b2 T cells + and V\u03b34+ \u03b3\u03b4 T cells are major subpopulations of peripheral \u03b3\u03b4 T cells in mice. Although global gene expression profiles of all emergent \u03b3\u03b4 thymocyte subsets have been reported by the Immunological Genome (ImmGen) Project and much knowledge has been obtained about the early divergence of gene expression programs between different \u03b3\u03b4 thymocyte subsets + and V\u03b34+ \u03b3\u03b4 T cells isn\u2019t available. A major hurdle has been the limited number of cells that can be obtained from healthy mice.V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells simultaneously from a single pool of mouse splenocytes. Our results proved that in vitro TCR-induced expansion for a week did not significantly change the proportion of V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells. We provide a comprehensive gene expression profile of mouse peripheral V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells in the resting and activated state. Although V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells share similar transcript profiles, we identified subset specific genes defining characteristics of each subset.In this study, we resolved the limited cell count issue by establishing a primary culture method expanding V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells, and 20 transcripts differentially expressed after PMA/Ionomycin treatment. Consistent with \u03b3\u03b4 thymocytes, expression levels of Rorc, Sox13 and Scart2 were higher in V\u03b34+ \u03b3\u03b4 T cells compared with V\u03b31+ \u03b3\u03b4 T cells Rorc expression is reported in \u03b3\u03b4 T cells, Th22 cells, NKT cells, CD4+ CD8+ thymocytes, and others that do not belong to the T or B cell lineage Rorc is recognized as a lineage-specific transcription factor of Th17 and is also required for IL-17 production Sox13 serves a general role in the differentiation of \u03b3\u03b4 T cells Sox13 was indispensable for the maturation of V\u03b34+ Th17 cells Scart2 is a marker of \u03b3\u03b4 T cells prepared to secrete IL-17A + \u03b3\u03b4 T cells compared with V\u03b31+ \u03b3\u03b4 T cells produce significantly more IL-17A and IL-17F after PMA/Ionomycin treatment are also consistent with findings in \u03b3\u03b4 thymocytes + \u03b3\u03b4 T cells produce significantly more IL-4 and IL-5 after PMA/Ionomycin treatment compared with V\u03b34+ \u03b3\u03b4 T cells. This finding is consistent with earlier reports showing V\u03b31+ \u03b3\u03b4 T cells preferentially produce IL-4, and the depletion of V\u03b31+ subset cells increases host resistance against Listeria monocytogenes infection + \u03b3\u03b4 T cells suppress V\u03b34+ \u03b3\u03b4 T cell mediated antitumor function through IL-4 We identified 24 transcripts differentially expressed in resting V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells. We found Bclaf1 and Atf2 were preferentially expressed in V\u03b34+ \u03b3\u03b4 T cells while Hmga1 and Bcl11b were preferentially expressed in V\u03b31+ \u03b3\u03b4 T cells. As a transcriptional repressor, Bclaf1 interacts with several members of the Bcl2 protein family and plays a role in the regulation of apoptosis and DNA repair Bclaf1 also plays an important role in lymphocyte homeostasis and activation Atf2 transcription factor is a member of the leucine zipper family of DNA binding proteins and forms a homodimer or a heterodimer with c-Jun, stimulating cAMP responsive element (CRE) dependent transcription. Atf2 expression is lower in CD8+ T cells compared with CD4+ T cells, a functional explanation to the differential response to glucocorticoids between CD8+ and CD4+ T cells Hmga1 binds preferentially to the minor groove of AT rich regions in double stranded DNA. It is involved in many cellular processes including regulation of inducible gene transcription, insulin resistance, diabetes and malignant transformation Hmga1 in transcriptional silencing in T cell lineages and leukemic cells Bclaf1, Atf2 and Hmga1 in \u03b3\u03b4 T cells have not been reported. Bcl11b is a T-cell specific gene and required for T-lineage commitment. Aberrant expression of Bcl11b contributes to human T-ALL Bcl11b was preferentially expressed in V\u03b34+ \u03b3\u03b4 thymocytes Bcl11b preferentially expressed in activated V\u03b31+ \u03b3\u03b4 T cells. The role of the transcript isoform of Bcl11b in V\u03b31+ \u03b3\u03b4 T cells needs further study.Alternative splicing plays an important role in increasing functional diversity of eukaryotes. Compared with the ImmGen Project, one of the advantages of RNA-seq is able to quantify individual transcript isoforms and identify differentially expressed transcripts between V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells shared similar signaling pathways. We found higher expression of IL-4 and IL-5 in activated V\u03b31+ \u03b3\u03b4 T cells. This suggests a role in asthma given that V\u03b34+ \u03b3\u03b4 T cells suppress airway hyperresponsiveness, compared with V\u03b31+ \u03b3\u03b4 T cells that enhance airway hyperresponsiveness and raise levels of Th2 cytokines and eosinophils infiltration in the airways Many of the differentially expressed gene transcripts identified in activated V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells exhibited high levels of transcripts for several chemokines and chemokine receptors, including CCL4, CCL5, CCR2, CCR5 and CXCR3. These data highlight the role of V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells in immunoregulatory and inflammatory processes. For example, CCL4 (MIP-1beta) and CCL5 (RANTES) are both Th1-associated chemokines that bind to CCR5. Up-regulation of CCR5 ligands may play a role in the recruitment process of blood monocytes, memory T helper cells and eosinophils. CCR2 is expressed on both V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells, and is necessary for the accumulation of \u03b3\u03b4 TILs to the tumor bed + and V\u03b34+ \u03b3\u03b4 T cells. CXCR6 plays a critical role in NK cell memory of haptens and viruses + and V\u03b34+ \u03b3\u03b4 T memory cells needs further examination.Both resting V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells. For example, Itgae (Cd103), implicated in epithelial T cell retention, is highly expressed on V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells Itgae contributes to clustering and activation of V\u03b3 5 TCRs expressed by epidermal T cells Integrins play key roles in immune responses, leukocyte trafficking and many human diseases. Most integrin related research has been focused on \u03b1\u03b2 T cells, with little published on \u03b3\u03b4 T cells. Our results show several integrins were highly expressed in V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells. We show after PMA/Ionomycin treatment several activation markers of T cells were upregulated including CD25, CD69 and CD44, along with most cytokine genes in both subsets. In addition, activated V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells produced high levels of XCL1, CCL3, CCL4, CCL1, IFN-\u03b3, TNF\u03b1, Lta, Csf2 and IL-10. IFN-\u03b3 and TNF\u03b1 are Th1 type cytokines. Previous reports show V\u03b34+ \u03b3\u03b4 T cells are the major \u03b3\u03b4 T subset producing IFN-\u03b3, and they steer CD4+ T cells toward a dominant Th1 cell response + \u03b3\u03b4 T cells produced significantly more IFN-\u03b3 compared with V\u03b31+ \u03b3\u03b4 T cells, partly due to the high expression level of eomesodermin + \u03b3\u03b4 T cells were the major \u03b3\u03b4 T subset producing IFN-\u03b3 in response to L. monocytogenes infection + and V\u03b34+ \u03b3\u03b4 T cells produce high levels of IL-10.PMA/Ionomycin induces a robust non-TCR mediated response in V\u03b31+ \u03b3\u03b4 thymocytes expressed high levels of Stat4, Maf, Gata3 and Eomes compared with V\u03b31+ \u03b3\u03b4 thymocytes + and V\u03b34+ \u03b3\u03b4 T cells expressed high levels of these transcription factors and the levels of Gata3 were slightly higher in V\u03b31+ \u03b3\u03b4 T cells compared with V\u03b34+ \u03b3\u03b4 T cells after PMA/Ionomycin treatment. Gata3 is critical for Th2 cell differentiation and required for IL-4 production. The higher level of Gata3 expression in V\u03b31+ \u03b3\u03b4 T cells is consistent with the phenotype of V\u03b31+ \u03b3\u03b4 T cells producing more IL-4 than V\u03b34+ \u03b3\u03b4 T cells. T-bet is a major factor for Th1 cell differentiation and IFN-\u03b3 production Eomes is also involved in Th1 differentiation and IFN-\u03b3 production T-bet and Eomes is consistent with the phenotype of both V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells that produce high levels of IFN-\u03b3. The difference between our results with the ImmGen Project may be due to the source of \u03b3\u03b4 T cells. The cells used in the ImmGen Project are \u03b3\u03b4 thymocytes, however the cells in our study were peripheral \u03b3\u03b4 T cells derived from the spleen.Narayan et al. reported that V\u03b34+ and V\u03b34+ \u03b3\u03b4 T cells maintain inflammatory and regulatory phenotypes. Both demonstrate an inflammatory cell phenotype via IFN-\u03b3 and TNF\u03b1 expression. And, both display a regulatory cell phenotype via TGF-\u03b2 and IL-10 production. V\u03b31+ \u03b3\u03b4 T cells produced more Th2 type cytokines, while V\u03b34+ \u03b3\u03b4 T cells tended to produce more IL-17. Thus, Th2 type cytokines may explain how V\u03b31+ \u03b3\u03b4 T cells affect anti-inflammatory functions in different infection models, and describe the enhancing effect on airway hyperresponsiveness (AHR) + \u03b3\u03b4 T cells in the infection models and the inhibitory effect on airway hyperresponsiveness (AHR). Although this study was performed in V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells expanded in vitro, which may not fully represent the true status of V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells in vivo, our results support the hypothesis that distinct \u03b3\u03b4 TCR types direct cells to acquire a certain type of functional programming during thymic development Taken together, this study shows both V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells following PMA/Ionomycin treatment. Although both \u03b3\u03b4 T cell populations have similar transcript profiles, subset-specific transcripts define distinct characteristics and describe the inherent differences between V\u03b31+ and V\u03b34+ \u03b3\u03b4 T cells.Complementary to the ImmGen Project, this report provides a comprehensive gene expression profile of mouse peripheral V\u03b31Dataset S1Raw data and differential expression analysis in RNA-seq.(XLSX)Click here for additional data file.Dataset S2+ \u03b3\u03b4 T cells.Differentially expressed genes between the resting and activated V\u03b31(XLSX)Click here for additional data file.Dataset S3+ \u03b3\u03b4 T cells.Differentially expressed genes between the resting and activated V\u03b34(XLSX)Click here for additional data file.Dataset S4Transcription factors related to Th cell differentiation and cytokine secretion.(XLSX)Click here for additional data file."}
{"text": "The packing features supra\u00admolecular layers sustained by O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonding.A distorted square-pyramidal CdNS 6H12NOS2)2(C4H10N2)], features a distorted square-pyramidal coordination geometry about the central CdII atom. The di\u00adthio\u00adcarbamate ligands are chelating, forming similar Cd\u2014S bond lengths and define the approximate basal plane. One of the N atoms of the piperazine mol\u00adecule, which adopts a chair conformation, occupies the apical site. In the crystal, supra\u00admolecular layers propagating in the ac plane are formed via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy), hy\u00addroxy-O\u2014H\u22efN and coordinated-piperazine-N\u2014H\u22efO(hy\u00addroxy) hydrogen bonds; the layers also feature methine-C\u2014H\u22efS inter\u00adactions and S\u22efS [3.3714\u2005(10)\u2005\u00c5] short contacts. The layers stack along the b-axis direction with very weak terminal-piperazine-N\u2014H\u22efO(hy\u00addroxy) inter\u00adactions between them. An evaluation of the Hirshfeld surfaces confirms the importance of inter\u00admolecular inter\u00adactions involving oxygen and sulfur atoms.The title compound, [Cd(C Layers thus formed stack along the b axis, with very weak terminal-piperazine-N4\u2014H\u22efO2(hy\u00addroxy) inter\u00adactions between them, Table\u00a02In the extended structure, hy\u00addroxy-O1\u2014H\u22efO2(hy\u00addroxy), hy\u00addroxy-O2\u2014H\u22efN4 and (coordinated-piperazine)-N3\u2014H\u22efO1(hy\u00addroxy) hydrogen bonds Table\u00a02 lead to Crystal Explorer , and there is no contribution from C\u22efC contacts in the structure as the result of the absence of C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions. Finally, the presence of S\u22efS contacts can also be viewed in the delineated fingerprint plot, Fig.\u00a07g, by the density of points in the ed, id region around 1.7\u20132.4\u2005\u00c5 as a broken line segment.The overall two-dimensional fingerprint plot, Fig.\u00a072% Fig.\u00a07d, and tet al., 2014The identified inter\u00admolecular inter\u00adactions were further evaluated by an analysis of the enrichment ratios (ER) that give a qu\u00adanti\u00adtative measure of the likelihood of specific inter\u00admolecular inter\u00adactions to occur based on a Hirshfeld surface analysis 2]2 compounds are usually binuclear CH2CH2OH]2 CH2CH2OH]2\u00b7EtOH]x for x = 2 and, unprecedented, n  form transforming in solution to the thermodynamic, binuclear form (x = 2). Other recrystallization conditions led to decomposition of the di\u00adthio\u00adcarbamate ligands and subsequent formation of a co-crystal and some salts. This behaviour, along with the unexpected structure of {Cd[S2CN(iPr)CH2CH2OH]22] 2(MeOH)2 CH2CH2OH]2 : \u03bd (O\u2014H) 3281, \u03bd(C\u2014N) 1442, \u03bd (C\u2014O) 1169, \u03bd (C\u2014S) 1029.The reagents Cd[SUiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located in a difference Fourier map but were refined with a distance restraints of O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016000165/hb7558sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016000165/hb7558Isup2.hklStructure factors: contains datablock(s) I. DOI: 1445316CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In three potentially anti\u00adconvulsant compounds, of which two are isoindoline derivatives and one an iso\u00adquinoline derivative, the central moiety is planar. In the crystals of all three compounds, there are C\u2014H\u22efO hydrogen bonds present linking the mol\u00adecules into two-dimensional slabs for the isoindoline derivatives, and into a three-dimensional framework for the iso\u00adquinoline derivative. 9H7NO3, (1), C10H7NO5, (2), and C14H9NO5, (3), are three potentially anti\u00adconvulsant compounds. Compounds (1) and (2) are isoindoline derivatives and (3) is an iso\u00adquinoline derivative. Compounds (2) and (3) crystallize with two independent mol\u00adecules (A and B) in their asymmetric units. In all three cases, the isoindoline and benzoiso\u00adquinoline moieties are planar . The substituents attached to the N atom are almost perpendicular to the mean planes of the heterocycles, with dihedral angles of 89.7\u2005(3)\u00b0 for the N\u2014O\u2014Cmeth\u00adyl group in (1), 71.01\u2005(4) and 80.00\u2005(4)\u00b0 for the N\u2014O\u2014C(=O)O\u2014Cmeth\u00adyl groups in (2), and 75.62\u2005(14) and 74.13\u2005(4)\u00b0 for the same groups in (3). In the crystal of (1), there are unusual inter\u00admolecular C=O\u22efC contacts of 2.794\u2005(1) and 2.873\u2005(1)\u2005\u00c5 present in mol\u00adecules A and B, respectively. There are also C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid distance = 3.407\u2005(3)\u2005\u00c5] present, forming slabs lying parallel to (001). In the crystal of (2), the A and B mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming slabs parallel to (10-1), which are in turn linked via a number of \u03c0\u2013\u03c0 inter\u00adactions [the most significant centroid\u2013centroid distances are 3.4202\u2005(7) and 3.5445\u2005(7)\u2005\u00c5], forming a three-dimensional structure. In the crystal of (3), the A and B mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, forming a three-dimensional structure, which is consolidated by \u03c0\u2013\u03c0 inter\u00adactions [the most significant inter-centroid distances are 3.575\u2005(3) and 3.578\u2005(3)\u2005\u00c5].The title compounds, C The compound is a dual MES/6Hz active compound. Compounds (2) and (3) showed similar activity.2-Meth\u00adoxy\u00adisoindoline-1,3-dione, (1), studied by X-ray techniques, was inactive in MES and scPTZ in mice, but showed MES protection in rat studies at 50\u2005mg\u2005kgThe title compounds, containing either an isoindoline-1,3-dione moiety, (1) Fig.\u00a01 and (2) In compound (1), the isoindoline ring is planar [r.m.s. deviation = 0.017\u2005(4)\u2005\u00c5]. The meth\u00adoxy O atom, O3, deviates from this plane by 0.176\u2005(6)\u2005\u00c5 while the methyl C atom, C9, is out of the plane by 1.105\u2005(9)\u2005\u00c5. The meth\u00adoxy substituent is oriented almost perpendicular to the indoline ring with the dihedral angle between the mean planes of the indoline ring and the meth\u00adoxy substituent being 89.7\u2005(3)\u00b0.A and B) in the asymmetric unit. The isoindoline ring is planar [r.m.s. deviation = 0.0327\u2005(9) for A and 0.0147\u2005(9)\u2005\u00c5 for B] with the dione O atoms significantly out of the plane for mol\u00adecule A but not for mol\u00adecule B . The carbonato moiety is planar in both mol\u00adecules  and makes dihedral angles of 71.50\u2005(3) and 80.03\u2005(4)\u00b0 with the benzoiso\u00adquinoline ring in A and B, respectively, indicating that these substituents are oriented almost perpendicular to the benzoiso\u00adquinoline ring system.In compound (2), there are two mol\u00adecules (A and B) in the asymmetric unit. In both mol\u00adecules, the benzoiso\u00adquinoline ring systems are planar . The meth\u00adoxy O atom deviates from this plane by 0.126\u2005(1) for atom O5A in A and 0.156\u2005(1)\u2005\u00c5 for atom O5B in B. The methyl carbonate moieties are planar  and these substituents are oriented almost perpendicular to the iso\u00adquinoline rings, making dihedral angles of 71.50\u2005(3) and 80.04\u2005(4)\u00b0 for A and B, respectively. As in (2), these dihedral angles are significantly smaller than that found for (1).In compound (3), there are also two mol\u00adecules \u2005\u00c5; Cg1 and Cg2 are the centroids of rings N1/C1/C2/C7/C8 and C2\u2013C7, respectively; symmetry codes: (i) x\u00a0\u2212\u00a01, y, z; (ii) x\u00a0+\u00a01, y, z].In the crystal of (1), there are C\u2014H\u22efO hydrogen bonds Fig.\u00a04 and \u03c0\u2013\u03c0 A and B mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds  for Cg1\u22efCg5ii and 3.5445\u2005(7)\u2005\u00c5 for Cg2\u22efCg4ii .In the crystal of (2), the ds Fig.\u00a05, formingA and B mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds , Cg2\u22efCg3iii = 3.575\u2005(3)\u2005\u00c5 and Cg9\u22efCg10iv; Cg1, Cg2, Cg3, Cg9 and Cg10 are the centroids of rings N1A/C1A\u2013C5A, C2A/C3A/C6A\u2013C9A, C3A/C4A/C9A\u2013C12A, C2B/C3B/C6B\u2013C9B and C3B/C4B/C9B\u2013C12B, respectively; symmetry codes: (iii) x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0In the crystal of (3), the ds Fig.\u00a06, formingA and O1B) has a short inter\u00admolecular inter\u00adactions with the central C atom of the carbonato group , which is perpendicular to the carbonato plane indicating that both atoms, C9A and C9B, must have significant positive character. These inter\u00adactions link the mol\u00adecules into dimers as shown in Figs. 6A (but not for mol\u00adecule B), where a longer inter\u00admolecular inter\u00adaction of 3.060\u2005(3)\u2005\u00c5 is observed between atoms O2A and C13A, resulting in weakly associated dimers similar to that seen in the case of (2).Inter\u00adestingly, in the crystal of (2) one of the two dione moieties for each mol\u00adecule :N-hy\u00addroxy\u00adphthalimide  in absolute ethanol (350\u2005ml), and the red reaction mixture was stirred at room temperature for 30\u2005min. The brick-red precipitate was collected, washed with water, and dried in the oven at 373\u2005K for 30\u2005min to give 17.45\u2005g (95%) of sodium phthalimide oxide as brick-red crystals; m.p. > 573\u2005K. To the solution of sodium phthalimide oxide  in water (15\u2005ml) was added acetone (10\u2005ml), followed by a solution of bromo\u00admethane . The reaction mixture was stirred at room temperature for 16\u2005h, during which the red color disappeared. On standing at room temperature for 48\u2005h, the product solidified in the aqueous mixture and was collected. Recrystallization from 2-propanol gave 0.72\u2005g (78%) of compound (1) as plate-like colorless crystals: m.p. 395\u2013397\u2005K; 1H NMR (CDC13) \u03b4 3.36 , 5.52, s, 1 H,CH, 7.87 .To a freshly prepared solution of sodium  in absolute ethanol (60\u2005ml) was added a solution of Compound (2):1H NMR (CDC13) \u03b4 3.8 , 7.86 .To a solution of sodium phthalimide oxide  in water (15\u2005ml) was added acetone (10\u2005ml), followed by a solution of bromo\u00ad(meth\u00adoxy)methanone . The reaction mixture was stirred at room temperature for 16\u2005h, during which the red color disappeared. On standing at room temperature for 48\u2005h, the product solidified in the aqueous mixture and was collected. Recrystallization from ethanol gave 0.82\u2005g (74%) of compound (2) as colorless crystals: m.p. 410\u2013411\u2005K; Compound (3):1H NMR (CDCl3) \u03b4 3.79 , 5.66 , 7.65\u20138.50 .To a solution of sodium naphthalimide oxide, , in water (50\u2005ml), was added bromo\u00ad(meth\u00adoxy)methanone  in acetone (10\u2005ml). The red reaction mixture was stirred at room temperature. The red color disappeared within 5\u2005min and the reaction mixture was filled with a white precipitate. After standing for 4\u2005h, the white precipitate was collected, washed with water, and recrystallized from ethanol to give 1.46\u2005g (89%) of compound (3) as colorless crystals: m.p. 483\u2013485\u2005K; isoU(H) = 1.5Ueq(C) for methyl H atoms and = 1.2eqU(C) for other H atoms.Crystal data, data collection and structure refinement details for (1), (2) and (3) are summarized in Table\u00a0410.1107/S1600536814023769/su2795sup1.cifCrystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S1600536814023769/su27951sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814023769/su27952sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S1600536814023769/su27953sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S1600536814023769/su27951sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814023769/su27952sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814023769/su27953sup7.cmlSupporting information file. DOI: 1031391, 1031392, 1031393CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound, bis\u00ad\u00adcobalt(III) tris\u00ad(perchlorate) methanol monosolvate monohydrate, is a novel complex in which the metal centre is hexa\u00adcoordinated. 25H30N4O4)2](ClO4)3\u00b7CH3OH\u00b7H2O, the metal atom is coordinated by two tridentate crown ether terpyridine ligands, forming a distorted CoN6 octa\u00adhedron. The three pyridine rings in each crown\u2013terpyridine ligand are approximately coplanar [maximum deviations = 0.088\u2005(12) and 0.102\u2005(15)\u2005\u00c5] and the mean planes through the three pyridine rings are perpendicular to each other, making a dihedral angle of 89.95\u2005(17)\u00b0. An intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction is observed between the two terpyridine ligands. In the crystal, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, a \u03c0\u2013\u03c0 stacking inter\u00adaction [centroid\u2013centroid distance = 3.923\u2005(7)\u2005\u00c5] and a C\u2014H\u22ef\u03c0 inter\u00adaction connect the complex cation, the perchlorate anions and the two types of solvent molecules, forming a three-dimensional network.In the title compound, [Co(C M(R-terpy)]X2 , have been investigated because of their inter\u00adesting properties such as magnetic and photochemical characteristics. Cobalt(II) complexes with R-terpy ligands are known as spin-crossover compounds. Previously, we observed the unique spin-transition behavior in [Co(II)(R-terpy)2](BF4)2 with long-alkyl\u00adated terpyridine ligands, and showed that the magnetic behaviors are influenced not only by inter-chain inter\u00adactions between long alkyl chains but also by \u03c0\u2013\u03c0 stacking inter\u00adactions between terpyridine moieties  compounds. The Co\u2014N distances of the central pyridine in the terpyridine unit [1.844\u2005(9)\u2005\u00c5] are shorter than the Co\u2014N distances of the side pyridine in the terpyridine unit [1.910\u2005(10)\u20131.949\u2005(10)\u2005\u00c5], which induces a pronounced distortion of the CoN6 octa\u00adhedron. The three pyridine rings in each crown\u2013terpy ligand are approximately coplanar [maximum deviations 0.102\u2005(15) and 0.088\u2005(12)\u2005\u00c5], and the two mean planes through the three pyridine rings in the complex are nearly perpendicular to each other, making a dihedral angle of 89.95\u2005(17)\u00b0.The asymmetric unit of the title compound consists of one [Co(crown\u2013terpy)The overall packing of structure is shown in Fig.\u00a024)3  dissolved in methanol (20\u2005ml) was poured dropwise into a solution of the crown\u2013terpy ligand  in 1:1 methanol\u2013chloro\u00adform. The precipitate formed immediately and was filtered. Single crystals of the title compound suitable for X-ray diffraction were obtained from a methanol solution.The crown-terpyridine ligand was prepared by the reaction of 4\u2032-bromo-2,2\u2032:6\u2032,2\u2032\u2032-terpyridine  and 1,4,7,10-tetra\u00adoxa-13-aza\u00adcyclo\u00adpenta\u00addecane  in DMF. The mixed solution was evaporated to give the ligand as a white powder. Co(ClOUiso(H) = 1.2Ueq(C) and 1.5Ueq. The positions of the H atoms of the water mol\u00adecule were refined with restraints of O\u2014H = 0.85\u2005(2) and H\u22efH = 1.38\u2005(2)\u2005\u00c5, and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015014164/is5400sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014164/is5400Isup2.hklStructure factors: contains datablock(s) I. DOI: 1415327CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title complex is a centrosymmetric dimer with a copper\u2013copper distance of 4.0408\u2005(3)\u2005\u00c5. The Cu ions in the dimer are bridged by two triazole rings and oxygen donor ligands from water mol\u00adecules and nitrate anions in a distorted octa\u00adhedral coordination geometry. 2(C10H8N7)2(NO3)2(H2O)2]\u00b72H2O, consists of centrosymmetric dimeric units with a copper\u2013copper separation of 4.0408\u2005(3)\u2005\u00c5. The CuII ions in the dimer display a distorted octa\u00adhedral coordination geometry and are bridged by two triazole rings, forming an approximately planar Cu2N4 core (r.m.s. deviation = 0.049\u2005\u00c5). In the crystal, O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions link the mol\u00adecules into a three-dimensional network.The structure of the dinuclear title complex, [Cu The study of this type of coordination compound is promising since, as a result, a compound can be obtained with useful physical properties such as optical, magnetic or catalytic \u2005\u00c5 for atom N2], with a Cu\u22efCu separation of 4.0408\u2005(3)\u2005\u00c5, in good agreement with the values usually observed in \u03bc-triazolyl-bridged complexes \u2005\u00c5; \u03b82 = 88.62\u2005(16)\u00b0], while the five-membered Cu1/N2/C1/C2/N4 chelate ring adopts a flattened envelope conformation with the Cu atom as flap .The structure of the title complex mol\u00adecule Fig.\u00a01 has a crCg1\u22efCg2ii = 3.8296\u2005(13)\u2005\u00c5 and Cg3\u22efCg3iii = 3.5372\u2005(10), and perpendic\u00adular inter\u00adplanar distances Cg1\u22efCg2ii = 3.5584\u2005(9) and Cg3\u22efCg3iii = 3.3234\u2005(10)\u2005\u00c5 .In the crystal, the complex molecules and water mol\u00adecules of crystallization are linked through O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds Table\u00a01, forming2\u2013Cu. The most similar are: di\u00adaqua\u00adbis\u00ad-1,2,4-triazolato-N\u2032,N1,N2,N\u2032\u2032)bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonato-O)dicopper(II) -1,2,4-triazolato]di\u00adaqua\u00addicopper diperchlorate -5-(meth\u00adyl)-1,2,4-triazol-1-ide]tri\u00adaqua\u00adtricopper di\u00adperchlorate dihydrate bis(acetonitrile)\u00adbis\u00ad(perchlorato-O)dicopper 2\u00b73H2O  was added to a hot solution of 2-[5--triazol-1-yl-methyl-1H--triazol-3\u00adyl]pyridine  in water (7\u2005ml). The transparent blue solution was left to evaporate slowly in the air and after few hours, blue single crystals suitable for X-ray analysis were obtained (yield: 67%).A water solution of Cu(NOUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016003479/rz5185sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016003479/rz5185Isup2.hklStructure factors: contains datablock(s) I. DOI: 1456451CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The aza\u00adadamantane structure in (I) is slightly distorted, with N\u2014CH2\u2014CH2\u2014N torsion angles of 10.4\u2005(3) and \u22129.0\u2005(3)\u00b0. These values differ slightly from the corresponding torsion angles in the free aminal cage (0.0\u00b0) and in related co-crystalline adducts, which are not far from a planar geometry and consistent with a Dd2 mol\u00adecular symmetry in the tetra\u00adaza\u00adtri\u00adcyclo structure. The structures also differ in that there is a slight elongation of the N\u2014C bond lengths about the N atom that accepts the hydrogen bond in (I) compared with the other N\u2014C bond lengths. In the crystal, the two mol\u00adecules are not only linked by a classical O\u2014H\u22efN hydrogen bond but are further connected by weak C\u2014H\u22ef\u03c0 inter\u00adactions, forming a two-dimensional supra\u00admolecular network parallel to the bc plane.In the crystal of the title co-crystalline adduct, C Reaction between TATD with 4-chloro-3,5-di\u00admethyl\u00adphenol in solution yields symmetrical bis-benzoxazines -1,8,10,12-tetra\u00adaza\u00adtetra\u00adcyclo\u00adpenta\u00addecane with 4-nitro\u00adphenol -4-bromo\u00adphenol \u20134-chloro-3,5-di\u00admethyl\u00adphenol under solvent-free conditions by simply grinding together the components at room temperature. Herein, we describe the synthesis of the title co-crystalline adduct 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00addodecane (TATD) and a 4-chloro-3,5-di\u00admethyl\u00adphenol mol\u00adecule linked via an O\u2014H\u22efN hydrogen bond, forming a D motif ; p-bromo\u00adphenol (pKa = 9.37) and hydro\u00adquinone (pKa = 9.85) et al., 2007et al., 2015et al., 1987et al., 20142dD point group, two small differences are noted. The aza\u00adadamantane structure in (I)2\u2014CH2\u2014N torsion angles of 10.4\u2005(3)\u00b0 (N1\u2014C1\u2014C2\u2014N2) and \u22129.0\u2005(3)\u00b0 (N3\u2014C7\u2014C8\u2014N4). These values differ slightly from the values of the corresponding torsion angles in the free aminal cage  and 1.480\u2005(2)\u2005\u00c5], compared to the the other N\u2014C bond lengths \u2005\u00c5; symmetry operator: (i) x, \u2212y, z\u00a0\u2212\u00a0c-axis direction e Table\u00a02. Furtheron Fig.\u00a03.meth\u00adyl = 1.502\u2005(3), 1.500\u2005(3), 1.514\u2005(3) and 1.505\u2005(3)\u2005\u00c5]. For 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00addodecane, two comparable structures were retrieved from the CSD 3,8]dodecane co-crystallized with hydro\u00adquinone 3,8]dodecane is rather limited.The geometric parameters of 4-chloro-3,5-di\u00admethyl\u00adphenol in (I)3,8]dodecane (TATD)  and 4-chloro-3,5-di\u00admethyl\u00adphenol  was ground using a mortar and pestle, at room temperature for 15\u2005min., as required to complete the reaction (TLC). The mixture was then dissolved in methanol. Crystals suitable for X-ray diffraction were obtained from a methanol solution upon slow evaporation of the solvent at room temperature.A mixture of 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00ad[4.4.1.Uiso(H) values set at 1.2Ueq (1.5 for methyl groups) of the parent atom. The methyl groups were allowed to rotate but not to tip.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015010257/zs2335sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015010257/zs2335Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015010257/zs2335Isup3.cmlSupporting information file. DOI: 1403518CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Fe\u2014N bond lengths are indicative of a d6 low-spin state for the FeII ion in the complex. The dihedral angle between the phen ligands in the cation is 87.64\u2005(6)\u00b0. The Tf2N\u2212 counter-anion is non-coordinating, with the \u2013CF3 groups arranged in a trans fashion with respect to each other, leading to an anti,anti conformation of the \u2013CF3 groups and \u2013SO2N\u2013 moieties relative to the S\u2014C bonds. The water mol\u00adecule of crystallization connects two O atoms of the Tf2N\u2212 anions through weak hydrogen bonds. C\u2014H\u22efO hydrogen-bonding inter\u00adactions are also observed, consolidating the packing of the mol\u00adecules into a three-dimensional network structure.The crystal structure of the title complex, [Fe(C DOI: 10.1107/S2056989014026966/wm5100Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014026966/wm5100fig1.tif3 2+ 2 \u2212 2 x y z . DOI: 3]2+, Tf2N\u2212 and H2O mol\u00adecular units. Displacement ellipsoids are represented at the 30% probability level. Hydrogen atoms were omitted for clarity. [Symmetry code: i) \u2212x\u00a0+\u00a01,y,-z\u00a0+\u00a0View of the [Fe(phen)Click here for additional data file.10.1107/S2056989014026966/wm5100fig2.tif2 2 \u2212 x y z x y z . DOI: 2O mol\u00adecule and Tf2N\u2212 anions. [Symmetry codes: ii) x\u00a0\u2212\u00a0y\u00a0\u2212\u00a01/2,z, iii) \u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a0Hydrogen bonds between the H1038289CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cationic NiII center is in a distorted square-planar coordination environment chelated by the imine N and phenolate O donor atoms of the two Schiff base ligands. The N and O donor atoms of the two ligands are mutually trans with Ni\u2014N and Ni\u2014O bond lengths of 1.9242\u2005(10) and 1.8336\u2005(9)\u2005\u00c5, respectively. The fluoro\u00adphenyl ring is almost orthogonal to the coordination plane and makes a dihedral angle of 82.98\u2005(7)\u00b0 with the phenolate ring. In the crystal, mol\u00adecules are linked into screw chains by weak C\u2014H\u22efF hydrogen bonds. Additional C\u2014H\u22ef\u03c0 contacts arrange the mol\u00adecules into sheets parallel to the ac plane.The asymmetric unit of the title complex, [Ni(C In particular they can be photoluminescent -(4-fluoro\u00adbenz\u00adyl)imino\u00admeth\u00adyl]-6-meth\u00adoxy\u00adphenolato-\u03ba2N,O1}nickel(II) -(4-meth\u00adoxy\u00adbenz\u00adyl)imino\u00admeth\u00adyl]phenolato-\u03ba2N,O1}nickel(II) 2] (1), and its characterization by spectros\u00adcopy and elemental analysis. Crystal structure determination confirms the binding mode of the [(4-fluoro\u00adbenz\u00adyl)imino\u00admeth\u00adyl]phenolate ligand to the NiII cation \u00b0 and O1\u2014Ni1\u2014N1i = 87.44\u2005(4)\u00b0 . As expected under inversion symmetry, the trans angles (N11\u2014Ni1\u2014N1i and O1\u2014Ni1\u2014O1i) are found to be linear. The Ni1\u2014N1 and Ni1\u2014O1 distances in the N2O2 coordination plane are 1.9242\u2005(10)\u2005\u00c5 and 1.8336\u2005(9)\u2005\u00c5, respectively. These compare well with those observed in the two other closely related NiII complexes with N2O2 coordinating Schiff base ligands \u2005\u00c5, \u03b8 = 65.3\u2005(3) and \u03d5 = 4.0\u2005(3)\u00b0. Other bond lengths and angles observed in the structure are also normal. The fluoro\u00adphenyl ring (C9\u2013C14) makes a dihedral angle of 82.98\u2005(7)\u00b0 with the phenolate ring (C1\u2013C6).The asymmetric unit of (1) contains one-half of the mol\u00adecule with the Nind Fig.\u00a01. The catA\u22efF1 inter\u00adactions phenolate residues. No corresponding structures with a benzyl or substituted benzyl unit bound to the imino N atom were found. However extending the search to allow additional substitution on the phenolate ring resulted in eight discrete structures including the two closely related structures mentioned previously  revealed a total of 1191 NiE)-2-[(4-fluoro\u00adbenzyl\u00adimino)\u00admeth\u00adyl]phenol. Nickel(II) acetate tetra\u00adhydrate  was dissolved separately in absolute ethanol (10\u2005ml) and added to a flask containing the cooled ligand solution. The mixture was stirred and refluxed for 3\u2005h upon which a dark-green solid formed. This was filtered off, washed with ice-cold ethanol and air-dried at room temperature. The solid product was recrystallized from chloro\u00adform, yielding green crystals. Yield 68.6%; m.p. 471\u2013473\u2005K. Analytical data for C28H22F2N2O2Ni: C, 65.28; H, 4.30; N, 5.44. Found: C, 65.87; H, 4.39; N, 5.55. IR : \u03bd(C=N) 1612 (s), \u03bd(C\u2014N) 1390 (w), \u03bd(C\u2014O) 1221 (s), \u03bd(Ni\u2014N) 597 (w), \u03bd(Ni\u2014O) 451 (w). The infrared spectra of the title complex revealed a strong band of 1612\u2005cm\u22121 in the spectrum assignable to C=N stretching frequency upon complexation  was added to salicyl\u00adaldehyde , dissolved in absolute ethanol (2\u2005ml), forming a bright-yellow solution. The mixture was heated under reflux for an hour to produce the ligand,  = 0.95\u2005\u00c5 for aromatic and 0.99\u2005\u00c5 for CH2 hydrogen atoms. The Uiso values were constrained to be 1.2Ueq of the carrier atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814020546/sj5425sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814020546/sj5425Isup2.hklStructure factors: contains datablock(s) I. DOI: 1024161CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efF inter\u00adactions connect the mol\u00adecules, forming supra\u00admolecular chains propagating along the  22H23F2N3O2, the bicyclic ring system exists in a twin-chair conformation with an equatorial disposition of the 4-fluoro\u00adphenyl groups on the heterocycle. These aromatic rings are inclined to one another by 19.4\u2005(1)\u00b0. In the crystal, mol\u00adecules are linked by pairs of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds into inversion dimers, incorporating R12(7) and R22(8) ring motifs; the same O atom accepts both hydrogen bonds. These dimers are further linked by a pair of C\u2014H\u22efF hydrogen bonds, enclosing R22(28) ring motifs, forming supra\u00admolecular chains along [010]. The NH group of the pyridine ring is not involved in hydrogen bonding, probably due to the steric hindrance of the fluoro\u00adphenyl groups.In the title compound, C The fluoro\u00adphenyl groups on the heterocycle occupy equatorial positions and are inclined to one another by 19.4\u2005(1)\u00b0. The geometric parameters of the title mol\u00adecule agree well with those reported for similar structures, for example, 2,4-bis\u00ad(4-fluoro\u00adphen\u00adyl)-3-aza\u00adbicyclo\u00ad[3.3.1]nonan-9-one, (II) i and C2\u2014H2\u22efO3i .In the crystal, pairs of bifurcated acceptor N3\u2014H3\u22efO3i Table\u00a01 hydrogenfs Fig.\u00a02. These di Table\u00a01 hydrogenviz. compound (III)  in the asymmetric unit. In all three compounds, the bi\u00adcyclo rings have twin-chair conformations with equatorially disposed 4-fluoro\u00adphenyl groups on the heterocycle. The fluoro\u00adphenyl rings are oriented at an angle of 28.7\u2005(1)\u00b0 in (II), and 55.3\u2005(1) (mol\u00adecule A) and 56.4\u2005(1)\u00b0 (mol\u00adecule B) for (III), compared to 19.4\u2005(1)\u00b0 in the title compound, (I)38 \u2018hits\u2019 for crystal structures containing the 3-aza\u00adbicyclo\u00ad[3.3.1]nonane subunit were obtained for a search of the Cambridge Structural Database  medium, with the addition of few drops of acetic acid, was stirred for 10\u201312\u2005h. After completion of the reaction a solid mass was formed. The precipitate was filtered off and washed with an ethanol\u2013water mixture. The crude product was then recrystallized from ethanol\u2013chloro\u00adform to obtain colourless diffraction-quality crystals of title compound.A mixture of 2,4-diphenyl-3-aza\u00adbicyclo\u00ad[3.3.1]nonan-9-one (0.1\u2005mmol), methyl hydrazine\u00adcarboxyl\u00adate (1.5\u2005mmol) in an ethanol\u2013chloro\u00adform (1:1 Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814018935/su2773sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814018935/su2773Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814018935/su2773Isup3.cmlSupporting information file. DOI: 1020373CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the planes of the phen\u00adoxy and phthalo\u00adnitrile rings are oriented at a dihedral angle of 60.39\u2005(5)\u00b0. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, forming slabs parallel to (100). The slabs are linked by a pair of inversion-related C\u2014H\u22efN hydrogen bonds, forming a three-dimensional structure. 20H20N4O2\u00b7H2O, the planes of the phen\u00adoxy and phthalo\u00adnitrile rings are oriented at a dihedral angle of 60.39\u2005(5)\u00b0. The 3-(di\u00ad\u00admethyl\u00adamino)\u00adpropyl chain has an extended conformation and is cis with respect to the phthalo\u00adnitrile ring. In the crystal, O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules to form slabs parallel to (100). There are also C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions present within the slabs. The slabs are linked by a pair of inversion-related C\u2014H\u22efN hydrogen bonds, involving phthalo\u00adnitrile rings, forming a three-dimensional structure.In the title compound, C Well-known application fields for amino derivatives are their use as synthetic inter\u00admediates of anti\u00adcancer agents, anti\u00adbiotics and other drugs. They also exhibit exceptionally low ocular irritation and oral toxicity, being well tolerated by human tissue , O\u2014Hw. .Oamd and O\u2014Hw\u22efNdma (dma = di\u00admethyl\u00adamino) hydrogen bonds , and the O\u2014Hw\u22ef Oamd, C\u2014Hphen\u22efOamd and C\u2014Hphen\u22efOw hydrogen bonds form via a pair of inversion-related Cphn\u2014H\u22efNphn  hydrogen bonds, forming a three-dimensional structure phthalo\u00adnitrile \u00b0.A search of the Cambridge Structural Database  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the other H atoms.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a02N,N-di\u00admethyl\u00adpropane-1,3-di\u00adamine  and K2CO3  in dry tetra\u00adhydro\u00adfuran , stirred in an ice bath for 15\u2005min, was added over a period of 40\u2005min, 4-benzoyl chloride  in dry THF (5\u2005ml). The reaction mixture was then stirred for 5\u2005h at room temperature and monitored by thin-layer chromatography [THF\u2013hexane (3:4 v/v) as a mobile phase on silica-gel plates]. The oily residue obtained was dissolved in MeOH. The solvent was evaporated slowly and colourless block-like crystals appeared in ca 10\u2005d .To a mixture of 10.1107/S2056989015014991/su5187sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015014991/su5187Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015014991/su5187Isup3.cmlSupporting information file. DOI: 1418026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "P,S-donor set is observed in the title polymorph; an intra\u00admolecular Au\u22efO inter\u00adaction is noted. The packing is consolidated by C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions to generate a three-dimensional network.A linear geometry defined by a  8H7ClNOS)(C18H15P)], is a monoclinic  polymorph of the previously reported triclinic form  [Tadbuppa & Tiekink  coordination geometry [P\u2014Au\u2014S = 175.62\u2005(5)\u00b0 in the title polymorph], being coordinated by thiol\u00adate S and phosphane P atoms, a Z conformation about the C=N bond and an intra\u00admolecular Au\u22efO contact. The major conformational difference relates to the relative orientations of the residues about the Au\u2014S bond: the P\u2014Au\u2014S\u2014C torsion angles are \u22128.4\u2005(7) and 106.2\u2005(7)\u00b0 in forms \u03b1 and \u03b2, respectively. The mol\u00adecular packing of form \u03b2 features centrosymmetric aggregates sustained by aryl-C\u2014H\u22efO inter\u00adactions, which are connected into a three-dimensional network by aryl-C\u2014H\u22ef\u03c0 contacts. The Hirshfeld analysis of forms \u03b1 and \u03b2 shows many similarities with the notable exception of the influence of C\u2014H\u22efO inter\u00adactions in form \u03b2.The title compound, [Au(Ckink 2010. Acta Cr N-aryl-O-alkyl\u00adthio\u00adcarbamates, i.e. compounds of general formula R3PAu[SC(OR\u2032)=NR\u2032\u2032]  continues owing to their recently disclosed exciting biological activities. Thus, various tri\u00adphenyl\u00adphosphane derivatives display excellent cytotoxicity profiles against HT-29 colon cancer cells, a particularly virulent form of cancer, and mechanistic studies have shown these to induce both intrinsic and extrinsic pathways of cell death leading to apoptosis  et al., 2005et al., 2007i.e. 3.052\u2005(3)\u2005\u00c5. The pattern of bond angles about the quaternary carbon atom, C1, follow the expected trends with the widest angle involving the sulfur and doubly bonded nitro\u00adgen atom and with the narrowest angle involving the single-bonded atoms. The conformation about the formal C1=N1 bond, Table\u00a01Z.The mol\u00adecular structure of the new monoclinic form of (I)P21/n with Z\u2032 = 1. The earlier polymorph, by contrast, crystallizes in triclinic space group PZ\u2032 = 1. A comparison of the key geometric parameters is given in Table\u00a01Form \u03b2 crystallizes in the monoclinic space group a and Table\u00a02b and Table\u00a023P ligands align to form a so-called six-fold phenyl embrace (6PE) Supra\u00admolecular dimers feature in the mol\u00adecular packing of form \u03b2 of (I)i.e. forms \u03b1 and \u03b2, were studied through Hirshfeld surface analysis by mapping on the normalized contact distance (dnorm) upon computation of the inner (di) and outer (de) distances of the Hirshfeld surface to the nearest nucleus Supra\u00admolecular features, C\u2014H\u22ef\u03c0 inter\u00adactions feature in both structures. To a first approximation the decomposed fingerprint plots look similar, as seen from Fig.\u00a05b. However, relatively shorter contacts are found in form \u03b2 cf. form \u03b1, i.e. 2.62 vs 2.68\u2005\u00c5. The clear distinction between the two forms is readily noted from the decomposed fingerprint plots for the O\u22efH/H\u22efO contacts with very distinct spikes evident for form \u03b2, Fig.\u00a05c, correlating with the C\u2014H\u22efO inter\u00adactions leading to dimer formation. While beyond the sum of their respective van der Waals radii  and asphericity (\u03a9) indices. All these indicators suggest that the polymorphs arise as a result of a simple inter\u00adplay between mol\u00adecular conformation and crystal-packing effects.In general, the observation of generally shorter contacts in form \u03b2 may indicate greater crystal-packing efficiency ,  is inter\u00admediate between those found in the polymorphic forms of (I)The most closely related structure to (I)Chemical context, biological considerations motivate ongoing investigations into the chemistry of phosphanegold(I) N-aryl-O-alkyl\u00adthio\u00adcarbamates. This notwithstanding, the relative ease of growing crystals have prompted several crystal engineering studies. Thus, correlations between Au\u22efAu (aurophilic) and solid-state luminescence responses have been made for the series of compounds, R3PAu[SC(OMe)=NC6H4NO2-p] , and bidentate phosphane analogues, Ph2P\u2013(CH2)n\u2013PPh2 for n = 1\u20134 and when the bridge is Fc (ferrocen\u00adyl) 4PPh2){AuSC(OR\u2032)=NC6H4Y-p}2] for R\u2032 = Me, Et or iPr and Y = H, NO2 or Me was undertaken =NR\u2032\u2032], for R = Ph, o-tol, m-tol or p-tol, and R\u2032\u2019 = Ph, o-tol, m-tol, p-tol or C6H4NO2-p, where it proved possible to induce a conformational change in the mol\u00adecule so that an intra\u00admolecular Au\u22ef\u03c0 inter\u00adaction formed rather than Au\u22efO  species yielding binuclear mol\u00adecules also with intra\u00admolecular Au\u22ef\u03c0 inter\u00adactions  in MeOH , followed by addition of the thio\u00adcarbamide, MeOC(=S)N(H)C6H4Cl3 , prepared following literature precedents : 1434 (s) \u03bd(C=N), 1180 (s) \u03bd(C\u2014O), 1098 (s) \u03bd(C\u2014S).Preparation of (I)Uiso(H) set to 1.2\u20131.5Ueq(C). The maximum and minimum residual electron density peaks of 2.04 and 1.06\u2005e\u2005\u00c5\u22123, respectively, were located 1.01 and 0.77\u2005\u00c5 from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016010781/hb7598sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016010781/hb7598Isup2.hklStructure factors: contains datablock(s) I. DOI: 1489737CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the pyrrolidine and cyclo\u00adhexane rings exhibit envelope and chair conformations, respectively. In the crystal, C\u2014H\u22efO inter\u00adactions connect the mol\u00adecules into tape structures. 19H25NO2, the pyrrolidine ring adopts an envelope form, with the spiro C atom as the flap, while the cyclo\u00adhexane ring shows a chair form. A weak intra\u00admolecular C\u2014H\u22efO inter\u00adaction supports the mol\u00adecular conformation, generating an S(6) ring motif. In the crystal, pairs of C\u2014H\u22efO inter\u00adactions connect the mol\u00adecules into inversion dimers with an R22(16) ring motif. The dimers are linked by a second pair of C\u2014H\u22efO inter\u00adactions, enclosing an R42(12) ring motif, into a tape structure along the b axis.In the title compound, C N-hy\u00addroxy or N-alk\u00adoxy substituent have been widely explored in organic synthesis. These substances show specific and intriguing reactivity caused by a covalent bond between the electronegative heteroatoms. Among these compounds, for example, the N-alk\u00adoxy\u00adamines are known to be initiators for stable free radical polymerization  = 0.1965\u2005(16)\u2005\u00c5 and \u03c6(2) = 151.8\u2005(5)\u00b0. The flap atom C5 deviates from the mean plane of other four atoms by 0.314\u2005(2)\u2005\u00c5. For the N-alk\u00adoxy-N-alkyl\u00adamide moiety, the geometry around atom N1 is a little deformed from a planar to a pyramidal configuration. The shift of atom N1 from the C2/C5/O14 plane is 0.2163\u2005(13)\u2005\u00c5, and the sum of angles for C2\u2014N1\u2014O14, O14\u2014N1\u2014C5 and C5\u2014N1\u2014C2 is 353.0\u00b0.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01Q = 0.5782\u2005(17)\u2005\u00c5, \u03b8 = 1.82\u2005(17)\u00b0, \u03c6 = 347\u2005(5)\u00b0, Q(2) = 0.0197\u2005(17)\u2005\u00c5 and Q(3) = 0.5779\u2005(17)\u2005\u00c5. The equatorially oriented C10\u2014C11 bond makes an angle of 70.60\u2005(9)\u00b0 with the normal to the Cremer & Pople plane of the cyclo\u00adhexane ring, and the vinyl group (C11=C12) is positioned in syn-periplanar geometry to the cyclo\u00adhexane framework, with a C9\u2014C10\u2014C11=C12 torsion angle of 10.9\u2005(2)\u00b0.The cyclo\u00adhexane ring (C5\u2013C10), which is spiro-fused to the pyrrolidine ring, adopts a chair form with puckering parameters of S(6) graph-set motif. No intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction is observed.An intra\u00admolecular C\u2014H\u22efO inter\u00adaction (C15\u2014H15\u22efO13) supports the mol\u00adecular conformation, generating an i; Table\u00a01b axis by weak C\u2014H\u22efO inter\u00adactions , are registered , but no compound with an N-alk\u00adoxy substituent, (c).In the Cambridge Structural Database , which is related to the title compound, (e), has also been reported , the pyrrolidine ring adopts a similar conformation to the title compound. The spiro-C atom is at the flap of the envelope, and the geometry around the N atom shows a little deformation to a pyramidal configuration with the sum of the C(carbon\u00adyl)\u2014N\u2014O, O\u2014N\u2014C and C\u2014N\u2014C(carbon\u00adyl) angles being 345.8\u2005(5)\u00b0. No intra\u00admolecular C\u2014H\u22efO inter\u00adaction is observed in (d).The structure of an et al., 2015m/z calculated for C19H25NO2Na+ [M + Na]+: 322.1783; found: 322.1779. Analysis calculated for C19H25NO2: C 76.22, H 8.42, N 4.68%; found: C 76.31, H 8.44, N 4.58%.The title compound was synthesized convergently from hex-5-en-1-ol, methyl 4-chloro-4-oxobutyrate and 1-phenyl\u00adethanol (Yamamoto Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015021209/is5431sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021209/is5431Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021209/is5431Isup3.cmlSupporting information file. DOI: 1435676CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two tridentate terpyridine ligands define the coordination of the Ni2+ cation, resulting in a nearly octa\u00adhedral coordination sphere, although there is not any imposed crystallographic symmetry about the Ni2+ site. The two nearly linear dicyanidoaurate(I) anions [C\u2014Au\u2014C = 179.0\u2005(2) and 178.2\u2005(2)\u00b0] contain a short aurophilic inter\u00adaction of 3.1017\u2005(3)\u2005\u00c5. The structure does not demonstrate any \u03c0\u2013\u03c0 stacking. Non-classical C\u2014H\u22efN inter\u00adactions between the cations and anions build up a three-dimensional network.The title compound, [Ni(C M(terpy)2](X)  have been known since the 1970\u2032s 2][Au(CN)2]2, (I)Derivatives of the compound 2 was synthesized and analysed ]2+ cation with dicyanidoaurate(I) anions. However, the important difference between the two compounds is that there are no metal\u2013metal inter\u00adactions in the [Ni(terpy)][Au(Br)2(CN)2]2 structure containing the d8 Au(III) ion, whereas the [Ni(terpy)2][Au(CN)2]2 structure contains a d10 gold(I) dicyanidoaurate(I) anion that has a strong propensity to form aurophilic inter\u00adactions. This makes the title compound of inter\u00adest because it contains short aurophilic inter\u00adactions, contained within dimeric [Au(CN)2]2 moieties, with Au\u22efAu distances of 3.1017\u2005(3)\u2005\u00c5 \u2005\u00c5 Fig.\u00a01.D\u22efA distance of 3.5\u2005\u00c5 as the upper defined limit. Details of the inter\u00adactions can be found in Table\u00a01Structural commentary above. There are no \u03c0\u2013\u03c0 stacking inter\u00adactions in the structure.A packing diagram of the title compound is illustrated in Fig.\u00a02M Ni(NO3)2 (1\u2005ml) and 0.1 M 2,2\u2032:6\u2032.2\"-terpyridine (1\u2005ml) were mixed together. Following the mixture of these two compounds, 2\u2005ml of 0.05 M KAu(CN)2 (50:50 ethanol/water v/v) was added dropwise. A precipitate formed and the suspension was mixed thoroughly and centrifuged. The brownish-red solution was deca\u00adnted from the solid precipitate and placed in a test tube to allow for slow evaporation. After approximately one week, the formation of brownish-red crystals had begun. The grown single crystals were then gathered and isolated.Ethanol solutions of 0.1 Uiso(H) = 1.2Ueq(C) and C\u2014H distances of 0.93\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814024672/wm5063sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814024672/wm5063Isup2.hklStructure factors: contains datablock(s) I. DOI: 1033527CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains a quarter each of two crystallographically independent propane-1,3-di\u00adammonium dicat\u00adions, [AlF6]3\u2212 and [AlF4(H2O)2]\u2212 anions and four water mol\u00adecules. The cations, anions and three of the independent water mol\u00adecules are situated on special positions mm, while the fourth water mol\u00adecule is disordered about a mirror plane. In the crystal, inter\u00admolecular N\u2014H\u22efF and O\u2014H\u22efF hydrogen bonds link the cations and anions into a three-dimensional framework with the voids filled by water mol\u00adecules, which generate O\u2014H\u22efO hydrogen bonds and further consolidate the packing.The title compound, (C The [AlF6] octa\u00adhedron is regular whereas [AlF4(H2O)2] exhibits a pronounced distortion due to the strong influence of the crystal field created by the heteroligands (F\u2212/H2O). The value of the calculated valences (3.08 for Al1 and 3.01 for Al2) of the individual Al3+ cations 2] octa\u00adhedron is linked via N\u2014H\u22efF or O\u2014H\u22efF hydrogen bonds (Table\u00a01a axis. These chains are linked to each other by the AlF63\u2212 dications and form infinite (H2dap)[AlF4(H2O)2] layers parallel to the ac plane anions or extended 1D inorganic chains, 2D inorganic layers or 3D networks are mentioned. Eight compounds with AlF63\u2212 anions exist 2\u2212 anion 2\u2212 anions have been reported.In the Cambridge Structural Database  in 40% HF (1.5\u2005ml) and ethanol (5\u2005ml). 1,3-Di\u00adamino\u00adpropane (0.54\u2005ml) was added and mild hydro\u00adthermal conditions (463\u2005K) were applied in a Teflon-lined autoclave (25\u2005ml). The resulting product was washed with ethanol and dried in air giving colourless single crystals.The title compound was prepared from a starting mixture of AlF3 and CH2 groups of the organic mol\u00adecule were fixed geometrically [N\u2014H = 0.89\u2005(1) and C\u2014H = 0.97\u2005(1)\u2005\u00c5 with Uiso(H) = 1.2Ueq]. All H atoms of the water mol\u00adecules were located from a Fourier difference map. The O\u2014H distances and H\u2014O\u2014H angles were fixed [O\u2014H = 0.84\u2005(1) and H\u22efH = 1.34\u2005(1)\u2005\u00c5 with Uiso(H) =1.5Ueq(O)]. The water mol\u00adecule OW5 is disordered over two positions with the occupanies fixed to 0.5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814024155/cv5471sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814024155/cv5471Isup2.hklStructure factors: contains datablock(s) I. DOI: 1032262CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in the title complex is surrounded by a distorted Cl2N4 coordination set. In the crystal structure, adjacent complex mol\u00adecules are connected through C\u2014H\u22efCl hydrogen-bonding inter\u00adactions into a layered arrangement parallel to (100). Additional C\u2014H\u22efBr hydrogen-bonding inter\u00adactions along with \u03c0\u2013\u03c0 stacking inter\u00adactions complete a three-dimensional supra\u00admolecular network.The Ru 2(C12H9BrN2)2] or [RuCl2(PM-BrA)2] (PM-BrA = 4-bromo-N-(2\u2032-pyridyl\u00admethyl\u00adene)aniline), the RuII cation is located on a centre of inversion and is surrounded by four N atoms of two PM-BrA ligands in the equatorial plane and by two Cl atoms in a trans axial arrangement, displaying a distorted octa\u00adhedral coordination environment. Two C atoms in the benzene ring of the PM-BrA ligand are equally disordered over two sets of sites. The benzene and pyridine rings of the PM-BrA ligand are oriented at dihedral angles of 62.1\u2005(10) and 73.7\u2005(11)\u00b0 under consideration of the two orientations of the disordered benzene ring. In the crystal, the complex mol\u00adecules are connected via C\u2014H\u22efCl hydrogen-bonding inter\u00adactions into a layered arrangement parallel (100). C\u2014H\u22efBr hydrogen bonding and weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions complete a three-dimensional supra\u00admolecular network.In the title complex, [RuCl Their complexes have found utility in a wide range of applications \u2005\u00c5 with an N1\u2014Ru1\u2014N2 bite angle of 76.9\u2005(1)\u00b0. The reduced bite angle of the chelating ligand is one of the main factors accounting for the distortion from the ideal octa\u00adhedral geometry of the coordination polyhedron, with the the largest cis angle being 103.1\u2005(2)\u00b0. The Ru\u2014N bond lengths are 2.073\u2005(5) and 2.084\u2005(5)\u2005\u00c5, and the Ru\u2014Cl bond length is 2.3908\u2005(14)\u2005\u00c5, in agreement with those observed in the structures of similar compounds re Fig.\u00a01. The cooX  inter\u00adactions are compiled in Table\u00a01In the crystal, weak inter\u00admolecular C\u2014H\u22efCl hydrogen-bonding inter\u00adactions between the C atoms of the benzene ring and the Cl atoms connect the complex mol\u00adecules into a supra\u00admolecular layered arrangement parallel to (100) Fig.\u00a02. As showtrans-[RuCl2(Hpyrimol)2] (Hpyrimol = 4-methyl-2-N-(2-pyridyl\u00admethyl\u00adene)amino\u00adphenol) with a closely related Schiff base N2 donor set for each ligand has been reported aniline  in dry methanol (5\u2005ml) was placed in a test tube. A solution of RuCl3  in dry methanol (5\u2005ml) was then carefully layered on the top of a methano\u00adlic solution. After slow diffusion at room temperature for three days, pale-green plate- or block-like crystals of complex (I)A solution of the ligand 4-bromo-Uiso(H) = 1.2Ueq(C) using a riding model with C\u2014H = 0.95\u2005\u00c5. C atoms C11 and C12 and attached H atoms in the benzene ring are disordered over two set of sites and were refined using a split model with equal occupancy.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901501556X/wm5204sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901501556X/wm5204Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901501556X/wm5204Isup3.cdxSupporting information file. DOI: 1419653CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E conformation with respect to the azomethine C=N bond and the aromatic rings are inclined to one another by 3.29\u2005(4)\u00b0. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, forming zigzag chains along [10-1].The title compound has an  14H13NO2 {systematic name: (E)-2-[(4-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adphenol}, is a product of the condensation reaction between 4-meth\u00adoxy\u00adbenzaldehyde and 2-amino\u00adphenol. The mol\u00adecule adopts an E conformation with respect to the azomethine C=N bond and is almost planar, the dihedral angle between the two substituted benzene rings being 3.29\u2005(4)\u00b0. The meth\u00adoxy group is coplanar with the benzene ring to which it is attached, the Cmeth\u00adyl\u2014O\u2014C\u2014C torsion angle being \u22121.14\u2005(12)\u00b0. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond generating an S(5) ring motif. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, forming zigzag chains along [10-1]. The chains are linked via C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional structure.The title aza\u00adstilbene derivative, C The mol\u00adecule is almost planar with a dihedral angle of 3.29\u2005(4)\u00b0 between the two substituted benzene rings. The meth\u00adoxy group is co-planar with the benzene ring to which it is attached, the C14\u2014O1\u2014C4\u2014C5 torsion angle being \u22121.14\u2005(12)\u00b0. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond  ring motif. The bond lengths are comparable with those found for some closely related structures . Colourless block-shaped crystals, suitable for X-ray structure analysis, were obtained by recrystallization from methanol by slow evaporation at room temperature after several days (m.p. 388\u2013390\u2005K).A solution of 4-meth\u00adoxy\u00adbenzaldehyde  in water (20\u2005ml) and 2-amino\u00adphenol  in water (20\u2005ml) were mixed and stirred at room temperature for around 8\u2005h until a white precipitate appeared. The resulting white solid was filtered, washed several times with cold ethanol and then dried 3OH) \u03bbmax (log\u220a): 275 (1.93), 340 (0.61)\u2005nm; FT\u2013IR (KBr) \u03bd: 3337, 1595, 1510, 1248, 1027\u2005cm\u22121.; 1H NMR  \u03b4, p.p.m.: 8.87 , 8.61 , 7.98 , 7.18 , 7.06 , 7.03 , 6.83 , 6.09 , 3.84 . The UV\u2013Vis spectroscopic data showed absorption bands of an aza\u00adstilbene (275 and 340\u2005nm) while the FT\u2013IR spectrum exhibited the stretching vibrations of O\u2014H (3337\u2005cm\u22121), C=N (1595\u2005cm\u22121), C=C (1510\u2005cm\u22121), C\u2014N (1248\u2005cm\u22121) and C\u2014O (1027\u2005cm\u22121). The successful synthesis was also supported by the 1H NMR spectroscopic data, which showed the characteristic signals of an olefinic proton at 8.61  and para-substituted aromatic protons at 7.98  and 7.06 , respectively. Moreover the 1H NMR spectrum also showed typical signals of ortho-substituted aromatic protons at 7.18 , 7.03 , 6.83  and 6.09  and a meth\u00adoxy proton at 3.84 .UV\u2013Vis  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015008348/su5124sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008348/su5124Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008348/su5124Isup3.cmlSupporting information file. DOI: 1062128CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom within an S(di\u00adthio\u00adcarbamate) and P(phosphane) donor set.The centrosymmetric mol\u00adecule features a linearly coordinated Au 34H28FeP2)[Au(C5H8NS2)]2}, comprises half a mol\u00adecule, with the full mol\u00adecule being generated by the application of a centre of inversion. The independent AuI atom is coordinated by thiol\u00adate S and phosphane P atoms that define an approximate linear geometry [S\u2014Au\u2014P = 169.35\u2005(3)\u00b0]. The deviation from the ideal linear is traced to the close approach of the (intra\u00admolecular) non-coordinating thione S atom [Au\u22efS = 3.1538\u2005(8)\u2005\u00c5]. Supra\u00admolecular layers parallel to (100) feature in the crystal packing, being sustained by phen\u00adyl\u2013thione C\u2014H\u22efS inter\u00adactions, with the non-coordinating thione S atom in the role of a dual acceptor. Layers stack with no specific inter\u00adactions between them.The asymmetric unit of the title compound, {(C R3PAu(S2CNR\u20322), date back over a decade CH2CH2OH], R = Ph and Cy, exhibited specific activity against Gram-positive bacteria while the R = Et derivative displayed broad-range activity against both Gram-positive and Gram-negative bacteria. Motivated by observations that 1,1\u2032-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)ferrocene (dppf) derivatives also possess biological activity 4]}2, (I)Investigations into the potential anti-cancer activity of phosphanegold(I) di\u00adthio\u00adcarbamates, II atom in dppf{Au[S2CN(CH2)4]}2, (I)I central atom exists in the anti\u00adcipated linear geometry defined by thiol\u00adate-S and phosphane-P atoms. The Au\u2014S1 bond length is considerably longer than the Au\u2014P1 bond, i.e. 2.3378\u2005(8) cf. 2.2580\u2005(8)\u2005\u00c5. The di\u00adthio\u00adcarbamate ligand is orientated to place the S2 atom in close proximity to the AuI atom. However, the resulting intra\u00admolecular Au\u22efS2 inter\u00adaction is long at 3.1538\u2005(8)\u2005\u00c5, consistent with a monodentate mode of coordination for the di\u00adthio\u00adcarbamate ligand. The pattern of C1\u2014S1, S2 bond lengths supports this conclusion in that the strongly bound S1 atom forms a longer, i.e. weaker, C1\u2014S1 bond [1.757\u2005(3)\u2005\u00c5] cf. with C1\u2014S2 of 1.689\u2005(3)\u2005\u00c5. Nevertheless, the close approach of the S2 atom to the AuI central atom is correlated with the deviation from the ideal linear geometry, i.e. S1\u2014Au\u2014P1 is 169.35\u2005(3)\u00b0. The FeDatabase survey. The pyrrolidine ring is twisted about the C2\u2014C3 bond. Owing to being located on a centre of inversion, the FeII atom is equidistant from the ring centroids of the Cp rings  and the Cg\u2014Fe\u2014Cgi angle is constrained by symmetry to be 180\u00b0; symmetry operation (i): 1\u00a0\u2212\u00a0x, \u2212y, 2\u00a0\u2212\u00a0z. Again, from symmetry, the Cp rings have a staggered relationship.Similar features are noted in related structures as outlined below in the bc plane, Fig.\u00a02a axis, i.e. 10.9635\u2005(4)\u2005\u00c5, and the layers stack along this axis with no directional inter\u00adactions between them, Fig.\u00a03In the crystal packing, the most prominent inter\u00adactions are of the type C\u2014H\u22efS. Data for the phenyl-C\u2014H\u22efS(thione) inter\u00adactions are collected in Table\u00a01i.e. Ph3PAu(S2CNEt2), by Wijnhoven et al. (19723P 2\u00b72CHCl3, bis\u00ad[chlorido\u00adgold(I)] (synthesized by the reduction of KAuClUiso(H) set to 1.2Ueq(C). The maximum and minimum residual electron density peaks of 1.57 and 1.11\u2005e\u2005\u00c5\u22123, respectively, were located 0.92 and 0.79\u2005\u00c5 from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015016382/vn2097sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015016382/vn2097Isup2.hklStructure factors: contains datablock(s) I. DOI: 1421954CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Sodium bicarbonate intake has been shown to improve exercise tolerance, but the effects on high-intensity intermittent exercise are less clear. Thus, the aim of the present study was to determine the effect of sodium bicarbonate intake on Yo-Yo intermittent recovery test level 2 performance in trained young men.2max: 61.3\u2009\u00b1\u20093.3 mlO2\u2009\u00b7\u2009kg\u22121\u2009\u00b7\u2009min\u22121; means\u2009\u00b1\u2009SEM) performed the Yo-Yo intermittent recovery test level 2 (Yo-Yo IR2) on two separate occasions in randomized order with (SBC) and without (CON) prior intake of sodium bicarbonate (0.4 g\u2009\u00b7\u2009kg\u22121 body weight). Heart rate and rating of perceived exertion (RPE) were measured during the test and venous blood samples were taken frequently.Thirteen men aged 23\u2009\u00b1\u20091 year . Blood lactate was 0.9\u2009\u00b1\u20090.1 and 0.8\u2009\u00b1\u20090.1 mmol\u2009\u00b7\u2009l\u22121 at baseline and increased to 11.3\u2009\u00b1\u20091.4 and 9.4\u2009\u00b1\u20090.8 mmol\u2009\u00b7\u2009l\u22121 at exhaustion in SBC and CON, respectively, being higher (P\u2009=\u20090.03) in SBC. Additionally, peak blood lactate was higher (P\u2009=\u20090.02) in SBC than in CON (11.7\u2009\u00b1\u20091.2 vs 10.2\u2009\u00b1\u20090.7 mmol\u2009\u00b7\u2009l\u22121). Blood glucose, plasma K+ and Na+ were not different between trials. Peak heart rate reached at exhaustion was 197\u2009\u00b1\u20093 and 195\u2009\u00b1\u20093 bpm in SBC and CON, respectively, with no difference between conditions. RPE was 7\u00a0% lower (P\u2009=\u20090.003) in SBC than in CON after 440 m, but similar at exhaustion (19.3\u2009\u00b1\u20090.2 and 19.5\u2009\u00b1\u20090.2).Yo-Yo IR2 performance was 14\u00a0% higher (P\u2009=\u20090.04) in SBC than in CON . Blood pH and bicarbonate were similar between trials at baseline, but higher (P\u2009=\u20090.003) immediately prior to the Yo-Yo IR2 test in SBC than in CON (7.44\u2009\u00b1\u20090.01 vs 7.32\u2009\u00b1\u20090.01 and 33.7\u2009\u00b1\u20093.2 vs 27.3\u2009\u00b1\u20090.6 mmol\u2009\u00b7\u2009lIn conclusion, high-intensity intermittent exercise performance is improved by prior intake of sodium bicarbonate in trained young men, with concomitant elevations in blood alkalosis and peak blood lactate levels, as well as lowered rating of perceived exertion. The remaining whole blood was then centrifuged at 4000 rpm for 3 min  before plasma was extracted and stored on ice for ~30 min prior to being frozen at -80\u2009Denmark) .RPE was assessed at 160, 280, 440 m and exhaustion according to the 20-stage Borg scale .P\u2009<\u20090.05. Results are presented as mean\u2009\u00b1\u2009SEM unless stated otherwise.Differences between SBC and CON in Yo-Yo IR2 performance were analyzed using a paired-samples t-test. Differences between SBC and CON in blood and plasma variables were analyzed using a two-way ANOVA with repeated measures (supplement x time). If a significant F-value was observed, a Tukey post-hoc test was used to identify the points of difference. Statistical significance was accepted at Yo-Yo IR2 performance was 735\u2009\u00b1\u200961 m in SBC, which was 14\u00a0% higher (P\u2009=\u20090.04) than in CON  to 7.44\u2009\u00b1\u20090.01 in SBC before the Yo-Yo IR2 test and decreased (P\u2009=\u20090.005) in CON  in SBC before the Yo-Yo IR2 test (33.7\u2009\u00b1\u20093.2 mmol\u2009\u00b7\u2009l\u22121) and was unchanged in CON (27.3\u2009\u00b1\u20090.6 mmol\u2009\u00b7\u2009l\u22121) compared to baseline. At exhaustion, blood [bicarbonate] declined (P\u2009<\u20090.001) in SBC and CON (25.2\u2009\u00b1\u20092.6 and 20.2\u2009\u00b1\u20090.8 mmol\u2009\u00b7\u2009l\u22121). Pre-exercise and exhaustive blood [bicarbonate] was higher (P\u2009=\u20090.01 and 0.03) in SBC than in CON  11.3\u2009\u00b1\u20091.4 and 9.4\u2009\u00b1\u20090.8 mmol\u2009\u00b7\u2009l\u22121 at exhaustion in SBC and CON, respectively, being higher (P\u2009=\u20090.03) in SBC (Table\u00a0\u22121).Blood lactate was 0.9\u2009\u00b1\u20090.1 and 0.8\u2009\u00b1\u20090.1 mmol\u2009\u00b7\u2009l\u22121 at baseline to 5.1\u2009\u00b1\u20090.5 and 5.2\u2009\u00b1\u20090.6 mmol\u2009\u00b7\u2009l\u22121 at exhaustion, with no difference between trials (Table\u00a0Blood glucose rose (P\u2009<\u20090.05) from 4.2\u2009\u00b1\u20090.4 and 4.1\u2009\u00b1\u20090.2 mmol\u2009\u00b7\u2009l+] rose (P\u2009<\u20090.05) from 4.3\u2009\u00b1\u20090.4 and 4.2\u2009\u00b1\u20090.4 mmol\u2009\u00b7\u2009l\u22121 at baseline to 5.7\u2009\u00b1\u20090.5 and 5.8\u2009\u00b1\u20090.6 mmol\u2009\u00b7\u2009l\u22121 at exhaustion in SBC and CON, respectively, with no differences between trials  during the test, reaching 197\u2009\u00b1\u20093 and 195\u2009\u00b1\u20093 bpm at exhaustion in SBC and CON, respectively. No difference in heart rate response between conditions was determined during or after the test.RPE was not different between trials after 160 and 280 m , but was 7\u00a0% lower (P\u2009=\u20090.003) after 440 m in SBC than in CON (16.8\u2009\u00b1\u20090.4 vs 17.9\u2009\u00b1\u20090.3). At exhaustion, RPE was similar in SBC and CON (19.3\u2009\u00b1\u20090.2 and 19.5\u2009\u00b1\u20090.2).+ and Na+ as well as cardiovascular loading during high-intensity intermittent exercise were unaffected by sodium bicarbonate intake.In the present study, we observed that prior intake of sodium bicarbonate in capsular form using a protocol with gradual intake enhanced high-intensity intermittent exercise performance in young trained males. The performance improvement after sodium bicarbonate ingestion was accompanied by an elevated blood alkalosis and concentration of bicarbonate. In addition, blood lactate concentrations at exhaustion and peak values reached during the experimental protocol were higher, while the rating of perceived exertion was lower during intense exercise after sodium bicarbonate supplementation. In contrast, blood glucose, plasma KPerformance in the Yo-Yo IR2 test increased by 14\u00a0% after sodium bicarbonate intake, which is comparable to a 16\u00a0% increase after caffeine intake in a comparable athlete population , but lowIn the present study, we did not apply a placebo, since the gastrointestinal effects of high doses of bicarbonate are usually easy to trace . A poten+ gradient  and [Na+] between the sodium bicarbonate and control trials. However, since the potential fatiguing effect of a homeostatic imbalance in these ions is exerted in the muscle interstitial compared to intracellular environment [+ regulation, Street et al. [+ accumulation rate during intense exercise was attenuated after drug-induced alkalosis.Fatigue development during high-intensity intermittent exercise may be caused by a complex interplay between intra- and extracellular concentrations and gradients of ions such as K\u2212 and H+ , 29. In ironment \u201332, a soironment . In suppt et al.  found, umax and blood lactate and plasma K+ were markedly elevated. Moreover, although further distance was covered before exhaustion, the RPE scores remained the same as in the control trial at the point of fatigue. Thus, a higher performance level was achieved while reporting an equal level of perceived fatigue at exhaustion. Peripheral alterations are likely to lead to modulation of neural strategies, for example via group III and IV muscle afferents, widely distributed through muscle and responsive to a variety of chemical stimuli, including altered H+ [In the present study, RPE was lowered after 440 m of running in the Yo-Yo IR2 test in the sodium bicarbonate trial compared to the control, despite the fact that the heart rate and blood lactate concentration at this time-point were similar between trials. This may suggest that centrally mediated mechanisms were affected. The participants experienced less exertion late in the Yo-Yo IR2 test in the SBC trial when the heart rate was >95\u00a0% of HRtered H+ , 34, whitered H+ , 35.\u22121 body weight) improved high-intensity intermittent exercise performance in trained young men, with concomitant increased blood alkalosis. Sodium bicarbonate supplementation increased blood lactate levels at exhaustion and lowered rating of perceived exertion during intense intermittent exercise. The results indicate a link between improved fatigue resistance during high-intensity intermittent exercise and a sodium-bicarbonate-induced improved buffer capacity that may affect perceived exertion during intense intermittent exhaustive exercise.High-dose sodium bicarbonate intake (0.4 g\u2009\u00b7\u2009kg"}
{"text": "Single crystals were obtained from HSO3F by slow cooling in a sealed tube. The mol\u00adecular structure is characterized by the Xe atom covalently bonded to two O atoms of two fluoro\u00adsulfate tetra\u00adhedra in an almost linear fashion [O\u2014Xe\u2014O = 179.13\u2005(4)\u00b0]. The crystal packing is strongly influenced by inter\u00admolecular van der Waals forces.Thermally unstable Xe(SO For XeF(OSO2F), partial ionic bonding (XeF+\u00b7OSO2F\u2212) was discussed. Obviously, both XeF2 and Xe(SO3F)2 have a higher covalent character. The S\u2014O bonds in Xe(SO3F)2 involving the O atoms that are also bonded to the xenon atom (S1\u2014O1 and S2\u2014O4) are about 0.1\u2005\u00c5 longer than the terminal S\u2014O bonds  has fewer contacts  was warmed to 273\u2005K and the PFA tube placed in a dewar filled with 273\u2005K ethanol and cooled slowly to 193\u2005K in a freezer. The light-yellow single crystals of Xe(SO3F)2 that had formed were deca\u00adnted off and mounted in a cold nitro\u00adgen stream. At 100\u2005K, the crystals are colorless. The compound decomposes rapidly in moist air and can ignite organic materials.550\u2005mg fluoro\u00adsulfuric acid were placed in a 8\u2005mm PFA tube. 170\u2005mg (1\u2005mmol) of XeFCrystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015004788/wm5134sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004788/wm5134Isup2.hklStructure factors: contains datablock(s) I. DOI: 1052852CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit is composed of a copper(II) tetra\u00adacetate paddle-wheel complex, a Cl\u2212 anion situated on a twofold rotation axis, half a 1,3-bis\u00adimidazolium cation (the whole mol\u00adecule being generated by twofold rotation symmetry) and one and a half of a di\u00adchloro\u00admethane solvent mol\u00adecule (one being located about a twofold rotation axis). The central metal-organic framework comprises of a tetra\u00adnuclear copper(II) acetate \u2018paddle-wheel\u2019 complex which arises from the dimerization of the copper(II) tetra\u00adacetate core comprising of three \u03bc2-bidentate acetate and one \u03bc3-tridentate acetate ligands per binuclear paddle-wheel complex. Both CuII atoms of the binuclear component adopt a distorted square-pyramidal coordination geometry (\u03c4 = 0.04), with a Cu\u22efCu separation of 2.6016\u2005(2)\u2005\u00c5. The apical coordination site of one CuII atom is occupied by an O atom of a neighbouring acetate bridge [Cu\u2014O = 2.200\u2005(2)\u2005\u00c5], while that of the second CuII atom is occupied by a bridging chloride ligand [Cu\u22efCl = 2.4364\u2005(4)\u2005\u00c5]. The chloride bridge is slightly bent with respect to the Cu\u22efCu inter\u00adnuclear axis [Cu\u2014Cl\u2014Cu = 167.06\u2005(6)\u00b0] and the tetra\u00adnuclear units are located about a twofold rotation axis, forming the one-dimensional polymer that propagates along [101]. Charge neutrality is maintained by the inclusion of the 1,3-bis\u00adimidazolium cation within the crystal lattice. In the crystal, the cation and di\u00adchloro\u00admethane solvent mol\u00adecules are linked to the coordin\u00adation polymer by various C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds. There are no other significant inter\u00admolecular inter\u00adactions present.The title copper(II) complex, {(C For the al. 2005; Bull et al. 2008. For det al. 1964; Zhang e al. 2005; Cotton  al. 2000, and for al. 2003. For exa al. 1973; Ackerma al. 2000. For chl al. 2015. For imi al. 2015. For the al. 1984.27H37N2)[Cu4(C2H3O2)8Cl]\u00b73CH2Cl2 \u00c5b = 13.146 (2) \u00c5c = 23.607 (3) \u00c5\u03b2 = 117.122 (4)\u00b0V = 6103.5 (13) \u00c53Z = 4K\u03b1 radiationMo \u22121\u03bc = 1.74 mmT = 100 K0.22 \u00d7 0.13 \u00d7 0.05 mmBruker SMART CCD area-detector diffractometerSADABS; Bruker, 2001Tmin = 0.700, Tmax = 0.918Absorption correction: multi-scan (26111 measured reflections7274 independent reflectionsI > 2\u03c3(I)5215 reflections with Rint = 0.079R[F2 > 2\u03c3(F2)] = 0.054wR(F2) = 0.098S = 0.987274 reflections348 parametersH-atom parameters constrainedmax = 0.70 e \u00c5\u22123\u0394\u03c1min = \u22120.46 e \u00c5\u22123\u0394\u03c1SMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015013675/su5152Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015013675/su5152fig1.tif. DOI: A view of the mol\u00adecular structure of the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.Click here for additional data file.10.1107/S2056989015013675/su5152fig2.tifx y z x y z x y z x y z x y z . DOI: x, y, \u2212z\u00a0+\u00a0x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01; (c) x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0x, y, \u2212z\u00a0+\u00a0x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0A view of the tetra\u00adnuclear paddle-wheel unit of the title polymeric compound [symmetry codes: (a) \u2212Click here for additional data file.10.1107/S2056989015013675/su5152fig3.tifb 2 2 . DOI: b axis of the crystal packing of title compound. Colour code: coordination polymer black, organic cation red; CH2Cl2 solvent mol\u00adecules green and blue.A view along the 999046CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: interactive version of Fig. 1dEnhanced figure:"}
{"text": "The O\u2014O bond length of the peroxide is 1.485\u2005(6)\u2005\u00c5 and the mid-point of this bond is located at the inversion centre of the dimer. The U atom exhibits a distorted hexa\u00adgonal\u2013bipyramidal coordination geometry with two uran\u00adyl(VI) O atoms occupying the axial positions and one O atom of the monodentate nitrate ion, both O atoms of the peroxide ion and the three N atoms of the chelating tridentate 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine (terpy) ligand in the equatorial positions. Two of the N atoms of the terpy ligand lie above and below the mean plane containing the equatorial ligand atoms and the U atom . The dihedral angle between the terpy ligand and the mean plane is 35.61\u2005(7)\u00b0. The bond lengths around the U atom decrease in the order U\u2014N > U\u2014Onitrate > U\u2014Operoxo > U=O. The dimeric complexes pack in a three-dimensional network held together by weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.659\u2005(3)\u2005\u00c5] between pyridyl rings of the terpy ligands in neighbouring dimers, together with inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. Weak intra\u00admolecular C\u2014H\u22efO inter\u00adactions are also observed.In the title dimeric complex, [{UO For the al. 2001; Goff et al. 2008; John et al. 2004; Sigmon  al. 2009; Takao & al. 2009. For theuwer 2004.2(NO3)2(O2)O4(C15H11N3)2] = 0.030wR(F2) = 0.058S = 0.894695 reflections235 parametersH-atom parameters constrainedmax = 2.24 e \u00c5\u22123\u0394\u03c1min = \u22121.57 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015007987/cq2015Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015007987/cq2015fig1.tif2 3 15 11 3 2 2 x y z . DOI: 2(NO3)(C15H11N3)}2O2]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. Structure of the dimer [{UOClick here for additional data file.10.1107/S2056989015007987/cq2015fig2.tif2 3 15 11 3 2 2 . DOI: 2(NO3)(C15H11N3)}2O2]. Dashed lines and dotted lines are \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions, respectively.Packing diagram of [{UO1061056CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These complexes are relevant to catalysis for CO2 reduction.The structures of two facially coordinated Group VII metal complexes,  fac-[ReCl(C10H8N2O2)(CO)3]\u00b7C4H8O (I\u00b7THF) and fac-[MnBr(C10H8N2O2)(CO)3]\u00b7C4H8O (II\u00b7THF), are reported. In both complexes, the metal ion is coordinated by three carbonyl ligands, a halide ligand, and a 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine ligand in a distorted octa\u00adhedral geometry. Both complexes co-crystallize with a non-coordinating tetra\u00adhydro\u00adfuran (THF) solvent mol\u00adecule and exhibit inter\u00admolecular but not intra\u00admolecular hydrogen bonding. In both crystal structures, chains of complexes are formed due to inter\u00admolecular hydrogen bonding between a hy\u00addroxy group from the 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine ligand and the halide ligand from a neighboring complex. The THF mol\u00adecule is hydrogen bonded to the remaining hy\u00addroxy group.The structures of two facially coordinated Group VII metal complexes,  In this paper we report the synthesis and structural characterization of fac-[Re(CO)3Cl] as well as the synthesis and structural characterization of the related and previously unknown complex, fac-[Mn(CO)3Br]. Both complexes co-crystallize with a tetrahydrofuran (THF) solvent molecule.The fac-[Re(CO)3Cl]\u00b7THF (I\u00b7THF) and [Mn(CO)3Br]\u00b7THF (II\u00b7THF), respectively. Complexes I and II exhibit distorted octa\u00adhedral geometries and contain primary coord\u00adination spheres similar to those of other fac-[Re(\u03b1-di\u00adimine)(CO)3Cl] and fac-[Mn(\u03b1-di\u00adimine)(CO)3Br] complexes, including [Re(bi\u00adpyridine)(CO)3Cl] (III)    and 18.93\u2005(3)\u00b0 for the Re and Mn complexes, respectively. Neither I\u00b7THF nor II\u00b7THF exhibit intra\u00admolecular hydrogen bonding.In I, the bi\u00adpyridine rings present a bite angle of 74.09\u2005(8)\u00b0 to Re, similar to that found in III [74.41\u2005(9)\u00b0] and IV [74.9\u2005(2)\u00b0]. The bi\u00adpyridine\u2013Mn bite angle in II, 78.35\u2005(4)\u00b0, is similar to that in V [79.0\u2005(5)\u00b0]. The bi\u00adpyridine ligands are not strictly planar. The dihedral angles between the pyridine rings are 11.68\u2005(9)\u00b0 in I and 9.49\u2005(5)\u00b0 in II. Additionally, the bi\u00adpyridine ligands are not oriented strictly perpendicularly to the coordination planes of the metal ions. The dihedral angles between the mean plane through the \u03b1-di\u00adimine ligands and the COa axis is formed by an O\u2014H\u22efCl hydrogen bond between a hy\u00addroxy group (O16\u2014H16) and the chloride ligand from the neighboring complex. The other hy\u00addroxy group (O26\u2014H26) is hydrogen-bonded to the O atom of the THF mol\u00adecule. The nearest pyridine rings between neighboring complexes have centroid\u2013centroid distances of 3.9448\u2005(16)\u2005\u00c5, longer than the maximum distance typically given for \u03c0\u2013\u03c0 inter\u00adactions  is hydrogen-bonded to O1S of the solvent THF mol\u00adecule. There are weak \u03c0\u2013\u03c0 stacking inter\u00adactions between pairs of complexes from neighboring chains. The centroid\u2013centroid distance between pairs of pyridine rings is 3.7019\u2005(9)\u2005\u00c5 and the angle between the ring normal and the vector between the ring centroids is 9.3\u00b0, within the parameters typically given for such \u03c0\u2013\u03c0 inter\u00adactions 5 and ReCl(CO)5 were purchased commercially and used as received. The ligand 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine was synthesized according to the synthetic procedure of Umemoto et al.  were heated at 333\u2005K in 50\u2005mL methanol under nitro\u00adgen for five\u2005h. The flask was covered with aluminum foil to keep out light. The reaction was then allowed to cool to room temperature and the solvent was removed under vacuum to give a yellow precipitate. Slow cooling of a hot THF solution of the complex in a glove box under a nitro\u00adgen atmosphere gave yellow plate-shaped crystals suitable for single crystal X-ray diffraction. Due to limited solubility of the complex in THF, this method could not be used for a bulk recrystallization of the complex.I\u00b7THF: 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine  and ReCl(CO)5  were heated at 333\u2005K in 24\u2005mL methanol under nitro\u00adgen for five\u2005h. The flask was covered with aluminum foil to keep out light. The reaction was then allowed to cool to room temperature and the solvent was removed under vacuum to give an orange precipitate. The complex was recrystallized in bulk by layering pentane on a THF solution of the complex in a glove box under a nitro\u00adgen atmosphere at room temperature, giving the pure product in near qu\u00adanti\u00adtative yield. Slow diffusion of diethyl ether into a THF solution of the complex in a glove box under a nitro\u00adgen atmosphere gave yellow rod-shaped crystals suitable for single crystal X-ray diffraction.II\u00b7THF: 6,6\u2032-dihy\u00addroxy-2,2\u2032-bi\u00adpyridine  and MnBr(CO)Uiso(H) = 1.5 Ueq(O). C-bound H atoms were placed in calculated positions and refined with riding coordinates, with Uiso(H) = 1.2 Ueq(C). In I\u00b7THF, disorder occurs for one carbon and six hydrogens of the THF solvent with occupancies of 0.748\u2005(11) and 0.252\u2005(11). Rigid bond (DELU) and similar ADP (SIMU) restraints were used for atoms O1S, C1S, C2S, C3T, C3S and C4S.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016011841/is5457sup1.cifCrystal structure: contains datablock(s) Re_complex, Mn_complex, global. DOI: 10.1107/S2056989016011841/is5457Re_complexsup4.hklStructure factors: contains datablock(s) Re_complex. DOI: 10.1107/S2056989016011841/is5457Mn_complexsup5.hklStructure factors: contains datablock(s) Mn_complex. DOI: 1495018, 1495017CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The largest deviation from the ideal octa\u00adhedral geometry is reflected by the small N\u2014Fe\u2014N bite angle of 76.0\u2005(1)\u00b0. The Fe\u2014N coordination bonds have markedly different lengths [2.1361\u2005(17) and 2.243\u2005(2)\u2005\u00c5], with the shorter one to the pyrimidine N atom. The four Fe\u2014O coordination bond lengths vary from 2.1191\u2005(18) to 2.1340\u2005(17)\u2005\u00c5. In the crystal, the cations and anions are arranged by means of medium-strength O\u2014H\u22efO hydrogen bonds into layers parallel to the ab plane. Neighbouring layers further inter\u00adconnect by N\u2014H\u22efO hydrogen bonds involving the imidazole fragment as donor group to one sulfate O atom as an acceptor. The resulting three-dimensional network is consolidated by C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions.In the title compound, [Fe(C The distorted octa\u00adhedral environment of the central FeII ion is defined by two N donor atoms of the pyim ligand and by the O atoms of two water mol\u00adecules in the equatorial plane, while the two remaining water mol\u00adecules coordinate at the axial sites. The bite angle N1\u2014Fe\u2014N2 of 76.04\u2005(7)\u00b0 shows the most significant deviation from the ideal octa\u00adhedral geometry, with the other coordination angles deviating by 0.21\u2005(7) to 11.91\u2005(7)\u00b0.Fig.\u00a012O)4]SO4 complex where dmbpy is 5,5\u2032-dimethyl-2,2\u2032-bi\u00adpyridine \u00b0. The dihedral angle of 5.5\u2005(1) \u00b0 between the aromatic rings of the pyim ligand is within the range of the values reported for the eight independent mol\u00adecules in the crystal structure of the non-coordinating ligand SO4 complex, which range from 2.079\u2005(2) to 2.110\u2005(2)\u2005\u00c5.The Fe\u2014N coordination bonds with the chelate ligand have markedly different lengths, Fe\u2014N1 = 2.243\u2005(2) and Fe\u2014N2 = 2.1361\u2005(17)\u2005\u00c5, which are also dissimilar to those in the previously reported [Fe(dmbpy)(H2O)4]2+ unit is surrounded by five [SO4]2\u2212 anions. Similarly to the crystal structure of [Fe(dmbpy)(H2O)4]SO4, pairs of axially and equatorially coordinating water mol\u00adecules bind to pairs of O acceptor atoms from the same [SO4]2\u2212 group, forming eight medium-strength inter\u00adactions  = \u2212x\u00a0+\u00a0y\u00a0+\u00a0z; Cg1 is the centroid of the imidazole ring] and weak \u03c0\u2013\u03c0 inter\u00adactions . C\u2014H\u22efO inter\u00adactions are also observed s Table\u00a01. These hne Fig.\u00a02. Additione Fig.\u00a02. The vicd Table\u00a01.H-imidazole  and potassium tri\u00adcyano\u00admethanide KC(CN)3  in water-ethanol . The mixture was transferred to a Teflon-lined autoclave and heated at 423\u2005K for 48\u2005h. The autoclave was then allowed to cool to ambient temperature. Block-like yellow crystals of (I)The title compound was obtained under hydro\u00adthermal conditions from a mixture of iron(II) sulfate hepta\u00adhydrate , 2-(pyridin-2-yl)-1Uiso(H) = 1.2Ueq(C). The H atoms attached to O and N atoms were located in a difference Fourier map and were refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015004417/wm5132sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015004417/wm5132Isup2.hklStructure factors: contains datablock(s) I. DOI: 1051905CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the compound, a succession of MnII ions (situated on inversion centers) adopting a distorted octa\u00adhedral coordination and bridged by oxalate ligands forms parallel zigzag chains running along the c axis. These chains are inter\u00adconnected through O\u2014H\u22efO hydrogen-bonding inter\u00adactions to form anionic layers parallel to (010). Individual layers are held together via strong hydrogen bonds involving the guanidinium cations (N\u2014H\u22efO and N\u2014H\u22efCl) and the disordered non-coordinating water mol\u00adecule (O\u2014H\u22efO and O\u2014H\u22efCl), as well as by guanidinium \u03c0\u2013\u03c0 stacking. The structural data were confirmed by IR and UV\u2013Visible spectroscopic analysis.As part of our studies on the synthesis and the characterization of oxalate-bridged compounds  A bond-valence-sum calculation, assuming Mn\u2014O and Mn\u2014Cl bonds, gives a BVS value  and IDa = 0.22\u2005(4)%, respectively \u2005\u00c5] and one oxygen atom from the bridging oxalato group [Mn1\u2014O4 = 2.248\u2005(2)\u2005\u00c5]. The two oxalato groups are almost perpendicular with a dihedral angle of 89.09\u2005(6)\u00b0. The oxalate ion is located on an inversion center that also relates the two Mn atoms bonded to the oxalate ion with each other. The bridged metal ions are nearly coplanar with the oxalate plane with a mean deviation of 0.0147\u2005(8)\u2005\u00c5.The equatorial plane of the MnOII ion, as a d5 high-spin system with a spherical electron distribution, has a limited number of commonly observed coordination geometries that are based on minimization of ligand\u2013ligand repulsion. Among the Mn\u2014O distances, the shortest are those involving an oxygen atom from the oxalate ion trans to another oxygen atom from the second oxalate ion. The range of these distances is 2.180\u2005(1) to 2.194\u2005(1)\u2005\u00c5, which is in accord with those observed in other oxalate-bridged compounds such as one of the polymorphs of catena-poly[[di\u00adaqua\u00admanganese(II)]-\u03bc-oxalato-\u03ba4O1,O2:O1\u2032,O2\u2032]  and 2.248\u2005(2)\u2005\u00c5.The MnII chains running along the c axis. The intra-chain Mn\u22efMn distances through bridging oxalate are 5.695\u2005(2) and 5.778\u2005(2)\u2005\u00c5, somewhat longer than the value of 5.652\u2005\u00c5 previously observed for {[Mn(C2O4)(C8H7N3)]\u00b71.5H2O}n  \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z], leading to the formation of anionic layers parallel to (010). A disordered non-coordin\u00adating water mol\u00adecule acts as acceptor  x, y\u00a0\u2212\u00a01, z]. Both disorder components of the non-coordinating water mol\u00adecules act as hydrogen-bond donors towards oxygen atom O3  \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a02, \u2212z]. The combined water hydrogen bonds link the anionic layers into a 3D framework.Neighbouring oxalate-bridged zigzag chains are connected with each other s Table\u00a01 towards s Table\u00a01, OW1\u2014HW2or Fig.\u00a03 for the O3 Fig.\u00a03 via the A\u22efO2i, N1\u2014H1B\u22efO4, N2\u2014H2A\u22efCl1ii, N2\u2014H2B\u22efCl1iii, N2\u2014H2A\u22efO4, N3\u2014H3A\u22efO1iv and N3\u2014H3B\u22efCl1iii , consolidating the anionic layers and giving additional stability to the three-dimensional structure as illustrated in Fig.\u00a04via \u03c0\u2013\u03c0 stacking with an inter\u00adplanar distance of 3.547\u2005(3)\u2005\u00c5 between C3 and C3 \u22121 assigned to [\u03bd(O\u2014H) + \u03bdas(NH2)] and \u03bds(NH2), respectively ], 1312 and 1409\u2005cm\u22121 [\u03bds(COO)] and 793\u2005cm\u22121 [\u03b4(COO)]  et al., 2009et al., 1996n\u2192\u03c0* transition \u00b7H2O dissolved in 10\u2005cm3 of water in a 1:2:1 molar ratio. The resulting solution was left at room temperature and colourless crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.Aqueous solutions of ammonium oxalate and guanidine hydro\u00adchloride were added to Mn using adequate HFIX instructions and refined with AFIX instructions. Hydrogen atoms of the coordinating water mol\u00adecule were found in Fourier difference maps. O\u2014H distances were restrained to a value of 0.85\u2005(1)\u2005\u00c5 and H\u22efH distances were restrained to a value of 1.387\u2005(1)\u2005\u00c5.Supra\u00admolecular features section and Fig.\u00a03The oxygen atom of the non-coordinating water mol\u00adecule had unusually high displacement parameters, and was refined as disordered over two alternative mutually exclusive positions. The solvent mol\u00adecule may be considered as being located vertically between negative-charged anionic layers formed by hydrogen-bonded polymeric chains and located horizontally between positive-charged pairs of guanidinium cations. This pseudo-channel affects its hydrogen-bonding inter\u00adactions, see the discussion in the first paragraph of the W2 and OW2B which were restrained to have similar geometries. Their hydrogen atoms were located from the Fourier difference maps. The O\u2014H bond lengths were restrained to a value of 0.85\u2005(1)\u2005\u00c5 and the H\u22efH distances were restrained to a value of 1.387\u2005(1)\u2005\u00c5. The inter\u00adatomic distances between the two pairs OW2 and HW5 and OW2B and HW3 were restrained to be equal using a SADI instruction with an effective standard deviation of 0.02. The hydrogen-bonding distance of hydrogen atom HW6 to chlorine atom Cl1 was restrained to 2.80\u2005(1)\u2005\u00c5. Subject to these and the above conditions, the occupancy ratio of the disordered non-coordinating water mol\u00adecule refined to 0.816\u2005(13):0.184\u2005(13).The disordered oxygen atom was refined as disordered over two positions O10.1107/S2056989016006605/zl2659sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016006605/zl2659Isup2.hklStructure factors: contains datablock(s) I. DOI: 1474882CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "O\u2014H\u22efO inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings organize the crystal components into columns extending along the b axis while N\u2014H\u22efN hydrogen bonds link these columns into a two-dimensional framework parallel to (100).In C 6H6N2O2\u00b7H2O, consists of N-hy\u00addroxy\u00adpicolinamide and water mol\u00adecules connected through O\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds. The O\u2014H\u22efO inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distance = 3.427\u2005(1)\u2005\u00c5] organize the components into columns extending along the b axis and the N\u2014H\u22efN hydrogen bonds link these columns into a two-dimensional framework parallel to (100). The N-hy\u00addroxy\u00adpicolinamide mol\u00adecule adopts a strongly flattened conformation and only the O\u2014H group H atom deviates significantly from the mol\u00adecule best plane. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6\u2005(2)\u00b0. The conformation about the hydroxamic group C\u2014N bond is Z and that about the C\u2014C bond between the pyridine and hydroxamic groups is E.The crystal structure of the title compound, C R\u2014C(=O)\u2014NH\u2014OH. HA can exist as keto and imino\u00ad(enol) tautomers with two isomers, E and Z, for each form, and in the zwitterionic form (see Scheme below). They have found broad application in coordination chemistry due to their diversity and comparatively facile synthesis  are weak organic acids with the general formula N-Hy\u00addroxy\u00adpicolinamide, known also as picoline-2-hydroxamic acid (o-PicHA), has been used extensively for the synthesis of polynuclear complexes, especially in the synthesis of diverse metallacrowns  and 1.325\u2005(2)\u2005\u00c5, respectively] and a water mol\u00adecule. The N-hy\u00addroxy\u00adpicolinamide mol\u00adecule adopts a strongly flattened conformation and only the O\u2014H group H atom deviates significantly from the mol\u00adecular best plane. The maximum deviation from this plane for non-hydrogen atom is 0.083\u2005(1)\u2005\u00c5 for O1 and the hydroxyl group H2 atom is displaced from the mean plane by 0.80\u2005(1)\u2005\u00c5 in the direction of the water mol\u00adecule. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6\u2005(2)\u00b0. The configuration about the hydroxamic group C\u2014N bond is Z and that about the C\u2014C bond between the pyridine and hydroxamic groups is E .The mol\u00adecular structure of the title compound is presented in Fig.\u00a01b axis while the N\u2014H\u22efN hydrogen bonds link these columns into a two-dimensional framework parallel to (100) .The mol\u00adecular components of the title compound are connected by O\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds Table\u00a01 into a tet al., 2007et al., 2001et al., 2008A search of the Cambridge Structural Database  or Uiso = 1.5Ueq(O). The H atoms of the water mol\u00adecule were located in the difference Fourier maps, the O\u2014H distances standardized to 0.85\u2005\u00c5 and refined in riding-model approximation with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015024706/gk2650sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015024706/gk2650Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024706/gk2650Isup3.cmlSupporting information file. DOI: 1444026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the carbazole ring system is essentially planar (maximum deviation = 0.025\u2005\u00c5). The crystal packing is stabilized by inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular network. 29H24N2, the C=N bond of the central imine group adopts an E conformation. The dihedral angles between the mean plane of the essentially planar carbazole ring system [r.m.s. deviation = 0.039\u2005(2)\u2005\u00c5] and the two phenyl rings of the 3,3-di\u00adphenyl\u00adallyl\u00adidene unit are 75.9\u2005(1) and 64.6\u2005(1)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular network.In the title compound, C It has been reported that carbazole derivatives possess various biological activities, such as anti\u00adtumor (Itoigawa E conformation. The carbazole ring system (N1/C1\u2013C12) is essentially planar [maximum deviation = 0.039\u2005(2)\u2005\u00c5 for atom C9]. The phenyl rings C18\u2013C23 and C24\u2013C29 of the  unit are oriented at dihedral angles of 75.9\u2005(1) and 64.6\u2005(1)\u00b0, respectively, to the mean plane of the carbazole ring system. The dihedral angle between the two phenyl rings is 76.1\u2005(1)\u00b0. The sum of the bond angles around atom N1 (359.7\u00b0) of the pyrrole ring is in accordance with sp2 hybridization. The geometric parameters of the title mol\u00adecule agree well with those reported for similar structures , and a methyl\u00adene H atom of the ethyl group and a benzene ring of an adjacent mol\u00adecule (C13\u2014H13A\u22efCg1iii); see Table\u00a01In the crystal, mol\u00adecules are linked by six inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular network Table\u00a01. Four ofH-carbazol-3-amine (1\u2005mmol), 3,3-di\u00adphenyl\u00adacryl\u00adaldehyde (1\u2005mmol) and sulfated SnO2-Bi2O3-fly ash catalyst (20\u2005mg) in water (15\u2005ml) and the mixture was refluxed at 363\u2005K for 1h. On completion of the reaction (monitored by TLC with ethyl acetate and hexane as an eluent 20%) the mixture was cooled to ambient temperature. Di\u00adchloro\u00admethane (20\u2005ml) was then added to separate the organic and aqueous layers. The organic layer was filtered, dried on anhydrous Na2SO4 and the solvent removed using a rotary evaporator. The crude product obtained was purified by column chromatography on silica gel (200 mesh) with hexane and ethyl acetate (4:1) as eluent, to afford the title compound in good yield (93%). Red crystals suitable for X-ray diffraction analysis were obtained after recrystallization in CH2Cl2.A 25\u2005ml round-bottom flask was charged with 9-ethyl-9Uiso(H) = 1.5Ueq for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015005770/su5095sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015005770/su5095Isup2.hklStructure factors: contains datablock(s) I. DOI: 967497CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The hydroxide ion is surrounded by five caesium cations, which form a distorted quadratic pyramidal polyhedron. A three-dimensional network is formed by Cs\u2014Sn [3.8881\u2005(7)\u2005\u00c5 to 4.5284\u2005(7)\u2005\u00c5] and Cs\u2014NH3 [3.276\u2005(7)\u20133.636\u2005(7)\u2005\u00c5] contacts.The title compound, penta\u00adcaesium nona\u00adstannide hydroxide tetra\u00adammonia, crystallized from a solution of CsSnBi in liquid ammonia. The Sn DOI: 10.1107/S1600536814011817/ru2058Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004528CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound contains two crystallographically unique copper complexes. In each complex, the Cu atom is bound to two chloride ligands and to three N atoms of the 2-(4-tri\u00adfluoro\u00admethyl\u00adbenzyl\u00adidene\u00adamino)\u00adethyl\u00adamine-bis\u00ad(2\u20132amino\u00adeth\u00adyl)amine ligand to give a distorted square-based pyramidal geometry in which the axial Cu\u2014Cl bond is elongated, indicative of Jahn\u2013Teller distortion. A Cu atom from a symmetry-related mol\u00adecule is in nearby proximity to the remaining axial Cu site, thus the overall geometry about each Cu atom could be described as being between distorted square-based pyramidal and very elongated Jahn\u2013Teller-distorted octa\u00adhedral. II atom in the title compound, [CuCl2(C14H21F3N4)], adopts a coordination geometry that is between distorted square-based pyramidal and very Jahn\u2013Teller-elongated octa\u00adhedral. It is coordinated by three N atoms from the bis\u00ad(2-amino\u00adeth\u00adyl)(2-{[4-(tri\u00adfluoro\u00admeth\u00adyl)benzyl\u00adidene]amino}\u00adeth\u00adyl)amine and two chloride ligands. The two crystallographically unique copper complexes present in the asymmetric unit exhibit noticeable differences in the coordination bond lengths. Considering the CuII atoms as having square-pyramidal geometry, the basal Cu\u2014Cl bond lengths are typical [2.2701\u2005(12) and 2.2777\u2005(12)\u2005\u00c5], while the apical distances are considerably elongated [2.8505\u2005(12) and 2.9415\u2005(12)\u2005\u00c5]. For each mol\u00adecule, a CuII atom from inversion-related mol\u00adecules are in nearby proximity to the remaining axial CuII sites, but the Cu\u22efCl distances are very long [3.4056\u2005(12) and 3.1645\u2005(12)\u2005\u00c5], attributable to van der Waals contacts. Nonetheless, these contacts appear to have some structure-directing properties, leading to association into dimers. These dimers associate via stacking of the aromatic rings to form extended zigzag chains.The Cu However, an elongated Cu1\u22efCl2i distance of 3.4056\u2005(12)\u2005\u00c5 is also observed, which can be attributed to a van der Waals contact  direction \u2005\u00c5 and a dihedral angle of 10.6\u2005(3)\u00b0 Fig.\u00a03. Inspecton Fig.\u00a03.i, N3\u22efCl2, N7\u22efCl4; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z] have severely constrained N\u2014H\u22efCl angles and are merely contacts to chlorine atoms bonded to the same CuII atom. The remaining hydrogen-bond contacts are inter\u00admolecular inter\u00adactions, and while relatively long, they likely contribute to structure-directed organization.Inspection of inter\u00admolecular/intra\u00admolecular contacts reveals that amine nitro\u00adgen atoms N2, N3, N6 and N7 are involved in N\u2014H\u22efCl hydrogen-bonds Table\u00a02. HoweverN-2-bis(2-amino\u00adeth\u00adyl)amino\u00adethyl ligand skeleton  and 2.609\u2005(2)\u2005\u00c5 \u00adeth\u00adyl)amine ligand: In a drybox, tris(2-(amino)\u00adeth\u00adyl)amine  was dissolved in 100\u2005mL methanol in a 250\u2005mL round-bottom flask : \u03b4 2.94 , 3.70 , 7.56 , 8.08 . 13C NMR : \u03b4 55.62, 60.32, 122.85 (q), 125.73 (q), 128.35, 132.44 (q), 139.62, 160.42. FT\u2013IR (solid) v (cm\u22121): 1321 (s), 1169 (s), 1118 (s), 1062 (s), 834 (s). Melting Point: 344\u2005K. TOF\u2013ESI\u2013MS: (m/z) [M + (H)]+ calculated for C30H28N4F9 = 615.2165, found 615.2194 (4.8 p.p.m.).sk Fig.\u00a04. Ligand Synthesis of 2-(4-tri\u00adfluoro\u00admethyl\u00adbenzyl\u00adidene\u00adamino)\u00adeth\u00adyl)amine-bis(2-\u03b1minoeth\u00adyl)amine copper(II) chloride complex:tris(2-(4-Tri\u00adfluoro\u00admethyl\u00adbenzyl\u00adidene\u00adamino)\u00adeth\u00adyl)amine  was dissolved in 20\u2005mL methanol in a 100\u2005mL round-bottom flask. CuCl2  was added to the flask to give a teal-colored solution. The reaction was allowed to mix for six\u2005h then 20\u2005mL of pentane was slowly added to the solution to generate a teal-colored precipitate. Solvent was removed from the round-bottom flask by connecting it to a rotary evaporator. The precipitate obtained was washed twice by transferring 15\u2005mL of pentane into the flask and stirring vigorously for thirty minutes. Solvent was removed and precipitate dried under vacuum for one\u2005h to yield a teal-colored solid . FT\u2013IR (solid): v (cm\u22121) = 1636 (m), 1506 (s), 1473 (s), 1317 (s), 1163 (s), 1109 (br), 830 (s). UV\u2013Vis (MeOH) \u03bbmax = 668\u2005nm. TOF\u2013ESI\u2013MS: (m/z) [M \u2013 2(Cl)]2+ calculated for C30H27N4F9Cu = 677.1383, found 677.1381 (0.2 p.p.m.). Blue single crystal plates suitable for X-ray analysis were obtained by slow diffusion of diethyl ether into a complex solution made in aceto\u00adnitrile at room temperature. The structure obtained is indicative of hydrolysis occuring on two amine positions of the intended copper(II) complex.Uiso(H) = 1.2Ueq for methyl\u00adene, aromatic and amide groups with C\u2014H distances set at 0.99\u2005\u00c5 (methyl\u00adene), 0.95\u2005\u00c5 (aromatic) and N\u2014H = 0.91\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989015024147/pk2570sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015024147/pk2570Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024147/pk2570Isup3.pdfSupporting information file. DOI: 1442779CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E conformation about the C=N bond and the mol\u00adecules is planar . In the crystal, the lattice water mol\u00adecule (Ow) links the mol\u00adecules via Ow\u2014H\u22efO, Ow\u2014H\u22efN and N\u2014H\u22efOw hydrogen bonds, forming sheets lying parallel to (100).The title compound, has an  13H10BrN3O2\u00b7H2O, the conformation about the azomethine double bond is E. The mol\u00adecule exists in the amido form with a C=O bond length of 1.229\u2005(2)\u2005\u00c5. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond forming an S(6) ring motif. The whole mol\u00adecule is almost planar, with an r.m.s. deviation of 0.021\u2005\u00c5 for all non-H atoms, and the dihedral angle between the planes of the pyridine and benzene rings is 0.74\u2005(12)\u00b0. In the crystal, the water mol\u00adecule of crystallization links the organic mol\u00adecules via Ow\u2014H\u22efO, Ow\u2014H\u22efN and N\u2014H\u22efOw hydrogen bonds and short C\u2014H\u22efOw contacts, forming sheets lying parallel to (100). Within the sheets there is a weak \u03c0\u2013\u03c0 inter\u00adaction involving the pyridine and benzene rings [centroid-to-centroid distance = 3.8473\u2005(15)\u2005\u00c5]. The sheets are linked via C\u2014H\u22efBr inter\u00adactions, forming a three-dimensional network.In the title compound, C The two aromatic rings (C1\u2013C6 and N3/C9\u2013C13), are inclined to the almost planar hydrazone moiety  by 2.12\u2005(9) and 1.40\u2005(8)\u00b0, respectively, and to each other by 0.74\u2005(12)\u00b0. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond present in the mol\u00adecule that involves the phenolic oxygen, O1 and the azomethine nitro\u00adgen atom, N1, forming an S(6) ring motif nico\u00adtino\u00adhydra\u00adzide. The crystal structure of N\u2032-(2-hy\u00addroxy\u00adbenzyl\u00adidene)nicotinohydrazide itself is reported as a monohydrate \u00b0]. In the crystal structure of N\u2032-(2-hy\u00addroxy\u00adbenzyl\u00adidene)nico\u00adtino\u00adhydrazide monohydrate (IDASUB), the water mol\u00adecule forms three hydrogen bonds and is another example of a system where a single atom acts both as donor and acceptor.A search of the Cambridge Structural Database . Elemental analysis calculated for C13H10N3O2Br\u00b7H2O: C, 46.17, H, 3.58, N, 12.43%; found: C, 46.14, H, 3.57, N, 12.44%. IR FT\u2013IR  3059 (NH), 3269(OH), 1680 (C=O), 1584 (C=N).The title compound was prepared by adapting a reported procedure  = 1.2Ueq(C). Three reflections were omitted owing to bad agreement, viz. 100, 110 and 200.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015009627/su5132sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009627/su5132Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015009627/su5132Isup3.cmlSupporting information file. DOI: 1401825CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule is planar, with the hy\u00addroxy H atom forming an intra\u00admolecular O\u2014H\u22efN hydrogen bond. In the crystal, mol\u00adecules form centrosymmetric dimers via two O\u2014H\u22efN hydrogen bonds. Thus, the hy\u00addroxy H atoms are involved in bifurcated O\u2014H\u22efN hydrogen bonds, leading to the formation of a central planar four-membered N2H2 ring. The dimers are bound by inter\u00admolecular \u03c0\u2013\u03c0 stacking [the shortest C\u22efC distance is 3.2997\u2005(17)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions into a three-dimensional framework. The crystal grown represents a new monoclinic polymorph in the space group P21/n. The mol\u00adecular structure of the present monoclinic polymorph is very similar to that of the ortho\u00adrhom\u00adbic polymorph (space group Fdd2) studied previously . The structures of the two polymorphs are distinguished by the different geometries of the hydrogen-bonded dimers, which in the crystal of the ortho\u00adrhom\u00adbic polymorph possess twofold axis symmetry, with the central N2H2 ring adopting a butterfly conformation.In an attempt to grow 8-hy\u00addroxy\u00adquinoline\u2013acetamino\u00adphen co-crystals from equimolar amounts of conformers in a chloro\u00adform\u2013ethanol solvent mixture at room temperature, the title compound, C al. 1978. Acta CrSaha 1986. Acta Cr \u00c5b = 9.243 (4) \u00c5c = 11.070 (4) \u00c5\u03b2 = 90.718 (6)\u00b0V = 677.3 (5) \u00c53Z = 4K\u03b1 radiationMo \u22121\u03bc = 0.09 mmT = 100 K0.30 \u00d7 0.25 \u00d7 0.20 mmBruker APEXII CCD diffractometerSADABS; Bruker, 2003Tmin = 0.972, Tmax = 0.981Absorption correction: multi-scan (7049 measured reflections1795 independent reflectionsI > 2\u03c3(I)1494 reflections with Rint = 0.023R[F2 > 2\u03c3(F2)] = 0.039wR(F2) = 0.109S = 1.081795 reflections103 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.39 e \u00c5\u22123\u0394\u03c1min = \u22120.20 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXTL  global, I. DOI: 10.1107/S1600536814016110/rk2430Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814016110/rk2430Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814016110/rk2430fig1.tifI . DOI: I. Displacement ellipsoids are presented at the 50% probability level. H atoms are depicted as small spheres of arbitrary radius. The intra\u00admolecular O\u2014H\u22efN hydrogen bond is drawn by dashed line.Mol\u00adecular structure of Click here for additional data file.10.1107/S1600536814016110/rk2430fig2.tifI . DOI: I. The hydrogen bonds are drawn by dashed lines.The centrosymmetric H\u2013bonded dimers in the monoclinic polymorph of Click here for additional data file.10.1107/S1600536814016110/rk2430fig3.tifI . DOI: I, in which the mol\u00adecules are related by the twofold axis. The hydrogen bonds are drawn by dashed lines.The H\u2013bonded dimers in the ortho\u00adrhom\u00adbic polymorph of Click here for additional data file.10.1107/S1600536814016110/rk2430fig4.tifI . DOI: I. The hydrogen bonds are drawn by dashed lines.A portion of crystal packing of the H\u2013bonded dimers in the monoclinic polymorph of 1013310CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports5: Article number: 1580110.1038/srep15801; published online: 10302015; updated: 02022016This Article contains errors in Figure 4 and Figure 5.B/f.u.)\u2019 was incorrectly given as \u2018M(\u00b7B/f.u.)\u2019. In Figure 5, the y-axis \u2018\u2212\u0394SM (10\u22123Jule/Kg.K)\u2019 was incorrectly given as \u2018\u2212\u00b7SM (10\u22123Jule/Kg.K)\u2019. The correct Figure 4 and Figure 5 appear below as In Figure 4, the y-axis \u2018M (\u03bc"}
{"text": "The AgI atom adopts a slightly distorted linear coordination geometry. The symmetry-related right- and left-handed helical chains are arranged alternately via Ag\u22efAg and Ag\u22efF inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions, resulting in the formation of a two-dimensional supra\u00admolecular network.The reaction of AgBF L]\u00b7BF4\u00b70.5CH3OH}n, L = N-(pyridin-4-ylmeth\u00adyl)pyridine-3-amine, C11H11N3, contains one AgI ion, one ligand L, one tetra\u00adfluorido\u00adborate anion disordered over two orientations in a 0.669\u2005(13):0.331\u2005(13) ratio and one half of a methanol solvent mol\u00adecule situated on an inversion center. Each AgI ion is coordinated by two N atoms from two L ligands in a distorted linear geometry [N\u2014Ag\u2014N = 174.70\u2005(19)\u00b0]. Each L ligand bridges two AgI ions, thus forming polymeric helical chains propagating in [010]. In the crystal, Ag\u22efAg [3.3369\u2005(10)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings [centroid-to-centroid distance = 3.676\u2005(4)\u2005\u00c5] link these chains into layers parallel to (10-1). Ag\u22efF and weak N(C)\u2014H\u22efF inter\u00adactions further consolidate the crystal packing.The asymmetric unit of the title compound, {[Ag The helical chain propagates along [010] \u00b0 with respect to each other. The two pyridine rings in the L ligand are almost perpendicular, the dihedral angle between their mean planes being 89.34\u2005(15)\u00b0.The mol\u00adecular components of the title structure are shown in Fig.\u00a010] Fig.\u00a02 with a p al. 2014. The twoA = 2.84\u2005(2), Ag1\u22efF1B = 2.815\u2005(15) and Ag1\u22efF4B  = 2.879\u2005(10)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of adjacent helical chains [centroid-to-centroid distance = 3.676\u2005(4)\u2005\u00c5], resulting in the formation of a two-dimensional supra\u00admolecular network parallel to the \u2005\u00c5] and Ag\u22efF inter\u00adactions [Ag1\u22efF1ne Fig.\u00a02. Furtherne Fig.\u00a02 between et al.  nitrate and perchlorate complexes of the same ligand have been reported by Zhang  al. 2013. Our groN-(pyridin-4-ylmeth\u00adyl)pyridine-3-amine ligand was synthesized according to a literature method  = 0.95\u2005\u00c5 for Csp2\u2014H, 0.88\u2005\u00c5 for amine N\u2014H, 0.84\u2005\u00c5 for hydroxyl O\u2014H, 0.98\u2005\u00c5 for methyl C\u2014H and 0.99\u2005\u00c5 for methyl\u00adene C\u2014H. For all H atoms Uiso(H) = 1.2\u20131.5Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901501837X/cv5498sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901501837X/cv5498Isup2.hklStructure factors: contains datablock(s) I. DOI: 1428966CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Co\u2014O bond lengths in the [Co(H2O)6]2+ complex cation show very similar distances as in the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2 [average 2.093\u2005(17)\u2005\u00c5], but are significantly longer than in the isotypic NiII compound (\u0394d \u2243 0.04\u2005\u00c5). The cobalt cation reaches an overall bond-valence sum of 1.97 valence units. The S\u2014O distances are nearly equal, ranging from 1.454\u2005(4) to 1.470\u2005(3)\u2005\u00c5 [mean 1.465\u2005(12)\u2005\u00c5]; however, the O\u2014S\u2014O angles vary clearly from 108.1\u2005(2) to 110.2\u2005(2)\u00b0 [average bond angle 109.5\u2005(9)\u00b0]. The non-coordinating water mol\u00adecules and di\u00admethyl\u00adammonium cations connect the sulfate tetrahedra and the [Co(H2O)6]2+ octa\u00adhedron via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds of weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel to (001).The title salt, (C DOI: 10.1107/S2056989015003400/fk2085Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015003400/fk2085fig1.tifx y z . DOI: x, \u2212y\u00a0+\u00a01, \u2212z\u00a0\u2212\u00a01.]The mol\u00adecular entities in the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) \u2212Click here for additional data file.10.1107/S2056989015003400/fk2085fig2.tif. DOI: (100)-projection of the crystal structure of the title compound. Colour scheme: S (yellow), Co (red), O (blue), N (orange), C (grey), H (colourless), H\u22efO bonds up to 1.8\u2005\u00c5 are given as red dashed lines, and from 1.85 to 2.7\u2005\u00c5 as light-blue dashed lines.1050102CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N)bis\u00ad[bis\u00ad(pyridin-2-yl-\u03baN)amine]\u00adcobalt(III)} sulfate dihydrate is comprised of discrete [Co(dpa)2(N3)2]+ cations, SO42\u2212 anions and solvent water mol\u00adecules in a 2:1:2 ratio; extensive hydrogen-bonding inter\u00adactions link the species into a three-dimensional supra\u00admolecular framework.The crystal structure of bis\u00ad{bis\u00ad(azido-\u03ba 10H9N3) as a chelating ligand, led to the synthesis and structure determination of the title compound, [Co(N3)2(dpa)2]2SO4\u00b72H2O. The crystal structure comprises discrete [Co(dpa)2(N3)2]+ cations, sulfate anions, as well as H2O solvent mol\u00adecules. The CoIII cations display a slightly distorted octa\u00adhedral coordination sphere defined by two N atoms from azide anions and four N atoms from the pyridyl rings of two dpa ligands. In the crystal, extensive C\u2014H\u22efO, N\u2014H\u22efO, and O\u2014H\u22efO inter\u00adactions result in supra\u00admolecular sheets that lie parallel to the ab plane. The sheets are further linked through O\u2014H\u22efN inter\u00adactions between the water mol\u00adecules of one sheet and azide anions of another sheet, forming a supra\u00admolecular framework.The search for new mol\u00adecular materials with inter\u00adesting magnetic properties, using the pseudohalide azide ion and di-2-pyridyl\u00adamine (dpa, C The sul\u00b0 Table\u00a01. While t0 Table\u00a01, and the0 Table\u00a01. The twoet al., 2004et al., 2004et al., 2001et al., 2005et al., 20052(N3)2]\u00b72H2O, the two pyridyl rings of each chelating dpa ligand still coordinate to the metal in a cis-disposition, but the azide anions are coordinated trans to each other [CSD refcode: XUYWIX 2]ClO4 +, the Py1cent\u2014N2\u2014Py3cent and N1\u2014Co1\u2014N3 angles are 120.92\u2005(7) and 86.48\u2005(7)\u00b0, and the Py4cent\u2014N5\u2014Py5cent and N4\u2014Co1\u2014N6 angles are 125.49\u2005(7) and 88.08\u2005(7)\u00b0  (Table\u00a01In [Co(dpa)) Table\u00a01. The C\u2014N) Table\u00a01.III cation 2(N3)2]+ complex cation inter\u00adacts with one water mol\u00adecule through a C\u2014H\u22efO hydrogen bond (C10\u2014H10\u22efO3). The sulfate anions are sandwiched between two symmetry-related layers of complex cations and water mol\u00adecules 2(N3)2]+ cations through twelve hydrogen bonds . The extensive C\u2014H\u22efO, N\u2014H\u22efO, and O\u2014H\u22efO inter\u00adactions result in two-dimensional supra\u00admolecular sheets parallel to the ab plane , forming a supra\u00admolecular framework  are observed between neighboring dpa ligands and azide anions within the coordination sphere of the Con Table\u00a02. The comes Fig.\u00a04. Each suds Fig.\u00a05. As the ne Fig.\u00a05. Finallyrk Fig.\u00a06.cis\u2013trans conformation with an intra\u00admolecular C\u2014H\u22efN hydrogen bond between the two pyridyl rings \u00b7H2O with M = Mn [CSD refcode: JANPOE 2(N3)2]\u00b72H2O, the azide anions coordinate to the CuII ion weakly in a trans-fashion, resulting in a tetra\u00adgonally elongated octa\u00adhedral coordination sphere for the CuII ion, and hydrogen bonding and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions result in two-dimensional supra\u00admolecular sheets that lie parallel to the bc-plane [CSD refcode: XUYWIX 2]ClO4 is most closely related to the title complex in that the CoIII ions are coordinated by two chelating dpa ligands and two azide anions in a cis-fashion to form [Co(dpa)2(N3)2]+ complex cations [CSD refcode: HUFNUR  in water\u2013methanol . The mixture was sealed in a Teflon-lined autoclave and heated at 423\u2005K for two days and cooled to room temperature at 10\u2005K\u2005h\u22121. The crystals were obtained in ca 20% yield based on cobalt.The title compound was synthesized hydro\u00adthermally under autogenous pressure from a mixture of cobalt(II) sulfate hepta\u00adhydrate , di-2-pyridyl\u00adamine  and sodium azide NaNCAUTION! Although not encountered in our experiments, azido compounds of metal ions are potentially explosive. Only a small amount of the materials should be prepared, and it should be handled with care.Uiso(H) = 1.2Ueq(C). The N\u2014H and O\u2014H-atoms were located in difference Fourier maps and then refined as riding on the carrying nitro\u00adgen or oxygen atom with Uiso(H) = 1.2Ueq(N) or Uiso(H) = 1.5Ueq(O). Two reflections considered to be affected by beam stop inter\u00adference, 0 0 2 and 2 0 0, were omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989016003662/zl2656sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016003662/zl2656Isup2.hklStructure factors: contains datablock(s) I. DOI: 1457112CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The amide group of the ACP\u2013AZT anion is disordered (occupancy ratio 0.5:0.5), with one part forming an N\u2014H\u22efO (involving C=O\u22efH4N+) hydrogen bond and the other an O\u2014H\u22efN (involving C\u2014NH2\u22efOH2) hydrogen bond with the components of the split NH4+/H2O position. The pseudorotation parameters of ACP\u2013AZT set it apart from previously studied AZT and thymidine. In the crystal, the various components are linked by N\u2014H\u22efO, O\u2014H\u22efO, N\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming a three-dimensional framework.The asymmetric unit of the title compound, NH Atoms C3\u2032 and C4\u2032 deviate from the plane of atoms C1\u2032/O4\u2032/C2\u2032 by 0.458 and \u22120.101\u2005\u00c5, respectively. Unlike the AZT mol\u00adecules and the mol\u00adecule of thymidine, which exhibit a C3\u2032-exo- class of pucker, the ACP\u2013AZT mol\u00adecule exhibits a C3\u2032-endo pucker. The orientation of the thymine base relative to the de\u00adoxy\u00adribose ring in the ACP\u2013AZT mol\u00adecule is anti, similar to that in natural thymidine and AZT, the glycosyl torsion angle \u03c7ACP\u2013AZT(O4\u2032\u2014C1\u2032\u2014N1\u2014C2) = \u2212147.75\u2005(16)\u00b0. The geometric parameters of the azido residue and the orientation relative to the de\u00adoxy\u00adribose ring in ACP\u2013AZT and AZT coincide within experimental error.The mol\u00adecular structure of the title compound, ACP\u2013AZT, is illustrated in Fig.\u00a012 group of ACP\u2013AZT is disordered, one part forming a C=O\u22efH4N+ hydrogen bond and the other a C\u2014NH2\u22efOH2 hydrogen bond with the components of the NH4+/H2O position NHn Table\u00a01. In the n Table\u00a01, formingon Fig.\u00a02; howeveret al., 1986et al., 1987et al., 1987et al., 1988et al., 1988Earlier, in 1986, we studied the crystal and mol\u00adecular structures of AZT and then some other HIV replication inhibitors by X-ray analysis  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The other distance restraints and SIMU parameters are given below: DFIX 1.234 0.005 O7A C6\u2032 O7 C6\u2032; DFIX 0.9 N7 H7a N7 H7b; DFIX 0.95 N2S H2Sc N2S H2Sd N2S H2Sa N2S H2Sb O2S H2Sb O2S H2Sa; DFIX 1.325 0.005 N7 C6\u2032 N7A C6\u2032; DFIX 0.9 N7A H7Aa N7A H7Ab; SIMU 0.01 0.005 1.7 N2S O2S; SIMU 0.01 0.005 1.7 N7A O7 O7A N7. The split NH4+/H2O position was refined with an occupancy of 0.5 for each atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814022405/su2792sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814022405/su2792Isup2.hklStructure factors: contains datablock(s) I. DOI: 1028847CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This induces a geometry quite different than that predicted by theory.In the crystal, mol\u00adecules pack in a centrosymmetric fashion and inter\u00adact  14H10Br2O4, the dihedral angle between the aromatic rings is 67.29\u2005(19)\u00b0. Both meth\u00adoxy-group C atoms lie close to the plane of their attached ring [deviations = \u22120.130\u2005(4) and 0.005\u2005(5)\u2005\u00c5]. In the crystal, mol\u00adecules pack in a centrosymmetric fashion and inter\u00adact via a mixture of weak \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centoid separations = 4.044\u2005(2) and 4.063\u2005(3)\u2005\u00c5], weak C\u2014H\u22efO hydrogen bonding, and Br\u22efBr halogen bonding. This induces a geometry quite different than that predicted by theory.In the title compound, C This effect is rationalized as a loss of overlap between two \u03c0 systems. Inter\u00adrupting conjugation is a prerequisite for the design of unimolecular rectifiers \u00b0 in the crystal structure. DFT (B3LYP-DGDZVP) calculations performed on the target mol\u00adecule in the gas phase predict an angle of \u221238.54\u00b0. This significant discrepancy is probably due to packing inter\u00adactions in the solid phase.ortho to these positions. Finally, the quinone ring is slightly buckled (r.m.s. deviation = 0.064\u2005\u00c5), probably due to supra\u00admolecular packing effects.Substituents on the HBQ system behave as expected. The C\u2014Br bond distances reflect the natures of the electron-deficient quinone and electron-rich di\u00admeth\u00adoxy\u00adbenzene rings: the C1\u2014Br1 bond distance is 1.872\u2005(5)\u2005\u00c5, while the C10\u2014Br2 bond is 1.897\u2005(4)\u2005\u00c5. Thus Br1 has a slightly stronger \u03c0-donating character into the quinone moiety, strengthening the bond relative to the C10\u2014Br2 bond of the di\u00admeth\u00adoxy\u00adbenzene ring. The meth\u00adoxy substituents are nearly coplanar to the benzene ring, with a C12\u2014C11\u2014O4\u2014C14 torsion angle of 1.5\u2005(6)\u00b0 and a C9\u2014C8\u2014O3\u2014C13 torsion angle of \u22124.4\u2005(5)\u00b0. The methyl portions of each of these groups point away from the sterically restricting groups c axis show some face-to-face \u03c0-stacking.Each mol\u00adecule is surrounded by eight neighboring mol\u00adecules, which inter\u00adact through hydrogen bonding, halogen bonding, and \u03c0\u2013\u03c0 inter\u00adactions Figs. 2 and 3 \u25b8.a axis, the benzene rings \u2018nestle\u2019 closely to one another in an anti\u00adparallel geometry, where one quinone points up and the layer behind it points down. Within the cb plane, the benzene rings are coplanar; hydrogen atoms from C14 on one mol\u00adecule project closely to O3 on the adjacent mol\u00adecule and vice versa for a hydrogen atom attached to C13 to the adjacent O4 . The Br1\u22efBr2 separation is 3.4204\u2005(8)\u2005\u00c5, with almost linear C1\u2014Br1\u22efBr2 and C10\u2014Br2\u22efBr1 angles of 178.2\u2005(4) and 170.9\u2005(4)\u00b0, respectively. Equivalent rings from mol\u00adecules packed along this axis are parallel to one another; the quinone and benzene rings aligned coplanar to the corresponding ring in the next mol\u00adecule.Mol\u00adecules are aligned linearly in a head-to-tail manner where the bromine atoms participate in Br\u22efBr halogen bonding Fig.\u00a03. As disc2O. A solution of 2-bromo-1,4-di\u00admeth\u00adoxy\u00adbenzene  in 25\u2005ml of aceto\u00adnitrile was quickly added with vigorous stirring. After three hours, the product had precipitated as a grey\u2013green powder. The precipitate was filtered, washed with water, and dried. The crude product was purified using flash chromatography , yielding 0.0959\u2005g of the desired product (20.3%). Crystals were obtained by slow evaporation of a solution in chloro\u00adform.Cerium(IV) ammonium nitrate  was dissolved in 30\u2005ml of HUiso(H) = 1.5Ueq(C) for methyl H atoms, C\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for other H atoms]. Hydrogen atoms on methyl groups were refined with a riding rotating model. Crystal data, data collection and structure refinement details are summarized in Table\u00a02Hydrogen atoms were placed in calculated positions, and their coordinates and displacement parameters were constrained to ride on the carrier atom [C\u2014H = 0.98\u2005\u00c5 and 10.1107/S2056989015020472/hb7514sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020472/hb7514Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020472/hb7514Isup3.cmlSupporting information file. DOI: 1433845CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A receptors are the main inhibitory neurotransmitter receptors in the brain and are targets for numerous clinically important drugs such as benzodiazepines, anxiolytics and anesthetics. We previously identified novel ligands of the classical benzodiazepine binding pocket in \u03b11\u03b22\u03b32 GABAA receptors using an experiment-guided virtual screening (EGVS) method. This screen also identified novel ligands for intramembrane low affinity diazepam site(s). In the current study we have further characterized compounds 31 and 132 identified with EGVS as well as 4-O-methylhonokiol. We investigated the site of action of these compounds in \u03b11\u03b22\u03b32 GABAA receptors expressed in Xenopus laevis oocytes using voltage-clamp electrophysiology combined with a benzodiazepine site antagonist and transmembrane domain mutations. All three compounds act mainly through the two \u03b2+/\u03b1\u2212 subunit transmembrane interfaces of the GABAA receptors. We then used concatenated receptors to dissect the involvement of individual \u03b2+/\u03b1\u2212 interfaces. We further demonstrated that these compounds have anesthetic activity in a small aquatic animal model, Xenopus laevis tadpoles. The newly identified compounds may serve as scaffolds for the development of novel anesthetics.GABA A) receptor. These receptors are composed of five homologous subunits organized around a central Cl\u2212 selective channelA receptor have been cloned , integrating experimental data with homology modeling of the GABAin vivo, revealing potencies similar to propofol.Here we describe the actions of two compouds identified by EGVS, 31 and 132A receptors we screened 198 compounds for displacement of the high affinity benzodiazepine site  antagonist [3H]-Ro 15-1788 at receptors expressed in HEK-cells. Many high affinity ligands were identified3H]-Ro 15-1788 from site 1 but potently enhanced GABAA receptor activation. 4-O-methylhonokiol shares these characteristics, potentiating \u03b11\u03b22\u03b32 receptors with an EC50 of 5.4\u2009\u00b1\u20091.8\u2009\u03bcM, independent of the high affinity site for benzodiazepinesIn an attempt to find novel ligands for the high affinity site for benzodiazepines on GABA1\u03b22\u03b32 GABAA receptors expressed in Xenopus oocytes. These compounds elicited at the concentration of 3\u2009\u03bcM and 30\u2009\u03bcM currents amounting to 0.1\u2009\u00b1\u20090.06%  and 0.3\u2009\u00b1\u20090.13% , respectively of the maximal current amplitude elicited by GABA in the same oocytes. Thus neither of the compounds tested acts as an appreciable agonist on \u03b11\u03b22\u03b32 receptors.First, we investigated if compounds 31 and 132 were able to act as agonists. 1\u03b22\u03b32 receptors. For compound 31, at high concentrations apparent desensitization was observed, that could be partly due to open channel blocker effect. For both compounds no saturation at the highest concentration was obtained, because of poor solubility we could not test higher concentrations.Both compounds strongly enhanced currents elicited by GABA. We established the concentration response curves of this positive allosteric modulation. After two applications of GABA at a concentration eliciting 0.5\u20131.5% of the maximal current amplitude, the same concentration of GABA was co-applied with increasing concentrations of the tested compounds. 1\u03b22\u03b32 receptors. Nevertheless, we tested whether 1\u2009\u03bcM of the site 1 antagonist Ro 15-1788 inhibits potentiation of GABA currents by compounds 31 or 132. Either compound (3\u2009\u03bcM) strongly potentiated currents elicited by GABA. Potentiation by either drug was not inhibited by 1\u2009\u03bcM Ro 15-1788 (t test) for compound 31, and 115\u2009\u00b1\u200914%  for compound 132. This confirms that potentiation by compounds 31 and 132 does not result from action at the benzodiazepine site 1.From the binding data we did not expect that the two compounds are acting through the high affinity benzodiazepine binding site 1 in \u03b1 15-1788 . Relativ1\u03b22\u03b32 receptors, \u03b11S269I, \u03b22N265I and \u03b32S280I, eliminated the potentiation by high concentrations of diazepam1M, \u03b22M and \u03b32M. Recently, we described the potency of GABA to activate all of these receptor subtypes expressed in Xenopus oocytes3 receptor3 subunits were renamed \u03b11, \u03b22 and \u03b32 , and by compound 132 to 118\u2009\u00b1\u200944% . Modulation in \u03b11\u03b22\u03b32M receptors by compound 31 was 87\u2009\u00b1\u200952% , and by compound 132 was 91\u2009\u00b1\u200921% . In contrast, modulation by both compounds was strongly impaired in \u03b11\u03b22M\u03b32 and triply mutated \u03b11M\u03b22M\u03b32M receptors. Potentiation by 3\u2009\u03bcM compound 31 in \u03b11\u03b22M\u03b32 was 10.4\u2009\u00b1\u20098.5% , and in \u03b11M\u03b22M\u03b32M receptors was 2.3\u2009\u00b1\u20090.8% . Potentiation by compound 132 relative to that in \u03b11\u03b22\u03b32 was also dramatically reduced in \u03b11\u03b22M\u03b32 7.3\u2009\u00b1\u20096.8%  and \u03b11M\u03b22M\u03b32M \u22120.4\u2009\u00b1\u20095.1% , respectively.1\u03b22M\u03b32 and \u03b11M\u03b22M\u03b32M receptors, similar to compounds 31 and 132. Relative to wild-type \u03b11\u03b22\u03b32 receptors, modulation in \u03b11M\u03b22\u03b32 mutated amounted to 63\u2009\u00b1\u20096% , and in \u03b11\u03b22\u03b32M receptors to 79\u2009\u00b1\u200916% . Relative to \u03b11\u03b22\u03b32, residual potentiation in \u03b11\u03b22M\u03b32 receptors amounted to 15.6\u2009\u00b1\u20091.5% , and to 2.2\u2009\u00b1\u20090.2%  in \u03b11M\u03b22M\u03b32M.Potentiation by 1\u2009\u03bcM 4-O-methylhonokiol was also significantly reduced only in \u03b11\u03b22\u03b32 GABAA receptors.The above data suggests that the modulatory site(s) for the three compounds we studied is located in one or both of the \u03b2+/\u03b1\u2212 TMD subunit interfaces on \u03b1A receptor contains two \u03b2+/\u03b1\u2212 subunit interfaces. Combined mutation at these interfaces greatly reduces the modulatory effects of compounds 31, 132 and 4-O-methylhonokiol. Using \u03b11-\u03b22-\u03b11 and \u03b32-\u03b22 subunit concatemers, we studied the effects of individual mutated interfaces. We designated receptors containing the mutant in the \u03b32-\u03b22 construct interface 1 M, and the mutation in the \u03b11-\u03b22-\u03b11 construct interface 2 M  potentiation for all three compounds was abolished. Relative to \u03b11-\u03b22-\u03b11/\u03b32-\u03b22 concatenated receptors, in the double mutant \u03b11-\u03b22M-\u03b11/\u03b32-\u03b22M receptor modulation by compound 31 was reduced to 1\u2009\u00b1\u20095% , by compound 132 to \u22122\u2009\u00b1\u20090.4% , and by 4-O-methylhonokilol to 1\u2009\u00b1\u20090.6% . In receptors containing only one mutation, either interface 1 or interface 2, modulation by compound 31 was reduced significantly compared to concatenated wild type receptors \u03b11-\u03b22-\u03b11/\u03b32-\u03b22. With interface 1 M, residual relative potentiation was 28\u2009\u00b1\u20096%  and with interface 2\u2009M it was 51\u2009\u00b1\u20093%  of wild-type. Potentiation of interface 1\u2009M and interface 2\u2009M receptors differed significantly . Therefore, both TMD \u03b2+/\u03b1\u2212 sites seem to contribute differently to modulation by compound 31, interface 1 being more efficacious.Wild type concatenated receptors \u03b1Tukey posthoc test), and in interface 2\u2009M receptors to 39\u2009\u00b1\u200919% . Again, interface 1\u2009M produced a larger impact than 2\u2009M, although the difference was at the statistical limit . Modulation by 4-O-methylhonokiol in interface 1\u2009M and 2\u2009M receptors was reduced to 11\u2009\u00b1\u20096%  and 28\u2009\u00b1\u20098% , respectively. The two mutations produced significantly different effects , with the interface 1\u2009M effect again larger.Likewise, modulation by compound 132 was sensitive to the mutations at both sites. In interface 1 M receptors relative potentiation was reduced to 8\u2009\u00b1\u20094% , to 125\u2009\u00b1\u200925% in the mutated receptor . In contrast, this mutation did not significantly reduce potentiation by 3\u2009\u03bcM compound 132: 415\u2009\u00b1\u2009126% in wild-type receptors (mean\u2009\u00b1\u2009SD n\u2009=\u20096) versus 280\u2009\u00b1\u200936% in the mutated receptor . We have shown earlier that potentiation by 4-O-methylhonokiol in receptors carrying the \u03b22N265S mutation was greatly reduced to about 40%The \u03b21 subunit by different \u03b1 subunit isoforms: \u03b11\u03b22\u03b32, \u03b12\u03b22\u03b32, \u03b13\u03b22\u03b32, \u03b14\u03b22\u03b32, \u03b15\u03b22\u03b32 and \u03b16\u03b22\u03b32 , \u03b12\u03b22\u03b32 receptors, 407\u2009\u00b1\u2009172% , \u03b13\u03b22\u03b32 receptors, 735\u2009\u00b1\u2009234%, , and \u03b14\u03b22\u03b32 receptors, 412\u2009\u00b1\u2009175% . The \u03b15\u03b22\u03b32 receptor showed a significant decrease in potentiation compared to \u03b11\u03b22\u03b32 receptors to 253\u2009\u00b1\u200992% , and the \u03b16\u03b22\u03b32 receptor an increase in potentiation, amounting to 780\u2009\u00b1\u2009236% . This discrepancy in modulation of \u03b15\u03b22\u03b32 and \u03b16\u03b22\u03b32 receptors maybe explained by the fact that 3 of the first 7 residues of M1 located at the minus side of the \u03b1 subunit are different  in \u03b12\u03b22\u03b32 receptors, 652\u2009\u00b1\u2009215%  in \u03b13\u03b22\u03b32 receptors, 476\u2009\u00b1\u2009152%  in \u03b14\u03b22\u03b32 receptors, 399\u2009\u00b1\u2009147%  in \u03b15\u03b22\u03b32 receptors, and 542\u2009\u00b1\u2009175%  in \u03b12\u03b22\u03b32 receptor type. These results indicate that although the type of \u03b1 subunit has differential effects on potentiation between compounds 31 and 132, these compounds modulate all receptor subtypes studied.From the above experiments we inferred that the \u03b2+/\u03b1\u2212 TMD subunit interfaces mediate potentiation of compounds 31 and 132. We also wanted to know if potentiation by these compounds depends on subunit isoforms. First we replaced the \u03b1d \u03b16\u03b22\u03b32 . Compounifferent . Compoun2 by \u03b21 or \u03b23. For compounds 31 and 132, \u03b11\u03b23\u03b32 receptors showed a similar potentiation as \u03b11\u03b22\u03b32 receptors. Amounting to 381\u2009\u00b1\u2009115% for compound 31 and 555\u2009\u00b1\u2009169% for compound 132 . In the case of \u03b11\u03b21\u03b32 receptors, potentiation by both compounds was significantly reduced compared to that in \u03b11\u03b22\u03b32, 41\u2009\u00b1\u200913% for compound 31 and 37\u2009\u00b1\u20097% for compound 132 . These results indicate that the type of \u03b2 subunit is important for the potentiation by both compounds. It is interesting to note in this context that \u03b21 and \u03b22/\u03b23 differ not only in the residue 265, but also in the fourth residue of M3 predicted to be close to the latter residue . Compound 132 also showed a similar potentiation between both receptors, potentiation in \u03b11\u03b22 receptors amounting to 625\u2009\u00b1\u2009219% . When the \u03b32 subunit was replaced by a \u03b4 subunit, in the case of \u03b11\u03b22\u03b4 receptors, potentiation was affected only in the case of compound 31, where a significant reduction was observed relative to \u03b11\u03b22\u03b32 receptors. Where potentiation amounted to 168\u2009\u00b1\u200948%  for compound 31, and 640\u2009\u00b1\u2009275%  for compound 132. In \u03b14\u03b23\u03b4 receptors, potentiation by both compounds was statistically reduced relative to \u03b14\u03b23\u03b32 receptors. For compound 31 potentiation amounted to 345\u2009\u00b1\u200977%  in \u03b14\u03b23\u03b32 receptors, and was reduced to 125\u2009\u00b1\u200922%  in \u03b14\u03b23\u03b4 receptors. Potentiation of compound 132 in \u03b14\u03b23\u03b32 receptors was 728\u2009\u00b1\u2009203% , and was reduced to 214\u2009\u00b1\u200971%  in \u03b14\u03b23\u03b4 receptors.When the \u03b35 and \u03b16 subunits. The type of \u03b2 subunit was also important, as the presence of the \u03b21 subunit strongly reduced potentiation by this compound. On the contrary, the presence of a \u03b3 or a \u03b4 subunit did not affect potentiation.Previous workXenopus tadpoles, 50 of 2.7\u2009\u03bcM , while the EC50 compound 132 was 1.2\u2009\u03bcM , and 4-O-methylhonokiol EC50\u2009=\u20091.0\u2009\u03bcM . For comparison, the EC50 for propofol-induced LoRR in tadpoles is 1.3\u2009\u03bcMThe anesthetic activity for compounds 31, 132 and 4-O-methylhonokiol was determined as loss of righting reflex (LoRR) in 1\u03b22\u03b32 GABAA receptors that do not act at site 1. We suspected that they instead act through the low affinity TMD site(s) for benzodiazepines (site 3). Indeed, potentiation by compounds 31, 132 and 4-O-methylhonokiol was abolished in the triple mutant receptor \u03b11S269I\u03b22N265I\u03b32S280I as well as by the single mutation \u03b22N265I, but unaffected by the homologous mutations \u03b11S269I and \u03b32S280I. Assuming that these TM2 mutations alter drug actions through local steric effects in adjacent TMD interfacial sites, our results indicate that of the five such sites, only the two \u03b2+/\u03b1\u2212 interfaces 1 and 2 mediate the potentiating effects of these three compounds.Here we functionally characterized compounds 31, 132 and further investigated the properties of 4-O-methylhonokiol. All three compounds are potent allosteric potentiators of \u03b1We further dissected the contribution of the individual \u03b2+/\u03b1- subunit interfaces using concatenated subunit assemblies. The \u03b3\u03b2+/\u03b1\u2212\u03b2 interface (interface 1) and \u03b1\u03b2+/\u03b1\u2212\u03b3 interface (2) participated differently in modulation by the three compounds studied. For all compounds the contribution of the interface 1 to drug modulation is apparently greater than that of the interface 2.1\u03b22\u03b32 receptors, \u03b22N265I reduced potentiation by all compounds, \u03b11S269I reduced potentiation exclusively by pentobarbital, and the \u03b32S280I mutation increased potentiation by etomidate, while reducing potentiation by propofol and pentobarbital23243342We and others have shown that the intravenous anesthetics etomidate, propofol and pentobarbital also act via TMD interfacial sites262728292M286W) and different concatenated subunit assemblies suggest that etomidate interactions are equivalent in the two \u03b2+/\u03b1\u2212 sites of \u03b11\u03b22\u03b32 receptorsWork by our group using receptor concatenation determined that both \u03b2+/\u03b1\u2212 subunit interfaces participated equally in modulation by propofol. In contrast, modulation by etomidate was found to be more affected by the \u03b3\u03b2+/\u03b1\u2212\u03b2 interface site (interface 1) than the \u03b1\u03b2+/\u03b1\u2212\u03b3 site (interface 2)2N265 in \u03b21 and \u03b23 are serine and asparagine, respectively, and this single residue dramatically influences sensitivity to loreclezole262829391\u03b21\u03b32 receptors, compared to \u03b11\u03b22\u03b32 receptors. Potentiation by 4-O-methylhonokiol is also reduced by the \u03b22N265S mutation or substitution of \u03b21 for \u03b22The homologs of \u03b24 and \u03b16 subunits, contrasting with benzodiazepine site 1 agonists. Both compounds also potentiated receptors carrying the \u03b4 subunit, although to different degrees. Thus, these compounds not only acted at receptors shown to be located synaptically as \u03b11\u03b22\u20133\u03b32, \u03b12\u03b22\u03b32 and \u03b13\u03b22\u03b325\u03b22\u03b32 receptors and receptors containing the \u03b4 subunit, which are all located extra-synaptically546In subunit specificity studies, compounds 31 and 132 potentiated receptors containing the \u03b1Xenopus laevis tadpoles with EC50s comparable to the anesthetics propofolThe similarities between the three compounds we studied and the clinical anesthetics propofol, etomidate and pentobarbital suggested their possible use as sedative-hypnotics in animals. Indeed, all three compounds induced reversible loss of righting reflexes (LoRR) in A receptors at molecular sites different from the classical benzodiazepine pocket. These compounds, together with 4-O-methylhonokiol, act through \u03b2+/\u03b1\u2212 TMD interfaces, with strongest effects through the interface 1. These compounds potently produced LoRR in aquatic animals and thus may be useful lead compounds in the search for novel anesthetic, sedative-hypnotic or anxiolytic drugs.In summary, the newly identified compounds 31 and 132 modulate both synaptic and extrasynaptic GABA1S269I, \u03b22N265I, \u03b22N265S and \u03b32S280I were prepared using the QuikChangeTM mutagenesis kit .The point mutations \u03b12-\u03b22, and triple construct \u03b11-\u03b22-\u03b11 has been described previously2N265 to I was done in the tandem construct and the triple construct using the QuikChangeTM mutagenesis kit .Construction of tandem and triple subunit cDNAs. The tandem construct \u03b3Capped cRNAs were synthesized  from the linearized plasmids with a cytomegalovirus promotor (pCMV vectors) containing the different subunits, respectively. A poly-A tail of about 400 residues was added to each transcript using yeast poly-A polymerase . The concentration of the cRNA was quantified on a formaldehyde gel using Radiant Red stain (Bio-Rad) for visualization of the RNA. Known concentrations of RNA ladder (Invitrogen) were loaded as standard on the same gel. cRNAs were precipitated in ethanol/isoamylalcohol 19:1, the dried pellet dissolved in water and stored at \u221280\u2009\u00b0C. cRNA mixtures were prepared from these stock solutions and stored at \u221280\u2009\u00b0C.1, \u03b22 and \u03b32 subunits of the GABAA receptors at a concentration of 10 nM:10 nM:50 nMAnimal experiments were carried out in strict accordance to the Swiss ethical guidelines, and have been approved by the local committee of the Canton Bern Kantonstierarzt, Kantonaler Veterin\u00e4rdienst Bern (BE85/15). Surgery was done under anesthesia, and all efforts were made to diminish animal suffering. Xenopus laevis oocytes were prepared, injected and defolliculated as described previously492, 1\u2009mM CaCl2, and 5\u2009mM Na-HEPES (pH 7.4). Concentration response curves for the compounds were fitted with the equation I(c)\u2009=\u2009Imax/[1 + (EC50/c)n], where c is the concentration of the compound, EC50 the concentration eliciting half-maximal current amplitude, Imax is the maximal current amplitude, I the current amplitude, and n is the Hill coefficient. Maximal current amplitudes (Imax) were obtained from the fits of the concentration-response curves. For all receptors studied, modulation was measured at a GABA concentration eliciting 0.5\u20131.5% of the maximal GABA current amplitude. GABA was applied twice alone for 20\u201360\u2009s, and then in combination with the different compounds for 45\u2009s or 1\u2009min. The duration of washout periods was 4\u2009min in between agonist or agonist/drug aplications to prevent receptor desentization. At the beginning of the experiments, GABA applications were repeated when the elicited current amplitude altered by >5%. Potentiation was calculated by the following equation: (IModulator + GABA/IGABA\u2009\u2212\u20091) * 100%. The perfusion solution was applied through a glass capillary with an inner diameter of 1.35\u2009mm, the mouth of which was placed about 0.4\u2009mm from the surface of the oocyte. This allowed fast changes in agonist concentration around the oocyte. The rate of change was estimated 70% in less than 0.5\u2009sCurrents were measured using a modified two-electrode voltage clamp amplifier Oocyte clamp OC-725 (Warner Instruments) in combination with a XY-recorder (90% response time 0.1\u2009s) or digitized at 100\u2009Hz using a PowerLab 2/20 (AD Instruments) using the computer programs Chart . Tests with a model oocyte were performed to ensure linearity in the larger current range. The response was linear up to 15\u2009\u03bcA. The holding potential was \u221280\u2009mV. The perfusion medium contained 90\u2009mM NaCl, 1\u2009mM KCl, 1\u2009mM MgClt test was used to compare two means. One-way analysis of variance (ANOVA) was used for multiple comparisons followed by a Tukey post hoc test. *p\u2009<\u20090.05; **p\u2009<\u20090.01; ***p\u2009<\u20090.001.All data are from at least two different batches of oocytes. Data represent mean\u2009\u00b1\u2009SD. An unpaired Xenopus laevis tadpoles as previously described415250\u2009\u2212\u2009Log[Drug])*HillSlope)) using Graphpad Prism 6. Results are reported as EC50s and 95% confidence intervals.Animals were used and experiments were carried out with approval and according to the guidelines of the MGH Institutional Animal Care and Use Committee. General anesthetic potency was assessed in How to cite this article: Maldifassi, M. C. et al. Novel positive allosteric modulators of GABAA receptors with anesthetic activity. Sci. Rep.6, 25943; doi: 10.1038/srep25943 (2016)."}
{"text": "The mol\u00adecule is arranged around a center of symmetry with half the crown ether mol\u00adecule and one mol\u00adecule of aceto\u00adnitrile symmetry independent. All O\u2014C\u2014C\u2014O torsion angles are gauche while all C\u2014O\u2014C\u2014C angles are trans. The sequence of torsion angles is [(+ttg)(\u2212ttg)]3; the geometry of oxygen atoms is close to pseudo-Dd3 with three atoms below and three atoms above the mean plane, with an average deviation of \u00b10.16\u2005(1)\u2005\u00c5 from the mean plane. This geometry is identical to that observed in metal ion complexes of di\u00adcyclo\u00adhexane-18-crown-6 but differs significantly from the conformation of a free unsolvated mol\u00adecule. Each aceto\u00adnitrile mol\u00adecule connects to a crown ether mol\u00adecule via two of its methyl group H atoms (C\u2014H\u22efO). Weaker inter\u00adactions exist between the third H atom of the aceto\u00adnitrile methyl group and an O atom of a neighbouring crown ether mol\u00adecule (C\u2014H\u22efO); and between the N atom of the aceto\u00adnitrile mol\u00adecule and a H atom of another neighbouring crown ether mol\u00adecule. All these inter\u00admolecular inter\u00adactions create a three-dimensional network stabilizing the disolvate.The title compound (systematic name:  \u00c5b = 9.5286 (5) \u00c5c = 9.8927 (6) \u00c5\u03b1 = 80.415 (2)\u00b0\u03b2 = 81.697 (2)\u00b0\u03b3 = 80.927 (2)\u00b0V = 632.53 (6) \u00c53Z = 1K\u03b1 radiationMo \u22121\u03bc = 0.09 mmT = 173 K0.49 \u00d7 0.34 \u00d7 0.28 mmBruker PHOTON-100 CMOS diffractometerSADABS; Bruker, 2014Tmin = 0.956, Tmax = 1.000Absorption correction: multi-scan (20203 measured reflections3045 independent reflectionsI > 2\u03c3(I)2476 reflections with Rint = 0.031R[F2 > 2\u03c3(F2)] = 0.041wR(F2) = 0.104S = 1.073045 reflections229 parametersAll H-atom parameters refinedmax = 0.29 e \u00c5\u22123\u0394\u03c1min = \u22120.19 e \u00c5\u22123\u0394\u03c1APEX2  used to solve structure: SHELXT  I. DOI: 10.1107/S2056989015011056/zl2627Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627fig1.tifx z . DOI: x, 1 \u2212 y, 1\u00a0\u2212\u00a0z).Structure of the title compound with atom labeling. The second half of the crown ether mol\u00adecule and the second aceto\u00adnitrile mol\u00adecule mol\u00adecule are created by an inversion center located at the center of the crown ether mol\u00adecule (symmetry operator: 1\u00a0\u2212\u00a0Click here for additional data file.10.1107/S2056989015011056/zl2627fig2.tif. DOI: Inter\u00admolecular short contacts of aceto\u00adnitrile mol\u00adecules with neighboring crown ether mol\u00adecules.1405283CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The coordinating water mol\u00adecule is located on a twofold rotation axis while the L2\u2212 anion sits about an inversion center. The L2\u2212 anions bridge the CuII cations, forming polymeric chains propagating along the [101] direction. In the crystal, O\u2014H\u22efO, N\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adaction link the polymeric chains and the solvent water mol\u00adecules into a three-dimensional supra\u00admolecular architecture.In the title polymeric complex, {[Cu(C DOI: 10.1107/S205698901500626X/xu5844Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500626X/xu5844fig1.tifx y z x y z . DOI: x, y, \u2212z\u00a0+\u00a0x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01]The mol\u00adecular structure of (I), a drawing of the asymmetric unit (multi-colored portion) with displacement ellipsoids at the 30% probability level. [symmetry code: (i) 1\u00a0\u2212\u00a0Click here for additional data file.10.1107/S205698901500626X/xu5844fig2.tif. DOI: The polymeric chain of (I).1056415CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The geometry around the cationic PdII centre is distorted square planar, chelated by the imine N- and phenolate O-donor atoms of the two Schiff base ligands. The N- and O-donor atoms of the two ligands are mutually trans, with Pd\u2014N and Pd\u2014O bond lengths of 2.028\u2005(2) and 1.9770\u2005(18)\u2005\u00c5, respectively. The fluoro\u00adphenyl ring is tilted away from the coordination plane and makes a dihedral angle of 66.2\u2005(2)\u00b0 with the phenolate ring. In the crystal, mol\u00adecules are linked into chains along the [101] direction by weak C\u2014H\u22efO hydrogen bonds. Weak \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of 4.079\u2005(2)\u2005\u00c5 stack the mol\u00adecules along c.The asymmetric unit of the title complex, [Pd(C II and NiII complexes of Schiff bases have attracted much attention as they play important roles in bioinorganic chemistry and may provide the basis for models of active sites of biological systems 2], is related to the previously reported compound bis\u00ad{2-[(E)-(4-fluoro\u00adbenz\u00adyl)imino\u00admeth\u00adyl]phen\u00ado\u00adlato-\u03ba2N,O1}nickel(II)  was screened for catalytic activity in the Suzuki cross-coupling reaction between phenyl\u00adboronic acid and iodo\u00adbenzene with a catalyst loading of 1\u2005mmol%. The conversion of iodo\u00adbenzene was found to occur with a yield of 52%.II cation lying on an inversion centre and the Schiff base anion acting as an N,O bidentate chelate ligand \u2005\u00c5, \u03b8 = 112.8\u2005(3) and \u03d5 = 206.9\u2005(3)\u00b0. Other bond lengths and angles observed in the structure are also normal. The fluoro\u00adphenyl ring (C1\u2013C6) makes a dihedral angle of 66.2\u2005(2)\u00b0 with the phenolate ring (C9\u2013C14).The asymmetric unit of (1) contains one-half of the mol\u00adecule with the Pdnd Fig.\u00a01. The PdIs Table\u00a01 are typiA\u22efO1 inter\u00adactions \u2005\u00c5 . These combine with the C\u2014H\u22efO contacts to generate sheets in the ac plane , the mol\u00adecules are linked into chains along the [101] direction by weak C4\u2014H4ns Fig.\u00a02. A weak ns Fig.\u00a02, with a ne Fig.\u00a04. These sII complexes with related Schiff base N2O2 donor sets have been reported -2-(1-(4-fluoro\u00adbenzyl\u00adimino)\u00adeth\u00adyl)phenol  in a round-bottomed flask. Palladium(II) acetate  was dissolved separ\u00adately in CH3CN (20\u2005mL) and was then added into the flask containing the ligand solution. The mixture was stirred and refluxed for 5\u2005h upon which a turmeric yellow solid was formed. The solid was filtered off, washed with ice-cold CH3CN and air dried at room temperature. The solid product was recrystallized from chloro\u00adform, yielding yellow crystals (yield 48.5%). 1H NMR, 13C NMR and IR spectral bands have been studied and agree well with the structure obtained from the values of the CHN analyses and X-ray structure determination.The ligand, : 1598 \u03bd(C=N), 1319 \u03bd(C\u2014N), 1216 \u03bd(C\u2014O), 1321 \u03bd(CH3), 556 \u03bd(Pd\u2014N), 450 \u03bd(Pd\u2014O). 1H NMR : \u03b4 (p.p.m.) 2.32 , 5.11 , 6.53\u20137.46 (ArC). 13C NMR : \u03b4 (p.p.m.) 19.5 (C\u2014CH3), 54.2 (CH2), 115.3, 115.6, 121.3, 128.6, 130.2 (ArC), 169.8 (C=N).Melting point 508\u2013510\u2005K. Analytical data for C\u22121 assignable to the C=N stretching frequency of the azomethine moiety. Weak bands at 556 and 450\u2005cm\u22121 attributable to Pd\u2014N and Pd\u2014O vibrations, respectively  as that observed by Gupta et al. (20132) and methyl (\u2013CH3) protons appear at 5.11 and 2.32 p.p.m., respectively. The 13C chemical shift for the imine carbon (C=N) is found at 169.8 p.p.m., agreeing with data reported by \u015eenol et al. (2011The infrared spectrum of (1) exhibits a strong band at 1598\u2005cm al. 2013. Singlet al. 2011.The title compound was screened for catalytic activity in the Suzuki cross-coupling reaction between phenyl\u00adboronic acid with iodo\u00adbenzene. The reaction was carried out under nitro\u00adgen at 373\u2005K in di\u00admethyl\u00adacetamide with a catalyst loading of 1\u2005mmol%. The conversion of iodo\u00adbenzene was monitored using GC\u2013FID after 24\u2005hours of reaction time. This resulted in a 52% conversion of iodo\u00adbenzene in the reaction.d(C\u2014H) = 0.93\u2005\u00c5 for aromatic, 0.97\u2005\u00c5 for CH2 and 0.96\u2005\u00c5 for CH3 hydrogen atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.Crystal data, data collection and crystal structure refinement details are summarized in Table\u00a0310.1107/S2056989015004405/sj5444sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015004405/sj5444Isup2.hklStructure factors: contains datablock(s) I. DOI: 1045879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular conformation and crystal packing are governed by a network of hydrogen bonds and by \u03c0\u2013\u03c0 stacking.The crystal structure of the title compound allowed the  14H15ClN2O4, prepared by reaction of a methacryloyl dimer with nitro\u00adaniline, was determined to establish the relative substituent orientation on the cyclo\u00adpenta\u00adnone ring. In agreement with an earlier proposed reaction mechanism, the amide group and the methyl group adjacent to the chloro substituent adopt equatorial positions and relative cis orientation, whereas the Cl substituent itself and the methyl group adjacent to the amide have axial orientations relative to the mean plane of the five-membered ring. The conformation of the mol\u00adecule is stabilized by one classical N\u2014H\u22efO (2.18\u2005\u00c5) and one non-classical C\u2014H\u22efO (2.23\u2005\u00c5) hydrogen bond, each possessing an S(6) graph-set motif. The crystal packing is defined by several non-classical intra\u00admolecular hydrogen bonds, as well as by partial stacking of the aromatic rings.The structure of the title compound, C Compounds (3) and (4) show similar 1H and 13C NMR spectra, making the direct assignment of the relative orientation of the cyclo\u00adpenta\u00adnone substituents almost impossible. The crystal structure of (1), as well as the crystal structure of another aromatic amide, cis-3-chloro-N--1,3-dimethyl-2-oxo\u00adcyclo\u00adpenta\u00adnecarboxamide, solved and reported earlier -1,3-dimethyl-2-oxo\u00adcyclo\u00adpenta\u00adne\u00adcarboxamide with cis orientation of two methyl groups, see Fischer et al. (1985Dimer (2) forms in the oxa-Diels\u2013Alder reaction of two methacryloyl chloride mol\u00adecules and, in the presence of a Lewis acid \u2005\u00c5 for N1. The conformation of the amide is stabilized by one classical N1\u2014H1\u22efO1 (2.18\u2005\u00c5) and one non-classical C10\u2014H10\u22efO2 (2.23\u2005\u00c5) hydrogen bonds  graph-set motif \u2005\u00c5], the aromatic rings of neighboring mol\u00adecules show partial stacking with several short contacts centered near their nitro-substituent: C14\u22efC13i , and C13\u22efN2i [3.1860\u2005(14)\u2005\u00c5]. The C7\u2014H7A\u22efO1i hydrogen bond (2.53\u2005\u00c5) provides additional cohesion between neighboring enanti\u00adomeric mol\u00adecules in the columns  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01], and along the a axis by C7\u2014H7C\u22efO4ii  non-classical hydrogen bonds  \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a0The crystal packing is governed by several short contacts, which may be classified as non-classical hydrogen bonds  and readily afforded large transparent X-ray quality crystals upon slow evaporation of CHCl3/heptane solution (m.p. 402\u2013403\u2005K). 1H NMR : \u03b4 8.89 , 8.26\u20138.16 , 7.78\u20137.70 , 2.91\u20132.78 , 2.49\u20132.40 , 2.12\u20132.05 , 2.05\u20131.98 , 1.75 , 1.51 . 13C NMR : \u03b4 212.4, 168.9, 143.7, 143.3, 125.0, 119.3, 69.7, 55.0, 35.6, 29.4, 25.0, 24.1. MS (EI): m/z (%) 310\u2005(85) [M]+., 173\u2005(85) [M\u2013NHAr]+. HRMS (EI): m/z [M]+ calculated for C14H15ClN2O4 310.07203, found 310.07170.The title compound was prepared as described by Warneke  al. 2014 by reactUiso(H) values were fixed at 1.5Ueq(C) for methyl H atoms, and 1.2Ueq for all other carrier atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S1600536814017711/hg5403sup1.cifCrystal structure: contains datablock(s) 1. DOI: 10.1107/S1600536814017711/hg54031sup2.hklStructure factors: contains datablock(s) 1. DOI: 1017486CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The three mol\u00adecular components are held together through hydrogen bonds.The crystal structure of the title salt hydrate contains discrete DABCOH 6H13N2+\u00b7S2O32\u2212\u00b72H2O, contains a centrosymmetric cyclic motif of eight hydrogen-bonded mol\u00adecular subunits. Two DABCOH+ cations  are linked to two water mol\u00adecules and two thio\u00adsulfate anions via O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds, respectively. Two other water mol\u00adecules close the cyclic motif through O\u2014H\u22efO contacts to the first two water mol\u00adecules and to the two thio\u00adsulfate anions. A second pair of DABCOH+ cations is N\u2014H\u22efO hydrogen bonded to the two anions and is pendant to the ring. Adjacent cyclic motifs are bridged into a block-like arrangement extending along [100] through O\u2014H\u22efO inter\u00adactions involving the second pair of water mol\u00adecules and neighbouring thio\u00adsulfate anions.The crystal structure of the hydrated title salt, 2C The thio\u00adsulfate anion exhibits approximate Cv3 symmetry. However, in the crystal it has C1 symmetry with S\u2014O distances in the range 1.4688\u2005(8) to 1.4898\u2005(8)\u2005\u00c5 and an S\u2014S bond length of 2.0047\u2005(4)\u2005\u00c5, and O\u2014S\u2014O and S\u2014S\u2014O angles ranging from 107.47\u2005(4) to 110.48\u2005(5)\u00b0. In both DABCOH+ cations, the three N\u2014C bonds involving the protonated N atom are elongated [mean value 1.499\u2005(2)\u2005\u00c5] compared to the three N\u2014C bonds involving the non-protonated N atoms [mean value 1.472\u2005(4)\u2005\u00c5].The asymmetric unit Fig.\u00a01 consistsvia charge-assisted N\u2014H\u22efO hydrogen bonds to two DABCOH+ cations. The third oxygen atom (O2) of the anion acts as a hydrogen-bond acceptor for one of the water mol\u00adecules (O4). The second hydrogen bond involving this water mol\u00adecule is directed towards a symmetry-related thio\u00adsulfate anion. The second water mol\u00adecule (O5) is the donor of one O\u2014H\u22efO hydrogen bond to the other water mol\u00adecule and of one N\u2014H\u22efO hydrogen bond to one of the DABCOH+ cations. Numerical details of the hydrogen-bonding inter\u00adactions are given in Table\u00a01+ cations  global, I. DOI: 10.1107/S2056989016001535/wm5264Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016001535/wm5264Isup3.cmlSupporting information file. DOI: 1449673CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Weak \u2018secondary\u2019 Te bonds and O\u2014H\u22efO hydrogen-bonding inter\u00adactions, involving water mol\u00adecules and layer O atoms, link the layers and inter\u00adlayer species. IR spectroscopic data are also presented.A new hydrated yttrium copper tellurite nitrate, yttrium(III) copper(II) bis\u00ad[trioxidotellurate(IV)] nitrate trihydrate, has been synthesized hydro\u00adthermally in a Teflon-lined autoclave and structurally determined using synchrotron radiation. The new phase is the first example containing yttrium, copper and tellurium in one structure. Its crystal structure is unique, with relatively strongly bound layers extending parallel to (020), defined by YO Tellurite and nitrate anions (involving atoms O1\u2013O9) are clearly distinguished from water mol\u00adecules OW1\u2013OW3 by their bond-valence sums (Table\u00a012\u2212 and 2 \u00d7 H2O at 2.290\u2005(3)\u20132.497\u2005(3)\u2005\u00c5. Cu is in square-planar coordination, with four close oxygen neighbours at 1.904\u2005(3)\u20131.999\u2005(3)\u2005\u00c5. Two more oxygen ligands at 2.811\u2005(4) and 2.817\u2005(4)\u2005\u00c5 complete an octa\u00adhedron that is very elongated due to the Jahn-Teller distortion. Te1 is trigonal\u2013pyramidally coordin\u00adated by three oxygen atoms at 1.883\u2005(3)\u20131.911\u2005(3)\u2005\u00c5. Three \u2018secondary bonds\u2019 to O atoms at 2.657\u2005(3)\u20132.837\u2005(3)\u2005\u00c5 complete a polyhedron that can be described as an octa\u00adhedron that is very distorted due to the lone-pair stereoactivity. Te2 has very similar coordination, with three primary Te\u2014O bonds of 1.893\u2005(3)\u20131.905\u2005(3)\u2005\u00c5 and three secondary bonds of 2.681\u2005(4)\u20132.798\u2005(3)\u2005\u00c5. In each case, two of the secondary bonds provide additional bracing within the {Y\u22efCu\u22efTe} layer, while the third is to a nitrate oxygen , and thus provides weak bridging between the layers and inter\u00adlayer species. The nitrate oxygen atom O9 makes a seventh very distant ligand for both Te1 [3.231\u2005(4)\u2005\u00c5] and Te2 [3.350\u2005(4)\u2005\u00c5], further than the shortest Te\u22efCu distances and with bond valences < 0.05 valence units, using the parameters of Mills & Christy  are defined by YOs Table\u00a01. Within isty 2013.et al. 4]4\u2212 of {Cu\u22efTe\u22efCu\u22efTe} squares running parallel to [001] 8 polyhedra 2] and its Er\u2014Cl and Er\u2014Br analogues , DTGS (Deuterated Triglycine Sulfate) detector, 4\u2005cm al. 2013. Numeric3)2(NO3)(H2O)3 were synthesized hydro\u00adthermally. For the synthesis, Y(NO3)3\u00b76H2O , Cu(NO3)2\u00b73H2O (Sigma\u2013Aldrich \u226599%) and Te 200\u2005mm mesh  were used as starting materials. A 1:1:1 molar ratio of the reagents in 20\u2005ml water was reacted in a Teflon autoclave bomb at 473\u2005K for 3 days. Crystals of YCu(TeO3)2(NO3)(H2O)3 were separated manually from a blue powder of undetermined composition in a few percent yield. Several unsuccessful attempts were made to synthesize YCu(TeO3)2(NO3)(H2O)3 from a stoichiometric mixture of the reagents, using the molar ratio 1:1:2. We also were unsuccessful in producing new compounds, with the same structure type or not, using La, Ce, Nd or Gd in place of Y.Dark blue prisms of YCu\u2005\u00c5.Single crystal X-ray diffraction experiments were carried out on the micro-focus macromolecular beam line MX2 of the Australian Synchrotron. Details of data collection and structure refinement are provided in Table\u00a0410.1107/S2056989016011464/wm5307sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016011464/wm5307Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016011464/wm5307sup3.pdfSupporting information file. DOI: 1493330CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecules form a closely spaced lattice structure in which neighbouring porphyrins are oriented in inversion-related dimers.The title compound contains one independent mol\u00adecule which exhibits an overall  48H60N4O2)], contains one independent mol\u00adecule. The average Ni\u2014N bond length is 1.917\u2005(13)\u2005\u00c5. The mol\u00adecules are arranged in a closely spaced lattice structure in which neighbouring porphyrins are oriented in inversion-related dimers. The nickel(II) porphyrin is characterized by a significant degree of a ruffled (Bu1) conformation with small contributions from saddle (Bu2) and wave (y) [gE(y)], as determined using normal structural decomposition. Disorder in the 2,5-di\u00ad\u00admeth\u00adoxy\u00adphenyl substituent was modelled over two positions with a 60% occupancy for the major moiety. One of the ethyl groups is also disordered over two positions and was modelled with the major moiety being present in 51.3% occupancy.The asymmetric unit of the title nickel(II) porphyrin, [Ni(C There are many studies available on metal coordination porphyrinato]nickel(II), which has an average Ni\u2014N bond length of 1.925\u2005\u00c5  and the meso carbon (Cm) can be used to determine structural differences between similar porphyrins and differences within the individual porphyin structure. The C\u03b1\u2014Cm(but\u00adyl)\u2014C\u03b1 angle of 119.12\u2005(2)\u00b0 is smaller than the C\u03b1\u2014Cm(H)\u2014C\u03b1 angle, and the C\u03b1\u2014Cm\u2014C\u03b1 angle at 123.2\u2005(2)\u00b0 is similar to both C\u03b1\u2014Cm(H)\u2014C\u03b1 angles, 122.1\u2005(3)\u00b0 (C20) and 124.8\u2005(3)\u00b0 (C15). The 2,5-di\u00admeth\u00adoxy\u00adphenyl group is tilted at an angle of 75.80\u2005(7)\u00b0 from the 24-atom least-squares plane of the porphyrin ring.The average Ni\u2014N distance is 1.917\u2005(13)\u2005\u00c5. The largest deviation occurs at the Ni\u2014N2 bond [1.906\u2005(2)\u2005\u00c5], which lies between both substituted et al., 1998ruffled (Bu1) with small contributions from saddle (Bu2) and wave (y) [gE(y)] , [gE(x)] and domed (Au2), which is similar to both highly substituted and other Ni(II) porphyrins . The tilt of the pyrrole rings against the 24-atom plane are N1 [24.85\u2005(8)\u00b0], N2 [25.22\u2005(8)\u00b0], N3 [15.79\u2005(10)\u00b0] and N4 [17.58\u2005(8)\u00b0], with the highest deviation from the mean plane associated with the pyrrole rings closest to the butyl group at C5. The maximum deviations from the least-squares plane are associated with the meso C atoms. C5 deviates from the least-squares plane by 0.880\u2005(2)\u2005\u00c5, whereas C10, C15 and C20 deviate from the plane at 0.551\u2005(2), 0.512\u2005(3) and 0.667\u2005(2)\u2005\u00c5, respectively. Table\u00a01A conformational analysis was performed using the NSD  method developed by Shelnutt and co-workers (Shelnutt )] Fig.\u00a02. There an-butyl group (C51 > C54) with the phenyl meth\u00adoxy unit, specifically between H54A\u22efC104, at 2.851\u2005(4)\u2005\u00c5, the meth\u00adoxy group (O1 > C111) with the ethyl group (C181 > C182) between O1\u22efH18C at 2.552\u2005(4)\u2005\u00c5, the meth\u00adoxy group (O2B > C108) with the ethyl group (C21 > C22) between O2B\u22efH22A at 2.486\u2005(3)\u2005\u00c5 and the ethyl group (C121 > C122) with the C15 atom, between C15\u22efH12E at 2.833\u2005(3)\u2005\u00c5. However, there are no \u03c0\u2013\u03c0 inter\u00adactions or hydrogen bonds evident in the crystal structure.The unit cell of the title compound consists of two mol\u00adecules, each at a distance of 4.949\u2005\u00c5 from the 24-atom mean plane of the other. The mol\u00adecules are arranged in a closely spaced lattice structure in which ethyl groups and butyl groups point towards each other to form a cage-like inversion-related dimer Fig.\u00a03. Mol\u00adecuet al. (1992a\u2014Cm(H)\u2014Ca angles (122.85\u2013123.58\u00b0) compared to the title compound. We also determined the structure of nickel(II) with and without deuterated chloro\u00adform nickel(II) and zinc(II)  derivative exhibits angles that are similar to the title compound, 122.12\u2013122.35\u00b0 for the substituted meso-positions and 123.42\u2013123.78\u00b0 for the unsubstituted meso-positions. The average Ni\u2014N bond length of 1.923\u2005\u00c5 is comparable to that of the title compound. The zinc derivative of this compound exhibits a larger average metal\u2013nitro\u00adgen bond length of 2.054\u2005\u00c5 and wider C\u03b1\u2014Cm\u2014C\u03b1 angles, 124.85\u2013125.95\u00b0 for the substituted meso-positions and 126.81\u2013127.78\u00b0 for unsubstituted meso-positions, as to be expected for zinc porphyrins.A search of the Cambridge Structural Database . The solution was heated to room temperature and over the course of 1\u2005h added to a solution of nickel(II)  yielding purple crystals of the title compound . The compound was recrystallized from a solution of 1%vol MeOH in CH2Cl2 layered with hexane to yield single crystals suitable for X-ray diffraction.The title compound was prepared as reported previously (Senge Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Disorder in the 2,5-di\u00admeth\u00adoxy\u00adphenyl substituent was modelled over two positions with a 60% occupancy for the major moiety. The ethyl group at C12 was modelled over two positions with the major moiety being present in 51.3% occupancy. Restraints and constraints were used to model the disorder with SHELXL2014  I, publication_text. DOI: 10.1107/S2056989015020058/wm5222Isup2.hklStructure factors: contains datablock(s) I. DOI: 1427139CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Each Cd2+ cation is coordinated by two N atoms and one O atom of the tridentate ligand and three chloride anions, forming a distorted CdNOCl3 octahedron. Each pair of adjacent metal cations is linked by two bridging chloride ligands, resulting in a dinuclear complex unit. The mol\u00adecular conformation is stabilized by intra\u00admolecular N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds. In the crystal, mol\u00adecules are linked by nonclassical C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds into a three-dimensional network. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.777\u2005(2) and 3.631\u2005(2)\u2005\u00c5] contribute to the stabilization of the crystal packing.The title compound, [Cd DOI: 10.1107/S1600536814010630/rz5124Isup2.hklStructure factors: contains datablock(s) I. DOI: 1001915CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S)-ABOC], two amino acid residues [(S)-Ala and (S)-Phe], and protecting groups of Boc and OBn. The tetra\u00admer folds into a right-handed mixed 11/9 helix stabilized by intra\u00admolecular i,i + 3 and i,i-1 C=O\u22efH\u2014N hydrogen bonds. The oligomers are linked into chains by N\u2014H\u22efO=C hydrogen bonds with the chloro\u00adform solvent mol\u00adecules inter\u00adcalated between the folded chains via C\u2014H\u22efO=C inter\u00adactions.In the title compound, the \u03b1,\u03b2-hybrid peptide contains two non-proteinogenic amino acid residues [( S)-2-[(S)-(1-{2-[(S)-(1-{[(tert-but\u00adoxy)carbon\u00adyl]amino}\u00adbicyclo\u00ad[2.2.2]octan-2-yl)formamido]\u00adpropanamido}\u00adbicyclo\u00ad[2.2.2]octan-2-yl)formamido]-3-phenyl\u00adpropano\u00adate chloro\u00adform monosolvate, C42H56N4O7\u00b7CHCl3, the \u03b1,\u03b2-hybrid peptide contains two non-proteinogenic amino acid residues of (S)-1-amino\u00adbicyclo\u00ad[2.2.2]octane-2-carb\u00adoxy\u00adlic acid [(S)-ABOC], two amino acid residues of (S)-2-amino\u00adpropanoic acid [(S)-Ala] and (S)-2-amino-3-phenyl\u00adpropanoic acid [(S)-Phe], and protecting groups of tert-but\u00adoxy\u00adcarbonyl (Boc) and benzyl ester (OBn). The tetra\u00admer folds into a right-handed mixed 11/9 helix stabilized by intra\u00admolecular i,i\u00a0+\u00a03 and i,i\u00a0\u2212\u00a01 C=O\u22efH\u2014N hydrogen bonds. In the crystal, the oligomers are linked by N\u2014H\u22efO=C hydrogen bonds into chains along the a-axis direction. The chloro\u00adform solvent mol\u00adecules are inter\u00adcalated between the folded chains via C\u2014H\u22efO=C inter\u00adactions.In the title compound, phenyl ( S)-1-amino\u00adbicyclo\u00ad[2.2.2]octane-2-carb\u00adoxy\u00adlic acid [(S)-ABOC] is a \u03b22,3,3-tris\u00adubstituted bicyclic amino acid which exhibits a high propensity to induce both a reverse turn into short peptides and helices in oligoureas and in \u03b1,\u03b2-hybrid peptides  and the NH of the \u03b1-residue (i\u00a0+\u00a03) and two C9 pseudocycles between the CO of the \u03b1-residue (i) and the NH of the \u03b2-residue (i\u00a0\u2212\u00a01). The backbone torsion angles are quite similar to those of the characteristic 11/9 helix reported in the same \u03b1,\u03b2-hybrid oligomers \u2005\u00c5] and a C\u2014H\u22efO hydrogen bond [C\u22efO = 3.071\u2005(4)\u2005\u00c5].The inter\u00admolecular inter\u00adaction N2\u2014H2\u22efO5i Table\u00a01 connectson Fig.\u00a02. In the iPrCO instead of Boc are not isomorphous. This latter crystallized in the space group P21 with two independent mol\u00adecules in the asymmetric unit. One independent mol\u00adecule shows a single fully folded 11/9 helix as the title compound while the hydrogen-bond network is incomplete in the other mol\u00adecule. The last C9 hydrogen bond between the carbonyl of the Phe residue and the \u03b2-residue amide proton was disrupted by the incorporation of a water mol\u00adecule  parameters were fixed at 1.2Ueq for methine, methyl\u00adene, aromatic groups and NH groups, and at 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015016941/is5415sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016941/is5415Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015016941/is5415Isup3.cmlSupporting information file. DOI: 1423394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal packing features C\u2014H\u22ef\u03c0 and \u03c0\u2014\u03c0 inter\u00adactions, which generate a three-dimensional network.In the title compound, C 25H20ClN3O, the C=N bond of the central imine group adopts an E conformation. The mean planes through the essentially planar carbazole [maximum deviation = 0.052\u2005(2)\u00c5] and quinoline [maximum deviation = 0.050\u2005(2)\u2005\u00c5] ring systems form a dihedral angle of 50.2\u2005(1)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 and \u03c0\u2014\u03c0 inter\u00adactions [centroid\u2013centroid distances ranging from 3.635\u2005(2) to 3.739\u2005(2)\u2005\u00c5], forming a three-dimensional supra\u00admolecular network.In the title compound, C The sum of the bond angles around N1 (360.05\u00b0) of the pyrrole ring is in accordance with sp2 hybridization. Atom Cl1 deviates from the plane of the attached quinoline ring system by 0.100\u2005(1)\u2005\u00c5. The geometric parameters of the title mol\u00adecule agree well with those reported for similar structures , 3.739\u2005(2), 3.739\u2005(2), 3.635\u2005(2) and 3.635\u2005(2)\u2005\u00c5, respectively, forming a three-dimensional supra\u00admolecular network  \u2212x, \u2212y, 1\u00a0\u2212\u00a0z; (ii) 1\u00a0\u2212\u00a0x, y, z; (iii) 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z and (iv) \u2212x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z).In the crystal, mol\u00adecules are linked by two C\u2014H\u22ef\u03c0 inter\u00adactions; the first one between the benzene H atom of the carbazole ring system and the benzene ring of an adjacent mol\u00adecule, with a C1\u2014H1\u22efH-carbazol-3-amine (1\u2005mmol) and sulfated SnO2-fly ash catalyst (50\u2005mg) in water (15\u2005ml) and was refluxed at 353\u2005K for 5\u201310 minutes. The completion of the reaction was monitored by TLC (ethyl acetate and hexane as an eluent 20%). After completion, the reaction mixture was cooled to ambient temperature. Then di\u00adchloro\u00admethane (20\u2005ml) was added and the organic layer filtered, dried on anhydrous Na2SO4 and the solvent removed using a rotary evaporator. The crude product was purified by column chromatography on silica gel (200 mesh) with hexane and ethyl acetate (4:1) as eluent to afford the title compound in good yield (10%). Red blocks suitable for X-ray diffraction analysis were obtained by recrystallization from di\u00adchloro\u00admethane solution at room temperature.A 25\u2005ml round-bottom flask was charged with dimedone (1\u2005mmol), 2-chloro-6-meth\u00adoxy\u00adquinoline-3-carbaldehyde (1\u2005mmol) 9-ethyl-9Uiso(H)=1.5Ueq for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989015005794/hb7384sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015005794/hb7384Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015005794/hb7384Isup3.cmlSupporting information file. DOI: 1027676CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two independent cations are conformationally similar with the comparative dihedral angles between the central pyridine ring and the three benzene substituent rings being 3.0\u2005(2), 36.4\u2005(1) and 24.2\u2005(1)\u00b0, and 3.7\u2005(2), 36.5\u2005(1) and 24.8\u2005(1)\u00b0, respectively. In the crystal, the cations, anions and water mol\u00adecules are linked through O\u2014H\u22efO and O\u2014H\u22efBr hydrogen bonds, forming an insular unit. Within the cations there are also intra\u00admolecular N\u2014H\u22efO hydrogen bonds. Adjacent centrosymmetrically related aggregates are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine ring and a benzene ring in both cations [ring-centroid separations = 3.525\u2005(3) and 3.668\u2005(3)\u2005\u00c5], forming chains extending across the ac diagonal. Voids between these chains are filled by dichloromethane molecules.The asymmetric unit in the structure of the title compound, C DOI: 10.1107/S2056989015021386/zs2352Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352fig1.tif. DOI: The asymmetric unit in the structure of the title compound, with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines.Click here for additional data file.10.1107/S2056989015021386/zs2352fig2.tifx y z . DOI: x\u00a0+\u00a0y\u00a0+\u00a0z operation.The result of superposition of one independent cation with another shifted by an Click here for additional data file.10.1107/S2056989015021386/zs2352fig3.tifA x y z . DOI: A indicates the symmetry operator \u2212x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a0Insular hydrogen bonded aggregates in the structure. Hydrogen bonds are shown as dashed lines. Suffix Click here for additional data file.10.1107/S2056989015021386/zs2352fig4.tif. DOI: Chains formed by \u03c0\u2013\u03c0 stacking inter\u00adactions between aromatic ring systems in adjacent H-bonded frameworks.1436252CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mononuclear complex exhibits a distorted tetra\u00adhedral coordination geometry about the metal atom, arising from one S atom of the benzene\u00adcarbo\u00adthio\u00adamide ligand, two P atoms of two tri\u00adphenyl\u00adphosphane mol\u00adecules and one bromide ion. An intra\u00admolecular N\u2014H\u22efBr hydrogen bond is observed and in the crystal structure, inversion dimers linked by pairs of N\u2014H\u22efBr and C\u2014H\u22efBr hydrogen bonds are observed. In addition, C\u2014H\u22ef\u03c0 inter\u00adactions occur, leading to [101] chains. 7H7NS)(C18H15P)2], was obtained from the reaction of silver(I) bromide with benzene\u00adcarbo\u00adthio\u00adamide (C7H7NS) and tri\u00adphenyl\u00adphosphane (C18H15P) in the mixed solvent of aceto\u00adnitrile and ethanol. The mononuclear complex exhibits a distorted tetra\u00adhedral coordination geometry about the metal atom, arising from one S atom of a benzene\u00adcarbo\u00adthio\u00adamide ligand, two P atoms of two tri\u00adphenyl\u00adphosphane mol\u00adecules and one bromide ion. An intra\u00admolecular N\u2014H\u22efBr hydrogen bond is observed and in the crystal structure, inversion dimers linked by pairs of N\u2014H\u22efBr and C\u2014H\u22efBr hydrogen bonds are observed. In addition, C\u2014H\u22ef\u03c0 inter\u00adactions occur, leading to [101] chains. Hirshfeld-surface analyses are presented and discussed.The title complex, [AgBr(C I-containing phospho\u00adrus and sulfur donor ligands have been studied and published extensively in recent years (C18H15P)2] previously synthesized by us (C18H15P)2], 2.5580\u2005(5)\u2005\u00c5. The Ag\u2014P bond lengths of 2.4682\u2005(7) and 2.4671\u2005(6)\u2005\u00c5 for Ag1\u2014P1 and Ag1\u2014P2, respectively, are similar to those of the Ag\u2014P bond lengths in [AgCl(C7H7NS)(C18H15P)2] [2.4529\u2005(5) and 2.4578\u2005(5)\u2005\u00c5], and similar to the Ag\u2014P distances of analogous tetra\u00adhedrally coordinated AgI complexes such as [Ag(NO3)(C2H3N3S)(C18H15P)2]  \u00b72NO3  and C17\u2014H17\u22efBr1i [3.789\u2005(3)\u2005\u00c5]  hydrogen bonds between a pair of adjacent complex mol\u00adecules; these are similar to the those in the above-mentioned complex [AgCl(C7H7NS)(C18H15P)2] \u2005\u00c5].In the crystal, the dimeric inter\u00admolecular inter\u00adactions are generated through a crystallographic inversion center by linking through the N1\u2014H1et al., 2004Crystal Explorer 3.1  and outside (de) of the Hirshfeld surface analyse the inter\u00admolecular inter\u00adactions via the mapping of normd, as depicted in Fig.\u00a04a\u2013d) for Hirshfeld surfaces of the complex are shown with characteristic pseudo-symmetry wings in the upper left and lower right sides of the de and di diagonal axes that represent the overall 2D fingerprint plot and those delineated into H\u22efH, H\u22efBr/Br\u22efH, and C\u22efH/H\u22efC contacts are shown in Fig.\u00a05a\u2013d, respectively. The fingerprint plot of H\u22efH contacts represented by the largest contribution within the Hirshfeld surfaces (60.8%) are shown as one distinct pattern with a minimum value of de + id \u223c2.6\u2005\u00c5. The reciprocal H\u22efBr/Br\u22efH contacts consist of 5.4% of the total Hirshfeld surface with de + id \u223c3.3\u2005\u00c5, exhibited by two symmetrical narrow pointed wings indicating the inter\u00admolecular hydrogen-bond inter\u00adactions N1\u2014H1A\u22efBr1 and C17\u2014H17\u22efBr1 in the crystal packing. The presence of C\u2014H\u22ef\u03c0 inter\u00adactions on the fingerprint plot, which contribute 29.7% of overall Hirshfeld surface, are indicated by de + id \u223c3.0\u2005\u00c5.For the title complex, the Hirshfeld-surfaces analysis  bromide  was dissolved in the mixed solvent of 15\u2005ml of aceto\u00adnitrile and 15\u2005ml of ethanol and then tri\u00adphenyl\u00adphosphane  was added. The mixture was refluxed for 2\u2005h at 343\u2005K and a white precipitate was formed. After that, benzene\u00adcarbo\u00adthio\u00adamide  was added and continually refluxed for 5\u2005h. At that time, the white precipitate dissolved. The clear yellow solution was filtered and left to evaporate at room temperature. After a day, pale-yellow blocks of the title compound were filtered off and dried Uiso(H) = 1.2 Ueq(C). N-bound H atoms were found from difference maps and refined isotropically with distance restraint N\u2014H = 0.85\u20130.86\u2005\u00c5.Crystal data and details of structure determination are summarized in Table\u00a0210.1107/S2056989016009518/hb7592sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016009518/hb7592Isup2.hklStructure factors: contains datablock(s) I. DOI: 1484796CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The PH 21H21O5PS\u00b7H2O\u00b7CH2Cl2, the phospho\u00adnium\u2013sulfonate zwitterion has the acidic H atom located on the P atom rather than the sulfonate group. The S\u2014O bond lengths [1.4453\u2005(15)\u20131.4521\u2005(14)\u2005\u00c5] are essentially equal. In the crystal, the water mol\u00adecules bridge two zwitterions via Owater\u2014H\u22efOsulfonate hydrogen bonds into a centrosymmetric dimer. The dimers are further linked by weak CAr\u00adyl\u2014H\u22efOsulfonate hydrogen bonds into chains extending along [100]. The PH+ group is not involved in inter\u00admolecular inter\u00adactions.In the title compound, C Addition of an H+ at phospho\u00adrous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo3 conformation. The Ometh\u00adoxy\u22efP distances, 2.7691\u2005(14) and 2.7940\u2005(14)\u2005\u00c5, are shorter than the sum of the O and P van der Waals radii (3.35\u2005\u00c5). The O3\u22efH1(P1) distance is 2.44\u2005(2)\u2005\u00c5.Compound up Fig.\u00a01. The S\u2014Oexo3 conformation versus alternative exo2 and exo1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0  or two (exo1) meth\u00adoxy groups were rotated away from the PH+ group. The exo2 and exo1 conformers were calculated to be 1.2 and 2.5 kcal mol\u22121 less stable than the exo3 isomer, respectively. The HOMO of the exo3 conformer is comprised of p orbitals of the sulfonate O atoms, while the LUMO is delocalized over the phenyl rings and P\u2014Caromatic bonds  and 1.98\u2005(3)\u2005\u00c5 (H2O)][2-{(o-CF3-Ph)2P}-4-Me-benzene\u00adsulfonate] . The structure of the tri\u00adethyl\u00adammonium salt of 2-[bis\u00ad(2-meth\u00adoxy\u00adphen\u00adyl)phos\u00adphanyl]benzene\u00adsulfonate has also been reported . The product was purified by recrystallization . Crystals of 1\u00b7H2O\u00b7CH2Cl2 (I) suitable for the X-ray diffraction analysis were obtained by layering Et2O on a CH2Cl2 solution of 1 at 277\u2005K.Compound Uiso(H) set to 1.2\u20131.5Ueq(C). The P- and O-bound H atoms were located in a difference Fourier map and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016000669/cv5502sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016000669/cv5502Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016000669/cv5502Isup3.cmlSupporting information file. DOI: 1447138CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Melting points of compounds Cu3V2O8 and Cu2V2O7 are 780\u00b0C and 790\u00b0C, respectively. The addition of small amounts of Mg (II), MgxCu3-xV2O8 (x\u2009<\u20091.0) and MgyCu2-yV2O7 (y\u2009<\u20090.5) fused compositions, was not sufficient to stabilize structures at 800\u00b0C. For the Mg2CuV2O8 (x\u2009=\u20092.0) composition fired at 800\u00b0C, Mg (II) incorporated into the monoclinic Cu3V2O8 structure stabilizes this crystalline phase. At 1000\u00b0C, orthorhombic Mg3V2O8 structure from this composition was obtained. Solid solutions with orthorhombic symmetry were detected from the prepared compositions fired at 1000\u00b0C when 1.0\u2009\u2264\u2009x\u2009\u2264\u20093.0. The difference of coloration of Cu, Mg vanadates might be explained by the presence of a strong charge transfer band in visible spectra.In this study, MgThe online version of this article (doi:10.1186/s40064-015-0908-8) contains supplementary material, which is available to authorized users. Charge transfer effects in which an electron is transferred between an anion and a cation are often responsible for intense colours as in, for example, permanganate (purple) and chromates (yellow). In solids, there is an additional source of colour; it involves the transition of electrons between energy bands. Colour may be measured in a quantitative way by spectroscopic techniques. At higher frequencies than the infrared, electronic transitions associated with d-level splitting, impurity ions, crystal defects, etc., are possible. Many of these occur in the visible region and are responsible for colour.3V2O8 compound with monoclinic symmetry and space group P121/c1 is similar to the orthorhombic structure of Mg3V2O8 compound with space group Cmca  and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions was made to investigate the possible formation of solid solutions with orthovanadate or divanadate structure. Coloration of these materials was also measured and related with structure in prepared compositions. A partial substitution of Cu (II) by Mg (II) ions might increase the melting point of materials with orthovanadates and divanadates structures. These potential solid solutions could be applied in ceramic industry.In this study, structural characterization of MgxCu3-xV2O8 (0\u2009\u2264\u2009x\u2009\u2264\u20093) and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions were synthesized by the chemical coprecipitation method. The starting materials were Cu(NO3)2\u2009\u00b7\u20092.5H2O , MgCl2.6H2O (Panreac) of reagent grade chemical quality, and NH4VO3 . The stoichiometric amount of NH4VO3, Cu(NO3)2\u2009\u00b7\u20092.5H2O and MgCl2\u2009\u00b7\u20096H2O was added on 200\u00a0mL of water with vigorous stirring at room temperature. These starting materials were added in solid state and the concentration of the various cations is different in each prepared composition. After that, a solution of ammonium hydroxide was added dropwise until pH\u2009=\u20098. The obtained precipitates were dried by an infrared lamp and dry samples were fired at 300\u00b0C for 12\u00a0hours, 600\u00b0C for 12\u00a0hours, 800\u00b0C for 1\u00a0hour and 1000\u00b0C for 1\u00a0hour.MgxCu3-xV2O8 (0\u2009\u2264\u2009x\u2009\u2264\u20093) and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) fired compositions to investigate the possibility of formation of solid solution in these synthetic conditions. The diffraction patterns were collected running from 5 to 110 o2\u03b8, using monochromatic CuK\u03b1 radiation, a step size of 0.02 o2\u03b8 and a sampling time of 10\u00a0s. The initial structural information was obtained of the Inorganic Crystal Structure Database  Rietveld . Unit ceUV\u2013vis-NIR spectroscopy (diffuse reflectance) allows the Cu (II) site and the V (V)-O and Cu (II)-O charge bands in samples to be studied. A Jasco V-670 spectrophotometer was used to obtain the UV\u2013vis-NIR (ultraviolet visible near infrared) spectra in the 200 to 2500\u00a0nm range. X-Rite spectrophotometer  was used to obtain CIEL*a*b* colour parameters on fired samples: L* is the lightness axis (black (0)\u2009\u2192\u2009white (100)), a* the green (\u2212)\u2009\u2192\u2009red (+) axis, and b* is the blue (\u2212)\u2009\u2192\u2009yellow (+) axis CIE .xCu3-xV2O8 (0\u2009\u2264\u2009x\u2009\u2264\u20093) and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions. XRD patterns from MgxCu3-xV2O8 and MgyCu2-yV2O7 compositions are shown in Additional files Tables\u00a0xCu3-xV2O8 (0\u2009\u2264\u2009x\u2009<\u20091.0) compositions the major crystalline phase is the triclinic Cu3V2O8 polymorph at 600\u00b0C. Cu3V2O8 compound melts incongruently at 780\u00b0C. This fact can explain the melting of samples with a presence higher than 50% in Cu3V2O8 triclinic crystalline phase . This crystalline phase with triclinic structure is not detected in samples fired at 800 and 1000\u00b0C.In Mg3V2O8 structure and monoclinic symmetry was obtained at 300 and 600\u00b0C in compositions with 1.0\u2009\u2264\u2009x\u2009\u2264\u20092.0. This crystalline phase with monoclinic Cu3V2O8 structure is also present when 1.5\u2009\u2264\u2009x\u2009\u2264\u20092.0 at 800\u00b0C. The crystalline phase with the structure of MgCu2V2O8 compound (\u03b2\u2009=\u200990.44 (2) and Z\u2009=\u20094) is detected when 1.0\u2009\u2264\u2009x\u2009\u2264\u20092.0 at 800\u00b0C but the crystalline phase with the ordered metal distributions in Mg2CuV2O8 compound (\u03b2\u2009=\u2009116.22 (3), Z\u2009=\u20092, Cu1 in 2a sites and Mg1 in 4e sites, ICSD-404851) is not detected in conditions of this study. In the prepared Mg2CuV2O8 composition (MgxCu3-xV2O8 with x =2.0), crystalline phase with Cu3V2O8 structure and monoclinic symmetry  in 2b sites and M2  in 4e sites) is the only crystalline phase detected at 800\u00b0C. Figure\u00a02V2O8 (x\u2009=\u20091.0), Mg2CuV2O8 (x\u2009=\u20092.0) and Mg2.5Cu0.5V2O8 (x\u2009=\u20092.5) compositions fired at 800\u00b0C.A crystalline phase with Cu3V2O8 structure is obtained when 2.0\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 600\u00b0C and when 2.5\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 800\u00b0C. At 1000\u00b0C, this phase is the major crystalline phase in the unfused samples (x\u2009\u2265\u20091.0). Figure\u00a0xCu3-xV2O8 compositions with x\u2009=\u20091.0, x\u2009=\u20092.0 and x\u2009=\u20092.5 fired at 1000\u00b0C. The orthorhombic Mg3V2O8 crystalline phase is the major phase in them.Crystalline phase with orthorhombic MgCu divanadates and Mg divanadates are present together with Cu and Mg orthovanadates in some samples.2V2O7 structure (orthorhombic symmetry) is only present in MgyCu2-yV2O7 compositions when y\u2009<\u20090.5 at 600\u00b0C. These compositions melt at 800\u00b0C. Diffraction peak intensity associated with this crystalline phase is weak or very weak at 300\u00b0C.Crystalline phase with \u03b1-Cu2V2O7 structure (monoclinic symmetry) is more extended than the crystalline phase with \u03b1-Cu2V2O7 structure in the prepared compositions. At 300\u00b0C, crystalline phase with \u03b2-Cu2V2O7 structure is present when y\u2009<\u20090.5 with diffraction peaks of medium intensity. This crystalline phase is present when 0.25\u2009\u2264\u2009y\u2009<\u20091.50 at 600\u00b0C and when 0.50\u2009\u2264\u2009y\u2009\u2264\u20090.75 with diffraction peak of strong or medium intensity. Figure\u00a00.25Cu1.75V2O7 composition fired at 600\u00b0C.Presence of crystalline phase with \u03b2-Cu2V2O7 structure (triclinic symmetry) is present in compositions when 0.25\u2009\u2264\u2009y\u2009\u2264\u20090.50 at 300\u00b0C but its intensity of diffraction peak is weak at 600 and 800\u00b0C  is detected in a compositional range more extended than the crystalline phase with triclinic Mg2V2O7 structure from MgyCu2-yV2O7 prepared compositions. Crystalline phase with monoclinic \u03b1-Mg2V2O7 structure is identified when 0.75\u2009\u2264\u2009y\u2009\u2264\u20092.00 at 600\u00b0C, when 0.50\u2009\u2264\u2009y\u2009\u2264\u20092.00 at 800\u00b0C, and when 1.50\u2009\u2264\u2009y\u2009\u2264\u20092.00 at 1000\u00b0C.Crystalline phase with \u03b1-Mg2V2O7 structure is observed when 1.5\u2009\u2264\u2009y\u2009\u2264\u20092.00 in compositions fired at 800\u00b0C and only when y\u2009=\u20092.0 at 300\u00b0C.Crystalline phase with triclinic MgTables\u00a0xCu3-xV2O8 compositions solid solutions with triclinic Cu3V2O8 structure are obtained when 0.0\u2009\u2264\u2009x\u2009\u2264\u20091.0 at 600\u00b0C. At this temperature, the c unit cell parameter increases slightly with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)) from MgxCu3-xV2O8 compositions when 0.0\u2009\u2264\u2009x\u2009\u2264\u20091.0. Ionic radii values do not explain this fact. A slight contraction of unit cell is expected. Structural distortion might explain the c increase with incorporation of Mg (II) ions in a structure (Tena From Mgure Tena .xCu3-xV2O8 (x\u2009\u2265\u20091.0) compositions fired at 800\u00b0C is noticeable in monoclinic Cu3V2O8 structure (detected when 1.5\u2009\u2264\u2009x\u2009\u2264\u20092.0) and it indicates the formation of solid solutions with monoclinic Cu3V2O8 structure in 1.5\u2009\u2264\u2009x\u2009\u2264\u20092 compositional range at 600\u00b0C and 800\u00b0C.Variation of unit cell parameters obtained from Mg3V2O8 structure are also obtained when 2.5\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 600, 800\u00b0C and when 1.0\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 1000\u00b0C. Figure\u00a0xCu3-xV2O8 samples fired at 1000\u00b0C/1\u00a0h. At 1000\u00b0C, the a and b unit cell parameters decrease with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)). Average changes of interatomic distances are very slight. Changes in intensities with composition  are detected in some samples  is slightly different at 600 and 800\u00b0C in the conditions of this study. This slight difference between the two crystalline phases with the same structure is evidenced with differences in unit cell parameters values obtained. In MgyCu2-yV2O7 compositions fired at 600\u00b0C, the values of a and \u03b2 parameters decrease when y increases in \u03b2-Cu2V2O7 structure . At 800\u00b0C this crystalline phase is obtained with a weight fraction\u2009>\u200935% only when 0.5\u2009\u2264\u2009y\u2009\u2264\u20090.75. In crystalline phase with \u03b1-Mg2V2O7 structure, \u03b2 angle value is close to 100\u00b0 at 300\u00b0C and it is close to 90\u00b0 at 800\u00b0C. When two crystalline phases with this structure are detected in the same sample, unit cell parameters are 0.2\u00a0\u00c5  or 8 degrees (\u03b2 parameter) longer and wider in one of them. This fact is in accordance with the formation of solid solutions in this monoclinic \u03b1-Mg2V2O7 structure with the replacement of Mg (II) ion by Cu (II) and with an important distortion structural in these formed solid solutions. Solid solutions with monoclinic \u03b1-Mg2V2O7 structure are obtained when 0.5\u2009\u2264\u2009y\u2009\u2264\u20092.0 at 600 and 800\u00b0C. At 1000\u00b0C, these last solid solutions are obtained when y\u2009\u2265\u20091.5, including all unmelted samples  and Mg (II) ions are also six.Coordination number of V (V) ion in Cu and Mg orthovanadate and divanadate structures is four. Coordination number of Cu (II) ion is four and five and coordination number of Mg (II) ion is six in these structures. Values obtained from samples are in accordance with literature about these structures. In distorted monoclinic structure of CuyCu2-yV2O7 compositions considering all the crystalline phases in each composition and its weight fraction in samples fired at 600, 800 and 1000\u00b0C. These M-O  interatomic distances increase with magnesium amount (y) when 0\u2009\u2264\u2009y\u2009\u2264\u20091.25. This increased average M-O distance is coincident with destabilization of structures of Cu divanadate and a change is observed when y\u2009>\u20091.25. Structures of Cu divanadate are unstable with temperature and structures of Mg divanadates are stable at 1000\u00b0C when 1.5\u2009\u2264\u2009y\u2009\u2264\u20092.0  and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions fired at 600, 800 and 1000\u00b0C. Visible spectra obtained from MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions fired at 800\u00b0C/1\u00a0h and MgxCu2-xP2O7 (0\u2009\u2264\u2009x\u2009\u2264\u20091.5) compositions fired at 800\u00b0C/5d (Tena 9) a transition d-d is allowed. Experimentally electronic spectra of Cu (II) ion are often characterized by a single highly asymmetric band. In this study spectra show a strong absorbance in 700\u20131400\u00a0nm wavelength range with the absorption maximum at 800\u2013900\u00a0nm. It can be associated with Cu (II) d-d transition. Bands due to d-d transitions are not expected from V (V) ion. Strong absorbance in 430\u2013600\u00a0nm wavelength range (in visible wavelength range) with the absorption maximum depending of copper amount in the sample  is detected in MgxCu3-xV2O8 (0\u2009\u2264\u2009x\u2009\u2264\u20093) and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) compositions at 300\u00b0C/12\u00a0h, 600\u00b0C/12\u00a0h, 800\u00b0C/1\u00a0h and 1000\u00b0C/1\u00a0h. The strong absorbance in 350\u2013600\u00a0nm wavelength range is not observed in MgxCu2-xP2O7 compositions  and MgyCu2-yV2O7 (y\u2009=\u20092) compositions. It is associated with charge transfer between Cu-O in orthovanadates and divanadates when 0\u2009\u2264\u2009x\u2009<\u20093 or when 0\u2009\u2264\u2009y\u2009<\u20092. When x\u2009=\u20093 or y\u2009=\u20092, the charge transfer is associated with V-O charge transfer (\u03bb\u2009<\u2009430\u00a0nm in studied temperature range). Maximum of this band is observed at higher wavelength when copper amount is hight than when the copper amount is low. This strong absorbance in visible wavelength range explains the colour of these materials. At 600 and 800\u00b0C, coloration from samples with vanadate structures is red-brown, orange and yellow and is very different to the weak blue coloration obtained from samples with phosphate structures (Tena xCu3-xV2O8 (x\u2009\u2260\u20093) compositions and in MgxCu2-yV2O7 (y\u2009\u2260\u20092) compositions with different crystalline phases detected by XRD  and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009\u2264\u20092) samples fired at 600, 800 and 1000\u00b0C are shown in Table\u00a0CIE L*, a* and b* parameters of Mg3V2O8 structure is detected. The best yellow colour is obtained from Mg2CuV2O8 (x\u2009=\u20092.0) solid solution with monoclinic Cu3V2O8 structure. This is the only crystalline phase detected at 800\u00b0C in conditions of this study. The Mg (II) incorporated into this structure stabilizes this crystalline phase at temperatures higher than 780\u00b0C (melting point of Cu3V2O8). In Mg2CuV2O8 composition fired at 800\u00b0C, average distances of M1-O \u2009=\u20091.9587\u00a0\u00c5 and M2-O \u2009=\u20092.1129\u00a0\u00c5 are obtained. Yellow colorations are not obtained from Cu, Mg divanadates.Interesting yellow colorations are obtained when x\u2009=\u20091.5 and 2.0 at 600\u00b0C/12 and when x\u2009=\u20092.0 at 800\u00b0C/1\u00a0h. In these samples that development yellow colorations, crystalline phase with monoclinic Cu0.5Cu1.5V2O7 (y\u2009=\u20090.5) fired at 600\u00b0C /12\u00a0h is the most noticeable colour but it is unstable at 800\u00b0C /1\u00a0h. Dark brown colour is obtained from this composition at 800\u00b0C. The major crystalline phase detected by XRD is the crystalline phase with \u03b2-Cu2V2O7 structure in this sample fired at 600\u00b0C.The colour red-brown obtained from Mg2V2O7 and Cu3V2O8 or \u03b2-Cu2V2O7 and \u03b1-Mg2V2O7 structures is detected by XRD.Orange colour is obtained when y\u2009=\u20090.75, 1.00 and 1.25 at 600\u00b0C/12\u00a0h and when y\u2009=\u20091.25 and 1.50 at 800\u00b0C/1\u00a0h. In these orange materials, a mixture of monoclinic crystalline phases with \u03b2-CuyCu2-yV2O7 compositions fired at 600\u00b0C/12\u00a0h  are obtained. These solid solutions with monoclinic Cu3V2O8 structure are obtained when 1.5\u2009\u2264\u2009x\u2009\u2264\u20092.0 at 600\u00b0C and 800\u00b0C. Solid solutions with orthorhombic Mg3V2O8 structure are obtained when 2.5\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 600, 800\u00b0C and when 1.0\u2009\u2264\u2009x\u2009\u2264\u20093.0 at 1000\u00b0C. In this study, the most stable solid solutions are obtained with Mg orthovanadate structure (orthorhombic).From MgyCu2-yV2O7 compositions, the formation of two kind of solid solutions with \u03b2-Cu2V2O7 and \u03b1-Mg2V2O7 structures is detected. Solid solutions with monoclinic \u03b2-Cu2V2O7 structure are obtained when 0.25\u2009\u2264\u2009y\u2009\u2264\u20091.50 at 600\u00b0C and when 0.50\u2009\u2264\u2009y\u2009\u2264\u20090.75 at 800\u00b0C. Solid solutions with monoclinic \u03b1-Mg2V2O7 structure are obtained when 0.5\u2009\u2264\u2009y\u2009\u2264\u20092.0 at 600 and 800\u00b0C and showing an important structural distortion. At 1000\u00b0C, solid solutions with \u03b1-Mg2V2O7 structure are obtained in 1.5\u2009\u2264\u2009y\u2009\u2264\u20092.0 compositional range. It is proposed the existence of a new polymorph of Mg2V2O7 compound with \u03b1-Mn2V2O7 structure detected when y\u2009\u2265\u20091.25 at 300\u00b0C.From MgxCu3-xV2O8 (0\u2009\u2264\u2009x\u2009<\u20093) and MgyCu2-yV2O7 (0\u2009\u2264\u2009y\u2009<\u20092) compositions which is associated with charge transfer between Cu-O in orthovanadates and divanadates. Wavelength of the abrupt change in absorbance is in accordance with Cu-O interatomic distances in these structures. In this study, the best yellow colour is obtained from Mg2CuV2O8 (x\u2009=\u20092.0) solid solution with monoclinic Cu3V2O8 structure. The colour red-brown is obtained from Mg0.5Cu1.5V2O7 (y\u2009=\u20090.5) fired at 600\u00b0C /12\u00a0h and it is unstable at 800\u00b0C /1\u00a0h. This red-brown colour is obtained when the average M-O distances are the shortest from divanadates. Orange colour is also obtained from some divanadates when average M-O distance is long.Strong absorbance in visible spectra is detected in MgStructural changes must be also considered to explain the colour of these materials. Thus, yellow colorations are obtained from orthovanadates and red-brown and orange colorations are obtained from divanadates."}
{"text": "The cationic diruthenium tetra\u00adacetate core lies on a crystallographic inversion center with Ru\u2014Ru and Ru\u2014N bond lengths of 2.2738\u2005(3) and 2.2920\u2005(17)\u2005\u00c5, respectively. The Ru\u2014Ru\u2014N bond angle is close to linear at 176.48\u2005(4)\u00b0, and a significant \u03c0-stacking inter\u00adaction of 3.5649\u2005(16)\u2005\u00c5 is seen between overlapping pyridine rings of adjacent cations.The title compound, [Ru Then, 3-chloro\u00adpyridine  was added and the solution allowed to stir for 5\u2005min at room temperature. The volume of the solution was then reduced to 5\u2005ml under vacuum and allowed to cool to 278\u2005K overnight. The crystalline product was collected via suction filtration. Yield = 0.098\u2005g (63%). Crystals suitable for X-ray diffraction were obtained by slow diffusion of diethyl ether into a 1,2-di\u00adchloro\u00adethane solution of the complex. IR (cm\u22121): 2947 (\u03bdC\u2014H), 1447 (asym. \u03bdCOO), 1396 (sym. \u03bdCOO), 841, (\u03bdPF6), 766 (\u03bdC\u2014Cl), 692 (\u03b4C\u2014CH3). UV\u2013vis ): 427 (2.95), 263 (4.05), 210 (4.33).Synthesis of the title compound followed an earlier method developed in our lab (Vamvounis F2(obs) and F2, PLATON  I. DOI: 10.1107/S2414314622002498/wm4161Isup2.hklStructure factors: contains datablock(s) I. DOI: 2156199CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Calophyllum gracilentum, is reported. The mol\u00adecule is characterized by a xanthone skeleton of three fused six-membered rings plus an additional fused pyrano ring and one 3-methyl\u00adbut-2-enyl side chain.The crystal structure of brasixanthone B, a naturally occurring xanthone isolated from the stem bark of  23H22O5, isolated from Calophyllum gracilentum, is characterized by a xanthone skeleton of three fused six-membered rings plus an additional fused pyrano ring and one 3-methyl\u00adbut-2-enyl side chain. The core xanthone moiety is almost planar, with a maximum deviation 0.057\u2005(4)\u2005\u00c5 from the mean plane. In the mol\u00adecule, an intra\u00admolecular O\u2014H\u22efO hydrogen bond forms an S(6) ring motif. The crystal structure features inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions.The title compound , C Calophyllum, frequently referred as \u2018bintangor\u2019 or \u2018penaga\u2019 in Malay is a part of the Calophyllaceae family  and 94.2\u2005(4)\u00b0, respectively, suggesting a synclinal conformation \u2005\u00c5, \u03b8 = 65.4\u2005(7)\u00b0 and \u03c6 = 38.2\u2005(7)\u00b0. The core xanthone moiety  is almost planar, with maximum deviation of 0.057\u2005(4)\u2005\u00c5 from the mean plane for C16. The dihedral angles between xanthone rings are: 2.29\u2005(19)\u00b0 for B and C, 2.94\u2005(19)\u00b0 for B and D, and 0.75\u2005(19)\u00b0 between C and D. There are two methyl groups attached to atom C1 in ring A with C\u2014C distances of 1.488\u2005(6) and 1.483\u2005(6)\u2005\u00c5.The orientation of the 3-methyl\u00adbut-2-enyl side chain attached to ring O3\u22efO4, forms an S(6) ring motif. In the crystal, the mol\u00adecules are linked by inter\u00admolecular hydrogen bonds O5\u2014H1O5\u22efO4, C11\u2014H11A\u22efO3 and C12\u2014H12A\u22efO5  mol\u00adecules are stacked by \u03c0\u2013\u03c0 inter\u00adactions with an inter\u00adplanar spacing of 3.319\u2005(4)\u2005\u00c5 between corresponding xanthone rings.In the title compound Fig.\u00a01, an intr5 Table\u00a01, forming5 Table\u00a01. Inversicalophyllum gracilentum was ground and extracted with n-hexane, chloro\u00adform, ethyl acetate and methanol. Fractionation of the hexane extract by gravity column chromatography over (Merck Kieselgel No. 1.09385.1000) silica gel with elution of n-hexa\u00adne: ethyl acetate and ethyl acetate: methanol in a step-wise gradual increment in polarity. This produced 28 fractions, which were combined and pooled together as 10 sub-fractions based on the TLC profile. Fraction 5 was subjected to further isolation by column chromatography over Sephadex LH20 eluted with methanol and several more purification steps using radial chromatography over silica (Merck Kieselgel No. 1.07749.1000), eluting with an n-hexa\u00adne:ethyl acetate (8:2) mixture. Yellow needle-like crystals were obtained. The melting point was found to be 500\u2013502\u2005K  of Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622011981/pk4037sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011981/pk4037Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011981/pk4037Isup3.cmlSupporting information file. DOI: 2227328CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-1,2,3-triazol-1-yl)eth\u00adyl]phospho\u00adnate ester, which was then hydrolyzed under acidic conditions (HCl) to give the \u2018free\u2019 phospho\u00adnic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl\u2212 anion.This new triazole-functionalized phospho\u00adnic acid, PTEPHCl, was synthesized by the \u2018click\u2019 reaction of the alkyl azide diethyl-(2-azido\u00adeth\u00adyl)phospho\u00adnate with phenyl\u00adacetyl\u00adene to give the dieth\u00adylphospho\u00adnate ester, which was then hydrolyzed under acidic conditions (HCl) to give the \u2018free\u2019 phospho\u00adnic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl\u2212 anion. There are extensive hydrogen-bonding inter\u00adactions in the structure of PTEPHCl, involving the phospho\u00adnic acid (\u2013PO3H2) group, the triazolium ring and the Cl\u2212 anion.The new triazole-functionalized phospho\u00adnic acid 5-phenyl-3-(2-phosphono\u00adeth\u00adyl)-1,2,3-triazol-1-ium chloride, C This ester was then hydrolyzed in acidic conditions to give 5-phenyl-3-(2-phosphono\u00adeth\u00adyl)-1,2,3-triazol-1-ium chloride (PTEPHCl). In the present work, we report the crystal structure of the above-mentioned triazole-functional\u00adized phospho\u00adnic acid PTEPHCl.The reaction of an organic azide with an alkyne to give a triazole is a well-known process  and P1\u2014O2 = 1.5513\u2005(16)\u2005\u00c5] and one \u2018short\u2019 P\u2014O bond [P1\u2014O3 = 1.4805\u2005(14)\u2005\u00c5]. The \u2018long\u2019 P\u2014O bonds correspond to the P\u2014O\u2014H moieties and the \u2018short\u2019 P\u2014O bond corresponds to the phosphoryl P=O moiety. All P\u2014O bond lengths have the expected values \u2005\u00c5 and O2\u22efCl1 = 2.9422\u2005(17)\u2005\u00c5. The phosphoryl P=O group forms a hydrogen bond with the N\u2014H portion of the triazolium ring [O3\u22efN3 2.610\u2005(2)\u2005\u00c5]. Finally, the benzene ring inter\u00adacts with a phospho\u00adnate oxygen through a weak C\u2014H\u22efO contact at 3.476\u2005(3)\u2005\u00c5 (C6\u22efO2).The phospho\u00adnic acid moiety forms four hydrogen-bonding inter\u00adactions Fig.\u00a02. Specifi\u03c0\u2013\u03c0 stacking inter\u00adactionsThere is only one type of very weak \u03c0\u2013\u03c0 stacking inter\u00adaction in the structure of 5-phenyl-3-(2-phosphono\u00adeth\u00adyl)-1,2,3-triazol-1-ium chloride. The centroid-to-centroid distance is 4.0423\u2005(15)\u2005\u00c5, with the rings being \u2018shifted\u2019 from one another (slippage distance between the rings: 2.222\u2005\u00c5) and parallel.Crystal packingb axis. The chloride anions form corrugated sheets [\u2018short\u2019 Cl\u22efCl distances at 4.9455\u2005(12)\u2005\u00c5 and \u2018long\u2019 Cl\u22efCl distances at 6.4564\u2005(9)\u2005\u00c5] that are parallel to the bc plane.Fig.\u00a03Reagents and materialsl-ascorbic acid were from Serva. Sodium sulfate was from Merck. Di\u00adchloro\u00admethane, tetra\u00adhydro\u00adfuran (THF), hydro\u00adchloric acid (37%) and nitric acid (70%) were from Scharlau. Ion-exchange-column deionized water was used.All starting materials were obtained from commercial sources and used without further purification. The reagents diethyl 2-bromo\u00adethyl\u00adphospho\u00adnate (97%), phenyl\u00adacetyl\u00adene (98+%), copper sulfate penta\u00adhydrate (99%), zinc nitrate hexa\u00adhydrate (98%) and ethyl\u00adenedi\u00adamine\u00adtetra\u00adacetic acid (98%) were from Alfa Aesar. Sodium azide and Synthesis of 5-phenyl-3-(2-phosphono\u00adeth\u00adyl)-1,2,3-triazol-1-ium chloride (PTEPHCl)et al., 2018l-ascorbic acid  to produce dieth\u00adyl[2-eth\u00adyl]phospho\u00adnate ester. The reaction mixture was heated at 313\u2005K under vigorous stirring for 48\u2005h. After filtration, the filtrate was mixed with di\u00adchloro\u00admethane (50\u2005mL) and an aqueous solution of the Cu2+ chelant ethyl\u00adenedi\u00adamine\u00adtetra\u00adacetic acid  and the mixture was stirred for \u223c1\u2005h. After extraction with di\u00adchloro\u00admethane (4 \u00d7 50\u2005mL) and evaporation, dieth\u00adyl[2-eth\u00adyl]phospho\u00adnate ester was obtained in solid form. Finally, the latter (0.5\u2005g) was hydrolyzed with 25\u2005mL of H2O and 30\u2005mL of HCl at 373\u2005K for 48\u2005h, giving 5-phenyl-3-(2-phosphono\u00adeth\u00adyl)-1,2,3-triazol-1-ium chloride in crystalline form . The crystal used for the data collection was handled under inert conditions. It was manipulated while immersed in a perfluoro\u00adpolyether protecting oil and mounted on a MiTeGen Micromount\u2122.Three distinct steps were followed for the syntheses of the ligand PTEP. The first step was the synthesis of diethyl-(2-azido\u00adeth\u00adyl)phospho\u00adnate, following a properly adapted published procedure  \u03b4 8.51 , 7.93 , 7.67 , 4.82 , 2.52 . 13C NMR  \u03b4 146.71, 131.27, 129.38, 128.28, 125.53, 121.87, 45.42, 30.45 . 31P NMR  \u03b4 20.17.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622001894/tx4001sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622001894/tx4001Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001894/tx4001Isup5.molSupporting information file. DOI: Click here for additional data file.10.1107/S2414314622001894/tx4001Isup4.cmlSupporting information file. DOI: 2145106CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title salt, all O\u2014H and N\u2014H groups in the cations (metforminium and ammonium) and lattice water mol\u00adecules are donor groups for hydrogen bonds, giving a highly compact crystal structure. 4)4(C4H12N5)2[V10O28]\u00b76H2O, crystallizes with the deca\u00advanadate anion placed on an inversion centre in space group PThe title compound, (NH The HMetf+ monocation has its charge located mainly on N2. Furthermore, this cation is characterized by a dihedral angle of 54.85\u2005(5)\u00b0 between planes C2\u2013C4/N3\u2013N5 and C1/N1\u2013N3. This twisted geometry is observed in several other compounds of metforminium(1+). Indeed, metformin and its cations HMetf+ and H2Metf2+ are highly flexible entities: the twist angle for 93 structures recovered from the CSD  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01], as well as between the anion and a water mol\u00adecule \u00b78H2O and [H2Metf]2[NH4]2(V10O28)\u00b710H2O \u00b76H2O (ca. 5% yield). These yields are poorly reproducible, and no powder diffraction was performed on the solid phases obtained by fractional crystallization to check their purity. Therefore, we cannot rule out the presence of other crystallized compounds in this reaction.Good-quality single crystals of the title compound were obtained during the reaction between ammonium metavanadate  I. DOI: 10.1107/S2414314621006349/im4012Isup2.hklStructure factors: contains datablock(s) I. DOI: 2090930CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the dihedral angle between the mean planes of the cyclo\u00adhexane and 1,3-dithietane rings is 9.1\u2005(3)\u00b0. A short S\u22efO contact is observed in the crystal. 8H8O2S2, contains a cyclo\u00adhexane-1,3-dione ring, which has a twist-boat conformation. The C2S2 ring is close to planar (r.m.s. deviation = 0.023\u2005\u00c5) and the dihedral angle between the mean planes of the cyclo\u00adhexane and 1,3-dithietane rings is 9.1\u2005(3)\u00b0. Short intra\u00admolecular S\u22efO contacts occur [2.719\u2005(5) and 2.740\u2005(5)\u2005\u00c5]. In the crystal, the mol\u00adecules are linked by weak C\u2014H\u22efS hydrogen bonds and short [3.165\u2005(5)\u2005\u00c5] S\u22efO contacts, forming (010) layers. The prevalence of these inter\u00adactions is illustrated by an analysis of the three-dimensional Hirshfeld surface and by two-dimensional fingerprint plots.The title compound, C Ketene di\u00adthio\u00adacetals are useful inter\u00admediates in organic synthesis and have been used for the preparation of heterocyclic compounds \u2005\u00c5 whereas the C8\u2014S1 and C8\u2014S2 bond lengths differ slightly . The mol\u00adecule has local sC symmetry with a non-crystallographic mirror plane passing through atoms C8, C1, C2 and C5. The dihedral angle between the cyclo\u00adhexane  and dithietane rings is 9.1\u2005(3)\u00b0 and short intra\u00admolecular S1\u22efO2 [2.719\u2005(5)\u2005\u00c5] and S2\u22efO1 [2.740\u2005(5)\u2005\u00c5] contacts are observed ed Fig.\u00a01.3.b-axis direction. The mol\u00adecules are linked by C5\u2014H5A\u22efS2 hydrogen bonds (Table\u00a01ii  contacts, forming (010) layers a. A contribution of 30.7% was found for the H\u22efO/O\u22efH inter\u00adactions, representing the largest contribution; these contacts are represented by the spikes in the top left  and bottom right  of Fig.\u00a04b. Inter\u00adactions of the type H\u22efH appear in the middle of the scattered points in the fingerprint plots with a pair of spikes at de + di = 2.5\u2005\u00c5 and comprise 25.9% of the entire surface ; the van der Waals radius for this inter\u00adaction is 2.4\u2005\u00c5, which means it is a weak inter\u00adaction. The S\u22efH/H\u22efS contacts , which account for 23.8% of the Hirshfeld surface, are displayed on the fingerprint plot as a pair of long spikes at de + di = 2.7\u00c5. This distance differs by 0.3\u2005\u00c5 from the sum of the van der Waals radii, which means it is the strongest inter\u00adaction present. The S\u22efC/C\u22efS  and S\u22efO/O \u22efS  contacts are seen as pairs of spikes at de + di = 3.2 and 3.05\u2005\u00c5, respectively. These distances are shorter than the sums of the van der Waals radii of 3.5 and 3.32\u2005\u00c5, respectively. The C\u22efO/O\u22efC inter\u00adactions make a contribution of 0.7% to the Hirshfeld surface , their inter\u00adatomic distances (de + di = 3.3\u2005\u00c5) being larger than the sum of the van der Waals radius (3.22\u2005\u00c5), so this inter\u00adaction is very weak in this structure. The fingerprint plot corresponding to C\u22efH/H\u22efC contacts  shows a fin-like distribution of points with the edges at de + di = 2.8\u2005\u00c5.The nature of the inter\u00admolecular inter\u00adactions in (I)ot Fig.\u00a03 shows rece Fig.\u00a04c; the vts Fig.\u00a04d, whichce Fig.\u00a04h, theirts Fig.\u00a04e shows 5.et al., 2016et al., 2002trans-2,4-bis\u00ad(isoprop\u00adyl)-2,4-bis\u00ad[(2-methyl-1-thioxo)propyl\u00adsulfan\u00adyl]-1,3-dithietane cyclo\u00adhexane-1,3-dione -5,5-dimethyl-2- [3-(4- nitro\u00adphen\u00adyl)allyl\u00adidene]cyclo\u00adhexane-1,3-dione -2-[(E)-amino]\u00adcyclo\u00adhex\u00adyl}isoindoline-1,3-di\u00adone  \u03bbmax, 335\u2005nm (\u025b 18760); IR : 1640 (C=O), 1H NMR (CDCl3) \u03b4 (ppm): 4.35 , 2.52 , 1.97 ; 13C NMR (CDCl3) \u03b4 (ppm): 197.28 (CO),189.73 (C=C\u2014S), 119.93 (C=C\u2014S), 37.31 (CH2\u2014CH2\u2014CH2), 33.39 (CH2\u2014S), 18.62 (CH2\u2014CH2\u2014CH2).Potassium carbonate  in DMF (50\u2005ml) was well stirred at room temperature. To this mixture, cyclo\u00adhexane-1,3-dione (0.1\u2005mol) was added and the resultant solution stirred at room temperature for 20\u2005min. Carbon di\u00adsulfide  was then added in one lot. The reaction mixture was stirred and kept for 10\u2005min at room temperature. Di\u00adiodo\u00admethane (0.12\u2005mol) was added dropwise over 20\u2005min and the reaction mixture stirred for 7\u2005h at room temperature. Ice\u2013water (500\u2005ml) was added to the reaction mass, the solid was filtered and washed with water, dried and recrystallized from ethanol solution to give (I)7.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details for the title compound are summarized in Table\u00a0310.1107/S2056989022009872/hb8028sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022009872/hb8028Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022009872/hb8028Isup3.cmlSupporting information file. DOI: 2211891CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One hydro\u00adnium ion is complexed with an ordered 18-crown-6 mol\u00adecule with H2OH\u22efOC distances of 1.90\u20132.19\u2005\u00c5, and another hydro\u00adnium ion with a disordered 18-crown-6 mol\u00adecule with distances of 1.85\u20132.36\u2005\u00c5.The structure of the title compound, [H 3O+\u00b7C2F6NO4S2\u2212\u00b7C12H24O6 or [H3O+\u00b7C12H24O6][N(SO2CF3)2\u2212], which is an ionic liquid with a melting point of 341\u2013343\u2005K, has been determined at 113\u2005K. The asymmetric unit consists of two crystallographically independent 18-crown-6 mol\u00adecules, two hydro\u00adnium ions and two bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amide anions; each 18-crown-6 mol\u00adecule complexes with a hydro\u00adnium ion. In one 18-crown-6 mol\u00adecule, a part of the ring exhibits conformational disorder over two sets of sites with an occupancy ratio of 0.533\u2005(13):0.467\u2005(13). One hydro\u00adnium ion is complexed with the ordered 18-crown-6 mol\u00adecule via O\u2014H\u22efO hydrogen bonds with H2OH\u22efOC distances of 1.90\u2005(6)\u20132.19\u2005(7)\u2005\u00c5, and the other hydro\u00adnium ion with the disordered crown mol\u00adecule with distances of 1.85\u2005(6)\u20132.36\u2005(6)\u2005\u00c5. The hydro\u00adnium ions are also linked to the anions via O\u2014H\u22efF hydrogen bonds. The crystal studied was found to be a racemic twin with a component ratio of 0.55\u2005(13):0.45\u2005(13).The structure of the title compound, H The asymmetric unit contains two crystallographically independent ion-pairs \u20132.19\u2005(7)\u2005\u00c5, and the other hydro\u00adnium ion with the disordered 18-crown-6 mol\u00adecule with 1.85\u2005(6)\u20132.36\u2005(6)\u2005\u00c5 distances (Table\u00a01via O\u2014H\u22efF hydrogen bonds with H2OH\u22efF3C distances of 2.12\u2005(4)\u20132.14\u2005(6)\u2005\u00c5, while the hydro\u00adnium ion with the disordered crown exhibits a weak O\u2014H\u22efF inter\u00adaction [H\u22efF = 2.50\u2005(4)\u2005\u00c5].Hydro\u00adnium\u00b718-crown-6 bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amide is an ionized form of ternary equimolar mixture of 18-crown-6, imide superacid and water, the molten salt of which is known as a hydro\u00adnium solvate ionic liquid (m.p. 341 \u2212343\u2005K) with very strong Br\u00f8nsted acidity  were used to correct the geometry of the disordered crown ether mol\u00adecule and hydro\u00adnium ion, and the displacement parameters of the disordered crown ether mol\u00adecule.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620001625/is4042sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620001625/is4042Isup2.hklStructure factors: contains datablock(s) I. DOI: 1982024CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R(8)22 geometry.Pairs of mol\u00adecules related by inversion symmetry are linked by inter\u00admolecular C\u2014H\u22efF contacts with  25H18ClF2N5S, comprises almost co-planar fluoro\u00adphenyl, methyl\u00adthia\u00adzolyl, pyrazolyl and chloro\u00adphenyl rings with the second fluoro\u00adphenyl ring almost perpendicular to this plane. One fluoro\u00adphenyl group is disordered over two components of occupancy ratio 0.767\u2005(10):0.233\u2005(10) related by a 24.2\u2005(8)\u00b0 twist. In the crystal, two mol\u00adecules related by inversion symmetry are linked by a pair of C\u2014H\u22efF contacts in an R(8)22 geometry.The mol\u00adecule of the title compound, C Fluoro\u00adphenyl group E is disordered over two components with an occupancy ratio of 0.767\u2005(10):0.233\u2005(10) and related by a twist of 24.2\u2005(8)\u00b0.The mol\u00adecule of the title compound Fig.\u00a01 includesA\u2013D are close to coplanar with twist angles A/B, B/C and C/D of 4.76\u2005(10)\u00b0, 6.51\u2005(11)\u00b0 and 10.46\u2005(11)\u00b0 respectively. Ring E is almost perpendicular to A\u2013D with a C/E twist angle of 72.66\u2005(3)\u00b0 for the major component of E.Rings R(8)22 geometry to form a dimer. The pyrazolyl and fluoro\u00adphenyl rings of neighbouring mol\u00adecules are almost parallel with a centroid-to-centroid distance of 3.6510\u2005(13)\u2005\u00c5.In the crystal structure, two mol\u00adecules related by inversion symmetry are linked by a pair of C\u2014H\u22efF contacts Table\u00a01 with R, N\u2032-(4-fluoro\u00adphen\u00adyl)-2-oxo\u00adpropane\u00adhydrazonoyl bromide , and tri\u00adethyl\u00adamine  in anhydrous ethanol (20\u2005ml) was stirred for 2\u2005h under reflux. The solid obtained on cooling was collected by filtration, washed with ethanol, dried and recrystallized from di\u00admethyl\u00adformamide solution to give colourless crystals of the title compound in 86% yield , m.p. 243\u00b0C, IR : 1590 (N=N), 1625 (C=C), 1650 (C=N).A mixture of 3-(4-chloro\u00adphen\u00adyl)-5-(4-fluoro\u00adphen\u00adyl)-4,5-di\u00adhydro-1SHELXL, e.s.d. = 0.01 and 0.02\u2005\u00c5) and Uij components of disordered atoms\u2019 ADPs were restrained to be similar to each other if within 2.0\u2005\u00c5 distance . Refinement gave an occupancy ratio of 0.767\u2005(10):0.233\u2005(10) for the two components related by a twist of 24.2\u2005(8)\u00b0.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620007002/zl4041sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620007002/zl4041Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620007002/zl4041Isup3.cmlSupporting information file. DOI: 2005280CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compounds show different packing motifs including chains mediated by N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds. viz. N\u2032-[(E)-pyridin-3-yl\u00admethyl\u00adidene]thio\u00adphene-2-carbohydrazide, C11H9N3OS, (I), N\u2032-[(E)-pyridin-2-yl\u00admethyl\u00adidene]thio\u00adphene-2-carbohydrazide, C11H9N3OS, (II), N-methyl-N\u2032-[(E)-pyridin-2-yl\u00admethyl\u00adidene]thio\u00adphene-2-carbohydrazide, C12H11N3OS, (III) and N\u2032-[(E)-pyridin-2-yl\u00admethyl\u00adidene]-2-(thio\u00adphen-2-yl)ethano\u00adhydrazide, C12H11N3OS, (IV) are described. The dihedral angles between the thio\u00adphene ring and the pyridine ring are 21.4\u2005(2), 15.42\u2005(14), 4.97\u2005(8) and 83.52\u2005(13)\u00b0 for (I)\u2013(IV), respectively. The thio\u00adphene ring in (IV) is disordered over two orientations in a 0.851\u2005(2):0.149\u2005(2) ratio. Key features of the packing include N\u2014H\u22efNp (p = pyridine) hydrogen bonds in (I), which generate C(7) chains propagating in the [001] direction; N\u2014H\u22efNp links also feature in (II), but in this case they lead to C(6) [001] chains; in (IV), classical amide (C4) N\u2014H\u22efO links result in [010] chains; in every case adjacent mol\u00adecules in the chains are related by 21 screw axes. There are no classical hydrogen bonds in the extended structure of (III). Various weak C\u2014H\u22efX  inter\u00adactions occur in each structure, but no aromatic \u03c0\u2013\u03c0 stacking is evident. The Hirshfeld surfaces and fingerprint plots for (I)\u2013(IV) are compared.The crystal structures of four thio\u00adphene\u2013carbohydrazide\u2013pyridine derivatives,  The oxygen atom of the carbonyl group and the sulfur atom of the thio\u00adphene ring lie on the same side of the mol\u00adecule [S1\u2014C4\u2014C5\u2014O1 = \u22124.9\u2005(6)\u00b0] whereas atom N3 of the pyridine ring lies on the opposite side. The dihedral angle between the thio\u00adphene and pyridine rings is 21.4\u2005(2)\u00b0 and the largest twist in the mol\u00adecule occurs about the C6\u2014C7 bond [N2\u2014C6\u2014C7\u2014C8 = \u221211.8\u2005(7)\u00b0]. The N1\u2014N2 bond length of 1.384\u2005(5)\u2005\u00c5 in (I)et al., 2016cIn (I)E configuration and C5\u2014N1\u2014N2\u2014C6 = 173.74\u2005(19)\u00b0 but unlike (I)In (II)N-methyl\u00adated derivative of (II)E configuration and C5\u2014N1\u2014N2\u2014C7 = 179.40\u2005(12)\u00b0. As with (II)et al., 2020Compound (III)et al., 2016cE and C6 and C7 are close to anti about the N\u2014N bond [C6\u2014N1\u2014N2\u2014C7 = \u2212177.90\u2005(14)\u00b0]. The dihedral angle between the aromatic rings (major disorder conformation for the thio\u00adphene moiety) in (IV)In (IV)3.p (p = pyridine) hydrogen bonds: in the former, these links generate [001] C(7) chains 1 screw axis but here the graph-set motif is C(6). The packing for (IV)C(4) amide N\u2014H\u22efO hydrogen bonds p link arising from the N-methyl group. The structures of (I)X  inter\u00adactions although these are presumably very weak, given their H\u22efX lengths.Geometrical data for the directional inter\u00admolecular inter\u00adactions in (I)\u2013(IV) are listed in Tables 1ns Fig.\u00a05, with adds Fig.\u00a07 leading t\u22ef\u03c0p  = 4.046\u2005(2)\u2005\u00c5 (slippage = 1.546\u2005\u00c5) for (I)t\u22ef\u03c0p = 4.0509\u2005(12)\u2005\u00c5 (slippage = 1.929\u2005\u00c5) for (II)t\u22ef\u03c0p = 4.7831\u2005(9)\u2005\u00c5 for (III)t\u22ef\u03c0p = 4.643\u2005(2)\u2005\u00c5 for (IV)The shortest aromatic ring centroid\u2013centroid separations in these structures are \u03c0CrystalExplorer  show the expected red spots (close contacts) in the vicinities of the various donor and acceptor atoms.In order to gain more insight into these different packing motifs, the Hirshfeld surfaces and fingerprint plots for (I)\u2013(IV) were calculated using  al. 2019. The HirThe fingerprint plots for (I)\u2013(IV) decomposed into the different percentage contact types Table\u00a05 show tha4.et al., 20162\u2014C(=O)\u2014NH\u2014N=CH\u2014Q sequence. None of these structures features a pyridine ring in the \u2018Q\u2019 position.A survey of the Cambridge Structural Database l. 2016a and Card al. 2014, respect6.SHELXL were used for the Uij values of equivalent atom pairs  and a SAME card was used to restrain the nearest-neighbour and next-nearest-neighbour bond distances in the two disorder components to be equal with standard deviations of 0.02 and 0.04\u2005\u00c5, respectively. The N-bound H atoms in (I)Uiso(H) = 1.2Ueq(N). All C-bound H atoms were located geometrically (C\u2014H = 0.95\u20130.99\u2005\u00c5) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl group in (III)Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989022005151/zl5030sup1.cifCrystal structure: contains datablock(s) I, II, III, IV, global. DOI: 10.1107/S2056989022005151/zl5030Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022005151/zl5030IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989022005151/zl5030IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989022005151/zl5030IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030Isup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IIsup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IIIsup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IVsup9.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030sup10.docxHirshfeld surfaces. DOI: 2172437, 2172436, 2172435, 2172434CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is an di\u00adiodo Schiff base mol\u00adecule under investigation for possible anti\u00admicrobial activity as well as for a ligand for medicinal activity. 20H14I2N2O2, a di\u00adiodo-Schiff base, crystallizes in space group Pbca with one mol\u00adecule per asymmetric unit. The mol\u00adecular structure reveals two intra\u00admolecular O\u2014H\u22efN hydrogen bonds that give the mol\u00adecule a twisted structure with non-coplanar rings. In the crystal structure, the mol\u00adecular packing is stabilized by \u03c0\u2013\u03c0 stacking, hydrogen- and halogen-bonding  inter\u00adactions.The title compound, C E,1\u2032E)-bis\u00ad(methanylyl\u00adidene)}bis\u00ad(4-iodo\u00adphen\u00adol) (I)  covalently bound through the imine C atoms, C7 and C14 respectively, to I1\u2014Ar(O1\u2014H1) and I2\u2014Ar(O2\u2014H2) rings , and 39.37\u2005(5)\u00b0 versus I2\u2014Ar(O2\u2014H2)] \u00adphen\u00adyl]salicylaldimine  to I2\u2014Ar(O2\u2014H2) ring inter\u00adactions  to T  repeating pattern with the I1 and I2 atoms of the I1\u2014Ar(O1\u2014H1) and I2\u2014Ar(O2\u2014H2) rings inter\u00addigitated along the c-axis direction  consists of a central ring (C8\u2013C13) with gs Fig.\u00a01. Two intgs Fig.\u00a01, O1\u2014H1\u22efN)] Fig.\u00a01. The intns Fig.\u00a02. This rens Fig.\u00a02. The addns Fig.\u00a02. Along ton Fig.\u00a03.o-phenyl\u00adenedi\u00adamine , and the reaction mixture brought to reflux with vigorous stirring for 2\u2005h. Upon cooling, the title compound (I) precipitated as an orange solid, and was filtered, washed with ethanol and dried under vacuum. Crystals of (I) suitable for single-crystal X-ray diffraction were grown from acetone layered with hexane. Yield: 4.37\u2005g (83%), m.p. 212\u2013214\u00b0C. 1H NMR  \u03b4 8.54 , 7.73\u20137.54 , 7.37 , 7.22 , 6.84 . +: 568.9; observed: 568.8.To a solution of 2-hy\u00addroxy-5-iodo\u00adbenzaldehyde  in ethanol (200\u2005ml) was added an ethanol (10\u2005ml) solution of Crystal data, data collection and structure refinement details of (I) are summarized in Table\u00a0210.1107/S2414314622008951/gg4010sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622008951/gg4010Isup2.hklStructure factors: contains datablock(s) I. DOI: 2205660CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "It crystallizes in the monoclinic space group P21/n.A dual emissive fluorescent substituted benzocarbazole moieties and carbon\u00adyl\u2013carbonyl inter\u00adactions between the two acetyl groups.The crystal of the title compound, C We obtained N-acetyl carbazole 2 in qu\u00adanti\u00adtative yield utilizing Buchwalds\u2019 method by treatment of di\u00adphenyl\u00adphenanthrene 1 as a substrate in the presence of Pd(OAc)2 (10\u2005mol %), NaOAc (1.0 equiv.), Cu(OAc)2 (2.0 equiv.) and powdered mol\u00adecular sieves in toluene under oxygen at 393\u2005K for 24\u2005h. Single crystals of 2 were grown from the a mixture of hexa\u00adnes and DCM (v/v = 1:1) at room temperature by slow thermal evaporation.In order to obtain the benzocarbazole, which are 22.2\u2005(1), 25.7\u2005(2)\u00b0 and 50.8\u2005(2), 59.7\u2005(2)\u00b0, respectively.In the structure of 3.2  to 4.553\u2005(1)\u2005\u00c5 , acet\u00adyl\u2013acetyl dipolar inter\u00adactions of 3.459\u2005(3) to 3.689\u2005(3)\u2005\u00c5 , C\u2014H\u22ef\u03c0 inter\u00adactions of 2.935\u2005(2) to 3.314\u2005(3)\u2005\u00c5 , and \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of 3.801\u2005(2) to 5.672\u2005(2)\u2005\u00c5  between phenyl alkynyl moieties. Specifically, the crystal is stabilized by the phenyl groups of the alkynyl moiety, which inter\u00adacts weakly with each other  through \u03c0\u2013\u03c0 stacking. Furthermore, the phenyl group also inter\u00adacts with another neighboring phenyl moiety and with the phenyl alkynyl moiety through C\u2014H\u22ef\u03c0 inter\u00adactions benzo[def]carbazoledi\u00adchloro\u00admethane solvate , Pd(OAc)2 , Cu(OAc)2 , NaOAc  and powdered mol\u00adecular sieves  were added under air and covered with a septum. The tube was evacuated and refilled with N2. Under a positive N2 pressure, toluene (2\u2005mL) was added via a syringe followed by degassing under a weak vacuum to this tube, and it was refilled with O2 three times. The reaction mixture was sealed and stirred at 293\u2005K for 24\u2005h under an O2 atmosphere. After completion of the reaction, the solution was cooled to room temperature and diluted with ethyl acetate followed by filtration through a thin pad of Celite. The crude product was purified by flash chromatography (hexa\u00adnes/EtOAc) on silica gel to afford N-acetyl benzo[def]carbazole 2. Crystals of the title compound were obtained by thermal evaporation of the pure compound from a 1:1 solution of di\u00adchloro\u00admethane and hexa\u00adnes.To a dried reaction tube, phenanthrene 6.Uiso(H) = 1.2 or 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022004509/ex2054sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004509/ex2054Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022004509/ex2054Isup3.cmlSupporting information file. DOI: 2101657CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Z)-ethene-1,2-bis\u00ad(di\u00adphenyl\u00adphosphine) as well as its complex with PtII are described here. The structure of the phosphine sulfide features intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions and C\u2014H\u22efS hydrogen bonds, as well as inter\u00admolecular \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions. The structure of the platinum(II) complex features inter\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efS hydrogen bonds.The crystal structures of the di\u00adsulfide derivative of ( Z)-bis\u00ad(di\u00adphenyl\u00adphosphine sulfide), C26H22P2S2 (I), along with its complex with PtII dichloride, di\u00adchloridoplatinum(II), [PtCl2(C26H22P2S2)] (II), are described here. Compound I features P=S bond lengths of 1.9571\u2005(15) and 1.9529\u2005(15)\u2005\u00c5, with a torsion angle of 166.24\u2005(7)\u00b0 between the two phosphine sulfide groups. The crystal of compound I features both intra\u00admolecular C\u2014H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions. Mol\u00adecules of compound I are held together with inter\u00admolecular \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions to form chains that run parallel to the z-axis. The inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction has a H\u22efCg distance of 2.63\u2005\u00c5, a D\u22efCg distance of 3.573\u2005(5)\u2005\u00c5 and a D\u2014H\u22efCg angle of 171\u00b0 (where Cg refers to the centroid of one of the phenyl rings). These chains are linked by relatively long C\u2014H\u22efS hydrogen bonds with D\u22efA distances of 3.367\u2005(4) and 3.394\u2005(4)\u2005\u00c5 with D\u2014H\u22efA angles of 113 and 115\u00b0. Compound II features Pt\u2014Cl and Pt\u2014S bond lengths of 2.3226\u2005(19) and 2.2712\u2005(19)\u2005\u00c5, with a P=S bond length of 2.012\u2005(3)\u2005\u00c5. The PtII center adopts a square-planar geometry, with Cl\u2014Pt\u2014Cl and S\u2014Pt\u2014S bond angles of 90.34\u2005(10) and 97.19\u2005(10)\u00b0, respectively. Mol\u00adecules of compound II are linked in the crystal by inter\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efS hydrogen bonds.The crystal structures of ( Unfortu2.I was solved in the ortho\u00adrhom\u00adbic space group P212121. The mol\u00adecular structure of this compound is shown in Fig.\u00a02I has P=S bond lengths of 1.9571\u2005(15) and 1.9529\u2005(15)\u2005\u00c5, P\u2014C bond lengths that range from 1.804\u2005(4) to 1.824\u2005(4)\u2005\u00c5 and a C=C bond length of 1.338\u2005(5)\u2005\u00c5. The P=S bonds are oriented in opposite directions with a S1\u2014P1\u2014P2\u2014S2 torsion angle of 166.24\u2005(7)\u00b0. The \u03c44 descriptor for fourfold coordination around both phospho\u00adrus atoms P1 and P2 is 0.94, indicating a near tetra\u00adhedral geometry of the phosphine sulfide groups  and 3.360\u2005(4)\u2005\u00c5 with D\u2014H\u22efA dihedral angles of 113 and 116\u00b0, respectively (Table\u00a01D\u22efA distances of 3.367\u2005(4) and 3.394\u2005(4)\u2005\u00c5 with D\u2014H\u22efA dihedral angles of 113 and 115\u00b0, respectively. The Flack parameter for this structure is \u22120.10\u2005(5)  and 97.19\u2005(10)\u00b0, respectively . The \u03c44 descriptor for fourfold coordination around the PtII center is 0.05, indicating a nearly perfect square-planar orientation of the sulfur and chlorine atoms around the metal  to 1.816\u2005(9)\u2005\u00c5, with a C=C bond length of 1.312\u2005(18)\u2005\u00c5. The \u03c44 descriptor for fourfold coordination of the phospho\u00adrus atom P1 is 0.91, indicating a slightly distorted tetra\u00adhedral geometry of the groups bonded to this atom, and that this tetra\u00adhedron is more distorted than what was observed for compound I.For the Pt3.I are held together in the crystal by inter\u00admolecular \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions \u2005\u00c5 and a D\u2014H\u22efCg angle of 171\u00b0 (Cg is the centroid of the C15\u2013C20 ring). Together, these inter\u00admolecular \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into chains that propagate parallel to the z-axis  and 3.561\u2005(5)\u2005\u00c5 with D\u2014H\u22efA angles of 155 and 135\u00b0, respectively. These hydrogen-bonding inter\u00adactions occur between the supra\u00admolecular chains of compound I.Mol\u00adecules of compound s Table\u00a01. Ring C9is Fig.\u00a05. Two potII are held together by C\u2014H\u22efCl \u2005\u00c5 with a D\u2014H\u22efA angle of 141\u00b0 . Sulfur atom S1 hosts the other inter\u00admolecular hydrogen bond with atom C3(H3) (symmetry code: x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0D\u22efA distance of 3.538\u2005(9) with a D\u2014H\u22efA angle of 133\u00b0. The inter\u00admolecular C\u2014H\u22efCl inter\u00adactions form chains of compound II that run parallel to the z-axis. These chains are then linked into a three-dimensional network through the inter\u00admolecular C\u2014H\u22efS hydrogen bonds.Mol\u00adecules of compound 4.et al., 2016I resulted in 17 hits. The majority of these hits were metal\u2013ligand complexes, where the ligand was a triazole ring bearing two di\u00adphenyl\u00adphosphine sulfide groups. Crystal structures of this ligand bonded to copper(II), zinc(II), palladium(II), and cadmium(II) were reported  and elemental sulfur  were combined in a round-bottom flask and dissolved in tetra\u00adhydro\u00adfuran (5\u2005mL). The reaction mixture was stirred for three\u2005h at room temperature. The solvent was removed under reduced pressure to give a white, gelatinous solid. The crude product was recrystallized from benzene (5\u2005mL) at 333\u2005K and isolated by vacuum filtration with a Hirsch funnel to give a white solid. Analysis of the solid by 31P NMR (CDCl3) showed that the target compound I was present along with trans-dppeS2 and unreacted starting material. Single crystals of compound I grew serendipitously upon slow evaporation of this solution. 31P NMR : Compound I: 32.3 ppm; trans-dppeS2: 36.6 ppm; cis-dppe: \u221222 ppm.Compound II: Equimolar amounts of compound I  and Pt(PhCN)2Cl2  were combined in a small vial and dissolved in 1\u2005mL CDCl3. Crystals of compound II formed serendipitously via slow evaporation of the solvent.Compound 6.I and II, all hydrogen atoms bonded to carbon atoms were placed in calculated positions and refined as riding: C\u2014H = 0.95\u20131.00\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for vinylic and aromatic hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022011847/pk2674sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022011847/pk2674Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022011847/pk2674IIsup5.hklStructure factors: contains datablock(s) II. DOI: 1481532, 2226172CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Heterodimers between nearly identical mol\u00adecules are connected via three hydrogen bonds from benzylic and ester methyl\u00adene groups to phospho\u00adnate. The dimers form chains along the a-axis direction, stabilized by C\u2014H\u22efO bridges.The title compound was prepared in three steps from  12H17I2O3P, was prepared in three steps from p-xylene. Heterodimers between nearly identical mol\u00adecules are connected via three hydrogen bonds from benzylic and ester methyl\u00adene groups to phospho\u00adnate. The dimers form chains along the a-axis direction, stabilized by C\u2014H\u22efO bridges.The title compound, C The A,B dimers are connected via three slightly bent C\u2014H\u22efO hydrogen bridges: C7A\u2014H7A\u22efO9B , C14A\u2014H14B\u22efO9B , and C11B\u2014H11D\u22efO9A . Three further C\u2014H\u22efO bridges connect neighbouring dimers to form chains along the a-axis direction \u2005\u00c5 157.9\u00b0, B shifted \u22121 along a], C7B\u2014H7C\u22efO9A  and C14B\u2014H14D\u22efO9A .In a project focusing on phenyl\u00adene\u00advinyl\u00adene emissive materials  I, global. DOI: 10.1107/S2414314621006544/bt4116Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621006544/bt4116Isup3.cmlSupporting information file. DOI: 2091488CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the original publication , referenFigure 1. Frequency of use of A. rhizogenes strains in the world: 1\u2014ATCC15834; 2\u2014A4+ATCC43057; 3\u2014LBA9402; 4\u2014R1000; 5\u2014K599+NCPPB2659; 6\u2014NCIB8196; 7\u2014R1601; 8\u2014C58C1; 9\u2014NCPPB1855; 10\u2014MAFF301724; 11\u2014A4T; 12\u2014TR7; 13\u2014A4RS; 14\u2014ARqual; 15\u2014TR101; 16\u2014ATCC11325; 17\u20141334; 18\u2014TR105; 19\u2014MSU440; 20\u2014MTCC532; 21\u2014HRI; 22\u2014LMG150; 23\u2014A13; 24\u2014R1600 (this is a modified figure from ref. [68]).Biomics2015, 7, 70\u2013120.Newly added reference [68] should read: Kuluev, B.R.; Vershinina, Z.R.; Knyazev, A.V.; Chemeris, D.A.; Baymiev, A.K.; Chumakov, M.I.; Baymiev, A.K.; Chemeris, A.V. Plant hairy roots are important instrumentation for researchers and powerful phytochembiofactory for manufacturers. With this correction, newly added reference [68] and the order of some references has been adjusted accordingly.The authors would like to apologize for any inconvenience caused to the readers by these changes. The original article has been updated."}
{"text": "The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C\u2013H\u22efO, O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 stacking. The inter\u00admolecular inter\u00adactions of the synthesized compound were qu\u00adanti\u00adfied by Hirshfeld surface analysis.The title compound was synthesized  6H15N2O+\u00b7C6H2N3O7\u2212\u00b7H2O, was synthesized via slow evaporation of an aqueous solution of picric acid with the substituted morpholine base and crystallized with one cation (C6H15N2O)+, one anion (C6H2N3O7)\u2212 and a water mol\u00adecule in the asymmetric unit. The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C\u2014H\u22efO, O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 stacking. The inter\u00admolecular inter\u00adactions of the synthesized compound were qu\u00adanti\u00adfied by Hirshfeld surface analysis.The title compound, C All three protons of the NH3+ group are involved in hydrogen bonding. The cation forms a strong charge-assisted hydrogen bond N5\u2014H5A\u22efO1  with the picrate anion, while H5C inter\u00adacts with O9 from the solvating water mol\u00adecule [D\u22efA = 2.741\u2005(2)\u2005\u00c5] and H5B is involved in a bifurcated hydrogen bond with O5 from a neighbouring picrate anion  and O9 from other water mol\u00adecule , respectively. Additionally, the two protons of the water mol\u00adecule inter\u00adact with a picrate anion or the nitro\u00adgen atom of the morpholinyl moiety . Further geometric details of these hydrogen bonds can be found in Table\u00a01The title compound crystallizes in the triclinic up Fig.\u00a01 with twoup Fig.\u00a01. The asypara-bound nitro group is nearly coplanar with the plane of the benzene ring [dihedral angle of \u22121.0\u2005(2)\u00b0] and two ortho-oriented nitro groups are, probably as a result of repulsion with the phenolic oxygen atom, twisted from the ring plane by \u221251.9\u2005(2) and 43.8\u2005(2)\u00b0. It has been mentioned previously that the nitro groups of the picrate anion play an important role in stabilizing the crystal packing via weak coulombic inter\u00adactions , C10\u2014H10B\u22efO6 and C12\u2014H12A\u22efO2 non-classical hydrogen bonds  and 4.0303\u2005(19)\u2005\u00c5, respectively, for the rings related by symmetry operations 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z and 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z. Finally, a centrosymmetric twelve-membered ring [(picrate)O\u2212\u22efH\u2014N\u2014H\u22efO\u2014H]2 with a third order graph set Fig.\u00a03s Table\u00a01. Severalup Fig.\u00a05. Furtheral Fig.\u00a06.CrystalExplorer 21.5  Hirshfeld surface of the title compound mapped over the limits \u22120.6471 to 1.3714 a.u. with close contacts to neighboring mol\u00adecules is shown in Fig.\u00a07et al., 2016Analysis of the Hirshfeld surface and the associated two-dimensional fingerprint plot for 2-(morpholin\u00adyl)ethyl\u00adammonium picrate monohydrate was performed with de and di represent the distances from a point on the Hirshfeld surface to the nearest atoms outside and inside the surface, respectively morpholinium] tetra\u00adkis\u00ad[(\u03bc3-phosphito)tri\u00adzinc(II)] hemihydrate morph\u00ado\u00adlinium] tetra\u00adkis\u00ad(\u03bc-iodo)\u00adtetra\u00adkis\u00ad(iodo)\u00addilead(II)] and : 3384 (O\u2014H), 2905 (NH3), 3110 (C\u2014H), 1382 (CH2), 993 (C\u2014O); 1H NMR : 8.831 , 3.63 , 3.03 , 2.58 , 2.46 . A suitable single crystal of 2-(morpholin\u00adyl)ethyl\u00adammonium picrate monohydrate was selected for X-ray diffraction studies.2-(Morpholin\u00adyl)ethyl\u00adammonium picrate monohydrate was synthesized by mixing one mole of 4-(2-ammonio\u00adeth\u00adyl)morpholine and one mole of picric acid in double-distilled water at about 303\u2005K. The solution was then allowed to evaporate at room temperature, which yielded yellow plate-like crystals of 2-(morpholin\u00adyl)ethyl\u00adammonium picrate monohydrate. The reaction scheme is shown in Fig.\u00a096.Uiso(H) = 1.2 Ueq(C). The acidic protons were localized from the residual electron-density map and refined with distance restraints (0.82\u2005\u00c5 for O\u2014H and 0.86\u2005\u00c5 for N\u2014H) and Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022011409/jq2022sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022011409/jq2022Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022011409/jq2022Isup3.cmlSupporting information file. DOI: 2222322CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S-(Pyridn-2-yl) benzo\u00adthio\u00adesters are presented with varying para-phenyl motifs . These structures presented are the first in their class. Distinct changes are observed in the inter\u00adaction types present in the crystal lattice as a direct result of the electronic influence of the para-phenyl motif.The structures of three  S-(pyridin-2-yl) benzo\u00adthio\u00adesters with varying para-phenyl substituents are presented, namely, S-(pyridin-2-yl) 4-nitro\u00adbenzo\u00adthio\u00adate , S-(pyridin-2-yl) 4-methyl\u00adbenzo\u00adthio\u00adate  and S-(pyridin-2-yl) 4-meth\u00adoxy\u00adbenzo\u00adthio\u00adate . This class of compounds are used in the mono-acyl\u00adation of pyrrolic species to yield multifunctional tetra\u00adpyrroles. The structures presented herein are the first of their compound class. The dominant inter\u00adactions present in this series are \u03c0\u2013\u03c0 stacking and C\u2014H\u22efO inter\u00adactions, and as the para-phenyl motif changes from electron withdrawing  to electron donating , changes are observed in the inter\u00adactions present in the crystal packing, from predominant \u03c0\u2013\u03c0 stacking in 1 to exclusively C\u2014H\u22efO/N inter\u00adactions  in 3.The crystal structures of three  Each mol\u00adecular structure shows an S-(pyridin-2-yl) benzo\u00adthio\u00adate where the para-phenyl motif is modified, from NO2 in 1, CH3 in 2, and OCH3 in 3. All of the groups utilized herein are found extensively in the field of tetra\u00adpyrroles.The single-crystal XRD structures of title compounds 3 Figs. 2\u20134 \u25b8 \u25b8, 1\u20133, the substituted phenyl moieties are all essentially planar with the pyridine ring twisted relative to this plane. This is seen in the plane normal to plane normal angle and the torsion angle described by C8\u2014S1\u2014C6\u2014N1. The twist of the methane\u00adthio\u00adate moiety to the phenyl ring also describes the change in the angle of the rings to each other. These values are shown in Table\u00a01In all structures 1 . Furthermore, considering the respective previously determined Hammett constants, it is observed that the most electron donating is the OCH3 group in 3 (\u03c3p = \u22120.27), with 2 (CH3) lying somewhere in between (\u03c3p = \u22120.17)  and 3.371\u2005(5)\u2005\u00c5]. The pyridine N1 is also an acceptor to the phenyl C12-H [D\u22efA = 3.315\u2005(5)\u2005\u00c5]. The nitro group is a dual acceptor with inter\u00adactions between O18 and one pyridyl C3-H [D\u22efA = 3.396\u2005(5)\u2005\u00c5] and also a bifurcated inter\u00adaction between O17 and phenyl C14-H and C15-H .Compound s Table\u00a02 to the c2 presents C\u2014H\u22efN-paired dimers between the H6-pyridyl protons C2-H2 and N1  and a C16-H\u22efO9 inter\u00adaction [D\u22efA = 3.460\u2005(2)\u2005\u00c5].Compound 3 presents a multitude of non-classical hydrogen-bonding inter\u00adactions, of the C\u2014H\u22efOcarbon\u00adyl and the C\u2014H\u22efNpyrid\u00adyl type (Table\u00a04D\u22efA = 3.2566\u2005(15) and 3.4270\u2005(16)\u2005\u00c5, respectively]. There is another bifurcated hydrogen-bond inter\u00adaction between the pyridine N1 and C11 and C12 , linking the mol\u00adecules head to tail. The meth\u00adoxy groups form C17-H\u22efO16 inter\u00adactions [D\u22efA = 3.4475\u2005(17)\u2005\u00c5], comprising a supra\u00admolecular synthon linking two mol\u00adecules together. The meth\u00adoxy oxygen O16 is further linked by a phenyl C14-H\u22efO16 inter\u00adaction [D\u22efA = 3.3340\u2005(15)\u2005\u00c5].Compound e Table\u00a04. The car1 and 2. Weak dimeric offset \u03c0\u2013\u03c0 stacking is observed in 1 with columns of anti-parallel non-inter\u00adacting mol\u00adecules when viewed normal to (001)  x, y, \u22121\u00a0+\u00a0z; x, y, 1\u00a0+\u00a0z] is 3.850\u2005(3)\u2005\u00c5 with a slippages of 1.823 and 1.856\u2005\u00c5, respectively, and angles between planes of 0.0\u2005(2)\u00b0. In 2, \u03c0-stacking occurs only through phenyl ring pairs with the closest centroid\u2013centroid distance being 3.8783\u2005(11)\u2005\u00c5, a slippage of 1.575\u2005\u00c5, and an angle between planes of 0.03\u2005(9)\u00b0, as seen normal to the (011) plane. In 3 there is no relevant \u03c0\u2013\u03c0 stacking, with the closest centroid\u2013centroid distance being 4.0847\u2005(7)\u2005\u00c5, with a slippage of 2.042\u2005\u00c5 and an angle between the planes of 5.14\u2005(6)\u00b0.\u03c0\u2013\u03c0 stacking is evident in both 1) Fig.\u00a06. The clo4.et al., 2016S-phenyl benzo\u00adthio\u00adate . The distinct C\u2014H\u22efN inter\u00adactions seen particularly in 3 do not exist in the phenyl homologue.A search in the Cambridge Structural Database benzo\u00adthio\u00adate benzo\u00adthio\u00adate  \u00adbenzene-1,4-dicarbo\u00adthio\u00adate -5.1, 2, and 3 were synthesized following the reported procedure  in a solution of CH2Cl2 was added dropwise over 0.5\u2005h to a stirring solution of 2-mercapto\u00adpyridine  in CH2Cl2. The solution was left to stir for a further 2\u2005h at room temperature. Throughout the addition processes, minor exotherms were noted, particularly for 1. The solution was diluted with the same volume again of CH2Cl2, and the solution was washed with NaOH (2 M), water, brine, and the organic layer then dried (MgSO4). Excess solvent was removed under reduced pressure and the title compounds were purified in the following ways: for 1, crystals were generated via hot recrystallization from ethyl acetate, and for 2 and 3, crystals were generated via precipitation from diethyl ether and hexa\u00adnes. Compound 1 was yielded in 69%, with yields for 2 and 3 comparable to those previously reported .1:Analytical data for 1H NMR  \u03b4 = 8.66\u20138.68 , 8.31 , 8.14 , 7.77\u20137.81 , 7.68\u20137.70 , 7.33\u20137.37 ; 13C{1H} NMR : \u03b4 = 188.3, 150.9, 150.3, 141.3, 137.7, 130.9, 128.7, 124.3, 124.2 ppm; RF = 0.58 ; m.p. = 427\u2013429\u2005K. Multiple attempts have been made to obtain a mol\u00adecular ion peak via ESI\u2013MS and all have been unsuccessful.6.Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989023001056/yz2028sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989023001056/yz20281sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989023001056/yz20282sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989023001056/yz20283sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20281sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20282sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20283sup7.cmlSupporting information file. DOI: 10.1107/S2056989023001056/yz2028sup8.pdf1H, 13C, and 1H-13C-HSQC NMR spectra of compound 1, along with overlayed aromatic regions of the 1H NMR spectra of compounds 1, 2, and 3. DOI: 2239845, 2239844, 2239843CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the packing of the title compound, \u03c0\u2013\u03c0, C\u2014H\u22efO, C\u2014H\u22efBr, and N\u2014H\u22efN inter\u00adactions are present. 12H14BrN3O2, the pyrazole and benzene rings are nearly co-planar with a dihedral angle between the rings of 2.36\u2005(5)\u00b0. In the crystal, inversion dimers linked by pairwise N\u2014H\u22efN hydrogen bonds generate R22(8) loops. The dimers are linked into a three-dimensional network by weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separation = 3.7394\u2005(6)\u2005\u00c5] and C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds.In the title compound, C Very weak C2\u2014H2\u22efO2, C11\u2014H11C\u22efO2 and C12\u2014H12B\u22efO2 intra\u00admolecular inter\u00adactions are present  = 3.7394\u2005(6)\u2005\u00c5, where Cg1 is the centroid of the pyrazole ring.In the extended structure, pairwise N3\u2014H3if Fig.\u00a02. The dimon Fig.\u00a03 also occ5-Bromo-1H-indazol-3-amine (1): To a solution of 5-bromo-2-fluoro benzo\u00adnitrile (1.0\u2005mmol) in ethanol (20\u2005ml) was added hydrazine hydrate (99%) (10.0\u2005mmol). The reaction mixture was heated in sealed tube at 343\u2005K for 4\u2005h and progress of the reaction was monitored by TLC. The reaction mixture was concentrated to dryness. The brown-coloured solid was purified by recrystallization from ethanol solution to afford pale-yellow needles (90%), m.p. 407\u2005K : To a solution of compound (1) (5.0\u2005mmol) in di\u00adchloro\u00admethane (40\u2005ml) was added DMAP (5.0\u2005mmol). The reaction mixture cooled to 273\u2005K and boc anhydride (5.0\u2005mmol) was added. The reaction mixture was slowly warmed to room temperature and stirred for 15\u2005h. Progress of the reaction was monitored by TLC. The reaction mixture was diluted with di\u00adchloro\u00admethane (50\u2005ml) and washed with water and brine (25\u2005ml), dried over anhydrous sodium sulfate and concentrated. The crude compound was purified by column chromatography  to afford a gummy solid, which solidifies as transparent crystals after 2\u2005d (62%), m.p. 389\u2005K.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621006945/hb4388sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314621006945/hb4388Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621006945/hb4388Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2414314621006945/hb4388Isup4.cmlSupporting information file. DOI: 2094667CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Water mol\u00adecules donate O\u2014H\u22efO and accept N\u2014H\u22efO hydrogen bonds, forming helical arrangements.In the crystal, mol\u00adecules of the title compound, C 24H20N2O4\u00b7H2O, crystallizes with half a mol\u00adecule of 2--N\u2032-[2-acet\u00adyl]acetohydrazide and half a water mol\u00adecule in the asymmetric unit. In the crystal, mol\u00adecules form planes parallel to (011). Two mol\u00adecules are connected by water mol\u00adecules via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds.The title compound, C An ORTEP representation is shown in Fig.\u00a01et al., 2020The asymmetric unit comprises half a mol\u00adecule of 2--N\u2032-[2-acet\u00adyl]acetohydrazide mol\u00adecules are connected by a water mol\u00adecule via O\u2014H\u22efO and N\u2014H\u22efO bonds  Fig.\u00a02. Two 2- and 2-acetohydrazide  in dry ethanol (10\u2005mL) was heated with stirring under reflux for 2\u2005h. The solid formed on cooling to room temperature. It was collected by filtration, washed with ethanol, dried and recrystallized from di\u00admethyl\u00adformamide to give colourless crystals, m.p. > 300\u00b0C  I. DOI: 10.1107/S241431462100314X/bt4110Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S241431462100314X/bt4110Isup3.cmlSupporting information file. DOI: 2072979CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Thereby, the titanium atom is stabilized by the Lewis bases tri\u00adphenyl\u00adphosphine oxide ( 6H11)2N]3Ti\u2014CH3 with the Lewis acid B(C6F5)3, followed by addition of the Lewis bases (C6H5)3PO and p-F\u2014C6H4CN led to the complex salts tris\u00ad(di\u00adcyclo\u00adhexyl\u00adamido)(tri\u00adphenyl\u00adphosphine oxide)titanium methyl\u00adtris(penta\u00adfluoro\u00adphen\u00adyl)borate toluene sesquisolvate, [Ti(C12H22N)3(C18H15OP)](C19H3F15B)\u00b71.5C7H8, (1), and tris\u00ad(di\u00adcyclo\u00adhexyl\u00adamido)(4-fluoro\u00adbenzo\u00adnitrile)\u00adtitanium methyl\u00adtris\u00ad(penta\u00adfluoro\u00adphen\u00adyl)borate toluene sesquisolvate, [Ti(C12H22N)3(C7H4FN)](C19H3F15B)\u00b71.5C7H8, (2), both crystallizing with 1.5 equivalents of toluene solvent mol\u00adecules. The Lewis acid\u2013base adducts (1) and (2) can be described by dative donor bonds. The packing of the complex cations, anions and solvent mol\u00adecules in the crystal structure is consolidated by an intricate three-dimensional network of non-classical C\u2014H\u22efF inter\u00adactions. Disorder of some of the cyclo\u00adhexyl groups and the toluene solvent mol\u00adecules is observed.The reaction of [(C An intricate three-dimensional network of non-classical C\u2014H\u22efF inter\u00adactions is formed in the crystals of (1) and (2), involving the C\u2014H groups of both cations and solvent mol\u00adecules as donors, and some F atoms of the [H3CB(C6F5)3]\u2212 anions as acceptors  and (2) were obtained from a saturated solution of toluene at 243\u2005K.All reactions were carried out under a dry nitro\u00adgen atmosphere using Schlenk techniques or in a glove box. Solvents were dried according to standard procedures over Na/K alloy with benzo\u00adphenone as an indicator and distilled under a nitro\u00adgen atmosphere. The cationic titanium complex was synthesized by reacting tris-(di\u00adcyclo\u00adhexyl\u00adamido)\u00admethyl\u00adtitanium and tris-penta\u00adfluorphenyl\u00adborane (Adler 5.1) shows disorder of one cyclo\u00adhexyl residue (C25 to C30), located at N3, over two sets of sites, with refined site occupancy factors 0.87:0.13. Compound (2) shows disorder of two of the six cyclo\u00adhexyl residues , located at the N1 and N3 atoms, respectively, with refined site occupation factors of 0.76:0.24 and 0.85:0.15. No restraints or constraints were applied during the refinement of this kind of disorder. All non-H atoms were refined anisotropically with the exception of the minor components of the disordered parts, which have been refined isotropically. In addition, the toluene solvent mol\u00adecule in compounds (1) and (2) are disordered. In (1), one toluene mol\u00adecule (C81\u2013C87) is equally disordered over an inversion centre, and one (C74\u2013C80) over two sets of sites, with refined site occupation factors of 0.764\u2005(4):0.236\u2005(4). In (2), one toluene mol\u00adecule (C63\u2013C69) is disordered over two sets of sites, the site occupancy was constrained to 0.5 for each component. The other toluene mol\u00adecule (C70\u2013C76) is disordered over two sets of sites with refined occupation factors of 0.29\u2005(3):0.210\u2005(3), both of which are additionally disordered over an inversion centre, resulting in a disorder over four sites.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022007952/wm5649sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989022007952/wm56491sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989022007952/wm56492sup3.hklStructure factors: contains datablock(s) 2. DOI: 2195527, 2195526CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "HLA\u2010DRB5*01:01:01\u2010DRB1*15:01:01\u2010DQA1*01:02:01\u2010DQB1*06:02:01 haplotype.Multiple sclerosis (MS) is a chronic neurological disease believed to be caused by autoimmune pathogenesis. The aetiology is likely explained by a complex interplay between inherited and environmental factors. Genetic investigations into MS have been conducted for over 50 years, yielding\u00a0>100 associations to date. Globally, the strongest linkage is with the human leukocyte antigen (HLA) DRB3, DRB4, DRB5, DRB1, DQA1, DQB1, DPA1 and DPB1 as well as their extended haplotypes and genotypes in 100 Swedish MS patients. Results were compared to 636 population controls.Here, high\u2010resolution sequencing of HLA was used to determine the alleles of HLA\u2010DR\u2010DQ genotypes were found. Three extended HLA\u2010DR\u2010DQ genotypes were found to be correlated to MS; HLA\u2010DRB5*01:01:01\u2010DRB1*15:01:01\u2010DQA1*01:02:01\u2010DQB1*06:02:01 haplotype together withThe heterogeneity in HLA associations with MS was demonstrated; among 100 patients, 69 extended HLA\u2010DRB4*01:01:01//DRB4*01:01:01:01\u2010DRB1*07:01:01\u2010DQA1*02:01//02:01:01\u2010DQB1*02:02:01,(A) HLA\u2010DRBX*null\u2010DRB1*08:01:01\u2010DQA1*04:01:01\u2010DQB1*04:02:01, and(B) HLA\u2010DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01.(C) HLA\u2010DRB3*01:01:02 was considered protective against MS. However, when combined with HLA\u2010DRB3*01:01:02\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01, this extended haplotype was considered a predisposing risk factor. This highlights the limitations as included with investigations of single alleles relative to those of extended haplotypes/genotypes.At the allelic level, HLA\u2010DRB5*01:01:01\u2010DRB1*15:01:01\u2010DQA1*01:02:01\u2010DQB1*06:02:01.In conclusion, with 69 genotypes presented among 100 patients, high\u2010resolution sequencing was conducted to underscore the wide polymorphisms present among MS patients. Additional studies in larger cohorts will be of importance to define MS among the patient group not associated with  Studies in African\u2010Americans, among whom the HLA\u2010DQB1*06:02 allele is not found on HLA\u2010DRB1*15:01 haplotypes, has attributed the risk of MS to HLA\u2010DRB1*15:01. Additional HLA\u2010DRB1\u2010DQB1 alleles and haplotypes associated with MS includeHLA\u2010DRB1*03:01\u2010DQA1*05:01\u2010DQB1*02:01  is the most common inflammatory disease affecting the central nervous system. Epidemiological findings suggest a gene\u2013environment interaction, and the pathogenesis of MS is widely assumed to be of autoimmune origin  included blood samples collected from the Neurology Department of the Sk\u00e5ne University Hospital in Malm\u00f6. The MS diagnosis of the patients was validated by treating physician (Table\u00a0n\u00a0=\u00a0636) included in the HLA Next Generation Sequencing (NGS) analysis were obtained as previously described  and (B) LifeGene controls  .2.2DNA was extracted using Qiagen Blood Maxi Kit according to manufacturer's protocol and as previously described , and second occasion: LifeGene controls (n\u00a0=\u00a0188)]; in the meantime the resolution of typing was improved; therefore, that some alleles are written as follows in the manuscript DRB4*01:01:01//DRB4*01:01:01:01.HLA NGS was performed by Scisco Genetics . Samples  were sent blindly to the investigators. HLA NGS makes use of PCR\u2010based HLA amplification and sequencing with Illumina MiSeq technology, as described in previous studies , as previously described .A reference haplotype with a similar frequency between the study groups was selected in HLA 6 haplotypes with positive (A) and 1 haplotypes with negative (B) association for MS patients in comparison to population controls were identified :HLA\u2010DRB3*02:02:01\u2010DRB1*03:01:01\u2010DQA1*05:01:01\u2010DQB1*02:01:01, (2) HLA\u2010DRB4*01:03:01\u2010DRB1*04:02:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01, (3) HLA\u2010DRB4*01:03:01\u2010DRB1*04:03:01\u2010DQA1*03:01:01\u2010DQB1*03:02:01, (4) HLA\u2010DRB5*01:01:01\u2010DRB1*15:01:01\u2010DQA1*01:02:01\u2010DQB1*06:02:01, (5) HLA\u2010DRB5*02:02//DRB5*02:02:01\u2010DRB1*16:01:01\u2010DQA1*01:02:02\u2010DQB1*05:02:01 and (6) HLA\u2010DRBX*null\u2010DRB1*01:02:01\u2010DQA1*01:01:02\u2010DQB1*05:01:01.Identified haplotypes with higher frequency among MS patients compared to GP were (1) HLA\u2010DRB4*01:03:01\u2010DRB1*07:01:01\u2010DQA1*02:01//*02:01:01\u2010DQB1*03:03:02 (Table\u00a0Identified haplotypes with lower frequency among MS patients compared to GP were (1) Based on the Haplo\u2010Score, 3.3HLA\u2010DRB3, DRB4, and DRB5 alleles, 47 different HLA\u2010DRB1 alleles, 23 different HLA\u2010DQA1 alleles, 24 different HLA\u2010DQB1 alleles, 14 HLA\u2010DPA1 and 30 HLA\u2010DPB1 alleles were found. The complete results and associations for all the different alleles found in the study are reported in Supplementary Table HLA\u2010DRB3*03:01:01 , HLA\u2010DRB1*03:01:01 , HLA\u2010DQA1*03:01:01 , HLA DQB1*02:01:01 , HLA\u2010DPA1*01:03:01  and HLA\u2010DPB1*02:01:02 . Based on the Haplo\u2010Score, 9 alleles with positive and 7 alleles with negative association for MS patients in comparison to population controls were identified , HLA\u2010DRB3*01\u2010DR3\u2010DQ2, while the association with HLA\u2010DR7\u2010DQ2 appear novel.From the present study, we first report that previously found HLA\u2010associations to MS, most prominently to HLA\u2010DPB1*104:01 (predisposing), HLA\u2010DQB1*03:01 and HLA\u2010DQB1*03:03 (protective), and HLA\u2010DRB1*14:04:01 (protective) . Due to high degree of polymorphism presented, we suggest that mechanistic studies would be necessary to fully determine the role of HLA\u2010DQB1*03:01 to risk and progression of MS.Here, we could not confirm recent allelic MS associations using high\u2010resolution sequencing to HLA\u2010DRB3*01:01:02 was considered protective against MS at the allelic level, the extended genotype, abbreviated HLA\u2010DR15\u2010DQ6\u2010DRB3*01\u2010DR3\u2010DQ2, was considered a predisposing risk factor. This highlights the limitations of studies of single alleles relative to studies of extended haplotypes and genotypes. We speculate that the shifting association for HLA\u2010DRB3*01:01:02 from protective to predisposing, could be related to mechanisms of epistasis. Previously, HLA\u2010DQA1*01:02 was demonstrated to increase risk of MS if found in trans position to the haplotype of HLA\u2010DR15\u2010DQ6  and two\u2010thirds of all patients (68 of 100) encompassed haplotypes of either HLA\u2010DR15\u2010DQ6, HLA\u2010DRB3*01\u2010DR3\u2010DQ2 or HLA\u2010DRB3*02\u2010DR3\u2010DQ2.Lastly, we report heterogeneity in HLA associations to MS given that, among 100 patients, 69 different extended HLA\u2010DR15\u2010DQ6 haplotype is consistently reported, both here and elsewhere, as the major genetic contributor to MS. Some suggestions of the presence of this extended haplotype at the age at onset  as compared to 6%  is of interest, complementary triggers and pathways of autoimmunity could be present. It cannot be excluded that environmental factors are different between MS patients negative for HLA\u2010DR15\u2010DQ6 but positive for HLA\u2010DR7\u2010DQ2. Studies in larger and diversified cohorts would be needed to define MS in this group of patients.The group of non\u2010HLA\u2010DRB1*03:01 allele has been associated with MS. An increased risk was reported when the HLA\u2010DRB1*03:01 allele is homozygous  among both patients and controls, which precluded computation of the other rare allele variants among the families that were used as templates (Lind et\u00a0al., HLA\u2010DR15\u2010DQ6 patients.A weakness of our study was the fact that the It appears overly simplistic to characterize MS as having a single aetiology and pathogenesis. The heterogeneous clinical presentation, variable clinical course, inconsistency in genetic markers, unpredictable therapeutic response and diverse histopathological findings may be indicative of divergence in the demyelination pathways (Lucchinetti et\u00a0al., HLA\u2010DR15\u2010DQ6.2.In summary, we have confirmed previous HLA associations to MS, while also offering plausible explanations to help guide future research. Using high\u2010resolution sequencing, we have highlighted the widespread polymorphisms as 69 distinct genotypes present among 100 Swedish MS patients and further studies in a larger number of patients will be needed to further delineate MS not associated with There are no conflicts of interest.Supplement MaterialClick here for additional data file.Supplement MaterialClick here for additional data file."}
{"text": "There is a high carrying rate of \u03b1\u2010thalassemia in Fujian province. However, there are few large\u2010scale studies on the correlation between genotype and phenotype in Fujian province. The purpose of this study was to analyze the phenotype and genotype in a cohort of 2923 patients with \u03b1\u2010thalassemia in Fujian province, so as to provide reference data for screening and diagnosis of \u03b1\u2010thalassemia in Fujian province.The genotype of \u03b1\u2010thalassemia was detected by PCR reverse dot blot assay, gap\u2010PCR, single PCR, nested PCR, and sequencing. Clinical and hematological indices of 2923 patients were collected, and the correlation between genotype and phenotype was analyzed.SEA/\u03b1\u03b1 was the most common genotype, accounting for 64.80%. In addition, rare \u03b1\u2010thalassemia genotypes were detected in Fujian province, including \u2010\u2010THAI/\u03b1\u03b1 (0.41%), HK\u03b1\u03b1/\u2010\u2010SEA (0.03%), and the novel \u03b1\u2010thalassemia gene mutation CD5 (GCC>ACC) (HGVS named HBA1: c.16G>A) (0.03%). Patients with deletional genotypes of \u03b1\u2010thalassemia were found to have higher RBC and lower Hb, MCV, MCH, and HbA2 than patients with non\u2010deletional genotypes of \u03b1\u2010thalassemia (p\u2009<\u20090.05).Among 10,350 patients, 2923 cases were found with \u03b1\u2010thalassemia, with a detection rate of 28.24%. Among them, \u2010\u2010The clinical phenotype of \u03b1\u2010thalassemia is influenced by molecular mechanisms. HBA1: c.16G>A mutation is a novel mutation that was first reported in Fujian province, which enriches the human hemoglobin mutation spectrum. There were double peaks at nt224, G>A, in HBA1, corresponding to CD5 (GCC>ACC). It was named HBA1: c.16G>A using the Human Genome Variation Society (HGVS) nomenclature. HBA1: c.16G>A is a novel mutation that was first reported in Fujian province. The discovery of this novel mutation in \u03b1\u2010globin gene has enriched the database of hemoglobin variants, and the detailed genetic analysis and clinical symptom description of this mutation will contribute to the further study of hemoglobin function in the future. Its pathogenesis is due to the defect of \u03b1\u2010globin gene; the synthesis of \u03b1\u2010globin peptide chain was partially or completely inhibited, resulting in hereditary hemolytic anemia. It is one of the most common monogenic diseases with the highest incidence in the world and has attracted extensive attention at home and abroad because of its fatal and disabling nature, which can lead to birth death or birth defects.However, there are few large\u2010scale studies on the correlation between genotype and phenotype in \u03b1\u2010thalassemia patients in Chinese population. In this study, 10,350 patients from Fujian province were analyzed for genotype and phenotype. Such a study may provide more data for genetic counseling and clinical diagnosis in this region.22.1This study was reviewed and approved by the Ethics Review Committee of Fujian Maternity and Child Health Hospital College of Clinical Medicine for Obstetrics & Gynecology and Pediatrics, Fujian Medical University. Signed informed consent was obtained from all participants following a detailed description of the purpose of the study. All experiments were performed in accordance with relevant guidelines and regulations.2.2From January 2019 to November 2021, peripheral blood samples of patients who underwent thalassemia\u2010related examinations in outpatients and inpatients of Fujian Maternity and Child Health Hospital College of Clinical Medicine for Obstetrics & Gynecology and Pediatrics, Fujian Medical University were collected. A total of 10,350 patients  with household registration in Fujian province were screened, including 2923 cases of \u03b1\u2010thalassemia. \u03b1\u2010thalassemia was confirmed by molecular analyses. Information about patients diagnosed with \u03b1\u2010thalassemia was collected, and their genotypes and phenotypes were statistically analyzed. The median age was 27 (8.31) years. The median age was 5.5 (1.30) years for males and 28 (25.31) years for females. Exclusion criteria are as follows: (1) \u03b2\u2010thalassemia; (2) other blood diseases such as iron deficiency anemia and megaloblastic anemia; (3) malignant tumor; (4) systemic immune disorders; and (5) allergic constitution. Peripheral blood samples were collected from selected subjects and anticoagulated with EDTA\u2010K2. Approximately 2\u2009ml of the anticoagulated blood sample was used for analysis of blood cell parameters on a Sysmex XN\u20102000 automatic hematology analyzer , and the hemoglobin components and levels were analyzed using an automated capillary electrophoresis system . Serum ferritin (SF) concentration, as a measure of iron status, was determined by the chemiluminescent microparticle immunoassay (CMIA) .2.3SEA/, \u2010\u03b13.7/, and \u2010\u03b14.2/) and the mutations  of \u03b1\u2010thalassemia were analyzed by PCR reverse dot blot assay using commercial kits  as described. The 17 common \u03b2\u2010thalassemia was performed using PCR reverse dot blot assay with the thalassemia gene detection kit  following the manufacturer's instructions.DNA was extracted using the DNA Blood Extraction Kit . The deletions (\u2010\u20102.4THAI genotype was tested using gap polymerase chain reaction (gap\u2010PCR), and HK\u03b1\u03b1 genotype was tested by single PCR and nested PCR, as described previously.\u2010\u20102.5p\u2009<\u20090.05 were considered statistically significant.All data were entered into and managed using Microsoft Excel 2007 . The data were analyzed using the Statistical Package for the Social Sciences (SPSS) version 25 . Associations between hematological indices and the variant genotypes were assessed by a nonparametric Kruskal\u2013Wallis test, presented as median . The results with 33.1Among 10,350 patients, 2923 patients with \u03b1\u2010thalassemia mutation were detected, with a detection rate of 28.24%, including 2666 cases (91.21%) of \u03b1 deletional genotype, 181 cases (6.19%) of \u03b1 mutational genotype, 12 cases (0.41%) of \u03b1 deletion combined with mutation, and 64 cases (2.19%) of \u03b1/\u03b2 complex mutants.SEA/\u03b1\u03b1 (64.80%), \u2010\u03b13.7/\u03b1\u03b1 (18.95%), \u2010\u03b14.2/\u03b1\u03b1 (4.96%), \u03b1QS\u03b1/\u03b1\u03b1 (3.63%), \u03b1CS\u03b1/\u03b1\u03b1 (1.47%), \u2010\u2010SEA/\u2010\u03b13.7 (1.20%), and \u03b1WS\u03b1/\u03b1\u03b1 (0.99%). In addition, rare \u03b1\u2010thalassemia genotypes including \u2010\u2010THAI/\u03b1\u03b1 (0.41%), HK\u03b1\u03b1/\u2010\u2010SEA (0.03%), and the novel \u03b1\u2010thalassemia gene mutation CD5 (GCC>ACC) (HGVS named HBA1: c.16G>A) (0.03%) were detected in Fujian province \u2009\u00d7\u20091012/L) (p\u2009<\u20090.05).Conversely, the levels of Hb, MCV, MCH, and HbA2 in patients with deletional genotypes of \u03b1\u2010thalassemia were lower than that in patients with non\u2010deletional genotypes of \u03b1\u2010thalassemia  g/L vs 119.0  g/L, 67.5  fl vs 76.1  fl, 21.2  pg vs 24.7  pg, and 2.3  % vs 2.5  %) (p\u2009<\u20090.05).  in patients with deletional genotypes of \u03b1\u2010thalassemia was higher than that in patients with non\u2010deletional genotypes of \u03b1\u2010thalassemia \u2009\u00d7\u200910SEA/\u03b1\u03b1 were found to have higher RBC, HbF, and SF and lower Hb, MCV, MCH, and HbA2 than patients with \u2010\u03b13.7/\u03b1\u03b1 (p\u2009<\u20090.05). What is more, patients with \u2010\u2010SEA/\u03b1\u03b1 were found to have higher RBC and lower Hb, MCV, MCH, and HbA2 than patients with \u2010\u03b14.2/\u03b1\u03b1 (p\u2009<\u20090.05). Age of \u2010\u2010SEA/\u03b1\u03b1 was lower than that of \u2010\u03b13.7/\u03b1\u03b1 and \u2010\u03b14.2/\u03b1\u03b1 (p\u2009<\u20090.05) Among the non\u2010deletional genotypes of \u03b1\u2010thalassemia, patients with \u03b1QS\u03b1/\u03b1\u03b1 were found to have higher RBC and HbA2 and lower MCV and MCH than patients with \u03b1CS\u03b1/\u03b1\u03b1 (p\u2009<\u20090.05). Patients with \u03b1QS\u03b1/\u03b1\u03b1 were found to have lower MCV and MCH than patients with \u03b1WS\u03b1/\u03b1\u03b1 (p\u2009<\u20090.05). In addition, patients with \u03b1CS\u03b1/\u03b1\u03b1 were found to have lower HbA2 than patients with \u03b1WS\u03b1/\u03b1\u03b1 (p\u2009<\u20090.05).  that was suspected to be a \u03b1\u2010thalassemia carrier. Sequencing the full\u2010length \u03b11\u2010globin gene and of the full\u2010length \u03b12\u2010globin gene of the DNA from the peripheral blood sample was done. The results showed there were double peaks at nt224, G>A, in HBA1, corresponding to CD5 (GCC>ACC). It was named HBA1: c.16G>A using the Human Genome Variation Society (HGVS) nomenclature  with\u2010\u2010SEA/\u03b1\u03b1, 554 cases (18.95%) with \u2010\u03b13.7/\u03b1\u03b1, and 145 cases (4.96%) with \u2010\u03b14.2/\u03b1\u03b1, suggesting that the most common genotype of \u03b1 \u2010thalassemia in this region was \u2010\u2010SEA/\u03b1\u03b1, which was consistent with the reports from Guangxi, Guangdong, Chongqing, and Hainan.QS\u03b1/\u03b1\u03b1 (3.63%), followed by \u03b1CS\u03b1/\u03b1\u03b1 (1.47%) and \u03b1WS\u03b1/\u03b1\u03b1 (0.99%), which were the same as those in Chongqing and slightly different from those in Guangxi, Guangdong, and Hainan,SEA/\u03b1\u03b1 was dominant in these provinces, and the frequencies were respectively 57.55%, 52.78%, and 83.87%.There are two types of \u03b1\u2010thalassemia: deletional genotype and non\u2010deletional genotype. In addition to the most common deletional genotype, rare deletional genotype of \u03b1\u2010thalassemia has been found in different populations.THAI/\u03b1\u03b1 , HK\u03b1\u03b1/\u2010\u2010SEA , and the novel \u03b1\u2010thalassemia gene mutation CD5 (GCC>ACC)  in Fujian Province. \u2010\u2010THAI genotype has been gradually found in the population of southern China, mainly distributed in Guangxi, Guangdong, Taiwan, and Fujian.SEA genotype, the phenotype of \u2010\u2010THAI is manifested as microcytic hypochromic anemia and the Thai\u2010type homozygote or Thai\u2010type heterozygotes with SEA\u2010type \u03b1\u2010thalassemia are manifested as Bart's hydrops fetalis.3.7 fragment and \u03b1\u03b1\u03b1anti4.2 fragment formed by recombination and unequal transposition of the homologous X segment of the \u03b1\u2010globin gene cluster. So far, \u03b1\u03b1\u03b1anti4.2 fragments cannot be detected through the routine thalassemia diagnostic kit. The genotype of \u2010\u03b13.7/\u03b1\u03b1, HK\u03b1\u03b1/\u2010\u03b13.7, and HK\u03b1\u03b1/\u03b1\u03b1 is entirely the result of \u2010\u03b13.7/\u03b1\u03b1 by gap\u2010PCR.3.7/\u03b1\u03b1. Therefore, the symptoms of thalassemia associated with HK\u03b1\u03b1/\u03b1\u03b1 and \u2010\u2010SEA were milder than those of hemoglobin H disease associated with \u2010\u03b13.7 and \u2010\u2010SEA, and only mild globin production disorder was observed . If both husband and wife carry HK\u03b1\u03b1/\u03b1\u03b1 and \u2010\u2010SEA respectively, the fetus can be kept. However, if the HK\u03b1\u03b1/\u03b1\u03b1 or anti\u2010HK\u03b1\u03b1/\u03b1\u03b1 genotypes are incorrectly identified as \u2010\u03b13.7/\u03b1\u03b1, it may lead to incorrect clinical treatment.Three rare \u03b1\u2010thalassemia genotypes were also detected in this study, including \u2010\u2010SEA/\u03b1\u03b1/\u03b2IVS\u20102\u2010654(C\u2192T)/\u03b2N (11 cases), \u2010\u03b13.7/\u03b1\u03b1/\u03b2IVS\u20102\u2010654(C\u2192T)/\u03b2N (11 cases), \u2010\u2010SEA/\u03b1\u03b1/\u03b2CD41\u201042(\u2010CTTT)/\u03b2N (11 cases), \u2010\u03b13.7/\u03b1\u03b1/\u03b2CD41\u201042(\u2010CTTT)/\u03b2N (4 cases), and \u2010\u2010SEA/\u03b1\u03b1/\u03b2\u221228(A\u2192G)/\u03b2N (4 cases). While patients with \u03b1\u2010 and \u03b2\u2010thalassemia have milder symptoms, their offspring are more likely than the general population to develop severe thalassemia, and the long\u2010term damage is much greater. Therefore, the clinical diagnosis of concurrent \u03b1\u2010 and \u03b2\u2010thalassemia should not be ignored. According to Xiong Fu et al.,In addition, 64 cases (2.19%) with concurrent \u03b1\u2010 and \u03b2\u2010thalassemia were detected in 2923 positive samples. Patients with concurrent \u03b1\u2010 and \u03b2\u2010thalassemia have been reported to suffer from mild anemia due to a reduction in \u03b1\u2010 and \u03b2\u2010globin chain synthesis, which alleviates the imbalance caused by reduced globin chain synthesis and thus reduces the severity of anemia.SEA/\u03b1\u03b1 was lower than that of \u2010\u03b13.7/\u03b1\u03b1 and \u2010\u03b14.2/\u03b1\u03b1 (p\u2009<\u20090.05); this may be related to the number of inactivated \u03b1\u2010globin genes of \u2010\u2010SEA/\u03b1\u03b1 were more than \u2010\u03b13.7/\u03b1\u03b1 and \u2010\u03b14.2/\u03b1\u03b1. Patients with \u2010\u2010SEA/\u03b1\u03b1 were associated with more severe anemia and came to the hospital earlier for diagnosis and treatment. Chen Suqin et al.4.2 or \u2010\u03b13.7 variants. Thus, the absence of \u03b1\u2010globin peptide chains or the relative excess of \u03b2\u2010globin peptide chains is more severe in non\u2010deletional patients. The hematologic appearance of patients with non\u2010deletional genotype of \u03b1\u2010thalassemia differs from that patients with deletional genotype of \u03b1\u2010thalassemia; anemia is more severe in patients with non\u2010deletional genotype of \u03b1\u2010thalassemia.p\u2009<\u20090.05).It may be related to the damage of erythrocyte membrane caused by excess \u03b2\u2010chain oxidation and \u03b1QS\u03b1 or \u03b1CS\u03b1 chain oxidation. This results in decreased EPO production and RBC in non\u2010deletional genotypes of \u03b1\u2010thalassemia.QS\u03b1/\u03b1\u03b1's Hb was lower than \u2010\u03b13.7/\u03b1\u03b1 and \u2010\u03b14.2/\u03b1\u03b1, which was partly supported that anemia in the non\u2010deletional genotype was more severe than in the deletional genotype. Patients with \u2010\u2010SEA/\u03b1\u03b1 were found to have higher RBC, HbF, and SF, it may be related to \u2010\u2010SEA/\u03b1\u03b1 was associated with more \u03b3\u2010globin mutations, and its RBC synthesis requires more iron, so the RBC, HbF, and SF were higher than \u2010\u03b13.7/\u03b1\u03b1.SEA/\u03b1\u03b1 were lower than \u2010\u03b13.7/\u03b1\u03b1 and \u2010\u03b14.2/\u03b1\u03b1 in the three common deletional genotypes, suggesting that the severity of anemia depends on the number of inactivated \u03b1\u2010globin genes.There is significant variation in clinical severity among patients with \u03b1\u2010thalassemia, which is indirectly reflected by the span of age at first diagnosis. Age of \u2010\u2010In conclusion, the clinical manifestations and hematologic phenotypes of \u03b1 \u2010thalassemia are related to genotype. The clinical phenotype of \u03b1\u2010thalassemia is influenced by molecular mechanisms. HBA1: c.16G>A is a novel mutation that was first reported in Fujian province. The discovery of this novel mutation in \u03b1\u2010globin gene has enriched the database of hemoglobin variants, and the detailed genetic analysis and clinical symptom description of this mutation will contribute to the further study of hemoglobin function in the future.Yali Pan, Meihuan Chen, Na Lin, Liangpu Xu, and Hailong Huang designed and prepared the study. YanHong Zhang, Min Zhang, and Lingji Chen collected the literature and the data and prepared the study. All authors approved the final study.This work was funded by the National Natural Science Foundation of China (no.81970170), the National Natural Science Foundation of Fujian Province (no.2019J01510), and the Fujian provincial health technology project (no.2018\u20101\u201021).The authors confirm that they have no competing interests."}
{"text": "Erratum to:Z Gerontol Geriat 202110.1007/s00391-021-02003-5The authors would like to apologize for an error concerning the mCAM-ED and make the following corrections:Page 109, Table\u00a02, mCAM-EDColumn: Screening vs. monitoring/Items:2.\u00a0If inattention present\u202f\u2192\u2009MSQ for identifying cognitive impairment, Comprehension subtest of CTD for identifying disorganized thinkingColumn: ScoringModified CAM algorithm: 1a\u00a0(acute onset) AND 1b\u00a0(fluctuating course)\u202f+\u20092\u202f+\u2009(3\u00a0or 4) positive\u202f=\u2009diagnosed delirium1a\u00a0OR 1b\u202f+\u20092\u202f+\u2009(3\u00a0or 4) positive\u202f=\u2009suspected delirium.Page 111, Legend table\u00a02:SPMSQ: MSQ mental status questionnaire.As a\u00a0replacement for"}
{"text": "Erep) is dominant.In the crystal, hydrogen-bonding inter\u00adactions between the 2,4,6-tri\u00adamino\u00adpyrimidine cation and the nitrate anions lead to a one-dimensional supra\u00admolecular network with weak anionic inter\u00adactions forming a three-dimensional network. Energy framework analysis showed that of the components of the framework energies, electrostatic repulsion \u00b0 between the mean plane of the cation and that defined by both anions. In the crystal, hydrogen-bonding inter\u00adactions between the 2,4,6-tri\u00adamino\u00adpyrimidine cation and the nitrate anions lead to a one-dimensional supra\u00admolecular network with weak anionic inter\u00adactions forming a three-dimensional network. These inter\u00adactions were investigated using Hirshfeld surface analysis, which indicates that the most important contributions for the packing arrangement are from O\u22efH/H\u22efO (53.2%), N\u22efH/H\u22efN (12.5%) and C\u22efH/H\u22efC (9.6%) inter\u00adactions. Energy framework analysis showed that of the components of the framework energies, electrostatic repulsion (Erep) is dominant.The title compound, C The plane of the anion containing N6 is inclined to the mean plane of the cation by 3.25\u2005(6)\u00b0 while that of the other anion is inclined by 2.84\u2005(6)\u00b0. Thus the whole asymmetric unit lies close to a common plane . The ring C\u2014N bond lengths in the cation [C1\u2014N2 = 1.3531\u2005(16)\u2005\u00c5 and C2\u2014N3 = 1.3267\u2005(16)\u2005\u00c5] are only slightly altered from those in the corresponding conjugate base . Pairs of adjacent ribbons are linked by N1\u2014H1B\u22efO3, N2\u2014H2\u22efO1 and N3\u2014H3A\u22efO3 hydrogen bonds  with O3\u22efCg1i = 3.1369\u2005(11)\u2005\u00c5, N6\u22efCg1i = 3.4241\u2005(12)\u2005\u00c5, N6=O3\u22efCg1i = 92.16\u2005(7)\u00b0; O5\u22efCg1ii = 3.0265\u2005(11)\u2005\u00c5; N7\u22efCg1ii = 3.5176\u2005(12)\u2005\u00c5; N7=O5\u22efCg1ii = 102.62\u2005(7)\u00b0 \u00b0 Fig.\u00a03.4.et al. 2009et al., 2007Crystal Explorer17  through white to blue . Top and bottom views of the surface together with curvedness, and shape-index plots are given in Fig.\u00a04a\u2013d. The red spots symbolize N\u2014H\u22efO contacts and C\u2014H\u22efO inter\u00adactions. The fingerprint plots , followed by N\u22efH/H\u22efN contacts at 12.5%  and C\u22efH/H\u22efC contacts at 9.6% .The Hirshfeld surface is mapped over ts Fig.\u00a05 give an 2% Fig.\u00a05b, follo5% Fig.\u00a05c and C\u22ef6% Fig.\u00a05d.5.To synthesize the title compound, 20\u2005mg of 2,4,6-tri\u00adamino\u00adpyrimidine were dissolved in ethanol (10\u2005mL) and the solution stirred for 3\u2005h. A mixture of ethanol (5\u2005mL) and nitric acid (0.5\u2005mL) was taken in a separate round-bottom flask and stirred for 3\u2005h at 333\u2005K. Afterwards, the 2,4,6-tri\u00adamino\u00adpyrimidine solution was added dropwise to the above mixture. The reaction was continued for 4\u2005h at the same temperature. After completion of the reaction, a pale-yellow solution was obtained, which was filtered and kept for slow evaporation at room temperature. After 15 days, pale-yellow crystals were obtained that were suitable for data collection Fig.\u00a06.6.CrystalExplorer 17.5. Electrostatic (Eele), polarization (Epol), dispersion (Edisp), and exchange-repulsion (Erep) are the four energy variables that make up the total inter\u00admolecular inter\u00adaction energy (Etot). Cylinder-shaped energy frameworks represent the relative strengths of inter\u00adaction energies in individual directions and give the topologies of pair-wise inter\u00admolecular inter\u00adaction energies within the crystal  = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022005333/mw2185sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022005333/mw2185Isup2.hklStructure factors: contains datablock(s) I. DOI: 2173730CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The layers are connected by C\u2014H\u22efCl hydrogen bonds and C\u2014H\u22ef\u03c0(ring) inter\u00adactions, forming a three-dimensional structure.The meth\u00adoxy group lies very close to the plane of the phenyl ring while the acetamido group is twisted out of this plane. In the crystal, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds form layers of mol\u00adecules parallel to the  9H10ClNO2, the meth\u00adoxy group lies very close to the plane of the phenyl ring while the acetamido group is twisted out of this plane by 28.87\u2005(5)\u00b0. In the crystal, a three-dimensional structure is generated by N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds plus C\u2014H\u22ef\u03c0(ring) inter\u00adactions. A Hirshfeld surface analysis of the inter\u00admolecular inter\u00adactions was performed and indicated that C\u22efH/H\u22efC inter\u00adactions make the largest contribution to the surface area (33.4%).In the title mol\u00adecule, C The Cl1\u2014C1\u2014C2\u2014O1 torsion angle is 52.89\u2005(12)\u00b0, illustrating a + synclinal (+ gauche) conformation about the C1\u2014C2 bond. This places atom Cl1 at 1.299\u2005(1)\u2005\u00c5 from the plane defined by C1, C2, N1 and O1.The meth\u00adoxy group lies close to the mean plane of the phenyl ring C3\u2013C8, as indicated by the C7\u2014C6\u2014O2\u2014C9 torsion angle of \u2212174.61\u2005(10)\u00b0 and atom C9 deviating by only 0.065\u2005(1)\u2005\u00c5 from the mean plane through the C3\u2013C8 ring. In contrast, the acetamido group is rotated out of the above plane with the dihedral angle between the mean plane through the C3\u2013C8 ring and that defined by N1/C2/C1/O1 being 28.87\u2005(5)\u00b0 Fig.\u00a01. The sum3.1 axes. These chains are linked by C1\u2014H1A\u22efO2 hydrogen bonds  yielded 15 hits of which 13 had X = Cl and R = OEt ) (SPh)(NO2) , O\u22efH/H\u22efO (19.5%) and Cl\u22efH/H\u22efCl (20%) inter\u00adactions, respectively.The analysis was performed with 6.0.047\u2005mol of 4-methoxyaniline were dissolved in 40\u2005mL of pure acetic acid and put in an ice bath. Subsequently, chloro\u00adacetyl chloride (0.047\u2005mol) was added portionwise under stirring. At the end of the reaction, a solution of sodium acetate (35\u2005mL) was added and a solid precipitate appeared after 30\u2005min of stirring at room temperature. The resulting solid was filtered and washed with cold water, dried and recrystallized from ethanol to give the title compound as colourless crystals.\u22121) 3292 (\u03c5 N\u2014H amide), 1029 (\u03c5 N\u2014C amide), 1660 (\u03c5 C=O amide), 3073 (\u03c5 C\u2014Harom), 827 (\u03c5 C\u2014Cl), 2959 , 1H NMR (DMSO\u2013d6) \u03b4 pm: 3.74 ; 4.24 , 6.93\u20137.5 , 10.23 , 13C NMR (DMSO\u2013d6) \u03b4 ppm: 43.48 (CH2), 55.23 (CH3), 131.53 (Carom\u2014N), 155.51 (Carom\u2014O), 113.92\u2013120.92 (Carom), 164.13 (C=O); HRMS (ESI\u2013MS) (m/z) calculated for C9H10ClNO2 199.04, found 199.0105.Yield 80%, m.p. = 398.6\u2013400.3\u2005K, FT\u2013IR  (1.5 for the methyl group). The N-bound H atom was found in a difference-Fourier map and refined with a DFIX 0.91 0.01 instruction and an independent isotropic displacement parameter.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902200576X/vm2264sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698902200576X/vm2264Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902200576X/vm2264Isup3.cmlSupporting information file. DOI: 2175514CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing of the title compound features weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. 22H20O3, the dihedral angle between the aromatic rings linked by the methine group is 81.265\u2005(4)\u00b0 and the eth\u00adoxy side chain adopts an extended conformation [C\u2014O\u2014C\u2014C = 177.24\u2005(10)\u00b0]. In the crystal, weak C\u2014H\u22ef\u03c0 and C\u2014H\u22efO inter\u00adactions link the mol\u00adecules into sheets.In the title compound, C These link the mol\u00adecules into sheets lying perpendicular to the c-axis direction \u00b0. In the crystal, weak C\u2014H\u22efO Table\u00a01 and C\u2014H\u22efon Fig.\u00a02.3-Eth\u00adoxy-4-hy\u00addroxy benzaldehyde (0.20\u2005mmol) and potassium carbonate (0.40\u2005mmol) were mixed in di\u00admethyl\u00adformamide (25\u2005ml) and stirred for 0.5\u2005h. A solution of di\u00adphenyl\u00adbromo\u00admethane (0.2\u2005mmol) in ethanol (20\u2005ml) was added dropwise and the mixture was stirred at 80\u00b0C for 24\u2005h. After that, the solution was concentrated under reduced pressure. The cream precipitate of the title compound formed by adding cold water (250\u2005ml) was filtered off and washed several times with cold ethanol. Colourless slabs were recrystallized from the mixed solvents of chloro\u00adform and ethanol (1:1).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621003564/hb4378sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314621003564/hb4378Isup2.hklStructure factors: contains datablock(s) I. DOI: 2075001CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Such ICCs are of potential utility, and there arenumerous examples of phenolic compounds that are biologically active,some of which suffer from low aqueous solubility. The propensity toform ICCs sustained by the PhOH\u00b7\u00b7\u00b7PhO\u2013 supramolecular heterosynthon was evaluated through a combinationof Cambridge Structural Database (CSD) mining, structural characterizationof nine novel ICCs, and calculation of interaction energies. Our analysisof these 9 ICCs and the 41 relevant entries archived in the CSD revealedthat phenol groups can reliably form ICCs through charge-assistedPhOH\u00b7\u00b7\u00b7PhO\u2013 interactions. This conclusionis supported by hydrogen-bond strength calculations derived from CrystalExplorerthat reveal the PhOH\u00b7\u00b7\u00b7PhO\u2013 interactionto be around 3 times stronger than the phenol\u2013phenol hydrogenbond. The PhOH\u00b7\u00b7\u00b7PhO\u2013 supramolecularheterosynthon could therefore enable crystal engineering studies ofa large number of phenolic pharmaceutical and nutraceutical compoundswith their conjugate bases.Although crystalengineering strategies are generally well exploredin the context of multicomponent crystals  formed by neutralcoformers , cocrystals comprised of one or moresalts  are understudied. We herein addressthe design, preparation, and structural characterization of ICCs formedby phenolic moieties, a common group in natural products and drugmolecules. Organic and inorganic bases were reacted with the followingphenolic coformers: phenol, resorcinol, phloroglucinol, 4-methoxyphenol,and 4-isopropylphenol. Nine ICCs were crystallized, each of them sustainedby the phenol\u2013phenolate supramolecular heterosynthon (PhOH\u00b7\u00b7\u00b7PhO CambridgeStructural Database mining and experimental studiesof model compounds reveal that ionic cocrystals sustained by phenol\u00b7\u00b7\u00b7phenolatehydrogen bonds are formed reliably Etter systematicallyclassified common hydrogen-bonding motifs using \u201cgraph set\u201dnotation Gda(r), where G is the pattern designator that could be C (chain), R (ring),and D (dimer or other finite set); a represents the number of acceptors; d is the number of donors; and r is thenumber of atoms in the repeat unit.18 Graph settheory remains a valuable tool for researchers to compare structuresto this day. Shortly after, Desiraju introduced the term \u201csupramolecularsynthon\u201d to represent a structural unit or building block incrystal structures.19 Supramolecular synthonswere subclassified by us in 2003 into supramolecular homosynthons,between the same functional groups  and supramolecular heterosynthons and between differentbut complementary functional groups .14 The understandingof supramolecular synthons, their geometries, and their frequencyof occurrence in the Cambridge Structural Database (CSD) is key tothe rational design of novel multicomponent crystal forms such ascocrystals and hydrates.20Certain intermolecular interactions,such as neutral and charge-assistedhydrogen bonds, and coordination bonds, are amenable to crystal engineeringstudies thanks to their relatively high strength, predictability,ubiquity, and directionality.21 Cocrystals are of interestin part because they can be readily accessible and amenable to crystalengineering. Cocrystals include molecular cocrystals22 (MCCs), which are comprised of two or more nonvolatileneutral molecules (coformers), and ionic cocrystals23 (ICCs), which involve at least one coformer that is a salt.ICCs are necessarily sustained by charge-assisted hydrogen bonds or,if metal ions are involved, coordination bonds.25 ICCs are therefore comprised of at least three components, a cation,an anion, and an additional molecule or salt. Given that MCCs of acompound typically offer a single variable, the coformer, ICCs canexhibit greater diversity in terms of composition and physicochemicalproperties compared to MCCs.4 Additionally,if an ICC is formed in which one coformer is an API and another isan API salt, then this type of ICC provides an opportunity to generatelow-dosage solid forms since the biologically active component(s)represent most of the mass of the ICC. Although ICCs are generallyless studied than MCCs, the first cocrystal involving sodium chlorideand urea was an ICC26 and, to our knowledge,at least five ICCs have been selected and developed for use in marketeddrug products: Depakote 27 in 1983; Lexapro 28 in 2002; Odomzo 29 in 2015; Entresto 30 in 2015; Seglentis (celecoxib and tramadol hydrochloride)31 in 2021.Cocrystalsare solids that are crystalline single-phase materialscomprised of two or more different molecular and/or ionic compoundsgenerally in a stoichiometric ratio that are neither simple saltsnor solvates.2+ and l-ascorbicacid, and inhibit the formation of oxygen free radicals.33 Statistically, ca. 8.7% of approved small-molecule drugs containedin DrugBank Online (Version 5.1.9.)34 arephenolic drugs, and phenol groups are present in ca. 10.1% of single-componentbiologically active compounds archived in the CSD (Scheme S1). However, many such compounds exhibit low aqueoussolubility and would therefore be classified as BCS class II.35 Their efficacy would therefore be hindered andan otherwise promising drug molecule could be rendered unsuitablefor use in an orally delivered drug product.37 Molecular cocrystals are now well known to modulate the physicochemicalproperties of phenolic compounds including solubility,38 bioavailability,39 stability,40 and mechanical properties41 while preserving their inherent biological activity.Phenolic drug molecules and nutraceuticalcompounds are of topicalinterest because they can exhibit biological effects such as antioxidantand anti-inflammatory activity, inhibit lipid peroxidation initiatedin rat brain homogenates by Fe20 carboxylate moieties,42 and aromatic nitrogen bases.43 Conversely,the phenol\u2013phenolate (PhOH\u00b7\u00b7\u00b7PhO\u2013) interaction is considered to be a strong hydrogen bond. In solution,PhOH\u00b7\u00b7\u00b7PhO\u2013 systems known as homoconjugatedcomplexes readily form as measured by their conjugated constants.44 PhOH\u00b7\u00b7\u00b7PhO\u2013 complexes can have a negative impact on titration experiments andplay an important role in enzyme catalysis.45 Buytendyk et al. reported the PhOH\u00b7\u00b7\u00b7PhO\u2013 interaction energy in the gas phase to be as high as 26\u201330kcal/mol, 60% of that of the HF\u00b7\u00b7\u00b7F\u2013 interaction, the strongest hydrogen bond known.46 Crystal structures involving PhOH\u00b7\u00b7\u00b7PhO\u2013 interactions archived in the CSD were mainly studiedfor structural insight47 or applicationssuch as organic synthesis (Kolbe\u2013Schmitt synthesis)49 and NLO.50 As such, there remains a lackof systematic crystal engineering studies on ICCs containing the PhOH\u00b7\u00b7\u00b7PhO\u2013 supramolecular heterosynthon.With respect to crystal engineering, phenols offer medium hydrogen-bonddonor strength and are established as being able to form supramolecularheterosynthons with hydrogen-bond acceptors such as chloride anions,\u2013 supramolecular heterosynthons. Specifically, phenoland four other substituted phenol derivatives were selected as modelcompounds and reacted with tetraalkylammonium hydroxides and potassiumhydroxide (\u2013 and phenol\u2013phenol (PhOH\u00b7\u00b7\u00b7PhOH)interactions in the obtained ICCs were examined using CrystalExplorer.In this contribution,we address ICC formation involving phenolsthrough a systematic CSD and experimental study that explores PhOH\u00b7\u00b7\u00b7PhOydroxide 1.In addPHNTMA; phenol\u00b7phenolate\u00b7potassium, PHNKOH; 1,3,5-benzentriol\u00b71,3,5-benzentriolate\u00b7tetramethylammonium, PGNTMA; 1,3,5-benzentriol\u00b71,3,5-benzentriolate\u00b7tetraethylammonium, PGNTEA; 4-isopropylphenol\u00b74-isopropylphenolate\u00b7potassium, IPPKOH; 4-isopropylphenol\u00b74-isopropylphenolate\u00b7tetrapropylammonium, IPPTPA; 4-isopropylphenol\u00b74-isopropylphenolate\u00b7tetrabutylammonium, IPPTBA; 4-methoxyphenol\u00b74-methoxyphenolate\u00b7tetrabutylammonium, MOPTBA; and resorcinol\u00b7resorcinolate\u00b7tetramethylammonium, RESTMA.A library of cocrystal formers containing five phenolderivatives,four organic bases, and one inorganic base was chosen for this study1. CocrysAll reagents and chemicals were purchasedfrom Sigma-Aldrich and used without further purification. Single crystalsof ICCs were obtained via slow evaporation of stoichiometric amountsof starting materials in a range of solvents at room temperature andharvested from solution before complete evaporation of their motherliquors had occurred.PHN  andTMA  were dissolved in 10 mL of acetonitrile (MeCN).The solvent was evaporated under vacuum until a viscous liquid wasobtained. Colorless crystals were harvested after exposing the viscousliquid to ambient conditions overnight.PHN  and KOH  were dissolved in 1 mL of methanol (MeOH). Thesolution was slowly evaporated at room temperature, and colorlesscrystals were obtained after 1 day.PGN  and TMA  were dissolved in 1 mL of MeOH. The solutionwas slowly evaporated at room temperature, and colorless crystalswere obtained after 1 day.PGN  andTEA  were dissolved in 1 mL of MeOH. The solutionwas slowly evaporated at room temperature, and colorless crystalswere obtained after several hours.2O) were dissolved in 1 mL of MeOH. Thesolution was slowly evaporated at room temperature, and colorlesscrystals were obtained after 1 day.IPP  and KOH  were dissolved in 1 mL of MeCN. The solutionwas slowly evaporated at room temperature, and colorless crystalswere obtained after 1 day.IPP  and TPA  were slurried in 1 mL of H2O overnight. The undissolved solid was isolated by filtration anddried in an oven. Colorless single crystals were obtained by dissolvingthe solid in MeOH, followed by slow evaporation at room temperature.IPP  andTBA , followed by slow evaporation at room temperature.MOP  and TBA  were slurried in 2 mL of HRES , IPP ,and TMA  were dissolved in 1 mLof MeOH. The solution was slowly evaporated at room temperature, andcolorless crystals were obtained after 1 week.All PXRD data werecollected on an Empyrean diffractometer  with the followingexperimental parameters: Cu K\u03b1 radiation (\u03bb = 1.54056\u00c5); 40 kV and 40 mA; scan speed 8\u00b0/min; step size 0.05\u00b0,2\u03b8 = 5\u201340\u00b0.51 Structures were solved using SHELXT and refinedusing SHELXL contained in Olex2.52 Reflectiondata for the nonhydrogen atoms were refined anisotropically. All hydrogenatoms bonded to carbon  were placed geometrically and refined using a ridingmodel with isotropic thermal parameters: Uiso(H) = 1.5Ueq(\u2212CH3), Uiso(H) = 1.2Ueq(\u2212CH), Uiso(H) = 1.2Ueq(\u2212CH2). Hydrogen atoms on water (AFIX 5) and methanol (AFIX 147)were calculated geometrically and refined using a riding model withisotropic thermal parameter: Uiso(H) =1.5Ueq(\u2212OH). The hydrogen atomsof phenolic hydroxyl groups were located from electron density differencemaps and included in the refinement process using a riding model with Uiso(H) = 1.2Ueq(\u2212OH).Single-crystal data are presented in Crystal structureswere determined by single-crystal X-ray diffraction(SCXRD) with either Cu K\u03b1 (\u03bb = 1.5418 \u00c5) radiationor Mo K\u03b1 (\u03bb = 0.71073 \u00c5) radiation and a Bruker D8Quest fixed-chi diffractometer equipped with a Photon 100 detectorand the nitrogen-flow Oxford Cryosystem attachment. Unit cell determination,data reduction, and absorption correction (multiscan method) wereconducted using the Bruker APEX3 suite with implemented SADABS software.R factor \u2264 0.05, no disorder andsingle-crystal structure only) was conducted to find crystal structuresthat contain PhOH\u00b7\u00b7\u00b7PhO\u2013 interactions.The following parameters were addressed by the search: (1) numberof structures that exhibit phenol\u2013phenolate interactions excludingsingle-component structures, salts, and zwitterions; (2) number ofstructures that form a PhOH\u00b7\u00b7\u00b7PhOH supramolecular homosynthon;(3) number of structures that contain a phenol group or a phenolateanion with the restriction that only C, H, and O were considered assubstituents on the phenyl ring . The distance distribution of phenol\u2013phenolateand phenol\u2013phenol hydrogen bonds and the bond length distributionof the C\u2013O bond of the phenol or phenolate group were plottedbased on data from Searches 1, 2, and 3. The schematic structuresused in searches 1, 2, and 3 are presented in ACSD survey  level in the CrystalExplorerprogram package followed by geometry optimization carried out usingthe CASTEP module with GGA-type PBE functional contained in MaterialsStudio 8.0. The total interaction energy was partitioned into electronic(E_ele), polarization (E_pol), dispersion (E_dis), and repulsion (E_rel)components.\u2013 interactions are present. Of these entries, 69 (44.2%)are single-component compounds with phenol and phenolate moietiesin the same molecule; 30 entries (19.2%) are salts, and 15 (9.6%)are zwitterionic cocrystals or solvates composed of a zwitterion anda neutral molecule; 42 (26.9%) structures meet the definition of anICC that contains a phenol molecule, phenolate anion, and cation.However, of these 42 cocrystals, only one paper54 classifies them as cocrystals (refcode: JICKIS).Our CSD search retrieved 156 entries in which PhOH\u00b7\u00b7\u00b7PhO\u2013 O\u00b7\u00b7\u00b7O\u2013 bond distance determined from 42 ICC structures rangedfrom 2.4195(52)\u20132.6599(24) \u00c5 with an average of 2.528\u00b1 0.08\u00c5. A histogram of the O\u00b7\u00b7\u00b7O\u2013 distance distribution for PhOH\u00b7\u00b7\u00b7PhO\u2013 interactions is presented in The PhOH\u00b7\u00b7\u00b7PhOO\u2013H\u00b7\u00b7\u00b7Obond distances of PhOH\u00b7\u00b7\u00b7PhOH interactions determinedfrom search 2 ranged from 2.5218(28)\u20133.0381(45) \u00c5, averaging2.812 \u00b1 0.103 \u00c5. A histogram of the O\u2013H\u00b7\u00b7\u00b7Ohydrogen-bond distance distribution for PhOH\u00b7\u00b7\u00b7PhOHinteractions is presented in \u2013 bonds range from 1.2341(27) to 1.3776(95) \u00c5 witha mean of 1.307 (0.023) \u00c5. The distribution plots in CSD search3 addressed the C\u2013O bond length in phenols vs phenolates. TheCSD was found to contain 8277 and 192 entries for phenols and phenolates,respectively. \u2013\u00b7\u00b7\u00b7PhOH; PhOH\u00b7\u00b7\u00b7PhOH;PhO\u2013\u00b7\u00b7\u00b7H2O/MeOH; PhOH\u00b7\u00b7\u00b7H2O/MeOH. Tetramethylammonium (TMA), tetraethylammonium (TEA),tetrapropylammonium (TPA), and tetrabutylammonium (TBA) cations exhibitno strong hydrogen bonds. Rather, coulombic forces occur with phenolateanions. The neutral or ionic nature of phenolic groups in the nineICCs was addressed through proton location56 from difference Fourier map inspection and C\u2013O bond lengths. Table S1 lists the C\u2013O bond lengths inthe neutral (C\u2013OH) and deprotonated (C\u2013O\u2013) moieties.Hydrogen bonds werefound to be present in each of the nine novel ICCs reported herein:PhO\u2013 and PhO\u2013\u00b7\u00b7\u00b7H2O hydrogen bonds. PHNTMA crystallized in the space group P21/c. Theasymmetric unit of PHNTMA contains three phenol molecules, three phenolateanions, three TMA cations, and three water molecules in the ratioof 1:1:1:1 (R1410(28) (\u2013 hydrogen bonds withinthe discrete unit exhibit O\u00b7\u00b7\u00b7O\u2013 bonddistances of 2.438(2), 2.434(2), and 2.466(2) \u00c5. At the (100)plane, adjacent discrete units are arranged vertically and interactvia TMA cations. The discrete units align along the a-axis.PHNTMA, IPPTPA, IPPTBA, and MOPTBA formed discreteadducts. PHNTMA and IPPTBA crystallized as hydrates sustained by PhOH\u00b7\u00b7\u00b7PhO 1:1:1:1 2a. Four 1410(28) 2b. The rP21/c (R42(8) hydrogen-bondedring with each molecule interacting with an extra IPP molecule outsidethe ring to generate a discrete unit (\u2013 hydrogen bond with O\u00b7\u00b7\u00b7O\u2013 = 2.528(3) \u00c5. IPP serves as a hydrogen-bond donor and is hydrogen-bondedto a water molecule in each motif. The discrete units are connectedby TBA cations and aligned along the a-axis.IPPTBA crystallized as a 2:1:1:1 ICC of 4-isopropylphenol, 4-isopropylphenolate,TBA, and water in the space group P21/c 2c. Two 4ete unit 2d. The rP1\u0305 with one (Z\u2032 = 1) and two (Z\u2032 = 2) formula units in the asymmetric unit, respectively.In both structures, two discrete hydrogen-bonding assemblies existin each asymmetric unit, forming two different motifs C32(7) and C21(5) in IPPTPA (C32(7) motifs in MOPTBA \u00c5, 2.562(2) \u00c5, 2.571(3) \u00c5, 2.589(3) \u00c5; O\u00b7\u00b7\u00b7O\u2013 distances in MOPTBA: 2.5920(16) \u00c5, 2.4413(17)\u00c5, 2.4369(17) \u00c5, 2.6111(17) \u00c5). CH\u00b7\u00b7\u00b7Ointeractions and cations link the discrete units.IPPTPA and MOPTBA both crystallized in space group n IPPTPA 3a andtwn MOPTBA 3b. These48 Herein,single crystals of PHNKOH were grown from MeOH and are isostructuralwith HERCIQ but with a lower unit cell volume (4359.37 vs 4494.18\u00c53), presumably due to data collection at 150 K vsroom temperature. IPPKOH crystallized in P21/n. Althoughthey adopt different space groups, PHNKOH and IPPKOH both exhibitasymmetric units comprising three phenol molecules, one potassiumcation, and one phenolate anion in a 3:1:1 ratio. Each potassium cationadopts octahedral coordination geometry with five oxygen atoms fromphenol molecules (or phenol moieties of IPP), and the sixth coordinationsite is occupied by the \u03c0 system of a phenolate anion (S1a). The 1D coordination polymers in PHNKOHand IPPKOH form zigzag chains (S1b) that are supportedby three nonequivalent charge-assisted hydrogen bonds between eachphenolate moiety and three phenol moieties (O\u00b7\u00b7\u00b7O\u2013 in PHNKOH = 2.5276(18) \u00c5, 2.6052(19) \u00c5,2.6315(19) \u00c5; O\u00b7\u00b7\u00b7O\u2013 in IPPKOH= 2.541(2) \u00c5, 2.617(2) \u00c5, 2.546(3) \u00c5).PHNKOH and IPPKOH form one-dimensional (1D) coordinationpolymers.The structure of PHNKOH  and its 2:1:1 variant (CSD Refcode HEQZUY) were previouslyreported as phenol solvates of potassium phenolate from high-resolutionPXRD data by Dinnebier et al.RESTMA isa 1:1:1 ICC of resorcinol, resorcinolate,and TMA  hydrogen-bonded networks. Deprotonated resorcinol serves as ahydrogen-bond donor and acceptor since only one hydroxyl group isdeprotonated. The phenolate moieties of the resorcinolate anion formthree charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds. The resorcinolate anions interact with each otherto form a chain supported by PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds. These interactions result in perpendicular chainsbridged by resorcinol molecules, resulting in grid-like networks  and one water molecule (PhO\u2013\u00b7\u00b7\u00b7H2O). Two phenolate moieties hydrogen-bond to phenolic groupsvia PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds  ring motif to expandinto a ladder-like plane composed of rails  hydrogen-bonded networks through PhO\u2013\u00b7\u00b7\u00b7MeOHand PhOH\u00b7\u00b7\u00b7MeOH hydrogen bonds, respectively  also feature PhOH\u00b7\u00b7\u00b7PhOHsupramolecular homosynthons. The two most common motifs observed arethose in which a phenolate moiety interacts with two  or three hydroxyl donors . Phenols are generally more acidic than aliphaticalcohols but less acidic than most carboxylic acids. This study presentsa strategy to form ICCs of phenols and their conjugate bases by PhOH\u00b7\u00b7\u00b7PhO\u2013 interactions to drive and sustain crystal packing.It is a well-recognized rule of thumb for salt and cocrystal screeningthat if \u0394pKa (\u0394pKa = pKa (base)-pKa (acid)) is >3, then a salt is formed and that if \u0394pKa is <0, then a cocrystal is favored.57 In this work, \u0394pKa is >3 for all bases used, and as such, proton transferwasanticipated even though proton transfer could have been affected byfactors such as solvent and the composition of starting materials.In this study, several solvent systems were used for ICC screening.Except for PHNTMA, only the use of MeOH or H2O as solventafforded high-quality single crystals suitable for SCXRD data collection.Poor quality crystals or gel-like phases were produced using ethanol,2-propanol, or acetone.As detailed above, charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 and PhOH\u00b7\u00b7\u00b7PhOHinteractions in the nine new ICCs reported herein are tabulated in Table S2 and presented as a scatter plot in Table S2), and the average strengthis presented in Selectedhydrogen bond lengthsfor PhOH\u00b7\u00b7\u00b7PhO\u2013 and PhOH\u00b7\u00b7\u00b7PhOH hydrogen-bond distancesin the ninenovel ICCs fall in the \u201cred zone\u201d and \u201cgreenzone\u201d, respectively. These distance zones are based upon O\u00b7\u00b7\u00b7O\u2013 distance ranges in PhOH\u00b7\u00b7\u00b7PhO\u2013 and PhOH\u00b7\u00b7\u00b7PhOH hydrogen bonds (\u00c5), respectively,determined from crystal structures archived in the CSD. PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds were found to exhibit relatively shortdistances (2.427(2)\u20132.658(2) \u00c5) and angles nearing 180\u00b0,whereas PhOH\u00b7\u00b7\u00b7PhOH hydrogen-bond distances were longer(2.825(3)\u20132.6289(19) \u00c5) and angles were more acute (149(5)\u2013177(8)\u00b0).Some charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogenbonds have relatively long O\u00b7\u00b7\u00b7O\u2013 distances or small angle values (2.6315(19) \u00c5, 161(3)\u00b0in PHNKOH; 2.617(2) \u00c5, 158(8)\u00b0 in IPPKOH; 2.726(3) \u00c5,180(7)\u00b0 in PGNTEA). These parameters are likely affected by thedifferent crystal packing environment in each crystal structure. Nevertheless,as expected, charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds were found to be consistently shorter than PhOH\u00b7\u00b7\u00b7PhOHhydrogen bonds. Further, as presented in \u2013 interactions were calculated to offer ca. 3 times the energy ofPhOH\u00b7\u00b7\u00b7PhOH interactions, with average energies of91.6 \u00b1 8.1 and 28.53 \u00b1 0.67 kJ/mol, respectively. As alsodetailed in \u2013 and PhOH\u00b7\u00b7\u00b7PhOHhydrogen-bond strength. Specifically, for PhOH\u00b7\u00b7\u00b7PhOHinteractions, the electrostatic contribution comes from dipole\u00b7\u00b7\u00b7dipoleinteractions, whereas for PhOH\u00b7\u00b7\u00b7PhO\u2013 interactions, the phenolate oxygen and phenolic hydrogen are keyto the electrostatic contribution. The greater electrostatic energiesin PhOH\u00b7\u00b7\u00b7PhO\u2013 can therefore be attributedto coulombic forces. Polarization contributes to total energy forPhOH\u00b7\u00b7\u00b7PhO\u2013, while it is negligiblefor PhOH\u00b7\u00b7\u00b7PhOH. A small dispersion contribution wascalculated for all hydrogen bonds. Repulsion forces for PhOH\u00b7\u00b7\u00b7PhO\u2013 were consistently calculated to be greater than forPhOH\u00b7\u00b7\u00b7PhOH hydrogen bonds. Overall, although repulsiveforces for the charge-assisted hydrogen bonds are relatively high,the increase is more than offset by increases in permanent chargeand electronic and polarization forces. These high intermolecularinteraction energies and desirable hydrogen-bond geometry featuresvalidate that charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 hydrogen bonds are a strong and reliable interaction to enable theformation of ionic cocrystals.As shown by the scatter plot of \u2013 supramolecular heterosynthon is understudied in thecontext of crystal engineering of ICCs. To address this issue, ninenovel ICCs involving phenol and phenol-substituted compounds wereformed by reaction with bases and their crystal structures were determinedby SCXRD. Analysis of the resulting crystal structures revealed thatall nine ICCs are sustained by the phenol\u2013phenolate supramolecularheterosynthon with O\u00b7\u00b7\u00b7O\u2013 distancesranging from 2.427(2) to 2.658(2) \u00c5. A computational study validatedthe robustness of the charge-assisted PhOH\u00b7\u00b7\u00b7PhO\u2013 supramolecular heterosynthon vs. the phenol\u2013phenolsupramolecular homosynthon from an energetic perspective. Based onthese results, we consider that the PhOH\u00b7\u00b7\u00b7PhO\u2013 supramolecular heterosynthon is suitable for the reliableformation of ICCs of phenolic compounds, which are prevalent in drugmolecules and nutraceuticals. That phenols form ICCs with their conjugatebases is important from a pharmaceutical perspective as it means thatthe mass of a dosage form can be close to that of the parent phenol.Future studies will focus on pharmaceutical and nutraceutical cocrystals,their physicochemical properties, and polymorphism.Phenolgroups are found in 8.7% of approved small-molecule drugsin the DrugBank database and in 10.1% of bioactive single-componentcompounds deposited in the CSD. Our CSD survey revealed that the PhOH\u00b7\u00b7\u00b7PhO"}
{"text": "The packing of the title compound is consolidated by C\u2014H\u22efO inter\u00adactions. 23H19NO5, the cyano group adopts an axial orientation and the ester group an equatorial orientation. The dihedral angle between the pendant phenyl group and the benzene ring of the fused-ring system is 25.97\u2005(8)\u00b0. Intra\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds are observed and the packing is consolidated by C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, C H-benzo[c]chromen-6-ones or 3,4,5,6-dibenzo-\u03b1-pyran\u00adones) form an important group of biologically active natural products that occur in bacteria, fungi, lichens, higher plants and animal waste \u00b0. The Cremer\u2013Pople puckering parameters of the O1/C9/C10/C13\u2013C15 and C14/C15/C17\u2013C20 rings indicate half-chair conformations in each case with puckering amplitudes Q = 0.359\u2005\u00c5; \u03b8 = 104.52\u00b0; \u03c6 = 9.27\u00b0 and Q = 0.49\u2005\u00c5; \u03b8 = 134.17\u00b0; \u03c6 = 327.35\u00b0, respectively. The O atom attached to C17 is stabilized in its enol (hy\u00addroxy) form, presumably as a result of forming a strong intra\u00admolecular hydrogen bond to O2. The packing is consolidated by weak C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions , phenyl\u00adboronic acid , K3PO4  and Pd(PPh3)4  in degassed 1,4-dioxane (10\u2005mL) was stirred at 100\u00b0\u2005C for 12\u2005h under nitro\u00adgen. After completion of the coupling reaction (TLC), the mixture was cooled to room temperature, diluted with di\u00adchloro\u00admethane  and deca\u00adnted. The residue was extracted with DCM (10\u2005mL \u00d7 2) twice. The solvent was removed from the combined DCM layers and the residue was subjected to column chromatography on silica gel (100\u2013200 mesh) by using increasing amounts of ethyl acetate in hexane (5% to 15%) as eluent to afford the title compound as a light-yellow solid in 90% yield (84\u2005mg); Rf = 0.4 ; m.p. 155\u2013158\u00b0\u2005C. A sample suitable for single-crystal X-ray analysis was obtained by recrystallization the 50\u2005mg of the solid from a mixture of 1\u2005mL of distilled chloro\u00adform and 0.5\u2005mL of distilled methanol.A mixture of ethyl 10-cyano-7-hy\u00addroxy-6-oxo-3-{[(tri\u00adfluoro\u00admeth\u00adyl)sulfon\u00adyl]\u00adoxy}-8,9,10,10Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622001997/hb4401sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622001997/hb4401Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001997/hb4401Isup3.cmlSupporting information file. DOI: 2153368CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-isopropylacrylamide) (pNIPAM) and poly(N-tert-butylacrylamide) (pNTBAM) hydrogels were assessed in terms of their chemical differences, mechanical strength, internal architecture, porosity and capacity to support cell viability, migration, and differentiation. pNTBAM polymerized with a Young\u2019s modulus of up to 371\u2009\u00b1\u200931\u00a0kPa compared to the more flexible pNIPAM, 16.5\u2009\u00b1\u20090.6\u00a0kPa. Viability testing revealed biocompatibility of both hydrogels with significantly increased cell numbers observed in pNTBAM (500\u2009\u00b1\u200995 viable cells/mm2) than in pNIPAM (60\u2009\u00b1\u20093 viable cells/mm2) (P\u2009\u2264\u20090.05). Mineralization determined through alkaline phosphatase (ALP) activity, calcium ion and annexin A2 markers of mineralization) and osteogenic behaviour (collagen I expression) were supported in both hydrogels, but to a greater extent in pNTBAM. pNTBAM supported significantly elevated levels of chondrogenic markers as evidenced by collagen II and glycosaminoglycan expression in comparison to little or no evidence in pNIPAM (P\u2009\u2264\u20090.05). In conclusion, structurally similar, chemically distinct, acrylamide hydrogels display variable capacities in supporting osteochondral cell behaviours. These systems demonstrate spatial control of cell interaction through simple changes in monomer chemistry. Fine control over chemical presentation during the fabrication of biomaterial implants could lead to greater efficacy and targeted regeneration of semi-complex tissues.Regeneration solutions for the osteochondral interface depth are limited, where multi-material implants have the potential to delaminate affecting the regeneration process and impacting the final integrity of tissue interface. Here we explore regionally mixed hydrogel networks, presenting distinct chemical features to determine their compatibility in supporting osteogenic or chondrogenic cell behaviour and differentiation. Poly( Furthermore, material characteristics influence the cellular capacity to perform biological functions  and N-tert-butylacrylamide (NTBAM) have been described as co-polymers with potential to stimulate tissue regeneration including that of bone and cartilage  was used to link the polymer network. Ammonium persulfate (APS) 10% w/v initiator was used alongside N,N,N\u2032,N\u2032-tetramethylethylenediamine (TMED) 2.6% v/v as an accelerator. NIPAM formed a transparent soft gelatinous structure requiring 2\u20133\u00a0min to form after rapid addition of the initiator. NTBAM was formed in a 1:1 combination of water and methanol heated to 37\u00a0\u00b0C. pNTBAM hydrogel formation required 10\u201315\u00a0min to completely gelate.Hydrogels were prepared by liquid phase atom transfer radical polymerization (Matyjaszewski Hydrogels were observed using a bench-top Hitachi S4500 scanning electron microscope (SEM) at 5\u00a0kV. Hydrogels were frozen at \u2013\u00a020\u00a0\u00b0C, freeze dried, mounted onto carbon tape, and gold sputter coated. Pore size measurements were performed using Image J, with over 100 features measured per sample and 3 repeat samples measured.Measurement of water contact angle was performed using a \u201cTheta Lite Attension One Attension version 2.4\u201d system. Samples were placed on a glass petri dish and compressed with a cover slip to acquire a flat surface while being dried at 70\u00a0\u00b0C in an oven. Water droplets, measured at 1 \u03bcL, were slowly placed onto test surfaces. Four measures were collected from each sample out of 4 samples.Compressive strengths were measured with the BOSE Electroforce system equipped with a 20\u00a0N loading cell and cross head speed of 0.05\u00a0mm/s. The samples were cylindrical in shape with dimensions of 4.5\u20135.0\u00a0mm height and 9.4\u201311.5\u00a0mm diameter. The load was applied until strain reached 90%. Compressive strength was determined from the maximum load of the applied stress\u2013strain curve. Four samples of each hydrogel were tested, and an average obtained.L-glutamine. Culture environments were 37\u00a0\u00b0C in 5%\u00a0CO2 culture incubators with media changed every 5\u00a0days. Primary human osteoblasts (hOB) and primary human chondrocytes (hCH) were obtained commercially from Promo Cell\u00ae and cultured under the conditions described above. Routine trypsinization protocols were followed for cell passaging  and immortalized (human telomerase transcriptase (hTERT) transduced) chondrocytes (OK3H)  or chondrogenic induction supplements .Differentiation was induced by addition of either osteogenic induction supplements . The major components of the assay kit are calcein AM and ethidium homodimer-1 reagents. Calcein AM identifies the presence of live cells by detecting intracellular esterase activity and cell membrane integrity. Live/dead staining solution was prepared by mixing both reagents with PBS at the following rates; 1:200 of calcein AM and 1:50 of ethidium homodimer-1 in PBS. The cells viability profile was assessed after 21\u00a0days of cell culturing. The hydrogel samples were removed from media and washed 3 times with PBS. Next, these samples were incubated with 1\u00a0mL/sample of live/dead staining solution for 30\u00a0min at room temperature protected from light. Hydrogels were viewed under an Olympus U-TBI90 confocal microscope to observe the viable (green fluorescence) and the dead (red fluorescence) cells. The viability of cells upon hydrogel samples was identified by calculating the number of live and dead cells per specific regions of each sample. The number of live cells (green) and dead cells (red) were counted over a 1 mm2 area for a maximum of 5 regions of a captured\u2009\u00d7\u20094 microscopic images obtained for individual samples and the average was taken. The whole process was carried out using the cell counting tool of Image J software.Viability of cells was examined with the live/deadCell migration was established after 21\u00a0days culture within the hydrogels. Hydrogel samples were removed from media, washed 3 times with PBS, and fixed in 10% paraformaldehyde for 30\u00a0min at room temperature. Then, each sample was incubated with 1\u00a0mL DAPI stain solution for 30\u00a0min at room temperature. Samples were then scanned across the z-axis using a 2\u00a0\u00b5m step size reaching a maximum of 150 slices of sample down from the top layer. The scanned distance for each sample was set to a maximum of 300\u00a0\u00b5m starting from the surface. Scanned files were processed via Image J software. The depth location was determined by nuclei localisation within the depth of the hydrogel.Primary antibodies for collagens type I, II, and X  confirmed differentiation. Visualization was enabled through appropriate secondary antibodies; Goat Anti-Rabbit IgG H&L, Abcam cat. No. 6718 and 6717, respectively). Hydrogel samples were fixed with 10% formaldehyde for 30\u00a0min at room temperature. Samples were blocked with 5% bovine serum albumin (BSA) in PBS for 2\u20133\u00a0h at 4\u00a0\u00b0C. This was followed by sample incubation with primary antibody solution overnight at 4\u00a0\u00b0C. The primary solution was prepared by mixing primary antibody  with 5% BSA in PBS at 1:200 ratio. The primary solution was then aspirated, and samples washed 4 times with 1% BSA in PBS solution. Samples were then incubated with secondary antibody (conjugated with either FITC or TRITC) in 5% BSA in PBS solution at 1:200 ratio at 4\u00a0\u00b0C for 4\u00a0h in the dark. Samples were then washed with 1% BSA in PBS followed by additional PBS washes. Nuclear staining was through DAPI stain for 30\u00a0min at room temperature followed by PBS washes. Hydrogels were imaged with an Olympus U-TBI90 laser fluorescent confocal microscope.Extraction of calcium minerals from hydrogel samples was performed using 0.5\u00a0M HCl solution. Hydrogels were first fixed with 10% paraformaldehyde in phosphate buffer saline (PBS) for 30\u00a0min at room temperature. Each hydrogel sample was incubated with 500 \u00b5L of HCl extraction solution at room temperature overnight on a rotary shaker. Calcium mineral was assessed using the calcium colorimetric assay kit (Sigma Aldrich MAK022) following manufacturer\u2019s instructions with calcium ions present in samples Morin  detectedGAGs matrix proteins were assessed by dimethylmethylene blue (DMMB) assay . Hydrogels were digested in papain lysis buffer at 60\u00a0\u00b0C overnight. Cell lysates were then assessed for collagens I, II  and annexin A2  subsequent to the application of the assay protocol specific for each marker. Absorbance was measured with a Synergy II BioTek plate reader.P\u2009\u2264\u20090.05)  Fig.\u00a0B. pNTBAMP\u2009\u2264\u20090.05). Pore size increased with lowering hydrogel monomeric concentrations for both hydrogels (p\u2009\u2264\u20090.05). For pNIPAM, 0.058\u00a0g/mL and 0.04\u00a0g/mL concentration resulted in mean pore diameters of 29.9\u2009\u00b1\u20097.7\u00a0\u00b5m and 35.7\u2009\u00b1\u20099\u00a0\u00b5m, respectively. Similarly, with pNTBAM, 0.058\u00a0g/mL and 0.04\u00a0g/mL concentrations resulted in mean pore diameters of 16.3\u2009\u00b1\u20093.6 \u00b5mand 21.2\u2009\u00b1\u20095\u00a0\u00b5m, respectively   .Osteosarcoma MG63 and chondrogenic OK3H cells seeded onto pNIPAM samples formed distinct aggregates or clusters while conversely, with pNTBAM, they attach and spread out across the hydrogel surface Fig.\u00a0A, B. ThiP\u2009\u2264\u20090.05) and 0.058\u00a0g/mL (44.8\u2009\u00b1\u200919 pNIPAM \u00b5m)  and 0.042\u00a0g/mL (pNIPAM) for primary cell experimentation. Further, based on identified properties (stiffer mass and high cellular density) pNTBAM was selected as a putative best choice for support of mineralization while the smaller pores, hydrophobicity, lower cellular density, cluster growth, and flexibility suggested pNIPAM as a putative choice for chondrogenic tissue growth.2) when compared to hOBs (243.6\u2009\u00b1\u200938.26 cells/ mm2) on pNTBAM (P\u2009\u2264\u20090.05). We again noted that pNIPAM displayed reduced cell numbers (58\u2009\u00b1\u20097.3 cells/mm2 for hOBs and 65\u2009\u00b1\u20093.3 cells/mm2) when compared to pNTBAM, . pNTBAM produced 2.09\u2009\u00b1\u20090.04 versus 0.37\u2009\u00b1\u20090.04\u00a0\u00b5g/\u00b5L calcium ions whilst pNIPAM produced the lower amount of 1.15\u2009\u00b1\u20090.04 versus 0.47\u2009\u00b1\u20090.06\u00a0\u00b5g/\u00b5L calcium ions (P\u2009\u2264\u20090.05). Collagen I levels produced by hOBs were significantly elevated in osteogenic media when compared to control samples  (P\u2009\u2264\u20090.05) . Complementary to increases in collagen I and calcium ion production we noted that ALP activity levels were increased from 0.2 \u00d7 103\u2009\u00b1\u20090.1 \u00d7 103 for controls to 3.3 \u00d7 103\u2009\u00b1\u20090.6 \u00d7 103 U/\u00b5L for pNTBAM osteogenic samples (P\u2009\u2264\u20090.05) which were themselves in turn significantly elevated (P\u2009\u2264\u20090.05) when compared to pNIPAM values of 1.4 \u00d7 103\u2009\u00b1\u20090.2 \u00d7 103 U/\u00b5L versus 0.3 \u00d7 103\u2009\u00b1\u20090.1 \u00d7 103 U/\u00b5L in untreated controls (P\u2009\u2264\u20090.05)  Fig.\u00a0A.Fig. 7OP\u2009\u2264\u20090.05). pNTBAM produced 31.3 \u00d7 103\u2009\u00b1\u20094.7 \u00d7 103 in osteogenic compared to 2.7 \u00d7 103\u2009\u00b1\u20091.8\u00a0ng/g control, whereas pNIPAM produced 17.2 \u00d7 103\u2009\u00b1\u20092.4 \u00d7 103 versus 2.3 \u00d7 103\u2009\u00b1\u20091.2 \u00d7 103\u00a0ng/g of controls   when compared to pNTBAM (0.52\u2009\u00b1\u20090.06\u00a0\u00b5g/\u00b5L pNIPAM versus 0.14\u2009\u00b1\u20090.06\u00a0\u00b5g/\u00b5L for pNTBAM). Both were significantly lower (P\u2009\u2264\u20090.05) than hOB samples in osteogenic media. Hydrogels seeded with hCHs in chondrogenic media displayed increased collagen I levels when compared to controls (pNTBAM (85\u2009\u00b1\u200923 versus 26\u2009\u00b1\u20096\u00a0ng/g) and pNIPAM (133\u2009\u00b1\u200933 versus 78\u2009\u00b1\u200919\u00a0ng/g) (P\u2009>\u20090.05)   Fig.\u00a0A. Howeve Fig.\u00a0A. P\u2009\u2264\u20090.05). pNIPAMhCHs samples were not significantly different compared to their controls and were significantly lower (P\u2009\u2264\u20090.05) than pNTBAM (1.15\u2009\u00b1\u20090.49\u00a0\u00b5g pNIPAM versus 25\u2009\u00b1\u20090.74\u00a0\u00b5g for pNTBAM chondrogenic samples).Chondrogenic hCHs samples revealed significant elevation in GAG expression for pNTBAM hydrogels (25\u2009\u00b1\u20090.7\u00a0\u00b5g versus 12.26\u2009\u00b1\u20091.5\u00a0\u00b5g control) (P\u2009\u2264\u20090.05). pNIPAM displayed no significant changes (224\u2009\u00b1\u2009112 versus 74.8\u2009\u00b1\u200964.7\u00a0ng/g control). pNTBAM, again, showed significant elevation when compared to pNIPAM chondrogenic samples (3105\u2009\u00b1\u2009282 versus 224\u2009\u00b1\u2009112\u00a0ng/g for pNIPAM)   (pNIPAM) and poly(N-tert-butylacrylamide) (pNTBAM) hydrogels were produced by polymerization induced phase separation resulting from differing wettablity between monomer and polymer network, a widely applied method in the production of porous polymer scaffolds  with chondrogenic differentiation. We conclude that when taken together, these unique polymer characteristics create a potentially tuneable platform for 3D osteochondral scaffold generation for application in future tissue engineered complex repair situations."}
{"text": "The structure of a copper(II) complex is described. 6H4O2N)2]\u00b72C9H6O6\u00b72H2O, the Cu2+ ion lies on a center of inversion and coordinates with symmetry related pyridine nitro\u00adgen and carboxyl oxygen atoms from two pyridine-2-carb\u00adoxy\u00adlic acid anions, giving rise to a square-planar coordination geometry. There are weak axial bonds between Cu and an O atom of a symmetry-related trimesic acid moieties [Cu\u22efO = 2.837\u2005(2)\u2005\u00c5] The Cu\u22efO weak inter\u00adactions and hydrogen bonds stabilize the whole structure.In the title complex, [Cu(C In the axial position, a very weak inter\u00adaction Cu1\u22efO3 [2.837\u2005(2)\u2005\u00c5] is observed. Inter\u00adestingly, the 1,4-bis\u00ad(3-pyrid\u00adyl)-2,3-di\u00adaza-1,3-butadiene ligand decomposed during the hydro\u00adthermal process and is oxidized into pyridine-2-carb\u00adoxy\u00adlic acid. According to our earlier research, the occurrence of oxidation may be caused by excess of CuII salt, which may act as an oxidative agent to promote the formation of the carboxyl group  ligand and one crystal water mol\u00adecule Fig.\u00a01. The Cu23\u2212 ligands  are short, there are no \u03c0\u2013\u03c0 inter\u00adactions because the inter-centroid distance between the two benzene rings is 5.4029\u2005(15)\u2005\u00c5, which is much larger than the normal \u03c0\u2013\u03c0 stacking distance of 3.3\u20133.8\u2005\u00c5. The shortest distance between the two carbon atoms (C1 and C1\u2032) is 3.379\u2005(4)\u2005\u00c5. The other C\u22efC distances of the two rings are longer than 3.94\u2005\u00c5. In addition, the distance between the centroid of one benzene ring and the C atoms of another is longer than 4.28\u2005\u00c5.In the crystal, C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds Table\u00a01 and toge2\u00b72H2O  in 5\u2005mL of distilled H2O was stirred for 10\u2005min in air, and then the mixture was turned into a Parr Teflon-lined stainless steel vessel and heated at 160\u00b0C for 60\u2005h. Dark-red crystals suitable for X-ray diffraction were obtained in a yield of 78% (based on CuCl2\u00b72H2O).A mixture of trimesic acid , 1,4-bis\u00ad(3-pyrid\u00adyl)-2,3-di\u00adaza-1,3-butadiene  and CuClCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621006726/bv4039sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621006726/bv4039Isup3.hklStructure factors: contains datablock(s) I. DOI: 2092720CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In thermophiles, tRNAs are heavily modified to maintain their thermal stability under extreme growth temperatures6. Here we identified 2\u2032-phosphouridine (Up) at position 47 of tRNAs from thermophilic archaea. Up47 confers thermal stability and nuclease resistance to tRNAs. Atomic structures of native archaeal tRNA showed a unique metastable core structure stabilized by Up47. The 2\u2032-phosphate of Up47 protrudes from the tRNA core and prevents backbone rotation during thermal denaturation. In addition, we identified the arkI gene, which encodes an archaeal RNA kinase responsible for Up47 formation. Structural studies showed that ArkI has a non-canonical kinase motif surrounded by a positively charged patch for tRNA binding. A knockout strain of arkI grew slowly at high temperatures and exhibited a synthetic growth defect when a second tRNA-modifying enzyme was depleted. We also identified an archaeal homologue of KptA as an eraser that efficiently dephosphorylates Up47 in vitro and in vivo. Taken together, our findings show that Up47 is a reversible RNA modification mediated by ArkI and KptA that fine-tunes the structural rigidity of tRNAs under extreme environmental conditions.Post-transcriptional modifications have critical roles in tRNA stability and function Reversible internal RNA phosphrylation contributes to thermal stability and nuclease resistance of tRNA, and cellular thermotolerance of hyperthermophiles.\u00a0 Thus far, about 150 types of RNA modification have been reported in various RNA molecules from all domains of life7. In particular, tRNAs contain the widest variety and largest number of modified nucleosides, with 80% of RNA modifications identified in tRNA molecules. Diverse RNA modifications are clustered in the anticodon loop, especially at positions 34 and 37 (refs. 8). These modifications have critical roles in stabilizing and modulating codon\u2013anticodon interactions on the ribosome, ensuring accurate and efficient protein synthesis. Many RNA modifications are also found in the tRNA body composed of the D-loop, T\u03a8C loop (T-loop) and variable loop (V-loop)10  confer conformational rigidity to the tRNA core region by fixing C3\u2032-endo ribose puckering11.Recent advances in epitranscriptomics research have demonstrated the chemical diversity and biological importance of RNA modifications)10 Fig. . These R6. 5-Methyl-2-thiouridine (m5s2U or s2T) is found at position 54 in the T-loop of tRNAs from thermophiles12. m5s2U54 adopts a rigid conformation with C3\u2032-endo ribose puckering, thereby stabilizing the tRNA body in high-temperature environments11. The 2-thiolation level of m5s2U54 increases as the growth temperature rises14. m5s2U54 contributes to the thermotolerance of Thermus thermophilus15. In Pyrococcus furiosus, the relative abundance of N4-acetylcytidine (ac4C) and its 2\u2032-O-methyl derivative (ac4Cm) were markedly increased with rising growth temperature14. ac4C is a prevalent modification that is present in tRNAs, rRNAs and other RNAs in hyperthermophilic archaea16. ac4C favours the C3\u2032-endo form and stabilizes tRNAs18. Loss of ac4C results in a growth defect in Thermococcus kodakarensis at high temperature, contributing to cellular\u00a0thermotolerance19. In Bacillus stearothermophilus, 2\u2032-O-methylation in tRNAs increases when the growth temperature rises20. Archaeosine (G+) is a unique 7-deazaguanosine derivative found at position 15 in the D-loop of archaeal tRNAs21. On the basis of quantum mechanics calculations, G+15 stabilizes the Levitt base pair with C48 (ref. 22). In line with this, biochemical and genetic studies have shown that G+ confers thermal stability to tRNAs and contributes to thermotolerance23.In thermophilic bacteria and archaea, unique RNA modifications contribute to the thermal adaptation of tRNAsp) in tRNAs, which, to our knowledge, is the first known instance of internal RNA phosphorylation. Biochemical, structural and genetic studies showed that Up47 is a reversible RNA modification and confers thermal stability to tRNA, thereby contributing to cellular thermotolerance.Here we report the identification of 2\u2032-phosphouridine  27 and mapped 13 types of RNA modification at 18 positions in this tRNA molecule  at position 47 of the RNA fragments digested with RNases  modification in class I tRNAs bearing U47 in the V-loop, but not in class II tRNAs with a long V-loop , with a low error value of 4.4\u2009millimass unit\u00a0, indicating that N324 is a phosphorylated uridine residue. This prediction explains why the N324 nucleoside was not detected in our nucleoside analysis  and biochemical approaches   Fig. .p47 is a thermophile-specific modification found in the tRNA core region, we investigated whether Up47 stabilizes the tertiary structure of tRNA. To this end, we treated S.\u2009tokodaii tRNAVal3 with yeast Tpt1p (2\u2032-phosphotransferase) to remove the 2\u2032-phosphate of Up47. We measured the melting temperature (Tm) of S.\u2009tokodaii tRNAVal3 with and without Up47  . According to our analysis of Up47 distribution in archaeal species  nucleotide analysis. A pUpm5C dimer was clearly observed in the parental strain (wild type) of T.\u2009kodakarensis (KU216), but was absent in the \u0394tk2051 strain .To identify a gene responsible for Uies Fig. . Among tp47 Fig. . Among tp47 Fig. . We chosp47 Fig. . STK_095ain Fig. . Therefop47 in T.\u2009kodakarensis. The \u0394arkI strain grew as well as the wild-type strain (KU216) at the nearly optimal temperature of 83\u2009\u00b0C  formation, because G+15 thermally stabilizes tRNAs and contributes to cellular thermotolerance19. We confirmed the absence of Up47 and G+15 in tRNAs from the double-knockout strain  and examined in vitro Up47 formation. Up47 was efficiently reconstituted only in the presence of ATP    Fig. , TkArkI The electrostatic surface potential showed a large positive area on one side of the TkArkI structure Fig. . The posTo characterize the conserved residues in TkArkI, we constructed 14 TkArkI mutants in which targeted residues were replaced by alanine Fig. . All mut33. Tpt1/KptA homologues are distributed across all domains of life35  in the presence of NAD+, with the results indicating that the 2\u2032-phosphate of Up47 was efficiently removed , because N.\u2009viennensis is a mesophilic archaeon and its ArkI homologue was predicted to have efficient activity in E.\u2009coli. The class I tRNA fraction prepared from this strain was subjected to shotgun analysis to detect the Up47 modification. We clearly detected four Up47-containing fragments derived from various E.\u2009coli tRNA species -inducible promotor and quantified the peak intensity of each Up47-containing fragment when TkKptA expression was induced by addition of 10 or 100\u2009\u03bcM IPTG   and two class II tRNAs (tRNALeu4 and tRNASer3)  Fig.  but was 2+. Especially at high temperatures, RNA is rapidly degraded. Similarly to 2\u2032-O-methylation, the 2\u2032-phosphorylation of Up47 also serves to prevent tRNA degradation. This property partly explains the RNase resistance of tRNA conferred by Up47  with different conformations in the core region  to fill in for the missing G46, forming the non-canonical base triple \u03a813\u2013G22\u2013C9  has a critical role in RNA metabolism and function as a reversible RNA modification45. If Up47 is a reversible modification, it is expected that tRNA function and stability are dynamically regulated by a writer and eraser, raising the possibility of epitranscriptomic regulation of tRNAs in translation. The mechanism closely resembles post-translational modification of proteins. Phosphorylation and dephosphorylation rapidly and dynamically control protein function48. Because tRNA is a stable molecule with a low turnover rate and long lifetime in the cell, it would be reasonable for tRNA function to be regulated by Up47 modification. We found efficient dephosphorylation of Up47 by TkKptA in vitro , T. Yokogawa (Gifu University) and H. Hori (Ehime University), respectively. Sulfolobus acidocaldarius (JCM no. 8929), Saccharolobus solfataricus (JCM no. 8930), Aeropyrum pernix (JCM no. 9820), Pyrobaculum oguniense (JCM no. 10595) and N.\u2009viennensis (JCM no. 19564) were obtained from\u00a0Japan Collection of Microorganisms, RIKEN BRC which is participating in the National BioResource Project of the MEXT, Japan.S.\u2009tokodaii and S.\u2009acidocaldarius were cultured at 80\u2009\u00b0C in JCM medium no. 165 consisting of 1\u2009g\u2009l\u20131 yeast extract, 1\u2009g\u2009l\u20131 casamino acids, 1.3\u2009g\u2009l\u20131 (NH4)2SO4, 0.28\u2009g\u2009l\u20131 KH2PO4, 0.25\u2009g\u2009l\u20131 MgSO4\u00b77H2O, 0.07\u2009g\u2009l\u20131 CaCl2\u00b72H2O, 2.0\u2009mg\u2009l\u20131 FeCl3\u00b76H2O, 1.8\u2009mg\u2009l\u20131 MnCl2\u00b74H2O, 4.5\u2009mg\u2009l\u20131 Na2B4O7\u00b710H2O, 0.22\u2009mg\u2009l\u20131 ZnSO4\u00b77H2O, 0.05\u2009mg\u2009l\u20131 CuCl2\u00b72H2O, 0.03\u2009mg\u2009l\u20131 Na2MoO4\u00b72H2O, 0.03\u2009mg\u2009l\u20131 VOSO4\u00b7H2O and 0.01\u2009mg\u2009l\u20131 CoSO4\u00b77H2O (adjusted to pH\u20092.5 with H2SO4). S.\u2009solfataricus was cultured at 80\u2009\u00b0C in JCM medium no. 171 consisting of 1\u2009g\u2009l\u20131 yeast extract, 2.5\u2009g\u2009l\u20131 (NH4)2SO4, 3.1\u2009g\u2009l\u20131 KH2PO4, 0.2\u2009g\u2009l\u20131 MgSO4\u00b77H2O, 0.25\u2009g\u2009l\u20131 CaCl2\u00b72H2O, 1.8\u2009mg\u2009l\u20131 MnCl2\u00b74H2O, 4.5\u2009mg\u2009l\u20131 Na2B4O7\u00b710H2O, 0.22\u2009mg\u2009l\u20131 ZnSO4\u00b77H2O, 0.05\u2009mg\u2009l\u20131 CuCl2\u00b72H2O, 0.03\u2009mg\u2009l\u20131 Na2MoO4\u00b72H2O, 0.03\u2009mg\u2009l\u20131 VOSO4\u00b7H2O and 0.01\u2009mg\u2009l\u20131 CoSO4\u00b77H2O (adjusted to pH\u20094.0 with H2SO4). A.\u2009pernix was cultured at 90\u2009\u00b0C in JCM medium no. 224 consisting of 1\u2009g\u2009l\u20131 yeast extract, 1\u2009g\u2009l\u20131 peptone, 1\u2009g\u2009l\u20131 Na2S2O3\u00b75H2O, 24.0\u2009g\u2009l\u20131 NaCl, 7.0\u2009g\u2009l\u20131 MgSO4\u00b77H2O, 5.3\u2009g\u2009l\u20131 MgCl2\u00b76H2O, 0.7\u2009g\u2009l\u20131 KCl and 0.1\u2009g\u2009l\u20131 CaCl2\u00b72H2O (adjusted to pH\u20097.0 with NaOH). P.\u2009oguniense was cultured at 90\u2009\u00b0C in JCM medium no. 165 with addition of 1.0\u2009g\u2009l\u20131 Na2S2O3\u00b75H2O (adjusted to pH\u20097.25 with NaOH). N.\u2009viennensis was cultured at 42\u2009\u00b0C in JCM medium no. 1004 consisting of 1\u2009g\u2009l\u20131 NaCl, 0.5\u2009g\u2009l\u20131 KCl, 0.4\u2009g\u2009l\u20131 MgCl2\u00b76H2O, 0.2\u2009g\u2009l\u20131 KH2PO4, 0.1\u2009g\u2009l\u20131 CaCl2\u00b72H2O, 1.0\u2009ml\u2009l\u20131 modified trace element mixture , 1.0\u2009ml\u2009l\u20131 vitamin solution ), 1.0\u2009ml\u2009l\u20131 7.5\u2009mM EDTA\u00b7Na\u00b7Fe(III) solution (pH\u20097.0), 2.0\u2009ml\u2009l\u20131 1\u2009M NaHCO3 solution, 10\u2009ml\u2009l\u20131 HEPES solution (238.4\u2009g\u2009l\u20131 HEPES (free acid) and 24\u2009g\u2009l\u20131 NaOH), 1.0\u2009ml\u2009l\u20131 1\u2009M NH4Cl solution and 1.0\u2009ml\u2009l\u20131 1\u2009M sodium pyruvate solution (adjusted to pH\u20097.6 with NaOH).T.\u2009kodakarensis was cultured at 83\u2009\u00b0C, 87\u2009\u00b0C or 91\u2009\u00b0C, in nutrient-rich medium (ASW-YT-S0 or MA-YT-Pyr) or synthetic medium containing amino acids (ASW-AA-S0), under strict anaerobic conditions. ASW-YT-S0 medium contains 0.8\u00d7 artificial sea water (ASW)50, 10\u2009g\u2009l\u20131 yeast extract, 5.0\u2009g\u2009l\u20131 tryptone, 2.0\u2009g\u2009l\u20131 elemental sulfur and 0.1% (wt/vol) resazurin. MA-YT-Pyr medium contains 30.5\u2009g\u2009l\u20131 Marine Art SF-1 (Osaka Yakken), 10\u2009g\u2009l\u20131 yeast extract, 5.0\u2009g\u2009l\u20131 tryptone, 5.0\u2009g\u2009l\u20131 pyruvate sodium and 0.1% (wt/vol) resazurin. ASW-AA-S0 medium contains 0.8\u00d7 ASW, 0.5\u00d7 amino acid solution50, modified Wolfe\u2019s trace minerals 2, 0.01\u2009g\u2009l\u20131 H3BO3 and 0.01\u2009g\u2009l\u20131 NaMoO4\u00b72H2O), 5.0\u2009ml\u2009l\u20131 vitamin mixture51, 2.0\u2009g\u2009l\u20131 elemental sulfur and 0.1% (wt/vol) resazurin. For plate cultivation, 2.0\u2009ml\u2009l\u20131 polysulfide solution  was added instead of elemental sulfur, and the media were solidified with 1.0% Gelrite . When pyrF-negative transformants were selected0, 75% 5-fluoroorotic acid (5-FOA) was added. We used ASW-YT-S0 medium for standard cultivation, MA-YT-Pyr medium for growth comparisons and ASW-AA-S0 medium for construction of the gene knockout strain.N-lauroylsarcosine sodium salt and 1\u2009mM 2-mercaptoethanol) and mixed with an equal volume of water-saturated phenol and 1/10 volume of 3\u2009M sodium acetate (pH\u20095.3). The mixture was shaken for 1\u2009h on ice and mixed with 1/5 volume of chloroform, followed by centrifugation at 8,000g for 10\u2009min at 4\u2009\u00b0C. The supernatant was collected and mixed with an equal volume of chloroform, followed by centrifugation at 8,000g for 10\u2009min at 4\u2009\u00b0C. Total RNA was obtained from the resultant supernatant by isopropanol precipitation. The total RNA prepared in this manner was separated by 10% denaturing PAGE, followed by staining with SYBR Gold or toluidine blue. The visualized tRNA fraction including class I and class II tRNAs was cut out and eluted from the gel slice with elution buffer (0.3\u2009M sodium acetate (pH\u20095.3) and 0.1% (wt/vol) SDS), followed by filtration to remove the gel pieces and ethanol precipitation for RNA-MS analysis of the tRNA fraction.For small-scale preparation (~100-ml culture), archaeal cells were resuspended in 3\u2009ml solution D , 0.5% (wt/vol) S.\u2009tokodaii, cell pellets (53\u2009g) were resuspended in 530\u2009ml solution D and then mixed with 53\u2009ml of 3\u2009M sodium acetate (pH\u20095.3) and 425\u2009ml neutralized phenol. The mixture was shaken for 1\u2009h on ice to which 106\u2009ml chloroform/isoamyl alcohol (49:1) was added, followed by centrifugation at 4,500g for 20\u2009min at 4\u2009\u00b0C. The supernatant was collected and mixed with 106\u2009ml chloroform/isoamyl alcohol (49:1), followed by centrifugation at 4,500g for 15\u2009min at 4\u2009\u00b0C. The aqueous phase was collected and then subjected to isopropanol precipitation. The collected RNA was resuspended in 53\u2009ml water and mixed with 80\u2009ml TriPure Isolation Reagent (Roche), followed by centrifugation at 10,000g for 20\u2009min at 4\u2009\u00b0C. The supernatant was collected and mixed with 36\u2009ml chloroform/isoamyl alcohol (49:1), followed by centrifugation at 10,000g for 10\u2009min at 4\u2009\u00b0C. The aqueous phase was collected and precipitated with isopropanol. The prepared total RNA (608\u2009mg) was dissolved in 250\u2009ml of buffer consisting of 20\u2009mM HEPES-KOH (pH\u20097.6), 200\u2009mM NaCl and 1\u2009mM DTT and then loaded on a DEAE Sepharose Fast Flow column (320-ml beads) and fractionated with a gradient of NaCl from 200 to 500\u2009mM. Fractions containing tRNA were collected by isopropanol precipitation.For large-scale preparation of tRNA fractions from 24 or chaplet column chromatography (CCC)52. Approximately 200 absorbance at 260\u2009nm (A260) units of the S.\u2009tokodaii tRNA fraction was subjected to RCC. The isolation procedure was carried out as follows: hybridization at 66\u2009\u00b0C in 6\u00d7 NHE buffer (30\u2009mM HEPES-KOH (pH\u20097.5), 15\u2009mM EDTA (pH\u20098.0), 1.2\u2009M NaCl, 1\u2009mM DTT), washing at 50\u2009\u00b0C with 0.1\u00d7 NHE buffer (0.5\u2009mM HEPES-KOH (pH\u20097.5), 0.25\u2009mM EDTA (pH\u20098.0), 20\u2009mM NaCl, 0.5\u2009mM DTT) and elution at 72\u2009\u00b0C with 0.1\u00d7 NHE buffer. Eluted tRNAs were recovered by ethanol precipitation. Mature and precursor tRNAs were separated by 10% denaturing PAGE and stained with SYBR Gold. Visualized bands of mature and precursor tRNAs were cut out and eluted from the gel slices with elution buffer, followed by filtration to remove the gel pieces and precipitation with ethanol.Isolation of individual tRNAs from thermophilic organisms is extremely difficult owing to their high melting temperatures, which are the consequence of their high G+C content and complex modifications. We thus optimized our original method for RNA isolation by RCCp47, we conducted large-scale isolation of S.\u2009tokodaii tRNAVal3 using CCC52. The S.\u2009tokodaii tRNA fraction  was subjected to CCC with tandem affinity chaplet columns for tRNAVal3, tRNAIle2 and tRNAPhe. The isolation procedure was carried out as follows: hybridization at 66\u2009\u00b0C in 6\u00d7 NHE buffer, washing separately at 50\u2009\u00b0C with 0.1\u00d7 NHE buffer and elution at 72\u2009\u00b0C with 0.1\u00d7 NHE buffer. The eluted tRNAs were recovered by isopropanol precipitation. The sequences of the DNA probes are shown in Supplementary Table Val3 was further purified by anion exchange chromatography to completely remove tRNAVal2, as described below.To crystalize native tRNA bearing U 2,000\u2009A20 units w1 (Epicentre or Thermo Fisher Scientific) or RNase\u2009A (Ambion) and analysed with a linear ion trap\u2013Orbitrap hybrid mass spectrometer  equipped with a custom-made nanospray ion source and a splitless nanoHPLC system  as described previously27. To analyse \u03a8 sites, tRNA was treated with acrylonitrile to cyanoethylate \u03a853 and subjected to RNA-MS. For dephosphorylation of the Up47-containing fragment . To precisely map tRNA modifications, RNA fragments were decomposed by CID in the instrument. The normalized collision energy of LTQ Orbitrap XL was set to 40%. Mongo Oligo Mass Calculator v2.08  was used for assignment of the product ions in CID spectra.For tRNA fragment analysis by RNA-MS, 30\u2009ng (900\u2009fmol) of the isolated tRNA or 150\u2009ng (4.5\u2009pmol) of tRNA mixture was digested with RNase\u2009TVal3 was digested with 0.09\u2009U nuclease\u2009P1  in 20\u2009mM ammonium acetate (pH\u20095.2) at 50\u2009\u00b0C for 1\u2009h and mixed with 1/8 volume of 1\u2009M trimethylamine-HCl (TMA-HCl) (pH\u20097.2) and 0.06\u2009U phosphodiesterase\u2009I , followed by incubation at 37\u2009\u00b0C for 1\u2009h. To this mixture, 0.08\u2009U BAP was added, and the sample was incubated at 50\u2009\u00b0C for 1\u2009h. After that, 9 volumes of acetonitrile were added, followed by LC\u2013MS/MS analysis as described in refs. 54 with some modifications as follows. The samples were chromatographed with a ZIC-cHILIC column  and eluted with 5\u2009mM ammonium acetate (pH\u20095.3) (solvent\u2009A) and acetonitrile (solvent\u2009B) at a flow rate of 100\u2009\u03bcl\u2009min\u20131 with a multistep linear gradient: 90\u201350% solvent\u2009B for 30\u2009min, 50% solvent\u2009B for 10\u2009min, 50\u201390% solvent\u2009B for 5\u2009min and then initialization with 90% solvent\u2009B. The chromatographed eluent was directly introduced into the electrospray ionization source of the Q Exactive Hybrid Quadrupole\u2013Orbitrap mass spectrometer (Thermo Fisher Scientific).For nucleoside analysis, 800\u2009ng (24\u2009pmol) of the isolated tRNA1 in 20\u2009mM ammonium acetate (pH\u20095.2) at 50\u2009\u00b0C for 1\u2009h and then mixed with 9 volumes of acetonitrile for LC\u2013MS. The digests were chromatographed with a ZIC-cHILIC column and analysed by Q Exactive Hybrid Quadrupole\u2013Orbitrap mass spectrometer (Thermo Fisher Scientific) or LTQ Orbitrap XL (Thermo Fisher Scientific) with a multistep linear gradient: 90\u201350% solvent\u2009B for 30\u2009min, 50% solvent\u2009B for 10\u2009min, 50\u201390% solvent\u2009B for 5\u2009min and then initialization with 90% solvent\u2009B.For nucleotide analysis, 800\u2009ng (24\u2009pmol) of the tRNA fraction or individual tRNA was digested with 0.09\u2009U nuclease\u2009PThe acquired LC\u2013MS data were analysed using Xcalibur 4.1 (Thermo Fisher Scientific) and were visualized with Canvas X .A260 units of the S.\u2009tokodaii tRNA fraction was completely digested with nuclease\u2009P1. Digests containing pN324m5C dinucleotide were subjected to periodate oxidation with 10\u2009mM NaIO4 for 1\u2009h on ice in the dark. The reaction was stopped by addition of 1\u2009M l-rhamnose and incubation for 30\u2009min. For \u03b2-elimination, an equal volume of 2\u2009M lysine-HCl (pH\u20098.5) was added, and the sample was incubated at 45\u2009\u00b0C for 90\u2009min. The product containing pN324p was then subjected to anion exchange chromatography with a Q Sepharose Fast Flow column  equilibrated with 20\u2009mM triethylammonium bicarbonate (TEAB) (pH\u20098.2). The eluate with 2\u2009M TEAB was collected and dried by evaporation in vacuo. The pellet was dissolved with water and mixed with an equal volume of chloroform, followed by centrifugation at 20,000g for 5\u2009min at 4\u2009\u00b0C. The supernatant was recovered and dried again. This process was repeated five times. The resultant digest was mixed with 9 volumes of acetonitrile and subjected to LC\u2013MS/MS using an LCQ-Advantage ion trap mass spectrometer (Thermo Scientific), equipped with an electrospray ionization source and an HP1100 LC system (Agilent Technologies). For LC, the digest was chromatographed with a ZIC-HILIC column  and eluted with 5\u2009mM formic acid (pH\u20093.4) (solvent\u2009A) and acetonitrile (solvent\u2009B) at a flow rate of 100\u2009\u03bcl\u2009min\u20131 with a multistep gradient: 90\u201370% solvent\u2009B for 25\u2009min, 70\u201310% solvent\u2009B for 15\u2009min, 10% solvent\u2009B for 5\u2009min and then initialized with 90% solvent\u2009B.Five arkI from T.\u2009kodakarensis, Methanocaldococcus fervens, P.\u2009oguniense, Aquifex aeolicus, Nautilia profundicola and Leptolyngbya sp. PCC7376 were designed with codons optimized for E.\u2009coli expression and synthesized by GENEWIZ or Thermo Fisher Scientific. Each gene was cloned into the pE-SUMO-TEV vector by the SLiCE method55. N.\u2009viennensis arkI was PCR amplified from genomic DNA with a set of primers (Supplementary Table Synthetic genes for E.\u2009coli BL21(DE3) or Rosetta2(DE3) cells transformed with the pE-SUMO-TEV vector carrying each arkI gene were cultured in 250\u2009ml or 1\u2009l of LB containing 50\u2009\u03bcg\u2009ml\u20131 kanamycin and 20\u2009\u03bcg\u2009ml\u20131 chloramphenicol when necessary. His6\u2013SUMO-tagged recombinant protein was expressed at 37\u2009\u00b0C for 3\u20134\u2009h by induction with 0.1 or 1\u2009mM IPTG or 2% (wt/vol) lactose when the cells reached OD610\u2009=\u20090.4\u20130.6. P.\u2009oguniense ArkI was expressed in cells cultured overnight at 18\u2009\u00b0C. The collected cells were resuspended in lysis buffer (50\u2009mM HEPES-KOH (pH\u20098.0), 150\u2009mM KCl, 2\u2009mM MgCl2, 20\u2009mM imidazole, 12% (vol/vol) glycerol, 1\u2009mM 2-mercaptoethanol and 1\u2009mM PMSF) and disrupted by sonication, followed by centrifugation at 15,000g for 15\u2009min at 4\u2009\u00b0C. The supernatant was boiled at 60\u2009\u00b0C for 20\u2009min  and centrifuged at 15,000g for 15\u2009min at 4\u2009\u00b0C. The recombinant protein was affinity captured on an Ni-Sepharose 6 Fast Flow column  and then eluted with lysis buffer containing 300\u2009mM imidazole, followed by gel filtration with a PD-10 column  to remove the imidazole. The recombinant protein for N.\u2009viennensis ArkI was purified using a HisTrap column  with a linear gradient of 0\u2013500\u2009mM imidazole, followed by dialysis using a Slide-A-Lyzer Dialysis Cassette (Thermo Fisher Scientific) to remove imidazole. The purified protein was subjected to Ulp1 digestion at 4\u2009\u00b0C overnight to cleave the His6\u2013SUMO tag and then passed through a Ni-Sepharose 6 Fast Flow column to remove the tag. Because ArkI homologues from M.\u2009fervens (MfArkI) and Leptolyngbya sp. PCC7376 (LeArkI) aggregated following tag removal, His6\u2013SUMO tag-fused proteins of these homologues were used for the phosphorylation assay. Purified protein was quantified by the Bradford method using BSA as a standard.T.\u2009kodakarensis ArkI for crystallization, the E.\u2009coli BL21(DE3) strain carrying pE-SUMO-TkArkI was cultured in 2\u2009l of LB containing 50 \u03bcg\u2009ml\u20131 kanamycin and TkArkI was expressed at 25\u2009\u00b0C overnight by induction with 0.1\u2009mM IPTG when the cells reached OD610\u2009=\u20090.4. The cells were collected and disrupted by sonication in lysis buffer (50\u2009mM HEPES-KOH (pH\u20098.0), 150\u2009mM KCl, 2\u2009mM MgCl2, 20\u2009mM imidazole, 12% (vol/vol) glycerol, 1\u2009mM 2-mercaptoethanol and 1\u2009mM PMSF). The protein was purified using a HisTrap column with a linear gradient of 20\u2013520\u2009mM imidazole. Fractions containing TkArkI were pooled and subjected to Ulp1 digestion at 4\u2009\u00b0C overnight to cleave the tag, followed by passage through a Ni-Sepharose 6 Fast Flow column to remove the tag fragment. The flow-through fraction was filtered through a 0.45-\u03bcm PVDF membrane to remove the resin. The protein was further purified by affinity chromatography with a HiTrap Heparin HP column  using a linear gradient of 150\u20131,150\u2009mM KCl. TkArkI was further purified by size exclusion chromatography using a Superdex 75 10/300 GL column  with buffer containing 20\u2009mM Tris-HCl (pH\u20098.0), 150\u2009mM NaCl and 10\u2009mM 2-mercaptoethanol and then concentrated to 5.74\u2009mg\u2009ml\u20131 and stored at \u201380\u2009\u00b0C.For large-scale preparation of T.\u2009kodakarensis kptA gene was PCR amplified from genomic DNA from T.\u2009kodakarensis with the primers listed in Supplementary Table tkkptA. The E.\u2009coli Rosetta2(DE3) strain carrying pE-SUMO-TEV-tkkptA was cultured in 1\u2009l LB containing 50\u2009\u03bcg\u2009ml\u20131 kanamycin and 20\u2009\u03bcg\u2009ml\u20131 chloramphenicol, and TkKptA was expressed at 37\u2009\u00b0C for 3\u2009h by induction with 0.1\u2009mM IPTG when the cells reached OD610\u2009=\u20090.6. The recombinant TkKptA was purified as described above. The gene encoding Tpt1p was PCR amplified from the genomic DNA of S.\u2009cerevisiae BY4742 with the set of primers listed in Supplementary Table The p47 by yeast Tpt1p was performed as described33. Individual tRNAs or the tRNA fraction was incubated for 3\u2009h at 30\u2009\u00b0C in a reaction mixture (25\u2009\u03bcl) consisting of 20\u2009mM Tris-HCl (pH\u20097.4), 0.5\u2009mM EDTA (pH\u20098.0), 1\u2009mM NAD+, 2.5\u2009mM spermidine, 0.1\u2009mM DTT, 0.9\u2009\u03bcM tRNA and 0.1\u2009\u03bcg\u2009\u03bcl\u20131 recombinant Tpt1p. The tRNA was extracted by phenol/chloroform treatment and recovered by ethanol precipitation, followed by desalting with Centri-Sep spin columns (Princeton Separations). For crystallization of Tpt1p-treated tRNA, S.\u2009tokodaii tRNAVal3 (202.5\u2009\u03bcg) was dephosphorylated by yeast Tpt1p in a 200-\u03bcl reaction mixture.Removal of the 2\u2032-phosphate of US.\u2009tokodaii tRNAVal3 (25\u2009pmol) with or without Up47 was dissolved in degassed buffer consisting of 50\u2009mM Tris-HCl (pH\u20097.4), 100\u2009mM NaCl and 1\u2009mM MgCl2 and incubated at 80\u2009\u00b0C for 5\u2009min, followed by cooling to 25\u2009\u00b0C at a rate of 0.1\u2009\u00b0C\u2009s\u20131. The samples were placed onto a Type 8 multi-micro UV quartz cell . The hyperchromicity of tRNA was monitored on a UV\u2013visible light spectrophotometer . The gradients were as follows: 25\u2009\u00b0C for 30\u2009s, 25\u201340\u2009\u00b0C at 5\u2009\u00b0C\u2009min\u20131, 40\u2009\u00b0C for 5\u2009min and 40\u2013105\u2009\u00b0C at 0.5\u2009\u00b0C\u2009min\u20131. The Tm was calculated using Spectra Manager v2 (JASCO). Melting curves were generated using Microsoft Excel.S.\u2009tokodaii tRNAVal3 (25\u2009pmol) with or without Up47 was labelled with 32P at the 3\u2032\u2009terminus by ligation with [5\u2032-32P]cytidine 3\u2032,5\u2032-bisphosphate (PerkinElmer). The labelled tRNA was separated on a 7.5% (wt/vol) polyacrylamide gel containing 7\u2009M urea, 1\u00d7 TBE and 10% (vol/vol) glycerol and was purified by gel extraction. Labelled tRNA was mixed with the S.\u2009tokodaii tRNA fraction as a carrier to a concentration of 100,000\u2009counts per minute (c.p.m.) per A260 unit and was precipitated with ethanol. The pellet was dissolved in water to a concentration of 0.1\u2009A260 units per \u03bcl. For the RNase degradation assay, the labelled tRNA  was incubated at 65\u2009\u00b0C in a reaction mixture consisting of 10\u2009mM HEPES-KOH (pH\u20097.6), 0.5\u2009mM MgCl2, 100\u2009mM NaCl and 0.1\u2009U\u2009\u03bcl\u20131 RNase\u2009I (Promega). At time points of 1, 3, 5, 10, 15 and 30\u2009min after starting the reaction, aliquots were taken from the mixture and mixed well with chilled phenol/chloroform/isoamyl alcohol  to stop the reaction, followed by centrifugation at 15,000g for 15 min at 4\u2009\u00b0C. The supernatant was collected and treated with an equal volume of chloroform, followed by centrifugation at 15,000g for 5\u2009min at 4\u2009\u00b0C. The supernatant was mixed with 2\u00d7 loading solution  sucrose, 0.05% (wt/vol) xylene cyanol and 0.05% (wt/vol) bromophenol blue) and subjected to 10% denaturing PAGE. The gel was exposed to an imaging plate, and radioactivity was visualized by using an FLA-7000 imaging analyser (Fujifilm). Graphs were generated using Microsoft Excel.S.\u2009tokodaii tRNAVal3 (500\u2009\u03bcg), isolated as described above, was refolded in annealing buffer (50\u2009mM HEPES-KOH (pH\u20097.6), 5\u2009mM MgCl2 and 1\u2009mM DTT) by incubation for 5\u2009min at 80\u2009\u00b0C and cooling to 25\u2009\u00b0C with a rate of 0.1\u2009\u00b0C\u2009s\u20131. tRNAVal3 was further purified by anion exchange chromatography using a Mono Q 5/50 GL column  with a linear gradient of 200\u20131,000\u2009mM NaCl. The major peak was collected, precipitated with isopropanol, dissolved in water and precipitated with ethanol. Tpt1p-treated tRNAVal3 was prepared with the same procedure as described above. The purified tRNA was dissolved in buffer consisting of 10\u2009mM Tris-HCl (pH\u20097.1) and 5\u2009mM MgCl2 to a concentration of 50\u2009\u03bcM. One microlitre of tRNA solution was mixed with 1\u2009\u03bcl Natrix 2 no. 32  and 30% (vol/vol) MPD) (Hampton Research) on silicon-coated glass and crystalized by the hanging drop vapor diffusion method at 20\u2009\u00b0C.\u20131 before crystallization. One microlitre of the protein solution was mixed with 0.5\u2009\u03bcl reservoir solution, containing 25% (vol/vol) ethylene glycol. TkArkI was crystallized by the hanging drop vapor diffusion method at 20\u2009\u00b0C.The concentration of TkArkI was adjusted to 5\u2009mg\u2009mlVal3 crystals, the crystals were cryoprotected with a portion of the reservoir solution. For data collection for the native TkArkI crystal, the crystal was cryoprotected with solution containing 25% (vol/vol) ethylene glycol, 2\u2009mM MgCl2 and 1\u2009mM ATP. For data collection for the iodide-derivative TkArkI crystal, the crystal was briefly soaked in and cryoprotected with solution containing 300\u2009mM potassium iodide and 22.5% (vol/vol) ethylene glycol, and the diffraction dataset was collected at a wavelength of 1.5\u2009\u00c5. The datasets were indexed, integrated and scaled using xds56. The initial phase of tRNAVal3 was determined by molecular replacement with Phaser57. The structure of T.\u2009thermophilus tRNAVal 58 was used for the model. The initial phase of TkArkI was determined by the SAD method using the anomalous signal of iodide ions. The iodine sites were located by SHELX59, and the initial phase was calculated by Phaser. Subsequent density modification and initial model building were performed with RESOLVE60. The model was further modified with Coot61 and refined with Phenix62. Crystal structures and their electron density maps were visualized using PyMOL, Cuemol or Coot. Torsion angles of the tRNAs were analysed with DSSR software63.The datasets were collected at beamline BL-17A at the Photon Factory at KEK, Japan. For data collection for the tRNA15N]adenosine (10\u2009pmol) and [15N]guanosine (10\u2009pmol) as tracer molecules, followed by addition of 4 volumes of methanol, an equal volume of chloroform and 3 volumes of water and vigorous mixing. The denatured protein was removed by centrifugation at 15,000g for 1\u2009min at 4\u2009\u00b0C. The supernatant was dried in vacuo and dissolved in 20\u2009\u03bcl water. Half of the extract was analysed by LC\u2013MS. The tracer molecules were prepared by dephosphorylation of [15N]ATP and [15N]GTP as follows: 1,000\u2009pmol each of [15N]ATP (Silantes) and [15N]GTP (Silantes) was treated with 0.04\u2009U alkaline phosphatase  in 20\u2009mM ammonium acetate (pH\u20098.0) at 60\u2009\u00b0C for 30\u2009min. After dephosphorylation, PAP was heat denatured at 95\u2009\u00b0C for 5\u2009min.TkArkI purified by affinity chromatography with a HiTrap Heparin HP column  (100\u2009pmol) was mixed with ATP to tRNA similarly to the kinetic studies of TkArkI (see below). tRNA phosphorylation was performed at 70\u2009\u00b0C for 15\u2009min in an 8-\u03bcl reaction mixture. For PAGE analysis, 4\u2009\u03bcl of the reaction mixture was mixed with 4\u2009\u03bcl of 2\u00d7 loading solution, resolved by 10% denaturing PAGE and exposed to an imaging plate to visualize radiolabelled RNA with an FLA-9000 imaging analyser (Fujifilm). The gel image was analysed using Multi Gauge (Fujifilm). Bar graphs with independent plots were prepared with R (R Foundation). For phosphorylation of total RNA, the reaction was performed at 70\u2009\u00b0C for 30\u2009min in an 8-\u03bcl reaction mixture consisting of 50\u2009mM HEPES-NaOH (pH\u20097.5), 1\u2009mM MgCl2, 1\u2009mM MnCl2, 1\u2009mM DTT, 10% (vol/vol) glycerol, 100\u2009\u03bcM [\u03b3-32P]ATP , 1.8\u2009\u03bcM TkArkI and 50\u2009ng\u2009\u03bcl\u20131 total RNA fraction (from the T.\u2009kodakarensis \u0394arkI strain). Then, 0.5\u2009\u03bcl of 50\u2009mM EDTA (pH\u20098.0) was added, and 4\u2009\u03bcl of reaction mixture was mixed with 2\u00d7 loading solution, resolved by 10% denaturing PAGE and visualized as described above.Up47 by other ArkI homologues was carried out at 70\u2009\u00b0C for 30\u2009min in a reaction mixture (30\u2009\u03bcl) containing 50\u2009mM PIPES-NaOH (pH\u20096.9), 125\u2009mM NaCl, 1\u2009mM MgCl2, 1\u2009mM MnCl2, 1\u2009mM DTT, 10% (vol/vol) glycerol, 500\u2009\u03bcM ATP, 0.05\u2009mg\u2009ml\u20131 BSA (Takara), 1\u2009\u03bcM tRNA transcript and 0.5\u2009\u03bcM ArkI protein. For NvArkI, the reaction temperature was set to 45\u2009\u00b0C. For ArkI homologue from N.\u00a0profundicola\u00a0(NpArkI), the reaction was carried out at 50\u2009\u00b0C for 60\u2009min. After the reaction, tRNA was prepared as described above. For PAGE analysis, Up47 formation was carried out in a reaction mixture (8\u2009\u03bcl) containing 50\u2009mM PIPES-NaOH (pH\u20096.9), 125\u2009mM NaCl, 1\u2009mM MgCl2, 1\u2009mM MnCl2, 1\u2009mM DTT, 10% (vol/vol) glycerol, 100\u2009\u03bcM [\u03b3-32P]ATP , 0.1\u2009mg\u2009ml\u20131 BSA (Takara), 0.75\u2009\u03bcM recombinant ArkI homologue  and 50\u2009ng\u2009\u03bcl\u20131 E.\u2009coli total RNA. Then, the reaction mixture was mixed with 2\u00d7 loading solution, resolved by 10% denaturing PAGE and visualized as described above.Formation of Up47 by TkKptA was carried out at 60\u2009\u00b0C for 1\u2009h in a reaction mixture (30\u2009\u03bcl) containing 20\u2009mM Tris-HCl (pH\u20097.4), 0.5\u2009mM EDTA (pH\u20098.0), 1\u2009mM NAD+, 2.5\u2009mM spermidine, 0.1\u2009mM DTT, 0.9\u2009\u03bcM T.\u2009kodakarensis tRNA fraction and 0.1\u2009\u03bcg\u2009\u03bcl\u20131 recombinant TkKptA. After the reaction, the tRNA was extracted by acidic phenol/chloroform, desalted on a NAP-5 column  and precipitated with isopropanol. For RNA-MS, the prepared tRNA was desalted by drop dialysis as described above.Dephosphorylation of Up47 formation was quantified by \u03b3-phosphate transfer from [\u03b3-32P]ATP to tRNA. For kinetic measurement of the tRNA substrate, tRNA phosphorylation was performed at 70\u2009\u00b0C in a reaction mixture (25\u2009\u03bcl) consisting of 50\u2009mM PIPES-NaOH (pH\u20096.9), 125\u2009mM NaCl, 1\u2009mM MgCl2, 1\u2009mM MnCl2, 1\u2009mM DTT, 10% (vol/vol) glycerol, 100\u2009\u03bcM [\u03b3-32P]ATP , 0.05\u2009mg\u2009ml\u20131 BSA (Takara), 0.05\u2009\u03bcM TkArkI and 0.1\u20135.0\u2009\u03bcM of in vitro-transcribed T.\u2009kodakarensis tRNAVal3. For kinetic measurement of the ATP substrate, the ATP concentration was altered from 15.6 to 1,000\u2009\u03bcM [\u03b3-32P]ATP  and the tRNA concentration was increased to 1.0\u2009\u03bcM. At each time point (2 and 5\u2009min), 8-\u03bcl aliquots were taken and mixed with an equal volume of 2\u00d7 loading solution  bromophenol blue, 0.2% (wt/vol) xylene cyanol and 50\u2009mM EDTA (pH\u20098.0)) to quench the reaction. Each sample was subjected to 10% denaturing PAGE. The gel was exposed on an imaging plate to measure radiolabelled tRNAs using an FLA-9000 imaging analyser. Kinetic parameters were calculated using Prism 7 (GraphPad).TkArkI-mediated Up47 was quantified by measuring the reduction in radioactivity for tRNA. In vitro-transcribed T.\u2009kodakarensis tRNAVal3 was phosphorylated by TkArkI with [\u03b3-32P]ATP as described above and then purified by gel extraction and isopropanol precipitation. In addition, the same tRNA was phosphorylated by TkArkI with unlabelled ATP. By mixing labelled and unlabelled tRNAs, the specific activity of the labelled tRNA was adjusted to 6,250\u2009c.p.m. per pmol in buffer consisting of 50\u2009mM HEPES-KOH (pH\u20097.6), 5\u2009mM MgCl2 and 1\u2009mM DTT. The labelled tRNA was incubated at 80\u2009\u00b0C for 5\u2009min and then cooled at room temperature, followed by isopropanol precipitation. The labelled tRNA was dissolved in water to a concentration of 8\u2009\u03bcM . Dephosphorylation of the labelled tRNA by TkKptA was performed at 70\u2009\u00b0C in a reaction mixture (30\u2009\u03bcl) consisting of 50\u2009mM PIPES-NaOH (pH\u20096.9), 125\u2009mM NaCl, 1\u2009mM MgCl2, 1\u2009mM MnCl2, 1\u2009mM DTT, 10% (vol/vol) glycerol, 1\u2009mM NAD+, 0.05\u2009mg\u2009ml\u20131 BSA (Takara), 1\u2009nM TkKptA and 12.5\u2013800\u2009nM 32P-labelled tRNA. At each time point (2 and 5\u2009min), 8-\u03bcl aliquots were spotted on Whatman 3MM filter paper, which was immediately soaked in 5% (wt/vol) trichloroacetic acid. The filter paper was washed three times for 15 min with ice-cold 5% (wt/vol) trichloroacetic acid, rinsed for 5\u2009min with ice-cold ethanol and dried in air. Radioactivity on the filter paper was measured by liquid scintillation counting . Kinetic parameters were calculated using Prism 7.TkKptA-mediated dephosphorylation of UN.\u2009viennensis arkI was PCR amplified and cloned into pMW118 (Invitrogen) under the control of the synthetic constitutive J23106 promoter68, followed by insertion of sequences encoding a His6 tag and a 3\u00d7Flag tag at the C terminus of the N.\u2009viennensis arkI gene, yielding pMW-J23106-nvarkI . The ampicillin resistance cassette (Ampr) was replaced with a chloramphenicol resistance cassette (Camr), yielding pQE-80LC-tkkptA, pQE-80LC-eckptA and pQE-80LC-sctpt1, respectively (Supplementary Table E.\u2009coli \u0394trmB\u0394tapT (Kanr) strain was transformed with pMW-J23106-nvarkI and further transformed with pQE-80LC-tkkptA, pQE-80LC-eckptA or pQE-80LC-sctpt1. The transformants were inoculated in 3\u2009ml LB supplemented with 20\u2009\u03bcg\u2009ml\u20131 chloramphenicol, 50\u2009\u03bcg\u2009ml\u20131 kanamycin and 100\u2009\u03bcg\u2009ml\u20131 ampicillin and cultured at 37\u2009\u00b0C until mid-log phase. When the OD610 reached 0.6, IPTG was added to a final concentration of 10 or 100\u2009\u03bcM to induce expression of the KptA/Tpt1p homologue and cells were cultured for 3.5\u2009h. A 1.5-ml aliquot of the culture was taken, and the tRNA fraction was extracted and analysed by shotgun RNA-MS as described above. Primers, E.\u2009coli strains and plasmids used are listed in Supplementary Tables Chemical structures were drawn with chemical structure drawing tools, including ACD/ChemSketch (ACD/Labs) or ChemDraw (PerkinElmer).Further information on research design is available in the\u00a0Any methods, additional references, Nature Research reporting summaries, source data, extended data, supplementary information, acknowledgements, peer review information; details of author contributions and competing interests; and statements of data and code availability are available at 10.1038/s41586-022-04677-2.Supplementary InformationThis file contains Supplementary Notes 1\u20137, Supplementary Figs. 1\u201310, Supplementary Tables 1\u20137 and the legend for Supplementary Video 1.Reporting SummaryPeer Review FileSupplementary Video 1S. tokodaii tRNAVal3.Structural switch of the core region in"}
{"text": "The crystal structure of 1 is similar to that of the bromide salt (2), possessing anion\u00b7\u00b7\u00b7C5F5N\u00b7\u00b7\u00b7C6H5 motifs, whilst that of 3 contains columns of alternating iodide anions and parallel tetrafluoropyridyl rings. All three crystal structures possess C(1)\u2013H\u2219\u2219\u2219X\u2212 and C(2)\u2013H\u2219\u2219\u2219X\u2212 hydrogen bonding. DFT calculations reveal that the strengths of the hydrogen bonding interactions lie in the order C(1)\u2013H\u00b7\u00b7\u00b7X\u2212 > C(3)\u2013H\u00b7\u00b7\u00b7X\u2212 > C(2)\u2013H\u00b7\u00b7\u00b7X\u2212 for the same halide (X\u2212) and Cl\u2212 > Br\u2212 > I\u2212 for each position. It is suggested that salt 3 adopts a different structure to salts 1 and 2 because of the larger size of iodide.The crystal structures of 1--3-benzylimidazolium chloride ( However, we hypothesize that simple monoatomic anions, which differ in size and consequent properties, such as polarizability, can also exert a strong influence on the crystal structures adopted by 1-polyfluoroaryl-3-benzylimidazolium salts. In order to test this hypothesis we chose to investigate the crystal structures of the halide salts of 1--3-benzylimidazolium  and polively + and [(NC5F4NC3H3NCH2Ph).2X]\u2212 peaks in the positive and negative ion mass spectra, respectively of 1 (X = Cl) and 3 (X = I), and the absence of [(NC5F4NC3H3NCH2Ph)2.Br]+ and [(NC5F4NC3H3NCH2Ph).2Br]\u2212. Attempts to prepare the fluoride analogue by the same method were unsuccessful. Salt 1 crystallized from chloroform in the polar orthorhombic space group Pna21, the same as that of 2. Salt 3 crystallized from dichloromethane in the centrosymmetric monoclinic space group P21/c. Crystal data are given in 1 and 3, together with the positions of the closest halide anions, are shown in 1--3-benzylimidazolium chloride \u2013C(9) for 1 and 2, but parallel for 3 \u2013H\u00b7\u00b7\u00b7X\u2212 hydrogen bonding, with that of salt 3 possessing two C(1)\u2013H\u00b7\u00b7\u00b7X\u2212 interactions. As expected, the C\u00b7\u00b7\u00b7X\u2212 distances  \u2212 378.0516. C30H20F8N635Cl3 requires 723.0784; found [2M + Cl]\u2212 723.1200.MS (positive ion): C3.\u00a0\u00a015H10F4N3 requires 308.0811; found [M \u2212 I]+ 308.1033. C30H20F8N6I requires 743.0666; found [2M \u2212 I]+ 743.1140. MS (negative ion): I requires 126.9045; found [M \u2212 C15H10F4N3]\u2212 126.9181. C15H10F4N3I2 requires 561.8900; found [M + I]\u2212 561.9393.MS (positive ion): C1 and 3 were obtained by slow evaporation of solvent from solutions in chloroform and dichloromethane, respectively. Crystal data are listed in \u03b1 radiation. The structures of 1 and 3 were solved using Olex2 [3)) was used for subsequent refinements. The function minimized was [w(|Fo|2 \u2212 |Fc|2)] with reflection weights w\u22121 = [\u03c32 |Fo|2 + (g1P)2 + (g2P)] where p = [max |Fo|2 + 2|Fc|2]/3. Crystals of ng Olex2  and refing Olex2  refineme1) and 2063364 (3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.CCDC 2063365 -3-benzylimidazolium bromide are 1.083 \u00c5 within experimental error [ 1.322 \u00c5 .\u2212\u00b7\u00b7\u00b7C5F4N\u00b7\u00b7\u00b7C6H5 motifs, whilst the iodide salt, because of the larger size of the anion, adopts a different crystal structure containing columns of alternating tetrafluoropyridyl rings and iodide anions. The strength of charge-assisted hydrogen bonding interactions lie in the order C(1)\u2013H\u00b7\u00b7\u00b7X\u2212 > C(3)\u2013H\u00b7\u00b7\u00b7X\u2212 > C(2)\u2013H\u00b7\u00b7\u00b7X\u2212 for the same anion and Cl\u2212 > Br\u2212 > I\u2212 for each position. The strengths of the X\u2212\u00b7\u00b7\u00b7C5F4N interactions also decreases in the order Cl\u2212 > Br\u2212 > I\u2212.1--3-benzylimidazolium chloride and bromide adopt similar crystal structures with X"}
{"text": "Correction to: BMC Biotechnol (2022) 22:33 10.1186/s12896-022-00765-3Following publication of the original article , the autIncorrect 22ama121022j0001\u2009\u2192\u2009Correct JP22ama121022j0001Incorrect 17H06305\u2009\u2192\u2009Correct JP17H06305Incorrect 20H03243\u2009\u2192\u2009Correct JP20H03243The original article has been corrected."}
{"text": "II ion has an N4 square-planar coordination geometry defined by the four N atoms of two bidentate 2,3-di-2-pyridyl\u00adpyrazine ligands.In the title complex, the central Pd 14H10N4)2](NO3)2\u00b7CH3CN, consists of a cationic PdII complex, two anions and one lattice solvent mol\u00adecule, all in general positions. In the complex, the PdII cation is four-coordinated in a slightly distorted square-planar geometry defined by the four N atoms of two bidentate 2,3-di-2-pyridyl\u00adpyrazine ligands. The complex, anions and solvent mol\u00adecule are linked by weak C\u2014H\u22efO inter\u00admolecular hydrogen bonds. In the crystal, the complex mol\u00adecules are stacked in columns along the a axis.The title compound, [Pd(C The Pd\u2014N bond lengths are almost equal [2.0170\u2005(18) to 2.0286\u2005(19)\u2005\u00c5]. In the crystal, the pyridine rings are considerably inclined to the least-squares plane of the [PdN4] unit [maximum deviation = 0.0204\u2005(7)\u2005\u00c5], with dihedral angles of 70.56\u2005(7) (ring N3\u22efC9), 67.63\u2005(6) (ring N4\u22efC14), 71.32\u2005(6) (ring N7\u22efC23) and 71.64\u2005(7)\u00b0 (ring N8\u22efC28). The nearly planar pyrazine rings [maximum deviation = 0.027\u2005(2)\u2005\u00c5] are fairly perpendicular to the [PdN4] unit plane, with dihedral angles of 82.07\u2005(7) (ring N1\u22efC4) and 84.20\u2005(7)\u00b0 (ring N5\u22efC18).The title compound consists of a cationic Pdle Fig.\u00a01. In the a axis. In the columns, numerous intra- and inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring N4\u22efC14) and Cg1i [symmetry code: (i) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01), the centroid-to-centroid separation is 3.688\u2005(2)\u2005\u00c5 and the planes are parallel and shifted by 1.683\u2005\u00c5.In the crystal structure Fig.\u00a02, the com3)2\u00b72H2O  and stirred for 1\u2005h at room temperature. The formed precipitate was recrystallized from MeOH/ether, washed with ether, and dried under vacuum, to give a white powder (0.378\u2005g). Crystals suitable for X-ray analysis were obtained by slow evaporation of a MeOH/CH3CN solution, at room temperature.To a solution of 2,3-di-2-pyridyl\u00adpyrazine  in acetone (30\u2005ml) was added Pd(NO\u22123) and the deepest hole (\u22120.49\u2005e\u2005\u00c5\u22123) in the last difference-Fourier map are located 1.02 and 0.97\u2005\u00c5, respectively, from atom O3.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S241431462100153X/bh4059sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S241431462100153X/bh4059Isup2.hklStructure factors: contains datablock(s) I. DOI: 2062092CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of a biologically important pharmacophore containing chalcone is reported. 18H17FO5, the conformation about the C=C bond of the central enone group is trans. The dihedral angle between the benzene rings is 13.08\u2005(3)\u00b0. The hy\u00addroxy group attached to the benzene ring is involved in an intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into chains along [001].In the title mol\u00adecule, C Especially when they have a hydroxyl group at the ortho position of an aromatic ring adjacent to the carbonyl group, they play important roles as precursors to form other flavonoids such as flavones, flavanones, flavonols and isoflavones \u00b0. An intra\u00admolecular O5\u2014H5\u22efO1 hydrogen bond \u00b0] and the para meth\u00adoxy group is almost coplanar with the ring [C6\u2014C7\u2014O4\u2014C12 = 177.1\u2005(2)\u00b0]. The meth\u00adoxy group at the ortho position is rotated significantly from the ring plane [C4\u2014C5\u2014O2\u2014C10 = \u2212123.9\u2005(2)\u00b0]. In the crystal, weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into chains propagating along [001] ethanone  in 40\u2005ml of anhydrous ethanol was added 2,3,4-tri\u00admeth\u00adoxy\u00adbenzaldehyde  and the temperature was adjusted to around 275\u2013277\u2005K in an ice bath. To the cooled reaction mixture was added 3\u2005ml of 40% aqueous KOH solution and the reaction mixture was stirred at room temperature for 20\u2005h. After completion of the reaction (monitored by thin-layer chromatography), this mixture was poured into ice water (100\u2005ml) and the resulting solution acidified with 6 Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620000711/lh4051sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620000711/lh4051Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620000711/lh4051Isup3.cmlSupporting information file. DOI: 1979111CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complexes bearing a tridentate polypyridine ligand and N-coordinating thio\u00adcyanato ligands at the axial or equatorial position are compared.The crystal structures of two Ru viz. cis-aqua\u00ad(thio\u00adcyanato-\u03baN)(tri\u00adphen\u00adyl\u00adphosphine-\u03baP)ruthenium(II) hexa\u00adfluorido\u00adphosphate\u2013acetone\u2013water (1/0.5/1), [Ru(NCS)(C21H13N5)(C18H15P)(H2O)]PF6\u00b70.5C3H6O\u00b7H2O (I) and trans-bis\u00ad(pyridine-\u03baN)(thiocyanato-\u03baN)ruthenium(II) thio\u00adcyanate, [Ru(NCS)(C21H13N5)(C5H5N)2]NCS (II), with an N-coordinating thio\u00adcyanato group and a tridentate polypyridyl supporting ligand, are reported. The RuII atom in each of the cationic complexes adopts a distorted octa\u00adhedral coordination sphere, defined by an N atom of the thio\u00adcyanato ligand, three N atoms from the tridentate polypyridyl ligand, and an O and P atom in (I) or two pyridine-N atoms in (II) derived from monodentate ligands. The thio\u00adcyanato ligand in (I) coordinates in an axial manner to the {Ru-dnp} unit , whereas it coordinates in an equatorial manner in (II). In the crystal structure of compound (I), intra\u00admolecular C\u2014H\u22efO, C\u2014H\u22efN and O\u2014H\u22efN hydrogen bonds as well as \u03c0\u2013\u03c0 contacts are present, in addition to inter\u00admolecular C\u2014H\u22efF, C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds. In the crystal structure of compound (II), intra\u00admolecular C\u2014H\u22efN hydrogen bonds are observed along with inter\u00admolecular C\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds as well as a \u03c0\u2013\u03c0 inter\u00adaction.The mol\u00adecular and crystal structures of two ruthenium(II) complexes,  Their crystal structures are reported and compared in this communication.During the current study, the reaction of precursors with different axially bound ligands with the NCS2.II atoms in (I)et al., 20133 or pyridine and the non-coordinating N atoms in dnp or the monodentate ligands [OH2 in (I)NCS in (II)]. In (I)Cg1\u22efCg2 = 3.640\u2005(4)\u2005\u00c5 and Cg3\u22efCg4 = 3.749\u2005(3)\u2005\u00c5 where Cg1, Cg2, Cg3, and Cg4 are the centroids of the N1/C1\u2013C5, C29\u2013C34, N3/C9\u2013C13, and C35\u2013C40 rings, respectively] are present, with a slippage of 1.2\u2005\u00c5 for Cg1\u22efCg2. It is inferred from these results that both \u03c0\u2013\u03c0 inter\u00adactions are not exactly cofacial. The slippage angle \u03b2 is 19.2\u00b0 for Cg1\u22efCg2 and 16.2\u00b0 for Cg3\u22efCg4.Figs. 1II complexes containing polypyridines have been determined structurally, but the N-atom coordination is overwhelmingly dominant. These complexes can be distinguished crystallographically by the Ru\u2014X\u2014C bond angle (X = N or S) through the coordinating atom. For example, the Ru\u2014S\u2014C bond angles (for S-ligating examples) are 104\u2013106\u00b0 II atoms in both compounds exhibit an N-coordination.As mentioned above, it is important to distinguish the coordination atom of the thio\u00adcyanato ligand because of its ambidentate coordination mode. Both S- and N-coordinated RuII atom and the nitro\u00adgen atom in (I)II\u2013NCS}+ moieties  per formula unit. Apart from Coulombic forces, there are weak C\u2014H\u22efF hydrogen bonds between the complex cation and the PF6\u2212 anion n Table\u00a01 and the n Table\u00a01.X (X = N or S) hydrogen-bonding inter\u00adactions exist between the complex cation and the NCS\u2212 anion (Table\u00a02Cg5\u22efCg5i = 4.0093\u2005(15)\u2005\u00c5; Cg5 is the centroid of the N5/C17\u2013C21 ring; symmetry code: (i) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] with a centroid slippage of 1.263\u2005\u00c5 for Cg5\u22efCg5i are present. The slippage angle \u03b2 is 18.4\u00b0 for Cg5\u22efCg5i. These inter\u00adactions lead to the formation of a three-dimensional network structure n Table\u00a02 along wire Fig.\u00a04.4.II complexes with both N-coordinating thio\u00adcyanato and tridentate terpyridine derivative ligands (tpyR) of the form [Ru(tpyR)(NCS)L2]n  have been reported, as revealed by a search of the Cambridge Crystal Structure Database 2(H2O)](PF6)2  . Crystals suitable for use in X-ray diffraction (XRD) studies were grown by vapor diffusion of diethyl ether into an acetone solution of (I)CN at 2130\u2005cm\u22121.A methano\u00adlic solution (40\u2005ml) containing [Ru(dnp)(PPh2(H2O)](PF6)2  . The yield was 9\u2005mg (40%). Single crystals suitable for XRD studies were obtained by recrystallization from acetone. FTIR using a KBr pellet showed \u03bdCN at 2121 (ligand) and 2055\u2005cm\u22121 (counter-ion).For the synthesis of compound (II)6.Uiso(H) = 1.2Ueq(C). The acetone solvent mol\u00adecule in (I)Table\u00a0310.1107/S2056989022004443/wm5641sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989022004443/wm5641Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004443/wm5641IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2168839, 2168838CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule is planar (r.m.s. deviation = 0.0164\u2005\u00c5) and in the crystal, inversion-symmetric dimers are formed as a result of pairs of strong O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds. A brief comparison is made with structurally related compounds deposited in the CSD. In addition, the synthesis and some spectroscopic details are presented.The structure of 2-chloro-1-(3-hy\u00addroxy\u00adphen\u00adyl)ethanone, C All bond lengths and angles fall within the expected ranges for organic structures.The mol\u00adecule of I Fig.\u00a01 is plana3.O\u22efO2i and O1i\u2014H1Oi\u22efO2 , giving an i and C2i\u2014H2i\u22efO2 (Table\u00a01i = 2.22\u2005(3)\u2005\u00c5]. These inter\u00adactions are all illustrated in Fig.\u00a02ii [symmetry code: (ii) \u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a01 screw-related mol\u00adecules, which loosely connect the dimers into layers parallel to . QAJNAS  was added dropwise to a stirred mixture of 3-hy\u00addroxy\u00adaceto\u00adphenone  in 5\u2005ml of methanol and 10\u2005ml of ethyl acetate/di\u00adchloro\u00admethane at 293\u2013303\u2005K. After completion of the addition, it was allowed to return to RT with stirring for 1\u2005h. The reaction was monitored by TLC. Then the solvent was removed under reduced pressure by rotary evaporation to give the desired product in 95% yield. An overall reaction scheme is depicted in Fig.\u00a04Spectroscopic data: Infrared and NMR spectroscopic details are as follows.\u22121): 3400 , 2987 (C\u2014H stretching), 1694 (C=C stretching), 1789 , 832 .FTIR : 4.7 , 5.671 , 7.14 , 7.36\u20137.4 , 7.493\u20137.51 .6.sp2\u2014H) and 0.99\u2005\u00c5 (R2CH2). The hydroxyl hydrogen atom coordinates were refined freely. In all cases, Uiso(H) values were set to 1.2Ueq of the attached atom.Crystal data, data collection, and structure refinement details are given in Table\u00a0210.1107/S2056989022009835/vm2272sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022009835/vm2272Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022009835/vm2272Isup3.cmlSupporting information file. DOI: 2211527CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-[1-(2-pyrazin\u00adyl)ethyl\u00adidene]propane\u00adhydrazide, is a ligand able to form polynuclear metal complexes. The mol\u00adecule is not planar due to a twist between the oxime and amide groups. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds into supra\u00admolecular chains.The title compound, 2-hy\u00addroxy\u00adimino- 9H11N5O2, the oxime and hydrazide groups are situated in a cis-position in relation to the C\u2014C bond linking the two functional groups. The CH3C(=NOH)C(O)NH fragment deviates from planarity because of a twist between the oxime and amide groups. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming zigzag chains in the [013] and [0In the mol\u00adecule of the title compound, C In recent decades, a number of ligands based on 2-hy\u00addroxy\u00adimino\u00adpropane\u00adhydrazide have been obtained. It was shown that such a type of ligand reveals a strong tendency for the formation of polynuclear complexes (Anwar N-[1-(pyrazin-2-yl)ethyl\u00adidene]propano\u00adhydrazide (1), was first described in the work of Feng and co-workers \u00adpropane\u00adhydrazide derivatives. Such a conformation is stabilized additionally by an H4\u22efN5 attractive inter\u00adaction (2.33\u2005\u00c5). Despite the distance being shorter than the sum of the van der Waals radii C(O)NH fragment deviates from planarity (r.m.s. deviation of 0.362\u2005\u00c5) because of a twist between the oxime and the amide groups about the C7\u2014C8 bond. The maximum deviations are 0.8763\u2005(9) and 0.3355\u2005(18)\u2005\u00c5, respectively, for hydrogen (H9C) and non-hydrogen (O1) atoms. The O1\u2014C7\u2014C8\u2014N5 torsion angle is 165.1\u2005(3)\u00b0, significantly less than the average value in 2-(hy\u00addroxy\u00adimino)\u00adpropane\u00adhydrazide derivatives published previ\u00adously [172.1\u2005(4)\u00b0]. Thus, such a twist distortion of the mol\u00adecule seems to be a result of the crystal packing.The CH3.i and C2\u2014H2A\u22efO2ii inter\u00admolecular hydrogen bonds [symmetry codes: (i) \u2212x\u00a0+\u00a0y\u00a0+\u00a01, z\u00a0+\u00a0x\u00a0+\u00a0y\u00a0\u2212\u00a01, z\u00a0\u2212\u00a0A\u22efN2iii inter\u00admolecular hydrogen bonds [symmetry code: (iii) \u2212x\u00a0+\u00a01, \u2212y\u00a0\u2212\u00a01, z\u00a0+\u00a0In the crystal, mol\u00adecules are linked by O2\u2014H2\u22efO1ns Fig.\u00a02. These c4.et al., 2007CrystalExplorer17  from red  through white to blue . The Hirshfeld surface of the title compound mapped over dnorm, in the colour range \u22120.6441 to 1.3084 a.u. is shown in Fig.\u00a03A\u22efN2 are the most noticeable inter\u00admolecular inter\u00adactions. In addition, a C2\u2014H2A\u22efO2 weak inter\u00admolecular inter\u00adaction is observed.The Hirshfeld surface analysis  pair with the full fingerprint plot outlined in grey. Fig.\u00a04d) reveals two sharp spikes along 1.9\u2005\u00c5 < id + ed < 2.4\u2005\u00c5, which are associated with the O2\u2014H2\u22efO1 hydrogen bond.A fingerprint plot delineated into specific inter\u00adatomic contacts contains information related to specific inter\u00admolecular inter\u00adactions. The blue colour refers to the frequency of occurrence of the  level .The calculated geometric parameters are in good agreement with experimental values. It is important to note that the accuracy of the semi-empirical GFN2-xTB method is close to that of the DFT calculations, even though GFN2-xTB calculations are significantly computationally \u2018cheaper\u2019  and C7\u2014N4 is shorter  than calculated. Such calculation errors are probably typical for hydrazide derivatives at this level of theory . The maximum number of metal centres per mol\u00adecule for the discrete complexes of this type is 12 \u00adpropane\u00adhydrazide derivatives. Most of them are polynuclear 37.et al., 20181H NMR, 400.13\u2005MHz, (DMSO-d6): 11.97 , 10.21 , 9.31 , 8.56 , 8.55 , 2.37 , 2.02 . IR : 1658 (CO amid I), 1034 (NO oxime). Analysis calculated for C9H11N5O2: C 48.86, H 5.01, N 31.66%; found: C 48.49, H 5.22, N 31.42%.The title compound was prepared according to a slightly modified procedure (Feng 8.Uiso = nUeq of the carrier atom (n = 1.5 for methyl groups and n = 1.2 for other hydrogen atoms).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022007927/vm2270sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007927/vm2270Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022007927/vm2270Isup3.cdxSupporting information file. DOI: 2195126CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound was redetermined at 100\u2005K in order to achieve improved structural data, especially with respect to the C\u2014C distances and the hydrogen bonding. 2(C4H9)4Cl2(OH)2], was redetermined at 100\u2005K by use of an area detector to provide new data to improve the structural parameters for detailed analysis. Noteworthy is the folding of the central, non-symmetric, four-membered [SnO]2 ring [dihedral angle about the O\u22efO axis = 1.09\u2005(3)\u00b0], as well as the elongation of the Sn\u2014Cl bonds [mean value = 2.5096\u2005(4)\u2005\u00c5], as a result of inter\u00admolecular O\u2014H\u22efCl hydrogen bonds; the latter lead to a chain-like arrangement of dimeric mol\u00adecules along [101].The structure of the dimeric title compound, [Sn The structure of the title compound has been determined previously at room temperature using point detector data as part of a paper describing the series of dimeric di-tert-butyl\u00adtin(IV) hydroxide halides, [tBu2Sn(OH)X]2 with X = F, Cl and Br I]2 I]2 compounds [pure state: d(Sn\u2014C)mean = 2.190\u2005(3)\u2005\u00c5 mean = 2.193\u2005(10)\u2005\u00c5  to 1.532\u2005(2)\u2005\u00c5 [mean value: 1.527\u2005(4)\u2005\u00c5], Cmeth\u00adyl\u2014C\u2014Cmeth\u00adyl angles in the range 107.1\u2005(1) to 111.1\u2005(1)\u00b0 [mean value: 109.5\u2005(11)\u00b0] and Sn\u2014C\u2014C angles of 107.1\u2005(1) to 111.1\u2005(1)\u00b0 [mean value: 108.9\u2005(12)\u00b0]. These new data are of the same precision and absolute values as those found in the iodide compound both in the pure state , which are considerably longer in comparison with other Br\u00f8nstedt-Base (BB) stabilized diorganotin(IV)-hydroxide-chlorides 2 mol\u00adecules along [101], Fig.\u00a03These unusually long Sn\u2014Cl bonds in the title compound arise from the fact that the chloride atoms are involved in inter\u00admolecular O\u2014H\u22efCl hydrogen bonds Table\u00a01, resultiet al.  I. DOI: 10.1107/S2414314623000561/tk4087Isup2.hklStructure factors: contains datablock(s) I. DOI: 2237568CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-indole ring system is nearly planar, while the conformation of the 4H-pyran ring is close to a flattened boat. The mean planes of these fragments are approximately perpendicular to each other. In the crystal, the mol\u00adecules are connected into layers by N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds.In the title structure, the 2,3-di\u00adhydro-1 17H14BrN3O4, an admixture [0.0324\u2005(11)] of its 7-bromo isomer. The 2,3-di\u00adhydro-1H-indole ring system is nearly planar, while the conformation of the 4H-pyran ring is close to a flattened boat. The mean planes of these fragments form a dihedral angle of 86.67\u2005(9)\u00b0. The carboxyl\u00adate group lies near the plane of 4H-pyran, its orientation is stabilized by an intra\u00admolecular C\u2014H\u22efO contact. In the crystal, the mol\u00adecules are connected into layers by N\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds. The most important contributions to the crystal packing are from H\u22efH (33.1%), O\u22efH/H\u22efO (16.3%), N\u22efH/H\u22efN (12.1%), Br\u22efH/H\u22efBr (11.5%) and C\u22efH/H\u22efC (10.6%) inter\u00adactions.The crystal used for structure determination contained, along with the title compound, C The mean planes of the 2,3-di\u00adhydro-1H-indole system and the 4H-pyran ring are approximately perpendicular to each other, forming a dihedral angle of 86.67\u2005(9)\u00b0. The carboxyl\u00adate group lies near the plane of 4H-pyran, with O3\u2014C13\u2014C10\u2014C11 and O4\u2014C13\u2014C10\u2014C3 torsion angles of \u221213.4\u2005(3) and \u22128.8\u2005(2)\u00b0, respectively. An intra\u00admolecular C16\u2014H16A\u22efO3 contact stabilizes the conformation of the mol\u00adecule  ring motif :0.0324\u2005(11) ratio, whereas the positions of other atoms of these isomers coincide with each other Fig.\u00a02. The 2,3le Fig.\u00a02, generat3.H-pyran and benzene rings link adjacent mol\u00adecules within these layers  Table\u00a01 \u25b8 \u25b8. ICrystalExplorer17  ring motif. The mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds into ribbons extending along the b-axis direction and consisting of In the crystal of II, the six-membered pyran ring adopts a conformation close to a flattened boat, as in the title structure. The mol\u00adecules are joined by pairs of N\u2014H\u22efN hydrogen bonds into dimers, those are linked by N\u2014H\u22efO contacts to form ribbons along the a-axis direction.In the crystal of III, the pyran ring is nearly planar. The mol\u00adecules are joined by pairs of N\u2014H\u22efN hydrogen bonds into centrosymmetric dimers, which are linked by N\u2014H\u22efO contacts into ribbons along the c-axis direction.In the crystal of 5.The title compound was synthesized using the reported procedure , N8\u2014H8A = 0.88\u2005(3) and N8\u2014H8B = 0.86\u2005(3)\u2005\u00c5], but their isotropic displacement parameters were constrained to take a value of 1.2Ueq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C\u2014H = 0.95 (aromatic), 0.99 (methyl\u00adene) and 0.98\u2005\u00c5 (meth\u00adyl), withUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all others.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989022008271/yk2174sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022008271/yk2174Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022008271/yk2174Isup3.cmlSupporting information file. DOI: 2202347CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The compound crystallizes with one mol\u00adecule in the asymmetric unit in the monoclinic space group P21/n with a rather long b axis [33.8752\u2005(2)\u2005\u00c5]. Weak C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions consolidate the crystal packing. The nitrite-O atoms each occupy a single position in the coordination geometry.The mol\u00adecular structure of the title compound, [Ag(NO The nitrito ligand coordinates in a near symmetric fashion with similar bond lengths . The pseudo-tetra\u00adhedral coordination environment exhibited around the AgI atom stems from the three coordinating ligands, with corresponding bond angles of P1\u2014Ag1\u2014P2 [124.597\u2005(16)\u00b0], P1\u2014Ag1\u2014O1 [116.26\u2005(6)\u00b0], P1\u2014Ag1\u2014O2 [125.62\u2005(4)\u00b0], P2\u2014Ag1\u2014O1 [107.68\u2005(7)\u00b0], and P2\u2014Ag1\u2014O2 [107.83\u2005(4)\u00b0]. The bidentate coordination of the nitrito ligand is underpinned by the O1\u2014Ag1\u2014O2 bite angle of 50.80\u2005(7)\u00b0. The ipso-aryl carbon atoms of each of the phosphine ligands overlap in a near-staggered fashion when viewed down the P1\u2014Ag1\u2014P2 axis, presumably due to the steric effect of the bulky phosphine ligands. Corresponding torsion angles are P2\u2014Ag1\u2014P1\u2014C1 = 9.90\u2005(7)\u00b0, P2\u2014Ag1\u2014P1\u2014C8 = \u2212108.02\u2005(8)\u00b0, P2\u2014Ag1\u2014P1\u2014C15 = 128.73\u2005(9)\u00b0, P1\u2014Ag1\u2014P2\u2014C22 = \u2212172.57\u2005(7)\u00b0, P1\u2014Ag1\u2014P2\u2014C36 = 70.75\u2005(8)\u00b0, and P1\u2014Ag1\u2014P2\u2014C29 = \u221247.35\u2005(7)\u00b0. All of the aforementioned bond lengths and angles closely correspond to those of related AgI phosphine complexes  and silver nitrite (1\u2005mmol) were dissolved separately in aceto\u00adnitrile (10\u2005ml). The two solutions were carefully mixed together and heated to 353\u2005K for approximately 2\u2005h. The solution was left to crystallize, and small clear colourless crystals were obtained.Tris-Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622011488/wm4174sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011488/wm4174Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011488/wm4174Isup3.cdxSupporting information file. DOI: 2223249CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure, the cations and anions are inter\u00adconnected via several N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds.The title compound, C 6H2N3O7\u2212\u00b7C10H13Cl2N2+, crystallizes with one 1-piperazine (DP) cation and one picrate (PA) anion in the asymmetric unit. In the crystal structure, the DP cation and PA anion are inter\u00adconnected via several N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. The DP cation and PA anion are further connected through C\u2014Cl\u22ef\u03c0  and N\u2014O\u22ef\u03c0 [3.7814\u2005(4)\u2005\u00c5] inter\u00adactions. The DP cations are further inter\u00adconnected via a weak inter\u00admolecular Cl\u22efCl [3.2613\u2005(4)\u2005\u00c5] halogen\u2013halogen inter\u00adaction. The combination of these supra\u00admolecular inter\u00adactions leads to a herringbone like supra\u00admolecular architecture.The title compound, C Inversion-related cation\u2013anion pairs are also linked through N1\u2014H1A\u22efO4, N1\u2014H1B\u22efO2 and C17\u2014H17\u22efO1 hydrogen bonds, forming an Cg1, C\u2014Cl\u22efCg3v and N\u2014O\u22efCg3; symmetry codes: (v) 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] with C\u22ef\u03c0 distances of 3.8201\u2005(4) and 3.7785\u2005(4)\u2005\u00c5, and N\u22ef\u03c0 = 3.782\u2005(2)\u2005\u00c5, with C\u2014Cl\u22ef\u03c0 angles of 74.15\u2005(7) and 76.91\u2005(7)\u00b0 and an N\u2014O\u22ef\u03c0 angle of 68.80\u2005(12)\u00b0. The combination of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014Cl\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions leads to the formation of a three-dimensional supra\u00admolecular herringbone architecture, which propagates along the a- and c-axis directions  inter\u00adactions [3.2613\u2005(4)\u2005\u00c5] piperazine (DP)  and picric acid (PA)  were dissolved independently in water and ethanol. The reactants were then mixed together in a 100\u2005ml beaker and heated over a water bath at 90\u00b0C for 1\u2005h Fig.\u00a05. The cleCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621003795/bv4037sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621003795/bv4037Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621003795/bv4037Isup3.cmlSupporting information file. DOI: 2076126CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the pento\u00adfuran\u00adose ring has a twisted conformation while the other five-membered ring has an envelope conformation; the two hy\u00addroxy groups C are involved in an infinite network of O\u2014H\u22ef O bonds, forming a layer parallel to the (001) plane. 8H14O5, the pento\u00adfuran\u00adose five-membered ring has a twisted conformation on two carbon atoms while the five-membered ring of the iso\u00adpropyl\u00adidene group has an envelope conformation on an oxygen atom. Hy\u00addroxy groups are involved an infinite network of O\u2014H\u22efO hydrogen bonds that leads to the formation of a layer parallel to the (001) plane. Only weak C\u2014H\u22efO contacts exist between neighboring layers.In the title compound C Our inter\u00adest in 1 stems from the possibility of conducting de\u00adoxy\u00adgenation at its C3 position to obtain 3-de\u00adoxy-1,2-O-iso\u00adpropyl\u00adidene-\u03b2-d-threo-pento\u00adfuran\u00adose as a chiral synthon for further synthetic work  side to furnish 1,2-O-iso\u00adpropyl\u00adidene-5-O\u2013t-butyl\u00addiphenyl\u00adsilyl-\u03b2-d-lyxo-furan\u00adose, whose desilylation gave the target 1. It should be pointed out that under these iso\u00adpropyl\u00adidenation conditions, d-lyxose furnished only its \u03b1,\u03b2-2,3-O-iso\u00adpropyl\u00adidene\u00adfuran\u00adose \u2005\u00c5, \u03c6 = 117.6\u2005(2)\u00b0]. The five-membered ring of the iso\u00adpropyl\u00adidene group has an envelope conformation on atom O1 . Puckering parameters  distance is 3.389\u2005(2)\u2005\u00c5. Similar hydrogen bonds have been observed in various carbohydrates  plane Table\u00a01. Only wep Table\u00a01 may addiet al.  and a probability of the absolute configuration being correct of 1.000.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620016302/zq4044sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620016302/zq4044Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620016302/zq4044Isup3.cdxSupporting information file. DOI: 10.1107/S2414314620016302/zq4044sup4.txtCuK CIF file for chirality confirmation. DOI: 2050681CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds connect the mol\u00adecules into [001] chains. 12H9ClN2O, the dihedral angle between the aromatic rings is 1.78\u2005(4)\u00b0 and an intra\u00admolecular O\u2014H\u22efN hydrogen bond closes an S(6) ring. In the crystal, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds connect the mol\u00adecules into [001] chains.In the title compound, C S(6) ring. The disposition of the aromatic rings is trans as indicated by the C2\u2014N2\u2014C13\u2014C7 torsion angle of \u2212179.7\u2005(2)\u00b0 \u00b0 and an intra\u00admolecular O\u2014H\u22efN hydrogen bond closes an )\u00b0 Fig.\u00a01. In the )\u00b0 Fig.\u00a01 generateps Fig.\u00a02. These aps Fig.\u00a02.et al.  and 2-hy\u00addroxy benzaldehyde (1.2\u2005mmol) were mixed in 20\u2005ml of absolute ethanol with the addition of few drops of piperidine as catalyst. The mixture was refluxed for 5\u2005h at 60\u201370\u00b0C. Colourless blocks of the title compound were obtained from the mother solution on cooling.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620000115/hb4333sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314620000115/hb4333Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620000115/hb4333Isup3.cmlSupporting information file. DOI: 1975774CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-021-00096-x, published online 19 October 2021Correction to: The original version of this Article contained an error in the legend of Figure\u00a01.A) Effect on IFN-\u03b3 (a) and IL-10 expression (b) and IFN-\u03b3 to IL-10 expression ratio (c) in LPS-stimulated macrophage cells. (B) Effect on IFN-\u03b3 (a) and IL-10 expression (b) and IFN-\u03b3 to IL-10 expression ratio (c) in resident macrophage cells. Macrophage cells (1\u2009\u00d7\u2009106/mL) isolated from peritoneal cavity were incubated with\u00a0Lactobacillus rhamnosus\u00a0NK210  or\u00a0Bifidobacterium longum\u00a0NK219  in the absence or presence of LPS. Normal control group (CON) was treated with saline instead of LPS. Data values were described as mean\u2009\u00b1\u2009SD (n\u2009=\u20094). Data values indicate mean\u2009\u00b1\u2009SD.\u00a0#p\u2009<\u20090.05 versus NC group. *p\u2009<\u20090.05 versus LP group.\u201d\u201cEffect of NK210 and NK219 on the expression of interferon (IFN)-\u03b3 and IL-10 in macrophages stimulated with or without LPS. (now reads:A) Effect on IFN-\u03b3 (a) and IL-10 expression (b) and IFN-\u03b3 to IL-10 expression ratio (c) in resident macrophage cells. (B) Effect on IFN-\u03b3 (a) and IL-10 expression (b) and IFN-\u03b3 to IL-10 expression ratio (c) in LPS-stimulated macrophage cells. Macrophage cells (1\u2009\u00d7\u2009106/mL) isolated from peritoneal cavity were incubated with\u00a0Lactobacillus rhamnosus\u00a0NK210  or\u00a0Bifidobacterium longum\u00a0NK219  in the absence or presence of LPS. Normal control group (CON) was treated with saline instead of LPS. Data values were described as mean\u2009\u00b1\u2009SD (n\u2009=\u20094). Data values indicate mean\u2009\u00b1\u2009SD.\u00a0#p\u2009<\u20090.05 versus NC group. *p\u2009<\u20090.05 versus LP group.\u201d\u201cEffect of NK210 and NK219 on the expression of interferon (IFN)-\u03b3 and IL-10 in macrophages stimulated with or without LPS. (The original Article has been corrected."}
{"text": "In the title Schiff base, the dihedral angle between the phenyl rings of the benzil unit is 74.14\u2005(5)\u00b0. 20H14ClNO, obtained from the reaction of 4-chloro aniline with benzil, has an approximate T shape. The dihedral angle between the phenyl rings of the benzil unit is 74.14\u2005(15)\u00b0. The extended structure features C\u2014H\u22efO hydrogen bonds.The title Schiff base, C The C1\u2013C6 phenyl ring makes dihedral angles of 20.56\u2005(6) and 74.03\u2005(6)\u00b0with the C9\u2013C10 and C15\u2013C16 phenyl ring, respectively, of the benzil unit. The dihedral angle between the phenyl rings of the benzil unit is 74.14\u2005(5)\u00b0. The C\u2014N iminium bond length [1.268\u2005(3)\u2005\u00c5] is comparable to that observed in (E)-1-[4-({4-[(4-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adphen\u00adyl}sulfan\u00adyl)phen\u00adyl]ethan-1-one . Together, these hydrogen bonds lead to the formation of a three-dimensional network. Aromatic \u03c0\u2013\u03c0 stacking generates inversion dimers featuring the C15\u2013C20 phenyl rings with a centroid\u2013centroid distance of 3.744\u2005(3)\u2005\u00c5 [Fig.\u00a03b)]. Along the c-axis direction, weak C\u2014H\u22ef\u03c0(ring) inter\u00adactions occur.In the crystal, the mol\u00adecules are aligned head-to-foot along the g Table\u00a01. The C18Crystal Explorer 3.1  and shape-index. The red spots in Fig.\u00a04a) reflect the formation of C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions. In the shape-index map [Fig.\u00a04b)], the adjacent red and blue triangle-like patches represent concave regions that indicate C\u2014H\u22ef\u03c0(ring) and \u03c0\u2013\u03c0 stacking inter\u00adactions. The two-dimensional FP plots indicate that the most important contributions to the packing, in descending percentage contribution, are from H\u22efC (37.7%), H\u22efH (34.6%), H\u22efCl (14.0%), H\u22efO (6.1%), H\u22efN (4.0%) and C\u22efC (1.9%) contacts.A Hirshfeld surface (HS) analysis was performed and the associated two-dimensional fingerprint (FP) plots , 1660 (C=O), 3064 (aromatic C\u2014H), 1212 (C\u2014N) and 718 (C\u2014Cl).To a solution of benzil  and 1\u2005ml of acetic acid in ethanol (20\u2005ml) was added 4-chloro aniline (0.01\u2005mmol) dissolved in ethanol (15\u2005ml). The mixture was stirred for 3\u2005h under reflux. The product was isolated, recrystallized from ethanol solution and then dried in a vacuum to give the title compound . Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution. IR \u03bd, cmCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623000652/hb4414sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623000652/hb4414Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623000652/hb4414Isup3.cmlSupporting information file. DOI: 2237868CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Compounds 1\u20133 are obtained by reacting Me\u2010cAAC=PK (amino)carbene) and dihaloaryl borane in toluene. All three compounds were characterized by X\u2010ray crystallography. Quantum mechanical studies indicated that these compounds have two lone pairs on the P center viz., an \u03c3\u2010type lone pair and a \u201chidden\u201d \u03c0\u2010type lone pair. Hence, these compounds can act as double Lewis bases, and the basicity of the \u03c0\u2010type lone pair is higher than the \u03c3\u2010type lone pair.Herein, the synthesis and characterization of the carbene\u2010stabilized boryl phosphinidenes  What hides within: Three different singlet boryl phosphinidenes were synthesized by using cAAC carbene, and their inversely polarized phosphaalkene characteristics were investigated. Quantum mechanical studies suggest that the P center of these boryl phosphinidenes contains two lone pairs viz., an \u03c3\u2010type lone pair and a \u201chidden\u201d \u03c0\u2010type lone pair. FoiPr2NP\u0308:), which was formed as a transient intermediate while thermolysis of dibenzo\u20107\u2010phosphanorbornadiene (Scheme\u2005h).i). The reactivities of phosphino\u2010phosphinidene were studied using several nucleophiles such as CO, isocyanides, carbenes, and phosphines, etc. \u20131\u20133) which are also characterized as inversely polarized phosphaalkenes. DFT calculations are employed to obtain further insight into the bonding and structure\u2013property relationship of the newly developed carbene\u2010stabilized boryl phosphinidenes.In 2012, Cummins et\u2005al. reported a mono\u2010coordinated phosphinidene  in a 1\u2009:\u20091 molecular ratio.Compounds 1, 2, and 3 were obtained in good yield at 0\u2009\u00b0C from the concentrated toluene solution. Compounds 1\u20133 were fully characterized by NMR  and mass spectrometry (LIFDI). All these compounds are highly stable in the solid\u2010state and in solutions at room temperature under an inert atmosphere for months. However, they are unstable under ambient conditions and slowly change their intense yellow color to a colorless form. Single\u2010crystal X\u2010ray diffraction and elemental analysis confirmed the compositions of 1, 2, and 3.The block\u2010shaped yellow crystals of 13C, 31P, and 11B NMR spectroscopy provided a wealth of structural information on the inversely polarized phosphaalkene. The 13C{1H} signal of C=P unit of inversely polarized phosphaalkenes appeared at 220.9 , 220.8 , and 220.7  ppm for compounds 1, 2, and 3 respectively. The observed 13C{1H} NMR signals and JC\u2010P coupling constants for the C=P units are similar to the reported phosphaalkenes.31P NMR shifts for the compounds are strongly affected by the electronic nature of the substituents and the hybridization of the phosphorus atom. The introduction of an electropositive boryl group provides a deshielding effect on the phosphorus chemical shift. Also, the halogen atoms such as Cl, Br, and I on the boron center typically move the chemical shift significantly downfield. The 31P{1H} NMR signal appeared at 35.5, 47.1, and 66.9\u2005ppm for compounds 1, 2, and 3, respectively. This observation is in accordance with the increasing order of Lewis acidity of the boron center, which increases when the halogen changes from Cl to I.31P{1H} NMR spectroscopy supports the formation of delocalized C\u2212P\u2212B \u03c0\u2010system and the extent of delocalization increases from compound 1 to 3. Note that the 31P chemical shift values move downfield compared to inversely polarized phosphaalkenes.31P chemical shifts for phosphatriafulvenes show inverse polarity around \u221223.2 to \u221274.1\u2005ppm.11B{1H} nucleus and the asymmetric local fields in compounds usually result in broad 11B{1H} NMR resonances. The 11B{1H} NMR resonances appear at 72.83, 71.81, and 69.80\u2005ppm for the compounds 1, 2, and 3, respectively. The 31P and 11B NMR data indicate that the B\u2212P bond has considerable double\u2010bond character and 31P and 11B resonances are similar to those reported phosphinidene boranes (R\u2212B=P\u2212R).1, 2, and 3 consist of a C\u2212P\u2212B backbone with an almost coplanar halogen  atom \u00b0 (1), 179.02 (6)\u00b0 (2), and 177.70 (6)\u00b0 (3). The C=P=B skeleton is significantly bent with a bond angle of 114.68\u00b0, 111.94\u00b0, 110.78\u00b0 and the dihedral angles between C17\u2212C16\u2212N1 and X1\u2212B1\u2212C1 planes are 25.06\u00b0, 21.43\u00b0 and 31.50\u00b0 for compounds 1, 2, and 3, respectively.The solid\u2010state structures of complexes cis to the C\u2212P bond (C16\u2212P1 1.7709 (15)\u2005\u00c5) in complex 1, whereas the B\u2212X bonds in complexes 2 (B1\u2212Br1 2.0085(15)\u2005\u00c5), and 3 (B1\u2212I1 2.2504 (15)\u2005\u00c5) are in trans position to the C\u2212P bonds, respectively. Furthermore, the nearly anti\u2010periplanar alignment represented by torsion angles N\u2212C\u2212P\u2212B (1 172.74(12)\u00b0, 2 164.82(9)\u00b0, 3 157.78(10)\u00b0) decrease from species 1 to 3. The P1\u2212C16 (1 1.7709 (15)\u2005\u00c5, 2 1.7850 (14)\u2005\u00c5, 3 1.7944(14)\u2005\u00c5) bond lengths are longer than reported double bond lengths in phosphaalkenes (1.61\u20131.71\u2005\u00c5)The molecular structures reveal that in the solid state, the B1\u2212Cl1 (1.8046(18)\u2005\u00c5) bond is 1 1.8607(18)\u2005\u00c5, 2 1.8607(15)\u2005\u00c5, 3 1.8456(15)\u2005\u00c5) bond lengths are elongated compared to phosphaborenes (1.8211(16)\u20131.8309(16)\u2005\u00c5)tert\u2010butyl\u20101\u2010phosphaethene)(diethylhydroborato)titanocene] (2.054(3)\u2005\u00c5)3 complex (1.931(4)\u20131.943(4)\u2005\u00c5)1\u20133), the most elongated P\u2212C bond length (1.7944(14)\u2005\u00c5) and the shortest B\u2212P bond length (1.8456(15)\u2005\u00c5) were found in 3 (X=I). This is due to the high Lewis acidity of the boron center of compound 3 compared to 1\u20132 (X=Cl and Br), and the phosphinidene lone pair being relatively more engaged in donating to the boron center and compared to back\u2010bonding to the carbene center of cAAC. Additionally, Ccarbene\u2212N bond lengths in 1\u20133 (1 1.3352(19)\u2005\u00c5, 2 1.3379(16)\u2005\u00c5, 3 1.3306(16)\u2005\u00c5) are elongated (1.9\u20132.5\u2009%) compared to that in free cAAC (1.3053(13)\u2005\u00c5),Similarly, P1\u2212B1  to I . The isomer 1\u2032, where the B\u2212Cl bond is oriented similar to B\u2212X bonds in complexes 2 and 3, is less stable by 1.82\u2005kcal\u2009mol\u22121. It can be attributed to the shorter P\u2212Cl distance (2.97\u2005\u00c5), resulting in strong repulsions between the lone pairs on P and Cl centers .Quantum mechanical calculations were carried out at the M06\u20102X/def2\u2010TZVPP//BP86/def2\u2010TZVP level of theory by incorporating Grimme empirical dispersion correction with Becke\u2013Johnson damping (GD3BJ) to explore the bonding and reactivity of the molecules 1 reveals that HOMO\u20102 is a \u03c3\u2010type lone pair orbital with a larger contribution from the P atom , P\u2212B (1.31\u20131.41) and Ccarbene\u2212N (1.29\u20131.32) bonds. Note that these Wiberg bond indices are lower than the Ccarbene\u2212N Wiberg bond index of free cAAC . The difference in electronegativity also induces polarity in the Ccarbene\u2212P, P\u2212B and Ccarbene\u2212N bonds, reducing the bond index values. These bond index values support the partial double bond character observed in these bonds. The overall high positive group charge on cAAC (0.14\u20130.18) implies that \u03c3\u2010donation from cAAC is higher than the \u03c0\u2010back donation from the P center. The NBO analysis shows considerable polarization of the P\u2212CcAAC \u03c3\u2010MO and \u03c0\u2010MO in opposite directions (Table\u2005S8), thus indicating the inversely polarized phosphaalkene nature. However, the net polarization is minimal, as seen from the natural charges on CcAAC (0.10\u20130.13 e) and P (0.06\u20130.08 e).The molecular orbital (MO) analysis of \u22121 when halogen atom is Cl (1), 2.6\u2005kcal\u2009mol\u22121 for Br (2), and 2.7\u2005kcal\u2009mol\u22121 for I (3). On the other hand, the energetics corresponding to the donation from halogen to B center is significantly high and decreases as 40.7\u2005kcal\u2009mol\u22121 for 1, 35.3\u2005kcal\u2009mol\u22121 for 2, and 30.31\u2005kcal\u2009mol\u22121 for 3. The strength of the donation from the halogen atom is a deciding factor for the P\u2212B and B\u2212X bond lengths. The P\u2212B bond length is shortest for 3 (1.860\u2005\u00c5); this is in agreement with the weaker donation of I lone pairs to the formally empty p\u2010orbital on B. Note that the strength of the donation from P\u2212C \u03c0\u2010NBO to the B center is also significant viz., 38.4\u2005kcal\u2009mol\u22121 for 1, 49.6\u2005kcal\u2009mol\u22121 for 2, and 56.0\u2005kcal\u2009mol\u22121 for 3. The balance between these second\u2010order interactions results in the intermediate dihedral angles between the planes defined by terminal B and C atoms with their corresponding substituents (23.5\u201333.7\u00b0).Three major interactions are responsible for the geometry of the compounds viz., the donation of \u03c3\u2010lone pair on P to B center, the donation of lone pair of electrons from halogen atom to B center, and the donation from P\u2212C \u03c0\u2010NBO to the B center. The strength of interaction corresponding to the donation of \u03c3\u2010lone pair on P to B center is 5.4\u2005kcal\u2009mol1\u20133 is monovalent, forming an electron sharing bond with B center while accepting a lone pair of electrons from cAAC. The bonding is schematically represented in Figure\u2005\u22121 . Hence, the P atom can act as a coordinating center for accepting electrons from cAAC. The calculated dissociation energy of compounds 1\u20133 to respective singlet boryl phosphinidene and cAAC was found to be moderately high, indicative of the strong binding between P\u2212C centers . P\u2212C bond dissociation energy values for carbene stabilized phosphinidenes have been calculated to fall in the range 43\u201375\u2005kcal\u2009mol\u22121 at BP86/TZ2P level of theory.Based on the geometrical, MO and NBO analyses, the P center in \u22121) and close to that of NHCs  and C(PH3)2  but less than that in carbodicarbenes, C(NHCMe)2 .1\u20133. This suggests that the delocalized \u03c0\u2010MO in 1\u20133 is more basic than the \u03c3\u2010lone pair having a very high s\u2010character (53.8\u201354.4\u2009%). Hence, the delocalized \u03c0\u2010MO can be considered as a hidden lone pair. Frenking and co\u2010workers have used the term hidden lone pair for a delocalized \u03c0\u2010MO in carbodicarbenes and related C(0) compounds, which show very high proton affinity.A bent geometry with an active \u03c3\u2010lone pair and a delocalized \u03c0\u2010MO is the prominent feature of carbones and related species.carbene\u2212P (0.7\u20131.3\u2009%) and P\u2212B (2.5\u20132.7\u2009%) bonds and a shortening of the Ccarbene\u2212N bond . This corroborated well with increased cAAC group charge (0.49\u20130.52) and decreased negative natural charge on N (\u22120.35) atom. The MO analysis indicates an active lone pair (35.0\u201338.2\u2009% s character) with a major coefficient on the P atom . The presence of an active lone pair with relatively low s\u2010character induces the addition of the second proton at the P center. The calculated second proton affinity is also quite high , indicating that P (I) center in molecules 1\u20133 can act as a double Lewis base.The first protonation induces an elongation in C1\u20133 feature a P(I) center with two lone pairs, viz. a highly reactive \u201chidden\u201d \u03c0\u2010lone pair and a \u03c3\u2010lone pair.In conclusion, we have designed, synthesized, and characterized three cAAC\u2010stabilized boryl\u2010phosphinidenes, which also show inversely polarized phosphaalkene characteristics. Quantum mechanical calculations reveal that compounds Essential experimental: Crystal data for 1 at 100(2) K: C35H54Cl2BClNP, Mr=566.02\u2005g/mol, 0.401\u00d70.303\u00d70.139\u2005mm, monoclinic, P21/n, a=9.810(2)\u2005\u00c5, b=17.822(3)\u2005\u00c5, c=19.840(3)\u2005\u00c5, \u03b2=92.64(2)\u00b0, V=3465.0(11)\u2005\u00c53, Z=4, \u03bc(MoK\u03b1)=0.179\u2005mm\u22121, \u03b8max=25.510\u00b0, 78252 reflections measured, 6411 independent (Rint=0.0530), R1=0.0364 [I>2\u03c3(I)], wR2=0.0943 , res. density peaks: 0.383 to \u22120.237\u2005e\u2009A\u22123, CCDC: 2058117.2 at 100(2) K: C35H54BBrNP, Mr=610.48\u2005g/mol, 0.584\u00d70.317\u00d70.309\u2005mm, triclinic, P1\u203e, a=9.805(2)\u2005\u00c5, b=11.181(2)\u2005\u00c5, c=16.560(3)\u2005\u00c5, \u03b1=73.82(2)\u00b0, \u03b2=82.35(2)\u00b0, \u03b3=88.07(3)\u00b0, V=1728.0(6)\u2005\u00c53, Z=2, \u03bc(MoK\u03b1)=1.258\u2005mm\u22121, \u03b8max=27.934\u00b0, 53463 reflections measured, 8274 independent (Rint=0.0469), R1=0.0265 [I>2\u03c3(I)], wR2=0.0674 , res. density peaks: 0.368 to \u22120.357\u2005e\u2009A\u22123.Crystal data for 3 at 100(2) K: C42H62BINP, Mr=749.60\u2005g/mol, 0.341\u00d70.253\u00d70.235\u2005mm, triclinic, P1\u203e, a=10.676(2)\u2005\u00c5, b=12.167(2)\u2005\u00c5, c=16.836(3)\u2005\u00c5, \u03b1=107.24(2)\u00b0, \u03b2=94.60(2)\u00b0, \u03b3=101.62(3)\u00b0, V=2022.8(7)\u2005\u00c53, Z=2, \u03bc(Mo K\u03b1)=0.859\u2005mm\u22121, \u03b8max=27.200\u00b0, 82576 reflections measured, 9022 independent (Rint=0.0303), R1=0.0213 [I>2\u03c3(I)], wR2=0.0531 , res. density peaks: 0.452 to \u22120.462\u2005e\u2009A\u22123.Crystal data for \u03bb correction1 was applied using SADABS.F2 using SHELXLAll crystals were selected under cooling by using an X\u2010Temp2 device.1), 2058118 (2), and 2058119 (3)2058117  should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the title 1:2 co-crystal, C\u2014I\u22efN halogen bonds between one of the 1,2,3,5-tetra\u00adfluoro-4,6-di\u00adiodo\u00adbenzene mol\u00adecules and the 5-{[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]ethyn\u00adyl}pyrimidine mol\u00adecule form [110] chains while the second 1,2,3,5-tetra\u00adfluoro-4,6-di\u00adiodo\u00adbenzene mol\u00adecule resides in [100] channels. 14H13N3\u00b72CF4I2. In the extended structure, two unique C\u2014I\u22efN halogen bonds from one of the 1,2,3,5-tetra\u00adfluoro-4,6-di\u00adiodo\u00adbenzene mol\u00adecules to the pyrimidine N atoms of the 5-{[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]ethyn\u00adyl}pyrimidine mol\u00adecule generate [110] chains and layers of these chains are \u03c0-stacked along the a-axis direction. The second 1,2,3,5-tetra\u00adfluoro-4,6-di\u00adiodo\u00adbenzene mol\u00adecule resides in channels formed parallel to the a-axis direction between stacks of 5-{[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]ethyn\u00adyl}pyrimidine mol\u00adecules and inter\u00adacts with them via C\u2014I\u22ef\u03c0 contacts.The treatment of 5-{[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]ethyn\u00adyl}pyrimidine with a threefold excess of 1,2,3,5-tetra\u00adfluoro-4,6-di\u00adiodo\u00adbenzene in di\u00adchloro\u00admethane solution led to the formation of the unexpected 1:2 title co-crystal, C The APEP and the halogen-bonded 13DIFP mol\u00adecule are essentially coplanar: the inter\u00adplanar angle between the pyrimidine ring and the amino\u00adphenyl ring is 4.24\u2005(15)\u00b0 and the inter\u00adplanar angle between the pyrimidine ring and the halogen-bonded 13DIFP mol\u00adecule is 6.63\u2005(15)\u00b0. The two unique C\u2014I\u22efN halogen bonds that combine to form a zigzag alternating halogen-bonded chain, shown in Fig.\u00a02i = 2.853\u2005(2) and 2.901\u2005(2)\u2005\u00c5 and angles C15\u2014I1\u22efN1 and C17\u2014I2\u22efN2i = 174.8\u2005(9) and 173.8\u2005(8)\u00b0, respectively . These distances and angles are similar to those previously reported in the 1:1 co-crystal formed between these two mol\u00adecules of 2.920\u2005(2)\u2005\u00c5 and 178.27\u2005(6)\u00b0  1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] separations of 3.276\u2005(3) and 3.316\u2005(3)\u2005\u00c5, respectively. These are significantly less than the sum of the van der Waals radii of 3.68\u2005\u00c5 at 89 and 90%, respectively. The second I atom has close I\u22efF contacts to two neighboring 13DIFB mol\u00adecules with I3\u22efF6iii and I3\u22efF3iv separations of 3.2142\u2005(17) and 3.30129\u2005(15)\u2005\u00c5 as compared to the sum of the van der Waals radii of 3.38\u2005\u00c5 .The pair of loosely \u03c0-stacked 13DIFB mol\u00adecules inter\u00adact with the surrounding mol\u00adecules as shown in the Hirshfeld surface plot in Fig.\u00a05The pyrimidine APEP (8.3\u2005mg) was dissolved in 2\u2005ml of di\u00adchloro\u00admethane in a screw-cap vial. Three equivalents of 13DIFB were added and the solvent was allowed to slowly evaporate until crystals formed when the vial was sealed to prevent further loss of solvent.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314622003807/hb4404sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622003807/hb4404Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622003807/hb4404Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2414314622003807/hb4404Isup4.cmlSupporting information file. DOI: 2164881CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two of the copper(I) atoms are additionally linked to PMe3 ligands, giving a distorted trigonal coordination.The mol\u00adecular structure of the title complex consists of an eight-membered Cu 4(C9H11)4(C3H9P)2] or [Cu4(Mes)4(PMe3)2] , was synthesized from copper(I) mesityl and tri\u00admethyl\u00adphosphane in THF as solvent. The mol\u00adecular structure of the complex has C2 symmetry and consists of four copper(I) atoms bridged by four \u03bc-mesityl groups, giving an eight-membered puckered {Cu4C4} ring. Additionally, two copper(I) atoms at opposite corners of the Cu4 rhomb are each linked to a terminal PMe3 ligand. The PMe3-bearing copper(I) atoms exhibit a distorted trigonal\u2013planar coordination mode whereas the remaining Cu atoms linked to two mesityl groups are nearly linearly coordinated.The title compound, [Cu I organyls, mesitylcopper is one of the most extensively studied compounds. Since its first synthesis in 1981 , the reaction proceeds under retention of the tetra\u00adnuclear cluster structure to form [Cu4(Mes)4(THT)2] 2]\u00b7C7H8 with a yet unknown crystal structure 2Cu][CuMes2] 4(PMe3)2] (1).In order to get some insight into the reactivity of mesitylcopper towards sterically less demanding phosphanes, tri\u00admethyl\u00adphosphane was chosen as a ligand. Treatment of a solution of mesitylcopper in THF with PMe1) comprises four copper(I) atoms that are linked by four \u03bc-mesityl groups to give an eight-membered {Cu4C4} ring \u20132.4625\u2005(5)\u2005\u00c5] suggest cuprophilic inter\u00adactions. The Cu\u22efCu separations between the copper atoms at opposite corners of the rhomb are 4.2013\u2005(5)\u2005\u00c5 for Cu2\u22efCu2i , [Cu4(o-Tol)4(SMe2)2] 2]  exhibits two types of differently coordin\u00adated Cu atoms \u00b0] is clearly more pronounced than in [Cu4Mes4] (164.05\u2013165.70\u00b0). Apart from two mesityl groups, Cu2 bears a PMe3 unit as a third ligand. The increased coordination number leads to a further enlargement of the Cu\u2014C distances with values of 2.093\u2005(3) and 2.095\u2005(3)\u2005\u00c5. The coordination around Cu2 is planar with a C\u2014Cu\u2014C angle of 163.0\u2005(1)\u00b0 and C\u2014Cu\u2014P angles of 97.9\u2005(1)\u00b0 and 99.0\u2005(1)\u00b0 (sum of the angles around Cu2: 359.9\u00b0). Comparison of the bond lengths of compound (1) and related [Cu4Mes4L2] complexes reveals that the ligand PMe3 leads to a larger increase of the Cu\u2014C distances for the tricoordinate copper atoms than other ligands investigated so far. In [Cu4Mes4L2] complexes with L = piperidine, allyl methyl sulfide, 2,5-di\u00adthia\u00adhexane, tetra\u00adhydro\u00adthio\u00adphene and bis\u00ad{2-[1-(di\u00admethyl\u00adamino)\u00adeth\u00adyl]phenyl\u00adthiol\u00adato}magnesium, the mean Cu\u2014C distances for the tricoordinated copper atoms are in the range 2.054\u20132.064\u2005\u00c5. In the case of the dicoordinated Cu there is no particular effect. Furthermore, there is a slight influence on the C\u2014Cu\u2014C angles for the dicoordinated [138.3\u2005(1)\u00b0] and the tricoordinate copper atoms [163.0\u2005(1)\u00b0], which are smaller than in the [Cu4Mes4L2] complexes mentioned above .The mol\u00adecular structure of  = 2.87\u2005\u00c5, C17\u2014H17A\u22efCg2 = 167\u00b0 .The mol\u00adecular packing reveals no special supra\u00admolecular features Fig.\u00a02. Most ofI aryl compounds with auxiliary phosphane ligands are relatively rare. According to the CSD database ] -type compounds are 1.922\u2005\u00c5 for the PPh3 derivative 4(PMe3)2] may be attributed to the lower coordination number of the copper atoms. The same effect is also visible for the Cu\u2014P distances of 2.189\u2005\u00c5 2] (R\u2032= Et) with two phosphane units attached to copper. In this case, the copper atom exhibits a distorted trigonal\u2013planar coordination with markedly enlarged Cu\u2014C (1.979\u2005\u00c5) and Cu\u2014P (2.250 and 2.256\u2005\u00c5) distances magnesium units as ligands 4(PMe3)2] (1) was precipitated by the addition of 30\u2005ml of n-hexane. After filtration, the colorless product was washed with diethyl ether (2 \u00d7 5\u2005ml) and dried under vacuum. Single crystals suitable for X-ray analysis were obtained by slow diffusion of n-hexane into a THF solution of the product. Yield: 0.33\u2005g (60%). C42H62Cu4P2 (883.01\u2005g\u2005mol\u22121). Analysis: Cu 29.0%  IR (cm\u22121) 2997(w), 2963(m), 2901(m), 2855(w), 2842(w), 2802(w), 2705(w), 1589(w), 1637(w), 1376(w), 1448(w), 1418(m), 1362(w), 1302(w), 1286(m), 1257(w), 1215(w), 1164(w), 1024(w), 939(s), 873(w), 844(s), 730(s), 710(w), 670(m), 576(w), 538(m), 484(w), 357(m), 328(m), 301(m), 275(w). 1H NMR (C6D6): \u03b4 0.60 , 2.08 , 2.73 , 6.68 . 13C{1H} NMR (C6D6): \u03b4 15.4 , 21.4 , 28.7 , 125.6 , 127.4 , 134.4 , 150.0 . 31P{1H} NMR (C6D6): \u03b4 \u221244.6 (s br).A solution of 0.46\u2005g (2.5\u2005mmol) mesitylcopper  I. DOI: 10.1107/S2414314621005940/wm4146Isup2.hklStructure factors: contains datablock(s) I. DOI: 2088681CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "It exhibits a defect disk-shaped architecture. DC magnetic property studies in the 2.0\u2013300\u2005K range revealed anti\u00adferromagnetic inter\u00adactions between the CoII ions.A mixed-valence Co 2L) bearing O2N donors for the preparation of a novel Co6 cluster is reported. The hexa\u00adnuclear cobalt com\u00adplex, namely, di-\u03bc2-acetato\u00adtetra\u00adkis\u00ad{\u03bc2-2-[(4-chloro-2-oxido\u00adbenzyl\u00adidene\u00adamino)\u00admeth\u00adyl]phenolato}tetra-\u03bc3-methano\u00adlato-tetra\u00adcobalt(II)dicobalt(III), [CoII4CoIII2(C14H10ClNO2)4(CH3COO)2(CH3O)4], was obtained using Co(CH3COO)2\u00b74H2O and H2L as starting materials in MeOH under solvothermal conditions. The six metal ions are linked together by the \u03bc3-O atoms of four deprotonated MeOH mol\u00adecules, two CH3COO\u2212 units and six phenolate O atoms of four L2\u2212 ligands to form a defect disk-shaped topology. DC magnetic susceptibility investigations revealed the existence of anti\u00adferromagnetic inter\u00adactions in the Co6 cluster.The employment of the new Schiff base ligand 2-[(4-chloro-2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00admeth\u00adyl]phenol (H The tube was sealed and heated at 80 \u00b0C for 48\u2005h under autogenous pressure. It was then cooled to room temperature and dark-red needle-like crystals were obtained. The crystals were collected, washed with MeOH (2\u2005ml) and dried in air . Analysis calculated (%) for C64H58Cl4Co6N4O16: C 47.03, H 3.58, N 3.43; found (%): C 46.18, H 4.048, N 3.280. Selected IR data for 1 (cm\u22121): 1637 (s), 1590 (s), 1523 (s), 1450 (m), 1419 (m), 1286 (w), 1248 (s), 1185 (s), 1089 (m), 1021 (m), 933 (s), 874 (m), 852 (w), 755 (s).To a Pyrex tube (10\u2005ml) was added a mixture of HPLATON  = 1.2Ueq(C). The H atoms of CH3 groups were refined as rotating groups, with Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a012L and Co(CH3COO)2\u00b74H2O in MeOH in the presence of NEt3 under solvothermal conditions led to the isolation of 1 in moderate yield. Co(CH3COO)2\u00b74H2O is a good starting material because it not only serves as a convenient metal source, but also provides CH3COO\u2212 bridging ligands. In the solid state, com\u00adplex 1 is stable in air and its elemental analysis is consistent with the given mol\u00adecular formula.The reaction of H1 . The signals of the carb\u00adoxy\u00adl \u03bdas(CO2) and \u03bds(CO2) vibrations were found in the 1637\u20131419\u2005cm\u22121 range. The vibrations of the C=N bond appear at 1450\u2005cm\u22121. Several bands in the 1286\u20131185\u2005cm\u22121 range were assigned to the vibrations of the aromatic rings. The sharp signals in the 979\u2013766\u2005cm\u22121 range were ascribed to the vibrations of C\u2014H bonds.The vibrational bands in the IR spectrum agree well with the formulation of com\u00adplex 1 were obtained from MeOH under solvothermal conditions. Complex 1 crystallized in the ortho\u00adrhom\u00adbic space group P212121. The structure is shown in Fig.\u00a011 is com\u00adposed of six cobalt ions, four 2-[(4-chloro-2-oxido\u00adbenzyl\u00adidene\u00adamino)\u00admeth\u00adyl]phenolate (L2\u2212) ligands, two acetate ligands and four methanol-solvent-derived MeO\u2212 ligands. There exists an approximate C2 symmetry in the mol\u00adecule. The imine N atom and both phenolate O-atom donors of each L2\u2212 ligand coordinate each cobalt centre. Bond valence calculations ]. Of the six cobalt centres, the Co1, Co3, Co4 and Co5 ions are six-coordinated, and the Co2 and Co6 ions are five-coordinated. The coordination environments of the Co2 and Co6 ions, and the Co3 and Co5 ions are individually identical. The Co1 centre is present in a distorted octa\u00adhedral O6 coordination environment, among which two O atoms are from two \u03bc2-\u03ba4O:O,O\u2032,N L2\u2212 ligands and four O atoms are from four \u03bc3-O\u2212 MeO\u2212 ligands. The Co2 centre is enclosed by the N and O atoms of one \u03bc2-\u03ba4O:O,O\u2032,N L2\u2212 ligand, one O atom of a \u03bc3-\u03ba5O:O,N,O\u2032:O\u2032 L2\u2212 ligand and one O atom of one \u03bc3-O\u2212 MeO\u2212 ligand. The six-coordinate NO5 environment around the Co3 ion is accom\u00adplished by two \u03bc3-O\u2212 MeO\u2212 groups, one O atom from one acetate bridge and the N and O atoms of one \u03bc3-\u03ba5O:O,N,O\u2032:O\u2032 L2\u2212 ligand. The six O-donor atoms around the Co6 centre originate from bridging acetate ligands, two \u03bc3-O\u2212 MeO\u2212 groups and two \u03bc3-\u03ba5O:O,N,O\u2032:O\u2032 L2\u2212 ligands. The H2L ligand exhibits two types of coordination mode.Single crystals of SHAPE  geometry for both atoms, with a minimum CShM (contunuous shape measure) value of 1.065 for Co2 and 1.172 for Co6.The geometries of the five-coordinated Co2 and Co6 atoms were analyzed with the program 1 joins a small family of Co6 clusters. Hexa\u00adnuclear cobalt com\u00adplexes mainly exhibit wheel, cage and ring topologies /C. The Curie constant C\u00a0= 12.09\u2005cm3\u2005mol\u22121\u2005K and the Weiss constant \u03b8\u00a0= \u221237.24\u2005K were obtained. The negative \u03b8 value proves the anti\u00adferromagnetic inter\u00adactions.Magnetic susceptibility data as a function of temperature for com\u00adplex 1 was also explored. The ac magnetic susceptibilities for 1 at 1000\u2005Hz under a zero-dc field in the temperature range 2\u201325\u2005K were shown in Fig. S2 (see supporting information). The \u03c7\u2032\u2032 susceptibilities at 1000\u2005Hz did not increase upon lowering the temperature and no peaks were determined. These phenomena revealed that com\u00adplex 1 is not a single-mol\u00adecule magnet.The magnetic dynamic behaviour of 2IIICo4II(L)4(CH3COO)2(MeO)4] (1), based on the hydroxy-con\u00adtaining Schiff base ligand 2-[(4-chloro-2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00admeth\u00adyl]phenol (H2L) was prepared and char\u00adacterized. Complex 1 exhibits a defect disk-shaped top\u00adol\u00adogy. Four cobalt ions are six-coordinated and two cobalt ions are five-coordinated. An investigation of the magnetic properties revealed that there exist anti\u00adferromagnetic inter\u00adactions between the CoII ions.A hexa\u00adnuclear cobalt com\u00adplex of com\u00adposition [Co10.1107/S2053229622005885/wv3009sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2053229622005885/wv3009Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2053229622005885/wv3009sup3.pdfIR spectrum, magnetic susceptibility figure, geometry details and table of CShM values. DOI: 1991979CCDC reference:"}
{"text": "I atom exhibits a distorted tetra\u00adhedral coordination environment, defined by three P atoms of three benzyl-di\u00adphenyl\u00adphosphane ligands and one O atom of a nitrato ligand.The central Ag 3)(C19H17P)3], exhibits a severely distorted tetra\u00adhedral coordination environment around the central AgI atom, comprising one O and three P atoms. Apart from a primary Ag\u2014O coordination of the nitrato ligand of 2.667\u2005(3)\u2005\u00c5, a second (weaker) secondary inter\u00adaction of the nitrato ligand via the other O atom of 3.118\u2005(4)\u2005\u00c5 is observed. The compound crystallizes with a complete mol\u00adecule in the asymmetric unit. Weak C\u2014H\u22efO inter\u00adactions consolidate the packing.The mol\u00adecular structure of the title complex, [Ag(NO The nitrato coordinates to the AgI atom via O2 (Ag1\u2014O2 = 2.667\u2005(5)\u2005\u00c5). A secondary weak inter\u00adaction between O1 and Ag1 is also observed, with an inter\u00adaction distance of 3.118\u2005(4)\u2005\u00c5, which is thought to help stabilize the coordination around Ag1. The three N\u2014O bond lengths of the nitrato ligand are nearly identical with a range between 1.221\u2005(3) and 1.233\u2005(3)\u2005\u00c5. The NO3 ligand and the Ag1\u2014P3 bond all lie  within the same plane, with P1 and P2 on either side of the plane. Corresponding torsion angles are N1\u2014O2\u2014Ag1\u2014P1 = 110.78\u2005(18)\u00b0, N1\u2014O2\u2014Ag1\u2014P2 = \u2212127.26\u2005(19)\u00b0, and N1\u2014O2\u2014Ag1\u2014P3 = \u22125.9\u2005(2)\u00b0. The concentration of bulky arene groups from the three phosphine ligands also does not appear to notably affect the tetra\u00adhedral environment of each of the P atoms, with typical C\u2032\u2014P\u2014C\u2032\u2032 bond angles between 99.02\u2005(10)\u2013105.80\u2005(11)\u00b0, and an average of 103.40\u00b0.The mol\u00adecular structure of the title compound is shown in Fig.\u00a013 rich layer and an alternating arene-rich layer  was added to a solution of silver nitrate (1\u2005mmol) in 20\u2005ml aceto\u00adnitrile. The reaction mixture was heated under reflux for a few hours. It was filtered and left to form crystals. Small colourless crystals were obtained overnight.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622011476/wm4175sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011476/wm4175Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011476/wm4175Isup3.cdxSupporting information file. DOI: 2223250CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title mol\u00adecule is essentially flat. In the crystal the mol\u00adecules are linked by a system of N\u2014H\u22efN hydrogen bonds formed by the hydrazinyl group, a Br\u22efBr halogen bond, and \u03c0-stacking between the pyridine rings. 5H6BrN3, crystallizes in the ortho\u00adrhom\u00adbic space group P212121 with two mol\u00adecules with different conformations in the asymmetric unit. In the crystal, N\u2014H\u22efN and bifurcated N\u2014H\u22ef hydrogen bonds link the mol\u00adecules into [100] chains; a short Br\u22efBr halogen bond and \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed.The title compound, C The asymmetric unit contains two conformationally non-equivalent mol\u00adecules of 6-bromo\u00adpyridin-2-ylhydrazine, (I1) and (I2), as shown in Fig.\u00a01I1) and (I2), respectively. The spatial arrangements of the hydrazino groups, as defined by the torsion angles H2A\u2014N2\u2014N3\u2014H3A = 137\u2005(3)\u00b0 and H5\u2014N5\u2014N6\u2014H6A = 121\u2005(3)\u00b0, correspond to the low-energy conformation that has been calculated for acyl hydrazides  and (I2), however. While in (I1) the hydrazine nitro\u00adgen atom N3 is in the syn-disposition with respect to the pyridine nitro\u00adgen atom N1, with N1\u2014C5\u2014N2\u2014N3 = 5.4\u2005(3)\u00b0, in (I2) the hydrazine group is in the anti-conformation, with the corresponding torsion angle N4\u2014C10\u2014N5\u2014N6 = 171.0\u2005(2)\u00b0. For comparison, in 3-chloro\u00adpyrid-2-ylhydrazine  for which X-ray diffraction data are available is 2-hydrazino\u00adpyridine; however, no crystal structure of this mol\u00adecule as a free base is known. In crystalline palladium(II)  is extensive and involves all nitro\u00adgen atoms of both hydrazine groups and pyridine rings (Table\u00a01I1) and (I2), as shown in Fig.\u00a01A and H3B, and N6 acts as a double acceptor \u2005\u00c5, symmetry code: (i) \u22121\u00a0+\u00a0x, y, z] is about 0.18\u2005\u00c5 shorter than the sum of the van der Waals radii. The aromatic rings of both (I1) and (I2) are involved in a well-defined system of staggered \u03c0\u2013\u03c0 stacking inter\u00adactions \u2005\u00c5], which satisfies the distance and directionality conditions Table\u00a02 for a has Table\u00a03. These vs Table\u00a03.et al., 2004The title compound was prepared following an established synthetic route  I. DOI: 10.1107/S2414314623001694/hb4424Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623001694/hb4424Isup3.cmlSupporting information file. DOI: 2243041CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal and mol\u00adecular structure of 2-amino-4-ferrocenyl\u00adthia\u00adzole has been determined. The crystal packing features inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22ef\u03c0 inter\u00adactions. 5H5)(C8H7N2S)], was synthesized by the direct reaction of acetyl\u00adferrocene, thio\u00adurea and resublimed iodine. The structure shows one mol\u00adecule in the asymmetric unit. The amino\u00adthia\u00adzole ring makes an angle of 14.53\u2005(13)\u00b0 with the ferrocenyl ring to which it is attached. In the crystal, pairs of complex mol\u00adecules inter\u00adact via inter\u00admolecular N\u2014H\u22efN hydrogen bonds, forming a cyclic dimer which then inter\u00adacts with other dimers through C\u2014H\u22ef\u03c0 inter\u00adactions.The title compound, [Fe(C The steric effect is also evident in the dihedral angle of 14.77\u2005(17)\u00b0 subtended by the planes of the heterocycle (C14/C15/S11/C12/N13) and the Cp plane (C1\u2013C5).3.Cg(C1\u2013C5) the H-to-ring distance is 2.89\u2005\u00c5, as shown in Table\u00a01bc plane  and C\u2014H\u22ef\u03c0 inter\u00adactions. For C10\u2014H10\u22efne Fig.\u00a02. The str4.et al., 2016et al., 2005et al., 2007et al., 2006bet al., 2006aet al., 2005et al., 2006aet al., 2020et al., 20052sp hybridization for all C and N atoms.A search of the Cambridge Structural Database  \u03bd 3099 (ArCH), 2921 (CH3), 1658 (C=N); 1H NMR : 4.62 ; 4.25 ; 4.10 ; 5.00 , 6.35 .The title compound was synthesized according to the reported method (Chopra 6.Uiso(H) = 1.2Ueq(N). C-bound H atoms were positioned geometrically (C\u2014H = 0.93\u20130.98\u2005\u00c5) and refined with isotropically Uiso(H) = 1.2Ueq(C) using a riding model.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022007228/dj2046sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007228/dj2046Isup3.hklStructure factors: contains datablock(s) I. DOI: 1841501CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the salicyl\u00adaldehyde alcohol group is engaged in an intra\u00admolecular O\u2014H\u22efN hydrogen bond with the imine nitro\u00adgen atom, while the tertiary alcohol is engaged in a weak inter\u00admolecular O\u2014H\u22efF hydrogen bond with an adjacent mol\u00adecule. 28H24FNO2, crystallizes in the ortho\u00adrhom\u00adbic space group P212121. A hydrogen-bonding network between the tertiary alcohol group and the fluoro substituent results in [010] chains in the solid state.The title compound, C S)- or (R)-2-amino-1,1,3-tri\u00adphenyl\u00adpropanol  imine, C28H24FNO2, crystallizes in the ortho\u00adrhom\u00adbic space group P212121 as shown in Fig.\u00a01l-enanti\u00adomer structure was collected at 100\u2005K while the d-enanti\u00adomer was collected at 293\u2005K. The unit-cell parameters in the current room-temperature structure are slightly larger (average 1.3%), presumably due to the higher temperature of the data collection. The absolute structure parameter of \u22120.1\u2005(3) has a large uncertainty but the absolute configuration was verified by synthesis and polarimetry.2-Hy\u00addroxy-5-fluoro-benzaldehyde 2The compound has the expected imine\u2013phenol structure as opposed to the iminium\u2013phenoxide tautomer seen in derivatives with less steric bulk. The C23\u2013C28 phenol aromatic ring is close to co-planar with atoms O2 [deviation from the ring plane = 0.040\u2005(2)\u2005\u00c5], C22 [\u20130.061\u2005(2)\u2005\u00c5], N1 [\u20130.034\u2005(2)\u2005\u00c5] and C2 [\u20130.039\u2005(2)\u2005\u00c5]. These four atoms exhibit less deviation from the plane than the enanti\u00adomer. The C22\u2014N1\u2014C2\u2014C1 torsion angle is 110.2\u2005(2)\u00b0, which places atom O1 1.555\u2005(2)\u2005\u00c5 above the plane of the ring. This deviation is 0.166\u2005\u00c5 larger than that for the enanti\u00adomer at 100\u2005K, although the torsion angle is almost identical.et al., 2019The bonds between C27\u2014C28, C23\u2014C28 and C23\u2014C24 are long at 1.39\u20131.41\u2005\u00c5 while those between C24\u2014C25, C25\u2014C26 and C26\u2014C27 are shorter at 1.36\u20131.37\u2005\u00c5. In contrast, the aromatic rings on the benzyl and phenyl substituents have typical C\u2014C bond distances ranging from 1.37\u20131.39\u2005\u00c5. The aromatic C28\u2014O2 bond at 1.349\u2005(3)\u2005\u00c5 is substanti\u00adally shorter than the aliphatic C1\u2014O1 bond [1.439\u2005(3)\u2005\u00c5]. This bonding motif has been seen in related structures (Sha S(6) ring and a long-range inter\u00admolecular hydrogen bond between the tertiary alcohol O1\u2014H1 and the F1 atom of an adjacent mol\u00adecule as shown in Fig.\u00a02There is an intra\u00admolecular O2\u2014H2\u22efN1 hydrogen bond Table\u00a01 between et al., 2019Preparative details of the material have been reported previously  global, I. DOI: 10.1107/S2414314620015801/hb4369Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620015801/hb4369Isup3.cmlSupporting information file. DOI: 1970566CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Zr\u2010bptc  shows a high SO2 uptake of 6.2\u2005mmol\u2009g\u22121 at 0.1\u2005bar and 298\u2005K, reflecting excellent capture capability and removal of SO2 at low concentration (2500\u2005ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically\u2010dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N\u2010aminosulfonamide, thus converting waste to chemical values. In situ X\u2010ray diffraction, infrared micro\u2010spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host\u2013guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.We report reversible high capacity adsorption of SO 2 uptake. The incorporation of atomically\u2010dispersed CuII, amine or heteroatomic sulphur sites enhances the uptake of SO2 at low concentrations. This work confirms that control of pore environments is an important approach for optimising the adsorption of SO2 at low concentrations.A series of Zr\u2010based metal\u2013organic framework materials have been investigated for reversible SO MOFs constructed from {Zr6} clusters are renowned for their high stability. and Zr\u2010DMTDC6(\u03bc3\u2010O)4(\u03bc3\u2010OH)4(OOCR)12} clusters bridged by dicarboxylates to give cubic structures of fcu topology 4(\u03bc3\u2010OH)4(OOCR)12} clusters and tetracarboxylate ligands in an open framework of ftw topology.2\u2009g\u22121. MFM\u20101336(OH)8(OH)8(OOCR)8} clusters and thcb4\u2212 ligands \u20102,2\u2032,4,4\u2032,6,6\u2032\u2010hexamethyl\u20101,1\u2032\u2010biphenyl) to form a flu topology. MFM\u2010133 shows an axially elongated octahedral cage (10.4\u00d710.4\u00d725.9\u2005\u00c5) and a BET surface area of 2156\u2005m2\u2009g\u22121 8(OH)8(OOCR)8} clusters with the tetratopic ligand 3,3\u2032\u2032,5,5\u2032\u2032\u2010tetrakis(4\u2010carboxyphenyl)\u2010p\u2010terphenyl (H4tcpt) to give a neutral framework of sqc topology. MFM\u2010422 is comprised of a trigonal cage  and a hexagonal cage .Zr\u2010bptc is built from 12\u2010connected {Zr2 have been recorded for these MOFs at 273\u2013298\u2005K and from 0\u20131\u2005bar  (36.7\u2005mmol\u2009g\u22121) under the same conditions.2, UiO\u201066\u2010CuII, Zr\u2010DMTDC, Zr\u2010bptc, MFM\u2010133 and MFM\u2010422, show fully reversible uptakes of SO2 of 8.6, 8.8, 8.2, 9.6, 7.8, 8.9 and 13.6\u2005mmol\u2009g\u22121, respectively . The comparable adsorption uptakes of UiO\u201066, UiO\u201066\u2010NH2 and UiO\u201066\u2010CuII at 1\u2005bar (8.2\u20138.8\u2005mmol\u2009g\u22121) suggest that decoration of the pore environment with functional groups or open CuII sites has little impact on the total uptake capacity, which is determined primarily by the surface area. The slightly higher uptake of Zr\u2010DMTDC (9.6\u2005mmol\u2009g\u22121) is consistent with its higher surface area (1345\u2005m2\u2009g\u22121), compared with the other three UiO\u201066 materials. In contrast, enhancements in the uptake at 0.1\u2005bar were observed for UiO\u201066\u2010NH2, UiO\u201066\u2010CuII and Zr\u2010DMTDC, compared with UiO\u201066  for SO2 uptake show decreasing values of 45\u201350, 44\u201332, 38\u201334, 32\u201329, 37\u201327, 31\u201327 and 26\u201319\u2005kJ\u2009mol\u22121 for Zr\u2010bptc, UiO\u201066\u2010NH2, UiO\u201066\u2010CuII, Zr\u2010DMTDC, UiO\u201066, MFM\u2010422 and MFM\u2010133, respectively. Compared with UiO\u201066, the materials UiO\u201066\u2010NH2, UiO\u201066\u2010CuII and Zr\u2010DMTDC show higher values for Qst, consistent with the enhanced adsorption at low pressure. The relatively low values of Qst for MFM\u2010133 and MFM\u2010422 are consistent with their large pores, reducing the strength of host\u2013guest interactions.Gravimetric adsorption isotherms of SO2 and N2 have also been recorded for Zr\u2010bptc, UiO\u201066\u2010NH2, UiO\u201066\u2010CuII, Zr\u2010DMTDC and UiO\u201066 to assess the adsorption selectivity 2/CO2 (1/99) and SO2/N2 (1/99)  at 298\u2005K and 1.0\u2005bar. UiO\u201066, UiO\u201066\u2010NH2, Zr\u2010DMTDC and UiO\u201066\u2010CuII exhibit retention times for SO2 in the expected order of 33, 53, 58 and 100\u2005min\u2009g\u22121, respectively  with retention times of 80, 175, 157 and 175\u2005min\u2009g\u22121 for UiO\u201066, UiO\u201066\u2010NH2, Zr\u2010DMTDC and UiO\u201066\u2010CuII, respectively  and SO2/N2 (2500\u2005ppm SO2/75\u2009% CO2 in He), respectively 4(bdc)6\u2009\u22c5\u2009(SO2)7.7] reveal two binding sites I and II located in cage T (SO2/{Zr6}=5.1) and cage O (SO2/{Zr6}=2.6), respectively \u2005\u00c5] and dipole\u2013dipole interaction [O2S\u22c5\u22c5\u22c5phenyl ring=3.69(2)\u2005\u00c5] stabilise SO2 (I)  is stabilised by two hydrogen bonds  4(bdc\u2212NH2)6\u2009\u22c5\u2009(SO2)8.1], two binding sites I\u2032 and II\u2032 are observed in cage T (SO2/{Zr6}=4.7) and cage O (SO2/{Zr6}=3.4), respectively \u2005\u00c5] was identified and works together with an interaction [O2S\u22c5\u22c5\u22c5phenyl ring=3.58(1)\u2005\u00c5] and hydrogen bonding [OSO\u22c5\u22c5\u22c5\u03bc3\u2010HO=2.94(5)\u2005\u00c5] that stabilise SO2 binding at site I\u2032 \u2005\u00c5, SO2\u22c5\u22c5\u22c5NH2=1.73(3), 2.43(6), 2.87(7), 3.21(1), 3.30(3) and 3.63(8)\u2005\u00c5], which work together with two further dipole\u2013dipole interactions [O2S\u22c5\u22c5\u22c5NH2=2.40(4) and 3.10(7)\u2005\u00c5] to stabilise SO2 at site II\u2032 4(DMTDC)2\u2009\u22c5\u2009(SO2)13.1], four binding sites were revealed (I\u2032\u2032\u2010IV\u2032\u2032). Sites I\u2032\u2032, II\u2032\u2032 and III\u2032\u2032 are localised in cage T   and 3.52(7)\u2005\u00c5; O2S\u22c5\u22c5\u22c5thiophene ring=3.65(3)\u2005\u00c5]  and 2.70(4)\u2005\u00c5; O2S\u22c5\u22c5\u22c5thiophene ring=3.72(3) and 3.72(3)\u2005\u00c5] and supramolecular interaction [O2S\u22c5\u22c5\u22c5\u03bc3\u2010O=3.63(9)\u2005\u00c5]. In addition, dipole\u2013dipole interaction between SO2 at sites I\u2032\u2032 and II\u2032\u2032 [OSO(I\u2032\u2032)\u22c5\u22c5\u22c5SO2(II\u2032\u2032)=2.81(7)\u2005\u00c5] was identified \u2005\u00c5] and [OSO\u22c5\u22c5\u22c5S\u2010ring=3.97(6)\u2005\u00c5] were identified between SO2(III\u2032\u2032) and the framework  and 3.77(8)\u2005\u00c5] and a hydrogen bond [OSO\u22c5\u22c5\u22c5H3C=2.42(2)\u2005\u00c5] 4(bptc)3\u2009\u22c5\u2009(SO2)5.8], six binding sites were revealed (I\u2013VI) \u2005\u00c5] and by two hydrogen bonds [OSO\u22c5\u22c5\u22c5H\u2212C=2.79(8)\u2005\u00c5 and OSO\u22c5\u22c5\u22c5\u03bc3\u2010OH=2.36(5)\u2005\u00c5] \u22c5\u22c5\u22c5SO2(I)=2.06(8) and 3.07(2)\u2005\u00c5, OSO(I)\u22c5\u22c5\u22c5SO2(II)=3.28(1)\u2005\u00c5] with SO2 at site I \u22c5\u22c5\u22c5OSO(V)=2.99(7)\u2005\u00c5, OSO(III)\u22c5\u22c5\u22c5SO2(V)=3.13(5)\u2005\u00c5] with SO2 at site V immobilised by dipole\u2013dipole interactions [O2S\u22c5\u22c5\u22c5phenyl ring=3.72(5)\u2005\u00c5] and two\u2010fold electrostatic interactions [OSO\u22c5\u22c5\u22c5H\u2212C=2.78(1) and 2.93(9)\u2005\u00c5] \u2005\u00c5] and dipole\u2013dipole interaction [OSO(IV)\u22c5\u22c5\u22c5SO2(VI)=3.83(5)\u2005\u00c5] with SO2 at site VI , 1.88(6), 2.23(5), 2.23(5) and 2.69(7)\u2005\u00c5] and two dipole\u2013dipole interactions [O2S\u22c5\u22c5\u22c5OOC=3.07(2) and 3.07(2)\u2005\u00c5]  and carboxylic groups and multiple strong hydrogen bonding at site VI jointly facilitate the exceptional SO2 uptake at low pressure.In SO2 (0\u20131\u2005bar) in the UiO\u201066 type systems have been analysed by in situ synchrotron infrared micro\u2010spectroscopy. For all the MOFs, clear binding of SO2 to the hydroxyl group is observed with a red shift of the \u2212OH stretching vibration at \u22483671\u2005cm\u22121 by 86, 95, 83 and 82\u2005cm\u22121 in UiO\u201066, UiO\u201066\u2010NH2, UiO\u201066\u2010CuII and Zr\u2010DMTDC, respectively  mode was monitored to examine the displacement of bound CO2 by SO2  stretch corresponding to the bare and CO2\u2010loaded materials are approximately equal. Due to weak interaction between CO2 and the \u03bc3\u2010OH group, the bare \u03bc3\u2010OH band is not fully depleted but a new peak at 3643\u2005cm\u22121 appears and is assigned to the [OH\u22c5\u22c5\u22c5OCO] band , there is a steady change in the \u03bd(\u03bc3\u2010OH) region that includes new bands appearing in a similar manner to the pure SO2 experiment, indicating that bound CO2 does not impede SO2 adsorption . Upon 30\u2009% SO2\u2010loading, the characteristic [OH\u22c5\u22c5\u22c5OCO] band has fully disappeared showing that SO2 readily displaces bound CO2 in the pore as a result of stronger binding. Hence, selective capture of SO2 from a mixture of SO2/CO2 can be achieved as demonstrated in separation experiments. Furthermore, 40\u2009%, 45\u2009% and 50\u2009% SO2\u2010loadings fully displace CO2 in UiO\u201066\u2010NH2, Zr\u2010DMTDC and UiO\u201066, respectively . The competitive binding studies of SO2/CO2 further confirm enhanced SO2 binding in the decorated MOFs. The decreasing partial pressure of SO2 on full displacement of CO2 in UiO\u201066\u2010CuII, UiO\u201066\u2010NH2 and Zr\u2010DMTDC is consistent with that observed in static and dynamic adsorption studies.Upon stepwise dosing of the COIn situ INS, coupled with DFT calculations, enables the visualization of binding dynamics for SO2\u2010loaded Zr\u2010bptc. Seven major changes in the INS spectra were observed on the adsorption of SO2 in Zr\u2010bptc  was observed at 0.1\u2005bar and 298\u2005K. Furthermore, the captured SO2 in Zr\u2010bptc can be converted readily into fine chemicals, paving new pathways to \u201cwaste\u2010to\u2010chemicals\u201d technologies. In situ SXPD, microFTIR and INS studies, coupled with DFT calculations, unravel the molecular details of host\u2013guest binding that result in the enhancement of SO2 adsorption at low pressure in these materials. These studies confirm that control of pore environments is an important approach for improving the adsorption of SO2.Powerful drivers exist for the development of new regenerable sorbents for SO6(OH)8(OH)8(tcpt)2], [Zr6O4(OH)4(bptc)3\u2009\u22c5\u2009(SO2)5.8], [Zr6O4(OH)4(DMTDC)6\u2009\u22c5\u2009(SO2)13.1], [Zr6O4(OH)4(bdc)6\u2009\u22c5\u2009(SO2)7.7] and [Zr6O4(OH)4(bdc\u2212NH2)6\u2009\u22c5\u2009(SO2)8.1] are available free of charge from the Cambridge Crystallographic Data Centre .Additional crystallographic information, gas adsorption data, thermogravimetric analysis, density function theory (DFT) calculations and breakthrough data are available in the Supporting Information. The crystal structures of [ZrThe authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file."}
{"text": "In the crystal, the mol\u00adecules are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds into a three-dimensional network. 6H8NO+\u00b7C2H3O2\u2212, the cations and anions are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, generating a three-dimensional network.In the title molecular salt, C The C\u2014OH bond length (C2\u2014O1) of 1.3520\u2005(9)\u2005\u00c5 is similar to that observed for structures containing 2-hy\u00addroxy\u00adbenzenaminium as a cation [1.350\u2005(3)\u2005\u00c5; Jin & Wang, 2013C\u22efO3 cation\u2013anion hydrogen bonds generate a succession of infinite chains [graph set c-axis direction  and acetic acid. This mixture was obtained by dissolution and agitation under reflux for 3\u2005h of 0.5\u2005g of the 2-amino\u00adphenol and 0.27\u2005g of acetic acid in a 1:1 stoichiometric ratio in a hot ethano\u00adlic solution (20\u2005ml). After warming for a few minutes using a water bath, the solution was cooled and kept at room temperature. Within a few days, yellow needle-like crystals suitable for the X-ray analysis were obtained (yield 60%) by evaporation of the solution.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622001122/vm4050sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622001122/vm4050Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001122/vm4050Isup3.cmlSupporting information file. DOI: 2149479CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The plane resulting from the NO2 coordination to Ag is nearly perpendicular to the plane from the coordination of the phosphine-P atoms to Ag [dihedral angle = 86.43\u2005(9)\u00b0].The title Ag P21/c with Z = 4. The asymmetric unit contains one complete silver complex mol\u00adecule, featuring an AgI atom, two diphenyl-p-tolyl\u00adphosphine ligands, and one NO2 coordinating in a bidentate fashion. Near-identical Ag\u2014P bond lengths are observed [Ag1\u2014P1 = 2.4209\u2005(7)\u2005\u00c5 and Ag1\u2014P2 = 2.4251\u2005(8)\u2005\u00c5]. The nitrito ligand is similarly coordinating in a near symmetric fashion (Ag1\u2014O1 = 2.422\u2005(2), Ag1\u2014O2 = 2.415\u2005(2), N1\u2014O1 = 1.253\u2005(4) and N1\u2013O2 = 1.255\u2005(4)\u2005\u00c5). As seen in Fig.\u00a01ipso-carbon atoms of each of the phosphine ligands overlap in a near-eclipsed fashion when viewed down the P1\u2014Ag1\u2014P2 plane Pl2. Corresponding torsion angles are Ag1\u2014P1\u2014C1\u2014C2 = \u221223.4\u2005(3)\u00b0, Ag1\u2014P1\u2014C7\u2014C8 = \u221251.9\u2005(3)\u00b0, Ag1\u2014P1\u2014C13\u2014C14 = 147.8\u2005(3)\u00b0, Ag1\u2014P2\u2014C20\u2014C21 = \u221229.0\u2005(3)\u00b0, Ag1\u2014P2\u2014C26\u2014C27 = 133.3\u2005(3) and Ag1\u2014P2\u2014C32\u2014C33 = 132.3\u2005(3)\u00b0. The complex packs in three dimensions as layers of mol\u00adecules, leaving thin corrugated channels in between the inorganic layers when viewed along the a axis  was dissolved in aceto\u00adnitrile (10\u2005ml). Silver nitrite (1\u2005mmol) was dissolved in aceto\u00adnitrile (5\u2005ml). The diphenyl-p-tolyl\u00adphosphine solution (10\u2005ml) was added to the silver nitrite solution (5\u2005ml), to give a 2:1 molar ratio reaction. The mixture was heated under reflux for 2\u2005h after which the solution was left to crystallize.Diphenyl-For full experimental details including crystal data, data collection and structure refinement details, refer to Table\u00a0110.1107/S2414314622007714/tk4082sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622007714/tk4082Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622007714/tk4082Isup3.cdxSupporting information file. DOI: 2193913CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, weak C\u2014H\u22efCl/O/\u03c0 inter\u00adactions are observed.The title compound, [RuCl 2(C10H14)(C21H21O3P)], crystallizes with two complex mol\u00adecules in the asymmetric unit. The RuII atom has a classical three-legged piano-stool environment being coordinated by a cymene ligand [Ru\u2014centroid = 1.707\u2005(2)/1.704\u2005(2)\u2005\u00c5], a tris\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)phosphane ligand [Ru\u2014P = 2.3629\u2005(15)/2.3665\u2005(15)\u2005\u00c5] and two chloride atoms with the Ru\u2014Cl bonds adopting two distinct values of 2.4068\u2005(16)/2.4167\u2005(16) and 2.4016\u2005(15)/2.4244\u2005(16)\u2005\u00c5. The effective cone and solid angles for the phosphane ligands were calculated to be 149.5/150.2\u00b0 and 25.3/25.6\u00b0, respectively. In the crystal, weak C\u2014H\u22efCl/O/\u03c0 inter\u00adactions are observed. The crystal was refined as a two-component twin.The title compound, [RuCl II\u2013arene complexes is well known in the catalytic transfer hydrogenation of carbonyl compounds 3, as part of ongoing structural investigations into these type of complexes.The activity of the half-sandwich RuPZ = 4), with its two unique mol\u00adecules adopting a distorted pseudo-octa\u00adhedral arrangement, revealing the typical three-legged piano-stool geometry. The coordination sphere of the ruthenium is occupied by a cymene, a tris\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)phosphane and two chloride atoms  and 1.704\u2005(2)\u2005\u00c5 for the two independent mol\u00adecules; the mean Ru\u2014C bond lengths are 2.217\u2005(6) and 2.214\u2005(6)\u2005\u00c5. The coordination of the remaining ligands to the Ru atom shows a slight deviation from the typical octa\u00adhedral geometry with Cl\u2014Ru\u2014Cl = 88.47\u2005(6) and 88.77\u2005(6)\u00b0, respectively; Cl\u2014Ru\u2014P = 86.50\u2005(5)/88.03\u2005(5) and 86.05\u2005(5)/88.21\u2005(6)\u00b0. The Ru\u2014P bond lengths are 2.3629\u2005(15) and 2.3665\u2005(15)\u2005\u00c5, while the Ru\u2014Cl bonds adopt two distinct values of 2.4068\u2005(16)/2.4167\u2005(16) and 2.4016\u2005(15)/2.4244\u2005(16)\u2005\u00c5 for Ru1 and Ru2, respectively. The above bond lengths are within normal ranges as data extracted from the Cambridge Structural Database RuCl2(PR3) systems from 429 hits, containing 535 usable Ru\u2014Cl observations, show a mean value of 2.412\u2005(12)\u2005\u00c5 in a range from 2.378 to 2.459\u2005\u00c5. The same group of structures show for the Ru\u2014P distance a mean value of 2.34\u2005(3)\u2005\u00c5 in a range from 2.235 to 2.434\u2005\u00c5. The geometries of the two independent mol\u00adecules are virtually identical, as seen from a superimposed fit with an r.m.s. deviation of 0.0525\u2005\u00c5 3  in CH2Cl2 (10\u2005ml) was added to a stirred orange solution of [Ru(p-cymene)Cl2]2  under Ar in the same solvent (15\u2005ml) and stirred at r.t. for 24\u2005h. The resulting red reaction mixture was filtered, the filtrate concentrated under reduced pressure to ca 5\u2005ml. Cold diethyl ether (10\u2005ml) was carefully added and the solvent left to slowly evaporate whereby a sample of [RuCl2(C10H14)(C21H21O3P)] suitable for single-crystal X-ray diffraction was obtained as orange crystals.A solution of P: \u03b4 (p.p.m.) 21.39 (s). 1H NMR : \u03b4 (p.p.m.) 1.11 ; 1.84 ; 2.87 ; 3.78 ; 4.93 ; 5.20 ; 6.85 ; 7.69 .Analytical data: \u22123) is located at 0.59\u2005\u00c5 from Ru1 and the highest peak (3.95\u2005e\u2005\u00c5\u22123) 0.90\u2005\u00c5 from Ru1. Initial refinement of data indicated a two-component twin with a 180\u00b0 rotation about the [100] reciprocal direction. Refinement with the appropriate twin law yields a batch scaling factor of 0.18.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621012591/tk4072sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314621012591/tk4072Isup2.hklStructure factors: contains datablock(s) I. DOI: 2124507CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal features 4 16H13ClN2O3)(C3H4N2)], the NiII ion is coordinated by two O atoms and one N atom derived from the dianionic N\u2032-[(1E)-1-(5-chloro-2-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene]-4-meth\u00adoxy\u00adbenzohydrazide ligand and one N atom from the imidazole mol\u00adecule. The N2O2 donor set defines an approximate square-planar geometry. The dihedral angles between the imidazole ring and the fused six-membered and meth\u00adoxy\u00adbenzene rings are 17.78\u2005(14) and 13.23\u2005(16)\u00b0, respectively; the dihedral angle between the C6 rings is 6.63\u2005(12)\u00b0. The most prominent feature of the mol\u00adecular packing is the formation of 41-helical chains  mediated by imidazole-N\u2014H\u22efO(phenoxide) hydrogen bonding; these are linked by methyl-C\u2014H\u22efCl inter\u00adactions.In the title complex, [Ni(C In this complex, the Ni atom is located in a slightly distorted square-planar environment  and C10\u2013C15 (B), and the imidazole ring (C) make dihedral angles of 6.63\u2005(12)\u00b0 (A/B), 17.78\u2005(14)\u00b0 (A/C) and 13.23\u2005(16)\u00b0 (B/C).The Nint Fig.\u00a01. The Ni\u2014c axis, which leads to a 41 helical chain. The chains are connected by C\u2014H\u22efCl inter\u00adactions (Table\u00a02The mol\u00adecular packing is consolidated by imidazole-N\u2014H\u22efO(phenoxide) hydrogen bonding Table\u00a02 along ths Table\u00a02 into a tN\u2032-[(1E)-1-(5-chloro-2-hy\u00addroxyphen\u00adyl)ethyl\u00adidene]-4-meth\u00adoxy\u00adbenzohydrazide , 1H-imidazole , Ni(NO3)2\u00b76H2O , methanol (10\u2005ml) and distilled water (5\u2005ml) were mixed in a 50\u2005ml flask. The mixture was stirred at room temperature for 1\u2005h, the pH was adjusted with saturated sodium carbonate solution to about 8 followed by filtration. Red rectangular block-shaped crystals were obtained after about one month by evaporating the filtrate in air (yield 31%).The Schiff base ligand, Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2414314622002954/tk4076sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622002954/tk4076Isup2.hklStructure factors: contains datablock(s) I. DOI: 2159183CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "STING is an innate immune sensor for immune surveillance of viral/bacterial infection and maintenance of an immune\u2010friendly microenvironment to prevent tumorigenesis. However, if and how STING exerts innate immunity\u2010independent function remains elusive. Here, the authors\u00a0report that STING expression is increased in renal cell carcinoma (RCC) patients and governs tumor growth through non\u2010canonical innate immune signaling involving mitochondrial ROS maintenance and calcium homeostasis. Mitochondrial voltage\u2010dependent anion channel VDAC2 is identified as a new STING binding partner. STING depletion potentiates VDAC2/GRP75\u2010mediated MERC (mitochondria\u2010ER contact) formation to increase mitochondrial ROS/calcium levels, impairs mitochondria function, and suppresses mTORC1/S6K signaling leading to RCC growth retardation. STING interaction with VDAC2 occurs through STING\u2010C88/C91 palmitoylation and inhibiting STING palmitoyl\u2010transferases ZDHHCs by 2\u2010BP significantly impedes RCC cell growth alone or in combination with sorafenib. Together, these studies reveal an innate immunity\u2010independent function of STING in regulating mitochondrial function and growth in RCC, providing a rationale to target the STING/VDAC2 interaction in treating RCC. STING is a canonical innate immune sensor triggering type\u2010I interferon production. Here, an innate immunity\u2010independent STING function in governing renal cancer cell (RCC) proliferation is reported through regulating mitochondria calcium homeostasis by binding mitochondrial calcium transporter VDAC2, as well as its therapeutic potential in treating RCC. Viral and bacterial DNA, as well as damaged genomic and mitochondria DNA, are sensed by the cytosolic DNA sensor cGAS (cyclic GMP\u2010AMP\u00a0synthase). Binding of DNA to cGAS activates its enzymatic activity by triggering cGAS dimerization and phase transition toward synthesizing a special unsymmetric cyclic dinucleotide 2\u20323\u2032\u2010cGAMP. Subsequently, 2\u20323\u2032\u2010cGAMP binds STING (stimulator of interferon response cGAMP interactr 1) on the endoplasmic reticulum (ER) to promote its trafficking to Golgi and other peri\u2010nuclear membrane\u2010coated compartments, where STING recruits TBK1 to phosphorylate IRF3. Phosphorylated IRF3 dimerizes and translocates into nuclei in triggering the expression of interferon \u03b2 (IFN\u03b2). This leads to expression of immune modulatory genes and activation of adaptive immunity. However, STING can also promote autophagy, lysosome\u2010mediated cell death of myeloid cells, and inhibition of viral replication via IFN\u03b2 \u2010independent mechanisms. In addition, STING also plays a critical role in responding to RNA viruses including influenza A viruses (IAV), vesicular stomatitis virus (VSV), dengue virus (DENV) and others, through directly binding and modulating function of essential RNA sensors RIG\u2010I and MAVS and other mechanisms.Innate immunity serves as the first line of defense against infectious pathogens in vertebrates to restrain pathogen invasion and activate adaptive immunity. Pathogen\u2010associated molecular patterns (PAMPs) help distinguish between self\u2010 and non\u2010self\u2010materials and initiate recognition and activation of innate immunity.1 Nucl) and genetic animal models . Moreover, evidence from gt/gtSting (Sting knockout) mice suggests that activation of the STING signaling creates an immune\u2010responsive microenvironment that suppresses tumorigenesis, and STING loss has been observed in colon cancer, gastric cancer and melanoma and restrains IFN\u2010mediated tissue repair and T cell priming. Activating STING has been shown to improve therapeutic effects of immune\u2010checkpoint blockades. STING also exerts a protective effect in metabolic diseases such as alcoholic liver disease, cardiovascular diseases including myocardial infarction, aging, and others through promoting IRF3 phosphorylation and activation of innate immune signaling.Other than nucleotide sensing, hyperactivation of STING has been observed and connected with inflammatory diseases from both pathological perspectives  disease is caused by GOF mutations in STING18) an\u03b2 \u2010independent T cell death by inducing ER stress in T cells. STING depletion has been shown to promote cancer cell growth via accelerated S\u2010phase entry and increased chromosome instability in the absence of an immune environment. Interestingly, STING activation can mediate mitochondrial damage that leads to renal fibrosis and renal failure. Although extensive studies demonstrate that STING is involved in controlling tumorigenesis and renal failure, there is no evidence of STING involvement in the development of RCC, especially through a non\u2010canonical and innate immunity\u2010independent manner.Innate immunity\u2010independent STING function has also been investigated but is less understood. To this end, although STING activation mediates T cell tumor infiltration, STING was also reported to mediate IFN T cells.29 STI22.1 Our analyses of the TCGA dataset identified gene amplification of STING  but not cGAS (MB21D1)  showed STING overexpression.33 Our) Figure\u00a0. Further cGAS MB21  Figure\u00a0. Depleti) Figure\u00a0 led to r) Figure\u00a0 and decr) Figure\u00a0 with the) Figure\u00a0. In cont) Figure\u00a0 also red) Figure\u00a0. We next2.2STING\u2010S366A knockin A498 cells by CRISPR  and mitochondrial ROS (by MitoSOX Red), but also mitochondrial calcium levels (by Rhod\u20102 AM)  Figure\u00a0 were incA Figure\u00a0, suggest2.4 ATP2A2 (SERCA Ca\u2010ATPase located on ER membrane), and ATP1A1  . Binding of STING with VDAC2, ATP2A2, and ATP1A1 was confirmed in both A498  and mitochondrial calcium uniporters (such as VDACs). In this process, GRP75 (glucose\u2010regulated protein 75) at the mitochondria\u2010associated membrane (MAM) bridges IR3R interaction with VDACs. Given we observed STING depletion induced increased Ca2+ flux into mitochondria and upregulated mito\u2010ROS levels  and ECAR (extracellular acidification rate) by seahorse. STING\u2010depleted A498 cells displayed a decreased basal respiration rate compared with control cells and a decreased ATP\u2010driven synthesis ability Figure\u00a0 may caus\u03b2L, Raptor, and Sin1  could promote mTORC1/S6K activation in A498 cells  would be an approach to maximize tumor inhibition. In addition, considering that VDAC2 cysteine residue palmitoylation and oxidation were also previously detected by mass spectrometry, we analyzed if any of these cysteine mutations may affect VDAC2 binding to STING. We generated VDAC2\u2010C103A, C210A, C227A, and C103A/C210A/C227A (3A) mutants and found none of these mutants significantly affect VDAC2 binding to STING , we depleted the protein acyl transferases ZDHHC3 or ZDHHC7 using shRNAs Figure\u00a0, mimicki65 2\u2010Bs Figure\u00a0 and STINs Figure\u00a0, 2\u2010BP trs Figure\u00a0 to facils Figure\u00a0. Notablys Figure\u00a0 through s Figure\u00a0 as STINGs Figure\u00a0. Like STs Figure\u00a0, 2\u2010BP trs Figure\u00a0. As a res Figure\u00a0, while ds Figure\u00a0. Moreoves Figure\u00a0. Interess Figure\u00a0. Like STs Figure\u00a0, 2\u2010BP tr2.8 and currently various targeted therapies have been approved in treating RCC patients in clinic including tyrosine kinase inhibitors , HIF inhibitors (belzutifan) and mTOR inhibitors (temsirolimus and everolimus), we next examined if 2\u2010BP exerts any synergistic effects with clinically approved agents. To this end, although 2\u2010BP reduced mTORC1/S6K activation in RCC cells  and THCA (thyroid carcinoma). If STING is also a vulnerability in these two types of cancers or if STING regulates mitochondria ROS/calcium homeostasis in STAD and THCA remains an interesting topic for further investigations.It remains unclear why unlike other cancers including colon cancer,21 gasTMEM173 (STING) gene is observed in different ethnic populations\u2010 for example, HAQ (R71H\u2010G230A\u2010R293Q) is dominant in East Asian, while Africans have no HAQ. If these various STING variants affect STING binding with VDAC2 and determine STING dependency for cell growth in cancers beyond RCC warrants further in\u2010depth investigations.Notably, the heterogeneity of e no HAQ.69 If 4l\u2010Glutathione (reduced) was purchased from Gold Biotechnology (G\u2010155\u201025). 4\u2010hydroxy Nonenal (4\u2010HNE) (32100) was purchased from Cayman. Sulfobutylether\u2010\u03b2\u2010Cyclodextrin (HY\u201017031), Sorafenib (HY\u201010201A), and RSL3 (HY\u2010100218A) were purchased from MedChemExpress. Everolimus (A8169) was purchased from ApexBio Technology. Temsirolimus (T3574) was purchased from TCI. H\u2010151 (6675) was purchased from Tocris.Bafilomycin A1 (S1413), cycloheximide (S6611), erastin (S7242), MG132 (S2619), MLN4924 (S7109), S6K1\u2010I (S2163), tBHQ (S4990) and rapamycin (AY\u201022989) were purchased from Selleck. 2\u2010bromohexadecanoic acid (2\u2010BP) (238422), puromycin (P8833), hygromycin (H3274), and blasticidin (15205) were purchased from Sigma. \u03b1 antibody (5324), anti\u2010GRP75 antibody (3593), anti\u2010HA antibody (3724), anti\u2010HIF\u20101\u03b1 antibody (36169), anti\u2010IRF3 antibody (4302), anti\u2010MCU antibody (14997), anti\u2010p\u20104E\u2010BP1 (Thr37/46) (2855), anti\u2010p62 antibody (88588), anti\u2010p70 S6 Kinase (2708), anti\u2010p\u2010Akt (Ser473) (4060), anti\u2010p\u2010eIF2\u03b1 (Ser51) antibody (3398), anti\u2010p\u2010Histone H2A.X (Ser139) antibody (9718), anti\u2010p\u2010IRF3 (Ser396) antibody (29047), anti\u2010PLK1 antibody (4513), anti\u2010p\u2010p70 S6 Kinase (Thr389) (9234), anti\u2010p\u2010S6 Ribosomal Protein (Ser235/236) (4858), anti\u2010p\u2010S6 Ribosomal Protein (Ser240/244) (5364), anti\u2010p\u2010STING (Ser366) (50907), anti\u2010p\u2010TBK1/NAK (Ser172) (5483), anti\u2010TBK1 antibody (51872), anti\u2010Skp2 antibody (2562), anti\u2010STING antibody (for WB and IP) (13647), anti\u2010STING antibody (for IF) (90947), anti\u2010ubiquitin antibody (3936), anti\u2010VDAC2 antibody (9412), anti\u2010rabbit IgG, HRP\u2010linked antibody (7074) and anti\u2010mouse IgG, HRP\u2010linked antibody (7076) were obtained from Cell Signaling Technology. Anti\u2010cyclin A antibody (sc\u2010751), anti\u2010GAPDH antibody (sc\u201047724), anti\u2010GST antibody (sc\u2010459), anti\u2010NQO1 antibody (sc\u201032793), anti\u2010p27\u2010antibody (sc\u20101641), anti\u2010PARP\u20101\u2010antibody (sc\u20108007), anti\u2010Ribosomal Protein S6 antibody (sc\u201074459) and anti\u2010vinculin antibody (sc\u201025336) were obtained from Santa Cruz Biotechnology. Polyclonal anti\u2010Flag antibody (F\u20107425), monoclonal anti\u2010Flag antibody , anti\u2010\u03b1\u2010tubulin antibody (T\u20105168), anti\u2010Flag agarose beads (A\u20102220), anti\u2010HA agarose beads (A\u20102095) and glutathione agarose beads (G4510) were obtained from Millipore Sigma. Anti\u2010ATP1A1 antibody (14418\u20101\u2010AP), anti\u2010COX IV antibody (11242\u20101\u2010AP), anti\u2010HIF\u20102\u03b1 antibody (26422\u20101\u2010AP), anti\u2010Histone H2A.X antibody (10856\u20101\u2010AP) and anti\u2010VDAC2 antibody (11663\u20101\u2010AP) were obtained from Proteintech. Anti\u2010Nrf2 antibody (ab62352) was obtained from Abcam. Invitrogen Alexa Fluor 488 goat anti\u2010rabbit IgG (H+L) (A11034), Invitrogen Alexa Fluor 594 goat anti\u2010mouse IgG (H+L) (A11032), and Invitrogen Alexa Fluor 594 Donkey anti\u2010Rabbit IgG (H+L) (A21207) were obtained from ThermoFisher Scientific.All antibodies were used at a 1:1000 dilution in TBST buffer with 5% bovine serum albumin or non\u2010fat milk for western blotting. Anti\u2010Akt antibody (4691), anti\u2010ATP2A2 antibody (9580), anti\u2010calnexin antibody (2679), anti\u2010cGAS antibody (83623), anti\u2010CHOP antibody (2895), anti\u2010c\u2010Myc antibody (18583), anti\u2010cyclin B1 antibody (4135), anti\u2010eIF2The renal cell carcinoma tumor specimens were obtained from the University of North Carolina at Chapel Hill Lineberger Comprehensive Cancer Center Tissue Procurement Facility reviewed and approved by the Office of Human Research Ethics as described previously.71\u22121 streptomycin unless otherwise stated.Human renal cell carcinoma cell lines 786\u2010o, A498, ACHN, Caki\u20101, RCC4, RCC10, RXF\u2010393, UMRC2, and UMRC6, human immortalized kidney cell lines HEK293, HEK293T, and HKC\u20108, human cervical adenocarcinoma cell line HeLa and human glioblastoma cell line U87MG were cultured in DMEM medium supplemented with 10% FBS. Human benign prostatic hyperplasia cell line BPH\u20101 cells were cultured in RPMI\u20101640 medium supplemented with 10% FBS. All cell culture media were supplemented with 100 units of penicillin and 100\u00a0mg\u00a0mL Packaging of lentiviral shRNA or cDNA expressing viruses, as well as subsequent infection of various cell lines were performed according to the protocols described previously. Following viral infection, cells were maintained in the presence of hygromycin (200\u00a0\u00b5g\u00a0mL\u22121) or puromycin (2\u00a0\u00b5g\u00a0mL\u22121), depending on the viral vector used to infect cells. Gene knockdown in shRNA\u2010tet\u2010on cells was achieved by refreshing medium containing 1\u00a0\u00b5g\u00a0ml\u22121 of doxycycline  every 3 days.Cell transfection was performed using lipofectamine 3000 or polyethylenimine (PEI), as described previously.71 PacSTING into pCDNA3.0 vector using primer sets listed below. Flag\u2010STING\u2010HAQ\u2010H232R was constructed by PCR cloning HAQ\u2010H232R variant from THP\u20101 cell cDNA into pCDNA3.0 vector. Flag\u2010STING\u2010H232R was constructed by PCR cloning H232R variant from hORFeome V5.1 collection into pCDNA3.0 vector. Flag\u2010STING\u2010HAQ\u2010Y199C\u2010H232R was constructed by overlapping PCR to clone HAQ\u2010H232R variant into pCDNA3.0 vector using primers listed below. pBabe\u2010Flag\u2010STING\u2010WT, C91A and C88A/C91A were constructed by PCR cloning WT, C91A and C88A/C91A into pBabe\u2010hygro vector. pLenti\u2010Flag\u2010STING\u2010WT, C88A/C91A and R238A were constructed by cloning WT, R238A and C88A/C91A into pLenti\u2010hygro vector. CMV\u2010GST\u2010STING\u2010WT and S366A were constructed by (overlap) PCR cloning WT and S366A into CMV\u2010GST vector. Flag\u2010STING\u20101\u2010110, 1\u2013150, 42\u2013150, 82\u2013150, 111\u2013150, and 151\u2013379 were constructed by PCR cloning respective STING truncations into CMV\u2010GST vector using primer sets listed below. Flag\u2010cGAS was as described previously. His\u2010Ub was as described previously. HA\u2010VDAC2\u2010WT, C103A, C210A, C227A, C103A/C210A/C227A (3A), E84Q, Q101K, S128A, and L136F were constructed by (overlap) PCR cloning VDAC2 into pCDNA3 vector using primer sets listed below. pLenti\u2010HA\u2010VDAC2 and ATP2A2 were constructed by PCR cloning VDAC2 and ATP2A2 into pLenti\u2010GFP\u2010hygro vector using primer sets listed below. CMV\u2010GST\u2010GRP75 was constructed by PCR cloning GRP75 from hORFeome V5.1 collection into CMV\u2010GST vector. CMV\u2010GST\u2010ZDHHC7\u2010WT and C160S were constructed by (overlap) PCR cloning ZDHHC7 into CMV\u2010GST vector using primer sets listed below.Flag\u2010STING\u2010WT, C88A, C91A, C88A/C91A were constructed by (overlap) PCR cloning eviously.73 HisSTING\u2010BamHI\u2010F: GACACCGACTCTAGAGGATCCATGCCCCACTCCAGCCTGCASTING\u2010SalI\u2010Flag\u2010R: ATCCAGAGGTTGATTGTCGACTCACTTGTCGTCATCGTCTTTGTAGTC AGAGAAATCCGTGCGGAGAGSTING\u2010C88A\u2010F: TGGAGGACTGTGCGGGCCGCCCTGGGCTGCCCCCTCCGSTING\u2010C88A\u2010R: CGGAGGGGGCAGCCCAGGGCGGCCCGCACAGTCCTCCASTING\u2010C91A\u2010F: TGCGGGCCTGCCTGGGCGCCCCCCTCCGCCGTGGGGCCCSTING\u2010C91A\u2010R: GGGCCCCACGGCGGAGGGGGGCGCCCAGGCAGGCCCGCASTING\u2010C88A/C91A\u2010F: TGGAGGACTGTGCGGGCCGCCCTGGGCGCCCCCCTCCGCCGTGGGGCCCSTING\u2010C88A/C91A\u2010R: GGGCCCCACGGCGGAGGGGGGCGCCCAGGGCGGCCCGCACAGTCCTCCASTING\u2010P141A\u2010F: CAAGGGCCTGGCCGCAGCTGAGATCTCTGCAGTGSTING\u2010P141A\u2010R: CACTGCAGAGATCTCAGCTGCGGCCAGGCCCTTGSTING\u2010Y199C\u2010F: AGTGAGCCAGCGGCTGTGTATTCTCCTCCCATTGGSTING\u2010Y199C\u2010R: CCAATGGGAGGAGAATACACAGCCGCTGGCTCACTSTING\u2010R238A\u2010F: GCTGGCATCAAGGATGCGGTTTACAGCAACAGCATCTATGAGCSTING\u2010R238A\u2010R: GCTCATAGATGCTGTTGCTGTAAACCGCATCCTTGATGCCAGCSTING\u2010S366A\u2010F: AGCCTGAGCTCCTCATCGCTGGAATGGAAAAGCCCCTSTING\u2010S366A\u2010R: AGGGGCTTTTCCATTCCAGCGATGAGGAGCTCAGGCTSTING\u201042\u2010BamHI\u2010F: GCAT GGATCCATGCACACTCTCCGGTACCTGGTSTING\u201082\u2010BamHI\u2010F: GCAT GGATCCATGTGGAGGACTGTGCGGGCCTGSTING\u2010111\u2010BamHI\u2010F: GCAT GGATCCATGAATGCGGTCGGCCCGCCCTTSTING\u2010110\u2010SalI\u2010Flag\u2010R: GCATGTCGACTCACTTGTCGTCATCGTCTTTGTAGTCTGGGAGGGAGTAGTAGAAATSTING\u20101/150\u2010SalI\u2010Flag\u2010R: GCATGTCGACTCACTTGTCGTCATCGTCTTTGTAGTCTTTTTCACACACTGCAGAGASTING\u2010151\u2010BamHI\u2010F: GCATGGATCCATGGGGAATTTCAACGTGGCCCAVDAC2\u2010HA\u2010EcoRI\u2010F (for pCDNA3):GCATGAATTCATGTATCCATATGATGTTCCAGATTATGCTGCGACCCACGGACAGACTTGVDAC2\u2010HA\u2010XbaI\u2010F (for pLenti\u2010GFP hygro):GCATTCTAGAATGTATCCATATGATGTTCCAGATTATGCTGCGACCCACGGACAGACTTGVDAC2\u2010SalI\u2010R: GCAT GTCGAC TTAAGCCTCCAACTCCAGGGVDAC2\u2010C103A\u2010F: CAATTGAAGACCAGATTGCTCAAGGTTTGAAACTGAVDAC2\u2010C103A\u2010R: TCAGTTTCAAACCTTGAGCAATCTGGTCTTCAATTGVDAC2\u2010C210A\u2010F: CAATTTATCAGAAAGTTGCTGAAGATCTTGACACTTVDAC2\u2010C210A\u2010R: AAGTGTCAAGATCTTCAGCAACTTTCTGATAAATTGVDAC2\u2010C227A\u2010F: GGACATCAGGTACCAACGCCACTCGTTTTGGCATTGVDAC2\u2010C227A\u2010R: CAATGCCAAAACGAGTGGCGTTGGTACCTGATGTCCVDAC2\u2010E84Q\u2010F: GAGTATGGTCTGACTTTCACACAAAAGTGGAACACTGATAACACTCTGVDAC2\u2010E84Q\u2010R: CAGAGTGTTATCAGTGTTCCACTTTTGTGTGAAAGTCAGACCATACTCVDAC2\u2010Q101K\u2010F: CAGAAATCGCAATTGAAGACAAGATTTGTCAAGGTTTGAAACTGACVDAC2\u2010Q101K\u2010R: GTCAGTTTCAAACCTTGACAAATCTTGTCTTCAATTGCGATTTCTGVDAC2\u2010S128A\u2010F: GAAAAGTGGTAAAATCAAGTCTGCTTACAAGAGGGAGTGTATAAACCVDAC2\u2010S128A\u2010R: GGTTTATACACTCCCTCTTGTAAGCAGACTTGATTTTACCACTTTTCVDAC2\u2010L136F\u2010F: CAAGAGGGAGTGTATAAACTTTGGTTGTGATGTTGACTTTGATTTTGCVDAC2\u2010L136F\u2010R: GCAAAATCAAAGTCAACATCACAACCAAAGTTTATACACTCCCTCTTGATP2A2\u2010BglII\u2010HA\u2010F: GCATAGATCTATGTATCCATATGATGTTCCAGATTATGCTGAGAACGCGCACACCAAGACATP2A2\u2010Flag\u2010SalI\u2010R: GCATGTCGACTCACTTGTCGTCATCGTCTTTGTAGTCAGACCAGAACATATCGCTAAGRP75\u2010BamHI\u2010F: GCAT GGATCC ATGATAAGTGCCAGCCGAGCGRP75\u2010SalI\u2010R: GCAT GTCGAC TTACTGTTTTTCCTCCTTTTGZDHHC7\u2010BamHI\u2010F: GCATGGATCCATGCAGCCATCAGGACACAGZDHHC7\u2010SalI\u2010R: GCAT GTCGAC TCACACTGAGAACTCCGGGCZDHHC7\u2010sh3\u2010resist\u2010F: AGTGATTTTTCACCTCCCATTACAGTAATCCTGTTGATCTTZDHHC7\u2010sh3\u2010resist\u2010R: AAGATCAACAGGATTACTGTAATGGGAGGTGAAAAATCACTZDHHC7\u2010C160S\u2010F: GAAAATGGATCATCACTCCCCGTGGGTGAACAATTZDHHC7\u2010C160S\u2010R: AATTGTTCACCCACGGGGAGTGATGATCCATTTTCRT\u2010PCR primers are listed below:STING1\u2010F: CACTTGGATGCTTGCCCTCSTING1\u2010R: GCCACGTTGAAATTCCCTTTTTHMOX1\u2010F: AAGACTGCGTTCCTGCTCAACHMOX1\u2010R: AAAGCCCTACAGCAACTGTCGCYB5R3\u2010F: TCTACCTCTCGGCTCGAATTGCYB5R3\u2010R: CCTTGTCATCATCGCTGGAGATTXNIP\u2010qPCR\u2010F: ATATGGGTGTGTAGACTACTGGGTXNIP\u2010qPCR\u2010R: GACATCCACCAGATCCACTACTZDHHC3\u2010F: CCACTTCCGAAACATTGAGCGZDHHC3\u2010R: CCACAGCCGTCACGGATAAAZDHHC7\u2010F: CCCAAAGGAAACGCTACGAAAZDHHC7\u2010R: CGCGCTCGGGTTTAATACAGRNA18S\u2010F: TGCGGAAGGATCATTAACGGARNA18S\u2010R: AGTAGGAGAGGAGCGAGCGACCU6\u2010qPCR\u2010F: CTCGCTTCGGCAGCACAU6\u2010qPCR\u2010R: AACGCTTCACGAATTTGCGTPrimers used in generating plasmids used in this study are listed below:STING, cGAS, ZDHHC3, and ZDHHC7 were purchased from Sigma. Their target sequence is listed below:shScr: CCGGAACAGTCGCGTTTGCGACTGGCTCGAGCCAGTCGCAAACGCGACTGTTTTTTTTGshSTING\u20101: CCGGCCAACATTCGCTTCCTGGATACTCGAGTATCCAGGAAGCGAATGTTGGTTTTTTGshSTING\u20102: CCGGGCAGAGCTATTTCCTTCCACACTCGAGTGTGGAAGGAAATAGCTCTGCTTTTTTGshSTING\u20103: CCGGGTCCAGGACTTGACATCTTAACTCGAGTTAAGATGTCAAGTCCTGGACTTTTTTGshcGAS\u20101: CCGGCGTGAAGATTTCTGCACCTAACTCGAGTTAGGTGCAGAAATCTTCACGTTTTTTGshcGAS\u20102: CCGGATCTATTCTCTAGCAACTTAACTCGAGTTAAGTTGCTAGAGAATAGATTTTTTGshZDHHC3\u201010: CCGGGTATAGCATCATCAACGGAATCTCGAGATTCCGTTGATGATGCTATACTTTTTTGshZDHHC3\u201018: CCGGGCTTTGAAGAAGATTGGACAACTCGAGTTGTCCAATCTTCTTCAAAGCTTTTTTGshZDHHC3\u201079: CCGGCCAGAAGTACTTCGTCCTGTTCTCGAGAACAGGACGAAGTACTTCTGGTTTTTTGshZDHHC7\u20103: CCGGGATAACTGTAATCCTGTTGATCTCGAGATCAACAGGATTACAGTTATCTTTTTTGshZDHHC7\u201034: CCGGACTGCCCGTGGGTGAACAATTCTCGAGAATTGTTCACCCACGGGCAGTTTTTTTGshRNA plasmids to deplete endogenous shMCU: CCGGGCAAGGAGTTTCTTTCTCTTTCTCGAGAAAGAGAAAGAAACTCCTTGCTTTTTG\u03b1: CCGGCCAGTTATGATTGTGAAGTTACTCGAGTAACTTCACAATCATAACTGGTTTTTTGshHIF\u20101\u03b1: CCGGGGAGACGGAGGTGTTCTATTTCAAGAGAATAGAACACCTCCGTCTCCTTTTTTGshHIF\u20102shGRP75\u201051:CCGGGCACATTGTGAAGGAGTTCAACTCGAGTTGAACTCCTTCACAATGTGCTTTTTTGshGRP75\u201052:Other shRNA plasmids were constructed by inserting synthesized shRNAs into pLKO\u2010puro or pLKO\u2010hydro vectors. Their target sequence is listed below:shVDAC2: CCGGAAGGATGATCTCAACAAGAGCCTCGAGGCTCTTGTTGAGATCATCCTTTTTTTTGTet\u2010inducible shRNA plasmids were constructed by inserting synthesized shRNAs into Tet\u2010pLKO\u2010neo vector. Target sequence of STING was the same as that of shSTING\u20102 and \u20103. Target sequence of shVDAC2 is listed below:sgSTING\u20101B: GCTGGGACTGCTGTTAAACGsgSTING\u20106: CATTACAACAACCTGCTACGsgcGAS\u20101: CACGTGCTCATAGTAGCTCCsgcGAS\u20102: GGCCGCCCGTCCGCGCAACTsgIRF3\u20101: CGCTCACTGCCCAGTATGTGsgIRF3\u20104: GGCACCAACAGCCGCTTCAGsgMCU: GTGTTTTCTAGGTACACCAGsgRNA plasmids were constructed by inserting synthesized sgRNAs into lentiCRISPRv2\u2010puro vector. Their target sequence is listed below:STING\u2010S366A\u2010KI\u2010sgF: CACCGGCTTTTCCATTCCACTGATGSTING\u2010S366A\u2010KI\u2010sgR: AAACCATCAGTGGAATGGAAAAGCCSTING\u2010S366A\u2010KI\u2010ssODNAGGGCAGCTTGAAGACCTCAGCGGTGCCCAGTACCTCCACGATGTCCCAAGAGCCTGAGCTATTAATCGCTGGAATGGAAAAGCCCCTCCCTCTCCGCACGGATTTCTCTTGAGACCCAGGGTCACCAGGCCAGAGCCTCCSTING\u2010S366A knockin experiment was performed using STING sgRNAs and ssoDNA as listed below:STING\u2010S366A\u2010KI\u2010PCR\u2010F: GAGTGGGAATGGGTAAGATCCTCSTING\u2010S366A\u2010KI\u2010PCR\u2010R: GACGCATCTTAAGATGTCAAGTCCKnockin clones were screened by PCR using primers listed below to search for clones loss of SacI but gain of AseI site after knockin. Equal amounts of whole cell lysates were resolved by SDS\u2010PAGE and immunoblotted with indicated antibodies. For immunoprecipitations analysis, unless specified, 1\u00a0mg lysates were incubated with the indicated antibody (1\u20132\u00a0\u00b5g) for 3\u20134\u00a0h at 4\u00a0\u00b0C followed by 1\u00a0h incubation with 10\u00a0\u00b5L Protein A/G XPure Agarose Resin . Or 1\u00a0mg lysates containing tagged molecules were incubated with agarose beads coupled antibodies for the specific tag for 3\u20134\u00a0h at 4\u00a0\u00b0C. For endogenous IPs, incubation of cell lysates with antibodies was extended to overnight. The recovered immuno\u2010complexes were washed five times with NETN buffer  before being resolved by SDS\u2010PAGE and immunoblotted with indicated antibodies. For VDAC2 oligomerization detection, cells were incubated with 250\u00a0\u00b5M ethylene glycol bis (succinimidyl succinate) , lyzed in Triton X\u2010100 buffer and nixed with 4 \u00d7 lithium dodecyl sulfate sample buffer . Load protein without boiling in SDS\u2010free PAGE gel and immunoblotted with indicated antibodies.Cells were lysed in EBC buffer  or Triton X\u2010100 buffer  supplemented with protease inhibitor cocktail  and phosphatase inhibitor cocktail . The protein concentrations of whole cell lysates were measured by NanoDrop OneC using the Bio\u2010Rad protein assay reagent as described previously.71 Equ 1\u2010day post\u2010transfection, cells were selected with 1\u00a0\u00b5g\u00a0ml\u22121 puromycin for 3 days. Surviving cells were counted and each single cell was seeded into 96\u2010well plates. Each single clone grown up in 96\u2010well plates was amplified and one copy was used for genomic DNA extraction, followed by PCR and AseI/SacI digestion to screen for potential knockin clones. SacI negative but AseI positive clones are selected and sequenced to verify the knockin at the DNA level.Parental A498 cells were split into 24\u2010well plates and transfected with sgRNA against endogenous STING together with STING\u2010S366A\u2010ssoDNA following protocols as described.60 1\u2010dm urea  to 100\u00a0\u00b5g\u00a0\u00b5l\u22121 and subjected to FASP trypsin digestion protocol. Briefly, proteins were reduced using 50\u00a0mM DTT  for 15\u00a0min at 65\u00a0\u00b0C. Proteins were then transferred to a 30\u00a0000 MWCO spin filter , diluted with 200\u00a0\u00b5l of 8\u00a0m urea, and centrifuged at 10\u00a0000 \u00d7 g for 30\u00a0min at RT. The proteins were washed twice using 200\u00a0\u00b5l of 8\u00a0m urea\u00a0followed by 30 minutes of centrifugation at 10\u00a0000 \u00d7 g between each wash.\u00a0Proteins were alkylated using 100\u00a0\u00b5l of 15\u00a0mM 2\u2010chloroacetamide  prepared in 8\u00a0m urea for 20\u00a0min in the dark at RT. The spin filter was then centrifuged at 10\u00a0000\u00a0\u00d7\u00a0g for 20\u00a0min at RT followed by two washes with 200\u00a0\u00b5l of 8\u00a0M urea with 20\u00a0min of centrifugation at 10000\u00a0\u00d7\u00a0g in between each wash. Buffer exchange into 50\u00a0mM ammonium bicarbonate (ABC) pH 8.0 was performed with two washes of 200\u00a0\u00b5l of 50\u00a0mM ABC with centrifugation at 10\u00a0000\u00a0\u00d7\u00a0g for 15\u00a0min at RT between each wash. 100\u00a0\u00b5l of 50\u00a0mM ABC was added to the spin filter along with 2.5\u00a0\u00b5g of trypsin (Promega V511C). Proteins were trypsinized overnight at 37\u00b0C for 18\u00a0h. Following trypsinization, peptides were recovered in a new receiver tube by centrifugation at 10\u00a0000\u00a0\u00d7\u00a0g for 15\u00a0min. Peptides were eluted twice\u00a0using 50\u00a0\u00b5l of 0.5% TFA in water at 10\u00a0000\u00a0\u00d7\u00a0g for 10\u00a0min.\u00a0Samples were then concentrated to 100\u00a0\u00b5l using a\u00a0speedvac followed by C18 desalting . Samples were then concentrated using a speedvac and resolubilized in 100\u00a0\u00b5l of LC\u2010Optima\u00a0MS\u2010grade water (Thermo). Ethyl acetate extraction followed by speedvac was performed to remove residual detergents.\u00a0QFP assay  was performed for peptide quantification.A498 cells stably expressing either FLAG\u2010EV or FLAG\u2010STING were lysed in EBC lysis buffer FLAG immunoprecipitants were washed with NETN buffer. Proteins were diluted in 8\u00a0 Data was searched using MaxQuant (version 1.6.6.7), and all statistical analyses were done in Perseus (version 1.6.3.4).Detailed liquid chromatography\u2010mass spectrometry/mass spectrometry\u00a0methods and data filtering methods were described previously.76 DatRNA extraction was performed with an RNA miniprep super kit  and QIAshredder . The final elution step was done with 50\u00a0\u00b5L of RNAse\u2010free water. The relative enrichment of mRNA was quantified with the NanoDrop OneC (ThermoFisher Scientific). At least two biological replicates were performed for RNA extraction. Reverse transcription was performed with iScript cDNA synthesis kit . Quantitative real\u2010time PCR was performed with iTaq universal SYBR green supermix  using a QuantStudio\u202f6 Flex Real\u2010Time PCR Systems (ThermoFisher Scientific). Each mRNA level was normalized to RNA18S or U6 snRNA. The comparative Ct method was used to calculate fold change in expression. Statistical significance was determined by one\u2010way ANOVA tests.2) for 3\u00a0h. After thorough mixing, absorbance at 450\u00a0nm was measured using the BioTek Cytation 5 Cell Imaging reader. Combination index (CI) of co\u2010treatment of 2\u2010BP and sorafenib was calculated by CompuSyn software .Indicated number of cells were seeded in each well of 96\u2010well plates for cell viability assay to monitor cell viability at indicated time periods using Cell Counting Kit 8  according to manufacturer's instruction. Briefly, at indicated time points post\u2010cell seeding, 10\u00a0\u00b5L CCK8 solution was added into each well and incubated in the culture incubator (37\u00a0\u00b0C with 5% CO2 for 7\u201315 days (as indicated in figure legends) until formation of visible colonies. Colonies were washed with 1x PBS, fixed with methanol for 30\u00a0min, and stained with 0.5%\u00a0crystal violet for 30\u00a0min. Colonies were then washed with distilled water and air\u2010dried. Colony numbers were manually counted. Three independent experiments were performed to generate the error bars.Indicated cells were seeded into 6\u2010well or 24\u2010well plates (500 cells/well) and cultured in 37\u00a0\u00b0C incubator with 5% CO Briefly, the assays were preformed using 6\u2010well plates where the solid medium consists of two layers. The bottom layer contains 0.8% noble agar, and the top layer contains 0.4% agar suspended with 3\u00a0\u00d7 104 or indicated number of cells. 500\u00a0\u00b5L complete DMEM medium with 10% FBS was added every 4 days. About 4\u20136 weeks later the cells were stained with iodonitrotetrazolium chloride (1\u00a0mg\u00a0mL\u22121) (Sigma I10406) overnight for colony visualization, imaging, and counting. Three independent experiments were performed to generate the error bar.The anchorage\u2010independent cell growth assays were performed as described previously.53 Bri Briefly, for mouse xenograft growth experiments, A498 cells were infected with viruses expressing shScr or shSTING2/3. Two days later, 1\u00a0\u00d7 106 A498 cells in PBS were injected into the flank of indicated female nude mice . Tumor size was measured every two days with a digital caliper, and the tumor volume was determined with the formula: L \u00d7 W2 \u00d7 0.5, where L is the longest diameter and W is the shortest diameter. After 66 days, mice were sacrificed, and tumors were dissected and weighed. For inducible STING shRNA, 1\u00a0\u00d7 107 A498 cells in DMEM were injected into flank of male nude mice . When tumors became visible after 15 days, 2\u00a0mg\u00a0ml\u22121 doxycycline was added to drinking water containing 2% sucrose. Water was changed every three days and protected from light. Mice were sacrificed 39 days after injection. For combination therapy, 1\u00a0\u00d7 107 A498 cells in DMEM were injected into flank of male nude mice . After 25 days, when tumors reached a volume of \u2248150 mm3, mice were randomly divided into four groups. 2\u2010BP was dissolved in 10% DMSO+40% PEG300+5% Tween 80+ 45% saline. Sorafenib was dissolved in 3% DMSO+97% sulfobutylether\u2010\u03b2\u2010Cyclodextrin solution . Mice were daily treated with 40\u00a0mg\u00a0kg\u22121 2\u2010BP given by intraperitoneal injection or 40\u00a0mg\u00a0kg\u22121 sorafenib given by oral gavage or both drugs or their solvents. Tumor size was measured regularly, and the tumor volume was determined with the formula: L x W2 x 0.5, Mice were sacrificed after 13 days of treatment.All mouse work has been reviewed and approved by UNC Institutional Animal Care and Use Committee under IACUC#19\u2010031 which has been continued as #22\u2010056. Mouse xenograft assays were performed as described previously.71 Bri Reads overlapping blacklisted regions of the genome were then removed. Transcript abundance was then estimated using Salmon, and differentially expressed genes were detected using DESeq2 with the criteria of adjusted p\u2010values (adjP) <0.05. The ClusterProfiler R package (v3.14.3) was employed to analyze the Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) for functional pathway annotation. Enrichment analysis for GO terms and KEGG pathways utilize enrichGO and enrichKEGG functions and visualizes the result with bubble plots. RNA\u2010seq data are deposited to GEO under accession number GSE190816.Total RNA from triplicate samples of A498 cells infected with shScr or shSTING was extracted with RNeasy mini kit . Library preparation and sequencing were performed by GENEWIZ as paired\u2010end 150\u2010bp reads. Reads were then filtered for adaptor contamination using cutadapt and filtered such that at least 90% of bases of each read had a quality score > 30. Reads were aligned to the reference genome (hg19) using STAR version 2.5.2b retaining only primary alignments.77 Rea4, 1\u00a0\u00b5M Alexa 647\u2010azide (Life Technologies), and 100\u00a0mM ascorbic acid (fresh) for 30\u00a0min. at room temperature in the dark. Finally, cells were resuspended in 1% BSA\u2010PBS with 1\u00a0\u00b5g\u00a0mL\u22121 DAPI (Life Technologies) and 100\u00a0\u00b5g\u00a0mL\u22121 RNAse A (Sigma Aldrich) and incubated overnight at 4\u00a0\u00b0C in the dark. Data were collected on an Attune NxT flow cytometer (Thermo Fisher Scientific) and analyzed using FCS Express 7 software (De Novo Software).To measure cell cycle phase distribution, cells were treated with 10\u00a0\u00b5M EdU  for 30\u00a0min. before harvesting by trypsinization. Cells were washed with PBS and then fixed in 4% paraformaldehyde in PBS for 15\u00a0min. at room temperature. 1% BSA\u2010PBS was added, mixed, and cells were centrifuged. Fixed cells were permeabilized with 0.5% triton X\u2010100 in 1% BSA\u2010PBS at room temperature for 15\u00a0min. and centrifuged. Cells were then processed for EdU detection as follows: samples were incubated in PBS with 1\u00a0mM CuSOTo measure general ROS level, trypsinized cells were incubated with 10\u00a0\u00b5M CM\u2010H2DCFDA  in PBS at 37\u00a0\u00b0C for 30\u00a0min. To measure mitochondrial ROS level, trypsinized cells were incubated with 1\u00a0\u00b5M MitoSOX Red mitochondrial superoxide indicator  in PBS at 37\u00a0\u00b0C for 20\u00a0min. To measure mitochondrial calcium level, trypsinized (without EDTA) cells were incubated with 5\u00a0\u00b5M Rhod\u20102, AM  in PBS solution containing 10% FBS and 10\u00a0mM glucose at 37\u00a0\u00b0C for 1\u00a0h. To measure mitochondrial membrane potential, cells were incubated with 2\u00a0\u00b5M JC\u20101  in PBS at 37\u00a0\u00b0C for 15\u00a0min. Cells were washed with PBS twice and analyzed with BD FACScanto II or BD FACSfortessa (BD Biosciences) with the BD Diva software (BD Biosciences). A minimum of 10\u00a0000 events were acquired for each sample. Data were analyzed using Flowjo 7.6.1 (Tree Star).Cells plated onto glass coverslips were fixed with 4% paraformaldehyde in PBS for 20\u00a0min at room temperature and permeabilized with 0.2% Triton X\u2010100 for 20\u00a0min at room temperature. Cells were incubated with blocking buffer  for 1\u00a0h, incubated with primary antibodies at 4\u00a0\u00b0C overnight, incubated with secondary antibodies and/or mitochondria dye MitoView Green  at room temperature for 1\u00a0h and mounted with ProLong Gold antifade reagent . Fluorescent signals were observed with an Olympus 1 \u00d7 51 inverted microscope at \u00d7 20 magnification, or with an Olympus FV1000 confocal microscope at 60\u00d7 magnification.\u22121. Added 800\u00a0\u00b5l reagent C and invert tubes several times to mix. Centrifuged tubes at 700 \u00d7 g for 10\u00a0min and collect supernatant as a mixture containing mitochondria, lysosome, and peroxisome. Centrifuged supernatant at 3000 \u00d7 g for 15\u00a0min and this pellet contains isolated mitochondria. Centrifuged supernatant at 12\u00a0000 \u00d7 g for 15\u00a0min and transferred new supernatant containing cytosolic fraction to a new tube. The pellet was a mixture of lysosome, peroxisome, and some mitochondria. Resuspended mitochondria pellet in 500\u00a0\u00b5l reagent C and centrifuged at 12\u00a0000 \u00d7 g for 5\u00a0min to obtain pure mitochondrial fraction. Samples were kept at 4\u00a0\u00b0C throughout the procedure.Cytosolic and mitochondrial fractions of cells were isolated with Mitochondria isolation kit  for cultured cells according to manufacturer's instruction. Briefly, add 800\u00a0\u00b5l reagent A to cell pellets and incubate for 2\u00a0min. Added 10\u00a0\u00b5l reagent B and vortex 5 s\u00a0min Image analysis was performed using Adobe Illustrator.Electron microscopic analysis of indicated A498 cells was performed as detailed below. Sample prep: indicated A498 cell culture pellets were embedded in 2% agarose, secondary fixation with osmium tetroxide, dehydration , followed by embedding in EPON.\u00a0Sectioning: \u224880\u00a0nm thin sections on Cu grids, stained with UA and LC. Imaging: FEI Tecnai 12 at 120\u00a0kV, Gatan Rio16 CMOS camera. Cells were randomly selected for imaging. Images at 4400\u00d7 magnification were used for counting total and abnormal mitochondria. All clearly identified mitochondria in the images were analyzed. Images at 26\u00a0000\u00d7 magnification were randomly selected for mitochondria\u2010ER contact (MERC) length measurement. All clearly identified mitochondria membranes and associated ER membranes in the images were evaluated. Only MERC sites with a distance no more than 30\u00a0nm were regarded as MERC enabling calcium transfer from ER to mitochondria and their length was measured according to.80 Ima4 cells were seeded into XF24 cell culture microplate  before the assay. Added 1\u00a0mL of Seahorse XF24 calibrant solution (pH 7.4)  to each well of XF24 microplate and replaced green sensor cartridge on the top. Incubated entire cartridge in a non\u2010CO2 incubator at 37\u00b0C overnight. On the day following cell seeding, media was changed to phenol red\u2010free, Seahorse XF DMEM medium, pH 7.4  supplemented with 25\u00a0mM glucose and 1\u00a0mM sodium pyruvate for OCR or 2\u00a0mM glutamine and 1\u00a0mM sodium pyruvate for ECAR. Cells were equilibrated within 1\u00a0h in 37\u00a0\u00b0C non\u2010CO2 incubator. Loaded the sensor cartridge for the calibration process and replaced calibration plate with cell plate after that. The basal mitochondrial respiration or extracellular acidification rate was first measured by recording extracellular oxygen concentration. Then the OCR or ECAR trace was recorded in response to sequential addition of indicated compounds in the Seahorse XF Cell Mito Stress Test Kit  or Glycolysis Stress Test Kit . Concentration of compounds for OCR was: 1\u00a0\u00b5M of oligomycin A, 1\u00a0\u00b5M of FCCP, and 1\u00a0\u00b5M of rotenone/antimycin A. Concentration of compounds for ECAR was: 10\u00a0mM of glucose, 1\u00a0\u00b5M of oligomycin, and 50\u00a0mM of 2\u2010DG. 3 to 5 technical replicates were utilized per sample to calculate OCR or ECAR.The OCR and ECAR were measured by an XFe24 extracellular flux analyzer (Agilent Technologies), according to the manufacturer's instructions. Briefly, 5 \u00d7 10 Briefly, cells were lysed in lysis buffer (LB)  supplemented with protease inhibitor, PMSF and 50\u00a0mM N\u2010ethylmaleimide (NEM) . Equal amounts of lysates were incubated with the STING antibody overnight at 4\u00a0\u00b0C followed by 1\u00a0h incubation with 60\u00a0\u00b5L Protein A/G XPure Agarose Resin, or incubated with Flag agarose beads for 3\u20134\u00a0h at 4\u00a0\u00b0C. Beads were resuspended in LB+10\u00a0mM NEM and split into triplicates. 1/3 of beads were used as \u2010HAM control and 2/3 were used as +HAM treatment. Beads were resuspended with LB (pH 7.2)+0.1% SDS quickly, washed with LB (pH\u00a0= 7.2) three times, resuspended in LB (pH 7.2) with or without 1\u00a0m hydroxylamine (HAM)  and incubated at room temperature for 1\u00a0h. Then, beads were washed with LB (pH 6.2) once and resuspended in LB (pH\u00a0= 6.2)+2\u00a0\u00b5M Biotin\u2010BMCC  at 4\u00a0\u00b0C for 1\u00a0h. Beads were then washed with LB (pH\u00a0= 6.2) once and LB (pH 7.5) for three times. Beads were boiled and resolved by SDS\u2010PAGE and immunoblotted with streptavidin\u2010HRP antibody to detect biotin\u2010labeled palmitoylated STING.Protein palmitoylation detection was performed by immunoprecipitation and acyl\u2010biotin exchange as described previously.81 Brip \u2264 0.05 was considered statistically significant. The results were shown as means \u00b1 SD from at least two or three independent experiments as indicated in figure legends. Differences between control and experimental conditions were evaluated by One\u2010way ANOVA.Statistical analyses were performed using the Graphpad Prism 8 Software. The authors declare no conflict of interest.Conceptualization: ZZ, PL; Methodology: ZZ, JGC, BM, XT, HY, GD, PL; Investigation: ZZ, HD, XZ, EWC, JZ, LM, YW, XT, TS, JS; Visualization: ZZ, YW, JZ; Funding acquisition: JGC, DH, GD, PL; Project administration: JLS, EH; Supervision: JGC, BM, GD, PL; Writing \u2013 original draft: ZZ, PL; Writing \u2013 review & editing: HY, JGC, BM, GD.Supporting InformationClick here for additional data file."}
{"text": "The crystal structure of the title salt is held by N\u2014H\u22efBr charge-assisted hydrogen bonds and dipole\u2013dipole inter\u00adactions. In comparison with reference structures, elongation of C\u2014S bonds is observed. 12H13N2S+\u00b7Br\u2212, which crystallizes in the monoclinic P21/c centrosymmetric space group. The asymmetric unit contains one 2-[meth\u00adyl]iso\u00adthio\u00aduronium cation and one bromide anion. The methyl\u00adene carbon lies in plane of the naphthalene core. In comparison with reference structures, elongation of C\u2014S bonds as well as tilting of the iso\u00adthio\u00aduronium group is observed. Given the ionic nature of the compound, the structure is held by charge-assisted N\u2014H\u22efBr hydrogen bonds, with a noteworthy contribution of dipole\u2013dipole inter\u00adactions, which form bilayers in the structure. The bilayers are held by the weak London forces.Herein we report the crystal structure of 2-[meth\u00adyl]iso\u00adthio\u00aduronium bromide, C Since the relevant torsion angle of the title compound is \u221268.1\u2005(3)\u00b0, only the non-linear 2-benzyl\u00adiso\u00adthio\u00aduronia, will be used as a reference group [CCDC codes EBIFOK meth\u00adyl]iso\u00adthio\u00aduronia structures in the the CSD; therefore, we decided to compare the title compound with 2-benzyl\u00adiso\u00adthio\u00aduronia structures. The published structures of 2-benzyl\u00adiso\u00adthio\u00aduronia can be divided according to the CThe C11\u2014S1 bond is almost perpendicular to the naphthalene core, with C1\u2014C2\u2014C11\u2014S1 and C3\u2014C2\u2014C11\u2014S1 torsion angle values of 91.8\u2005(3) and \u221288.0\u2005(3)\u00b0, respectively. Among the reference group, such a conformation is unusual, with average values being 61.45 and 120.53\u00b0. The iso\u00adthio\u00aduronium group is significantly tilted, with C11\u2014S1\u2014C12\u2014N1 and C11\u2014S1\u2014C12\u2014N2 torsion angles of \u221268.5\u2005(3) and 110.7\u2005(3)\u00b0, respectively. Such a tilt is not observed among the reference group, where the average values are 20.46 and 160.94\u00b0. The tilting of the group can be explained by the steric demands of the 2-naphthyl\u00admethyl unit on the packing.n1\u22efBr1\u22efH2n1iii\u2014N1iii, and N2\u2014H1n2\u22efBr1ii\u22efH2n2ii\u2014N2ii classified as n1\u22efBr1\u22efH1n2iv\u2014N2iv\u2014C12iv\u2014N1iv, N1\u2014H2n1\u22efBr1i\u22efH1n2v\u2014N2v\u2014C12v\u2014N1v, and N1\u2014H2n1\u22efBr1i\u22efH2n2i\u2014N2i\u2014C12i\u2014N1i classified as x, y\u00a0\u2212\u00a01, z; (ii) x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0x, y\u00a0+\u00a01, z; (iv) x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0vi iso\u00adthio\u00aduronium bromide.The 2-[meth\u00adyl]iso\u00adthio\u00aduronium bromide (20\u2005mg) was dissolved in 10\u2005ml of methanol and left to slowly evaporate at room temperature. After 5\u2005d, colorless platelets were collected.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620015114/sj4217sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314620015114/sj4217Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620015114/sj4217Isup3.molSupporting information file. DOI: 2044275CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The coordination sphere around each Cd2+ ion is completed by three N atoms of a tridentate 8-[2-(di\u00admethyl\u00adamino)\u00adethyl\u00adamino]quinoline ligand and another chloride ion to form a distorted fac-CdN3Cl3 octa\u00adhedron. The ethanol mol\u00adecule is both an acceptor of an N\u2014H\u22efO and a donor of an O\u2014H\u22efCl hydrogen bonds to its adjacent complex unit. In the crystal, weak aromatic \u03c0\u2013\u03c0 stacking is observed.The title solvated bimetallic complex, [Cd Similar perpendicular arrangement of the pendant Cl\u2212 ions is observed in the Cl\u2013(Cd2Cl2)\u2013Cl fragments of other complexes with different ligands \u00b0 (N3\u2014Cd1\u2014N2) to 105.73\u2005(3)\u00b0 (Cl1\u2014Cd1\u2013Cl2) for one Cd2+ ion and 71.04\u2005(9) \u00b0 (N6\u2014Cd2\u2014N5) to 102.09\u2005(7)\u00b0 (N5\u2014Cd2\u2014Cl2) for the other. The corres\u00adponding angles for the hydrate structure are in the range 69.48\u2005(5) to 101.08\u2005(4)\u00b0. The N\u2014C\u2014C\u2014N torsion angles in the ethane di\u00adamine are almost the same for both independent ligands [N1\u2014C3\u2014C4\u2014N2 = 63.0\u2005(4)\u00b0 and N4\u2014C16\u2014C17\u2014N5 = 63.3\u2005(5)\u00b0] in I.Both CdR(6)22 loop. In the extended structure, the quinoline ring systems of neighbouring complex units are involved in weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions. The groups involved are related by inversion symmetry with a c(i)\u22efc(i)\u2032 separation of 3.93\u2005(1)\u2005\u00c5 [c(i) = the midpoint of the C9\u2014C10 bond of the C5\u2013C13/N3 ring system]. If a second longer inversion-related contact c(ii)\u22efc(ii)\u2032 of 4.56\u2005(1)\u2005\u00c5 [c(ii) = midpoint of the C22\u2014C23 bond of the C18\u2013C26/N6 ring system] is considered to be a significant inter\u00adaction, infinite chains running parallel to [101] result \u00adethyl\u00adamino]\u00adquinoline ligand and cadmium dichloride were mixed in dry ethanol solvent at room temperature under a positive nitro\u00adgen pressure and the mixture was stirred at room temperature for several hours. The solution was then warmed to dissolve the material and the product was recrystallized on cooling to produce colourless crystals of Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621001504/hb4375sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621001504/hb4375Isup2.hklStructure factors: contains datablock(s) I. DOI: 2062006CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of a resveratrol\u2013oxime ester is reported. 22H25NO6, the C=C double bond linking the benzene rings adopts an E configuration and the dihedral angle between the rings is 47.1\u2005(2)\u00b0. The oxime unit contains a C=N double bond, which also has an E configuration. In the crystal, pairs of C\u2014H\u22efN hydrogen bonds generate inversion dimers and weak C\u2014H\u22efO inter\u00adactions link the dimers into chains propagating along the b-axis direction.In the title compound, C The dihedral angle formed by benzene rings is 47.1\u2005(2)\u00b0. The C17=N1 imine double bond in the oxime unit also adopts an E configuration, which is defined by a torsion angle of 178.3\u2005(1)\u00b0 for C4\u2014C17\u2014N1\u2014O3. There are three meth\u00adoxy groups attached to carbon atoms C1, C5 and C13 in the benzene rings: those at the meta positions  are essentially co-planar with their attached benzene rings [C6\u2014C1\u2014O1\u2014C7 = \u22120.2\u2005(2)\u00b0 and C6\u2014C5\u2014O6\u2014C22 = 3.9\u2005(2)\u00b0] whereas the meth\u00adoxy group at the para position (C13) is slightly twisted from the corresponding ring plane [C12\u2014C13\u2014O2\u2014C16 = 8.9\u2005(2)\u00b0]. In the crystal, pairs of C22\u2014H22\u22efN1 hydrogen bonds generate inversion dimers benz\u00adaldehyde  I. DOI: 10.1107/S2414314621009500/hb4391Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621009500/hb4391Isup3.cmlSupporting information file. DOI: 2109339CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Using the equation-of-motion coupled-cluster singles and doubles method and Fermi\u2019s golden rule, we quantitatively reproduced all rate constants relevant to the emission mechanism; prompt and delayed fluorescence, internal conversion (IC), intersystem crossing, and reverse intersystem crossing (RISC). In addition, the photoluminescence quantum yield and its prompt and delayed contributions were quantified by calculating the population kinetics of excited states and the transient photoluminescence decay curve. The calculations also revealed that TADF occurred via a stepwise process of 1)\u00a0thermally activated IC from the electronically excited lowest triplet state T1 to the second-lowest triplet state T2, 2)\u00a0RISC from T2 to the lowest excited singlet state S1, and 3)\u00a0fluorescence from S1.Molecules that exhibit multiple resonance (MR) type thermally activated delayed fluorescence (TADF) are highly efficient electroluminescent materials with narrow emission spectra. Despite their importance in various applications, the emission mechanism is still controversial. Here, a comprehensive understanding of the mechanism for a representative MR-TADF molecule  are highly efficient electroluminescent materials, but their emission mechanism is still not fully understood. Here, the emission mechanism of a representative MR-TADF molecule is studied through quantum chemistry calculations, with two consecutive decay processes unveiled. An important factor for TADF efficiency is the energy difference between the lowest triplet state (T1) and the lowest excited singlet state (S1), \u2206E(T1\u2009\u2192\u2009S1); a small \u2206E(T1\u2009\u2192\u2009S1) (<200\u2009meV) is required to induce T1\u2009\u2192\u2009S1 reverse intersystem crossing (RISC). Another important factor is a large transition-dipole moment between S1 and ground-state S0 to accelerate the rate of S1\u2009\u2192\u2009S0 fluorescence. Experimentally, efficient RISC and high photoluminescence quantum yields (PLQYs) have been simultaneously realized by combining suitable donor and acceptor units that control the spatial overlap between the highest-occupied molecular orbitals (HOMOs) and the lowest-unoccupied molecular orbitals (LUMOs)9. It is important to note that the fluorescence spectra were broadened because of the charge-transfer character of S1, which was a significant drawback for OLED applications in displays.Since highly efficient thermally activated delayed fluorescence (TADF) was used in organic light-emitting diodes (OLEDs)10. Using a triphenylboron core possessing two nitrogen atoms . However, \u2206E(T1\u2009\u2192\u2009S1) and \u2206E(T1\u2009\u2192\u2009T2) were large, 0.59\u2009eV and 0.61\u2009eV, respectively, which could not explain efficient RISC from T1 to S1. Gao et al. examined the density-functional dependence of \u2206E(T1\u2009\u2192\u2009S1) within the framework of TD-DFT41. The MPWK1CIS functional reproduced the experimental \u2206E(T1\u2009\u2192\u2009S1)41, as reviewed by Suresh et al.21. However, the RISC rate constant (kRISC) was not calculated and the TADF mechanism was unclear. Also, they considered TADF in terms of direct (one-step) T1\u2009\u2192\u2009S1 RISC, which differed from the work of Northey et al40. Pershin et al. reported that TD-DFT methods overestimated \u2206E(T1\u2009\u2192\u2009S1) for MR molecules, and that the spin-component-scaling second-order approximate coupled-cluster (SCS-CC2) method outperformed TD-DFT for predicting \u2206E(T1\u2009\u2192\u2009S1)43. The partial inclusion of double excitations within the SCS-CC2 method was responsible for the improved accuracy in predicting \u2206E(T1\u2009\u2192\u2009S1). The SCS-CC2 calculation of DABNA-1-based molecules revealed the relationship between its molecular structure and electronic properties, \u2206E(T1\u2009\u2192\u2009S1), and the fluorescence rate constant. However, the TADF mechanism was still unclear because the kRISC was not calculated. Lin et al. calculated rate constants for fluorescence (kF), ISC (kISC), kRISC, and internal conversion (IC) (kIC) for DABNA-144. However, the calculated kRISC was 6.7\u2009\u00d7\u2009102\u2009s\u22121, which was much less than the experimental value of 1.0\u2009\u00d7\u2009104\u2009s\u2212110. The calculated kISC of 1.4\u2009\u00d7\u2009104\u2009s\u22121 was two orders of magnitude less than the experimental value of 4.5\u2009\u00d7\u2009106\u2009s\u2212110. In addition, the calculated nonradiative decay, kIC(S1\u2009\u2192\u2009S0), was greater than the kF(S1\u2009\u2192\u2009S0), suggesting that the PLQY of DABNA-1 was less than 50%, in contrast with the 88% experimental value10. All these previous studies44 only partially explained the photophysical properties of MR-TADF mainly because crucial RISC was not elucidated.Several theoretical studies have attempted to reveal the TADF mechanism in MR molecules. Northey et al. investigated an intersystem-crossing (ISC) mechanism in DABNA-1 using quantum dynamics and time-dependent density-functional theory (TD-DFT) at the PBE0/6-31\u2009G(d) levelE(T1\u2009\u2192\u2009S1) (and spin\u2013orbit coupling (SOC) in some cases) and oscillator strength have been considered to understand the TADF mechanism and to design TADF molecules. However, these are not sufficient for the above aim; quantifications of all types of rate constants and those of energy levels, including higher-lying states relevant to the emission process, are required for the complete understanding of the emission mechanism. Recently, we reported rate-constant predictions enabled by a proposed cost-effective calculation method based on Fermi\u2019s golden rule45. Using the method, we calculated kIC, kISC, kRISC, kF, and the rate constant for phosphorescence (kPhos), of benzophenone as an example. The calculated rate constants agreed well with experimental values. Here, we applied the same method to DABNA-1 and determined all relevant rate constants. We also determined the lifetime of the delayed component in transient PL (trPL), the rate constant of TADF (kTADF), and the PLQY, by calculating the population kinetics of the excited states and the trPL decay curve. The calculations also indicated that, after photoexcitation, T1 was first generated via S1\u2009\u2192\u2009T2 ISC and T2\u2009\u2192\u2009T1 IC. Then, triplet-to-singlet conversion occurred via thermally activated T1\u2009\u2192\u2009T2 IC and T2\u2009\u2192\u2009S1 RISC.Here, we report a comprehensive understanding of the TADF mechanism using the representative MR molecule, DABNA-1. So far, \u22060, S1, T1, and T2 geometries of DABNA-1 were obtained at the TPSSh/6-31+G(d) level. Then, excited states were computed using the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method (see \u201cMethods\u201d section). At the TD-TPSSh level, S1 and T1 local-energy minima were located at the S1- and T1-optimized geometries, respectively. However, as shown in Supplementary Table\u00a01 and T1 energy levels calculated at the EOM-CCSD level were both located at the T1 geometry . In addition, the S1 and T1 structures were nearly the same, including the dihedral angles . Because S2 states were 0.89\u2009eV higher in energy than the S1 states, their contributions were neglected  and that from T2 to T3 was smaller than that from T2 to T1  was only 0.06\u2009eV larger than the experimentally obtained 0.2\u2009eV. Thus, EOM-CCSD significantly improved the overestimation of \u2206E(T1\u2009\u2192\u2009S1), relative to those by previously reported TD-DFT methods44.S1. Figure\u00a0kIC, kISC, kRISC, kF, and kPhos. The raw rate constants in Table\u00a0kIC, kISC, kRISC, kF, and kPhos are given in Supplementary Equations\u00a0We examined triplet formation from SkF(S1\u2009\u2192\u2009S0) (1.4\u2009\u00d7\u2009108\u2009s\u22121) and kIC(S1\u2009\u2192\u2009S0) (1.2\u2009\u00d7\u2009107\u2009s\u22121) agreed quantitatively with experimental results  determined by Hatakeyama et al.10 from PL decay curves of a 1-wt% DABNA-1: 9,9\u2032-biphenyl-3,3\u2032-diylbis-9H-carbazole film at 300\u2009K  agreed with kISC(S1\u2009\u2192\u2009T2) (5.4\u2009\u00d7\u2009106\u2009s\u22121), rather than kISC(S1\u2009\u2192\u2009T1) (1.7\u2009\u00d7\u2009105\u2009s\u22121), suggesting that the experimental kISC should be assigned to kISC(S1\u2009\u2192\u2009T2). The kISC(S1\u2009\u2192\u2009T2) was ten times greater than kISC(S1\u2009\u2192\u2009T1), because of the larger S1\u2013T2 SOC (1.52\u2009cm\u22121) relative to that of S1\u2013T1 (0.06\u2009cm\u22121). The large S1\u2009\u2192\u2009T2 SOC enhanced S1\u2009\u2192\u2009T2 ISC, despite the uphill transition from S1 to T2 . The small S1\u2013T1 SOC resulted from very similar S1 and T1 orbital configurations (HOMO\u2009\u2192\u2009LUMO transition). These results suggested that the ISC (S1\u2009\u2192\u2009T1 conversion) of DABNA-1 occurred via the stepwise S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1 process, rather than by the one-step S1\u2009\u2192\u2009T1 ISC, irrespective of the geometry relaxation  is sufficiently small46. Because T2\u2009\u2192\u2009T1 IC was much faster than S1\u2009\u2192\u2009T2 ISC, the latter was the rate-determining step of the S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1 process  was approximately equal to kISC (S1\u2009\u2192\u2009T2)\u2009=\u20095.4\u2009\u00d7\u2009106\u2009s\u22121  (2.5\u2009s\u22121) was considerably less than the experimental value (1\u2009\u00d7\u2009104\u2009s\u22121)10, indicating that T1\u2009\u2192\u2009S1 conversion did not occur in one-step but via a more effective process. Because the S2 and T3 energy levels, as well as higher singlet and triplet states, could not contribute to the RISC from T1, as discussed above, and T2 was close to S1 , we calculated the trPL decay curve  were then obtained from the trPL decay curve  were calculated fromISC) was calculated fromFor RISC from TT1\u2009\u2192\u2009S1) .5\u2009s\u22121 waT1\u2009\u2192\u2009S1) .5\u2009s\u22121 wakTADF was determined from10Then, k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1) was calculated fromFinally, P, \u03a6TADF, \u03a6ISC, \u03c4TADF, kTADF, k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1), and k(S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1) values. The \u03a6, \u03a6P, \u03a6TADF, and \u03a6ISC values were quantitatively consistent with the experimental values because of the quantitative predictions for kF(S1\u2009\u2192\u2009S0), kIC(S1\u2009\u2192\u2009S0), kISC(S1\u2009\u2192\u2009T2), and kISC(S1\u2009\u2192\u2009T1). The calculated conversion rate constant k(S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1) was consistent with the experimental 1\u2009\u2192\u2009T2\u2009\u2192\u2009T1 ISC rather than direct S1\u2009\u2192\u2009T1 ISC. All the calculated single-step rate constants and k(S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1) agreed well with the experimental values. However, the agreements of the calculated kTADF and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1)  and the experiments  were not as good as we expected, compared with the case of k(S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1). Considering that they included the uphill-energy T1\u2009\u2192\u2009T2 IC, there was a possibility that the overestimation of\u00a0\u2206E(T1\u2009\u2192\u2009T2) leads to an underestimation of kIC(T1\u2009\u2192\u2009T2), kTADF, and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1).Table\u00a0E(T1\u2009\u2192\u2009T2) on kIC(T1\u2009\u2192\u2009T2), kTADF, and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1), we recalculated these rate constants using a corrected \u2206E(T1\u2009\u2192\u2009T2). The rate-determining step for the T2-mediated RISC was T1\u2009\u2192\u2009T2 IC; hence, \u2206E(T1\u2009\u2192\u2009T2) could be viewed as the activation energy for DABNA-1 TADF and RISC. As discussed above, the energy difference between the calculated and experimental T1\u2009\u2192\u2009S1 was 60\u2009meV. Thus, 60\u2009meV was subtracted from the EOM-CCSD-calculated \u2206E(T1\u2009\u2192\u2009T2) value of 252\u2009meV. The energy levels and rate constants calculated with the corrected \u2206E(T1\u2009\u2192\u2009T2) are also listed in Table\u00a0k(S1\u2009\u2192\u2009T2\u2009\u2192\u2009T1) was unchanged, suggesting that the T1 energy correction had little effect on the ISC. In contrast, kIC(T1\u2009\u2192\u2009T2) increased from 1.1\u2009\u00d7\u2009107\u2009s\u22121 to 3.3\u2009\u00d7\u2009108\u2009s\u22121. As a result, kTADF and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1) increased to 1.8\u2009\u00d7\u2009104\u2009s\u22121 and 1.9\u2009\u00d7\u2009104\u2009s\u22121, respectively, which were in much better agreements with the experiments. These results suggested that the \u2206E(T1\u2009\u2192\u2009T2) overestimation was responsible for the underestimation of kTADF and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1). Thus, kTADF and k(T1\u2009\u2192\u2009T2\u2009\u2192\u2009S1) depended largely on kIC(T1\u2009\u2192\u2009T2), which was the sum of IC rate constants for individual molecular vibrations, k\u03b1IC,(T1\u2009\u2192\u2009T2), where \u03b1 denoted the \u03b1th vibrational mode (Supplementary Equations\u00a0\u22121) had the largest k\u03b1IC,(T1\u2009\u2192\u2009T2) value  method, whereas those of S1, T1, and T2 were performed using the TD-TPSSh/6-31+G(d) method with spin multiplicity\u2009=\u20091 -PCM model reproduced experimental DABNA-1 emission and absorption wavelengths in CH2Cl241. The\u00a0geometry optimization and frequency analysis were performed with the Gaussian 16 program package47. For MR molecules, EOM-CCSD method and algebraic diagrammatic construction of the second order, have been shown to be suitable for calculating singlet\u2013triplet energy differences50. Here, excited-state calculations were performed using the EOM-CCSD/6-31\u2009G method implemented in the Q-Chem program package51. Excitation energies, SOCs, vibronic couplings, transition-dipole moments, and permanent dipole moments were calculated using EOM-CCSD wave functions. Examples of Q-Chem input files for running SOC calculations are shown in the Supplementary Methods.Geometry optimization and frequency analysis of SkIC is described elsewhere52 and reviewed in Supplementary Equation\u00a0\u03b1 and each \u03b1 (Supplementary Equation S5). This protocol was also used for calculating the IC rate constants for Mathematical formulation of a method of calculating vibronic couplings and Supplementary InformationPeer Review File"}
{"text": "To the Editor:TP53 encodes the tumour suppressor protein p53, a master regulator of genomic integrity and cell survival, and is the most frequently mutated gene.3\u2010p53m\u2010RA competitively abolished p53\u2010R175H pulldown from cell lysates with N3\u2010p53m\u2010RA\u2010biotin. By contrast, there was almost no pulldown of wild\u2010type p53 (p53\u2010WT)  Figure\u00a0. Structu) Figure\u00a0, but the) Figure\u00a0. Moreove) Figure\u00a0. TherefoA Figure\u00a0.3\u2010p53m\u2010RA, indicating successful conjugation  for H1299\u2010p53\u2010R175H and SKBR3 cells were 1.06 and 1.28\u00a0\u00b5M, respectively  demonstrated a slight difference in dp53m\u2010RA migration relative to Nn Figure\u00a0. Simulatn Figure\u00a0. Indeed,n Figure\u00a0, suggestn Figure\u00a0. Time\u2010con Figure\u00a0. To subsn Figure\u00a0. The haly Figure\u00a0. When thy Figure\u00a0. The expy Figure\u00a0. Furthery Figure\u00a0. Moreovey Figure\u00a0, and dp5y Figure\u00a0. These fWe next examined the biological consequences of dp53m\u2010RA\u2010mediated p53\u2010R175H degradation in cancer cells. dp53m\u2010RA treatment dramatically inhibited the proliferation of p53\u2010R175H\u2010expressing H1299 cells and SKBR3 cells. By contrast, dp53m\u2010RA treatment did not affect the proliferation of p53\u2010WT\u2010expressing H1299 cells and A549 cells Figure\u00a0. dp53m\u2010RTP53 mutation with dominant\u2010negative and oncogenic gain\u2010of\u2010function activities, as a binder in PROTAC design, we report the first selective mutant p53 degrader, dp53m\u2010RA. dp53m\u2010RA degraded p53\u2010R175H but not wild\u2010type p53 or other p53 mutants in a ubiquitin\u2010proteasome\u2010dependent manner. Importantly, dp53m\u2010RA inhibited the proliferation and migration of cancer cells specifically harbouring the p53\u2010R175H mutation (Figure\u00a0In summary, by harnessing an RNA aptamer specifically targeting p53\u2010R175H, the most common n Figure\u00a0, suggestThe authors declare they have no conflicts of interest.Supporting InformationClick here for additional data file."}
{"text": "E. The terminal benzene ring is approximately perpendicular to the central 1,4-di\u00adaza\u00adbutadiene mean plane, forming a dihedral angle of 81.2\u2005(3)\u00b0.The title mol\u00adecule is disposed about a centre of inversion and the conformation about the imine bond is  52H40N2, is disposed about a centre of inversion and the conformation about the imine bond [1.268\u2005(3)\u2005\u00c5] is E. The terminal benzene ring is approximately perpendicular to the central 1,4-di\u00adaza\u00adbutadiene mean plane, forming a dihedral angle of 81.2\u2005(3)\u00b0. Weak C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [inter-centroid distance = 4.021\u2005(5)\u2005\u00c5] inter\u00adactions help to consolidate the packing.The title compound, C \u00c5] has an anti-disposition and the imine bonds [1.268\u2005(3)\u2005\u00c5] are E-configured. The dihedral angle between the pendent benzene ring and the 1,4-di\u00adaza\u00adbutadiene least-squares plane is 81.2\u2005(3)\u00b0, consistent with an almost perpendicular relationship. In the crystal, C\u2014H\u22ef\u03c0, Table\u00a01x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z.In this study, we designed and synthesized the title compound Fig.\u00a01 as a pot2O led to the corresponding triphenyl-substituted aniline  I, New_Global_Publ_Block. DOI: 10.1107/S2414314620005313/tk4062sup3.txtL1-cif. DOI: 1949863CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The main inter\u00admolecular inter\u00adactions in the two title salts are O\u22efH/H\u22efO contacts, as revealed by Hirshfeld surface analyses. 5H5N4O+\u00b7C7H5O6S\u2212\u00b72H2O, (I), and 6-oxo-1,9-di\u00adhydro\u00adpurin-7-ium perchlorate monohydrate, C5H5N4O+\u00b7ClO4\u2212\u00b7H2O, (II), have been synthesized and characterized using single-crystal X-ray diffraction and Hirshfeld analysis. In both salts, the hypoxanthine mol\u00adecule is protonated at the N7 position of the purine ring. In salt (I), the cation and anion are connected through N\u2014H\u22efO inter\u00adactions. The protonated hypoxanthine cations of salt (I) form base pairs with another symmetry-related hypoxanthine cation through N\u2014H\u22efO hydrogen bonds with an R22(8) ring motif, while in salt (II), the hypoxanthine cations are paired through a water mol\u00adecule via N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds with an R33(11) ring motif. The packings within the crystal structures are stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions in salt (I) and C\u2014O\u22ef\u03c0 inter\u00adactions in salt (II). The combination of several inter\u00adactions leads to the formation of supra\u00admolecular sheets extending parallel to (010) in salts (I) and (II). Hirshfeld surface analysis and fingerprint plots reveal that O\u22efH/H\u22efO contacts play the major role in the crystal packing of each of the salts, with a 54.1% contribution in salt (I) and 62.3% in salt (II).Two salts of 1,9-di\u00adhydro\u00adpurin-6-one (hypoxanthine), namely, 6-oxo-1,9-di\u00adhydro\u00adpurin-7-ium 5-sulfosalicylate dihydrate, C When hypoxanthine inter\u00adacts with strong acids, it becomes protonated at position N7 or N9. A limited number of hypoxanthine salts like hypoxanthine nitrate , a potential oxygen-free radical generator, is a strong agent against cancer cells (Susithra I), and hypoxan\u00adthin\u00adium perchlorate monohydrate, (II), salts and the noncovalent inter\u00adactions that govern their crystal packings.The current article reports the crystal structures of hypoxanthinium 5-sulfosalicylate dihydrate, (2.I) crystallizes with two hypoxanthinium cations (A+ and B+), two 5-sufosalicylate anions  and four solvent water mol\u00adecules  in the asymmetric unit, as shown in Fig.\u00a01I), the B cation is equally disordered over two sets of sites for atoms C5B/C5C, C6B/C6C and O6B/O6C. Atoms H1B/H1C and H7B/H7C attached to N1B and N7B, respectively, are also disordered. The solvent water mol\u00adecule O3W is also disordered over two positions. Atoms N7A and N7B are protonated, which is confirmed by widening of the C5A\u2014N7A\u2014C8A angle to 107.1\u2005(4)\u00b0 compared to the value of 103.8\u00b0 in the two polymorphic forms of the neutral HX mol\u00adecule \u00b0 and N3B\u2014C4B\u2014C5C\u2014N7B\u00a0= \u2212178.3\u2005(6)\u00b0 are similar to those of the two forms of the neutral HX mol\u00adecule \u00b0 and O7B\u2014C9B\u2014C10B\u2014C11B\u00a0= 175.9\u2005(4)\u00b0], a situation that is likewise observed for previously reported crystal structures involving 5SCA\u2212 anions.Salt (II) crystallizes with one hypoxanthinium cation, one perchlorate anion (PCA\u2212) and one solvent water mol\u00adecule in the asymmetric unit. The mol\u00adecular structure of salt (II) is shown in Fig.\u00a02I). The PCA\u2212 anion has the characteristic tetra\u00adhedral shape, with Cl\u2014O bond lengths between 1.4116\u2005(15) and 1.4421\u2005(15)\u2005\u00c5, and O\u2014Cl\u2014O angles between 108.29\u2005(9) and 111.24\u2005(12)\u00b0.Salt (3.I), (010) sheets of cations and sheets of anions are stacked alternately along [010]. The crystal packing is governed by N\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds  self assemble into sheets by inter\u00adaction of symmetry-related counterparts through O7A\u2014H7D\u22efO10A and O7B\u2014H7E\u22efO10B, respectively  via N1B\u2014H1C\u22efO11A and C2B\u2014H2B\u22efO11A with an W\u2014H1WA\u22efO10B, O1W\u2014H1WB\u22efO12B, O2W\u2014H2WA\u22efN3A and O2W\u2014H2WB\u22efO12A  is consolidated by \u03c0\u2013\u03c0 inter\u00adactions between the phenyl rings of the two 5SCA anions (C10A\u2013C15A and C10B\u2013C15B), and the imidazole ring (C4A\u2013N9A) and the pyrimidine ring (N1A\u2013C6A) of cation A+, with centroid-to-centroid distances of 3.547\u2005(3), 3.562\u2005(3), 3.554\u2005(3) and 3.533\u2005(3)\u2005\u00c5, and slippages of 0.815, 1.300, 1.182 and 1.105\u2005\u00c5 , (010) sheets of cations and sheets of anions are stacked alternately along [010]. The crystal packing of salt (II) is dominated by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, and to a minor extent by C\u2014H\u22efO hydrogen bonds  is shown in Fig.\u00a08In the crystal structure of salt (s Table\u00a02. The pro4.I) and (II) were performed using CrystalExplorer17  and 10(b) for (I) and (II), respectively. Corresponding two-dimensional fingerprint plots  and (II) are shown in Figs. 11I), 62.3% (II); N\u22efH/H\u22efN 3.1% (I), 6.8% (II); C\u22efH/H\u22efC 5.9% (I), 5.4% (II); H\u22efH/H\u22efH 16.0% (I), 5.3% (II); C\u22efC/C\u22efC 0.9% (I), 0.1% (II).Hirshfeld surface (HS) analyses of salts  and (II) with the related salt forms of guanine, xanthinium and hypoxanthine reveal that, in most of the crystal structures containing purine derivatives, the purine forms base pairs through pairs of N\u2014H\u22efO or N\u2014H\u22efN hydrogen bonds with an et al., 2014I) and (II) and related systems compiled in Table\u00a03A comparison of salts (6.I) was synthesized by mixing an equimolar ratio of hypoxanthine (0.0340\u2005g) and 5-sulfosalicylic acid (0.0545\u2005g) in hot water. The solution was heated to 333\u2005K for 1\u2005h and then allowed to cool slowly to room tem\u00adper\u00adature. Colourless needle-shaped crystals were harvested from the mother liquid after one week.Salt (II) was synthesized by mixing an equimolar ratio of hypoxanthine (0.0340\u2005g) and iron perchlorate monohydrate (0.0681\u2005g) in hot water. The solution was heated to 333\u2005K with constant stirring for 1\u2005h and then allowed to cool slowly to room tem\u00adper\u00adature. Colourless plate-like crystals were harvested from the mother liquid after one week.Salt (7.I) and (II) are summarized in Table\u00a04I), carbon (C5 and C6) and oxygen (O6) atoms of cation B are equally disordered over two sets of sites, with a refined occupancy ratio of 0.503\u2005(18):0.497\u2005(18). The solvent water mol\u00adecule O3W is disordered over two positions, with a refined site-occupancy ratio of 0.58\u2005(6):0.42\u2005(6). The H atoms of water mol\u00adecules O1W and O2W were located from a difference Fourier map, and the O\u2014H distance restrained to 0.82\u2005\u00c5. Attempts to localize the H atoms of O3W and O4W in (I) from difference Fourier maps failed as there were no relevant electron densities close to these atoms. Hence, these H atoms are not part of the model but are included in the formula. All C- and N-bound H atoms in (I) were placed in idealized positions and refined freely using a riding model, with C\u2014H\u00a0= 0.95\u2005\u00c5 and N\u2014H\u00a0= 0.86\u2005\u00c5, and with Uiso(H)\u00a0= 1.2Ueq. In salt (II), the N-bound H atoms were located in a difference Fourier map and refined freely. The H atoms of the water mol\u00adecule were likewise located from a difference Fourier map. The geometry of the water mol\u00adecule was restrained using DFIX commands with an O\u2014H distance of 0.85\u2005\u00c5 and an H\u22efH distance of 1.36\u2005\u00c5. All C-bound H atoms were treated as for salt (I).Crystal data, data collection and structure refinement details of salts  I, II, global. DOI: 10.1107/S2056989022004753/wm5640Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004753/wm5640IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2170315, 2170314CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 1,3-oxazolidine ring adopts an envelope conformation with the N atom in an endo position. The mean plane of the oxazolidine ring makes dihedral angles of 77.74\u2005(10) and 45.50\u2005(11)\u00b0, respectively, with the 4-bromo\u00adphenol and 1,3,5-tri\u00admethyl\u00adbenzene rings. In the crystal, adjacent mol\u00adecules are connected via C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions into layers parallel to the (200) plane. The packing is strengthened by van der Waals inter\u00adactions between parallel mol\u00adecular layers. A Hirshfeld surface analysis shows that H\u22efH (58.2%), C\u22efH/H\u22efC (18.9%), and Br\u22efH/H\u22efBr (11.5%) inter\u00adactions are the most abundant in the crystal packing.The title compound, C The mean plane of th oxazolidine ring makes dihedral angles of 77.74\u2005(10) and 45.50\u2005(11)\u00b0, respectively, with the 4-bromo\u00adphenol (C6\u2013C11) and the 1,3,5-tri\u00admethyl\u00adbenzene (C14\u2013C19) rings. The mol\u00adecular conformation is stabilized by intra\u00admolecular O11\u2014H11\u22efN3 and C20\u2014H20C\u22efO1 hydrogen bonds  plane , C\u22efH/H\u22efC (18.9%), and Br\u22efH/H\u22efBr (11.5%) contacts are shown in Fig.\u00a05b\u2013d, while numerical details of the different contacts are given in Table\u00a02A Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were obtained with 4.et al., 2016S)-5-chloro-N-({2-oxo-3-[4-(3-oxomorpholin-4-yl)phen\u00adyl]oxa\u00adzolidin-5-yl}meth\u00adyl)-thio\u00adphene-2-carboxamide [(I): Shen et al., 2018et al., 2010et al., 2010et al., 2012R)-2-phen\u00adoxy-1-ethanone [(V): Caracelli et al., 2011A search of the Cambridge Structural Database , adjacent mol\u00adecules are connected via O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions into a zigzag chain along the b-axis direction. In (V), mol\u00adecules are linked into supra\u00admolecular arrays two mol\u00adecules thick in the bc plane through C\u2014H\u22efO, C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions.In the crystal of (I)5.The title compound was synthesized using our recently reported procedure  = 1.2 or 1.5Ueq(C). The hydroxyl H atom was found in a difference-Fourier map and was refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022005928/tx2051sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022005928/tx2051Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022005928/tx2051Isup3.cmlSupporting information file. DOI: 2176709CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The first crystal structure is reported of a mol\u00adecule containing the 1,4,2-di\u00adthia\u00adzole-5-thione heterocycle. The packing features aromatic \u03c0\u2013\u03c0 stacking, weak C\u2014H\u22efS inter\u00adactions and short S\u22efS inter\u00adactions. 8H5NS3, the dihedral angle between the heterocyclic ring and the phenyl ring is 2.62\u2005(5)\u00b0. In the extended structure, aromatic \u03c0\u2013\u03c0 stacking between the 1,4,2-di\u00adthia\u00adzole-5-thione moiety and the phenyl ring is observed [centroid\u2013centroid distances = 3.717\u2005(6) and 3.712\u2005(6)\u2005\u00c5]. The almost planar mol\u00adecules arrange themselves in parallel chains of head-to-tail mol\u00adecules oriented by a network of weak C\u2014H\u22efS contacts close to the sum of their van der Waals radii within the chains. All the hydrogen atoms participate in hydrogen-bonding inter\u00adactions with the sulfur and nitro\u00adgen atoms of adjacent mol\u00adecules. C=S\u22efS contacts between the chains that are significantly shorter than the sum of their van der Waals radii also impact the overall packing.In the title compound, C This pattern of bond lengths is in agreement with a more extensive, and less localized, \u03c0 delocalization in this heterocycle than in the comparable oxa\u00adthia\u00adzolone derivatives.Within the heterocycle moiety, the mol\u00adecule shows significant  \u00b0] on the a axis. Head-to-toe hydrogen-bonding inter\u00adactions between C5 and C6 donors to the exocyclic thione S3 with H\u22efS distances of 2.96 and 3.11\u2005\u00c5, respectively , H5\u22efS1 (3.04\u2005\u00c5), H7\u22efS3 (3.06\u2005\u00c5) and H8\u22efS2 (3.10\u2005\u00c5). The sulfur\u2013sulfur inter\u00adactions occur as a chain out of plane between the thione S3 and S1 atoms within the ring  = 0.671; UV\u2013visible (CH2Cl2) \u03bbmax nm (log \u025b): 256 (4.29), 361 (4.20), 1H NMR 60\u2005MHz, CDCl3) \u03b4 = 7.53 ppm (multiplet).A solution of tri\u00adchloro\u00admethane\u00adsulfenyl chloride  in chloro\u00adform (10.17\u2005g) was added dropwise to a warmed solution of thio\u00adbenzamide  in chloro\u00adform (240\u2005ml) according to a literature procedure (Greig 6.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902200888X/hb8037sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902200888X/hb8037Isup2.hklStructure factors: contains datablock(s) I. DOI: 2205416CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular structure features an angular (phenyl\u00adiodos\u00adyl)benzene cation, the geometry of which was hitherto undescribed in the literature: in the cation, both I\u2014C bonds are approximately normal to the I=O bond, forming a C\u2014I\u2014C angle of 95.36\u2005(4)\u00b0. The crystal structure displays O\u2014H\u22efO, O\u2014H\u22efI and O\u2014H\u22efS hydrogen bonding.The structure of the title salt (systematic name: oxodiphenyl-\u03bb This iodosyl salt arose from the reaction of iodoxybenzene with sodium hydroxide benzene tosyl\u00adate dihydrate \u00b0. The bond lengths of C1\u2014I1 and C7\u2014I1 are 2.1289\u2005(11) and 2.1370\u2005(12)\u2005\u00c5, respectively. These values are comparable to the sum of the van der Waals radii -one, i.e. the Dess\u2013Martin periodinane, with a C\u2014I bond length between the phenyl and iodine of 2.1025\u2005(16)\u2005\u00c5 \u2005\u00c5], resides nearly perpendicular at 77.55\u2005(4)\u00b0 to the I1\u2014O1 bond. This bond length is shorter than the sum (3.05\u2005\u00c5) of the covalent radii, and this is analogous to secondary bonding that was observed by Rentzeperis in his bis\u00ad(di\u00adphenyl\u00adiodo\u00adnium I-oxide) di\u00adacetate trihydrate, between the acetate anion and the iodo\u00adnium I-oxide centre  di\u00adacetate trihydrate  and 2.8118\u2005(10)\u2005\u00c5, respectively.Zhdankin synthesized a tosyl\u00adate derivative of 2-iodoxybenzoic acid. Crystals of the final product could not be isolated, but the inter\u00admediate mixed tosyl\u00adate-acetate derivative was analysed. The I\u2014O bond lengths in this iodine(V) compound had distances of 2.080\u2005(2), 2.213\u2005(2), 2.027\u2005(2) and 1.998\u2005(2)\u2005\u00c5 (Yusubov I-oxide) di\u00adacetate trihydrate also adopted a distorted octa\u00adhedral geometry, albeit via a dimeric coordinating structure \u00b0, the C7\u2014I1\u2014O3 angle of 176.33\u2005(4)\u00b0, the O1\u2014I1\u2014O4 angle of 77.55\u2005(4)\u00b0 with the coordinating tosyl\u00adate anion and the C1\u2014I1\u2014C7 angle of 95.36\u2005(4)\u00b0 complete the distorted octa\u00adhedral geometry. The accompanying tosyl\u00adate anion and water mol\u00adecules occupy apical and equatorial positions to stabilize the monomeric complex. Bis and 1.99\u2005(2)\u2005\u00c5, respectively, as viewed down the a axis  di\u00adacetate trihydrate  was added to the cooled filtrate and a white precipitate formed. The suspension was stirred for an additional 30\u2005min and then filtered. The compound was washed with a minimal amount of diethyl ether (10\u2005ml) and ice-cold water (10\u2005ml). The product  matched known 1H, 13C and FTIR data benzene tosyl\u00adate dihydrate was synthesized according to a modified procedure by Chen 2007 and is iCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622005223/bh4069sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314622005223/bh4069Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622005223/bh4069Isup3.cmlSupporting information file. DOI: 2173122CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "At 293\u2005K, [tBuNHC2Me][Br]2\u00b7H2O crystallizes in the P21/c space group, while [tBuNHC2Et][Br]2\u00b72H2O crystallizes in the P21/n space group at 100\u2005K. At 112\u2005K, [MesNHC2Me][Br]2\u00b72H2O crystallizes in the ortho\u00adrhom\u00adbic space group Pccn while [MesNHC2Et][Br]2\u00b74H2O crystallizes in the P21/c space group at 100\u2005K.The crystal structures of ligand precursor bis\u00ad(imidaozolium) salts 1,1\u2032-methyl\u00adenebis(3- tert-butyl\u00adimidazolium) dibromide monohydrate, C15H26N4+\u00b72Br\u2212\u00b7H2O or [tBuNHC2Me][Br]2\u00b7H2O, 1,1\u2032-bis\u00ad(3-tert-butyl\u00adimidazolium) dibromide dihydrate, C16H28N4+\u00b72Br\u2212\u00b72H2O or [tBuNHC2Et][Br]2\u00b72H2O, 1,1\u2032-methyl\u00adenebis[3-imidazolium] dibromide dihydrate, C25H30N42+\u00b72Br\u2212\u00b72H2O or [MesNHC2Me][Br]2\u00b72H2O, and 1,1\u2032-bis\u00ad[3-imidazolium] dibromide tetra\u00adhydrate, C26H32N42+\u00b72Br\u2212\u00b74H2O or [MesNHC2Et][Br]2\u00b74H2O, are reported. At 293\u2005K, [tBuNHC2Me][Br]2\u00b7H2O crystallizes in the P21/c space group, while [tBuNHC2Et][Br]2\u00b72H2O crystallizes in the P21/n space group at 100\u2005K. At 112\u2005K, [MesNHC2Me][Br]2\u00b72H2O crystallizes in the ortho\u00adrhom\u00adbic space group Pccn while [MesNHC2Et][Br]2\u00b74H2O crystallizes in the P21/c space group at 100\u2005K. Bond distances and angles within the imidazolium rings are generally comparable among the four structures. All four bis\u00ad(imidazolium) salts co-crystallize with one to four mol\u00adecules of water.The crystal structures of ligand precursor bis\u00ad(imidazolium) salts 1,1\u2032-methyl\u00adenebis(3- Bis(imidazolium) salts, [RNHC2R1][X]2 are relatively modular in that modifications can be relatively easily made to exterior groups attached to each NHC (R), the moiety linking the two NHC groups (R1), and the counter-ion (X). One general synthetic approach for synthesizing bis(imidazolium) salts is where two equivalents of an alkyl or aryl imidazole are combined with one equivalent of an organic dihalide reagent and refluxed to afford the final product  salts can be relatively easily synthesized from alkyl or aryl imidazoles, and some are also commercially available.Bis(imidazolium) salts are common precursors for the synthesis of bidentate tert-butyl (tBu) and mesityl (Mes) exterior R groups and methyl\u00adene (Me) or ethyl\u00adene (Et) linking R1 groups. [MesNHC2Et][Br]2 was even reported to be a stand-alone catalyst for the conversion of aryl\u00adaldehydes to carb\u00adoxy\u00adlic acids in combination with water and K2CO3 in DMSO  were reported to be more effective for hydro\u00adsilylation reactions with RhI complexes than ethyl\u00adene linkers  salts are those with tBuNHC2Me][Br]2 and [tBuNHC2Et][Br]2 were used as precursors for synthesis of rhodium complexes 2-assisted deprotometalation  salts with tert-butyl and mesityl ancillary groups.While bis\u00ad(imidazolium) salts are common ligand precursors, few have been structurally characterized  salts were recrystallized from hot methanol and each compound co-crystallizes with one or more mol\u00adecules of water. Fig.\u00a01tBuNHC2Me][Br]2\u00b7H2O and [tBuNHC2Et][Br]2\u00b72H2O are mostly the same within experimental error, with backbone C2\u2014C3 distances of 1.348\u2005(4) and 1.349\u2005(3)\u2005\u00c5, respectively. The N\u2014C distances are also mostly comparable with [tBuNHC2Me][Br]2\u00b7H2O having an N1\u2014C2 and an N2\u2014C3 distance of 1.389\u2005(3)\u2005\u00c5 and N1\u2014C1 and N2\u2014C1 distances both being 1.337\u2005(3)\u2005\u00c5, while [tBuNHC2Et][Br]2\u00b72H2O has an N1\u2014C2 distance of 1.388\u2005(3)\u2005\u00c5, an N2\u2014C3 distance of 1.384\u2005(3)\u2005\u00c5, an N1\u2014C1 distance of 1.327\u2005(3)\u2005\u00c5 and an N2\u2014C1 distance of 1.331\u2005(3)\u2005\u00c5. For the linker, the N2\u2014C7 distance is 1.463\u2005(3)\u2005\u00c5 for [tBuNHC2Me][Br]2\u00b7H2O and 1.468\u2005(3)\u2005\u00c5 for [tBuNHC2Et][Br]2\u00b72H2O.Bond distances in the imidazolium rings of [tBuNHC2Me][Br]2\u00b7H2O and [tBuNHC2Et][Br]2\u00b72H2O. For [tBuNHC2Me][Br]2\u00b7H2O, bond angles include C1\u2014N1\u2014C2 at 108.2\u2005(2)\u00b0, N1\u2014C2\u2014C3 at 107.6\u2005(2)\u00b0, C2\u2014C3\u2014N2 at 106.9\u2005(2)\u00b0, C3\u2014N2\u2014C1 at 108.6\u2005(2)\u00b0, and N2\u2014C1\u2014N1 at 108.7\u2005(2)\u00b0. For [tBuNHC2Et][Br]2\u00b7H2O, bond angles include C1\u2014N1\u2014C2 at 108.21\u2005(19)\u00b0, N1\u2014C2\u2014C3 at 107.3\u2005(2)\u00b0, C2\u2014C3\u2014N2 at 106.9\u2005(2)\u00b0, C3\u2014N2\u2014C1 at 108.54\u2005(19)\u00b0, and N2\u2014C1\u2014N1 at 109.02\u2005(19)\u00b0.Bond angles in the imidazolium rings are also quite similar in [MesNHC2Me][Br]2\u00b72H2O while Fig.\u00a04MesNHC2Et][Br]2\u00b74H2O. Notably, [MesNHC2Et][Br]2\u00b74H2O is the only compound of the four for which the asymmetric unit contains only half of the mol\u00adecule.Fig.\u00a03MesNHC2Me][Br]2\u00b72H2O and [MesNHC2Et][Br]2\u00b74H2O are mostly the same within experimental error, with backbone C2\u2014C3 distances of 1.344\u2005(3) and 1.3506\u2005(19)\u2005\u00c5, respectively. N\u2014C distances are also mostly the same with [MesNHC2Me][Br]2\u00b72H2O having an N1\u2014C2 distance of 1.387\u2005(3)\u2005\u00c5, an N2\u2014C3 distance of 1.380\u2005(3)\u2005\u00c5, an N1\u2014C1 distance of 1.326\u2005(3)\u2005\u00c5, and an N2\u2014C1 distance of 1.341\u2005(3)\u2005\u00c5. Similarly, [MesNHC2Et][Br]2\u00b74H2O has an N1\u2014C2 distance of 1.3872\u2005(16)\u2005\u00c5, an N2\u2014C3 distance of 1.3841\u2005(16)\u2005\u00c5, an N1\u2014C1 distance of 1.3322\u2005(16)\u2005\u00c5 and an N2\u2014C1 distance of 1.3314\u2005(16)\u2005\u00c5. For the linker, the N2\u2014C7 distance is 1.457\u2005(3)\u2005\u00c5 for [MesNHC2Me][Br]2\u00b72H2O and 1.4653\u2005(16)\u2005\u00c5 for [MesNHC2Et][Br]2\u00b74H2O.Bond distances in the imidazolium rings of [MesNHC2Me][Br]2\u00b72H2O and [MesNHC2Et][Br]2\u00b74H2O. For [MesNHC2Me][Br]2\u00b72H2O, bond angles include C1\u2014N1\u2014C2 at 108.92\u2005(17)\u00b0, N1\u2014C2\u2014C3 at 107.20\u2005(19)\u00b0, C2\u2014C3\u2014N2 at 106.95\u2005(19)\u00b0, C3\u2014N2\u2014C1 at 108.96\u2005(17)\u00b0, and N2\u2014C1\u2014N1 at 107.96\u2005(18)\u00b0. For [MesNHC2Et][Br]2\u00b74H2O, bond angles include C1\u2014N1\u2014C2 at 108.51\u2005(11)\u00b0, N1\u2014C2\u2014C3 at 107.19\u2005(11)\u00b0, C2\u2014C3\u2014N2 at 106.87\u2005(11)\u00b0, C3\u2014N2\u2014C1 at 108.89\u2005(11)\u00b0, and N2\u2014C1\u2014N1 at 108.54\u2005(11)\u00b0. Overall, these data support that changing the linker R1 group from methyl\u00adene to ethyl\u00adene does not significantly affect the imidazolium ring structures.Bond angles in the imidazolium rings are also mostly the same for [3.tBuNHC2Me][Br]2\u00b7H2O is stabilized by hydrogen bonding \u2005\u00c5. One tert-butyl group has positional disorder.The supra\u00admolecular structure of [ng Fig.\u00a05. Distancng Fig.\u00a05. HydrogetBuNHC2Et][Br]2\u00b72H2O is stabilized by extensive hydrogen bonding  and Br1\u22efH1A (2.398\u2005\u00c5).The supra\u00admolecular structure of [ng Fig.\u00a06. Distancng Fig.\u00a06. SeveralMesNHC2Me][Br]2\u00b72H2O is also stabilized by hydrogen bonding \u2005\u00c5, O2\u22efH1E at 2.001\u2005(3)\u2005\u00c5, and Br1\u22efH1D at 2.585\u2005(2)\u2005\u00c5.The supra\u00admolecular structure of [Br]2\u00b7H2O, [tBuNHC2Et][Br]2\u00b72H2O, or [MesNHC2Et][Br]2\u00b74H2O. A deposited dataset for [MesNHC2Me][Br]2\u00b72H2O was found . The procedure was adapted from a literature procedure , approximately 100\u2005mL of methanol, and approximately 25\u2005mL of deionized water and a stir bar, then heated to 343\u2005K under reflux. 7.81\u2005mL of 37% formaldehyde  were added, followed by 3.70\u2005mL of ammonium hydroxide  added dropwise over 5 minutes while stirring. The solution was refluxed at 343\u2005K for 5\u2005h, resulting in a light red\u2013orange solution. Excess solvent was removed in vacuo, and the resulting product was diluted with approximately 150\u2005mL of di\u00adchloro\u00admethane and washed twice with 50\u2005mL of deionized H2O until the aqueous layers ran clear. The product was vacuum distilled at \u223c373\u2005K, yielding a clear liquid, which was weighed in a tared vial, resulting in 7.95\u2005g (34% yield) of tBuIm, and characterized by 1H NMR spectroscopy in CDCl3.Synthesis of 1--1HMesIm).-imidazole,  of tan\u2005crystals, which were characterized by 1H NMR spectroscopy and identified as MesIm.Synthesis of 1,1\u2032-di(tert-but\u00adyl)-3,3\u2032-methyl\u00adene-diimidazolium dibromide, [tBuNHC2Me][Br]2. 1.850\u2005g  of tbuIm and 0.4194\u2005mL  of di\u00adbromo\u00admethane, a stir bar, and \u223c20\u2005mL of toluene were stirred in a 50\u2005mL round-bottomed flask. The solution was then heated to 423\u2005K and refluxed for 46\u2005h, resulting in the formation of a dark orange\u2013brown solution. The solution was cooled in an ice bath, resulting in a fine white precipitate which was collected via vacuum filtration, washed twice with \u223c5\u2005mL of cold toluene, filtered and dried. 1.120\u2005g (78.02% yield) of a fine white solid identified as [tBuNHC2Me][Br]2 were isolated. Crystals suitable for X-ray diffraction were obtained by recrystallization from hot methanol. The product was characterized by 1H NMR spectroscopy. The 1H NMR data were consistent with those previously reported -3,3\u2032-ethyl\u00adene-diimidazolium dibromide [tBuNHC2Et][Br]2. A 250\u2005mL round-bottomed flask was charged with 2.017\u2005g  of tbuIm, 0.562\u2005mL  of di\u00adbromo\u00adethane, a stir bar, and \u223c20\u2005mL of toluene. The mixture was refluxed at 423\u2005K and stirred for 46\u2005h, at which point the solution was a rusty brown color. The flask was then placed in an ice bath, and the resulting precipitate was collected via vacuum filtration and washed twice with \u223c5\u2005mL of cold toluene. The resulting solids were dried and weighed, yielding 1.727\u2005g (61% yield) of [tBuNHC2Et][Br]2 and single crystals suitable for X-ray diffraction were obtained via recrystallization from hot methanol. 1H NMR data were consistent with those previously reported -3,3\u2032-methyl\u00adene-diimidazolium dibromide, [Br]2 suitable for X-ray diffraction and characterized by 1H NMR.MesNHC2Et][Br]2.Synthesis of 1,1\u2032-di(mesit\u00adyl)-3,3\u2032-ethyl\u00adene-diimidazolium dibromide, [Br]2.6.SHELXL and included as riding contributions with distances of 0.95\u2005\u00c5 for C\u2014H, 0.99\u2005\u00c5 for CH2 and 0.98\u2005\u00c5 for CH3. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Uiso values of riding H atoms were set to 1.2 times Ueq(C) for CH and CH2, and 1.5 times Ueq(C) for CH3 and H2O. For [tBuNHC2Me][Br]2, the SADI command of SHELX was used to model disorder in one of the tert-butyl moieties for N4\u2014C0AA and N4\u2014C12, C0AA\u2014C00N and C14\u2014C12, and C1AA\u2014C0AA and C13\u2014C12 to restrain distances within a sigma of 0.02\u2005\u00c5. The population parameters for the disordered tert-butyl groups are 0.54019 for C12\u2013C14, and 0.45981 for C00N, C0AA, and C1AA. The highest peak and deepest hole are both near a heavy atom Br1 with a distance of 0.88\u2005\u00c5 from the highest peak of 1.49\u2005e\u2005\u00c5\u22123 and a distance of 0.73\u2005\u00c5 from the deepest hole of \u22121.10\u2005e\u2005\u00c5\u22123.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022008003/mw2188sup1.cifCrystal structure: contains datablock(s) sces01006_0m, est01043_0m, at01019_0ma, est01041d_0ma, global. DOI: 10.1107/S2056989022008003/mw2188sces01006_0msup2.hklStructure factors: contains datablock(s) sces01006_0m. DOI: 10.1107/S2056989022008003/mw2188est01043_0msup3.hklStructure factors: contains datablock(s) est01043_0m. DOI: 10.1107/S2056989022008003/mw2188at01019_0masup4.hklStructure factors: contains datablock(s) at01019_0ma. DOI: 10.1107/S2056989022008003/mw2188est01041d_0masup5.hklStructure factors: contains datablock(s) est01041d_0ma. DOI: Click here for additional data file.10.1107/S2056989022008003/mw2188sces01006_0msup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022008003/mw2188est01043_0msup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022008003/mw2188at01019_0masup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022008003/mw2188est01041d_0masup9.cmlSupporting information file. DOI: 2195736, 2195735, 2195734, 2195733CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In recent years, a number of mass spectrometric and laser spectroscopic techniques have been developed and are increasingly used by the research community. Advances in this active research area, however, critically depend on the availability of suitable N2O isotope Reference Materials (RMs).Information on the isotopic composition of nitrous oxide  have been analysed by specialised laboratories against isotope reference materials. A particular focus was on the 15N site\u2010specific isotopic composition, as this measurand is both highly diagnostic for source appointment and challenging to analyse and link to existing scales.Within the project Metrology for Stable Isotope Reference Standards (SIRS), seven pure N2O isotope RMs offer a wide spread in delta (\u03b4) values: \u03b415N: 0 to +104\u2030, \u03b418O: +39 to +155\u2030, and \u03b415NSP: \u22124 to +20\u2030. Conversion and uncertainty propagation of \u03b415N and \u03b418O to the Air\u2010N2 and VSMOW scales, respectively, provides robust estimates for \u03b415N(N2O) and \u03b418O(N2O), with overall uncertainties of about 0.05\u2030 and 0.15\u2030, respectively. For \u03b415NSP, an offset of >1.5\u2030 compared with earlier calibration approaches was detected, which should be revisited in the future.The established N2O isotope RMs anchored to the international isotope\u2010ratio scales was developed that will promote the implementation of the recommended two\u2010point calibration approach. Particularly, the availability of \u03b417O data for N2O RMs is expected to improve data quality/correction algorithms with respect to \u03b415NSP and \u03b415N analysis by mass spectrometry. We anticipate that the N2O isotope RMs will enhance compatibility between laboratories and accelerate research progress in this emerging field.A set of seven N For nitrogen, the 15N/14N isotope ratio is used, R(15N/14N)\u2009=\u00a0x(15N)/x(14N), where x is the isotopic abundance and tropospheric N2 is the international reference material for the Air\u2010N2 scale. For oxygen, the 18O/16O and 17O/16O ratios are used, which are related to the Vienna Standard Mean Ocean Water (VSMOW) scale. In addition, we adopt the following notation conventions: \u03b415N\u2009=\u00a0\u03b4 (average of both nitrogen atoms) and \u03b418O\u2009=\u00a0\u03b4. The 15N site preference (SP) is defined by the predominance of 15N substitution in the central (\u03b1) position as compared to the terminal (\u03b2) position, and calculated accordingly as \u03b415NSP\u00a0=\u00a0\u03b415N\u03b1\u00a0\u2212\u00a0\u03b415N\u03b2. All \u03b4 values in this paper are reported against Air\u2010N2 (for 15N/14N ratios) and against VSMOW (for 18O/16O and 17O/16O ratios).The isotopic composition of a sample is reported using the delta  as well as \u03b417O and \u03b418O (water) have a different chemical identity than N2O sample gas. Thus, a chemical conversion reactionFurther progress in N2O by thermal decomposition of isotopically characterised ammonium nitrate (NH4NO3) has been suggested as an approach to link the position\u2010dependent nitrogen isotopic composition of N2O to the Air\u2010N2 scale.\u03b1\u2010position of of the formed N2O originates from NO3\u2212, while the \u03b2\u2010nitrogen comes from NH4+.4NO3 decomposition technique has been confirmed,\u03b415N\u03b1 and \u03b415N\u03b2 was found to be limited by non\u2010quantitative NH4NO3 decomposition in combination with substantially different isotope enrichment factors of \u22124 or \u221219\u2030 for the conversion of the NO3\u2212 or NH4+ nitrogen atom into the \u03b1\u2010 or \u03b2\u2010position of the N2O molecule.2O reference gases, USGS51 and USGS52, recently became available with assigned \u03b4 values based on a preliminary assessment by Naohiro Yoshida and Sakae Toyoda (Tokyo Institute of Technology).\u03b415N and \u03b418O values (< 1\u2030), which is not suitable for a two\u2010point calibration approach.The synthesis of N2O RMs within the framework of the European Metrology Programme for Innovation and Research (EMPIR) 16ENV06 project \u2018Metrology for Stable Isotope Reference Standards (SIRS)\u2019. The target isotopic composition of N2O RMs was selected according to discussions at a stakeholder workshop at the 19th GGMT conference at Empa (29 August 2017).2O RMs compared to RMs presented in Ostrom et al\u03b417O data in order to improve data quality/correction algorithms with respect to \u03b415NSP and \u03b415N analysis by mass spectrometry. In addition, the link of \u03b4 values to the international isotope\u2010ratio scales was revisited.In the present study, we report the development of additional N22O RMs, covering an extended range of delta values as compared to existing gases. Figure\u00a02O RMs.The main purpose of this study is the provision of isotopically characterised N15N/14N isotope ratios on the Air\u2010N2 scale were propagated from NH4+ and NO3\u2212 salts supplied by IAEA/USGS, through isotopic analysis of gravimetrically prepared NH4NO3 salts (section\u00a0\u03b415N\u03b2(N2O) /\u03b415N\u03b1(N2O) in the novel N2O RMs. The international RMs applied in this study are listed in Table\u00a02O site\u2010specific isotopic composition, the NH4NO3 decomposition reaction was optimised for high yield, reproducibility, and N2O purity , \u03b418O(N2O), \u03b417O(N2O) and \u03b415NSP(N2O) is described. In one laboratory (Empa), \u03b415NSP(N2O) in the N2O RMs was linked to the Air\u2010N2 scale making use of the traceability chain established in section\u00a0In section\u00a02.12.1.14NO3 salts (S1\u2013S6), covering a wide range of \u03b415N(NH4+) and \u03b415N(NO3\u2212) values, were produced by gravimetric mixing of five commercially available NH4NO3 salts (A\u2013E). A: unlabelled NH4NO3 , B: 15NH4NO3 , C: NH415NO3 , D: 15NH4+\u2010depleted NH4NO3 , E: 15NO3\u2212\u2010depleted NH4NO3 .Six NH4NO3 salts (Table\u00a04NO3 (A) was ground to a fine powder using a mortar and pestle and then dried at 120\u00b0C for 1\u00a0h (a temperature low enough to avoid triggering decomposition). From this, around 100\u2009g (S1\u2013S5) or around 40\u2009g (S6) were gravimetrically  mixed with appropriate amounts of salts B, C, D, and E to obtain the desired isotopic composition. The salt mixtures were dissolved in deionised water , recrystallised, dried, and then stored in air\u2010tight sample containers. The isotopic homogeneity of S1\u2013S6 was confirmed by repeated IRMS analysis (MPI\u2010BGC), demonstrating \u03b415N(NH4NO3) values within <0.2\u2030 .For preparation of these six NHts Table\u00a0, approxi2.1.24NO3 salts (S1\u2013S6) were sent together with international reference materials ((NH4)2SO4, NaNO3, KNO3) provided by the IAEA  and by USGS   Table\u00a0.\u03b415N(NH4NO3), \u03b415N(NH4+) and \u03b415N(NO3\u2212) results from all laboratories were calibrated using the provided international IAEA and USGS reference materials, with \u03b415N values and uncertainties according to Brand et al\u03c3cal) was estimated from the uncertainty  in the linear calibration function (Equation\u00a0\u03c3meas) in \u03b415Nmeas, following the law of error propagation  from individual laboratories i were combined to a weighted mean value  were weighed into round\u2010bottomed glass flasks with a break\u2010seal . In a variant of the NH4NO3 decomposition reaction according to Szab\u00f3 et al,4HSO4  and 0.2\u00a0g (NH4)2SO4  were added. Adding surplus NH4+ salt will lead to a loss in \u03b415N\u03b2 information but was included to test if very high reaction yields can be achieved, which might still be attractive. Therefore, for S1, both variants (with/without NH4HSO4/(NH4)2SO4) were tested, while for S2\u2013S6 only decomposition without NH4+ addition was performed. Thereafter, the flasks were evacuated (<10\u22121\u00a0mbar) and flame\u2010sealed. The sealed flasks were placed in a circulating\u2010air oven  and heated to 270\u00b0C for 24\u2009h.Aliquots of approximately 1.0\u00a0g (12.5\u00a0mmol) of NH2O product gas, e.g. S1\u2010derived\u2010N2O (here: S1\u2010N2O) or S6\u2010derived\u2010N2O (S6\u2010N2O), was purified on a vacuum manifold by cryogenic distillation. Reaction by\u2010 and side\u2010products  were trapped at \u221278\u00b0C (dry ice/ethanol bath); N2O was trapped at \u2212196\u00b0C (liquid N2) in a coiled stainless\u2010steel tube, while N2 and O2 (side products) were removed by evacuation with an oil\u2010sealed rotary vane pump . Thereafter, the N2O product was condensed into 10\u00a0mL stainless\u2010steel flasks  under liquid\u2010nitrogen cooling. The cryogenic extraction was repeated five times to fully capture the produced N2O. Finally, the N2O yield was determined gravimetrically . The N2O purity, i.e. the absence of IR\u2010active impurities , was confirmed by FTIR spectroscopy .2 (<0.01%) and N2O recovery (>99.4%), using different gravimetric mixtures of high\u2010purity N2O and N2 .After the decomposition reaction, the N4NO3 decomposition reaction across the large range of \u03b4 values  was tested. In detail, such tests were made by comparing \u03b415N\u03b1 of NH4NO3\u2010derived N2O gases (S1\u2010N2O\u2013S6\u2010N2O) with the \u03b415N(NO3\u2212) of substrate NH4NO3 salts (S1\u2013S6) and \u03b415N\u03b2 with \u03b415N(NH4+), respectively. While the link provided by the NH4NO3 decomposition reaction was assumed to be valid across a wide range of \u03b4 values, the analytics involved in \u03b415N\u03b1, \u03b415N\u03b2 or \u03b415N(NO3\u2212), \u03b415N(NH4+) analysis might display non\u2010linearities.First, the consistency of the NH2O gases S2\u2010N2O, S3\u2010N2O, S5\u2010N2O and S6\u2010N2O were analysed together with S1\u2010N2O and S4\u2010N2O using the QCLAS analyser  and in preliminary experiments displayed a consistent offset between \u03b415N\u03b1(N2O), \u03b415N\u03b2(N2O) and \u03b415N(NO3\u2212), \u03b415N(NH4+) values (data not shown). For actual \u03b415N\u03b1 and \u03b415N\u03b2 of S1\u2010N2O and S4\u2010N2O, known \u03b415N(NO3\u2212) and \u03b415N(NH4+) values of the respective NH4NO3 salts were adopted and no correction for fractionation effects due to incomplete decomposition or branching isotope effects due to N2 production was applied. The uncertainty of actual \u03b415N\u03b1 and \u03b415N\u03b2 for S1\u2010N2O and S4\u2010N2O was estimated from the uncertainty of weighted mean \u03b415N(NO3\u2212) and \u03b415N(NH4+) values  of the educt NH4NO3 salts S1/S4, were used to define a linear calibration function  was tested against the actual \u03b415N\u03b1 values, i.e. the \u03b415N(NO3\u2212) of the respective NH4NO3 salts (S1\u2013S6). The same procedure was applied to \u03b415N\u03b2 and \u03b415N(NH4+).Measured 2.22.2.12O gases offer only limited isotopic variability. Therefore, high\u2010purity N2O  was supplemented with defined amounts of 15N\u2010enriched/15N\u2010depleted and 18O\u2010enriched N2O dopant gas using a ten\u2010port two\u2010position valve  with sample loops of different volumes , as well as 18O\u2010enriched N2O ((36.25\u2009\u00b1\u00a00.10)% NN16O, (63.75\u2009\u00b1\u00a00.76)% NN18O) and 15N\u03b2\u2010depleted N2O (\u03b415N\u03b1\u00a0=\u2009(\u22122.54\u2009\u00b1\u00a00.005)\u2030, \u03b415N\u03b2\u00a0=\u2009(\u2212162.21\u2009\u00b1\u00a00.03)\u2030, \u03b418O\u2009=\u2009(+38.92\u2009\u00b1\u00a00.003)\u2030), both produced and characterised at Empa. Details on the production and analysis of 18O\u2010enriched N2O and 15N\u03b2\u2010depleted N2O are provided in the supporting information\u00a0 or 150\u2009mL (Lab MPI) stainless\u2010steel flasks  for isotopic analysis.The dopant gases were commercial ormation\u00a0. N2O RMs2.2.2\u03b415N\u03b1, \u03b415N\u03b2 and \u03b418O in the N2O gases, a QCLAS spectrometer \u22121 and an astigmatic Herriott multi\u2010pass absorption cell (204\u2009m path length) was applied. Prior to analysis, pure N2O gases  were diluted to around 50\u2009\u03bcmol\u2009mol\u22121 using one cylinder of synthetic air ((20.5\u00a0\u00b1\u00a00.5)% O2 in N2, Messer Schweiz AG, Switzerland) into 2\u00a0L high\u2010pressure stainless\u2010steel cylinders  using a ten\u2010port two\u2010position valve . A singular cylinder of synthetic air was used for all experiments to minimise differences in the oxygen content, which would otherwise affect pressure broadening of absorption lines, result in differences in apparent isotopologue mole fractions and increase uncertainties. The selection of synthetic air as diluent is somewhat arbitrary and not meant to represent an alternative for a full\u2010air matrix for high\u2010accuracy ambient N2O isotope analysis, which would enclose noble and trace gases depending on the analytics and accuracy requirements.For analysis of \u03b415N\u03b1\u00a0=\u2009(+25.73\u2009\u00b1\u00a00.24)\u2030, \u03b415N\u03b2\u00a0=\u2009(+25.44\u2009\u00b1\u00a00.36)\u2030, \u03b418O\u2009=\u2009(+35.86\u2009\u00b1\u00a00.22)\u2030) and CG2 (\u03b415N\u03b1\u00a0=\u2009(\u221248.59\u2009\u00b1\u00a00.25)\u2030, \u03b415N\u03b2\u00a0=\u2009(\u221246.11\u2009\u00b1\u00a00.43)\u2030, \u03b418O\u2009=\u2009(+27.37\u2009\u00b1\u00a00.11)\u2030). The isotopic composition of the calibration gases had been previously analysed by Sakae Toyoda at the Tokyo Institute of Technology using their analytical technique as a link to the international scales.The spectroscopically determined isotope ratios were related to the isotope\u2010ratio scales realised by Toyoda et al2O RMs by QCLAS, the site\u2010specific isotopic information provided by NH4NO3\u2010derived N2O gases S1\u2010N2O (\u03b415N\u03b1\u00a0=\u2009(\u22121.41\u2009\u00b1\u00a00.21)\u2030, \u03b415N\u03b2\u00a0=\u2009(+0.33\u2009\u00b1\u00a00.12)\u2030) and S4\u2010N2O (\u03b415N\u03b1\u00a0=\u2009(+52.36\u2009\u00b1\u00a00.15)\u2030, \u03b415N\u03b2\u00a0=\u2009(+53.06\u2009\u00b1\u00a00.16)\u2030) was propagated to the N2O RMs (RM1\u2013RM5). For this, the N2O RMs were analysed together with S1\u2010N2O and S4\u2010N2O, as described in the preceding section, to propagate the moiety\u2010specific isotopic composition defined by S1 and S4 to the novel RMs  MAT 252 mass spectrometer  against an isotopically characterised laboratory tank of pure N2O ; C1: \u03b415N\u2009=\u2009(\u22122.4\u00a0\u00b1\u00a00.4)\u2030, \u03b415N\u03b1\u00a0=\u2009(\u22124.5\u00a0\u00b1\u00a00.4)\u2030, \u03b415N\u03b2\u00a0=\u2009(\u22120.3\u00a0\u00b1\u00a00.8)\u2030, \u03b418O\u2009=\u2009(+23.3\u00a0\u00b1\u00a01.2)\u2030. IRMS analysis of the N2O intramolecular 15N distribution was based on the quantification of the fragment NO+ (m/z 30 and 31) and molecular N2O+  ions to calculate isotope ratios for the entire molecule and the central (\u03b1) and terminal (\u03b2) N atom. Analysis of \u03b415N (45/44) and \u03b415N\u03b1 involves correction for interfering 14N217O+ (m/z 45) and 14N17O+ (m/z 31) using actual \u039417O values analysed at the University of East Anglia (UEA). For the analysis of \u03b415N\u03b1 and \u03b415N\u03b2, rearrangement of N atoms (N\u03b1 and N\u03b2) in the ion source was considered. The \u03b415N, \u03b415N\u03b1 and \u03b415N\u03b2 values of the local reference gas were previously anchored to Air\u2010N2 by NH4NO3 decomposition,\u03b418O value was anchored to VSMOW by converting N2O into CO2 with graphite and a platinum foil . The analytical uncertainties were calculated from the uncertainty of the in\u2010house working N2O standard gases and the standard deviation for repeated measurements of the sample gas (N2O RM) and the in\u2010house working N2O standard following the law of error propagation. Specifically, the uncertainty of the in\u2010house working N2O standard gas for \u03b415N, \u03b415N\u03b1 and \u03b415N\u03b2 values comprises both the uncertainty in the \u03b415N(NH4+) and \u03b415N(NO3\u2212) analysis and the repeatability of the NH4NO3 decomposition reaction. For \u03b418O, the uncertainty of the in\u2010house working N2O standard gas includes the repeatability of the conversion reaction of N2O into CO2 with graphite. \u03b417O signatures of three N2O RMs  were analysed by high\u2010resolution IRMS . Experimental details of this prototype analyses are provided in the supporting information . The system and the method used have been described by Sperlich et al.\u03b415N values of the sample N2O were scaled to IAEA\u2010N\u20101 and USGS32. In addition to the sample gases, an in\u2010house standard N2O gas NINO was analysed in each sample run, which was used as an anchor for \u03b415N measurements by DI\u2010IRMS. USGS40, and the in\u2010house standards Ali\u2010j3 (\u03b415N\u2009=\u2009(\u22121.51\u2009\u00b1\u00a00.1)\u2030; acetic anilide) and Caf\u2010j3 (\u03b415N\u2009=\u2009(\u221215.46\u2009\u00b1\u00a00.1)\u2030; caffeine), were analysed in each daily run as quality controls, but not used for data correction.2O RMs were analysed twice  on a DI\u2010IRMS system  using separately subsampled flasks. We note that the published \u03b4 values for USGS51 and USGS52 are average values with a rather large deviation between laboratories. Therefore, we scaled the DI\u2010IRMS \u03b415N analyses to the in\u2010house standard NINO using the value reported for the primary calibration using EA/IRMS (\u03b415N\u2009=\u2009(+0.54\u2009\u00b1\u00a00.21)\u2030). The \u03b418O value of NINO (\u03b418O\u2009=\u2009(+39.94\u2009\u00b1\u00a00.34)\u2030) was determined by setting the \u03b418O of USGS51 equal to the average value from the interlaboratory comparison (\u03b418O\u2009=\u2009(+41.45\u2009\u00b1\u00a00.34)\u2030) published by Ostrom et al.The N\u03b415N is measured from N2 gas, the DI\u2010IRMS method allows the analyses of \u03b415N and \u03b418O values by simultaneously recording m/z 44 (14N14N16O+), 45  and 46  ion currents. \u03b415N and \u03b418O values for N2O RMs were calculated according to Kaiser et al17O values determined by UEA were used.In contrast to the EA/IRMS technique, where \u03b415N and \u03b418O measurements of the N2O standard gases  and from the standard deviation for repeated measurements of the sample gas (N2O RM) and the N2O standards, following the law of error propagation.The uncertainty of the analyses was calculated from the uncertainty of 2.2.52O RM samples and a N2O\u2010MG\u20106.0 working reference  were diluted to 0.09\u2009mmol\u2009mol\u22121 in N2 , filled into 20\u2009mL serum vials  and analysed for \u03b4(\u039d2\u039f) and \u03b4(\u039d2\u039f) on a custom\u2010built automated cryogenic extraction and purification system comprised of an autosampler, a valve system, and PoraPLOT Q pre\u2010 and main columns , coupled to a GEO 20\u201020 isotope ratio mass spectrometer .The N\u03b4(O2)\u2009=\u00a0\u03b417O,\u00a0\u03b4(O2)\u2009\u2248\u00a0\u03b418O (the error of this approximation is <0.01\u2030) and 29\u03b4(\u039d2)\u2009=\u00a0\u03b415\u039d after cryogenic N2O extraction and decomposition to N2 and O2 with a 500\u2009mm long pure gold tube  held at 854\u00b0C. N2 and O2 were separated directly (without further cryofocussing) on a molecular\u2010sieve 5\u2010\u00c5 PLOT main column ). The quantitative conversion of N2O was verified by swapping the molecular\u2010sieve main column for the PoraPLOT Q main column and testing for residual N2O with the mass spectrometer. The raw \u03b417O and \u03b418O measurements were affected by scale compression. To correct for this, a logarithmic scale normalisation\u03b418O value of +112.4\u2030 (relative to N2O\u2010MG\u20106.0) derived from the \u03b4(\u039d2\u039f) measurements of the diluted RM4 sample measured on the GEO 20\u201020 mass spectrometer. The same normalisation was used for \u03b417O as for \u03b418O because no N2O reference material with a calibrated \u03b417O value was available. No scale\u2010normalisation was applied to the \u03b415N measurements. Uncertainties were calculated using the law of error propagation from the standard deviations of replicate measurements against the working reference gas and the calibration uncertainties of the working reference gas against Air\u2010N2 and VSMOW.Using the same mass spectrometer, these samples were also analysed for 2O RM samples were analysed for \u03b4(\u039d2\u039f) and \u03b4(\u039d2\u039f) with respect to the N2O working reference N2O\u2010MG\u20106.0 using the dual\u2010inlet system of a Finnigan MAT 253 isotope ratio mass spectrometer . The N2O\u2010MG\u20106.0 working reference has been calibrated by Kaiser et al,\u03b415N\u2009=\u2009(+1.01\u2009\u00b1\u00a00.06)\u2030 with respect to Air\u2010N2, as well as \u03b418O\u2009=\u2009(+38.45\u2009\u00b1\u00a00.22)\u2030 and \u03b417O\u2009=\u2009(+19.66\u2009\u00b1\u00a00.11)\u2030 with respect to VSMOW.\u03b417O values of N2O RMs analysed with the Sercon GEO 20\u201020 were used for the data correction according to Kaiser et al.2 and VSMOW.The N33.1\u03b415N\u03b1 and \u03b415N\u03b2 in N2O to the Air\u2010N2 scale and calculating uncertainties are described. Section\u00a0\u03b415N(NH4+) and \u03b415N(NO3\u2212) analyses in NH4NO3 salts (S1\u2013S6) by eight isotope laboratories against international IAEA and USGS standards. Section\u00a04NO3 decomposition at high yield, repeatability, and N2O purity. To enable the two\u2010point calibration, a number of NH4NO3 salts with different isotopic composition were produced and decomposed and the consistency of \u03b415N\u03b1 and \u03b415N\u03b2 of the N2O gases (S1\u2010N2O\u2013S6\u2010N2O) and the \u03b415N(NH4+) and \u03b415N(NO3\u2212) of NH4NO3 salts (S1\u2013S6) was tested , as analysed by the eight isotope laboratories and calibrated to Air\u2010N2 by analysis of IAEA and USGS standards, is indicated in Table\u00a04NO3 samples , all results obtained by EA/IRMS were included for calculation of the weighted mean value except for results by one laboratory (Lab 4), as this laboratory used a more complicated analytical procedure with higher uncertainties. For \u03b415N(NO3\u2212) and \u03b415N(NH4+), all laboratory results were included to calculate the weighted mean values, irrespective of the applied analytical technique.For \u03b415N(NH4NO3) with average \u03b415N(NH4+)/\u03b415N(NO3\u2212) values indicates a good agreement to within <0.2\u2030. Nonetheless, results by individual laboratories for moiety\u2010specific \u03b4 values deviate substantially from the weighted mean. As an example, \u03b415N(NO3\u2212) results from Lab 8 are substantially higher than those from other laboratories by an average of (+2.15\u2009\u00b1\u00a00.58)\u2030. This may be due to the specific preparation technique applied, NH4+ removal by ion exchange, a technique which is prone to preferential retention/elution of 15NO3.\u03b415N values of both NO3\u2212 and NH4+, which may be reflected in the \u03b415N(NH4+) values of Lab 6 but not those of Lab 5, where a similar technique was used. Conversely, systematic fractionation effects by preparation techniques should be accounted for by identical treatment (IT) of the provided IAEA and USGS standards used for data correction. In summary, analysis of \u03b415N(NH4+) and \u03b415N(NO3\u2212) is still challenging; however, the ensemble of techniques applied in this study provides good agreement with \u03b415N(NH4NO3) values.A comparison of 3.1.22O yield of 93\u201395% was achieved for the decomposition of NH4NO3 salts S1\u2013S6 (Table\u00a0n\u00a0=\u00a03), surpasses results by Westley et aln\u00a0=\u200920). A further increase in the yield of the NH4NO3 decomposition was achieved by conducting the reaction in a NH4HSO4\u2013(NH4)2SO4 melt (around 2%), as suggested for industrial applications by Szab\u00f3 et al\u03b415N\u03b1 values but a loss in the \u03b415N\u03b2 information due to NH4+ salt addition, and was thus not continued.Under optimised reaction conditions  and distillation procedure, an average N\u03b415N\u03b1 and \u03b415N\u03b2 for the loss in N2O (around 5\u20137%), mainly due to uncertainties in the reaction mechanisms (incomplete decomposition or side\u2010reaction), which makes it difficult to estimate the effect on \u03b4 values. Assuming incomplete reaction accompanied by fractionation effects, according to our earlier study,\u03b415N\u03b1/\u03b415N\u03b2/\u03b415N values, respectively. However, a much smaller difference in \u03b415N was observed when comparing results of N2O RMs analysed by QCLAS  with IRMS analyses. Therefore, our assumption is that the decrease in yield is at least partly caused by a \u201cbranching\u201d side reaction, e.g. nitrogen gas (N2) production,\u03b415N(N2) values.2 production has a minor effect on \u03b415N\u03b1, \u03b415N\u03b2 and \u03b415NSP, but the effect is expected to depend on the timing of N2 generation, which is not known.No correction was applied to 3.1.32 scale and to determine the N2O site\u2010specific isotopic composition across a wide range of \u03b4 values. Therefore, the consistency of the isotopic composition of the N2O gases  and the NH4NO3 salts (\u03b415N(NH4+) and \u03b415N(NO3\u2212), S1\u2013S6) was tested. The detailed procedure is described in section\u00a04NO3 decomposition reaction, measured \u03b415N\u03b1 values of S1\u2010N2O/S4\u2010N2O and actual \u03b415N\u03b1 values, i.e. \u03b415N(NO3\u2212) of the educt NH4NO3 salts S1/S4, were used to define a linear calibration function. \u03b415N\u03b1cal values of S2\u2010N2O, S3\u2010N2O, S5\u2010N2O and S6\u2010N2O were calculated from measured \u03b415N\u03b1 using this correction function and compared against actual values /\u03b415N(NH4+)/\u03b415N(NO3\u2212) \u2013 \u03b415N(NH4+) of the respective salts . Assuming similar fractionation effects for decomposition of all NH4NO3 salts (S1\u2013S6), provided the comparable decomposition yield  and \u03b415N(NH4+) analyses of the NH4NO3 salts. The latter is more plausible, as the QCLAS analyses using the same calibration approach showed good agreement with independent IRMS measurements for N2O RM with high 15N enrichment  (e.g. S5), which agrees with earlier studies indicating challenges in \u03b415N(NH4+) analysis, but this may also be due to the lack of available international standards for \u03b415N(NH4+) that cover \u03b4 values above (+53.75\u2009\u00b1\u00a00.24)\u2030 (USGS26) and below (\u221230.41\u2009\u00b1\u00a00.27)\u2030 (USGS25).Results of O3 salts \u2013S6, prov2O gases from around zero (S1\u2010N2O) to 15N\u2010enriched (S4\u2010N2O) and of the substrate NH4NO3 salts (S1\u2013S4). Thereby, our study covers a much larger range of \u03b4 values  than earlier studies,2 scale. At very high and low 15N enrichment , the calibration approach using NH4NO3 decomposition is more challenging, probably due to less satisfying analytical accuracy of \u03b415N(NH4+) measurements to date. As the N2O gases S5\u2010N2O and S6\u2010N2O were not included in the analysis of N2O RMs, their enhanced uncertainty in \u03b415N\u03b1cal and \u03b415N\u03b2cal does not affect the data quality of N2O RMs.In summary, our results demonstrate consistency of the isotopic composition of the N3.23.2.12O RMs (RM1\u2013RM5) were calibrated against Air\u2010N2 by both QCLAS (Lab Empa) and IRMS (Lab TT) analyses. For QCLAS analyses, two N2O gases produced by NH4NO3 decomposition  were applied to define a calibration function and propagate the isotopic information of the NH4NO3 salts (\u03b415N(NO3\u2212), \u03b415N(NH4+)) to the N2O RMs . \u03b415NSP and \u03b415N were calculated using definitions and their uncertainty estimated using the law of error propagation. In Table\u00a0\u03b415NSP values acquired by QCLAS (Lab Empa) using the calibration approach established in this study are compared with results provided by DI\u2010IRMS (Lab TT) using a previously published link to the Air\u2010N2 scale.2O RMs are shown in Tables\u00a0The novel N\u03b415NSP measurements by DI\u2010IRMS  and QCLAS (Lab Empa) across all N2O RMs. This is most likely attributable to the calibration of the position\u2010dependent \u03b4 values with respect to Air\u2010N2 via the NH4NO3 decomposition technique, which were performed independently for the two labs. Incidentally, for the NH4NO3 salts S1\u2013S4, the \u03b415N(NO3\u2212) results provided by Lab TT were always lower ((\u22120.63\u2009\u00b1\u00a00.59)\u2030), while \u03b415N(NH4+) values were higher than the respective weighted mean values ((+0.49\u2009\u00b1\u00a00.25)\u2030), which would lead to 1.12\u2030 lower \u03b415NSP values \u2030 vs. (+18.7\u00a0\u00b1\u00a02.2)\u2030 for ambient tropospheric N2O.\u03b415NSP measurements by the Tokyo Institute of Technology, using the NH4NO3 decomposition technique.A similar 1.5\u20132.0\u2030 difference in \u03b415NSP and the Air\u2010N2 scale with high accuracy is still challenging and the current realisation of the Air\u2010N2 scale for \u03b415NSP provided by USGS51 and USGS52\u03b415NSP values and should be revisited in future studies.We conclude that the realisation of the link between 3.2.2\u03b415N values of N2O RMs were analysed by IRMS in three different laboratories using independent links to the Air\u2010N2 scale \u2030 (USGS51) and (+0.07\u2009\u00b1\u00a00.22)\u2030 (USGS52). These values fall between results published by laboratories 7 and 8 (USGS and BGC\u2010IsoLab) in Ostrom et al,\u03b415N(N2O) measurements. A similar offset between laboratories had already been detected earlier and was attributed to differences in the propagation of the Air\u2010N2 scale to \u03b415N(N2O).2O RMs.le Table\u00a0. Results52 Table\u00a0 by a com17O data are available. Consistency of N2O RM flask subsamples was demonstrated using DI\u2010IRMS  and 0.03\u2030 for \u03b418O(N2O) .In contrast, differences between analytical techniques applied within one lab, thus using the same link to the scale, were smaller than offsets between laboratories: (+0.10\u00a0\u00b1\u00a00.04)\u2030 for Lab MPI and (+0.12\u2009\u00b1\u00a00.14)\u2030 for Lab UEA. This indicates that both EA/IRMS and GC\u2010IRMS and DI\u2010IRMS can achieve high accuracy, provided that an accurate link to the scale and \u03943.2.3\u03b418O values of N2O RMs were analysed by IRMS in three different laboratories , indicating a potential scaling or scale compression issue. Measurements were not completely independent for all laboratories, as the results for Lab MPI\u2010II were referenced to average \u03b418O values of USGS51 in Ostrom et al,es Table\u00a0. Results\u03b417O values were determined by GC/IRMS at UEA (Lab UEA\u2010I) and showed a (0.98\u2009\u00b1\u00a00.27)\u2030 offset to prototypical measurements by HR\u2010IRMS (MAT253 ULTRA) at the Tokyo Institute of Technology 2SO4 melt. n indicates the number of decomposition experiments.Table S2. Isotopic composition of RMs, analysed by QCLAS at Empa versus S1\u2010N2O and S4\u2010N2O to calculate \u03b415N\u03b1, \u03b415N\u03b2, \u03b415NSP, and \u03b415N values. n indicates the number of analyses. Uncertainties are calculated using the law of error propagation involving the uncertainties in S1\u2010N2O and S4\u2010N2O, their analyses, and the analyses of N2O RMs but do not enclose deviations due to fractionation or branching effects during NH4NO3 decomposition. All values are reported in \u2030.Table S3. Isotopic composition of RMs, analysed by IRMS at Tokyo Institute of Technology (Lab TT) versus an isotopically characterised in\u2010house working standard to calculate \u03b415N\u03b1, \u03b415N\u03b2, \u03b415NSP, \u03b415N, and \u03b418O values on the \u201cTokyo Tech scale\u201d. n indicates the number of analyses. Uncertainties are calculated using the law of error propagation. All values are reported in \u2030.Table S4.\u03b415N of RMs, the in\u2010house N2O standard gas (NINO), and a number of quality control standards, analysed by Lab MPI  versus primary reference materials and second scale anchor of the Air\u2010N2 scale . n indicates the number of analyses. Expanded uncertainties are calculated following the law of error propagation. For the quality control, standards target values and references are provided as well. All values are reported in \u2030.Table S5. Isotopic composition of RMs, analysed as N2O diluted to 0.09\u2009mmol\u2009mol\u22121 on Sercon GEO 20\u201320 IRMS (UEA\u2010I) after gold decomposition, scale\u2010normalised to the \u03b418O value of RM4. n indicates the number of analyses. Uncertainties are calculated using the law of error propagation from the standard deviations of replicate measurements against the working reference gas and the calibration uncertainties of the working reference gas against Air\u2010N2 and VSMOW.14 All values are reported in \u2030.Table S6. Isotopic composition of RMs, analysed as pure N2O on Finnigan MAT 253 IRMS (UEA\u2010II) using the actual \u039417O measurements. n indicates the number of analyses. Uncertainties are calculated using the law of error propagation from the standard deviations of replicate measurements against the working reference gas and the calibration uncertainties of the working reference gas against Air\u2010N2 and VSMOW.15 All values are reported in \u2030.Click here for additional data file."}
{"text": "The main difference between mol\u00adecules A and B involves the dihedral angles of the phenyl groups. One phenyl ring makes dihedral angles of 71.14\u2005(6)\u00b0 (mol\u00adecule A) and 82.81\u2005(7)\u00b0 (mol\u00adecule B) with respect to the core (C4N3O2) of the mol\u00adecule [14.56\u2005(9)\u00b0 (mol\u00adecule A) and 5.7\u2005(1)\u00b0 (mol\u00adecule B) for the other phenyl ring]. Another prominent feature is the intra\u00admolecular N\u2014H\u22efO hydrogen bond present in both crystallographically independent mol\u00adecules.The title compound, C E)-N-Phenyl-N-(phenyl\u00adcarbamo\u00adyl)-3-[prop\u00adyl(tri\u00admethyl\u00adsil\u00adyl)amino]\u00adacryl\u00adamide is an insertion product from prop\u00adyl(tri\u00admethyl\u00adsil\u00adyl)[2-(tri\u00admethyl\u00adsil\u00adyl)ethen\u00adyl]amine and phenyl iso\u00adcyanate. It was obtained in the course of our work on different types of silicon\u2013nitro\u00adgen compounds  carbamo\u00adyl]-3-(meth\u00adyl\u00adsulfan\u00adyl)acryl\u00adamide \u2005\u00c5 in mol\u00adecule B] The planarity is presumably due to the conjugated system of double bonds. The C14\u2013C19 phenyl rings in both mol\u00adecules are not coplanar to the core of the mol\u00adecules but adopt dihedral angles to the latter of 14.56\u2005(9)\u00b0 (mol\u00adecule A) and 5.7\u2005(1)\u00b0 (mol\u00adecule B). This small deviation from planarity still allows conjugation between the C14\u2013C19 phenyl ring and the urea part of the mol\u00adecule.The core of the mol\u00adecule formed by N1, C4\u2013C6, O1, N2, C7, O2 and N3 is almost planar in both mol\u00adecules of the title compound [the average deviation from the plane is 0.05\u2005(6)\u2005\u00c5 in mol\u00adecule A) and 82.81\u2005(7)\u00b0 (mol\u00adecule B) with the core of the mol\u00adecule. This almost perpendicular conformation may be explained by the presence of the oxygen atom O2 in a vicinal position to the respective phenyl group.The C8\u2013C13 phenyl rings in both mol\u00adecules subtend dihedral angles of 71.14\u2005(6)\u00b0 -N-phenyl-N-(phenyl\u00adcarbamo\u00adyl)-3-[prop\u00adyl(tri\u00admethyl\u00adsil\u00adyl)amino])acryl\u00adamide was obtained from the reaction of prop\u00adyl(tri\u00admethyl\u00adsil\u00adyl)[2\u2013(tri\u00admethyl\u00adsil\u00adyl)ethen\u00adyl]amine and phenyl iso\u00adcyanate. As shown in Fig.\u00a04et al., 2018(n-pentane were added dropwise 0.35\u2005g (3\u2005mmol) phenyl\u00adiso\u00adcyanate at 0\u00b0C. After standing for six days at room temperature, volatiles were removed under reduced pressure. Storing the product mixture for five years at \u221228\u00b0C yielded crystals suitable for single-crystal X-ray diffraction. No qu\u00adanti\u00adtative yield can be given here, since only a few crystals at the wall of the Schlenk tube were available. NMR spectroscopy showed that the batch product is a mixture of many components. Further purification of the product mixture was not successful.To a solution of 0.46\u2005g (2\u2005mmol) prop\u00adyl(tri\u00admethyl\u00adsil\u00adyl)[2-(tri\u00admethyl\u00adsil\u00adyl)ethen\u00adyl]amine in 10\u2005ml Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623001177/im4017sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623001177/im4017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623001177/im4017Isup3.cmlSupporting information file. DOI: 2240673CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound has been characterized by single-crystal X-ray diffraction and Hirshfeld surface analyses. The mol\u00adecular structure and frontier orbitals were also investigated using DFT. 11H9BrN2O, is almost planar. The benzene and pyrimidine rings are essentially coplanar, with r.m.s. deviations of 0.0130\u2005\u00c5, and the largest displacement is for the flap atom of the di\u00adhydro\u00adpyrrole moiety [0.154\u2005(7)\u2005\u00c5]. Hirshfeld surface analyses revealed that the crystal packing is dominated by H\u22efH, Br\u22efH/H\u22efBr and O\u22efH/H\u22efO inter\u00adactions, and Br\u22efBr inter\u00adactions in the crystal structure are also observed. Theoretical calculations using density functional theory (DFT) with the B3LYP functional basis set gave numerical parameters for the frontier molecular orbitals.The mol\u00adecular structure of the title compound, C In comparison with a reported literature procedure  at room temperature (293\u2013298\u2005K) and the reaction products separated by extraction after the reaction mixture was reduced to pH = 9\u201310 with NH4OH. As distinguished from the reported procedure, we carried out these reactions by cooling in an ice bath at a much lower temperature (273\u2013275\u2005K) and for a relatively longer period of time. The reaction products were finally separated by cold NH4OH at pH = 10\u201311. In general, the inter\u00adactions of 7-bromo-2,3-di\u00adhydro\u00adpyrrolo\u00adquinazolin-9(1H)-one with aldehydes are well-studied  with the B3LYP functional basis set.2.et al., 2009et al., 2007aet al., 1992et al., 2009et al., 2005The mol\u00adecular structure of the title compound is shown in Fig.\u00a013.et al., 1964Cg inter\u00adactions, with Br\u22efCg1 = 3.6428\u2005(15)\u2005\u00c5, forming a layered network \u2005\u00c5  and a ring slippage of 1.569\u2005\u00c5, and Cg2\u22efCg3ii being 3.7513\u2005(16)\u2005\u00c5  and a ring slippage of 1.194\u2005\u00c5. Both short inter\u00admolecular contacts help to stack parallel mol\u00adecules along [100]. The resulting two-dimensional network extends parallel to (002), with neighbouring layers linked through C1\u2014H1B\u22efN4 short inter\u00admolecular contacts, H1B\u22efN4 = 2.73\u2005\u00c5, C1\u2014H1B\u22efN4 = 169\u00b0, to form the full three-dimensional structure \u2005\u00c5, which is shorter than the sum of van der Waals radii  to the Hirshfeld surface . Besides these contacts, Br\u22efH/H\u22efBr (19.6%), O\u22efH/H\u22efO (11.3%), N\u22efH/H\u22efN (8.1%) and C\u22efH/H\u22efC (6.9%) inter\u00adactions contribute significantly to the total Hirshfeld surface; their decomposed fingerprint plots are shown in Fig.\u00a06c\u2013f. The contributions of further contacts are only minor and amount to N\u22efC/C\u22efN (3.5%), O\u22efC/C\u22efO (2.0%), Br\u22efC/C\u22efBr (0.9%), Br\u22efBr (0.8%), O\u22efN/N\u22efO (0.5%) and Br\u22efN/N\u22efBr (0.3%).In order to qu\u00adantify the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis , chemical hardness (h) and chemical softness (s) can be calculated as follows: c = (I + A)/2; h = (I - A)/2; s = 1/2h, where I and A are the ionization potential and electron affinity, respectively, where I = \u2013EHOMO and A = \u2013ELUMO , hardness (h), potential (m), electrophilicity (w) and softness (s) for the title mol\u00adecule were calculated at the DFT/B3LYP level using the 6-311++G basis set  indicates the relatively high stability of the title mol\u00adecule.t Table\u00a01. The val6.et al., 2016b]quinazolin-9(1H)-one moiety with a similar conformation to that in the title structure: de\u00adoxy\u00advasicinone -one moiety gave only two hits: N-propanamide sesquihydrate -one mono\u00adhydrate  (0.142\u2005mol) of phospho\u00adroxychloride were added dropwise over 1\u2005h at 273\u2013275\u2005K. The reaction mixture was then heated at 368\u2013371\u2005K for 2\u2005h, it was subsequently cooled and finally poured over ice. The temperature of the mixture was kept at around 273\u2013275\u2005K. When the reaction mixture was completely decomposed, it was brought to pH = 10\u201311 with 25%wt ammonium hydroxide solution. The light-yellow precipitate was filtered off, dried and recrystallized from methanol. The yield of the product was 4.35\u2005g (82%), m.p. 431\u2013433\u2005K : 8.4 , 7.8 , 7.5 , 4.2 , 3.18 , 2.31 .8.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022007800/wm5655sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007800/wm5655Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022007800/wm5655Isup3.cmlSupporting information file. DOI: 2194365CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the title flavone derivative, O\u22efI halogen bonding and T\u2013shaped \u03c0\u2013stacking combine to generate a herringbone packing motif. 19H13IO2, the dihedral angle between the naphthyl ring system and the pendant iodo\u00adphenyl ring is 72.48\u2005(11)\u00b0. In the crystal, C\u2014H\u22ef\u03c0 inter\u00adactions and I\u22efO [3.293\u2005(2)\u2005\u00c5] halogen bonds are observed, which combine to generate a herringbone packing motif.In the title compound, C Our group is particularly inter\u00adested in the extended flavonol motif as it has been shown to release CO qu\u00adanti\u00adtatively with visible light (Popova Cg1\u22efCg2i = 4.929\u2005(2)\u2005\u00c5  and C6\u2014H6\u22efCg2i = 154.5\u2005(3)\u00b0, where Cg1 is the centroid of the pyran\u00adone ring containing atoms C4\u2013C7/C12/C13 and Cg2 is the centroid of the iodo\u00adphenyl ring containing atoms C14\u2013C19 \u2005\u00c5, with C17\u2014I1\u22efO2ii and I1\u22efO2ii\u2014C1ii angles of 177.21\u2005(10) and 127.9\u2005(2)\u00b0, respectively . This I\u22efO separation is some 0.25\u2005\u00c5 shorter than van der Waals\u2019inter\u00adaction distance of 3.5\u2005\u00c5  was added and the reaction was stirred until a precipitate formed. The reaction mixture was acidified to pH 4 with glacial acetic acid. The solids were filtered and taken directly to the next step. (E)-1--3-(4-iodo\u00adphen\u00adyl)prop-2-en-1-one was then suspended in ethanol (10\u2005ml). An NaOH solution  was added and the reaction stirred until a precipitate formed. The reaction mixture was acidified to pH 1 with HCl (6 M). The white solid was collected by filtration and slow evaporation of a solution of the title compound in ethyl acetate gave colorless crystals .1-Acetyl-2-naphthol  and 4-iodo\u00adbenzaldehyde  were dissolved in ethanol (5\u2005ml). An NaOH solution  \u03b4 = 9.46 , 7.95 , 7.80\u20137.75 , 7.65 , 7.44 , 7.26 , 7.16 , 5.54 , 3.16 , 2.95  ppm.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314620001108/hb4334sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620001108/hb4334Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620001108/hb4334Isup3.cmlSupporting information file. DOI: 1980111CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The TaV atom has a distorted tetra\u00adhedral coordination environment in a three-legged piano-stool fashion. The conformation of the penta\u00adfulvene exocyclic C atom to the three other ligands is staggered and not eclipsed, as found in the crystal structure of 1. Inter\u00admolecular inter\u00adactions include \u03c0\u2013\u03c0 stacking, H\u22ef\u03c0 inter\u00adactions and weak C\u2014H\u22efCl hydrogen bonds.The reaction of (\u03b7 The C6exo atom coordinates roughly opposite of Cl2 to the central tantalum atom [C6\u2014Ta1\u2014Cl2: 171.58\u2005(3)\u00b0]. Relative to the centroid of the five-membered ring (Ct), the angles to the chloride ligands are smaller than to the nitro\u00adgen ligands . The bond length Ta1\u2014N1 [2.0433\u2005(9)\u2005\u00c5] and the sum of angles at N1 [347.1\u2005(2)\u00b0] indicates a weak inter\u00adaction of the nitro\u00adgen lone pair with the metal. The penta\u00adfulvene coordinates in a \u03c0-\u03b75:\u03c3-\u03b71 fashion and exhibits typical distortion parameters . The C\u2014C bond lengths within the penta\u00adfulvene are summarized in Fig.\u00a02b. The penta\u00adfulvene has a ring slippage \u0394 of 0.31\u2005\u00c5 and a \u03b8 angle of the Cipso\u2014Cexo bond out of the plane of the five-membered ring of 36.30\u2005(12)\u00b0. The Cipso\u2014Cexo bond is a single to double bond . Consequently, the Ta1\u2014Cl2 bond [2.3965\u2005(3)\u2005\u00c5) is longer than the Ta1\u2014Cl1 bond [2.3452\u2005(3)\u2005\u00c5]. These pairs form a double-chain , linked by supra\u00admolecular contacts of the penta\u00adfulvene and the carbazolide ligands via \u03c0\u2013\u03c0 stacking [C1\u22efC17: 3.3867\u2005(15)\u2005\u00c5] and an H\u22ef\u03c0 inter\u00adaction [C15\u22efH10c: 2.773\u2005(6)\u2005\u00c5]. Numerical details of other hydrogen-bonding inter\u00adactions are summerized in Table\u00a01On the supra\u00admolecular level, around an inversion center, two mol\u00adecules mutually inter\u00adact in Fig.\u00a03b, linke1 was prepared according to Riley et al.  was dissolved in tetra\u00adhydro\u00adfuran (20\u2005ml) and cooled to 223\u2005K. One equivalent of etheric HCl  was added dropwise and the solution was slowly brought to room temperature. After stirring over night, the solvents were removed in vacuo and the residue was extracted with toluene (10\u2005ml). The solution was diluted with n-hexane (10\u2005ml) and stored at 277\u2005K for three days to yield a red crystalline material containing 1 and 2 (1:1). 1H NMR : \u03b4 = 0.79 , 0.85 , 1.27 , 1.49 , 1.53 , 2.13 , 2.62 , 3.27 , 3.65 , 6.30\u20138.29  p.p.m.Complex SHELXL . Refinement with OLEX2 . Refining all atoms anharmonically was dismissed, because it lowers the reliability factors only marginally, but more than triples the refinement parameters (263 versus 888 parameters).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622012019/wm4176sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622012019/wm4176Isup2.hklStructure factors: contains datablock(s) I. DOI: 2231842CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Cp rings in both ferrocene groupings are close to eclipsed. In the crystal, O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into [100] chains.In the title compound, [CoFe The resulting complexes may have applications in the fields of electroluminescent devices, environmental sensors, photodynamic therapy and biological imaging \u00b0. The Cp rings of both ferrocene groups are in nearly eclipsed conformations.The cobalt(II) atom has a octa\u00adhedral coordination environment defined by two tri\u00adfluoro\u00admethyl-\u03b2-diketone ferrocene ligands and two water ligands Fig.\u00a01 with thex, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z) contact .In the crystal, the mol\u00adecules are linked into [100] chains by O\u2014H\u22efO hydrogen bonds arising from the water mol\u00adecules Table\u00a01; an intrIn a 250\u2005ml round-bottom flask, tri\u00adfluoro\u00admethyl-\u03b2-diketone ferrocene (0.52\u2005g 1.6\u2005mmol), tri\u00adethyl\u00adamie (0.25\u2005g 2.45\u2005mmol) and cobalt acetate (0.13\u2005g 0.5\u2005mmol) were dissolved in 100\u2005ml of methanol and the mixture was stirred at 343\u2005K for 12\u2005h and then cooled to room temperature. A red solid was obtained by suction filtration. Crystals for X-ray analysis were obtained by recrystallization from methanol solution.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620012407/hb4360sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620012407/hb4360Isup3.hklStructure factors: contains datablock(s) I. DOI: 2031062CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A series of O\u2014H\u22efN inter\u00adactions connect the mol\u00adecules into twisting wires, which are cross-linked through van der Waals inter\u00adactions.A co-crystal consisting of a 1:1 ratio of  p-vanillic acid (1/1)], C12H10N2\u00b7C8H8O4, the dihedral angle between the pyridine rings is 59.51\u2005(5)\u00b0. In the crystal, the mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds, generating [401] chains of alternating C12H10N2 and C8H8O4 mol\u00adecules.In the title 1:1 co-crystal [alternatively called bi\u00adpyridine ethyl\u00adene\u2013 The vanillic acid has two distinct O\u2014H\u22efN-type hydrogen-bonding inter\u00adactions (Table\u00a01para-position hydroxyl group and the other pyridine N atom of a BPyE mol\u00adecule resulting in a 2.6868\u2005(13)\u2005\u00c5 distance between heteroatoms  was added to a 25\u2005ml scintillation vial to which methanol was added until both compounds dissolved (approximately 20\u2005ml). The resulting solution was vortexed for 30\u2005s at 3000 rpm on a VWR Mini Vortexer MV I. The solution was then stored in the dark uncapped to allow for crystal formation while the solvent slowly evaporated.A 1:1 molar ratio of bi\u00adpyridine ethyl\u00adene  and Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2414314622003042/hb4402sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622003042/hb4402Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622003042/hb4402Isup3.cmlSupporting information file. DOI: 2160226CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structure exhibits disorder of one of the 4-meth\u00adoxy\u00adbenzyl groups, the hy\u00addroxy group bonded to the 1,3-diazinan ring, and the methyl group of the meth\u00adoxy residue. The crystal packing is sustained by C\u2014H\u22efO and O\u2014H\u22ef\u03c0 inter\u00adactions, giving rise to infinite chains running along the b-axis direction.The title compound resulted from the condensation reaction between 1,3-bis\u00ad{[(4-meth\u00adoxy\u00adphen\u00adyl)meth\u00adyl]amino}\u00adpropan-2-ol and 2-hy\u00addroxy\u00adbenzaldehyde in CH 26H30N2O4, at 173\u2005K has ortho\u00adrhom\u00adbic (Pbca) symmetry. It was previously described by Bolte et al. . The title compound resulted from the condensation reaction between 1,3-bis\u00ad{[(4-meth\u00adoxy\u00adphen\u00adyl)meth\u00adyl]amino}\u00adpropan-2-ol and 2-hy\u00addroxy\u00adbenzaldehyde in CH3OH. The structure exhibits disorder. One of the 4-meth\u00adoxy\u00adbenzyl groups, the hy\u00addroxy group bonded to the 1,3-diazinan ring, and the methyl group of the meth\u00adoxy residue are disordered over two orientations, with occupancies of 0.807\u2005(3)/0.193\u2005(3), 0.642\u2005(5)/0.358\u2005(5), and 0.82\u2005(4)/0.18\u2005(4), respectively. The dihedral angles between the mean planes of the central 1,3-diazinan-5-ol and the 4-meth\u00adoxy\u00adphenyl rings (both occupancy components of the disordered ring) are 88.65\u2005(13), 85.79\u2005(14) and 83.4\u2005(7)\u00b0. The crystal packing is sustained by C\u2014H\u22efO and O\u2014H\u22ef\u03c0 inter\u00adactions, giving rise to infinite chains running along the b-axis direction.The redetermined structure of 2-(2-hy\u00addroxy\u00adphen\u00adyl)-1,3-bis\u00ad(4-meth\u00adoxy\u00adbenz\u00adyl)-1,3-diazinan-5-ol, C It is noteworthy that the coupling constants with magnitudes between 2.9 and 3.1\u2005Hz provide a strong evidence of the presence of an axial OH group. In this regard, it has been reported that the presence of an intra\u00admolecular hydrogen bond may stabilize the hydroxyl group in the otherwise non-preferred axial position meth\u00adyl]amino}\u00adpropan-2-ol, easily obtained following the reported method \u2005\u00c5, \u03b8 = 3.1\u2005(3)\u00b0, \u03c6 = 250\u2005(4)\u00b0, Q(2) = 0.035\u2005(3)\u2005\u00c5 and Q(3) = \u22120.561\u2005(3)\u2005\u00c5. Atoms C2 and C3 deviate from the mean plane of the other four atoms by \u22120.242\u2005(3) and 0.249\u2005(3)\u2005\u00c5, respectively. Atoms N1 and N2 are essentially tetra\u00adhedral (bond-angle sums are 331.8\u00b0 for N1 and 330.1\u00b0 for N2), while the usual \u03a3H\u2013N\u2013H angle in an ammonia mol\u00adecule is 321\u00b0 \u2005\u00c5] and the C21\u2013C26, C31\u2013C36 and C31\u2032\u2013C36\u2032 phenyl rings of the 1,3- benzyl groups are 88.65\u2005(13), 85.79\u2005(19) and 83.4\u2005(7)\u00b0, respectively, whereas the mean plane is rotated by 81.22\u2005(13)\u00b0 towards the C11\u2013C16 phenyl ring of the 2-hy\u00addroxy\u00adphenyl substituent. The dihedral angles between this phenyl ring and the other two phenyl rings are 55.54\u2005(13)\u00b0 (C21\u2013C26), 84.27\u2005(19)\u00b0 (C31\u2013C36) and 77.9\u2005(7)\u00b0 (C31\u2032\u2013C36\u2032), respectively.S(6) graph-set motif (Table1). The N\u22efO distance [2.740\u2005(3)\u2005\u00c5] is long in comparison with the values observed in related structures  is shorter than 4\u2005\u00c5. It is noteworthy that the inter\u00adplanar distance between the symmetry-related main parts of the C31\u2013C36 ring is only 3.66\u2005\u00c5; however, the corresponding Cg\u22efCg distance is too long at 4.619\u2005(3)\u2005\u00c5, indicating a significant horizontal shift of the rings precluding \u03c0\u2013\u03c0 stacking.In the crystal structure, the mol\u00adecules are inter\u00adlinked ds Fig.\u00a03 into chas Table\u00a01 amino}\u00adpropan-2-ol  in methanol (20\u2005mL) salicyl\u00adaldehyde  was added dropwise. The resulting mixture was heated at reflux for 2\u2005h and allowed to cool to room temperature. The solvent was removed under vacuum and the crude solid was washed with cold methanol and dried 1H NMR  \u03b4 7.15 , 7.12\u20137.13 , 7.11 , 6.99 , 6.85 , 6.81 , 3.88 , 3.76 , 3.72\u20133.74 , 3.03 , 2.99 , 2.98 , 2.22 , 1.60 . The hydrogen atom of a hydroxyl group could not be assigned because of the overlaping and widening of that signal with those due to hydrogen bonds.26H30N2O4. Calculated, %: C, 71.89; H, 6.91; N, 6.45; O, 14.75.Elemental analysis : Found, %: C 71.87; H 6.91; N 6.45; O 14.74. C6.Uiso values of methyl H atoms were set to 1.5Ueq(C), while the Uiso values of H atoms bonded to the remaining C atoms were set to 1.2Ueq(C). The H atom bonded to O in the major occupied site was freely refined. The H atom bonded to O in the minor occupied site was refined using a riding model with Uiso(H) set to 1.5Ueq(O). In addition, the H\u2014O\u2014C\u2014C torsion angle was allowed to refine. The displacement ellipsoids of O4 and O4\u2032 were restrained to be similar. The distances O4\u2014C3 and O4\u2032\u2014C3 were restrained to be similar. Bond lengths and angles in the fragments C24\u2013O2\u2013C27\u2032 and C24\u2013O2\u2013C27 were restrained to be similar. The displacement ellipsoids of O2 and C27/C27\u2032 were restrained to be similar. Bond lengths, angles and displacement parameters in the fragments N2\u2013O3\u2032\u2013C31\u2032\u2013C32\u2032\u2013C33\u2032\u2013C34\u2032\u2013C35\u2032\u2013C36\u2032\u2013C37\u2032\u2013C8\u2032 and N2\u2013O3\u2013C31\u2013C32\u2013C33\u2013C34\u2013C35\u2013C36\u2013C37\u2013C8 were restrained to be similar. The following restraints implemented in SHELXL  were used to restrain the geometry  and ijU  of the disordered parts.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022006508/jq2018sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022006508/jq2018Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022006508/jq2018Isup3.cmlSupporting information file. DOI: 2092230CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II part of aqua\u00adzinc(II) diperchlorate, [Zn(C8H20N4)H2O](ClO4)2, exhibits a slightly distorted square-pyramidal coordination environment with a water mol\u00adecule in the apical position.The cationic Zn II part of aqua\u00adzinc(II) bis\u00ad(perchlorate), [Zn(C8H20N4)(H2O)](ClO4)2, exhibits a slightly distorted square-pyramidal coordination environment with a water mol\u00adecule in the apical position. In the crystal, the macrocyclic ring alternates between two conformations with equal occupancies. Two of the three perchlorate anions are situated about a twofold rotation axis, and one of them shows disorder of the O atoms with occupancies of 0.62\u2005(7) and 0.38\u2005(7). In the crystal, the complexes are connected by inter\u00admolecular hydrogen bonding via the perchlorate anions.The cationic Zn The macrocyclic ring is disordered, and two alternate conformations of each N\u2013C\u2013C\u2013N bridge can be observed (conformation A and B)  in the basal plane, with a ZnII-bound H2O mol\u00adecule occupying the apical position. Addison et al. (1984\u03b2\u00a0\u2212\u00a0\u03b1)/60\u00b0] to determine if the five-coordinate atom has a square-pyramidal or trigonal\u2013pyramidal coordination environment. The bond angles \u03b2 and \u03b1 are the largest and second-largest in the coordination sphere, respectively; an ideal square pyramid and an ideal trigonal bipyramid have \u03c4 = 0 and 1, respectively. In conformation A, the N\u2014ZnII\u2014N bond angles \u03b1 and \u03b2 are 138.2\u2005(3)\u00b0 and 138.7\u2005(3)\u00b0, respectively; the corresponding bond angles in conformation B are 137.4\u2005(4)\u00b0 and138.7(4)\u00b0. The \u03c4 values are 0.008 and 0.022 for conformations A and B, respectively. Therefore, the coordination geometry around the central ZnII cation can be described as slightly distorted square-pyramidal. The occupancies for the non-hydrogen atoms of cyclen except for the four carbon atoms  were set to 0.50. Atom Zn1 is 0.755\u2005(5) and 0.763\u2005(3)\u2005\u00c5 above the basal plane formed by four N atoms in conformations A and B, respectively. The Zn1\u2014O1 bond length [1.9721\u2005(4)\u2005\u00c5] is within the typical range [1.94\u20132.03\u2005\u00c5] for similar five-coordinated Zn complexes 2  Fig.\u00a01, in whic al. 1984 proposedII complex  I. DOI: 10.1107/S2414314621003977/vm4048Isup2.hklStructure factors: contains datablock(s) I. DOI: 2067247CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Three new styryl\u00adquinoline\u2013chalcone hybrids are been syntheized using a three-step reaction sequence. In two of them, a combination of hydro\u00adgen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions generates three-dimensional assemblies, but in the third, only a single weak \u03c0\u2013\u03c0 stacking inter\u00adaction is present, linking the mol\u00adecules into chains. 1H/13C NMR spectroscopy, and by high-resolution mass spectrometry, and the three products have been characterized by single-crystal X-ray diffraction. The mol\u00adecular conformations of (E)-3-{4-[(E)-2-phenyl\u00adethen\u00adyl]quinolin-2-yl}-1-(naph\u00adtha\u00adlen-1-yl)prop-2-en-1-one, C30H21NO, (IVa), and (E)-3-{4-[(E)-2-(4-fluoro\u00adphen\u00adyl)ethen\u00adyl]quinolin-2-yl}-1-(naph\u00adtha\u00adlen-1-yl)prop-2-en-1-one, C30H20FNO, (IVb), are very similar. In each com\u00adpound, the mol\u00adecules are linked into a three-dimensional array by hydro\u00adgen bonds, of the C\u2014H\u22efO and C\u2014H\u22efN types in (IVa), and of the C\u2014H\u22efO and C\u2014H\u22ef\u03c0 types in (IVb), and by two independent \u03c0\u2013\u03c0 stacking inter\u00adactions. By contrast, the conformation of the chalcone unit in (E)-3-{4-[(E)-2-(2-chloro\u00adphen\u00adyl)ethen\u00adyl]quinolin-2-yl}-1-(naph\u00adtha\u00adlen-1-yl)prop-2-en-1-one, C30H20ClNO, (IVc), differs from those in (IVa) and (IVb). There are only weak hydro\u00adgen bonds in the structure of (IVc), but a single rather weak \u03c0\u2013\u03c0 stacking inter\u00adaction links the mol\u00adecules into chains. Comparisons are made with some related structures.Three new styryl\u00adquinoline\u2013chalcone hybrids have been synthesized using a three-step pathway starting with Friedl\u00e4nder cyclo\u00adcondensation between (2-amino\u00adphen\u00adyl)chalcones and acetone to give 2-methyl-4-styryl\u00adquinolines, followed by selective oxidation to the 2-formyl analogues, and finally Claisen\u2013Schmidt condensation between the formyl inter\u00admediates and 1-acetyl\u00adnaph\u00adtha\u00adlene. All inter\u00admediates and the final products have been fully characterized by IR and  Compound (IIc): reaction time 14\u2005h, yield 0.21\u2005g (73%), yellow solid, m.p. 388\u2013390\u2005K, RF\u00a0= 0.22 (12.5% ethyl acetate\u2013hexa\u00adne).Compound (IIa): reaction time 15\u2005h, yield 0.19\u2005g (86%), yellow solid, m.p. 367\u2013369\u2005K, v/v) to give the required formyl inter\u00admediates (IIIa)\u2013(IIIc) as solid com\u00adpounds.For the synthesis of com\u00adpounds (III), a suspension of the appropriate 2-methyl-4-styryl\u00adquinoline (II) (1.0\u2005mmol) and selenium dioxide (2.0\u2005mmol) in 1,4-dioxane (5\u2005ml) was stirred and heated at 373\u2005K for the appropriate time. After the complete consumption of (II) [as monitored by thin-layer chromatography (TLC)], di\u00adchloro\u00admethane (15\u2005ml) was added and the residual solid was removed by filtration. The solvent was removed under reduced pressure and the resulting crude products were purified by flash column chromatography on silica gel using hexa\u00adne\u2013ethyl acetate mixtures as eluent (compositions ranged from 7:1 to 2:1 RF\u00a0= 0.31 (9.1% ethyl acetate\u2013hexa\u00adne). Compound (IIIb): reaction time, 1\u2005h, yield 0.14\u2005g (89%), yellow solid, m.p. 417\u2013419\u2005K, RF\u00a0= 0.20 (9.1% ethyl acetate\u2013hexa\u00adne). Compound (IIIc): reaction time, 2\u2005h, yield 0.21\u2005g (92%), pale orange solid, m.p. 431\u2013433\u2005K, RF\u00a0= 0.28 (9.1% ethyl acetate\u2013hexa\u00adne).Compound (IIIa): reaction time, 1\u2005h, yield 0.23\u2005g (96%), yellow solid, m.p. 421\u2013423\u2005K, For the synthesis of com\u00adpounds (IV), a mixture of the appropriate 2-formyl inter\u00admediate (III) (1.0\u2005mmol), 1-aceto\u00adnaphthone (1.0\u2005mmol) and potassium hydroxide (1.1\u2005mmol) in ethanol (3\u2005ml) was stirred at 298\u2005K for the appropriate time. After complete consumption of (III) (monitored by TLC), the resulting precipitate was collected by filtration, washed with water (15\u2005ml) and ethanol (10\u2005ml), and then recrystallized from chloro\u00adform\u2013ethanol to afford the target mol\u00adecular hybrids (IV).RF\u00a0= 0.22 (13% ethyl acetate\u2013hexa\u00adne). Compound (IVb)RF\u00a0= 0.31 (13% ethyl acetate\u2013hexa\u00adne). Compound (IVc)RF\u00a0= 0.20 (9% ethyl acetate\u2013hexa\u00adne).Compound (IVa)supporting information.Full details of the spectroscopic characterization are included in the Uiso(H)\u00a0= 1.2Ueq(C).Crystal data, data collection and refinement details for com\u00adpounds (IVa)\u2013(IVc) are summarized in Table\u00a01et al., 20221H/13C NMR spectroscopy, and by high-resolution mass spectrometry (HRMS); full details of the spectroscopic characterization are provided in the supporting information.We have recently reported  and (IIc) matched perfectly those of previously reported analogues \u2013(IVc). The formation of mol\u00adecular hybrids (IV) was established by disappearance of the formyl signals from both the 1H and 13C NMR spectra, and by the appearance of signals from the newly formed 3-aryl\u00adpropen-1-one fragment. As far as the Claisen\u2013Schmidt condensation is con\u00adcerned, it proceeded in a highly stereoselective manner, giving exclusively the E-stereoisomers, as indicated by the 1H NMR spectra. The trans configuration of the aryl\u00adpropen-1-one fragment was deduced on the basis of the coupling constant values  between HA and HB , whose signals in the 1H NMR spectra appear at \u03b4 7.91\u20137.93 and 7.78\u20137.79, respectively.The presence of stretching vibration bands in the range 1727\u20131731\u2005cmE-configuration of both the styryl and the chalcone moieties \u2013(IVc) which fully confirm the mol\u00adecular structures deduced from the spectroscopic data, in particular, the s Figs. 1\u20133 \u25b8 \u25b8. et al., 2022et al., 2022ca 180\u00b0 around the C22\u2014C23 bond (Table\u00a02For each of (IVa)\u2013(IVc), the atom labelling Figs. 1\u20133 \u25b8 \u25b8 fet al., 1998abet al., 2000et al., 1990et al., 1995The supramolecular assembly in com\u00adpound (IVa)n, n) alternate with n, n), where n represents an integer in each case. The pyri\u00addine rings of the mol\u00adecules at  and  are strictly parallel with an inter\u00adplanar spacing of 3.2877\u2005(5)\u2005\u00c5 and a ring-centroid separation of 3.5372\u2005(7)\u2005\u00c5, corresponding to a ring-centroid offset of 1.305\u2005(2)\u2005\u00c5. This inter\u00adaction links the x, y, z) and the styryl ring at  make an inter\u00adplanar angle of only 6.37\u2005(7)\u00b0; the ring-centroid separation is 3.7818\u2005(9)\u2005\u00c5 and the shortest perpendicular distance between the centroid of one ring and the plane of the other is 3.4535\u2005(6)\u2005\u00c5, corresponding to a ring-centroid offset of 1.541\u2005(2)\u2005\u00c5. This inter\u00adaction links the The linking of these dimeric units by C\u2014H\u22efN hydro\u00adgen bonds gives rise to a ribbon running parallel to the  and quinoline, the mol\u00adecules are linked into cyclic centrosymmetric dimers by hydro\u00adgen bonds, of the C\u2014H\u22efN and C\u2014H\u22ef\u03c0 types, respectively, and these dimers are further linked by \u03c0\u2013\u03c0 stacking inter\u00adactions to form sheets in the fluoro com\u00adpound and chains in the tri\u00adfluoro\u00admethyl analogue. By contrast, there are no significant inter\u00admolecular inter\u00adactions in the structure of (E)-4--2-methyl\u00adquinoline. All of these type (II) com\u00adpounds have mol\u00adecular skeletons in which the styryl and quinoline units are non-coplanar, as reported here for com\u00adpounds (IVa)\u2013(IVc). This appears to be the case for all of the 4-styryl\u00adquinolines which have been structurally characterized so far, in contrast to the 2- and 8-styryl\u00adquinolines, where the two ring systems appear always to be effectively coplanar  three products and all of the inter\u00admediates on the pathways leading to them, and we have determined the mol\u00adecular and supra\u00admolecular structures of the three products.We have developed a highly versatile and efficient three-step synthesis of a novel class of styryl\u00adquinoline\u2013chalcone hybrids based on only very simple and readily available starting materials, such as simple aldehydes and ketones, and we have characterized by spectroscopic means  global, IVa, IVb, IVc. DOI: 10.1107/S2053229622011263/ov3164IVasup2.hklStructure factors: contains datablock(s) IVa. DOI: 10.1107/S2053229622011263/ov3164IVbsup3.hklStructure factors: contains datablock(s) IVb. DOI: 10.1107/S2053229622011263/ov3164IVcsup4.hklStructure factors: contains datablock(s) IVc. DOI: 10.1107/S2053229622011263/ov3164sup5.txtSpectroscopic data. DOI: 2221749, 2221750, 2221751CCDC references:"}
{"text": "A and B) are present in the asymmetric unit, with different conformations. The dihedral angle between the mean planes of the carbazole systems for mol\u00adecule A is 49.1\u2005(2)\u00b0 compared to 84.0\u2005(1)\u00b0 for mol\u00adecule B. In the crystal, numerous aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid separation = 3.7069\u2005(19)\u2005\u00c5] help to establish the three-dimensional supra\u00admolecular network.In the title compound, two independent mol\u00adecules  are present in the asymmetric unit, with different conformations. The dihedral angle between the mean planes of the carbazole systems for mol\u00adecule A is 49.1\u2005(2)\u00b0 compared to 84.0\u2005(1)\u00b0 for mol\u00adecule B. In the crystal, numerous aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [shortest centroid\u2013centroid separation = 3.7069\u2005(19)\u2005\u00c5] help to establish the three-dimensional supra\u00admolecular network.In the title compound, C Two independent mol\u00adecules (A and B) are present in the asymmetric unit, with different conformations. Each of the independent mol\u00adecules is composed of two carbazole systems connected by an iodo\u00adbenzene bridge \u00b0 compared to 84.0\u2005(1)\u00b0 for the N3 and N4 ring systems in mol\u00adecule B. In the crystal, numerous face-to-face [shortest centroid\u2013centroid separation = 3.7069\u2005(19)\u2005\u00c5] and edge-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions connect the mol\u00adecules into a three-dimensional supra\u00admolecular network , t-BuOK , and dimethyl sulfoxide (10\u2005ml) was stirred at 120\u00b0C before 1-iodo-3,5-di\u00adfluoro\u00adbenzene  was injected. The reaction mixture was stirred at 140\u00b0C for 2\u2005h. After being cooled, the mixture was extracted with chloro\u00adform and the organic extracts were combined, washed with water, and the organic layer was dried over anhydrous MgSO4. After evaporating the solvent, the crude product was purified by column chromatography on silica gel with chloro\u00adform/n-hexane as the eluent to give a white powder. Yield: 83%. 1H NMR  \u03b4 8.17 , 8.08 , 7.84 , 7.56 , 7.49 , 7.35 . Colourless blocks were obtained by recrystallization from mixed solvents of methyl\u00adene chloride and n-hexane (v:v = 1.2).A mixture of 9Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314621004284/hb4376sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621004284/hb4376Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621004284/hb4376Isup3.cmlSupporting information file. DOI: 2079137CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Nickel(II) Schiff base complexes containing thiol\u00adate S and polyamine N donor atoms exhibit electrocatalytic activity for proton reduction. The piperazine moiety in the Schiff base ligand gives a smaller bite angle, which is effective in reducing the overpotential. N)(meth\u00adyl)amino-\u03baN]eth\u00adyl}imino-\u03baN)meth\u00adyl]benzene\u00adthiol\u00adato-\u03baS}nickel(II) chloride, [Ni(C12H18N3S)]Cl (1), and [2-eth\u00adyl]imino-\u03baN}meth\u00adyl)benzene\u00adthiol\u00adato-\u03baS]nickel(II) hexa\u00adfluoro\u00adphosphate di\u00adchloro\u00admethane monosolvate, [Ni(C13H18N3S)]PF6\u00b7CH2Cl2 (2), were synthesized by the reactions of 2-(tert-butyl\u00adthio)\u00adbenzaldehyde, tri\u00adamines, and nickel(II) salts. Both complexes have a nickel ion surrounded by an N,N\u2032,N\u2032\u2032,S-tetra\u00addentate ligand, forming a square-planar geometry. The terminal N,N-chelating moiety is N,N-di\u00adalkyl\u00adethane-1,2-di\u00adamine for 1 and 1-alkyl\u00adpiperazine for 2. The N\u2014Ni\u2014N bite angle in the terminal N,N-chelate ring in 2 [76.05\u2005(10)\u00b0] is much smaller than that in 1 [86.16\u2005(6)\u00b0]. Cyclic voltammograms of 1 and 2 in aqueous media indicated that the reduction and oxidation potentials of 2 are more positive than those of 1. The smaller bite angle of the terminal piperazine chelate in 2 reduces the electron-donating ability of the tetra\u00addentate ligand, resulting in a positive shift of the redox potentials. Both complexes exhibit catalytic activity for proton reduction, and the piperazine moiety in 2 is effective in reducing the overpotential.The thiol\u00adate nickel complexes {2-[({2-[(2-amino\u00adethyl-\u03ba In the electrocatalytic proton reduction, the electrochemical properties of the precatalysts are directly related to the formation of real catalysts. Therefore the tuning of the redox properties is also required in the ligand design.The nickel(II) complex Cl (1) and [Ni(C13H18N3S)]PF6 (2), in which the N,N\u2032,N\u2032\u2032,S-tetra\u00addentate Schiff base ligands contain an additional N-methyl group and a terminal piperazine moiety, respectively. The electrochemical properties of these complexes were investigated by cyclic voltammetry in water, and compared with those of [Ni(C11H16N3S)]Cl (3) without N-substituents.In this work we synthesized two water-soluble N2.1 and 2 consist of an Ni2+ ion and a monoanionic N,N\u2032,N\u2032\u2032,S-tetra\u00addentate ligand, giving a square-planar geometry. The asymmetric unit in 1 comprises the complex cation and a chloride anion, whereas in 2 a hexa\u00adfluoro\u00adphosphate anion and a di\u00adchloro\u00admethane mol\u00adecule are incorporated into the crystal lattice.The complex cations in N,S-chelate, the N1\u2014Ni1\u2014S1 angles are 97.77\u2005(5)\u00b0 in 1 (Table\u00a012 (Table\u00a023 [98.5\u2005(2)\u00b0] and the tetra\u00adphenyl\u00adborate salt [Ni(C11H16N3S)]B(C6H5)4 . The bond distances in the chelate rings are also comparable \u00b0 in 1, 87.80\u2005(10)\u00b0 in 2, 86.1\u2005(3)\u00b0 in 3  complexes with S,N,N,S-tetra\u00addentate ligands, which have two amine N or two imine N donor atoms besides two S atoms \u00b0] is much smaller than those of 1 [86.16\u2005(6)\u00b0], 3  and 2 [N1\u2014C8\u2014C9\u2014N2 = 45.1\u2005(3)\u00b0], this bending is due to the rigid structure of the piperazine chelate, which fixes the direction of the methyl\u00adene groups on the tertiary amine N atom.In complex 3.1 shows hydrogen bonds between the terminal amine nitro\u00adgen atom in the complex cation and two chloride ions with the N3\u22efCl1 and N3\u22efCl1 and 3.8965\u2005(13)\u2005\u00c5].The crystal structure of y Table\u00a03, which aon Fig.\u00a03. The dis2 between the methyl\u00adene hydrogen atoms of the polyamine moiety and the \u03c0 system of the benzene ring  distance of 3.114\u2005(3)\u2005\u00c5  = 2.47\u2005(4)\u2005\u00c5].Several inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions exist in g Table\u00a04. The pip\u00c5 Table\u00a04. In addi4.N,N\u2032,N\u2032\u2032,S-tetra\u00addentate Schiff base ligands studied here have not been reported so far for other transition-metal ions. A similar Schiff base structure that contains benzene\u00adthiol\u00adate and polyamines is found in a trinuclear nickel(II) complex with a C3-symmetric ligand based on a 1,3,5-trimercapto\u00adbenzene backbone \u00b0  complexes 1, 2, and 3 was investigated by cyclic voltammetry. Measurements were performed in 5 \u00d7 10\u22124M (1\u2005M = 1\u2005mol\u2005dm\u22123) aqueous solution containing KNO3 (0.1\u2005M) at a scan rate of 0.1\u2005V\u2005s\u22121. The working electrode was a glassy carbon disk electrode with a diameter of 3\u2005mm, the auxiliary electrode was a platinum wire, and the reference electrode was Ag/AgCl/saturated KCl. All complexes exhibit irreversible reduction and oxidation processes  suggest the adsorption of the reduced species. In the oxidation process, the anodic wave appeared at 0.73\u2005V for 1, 0.79\u2005V for 2, and 0.68\u2005V for 3. In both processes, the redox potentials of 1 are slightly shifted to more positive values than those of 3, which suggests that the electronic and steric effects of the methyl group on the central N atom are not so significant. The voltammogram of 2 shows further positive shifts, and the shift in the reduction process is more pronounced. This is probably related to the smaller bite angle of the terminal piperazine chelate, which reduces the electron-donating ability of the Schiff base ligand toward the nickel center.The redox behavior of the es Fig.\u00a05. In the 1 and 2 were compared in a buffer solution of pH 4.6 (0.1 M acetic acid/sodium acetate). A catalytic current was observed during the reduction process, giving a peak at \u22121.28\u2005V for 1 and \u22121.23\u2005V for 2  under N2. Elemental analyses were performed by the Analytical Research Service Center at Osaka City University or A Rabbit Science Co., Ltd.12H18N3S)]Cl (1).PF6 (2).[Ni(C To a solution of N-(2-amino\u00adeth\u00adyl)piperazine  and 2-(t-butyl\u00adthio)\u00adbenzaldehyde  in ethanol (20\u2005mL) was added NiCl2\u00b76H2O . The resulting suspension was refluxed under a nitro\u00adgen atmosphere for 8\u2005h, during which time the color of the solution turned orange and a yellow\u2013green precipitate formed. The reaction mixture was filtered, and an ethanol solution (5\u2005mL) of ammonium hexa\u00adfluoro\u00adphosphate  was added to the filtrate. The resulting orange precipitate was collected by filtration and dried under reduced pressure to give an orange powder of 2 . Suitable crystals for X-ray diffraction analysis were grown from a di\u00adchloro\u00admethane solution by layering with diethyl ether. 1H NMR : \u03b4 2.76\u20132.94 2NH), 2.83 , 3.91\u20134.03 2NH), 4.16\u20134.27 2NH), 4.31 , 7.10 , 7.28 , 7.52 , 7.74 , 8.16 . Analysis calculated for C13H18F6N3NiPS\u00b70.75CH2Cl2: C, 32.02; H, 3.81; N, 8.15. Found: C, 32.11; H, 3.93; N, 8.14.8.N,N-chelating moieties in 1 were modeled as disordered over two positions each, and the occupancy factors refined to 0.864\u2005(3) and 0.136\u2005(3). Hydrogen atoms on the disordered C atoms and the adjacent C atoms that belong to the minor site were placed in calculated positions with C\u2014H(meth\u00adyl) = 0.98\u2005\u00c5 and C\u2014H(methyl\u00adene) = 0.99\u2005\u00c5 and refined using a riding model with Uiso(H) = 1.5Ueq(C) and 1.2Ueq(C), respectively. Other H atoms were found in a difference-Fourier map and freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989022003954/dj2045sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989022003954/dj20451sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989022003954/dj20452sup3.hklStructure factors: contains datablock(s) 2. DOI: 2165891, 2165890CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ions both show a distorted N3Cl3 octa\u00adhedral coordination environment defined by three N atoms of the tridentate 2,4,6-tri-2-pyridyl-1,3,5-triazine ligand, two bridging Cl\u2212 ligands and a Cl\u2212 anion.The Ni 2Cl4(C18H12N6)2], the NiII ions are hexa-coordinated in a distorted octa\u00adhedral coordination environment defined by three N atoms of the tridentate 2,4,6-tri-2-pyridyl-1,3,5-triazine ligand and three Cl\u2212 anions in a meridional geometry. The two NiII ions are bridged by two Cl anionic ligands, thereby forming a dinuclear complex. A crystallographic centre of inversion is located at the centroid of the Ni2Cl2 ring.In the title compound, [Ni On the other hand the Cl2\u2014Ni1\u2014Cl1i axis (symmetry code: (i) \u2212x, \u2212y\u00a0+\u00a01, \u2212z) is almost linear [Cl2\u2014Ni1\u2014Cl1i = 176.25\u2005(2)\u00b0]. The Ni\u2014N(pyrid\u00adyl) bonds [Ni1\u2014N4/N6 = 2.130\u2005(2) and 2.129\u2005(2)\u2005\u00c5] are slightly longer than the Ni\u2014N(triazine) bond [Ni1\u2014N1 = 1.970\u2005(2)\u2005\u00c5]. The three Ni\u2014Cl bond lengths are somewhat different . The two pyridyl rings that coordinat to the NiII atom are located approximately parallel to the respective triazine ring, making dihedral angles of 4.51\u2005(6) and 4.95\u2005(6)\u00b0, respectively. The dihedral angle between the non-coordinating pyridyl substituent and the triazine ring is 7.56\u2005(6)\u00b0.In the complex, the two Niex Fig.\u00a01. Each NiCg1 (the centroid of ring N5/C8\u2013C12) and Cg2ii [the centroid of ring N6/C14\u2013C18; symmetry code: (ii) x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0The complex displays numerous inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent six-membered rings. For e Table\u00a01.2\u00b76 H2O  in ethanol (30\u2005ml) was added 2,4,6-tri-2-pyridyl-1,3,5-triazine . The solution was stirred for 12\u2005h at room temperature. The formed precipitate was separated by filtration, washed with ethanol and acetone, and dried at 323\u2005K, to give a pale-green powder . Brown crystals suitable for X-ray analysis were obtained by slow evaporation from a dimethyl sulfoxide (DMSO) solution at 363\u2005K.To a solution of NiCl\u22123) and minimum (\u22120.20\u2005e\u2005\u00c5\u22123) electron density in the difference Fourier map are located 0.73 and 1.28\u2005\u00c5, respectively, from atoms C2 and C9.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621000936/im4011sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621000936/im4011Isup2.hklStructure factors: contains datablock(s) I. DOI: 2058987CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The units are further linked by O\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds.In the crystal of the title organic salt, the cation and the anion are connected  H-benzimidazol-3-ium] 2,5-di\u00adchloro-3,6-dioxo\u00adcyclo\u00adhexa-1,4-diene-1,4-diolate}, 2C13H11N2O+\u00b7C6Cl2O42\u2212, the chloranilate anion is located on an inversion centre, so that the asymmetric unit contains one cation and one half of the chloranilate anion. In the crystal, the cation and the anion are connected by a bifurcated N\u2014H\u22ef hydrogen bond, forming a 2:1 unit. The units are linked into a layer lying parallel to -1 D\u2014H\u22efA hydrogen bonding  in chloranilic acid\u2013organic base systems ; symmetry code as given in Table\u00a01via O\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds \u2005\u00c5 and C2\u2014Cl1\u22efCg3iv = 139.21\u2005(5)\u00b0; symmetry code: (iv) x, y, z\u00a0\u2212\u00a01] is observed between the layers, where Cg3 is the centroid of the C11\u2013C16 ring.We have prepared the title compound in order to continue our studies of H-benzimidazole in a ca 1:1 molar ratio at room temperature [150\u2005ml methanol solution of chloranilic acid (0.45\u2005g) and 2-(2-hy\u00addroxy\u00adphen\u00adyl)-1H-benzimidazole (0.45\u2005g)].Single crystals of the title salt were obtained by slow evaporation from a methanol solution of chloranilic acid with 2-(2-hy\u00addroxy\u00adphen\u00adyl)-1Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621011500/hb4396sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314621011500/hb4396Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621011500/hb4396Isup3.cmlSupporting information file. DOI: 2119367CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Targeted drug delivery systems hold the remarkable potential to improve the therapeutic index of anticancer medications markedly. Here, we report a targeted delivery platform for cancer treatment using clathrin light chain (CLC)\u2010conjugated drugs. We conjugated CLC to paclitaxel (PTX) through a glutaric anhydride at high efficiency. Labeled CLCs localized to 4T1 tumors implanted in mice, and conjugation of PTX to CLC enhanced its delivery to these tumors. Treatment of three different mouse models of cancer\u2014melanoma, breast cancer, and lung cancer\u2014with CLC\u2010PTX resulted in significant growth inhibition of both the primary tumor and metastatic lesions, as compared to treatment with free PTX. CLC\u2010PTX treatment caused a marked increase in apoptosis of tumor cells and reduction of tumor angiogenesis. Our data suggested HSP70 as a binding partner for CLC. Our study demonstrates that CLC\u2010based drug\u2010conjugates constitute a novel drug delivery platform that can augment the effects of chemotherapeutics in treating a variety of cancers. Moreover, conjugation of therapeutics with CLC may be used as means by which drugs are delivered specifically to primary tumors and metastatic lesions, thereby prolonging the survival of cancer patients. ACNacetonitrileADCantibody\u2010drug conjugateBUNblood urea nitrogenCD31cluster of differentiation 31CLCclathrin light chainDAPIdiamidino\u20102\u2010phenylindoleDLSdynamic light scatteringDMEMDulbecco's modified Eagle's mediumDMSOdimethyl sulfoxideECMextracellular matrixEDC1\u2010ethyl\u20103\u2010(3\u2010dimethylaminopropyl)carbodiimideESIMSelectron spay ionization mass spectrometryE. coliEscherichia coliFBSfetal bovine serumGAPDHglyceraldehyde\u20103\u2010phosphate dehydrogenaseHPLChigh\u2010performance liquid chromatographyHRPhorseradish peroxidaseHSP70heat shock protein 70H&Ehematoxylin and eosinLLC1Lewis lung carcinoma 1LYVE1lymphatic vessel endothelial hyaluronan receptor 1MALDI\u2010TOFmatrix\u2010assisted laser desorption ionization time\u2010of\u2010flightMFImean fluorescence intensityMSmass spectrometryNHSN\u2010hydroxysuccinimideNMRnuclear magnetic resonancePDBprotein data bankPKpharmacokineticsPTXpaclitaxelROIregion of interestRPMIRoswell park memorial instituteSDstandard deviationSDS\u2010PAGEsodium dodecyl sulfate\u2010polyacrylamide gel electrophoresissiRNAsmall interfering ribonucleic acidTDLNtumor\u2010draining lymph nodeTGItumor growth inhibitionUV\u2013Visultraviolet\u2013visible1Targeted drug delivery systems can amplify the concentration of transported payloads at various tissues of interest, including tumors.Antibody\u2010drug conjugates (ADCs) are emerging platforms for the delivery of a range of cancer drugs.Here, we report a novel application of clathrin light chain A (CLC)\u2010based drug delivery. CLC is an endogenous small protein that forms a network of triskelions that constitute a polyhedral lattice around vesicles that assist in the sorting of cargo for intracellular trafficking.First, we confirmed that CLCs interact with cancer cells and could be used as vehicles for targeted delivery to malignant tumors. Next, CLCs were conjugated to the antineoplastic agent paclitaxel (PTX) via reaction with glutaric anhydride (CLC\u2010PTX) to evaluate their utility for cancer\u2010targeted delivery and treatment in a series of mouse models. CLC\u2010PTX enhanced the concentration of PTX at the tumor site and suppressed tumor growth in mouse models of breast cancer, melanoma, and lung carcinoma. In addition, CLC\u2010PTX was found to reduce the size of metastatic lesions in breast cancer.22.1Escherichia coli (E. coli), confirmed by sodium dodecyl sulfate\u2010polyacrylamide gel electrophoresis (SDS\u2010PAGE), and extracted at a purity of >85%, as demonstrated by Western blot (data not shown). PTX is a chemotherapeutic drug used for the treatment of numerous cancers.1H\u2010NMR  was expressed in R Figure\u00a0 and 13C\u2010R Figure\u00a0. In the N\u2010hydroxysuccinimide (NHS) coupling to produce CLC\u2010PTX*, which was verified by ultraviolet\u2013visible (UV\u2013Vis) spectroscopy  was used to confirm the conjugation of PTX to CLC. The maximal absorbance of PTX* is observed at a wavelength of around 500\u2009nm. We conjugated 2\u2032\u2010glutaryl PTX* to CLC via 1\u2010ethyl\u20103\u2010(3\u2010dimethylaminopropyl)carbodiimide (EDC)/sulfo\u2010y Figure\u00a0. The absy Figure\u00a0. After cy Figure\u00a0, whereasy Figure\u00a0. Next, Cy Figure\u00a0. Intravey Figure\u00a0A. In addy Figure\u00a0B and C.2.2We sought to determine whether CLC was internalized by 4T1 mouse breast cancer cells by incubating these cells with CLCs attached to Alexa Fluor\u2122 488 dye. The colocalization of the CLCs with a lysosome marker was confirmed Figure\u00a0, which iA virtual screening between CLC and a protein data bank (PDB) was conducted, resulting in the identification of three proteins with high binding energy Table\u00a0. Interes2.3iv to 4T1 tumor\u2010bearing BALB/c mice. The mice were euthanized at 1\u00a0day (1\u00a0d), 2\u2009days, and 3\u2009days following administration of CLCs, at which time points we measured the fluorescent signal of CLC\u2010IR800 in various organs, using an iBox Exploreriv with CLC\u2010PTX* and quantified the fluorescence of PTX*. PTX* did not clear significantly from the tumor within the span of the study, whereas the PTX* signal declined in the liver and the kidney over time  e Figure\u00a0.The lung is the most common site of metastasis for breast cancer. Lung with 4T1 metastasis showed enhanced targeting signals of CLC as compared with na\u00efve lung Figure\u00a0. Interesiv administration to 4T1 breast tumor\u2010bearing BALB/c mice. Ex vivo fluorescent images of the tumors were acquired 1\u00a0day following administration of PTX* or CLC\u2010PTX* at an equivalent PTX* dose of 0.5\u00a0mg/kg, which showed that the accumulation of CLC\u2010PTX* in the tumor was higher than free PTX*  quantified PTX. We detected significant amounts of PTX in the sera of the CLC\u2010PTX group as compared with the free PTX group at 6\u00a0h, indicating that conjugation to CLC enhanced the blood circulation of PTX . The tumors in the CLC\u2010PTX group displayed slower tumor progression in comparison to the two other treatment groups  of 4T1 tumor\u2010bearing mice at 27\u2009days following implantation Figure\u00a0. The exp2.63, following a schedule and dosing identical to the 4T1 study above. Again, CLC\u2010PTX displayed the most potent inhibitory effect on tumor growth: at the end of the study, the tumors of the mice treated iv with CLC\u2010PTX were the smallest (0.81\u2009\u00b1\u20090.30\u2009\u00d7\u2009103\u2009mm3), as compared to the PBS\u2010treated mice (2.36\u2009\u00b1\u20090.61\u2009\u00d7\u2009103\u2009mm3) and free PTX\u2010treated mice (1.29\u2009\u00b1\u20090.50\u2009\u00d7\u2009103\u2009mm3) . Immunostaining demonstrated a decline of Melan\u2010A+ cells with an increase in caspase\u20103 expression in the CLC\u2010PTX\u2010treated mice as compared to other groups  Figure\u00a0. TGI by s Figure\u00a0. The B16s Figure\u00a0.2.7iv to C57BL/6 mice bearing LLC1 murine lung carcinoma, following a schedule identical and dosing in the aforementioned tumor models. The tumors in the CLC\u2010PTX group (0.80\u2009\u00b1\u20090.21\u2009\u00d7\u2009103\u2009mm3) were significantly smaller than those in the mice that received PBS (1.68\u2009\u00b1\u20090.30\u2009\u00d7\u2009103\u2009mm3) and free PTX (1.21\u2009\u00b1\u20090.31\u2009\u00d7\u2009103\u2009mm3) . Next, we stained LLC1 tumor tissue sections with the cancer marker pan\u2010cytokeratin, apoptosis marker caspase\u20103, proliferation marker Ki67, and vascular marker CD31, and examined them by fluorescence microscopy. Treatment with CLC\u2010PTX reduced the amount of Pan\u2010Cytokeratin+ cancer cells significantly, whereas Caspase\u20103+ apoptotic cells increased  Figure\u00a0. In addid Figure\u00a0. Consistd Figure\u00a0. Furtherd Figure\u00a0. Thus, t3Targeted drug delivery systems have attracted major interest and already entered into clinical practice for various diseases, but their application to cancer remains to be developed.Metastasis is the primary factor of cancer morbidity and mortality.Nonetheless, future in vivo targeting studies are required to define the mechanisms by which HSP70 functions as a target of CLC\u2010conjugated drug delivery. In addition, HSP70 produced by tumor cells may undergo differential glycosylation, so kinetic studies tailored to each type of cancer may be required for more specific and accurate assessment of the binding affinity of HSP70 to CLC. The performance of a mutational study to identify putative binding site of CLCOur data suggest that CLC targeted the primary tumor and metastatic lung lesions of 4T1 breast cancer in mice with high efficacy. While there was an increase in CLCs in the peripheral organs, in particular, the kidney; however, this retention faded after 3\u2009days. Nonetheless, the tumor uptake of exogenously administered CLCs remains relatively stable over time.CLC\u2010PTX enhanced the therapeutic efficacy of PTX on the primary 4T1 tumor, as demonstrated by suppression of tumor growth, enhancement of cancer cell apoptosis, and especially inhibition of angiogenesis. CLC\u2010PTX treatment was also found to reduce the density of lymphatic vasculature, which often contributes to the immunosuppressive environment of TDLN. Concomitantly, distant lung metastasis was also inhibited more effectively by treatment with CLC\u2010PTX than free PTX. Excessive accumulation of extracellular matrix (ECM) in the tumor stroma is referred to as the desmoplastic reaction, commonly reported as a major obstacle to the treatment of cancers.44.14T1 mouse breast cancer (ATCC\u00ae CRL\u20102539\u2122), B16 mouse melanoma (ATCC\u00ae CRL\u20106322\u2122), LLC1 mouse lung carcinoma (ATCC\u00ae CRL\u20101642\u2122), and HK02 human kidney tubular epithelial cell lines (ATCC\u00ae CRL\u20102190\u2122) were purchased from American Type Culture Collection . 4T1, B16, LLC1, and HK02 cells were cultured in RPMI\u20101640 or Dulbeccos modified Eagles medium with 10% fetal bovine serum and 1% penicillin/streptomycin (pen/strep).4.2C57BL/6 (JAX# 000664) and BALB/c (JAX# 000651) mice were obtained from The Jackson Laboratories. All animal experiments and methods were performed in accordance with the relevant guidelines and regulations approved by the Institutional Animal Care and Use Committee (protocols: 2016\u2009N000167/04977) of Brigham and Women's Hospital .4.3E. coli expression system as follows. The human CLC gene was codon\u2010optimized for expression in E. coli and chemically synthesized by Biomatik. The synthesized gene was subsequently cloned into NdeI/HindIII sites with pET30a vector. These expression plasmids were used to transform the E. coli BL21(DE3). His\u2010tag was applied to a Ni\u2010NTA column and eluted in a buffer containing 10\u2009mM Tris, 0.15\u2009M NaCl, 8\u00a0M urea, and 0.3\u00a0M imidazole at a pH of 8.0.Human CLC was expressed and optimized for an Gene sequence; ATGGCGGAACTGGACCCGTTCGGCGCTCCGGCAGGCGCACCGGGCGGTCCGGCGCTGGGTAACGGCGTTGCGGGTGCTGGTGAAGAAGACCCGGCAGCAGCGTTCCTGGCGCAGCAGGAATCTGAAATCGCAGGTATCGAAAACGATGAAGCGTTCGCGATCCTGGACGGTGGTGCTCCGGGTCCGCAGCCGCACGGTGAACCGCCGGGTGGTCCGGATGCGGTTGACGGTGTTATGAACGGCGAGTACTACCAGGAGTCTAACGGTCCGACCGATTCTTACGCGGCAATTAGCCAGGTTGATCGTCTGCAATCCGAACCGGAATCTATCCGTAAATGGCGTGAGGAGCAGATGGAACGCCTGGAAGCTCTGGACGCGAACTCTCGCAAACAGGAGGCGGAATGGAAAGAAAAAGCGATCAAAGAGCTGGAAGAATGGTATGCGCGTCAGGACGAACAGCTGCAAAAAACCAAAGCGAACAACCGTGTGGCGGACGAAGCATTCTACAAACAGCCGTTTGCGGACGTTATCGGTTACGTTACCAACATCAACCATCCGTGCTACTCTCTGGAGCAGGCAGCGGAAGAAGCGTTCGTGAACGACATCGACGAATCTAGCCCAGGCACCGAATGGGAACGTGTTGCGCGCCTGTGCGACTTCAACCCGAAATCTTCTAAACAGGCTAAAGACGTTTCTCGTATGCGTTCTGTTCTGATCTCTCTGAAGCAGGCTCCGCTGGTTCAC.Amino sequence; MAELDPFGAPAGAPGGPALGNGVAGAGEEDPAAAFLAQQESEIAGIENDEAFAILDGGAPGPQPHGEPPGGPDAVDGVMNGEYYQESNGPTDSYAAISQVDRLQSEPESIRKWREEQMERLEALDANSRKQEAEWKEKAIKELEEWYARQDEQLQKTKANNRVADEAFYKQPFADVIYVTNINHPCYSLEQAAEEAFVNDIDESSPGTEWERVARLCDFNPKSSKQAKDVSRMRSVLISLKQAPLVH.The purity of CLC was >85%, as estimated by a Coomassie blue\u2010stained SDS\u2010PAGE gel. The concentration of CLC was determined by Bradford protein assay, using BSA as a standard. Its molecular weight was 28.1\u00a0kDa, and its isoelectric point was 4.37.4.4www.rcsb.org. Three proteins with the highest binding energy were identified through AutoDock Vina: ADP\u2010ribosylation factor 3, HSP70, and serine/threonine\u2010protein phosphatase PP1\u2010beta catalytic subunit  was labeled with Alexa Fluor\u2122 488 NHS Ester (Thermo Fisher Scientific) or Alexa Fluor\u2122 594 NHS Ester (Thermo Fisher Scientific) and incubated with 4T1 cells for 2\u00a0h at 37\u00b0C. After five washes with PBS buffer, 4T1 cells were stained with lysosomal staining kit . 4T1 cells were fixed with 4% paraformaldehyde (Electron Microscopy Sciences), and diamidino\u20102\u2010phenylindole (DAPI)  was used to counterstain the cell nuclei. The cells were visualized using an EVOS\u2122 FL Auto 2 Imaging System (Thermo Fisher Scientific). After splitting each color channel, the area with fluorescence was measured for each color channel with Image J . The percent of uptake of CLC was calculated by dividing with measured area from DAPI channel.4.62O with 0.1% formic acid for 20\u2009min), using a Phenomenex Luna 5\u00a0\u03bcm C18 column . The product was detected at 14.1\u00a0min, and molecular weight was confirmed as 969\u2009g/mol by electron spay ionization mass spectrometry analysis ([M\u2010H]\u2212 m/z at 968]). 2'\u2010Glutaryl PTX was purified by reversed\u2010phase HPLC  with a gradient solvent system (15%\u201375% ACN/H2O with 0.1% formic acid for 40\u2009min). The product was eluted at a retention time of 13.4\u00a0min under these HPLC conditions. 2\u2032\u2010Glutaryl PTX was confirmed by 1H\u2010NMR (proton nuclear magnetic resonance) and 13C\u2010NMR (carbon nuclear magnetic resonance) spectra. 2'\u2010glutaryl PTX (0.2\u00a0mg) dissolved in dimethyl sulfoxide (DMSO) (Thermo Scientific Fisher) was activated with 1\u2010ethyl\u20103\u2010(3\u2010dimethylaminopropyl)carbodiimide hydrochloride  and Sulfo\u2010NHS (N\u2010hydroxysulfosuccinimide)  for 15\u2009min at RT in 2\u2010(N\u2010morpholino)ethanesulfonic acid (MES) buffer  . The EDC was quenched by 2\u2010mercaptoethanol  for 10\u00a0min. Immediately, the pH of the solution was increased by NaHCO3  to ~8. CLC dissolved in PBS  was mixed with the activated 2\u2032\u2010glutaryl PTX for 2\u00a0h at RT . Dialysis was performed twice by a centrifugal filter  at 10,000\u2009rpm for 15\u2009min to remove the free PTX. The solution was purified further by a desalting column .Glutaric anhydride  and PTX  were prepared in a 4\u00a0ml vial dried under high vacuum for 24\u2009h and dissolved in 1\u00a0ml of pyridine. The solution was stirred at room temperature under Ar atmosphere for 2\u00a0h. The mixture was diluted with 300\u2009\u03bcl of methanol, and 5\u00a0\u03bcl of solution was injected into liquid chromatography/mass spectrometery (LC/MS)  with a gradient reversed\u2010phase system (10%\u2013100% ACN/H4.7280\u2009nm) of CLC was extracted from the absorption spectrum of CLC solutions at different concentrations. The \u03b5CLC,280\u2009nm was 4.8\u2009\u00d7\u2009104, whereas \u03b5PTX,500\u2009nm was 4.2\u2009\u00d7\u2009104. The concentration of CLC (CCLC) in the CLC\u2010PTX* solution was calculated by /\u03b5CLC,280\u2009nm, and CPTX* was by .Absorbance was measured by UV\u2013Vis spectroscopy . The molar extinction coefficient  at 1:1 ratio. The 2\u2009\u03bcl of the samples was spotted, air\u2010dried, and detected with a linear detector. The data were analyzed using Bruker Daltonics flexAnalysis. External calibration was performed with BSA with [M\u2010H] average mass (m/z) of 66,428.MALDI mass analyses of CLC and CLC\u2010PTX were performed with a Bruker MicroFlex\u2122 MALDI\u2010TOF in negative mode. The protein solution was mixed with sinapinic acid matrix solution  was incubated in acetate buffer  or phosphate buffer  at 37\u00b0C. The solutions were dialyzed with 5% DMSO solution, and filtrates were analyzed by UV\u2013Vis spectroscopy to quantify the amount of free PTX* in comparison to the absorbance of the solution prior to incubation.4.105) was stained with CLC\u2010Alexa 594 or anti\u2010HSP70\u2010Alexa 594 in FACS buffer  at 4\u00b0C for 30\u2009min. Cells were washed by FACS buffer and fixed with FACS buffer containing 1% formalin. The autofluorescence from the cell itself was unmixed and only single cells were gated (Cytek\u00ae Aurora). Analysis of flow cytometry data was performed by FlowJo software . The histogram over Alexa 594 channel was extracted and the total fluorescence signal was divided by the total number of the cell.The surface of 4T1 cells (1.0\u00a0\u00d7\u2009104.11Cells were transfected with Lipofectamine 2000 (Invitrogen), according to the manufacturer's instructions. Briefly, cells were plated at 20%\u201330% density in 12\u2010well plates 24\u2009h prior to transfection. For siRNA transfection, the equivalent of 200\u2009nM of siRNA per well of a 12\u2010well plate was utilized. After a 48\u2009h incubation period, the lysates of the cells were measured using the Bradford assay. Equal amounts of protein were separated by SDS\u2010PAGE and transferred to a polyvinylidene fluoride (PVDF) membrane. The membranes were immunoblotted with the following specific antibodies: anti\u2010HSP70, anti\u2010rabbit IgG\u2010HRP (Sigma\u2010Aldrich), anti\u2010rat IgG\u2010HRP (Sigma\u2010Aldrich), and anti\u2010GAPDH (Sigma\u2010Aldrich), using standard protocols. The blots were developed with West Dura chemiluminescent substrates using a Bio\u2010Rad ChemiDoc imaging system.4.12s.c. with 1.0\u2009\u00d7\u2009105 4T1 cells. At 14\u2009days postimplantation, these mice received a single iv injection of CLC\u2010IR800 conjugate (4\u00a0mg/kg). At 1\u00a0day, 2\u2009days, and 3\u2009days following injection, the mice were euthanized via carbon dioxide inhalation and cervical dislocation, and their major organs were harvested and imaged by using a UVP iBOX Explorer Imaging Microscope (UVP) equipped with a 750\u2013780\u2009nm band\u2010pass excitation filter and an 800\u2009nm long\u2010pass emission filter. MFI for each organ was measured using the region of interest (ROI) function of ImageJ .Animal studies were approved and conducted according to the Institutional Animal Care and Use Committee of Brigham and Women's Hospital, Boston, MA. CLC\u2010IR800 was prepared by incubating CLC with IRdye 800CW NHS ester  for 2\u00a0h at RT. The crude was purified by a desalting column . For ex vivo biodistribution studies, BALB/c mice were injected 4.13s.c. implanted with 1.0\u2009\u00d7\u2009105 4T1 cells. At 14\u2009days postimplantation, these mice received a single iv injection of CLC\u2010PTX* conjugate . After 1\u00a0day, the mice were euthanized via carbon dioxide inhalation and cervical dislocation, and their major organs were harvested and imaged by using a UVP iBOX Explorer Imaging Microscope (UVP) equipped with a 455\u2013495\u2009nm band\u2010pass excitation filter and a 513\u2013557\u2009nm band\u2010pass emission filter. MFI of the organs was measured following subtraction of autofluorescence, using the ROI function of ImageJ.CLC\u2010PTX* was prepared with the identical protocol for the synthesis of CLC\u2010PTX except the use of PTX* . BALB/c mice were 4.1418: 100\u2009\u00d7\u20092.1\u2009mm, 2.6\u00a0\u03bcm) under the following gradient elution system: 10% acetonitrile/water to 100% acetonitrile/water for 20\u2009min with a flow rate of 0.3\u00a0ml/min. Extracted ion is 854\u2009m/z.BALB/c mice  were injected intravenously with PTX or CLC\u2010PTX at an equivalent PTX dose of 2.5\u00a0mg/kg. Sera from three mice were collected at 6\u00a0h and 2\u2009days following drug administration. The serum samples were stored at \u221220\u00b0C until analysis. Serum samples (200\u2009\u03bcl) were mixed with acetate buffer  for 1\u00a0day at 37\u00b0C. PTX in the serum was extracted by incubation with acetonitrile (6\u00a0ml) for 2\u00a0h at 37\u00b0C. After centrifugation , the supernatants were analyzed by HPLC. High\u2010resolution electrospray ionization mass spectra were acquired using Agilent LC\u2010q\u2010TOF Mass Spectrometer 6530\u2010equipped with a 1290 uHPLC system. The collected samples were injected into a reversed\u2010phase HPLC column  were 4.165 4T1 cells in the left fourth mammary gland. C57BL/6 mice  were inoculated subcutaneously with 1.0\u2009\u00d7\u2009105 B16, LLC1, or Pan02 cells in the right rear flanks. When the tumor size reached ~100\u2009mm3, the mice were randomly divided into three groups (n\u00a0=\u00a06). All groups received treatments iv; the first group was injected with PBS (control), the second group with free PTX , and the final group with CLC\u2010PTX . The treatment schedule consisted of twice\u2010per\u2010week injections for 2\u2009weeks. The tumor size and body weight of the mice were monitored during the treatment course. The length (l) and width (w) of the tumor was measured by a digital Vernier caliper, and tumor volume (V) was defined as V=l\u00d7w2/2. We evaluated the TGI rate of each group (TGI%=Vc\u2212Vt/Vc\u2212Vi\u00d7100), in which Vc is the volume of the control tumor at the end of the study, Vt is the volume of drug\u2010treated tumor at the end of the study, and Vi is the volume of tumor at the initial treatment.BALB/c mice  were implanted subcutaneously with 1.0\u2009\u00d7\u200910Before the diameter of the tumor reached ~2\u00a0cm, the mice were euthanized, and lungs, livers, kidneys, spleen, tumor, and draining inguinal lymph nodes were harvested and embedded in optimum cutting temperature (OCT) compound .4.17Frozen OCT blocks of tumors and LNs were cut using a cryostat (Leica) into 8\u2010\u03bcm thick sections and cells were incubated in glass\u2010bottomed well plate (Lab Tek\u2122). Meanwhile, cell samples were also stained by the following procedure. The samples were stained using anti\u2010pan\u2010cytokeratin , anti\u2010Melan\u2010A , anti\u2010LYVE\u20101 , anti\u2010fibronectin , anti\u2010CD31 , anti\u2010caspase\u20103 , anti\u2010mouse/human Ki\u201067  antibodies, or anti\u2010HSP70 . Dye\u2010conjugated secondary antibodies  were used for the addition of the fluorescence signals. DAPI  was used to stain the cell nuclei. The stained tissue sections were imaged using a fluorescent confocal microscope and an EVOS FL2 auto microscope or FluoView FV\u201010i Olympus Laser Point Scanning Confocal Microscope . After splitting each color channel, the fluorescent area for each color channel was measured with ImageJ . The expression level for each marker was calculated on the basis of normalization with the DAPI signal.4.18Major organs were immediately fixed in 4% paraformaldehyde, embedded in paraffin, and sliced into 5\u2010\u03bcm\u2010thick sections, which were then stained with H&E for histological examination. Organ histology was viewed and imaged under light microscopy (EVOS FL2).4.19iv injection of CLCs  was measured by the Infinity Urea kit (Thermo Fisher Scientific) and compared against a standard BUN solution of 100\u2009mg/dl (Sigma\u2010Aldrich) using a VersaMax microplate reader , as per the protocol provided by Thermo Fisher Scientific. The creatinine (Cr) of the serum following iv injection of CLCs  was measured using the microplate reader, according to the instructions provided in the Mouse Creatinine Assay Kit .BUN of the C57BL/6 mice serum following 4.20n) in the experiments was as follows: six for tumor growth analysis, six for lung metastatic foci assay, three for the fluorescent biodistribution, and three for the tissue immunostaining study. The fluorescence in vitro assay was independently conducted three times for statistical analysis. All data are expressed as the mean\u2009\u00b1\u2009SD from at least three independent samples or experiments. Differences between the two groups were analyzed by an unpaired Student's t\u2010test. Comparisons between multiple groups were determined using one or two\u2010way analysis of variance with Holm\u2010Sidak's post hoc test. A p value <0.05 was considered statistically significant .All statistical analysis was conducted using GraphPad Prism 7 software . The expression level of each marker in the immunostaining experiments was determined by dividing each DAPI level. The sample size ; data curation (lead); formal analysis (lead); investigation (lead); methodology (lead); validation (lead); visualization (lead). Liwei Jiang: Conceptualization ; data curation (lead); formal analysis (lead); investigation ; methodology . Jing Zhao: Data curation (supporting); investigation ; methodology . Leonard D. Shultz: Funding acquisition ; resources ; supervision . Dale L. Greiner: Methodology ; resources ; supervision . Munhyung Bae: Data curation (supporting); methodology (supporting). Xiaofei Li: Data curation (supporting); methodology (supporting). Farideh Ordikhani: Conceptualization (supporting); formal analysis (supporting); methodology (supporting). Rui Kuai: Supervision (supporting); validation (supporting). John Joseph: Data curation (supporting); formal analysis (supporting); methodology (supporting). Vivek Kasinath: Data curation (supporting); formal analysis (supporting); funding acquisition ; supervision (supporting); validation (supporting). David R. Elmaleh: Conceptualization ; formal analysis (supporting); methodology (supporting); resources (supporting); supervision (supporting). Reza Abdi: Conceptualization (lead); data curation (lead); formal analysis (lead); funding acquisition (lead); investigation (lead); methodology (lead); project administration (lead); resources (lead); software (lead); supervision (lead); validation (lead); visualization (lead).All authors declare no conflict of interests.https://publons.com/publon/10.1002/btm2.10273.The peer review history for this article is available at Appendix S1: Supporting informationClick here for additional data file."}
{"text": "These aluminates have been characterised by X\u2010ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non\u2010covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(tBuDHP)(TMP)Al(iBu)2] and [(TMEDA)Na(tBuDHP)(TMP)Al(iBu)2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali\u2010metal\u2010aluminium hydride surrog[ATES].A series of group\u20051 hydrocarbon\u2010soluble donor free aluminates [AM( Saturated 2,2,6,6\u2010tetramethylpiperidide, TMP, has long played a key role in synthesis, here combined with an unsaturated dihydropyridine unit, 2\u2010tBuC5H5N, both contribute to the stability of a series of alkali metal aluminate structures by engaging in non\u2010covalent interactions with alkali metal cations, the extent of which depends on the alkali metal. Thermal Volatility Analysis (TVA) of the resultant samples showed that the propensity of hydride expulsion of the AM(tBuDHP) complexes increased down the group from lithium to potassium, following the trend of decomposition of saline hydrides.In 2015, our group reported another strategy, wherein a saturated C\u2212H bond in an alkyldihydropyridyl anion bound to lithium in  has a track record in stabilizing a range of organolithium components to form heterobimetallic \u2018ate\u2019 complexes. These ates have had an important role to play in the development of bimetallic cooperativity.[iBu)2Al(TMP)] in tandem have ascertained that the sterically encumbered TMP ligands allow the lithium amide to display its basic function by deprotonation of an aryl/alkyl substrate, while the organoaluminium moiety traps the new, less hindered organolithium molecule in a method labelled as \u201ctrans\u2010metal\u2010trapping\u201d (TMT).[tBuDHP)], an amide carrying a surrogate hydride, as an alternative to Li(TMP). From a structural perspective this would open up a new avenue to isolate rarer aluminates of heavier alkali metals. Hence, our target here was to synthesise and characterise a new class of ate compound combining the complete set of alkali metal dihydropyridines with the dialkylamidoaluminium reagent [(iBu)2Al(TMP)], in effect heteroleptic alkali metal aluminium hydride surrog[ATES].Di\u2010iso\u2010butylaluminium\u20102,2,6,6\u2010tetramethylpiperidide [2Al(TMP)] was subjected to a suspensiontBuDHP)] in n\u2010pentane, the resultant mixture turned homogeneous at room temperature (Scheme\u20056D6 solution hinted at the formation of a new species as evident from a definite shift in the dihydropyridyl C\u2212H resonances in comparison to those in free Li(tBuDHP) . Meanwhile, a concentrated solution of the above mixture in n\u2010pentane cooled to \u221220\u2009\u00b0C overnight yielded colourless crystalline blocks. Single crystal X\u2010ray analysis of the crystals unveiled a solvent\u2010free monomer of a bimetallic ate complex, [Li(tBuDHP)(TMP)Al(iBu)2] (1)  analogues ether, PMDETA=N,N,N\u2032,N\u2032\u2032,N\u2032\u2032\u2010pentamethyldiethylenetriamine, and Me6TREN=tris[2\u2010(dimethylamino)ethyl]amine].4H4)]n allows the alkali metal to modify its bonding nature towards the anionic N\u2010heterocyclic ligand from \u03c3\u2010bonding in [(PMDETA)Na(NC4H4)]2 to \u03c0\u2010bonding in the corresponding lower\u2010order and higher\u2010order zincate derivatives .1 fall in the range of 2.272(3)\u2005\u00c5 to 2.411(3)\u2005\u00c5. The sp3 hybridized ring carbon is slightly elevated from the conjugated plane lying at a distance of 2.705(3)\u2005\u00c5 from lithium. The alternating arrangement of short and long bond lengths within C6\u2212C7\u2212C8\u2212C9\u2212N1 \u2005\u00c5 in contrast to those in the solvated structures of Li(tBuDHP) reported earlier by our group .1 is related to some of the diamido\u2010dialkyl lithium aluminate examples in the literature1 is unusual being a structurally well\u2010defined example of a donor\u2010free monomeric ate featuring \u03c0\u2010stabilization.Pleasingly, it was found that when an equivalent amount of  (1\u2009a)  cannot be cast as a substitute to Li(TMP) since one decisive criterion for a TMT system states that the lithium and aluminium species should not co\u2010complex with each other to any significant extent to form an ate in order to display unique reactivity profiles. The lower steric profile of Li(tBuDHP) rules it out of consideration as a partner in trans\u2010metal\u2010trapping chemistry as it readily co\u2010complexes with the organoaluminium moiety. However, the formation of 1 and 1\u2009a can be treated as among the first illustrations of a trapped amido anion with a surrogate hydride as opposed to the trapped carbanions in all previous examples.It may be assumed that Li(tBuDHP) and having recently reported rubidium and caesium aluminyl compounds,tBuDHP). Owing to the practical difficulties involved in the process of isolating a pure batch of heavy alkali metal tert\u2010butoxide, in benzene provided the corresponding alkali metal alkoxides [Rb\u2212OtAm and Cs\u2212OtAm], obtained as white powders upon evacuation of the solvent and other volatiles under reduced pressure (Scheme\u2005tBuDHP) in benzene at room temperature allowed the precipitation of unsolvated hydride surrogates of rubidium [Rb(tBuDHP)] and caesium [Cs(tBuDHP] in quantitative yields. Each compound can be stored under inert conditions as a solid powder after washing away any lithium impurities with benzene. The identities of the above compounds were confirmed by multinuclear NMR spectroscopy (See Supporting Information for NMR characterisation). The dihydropyridyl signals in the 1H\u2005NMR spectra were in the range of 3.2\u2005ppm to 6.7\u2005ppm and comparable to those of the lighter congeners.tBuDHP) and Cs(tBuDHP) respectively in deuterated THF. Following the solubility trend of alkali metal dihydropyridines, Rb(tBuDHP) and Cs(tBuDHP) were found to be insoluble in hydrocarbon solvents. A possible explanation for this observation is that with increase in atomic radii down the group, the tendency to form higher order oligomers/polymers also intensifies.On the back of the progress made with Li2Al(TMP)] to combine with the heavier members of the group one tBuDHPs and remain homogeneous in solution (Scheme\u2005tBuDHP) and [(iBu)2Al(TMP)] produced colourless blocks of crystals after leaving the mixture with slow evaporation of hexane at room temperature. The structure of the compound was determined by single crystal X\u2010ray diffraction studies and identified as [Na(tBuDHP)(TMP)Al(iBu)2]\u221e  contact of 2.977(2)\u2005\u00c5 from a neighbouring dihydropyridyl anion to construct a polymeric zig\u2010zag chain. The asymmetric unit of 2 bears a resemblance to 1 by virtue of having a similar bridging alignment [M\u2212N1\u2212Al\u2212N2] with a distorted tetrahedral geometry at the aluminium centre.Benzene was found to be a suitable medium for [Na(tBuDHP)(TMP)Al(iBu)2] (2\u2009a) were formed  aluminate [(TMEDA)Na(TMP)(iBu)Al(iBu)2]  protons were found to be split into three separate multiplets in the 1H NMR spectrum , of which two protons appear shielded at \u22120.02 (1H) and \u22120.30\u2005ppm (1H) respectively  indicating the close interaction of the sodium centre to the axial H\u2010 atoms of the TMP moiety in the donor\u2010free aluminate. The structures of 2 and 2\u2009a bear significance on the grounds of the paucity of structures of bisamido bridged sodium aluminates with only a few crystallographically characterised examples present in the literature from the Fedyushkin and Chivers groups.[When an equivalent amount of TMEDA was added to a benzene solution of d Figure\u2005\u2010top. Inte Figure\u2005\u2010bottom. s groups.21biBu)Al(iBu)2] .[iBu)2Al(TMP)] induced the deprotonation of one \u03b1\u2010CH3 of a TMP unit to give the monomer [(TMEDA)K(\u03bc\u2010TMP*)(\u03bc\u2010iBu)Al(iBu)], where TMP* represents a CH3\u2010 and NH\u2010deprotonated dianionic variant of TMP.tBuDHP) produced the first donor free bis\u2010amido potassium aluminate in [K(tBuDHP)(TMP)Al(iBu)2]\u221e (3) in a 74\u2009% yield. Similarly, crystals from a Rb\u2212Al combination in benzene were obtained in a yield of 75\u2009% after removing the solvent in vacuo followed by adding hexane to the resultant yellow oil at room temperature. Aluminates 3, and [Rb(tBuDHP)(TMP)Al(iBu)2]\u221e (4) K(\u03bc\u2010amide), which lies opposite to the sp3 carbon (C5) atom [3.926\u2005\u00c5 in 2>3.319\u2005\u00c5 in 3>3.294\u2005\u00c5 in 4]. Contrary to the above observation, it is found that the distances between neighbouring methyl groups (C1) on the tBu substituent and the alkali metal follows a reverse order . While Li prefers to sit \u2018trans\u2019 to the tBu group of the tBuDHP, Na likes to rest itself on the site \u2018cis\u2019 to the tBu group of the tBuDHP ligand. This is evident from the contrasting CH3(TMP)\u22c5\u22c5\u22c5AM contacts Na(TMP)(iBu)Al(iBu)2}iBu)Al(iBu)2}].4 are distinctively shorter than the ones reported earlier by our group in the homoleptic TMEDA solvate [(TMEDA)Rb(TMP)]2.The \u03c0\u2010stabilization offered by the tBuDHP) and [(iBu)2Al(TMP)] in benzene solution could be proved from the comparable 1H\u2005NMR resonances  against those of its lighter siblings, attempts to crystallize the same from its oil were unsuccessful. Addition of hexane to the oily substance resulted in the formation of a sticky solid. The presence of a variety of nitrogen and oxygen donors such as PMDETA, TMEDA, THF or 18\u2010crown\u20106\u2010ether in a hexane suspension of the bimetallic mixture failed to produce crystalline samples suitable for X\u2010ray crystallographic study. However, the solubility of the compound in benzene, points to the effectiveness of the aluminium agent in minimizing the oligomerization of the surrogate caesium hydride.While the formation of a co\u2010complexation product from a mixture of Cs. The electrostatic interaction energy was calculated according to Equation\u2005(1). We minimized basis set superposition error (BSSE) by calculating a counterpoise corrected interaction energy which increased electronic interaction energies of these four complexes by an average of 32\u2005kJ\u2009mol\u22121.It has been well documented that attractive London Dispersion Forces (LDF) influence the stability, structure, and reactivity of organometallic compounds.28b Late\u22121 for lithium to \u2212393\u2005kJ\u2009mol\u22121 for rubidium. As evident from Figure\u2005E) (kJ\u2009mol\u22121) in order of increasing stability=\u2212630.23 (Li)>\u2212511.65 (Na)>\u2212410.02 (K)>\u2212370.45 (Rb)], which is antithetical to the calculated LDF values [Energy (E) (kJ\u2009mol\u22121) in order of increasing stability=\u22124.47 (Li)<\u221215.07 (Na)<\u221218.92 (K)<\u221222.67 (Rb)] . These results support the existence of the observed short contacts [AM\u22c5\u22c5\u22c5H\u2212C(TMP)] in the donor\u2010free heavy alkali\u2010metal aluminates (3 and 4). Surprisingly, considering the high utility of TMP and the numerous structures it is found in,In order to better visualize and understand the myriad of non\u2010covalent interactions (NCI) we used the NCIPlot software with ultrafine integration to generate the representations in Figure\u20051\u20134 at 85\u2009\u00b0C in deuterated benzene. This showed that lithium aluminate 1 is the most stable, with no evidence of MH elimination/rearomatized pyridine formation even after heating for 24\u2005h. However, this study provided evidence of metal hydride elimination, as seen by the appearance of the characteristic 2\u2010t\u2010butylpyridine resonances in the 1H\u2005NMR spectra  over 2\u20133\u2005days. In order to preliminarily test the surrogate hydride reactivity of these aluminates, experiments with the lightest and heaviest aluminates of the series (Li and Cs) were carried out at room temperature in hexane and benzene solution respectively with stoichiometric amounts of benzophenone. Quenching these mixtures with H2O resulted in the precipitation of insoluble hydroxide salts along with the formation of benzhydrol, which was characterised by NMR spectroscopy . However, these results do not explain the origin of the hydride source, since a previous report by our group indicated the availability of masked (\u03b2) hydride on the isobutyl groups bound to aluminium in the reduction of benzophenone, mimicking a Meerwein\u2010Pondorf\u2010Verley type mechanism.1 in C6D6 at room temperature . The appearance of characteristic isobutene resonances (\u03b4=4.73 and 1.59\u2005ppm) in the 1H\u2005NMR spectrum suggests the role of the masked hydride from the isobutyl groups. Addition of a further equivalent of benzophenone to this mixture revealed a complete loss of isobutyl resonances, confirming the aforementioned possibility. To our surprise, addition of a third equivalent of benzophenone at room temperature did not yield any 2\u2010t\u2010butylpyridine. The dihydropyridyl resonances appear shifted compared to both the starting material and also homometallic [Li(tBuDHP)], while the 7Li resonance shifts from \u22122.10 in 1 to 1.90\u2005ppm , suggesting an unidentified bimetallic species is formed. This lack of reactivity of the dihydropyridyl moiety suggests that the presence of the aluminium component provides a stabilizing influence since [Li(tBuDHP)] itself readily reduces benzophenone with concomitant generation of 2\u2010t\u2010butylpyridine. When this experiment was replicated with isolated crystals of the rubidium aluminate (4), the appearance of both isobutene as well as the 2\u2010t\u2010butylpyridine resonances in the 1H NMR spectrum were seen, hinting towards increased surrogate hydride reactivity of the heavier group one aluminates . Resonances at 6.09 and 6.27\u2005ppm in the 1H\u2005NMR spectrum allude to the fact that there are potentially two distinct \u2212OC(H)Ph2 environments in the product which has been witnessed previously in homometallic [(TMP)(Ph2(H)CO)Al(\u03bc\u2010OC(H)Ph2)]2 which shows distinct bridging and terminal resonances.We next attempted to study the stability of these complexes in light of the presence of these stabilizing interactions, by heating samples of the donor free ates tBuDHP)] into the chemistry of aluminates. The dialkyl amido aluminium compound [(iBu)2Al(TMP)] plays a fundamental role as a stabilizer by delivering the alkali metal surrogate hydride [AM(tBuDHP)] into a hydrocarbon solvent when added in stoichiometric quantities. The crystal structures of [Li(tBuDHP)(TMP)Al(iBu)2] (1), [Na(tBuDHP)(TMP)Al(iBu)2]\u221e (2), [K(tBuDHP)(TMP)Al(iBu)2]\u221e (3), and [Rb(tBuDHP)(TMP)Al(iBu)2]\u221e (4) demonstrated that the dihydropyridyl anion can act as a N\u2010heterocyclic group with a surrogate hydride providing stability to the alkali metals through \u03c0\u2010donation. These structures are one of the first in a series of donor free ates with two distinct amido bridges. The difference in the aggregation states is reflected in their solubility. While the lithium congener is soluble in an aliphatic hydrocarbon solvent, it takes an aromatic (benzene) solvent to dissolve the other group one aluminates. The polymers can be broken down into monomeric units by the employment of neutral Lewis base donors as observed during the isolation of [(THF)Li(tBuDHP)(TMP)Al(iBu)2] (1\u2009a) and [(TMEDA)Na(tBuDHP)(TMP)Al(iBu)2] (2\u2009a). Energy calculations on the stable donor free complexes provided us with an insight into the nature of alkali\u2010metal\u2010ligand interactions where a definite trend in increased contribution of attractive London Dispersion Forces can be observed on moving down group one, which is in sharp contrast to the electrostatic forces of attraction. The NCI plots demonstrated that the methylene groups of a saturated TMP ligand can lend stability to the large cations of group one. Preliminary test reactions suggest that the stability imparted on the dihydropyridyl unit as a consequence of the presence of the organoaluminium fragment modifies its reactivity as a metal hydride source, with the degree of modification depending upon the identity of the alkali metal. Our ongoing work is to investigate further this facet of their behaviour as well as to probe other reactivity scenarios in both stoichiometric and catalytic applications.In summary, this study has exported alkali metal dihydropyridines : \u03b4 0.98\u2005ppm , \u03b4 3.83\u2005ppm , \u03b4 4.94\u2005ppm , \u03b4 5.34\u2005ppm , \u03b4 6.27\u2005ppm , \u03b4 7.14\u2005ppm , \u03b4 1.72\u2005ppm , \u03b4 0.92\u2005ppm , \u03b4 0.80\u2005ppm , \u03b4 1.96\u2005ppm , \u03b4 1.47\u20131.54\u2005ppm , \u03b4 1.11\u20131.16\u2005ppm , \u03b4 2.13\u2005ppm , \u03b4 0.19\u20130.35\u2005ppm , \u03b4 0.49\u20130.57\u2005ppm ; 13C {1 H} NMR : \u03b4 147.62\u2005ppm (\u2212CH(6)[DHP]), \u03b4 123.42\u2005ppm (\u2212CH(4)[DHP]), \u03b4 107.16\u2005ppm (\u2212CH(3)[DHP]), \u03b4 99.09\u2005ppm (\u2212CH(5)[DHP]), \u03b4 59.70\u2005ppm (\u2212CH(2)[DHP]), \u03b4 24.76\u2005ppm (\u2212tBu[DHP]), \u03b4 40.68\u2005ppm (quaternary[DHP]), \u03b4 45.45+46.24\u2005ppm (\u03b2\u2010CH2[TMP]), \u03b4 17.81\u2005ppm (\u03b3CH2[TMP]), \u03b4 36.69+38.01\u2005ppm (CH3[TMP]), \u03b4 51.99+51.76\u2005ppm (2\u00d7quaternary[TMP]), \u03b4 26.73\u2005ppm (\u2212CH[iBu]), \u03b4 27.97+28.10\u2005ppm (\u2212CH3[iBu]), The resonances of \u2212CH2[iBu] could not be observed;7Li  \u03b4=\u22121.71\u2005ppm (s).tBuDHP)(TMP)Al(iBu)2)] (1\u2009a)Synthesis of [(THF)Li(: Li(tBuDHP)iBu2AlTMPtBuDHP)(TMP)Al(iBu)]\u221e (2)Synthesis of [Na(: Na(tBuDHP)iBu2AlTMP26H50AlNaN2] (440.66\u2005g\u2009mol\u22121): C 70.87, H 11.44, N 6.36; Found: C 70.80, H 11.36, N 5.98. 1H\u2005NMR : \u03b4 1.18\u2005ppm , \u03b4 3.76\u2005ppm , \u03b4 4.59\u2005ppm , \u03b4 4.74\u2005ppm , \u03b4 5.85\u2005ppm , \u03b4 7.11\u2005ppm , \u03b4 1.35\u2005ppm , \u03b4 \u22120.30\u2005ppm , \u03b4 \u22120.02\u2005ppm , \u03b4 1.73\u2005ppm , \u03b4 1.09+1.15+1.39+1.51\u2005ppm , \u03b4 1.09\u2005ppm , \u03b4 1.43\u20131.47\u2005ppm , \u03b4 2.46\u2005ppm , \u03b4 0.38\u20130.87\u2005ppm ; 13C {1 H} NMR : \u03b4 147.65\u2005ppm (\u2212CH(6)[DHP]), \u03b4 125.41\u2005ppm (\u2212CH(4)[DHP]), \u03b4 105.02\u2005ppm (\u2212CH(3)[DHP]), \u03b4 94.96\u2005ppm (\u2212CH(5)[DHP]), \u03b4 59.96\u2005ppm (\u2212CH(2)[DHP]), \u03b4 25.66\u2005ppm (\u2212tBu[DHP]), \u03b4 41.55\u2005ppm (quaternary[DHP]), \u03b4 45.27\u2005ppm (\u03b2\u2010CH2[TMP]), \u03b4 17.72\u2005ppm (\u03b3CH2[TMP]), \u03b4 37.56+38.80\u2005ppm (CH3[TMP]), \u03b4 27.34+27.51\u2005ppm (\u2212CH[iBu]), \u03b4 28.24+28.59+29.27+29.94\u2005ppm (\u2212CH3[iBu]), The resonances of \u2212CH2[iBu] and quatenary[TMP] could not be observed.tBuDHP)(TMP)Al(iBu)] (2\u2009a)Synthesis of [(TMEDA)Na(: Na(tBuDHP)iBu2AlTMPtBuDHP)(TMP)Al(iBu)2] (2a) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for C32H66AlN4Na (556.86\u2005g\u2009mol\u22121): C 69.02, H 11.95, N 10.06; Found: C 68.98, H 11.73, N 7.59. 1H\u2005NMR : \u03b4 0.94\u2005ppm , \u03b4 3.74\u2005ppm , \u03b4 4.70\u2005ppm , \u03b4 4.76\u2005ppm , \u03b4 6.02\u2005ppm , \u03b4 7.04\u2005ppm , \u03b4 2.37\u2005ppm , \u03b4 2.27\u2005ppm , \u03b4 1.70\u2005ppm , \u03b4 1.31\u20131.41\u2005ppm , \u03b4 1.04\u2005ppm , \u03b4 2.06\u2005ppm , \u03b4 0.04\u20130.47\u2005ppm ; 13C {1 H} NMR : \u03b4 147.06\u2005ppm (\u2212CH(6)[DHP]), \u03b4 123.98\u2005ppm (\u2212CH(4)[DHP]), \u03b4 105.62\u2005ppm (\u2212CH(3)[DHP]), \u03b4 93.75\u2005ppm (\u2212CH(5)[DHP]), \u03b4 60.21\u2005ppm (\u2212CH(2)[DHP]), \u03b4 25.19\u2005ppm (\u2212(CH3)3[DHP]), \u03b4 41.32\u2005ppm (quaternary[DHP]), \u03b4 57.91\u2005ppm (\u2212CH2[TMEDA]), \u03b4 46.73\u2005ppm (\u2212CH3[TMEDA]), \u03b4 45.83\u2005ppm (\u03b2\u2010CH2[TMP]), \u03b4 18.16\u2005ppm (\u03b3CH2[TMP]), \u03b4 26.09\u2005ppm (CH3[TMP]), \u03b4 51.65\u2005ppm (quaternary[TMP]), \u03b4 26.92+27.03\u2005ppm (\u2212CH[iBu]), \u03b4 27.97+28.60+29.06\u2005ppm (\u2212CH3[iBu]), The resonances of \u2212CH2[iBu] could not be observed.tBuDHP)(TMP)Al(iBu)]\u221e (3)Synthesis of  (3) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for [C26H50AlKN2] (456.77\u2005g\u2009mol\u22121): C 68.37, H 11.03, N 6.13; Found: C 67.84, H 9.98, N 4.67. 1H\u2005NMR : \u03b4 1.25\u2005ppm 3[DHP]+6H, \u2212CH3[TMP]+2H, \u03b2\u2010CH2[TMP]), \u03b4 3.79\u2005ppm , \u03b4 4.54\u2005ppm , \u03b4 4.67\u2005ppm , \u03b4 5.74\u2005ppm , \u03b4 7.04\u2005ppm , \u03b4 1.38\u2005ppm , \u03b4 0.87\u2005ppm , \u03b4 1.47\u2005ppm , \u03b4 2.50\u2005ppm , \u03b4 0.41\u20130.83\u2005ppm ; 13C {1 H} NMR : \u03b4 147.92\u2005ppm (\u2212CH(6)[DHP]), \u03b4 125.67\u2005ppm (\u2212CH(4)[DHP]), \u03b4 104.02\u2005ppm (\u2212CH(3)[DHP]), \u03b4 95.18\u2005ppm (\u2212CH(5)[DHP]), \u03b4 66.28\u2005ppm (\u2212CH(2)[DHP]), \u03b4 26.08\u2005ppm (\u2212tBu[DHP]), \u03b4 41.78\u2005ppm (quaternary[DHP]), \u03b4 18.13\u2005ppm (\u03b3CH2[TMP]), \u03b4 51.50\u2005ppm (quaternary[TMP]), \u03b4 27.44+27.73\u2005ppm (\u2212CH[iBu]), \u03b4 28.44+28.76+29.63+29.88\u2005ppm (\u2212CH3[iBu]). The resonances of \u2212CH2[iBu] could not be observed. The resonances of \u03b2\u2010CH2[TMP] and \u2212CH3[TMP] were not assigned due to overlap of the methyl signals (from TMP and iBu groups) in 1H13C\u2010HSQC NMR spectrum.iBu)]\u221e (4)Synthesis of  (4) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for [C26H50AlRbN2] (503.14\u2005g\u2009mol\u22121): C 62.07, H 10.02, N 5.57; Found: C 61.75, H 9.73, N 4.62. 1H\u2005NMR : \u03b4 1.30\u2005ppm , \u03b4 3.85\u2005ppm , \u03b4 4.56\u2005ppm , \u03b4 4.61\u2005ppm , \u03b4 5.66\u2005ppm , \u03b4 7.03\u2005ppm , \u03b4 0.83\u2005ppm , \u03b4 1.63\u2005ppm , \u03b4 1.34\u2005ppm , \u03b4 1.48\u2005ppm , \u03b4 2.50\u2005ppm , \u03b4 0.43\u20130.75\u2005ppm ; 13C {1 H} NMR : \u03b4 148.13\u2005ppm (\u2212CH(6)[DHP]), \u03b4 125.87\u2005ppm (\u2212CH(4)[DHP]), \u03b4 103.95\u2005ppm (\u2212CH(3)[DHP]), \u03b4 94.94\u2005ppm (\u2212CH(5)[DHP]), \u03b4 60.59\u2005ppm (\u2212CH(2)[DHP]), \u03b4 26.30\u2005ppm (\u2212tBu[DHP]), \u03b4 41.88\u2005ppm (quaternary[DHP]), \u03b4 43.66\u2005ppm (\u03b2\u2010CH2[TMP]), \u03b4 18.33\u2005ppm (\u03b3CH2[TMP]), \u03b4 33.69+34.08\u2005ppm (CH3[TMP]), \u03b4 51.55\u2005ppm (quaternary[TMP]), \u03b4 27.41+27.75\u2005ppm (\u2212CH[iBu]), \u03b4 28.58+29.09+29.68+29.76\u2005ppm (\u2212CH3[iBu]), The resonances of \u2212CH2[iBu] and quaternary[TMP] could not be observed.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the crystal structure, centrosymmetric mol\u00adecules are linked through inter\u00admolecular N\u2014H\u22efO hydrogen bonds into sheets extending parallel to (0 2(en)2)] , has been synthesized. The complex mol\u00adecules are located on inversion centers. Two DNBA anions monodentately coordinate the CdII atom through an oxygen atom of the carboxyl\u00adate group while two en mol\u00adecules coordinate in a chelate fashion, resulting in a distorted O2N4 coordination set. There is a weak intra\u00admolecular hydrogen bond of 3.099\u2005(4)\u2005\u00c5 between the non-coordinating oxygen atom of the carboxyl\u00adate group and one of the en amine groups. Three relatively weak inter\u00admolecular N\u2014H\u22efO hydrogen bonds associate complex mol\u00adecules into sheets extending parallel to  and H\u22efH (21.1%) inter\u00adactions.During systematic investigations of bioavailability and biological action enhancement of well known compounds with low bioactivity, a new mixed-ligand metal complex, [Cd(DNBA) It is a well known bidentate chelating ligand for coordination complexes  to 102.66\u2005(12)\u00b0, indicating a rather strong distortion from the ideal octa\u00adhedral shape. The conformation of the complex mol\u00adecule is stabilized through a weak intra\u00admolecular hydrogen bond [3.099\u2005(4)\u2005\u00c5 and 143\u2005(3)\u00b0] between the N4\u2014H4A donor and the O2 acceptor (Table\u00a01S(6). Most coplanar with the aromatic ring is the N1O2 nitro group [dihedral angle of 3.873\u2005(3)\u00b0] while the carboxyl\u00adate group is considerably twisted from the aromatic ring [dihedral angle = 19.332\u2005(9)\u00b0]. The arrangement of the N2O2 nitro group is inter\u00admediate between the latter two, the corresponding dihedral angle being 13.529\u2005(6)\u00b0.In the crystal of the title compound, the complex mol\u00adecules are located on inversion centers. Two symmetry-related DNBA anions monodentately coordinate to Cdms Fig.\u00a01. The bonr Table\u00a01 definingA\u22efO4i and N4\u2014H4B\u22efO4ii hydrogen bonds define rings with graph-set notation via N3\u2014H3B\u22efO5iii hydrogen bonds, forming sheets extending parallel to (0Cg1\u22efCg1 = 3.715\u2005(3)\u2005\u00c5, slippage = 1.608\u2005\u00c5, symmetry operation: 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z; Cg1 is the centroid of the phenyl (C1\u2013C6) ring].There are three relatively weak inter\u00admolecular hydrogen bonds in the crystal structure Table\u00a01. N4\u2014H4A\u22ef1) Fig.\u00a02. The sheCrystal Explorer 17.5  analysis was carried out using rm Fig.\u00a03 shows thet al., 20162(en)2)] complex. The silver complexes with refcodes EQOKEA 2  was slowly added an ethanol solution (4\u2005ml) containing en (60 \u03bcl) and DNBA  under constant stirring. A colourless crystalline product was obtained at room temperature by slow solvent evaporation after 6\u2005d. Single crystals for X-ray structure determination were selected from this product. Yield: 65%. Elemental analysis for C18H22CdN8O12 (654.83): calculated C 33.02; H 3.39; N 17.11%; found: C 32.96; H 3.32; N 17.08%.To an aqueous solution (2.5\u2005ml) of Cd I. DOI: 10.1107/S2414314620008433/wm4132Isup2.hklStructure factors: contains datablock(s) I. DOI: 2011747CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-022-13747-4, published online 11 June 2022Correction to: The original version of this\u00a0Article contained an error in the y-axis\u00a0label of\u00a0Figure\u00a04(C), where \u201cstereoacuity improvement (%)\u201d should read \u201cstereoacuity improvement\u201d.The original Figure\u00a0The original Article has been corrected."}
{"text": "In the crystal, corrugated layers parallel to the ab plane are formed by a combination of C\u2014H\u22efO, C\u2014H\u22ef\u03c0(ring) and \u03c0-stacking inter\u00adactions.The inner part of the ester substituent is nearly perpendicular to the di\u00adhydro\u00adpyridazine ring while the  17H20N2O4, the inner part of the ester substituent is nearly perpendicular to the di\u00adhydro\u00adpyridazine ring, forming a dihedral angle of 83.21\u2005(7)\u00b0. In the crystal, inversion dimers are formed by pairwise C\u2014H\u22efO inter\u00adactions with the dimers connected into chains extending along the b-axis direction by C\u2014H\u22ef\u03c0(ring) inter\u00adactions. The chains are connected by \u03c0-stacking inter\u00adactions to give corrugated layers parallel to the ab plane. The terminal ethyl group is disordered over two two sets of sites with the major component having a site occupancy factor of 0.715\u2005(10)In the title mol\u00adecule, C This latter angle indicates that the inner end of the substituent on N2 is nearly perpendicular to the tetra\u00adhydro\u00adpyridazine ring. The C2\u2014C3\u2014C5\u2014C6 torsion angle of \u22129.4\u2005(2)\u00b0 indicates that the centroid of the 4-meth\u00adoxy\u00adphenyl ring is only slightly below the plane of the pyridazine ring. This conformation appears to be the result of the inter\u00admolecular \u03c0-stacking inter\u00adaction (see below).B\u22efO1 inter\u00adactions (Table\u00a01b-axis direction by C16\u2014H16B\u22efCg1 inter\u00adactions (Table\u00a01i\u2013C11i rings [symmetry code: (i) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0ab plane -one pre\u00adcursor. To this pyridazine derivative (0.05\u2005mol) was added potassium carbonate (0.1\u2005mmol), tetra\u00adbutyl\u00adammonium bromide (0.01\u2005mmol) and 2-ethyl bromo\u00adacetate (0.1\u2005mol) in di\u00admethyl\u00adformamide (20\u2005ml). The mixture was stirred for 24\u2005h at room temperature. At the end of the reaction, the solution was filtered and the solvent evaporated under reduced pressure. The residue was washed with water and methyl\u00adene chloride. The solvent was removed and colourless blocks of the title compound were obtained by recrystallization of the product from its acetone solution.A mixture of 3-(4-meth\u00adoxy\u00adbenzyl\u00adidene)-4-oxo\u00adpenta\u00adnoic acid (0.05\u2005mol) and hydrazine hydrate (0.1\u2005mol) in ethanol (100\u2005ml) was refluxed for 2\u2005h. The precipitate that formed was filtered off and recrystallized from acetone solution to obtain the 5-(4-meth\u00adoxy\u00adbenz\u00adyl)-6-methyl\u00adpyridazin-3(2\u22121): 1743 , 1660 (C=ON), 1599 (C=C), 1205 (C\u2014N), 1011 and 1145 . 1H NMR (p.p.m.): 1.23 ; 2.22 ; 2.33 ; 3.85 ; 4.17 ; 4.87 ; 6.48 ; 6.93\u20136.96 ; 7.25\u20137.27 . 13C NMR (p.p.m.): 14.11 (CH3); 21.03 ; 25.21 ; 37.67 (CH2); 51.34 (CH2); 60.95 (CH2); 127.13\u2013127.44 (CH aromatic); 129.13\u2013130.35 (CH aromatic); 132.12 (C\u2014C\u03b1 aromatic); 136.51 ; 138.49 ; 144.97 ; 147.17 (C=N); 161.19 ; 169.52 .Yield 79%; m.p. 406\u2013408\u2005K. IR  global, I. DOI: 10.1107/S241431462200582X/tk4077Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S241431462200582X/tk4077Isup3.cmlSupporting information file. DOI: 2175897CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion has an N4Cl2 octa\u00adhedral coordination sphere defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridyl\u00adpyrazine ligand, one N atom of the pyridine ligand and two Cl\u2212 anions.The central Ni 2(C5H5N)(C24H16N6)], the NiII ion is six-coordinated in a distorted octa\u00adhedral coordination environment defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridyl\u00adpyrazine ligand, one N atom of the pyridine ligand and two Cl\u2212 anions, with the latter being mutually trans. The complex is disposed about a twofold rotation axis along the a axis. The complex molecules are connected in the crystal via C\u2014H\u22efCl, C\u2014H\u22efN and \u03c0\u2013\u03c0 [closest inter-centroid separation = 3.7446\u2005(14)\u2005\u00c5 between pyridyl rings].In the title complex, [NiCl The Ni\u2014N[pyrazine\u00ad(N1) or pyrid\u00adyl] bond lengths are roughly equivalent, with distances of 2.008\u2005(3) \u2013 2.1026\u2005(19)\u2005\u00c5. The pyrazine ring (N1\u2014C1i) slightly deviates from planarity, with a maximum deviation of 0.057\u2005(2)\u2005\u00c5 for the C2 atom from the least-squares plane of the ring. The dihedral angles between the nearly planar pyridyl rings and the least-squares plane of their carrier pyrazine ring are 14.90\u2005(4)\u00b0 for the coordinating pyridyl ring (N3\u2014C7) and 54.42\u2005(9)\u00b0 for the non-coord\u00adinating pyridyl ring (N4\u2014C12), respectively. The dihedral angle between the pyrazine ring and the pyridine ligand (N5\u2014C13i) is 57.8\u2005(1)\u00b0.In the title complex, the central Nins Fig.\u00a01. The comCg1 (the centroid of the ring N3/C3\u2013C7) and Cg1ii [symmetry code: (ii) x, x\u00a0\u2212\u00a0y, \u2212z\u00a0+\u00a0In the crystal, the complex displays numerous inter- and intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent six-membered rings. The most significant inter\u00adaction of this kind is that between s Table\u00a01 that cons Table\u00a01.2\u00b76H2O  in ethanol (20\u2005ml) was added 2,3,5,6-tetra-2-pyridyl\u00adpyrazine , followed by stirring for 24\u2005h at rooom temperature. The formed precipitate was separated by filtration, washed with ethanol and acetone, and dried at 323\u2005K, to give a brown powder (0.5045\u2005g). Brown crystals suitable for X-ray analysis were obtained by slow evaporation from its pyridine/N,N-di\u00admethyl\u00adformamide (DMF) solution at 333\u2005K.To a solution of NiClCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621000948/wm4144sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621000948/wm4144Isup2.hklStructure factors: contains datablock(s) I. DOI: 2058988CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Yarrowia\u2009lipolytica as an alternative host for ergothioneine production. We expressed the biosynthetic enzymes EGT1 from Neurospora\u2009crassa and EGT2 from Claviceps\u2009purpurea to obtain 158\u2009mg\u00b7L\u22121 of ergothioneine in small\u2010scale cultivation, with an additional copy of each gene improving the titer to 205\u2009mg\u00b7L\u22121. The effect of phosphate limitation on ergothioneine production was studied, and finally, a phosphate\u2010limited fed\u2010batch fermentation in 1\u2009L bioreactors yielded 1.63\u2009\u00b1\u20090.04\u2009g\u00b7L\u22121 ergothioneine in 220\u2009h, corresponding to an overall volumetric productivity of 7.41\u2009mg\u00b7L\u22121\u00b7h\u22121, showing that Y.\u2009lipolytica is a promising host for ergothioneine production.Ergothioneine is a naturally occurring antioxidant that has shown potential in ameliorating neurodegenerative and cardiovascular diseases. In this study, we investigated the potential of the Crabtree\u2010negative, oleaginous yeast  Yarrowia\u2009lipolytica is a viable host to produce the antioxidant ergothioneine. Yarrowia\u2009lipolytica could reach ergothioneine production levels comparable to or exceeding those reported in other hosts, such as Escherichia\u2009coli and Saccharomyces\u2009cerevisiae, by genomic integration of the ergothioneine biosynthetic pathway and fed\u2010batch fermentation on mineral medium.Here, we report that the oleaginous yeast  CDW, cell dry weightERG, ergothioneineMES, 2\u2010(N\u2010morpholino)ethanesulfonic acidSAM, S\u2010adenosylmethionineThe amino acid\u2010derived nutraceutical ergothioneine (ERG) has recently gained much scientific interest for its potential application in preventing or treating neurodegenerative and cardiovascular diseases , 2. CurrS\u2010adenosylmethionine  was bought from Sigma\u2010Aldrich . Synthetic genes were ordered through the GeneArt Gene Synthesis service of Thermo Fisher Scientific  or the custom gene synthesis service of IDT . Sequencing results were obtained through Eurofins Genomics  using their Mix2Seq kit.The n ST6512  was used\u22121 of glucose, 7.5\u2009g\u00b7L\u22121 of (NH4)2SO4, 14.4\u2009g\u00b7L\u22121 of KH2PO4, 0.5\u2009g\u00b7L\u22121 of MgSO4.7H2O, 2\u2009mL\u00b7L\u22121 of trace metal solution, and 1\u2009mL\u00b7L\u22121 of vitamin solution, adjusted to pH 6.0 using 2\u2009m of NaOH. Mineral medium without phosphate was prepared using the same recipe, but KH2PO4 was substituted with the same concentration of 2\u2010(N\u2010morpholino)ethanesulfonic acid (MES) hydrate. High glucose mineral medium without phosphate consisted of 50\u2009g\u00b7L\u22121 of glucose, 20\u2009g\u00b7L\u22121 of (NH4)2SO4, 30\u2009g\u00b7L\u22121 of MES hydrate, 1.25\u2009g\u00b7L\u22121 of MgSO4.7H2O, 5\u2009mL\u00b7L\u22121 of trace metal solution, and 2.5\u2009mL\u00b7L\u22121 of vitamin solution, adjusted to pH 6.0 using 2\u2009m of NaOH.Mineral medium consisted of 20\u2009g\u00b7L\u22121 of CaCl2.2H2O, 4.5\u2009g\u00b7L\u22121 of ZnSO4.7H2O, 3\u2009g\u00b7L\u22121 of FeSO4.7H2O, 1\u2009g\u00b7L\u22121 of H3BO3, 1\u2009g\u00b7L\u22121 of MnCl2.4H2O, 0.4\u2009g\u00b7L\u22121 of Na2MoO4.2H2O, 0.3\u2009g\u00b7L\u22121 of CoCl2.6H2O, 0.1\u2009g\u00b7L\u22121 of CuSO4.5H2O, 0.1\u2009g\u00b7L\u22121 of KI, and 15\u2009g\u00b7L\u22121 of EDTA. Vitamin solution consisted of 50\u2009mg\u00b7L\u22121 of biotin, 200\u2009mg\u00b7L\u22121 of p\u2010aminobenzoic acid, 1\u2009g\u00b7L\u22121 of nicotinic acid, 1\u2009g\u00b7L\u22121 of calcium pantothenate, 1\u2009g\u00b7L\u22121 of pyridoxine HCl, 1\u2009g\u00b7L\u22121 of thiamine HCl, and 25\u2009g\u00b7L\u22121 of myo\u2010inositol.Trace metal solution consisted of 4.5\u2009g\u00b7LY.\u2009lipolytica was performed using the EasyCloneYALI method . , 9. Y.\u2009lY.\u2009lipolytica. Phosphate limitation was a viable strategy to limit biomass accumulation in the bioreactors. ERG titer reached 1.63\u2009\u00b1\u20090.04\u2009g\u00b7L\u22121 after 220\u2009h of fermentation in mineral medium with glucose as the only carbon source.In conclusion, we integrated the ERG biosynthesis pathway into oleaginous yeast SH, DBK, and IB are named inventors on a European Patent application covering parts of the work described above.IB and DBK conceived the study; IB and JLM supervised the study; SAH, IHJ, and JLM designed the experiments; SAH, IHJ, and MR performed the experiments and data analysis; SAH and IB wrote the manuscript; SAH, IB, DBK, IHJ, and JLM reviewed and revised the manuscript; IB and JLM provided resources for the study; IB acquired funding for the study.Fig.\u2009S1. Bacterial ergothioneine biosynthesis pathway.Fig.\u2009S2. The effect of phosphate limitation on the growth of the ergothioneine\u2010producing Yarrowia lipolytica strain ST10264.Fig.\u2009S3. Ergothioneine production and biomass accumulation of ST10264 under phosphate\u2010limited fed\u2010batch conditions in a single 1 L bioreactor with an initial amount of 240\u2009mg KH2PO4.Table\u2009S1. List with genes and their DNA sequences used in this paper.Table\u2009S2. List of primers used in this study for cloning purposes.Table\u2009S3. List of primers used in this study for sequencing.Table\u2009S4. List of biobricks used in this study.Table\u2009S5. List of plasmids used in this study, made by USER cloning.Table\u2009S6. List of strains used in this study.Click here for additional data file."}
{"text": "The crystal structure of the \u2018magic\u2019 mushroom natural product baeocystin is reported for the first time. N-methyl\u00adtryptamine {systematic name: 3-[2-(methylazaniumyl)ethyl]-1H-indol-4-yl hydrogen phosphate}, C11H15N2O4P, has a single zwitterionic mol\u00adecule in the asymmetric unit. The mol\u00adecule has an intra\u00admolecular N\u2014H\u22efO hydrogen bond between the ammonium cation and the hydro\u00adphosphate anion. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds into a three-dimensional network.The title compound, baeocystin or 4-phosphor\u00adyloxy- This minor tryptamine natural product was first isolated from the Psilocybe baeocystis mushroom in 1968 , the metabolite of baeocystin, as a Psilocybe natural product  in mice, which is strongly correlated with 5-HT2A receptor-mediated psychoactive effects \u00b0. The phosphor\u00adyloxy group is similarly turned away from the indole plane, with a C5\u2014C6\u2014O1\u2014P1 torsion angle of 33.8\u2005(3)\u00b0. Both groups are turned to the same side of the indole ring, which is likely supported by an intra\u00admolecular N2\u2014H2A\u22efO4 hydrogen bond  distance of 0.87\u2005(1)\u2005\u00c5, N\u2014H(ammonium) distances of 0.90\u2005(1)\u2005\u00c5, and an O\u2014H distance of 0.90\u2005(1)\u2005\u00c5. Isotropic displacement parameters were set to 1.2 Ueq of the parent nitro\u00adgen atoms and 1.5 Ueq of the parent oxygen atom. All other hydrogen atoms were placed in calculated positions . Isotropic displacement parameters were set to 1.2 Ueq of the parent carbon atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022004467/hb8018sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004467/hb8018Isup2.hklStructure factors: contains datablock(s) I. DOI: 2169087CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound crystallizes with two mol\u00adecules in the asymmetric unit. In the crystal, asymmetric, bifurcated N\u2014H\u22ef hydrogen bonds link the mol\u00adecules into [100] chains. The packing is consolidated by weak C\u2014H\u22efO inter\u00adactions. 25H25N3O4, crystallizes with two mol\u00adecules in the asymmetric unit. In both mol\u00adecules, the central ethane hydrazide moiety is almost planar. In the crystal, asymmetric, bifurcated N\u2014H\u22ef hydrogen bonds link the mol\u00adecules into [100] chains. The packing is consolidated by weak C\u2014H\u22efO inter\u00adactions.The title compound, C This latter ring and the C1A toluyl ring are almost perpendicular, with a dihedral angle of 82.1\u2005(1)\u00b0The title compound crystallizes with two mol\u00adecules, B, the central ethane hydrazide moiety N2B/N3B/C17B/O3B is also close to planar, with an r.m.s. deviation of 0.01\u2005\u00c5 for the fitted atoms. The equivalent dihedral angles to those in mol\u00adecule A are 13.3\u2005(2), 80.5\u2005(2) and 86.1\u2005(1)\u00b0, respectively.For mol\u00adecule A and B mol\u00adecules into a zigzag chain propagating in the a-axis direction, as shown in Fig.\u00a02In the crystal, bifurcated, asymmetric N\u2014H\u22ef hydrogen bonds Table\u00a01 link altet al., 2004o-tolyl groups at the other end of the mol\u00adecule: in the current structure these are 82.1\u2005(1) and 86.1\u2005(1)\u00b0 while in JUFCIY the equivalent angles are 46.98\u2005(5) and 48.23\u2005(4)\u00b0.A search for related structures resulted in two close matches. The first is the parent azide from which the current structure is derived (Chopra E)-2-(Meth\u00adoxy\u00adimino)-2-{2-[(2-methyl\u00adphen\u00adoxy)meth\u00adyl]phen\u00adyl}ethano\u00adhydrazide  was refluxed for 8\u2005h with p-meth\u00adoxy\u00adbenzaldehyde  in 20\u2005ml of absolute ethanol with the addition of 5 drops of glacial acetic acid to obtain a white-colored product. This was dissolved in DMSO and, by the process of slow evaporation, colourless needles of the title compound grew. I. DOI: 10.1107/S2414314620010603/hb4356Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620010603/hb4356Isup3.cmlSupporting information file. DOI: 2020760CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title hydro\u00adchloride salt, the cation shows an unusually long Si\u2014C bond length. In the crystal, the cations and anions are linked by N\u2014H\u22efCl hydrogen bonds to generate [001] chains. N-{[Diphen\u00adyl(vin\u00adyl)sil\u00adyl]meth\u00adyl}-2-methyl\u00adpropan-2-amine, C19H25NSi, is a newly synthesized secondary amino\u00admethyl\u00adsilane that can be used, for example, to study carboli\u00adthia\u00adtion reactions of vinyl\u00adsilanes. Because the neutral compound did not crystallize well, the hydro\u00adchloride salt, C19H26NSi+\u00b7Cl\u2212, was formed, in which the two chloride ions in the asymmetric unit have crystallographic + species. In the crystal, the cations and anions are linked by N\u2014H\u22efCl hydrogen bonds to generate [001] chains. To further investigate the inter\u00admolecular inter\u00adactions, a Hirshfeld surface analysis was performed, which showed that H\u22efH, C\u22efH/H\u22efC and H\u22efCl/Cl\u22efH contacts contribute 70.4, 20.0 and 8.3%, respectively. Because the (amino\u00admeth\u00adyl)silane 1 did not crystallize well, the hydro\u00adchloride salt 2 was formed to characterize the compound via X-ray diffraction. For example, the newly synthesized (amino\u00admeth\u00adyl)vinyl\u00adsilane 1, C19H25NSi, can be used for investigations of a carboli\u00adthia\u00adtion reaction of the silane\u2019s vinyl group via lithiumalkyls. The received product can be used for the synthesis of functionalized alcohols by a Tamao oxidation silanes known to date because the synthesis is not feasible due to the high energy requirement and reaction time. With the assistance of a 2.2 crystallized in a few minutes from an aqueous 1\u2005M HCl solution of 1 at room temperature as a hydro\u00adchloride salt, C19H26NSi+\u00b7Cl\u2212, in the form of colorless needles in the centrosymmetric space group P21/n. The mol\u00adecular structure is illustrated in Fig.\u00a01Compound 3sp\u2014SiX3 compounds \u00b0, which is caused by the steric repulsion of the aromatic hydrogen atoms. The Si1\u2014C1 bond length is 1.8577\u2005(11)\u2005\u00c5 and C1\u2014C2 is 1.3293\u2005(16)\u2005\u00c5; the latter is positioned at the end of the default range of Csp2\u2014Csp2 bonds, which lie between 1.299 and 1.328\u2005\u00c5.The Si1\u2014C15 bond length in the cation is 1.9117\u2005(10)\u2005\u00c5, which is slightly longer than the average for an Si\u2014C bond and the Si1\u2014C15\u2014N1 bond angle is 116.21\u2005(7)\u00b0. The Si\u2014C bond lengths are normally in the range of 1.857 to 1.905\u2005\u00c5 for CA\u2014N1\u2014H1B), the angles between the C atoms and the H atoms are 107.8\u2005(10)\u00b0 (H1B\u2014N1\u2014C15) and 109.6\u2005(9)\u00b0 (H1A\u2014N1\u2014C15). Between the carbon atoms, the angle is 117.10\u2005(7)\u00b0 (C15\u2014N1\u2014C16). All angles vary slightly from the ideal tetra\u00adhedron angles of 109.5\u00b0: the large C\u2014N\u2014C angle results from the bigger space requirement of the carbon atoms in comparison to the H atoms. The sum of angles around the nitro\u00adgen atom is 441.7\u00b0, so the overall structure is distorted tetra\u00adhedral. The bond length between N1 and C15 is 1.4928\u2005(12)\u2005\u00c5 and it is 1.5330\u2005(13)\u2005\u00c5 between N1 and C16. In the literature, C3sp\u2014N bond lengths are in the range of 1.4816 to 1.5034\u2005\u00c5, so the N1\u2014C16 bond is slightly extended.The cationic nitro\u00adgen center features a slightly disordered tetra\u00adhedral geometry. The angle between the hydrogen atoms is 107.2\u2005(13)\u00b0 \u2005\u00c5. This may be due to the different surroundings of the Cl1 and Cl2 ions in the crystal. As shown in Fig.\u00a03para-hydrogen atoms H6 with a C6\u22efCl1 distance of 4.0013\u2005(11)\u2005\u00c5 while Cl2 accepts two weak, near linear hydrogen-bond contacts [C7\u2014H7\u22efCl2: 165.74\u2005(7)\u00b0] from the aromatic meta-hydrogen atoms H7 with a C7\u22efCl2 distance of 3.9419\u2005(12)\u2005\u00c5. Both contacts are formed by the same aromatic ring. The bond angle for N1\u2014H1B\u22efCl2 is 164.0\u2005(13)\u00b0, compared to 172.8\u2005(13)\u00b0 for N1\u2014H1A\u22efCl1. They differ from the optimal angle of 180\u00b0 because of the different surroundings in the crystal packing.In the extended structure of 2 Fig.\u00a02, the cat2 Fig.\u00a02 to generdnorm in the range from \u22120.54 to 1.49 arbitrary units, generated by CrystalExplorer2021  and D12(3), which means that the hydrogen bond extends from N1\u2014H1A\u22efCl1 to another H1A\u2014N1 grouping of a neighboring mol\u00adecule. H2 can also be assigned D11(2) and D12(3) -2-meth\u00adoxy\u00admethyl-1-[1-phenyl\u00adeth\u00adyl(dimeth\u00adyl)sil\u00adyl\u00admeth\u00adyl]pyrrolidinium iodide, C17H30NOSi+\u00b7I\u2212 \u2005\u00c5] and the Si\u2014C\u2014N bond angle is comparable [115.86\u2005(14)\u00b0]. The lengths between the carbon atoms and the cationic nitro\u00adgen center are similar to the corresponding bond lengths in 2 [1.498\u2005(3) and 1.494\u2005(3)\u2005\u00c5].In LAGLUE, the N\u2014H\u22efCl hydrogen bond has a slightly longer N\u22efCl separation (3.124\u2005\u00c5) than compound 2 but the Si\u2014C\u2014N bond angle is similar [114.9\u2005(2)\u00b0] and the C\u2014N bond is a bit extended [1.505\u2005(6)\u2005\u00c5]. This could be caused by the ring strain of the aziridine ring and the electron-withdrawing effect of the (nitro\u00adphen\u00adyl)sulfonyl group located at the nitro\u00adgen center. In addition, the Si\u2014Csp2 bond length is 1.859\u2005(7)\u2005\u00c5, which is only slightly longer that the value for 2.In WOLSEY, the Si\u2014C distance of 1.871\u2005(4)\u2005\u00c5 is shorter than in Finally, in AGILIL, the Si\u2014C bond length is slightly shorter [1.907\u2005(7)\u2005\u00c5] and the Si\u2014C\u2014N bond angle is slightly extended [120.8\u2005(4)\u00b0], which is caused by the cyclic structure of the compound. The C\u2014N distance is equal [1.498\u2005(8)\u2005\u00c5] and the cyclic N\u2014C bond lengths marginally shorter [1.509\u2005(8) and 1.516\u2005(8)\u2005\u00c5], again due to the cyclic structure.+) to 2. In WAVXAW and DAFKUT, the Si\u2014C bond lengths are 1.9074\u2005(11) and 1.907\u2005(3)\u2005\u00c5, respectively, comparable to the value in 2. These extended bond lengths are due to the same electronic effects already described.The structures of WAVXAW and DAFKUT contain a similar structure motive  was added to N-{[diphen\u00adyl(vin\u00adyl)sil\u00adyl]meth\u00adyl}-2-methyl\u00adpropan-2-amine (1)  at room temperature. The product (2) was formed after five minutes as colorless needles.The reaction scheme for the synthesis of compound 6.A and H1B were positioned geometrically (C\u2014H = 0.95\u20131.00\u2005\u00c5) and refined using a riding model, with Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022009112/hb8033sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022009112/hb8033Isup2.hklStructure factors: contains datablock(s) I. DOI: 2207007CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "IV\u2014S bond lengths. The packing of the complexes enable inter\u00admolecular inter\u00adactions between the qdt ligands  and an amine hydrogen atom (hydrogen bonding) or other qdt ligands (\u03c0\u2013\u03c0 stacking).The title compound exhibits typical Pt 8H4N2S2)2(C5H6N2)2]\u00b7C2H6OS or trans-[Pt(4-ap)2(qdt)2]\u00b7dmso  the centrosymmetric complex exhibits Pt\u2014S distances in agreement with other PtIV\u2014S bond lengths found in platinum(IV) di\u00adthiol\u00adene complexes. The qdt ligands have inter\u00admolecular inter\u00adactions with an amine hydrogen atom on a 4-ap ligand (hydrogen bonding) and have sandwich \u03c0\u2013\u03c0 inter\u00adactions with a neighboring qdt ligand.In the structure of the title solvated complex, [Pt(C These distances are similar to those in other platinum(IV) complexes containing bis\u00ad(di\u00adthiol\u00adene) ligands and either trans-bis\u00ad(NH3) co-ligands, with Pt\u2014S distances of 2.3434\u2005(8) and 2.3461\u2005(7)\u2005\u00c5  co-ligands, with a Pt\u2014S distance of 2.3619\u2005(8)\u2005\u00c5 2(mnt)2] complex  and S2 . This tilt enables sandwich packing between inter\u00admolecular qdt ligands with a distance between centroids of the two qdt rings of 3.610\u2005\u00c5  atom on a neighboring qdt ligand, with a distance of 2.23\u2005\u00c5 (Table\u00a01The chelating qdt ligands of this platinum(IV) complex are slightly canted relative to the platinum-sulfur atoms, with a 15.59\u2005(11)\u00b0 angle between the plane of all the non-H atoms of the qdt ligand \u2005\u00c5 Fig.\u00a02, within \u00c5 Table\u00a01. N\u2014H\u22efO ha3 with 25\u2005ml of water and heating at 333\u2005K for 5\u2005h. Upon cooling to room temperature, the orange solution was added, via cannula, to a Schlenk flask containing 34.3\u2005mg of [Pt(4-ap)4](BF4)2, prepared in a similar manner to [Pt(pyz)4](BF4)2 2(qdt)]). Oxidation of platinum(II) to platinum(IV) likely occurred upon prolonged air exposure of the compound in solution  I. DOI: 10.1107/S2414314622001018/wm4160Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001018/wm4160Isup3.molSupporting information file. DOI: 2145270CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title piperidine derivative, the mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions into dimers related by twofold symmetry. 20H21NO, the dihedral angle between the phenyl ring is 47.5\u2005(1)\u00b0 and the piperidine ring adopts a chair conformation. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions into dimers with the mol\u00adecules related by twofold symmetry.In the title compound, C This leads to dimers with the mol\u00adecules related by twofold rotation symmetry  and the C6\u2013C11 and C15\u2013C20 benzene rings are 70.31\u2005(11) and 79.00\u2005(11)\u00b0, respectively. The dihedral angle between the C6\u2013C11 and C15\u2013C20 benzene rings is 47.51\u2005(12)\u00b0. In the crystal, a C2\u2014H2\u22efry Fig.\u00a02. The N1\u2014A mixture of hexene-2-one (0.05\u2005mol), benzaldehyde (0.1\u2005mol), ammonium acetate (0.05\u2005mol) and ethanol (40\u2005ml) was heated gently and poured into ether (50\u2005ml) and treated with concentrated hydro\u00adchloric acid (25\u2005ml). The precipitated hydro\u00adchloride was washed with an ethanol\u2013ether mixture. The base was liberated by adding strong ammonia until the hydro\u00adchloride dissolved. Dilution with water afforded the free base. The pure compound was was further recrystallized with benzene\u2013petroleum ether to yield the title compound.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S241431462000526X/hb4345sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S241431462000526X/hb4345Isup2.hklStructure factors: contains datablock(s) I. DOI: 1996936CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II centre is coordinated by four pyrrole N atoms of the porphyrin ring and one S atom of the axial 4-methyl\u00adbenzene\u00adthiol\u00adate ligand. Two tetra\u00adhydro\u00adfuran mol\u00adecules and a potassium cation chelated inside a [2.2.2]cryptand  are also present.The Mn 18H36N2O6)][Mn(C44H24Cl4N4)(C7H7S)]\u00b72C4H8O, were obtained by the solvent evaporation method. The MnII cation is coordinated by four pyrrole N atoms (Np) of the porphyrin ring and one S atom of the apical 4-methyl\u00adbenzene\u00adthiol\u00adate ligand with the average Mn\u2014Np and the apical Mn\u2014S bond lengths being 2.160\u2005(9) and 2.4642\u2005(8)\u2005\u00c5, respectively. Two tetra\u00adhydro\u00adfuran solvent mol\u00adecules and a potassium cation chelated inside a [2.2.2]cryptand  are also present.Single crystals of the title compound, [K(C II porphyrin analogues are often used as substitutes and supplements for FeIII porphyrin model compounds when simulating the relevant reactions of heme-active sites, so as to provide a more comprehensive understanding of structure\u2013function relationships in hemoproteins  [Mn(TPP)(1-MeIm)] has a large metal out-of-plane distance (\u039424 and \u03944 \u2265 0.51), and the authors suggested that when the dy2x2\u2013 orbital is populated, the metal atom is too far out of the porphyrin plane to permit effective inter\u00adaction with a sixth ligand. Subsequently, some other crystal structures of five-coordinate manganese porphyrins were reported, e.g. [K(222)][Mn(TPP)(CN)] ] (p-CH3PhS\u2212)].MnII porphyrinate, i.e. the [MnII(TpClPP)(p-CH3PhS\u2212)]\u2212 anion, is a [K(222)]+ cation in which the potassium ion is chelated inside a [2.2.2]cryptand mol\u00adecule. Six O and two N atoms of the [2.2.2]cryptand bind to the potassium cation, and the average K\u2014O and K\u2014N distances are 2.85\u2005(4) and 2.989\u2005(11)\u2005\u00c5, respectively. There are also two tetra\u00adhydro\u00adfuran (THF) solvent mol\u00adecules in the asymmetric unit, one of which is disordered.The mol\u00adecular entities of the title compound are shown in Fig.\u00a01II has a larger ionic radius than FeIII , longer M\u2014Np (Np is a porphyrin N atom) bond lengths [2.160\u2005(9)\u2005\u00c5 versus 2.057\u2005(5)\u20132.06\u2005(12)\u2005\u00c5], and a longer Mn\u2014S apical distance [2.4642\u2005(8)\u2005\u00c5 versus 2.298\u2005(5)\u20132.311\u2005(3)\u2005\u00c5] Cl], and [Mn(TpClPP)OH] were prepared according to a literature method ] was prepared by reduction of [MnIII(TpClPP)OH]  with ethane\u00adthiol (1.5\u2005ml) in benzene (5\u2005ml)  atmosphere using standard Schlenk techniques, and all solvents used were treated under anhydrous and anaerobic conditions. Benzene and tetra\u00adhydro\u00adfuran  were distilled over sodium/benzo\u00adphenone. Hexane  was distilled from sodium/potassium alloy under argon. Pyrrole, Synthesis of ([2.2.2]cryptand)potassium (4-methyl\u00adbenzene\u00adthiol\u00adato)mang\u00adanese(II) tetra\u00adhydro\u00adfuran disolvateII(TpClPP)]  powder was dried under vacuum and then dissolved in 5\u2005ml of tetra\u00adhydro\u00adfuran. 6.0\u2005mg (0.050\u2005mmol) of p-CH3PhSK and 17.0\u2005mg (0.045\u2005mmol) of Kryptofix 222 were added to the solution. The mixture was stirred for about 30 minutes and hexane was layered. After 2 weeks, X-ray quality dark-purple flake-shaped crystals of [K(222)][Mn(TpClPP)(p-CH3PhS\u2212)] were obtained and a large well-formed specimen was selected for the diffraction experiment.The purple [MnA, C71A and C72A were restrained with the RIGU instruction to get a better disorder model. The refined occupancy ratio of the disordered atoms is 0.576\u2005(7):0.524\u2005(7).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314622002413/bt4121sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622002413/bt4121Isup3.hklStructure factors: contains datablock(s) I. DOI: 2142607CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-benzoyl\u00adamido\u00adphosphate is reported and discussed.The crystal structure of the caesium salt of dimethyl- N-benzoyl\u00adamido\u00adphosphate, namely, aqua\u00ad[di\u00admeth\u00adyl (N-benzoyl\u00adamido-\u03baO)phospho\u00adnato-\u03baO]caesium, [Cs(C9H11NO4P)(H2O)] or CsL\u00b7H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoyl\u00adamido\u00adphosphate anions towards the caesium cations.The caesium salt of dimethyl- In addition, the phosphoryl or the carbonyl oxygen atom or both usually bridge the cations. Caesium salts of CAPhs have not been reported to date and are of inter\u00adest as possible dopants in oxide film materials for the improvement of their electric and electron functional characteristics . The oxygen atoms of the carbonyl and phosphoryl groups of the dimethyl-N-benzoyl\u00adamido\u00adphosphate anions act as \u03bc2-bridges between Cs+ cations , and each Cs+ cation links four ligand anions. Additionally, a water mol\u00adecule acts as a \u03bc2-bridge between two Cs+ cations.The asymmetric unit contains the Csle Fig.\u00a02a. The ons Fig.\u00a01. Additions Fig.\u00a02b, and e+ ion contacts nine oxygen atoms. It is involved in the six-membered Cs1\u2013O1\u2013C1\u2013N1\u2013P1\u2013O2 ring with one ligand by bonding with the oxygen atoms of the carbonyl and phosphoryl groups, in the four-membered Cs1\u2013O2\u2013P1\u2013O4 ring with another CAPh ligand by bonding with the oxygen atoms of the phosphoryl and meth\u00adoxy groups and in the six-membered Cs1\u2013O1\u2013C1\u2013N1\u2013P1\u2013O3 ring with the third ligand by bonding with the \u03bc2-oxygen atoms of the carbonyl and meth\u00adoxy groups. In addition, the Cs+ ion contacts with the \u03bc2-O3 atom of the fourth neighboring CAPh as well as with two mol\u00adecules of water , so the majority of the Cs\u2014O contacts might be considered as a mainly ionic type of bond. The Cs1\u2014O1 distance is the longest LH = 1.219\u2005(6)\u2005\u00c5, d(P\u2014O)LH = 1.461\u2005(4)\u2005\u00c5] and the C\u2014N and P\u2014N bond lengths are decreased , 1591 [\u03bd(CC)], 1535 [\u03bd(CO)], 1378 [\u03bd(CN)], 1205 [\u03bd(PO)], 1076, 1038, 928 [\u03bd(PN)], 838, 800, 734, 710, 540, 502,466, 452\u2005cm\u22121. The low-frequency shift of \u03bd(P=O) and \u03bd(C=O) bands in the IR spectrum of CsL\u00b7H2O with respect to HL(\u0394\u03bdLH(P=O) \u223c37cm\u22121, \u0394\u03bdLH(C=O) \u223c147cm\u22121] is typical for bidentate coordination of dimethyl-N-benzoyl\u00adamido\u00adphosphate. 1H NMR (DMSO-d6): \u03b4 = 3.24 , 3.54 , 7.27 , 8.04 . 31P NMR (acetone): \u03b4 = 15.2 (s).Cs7.Uiso(H) = 1.2\u20131.5Ueq(C). O-bound H atoms were refined with the restraints O5\u2014H5A = O5\u2014H5B = 0.84\u00b10.01\u2005\u00c5 and H5A\u22efH5B = 1.62\u00b10.02\u2005\u00c5 with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022012166/mw2194sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989022012166/mw2194Isup2.hklStructure factors: contains datablock(s) I. DOI: 2232690CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Iclaprim and mesylate mol\u00adecules are linked into a hydrogen-bonded mol\u00adecular tape, the central section of which is composed of fused rings. 2H-1-benzo\u00adpyran-5-yl)meth\u00adyl]pyrimidin-1-ium methane\u00adsulfonate, C19H23N4O3+\u00b7CH3O3S\u2212, is a salt made up from a protonated iclaprim mol\u00adecule and a mesylate anion. The pyrimidine and chromene units of the iclaprim mol\u00adecule form an orthogonal arrangement [inter\u00adplanar angle of 89.67\u2005(6)\u00b0], and the 3-nitro\u00adgen position of the pyrimidine ring is protonated. Four distinct N\u2014H\u22efO inter\u00adactions and an additional N\u2014H\u22efN hydrogen bond connect iclaprim and mesylate mol\u00adecules to one another, resulting in an infinite hydrogen-bonded mol\u00adecular tape structure. The central section of the tape is formed by a sequence of fused hydrogen-bonded rings involving four distinct ring types.The title compound, 2,6-di\u00adamino-5-[(2-cyclo\u00adpropyl-7,8-dimeth\u00adoxy- Iclaprim was synthesized according to the original route described by Jaeger  al. 2005, using 32.3SO3\u2212 anion and an iclaprim cation in which the 3-nitro\u00adgen atom of the pyrimidine ring is protonated, i.e. N1  with the fused benzene ring of the chromene unit . With regard to the two bridging bonds, the torsion angles C3\u2014C4\u2014C5\u2014C6 [\u2013160.8\u2005(2)\u00b0] and C4\u2014C5\u2014C6\u2014C7 [\u201396.5\u2005(3)\u00b0] indicate that the C5\u2014C6 bond is twisted slightly out of the pyrimidine plane, whilst the C4\u2014C5 bond is oriented approximately perpendicular to the benzene ring. Accordingly, the two six-membered rings linked via C5 form an orthogonal arrangement with an inter\u00adplanar angle of 89.67\u2005(6)\u00b0. In the chromene moiety, the 7-meth\u00adoxy substituent is significantly twisted out of the ring plane [C10\u2014C9\u2014O3\u2014C19 = \u221270.3\u2005(3)\u00b0], whilst the 8-meth\u00adoxy substituent is almost coplanar with the plane of the fused benzene ring [C9\u2014C8\u2014O2\u2014C18 = 167.6\u2005(2)\u00b0]. The 2H-pyran ring displays the expected bond lengths [C12\u2014C13 = 1.323\u2005(4)\u2005\u00c5]. The program PLATON \u00b0, \u03c6 = 328.4\u2005(7)\u00b0 and q = 0.253\u2005(3)\u2005\u00c5, are consistent with the presence of a skew-boat conformation N1 Fig.\u00a01. The mol3.2 groups attached to the pyrimidine ring  and the protonated N1 atom of the pyrimidine ring as potential hydrogen-bond donor groups. These hydrogen-bond donor functions are engaged in five distinct inter\u00admolecular N\u2014H\u22efA inter\u00adactions .Iclaprim mesylate was prepared according to a modified procedure based on the original synthesis by Jaeger  al. 2005 shown in6.a axis. The refined value of the minor twin component fraction was 0.260\u2005(1). All H atoms were identified in difference-Fourier maps and those of NH and NH2 groups were refined with a restrained N\u2014H distance of 0.88\u2005(2)\u2005\u00c5 and their Uiso parameters refined freely. The H atoms at the cyclo\u00adpropyl ring  were refined with a restrained C\u2014H distance of 0.96\u2005(2)\u2005\u00c5 and with Uiso(H) = 1.2Ueq(C). Other H atoms bonded to secondary CH2 (C\u2014H = 0.98\u2005\u00c5) or aromatic CH (C\u2014H = 0.94\u2005\u00c5) carbon atoms were positioned geometrically. Their Uiso parameters were set to 1.2Ueq(C). Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip (C\u2014H = 0.97\u2005\u00c5) and their Uiso parameters were set to 1.5 Ueq(C) of the parent carbon atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022011689/wm5666sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022011689/wm5666Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022011689/wm5666Isup3.cmlSupporting information file. DOI: 2224639CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-butyl-2,3-bis\u00ad(di\u00adcyclo\u00adhexyl\u00adamino)\u00adcyclo\u00adpropenimine is reported.The structure of the acid chloride salt of the superbase  N-Butyl-2,3-bis\u00ad(di\u00adcyclo\u00adhexyl\u00adamino)\u00adcyclo\u00adpropenimine (1) crystallizes from benzene and hexa\u00adnes in the presence of HCl as a mono\u00adbenzene solvate of the hydro\u00adchloride salt, [1H]Cl\u00b7C6H6 or C31H54N3+\u00b7Cl\u2212\u00b7C6H6, in the P21/n space group. The protonation of 1 results in the generation of an aromatic structure based upon the delocalization of the cyclo\u00adpropene double bond around the cyclo\u00adpropene ring, giving three inter\u00admediate C\u2014C bond lengths of \u223c1.41\u2005\u00c5, and the delocalization of the imine-type C\u2014N double bond, giving three inter\u00admediate C\u2014N bond lengths of \u223c1.32\u2005\u00c5. Ion\u2013ion and ion\u2013benzene packing inter\u00adactions are described and illustrated. Originally reported as four-electron Lewis donors \u00adcyclo\u00adpropenimine (1) is a newer version of superbase with improved basicity, which has been explored as a catalyst for ring-opening polymerization. Cyclo\u00adpropenimines have a conjugate acid apK of about 27, an improvement over that of the superbase 2-tert-butyl-1,1,3,3-tetra\u00admethyl\u00adguanidine (BTMG), which has a apK of 23.56 \u2005\u00c5 on average. The C\u2014N bond to the protonated butyl nitro\u00adgen is only slightly shorter at 1.319\u2005(2)\u2005\u00c5. The three cyclo\u00adpropene C\u2014C bonds exhibit lengths consistent with aromaticity; the unique C\u2014C bond opposite the n-butyl group is 1.388\u2005(2)\u2005\u00c5, while the other two C\u2014C bonds are similar or slightly shorter at 1.377\u2005(2) and 1.383\u2005(2)\u2005\u00c5. Though these latter two bonds are equivalent under mol\u00adecular point symmetry, their differences are attributed to the asymmetric crystal packing environment of the P21/n space group. The comparable nature of the bond metrics of the three C\u2014N bonds and the three cyclo\u00adpropenyl C\u2014C bonds is consistent with aromatization, and an analogous aromatization of the C3N3 core of 1-mesityl-2,3-bis\u00ad(diiso\u00adpropyl\u00adamino)\u00adcyclo\u00adpropeniminium tetra\u00adfluoro\u00adborate was observed in the crystal structure of this salt , which ranges from about 6\u201325\u2005kJ\u2005mol\u22121 per \u03c0 electron , and 2.7169\u2005(6)\u2005\u00c5 from an intra\u00admolecular axial cyclo\u00adhexyl proton, H29A (+0.050). The crystal packing demonstrates that the C3N3 planes of all mol\u00adecules pack parallel to each other (as required by the space-group symmetry), with a normal slightly oblique to the (101) plane \u2005\u00c5, Fig.\u00a03n-butyl chain Cl\u00b7C6H6 were observed inside. The yield of crystalline [1H]Cl\u00b7C6H6 was significantly improved by the addition of HCl. To a glass shell vial containing 7.2\u2005mg of N-butyl-2,3-bis\u00ad(di\u00adcyclo\u00adhexyl\u00adamino)\u00adcyclo\u00adpropenimine, 2\u2005mL of benzene were added. A drop of dilute HCl (0.730 M) was added. This was diffused with 3\u2005mL of hexa\u00adnes in the outer vial for 2\u20133 days. Crystallization works best when the drop is not in contact with the walls of the vial where the crystals grow. Crystals were isolated by deca\u00adnting the liquid from the inner vial using a disposable pipette, and taking care to remove the visible aqueous HCl droplet with the first pipette draw. After removing the mother liquor, the crystals were rinsed with hexa\u00adnes. Yield 6.3\u2005mg (70%). Yields in this small-scale preparation ranged from 22% to 70% across multiple attempts. 1H NMR (ppm) 400\u2005MHz, CDCl3): \u03b4(ppm): 0.97 , 1.62\u20131.82 , 1.62\u20131.76 , 1.80 , 1.96 , 3.34 , 3.56 , 7.4 . 13C NMR (ppm) : \u03b4(ppm): 13.97, 19.94, 24.58, 25.84, 32.34, 33.79, 46.15, 59.55, 114.01, 128.35. FTIR (cm\u22121): 2926 (m), 2851 (m), 1503 (s), 1445 (m), 1383 (w), 1374 (w), 1345 (w), 1324 (w), 1253 (w), 1188 (w), 1180 (w), 1102 (w), 1092 (w), 1004 (w), 895 (w), 696 (m). Analysis calculated for C31H53N3\u00b70.5 C6H6 (%): C, 76.31; H, 10.38; N, 7.22. Found: C, 75.873; H, 10.83; N, 7.24. M.p. 353\u2013356\u2005K (decomposes).Initially, crystals of Cl\u00b7C6H6 using ORCA  I. DOI: 10.1107/S2056989022008076/jq2013Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022008076/jq2013Isup3.cdxSupporting information file. DOI: 2200141CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Anopheles gambiae sensu lato (s.l.) mosquitoes to pyrethroids and their expression of metabolic enzymes.Malaria remains one of the most devastating diseases globally, and the control of mosquitoes as the vector is mainly dependent on chemical insecticides. Elevated temperatures associated with future warmer climates could affect mosquitoes' metabolic enzyme expression and increase insecticide resistance, making vector control difficult. Understanding how mosquito rearing temperatures influence their susceptibility to insecticide and expression of metabolic enzymes could aid in the development of novel tools and strategies to control mosquitoes in a future warmer climate. This study evaluated the effects of temperature on the susceptibility of Anopheles gambiae s.l. eggs obtained from laboratory-established colonies were reared under eight temperature regimes . Upon adult emergence, 3- to 5-day-old female non-blood-fed mosquitoes were used for susceptibility tests following the World Health Organization (WHO) bioassay protocol. Batches of 20\u201325 mosquitoes from each temperature regime (25\u201334\u00a0\u00b0C) were exposed to two pyrethroid insecticides (0.75% permethrin and 0.05% deltamethrin). In addition, the levels of four metabolic enzymes  were examined in mosquitoes that were not exposed and those that were exposed to pyrethroids.An. gambiae s.l. mosquitoes exposed to deltamethrin and permethrin decreased at temperatures above 28\u00a0\u00b0C. In addition, mosquitoes reared at higher temperatures were more resistant and had more elevated enzyme levels than those raised at low temperatures. Overall, mosquitoes that survived after being exposed to pyrethroids had higher levels of metabolic enzymes than those that were not exposed to pyrethroids.Mortality in An. gambiae s.l. mosquitoes' susceptibility to pyrethroids and increased the expression of metabolic enzymes. This evidence suggests that elevated temperatures projected in a future warmer climate could increase mosquitoes' resistance to insecticides and complicate malaria vector control measures. This study therefore provides vital information, and suggests useful areas of future research, on the effects of temperature variability on mosquitoes that could guide vector control measures in a future warmer climate.This study provides evidence that elevated temperatures decreased The online version contains supplementary material available at 10.1186/s13071-022-05273-z. Anopheles gambiae could affect malaria control measures. The An. gambiae complex consists of nine morphologically identical sibling species. They include An. gambiae sensu stricto (s.s.), An. arabiensis, An. merus, An. melas, An. quadriannulatus, An. amharicus, An. bwambae, An. coluzzii, and An. fontenillei ) were first used to identify species of the protocol . Subsequectively . The PCRAn. gambiae s.l. mosquitoes  raised at 25, 28, 30, 32, and 34\u00a0\u00b0C. Permethrin and deltamethrin insecticides were selected because they are the most common insecticides used in malaria control programs  compared to those reared at 34\u00a0\u00b0C [1.94\u2009\u00d7\u200910\u20139 ], 30\u00a0\u00b0C [1.49\u2009\u00d7\u200910\u20139 ], 28\u00a0\u00b0C [8.85\u2009\u00d7\u200910\u201310 ], and 25\u00a0\u00b0C [7.21\u2009\u00d7\u200910\u201310  mol cytochrome P450/min/mg protein]  with increasing temperature. Dunn's multiple range test showed that all but 30 vs 28\u00a0\u00b0C (P\u2009=\u20090.113) and 34 vs 30\u00a0\u00b0C (P\u2009=\u20090.010) showed a statistically significant difference in oxidase level  mol cytochrome P450/min/mg protein] levels compared to those reared at 32\u00a0\u00b0C [2.40\u2009\u00d7\u200910\u20139 ], 25\u00a0\u00b0C [2.07\u2009\u00d7\u200910\u20139 ], and 28\u00a0\u00b0C [1.34\u2009\u00d7\u200910\u20139  mol cytochrome P450/min/mg protein]  in MFO levels among the different temperature regimes. Further tests using Dunn's multiple range test showed a significant difference (P\u2009<\u20090.008) in the various temperature regime comparisons , 28\u00a0\u00b0C , and 30\u00a0\u00b0C  and not exposed to pyrethroids were significantly lower than those that were exposed to pyrethroids. However, mosquitoes reared at 32\u00a0\u00b0C and not exposed to pyrethroids had significantly higher  MFO levels than those exposed to pyrethroids  in the GST levels in mosquitoes among the different temperature regimes. However, further analysis using Dunn's multiple range test showed statistically significant differences for 32 vs 25\u00a0\u00b0C (P\u2009<\u20090.001), 34 vs 25\u00a0\u00b0C (P\u2009=\u20090.002), 32 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), 32 vs 30\u00a0\u00b0C (P\u2009<\u20090.001), and 34 vs 32\u00a0\u00b0C (P\u2009<\u20090.001)  similar to that of the MFO level ], followed by 25\u00a0\u00b0C [2.72\u2009\u00d7\u200910\u20133 ], 30\u00a0\u00b0C [2.62\u2009\u00d7\u200910\u20133 ] and the lowest recorded at 28\u00a0\u00b0C [1.35\u2009\u00d7\u200910\u20133  mol cDNB/min/mg protein]  in the GST level in mosquitoes among the different temperature regimes. Further statistical tests using Dunn's multiple range test showed statistically significant differences for 28 vs 25\u00a0\u00b0C (P\u2009=\u20090.002), 32 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), and 32 vs 30\u00a0\u00b0C (P\u2009=\u20090.005)  showed a statistically significant difference in GST levels ], followed by 34\u00a0\u00b0C [4.04\u2009\u00d7\u200910\u20137 ], 28\u00a0\u00b0C [2.83\u2009\u00d7\u200910\u20137 ], 25\u00a0\u00b0C [2.52\u2009\u00d7\u200910\u20137 ] and 30\u00a0\u00b0C [2.12\u2009\u00d7\u200910\u20137  mol \u03b1-naphthol/min/mg protein]  in \u03b1-esterase level in mosquitoes among the different temperature regimes. Further statistical tests using Dunn's multiple range test showed a statistically significant difference for 32 vs 25\u00a0\u00b0C (P\u2009<\u20090.001), 34 vs 25\u00a0\u00b0C (P\u2009<\u20090.001), 32 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), 32 vs 30\u00a0\u00b0C (P\u2009<\u20090.001), 34 vs 30\u00a0\u00b0C (P\u2009<\u20090.001), and 34 vs 32\u00a0\u00b0C (P\u2009<\u20090.001) ] and lowest at 28\u00a0\u00b0C [1.44\u2009\u00d7\u200910\u20137 (2.40\u2009\u00d7\u200910\u20137) mol \u03b1-naphthol/min/mg protein]  in \u03b1-esterase levels in mosquitoes among the different temperature regimes. According to Dunn's multiple range tests, a statistical difference existed only for 30 vs 28\u00a0\u00b0C (P\u2009=\u20090.003) and 32 vs 28\u00a0\u00b0C (P\u2009=\u20090.001)  showed a statistically significant difference in \u03b1-esterase level ]\u2009>\u200932\u00a0\u00b0C [2.87\u2009\u00d7\u200910\u20137 ]\u2009>\u200928\u00a0\u00b0C [1.38\u2009\u00d7\u200910\u20137 ]\u2009>\u200925\u00a0\u00b0C [1.36\u2009\u00d7\u200910\u20137 ]\u2009>\u200930\u00a0\u00b0C [1.30\u2009\u00d7\u200910\u20137  mol \u03b2-naphthol/min/mg protein]  in \u03b2-esterase levels in mosquitoes with increasing temperature. However, post hoc analysis using Dunn's multiple range test showed a statistically significant difference for 32 vs 25\u00a0\u00b0C (P\u2009=\u20090.001), 34 vs 25\u00a0\u00b0C (P\u2009<\u20090.001), 34 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), 34 vs 30\u00a0\u00b0C (P\u2009<\u20090.001), and 34 vs 32\u00a0\u00b0C (P\u2009=\u20090.003)  at 28\u00a0\u00b0C to 2.64\u2009\u00d7\u200910\u20137 (1.63\u2009\u00d7\u200910\u20137) mol \u03b2-naphthol/min/mg protein at 32\u00a0\u00b0C  in \u03b2-esterase levels in mosquitoes raised at different temperatures. Multiple comparisons using Dunn's test showed statistically significant differences for 28 vs 25\u00a0\u00b0C (P\u2009<\u20090.001), 30 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), 32 vs 28\u00a0\u00b0C (P\u2009<\u20090.001), and 32 vs 30\u00a0\u00b0C (P\u2009=\u20090.007)  in \u03b2-esterase levels  to pyrethroids decreased with increasing temperature. Another important finding was that deltamethrin induced higher mortality in mosquitoes than permethrin, indicating that mosquitoes were resistant to permethrin based on WHO criteria [An. gambiae s.l. mosquitoes were more susceptible to deltamethrin than permethrin. With projections of warmer temperatures in coming years, especially in sub-Saharan Africa, high resistance to pyrethroids with increasing temperatures could affect the effectiveness of malaria control programs using pyrethroids [Mosquito susceptibility to pyrethroids decreased with increasing temperature. This may be attributed to the higher expression of enzymes at high temperatures . At highcriteria . These fcriteria . This cocriteria , which sethroids . In Ghanethroids , and anyDrosophila melanogaster adapted to high temperatures as compared with those acclimatized to low temperatures [With regard to metabolic enzymes, MFO and GST levels in mosquitoes that were not exposed to pyrethroids increased with increasing temperature from 25 to 32\u00a0\u00b0C. On the other hand, enzyme expression levels decreased at 34\u00a0\u00b0C, suggesting that enzyme expression may be impaired above a certain optimum temperature range . In addieratures . The eleeratures .An. gambiae s.s. mosquitoes exposed to permethrin insecticides were higher than in mosquitoes that were not exposed to insecticides.Comparing the enzyme levels in mosquitoes that were not exposed and those exposed to pyrethroids, levels of MFO, GST, \u03b1-esterase, and \u03b2-esterase were higher in those exposed to pyrethroids than in those that were not exposed, especially at 25 and 30\u00a0\u00b0C. The high resistance of mosquitoes to insecticides might have involved metabolic detoxification due to the elevated enzyme expression in mosquitoes exposed to pyrethroids . These fAn. arabiensis mosquitoes. However, the findings of the current study are contrary to those reported by Leong et al. [A. aegypti mosquitoes. These findings raise the possibility that the levels of metabolic enzymes may differ among mosquito species [The study further revealed that MFO was the least expressed enzyme in mosquitoes. The findings are in agreement with those of Alemayehu et al. , who obsg et al. , who fou species . TherefoAn. gambiae s.l. mosquitoes' susceptibility to insecticides and metabolic enzyme expression. The results suggest that An. gambiae s.l. mosquitoes reared at higher temperatures have increased insecticide resistance than those reared at lower temperatures. In addition, increased rearing temperatures of An. gambiae s.l. mosquitoes were associated with increased expression of metabolic enzymes. Increased metabolic enzyme levels are usually associated with insecticide resistance. This suggests that elevated temperatures projected in a future warmer climate could increase mosquitoes' resistance to insecticides and thus reduce the effectiveness of vector control measures for diseases such as malaria. Therefore, it is essential to research new tools for vector management rather than depending only on chemical insecticides.This study contributes to the knowledge of the effects of temperature variability on Additional file 1: Table S1. Ambient and rearing water conditions for each temperature regime. Table S2. Mortality in An. gambiae s.l. mosquitoes exposed to pyrethroids. Table S3. Median levels of metabolic enzymes in An. gambiae s.l. mosquitoes reared at different temperature regimes. Table S4. Pairwise comparisons of enzyme levels in An. gambiae s.l. mosquitoes reared at different temperature regimes. Table S5. Mann\u2013Whitney U-test between mosquitoes that were not exposed and those exposed to pyrethroids."}
{"text": "H = DSz2 \u2212 \u03b3NV(Sx(BAx + Bx) + Sy(BAy + By) + Sz(BAz + Bz))\u201d. It should read \u201cH = DSz2 \u2212 \u03b3NV(Sx(BAx + Bx) + Sy(BAy + By) + Sz(BAz + Bz))\u201d. On line 7 in the left column on page 180 of the original article, the text originally read \u201cBmin \u2245 4 \u0393 (33 \u03b3NV \u00d7 C)\u22121 (I0 \u00d7 t)\u22121\u201d. It should read \u201cBmin \u2245 4 \u0393 (3\u221a3 \u03b3NV \u00d7 C)\u22121 (I0 \u00d7 t)\u22121/2\u201d. On line 23 in the left column on page 180 of the original article, the text originally read \u201cS = Fl(f1) \u2212 Fl(f2))/(Fl(f1) + Fl(f2)\u201d. It should read \u201cS = (Fl(f1) \u2212 Fl(f2))/(Fl(f1) + Fl(f2))\u201d.The authors regret that there were errors that appear in the Results and discussion section. On line 47 in the right column on page 179, the text originally read \u201cThe authors regret that there was an error in the text in the Author contributions section on line 24 in the right column on page 183 of the original article. The text originally read \u201cASQ\u201d. It should read \u201cSQAS\u201d.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers."}
{"text": "The hypoxanthinium and xanthinium cations in salts I and II are both in the oxo-N(9)\u2013H tautomeric form. The crystal packing of the two salts is governed predominantly by N\u2014H\u22efO, N\u2014H\u22efBr, C\u2014H\u22efBr and O\u2014H\u22efBr inter\u00adactions described by Two new crystalline salts, namely, hypoxanthinium bromide monohydrate, C 5H5N4O+\u00b7Br\u2212\u00b7H2O (I) and xanthinium bromide monohydrate, C5H5N4O2+\u00b7Br\u2212\u00b7H2O (II), were synthesized and characterized by single-crystal X-ray diffraction technique and Hirshfeld surface analysis. The hypoxanthinium and xanthinium cations in salts I and II are both in the oxo-N(9)\u2013H tautomeric form. The crystal packing of the two salts is governed predominantly by N\u2013H\u22efO, N\u2013H\u22efBr, C\u2013H\u22efBr and O\u2013H\u22efBr inter\u00adactions described by R23(9) and R22(8) synthons. The crystal packing is also consolidated by carbon\u00adyl\u22ef\u03c0 inter\u00adactions between symmetry-related hypoxanthinium (+HX) cations in salt I and xanthinium cations (+XA) in salt II. The combination of all these inter\u00adactions leads to the formation of wave- and staircase-like architectures in salts I and II, respectively. The largest contributions to the overall Hirshfeld surface are from Br\u22efH/H\u22efBr contacts (22.3% in I and 25.4% in II) .Two new crystalline salts, namely, hypoxanthinium bromide monohydrate, C Similarly, xanthinium nitrate monohydrate, xanthinium hydrogensulfate monohydrate  crystallizes in the monoclinic space group P21/c with one hypoxanthinium cation (+HX), one bromide anion (\u2212Br) and one water mol\u00adecule in the asymmetric unit, as shown in Fig.\u00a01+HX cation exists in the oxo-N(9)\u2013H tautomeric form with the N7 atom of the purine ring protonated, as can be seen from the N\u2014C bond distance [N7\u2014C8 = 1.3219\u2005(17)\u2005\u00c5 vs N9\u2014C8 = 1.3419\u2005(18)\u2005\u00c5] and C\u2014N\u2014C bond angles [C5\u2014N7\u2014C8 = 107.98\u2005(11)\u00b0 and C4\u2014N9\u2014C8 = 108.32\u2005(10)\u00b0]. Those values are similar to those in the crystal structure of hypoxanthinium chloride monohydrate  shorter than N9\u2013C8 one [1.344\u2005(5)\u2005\u00c5]. The C\u2014N\u2014C bond angles are C5\u2014N7\u2014C8 = 108.2\u2005(3)\u00b0 and C4\u2014N9\u2014C8 = 107.7\u2005(3)\u00b0 and, therefore, the cation can also be described as the oxo-N(9)\u2013H tautomer. These values are similar to those in xanthinium perchlorate dihydrate  . The dimer is flanked on both sides by a water mol\u00adecule (O1W), forming a pair of O1W\u2014H2W\u22efO2iv and O1W\u2014H1W\u22efO6ii hydrogen bonds with an HDADA array  along the ac plane. Neighbouring tetra\u00admeric units are then connected through two sets of W and O1W\u2014H1W\u22efO6ii hydrogen bonds and an L) motif formed by a pair of O1W\u2014H1W\u22efO6ii inter\u00adactions. The tetra\u00admeric units combine into a supra\u00admolecular ribbon extended along the ac plane  of the +XA unit) with C=O\u22efCg2vi and C=O\u22efCg2vii distances of 3.366\u2005(3) and 3.477\u2005(3)\u2005\u00c5, respectively, and angles of 108.2\u2005(2) and 118.7\u2005(2)\u00b0 [symmetry codes: (vi) 1\u00a0+\u00a0x, y, z; (vii) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; Fig.\u00a08In the crystal structure of salt s Table\u00a02 with an ne Fig.\u00a05. Neighbo4.et al., 2007Crystal Explorer 17.5  inter\u00adactions  or shorter (red) than the sum of the van der Waals radii of the two inter\u00adacting atoms. The Hirshfeld surfaces of salts I and II are shown in Fig.\u00a09a and 10aI and II and the respective neighbouring moieties are shown in Fig.\u00a09b and 10bI and II are shown in Figs. 11I 19.7%, II 23.4%), N\u22efH/H\u22efN  C\u22efH/H\u22efC , H\u22efH/H\u22efH  and C\u22efC/C\u22efC  (Table\u00a05), indicating that the most abundant contact is Br\u22efH/H\u22efBr with 22.3% in I and 25.4% in II, respectively.Hirshfeld surface analyses and their associated two-dimensional fingerprint plots   and xanthinium bromide monohydrate (II) using the following qu\u00adanti\u00adties: 0.0340\u2005mg (0.25mmol) of hypoxanthine for I and 0.0380\u2005mg (0.25\u2005mmol) of xanthine for II.A general method was used for the preparation and crystallization of the hypoxanthinium bromide monohydrate (The indicated amount of the base was dissolved in 20\u2005mL of distilled water and 2\u2005mL of hydro\u00adbromic acid (5% in water) were added. The reaction mixture was heated to 358\u2005K for 30\u2005min using a water bath. The resulting solution was allowed to slowly evaporate at room temperature. After a few days, colourless plate-like crystals were obtained.8.I and II are summarized in Table\u00a04Uiso(H) = 1.2Ueq (C). The H atoms of the water mol\u00adecule were located in a difference-Fourier map and refined with the O\u2014H distance restrained to 0.85\u20130.86\u2005\u00c5 and with Uiso(H) = 1.5 Ueq(O). The hydrogen atoms bound to the nitro\u00adgen atoms in salts I and II were located in difference-Fourier maps and either refined freely (in I) or with the distance restraint N\u2014H = 0.82\u2005\u00c5 and with Uiso(H) = 1.2Ueq(N) (in II).Crystal data, data collection and structure refinement details for salts 10.1107/S2056989022005278/jq2017sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022005278/jq2017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022005278/jq2017Isup4.cmlSupporting information file. DOI: 10.1107/S2056989022005278/jq2017IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022005278/jq2017IIsup5.cmlSupporting information file. DOI: 2170923, 2170922CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds link mol\u00adecules in the crystal into layers parallel to (011). The crystal packing is consolidated through C\u2014Br\u22ef\u03c0 and C\u2014F\u22ef\u03c0 inter\u00adactions, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions. 14H8Br2FN3O2, the 4-fluoro\u00adphenyl ring and the nitro-substituted phenyl ring form a dihedral angle of 64.37\u2005(10)\u00b0. Mol\u00adecules in the crystal are connected by C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds into layers parallel to (011). The crystal packing is consolidated by C\u2014Br\u22ef\u03c0 and C\u2014F\u22ef\u03c0 inter\u00adactions, as well as by \u03c0\u2013\u03c0 stacking inter\u00adactions. According to a Hirshfeld surface analysis of the crystal structure, the most significant contributions to the crystal packing are from O\u22efH/H\u22efO (15.0%), H\u22efH (14.3%), Br\u22efH/H\u22efBr (14.2%), C\u22efH/H\u22efC (10.1%), F\u22efH/H\u22efF (7.9%), Br\u22efBr (7.2%) and Br\u22efC/C\u22efBr (5.8%) contacts.In the title compound, C Depending on the attached substituents, azo compounds have attracted attention because of their high synthetic potential for organic and inorganic chemistry and numerous useful properties. For example, azo dyes find applications in the design of functional materials attributed to smart hydrogen bonding, as self-assembled layers, photo-triggered structural switching, liquid crystals, ionophors, indicators, semiconductors, spectrophotometric reagents for determination of metal ions, catalysts, photoluminescent materials, optical recording media, spin-coating films and anti\u00admicrobial agents -1--2-(4-fluoro\u00adphen\u00adyl)diazene, the mol\u00adecular and crystal structure of which along with a Hirshfeld surface analysis are reported here.In the above context, we have attached F, Br and NO2.trans-configured with regard to the N=N double bond and are practically coplanar as revealed by the C2\u2014N2=N3\u2014C9 torsion angle of \u2212178.63\u2005(16)\u00b0. All of the bond lengths and angles in the title compound are similar to those for the related azo compounds reported in the Database survey section.The mol\u00adecular conformation of the title compound is not planar, as seen in Fig.\u00a013.Cg1  = 3.6016\u2005(9)\u2005\u00c5, C1\u2014Br1\u22efCg1 = 104.24\u2005(7)\u00b0] and C\u2014F\u22ef\u03c0  inter\u00adactions, and weak \u03c0\u2013\u03c0 stacking , where Cg1 and Cg2 are the centroids of the C3\u2013C8 and C9\u2013C14 rings, respectively,  Table\u00a01\u20134 \u25b8 \u25b8. 4.Crystal Explorer 17.5  to 1.1463 (blue) a.u. -1--2-phenyl\u00addiazene moiety resulted in 27 hits. Eight compounds are closely related to the title compound, viz. those with CSD refcodes GUPHIL (I)        , mol\u00adecules are linked into inversion dimers via short halogen\u22efhalogen contacts  compared to the van der Waals radius sum of 3.50\u2005\u00c5 for two chlorine atoms. No other directional contacts could be identified, and the shortest aromatic ring centroid separation is greater than 5.25\u2005\u00c5. In the crystals of (II) and (III), mol\u00adecules are linked through weak X\u22efCl contacts [X = Cl for (II) and Br for (III)], C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets lying parallel to (001). In the crystal of (IV), mol\u00adecules are stacked in columns parallel to [100] via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In (V), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running parallel to [001]. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In (VI), C\u2014H\u22efN and short Cl\u22efCl contacts are observed, and in (VII), C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short Cl\u22efO contacts occur. In the crystal of (VIII), mol\u00adecules are linked into chains running parallel to [001] by C\u2014H\u22efO hydrogen bonds. The crystal packing is consolidated by C\u2014F\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions, and short Br\u22efO [2.9828\u2005(13)\u2005\u00c5] contacts are also observed.In the crystal of (6.ababE)-1-(4-fluoro\u00adphen\u00adyl)-2-(4-nitro\u00adbenzyl\u00adidene)hydrazine (1\u2005mmol), tetra\u00admethyl\u00adethylenedi\u00adamine , CuCl  and CBr4 (4.5\u2005mmol). After 1\u20133\u2005h , the reaction mixture was poured into a 0.01\u2005M HCl solution , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined organic phase was washed with water (3 \u00d7 50\u2005ml), brine (30\u2005ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (v/v 3/1\u20131/1). Light-orange solid (yield 52%); m.p. 377\u2005K. Analysis calculated for C14H8Br2FN3O2 (M = 429.04): C 39.19, H 1.88, N 9.79; found: C 39.17, H 1.85, N 9.76%. 1H NMR  \u03b4 7.36\u20137.14 . 13C NMR  \u03b4 164.35, 153.13, 152.46, 133.69, 133.24, 131.74, 127.98, 127.89, 127.75, 127.42, 119.07, 89.02. ESI\u2013MS: m/z: 430.06 [M\u00a0+\u00a0H]+. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.The title compound was synthesized according to a reported method  = 1.2Ueq(C). The maximum electron density in the final difference map is located 0.75\u2005\u00c5 from atom Br1, while the minimum electron density is located 0.72\u2005\u00c5 from Br2.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989022004388/wm5642sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004388/wm5642Isup2.hklStructure factors: contains datablock(s) I. DOI: 2168678CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Colorless, block-shaped crystals were grown in a potassium hydro\u00adflux, i.e. under ultra-alkaline conditions, within 10\u2005h. K2SeO3 crystallizes isostructural with Na2SO3 and K2TeO3 in the trigonal space group Pa = 6.1063\u2005(4)\u2005\u00c5 and c = 6.9242\u2005(4)\u2005\u00c5 at 100\u2005(1)\u2005K. In the trigonal\u2013pyramidal, C3v-symmetric [SeO3]2\u2013 anion, the bond length is 1.687\u2005(1)\u2005\u00c5, and the bond angle is 103.0\u2005(1)\u00b0. Two of the three unique potassium cations exhibit a coordination number of six, and the third a coordination number of nine.Crystal structure data for potassium orthoselenate(IV), K K2Se2O5  are a long-known but poorly studied class of compounds. After the discovery of the first salts of selenic acid by Berzelius, comprehensive studies on these salts were not carried out until the beginning of the 1930s, when Janitzki reported the syntheses of sodium and potassium salts of selenic acid 2] , K2.2SeO3, one selenium atom , three potassium atoms  and one oxygen atom . The unit cell of K2SeO3 is depicted in Fig.\u00a01C3v-symmetric [SeO3]2\u2013 anion can be attributed to the electron lone pair of the selenium(IV) atom. This oxidation state is supported by the bond-valence sum calculation  = \u2211exp\u2005[(RSeO \u2013 dSeO)/b)] = 3 \u00b7 exp\u2005[(1.811\u2005\u00c5 \u2013 1.687\u2005(1)\u2005\u00c5) / 0.37\u2005\u00c5)] = 4.2 valence units. The potassium cations K1 and K2 are octa\u00adhedrally coordinated by oxygen atoms with K\u2014O distances of 2.631\u2005(1) and 2.771\u2005(1)\u2005\u00c5, respectively. K3 has nine oxygen neighbors at distances of 2.792\u2005(1), 3.020\u2005(1)\u2005\u00c5, and 3.474\u2005(1)\u2005\u00c5  groups is responsible for the symmetry reduction to PK4.2SeO3, was synthesized in a potassium hydroxide hydro\u00adflux with a molar water-base ratio of 1.7. The reaction was carried out in a PTFE-lined 50\u2005mL Berghof-type DAB-2 stainless steel autoclave to prevent evaporation of water. The starting material SeO2  was dissolved in 3\u2005ml of water before adding 6.3\u2005g of KOH . After closing the autoclave, the reaction mixture was heated to 473\u2005K at a rate of 2\u2005K\u2005min\u22121 and, after 8\u2005h, cooled to room temperature at a rate of \u22121\u2005K\u2005min\u22121. The solid reaction product was washed twice with 2\u2005ml of methanol on a Schlenk frit under inert conditions to remove adherent hydro\u00adflux. The colorless, block-shaped crystals of K2SeO3 , KO3 Fig.\u00a04 dissolveO3 Fig.\u00a04. Due to JANA2006 was used . The composition of selected single crystals was determined by semi-qu\u00adanti\u00adtative energy dispersive X-ray analysis (Ua = 15\u2005kV) using a Silicon Drift Detector X\u2013MaxN (Oxford Instruments). The data were processed applying the AZtec software package  global, I. DOI: 10.1107/S2056989022005175/wm5645Isup2.hklStructure factors: contains datablock(s) I. DOI: 2172487CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: BMC Neuroscience (2022) 23:68 10.1186/s12868-022-00754-4fMRI data acquisition section.Following the publication of the original article , an errobold typeface.The updated text is given below, and the changes have been highlighted in fMRI data acquisition8\u00b0, 256\u2009\u00d7\u2009256 matrix, voxel size 0.7\u2009\u00d7\u20090.7\u2009\u00d7\u20090.7\u00a0mm3. For the resting state scans before and after stress induction (RS1 and RS2), 355 volumes of T2*-weighted echo-planar images were acquired for each session with the following parameters: 34 axial slices covering the whole brain, repetition time\u2009=\u20092000\u00a0ms, echo time\u2009=\u200930\u00a0ms, flip angle\u2009=\u200990\u00b0, 9696 matrix, field of view\u2009=\u2009240,240\u00a0mm2, voxel size\u2009=\u20092.5\u2009\u00d7\u20092.5\u2009\u00d7\u20093\u00a0mm3.A Philips 3T scanner was used for fMRI data acquisition. Structural T1-weighted images for spatial normalization were measured using a turbo field echo sequence with the following parameters: 274 sagittal slices covering the whole brain, flip angle\u2009=\u2009Moreover, the authors identified an error in Table 1. The correct Table Finally, the authors identified an error in Fig. 4. The correct Fig.\u00a0The original article  has been"}
{"text": "E responded in opposite manner 5\u00a0min post\u2010exercise compared to E\u2009+\u2009C (p\u00a0=\u00a00.013) and C (p\u00a0=\u00a00.032) in routine respiration, and to E\u2009+\u2009C in free routine activity (p\u00a0=\u00a00.013). E\u2009+\u2009C\u2009>\u2009C\u2009>\u2009E was observed for increased lactate levels and decreased isometric force that correlated with routine respiration . Lactate and pH change did not affect bioenergetics of PBMCs. Acute resistance exercise affected cellular respiration of PBMCs, with training volume and the amount of metabolic stress appear influential. Results suggest that acute inflammation response does not contribute to changes seen in cellular respiration, but the level of peripheral muscle fatigue and metabolic stress could be explaining factors.Little is known how acute exercise\u2010induced inflammation and metabolic stress affect immune cell bioenergetics and the portion of its components. Therefore, we investigated acute effects of eccentric\u2010only (E), concentric\u2010only (C) and combined eccentric\u2010concentric resistance exercise (E\u2009+\u2009C) bouts on cellular respiration of peripheral blood mononuclear cells (PBMCs). Twelve strength\u2010trained young men performed bench press resistance exercises in randomized order. Venous blood samples were drawn at pre\u2010, 5\u00a0min post\u2010 and 24\u2009h post\u2010exercise. Several PBMC respiration states were measured using high\u2010resolution respirometry. Levels of leukocytes, interleukin 6 (IL\u20106), C\u2010reactive protein (CRP), creatine kinase (CK), blood lactate and maximum voluntary isometric force were measured from the same time points. Effects of blood lactate and pH change on bioenergetics of PBMCs were investigated ex vivo. PBMC routine respiration ( Resistance exercise with different workloads have distinct effect on cellular respiration of PBMCs. Training volume and amount of metabolic stress are influential. However, an exercise model comparing responses to eccentric and concentric exercise could reveal differences in bioenergetics of PBMCs accompanying the expected differences in metabolic cost and inflammation response. Consequently, our study investigated the acute effects of three resistance exercise bouts, eccentric\u2010only (E), concentric\u2010only (C) and combined eccentric and concentric contractions (E\u2009+\u2009C), on cellular respiration of PBMCs. It was hypothesized that metabolic cost and inflammation response to C versus E are different and would lead to different respiration responses of PBMCs. Combined eccentric and concentric contractions would reveal whether high metabolic cost and high inflammation response has an additive effect on cellular respiration of PBMCs. Finally, we studied ex vivo if lactate concentration and change in pH specifically affects cellular respiration of PBMCs.22.1Twelve healthy male subjects were recruited to the study through local advertisement . Inclusion criteria were experience in resistance training (>100\u2009kg bench press or \u22651.25 times bodyweight). We hypothesized that inflammation response in untrained test subjects might vary largely, therefore only trained test subjects were chosen to obtain more homogenous responses. In addition, inclusion criteria included no use of anabolic agents such as steroids or medication known to affect the inflammatory status.n with calculated effect sizes for study design by using G*Power program  with 80% power.We estimated the appropriate n\u00a0=\u00a011.All subjects gave their written informed consent prior to participation. All participants filled a PAR\u2010Q+ questionnaire  . All exercise protocols were completed with this isokinetic bench press device. The machine operated with a speed of 0.1\u00a0m/s in all three exercises, independent of the force produced against it. Ground reaction forces were recorded with a 2\u2010D strain gauge force plate  positioned under the bench. During the concentric and eccentric loadings, the bar's movement paused for 500\u2009ms at the top and bottom position, to aid pacing the contractions. In E, subjects were asked to start to maximally contract their muscles, once the bar stopped at the top position and continue pushing as hard as possible until the bar stopped at the bottom position . In C, subjects were asked to maximally contract their muscle once the bar stopped at the bottom position and continue pushing until the bar stopped at the up position. During the unloaded traveling phase of the machine, subjects were instructed to rest their arms while grasping the bar to avoid activation of the targeted muscles. During E\u2009+\u2009C, only 1\u00a0ms \u20182.4Maximal isometric force was recorded at 90\u00b0 of elbow flexion, measured with a custom\u2010made isometric bench press  were drawn from the antecubital vein from each subject while seated pre\u2010, 5\u00a0min post\u2010 and 24\u2009h post\u2010exercise to Vacutainer VACUETTE K3EDTA (Greiner Bio\u2010One) tubes containing anticoagulant (EDTA). Whole blood count and the number of lymphocytes and monocytes were assessed by Sysmex XP\u2010300 (Sysmex Corporation) to obtain the number of leukocytes and platelets. 18\u2009ml of blood was used for isolation of PBMCs and 12\u00a0ml for serum isolation.g). Serum was stored in \u221220\u00b0C for later analysis, which was performed using IMMULITE 2000 XPi Immunoassay System  according to manufacturers\u00b4 instructions. Lactate was measured from fingertip blood samples, which were collected into capillary tubes (20\u2009\u03bcl) at all three time points. Samples were then placed in a 1\u2009ml hemolyzing solution and analyzed automatically with Biosen C\u2010line lactate analyzer .For the detection of IL\u20106, CK and CRP, serum was isolated from blood samples by centrifugation . Standing time did not have a statistical effect on cellular respiration.g . The layer of PBMCs and platelets was collected and washed twice with RPMI\u20101640  in order to reduce PLT/PBMC ratio below 7  with 15\u00a0ml of Ficoll\u2010Paque TM PLUS  . Substrate\u2010uncoupler\u2010inhibitor titration 3 (SUIT3) protocol designed for intact cells was chosen for measurements  from five resistance trained men and isolated PBMCs and measured the cellular respiration by using the same methods as described above.To test whether lactate had an impact on the cellular respiration of PBMCs, 20\u2009mmol of sodium L\u2010lactate (Sigma Aldrich) was added to the HRR measurement chamber after measurements of routine respiration of PBMCs and SUIT3 protocol was completed \u2010lactic acid (Sigma Aldrich) to the HRR measurement chamber after routine respiration of PBMCs and SUIT3 protocol was completed. According to studies, a vigorous exercise can drop the pH of blood near 7.10 and could be under 7.0 in skeletal muscle .Statistical analyses were carried out using the Statistical Package for Social Sciences . Values are reported as mean\u2009\u00b1\u2009standard deviation (SD), unless otherwise stated. All values were verified for outliers, which were excluded from the analysis (>3\u00d7 interquartile range [IQR]). Significance level was set at 0.05 in all analyses. ANOVA with repeated measures was used to examine whether there were differences in the study variables between the groups over time . Mauchly's test was used to test the assumption of sphericity and Greenhouse\u2013Geisser corrections were applied if the assumption was violated. To study the effect of time separately within resistance exercises and group\u2009\u00d7\u2009time interaction between adjacent time points, within\u2010subject contrasts were used as post hoc comparison. Hedges' 33.1Cellular respiration of PBMCs was analyzed through several respiration states Table\u00a0, which i1)\u00a0=\u00a08.2, p\u00a0=\u00a00.017, g\u2009=\u2009\u22120.83), free routine activity (F(1)\u00a0=\u00a06.8, p\u00a0=\u00a00.025, g\u2009=\u2009\u22120.73) and ET\u2010 capacity (F(1)\u00a0=\u00a05.7, p\u00a0=\u00a00.038, g\u2009=\u2009\u22120.69) decreased significantly immediately after E\u2009+\u2009C \u00a0=\u00a010.8, p\u00a0=\u00a00.008, g\u2009=\u00a00.95) \u00a0=\u00a06.5, p\u00a0=\u00a00.032, g\u2009=\u00a00.73) and E\u2009+\u2009C (F(1)\u00a0=\u00a09.6, p\u00a0=\u00a00.013, g\u2009=\u00a00.94) in routine respiration \u00a0=\u00a09.5, p\u00a0=\u00a00.013, g\u2009=\u00a00.87)  in respiration states immediately after resistance exercise (from pre\u2010exercise to 5\u00a0min post\u2010exercise response) were compared between resistance exercises Figure\u00a0. Post hon Figure\u00a0. Free ro) Figure\u00a0.1)\u00a0=\u00a07.4, p\u00a0=\u00a00.026, g\u2009=\u00a01.17) .Main effects of group and time, and their interaction did not show statistical significances on CRP, CK or IL\u20106, hence there were no major changes between time points or between resistance exercises. Mean values and SDs of the data are represented in supplementary data \u00a0=\u00a089.3, p\u2009<\u20090.001, g\u2009=\u2009\u22122.74; E: \u221222\u2009\u00b1\u20096%, F(1)\u00a0=\u00a0131.2, p\u2009<\u20090.001, g\u2009=\u2009\u22123.32; E\u2009+\u2009C: \u221241\u2009\u00b1\u200910%, F(1)\u00a0=\u00a0160.6, p\u2009<\u20090.001, g\u2009=\u2009\u22123.84) and this was reversed at 24\u2009h post\u2010exercise \u00a0=\u00a046.1, p\u2009<\u20090.001, g\u2009=\u2009\u22122.14) and C (F(1)\u00a0=\u00a06.4, p\u00a0=\u00a00.032, g\u2009=\u2009\u22120.79) showed a statistically greater decrease than E \u00a0=\u00a013.8, p\u00a0=\u00a00.005, g\u2009=\u00a01.19)  in isometric force (from pre\u2010 to 5\u00a0min post\u2010exercise response) were compared between resistance exercises Figure\u00a0. E\u2009+\u2009C  Figure\u00a0.3.2.31)\u00a0=\u00a0103.1, p\u2009<\u20090.001, g\u2009=\u00a03.08; E: F(1)\u00a0=\u00a064.0, p\u2009<\u20090.001, g\u2009=\u00a02.32; E\u2009+\u2009C: F(1)\u00a0=\u00a0171.6, p\u2009<\u20090.001, g\u2009=\u00a03.80)  Figure\u00a0 and this1)\u00a0=\u00a014.8, p\u00a0=\u00a00.004, g\u2009=\u00a01.27) and C (F(1)\u00a0=\u00a05.3, p\u00a0=\u00a00.047, g\u2009=\u00a00.70) showed a statistically greater increase than E. Also, the increase from E\u2009+\u2009C was greater than the increase from C (F(1)\u00a0=\u00a05.2, p\u00a0=\u00a00.048, g\u2009=\u00a00.69)  in lactate levels (from pre\u2010 to 5\u00a0min post\u2010exercise response) were compared between resistance exercises Figure\u00a0. E\u2009+\u2009C  Figure\u00a0.3.3Pearson correlation coefficients for 5\u00a0min post\u2010exercise response in routine respiration, free routine activity and ET\u2010capacity in relation to 5\u00a0min post\u2010exercise response in lactate, isometric force and inflammation and muscle injury markers are presented in Table\u00a03.43)\u00a0=\u00a0\u22123.583, p\u00a0=\u00a00.035)  Figure\u00a0.3.5WBCs, as well as lymphocytes and monocytes, which are the main components of PBMCs, were counted at each time point and analyzed between timepoints and resistance exercises. The effect of plasma volume change was examined (according to Dill & Costill 1974] equation) \u00a0=\u00a037.4, p\u2009<\u20090.001, g\u2009=\u00a01.70; E: F(1)\u00a0=\u00a09.9, p\u00a0=\u00a00.010, g\u2009=\u00a00.91; E\u2009+\u2009C: F(1)\u00a0=\u00a018.7, p\u00a0=\u00a00.001, g\u2009=\u00a01.20) (Table\u00a01)\u00a0=\u00a05.7, p\u00a0=\u00a00.039, g\u2009=\u2009\u22120.72) and E\u2009+\u2009C (F(1)\u00a0=\u00a09.0, p\u00a0=\u00a00.012, g\u2009=\u2009\u22120.84). In C, the difference between pre\u2010 and 24\u2009h post\u2010exercise WBC counts were also significantly different (F(1)\u00a0=\u00a014.0, p\u00a0=\u00a00.003, g\u2009=\u00a01.04)  Table\u00a0. The dif1)\u00a0=\u00a018.6, p\u00a0=\u00a00.001, g\u2009=\u00a01.16; E: F(1)\u00a0=\u00a08.8, p\u00a0=\u00a00.014, g\u2009=\u00a00.83; E\u2009+\u2009C: F(1)\u00a0=\u00a020.6, p\u00a0=\u00a00.001, g\u2009=\u00a01.22) (Table\u00a01)\u00a0=\u00a011.7, p\u00a0=\u00a00.006, g\u2009=\u2009\u22120.92). The difference between pre\u2010 and 24\u2009h post\u2010exercise lymphocyte count was significantly different in C (F(1)\u00a0=\u00a011.1, p\u00a0=\u00a00.007, g\u2009=\u00a00.89). The number of monocytes was elevated after C (F(1)\u00a0=\u00a06.5, p\u00a0=\u00a00.027, g\u2009=\u00a00.68) and E (F(1)\u00a0=\u00a05.3, p\u00a0=\u00a00.045, g\u2009=\u00a00.64) and pre\u2010 and 24\u2009h post\u2010exercise count reached statistically significant difference in E (F(1)\u00a0=\u00a07.7, p\u00a0=\u00a00.019, g\u2009=\u00a00.77).Each resistance exercise elevated the number of lymphocytes (C: F(2) Table\u00a0. The dif1)\u00a0=\u00a011.7, p\u00a0=\u00a00.007, g\u00a0=\u00a00.66) and E (F(1)\u00a0=\u00a05.0, p\u00a0=\u00a00.048, g\u00a0=\u00a00.55). The number of lymphocytes was significantly higher after E\u2009+\u2009C when compared to C (F(1)\u00a0=\u00a010.1, p\u00a0=\u00a00.010, g\u00a0=\u00a00.66). There were no significant differences in the response between exercises among monocytes.Change (\u2206) in WBC, lymphocyte and monocyte counts (5\u00a0min post\u2010 exercise response) were compared between resistance exercises  contractions caused an acute decrease in cellular respiration of PBMCs as assessed by routine respiration, free routine capacity and ET\u2010capacity Figure\u00a0. ResultsChanges seen in routine control ratio were comparable with respiration results normalized to cell concentration Figure\u00a0. E\u2009+\u2009C c4.1PBMCs have a central role in muscle repair and exercise\u2010related anti\u2010inflammatory response by producing anti\u2010inflammatory cytokines  were somewhat lower than a previous study (10\u201312\u2009mmoL/L)  correlated negatively with the change in routine respiration Table\u00a0, indicat4.3Peripheral muscle fatigue is a result of several mechanisms including metabolic acidosis and reduction of ATP  axis eventually leading to elevated cortisol levels  exercise\u2010induced inflammation nor (2) anaerobic metabolites were contributing factors to the acute respiration responses.Experimental design: M.L., S.W., E.I.L., M.K. and I.K. Investigation and data collection: E.I.L, M.K., I.K., E.L. and A.K. Writing and manuscript preparation: E.I.L, M.K., A.K., H.K., S.W. and M.L. Review and editing of the manuscript: S.W., M.L., E.I.L. and H.K. Funding acquisition: H.K. All authors have read and agreed the final version of the manuscript.No conflicts of interest are declared by the authors."}
{"text": "The title compound arose from an unexpected alcoholysis of a prodrug by the methanol solvent. 14H13ClN2O2, was obtained during an attempt to grow single crystals of 4-acetyl\u00adphenyl 2-[(3-chloro-2-methyl\u00adphen\u00adyl)amino]\u00adnicotinate in methanol, and was probably generated by alcoholysis. Two intra\u00admolecular hydrogen bonds are formed, one between the N\u2014H group and the carbonyl O atom of the ester and the other between the ortho sp2CH group of the benzene ring and the pyridine N atom. Aromatic \u03c0\u2013\u03c0 stacking [shortest centroid\u2013centroid separation = 3.598\u2005(2)\u2005\u00c5] is observed in the extended structure.The title compound, C I) was first synthesized when preparing esters of anthranilic acid as possible analgesic and anti-inflammatory agents \u00b0 between the C1\u2013C6 benzene and N2/C8\u2013C12 pyridine rings \u2005\u00c5]: both of these close S(6) rings. The cohesion of the crystal structure is ensured by aromatic \u03c0\u2013\u03c0 stacking between the benzene and pyridine rings [shortest centroid\u2013centroid separation = 3.598\u2005(2)\u2005\u00c5] and hydro\u00adphobic inter\u00adactions amino]\u00adnicotin\u00adate, synthesized by a condensation reaction between clonixin and paracetamol  global, I. DOI: 10.1107/S2414314621005393/hb4383Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621005393/hb4383Isup3.cmlSupporting information file. DOI: 2085247CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound is consolidated by N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonding inter\u00adactions. 2H8N2)3][ZnCl4], exists as discrete ions. The [Zn(C2H8N2)3]2+ cation exhibits a distorted octa\u00adhedral shape. In the [ZnCl4]2\u2212 anion, the ZnII atom is in an almost regular tetra\u00adhedral environment. The crystal packing is consolidated by N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds.The title complex, [Zn(C X hydrogen bonds. Metal complexes containing an ethyl\u00adenedi\u00adamine (\u2013NCH2CH2N) backbone have attracted significant inter\u00adest as potential anti\u00adcancer agents because of their rich redox chemistry and relative ease of manipulation  is a common chelating ligand that is widely used in transition-metal complexes. It cannot only chelate metal cations by two nitro\u00adgen atoms, but also offers hydrogen atoms to form N\u2014H\u22efMetals such as zinc act as a key structural component in many proteins and enzymes, including transcription factors, cellular signalling proteins and DNA repair enzymes 3][ZnCl4], which comprises an ZnCl42\u2212 anion and a [Zn(en)3]2+complex cation. The ZnII atom of the tetra\u00adchlorido\u00adzincate(II) anion is in an almost regular Cl4 tetra\u00adhedral environment, with Zn\u2014Cl bond lengths in the range 2.255\u2005(1)-2.272\u2005(9)\u2005\u00c5. The zinc cation displays a distorted octa\u00adhedral coordination geometry defined by six N atoms from three ethyl\u00adenedi\u00adamine ligands, with Zn\u2014N distances in the range of 2.173\u2005(3)\u20132.219\u2005(3)\u2005\u00c5. The N\u2014Zn\u2014N angles of the en ligands are about 80\u00b0. They are noticeably smaller than the ideal octa\u00adhedral angle of 90\u00b0. The five-membered chelate rings are non-planar, with N\u2014C\u2014C\u2014N torsion angles of \u221257.5\u2005(4), \u221255.4\u2005(4) and \u221255.9\u2005(5)\u00b0. All of the three en ligands assume a synclinal conformation about the C\u2014C bond.Fig.\u00a01via inter\u00admolecular hydrogen bonds. The N\u2014H\u22efCl hydrogen-bonding inter\u00adactions between the N atoms of the ethyl\u00adenedi\u00adamine ligands and Cl atoms of the tetra\u00adchlorido\u00adzincate anion connect the mol\u00adecules, together with the weak C\u2014H\u22efCl intra\u00admolecular inter\u00adactions, generating a three-dimensional network  mixture. To this solution, ethyl\u00adenedi\u00adamine  in 25\u2005ml of an HCl/EtOH (2:3 v/v) mixture was added dropwise. The mixture was stirred and heated to 338\u2005K for 2\u2005h and allowed to stand at room temperature until colourless crystals separated (3\u20134 weeks). Crystals suitable for single-crystal XRD were collected after recrystallization using acidified water.Zinc chloride  was dissolved in 25\u2005ml of EtOH/HCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314620006185/bt4091sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314620006185/bt4091Isup2.hklStructure factors: contains datablock(s) I. DOI: 2001547CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In Table 1, the fraction of p\u2010c\u2010Jun+neurons in NeuroTrace+ neurons for AR group (Estimate and 95%CI) is shown as \u201c10.3% (10.1\u201310.5%).\u201d This should be \u201c13.0% (12.8\u201313.3%).\u201d The corrected Table 1 is shown below:<New Table 1 here>In Table S3, the fraction of p\u2010c\u2010Jun+neuronal population for AR group (Estimate and 95%CI) is shown as \u201c10.3% (10.1\u201310.5%).\u201d This should be \u201c13.0% (12.8\u201313.3%).\u201d Corrected version of Table S3 is corrected online.In the article by Ogino et al.,"}
{"text": "The structure of hexa\u00adaqua\u00adnickel(II) bis\u00ad(3-carb\u00adoxy-4-hy\u00addroxy\u00adbenzene\u00adsulfonate) dihydrate consists of alternating layers of inorganic cations and organic anions linked by O\u2014H\u22efO hydrogen bonds that also include non-coordinated water mol\u00adecules of crystallization. The structure of hexa\u00adaqua\u00adcobalt(II) bis\u00ad(3-carb\u00adoxy\u00adbenzene\u00adsulfonate) dihydrate is also built of alternating layers of complex cations and organic anions without direct coordination to the metal by the protonated carboxyl\u00adate or unprotonated sulfonate groups. A robust O\u2014H\u22efO hydrogen-bonding network involving primarily the coordinated and non-coordinated water mol\u00adecules and sulfonate groups directs the packing. 2O)6][C6H3(CO2H)(OH)SO3]2\u00b72H2O, (I), crystallizes in the triclinic space group P2O)6][C6H4(CO2H)SO3]2\u00b72H2O, (II), also crystallizes in triclinic PHexa\u00adaqua\u00adnickel(II) bis\u00ad(3-carb\u00adoxy-4-hy\u00addroxy\u00adbenzene\u00adsulfonate) dihydrate, [Ni(H As a result of the symmetry, the nickel ion has a very regular octa\u00adhedral coordination of six water mol\u00adecules  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z], and two in which the water hydrogen atoms H41 and H42 are donors to sulfonate oxygen atoms O1 and O2, respectively.The product of the reaction of nickel nitrate hexa\u00adhydrate and 5-sulfosalicylic acid (3-carb\u00adoxy-4-hy\u00addroxy\u00adbenzene\u00adsulfonic acid) is [Ni6](C6H4(CO2H)SO3)2\u00b72H2O, (II)Pet al., 1993vs C7\u2014O5 = 1.213\u2005(2)\u2005\u00c5] and rotated slightly out of the plane of the ring [torsion angle C2\u2014C3\u2014C7\u2014O4 = 4.6\u2005(2)\u00b0]. The sulfon\u00adate group is rotated about 19\u00b0 from its position in (I)vs \u221225.29\u2005(12)\u00b0 in (I)]. Presumably this difference is driven by the hydrogen-bonding patterns. The non-coordinated water mol\u00adecule has a different hydrogen-bonding environment , respectively. These inter\u00adactions are somewhat longer and less linear than those seen in (I)The reaction of cobalt nitrate hexa\u00adhydrate and sodium 3-sulfobenzoate (3-carb\u00adoxy\u00adbenzene\u00adsulfonate) produced crystals that have been identified as (C6H3(CO2H)(OH)SO3)2\u00b74H2O structure has also been reported for cobalt 6](C6H3(CO2H)(OH)SO3)2\u00b72H2O have been reported for manganese  salt of 3-carb\u00adoxy-4-hy\u00addroxy\u00adbenzene\u00adsulfonate has been reported previously ns Fig.\u00a04. Two watns Fig.\u00a04. The nonns Fig.\u00a04, and as ns Fig.\u00a04. Other O4.et al., 2016et al., 2005aet al., 2004et al., 2003det al., 2005et al., 2003bet al., 2003aet al., 2003eet al., 2003cet al., 2011et al., 2019A search of the Cambridge Structural Database 2.6H2O (Aldrich) in 50\u2005ml of water. The resulting clear green solution was stirred for about 30 minutes and transferred to a porcelain evaporating dish that was set out to evaporate in a fume hood. After several days, the water had completely evaporated leaving behind large elongated (>1\u2005cm) green slab-shaped crystals, 2.57\u2005g of which were collected by hand from the dish. These were identified as (I)3)2.6H2O (Aldrich) in 50\u2005ml of water. The resulting red solution was stirred for 30 minutes, transferred to a porcelain dish, and set out to evaporate. The final red product was primarily polycrystalline but some small red\u2013pink plates were found to be suitable for single-crystal X-ray analysis, leading to their identification as (II)A 2.54\u2005g (10.0\u2005mmol) sample of 5-sulfosalicylic acid (3-carb\u00adoxy-4-hy\u00addroxy\u00adbenzene\u00adsulfonic acid)  was dissolved in 100\u2005ml of water. To this colorless solution was added a green solution of 2.91\u2005g (10.0\u2005mmol) of Ni(NO6.Uiso constrained to be 1.2 times the Ueq of the bonding atom. Oxygen-bound hydrogen atoms were located in difference electron-density maps and refined with isotropic displacement parameters while the O\u2014H distances were restrained to 0.84\u2005(1)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022008295/mw2190sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989022008295/mw2190Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022008295/mw2190IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2202460, 2202459CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, the dimesitylboron group acts to reduce the delocalization of the nitro\u00adgen atom\u2019s lone pair into the pyrrole ring, with increases in the two N\u2014C bond lengths compared to pyrrole itself. The N\u2014B bond is 1.44125\u2005(15)\u2005\u00c5 long. 22H26BN, the B atom acts to reduce the delocalization of the nitro\u00adgen lone-pair electron density into the pyrrole ring, so that the two N\u2014C bonds increase in length to 1.4005\u2005(14) and 1.3981\u2005(14)\u2005\u00c5. The N\u2014B bond length is 1.4425\u2005(15)\u2005\u00c5, which is longer than a typical N\u2014B bond because the nitro\u00adgen lone pair is not fully available to participate in the bond.In the crystal structure of the title compound, C This mol\u00adecule has been investigated previously for its fluorescence, and shows a large Stokes shift, which involves twisted intra\u00admolecular charge transfer (TICT) of the excited state, by rotation about the N\u2014B bond  and 3.736\u2005(3)\u2005\u00c5], and is supported by the widening of the C\u2014B\u2014C bond angle [125.18\u2005(9)\u00b0], compared to the two N\u2014B\u2014C bond angles [118.30\u2005(10) and 116.42\u2005(9)\u00b0]. The mesityl groups\u2019 planes lie at 77.14\u2005(4)\u00b0 to each other, and at 69.18\u2005(3) and 67.06\u2005(4)\u00b0 to the pyrrole ring\u2019s best plane. The hydrogen atoms of three methyl groups  were modelled in two orientations. The positions and displacement parameters of hydrogen atoms on the pyrrole ring were refined, and for those attached to the C\u03b1 atoms, the H\u2014C\u03b1\u2014C\u03b2 angle showed widening to 131\u2013132\u00b0, similar to that in pyrrole (pyrrol-1-yl)borane ca 0.04\u2005\u00c5 longer than in similar compounds where the nitro\u00adgen atom is attached to two sp3 carbon atoms  and where the nitro\u00adgen lone pair is fully available for donation to boron. Compared to the mol\u00adecular geometry of pyrrole itself, as determined by X-ray crystallography at 103\u2005K  and 1.3514\u2005(17)\u2005\u00c5 and the C\u03b2\u2014C\u03b2 bond length is 1.4290\u2005(17)\u2005\u00c5. Thus, in contrast to pyrrole, the N\u2014C\u03b1 and C\u03b1\u2014C\u03b2 bonds are no longer similar in length, due to a reduction in the contribution of the nitro\u00adgen atom\u2019s lone pair to the electronic \u03c0 system of the pyrrole ring. When the mesityl groups are replaced by penta\u00adfluoro\u00adphenyl groups in derivative 2, the N\u2014B bond is considerably shorter than in 1 [1.4094\u2005(9) cf. 1.4425\u2005(15)\u2005\u00c5] due to greater lone-pair donation from nitro\u00adgen towards the more electron-deficient boron. Consequently, compared to 1, the pyrrole ring shows slightly longer N\u2014C bonds [1.4033\u2005(6)\u2005\u00c5] and a longer C\u03b2\u2014C\u03b2 bond [1.4418\u2005(9)\u2005\u00c5], though similar lengths for the C\u03b1\u2014C\u03b2 bonds [1.3553\u2005(6)\u2005\u00c5] (Table\u00a011 is similar to that when the pyrrole nitro\u00adgen atom is substituted with a carbonyl group to form an amide (Table\u00a01The N\u2014B bond is 1.4425\u2005(15)\u2005\u00c5 long. This is ] Table\u00a01. For come Table\u00a01.3.ab plane . Within a layer, the mol\u00adecules are related by centres of symmetry and translations along a and b. Adjacent layers are related by the twofold screw and n-glide planes. The four shortest inter\u00admolecular C\u22efH distances are in the range 2.81\u20132.83\u2005\u00c5. Two of these involve the meta-C atom, C18, with a methyl hydrogen atom and a pyrrole ring\u2019s hydrogen atom, which are directed to opposite sides of the phenyl ring [C18\u22efH12A and C18\u22efH3]. The two others involve both a meta and a para-C atom of the second phenyl ring and the pyrrole hydrogen atom H2 [C8\u22efH2 and C9\u22efH2].The mol\u00adecules are packed in layers in the ne Fig.\u00a02. There a4.1 bearing two 2\u2032-thienyl groups in the pyrrole\u2019s 2- and 5-positions \u20131.457\u2005(3)\u2005\u00c5] with a correlation between the increasing angle between bonding planes and longer N\u2014B bonds  and 1.440\u2005(3)\u2005\u00c5, similar to those in 1  using hexa\u00adne:di\u00adchloro\u00admethane (8:1) as eluent to give 1  as a slightly oily white solid, from which crystals were grown using ethyl acetate, m.p. 411\u2005K. 1H NMR  [ppm]: \u03b4 = 6.84 , 6.81 , 6.37 , 2.32 , 2.11 ; 13C NMR  [ppm]: \u03b4 = 141.7 , 139.0 (2 \u00d7 4\u2032-C), 136.5 br (2 \u00d7 1\u2032-C), 128.3 , 126.5 , 114.6 , 22.8 , 21.5 (2 \u00d7 4\u2032-CH3); IR (ATR): 2920, 2853, 1606, 1472, 1451, 1421, 1399, 1378, 1329, 1310, 1287, 1252, 1156, 1122, 1080, 1074, 1043, 1030, 850, 817, 763, 733, 717, 677, 656, 619, 560, 516\u2005cm\u22121.A solution of pyrrole  in THF (10\u2005mL) under nitro\u00adgen was treated with sodium hydride  and the mixture stirred at 293\u2005K for 2\u2005h. Dimesitylboron fluoride (CARE: gives HF with moisture)  in dry THF (10\u2005mL) was added at room temperature. The mixture was left to stir overnight. The bright orange\u2013yellow mixture was quenched with water (20\u2005mL), extracted with ether (2 \u00d7 30\u2005mL) and the combined organic phase was dried over MgSO6.Ueq of the parent atom for aromatic groups and at 1.5Ueq for methyl groups.Crystal data and details of data collection and structure refinement are summarized in Table\u00a0210.1107/S2056989022011768/zv2023sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022011768/zv2023Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022011768/zv2023sup3.docxThis is NMR data requested by the referee. DOI: Click here for additional data file.10.1107/S2056989022011768/zv2023Isup4.cmlSupporting information file. DOI: 2166138CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Due to a production error, there were inaccuracies in the section numbering. The corrected subsection numbering should read as follows:1. Introduction2. Immunotheraputic Strategies Targeting the TME\u20032.1 Therapeutic Strategies Based on TME Inhibitory Signaling\u2003\u20032.1.1 Targeting TME Physical Barriers\u2003\u20032.1.2 Targeting Immune Checkpoints\u2003\u20032.1.3 Targeting Immunosuppresive Cells\u2003\u20032.1.4 Targeting Inhibitory Cytokines\u2003\u20032.1.5 Targeting Metabolic Inhibition Signaling\u20032.2 Therapeutic Strategies Based on TME Stimulatory Signals\u2003\u20032.2.1 Targeting Stimulatory Checkpoints\u2003\u20032.2.2 Application of Stimulating Cytokines\u2003\u20032.2.3 Enhancing Antigen Presentation\u2003\u20032.2.4 Application of Immune Effector cells3. Challenges Faced by Time Research and Solutions\u20033.1 Complexity of TIME\u20033.2 Spatiotemporal Heterogenity of TIME\u20033.3 Systemic Immunity Affects TME Immune Response4. Summary and ProspectThe publisher apologizes for this mistake.The original version of this article has been updated."}
{"text": "MAPK can underlie the pro-differentiation effect of CP-673451 on GBM cells. Overall, the present study identifies a potential novel therapeutic option that could benefit GBM patients in the future, through differentiation of residual GSCs post-surgery, with the aim to limit recurrence and improve quality of life.Glioblastoma (GBM) is the most common and fatal primary brain tumour in adults. Considering that resistance to current therapies leads to limited response in patients, new therapeutic options are urgently needed. In recent years, differentiation therapy has been proposed as an alternative for GBM treatment, with the aim of bringing cancer cells into a post-mitotic/differentiated state, ultimately limiting tumour growth. As an integral component of cancer development and regulation of differentiation processes, kinases are potential targets of differentiation therapies. The present study describes how the screening of a panel of kinase inhibitors (KIs) identified PDGF-R\u03b1/\u03b2 inhibitor CP-673451 as a potential differentiation agent in GBM. We show that targeting PDGF-R\u03b1/\u03b2 with CP-673451 in vitro triggers outgrowth of neurite-like processes in GBM cell lines and GBM stem cells (GSCs), suggesting differentiation into neural-like cells, while reducing proliferation and invasion in 3D hyaluronic acid hydrogels. In addition, we report that treatment with CP-673451 improves the anti-tumour effects of temozolomide in vivo using a subcutaneous xenograft mouse model. RNA sequencing and follow-up proteomic analysis revealed that upregulation of phosphatase DUSP1 and consecutive downregulation of phosphorylated-p38 Glioblastoma (GBM) is the most common and fatal primary brain tumour in adults , 2 with While numerous therapeutic approaches aim for cancer cell death, a few studies have instead started exploring treatments that induce cancer cell differentiation into non-neoplastic cells as a novel strategy . Indeed,GBM treatment could highly benefit from differentiation therapies. High resistance to classic cytotoxic treatments and the presence of pluripotent cancer stem cells (CSCs) in residual tumour tissues due to incomplete surgical excision make GBM a good candidate for differentiation therapies \u201316. SeveIn accordance with these reports, the present study describes the screening of a panel of KIs that led to the identification of a receptor tyrosine kinase (RTK) inhibitor, namely CP-673451, which targets the platelet-derived growth factor receptor \u03b1/\u03b2 (PDGF-R\u03b1/\u03b2) as a potential differentiation agent in GBM. Herein, we propose that CP-673451 treatment can induce the upregulation of phosphatase dual-specificity phosphatase 1 (DUSP1) and consecutive downregulation of phosphorylated p38 mitogen-activated protein kinase (MAPK), leading to the onset of differentiation of GBM cells, thus limiting proliferation and invasion in vitro, while improving the anti-tumour effects of temozolomide in vivo.50, no previously identified undesirable effects  at the required concentrations and with the ability to cross the blood-brain barrier (BBB) [p-value) can be found in Table Forty-seven KIs were selected from the KI library (SelleckChem) on the basis of high potency with low ICer (BBB) \u201327. A fun\u2009=\u200947) for 24\u2009h before nine images were taken per well. All images were analysed for total neurite-like process length and normalised by cell number to obtain an average neurite-like process length per cell , pink, blue and red triangles indicate KIs with significant effects compared to the control . Inhibitors showing effects with p\u2009\u2264\u20090.001 were selected for further experiments, namely: LY2835219, a potent and selective inhibitor of CDK4/6 [Neurite-like process outgrowth was quantified following treatment to select KIs with potential differentiating effects. A schematic diagram illustrates the experimental design Fig.  with U87ell Fig. . The gref CDK4/6 , CP-6734f CDK4/6  and pacrf CDK4/6  Fig. 1Bn\u2009=\u200947 fop\u2009\u2264\u20090.001), 30.5\u2009\u00b1\u20095.1\u2009\u03bcm (p\u2009\u2264\u20090.01), 52.8\u2009\u00b1\u20096.9\u2009\u03bcm (p\u2009\u2264\u20090.001) and 32.1\u2009\u00b1\u20093.6\u2009\u03bcm (p\u2009\u2264\u20090.01), respectively. In AS, a significant increase of the average neurite-like process length per cell was observed following treatment with CP-673451 (72.1\u2009\u00b1\u200924.63\u2009\u03bcm (p\u2009\u2264\u20090.05)) as compared to the control (28.2\u2009\u00b1\u20095.3\u2009\u03bcm). CP-673451 similarly caused the average neurite-like process length per cell to increase significantly in LN229 cells (25.3\u2009\u00b1\u20097.7\u2009\u03bcm (p\u2009\u2264\u20090.01)) as compared to the control (0.9\u2009\u00b1\u20090.5\u2009\u03bcm). Finally, LY2835219, pelitinib and CP-673451 treatments caused a significant increase in the average neurite-like process length (15.3\u2009\u00b1\u20095.2\u2009\u03bcm (p\u2009\u2264\u20090.05), 15.9\u2009\u00b1\u20096.4\u2009\u03bcm (p\u2009\u2264\u20090.05) and 56.0\u2009\u00b1\u20099.6 (p\u2009\u2264\u20090.001) respectively) in the U138 cells compared to the control (3.9\u2009\u00b1\u20090.3\u2009\u03bcm) , as a normal brain cell type control . Neurite\u03bcm) Fig. .Fig. 2Sep\u2009\u2264\u20090.01) compared to the control, while a slight decrease in viability was observed in U138 and LN229 GBM cells following treatment with pacritinib (0.9\u2009\u00b1\u20090.05\u2009RAU (p\u2009\u2264\u20090.05) and 0.8\u2009\u00b1\u20090.06\u2009RAU (p\u2009\u2264\u20090.05), respectively). Treatments with LY2835219, pelitinib and pacritinib were also observed to significantly affect LN229 cell proliferation compared to the control (0.8\u2009\u00b1\u20090.09\u2009RAU (p\u2009\u2264\u20090.01), 0.8\u2009\u00b1\u20090.1\u2009RAU (p\u2009\u2264\u20090.05) 0.8\u2009\u00b1\u20090.1\u2009RAU (p\u2009\u2264\u20090.05), respectively). Altogether, treatment with 1\u2009\u03bcM of the selected KIs appeared to stimulate neurite-like process outgrowth in most studied GBM cell lines and astrocytes, with limited impact on cell viability and proliferation.To examine how various treatments affected cell viability and growth, metabolic activity and proliferation were measured following treatment with the inhibitors of interest using WST-1 ) in G166 cells as compared to control (1.2\u2009\u00b1\u20090.6\u2009\u03bcm). In addition, 1\u2009\u00b5M LY2835219, CP-673451 and pacritinib led to significant increases in the average neurite-like process length (35.9\u2009\u00b1\u20097.0\u2009\u03bcm (p\u2009\u2264\u20090.01), 21.6\u2009\u00b1\u20092.7\u2009\u03bcm (p\u2009\u2264\u20090.01) and 20.3\u2009\u00b1\u20095.1\u2009\u03bcm (p\u2009\u2264\u20090.05), respectively) in GS090 GSCs compared to the control (13.8\u2009\u00b1\u20092.5\u2009\u03bcm). Finally, 1\u2009\u00b5M LY2835219, pelitinib and CP-673451 significantly increased the average neurite-like process length per cell (26.7\u2009\u00b1\u20096.0\u2009\u03bcm (p\u2009\u2264\u20090.05) 25.2\u2009\u00b1\u20093.2\u2009\u03bcm (p\u2009\u2264\u20090.05) and 28.1\u2009\u00b1\u20094.6\u2009\u03bcm (p\u2009\u2264\u20090.05), respectively) in G179 GSCs, compared to the control (12.3\u2009\u00b1\u20094.4\u2009\u03bcm). Representative light microscopic images are shown, with neurite-like processes indicated by red arrows.As one of the drivers of GBM recurrence with multipotent abilities, GSCs are the putative main targets of differentiation therapy. For these reasons, the selected KIs were used to treat different GSC lines, including G166, GS090 and G179. Their morphology was observed using light microscopy following treatment and the average neurite-like process length per cell was calculated as before Fig. . Treatmep\u2009\u2264\u20090.05) and 0.9\u2009\u00b1\u20090.07\u2009RAU (p\u2009\u2264\u20090.05), respectively). On the other hand, cell viability increased significantly following treatment with CP-673451 (1.04\u2009\u00b1\u20090.02\u2009RAU (p\u2009\u2264\u20090.05)) as compared to the control. Further, proliferation assays indicated that G166 cell proliferation decreased after pelitinib treatment (0.9\u2009\u00b1\u20090.04\u2009RAU (p\u2009\u2264\u20090.01)) but increased upon treatment with CP-673451 (1.3\u2009\u00b1\u20090.14\u2009RAU (p\u2009\u2264\u20090.05)) as compared to the control. Regarding GS090 cells, CP-673451 treatment decreased proliferation (0.99\u2009\u00b1\u20090.01\u2009RAU (p\u2009\u2264\u20090.01)) as compared to the control. None of the KI treatments caused significant changes in G179 proliferation.GSC viability (WST-1) -PDGF-R\u03b1/\u03b2 (tyr849/tyr857) was measured as well as PDGF-R\u03b2 upon treatment with CP-673451. U87 GBM cells were treated with 1\u2009\u00b5M CP-673451 for 0, 15\u2009min, 1, 4, 24 and 48\u2009h ), PROM-1 (1.64\u2009\u00b1\u20090.18\u2009fc (p\u2009\u2264\u20090.01)) and VEGFA (1.29\u2009\u00b1\u20090.05\u2009fc (p\u2009\u2264\u20090.001)). Treatment also indicated significant decreases in GFAP (0.54\u2009\u00b1\u20090.07\u2009fc (p\u2009\u2264\u20090.001)), CSPG4 (0.57\u2009\u00b1\u20090.04\u2009fc (p\u2009\u2264\u20090.0001)) and CD44 (0.7\u2009\u00b1\u20090.03\u2009fc (p\u2009\u2264\u20090.001)). Upon treatment with 1\u2009\u03bcM CP-673451, G179 GSCs also showed a significant increase in the expression of NEFL (3.47\u2009\u00b1\u20090.51\u2009fc (p\u2009\u2264\u20090.0001) and significant decreases in the expression of nestin and PROM1 (0.69\u2009\u00b1\u20090.09\u2009fc (p\u2009\u2264\u20090.001) and 0.18\u2009\u00b1\u20090.37\u2009fc (p\u2009\u2264\u20090.01), respectively), CSPG4 (0.65\u2009\u00b1\u20090.06\u2009fc (p\u2009\u2264\u20090.001) and VEGFA (0.66\u2009\u00b1\u20090.03\u2009fc (p\u2009\u2264\u20090.001).Gene expression of specific differentiation markers was quantified using qRT-PCR in order to determine which specific normal brain cell lineage  the GBM cells were differentiating into upon CP-673451 treatment. The selected differentiation markers were as follows; Astrocytic (GFAP and ALDH1L1), Neuronal (\u03b23-tubulin and NEFL), stem cell (nestin and PROM-1 (CD133), oligodendrocyte (OLIG2 and CSPG4) and mesenchymal (VEGFA and CD44). Upon treatment of U87 GBM cells with 1\u2009\u00b5M CP-673451 for 96\u2009h Fig. , cells sAltogether our data showed that treatment with CP-673451 could trigger a neuron-like differentiation in GBM cells, as supported by the formation of neurite-like processes and expression of the neuronal NEFL marker in GBM cells, with concomitant decrease of expression of markers for stem cells and other brain cell types.p\u2009\u2264\u20090.05)). Conversely, a significant decrease in cell proliferation was observed in GS090 cells upon treatment with 5\u2009\u00b5M CP-673451 (0.7\u2009\u00b1\u20090.03\u2009RAU (p\u2009\u2264\u20090.01)), as compared to the control. All three cell lines showed a significant decrease in proliferation when treated with 10\u2009\u00b5M CP-673451: U87 (0.7\u2009\u00b1\u20090.04\u2009RAU (p\u2009\u2264\u20090.001)), GS090 (0.6\u2009\u00b1\u20090.07\u2009RAU (p\u2009\u2264\u20090.001)) and G179 (0.7\u2009\u00b1\u20090.06\u2009RAU (p\u2009\u2264\u20090.01)), as compared to the control.To further characterise the effect of CP-673451 on proliferation, additional experiments with increasing concentrations of the inhibitor were performed. The U87 GBM cell line and GS090 and G179 GSCs were treated with increasing concentrations of CP-673451  for 48\u2009h, while a proliferation assay  was also performed Fig. . A signip\u2009\u2264\u20090.001) and G179: 0.6\u2009\u00b1\u20090.07 (p\u2009\u2264\u20090.001). Following CP-673451 treatment, significant decreases in cell colony size were observed at 1, 5 and 10\u2009\u00b5M in U138 (0.7\u2009\u00b1\u20090.17 (p\u2009\u2264\u20090.05), 0.6\u2009\u00b1\u20090.11 (p\u2009\u2264\u20090.01), 0.5\u2009\u00b1\u20090.05 (p\u2009\u2264\u20090.0001)) and GS090 (0.8\u2009\u00b1\u20090.09 (p\u2009\u2264\u20090.05) 0.7\u2009\u00b1\u20090.08 (p\u2009\u2264\u20090.01) and 0.5\u2009\u00b1\u20090.1 (p\u2009\u2264\u20090.01)). No significant alterations of the number of colonies were observed in the tested cell lines upon CP-673451 treatment. Yet, a significant decrease in U87 cell metabolic activity  and 0.8\u2009\u00b1\u20090.06 (p\u2009\u2264\u20090.01), respectively). Similarly, U138 showed a significant decrease in metabolic activity upon treatment with 1, 5 and 10\u2009\u03bcM CP-673451 (0.7\u2009\u00b1\u20090.05 (p\u2009\u2264\u20090.001), 0.7\u2009\u00b1\u20090.07 (p\u2009\u2264\u20090.01), 0.7\u2009\u00b1\u20090.06 (p\u2009\u2264\u20090.001)), while both GS090 and G179 GSCs showed a significant decrease in metabolic activity upon CP-673451 treatment at 10\u2009\u00b5M (0.6\u2009\u00b1\u20090.11 (p\u2009\u2264\u20090.01)) and (0.9\u2009\u00b1\u20090.04 (p\u2009\u2264\u20090.01)), respectively. Altogether, it appears that treatment with CP-673451 limits the proliferation and invasiveness of GBM cells while stimulating their neuron-like differentiation in vitro.A HA based hydrogel assay was implemented to assess the invasiveness and colony forming ability of the U87 and U138 GBM cell lines and GS090 and G179 GSCs in a 3D model when treated with increasing concentrations of CP-673451 . Cell metabolic activity was also measured in parallel (using a CellTiter-Glo luminescent cell viability assay). Both the colony areas Fig.  and coloity Fig.  was measIn the interest of ensuring the effects from pharmacological inhibition in U87 GBM cells upon CP-673451 treatment were due to specific inhibition of its targets PDGF-R\u03b1 and PDGF-R\u03b2, gene silencing using siRNA was performed.p\u2009\u2264\u20090.0001) and 95% 0.05\u2009\u00b1\u20090.03 (p\u2009\u2264\u20090.0001), respectively. In addition, PDGF-R\u03b2 expression was also reduced at both 50\u2009nM and 100\u2009nM by 47% 0.53\u2009\u00b1\u20090.18 (p\u2009\u2264\u20090.01) and 46% 0.53\u2009\u00b1\u20090.23 (p\u2009\u2264\u20090.05), respectively. KD of PDGF-R\u03b1 and \u03b2 was also validated in G179 cells ) and PDGF-R\u03b2 48% (0.52\u2009\u00b1\u20090.2 (p\u2009\u2264\u20090.01)) compared to the control. At 100\u2009nM siRNA, the gene expression of PDGF-R\u03b1 was reduced by 57% (0.43\u2009\u00b1\u20090.1 (p\u2009\u2264\u20090.0001)) while gene expression of PDGF-R\u03b2 was reduced by 48% (0.52\u2009\u00b1\u20090.02 (p\u2009\u2264\u20090.001)). Further validating the siRNA transfection, the protein expression of PDGF-R\u03b1 and PDGF-R\u03b2 was decreased in U87 GBM cells and G179 GSCs. PDGF-R\u03b2 protein expression was reduced by 72% in U87 GBM cells at both 50\u2009nM and 100\u2009nM concentrations of siRNA compared to control (0.28\u2009\u00b1\u20090.1 (p\u2009\u2264\u20090.0001))  and PDGF-R\u03b2 by 33% 0.67\u2009\u00b1\u20090.2 (p\u2009\u2264\u20090.05). 100\u2009nM siRNA reduced PDGF-R\u03b1 protein expression by 26% 0.74\u2009\u00b1\u20090.1 (p\u2009\u2264\u20090.05) and PDGF-R\u03b2 by 40% 0.60\u2009\u00b1\u20090.2 (p\u2009\u2264\u20090.05) ). Treatment of U87 GBM cells with 100\u2009nM PDGF-R\u03b2 siRNA compared to the control (18.9\u2009\u00b1\u20091.7\u2009\u00b5m) displayed a significant increase in neurite-like process length average per cell (29.8\u2009\u00b1\u20092.9\u2009\u00b5m (p\u2009\u2264\u20090.001)), as did the combination of PDGF-R\u03b1 and \u03b2 siRNA (29.1\u2009\u00b1\u20096.8\u2009\u00b5m (p\u2009\u2264\u20090.05)). Similarly, KD PDGF-R\u03b1 in G179 cells with siRNA at 50 and 100\u2009nM significantly increased the average length of neurite-like process per cell (10.7\u2009\u00b5m\u2009\u00b1\u20092.1 (p\u2009\u2264\u20090.05)) compared to the control (7.9\u2009\u00b1\u20091.5\u2009\u00b5m) and (12.4\u2009\u00b1\u20092.9\u2009\u00b5m (p\u2009<\u20090.05)) compared to the control (8.8\u2009\u00b1\u20091.3\u2009\u00b5m), respectively. KD of both PDGF-R\u03b1 and \u03b2 also increased neurite-like process outgrowth compared to the controls (10.7\u2009\u00b1\u20091.2\u2009\u00b5m (p\u2009\u2264\u20090.05)) ) Fig. .Fig. 4GeAs specific gene silencing of PDGF-R\u03b1 and PDGF-R\u03b2 enhanced neurite-like process growth in U87 GBM cells and G179 GSCs, these data suggest that the observed impact of CP-673451 treatment on GBM cells should be, at least partly, due to specific PDGF-R\u03b1/\u03b2 inhibition.3): TMZ: 16.75\u2009\u00b1\u20095.4\u2009mm3 (p\u2009\u2264\u20090.01), CP-673451: 35.9\u2009\u00b1\u200916.9\u2009mm3 (p\u2009\u2264\u20090.01) and TMZ\u2009+\u2009CP-673451: 6.06\u2009\u00b1\u20092.3 mm3 (p\u2009\u2264\u20090.01). Tumour volumes from the combination treatment group were significantly reduced compared to both singular treatments.The in vivo anti-tumour activity of CP-673451 was evaluated using a U87 xenograft GBM mouse model Fig. . Treatmep\u2009\u2264\u20090.01), CP-673451: 352.4\u2009\u00b1\u2009115.6 (p\u2009\u2264\u20090.05) and TMZ\u2009+\u2009CP-673451: 36.2\u2009\u00b1\u200912.1 (p\u2009\u2264\u20090.001). There were significantly fewer ki67-positive cells in the TMZ\u2009+\u2009CP-673451 group compared to CP-673451 treatment alone. Altogether it appeared that CP-673451 treatment can improve the inhibitory effect of TMZ on tumour growth in vivo.Tumour samples were stained for proliferation marker Ki67 Fig. . The numTo decipher the signalling mechanism underlying the effect of CP-673451 on GBM cell differentiation, RNA-seq was performed on U87 GBM cells treated with CP-673451 for 48\u2009h (compared to DMSO control). Whole transcriptome correlation matrix showed a high similarity between the replicate samples Fig. . DESEQ2 p-value\u2009=\u20090.003) and Hallmark NF-\u03baB signalling  in comparison to U87 GBM cells treated with DMSO  in CP-673451 treated U87 GBM cells compared to control [p\u2009\u2264\u20090.0001), 2.5\u2009\u00b1\u20091.0 (ns), respectively) ) and 45% (0.55\u2009\u00b1\u20090.14\u2009fc (p\u2009\u2264\u20090.001)) compared to the control siRNA (siCTRL)  simultaneously at 50\u2009nM for 24\u2009h. G179 GSCs were treated by reverse transfection with 100\u2009nM DUSP1 siRNA (SMPs 3 and 4) simultaneously for 48\u2009h. DUSP1 KD was validated by qRT-PCR in U87 GBM cells and G179 GSCs 62% (0.38\u2009\u00b1\u20090.04\u2009fc (vs 53.8\u2009\u00b1\u20098.27\u2009\u03bcm (p\u2009\u2264\u20090.01)) and G179 GSCs (30% (13.0\u2009\u00b1\u20091.1\u2009\u00b5m vs 18.5\u2009\u00b1\u20092.2\u2009\u00b5m (p\u2009\u2264\u20090.01)) ) and 21% (14.2\u2009\u00b1\u20090.8\u2009\u00b5m vs 18.0\u2009\u00b1\u20092.3\u2009\u03bcm (p\u2009\u2264\u20090.05)), respectively ) Fig. . In addiely Fig. .Fig. 7DUp\u2009\u2264\u20090.05)) and G179 GSCs (3.7\u2009\u00b1\u20091.4 fold increase (p\u2009\u2264\u20090.05)) compared to control  fold in U87 GBM cells and 30.8\u2009\u00b1\u200913.1 fold (p\u2009\u2264\u20090.05) in G179 GSCs compared to control . In G179 GSCs, transfection with the DUSP1 plasmid increased the average neurite-like process length by 47% compared to the control 7.9\u2009\u00b1\u20090.3\u2009\u00b5m vs 5.4\u2009\u00b1\u20090.6\u2009\u03bcm (p\u2009\u2264\u20090.01)  and 0.72\u2009\u00b1\u20090.16 (p\u2009\u2264\u20090.05), respectively). Co-treatment with DUSP1 inhibitor BCI abrogated this decrease in p38MAPK phosphorylation  is essential to the growing neurites of the developing neurons , 35, 36.MAPK, one of DUSP1 down-stream targets, also including p44/p42MAPK (ERK1/2) and SAPK/JNK [via p38MAPK inhibition due to DUSP1 activity. Interestingly, a separate study reported that high DUSP1 levels correlate with increased GBM patient survival. Authors revealed that overexpression of DUSP1 in GSCs impedes self-renewal and induces differentiation via deactivation of p38MAPK in vitro, reducing tumourigenicity and increasing sensitivity to TMZ therapy [Further supporting this observation, our RNA-seq analysis identified DUSP1 expression to be significantly upregulated in GBM cells upon treatment with CP-673451. DUSP1 has been reported to be essential in the early hours of neuronal differentiation during embryogenesis. Its activity is required for both limiting cell proliferation and ensuring proper neurite outgrowth. DUSP1 is also directly implicated in the maintenance of neuronal integrity . PreviouSAPK/JNK , 38, 41.Taken together, these results thus suggest that CP-673451 treatment could hold great promise as part of a novel therapeutic strategy against GBM. CP-673451 is a low molecular weight kinase inhibitor (molecular weight\u2009=\u2009417.52)  with thevia DUSP1 is being reported. Yet, our present investigation presents some limitations that would need to be addressed in follow-up studies. Among these, the upstream mechanism between PDGF-R inhibition and upregulation of DUSP1 is yet to be elucidated. However, our RNA-seq data demonstrated a significant enrichment of genes linked to the NF-\u03baB pathway upon treatment of GBM cells with CP-673451. Accordingly, the promoter region of the DUSP1 gene contains binding sites for NF-\u03baB [To our knowledge, this is the first time such an effect of PDGF-R inhibition on GBM cell differentiation or NF-\u03baB . In addior NF-\u03baB , 45. Lasor NF-\u03baB , 51.Altogether, this study has identified a KI, CP-673451, able to induce differentiation in GBM cells, with the potential to target GSCs, which are known to be directly implicated in GBM therapeutic resistance and inevitable recurrence. CP-673451 treatment could thus refine therapeutic strategies against GBM, through reducing side effects and enhancing response to current therapies, consequently improving patients\u2019 quality of life.2 atmosphere. Astrocytes and established human GBM cell lines were purchased from the American Type Culture Collection (ATCC). Astrocytes (AS) were seeded onto flasks and plates pre-treated with 2\u2009\u03bcg/cm2 poly-L-lysine (Sigma-Aldrich) and required Astrocyte growth medium (Sigma-Aldrich) 10% foetal bovine serum (FBS) (Sigma-Aldrich) and 100 units ml\u22121 penicillin, 100\u2009\u03bcg\u2009ml\u22121 streptomycin and L-glutamine (1% PSG) (Sigma-Aldrich). U87 and U138 cells required minimum essential medium (MEM) 10% FBS and 1% PSG. LN229 cells required Dulbecco\u2019s modified eagle medium (DMEM) 10% FBS and 1% PSG.Cells were maintained at 37\u2009\u00b0C in a humidified 5% COPatient-derived GSCs  were a kind gift from Dr. Angela Bentivegna, University of Milan-Bicocca, Italy and Dr. David Nathanson, University of California, Los Angeles, US. GSCs were isolated from GBM tumour samples following local ethical board approval. GSCs were maintained as neurospheres in DMEM/F12 Ham (Sigma-Aldrich), 1% B27 without vitamin A (Gibco), 1% Glutamax (Gibco) and 1% PSG with a mix of growth factors . Medium was changed twice a week. GBM cell lines and astrocytes were detached at confluence using trypsin/EDTA (Sigma-Aldrich). GSCs were disassociated using TrypleE express enzyme (Gibco) and separated into single cells through a 70\u2009\u03bcm cell strainer (Starstedt). All cells were tested for mycoplasma at the beginning of the study.3 cells per well) into a 96-well plate and treated with 1\u2009\u03bcM of 47 KIs from a library of 378 (SelleckChem) for 24\u2009h in 10% FBS. The automated liquid handler Biomek 4000 was used for performing this screening (Beckman Coulter). Dimethyl sulfoxide (DMSO) was used as a vehicle control. GSCs were treated with 10% FBS to enhance cell attachment. Following 24\u2009h (GBM cell lines) and 48\u2009h (GSCs) treatment with KIs, images of the cells were taken, and length of neurite-like process was measured as described below.Cells were counted using the automated cell counter Countess (Invitrogen), seeded (2\u2009\u00d7\u200910Light microscopic images were taken at 20x magnification (mag) using the Olympus IX71 microscope with Micromanager software. The length of long thin extensions termed \u2018neurite-like processes\u2019 were analysed. Three technical repeats were performed with nine images taken per well and all neurite-like processes analysed. The semi-automatic Fiji (ImageJ) plugin \u2018simple neurite tracer\u2019 was used to measure the lengths of the neurite-like processes. The total lengths of neurite-like processes per well were quantified and normalised by the total number of cells per well to calculate the average length of neurite-like process per cell. Graphs display the mean\u2009\u00b1\u2009SD of at least three independent experiments, representative images shown, red arrows indicating neurite-like processes.3 or 5\u2009\u00d7\u2009103 cells per well) into a 96-well plate with 10% FBS 1% PSG for 24\u2009h before the treatments were applied. Cells were then treated with 0, 1, 5 or 10\u2009\u00b5M of the stated KIs. Following 24\u2009h (GBM cell lines) or 48\u2009h (GSCs) treatment, cells were fixed with 4% paraformaldehyde (PFA) in 1x phosphate buffered saline (PBS) (Sigma-Aldrich) and incubated at room temperature (temp) for 30\u2009min. PFA was removed and plates left to dry at room temp for 10\u2009min. They were then washed once with PBS and stained with 0.1% crystal violet solution at room temp for 30\u2009min. The solution was then aspirated and washed in 1x PBS twice and water once and left open overnight to dry. When ready to read, 50\u2009\u03bcl of 10% acetic acid was added to each well, plates were agitated on a plate rocker for 20\u2009min and absorbance was recorded at 600\u2009nm using a GloMax Explorer reader (Promega). Graphs show the mean\u2009\u00b1\u2009SD of at least three independent experiments.Cells were seeded (2\u2009\u00d7\u2009103 cells per well) into a 96-well plate with 10% FBS 1% PSG for 24\u2009h before the treatments were applied. Cells were then treated with DMSO or 1\u2009\u00b5M of the stated KIs. Following 24\u2009h (GBM cell lines) or 48\u2009h (GSCs) treatment, 10\u2009\u03bcl of water-soluble tetrazolium salts-1 (WST-1) reagent was added to each well and incubated at 37\u2009\u00b0C, 5% CO2 for 2\u2009h. The plate was then agitated on a plate rocker at room temp for 1\u2009min and the absorbance recorded at 450\u2009nm using a GloMax Explorer reader (Promega). Graphs show the mean\u2009\u00b1\u2009SD of at least three independent experiments.Cells were seeded (2\u2009\u00d7\u200910U87 GBM cells were treated with DMSO or CP-673451 (CP) for 48\u2009h and RNA was purified following PureLink RNA Mini Kit (Life technologies) protocol, as described before . All conhttp://hannonlab.cshl.edu/fastx_toolkit/license.html). The quality of reads were confirmed using the fastqc tool kit (v 0.11.5) (http://www.bioinformatics.babraham.ac.uk/projects/fastqc/), and only high-quality clean read were used for down-stream analyses. The high-quality reads were mapped to the ENSEMBL built GRCH37 using the STAR aligner (v2.5.3a) [p value (Padj\u2009\u2264\u20090.05) and Log2 fold change\u2009\u2265\u2009|1| were used as the threshold to screen significance of differentially expressed genes (DEGs). Gene set enrichment function from the enrichplot package (https://github.com/YuLab-SMU/enrichplot) was used to perform gene set enrichment analysis for Hallmark gene sets and CAHOY CNS neural cell type gene sets deposited in the MSIGDB (https://www.gsea-msigdb.org/gsea/msigdb/index.jsp).High-quality clean reads were obtained by trimming the adaptor sequences and removing reads that contained poly-N or were of low-quality from the raw data using the fastX tool kit (v 0.0.14) (v2.5.3a)  with thev2.5.3a) . Differe5 cells per T75\u2009cm2 or 1\u2009\u00d7\u2009105 per well into a 6-well plate) and were treated with drug/control or target/control siRNA plasmid/control for the concentration and time stated. Cells were lysed, RNA was then purified following PureLink RNA Mini kit (Life technologies) protocol. Reverse transcription was carried out using a cDNA synthesis kit (Applied Biosystems). Taqman (Applied Biosystems) or SYBR Green (Applied Biosystems) gene expression master mix and synthesised cDNA was mixed with primers (Applied Biosystems) (Tables Cells were seeded (5\u2009\u00d7\u200910) Tables  and run 5 cells were seeded per T75cm2 flask and incubated for 24\u2009h before treatment with: 1\u2009\u00b5M CP-673451 for 0, 15\u2009min, 1, 4, 24 and 48\u2009h vs DMSO (control) in 0% FCS medium; 1\u2009\u03bcM CP-673451 and 1\u2009\u03bcM DUSP1 inhibitor BCI ((E)\u22122-benzylidene-3-(cyclohexylamino)\u22122,3-dihydro-1H-inden-1-one) (Merck Millipore) vs 1\u2009\u03bcM BCI and DMSO vs 1\u2009\u03bcM CP-673451 vs DMSO (control) for 24\u2009h in 10% FCS medium. Cells were collected and protein extracted using RIPA buffer (Sigma) including fresh protease and phosphatase inhibitors (Roche). Standard western blotting protocol was performed [MAPK , anti-p38MAPK , anti-phos-SAPK/JNK , anti-SAPK/JNK , anti-phos-p44/p42MAPK , anti-p44/p42MAPK  and anti-\u03b2-actin (Genscript #A00702 1:1000 dilution)) were prepared in the same solution used for blocking and incubated on a rocker at 4\u2009\u00b0C overnight (Table 5\u2009\u00d7\u200910erformed  with a 15 cells per well) into a 96-well HA hydrogel assay plate. As per instructions, 40\u2009\u00b5l of cell suspension was added as a drop on top of the gel, incubated for 30\u2009min then 100\u2009\u00b5l media was added, as previously described [Cells were seeded . Cells were incubated at room temp for 30\u2009min before 100\u2009\u00b5l CellTiter-Glo reagent was added to each well, agitated on a plate rocker for 2\u2009min and incubated at room temp for 10\u2009min. Luminescence was recorded with an integration time of 0.3\u2009s using a GloMax Explorer reader (Promega). Graphs show the mean\u2009\u00b1\u2009SD of at least three independent experiments.3 (U87 GBM cells) or 5\u2009\u00d7\u2009103 (G179 GSCs) cells per well) into a 96-well plate and incubated at 37\u2009\u00b0C, 5% CO2 for 24\u2009h. Transfection was performed according to the Lipofectamine 3000 (Invitrogen) user guide. Lipofectamine and siRNA complexes were diluted separately in Opti-MEM (Gibco). These solutions were mixed and incubated at room temp for 15\u2009min. Media was then aspirated, fresh media  was added to the cells and the mixed siRNA/Lipofectamine/Opti-MEM solution was added dropwise. Cells were transfected for 48\u2009h with 50\u2009nM and 100\u2009nM siRNA (control (CTRL), PDGF-R\u03b1, PDGF-R\u03b2 or a combination of PDGF-R\u03b1 and \u03b2) (Table 5 cells per well) into a 6-well plate, transfected as described with 50\u2009nM and 100\u2009nM CTRL siRNA or a combination of PDGF-R\u03b1 and PDGF-R\u03b2 siRNA. At 48\u2009h cells were lysed, RNA purified, cDNA synthesised and mixed with SYBR Green master mix (Applied Biosystems) plus primers (Table Cells were seeded (2\u2009\u00d7\u200910Plasmid transfection was performed with 1\u2009ng/\u00b5l pCMV6 empty vector or DUSP1 plasmid (Origene RC205220) for 48\u2009h using transfection reagent HiPerFect. Graphs display the mean\u2009\u00b1\u2009SD of at least three independent experiments, representative images shown.6 U87 GBM cells subcutaneously into 6-week-old immunocompromised athymic nude mice . Once tumours were palpable (tumour diameter ~ 3\u2009mm3), mice were randomly divided into the separate groups: DMSO control (n\u2009=\u20096), TMZ (25\u2009mg/kg/day) (n\u2009=\u20099), CP-673451 (40\u2009mg/kg/day) (n\u2009=\u20099) or combination of TMZ (25\u2009mg/kg/day) and CP-673451 (40\u2009mg/kg/day) (n\u2009=\u20099). Treatments were administered by oral gavage 5 days per week for 3 weeks after which the mice were sacrificed, tumours extracted and tumour volumes measured using the formula: (volume (mm3)\u2009=\u2009(length\u2009x\u2009height2)/2). Paraffin-embedded tumours were sectioned at a thickness of 4\u2009mm with five tissue samples obtained per tumour. Samples were placed in a pressure cooker for 15\u201320\u2009min in 0.01\u2009M citrate buffer (pH 6.0) to remove aldehyde links formed during initial fixation of tissues. Specimens were incubated with antibodies specific for Ki-67 (1:100) overnight at 4\u2009\u00b0C and immunodetection performed the following day using 3,3\u2032-diaminobenzidine (DAB) (Dako) according to manufacturer\u2019s instructions. Images were obtained using Olympus BX63 microscope (200x mag) and the number of cells per field quantified.Following local authority ethical approval by Sun Yat-sen University Animal Care and Use Committee, xenograft mouse models were developed by injecting 2\u2009\u00d7\u200910T-tests were used to compare control group with each treatment group. Differences were considered statistically significant at p\u2009\u2264\u20090.05. .Sample size was set to a minimum of three independent experiments  and experimental findings were reliably reproducible. GraphPad Prism was used for data analysis and graphs. All data are presented as mean\u2009\u00b1\u2009SD. Supplementary Figures 1\u20135"}
{"text": "The results obtained from crystal packing and DFT analysis suggest that the mol\u00adecules are held together by forces such as hydro\u00adgen bonding and \u03c0\u2013\u03c0 inter\u00adactions.Three  o-nitro\u00adsul\u00adfonamides and N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides were synthesized and characterized using techniques including 1H NMR, 13C NMR and FT\u2013IR spectroscopy, and single-crystal X-ray diffraction (SC-XRD). The calculated density functional theory (DFT)-optimized geometry of the mol\u00adecules showed similar conformations to those obtained by SC-XRD. Mol\u00adecular docking of N-piperidinyl-o-sul\u00adfan\u00adil\u00adamide and N-indolinyl-o-sul\u00adfan\u00adil\u00adamide supports the notion that o-sul\u00adfan\u00adil\u00adamides are able to bind to human carbonic anhydrase II and IX inhibitors . Hirshfeld surface analyses and DFT studies of three o-nitro\u00adsul\u00adfonamides {1-[(2-nitro\u00adphen\u00adyl)sul\u00adfon\u00adyl]pyrrolidine, C10H12N2O4S, 1, 1-[(2-nitro\u00adphen\u00adyl)sul\u00adfon\u00adyl]piperidine, C11H14N2O4S, 2, and 1-[(2-nitro\u00adphen\u00adyl)sul\u00adfon\u00adyl]-2,3-di\u00adhydro-1H-indole, C14H12N2O4S, 3} and three N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides  suggested that forces such as hydro\u00adgen bonding and \u03c0\u2013\u03c0 inter\u00adactions hold mol\u00adecules together and further showed that charge transfer could promote bioactivity and the ability to form biological inter\u00adactions at the piperidinyl and phenyl moieties.In the search for new \u2018sulfa drugs\u2019 with therapeutic properties,  Sulfonamides E are derivatives of sul\u00adfan\u00adil\u00adamide and remain an important class of drugs, with anti\u00adbacterial and non-anti\u00adbacterial potencies, such as diuretic, anti\u00admicrobial, anti-epileptic, anti\u00adleprotic, anti\u00admalarial, hypoglycemic, anti\u00adretro\u00adviral, anti\u00adthyroid and anti-inflammatory activities sul\u00adfon\u00adyl]pyrrolidine, 1, 1-[(2-nitro\u00adphen\u00adyl)sul\u00adfon\u00adyl]pi\u00adperi\u00addine, 2, and 1-[(2-nitro\u00adphen\u00adyl)sul\u00adfon\u00adyl]-2,3-di\u00adhydro-1H-indole, 3, and the N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 2-(pyrrolidine-1-sul\u00adfon\u00adyl)aniline, 4, 2-(piperidine-1-sul\u00adfon\u00adyl)aniline, 5, and 2-aniline, 6. The crystal structures, density functional theory (DFT) studies, Hirshfeld surface analysis, mol\u00adecular electrostatic potential and electronic properties of the title sul\u00adfonamides and sul\u00adfan\u00adil\u00adamides (1\u20136) have been discussed. Mol\u00adecular docking experiments with carbonic anhydrase II (PDB entry 4iwz) and IX (5fl4) active sites were conducted in order to predict their binding inter\u00adactions with 1\u20136  solvent system visualized under a UV lamp (254\u2005nm). Column chromatography was performed with silica gel (70\u2013230 mesh ASTM) and mobile phases were as indicated. Sample crystallization was achieved by the slow evaporation of the indicated solvent systems at ambient tem\u00adper\u00adature. IR spectra were obtained using a Bruker Tensor 27 platinum ATR\u2013FT\u2013IR spectrometer. The ATR\u2013FT\u2013IR spectra were acquired in a single mode with a resolution of 4\u2005cm\u22121 over 32 scans, in the region 4000\u2013650\u2005cm\u22121. 1H and 13C NMR spectra were recorded, in CDCl3, on a Bruker 400\u2005MHz spectrometer. Chemical shift (\u03b4) values were measured in parts per million (ppm) downfield from tetra\u00admethyl\u00adsilane (TMS) and coupling constants (J) are reported in hertz (Hz). Theoretical studies were performed for the com\u00adpounds and, in each case, their SC-XRD structures were used for optimization and global reactivity descriptor (GRD) calculations.All reagents were purchased from Millipore Sigma (Ger\u00admany and South Africa) and were used without purification. The melting points were determined on an Electrothermal digital melting-point apparatus and are uncorrected. Reactions were monitored by thin-layer chromatography (TLC) on Merck silica gel 60 Fo-Nitro\u00adbenzene\u00adsul\u00adfonyl chloride (1.00\u2005mmol) was added slowly to a stirring dried toluene solution (30\u2005ml) of the cyclo\u00adamine (2.20\u2005mmol) at ambient tem\u00adper\u00adature and stirred for 12\u2005h, monitored by TLC. The reaction mixture was then diluted with di\u00adchloro\u00admethane (30\u2005ml) and washed with distilled water (3 \u00d7 10\u2005ml). The organic layer was separated, dried over anhydrous sodium sulfate, filtered and concentrated to an oil, which was purified by column chromatography on silica gel . Crystals were obtained by the slow solvent evaporation of the requisite eluates at ambient tem\u00adper\u00adature, except for 5, which was recrystallized from di\u00adchloro\u00admethane, slowly evaporated and filtered to give single crystals.1. o2.2.1.1. N-Pyrrolidinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide, -Nitro\u00adbenzene\u00adsul\u00adfonyl chloride  and pyrrolidine . Yellow crystals ; RF\u00a0= 0.44 ; m.p. 81.7\u201381.9\u2005\u00b0C. IR : 3080 (aryl C\u2014H str.), 2968 (sp3-C\u2014H str.), 1597 (aryl C=C str.), 1543 (asym C\u2014NO2 str.), 1344 (sym C\u2014NO2 str.), 1342 (asym SO2\u2014N str.), 1163 (sym SO2\u2014N str.), 1078 (C\u2014N str.). 1H NMR : 7.94 , 7.62 , 7.54 , 3.37\u20133.35 , 1.85 . 13C NMR : 148.4, 133.5, 132.1, 131.5, 130.6, 123.9 (ArH), 48.2 (\u2013CH2NCH2\u2013), 25.9 (\u2013CH2CH2\u2013).2. o2.2.1.2. N-Piperidinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide, -Nitro\u00adbenzene\u00adsul\u00adfonyl chloride  and piperidine . Yellow crystals ; RF\u00a0= 0.56 ; m.p. 91.6\u201391.8\u2005\u00b0C. IR : 3076 (aryl C\u2014H str.), 2947 (sp3-C\u2014H str.), 1552 (aryl C=C str.), 1550 (asym C\u2014NO2 str.), 1354 (sym C\u2014NO2 str.), 1350 (asym SO2\u2014N str.), 1166 (sym SO2\u2014N str.), 1056 (C\u2014N str.). 1H NMR : 7.96 , 7.70 , 7.59 , 3.26\u20133.24 , 1.64\u20131.63 , 1.55\u20131.54 . 13C NMR : 148.5, 133.6, 131.6, 131.5, 130.8, 123.5 (ArH), 47.0 (\u2013CH2NCH2\u2013), 25.4 (\u2013CH2CH2CH2\u2013), 23.5 (\u2013CH2CH2CH2\u2013).3. o2.2.1.3. N-Indolinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide, -Nitro\u00adbenzene\u00adsul\u00adfonyl chloride  and indoline . Yellow crystals ; RF\u00a0= 0.79 ; m.p. 106.5\u2013106.8\u2005\u00b0C. IR : 3077 (aryl C\u2014H str.), 2976 (sp3-C\u2014H str.), 1594 (aryl C=C str.), 1536 (asym C\u2014NO2 str.), 1356 (sym C\u2014NO2 str.), 1355 (asym SO2\u2014N str.), 1161 (sym SO2\u2014N str.), 1051 (C\u2014N str.). 1H NMR : 7.95 , 7.71 , 7.62 , 7.48 , 7.21 , 7.05 , 4.17 , 3.10 . 13C NMR : 148.4, 141.1, 134.1, 131.8, 131.7, 131.6, 130.2, 127.8, 125.5, 124.3, 124.2, 114.5 (ArH), 50.5 (\u2013NCH2\u2013), 28.0 (\u2013NCH2CH2\u2013).N-cyclo\u00adamino-o-nitro\u00adbenzene\u00adsul\u00adfonamides 1\u20133 (15.63\u2005mmol) dissolved in ethanol (30\u2005ml), at ambient tem\u00adper\u00adature, and 10% palladium-on-charcoal catalyst (3.35\u2005mol%) was added, with stirring. Hydrogen gas was then introduced via a balloon and stirring continued at ambient tem\u00adper\u00adature for 12\u2005h. The reaction mixture was filtered and the solvent was evaporated in vacuo. The resulting residue was extracted into di\u00adchloro\u00admethane (50\u2005ml), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to afford an oil, which was purified on a silica-gel column using di\u00adchloro\u00admethane and n-hexane (2:1 v/v). Crystals were obtained via slow solvent evaporation of the eluates at ambient tem\u00adper\u00adature.An evacuated nitro\u00adgen-gas-filled round-bottomed flask was charged with 4. N2.2.2.1. N-Pyrrolidinyl-o-sul\u00adfan\u00adil\u00adamide, -Pyrrolidinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide 1  with 10% palladium-on-charcoal catalyst . Off-white crystals ; RF\u00a0= 0.40 ; m.p. 75.2\u201375.4\u2005\u00b0C. IR : 3464, 3363 (N\u2014H str.), 3003 (aryl C\u2014H str.), 2947 (sp3-C\u2014H str.), 1620 (aryl C=C str.), 1323 (asym SO2\u2014N str.), 1132 (sym SO2\u2014N str.), 1307 (C\u2014N str.). 1H NMR : 7.63 , 7.28 , 6.74 , 5.13 , 3.31 , 1.80 . 13C NMR : 146.4, 134.0, 130.2, 119.1, 117.6, 117.1 (ArH), 47.8 (\u2013CH2NCH2\u2013), 25.2 (\u2013CH2CH2\u2013).5. N2.2.2.2. N-Piperidinyl-o-sul\u00adfan\u00adil\u00adamide, -Piperidinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide 2  with 10% palladium-on-charcoal catalyst . Off-white crystals ; RF\u00a0= 0.57 ; m.p. 76.6\u201376.8\u2005\u00b0C. IR : 3487; 3383 (N\u2014H str.), 3072 (aryl C\u2014H str.), 2947 (sp3-C\u2014H str.), 1606 (aryl C=C str.), 1309 (asym SO2\u2014N str.), 1136 (sym SO2\u2014N str.), 1336 (C\u2014N str.). 1H NMR : 7.48 , 7.21 , 6.67 , 6.64 , 4.99 , 3.03\u20133.00 , 1.56\u20131.53 , 1.39\u20131.37 . 13C NMR : 146.3, 134.0, 130.1, 118.0, 117.6, 117.0 (ArH), 46.8 (\u2013CH2NCH2\u2013), 25.2 (\u2013CH2CH2CH2\u2013), 23.6 (\u2013CH2CH2CH2\u2013).6. N2.2.2.3. N-Indolinyl-o-sul\u00adfan\u00adil\u00adamide, -Indolinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide 3  with 10% palladium-on-charcoal catalyst . Off-white crystals ; RF\u00a0= 0.80 ; m.p.: 111.9\u2013112\u2005\u00b0C. IR : 3448, 3367 (N\u2014H str.), 3070 (aryl C\u2014H str.), 2924 (sp3-C\u2014H str.), 1597 (aryl C=C str.), 1327 (asym SO2\u2014N str.), 1138 (sym SO2\u2014N str.), 1330 (C\u2014N str.). 1H NMR : 7.48 , 7.16 , 7.08 , 7.03 , 6.90 , 6.58 , 6.55 , 5.00 , 3.96 , 2.86 . 13C NMR : 146.4, 142.3, 134.4, 132.1, 129.8, 127.6, 125.1, 123.7, 119.4, 117.7, 117.3, 115.1 (ArH), 50.0 (\u2013NCH2\u2013), 28.1 (\u2013NCH2CH2). Reaction synthesis of nitro\u00adsul\u00adfonamides 1\u20133 and amino\u00adsul\u00adfonamides 4\u20136 are presented in Scheme S1 in the supporting information. The FT\u2013IR, MS and 1H/13C NMR spectra of com\u00adpounds 1\u20136 are also presented in the supporting information.1\u20136 (CIF files) were imported directly into the Schr\u00f6dinger Suite -2-(thio\u00adphen-2-yl)acetamide (A) and 5-thio\u00adphene-2-sul\u00adfon\u00adamide (B) were based on chemical structures downloaded from the PubChem (https://pubchem.ncbi.nlm.nih.gov/) web\u00adsite in SDF format. A and B were used as reference com\u00adpounds because they are natural ligands in the crystalline state of 5fl4 and 4iwz. The Ligprep module of the mol\u00adecular model\u00adling platform of the Schr\u00f6dinger Suite  Protein Data Bank (PDB). Retrieved crystal coordinates were prepared in the \u2018Protein Preparation Wizard\u2019 of the Schr\u00f6dinger Suite  and XII (4iw7) isoforms will provide a selectivity profile that may be inter\u00adesting for the development of novel anti\u00adcancer agents with limited side effects. The hCA II (PDB entry 5fl4) and XII (4iw7) carbonic anhydrase iso\u00adforms have recently emerged as excellent targets for the design of novel therapeutic strategies for cancer, due to their involvement in the survival of tumour cells, as well as in the insurgence of resistance to classical anti\u00adcancer protocols  mode of the 1\u20136 whereupon the SC-XRD structures of the com\u00adpounds were used for optimization and global reactivity descriptor (GRD) calculations. Computational studies and mol\u00adecular electrostatic potential (MEP) for 1\u20136 were carried out using the GAUSSIAN16 software package .Theoretical studies were performed for com\u00adpounds Crystal data, data collection and structure refinement details are summarized in Table\u00a01N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 were prepared via a two-step reaction, starting from the condensation reaction of o-nitro\u00adbenzene\u00adsul\u00adfonyl chloride with alicyclic amines in tolu\u00adene, at ambient tem\u00adper\u00adature, to afford N-cyclo\u00adamino-o-nitro\u00adbenzene\u00adsul\u00adfonamide adducts 1\u20133 (Scheme S1 in the supporting information). The use of toluene as a nonpolar reaction medium was, amongst other reasons, to drive the forward reaction. In the second step, adducts 1\u20133 were hydro\u00adgenated with hydro\u00adgen gas, in ethanol at ambient tem\u00adper\u00adature, in the presence of 10% palladium-on-activated charcoal catalyst to give the target N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 in 72\u201386% yield. The reactions were monitored by TLC.The 1H/13C NMR and MS spectra. In the IR spectra of o-nitro\u00adsul\u00adfonamide adducts 1\u20133, the strong absorption bands observed at 1355\u20131342 and 1171\u20131161\u2005cm\u22121 were ascribed to the asymmetric and symmetric stretching frequencies, respectively, of the SO2\u2014N moiety, thereby alluding to the formation of the sul\u00adfonamide bond. The disappearances of the SO2\u2014Cl (1420 and 1220\u2005cm\u22121) and N\u2014H (3286\u20133265\u2005cm\u22121) stretching bands in the IR spectra of o-nitro\u00adbenzene\u00adsul\u00adfonyl chloride and cyclo\u00adamines, respectively, were good indicators of a successful condensation reaction. This was corroborated by the shift of the sul\u00adfonyl (\u2013SO2\u2013) absorption bands from 1420 and 1220 (in o-nitro\u00adbenzene\u00adsul\u00adfonyl chloride) to 1355\u20131342 and 1171\u20131161\u2005cm\u22121 (in 1\u20133). It is noteworthy that the lower wavenumbers observed in the IR spectra of o-nitro\u00adsul\u00adfonamides 1\u20133 for \u2013SO2\u2013 were not unusual as the Cl atom bonded to it had been replaced by a less electronegative N atom. In the IR spectra of o-sul\u00adfan\u00adil\u00adamides 4\u20136, the appearance of two N\u2014H stretching bands in the higher frequency region around 3467\u2005\u00b1\u200520 and 3383\u2005\u00b1\u200510\u2005cm\u22121, and the disappearance of the nitro (NO2) absorption bands (observed at 1550\u20131536 and 1369\u20131342\u2005cm\u22121) in the spectra of 1\u20133 were attributed to the successful catalytic reduction of the nitro group to the amino group.All the com\u00adpounds synthesized were characterized by their melting points and IR, 1H NMR spectra of o-nitro\u00adsul\u00adfonamides 1\u20133 were additive of the individual spectra of the starting materials (i.e. o-nitro\u00adbenzene\u00adsul\u00adfonyl chloride and cyclo\u00adamines), with the disappearance of the nitro\u00adgen proton peaks of cyclo\u00adamines. The aromatic protons of o-sul\u00adfan\u00adil\u00adamides 4\u20136 resonated upfield in com\u00adparison to the same aromatic protons in precursors 1\u20133. This general shift towards tetra\u00admethyl\u00adsilane (TMS) was credited to the newly formed amino groups whose lone-pair electrons are suspected of having caused the increased mesomeric shielding of the aromatic protons. D2O-exchangeable singlets were also observed in the 1H NMR spectra of 4\u20136 between 5.13 and 4.99\u2005ppm for the newly-formed amino protons. The success of the catalytic hydro\u00adgenation of nitro adducts 1\u20133 was corroborated by the 13C NMR spectra of 4\u20136, where the requisite C atoms (C\u2014NO2 \u2192 C\u2014NH2) resonated upfield in the range 133.9\u2013130.1\u2005ppm. The spectroscopic data analyses of the synthesized com\u00adpounds were consistent with the assigned structures of the com\u00adpounds.The 1\u20133 and 4\u20136 crystallized in the monoclinic space group P21/n or P21/c (No. 14), except for 5, which crystallized in the ortho\u00adrhom\u00adbic space group Pbca (No. 61). In addition, they all had one mol\u00adecule in the asymmetric unit, with the exception of 4, with two independent mol\u00adecules per asymmetric unit cell. The two mol\u00adecules per unit cell of com\u00adpound 4 were identical but for the conformation of the pyrrolidine group . It is noteworthy that the pyrrolidine ring in 1 is disordered. The mol\u00adecular structures of 1\u20133 and 4\u20136 are shown in Fig.\u00a02o-nitro\u00adsul\u00adfonamides 1\u20133 and N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 are presented in Table\u00a01para-sul\u00adfan\u00adil\u00adamide and ortho-sul\u00adfan\u00adil\u00adamide, which crystallize in the ortho\u00adrhom\u00adbic Pbca (No. 61) and monoclinic P21/c (No. 14) space groups, respectively .The mol\u00adecules of 2) group in N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 contributed significantly to their hydro\u00adgen-bond inter\u00adactions (cf. Table\u00a02S(6) graph-set descriptors  descriptors. Inter\u00adestingly, no infinite chain inter\u00adaction was observed in 4; instead, four mol\u00adecules were linked into a ring structure with an p-sul\u00adfan\u00adil\u00adamide  strength \u2005\u00c5 were observed between the centrosymmetric indo\u00adline moieties. An N=O\u22ef\u03c0 ring inter\u00adaction of 3.657\u2005(2)\u2005\u00c5 was also evident in 3, whereas inter\u00admolecular C\u2014H\u22ef(\u03c0 ring) inter\u00adactions of 2.97\u2005\u00c5 and S=O\u22ef(\u03c0 ring) inter\u00adactions of 3.5773\u2005(15)\u2005\u00c5 were present in the structure of its hydro\u00adgenated analogue 6. The packing diagrams of the crystal structures of com\u00adpounds 1\u20136 are shown in Fig. S2 in the supporting information.The only \u03c0\u2013\u03c0 stacking inter\u00adaction of note occurred in et al., 20171\u20136 showed inter\u00admolecular inter\u00adactions such as O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22ef\u03c0. Two sharp O\u2014H spikes typical of an O\u2014H\u22efO inter\u00adaction from 1 contributed the highest O\u22efH inter\u00adaction of 42.3%. The fingerprint plots showed that C\u22efH contacts were highest for 6 (30.4%), and this is closely related to C\u2014H\u22ef\u03c0 inter\u00adactions  visible on the dnorm surfaces typically indicate that the mol\u00adecule has a donor site(s) (e.g. amine and/or sul\u00adfone) or inter\u00adactions with proteins.The mol\u00adecular Hirshfeld surfaces, mapped as o-nitro\u00adsul\u00adfonamides 1\u20133 and N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 in full and resolved into C\u22efH, O\u22efH and N\u22efH are presented in Fig. S4 (supporting information). The inter\u00admolecular O\u22efH and N\u22efH inter\u00adactions appear as two distinct spikes of almost equal length in the 2D  fingerprint plots in the region 1.2 < (de + di) < 2.9\u2005\u00c5 as light-sky-blue patterns in full fingerprint 2D plots and characterized to be 2.56\u2005\u00b1\u20050.21\u2005\u00c5 corresponds to O\u22efH contacts which contributes the majority of the surface area. 2D fingerprint plots reveal the contributions of these inter\u00adactions in the crystal structure qu\u00adanti\u00adtatively and are presented in Table\u00a04dnorm, di and de provided). Complementary regions are also visible in the fingerprint plots , where one mol\u00adecule acts as a donor (de > di) and the other acts as an acceptor (de < di). This finding was validated by the calculated mol\u00adecular electrostatic potential of 1\u20136 . The negative potential (acceptor) is indicated as a red surface around the O atoms attached to sulfur (\u2013SO2) and the N atoms attached to oxygen (\u2013NO2). The blue/purple surface area indicates that the positive potential (donor) is mapped in the proximity of the H atoms .Fingerprint plots of 1\u20136 presented bond lengths similar to those obtained from the crystal data. A com\u00adparison of selected torsion angles of the crystal structures of 1\u20136 and the DFT-optimized mol\u00adecules showed that con\u00adformation of the mol\u00adecules did not change significantly in the DFT-optimized state . Generally, the observed, almost flat, O\u2014S\u2014N\u2014C torsion angle of the DFT-optimized mol\u00adecules suggest that the lone pairs on sulfur may have con\u00adtributed to the \u03c0-electron delocalization that is observed in the DFT mol\u00adecules.The full geometry of optimized mol\u00adecules 3 and 5. The LUMO is mainly spread over the phenyl moieties. This indicates that there is a transfer of charge between the indolin\u00adyl/pyrrolidinyl rings and the phenyl moieties within the mol\u00adecule.The highest occupied mol\u00adecular orbital (HOMO) and lowest unoccupied mol\u00adecular orbital (LUMO) electrons are distributed around various moieties within the various mol\u00adecules Fig.\u00a04. Generalet al., 2020N-Indolinyl-o-nitro\u00adbenzene\u00adsul\u00adfonamide 3 displayed the smallest energy gap (3.24\u2005eV), indicating that it was the softest mol\u00adecule with good polarizability and reactivity, whereas N-piperidinyl-o-sul\u00adfan\u00adil\u00adamide 5 presented the largest energy gap of 4.924\u2005eV, thereby corroborating its high chemical hardness of 2.462\u2005eV (cf. Table\u00a053 (ELUMO\u00a0= \u22123.175\u2005eV), indicating that it is the best electron acceptor of the mol\u00adecules analyzed, whereas 6 was the best electron donor in the series, with the highest HOMO energy (EHOMO) of \u22126.142\u2005eV , electron affinity (A), chemical potential (\u03bc), electronegativity (\u03c7), global hardness (\u03b7), global softness (S) and global electrophilicity (\u03c9) values were calculated using the HOMO and LUMO energy values and are collated in Table\u00a05I value of 6.142\u2005eV originated from sul\u00adfan\u00adil\u00adamide 6, whereas sul\u00adfonamide 3 gave the largest A value of 3.175\u2005eV. Amongst the com\u00adpounds studied, 2 gave the highest \u03c7 value of 5.1795\u2005eV. Inter\u00adestingly, sul\u00adfan\u00adil\u00adamide 5 displayed the highest \u03b7 value of 2.462\u2005eV and the lowest chemical softness (S) of 0.406\u2005eV, thus alluding to its having the most reactive nature of all the mol\u00adecules investigated. The highest global electrophilicity of 29.597\u2005eV was also recorded for sul\u00adfonamide 2, indicating that it is a strong electro\u00adphile. In general, the chemical reactivities of com\u00adpounds 1\u20136 have been shown to vary with the groups attached to the com\u00adpounds   -2-(thio\u00adphen-2-yl)acetamide (A) and 5-thio\u00adphene-2-sul\u00adfonamide (B) were also docked with respective proteins 4iwz and 5fl4, and taken as reference or standard drugs. Docking poses for the synthesized com\u00adpounds are displayed in Figs. S7\u2013S18, while those for the reference drugs are shown in Figs. 5Docking studies of synthesized 4iwz and A (reference drug) displayed a docking score of \u22122.252 kcal mol\u22121, which is higher than for all synthesized com\u00adpounds 1\u20136  and HIE64 (2.24\u2005\u00c5) via hydro\u00adgen-bonding inter\u00adactions and with amino acid residue HIS94 (4.75\u2005\u00c5) via \u03c0\u2013\u03c0 stacking inter\u00adactions  and TRP5 (2.11\u2005\u00c5), and through \u03c0\u2013\u03c0 stacking with THR199 (1.81\u2005\u00c5) .Also,  A Fig.\u00a05. Compoun5fl4, and the results obtained were com\u00adpared with the docked results of the reference drug B. We observed that the reference drug inter\u00adacts with amino acid residues ASP13 (1.59\u20132.73\u2005\u00c5) and VAL130 (2.53\u2005\u00c5) via hydro\u00adgen bonding, and with HID94 (5.49\u2005\u00c5) via \u03c0\u2013cation inter\u00adactions , displayed significantly good docking scores; however, they were lower than the reference drug .To determine the mode of inter\u00adaction of the synthesized com\u00adpounds with human carbonic anhydrase IX inhibitor (hCA IX), the synthesized com\u00adpounds were docked into the active site of 31 Fig.\u00a06. Benzene2 with 4iwz and 5fl4 are close to those obtained for A with 4iwz and B with 5fl4. Docking scores of mol\u00adecules with ring structures 1 and 3\u20136  also correlated with the electronegativity and electrophilicity values presented in Table\u00a05et al., 2018We observed that the docking scores of o-Nitro\u00adsul\u00adfonamides 1\u20133 and N-cyclo\u00adamino-o-sul\u00adfan\u00adil\u00adamides 4\u20136 have been successfully synthesized, characterized and the intermolecular interactions analysed, as well as being tested in silico for carbonic anhydrase II (4iwz) and IX (5fl4) inhibitory activities. The results obtained from crystal packing and DFT analysis suggests that the mol\u00adecules are held together by forces such as hydro\u00adgen bonding and \u03c0\u2013\u03c0 inter\u00adactions. The results of the DFT study of com\u00adpounds 1\u20136 were correlated with the mol\u00adecular docking data and indicate that electronegativity and electrophilicity of the title com\u00adpounds play an important role in their inter\u00adaction with carbonic anhydrase II (4iwz) and IX (5fl4).O-Nitro\u00adsul\u00adfonamide 2 displayed a good docking score against 4iwz (lower than the reference drug) and the best against 5fl4 (higher than the reference drug). These results provided a valuable synthesis approach and structural and docking information for com\u00adpounds 1\u20136 that may be used for the development of potent anti\u00adbacterial drugs.10.1107/S2053229622010130/oj3005sup1.cifCrystal structure: contains datablock(s) ka097, ja198, ja250, ja192, ka115, ja189, global. DOI: 10.1107/S2053229622010130/oj3005ka097sup2.hklStructure factors: contains datablock(s) ka097. DOI: 10.1107/S2053229622010130/oj3005ja198sup3.hklStructure factors: contains datablock(s) ja198. DOI: 10.1107/S2053229622010130/oj3005ja250sup4.hklStructure factors: contains datablock(s) ja250. DOI: 10.1107/S2053229622010130/oj3005ja192sup5.hklStructure factors: contains datablock(s) ja192. DOI: 10.1107/S2053229622010130/oj3005ka115sup6.hklStructure factors: contains datablock(s) ka115. DOI: 10.1107/S2053229622010130/oj3005ja189sup7.hklStructure factors: contains datablock(s) ja189. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ka097sup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ja198sup9.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ja250sup10.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ja192sup11.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ka115sup12.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2053229622010130/oj3005ja189sup13.cmlSupporting information file. DOI: 10.1107/S2053229622010130/oj3005sup14.pdfAdditional figures, tables and spectra. DOI: 2014232, 2039638, 2014231, 2014230, 2014229, 2039639CCDC references:"}
{"text": "Fragment ligation with formylglycine occurred in\u2005situ in aqueous physiological buffer. Structures and kinetics were validated by NMR spectroscopy. Screening and hit validation revealed fluorinated and non\u2010fluorinated hit fragments being able to replace the native phosphotyrosine residue. The formylglycine probe identified low\u2010affinity fragments with high spatial resolution as substantiated by molecular modelling. The best fragment hit, 4\u2010amino\u2010phenyl\u2010acetic acid, was converted into a cellularly active, nanomolar inhibitor of the protein tyrosine phosphatase SHP2.Discovery of protein\u2010binding fragments for precisely defined binding sites is an unmet challenge to date. Herein, formylglycine is investigated as a molecular probe for the sensitive detection of fragments binding to a spatially defined protein site . Formylglycine peptide  Site\u2010directed screening? Formylglycine (red) is a reactive amino acid that can be utilized in fragment ligation assays. Incorporated into a site\u2010directing hexapeptide it can effectively probe the active site of PTP1B, yielding new phosphotyrosine mimetics derived from different nucleophiles, such as aryl amines (green). DK values to enable detection.Site\u2010directed discovery of small protein\u2010binding fragments with M<250\u2005Da is a challenge due to the low affinities of most fragments and due to the lack of analytical methods that enable the detection of binding fragments at precisely defined positions on the protein surface.Fragment ligation has been introduced as a method to enhance binding of a primary fragment by a covalent, typically protein\u2010templated reaction with a secondary ligand.We reasoned that peptides and proteins carrying a reactive side chain electrophile should enable the site\u2010specific ligation of nucleophiles and thus might serve as tools for the site\u2010directed discovery of binding fragments for defined protein pockets Figure\u2005. FormylgThese findings encouraged us to investigate formylglycine peptides for the site\u2010directed discovery of protein\u2010binding fragments. As a model system, we selected the active sites of protein tyrosine phosphatases (PTP) which recognize and hydrolyze phosphotyrosine residues  as substrates.1 (X=O) or the potent inhibitor 2 derived from it (X=CF2) and replaced the phosphotyrosine residue by formylglycine  1 contains the autophosphorylation sequence 988\u2013993 of epidermal growth factor receptor (EGF\u2212R) including the O\u2010phosphorylated tyrosine 992  and has been recognized as a substrate of the phosphotyrosine phosphatase PTP1B with a MK value of 3.6\u2005\u03bcM \u20104 was synthesized following a published 7\u2010step protocol from L\u2010serine,4 instead and established a facilitated access to 4 in only 3 steps starting from O\u2010ethyl 2\u2010nitro\u2010acetate 5. Treatment of 5 with titanium tetrachloride, N,N\u2010diisopropylethylamine, and triethyl orthoformate afforded the diethyl acetal 6 (conditions a).6 in the presence of Raney nickel furnished ethyl 2\u2010amino\u20103,3\u2010diethoxypropionate 7. Alternatively, under conditions b, N\u2010formylglycine ethylester 8 was formylated in C2 position with ethyl formate and tBuOK, followed by acetalization with HCl in EtOH at \u221225\u2009\u00b0C and cleavage of the N\u2010formyl group under basic conditions leading to the same diethylacetal 7.7 followed by N\u2010Fmoc protection with Fmoc\u2010OSu afforded the desired N\u2010Fmoc\u2010formylglycine 4  in a total yield of 68\u2009% over 4 steps  or 43\u2009% over 3 steps .The phospho\u2010hexapeptide Ac\u2010Asp\u2010Ala\u2010Asp\u2010Glu\u2010Tyr*\u2010Leu\u2010NH4 was then used in solid phase peptide synthesis on polystyrene with Rink amide linker by diisopropyl carbodiimide/HOBt activation. Cleavage and complete deprotection was achieved with TFA/H2O. (95\u2009:\u20095 v/v) and the formylglycine peptide 3 was isolated by HPLC in 73\u2009% yield. Peptide 3 was highly soluble in water, buffer, and DMSO, so that we were able to analyze its structure and reactivity in solution .Building block 3 synthesized from (S)\u2010fGly and rac\u2010fGly were identical. In DMSO the fGly\u2010residue appears as a mixture of the aldehyde form 3, the hydrate form 9, and the enol form 10. In H2O/D2O 9\u2009:\u20091, exclusively the hydrate form 9 was observed with both diastereomeric H\u03b1 at 4.3\u2005ppm and both H\u03b2 at 5.3\u2005ppm. In the DQF\u2010H,H\u2010COSY spectrum all backbone NH protons were detectable suggesting that no cyclization with any of the backbone amides occurred and the formyl moiety thus was available for ligation. High resolution Q\u2010TOF MS analysis further confirmed the predominant hydration of the formylglycine peptide 3.NMR\u2010spectra of 3 were investigated with several nucleophilic fragments F detected in a primary screening experiment (see below) using NMR spectroscopy . One can suspect that the Z\u2010configuration of 11 is strongly favored over the E\u2010configuration due to an H\u2010bond between the enamine\u2010NH and the carbonyl residue of Glu4 resulting in a 7\u2010membered ring . Formation of the ligation product 11 was followed in Watergate 1H\u2005NMR for 1000\u2005min by integration of the benzylic CH2 group in starting material F1 and product 11 and indicated product formation with an average half reaction time of 10.7\u2005min \u2010trifluoromethyl sulfonamide F2 yielded enamine 12  formed hydrazone 13 with 100\u2009% conversion of 3 instantaneously (<2\u2005min). 13 was characterized by a shifted H\u03b1 of the fGly residue at 5.0 coupling with the H\u03b2 at 7.2 and the fGly\u2010NH at 8.3\u2005ppm. A single configuration of the hydrazone double bond was formed, presumably the thermodynamically favored E\u2010isomer. One might suspect as the preferred conformation the one establishing an H\u2010bonded, 6\u2010membered ring between the double\u2010bonded hydrazine\u2010N1 and the NH of Leu4  (1\u2009:\u20095), a common reducing agent in biochemistry and especially in assays with protein tyrosine phosphatases, yielded a ligation product detectable in HPLC\u2010MS with a mass corresponding to the hemi\u2010thioacetal 14 . 14 could not be detected in NMR or isolated, which is in full agreement with earlier results on the transient formation of bioactive hemi\u2010(thio)\u2010acetals formed by protein\u2010templated ligation reactions.3 DTT was found to compete with other nucleophiles such as amines or hydrazines. Therefore, it had to be replaced in enzyme assays with a non\u2010nucleophilic reducing agent. No ligation reaction was observed between formylglycine peptide 3 and tris\u2010carboxyethyl phosphane (TCEP) which was found to sustain the enzymatic activity of protein tyrosine phosphatases reliably at 50\u2005\u03bcM for several hours and therefore was employed in all ligation experiments.Incubation of 3 was tested as an inhibitor of two protein tyrosine phosphatases, PTP1B and SHP2, in an enzyme activity assay using DiFMUP  as a fluorogenic substrate. Peptide 3 bound to and inhibited PTP1B with a IK value of 484\u2005\u03bcM and SHP2 with a IK of 341\u2005\u03bcM  were selected and tested as inhibitors of PTP1B alone and in combination with peptide 3 . Fragments were pre\u2010selected for library composition based upon representation of potential phosphate\u2010mimetic substructures including carboxylic acids, sulfonic acids, sulfonamides, and fluorine\u2010rich functional groups, which were to be investigated for fluorine\u2010specific interactions with phosphotyrosine binding sites., 687.2711\u2005Da. calcd m/z 688.2790 [M+H]+, 710.2609 [M+Na]+, found m/z 688.2792 [M+H]+, 710.2607 [M+Na]+.3,3\u2010Diethoxy\u20102\u2010(9H\u2010fluoren\u20109\u2010ylmethoxycarbonylamino)\u2010 propanoic acid 4: Ethyl 2\u2010amino\u20103,3\u2010diethoxypropanoate 7  was suspended in 0.5\u2005M aq. LiOH solution (5\u2005mL) and methanol was added until a clear solution remained. It was stirred at room temperature for 2\u2005h. TLC control after this time revealed the hydrolysis of 7 after which the mixture was neutralized with Amberlite\u00ae IR\u2010120 loaded with H+. The resin was filtered off and washed with water and concentrated under reduced pressure. The product of hydrolysis and NaHCO3  were stirred in H2O (10\u2005mL) at 0\u2009\u00b0C. To this solution was added dropwise 9\u2010fluorenylmethyl N\u2010succinimidyl carbonate  dissolved in 1,4\u2010dioxane (10\u2005mL) at 0\u2009\u00b0C. The mixture was stirred for 1\u2005h at 0\u2009\u00b0C, warmed to room temperature and then stirred for another 12\u2005h. The reaction mixture was concentrated under reduced pressure and purified by column chromatography to provide 4 as white solid ; Rf=0,46 . 1H NMR: : \u03b4=7.75 , 7.61 , 7.39 , 7.31 , 5.67 , 4.85 , 4.59 , 4.39 , 4.24 , 3.88\u20133.77 , 3.76\u20133.6 , 3.65\u20133.57 , 1.32 , 1.21  ppm. 13C NMR: : \u03b4=172.33 (COOH), 156.59 (CONH), 143.80 (Ar\u2212Cquart), 141.37 (Ar\u2212Cquart), 127.83 (Ar\u2212C), 127.19 (Ar\u2212C), 125.28 (Ar\u2212C), 120.06 (Ar\u2212C), 101.17 (C\u03b2), 67.53 (Fmoc CH2), 64.74 (CH2CH3), 64.69 (CH2CH3), 56.73 (C\u03b1), 47.15 (Fmoc CH), 15.20 (CH2CH3), 15.08 (CH2CH3) ppm. HRMS: (ESI): C22H25NO6 [M], 399.1682\u2005Da. calcd m/z 398.1604 [M\u2212H]\u2212, 422.158 [M+Na]+, found m/z 398.1609 [M+H]+, 422.1578 [M+Na]+.Ethyl 3,3\u2010diethoxy\u20102\u2010nitropropanoate 6: To a solution of ethyl\u2010nitroacetate 5  in anhydrous methylene dichloride (25\u2005mL) held at \u2010 10\u2009\u00b0C under an argon atmosphere was slowly added by syringe titanium(IV)\u2010chloride . The mixture was stirred for 10\u2005min and N,N\u2010diisopropylethylamine  was added to the mixture dropwise over 30\u2005min. The Mixture was held at \u221210\u2009\u00b0C with stirring for 1\u2005h. triethyl\u2010orthoformate  was added to the mixture dropwise and stirring was continued for 2\u2005h at \u221210\u2009\u00b0C. The reaction mixture was diluted with a 20\u2009% solution of ethanol in saturated aqueous NaHCO3 (100\u2005mL) and the mixture was stirred vigorously for 10\u2005min. Organic solvents were removed from the mixture under reduced pressure. Water (200\u2005mL) was added to the concentrated reaction mixture and the aqueous phase was extracted three times with ethylacetate. The combined organic phases were filtered over celite and dried over Na2SO4. Evaporation of the solvents under reduced pressure afforded compound 6 as yellow oil ; Rf=0,46 . 1H NMR: : \u03b4=5.24 , 5.17 , 4.28 , 3.81\u20133.75 , 3.69\u20133.61 , 1.30 , 1.19  ppm. 13C NMR: : \u03b4=161.77 (COOEt), 100.08 (C\u03b2), 88.52 (C\u03b1), 64.79 (OCH2CH3), 64.60 (OCH2CH3), 63.18 (COOCH2CH3), 15.16 (OCH2CH3), 15.07 (OCH2CH3), 13.94 (COOCH2CH3) ppm. HRMS: C9H17NO6 [M], 235.1056\u2005Da. calcd m/z 258.0948 [M+Na]+, 274.0687 [M+K]+, found m/z 258.0948 [M+Na]+, 274.0680 [M+K]+.Ethyl 2\u2010amino\u20103,3\u2010diethoxypropanoate 7 (Method A): Ethyl 3,3\u2010diethoxy\u20102\u2010nitropropanoate 6  was dissolved in absolute ethanol (5\u2005mL) and hydrogen was bubbled through the mixture for 5\u2005min. raney nickel was added and the mixture was hydrogenated at atmospheric pressure for 12\u2005h at room temperature. The reaction mixture was filtered through celite, and the filter cake was washed plentiful with ethanol. Filtrate was concentrated under reduced pressure, leaving a reddish oil. Vacuum distillation of this afforded 7 as yellowish oil ; Rf=0,29 . 1H NMR: : \u03b4=4.61 , 4.24\u20134.16 , 3.77\u20133.67 , 3.61 , 3.58\u20133.51 , 2.05\u20131.95  1.30\u20131.25 , 1.23\u20131.19 , 1.19\u20131.15  ppm. 13C NMR: : \u03b4=161.8 (COOEt), 100.1 (C\u03b2), 88.5 (C\u03b1), 64.8 (OC2CH3), 64.60 (OC2CH3), 63.2 (COOC2CH3), 15.2 (OC2CH3), 15.1 (OC2CH3), 13.9 (COOC2CH3) ppm. HRMS: (ESI): C9H19NO4 [M], 205.1314\u2005Da. calcd m/z 206.1392 [M+H]+, 228.1206 [M+Na]+, found m/z 206.1379 [M+H]+, 228.1195 [M+Na]+.Ethyl 2\u2010amino\u20103,3\u2010diethoxypropanoate 7 (Method B): A solution of N\u2010formylglycine ethylester 8  in ethylformate  was added dropwise to a mixture of potassium tert\u2010butoxide  in toluene (60\u2005mL) at 10\u2009\u00b0C over a periode of 2\u2005h. Stirring was continued for additional 2\u2005h after which the mixture was allowed to stand at 4\u2009\u00b0C for 18\u2005h. The supernatant was discarded and the gelantinious residue dissolved in ethanol (35\u2005mL). This solution was the diluted with methylene dichloride (50\u2005mL) and cooled to \u221225\u2009\u00b0C and treated with HCl gas for 3\u2005h. The mixture was then stirred for 24\u2005h at room temperature. The solution was concentrated under reduced pressure and the residue was suspended in diethyl ether (80\u2005mL). This suspension was treated with saturated K2CO3 until strongly basic when the phases were separated, and the organic phase was washed further with water and dried over Na2SO4 and evaporated under reduced pressure to afford an oil. Vacuum distillation of this afforded 8 as yellowish oil .NMR ligation experiments: The ligation of peptide 3 with fragments F1, F2 or F3 was confirmed by NMR experiments. The respective fragments were dissolved in a solution of 3, to yield a sample with a final concentration of 10\u2005mM of the fragment and 5\u2005mM of 3. Experiments were performed in 9\u2009:\u20091 H2O/D2O or buffer  at 300\u2005K. Experiments were performed using a WATERGATE water suppression.Peptide 15: Formylglycine peptide 3  and amine F1  were stirred in dry MeOH (1\u2005mL) and AcOH (20\u2005\u03bcL) with molecular sieve  for 1\u2005h at room temperature. NaCNBH3 (2.5\u2005equiv) was added and the mixtures was stirred for 18\u2005h. Molecular sieves were filtered off and the mixture was concentrated under reduced pressure. The residue was purified by RP flash column chromatography yielding 15 as a white solid ; HRMS: (ESI): C35H50N8O15 [M], 822.3396\u2005Da. calcd m/z 823.3474 [M+H]+, 821.3317 [M\u2212H]\u2212, found m/z 823.3477 [M+H]+, 821.3316 [M\u2212H]\u2212.Peptide 16: Following the procedure for peptide 15, 3  and F4  yielded 16 as white solid ; HRMS: (ESI): C35H50N8O16 [M], 838.3345\u2005Da. calcd m/z 839.3423 [M+H]+, 837.3267 [M\u2212H]\u2212, found m/z [M+H]+, [M\u2212H]\u2212.Peptide 17: Following the procedure for peptide 15, 3  and barbituric acid  yielded 17 as white solid ; HRMS: (ESI): C31H45N9O16 [M], 799.2984\u2005Da. calcd m/z 800.3063 [M+H]+, 798.2906 [M\u2212H]\u2212, found m/z 800.3058 [M+H]+, 798.2912 [M\u2212H]\u2212.Peptide 18: Following the procedure for peptide 3, using the unnatural amino acid 19, 18 was obtained as a white solid  from 200\u2005mg resin. 1H\u2005NMR: : \u03b4=8.21 , 8.16 , 8.06 , 8.03 , 7.97 , 7.78 , 7.23 , 7.04 , 6.98 , 6.64 , 4.59\u20134.54 , 4.54\u20134.50 , 4.44 , 4.30\u20134.24 , 4.26\u20134.24 , 4.21 , 4.18 , 3.34 , 3.23 , 2.77\u20132.69 , 2.69\u20132.66 , 2.59\u20132.55 , 2.26\u20132.19 , 1.97\u20131.89 , 1.85 , 1.81\u20131.73 , 1.63\u20131.56 , 1.51\u20131.45 , 1.22 , 0.87 , 0.82 . HRMS: (ESI): C34H48F3N9O15S [M], 911.2943\u2005Da. calcd m/z 912.3021 [M+H]+, 934.2840 [M+Na]+, found m/z 912.3021 [M+H]+, 934.2838 [M+Na]+.2\u2010N\u2010(9H\u2010Fluoren\u20109\u2010ylmethoxycarbonylamino)\u20103\u2010(4\u2010trifluoromethyl\u2010sulfonamido)\u2010phenyl)\u2010amino\u2010propanoic acid 19: To a solution of 20  and NaHCO3  in water (10\u2005mL) was added N\u2010(9\u2010fluorenylmethoxy\u2010carbonyloxy)\u2010succinimide  dissolved in 1,4\u2010dioxane (10\u2005mL) dropwise at 0\u2009\u00b0C. The mixture was allowed to slowly warm up to room temperature and was subsequently stirred for 18\u2005h. Water was added (25\u2005mL) and the mixture extracted with ethyl acetate (3\u00d750\u2005mL). The organic layer was washed with 0.2\u2005M HCl (40\u2005mL) and brine (40\u2005mL) and dried over Na2SO3. The solvents were removed under reduced pressure and the crude product purified via MPLC yielding 19 as a brown solid . 1H NMR:  \u03b4=7.90 , 7.72 , 7.68 , 7.42 , 7.33 , 7.31 , 6.99 , 6.63 , 4.35\u20134.29 , 4.24 , 4.23\u20134.20 , 3.42 , 3.36 . 13C NMR:  \u03b4=172.88 (COOH), 156.62 (CONH), 147.93 (Ar\u2212Cquart), 144.25 (Fmoc Ar\u2212Cquart), 141.18 (Fmoc Ar\u2212Cquart), 128.09 (Fmoc Ar\u2212C), 127.54 (Fmoc Ar\u2212C), 127.17 (Fmoc Ar\u2212C), 125.68 (Fmoc Ar\u2212C), 122.78 (Ar\u2212Cquart), 121.26, 120.57 (Ar\u2212C), 119.42 (CF3), 112.83 (Ar\u2212C), 66.17 (Fmoc CH), 53.75 (C\u03b1), 47.08 (Fmoc CH2), 44.52 (C\u03b2). HRMS: (ESI): C25H22F3N3O6S [M], 549.1181\u2005Da. calcd m/z 550.1260 [M+H]+, 572.1079 [M+Na]+, found m/z 550.1260 [M+H]+, 572.1080 [M+Na]+.2\u2010Amino\u20103\u2010(4\u2010trifluoromethyl\u2010sulfonamido\u2010phenyl)\u2010amino\u2010propanoic acid 20: A mixture of L\u20102\u2010N\u2010Boc\u20102,3\u2010diamino\u2010propanoic acid (Boc\u2010Dap\u2010OH) , 1\u2010fluoro\u20104\u2010nitrobenzene  and K2CO3  in ethanol (15\u2005mL) was stirred for 24\u2005h at 90\u2009\u00b0C. To the crude residue of this reaction was added 10\u2009% Pd/C and the flask wash flushed with H2 and left under H2 atmosphere for 18\u2005h at room temperature. The catalyst was filtered off, the solvent evaporated under vacuum and purified by column chromatography to provide N\u20102\u2010Boc\u20103\u2010(4\u2010aminophenyl)\u20102,3\u2010diamino\u2010propanoic acid as brownish solid . 1H NMR:  \u03b4=6.41 , 6.33 , 6.08  3.64 , 3.11 , 2.94 , 1.38 . 13C NMR:  \u03b4=172.95 (COOH), 155.55 (Boc CO), 141.09 (Ar\u2212Cquart), 139.52 (Ar\u2212Cquart), 116.07 (Ar\u2212C), 114.29 (Ar\u2212C), 78.08 (Boc Cquart), 54.97 (C\u03b1), 48.36 (C\u03b2), 28.79 (Boc CH3). HRMS: (ESI): C14H21N3O4 [M], 295.1532\u2005Da. calcd m/z 296.1610 [M+H]+, 294.1454 [M\u2212H]\u2212, found m/z 296.1612 [M+H]+, 294.1451 [M\u2212H]\u2212. The obtained intermediate  was dissolved in anhydrous DCM (10\u2005mL) under an argon atmosphere and the reaction mixture was cooled to 0\u2009\u00b0C. Trifluoromethanesulfonic anhydride  was added dropwise to the reaction mixture and stirred for 30\u2005min at 0\u2009\u00b0C, after which the mixture was slowly warmed to room temperature and stirred further for 18\u2005h. The reaction was diluted with water (20\u2005mL), filtered and the feed was washed twice with MeCN/H2O . The solvents were evaporated under vacuum and purified by column chromatography to provide 20 as brownish solid . 1H NMR:  \u03b4=7.20 , 6.86 , 6.77 , 6.45 , 3.53 , 3.42 , 3.22 . 13C NMR:  \u03b4=174.37 (C\u20102), 143.13 (C\u20105), 125.16 (C\u20106), 123.58 (C\u20108), 118.43 (C\u201010), 113.56 (C\u20107), 53.77 (C\u20101), 45.69 (C\u20103). HRMS: (ESI): C10H12F3N3O4S [M], 327.0501\u2005Da. calcd m/z 328.0579 [M+H]+, 326.0422 [M\u2212H]\u2212, found m/z 328.0582 [M+H]+, 326.0419 [M\u2212H]\u2212.Z)\u20102\u2010\u20105\u2010oxo\u20101,5\u2010dihydro\u20104H\u2010pyrazol\u20104\u2010ylidene)\u2010hydrazinyl)\u2010phenyl)\u2010acetic acid (21)(: A solution of NaNO2 (0.17\u2005mmol) in H2O (100\u2005\u03bcL) was added at 0\u2009\u00b0C to a suspension of 2\u2010(4\u2010aminophenyl)\u2010acetic acid (0.17\u2005mmol) in 4\u2005M HCl (0.3\u2005mL). The acidic solution was stirred for 1\u2005h at 0\u2009\u00b0C, after which a solution of 2,5\u2010bis(4\u2010nitrophenyl)\u20102,4\u2010dihydro\u20103H\u2010pyrazol\u20103\u2010one (0.15\u2005mmol) in THF (2\u2005mL) was added and the mixtures was stirred for 10\u2005min at 0\u2009\u00b0C. Afterwards a solution of 1.3\u2005M NH4OH (0.2\u2005mL) was added, stirred for 1\u2005h at 0\u2009\u00b0C and for 24\u2005h at r.t. The suspension was filtered under suction, the solid was washed with H2O (2\u00d720\u2005mL), and dried in air. A mixture of EtOAc:DCM:n\u2010Hex  was added in a sealed flask for 2\u2005h. The suspension was filtered off, washed with Et2O and dried under vacuo to provide product 21. 1H\u2005NMR: : \u03b4=8.55 , 8.51 , 8.34 , 8.29 , 7.54 , 7.29 , 3.56  ppm. 13C\u2005NMR: : \u03b4=173.6 (COOH) 157.9 (C\u20107), 147.1 (Pyr Cquart), 146.3 (Ar\u2212Cquart), 143.88 (Pyr Cquart), 142.4 (Ar\u2212Cquart), 141.3 (Ar\u2212Cquart), 130.4 (Ar\u2212C), 130.0 (Ar\u2212Cquart), 129.1(Ar\u2212C), 125.4 (Ar\u2212C), 123.9 (Ar\u2212C), 122.3 (Ar\u2212Cquart), 121.2 (Ar\u2212Cquart), 120.9 (Ar\u2212C), 117.6 (Ar\u2212C), 32.0 (CH2) ppm. HRMS: (ESI): C23H16N6O7 [M], 488.1080\u2005Da. calcd m/z 489.1159 [M+H]+, 487.1002 [M\u2212H]\u2212, found m/z 489.1162 [M+H]+, 487.1005 [M\u2212H]\u2212. Anal: calcd for C22H14F3N7O7S: C, 56.56; H, 3.30; N, 17.21; found: C, 57.12; H, 3.58; N, 17.56.(Z)\u20104\u2010\u20105\u2010oxo\u20101,5\u2010dihydro\u20104H\u2010pyrazol\u20104\u2010ylidene)\u2010hydrazinyl)\u2010phenyl)\u20101,1,1\u2010trifluoromethanesulfonamide (22): Following the procedure for compound 21, using N\u2010(4\u2010aminophenyl)\u20101,1,1\u2010trifluoromethanesulfonamide  and 2,5\u2010bis(4\u2010nitrophenyl)\u20102,4\u2010dihydro\u20103H\u2010pyrazol\u20103\u2010one , 22 was obtained as an orange solid . HRMS: (ESI): C22H14F3N7O7S [M], 577.0628\u2005Da. calcd m/z 578.0706 [M+H]+, found m/z 578.0696 [M+H]+. Anal: calcd for C22H14F3N7O7S: C, 45.76; H, 2.44; N, 16.98; found: C, 45.78; H, 2.54; N, 16.98.Z)\u20102\u2010\u20105\u2010oxo\u20101,5\u2010dihydro\u20104H\u2010pyrazol\u20104\u2010ylidene)\u2010hydrazinyl)\u2010phenoxy)\u2010acetic acid (23)\u2010acetic acid  and 2,5\u2010bis(4\u2010nitrophenyl)\u20102,4\u2010dihydro\u20103H\u2010pyrazol\u20103\u2010one , 23 was obtained as an orange solid . HRMS: (ESI): C23H16N6O8 [M], 504.1030\u2005Da. calcd m/z 505.1108 [M+H]+, 503.0951 [M\u2212H]\u2212, found m/z 505.1106 [M+H]+, 503.0976 [M\u2212H]\u2212. Anal: calcd for C23H16N6O8: C, 54.77; H, 3.20; N, 16.66; found: C, 55.23; H, 3.18; N, 15.62.Protein Expression and purification: DNA encoding the catalytic domain of human PTP1B (amino acids 1\u2013321) was subcloned into the pQLinkH vector. The gene encoding the N\u2010terminal His7\u2010tagged protein was over\u2010expressed at 17\u2009\u00b0C in E. coli Rosetta (DE3). The purification procedure comprises an affinity chromatography on a 5\u2005mL HisTrap FF crude column , charged with Ni2+, and a size\u2010exclusion chromatography on a Superdex 26/60 column  equilibrated with 25\u2005mM HEPES\u2010NaOH (pH=7.5), 50\u2005mM NaCl, 1\u2005mM DTT. The His7\u2010tag was cleaved with tobacco etch virus protease at 20\u2009\u00b0C prior to the gel\u2010filtration step. The catalytic domain of human SHP2 (amino acids 225\u2013541) was purified from E. coli B21 (DE3). The overexpressed protein was fused to an N\u2010terminal His10\u2010tag. Cells were harvested and resuspended in 25\u2005mM Tris\u2010HCl (pH=7.5), 50\u2005mM NaCl, 1\u2009% (v/v) Triton X\u2010100, 10\u2009% (v/v) glycerol, 1\u2005mM DTT. After cell lysis, debris was removed by centrifugation at 12,000\u2005rpm for 30\u2005min. The supernatant was filtered prior to affinity purification with Ni\u2010NTA agarose (Qiagen). The slurry was washed with 50\u2005mM Tris\u2010HCl (pH=8.0), 500\u2005mM NaCl supplemented with 25\u2005mM imidazole. Reasonably pure protein was eluted with 200\u2013300\u2005mM imidazole. The purification was completed by size\u2010exclusion chromatography with a Superdex 75 16/600 column  equilibrated with 20\u2005mM HEPES\u2010NaOH (pH=7.5), 50\u2005mM NaCl, 1\u2005mM DTT.Enzyme activity assays of SHP2 and PTP1B: The catalytic activity of SHP2 catalytic domain and PTP1B were monitored using the fluorogenic substrate DiFMUP . Phosphatase reactions were performed at room temperature in 384\u2010well black plate, clear flat bottom, low flange, non\u2010binding surface  using a final volume of 20\u2005\u03bcL and the following assay buffer conditions: 50\u2005mM MOPS, pH=6.5, 200\u2005mM NaCl, 50\u2005\u03bcM TCEP, 0.03\u2009% Tween\u201020 (freshly added prior to each measurement). Test compounds were dissolved in DMSO or buffer at stock concentrations of 50, 20 or 10\u2005mM and serially diluted. Enzyme  and different concentrations of the tested compounds were incubated in buffer for 30\u201360\u2005min at room temperature. Measurements were performed with a final concentration of 2.5\u2009% DMSO unless stated otherwise at 37\u2009\u00b0C and were performed in triplicate. Enzymatic reactions were started by adding DiFMUP  concentrations matching the experimentally determined MK values of the enzymes of 67\u2005\u03bcM (PTP1B) or 72\u2005\u03bcM (SHP2). Samples were excited at a wavelength of 360\u2005nm and emitted fluorescence was recorded at 460 for 10\u2005min using a microplate reader . Initial slope of fluorescence was determined in triplicate and 50IC values were calculated with GraphPad Prism 5. Determined 50IC values were converted into the corresponding IK values applying the Cheng Prusoff equation IK=50IC/(1+[S]/MK ).Dynamic ligation screening of nucleophilic fragments with 3: Under assay conditions described above, PTP1B or SHP2 were pre\u2010incubated with 3 (100\u2005\u03bcM) for 5\u2005min. Subsequently, (200\u2005\u03bcM) of the respective fragments were added and the resulting mixtures were incubated for 30\u2005min at RT, prior to DiFMUP addition.Determination of apparentKI\u2010values of 11\u2009in a time\u2010dependent assay: Under the conditions described above, PTP1B was pre\u2010incubated with peptide 3 in different concentrations  for 5\u2005mins. Subsequently, over the course of 60\u2005mins (every 15\u2005min), 2 equivalents of fragment F1 were added to each of the different concentrations of 3 at RT, prior to DiFMUP addition.Determination of apparentKI\u2010values of 12\u2009in a concentration\u2010dependent assay: Under the conditions described above, PTP1B was pre\u2010incubated with peptide 3 at different concentrations  for 5\u2005min. Subsequently, fragment F2 was added at three different concentrations  and the resulting mixtures were incubated for 30\u2005min at RT, prior to DiFMUP addition.Computational Methods: The protein X\u2010ray diffraction crystal structure of mutated PTP1B (PDB code: 1PTU)3, 9, 11, 12, 15, 16, and 18 were docked to the binding pocket of PTP1B using Schr\u00f6dinger's GLIDE.Cellular experiments: HeLa cells were cultivated in DMEM buffer with 10\u2009% FCS in 75\u2005cm2 cell culture flasks at 37\u2009\u00b0C, 5\u2009% CO2. At confluency of about 75\u2009%, cells were seeded in a density of 250,000\u2005cells/mL in 6\u2010well plates and incubated for 24\u2005h. Subsequently, medium was removed and replaced by DMEM buffer with 0.1\u2009% BSA (1\u2005mL per well) and incubated for another 16\u2005h. Hepatocyte growth factor  and test compounds in different final concentrations  were added. Control wells received the same amount of DMSO  or no addition. Plates were incubated for 1\u2005h, then washed with cold PBS and shaken with lysis buffer  for 5\u2005min. Cell lysates were transferred to Eppendorf cups and centrifuged at 4\u2009\u00b0C with 10,000\u2005g for 10\u2005min. Total protein was quantified in cell lysates using RotiNanoquant (Carl Roth # K880.1) and 30\u2005\u03bcg of protein was applied to 12\u2009%\u2010SDS\u2010PAGE with a run time of 90\u2005min at 150\u2005V. Then protein was blotted in Towbin bufer to an PVDF\u2010membrane over 1\u2005h at 100\u2005V, and the membrane was saturated with 20\u2005ml TBS\u2010Tween/ 2\u2009% BSA, 1\u2005h at RT. The blot was incubated with anti\u2010phospo\u2010ERK as primary antibody  overnight at 4\u2009\u00b0C, washed 3\u00d75\u2005min with TBS\u2010Tween, and incubated with anti\u2010mouse IgG\u2010hrp as secondary antibody . The blot was again washed 3\u00d75\u2005min with TBS\u2010Tween and imaged with the ECL system (ThermoScientific # 34080) at Syngene PXi Imager. From the same lysis sample, under the same conditions, ERK 1/2 and \u03b2\u2010tubulin were blotted. For \u03b2\u2010tubulin, the antibody incubation time was adjusted to 2\u2005h at RT.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The chains are inter\u00addigitated.The nearly planar mol\u00adecule is centrosymmetric with two all- 70H112N6O6, is centrosymmetric with two all-s-trans chains, the other two chains have an s-cis unit starting with the oxygen atoms. The chains are inter\u00addigitated in the packing.The nearly planar mol\u00adecule of the title compound, C The centrosymmetric mol\u00adecule is located parallel to the (110) plane, the five aromatic rings are almost coplanar with torsion angles of \u22120.4\u2005(4)\u00b0 (N6\u2014C5\u2014C3\u2014C2) and \u22122.0\u2005(4)\u00b0 (C11\u2014C10\u2014C8\u2014N7). Two dodec\u00adyloxy chains per mol\u00adecule are completely all-s-trans organized whereas the other pair shows an s-cis-conformation of the O16\u2014C17\u2014C18\u2014C19 unit. Torsion angles at the all-trans chains are 179.3\u2005(2) for C13\u2014C14\u2014O29\u2014C30, 177.9\u2005(5)\u00b0 for C14\u2014O29\u2014C30\u2014C31 and 178.1\u2005(2)\u00b0 for O29\u2014C30\u2014C31\u2014C32 but for the other chain, 15.8\u2005(3)\u00b0 (C17\u2014O16\u2014C12\u2014C13), 176.2\u2005(2)\u00b0 (C12\u2014O16\u2014C17\u2014C18), and \u221255.3\u2005(3)\u00b0 for the O16\u2014C17\u2014C18\u2014C19 unit. The packing is controlled by inter\u00adaction of the aliphatic chains  is located above the pyrazine centroid.Electron-deficient conjugated oligomers are inter\u00adesting as electron-transporting mat\u00aderials in organic electronics : 2916, 2848, 1602, 1544, 1468, 1442, 1429, 1174; 1H NMR , 6.66 , 4.04 , 3.17 , 1.82 , 1.55-1.42 , 1.42-1.20 , 0.93-0.83 . Whereas the absorption spectrum of the title compound in cyclo\u00adhexane peaks at 348\u2005nm, three maxima appear in methanol , indicating aggregation. The emission of a solution in cyclo\u00adhexane is centered at 403\u2005nm, and in toluene at 409\u2005nm. Crystallization was via slow evaporation of a solution in chloro\u00adform/2-propanol.The title compound was prepared Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2414314623000342/bt4131sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314623000342/bt4131Isup2.hklStructure factors: contains datablock(s) I. DOI: 2235881CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains three independent mol\u00adecules differing slightly in conformation. Portions of the observed conformations are determined by intra\u00admolecular N\u2014H\u22efO hydrogen bonds. In the crystal, O\u2014H\u22efO hydrogen bonds form chains of mol\u00adecules which are linked into corrugated sheets parallel to ( 14H13NO4, contains three independent mol\u00adecules, which differ slightly in conformation. Each contains an intra\u00admolecular N\u2014H\u22efO hydrogen bond. In the crystal, O\u2014H\u22efO hydrogen bonds form chains of mol\u00adecules, which are linked into corrugated sheets parallel to (The asymmetric unit of the title compound, C These compare quite favorably with those found in mol\u00adecules with R = Me  differ modestly in the orientations of the methyl groups while the third differs more in conformation from the other two Fig.\u00a01. In each3.B\u22efO7, O5\u2014H5B\u22efO11 and O9\u2014H9B\u22efO3 hydrogen bonds repeating in that order \u2005\u00c5, C10\u22efCg2 = 3.731\u2005(2)\u2005\u00c5, C10=O2\u22efCg2 = 91.41\u2005(13)\u00b0 \u2005\u00c5, C24\u22efCg6 = 3.694\u2005(2)\u2005\u00c5, C24=O6\u22efCg6 = 91.12\u2005(14)\u00b0 ; O10\u22efCg4 = 3.4110\u2005(18)\u2005\u00c5, C38\u22efCg4 = 3.656\u2005(2)\u2005\u00c5, C38=O10\u22efCg4 = 91.00\u2005(13)\u00b0 ]. The layers are held together by C11\u2014H11C\u22efO6 hydrogen bonds  are smaller than 1.0% with low densities of points.In order to visualize the inter\u00admolecular inter\u00adactions, a Hirshfeld surface (HS) analysis  using the standard B3LYP functional and 6\u2013311\u2005G basis-set calculations , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are recorded in Table\u00a03E)-3-[1-(2-hy\u00addroxy\u00adphenyl\u00adamino)\u00adethyl\u00adidene]-6-methyl-3H-pyran-2,4-dione ring. The energy band gap [\u0394E = ELUMO\u00a0\u2212\u00a0EHOMO] of the mol\u00adecule is 4.54\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22126.12 and \u22121.58\u2005eV, respectively.The optimized structure of the title compound in the gas phase was generated theoretically 6.Gaussview software  was used to broadly predict reactive sites for electrophilic and nucleophilic attack in the title compound by B3LYP/6-31G optimized geometries using 7.et al., 2016A  yielded 66 hits of which 15 were deemed most similar to the title mol\u00adecule. These include mol\u00adecules with R = Me  in 30\u2005mL of ethanol, 2.5\u2005mmol of de\u00adhydro\u00adacetic acid were added. The mixture was refluxed for 1\u2005h. After cooling, the precipitate that formed was recrystallized from ethanol solution to give yellow crystals in 88% yield.9.Uiso(H) = 1.2Ueq or 1.5Ueq.Crystal, data collection and refinement details are presented in Table\u00a0410.1107/S2056989022007514/zn2020sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022007514/zn2020Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022007514/zn2020Isup3.cmlSupporting information file. DOI: 2192044CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2010Acetylneuraminic acid  is one of a large, diverse family of nine\u2010carbon monosaccharides that play roles in many biological functions such as immune response. Neu5Ac has previously been identified as a potential biomarker for the presence and pathogenesis of cardiovascular disease (CVD), diabetes and cancer. More recent research has highlighted acetylated sialic acid derivatives, specifically Neu5,9Ac2, as biomarkers for oral and breast cancers, but advances in analysis have been hampered due to a lack of commercially available quantitative standards. We report here the synthesis of 9\u2010O\u2010 and 4\u2010O\u2010acetylated sialic acids  with optimisation of previously reported synthetic routes. Neu5,9Ac2 was synthesised in 1 step in 68\u2009% yield. Neu4,5Ac2 was synthesised in 4 steps in 39\u2009% overall yield. Synthesis was followed by analysis of these standards via quantitative NMR (qNMR) spectroscopy. Their utilisation for the identification and quantification of specific acetylated sialic acid derivatives in biological samples is also demonstrated. Synthesised acetylated derivatives of N\u2010acetylneuraminic acid, Neu5,9Ac2 and Neu4,5Ac2, alongside commercially available Neu5Ac and Neu5Gc were utilised as standards for the quantitative analysis of these derivatives in plasma and serum samples. Multiple derivatives could be detected in one assay, which exhibited high specificity and low limits of detection and quantitation. Neu5Ac is a nine\u2010carbon backbone monosaccharide with a carboxylic acid functional group Figure\u2005 and is oN\u2010glycans as the terminating unit  was treated with trimethyl orthoacetate in the presence of catalytic p\u2010toluene sulfonic acid for 20\u2005minutes to afford Neu5,9Ac2(2) in 68\u2009% yield after purification using ion\u2010exchange chromatography  to 3.95 and 4.26\u2005ppm in (2).Neu5,9Ac, Neu5Ac  was trea2(3) was based on work by Ogura et\u2005al.(3) therefore commenced with protection of the carboxylic acid group to give a methyl ester using conditions developed by Malapelle et\u2005al. employing methanol and trifluoroacetic acid to give (4) in quantitative yield.+ resin to give (5) in 65\u2009% yield. Deprotection of the methyl ester is required in the next step. The method put forth by Ogura et\u2005al. using 1\u2005M NaOH was utilised to give (6) in quantitative yield. The acetyl group was installed at the 4\u2010position using excess pyridine and acetic anhydride and the crude mixture was then purified using ion exchange chromatography using 1\u2005M formic acid as the eluent. Removal of the formic acid under reduced pressure at 35\u2009\u00b0C, as opposed to the use of lyophilisation by Ogura et\u2005al. then afforded (3) in 60\u2009% yield  to 5.17\u2005ppm in the target compound (3).The route chosen to synthesise Neu4,5Ac2 and Neu4,5Ac2 in hand, the next step was to determine the purity of the standards using qNMR techniques. The method chosen for this was based on the pulse length based concentration determination (PULCON) method,20D\u221213\u2009\u00b0 ; mp. 153\u2013155\u2009\u00b0C; 1H NMR : \u03b4 4.26 , 4.07 , 4.00\u20133.90 , 3.87\u20133.77 , 3.49 , 2.19 , 2.00 , 1.94 , 1.81\u20101.72 : \u03b4 174.73 (C13), 174.41 (C11), 171.22 (C14), 95.48 (C2), 70.15 (C7), 69.2 (C8), 67.59 (C6), 66.80 (C4), 66.26 (C9), 52.03 (C5), 38.89 (C3), 22.6 (C12), 20.19 (C15) ppm; IR vmax [cm\u22121] (powder) 3295 , 1719 (C=O), 1034 (C\u2212O); HRMS (ESI): m/z calc for C13H22O10N: 352.1238 [M+H]+; found: 351.1239.Methyl 5\u2010Acetamido\u20103,5\u2010dideoxy\u2010D\u2010glycero\u2010D\u2010galactononulopyranosonate (4):N\u2010acetylneuraminic acid 1  in methanol (40\u2005mL) was added TFA . This was stirred at room temperature for 48\u2005hrs. The solvent was removed under reduced pressure to give the methyl ester 4 as a white solid  [\u03b1]20D\u221226\u2009\u00b0 ; mp. 177\u2013178\u2009\u00b0C; 1H NMR : \u03b4 3.94 , 3.80 , 3.72 , 3.60 , 3.50 , 3.42 , 2.19 , 1.92 , 1.79  ppm 13C NMR : \u03b4 174.79 (C13), 171.36 (C11), 95.29 (C2), 70.29 (C6), 70.05 (C8), 68.14 (C7), 66.62 (C4), 63.10 (C9), 53.43 (C14), 52.00 (C5), 38.60 (C3), 22.00 (C12) ppm; IR vmax [cm\u22121] (powder) 3256 , 2944 (C\u2212H), 1751 (C=O), 1026 (C\u2212O); HRMS (ESI): m/z calc for C12H21O9NNa: 352.1109 [M+H]+; found: 346.1102.O\u2010isopropylidene\u2010D\u2010glycero\u2010\u03b2\u2010D\u2010galactononulopyranosonate (5)Methyl 5\u2010acetamido, 3,5\u2010dideoxy\u20108,9\u2010:4  in acetone (50\u2005mL) was added Amberlyst 15 H+ resin (1.5\u2005g) and 2,2\u2010dimethoxypropane . This was stirred for 3.5\u2005hrs at room temperature before being filtered to remove the resin. The resin was washed with acetone and the filtrate collected. After removing the solvent under reduced pressure, the resulting crude material was passed over a silica plug and eluted with ethyl acetate (4\u00d7200\u2005mL) to give acetonide 5 as a beige foam  [\u03b1]20D\u221224\u2009\u00b0 ; mp. 164\u2013166\u2009\u00b0C; 1H NMR : \u03b4 8.07 , 6.71 , 4.82 , 4.75 , 4.02\u20103.94 , 3.90\u20103.86 , 3.85\u20103.78 , 3.68 , 3.56 , 3.52\u20103.49 , 2.03 , 1.88 , 1.61 , 1.26 , 1.23  ppm 13C NMR : \u03b4 179.94 (C13), 171.68 (C11), 107.22 (C15), 94.57 (C2), 75.92 (C8), 71.70 (C7), 68.38 (C6), 65.20 (C9), 64.94 (C4), 52.89 (C14), 52.12 (C5), 40.23 (C3), 26.55 (C16), 25.72 (C16), 22.55 (C12) ppm; IR vmax [cm\u22121] (powder) 3291 , 2926 (C\u2212H), 1740 (C=O), 1032 (C\u2212O); HRMS (ESI): m/z calc for C15H25O9NNa: 386.1422 [M+Na]+; found: 386.1416.O\u2010isopropylidene\u2010D\u2010glycero\u2010D\u2010galactononulopyranosonate (6)5\u2010Acetamido\u20103,5\u2010dideoxy\u20108,9\u2010:5  was dissolved in 1\u2005M NaOH (5\u2005mL) and stirred for 4\u2005hrs at room temperature. This was then diluted with water (10\u2005mL) and deionised with Amberlyst H+ resin. The mixture was filtered, the filtrate was collected and lyophilised to give a white solid 6 . [\u03b1]20D\u221225\u2009\u00b0 ; mp. 157\u2013158\u2009 \u00b0C; 1H NMR : \u03b4 4.25 , 4.20\u20104.11 , 4.07\u20103.97 , 3.95\u20103.85 , 3.62 , 2.09 , 1.46 , 1.36  ppm; 13C NMR : \u03b4 176.75 (C13), 174.43 (C11), 168.30 (C2), 109.58 (C14), 75.10 (C8), 70.59 (C7), 69.07 (C6), 66.99 (C9), 66.14 (C4), 52.16 (C5), 25.77 (C15), 24.27 (C15), 21.99 (C12) ppm; IR vmax [cm\u22121] (powder) 3282 , 1735 (C=O), 1427 (COOH) 1057 (C\u2212O); HRMS (ESI): m/z calc for C14H23O9NNa: 372.1265 [M+H]+; found: 372.1263.O\u2010acetyl\u2010D\u2010glycero\u2010D\u2010galactononulopyranosonate (3)5\u2010Acetamido\u20103,5\u2010dideoxy\u20104\u2010:6  in dry pyridine (0.5\u2005mL) under nitrogen was added acetic anhydride . This was stirred at room temperature for 18\u2005hours after which ethanol was added to remove excess acetic anhydride and solvent removed under reduced pressure by co\u2010evaporation with toluene (3\u00d7100\u2005mL). The resultant residue was dissolved in water (10\u2005mL) and passed through a column (2\u00d710\u2005cm) of DOWEX\u20101X8 formate anion exchange resin (100\u2013200\u2005mesh). The column was washed with water (3\u00d710\u2005mL) and eluted with formic acid (50\u2005mL). The formic acid was removed under reduced pressure to give a clear residue. The residue was dissolved in water (5\u2005mL) and lyophilised to give 4\u2010O N\u2010acetylneuraminic acid 3 as a white solid . [\u03b1]20D\u221234\u00b0 ; mp. 170\u2013172\u2009\u00b0C; 1H NMR : 5.22\u20105.12 , 4.18\u20103.99 , 3.76\u2010 3.72 , 3.63 , 3.50 , 2.24 , 1.95 , 1.87 ; 13C NMR : \u03b4 174.7 (C14), 173.38 (C13), 173.31 (C11), 95.24 (C2), 70.07 (C8), 70.00 (C7), 68.01 (C6), 63.09 (C4), 53.50 (C9), 49.38 (C5), 36.02 (C3), 21.85 (C12), 20.30 (C15) ppm; IR vmax [cm\u22121] (powder) 3340 , 2933 (C\u2212H), 1727 (C=O), 1019 (C\u2212O); HRMS (ESI): m/z calc for C13H22O10N: 352.1238 [M+H]+; found: 351.1239.Quantitative NMR analysis: Into an NMR tube was placed 600\u2005\u03bcL of a 5.03\u2005mMol maleic acid solution in D2O. A 1.8\u2005mg quantity of synthesised standard was dissolved in 1.8\u2005mL of D2O. This was split into three 600\u2005\u03bcL samples in order to analyse the standards in triplicate. After matching and tuning, each NMR sample was analysed on a 500\u2005MHz NMR spectrometer where a 1D 1H spectrum with water suppression was obtained with a relaxation delay of 20 seconds. The 360\u2009\u00b0 pulse was obtained for each spectrum using pulsecal. The pulse sequence used was noesypr1D. Equation\u20051 was used to determine the concentration and purity of each synthesised standard.2 and Neu4,5Ac2 standardsDMB labelling of the Neu5Ac, Neu5Gc, Neu5,9Ac: Neu5Ac, Neu5Gc, Neu5,9Ac2 and Neu4,5Ac2 standards were labelled using LudgerTagTM DMB Sialic Acid (LT\u2010KDMB\u201096). DMB labelling solution (20\u2005\u03bcL) was added to the standards. The samples were then vortexed and centrifuged followed by incubation at 50\u2009\u00b0C for 3\u2005hours. The labelling reaction was quenched by the addition of water to give a final volume of 500\u2005\u03bcL (480\u2005\u03bcL). Standard curves were prepared by performing serial dilution to create a standard curve with points: 0.01, 0.02, 0.1, 0.2, 0.5, 1.0 nmol. The procedure was carried out using a Hamilton MICROLAB STARlet Liquid Handling Robot.Sialic acid release and DMB labelling of human plasma and guinea pig serum: Release of sialic acid and DMB labelling of the samples was achieved using LudgerTagTM DMB Sialic Acid (LT\u2010KDMB\u201096). A 5 \u03bcL aliquot of each sample was dispensed into a 96\u2010well plate in triplicate. To this was added 25 \u03bcL of 2\u2005M acetic acid. The sample was vortexed and centrifuged followed by incubation at 80\u2009\u00b0C for 2\u2005hours. The sample was allowed to cool to room temperature and a 5 \u03bcL aliquot of each sample was transferred to a new 96\u2010well plate. To this was added 20\u2009\u03bcL of DMB labelling solution. The sample was then vortexed and centrifuged followed by incubation at 50\u2009\u00b0C for 3\u2005hours. The labelling reaction was quenched by the addition of water to give a final volume of 500\u2005\u03bcL (475\u2005\u03bcL). The samples were then subjected to a 1 in 10 dilution . All procedures, except the dispensing of the samples on the plate, were conducted using a Hamilton MICROLAB STARlet Liquid Handling Robot.Sialic acid release and DMB labelling of porcine and ovine serum: Release of sialic acid and DMB labelling of the samples was achieved using LudgerTagTM DMB Sialic Acid (LT\u2010KDMB\u201096). A stock solution was first prepared by dissolving 10\u2005mg of porcine or ovine serum in 1\u2005mL ultra\u2010pure water. A 10 \u03bcL aliquot taken from the solution of each sample was dispensed into a 96\u2010well plate in triplicate. To this was added 25\u2005\u03bcL of 2\u2005M acetic acid. The sample was vortexed and centrifuged followed by incubation at 80\u2009\u00b0C for 2\u2005hours. The sample was allowed to cool to room temperature and a 5 \u03bcL aliquot of each sample was transferred to a new 96\u2010well plate. To this was added 20\u2005\u03bcL of DMB labelling solution. The sample was then vortexed and centrifuged followed by incubation at 50\u2009\u00b0C for 3\u2005hours. The labelling reaction was quenched by the addition of water to give a final volume of 500\u2005\u03bcL (475\u2005\u03bcL). The samples were then subjected to a 1 in 10 dilution . All procedures, except the dispensing of the samples on the plate, were carried out using a Hamilton MICROLAB STARlet Liquid Handling Robot.2Sialic acid release and DMB labelling of plasma for Neu5,9Ac: Release of Sialic Acid and DMB labelling of the samples was achieved using LudgerTagTM DMB Sialic Acid (LT\u2010KDMB\u201096). A 25 \u03bcL aliquot of each sample was dispensed into a 96\u2010well plate in triplicate. To this was added 75 \u03bcL of 2.666\u2005M acetic acid. The sample was vortexed and centrifuged followed by incubation at 80\u2009\u00b0C for 2\u2005hours. The sample was allowed to cool\u2010room temperature and a 20 \u03bcL aliquot of each sample was transferred to a new 96\u2010well plate. To this was added 20\u2005\u03bcL of DMB labelling solution. The sample was then vortexed and centrifuged followed by incubation at 50\u2009\u00b0C for 3\u2005hours. The labelling reaction was quenched by the addition of water to give a final volume of 500\u2005\u03bcL (475\u2005\u03bcL). The sample was subjected to filtration through a Ludger Clean Protein Binding Membrane filtration plate (LC\u2010PBM\u2010plate) to remove excess protein. All procedures, except the dispensing of the samples on the plate and LC\u2010PBM\u2010plate filtration, were carried out using a Hamilton MICROLAB STARlet Liquid Handling Robot.Fluorescence analysis of DMB labelled sialic acid derivatives by LC\u2010fluorescence detection: DMB labelled sialic acid derivatives were analysed by LC\u2010FLD. A 5\u2009\u03bcL aliquot of each sample was injected to a LudgerSep\u2122 uR2 UHPLC column  at 30\u2009\u00b0C on a Dionex UltiMate\u21223000 RSLCnano system with a fluorescent detector . For Neu5Ac analysis, an isocratic solvent system was used (7\u2009:\u20099\u2009:\u200984 MeOH : ACN : H2O) for 15 minutes including an ACN wash. For Neu5,9Ac2 analysis a variable solvent system was used: 7\u2009:\u20096\u2009:\u200987 MeOH:ACN:H2O for 6.5 minutes followed by 6\u2009:\u20099\u2009:\u200985 MeOH:ACN:H2O for 11.5\u2005minutes. Integration of resultant peaks was performed using Chromeleon 7. LOD and LOQ regression analysis and calculation was performed using Microsoft Excel 2019.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The bridging O2\u2212 ligand is located on a twofold rotation axis, resulting in point group 2 for the entire complex. The MnIII atom is displaced out of the 24-atom mean plane of the porphyrine entity by 0.52\u2005\u00c5. C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions help to stabilize the mol\u00adecular packing within the crystal structure.In the crystal structure of the title oxido-bridged binuclear complex, [Mn The two MnIII ions are displaced by 0.48 and 0.52\u2005\u00c5 from their respective 24-atom mean plane. It is inter\u00adesting to note that the \u03bc-oxido species [Mn(OEP)]2O is very unstable in halocarbon solvents . Figs. 12O are bridged by a single oxido ligand with an Mn\u2014O distance of 1.7600\u2005(3)\u2005\u00c5 and an Mn\u2014O\u2014Mn bridging angle of 176.1\u2005(2)\u00b0. The Mn1\u22efMn1\u2032 separation 2(OH)}ClO4, the title compound shows virtually the same metal displacement from the 24-atom mean plane (0.52\u2005\u00c5), while a larger Mn\u2014O\u2014Mn bridging angle [176.1\u2005(2) versus. 160.4\u2005(8)\u00b0] and a shorter Mn\u2014O distance [1.7600\u2005(3) versus. 2.026\u2005(1)\u2005\u00c5] is observed.In the crystal structure of the title complex, the asymmetric unit contains one deprotoanted porphyrin mol\u00adecule located in general position and an oxygen atom on a twofold rotation axis ]Cl were prepared according to literature protocols ]2O (10\u2005mg) was dissolved in 4\u2005ml of chloro\u00adbenzene and cannula-transferred into 8\u2005mm glass tubes, then carefully layered with hexa\u00adnes before sealing the tubes. X-ray quality crystals were obtained several weeks later.The title compound was prepared following a reported procedure  I. DOI: 10.1107/S2414314622008690/wm4172Isup2.hklStructure factors: contains datablock(s) I. DOI: 2204345CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Longer N\u2014H\u22efO hydrogen bonds link the tetra\u00admers into [010] chains.In the title hydrated Schiff base, the dihedral angle between the aromatic rings is 5.06\u2005(11)\u00b0 and an intra\u00admolecular O\u2014H\u22efN hydrogen bond closes an S(6) ring. In the crystal, O 13H12N4O3\u00b7H2O, the dihedral angle between the aromatic rings is 5.06\u2005(11)\u00b0 and an intra\u00admolecular O\u2014H\u22efN hydrogen bond closes an S(6) ring. In the crystal, Ow\u2014H\u22efO and Ow\u2014H\u22efN (w = water) hydrogen bonds link the components into centrosymmetric tetra\u00admers (two Schiff bases and two water mol\u00adecules). Longer N\u2014H\u22efO hydrogen bonds link the tetra\u00admers into [010] chains. A weak C\u2014H\u22efO hydrogen bond and aromatic \u03c0\u2013\u03c0 stacking between the pyrazine and phenyl rings [centroid\u2013centroid separations = 3.604\u2005(2) and 3.715\u2005(2)\u2005\u00c5] are also observed.In the title hydrated Schiff base, C Their applications include mol\u00adecular switches (Coskun S(6) ring. The C7\u2014N2 bond length [1.278\u2005(3)\u2005\u00c5] is consistent with a normal carbon\u2013nitro\u00adgen double bond. In the crystal, Ow\u2014H\u22efO and Ow\u2014H\u22efN (w = water) hydrogen bonds link the components into centrosymmetric tetra\u00admers (two Schiff base and two water mol\u00adecules). Longer N\u2014H\u22efO hydrogen bonds link the tetra\u00admers into [010] chains \u00b0 and an intra\u00admolecular O2\u2014H2\u22efN2 hydrogen bond closes an s Table\u00a01. The pacPyrazine-2-carbohydrazide  was reacted with 2-hy\u00addroxy-3-meth\u00adoxybenzaldehyde  under reflux in 25\u2005ml methanol for 8\u2005h. After cooling and solvent removal by rotary evaporation, a light yellow solid was obtained, which was recrystallized from methanol solution at room temperature to obtain colourless crystals of the title compound.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314619017310/hb4335sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314619017310/hb4335Isup2.hklStructure factors: contains datablock(s) I. DOI: 1973543CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Orientogalba ollula has been reported as intermediate hosts of many zoonotic trematodes. Here, we investigated the prevalence of zoonotic trematodes within O. ollula in Guangxi, China, and assessed their zoonotic potential.Food-borne parasitic diseases decrease food safety and threaten public health. The snail species is an intermediate host for numerous human parasitic trematodes. Echinostoma revolutum was recorded by dissecting infected ducklings from 1-day post infection (dpi) to 10 dpi.Snails were collected from 54 sites in 9 cities throughout Guangxi. The snail and trematode larvae species were determined by combining morphological characteristics and molecular markers. The trematodes prevalence and constituent ratio were calculated and compared among different habitat environments. Phylogenetic trees of the trematode species were constructed using the neighbor-joining method with nuclear internal transcribed spacer 2 (ITS2) sequences. The developmental cycles of the isolated trematodes were examined by experimental infection in ducks. The developmental characteristics of O. ollula from 11 sample sites. Morphological together with molecular identification, showed that E. revolutum, Australapatemon sp., Hypoderaeum conoideum, Pharyngostomum cordatum, and Echinostoma sp. parasitized O. ollula, with the highest infection rate of E. revolutum (13.0%). However, no Fasciola larvae were detected. The trematodes prevalence and constituent ratio varied in two sub-biotypes (P\u2009<\u20090.01). A neighbor-joining tree analysis of ITS2 sequences resulted in distinct monophyletic clades supported by sequences from isolated larvae with high bootstrap values. Ducklings exposed to O. ollula infected with Echinostoma sp., E. revolutum, and H. conoideum larvae were successfully infected. The animal model for Echinostoma revolutum was successfully established. E. revolutum matured from larvae to adult at 10 dpi in the intestine of the duck, and the developmental characteristics of E. revolutum were characterized by the maturation of the reproductive and digestive organs at 6\u20138 dpi.The overall prevalence of trematode larvae was 22.1% (1818/8238) in O. ollula from Guangxi, China. Existing trematodes infection in animals and human clinical cases, coupled with the wide geographical distribution of O. ollula, necessitate further evaluations of the potential risk of spillover of zoonotic infection from animal to human and vice versa.This study revealed a high prevalence of zoonotic trematodes in The online version contains supplementary material available at 10.1186/s40249-022-01014-7. Corresponding trematodes belong to the families Fasciolidae, Paragonimidae and Echinostomatidae  in the feces, and the morphological characteristics of adult Echinostoma sp. were presented as measurements: body length (9.8\u2009\u00b1\u20091.8\u00a0mm), width (1.2\u2009\u00b1\u20092.3\u00a0mm), oral sucker [(638.9\u2009\u00b1\u20091.9)\u2009\u00d7\u2009(399.2\u2009\u00b1\u200915.8) \u03bcm], acetabulum [(1591.2\u2009\u00b1\u200917.8)\u2009\u00d7\u2009(1338.2\u2009\u00b1\u200919.6) \u03bcm], pharynx [(492.6\u2009\u00b1\u200954.3)\u2009\u00d7\u2009(331.7\u2009\u00b1\u200974.8) \u03bcm], anterior testis [(1120.5\u2009\u00b1\u2009139.6)\u2009\u00d7\u2009(707.4\u2009\u00b1\u200949.2) \u03bcm], posterior testis [(1274.9\u2009\u00b1\u2009181.1)\u2009\u00d7\u2009(880.4\u2009\u00b1\u200949.2) \u03bcm], and ovary [(818.9\u2009\u00b1\u200910.2)\u2009\u00d7\u2009(527.9\u2009\u00b1\u200948.3) \u03bcm].We conducted an infection experiment for three kinds of trematode to evaluate the rates of parasite establishment in ducklings. Ducklings were individually exposed to H. conoideum eggs in ducklings fed with infected O. ollula from three sites after a median duration of 12 dpi (range: 9 dpi to 14 dpi). The morphological characteristics of adult H. conoideum were as follows: body length (1.05\u2009\u00b1\u20090.61\u00a0mm), width (1.5\u2009\u00b1\u20090.27\u00a0mm), oral sucker [(424.2\u2009\u00b1\u200916.1)\u2009\u00d7\u2009(293\u2009\u00b1\u200911.2) \u03bcm], acetabulum [(1610.2\u2009\u00b1\u200998.4)\u2009\u00d7\u2009(1594.6\u2009\u00b1\u2009198.7) \u03bcm], pharynx [(379.8\u2009\u00b1\u200953.2)\u2009\u00d7\u2009(253.6\u2009\u00b1\u200944.9) \u03bcm], anterior testis [(1902.6\u2009\u00b1\u2009164.6)\u2009\u00d7\u2009(875.3\u2009\u00b1\u2009140.8) \u03bcm], posterior testis [(2045.2\u2009\u00b1\u2009255.8)\u2009\u00d7\u2009(898.2\u2009\u00b1\u2009139.2) \u03bcm], ovary [(751.7\u2009\u00b1\u2009129.3)\u2009\u00d7\u2009(553.9\u2009\u00b1\u2009110.6) \u03bcm], and the possession of 50 spines. E. revolutum eggs [(104.1\u2009\u00b1\u200915.1)\u2009\u00d7\u2009(63.1\u2009\u00b1\u200912.6\u00a0\u03bcm] were found on 10 dpi. The morphology of the adult E. revolutum was characterized by: body length (8.5\u2009\u00b1\u20091.2\u00a0mm), width (2.2\u2009\u00b1\u20090.7\u00a0mm), oral sucker [(260.0\u2009\u00b1\u200932.5)\u2009\u00d7\u2009(180.1\u2009\u00b1\u200919.8) \u03bcm], acetabulum [(741.6\u2009\u00b1\u200923.7)\u2009\u00d7\u2009(598.3\u2009\u00b1\u200925.1) \u03bcm], pharynx [(193.1\u2009\u00b1\u200930.5)\u2009\u00d7\u2009(150.6\u2009\u00b1\u200927.8) \u03bcm], anterior testis [(628.0\u2009\u00b1\u200931.2)\u2009\u00d7\u2009(459.4\u2009\u00b1\u200927.8) \u03bcm], posterior testis (725.5\u2009\u00b1\u200917.1\u2009\u00d7\u2009557.9\u2009\u00b1\u200918.7\u00a0\u03bcm), ovary [(411.8\u2009\u00b1\u200918.5)\u2009\u00d7\u2009(311.2\u2009\u00b1\u200915.4) \u03bcm], and the presence of a head collar with 37 spines.In contrast, we found E. revolutum in duckling hosts, because there were insufficient snails infected with metacercariae of Echinostoma sp. and H. conoideum. The developmental characteristics of E. revolutum were recorded by dissecting infected ducklings from 1 to 10 dpi when eggs in the feces were first detected. E. revolutum could be obtained in the small intestine from 1 to 7 dpi and then migrate and reside in the cecum and colon from 8 to 10 dpi. The body length developed from 490\u00a0\u03bcm to 8500.5\u00a0\u03bcm (a 17-fold increase). At 1 dpi, juveniles had a circumoral collar bearing 37 spines in a double circle and characterized by clearly visible oral suckers, acetabulum, pharynx, esophagus, and cecum. At 1 dpi, the tiny structure of the testis appeared. By 4 dpi, the ovaries were beginning to organize and develop, and the seminal receptacle began to form. The tubular-shaped uterus loomed at 4 dpi, and maturation of the reproductive and digestive organs occurred at 6 to 8 dpi. The vitelline glands were the last to appear, and several eggs deposited in the uterus were observed at 9 dpi. E. revolutum larvae matured at 10 dpi and excreted eggs ."}
{"text": "Aqua\u00adtri\u00adfluorido\u00adboron and ethyl\u00adene carbonate form a 1:2 co-crystal with a C=O\u22efH\u2014O\u2014H\u22efO=C hydrogen-bonding motif. 3H2O\u00b72OC(OCH2)2, was determined by low-temperature single-crystal X-ray diffraction. The co-crystal crystallizes in the ortho\u00adrhom\u00adbic space group P212121 with four formula units per unit cell. The asymmetric unit consists of an aqua\u00adtri\u00adfluorido\u00adboron mol\u00adecule and two ethyl\u00adene carbonate mol\u00adecules, connected by O\u2014H\u22efO=C hydrogen bonds. This crystal structure is an inter\u00adesting example of a superacidic BF3H2O species co-crystallized with an organic carbonate.The crystal structure of the co-crystal of aqua\u00adtri\u00adfluorido\u00adboron with two ethyl\u00adene carbonate  mol\u00adecules, BF The overall shape of the BF3 moiety in BF3H2O in terms of bond lengths and angles is similar to that of the BF4\u2212 anion  graph-set motif 2 co-crystal were discovered when a crystalline sample of the air-sensitive BF3\u00b7OC(OCH2)2 adduct was examined under a protective cold nitro\u00adgen stream at about \u221250\u2005\u00b0C. The BF3\u00b7OC(OCH2)2 compound was synthesized from dry ethyl\u00adene carbonate and BF3 gas under anhydrous conditions, as described previously 2 were located in a droplet at the tip of the aluminium trough  I. DOI: 10.1107/S2414314623000627/wm4182Isup2.hklStructure factors: contains datablock(s) I. DOI: 2237804CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "D2 symmetry. They show a largely twisted double bond, the mol\u00adecular halves enclosing dihedral angles of 62.86\u2005(4) and 61.22\u2005(3)\u00b0.The asymmetric unit of the title compound contains two almost identical mol\u00adecules, which have approximate  42H24, contains two almost identical mol\u00adecules. The mol\u00adecules have approximate D2 symmetry. They show a largely twisted double bond, the mol\u00adecular halves enclosing dihedral angles of 62.86\u2005(4) and 61.22\u2005(3)\u00b0. The crystal studied was twinned by non-merohedry.The asymmetric unit of the title compound, C The dihedral angle between these planes is 62.86\u2005(4)\u00b0 and the length of the central C1A\u2014C22A bond is 1.408\u2005(5)\u2005\u00c5. The values for mol\u00adecule B are very similar: maximum deviations from the mean planes are \u22120.293\u2005(4)\u2005\u00c5 for C5 (B1) and 0.170\u2005(4)\u2005\u00c5 for C26 (B2). The dihedral angle amounts to 61.22\u2005(3)\u00b0 and the length of the central C1B\u2014C22B bond is 1.395\u2005(5)\u2005\u00c5. Whereas the length of the twisted and elongated bond connecting the two halves of mol\u00adecules A and B  correlates very well with the calculated value of 1.408\u2005\u00c5, the calculated torsion angle of 52\u00b0 is about 10\u00b0 too small. The solid material gives a very weak single ESR signal.Benzoannulated fulvenes attract chemists because of their electronic properties  I, global. DOI: 10.1107/S2414314622001699/bt4120Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001699/bt4120Isup3.cmlSupporting information file. DOI: 2151512CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The different intra and inter\u00admolecular hydrogen-bonding inter\u00adactions in the crystal structure of the title salt are discussed. 11H17N2O+\u00b7C7H3N2O7\u2212, exhibits secondary nitro\u00adgen atoms (N\u2014H) in the 2-meth\u00adoxy\u00adphenyl\u00adpiperazine (2MeOPP) cation, which is protonated with a phenolic hydrogen atom of 3,5-di\u00adnitro\u00adsalicylic acid (DNSA). One of the oxygen atoms of the nitro group in the 3,5-di\u00adnitro\u00adsalicylate anion is disordered over two orientations with occupancy factors of 0.65\u2005(7) and 0.35\u2005(7) . The 2-meth\u00ad\u00adoxy\u00adphenyl\u00adpiperazinium cation and 3,5-di\u00adnitro\u00adsalicylate anion are linked in the asymmetric unit by a bifurcated N\u2014H\u22efO hydrogen bond, which formed is between the H atom in the protonated piperazinium unit of the cation and the carb\u00adoxy\u00adlic acid group in the anion. The piperazine ring adopts a chair conformation. The crystal structure features N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds inter\u00adactions, which lead to the formation of a sandwich-like arrangement. Hirshfeld surface analysis was used to determine the relative contributions of various inter\u00admolecular inter\u00adactions, indicating that that H\u22efO/O\u22efH (38. 3%) and H\u22efH (31. 8%) contacts are the major contributors.The title salt , C Piperazine and substituted piperazine derivatives are often used as inter\u00admediates for a wide range of pharmaceuticals, polymers, dyes, corrosion inhibitors and surfactants. In particular, (2-meth\u00adoxy\u00adphen\u00adyl)piperazine derivatives are used as 5-HT1A receptor ligands with reduced \u03b11-adrenergic activity -tartaric acid] salts and their supra\u00admolecular features have been reported piperazine is a substituted cyclo aliphatic amine with two nitro\u00adgen atoms at opposite positions of the six-membered ring. A substituent 2-meth\u00adoxy\u00adphenyl group is attached to one of the nitro\u00adgen atoms while the other has one attached hydrogen atom , 3,5-di\u00adnitro-2-oxidobenzoate and piperazine, we have now investigated the crystal structure of 1-(2-meth\u00adoxy\u00adphen\u00adyl) piperazinium 3,5-dinitro\u00adsalicylate (I)2.P\u012b with the asymmetric unit comprising one 2-meth\u00adoxy\u00adphenyl\u00adpiperazinium (2MeOPP)1+ cation and one 3,5-di\u00adnitro\u00adsalicylate (DNSA)1\u2212 anion \u2005\u00c5, \u03b8 = 176.3\u2005(3)\u00b0, \u03c6 = 338\u2005(4)\u00b0. One of the oxygen atoms of the nitro group (atom O4) in the 3,5-di\u00adnitro\u00adsalicylate anion is disordered over two orientations with occupancy factors of 0.65\u2005(7) and 0.35\u2005(7). Both nitro groups, the phen\u00adoxy\u00adlate oxygen atom and a carb\u00adoxy\u00adlic acid group in the anion are coplanar with an r.m.s. deviation of 0.0074\u2005\u00c5. A bifurcated inter\u00admolecular N\u2014H\u22efO hydrogen bond [N3\u2014H3A\u22efO5 = 2.936\u2005(3)\u2005\u00c5 and N3\u2014H3A\u22efO6 = 3.153\u2005(3)\u2005\u00c5] links the cation and anion in the asymmetric unit.The title salt crystallizes in the triclinic space group on Fig.\u00a01. The pipK\u03b1 COOH = 2.2) is easier than that of the phenolic \u2013OH group (pK\u03b1 OH = 6.8). 62 carboxyl\u00adate moiety structures (COO\u2212) and 70 phenolate anion structures (O\u2212) were found in a search of the Cambridge Structural Database \u2005\u00c5, which also indicates that the strong intra\u00admolecular hydrogen bond between the O6 and O7 atoms. Similar types of intra\u00admolecular hydrogen bonds were observed in salicylic acid with a distance of 2.62\u2005\u00c5  inter\u00adaction, which links two neighbouring cations and anions into a centrosymmetric tetra\u00admeric architecture, which is further stabilized by the C14\u2014H14\u22efO5v inter\u00adaction [3.481\u2005(3)\u2005\u00c5] and yields a macrocyclic ring structure with an ii inter\u00adaction [3.581\u2005(3)\u2005\u00c5], which links two neighbouring (DNSA)1\u2212 units with an 1\u2212 units are further linked through the previously mentioned bifurcated N3\u2014H3A\u22ef inter\u00adaction and the N3\u2014H3B\u22efO7i [2.787\u2005(3)\u2005\u00c5], C10\u2014H10A\u22efO4A [3.118\u2005(10)\u2005\u00c5] inter\u00adactions into a layered structure propagating parallel to the b axis , and N3\u2014H3B\u22efO7], the N3\u2014H3B\u22efO7 inter\u00adaction is stronger [D\u22efA = 2.787\u2005(3)\u2005\u00c5] than the other two, which is due to the fact that two charged components are involved in this inter\u00adaction, i.e. the phenolate O7 atom in DNSA\u22121 and the protonated N3\u2014H3B unit in 2MeOPP+1. All of the above inter\u00adactions facilitate the arrangement of the DNSA1\u2212 ions in a layered mol\u00adecular structure. The top and bottom sides of the DNSA1\u2212 layers are stabilized by the two adjacent cationic layers. As a result, a sandwich-like arrangement is observed. Briefly, the layered DNSA1\u2212 units form the core with the top and bottom sides of the cation layers arranged facing. An overall packing diagram is shown Fig.\u00a06The oxygen atoms in both nitro groups (O1\u2013O4), the carb\u00adoxy\u00adlic acid group (O5 and O6) and a phenolate moiety (O7) in the DNSA anion all act as acceptors for various inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions, except for atom O4 Table\u00a01. In the if Fig.\u00a03. Atom O1if Fig.\u00a04. Neighbois Fig.\u00a05. Of the 4.Crystal Explorer 17.5  are shown in Fig.\u00a07A, O7, O6, H10B and H3B suggest that these atoms participate in hydrogen-bonding inter\u00adactions (see Table\u00a01de + di = 1.8\u2005\u00c5] make the most significant contribution (38.3%), followed by H\u22efH contacts [symmetrical blunt spikes at de + di = 2.4\u2005\u00c5], which contribute 31.8%, while C\u22efH, N\u22efH, C\u22efO, O\u22efN, C\u22efN and C\u22efC contacts contribute 11.6%, 1.7%, 6.7%, 2.7%, 1.9%, 0.5% and 2.8%, respectively. Other significant peaks for various non-covalent contacts are indicated in the FP plot piperazine  and 3,5-di\u00adnitro\u00adsalicylic acid  in an equimolar ratio. The stoichiometrically (1\u2005mmol) weighed starting materials were completely dissolved in 50\u2005mL of methanol at room temperature and stirred continuously for 3\u2005h. The homogeneous solution was filtered using Whatmann filter paper and placed in a dust-free atmosphere, and allowed to evaporate slowly at room temperature. A suitable single crystal was harvested after a growth period of 25 days.7.Uiso(H) = 1.2Ueq(C)].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022006831/ex2058sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 2183987CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds form a three-dimensional network in the crystal, connecting mol\u00adecules through the O atoms of solvent mol\u00adecules. 16H11BrN6O\u00b72C2H6OS, the 1,2,3,7-tetra\u00adhydro\u00adimid\u00adazopyridine ring system and the oxindole moiety are both nearly planar  and their planes form a dihedral angle of 86.04\u2005(5)\u00b0 with each other. Inter\u00admolecular N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds link mol\u00adecules in the crystal through the O atoms of the solvent mol\u00adecules, generating a three-dimensional network. A Hirshfeld surface analysis was performed to further analyse the inter\u00admolecular inter\u00adactions.In the title compound, C These ring systems make a dihedral angle of 86.04\u2005(5)\u00b0 with each other. The cyano (\u2013C\u2261N) and amine (NH2) groups form an inter\u00admolecular hydrogen bond with one dimethyl sulfoxide (DMSO) group, giving an S(10) motif  (see Scheme3.A\u2014N1 bond (which has some multiple-bond character) acts as an electron donor to Br1 in a kind of \u2018halogen bond\u2019, with a Br1\u22efC8A distance of 3.284\u2005(2)\u2005\u00c5.In the crystal, mol\u00adecules are linked through the O atoms of the DMSO solvent mol\u00adecules by inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds which, together with C\u2014H\u22efN hydrogen bonds, form a three-dimensional (3D) network Table\u00a01. The \u03c0-cCrystalExplorer  plotted over the range from \u22120.6206 to 1.3180 a.u. The inter\u00adactions given in Table\u00a01The Hirshfeld surfaces were calculated and the two-dimensional (2D) fingerprint plots generated using a), and those delineated into H\u22efH, N\u22efH/H\u22efN, O\u22efH/H\u22efO, C\u22efH/H\u22efC and Br\u22efH/H\u22efBr contacts are shown in Figs.\u00a04b)\u2013(f). The percentage contributions to the Hirshfeld surfaces from the various inter\u00adatomic contacts are as follows: H\u22efH , N\u22efH/H\u22efN , O\u22efH/H\u22efO , C\u22efH/H\u22efC  and Br\u22efH/H\u22efBr . Other minor contributions to the Hirshfeld surface are from Br\u22efC/C\u22efBr (3.9%), Br\u22efN/N\u22efBr (2.0%), C\u22efC (1.5%), S\u22efC/C\u22efS (0.8%), S\u22efH/H\u22efS (0.6%), S\u22efN/N\u22efS (0.4%), O\u22efN/N\u22efO (0.4%) and Br\u22efO/O\u22efBr (0.3%).The overall 2D fingerprint plot for (1) is given in Fig.\u00a044.et al., 2016H-indol-2-one unit of (1) gave 87 hits. The three compounds most resembling (1) are (I)   , N\u2014H\u22efO hydrogen bonds lead to the formation of chains along the c-axis direction. Within the chains there are further N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds enclosing via N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds involving the dimethyl sulfoxide solvent mol\u00adecule which acts as both an acceptor and a donor.In the crystal of (II), the asymmetric unit contains two independent mol\u00adecules (A and B) having similar conformations. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds, forming chains along the a axis which enclose In (III), two intra\u00admolecular N\u2014H\u22efO hydrogen bonds are formed, each closing an S(6) loop. In the crystal, strong N\u2014H\u22efO hydrogen bonds lead to the formation of zigzag chains along the c axis. These are consolidated in the 3D crystal packing by weak N\u2014H\u22efO hydrogen bonding, as well as by C\u2014H\u22efO, C\u2014H\u22efBr and C\u2014H\u22ef\u03c0 inter\u00adactions.In  solution . Single crystals of (1) were grown from DMSO solution.To a solution of 2-(5-bromo-2-oxoindolin-3-yl\u00adidene)malono\u00adnitrile , which was previously prepared by a known procedure : \u03b4 3.50 , 6.61 , 6.78 , 7.35 , 7.37 , 7.73 , 10.44 . 13C NMR : \u03b4 42.46 (CH2N), 45.15 (CH2N), 51.24 (Cquat), 51.71 (=Cquat), 54.69 (=Cquat), 112.02 (CHarom), 114.43 (Br\u2014Carom), 119.63 (CN), 120.15 (CN), 128.02 (CHarom), 131.90 (CHarom), 137.83 (Carom), 140.80 (Carom), 152.19 (=Cquat), 154.76 (=Cquat), 179.67 (O=C).6.Uiso(H)\u00a0= 1.2Ueq(N), and C\u2014H\u00a0= 0.95\u20130.99\u2005\u00c5 with Uiso(H)\u00a0= 1.2 or 1.5Ueq(C). Both DMSO solvent mol\u00adecules are disordered over two positions, with final occupancies of 0.90:0.10 for the first and 0.95:0.05 for the second mol\u00adecule. In the first disordered DMSO molecule, the C17B and C18B atoms of the minor component were refined isotropically. The disordered atoms O2A/O2B, O3A/O3B, C19A/C19B and C20A/C20B were refined with anisotropic displacement parameters, constrained to be the same for both components. The S\u2014C and S\u2014O bond lengths in both disordered DMSO mol\u00adecules were restrained to similarity.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022004741/zv2013sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022004741/zv2013Isup2.hklStructure factors: contains datablock(s) I. DOI: 2170241CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The correct data result is \u2018IBL clear presentation time (23.59 \u00b1\u20094.47 vs. 1026.80 \u00b1\u2009318.34 s) (p <\u20090.001)\u2019 instead of \u2018IBL clear presentation time (23.6 \u00b1\u20094.4 vs. 23.6 \u00b1\u20094.4 s) (p <\u20090.01)\u2019. The results section should read as below:Results: An IBL was visible in 98% of patients in the ICGF\u2010based group, even with low doses of ICG. The ICGF\u2010based group was significantly associated with a shorter IBL clear presentation time (23.59\u2009\u00b1\u20094.47\u2009vs.\u20091026.80\u2009\u00b1\u2009318.34 s) (p\u2009<\u20090.001) and operative time (89.3\u2009\u00b1\u200931.6 vs. 112.9\u2009\u00b1\u200933.3\u2009min) (p\u2009<\u20090.01) compared to the MID group. The incidence of postoperative prolonged air leaks was higher in the MID group than in the ICGF\u2010based group . There were no significant differences in bleeding volume, chest tube duration, postoperative hospital stays, surgical margin width, and other postoperative complications.The authors apologize for the error and any inconvenience it may have caused."}
{"text": "The title compound features a B\u2014O\u2014B bond angle of 132.75\u2005(13)\u00b0. 40H36B2N4O5, the B\u2014O\u2014B bond angle is 132.75\u2005(13) and the dihedral angle between the benzodiazborole rings is 73.02\u2005(5)\u00b0. In the crystal, weak C\u2014H\u22efO inter\u00adactions link the mol\u00adecules.In the title compound, C Additionally, it is likely that a p-type electronic inter\u00adaction exists between O1 and the adjacent boron atoms (B1A and B1B) that would serve to open up the bond angle substanti\u00adally beyond the textbook angle of 109.5\u00b0 for an O atom bearing two lone pairs of electrons. As a result of steric encumbrance, the B1A and B1B benzodi\u00adaza\u00adborole rings are angled away from one another to a near perpendicular orientation, with a plane-to-plane tilt of 73.02\u2005(5)\u00b0. The dihedral angles between the B1A benzodi\u00adaza\u00adborole ring system and its pendant p-meth\u00adoxy\u00adbenzene rings are 80.49\u2005(6) and 49.84\u2005(7)\u00b0 for the C7A and C14A rings, respectively. Comparable data for the B1B ring system and its pendant C7B and C14B rings are 78.32\u2005(6) and 65.96\u2005(7)\u00b0, respectively. The C atoms of the meth\u00adoxy groups are all close to their respective ring planes: C13A [deviation = 0.333\u2005(2)\u2005\u00c5]; C20A [0.254\u2005(2)\u2005\u00c5]; C13B [\u22120.040 (2\u2005\u00c5)]; C20B [0.193\u2005(2)\u2005\u00c5].The B1In the crystal, weak C\u2014H\u22efO inter\u00adactions Table\u00a01 link theN1,N2-bis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)benzene-1,2-di\u00adamine , was obtained in 87% yield. The single-crystal X-ray structure of the di\u00adaza\u00adborole chloride has been deposited with the Cambridge Structural Database . After stirring overnight, a white precipitate of the tri\u00adethyl\u00adammonium chloride formed that was then filtered and discarded. The filtrate was dried under reduced pressure to give the crude product. The solid was extracted in a fritted glass filter with a minimum volume of benzene, and the filtrate was evaporated under reduced pressure to give the title compound in 85% yield.Under an anhydrous nitro\u00adgen atmosphere, a solution was prepared that contained 3.0\u2005mmol of (II), four equivalents of tri\u00adethyl\u00adamine, and \u223c200\u2005ml of 1,2-di\u00admeth\u00adoxy\u00adethane. This solution was then treated with half an equivalent of water  global, I. DOI: 10.1107/S2414314620012481/hb4361Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620012481/hb4361Isup4.cmlSupporting information file. DOI: 2031384CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit is composed of half a binuclear silver complex located about a center of symmetry, a potassium cation and 2.6 disordered water mol\u00adecules. The whole binuclear silver complex is generated by inversion symmetry with the pyrazine ring being located about an inversion centre. The ligand coordinates in a bis-tetra\u00addentate manner. The binuclear silver complex anions are linked via bridging Ag\u22efS\u22efAg zigzag bonds, forming a network lying parallel to the bc plane. The networks are linked by Ocarboxyl\u00adate\u22efK+\u22efOcarboxyl\u00adate bridging bonds to form a framework. The disordered water mol\u00adecules are present near to the K+ cations.The reaction of AgNO In I this value is 2.550\u2005(5)\u2005\u00c5. For Ag\u2014Ocarboxyl\u00adate there were over 2,800 hits with the bond lengths varying from 1.967 to 3.089\u2005\u00c5 . In I the Ag\u2014Ocarboxyl\u00adate bond lengths are almost equal; 2.470\u2005(5) and 2.466\u2005(6)\u2005\u00c5. Finally for the Ag\u2014S(CH2)2\u2014 bond-length type there were over 1,000 hits with the bond length varying from 2.361 to 3.583\u2005\u00c5 . In I the Ag\u2014S(CH2)2\u2013 bond lengths vary from 2.604\u2005(2) to 2.926\u2005(2)\u2005\u00c5, both values involve the bridging atom S1, while distance Ag1\u2014S2ii is 2.824\u2005(2)\u2005\u00c5  \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].The three chelate rings are far from flat, as indicated by the torsion angles given in Table\u00a01K+\u22efOcarboxyl\u00adate bonds lengths vary from 2.608\u2005(6) to 2.751\u2005(6)\u2005\u00c5, and there is one weak contact K1\u22efO1 at 3.289\u2005(6)\u2005\u00c5 potassium] potassium]  to 2.8668\u2005(13)\u2005\u00c5 in UBUPAK and from 2.8197\u2005(14) to 3.0449\u2005(15)\u2005\u00c5 in MUMPIW. In UBUPAK the K+ cation has a coordination number of 8 (KO8) and a distorted dodeca\u00adhedral geometry, while in MUMPIW the K+ ion has a coordination number of 7 (KO6N) and has an edge-sharing penta\u00adgonal anti\u00adprism geometry. In I, the stronger K\u22efO bond lengths are shorter and, owing to the presence of the disordered water mol\u00adecules, it is not clear what the K+ ion coordination number or geometry are.Selected bond lengths and bond angles involving atom K1 are also given in Table\u00a01\u2005\u00c5 Fig.\u00a03. A searcI, the networks of the binuclear silver complex anions are linked by the bridging Ocarboxyl\u00adate\u22efK+\u22efOcarboxyl\u00adate bonds to form a framework ] tetra\u00adkis\u00ad(sulfanedi\u00adyl)}tetra\u00adacetato)}-bis\u00ad[silver(I)]-bis\u00ad[potassium] 5.2(hydrate)} (I):3  and 4L1H  were mixed in 20\u2005ml of a 1M potassium acetate buffer solution. The mixture was left at 323\u2005K under stirring and nitro\u00adgen conditions for 1\u2005h. The mixture was then filtered and left to evaporate in air for six weeks, yielding yellow rod-like crystals of compound I (m.p. 553\u2005K decomposition).AgNO16H16Ag2N2O8S4, K2, 5.2(H2O), Mw = 880.175\u2005g\u2005mol\u22121: Calculated (%): C 21.88, H 2.99, N 3.18. Found (%): C 23.03, H 2.91, N 3.03. The small deviation is probably due to the loss of water mol\u00adecules of crystallization.Analysis for CESI\u2013MS: unstable under mass spectroscopy experimental conditions.\u22121) \u03bd: 3401(s), 2938(m), 1599(s), 1385(s), 1223(m).IR . It was not possible to locate the H atoms of the disordered water mol\u00adecules of crystallization. The residual electron density peaks of 1.14 and \u22121.10 e\u00c53 are at distances of 0.96 and 0.91\u2005\u00c5, respectively, from atom Ag1.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622000773/im4015sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2414314622000773/im4015Isup2.hklStructure factors: contains datablock(s) I. DOI: 2143798CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2010hydroxyalkyl phenylbenzoisoquinolindiones (PBIQs) has been developed. Incubation of plant material of Xiphidium caeruleum with hydroxylamines of various chain lengths  resulted in 11 new 5\u2010hydroxy\u2010 and 5\u2010methoxy PBIQs with different N\u2010hydroxyalkyl side chain lengths. The antiproliferative effect and the cytotoxicity against HUVEC, K\u2010562, and HeLa cell lines of 26 previously reported PBIQs and the 11 newly synthesized N\u2010hydroxyalkyl PBIQs was determined for the first time. The results revealed that introducing long\u2010chain N\u2010aliphatic amine moieties improved the antiproliferative effect and cytotoxicity of PBIQs when compared to derivatives with N\u2010amino acids as side chains.A precursor\u2010directed approach to access  Direct incubation ofXiphidium caeruleumplant material with \u03c9\u2010amino alcohols followed by extraction and purification results in N\u2010hydroxyalkyl phenylbenzoisoquinolindiones (PBIQs). Long\u2010chain derivatives show good antiproliferative effects together with low cytotoxicity. H\u2010benzo[de]isoquinoline\u20101,3(2H)\u2010diones,Xiphidium caeruleumLachnanthes tinctoriaWachendorfia thyrsiflora.Isoquinolines, which represent one of the largest groups of naturally occurring alkaloids, show a wide spectrum of biological activities.X. caeruleum were derived from a series of enzymatic hydrolyses and spontaneous conversions from three native phenylbenzoisochromenone (PBIC) glucosides, 1\u20133, and plant proteinogenic amino acids  (see Supporting Information Table ST1).isoquinoline\u20101,6\u2010dione (31): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 7.5\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 240, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 348.1237 [M+H]+ .2\u2010(4\u2032\u2032\u2010Hydroxybutyl)\u20105\u2010hydroxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (32): Orange powder. HPLC\u2010PDA\u2010ESIMS gradient 2, tR 9.4\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 238, 322, 442\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 362.1394 [M+H]+ .2\u2010(4\u2032\u2032\u2010Hydroxybutyl)\u20105\u2010methoxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (33): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 8.4\u2005min; UV (MeCN\u2010H2O) \u03bbmax 196, 238, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 376.1541 [M+H]+ .2\u2010(6\u2032\u2032\u2010Hydroxyhexyl)\u20105\u2010hydroxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (34): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 12.3\u2005min; UV (MeCN\u2010H2O) \u03bbmax 224, 324, 444\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 390.1708 [M+H]+ .2\u2010(6\u2032\u2032\u2010Hydroxyhexyl)\u20105\u2010methoxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (35): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 10.9\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 238, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 404.1863 [M+H]+ .2\u2010(8\u2032\u2032\u2010Hydroxyoctyl)\u20105\u2010hydroxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (36): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 15.3\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 218, 238, 324, 444\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST5; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 418.2030 [M+H]+ .2\u2010(8\u2032\u2032\u2010Hydroxyoctyl)\u20105\u2010methoxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (37): Orange powder. HPLC\u2010DAD\u2010ESIMS gradient 2, tR 14.1\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 238, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST6; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 432.2171 [M+H]+ .2\u2010(10\u2032\u2032\u2010Hydroxydecyl)\u20105\u2010hydroxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (38): Orange powder. HPLC\u2010PDA\u2010HRESIMS gradient 2, tR 18.7\u2005min; UV (MeCN\u2010H2O) \u03bbmax 208, 234, 324, 444\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST6; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 446.2326 [M+H]+ .2\u2010(10\u2032\u2032\u2010Hydroxydecyl)\u20105\u2010methoxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (39): Orange powder. HPLC\u2010DAD\u2010ESIMS gradient 2, tR 17.6\u2005min; UV (MeCN\u2010H2O) \u03bbmax 204, 238, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST6; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 460.2482 [M+H]+ .2\u2010(12\u2032\u2032\u2010Hydroxydodecyl)\u20105\u2010hydroxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (40): Orange powder. HPLC\u2010DAD\u2010ESIMS gradient 2, tR 22.3\u2005min; UV (MeCN\u2010H2O) \u03bbmax 206, 242, 324, 444\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST6; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 474.2649 [M+H]+ .2\u2010(12\u2032\u2032\u2010Hydroxydodecyl)\u20105\u2010methoxy\u20107\u2010phenyl\u20102H\u2010benzo[de]isoquinoline\u20101,6\u2010dione (41): Orange powder. HPLC\u2010DAD\u2010ESIMS gradient 2, tR 21.2\u2005min; UV (MeCN\u2010H2O) \u03bbmax 204, 236, 320, 434\u2005nm; 1H\u2005NMR data, see Supporting Information Table ST6; 13C\u2005NMR data, see Supporting Information Table ST7; HRESIMS m/z 488.2806 [M+H]+ .30\u201341 were dissolved in dimethylsulfoxide . Five replicates were investigated for each assay. Cell toxicity assays were conducted using a HeLa cell line (DSM ACC 57), and antiproliferative activity was assayed using HUVEC (ATCC CRL\u20101730) and K\u2010562\u2005cell lines (DSM ACC 10). The test substances were dissolved in DMSO before being diluted in the respective cell culture medium to concentrations of between 1 and 100\u2005\u03bcg\u2009mL\u22121. The adherent cells were harvested in the logarithmic growth phase after soft trypsinization, using 0.25\u2009% trypsin in phosphate\u2010buffered saline containing 0.02\u2009%\u2009ethylenediaminetetraacetic acid. For each experiment, approximately 10,000 cells were seeded with 0.1\u2005mL culture medium per well of a 96\u2010well microplate. HeLa cells were pre\u2010incubated for 48\u2005h prior to the application of the test compounds to give subconfluent monolayers. Incubation was then conducted in a humidified atmosphere at 37\u2009\u00b0C and 5\u2009% CO2. In the case of K\u2010562 cells, the antiproliferative effect was determined using the CellTiter\u2010Blue1 assay.n HCl from the wells. The optical densities were measured at 660\u2005nm in a SUNRISE microplate reader .To determine cell toxicity and antiproliferative activity, PBIQs PLUS  was performed as described earlier.Cell Death Detection ELISAAn overview of the compounds used for the bioassays together with their analytical data (MS and NMR) is provided in the Supporting Information. Furthermore, the results of the bioassays in graphical form and microscopic images of cells treated with PBIQs are given.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The chains are connected by C\u2014F\u22ef\u03c0(ring), C=O\u22ef\u03c0(ring) and slipped \u03c0-stacking inter\u00adactions. A Hirshfeld surface analysis of these inter\u00adactions was performed.The asymmetric unit consists of two independent mol\u00adecules differing in the orientation of the azido group. Each mol\u00adecule forms N\u2014H\u22efO hydrogen-bonded chains extending along the  8H7FN4O, consists of two independent mol\u00adecules differing in the orientation of the azido group. Each mol\u00adecule forms N\u2014H\u22efO hydrogen-bonded chains along along the c-axis direction with its symmetry-related counterparts and the chains are connected by C\u2014F\u22ef\u03c0(ring), C=O\u22ef\u03c0(ring) and slipped \u03c0-stacking inter\u00adactions. A Hirshfeld surface analysis of these inter\u00adactions was performed.The asymmetric unit of the title compound, C They have found valuable applications in medicinal chemistry \u2005\u00c5, C15\u22efCg1 = 3.902\u2005(2)\u2005\u00c5, C15=O2\u22efCg1 = 80.88\u2005(13)\u00b0] as shown in Fig.\u00a01p-tolyl analog  x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0A\u22efO2i hydrogen bonds form parallel chains for the second independent mol\u00adecule  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (iii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a02] inter\u00adactions as well as by the C15=O2\u22efCg1 inter\u00adaction noted above and weak, slipped \u03c0-stacking between centrosymmetrically related C1\u2013C6 benzene rings  , H\u22efH (13.5%), O\u22efH/H\u22efO (12.2%), C\u22efH/H\u22efC (11.9%) and F\u22efH/H\u22efF (9.7%), respectively. The two spikes in Fig.\u00a06d primarily represent the N\u2014H\u22efO hydrogen bonds but their breadth at longer values of di + de than at the tips indicate the contributions from C\u2014H\u22efO hydrogen bonds. Fig.\u00a07a showing all inter\u00admolecular inter\u00adactions and Fig.\u00a07b\u20137f those delineated into N\u22efH/H\u22efN (28.8%), H\u22efH (18.2%), C\u22efH/H\u22efC (12.6%), F\u22efH/H\u22efF (12.6%) and O\u22efH/H\u22efO (11.6%), respectively. Although the ordering of inter\u00adactions based on their percentage of the total is not the same as in the other mol\u00adecule, the percentages are not greatly different between the two and the corresponding plots are very similar type by type.A Hirshfeld surface analysis was performed with 6.N-(4-fluoro\u00adphen\u00adyl)acetamide (0.011\u2005mol), and sodium azide (0.015\u2005mol) were dissolved in a mixture of ethanol/water (70:30) and refluxed for 24\u2005h at 353\u2005K. After completion of the reaction , the 2-azido-N-(4-fluoro\u00adphen\u00adyl)acetamide that precipitated was filtered off and washed with cold water. A portion of the product was dissolved in hot ethanol, the solution was filtered, and the filtrate was left undisturbed for 7 days to form colorless, thick plate-like crystals.2-Chloro-\u22121) 3254 \u03c5 (N\u2014H amide), 1027 \u03c5 (N\u2014C amide), 1660 \u03c5 (C=O amide), 3073 \u03c5(C\u2014Harom), 1175 \u03c5(C\u2014N), 2961 \u03c5, 2109 \u03c5 (N3), 1H NMR (DMSO\u2013d6) \u03b4 ppm: 4.02 , 6.93\u20137.11 , 10.05 , 13C NMR (DMSO\u2013d6) \u03b4 ppm: 51.18 (CH2), 131.47 (Carom\u2014N), 113.90\u2013120.86 (Carom); 165.71 (C=O); HRMS (ESI\u2013MS) (m/z) calculated for C8H7FN4O 194.18; found 194.1165.Yield 69%, m.p. 358\u2013360K, FT\u2013IR  global, I. DOI: 10.1107/S2056989022006764/vm2266Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022006764/vm2266Isup3.cmlSupporting information file. DOI: 2183049CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ability of 4-[(benzyl\u00adamino)\u00adcarbon\u00adyl]-1-methyl\u00adpyridinium bromide salt to form hydrates was studied. Hirshfeld surfaces analysis was performed for identification of inter\u00admolecular inter\u00adactions. 14H15N2O+\u00b7Br\u2212\u00b70.5H2O, was studied by single-crystal and powder X-ray diffraction methods. In the asymmetric unit, two organic cations of similar conformation, two bromide anions and one water mol\u00adecule are present. In the crystal, N\u2014H\u22efBr hydrogen bonds link the cations and anions. The formation of a set of inter\u00admolecular C\u2014H\u22efBr and C\u2014H\u22ef\u03c0 inter\u00adactions result in double chains extending parallel to [011]. A Hirshfeld surface analysis showed high contributions of H\u22efH and C\u22efH/H\u22efC short contacts to the total Hirshfeld surfaces of the cations.The hemihydrate of 4-[(benzyl\u00adamino)\u00adcarbon\u00adyl]-1-methyl\u00adpyridinium bromide, C Polymorphic screening for this salt resulted in the crystallization of a hemihydrate. In this communication we present the mol\u00adecular and crystal structures of 4-[(benzyl\u00adamino)\u00adcarbon\u00adyl]-1-methyl\u00adpyridinium bromide hemihydrate, (C2.A and B), two bromide anions (A and B) and one water mol\u00adecule . The contribution of C\u22efH/H\u22efC short contacts is also significant . The Br\u22efH/H\u22efBr and O\u22efH/H\u22efO inter\u00adactions contribute to the total Hirshfeld surface in the same way .Inter\u00admolecular inter\u00adactions were analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots by using rm Fig.\u00a04. The redrm Fig.\u00a04. The mairm Fig.\u00a04g,h. Thent Fig.\u00a05i,j. The5.et al., 2016et al., 2017sp3 and Csp3\u2014Car\u00adyl bonds.A search of the Cambridge Structural Database . A Rietveld refinement \u00adcarbon\u00adyl]-1-methyl\u00adpyridinium iodide , silver bromide  and 700\u2005ml of water were loaded into a glass flask. The mixture was stirred for 72\u2005h, and the resulting precipitate was filtered off. The solvent was evaporated under reduced pressure. To the precipitate were added 300\u2005ml of aceto\u00adnitrile and refluxed for 2\u2005h. The reaction then was spontaneously cooled to a temperature of 303\u2005K and the precipitate filtered off and rinsed on the filter with 50\u2005ml of cooled aceto\u00adnitrile. The product was dried at 313\u2005K for 12\u2005h. Yield: 14\u2005g of 4-[(benz\u00adyl\u00adamino)\u00adcarbon\u00adyl]-1-methyl\u00adpyridinium bromide (28%); colourless crystals.8.Uiso(H) = 1.5Ueq for methyl groups and with Car\u2014H = 0.93\u2005\u00c5, Csp2\u2014H = 0.97\u2005\u00c5, Uiso(H) = 1.2Ueq for all other hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989022003784/wm5623sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022003784/wm5623Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022003784/wm5623Isup3.cmlSupporting information file. DOI: 2164796CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The \u2018tromancenium-8-carb\u00adoxy\u00adlic acid\u2019 entity with a hexa\u00adfluorido\u00adphosphate counter-ion represents a rare case of a cationic carb\u00adoxy\u00adlic acid. 7H7)(C6H5O2)]PF6 or [(Cht)Mn(Cp\u2019CO2H)]PF6, with Cht = cyclo\u00adhepta\u00adtrienyl and Cp\u2019 = C5H4, is an air-stable, purple, heteroleptic, cationic sandwich complex with manganese in oxidation state +I and \u03c0-coordinating cyclo\u00adhepta\u00adtrienyl and cyclo\u00adpenta\u00addienyl ligands. The latter ligand carries the carb\u00adoxy\u00adlic acid functionality. This \u2018tromancenium-8-carb\u00adoxy\u00adlic acid\u2019 with hexa\u00adfluorido\u00adphosphate as counter-ion represents a rare case of a cationic carb\u00adoxy\u00adlic acid. Structurally, this organometallic carb\u00adoxy\u00adlic acid displays the common motif of planar Osp2\u22efH\u2014Osp3/Osp3\u2014H\u22efOsp2 hydrogen-bonded carb\u00adoxy\u00adlic acid dimers with anti-oriented metallocenyl moieties, the cationic charge of which is balanced by octa\u00adhedrally shaped hexa\u00adfluorido\u00adphosphate anions. Positional disorder is observed in the cyclo\u00adhepta\u00adtrienyl ring and the PF6\u2212 anion.The title compound, [Mn(C As a result of the instability against nucleophiles of the parent compound tromancenium hexa\u00adfluorido\u00adphosphate \u2005\u00c5 is typical for a carbon\u2013carbon single bond. The C13\u2014O1 bond length of 1.205\u2005(10)\u2005\u00c5 is shorter than the C13\u2014O2 bond length of 1.303\u2005(10)\u2005\u00c5, which is coherent with the expectations.The mol\u00adecular entities of the title compound are shown in Fig.\u00a01y Table\u00a01, with tret al., 2014Cht/Cp bond lengths in the title compound. The C=O bond in cobaltocenium carb\u00adoxy\u00adlic acid is of the same length as the C\u2014O bond, due to disorder.The comparable organometallic compound cobaltocenium carb\u00adoxy\u00adlic acid hexa\u00adfluorido\u00adphosphate (Vanicek 6\u2212), which fill the space within the packing of the dimers  were added. The solvents were removed on a rotary evaporator and the crude material dried in vacuo. The product was dissolved in aceto\u00adnitrile and filtered through a folded paper filter. Aceto\u00adnitrile was removed on a rotary evaporator and the product was dried in vacuo giving pure 8-tromancenium carb\u00adoxy\u00adlic acid hexa\u00adfluorido\u00adphosphate in 92% yield . Single crystals were obtained by diffusion crystallization in aceto\u00adnitrile out of diethyl ether at room temperature.A round-bottom flask was charged with 0.0563\u2005g of 8-carbo\u00admeth\u00adoxy\u00adtromancenium hexa\u00adfluorido\u00adphosphate  \u03b4 = 4.89 , 5.21 , 6.93 ; signal of CO2H not observed due to rapid exchange. 13C NMR  \u03b4 = 78.6 (ipso-carbon of Cp), 79.4 (C10/C11 of Cp), 80.3 (C9/C12 of Cp), 99.0 (C1\u20137 of Cht), 156.4 (CO2H). 55Mn NMR  \u03b4 = 529. IR : 3000 (\u03bdO\u2014H + \u03bdC\u2014H), 1696 (\u03bdC=O), 1489, 1448, 1413, 1375 (\u03bdC\u2014OH + \u03bdC=C), 815 (\u03bdP\u2014F), 749 ), 600, 554 , 467, 437 (\u03bdMn). HRMS  255.0211 ([M\u00a0\u2212\u00a0PF6]+), calculated for C13H12O2Mn: 255.0212. UV\u2013vis  \u03bbmax1 = 283, \u03bbmax2 = 559. Cyclic voltammetry (CV): \u0394E1/2 (Mn+/Mn2+) = 1.00\u2005V versus ferrocene/ferrocenium+ (irreversible).Properties: m.p.: 395.8\u2005K dec. d = 0.83\u2005\u00c5). A positional disorder in a ratio of 1:1 for the carbon atoms and attached hydrogen atoms of the seven-membered ring: C1\u2013C7: C1A\u2013C7A was considered; the corresponding carbon atoms were refined with isotropic displacement parameters. A further positional disorder of all fluorine atoms of the PF6\u2212 anion was refined in ratio 45:55 for F1\u2013F6:F1A\u2014F6A with anisotropic displacement parameters. In an alternative model, the crystal structure was also refined in the non-centrosymmetric space group P1 with a new data set, for which TWINABS  in the P1 model and several remaining electron-density peaks between the carbon atoms of the two seven-membered rings clearly show that the disorder will be retained in the non-centrosymmetric space group. Hence, the latter was discarded and the centrosymmetric model used for final processing.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314623001074/wm4180sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623001074/wm4180Isup2.hklStructure factors: contains datablock(s) I. DOI: 2239883CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: \u201cAbsolute quantitation of microbes using 16S rRNA gene metabarcoding: A rapid normalization of relative abundances by quantitative PCR targeting a 16S rRNA gene spike\u2010in standard\u201d by Olivier Zemb | Caroline S. Achard | Jerome Hamelin | Marie\u2010L\u00e9a De Almeida | B\u00e9atrice Gabinaud | Laurent Cauquil | Lisanne M.G. Verschuren | Jean\u2010Jacques Godon published online on 11 January\u00a0Figure 1 of the original version of published article has been replaced. The correct figure is placed below: In the original version, in the text (section 2.3) \u201cforward and reverse primers E 5\u2032\u2010CAGATGTGAAATCATCGATCG/5\u2032\u2010CCGATTTCAATCGTACACCTG\u201d should read \u201cforward and reverse primers E 5\u2032\u2010ACGTAGAATTCCAGGTGTACGAT/5\u2032\u2010ACCTGAGCGTCAGTCTTCGT\u201d."}
{"text": "Scientific Reports 10.1038/s41598-021-82599-1, published online 04 February 2021Correction to: The original version of this Article contained an error in the Methods section, where \u201c7.8\u2009\u00d7\u2009300\u00a0mm\u201d was incorrectly given as \u201c4.6\u2009\u00d7\u2009300\u00a0mm\u201d.In the Methods section, under the subheading \u2018Size-exclusion chromatography\u2019,\u201cA SEPAX SRT SEC-1000 column (4.6\u2009\u00d7\u2009300\u00a0mm) and guard column  were used for all SEC-MALS experiments.\u201dnow reads:\u201cA SEPAX SRT SEC-1000 column (7.8 \u00d7 300 mm) and guard column  were used for all SEC-MALS experiments.\u201dThe original Article has been corrected."}
{"text": "The a new polymorph of the title compound is reported in which the C\u2014H\u22efO hydrogen bonds and \u03c0-\u03c0 stacking inter\u00adactions link mol\u00adecules into the layers in the crystal. 14H8Br3N3O2, (form-2) was obtained in the same manner as the previously reported form-1 . The structure of the new polymorph is stabilized by a C\u2014H\u22efO hydrogen bond that links mol\u00adecules into chains. These chains are linked by face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions, resulting in a layered structure. Short inter-mol\u00adecular Br\u22efO contacts and van der Waals inter\u00adactions between the layers aid in the cohesion of the crystal packing. In the previously reported form-1, C\u2014H\u22efBr inter\u00adactions connect mol\u00adecules into zigzag chains, which are linked by C\u2014Br\u22ef\u03c0 inter\u00adactions into layers, whereas the van der Waals inter\u00adactions between the layers stabilize the crystal packing of form-2. Hirshfeld mol\u00adecular surface analysis was used to compare the inter\u00admolecular inter\u00adactions of the polymorphs.A new polymorph of the title compound, C al. 2022. Acta Cr Crystal Explorer 17.5  to +1.1715 (blue) a.u. , H\u22efH (12.8%), C\u22efH/H\u22efC (11.5%) and O\u22efH/H\u22efO (10.6%) contacts are shown in Fig.\u00a06b\u2013e, while the numerical details for the shortest contacts are given in Table\u00a02viz. Br\u22efH/H\u22efBr, H\u22efH, C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts -1--2-(4-bromo\u00adphen\u00adyl)diazene unit showed that the ten closest are those of CSD refcodes HEHKEO (I)          , resulting in zigzag C(8) chains along the [100] direction. These chains are connected by C\u2014Br\u22ef\u03c0 inter\u00adactions into layers parallel to (001). van der Waals inter\u00adactions between the layers contribute to the crystal cohesion.C\u2014H\u22efBr inter\u00adactions connect the mol\u00adecules in the crystal of the form-1 polymorph of the title compound, (II) are joined into layers parallel to (011) by C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds. C\u2014Br\u22ef\u03c0 and C\u2014F\u22ef\u03c0 contacts, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions, strengthen the crystal packingThe mol\u00adecules in (III) are connected into chains running parallel to [001] by C\u2014H\u22efO hydrogen bonds. C\u2014F\u22ef\u03c0 contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions help to consolidate the crystal packing, and short Br\u22efO [2.9828\u2005(13)\u2005\u00c5] distances are also observed.The mol\u00adecules in the crystal of (IV), the mol\u00adecules are linked into inversion dimers via short halogen\u2013halogen contacts . No other directional contacts could be identified, and the shortest aromatic ring-centroid separation is greater than 5.25\u2005\u00c5.In the crystal of (V) and (VI), the mol\u00adecules are linked through weak X\u22efCl contacts [X = Cl for (V) and Br for (VI)], C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets lying parallel to (001).In the crystals of (VII), the mol\u00adecules are stacked in columns along [100] via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts.In the crystal of (VIII), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running parallel to [001]. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions.In (IX), C\u2014H\u22efN and short Cl\u22efCl contacts are observed, and in (X), C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short Cl\u22efO contacts occur.In -1-(4-bromo\u00adphen\u00adyl)-2-(3-nitro\u00adbenzyl\u00adidene)hydrazine (1\u2005mmol), tetra\u00admethyl\u00adethylenedi\u00adamine , CuCl  and CBr4 (4.5\u2005mmol). After 1\u20133\u2005h , the reaction mixture was poured into a 0.01 M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005mL). The combined organic phase was washed with water (3 \u00d7 50\u2005mL), brine (30\u2005mL), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Red solid (62%); m.p. 391\u2005K. Analysis calculated for C14H8Br3N3O2 (M = 489.95): C 34.32, H 1.65, N 8.58; found: C 34.29, H 1.66, N 8.55%. 1H NMR  \u03b4 7.90\u20137.44 . 13C NMR  \u03b4 150.88, 148.57, 148.12, 132.81, 132.47, 132.25, 130.04, 126.40, 125.30, 124.53, 123.57, 94.10. ESI-MS: m/z: 490.91 [M + H]+.This dye was synthesized according to the reported method (Akkurt 6.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022007113/yk2172sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007113/yk2172Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022007113/yk2172Isup3.cmlSupporting information file. DOI: 2189348CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Over the past 20\u00a0years, the interest in the biological chemistry of HNO has increased significantly due to the numerous beneficial pharmacological effects of its donors. Increased availability of various HNO donors was accompanied by great progress in the understanding of HNO chemistry and chemical biology. This review is focused on the chemistry of HNO, with emphasis on reaction kinetics and mechanisms in aqueous solutions.Azanone  is the protonated form of the product of one-electron reduction of nitric oxide ( Formallificance . Interesificance . This resulfide HS and azaazanone\u201d or \u201chydridooxidonitrogen\u201d (which name is based on additive nomenclature). The commonly used name is \u201cnitroxyl.\u201d It has also been used to describe azanone anion, NO\u2212 [which IUPAC recommended name is \u201coxidonitrate (1\u2212)\u201d]. The term \u201cnitroxyl\u201d may be misleading as aminoxyl radicals, of the general formula R2N-O\u2022, are known as \u201cnitroxyl radicals.\u201d Therefore, the reader must be aware that a literature search with the keyword \u201cnitroxyl\u201d may yield references to aminoxyl radicals R2N-O\u2022. In some of the scientific literature names \u201cnitroso hydrogen,\u201d \u201cmonomeric hyponitrous acid,\u201d \u201cnitrosyl hydride\u201d or \u201chydrogen oxonitrate,\u201d were also used. For the compliance with the IUPAC recommendations and to avoid ambiguity, we suggest the use of the name \u201cazanone\u201d for HNO and \u201cazanone anion\u201d for NO\u2212.Prior to describing HNO chemistry, it is important to briefly discuss the recommended and the used nomenclature. The IUPAC recommended name of HNO is \u201cN-O, the N-H bond length rN-H and the H-N-O angle \u03b8H-N-O. The qualitative discussion of the electronic structure of HNO has been given by N-O = 1.212\u00a0\u00c5, rN-H = 1.063\u00a0\u00c5, and \u03b8H-N-O = 108.6\u00b0. HNO structure and NO bond vibrational frequency \u03c5NO has been the subject of numerous theoretical studies . Deprot\u2212 a pKa value of 4.7 for HNO was reported in 1970 (Ka(1HNO/3NO\u2212) value of 11.4  is recommended. Shafirovich and Lymar have also estimated the pKa values for other HNO acid-base equilibria: pKa(1HNO/1NO\u2212) \u223c 23, pKa(3HNO/3NO\u2212) = \u22121.8  = \u22121.8 , suggest\u2022NO, due to its electronic structure, has very low value \u2014 Eea = 0.026 \u00b1 0.005\u00a0eV  = \u22120.81\u00a0V, and practically outside of the biologically compatible range (\u2022NO reduction leads to the formation of HNO. Taking into account the postulated pKa(1HNO/3NO\u2212) value of 11.4, Lymar and co-workers, estimated standard redox potential for \u2022NO/HNO redox pair to be equal to \u22120.14\u00a0V (E\u00b0(\u2022NO/HNO) = \u22120.14\u00a0V, and E\u00b0\u2019(\u2022NO/HNO) = \u22120.55\u00a0V for pH 7) (E\u00b0(\u2022NO/HNO) = 0.27\u00a0V, and E\u00b0\u2019(\u2022NO/HNO) = \u22120.14\u00a0V for pH 7, based on the computational reevaluation of HNO solvation free energy (2/O2\u2022\u2013 redox couple), would suggest the feasibility of \u2022NO reduction to HNO by a variety of cellular enzymatic redox centers. The \u2022NO/HNO interconversion under physiological conditions has been recently discussed in detail (Electron affinity of 0.005\u00a0eV . \u2022NO redle range . At physor pH 7) . Those ve energy . Such van detail , and is 2N2O2 (k1a = (8 \u00b1 3) \u00d7 106\u00a0M\u22121s\u22121) (2N2O2 have been reported with pKa (H2N2O2/HN2O2\u2212) = 7.0 and pKa (HN2O2\u2212/N2O22\u2013) = 10.9. Therefore, at physiological pH (pH > 7), H2N2O2 exists predominantly in its mono-deprotonated form (HN2O2\u2212). This form is responsible for the instability of H2N2O2 in aqueous solutions and for the formation of N2O .It should be noted, that direct experimental determination of the chemical reactivity of HNO is hampered by its rapid dimerization to hyponitrous acid H\u00a0M\u22121s\u22121) . This rain situ, e.g., with the use of radiation techniques  involving one-electron reduction of \u2022NO by solvated electrons or by hydrogen atoms (H\u2022), or photochemical techniques , including photolysis of alkaline aqueous solutions of trioxodinitrate . Below, the radiation chemistry of aqueous solutions of \u2022NO and the laser flash photolysis of aqueous solutions of N2O32\u2212 will be described, as those methods greatly contributed to our understanding of azanone chemistry and to the determination of the rate constants of the reactions involved. Further development of such methodologies for rapid in situ formation of HNO/NO\u2212and for monitoring their reactions may overcome current obstacles in the studies of HNO/NO\u2212chemistry and result in improved knowledge of the azanone chemistry and its biological fates.Due to the instability of HNO in aqueous solutions, in chemical studies on HNO reactivity it is necessary to use HNO donors, that release HNO in a controlled manner, or produce azanone \u2022NO leads to the formation of nitrite (NO2\u2212) and N2O. The primary transient reactive species produced within approximately 10\u20138\u00a0s after the exposition of water to ionizing radiation are hydroxyl radical (\u2022OH), hydrated electron (eaq\u2212), and hydrogen atom (H\u2022) [ONOO\u2212]where kvi in the presence of azanone scavenger is expressed by 2 and the scavenger studied.\u2212, or such reaction is outcompeted by the reaction between ONOO\u2212and the boronate probe; 3) the scavenger does not react with or interferes with the detection of the product of oxidation of the boronic probe; and 4) the amount of HNO released is significantly lower than the amount of the scavenger and of O2 in the solution.The rate of ArOH formation r[donor]Comparis2\u2212 was determined to be equal to (5.0 \u00b1 0.9) \u00d7 103\u00a0M\u22121s\u22121  results in the formation of molecular nitrogen (N2) and water (k23 = (4.0 \u00b1 0.3) \u00d7 103\u00a0M\u22121s\u22121. Recent analysis of the competition between O2 and NH2OH for HNO using the boronate reporter for ONOO\u2212, resulted in the rate constant equal to (2.1 \u00b1 0.4) \u00d7 104\u00a0M\u22121s\u22121  \u00d7 106\u00a0M\u22121s\u22121, k25 = (1.2 \u00b1 0.2) \u00d7 106\u00a0M\u22121s\u22121 and k26 = (2.2 \u00b1 0.7) \u00d7 104\u00a0M\u22121s\u22121, for HS\u2212, HSO3\u2212, and S2O32\u2212, respectively (2O32\u2212 (4\u00a0M\u22121s\u22121 (\u2212 and HNO (\u2212 to form HS2\u2212 and release NH2OH (\u2212O3SSNHOH adduct (the product of 2O32\u2212 could result in the formation of NH2OH and S4O62\u2212 anion (2OH (2S shows that this reaction leads to the formation of hydrogen polysulfides (H2Sn) or sulfur S8, depending on the relative concentrations of H2S and HNO. The reactivity of HNO towards selected inorganic scavengers is summarized in The second-order rate constants were determined to be equal to: ectively . The rat  and the glutathione disulfide  NH2 are formed from a single transient intermediate, supporting the hypothesis of GSNHOH formation (2 is not observed with other reactive nitrogen species (RNS): \u2022NO, nitrogen dioxide (\u2022NO2), ONOO\u2212, or N2O3, making GS(O)NH2 a unique and HNO-specific product. GS(O)NH2 was, therefore, used as a marker for HNO generation from several biologically-relevant pathways: thiol-mediated decomposition of S-nitrosothiols, peroxidase-dependent NH2OH and N-hydroxy-L-arginine oxidation (Exposure of reduced glutathione (GSH) to HNO was shown to lead to the formation of both the sulfinamide derivative (GS(O)NHe, GSSG) . Higher ormation . It has xidation .It has been long assumed that HNO-driven oxidative transformation of thiols to sulfinamides is irreversible. C-terminal cysteines the nature of HNO-derived modifications is highly affected by the C-terminal carboxylate   .2\u2212 and O2, it was concluded that the rate constant for the reaction of GSH with NO\u2212/HNO is significantly higher than 1 \u00d7 105\u00a0M\u22121s\u22121 (N-acetyl cysteine (NAC) were determined to be equal to 2 \u00d7 106\u00a0M\u22121s\u22121 and 5 \u00d7 105\u00a0M\u22121s\u22121, respectively (6\u00a0M\u22121s\u22121 (2 for HNO (using boronate probes for ONOO\u2212), yielded the following values of the rate constants in aqueous solutions at pH 7.4: cysteine (kCys = (4.5 \u00b1 0.9) \u00d7 106\u00a0M\u22121s\u22121, pKa = 8.3), glutathione (kGSH = (3.1 \u00b1 0.6) \u00d7 106\u00a0M\u22121s\u22121, pKa = 8.8), N-acetylcysteine (kNAC = (1.4 \u00b1 0.3) \u00d7 106\u00a0M\u22121s\u22121, pKa = 9.5) and captopril (kCap = (6 \u00b1 1) \u00d7 105\u00a0M\u22121s\u22121, pKa = 9.8)  is the active form reacting with HNO. The second order rate constants for HNO reaction with protein-bound thiols were also determined in that study for human and bovine serum albumins (pKa \u223c 8.5 for Cys34) (kHSA = (1.4 \u00b1 0.4) \u00d7 106\u00a0M\u22121s\u22121, kBSA = (1.4 \u00b1 0.3) \u00d7 106\u00a0M\u22121s\u22121). Such a high reactivity of thiols towards HNO, together with high concentrations of GSH and albumin in cells and plasma, respectively, suggest that thiols may be the potential targets of HNO in biological systems.Several groups studied the kinetics of the reaction of HNO with GSH. Based on the effect of GSH on the rate of Angeli\u2019s salt decomposition in aqueous solution at pH 7.4 in the presence of NO5\u00a0M\u22121s\u22121 . In an iectively . The rat6\u00a0M\u22121s\u22121 . More rea = 9.8) . It was N-acetylcysteine, bovine serum albumin and human serum albumin was also recently reported (kobs) can be expressed as a function of pH, which depends on thiol pKa, and the rate constants of azanone reaction with RS\u2212 (kthiolate) and with RSH (kthiol) (\u2212) is favored (kthiolate \u223c 107\u00a0M\u22121s\u22121) over reactions with the thiol . Such observation is consistent with the observed inverse correlation between the reaction rate constant and the pKa value of the thiol.The pH-dependent kinetics of HNO reactions with selected thiols\u2013glutathione, reported . It was kthiol) :kobs=ktKa  and inc species .6H5SO2\u2212), the decomposition product of Piloty\u2019s acid, has been determined as kbenzenesulfinate = (4.4 \u00b1 0.9) \u00d7 104\u00a0M\u22121s\u22121  would be expected to be the products of those reactions . The rat4\u00a0M\u22121s\u22121 .RSO2-+H2\u2212, 2-ClPhSO2\u2212 and 2-CF3PhSO2\u2212) were also determined and are equal to (5.0 \u00b1 1.2) \u00d7 104\u00a0M\u22121s\u22121, (3.0 \u00b1 0.7) \u00d7 104\u00a0M\u22121s\u22121 and (1.1 \u00b1 0.2) \u00d7 104\u00a0M\u22121s\u22121, respectively (3\u00a0M\u22121s\u22121), the rate constant for the reaction between HNO and benzenesulfinate  is one order of magnitude higher.The rate constants of HNO reactions with 2-bromo-, 2-chloro- and 2-trifluoromethylbenzenesulfinates  was reported  with reported . It was S-diazeniumdiolate transient product has also been recently proposed for the reaction of thiols with \u2022NO, resulting in the formation of HNO  \u00d7 104\u00a0M\u22121s\u22121 .C- and S-nitroso compounds resulting in the formation of phosphine oxides and aza-ylides (kGSH = 2 \u00d7 106\u00a0M\u22121s\u22121), the rate constant for the reaction of HNO with a water-soluble phosphine, trisphosphine trisodium salt, was estimated at 37\u00b0C and pH 7.4 to be equal to 9 \u00d7 105\u00a0M\u22121s\u22121  \u00d7 107\u00a0M\u22121s\u22121  were recently re-evaluated and the values determined at pH 7.4 and 25\u00b0C are equal to (3.0 \u00b1 0.5) \u00d7 107\u00a0M\u22121s\u22121 . The val6\u00a0M\u22121s\u22121 .5\u00a0M\u22121s\u22121.In 2015 C-nucleophiles can act as efficient scavengers of HNO , 1,3-cyclohexanedione (C6H8O2), and 1,3-cycloheptanedione (C7H10O2) was studied and the obtained second order rate constants were equal to 2.8 \u00d7 102\u00a0M\u22121s\u22121, 2.2 \u00d7 103\u00a0M\u22121s\u22121 and 6.8 \u00d7 103\u00a0M\u22121s\u22121, respectively. This indicates that the reactivity of cyclic C-nucleophiles toward HNO significantly increases with an increase in their ring size -2,4-piperidinedione = 1.4 \u00d7 104\u00a0M\u22121s\u22121.The substitution of one or more carbon atoms in the ring of 1,3-cyclohexanedione with nitrogen resulted in an increase in ward HNO . In the k2-thiobarbituric acid = 8.2 \u00d7 102\u00a0M\u22121s\u22121 and kMeldrum\u2019s acid = 8.7 \u00d7 102\u00a0M\u22121s\u22121.The reactivity of barbituric acid, 1,3-dimethylbarbituric acid, 2-thiobarbituric acid and Meldrum\u2019s acid  towards azanone  was alsoThe reactivity of HNO towards different classes of organic nucleophiles has been summarized in \u2022NO (E\u00b0\u2019 (\u2022NO/1HNO) = \u22120.16\u00a0V for pH 7) )  , it coul 0.256\u00a0V ), Cu,Zn- 0.403\u00a0V ), aminox 0.204\u00a0V ), TEMPOL 0.204\u00a0V ) and 3-c 0.102\u00a0V ) and nit 0.270\u00a0V ) and c-P 0.270\u00a0V ).c(Fe3+) with an excess of Angeli\u2019s salt in phosphate buffer at pH 7.0 at 25\u00b0C leads to the formation of ferrocytochrome c (cyt c(Fe2+)) (c(Fe3+) reduction was nearly zero order in the concentration of cyt c(Fe3+) and first order in the concentration of HN2O3\u2212, suggesting that the decomposition of Angeli\u2019s salt was controlling the rate of the reaction, consistent with HNO acting as the reductant of cyt c (Fe3+) (c reduction at low [HN2O3\u2212]0/[cyt c (Fe3+)]0 ratio was close to 50%.In 1988 it was reported that the treatment of cyt c(Fe2+)) . The inic (Fe3+) . The repc(Fe3+) reduction by HNO have been reported in the literature: k39 = 2 \u00d7 104\u00a0M\u22121s\u22121, (k39 = 4 \u00d7 104\u00a0M\u22121s\u22121 (c(Fe3+) in aqueous solutions of Angeli\u2019s salt was not observed in the presence of O2 (c (Fe2+) is oxidized to cyt c(Fe3+) in aerated solutions of Angeli\u2019s salt (\u2212 in the reaction of HNO and O2 (c(Fe2+) by ONOO\u2212  or ONOO authors .cyt\u00a0c. In an elegant kinetic study on the reactivity of nitroxides toward HNO with the use of EPR spectrometry, the reduction of cyclic stable aminoxyl radicals (RN-O\u2022) by HNO to the corresponding hydroxylamines (RN-OH) (Other mild one-electron oxidants reported to oxidize HNO to  (RN-OH)  was repo (RN-OH) .RN-O\u2022\u00a0+\u2022 radicals have been determined with the use of the competition kinetics against the reference reaction of HNO with ferric myoglobin (MbFeIII). In the presence of HNO donor, MbFeIII undergoes reductive nitrosylation with the formation of relatively stable ferrous nitrosyl complex, MbFeIINO, which can be followed by UV-Vis absorption spectroscopy. Using kMbFe(III) = 8 \u00d7 105\u00a0M\u22121s\u22121 (kTEMPO = (1.4 \u00b1 0.2) \u00d7 105\u00a0M\u22121s\u22121), TEMPOL (kTEMPOL = (1.4 \u00b1 0.2) \u00d7 105\u00a0M\u22121s\u22121) and 3-carbamoyl-PROXYL (k3-CP = (4.3 \u00b1 0.4) \u00d7 104\u00a0M\u22121s\u22121) (kTEMPOL = 8 \u00d7 104\u00a0M\u22121s\u22121) (kTEMPO = 6.3 \u00d7 104\u00a0M\u22121s\u22121) (k = (8 \u00b1 2) \u00d7 104\u00a0M\u22121s\u22121) \u00a0\u00d7\u00a0104\u00a0M\u22121s\u22121) (The second-order rate constants of HNO reactions with RN-O5\u00a0M\u22121s\u22121  as a ref\u00a0M\u22121s\u22121) . Those v\u00a0M\u22121s\u22121)  and TEMP\u00a0M\u22121s\u22121)  and a mo\u00a0M\u22121s\u22121) . Nitroxi\u00a0M\u22121s\u22121) . This pr\u00a0M\u22121s\u22121) . The pro4\u00a0M\u22121s\u22121 , a value\u00a0M\u22121s\u22121) . Due to \u2022NO will react with HNO to form the N2O2\u2022\u2212 radical anion , are widely used in redox biology studies as scavengers of \u2022NO  of characteristic EPR spectrum and \u2022NO2 (\u2022NO are in the range (0.4\u201316) \u00d7 104\u00a0M\u22121s\u22121  = 8 \u00d7 105\u00a0M\u22121s\u22121 (kPTIO = kc-PTIO = (1.4 \u00b1 0.2) \u00d7 105\u00a0M\u22121s\u22121. Independently, the kinetics of c-PTIO reaction with HNO was determined using NH2OH as a competing agent and the kC-PTIO/k23 ratio of 5.5 \u00b1 0.9 was obtained (k23 = (4.0 \u00b1 0.3) \u00d7 103\u00a0M\u22121s\u22121 (k23 = (2.1 \u00b1 0.4) \u00d7 104\u00a0M\u22121s\u22121 (kC-PTIO = (2.2 \u00b1 0.5) \u00d7 104\u00a0M\u22121s\u22121 (kC-PTIO = (1.2 \u00b1 0.4) \u00d7 105\u00a0M\u22121s\u22121. It has been also shown, that \u2022NO2 radicals formed in such a system can oxidize Angeli\u2019s salt anion to transient radical product, that decomposes to NO2\u2212 and \u2022NO (k43 = 7.7 \u00d7 106\u00a0M\u22121s\u22121)  .N2O32-+64\u2212 anion as a \u2022NO2 radical scavenger (64\u2212 and Fe(CN)63\u2212 anions are in redox equilibrium with nitronyl nitroxide radicals and Fe(CN)63\u2212 anion is an oxidant of HNO. Based on the established competition, the kc-PTIO/k23\u00a0ratio of 1.7 \u00b1 0.2 and k23 = (4.0 \u00b1 0.3) \u00d7 103\u00a0M\u22121s\u22121 (k23 = (2.1 \u00b1 0.4) \u00d7 104\u00a0M\u22121s\u22121 (kc-PTIO = (6.8 \u00b1 1.3) \u00d7 103\u00a0M\u22121s\u22121 and 2\u00a0M\u22121s\u22121 (kC-PTIO = (3.6 \u00b1 1.1) \u00d7 104\u00a0M\u22121s\u22121 and 3\u00a0M\u22121s\u22121 cavenger . Such a 3\u00a0M\u22121s\u22121  or k23 4\u00a0M\u22121s\u22121  one can 2\u00a0M\u22121s\u22121  or kC-P3\u00a0M\u22121s\u22121 .c (cyt c), soluble guanylate cyclase (sGC), and cytochromes P450 (CYP450) (II)O2) reacts with HNO forming ferric heme and possibly \u2022NO and H2O2 (k44 = 1 \u00d7 107\u00a0M\u22121s\u22121 (\u2022NO formed upon HNO oxidation reacts with another Mb (FeII)O2 molecule with rate constant k45 = 3\u20135 \u00d7 107\u00a0M\u22121s\u22121 producing ferric heme and NO3\u2212 (II)O2 (II)O2 and Hb(FeII)O2 convert HNO to \u2022NO rapidly. It is worth to emphasize that in the literature an alternative mechanism for the heme (FeII)O2/HNO reaction was also proposed. In that mechanism, two ferric hemes, hydroxylamine and O2 are the final products (The reaction of HNO with heme-proteins has been studied extensively for nearly 40\u00a0years. Among the studied heme-enzymes are myoglobin (Mb), hemoglobin (Hb), horseradish peroxidase (HRP), catalase (cat), cytochrome (CYP450) . The reaand H2O2  (Doyle aand H2O2  and the 7\u00a0M\u22121s\u22121 . \u2022NO fornd NO3\u2212  (Doyle and NO3\u2212 . Identic\u2212 (II)O2 . Overallproducts .heme-FeII)) reacts with HNO forming coordination complex Mb (FeII)HNO (4\u00a0M\u22121s\u22121 (5\u00a0M\u22121s\u22121 (II) with HNO is followed by subsequent reaction of Mb (FeII)HNO with HNO yielding Mb (FeIII)NO, with the rate constant estimated as 1.67 \u00d7 104\u00a0M\u22121s\u22121 (II) is equal to ca. 2.0 \u00d7 105\u00a0M\u22121s\u22121 (5\u00a0M\u22121s\u22121 (Deoxymyoglobin (Mb (FeFeII)HNO . Origina4\u00a0M\u22121s\u22121 . The re-5\u00a0M\u22121s\u22121 . The rea4\u00a0M\u22121s\u22121  (Zapata 4\u00a0M\u22121s\u22121 . For deo5\u00a0M\u22121s\u22121 . For oth5\u00a0M\u22121s\u22121 .heme-FeII)NO and Hb(FeII)NO, respectively   .heme-FeThe rate constant of reductive nitrosylation of metHb is difficult to determine due to the side reaction of HNO with \u03b2-93 cysteines of hemoglobin . Nonethe5\u00a0M\u22121s\u22121 and 2 \u00d7 106\u00a0M\u22121s\u22121  with HNO results in the reduction of iron heme and the formation of \u2022NO, as already discussed in Oxidation of HNO to NO) (The reaction of cyt O to NO) . It has O to NO) .\u2022NO (II)HNO complex (II)NO. sGC(FeIII) is unreactive toward HNO or \u2022NO. However, a contrary report was published, where the HNO-dependent activation of sGC was excluded (II)HNO and HNO that follows to the formation of sGC(FeII)NO (In the case of sGC there is no estimated rate constant for its reaction with HNO. Miller and coworkers proposed that activation of sGC proceeds directly through HNO and the ferrous heme reaction without conversion of HNO to \u2022NO . The exp complex  but not excluded . That re(FeII)NO  is respo(FeII)NO .II(NO) complex similarly to other heme enzymes   .4\u00a0M\u22121s\u22121)   is in re\u00a0M\u22121s\u22121)  indicatiThe kinetics of HNO reaction with other porphyrins containing iron and manganese were also studied and the appropriate rate constants are compiled in via the possible metal porphyrin-donor complex ) is an important example, since it occurs naturally and is an essential mammalian coenzyme. It was shown that aquacobalamin (H2O-Cbl+) and hydroxycobalamin (HO-Cbl) in the presence of Angeli\u2019s salt are converted to the nitroxyl cobalamin (NO\u2212-CoIIICbl) (2O-Cbl+ occurs and the complex was observed. The rate constant for the AS/H2O-Cbl+ reaction at acidic pH was determined to be 122.6 \u00b1 5.3 M\u22121s\u22121 (2O-Cbl+ and Piloty\u2019s acid (PA) has shown that PA also reacts directly with H2O-Cbl+ at neutral pH (28.4 \u00b1 0.4\u00a0M\u22121s\u22121) (\u2212-CoIIICbl)  . The mec3 M\u22121s\u22121 . Recent \u00a0M\u22121s\u22121) . In turn\u00a0M\u22121s\u22121) . The mec\u00a0M\u22121s\u22121) ; 2016. ToIIICbl) ; 2016.To summarize, the reaction scheme of HNO with heme-proteins is very complex and still remains an area that requires further studies and analyses. In addition, an interesting aspect relates to the direct reactions of HNO-donors with metal-porphyrins, of potential pharmacological relevance.2O3\u2212, however the exact stoichiometry of this reaction with respect to HNO is unclear (c(Fe3+) (10\u201340\u00a0\u03bcM), the Cu,Zn-SOD-inhibitable reduction of cyt c(Fe3+) was observed. The Cu,Zn-SOD concentration was selected to be sufficient to compete with cyt c(Fe3+) for O2\u2022\u2013, but too low to detectably inhibit NADPH oxidation. That experiment strongly suggested the generation of O2\u2022\u2013 in HNO/O2/NADPH system. The authors proposed that NADPH is oxidized in such a solution to NADP\u2022 radicals, which subsequently reduce O2 to O2\u2022\u2212 with the formation of NADP+. At higher concentration (\u223c2\u00a0\u03bcM), Cu,Zn-SOD inhibited by \u223c50% the oxidation of NADPH  \u00d7 104\u00a0M\u22121s\u22121 was reported (k52 = (1.3 \u00b1 0.4) \u00d7 104\u00a0M\u22121s\u22121 was also determined for NADPH. In the direct reaction of HNO with NADH or NADPH in deaerated Angeli\u2019s salt solution, one may expect the formation of hydroxylamine as an HNO reduction product  with Angeli\u2019s salt in aerobic buffered aqueous solutions (pH 7.4) has been presented in several scientific reports (N-nitroso derivative as the main product. The yield of its formation is rather low (below 20%) and depends on the indolic compound: Angeli\u2019s salt concentrations ratio (N-nitroso derivative is significantly higher in the presence of bicarbonate (N-nitrosation mechanism. The recent study of N-acetyl-L-tryptophan and small peptides containing either tryptophan or both tryptophan and cysteine residues, has shown that in the presence of cysteine, excess HNO is required for efficient TrpNO formation, clearly indicating, that tryptophan residues are significantly less reactive towards HNO, than cysteine residues.The results of the studies on the reaction of various indolic compounds (e.g.,  reports . All thens ratio . It was arbonate , which m\u2022NO, and may be expected to exhibit unique physiological activity. The experimental limitations due to its instability under physiological conditions provide a significant hindrance in study design to further explore HNO chemistry. The development of new donors and rapid generation methods for time-resolved kinetic studies may overcome some of those obstacles. In addition, the combination of the experimental data with theoretical calculations may help with drawing reliable mechanistic conclusions. Finally, as a note of caution, it has to be emphasized that many rate constants of HNO reactions listed in this review were determined by competition kinetics, via kinetic simulations or other indirect approaches, and are based on very few values determined directly. Therefore, it can be expected that with the development of new experimental methods, the rate constants may need to be re-evaluated and the mechanistic conclusions adjusted.HNO show a different chemical reactivity than"}
{"text": "The tetrel bond strength for the [I4C\u00b7\u00b7\u00b7X\u2212] series and [I4Tt\u00b7\u00b7\u00b7X\u2212] , was weak-to-moderate, whereas that in the remaining 16 complexes was dative tetrel bond type with very large interaction energies and short Tt\u00b7\u00b7\u00b7X close contact distances. The basis set superposition error corrected interaction energies calculated with the highest-level theory applied, [CCSD(T)/def2-TZVPPD], ranged from \u22123.0 to \u2212112.2 kcal mol\u22121. The significant variation in interaction energies was realized as a result of different levels of tetrel bonding environment between the interacting partners at the equilibrium geometries of the complex systems. Although the \u03c9B97X-D computed intermolecular geometries and interaction energies of a majority of the [I4Tt\u00b7\u00b7\u00b7X\u2212] complexes were close to those predicted by the highest level of theory, the MP2 results were shown to be misleading for some of these systems. To provide insight into the nature of the intermolecular chemical bonding environment in the 25 molecule\u2013anion complexes investigated, we discussed the charge-density-based topological and isosurface features that emanated from the application of the quantum theory of atoms in molecules and independent gradient model approaches, respectively.Twenty-five molecule\u2013anion complex systems [I Ion\u2013molecule interactions are fascinating in chemistry ,2,3,4, b\u2212, Br\u2212, or I\u2212) attracts the electrophiles on bonded Si atoms in the neutral molecules. Neither anion is located precisely at the centroid of the neutral molecule(s). When the anion (Cl\u2212) is entrapped inside the Si20 cage of a fully or partially chlorinated icosasilane molecular entity (20 cage to stabilize the tetrel-centered (Cl\u2212)Si\u00b7\u00b7\u00b7Cl and/or (H\u2212)Si\u00b7\u00b7\u00b7Cl close contacts.r entity e,f, its The fundamental phenomena that drive isolated neutral molecules to self-assemble with anions play a significant role in the processes of anion recognition and anion transport, among others ,17,18. O4, of the tetrel tetrahalide family (TtX4), where Tt stands for the elements in Group 14 of the periodic table and X represents the halide derivative . The anions considered were the halide derivative, X\u2212. It is worth mentioning that the theoretical chemistry of 1:1 complexes formed of lighter members of the TtX4  family with the first three halide anions was recently reported  complexes be called ordinary tetrel bonds . Density functional theory  ,31,32,33 (QTAIM) ,41,42,43 (QTAIM) ,45-based (QTAIM) ,46 respo(\u03c9B97X-D ) and ab  methods, in conjunction with the def2-TZVPPD basis set, were also employed to demonstrate the accuracy of MP2 and \u03c9B97X-D geometries and energies of [I4Tt\u00b7\u00b7\u00b7X\u2212]. Standard non-relativistic calculations were performed without considering the effect of spin-orbit coupling for heavy atoms such as Pb, following a previous study  level. An isoelectron density envelope of 0.001 a.u. was used on which to compute the potential, even though the use of higher isoelectron density envelopes was suggested in other studies for chemical systems containing low-polarizable atomic basins  are consistent with the topological charge-density-based features emanated using QTAIM. Both Multiwfn . The AIMAll code was used  and [\u03c9B97X-D/def2-QZVPPD]. The best agreement between experiment and theory is observed with [\u03c9B97X-D/def2-QZVPPD], and MP2 shows a tendency to underestimate r(Tt\u2013I). A very similar trend was obtained with these methods in conjunction with the def2-QZVPPD basis set.Crystals of TtIe (ICSD) ,78,79,804. From these, it may be seen that the atomic basins are connected to each other in each isolated monomer through bond paths (solid lines between atomic basins in atom color) that pass-through bond critical points (tiny green spheres), thus recovering the expected tetrahedral Td shape of TtI4.b is larger at the C\u2013I bcps in CI4 than at the Pb\u2013I bcps in PbI4. It follows the trend across the series: \u03c1b (C\u2013I) > \u03c1b (Si\u2013I) > \u03c1b (Ge\u2013I) > \u03c1b (Sn\u2013I) > \u03c1b (Pb\u2013I). The trend signifies that the charge concentration is predominant at the C\u2013I bcps in CI4 relative to that at the Pb\u2013I bcps in PbI4.The charge density \u03c1b, b is stabilizing (Hb < 0) at the Tt\u2013I bcps, which is due to the potential energy density Vb that dominates over the gradient kinetic energy density Gb at the bcp. Hb is increasingly more positive at the Tt\u2013I bcps across the series from CI4 through SiI4 to GeI4 to SnI4 to PbI4. This is consistent with the character of Tt\u2013I bonds in TtI4, in which it progressively becomes less covalent than ionic, passing from CI4 through SiI4 to PbI4. That is, the covalency of the Tt\u2013I bond follows this order: C\u2013I > Si\u2013I > Ge\u2013I > Sn\u2013I > Pb\u2013I. Furthermore, the sign of \u22072\u03c1b at Tt\u2013I bcps is also negative for all monomers except for the Tt\u2013I  bcps, giving an indication that the Tt\u2013I bonds in CI4, SiI4, and GeI4 are relatively more covalent than those in SnI4 and PbI4. Typically, \u22072\u03c1b < 0 and Hb < 0 represent covalent (shared-type) interactions; \u22072\u03c1b > 0 and Hb > 0 represent ionic (closed-shell) interactions; and \u22072\u03c1b > 0 and Hb < 0 represents mixed  interactions  complexes. They are shown in The five halide anions have linearly approached the Tt atom from the opposite side of the I\u2013Tt covalent bond in TtI4 with the five halide anions. Because the \u03c3-hole on the carbon atom in CI4 is the weakest compared to that on the Tt atom in TtI4   , the strC\u00b7\u00b7\u00b7At\u2212] , respect4C\u00b7\u00b7\u00b7X\u2212] increases as the halogen derivative becomes more polarizable; it is smallest in [I4C\u00b7\u00b7\u00b7F\u2212], with r(Tt\u00b7\u00b7\u00b7F) = 2.665 \u00c5 with [CCSD/def2-TZVPPD]. By contrast, the I\u2013C\u2013I angle in complexed [I4C\u00b7\u00b7\u00b7F\u2212] either increases or decreases compared to that of its uncomplexed counterpart (\u2220I\u2013C\u2013I = 109.47\u00b0). For instance, the I\u2013C bond linearly attached to the anion forms smaller \u2220I\u2013C\u2013I with the three nearest-neighbor I atoms, whereas the remaining I\u2013C bonds that are not directly involved in the formation of tetrel bond are associated with larger \u2220I\u2013C\u2013I. These two angles types are 107.5 (111.3\u00b0), 108.1 (110.8\u00b0), 108.4 (110.5), 108.8 (110.1\u00b0), and 108.8 (110.1\u00b0) in [I4C\u00b7\u00b7\u00b7F\u2212], [I4C\u00b7\u00b7\u00b7Cl\u2212], [I4C\u00b7\u00b7\u00b7Br\u2212], [I4C\u00b7\u00b7\u00b7I\u2212], and [I4C\u00b7\u00b7\u00b7At\u2212], respectively.The C\u00b7\u00b7\u00b7X intermolecular distance in [I4C\u00b7\u00b7\u00b7F\u2212], 4C\u00b7\u00b7\u00b7F\u2212]. The latter ones mimic the I\u00b7\u00b7\u00b7X  links in the other four members of the same family , a feature that has been recommended for identifying hydrogen bonds [4C\u00b7\u00b7\u00b7F\u2212], [I4C\u00b7\u00b7\u00b7Cl\u2212], [I4C\u00b7\u00b7\u00b7Br\u2212], [I4C\u00b7\u00b7\u00b7I\u2212], and [I4C\u00b7\u00b7\u00b7At\u2212] are ca. 2.871, 3.626, 3.892, 4.274, and 4.322 \u00c5, respectively. The former three are less than their respective sum of vdW radii of 3.50 (I + F), 3.86 (I + Cl), and 3.90 \u00c5 (I + Br), whereas the latter two are slightly greater than the sum of their respective sum of vdW radii of 4.08 (I + I) and 4.04 \u00c5 (I + At). . Since rom ref. ,62,97,99re known ,101, whi4C\u00b7\u00b7\u00b7X\u2212], as CCSD. However, the increase in the size of the basis set from def2-TZVPPD to def2-QZVPPD has resulted in a slight increase in the Tt\u00b7\u00b7\u00b7X intermolecular distance with \u03c9B97X-D and MP2. Whatever is the size of the basis set, the intermolecular distances predicted using MP2 are underestimated relative to \u03c9B97X-D and CCSD. Furthermore, [MP2/def2-TZVPPD] has predicted the C\u00b7\u00b7\u00b7I and C\u00b7\u00b7\u00b7At bond distances to be 4.091 and 4.083 \u00c5 for [I4C\u00b7\u00b7\u00b7I\u2212] and [I4C\u00b7\u00b7\u00b7At\u2212], respectively; they were 3.990 and 4.009 \u00c5 with def2-QZVPPD, respectively. This means that MP2 does not correctly predict the trend in C\u00b7\u00b7\u00b7I and C\u00b7\u00b7\u00b7At bonding distances, as predicted by \u03c9B97X-D and CCSD  and Hb (Hb < 0) at the bcps of the three equivalent bonds, were equivalent  > [I4C\u00b7\u00b7\u00b7Cl\u2212] (\u03b4 = 0.030) > [I4C\u00b7\u00b7\u00b7Br\u2212] (\u03b4 = 0.023) > [I4C\u00b7\u00b7\u00b7I\u2212] (\u03b4 = 0.019) > [I4C\u00b7\u00b7\u00b7At\u2212] (\u03b4 = 0.017), in consistent with the trend found for interaction energy  is completely lost.The nature of the intermolecular bonding environment found in  c\u2013e. Simil, or Br a\u2013c, but Ge\u00b7\u00b7\u00b7X\u2212] d,e. This4Si\u00b7\u00b7\u00b7Br\u2212], in which, the responsible interacting units were involved in the formation of a dative tetrel bond; it is in a manner similar to that found for [I4Si\u00b7\u00b7\u00b7X\u2212] . On the other hand, MP2 has recognized the attraction between I4Si and X\u2212 in the first four members of the [I4Si\u00b7\u00b7\u00b7X\u2212] series to be unusually strong and that in [I4Si\u00b7\u00b7\u00b7At\u2212] to be moderate. The former result with MP2 is applicable to the [I4Ge\u00b7\u00b7\u00b7X\u2212] series as well. This means that the Tt\u00b7\u00b7\u00b7X close contacts in the above-mentioned molecule\u2013anion systems are not ordinary tetrel bonds; they are dative tetrel bonds.While the bonding features noted above were obtained from [\u03c9B97X-D/def2-QZVPPD], the [CCSD/def2-QZVPPD] method has predicted an exception for [Ib is appreciable at the Ge\u00b7\u00b7\u00b7X bcps in [I4Ge\u00b7\u00b7\u00b7X\u2212] when X points to F, Cl, and Br. For [I4Ge\u00b7\u00b7\u00b7I\u2212], the \u03c1b is small at Ge\u00b7\u00b7\u00b7I bcp (\u03c1b = 0.0048 a.u.), and the interaction between the monomers is also reinforced by I\u00b7\u00b7\u00b7I interactions  bcps in [I4Ge\u00b7\u00b7\u00b7X\u2212] are not only typical for coordinate bonds but larger than that can be expected for ordinary non-covalent interactions such as hydrogen bonds, and halogen bonds, among others (\u03c1b < 0.05 a.u.). They may be comparable with the \u03c1b values of the Tt\u2013I coordinate bonds in isolated and complexed TtI4. A similar conclusion might be arrived at for Si\u00b7\u00b7\u00b7X bcps in [I4Si\u00b7\u00b7\u00b7X\u2212] , Our QTAIM analysis, ractions d. The \u03c1b2\u03c1b (\u22072\u03c1b > 0) and Hb (Hb < 0), 4Si\u00b7\u00b7\u00b7X\u2212] provided [CCSD/def2-TZVPPD] results are considered. The large \u03b4 values corresponding to atom\u2013atom pairs responsible for the Si\u00b7\u00b7\u00b7X and Ge\u00b7\u00b7\u00b7X  close contacts provide further evidence that there are no \u03c0-type interactions involved; they are purely \u03c3-type coordinate dative bonds. By contrast, the \u03b4 values are very small for atom\u2013atom pairs causing the Si\u00b7\u00b7\u00b7X and Si\u00b7\u00b7\u00b7X close contacts in [I4Ge\u00b7\u00b7\u00b7X\u2212] and [I4Ge\u00b7\u00b7\u00b7X\u2212] , respectively, indicative of closed-shell interactions. The three equivalent I\u00b7\u00b7\u00b7X halogen\u00b7\u00b7\u00b7halogen close contacts in each of [I4Ge\u00b7\u00b7\u00b7X\u2212] and [I4Ge\u00b7\u00b7\u00b7X\u2212]  are described by small \u03b4 values, and positive \u22072\u03c1b and Hb. Similarly, the Si\u00b7\u00b7\u00b7X and Ge\u00b7\u00b7\u00b7X  tetrel bonds are described by small \u03b4 values, as expected.From the sign and magnitude of \u22074 and PbI4, respectively, are stronger than those of TtI4 . Therefore, their acidic strengths are adequate enough to recognize the five halide anions when in close proximity. This may be rationalized from QTAIM\u2019s molecular graphs of resulting configurations, [I4Sn\u00b7\u00b7\u00b7X\u2212] and [I4Pb\u00b7\u00b7\u00b7X\u2212] , illustrated in 4 and PbI4. This means that the TtI4 molecule is structurally fully deformed in the presence of each of the five halide anions. There is no secondary intermolecular interaction that can play a role in the geometrical stability of the resulting complex anions, as found for other series (see above). In all cases, the tetrel center adopts a trigonal bipyramidal geometry . Clearly, the resulting complex anions each is nothing but a coordination compound, and the Tt\u00b7\u00b7\u00b7X close-contact is formally a Tt\u2013X dative tetrel bond. In such cases, charge transfer from the anion to the \u03c3*(I\u2013Tt) anti-bonding orbital is expected, and the SN2 mechanism is likely to play a role in driving the dative bond formation between the interacting species [The \u03c3-holes on Sn and Pb in SnI species .4Pb\u00b7\u00b7\u00b7X\u2212] series and the smallest for the [I4C\u00b7\u00b7\u00b7X\u2212] series. In particular, the [\u03c9B97X-D/def2-QZVPPD] level QTAIM charge transfer from X\u2212 to PbI4 is 0.263, 0.371, 0.424, 0.515 and 0.588 e for [I4Pb\u00b7\u00b7\u00b7F\u2212], [I4Pb\u00b7\u00b7\u00b7Cl\u2212], [I4Pb\u00b7\u00b7\u00b7Br\u2212], [I4Pb\u00b7\u00b7\u00b7I\u2212], and [I4Pb\u00b7\u00b7\u00b7At\u2212], respectively. The corresponding charge transfer values were 0.229, 0.334, 0.382, 0.460, and 0.519 e for [I4Sn\u00b7\u00b7\u00b7F\u2212], [I4Sn\u00b7\u00b7\u00b7Cl\u2212], [I4Sn\u00b7\u00b7\u00b7Br\u2212], [I4Sn\u00b7\u00b7\u00b7I\u2212], and [I4Sn\u00b7\u00b7\u00b7At\u2212], respectively. These results imply that the nature of charge-transfer in the Sn- and Pb-based anions is virtually similar and that the charge-transfer preference is consistent with the interaction energy preference across a given series, indicating that the charge-transfer phenomenon is likely to be one of the most prominent contributors to the interaction. Our calculation suggests that the extent of charge transfer is the largest for the [Ie calculated for [I4C\u00b7\u00b7\u00b7F\u2212], [I4C\u00b7\u00b7\u00b7Cl\u2212], [I4C\u00b7\u00b7\u00b7Br\u2212], [I4C\u00b7\u00b7\u00b7I\u2212], and [I4C\u00b7\u00b7\u00b7At\u2212], respectively. These results may lead to a conclusion that the formation of stronger complexes accompanies an appreciable amount transfer of charge between the interacting monomers, and is not very surprising   is non-negligible; it may be comparable to that of the Tt\u2013I bcps of complexed I4Tt. The Tt\u2013I and Tt\u00b7\u00b7\u00b7X bcps are both characterized by \u22072\u03c1b > 0 and Hb < 0, indicating the presence of a mixed covalent and ionic character. Since Hb becomes increasingly more positive at the Tt\u00b7\u00b7\u00b7X bcp passing from [I4Tt\u00b7\u00b7\u00b7F\u2212] through [I4Tt\u00b7\u00b7\u00b7Cl\u2212] to [I4Tt\u00b7\u00b7\u00b7Cl\u2212] to [I4Tt\u00b7\u00b7\u00b7Br\u2212] to [I4Tt\u00b7\u00b7\u00b7I\u2212] to [I4Tt\u00b7\u00b7\u00b7At\u2212], it is clear that these interactions are less covalent in the same order. The \u22072\u03c1b values are decreasing in the series from [I4Tt\u00b7\u00b7\u00b7F\u2212] through [I4Tt\u00b7\u00b7\u00b7Cl\u2212] to [I4Tt\u00b7\u00b7\u00b7At\u2212], indicating that the Tt\u00b7\u00b7\u00b7F tetrel bond is more ionic than the Tt\u00b7\u00b7\u00b7At tetrel bond. In the case of Tt = Si and Ge, the Tt\u00b7\u00b7\u00b7X  bcps show \u22072\u03c1b > 0 and Hb < 0  bond in the respective system. The characteristics of Si\u2013I bonds in I4Si resemble the C\u2013I bonds in I4C.From the molecular graphs of QTAIM in d Hb < 0 . The fou4Tt\u00b7\u00b7\u00b7X\u2212]  is considerably larger than what were calculated for ordinary tetrel bonds  upon its attractive engagement with the halide anions. For comparison, we note that the \u03b4 values for Tt\u2013I and Tt\u00b7\u00b7\u00b7X coordinate and dative tetrel bonds in [I4Tt\u00b7\u00b7\u00b7X\u2212] are smaller than, and comparable to, those reported for metal\u2013C(O) coordinate bonds ; however, those of Tt\u00b7\u00b7\u00b7X ordinary tetrel bonds are comparable with what were reported for metal\u00b7\u00b7\u00b7metal  interactions  in [M2(CO)10] and [M3(\u03bc-H)3(CO)12]  complexes  (Tt = C). The I\u00b7\u00b7\u00b7X closed contacts in several of these systems appeared at larger IGM-inter\u03b4g isovalues (Top). On the other hand, the Tt\u00b7\u00b7\u00b7X close contacts showed up at lower IGM-inter\u03b4g isovalues (Bottom). This is not very surprising since smaller isolvalues are typically necessary for the physical appearances of isosurfaces corresponding to weakly bonded interactions. By contrast, the relatively stronger interactions can be traceable with larger isovalues since charge density around the critical bonding region is generally appreciable. The bluish isosurface originated with large IGM-inter\u03b4g isovalues for [I4C\u00b7\u00b7\u00b7F\u2212] indicates that the attraction between the interacting units is very prominent . The view is also transferable to the [I4Ge\u00b7\u00b7\u00b7X\u2212] systems (not shown).The [I4Sn\u00b7\u00b7\u00b7X\u2212] and [I4Pb\u00b7\u00b7\u00b7X\u2212] , the IGM-inter\u03b4g isosurfaces were visualizable with an isovalue close to 0.055 a.u. 4Pb\u00b7\u00b7\u00b7X\u2212] series. Passing from the left to the right of 4Tt\u00b7\u00b7\u00b7F\u2212] through [I4Tt\u00b7\u00b7\u00b7Cl\u2212] to [I4Tt\u00b7\u00b7\u00b7Br\u2212] to [I4Tt\u00b7\u00b7\u00b7I\u2212] to [I4Tt\u00b7\u00b7\u00b7At\u2212] .In the case of [I4C\u00b7\u00b7\u00b7X\u2212] series and [I4Tt\u00b7\u00b7\u00b7X\u2212] , the int (BSSE)E values for all other molecule\u2013anion systems are much larger than the so-called covalent limit for hydrogen bonds  [4Tt\u00b7\u00b7\u00b7X\u2212], it is clear that the complex stability is largely determined by the polarizability of the Tt atom in I4Tt and the halogen derivative. These energies calculated in the range from \u22123.0 to \u2212112.2 kcal mol\u22121 with [CCSD(T)/def2-TZVPPD], \u22121 < int (BSSE)E < \u22125.0 kcal mol\u22121), moderate E < \u221210.0 kcal mol\u22121), strong E < \u221225.0 kcal mol\u22121), very strong E \u2264 \u221240.0 kcal mol\u22121), and ultra-strong (int (BSSE)E >> \u221240.0 kcal mol\u22121 . At the highest level of theory applied, [CCSD(T)/def2-TZVPPD], the weakest and strongest of the [I4Tt\u00b7\u00b7\u00b7X\u2212] systems are found to be [I4C\u00b7\u00b7\u00b7At\u2212] (int (BSSE)E = \u22123.20 kcal mol\u22121) and [I4Si\u00b7\u00b7\u00b7F\u2212] (int (BSSE)E = \u2212112.15 kcal mol\u22121), respectively.Except for the  with def2-TZVPPD and def2-QZVPPD, respectively; these are indicative of the fact that the strength of the tetrel bond between Si of I4Si and Br\u2212 is moderate. As mentioned already above, this is not the case with MP2 since the intE (BSSE) for the same system, for instance, with def2-QZVPPD, is predicted to be \u221260.0 kcal mol\u22121; the large intE (BSSE) implies that the attraction between I4Si and Br\u2212 causes the formation of Si\u2013Br dative tetrel bond. This result is consistent with [CCSD(T)/def2-TZVPPD], which has predicted an intE (BSSE) of \u221253.16 kcal mol\u22121 for the same system. Second, the [\u03c9B97X-D/def2-TZVPPD] level intE (BSSE) values for the remaining four systems of the [I4Si\u00b7\u00b7\u00b7X]\u2212 series are in qualitative and quantitative agreement with [CCSD(T)/def2-TZVPPD]. MP2, however, unusually overestimated the interaction energies for [I4Si\u00b7\u00b7\u00b7I\u2212] and [I4Si\u00b7\u00b7\u00b7At\u2212]. The discrepancy between the DFT (or CCSD(T)) and MP2 energies is likely due to the latter method\u2019s misleading prediction of the Si\u00b7\u00b7\u00b7I and Si\u00b7\u00b7\u00b7At close contacts, thus pushing the interacting atoms in [I4Si\u00b7\u00b7\u00b7I\u2212] to be bonded with each other via a dative tetrel bond. These peculiar results indicate that applying the MP2 approach to predict the correct nature of the tetrel bond in molecule\u2013anion complex systems formed by heavier tetrel derivatives in molecular entities should be exercised with caution.From int(BSSE),E between the five members of each series [I4Tt\u00b7\u00b7\u00b7X]\u2212 follows the trend: [I4Tt\u00b7\u00b7\u00b7F\u2212] > [I4Tt\u00b7\u00b7\u00b7Cl\u2212] > [I4Tt\u00b7\u00b7\u00b7Br\u2212] > [I4Tt\u00b7\u00b7\u00b7I\u2212] > [I4Tt\u00b7\u00b7\u00b7At\u2212] . Note that changing the basis set from def2-TZVPPD to def2-QZVPPD somehow restored the [CCSD(T)/def2-TZVPPD] level energy preference at the \u03c9B97X-D level (but not at the MP2 level) when Tt = C, but not when Tt = Pb. One reason for the anomalous change in the preference of energy ordering between [I4Tt\u00b7\u00b7\u00b7I\u2212] and [I4Tt\u00b7\u00b7\u00b7At\u2212] is that the post-HF MP2 method greatly overestimates the BSSE, as well as the electron-electron correlation energy, relative to the DFT and CCSD(T). On the other hand, the CCSD(T) method has properly accounted for electron-electron correlation energy, which ensured the correct preference of stabilization energies among the five members of any given series, [I4Tt\u00b7\u00b7\u00b7X\u2212].The preference of BSSE-corrected interaction energy, t\u00b7\u00b7\u00b7At\u2212] . This isint(BSSE)E on the distance of separation r(Tt\u00b7\u00b7\u00b7X) for 25 molecule\u2013anion complexes, [I4Tt\u00b7\u00b7\u00b7X\u2212], obtained using \u03c9B97X-D, MP2 and CCSD(T). Regardless of the different calculation methods utilized, the dependence was found to be quadratic. The square of the regression coefficient R2 was moderately higher (R2 = 0.9325) for \u03c9B97X-D compared to CCSD(T) and lower (R2 = 0.8923) for MP2.\u22121, from 2.60 to 13.58 kcal mol\u22121, and from 1.42 to 13.44 kcal mol\u22121, respectively. However, when using the def2-QZVPPD basis set, the BSSE in energy has decreased sharply, giving rise to values in the range from 0.02 to 0.13 kcal mol\u22121 with \u03c9B97X-D and from 1.01 to 5.01 kcal mol\u22121 with MP2. CCSD(T) with def2-QZVPPD was computationally very expensive; no conclusions could be drawn about the range of BSSE in energy with this method. int(BSSE)E and intE, obtained using [\u03c9B97X-D/def2-QZVPPD], [MP2/def2-QZVPPD] and [CCSD(T)/def2-TZVPPD], respectively, showing a perfect linear dependence at the former level than that at the latter two. We note further that the BSSE in energy is minimal with DFT but larger with MP2 and CCSD(T). It is very large with the def2-TZVPPD basis set than with the def2-QZVPPD basis set. For example, for \u03c9B97X-D, MP2, and CCSD(T) with def2-TZVPPD, the BSSE in energy ranged from 0.05 to 9.68 kcal mol4Tt\u00b7\u00b7\u00b7X\u2212]  was theoretically investigated to clarify the nature of the selectivity of the I4Tt host for five guest  anions. The MP2 geometries and interaction energies for the 25 molecule\u2013anion systems were underestimated and overestimated, respectively, relative to DFT and CCSD methods, and in some cases, the MP2 results were unreliable. The chemical bonding features obtained using DFT were consistent with the computationally expensive CCSD and CCSD(T) results, with an exception for [I4Si\u00b7\u00b7\u00b7Br\u2212]. For the latter, the tetrel bonding characteristics predicted by CCSD could not be reproduced by DFT-\u03c9B97X-D. Similarly, the significant overestimation of the interaction energy of [I4Si\u00b7\u00b7\u00b7I\u2212] with MP2 was in sharp disagreement with that computed using \u03c9B97X-D and CCSD(T).In this study, the series    systems, except for [I4C\u00b7\u00b7\u00b7X\u2212]  and [I4Si\u00b7\u00b7\u00b7X\u2212] . This was the case with [\u03c9B97X-D/def2-TZVPPD] and [\u03c9B97X-D/def2-QZVPPD], but [I4Ge\u00b7\u00b7\u00b7At\u2212] was added to the exclusion list. The result was different from [MP2/def2-QZVPPD] in that it predicted exceptions only for [I4C\u00b7\u00b7\u00b7X\u2212] , and is not surprising given it is an MP2\u2019s tendency to underestimate intermolecular distances. Although these latter two computational methods exclude intermolecular interactions in systems that do not follow the stringent \u201cless than the sum of vdW radii rule,\u201d the exclusion was also consistent with the nature of bond path topology revealed using QTAIM. For example, for [I4C\u00b7\u00b7\u00b7X\u2212] , [I4Tt\u00b7\u00b7\u00b7X\u2212]  and [I4Tt\u00b7\u00b7\u00b7X\u2212] , no QTAIM-based bond path topology exists between Tt and X at the [\u03c9B97X-D/def2-QZVPPD] level. This means that QTAIM does not recognize the existence of Tt\u00b7\u00b7\u00b7X tetrel bonding in the host\u2013guest systems when the tetrel bond distance between Tt and X exceeds the sum of the vdW radii of Tt and X, even though this type of limitation of QTAIM has been attributed to the arbitrary nature of the space partitioning scheme. Even so, it should be borne in mind that the Tt and X atoms of the interacting monomers in all complex systems were indeed tetrel bonded to each other, evidenced by the IGM-inter\u03b4g-based isosurfaces.The Tt\u00b7\u00b7\u00b7X separation distance calculated by [CCSD/def2-TZVPPD] was smaller than the vdW radii of the Tt and X atoms for all [I"}
{"text": "The mol\u00adecular packing is consolidated by van der Waals inter\u00adactions between these ribbons.The whole mol\u00adecule of the title compound is generated by twofold rotational symmetry. In the crystal, mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efO inter\u00adactions with  22H19NO2, is generated by twofold rotational symmetry. The N atom exhibits a trigonal-planar geometry and is located on the twofold rotation axis. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO contacts with R22(12) ring motifs, and C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in ribbons along the c-axis direction. van der Waals inter\u00adactions between these ribbons consolidate the mol\u00adecular packing. Hirshfeld surface analysis indicates that the greatest contributions to the crystal packing are from H\u22efH (45.5%), C\u22efH/H\u22efC (38.2%) and O\u22efH/H\u22efO (16.0%) inter\u00adactions.The whole mol\u00adecule of the title compound, C The phenyl ring (C1\u2013C4/C2A/C3A) attached to the N1 atom and the phenyl rings (C7\u2013C12 and C7A\u2013C12A) of the two symmetry-related 1-phenyl\u00adethan-1-one groups are oriented at 89.65\u2005(6)\u00b0 to each other.The asymmetric unit of the title compound contains half a mol\u00adecule, the complete mol\u00adecule being generated by the twofold rotational axis. Atoms N1, C1 and C4 are located on the twofold rotation axis Fig.\u00a01. The N1 3.A\u22efO1 to 1.2546 (blue) a.u  reveal that H\u22efH (45.5%), C\u22efH/H\u22efC (38.2%) and O\u22efH/H\u22efO (16.0%) inter\u00adactions make the greatest contributions to the surface contacts. N\u22efH/H\u22efN (0.3%) contacts also contribute to the overall crystal packing of the title compound. The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, C\u22efH/H\u22efC and O\u22efH/H\u22efO inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing sulfon\u00adyl]-N-phenyl\u00adbenzene\u00adsulfonamide bis\u00ad(pyridine-2-carboxamide) bis\u00ad(3-phenyl\u00adacrylate) [XEBWUY (III); Sabari et al., 2012I) possesses twofold rotational symmetry. The N atom has a trigonal-planar geometry and is located on the twofold rotation axis. Weak C\u2014H\u22efO hydrogen bonds connect the mol\u00adecules, forming a three-dimensional network. The asymmetric unit of (II) contains two independent mol\u00adecules with similar conformations. In the crystal, N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular structure. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are also observed. In (III), the C=C double bonds adopt an E configuration. In the crystal, pairs of C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into inversion dimers.A search of the Cambridge Structural Database  = 1.2Ueq(C). Owing to poor agreement between observed and calculated intensities, eighteen outliers  were omitted during the final refinement cycle.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022005382/tx2050sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022005382/tx2050Isup2.hklStructure factors: contains datablock(s) I. DOI: 2173928CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are cross-linked via inter\u00admolecular C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions into a three-dimensional network.In the title compound, the mol\u00adecule adopts an  33H33N3, is a carbazolophane, which is a cyclo\u00adphane composed of two carbazole fragments. It has a planar chirality but crystallizes as a racemate in the space group Panti-configuration, in which two carbazole fragments are partially overlapped. Both carbazole ring systems are slightly bent, with the C atoms at 3-positions showing the largest deviations from the mean planes. The dihedral angle between two carbazole fragments is 5.19\u2005(3)\u00b0, allowing an intra\u00admolecular slipped \u03c0\u2013\u03c0 inter\u00adaction [Cg\u22efCg = 3.2514\u2005(8)\u2005\u00c5]. In the crystal, the mol\u00adecules are linked via inter\u00admolecular C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions into a network sheet parallel to the ab plane. The mol\u00adecules of different sheets form other C\u2014H\u22ef\u03c0 inter\u00adactions, thus forming a three-dimensional network.The title compound, C Previously, our group reported the EPR spectrum of the title compound, but no other chemical properties were examined because of the very low yield \u2005\u00c5 for the N1/C4\u2013C15 ring system and 0.062\u2005(1)\u00c5 for N2/C16\u2013C27 ring system. In both carbazole fragments, the C atoms at the 3-positions bridged through the di\u00admethyl\u00adene\u00adamino group show the largest deviations from the mean planes [0.1177\u2005(14)\u2005\u00c5 for C7 and \u22120.1082\u2005(14)\u2005\u00c5 for C19]. The dihedral angle formed by two carbazole fragments is 5.19\u2005(3)\u00b0, providing an intra\u00admolecular slipped parallel \u03c0\u2013\u03c0 inter\u00adaction . In comparison, in the related PO compounds, the dihedral angles between two carbazole fragments and the centroid\u2013centroid distances are 5.96\u2005(6)\u00b0 and 3.294\u2005(4)\u2005\u00c5 for N-cyanamide-bridged [3.3]carbazolophane carbazolophane \u00b0, smaller than those in the related compounds , that is, the hybridization of N3 atom is closer to sp3 than to sp2, reflecting the difference in the resonance effect of the substituent at the N3 atom.The title compound has a planar chirality but crystallizes as a racemate in the centrosymmetric space group 3.C(9) chain motif running parallel to the b axis. The mol\u00adecules are further joined into columns along the a-axis direction by pairs of C\u2014H\u22ef\u03c0 inter\u00adactions , forming a centrosymmetric dimer  forms another centrosymmetric dimer -10,11,22,23-tetra\u00adhydro-9H,21H-5,8:15,12-bis\u00ad(metheno)tri\u00adaza\u00adcyclo\u00adhexa\u00addecino-di\u00adindole carbazolophane, YUKYEL; Tani et al., 2020anti-3-cyano-3-aza-1,3-dicarbazola\u00adcycloocta\u00adphane carbazolophane, BACKOG; Tani et al., 2001N-cyanamide-bridged FO [3.3]carbazolophane, syn-3-cyano-3-aza-1,3-dicarbazola\u00adcyclo\u00adocta\u00adphane benzene clathrate \u2005\u00c5 for the benzene rings bridged by cyanamide, 3.447\u2005(2)\u2005\u00c5 for the central pyrrole rings and 3.792\u2005(3)\u2005\u00c5 for the outer benzene rings. Three of the remaining four structures are PO [m.n]carbazolophanes; anti-ethenylene and 1,3-xylylene-bridged [2.5]carbazolophane carbazolophane carbazolophane \u00b0 and 3.8062\u2005(15)\u2005\u00c5 for ethenylene and 1,3-xylylene-bridged [2.5]carbazolophane; 15.04\u2005(9)\u00b0 and 3.732\u2005(3)\u2005\u00c5 for cyanamide-bridged [3.4]carbazolophane; 24.87\u2005(11)\u00b0 and 3.901\u2005(3)\u2005\u00c5  for oxa-bridged [3.5]carbazolophane. The last of the seven compounds is a FO carbazolophane, syn-cyclo\u00adbutane-bridged [2.4]carbazolophane  in di\u00adchloro\u00admethane (150\u2005mL) and sodium hydroxide  in water (10\u2005mL). Then, the flask was filled with argon and was stirred at room temperature for 3\u2005d. The reaction mixtures were washed with water, then dried over anhydrous sodium sulfate. Solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography . Elution from hexa\u00adne:ethyl acetate (19:1) gave a white solid . Elution from hexa\u00adne:ethyl acetate (10:1) gave mixtures including a syn-configuration (FO isomer), but they were difficult to separate. A part of the title compound was recrystallized from di\u00adchloro\u00admethane:ethanol (1:3) to give a colorless crystal suitable for X-ray diffraction. Melting point: 482\u2013484\u2005K. 1H NMR  \u03b4 = 1.08 , 1.57\u20131.60 ,1.78 , 2.81\u20132.97 , 3.74\u20133.90 , 4.10\u20134.17 , 5.34 , 6.38 , 7.25-7.30 , 7.46\u20137.53 , 7.67 , 8.11 .A solution of 9,9\u2032-bis\u00ad[3-(bromo\u00admeth\u00adyl)-96.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022003383/yk2167sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989022003383/yk2167Isup2.hklStructure factors: contains datablock(s) I. DOI: 2161895CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "IIIS2N2O2 chromophore contains two O,N,S-donating dianionic ligands in perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. The FeIII ion is in the high-spin state at 100\u2005K. The variable-tem\u00adper\u00adature magnetic susceptibility measurements (5\u2013320\u2005K) are consistent with the presence of a high-spin S\u00a0= 5/2 FeIII ion.The Fe 3)2NH2][Fe(C10H11O2N3S)2], are reported. The asymmetric unit consists of an octa\u00adhedral [FeIII(L)2]\u2212 fragment, where L2\u2212 is 3-eth\u00adoxy\u00adsalicyl\u00adaldehyde thio\u00adsemi\u00adcar\u00adba\u00adzon\u00adate(2\u2212), and a di\u00admethyl\u00adammonium cation. Each L2\u2212 ligand binds with the thiol\u00adate S, the imine N and the phenolate O atoms as donors, resulting in an FeIIIS2N2O2 chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions, and mutually trans N atoms. The FeIII ion is in the high-spin state at 100\u2005K. The variable-tem\u00adper\u00adature magnetic susceptibility measurements (5\u2013320\u2005K) are consistent with the presence of a high-spin FeIII ion with D\u00a0= 0.83\u2005(1)\u2005cm\u22121 and g\u00a0= 2.The synthesis and crystal structure (100\u2005K) of the title com\u00adpound, [(CH IR spectroscopic measurements of (I)\u22121 were carried out at room tem\u00adper\u00adature using an ATR  PerkinElmer FT\u2013IR Frontier spectrometer.A room-tem\u00adper\u00adature IR spectrum of 3-eth\u00adoxy\u00adsalicyl\u00adalde\u00adhyde thio\u00adsemicarbazone within the range 4000\u2013400\u2005cm1H and 13C NMR spectra were recorded in DMSO-d6 (dimethyl sulfoxide) using a Bruker cryomagnet BZH 300/52 spectrometer (300\u2005MHz), with the recorded chemical shifts in \u03b4 (in parts per million) relative to an inter\u00adnal standard of tetra\u00admethyl\u00adsilane (TMS).M, versus tem\u00adper\u00adature, T, were conducted between 5 and 320\u2005K, heating and cooling at a rate of 2\u2005K\u2005min\u22121 in an applied field, \u03bc0H, of 0.1\u2005T using a Quantum Design MPMS-5S super\u00adconducting quantum inter\u00adference device (SQUID) magnetometer. The SQUID magnetometer was calibrated using a standard palladium sample. The background due to the sample holder and the diamagnetic signal of the sample, estimated using Pascal\u2019s constants  magnetic susceptibility, \u03c72-3-OEt-thsa) was carried out according to the general procedure described by Yemeli Tido : \u03b4 (ppm) 11.39 , 9.02 , 8.40 , 7.90\u20138.13 , 6.72\u20137.50 , 4.05 , 1.35 . 13C NMR : \u03b4 (ppm) 182.8 (C=S), 147.4, 146.7 (C\u2014O), 140.1 (C=N), 119.5, 118.7, 114.5 (C aromatic), 64.6 (C\u2014N), 74.0 (O\u2014CH2), 15.1 (O\u2014C\u2014CH3). IR : 3400 (\u03bdOH), 3169 (\u03bdNH), 3249 (\u03bdNH2), 2935 (\u03bdCH3), 2896 (\u03bdCH2), 1618 (\u03bdC=N), 1535\u20131600 (\u03bdC=C), 1270 (\u03bdC\u2014N), 1167 (\u03bdC=S).The synthesis of 3-eth\u00adoxy\u00adsalicyl\u00adaldehyde thio\u00adsemi\u00adcar\u00adba\u00adzone (HTido 2010 (yield: 3)2NH2][Fe(3-OEt-thsa)2], (I)3)3\u00b79H2O  was dissolved in water (10\u2005ml). The ligand H2-3-OEt-thsa  was dissolved in methanol (60\u2005ml) with the addition of di\u00admethyl\u00adamine, 40\u2005wt% in water . To this mixture, the FeIII salt solution was added dropwise with constant stirring. The resulting dark-green solution was stirred and heated to 80\u2005\u00b0C for approximately 10\u2005min. The solution was then allowed to stand at room tem\u00adper\u00adature until crystals had formed. The dark-green microcrystals were isolated by filtration and dried . IR : 3436, 3414 (\u03bdNH), 3265, 3098 (\u03bdNH2), 3012 (\u03bdCH3), 2971 (\u03bdCH2), 1614, 1586 (\u03bdC=N), 1570\u20131541 (\u03bdC=C ring), 1238 (\u03bdC\u2014O), 1215 (\u03bdN\u2014N), 1078 (\u03bdC\u2014N), 736 (\u03bdC\u2014S).The synthesis of ferrate(III), (I)P21/n, with Z\u00a0= 4. The asymmetric unit consists of one formula unit, [(CH3)2NH2][Fe(3-OEt-thsa)2], with no atom on a special position. The FeIII cation is coordinated by the thiol\u00adate S, phenolate O and imine N atoms of each of the two dianionic O,N,S-tridentate L2\u2212 ligands. The donor atoms of the ligands are situated in two perpendicular planes, with the O and S atoms in cis positions, and mutually trans N atoms. Selected geometric parameters are listed in Table\u00a02The structure of di\u00admethyl\u00adammonium bis\u00ad com\u00adpound at 103 (and 298\u2005K)  confirm that the FeIII cation can be related to the bond angles of the FeO2N2S2 coordination core. An analysis of the bond angles involving the opposite ligand donor atoms at 100\u2005K is very enlightening, as it shows that the octa\u00adhedral geometry of the present high-spin FeIII com\u00adpound, with O1\u2014Fe1\u2014S1\u00a0= 158.48\u2005(5)\u00b0, O101\u2014Fe1\u2014S101\u00a0= 158.89\u2005(5)\u00b0 and N1\u2014Fe1\u2014N101\u00a0= 167.63\u2005(7)\u00b0, is considerably less regular than that of the low-spin com\u00adpound Cs[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH, with the bond angles S11\u2014Fe\u2014O11\u00a0= 177.83\u2005(14)\u00b0, S21\u2014Fe\u2014O21\u00a0= 178.01\u2005(13)\u00b0 and N11\u2014Fe\u2014N21\u00a0= 178.9\u2005(2)\u00b0 \u00b0 and O101\u2014Fe\u2014N101\u00a0= 84.03\u2005(7)\u00b0] than the five-mem\u00adbered chelate ring [S1\u2014Fe\u2014N1\u00a0= 78.45\u2005(5)\u00b0 and S101\u2014Fe\u2014N101\u00a0= 78.93\u2005(5)\u00b0]. The r.m.s. deviations from their least-squares plane of atoms of the six-mem\u00adbered chelate ring of both coordinated ligands are 0.197 and 0.177\u2005\u00c5 for Fe1/N11/C17/C11/C12/O11 and Fe1/N101/C107/C101/C102/O101, respectively, and the corresponding values for the five-mem\u00adbered chelate rings are 0.129 and 0.102\u2005\u00c5 for Fe1/N11/C12/C18/S11 and Fe1/N101/C102/C108/S101, respectively. It appears that the metal chelate rings deviate slightly from the ideal planar structure. Furthermore, the O\u2014Fe\u2014N and S\u2014Fe\u2014N bite angles of the six- and five-mem\u00adbered chelates are deficient by ca 38 and 30\u00b0, respectively, com\u00adpared to the angle at the vertex of a regular hexa\u00adgon (120\u00b0) or penta\u00adgon (108\u00b0), respectively. In com\u00adparison to other (cation+)[Fe(L2\u2212)2]\u00b7x(solvent) com\u00adpounds of related ligands  com\u00adpounds contain FeIII in the low-spin state, whereas the present com\u00adpound contains FeIII in the high-spin state. Consequently, (I) displays longer FeIII\u2013donor atom bond lengths, which are associated with more restricted bite angles. Moreover, the remaining bond angles involving each six-mem\u00adbered chelate ring  or the thiol\u00adate S (S1 and S101) atoms. The charge of the two g Table\u00a02 are, as III com\u00adplex is further enhanced by the high degree of electron delocalization throughout the chelated ligands, which is evident from the geometric parameters. The C\u2014S, C\u2014N and N\u2014N bond lengths of (I)i.e. single bond) and 2 (i.e. double bond). The C8\u2014S1 bond length of 1.746\u2005(3)\u2005\u00c5 and the C108\u2014S101 bond length of 1.752\u2005(2)\u2005\u00c5 suggest partial electron delocalization of these C\u2014S bonds. This feature has also been found in the structure of the related high-spin FeIII com\u00adpound Cs[Fe(thsa)2] at 103\u2005K  at 100\u2005K of 1.301\u2005(3) and 1.301\u2005(3)\u2005\u00c5, respectively, which correspond to the C\u2014N bond lengths of 1.314\u2005(10) and 1.303\u2005(11)\u2005\u00c5, respectively, for Cs[Fe(thsa)2] at 103\u2005K OLEX2 versus tem\u00adper\u00adature measurements for (I)III ion. The data collected on heating and cooling coincide over the tem\u00adper\u00adature range studied. The tem\u00adper\u00adature dependence of \u03c7MT collected on cooling between 320 and 5\u2005K is displayed in Fig.\u00a03MT is tem\u00adper\u00adature independent with a value of 4.41\u2005(1)\u2005cm3\u2005K\u2005mol\u22121 [5.94\u2005(1)\u2005\u00b5B/Fe]. This is just above the expected value of 4.38\u2005cm3\u2005K\u2005mol\u22121 (5.92\u2005\u00b5B/Fe) for FeIII in its high-spin (S\u00a0= 5/2) state with an electronic g factor of 2. \u03c7M\u22121(T) is linear in T and a fit to a Curie\u2013Weiss law between 100 and 320\u2005K shown in Fig.\u00a04B/Fe.Magnetic susceptibility MT drops rapidly below 100\u2005K. This may be due to weak (anti\u00adferro)magnetic inter\u00adactions between neighbouring spins or may reflect a splitting of the S\u00a0= 5/2 state  term HCEF\u00a0= D[zS2 \u2212 S(S\u00a0+\u00a01)/3] + E(xS2 \u2013 yS2), with D and E being the axial and rhombic zero-field splitting, respectively. The 6S high-spin state is split into three Kramers doublets. For E\u00a0= 0, the doublets are separated by 2D and 6D from the lowest energy doublet. The Zeeman energy zH\u00a0= g\u03bcBzHS and the molar susceptibility with a field along z isX\u00a0= D/kBT, NA is Avogadro\u2019s number and kB is the Boltzmann constant \u2005cm\u22121 with g\u00a0= 2. D is in the range expected for high-spin FeIII  spectroscopy.\u03c7 al. 2002, but theIII com\u00adpounds that have so far been reported to contain the 3-eth\u00adoxy\u00adsalicyl\u00adaldehyde 4-R\u2032-thio\u00adsemi\u00adcar\u00adba\u00adzon\u00adate(2\u2212) dianion. In Cs[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH 2NH2][Fe(3-OEt-thsa)2] com\u00adpound, (I)R\u2032 substituent on the terminal N atom of the thio\u00adsemicarbazide moiety, as (I) contains a H atom, whereas Cs[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH 2NH2+versus Cs+; and (iii) the presence of a methanol solvent mol\u00adecule in the crystal lattice of Cs\u00ad[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH , whereas Cs\u00ad[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH forms inter\u00admole\u00adcular hydro\u00adgen-bonded ring systems which link neighbouring FeIII entities. These factors determine the arrangement of the FeIII entities within the unit cell, which is further characterized by the space group P21/n, with Z\u00a0= 4 and V\u00a0= 2576.35\u2005(17)\u2005\u00c53 for (I), with a volume of 644.09\u2005\u00c53 per high-spin FeIII formula unit, and the space group PZ\u00a0= 2 and V\u00a0= 1369.5\u2005(8)\u2005\u00c53 for Cs[Fe(3-OEt-thsa-Me)2]\u00b7CH3OH, with a volume of 684.75\u2005\u00c53 per low-spin FeIII formula unit [Fe(L2\u2212)2]\u00b7x(solvent) materials and allows for a variation of the spin state of FeIII, with some members dis\u00adplaying tem\u00adper\u00adature-dependent spin-crossover behaviour  I, global. DOI: 10.1107/S2053229622011597/jx3075Isup2.hklStructure factors: contains datablock(s) I. DOI: 2223775CCDC reference:"}
{"text": "C(8) chains along the [100] direction. C\u2014Br\u22ef\u03c0 inter\u00adactions connect these chains into parallel layers to (002). van der Waals inter\u00adactions between the layers aid in the cohesion of the crystal packing.C\u2014H\u22efBr inter\u00adactions connect mol\u00adecules in the crystal, resulting in zigzag  14H8Br3N3O2, consists of three almost planar groups: the central di\u00adbromo\u00adethenyldiazene fragment and two attached aromatic rings. The mean planes of these rings form dihedral angles with the plane of the central fragment of 26.35\u2005(15) and 72.57\u2005(14)\u00b0 for bromine- and nitro-substituted rings, respectively. In the crystal, C\u2014H\u22efBr inter\u00adactions connect mol\u00adecules, generating zigzag C(8) chains along the [100] direction. These chains are linked by C\u2014Br\u22ef\u03c0 inter\u00adactions into layers parallel to (001). van der Waals inter\u00adactions between the layers aid in the cohesion of the crystal packing. The most substantial contributions to crystal packing, according to a Hirshfeld surface analysis, are from Br\u22efH/H\u22efBr (20.9%), C\u22efH/H\u22efC (15.2%), O\u22efH/H\u22efO (12.6%) and H\u22efH (11.7%) contacts.The mol\u00adecule of the title compound, C The crystal packing is consolidated by C\u2014F\u22ef\u03c0 contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions, and short Br\u22efO [2.9828\u2005(13)\u2005\u00c5] distances are also observed. In the crystal of (III), the mol\u00adecules are linked into inversion dimers via short halogen\u2013halogen contacts  compared to the van der Waals radius sum of 3.50\u2005\u00c5 for two chlorine atoms. No other directional contacts could be identified, and the shortest aromatic ring centroid separation is greater than 5.25\u2005\u00c5. In the crystals of (IV) and (V), the mol\u00adecules are linked through weak X\u22efCl contacts [X = Cl for (IV) and Br for (V)], C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets lying parallel to (001). In the crystal of (VI), the mol\u00adecules are stacked in columns parallel to [100] via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In (VII), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running parallel to [001]. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In (VIII), C\u2014H\u22efN and short Cl\u22efCl contacts are observed, and in (IX), C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short Cl\u22efO contacts occur.In -1-(4-bromo\u00adphen\u00adyl)-2-(4-nitro\u00adbenzyl\u00adidene)hydrazine (1\u2005mmol), tetra\u00admethyl\u00adethylene\u00addi\u00adamine , CuCl  and CBr4 (4.5\u2005mmol). After 1-3\u2005h , the reaction mixture was poured into 0.01 M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005mL). The combined organic phase was washed with water (3 \u00d7 50\u2005mL), brine (30\u2005mL), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Red solid (58%); m.p. 398\u2005K. Analysis calculated for C14H8Br3N3O2 (M = 489.95): C 34.32, H 1.65, N 8.58; found: C 34.27, H 1.70, N 8.56%. 1H NMR  \u03b4 8.16\u20137.41 . 13C NMR  \u03b4 150.89, 149.62, 148.26, 136.43, 132.25, 127.77, 125.57, 124.53, 123.57, 93.24. ESI\u2013MS: m/z: 490.96 [M + H]+.This dye was synthesized according to the reported method (Akkurt 6.Uiso(H) = 1.2Ueq(C). One reflection (110), affected by the beam stop, was omitted in the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902200620X/yk2170sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902200620X/yk2170Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902200620X/yk2170Isup3.cmlSupporting information file. DOI: 2178832CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The synthesis and structures of dinuclear palladium complexes with 1,3-benzimidazolidine-2-thione and 1,3-imidazoline-2-thione are reported. H-benzimidazole-2-thiol\u00adato)-\u03ba2N3:S;\u03ba2S:N3-bis\u00ad[cyanido(tri\u00adphenyl\u00adphosphine-\u03baP)palladium(II)], [Pd2(C7H5N2S)2(CN)2(C18H15P)2] or [Pd22(CN)2(PPh3)2] (1), and bis\u00ad(\u03bc-1H-imidazole-2-thiol\u00adato)-\u03ba2N3:S;\u03ba2S:N3-bis\u00ad[cyanido(tri\u00adphenyl\u00adphosphine-\u03baP)palladium(II)] aceto\u00adnitrile 0.58-solvate, [Pd2(C3H3N2S)2(CN)2(C18H15P)2]\u00b70.58C2H3N or [Pd22(CN)2(PPh3)2]\u00b70.58C2H3N (2). The compound [Pd22(CN)2(PPh3)2] is located on a crystallographic twofold axis while [Pd22(CN)2(PPh3)2]. 0.58(C2H3N) contains two partially occupied aceto\u00adnitrile solvent mol\u00adecules with occupancies of 0.25 and 0.33. In both of these compounds, the anionic bzimtH\u2212 and imtH\u2212 ligands coordinate through N,S-donor atoms in a bridging mode, covering four coordination sites of two metal centers and other two sites are occupied by two PPh3 ligand mol\u00adecules. Finally, the remaining two sites of two metal centers are occupied by cyano groups, abstracted by the metals from the solvent during reaction. In the packing of the 1,3-benzimidazolidine- 2-thione and 1,3-imidazoline-2-thione complexes, there are intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions involving the thione moiety as well as an N\u2014H\u22efN hydrogen bond linking the thione and cyano ligands. In addition, in 2, as well as the \u03c0\u2013\u03c0 inter\u00adaction involving the thione moieties, there is an additional \u03c0\u2013\u03c0 inter\u00adaction involving one of the thione moieties and an adjacent phenyl ring from the tri\u00adphenyl\u00adphosphine ligand. There are also C\u2014H\u22efN inter\u00adactions between the imidazoline rings and the aceto\u00adnitrile N atoms.The synthesis and structures of dinuclear palladium complexes with 1,3-benz\u00adimidazolidine-2-thione (bzimtH) and 1,3-imidazoline-2-thione (imtH) are reported, namely, bis\u00ad(\u03bc-1 However, the X-ray crystal structure of the product revealed the formation of the unexpected dinuclear compound [Pd22(CN)2(PPh3)2] (1). Another thio-ligand, imtH2 yielded a similar dinuclear compound, [Pd22-(CN)2(PPh3)2] (2). In both these compounds, the anionic bzimtH\u2212 and imtH\u2212 ligands coordinate through N,S donor atoms in a bridging mode, covering four coordination sites of two metal centers, and other two sites are occupied by two PPh3 ligand mol\u00adecules. Finally, the remaining two sites of two metal centers are occupied by cyano groups, abstracted by the metals from the solvent during reaction.The reaction of PdCl1 crystallizes in the monoclinic space group C2/c, and compound 2 in the monoclinic space group, P21/c. Selected bond distances and bond angles are given in Tables 11 is shown in Fig.\u00a012 is shown in Fig.\u00a021, here only half of the mol\u00adecule is unique as the mol\u00adecule lies on a crystallographic twofold axis. In 1, the Pd metal atom is bonded to one P, one S, one N and one C atoms with the respective bond distances as follows: Pd\u2014P = 2.2861\u2005(6), Pd\u2014S = 2.3547\u2005(6), Pd\u2014N = 2.0545\u2005(17), and Pd\u2014C = 1.959\u2005(2)\u2005\u00c5. The trans bond angles, P\u2014Pd\u2014S and N\u2014Pd\u2014C, of 172.26\u2005(2) and 178.31\u2005(8)\u00b0, as well as the cis bond angles in the range 84.93\u2005(6)\u201394.24\u2005(5)\u00b0, reveal the distorted square-planar geometry of each metal center. One of the major factors in the conformation adopted by the mol\u00adecule is the strong \u03c0\u2013\u03c0 inter\u00adaction between the thione moieties , as seen in Fig.\u00a01Cg\u22efCg = 3.3560\u2005(9)\u2005\u00c5 with a slippage of 1.408\u2005\u00c5].Compound 2 is similar to that of 1. Nevertheless, there are minor differences in the bond distances and angles pertaining to the two metal centers of compound 2 , 2.3541\u2005(5), 2.0345\u2005(17) and 1.957\u2005(2)\u2005\u00c5 , and 2.2984\u2005(5), 2.3542\u2005(5), 2.0345\u2005(17) and 1.943\u2005(2)\u2005\u00c5 . For both metal centers, the trans bond angles [P\u2014Pd\u2014S and N\u2014Pd\u2014C = 173.86\u2005(2)\u2013179.31\u2005(8)\u00b0] and the adjacent bond angles [86.54\u2005(7)\u2013 92.80\u2005(4)\u00b0] are similar to those of compound 1. These bond angles again reveal the distorted square-planar geometry of each metal center of compound 2. The various bond distances described above are normal and none unusual. Compound 1 has carbon\u2013sulfur (C\u2014S) bond distance of 1.728\u2005(2), while in compound 2 it is 1.734\u2005(2)\u2005\u00c5. These distances are in between single (1.81\u2005\u00c5) and double-bond (1.68\u2005\u00c5) C\u2014S distances  /1.148\u2005(3)\u2005\u00c5 in compound 2. These distances are less than the expected C=N double bond (1.28\u2005\u00c5) and are close to the C\u2261N triple bond distance \u2005\u00c5], as seen in Fig.\u00a02Cg\u22efCg distances of 3.3065\u2005(8)\u2005\u00c5 and 3.3218\u2005(8), respectively, with a slippage for the latter of 1.154\u2005\u00c5].The coordination pattern of compound  2 Fig.\u00a02. Thus, t2 ligand showed a \u03bd(N\u2014H) band at 3113 (m), and in compound 1, this band appeared at a lower energy, 3055 (m) cm\u22121. The ligand showed a diagnostic \u03bd(C=S) band at 1179\u2005cm\u22121, which shifted to \u03bd(C=S), 1033(s) cm\u22121, owing to the change of neutral bzimtH2 ligand to the bzimtH\u2212 anionic form, coordinating through N,S donor atoms. The PPh3 ligand showed its characteristic \u03bd(P\u2014CPh) band at 1097(s) cm\u22121 in compound 1. A band at 1734\u2005cm\u22121 was assigned to the coordinated cyano group. The IR spectroscopic bands of compound 2 are similarly assigned: \u03bd(N\u2014H), 3050 (m), \u03bd(C=S), 1020 (m), \u03bd(P\u2014CPh), 1105 (s) and \u03bd(C\u2261N), 1740(s) cm\u22121.The IR spectrum of the bzimtH2) has formed an N,S-bonded symmetrically bridged dinuclear compound, and so is the case with 1,3-imidazolidine-2-thione, and these are analogous to literature reports , 1,3-benzimidazoline-2-thione (bzimtH2), 1,3-imidazoline-2-thione (imtH2), and tri\u00adethyl\u00adamine were procured from Aldrich. The solvents  were of HPLC grade and were stored over mol\u00adecular sieves. The precursor, PdCl2(PPh3)2, was prepared by a literature procedure  chloride, tri\u00adphenyl\u00adphosphine (PPh2(PPh3)2]Preparation of the precursor, [PdClin vacuo, m.p. 551-553\u2005KPalladium(II) chloride  was dissolved in hot aceto\u00adnitrile (25\u2005mL) in a 50\u2005mL round-bottom flask, and to it was added tri\u00adphenyl\u00adphosphine . The contents were refluxed for 1\u2005h and the yellow complex formed was filtered and dried 1Preparation of 2(PPh3)2  in 10\u2005mL of CH3CN, was added solid bzimtH2  followed by the addition of Et3N base (0.5\u2005mL). The solution became yellowish orange and was refluxed for 6\u2005h. The orange compound was formed on refluxing. It was separated and dissolved in a solution of methanol (4\u2005mL) and di\u00adchloro\u00admethane (1\u2005mL) in a culture tube. A slow evaporation of the reaction mixture over a period of one month, resulted in the formation of orange crystals of compound 1. Yield: 0.015\u2005g; 65%; m.p. 511\u2013513\u2005K. Analysis found: C, 57.71; H, 3.84; N, 7.50; C52H40N6P2Pd2S2 (1087.8) requires: C, 57.40; H, 3.70; N, 7.72%. IR Data : \u03bd(N\u2014H), 3055 (m); \u03bd(C\u2013H), 2950 (m), 2920 (s), 2852 (m); \u03bd(C\u2261N), 1734 (s), \u03bd(C\u2014C) + \u03b4(N\u2014H) + \u03b4(C\u2014H), 1635 (m), 1440 (s), 1380 (m); \u03bd(P\u2014CPh), 1097 (s); \u03bd(C=S), 1033 (s). Ligand IR Data: \u03bd(N\u2014H), 3113 (m), \u03bd(C\u2014H), 3078 (m); 2981 (s); \u03bd(C\u2261N) 1513 (s), \u03b4(N\u2014H), 1467 (s), 1381 (m); \u03bd(C=S), 1179 (s). The compound is partially soluble in di\u00adchloro\u00admethane, but soluble in methanol and chloro\u00adform.To a solution of PdCl2Preparation of 2(PPh3)2  in 10\u2005mL of CH3CN, was added solid imtH2  followed by the addition of Et3N base (0.5\u2005mL). The solution became yellowish orange and was refluxed for 6\u2005h. The orange compound was formed on refluxing and was separated. It was dissolved in a solution of methanol (4\u2005mL) and di\u00adchloro\u00admethane (1\u2005mL) in a culture tube. Slow evaporation of the reaction mixture over a period of one month formed yellowish-orange crystals of compound 2. Yield: 0.020\u2005g; 69%; m.p. 485\u2013488\u2005K. Analysis found: C, 53.21; H, 3.92; N, 8.48; C44H36N6P2Pd2S2\u00b70.58(CH3CN) (1011.5) requires: C, 53.58; H, 3.73; N, 8.36%. IR bands : \u03bd(N\u2014H), 3050 (m); \u03bd(C\u2014H), 3081 (s), 3005 (m), 2968 (m), 2938 (m); \u03bd(C\u2261N), 1740 (s), d(N\u2014H) + \u03bd(C\u2261N) + \u03b4(C\u2014H), 1581 (s), 1479 (s), 1401(s); \u03bd(C=S), 1020 (m); \u03bd(P\u2014CPh), 1105 (s); Ligand IR data: \u03bd(N\u2014H), 3130 (s), \u03bd(C\u2014H), 2983 (m); 2876 (s); \u03bd(C\u2261N) 1586 (s), \u03b4(N\u2014H), 1478 (s), 1266 (m); \u03bd(C=S), 1120 (m). The compound is soluble in methanol, chloro\u00adform and partially in di\u00adchloro\u00admethane.To the solution of PdCl6.Uiso(H) = 1.2Ueq(C). The structure of 2 contains partially occupied aceto\u00adnitrile solvent mol\u00adecules with occupancies of 0.33 and 0.25.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989023000166/ex2063sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989023000166/ex20631sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989023000166/ex20632sup3.hklStructure factors: contains datablock(s) 2. DOI: 2234599, 2234598CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title charge-neutral complex is a low-spin complex with a moderately distorted pseudo-octa\u00adhedral coordination environment of the metal ion. As a result of their asymmetric shape, the mol\u00adecules stack into chains, which eventually pack into layers and, finally, into a three-dimensional network connected by weak C\u2014H\u22efN, C\u2014H\u22efC hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. II(C17H12BrN6O)2]\u00b72MeOH, consists of a charge-neutral complex mol\u00adecule and two independent mol\u00adecules of methanol. In the complex mol\u00adecule, the two tridentate ligand mol\u00adecules 2--6-(1H-pyrazol-1-yl)pyridine coordinate to the FeII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa\u00adhedral coordination sphere around the central ion. In the crystal, neighbouring asymmetric mol\u00adecules are linked through weak C\u2014H(pz)\u22ef\u03c0(ph) inter\u00adactions into chains, which are then linked into layers by weak C\u2013H\u22efN/C inter\u00adactions. Finally, the layers stack into a three-dimensional network linked by weak inter\u00adlayer C\u2014H\u22ef\u03c0 inter\u00adactions between the meth\u00adoxy groups and the phenyl rings. The inter\u00admolecular contacts were qu\u00adanti\u00adfied using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H\u22efH 34.2%, H\u22efC/C\u22efH 25.2%, H\u22efBr/Br\u22efH 13.2%, H\u22efN/N\u22efH 12.2% and H\u22efO/O\u22efH 4.0%. The average Fe\u2014N bond distance is 1.949\u2005\u00c5, indicating the low-spin state of the FeII ion. Energy framework analysis at the HF/3\u201321\u2005G theory level was performed to qu\u00adantify the inter\u00adaction energies in the crystal structure.The unit cell of the title compound, [Fe The two independent methanol mol\u00adecules form O\u2014H\u22efN hydrogen bonds with the triazole (trz) rings of the ligand mol\u00adecules Fig.\u00a01. The cends Fig.\u00a01.6 coordination environment , where \u03c6i is the angle N\u2013Fe\u2013N\u2032 , where \u03b8i is the angle generated by superposition of two opposite faces of an octa\u00adhedron  but is, however, in the expected range for bis\u00adazole\u00adpyridines and similar ligands (see below). The calculated continuous shape measure (CShM) value relative to the ideal hO symmetry is 2.24 \u2005\u00c5 . Through weak inter\u00admolecular C\u2014H\u22ef N/C inter\u00adactions in the range 3.128\u2005(14)\u20133.734\u2005(11)\u2005\u00c5 . The layers stack with inter\u00adlayer inter\u00adactions limited to C\u2014H\u22efN(trz) and C\u2014H\u22ef\u03c0(ph) contacts involving the methyl groups . The voids between the layers are occupied by methanol mol\u00adecules, which also participate in bonding between neighbouring layers \u22ef\u03c0(ph) inter\u00admolecular contact between the pyrazole (pz) and phenyl (ph) groups respectively Table\u00a01. The mon\u00c5 Table\u00a01, neighbone Fig.\u00a02b,c. Theps Fig.\u00a02c. The v4.CrystalExplorer  to 2.4335 (blue) a.u. , the dispersion forces (Edis) and the total energy diagrams (Etot), are shown in Fig.\u00a05Edis), reflecting the dominating inter\u00adactions in the lattice of the neutral asymmetric mol\u00adecules. The topology of the energy framework resembles the topology of the inter\u00adactions within and between the layers described above. The calculated values Etot are in the range 65.2\u201387.6\u2005kJ\u2005mol\u22121 for intra\u00adchain and intra\u00adlayer inter\u00adactions, whereas for the inter\u00adlayer inter\u00adactions they are within 7.7\u201323.4\u2005kJ\u2005mol\u22121. The colour-coded inter\u00adaction mappings within a radius of 3.8\u2005\u00c5 of a central reference mol\u00adecule for the title compound together with full details of the various contributions to the total energy (Etot) are given in the supporting information.The energy framework  change correspondingly, and in the low-spin state they are systematically lower than in the high-spin state. Table\u00a02A search of the Cambridge Structural Database ](BF4)2 prepared by dissolving L = 2--6-(1H-pyra\u00adzol-1-yl)pyridine  and Fe(BF4)2\u00b76H2O  in boiling acetone, to which chloro\u00adform (5\u2005ml) was then added. The middle layer was a methanol\u2013chloro\u00adform mixture , which was covered by a layer of methanol (10\u2005ml), to which 100\u2005\u00b5l of NEt3 was added dropwise. The tube was sealed, and black cubic single crystals appeared in 3\u20134 weeks (yield ca 60%). Elemental analysis calculated for C36H32Br2FeN12O4: C, 47.39; H, 3.54; N, 18.42. Found: C, 47.11; H, 3.74; N, 18.40.The synthesis of the title compound is identical to that reported recently for a similar complex (Seredyuk 8.Uiso(H) = 1.2\u20131.5Ueq(C)]. O-bound H atoms were refined with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022010179/dj2053sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022010179/dj2053Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022010179/dj2053Isup4.cdxSupporting information file. DOI: 10.1107/S2056989022010179/dj2053sup3.pdfIncludes energy framework data and schematic structures of similar neutral Fe(II) complexes. DOI: 2215273CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Mutations can occur in G\u03b1 proteins which prevent GTP hydrolysis; this allows the G proteins to signal independently of G protein\u2013coupled receptors and can result in various cancers, such as uveal melanoma (UM). Most UM cases harbor Q209L, Q209P, or R183C mutations in G\u03b1q/11 proteins, rendering the proteins constitutively active (CA). Although it is generally thought that active, GTP-bound G\u03b1 subunits are dissociated from and signal independently of G\u03b2\u03b3, accumulating evidence indicates that some CA G\u03b1 mutants, such as G\u03b1q/11, retain binding to G\u03b2\u03b3, and this interaction is necessary for signaling. Here, we demonstrate that disrupting the interaction between G\u03b2\u03b3 and G\u03b1q is sufficient to inhibit aberrant signaling driven by CA G\u03b1q. Introduction of the I25A point mutation in the N-terminal \u03b1 helical domain of CA G\u03b1q to inhibit G\u03b2\u03b3 binding, overexpression of the G protein G\u03b1o to sequester G\u03b2\u03b3, and siRNA depletion of G\u03b2 subunits inhibited or abolished CA G\u03b1q signaling to the MAPK and YAP pathways. Moreover, in HEK 293\u00a0cells and in UM cell lines, we show that G\u03b1q-Q209P and G\u03b1q-R183C are more sensitive to the loss of G\u03b2\u03b3 interaction than G\u03b1q-Q209L. Our study challenges the idea that CA G\u03b1q/11 signals independently of G\u03b2\u03b3 and demonstrates differential sensitivity between the G\u03b1q-Q209L, G\u03b1q-Q209P, and G\u03b1q-R183C mutants.Heterotrimeric G protein stimulation  Q209L or Q209P mutations in G\u03b1q or G\u03b111 occur in 90% of UM patients, and mutations at R183 occur in about 5% of patients (Heterotrimeric G proteins (G\u03b1\u03b2\u03b3) are canonically activated through G protein\u2013coupled receptors (GPCRs), which allows for GDP release from the G\u03b1 subunit and further GTP binding. It is generally accepted that GTP binding on the G\u03b1 subunit promotes an active conformation and allows for the dissociation from G\u03b2\u03b3. Active GTP-bound G\u03b1 proteins can further bind and stimulate downstream effectors , 2. Hydrc tumors , 6. Mutapatients . Approxipatients .q/11 in UM, driven by the activating Q209L/P and R183 mutations, promotes the stimulation of two major signaling pathways: 1) the mitogen-activated protein kinase (MAPK) pathway and 2) the Yes-associated protein and Transcriptional coactivator with PDZ-binding motif (YAP/TAZ) pathway. The MAPK cascade is stimulated by the direct binding of CA G\u03b1q/11 to phospholipase C\u2013\u03b2 (PLC-\u03b2), which hydrolyzes phosphatidylinositol 4,5-bisphosphate into diacylglycerol and inositol 1,4,5-trisphosphate. Diacylglycerol further activates PKC, which phosphorylates and activates RasGRP3. The further activation of Ras promotes the stimulation of the MAPK cascade and results in the phosphorylation and activation of ERK. Phospho-ERK (pERK) dimerizes and translocates into the nucleus to bind transcription factors and promote the transcription of proliferative genes  transcription factor in the nucleus to promote the transcription of genes involved in proliferation and cell survival  and FR900359 (FR) have been shown to inhibit both WT and CA G\u03b1q/11 and have shown promising results in cancer cell models , Q209P (QP), and R183C (RC)\u2014is sufficient to inhibit oncogenic signaling of these mutationally active G\u03b1q. We provide evidence that disrupting the interaction between CA G\u03b1q and G\u03b2\u03b3 significantly inhibits G\u03b1q-mediated activation of the MAPK and YAP/TAZ pathways. Surprisingly, we show differential sensitivity between G\u03b1q-QL and the G\u03b1q-QP/RC mutants in that oncogenic signaling by G\u03b1q-QP and G\u03b1q-RC is more sensitive to the disruption of G\u03b2\u03b3 binding than G\u03b1q-QL.Here, we tested the hypothesis that disrupting the interaction between G\u03b2\u03b3 and the CA G\u03b1q, such as PLC-\u03b2, requires the binding of G\u03b1q to G\u03b2\u03b3 , Q209P (QP), and R183C (RC) mutants. To monitor the activity of the YAP/TAZ pathway, we transfected the CA mutants, with and without the I25A mutation, into HEK 293\u00a0G\u03b1q/11 CRISPR-Cas9 KO cells and monitored YAP activity using the TEAD luciferase reporter assay, which is stimulated in response to YAP activation and nuclear translocation. G\u03b1q-QL, G\u03b1q-QP, and G\u03b1q-RC all showed strong activation in the assay. Cells expressing the pcDNA3 vector and WT G\u03b1q were used as negative controls and indicated no significant change in TEAD luciferase reporter activity (A). The G\u03b1q-QL-C9,10S palmitoylation-deficient mutant was used as a negative control for G\u03b1q-QL. The C9,10S mutation in WT G\u03b1q has been previously established to prevent plasma membrane localization and consequently prevent GPCR-dependent activation . It has been previously established that activation of the Rho-dependent YAP pathway results in stabilization and dephosphorylation of YAP and its subsequent translocation into the nucleus  as a control resulted in the loss of nuclear YAP and its accumulation in the cytoplasm. G\u03b1q-I25A-QL also promoted nuclear localization of YAP, consistent with its retention of signaling in the TEAD-luciferase assay (A). Cells expressing CA G\u03b1q-QP and G\u03b1q-RC had robust nuclear YAP localization, indicating stimulation of this pathway. However, G\u03b1q-I25A-QP and G\u03b1q-I25A-RC failed to stimulate the nuclear localization of YAP, as indicated by the cytoplasmic localization of YAP. Similar to the TEAD-luciferase reporter assay results, this data suggests that G\u03b1q-I25A-QL is more resistant to disruption of signaling than the G\u03b1q-I25A-QP and G\u03b1q-I25A-RC mutants. In immunofluorescence microscopy studies, we also examined the subcellular localization of the CA G\u03b1q mutants with and without the I25A mutation . Expression of CA G\u03b1q-QL resulted in pERK stimulation >4-fold compared to cells transfected with pcDNA3 or WT G\u03b1q. The G\u03b1q-I25A-QL mutant also activated pERK at a slightly decreased level compared to G\u03b1q-QL, although the difference was not statistically significant. Interestingly, the G\u03b1q-QP and G\u03b1q-RC mutants stimulated pERK, but pERK activity was significantly decreased in cells expressing the G\u03b1q-I25A-QP and G\u03b1q-I25A-RC mutants (C and D). The effects of the I25A mutants on MAPK activity were further validated with the serum response element (SRE) luciferase reporter assay, which monitors both Rho and MAPK-dependent activity (E). As indicated, the CA G\u03b1q-QL mutant robustly stimulated SRE-dependent luciferase activity. Introduction of the I25A mutation into G\u03b1q-QL (G\u03b1q-I25A-QL) strongly inhibited the ability to stimulate SRE luciferase activity, similar to the lack of signaling by the G\u03b1q-QL-C9,10S palmitoylation-deficient mutant and the loss of signaling upon treatment of cells expressing G\u03b1q-QL with YM. As expected, the CA G\u03b1q-QP and G\u03b1q-RC mutants also robustly stimulated SRE luciferase activity, while the G\u03b1q-I25A-QP and G\u03b1q-I25A-RC mutants completely failed to stimulate luciferase activity, similar to cells treated with YM (E). The decreased signaling by G\u03b1q-I25A-QL in comparison to G\u03b1q-QL is much more drastic in the SRE luciferase assay than the pERK immunoblot assay (C and D). Although this is somewhat surprising since the SRE luciferase readout is downstream of the MAPK pathway, we note that the SRE luciferase assay provides a very high signal-to-noise readout for G\u03b1q-QL signaling  and is consistently very sensitive to disruption of G\u03b1q-QL signaling . Taken together, these results indicate that the introduction of the I25A mutation to disrupt binding to G\u03b2\u03b3 inhibited oncogenic signaling of the CA G\u03b1q mutants through the YAP and MAPK pathways, and the G\u03b1q-QP and G\u03b1q-RC mutants are more sensitive to the I25A mutation than G\u03b1q-QL.Along with stimulation of the YAP pathway, CA G\u03b1 mutants , C and D mutants , C and Dactivity E. As ind with YM E. The deot assay , C and Dq-QL has an increased association with G\u03b2\u03b3 compared to G\u03b1q-RC  and was further quantified (B). As expected, WT G\u03b1q displayed a strong pull down with G\u03b21\u03b32, but the introduction of the I25A mutation into WT G\u03b1q strongly decreased this interaction, indicating that the I25A mutation disrupts binding between G\u03b1q and G\u03b2\u03b3. Interestingly, G\u03b1q-QL had a similar binding association to G\u03b21\u03b32 with that of WT G\u03b1q, and G\u03b1q-QL bound significantly stronger to G\u03b21\u03b32 than G\u03b1q-QP and G\u03b1q-RC (A and B). Furthermore, G\u03b1q-I25A-QL was more strongly bound to G\u03b21\u03b32 than G\u03b1q-I25A-QP and G\u03b1q-I25A-RC (A and B). We did not see a statistically significant difference in association with G\u03b2\u03b3 between G\u03b1q-QP and G\u03b1q-RC and their corresponding I25A mutants. This is likely due to the low initial binding to G\u03b2\u03b3 with both G\u03b1q-QP and G\u03b1q-RC. Although we previously demonstrated the surprising ability of G\u03b1q-QL to interact strongly with G\u03b2\u03b3 and the poor interaction of G\u03b1q-RC with G\u03b2\u03b3, we now show a dramatically decreased association of G\u03b1q-QP with G\u03b2\u03b3 compared to G\u03b1q-QL, even though both have a mutation of Q209. This differential binding to G\u03b2\u03b3 between the CA G\u03b1q mutants likely contributes to the varying sensitivity in oncogenic signal disruption between the I25A mutants . Interestingly, cotransfection with 200\u00a0ng of the G\u03b1o DNA was required to decrease G\u03b1q-QL stimulation of TEAD luciferase activity by 63%. In comparison, cotransfection with 100\u00a0ng of G\u03b1o plasmid DNA achieved 83% and 84% reduction in signaling by G\u03b1q-QP and G\u03b1q-RC, respectively. Transfection with the control G\u03b1o G2A constructs did not reduce the luciferase reporter activity in response to the CA G\u03b1q mutants (A). The ability of the expression of G\u03b1o to reduce CA G\u03b1q-stimulated YAP activity was also monitored through nuclear localization of YAP by immunofluorescence microscopy. G\u03b1o\u00a0localized strongly at cellular membranes, while the G\u03b1o G2A mutant was primarily cytoplasmic, indicating the expected localization of the proteins. Strong nuclear YAP was detected with the CA G\u03b1q-QL, G\u03b1q-QP, and G\u03b1q-RC mutants, indicating stimulation of the YAP pathway (B). As expected, expression of G\u03b1o G2A with the CA G\u03b1q mutants did not disrupt nuclear localization of YAP. Overexpression of G\u03b1o inhibited YAP nuclear localization stimulated by G\u03b1q-QP and G\u03b1q-RC (B). Conversely, cotransfection of G\u03b1o with G\u03b1q-QL failed to prevent strong YAP nuclear localization (B), further suggesting that the G\u03b1q-QP and G\u03b1q-RC mutants are more sensitive to G\u03b2\u03b3 binding disruption than G\u03b1q-QL.Considering that inhibiting the association between the CA G\u03b1in cells , 42, 43.embranes . YAP actplasmids A. Intere mutants A. The ab pathway B. As expd G\u03b1q-RC B. Converlization B, furtheo expression and subsequent G\u03b2\u03b3 sequestration on CA G\u03b1q-promoted MAPK activity, we immunoblotted for pERK levels (A and B). The expression of the CA G\u03b1q mutants resulted in strong stimulation of pERK. Expression of G\u03b1o resulted in no significant decrease in pERK activity for G\u03b1q-QL. However, cotransfection of G\u03b1q-QP or G\u03b1q-RC with 50\u00a0ng and 100\u00a0ng of G\u03b1o plasmid resulted in a strong decrease in pERK activity (A and B). There was no significant change in pERK levels with the G\u03b1o G2A control (A and B). These results were further validated using the SRE luciferase reporter assay (C). Expression of G\u03b1q-QL, G\u03b1q-QP, and G\u03b1q-RC robustly activated SRE-dependent luciferase activity, while treatment with YM abolished luciferase activity. Consistent with results from the other signaling assays (A and B), cotransfection with 50\u00a0ng\u00a0G\u03b1o plasmid was sufficient to completely abolish G\u03b1q-QP\u2013 and G\u03b1q-RC\u2013stimulated SRE luciferase activity, while up to 250\u00a0ng of G\u03b1o plasmid was required for near complete inhibition of G\u03b1q-QL\u2013stimulated SRE luciferase activity (C). These findings indicate that the expression of G\u03b1o to sequester endogenous G\u03b2\u03b3 inhibits the signaling activity of G\u03b1q-QL/P and G\u03b1q-RC. The results also further validate that the G\u03b1q-QL CA mutant is less sensitive to signaling disruption than the G\u03b1q-QP and G\u03b1q-RC mutants.To monitor the effects of G\u03b1K levels , A and Bactivity , A and B control , A and Ber assay C. Expresg assays , A and Bactivity C. These o could sequester G\u03b2\u03b3 and inhibit the binding of G\u03b2\u03b3 to G\u03b1q-QL/P and G\u03b1q-RC. To examine this, we coexpressed G\u03b1o or G\u03b1o G2A with the CA G\u03b1q mutants in 6x-His-G\u03b21y2 HEK 293 stable cells and pulled down G\u03b21\u03b32 with Ni-NTA beads. Immunoblots were used to detect G\u03b1q and G\u03b1o bound to G\u03b21 (A and B). As indicated in q-QL had a stronger binding association with G\u03b21 than G\u03b1q-QP and G\u03b1q-RC. G\u03b1o was bound to G\u03b21 in the pull-down extract, but G\u03b1o G2A had minimal to no interaction with G\u03b21 as expected. The expression of G\u03b1o resulted in significantly decreased binding of G\u03b1q-QL to G\u03b21 (A and B). Expression of G\u03b1o consistently resulted in a noticeable decrease in the pull down of G\u03b1q-QP and G\u03b1q-RC with G\u03b2\u03b3, but this did not reach statistical significance due to the already low level of G\u03b1q-QP and G\u03b1q-RC association with G\u03b2\u03b3 in the absence of G\u03b1o expression. These findings confirm that overexpression of G\u03b1o sequesters G\u03b2\u03b3 and prevents binding of G\u03b1q-QL/P and G\u03b1q-RC to G\u03b2\u03b3.Next, we wanted to confirm that the expression of G\u03b1d to G\u03b21 , A and BL to G\u03b21 , A and Bq through the N-terminal I25A mutation or expression of G\u03b1o is sufficient to inhibit overactive G\u03b1q signaling in HEK 293\u00a0G\u03b1q/11 KO cells. We next wanted to determine if inhibiting G\u03b2\u03b3 binding to CA G\u03b1q would be sufficient to disrupt oncogenic signaling in UM cells containing the G\u03b1q-QL or G\u03b1q-QP mutants. To study this, we depleted G\u03b21 and G\u03b22, two predominant G\u03b2 subunits, through siRNA transfections. Sufficient knockdown of G\u03b21 and G\u03b22 was first validated in HEK 293\u00a0G\u03b1q/11 KO cells (A and B). siRNA molecules specific for G\u03b21, G\u03b22, and both G\u03b21 and G\u03b22 were transfected into the HEK 293\u00a0G\u03b1q/11 KO cells, and WT G\u03b1q, G\u03b1q-QL, or G\u03b1q-QP constructs were transfected after 24\u00a0h. pERK levels were detected and quantified through immunoblotting (A and B). The results indicate that siRNA depletion of G\u03b21/2 significantly disrupted pERK activity driven by both G\u03b1q-QL and G\u03b1q-QP (A and B). G\u03b21 or G\u03b22 siRNA knockdown alone was insufficient to significantly inhibit pERK activation (A and B). Considering the effectiveness of G\u03b21/2 depletion on pERK activity in the HEK 293\u00a0G\u03b1q/11 KO cells, we decided to knock down G\u03b21/2 in four UM cell lines: 1) Mel202 (G\u03b1q-Q209L mutation), 2) 92.1 (G\u03b1q-Q209L mutation), 3) OMM1.3 (G\u03b1q-Q209P mutation), and 4) UM001 (G\u03b1q-Q209P mutation). We also used the OCM-3\u00a0cell line as a control. The oncogenic activity of OCM-3\u00a0cells is driven by mutant BRAF (V600E) as opposed to mutant G\u03b1q/11; thus, we would expect G\u03b21/2 depletion to have minimal effect on pERK activity  and quantified (D). Interestingly, the OMM1.3 and UM001\u00a0cell lines which contain the G\u03b1q-Q209P mutation had significantly decreased pERK levels with G\u03b21/2 knockdown, similar to that of YM treatment (C and D). There was no significant difference in pERK levels with G\u03b21/2 depletion in the Mel202 and 92.1\u00a0cells which contain the G\u03b1q-Q209L mutation (C and D). This data further suggests that there is differential sensitivity to the inhibition of oncogenic signaling between cell lines with the G\u03b1q-Q209L and G\u03b1q-Q209P mutations.Our studies demonstrate that disrupting the interaction between G\u03b2\u03b3 and CA G\u03b1KO cells , A and Bblotting , A and Bd G\u03b1q-QP , A and Btivation , A and Bactivity . All celoblotted C and quaantified D. Interereatment , C and Dmutation , C and Dq and show a surprising differential sensitivity of CA G\u03b1q mutants to the inhibition of signaling upon disruption of their interaction with G\u03b2\u03b3. We used two methods to disrupt G\u03b2\u03b3 interaction with CA G\u03b1q\u2014introduction of a G\u03b2\u03b3-binding disrupting mutation, I25A, into CA G\u03b1q and sequestration of endogenous G\u03b2\u03b3 by expression of G\u03b1o\u2014to show that inhibiting interaction with G\u03b2\u03b3 can drastically reduce CA G\u03b1q-stimulated signaling to both the MAPK and YAP/TAZ pathways. Moreover, signaling by CA G\u03b1q-Q209P, as well as CA G\u03b1q-R183C, was much more effectively prevented by G\u03b2\u03b3 binding disruption than signaling by CA G\u03b1q-Q209L. Lastly, we extended the analysis to UM cell lines containing either the oncogenic driver mutant G\u03b1q-Q209L or G\u03b1q-Q209P and showed that depletion of G\u03b21/2 strongly inhibited activation of the MAPK pathway in cells with the G\u03b1q-Q209P mutant but not in cells with the G\u03b1q-Q209L. Our results suggest that disrupting the interaction between G\u03b2\u03b3 and CA G\u03b1q may be a novel approach for inhibiting aberrant G\u03b1q/11 signaling.The results presented in this study demonstrate the importance of G\u03b2\u03b3 for signaling by CA mutants of G\u03b1q mutants studied herein, it would be expected that CA G\u03b1 mutants would not retain binding to G\u03b2\u03b3. However, several studies have challenged the classical heterotrimer dissociation model, indicating that at least some G\u03b1 subunits maintain association with G\u03b2\u03b3 when they are in the active, GTP-bound state due to the presence of a GTPase-inhibiting mutation or in response to GPCR activation  a central switch region, which undergoes a conformational change upon GTP binding and 2) an N-terminal \u03b1 helical domain . Thus, one reason why CA G\u03b1q mutants in this study showed decreased or loss of signaling to the MAPK and YAP pathways when interaction with G\u03b2\u03b3 is disrupted is a failure to be efficiently palmitoylated and membrane-bound. Indeed, G\u03b1q-I25A-QL retains stronger plasma membrane localization than G\u03b1q-I25A-QP and G\u03b1q-I25A-RC , although only partial loss of signaling was observed in when measuring pERK (C and D). Expression of the increasing amounts of G\u03b1o to sequester G\u03b2\u03b3 provided a powerful tool to demonstrate titratable differences in sensitivity to disruption of G\u03b2\u03b3 binding to the CA G\u03b1q mutants . Using the SRE-luciferase assay, transfection with 50\u00a0ng of G\u03b1o expression plasmid was sufficient to completely abolish signaling of G\u03b1q-QP and G\u03b1q-RC, while transfection with 250\u00a0ng of G\u03b1o plasmid was required to observe a similar almost-complete inhibition of G\u03b1q-QL signaling (C). Likewise, transfection with 50 or 100\u00a0ng of G\u03b1o plasmid failed to inhibit G\u03b1q-QL\u2013stimulated pERK levels, but transfection with 50 or 100\u00a0ng of G\u03b1o plasmid provided significant inhibition of G\u03b1q-QP\u2013 and G\u03b1q-RC\u2013stimulated pERK (A and B). G\u03b2\u03b3 pull-down experiments showed the interaction of G\u03b1q-QL with G\u03b2\u03b3, similar to the levels of WT G\u03b1q interaction with G\u03b2\u03b3, and, importantly, the I25A mutation and expression of G\u03b1o only partially disrupted the interaction . The G\u03b1q-I25A, G\u03b1q-I25A-QL, and G\u03b1q-I25A-RC constructs were previously described . YFP-tagged G\u03b1q was provided by Catherine Berlot. G\u03b1o and G\u03b1o-G2A plasmids were described previously (q and G\u03b1o transient transfections was obtained from Invitrogen (Cat # 11668-019). siRNA targeting G\u03b21 (GGAUAACAUUUGCUCCAUU), G\u03b22 (ACUGGGUACCUGUCGUGUU), and both G\u03b21 and G\u03b22 (G\u03b21/2) (ACGACGACUUCAACUGCAA) were previously described  (for immunoblots with HEK 293\u00a0G\u03b1q/11 KO lysates), GAPDH (Cat # 60004-1-Ig), and G\u03b1o (Cat # 12635-1-AP) were from Proteintech. The G\u03b1q (Cat # ab199533) (for immunofluorescence experiments), G\u03b21 (Cat # ab137635), and G\u03b22 (Cat # ab108504) antibodies were obtained from Abcam. The YAP antibody (Cat # sc-101199) was purchased from Santa Cruz. The G\u03b1q (Cat # 14373S) , ERK (Cat # 4696S), pERK (Cat # 9101S), and Myc-tag (Cat # 2272S) antibodies were obtained from Cell Signaling Technologies. The HA-tag antibody 12CA5 was from Covance. The GRK4-6 antibody (Cat # 05-466) was obtained from Sigma-Aldrich. For immunofluorescence microscopy, the secondary antibodies Alexa Fluor 488 (goat anti-rabbit) (Cat # A-11034), Alexa Fluor 594 (goat anti-mouse) (Cat # A-11032), Alexa Fluor 594 (goat anti-rabbit) (Cat # A-11037), and Alexa Fluor 647 (goat anti-mouse) (Cat # A-32728) were purchased from Invitrogen. The secondary antibodies IRDye 680RD goat anti-rabbit IgG (H\u00a0+ L) (Cat # 92568071) and IRDye 800CW donkey anti-mouse IgG (H\u00a0+ L) (Cat # 92532212) were obtained from LI-COR and were used to visualize protein from all of the immunoblots.The antibodies for G\u03b1q/11 KO cells were generously provided by Dr Asuka Inoue and were described previously  with 10% fetal bovine serum (FBS)  and 1% penicillin/streptomycin . HEK 293\u00a0G\u03b21\u03b32 stable cells were described previously . The SRE luciferase reporter plasmid was described previously  with 1% Triton X-100. For the G\u03b1q-I25A experiments, the cells were incubated with the anti-rabbit G\u03b1q antibody (Abcam) and the anti-mouse YAP antibody in 2.5% milk/TBS-Triton X-100. For the G\u03b1o experiments, the cells were incubated with the anti-rabbit G\u03b1o antibody and the anti-mouse YAP antibody in 2.5% milk/TBS-Triton X-100. The primary antibodies were incubated for 60\u00a0min. The cells were washed 5 times with 2.5% milk/TBS-Triton X-100. For the G\u03b1q-I25A experiments, the cells were incubated with goat anti-rabbit Alexa Fluor 488 and goat anti-mouse Alexa Fluor 594 antibodies in 2.5% milk/TBS-Triton X-100. For the G\u03b1o experiments, the cells were incubated with goat anti-rabbit Alexa Fluor 594 and goat anti-mouse Alexa Fluor 647 antibodies in 2.5% milk/TBS-Triton X-100. The secondary antibodies were incubated for 30\u00a0min. The cells were washed 5 times in TBS/1% Triton X-100. The cells were incubated in DAPI  diluted in warmed PBS for 5\u00a0min. The coverslips were rinsed in distilled water and mounted onto glass slides with ProLong Diamond Anti-fade Mountant . The images were acquired using the Olympus IX83 microscope with a 60\u00d7 oil immersion objective and an ORCA Fusion sCMOS camera (Hamamatsu) controlled by Olympus cellSens software.HEK 293\u00a0G\u03b11\u03b32 pull-down assay was done as previously described . The cell lysates were incubated for 1\u00a0h on ice and were then centrifuged at 13,000\u00a0rpm  to pellet the nuclei and insoluble material. Forty microliters of the lysate were reserved separately for the input fraction. The remaining lysate was added to 30\u00a0\u03bcl of Ni-NTA beads  and rotated in an end-over-end rotator for 2\u00a0h at 4 \u00b0C. The tubes were placed in a magnetic rack, and the remaining supernatant was aspirated. The beads were washed 3 times with lysis buffer C. Fifty microliters of elution buffer (lysis buffer C with 0.25\u00a0M Imidazole) were added to elute G\u03b21 and any bound proteins from the Ni-NTA beads. Forty microliters of the pull-down eluate were transferred to a new tube. Ten microliters of 5\u00d7 SDS-PAGE sample buffer with 3.5% \u03b2-mercaptoethanol were added to the input fraction and the pull-down fraction. The input and pull-down lysates were separated on a 10% SDS-PAGE gel and protein bound was detected via immunoblotting. The blots were probed with the HA-tag and Myc-tag antibody . The blots for the G\u03b1o experiments were also probed with G\u03b1o and GAPDH. The blots were imaged on LI-COR, and the bands were quantified on the ImageJ software (https://imagej.nih.gov/ij/). The pull-down samples in G\u03b1q-I25A experiments were normalized to its respective input fraction. The pull-down samples in the G\u03b1o experiments were normalized to WT G\u03b1q.The G\u03b2escribed . Brieflyq  for the HEK 293\u00a0G\u03b1q/11 KO cells or Cell Signaling G\u03b1q  for the UM cells, along with GAPDH  as a loading control. The ERK and pERK bands were quantified by densitometry using the ImageJ software, and the relative pERK signal was divided by ERK. The quantified signals were normalized to WT G\u03b1q (D), the individual CA G\u03b1q mutants (B), or control siRNA between the CA G\u03b1q mutants (B) or the UM cell lines (D).Cells were lysed in SDS-PAGE sample buffer. Lysates were run on a 10% SDS-PAGE gel and transferred to a nitrocellulose membrane. The membrane was blocked in 2.5% bovine serum albumin (BSA)  in 1\u00d7 TBS supplemented with 0.05% Tween 20. The blots were incubated with both pERK  and ERK  antibodies overnight. A duplicate immunoblot was performed and was probed with either Proteintech G\u03b1o WT G\u03b1q D, the in mutants B, or con mutants B or the ll lines D.q/11 KO cells and 12-well plates for the UM cells. For the HEK 293\u00a0G\u03b1q/11 KO experiments, 30 pmol of control, G\u03b21, G\u03b22, or G\u03b21/2 siRNA were transfected into cells using Lipofectamine RNAiMax , according to manufacturer's instructions. The media was changed after 5\u00a0h. After 24\u00a0h, the corresponding WT G\u03b1q, G\u03b1q-QL, or G\u03b1q-QP constructs were transfected into the cells using Lipofectamine 2000 . The media was changed to serum-free media after 24\u00a0h and corresponding cells were treated with 1\u00a0\u03bcM of YM. The cells were lysed in 1\u00d7 SDS-PAGE sample buffer with 0.7% \u03b2-mercaptoethanol after 16\u00a0h. For experiments with the UM cells, 15pmol of control or G\u03b21/2 siRNA were transfected into cells using Lipofectamine RNAiMax . The media was changed after 5\u00a0h. After 72\u00a0h, the media was changed to serum-free media, and the corresponding cells were treated with 1\u00a0\u03bcM of YM. The cells were further lysed after approximately 16\u00a0h in 1\u00d7 SDS-PAGE sample buffer with 0.7% \u03b2-mercaptoethanol. The lysates were run on 10% SDS-PAGE gels and were immunoblotted for pERK , ERK , G\u03b21 , G\u03b22 , GAPDH , and Proteintech G\u03b1q (Cat #13927-1-AP) for the HEK 293\u00a0G\u03b1q/11 KO cells or Cell Signaling G\u03b1q (Cat # 14373S) for the UM cells.Cells were plated in 6-well plates for the HEK 293\u00a0G\u03b1Protein lysates were run on 10% SDS-PAGE gels and transferred to LI-COR nitrocellulose membranes (Cat # nc9680617). The membranes were blocked in either 2.5% BSA or 2.5% milk in 1\u00d7 TBS/0.05% Tween 20 at room temperature for 60\u00a0min. The blots were incubated in corresponding primary antibodies in 2.5% BSA or milk in 1\u00d7 TBS/0.05% Tween 20 at 4 \u00b0C overnight. The blots were washed three times in 1\u00d7 TBS/0.05% Tween 20 and incubated in LI-COR anti-rabbit (Cat # 92568071) and anti-mouse (Cat # 92532212) secondary antibodies for 60\u00a0min at room temperature. The immunoblots were further washed three times in 1\u00d7 TBS/0.05% Tween 20 and once with PBS. The blots were then imaged on the LI-COR Odyssey imager.B and D) multiple comparison test were used to calculate significance. Error bars in all experiments indicate mean\u00a0\u00b1 SD with significant differences indicated as \u2217p\u00a0< 0.05; \u2217\u2217p\u00a0< 0.01; \u2217\u2217\u2217p\u00a0< 0.005; \u2217\u2217\u2217\u2217p\u00a0< 0.0001.GraphPad Prism was used to analyze the data for all of the figures. A two-way ANOVA followed by \u0160id\u00e1k's or Tukey\u2019s , B and DAll data is contained within the article.This article contains The authors declare that they have no conflicts of interest with the contents of this article."}
{"text": "The synthesis and crystal structure of a new Schiff base, namely, 4-bromo-2-[({2-[(2-hy\u00addroxy\u00adeth\u00adyl)amino]\u00adeth\u00adyl}imino)\u00admeth\u00adyl]phenol, is reported. 11H15BrN2O2, crystallizes in the monoclinic space group P21 with two independent mol\u00adecules in the asymmetric unit. It was prepared by the condensation reaction of 5-bromo-2-hy\u00addroxy\u00adbenzaldehyde and amino\u00adethyl\u00adethano\u00adlamine. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond with an S(6) ring motif. Moreover, there are inter\u00admolecular C\u2014H\u22efN, C\u2014H\u22efO and Br\u22efO inter\u00adactions in the crystal structure of the title compound.The new title Schiff base compound, C Moreover, the O2a and O2b atoms are involved in a second intra\u00admolecular hydrogen bond. The mol\u00adecules are connected through inter\u00admolecular O\u2014H\u22efN hydrogen bonds and Br\u22efO inter\u00adactions with distances Br1a\u22efO2b = 3.206\u2005(2)\u2005\u00c5 and Br1b\u22efO2a = 3.282\u2005(2)\u2005\u00c5  was dissolved in ethanol (10\u2005ml) and stirred for 10\u2005min. Then, a solution of amino\u00adethyl\u00adethano\u00adlamine (0.2\u2005mmol) dissolved in ethanol (5\u2005ml) was added dropwise. The mixture was stirred and refluxed for 6\u2005h. After that, the solution was concentrated under reduced pressure. Yellow crystals suitable for X-ray analysis were obtained by slow evaporation of solvent at room temperature for several days. These were filtered off and washed several times with cold ethanol.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621003357/bt4109sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314621003357/bt4109Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621003357/bt4109Isup3.cmlSupporting information file. DOI: 2074082CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion of the complex cation has an N3O square-planar coordination sphere defined by the three N atoms of the tridentate 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine ligand and one O atom from the NO3\u2212 anion.The central Pd 3)(C15H11N3)]NO3, comprises a cationic PdII complex and a nitrate anion. In the complex, the PdII cation is four-coordinated in a distorted square-planar coordination geometry defined by the three N atoms of the tridentate 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine ligand and one O atom from the NO3\u2212 anion. In the crystal, the complex mol\u00adecules are stacked in columns along the a axis being connected by \u03c0\u2013\u03c0 stacking [closest inter-centroid separation between pyridyl rings = 3.878\u2005(3)\u2005\u00c5]. The connections between columns and anions to sustain a three-dimensional architecture are C\u2014H\u22efO hydrogen bonds.The title complex, [Pd(NO The Pd\u2014N [1.917\u2005(4) to 2.030\u2005(4)\u2005\u00c5] and Pd\u2014O [2.028\u2005(3)\u2005\u00c5] bond lengths are close. The pyridine rings of the terpy ligand are located approximately parallel to the least-squares plane of the PdN3O unit [maximum deviation = 0.023\u2005(2)\u2005\u00c5], with dihedral angles of 1.4\u2005(2)\u00b0 (ring N1/C1\u2013C5), 3.1\u2005(2)\u00b0 (ring N2/C6\u2013C10) and 3.0\u2005(2)\u00b0 (ring N3/C11\u2013C15). In the crystal  and Cg2i , the centroid-centroid distance is 3.878\u2005(3)\u2005\u00c5 and the dihedral angle between the ring planes is 3.2\u2005(3)\u00b0 2\u00b72H2O  in acetone (30\u2005ml) was added 2,2\u2032:6\u2032,2\u2032\u2032-terpyridine  followed by stirring for 3\u2005h at room temperature. The formed precipitate was separated by filtration, washed with acetone and dried at 323\u2005K to give a light-yellow powder (0.2123\u2005g). Yellow crystals of the product suitable for X-ray analysis were obtained by slow evaporation of its CH3NO2 solution at room temperature.To a solution of Pd I. DOI: 10.1107/S2414314621000857/tk4067Isup2.hklStructure factors: contains datablock(s) I. DOI: 2058389CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "P-substituent benzoate anions or a tri\u00adfluoro\u00adacetate anion. They are hydrated and there are three crystallized as 1:1 salts while the fourth is a 2:2 salt. Their crystal packing depends on strong ribbons or sheets stabilized by hydrogen bonds of type N\u2014H\u22efO and O\u2014H\u22efO and other inter\u00adactions as C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and C\u2014H\u22efF in the tri\u00adfluoro\u00adacetate-based one.Four novel piperazinium salts are reported, and based on 1-phenyl\u00adpiperazinium as a common cation in the asymmetric units that include additionally water mol\u00adecules, and different  9H9O3\u00b7C10H15N2\u00b7H2O (I); 4-phenyl\u00adpiperazin-1-ium 4-meth\u00adoxy\u00adbenzoate monohydrate, C10H15N2\u00b7C8H7O3\u00b7H2O (II); 4-phenyl\u00adpiperazin-1-ium 4-methyl\u00adbenzoate monohydrate, C10H15N2\u00b7C8H7O2\u00b7H2O (III); and 4-phenyl\u00adpiperazin-1-ium tri\u00adfluoro\u00adacetate 0.12 hydrate, C10H15N2\u00b7C2F3O2\u00b70.12H2O (IV), have been synthesized. The single-crystal structures of these compounds reveal that all of them crystallize in the triclinic PI)\u2013(III) is built up of ribbons formed by a combination of hydrogen bonds of type N\u2014H\u22efO, O\u2014H\u22efO and other weak inter\u00adactions of type C\u2014H\u22efO and C\u2014H\u22ef\u03c0, leading to a three-dimensional network. In the crystal of (IV), the cations and the anions are connected by C\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds and by C\u2014H\u22ef\u03c0 inter\u00adactions, forming sheets which in turn inter\u00adact to maintain the crystal structure by linking through the oxygen atoms of water mol\u00adecules and van der Waals inter\u00adactions, giving the whole structure.In this study, four new piperazinium salts, namely, 4-phenyl\u00adpiperazin-1-ium 4-eth\u00adoxy\u00adbenzoate monohydrate, C In compound (II) the asymmetric unit \u2005\u00c5, \u03b8 = 175.89\u2005(17)\u00b0 and \u03c6 = 346\u2005(3)\u00b0. Compound (III) presents an asymmetric unit \u2005\u00c5, \u03b8 = 9.38\u2005(19)\u00b0 and \u03c6 = 167.9\u2005(13)\u00b0. On the other hand, the asymmetric unit of (IV)  and two tri\u00adfluoro\u00adacetate anions  and a 0.12 occupancy water molecule. The aromatic rings of the cations  are essentially planar while the protonated piperazine rings adopt a chair conformation for cation A1, with puckering parameters \u2005\u00c5, \u03b8 = 0.0\u2005(4)\u00b0 and \u03c6 = 207\u2005(14)\u00b0, and a distorted chair conformation for the cation A2, with puckering parameters QT = 0.559\u2005(5)\u2005\u00c5, \u03b8 = 6.6\u2005(4)\u00b0 and \u03c6 = 168\u2005(4)\u00b0.The asymmetric unit of the compound , Fig.\u00a01, consist), Fig.\u00a01 QT = 0.it Fig.\u00a02 compriseit Fig.\u00a03 composedV) Fig.\u00a04 contains3.I), the cation pairs are connected across two water mol\u00adecules by C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming an a-axis direction (Table\u00a01a). In addition, a set of C\u2014H\u22ef\u03c0 inter\u00adactions, through the benzene rings of the anions and the cations, connect the mol\u00adecules together in ribbons along the a-axis direction (Table\u00a01b). The C\u2014H\u22efO, N\u2014H\u22efO, O\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions together form a three-dimensional network, contributing to the stabilization of the crystal structure.In the crystal structure of (n Table\u00a01a. In adn Table\u00a01b. The CII), the cations, the anions and the water mol\u00adecules are connected by C\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming ribbons along the a-axis direction (Table\u00a02a). Furthermore, the cations inter\u00adact via C\u2014-H\u22ef\u03c0 inter\u00adactions through the benzene ring of the anion, forming ribbons along the b-axis direction (Table\u00a02b). The C\u2014H\u22efO, N\u2014H\u22efO, O\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions together form a three-dimensional network, contributing to the stabilization of the crystal structure.In the crystal structure of (n Table\u00a02a. Furthn Table\u00a02b. The CIII), the cations, the anions and the water mol\u00adecules are connected by C\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming ribbons along the a-axis direction , the cations and the anions are connected by C\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds (Table\u00a04a) and C\u2014H\u22ef\u03c0 inter\u00adactions, generating sheets parallel to the (100) plane (Table\u00a04IV) involve the oxygen atoms of carboxylate groups, while the 0.12 fraction of the water molecule contributes with one interaction of the type C\u2014H\u22efO and it is weak in comparison to the other oxygen-based ones.In the crystal structure of \u2013(III) gave no hits. However, searching for a branched phenyl piperazinium cation and para-substituted benzoate anion gave comparable hits, namely; 4-(4-meth\u00adoxy\u00adphen\u00adyl)piperazin-1-ium 4-fluoro\u00adbenzoate monohydrate, 4-(4-meth\u00adoxy\u00adphen\u00adyl)piperazin-1-ium 4-chloro\u00adbenzoate monohydrate, 4-(4-meth\u00adoxy\u00adphen\u00adyl)piperazin-1-ium 4-bromo\u00adbenzoate monohydrate \u2013(IV) have no substituent. They also crystallize as monohydrates, and their crystal structures are based on differently sized chains of rings formed via a combination of hydrogen bonds of the type N\u2013H\u22efO and O\u2013H\u22efO and other weak inter\u00adactions of types C\u2014H\u22efO and C\u2014H\u22ef\u03c0 to form sheets. In 4-(4-meth\u00adoxy\u00adphen\u00adyl)piperazin-1-ium 4-amino\u00adbenzoate monohydrate  gave no hits.A search of the Cambridge Structural Database \u2013(IV), a solution of commercially available (from Sigma\u2013Aldrich) 1-phenyl\u00adpiperazine  in methanol (10\u2005ml) was mixed with equimolar solutions of the appropriate organic acids in methanol (10\u2005ml) viz., 4-eth\u00adoxy\u00adbenzoic acid  for (I), 4-meth\u00adoxy\u00adbenzoic acid  for (II), 4-methyl\u00adbenzoic acid  for (III) and tri\u00adfluoro\u00adacetic acid  for (IV). The corresponding solutions were stirred for 15\u2005min at room temperature and allowed to stand at the same temperature. X-ray quality crystals were formed on slow evaporation in a week for all compounds, where ethanol:ethyl\u00adacetate (1:1) was used for crystallization. The corresponding melting points were 353\u2013355\u2005K for (I), 368\u2013370\u2005K for (II), 338\u2013340\u2005K for (III) and 385\u2013387\u2005K for (IV).For the synthesis of salts (6.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). For the H atoms bonded to the N and O atoms, the atomic coordinates were refined with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O), . In (IV), the atoms of the CF3 groups of two tri\u00adfluoro\u00adacetate anions  are disordered over two sets of sites with site occupancies of 0.737\u2005(3) and 0.263\u2005(3). The corresponding bond distances in the disordered groups were restrained to be equal. The Uij components of these atoms were restrained to be equal and were restrained to approximate isotropic behaviour. The OW1 water molecule was refined with a resulting occupation factor of 0.245\u2005(10) and the H atoms of the water molecule were placed geometrically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989022006004/dj2048sup1.cifCrystal structure: contains datablock(s) global, I, II, III, IV. DOI: 10.1107/S2056989022006004/dj2048Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022006004/dj2048Isup6.cmlSupporting information file. DOI: 10.1107/S2056989022006004/dj2048IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022006004/dj2048IIsup7.cmlSupporting information file. DOI: 10.1107/S2056989022006004/dj2048IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989022006004/dj2048IIIsup8.cmlSupporting information file. DOI: 10.1107/S2056989022006004/dj2048IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989022006004/dj2048IVsup9.cmlSupporting information file. DOI: 2177037, 2177036, 2177035, 2177034CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A new organic salt of diclofenac, [2-phen\u00adyl]acetate, with mono\u00adethano\u00adlammonium and water has been obtained, and its structure has been established by X-ray analysis. 2H8NO+\u00b7C14H10Cl2NO2\u2212\u00b7H2O, the asymmetric unit contains one cation, one anion and a water mol\u00adecule, all in general positions. A complex network of hydrogen bonds is present in the crystal structure.In the solid-state structure of the title compound derived from diclofenac, C The dicb-axis direction, due to the crystallographic twofold screw axis, via N2\u2014H2B\u22efO1Wii hydrogen bond [2.947\u2005(4)\u2005\u00c5, symmetry code: (ii) \u2212x, y\u00a0\u2212\u00a0z\u00a0+\u00a0c [O1W\u22efO1iv, symmetry code: (iv) x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0i, symmetry code: (i) \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01, 2.811\u2005(4)\u2005\u00c5, Fig.\u00a02X\u22efCg \u03c0\u2013ring inter\u00adactions, for C3\u2014H3 and C7\u2014Cl1 bonds, for which the X\u22efCg separations and \u03b3 angles range from 3.533 to 3.958\u2005\u00c5 and from 25.03 to 28.79\u00b0.The ionic form of the title compound serves as a building block for the supra\u00admolecular architecture. In the crystal, the building blocks form screw-like chains along the Crystal Explorer 17.5  at 298\u2005K for 5\u2005min. The solution was then placed in a loosely closed bottle and kept at 298\u2005K for 10 days. The precipitated prismatic crystals were selected for the single-crystal X-ray diffraction analysis.To a solution of 0.1\u2005g (0.52\u2005mmol) of D in 4\u2005ml of ethanol, 32\u2005\u00b5Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314622004412/bh4068sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622004412/bh4068Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622004412/bh4068Isup3.cmlSupporting information file. DOI: 2168795CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom of the cationic complex of the title compound, [Ir(C8H12)(C18H15P)(C6H11N3)][BF4] \u00b70.8CH2Cl2, exhibits a distorted square-planar coordination environment.The central Ir 8H12)(C18H15P)(C6H11N3)]BF4\u00b70.8CH2Cl2, has been synthesized and structurally characterized. The central IrI atom of the cationic complex has a distorted square-planar coordination environment, formed by a bidentate cyclo\u00adocta-1,5-diene (COD) ligand, an N-heterocyclic carbene, and a tri\u00adphenyl\u00adphosphane ligand. The crystal structure comprises C\u2014H\u22ef\u03c0(ring) inter\u00adactions that orient the phenyl rings; non-classical hydrogen-bonding inter\u00adactions between the cationic complex and the tetra\u00adfluorido\u00adborate anion are also present. The complex crystallizes in a triclinic unit cell with two structural units and an incorporation of di\u00adchloro\u00admethane solvate mol\u00adecules with an occupancy of 0.8.A new triazole-based N-heterocyclic carbene iridium(I) cationic complex with a tetra\u00adfluorido\u00adborate counter-anion, [Ir(C The distorted square-planar environment around the IrI atom is defined by the bidentate cyclo\u00adocta-1,5-diene (COD) ligand, the carbene C1 atom of the triazole NHC ligand, and the P atom of the tri\u00adphenyl\u00adphosphane ligand. The P1\u2014Ir1\u2014C1 bond angle is 93.88\u2005(10)\u00b0. The N1\u2014C1\u2014N3 bond angle of the coordinating carbene atom significantly differs with a value of 103.3\u2005(3)\u00b0 from the expected 2sp hybridization.The mol\u00adecular structure of the title complex 4]\u2212 group. Additionally, there are non-classical inter\u00admolecular hydrogen-bonding inter\u00adactions between the hydrogen atom of a phenyl group (H10) and a nitro\u00adgen atom of the NHC ligand (N2). Non-classical hydrogen bonding inter\u00adactions are shown as dotted green lines in Fig.\u00a02The crystal packing of the title compound is displayed in Fig.\u00a02A) and a phenyl phosphane ring (C19\u2013C24). This intra\u00admolecular inter\u00adaction displays an H\u22efcentroid distance of 2.61\u2005\u00c5 and a C\u2014H\u22efcentroid angle of 168\u00b0. The inter\u00admolecular C\u2014H\u22ef\u03c0(ring) inter\u00adaction orients phenyl phosphane rings of adjacent moieties as it occurs between a hydrogen atom of a phenyl ring (H21) and an adjacent phenyl ring (C13\u2013C18). The inter\u00admolecular C\u2014H\u22ef\u03c0(ring) inter\u00adaction has an H\u22efcentroid distance of 2.73\u2005\u00c5 and a C\u2014H\u22efcentroid angle of 157\u00b0. The C\u2014H\u22ef\u03c0(ring) inter\u00adactions orient phenyl rings on adjacent moieties (C13\u2013C18 and C19\u2013C24) into an approximately perpendicular arrangement, shown in Fig.\u00a03Both inter\u00admolecular and intra\u00admolecular C\u2014H\u22ef\u03c0(ring) inter\u00adactions are observed and shown as dashed orange lines in Figs. 2 chloro\u00adiridium (1) was synthesized by a previously published procedure  Varian spectrometer and referenced to the residual solvent peak of CDCl3 (\u03b4 in p.p.m.).(tri\u00adphenyl\u00adphosphane)iridium(I) tetra\u00adfluorido\u00adborate (2): Tri\u00adphenyl\u00adphosphane  and AgBF4 (0.048\u2005g 0.245\u2005mmol) were added to an oven-dried flask containing complex (1)  in 10\u2005ml of CH2Cl2, and stirred under N2 in the dark for 90\u2005min. The mixture was filtered through Celite and the solvent was removed under reduced pressure. The bright orange\u2013red solid was washed with pentane and dried under vacuum yielding 0.165\u2005g (86.9%) of the title compound 2. 1H NMR: \u03b4 (p.p.m.) 8.18 , 7.49\u20137.32 , 5.36 2), 4.38, 3.99 , 4.05 , 2.27\u20131.6 , 1.56 . 13C NMR: \u03b4 177.74 (Ir\u2014C), 140.32 (N\u2014CH\u2014N), 132.46\u2013128.38 (Carom), 87.82, 87.43, 85.34, 85.01 (CH of COD), 53.23 [CH(CH3)2], 41.31 (N\u2014CH3), 33.41, 33.18, 31.45, 30.39 CH2 of COD, 24.37, 22.15 [CH(CH3)2]. 31P: \u03b4 17.23.2 was crystallized by slow diffusion of pentane into a CH2Cl2 solution.The title compound Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2414314623000640/wm4181sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623000640/wm4181Isup2.hklStructure factors: contains datablock(s) I. DOI: 2237810CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The syntheses and low-temperature crystal structures of four organic salts of 4-(4-nitro\u00adphen\u00adyl)piperazine are presented. 10H14N3O2+\u00b7C4H5O4\u2212 (I), 4-(4-nitro\u00adphen\u00adyl)piperazinium 4-amino\u00adbenzoate monohydrate, C10H14N3O2+\u00b7C7H6NO2\u2212\u00b7H2O (II), 4-(4-nitro\u00adphen\u00adyl)piperazinium 2-(4-chloro\u00adphen\u00adyl)acetate, C10H14N3O2+\u00b7C8H6ClO2\u2212 (III) and 4-(4-nitro\u00adphen\u00adyl)piperazinium 2,3,4,5,6-penta\u00adfluoro\u00adbenzoate, C10H14N3O2+\u00b7C7F5O2\u2212 (IV). The salts form from mixtures of N-(4-nitro\u00adphen\u00adyl)piperazine and the corresponding acid  in mixed solvents of methanol and ethyl acetate. Salts I, III, and IV are anhydrous, whereas II is a monohydrate. In each structure, the overall conformation of the cation is determined by the disposition of the exocyclic N\u2014C bond of the piperazine ring  and twists about the N\u2014C bond between the piperazine ring and its attached 4-nitro\u00adphenyl ring. The packing motifs in each structure are quite different, though all are dominated by strong N\u2014H\u22efO hydrogen bonds, which are augmented in I and II by O\u2014H\u22efO hydrogen bonds, and in III by a \u03c0\u2013\u03c0 stacking inter\u00adaction between inversion-related 4-nitro\u00adphenyl groups.The syntheses and crystal structures are presented for four organic salts of the 4-(4-nitro\u00adphen\u00adyl)piperazinium cation, namely, 4-(4-nitro\u00adphen\u00adyl)piperazinium hydrogen succinate, C The relative twist about these N2\u2014C5 bonds, e.g. qu\u00adanti\u00adfied by the C2\u2014N2\u2014C5\u2014C6 torsional angles  determine the overall cation shape. In each case, the 4-nitro group is essentially coplanar with its attached phenyl ring.The overall conformations of the 4-nitro\u00adphenyl\u00adpiperazinium cations in s Figs. 1 \u25b8 \u25b8. WI has minor twists about its three C\u2014C bonds , which leads to a dihedral angle of 34.63\u2005(9)\u00b0 between its carboxyl\u00adate/carb\u00adoxy\u00adlic acid groups. The 4-amino\u00adbenzoate anion of II is close to planar, having a dihedral angle between the carboxyl\u00adate group and its benzene ring of 10.70\u2005(7)\u00b0. The amine group at N4 is also slightly non-planar [the sum of angles about N4 is 349\u2005(2)\u00b0]. In the 2-(4-chloro\u00adphen\u00adyl)acetate anion of III, twists about the C11\u2014C12 and C12\u2014C13 bonds place the carboxyl\u00adate group almost perpendicular [85.02\u2005(9)\u00b0] to the benzene ring. Lastly, in the penta\u00adfluoro\u00adbenzoate anion of IV, the carboxyl\u00adate group is 55.95\u2005(10)\u00b0 out of coplanarity with the phenyl ring.The succinate anion in I, which will be described in more detail in the next section (Supra\u00admolecular features).Throughout all four structures, individual bond lengths and angles take on normal values except for an elongated O\u2014H bond [1.17\u2005(2)\u2005\u00c5] in 3.2 group and the anionic carboxyl\u00adate groups. In I, II, and IV, these hydrogen bonds to the anion are equatorial relative to the piperazine ring, while that in III is axial. Nevertheless, in each structure, the NH2+ group acts as a hydrogen-bond donor through both its hydrogen atoms. In I, III, and IV this is to a second anion, whereas in II it is to the included water mol\u00adecule. Throughout the four structures, all conventional N\u2014H\u22efO and all but one O\u2014H\u22efO  hydrogen bonds take on normal distances and angles  hydrogen bond [O\u22efO = 2.4367\u2005(10)\u2005\u00c5], which links adjacent hydrogen-succinate anions into chains that propagate parallel to the b-axis direction  anions and as an acceptor for an N\u2014H\u22efO hydrogen bond, generates a double-layer network lying parallel to (011)  Fig.\u00a07. Of the III joins two pairs of inversion-related ammonium cations and carboxyl\u00adate anions, forming an III also includes the only \u03c0\u2013\u03c0 inter\u00adactions of the four structures, which occurs between inversion-related  nitro\u00adphenyl rings, giving an inter\u00adplanar spacing of 3.3352\u2005(15)\u2005\u00c5, though the offset (\u22431.92\u2005\u00c5) is large, leading to a centroid\u2013centroid distance of 3.8495\u2005(15)\u2005\u00c5 piperazine as a guest mol\u00adecule  for I, 4-amino\u00adbenzoic acid  for II, 2-(4-chloro\u00adphen\u00adyl)acetic acid  for III, and 2,3,4,5,6-penta\u00adfluoro\u00adbenzoic acid  for IV. The resulting solutions were stirred for 30 minutes at 333\u2005K and allowed to stand at room temperature. X-ray quality crystals formed on slow evaporation of solutions in ethanol:aceto\u00adnitrile (1:1) over the course of a week for all four compounds. The melting points are 398\u2013400\u2005K (I), 473\u2013475\u2005K (II), 431\u2013435\u2005K (III) and 411\u2013415\u2005K (IV).A solution of commercially available (Sigma-Aldrich) 4-nitro\u00adphenyl\u00adpiperazine  in methanol (10\u2005ml) was mixed with equimolar solutions of the appropriate acid in methanol (10\u2005ml) and ethyl acetate (10\u2005ml) 6.sp2\u2014H) and 0.99\u2005\u00c5 (R2CH2), using Uiso(H) values constrained to 1.2Ueq of the attached carbon atom. All N\u2014H and O\u2014H hydrogen atoms were refined freely (both coordinates and Uiso).Crystal data, data collection, and structure refinement details are given in Table\u00a0510.1107/S2056989023001093/hb8053sup1.cifCrystal structure: contains datablock(s) I, II, III, IV, global. DOI: 10.1107/S2056989023001093/hb8053Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023001093/hb8053IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989023001093/hb8053IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989023001093/hb8053IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989023001093/hb8053Isup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001093/hb8053IIsup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001093/hb8053IIIsup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001093/hb8053IVsup9.cmlSupporting information file. DOI: 2239906, 2239905, 2239904, 2239903CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction: BMC Musculoskelet Disord 23, 630 (2022)https://doi.org/10.1186/s12891-022-05517-0Following the publication of the original article  the auth\u201cTheir mean age at surgery was 60.8\u2009\u00b1\u200910.3 years and the average symptom duration was 40.7\u2009\u00b1\u200934.1 months.\u201dShould be corrected to:\u201cTheir mean age at surgery was 61.2\u2009\u00b1\u200910.8 years and the average symptom duration was 23.36\u2009\u00b1\u200922.11 months.\u201dThe original article  has been"}
{"text": "II(C68H44N12O4)(C4H6N2)2]\u00b7C4H6N2\u00b71.5C4H8O is investigated.The crystal structure of the bis\u00ad(1-methyl\u00adimidazole)-ligated iron(II) picket-fence porphyrin derivative [Fe II(C68H44N12O4)(C4H6N2)2]\u00b7C4H6N2\u00b71.5C4H8O, the central FeII ion is coordinated by four pyrrole N atoms of the porphyrin core and two N atoms of the 1-methyl\u00adimidazole ligands in the axial sites. One 1-methyl\u00adimidazole and one and a half tetra\u00adhydro\u00adfuran solvent mol\u00adecules are also present in the asymmetric unit. The complex exhibits a near planar porphyrin core conformation, in which the iron centre is slightly displaced towards the hindered porphyrin side (0.01\u2005\u00c5). The average Fe\u2014Np (Np refers to the pyrrole nitro\u00adgen atoms in the porphyrin) bond length is 1.990\u2005(9)\u2005\u00c5, and the axial Fe\u2014NIm (NIm refers to the imidazole nitro\u00adgen atoms) bond lengths are 1.993\u2005(3) and 2.004\u2005(3)\u2005\u00c5. The dihedral angle between the two coordinated 1-methyl\u00adimidazole planes is 56.6\u2005(2)\u00b0. The dihedral angles between the 1-methyl\u00adimidazole planes and the planes of the closest Fe\u2014Np vector are 16.8\u2005(2) and 39.8\u2005(2)\u00b0. N\u2014H\u22efN and N\u2014H\u22efO inter\u00adactions are observed in the crystal structure.In the title compound, [Fe Additional qu\u00adanti\u00adtative information on the structure is given in Fig.\u00a02p vector are 16.8\u2005(2) and 39.8\u2005(2)\u00b0. The dihedral angle between the two coordinated imidazole planes is 56.6\u2005(2)\u00b0, showing a relative perpendicular orientation. Fig.\u00a02p\u2014Fe\u2014Np angle is ideal at 90.01\u2005(9)\u00b0, and the axial Fe\u2014NIm bond lengths are 1.993\u2005(3) and 2.004\u2005(3)\u2005\u00c5. The average Fe\u2014Np distance of 1.990\u2005(9)\u2005\u00c5 is a typical value for low-spin ferrous porphyrin derivatives  was distilled from Na/benzo\u00adphenone under N2. Hexanes were distilled over sodium/potassium alloy under N2. Solvents were degassed by repeated freeze\u2013pump\u2013thaw cycles. 1-MeIm was distilled under argon before use. Precursors H2TPyPP, [Fe(TPyPP)]Cl, and [Fe(TPyPP)]OH were prepared following literature methods , with slight modifications.Synthesis of the title compound. [Fe(TPyPP)]OH  and 1-MeIm  were dissolved in 3\u2005ml of THF. The mixture was stirred for 15\u2005min and transferred into glass tubes (8\u2005mm \u00d7 10\u2005cm), which were layered with hexa\u00adnes. Several days later, X-ray quality black block-shaped crystals were collected.bCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2414314621005319/bh4061sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621005319/bh4061Isup2.hklStructure factors: contains datablock(s) I. DOI: 2068473CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The study investigated clinical features of sellar and suprasellar tumors with optic nerve bending. Twenty-five patients  with optic nerve bending in one eye who underwent tumor resection for sellar and suprasellar tumors were included. The other eye, without optic nerve bending, was the control. The pre- and postoperative best-corrected visual acuity (BCVA) and ganglion cell layer (GCL)\u2009+\u2009inner plexiform layer (IPL) thickness were studied retrospectively using optical coherence tomography. Preoperative BCVA in the eye with optic nerve bending was significantly poor and improved significantly after tumor resection. Eyes with optic nerve bending had significantly less GCL\u2009+\u2009IPL thickness on the temporal side than eyes without optic nerve bending. Preoperative GCL\u2009+\u2009IPL thickness of the entire macula was reduced in eyes with optic nerve bending and poor postoperative BCVA compared to those with good postoperative BCVA. There was no significant difference in GCL\u2009+\u2009IPL thickness of eyes with optic nerve bending before and after tumor resection. Optic nerve bending caused by sellar and suprasellar tumors resulted in visual impairment and decreased retinal ganglion cells. Eyes with optic nerve bending and severely reduced GCL\u2009+\u2009IPL thickness may have less BCVA improvement after tumor resection. Visual field impairment progresses gradually as the tumor grows, resulting in visual impairment3. However, even a relatively slight compression of the optic chiasm can cause visual impairment. We investigated the visual acuity impairment in the patients with sellar and suprasellar lesions using magnetic resonance (MR) T2\u00a0weighted imaging4. We also reported a new concept that the optic nerve sometimes bends at the entrance of the optic canal from the intracranial subarachnoid space. Further, a combination of preoperative optic nerve bending and optic chiasm compression is associated with visual impairment  can measure ganglion cell layer (GCL)\u2009+\u2009inner plexiform layer (IPL) thickness in the macula with high reliability. Previous reports showed the usefulness of macular GCL\u2009+\u2009IPL parameters in discriminating early glaucoma from normal eyes5. Morphological changes in retinal ganglion cells might also be observed using OCT in patients with sellar and suprasellar tumors with optic nerve bending. Here, we investigated the OCT findings of patients with sellar and suprasellar tumors with optic nerve bending before and after tumor resection.Sellar and suprasellar tumors, including pituitary adenomas, show visual field defects, such as bilateral hemianopsia, due to the optic chiasm compression by the tumorTable All 25 patients with optic nerve bending were classified by age into groups of 30\u201340\u00a0s (n\u2009=\u20096), 50\u00a0s (n\u2009=\u20097), 60\u00a0s (n\u2009=\u20095), and 70\u00a0s (n\u2009=\u20097). Postoperative BCVAs (logMAR) were \u2212\u00a00.08\u2009\u00b1\u20090.00 (30\u201340\u00a0s),0.01\u2009\u00b1\u20090.17 (50\u00a0s), 0.08\u2009\u00b1\u20090.31 (60\u00a0s) and 0.13\u2009\u00b1\u20090.25 (70\u00a0s), respectively. Postoperative BCVA showed no significant differences among these 4 groups .The preoperative GCL\u2009+\u2009IPL thicknesses in bending and non-bending eyes were 65.6\u2009\u00b1\u200912.8\u00a0\u00b5m and 71.4\u2009\u00b1\u20099.7\u00a0\u00b5m in the superior sector, 64.8\u2009\u00b1\u200913.1\u00a0\u00b5m and 68.8\u2009\u00b1\u200911.1\u00a0\u00b5m in the superior nasal sector, 61.9\u2009\u00b1\u200912.4\u00a0\u00b5m and 64.8\u2009\u00b1\u200910.6\u00a0\u00b5m in the inferior nasal sector, 63.8\u2009\u00b1\u200912.9\u00a0\u00b5m and 70.0\u2009\u00b1\u20098.4\u00a0\u00b5m in the inferior sector, 72.9\u2009\u00b1\u200912.8\u00a0\u00b5m and 80.6\u2009\u00b1\u200911.5\u00a0\u00b5m in the inferior temporal sector, and 69.9\u2009\u00b1\u200911.8\u00a0\u00b5m and 75.8\u2009\u00b1\u20098.0\u00a0\u00b5m in the superior temporal sector, respectively. The postoperative GCL\u2009+\u2009IPL thicknesses in the bending and non-bending eyes were 65.2\u2009\u00b1\u200912.7\u00a0\u00b5m and 71.0\u2009\u00b1\u20099.1\u00a0\u00b5m in the superior sector, 63.6\u2009\u00b1\u200913.7\u00a0\u00b5m and 68.2\u2009\u00b1\u200910.7\u00a0\u00b5m in the superior nasal sector, 60.8\u2009\u00b1\u200912.6\u00a0\u00b5m and 64.6\u2009\u00b1\u200910.5\u00a0\u00b5m in the inferior nasal sector, 64.6\u2009\u00b1\u200911.4\u00a0\u00b5m and 68.4\u2009\u00b1\u20098.2\u00a0\u00b5m in the inferior sector, 72.3\u2009\u00b1\u200912.7\u00a0\u00b5m and 79.9\u2009\u00b1\u200912.3\u00a0\u00b5m in the inferior temporal sector, and 69.1\u2009\u00b1\u200912.4\u00a0\u00b5m and 75.6\u2009\u00b1\u20098.0\u00a0\u00b5m in the superior temporal sector, respectively  of 0 or better as good visual outcome and 6 eyes with postoperative BCVA (logMAR) of less than 0 as poor visual outcome. The preoperative GCL\u2009+\u2009IPL thicknesses in the good visual outcome eyes and the poor visual outcome eyes were 69.9\u2009\u00b1\u20098.1\u00a0\u00b5m and 52.0\u2009\u00b1\u200915.3\u00a0\u00b5m in the superior sector, 68.7\u2009\u00b1\u200910.5\u00a0\u00b5m and 52.3\u2009\u00b1\u200912.8\u00a0\u00b5m in the superior nasal sector, 65.7\u2009\u00b1\u20099.6\u00a0\u00b5m and 49.8\u2009\u00b1\u200912.5\u00a0\u00b5m in the inferior nasal sector, 68.9\u2009\u00b1\u20096.6\u00a0\u00b5m and 47.8\u2009\u00b1\u200914.6\u00a0\u00b5m in the inferior sector, 76.9\u2009\u00b1\u20096.7\u00a0\u00b5m and 60.0\u2009\u00b1\u200917.9\u00a0\u00b5m in the inferior temporal sector, and 73.6\u2009\u00b1\u20096.7\u00a0\u00b5m and 58.2\u2009\u00b1\u200916.0\u00a0\u00b5m in the superior temporal sector, respectively  analysis, of sellar and suprasellar tumors with sagittal bending of the optic nerve and compared them with those of non-bending optic nerve controls. Eyes with optic nerve bending due to sellar and suprasellar tumors had worse visual acuity and reduced GCL\u2009+\u2009IPL thickness in the temporal sectors, as measured by OCT, than eyes without optic nerve bending. In addition, eyes with optic nerve bending showed rapid improvement in visual acuity after tumor resection. Furthermore, in six eyes with poor visual outcome, the preoperative GCL\u2009+\u2009IPL thickness was significantly lesser than that in 19 eyes with good visual outcome.4. ONCBA basically affects ipsilateral vision4. Moreover, ipsilateral ONCBA is anatomically unrelated to contralateral visual dysfunction. However, when the ONCBA is large, the tumor is often large; therefore, the visual field defect due to chiasma compression may occur bilaterally. In addition, if the tumor is larger, the ONCBA on the contralateral side may be large. In this study, eyes with optic nerve bending had preoperative visual impairment, whereas eyes without optic nerve bending had good preoperative visual acuity , the preoperative OCT of the optic nerve bending eye showed only a mild decrease in GCL\u2009+\u2009IPL in the predominantly superior nasal sector, and the postoperative BCVA improved  made evaluations, and any disagreements regarding conclusions were resolved by consensus. Optic nerve bending (large ONCBA) was defined as ONCBA\u2009\u2265\u200945\u00b0, and non-optic nerve bending (moderate ONCBA) was defined as ONCBA\u2009<\u200945\u00b0, as previously reported4. The exclusion criteria were as follows: (1) patients with a history of glaucoma or evident glaucomatous optic neuropathy; (2) high myopia (refractive error less than\u2009\u2212\u20096 diopters); (3) retinal diseases, including epiretinal membrane and macular edema; (4) severe cataract, and (5) unclear optic nerve on MR imaging.All experiments followed the tenets of the Declaration of Helsinki and were approved by the Institutional Review Board of the Gunma University Graduate School of Medicine (HS2021-097). Informed consent was obtained from all individual participants in the present study. We retrospectively studied 25 patients with visual impairment due to sellar and suprasellar tumors who underwent endoscopic transsphenoidal tumor resection at Gunma University Hospital from June 2015 to July 2021 and had optic nerve bending in only one eye. The other eye, without optic nerve bending, was used as the control. MR imaging of the sellar and suprasellar lesions in all 25 patients with a 1.5\u00a0T or 3\u00a0T MR imaging system was performed. The presence of optic nerve bending was determined by measuring the sagittal ONCBA on MR images before tumor resection, as previously reported5.All patients underwent ophthalmologic examinations, including best-corrected visual acuity (BCVA), intraocular pressure assessment, refraction, slit-lamp biomicroscopy, fundus examination, and GCL\u2009+\u2009IPL thickness measurement, using Cirrus high definition-OCT  in both the optic nerve bending and non-bending eyes before and 1\u00a0month after tumor resection Fig.\u00a0. BCVA waData are presented as the mean\u2009\u00b1\u2009standard deviation. An unpaired t-test was conducted to compare BCVA and GCL\u2009+\u2009IPL thickness measurements between the bending and non-bending eyes. The paired t-test was conducted to compare changes in BCVA and GCL\u2009+\u2009IPL thickness before and 1\u00a0month after surgery. The correction between BCVA and ONCBA was examined using Spearman\u2019s correlation coefficient. Statistical significance was set at p\u2009<\u20090.05. Statistical analyses were performed using GraphPad Prism version 6 ."}
{"text": "In the crystal, ion pairs are linked by C\u2014H\u22efBr and N\u2014H\u22efBr hydrogen bonds and are connected into helical chains extending along the c-axis direction by weak, electrostatic S\u22efBr\u2212 inter\u00adactions. A Hirshfeld surface analysis was performed, which showed the dominant role of H\u22efH contacts (51.3%).In the title mol\u00adecular salt, C The dihedral angle between the mean planes of the thia\u00adzole and C2\u2013C7 rings is 13.1\u2005(1)\u00b0. A puckering analysis of the C1/C2/C7\u2013C10 ring yielded the parameters Q = 0.499\u2005(3)\u2005\u00c5, \u03b8 = 58.6\u2005(3)\u00b0 and \u03c6 = 225.6\u2005(3)\u00b0, indicating a half-chair conformation.As expected, the C11/C12/C13/N3/S1 thia\u00adzole ring in \u2212 contacts of this length or shorter are present in the Cambridge Structural Database, two examples being reported by Auffinger et al. .In the crystal, the S1\u22efBr1 distance of 3.5017\u2005(7)\u2005\u00c5 is some 0.15\u2005\u00c5 less than the sum of the van der Waals radii and likely represents an electrostatic inter\u00adaction between the two atoms since S1 is near to the cationic charge. Over 200 structures having S\u22efBr al. 2004 and Thom al. 2004. This ins Table\u00a01 form helon Fig.\u00a02. It may ts Fig.\u00a03, in agreet al., 2016A yielded 30 hits of which 11 were considered similar to I. Among these, (Z)-1--2-[1-(4-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene]hydra\u00adzinium bromide unknown solvate -2-[(2-nitro\u00adphen\u00adyl)methyl\u00adidene]-1-hydrazinium bromide -yl\u00adidene)hydrazinyl\u00adidene]eth\u00adyl}pyridinium bromide monohydrate . Fig.\u00a04a presents the Hirshfeld surface plotted over dnorm with a second cation closest to the bromide ion also present, clearly showing the N\u2014H\u22efBr and C\u2014H\u22efBr inter\u00adactions as well as the S1\u22efBr1 short contact (dashed lines). The surface plotted over shape  and curvature indices  do not show much flat surface or evidence for \u03c0-stacking inter\u00adactions, in agreement with the results given in Section 3. Fig.\u00a05a) and resolved into all H\u22efH contacts , H\u22efC/C\u22efH contacts , Br\u22efH/H\u22efBr contacts  and S\u22efH/H\u22efS contacts . The N\u22efH/H\u22efN contacts contribute only 1.3%.The Hirshfeld surface for pe Fig.\u00a04b and cues Fig.\u00a04c do notet al., 2013I suitable for X-ray diffraction were obtained by recrystallization of the crude product from ethanol solution.The title compound was prepared according to our previously reported method  global, I. DOI: 10.1107/S2056989021002863/hb7963Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989021002863/hb7963sup3.pdfGeometrical data for title compound and related phases. DOI: Click here for additional data file.10.1107/S2056989021002863/hb7963Isup5.cmlSupporting information file. DOI: 2071135CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of 1 consists of two crystallographically independent TPRS-{NdIIIO9}  units that form an edge-sharing dinuclear cluster inter\u00adconnected to neighbouring dimers by the \u03bc3-SO42\u2013 anions, yielding a cationic two-dimensional {Nd2(H2O)6(SO4)2}nn+2 sheet. Adjacent cationic layers are then linked via the \u03bc4-glutarato2\u2013 ligands into a three-dimensional coordination network. Strong O\u2014H\u22efO hydrogen bonds are the predominant inter\u00adaction in the crystal structure.A three-dimensional coordination polymer, poly[hexa\u00adaqua\u00ad(\u03bc These properties are cooperatively provided by both the inorganic building units and the organic counterparts (Furukawa 2(H2O)6(glutarato)(SO4)2]n (1). The crystal structure reveals that the glutarates act as bridging ligands binding the cationic {Nd2(H2O)6(SO4)2}nn+2 sheets into a three-dimensional network.Herein, we report a microwave synthesis of a new three-dimensional coordination polymer, n crystallizes in the monoclinic P21/c space group. There are two crystallographically independent NdIII cations (Nd1 and Nd2), two sulfate anions, and six coordinated water mol\u00adecules in the asymmetric unit, as illustrated in Fig.\u00a01The coordination network III cations are nine-coordinated to O atoms from one bridging glutarate2\u2212, two chelating glutarate2\u2212, two chelating sulfate anions and three coordinated H2O, adopting a distorted tricapped trigonal\u2013prismatic geometry, TPRS-{NdIIIO9} , forming an edge-sharing dinuclear unit with its symmetry-related NdIIIO9 polyhedron. The NdIII\u2014O bond distances are in the range of 2.383\u2005(2)\u20132.785\u2005(2)\u2005\u00c5, which are reasonable and comparable to those reported for other NdIII coordination polymers such as [Nd(H2O)4(glutarato)]Cl 4(glutarato)]Cl\u00b72H2O 2(glutarato)]\u00b72H2O 4]Cl 4]Cl\u00b72H2O x(glutarato)}nn+  subunits compensated by uncoordinated chloride anions, each of the tetra\u00adhedral SO42\u2013 ligands in 1 links three adjacent NdIII atoms, forming a neutral two-dimensional network of [Nd2(H2O)6(glutarato)(SO4)2]n. The S\u2014O bond distances are in the range 1.449\u2005(3)\u20131.485\u2005(2)\u2005\u00c5, with O\u2014S\u2014O angles ranging from 107.78\u2005(16) to 111.67\u2005(15)\u00b0. The flexible glutarate linker exhibits a .Both Nd1 can be described as a three-dimensional non-porous framework, which is constructed from edge-sharing TPRS-{NdIIIO9} polyhedra linked through sulfate anions, acting as tritopic inorganic linkers, into a cationic [Nd2(H2O)6(SO4)2]nn+2 sheets parallel to the (011) layers, as illustrated in Fig.\u00a03a. It is noteworthy that these sheets also contain large inorganic [Nd(SO4)]4 rings further stabilized by O\u2014H\u22efO hydrogen bonds between the water mol\u00adecules and sulfate anions (Table\u00a01b). This three-dimensional arrangement also features O\u2014H\u22efO hydrogen bonds between two water mol\u00adecules or between a water mol\u00adecule and oxygen atoms of the glutarate ligands . In total, all but one hydrogen atom from the six crystallographically independent water mol\u00adecules are involved in hydrogen bonding tetra\u00adaqua\u00adneo\u00addym\u00adium chloride] tetra\u00adaqua\u00addineodymium chloride dihydrate] di\u00adaqua\u00addi\u00adneo\u00addym\u00adium(III) tetra\u00adhydrate] diaqua\u00addi\u00adneodymium(III) dihydrate] 3\u00b78H2O , glutaric acid , and 4,4\u2032-bi\u00adpyridine  in 40.0\u2005mL of deionized water under ambient conditions. The solution was transferred into an open glass reactor and then irradiated by microwaves (800\u2005W) for 10 minutes. The solution was let to cool to ambient temperature. Pale-purple block-shaped crystals crystallized from the solution within a few minutes. FT\u2013IR  of 1: stretch\u03bd(O\u2014H) 3364, stretch\u03bd(C\u2014H) 2990, as\u03bd(COO\u2212) 1531, s\u03bd(COO\u2212) 1430, \u03b4(O\u2014H) 1355, s\u03bd(S\u2014O) 1101, s\u03bd(S\u2014O) 1077, s\u03bd(SO42\u2013) 596.Complex Uiso(H) = 1.2Ueq(C). The H atoms from the water mol\u00adecules were located in the residual electron-density map, and where necessary, refined with distance and angle restraints or riding on the parent oxygen atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022000159/jq2009sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022000159/jq2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022000159/jq2009Isup3.molSupporting information file. DOI: 2107848CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Pistacia vera is one of the most important cash crops in Iran that is scattered in arid and semi-arid regions. During a survey of plant-parasitic nematodes of pistachio in Ardakan city in Yazd Province, a species of root-lesion nematode was isolated and identified by morphological, morphometrical, and molecular methods as Pratylenchus oleae Palomares-Rius et al., 2014. This species was isolated from several pistachio trees rhizosphere regarding to molecular analysis, D2\u2013D3 expansion segments of 28S rRNA was amplified by PCR and sequenced. The sequence was deposited in GenBank (Accession No. MW338666). Along with the related phylogenetic analysis, placed this species in a monophyletic clade with other Pratylenchus oleae isolates, based on Bayesian inference (BI) phylogeny. A PCR reaction with the P. oleae specific primer set produced a 547\u00a0bp fragment. This is the first report of P. oleae infecting Pistachio tree in the world.Pistachio,  Pistacia. P. vera is one of the most important commercial cultivars among the 11 identified species. More than 498,000 hectares of Iranian lands are cultivated with pistachio trees and its product with nearly 173000 tones has a high domestic and foreign acceptance  and crushed with a microhomogeniser Vibro Mixer . Two microliters proteinase K (600\u00a0\u03bcg/ml)  were added and the tubes were frozen at \u201280\u00b0C for at least 10\u2009\u2009min and then incubated at 65\u00b0C (1 hr) and 95\u00b0C (10\u2009\u2009min) consecutively. After incubation, the tubes were centrifuged for 2\u2009\u2009min at 14,000\u2009\u2009rpm and kept at \u201220\u00b0C until use. The PCR was carried out in a 30\u2009\u2009\u03bcl reaction comprising of 2\u2009\u2009\u00b5L DNA template, 1\u2009\u2009\u03bcl forward and reverse primers, 15\u2009\u2009\u03bcl Taq DNA Polymerase 2\u00a0\u00d7\u00a0Master Mix (Ampliqon), and 11\u2009\u2009\u03bcl distilled water. The forward primer D2A (5\u2032-ACAAGTACCGTGA GGGAAAGTTG-3\u2032) and the reverse primer D3B (5\u2032-TCGGAAGGAACCAGCTACTA-3\u2032) (P. oleae-specific primer pairs Poleae_fw1_4_36 (5\u2032-GACAGATTAGAATGGAATCTGTTCG-3\u2032) and Poleae_rv1_ _525_551 (5\u2032ATCGCTTTTGGATTCAATAATATA-3\u2032) as described by P. oleae sequence was aligned with related sequences from GenBank through National Center for Biotechnology Information (NCBI) BLASTn homology search, using ClustalW implemented by MEGA version 10.0. The GTR\u00a0+\u00a0I\u00a0+\u00a0G model was selected as the best by jModeltest v.2.1.10. Bayesian tree generated using the Bayesian inference method as implemented in the program MrBayes v.3.2.6   were use v.3.2.6 . Markov datasets .P. oleae, found in roots and around soil from Pistachio tree in Iran are presented in P. oleae as well. P. oleae is characterized by morphological features in females: Vermiform body, lip region with three annuli, slightly offset. Stylet well developed with distinct rounded knobs slightly directed anteriorly. Lateral field with four incisures, metacorpus oval to rounded, isthmus rather short, surrounded by nerve ring, pharyngeal glands well developed, with rather long ventral overlap. Excretory pore either slightly anterior pharyngo-intestinal junction or opposite. Genital branch with one row of oocyte, spermathecal rounded, vagina a straight tube. Vulva transverse slit. Post-vulval uterine sac short, not differentiated. Tail sub-cylindrical, terminus rounded to conical, smooth, male unknown : L\u2009\u2009=\u2009\u2009522.5 \u00b1\u00a034.9 (463.0\u2013565.0) \u03bcm; a\u2009\u2009=\u2009\u200928.3\u00a0\u00b1\u00a01.6 (25.7\u201331.0)\u2009\u2009\u03bcm; b\u2009\u2009=\u2009\u20095.9\u00a0\u00b1\u00a00.4 (5.2\u20136.7)\u2009\u2009\u03bcm; c\u2009\u2009=\u2009\u200920.2\u00a0\u00b1\u00a00.8 (19.1\u201321.0) \u03bcm; Stylet length\u2009\u2009=\u2009\u200917.3\u00a0\u00b1\u00a00.7 (16.0\u201318.0) \u03bcm; Median bulb 55.6\u00a0\u00b1\u00a02.3 (51.0\u201359.0) \u03bcm; Anterior to Excretory Pore 88.9\u00a0\u00b1\u00a02.7 (85.0\u201393.0) \u03bcm; Anterior end to pharyngeal junction 89.0\u00a0\u00b1\u00a04.6 (78.0\u201394.0) \u03bcm; Pharynx Length 123.5\u00a0\u00b1\u00a03.4 (118.0\u2013129.0) \u03bcm; Max. Body diam. 18.5 \u00b1\u00a01.0 (17.0\u201320.0) \u03bcm; Body diam. at anus 12.6\u00a0\u00b1\u00a00.5 (12.0\u201313.0)\u2009\u2009\u03bcm and tail length\u2009\u2009=\u2009\u200925.9\u00a0\u00b1\u00a01.7\u2009\u2009(22.0\u201327.0)\u2009\u2009\u03bcm \u2009\u2009\u03bcm .P. oleae belong to Spain  and Tunisia . Pratylenchus capsici, 9 isolates are most similar to P. oleae, but differs in presence of males, a functional spermatheca, a larger body and shorter stylet  with P. oleae Spain isolate (KJ510861) and 99% (2\u20137 nucleotide differences) similar to P. oleae Spain isolates  and P. oleae Tunisia isolates , while P. dunensis and P. penetrans are 89% and 87% similar (61 and 82 nucleotide differences with 6 and 13 Gaps). The gap variations and nucleotide differences between 9 isolates of P. capsici and P. oleae (MW338666) are between 3\u20139 and 30\u201337 nucleotides respectively  and one location of Tunisia (Ouled Chamekh)  , But somP. oleae deposited in GenBank database. The test population had no gap (base pair), which was different to those of P. oleae from Spain (KJ510855 and KJ510861) with 100% similarity, one gap with Spain (KJ510856 and KJ510857) and Tunisia (KJ510858) with 99% similarity respectively and two gaps with Tunisia (KJ510859 and KJ510860) with 99% similarity. In summary, Iranian P. oleae was isolated from pistachio trees in Ardakan, Yazd province. It is reported for the first time from Iran and pistachio tree in the world. This nematode can be considered as a risk to the economy in pistachio orchards.The sequence of Iranian isolate showed high nucleotide similarity with D2-D3 region of"}
{"text": "The Mg atoms in the title compound are located at an inter\u00adstitial site of the Dy2.1B37Si9-type structure with an occupancy of 0.5. The (001) layers of B12 icosa\u00adhedra stack along the c-axis direction with shifting in the  direction. A three-dimensional framework structure of the layers is formed via B\u2014Si bonds and {Si8} units of [Si]3\u2014Si\u2014Si\u2014[Si]3.Single crystals of a novel sodium\u2013magnesium boride silicide, Na The structure is composed of B12 icosa\u00adhedral clusters: the B\u2014B distances of the 30 distinct bonds in the cluster are in the range of 1.791\u2005(3)\u20131.843\u2005(5)\u2005\u00c5 and the average distance is 1.811\u2005\u00c5 \u2005\u00c5] on the (001) plane and form layers that stack along the c axis with a sequence of ABCABC by shifts of  \u2005\u00c5 for Si3\u2014Si3 and 2.3951\u2005(9)\u2005\u00c5 for Si2\u2014Si3 are comparable with the bond length in crystalline silicon (2.35\u2005\u00c5). The bond angles of Si2\u2014Si3\u2014Si2 and Si2\u2014Si3\u2014Si3 are 113.86\u2005(3)\u00b0 and 104.61\u2005(4)\u00b0, respectively, which are distorted from the regular tetra\u00adhedral bond angle of 109.47\u00b0. The Si2\u2014B1 distance is 2.043\u2005(2)\u2005\u00c5, which is close to the Si\u2014B distances (1.973\u20132.027\u2005\u00c5) found in \u03b2-silicon boride, SiB3    \u2005\u00c5] and Si1/B5\u2014Si1/B5 pairs that bind to the B atoms at B3 connect the B12 layers of Na3MgB37Si9 .The framework structure of Bi9 Fig.\u00a01. Because8} unit between the B12 cluster layers. The Na1\u2014Si2 distance is 2.8620\u2005(4)\u2005\u00c5 and the Na1\u2014B1 and Na1\u2014B2 distances are 2.811\u2005(2) and 2.793\u2005(2)\u2005\u00c5, respectively. These distances are almost the same as the Na\u2014Si distance of Na4Si4 [2.878\u2005(3)\u2005\u00c5; Morito et al., 201515 \u2005\u00c5 and 2.333\u2005(3)\u2005\u00c5, respectively, which are close to the Mg\u2014Si (2.436\u2005\u00c5) and Mg\u2014B distances (2.353\u2005\u00c5) in MgB12Si2     provide six and 6.3 electrons, respectively, and approximately six electrons are supplied from RE in REx1\u2013B12Si\u03b43.3\u2013   and REx1\u2013B36Si9C . The lattice constants and unit-cell volume of Mg3B36Si9C are a = 10.0793\u2005\u00c5, c = 16.372\u2005\u00c5, and V = 1440.4\u2005\u00c53   are a = 10.046\u201310.095\u2005\u00c5, c = 16.298\u201316.467\u2005\u00c5, and V = 1429\u20131454\u2005\u00c53  are a = 10.000\u201310.096\u2005\u00c5, c = 16.225\u201316.454\u2005\u00c5, and V = 1405\u20131452\u2005\u00c53    . Then, 10\u2005mg of B2O3 powder  were added to the crucible, which was stacked on another BN crucible containing 30\u2005mg of Mg powder , and these crucibles were encapsulated in a stainless steel container  with Ar gas. The container was heated at 1373\u2005K for 24\u2005h using an electric furnace. After cooling, the crucible was taken out from the reaction container, and any Na and NaSi remaining in the crucible were reacted and removed with 2-propanol and ethanol. Then, the sample was washed with pure water to remove water-soluble compounds such as sodium borate and alkoxide produced by the reaction of Na and alcohol to leave black plates of the title compound. An electron probe microanalyzer  was used to analyze the composition of the obtained single crystal as Na 5.49\u2005(8), Mg 2.37\u2005(7), B 74.8\u2005(7), Si 17.3\u2005(4) atom %, which is nearly matched by Na3MgB37Si9 . Other elements such as O were not found.Na metal pieces , crystalline B powder  and Si powder  were weighed in a BN crucible , with a molar ratio of Na:B:Si = 5:4:3  in a high-purity Ar-filled glove box  twinning, which reduced the R-value  from 0.0651 to 0.0380.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022000494/hb8005sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022000494/hb8005Isup2.hklStructure factors: contains datablock(s) I. DOI: 2141726CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif. Inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, as well as N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions create a three-dimensional network in the crystal.The mol\u00adecular conformation of the title compound is stabilized by an intra\u00admolecular O\u2014H\u22efO hydrogen bond, forming an  20H15Cl2N3O2, is stabilized by an intra\u00admolecular O\u2014H\u22efO hydrogen bond, forming an S(6) ring motif. The central pyridine ring is almost planar [maximum deviation = 0.074\u2005(3)\u2005\u00c5]. It subtends dihedral angles of 86.10\u2005(15) and 87.17\u2005(14)\u00b0, respectively, with the phenyl and di\u00adchloro\u00adphenyl rings, which are at an angle of 21.28\u2005(15)\u00b0 to each other. The =C(\u2014OH)CH3 group is coplanar. In the crystal, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, and N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network. The most important contributions to the crystal packing are from H\u22efH (33.1%), C\u22efH/H\u22efC (22.5%), Cl\u22efH/H\u22efCl (14.1%), O\u22efH/H\u22efO (11.9%) and N\u22efH/H\u22efN (9.7%) inter\u00adactions.The mol\u00adecular conformation of the title compound, C A strong intra\u00admolecular O2\u2014H2\u22efO1 hydrogen bond  ring motif  create a three-dimensional network in the crystal  in the range of \u22120.4290 to 1.5192 a.u. The red patches that appear around N2 are caused by the inter\u00admolecular N3\u2014H3A\u22efN2 and C16\u2014H16\u22efN2 inter\u00adactions, which are important in the packing of the title mol\u00adecule. Bright red dots near N2 and amine hydrogen atoms H3A and H3B highlight their functions as hydrogen-bonding acceptors and donors, respectively; these also appear as blue and red areas on the Hirshfeld surface mapped over electrostatic potential , C\u22efH/H\u22efC , Cl\u22efH/H\u22efCl , O\u22efH/H\u22efO  and N\u22efH/H\u22efN . Other Cl\u22efC/C\u22efCl, C\u22efC, Cl\u22efO/O\u22efCl, Cl\u22efN/N\u22efCl, N\u22efC/C\u22efN, O\u22efN/N\u22efO, Cl\u22efCl, O\u22efC/C\u22efO and N\u22efN contacts contribute less than 2.1% to Hirshfeld surface mapping and have little directional influence on mol\u00adecular packing  and SETWUK (space group: P21/n), adopt nearly planar structures. The crystal structure of SETWOE is stabil\u00adized by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. The C\u2014H\u22efO hydrogen bonds generate rings with 22R(14) and 22R(20) motifs. The crystal structure of SETWUK is stabilized by inter\u00admolecular C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions. The C\u2014H\u22efF bond generates a linear chain with a C(14) motif. In addition, in SETWOE and SETWUK, intra\u00admolecular O\u2014H\u22efO inter\u00adactions are found, which generate an S(6) graph-set motif. No significant ar\u00adyl\u2013aryl or \u03c0\u2013\u03c0 inter\u00adactions exist in these structures. All this bears some resemblance to the title compound.The polysubstituted pyridines, SETWOE (space group: PP22R(8) ring motif. In the hydrated salt JEBREQ, the presence of the water mol\u00adecule prevents the formation of the familiar i.e. R32(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water mol\u00adecule. Both salts form a supra\u00admolecular homosynthon . Their isotropic displacement parameters were refined using a riding model with Uiso(H) set to either 1.2Ueq(N) for the NH2 group or 1.5Ueq(O) for the OH group. The C-bound H atoms were positioned geometrically (C\u2014H = 0.95\u20131.00\u2005\u00c5) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for the methyl group and Uiso(H) = 1.2Ueq(C) for aromatic and methine H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989021007994/yz2010sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021007994/yz2010Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007994/yz2010Isup3.cmlSupporting information file. DOI: 2101203CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R/S,E)-2-(4-hy\u00addroxy\u00adphen\u00adyl)-4-(2-phenyl\u00adhydrazin-1-yl\u00adidene)chromane-5,7-diol ethanol monosolvate, has been determined. The packing is assisted by C\u2014H\u22efO, O\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efC(\u03c0) type hydrogen bonds, and the pyran ring has an envelope pucker.The structure of racemic -2-(4-hy\u00addroxy\u00adphen\u00adyl)-4-(2-phenyl\u00adhydrazin-1-yl\u00adidene)chromane-5,7-diol ethanol monosolvate, C21H18N2O4\u00b7C2H6O, in a centrosymmetric lattice is reported. The two racemates occupy the same position in the asymmetric unit \u2013 a disordered mixed enanti\u00adomeric structure. Hydrogen bonds of the type O\u2014H\u22efC(\u03c0) in addition to typical C\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN are identified. A positional disorder is seen in the solvent mol\u00adecule (ethanol) as well. The phenyl\u00adhydrazone group is nearly coplanar with the chromane ring system [dihedral angle = 15.5\u2005(1)\u00b0], while the the 4-hy\u00addroxy\u00adphenyl ring is perpendicular [dihedral angle = 87.2\u2005(1)\u00b0] to the chromane. The pyran ring has an envelope pucker .The crystal structure of racemic ( Enanti\u00adomeric structures in centrosymmetric lattices have been discussed by Flack (2003Q = 0.363\u2005(3)\u2005\u00c5, \u03b8 = 57.6\u2005(3)\u00b0; and for the enanti\u00adomer: Q = 0.364\u2005(3)\u2005\u00c5, \u03b8 = 127.4\u2005(4)\u00b0]. An intra\u00admolecular O\u2014H\u22efN hydrogen bond exists between one of the hy\u00addroxy groups on the chromane ring and the nitro\u00adgen of the hydrazone group  mol\u00adecule in 1:1 ratio, yielded a disordered mixed enanti\u00adomeric crystal in a centrosymmetric lattice  type hydrogen-bond inter\u00adactions between the solvent ethanol and phenyl ring are observed Table\u00a01. The phe al. 1993. The strce Fig.\u00a02.et al., 2016Chemical context section. The most similar structures for which crystal data have been reported include acyl hydrazone derivatives of 2-phenyl\u00adchroman-4-one and hesperetin. In particular, crystal structures for 2\u2032-[2-(4-fluoro\u00adphen\u00adyl)chroman-4-yl\u00adidene]isonicotino\u00adhydra\u00adzide -amino}\u00adbenz\u00ada\u00admide  was performed in the Cambridge Structural Database , 0.97\u2005\u00c5 (CH2), 0.86\u2005\u00c5 (NH) or 0.82\u2005\u00c5 (OH). Isotropic displacement parameters for these atoms were set to 1.2  or 1.5  times Ueq of the parent atom. Idealized Me of the ethanol mol\u00adecule were refined as rotating group(s): C22A and C22B (H22A through F) and its idealized tetra\u00adhedral OH refined as a rotating group: O5A and O5B .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022002079/jy2016sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022002079/jy2016Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022002079/jy2016Isup3.cmlSupporting information file. DOI: 2153764CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Z-shaped conformation with the carboxyl group nearly coplanar with the di\u00adhydro\u00adquinoline unit. In the crystal, two sets of C\u2014H\u22efO hydrogen bonds form chains along the b-axis direction, which are connected into corrugated layers parallel to (103) by additional C\u2014H\u22efO hydrogen bonds. The layers are connected by C\u2014H\u22ef\u03c0(ring) inter\u00adactions.The mol\u00adecule adopts a  20H15NO3, adopts a Z-shaped conformation with the carboxyl group nearly coplanar with the di\u00adhydro\u00adquinoline unit. In the crystal, corrugated layers are formed by C\u2014H\u22efO hydrogen bonds and are stacked by C\u2014H\u22ef\u03c0(ring) inter\u00adactions. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (43.3%), H\u22efC/C\u22efH (26.6%) and H\u22efO/O\u22efH (16.3%) inter\u00adactions. The optimized structure calculated using density functional theory at the B3LYP/ 6\u2013311\u2005G level is compared with the experimentally determined structure in the solid state. The calculated HOMO\u2013LUMO energy gap is 4.0319\u2005eV.The title mol\u00adecule, C This moiety is planar to within 0.0340\u2005(6)\u2005\u00c5 (r.m.s. deviation = 0.0164) with N1 and C9 being, respectively, 0.0340\u2005(6) and \u22120.0279\u2005(7)\u2005\u00c5 from the mean plane, resulting in a slight twist at this location. The carboxyl group is nearly coplanar with the di\u00adhydro\u00adquinoline as seen from the 1.04\u2005(5)\u00b0 dihedral angle between the plane defined by C7/C13/O2/O3 and that of the di\u00adhydro\u00adquinoline (C1\u2013C9/N1/O1). This is likely due, in part, to the intra\u00admolecular C5\u2014H5\u22efO2 inter\u00adaction Table\u00a01. The prob-axis direction, which are connected by inversion-related pairs of C4\u2014H4\u22efO2 hydrogen bonds . The positive electrostatic potential (blue region) over the surface indicates hydrogen-donor potential, whereas the hydrogen-bond acceptors are represented by negative electrostatic potential (red region).The nd Fig.\u00a04b. The pet al., 2007a, while those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efC, O\u22efC/C\u22efO, H\u22efN/N\u22efH, N\u22efC/C\u22efN and N\u22efO/O\u22efN contacts are illustrated in Fig.\u00a05b\u2013i, respectively, together with their relative contributions to the Hirshfeld surface (HS). The most important inter\u00adaction is H\u22efH, contributing 43.3% to the overall crystal packing, which is reflected in Fig.\u00a05b as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule, with its tip at de = di = 1.19\u2005\u00c5. In the presence of C\u2014H inter\u00adactions, the pair of characteristic wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts  has tips at de + di = 3.07\u2005\u00c5. The pair of scattered points of spikes in the fingerprint plot delineated into H\u22efO/O\u22efH contacts  have tips at de + di = 2.08\u2005\u00c5. The C\u22efC contacts  have tips at de + di = 3.34\u2005\u00c5. The O\u22efC/C\u22efO contacts, Fig.\u00a05f, contribute 1.5% to the HS and appear as a pair of scattered points of spikes with tips at de + di = 3.55\u2005\u00c5. The H\u22efN/N\u22efH contacts  have tips at de + di = 3.28\u2005\u00c5. Finally, the C\u22efN/N\u22efC and O\u22efN/N\u22ef O contacts, Fig.\u00a05h\u2013i, contribute only 0.5% and 0.1% respectively to the HS and have a low-density distribution of points.The overall two-dimensional fingerprint plot , hardness (\u03b7), ionization potential (I), dipole moment (\u03bc), electron affinity (A), electrophilicity (\u03c9) and softness (\u03c3) are collated in Table\u00a03\u0394E = ELUMO\u00a0\u2212\u00a0EHOMO) of the mol\u00adecule is 4.0319\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO, are \u22126.3166 and \u22122.2847\u2005eV, respectively.The structure in the gas phase of the title compound was optimized by means of density functional theory. The density functional theory calculation was performed by the hybrid B3LYP method and the 6\u2013311\u2005G basis-set, which is based on Becke\u2019s model , benzyl chloride  and tetra n-butyl\u00adammonium bromide as a catalyst in DMF (30\u2005mL) was stirred at room temperature for 48\u2005h. After removal of the salts by filtration, the solvent was evaporated under reduced pressure and the residue obtained was dissolved in di\u00adchloro\u00admethane. The organic phase was dried over Na2SO4 and concentrated under vacuum. The crude product obtained was purified by chromatography on a column of silica gel (eluent: hexa\u00adne/ ethyl acetate: 9/1). 1H NMR  \u03b4 ppm: 3.08 ; 4.37 ; 5.12 ; 7.08\u20138.74 ; 13C NMR  \u03b4 ppm: 34.3 (CH3\u2014N); 66.2 (CH2\u2014O); 72.1 (\u2013C\u2261); 73.2 (CH\u2261); 115.6-148.7 (CHarom and Cquat arom); 162. 5 (C=Oquinol); 168.2 (C=Ocarbox\u00adyl). MS (ESI): m/z = 318 (M + H)+.A mixture of 2-oxo-1-(prop-2-yn-1-yl)-1,2-di\u00adhydro\u00adquinoline-4-carb\u00adoxy\u00adlic acid , KCrystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989021007416/tx2040sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021007416/tx2040Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007416/tx2040Isup3.cmlSupporting information file. DOI: 2097267CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-021-02868-x, published online 10 December 2021Correction to: The original version of this Article contained an error in the legend of Figure\u00a01.a) Garadagh mud volcano in onshore Azerbaijan (40.24\u00b0N and 49.51\u00b0E).\u201d\u201c(now reads:(a) Otmanbozdag mud volcano (within the Garadagh structure) in onshore Azerbaijan (40.24\u00b0N and 49.51\u00b0E).\u201d\u201cThe original Article has been corrected."}
{"text": "This compound crystallized in the space group P\u03b75-coordinated Cp\u2032 rings and a \u03ba3-coordinated (BH4)\u2212 ligand.New syntheses have been developed for the synthesis of (borohydrido-\u03ba For example, \u03ba1, \u03ba2, and \u03ba3 U\u2013(BH4) binding has previously been reported 4  (Cp\u2032 = C5H4SiMe3), made in 1992 \u2212 within the tris-cyclo\u00adpenta\u00addienyl uranium platform using single-crystal X-ray diffraction. Toward this end, we developed new synthetic routes to the Cp\u20323U(BH4) compound.Actinide borohydrides have been of inter\u00adest since the 1940s, owing to their potential volatility and applied use in vapor deposition technologies for the production of thin films  compound was originally synthesized by reacting Cp\u20323UH with H3B-PPh3  from Cp\u20323UH with H3B-PPh3 in hot THF solvent. We also observed Cp\u20323U(BH4) could be prepared in high yield (96%) by reacting Cp\u20323UI with NaBH4 in the presence of 15-crown-5. When this reaction was carried out in toluene at room temperature, the I\u2212 ligand was substituted by the (BH4)\u2212 anion. Another method we developed for synthesizing Cp\u20323U(BH4) involved reacting U(BH4)4 with KCp\u2032 (3 equiv.) in diethyl ether. This reaction, where (BH4)\u2212 was substituted by (Cp\u2032)\u2212, also proceeded in high yield (89%). X-ray quality crystals of Cp\u20323U(BH4) formed at 253\u2005K overnight from diethyl ether solutions.The Cp\u20323U(BH4) from Cp\u20323UI over U(BH4)4 because the U(BH4)4 starting material was more challenging to isolate in a chem\u00adic\u00adally pure form. Another inter\u00adesting comparison between the two synthetic methods involved the substitution chemistry. The (Cp\u2032)\u2212 anion displaced (BH4)\u2212 from U(BH4)4 and (BH4)\u2212 displaced I\u2212 in Cp\u20323UI. Hence, we qualitatively concluded that the stability of the U\u2014X bond for mol\u00adecular compounds dissolved in organic solvents was largest for (Cp\u2032)\u2212, inter\u00admediate for (BH4)\u2212, and lowest for I\u2212. The generality of this conclusion is limited, and we acknowledge the solubility of the other reaction products (such as NaI) might significantly influence the substitution chemistry on uranium.Of our two synthetic routes, we preferred making Cp\u20323U(BH4) were refined in the triclinic Pet al., 20104)3(DME)]2(\u03bc-O) , 2.574\u2005(6), 2.584\u2005(6), and 2.635\u2005(7)\u2005\u00c5 3U(BH4) was reported to be 2.48\u2005\u00c5 3U(BH4) in the gas phase and in solution predicted U\u2014B distances of 2.533 and 2.557\u2005\u00c5 2U(BH4)2 structures showed similar U\u2014B distances of 2.56\u2005(1)\u2005\u00c5 for [C5H3(SiMe3)2]2U(BH4)2 2U(BH4)2 2U(BH4)2  range from 2.458\u20132.500\u2005\u00c5 and average 2.48\u2005(2)\u2005\u00c5 (uncertainty reported as the standard deviation from the mean at 1\u03c3). These uranium\u2013(Cp\u2032 centroid) distances compare well with the 2.473\u2005\u00c5 analogous metric in Cp\u20323UCl  3]  is more acute than the 117.0\u00b0 angle in Cp\u20323UCl and other Cp\u20323UX structures, where the average (Cp\u2032 centroid)\u2014U\u2014(Cp\u2032 centroid) angles were reported as 117\u2005(1)\u00b0 in Cp\u20323UI, 112\u2005(2)\u00b0 in Cp\u20323U(\u03b71-CH=CH2), and 118.7\u2005(4)\u00b0 in Cp\u20323U[Si(SiMe3)3]. The more acute (Cp\u2032 centroid)\u2014U\u2014(Cp\u2032 centroid) angles are complemented by a more obtuse average (Cp\u2032 centroid)\u2014U\u2014B angle of 104.4\u2005(4)\u00b0 in Cp\u20323U(BH4), likely due to the close proximity of the (BH4)1\u2212 ligand compared with (Cp\u2032 centroid)\u2014U\u2014X angles of 100.0\u00b0 in Cp\u20323UCl, 100\u2005(2)\u00b0 in Cp\u20323UI, 98\u2005(3)\u00b0 in Cp\u20323U(\u03b71-CH=CH2), and 96.7\u2005(9)\u00b0 in Cp\u20323U[Si(SiMe3)3], see Table\u00a01The uranium\u2013(Cp\u2032 centroid) distances in Cp\u20323U(BH4) structure is that all three of the tri\u00admethyl\u00adsilyl groups are oriented in a single direction towards the (BH4)\u2212 unit. This orientation has not been observed in other Cp\u20323U(anion) and Cp\u20323U(\u03bc-dianion)UCp\u20323 structures, which are shown in Figs. 23UCl structure  3] complex 3]1\u2212 unit. Since Cp\u20323U(BH4) has the smallest mono-anion of the Cp\u20323U(anion) complexes and the correspondingly smallest (Cp\u2032 centroid)\u2014U\u2014(Cp\u2032 centroid), and the largest (Cp\u2032 centroid)\u2014U\u2014X angles, the orientation of the silyl groups could occur due to steric factors. However, it is also possible that some dispersion forces between the (BH4)\u2212 and the tri\u00admethyl\u00adsilyl groups could contribute to the orientation  piano-stool complexes: (C5H5)U(BH4)3 U(BH4)(SPSMe) Ph2)-1-Me, a \u03bb4-phosphinine with two lateral phosphino\u00adsulfide groups, and the tetra\u00admethyl\u00adphosphol (PC4Me4) compound (PC4Me4)(C8H8)U(BH4)(THF) 2, where Ring = C5H5 2  complex [LU(BH4)][B(C6F5)4] was also in the database  borohydrides, such as the mono borohydride [(PC4Me4)2U(BH4)]2 U(BH4)3]2 2(\u03bc-X) where X = O2\u2212 2\u2212 4(\u03bc-L)  complexes with Cp\u20323U(BH4) compound was also characterized by 1H, 11B{1H}, 13C{1H}, and 29Si{1H} multi-nuclear NMR spectroscopy. It was of particular inter\u00adest to examine the 29Si{1H} spectrum for comparison with previous studies of silicon-containing paramagnetic uranium complexes  and paramagnetically shifted over a range of \u03b4 9.6 to \u221222.6 ppm, in the 1H NMR spectrum, and a 29Si{1H} resonance at \u03b4 \u221257.4 ppm was observed, typical of other tetra\u00advalent uranium complexes \u2212 unit showed considerably more shifting and broadening, resonating at \u03b4 \u221259.5 (\u03bd1/2 = 300\u2005Hz) and 79.6 (\u03bd1/2 = 240\u2005Hz) in the 1H and 11B{1H} spectra, respectively. Since the (BH4)\u2212 ligand exhibited a single 1H NMR resonance whereas two distinct hydride environments are present in the solid state, it appears that the complex is fluxional in solution. This is in line with previous studies  were sparged with UHP argon (Praxair) and dried by passage through columns containing a copper(II) oxide oxygen scavenger (Q-5) and mol\u00adecular sieves prior to use or stirred over sodium benzo\u00adphenone ketyl, briefly exposed to vacuum several times to degas and distilled under vacuum. All ethereal solvents were stored over activated 4\u2005\u00c5 mol\u00adecular sieves. Deuterated solvents (Cambridge Isotopes) used for nuclear magnetic resonance (NMR) spectroscopy were dried over sodium benzo\u00adphenone ketyl, degassed by three freeze-pump-thaw cycles, and distilled under vacuum before use. The 1H, 11B{1H}, 13C{1H} and 29Si{1H} NMR spectra were recorded on a GN 500, Cryo 500 or Bruker Avance 600 spectrometer operating at 500.2\u2005MHz, 160.1\u2005MHz, 125.8\u2005MHz, and 99.1\u2005MHz for the 500\u2005MHz spectrometers, respectively, and 600.1\u2005MHz, 192.6\u2005MHz, 150.9\u2005MHz and 119.2\u2005MHz for the 600\u2005MHz spectrometer, respectively, at 298\u2005K unless otherwise stated. The 1H and 13C{1H} NMR spectra were referenced inter\u00adnally to solvent resonances, 11B and 29Si{1H} NMR spectra were referenced externally to BF3(Et2O) and SiMe4, respectively, the 29Si{1H} spectra were acquired using the INEPT pulse sequence. The 15-crown-5 (Aldrich) reagent was dried over activated mol\u00adecular sieves and degassed by three freeze\u2013pump\u2013thaw cycles before use. The NaBH4 (Aldrich) reagent was placed under vacuum (10 \u22123 Torr) for 12\u2005h before use. The following compounds were prepared following literature procedures: KCp\u2032 4  was added to a C7D8  solution of Cp\u20323UI  in a J-Young NMR tube, an excess of 15-crown-5 (1 drop) was added and the tube was sealed and removed from the glovebox and vortexed (30\u2005s). The NaBH4 was not fully soluble in C7D8 even in the presence of 15-crown-5. After 18\u2005h, NMR spectroscopy showed complete conversion to Cp\u20323U(BH4). The sample was brought back into the glovebox and the volatiles were removed under reduced pressure. The product was then extracted into Et2O, filtered away from white insoluble solids [presumably Na(15-crown-5)I and excess NaBH4] and the volatiles were removed under reduced pressure to give Cp\u20323U(BH4)  as a wine-red solid. 1H NMR : \u03b4 9.7 , \u22122.1 , \u221223.1 , \u221259.8 , 4H); 11B{1H} NMR : \u03b4 79.1 ; 13C{1H} NMR : \u03b4 233.1 (C5H4SiMe3), 214.0 (C5H4SiMe3), 185.6 (C5H4SiMe3), 0.4 (C5H4SiMe3); 29Si{1H} NMR : \u03b4 \u221257.7 ; 1H NMR : \u03b4 9.6 , \u22122.0 , \u221222.6 , \u221259.3 , 4H); 11B{1H} NMR : \u03b4 79.6 ; 13C{1H} NMR : \u03b4 232.0 (C5H4SiMe3), 214.2 (C5H4SiMe3), 186.5 (C5H4SiMe3), 0.6 (C5H4SiMe3); 29Si{1H} NMR : \u03b4 \u221257.4 .Solid NaBH2O (5\u2005mL) solution of KCp\u2032  was added to a pale-green solution of U(BH4)4 , also dissolved in Et2O (5\u2005mL). White solids precipitated (presumably KBH4) as the solution quickly turned orange and then slowly changed to dark red (30\u2005min). After stirring the mixture for an additional 12\u2005h, volatiles were removed under reduced pressure, and the product was extracted into hexane leaving white solids behind (presumably KBH4). Removal of the volatiles under reduced pressure gave Cp\u20323U(BH4)  as a dark wine-red solid. X-ray quality crystals were grown from a concentrated ether solution at 253\u2005K.An Ethttps://submission.iucr.org/jtkt/serve/z/Utgd9EjfTrqJVoXA/zz0000/0/.Crystal data, data collection and structure refinement details are summarized in Table\u00a023 moieties, respectively. Methyl torsion angles were not refined but constrained to be staggered. The borohydride H atoms were located from a difference-Fourier map and their positions were freely refined. Uiso(H) values were set to a multiple of Ueq(C/B) with 1.5 for CH3 and BH4 and 1.2 for C\u2014H units, respectively.C\u2014H bond distances were constrained to 0.95\u2005\u00c5 for cyclo\u00adpenta\u00addienyl C\u2014H moieties, and to 0.98\u2005\u00c5 for aliphatic CH10.1107/S2056989021002425/zl5005sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002425/zl5005Isup3.hklStructure factors: contains datablock(s) I. DOI: 2067867CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Inversion-related chains pack to form layers parallel to the bc plane.The cyclo\u00adhexene ring of the tetra\u00adhydro\u00adiso\u00adquinoline unit is non-planar. The two 4-chloro\u00adphenyl groups extend away from one side of this unit while the hydroxyl and acetyl groups extend away from the opposite side. An intra\u00admolecular O\u2014H\u22efO hydrogen bond fixes the rotational orientation of the acetyl group. In the crystal, N\u2014H\u22efO hydrogen bonds form chains of mol\u00adecules extending along the  28H25Cl2N3O3S, the heterocyclic portion of the tetra\u00adhydro\u00adiso\u00adquinoline unit is planar while the cyclo\u00adhexene ring adopts a twist-boat conformation. The two 4-chloro\u00adphenyl groups extend away from one side of this unit while the hydroxyl and acetyl groups extend away from the opposite side and form an intra\u00admolecular O\u2014H\u22efO hydrogen bond. The crystal packing consists of layers parallel to the bc plane. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H\u22efH (37.3%), Cl\u22efH/H\u22efCl (17.6%), O\u22efH/H\u22efO (11.1%), C\u22efH/H\u22efC (10.9%) and N\u22efH/H\u22efN (9.7%) inter\u00adactions.In the title mol\u00adecule, C The conformation of this ring approximates a twist-boat conformation. The best planes through the C10\u2013C15 and C23\u2013C28 rings are inclined to the N1/C5\u2013C9 plane by 76.05\u2005(6) and 74.04\u2005(6)\u00b0, respectively. The acetyl group on C2 is in an equatorial position while the hydroxyl group on C3 is axial and these are syn to one another. The C10\u2013C15 ring attached to C1 is close to equatorial and anti with respect to both other substituents \u2005\u00c5, O3\u22efCg1ii = 3.6287\u2005(11)\u2005\u00c5 and C22\u2014O3\u22efCg1ii = 115.38\u2005(8)\u00b0; symmetry code: (ii) x, y, z; where Cg1 is the centroid of the N1/C5-C9 ring) are also observed in the crystal structure.In the crystal, helical chains extending along the s Table\u00a01. Inversis Table\u00a01. In addiCrystal Explorer 17.5 , Cl\u22efH/H\u22efCl , O\u22efH/H\u22efO , C\u22efH/H\u22efC  and N\u22efH/H\u22efN . The other contacts are negligible with individual contributions of less than 2.9% and are given in Table\u00a03Fig.\u00a05et al., 2016et al., 2017et al., 2020H-spiro\u00adisoquinolin]-2(1H)-one -yl]-1,2-di\u00adphenyl\u00adethan-1-ol -6,7-dimeth\u00adoxy-3-(meth\u00adoxy\u00addiphenyl\u00admeth\u00adyl)-1-phenyl-1,2,3,4-tetra\u00adhydro\u00adiso\u00adquinoline  and graph-set motifs of the hydrogen-bonding network. In the crystal of DUSVIZ, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds. For the major disorder component, these form C(11) chains that propagate parallel to the a axis. In the crystal of AKIVUO, a layer structure with the layers parallel to  and (10via weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) inter\u00adactions. In the crystal structure of ENOCIU, various C\u2014H\u22ef\u03c0 and C\u2014H\u22efO inter\u00adactions link the mol\u00adecules. In the crystal of NIWPAL, the mol\u00adecules are linked by N\u2014H\u22efO inter\u00admolecular hydrogen bonds involving the sulfonamide function to form an infinite two-dimensional network parallel to the (001) plane.In the crystal of NAQRIJ, dimers form through complementary sets of inversion-related O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. These are connected into zigzag chains along the H)-thione,  with N-(4-chloro\u00adphen\u00adyl)-2-chloro\u00adacetamide  and  of anhydrous sodium acetate in pure ethanol (30\u2005ml) for 1\u2005h as shown in Fig.\u00a06The title compound was obtained by refluxing of 7-acetyl-8-(4-chloro\u00adphen\u00adyl)-4-cyano-1,6-dimethyl-6-hy\u00addroxy-5,6,7,8-tetra\u00adhydro\u00adiso\u00adquinoline-3(2\u22121 (O\u2014H), 3277\u2005cm\u22121 (N\u2014H), 2991, 2920\u2005cm\u22121 , 2217\u2005cm\u22121 (C\u2261N), 1694 , 1666\u2005cm\u22121 . 1H NMR : \u03b4 10.95 ; 8.17\u20138.24 ; 7.79\u20137.81 ; 7.26\u20137.32 ; 7.03\u20137.05 ; 4.88 ; 4.53\u20134.55 ; 4.19\u20134.20 ; 3.24\u20133.29 ; 2.87\u20132.90 ; 2.13 ; 1.86 ; 1.27 . Analysis calculated for C28H25Cl2N3O3S (554.47): C 60.65%, H 4.54%, N 7.58%, S 5.78%. Found: C 60.34%, H 4.57%, N 7.68%, S 5.97%.IR: 3522\u2005cmCrystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989021003674/vm2246sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989021003674/vm2246Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021003674/vm2246Isup3.cmlSupporting information file. DOI: 2075592CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ferrocenyl groups are linked by C\u2014H\u22ef\u03c0(ring) inter\u00adactions.The unsubstituted cyclo\u00adpenta\u00addienyl ring is rotationally disordered while the other Cp ring and its substituent are close to coplanar. In the crystal, the mol\u00adecules pack in \u2018bilayers\u2019 parallel to the  5H5)(C18H13ClN)], is nearly coplanar with the phenyl-1-(4-chloro\u00adphen\u00adyl)methanimine substituent, with dihedral angles between the planes of the phenyl\u00adene ring and the Cp and 4-(chloro\u00adphen\u00adyl)methanimine units of 7.87\u2005(19) and 9.23\u2005(10)\u00b0, respectively. The unsubstituted cyclo\u00adpenta\u00addienyl ring is rotationally disordered, the occupancy ratio for the two orientations refined to a 0.666\u2005(7)/0.334\u2005(7) ratio. In the crystal, the mol\u00adecules pack in \u2018bilayers\u2019 parallel to the ab plane with the ferrocenyl groups on the outer faces and the substituents directed towards the regions between them. The ferrocenyl groups are linked by C\u2014H\u22ef\u03c0(ring) inter\u00adactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (46.1%), H\u22efC/C\u22ef H (35.4%) and H\u22efCl/Cl\u22efH (13.8%) inter\u00adactions. Thus C\u2014H\u22ef\u03c0(ring) and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.The substituted cyclo\u00adpenta\u00addienyl ring in the title mol\u00adecule, [Fe(C They are, however, rotated along their long axis with respect to each other, and despite their nearly coplanar nature that predestines them for \u03c0-stacking inter\u00adactions, no such inter\u00adactions are observed in the solid state. Indeed, directional inter\u00adactions are sparse in the structure of the title compound. Ferrocenyl groups are tied together by C\u2014H\u22ef\u03c0 inter\u00adactions, facilitated by neighboring ferrocene units within each layer being roughly 90\u00b0 rotated against each other. Cp-H atoms thus point towards the \u03c0-system of neighboring Cp rings. The shortest C\u2014H\u22ef\u03c0 inter\u00adactions are between H5 and H7 towards the C atoms C7 and C10 of the substituted Cp ring at \u2212x\u00a0+\u00a0y\u00a0+\u00a0z , and between H3 and H10 towards C atoms C4 and C3 at \u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z . The shortest C\u2014H centroid inter\u00adaction is for C7\u2014H7\u22efCg2 . Also present is a C22\u2014H22\u22efCg5 inter\u00adaction  and a weak C4\u2014H4\u22efCl1 hydrogen bond , C\u22efN/N\u22efC  and Cl\u22efCl contacts  have only 0.5%, 0.2% and 0.1% contributions.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis  found three closely related, ferrocene-substituted Schiff base compounds:  . In a 250\u2005mL round-bottom flask, 1.0\u2005mmol of 4-ferrocenyl aniline in 15\u2005mL of dried methanol was mixed with an equimolar amount of 4-chloro\u00adphenyl aldehyde in 15\u2005mL of dried methanol. The mixture was agitated under reflux, the progress of the reaction was monitored by TLC, and the desired product was formed within 6\u2005h. The solvent was removed under vacuum and the solid that was obtained was recrystallized from methanol (yield: 87%) to yield brown crystals, m.p. 210\u2005K. 1H NMR  \u03b4 4.08 ; 4.36  ; 4.68 ; 7.20 ; 7.48 ; 7.53 ; 7.88  ; 8.52 . 13C NMR  \u03b4 66.42 ; 69.05 ; 69,64 ; 84.80 ; 121.10 ; 126.76 ; 129.09 ; 129.87 ; 134.92 ; 137.20 ; 137.72 ; 149.21  ; 157.62 .4-Ferrocenyl aniline was synthesized according to a reported procedure (Hu I/\u03c3(I) > 15 and chosen from the full data set with CELL_NOW  with a second component (14%) rotated 180\u00b0 about the b axis. To eliminate possible bias, the raw data were processed as triclinic using the multi-component version of SAINT . The data were corrected for absorption using TWINABS . ADPs of equivalent major and minor disordered C atoms were constrained to be identical. The occupancy ratio for the two orientations refined to a 0.666\u2005(7)/0.334\u2005(7) ratio.H atoms attached to carbon were placed in calculated positions (C\u2014H = 0.95\u20131.00\u2005\u00c5). All were included as riding contributions with isotropic displacement parameters 1.2\u20131.5 times those of the parent atoms. The unsubstituted cyclo\u00adpenta\u00addienyl ring is rotationally disordered over two sets of sites with the two components refined as rigid penta\u00adgons  I, global. DOI: 10.1107/S2056989021008033/zl5016Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021008033/zl5016Isup3.cdxSupporting information file. DOI: 2101472CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-021-85236-z, published online 02 April 2021Correction to: P values.The original version of this Article contained an error in the legend of Figure\u00a04, where the minus sign was missing in the A) Densities of Alpha  for low-stimulus and high-stimulus groups shows 1.23\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20092.9E04 (K\u2013S test). (B) Densities for Ea  shows 4.8\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20093.9E05 (K\u2013S test). (C) Densities for CV_Alpha shows 3.5\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20095.8E04 (K\u2013S test). (D) Densities for Theta/Beta ratio shows 1.13\u2009\u00d7\u2009difference in means . (E) Densities for Complexity shows 1.17\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20097.5E05 (K\u2013S test). (F) Average power spectrums of low- and high- stimulus groups. Error bars: average spatial variability across individuals.\u201d\u201cDifferences between low-stimulus and high-stimulus groups. (now reads:A) Densities of Alpha  for low-stimulus and high-stimulus groups shows 1.23\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20092.9E-04 (K\u2013S test). (B) Densities for Ea  shows 4.8\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20093.9E-05 (K\u2013S test). (C) Densities for CV_Alpha shows 3.5\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20095.8E-04 (K\u2013S test). (D) Densities for Theta/Beta ratio shows 1.13\u2009\u00d7\u2009difference in means . (E) Densities for Complexity shows 1.17\u2009\u00d7\u2009difference in means with\u00a0P\u2009<\u20097.5E-05 (K\u2013S test). (F) Average power spectrums of low- and high- stimulus groups. Error bars: average spatial variability across individuals.\u201d\u201cDifferences between low-stimulus and high-stimulus groups. (The original Article has been corrected."}
{"text": "An unusual and labile spirocyclic tetrahedral intermediate (72+) is observed in CO2\u2010pressurized (0.5\u20132.0\u2005bar) solutions of cation 4+ at low temperatures, as demonstrated by variable\u2010temperature NMR studies, which were confirmed crystallographically. In addition, cations 3+ and 4+ actively bind carbonyls, nitriles and acetylenes by 1,3\u2010dipolar cycloaddition, as shown by selected examples.Electrophilic fluorophosphonium triflates bearing pyridyl ( Extending the FLP library: Electrophilic fluorophosphonium triflates bearing pyridyl or imidazolyl substituents act as intramolecular N/P frustrated Lewis pairs that are capable of small molecule activation, that is, reversible CO2 sequestration and binding of carbonyls, nitriles and acetylenes. The corresponding 31P and 19F NMR spectra of the solution containing 3[OTf] reveal no interaction or reaction at ambient temperature indicated by the resonances for cation 3+ (\u03b4(31P)=54.8\u2005ppm, \u03b4(19F)=\u2212114.0\u2005ppm, 1JPF=996\u2005Hz) in the spectra. However, a VT NMR investigation disclosed the reversible and temperature\u2010dependent binding of CO2 by 3[OTf] , a small high field shifted doublet resonance at \u03b4(31P)=\u221255.5\u2005ppm , which is well in the region for a penta\u2010coordinate phosphorus atom, thus, indicating the formation of the CO2 adduct 5[OTf]. The corresponding resonance in the 19F NMR spectrum is detected as a downfield shifted doublet resonance at \u03b4(19F)=\u221230.0\u2005ppm. When the temperature is further decreased to 213\u2005K the integral ratio of 5[OTf] increases to 41\u2009:\u200959. The carbon atom of the bound CO2 is observed as a doublet resonance at \u03b4(13C)=141.8\u2005ppm (2JPC=3\u2005Hz). Further decrease of the temperature to 193\u2005K leads to the separation of a colorless precipitate, suggesting that 5[OTf] exhibits a reduced solubility in CD2Cl2 at low temperature. Accordingly, gradually increase to RT leads to the dissolution of 5[OTf] and its disappearance in the NMR spectrum. This process is reversible without decomposition of 3[OTf]. We investigate this interaction of 3[OTf] with CO2 theoretically with two different models  than model 3+\u20102CO_B (\u221218.4\u2005kJ/mol). Moreover, the calculated 31P NMR chemical shift change (\u0394\u03b4=\u03b4(3+\u20102CO_A)\u2212\u03b4(3+)) for model 3+\u20102CO_A (\u0394\u03b4(31P)=\u2212124\u2005ppm) is in the range of the experimental result (\u0394\u03b4(31P)=\u2212110.7\u2005ppm), while the calculated \u0394\u03b4(31P) for model 3+\u20102CO_B is only shifted by \u221217\u2005ppm which is not observed in the respective 31P NMR spectrum. Thus, the CO2 activation is proposed to proceed via the P and pyridyl N atoms, affording 5[OTf] in the configuration of model 3+\u20102CO_A. As the DFT calculation reveals a slightly improved CO2 binding energy (\u221223.0\u2005kJ/mol) for 4[OTf], we also investigated the reactivity of 4[OTf] towards CO2  at ambient temperature results in the immediate formation of a colorless solid. However, the solid re\u2010dissolves immediately after releasing the pressure and all our separation attempts ended up with the recovery of 4[OTf]. We therefore monitored the reaction of 4[OTf] with CO2 (1.5\u2005bar) by NMR spectroscopy in degassed CD3NO2. The 31P NMR spectrum at ambient temperature shows signals of two different adducts at \u03b4(31P)=\u221260.0\u2005ppm  and \u03b4(31P)=\u221261.5\u2005ppm  besides the signal of 4[OTf] (\u03b4(31P)=55.2\u2005ppm, \u03b4(19F)=\u2212111.5\u2005ppm, 1JPF=1045\u2005Hz, Figure\u200519F spectrum are detected at \u03b4(19F)=\u22128.1\u2005ppm (1JFP=737\u2005Hz) and \u03b4(19F)=\u221216.9\u2005ppm (1JFP=740\u2005Hz), respectively. Interestingly, the 13C NMR spectrum displays two signals for the bound CO2 moiety at \u03b4(13C)=139.9\u2005ppm (2JPC=7\u2005Hz) as a doublet resonance and at \u03b4(13C)=105.5\u2005ppm (2JPC=8\u2005Hz) as a triplet resonance suggesting a coupling to two phosphorus atoms.13 This strongly indicates the formation of a 1\u2009:\u20091 FLP\u2010CO2 adduct 6[OTf] (\u03b4(31P)=\u221261.5\u2005ppm, \u03b4(19F)=\u221216.9\u2005ppm, 1JPF=740\u2005Hz) and a 2\u2009:\u20091 FLP\u2010CO2 adduct 7[OTf]2 (\u03b4(31P)=\u221260.0\u2005ppm, \u03b4(19F)=\u22128.1\u2005ppm, 1JPF=737\u2005Hz). The 31P NMR chemical shift change of 6[OTf] (\u0394\u03b4=\u03b4(6+)\u2212\u03b4(4+), \u2212116.7\u2005ppm) is well in the range of calculated model 4+\u20102CO_A (\u0394\u03b4(31P)=\u2212108\u2005ppm). Decreasing the temperature stepwise to 243\u2005K, the integral ratio of 7[OTf]2 gradually increases to 66\u2009%, while the integral ratio of 6[OTf] increases to 28\u2009%. Variable\u2010temperature NMR studies at 0.5 or 2.0\u2005bar CO2 pressure did not show significant difference on the integral ratio of 6[OTf] and 7[OTf]2. Although the calculated electrophilicities are similar for 3[OTf]  and 4[OTf] ,2 with 3[OTf]. This suggests that a certain nucleophilicity of the Lewis basic site is crucial for the formation of the 2\u2009:\u20091 FLP\u2010CO2 adduct 7[OTf]2.The 6+ and 72+ by vapor diffusion of CH2Cl2 into a CH3NO2 solution of 4[OTf] under CO2 atmosphere (0.5\u2005bar) at \u221230\u2009\u00b0C  and aluminum (VII) complexes \u00b0. One oxygen is bound by the Lewis acidic P atom with a P1\u2212O1 bond length of 1.773(5)\u2005\u00c5 and the carbon atom is stabilized by the Lewis basic N atom to give a N1\u2212C1 bond length of 1.442(10)\u2005\u00c5. The C1\u2212O1 (1.307(8)\u2005\u00c5) and C1=O2 (1.206(10)\u2005\u00c5) bonds in the CO2 fragment are comparable to other FLP\u2010CO2 adducts . (+9\u2009a/+9\u2009b: \u03b4(31P)=\u221249.3/\u221265.0\u2005ppm, \u03b4(19F)=3.0/19.9\u2005ppm, 1JPF=738/702\u2005Hz, 71 and 95\u2009% isolated yield) are indicated by multinuclear NMR spectroscopy =101.8/96.7\u2005ppm, 2JCP=9/11\u2005Hz) are significantly shifted to higher field compared to the free acetone (\u03b4(13C)=207\u2005ppm).9\u2009a,b[OTf] are shifted to lower field (9\u2009a+/9\u2009b+: \u03b4(13C)=151.0/150.2\u2005ppm, 2JCP=18/19\u2005Hz). Interestingly, when compounds 9\u2009a,\u2009b[OTf] are reacted with acetone at room temperature, the formation of 8\u2009a,\u2009b[OTf] under release of CH3CN is observed after a reaction time of 1\u2005h  at room temperature for 4\u2005h, the formation of 10\u2009a,\u2009b and 11\u2009a,\u2009b[OTf]2 is observed, while 12\u2009a,\u2009b[OTf] are cleanly formed by fluoride abstraction from 10\u2009a,\u2009b to 11\u2009a,\u2009b2+ after reacting at 80\u2009\u00b0C overnight or at ambient temperature for 2 weeks  is more Lewis acidic than 3+ , thus, low reaction tendency from 11\u2009a,\u2009b+ to 12\u2009a,\u2009b+ seems to be influenced by solvent effects, which significantly decrease the Lewis acidity compared to the gas phase calculations.2 are found as singlet resonances in the 1P NMR spectra at \u03b4(31P)=6.9 and \u221215.0\u2005ppm, while 12\u2009a,\u2009b[OTf] are observed as doublet resonances in the 31P and 19F NMR spectra (12\u2009a+/12\u2009b+: \u03b4(31P)=\u221288.8/\u221298.8\u2005ppm, \u03b4(19F)=34.0/25.2\u2005ppm, 1JPF=707/718\u2005Hz, Table\u200511\u2009a[OTf]212\u2009b[OTf] (66\u2009%) as pure products for full characterization.When s Scheme\u2005, iii\u2013v. 8\u2009a,\u2009b[OTf], 9\u2009a,\u2009b[OTf] and 12\u2009b[OTf] are confirmed by X\u2010ray analysis of suitable single crystals which were obtained by slow vapor diffusion of n\u2010pentane into saturated CH2Cl2 solutions at \u221230\u2009\u00b0C  and the fluorine atoms occupy the axial position. The P\u2212F bonds (1.637(2) \u22121.673(13)\u2005\u00c5) are elongated compared to those of the starting materials 3+ and 4+, but comparable to those in difluorophosphoranes 3PF2: 1.638(2)\u2005\u00c5).8\u2009a+/8\u2009b+: 1.695(2)/1.695(3)\u2005\u00c5) are significantly shorter compared to the acetonitrile adducts (9\u2009a+/9\u2009b+: 1.777(2)/1.788(2)\u2005\u00c5) while the C\u2212N bonds are around 0.15\u2005\u00c5 longer (8\u2009a+/8\u2009b+: 1.495(4)\u2005\u00c5/1.411(5)\u2005\u00c5, 9\u2009a+/9\u2009b+: 1.250(3)/1.272(3)\u2005\u00c5, Table\u2005The molecular structures of compounds C Figure\u2005. All obt8\u2009a+/8\u2009b+: 1.495(4)/1.411(5)\u2005\u00c5 and the C\u2212N distances of the nitrile moiety (9\u2009a+/9\u2009b+: 1.250(3)/1.272(3)\u2005\u00c5) are typical for C\u2212O single bonds and C=N double bonds, respectively.12\u2009b+ shows that the pyridyl moiety is in the axial position, opposite to the fluorine atom , 2061971 (for 2[OTf]), 2061972 (for 3[OTf]\u2009\u22c5\u2009C6H5F), 2061973 (for 6[OTf]\u2009\u22c5\u20097[OTf]2\u2009\u22c5\u2009CH3NO2), 2061974 (for 8\u2009a[OTf]\u2009\u22c5\u2009CH2Cl2), 2061975 (for 8\u2009b[OTf]\u2009\u22c5\u2009CH2Cl2), 2061976 (for 9\u2009a[OTf]\u2009\u22c5\u2009(CH2Cl2)2\u2009\u22c5\u2009CH3CN), 2061977 (for 9\u2009b[OTf]), 2061978 (for 13), 2061979 (for 12b[OTf]), and 2061980 (for 14)2061970  or imidazolyl (4[OTf]) substituents, thus an additional Lewis basic site, represent a new type of intramolecular FLP that reacts with small molecules in a cooperative manner. The cyclizations of 3[OTf] and 4[OTf] with the 1,2\u2010dipolar compounds acetone, acetonitrile and acetylenes gave rise to the formation of the corresponding heterocyclic compounds, thus illustrating the cooperative reactivity of the new FLP derivatives. This is additionally demonstrated by the reversible formation of adducts with CO2 (5+ and 6+) at low temperature, which was investigated by variable\u2010temperature NMR studies and X\u2010ray analysis. Surprisingly, the bifunctional phosphonium cation 4+ forms an adduct with CO2 (72+) comprising one molecule of CO2 and two molecules of 4+, resulting in a spirocyclic geometry at the central carbon atom, which is hitherto unreported for an N/P FLP system. These novel bifunctional phosphonium cations extend the diverse library of FLP systems, and the reversible CO2 adduct formation might provide new applications for in FLP chemistry, which we are currently investigating.In summary, electrophilic fluorophosphonium compounds bearing pyridyl  should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the crystal, chains parallel to the c axis are generated by inter\u00admolecular N\u2014H\u22efO hydrogen bonds with the chains assembled into a three-dimensional network structure by inter\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0(ring) inter\u00adactions. The mol\u00adecule of (II), C22H21N3O, differs from (I) only in the substituent at the hydrazide N atom where a phenyl\u00admethyl\u00adene moiety for (II) is present instead of a furan\u00admethyl\u00adene moiety for (I). Hence, mol\u00adecules of (I) and (II) show similarities in their mol\u00adecular and crystal structures. The conformation of the central portion of the mol\u00adecule of (II) is also therefore partially determined by an intra\u00admolecular N\u2014H\u22efO hydrogen bond and inter\u00admolecular N\u2014H\u22efO hydrogen bonds form chains parallel to the c axis. Likewise, the chains are connected into a three-dimensional network by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0(ring) inter\u00adactions.The conformation about the central benzene ring in the mol\u00adecule of (I), C These cs Table\u00a01.c-axis direction n Table\u00a02, which ak Table\u00a02.et al., 2016N\u2032-methyl\u00adidene\u00adbenzohydrazide skeleton: N\u2032-[(4-chloro\u00adphen\u00adyl)methyl\u00adidene]-2-[amino]\u00adbenzohydrazide ethyl\u00adidene]-2-[amino]\u00adbenzohydrazide benzohydrazide benzohydrazide -2-[amino]-N\u2032-(2-methyl-5-(prop-1-en-2-yl)cyclo\u00adhex-2-en-1-yl\u00adidene)benzo\u00adhydra\u00adzide \u00b0. These rings make dihedral angles of 47.79\u2005(8) and 69.24\u2005(9)\u00b0, respectively, with the central benzene ring. In the crystal structure of VEDBAK, mol\u00adecules are linked into a three-dimensional supra\u00admolecular network by N\u2014H\u22efO, C\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions.In the crystal structure of LEBSET, mol\u00adecules are linked into a three-dimensional supra\u00admolecular network by N\u2014H\u22efN, N\u2014H\u22efO, C\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions.A and B) having differing conformations that mainly concern the dihedral angles between the hy\u00addroxy\u00adphenyl and di\u00admethyl\u00adphenyl rings relative to the central phenyl\u00adene ring, with values of 30.16\u2005(6) and 58.60\u2005(6)\u00b0 in mol\u00adecule A and of 13.42\u2005(7) and 60.31\u2005(7)\u00b0 in mol\u00adecule B. With the exception of the di\u00admethyl\u00adphenyl substituent, the conformations of the rest of each mol\u00adecule are largely determined by intra\u00admolecular O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds. In the crystal structure, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into chains extending parallel to the a axis where the types of mol\u00adecules alternate in an \u22efA\u22efB\u22efA\u22efB\u22ef fashion.The asymmetric unit of DABREG consists of two mol\u00adecules (S(6) ring motif. In the crystal structure of LEGHAI, mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds to the same acceptor atom, forming sheets lying parallel to the bc plane. The crystal packing also features C\u2014H\u22ef\u03c0 inter\u00adactions.In LEGHAI, the central benzene ring makes dihedral angles of 45.36\u2005(9) and 55.33\u2005(9)\u00b0 with the thio\u00adphene ring and the dimethyl-substituted benzene ring, respectively. The dihedral angle between the thio\u00adphene ring and dimethyl-substituted benzene ring is 83.60\u2005(9)\u00b0. The thio\u00adphene ring and the benzene ring are twisted from the mean plane of the C(=O)\u2014N\u2014N=C bridge [maximum deviation = 0.0860\u2005(13)\u2005\u00c5], with dihedral angles of 23.86\u2005(9) and 24.77\u2005(8)\u00b0, respectively. An intra\u00admolecular N\u2014H\u22efO hydrogen bond generates an S(6) ring motif in the mol\u00adecule, and a short intra\u00admolecular contact (H\u22efH = 1.88\u2005\u00c5) is also observed. In the crystal structure of LEGHIQ, mol\u00adecules are linked by pairs of N\u2014H\u22efN hydrogen bonds into inversion dimers. The crystal packing also features C\u2014H\u22ef\u03c0 inter\u00adactions.In LEGHIQ, the dihedral angle between the benzene rings is 58.05\u2005(9)\u00b0. The non-H atoms of the hydrazide group lie in a common plane (r.m.s. deviation = 0.0006\u2005\u00c5) and are close to co-planar with their attached benzene ring [dihedral angle = 8.02\u2005(9)\u00b0]. An intra\u00admolecular N\u2014H\u22efO hydrogen bond generates an via N\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonds, forming chains along the a-axis direction. In each mol\u00adecule, there is an intra\u00admolecular N\u2014H\u22efO hydrogen bond.The asymmetric unit of the compound YAXJUE comprises two mol\u00adecules. The dihedral angles between the benzene rings in the two mol\u00adecules are 59.7\u2005(2) and 61.27\u2005(18)\u00b0. The cyclo\u00adhexene rings adopt sofa and half-chair conformations. In the crystal structure of YAXJUE, mol\u00adecules are connected Synthesis of (I) A mixture of 1\u2005mmol of 2-furaldehyde (96\u2005mg) and 1\u2005mmol of 2-[amino]\u00adbenzohydrazide (255\u2005mg) in 20\u2005ml of ethanol was refluxed and monitored by TLC until completion. The reaction mixture was cooled to room temperature when the solid product was obtained. The crude product was filtered off, dried and recrystallized from ethanol to afford crystals suitable for X-ray diffraction. M.p. 479\u2013483\u2005K.Synthesis of (II) In a solution of 20\u2005ml of ethanol, a mixture of 106\u2005mg (1\u2005mmol) of benzaldehyde (106\u2005mg) and 255\u2005mg (1\u2005mmol) of 2-[amino]\u00adbenzohydrazide was refluxed for 4\u2005h. The solid product was obtained after the reaction mixture was cooled to room temperature. The crude product was filtered off, dried and recrystallized from ethanol to afford crystals suitable for X-ray diffraction. M.p. 466\u2013469\u2005K.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021001353/wm5599sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989021001353/wm5599Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989021001353/wm5599IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989021001353/wm5599Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021001353/wm5599IIsup5.cmlSupporting information file. DOI: 2061393, 2061392CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The -2,2\u2032-{[bis\u00ad[(aza\u00adniumylyl\u00adidene)methanylyl\u00adidene]}bis\u00ad(6-meth\u00adoxy\u00adphenolate) ligand, obtained from o-vanillin and -(\u2212)-1,2-di\u00adphenyl\u00adethyl\u00adenedi\u00adamine, exhibits a slightly distorted planar arrangement of the four coordinated O atoms. In the crystal, the complex shows intra\u00admolecular N\u2014H\u22efO hydrogen bonds and weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are from H\u22efH (33.5%), O\u22efH (34.1%) and C\u22efH (21.7%) contacts.In the title complex, [Sm(NO The bond lengths between the metal center and the nitrate oxygen atoms range from 2.475\u2005(5) to 2.633\u2005(5)\u2005\u00c5, showing more flexibility than those of the Schiff base ligand. In the Schiff base ligand, the imine moieties are protonated to form iminium cations, but the C=N bond lengths remain close to those of normal imine bonds at 1.287\u2005(8) and 1.30\u2005(1)\u2005\u00c5.et al., 2013Intra\u00admolecular hydrogen bonds occur between the iminium protons and the phenolic oxygen atoms, with lengths of 1.71\u20131.89\u2005\u00c5 Table\u00a01. The bonet al., 2009et al., 2004CrystalExplorer17.5 -3-(meth\u00adoxy)phen\u00adyl]methaniminiumato})tris(nitrato)samarium -{\u03bc-}bis[6-(meth\u00adoxy)phenolato]]}trinitratoeuropium(III)nickel(II) -(\u2212)-1,2-Di\u00adphenyl\u00adethyl\u00adenedi\u00adamine  and o-vanillin  were dissolved in ethanol (30\u2005mL) and the resulting mixture was stirred at 313\u2005K for 1\u2005h to afford a yellow solution. To this solution, samarium nitrate hexa\u00adhydrate  was added and it was stirred at 313\u2005K for 2\u2005h. A yellow precipitate appeared immediately. The precipitate was filtered and washed with ethanol and hexane. The title compound  was obtained as a yellow solid. IR  : 1624 (C=N double bond). Fluorescence bands in methanol solution were observed at 562 (4G5/2 \u2192 6H5/2), 597 (4G5/2 \u2192 6H7/2) and 644 (4G5/2 \u2192 6H 9/2) nm. Single crystals suitable for X-ray diffraction were obtained by recrystallization from methanol and diethyl ether  solution.(1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). SIMU, ISOR and AFIX 66 commands were used for C55, C56, C57, C58, C59, C60 to suppress temperature anisotropy and restrain bond lengths to appropriate values.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021004424/tx2039sup1.cifCrystal structure: contains datablock(s) 1R, I. DOI: 10.1107/S2056989021004424/tx2039Isup2.hklStructure factors: contains datablock(s) I. DOI: 2080014CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-020-72306-x, published online 17 September 2020Correction to: The original version of this Article contained an error.The p value stated in the text for differences in fasting blood sugar, between non-overweight and obese groups, was incorrect. The text,\u201cThere was no statistically significant difference in the level of ALT (98.9\u2009\u00b1\u200934.6 vs. 96.3\u2009\u00b1\u200924.1 p\u2009=\u20090.76), serum vitamin B12 (559\u2009\u00b1\u2009417.1 vs. 433\u2009\u00b1\u2009185.4 p\u2009=\u20090.18), fasting blood sugar  or the serum homocysteine levels (13.2\u2009\u00b1\u20094.0 vs. 14.04\u2009+\u20091.80 p\u2009=\u20090.49) between the non-overweight and obese groups.\u201dnow reads,\u201cThere was no statistically significant difference in the level of ALT (98.9\u2009\u00b1\u200934.6 vs. 96.3\u2009\u00b1\u200924.1 p\u2009=\u20090.76), serum vitamin B12 (559\u2009\u00b1\u2009417.1 vs. 433\u2009\u00b1\u2009185.4 p\u2009=\u20090.18) or the serum homocysteine levels (13.2\u2009\u00b1\u20094.0 vs. 14.04\u2009+\u20091.80 p\u2009=\u20090.49) between the non-overweight and obese groups. Though the fasting blood sugar  was significantly different, there was only one patient whose fasting blood sugar placed them within range of a diabetes mellitus diagnosis .\u201dThis has been corrected in the PDF and HTML versions of the Article."}
{"text": "Thereby, each signal alone only induces a moderate production of pro\u2010inflammatory cytokines and lipid mediators (LMs). However, MCs, which simultaneously sense (co\u2010sensing) IL\u201033 and ATP, display an enhanced and prolonged activation of the TAK1\u2010IKK2\u2010NF\u2010\u03baB signalling pathway. This resulted in a massive production of pro\u2010inflammatory cytokines such as IL\u20102, IL\u20104, IL\u20106 and GM\u2010CSF as well as of arachidonic acid\u2010derived cyclooxygenase (COX)\u2010mediated pro\u2010inflammatory prostaglandins (PGs) and thromboxanes (TXs), hallmarks of strong MC activation. Collectively, these data show that co\u2010sensing of ATP and IL\u201033 results in hyperactivation of MCs, which resembles to MC activation induced by IgE\u2010mediated crosslinking of the Fc\u03b5RI. Therefore, the IL\u201033/IL\u201033R and/or the ATP/P2X7 signalling axis are attractive targets for therapeutical intervention of diseases associated with the loss of integrity of cellular barriers such as allergic and infectious respiratory reactions.IL\u201033 and ATP are alarmins, which are released upon damage of cellular barriers or are actively secreted upon cell stress. Due to high\u2010density expression of the IL\u201033 receptor T1/ST2 (IL\u201033R), and the ATP receptor P2X7, mast cells (MCs) are one of the first highly sensitive sentinels recognizing released IL\u201033 or ATP in damaged peripheral tissues. Whereas IL\u201033 induces the MyD88\u2010dependent activation of the TAK1\u2010IKK2\u2010NF\u2010\u03baB signalling, ATP induces the Ca Co\u2010sensing of ATP and IL\u201033 triggers hyperactivation of mast cells resulting in an amplified production of pro\u2010inflammatory cytokines and eicosanoids. Imagewas created with BioRender.com. After centrifugation, cells were recovered in KREBS\u2010HEPES buffer supplemented with 1\u00a0mM CaCl2 and diluted to a final density of 1\u00a0\u00d7\u00a0106 cells/ml. Cells were transferred onto black 96\u2010well microplates PS F\u2010bottom (Greiner bio\u2010one), and the signal was monitored by a NOVOstar microplate reader (BMG Labtechnologies GmbH) at 37\u00b0C : emission at 510\u00a0nm, excitation at 340\u00a0nm (Ca2+\u2010bound Fura\u20102) and 380\u00a0nm (free Fura\u20102). By subsequent cell lysis with triton X\u2010100, the maximal fluorescence signals were determined, followed by chelating Ca2+ with 20\u00a0mM EDTA to assess the minimal fluorescence.To determine the effect of ATP (Sigma) and/ or IL\u201033 (50\u00a0ng/ml) (PeproTech) on the intracellular Ca3). BMMCs were treated with anti\u2010CD16/CD32 and rat\u2010IgG (Jackson) to prevent non\u2010specific binding of the staining antibodies. BMMCs were stained with PE\u2010anti\u2010CD117 or APC\u2010anti\u2010CD117, FITC\u2010anti\u2010Fc\u03b5RI or PE\u2010CD107\u03b1 . MC/9\u2010NFAT and MC/9\u2010NF\u2010\u03baB MC lines were stained with PE\u2010anti\u2010CD117. All cells were analysed with a LSR II flow cytometer (BD). Data were analysed with FlowJo 10 .BMMCs were harvested and washed with PBA  (PeproTech) and/or ATP (500\u00a0\u00b5M) (Sigma). Lysis of the cells was performed with lysis buffer , and the protein concentration was determined . Boiled samples (treated with 6\u00a0\u00d7\u00a0Laemmli buffer) were separated on 10% sodium dodecyl sulphate (SDS)\u2010Laemmli gels. Gels were transferred onto nitrocellulose membranes (biostep) by electroblotting. After blocking (with dry milk), membranes were incubated with either anti\u2010pT180/pY182\u2010p38, anti\u2010pS177/181\u2010IKK2, anti\u2010p184/187\u2010pTAK1, anti\u2010pT202/pY204\u2010ERK1/2, anti\u2010pS32\u2010I\u03baB\u03b1, and anti\u2010pS536\u2010p65 or the respective anti\u2010total antibodies (non\u2010phosphorylated proteins) . Washed membranes (TBS/0\u00b71% Tween) were incubated with HRP\u2010conjugated secondary anti\u2010rabbit\u2010Ig, or anti\u2010mouse\u2010Ig or anti\u2010goat\u2010Ig (SeraCare). Detection was performed with ECL reagent (Pierce).Washed BMMCs were seeded in IL\u20103\u2010free media at a density of 106 cells/ml) were seeded in IL\u20103\u2010free media. After 1\u00a0h, cells were pre\u2010treated with the inhibitors cyclosporine (4\u00a0\u00b5g/ml) , the Ca2+ chelator BAPTA\u2010AM (5\u00a0\u00b5M) (Ca2+ chel.) for Ca2+ depletion, U0126 (10\u00a0\u00b5M)  , the selective P2X7 inhibitor, A438079 (50\u00a0\u00b5M)  (Sigma) or skepinone\u2010L (1\u00a0\u00b5M) (Cayman)  or vehicle for 30\u00a0min. Afterwards, BMMCs were stimulated with IL\u201033 (50\u00a0ng/ml) (PeproTech) or ATP (500\u00a0\u00b5M) (Sigma) or both in combination for 24\u00a0h. Supernatants were transferred to ice\u2010cold methanol containing deuterium\u2010labelled internal standards  for the quantification of LM and sample recovery. Sample preparation was performed as recently shown recently reported [2O was added . Samples were subjected to solid\u2010phase extraction using Sep\u2010Pak\u00ae Vac 6cc 500\u00a0mg/6\u00a0ml C18 (Waters). After washing with H2O and n\u2010hexane, LM were eluted with methyl formate. Samples were dried using an evaporation system (TurboVap LV) and resuspended in methanol\u2010water  for UPLC\u2010MS\u2010MS automated injections. LM profiling was analysed with an Acquity\u2122 UPLC system (Waters) and a QTRAP 5500\u00a0mass spectrometer (ABSciex) equipped with a TurboV\u2122 Source and electrospray ionization. LM was eluted using an ACQUITY UPLC\u00ae BEH C18 column  at 50\u00b0C with a flow rate of 0\u00b73\u00a0ml/min and a mobile phase consisting of methanol\u2010water\u2010acetic acid of 42:58:0\u00b701 (v/v/v) that was ramped to 86:14:0\u00b701 (v/v/v) over 12.5\u00a0min and then to 98:2:0\u00b701 (v/v/v) for 3\u00a0min [BMMCs (1\u00a0\u00d7\u00a010reported . In brieor 3\u00a0min . The QTr6 cells/ml) were seeded in IL\u20103\u2010 and serum\u2010free media. After 1\u00a0h, cells were pre\u2010treated with the inhibitors cyclosporine A (4\u00a0\u00b5g/ml) , the Ca2+ chelator BAPTA\u2010AM (5\u00a0\u00b5M) (Ca2+ chel.) for Ca2+ depletion, U0126 (10\u00a0\u00b5M)   or skepinone\u2010L (1\u00a0\u00b5M) (Cayman)  or vehicle for 30\u00a0min. Afterwards, BMMCs were stimulated with IL\u201033 (50\u00a0ng/ml) (PeproTech) or ATP (500\u00a0\u00b5M) (Sigma) or both in combination for 24\u00a0h. Supernatants were transferred to pre\u2010coated ELISA plates and the competitive LTC4 ELISA was performed as described in the instructions (Cayman).BMMCs . Statistics were performed with IBM SPSS Statistics version 20.0 .All experiments were performed at least with three biological replicates. One biological replicate always is the bone marrow culture from at least 2 mice. Western blots intensities were determined with the ImageJ software (Fiji). The phospho\u2010specific Western blots were normalized to the total protein blots. The control (unstimulated sample) of wt BMMCs was set as 1. For analysis of CaThe authors declare no competing financial interests.P.M.J., N.A., M.G., O.W. and A. D. performed and analysed experiments, wrote and edited the manuscript; P.W., F.W., U.J. and C.K.: performed and analysed experiments, edited the manuscript; T.K. and E.S. provided material and edited the manuscript; S.D. developed the concept, designed the research, performed most of the experiments, analysed data, drafted, wrote and edited the paper.Fig S1Click here for additional data file.Fig S2Click here for additional data file.Fig S3Click here for additional data file.Fig S4Click here for additional data file.Fig S5Click here for additional data file.Fig S6Click here for additional data file.Fig S7Click here for additional data file.Fig S8Click here for additional data file.Fig S9Click here for additional data file."}
{"text": "C\u2014Br\u22ef\u03c0 and C=O\u22ef\u03c0 inter\u00adactions stabilize the mol\u00adecular packing, resulting in a three-dimensional network.In the crystal, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into dimers with an  20H16BrN3O2, was determined using an inversion twin. Its asymmetric unit comprises two crystallographically independent mol\u00adecules (A and B) being the stereoisomers. Both mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds, forming a dimer with an R22(16) ring motif. The dimers are connected by further N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming chains along the c-axis direction\u00b7C\u2014Br\u22ef\u03c0 inter\u00adactions between these chains contribute to the stabilization of the mol\u00adecular packing. Hirshfeld surface analysis showed that the most important contributions to the crystal packing are from H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO, Br\u22efH/H\u22efBr and N\u22efH/H\u22efN inter\u00adactions.The crystal structure of the title compound, C In mol\u00adecule A, the phenyl (C7\u2013C12) and bromo\u00adphenyl (C14\u2013C19) rings form dihedral angles of 64.0\u2005(4) and 86.3\u2005(4)\u00b0, respectively, with the mean plane of the central di\u00adhydro\u00adpyridine ring. In mol\u00adecule B, the corresponding dihedral angles are 77.2\u2005(4) and 83.9\u2005(4)\u00b0. The acetyl groups in both mol\u00adecules are almost planar  and they make the dihedral angles of 89.5\u2005(5) and 87.7\u2005(5)\u00b0 with the mean planes of the di\u00adhydro\u00adpyridine rings in these mol\u00adecules.The title compound crystallizes in the monoclinic space group it Fig.\u00a01. These mB\u22efO21 and N26\u2014H26A\u22efO1 hydrogen bonds \u2005\u00c5, C21=O21\u22efCg2 = 110.8\u2005(6)\u00b0, O1\u22efCg5 = 3.748\u2005(8)\u2005\u00c5, C1=O1\u22efCg5 = 125.1\u2005(6)\u00b0, where Cg2 and Cg5 are the centroids of the C7\u2013C12 phenyl ring in mol\u00adecule A and the C27\u2013C32 phenyl ring in mol\u00adecule B, respectively]. The dimers are connected by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds with an c-axis direction (Table\u00a01Cg6v = 3.407\u2005(4)\u2005\u00c5, C17\u2014Br1\u22efCg6v = 145.2\u2005(3)\u00b0; symmetry code (v) \u22121\u00a0+\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z; Cg6 is the centroid of the C34\u2013C39 ring]. Together with the other inter\u00admolecular contacts given in Table\u00a02Strong N6\u2014H6ds Fig.\u00a01 link moln Table\u00a01 and 5 \u25b8.A and B, CrystalExplorer17  indicate regions of N\u2014H\u22efO inter\u00adactions. The N\u2014H\u22efN and C\u2014H\u22efN inter\u00adactions , the mol\u00adecular conformation of the title compound is stabilized by an intra\u00admolecular O\u2014H\u22efO hydrogen bond, forming an S(6) ring motif. In the crystal, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, and N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network.In OZAKOS (space group: PPi.e. R32(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water mol\u00adecule. Both salts form a supra\u00admolecular homosynthon [In both the related salts, JEBREQ (space group: P21/n) and SETWOE (space group: P21/c), adopt nearly planar structures. The crystal structure of SETWUK is stabilized by inter\u00admolecular C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions. The C\u2014H\u22efF bond generates a linear chain with a C(14) motif. The crystal structure of SETWOE is stabilized by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. The C\u2014H\u22efO hydrogen bonds generate rings with 22R(14) and 22R(20) motifs. In addition, in SETWOE and SETWUK, intra\u00admolecular O\u2014H\u22efO inter\u00adactions are found, which generate an S(6) graph-set motif. No significant ar\u00adyl\u2013aryl or \u03c0\u2013\u03c0 inter\u00adactions exist in these structures. All this bears some resemblance to the title compound.The polysubstituted pyridines, SETWUK (space group: To a solution of 2-(4-bromo\u00adbenzyl\u00adidene)malono\u00adnitrile  and acetoacetanilide  in methanol (25\u2005mL), piperidine (2\u20133 drops) was added and the mixture was stirred at room temperature for 48\u2005h. Then 15\u2005mL of methanol were removed by rotary evaporation from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from ethanol/water (1:1) solution .1H NMR : 2.29 ; 4.15 ; 4.34 ; 5.98 ; 7.12\u20137.35 ; 7.40 ; 7.61 .13C NMR : 27.86 (CH3\u2014C=O), 37.94 (CH\u2014Ar), 57.24 (=Cquat), 62.41 (CH\u2014C=O), 117.21 (CN), 121.25 (Br-Car), 127.67 (CHar), 128.19 (2CHar), 129.58 (2CHar), 130.15 (2CHar), 130.74 (2CHar), 136.98 (Car), 140.37 (Car), 154.14 (=Cquat), 166.20 (N\u2014C=O), 202.55 (C=O).Uiso(H) = 1.2Ueq or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989022001232/yk2165sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001232/yk2165Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022001232/yk2165Isup3.cmlSupporting information file. DOI: 2149629CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two triclinic polymorphs of a new tetra\u00adkis-substituted pyrazine carb\u00adoxy\u00adlic acid, 3,3\u2032,3\u2032\u2032,3\u2032\u2032\u2032-[)tetra\u00adkis\u00ad(sulfanedi\u00adyl)]tetra\u00adpropionic acid, are reported, together with the crystal structures of two potassium-organic frameworks. 20H28N2O8S4, (4L1H), have been obtained, 4L1_AH and 4L1_BH. Each structure crystallized with half a mol\u00adecule in the asymmetric unit of a triclinic P4L1_BH were of poor quality, but the X-ray diffraction analysis does show the change in conformation of the \u2013CH2\u2014S\u2014CH2\u2014CH2\u2013 side chains compared to those in polymorph 4L1_AH. In the crystal of 4L1_AH, mol\u00adecules are linked by two pairs of O\u2014H\u22efO hydrogen bonds, enclosing R22(8) ring motifs forming layers parallel to plane (100), which are linked by C\u2014H\u22efO hydrogen bonds to form a supra\u00admolecular framework. In the crystal of 4L1_BH, mol\u00adecules are also linked by two pairs of O\u2014H\u22efO hydrogen bonds enclosing R22(8) ring motifs, however here, chains are formed propagating in the [001] direction and stacking up the a-axis. Reaction of 4L1H with Hg(NO3)2 in the presence of a potassium acetate buffer did not produce the expected binuclear complex, instead crystals of a potassium\u2013organic framework were obtained, poly[sulfan\u00adyl]meth\u00adyl}pyrazin-2-yl)meth\u00adyl]sulfan\u00adyl}propano\u00adato)potassium], [K(C20H27N2O8S4)]n (3L1KH). The organic mono-anion possesses inversion symmetry with the pyrazine ring being located about an inversion center. A carb\u00adoxy H atom is disordered by symmetry and the charge is compensated for by a potassium ion. A similar reaction with Zn(NO3)2 resulted in the formation of crystals of a dipotassium-organic framework, poly[sulfan\u00adyl]meth\u00adyl}pyrazine-2,5-di\u00adyl)bis(methyl\u00adene)]bis\u00ad(sulfanedi\u00adyl)}dipropionato)dipotassium], [K2(C20H26N2O8S4)]n (2H2L1K). Here, the organic di-anion possesses inversion symmetry with the pyrazine ring being located about an inversion center. Two symmetry-related acid groups are deprotonated and the charges are compensated for by two potassium ions.Two polymorphs of the title tetra\u00adkis-substituted pyrazine carb\u00adoxy\u00adlic acid, 3,3\u2032,3\u2032\u2032,3\u2032\u2032\u2032-{}tetra\u00adpropionic acid, C The first is pyrazine-2,3,5,6-tetra\u00adcarb\u00adoxy\u00adlic acid (pztca), which was originally synthesized by Wolff at the end of the 19th century , which was first synthesized by Jiang et al. )tetra\u00adkis\u00ad(sulfane\u00addi\u00adyl)]tetra\u00adpropionic acid , for which two nickel(II) binuclear complexes, I and II, were synthesized , crystallized with half a mol\u00adecule in the asymmetric unit )tetra\u00adkis\u00ad(sulfanedi\u00adyl)]tetra\u00adpropionic acid  of the centrosymmetric mol\u00adecule being positionally disordered . The difference in the two polymorphs is essentially in the orientation of the \u2013CH2\u2014S\u2014CH2\u2014CH2\u2014C\u2013 side arms, as shown in Fig.\u00a05a and b. Selected torsion angles are given in Table\u00a01In an attempt to form a co-crystal, equimolar amounts of _B Fig.\u00a04. It crysed Fig.\u00a04b. The d4L1H with Hg(NO3)2 in the presence a 1 M potassium acetate buffer led to the formation of colourless crystals that proved to be a potassium\u2013organic framework (3L1KH); see Fig.\u00a06+ ion is linked to the O atoms of the acid groups and has a coordination number of eight (KO8) and a distorted dodeca\u00adhedral geometry . The K\u22efO bond lengths vary between 2.682\u2005(2) and 3.069\u2005(3)\u2005\u00c5 (Table\u00a02\u2212) distances: 2.6823\u2005(2) and 2.828\u2005(2)\u2005\u00c5 compared to 3.056\u2005(3) and 3.069\u2005(3)\u2005\u00c5, respectively.Reaction of ry Fig.\u00a07a. The K\u00c5 Table\u00a02. Inter\u00ade4L1H with Zn(NO3)2 in the presence of a 1 M potassium acetate buffer led to the formation of colourless crystals that proved to be a dipotassium\u2013organic framework (2H2L1K); see Fig.\u00a08+ ions are linked to the O atoms of the acid groups and both K+ ions have a coordination number of six (KO6) and have edge-sharing bipyramidal geometries. The K+ ions are bridged by atoms O1 and O3, forming chains propagating along the b-axis direction . The K\u22efO bond lengths vary between 2.6682\u2005(12) and 2.8099\u2005(14)\u2005\u00c5 (Table\u00a03\u2212) bond lengths is much less significant  of the organic anion are similar, and similar to that in 4L1_BH , while the conformation of the second (involving atom S2) differs significantly  through white to blue . The Hirshfeld surfaces (HS) of 4L1_AH, and 4L1_BH mapped over dnorm are given in Fig.\u00a013a and b concern the O\u2014H\u22efO hydrogen bonds in the crystal structures of both compounds.The Hirshfeld surfaces are colour-mapped with the normalized contact distance, 4L1_AH, and 4L1_BH are shown in Fig.\u00a014The percentage contributions of inter-atomic contacts to the HS for both compounds are compared in Table\u00a094L1_AH, and 4L1_BH, respectively. These are followed by C\u22efH/H\u22efH contacts at, respectively, 4.5 and 4.9%. The N\u22efH/H\u22efN contacts contribute, respectively, 3.0 and 2.5%.The third most important contribution to the HS is from the S\u22efH/H\u22efS contacts at 13.4 and 16.1%, for 4L1_AH, and 4L1_BH, are given in Fig.\u00a015Etot) are also included there; see Tan et al. , the dispersion forces (Edis) and the total energy diagrams (Etot), are shown in Fig.\u00a016et al., 2017et al., 2019\u22121 within a radius of 6\u2005\u00c5 of a central reference mol\u00adecule. It can be seen that for both polymorphs the major contribution to the inter\u00admolecular inter\u00adactions is from electrostatic potential forces (Eele), reflecting the presence of the classical O\u2014H\u22efO hydrogen bonds.A comparison of the energy frameworks calculated for et al., 2016viz. 2,3,5,6-pyrazine\u00adtetra\u00adcarb\u00adoxy\u00adlic acid (pztca) and 2,3,5,6-tetra\u00adkis\u00ad(4-carb\u00adoxy\u00adphen\u00adyl)pyrazine (pztba). Ligand pztba has been shown to be extremely successful in forming metal\u2013organic frameworks potassium] . The asymmetric unit consists of half a mono-deprotonated ligand mol\u00adecule located about an inversion center, and half a potassium ion. The carb\u00adoxy H atom is disordered by symmetry, similar to the situation in the structure of 3L1KH. Here the K\u22efO bond lengths vary from 2.7951\u2005(11) to 2.8668\u2005(13)\u2005\u00c5. The K+ cation has a coordination number of 8 (KO8) and a distorted dodeca\u00adhedral geometry as in 3L1KH .Potassium salts of carb\u00adoxy\u00adlic acids are relatively common. A search for potassium salts of purely organic carb\u00adoxy\u00adlic acids and excluding hydrates, yielded over 200 hits. The potassium salt of L1 Fig.\u00a07a and 11pzdca; Fig.\u00a012-3-carb\u00adoxy\u00adpyrazine-2-carboxyl\u00adato)-di\u00adaqua\u00adpotassium], has been reported -hexa\u00adaqua\u00adbis\u00ad(6-carb\u00adoxy\u00adpyridine-2-carboxyl\u00adato-O)dipotassium potassium] , with the K\u22efO bonds lengths varying from 2.8197\u2005(14) to 3.0449\u2005(15)\u2005\u00c5. The K+ ion has a coordination number of seven (KO6N) and has an edge-sharing penta\u00adgonal anti\u00adprism geometry, forming chains . This structure can be compared to that of 2H2L1K where the two independent K+ ions, each with a coordination number of six (KO6), have edge-sharing bipyramidal geometries, also forming chains .The structure of MUMPIW is that of a potassium-organic framework Fig.\u00a017b, with s Fig.\u00a017b. This ns Fig.\u00a07b and 12et al., 1994The synthesis and crystal structure of the reagent tetra-2,3,5,6-bromo\u00admethyl-pyrazine (TBr) have been reported (Ferigo 4L1):Synthesis of 3,3\u2032,3\u2032\u2032,3\u2032\u2032\u2032-{tetra\u00adkis\u00ad(sulfanedi\u00adyl)}tetra\u00adpropionic acid  that X-ray diffraction analysis indicated to be triclinic polymorph 4L1_AH.Mercaptopropionic acid  was dissolved in 50\u2005ml THF. A minimum amount of water (a few ml) was added to dissolve 1.4166\u2005g  of NaOH. The volume of the mixture was increased to 100\u2005ml by adding THF and the reaction was stirred under reflux for 1\u2005h. Then TBr  dissolved in 50\u2005ml THF was added dropwise using an addition funnel. The mixture was stirred under reflux for 6\u2005h. After drying under vacuum, the residue was dissolved in 50\u2005ml of deionized water, and HCl puriss. was added dropwise until a clearly acid pH was obtained. This mixture was stirred at room temperature for 1\u20132\u2005h. The yellow precipitate that formed was filtered off and washed with a minimum amount of water and then CHCl4L1H in methanol gave colourless crystals of rather poor quality. However, X-ray diffraction analysis indicated that a second triclinic .1H NMR , \u03b4(ppm): 4.03 , 2.78  = 7.0, H3), 2.62  = 7.0, H4).13C NMR , \u03b4(ppm): 174.54 , 150.12 , 34.29 , 33.64 , 26.65 .20H28N2O8S4, Mw = 552.71\u2005g\u2005mol\u22121: Calculated: C 43.46, H 5.11, N 5.07%. Found: C 43.40, H 5.17, N 4.87%.Elemental Analysis for Cm/z: 591.04 [M + K]+; 575.06 [M + Na]+; 553.08 [M + H]+; 471.07; 449.09.ESI\u2013MS, \u22121) \u03bd: 2926(s), 2666(m), 2590(s), 1693(s), 1429(s), 1406(s), 1340(m), 1270(s), 1200(s), 1163(m), 1134(s), 1107(m), 1055(w), 918(s), 658(m), 489(m).IR :Synthesis of poly[sulfan\u00adyl]meth\u00adyl}pyrazin-2-yl)meth\u00adyl]sulfan\u00adyl}propano\u00adate)potas\u00adsium] (KH3)2  and 4L1H  were mixed together in 20\u2005ml of a 1\u2005M potassium acetate buffer. The mixture was left at 323\u2005K under stirring and nitro\u00adgen conditions for 1\u2005h. The mixture was then filtered and left to evaporate in air for six weeks. Colourless plate-like crystals were obtained, which were shown to be a potassium\u2013organic framework.Hg(NO\u22121) \u03bd: 3422(m), 2922(m), 1713(m), 1580(s), 1399(s), 1247(m), 1190(m), 1152(m), 1114(m), 811(m), 787(m).IR :Synthesis of poly[sulf\u00adan\u00adyl]meth\u00adyl}pyrazine-2,5-di\u00adyl)bis\u00ad(methyl\u00adene)]bis\u00ad(sulfanedi\u00adyl)}dipropionato)dipotassium] (K3)2  and 4L1H  were mixed together in 20\u2005ml of a 1M potassium acetate buffer. The mixture was left at 323\u2005K under stirring and nitro\u00adgen for 1\u2005h. The mixture was then filtered and left to evaporate in air for 6 weeks. Colourless plate-like crystals were obtained, which proved to be a dipotassium-organic framework.Zn(NO\u22121) \u03bd: 3401(m), 1579(s), 1401(s), 1303(m).IR . They were therefore included in calculated positions assuming the formation of carb\u00adoxy\u00adlic acid dimers; O\u2014H = 0.82\u2005\u00c5 and refined as riding with Uiso(H) = 1.5Ueq(O).For + salt of pyrazine tetra\u00adcarb\u00adoxy\u00adlic acid  = 1.2Ueq(C).For all four compounds, the C-bound H atoms were included in calculated positions and treated as riding on their parent C atom with C\u2014H = 0.97\u2005\u00c5 and 4L1_AH and 4L1_BH, the alert _diffrn_reflns_point_group_measured_fraction_full value  below minimum (0.95) was given. For 4L1_AH it involves 131 random reflections out of a total of 2180, viz. 6.0%, while for 4L1_BH it involves 158 random reflections out of a total of 2184, viz. 7.2%.For 4L1_AH, 4L1_BH and 2H2L1K the multiplicity of reflections was 2 or less and so an empirical absorption correction was applied.For 10.1107/S2056989021003479/pk2656sup1.cifCrystal structure: contains datablock(s) H4L1A, H4L1B, KH3L1, K2H2L1, Global. DOI: 10.1107/S2056989021003479/pk2656H4L1Asup2.hklStructure factors: contains datablock(s) H4L1A. DOI: 10.1107/S2056989021003479/pk2656H4L1Bsup3.hklStructure factors: contains datablock(s) H4L1B. DOI: 10.1107/S2056989021003479/pk2656KH3L1sup4.hklStructure factors: contains datablock(s) KH3L1. DOI: 10.1107/S2056989021003479/pk2656K2H2L1sup5.hklStructure factors: contains datablock(s) K2H2L1. DOI: Click here for additional data file.10.1107/S2056989021003479/pk2656H4L1Asup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021003479/pk2656H4L1Bsup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021003479/pk2656KH3L1sup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021003479/pk2656K2H2L1sup9.cmlSupporting information file. DOI: 2074770, 2074769, 2074768, 2074767CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two mol\u00adecules A and B are involved in inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds.The title compound, C 9H7NO2S crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit with Z = 8. Both mol\u00adecules are almost planar with a dihedral angle between the isoxazole and thio\u00adphen rings of 3.67\u2005(2)\u00b0 in mol\u00adecule A and 10.00\u2005(1) \u00b0 in mol\u00adecule B. The packing of mol\u00adecules A and B is of an ABAB\u22ef type along the b-axis direction, the configuration about the C=C bond is Z. In the crystal, the presence of C\u2014H\u22efO, C\u2014H\u22ef N and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances of 3.701\u2005(2) and 3.766\u2005(2)\u2005\u00c5] link the mol\u00adecules into a three-dimensional architecture. An analysis of Hirshfeld surfaces shows the importance of C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds in the packing mechanism of the crystalline structure.The title compound, C In the present study, we report on the synthesis, mol\u00adecular and crystal structure together with a Hirshfeld surface analysis of the title isoxazole derivative.Isoxazolones show some inter\u00adesting biological properties. They are inhibitors of the factorization of tumor necrosis alpha (TNF-\u03b1) (Laughlin A and B) in the asymmetric unit. The mol\u00adecular structure adopts a Z-configuration about the C=C [1.354\u2005(3)\u2005\u00c5 in mol\u00adecule A and 1.357\u2005(3)\u2005\u00c5 in mol\u00adecule B] double bonds. The mol\u00adecular structure of the title compound is shown in Fig.\u00a01. It crysA) and C11\u2014C12\u2014C13 (mol\u00adecule B) differing by 0.8\u2005(2)\u00b0. Also, a slight difference of 0.3\u2005(2)\u00b0 is observed between the angles C2\u2014C5\u2014C6 and C11\u2014C14\u2014C15. In mol\u00adecule A, the angle between the normal of the mol\u00adecular plane (O2A/N1A/C1A\u2013C3A) and the normal of the (S1A/C6A\u2013C9A) plane is 3.67\u2005(2)\u00b0. An important difference is observed in mol\u00adecule B, where the angle between the normal of the mol\u00adecular plane (O3B/N2B/C10B\u2013C12B) and the normal of the (S2B/C15B\u2013C18B) plane is 10.00\u2005(1)\u00b0. In the mol\u00adecular skeleton, the angle between the mean planes of the mol\u00adecules A and B is 4.09\u2005(1)\u00b0. Each of the two methyl groups, C4 and C13, has a C\u2014H bond lying in the mean plane of the mol\u00adecular skeleton, and they are oriented toward the thio\u00adphene group.The bond lengths in the two mol\u00adecules are practically equal, while there are slight differences in bond angles; with for example C2\u2014C3\u2014C4 \u2005\u00c5 and Cg3\u22efCg4ii = 3.766\u2005(2)\u2005\u00c5 where Cg1, Cg2, Cg3 and Cg4 are the centroids of the O2A/N1A/C1A\u2013C3A, S2B/C15B\u2013C18B, S1A/C6A\u2013C9A and O3B/N2B/C10B\u2013C12B rings, respectively; symmetry codes: (i) \u2212x, y, z; (ii) \u2212x, y, z]. The two mol\u00adecules A and B are involved in inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds . The H\u22efH contacts, accounting for about 35.4% of the Hirshfeld surface  represent the largest contribution and are seen in the fingerprint plot as a pair of shorts pikes at de + di = 2.2\u2005\u00c5; comparing this to van der Waals radius, we find the difference between them is about 1\u2005\u00c5, which means it is a very powerful inter\u00adaction. H\u22efO/O\u22efH contacts  make a contribution of 28.7%, with a distinctive peak in the fingerprint plot at de + di = 2.4\u2005\u00c5; the van der Waals radius sum for this inter\u00adaction is about 2.7\u2005\u00c5.The Hirshfeld surface analysis . Although the H\u22efN /N\u22efH inter\u00adactions have a notable contribution of 12% to the Hirshfeld surface , their inter\u00adatomic distances (de + di = 2.4\u2005\u00c5) are less than their van der Waals radius (2.7\u2005\u00c5), which means that it is a very strong inter\u00adaction in this structure. The presence of \u03c0\u2013\u03c0 stacking reflects the presence of C\u22efC contacts , which account for 7.9% of the Hirshfeld surface with de + di = 3.4\u2005\u00c5; the van der Waals radius is 3.4\u2005\u00c5, so we can confirm the presence of \u03c0\u2013\u03c0 stacking. Two further views of the Hirshfeld surface are shown in Fig.\u00a05The pair of short peaks at ce Fig.\u00a04e, theirts Fig.\u00a04f, whichet al., 2016Z)-4-(thio\u00adphen-2-yl\u00admethyl\u00adidene)isoxazol-5(4H)-one unit gave five hits: 4-(2-hydroxybenzyl\u00adidene)-3-methyl\u00adisoxazol-5(4H)-one -one -4-benzyl\u00adidene-3-methyl\u00adisoxazol-5(4H)-one -one -4-(4-hy\u00addroxy\u00adbenzyl\u00adidene)-3-methyl\u00adisoxazol-5(4H)-one , 10.00\u2005(1), 0.86\u2005(9), 7.02\u2005(8), 2.65\u2005(16), 4.55\u2005(15), 6.50\u2005(1), 7.98\u2005(8) and 3.18\u2005(8)\u00b0, respectively.The asymmetric unit of the title compound contains two crystallographically independent mol\u00adecules, as found for ERIXIN and WOYPIL while in AJESAK, MBYIOZ01 and VIDSAF, there is only one mol\u00adecule per asymmetric unit. The configuration about the C=C bond is via C\u2014H\u22efO hydrogen bonds, forming ABAB chains along the [10A and B is of an ABAB\u22ef type along the [100] direction. In our compound, the cohesion of the crystal is ensured by inter\u00adactions of the type C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [inter\u00adcentroid distances of 3.701\u2005(2) and 3.766\u2005(2)\u2005\u00c5 compared with 3.811\u2005(2) and 3.889\u2005(2)\u2005\u00c5 in ERIXIN and 3.767\u2005(2) and 3.867\u2005(2)\u2005\u00c5 in WOYPIL].In the crystal of WOYPIL, the individual mol\u00adecules are linked 5H4OS, 1\u2005mmol), hydroxyl\u00adamine hydro\u00adchloride , ethyl aceto\u00adacetate  and K2CO3 (5\u2005mol%) were mixed in a 25\u2005mL flask equipped with a magnetic stirrer. The mixture was refluxed in 5\u2005mL of water for 3h (followed by TLC). When the reaction was judged to be finished, the mixture was gradually poured into ice-cold water. Stirring was maintained for a few minutes and the obtained solid was filtered and purified by crystallization from ethanol (yield 72%).Thio\u00adphene-2-carbaldehyde (CUiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details for the title compound are summarized in Table\u00a0210.1107/S2056989021002632/zn2002sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002632/zn2002Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021002632/zn2002Isup3.cmlSupporting information file. DOI: 2069004CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Broussonetia kazinoki, on vascular endothelial growth factor\u2010A (VEGF\u2010A)\u2013stimulated endothelial cell responses in vitro and microvessel sprouting ex vivo. Treatment with broussonin A or B suppressed VEGF\u2010A\u2010stimulated endothelial cell proliferation by regulating the expression of cell cycle\u2013related proteins and the phosphorylation status of retinoblastoma protein. In addition, treatment with broussonin A or B abrogated VEGF\u2010A\u2010stimulated angiogenic responses including endothelial cell migration, invasion, tube formation and microvessel formation from rat aortic rings. These anti\u2010angiogenic activities of broussonin A and B were mediated through inactivation of VEGF\u2010A\u2010stimulated downstream signalling pathways, localization of vascular endothelial\u2010cadherin at cell\u2010cell contacts, and down\u2010regulation of integrin \u03b21 and integrin\u2010liked kinase. Furthermore, treatment with broussonin A or B inhibited proliferation and invasion of non\u2013small cell lung cancer and ovarian cancer cells. Taken together, our findings suggest the pharmacological potential of broussonin A and B in the regulation of angiogenesis, cancer cell growth and progression.In the present study, we demonstrate the regulatory effects and mechanism of broussonin A and B, diphenylpropane derivatives isolated from  Vascular endothelial growth factor (VEGF) has long been appreciated as a key therapeutic target for the treatment of diseases associated with pathological angiogenesis.These complex dynamics of VEGF\u2010mediated signalling networks may partially explain the limitation of anti\u2010VEGF/VEGFR therapy in the clinic. Therefore, in\u2010depth investigations of integrative signalling pathways within the tumour microenvironment may provide crucial therapeutic targets and strategies for improving clinical outcomes.Broussonetia kazinoki (B. kazinoki) Siebold (Moraceae), a deciduous shrub distributed in Eastern Asia including Korea, China and Japan, has been traditionally used as a folk medicine for the treatment of amblyopia, inflammation and oedema as well as a raw material for making high\u2010quality paper in Korea. The extract and bioactive components isolated from B. kazinoki have been reported to possess various pharmacological properties including myogenic, anti\u2010allergic, anti\u2010inflammatory, anti\u2010diabetic and anti\u2010tumour activities.B. kazinoki or marmesin, a furanocoumarin component isolated from B. kazinoki, negatively modulates VEGF\u2010A\u2010induced angiogenic responses by inactivation of VEGF\u2010A/VEGFR\u20102\u2010mediated signalling network.B. kazinoki, B. papyrifera and Anemarrhena asphodeloides (A. asphodeloides), has been reported to possess antiviral, anti\u2010inflammatory, anti\u2010adipogenic and oestrogenic properties.B. kazinoki and A. asphodeloides has been known to exert anti\u2010adipogenic and neurotrophic activities.B. kazinoki on endothelial cell and cancer cell responses.Broussonin A (2\u2010[3\u2010(4\u2010hydroxyphenyl)propyl]\u20105\u2010methoxyphenol), a diphenylpropane derivative isolated from several plants including 22.1\u00ae BulletKit media and used between passages 4 and 6 for all experiments, according to the manufacturer's instructions (Lonza). Human non\u2013small cell lung cancer (A549 and H1299) and ovarian cancer (SKOV\u20103) cells from the American Type Culture Collection  were cultured in 10% foetal bovine serum\u2010Dulbecco's modified Eagle's medium .Human umbilical vein endothelial cells (HUVECs) from Lonza  were grown in EGM\u201022.2B. kazinoki. High\u2010performance liquid chromatography (HPLC) analysis was performed on an Agilent 1200\u00a0series  using Kromasil\u00ae C18 column   with a stepwise gradient elution of methanol\u20100.05% trifluoroacetic acid in water (20%\u2013100% methanol) at a flow rate of 1\u00a0mL/min. The purity of broussonin A and B by HPLC analysis was >98%. 1H\u2010 and 13C\u2010nuclear magnetic resonance (NMR) spectra of broussonin A and B were recorded on a Bruker Ascend 700\u00a0MHz NMR spectrometer . Broussonin A: 1H\u2010NMR  7.00 , 6.92 , \u03b4 6.69 , 6.36 , 6.34 , 3.72 , 2.53 , 1.81 ; 13C\u2010NMR  \u03b4 158.9 (C\u20104\u2019), 155.6 (C\u20102\u2019), 154.8 (C\u20104'\u2019), 133.5 (C\u20101'\u2019), 129.7 (C\u20106\u2019), 128.9 , 121.0 (C\u20101\u2019), 114.6 , 104.0 (C\u20105\u2019), 100.9 (C\u20103\u2019), 54.1 (OCH3), 34.5 (C\u20103), 32.1 (C\u20102), 28.9 (C\u20101); ESI(electrospray ionization)\u2010MS (mass spectrometry) (positive mode) m/z 259 [M + H]+. Broussonin B: 1H\u2010NMR  6.98 , 6.88 , \u03b4 6.69 , 6.39 , 6.30 , 3.74 , 2.50 , 1.77 ; 13C\u2010NMR  \u03b4 158.9 (C\u20102\u2019), 156.9 (C\u20104\u2019), 155.4 (C\u20104'\u2019), 134.1 (C\u20101'\u2019), 130.4 (C\u20106\u2019), 129.5 , 122.0 (C\u20101\u2019), 115.2 , 106.7 (C\u20105\u2019), 98.9 (C\u20103\u2019), 54.8 (OCH3), 35.1 (C\u20103), 32.8 (C\u20102), 29.5 (C\u20101); ESI\u2010MS (positive mode) m/z 259 [M + H]+. The structures of broussonin A and B are presented in Figure\u00a0Broussonin A and B were isolated in an ethyl acetate fraction partitioned from the ethanolic extract of 2.3S6K (T421/S424), anti\u2010phospho\u2010Akt (S473), anti\u2010phospho\u2010ERK (T202/Y204), anti\u2010phospho\u2010p38MAPK (T180/Y182), anti\u2010phospho\u2010pRb (S780) and anti\u2010phospho\u2010pRb (S807/S811) ; anti\u2010phospho\u2010tyrosine ; anti\u2010VEGFR\u20102, anti\u2010vascular endothelial (VE)\u2010cadherin, anti\u2010integrin \u03b21, anti\u2010ILK, anti\u2010p70S6K, anti\u2010Akt, anti\u2010ERK, anti\u2010p38MAPK, anti\u2010Cdk2, anti\u2010Cdk4, anti\u2010cyclin D, anti\u2010cyclin E, anti\u2010actin antibodies and mouse and rabbit IgG\u2010horseradish peroxidase conjugates ; Alexa Fluor 488\u2013conjugated goat anti\u2010mouse IgG .The following agents were obtained from commercial sources: vascular endothelial growth factor\u2010A 165 ; anti\u2010phospho\u2010VEGFR\u20102 (Y951) ; anti\u2010phospho\u2010p702.45 cells/well, SPL Life Sciences, Gyeonggi\u2010do, Republic of Korea) were serum\u2010starved for 14\u00a0h in endothelial cell basal medium\u20102  and pretreated with broussonin A or B (0.1\u201310\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) stimulation for 24\u00a0h. In some experiments, human non\u2013small cell lung cancer (A549 and H1299) and ovarian cancer (SKOV\u20103) cells, plated on 6\u2010well plates (5\u00a0\u00d7\u00a0104 cells/well), were serum\u2010starved for 24\u00a0h in basal DMEM and pretreated with broussonin A or B (10\u00a0\u00b5M) for 30\u00a0min, followed by 10% FBS stimulation for 24\u00a0h. Cell proliferation and viability were determined as described previously.HUVECs, plated on 6\u2010well plates .Quiescent HUVECs were pretreated with broussonin A or B (10\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) stimulation for 24\u00a0h. Cells were fixed with ice\u2010cold 70% ethanol, stained with Muse\u2122 cell cycle reagent, and then analysed by a Muse2.6TM Total RNA Purification kit . RNA purity and concentration were determined using a NanoDropTM 2000\u00a0spectrophotometer . One microgram of RNA was used as template for RT\u2010mediated PCR using 1st Strand cDNA Synthesis kit . Primer sets for integrin \u03b21 were forward 5\u2019\u2010GAAGGGTTGCCCTCCAGA\u20103\u2019 and reverse 5\u2019\u2010GCTTGAGCTTCTCTGCTGTT\u20103\u2019; and the primer sets for glyceraldehydes\u20103\u2010phosphate dehydrogenase (GAPDH) were forward 5\u2019\u2010GAAGGTGAAGGTCGGAGTC\u20103\u2019 and reverse 5\u2019\u2010GAAGATGGTGATGGGATTTC\u20103\u2019.Total RNA was isolated using PureHelix2.7Quiescent HUVECs were pretreated with broussonin A or B (10\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) stimulation for the indicated time points. Cells were lysed by incubation in 50\u00a0mM Tris\u2010HCl (pH 7.4), 1% Triton X\u2010100, 150\u00a0mM NaCl, 0.5\u00a0\u03bcg/mL leupeptin, 1\u00a0\u03bcg/mL pepstatin A, 10\u00a0\u03bcg/mL aprotinin, 100\u00a0\u03bcg/mL 4\u2010(2\u2010aminoethyl)benzenesulfonyl fluoride, 1\u00a0mM EDTA, 1\u00a0mM sodium orthovanadate, 25\u00a0mM sodium fluoride, 80\u00a0mM \u03b2\u2010glycerophosphate and 10% glycerol for 30\u00a0min at 4\u00b0C. Cell lysates were subjected to immunoprecipitation and Western blot as previously described.2.8A single wound was created in the centre of confluent HUVEC monolayer by a sterile pipette tip. After serum starvation for 2\u00a0h, cells were pretreated with broussonin A or B (0.1\u201310\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) stimulation for 16\u00a0h. Following fixation with methanol, cells were stained with 0.04% Giemsa solution . The migration of cells across a wound field gap was quantified as previously described.2.9\u00ae (BD Biosciences)\u2010coated transwell inserts   were serum\u2010starved for 2\u00a0h and pretreated with broussonin A or B (1\u201310\u00a0\u03bcM) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) or 10% FBS stimulation for 16\u00a0h. After fixation with methanol, invasive cells were stained with 0.04% Giemsa solution and quantified from six different fields using x200 objective magnification.Transwell invasion assay was performed as previously described.2.10Quiescent HUVECs, plated on gelatin\u2010coated coverslips in 12\u2010well plates, were pretreated with broussonin A or B (10\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) stimulation for 30\u00a0min. Briefly, cells were fixed with 3.7% paraformaldehyde, permeabilized with 0.1% Triton X\u2010100, blocked with 5% BSA\u2010PBS, and incubated with anti\u2010VE\u2010cadherin antibody. Images were observed using a Carl Zeiss Microscope (Axio Imager.M2) and AxioVision Rel. 4.8\u00a0software .2.114 cells/mL) were plated on Matrigel\u00ae\u2010coated 24\u2010well plates and pretreated with broussonin A or B (1\u201310\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (10\u00a0ng/mL) for 6\u00a0h. Formation of capillary\u2010like structures was examined using an Olympus CKX41 inverted microscope (CAchN 10/0.25php objective) and ToupTek Toupview software .After serum starvation for 2\u00a0h, cells (4\u00a0\u00d7\u00a0102.12\u00ae were pretreated with broussonin A or B (10\u00a0\u00b5M) for 30\u00a0min, followed by VEGF\u2010A (500\u00a0ng/mL) for 3\u00a0days and then incubated with fresh broussonin A or B plus VEGF\u2010A every other day, and photographed on the 7th day using x40 objective magnification.Eight\u2010 to nine\u2010week\u2010old male Sprague Dawley rats (250\u00a0\u00b1\u00a010\u00a0g) were purchased from RaonBio Inc. . The animal experiments were conducted in accordance with the institutional guidelines. The experimental procedures were approved by the Institutional Animal Care and Use Committee at Dankook University . Thoracic aortic ring segments embedded in Matrigel2.13t test and was based on at least three different experiments. The results were considered to be statistically significant when p\u00a0<\u00a0.05.Statistical analysis was performed using Student's 33.11 cell cycle arrest, which is well correlated with suppression of cell proliferation \u2010cadherin from \u03b2\u2010catenin and plakoglobin and modulates angiogenic responses such as endothelial permeability, invasion, proliferation and tube formation.3.4S6K), Akt, extracellular signal\u2010regulated kinase (ERK) and p38\u00a0mitogen\u2010activated protein kinase (p38MAPK).S6K, Akt, ERK and p38MAPK, as compared with untreated controls , a key kinase in integrin downstream signalling pathways, which are closely associated with angiogenesis and tumour progression Figure\u00a0.39, 43.5Based on inhibitory effects of broussonin A and B on angiogenic responses, we next examined the ability of broussonin A and B to regulate proliferation and invasion in NSCLC p53 wild\u2010type A549 and p53\u2010deficient H1299 cells as well as ovarian cancer p53\u2010deficient SKOV\u20103 cells Figure\u00a0. Treatme4S6K and p38MAPK, redistribution of VE\u2010cadherin to cell\u2010cell contacts, and down\u2010regulation of integrin \u03b21 and ILK. In addition, both broussonin A and B exert anti\u2010proliferative and anti\u2010invasive activities against NSCLC and ovarian cancer cells. Our findings demonstrate the pharmacological potential of broussonin A and B in the regulation of pathological angiogenic responses associated with cancer growth and progression.In the current study, we report that both broussonin A and B negatively regulate VEGF\u2010A\u2010induced in vitro endothelial cell responses including proliferation, migration, invasion and capillary\u2010like structure formation as well as ex vivo angiogenesis. The mechanism of these anti\u2010angiogenic effects involves inactivation of VEGF\u2010A/VEGFR\u20102 downstream signalling pathways such as ERK, Akt, p70Integrins, transmembrane receptors that facilitate cell\u2010extracellular matrix and cell\u2010cell interactions, mediate a wide range of cellular responses including adhesion, migration, proliferation, invasion and angiogenesis associated with tumour growth and progression.Cell adhesion, migration and invasion are tightly controlled by the changes in the expression of adhesion molecules such as integrins and cadherins and/or activity of matrix metalloproteinases.In addition to anti\u2010angiogenic activity, both broussonin A and B have anti\u2010proliferative and anti\u2010invasive activities against NSCLC and ovarian cancer cells concomitant with suppression of integrin \u03b21 expression, independently of p53\u00a0levels. In conclusion, our results provide significant insights into the regulatory roles and therapeutic efficacy of broussonin A and B in angiogenesis and cancer progression and warrant preclinical evaluation and development as a promising therapeutic agent for the treatment of a wide range of angiogenesis\u2010related diseases including cancer.The authors declare that there are no conflicts of interest.Jae Hyeon Kim: Conceptualization ; Investigation (lead); Methodology (lead); Validation ; Visualization ; Writing \u2013 original draft ; Writing \u2013 review & editing . Sunho Kim: Data curation ; Formal analysis ; Investigation . Surim Han: Data curation ; Formal analysis ; Investigation . Eun\u2010Kyung Ahn: Conceptualization (supporting); Data curation ; Investigation (supporting). Young\u2010Rak Cho: Conceptualization (supporting); Data curation ; Investigation (supporting). Wonsik Jeong: Data curation ; Investigation (supporting). Sung Joon Kim: Data curation (supporting); Investigation (supporting). Gyu\u2010Un Bae: Conceptualization (supporting); Resources (supporting). Joa Sub Oh: Conceptualization (supporting); Resources (supporting). Dong\u2010Wan Seo: Conceptualization (lead); Data curation ; Funding acquisition (lead); Resources (lead); Supervision (lead); Writing \u2013 original draft (lead); Writing \u2013 review & editing (lead).Supplementary MaterialClick here for additional data file."}
{"text": "Three intra\u00admol\u00adecular hydrogen bonds are observed in the title compound. In the crystal, mol\u00adecules are connected by C\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds. 18H15ClN3O+\u00b7Cl\u2212\u00b72H2O, three intra\u00admol\u00adecular hydrogen bonds are observed, N\u2014H\u22efO, O\u2014H\u22efCl and O\u2014H\u22efO. In the crystal, mol\u00adecules are connected by C\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds. Strong C\u2014H\u22efCl, N\u2014H\u22efO, O\u2014H\u22efCl and O\u2014H\u22efO hydrogen-bonding inter\u00adactions are implied by the Hirshfeld surface analysis, which indicate that H\u22efH contacts make the largest contribution to the overall crystal packing at 33.0%.In the title compound, C For example, their biological activity and anti\u00admicrobial properties have been researched extensively (Neumann Database survey section). Three intra\u00admol\u00adecular hydrogen bonds are observed, N2\u2014H2C\u22efO2, O2\u2014H2A\u22efCl2 and O2\u2014H2B\u22efO3  between the pyridazine rings [centroid\u2013centroid distance = 3.4902\u2005(12)\u2005\u00c5], and also between the pyridine and benzene rings [3.7293\u2005(13) and 3.8488\u2005(13)\u2005\u00c5], forming sheets.The water mol\u00adecules and chloride anions are located in channels between the organic cations and are connected by O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds Table\u00a01 into chant Fig.\u00a02b betweeConQuest version 2021.3.0; Groom et al., 2016H)pyridazinone -one -one  on the Hirshfeld surface imply strong hydrogen-bonding inter\u00adactions of types C\u2014H\u22efCl, N\u2014H\u22efO, O\u2014H\u22efCl and O\u2014H\u22efO. In the shape-index map , the \u03c0\u2013\u03c0 inter\u00adactions are indicated by the red and blue triangles. Fig.\u00a04c and Fig.\u00a04d show di and de surfaces and Fig.\u00a04e and 4f the curvedness and fragment path surfaces. Fig.\u00a05a shows the overall two-dimensional fingerprint plot. The fingerprint plot delineated into H\u22efH contacts  has a point with the tip at de + di = 2.05\u2005\u00c5. The pair of wings in the fingerprint plot defined into H\u22efC/C\u22efH contacts (19.3 percent contribution to the HS), Fig.5c, has a pair of thin edges at de + di \u223c2.99\u2005\u00c5 while the pair of wings for the H\u22efCl/Cl\u22efH contacts  are seen as two spikes with the points at de + di = 2.97\u2005\u00c5 and de + di = 2.41\u2005\u00c5. The fingerprint plot for H\u22efO/O\u22efH contacts  has two spikes with the tips at de + di = 2.11\u2005\u00c5 and de + di = 1.83\u2005\u00c5. As seen in Fig.\u00a05f the C\u22efC contacts (7.4%) have an arrow-shaped distribution of points with tips at de + di = 3.37\u2005\u00c5. The contributions of the N\u22efH/H\u22efN contacts to the Hirshfeld surface (5.8%) are less important . Fig.\u00a06To investigate the effect of the mol\u00adecular inter\u00adactions on the crystal packing, the Hirshfeld surface Fig.\u00a03 and fingap Fig.\u00a04b, the \u03c0nt Fig.\u00a05g. Fig.\u00a0et al., 2019E)-6-(4-chloro\u00adstyr\u00adyl)-4,5-di\u00adhydro\u00adpyridazin-3(2H)-one  and nicotinaldehyde  in 30\u2005ml of ethanol, sodium ethano\u00adate  was added. The mixture was refluxed for 3\u2005h. The reaction mixture was cooled, diluted with cold water and acidified with concentrated hydro\u00adchloric acid. The precipitate was filtered, washed with water, dried and recrystallized from ethanol. White single crystals were obtained by slow evaporation at room temperature, yield 86%; m.p. 453\u2005K; FT\u2013IR (KBr): \u03bd 3322 (NH), 1651 (C=O), 1584\u2005cm\u22121 (C=N); 1H NMR  \u03b4 13.20  , 8.98 , 8.83 , 8.57 , 8.05  8.02 , 7.65 , 7.45 , 7.36 , 7.08 , 4.09 ppm ; 13C NMR  \u03b4 160.43, 145.98, 143.89, 141.87, 140.05, 139.25, 137.97, 134.90, 132.84,130.85, 128.82, 128.62, 128.54, 126.80, 125.08, 32.33 ppm. ESI-MS: m/z = 324.08 [M+H]+.The title compound was synthesized according to a previously published procedure (Daoui Uiso(H) = 1.2 Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022003346/jq2014sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022003346/jq2014Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022003346/jq2014Isup3.cmlSupporting information file. DOI: 2161716CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked by C\u2014H\u22efN inter\u00adactions along the a-axis direction, forming a C(6) chain. The mol\u00adecules are further connected by C\u2014Cl\u22ef\u03c0 inter\u00adactions and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions, forming ribbons along the a-axis direction. Hirshfeld surface analysis indicates that the greatest contributions to the crystal packing are from Cl\u22efH/H\u22efCl (35.1%), H\u22efH (10.6%), C\u22efC (9.7%), Cl\u22efCl (9.4%) and C\u22efH/H\u22efC (9.2%) inter\u00adactions.In the title compound, C The secondary important H\u22efH and C\u22efC inter\u00adactions contribute 10.6%  and 9.7% , respectively, to the Hirshfeld surface. The remaining contributions for the title compound are from Cl\u22efCl, C\u22efH/H\u22efC, Cl\u22efF/F\u22efCl, Cl\u22efC/C\u22efCl, F\u22efH/H\u22efF, N\u22efH/H\u22efN, N\u22efN and F\u22efC/ C\u22efF contacts, which are less than 9.7% and have a negligible effect on the packing. The percentage contributions of all inter\u00adactions are listed in Table\u00a03The overall two-dimensional fingerprint plot and those delineated into Cl\u22efH/H\u22efCl, H\u22efH, C\u22efC, Cl\u22efCl and C\u22efH/H\u22efC contacts in the title mol\u00adecule are illustrated in Fig.\u00a076% Fig.\u00a07c and 9.7% Fig.\u00a07d, respeet al., 2016E)-1--2-phenyl\u00addiazene unit resulted in 28 hits. Nine compounds are closely related to the title compound, viz. LEQXOX  and 60.31\u2005(14)\u00b0, respectively. In I, C\u2014H\u22efN and short Cl\u22efCl contacts are observed and in II, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short C\u2014Cl\u22efO contacts occur. In III, the benzene rings form a dihedral angle of 63.29\u2005(8)\u00b0 and the mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In IV, the benzene rings make a dihedral angle of 56.13\u2005(13)\u00b0. Mol\u00adecules are stacked in columns along the a-axis direction via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In V and VI, the aromatic rings form dihedral angles of 60.9\u2005(2) and 64.1\u2005(2)\u00b0, respectively. In the crystals, mol\u00adecules are linked through weak X\u22efCl contacts (X = Cl for V and Br for VI), C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets parallel to the ab plane. Additional van der Waals inter\u00adactions consolidate the three-dimensional packing. In VII, the dihedral angle between the two aromatic rings is 64.12\u2005(14)\u00b0. The crystal structure is stabilized by a short C\u2014H\u22efCl contact, C\u2014Cl\u22ef\u03c0 and van der Waals inter\u00adactions. In VIII, the benzene rings subtend a dihedral angle of 77.07\u2005(10)\u00b0. In the crystal, mol\u00adecules are associated into inversion dimers via short Cl\u22efCl contacts [3.3763\u2005(9)\u2005\u00c5]. In IX, the asymmetric unit comprises two similar mol\u00adecules, in which the dihedral angles between the two aromatic rings are 70.1\u2005(3) and 73.2\u2005(2)\u00b0. The crystal structure features short C\u2014H\u22efCl and C\u2014H\u22efO contacts and C\u2014H\u22ef\u03c0 and van der Waals inter\u00adactions.In the crystals of et al., 2018E)-1--2-(4-fluoro\u00adbenzyl\u00adidene)hydrazine , tetra\u00admethyl\u00adethylenedi\u00adamine (TMEDA) , CuCl  and CCl4 . After 1\u20133\u2005h , the reaction mixture was poured into \u223c0.01 M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005mL). The combined organic phase was washed with water (3 \u00d7 50\u2005mL) and brine (30\u2005mL), dried over anhydrous Na2SO4 and concentrated using a vacuum rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Colourless solid (44%); m.p. 345\u2005K. Analysis calculated for C14H7Cl4FN2 (M = 364.02): C 46.19, H 1.94, N 7.70; found: C 46.11, H 1.98, N 7.67%. 1H NMR  \u03b4 7.31\u20137.83 . 13C NMR  \u03b4 114.89, 115.12, 115.41, 115.74, 115.97, 118.33, 127.73, 128.08, 128.67, 129.17, 130.48, 132.04, 132.15 and 136.83. ESI\u2013MS: m/z: 365.11 [M + H]+.The title dye was synthesized according to the reported method  = 1.2Ueq(C). Five outliers Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989021010756/vm2255sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010756/vm2255Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021010756/vm2255Isup3.cmlSupporting information file. DOI: 2116300CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Each Tb atom is coordinated by two cyclo\u00adpenta\u00addienyl ligands in an \u03b7 5H5)2(C14H12NO2)], was synthesized from tris\u00ad(cyclo\u00adpenta\u00addien\u00adyl)(tetra\u00adhydro\u00adfuran)\u00adterbium and 2-{[(2-meth\u00adoxy\u00adphen\u00adyl)imino]\u00admeth\u00adyl}phenol. Each Tb atom is coordinated by two cyclo\u00adpenta\u00addienyl ligands in an \u03b75-coordination mode and by one N and two O atoms of the organic ligand in a tridentate \u03ba3O,N,O\u2032-mode.The air- and moisture-sensitive title compound, [Tb(C Such a combination of ligands provides an extremely broad structural diversity for cyclo\u00adpenta\u00addienyl derivatives (2-{[(2-meth\u00adoxy\u00adphen\u00adyl)imino]\u00admeth\u00adyl}phenolato)terbium, which is a product of the partial protonation of the tris(cyclo\u00adpenta\u00addien\u00adyl)terbium complex with 2-{[(2-meth\u00adoxy\u00adphen\u00adyl)imino]\u00admeth\u00adyl}phenol . Assuming that each cyclo\u00adpenta\u00addienyl ligand donates three electron pairs, the terbium atom may be considered to be ennea-coordinated. Both cyclo\u00adpenta\u00addienyl ligands are nearly symmetrically \u03b75-coordinated to the Tb3+ cation. Thus, the Cp(centroid)\u2014Tb distances [2.4207\u2005(11)\u2005\u00c5 for the C1\u2013C5 Cp ring and 2.4062\u2005(10)\u2005\u00c5 for the C6\u2013C10 Cp ring] are almost equal to the Cp(plane)\u2014Tb distances [2.4196\u2005(11)\u2005\u00c5 for C1\u2013C5 Cp ring and 2.4054\u2005(10) for C6\u2013C10 Cp ring], and the CCp\u2014Tb bond lengths are similar within each ring (Table\u00a01Cp\u2014Tb distance to the C1\u2013C5 ring is longer by 0.011\u2005\u00c5 than to the second Cp ligand. Such a slight asymmetry is caused by the presence of the tridentate asymmetric 2-{[(2-meth\u00adoxy\u00adphen\u00adyl)imino]\u00admeth\u00adyl}phenolate (L\u2212) ligand. Atoms of the ligand are situated in two planes formed by the following sets of atoms: O1, C11\u2013C16, N1, C24 (r.m.s. deviation = 0.0167\u2005\u00c5) and O2, C17\u2013C23, N1 (r.m.s. deviation = 0.0333\u2005\u00c5). The dihedral angle between these planes of 44.58\u2005(5)\u00b0 indicates a perceptible loss of conjugation between two parts of the ligand due to the tridentate \u03ba3N,O,O\u2032-coordination mode. The bond redistribution within the ligand (see table in the supporting information) and the Tb\u2014O and Tb\u2014N bond distances 2Ln(O2NC14H12)]  were previously synthesized in low yields  or protonated (LH) derivatives have been poorly studied, whereas the structures of complexes bearing their closest analogs \u2013 doubly charged 2-{[(2-oxidophen\u00adyl)imino]\u00admeth\u00adyl}phenolate and its various derivatives \u2013 have been studied moderately. This is, likely, due to the higher stability of the latter complexes, which is presumably caused, in short, by a higher degree of the optimization of electrostatic inter\u00adactions 3(thf) was obtained according to a literature procedure 3(thf)  in 15\u2005ml of THF. The reaction mixture was stirred for 24\u2005h. The solution was concentrated under vacuum to a volume of ca 8\u201310\u2005ml, and hexane (10\u2005ml) was carefully layered on top of the resulting solution to initiate crystallization. Crystals obtained after several days were dried under dynamic vacuum for 1\u2005h, yielding 0.315\u2005g . The terbium content was determined by direct complexometric titration with the disodium salt of EDTA, using xylenol orange indicator imino]\u00admeth\u00adyl}phenol  in 5\u2005ml of THF was added slowly to a solution of Tb = 1.5Ueq(C) for methyl group and Uiso(H) = 1.2Ueq(C) for others.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021013025/yk2162sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013025/yk2162Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013025/yk2162Isup3.cdxSupporting information file. DOI: 2127087CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Starting from this ligand monomeric [M(4\u2010BzhH2BoxCH)] (M=Na (7), K (18)) and dimeric [{M(4\u2010BzhH2BoxCH)}2] (M=K (28), Rb (9), Cs (10)) alkali metal complexes were synthesised by deprotonation. Abstraction of the potassium ion of 8 by reaction with 18\u2010crown\u20106 resulted in the solvent separated ion pair [{(THF)2K@(18\u2010crown\u20106)}{bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methanide}] (11), including the energetically favoured monoanionic \u2010(4\u2010BzhH2BoxCH) ligand. Further reaction of 4\u2212BzhH2BoxCH2 with three equivalents KH and two equivalents 18\u2010crown\u20106 yielded polymeric [{(THF)2K@(18\u2010crown\u20106)}{K@(18\u2010crown\u20106)K(4\u2010BzhBoxCH)}]n (n\u2192\u221e) (12) containing a trianionic ligand. The neutral ligand and herein reported alkali complexes were characterised by single X\u2010ray analyses identifying the latter as a promising precursor for low\u2010valent main group complexes.A novel sterically demanding bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methane ligand  4\u2212BzhH2BoxCH2)Bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methane ( provides a versatile platform for monomeric ligands in [M(4\u2010BzhH2BoxCH)]  and dimeric [{M(4\u2010BzhH2BoxCH)}2]  alkali metal complexes. Even more remarkable the reaction of 4\u2212BzhH2BoxCH2 with three equivalents KH and two equivalents 18\u2010crown\u20106 yields polymeric [{(THF)2K@(18\u2010crown\u20106)}{K@(18\u2010crown\u20106)K(4\u2010BzhH2BoxCH)}]n (n\u2192\u221e), containing a trianionic ligand. While the monoanions only provide N,N\u2010chelation like NacNac the latter trianion potentially provides C,N,N,C\u2010chelation and should be another promising ligand platform. N,N\u2019\u2010ligands like \u03b2\u2010diketiminatesDippNacNac . These findings initiated research into other ligand platforms, which mimic the coordination abilities of the ubiquitous NacNac ligand, in particular the \u03ba2\u2010N,N\u2010coordination of the two imine nitrogen atoms to a metal ion to form six\u2010membered metallaheterocycles. Starting from the bis(2\u2010pyridyl)methane ligand and its isoelectronically N,3N2M, M=cationic metal fragment) is maintained. In recent years the focus has been on symmetrical bis(benzoxazole\u20102\u2010yl)methanides I to IV in Scheme\u20053\u2010linker unit ethylbisimidate dihydrochloride derived from malonic acid.n\u2010butyllithium or potassium hydride.X2Al(\u2212I)]X=Cl, I). Despite of the steric demand provided by iPr\u2010 or tBu\u2010residues at C4\u2010position close to the coordination pocket in III or IV, mimicking the bulkiness provided by NacNac ligands, low\u2010oxidation or low\u2010valent Group 2 or 13 elements could so far not be synthesised. Therefore, we decided to introduce bulkier benzhydryl groups at the ligand scaffold inspired by compounds containing 2,6\u2010dibenzhydrylphenyl residues e.\u2009g. [:MH(L)]M=Ge or Sn, (L)=\u2010N(Ar)(SiiPr3), Ar=4\u2010iPr\u2010C6H2Bzh2) or [M(ArN)2CN=CtBu2]Ar=4\u2010tBu\u2010C6H2Bzh2). In the following paragraph, the six\u2010step synthesis of bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methane  and its behaviour in alkali metal coordination are discussed.Over the last decades, monoanionic bidentate 6, 4\u2010BzhH2BoxCH2), 2\u2010amino\u20103\u2010benzhydrylphenol was first synthesised according to the synthetic protocols of Quaranta et\u2005al.1\u20135 see Supporting Information). Thereafter, two equivalents of 2\u2010amino\u20103\u2010benzhydrylphenol and one equivalent of ethyl cyanoacetimidate hydrochloride C3\u2010linker unit were reacted by cyclocondensation reaction.) (7), starting material 6 and neat sodium metal were vigorously stirred until all metal was consumed (5 d). After all volatiles had been removed under reduced pressure, 7 was isolated as a white powder in excellent yields (98\u2009%). Crystals suitable for single crystal XRD experiments were grown from a saturated toluene solution at \u221228\u2009\u00b0C. Donor\u2010free 7 crystallises in the monoclinic space group P21/n with one molecule in the asymmetric unit ] (7) exhibits a distorted \u03ba2\u2010N,N\u2019\u2010coordination of the sodium ion by the imine ring nitrogen atoms. A negligible dislocation of the cation from the C3N2\u2010plane of 0.117(2) \u00c5 and a minor butterfly folding angle of 4.82(6)\u00b0 between the two benzoxazol\u20102\u2010yl moieties is observed (Table\u20057 (Na1\u2212N1 2.3392(16) \u00c5; Na1\u2212N2 2.3456(15) \u00c5) are similar to the Na1\u2212N1 2.358(6) \u00c5 bond of the six\u2010membered sodium \u03b2\u2010diketiminate complex [(THF)2NaL]3)C(Ph)}2CH) but are slightly shorter than neutral five\u2010membered TMEDA based [[{Na{N(SiMe3)(Dipp)}(TMEDA)}2] (Na1\u2212N2 2.4726(17) \u00c5; Na1\u2212N3 2.461(2) \u00c5)iPrNC(NAr)(HNiPr)}(THF)]2  (Na1\u2212N1 2.453(1) \u00c5, Na1\u2212N2 2.558(2) \u00c5).+ ion \u03c0\u2010arene, interactions are formed to one phenyl group of the benzhydryl groups each.Ar distances ranging from 2.8305(18) (Cortho) to 3.0414(18) \u00c5 (Cipso) indicate a dihaptic arene coordination.1H NMR spectra of 6 and deprotonated species 7 show a significant deshielding in toluene and simultaneous downfield shift of the methanide bridge from \u03b4(\u2212H2C\u2212)=3.85\u2005ppm to \u03b4(\u2212HC\u2212)=5.38\u2005ppm whereas benzylic protons experience a significant upfield shift from \u03b4(\u2212HCPh2)=6.41\u2005ppm to 5.27\u2005ppm. Furthermore, arene protons (Ph and NCOC6H3) are slightly upfield shifted in sodium complex 7 compared to ligand 6. Elemental analysis and mass spectrometry  confirmed the synthesis of bulk [Na(4\u2010BzhH2BoxCH)] (7).6 with potassium hydride (Scheme\u20054\u2010BzhH2BoxCH)]n with n=1 (18) and 2 (28), (YLD: 89\u2009%). Colourless crystals were grown from a saturated toluene solution at \u221230\u2009\u00b0C after 1 d. Single crystal XRD experiments revealed a monomeric as well as a dimeric species in the solid state. Monomeric [(toluene)K(4\u2010BzhH2BoxCH)] crystallises in the triclinic space group P1\u203ewith one molecule and half a toluene molecule in the asymmetric unit  \u00c5 is present. Due to the larger radius of potassium, longer K\u2212N (K1\u2212N1 2.7768(18) \u00c5; K1\u2212N2 2.6982(18) \u00c5) and a less acute N1\u2212K1\u2212N2 of 70.73(5)\u00b0 are observed. This is accompanied by an increasing butterfly folding angle to 5.54(8)\u00b0. Furthermore, potassium phenyl carbon distances suggest that the cation is \u03b72\u2010(K1\u2212C30 3.467(2) \u00c5, K1\u2212C31 3.224(2) \u00c5) and \u03b73\u2010coordinated (K1\u2212C23 3.314(2) \u00c5, K1\u2212C27 3.503(2) \u00c5, K1\u2212C28 3.236(2) \u00c5) by one phenyl residue of each benzhydryl group (A search in the CCDC version 5.41 (Aug. 2020)\u03b76\u2010coordinated ones provided a range of short contacts between K and Cortho of 2.77 to 3.76\u2005\u00c5).  (K\u2212H 2.64(4) to 3.37(3) \u00c5, K\u2212H\u2010C 117.8 to 120.7\u00b0)Ar)2] [M{N(SiMe3)2}3]  .9 and 10 also display interactions of metal ions and methanide bridges, but due to the increased residual electron density for the heavier homologues the determination of the freely refined hydrogen atom positions is not that reliable. Rising effective ionic radii,The second species derived from 0) YLD: 7\u2009% comple0) YLD: 7\u2009% comple0) YLD: 7\u2009% compleZ,Z)\u2010 and \u2010(4\u2010BzhH2BoxCH) (28: 2.775(2) to 3.015(2) \u00c5; 9: 2.905(5) to 3.063(4) \u00c5; 10: 3.033(3) to 3.285(3) \u00c5), more acute average N\u2212M\u2212N angles  as well as a growing dislocation of the metal from the C3N2 plane (28: 1.877(4) to 2.282(3) \u00c5; 9: 2.036(7) to 2.303(7) \u00c5; 10: 2.302(5) to 2.430(5) \u00c5) as well as from the \u2212HC2N unit (28: 0.85(5) to 2.18(3) \u00c5; 9: 0.699(13) to 2.196(9) \u00c5; 10: 1.16(8) to 2.60(5) \u00c5). Interestingly, the detected butterfly folding angles in both isomers \u2010(4\u2010BzhH2BoxCH)\u224823\u00b0; \u2010(4\u2010BzhH2BoxCH)\u224816\u00b0) are negligibly affected while coordinating the alkali metal ions. Additionally, all alkali metal complexes 28\u201310 were studied by 1H and 13C{1H} NMR spectroscopy in [D8]THF. Recorded 1H NMR spectra show a distinctive pattern of chemical shifts arising from the C2v symmetry of monoanionic bis(benzoxazol\u20102\u2010yl)methanide scaffold and the benzylic bound protons, whereas phenylic protons of the benzhydryl groups could not be clearly assigned due to their peak overlap. Deprotonation of 6 results in an accumulation of electron density in the benzene periphery of both benzoxazol\u20102\u2010yl moieties that again entails a general shielding of corresponding protons and an upfield shift. Concerning the 1H NMR shifts for the C\u2212H bridging position, a minute but continuous decline along K (4.66\u2005ppm)>Rb (4.65\u2005ppm)>Cs (4.64\u2005ppm) complexes is noticed. The opposite is found for para positioned protons  and benzylic protons. These protons exhibit a small but noticeable downfield shift =6.33\u2005ppm to 6.43\u2005ppm; \u03b4=6.03\u2005ppm to 6.17\u2005ppm) which is in tune with the negative charge being restored in the phenylic benzhydryl groups yielding a growing metal arene interaction. Remaining benzoxazol\u20102\u2010yl protons in ortho\u2010 and meta\u2010position shifts  do not seem to be influenced by varying alkali cations. Although 1H NMR spectra of 8\u201310 ([D8]THF) and sodium complex 7 ([D8]toluene) were measured in different solvents, benzylic protons  display a remarkable change of the average chemical shifts (\u25b5\u03b4=0.82\u2005ppm). The 87Rb NMR spectrum of 9 from THF solution shows two singlets. Most probably [{Rb(4\u2010BzhH2BoxCH)}2] rearranges to give a THF\u2010solvated rubidium cation [Rb(THF)n] (\u03b4=\u22121.69\u2005ppm) and a bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methanide} based anion [Rb(4\u2010BzhH2BoxCH)2]\u2212 (\u03b4=\u2212254.69\u2005ppm). The 133Cs NMR spectrum of 10 displays only one signal at \u03b4=\u221231.12\u2005ppm. Additionally, elemental analysis and mass spectrometry  confirmed the synthesis of heavier alkali complexes 8\u201310.These features Table\u2005 cause riZ,Z)\u2010 and \u2010isomers of complex 8\u201310 and based on former gained knowledge of sterically less demanding bis(benzoxazol\u20102\u2010yl)methanide potassium complexes+ [4\u2010BzhH2BoxCH]\u2212 (11) was isolated as a reddish solid in excellent yields (95\u2009%). Crystals suitable for single XRD experiments were grown by vapour diffusion of pentane to a saturated THF solution of 11 at ambient temperature after 3 d. The colourless crystals in the triclinic space group P1\u203econtain one bis(4\u2010benzhydryl\u2010benzoxazol\u20102\u2010yl)methanide anion and two halve (THF)2K(18\u2010crown\u20106)} cations in the asymmetric unit K(18\u2010crown\u20106)] . (11) was confirmed by mass spectrometry  and elemental analysis.On the basis of reported 2K(18\u2010crown\u20106)}{K2(4\u2010BzhBoxCH)}]n (n\u2192\u221e) 12 as very sensitive dark purple crystals by storing THF solutions at \u221230\u2009\u00b0C. The crystal selection and mounting was challenging due to the dark colour and high sensitivity of compound 12. Thus, a moderate single crystal XRD data set could be collected after many attempts. Furthermore, the synthesis of 12 was improved by using ligand 6 and the exact stoichiometric quantities (4\u2010BzhH2BoxCH2:KH:18\u2010crown\u20106=1\u2009:\u20093\u2009:\u20092) . Obtained THF solution was cooled to \u221230\u2009\u00b0C for crystallisation. Complex 12 crystallises in the monoclinic space group P2/n with half a formula unit in the asymmetric unit  \u00c5, C5\u2212K2 3.245(8) \u00c5) to the aryl moieties of two adjacent \u2010trianions and also coordinated by an equatorial crown ether molecule. The \u03b72\u2010coordination provides the link in the polymeric structure. Finally, a third potassium ion in the coordination pocket is surrounded by two nitrogen atoms in \u03ba2\u2010fashion (N\u2212K1 2.686(3) \u00c5) and a phenyl ring of each benzhydryl moiety in asymmetrically \u03b76\u2010fashion (CPh\u2212K1: 2.930(3) \u00c5 to 3.291(3) \u00c5), respectively. Determined nitrogen potassium distances and the perfect planarity of the ligand scaffold with the potassium ion in the plane of the trianion are in good agreement with the unsolvated \u03ba2\u2010N,N\u2010[K(DippNacNac)]ipso\u2010atoms are basically shortened (1.426(4) to 1.478(4) \u00c5) compared to HCbzh\u2212Cipso of complexes 6\u201311 (1.508(8) \u00c5 to 1.538(6) \u00c5) because of the deprotonation of the two benzylic positions (Cbzh) (benzhydryl group). The two anionic C9\u2010atoms are essentially in plane with the bound Cipso\u2010atoms  similar to previously studied potassium trityl complexes [KCPh3(THF)(PMDTA)],3(PMDTA)]3(L)]n .2\u2010hybridised carbon atoms (for details see Supporting Information), while the steric constraints prevent the phenyl rings from being coplanar leading to a propeller\u2010like arrangement. Within this arrangement, angles \u03c6 of the phenyl groups with respect to C2\u2212C10\u2212C16 plane (C3\u2010plane) are \u03c6=32.38(17)\u00b0 (C10 to C15), and 49.68(10)\u00b0 (C1 to C6), whereas the smallest angle and shortest bond (C9\u2212C16 1.426(4) \u00c5) involves the phenyl system to which the cation is coordinated. These parameters correspond to an increased \u03c0\u2010electron\u2010delocalisation that is correlated with the overlap of the C3\u2010plane (C2\u2212C10\u2212C16) and coordinating phenyl ring (C16 to C21) which is dependent on cos(\u03c6)2 function\u03c6=17.7\u00b0,\u224890\u2009%). Further direct analyses of 12 were challenging due to its low solubility in most solvents . To find further evidence for the synthesis of trifold deprotonated anion (4\u2010BzhBoxCH), suspensions of the dark red precipitate (12) were once again protonated (excess\u224820\u2005eq. H2O or D2O) in small scale (NMR experiment). These 1H and 2D NMR experiments (for details see Supporting Information), as well as mass spectrometry , confirmed the previous synthesis of 12.Since Brown or Buncel and Menon ascertained that triphenylmethane is deprotonated in THF by potassium hydride when DMFwn\u20106)}{K2\u2010BzhBoxCH6 (4\u2212BzhH2BoxCH2) comprising benzhydryl groups at both C4\u2010positions (ortho imine positions) in spatial proximity to the coordination pocket was presented. To get a better knowledge of its properties and find a possible precursor complex for subsequent salt metathesis reactions, 6 was deprotonated with alkali metal bases. Obtained products were analysed by NMR spectroscopy, mass spectrometry as well as single crystal XRD experiments. Crystals grown from toluene solutions unveiled monomeric [M(4\u2010BzhH2BoxCH)] (M=Na (7), K (18)) and dimeric [{M(4\u2010BzhH2BoxCH)}2] (M=K (28), Rb (9), Cs (10)) species in solid state. Latter alkali metal complexes display distorted \u03ba2\u2010N,N\u2010coordinated \u2010 and an \u2010(4\u2010BzhH2BoxCH) configurational isomers, which display various polyhaptic metal arene interactions. Furthermore, potassium ion sequestration of 8 by 18\u2010crown\u20106 resulted in [{(THF)2K(18\u2010crown\u20106)}(4\u2010BzhH2BoxCH)] (11) a solvent separated ion pair containing energetically favoured monoanionic \u2010(4\u2010BzhH2BoxCH) ligand. Additionally, reaction of 4\u2010BzhH2BoxCH2 with three equivalents KH and two equivalents 18\u2010crown\u20106 yielded polymeric [{(THF)2K@(18\u2010crown\u20106)}{K@(18\u2010crown\u20106)K(4\u2010BzhBoxCH)}]n (n\u2192\u221e) (12) featuring a remarkable trianionic ligand. The single crystal X\u2010ray diffraction experiment of 12 revealed one of the potassium ions to be \u03b72\u2010coordinated by the benzoxazol\u20102\u2010yl scaffold of two adjacent \u2010ligands plus a crown ether molecule. A second potassium ion is surrounded by two nitrogen atoms in \u03ba2\u2010fashion as well as one phenyl ring of each benzhydryl moiety in a symmetrically \u03b76\u2010fashion, respectively. Future work with regard to the mono\u2010 (4\u2010BzhH2BoxCH) and trianionic (4\u2010BzhBoxCH) ligand will focus on the coordination of other metal, i.\u2009e. those from Group 13 or lanthanides. The benzhydryl groups attached to the benzoxazol\u20102\u2010yl scaffold seem to exhibit similar qualities to the triphenylmethane, which is able to stabilise carbanionic, radical or carbonium ionic species owing to the extensive \u03c0\u2010delocalisation. With this in mind, future research might focus on the synthesis of 4\u2010BzhH2BoxCH2 based radical and carbonium ion compounds.Within this work, the six\u2010step synthesis and characterisation of a novel bulky bis(benzoxazol\u20102\u2010yl)methane ligand d6, thf\u2010 d8, toluene\u2010 d8).[45] Deuterated benzene and toluene were dried over K (65\u2009\u00b0C), THF was pre\u2010dried with LiAlH4 and stored over activated molecular sieve (3\u2005\u00c5) and stored in an argon dry box. Elemental analyses  were performed on a Vario EL3 at the Mikroanalytische Labor, Institut f\u00fcr Anorganische Chemie, University of G\u00f6ttingen. LIFDI\u2010MS spectra were measured on a Jeol AccuTOF spectrometer and ESI (HR\u2010MS) measurements were performed on Bruker maXis spectrometer. All pKa measurements in acetonitrile were carried out as in reference [13]. Shock\u2010cooled crystals were selected from a Schlenk flask under argon atmosphere using the X\u2010TEMP2 device.6, 18, 9, 10, 11) or Ag\u2010  I\u03bcS microfocus source.6 a 3\u03bb correction was applied.2 using the full\u2010matrix least\u2010squares methods of SHELXL6),2031908 (for 7), 2031909 (for 81), 2031910 (for 82), 2031911 (for 9), 2031912 (for 10), 2031913 (for 11), and 2031914 (for 12)Deposition Numbers 2031907  and 2D  NMR spectroscopic data were recorded on a Bruker Ascend 500\u2005MHz, 400\u2005MHz, and Avance 300\u2005MHz spectrometer and referenced to the deuterated solvent  should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The structures of the six hydrogen-bonded 1:1 compounds of 4-methyl\u00adquinoline with 2-chloro-4-nitro\u00adbenzoic acid, 2-chloro-5-nitro\u00adbenzoic acid, 2-chloro-6-nitro\u00adbenzoic acid, 3-chloro-2-nitro\u00adbenzoic acid, 4-chloro-2-nitro\u00adbenzoic acid and 5-chloro-2-nitro\u00adbenzoic acid have been determined at 185\u2013190\u2005K. In each crystal, the acid and base mol\u00adecules are linked by a short hydrogen bond between a carb\u00adoxy/carboxyl\u00adate O atom and an N atom of the base. 10H9N) with chloro- and nitro-substituted benzoic acids (C7H4ClNO4), namely, 4-methyl\u00adquinolinium 2-chloro-4-nitro\u00adbenzoate, C10H10N+\u00b7C7H3ClNO4\u2212, (I), 4-methyl\u00adquinoline\u20132-chloro-5-nitro\u00adbenzoic acid (1/1), C10H9N\u00b7C7H4ClNO4, (II), 4-methyl\u00adquinolinium 2-chloro-6-nitro\u00adbenzoate, C10H9.63N0.63+\u00b7C7H3.37ClNO40.63\u2212, (III), 4-methyl\u00adquinolinium 3-chloro-2-nitro\u00adbenzoate, C10H9.54N0.54+\u00b7C7H3.46ClNO40.54\u2212, (IV), 4-methyl\u00adquinolinium 4-chloro-2-nitro\u00adbenzoate, C10H10N+\u00b7C7H3ClNO4\u2212, (V), and 4-methyl\u00adquinolinium 5-chloro-2-nitro\u00adbenzoate, C10H10N+\u00b7C7H3ClNO4\u2212, have been determined at 185\u2013190\u2005K. In each compound, the acid and base mol\u00adecules are linked by a short hydrogen bond between a carb\u00adoxy (or carboxyl\u00adate) O atom and an N atom of the base. The O\u22efN distances are 2.5652\u2005(14), 2.556\u2005(3), 2.5485\u2005(13), 2.5364\u2005(13), 2.5568\u2005(13) and 2.5252\u2005(11)\u2005\u00c5, respectively, for compounds (I)\u2013(VI). In the hydrogen-bonded acid\u2013base units of (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.37\u2005(3):0.63\u2005(3) and 0.46\u2005(3):0.54\u2005(4), respectively, for (III) and (IV). The H atoms in the hydrogen-bonded units of (I), (V) and (VI) are located at the N-atom site, while the H atom in (II) is located at the O-atom site. In all the crystals of (I)\u2013(VI), \u03c0\u2013\u03c0 stacking inter\u00adactions between the quinoline ring systems and C\u2014H\u22efO hydrogen bonds are observed. Similar layer structures are constructed in (IV)\u2013(VI) through these inter\u00adactions together with \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of the adjacent acid mol\u00adecules. A short Cl\u22efCl contact and an N\u2014O\u22ef\u03c0 inter\u00adaction are present in (I), while a C\u2014H\u22efCl hydrogen bond and a \u03c0\u2013\u03c0 inter\u00adaction between the benzene ring of the acid mol\u00adecule and the quinoline ring system in (II), and a C\u2014H\u22ef\u03c0 inter\u00adaction in (III) are observed. Hirshfeld surfaces for the title compounds mapped over dnorm and shape index were generated to visualize the weak inter\u00admolecular inter\u00adactions.The structures of the six hydrogen-bonded 1:1 compounds of 4-methyl\u00adquinoline (C Ka values of the acids and bases as well as the inter\u00admolecular inter\u00adactions in the crystals. In our ongoing studies of crystal structures for the system of quinoline derivatives\u2013chloro- and nitro-substituted benzoic acids, we have shown that three compounds of quinoline with 3-chloro-2-nitro\u00adbenzoic acid, 4-chloro-2-nitro\u00adbenzoic acid and 5-chloro-2-nitro\u00adbenzoic acid  \u2013 pKa(acid)] values of these compounds are in the range 2.93\u20133.38. Although the pKa value of 4-methyl\u00adquinoline is 5.66, which is slight larger than quinoline (pKa = 4.90) and 6-methyl\u00adquinoline (pKa = 5.20), the system of 4-methyl\u00adquinoline\u2013chloro- and nitro-substituted benzoic acids is an attractive candidate for studying short hydrogen bonds and also weak inter\u00admolecular inter\u00adactions. We report here crystal structures of six hydrogen-bonded compounds, namely, 4-methyl\u00adquinolinium 2-chloro-4-nitro\u00adbenzoate, (I)Ka values are 3.62, 3.44, 4.04, 3.84, 3.69 and 3.80, respectively, for (I)\u2013(VI) (Table\u00a01The properties of hydrogen bonds formed between organic acids and organic bases depend on the p) Table\u00a01.The mol\u00adecular structures of compounds (I)\u2013(VI) are shown in Fig.\u00a01abKa value of each compound are also given in Table\u00a01The dihedral angles made by the benzene C1\u2013C6 ring, the carb\u00adoxy/carboxyl\u00adate O1/C7/O2 plane and the nitro O3/N1/O4 plane of the acid, and the quinoline N2/C8\u2013C16 ring system of the base in each hydrogen-bonded acid-base unit of (I)\u2013(VI) are summarized in Table\u00a01In all the compounds of 3-chloro-2-nitro\u00adbenzoic acid and 4-chloro-2-nitro\u00adbenzoic acid, the nitro O3/N1/O4 group is approximately perpendicular to the benzene C1\u2013C6 ring with dihedral angles of 74.4\u2005(3)\u201388.54\u2005(13)\u00b0, while in the 2-chloro-6-nitro\u00adbenzoic acid mol\u00adecule of compound (III)Ka value is observed for each system of quinoline and 6-methyl\u00adquinoline compounds, while for the title compounds (I)\u2013(VI) this correlation is somewhat low.The correlation between the H-atom position in the short hydrogen bond and the \u0394pCg2\u22efCg2, Cg2\u22efCg3 and Cg3\u22efCg3, are 3.4323\u2005(7)\u20133.7751\u2005(8), 3.5878\u2005(7)\u20133.9304\u2005(9) and 3.7719\u2005(8)\u20133.9227\u2005(9)\u2005\u00c5, respectively, where Cg2 and Cg3 are the centroids of the N2/C8\u2013C11/C16 and C11\u2013C16 rings of the quinoline ring system, respectively. The base mol\u00adecules in the crystals of (I)via these \u03c0\u2013\u03c0 inter\u00adactions, while in (III)\u2013(VI) inversion-related base mol\u00adecules are alternately stacked in column-like structures. On the other hand, \u03c0\u2013\u03c0 inter\u00adactions between the inversion-related acid mol\u00adecules are only observed in crystals (IV)\u2013(VI); the centroid-centroid distances, Cg1\u22efCg1, are 3.5702\u2005(7)\u20133.8602\u2005(6)\u2005\u00c5, where Cg1 is the centroid of the C1\u2013C6 ring. Detailed supra\u00admolecular features in the crystals formed through these \u03c0\u2013\u03c0 inter\u00adactions combined with other weak inter\u00admolecular inter\u00adactions are described below.In all the crystals of (I)\u2013(VI), \u03c0\u2013\u03c0 inter\u00adactions between the quinoline ring systems, related by an inversion centre to each other, are observed. The centroid\u2013centroid distances between the quinoline ring systems, namely, via \u03c0\u2013\u03c0 inter\u00adactions between the quinoline ring systems . The dimeric units are further linked via a C\u2014H\u22efO hydrogen bond \u2005\u00c5. Between the layers, an N\u2014O\u22ef\u03c0 inter\u00adaction \u2005\u00c5; symmetry code: (v) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a02] and a C\u2014H\u22efO hydrogen bond on Fig.\u00a02. The ribon Fig.\u00a02 via anotvia C\u2014H\u22efO hydrogen bonds  x, y\u00a0+\u00a01, z; (vi) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z]. The acid\u2013base units are linked via these \u03c0\u2013\u03c0 inter\u00adactions, forming a ribbon structure along the b-axis direction on Fig.\u00a04. The tapon Fig.\u00a05.i, C13\u2014H13\u22efO2ii and C14\u2014H14\u22efCg1ii; symmetry codes as in Table\u00a04c-axis direction  \u2212x, \u2212y, \u2212z\u00a0+\u00a01; (v) \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a01].In the crystal of (III)on Fig.\u00a06. The basms Fig.\u00a07, and thua-axis direction  \u2212x\u00a0+\u00a01, \u2212y, z\u00a0+\u00a01; (iv) \u2212x, \u2212y, \u2212z\u00a0+\u00a01]. The ribbons are further linked into a layer parallel to the (011) plane  of 3.6685\u2005(8)\u2005\u00c5 . The layers are linked by a C\u2014H\u22efO hydrogen bond on Fig.\u00a08 via C\u2014H\u22efne Fig.\u00a09 via a \u03c0\u2013a-axis direction , 3.7751\u2005(8), 3.7870\u2005(8), 3.9304\u2005(9) and 3.7719\u2005(8)\u2005\u00c5, respectively, for Cg1\u22efCg1vi, Cg2\u22efCg2iii, Cg2\u22efCg3ii, Cg2\u22efCg3iii and Cg3\u22efCg3ii . Between the layers, a C\u2014H\u22efO hydrogen bond is observed n Fig.\u00a010 via a C\u2014C2/c) is different from those of (IV)Pvia \u03c0\u2013\u03c0 inter\u00adactions between the quinoline ring systems and C\u2014H\u22efO hydrogen bonds . The ribbons are connected into a layer parallel to (10via a weak \u03c0\u2013\u03c0 inter\u00adaction between adjacent acid rings with Cg1\u22efCg1iv = 3.8602\u2005(6)\u2005\u00c5 .Uiso(H) = 1.5Ueq(N or O); the refined distances are given in Tables 4Uiso(H) = 1.2 or 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0810.1107/S2056989021010896/hb7991sup1.cifCrystal structure: contains datablock(s) global, I, II, III, IV, V, VI. DOI: 10.1107/S2056989021010896/hb7991Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991Isup8.cmlSupporting information file. DOI: 10.1107/S2056989021010896/hb7991IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991IIsup9.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991IIIsup10.cmlSupporting information file. DOI: 10.1107/S2056989021010896/hb7991IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991IVsup11.cmlSupporting information file. DOI: 10.1107/S2056989021010896/hb7991IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991Vsup12.cmlSupporting information file. DOI: 10.1107/S2056989021010896/hb7991Vsup6.hklStructure factors: contains datablock(s) V. DOI: Click here for additional data file.10.1107/S2056989021010896/hb7991VIsup13.cmlSupporting information file. DOI: 10.1107/S2056989021010896/hb7991VIsup7.hklStructure factors: contains datablock(s) VI. DOI: 2116680, 2116679, 2116678, 2116677, 2116676, 2116675CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Structures of three tetrahalophthalic anhydrides , Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair\u00b7\u00b7\u00b7\u03c0-hole (lp\u00b7\u00b7\u00b7\u03c0h) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X\u00b7\u00b7\u00b7O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the \u03c0 system (\u03c0-hole) of the anhydride ring (further lp(O)\u00b7\u00b7\u00b7\u03c0h) were observed. Computational studies by a number of theoretical methods  demonstrated that the X\u00b7\u00b7\u00b7O(anhydride) contacts in TCPA and TBPA and lp(O)\u00b7\u00b7\u00b7\u03c0h in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X\u00b7\u00b7\u00b7O(acyl) and X\u00b7\u00b7\u00b7X HaBs, and, for TIPA, the main contribution provided I\u00b7\u00b7\u00b7I HaBs. Charge transfer (CT) complexes are widely applied in different fields including sensors , ferroelIn the context of the discussion of noncovalent interactions, X\u00b7\u00b7\u00b7X  ,14,17,18Our experience in halogen bonding investigations ,21,22,23Literature structures of TXPA include one structure for TIPA: BOPDOZ, three for TCPA: TECLPA01-3, and five for TBPA: TBPHAN and TBPHAN01\u20134. TIPA and all TCPA structures were determined in the 1970s\u201380s and have poor quality by modern requirements. Because of this reason, we obtained a series of high-quality crystals of tetrahalophthalic anhydrides (including TBPA) and redetermined their structures (R \u2264 3%) using modern XRD equipment , C\u2013X\u00b7\u00b7\u00b7O(anhydride), and C\u2013X\u00b7\u00b7\u00b7X, where X is halogen atom  was carried out for each crystal with the aim to investigate the contribution of all intramolecular interactions in crystal packing (molecular surfaces are depicted in As it follows from Further contacts are considered in the order of their uniqueness and significance of the contribution to the supramolecular structure.RvdW [C\u2013X\u00b7\u00b7\u00b7O(anhydride) interaction between the halogen atom (Cl2/Br2) and the anhydride oxygen atom (O1) is the distinctive feature of crystal packing of TCPA and TBPA. The distances C4\u2013Cl2\u00b7\u00b7\u00b7O1 and C4\u2013Br2\u00b7\u00b7\u00b7O1 (3.0972(14) \u00c5 and 3.1873(19) \u00c5, respectively, RvdW ) \u00b7\u00b7\u00b7\u03c0h bifurcate interaction between anhydride oxygen and two adjacent carbon atoms of a fused furan ring was found. The distances O1\u00b7\u00b7\u00b7C7 and O1\u00b7\u00b7\u00b7C8 were 3.057(4) \u00c5 and 3.127(4) \u00c5, respectively, and the appropriate \u03a3H-carbazole (CCDC code VILFIF) and its N-methylated analogue (CCDC code WEXKEP) as well as the crystal of 2,3-dichloromaleic anhydride (CCDC code LIZCOM). The geometrical parameters of C\u2013X\u00b7\u00b7\u00b7O(anhydride) interactions in these structures are presented in vdW radii, the conducted theoretical DFT calculations  short contacts: the co-crystals of pyromellitic dianhydride with 3,6-dibromo-9arene interaction was observed only for TIPA.Besides C\u2013X\u00b7\u00b7\u00b7O(anhydride) contact in TCPA and TBPA, several types of HaB were observed in each crystal structure, which include HaB with acyl oxygen atom C\u2013X\u00b7\u00b7\u00b7O=C and type II halogen\u2013halogen contacts X\u00b7\u00b7\u00b7X. These interactions were presented in structures of all TXPA, whereas I\u00b7\u00b7\u00b7CRvdW . The angles \u2220(C\u2013X\u00b7\u00b7\u00b7O) varied in the range 173.08(7)\u2013177.59(9)\u00b0, satisfying the IUPAC criteria for HaB [In the structures of TXPA each molecule forms a HaB with the acyl oxygen. The X\u00b7\u00b7\u00b7O(acyl) distances equaled 3.0373(16) \u00c5, 3.093(2) \u00c5, and 3.141(3) \u00c5, respectively, which were shorter than the appropriate \u03a3 for HaB . NoncovaRvdW = 3.50 \u00c5); the distance Br1\u00b7\u00b7\u00b7Br2 was 3.5816(4) \u00c5 (vs. \u03a3RvdW was 3.70 \u00c5). The angles \u2220(C3\u2013Cl1\u00b7\u00b7\u00b7Cl2) = 174.58(7)\u00b0 and \u2220(C1\u2013Br1\u00b7\u00b7\u00b7Br2) = 173.89(8)\u00b0 satisfied the criteria of HaB [In the crystals of TCPA and TBPA, there are two types of halogen atoms, and one behaves as an acceptor and one as a donor of X\u00b7\u00b7\u00b7X HaB. The contact Cl1\u00b7\u00b7\u00b7Cl2 is rather elongated (the interatomic distance was 3.4978(7) \u00c5 vs. \u03a3a of HaB . The HaBa of HaB .RvdW (3.96 \u00c5). The angles \u2220(C4\u2013I2\u00b7\u00b7\u00b7I1) = 174.00(8)\u00b0 and \u2220(C5\u2013I3\u00b7\u00b7\u00b7I3) = 157.67(9)\u00b0 are consistent with the IUPAC criteria for HaB [The arrangement of C\u2013I\u00b7\u00b7\u00b7I bonds in TIPA is different from the noncovalent C\u2013X\u00b7\u00b7\u00b7X bonding in the TCPA and TBPA structures described above. Each molecule of TIPA has two HaB donor iodine atoms, which form contacts C4\u2013I2\u00b7\u00b7\u00b7I1 and C5\u2013I3\u00b7\u00b7\u00b7I3. The distances (3.7497(6) \u00c5 and 3.7760(5) \u00c5, respectively) were shorter than \u03a3 for HaB . The I3 RvdW . In the case of TBPA, the distance of Br4\u00b7\u00b7\u00b7C2 was slightly longer than the \u03a3RvdW (3.584(3) \u00c5 vs. 3.55 \u00c5).The from-the-atom lp(X)\u00b7\u00b7\u00b7\u03c0h interaction involving halogen atoms and a furan ring was observed in the TCPA and TBPA crystals . The disRvdW was 3.22 \u00c5. Additionally, another acyl oxygen atom O3 in the TCPA molecule takes part in from-the-atom lp(O)\u00b7\u00b7\u00b7\u03c0h binding O3\u00b7\u00b7\u00b7C8 with the furan ring (the distance was 3.209(2) \u00c5 vs. \u03a3RvdW = 3.22 \u00c5).In the cases of TCPA and TBPA, the acyl oxygen O2 forms from-the-bond lp(O)\u00b7\u00b7\u00b7\u03c0h bonding with C1 and C2 atoms of the fused five-membered ring. The distances O2\u00b7\u00b7\u00b7C1 and O2\u00b7\u00b7\u00b7C2 varied in the range of 2.939(3)\u20132.951(2) \u00c5 and 3.076(4)\u20133.043(3) \u00c5 for TCPA and TBPA, correspondingly, whereas the appropriate \u03a3Contrastingly, in the TIPA crystal lp\u00b7\u00b7\u00b7\u03c0h interactions were realized only at the expense of the O1 atom of the furan ring as discussed above.The strength and nature of interactions were investigated for the most relevant contacts (C\u2013X\u00b7\u00b7\u00b7O (acyl or anhydride) and C\u2013X\u00b7\u00b7\u00b7X, where X is a halogen atom) by a number of theoretical methods: the molecular electrostatic potential (MEP) ,28, the The MEP surface is important to understand the nature of noncovalent interactions regulated by electrostatic effects ,28. On tb) and Laplacian (\u22072\u03c1b) and total energy density (Hb) at the BCP. Low values of \u03c1b (0.008\u20130.010 a.u.), positive values f \u22072\u03c1b (0.024\u20130.040 a.u.), and virtually zero values of Hb are typical for HaBs of weak strength [2)\u03c1b (from \u22120.010 to \u22120.020 a.u.) indicates that these interactions between tetrahalophthalic anhydrides were attractive and that they fall into the van der Waals domain \u03c1b(r) function mapped on the \u03b4ginter isosurface and the 2D plot of the \u03b4ginter descriptor against sign(\u03bb2)\u03c1b(r) are shown in The contacts in question were additionally examined and visualized by the independent gradient model method. The IGMH approach provides a quantitative reference for the characterization of noncovalent interactions, such as the fully noninteracting gradient reference |\u2207\u03c1The charge transfer (CT) is another important factor that may determine HaB. The second-order perturbation energy (E(2)) and the charge transfer value (\u2206occ) can be used to measure the intermolecular interactions . One canIn order to provide further insight into the electron density changes upon the formation of a halogen bond, electron density difference maps (EDD) for bimolecular fragments tetrahalophthalic anhydrides were calculated and the results are illustrated in Red regions represent the accumulation of electron density as a result of the formation of the complex, and blue regions indicate loss of electron density. The EDD plots also show that polarization effects caused by the positive \u03c3-hole developed on the halogen atom tend to shift electron density from donor atoms and hence increase the electron density in the intermolecular space between halogen and oxygen atoms. The polarization of electron density between the halogen and donor atoms clearly implies the formation of the X\u00b7\u00b7\u00b7O/X interaction, which was also illustrated by the results of the NBO analysis .int) into its components , exchange (Eexch), induction (Eind), and dispersion (Edis) terms). Here, the SAPT0 level of theory was used to determine the Eint of the HaB bond in the bimolecular fragments in the X-ray structures  changed, which evidenced the critical role of packaging effects. Optimization of the TBPA fragment led to a contact switch from Br\u00b7\u00b7\u00b7O(anhydride) to two Br\u00b7\u00b7\u00b7O(carboxyl). The optimization of TIPAF1 led to a collapse of the structure, which was rearranged to the layered geometry. Thus, this interaction was dominated by the dispersion character over the electrostatic, which possibly led to the formation of a layered structure. Therefore, the O\u00b7\u00b7\u00b7C interactions between TIPA molecules were not sufficiently strong to be preserved in a gas phase.Finally, we investigated the dependence of X/C\u00b7\u00b7\u00b7O(anhydride) interactions on packing effects. To this aim, the full geometry optimization of the bimolecular fragments  was perf2Br2, and CH2I2 respectively.Tetrahlophthalic anhydrides are commercially available compounds and were purchased from Merck. Crystals of TCPA, TBPA, and TIPA suitable for X-ray studies were obtained via slow evaporation of solutions of the corresponding anhydrides in DMSO, CHwww.ccdc.cam.ac.uk/data_request/cif (accessed on 22 May 2021).X-ray diffraction studies were performed at 100 K on an Xcalibur Eos diffractometer (for TBPA and TIPA) using Mo-K\u03b1 (\u03bb = 0.71073 nm) radiation and SuperNova diffractometer (for TCPA) using Cu-K\u03b1 (\u03bb = 0.154184 nm) radiation. All structures were solved by direct methods by means of the SHELX program  incorporWave function calculations for the QTAIM, IGM, EDD, and NBO analyses were carried out using the crystallographic coordinate at the DFT PBE0 ,61 levelThe QTAIM, IGM, and EDD calculations were carried out using the Multiwfn 3.8 software ,71,72. TIn this work, we studied noncovalent interactions in the crystals of TXPA and recognized hitherto undescribed X\u00b7\u00b7\u00b7O(anhydride) short contacts in the structures of TCPA and TBPA. Based on the analysis of geometrical parameters, these contacts have been classified as HaBs. Contrastingly, in the crystal structure of TIPA, such HaB was not observed and anhydride oxygen was involved in the lp\u00b7\u00b7\u00b7\u03c0h interaction with C atoms of the anhydride system.int = \u22121.8 and \u22122.3 kcal/mol for TCPA and TBPA, respectively) and were apparently caused by packing effects. The structure of the TIPA crystal was predominantly directed by the strong I\u00b7\u00b7\u00b7I HaBs with a lesser role for the C\u2013I\u00b7\u00b7\u00b7O(acyl) interaction , which provide another crystal packing profile and, hence, the absence of X\u00b7\u00b7\u00b7O(anhydride) contact. In addition, the performed calculations established that described X\u00b7\u00b7\u00b7O(anhydride) HaBs have an electrostatic and dispersive nature.Theoretical calculations demonstrated that the greater contribution to the architecture of TCPA and TBPA crystals were made by the C\u2013X\u00b7\u00b7\u00b7O(acyl) and C\u2013X\u00b7\u00b7\u00b7X HaBs, whereas X\u00b7\u00b7\u00b7O(anhydride) HaBs were weaker (EOn the one hand, these findings should be taken into account when using TXPA as CT acceptors because formation of close contacts may influence the CT complex structure. On the other hand, the ability of TXPA to form different types of non-covalent interactions can be useful for crystal engineering purposes and makes these species attractive as building blocks for the assembling of supramolecular constructions."}
{"text": "N-haloimides form two types of short (imide)X\u00b7\u00b7\u00b7N and X\u2013X\u00b7\u00b7\u00b7N  halogen bonds. Nucleophilic substitution or ligand-exchange reaction on the peripheral X of X\u2013X\u00b7\u00b7\u00b7N with the chloride of N-chlorosuccinimide lead to Cl\u2013X\u00b7\u00b7\u00b7N halogen-bonded complexes. The 1:1 complexation of HMTA and ICl manifests the shortest I\u00b7\u00b7\u00b7N halogen bond [2.272(5) \u00c5] yet reported for an HMTA acceptor. Two halogen-bonded organic frameworks are prepared using 1:4 molar ratio of HMTA and N-bromosuccinimide, each with a distinct channel shape, one possessing oval and the other square grid. The variations in channel shapes are due to tridentate and tetradentate (imide)Br\u00b7\u00b7\u00b7N coordination modes of HMTA. Density Functional Theory (DFT) studies are performed to gain insights into (imide)X\u00b7\u00b7\u00b7N interaction strengths (\u0394Eint). The calculated \u0394Eint values for (imide)Br\u00b7\u00b7\u00b7N  are smaller than the values for (imide)I\u00b7\u00b7\u00b7N . The DFT additivity analysis of (imide)Br\u00b7\u00b7\u00b7N motifs demonstrates Br\u00b7\u00b7\u00b7N interaction strength gradually decreasing from 1:1 to 1:3 HMTA:N-bromosuccinimide complexes. Exceptionally similar charge density values \u03c1(r) for N\u2013I covalent bond and I\u00b7\u00b7\u00b7N non-covalent bond of a (saccharin)N\u2013I\u00b7\u00b7\u00b7N motif signify the covalent character for I\u00b7\u00b7\u00b7N halogen bonding.Hexamethylenetetramine (HMTA) and  Non-aromatics, such as 1,4-diazabicylcooctane (DABCO) and hexamethylenetetramine (HMTA), have become a critical design trait in supramolecular chemistry, and have inspired scholars to devise molecular rotors  and 2.432(3) \u00c5] are longer than in [DABCO]\u00b7[NBS]2 [2.347(2) and 2.364(2) \u00c5] due to steric and competitive HB interactions in the former structure. (ii) Solvent as the only varying parameter, six different [HMTA]\u00b7[N-iodosuccinimide]4 XBOFs have been characterized using X-ray diffraction analysis  find the \u2033ideal\u2033 HMTA:N-haloimide partner to access open-framework XBOF structures, and (iii) evaluate and compare the X\u00b7\u00b7\u00b7N interaction strengths.Our previous contributions in the field of HMTA halogen bonding include (i) the comparison of Br\u00b7\u00b7\u00b7N bond distances in bidentate complexes [HMTA]\u00b7[N-bromosuccinimide]1\u201313 of composition types [HMTA]\u00b7[dihalogen]n and [HMTA]\u00b7[N-haloimide]n  motifs, and complexes 2, 4, and 6 comprising hetero-halogen Y\u2013X\u00b7\u00b7\u00b7N  motifs. The Br2 source in 1 and I2 in 3 and 5 are consequences of N\u2013X bond cleavage reactions of NBS and NIS, respectively 2N\u2013Br\u00b7\u00b7\u00b7N gradually converts to Br\u2013Br\u00b7\u00b7\u00b7N motif by N\u2013Br bond cleavage reaction followed by the exchange of (CO)2N and Br anions. In the second step, NCS, a chloride anion source, was added to replace the terminal bromide anion to give 2.HMTA and five different N-haloimides, namely N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NCS), N-bromophthalimide (NBP), and N-iodosaccharin (NISac), were used to prepare 13 halogen-bonded complexes oimide]n . [HMTA]\u00b7 Filler, . The pre7\u201313 were obtained by slow evaporation of the corresponding HMTA and N-haloimide solutions . The 1:4 HMTA:NBS and 1:4 HMTA:NBP molar ratio reactions only gave the corresponding bidentate complexes 7 and 8 as the main products for structural analysis. Single-crystals isolated from different 1:4 HMTA:NBS experiments carried out by using various solvents also revealed the bidentate coordination for HMTA . Using a 1:4 HMTA:NBS molar ratio, complexes 9 and 10 were obtained employing different crystallization techniques. Complex 9, which contains a tridentate Br\u00b7\u00b7\u00b7N HMTA, was obtained using solvent-assisted grinding followed by solution crystallization, while 10, determined to be tetradentate Br\u00b7\u00b7\u00b7N HMTA, was crystallized by using the layering technique. Under the crystallization method of 9, the other HMTA-imide combinations produced crystals of either HMTA or corresponding imide. Even 9 is not reproducible and yields crystals of succinimide and bidentate complex 7. The lack of reproducibility is due to the influence of several uncontrolled factors in the crystallization process, such as N\u2013X bond cleavage reactions and complex hydrogen bonding patterns.Single-crystals of 11. A 1:2 HMTA:NISac molar ratio gives a monodentate complex 12. However, treating HMTA with an excess of NISac (12.5 eq) leads to the formation of unknown quantities of iodine-oriented ions consequently resulting in an iodonium complex [bis(HMTA)I]+13. A related method to prepare [bis(HMTA)I]+2 and [HMTA]\u00b7[Ditfb]2, respectively. The corresponding XB parameters are used for discussions here and their structural data is included in the Supporting Information.Experiments conducted using 1:4 molar ratio of HMTA and NIS in different solvents all exclusively produced crystals of 1\u201313 illustrate four types of coordination modes. All the X\u00b7\u00b7\u00b7N  distances are below the sum of the Van der Waals radii of respective halogen  and nitrogen (1.55 \u00c5)  are shown in HMTA in complexes ) Bondi, . Selecte1 and bidentate in 2 (3-center-4-electron [N\u2013Br\u2013N]+ XBs [2.086(5)\u22122.1862(4) \u00c5] \u22122.1572(2) \u00c5]  \u00c5] is remarkably short compared to I\u2013I\u00b7\u00b7\u00b7N distance of 3 [2.405(5) \u00c5] indicating better e-accepting power of ICl. The monodentate Cl\u2013I\u00b7\u00b7\u00b7N distance is shorter than +I\u2013N halogen bonds reported for [bis(HMTA)I]++ XBs [2.198(3)\u22122.349(18) \u00c5]. In the packing structure, 3 associates via HMTAN\u2013I\u2013I\u00b7\u00b7\u00b7NHMTA halogen bonds at distances of 3.519 \u00c5 forming zigzag 1D chains  \u00c5], 5 [2.480(4) \u00c5], and [HMTA]\u00b7[I\u2013I]3 [2.593(6) \u00c5]  and 2.426(4) \u00c5] are slightly shorter than our previously reported solvent-free bidentate [HMTA]\u00b7[NBS]2 [2.414(3) and 2.432(3) \u00c5]  \u00c5, HMTA is bidentate in molecule . The two9 prepared by solvent-assisted manual grinding, contains four crystallographically independent NBS donors of which one NBS does not participate in the X-bonding. Three Br\u00b7\u00b7\u00b7N distances vary from 2.371(8) to 2.411(9) \u00c5 (3/unit cell. The relative channel volume (rcv)  \u00c5 . The fouolecules , which a11 contains bidentate HMTA, and the I\u00b7\u00b7\u00b7N distances   \u00c5, 2 [2.879(5) and 2.864(4) \u00c5]  distances of [DMAP]\u00b7[NIS]. However, both the (imide)N\u2013I [2.26(2) \u00c5] and I\u00b7\u00b7\u00b7N(HMTA) distances [2.29(2) \u00c5] of 12 are remarkably close to [DMAP]\u00b7[NISac] [2.292(2) and 2.218(2) \u00c5]  and 2.299(15) \u00c5, and appear within 0.02 \u00c5 of the corresponding distances in the reported structure (Complex 18(2) \u00c5] . Complextructure .S, min, \u221230 kcal/mol), is comparable to values estimated at the O-atoms of NBS  and NBP . A VS, max of magnitude +16 kcal/mol is associated with the \u2013CH2- protons adjacent to the sp3 N-atom. In NBS, the VS, max at the bromine \u03c3-hole and the five-member ring-centroid are similar  is slightly smaller than in NBS but larger than in NBP. To our surprise, the electron-withdrawing \u2013SO2 group of NISac could only render a positive potential of +7 kcal/mol at the six-membered ring-centroid. The global MEP analysis suggests that the nucleophilic and electrophilic sites of HMTA and NBS/NIS molecules have equal propensity to form Br\u00b7\u00b7\u00b7N, C\u2013H\u00b7\u00b7\u00b7N, and C\u2013H\u00b7\u00b7\u00b7O=C interactions, which is in good agreement with packing forces discussed in the XBOF structures X\u00b7\u00b7\u00b7N motif in a 1:1 complex when donors are successively added to HMTA, are estimated for complexes [HTMA]\u00b7[NBS]int) were estimated by using their corresponding X-ray crystal structure coordinates. The calculated \u0394Eint values range from \u221211.2 to \u221212.5 kcal/mol for Br\u00b7\u00b7\u00b7N motifs. The \u0394Eint values decrease when the HMTA denticity increases, \u221212.5 kcal/mol for 7, \u221212.1 kcal/mol for 9, and \u221211.2 kcal/mol for 10, and the results are in good agreement with the additivity analysis. The \u0394Eint value of 7 is stronger than NBS\u00b7\u00b7\u00b7NPy   for N\u2013Br covalent bond and Br\u00b7\u00b7\u00b7N non-covalent bond are significantly different, indicating the absence of a shared-shell character  are slightly larger than in 7 . This agrees with the well-known fact that the fused six-membered ring in NBP removes electron density from the five-membered ring, consequently making the bromine more electrophilic. The \u0394Eint values of ancillary interactions, for example, N\u00b7\u00b7\u00b7\u03c0(ring-centroid) and C\u2013H\u00b7\u00b7\u00b7N hydrogen bond contacts in 7, are estimated to understand their interaction strengths relative to Br\u00b7\u00b7\u00b7N motifs  and C\u2013H\u00b7\u00b7\u00b7N  contacts are weaker than XBs . The presence of the BCPs and bond paths of their connecting atoms are other evidences for N\u00b7\u00b7\u00b7\u03c0 and C\u2013H\u00b7\u00b7\u00b7N contacts. This suggests that weak and moderately strong HBs, that originate from donor-acceptor components' electron-rich and deficient sites, are inevitable and may contribute to the XB stabilization energy.In contrast to the same \u03c3-hole strengths of NBS and NBP, the Br\u00b7\u00b7\u00b7N halogen bonds interaction strengths of tifs see . The \u0394Ei11  and [HMTA]\u00b7[NIS]4  are larger than corresponding bromine structures, and twice the energy of C\u2013I\u00b7\u00b7\u00b7N contacts  in [HMTA]\u00b7[Iodopentafluorobenzene]2 (see int and the \u03c1(r) values at the BCP of 11 are somewhat larger than [HMTA]\u00b7[NIS]4, which agrees with the additivity analysis. Complex 12 involving NISac has the largest interaction energy of all the (imide)I\u00b7\u00b7\u00b7NHMTA halogen bonds  owing to larger iodine \u03c3-hole strength in NISac . The \u03c1(r) values at the BCPs of I\u00b7\u00b7\u00b7N halogen bond, similar to N\u2013I covalent indicating a degree of covalency with shared-shell character, is remarkable. This agrees with the N\u2013I and I\u00b7\u00b7\u00b7N bonds covalent character discussion in [DMAP]\u00b7[NISac]  and are comparable to HB energies observed in 7. The AIM analysis reveals that C\u2013H\u00b7\u00b7\u00b7O=S and C\u2013H\u00b7\u00b7\u00b7\u03c0 interactions may contribute to the formation of I\u00b7\u00b7\u00b7NHMTA interactions.The I\u00b7\u00b7\u00b7N interaction energies of ne]2 see . The \u0394EiN-iodosaccharin even approaches the reported 3-center-4-electron halogen bonds of [(HMTA)N\u2013I\u2013N(HMTA)]+ [2.288(14) and 2.299(15) \u00c5]. The scope of halogen-bonded organic frameworks (XBOFs), previously accessed by (imide)I\u00b7\u00b7\u00b7N using a 1:4 [HMTA]:[NIS] building block, is expanded to (imide)Br\u00b7\u00b7\u00b7N halogen-bonded 1:3 [HMTA]:[NBS] and 1:4 [HMTA]:[NBS] structures. Different from (imide)I\u00b7\u00b7\u00b7N XBOFs, channel shape adaptability is achieved through HMTA tridentate and tetradentate coordination modes. DFT based MEPs provided us with important experimental insights into the nature of donor-donor and donor-acceptor interactions. Donors, such as NBS/NIS possessing \u03c3-hole  and C\u2013H acidic proton  values, have high probabilities to form XBOFs via (imide) X\u00b7\u00b7\u00b7N halogen bonds and orthogonal C\u2013H\u00b7\u00b7\u00b7O=C hydrogen bonds. The lack of acidic sp3 C\u2013H protons, like in NBP, encourage \u03c0-\u03c0 and other hydrogen bond interactions obstructing the formation of the desired 1:4 ratio [HMTA]:[NBP] and eventually affect XBOFs' self-assembly processes. In terms of DFT interactions energies, the (imide)N\u2013X\u00b7\u00b7\u00b7N(HMTA) halogen bonds varying from \u221211.2 to \u221212.5 kcal/mol for X = Br, and \u22128.4 to \u221229.0 kcal/mol for X = I, are stronger than corresponding (imide)N\u2013X\u00b7\u00b7\u00b7N(pyridines) halogen bonds. A comprehensive solution NMR study on [HMTA]\u00b7[N-haloimide]n complexes, optimization of crystallization conditions to synthesize XBOFs using other HMTA-imide combinations, and post-synthetic solvent exchange process of (imide)N\u2013Br\u00b7\u00b7\u00b7N XBOFs are currently under investigation in our laboratory.In summary, we investigated Y\u2013X\u00b7\u00b7\u00b7N  halogen bonds in 13 X-ray crystal structures obtained from HMTA and N-haloimides. Two complexes of HMTA with iodoperfluorobenzene and 1,4-diiodotetrafluorobenzene consisting of C\u2013I\u00b7\u00b7\u00b7N halogen bonds were also prepared, and their solid-state structures were studied for comparison purposes. The Y\u2013X\u00b7\u00b7\u00b7N distances depend on the nature of Y-atom and the donor scaffold. The Br/Cl\u2013Br\u00b7\u00b7\u00b7N [2.088(3)\u22122.167(3) \u00c5] are shorter than (imide)N\u2013Br\u00b7\u00b7\u00b7N [2.371(8)\u22122.426(4) \u00c5] halogen bonds. In contrast, the I/Cl\u2013I\u00b7\u00b7\u00b7N [2.328(3)\u22122.486(5) \u00c5] tend to be longer when compared to (imide)N\u2013I\u00b7\u00b7\u00b7N [2.29(3) and 2.502(10) \u00c5] halogen bonds. The shortest I\u00b7\u00b7\u00b7N [2.29(3) \u00c5] distance between HMTA and The datasets presented in this study can be found in online repositories. The names of the repository/repositories and accession number(s) can be found in the article/12, for X-ray crystallography, done in JYU, were prepared by GA, 12 was prepared by LG. Both JR and GP were external thesis supervisors for GA and LG, respectively. AF and AB were responsible for computational studies. KR was responsible for proofreading the final manuscript version. All authors have read and agreed to the published version of the manuscript.RP was responsible for supervision, methodology development, manuscript preparation, and SCXRD analysis. All halogen bond complexes, except The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest."}
{"text": "The mol\u00adecular structure is stabilized by an O\u2014H\u22efN hydrogen bond, forming an S(6) ring motif.The title compound, C 22H18N2O2, is a Schiff base that exists in the phenol\u2013imine tautomeric form and adopts an E configuration with respect to the C=N bond. The mol\u00adecular structure is stabilized by an O\u2014H\u22efN hydrogen bond, forming an S(6) ring motif. In the crystal, pairs of C\u2014H\u22efO hydrogen bonds link the mol\u00adecules to form inversion dimers. Weak \u03c0\u2013\u03c0 stacking inter\u00adactions along the a-axis direction provide additional stabilization of the crystal structure. The mol\u00adecule is non-planar, the aromatic ring of the benzaldehyde residue being nearly perpendicular to the phenyl and 4-methyl\u00adphenol rings with dihedral angles of 88.78\u2005(13) and 82.26\u2005(14)\u00b0, respectively. A mol\u00adecular docking study between the title mol\u00adecule and the COVID-19 main protease (PDB ID: 6LU7) was performed, showing that it is a potential agent because of its affinity and ability to adhere to the active sites of the protein.The title compound, C We report here the synthesis, crystal and mol\u00adecular structure of the title compound. We have also performed a mol\u00adecular docking study to determine possible inter\u00admolecular inter\u00adactions between the COVID-19 main protease (PDB ID: 6LU7) and the title compound.Schiff bases have wide applications inter\u00adests as corrosion inhibitors  ring motif, which stabilizes the mol\u00adecular structure. The di\u00adbenzyl\u00adidene hydrazine unit is approximately planar with the dihedral angle formed by the two terminal phenyl rings of 7.62\u2005(15)\u00b0. On the other hand, the mol\u00adecule is non-planar, because the C1\u2013C6 ring is nearly perpendicular to the C9\u2013C14 and C16\u2013C21 rings with dihedral angles of 88.78\u2005(13) and 82.26\u2005(14)\u00b0, respectively. The C17\u2014O2, C15\u2014N2 and C15\u2014C16 bond lengths in the mol\u00adecule are 1.359\u2005(5), 1.287\u2005(5), and 1.452\u2005(5)\u2005\u00c5, respectively. These results suggest single-bond character for C17\u2014O2 and C15\u2014C16 and double-bond character for the C15\u2014N2 bond as expected for a phenol\u2013imine structure  ring motif.The asymmetric unit of the title structure contains one mol\u00adecule Fig.\u00a01, which cCg2\u22efCg3 = 3.909\u2005(2)\u2005\u00c5; Cg2 and Cg3 are the centroids of the C9\u2013C14 and C16\u2013C21 rings, respectively] that stabilize the crystal structure, forming a three-dimensional network.In the crystal, mol\u00adecules are linked by pairs of C3\u2014H3\u22efO2 hydrogen bonds, forming inversion dimers with an f Table\u00a01. There aet al., 2016et al., 2011sp2\u2014Csp2 single bond, is slightly longer than observed for the title compound [1.472\u2005(5)\u2005\u00c5]. This bond length is shorter than in NOTZIH hydrazineyl\u00adid\u00adene}-1,2-di\u00adphenyl\u00adethan-1-one was prepared by refluxing a mixture of a solution containing 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde (0.02\u2005mmol) in ethanol (20\u2005mL) and a solution containing (E)-2-hydrazineyl\u00adidene-1,2-di\u00adphenyl\u00adethan-1-one (0.02\u2005mmol) in ethanol (20\u2005mL). The reaction mixture was stirred for 5\u2005h under reflux. The obtained crystalline material was washed with ethanol and dried at room temperature. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution.(Uiso(H) = 1.5Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model with C\u2014H = 0.93 and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and with C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021005442/yk2152sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021005442/yk2152Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021005442/yk2152Isup3.cmlSupporting information file. DOI: 2085577CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethanedi\u00adamine, C6H16N2, crystallizes in the monoclinic crystal system in the space group P21/c. For the investigation of the conformation, quantum chemical methods were used and for inter\u00admolecular inter\u00adactions, a Hirshfeld surface analysis was performed. N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethanedi\u00adamine, C6H16N2, is a bidentate amine ligand commonly used in organolithium chemistry for deaggregation. Crystals were grown at 243\u2005K from n-pentane solution. The complete mol\u00adecule is generated by a crystallographic center of symmetry and the conformation of the di\u00adamine is anti\u00adperiplanar. To investigate the inter\u00admolecular inter\u00adactions, a Hirshfeld surface analysis was performed. It showed that H\u22efH  inter\u00adactions dominate with a contact percentage of 92.3%.The title compound  N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethanedi\u00adamine  consists of two tertiary amine groups linked by an ethyl\u00adene bridge. It can be used in cross-coupling or in olefin polymerization reactions where, e.g., a complex between di\u00admethyl\u00adnickel and TMEDA is used as a catalyst  \u2212x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] = 180.0\u00b0 by symmetry. The conformations of the C1\u2014N1\u2014C3\u2014C3i and C2\u2014N1\u2014C3\u2014C3i groupings are anti [torsion angle = 167.33\u2005(6)\u00b0] and gauche [\u201371.17\u2005(8)\u00b0], respectively.Compound et al., 2013Gaussian 16   -tris\u00ad(tetra\u00admethyl\u00adethylenedi\u00adamine\u00adlithium)methyl\u00adthorium(IV) tetra\u00admethyl\u00adethylenedi\u00adamine -({[(S)-2-(meth\u00adoxy\u00admeth\u00adyl)pyrrolidin-1-yl]meth\u00adyl}di\u00admeth\u00adyl\u00adsil\u00adyl)(phen\u00adyl)meth\u00adyl]lithium N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethane\u00addi\u00adamine  was purchased by Sigma-Aldrich and was used without further purification. A solution of TMEDA (0.5\u2005mmol) in n-pentane (1\u2005ml) was prepared at 243\u2005K and 1 crystallized in the form of colorless blocks.Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021012457/hb8002sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021012457/hb8002Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021012457/hb8002Isup3.cmlSupporting information file. DOI: 2123810CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III complex with a multidentate NSO-containing mixed-ligand \u2212 2-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde thio\u00adsemicarbazone \u2013 is reported.The synthesis, crystal structure and spectroscopic characterization of the novel and, according to our knowledge the first to be obtained in crystalline form, Co III complex, bis\u00ad[bis\u00adcobalt(III)] di\u00adthio\u00adnate\u2013dimethylformamide\u2013methanol (1/4/3), [Co(C9H10N3O2S)2]2(S2O6)\u00b74C3H7NO\u00b73CH3OH, with monodeprotonated 2-hy\u00addroxy-3-meth\u00adoxy\u00adbenzaldehyde thio\u00adsemicarbazone as ligands crystallizes in the space group PL2]+ cations, one di\u00adthio\u00adnate anion (S2O6)2\u2212 as counter-anion and seven solvate mol\u00adecules (four di\u00admethyl\u00admethanamide and three methanol). Each CoIII ion has a moderately distorted octa\u00adhedral S2N2O2 geometry. In the crystal, the components are linked by numerous N\u2014H\u22efO and O\u2014H\u22efO contacts.The title Co Thus, the coordination geometry around each CoIII ion can be described as moderately distorted octa\u00adhedral with an S2N2O2 coordination sphere with N,O,N and S atoms in the equatorial plane and O and S atoms in the apical positions.The title complex crystallizes in the triclinic space group it Fig.\u00a01 consistset al., 2013II complexes with related semicarbazone ligands  to those in an analogous chromium complex with a similar ligand  approaches the standard C=S double-bond value and differs only slightly from the distance observed in the corresponding neutral ligand [1.688\u2005\u00c5 in BIZYAL  and twisted, as defined by the dihedral angles of 83.42\u2005(7)\u00b0 between the mean planes of atoms O1/C1/C6/C8/N1/N2/C9/S1 and O3/C10/C15/C17/N4/N5/C18/S2 around Co1, and 86.3\u2005(1)\u00b0 between the mean planes of atoms O7/C28/C33/C35/N10/N11/C36/S4 and O5/C19/C24/C26/N10/N8/C27/S3 around Co2.The ligands coordinated to the CoThe solid-state organization of the complex can be described as an insertion of the anions and solvent mol\u00adecules within the crystallographically independent complexes Fig.\u00a02. In the A\u22efO8, N2\u2014H2\u22efO3 and N2\u2014H2\u22efO4 are contacts between ligands through the nitro\u00adgen of the secondary amino group and meth\u00adoxy group oxygen;N8\u2014H8A\u22efO11 and N12\u2014H12B\u22efO9 are contacts between the nitro\u00adgen of the secondary and primary  amino groups of the ligands and oxygen atoms of the S2O6 anions .N3\u2014H32O6)2\u2212 anions act as a multiple-acceptor species for N,O donor atoms of neighboring complexes (by N\u2014H\u22efO inter\u00adactions) and methanol solvent mol\u00adecules (by O\u2014H\u22efO contacts). The oxygen atoms (O16) of the di\u00admethyl\u00admethanamide mol\u00adecules bridge adjacent cationic complexes  of the ligand in 1ml of di\u00admethyl\u00adformamide and 1ml of chloro\u00adform. Dark-brown crystals of the title compound, suitable for X-ray analysis, were formed within a few days (yield: 60%).The title compound was prepared according to a previously published procedure  due to aromatic =C\u2014H stretching at 3000\u20133100\u2005cm\u22121, the aromatic ring vibrations in the 1600\u20131400\u2005cm\u22121 region, weak absorption band at 738\u2005cm\u22121 due to \u03c5(C\u2014S) vibrations and the characteristic peak at 1608\u2005cm\u22121 assigned to azomethine \u03c5(C=N) group. The weak band at 3308\u2005cm\u22121 can be assigned to the N\u2014H group vibrations. All these data are in good agreement with literature data : C 38.19; N 14.33; H 5.16%. Found: C 38.21; N 14.40; H 5.21%.The IR spectrum of the title compound (as KBr pellets) is consistent with the above structural data. In the range 4000\u2013400\u2005cmII di\u00adthio\u00adnate used in this work was prepared by mixing aqueous solutions containing stoichiometric amounts of cobalt sulfate and BaS2O6\u00b72H2O. The white precipitate of BaSO4 was removed by filtration and the solution containing the metal di\u00adthio\u00adnate was evaporated to a small volume on a rotary evaporator and then cooled for crystallization. BaS2O6\u00b72H2O was prepared using the method described by Pfanstiel (1946The Cotiel 1946.Uiso(H) = 1.2Ueq(C) for aromatic CH and Uiso(H) = 1.5Ueq(C) for methyl groups. The H atoms of the NH and OH groups were also placed at calculated position using the corresponding AFIX instruction with Uiso(H) = 1.2Ueq(N) for NH/NH2 and Uiso(H) = 1.5Ueq(O) for OH hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021010616/tx2043sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010616/tx2043Isup2.hklStructure factors: contains datablock(s) I. DOI: 2115486CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title thio\u00adurea derivative adopts a U-shaped conformation, which incorporates an intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond. In the mol\u00adecular packing, supra\u00admolecular chains are formed through hydroxyl-O\u2014H\u22efS(thione) and amine-N\u2014H\u22efO hydrogen bonding. 17H19N3OS, adopts a U-shaped conformation with the dihedral angle between the terminal aromatic rings being 73.64\u2005(5)\u00b0. The major twist in the mol\u00adecule occurs about the ethane bond with the Ci\u2014Ce\u2014Ce\u2014Cb torsion angle being \u221278.12\u2005(18)\u00b0; i = imine, e = ethane and b = benzene. The configuration about the imine bond is E, the N-bound H atoms lie on opposite sides of the mol\u00adecule and an intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond is evident. In the mol\u00adecular packing, hydroxyl-O\u2014H\u22efS(thione) and amine-N\u2014H\u22efO hydrogen bonding feature within a linear, supra\u00admolecular chain. The chains are connected into a layer in the ab plane by a combination of methyl\u00adene-C\u2014H\u22efS(thione), methyl\u00adene-C\u2014H\u22efO(hydrox\u00adyl), methyl-C\u2014H\u22ef\u03c0(phen\u00adyl) and phenyl-C\u2014H\u22ef\u03c0(hy\u00addroxy\u00adbenzene) inter\u00adactions. The layers stack without directional inter\u00adactions between them. The analysis of the calculated Hirshfeld surface highlights the presence of weak methyl-C\u2014H\u22efO(hydrox\u00adyl) and H\u22efH inter\u00adactions in the inter-layer region. Computational chemistry indicates that dispersion energy is the major contributor to the overall stabilization of the mol\u00adecular packing.The title thio\u00adurea derivative, C Globally, both aromatic residues lie to the same side of the mol\u00adecule so that it has a U-shaped conformation.The mol\u00adecular structure of (I)E. The N-bound H atoms lie to opposite sides of the mol\u00adecule, a conformation that allows for the formation of an intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond, Table\u00a01The C1\u2014S1 bond length is 1.6910\u2005(15)\u2005\u00c5, the C1\u2014N1 bond [1.340\u2005(2)\u2005\u00c5] is marginally shorter than the C1\u2014N2 [1.356\u2005(2)\u2005\u00c5] bond, the formally C8\u2014N3 double bond is 1.284\u2005(2)\u2005\u00c5 and N2\u2014N3 is 1.3857\u2005(18)\u2005\u00c5. These values, coupled with the observed planarity in this region of the mol\u00adecule, is suggestive of some delocalization of \u03c0-electron density over this residue. The configuration about the C8=N3 imine bond is a). They are connected into a supra\u00admolecular layer parallel to the c axis via methyl\u00adene-C\u2014H\u22efS(thione) and methyl\u00adene-C\u2014H\u22efO(hydrox\u00adyl) inter\u00adactions as well as methyl-C\u2014H\u22ef\u03c0(phen\u00adyl) and phenyl-C\u2014H\u22ef\u03c0(hy\u00addroxy\u00adbenzene) contacts, Table\u00a01b). The layers thus formed are two mol\u00adecules thick and stack along the c-axis direction without directional inter\u00adactions between them, Fig.\u00a02c). Finally, as indicated in Fig.\u00a02b) and (c), the supra\u00admolecular connectivity brings two sulfur atoms into close proximity, with an S1\u22efS1i separation of 3.3534\u2005(6)\u2005\u00c5, cf. the sum of the van der Waals radii of 3.60\u2005\u00c5 , i.e. near the amine-H2N and thione-S1 atoms, correspond to the amine-N2\u2014H2N\u22efO1(hydrox\u00adyl), hydroxyl-O1\u2014H1O\u22efS1(thione) hydrogen bonds and the thione-S1\u22efS1(thione) short contact; these and other short contacts calculated using Crystal Explorer 17 are collated in Table\u00a02b), where the positive electrostatic potential (blue) and negative electrostatic potential (red) regions are observed around the amine-H2N and thione-S1 atoms, respectively. The faint red spots appearing near the thione-S1, hydroxyl-O1 and methyl\u00adene-H11A and H11B atoms  and phenyl-C6\u2014H6\u22ef\u03c0 inter\u00adactions are shown as faint red spots on the dnorm surface in Fig.\u00a05a) and as two distinctive orange \u2018potholes\u2019 on the shape-index-mapped over Hirshfeld surface in Fig.\u00a05b). It is noted that the phenyl-C4\u2014H4\u22ef\u03c0 inter\u00adaction, Table\u00a01dnorm-mapped Hirshfeld surface. However, this inter\u00adaction clearly shows up as an orange \u2018pothole\u2019 on the shape-index-mapped Hirshfeld surface in Fig.\u00a06The bright-red spots on the Hirshfeld surface mapped over ms Fig.\u00a04 correspoa) and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efS/S\u22efH and H\u22efO/O\u22efH contacts are illustrated in Fig.\u00a07b)\u2013(e), respectively. The percentage contributions to the Hirshfeld surface of (I)de = di \u223c2.1\u2005\u00c5, Fig.\u00a07b), corresponds to the intra-layer H1O\u22efH2N contact listed in Table\u00a02c), reflecting the significant C\u2014H\u22ef\u03c0 inter\u00adactions evinced in the packing analysis, Table\u00a01de = di \u2243 2.2\u2005\u00c5 in Fig.\u00a07d) and (e), respectively. The contributions from the other six inter\u00adatomic contacts summarized in Table\u00a03The overall two-dimensional fingerprint plot computed for (I)Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energy components  and Erep (12.2\u2005kJ\u2005mol\u22121) terms and having a total energy of 11.7\u2005kJ\u2005mol\u22121 is non-attractive.The energy frameworks were calculated for (I)Edis component. The greatest stabilization energy in the inter-layer region arises from methyl-C9\u2014H9B\u22efO1(hydrox\u00adyl)  and methyl\u00adene-H10\u22efH16(hy\u00addroxy\u00adbenzene) inter\u00adactions , which sum to \u221230.7\u2005kJ\u2005mol\u22121. Generally, the long-range H\u22efH contacts are the major inter\u00adactions stabilizing the mol\u00adecules within the inter-layer region.The stabilization energies in the inter-layer region are dominated by the a axis direction are shown in Fig.\u00a08Eele of all pairwise inter\u00adactions sum to \u2212145.4\u2005kJ\u2005mol\u22121, while the Edis totals \u2212342.1\u2005kJ\u2005mol\u22121.Views of the energy framework diagrams down the via an ethane link. Each of these is a N-methyl species, i.e. MeN(H)C(=S)N(H)N=C(Me)CH2CH2Ar, one with Ar = phenyl  torsion angle = \u221262.76\u2005(16)\u00b0], a conformation stabilized, at least in part, by an intra\u00admolecular amine-N\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adaction. By contrast, in the species with Ar = 4-meth\u00adoxy\u00adbenzene, the mol\u00adecule is close to planar as indicated by the Ci\u2014Cm\u2014Cm\u2014Cp torsion angles of 177.51\u2005(12) and \u2212175.80\u2005(12)\u00b0, respectively, for the two independent molecules comprising the asymmetric unit. Thus, to a first approximation, the conformation observed in (I)In the crystallographic literature, there are two precedents for mol\u00adecules related to (I)in vacuo. Single crystals were grown at room temperature in mixed solvents of dimethyformamide and aceto\u00adnitrile (1:2 v/v) by slow evaporation. 1H NMR : \u03b4 9.14 , 8.59 , 7.59 , 7.37 , 7.22 , 7.03 , 6.76 , 5.46 , 2.83 , 2.61 , 1.90 . 13C NMR : \u03b4 176.22, 154.16, 152.02, 137.93, 132.72, 129.39, 128.84, 126.16, 124.39, 115.57, 40.38, 31.58, 16.19.4-Phenyl-3-thio\u00adsemicarbazide (10\u2005mmol) dissolved in hot absolute ethanol (50\u2005ml) was combined with 4-(4-hy\u00addroxy\u00adphen\u00adyl)-2-butanone (10\u2005mmol), dissolved in hot absolute ethanol (50\u2005ml) with a few drops of concentrated hydro\u00adchloric acid added as catalyst. The mixture was heated (348\u2005K) and stirred for about 30\u2005min. The mixture was allowed to cool to room temperature while stirring. The white precipitate was filtered, washed with cold ethanol and dried Uiso(H) set to 1.2\u20131.5Ueq(C). The O-bound and N-bound H atoms were located in a difference-Fourier map but were refined with O\u2014H = 0.84\u00b10.01 and N\u2014H = 0.88\u00b10.01\u2005\u00c5 distance restraints, respectively, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989021006666/hb7978sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989021006666/hb7978Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021006666/hb7978Isup3.cmlSupporting information file. DOI: 2092413CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Further, cleavage of the [Fe\u2010S\u2010Fe] unit by CS2 is presented.A [Fe\u2010S\u2010Fe] subunit with a single sulfide bridging two low\u2010coordinate iron ions is the supposed active site of the iron\u2010molybdenum co\u2010factor (FeMoco) of nitrogenase. Here we report a dinuclear monosulfido bridged diiron(II) complex with a similar complex geometry that can be oxidized stepwise to diiron(II/III) and diiron(III/III) complexes while retaining the [Fe\u2010S\u2010Fe] core. The series of complexes has been characterized crystallographically, and electronic structures have been studied using, inter alia,  A dinuclear monosulfido bridged diiron(II) complex is reported that can be oxidized stepwise to diiron(II/III) and diiron(III/III) complexes while retaining the [Fe\u2010S\u2010Fe] core. This unprecedented series of low\u2010coordinate complexes has been thoroughly characterized using inter alia, 57Fe M\u00f6ssbauer spectroscopy and SQUID magnetometry. The reaction takes place at the iron\u2010molybdenum co\u2010factor (FeMoco), which constitutes a ligated [MoFe7S9C] unit.Nitrogenase (N2+ complex with an unsupported monosulfide bridge via the reaction of a two\u2010coordinate iron(I) silylamide with elemental sulfur. Subsequent oxidation leads to the first example of a mixed valent [2Fe\u20101S]3+ and an \u201call ferric\u201d [2Fe\u20101S]4+ form. The series of complexes was examined with respect to their spectroscopic and physical properties. The initial [2Fe\u20101S]2+ complex was further subjected to a variety of small molecule substrates that are transformed by the N2\u2010ase, however showing only a limited reactivity or stability. Most notably, its reaction with CS2 led to rupture of the Fe\u2010S\u2010Fe motif and formation of a mononuclear iron(II) thiocarbonate complex, revealing the structural lability of the [Fe\u2010S\u2010Fe] unit.This unit is assumed to open up during substrate turnover, as experimentally shown by displacement of the sulfide unit by CO or selenide.2, 6 A2] (L=\u2010N(Dipp)SiMe3, Dipp=2,6\u2010diisopropylphenyl), 1,2O with 1/16 S8 for 16\u2005h led to the formation of a colorless solid. X\u2010Ray diffraction analysis of suitable single crystals showed the formation of the dinuclear complex (K{18c6})2[(FeL2)2(\u03bc\u2010S)], 2 (Scheme\u2005The reaction of a suspension of K{18c6}FeL (L=\u2010N(Di2 features two three\u2010coordinate iron(II) ions bridged by a single sulfide in a nearly linear fashion (Fe\u2010S\u2010Fe 167.78(2)\u00b0) with slightly different Fe\u2212S distances of 2.2400(5)\u2005\u00c5 and 2.337(5)\u2005\u00c5  complex bearing an unsupported sulfide bridge.2 can be adjusted accordingly. The cyclic voltammogram of 2 in THF showed two quasi\u2010reversible one\u2010electron oxidation processes at E1/2=\u22121.55\u2005V and \u22120.55\u2005V 2] (monoanionic ligand L\u2212=nacnac) reported by Driess and co\u2010workers features redox events in THF at E1/2=\u22121.45\u2005V for the [2Fe\u20102S]2+/1+ and E1/2=\u22122.55\u2005V (\u0394E1/2=1.10\u2005V) for the [2Fe\u20102S]1+/0 redox couple.2(\u03bc\u2010S)2]2\u2212 2+ core in MeCN occurred at E1/2=\u22121.14\u2005V ([2Fe\u20102S]2+/1+) and E1/2=\u22122.10\u2005V .2 (\u0394E1/2=0.98\u2005V). In contrast, the positions of the redox events of these bis(\u03bc\u2010sulfido) complexes are shifted by around 0.9\u2005V or 0.6\u2005V to lower potentials, respectively, reflecting the additional sulfide ligation and higher coordination number of the iron ions in the two previously reported [2Fe\u20102S] systems.[The related bis(\u03bc\u2010sulfido) diferric complex [(LFe)2. Treatment of 2 with one equivalent of AgOTf in Et2O yielded reddish K{18c6}[(L2Fe)2(\u03bc\u2010S)], 3  led to a colour change to dark green, and the neutral complex [(L2Fe)2(\u03bc\u2010S)], 4, was obtained from a saturated pentane solution.Given the electrochemical data we attempted the chemical oxidation of 3 Scheme\u2005. Treatme3 and 4 are shown in Table\u20052, complexes\u20053 and 4 retain both a more or less linear Fe\u2010S\u2010Fe core. A gradual decrease of the Fe\u2212S and Fe\u2212N bond lengths was observed upon oxidation due to the contraction of the ionic radii of the metal ions. The structural features found for both iron ions are largely identical in 3 and 4, which prohibited an assignment of localized oxidation states for mixed\u2010valent 3 on a structural level.Important structural parameters of 2 showed no absorption beyond 400\u2005nm , 470\u2005nm (\u03f5=9540\u2005L\u2009mol\u22121\u2009cm) and 700\u2005nm (\u03f5=2270\u2005L\u2009mol\u22121\u2009cm), and it is tempting to assign the low\u2010energy absorption to an intervalence charge transfer (IVCT) transition. For 4 just one pronounced band at 430\u2005nm (\u03f5=5710\u2005L\u2009mol\u22121\u2009cm) was observed. Zero field 57Fe M\u00f6ssbauer spectroscopy  complex.\u03b4=0.86\u2005mm\u2009s\u22121 and |\u0394EQ|=0.58\u2005mm\u2009s\u22121), which can be explained by the weaker donor strength of the silylamide ligands as well as a less distorted trigonal planar ligand arrangement.4 is represented by a doublet with \u03b4=0.29\u2005mm\u2009s\u22121 and |\u0394EQ|=3.70\u2005mm\u2009s\u22121 indicating the presence of high\u2010spin iron(III) ions. The spectrum of the mixed valent complex\u20053, recorded at 7\u2005K, showed two doublets with \u03b4=0.36\u2005mm\u2009s\u22121 (|\u0394EQ|=3.70\u2005mm\u2009s\u22121) and \u03b4=0.57\u2005mm\u2009s\u22121 (|\u0394EQ|=0.71\u2005mm\u2009s\u22121). This evidences distinguishable iron(II/III) positions in solid 3 on the 57Fe M\u00f6ssbauer timescale at 7\u2005K, whereas the smaller separation in the isomer shifts (\u0394\u03b4(3)=0.21\u2005mm\u2009s\u22121 vs. \u0394\u03b4(2/4)=0.30\u2005mm\u2009s\u22121) is indicative of some degree of valence delocalisation. Given the lack of literature precedence of the three\u2010coordinate \u03bc\u2010sulfido complexes\u20053 and 4 their M\u00f6ssbauer spectroscopic features are compared best to low coordinate iron complexes bearing a [2Fe\u20102S] motif in the same oxidation states.[With this unprecedented series of low\u2010coordinate 2Fe\u20101S] complexes in three different oxidation states in hand, their spectroscopic and electronic features were studied in detail. UV/Vis spectroscopic examination of m Figure\u2005, which iy Figure\u2005 revealedS complex2\u20134 in solid state were obtained by SQUID measurements  (S=2) ions with a S=0 ground state. The coupling constant was determined to be J=\u221253\u2005cm\u22121 using \u0124=\u22122JSA\u22c5SB with g1=g2=2.01.Additional insights into the electronic situation of s Figure\u2005\u2013F. 2 exh3 showed at 295\u2005K a significantly lower \u03c7T value of 0.96\u2005cm3\u2009mol\u22121\u2009K which decreased to 0.44\u2005cm3\u2009mol\u22121\u2009K at 80\u2005K with a further drop to 0.38\u2005cm3\u2009mol\u22121\u2009K below 20\u2005K, which implies a ground state of S=1/2. The antiferromagnetic coupling is stronger with J=\u2212115\u2005cm\u22121 . For the all\u2010ferric compound\u20054 a similar value J=\u2212104\u2005cm\u22121  was observed with \u03c7T=1.3\u2005cm3\u22c5mol\u22121\u22c5K at 300\u2005K that decreased linearly to ca. 0.2\u2005cm3\u2009mol\u22121\u2009K below 50\u2005K due to a S=0 ground state. The differences in exchange coupling can be explained using a simplified orbital scheme under assumption of an idealized C2V symmetric ligand environment for each iron atom . Upon oxidation, electrons are removed from the lowest\u2010lying, co\u2010parallel dxy/dx2\u2010y2 orbitals, which have no impact onto the exchange mechanism. As such the variation in J values for 2\u20134 can be mainly attributed to differences in Fe\u22c5\u22c5\u22c5Fe distances, with different superexchange contributions due to changes in Fe\u2010(\u03bc\u2010S) covalency likely playing a further role. A significant stabilization of the antiferromagnetically coupled ground state upon oxidation from the diiron(II) to the mixed\u2010valent iron(II)/iron(III) and diiron(III) states was observed for the series of complexes [(LFe)2(\u03bc\u2010S)2]4\u2212/3\u2212/2\u2212 (L2\u2212=bis(benzimidazolato))., 5  thiocarbonate complex\u20057, which could alternatively be obtained via the oxidation of 6 by silver triflate. For the neutral complex\u20054 the reaction with CS2 remained inconclusive. The observation of facile Fe\u2013S bond cleavages suggests a rather weak FeII\u2013S interaction. The displacement of an iron(II) ion by other Lewis acids has possible implications for the situation found in the FeMo cofactor where cleavage of the belt Fe\u2010S\u2010Fe unit is discussed during substrate turnover using the local Lewis acid/base properties of the surroundings of the enzyme pocket.2 into a [Fe\u2010S\u2010Fe] function also reveals how CS2 might act as an inhibitor of nitrogenase FeMoco (and other iron\u2010sulfur clusters) which is thought to proceed by blocking of coordination sites3+ complex localized valence states in solid state at low temperatures. Magnetic measurements revealed for the diferrous [2Fe\u20101S]2+ a moderate antiferromagnetic coupling which becomes significantly enhanced for the [2Fe\u20101S]3+ and [2Fe\u20101S]4+ compounds. Reactivity studies on these complexes towards different nitrogenase relevant substrates revealed for CS2 the facile cleavage of the Fe\u2010S\u2010Fe unit. This led to the formation of an iron thiocarbonate which may suggest a possible inhibitory mechanism of CS2 with respect to the reactivity of FeMoco and related Fe/S clusters.We have synthesized a unique series of low\u2010coordinate [Fe\u2010S\u2010Fe] complexes in three oxidation states which resembles a Fe\u2010S\u2010Fe belt unit in the iron/sulfur/molybdenum co\u2010factor of the nitrogenase enzyme. These complexes were characterized for their magnetic and spectroscopic properties. 2] was synthesized according to the literature procedure. For details concernining data acquisition of solution and solid\u2010state analyses , see the Supporting Information.General considerations: All manipulations were carried out in a glovebox, or using Schlenk\u2010type techniques under a dry argon atmosphere. Used solvents were dried by continuous distillation over sodium metal for several days, degassed via three freeze\u2010pump cycles and stored over molecular sieves 4\u2005\u00c5. K{18c6}[FeL2[(FeL2)2(\u03bc\u2010S)] (2)[K{18\u2009c6}]: [K{18c6}][FeL2], 1,  was suspended in 5\u2005mL of Et2O. The slow addition of elemental sulfur  led to an immediate colour change of the solution from red to brown and the precipitation of a pale yellow solid. Decanting off the supernatant, washing the residue with 2\u00d75\u2005mL of pentane and drying under reduced pressure afforded the crude product as a pale yellow crystalline solid. Recrystallization in THF/ pentane at \u221235\u2009\u00b0C led to colourless crystals of 2 , suitable for X\u2010ray diffraction. 1H\u2010NMR : \u03b4=14.23, 9.30, 3.50, 1.96, \u22120.94, \u22121.70\u2005ppm. Evans: : eff\u03bc=3.98\u2005\u03bcB.FT\u2010IR (ATR): (cm\u22121): v\u0304=2896 (w), 1418 (w), 1352 (w), 1314 (w), 1235 (m), 1192 (w), 1103 (vs.), 962 (w), 907 (s), 835 (vs.), 775 (s), 664 (w), 529 (w), 423 (m). CHNS: calc. (C84H152Fe2K2N4O12Si4S 1744.44\u2005g\u2009mol\u22121): C 57.84 H 8.78 N 3.21 S 1.84 found: C 57.93 H 8.69 N 3.58 S 1.36.2)2(\u03bc\u2010S)] (3)[K{18\u2009c6}][(FeL: [K{18c6}]2[(FeL2)2(\u03bc\u2010S)], 2,  was suspended in 5\u2005mL of Et2O. Upon the addition of AgOTf  the pale yellow suspension turned into a red solution with beginning precipitation of a dark solid . After stirring for 2\u2005hours, the mixture was filtered, the residue washed with 2\u00d73\u2005mL Et2O and the combined filtrates were layered with 5\u2005mL of pentane. Storing the solution at \u221235\u2009\u00b0C for several days yielded to a dark red crystalline solid, suitable for X\u2010ray diffraction analysis. Decanting off the supernatant, washing the residue with 2\u00d75\u2005mL of pentane and drying under reduced pressure afforded [K{18c6}][(FeL2)2(\u03bc\u2010S)], 3, as a dark red crystalline solid . The aforementioned procedure to synthesize 3 leads to a pure product according to elemental analysis (vide infra). To obtain a magnetically pure sample several recrystallization steps in Et2O/pentane were required, which led to a decrease of the yield to less than 10\u2009%. 1H\u2010NMR: : \u03b4=14.58, 14.10, 3.26, 3.07, \u22120.92, \u22122.01\u2005ppm. Evans: : eff\u03bc=3.70\u2005\u03bcB. FT\u2010IR (ATR): (cm\u22121): v\u0304=2954 (w), 1456 (w), 1421 (m), 1353 (w), 1309 (w), 1232 (s), 1179 (s), 1101 (vs.), 961 (m), 896 (m), 832 (vs.), 781 (vs.), 733 (s), 673 (s), 637 (w), 541 (m), 434 (s). UV/VIS (THF): \u03bb/ nm (\u03f5/ L\u2009mol\u22121\u2009cm)=380 (11\u2009800), 470 (9540), 700 (2270). CHNS: calc. (C72H128Fe2K1N4O6Si4S 1441.03\u2005g\u2009mol\u22121): C 60.01 H 8.95 N 3.89 S 2.22 found: C 59.66 H 8.64 N 4.07 S 1.51.2)2(\u03bc\u2010S)] (4)[(FeL: [K{18c6}]2[(FeL2)2(\u03bc\u2010S)], 2,  was suspended in 5\u2005mL of Et2O. Upon the addition of AgOTf  the pale yellow suspension turned into a dark green solution and a dark precipitate. After stirring for 2\u2005hours, the mixture was filtered, the residue washed 2 times with 3\u2005mL of Et2O and the combined filtrates were dried in vacuo. The residue was extracted with 5\u2005mL of pentane. The solution was concentrated to 0.5\u2005mL in vacuo and stored at \u221230\u2009\u00b0C for several days. This resulted in the deposition of a dark green crystalline solid, suitable for X\u2010ray diffraction. Decanting off the supernatant and drying under reduced pressure afforded [(FeL2)2(\u03bc\u2010S)], 4, as a dark green crystalline solid . 1H\u2010NMR: : \u03b4=64.37, 34.82, 23.62, \u22120.89, \u221226.88\u2005ppm. Evans: : eff\u03bc=7.26\u2005\u03bcB. FT\u2010IR (ATR): (cm\u22121): v\u0304=2958 (m), 1423 (w), 1360 (w), 1310 (w), 1242 (s), 1169 (m), 1100 (s), 1024 (s), 908 (m), 826 (vs.), 783 (vs.), 728 (vs.), 678 (s), 632 (m), 535 (s), 436 (s). UV/VIS (THF): \u03bb/ nm (\u03f5/ L\u2009mol\u22121\u2009cm)=430 (5710). CHNS: calc. (C60H104Fe2N4Si4S 1137.61\u2005g\u2009mol\u22121): C 63.35 H 9.22 N 4.94 S 2.83 found: C 63.97 H 8.75 N 5.42 S 2.65.2[L2FeII(\u03b72\u2010CS3)] (5)[K(18\u2010crown\u20106]: [K{18c6}]2[(FeL2)2(\u03bc\u2010S)], 2,  was dissolved in 2\u2005mL of THF. The slow addition of CS2  led to a colour change of the solution from brown to clear orange. After stirring for 2 hours, the mixture was filtered and the filtrate layered by 20\u2005mL of pentane. Storing the solution at \u221235\u2009\u00b0C yielded to the precipitation of orange crystals, suitable for X\u2010ray diffraction. Decanting off the supernatant, washing of the residue with 2\u00d75\u2005mL of pentane and drying in vacuo afforded 5 as a dark orange crystalline solid . 1H\u2010NMR: : no identifiable signals besides for K{18c6}. FT\u2010IR (ATR): (cm\u22121): v\u0304=2954 (m), 2892 (m), 1453 (m), 1422 (m), 1350 (m), 1311 (w), 1234 (s), 1188 (m), 1104 (vs.), 1054 (m), 961 (s), 920 (s), 881 (m), 834 (vs.), 777 (s), 744 (m), 664 (m), 533 (m), 434 (m), 407 (w). CHN: calc. (C55H101Fe2K2N2O12Si2S3\u22c5THF 1268.81\u2005g\u2009mol\u22121): C 52.89 H 8.19 N 2.09 S 7.18 found: C 52.39 H 7.91 N 2.60 S 6.73.2[L2FeIII(\u03b72\u2010CS3)] (6)[K(18\u2009c6]: [K(18c6]2[L2FeII(\u03b72\u2010CS3)], 5,  was dissolved in 2\u2005mL of THF. Upon the addition of AgOTf  the solution turned dark red and the precipitation of a grey solid was observable. After stirring for 2\u2005hours, the mixture was filtered and the filtrate was layered with 2\u2005mL of pentane. Storing the solution at \u221235\u2009\u00b0C for several days led to the precipitation of dark red crystals, suitable for X\u2010ray diffraction. Decanting off the supernatant, washing of the residue with 2\u00d75\u2005mL of pentane and drying in vacuo afforded 6 as a dark red crystalline solid. K(18c6)OTf is the major side product of the reaction. As it has almost the same solubility as 6 in Et2O and THF, it was impossible to obtain an analytically pure sample of 6 upon recrystallization. Therefore 6 could only be characterized by X\u2010ray diffraction. It exhibits no identifiable 1H\u2005NMR spectroscopic signature.2), 2048164 (3), 2048165 (4), 2048166 (5) and 2048167 (6)Deposition Numbers 2048098  should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Post-etch cleaning and silane application have been proven to increase bond strength, however, this step varies for each material [All-ceramic restorations currently dominate the market of indirect restorative materials due to their biocompatibility, longevity and superior aesthetics . Silica-material . The aimG1 BIS-Silane ; G2 ESPE Sil Silane Coupling Agent ; G3 Monobond Plus . Each was then divided into two subgroups, according to the surface conditioning time: T1 (1\u2009min.) or T2 (5\u2009min.). Each block was acid etched (HF 9.5% \u2212 1\u2009min), post-etching cleaned  and silanized. Heat treatment was carried out at 100\u2009\u00b0C (1\u2009min.). Then a thin layer of Optibond FL (Kerr) adhesive was applied and each block was adhered to pre-heated resin at 55\u2009\u00b0C. The samples were light cured for 40\u2009s on each side (1200\u2009mW/cm2). Samples were sectioned into microspecimens (1\u2009\u00b1\u20090.2\u2009mm2) that were subjected to aging . The microspecimens were tested in tension at a crosshead speed of 0.5\u2009mm/min, until they debonded. Data analysis was carried out by a two-way ANOVA, at a significance level of 5%.Ten leucite reinforced glass ceramic blocks (IPS Empress CAD LT BL4/C 14) were divided into equal halves. Of the samples obtained, 6 were randomly divided into three groups according to the silane used: p\u2009<\u2009.001). Monobond Plus registered the lowest mean \u00b5TBS value (G3T1\u2009\u2212\u200918.5\u2009\u00b1\u20097.3\u2009MPa) and (G3T2\u2009\u2212\u200917.3\u2009\u00b1\u20095.8\u2009MPa). The type of silane coupling agent has shown to have a significant influence on the microtensile bond strength .The group featuring BIS-Silane with longer application time (G1T2) presented a mean \u00b5TBS value (32.4\u2009\u00b1\u200919.6\u2009MPa) significantly higher to all other groups (Some authors have previously suggested that silanization could benefit from longer application times, but seldom research has been found featuring this variation protocol ,4. Silan"}
{"text": "Additionally, the supra\u00admolecular inter\u00adactions were determined by Hirshfeld surface analysis to investigate the influence of these contacts on the crystal packing. 17H30NSi+\u00b7C2H5O4S\u2212, belongs to the class of a-amino\u00adsilanes and was synthesized by the alkyl\u00adation of 1-[(benzyl\u00addimethyl\u00adsil\u00adyl)meth\u00adyl]piperidine using diethyl sulfate. This achiral salt crystallizes in the chiral space group P21. One of the Si\u2014C bonds in the cation is unusually long [1.9075\u2005(12)\u2005\u00c5], which correlates with the adjacent quaternary N+ atom and was verified by quantum chemical calculations. In the crystal, the components are linked by weak C\u2014H\u22efO hydrogen bonds: a Hirshfeld surface analysis was performed to further investigate these inter\u00admolecular inter\u00adactions and their effects on the crystal packing.The title mol\u00adecular salt, C Consequently, the \u03c0-character of the Si\u2014C bond is more pronounced, leading to an elongation of the bond. Thus, a selective cleavage of the amino functionality due to the elongated Si\u2014C bond is also conceivable , the title compound, represents a compound that could lead to an extension of the aforementioned Si\u2014C bond to the nitro\u00adgen atom via the quaternary ammonium cation. Structural studies concerning this type of compound should better elucidate the reactivity as well as selectivity of Si\u2014C cleavages of the benzyl-substituted \u03b1-amino\u00adsilanes.Several derivates of these \u03b1-piperdino\u00adbenzyl\u00adsilanes have been synthesized by our research group: 1-[(benzyl\u00addimethyl\u00adsil\u00adyl)meth\u00adyl]-1-ethyl\u00adpiperidin-1-ium ethane\u00adsulfonate  symmetry. The chiral space group indicates that the achiral compound in the elementary cell is packed chirally; the Flack absolute structure parameter amounts to \u22120.005\u2005(6) \u00b0 (C7\u2014Si1\u2014C10) and the largest angle of 114.32\u2005(7)\u00b0 (C8\u2014Si1\u2014C10). This geometric distortion has been observed in many complex substituted silicon compounds and depends on the substituents  to 167\u2005(2)\u00b0 (C3\u2014H3\u22efO2i). The shortest hydrogen-bond length is 3.1815\u2005(16)\u2005\u00c5 and is the strongest supra\u00admolecular inter\u00adaction with an angle of 162.8\u2005(17)\u00b0 (C17\u2014H17A\u22efO4). Analysis of the hydrogen-bonding network shows that all the hydrogen bonds shown in Table\u00a02D11(2); Etter et al., 1990The crystal packing along the \u03b1-amino\u00adsilane derivatives that are structurally based on compound 1 and its starting compound 2. Examples of such \u03b1-piperidino\u00adsilanes found in the Cambridge Structural Database -1-methyl-1-{[meth\u00adyl(phen\u00adyl)(tri\u00admethyl\u00adgerm\u00adyl)sil\u00adyl]meth\u00adyl}piperidinium iodide, C17H32GeNSiI meth\u00adyl]gall\u00adium n-pentane solvate, C45H67GaN2Si4\u00b70.5(C5H12) -5,6-aza-C60fulleroid, C79H17NSi  (0.81\u2005mmol) was dissolved in acetone (3\u2005ml) and diethyl sulfate (0.81\u2005mmol) was added dropwise to the solution. The reaction mixture was stirred and heated for 6\u2005h at 329\u2005K. Afterwards the reaction was quenched by the addition of a mixture of H2O (2\u2005ml) and NH3 (2\u2005ml). The aqueous phase was extracted three times with CH2Cl2 and the combined organic phases were dried over Na2SO4. After the removal of volatile compounds, the raw product was dissolved in n-pentane (1\u2005ml) and stored at 243\u2005K. The title salt (1) was isolated as colorless crystalline blocks.The reaction scheme for the synthesis of 1H NMR : \u03b4 = 0.30 , 1.24\u20131.31 , 1.65\u20131.90 , 2.29 , 3.12 , 3.37\u20133.56 , 4.12 , 7.04 , 7.10\u20137.15 , 7.24  ppm.Uiso(H).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902101361X/hb8003sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902101361X/hb8003Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902101361X/hb8003Isup3.cmlSupporting information file. DOI: 2131144CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom in the title compound, which exhibits strong blue emission, adopts a highly distorted trigonal\u2013planar geometry coordinated by two pyridine N atoms of two crystallographically independent 2\u2032,6\u2032-di\u00adfluoro-2,3\u2032-bi\u00adpyridine ligands and one O atom of the tri\u00adfluoro\u00admetane\u00adsulfonate anion.The Ag 3SO3)(C10H6F2N2)2], the AgI centre adopts a highly distorted trigonal\u2013planar coordination environment resulting from its coordination by one O atom of the tri\u00adfluoro\u00admethane\u00adsulfonate anion and the pyridine N atoms of two crystallographically independent 2\u2032,6\u2032-di\u00adfluoro-2,3\u2032-bi\u00adpyridine ligands, which display very similar conformations to one another. Pairwise Ag\u22efO\u2013SO2CF3\u2212 [Ag\u22efO = 2.8314\u2005(14)\u2005\u00c5] inter\u00adactions and inter\u00admolecular C\u2014H\u22efO inter\u00adactions between inversion-related units lead to the formation of an eight-membered cyclic dimer in which the silver atoms are separated by 6.2152\u2005(3)\u2005\u00c5. In the crystal, the dimers are linked through C\u2014H\u22efO hydrogen bonds, halogen\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions, resulting in the formation of a three-dimensional supra\u00admolecular network. The title compound exhibits a strong and broad emission band from 400\u2005nm to 550\u2005nm in solution and its photoluminescence quantum efficiency is estimated to be ca 0.2, indicating that the title compound could have applications as an emitting material in organic light-emitting diodes (OLEDs).In the title compound, [Ag(CF III and PtII complexes by many researchers because of their applicability to OLEDs and solid-state lighting  and 53.10\u2005(7)\u00b0, respectively. As shown in Fig.\u00a01I ion is coordinated by two pyridine N atoms (N2 and N4) from two 2\u2032,6\u2032-di\u00adfluoro-2,3\u2032-bi\u00adpyridine ligands and one O atom from the tri\u00adfluoro\u00admethane\u00adsulfonate anion, forming a highly distorted trigonal\u2013planar geometry. Selected bond lengths and angles around the Ag1 atom are given in Table\u00a012CF3\u2212 inter\u00adaction between the metal ion and an O atom of an adjacent tri\u00adfluoro\u00admethane\u00adsulfonate anion . The AgI atom is displaced out of the trigonal N2, N4, O1 coordination plane by 0.1057\u2005(9)\u2005\u00c5. The C6\u2013C10/N2 and C16\u2013C20/N4 pyridine rings coordinated to the AgI centre are tilted by 25.75\u2005(10)\u00b0 with respect to each other. The pairwise Ag\u22efO links lead to the formation of an eight-membered [Ag\u2014O\u2014S\u2014O\u2014]2 cyclic dimer, in which the silver atoms are separated by 6.2152\u2005(3)\u2005\u00c5. The cyclic dimer is consolidated by C\u2014H\u22efO inter\u00adactions (Table\u00a02The asymmetric unit in the title compound consists of an Ags Table\u00a02.Cg4\u22efCg4ii = 3.9737\u2005(11)\u2005\u00c5; Cg4 is the centroid of the C16\u2013C20/N4 ring; symmetry code: (ii) \u2212x, \u2212y, \u2212z\u00a0+\u00a01] between the pyridine rings, forming a chain structure propagating along the a-axis direction. Neighbouring chains are connected by halogen\u22ef\u03c0 inter\u00adactions , thereby generating a two-dimensional supra\u00admolecular network lying parallel to the ab plane. Finally, these networks are stacked along the c-axis direction and connected by halogen\u22ef\u03c0 and weak \u03c0\u2013\u03c0 stacking inter\u00adactions , resulting in the formation of a three-dimensional supra\u00admolecular network.In the extended structure, the dimers are linked through C19\u2014H19\u22efO3 hydrogen bonds Table\u00a02 and weak2Cl2 solution, the title compound exhibits a strong and broad emission band with \u03bbmax = 400\u2005nm, as shown in Fig.\u00a053SO3) unit, significant blue-shifted emissions (> 50\u2005nm) are observed as compared with bi\u00adpyridine based IrIII complexes . The observed emission of the title compound is therefore attributed to ligand-centered \u03c0\u2013\u03c0* transitions with a minor contribution of an Ag-based metal-to-ligand charge-transfer transition. Similar dual-emission behaviour has been noted for some AgI complexes with 2-methyl\u00adthio\u00adthia\u00adzole   in MeOH (2\u2005ml) in the dark at room temperature and the mixture was stirred for 10\u2005min. After that, the mixture was slowly evaporated in the air and a dark environment to obtain crystals suitable for X-ray crystallographic analysis. 1H NMR  \u03b4 8.67 , 8.62 , 7.88\u20137.80 , 7.37\u20137.34 , 7.0.8 . 19F NMR  \u03b4 \u221269.7, \u221271.8, 79.1. Analysis calculated for C21H12F7N4O3SAg: C 39.33; H 1.89; N 8.74%; found: C 39.44, H 1.86, N 8.70%.All experiments were performed under a dry NUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021011282/hb7990sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989021011282/hb7990Isup2.hklStructure factors: contains datablock(s) I. DOI: 2118061CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The salan ligands coordinate to the molybdenum center in a \u03ba2N,\u03ba2O fashion, forming a distorted octa\u00adhedral geometry. These complexes crystallized as di\u00admethyl\u00adformamide and methanol solvated species.Two  cis-dioxomolybdenum complexes based on salan ligands with different backbones are reported. The first complex, dioxido{2,2\u2032-bis\u00ad(phenolato)}molybdenum(VI) di\u00admethyl\u00adformamide disolvate, [Mo(C20H18N2O2)O2]\u00b72C3H7NO , features a phenyl backbone, while the second complex, bis(aza\u00adnedi\u00adyl)]bis\u00ad(methyl\u00adene)}bis\u00ad)dioxidomolybdenum(VI) methanol disolvate, [Mo(C36H56N2O2)O2]\u00b72CH3OH , is based on a cyclo\u00adhexyl backbone. These complexes crystallized as solvated species, 1b\u00b72DMF and 2b\u00b72MeOH. The salan ligands PhLH2 (1a) and CyLH2 (2a) coordinate to the molybdenum center in these complexes 1b and 2b in a \u03ba2N,\u03ba2O fashion, forming a distorted octa\u00adhedral geometry. The Mo\u2014N and Mo\u2014O distances are 2.3475\u2005(16) and 1.9567\u2005(16)\u2005\u00c5, respectively, in 1b while the corresponding measurements are Mo\u2014N = 2.3412\u2005(12)\u2005\u00c5, and Mo\u2014O = 1.9428\u2005(10)\u2005\u00c5 for 2b. A key geometrical feature is that the N\u2014Mo\u2014N angle of 72.40\u2005(4)\u00b0 in CyLMoO2 is slightly less than that of the PhLMoO2 angle of 75.18\u2005(6)\u00b0, which is attributed to the flexibility of the cyclo\u00adhexane ring between the nitro\u00adgen as compared to the rigid phenyl ring in the PhLMoO2.Two  In this system, the salan ligand PhLH2 (1a) coordinates to the molybdenum center in a \u03ba2N,\u03ba2O fashion, forming a distorted octa\u00adhedral geometry. The angles formed around the molybdenum core are 80.23\u2005(6)\u00b0 for O1\u2014Mo01\u2014N1, 157.78\u2005(6)\u00b0 for O1\u2014Mo01\u2014O2, 75.18\u2005(6)\u00b0 for N1\u2014Mo01\u2014N2, and 109.80\u2005(7)\u00b0 for O3\u2014Mo01\u2014O4. These angles are consistent with a system that is significantly distorted from octa\u00adhedral geometry with bond angles resulting from the salan ligand ranging from 75.18\u2005(6) to 84.38\u2005(7)\u00b0, while the angle between the \u2018oxo\u2019 oxygens of 109.80\u2005(7)\u00b0 is close to the ideal tetra\u00adhedral angle of 109.5\u00b0. Analogous bond angles in the second molecule in the unit cell are the same within 0.01\u2005\u00c5. The bond distances between the molybdenum center and ligand atoms for Mo01\u2014N1 and Mo01\u2014O1 are 2.3475\u2005(16) and 1.9567\u2005(16)\u2005\u00c5, respectively. The notable bond distances from the salan ligand are O1\u2014C1 at 1.377\u2005(2)\u2005\u00c5, N1\u2014C7 at 1.486\u2005(3)\u2005\u00c5, C2\u2014C7 at 1.515\u2005(3)\u2005\u00c5, N1\u2014C8 at 1.389\u2005(8)\u2005\u00c5, and C8\u2014C13 at 1.419\u2005(3)\u2005\u00c5. Analogous bond distances in the second molecule in the unit cell are the same within 0.01\u2005\u00c5 as distances for O1\u2014C1 and N1\u2014C8, respectively. The other bond distances have variations of 0.2\u20130.3\u2005\u00c5, with N3\u2014C27 at 1.519\u2005(3)\u2005\u00c5, C26\u2014C27 at 1.490\u2005(3)\u2005\u00c5, and C28\u2014C33 at 1.392\u2005(3)\u2005\u00c5.The asymmetric unit of CyLMoO2 (2b) contains one mol\u00adecule of CyLMoO2 and two mol\u00adecules of methanol (MeOH)  binds in the same \u03ba2N,\u03ba2O fashion that complex 1b does. Fig.\u00a04CyLMoO2 with the hydrogen atoms removed for clarity. The complex also has a distorted octa\u00adhedral geometry with angles of O3\u2014Mo01\u2014O1 at 96.36\u2005(5)\u00b0, O1\u2014Mo01\u2014N1 at 76.73\u2005(4)\u00b0, N1\u2014Mo01\u2014N2 at 72.40\u2005(4)\u00b0, N2\u2014Mo01\u2014O2 at 78.91\u2005(4)\u00b0, O2\u2014Mo01\u2014O4 at 100.19\u2005(5)\u00b0, O2\u2014Mo01\u2014O3 at 94.58\u2005(5)\u00b0. These angles are between 5 and 10\u00b0 of the ideal 90\u00b0 for octa\u00adhedral geometry. The N1\u2014Mo01\u2014N2 angle at 72.40\u2005(4)\u00b0 is slightly less than that of the PhLMoO2 angle of 75.81\u2005(6)\u00b0, which is attributed to the flexibility of the cyclo\u00adhexane ring between the nitro\u00adgen atoms compared to the rigid phenyl ring in the PhLMoO2. Metal\u2013ligand bond distances are found for Mo01\u2014O1 at 1.9428\u2005(10)\u2005\u00c5, Mo01\u2014O2 at 1.9484\u2005(10)\u2005\u00c5, Mo01\u2014O3 at 1.7125\u2005(10)\u2005\u00c5, Mo01\u2014O4 at 1.7226\u2005(11)\u2005\u00c5, Mo01\u2014N1 at 2.3412\u2005(12)\u2005\u00c5, and Mo01\u2014N2 at 2.3384\u2005(12)\u2005\u00c5. Other ligand distances and bond lengths within the phenyl rings are consistent with analagous distances in PhLMoO2 (1b). The cylohexane bond distances are consistent with single C\u2014C bonds. The bond lengths observed are not statistically different than those reported by Ziegler et al. (2009R1 of 2.78% as compared to the previously reported R1 of 5.5% and higher solvent disorder in the reported structure.The asymmetric unit of H) Fig.\u00a03. The sal al. 2009. There aPhLMoO2 (1b): A single mol\u00adecule of PhLMoO2 is hydrogen bonded to one disordered DMF mol\u00adecule, as shown in Fig.\u00a05D with a distance of 2.16\u2005(3)\u2005\u00c5. Corresponding hydrogen bond distances in the second molecule in the unit cell are similar. There are three formula units within the contents of the unit cell. Perpendic\u00adular \u03c0-stacking between PhLMoO2 mol\u00adecules is observed between C5 and the aryl ring centroid (C35\u2013C39) with a distance of 4.597\u2005\u00c5.CyLMoO2 (2b): There are four mol\u00adecules of CyLMoO2 in the unit cell of this system and the complex is stabilized via hydrogen bonding to the solvent MeOH mol\u00adecule . There was a similar crystal structure found with the imine form of the ligand MoO2. A search for CyLMoO2 (2b) in the CSD  shows that there is a known structure of the mol\u00adecule with a different unit cell with accession code HUWGOW  was solved in space group P 21/n compared with P31 for HUWGOW. The primary additional differences in the structures is an improved R1 of 2.78% and more clearly resolved methanol solvent, as compared to the previously reported R1 of 5.5% and more disordered methanol solvent    and CyLH2 (2a) were synthesized as off-white solids in 86% and 58% yields, respectively. The reaction scheme is shown in Fig.\u00a071H NMR spectra of both ligands as compared to the precursor salen compounds was the disappearance of the aldimine peak (\u223c8.50 ppm) and the appearance of the benzylic resonances \u223c4.00 ppm. The molybdenum complexes PhLMoO2 (1b) and CyLMoO2 (2b) were synthesized in 86% and 42% yields, respectively, by the reaction of the corresponding ligands with MoO2(acac)2 in methanol or aceto\u00adnitrile as solvent. Complexes 1b and 2b were also characterized by NMR and IR spectroscopy. Both complexes exhibited stretches { characteristic of a cis-dioxo molybdenum core in the IR spectrum.The salan ligands used for stabilizing molybdenum(VI) )dioxidomolybdenum(VI) : A round-bottom flask equipped with a magnetic stirring bar was charged with MoO2(acac)2  and methanol (ca. 10\u2005mL). The solution was stirred, and 2a  was added to the MoO2(acac)2 dissolved in methanol. The solution was stirred overnight when it turned orange. The solution was filtered, and the solvent removed by evaporation under vacuum to obtain an orange precipitate. The precipitate was triturated with methanol, producing an orange solid, which was separated by gravity filtration and was washed twice with cold methanol . 1H NMR  \u03b4 7.26 , 6.86 , 5.28 , 4.18 , 2.34\u20132.28 , 1.43 , 1.30 , 1.19\u20131.17 , 0.88\u20130.85 . 13C{1H} NMR  \u03b4 157.1, 152.1, 142.8, 142.3, 142.0, 138.0, 137.7, 137.6, 125.7, 125.4, 124.1, 124.0, 123.0, 122.9, 120.0, 119.6, 65.19, 58.9, 57.6, 53.4, 50.9, 50.5, 35.2, 35.1, 34.3, 34.2, 33.0, 31.6, 31.6, 31.5, 29.9, 29.9, 28.9, 24.5, 24.3, 24.1. Selected IR (cm\u22121): 903, 875 \u03c5(Mo=O).bis\u00ad(aza\u00adnedi\u00adyl)]bis\u00ad(methyl\u00adene)}bis\u00ad = 1.2Ueq(C) for CH, CH2, and CH3. The structure for PhMoO2 (1b) was initially refined in the trigonal crystal system P3221; however, this resulted in the solvent DMF having a high level of disorder with many checkCIF errors.Crystal data, data collection, and refinement details are listed in Table\u00a0410.1107/S2056989022000524/tx2046sup1.cifCrystal structure: contains datablock(s) 2b, 1b. DOI: 10.1107/S2056989022000524/tx20462bsup3.hklStructure factors: contains datablock(s) 2b. DOI: 10.1107/S2056989022000524/tx20461bsup2.hklStructure factors: contains datablock(s) 1b. DOI: 2142074, 2142073CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A three-dimensional network of hydrogen bonds serves to hold the structure together.The polymer contains Li 4(C3H2N3O3)4(H2O)7]n, synthesized at room temperature from an aqueous solution of lithium hydroxide and cyanuric chloride, crystallizes in the triclinic space group P+ cations in the asymmetric unit, one of which, Li1, has distorted trigonal\u2013bipyramidal geometry and is coordinated via oxygen to two cyanurate anions occupying equatorial positions, and three water mol\u00adecules, two in the axial positions and the third in an equatorial position. One of the axial water ligands and the equatorial water ligand are involved in bridging to a crystallographically equivalent Li1 cation. A centre of inversion lies between the two Li1 cations and the Li1\u22efLi1 distance is 3.037\u2005(5)\u2005\u00c5. The remaining axial water ligand bridges to the second Li cation, Li2, which is disordered over two crystallographic sites with approximately equal occupancy, and has an Li1\u22efLi2 distance of 3.438\u2005(7)\u2005\u00c5. The terminal Li2 cation is coordinated to three water mol\u00adecules and an oxygen atom from a cyanuric anion and has a distorted tetra\u00adhedral geometry. A three-dimensional network of inter\u00admolecular hydrogen bonds involving N\u2014H\u22efO, O\u2014H\u22efO and O\u2014H\u22efN inter\u00adactions serves to hold the structure together. The title compound was further characterized using IR and UV\u2013vis spectroscopy and TG\u2013DTA analysis.The polymeric title complex, poly[hexa-\u03bc-aqua-diaquatetra-\u03bc-cyanurato-tetralithium] [Li The complex has been characterized by single-crystal X-ray diffraction, FTIR and UV\u2013Vis spectroscopy, and TG\u2013DTA analysis.As cyanuric acid has three hydrogen-bonding-donor amine sites and three hydrogen-bonding-acceptor keto sites, it has been the subject of several structural and crystal-design studies 4(H2O)7] . This coordination preference may be due to the hard acid, Li+, preferring to bond to the harder base i.e. oxygen.The two crystallographically distinct cyanurate ligands exist in resonance form (IV) Fig.\u00a01, in whicet al., 2020A and Li2B) and have slightly longer bond lengths: C2\u2014O3, 1.2439\u2005(18)\u2005\u00c5; C3\u2014O2, 1.2436\u2005(19)\u2005\u00c5; C5\u2014O5, 1.2442\u2005(18)\u2005\u00c5 and C6\u2014O6, 1.2430\u2005(18)\u2005\u00c5. The delocalization of the negative charge on the deprotonated nitro\u00adgen atoms (N2 and N5) over the adjacent keto groups is shown as dashed lines in Fig.\u00a02The C=O groups involved in coordination to Li1, namely C1=O1 and C4=O4 have bond lengths of 1.2207\u2005(19) and 1.2242\u2005(19)\u2005\u00c5, respectively Fig.\u00a03, which a+ cations in the asymmetric unit  in the axial positions and the third (H2O8) in an equatorial position. The Li1\u2014O bond lengths lie in the range 2.012\u2005(3)\u2013 2.201\u2005(3)\u2005\u00c5 and the bond angles of O4\u2014Li1\u2014O1 = 118.40\u2005(13)\u00b0, O4\u2014Li1\u2014O8 = 120.78\u2005(14)\u00b0, O1\u2014Li1\u2014O8 = 120.74\u2005(14)\u00b0 and O8i\u2014Li1\u2014O7 = 178.56\u2005(15)\u00b0 confirm the trigonal\u2013bipyramidal Li1 coordination geometry. One of the axial water ligands, H2O8i, and the equatorial water ligand, H2O7, bridge to a crystallographically equivalent Li1 cation. The Li1\u22efLi1i distance is 3.037\u2005(5)\u2005\u00c5, which is larger than the Li\u2014Li bond distance found in lithium metal. The Li1\u2014O\u2014Li1i bridge angle is 95.00\u2005(11)\u00b0. The Li1\u2014O8 and Li1\u2014O8i bond lengths are 2.032\u2005(3) and 2.086\u2005(3)\u2005\u00c5, respectively.There are two distinct Liit Fig.\u00a03. Li1 has2O7, bridges to the second Li+ cation, Li2, which is disordered over two sites, Li2A and Li2B, which have approximately equal occupancies. The Li1\u22efLi2A and Li1\u22efLi2B distances are 3.438\u2005(7) and 3.439\u2005(7)\u2005\u00c5, respectively. Li2 is coordinated to two more water mol\u00adecules, H2O9, H2O10 and an oxygen atom from a cyanurate ligand (either O3ii for Li2A or O2iii for Li2B) to complete its distorted tetra\u00adhedral coordination geometry. The Li2\u2014O bond lengths lie in the range 1.931\u2005(7)\u20132.057\u2005(7)\u2005\u00c5 and the O\u2014Li2\u2014O angles in the range 97.9\u2005(3)\u2013125.3\u2005(3)\u00b0The remaining axial water ligand, H4(C3H2N3O3)4(H2O)7] units into a three-dimensional network  and 2.7443\u2005(16)\u2005\u00c5, respectively].Strong inter\u00admolecular hydrogen-bonding inter\u00adactions Table\u00a01 link therk Fig.\u00a04. These ii, N3\u2014H3\u22efO5ii, N4\u2014H4\u22efO6iii and N6\u2014H6\u22efO6iv). Weaker hydrogen-bonding inter\u00adactions, with N\u22efO distances in the range 2.905\u2005(2)\u20133.0342\u2005(19)\u2005\u00c5 are also observed between the unprotonated N atoms of the cyanurate ions and nearby water mol\u00adecules .In addition, each cyanurate moiety forms two strong hydrogen bonds between the N\u2014H groups and oxygen atoms of adjacent mol\u00adecules with N\u22efO distances in the range 2.7964\u2005(16)\u20132.8054\u2005(17)\u2005\u00c5 \u00adbis\u00addicopper(I) tetra\u00adaqua\u00adstrontium(II)] bis\u00ad(\u03bc-aqua)\u00adtetra\u00adaqua\u00adcopper(II)disodium(I)]  and 3389\u2005cm\u22121 (br) correspond to \u03bd(O\u2014H)    1/2/h\u03bd, where t is the thickness of the crystal (1\u2005mm) and h\u03bd is the photon energy. A plot of (\u03b1h\u03bd)2versus h\u03bd is shown as the inset in Fig.\u00a07Eg) is estimated to be 5.22\u2005eV.The UV\u2013Vis NIR absorption spectrum was measured using a Perkin Elmer lambda 950 UV\u2013Vis\u2013NIR spectrophotometer Fig.\u00a06. The pea\u22121 with a resolution of 1\u2005\u00b5g under a dry N2 atmosphere. The thermogram  .Simultaneous TG\u2013DTA measurements and analysis of weight change and heat flow were performed using a Perkin Elmer STA 6000 instrument operating at a scanning rate of 10\u00b0C minam Fig.\u00a07 shows foLithium hydroxide  and cyanuric chloride  were dissolved in water (100\u2005ml). The resulting solution was stirred for 5\u2005h at ambient temperature (300-301\u2005K) and filtered twice using Whatman filter paper. The solvent was allowed to evaporate in a dust-free environment. After 22 days, good quality colourless crystals were harvested.A and Li2B, which were resolved using the PART command  = 1.2Ueq(N). The hydrogen atoms on the water mol\u00adecules were located in difference-Fourier maps and each Uiso(H) parameter was freely refined with the O\u2014H distance restrained to 0.85\u2005(2)\u2005\u00c5 using DFIX. The H\u2014O\u2014H angle distances were restrained using DFIX to a target value of 1.39\u2005(2)\u2005\u00c5 [or 1.41\u2005(2)\u2005\u00c5 for H9A\u2014O9\u2014H9B] in order to keep the water mol\u00adecules close to their standard geometries.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021009324/cq2044sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021009324/cq2044Isup2.hklStructure factors: contains datablock(s) I. DOI: 1991191CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "To evaluate the effect of toric intraocular lens implantation in cataract patients with irregular corneal steep and flat meridian.  Data of 112 eyes of 78 patients who underwent toric intraocular lens implantation were analyzed retrospectively. Steep meridian deviations (not 180\u00b0) and steep and flat meridian deviations (not 90\u00b0) were classified as 0, 1\u20139, 10\u201319, 20\u201329, 30\u201339, and over 30\u00b0. Meridian deviation was measured with a sagittal map of a rotating Scheimpflug camera  using PicPickTools . D) of 0  and 1\u20139  groups were significantly lower than that of 10\u201319 , 20\u201329 , and over 30\u00b0 groups  both in steep meridian deviations and horizontal and vertical meridian deviations at 6 months (P < 0.05). Postoperative mean UCVA (logMAR) of 0  (logMAR) and 1\u20139  groups was significantly improved compared to that of 10\u201319 , 20\u201329 , and over 30\u00b0 groups  both in steep meridian deviations and horizontal and vertical meridian deviations at 6 months (P < 0.05).  Residual astigmatism ( Correction of astigmatism with toric intraocular lens implantation is not accurate in corneas with steep meridian deviations and steep and flat meridian deviations of more than 10\u00b0. Therefore, care should be taken when we perform toric intraocular lens implantation in patients with irregular corneal meridian. D) of corneal astigmatism [D or greater [Cataract is the most common cause of visual impairment in elderly people . About 6igmatism , and 20% greater . If this greater . Toric i greater . Toric I greater . TherefoTo the best of our knowledge, no studies have reported the efficacy of toric IOL implantation in normal patients with irregular corneal astigmatism such as steep meridian deviations or steep and flat meridian deviation. Thus, the objective of this study was to evaluate outcomes of toric IOL implantation according to the amount of steep meridian deviations and angle deviation of steep and flat meridian.We performed a retrospective chart review and data analysis in this study. This study was conducted in compliance with Institutional Review Board regulations, informed consent regulations, sponsor and investigator obligations, and the Declaration of Helsinki. The Institutional Review Board (IRB)/Ethics Committee of Bucheon St. Mary Hospital approved this study protocol.A total of 112 eyes of 78 patients who underwent toric intraocular lens implantation in Bucheon St. Mary Hospital from July 2017 to April 2018 were enrolled. Steep meridian deviations (not 180\u00b0) were classified as 0, 1\u20139, 10\u201319, 20\u201329, 30\u201339, and over 30\u00b0. Steep and flat meridian deviations (not 90\u00b0) were classified as 0, 1\u20139, 10\u201319, 20\u201329, and over 30\u00b0. Inclusion criteria were advanced cataracts in patients with high corneal astigmatism more than 1.5D. Exclusion criteria were a history of any ocular injury or disorder, infection, inflammation, and surgery within prior 6 months.Steep meridian deviations and steep and flat meridian deviation were measured with a sagittal map of a rotating Scheimpflug camera  using PicPickTools . Steep meridian deviation was determined as an absolute value of 180 minus the steep axis angle. Steep and flat meridian deviation was determined as an absolute value of 90 minus steep and flat meridian angle .\u00ae, Oculus, Germany).All patients underwent a complete ophthalmological examination. Their demographic and perioperative data were recorded. Uncorrected and corrected distance visual acuities were expressed as logMAR. Manifest refraction, biometry, and keratometry with the IOLMaster partial coherence interferometry device (Carl Zeiss Meditec AG), corneal topography , slit lamp examination, and dilated funduscopy were examined at the preoperative period and postoperative 2, 4, and 6 months. The IOL manufacturer's web-based toric calculator was used to determine the required cylinder power and axis for the IOL that was going to be implanted. The total corneal astigmatism was measured using the Scheimpflug system  using an Intrepid Infiniti system . Corneal steep axis and 6.0\u2009mm ring were marked with gentian violet. Surgery was performed through a clear corneal incision at the steep astigmatic axis. After topical ocular anesthesia was applied, a 2.75\u2009mm clear corneal incision was made using a 2.75\u2009mm double-blade keratome (Alcon). Surgically induced astigmatism was set by 0.5 diopters. Sodium hyaluronate 1.0%  was used to reform and stabilize the anterior chamber. A continuous curvilinear capsulotomy was made according to a 6.0\u2009mm corneal marker using Inamura capsulorhexis forceps . Hydrodissection and hydrodelineation were achieved using a balanced salt solution. Phacoemulsification was performed using 2.75\u2009mm-sized phacotips and infusion/aspiration (I/A) cannulas for micro- and small-incision groups, respectively. A clear preloaded IOL  was implanted in the capsular bag. The IOL was rotated to the correct axis position according to the axis of total corneal astigmatism. The wound was not sutured. Postoperative treatment consisted of gatifloxacin 0.3%  and fluorometholone acetate 0.01%  eye drops four times a day for four weeks.P values\u2009<\u20090.05 were considered statistically significant.All statistical analyses were performed using a commercial program . The Wilcoxon signed rank test was used to compare pre- and postoperative BCVA and refractive and keratometer astigmatisms. A total of 112 eyes of 78 patients were enrolled in this study. Preoperative mean autorefractive cylinder was 2.21\u2009\u00b1\u20091.36 D. Mean total corneal astigmatism measured with the Scheimpflug camera was 2.35\u2009\u00b1\u20091.15 D. Mean UCVA was 0.83\u2009\u00b1\u20090.35 (logMAR), and mean BCVA was 0.56\u2009\u00b1\u20090.29 (logMAR) .P < 0.05). Postoperative mean total corneal astigmatism (1.96\u2009\u00b1\u20091.0 D) was also decreased compared to preoperative value (2.35\u2009\u00b1\u20091.15 D), but the decrease was statistically insignificant. Mean IOL rotation was 3.2\u2009\u00b1\u20091.5\u00b0 at 2 months after toric IOL implantation. Postoperative mean UCVA (0.09\u2009\u00b1\u20090.06) (logMAR) and mean BCVA (0.02\u2009\u00b1\u20090.01) were improved compared to preoperative values  (both P < 0.05)  was significantly decreased compared to its preoperative value (2.21\u2009\u00b1\u20091.36 D) ( < 0.05) .D) and mean UCVA (logMAR) of all groups were similar to each other . Postoperative mean UCVA (logMAR) of 0 (0.09\u2009\u00b1\u20090.04) (logMAR) and 1\u20139\u00b0 (0.10\u2009\u00b1\u20090.04) groups was significantly improved compared to that of 10\u201319 (0.14\u2009\u00b1\u20090.05), 20\u201329 (0.18\u2009\u00b1\u20090.08), and over 30\u00b0 groups (0.20\u2009\u00b1\u20090.09) in steep meridian deviations at 6 months  (D) values of 0 (0.51\u2009\u00b1\u20090.13) and 1\u20139\u00b0 groups (0.61\u2009\u00b1\u20090.16) were significantly lower than those of 10\u201319 (0.92\u2009\u00b1\u20090.24), 20\u201329 (0.10\u2009\u00b1\u20090.32), and over 30\u00b0 groups (1.12\u2009\u00b1\u20090.37) in steep meridian deviations at postoperative 6 months (P < 0.05) (D)   . Estimat < 0.05) . There w < 0.05) .P > 0.05). However, preoperative total corneal astigmatism (D) of 21\u201330\u00b0 (2.04\u2009\u00b1\u20090.86 D) and over 30\u00b0 groups (2.06\u2009\u00b1\u20091.05 D) was statistically higher than that of other groups  (P < 0.05). Postoperative mean UCVA (logMAR) values of 0 (0.09\u2009\u00b1\u20090.05) and 1\u20139\u00b0 (0.11\u2009\u00b1\u20090.08) were significantly improved compared to those of 10\u201319 (0.17\u2009\u00b1\u20090.10), 20\u201329 (0.21\u2009\u00b1\u20090.10), and over 30\u00b0 groups (0.22\u2009\u00b1\u20090.11) in steep and flat meridian deviations at 6 months (P < 0.05) (D) of 0 (0.55\u2009\u00b1\u20090.15) and 1\u20139\u00b0 groups (0.66\u2009\u00b1\u20090.19) was significantly lower than that of 10\u201319 (0.90\u2009\u00b1\u20090.28), 20\u201329 (1.01\u2009\u00b1\u20090.35), and over 30\u00b0 groups (1.14\u2009\u00b1\u20090.40) in steep and flat meridian deviations at postoperative 6 months (P < 0.05) (D)   values of all groups were similar to each other ( < 0.05) . Estimat < 0.05) . There w < 0.05) .D depending on preoperative astigmatism [Implantation of toric IOL in cataract surgery to correct corneal astigmatism has been popular due to its excellent clinical outcomes and increased patient demands . Howeverigmatism . Severaligmatism , ignorinigmatism , inaccurigmatism . Zhu et igmatism . In the If there are severe steep meridian deviations, the other marker of toric IOL and corneal steep meridian may be misaligned despite that surgeons have made a perfect alignment of one marker of toric IOL and corneal steep meridian. If there is a severe steep and flat meridian deviation, the toric IOL steep axis and corneal flat axis may be misaligned despite that the surgeon has made a perfect alignment of marker of toric IOL and corneal steep meridian.D) values of 0 (0.51\u2009\u00b1\u20090.13) and 1\u20139\u00b0 groups (0.61\u2009\u00b1\u20090.16) were significantly lower than those of 10\u201319 (0.92\u2009\u00b1\u20090.24), 20\u201329 (0.10\u2009\u00b1\u20090.32), and over 30\u00b0 groups (1.12\u2009\u00b1\u20090.37) in steep meridian deviations at postoperative 6 months (P < 0.05) (D) and mean UCVA (logMAR) values of all groups were similar to each other (P > 0.05). However, postoperative mean UCVA (logMAR) of 0 (0.09\u2009\u00b1\u20090.04) (logMAR) and 1\u20139\u00b0 (0.10\u2009\u00b1\u20090.04) groups was significantly improved compared to that of 10\u201319 (0.14\u2009\u00b1\u20090.05), 20\u201329 (0.18\u2009\u00b1\u20090.08), and over 30\u00b0 groups (0.20\u2009\u00b1\u20090.09) in steep meridian deviation at 6 months (P < 0.05)  . Preoper < 0.05) .D) values of 21\u201330\u00b0 and over 30\u00b0 groups were statistically higher than those of other groups (P < 0.05)  . We hypoD) of 0 (0.55\u2009\u00b1\u20090.15) and 1\u20139\u00b0 groups (0.66\u2009\u00b1\u20090.19) were significantly lower than that of 10\u201319 (0.90\u2009\u00b1\u20090.28), 20\u201329 (1.01\u2009\u00b1\u20090.35), and over 30\u00b0 groups (1.14\u2009\u00b1\u20090.40) in steep and flat meridian deviations at postoperative 6 months (P < 0.05) (P < 0.05)  . Also, p < 0.05) .D) at 6 months  (D)   . A posit < 0.05)  was alsoP < 0.05). Therefore, patients who had meridian deviations of less than 10\u00b0 had significantly lower residual astigmatism and better uncorrected visual acuity than those who had meridian deviation of more than 10\u00b0.Toric IOL rotations of less than 10\u00b0 changed the eye's refractive astigmatism to less than 0.50 diopters . In the D) also increased in patients with irregular corneal astigmatism. Therefore, the effect of toric IOL implantation is optimized in patients with regular corneal astigmatism. Toric IOL implantation should be performed cautiously when patients have steep meridian deviations or steep and flat meridian deviations.To the best of our knowledge, this was the first study to evaluate the outcomes of toric IOL implantation in cataract patients with irregular corneal astigmatism. The postoperative visual acuity of patients with regular astigmatism was significantly improved compared to that of patients with steep meridian deviations and the steep and flat meridian deviations. If steep meridian deviations and steep and flat meridian deviations increased, estimated residual astigmatism (A multicenter clinical trial with a larger sample size and longer follow-up period is needed to observe the long-term efficacy of toric intraocular lens implantation in cataract patients with irregular corneal astigmatism."}
{"text": "The packing of the units is dominated by C\u2014H\u22efO hydrogen bonding and weak dispersion forces, with a minor contribution from C\u2014H\u22ef\u03c0 bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions.The structure of tel\u00adlur\u00adium(VI)], [Sb3Te(C6H5)9O6], the hexa\u00adoxidotellurate(VI) ion is coordinated to three SbV ions via pairs of cis-positioned O atoms to form a discrete mol\u00adecular unit. The TeVI and SbV central ions exhibit distorted octa\u00adhedral [TeO6] and distorted trigonal\u2013bipyramidal [SbC3O2] coordination geometries, respectively. The linking of these polyhedra, by sharing the dioxide edges, results in the Te-based octa\u00adhedron having a mer-configuration. The packing of the mol\u00adecules is dominated by C\u2014H\u22efO hydrogen bonding and weak dispersion forces, with a minor contribution from C\u2014H\u22ef\u03c0 bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions. According to the Hirshfeld surface analysis, the contributions of the H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH contacts are 58.0, 32.6 and 7.8%, respectively. The title structure provides a model for the bonding of triorgano\u00adanti\u00admony dications to octa\u00adhedral oxoanions, and the observed doubly bridged motifs, Te(\u03bc-O)2Sb, may find application in the functionalization of polyoxometalate species.In the structure of the title compound [systematic name hexa-\u03bc-oxido-1:2\u03ba The latter are formally similar to 1,2-benzene\u00addiolate chelates, which have been observed in mol\u00adecular organo\u00adanti\u00admony compounds 3TeO6, which features the formation of discrete clusters, [Te{(\u03bc-O)2SbPh3}3].At the same time, PhC2/c, and contains the discrete mol\u00adecular unit shown in Fig.\u00a016] octa\u00adhedron and three [Ph3SbO2] polyhedra sharing oxide edges. Thus two oxide bridges are formed from TeVI to each of the three SbV ions with Te\u2014O\u2014Sb angles in the range 99.33\u2005(13)\u2013102.41\u2005(13)\u00b0 \u2005\u00c5, which occurs in the Te1(\u03bc-O)2Sb2 unit. Such fully substituted organometallic hexa\u00adoxotellurate(VI) units are exceedingly rare, with the only known example being an aliphatic SnIV derivative 4Te(OH)2] and [(Ph3SnO)2Te(OMe)4] \u2013174.49\u2005(13)\u00b0. The fivefold coordination around each of three Sb-atoms can best be described as distorted trigonal bipyramidal, with the O2\u2014Sb1\u2014C7 = 161.09\u2005(15)\u00b0, O4\u2014Sb2\u2014C19 = 164.73\u2005(16)\u00b0 and O5\u2014Sb3\u2014C37 = 165.43\u2005(16)\u00b0 bond angles defining the principal axes of the trigonal bipyramids. This assignment is supported by the calculated five-coordinate \u03c4-indices, which are 0.69, 0.75 and 0.65 for Sb1, Sb2 and Sb3, respectively \u20132.110\u2005(3)\u2005\u00c5] than the equatorial Sb\u2014Oeq bonds, Sb1\u2014O1, Sb2\u2014O3 and Sb3\u2014O6 [in the range 1.966\u2005(3)\u20131.992\u2005(3)\u2005\u00c5]. This observation coincides with the differentiation of the Te\u2014O bond lengths; three of which, Te1\u2014O2, Te1\u2014O4 and Te1\u2014O5, lie in the range 1.904\u2005(3)\u20131.918\u2005(3)\u2005\u00c5 and three, Te1\u2014O1, Te1\u2014O3 and Te1\u2014O6, lie in the range 1.949\u2005(3)\u20131.968\u2005(3)\u2005\u00c5. Thus when considering the six Te\u2014O\u2014Sb bridges, the shorter Sb\u2014O bonds are accompanied by the longer Te\u2014O bonds and vice versa. The distribution of the Te\u2014OaxSb and Te\u2014OeqSb bonds indicates that the coordination octa\u00adhedron around the Te atom has the mer-configuration 3Te(OH)3] \u2005\u00c5; symmetry code (ii) x, y\u00a0+\u00a01, z; Table\u00a02b direction iii and C41\u2014H41\u22efCg(C13\u2013C18)iv  x, \u2212y\u00a0+\u00a02, x\u00a0\u2212\u00a0x, \u2212y\u00a0+\u00a01, z\u00a0+\u00a0bc plane. In addition, to further consolidate the bilayers, there are weak slipped \u03c0\u2013\u03c0 stacking inter\u00adactions between pairs of inversion-related phenyl rings, with a centroid-to-centroid distance, Cg(C1\u2013C6)\u22efCg(C1\u2013C6)v = 3.807\u2005(6)\u2005\u00c5, an inter\u00adplanar distance of 3.603\u2005(5)\u2005\u00c5 and a slippage angle of 18.8\u2005(5)\u00b0 . There are no specific inter\u00adactions between the bilayers, and the shortest of their C\u22efC contacts [3.404\u2005(6)\u2005\u00c5] is not accompanied by any \u03c0\u2013\u03c0 overlap.Very weak mutual C\u2014H\u22efO bonding  and trans-[(Ph3SnO)2Te(OMe)4] 2[CH2(Ph2SnO)2]2Te -octa\u00adkis\u00ad(tri\u00admethyl\u00adsil\u00adyloxy)ditellurium and orthotelluric acid tris\u00adester 3Te(OH)3, 4Te(\u03bc-O)2Te(OR)4 . The latter contains double Te\u2014O\u2014Te bridges, which are formally similar to the double Te\u2014O\u2014Sb bridges found in the title compound. No tetra\u00adhedral TeO4 fragments have been reported in organometallic series to date. The only known example of a tetra\u00adhedral tellurate is the ionic salt [NEt4]2TeO4\u00b72H2O . These results are consistent with the weakness of the C\u2014H\u22efO bonds in the structure. It is evident that only a few of the H\u22efC/C\u22efH contacts correspond to C\u2014H\u22ef\u03c0 bonding. Therefore, the H\u22efC/C\u22efH plot represents a rather diffuse collection of points between the pair of poorly resolved features and there no \u2018wings\u2019 at the upper left and lower right, which are characteristic of C\u2014H\u22ef\u03c0 inter\u00adactions  bromide as follows:In previously reported syntheses, a range of silver salts were used in ion-exchange reactions to form Ph3H3TeO6, was synthesized according to the method of Gospodinov (19923H3TeO6 were added to a solution containing 0.612\u2005g (1.2\u2005mmol) of Ph4SbBr in 20\u2005mL of aceto\u00adnitrile. The mixture was stirred for 3\u2005h and then the AgBr precipitate removed by filtration. Evaporation of the solution yielded a colourless glassy material, which was then dissolved in 10\u2005mL of a 1:1 v/v mixture of benzene and butyl acetate. Slow evaporation of the solution to a volume of 2\u20133\u2005mL afforded 0.138\u2005g (27%) of the product in the form of long colourless prisms. The crystals were filtered and dried in air. Analysis (%) for C54H45O6Sb3Te: Found: C 50.12, H 3.39; Calculated: C 50.56, H 3.54. IR : 454s, 520m, 610s, 692vs, 732vs, 772w, 996w, 1066m, 1434s, 1478m, 1576w, 2824w, 3052m.The starting material, Aginov 1992. 0.220\u2005gUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021011294/cq2048sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021011294/cq2048Isup2.hklStructure factors: contains datablock(s) I. DOI: 2118082CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of 2-(2-hy\u00addroxy\u00adphen\u00adyl)quinoline-6-sulfonamide contains two crystallographically independent mol\u00adecules. The crystal structure features hydrogen bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions. 15H12N2O3S, there are two mol\u00adecules (A and B) in the asymmetric unit. The attached phenol and quinoline moieties of each mol\u00adecule are almost coplanar with a dihedral angle of 6.05\u2005(15)\u00b0 for mol\u00adecule A and 1.89\u2005(13)\u00b0 for mol\u00adecule B. The crystal structure features N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions. Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are C\u22efH/H\u22efC (29.2%), O\u22efH/H\u22efO (28.6%) and H\u22efH (28.5%).In the title compound, C This compound was prepared in a two-step reaction, A and B). The C6A\u2014C7A and C6B\u2014C7B bond lengths of 1.472\u2005(5) and 1.470\u2005(5)\u2005\u00c5, respectively, are notably shorter than the normal C\u2014C single bond due to conjugation but are comparable to those observed in related structures ortho-position of each independent mol\u00adecule in (I)S(6) ring motifs , with a dihedral angle between their planes of 4.0\u2005(2)\u00b0 for mol\u00adecule A and 1.49\u2005(17)\u00b0 for mol\u00adecule B.The hydroxyl group in the fs Fig.\u00a01, which sA and 1.89\u2005(13)\u00b0 for mol\u00adecule B , indicating a significant electron delocalization within the mol\u00adecules. The sulfonamide groups are twisted away from the attached quinoline fragment with an C11A\u2014C12A\u2014S1A\u2014N2A torsion angle of 91.8\u2005(4)\u00b0 for mol\u00adecule A and C11B\u2014C12B\u2014S1B\u2014N2B torsion angle of \u2212 79.9\u2005(3)\u00b0 for mol\u00adecule B. The sulfonamide atoms S1A and S1B deviate by 0.228\u2005(1) and 0.054\u2005(1)\u2005\u00c5 from the planes of the quinoline fragment in mol\u00adecules A and B respectively.The attached quinoline and phenol moieties are almost coplanar with a dihedral angle of 6.05\u2005(15)\u00b0 for mol\u00adecule  B Fig.\u00a02b, indica). The packing diagram of the title compound viewed down the a axis  shows that the layers are stacked perpendicular to the b axis at  and . These layers are formed by aggregation of c). In addition, the hydroxyl group of each mol\u00adecule is involved in a C\u2014H\u22efO hydrogen bond, forming an inversion dimer with an d). Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are also observed in the crystal packing, forming a chain along the a-axis direction .In the crystal of (I)is Fig.\u00a03b shows fs Fig.\u00a03c. In adup Fig.\u00a03d. Weak on Fig.\u00a03e.Cg2\u22efCg3 = 3.779\u2005(2)\u2005\u00c5  for A mol\u00adecules and Cg6\u22efCg7 = 3.6636\u2005(18)\u2005\u00c5  for B mol\u00adecules where Cg2, Cg3, Cg6 and Cg7 are the centroids of the C1A\u2013C6A, C10A\u2013C15A, C1B\u2013C6B and C10B\u2013C15B rings, respectively]. These result in the formation of a supra\u00admolecular ribbon parallel to the a axis based on the stacked mol\u00adecules .Cohesion of the crystal structure is enhanced by the presence of \u03c0\u2013\u03c0 stacking inter\u00adactions, the most significant being between the 2-hy\u00addroxy\u00adphenyl and benzene rings of the quinoline groups of each mol\u00adecule .Crystal data, details of data collection, and results of structure refinement are summarized in Table\u00a0310.1107/S2056989022002870/zn2017sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022002870/zn2017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022002870/zn2017Isup3.cmlSupporting information file. DOI: 2158517CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Apart from a slight site occupancy difference for the water mol\u00adecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetra\u00adhedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octa\u00adhedral anions of fluorinated early transition metals.The syntheses and crystal structures of two bimetallic mol\u00adecular compounds, namely, bis\u00ad\u00adcopper(I) hexa\u00adfluorido\u00adzirconate(IV) 1.134-hydrate, [Cu(dmbpy) 2]2[ZrF6]\u00b71.134H2O , (I), and bis[bis\u00ad\u00adcopper(I)] hexa\u00adfluorido\u00adhafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]\u00b70.671H2O, (II), are reported. Apart from a slight site occupany difference for the water mol\u00adecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetra\u00adhedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octa\u00adhedral anions of fluorinated early transition metals. The tetra\u00adhedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic inter\u00adactions between cations and anions and \u03c0\u2013\u03c0 stacking inter\u00adactions between heterochiral \u0394- and \u039b-[Cu(dmbpy)2]+ complexes. A comparison between the title compounds and other [Cu(dmbpy)2]+ compounds with monovalent and bivalent anions reveals a significant influence of the cation-to-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetra\u00adhedral copper compounds.The syntheses and crystal structures of two bimetallic mol\u00adecular compounds, namely, bis[bis\u00ad\u00adcopper(I)] hexa\u00adfluorido\u00adzir\u00adcon\u00adate(IV) 1.134-hydrate, [Cu(dmbpy) The octa\u00adhedral coordination environment of Zr1 is slightly distorted, with Zr1\u2014F bond lengths ranging from 1.9955\u2005(13) to 2.0183\u2005(12)\u2005\u00c5  Fig.\u00a01. The strd Table\u00a01. To qu\u00ada\u00c5 Table\u00a01. The min2 Table\u00a02].2]2[HfF6]\u00b70.671H2O and crystallizes in the triclinic space group P2]+ cations also have C2 symmetry, with the angle between the least squares planes containing Cu1 and each ligand being 84.14\u2005(8)\u00b0 \u00b0 between the N1/C1\u2013C5 and N2/C6\u2013C10 rings and 7.97\u2005(8)\u00b0 between the N3/C13\u2013C17 and N4/C18\u2013C22 rings. Moreover, the octa\u00adhedral coordination environment of Hf1 is also slightly distorted, with Hf1\u2014F bond lengths ranging from 1.9945\u2005(10) to 2.0111\u2005(11)\u2005\u00c5. Like in compound (I)trans position of HfF62\u2212 anions, but the geometry of the hydrogen bond is slightly different from that in compound (I)B\u22efF2 (Table\u00a04Compound (II) Fig.\u00a02. Compoun\u00b0 Table\u00a03 and the 2 Table\u00a04].2]+ cations and octa\u00adhedral MF62\u2212 anions are closely packed via Coulombic inter\u00adactions  of 3.6967\u2005(12) and 3.7016\u2005(8)\u2005\u00c5, for compounds (I)2]+ pairs pack into racemic chains along the c-axis direction with heterochiral parallel displaced \u03c0\u2013\u03c0 inter\u00adactions between the N3/C13\u2013C17 and N4/C18\u2013C22 rings with an inter\u00adplanar angle of 0\u00b0, inter\u00adplanar distances of 3.708 and 3.678\u2005\u00c5, and centroid\u2013centroid distances (dpy\u2013py) of 5.3726\u2005(13) and 5.3777\u2005(11)\u2005\u00c5, for compounds (I)MF62\u2212 anions with hydrogen-bonded water mol\u00adecules are inter\u00adlaced between the racemic chains to form the extended three-dimensional structure. Compared to other mol\u00adecular compounds with MF62\u2212 anions in an extended and complicated hydrogen network In the extended structures of compounds (I)ns Fig.\u00a03. The \u0394/\u039bet al., 20162]+ complexes: [Cu(dmbpy)2][BF\u00ad4]  et al., 2015A survey of compounds related to compounds (I)MF62\u2212, the compounds reported in the CSD are charge-balanced by monovalent anions and display two different types of packing architectures distinct from those of the title compounds: [Cu(dmbpy)2][BF\u00ad4], [Cu(dmbpy)2][PF\u00ad6], and [Cu(dmbpy)2][ClO\u00ad4] are isostructural, crystallizing in space group 1/cP2. Compared to compounds (I)Unlike compound (I)2][C16H9O8]\u00b7H2O, which crystallizes in space group P2]+ cations, \u03c0\u2013\u03c0 inter\u00adactions in the compound [Cu(dmbpy)2][C16H9O8]\u00b7H2O are dominant between [Cu(dmbpy)2]+ cations and [C16H9O8]\u2212 anions instead of between [Cu(dmbpy)2]+ cations. In this compound, the [Cu(dmbpy)2]+ cations and [C16H9O8]\u2212 anions are packed into charge-neutral chains via Coulombic inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions along c axis and inversion centers are present between the chains. Additionally, the [C16H9O8]\u2212 anions and free water mol\u00adecules generate a three-dimensional network via O\u2014H\u22efO hydrogen bonding inter\u00adactions, resulting in a different architecture.Another type of packing architecture is found in [Cu(dmbpy)et al., 1993\u22121 to 423\u2005K and held at 423\u2005K for 24\u2005h. The autoclaves were allowed to cool to room temperature at a rate of 6\u2005K\u2005h\u22121. Orangish red solid products were recovered by vacuum filtration with a moderate yield. Compound (I)2, 0.835\u2005mmol of 6,6\u2032-dimethyl-2,2\u2032-bipyridyl, 0.15\u2005ml (4.14\u2005mmol) of HF (aq) (48%), and 0.1\u2005ml (5.5\u2005mmol) of deionized H2O. Compound (II)2, 0.835\u2005mmol of 6,6\u2032-dimethyl-2,2\u2032-bipyridyl, 0.05\u2005ml (1.38\u2005mmol) of HF (aq) (48%), and 0.2\u2005ml (11\u2005mmol) of deionized H2O.The compounds reported here were synthesized by the hydro\u00adthermal pouch method (Harrison Uiso(H) = 1.2Ueq(C) within OLEX2  I, II. DOI: 10.1107/S2056989021007295/hb7977Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989021007295/hb7977IIsup3.hklStructure factors: contains datablock(s) II. DOI: 2096336, 2096335CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both the organic cation and the quasi-regular octa\u00adhedral inorganic anion are located about inversion centres. The organic cations and [SnCl6]2\u2212 anions lie in layers parallel to the ac plane with p-anisaldehyde mol\u00adecules occupying the space between the layers. A network of classical N\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds exists between the ethyl\u00adenedi\u00adammonium cations and the [SnCl6]2\u2212 anions and p-anisaldehyde mol\u00adecules. These inter\u00adactions, together with non-classical C\u2014H\u22efO inter\u00adactions between the ethyl\u00adenedi\u00adammonium cations and the p-anisaldehyde mol\u00adecules, serve to hold the structure together. The crystal studied was refined as a two-component twin.The asymmetric unit of the title organic\u2013inorganic hybrid complex , (C The Sn\u2014Cl2 bond involved in hydrogen bonding is slightly longer, at 2.4322\u2005(11)\u2005\u00c5, than the other Sn\u2014Cl bonds [Sn\u2014Cl1 = 2.4100\u2005(12)\u00c5 and Sn\u2014Cl3 = 2.4220\u2005(11)\u2005\u00c5]. These results are comparable to those reported by other research groups  dianion, [SnClde Fig.\u00a01. The envac plane in which each [SnCl6]2\u2212 dianion is surrounded by four ethyl\u00adenedi\u00adammonium cations \u2005\u00c5 for N1\u22efO2iii to 3.404\u2005(4)\u2005\u00c5 for N1\u22efCl3v. Non-classical inter\u00adactions between the p-anisaldehyde mol\u00adecules and the ethyl\u00adenedi\u00adammonium cations, C9\u2014H9\u22efO2vi at 2.62\u2005\u00c5, further serve to hold the structure together.The packed crystal structure contains sheets lying parallel to the ns Fig.\u00a02. The p-ats Fig.\u00a03. The cryts Fig.\u00a03. The NH36H22N4)[SnCl6]Cl2\u00b72H2O and (C8H24N4)[SnCl6]Cl2\u00b72H2O [SnCl6] 2[SnCl6], and (C7H10N)2[SnCl6] 3SnBr6\u00b7Br ] were purchased from Sigma-Aldrich and were used without any further purification. The solvent use for the synthesis was ethanol (96%).Chemicals \u00b72C8H8O2 crystallizes in the space group P21/n with the monoclinic angle, \u03b2, close to 90\u00b0. The crystals formed as non-merohedral twins with about one quarter of reflections overlapping. The twin law corresponds to rotation about c*. For the crystal investigated, the relative domain sizes amounted to 0.790\u2005(4): 0.210\u2005(4). The structure was solved by intrinsic phasing  = 1.2Uiso(C) or 1.5Uiso(C-meth\u00adyl)]. H atoms attached to N were located as local maxima in a difference-Fourier map and refined with a distance restraint N\u2014H = 0.9\u2005\u00c5 and an isotropic displacement parameter Uiso(H) = 1.2Uiso(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902100579X/cq2042sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902100579X/cq2042Isup2.hklStructure factors: contains datablock(s) I. DOI: 2063269CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "ARs) make them an attractive target for selective and persistent modulation of neuronal excitability. However, the availability of selective modulators targeting \u03b4-GABAARs remains limited. AA29504 -phenyl]-carbamic acid ethyl ester), an analog of K+ channel opener\u00a0retigabine, acts as an agonist and a positive allosteric modulator (Ago-PAM) of \u03b4-GABAARs. Based on electrophysiological studies using recombinant receptors, AA29504 was found to be a more potent and effective agonist in \u03b4-GABAARs than in \u03b32-GABAARs. In comparison, AA29504 positively modulated the activity of recombinant \u03b4-GABAARs more effectively than \u03b32-GABAARs, with no significant differences in potency. The impact of AA29504's efficacy- and potency-associated GABAAR subtype selectivity on radioligand binding properties remain unexplored. Using [3H]4'-ethynyl-4-n-propylbicycloorthobenzoate ([3H]EBOB) binding assay, we found no difference in the modulatory potency of AA29504 on GABA- and THIP -induced responses between native forebrain GABAARs of wild type and \u03b4 knock-out mice. In recombinant receptors expressed in HEK293 cells, AA29504 showed higher efficacy on \u03b4- than \u03b32-GABAARs in the GABA-independent displacement of [3H]EBOB binding. Interestingly, AA29504 showed a concentration-dependent stimulation of [3H]muscimol binding to \u03b32-GABAARs, which was absent in \u03b4-GABAARs. This was explained by AA29504 shifting the low-affinity \u03b32-GABAAR towards a higher affinity desensitized state, thereby rising new sites capable of binding GABAAR agonists with low nanomolar affinity. Hence, the potential of AA29504 to act as a desensitization-modifying allosteric modulator of \u03b32-GABAARs deserves further investigation for its promising influence on shaping efficacy, duration and plasticity of GABAAR synaptic responses.The unique pharmacological properties of \u03b4-containing \u03b3-aminobutyric acid type A receptors (\u03b4-GABA AR), members of the Cys-loop ligand-gated ion channels superfamily, are the major sites for fast-acting synaptic inhibition in the mammalian brain pyridin-3-yl]benzamide), a selective positive allosteric modulator of \u03b14/6\u03b2\u03b4 receptors, is a widely used pharmacological tool to probe \u03b4-GABAesponses , 22. It lability . AA29504,2-apyridtrations \u201327. In rtrations , 25, 28.subtypes \u201327. AA29le cells , 25. In  potency , 27. How potency . Earlierce versa . Hence, ARs. The selectivity of AA29504 to \u03b4-GABAARs was confirmed using wild-type (WT) and \u03b4 subunit knockout (\u03b4KO) C57BL/6\u00a0J mice forebrains, as well as recombinant receptors expressed in human embryonic kidney 293 (HEK293) cell line. Radioligands employed , a non-competitive blocker of GABA-gated chloride channel [3H]GABA, and [3H]muscimol, a universal GABAAR agonist with exceptionally high affinity to \u03b4-GABAARs Muscimol (22\u00a0Ci/mmol) and [3H]EBOB (48\u00a0Ci/mmol) were purchased from PerkinElmer Life and Analytical Sciences . [3H]GABA (30\u00a0Ci/mmol) was purchased from Moravek Biochemicals . Unlabeled GABA and picrotoxin were from Sigma Chemicals Co. . AA29504 and THIP were from Tocris Biosciences .muscimol (2\u00a0nM) and [3H]GABA (5\u00a0nM) were measured in assay buffer  at room temperature (22 \u00baC) in a total volume of 300\u00a0\u00b5l. Individually pooled triplicate membrane samples  were incubated with shaking for 15\u00a0min. The effect of AA29504 on binding was determined in the presence of various concentrations of AA29504. Non-specific binding was determined in the presence of 100\u00a0\u00b5M GABA. The incubation was terminated by filtration of the samples with a Brandel Cell Harvester  onto Whatman GF/B filters .The binding of [3H]muscimol (2\u00a0nM) binding to the membrane homogenates were as follows: WT , \u03b4KO , \u03b11\u03b22\u03b32 , \u03b16\u03b22\u03b32  and \u03b16\u03b22\u03b4 . For [3H]GABA (5\u00a0nM) the binding values were: WT  and \u03b4KO .The samples were rinsed twice with 4\u20135\u00a0ml of ice-cold assay buffer. Filtration and rinsing steps took a total time of 15\u00a0s. The filters were air-dried and immersed in 3\u00a0ml of Optiphase HiSafe 3 scintillation fluid  and vortexed. The radioactivity was determined in a Wallac model 1410 liquid scintillation spectrometer . The average specific counts per minute (CPM) and % specific [3H]muscimol binding was measured essentially as described by Benkherouf et al. [3H]muscimol was performed essentially as described by Uusi-Oukari and Korpi [3H]muscimol (1\u201350\u00a0nM) at room temperature (22 \u00baC) for 60\u00a0min in the absence and presence of 10\u00a0\u00b5M AA29504. Non-specific binding was determined in the presence of 100\u00a0\u00b5M GABA. The incubation was terminated by filtration and the radioactivity of the air-dried filters was measured using a scintillation spectrometer as described above.The effect of AA29504 on the association and dissociation of [f et al. . Saturatnd Korpi . Triplic3H]EBOB binding was measured in [3H]EBOB assay buffer  at room temperature (22 \u00baC) in a total volume of 400\u00a0\u00b5l in the absence and presence of various concentrations of GABA or THIP with and without 10\u00a0\u00b5M AA29504. Triplicate samples were incubated with shaking for 2\u00a0h. Non-specific binding was determined in the presence of 100\u00a0\u00b5M picrotoxin. The incubations were terminated as described above for [3H]muscimol binding. The average CPM and % specific [3H]EBOB (1\u00a0nM) binding to the membrane homogenates were as follows:WT , \u03b4KO , \u03b16\u03b23\u03b32 , \u03b16\u03b23\u03b4 , \u03b16\u03b23: .The displacement of 1\u00a0nM EBOB displacement from 0.20\u2009\u00b1\u20090.11\u00a0mM to 15.8\u2009\u00b1\u20096.5\u00a0\u00b5M in WT mice (p\u2009<\u20090.01) and from 0.22\u2009\u00b1\u20090.05\u00a0mM to 12.1\u2009\u00b1\u20091.5\u00a0\u00b5M in \u03b4KO mice . There were no significant differences between WT and \u03b4KO mouse binding values in the effects of GABA or THIP on forebrain GABAARs in the absence or presence of AA29504 .[3H]EBOB binding to recombinant GABAARs expressed in HEK293 cells as an indicator for allosteric agonist activity. The receptor subunit combinations \u03b16\u03b23\u03b32, \u03b16\u03b23\u03b4, and \u03b16\u03b23 were selected to further examine the influence of \u03b3 and \u03b4 subunits on [3H]EBOB binding displacement by AA29504. The results indicate that AA29504 was able to displace [3H]EBOB binding to all three receptor subtypes in a concentration-dependent manner .We assessed the potential of AA29504 to directly displace HEBOB binARs expressed in WT and \u03b4KO mice. The binding of [3H]muscimol and [3H]GABA was measured at room temperature (22\u00a0\u00b0C) with increasing concentrations of AA29504, where individually pooled forebrain membrane samples were incubated for 15\u00a0min. Figure\u00a03H]muscimol and [3H]GABA binding to both WT and \u03b4KO mice forebrains. Two-way ANOVA followed by Tukey's post hoc analysis indicated that AA29504 was more potent in stimulating [3H]muscimol (p\u2009<\u20090.01) and [3H]GABA (p\u2009<\u20090.001) binding in \u03b4KO than in WT mice.We further examined the modulatory effects of AA29504 on the high-affinity agonist binding to native GABAARs expressed in WT and \u03b4KO mice forebrains, we compared the role of \u03b3 and \u03b4 subunits on\u00a0AA29504 modulation of [3H]muscimol binding in recombinant \u03b11\u03b22\u03b32, \u03b16\u03b22\u03b32, and \u03b16\u03b22\u03b4 receptors expressed in HEK293 cells. As illustrated in Fig.\u00a03H]muscimol binding to \u03b11\u03b22\u03b32 and \u03b16\u03b22\u03b32 receptor subtypes in a concentration-dependent manner (p\u2009<\u20090.05). In contrast, it had no significant effect on the binding to \u03b16\u03b22\u03b4 receptor subtype (Two-way ANOVA followed by Tukey\u2019s post hoc test).Under the same conditions performed for native GABA3H]muscimol binding is due to\u00a0alterations in receptor-ligand binding kinetics as we assessed the influence of AA29504 on [3H]muscimol association and dissociation rates in WT and \u03b4KO forebrain membranes. The results indicate that [3H]muscimol association at 22\u00a0\u00b0C was faster in \u03b4KO compared to WT in the absence of AA29504, where the calculated association rate constants Kon were 5.9\u2009\u00b1\u20090.6\u2009\u00d7\u2009108\u00a0M\u22121\u2009\u00d7\u2009min\u22121 and 2.2\u2009\u00b1\u20090.3\u2009\u00d7\u2009108\u00a0M\u22121\u2009\u00d7\u2009min\u22121, respectively  . Co-incubation with AA29504 did not significantly affect [3H]muscimol Kon in either \u03b4KO (4.8\u2009\u00b1\u20090.9\u2009\u00d7\u2009108\u00a0M\u22121\u2009\u00d7\u2009min\u22121) or WT mice (3.9\u2009\u00b1\u20091.1\u2009\u00d7\u2009108\u00a0M\u22121\u2009\u00d7\u2009min\u22121) , but it notably increased the amount of specific radioligand binding in both mouse lines (p\u2009<\u20090.001). The increased binding was maximally 240\u2009\u00b1\u200923% of control binding without AA29504 in \u03b4KO mice, significantly higher than that in WT mice (166\u2009\u00b1\u20095% of control)   than in WT (0.38\u2009\u00b1\u20090.02\u00a0min\u22121) , reflecting a faster radioligand dissociation in the former mouse line . However, no evident effects were observed with AA29504 on [3H]muscimol.Similar to the association, the dissociation rate constant Koff in \u03b4KO (0.64\u2009\u00b1\u20090.05\u00a0min\u22121) and WT forebrains (0.43\u2009\u00b1\u20090.02\u00a0min\u22121)   , in the absence (control) or presence of AA29504, all tested groups except control WT membranes were best fit to the one-site binding model. Binding to control WT membranes was best fit to the two-site binding model , displaying two binding affinities at distinguishable receptor densities (Table (1)\u2009+\u2009Bmax(2)) in WT membranes, however, was equivalent to control \u03b4KO Bmax (no AA29504). The presence of 10\u00a0\u00b5M AA29504 in WT membranes rendered [3H]muscimol binding more favorable to one-site model as it displayed a single apparent affinity that was intermediate between the affinities obtained in control WT membranes. On the other hand, AA29504 significantly decreased the equilibrium dissociation constant (KD) reflecting an enhancement of [3H]muscimol binding affinity in \u03b4KOs (p\u2009<\u20090.001). Moreover, AA29504 increased [3H]muscimol Bmax in \u03b4KO (p\u2009<\u20090.05) as well as WT mouse lines (p\u2009<\u20090.01) (Two-way ANOVA followed by Tukey's post hoc test). The calculated [3H]muscimol Bmax and KD values are summarized in Table As a probable mechanism for AA29504-induced stimulation of EBOB binding to recombinant GABAARs in this study, and similar to the earlier findings with electrophysiological measurements [3H]EBOB directly (in the absence of GABA) in the former subtype  and dissociation (Koff) rate constants in either mouse line. Hence, the link between AA29504-induced stimulation of [3H]muscimol binding and alterations in receptor-ligand binding kinetics was not established.Modulating GABAed state , 65. Thu-GABAARs , 67 and -GABAARs . DespiteARs muscimol saturation analysis revealed AA29504-induced GABAAR shift to the high-affinity states. In WT mice, [3H]muscimol displayed two high-affinity receptor populations in the absence of AA29504: low-nanomolar (KD\u2009=\u20094.1\u2009\u00b1\u20093.6\u00a0nM) for \u03b4-GABAARs as earlier reported muscimol [AR population was suggested to rise from desensitized \u03b32-GABAARs\u00a0[3H]muscimol binding, especially in the\u00a0forebrain region muscimol binding  EBOB radioligand as a\u00a0unique probe for assessing drug enhancement of GABAAR function, we demonstrated for the first time the non-differential AA29504 modulatory potency on native GABAARs expressed in WT and \u03b4KO C57BL/6J mice. We further displayed AA29504\u2019s GABA-independent activity on recombinant GABAARs expressed in HEK293 cells, indicating higher selective agonist efficacy on \u03b4-GABAARs in relation to \u03b32-GABAARs. Interestingly, AA29504 showed a concentration-dependent stimulation of GABAA agonist binding to \u03b32 GABAARs but\u00a0not to \u03b4-GABAARs. This newly revealed selective modulation by AA29504 is attributed to its ability to shift the low-affinity \u03b32-GABAARs towards a higher affinity desensitized state, thereby rising new sites capable of binding GABAAR agonists with low nanomolar affinity. Hence, the potential of AA29504 to act as a desensitization-modifying allosteric modulator (DAM) of \u03b32-GABAARs deserves further investigation for its promising influence on shaping efficacy, duration and plasticity of GABAAR synaptic responses [This study sheds light on AA29504's modulatory activity, its direct actions and interactions with agonists in GABAesponses , 84, 85."}
{"text": "The mol\u00adecular and crystal structures were studied and a Hirshfeld surface analysis undertaken for the title benzo\u00adthia\u00adzine derivative, which has potential non-steroidal anti-inflammatory activity. 22H22ClN3O4S, which has potential non-steroidal anti-inflammatory activity, the benzo\u00adthia\u00adzine and cyclo\u00adhexenone rings both adopt a distorted sofa conformation while the 4H-pyrane ring adopts a very flattened sofa conformation. The two bicyclic fragments are skewed to each other, with the dihedral angle between their least-squares planes being 72.8\u2005(1)\u00b0. In the crystal, the mol\u00adecules form a hydrogen-bonded chain parallel to the a axis due to N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds. Neighbouring chains are linked by C\u2014H\u22efN, C\u2014H\u22efO and \u03c0\u2013\u03c0 stacking inter\u00adactions. Hirshfeld surface analysis was used to investigate the importance of the different types of inter\u00admolecular inter\u00adactions whose contributions are: H\u22efH = 44.7%, O\u22efH/H\u22efO = 21.8%, N\u22efH/H\u22efN = 11.9%, C\u22efH/H\u22efC = 9.5%, Cl\u22efH/H\u22efCl = 7.2%. Parts of the mol\u00adecule, viz. the phenyl ring and the ethyl side chain, are equally disordered over two sets of sites.In the title compound, C H-benzo[c]thia\u00adzine 2,2-dioxide moiety and its derivatives have been the focus of chemists and pharmacologists for decades  of the \u2018oxicame\u2019 group , \u0398 = 52.5\u2005(1)\u00b0, \u03a8 = 20.3\u2005(1)\u00b0. The S1 and C8 atoms deviate from the least-squares plane of the remaining atoms of the ring by 0.863\u2005(6) and 0.244\u2005(2)\u2005\u00c5 respectively. The phenyl ring of the benzo\u00adthia\u00adzine fragment is disordered over two positions (A and B) with equal occupancy. The partially saturated carbocycle has the same conformation as the hydro\u00adthia\u00adzine ring, with puckering parameters of S = 0.67\u2005(1), \u0398 = 41.9\u2005(1)\u00b0, \u03a8 = 11.8\u2005(1)\u00b0. The deviations of the C13 and C14 atoms from the least-squares plane of the remaining atoms in the ring are 0.717\u2005(2) and 0.132\u2005(2)\u2005\u00c5, respectively. The 4H-pyran ring adopts a very flattened sofa conformation with puckering parameters of S = 0.11\u2005(1), \u0398 = 59.3\u2005(1)\u00b0, \u03a8 = 3.2\u2005(1)\u00b0, where the C9 atom deviates by 0.118\u2005(2)\u2005\u00c5 from the plane of the remaining atoms in this ring. The C8\u2014C9 bond is elongated to 1.525\u2005(3)\u2005\u00c5 [the mean value \u00b0]. The presence of the vicinal substituents on the 4H-pyran moiety results in an elongation of the C16\u2014C17 bond to 1.347\u2005(3)\u2005\u00c5 .The di\u00adhydro\u00adthia\u00adzine ring of compound on Fig.\u00a02 with puc4 form hydrogen-bonded chains parallel to the a axis  1\u00a0+\u00a0x, y, z; Table\u00a01In the crystal, mol\u00adecules of is Fig.\u00a03 due to NH-pyran rings of mol\u00adecules belonging to neighbouring layers are found [the distance between ring planes is 3.38\u2005(1)\u2005\u00c5 and the plane shift is 1.247\u2005(1)\u2005\u00c5]. Mol\u00adecules are arranged in a head-to-tail manner in both types of stacking dimers. Additional C\u2014H\u22efN and C\u2014H\u22efO hydrogen-bonding inter\u00adactions of a weak nature  is provided by O\u22efH/H\u22efO inter\u00adactions , while the highest contribution is from H\u22efH contacts (44.7%). The contributions of N\u22efH/H\u22efN (11.9%), C\u22efH/H\u22efC (9.5%) and Cl\u22efH/H\u22efCl (7.2%)  inter\u00adactions are similar, but the presence of sharp spikes on the fingerprint plot containing only N\u22efH/H\u22efN or Cl\u22efH/H\u22efCl inter\u00adactions suggests that the latter contacts are much stronger.All of the hydrogen bonds and short contacts of the title compound are evident on the two-dimensional fingerprint plot presented in Fig.\u00a05ns Fig.\u00a05c, whileet al., 2016et al., 2014aet al., 2016et al., 2018et al., 2014bet al., 2017et al., 2018A search of the Cambridge Structural Database  , malono\u00adnitrile (2)  and 5,5-di\u00admethyl\u00adcyclo\u00adhexane-1,3-dione (3)  was dissolved in 20\u2005ml of i-PrOH and then tri\u00adethyl\u00adamine (0.1\u2005mol%) was added ; colourless crystals; m.p. > 523\u2005K.A mixture of 4-chloro-1-ethyl-1ed Fig.\u00a01. The mixsp3\u2014Csp3 = 1.54\u2005\u00c5 for the ethyl side chain C21\u2014C22; Csp2\u2014Csp2 = 1.38\u2005\u00c5 for the phenyl ring C1\u2013C6), and with an equal occupancy for the two sets of sites. All hydrogen atoms were located in difference-Fourier maps. They were included in calculated positions and treated as riding with C\u2014H = 0.96\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for methyl groups and with Car\u2014H = 0.93\u2005\u00c5, Csp3\u2014H = 0.97\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for all other hydrogen atoms. The hydrogen atoms of the amino group were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021002085/wm5596sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002085/wm5596Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021002085/wm5596Isup3.cmlSupporting information file. DOI: 2064493CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Transforming growth factor beta (TGF\u2010\u03b2) plays an important role in the viral liver disease progression via controlling viral propagation and mediating inflammation\u2010associated responses. However, the antiviral activities and mechanisms of TGF\u2010\u03b2 isoforms, including TGF\u2010\u03b21, TGF\u2010\u03b22 and TGF\u2010\u03b23, remain unclear. Here, we demonstrated that all of the three TGF\u2010\u03b2 isoforms were increased in Huh7.5 cells infected by hepatitis C virus (HCV), but in turn, the elevated TGF\u2010\u03b2 isoforms could inhibit HCV propagation with different potency in infectious HCV cell culture system. TGF\u2010\u03b2 isoforms suppressed HCV propagation through interrupting several different stages in the whole HCV life cycle, including virus entry and intracellular replication, in TGF\u2010\u03b2/SMAD signalling pathway\u2013dependent and TGF\u2010\u03b2/SMAD signalling pathway\u2013independent manners. TGF\u2010\u03b2 isoforms showed additional anti\u2010HCV activities when combined with each other. However, the elevated TGF\u2010\u03b21 and TGF\u2010\u03b22, not TGF\u2010\u03b23, could also induce liver fibrosis with a high expression of type I collagen alpha\u20101 and \u03b1\u2010smooth muscle actin in LX\u20102 cells. Our results showed a new insight into TGF\u2010\u03b2 isoforms in the HCV\u2010related liver disease progression. The expressions of TGF\u2010\u03b2 isoforms are promoted by HCV infection in cultured hepatocytes and in livers of HCV\u2010infected patients, which might be caused by HCV\u2010induced endoplasmic reticulum stress, unfolded protein response activation or HCV core expression.22.1The human hepatoma cell line Huh7.5 cells and the plasmid pFL\u2010J6/JFH/JC1 (HCV\u20102a) containing the full\u2010length chimeric HCV complementary DNA (cDNA) were kindly provided by Vertex Pharmaceuticals Inc.2.2TGF\u2010\u03b21 (100\u201021\u201010\u00a0\u03bcg), TGF\u2010\u03b22 (100\u201035B\u201010\u00a0\u03bcg) and TGF\u2010\u03b23 (100\u201036E\u201010\u00a0\u03bcg) proteins were purchased from PeProtech Inc (Peprotech). All TGF\u2010\u03b2 isoforms were dissolved according to the manufacturer's protocol and the cell viability after TGF\u2010\u03b2 isoforms treatment was determined by a methyl thiazolyl tetrazolium  assay.2.3The plasmids pcDNA3.1(+)\u2010TGF\u2010\u03b21 expressing TGF\u2010\u03b21, pcDNA3.1(+)\u2010TGF\u2010\u03b23 expressing TGF\u2010\u03b23, pcDNA3.1(+)\u2010TGF\u2010\u03b21\u2010His expressing TGF\u2010\u03b21 with His tag at the C\u2010terminal, pcDNA3.1(+)\u2010TGF\u2010\u03b23\u2010His expressing TGF\u2010\u03b23 with His tag at the C\u2010terminal and the part truncated mutant plasmids of pcDNA3.1(+)\u2010TGF\u2010\u03b21\u2010His or pcDNA3.1(+)\u2010TGF\u2010\u03b23\u2010His were generated by amplification of cDNA from Huh7.5 cell using primers shown in Table\u00a02.4\u2212\u0394\u0394CT method. Glyceraldehyde 3\u2010phosphate dehydrogenase (GAPDH) was served as the internal control for the quantification. The primer and probe sequences used for quantitative real\u2010time reverse transcriptase polymerase chain reaction (qRT\u2010PCR) are provided in Table\u00a0The cellular RNAs harvested by RNeasy Mini Kit (QIAGEN) from Huh7.5 cells were detected using the AgPath\u2010ID One\u2010Step RT\u2010PCR Kit (Applied Biosystems). Fluorescent signals were identified with 7500 fast real\u2010time PCR system (Applied Biosystems) according to the procedure recommended by the manufacturer. HCV RNA level was calculated according with the 2TGFB1, TGFB2, TGFB3, type I collagen alpha 1 (COL1A1) or alpha\u2010smooth muscle actin (\u03b1\u2010SMA) were quantified using GoTaq qPCR Master Mix according to the procedure. The primers are shown in Table\u00a0For mRNA quantitation by SYBR Green method, total RNAs were reverse\u2010transcribed with PrimeScript RT Master Mix , and the mRNAs of 2.5Huh7.5 cells were treated with HCV viral stock at different multiplicity of infection  for 72\u00a0hours or at MOI\u00a0=\u00a00.2 for 0, 3\u00a0days or 6\u00a0days, and then, intracellular mRNAs or proteins were extracted and quantified by qRT\u2010PCR or Western blot (WB) analysis.2.6Huh7.5 cells were inoculated with HCV viral stock (MOI\u00a0=\u00a00.5) and simultaneously treated with TGF\u2010\u03b2 isoforms or sofosbuvir. At 72\u00a0hours, intracellular proteins were harvested by the CytoBuster Protein Extraction Reagent  containing 1\u00a0mmol/L protease inhibitor cocktail (Roche Applied Science) and HCV core protein level in cells was determined by WB analysis.\u22121 to 10\u22128 and simultaneously treated with 0.5\u00a0nmol/L of TGF\u2010\u03b21, TGF\u2010\u03b22 and TGF\u2010\u03b23. At 72\u00a0hours post\u2010infection, HCV\u2010positive wells were examined using a microscope after immunostaining against HCV core protein.For measuring HCV infectivity, Huh7.5 cells were incubated with HCV viral stock at 10\u2010fold dilutions ranged from 10de novo HCV particle production, Huh7.5 cells were inoculated with HCV viral stock (MOI\u00a0=\u00a00.7) and 0.5\u00a0nmol/L of TGF\u2010\u03b21, TGF\u2010\u03b22 or TGF\u2010\u03b23 for 24\u00a0hours. The newly released infectious virus particles were collected at 48\u00a0hours and then quantified by 50% tissue culture infective dose (TCID50) assay. The infectivity titre was shown as TCID50 per mL.To identify the effects of TGF\u2010\u03b2 isoforms on GS4.3 cells were treated with 0.5\u00a0nmol/L of TGF\u2010\u03b2 isoforms or sofosbuvir (0.5\u00a0\u03bcmol/L) for 72\u00a0hours. Then, intracellular proteins were extracted by PER and HCV NS3 protein level was detected by WB analysis.2.7To evaluate the antiviral effective stages of TGF\u2010\u03b2 isoforms, Huh7.5 cells were pre\u2010treated with TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) for 2\u00a0hours followed by HCV infection for 2\u00a0hours, simultaneously treated with TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) and HCV for 2\u00a0hours, or infected with HCV (MOI\u00a0=\u00a00.5) for 2\u00a0hours followed by TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) 2\u00a0hours treatment. At 72\u00a0hours, intracellular HCV core protein level was detected by WB analysis. In order to further characterize the inhibition stages, a time\u2010of\u2010addition assay was performed. In brief, Huh7.5 cells were inoculated with HCV (MOI\u00a0=\u00a00.5) at 37\u00b0C for 2, 4, 6, 8\u00a0hours or 10\u00a0hours, and then, the HCV\u2010containing medium was replaced by TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) or sofosbuvir (0.5\u00a0\u03bcmol/L) containing medium. After 2\u00a0hours of treatment, the medium was replaced by fresh medium. At 72\u00a0hours, HCV core protein level in cells was determined by WB analysis.2.8HCV viral stock (MOI\u00a0=\u00a00.5) was pre\u2010treated with 0.2\u00a0nmol/L TGF\u2010\u03b21, 0.5\u00a0nmol/L TGF\u2010\u03b22 or 0.5\u00a0nmol/L TGF\u2010\u03b23 at 37\u00b0C and used to infect cells after 25\u2010fold dilution of the inoculum. Infection with untreated HCV stock was performed in parallel in the presence of TGF\u2010\u03b2 isoforms at indicated concentrations. At 72\u00a0hours, intracellular proteins were harvested and HCV core protein level was determined by WB.2.9Huh7.5 cells were incubated with HCV viral stock (MOI\u00a0=\u00a00.5) for 16\u00a0hours, and then, the cells were treated with TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L), sofosbuvir (0.5\u00a0\u03bcmol/L) or 0.1% BSA for 48\u00a0hours. The culture medium was replaced by adding fresh culture medium. After 24\u00a0hours, the cell viability was tested using MTT assay, the culture medium was collected for incubation to na\u00efve Huh7.5 cells, and intracellular RNA was extracted and quantified by qRT\u2010PCR. Meanwhile, na\u00efve Huh7.5 cells were incubated with above culture supernatants for 72\u00a0hours. Then, the intracellular RNA of Huh7.5 cells was extracted and quantified by qRT\u2010PCR.2.10q value was calculated with the improved B\u00fcrgi formula (Jin's equation), with q\u00a0<\u00a00.85, 0.85\u00a0~\u00a01.15, and >1.15 indicating antagonism, addition and synergy, respectively.Huh7.5 cells were inoculated with HCV viral stock (MOI\u00a0=\u00a00.5) and simultaneously treated with 0.04\u00a0nmol/L TGF\u2010\u03b21, 0.05\u00a0nmol/L TGF\u2010\u03b22, 0.1\u00a0nmol/L TGF\u2010\u03b23 alone, in combination or double concentration (2\u00d7), or sofosbuvir (0.5\u00a0\u03bcmol/L). At 72\u00a0hours, intracellular proteins were extracted and determined by WB analysis. To evaluate their combined effect, the combination index (CI) showed with 2.11Huh7.5 cells were incubated with T\u03b2RI or T\u03b2RII kinase inhibitors (20\u00a0\u03bcmol/L LY2109761 or 50\u00a0\u03bcmol/L RepSox) for 6\u00a0hours, and then, TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) and HCV (MOI\u00a0=\u00a00.5) were simultaneously added. After 72\u00a0hours incubation, intracellular HCV core protein was determined by WB analysis.2.12Huh7.5 cells were transfected with TGF\u2010\u03b21, TGF\u2010\u03b21\u2010His, TGF\u2010\u03b23, TGF\u2010\u03b23\u2010His, the mutants of TGF\u2010\u03b2 plasmids or plasmid control pcDNA3.1(+) applying HD transfection reagent (Promega), or transfected with siRNA for T\u03b2RI or SMAD2/3 or negative control siRNA\u2010A applying RNAiMAX transfection reagent (Invitrogen). After 48\u00a0hours, the cells were sub\u2010cultured and part of intracellular proteins was harvested to detect His tag or corresponding protein expression with WB. After 24\u00a0hours, cells were infected with HCV (MOI\u00a0=\u00a00.5) or added TGF\u2010\u03b2 isoforms (0.5\u00a0nmol/L) and HCV (MOI\u00a0=\u00a00.5). After 48\u00a0hours, intracellular proteins were extracted to detect HCV core protein level by WB.2.13COL1A1 and \u03b1\u2010SMA mRNA was quantified with qRT\u2010PCR.LX\u20102 cells were cultured in high glucose DMEM without FBS for 12\u00a0hours. Then, the cell supernatant was replaced by fresh medium with 2% FBS containing 0.5\u00a0nmol/L TGF\u2010\u03b2 isoforms. After 24\u00a0hours, intracellular RNA was extracted and 2.14The Western blot analysis was performed as previously described.2.15t test; P\u00a0<\u00a00.05 was considered as statistically significant.The data were presented as means\u00a0\u00b1\u00a0standard deviation (SD) more than three independent experiments. Statistical analyses were performed in GraphPad Prism 7 (GraphPad) using ANOVA analysis followed by the Student\u2019s 33.1In infectious HCV cell culture (HCVcc) system, the three TGF\u2010\u03b2 isoforms at mRNA Figure\u00a0, left anDe novo HCV production, Huh7.5 cells were infected with HCV and simultaneously treated with TGF\u2010\u03b2 isoforms for 24\u00a0hours, and newly released infectious virus particles were collected at 48\u00a0hours and then quantified by TCID50 assay. De novo produced HCV yielded a viral titre of about 104.17 TCID50 per mL, whereas treatment with TGF\u2010\u03b2 isoforms significantly decreased the TCID50 of the De novo produced HCV \u2010TGF\u2010\u03b22 could not well express TGF\u2010\u03b22 in Huh7.5 cells as TGF\u2010\u03b21 and TGF\u2010\u03b23 did. Therefore, we only test the ant\u2010HCV effects caused by overexpressing TGF\u2010\u03b21 and TGF\u2010\u03b23 to investigate which regions or amino acid residues of TGF\u2010\u03b2 isoforms were responsible for their anti\u2010HCV capacities. Overexpressing TGF\u2010\u03b21 and TGF\u2010\u03b23 with His tag at C\u2010terminal had equal anti\u2010HCV effects as TGF\u2010\u03b21 and TGF\u2010\u03b23, respectively Figure\u00a0, suggestCys77 or Cys109 in TGF\u2010\u03b2 isoforms is important to form homodimer for activation of their signalling activities.The amino acid residues Arg25, Val92 and Arg94 of TGF\u2010\u03b21 and TGF\u2010\u03b23 are responsible for their high\u2010affinity interaction with T\u03b2RII, once they are exchanged with Lys25, Ile92 and Lys94, respectively, TGF\u2010\u03b2 signalling activities of TGF\u2010\u03b21 and TGF\u2010\u03b23 are reduced.The \u03b1\u2010helix 3 of TGF\u2010\u03b2 isoforms is response for their binding surface for T\u03b2RI and truncating \u03b1\u2010helix 3 of TGF\u2010\u03b22 suppresses its signalling activity.Interestingly, by blocking the TGF\u2010\u03b2 receptor kinase activity or silencing SMAD2/3, we presumed the anti\u2010HCV activities of TGF\u2010\u03b21 and TGF\u2010\u03b22 might be through TGF\u2010\u03b2/SMAD signalling pathway, while TGF\u2010\u03b23 inhibited HCV replication independent on TGF\u2010\u03b2/SMAD signalling pathway Figure\u00a0. This di3.5COL1A1 and \u03b1\u2010SMA mRNA expression ; Data curation (lead); Methodology (lead); Writing\u2010original draft ; Writing\u2010review & editing (lead). Jian\u2010Rui Li: Data curation (lead); Methodology (lead). Hu Li: Methodology (supporting); Writing\u2010review & editing (supporting). Jia\u2010Li Tan: Data curation (supporting); Methodology (supporting); Writing\u2010review & editing (supporting). Mei\u2010Xi Wang: Writing\u2010review & editing (supporting). Nan\u2010Nan Liu: Writing\u2010review & editing (supporting). Rong\u2010Mei Gao: Data curation (supporting); Methodology (supporting). Hai\u2010Yan Yan: Data curation (supporting); Methodology (supporting). Xue\u2010Kai Wang: Writing\u2010review & editing (supporting). Biao Dong: Methodology (supporting). Yu\u2010Huan Li: Methodology (supporting). Zonggen Peng: Conceptualization (lead); Data curation (lead); Formal analysis (lead); Funding acquisition (lead); Methodology (lead); Project administration (lead); Writing\u2010review & editing (lead)."}
{"text": "Two crystallographically independent mol\u00adecules are present in the asymmetric unit. O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds form rings and chains and \u03c0\u2013\u03c0 stacks further connect mol\u00adecules in the crystal. 14H11NO2, with virtually identical geometries. The carbazole units are planar. The hy\u00addroxy group at position 1, carbaldehyde group at position 2, and methyl group at position 8 (with the exception of two H atoms) are coplanar with the attached benzene rings. The dihedral angle between the two benzene rings is 2.20\u2005(9)\u00b0 in mol\u00adecule A and 2.01\u2005(9)\u00b0 in mol\u00adecule B. The pyrrole ring makes dihedral angles of 0.82\u2005(10) and 1.40\u2005(10)\u00b0 [0.84\u2005(10) and 1.18\u2005(10)\u00b0 in mol\u00adecule B] with the (\u2013CH3)-substituted and (\u2013OH and \u2013CHO) substituted benzene rings, respectively. The mol\u00adecular structure is stabilized by the intra\u00admolecular O\u2014H\u22efO hydrogen bonds, while the crystal structure features N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. A range of \u03c0\u2013\u03c0 contacts further stabilizes the crystal structure.Two crystallographically independent mol\u00adecules are present in the asymmetric unit of the title compound, C Murraya koenigii spreng (Rutaceae) is a rich source of carbazole alkaloids \u00b0 in mol\u00adecule B. The pyrrole ring makes dihedral angles of 0.82\u2005(10) and 1.40\u2005(10)\u00b0 for mol\u00adecule A and 0.84\u2005(10) and 1.18\u2005(10)\u00b0 for mol\u00adecule B with the methyl-substituted and hydroxide/carbaldehyde-substituted benzene rings, respectively. The compound exhibits intra\u00admolecular O\u2014H\u22efO hydrogen bonding between the hydroxide and aldehyde groups  ring motifs, have previously been observed  and N2\u2014H2\u22efO2 hydrogen bonds. A C14\u2014H14\u22efO3 hydrogen bond is also present. A range of \u03c0\u2013\u03c0 contacts is also observed  = 3.4604\u2005(13)\u2005\u00c5, Cg1\u22efCg3  = 3.4896\u2005(13)\u2005\u00c5 and Cg7\u22efCg9  = 3.6279\u2005(13)\u2005\u00c5, where Cg1, Cg2, Cg3, Cg7 and Cg9 are the centroids of the N1/C7/C6/C10/C9, C2\u2013C7, C8\u2013C13, N2/C21/C20/C24/C23 and C22\u2013C27 rings, respectively.In the crystal, mol\u00adecules are connected into chains parallel to the s Table\u00a01. Both cred Fig.\u00a04. The diset al., 2016H-carbazole-2-carbaldehyde gave two hits, viz. 2,2,10-trimethyl-2,3-di\u00adhydro\u00adpyranocarbazol-4(11H)-one ethanone  in dry benzene (25\u2005ml) was added slowly and the reaction mixture was allowed to stir for another 36\u2005h. The reaction was monitored by TLC. After completion of the reaction, benzene was removed in vacuo and the contents in the flask were transferred to a beaker containing water. It was neutralized with dilute HCl, filtered, washed with water and dried to get crude 1-hy\u00addroxy-8-methyl-9H-carbazole-2-carbaldehyde. It was purified by column chromatography over silica using petroleum ether:ethyl acetate (95:5) as eluant. The brown pure product obtained was recrystallized using glacial acetic acid , m.p. 414\u2005K  was washed with dry benzene and taken into a round-bottom flask containing dry benzene (100\u2005ml). The flask was kept in an ice bath under stirring. Ethyl formate (8\u2005ml) was added dropwise to the solution over a period of 10 minutes. Then 8-methyl-2,3,4,9-tetra\u00adhydro-1\u2005K Fig.\u00a05.D and H3A were located in a difference-Fourier map and freely refined. The remaining hydrogen atoms were placed in calculated positions with C\u2014H bond distances of 0.93\u2005\u00c5 (aromatic H), or 0.96\u2005\u00c5 (methyl H) and were refined with anisotropic displacement parameters 1.2 and 1.5 times that of the parent carbon atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021007210/yy2001sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021007210/yy2001Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007210/yy2001Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021007210/yy2001Isup4.cmlSupporting information file. DOI: 1540679CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We report here the following nucleotide incorporations opposite Ua by various DNA polymerases: DNA polymerase \u03b1, dATP and dGTP (dATP > dGTP); DNA polymerase \u03b4, dATP; DNA polymerase \u03b6, dATP; Kf exo\u2212, dATP; Sulfolobus solfataricus P2 DNA polymerase IV (Dpo4), dGTP and dATP (dGTP > dATP); and DNA polymerase \u03b7, dCTP, dGTP, dATP, and dTTP (dCTP > dGTP > dATP > dTTP). DNA polymerases \u03b2 and \u03b5 were blocked by Ua. Elongation by DNA polymerases \u03b4 and \u03b6 stopped after inserting dATP opposite Ua. Importantly, the elongation efficiency to full-length beyond Ua using DNA polymerase \u03b7 and Dpo4 were almost the same as that of natural DNA.Urea (Ua) is produced in DNA as the result of oxidative damage to thymine and guanine. It was previously reported that Klenow fragment (Kf) exoThe online version contains supplementary material available at 10.1186/s41021-022-00236-3. Sulfolobus solfataricus P2 DNA polymerase IV (Dpo4) have not been analyzed to date. Herein, we describe our studies of nucleotide incorporations and translesion synthesis in relation to Ua with DNA polymerases \u03b1, \u03b4, \u03b5, \u03b7, \u03b6 and Dpo4. Also, we confirmed nucleotide incorporation and extension in relation to Ua using Kf exo\u2212 and DNA polymerase \u03b2.DNA damage is a major cause of cell death, mutations, cancer, neurological disease, and aging. Urea (Ua) is produced in DNA by ionizing radiation  due to o\u2212 was purchased from Fermentas . Yeast DNA polymerase \u03b6 was purchased from Enzymax . Human DNA polymerase \u03b4 [Saccharomyces cerevisiae DNA polymerase \u03b5 [T4 polynucleotide kinase was purchased from New England Biolabs . T4 DNA ligase was purchased from Takara . Calf thymus DNA polymerase \u03b1 and human DNA polymerase \u03b2 were purchased from Chimerx . Klenow fragment exonucleasemerase \u03b4 , human Dmerase \u03b4 , and Sacmerase \u03b5  were purThe DNA template , Alexa 680-labeled 15-mer primer (5\u2032-Alexa680-TATTGATTGTGAATT-3\u2032), 6-mer oligonucleotide containing 8oxoG (5\u2032-CTT8oxoGAA-3\u2032), 13-mer oligonucleotide (5\u2032-TTCACAATCAATA-3\u2032), and 11-mer oligonucleotide (5\u2032-CTCATCAACAT-3\u2032) were constructed by Japan Bio Services Co., Ltd. .2 and KI [The 30-mer DNA template containing Ua (30-merUa)  was constructed as follows. A 6-mer oligonucleotide containing 8oxoG (5\u2032-CTT8oxoGAA-3\u2032) was oxidized to a 6-mer oligonucleotide containing oxaluric acid (Oxa) using I2 and KI , then Ox2 and KI . This 6-2, 10\u2009mM NaCl, 45\u2009mM KCl, 1\u2009mM DTT, 100\u2009\u03bcg/mL bovine serum albumin (BSA); (for DNA polymerase \u03b2) 50\u2009mM Tris-HCl (pH\u20098.8), 10\u2009mM MgCl2, 1\u2009mM DTT, 100\u2009\u03bcg/mL BSA; (for DNA polymerase \u03b4) 50\u2009mM Tris-HCl (pH\u20097.4), 2\u2009mM MgCl2, 2\u2009mM DTT, 100\u2009\u03bcg/mL BSA; (for DNA polymerase \u03b5) 50\u2009mM Tris-HCl (pH\u20097.4), 8\u2009mM MgCl2, 2\u2009mM DTT, 100\u2009\u03bcg/mL BSA; (for DNA polymerases \u03b6 and \u03b7) 50\u2009mM Tris-HCl (pH\u20098.0), 2\u2009mM MgCl2, 5\u2009mM DTT, 100\u2009\u03bcg/mL BSA; (for Kf exo\u2212) 50\u2009mM Tris-HCl (pH\u20098.0), 5\u2009mM MgCl2, 1\u2009mM DTT, 100\u2009\u03bcg/mL BSA; (for Dpo4) 20\u2009mM HEPES (pH\u20096.5), 10\u2009mM MgCl2, 1\u2009mM MnCl2 100\u2009mM NaCl, 100\u2009\u03bcg/mL BSA.Polymerization reactions (5\u2009\u03bcL) were carried out using the following mixtures: (for DNA polymerase \u03b1) 40\u2009mM Tris-HCl (pH\u20098.0), 5\u2009mM MgCl\u2212 and Dpo4 contained 100 fmol of the template and 50 fmol of 5\u2032-Alexa680-labeled 15-mer primer. Other conditions and the concentrations of dNTPs and DNA polymerases are specified in the figure legends. Reactions were performed at 30\u2009\u00b0C for 30\u2009min for DNA polymerases \u03b1, \u03b2, \u03b4, \u03b5, \u03b6, Kf exo\u2212 and Dpo4, and at 37\u2009\u00b0C for 30\u2009min for DNA polymerase \u03b7. All reactions were stopped by adding 5\u2009\u03bcL of stop buffer , and 100\u2009\u03bcM rhodamine 6G). Aliquots (2.5\u2009\u03bcL) were subjected to electrophoresis in a denaturing 16% polyacrylamide (v/v) gel containing 8\u2009M urea at 30\u2009W for 90\u2009min. The fluorescence intensity of each n-mer band (In) was quantified using an Odyssey infrared imaging system from LI-COR  for 5\u2032-Alexa 680-labeled products. The nucleotide incorporation efficiency was calculated using the formula: \u03a3 In (n\u2009\u2265\u200916) / \u03a3 In (n\u2009\u2265\u200915). The DNA synthesis efficiency was calculated using the formula: I30 / \u03a3 In (n\u2009\u2265\u200915).The reaction mixtures for DNA polymerases \u03b1, \u03b2, \u03b4, \u03b5, \u03b7, \u03b6, Kf exoDNA polymerase \u03b1 was used for in vitro nucleotide insertion and the analysis of primer extension of template oligonucleotides containing Ua. Under the reaction condition in which DNA polymerase \u03b1 inserted only dCTP opposite guanine Fig.\u00a0A, lane 8We investigated whether DNA polymerase \u03b1 extends the primer beyond Ua. DNA polymerase \u03b1 slightly elongated the 15-mer primer to 30-mer (3%) across the Ua lesion  opposite Ua under the condition that incorporated only dCTP into guanine in the template Fig.\u00a0B, lane 7DNA polymerase \u03b6 predominantly inserted mainly dATP 3%) opposite Ua Fig.\u00a0A, lane 7% opposit\u2212 [\u2212, we re-analyzed nucleotide incorporation and translesion synthesis opposite Ua. The results of elongation efficiency by DNA polymerase \u03b2 beyond Ua -oxazolone (Oz) using DNA polymerase \u03b6 was approximately the same as that of natural DNA [DNA polymerase \u03b6 plays a critical role in an error-prone lesion bypass pathway \u201337. We pural DNA . AnalysiDNA polymerase \u03b7 can efficiently and accurately extend the primer beyond the cyclobutane pyrimidine dimer , as wellDpo4 is a thermostable translesion synthesis polymerase and elongated the primer to full-length across Ua  were obtained . However, these two products equilibrate with each other and thus could not be isolated separately. In a previous report [289H370N103O176P29) was confirmed by ESI-MS (m/z 9000.727) and then was used as 30-merUa in our experiment.s report , Dubey, Additional file 2: Fig. S2. DNA synthesis across urea (Ua) by Kf exo\u2212. DNA synthesis in Fig. S2 was conducted under the same condition as in Fig. \u2212 (75 \u03bcU) was incubated with templates containing G (lane 3) or Ua (lane 4) and 100\u2009\u03bcM of each of the four dNTPs (lanes 1\u20134). Lanes 1 and 2 contained no enzyme and are negative controls. The background darkness of panel A is adjusted in Panel B. Fig. S3. DNA synthesis across urea (Ua) by DNA polymerase \u03b7. DNA synthesis in Fig. S3 was conducted under the same condition as in Fig.  Ua lane  and 100"}
{"text": "Substitution of CO by phosphanes influences the bond parameters more than replacing the C5H5 ligand by C5H4Cl.The syntheses and structures of the cymantrenes [(C 3] (Cp\u00a0= \u03c0-C5H5 or \u03c0-C5H4Cl) in the presence of the phosphanes PPh3 or PCy3 (Cy\u00a0= cyclo\u00adhex\u00adyl) and Ph2PCH2CH2PPh2 yields the substitution products [CpMn(CO)2PR3] (R\u00a0= Ph or Cy) and [CpMn(CO)(Ph2PCH2CH2PPh2)], namely, dicarbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)(tri\u00adphenyl\u00adphosphane-\u03baP)manganese(I), [Mn(C5H5)(C18H15P)(CO)2], 1a, dicarbon\u00adyl(\u03b75-1-chloro\u00adcyclo\u00adpenta\u00addien\u00adyl)(tri\u00adphenyl\u00adphosphane-\u03baP)man\u00adganese(I), [Mn(C5H4Cl)(C18H15P)(CO)2], 1b, dicarbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)(tri\u00adcyclo\u00adhexyl\u00adphosphane-\u03baP)manganese(I), [Mn(C5H5)(C18H33P)(CO)2], 2a, di\u00adcarbon\u00adyl(\u03b75-1-chloro\u00adcyclo\u00adpenta\u00addien\u00adyl)(tri\u00adcyclo\u00adhexyl\u00adphosphane-\u03baP)manganese(I), [Mn(C5H4Cl)(C18H33P)(CO)2], 2b, carbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)manganese(I), [Mn(C5H5)(C26H24P2)(CO)], 3a, and carbon\u00adyl(\u03b75-1-chloro\u00adcyclo\u00adpenta\u00addien\u00adyl)manganese(I), [Mn(C5H4Cl)(C26H24P2)(CO)], 3b, The crystal structure determinations show a very small influence of the chlorine substitution and a moderate influence of the phosphane substitution on the bond lengths. The PR3 groups avoid being eclipsed with the C\u2014Cl bonds. All the com\u00adpounds employ weak C\u2014H\u22efO inter\u00adactions for inter\u00admolecular association, which are enhanced by C\u2014H\u22efCl contacts in the chlorinated products.UV irradiation of tetra\u00adhydro\u00adfuran solutions of [CpMn(CO) Limitation of the search to the fragment [(C5H5)Mn(CO)2PPh2] gave 10 hits, of which most contained unsymmetrical mono- or dinuclear diphos\u00adphanes. Relevant in the context of this study were an early determination of the structure of [(C5H5)Mn(CO)2(PPh3)] Mn(CO)2PPh2CH2Ph]  by other donor ligands, particularly phosphanes, is one of the most important textbook examples for the reactivity of metal carbonyl com\u00adplexes Mn(CO)3] (I) and a slight molar excess of the phosphane in tetra\u00adhydro\u00adfuran  was irradiated for 7\u2005h under argon. The colours of the solutions changed from yellow to red with concomitant gas evolution. After further stirring for 16\u2005h, the solvent was evacuated and the residue dissolved in diethyl ether (Et2O) and filtered through a plug of silica gel. The solvent was evaporated again and the residue dissolved in the minimum amount of petroleum ether. This solution was placed on top of a silica gel chromatography column  and the products were eluted with a petroleum ether/Et2O (9:1 v/v) mixture. Evaporation of the eluate yielded the products as yellow powders. Recrystallization from petroleum ether (with some added Et2O) by slow evaporation in a refrigerator at 5\u2005\u00b0C yielded crystals of all three com\u00adpounds.A solution of   and PCy3  in THF (120\u2005ml) was irradiated for 7\u2005h. After the usual work up (see above), a yellow solid was obtained, consisting of a 7:3 mixture of 2b and 2a. Recrystallization from petroleum ether (with some added Et2O) by slow evaporation in a refrigerator at 5\u2005\u00b0C yielded crystals. 1H NMR : \u03b4 4.63 (2H), 4.33 (2H), 2.02\u20131.07 (33H). 31P{1H} NMR : \u03b4 91.8. MS : m/z\u00a0= 490.4 (M+), 434.4 (M+ \u2212 2CO).A solution of impure [(C5H4Cl)Mn(CO)3]  and dppe  in THF (120\u2005ml) was irradiated for 7\u2005h. After usual work up, 3b  was isolated as an orange powder. 0.05\u2005g of the starting material  was recovered. Recrystallization from petroleum ether (with some added Et2O) by slow evaporation in a refrigerator at 5\u2005\u00b0C yielded crystals. 1H NMR : \u03b4 7.82\u20137.75 (4H), 7.47\u20137.35 (6H), 7.33\u20137.22 (6H), 7.19\u20137.09 (4H), 4.44 (2H), 3.56 (2H), 2.53\u20132.41 (2H), 2.36\u20132.22 (2H). 13C{1H} NMR : \u03b4 232.8 , 142.9 , 139.83\u2013138.89 (m), 133.1 , 131.4 , 129.4, 128.6, 128.1 , 97.5, 78.0, 77.9, 77.6, 30.6 . 31P{1H} NMR : \u03b4 117.6. IR : \u03bd (CO)\u00a0= 1847. MS : m/z\u00a0= 580.3 (M+), 552.3 (M+ \u2212 CO), 398.2 (C26H24P2), 183.0 (PPh2), 108.0 (PPh). HRMS (EI): m/z calculated 580.0684, found: 580.0681 (M+).A solution of  in the presence of PPh3 leads to 1a and 1b in moderate yields of 40\u201360% \u2005\u00c5] is significantly longer (>20\u03c3) than the Mn1\u2014P1 bond [2.2259\u2005(6)\u2005\u00c5]. All other bond lengths are identical in the two mol\u00adecules (Table\u00a02The major difference between the two mol\u00adecules is in the relative orientation of the Mn(CO)s Table\u00a02.supporting information). Three of them involve arene C\u2014H bonds, and carbonyl atom O22 accepts two of them .There are five inter\u00admolecular C\u2014H\u22efO hydrogen bonds  shorter in 1b. The most important bond parameters can be found in Table\u00a02The Mn\u2192P vector is nearly perpendicular to the C\u2014Cl bond (torsion angle C1\u2014Ct\u2014Mn\u2014P1 is 77.6\u00b0). The individual bond lengths are nearly identical to those in supporting information). The Cl atoms always bridge two different H atoms of the same symmetry-related arene ring along the a screw axis. Apparently, this inter\u00adaction enforces the orientation of this particular arene ring and generates the chirality.There is only one intra\u00admolecular C\u2014H\u22efCl hydrogen bond with a length shorter than the sum of the van der Waals radii (H16\u22efCl1). Additionally, there is one weak intra\u00admolecular and three inter\u00admolecular C\u2014H\u22efO hydrogen bonds, and one inter\u00admolecular C\u2014H\u22efCl hydrogen bond  and protonation studies followed soon afterwards  in very low yield. Despite long irradiation times, large amounts of the starting material could be recovered. In contrast to 1a, it was not possible to li\u00adthiate 2a with n-BuLi or t-BuLi and chlorinate the presumed inter\u00admediate lithium com\u00adpound with C2Cl6 to give 2b. It was possible, however, to obtain crystals of both com\u00adpounds suitable for X-ray diffraction.We prepared both com\u00adpounds according to Scheme\u00a012a crystallizes in the monoclinic space group P21/n, with one mol\u00adecule in the asymmetric unit   Table\u00a02. The dis3 ligand and carbonyl atom O1. A packing diagram shows that these inter\u00adactions mainly  join the individual mol\u00adecules in the c direction .There is one intra\u00admolecular and two inter\u00admolecular C\u2014H\u22efO hydrogen bonds involving exclusively methyl\u00adene H atoms of the PCy2b crystallizes in the monoclinic space group P21/c, with one mol\u00adecule in the asymmetric unit  than in 2a and have the same lengths as in 1b. This is also true for the distance of the Mn atom from the centroid of the cyclo\u00adpenta\u00addienyl ring. More bond parameters can be found in Table\u00a02Compound it Fig.\u00a03. The Mn\u2192X inter\u00adactions involving two methyl\u00adene H atoms of the PCy3 ligand and either the Cl atom or one carbonyl O atom. Additionally, an inter\u00admolecular C\u2014H\u22efCl hydrogen bond joins glide-plane-related mol\u00adecules along the b axis .There are intra\u00admolecular C\u2014H\u22ef3a was first prepared by the photochemical reaction of cymantrene with bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)ethane (dppe) in benzene (ca 85% yield after 50\u2005h irradiation), while the same reaction in cyclo\u00adhexane produced the dppe-bridged dinuclear com\u00adplex {[(C5H5)Mn(CO)2]2[\u03bc-dppe]} , again with substantial recovery of the starting material. Some weak signals in the NMR spectra showed small amounts of other products, most likely dinuclear ones. However, the influence of prolonged reaction times on product yields and distribution was not examined. In contrast to the reactivity of 1b, it was not possible to deprotonate 3b  and introduce more chlorine substituents via addition of C2Cl6. However, again it was possible to obtain crystals suitable for X-ray diffraction for both com\u00adpounds.Irradiation of THF solutions of the corresponding tricarbonyl com\u00adplexes in the presence of dppe for 7\u2005h yields 3a crystallizes in the monoclinic space group C2/c, with one mol\u00adecule in the asymmetric unit. Fig.\u00a04Compound 3 ligand or one C\u2014H group of the cyclo\u00adpenta\u00addienyl ring. The packing diagram shows that these inter\u00adactions connect the individual mol\u00adecules in the a direction .There are two inter\u00admolecular hydrogen bonds involving the carbonyl O atom and one methyl\u00adene H atom of the PCy3b crystallizes in the triclinic space group P3a. The same holds for the relative distances between manganese and the cyclo\u00adpenta\u00addienyl centroids, while the Mn\u2014CO bonds are virtually identical .There is one inter\u00admolecular C\u2014H\u22efCl hydrogen bond involving an arene H atom, which joins the individual mol\u00adecules in the 3 system, where a substantial elongation occurs. When com\u00adparing the two triads with different phosphanes, the Mn\u2014Ct (Ct des\u00adcribes the centroid of the cyclo\u00adpenta\u00addienyl ring) and Mn\u2014P distances show a slight increase in the order 3\u21921\u21922. The C\u2014O bonds follow the trend 1 \u2243 2 < 3 and the C\u2014Cl bonds follow the trend 2b < 1b \u2243 3b. The average C\u2014C bond lengths are the same within 2\u03c3 for all six com\u00adpounds. Comparison with the PPh2CH2Ph com\u00adpound GIXRIO and the ferrocenylbis\u00adphosphane chelate com\u00adpound EFUHAO shows more similarities with the PPh3 com\u00adplexes 1 than with the dppe chelates 3. The tendency of the Mn\u2014P bonds to eclipse one cyclo\u00adpenta\u00addienyl C\u2014H bond is obvious in all the com\u00adpounds. In all the chloro com\u00adpounds, the Mn\u2014P bonds avoid being eclipsed with the C\u2014Cl bond of the cyclopentadienyl ring.The introduction of a chlorine substituent in the cyclopentadienyl ring leads to a slight increase in the Mn\u2014Ct and Mn\u2014P distances for all the title phosphanes, while both the Mn\u2014CO and the C\u2014O bonds are only affected in the PCyvia the formation of C\u2014H\u22efCl hydrogen bonds.Apparently, the introduction of one chlorine substituent has only a small influence on the bond lengths, despite the relatively large effect on the spectroscopic data. Steric hindrance within the phosphanes seems to be of greater importance for the bond parameters than the differences in electronic effects. However, the presence of chlorine in the cyclo\u00adpenta\u00addienyl ring leads to additional lattice stabilization 10.1107/S2053229621009177/dv3012sup1.cifCrystal structure: contains datablock(s) compd1a, compd1b, compd2a, compd2b, compd3a, compd3b, global. DOI: 10.1107/S2053229621009177/dv3012compd1asup2.hklStructure factors: contains datablock(s) compd1a. DOI: 10.1107/S2053229621009177/dv3012compd1bsup3.hklStructure factors: contains datablock(s) compd1b. DOI: 10.1107/S2053229621009177/dv3012compd2asup4.hklStructure factors: contains datablock(s) compd2a. DOI: 10.1107/S2053229621009177/dv3012compd2bsup5.hklStructure factors: contains datablock(s) compd2b. DOI: 10.1107/S2053229621009177/dv3012compd3asup6.hklStructure factors: contains datablock(s) compd3a. DOI: 10.1107/S2053229621009177/dv3012compd3bsup7.hklStructure factors: contains datablock(s) compd3b. DOI: 10.1107/S2053229621009177/dv3012sup8.pdfAdditional figures and table. DOI: 2107491, 2107490, 2107489, 2107488, 2107487, 2107486CCDC references:"}
{"text": "In this work, practically important relationships between Eint and electron density, its Laplacian, curvature, potential, kinetic, and total energy densities at the bond critical point as well as bond length were derived for the structures of the [Z\u2013I\u00b7\u00b7\u00b7Hal]\u2212 and [Z\u2013Hal\u00b7\u00b7\u00b7I]\u2212 types bearing halogen bonds and involving iodine as interacting atom(s) . The mean absolute deviations for the correlations found were 2.06\u20134.76 kcal/mol.Bond energy is the main characteristic of chemical bonds in general and of non-covalent interactions in particular. Simple methods of express estimates of the interaction energy, E The halogen bond is one of the most important types of non-covalent interactions being second only to hydrogen bonds in its significance. According to the IUPAC definition, \u201ca halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity\u201d . Weak inThe supramolecular and cluster chemistry of halide anions currently attracts much attention ,27,28,29b) is a difficult task. Experimental methods  are usually associated with complex technical procedures and can be applied to a very limited number of structures. The direct theoretical calculations of Eb for the A\u00b7\u00b7\u00b7B bond as the energy difference between the structure A\u00b7\u00b7\u00b7B and the isolated molecules A and B may be successfully applied to intermolecular non-covalent interactions in the gas phase. However, in the condensed phase, molecules are usually bound with each other by a network of several non-covalent interactions, and an adequate fragmentation which affects only the bond of interest is often impossible. In such a situation, an approximation of Eb through other parameters easily accessible from experiment becomes very important \u2212 and [(A)nZ\u2013Y\u00b7\u00b7\u00b7I]\u2212 types  were calculated. The correlations between Eint and the electron density (\u03c1b), its Laplacian (\u22072\u03c1b), the curvature of \u03c1(r) which is parallel to the bond path direction (positive) , the potential, kinetic, and total energy densities  at BCP, and the halogen bond length (dY\u00b7\u00b7\u00b7X) were established.Recently, the author started a project to establish practically useful correlations between the interaction energy and properties which could be easily determined from experiment for halogen bonds of various types, including those formed by a halide anion. In the previous work , such renZ\u2013Y\u00b7\u00b7\u00b7X]\u2212 which include different types of second-order atoms Z and third-order groups A, otherwise, the relationships found may suffer a significant overfitting. Therefore, a large statistically significant set of 412 structures bearing twelve different types of the Z atom was used in this work.Two points should be mentioned here. First, the interactions with the iodine atom as a halogen bond donor are the most important among all halogen bonds since the existence of a prominent \u03c3-hole at the iodine atom provides particularly high stability of these interactions. Second, reliable relationships can be obtained only for sufficiently large sets of the structures [(A)Full geometry optimization of the main set of structures was carried out at the density functional theory (DFT) level by using the M06-2X functional  with thenZ\u2013Y\u00b7\u00b7\u00b7X]\u2212 structures  [int(Vb) correlations for the [(A)nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212 structures  obtained at the M06-2X level of theory have similar parameters as those for the MP4, CCSD, and CCSD(T) methods. On the other hand, it was found \u2212 were calculated using Equation (1):nZ\u2013Y fragments were unrelaxed and corresponded to those in [(A)nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212. The topological analysis of the electron density distribution was performed with the help of the Atoms in Molecules (AIM) method developed by Bader \u2212 and [(A)nZ\u2013Y\u00b7\u00b7\u00b7I]\u2212 types  were selected for the calculations. Among them, 70 structures were in each series [(A)nZ\u2013I\u00b7\u00b7\u00b7X]\u2212 with X = F, Cl, or Br and [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212, 65 structures were in the [(A)nZ\u2013I\u00b7\u00b7\u00b7I]\u2212 series, and 67 structures were in the [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series. For Z = C and N, different orbital hybridizations of these atoms were considered. For Z = S and P, different oxidation states of these atoms were considered. The groups A  vary from the electron donor to the electron acceptor ones providing a broad span of interaction energies for the halogen bond. The complete list of the calculated structures is given in Structures of the [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 type O2S\u2013I\u2026F]\u2212, [F3Si\u2013I\u2026F]\u2212, [p-H2N-C6H4-Br\u2013I\u2026F]\u2212, [Me3Si\u2013I\u2026F]\u2212, [MeO\u2013I\u2026F]\u2212, [(Me)O2S\u2013I\u2026F]\u2212, [Ph\u2013I\u2026F]\u2212, and [(p-Me-C6H4)2N\u2013I\u2026F]\u2212), which provide the Eint span from \u20139 to \u201373 kcal/mol.The M06-2X/ADZP\u2013DKH method was validated toward the reproduction of the experimental electron densities for the set of eleven structures bearing halogen bonds of different types  and for which the experimental electron densities are known. Performance of the M06-2X and PBE0-D3BJ functionals was also compared for the set of ten structures of the \u2212, HO\u2013H\u00b7\u00b7\u00b7Cl\u2212, HO\u2013H\u00b7\u00b7\u00b7I\u2212, H3C\u2013H\u00b7\u00b7\u00b7I\u2212, and [I\u2013I\u2013I]\u2212). As can be seen in \u2212. The experimental error is in the range of 0.1\u20131.6 kcal/mol, and theoretical M06-2X values fall within the 3\u03c3 interval for four of six structures. The interaction energies calculated at the CCSD and CCSD(T) levels were strongly underestimated when the CP correction was applied. The CCSD method performed worse than M06-2X for H3C\u2013H\u00b7\u00b7\u00b7F\u2212 and HO\u2013H\u00b7\u00b7\u00b7Cl\u2212 even with the aug-cc-pVTZ basis set, and only the CCSD(T) level with the triple-zeta basis set and without the CP correction provided better results than the DFT approach . Thus, considering that typical MAD values for the Eint property relationships found for the structures [(A)nZ\u2013Hal1\u00b7\u00b7\u00b7Hal2]\u2212 are 2\u20134 kcal/mol . cations . Here, tructures . The calty 1.07, . The PBEint(Vb) relationships obtained for the small set of ten structures of the [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 type were similar for both M06-2X and PBE0-D3BJ functionals  and it was 3.96 kcal/mol at Vb = 100 kcal/(mol\u2022bohr3). These deviations were lower than MAD for the whole set of seventy [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 structures . All these results indicate that the relationships found in this work at the M06-2X/ADZP\u2013DKH level are reliable for the determination of Eint using experimental electron density properties.Correspondingly, the Ectionals . The devnZ\u2013I\u00b7\u00b7\u00b7X]\u2212 and [(A)nZ\u2013Y\u00b7\u00b7\u00b7I]\u2212 types and the corresponding Eint property relationships were discussed (in this and the following sections). The calculated BSSE-corrected interaction energies for the halogen bonds in these structures varied between 2.53 and \u221288.43 kcal/mol. These bonds were the strongest for the [(A)nZ\u2013I\u00b7\u00b7\u00b7F\u2212] series. The highest dispersion of Eint was found for the [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 and [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series. The halogen bonds in the series [(A)nZ\u2013I\u00b7\u00b7\u00b7Cl]\u2212, [(A)nZ\u2013I\u00b7\u00b7\u00b7Br]\u2212, and [(A)nZ\u2013I\u00b7\u00b7\u00b7I]\u2212 have similar strengths and dispersion.After validation of the computational method, the interaction energies calculated for 412 structures of the [(A)int for the hydrogen bonds X\u2013H\u2026O and FH\u2026FR [nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212  bearing halide anions [int and Vb were found for all series except [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 (int(Gb) relationship was linear only for the [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 series and it was approximated by a binominal function for [(A)nZ\u2013I\u00b7\u00b7\u00b7X]\u2212  and [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212. Finally, the Eint(\u03c1b) dependence was quadratic for all series.These types of relationships were recommended for the predictions of End FH\u2026FR ,83 and fe anions . Here, tCl\u00b7\u00b7\u00b7I]\u2212 . The EinnZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series (int(Vb), Eint(Gb), or Eint(\u03c1b) function. Instead, the horizontal branch is clearly visible in the range of Eint of 10\u201320 kcal/mol. The interaction energy could be reasonably approximated by polynomial fourth-order functions, but such an approximation is usually associated with significant overfitting and cannot be recommended for practical use. The reasons of this peculiar situation are discussed below.An interesting relationship distinct from all other bonds with halide anions was obtained for the [(A)\u2212 series . These snZ\u2013Y\u00b7\u00b7\u00b7X]\u2212 in this and previous \u2212. Third, the slope of the relationships is strongly affected by the nature of the Y and X atoms. For instance, for the Vb estimator, the lowest slope (0.69\u20130.84) and the highest negative intercept (\u22123.68 \u00f7 \u22126.50) were found for X = F. The highest slopes were detected for [(A)nZ\u2013I\u00b7\u00b7\u00b7I]\u2212 (2.34) as well as for the [(A)nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212  series (1.55\u20132.12). The series with (X or/and Y) = Cl but (X and Y) \u2260 F exhibited an intermediate slope (1.26\u20131.46). Such a behavior can be qualitatively interpreted by the different properties of the halogen atoms forming the Y\u00b7\u00b7\u00b7X bond. First of all, the electronegativity of the X atom decreases along the series F > Cl > Br > I. There is a clear trend between the slope of the Eint(Vb) dependence and the difference of the electronegativities of X and Y nZ group on the Y\u00b7\u00b7\u00b7X bond are more pronounced if the electron shells of X are more diffuse, i.e., from X = F to I. Since the higher dispersion contribution and more diffuse electron shells are associated with lower concentration of electron or energy density at BCP, Eint values are higher for most electron acceptor groups (A)nZ at a given value of Eint in the case of heavier atom X.Analysis of the relationships obtained for the structures \u2212 + [(A)nZ\u2013I\u00b7\u00b7\u00b7Br]\u2212 + [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212, (ii) [(A)nZ\u2013I\u00b7\u00b7\u00b7Cl]\u2212 + [(A)nZ\u2013Cl\u00b7\u00b7\u00b7Cl]\u2212 + [(A)nZ\u2013Br\u00b7\u00b7\u00b7Cl]\u2212 + [(A)nZ\u2013Cl\u00b7\u00b7\u00b7Br]\u2212, and (iii) [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 + [(A)nZ\u2013Br\u00b7\u00b7\u00b7F]\u2212 + [(A)nZ\u2013Cl\u00b7\u00b7\u00b7F]\u2212 groups. Each of them may be approximated by a linear function . The Eint(Gb) and Eint(\u03c1b) dependences are characterized by a higher dispersion between series. They are more sensitive to the nature of the Y and X atoms and, therefore, such a grouping is not efficient for those relationships.Fourth, some series form distinct groups which can be approximated by a single relationship of a reasonable quality. There are three such groups when considering the EnZ\u2013Y\u00b7\u00b7\u00b7X]\u2212 structures were significantly different from those obtained previously for the hydrogen bonds X\u2013H\u2026O and FH\u2026FR \u2212 (this work) and [(A)nZ\u2013Br\u00b7\u00b7\u00b7F]\u2212 [int(\u22072\u03c1b) functions for other series are not well-defined nZ\u2013I\u00b7\u00b7\u00b7F]\u2212, [(A)nZ\u2013I\u00b7\u00b7\u00b7Cl]\u2212, and [(A)nZ\u2013I\u00b7\u00b7\u00b7Br]\u2212  relationship for the first of these series is linear and of a lower quality compared to the Eint(Vb), Eint(Gb), and Eint(\u03c1b) functions. The last two series are very well approximated by two exponential functions . For the series [(A)nZ\u2013I\u00b7\u00b7\u00b7I]\u2212 and [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212, the \u03bb||,b parameter is not sensitive to determine Eint at high values   fittings at lower Eint are also not reasonable. Finally, the Eint function is not well-defined for [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212.The curvature of the electron density distribution can serve for the estimates of EI\u00b7\u00b7\u00b7Br]\u2212 . The Eincal/mol) . The Einint depends on the nature of the Y and X atoms. It cannot be used for the [(A)nZ\u2013I\u00b7\u00b7\u00b7F]\u2212 series due to high dispersion of the Eint(Hb) function at lower Eint and its low sensitivity at higher Eint (int(Hb) relationship is not sensitive for the weakest interactions with Eint < 10 kcal/mol. However, for stronger interactions, good linear dependences were observed , except for the [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series which was approximated by a quadratic function  nZ\u2013I\u00b7\u00b7\u00b7I]\u2212, [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212, [(A)nZ\u2013Cl\u00b7\u00b7\u00b7Cl]\u2212, [(A)nZ\u2013Cl\u00b7\u00b7\u00b7Br]\u2212, and [(A)nZ\u2013Br\u00b7\u00b7\u00b7Br]\u2212) are described together by a single linear function of the reasonable quality   . Six sercal/mol) .nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 demonstrate reasonable exponential relationships between interaction energy and the length of the halogen bond nZ\u2013I\u00b7\u00b7\u00b7Br]\u2013 + [(A)nZ\u2013Br\u00b7\u00b7\u00b7I]\u2212 and [(A)nZ\u2013Br\u00b7\u00b7\u00b7Cl]\u2212 + [(A)nZ\u2013Cl\u00b7\u00b7\u00b7Br]\u2212. For other series, the fitting parameters are quite different from each other. Similarly to the other estimators, the Eint(dY\u2026X) dependence is complex for the [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series. There is a horizontal branch for the interval of Eint 5\u201315 kcal/mol. Meanwhile, in this case, the dependence may be quite reasonably approximated by a two-exponential function .All series except for [(A)gen bond . The quaint\u2013property relationships for the [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series have a peculiar character. The more detailed analysis shows that such behavior is due to the tremendous effect of the second-order atom Z and the third-order groups A. First, the Eint values are low and do not exceed 14 kcal/mol when Z = C, P, Si, B, or H  and those with Z = O, N, or S have a significant span of Eint .As was mentioned above, the E B, or H . The strint(Vb) trend slope for the combined series [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 (Z = Si + B) is 6.75 while the slope of the linear correlation for the series [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212  is 1.43  are not linear but exponential. The tangent slopes at the lowest energy points are 9.2 and 8.7.Second, the E is 1.43 . DependenN\u2013Cl\u00b7\u00b7\u00b7I]\u2212 structures could be divided into two distinct groups  and those with a stronger Cl\u00b7\u00b7\u00b7I interaction  imine and nitro compounds, Group II). The trend slope for these two groups is similar (2.1) but the intercept is very different . The different behavior of these two groups is apparently associated with a different nature of the (A)nN part of the molecule. In Group I, (A)nN exhibits either electron donor or weak electron acceptor properties. In Group II, (A)nN is a strong electron acceptor. Furthermore, the structures of Group II have more extended conjugation systems compared to those of Group I. All these relationships considered together provide such a peculiar trend for the whole [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series. Interestingly, this effect of Z and A is much smaller for other series making possible the existence of linear correlations. Similar behavior was also found for the Gb and \u03c1b estimators.Third, the \u2212 series. However, for the more narrow series \u2212, [(A)nC\u2013Cl\u00b7\u00b7\u00b7I]\u2212, and [(A)nP\u2013Cl\u00b7\u00b7\u00b7I]\u2212, these relationships are of a good quality  and they may be useful for practical applications. The d(Y\u2026X) estimator is much better for the description of the [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212 series because it permits the reasonable approximation of Eint by a single two-exponent function.The great effect of the Z atom and A group on Eint for the condensed phases is a much more difficult task than that for the gas phase. Both periodic solid state and cluster approaches often do not allow direct estimates of Eint as an energy difference because fragments may have multiple mutual weak intermolecular interactions. When it is possible, the adequate computational model is usually exceedingly large. For instance, accurate calculations of Eint for the A\u00b7\u00b7\u00b7B bond in a solid-state structure within the cluster approach requires explicit consideration of all intermolecular interactions which molecules A and B are involved in. An example of an adequate cluster for the direct estimates of Eint between the simple fragments I\u2013C4F8\u2013I and Cl\u2212 in the X-ray structure ACIPOU is shown in 4F8\u2013I\u00b7\u00b7\u00b7Cl\u2212 surrounded by all molecules which form short contacts with the I\u2013C4F8\u2013I or Cl\u2212 fragments).The estimate of EConsidering this situation, the practice of utilization of small bimolecular clusters which include only two molecules forming a contact of interest becomes increasingly popular. In other words, there are multiple attempts to approximate the properties of solid-state structures by gas phase calculations.int calculated for the I\u2013CF2CF2\u2013I\u00b7\u00b7\u00b7Cl\u2212 halogen bond in the X-ray structure ACIPIO using the bimolecular approach is 20.07 kcal/mol. However, when four molecules are considered .There are two points which invalidate this practice. First, such a bimolecular model ignores other intermolecular interactions in which both considered molecules participate. These secondary interactions may significantly affect the energy of the contact under study. For instance, Eint has little physical meaning.The second point is that geometry of bimolecular clusters is usually not optimized but taken from the X-ray structures since optimization often leads to the collapse of the structure compared to X-ray. In such calculations, the geometry considered is not equilibrium and does not belong to a minimum energy path for either adiabatic or vertical bond cleavage, and, hence, the resulting Eint in the condensed phase is free from the difficulties discussed above since it requires a single parameter  directly obtained from experiment.Application of the correlations established in this work for the rapid estimates of EnZ\u2013I\u00b7\u00b7\u00b7Hal]\u2212 and [(A)nZ\u2013Hal\u00b7\u00b7\u00b7I]\u2212 bearing the iodine atom . Thus, together with the results published previously \u2212, those with X = F demonstrate quite poor approximations of Eint with MAD of 3.29\u20134.76 kcal/mol. For other structures, except [(A)nZ\u2013Cl\u00b7\u00b7\u00b7I]\u2212, more reasonable correlations were obtained . Meanwhile, the approximations of Eint for halogen bonds formed by halide anions are worse than those obtained for homohalogen bonds formed by two neutral fragments \u2212 type. In fact, only two parameters were found to be able to adequately estimate Eint for this bond, i.e., Hb  and dY\u2026X.Second, the most difficult case is the structures of the [(A)int for all structures [(A)nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212. For the electron density-based properties, the highest slopes (linear correlations) or curvatures (non-linear correlations) were found for the bonds formed by heavy halogens (I and Br) while the lowest slopes and curvatures were observed for X = F.Third, there is no unique equation to approximate EFourth, the correlations derived for halogen bonds with halide anions are very different from those established for some hydrogen bonds and halogen bonds formed by two neutral fragments . This anb, Vb, Gb, and dY\u00b7\u00b7\u00b7X estimators behave similarly. In contrast, the \u22072\u03c1b, \u03bb||,b, and Hb parameters have limited significance as Eint estimators and they may be used only for some series or a certain range of the Eint values.Fifth, the \u03c1int of the structures [(A)nZ\u2013Y\u00b7\u00b7\u00b7I]\u2212 and [(A)nZ\u2013I\u00b7\u00b7\u00b7X]\u2212 are given in The relationships recommended for practical use to estimate E"}
{"text": "The distorted KO6 octa\u00adhedra share edges, resulting in chains running in the [010] direction.The title compound, C E)-2-{4-[3-(thio\u00adphen-3-yl)acrylo\u00adyl]phen\u00adoxy}acetic acid are described. Crystallization from an ethanol\u2013water mixture resulted in the title compound, C30H23KO8S2 or [K(C15H11O4S)(C15H12O4S)]n, containing one mol\u00adecule of the acid and one mol\u00adecule of the potassium salt in the asymmetric unit. Both mol\u00adecules share the H atom between their carboxyl groups and a potassium ion. The C=C bonds display an E configuration. The thio\u00adphene and phenyl rings in the two mol\u00adecules are inclined by 43.3\u2005(2) and 22.7\u2005(2)\u00b0. The potassium ion is octa\u00adhedrally coordinated by six O atoms. This distorted octa\u00adhedron shares on opposite sides two oxygen atoms with inversion-related octa\u00adhedra, resulting in chains of octa\u00adhedra running in the [010] direction, which form ladder-like chains by C\u2014H\u22ef\u03c0 inter\u00adactions. A Hirshfeld surface analysis indicates that the highest contributions to the surface contacts arise from inter\u00adactions in which H atoms are involved, with the most important contribution being from H\u22efH (31.6 and 31.9% for the two mol\u00adecules) inter\u00adactions.The synthesis and spectroscopic data of ( This compound is considered to be a good monomer for the synthesis of water-soluble polythio\u00adphene-based conjugated polyelectrolytes. A single-crystal structure determination indicates that after crystallization, crystals were obtained containing one mol\u00adecule of the acid and one mol\u00adecule of the potassium salt in the asymmetric unit.\u00b0 for mol\u00adecule B. The C=C bonds display an E configuration, resulting in short intra\u00admolecular C6\u2014H6\u22efO9 and C26\u2014H26\u22efO29 inter\u00adactions , K41\u22efO36ii = 3.347\u2005(3)\u2005\u00c5, symmetry codes: (ii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01, (iv) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].Potassium ion K41 is octa\u00adhedrally coordinated by six O atoms with K\u2014O distances between 2.672\u2005(2) and 2.906\u2005(3)\u2005\u00c5 Fig.\u00a03 and an oii, at the other side O20i and O20iv; symmetry codes: (i) x\u00a0+\u00a01, y, z, (ii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01, (iv) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01] with inversion-related octa\u00adhedra  and 4.8353\u2005(14)\u2005\u00c5 .In the crystal packing, the potassium ion K41 inter\u00adacts with six mol\u00adecules of which two occur in the carb\u00adoxy\u00adlic acid form Fig.\u00a04. The disa Figs. 3 and 5 \u25b8.Cg1v contacts .Despite the presence of many aromatic rings, the crystal packing of the title compound does not show \u03c0any \u2013\u03c0 inter\u00adactions. The shortest centroid\u2013centroid distance is 4.735\u2005(3)\u2005\u00c5 between thio\u00adphene rings S1/C2\u2013C5 and S21/C22\u2013C25 with an angle between the rings of 52.3\u2005(3)\u00b0. However, C\u2014H\u22ef\u03c0 inter\u00adactions are present and give rise to a ladder-like chain also running in the [010] direction Table\u00a01. In addiThe packing does not show any residual solvent-accessible voids.et al., 2007CrystalExplorer . The sharp tips at de + di \u2243 1.4\u2005\u00c5 arise from the O19\u2014H19\u22efO39 hydrogen bond. The principal contribution to the Hirshfeld surfaces involves H\u22efH contacts at 31.6 and 31.9% for mol\u00adecules A and B, respectively. These are followed by C\u22efH/H\u22efC (21.1 and 20.0%) O\u22efH/H\u22efO (17.4 and 17.3%) and S\u22efH/H\u22efS (8.8 and 9.9%) contacts.The Hirshfeld surface analysis \u2014p-C6H4\u2014R2 gave 619 hits (with C atoms double-bond acyclic). For only 33 cases (5.3%), the double bond has the Z configuration . The histogram of the dihedral angle between the planes of the double bond and the phenyl ring shows values between 0.0 and 86.2\u00b0 . A search with thio\u00adphene as R1 resulted in only four hits . Only one structure was found for which R2 is the same as in the title compound -2-{4-[3-(thio\u00adphen-3-yl)acrylo\u00adyl]phen\u00adoxy}acetic acid, is given in Fig.\u00a09The synthetic pathway to synthesize the target compound, (A mixture of ethyl 2-(4-acetyl\u00adphen\u00adoxy)acetate (5\u2005mmol), 3-thio\u00adphene\u00adcarbaldehyde (5\u2005mmol) and 50\u2005mL of ethanol was stirred in ice-cold water for 20 minutes. Then, 5\u2005mL of 50% KOH solution was added dropwise to the reaction mixture, which was then stirred continuously for 5\u2005h. At the end of the reaction, water was added to the reaction mixture and stirring was continued until all solids in the mixture were dissolved. Concentrated HCl was slowly added to the obtained solution until the solution changed from brown to yellow. The solution was then heated until crystals appeared. The solid then began to crystallize when the solution temperature started to decrease. The crystallized solid was filtered off, washed thoroughly with water and recrystallized from an ethanol\u2013water mixture to give 2-{4-[3-(thio\u00adphen-3-yl)acrylo\u00adyl]phen\u00adoxy}acetic acid (yield 62%) in the form of pale-yellow crystals (m.p. 455\u2005K).\u22121): 1017, 980 (=C\u2014H bend), 1597 (C=C), 1659 (C=O), 3457 .IR , J (Hz)]: 7.60 , 7.42 , 7.38 , 7.81 , 7.34 , 8.03 , 7.02 , 4.77 .13C NMR : 121.81 (C2), 128.75 (C3), 127.01 (C4), 125.41 (C5), 132.67 (C6), 130.87 (C7), 171.85 (C8), 169.73 (C9), 138.39 (C10 and C14), 137.96 (C11 and C13), 114.65 (C12), 64.68 (C15), 189.09 (C16). Calculation for C15H11O4S: M = 287 au.Uiso(H) value of 1.5Ueq of the parent atom O19. The other H atoms were placed in idealized positions and included as riding contributions with an Uiso(H) values of 1.2Ueq of the parent atom, with C\u2014H distances of 0.93 (aromatic) and 0.97\u2005\u00c5 (CH2). In the final cycles of refinement, 12 outliers with |error/e.s.d.| > 5.0 were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021004801/ey2007sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021004801/ey2007Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004801/ey2007Isup3.cmlSupporting information file. DOI: 2082049CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The natural convection boundary layer flow of a viscous incompressible fluid with temperature dependent viscosity and thermal conductivity in the presence of exothermic catalytic chemical reaction along a curved surface has been investigated. The governing non dimensional form of equations is solved numerically by using finite difference scheme. The numerical results of velocity profile, temperature distribution and mass concentration as well as for skin friction, heat transfer rate and mass transfer rate are presented graphically and in tabular form for various values of dimensionless parameters those are generated in flow model during dimensionalization. From the obtained results, it is concluded that the exothermic catalytic chemical reactions is associated with temperature dependent viscosity and thermal conductivity. Further, it is concluded that the body shape parameter also plays an important quantitative role for change in velocity profile, temperature field and mass concentration behavior in the presence of exothermic catalytic chemical reaction. Merkin and Chaudhary .At this time, please address the following queries:Please clarify the sources of funding  for your study. List the grants or organizations that supported your study, including funding received from your institution.State what role the funders took in the study. If the funders had no role in your study, please state: \u201cThe funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.\u201dIf any authors received a salary from any of your funders, please state which authors and which funders.If you did not receive any funding for this study, please state: \u201cThe authors received no specific funding for this work.\u201dPlease include your amended statements within your cover letter; we will change the online submission form on your behalf.Reviewers' comments:5. Review Comments to the AuthorReviewer #1:\u00a0The report presents the natural convection boundary layer flow of a viscous incompressible fluid with temperature-dependent viscosity and temperature-dependent thermal conductivity in the presence of exothermic catalytic\u00a0chemical reaction along a curved surface. I recommend major revision due to the following facts.1. In Eq. (3), the authors added (u^2/2x)n to the convective acceleration term.Comment: What does the new term means? How did you derive it?2. After Eq. (6), it was written that n = P(x) + Q(x). Whereas  is the wall temperature function and the  is the body shape function.Comment: The authors refer Readers to check \"Pop, I. and Takhar, H. S. Free convection from a curved surface. Journal of Applied Mathematicsand Mechanics, 73 (1993), pp. 534 -539\" for details.Comment: This is not acceptable. Update the research methodology with the derivation of such momentum equation.3. Research question is needed to harmonize the contribution of the report to the body of knowledge.Comment: Research questions are needed at the end of the introduction section. Research questions are needed. Note that the results in this report are typical answers to unknown questions. This is true because the manuscript provides some powerful answers to unknown questions. Note that the research questions must connect the title to the analysis of results, and conclusion. This would guide authors not to generate many results that are not consistent to provide insight. The author should update the manuscript with appropriate and relevant research questions at the end of the introduction section. This would guide the author to structure logical analysis of results. Logical questions are expected. This would help readers to link what is known in the literature with the novelty of this study.4. The similarity variables presented as Eq. (7) are dimensional. The unit of the first, u, is m^0.5 while that of v is m^{-1/4}, and that of y is also dimensional. Hence, the variables used to non-dimenzionalize the governing equation are not appropriate.Reviewer #2:\u00a0Recommendation: Minor revisionAuthors should revise the manuscript according to the following comments.\u2022 Nomenclature is must.\u2022 Some grammatical and typo mistakes are found in the manuscript.\u2022 The governing differential equations describing the flow are non-linear. Is the solution obtained unique?\u2022 Specify the applications of considered physical model or geometry.\u2022 Introduction section should be made more concise to show previous work in the field. At present a lot of related researches are stated in the introduction. However, not sufficient analysis is presented. The authors should ask themselves: what are the problems with the presented researches? Why is the recent work needed? Hope these can improve the present work by following past articles.\u2022 Effect of Joule heating on MHD non\u2010Newtonian fluid flow past an exponentially stretching curved surface\u2022 Magnetohydrodynamic Cattaneo-Christov flow past a cone and a wedge with variable heat source/sink\u2022 Heat and mass transfer in MHD Casson nanofluid flow past a stretching sheet with thermophoresis and Brownian motion\u2022 Effect of asymmetrical heat rise/fall on the film flow of magnetohydrodynamic hybrid ferrofluid\u2022 Simultaneous solutions for first order and second order slips on micropolar fluid flow across a convective surface in the presence of Lorentz force and variable heat source/sink\u2022 Effect of thermal radiation on MHD Casson fluid flow over an exponentially stretching curved sheet\u2022 Influence of non-uniform heat source/sink on the three-dimensional magnetohydrodynamic Carreau fluid flow past a stretching surface with modified Fourier\u2019s law\u2022 MHD Carreau Fluid Flow Past a Melting Surface with Cattaneo-Christov Heat Flux\u2022 Physical aspects on unsteady MHD\u2010free convective stagnation point flow of micropolar fluid over a stretching surface\u2022 Influence of viscous dissipation on MHD flow of micropolar fluid over a slendering stretching surface with modified heat flux model\u2022 A non\u2010Fourier heat flux model for magnetohydrodynamic micropolar liquid flow across a coagulated sheetNote: I want to see the revised version of the manuscript.https://pacev2.apexcovantage.com/. PACE helps ensure that figures meet PLOS requirements. To use PACE, you must first register as a user. Registration is free. Then, login and navigate to the UPLOAD tab, where you will find detailed instructions on how to use the tool. If you encounter any issues or have any questions when using PACE, please email PLOS at\u00a0figures@plos.org. Please note that Supporting Information files do not need this step.While revising your submission, please upload your figure files to the Preflight Analysis and Conversion Engine (PACE) digital diagnostic tool,\u00a0 13 Apr 2021Response to Reviewers Comments (PONE-D-21-04681)Effects of Temperature Dependent Viscosity and Thermal Conductivity on Natural Convection Flow along a Curved Surface in the Presence of Exothermic Catalytic Chemical ReactionReviewer #1: The report presents the natural convection boundary layer flow of a viscous incompressible fluid with temperature-dependent viscosity and temperature-dependent thermal conductivity in the presence of exothermic catalytic chemical reaction along a curved surface. I recommend major revision due to the following facts.In Eq. (3), the authors added (u^2/2x)n to the convective acceleration term.Comment: What does the new term means? How did you derive it.Response: During dimensionalization of the momentum equation we have equation of the form u \u2202u/\u2202x+v \u2202u/\u2202y+u^2/2 1/g_x (dg_x)/dx=\u03b3_\u03bc (\u2202\u03b8/\u2202y)(\u2202u/\u2202y) +(1+\u03b3_\u03bc \u03b8)((\u2202^2 u)/(\u2202y^2 ))+\u03b8+\u03d5,Here, as 1/x \u00ae (P(x \u00ae)+Q(x \u00ae))=1/g_x (dg_x)/(dx \u00ae )and P(x \u00ae )+Q(x \u00ae )=n and thus 1/x \u00ae (n)=1/g_x (dg_x)/(dx \u00ae )u \u2202u/\u2202x+v \u2202u/\u2202y+u^2/2x n=\u03b3_\u03bc (\u2202\u03b8/\u2202y)(\u2202u/\u2202y) +(1+\u03b3_\u03bc \u03b8)((\u2202^2 u)/(\u2202y^2 ))+\u03b8+\u03d5, 2. After Eq. (6), it was written that n = P(x) + Q(x). Whereas  is the wall temperature function and the  is the body shape function.Comment: The authors refer Readers to check \"Pop, I. and Takhar, H. S. Free convection from a curved surface. Journal of Applied Mathematics and Mechanics, 73 (1993), pp. 534 -539\" for details.Comment: This is not acceptable. Update the research methodology with the derivation of such momentum equation.Response: The detail derivation of n=P(x)+Q(x) is given in below steps:Since we know that d/dx (lnx)=1/xand d(lnx)=1/x dxwhich implies that 1/(d(lnx))=x/dx. (1) Also consider d/dx (ln g_x )=1/g_x (dg_x)/dxwhich implies d(ln g_x )=1/g_x dg_x. (2) Now combining the above two equations (1) and (2), we have (d lng_x)/(d lnx)=x/g_x (dg_x)/dx.Now using the non-dimensionless variables, we may write the above equations as(d lng_x)/(d lnx \u00ael)=(x \u00ael)/g_x (dg_x)/(dx \u00ael)which implies that(d lng_x)/(d lnx \u00ael)=x \u00ae/g_x (dg_x)/(dx \u00ae )and thus we have 1/x \u00ae (d lng_x)/(d lnx \u00ael)=1/g_x (dg_x)/(dx \u00ae ) (3)Also, we consider d/dx (lnT_w )=1/T_w (dT_w)/dx=0which implies that d lnT_w=0and thus, we can write (d lnT_w)/(d lnx \u00ael)=0 (4)Now from equation (3) and (4), we have 1/x \u00ae ((d lnT_w)/(d lnx \u00ae l)+(d lng_x)/(d lnx \u00ae l))=1/g_x (dg_x)/(dx \u00ae )which can also be written as 1/x \u00ae (P(x \u00ae)+Q(x \u00ae))=1/g_x (dg_x)/(dx \u00ae ) (5)Here, P(x \u00ae), the wall temperature function and Q(x \u00ae) the body shape function, are defined as P(x \u00ae )=(d lnT_w)/(d lnx \u00ae l), Q(x \u00ae )=(d lng_x)/(d lnx \u00ae l) . (6) 3. Research question is needed to harmonize the contribution of the report to the body of knowledge.Comment: Research questions are needed at the end of the introduction section. Research questions are needed. Note that the results in this report are typical answers to unknown questions. This is true because the manuscript provides some powerful answers to unknown questions. Note that the research questions must connect the title to the analysis of results, and conclusion. This would guide authors not to generate many results that are not consistent to provide insight. The author should update the manuscript with appropriate and relevant research questions at the end of the introduction section. This would guide the author to structure logical analysis of results. Logical questions are expected. This would help readers to link what is known in the literature with the novelty of this study.Response: The overall objectives of this research are to develop the mathematical model to study and compare the different modes of coupling the exothermic and catalytic chemical reaction via momentum, energy and mass concentration equation. Model predictions are used to assess the effects of different parameters on conversion of exothermic catalytic chemical reaction at heated curve generated by tangential component of acceleration due to gravity. The proposed model is used as the guidelines for the selection of a suitable coupling to achieve the desired applications. A numerical technique Finite Difference Method in conjunction with primitive variable formulation is used to investigate the coupling of exothermic reaction with catalyst particles. Furthermore, parametric effects of heated wall and mass concentration along the curved surface are studied and highlighted graphically and as well as in tabular form. 4. The similarity variables presented as Eq. (7) are dimensional. The unit of the first, u, is m^0.5 while that of v is m^{-1/4}, and that of y is also dimensional. Hence, the variables used to non-dimenzionalize the governing equation are not appropriate.Response: In the section of numerical analysis, we have used primitive variable formulation given as below: u=x^(1\u20442) U,v=x^((-1)\u20444) V, x=X,y=x^(1\u20444) Y,  \u03b8=\u0398(X.Y), C=\u03a6.  It is pertinent to mention that primitive variable are dimensionless, we use this transformation to get primitive form of partial differential equations, please see red terms in each equation  After using the aforementioned transformations, we have the following form of system of equations:U/2+X \u2202U/\u2202X-Y/4 \u2202U/\u2202Y+\u2202V/\u2202Y=0,[1/2+n/2] U^2+XU \u2202U/\u2202X+(V-YU/4) \u2202U/\u2202Y=\u03b3_\u03bc \u2202\u0398/\u2202Y \u2202U/\u2202Y+(1+\u03b3_\u03bc \u0398) (\u2202^2 U)/(\u2202Y^2 )+\u0398+\u03a6,XU \u2202\u0398/\u2202X+(V-YU/4) \u2202\u0398/\u2202Y=1/Pr [\u03be(\u2202\u0398/\u2202Y)^2+(1+\u03be\u0398) (\u2202^2 \u0398)/(\u2202Y^2 )]+\u03b2\u03bb^2 X^(1\u20442) (1+n\u03b3\u0398)exp((-E)/(1+\u03b3\u03b8))\u0398,XU \u2202\u03a6/\u2202X+(V-YU/4) \u2202\u03a6/\u2202Y=1/Sc (\u2202^2 \u03a6)/(\u2202Y^2 )+\u03bb^2 X^(1\u20442) (1+n\u03b3\u0398)exp((-E)/(1+\u03b3\u03b8))\u03a6.Reviewer #2: Recommendation: Minor revisionAuthors should revise the manuscript according to the following comments.\u2022 Nomenclature is must.Response: The nomenclature has been included in the revised manuscript.\u2022 Some grammatical and typo mistakes are found in the manuscript.Response: In the revised manuscript we have correct the grammatical issues.\u2022 The governing differential equations describing the flow are non-linear. Is the solution obtained unique?Response: Please if you focus on the graphs and boundary conditionsU_=0, V_=0,\u0398_ =1, \u03a6_=1 at Y_j=0 U_\u21920, \u3016 \u03b8\u3017_\u21920, \u03a6_(i.j)\u21920 as Y_j\u2192\u221e In these graphs and all other graphs given in this study, the solutions are satisfying by the boundary conditions, it is evident of the correctness of the obtained results. \u2022 Specify the applications of considered physical model or geometry.Response: The proposed model is used as the guidelines for the selection of a suitable coupling to achieve the desired applications. The curved shaped geometry is used to design many problems of civil engineering as pressure barrier.\u2022 Introduction section should be made more concise to show previous work in the field. At present a lot of related researches are stated in the introduction. However, not sufficient analysis is presented. The authors should ask themselves: what are the problems with the presented researches? Why is the recent work needed? Hope these can improve the present work by following past articles.\u2022 Effect of Joule heating on MHD non\u2010Newtonian fluid flow past an exponentially stretching curved surface\u2022 Magneto hydrodynamic Cattaneo-Christov flow past a cone and a wedge with variable heat source/sink\u2022 Heat and mass transfer in MHD Casson nanofluid flow past a stretching sheet with thermophoresis and Brownian motion.\u2022 Effect of asymmetrical heat rise/fall on the film flow of magneto hydrodynamic hybrid Ferro fluid\u2022 Simultaneous solutions for first order and second order slips on micro polar fluid flow across a convective surface in the presence of Lorentz force and variable heat source/sink.\u2022 Effect of thermal radiation on MHD Casson fluid flow over an exponentially stretching curved sheet\u2022 Influence of non-uniform heat source/sink on the three-dimensional magneto hydrodynamic Carreau fluid flow past a stretching surface with modified Fourier\u2019s law\u2022 MHD Carreau Fluid Flow Past a Melting Surface with Cattaneo-Christov Heat Flux\u2022 Physical aspects on unsteady MHD\u2010free convective stagnation point flow of micro polar fluid over a stretching surface\u2022 Influence of viscous dissipation on MHD flow of micro polar fluid over a slandering stretching surface with modified heat flux model\u2022 A non\u2010Fourier heat flux model for magneto hydrodynamics micro polar liquid flow across a coagulated sheetNote: I want to see the revised version of the manuscript.Response: Most relevant papers are added to enrich introduction (see in introduction ref [23] - [30]) in the revised manuscript.AttachmentResponse to Reviewers Comments.docxSubmitted filename: Click here for additional data file. 28 Apr 2021PONE-D-21-04681R1Effects of Temperature Dependent Viscosity and Thermal Conductivity on Natural Convection Flow along a Curved Surface in the Presence of Exothermic Catalytic Chemical ReactionPLOS ONEDear Dr. Ali,Thank you for submitting your manuscript to PLOS ONE. After careful consideration, we feel that it has merit but does not fully meet PLOS ONE\u2019s publication criteria as it currently stands. Therefore, we invite you to submit a revised version of the manuscript that addresses the points raised during the review process.plosone@plos.org. When you're ready to submit your revision, log on to https://www.editorialmanager.com/pone/ and select the 'Submissions Needing Revision' folder to locate your manuscript file.Please submit your revised manuscript by Jun 12 2021 11:59PM. If you will need more time than this to complete your revisions, please reply to this message or contact the journal office at Please include the following items when submitting your revised manuscript:A rebuttal letter that responds to each point raised by the academic editor and reviewer(s). You should upload this letter as a separate file labeled 'Response to Reviewers'.A marked-up copy of your manuscript that highlights changes made to the original version. 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Protocols.io assigns your protocol its own identifier (DOI) so that it can be cited independently in the future. For instructions see:\u00a0We look forward to receiving your revised manuscript.Kind regards,Naramgari Sandeep, Ph.DAcademic EditorPLOS ONEJournal Requirements:Please review your reference list to ensure that it is complete and correct. If you have cited papers that have been retracted, please include the rationale for doing so in the manuscript text, or remove these references and replace them with relevant current references. Any changes to the reference list should be mentioned in the rebuttal letter that accompanies your revised manuscript. If you need to cite a retracted article, indicate the article\u2019s retracted status in the References list and also include a citation and full reference for the retraction notice.Reviewers' comments:Reviewer's Responses to Questions6. Review Comments to the AuthorPlease use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. Reviewer #1:\u00a0The report presents the natural convection boundary layer flow of a viscous incompressible fluid with temperature-dependent viscosity and temperature-dependent thermal conductivity in the presence of exothermic catalytic chemical reaction along a curved surface. I recommend minor revision due to the following facts.Q1. In Eq. (3), the authors added (u^2/2x)n to the convective acceleration term.Comment: What does the new term means? How did you derive it.In the report, the derivation presented by the Authors is in isolation. You are expected to derive it as a convective acceleration of momentum equation.Q2. After Eq. (6), it was written that n = P(x) + Q(x). Whereas  is the wall temperature function andthe  is the body shape function.This is the exact contribution of the report to the body of knowledge and it should be introduced under the introduction section. In fact, a paragraph is needed to announce this novelty.Q3. How do you study a fluid flow along a vertical surface without buoyancy forces? This is true because there is nothing like the associated dimensionless parameter called buoyancy parameter or Grashof number.Q4. Before Eq. 7, was defined as the tangential component of acceleration due to gravity. What is r in the definition?Reviewer #2:\u00a0The revisions are Good but some references are not arranged properly. Hence I recommend for possible publication.https://pacev2.apexcovantage.com/. PACE helps ensure that figures meet PLOS requirements. To use PACE, you must first register as a user. Registration is free. Then, login and navigate to the UPLOAD tab, where you will find detailed instructions on how to use the tool. If you encounter any issues or have any questions when using PACE, please email PLOS at\u00a0figures@plos.org. Please note that Supporting Information files do not need this step.While revising your submission, please upload your figure files to the Preflight Analysis and Conversion Engine (PACE) digital diagnostic tool,\u00a0 14 May 2021Reply to Review PONE-D-21-04681R1Effects of Temperature Dependent Viscosity and Thermal Conductivity on Natural Convection Flow along a Curved Surface in the Presence of Exothermic Catalytic Chemical Reaction PLOS ONEReviewer #1: The report presents the natural convection boundary layer flow of a viscous incompressible fluid with temperature-dependent viscosity and temperature-dependent thermal conductivity in the presence of exothermic catalytic chemical reaction along a curved surface. I recommend minor revision due to the following facts.Q1. In Eq. (3), the authors added (u^2/2x)n to the convective acceleration term.Comment: What does the new term means? How did you derive it. In the report, the derivation presented by the Authors is in isolation. You are expected to derive it as a convective acceleration of momentum equation.Response: The detail derivation of momentum equation is given as below:The dimensioned form of momentum equation in article is given as underu \u2202u/\u2202x+v \u2202u/\u2202y=1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)+g_x \u03b2_T (T-T_\u221e )+g_x \u03b2_C (C-C_\u221e) (1)Dimensionless variables x \u00ae=x/l,y \u00ae=y/l Gr^(1/4),u \u00ae=u/U_s ,v \u00ae=v/V_s Gr^(1/4),\u03b8=(T-T_\u221e)/(T_w-T_\u221e ) ,\u03d5 =(C-C_\u221e)/(C_w-C_\u221e ) (2)To convert the equation (1) into dimensionless form we use the dimensionless variables defined in equation (2), for this we find the term s one by one appeared in the equation (1)u \u2202u/\u2202x=U_s u \u00ae (\u2202U_s u \u00ae)/(\u2202x \u00ael)=(U_s^2)/l u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+\u3016U_s u \u00ae\u3017^2/l (\u2202U_s)/(\u2202x \u00ae )u \u2202u/\u2202x=(U_s^2)/l u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+\u3016U_s u \u00ae\u3017^2/l \u2202/(\u2202x \u00ae ) (g_x \u03b2_T \u0394T)^(1/2)u \u2202u/\u2202x=(U_s^2)/l u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+\u3016U_s u \u00ae\u3017^2/l (g_x \u03b2_T \u0394T)^(1/2) 1/(2\u221a(g_x )) (dg_x)/(dx \u00ae ) u \u2202u/\u2202x=(U_s^2)/l [u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )] (3)Nowv \u2202u/\u2202y=U_s v \u00aeGr^(-1/4) (\u2202U_s u \u00ae)/(\u2202ly \u00aeGr^(-1/4) )=(U_s^2)/l v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae ) (4)Now1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)=1/\u03c1 [\u2202\u03bc/\u2202y \u2202u/\u2202y+\u03bc (\u2202^2 u)/(\u2202y^2 )] (5)Considering \u2202\u03bc/\u2202y=\u2202/\u2202y \u03bc_o (1+\u03b3^* (T-T_\u221e))\u2202\u03bc/\u2202y=\u2202/(\u2202y \u00aelGr^(-1/4) ) (\u03bc_o (1+\u03b3^* \u0394T\u03b8))\u2202\u03bc/\u2202y=(\u03bc_o \u03b3^* \u0394T)/(lGr^(-1/4) ) \u2202\u03b8/(\u2202y \u00ae )\u2202\u03bc/\u2202y=(\u03bc_o \u03b3_T)/(lGr^(-1/4) ) \u2202\u03b8/(\u2202y \u00ae ) (6)\u2202u/\u2202y=(\u2202U_s u \u00ae)/(\u2202y \u00aelGr^(-1/4) )=U_s/(lGr^(-1/4) ) (\u2202u \u00ae)/(\u2202y \u00ae ) (7)(\u2202^2 u)/(\u2202y^2 )=(\u2202U_s u \u00ae)/(\u2202y \u00aelGr^(-1/4) )=U_s/(lGr^(-1/2) ) (\u2202^2 u \u00ae)/(\u2202y \u00ae^2 ) (8)Put eqs. (6)-(8) in eq. (5) we have 1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)=1/\u03c1 [(\u03bc_o \u03b3_\u03bc)/(lGr^(-1/4) ) \u2202\u03b8/(\u2202y \u00ae ) U_s/(lGr^(-1/4) ) (\u2202u \u00ae)/(\u2202y \u00ae )+(\u03bcU_s)/(lGr^(-1/2) ) (\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)=1/\u03c1 [(\u03bc_o \u03b3_\u03bc U_s)/(l^2 Gr^(-1/2) ) \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+\u3016\u03bc_o (1+\u03b3_\u03bc \u03b8)U\u3017_s/(l^2 Gr^(-1/2) ) (\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)=(\u03bc_o U_s)/(\u03c1l^2 Gr^(-1/2) ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]Where \u03b3_(\u03bc=) \u03b3^* \u0394T1/\u03c1 \u2202/\u2202y (\u03bc \u2202u/\u2202y)=(\u03bc_o U_s)/(\u03c1l^2 Gr^(-1/2) ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )] (9)Put the eqs. (3-4) and Eq. (9) in eq. (1)(U_s^2)/l [u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )]=(\u03bc_o U_s Gr^(1/2))/(\u03c1l^2 ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]+g_x \u03b2_T \u0394T\u03b8+g_x \u03b2_C \u0394C\u03d5 [u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )]=(\u03bc_o Gr^(1/2))/(\u03c1lU_s ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]+(\u3016lg\u3017_x \u03b2_T \u0394T\u03b8)/(U_s^2 )+(\u3016lg\u3017_x \u03b2_C \u0394T\u03d5)/(U_s^2 ) u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=(\u03bdGr^(1/2))/(lU_s ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]+(\u3016lg\u3017_x \u03b2_T \u0394T\u03b8)/(U_s^2 )+(\u3016lg\u3017_x \u03b2_C \u0394C\u03d5)/(U_s^2 )u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=(\u03bdGr^(1/2))/(lU_s ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]+(\u3016lg\u3017_x \u03b2_T \u0394T\u03b8)/(U_s^2 )+(\u3016lg\u3017_x \u03b2_C \u0394C\u03d5)/(U_s^2 )Where U_s=(g_x \u03b2_T \u0394Tl)^(1/2),Gr=(g_x \u03b2_T \u0394Tl^3)/\u03bd^2 and U_sc=(g_x \u03b2_T \u0394Cl)^(1/2),Gr^*=(g_x \u03b2_T \u0394Cl^3)/\u03bd^2 So u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=(\u03bdGr^(1/2))/(lU_s ) [\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )]+(U_s^2 \u03b8)/(U_s^2 )+(U_s^2 \u03d5)/(U_s^2 )u \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )+\u03b8+\u03d5 (10)Where the detail derivation of n=P(x)+Q(x) is given in below steps:Since we know thatd/dx (lnx)=1/xandd(lnx)=1/x dxwhich implies that1/(d(lnx))=x/dx. Also considerd/dx (ln g_x )=1/g_x (dg_x)/dxwhich impliesd(ln g_x )=1/g_x dg_x. (d lng_x)/(d lnx)=x/g_x (dg_x)/dx.Now using the non-dimensionless variables, we may write the above equations as(d lng_x)/(d lnx \u00ael)=(x \u00ael)/g_x (dg_x)/(dx \u00ael)which implies that(d lng_x)/(d lnx \u00ael)=x \u00ae/g_x (dg_x)/(dx \u00ae )and thus we have 1/x \u00ae (d lng_x)/(d lnx \u00ael)=1/g_x (dg_x)/(dx \u00ae ) Also, we consider d/dx (lnT_w )=1/T_w (dT_w)/dx=0which implies that d lnT_w=0and thus, we can write (d lnT_w)/(d lnx \u00ael)=0 Now from equation (c) and (d), we have1/x \u00ae ((d lnT_w)/(d lnx \u00ae l)+(d lng_x)/(d lnx \u00ae l))=1/g_x (dg_x)/(dx \u00ae )which can also be written as 1/x \u00ae (P(x \u00ae)+Q(x \u00ae))=1/g_x (dg_x)/(dx \u00ae ) Here, P(x \u00ae), the wall temperature function and Q(x \u00ae) the body shape function, are defined asP(x \u00ae )=(d lnT_w)/(d lnx \u00ae l), Q(x \u00ae )=(d lng_x)/(d lnx \u00ae l) . Now (10) becomesu \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2(P(x \u00ae )+Q(x \u00ae))+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )+\u03b8+\u03d5 (11) Now P(x \u00ae )+Q(x \u00ae )=nThus (11) becomesu \u00ae (\u2202u \u00ae)/(\u2202x \u00ae )+u \u00ae^2/2 1/g_x (dg_x)/(dx \u00ae )+v \u00ae (\u2202u \u00ae)/(\u2202y \u00ae )=\u03b3_\u03bc \u2202\u03b8/(\u2202y \u00ae ) (\u2202u \u00ae)/(\u2202y \u00ae )+(1+\u03b3_\u03bc \u03b8)(\u2202^2 u \u00ae)/(\u2202y \u00ae^2 )+\u03b8+\u03d5 Which is dimensionless form of momentum equation along curved surface, and n is the body shape parameter.Q2. After Eq. (6), it was written that n = P(x) + Q(x). Whereas  is the wall temperature function andthe  is the body shape function. This is the exact contribution of the report to the body of knowledge and it should be introduced under the introduction section. In fact, a paragraph is needed to announce this novelty.Response: In current paper we are investigated the natural convection flow over a two dimensional body of arbitrary geometric configuration in the presence of exothermic catalytic chemical reaction. The momentum, energy, and mass concentration equations are a general form suitable for laminar natural convection flows along curved surface in the inclusion of exothermic catalytic reaction. For body of arbitrary shape, the special case in which P(x \u00ae )+Q(x \u00ae )=n, thus the body shape parameter (index parameter) n has chosen 0<n\u22641/2 which is main novelty of this work.Note: This paragraph has inserted in the introduction section.Q3. How do you study a fluid flow along a vertical surface without buoyancy forces? This is true because there is nothing like the associated dimensionless parameter called buoyancy parameter or Grashof number.Response: Please if you see the dimensionless variables used to dimensionalize the flow model Dimensionless variables x \u00ae=x/l,y \u00ae=y/l Gr^(1/4),u \u00ae=u/U_s ,v \u00ae=v/V_s Gr^(1/4),\u03b8=(T-T_\u221e)/(T_w-T_\u221e ) ,\u03d5 =(C-C_\u221e)/(C_w-C_\u221e )  Here Grashof number is used as y \u00ae=y/l Gr^(1/4), v \u00ae=v/V_s Gr^(1/4) where Gr=(g\u03b2\u2206Tx^3)/\u03bd^2 , which is infact responsible for buoyancy force and it is used in dimensionalization . Dimensionless temperature variable \u03b8=(T-T_\u221e)/(T_w-T_\u221e ), it is the ratio of temperature difference. The problem under consideration is based on natural convection heat transfer, natural convection occurred because of the difference in density, and difference in density is due to the difference in temperature. The contribution of \u03b8 in momentum is obvious and sufficient answer to question.Q4. Before Eq. 7, was defined as the tangential component of acceleration due to gravity. What is r in the definition?Response: Here, x is the boundary layer coordinate along the curved surface while r and z are the horizontal and vertical coordinates of the points of the shape curve z=z(r) respectively. It is pertinent to mention that here flow is along the curved surface and dr/dz=0 means there is no flow inner side of the curve. The coordinate z is the vertical distance measure from the lower stagnation point (Please see fig. 1 flow configuration and coordinate system).Reviewer #2: The revisions are Good but some references are not arranged properly. Hence I recommend for possible publication.Response: We have focused on references, all the references are now in good order and well targeted to the problem under consideration.AttachmentResponse to Reviewers Comments.docxSubmitted filename: Click here for additional data file. 17 May 2021Effects of Temperature Dependent Viscosity and Thermal Conductivity on Natural Convection Flow along a Curved Surface in the Presence of Exothermic Catalytic Chemical ReactionPONE-D-21-04681R2Dear Dr. Ali,We\u2019re pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it meets all outstanding technical requirements.Within one week, you\u2019ll receive an e-mail detailing the required amendments. When these have been addressed, you\u2019ll receive a formal acceptance letter and your manuscript will be scheduled for publication.http://www.editorialmanager.com/pone/, click the 'Update My Information' link at the top of the page, and double check that your user information is up-to-date. If you have any billing related questions, please contact our Author Billing department directly at authorbilling@plos.org.An invoice for payment will follow shortly after the formal acceptance. To ensure an efficient process, please log into Editorial Manager at onepress@plos.org.If your institution or institutions have a press office, please notify them about your upcoming paper to help maximize its impact. If they\u2019ll be preparing press materials, please inform our press team as soon as possible -- no later than 48 hours after receiving the formal acceptance. Your manuscript will remain under strict press embargo until 2 pm Eastern Time on the date of publication. For more information, please contact Kind regards,Naramgari Sandeep, Ph.DAcademic EditorPLOS ONEAdditional Editor Comments :The revised version is acceptable for publication.Reviewers' comments: 19 Jul 2021PONE-D-21-04681R2 Effects of Temperature Dependent Viscosity and Thermal Conductivity on Natural Convection Flow along a Curved Surface in the Presence of Exothermic Catalytic Chemical Reaction Dear Dr. Ali:I'm pleased to inform you that your manuscript has been deemed suitable for publication in PLOS ONE. Congratulations! Your manuscript is now with our production department. onepress@plos.org.If your institution or institutions have a press office, please let them know about your upcoming paper now to help maximize its impact. If they'll be preparing press materials, please inform our press team within the next 48 hours. Your manuscript will remain under strict press embargo until 2 pm Eastern Time on the date of publication. For more information please contact plosone@plos.org. 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{"text": "The electrophilic activation of B\u2212H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12\u2010 and 7\u2010[2\u2010(tBuN{H}CH)C6H4Te(CB11H11)] in ratios ranging from 62\u2009:\u200938 to 80\u2009:\u200920.The aryltellurenyl cation [2\u2010( B\u2212H bond activation: The Lewis superacidic aryltellurenyl cation [2\u2010(tBuNCH)C6H4Te]+ increases the Br\u00f8nsted acidity of the weakly coordinating carborane anion (CB11H12)\u2212 by more than 120 orders of magnitude. Upon heating, the formal B\u2212H bond is converted into an acidic N\u2212H bond, while a Te\u2212B bond is formed. A mechanism for the electrophilic substitution is proposed. Main\u2010group elements mediating bond activation of small molecules and catalytic transformations have attracted considerable attention in recent years.tBuNCH)C6H4Te]+ (I), containing an imino donor functionality can be regarded as an intramolecular regular N\u2192Te Lewis pair, however, the intramolecularly coordinating 2\u2010tert\u2010butyl\u2010iminomethylphenyl group compensates the electron deficiency at the tellurium atom only insufficiently .tBuNCH)C6H4Te][X] 3}4]\u2212) show significant Te\u22c5\u22c5\u22c5O and Te\u22c5\u22c5\u22c5F interactions in the solid state, whereas in nonpolar solvents the electrolytic dissociation remains incomplete. In an effort to obtain an essentially isolated [2\u2010(tBuNCH)C6H4Te]+ (I) cation, we turned our attention to an alternative WCA, namely, the closo\u2010carborane anion [CB11H12]\u2212, which is known as robust entity with a very low reactivity.tBuNCH)C6H4TeCl (II)11H12]tBuNCH)C6H4Te][CB11H12] (1), which was isolated as yellow crystals in 99\u2009% yield (Scheme\u20051 is shorter than that of (tBuNCH)C6H4Te][O3SCF3] (2.113(1)\u2005\u00c5), but longer than those of (tBuNCH)C6H4Te][SbF6] (2.076(2)\u2005\u00c5) and (tBuNCH)C6H4Te][Al{OC(CF3)3}4] (2.051(4)\u2005\u00c5). The cation and anion of 1 are associated by a prominent Te\u22c5\u22c5\u22c5H contact (2.550(1)\u2005\u00c5) with the B\u2212H functionality in the B12 position.1 is in fact only metastable and susceptible to further transformations at slightly elevated temperatures, both in CH2Cl2 and the solid state. Gentle heating of 1 in inert solvents produced a mixture of two isomeric dinuclear donor\u2010acceptor complexes [2\u2010(tBuNCH)C6H4Te\u22c5D][CB11H12] C6H4Te]CB11H11 (5\u2009a) and 2\u2009b, D=7\u2010[2\u2010(tBuN{H}CH)C6H4Te]CB11H11 (5\u2009b)) in ratio 80\u2009:\u200920,2\u2009a(2\u2009b) (3.034(1)\u2005\u00c5) is substantially longer than that of [MesTe(TeMes2)](O3SCF3) (2.808(1)\u2005\u00c5)2)](SbF6) (2.765(1)\u2005\u00c5)2\u2009a(2\u2009b) (2.228(1)\u2005\u00c5) is substantially longer than in 1. As a result, the corresponding Te\u2192Te vibration mode in Raman spectra of 2\u2009a(2\u2009b) (122\u2005cm\u22121) is considerably shifted bathochromically in comparison to ([MesTe(TeMes2)](SbF6) (143\u2005cm\u22121) indicating a rather weak Te\u2212Te bond.2\u2009a(2\u2009b) is virtually insoluble in CH2Cl2 and aromatic solvents, it very easily dissolves in THF via dissociation of the Te\u2192Te bond . Consequently, the formation of 1\u2005equiv. of [2\u2010(tBuNCH)C6H4Te\u22c5THF][CB11H12] (3) is observed along with releasing of (1\u2212x)\u2005equiv. of 12\u2010[2\u2010(tBuN{H}CH)C6H4Te]CB11H11 (5\u2009a) and x\u2005equiv. of 7\u2010[2\u2010(tBuN{H}CH)C6H4Te]CB11H11 (5\u2009b) from the mixture of 2\u2009a and 2\u2009b in molar ratio (1\u2212x):x (Scheme\u2005tBuNCH)C6H4TeCl with Ag[CB11H12] directly afforded the mononuclear donor\u2010acceptor complexes [2\u2010(tBuNCH)C6H4Te\u22c5D][CB11H12] 3 (D=THF) and 4 (D=DMAP) as yellowish crystals in 95\u2009% and 83\u2009% yield  with the following activation parameters: \u0394G\u2260298=118.4\u2005kJ\u2009mol\u22121; \u0394H\u2260=114.9\u2005kJ\u2009mol\u22121; \u0394S\u2260=\u221211.8\u2005J\u2009mol\u22121 K\u22121. The most straightforward way providing the quantitative yield of the zwitterionic species 5\u2009a and 5\u2009b (in a ratio of 62\u2009:\u200938) was heating of complex 3 in the solid state at 140\u2009\u00b0C for 2.5\u2005h, which effectively removes the THF (details in the Supporting Information). The formation of 5\u2009a and 5\u2009b (donors D in case of 2\u2009a(2\u2009b)) may be rationalized by hydrogen transfer from the B\u2212H functions in the B12 and B7 positionscloso\u2010carborane anion [CB11H12]\u2212 to the lone pair of the N atom in 1, upon which a Te\u2212B12(B7) bond is formed. This hydrogen transfer is facilitated by the cooperative reactivity of the intramolecular regular N\u2192Te Lewis pair. While the Lewis acidic Te site reverses the formal polarity of the B\u2212H bond from hydridic to protic, the Lewis basic N\u2010atom serves as a final proton acceptor within its gradual transfer from the Te atom to the N atom . Thus, the Lewis super acid [2\u2010(tBuNCH)C6H4Te]+ (I) has activated the closo\u2010carborane ion [CB11H12]\u2212, which serves as a proton donor. In fact, such a bond arrangement gives a unique insight into a long unresolved issue of electrophilic activation of closo\u2010[CB11H12]\u2212 (see below).3) to dark red, but also by a dramatic change in the \u03b4(125Te) valuesII site to neutral in the zwitterionic 5\u2009a(5\u2009b) by the Te\u2212B12(B7) bond formation. Consequently, the boron atom at the B12 position of the free [CB11H12]\u2212 anion of 3 resonating in 11B NMR at \u22127.3\u2005ppm is high\u2010field shifted upon formation of Te\u2212B12 bond in compound 5\u2009a to \u221211.5\u2005ppm. While the unsubstituted B12 atom in case of 5\u2009b containing Te\u2212B7 bond resonates slightly more low\u2010field at \u22125.8\u2005ppm, the signal of boron atom at the B7 position is shifted to high field from \u03b4(11B)=\u221213.7\u2005ppm in 3 to \u03b4(11B)=\u221217.3\u2005ppm. Interestingly, both Te\u2212B12 and Te\u2212B7 atoms in 5\u2009a and 5\u2009b are in 11B NMR significantly low\u2010field shifted (\u0394\u03b4 \u223c7\u2005ppm) in comparison to analogously monoiodo substituted derivatives of closo\u2010carbadodecaborate.5\u2009a(5\u2009b) features a weak intramolecular hydrogen bond of the type N\u2212H\u22c5\u22c5\u22c5Te (N\u2212H: 0.860(2)\u2005\u00c5, H\u22c5\u22c5\u22c5Te (2.568(1)\u2005\u00c5, N\u22c5\u22c5\u22c5Te: 3.320(1)\u2005\u00c5), in which Te serves as unprecedented hydrogen bond acceptor. This bonding situation is a result of the 5\u2009a(5\u2009b) formation mechanism (see below) enforcing the E configuration of the protonated imino CH=NH+ moiety for both products, which is manifested by observation of typical 3J values (acquired in CD2Cl2) of 17.3 and 17.4\u2005Hz, respectively. Although the intramolecular hydrogen bond of the type N\u2212H\u22c5\u22c5\u22c5Te was found in the solid state, the coupling constant 1J=85.3\u2005Hz for both 5\u2009a and 5\u2009b in the solution spectra lies in range for protonated imines.5\u2009a and 5\u2009b contain such bonding interaction, FTIR is showing no shift of the N\u2212H bond \u03bd vibration in the solid state sample (5\u2009a: 3244\u2005cm\u221215\u2009b: 3295\u2005cm\u22121) in comparison to adducts 2\u2009a and 2\u2009b (3244\u2005cm\u22121 and 3297\u2005cm\u22121) having no N\u2212H\u22c5\u22c5\u22c5Te interaction. Finally, deprotonation of 5\u2009a(5\u2009b) was achieved upon addition of triethylamine, which afforded a mixture of [Et3NH][12\u2010{2\u2010(tBuNCH)C6H4Te}CB11H11] (6\u2009a) and [Et3NH][12\u2010{2\u2010(tBuNCH)C6H4Te}CB11H11] (6\u2009b) in the same molar ratio as given by parent compounds 5\u2009a(5\u2009b), which was isolated as orange oil in quantitative yield (Scheme\u2005\u03b4(15N)=\u2212172.1\u2005ppm acquired in [D8]THF for 5\u2009a(5\u2009b) is shifted to low field for 6\u2009a and 6\u2009b up to \u221235.4 and \u221232.8\u2005ppm, respectively. Despite the assessable lone pair of the N atom in the 6\u2009a(6\u2009b) for coordination of Te atom, we can conclude that in this case no N\u2192Te interaction is present, as \u03b4(15N) for these compounds approaches the value of \u03b4(15N) for the unsubstituted parent Schiff base, namely (tBuNCH)C6H5 .The aryltellurenyl cation, + (I) induces an electrophilic activation of the 12\u2010 or 7\u2010B\u2212H bond in the closo\u2010carborane ion5\u2009a and 5\u2009b. The proton transfer from 1\u2019 to 5\u2009a is associated with an energy gain of 193.3\u2005kJ\u2009mol\u22121 and most likely proceeds via a concerted wagging motion involving the transition state TS with double triangular arrangement of N, Te and B12\u2212H, which accounts for an activation barrier of 118.1\u2005kJ\u2009mol\u22121  as discussed above. The AIM bond topology of TS reveals a curved Te\u2212H(B) bond path, indicating the onset of Te\u2212B bond formation ) of 0.59 e\u00c5\u20103 and considerably negative total energy over ED ratio (H/\u03c1(r)) of \u22120.38\u2005a.u., covalent bonding aspects of the Te\u2212H contact in the TS are much higher than in 1 (\u03c1(r)=0.34, H/\u03c1(r)=\u22120.21\u2005a.u.) and 5\u2009a (\u03c1(r)=0.23, H/\u03c1(r)=\u22120.14\u2005a.u.). This is supported by the NCI, which shows a ring\u2010shaped and red\u2010colored NCI basin enclosing the Te\u2212H and Te\u2212B bonding axes, in contrast to the disc\u2010shaped and blue\u2010colored NCI basins in 1 and 5 . In 5\u2009a, only the N (77\u2009%) and now protic H (23\u2009%) atoms contributions are relevant, supporting a coordinative Te\u22c5\u22c5\u22c5H bonding mode C6H4Te]+ (I), and the weakly coordinating closo\u2010carborane anion [CB11H12]\u2212 give rise to a metastable contact ion pair [2\u2010(tBuNCH)C6H4Te][CB11H12] (1), in which the B\u2212H bond in the 12\u2010 or 7\u2010position of closo\u2010[CB11H12]\u2212 is activated by the proximity of a Lewis superacidic cation, the Br\u00f8nsted acidity of the closo\u2010carborane is extremely increased, and this triggers proton transfer and the formation of 12\u2010[2\u2010(tBuN{H}CH)C6H4Te]CB11H11 (5\u2009a) and 7\u2010[2\u2010(tBuN{H}CH)C6H4Te]CB11H11 (5\u2009b) in ratios ranging from 62\u2009:\u200938 to 80\u2009:\u200920.1 can be regarded as a snapshot of the first step of the electrophilic substitution of closo\u2010[CB11H12]\u2212, which is poorly understood in general.closo\u2010[CB11H12]\u2212[22] involving the formation of three\u2010center bonded intermediate [MeBH]+. We are currently investigating the utility of I for the activation of small molecules.In summary, the aryltellurenyl cation [2\u2010 should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "The di\u00adhydro\u00adquinoxaline moiety, with the exception of the N atom, is essentially planar with the attached phenyl ring inclined to it by 11.64\u2005(6)\u00b0 and the inner part of the methyl\u00adpropano\u00adate group nearly perpendicular to it. In the crystal, inversion dimers formed by C\u2014H\u22efO hydrogen bonds are connected into oblique stacks by \u03c0-stacking and C\u2014H\u22ef\u03c0(ring) inter\u00adactions. 18H16N2O3, the di\u00adhydro\u00adquinoxaline moiety, with the exception of the N atom is essentially planar with the inner part of the methyl\u00adpropano\u00adate group (CH2\u2014CH2\u2014O) nearly perpendicular to it. In the crystal, inversion dimers formed by C\u2014H\u22efO hydrogen bonds are connected into oblique stacks by \u03c0-stacking and C\u2014H\u22ef\u03c0(ring) inter\u00adactions.In the title mol\u00adecule, C The overall conformation is determined in part by the intra\u00admolecular C5\u2014H5\u22efO3 and C14\u2014H14\u22efO1 hydrogen bonds \u2005\u00c5 (r.m.s. deviation of the nine fitted atoms = 0.0116\u2005\u00c5). N1 lies 0.0526\u2005(12)\u2005\u00c5 below the mean plane. The C9\u2013C14 phenyl ring is inclined to the above plane by 11.64\u2005(6)\u00b0 while the inner part \u2005\u00c5, dihedral angle = 12.20\u2005(6)\u00b0] and in addition C16\u2014H16B\u22efO3ii and C18\u2014H18A\u22efCg2iii inter\u00adactions . The crystal packing also shows a C17=O3\u22efCg2 inter\u00adaction .In the crystal, inversion dimers are formed by C4\u2014H4\u22efO3et al., 2016II yielded 30 hits of which those most similar to the title mol\u00adecule have the formula III with R = Me and R\u2032 = CH2CO2H   and side (bottom) views of the Hirshfeld surface plotted over dnorm in the range \u22120.1367 to 1.2965 a.u. One of the intra\u00admolecular C\u2014H\u22efO hydrogen bonds is indicated by the arrow at the left in the front view while those leading to the formation of the inversion dimers are shown by the arrows on the right of the front view. The C\u2014H\u22ef\u03c0(ring) inter\u00adaction and the \u03c0-stacking inter\u00adactions are represented by the red spots designated by arrows in the side view. Fig.\u00a03b presents the same two views of the surface plotted over the shape-index. In the front view, the \u03c0-stacking inter\u00adaction is evident at the center as an orange triangle surrounded by blue triangles. Fig.\u00a03c has the same two views of the surface plotted over the curvature index, with the flat area in the center indicating the locus of the \u03c0-stacking inter\u00adaction. Fig.\u00a04a) and those delineated into H\u22efH contacts , H\u22efO/O\u22efH contacts , H\u22efC/C\u22efH contacts  and C\u22efC contacts .An effective means of probing inter\u00admolecular inter\u00adactions is Hirshfeld surface analysis  were added 2-bromo\u00adethyl acetate , potassium carbonate  and a catalytic qu\u00adantity of tetra-n-butyl\u00adammonium bromide. The reaction mixture was stirred at room temperature for 24\u2005h. The solution was filtered and the solvent removed under reduced pressure. The residue thus obtained was chromatographed on a silica gel column using a hexa\u00adne/ethyl acetate 9.5: 0.5 mixture as eluent. The solid obtained was recrystallized from ethanol solution to afford colorless column-like specimen of the title compound. Yield: 0.50\u2005g, 67%; m.p. 471\u2013473\u2005K.To a solution of 2-oxo-3-phenyl-1,2-di\u00adhydro\u00adquinoxaline  in 1H NMR  \u03b4 (ppm): 8.24 ; 7.91 ; 7.82 ; 7.53 ; 7.25 ; 4.73 ; 3.92 ; 2.23 .13C NMR  \u03b4 (ppm):46.15 (N\u2014CH2); 61.15 (O\u2014CH2); 114.38, 123.82, 127.01, 127.72, 128.13, 128.96, 129.68, 130.33, 130.45,130.62 (CH\u2014Ar); 132.78, 133.36, 135.40, 136.05, 154.24(Cq); 156.92 (C=O); 177.82 (O\u2014C=O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021005247/vm2249sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021005247/vm2249Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021005247/vm2249Isup3.cmlSupporting information file. DOI: 2062956CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Additional N\u2014H\u22efO hydrogen bonds link the chains into layers parallel to (100).The title mol\u00adecule adopts an angular conformation. In the crystal, N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) inter\u00adactions form chains extending along the  13H16N4O, adopts an angular conformation. In the crystal a layer structure is generated by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) inter\u00adactions. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (53.8%), H\u22efC/C\u22efH (21.7%), H\u22efN/N\u22efH (13.6%), and H\u22efO/O\u22efH (10.8%) inter\u00adactions. The optimized structure calculated using density functional theory (DFT) at the B3LYP/ 6\u2013311\u2005G level is compared with the experimentally determined structure in the solid state. The calculated HOMO\u2013LUMO energy gap is 5.0452\u2005eV.The title mol\u00adecule, C Bond diB\u22efO1, and N2\u2014H2A\u22efN1 hydrogen bonds, together with C11\u2014H11\u22efCg2 inter\u00adactions . The positive electrostatic potential (blue region) over the surface indicates hydrogen-donor potential, whereas the hydrogen-bond acceptors are represented by negative electrostatic potential (red region). The shape-index . The most important inter\u00adaction is H\u22efH, contributing 53.8% to the overall crystal packing, which is reflected in Fig.\u00a06b as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule, with the tip at de = di = 1.18\u2005\u00c5. In the presence of C\u2014H inter\u00adactions, the pair of characteristic wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts (21.7% contribution to the HS), Fig.\u00a06c, has the tips at de + di = 2.76\u2005\u00c5. The pair of scattered points of spikes in the fingerprint plot delineated into H\u22efN/N\u22efH, Fig.\u00a06d (13.6%), have the tips at de + di = 2.01\u2005\u00c5. Finally, the H\u22efO/O\u22efH contacts, Fig.\u00a06e, make only a 10.8% contribution to the HS and have a low-density distribution of points.The overall two-dimensional fingerprint plot , hardness (\u03b7), ionization potential (I), dipole moment (\u03bc), electron affinity (A), electrophilicity (\u03c9) and softness (\u03c3) are collated in Table\u00a03N-(2-amino-5-methyl\u00adphen\u00adyl)-2-(5-methyl-1H-pyrazol-3-yl)acetamide system. The energy band gap [\u0394E = LUMOE\u00a0\u2212\u00a0HOMOE] of the mol\u00adecule is 5.0452\u2005eV, and the frontier mol\u00adecular orbital energies, HOMOE and LUMOE, are \u22125.3130 and \u22120.2678\u2005eV, respectively.The structure in the gas phase of the title compound was optimized by means of density functional theory. The density functional theory calculation was performed by the hybrid B3LYP method and the 6\u2013311\u2005G basis-set, which is based on Becke\u2019s model acetamide fragment yielded multiple matches. Of these, two had an N-(2-amino\u00adphen\u00adyl) substituent comparable to (I)et al., 2019cN-(2-{[(4-methyl\u00adphen\u00adyl)methyl\u00adidene]amino}\u00adphen\u00adyl) on nitro\u00adgen 2. The second one (III)  on nitro\u00adgen 2. The pyrazole ring (N3/N4/C10\u2013C12) in XITFUE is inclined to the C1\u2013C6 benzene ring by 70.83\u2005(8)\u00b0. In YODZEZ, the dihedral angle between the mean planes of the 2-amino\u00adphenyl and pyrazolyl rings is 65.63\u2005(8)\u00b0. In (I)A search of the Cambridge Structural Database -4-(2-oxo\u00adpropyl\u00adidene)-1,5-benzodiazepin-2-one and a stoichiometric amount of hydrazine were refluxed in ethanol (40\u2005mL) for 2\u2005h. After concentration of the solvent volume to 20\u2005mL, the solution was allowed to stand; the precipitate formed was filtered off and then recrystallized in ethanol. Single crystals were obtained after recrystallization from methanol in the presence of MnCl2\u00b74H2O, which was left at room temperature for 72\u2005h. Yield: 70%.2\u2005g (9.3\u2005mmol) of  global, I. DOI: 10.1107/S205698902100503X/dj2025Isup5.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902100503X/dj2025Isup3.cmlSupporting information file. DOI: 2083102CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The layered crystal packing is further consolidated by van der Waals and C\u2014H\u22ef\u03c0 inter\u00adactions.In the crystal, mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds into ribbons along the  14H12N4O7\u00b70.224H2O, is nearly planar with a maximum deviation from the least-squares plane of 0.352\u2005(1)\u2005\u00c5. The mol\u00adecular conformation is stabilized by an intra\u00admolecular N\u2014H\u22efO hydrogen bond, generating an S(6) ring motif. In the crystal, mol\u00adecules are linked by centrosymmetric pairs of N\u2014H\u22efO hydrogen bonds, forming ribbons along the c-axis direction. These ribbons connected by van der Waals contacts, forming sheets parallel to the ac plane. There are also inter\u00admolecular van der Waals contacts and and C\u2014H\u22ef\u03c0 inter\u00adactions between the sheets. A Hirshfeld surface analysis indicates that the most prevalent inter\u00adactions are O\u22efH/H\u22efO (41.2%), H\u22efH (19.2%), C\u22efH/H\u22efC (12.2%) and C\u22efO/ O\u22efC (8.4%).In the crystal, the whole mol\u00adecule of the title compound, C The title mol\u00adecule Fig.\u00a01 is nearlc-axis direction  to the Hirshfeld surface. The other large contributions to the Hirshfeld surface are from H\u22efH , C\u22efH/H\u22efC  and C\u22efO/O\u22efC  inter\u00adactions. All contributions to the Hirshfeld surface are listed in Table\u00a03The Hirshfeld surface for the title mol\u00adecule was performed and its associated two-dimensional fingerprint plots were prepared using et al., 2016H-imidazol-5-yl)methyl\u00adidene]-1-methyl\u00adhydrazin\u00adyl}pyridine methyl\u00adidene]-1-methyl\u00adhydrazin\u00adyl}-1H-benzimidazole monohydrate methyl\u00adidene]hydrazin\u00adyl}-1H-benzimidazole hydrate unknown solvate -2-methyl\u00adhydrazinyl\u00adidene]meth\u00adyl}-1H-imidazol-3-ium tri\u00adfluoro\u00admeth\u00adane\u00adsulfonate monohydrate methyl\u00adene]-1-methyl\u00adhydrazine\u00adyl}pyridin-1-ium) bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonate) , an inter\u00adesting example of a non-typical F\u22efO inter\u00adaction was found whose length, 2.859\u2005(2)\u2005\u00c5, is one of the shortest ever reported.Diazo\u00adtization: 2.09\u2005g (10\u2005mmol) of dimethyl 5-amino\u00adisophthalate were dissolved in 50\u2005mL of water, the solution was cooled on an ice bath to 273\u2005K and 0.69\u2005g (10\u2005mmol) of NaNO2 were added; 2.00\u2005mL of HCl were then added in 0.5\u2005mL portions over 1\u2005h. The temperature of the mixture should not exceed 278\u2005K.Azocoupling: NaOH  was added to a mixture of 10\u2005mmol (1.28\u2005g) of barbituric acid with 25.00\u2005mL of water. The solution was cooled on an ice bath and a suspension of 3,5-bis(meth\u00adoxy\u00adcarbon\u00adyl)benzene\u00addiazo\u00adnium chloride, prepared according to the procedure described above, was added in two equal portions under vigorous stirring for 1\u2005h. The formed precipitate of the title compound was filtered off, recrystallized from methanol and dried in air. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.The title compound: Yield, 68% (based on barbituric acid), yellow powder soluble in DMSO, methanol, ethanol and DMF. Analysis calculated for C14H12N4O7 (Mr = 348.27): C, 48.28; H, 3.47; N, 16.09; found: C, 48.25 H, 3.41; N, 16.03%. ESI\u2013MS: m/z: 349.2 [Mr + H]+. IR (KBr): 3160, 3090 and 2846 \u03bd(NH), 1745 and 1663 \u03bd(C=O), 1610 \u03bd(C=O\u22efH) cm\u22121. 1H NMR (300.130\u2005MHz) in DMSO-d6, inter\u00adnal TMS, \u03b4 (ppm): 8.20\u20138.36 , 11.32 , 11.54 , 14.08 . 13C{1H} NMR . \u03b4: 55.6 (2OCH3), 119.54 (2Ar\u2014H), 121.8 (Ar-H), 127.4 (2C\u2014COOCH3), 133.25 (C=N), 142.87 (C\u2014NHN=), 150.24 (C=O), 160.32 (C=O), 161.90 (C=O\u22efH) and 166.56 (2COOCH3).Uiso(H) = 1.2 or 1.5Ueq(C). There is a small cavity in the crystal, which is only partially occupied by a water mol\u00adecule, with an occupancy of 0.224\u2005(5), and its hydrogen atoms could not be located.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989021006563/yk2153sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021006563/yk2153Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021006563/yk2153Isup3.cmlSupporting information file. DOI: 2091530CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two fused five-membered rings and their N-bound aromatic substituents form a pincer-like motif. In the crystal, a combination of C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0(ring) inter\u00adactions leads to the formation of layers parallel to the  33H26N4O4, the two fused five-membered rings and their N-bound aromatic substituents form a pincer-like motif. The relative conformations about the three chiral carbon atoms are established. In the crystal, a combination of C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds and C\u2014H\u22ef\u03c0(ring) inter\u00adactions leads to the formation of layers parallel to the bc plane. A Hirshfeld surface analysis indicates that the most significant contributions to the crystal packing are from H\u22efH (44.3%), C\u22efH/H\u22efC (29.8%) and O\u22efH/H\u22efO (15.0%) contacts.In the title compound, C The pyrrolo\u00adoxazole fragment is folded along the C2\u22efC5 axis by 62.63\u2005(8)\u00b0 while the dihedral angle between the C2/C3/N2/C4/C5 and C27\u2013C32 rings is 67.11\u2005(8)\u00b0. The C9\u2013C14 and C15\u2013C20 rings are inclined to the C6/C7/N3/N4/C8 ring by 32.32\u2005(9) and 33.52\u2005(9)\u00b0, respectively.A puckering analysis of the oxazole fragment  and Fig.\u00a05b) show the front and back sides of the three-dimensional Hirshfeld surface of the title compound plotted over dnorm in the range \u22120.3067 to 1.6634 a.u. The red spots highlight the inter\u00adatomic contacts, including the C\u2014H\u22efO hydrogen bonds.A Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were performed with a\u2013d, respectively. The other minor contributions to the Hirshfeld surface are by N\u22efH/H\u22efN (6.5%), C\u22efC (1.8%), O\u22efC/C\u22efO (1.3%), N\u22efO/O\u22efN (0.5%), O\u22efO (0.5%) and N\u22efC/C\u22efN (0.3%) contacts. The large number of H\u22efH, C\u22efH/H\u22efC and O\u22efH/H\u22efO inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing , C\u22efH/H\u22efC (29.8%) and O\u22efH/H\u22efO (15.0%) contacts Table\u00a02 are illuR,7aS)-1,3,5,6,7,7a-hexa\u00adhydro-3-(2-hy\u00addroxy\u00adphen\u00adyl)-1,1-di\u00adphenyl\u00adpyr\u00adrolo\u00adoxazol-6-ol benz\u00aden\u00adamine oxide  in toluene (15\u2005ml) was heated at 373\u2005K under reflux for 24\u2005h, the reaction was monitored by TLC. The endo isomer was filtered off as a major product. The title compound was recrystallized from a mixture of toluene and petroleum ether as colorless crystals in 60% yield; mp: 469\u2013471\u2005K.A mixture of Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021002358/ex2041sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021002358/ex2041Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021002358/ex2041Isup3.cmlSupporting information file. DOI: 2067379CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "To predict the clinical manifestations of \u03b1-globin gene aberration for genetic counseling, we examined the prevalence of the \u03b1-globin triplication and the genotype\u2013phenotype correlation in this subpopulationA cohort of 7644 subjects was selected from nine ethnicities covering four regions in Guizhou province of China. Peripheral blood was collected from each participant for routine blood testing and hemoglobin electrophoresis. PCR-DNA sequencing and Gap-PCR were used to identify the thalassemia gene mutations. Chi-square tests and one-way\u00a0analysis of variance (ANOVA) were used to statistically analyze the data.anti4.2/\u03b1\u03b1 accounted for 0.523% (40/7644), the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 for 0.235% (18/7644), and the \u03b1\u03b1\u03b1anti3.7/\u2013SEA for 0.013% (1/7644). The \u03b1\u03b1\u03b1anti4.2/\u03b1\u03b1 is more prevalent than the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 in Guizhou. In addition, the frequency of the HK\u03b1\u03b1/\u03b1\u03b1 (that by GAP-PCR is like \u03b1\u03b1\u03b1anti4.2/-\u03b13.7) was 0.235% (18/7644). Ethnically, the Tujia group presented the highest prevalence (2.47%) of \u03b1-globin triplication. Geographically, the highest frequency of the \u03b1-globin triplication was identified in Qiannan region (2.23%). Of the triplicated \u03b1-globin cases, 5 coinherited with heterozygote \u03b2-thalassemia and presented various clinical manifestations of anemia.We found that the frequency of \u03b1-globin triplication in Guizhou province was 0.772% (59/7644). Genotypically, the \u03b1\u03b1\u03b1These data will be used to update the Chinese triplicated \u03b1-globin thalassemia database and provide insights into the pathogenesis of thalassemia. These findings will be helpful for the diagnosis of thalassemia and future genetic counseling in those regions. Based o\u03b1anti4.2 , 12. Theulations \u201313. In aunctions , 15. ButGuizhou province, located in southwestern China, is one of the regions with the highest rate of \u03b1-thalassemia in Asia . The popGuizhou province contains four regions. Two representative counties/cities from each region were taken for study. Inclusion criteria: subjects whose residence in these regions exceeded 3\u00a0years at the time of recruitment, regardless of age, sex, and ethnicity. In total, 7866 participants were recruited by simple random sampling method from 8 counties/cities  in four regions  of Guizhou province in China from February 2014 to June 2016. Eventually, blood samples and health information were collected from 7644 qualified people for investigation based on the inclusion criteria  and hemoglobin electrophoresis .http://www.HGVS.org/varnomen).Approximately 3\u00a0ml of peripheral blood was collected from each subject. DNA extraction was conducted by using the Magen nucleic acid extraction kit . Four pairs of globin gene specific PCR primers  were designed and synthesized by the Beijing Genome Institute (BGI)-Shenzhen. For identification of HK\u03b1\u03b1, next-generation sequencing plus Gap-PCR were adopted. All the globin gene-specific PCR primers were owned and patented by the BGI-Shenzhen, and unpublicized. PCR was carried out in a volume of 25\u00a0\u03bcl with an amplification reaction system containing 1 pair of tag primers, 50\u2013200\u00a0ng DNA, and 2\u2009\u00d7\u2009Gold Star Taq Master Mix (Kangwei century). The PCR amplification was performed using the ABI9700 . The PCR conditions: 95\u00a0\u00b0C 10\u00a0min; 95\u00a0\u00b0C 30\u00a0s, 60\u00a0\u00b0C 30\u00a0s, 72\u00a0\u00b0C 50\u00a0s, 35 cycles; 72\u00a0\u00b0C 5\u00a0min, 15\u00a0\u00b0C hold; PCR conditions for copy number variations: 95\u00a0\u00b0C 10\u00a0min; 95\u00a0\u00b0C 30\u00a0s, 60\u00a0\u00b0C 60\u00a0s, 24 cycle; 15\u00a0\u00b0C hold. Whole genome DNA sequencing was performed to detect globin gene defects by the Beijing Genome Institute (BGI)-Shenzhen through next-generation sequencing technology . Gap-PCRContinuous variables are summarized by descriptive statistics, including the mean and range or standard deviation. Categorical variables are presented as number and percentage, and the comparisons of frequencies and mean were completed by using the Chi-square test and\u00a0one-way\u00a0analysis of variance (ANOVA). A statistically significant difference was defined as a p\u2009<\u20090.05. Statistical analyses were performed with SPSS 17.0 .Of the 7644 qualified participants, 3817 were males and 3827 were females, the participants\u2019 ages ranged from 5 to 68 (average age 25\u2009\u00b1\u20093.4) years, 1027 (13.44%) were minors, and 6617 (86.56%) were adults. The geographical residence pattern of the subjects was as follows: Qianbei  region, 2904 (37.99%); Qiannan , 491 (6.42%); Qianxi , 952 (12.45%); and Qiandongnan , 3297 (43.13%). There were nine ethnicities inhabiting those regions: Han, 4475 (58.5%); Dong, 890 (11.6%); Miao, 737 (9.6%); Buyi, 486 (6.4%); Shui, 325 (4.3%); Tujia, 243 (3.2%); Yao, 151 (2%); Gelao, 141 (1.8%); and Zhuang 196 (2.6%).anti4.2/\u03b1\u03b1 accounted for 0.523% (40/7644), the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 for 0.235% (18/7644), and 1 subject carried a \u03b1\u03b1\u03b1anti3.7 allele and a \u2013SEA allele (genotype: \u03b1\u03b1\u03b1anti3.7/\u2013SEA), accounting for 0.013% (1/7644). Thus, the \u03b1\u03b1\u03b1anti4.2/\u03b1\u03b1 is more prevalent than the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 in Guizhou province (p\u2009<\u20090.05). In addition, we identified 18 cases of the HK\u03b1\u03b1/\u03b1\u03b1 carriers, accounting for 0.235% (18/7644).As listed in Table anti4.2/\u03b1\u03b1 was identified in the Tujia ethnic group (1.65%), followed by the Han, Dong, Shui, Buyi, and Miao. The frequency of the \u03b1\u03b1\u03b1anti4.2/\u03b1\u03b1 in the Tujia group was significantly higher than in the Miao (p\u2009=\u20090.015), Dong (p\u2009=\u20090.022), and Buyi (p\u2009=\u20090.045). For the \u03b1\u03b1\u03b1anti 3.7/\u03b1\u03b1 genotype, the highest rate was observed in the Tujia group as well, followed by the Dong, Han, Buyi, and Miao. No \u03b1\u03b1\u03b1anti 3.7/\u03b1\u03b1 carrier was observed in the Shui group. No triplicated \u03b1-globin genes were detected in the Zhuang, Yao, and Gelao groups.As listed in Table p\u2009=\u20090.03), Qianbei (p\u2009=\u20090.001), and Qianxi (p\u2009=\u20090.0045). There was no significant difference observed between the other regions. While the prevalence of the \u03b1\u03b1\u03b1anti 4.2/\u03b1\u03b1 genotype was significantly higher in Qiannan region than in other regions, the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 was commonly found in Qiannan and Qiandongnan regions. However, although the frequency of the \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1 was higher in Qiandongnan, there was no statistically significant distribution difference between those regions (p\u2009>\u20090.05). In addition, the HK\u03b1\u03b1/\u03b1\u03b1 was mainly distributed in Qiandongnan, but its distribution had no statistically significant difference between those regions (p\u2009>\u20090.05). The \u03b1\u03b1\u03b1anti3.7/\u2013 SEA was quite rare in those regions, and only one case was detected in Qiandongnan.As listed in Table anti3.7/\u2013SEA case, and 18 cases of the HK\u03b1\u03b1/\u03b1\u03b1 did not presented any clinical manifestations such as anemia at the time of examination. The blood parameters including the red blood cells (RBC), hemoglobin (HGB), mean corpuscular volume (MCV), mean corpuscular hemoglobin (MCH), HbA, HbA2, and HbF were measured and statistically analyzed through ANOVA. No significant parameter difference was identified among the three different genotype groups (p\u2009>\u20090.05) (Tables 0 (HBB: c.126_129delCTTT) and \u03b1\u03b1/\u03b1\u03b1\u03b1anti4.2 (Table 0 (HBB:c.52A\u2009>\u2009T) and the \u03b1\u03b1/\u03b1\u03b1\u03b1anti4.2.The frequency of thalassemia-gene carriers in Guizhou is 11.03%, with 7.41% of \u03b1-thalassemia-gene frequency and 3.23% of \u03b2-thalassemia-gene frequency (unpublished data). Therefore, the frequency of \u03b1-thalassemia is higher than \u03b2-thalassemia in Guizhou province, China. While deletion of \u03b1-globin genes causes \u03b1-thalassemia, the triplicated \u03b1-globin genes alone rarely cause obvious clinical symptoms. All 59 carriers of the triplicated \u03b1-globin genes including the \u03b1\u03b1\u03b1anti4.2/\u03b1\u03b1, \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1. Although the HK\u03b1\u03b1 shows by GAP-PCR the positivity for \u03b1\u03b1\u03b1anti4.2 and -\u03b13.7, it is not considered as \u03b1-globin triplication due to no real extra copy of the \u03b1-globin gene existed in the HK\u03b1\u03b1 allele. Observations have indicated that \u03b1-globin triplication alone does not cause detectable clinical manifestations [anti3.7 and \u03b1\u03b1\u03b1anti4.2 was different between the two subpopulations. In our study, the ratio of \u03b1\u03b1\u03b1anti3.7/\u03b1\u03b1\u03b1anti4.2 was 0.47 (0.248% \u03b1\u03b1\u03b1anti3.7/0.523% \u03b1\u03b1\u03b1anti4.2) in Guizhou province, while it was 3.0 (0.9% \u03b1\u03b1\u03b1anti3.7/0.3% \u03b1\u03b1\u03b1anti4.2) in Guangdong province. This finding suggests that the \u03b1\u03b1\u03b1anti4.2 triplication is rather common in Guizhou, while the \u03b1\u03b1\u03b1anti3.7 is prevalent in Guangdong region.To date, at least two genotypes of \u03b1-globin triplication have been described: \u03b1\u03b1\u03b1stations . Howeverstations , and in anti4.2 in Tujia was significantly higher (1.65%) than in any other ethnic group. This is the first report that Tujia have a higher frequency of \u03b1-globin triplication. Whether this higher rate of \u03b1-globin triplication is caused by a founder effect or not requires further investigation. Although previous studies have reported that the frequencies of \u03b1-globin defects in the Zhuang and Yao ethnic groups were significantly higher than that in the Han ethnic group in Guangxi, another province in southwestern China [Ethnically, the Tujia group presented the highest prevalence (2.47%) of the \u03b1-globin triplication. In particular, the prevalence of \u03b1\u03b1\u03b1rn China , we did anti4.2 in Qiannan was also higher than in other regions. The other type of \u03b1-globin triplication, \u03b1\u03b1\u03b1anti3.7/\u2013SEA, and the non-\u03b1-triplication HK\u03b1\u03b1/\u03b1\u03b1 had no significant geographical differences. In addition, we did not identify any anti-HK\u03b1\u03b1 allele, although we found that the frequency of HK\u03b1\u03b1 allele was 0.235%, significantly higher than previously reported. To exclude the presence of HK\u03b1\u03b1 in case of positivity for the -\u03b13.7 and \u03b1\u03b1\u03b1anti4.2, next-generation and Gap-PCR are needed to be simultaneously performed. Interestingly, while the HK\u03b1\u03b1 is hardly observed in other regions, it was relatively common in Qiandongnan and its frequency is comparable to that of the \u03b1\u03b1\u03b1anti 4.2 triplication there . The frequency difference of the \u03b1-globin triplication between Qiannan and any other region was statistically significant. Moreover, the frequency of \u03b1\u03b1\u03b1%. The franti4.2, and \u03b1\u03b1\u03b1anti3.7 carriers were all within the normal range, which is consistent with previous reports [anti4.2, and \u03b1\u03b1\u03b1anti3.7 will not present clinical manifestations such as anemia. Of note, although the HK\u03b1\u03b1 carriers presented a normal range of hematological parameters, their RBC, hemoglobin, MCH, and MCV were all slightly lower than the \u03b1\u03b1\u03b1anti4.2 and \u03b1\u03b1\u03b1anti3.7 carriers, implying that the particular cluster structure that could reduce the \u03b1-globin gene expression.In our study, the hematological parameters and hemoglobin electrophoresis data of the HK\u03b1\u03b1, \u03b1\u03b1\u03b1 reports , 22. Theanti3.7/\u2013SEA did not presented any clinical manifestations such as anemia at the time of examination, which is consistent with previous reports [As mentioned above, the triplicated \u03b1-globin genes alone barely lead to detectable clinical phenotypes. In this study, of the 59 cases of \u03b1-globin genes triplication, 5 cases coinherited with \u03b2-globin gene mutation(s) while the other 54 subjects did not present any clinical symptoms. Although many reports have stated that \u03b1-globin triplication can exacerbate the symptoms of \u03b2-thalassemia, the issue is still controversial because the expected worsened anemia has not occurred in all cases , 18. In  reports , 23.Currently, Gap-PCR and PCR combined with RDB (reverse dot blot) methods are commonly used to detect \u03b1-globin gene deletions and the \u03b2-globin gene defects, but they usually miss the triplicated \u03b1-globin genes. In this study, whole genome NGS combined with Gap-PCR was adopted to screen for all types of \u03b1-globin and \u03b2-globin gene alterations, including \u03b1-globin gene deletion, triplication, splicing mutations, which would be expected to increase the detection sensitivity and improve the diagnosis of \u03b2-thalassemia.This epidemiological study has identified the current \u03b1-triplication genotypes and their prevalence and distribution in Guizhou province, which will be used to update the triplicated \u03b1-globin thalassemia database, provide insights into the pathogenesis of thalassemia and shed light on the diagnosis of thalassemia in southwestern China."}
{"text": "The title compound crystallizes with half of a mol\u00adecule per asymmetric unit and exhibits bond lengths and angles typical of \u03b1-diketones. A network of C\u2014H\u22efF contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions is observed within the structure. 14H6F4O2, crystallizes with half of a mol\u00adecule per asymmetric unit and exhibits bond lengths and angles typical of \u03b1-diketones. A network of C\u2014H\u22efF contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions is observed within the structure.The title compound, C The title \u03b1-diketone, 1,2-bis\u00adethane-1,2-dione, is used as a precursor in the production of hexa\u00adbenzocoronenes  and similar \u03b1,\u03b1-diketones crystallize in trigonal or monoclinic space groups, respectively , and exhibits the expected bond lengths and angles for \u03b1-diketone sp2 hybridized atoms. Inter\u00adestingly, the C5\u2014C6\u2014C7\u2014O1 torsion angle [7.55\u2005(19)\u00b0] of the title compound is larger compared to the same torsion angle in bis\u00ad(4-fluoro\u00adphen\u00adyl)ethane-1,2-dione . A network of C\u2014H\u22efO inter\u00adactions is also observed between the carbonyl oxygen and H5. This inter\u00adaction is significantly weaker for 1,2-bis\u00adethane-1,2-dione in comparison to benzil (O\u22efH = 2.42\u2005\u00c5) and bis\u00ad(4-fluoro\u00adphen\u00adyl)ethane-1,2-dione (O\u22efH = 2.40\u2005\u00c5). As a result, the \u03c0\u2013\u03c0 stacking and C\u2014H\u22ef F inter\u00adactions play a vital role in how the compound packs within the crystal structure.A view of crystal packing of the title compound is presented in Fig.\u00a02ne Fig.\u00a03. Similaret al., 2016A search of the Cambridge Structural Database pentane-1,4-dione.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021005363/yk2148sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021005363/yk2148Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021005363/yk2148Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021005363/yk2148Isup4.cmlSupporting information file. DOI: 2085161CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular conformation is stabilized by an intra\u00admolecular O\u2014H\u22efO hydrogen bond between the hy\u00addroxy substituent on the benzene ring and one of the carbonyl groups of the acridinedione unit. 27H33NO5, a 3,3,6,6-tetra\u00admethyl\u00adtetra\u00adhydro\u00adacridine-1,8-dione ring system carries an ethyl acetate substituent on the acridine N atom and an o-hy\u00addroxy\u00adphenyl ring on the central methine C atom of the di\u00adhydro\u00adpyridine ring. The benzene ring is inclined to the acridine ring system at an angle of 80.45\u2005(7)\u00b0 and this conformation is stabilized by an intra\u00admolecular O\u2014H\u22efO hydrogen bond between the hy\u00addroxy substituent on the benzene ring and one of the carbonyl groups of the acridinedione unit. The ester C=O oxygen atom is disordered over major and minor orientations in a 0.777\u2005(9):0.223\u2005(9) ratio and the terminal \u2013CH3 unit of the ethyl side chain is disordered over two sets of sites in a 0.725\u2005(5): 0.275\u2005(5) ratio. In the crystal, C\u2014H\u22efO hydrogen bonds combine to link the mol\u00adecules into a three-dimensional network. van der Waals H\u22efH contacts contribute the most to the Hirshfeld surface (66.9%) followed by O\u22efH/H\u22efO (22.1%) contacts associated with weak hydrogen bonds.In the title compound, C In contrast, the central C13/N1/C1/C6\u2013C8 ring can best be described as a flattened boat with N1 and C7 displaced by 0.146\u2005(1) and 0.191\u2005(14)\u2005\u00c5, respectively, from the remaining four C atoms. The bond lengths and angles in the title mol\u00adecule agree reasonably well with those found in closely related mol\u00adecules . The relative contributions of the other inter\u00adactions in descending order are: O\u22efH/H\u22efO (22.1%), C\u22efH/H\u22efC (9.2%), O\u22efO (1.3%), N\u22efH/H\u22efN (0.2%) and N\u22efC/C\u22efN (0.2%). This illustrates that the C\u2014H\u22efO inter\u00adactions contribute significantly to the crystal packing.The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a04ts Fig.\u00a04b. The rH)-yl]acetic acid [Cam\u00adbridge Structural Database -yl]acetate -dione -dione -1,8-dioxo-2,3,4,5,6,7,8,9-octa\u00adhydro\u00adacridin-10(1S(8) ring. In the crystal, the mol\u00adecules are linked by O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network. In VANBUK, the central 1,4-di\u00adhydro\u00adpyridine ring adopts a shallow sofa conformation (with the C atom bearing the bromo\u00adphenol ring as the flap), whereas the pendant cyclo\u00adhexene rings both have twisted-boat conformations. The mol\u00adecule features an intra\u00admolecular O\u2014H\u22efO hydrogen bond, which closes an S(8) ring. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO inter\u00adactions, forming C(12) chains propagating along the c-axis direction. In the crystal of SILBIB, O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) hydrogen bonds combine with an Br\u2014O and unusual C\u2014Br\u22ef\u03c0(ring) halogen bonds to generate a three dimensional network with mol\u00adecules stacked along the a-axis direction. In the acridinedione moiety of PUSJEU, the central di\u00adhydro\u00adpyridine ring adopts a flattened-boat conformation, with the N atom and the methine C atom displaced from the mean plane of the other four atoms by 0.0513\u2005(14) and 0.1828\u2005(18)\u2005\u00c5, respectively. The two cyclo\u00adhexenone rings adopt envelope conformations, with the tetra\u00adsubsituted C atoms as the flap atoms. In the crystal, mol\u00adecules are linked via a pair of C\u2014H\u22efO hydrogen bonds, forming inversion dimers, which are, in turn, linked by C\u2014H\u22efO hydrogen bonds, forming slabs lying parallel to (001).The DABSAD compound crystallizes with two mol\u00adecules in the asymmetric unit. In each mol\u00adecule, the central 1,4-di\u00adhydro\u00adpyridine ring adopts a shallow sofa conformation (with the C atom bearing the phenol ring as the flap), whereas the pendant cyclo\u00adhexene rings both have twisted-boat conform\u00adations. Each mol\u00adecule features an intra\u00admolecular O\u2014H\u22efO hydrogen bond, which closes an To a mixture of dimedone , ethyl glycinate hydro\u00adchloride  and salicaldehyde  in ethanol (20\u2005ml), triethyl amine  was added. The reaction mixture was heated under reflux for 5\u2005h at 353\u2013358\u2005K then left to cool. The separated solid was filtered off, dried and recrystallized from ethanol solution as yellow plates of the title compound, yield 68%, m.p. 497\u2005K.Uiso(H) = 1.2Ueq (C) and O\u2014H = 0.84\u2005\u00c5, Uiso(H) = 1.5Ueq (O). Atom O3 of the oxo group and terminal methyl group (C17) of the ethyl acetate substituent are disordered over two sites in 0.777\u2005(9):0.223\u2005(9) (for O3 and O3A) and 0.725\u2005(5):0.275\u2005(5) (for C17 and C17A) ratios, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021001341/hb7967sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021001341/hb7967Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021001341/hb7967Isup3.cmlSupporting information file. DOI: 2061379CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A linear supra\u00admolecular chain featuring amine-N\u2014H\u22efO(nitro) hydrogen bonding is noted in the crystal.The N 22H17N4O2S)2], comprises two N,S-donor anions, leading to a distorted tetra\u00adhedral N2S2 donor set. The resultant five-membered chelate rings are nearly planar and form a dihedral angle of 73.28\u2005(3)\u00b0. The configurations about the endocyclic- and exocyclic-imine bonds are Z and E, respectively, and that about the ethyl\u00adene bond is E. The major differences in the conformations of the ligands are seen in the dihedral angles between the chelate ring and nitro\u00adbenzene rings [40.48\u2005(6) cf. 13.18\u2005(4)\u00b0] and the N-bound phenyl and nitro\u00adbenzene ring [43.23\u2005(8) and 22.64\u2005(4)\u00b0]. In the crystal, a linear supra\u00admolecular chain along the b-axis direction features amine-N\u2014H\u22efO(nitro) hydrogen bonding. The chains assemble along the 21-screw axis through a combination of phenyl-C\u2014H\u22efO(nitro) and \u03c0(chelate ring)\u2013\u03c0(phen\u00adyl) contacts. The double chains are linked into a three-dimensional architecture through phenyl-C\u2014H\u22efO(nitro) and nitro-O\u22ef\u03c0(phen\u00adyl) inter\u00adactions.The title zinc bis\u00ad(thio\u00adsemicarbazone) complex, [Zn(C These ligands usually act as monodentate or bidentate ligands and coordinate with transition and non-transition metal ions either in neutral or anionic form through thione/thiol\u00adate-sulfur and azomethine/imine-nitro\u00adgen donor atoms \u00b0 for the S1\u2014Zn\u2014N1 chelate angle, to a wide 131.16\u2005(2)\u00b0, for S1\u2014Zn\u2014S2, consistent with an approximate tetra\u00adhedral geometry. The mode of coordination of the thio\u00adsemicarbazone ligands leads to the formation of five-membered chelate rings. These are nearly planar with r.m.s. deviations of 0.0459 and 0.0152\u2005\u00c5 for the S1- and S2-containing rings, respectively. However, the maximum deviation from the plane through the S1-chelate ring of \u22120.0613\u2005(9)\u2005\u00c5 for the N1 atom suggests an alternate description of the conformation of the S1-ring might be valid. Another description might be an envelope conformation with the zinc atom lying 0.209\u2005(3)\u2005\u00c5 out of the plane of the four remaining atoms (r.m.s. deviation = 0.0005\u2005\u00c5). The dihedral angle between the mean plane through the rings is 73.28\u2005(3)\u00b0. There are three formal double bonds in each thio\u00adsemicarbazone anion. Owing to chelation, the configuration about the endocyclic imine bond is Z whereas that about the exocylic imine bond is E; the configuration of the ethyl\u00adene bond is E.The mol\u00adecular structure of (I)N-bound phenyl and nitro\u00adbenzene rings is 72.41\u2005(5), 16.96\u2005(11) and 40.48\u2005(6)\u00b0, respectively, for the S1-ring compared with 82.47\u2005(6), 20.33\u2005(5) and 13.18\u2005(4)\u00b0, respectively, for the S2-ring. Similarly, the pairs of dihedral angles between the imine- and N-bound phenyl rings, i.e. 59.15\u2005(6) and 76.48\u2005(8)\u00b0, and N-bound phenyl and nitro\u00adbenzene rings, i.e. 43.23\u2005(8) and 22.64\u2005(4)\u00b0, show notable differences; the dihedral angles between the imine-phenyl and nitro\u00adbenzene rings are comparable, i.e. 82.28\u2005(7) and 85.67\u2005(7)\u00b0. Finally, the nitro groups present different relative orientations with respect to the benzene rings they are connected to, with the N4-nitro group being twisted out of the plane. This is shown in the value of the C2\u2014C3\u2014N4\u2014O1 torsion angle of 161.88\u2005(18)\u00b0 compared with \u22120.4\u2005(3)\u00b0 for the C26\u2014C25\u2014N8\u2014O3 torsion angle.Some major differences are noted in the conformations of the ligands. Thus, the sequence of dihedral angles formed between the chelate ring and the imine-phenyl, b-axis direction, Table\u00a02a). The hydrogen bonds involve the N7-amine, there being no apparent role for the N3-amine in the supra\u00admolecular aggregation. A phenyl-C44\u2014H\u22efO4(nitro) contact provides extra stability to the chain and indicates the nitro-O4 atom forms two contacts. Chains assemble about the 21-screw axis via a combination of phenyl-C37\u2014H\u22efO3(nitro) and \u03c0\u2013\u03c0 contacts. The \u03c0\u2013\u03c0 contacts are of particular inter\u00adest in that the participating rings are a phenyl and a chelate ring, as highlighted in Fig.\u00a02b); such inter\u00adactions are now well recognized in the supra\u00admolecular chemistry of metal complexes and impart significant energies of stabilization to the packing \u22efCgi is 3.5559\u2005(11)\u2005\u00c5 with an inter-planar angle = 6.70\u2005(8)\u00b0 and slippage of 0.34\u2005\u00c5 for symmetry operation (i): x, y, z. The links between chains to consolidate the three-dimensional architecture are of the type phenyl-C14\u2014H\u22efO1(nitro) and nitro-O1\u22ef\u03c0(phen\u00adyl), Table\u00a02Cg(C23\u2013C28)ii = 3.4788\u2005(19)\u2005\u00c5 with angle at O1 = 108.71\u2005(13)\u00b0 for (ii): 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. A view of the unit-cell contents is shown in Fig.\u00a03Conventional amine-N7\u2014H\u22efO4(nitro) hydrogen bonds are noted in the crystal of (I)Crystal Explorer 17 dnorm-mapped Hirshfeld surface of Fig.\u00a06dnorm-mapped Hirshfeld surface. However, the \u03c0\u2013\u03c0 inter\u00adaction appears as a flat surface on the curvedness-mapped Hirshfeld surface of Fig.\u00a08a), the nitro-O\u22ef\u03c0 inter\u00adaction is shown as red concave and blue bump regions on the shape-index-mapped Hirshfeld surface of Fig.\u00a08b).The faint-red spots observed on the a)\u2013(f), respectively. The percentage contributions from each inter\u00adatomic contact are summarized in Table\u00a04b), with the peak tipped at de = di \u223c2.2\u2005\u00c5 corresponding to the H24\u22efH44 contact, Table\u00a03de + di \u223c2.0 and 2.6\u2005\u00c5, respectively, Fig.\u00a09c) and (d). The H\u22efS/S\u22efH contacts contribute 8.6% and appear as two blunt-symmetric wings at de + di \u223c2.9\u2005\u00c5 in Fig.\u00a09e). This feature reflects the long-range H\u22efS/S\u22efH contact evinced in the packing with a separation of 0.1\u2005\u00c5 shorter than the sum of their van der Waals radii, Table\u00a03de + di \u223c2.6\u2005\u00c5 in the fingerprint plot of Fig.\u00a09f), the contribution to the overall Hirshfeld surface is only 5.2%. The other 11 inter\u00adatomic contacts have a negligible effect on the mol\u00adecular packing as their accumulated contribution is below 11%, Table\u00a04The overall two-dimensional fingerprint plot for (I)d,p) level of theory. The total energy (Etot) was calculated by summing four energy components, comprising the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies. The independent energy components as well as the Etot are tabulated in Table\u00a05Edis energy term still makes the major contribution to the inter\u00adaction energies partly due to the presence of \u03c0\u2013\u03c0, N\u2014O\u22ef\u03c0, C\u2014H\u22efO and C\u2014H\u22efC inter\u00adactions. The total Edis components of all pairwise inter\u00adactions sum to \u2212432.1\u2005kJ\u2005mol\u22121, whereas the total Eele sums to \u2212190.2\u2005kJ\u2005mol\u22121. The stabilization of the crystal through the contribution of the dispersion forces is emphasized by the energy framework diagram, Fig.\u00a010b axis.The pairwise inter\u00adaction energies between mol\u00adecules in the mol\u00adecular packing of (I)N-bound ethyl species with a terminal phenyl ring -N-phenyl\u00adhydrazine-1-carbo\u00adthio\u00adamide, (VI), was filtered, washed with cold ethanol and dried in vacuo after which it was used without further purification. Compound (VI)  was dissolved in hot absolute ethanol (50\u2005ml), which was added to a solution of Zn(CH3COO)2\u00b72H2O  in hot absolute ethanol (40\u2005ml). The mixture was heated (348\u2005K) and stirred for about 10\u2005min, followed by stirring for about 1\u2005h at room temperature. The white precipitate obtained was filtered, washed with cold ethanol and dried in vacuo. Single crystals were grown at room temperature by slow evaporation of (I)v/v 20\u2005ml). Yield: 90%, m.p. 511\u2013512\u2005K. FT\u2013IR (ATR (solid) cm\u22121): 3428 \u03bd(N\u2014H), 1593 \u03bd(C=N), 1335 \u03bd(N\u2014N), 579 \u03bd(Zn\u2014N), 489 \u03bd(Zn\u2014S). UV\u2013Visible: \u03bbmax ): 250 , 292 , 433 . ICP\u2013AES: Experimental %Zn = 7.26, Theoretical %Zn = 7.53.Analytical grade reagents were used as procured and without further purification. 4-Phenyl-3-thio\u00adsemicarbazide  and 4-nitro\u00adchalcone  were dissolved separately in hot absolute ethanol (50\u2005ml) and mixed while stirring. About five drops of concentrated hydro\u00adchloric acid were added to the mixture and the mixture was heated (348\u2005K) while stirring for about 30\u2005min. The yellow precipitate, (2Uiso(H) set to 1.2Ueq(C). The N-bound H atoms were located in a difference-Fourier map, but were refined with an N\u2014H = 0.88\u00b10.01\u2005\u00c5 distance restraint, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989021007398/mw2178sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989021007398/mw2178Isup2.hklStructure factors: contains datablock(s) I. DOI: 2097106CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the aromatic rings in the title compound is 31.84\u2005(8)\u00b0; N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions connect mol\u00adecules in the crystal, producing a three-dimensional network. 16H12F5N3O, the dihedral angle between the aromatic rings is 31.84\u2005(8)\u00b0. In the crystal, the mol\u00adecules are linked into dimers possessing crystallographic twofold symmetry by pairwise N\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions link the dimers into a three-dimensional network. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from F\u22efH/H\u22efF (41.1%), H\u22efH (21.8%), C\u22efH/H\u22efC (9.7%) C\u22efC (7.1%) and O\u22efH/H\u22efO (7.1%) contacts. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine  in PLATON. The solvent contribution was not included in the reported mol\u00adecular weight and density.In the title compound, CSpek 2015. Acta Cr R)C=N\u2014NHR grouping possess controllable E/Z isomerization around the C=N double bond, which makes them good candidates for the construction of functional materials \u2005\u00c5. The backbone of the mol\u00adecule is non-planar with a dihedral angle of 31.84\u2005(8)\u00b0 between the C1\u2013C6 penta\u00adflouro\u00adbenzene and C11\u2013C16 benzene rings and the acetamide group lies almost perpendicular. The C5\u2014C6\u2014C7\u2014N2, C6\u2014C7\u2014N2\u2014N3, C7\u2014N2\u2014N3\u2014C11, N2\u2014N3\u2014C11\u2014C16 and C6\u2014C7\u2014C8\u2014N1 torsion angles are \u221228.19\u2005(17), 174.02\u2005(10), \u2212176.33\u2005(11), 5.90\u2005(18) and 122.80\u2005(12)\u00b0, respectively.The title mol\u00adecule Fig.\u00a01 crystallCg1\u22efCg1b = 3.7137\u2005(10)\u2005\u00c5, slippage = 1.158\u2005\u00c5, Cg1\u22efCg2b = 3.7015\u2005(9)\u2005\u00c5, slippage = 1.407\u2005\u00c5, and Cg1\u22efCg2a = 3.7016\u2005(9)\u2005\u00c5, slippage = 1.148\u2005\u00c5; where Cg1 and Cg2 are the centroids of the C1\u2013C6 and C11\u2013C16 rings, respectively; symmetry codes: (a) 1\u00a0\u2212\u00a0x, y, z; (b) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. Together, these generate a three-dimensional network  in blue and negative electrostatic potential is indicated in red (hydrogen-bond acceptors).a. The percentage contributions to the Hirshfeld surfaces from various inter\u00adatomic contacts (Table\u00a02b), H\u22efH , C\u22efH/H\u22efC  C\u22efC  and O\u22efH/H\u22efO . Other contact types including N\u22efH/H\u22efN, N\u22efC/C\u22efN and N\u22efN contacts account for less than 5.4% of the Hirshfeld surface mapping and presumably have minimal directional impact on the packing.The overall two-dimensional fingerprint map for the title compound is shown in Fig.\u00a04s Table\u00a02 are F\u22efH/s Table\u00a02b, H\u22efH -1-benzyl\u00adidene-2-phenyl\u00adhydrazine skeleton are (E)-3-chloro-N\u2032-(2-fluoro\u00adbenzyl\u00adidene)thio\u00adphene-2-carbohydrazide ethyl\u00adidene]isonicotinohydrazide -bis\u00ad[(thio\u00adphen-2-yl)meth\u00adyl\u00adidene]hydrazine ethyl\u00adidene]nicotinohydrazide \u2005\u00c5. The mol\u00adecular skeleton is approximately planar, the terminal five- and six-membered rings forming a dihedral angle of 5.47\u2005(9)\u00b0. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds into zigzag chains propagating in [100].The hydrazide derivative SOJQAL adopts an E conformation with respect to the azomethine bond. The pyridyl and fluoro\u00adbenzene rings make dihedral angles of 38.58\u2005(6) and 41.61\u2005(5)\u00b0 respectively with the central C(=O)N2CC unit, resulting in a non-planar mol\u00adecule. The inter\u00admolecular inter\u00adactions comprise two classical N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds and four non-classical C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds. These inter\u00adactions are augmented by a weak \u03c0\u2013\u03c0 inter\u00adaction between the benzene and pyridyl rings of neighbouring mol\u00adecules, with a centroid\u2013centroid distance of 3.9226\u2005(10)\u2005\u00c5. This leads to a three-dimensional supra\u00admolecular assembly in the crystal.The mol\u00adecule of HIXRAJ adopts an The asymmetric unit of MIHROK03 comprises two independent half-mol\u00adecules, each residing on a centre of symmetry. The two mol\u00adecules are essentially planar. In the crystal, weak C\u2014H\u22ef\u03c0 inter\u00adactions join the two symmetry-independent mol\u00adecules into inter\u00adlinked chains parallel to [011].E conformation with respect to the azomethine double bond whereas the N and methyl C atoms are in a Z conformation with respect to the same bond. The ketonic O and azomethine N atoms are cis to each other. The non-planar mol\u00adecule [the dihedral angle between the benzene rings is 7.44\u2005(11)\u00b0] exists in an amido form with a C=O bond length of 1.221\u2005(2)\u2005\u00c5. In the crystal, a bifurcated N\u2014H\u22ef hydrogen bond is formed between the amide H atom and the keto O and imine N atoms of an adjacent mol\u00adecule, leading to the formation of chains propagating along the b-axis direction.The mol\u00adecule of ZISSAX adopts an via hydrogen bonding of the carboxyl groups. In addition, there is an N\u2014H\u22efO hydrogen bond between the amino group and the carbonyl O atom.In TINWIX, the aromatic rings are almost perpendicular, making a dihedral angle of 89.26\u2005(5)\u00b0. The carboxyl group is coplanar with the aromatic ring to which it is attached [dihedral angle = 1.70\u2005(17)\u00b0]. The packing involves inversion-symmetric dimers bridged E)-1-[(perfluoro\u00adphen\u00adyl)methyl\u00adene]-2-phenyl\u00adhydrazine , tetra\u00admethyl\u00adethylenedi\u00adamine (TMEDA) , CuCl  and CCl4 . After 1\u20133\u2005h , the reaction mixture was poured into a 0.01 M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined organic phase was washed with water (3 \u00d7 50\u2005ml), brine (30\u2005ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Colourless prisms of the title compound suitable for X-ray analysis were obtained by slow evaporation of a di\u00adchloro\u00admethane solution (69%); m.p. 405\u2005K. Analysis calculated for C16H12F5N3O: C 53.79, H 3.39, N 11.76; found: C 53.73, H 3.36, N 11.71%. 1H NMR  \u03b4 3.04 , 6.50\u20137.33 . 13C NMR  \u03b4 33.58, 108.97, 116.87, 120.75, 124.11, 124.76, 140.95, 146.33, 149.87, 150.91, 155.21. ESI\u2013MS: m/z: 358.24 [M + H]+.A 20\u2005ml screw-neck vial was charged with DMSO (10\u2005ml), (Uiso(H) = 1.2 or 1.5Ueq (C). The residual electron density was difficult to model and therefore the SQUEEZE routine  contains approximately three electrons.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021007349/hb7979sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989021007349/hb7979Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007349/hb7979sup3.docxElectrostatic potential map. DOI: Click here for additional data file.10.1107/S2056989021007349/hb7979Isup4.cmlSupporting information file. DOI: 1878189CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III complex was synthesized from the substitution reaction between the (ppy)2Ir(\u03bc-Cl)2Ir(ppy)2  dimer and 1,1-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane  under an argon gas atmosphere. The IrIII atom is coordinated by two C,N-bidentate ppy anions, a unidentate dppm ligand and a chloride anion in a distorted octa\u00adhedral IrC2N2PCl arrangement.The title Ir III complex, [Ir(C11H8N)2Cl(C25H22P2)], was synthesized from the substitution reaction between the (ppy)2Ir(\u03bc-Cl)2Ir(ppy)2  dimer and 1,1-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane  under an argon gas atmosphere for 20\u2005h. The IrIII atom is coordinated by two C,N-bidentate ppy anions, a unidentate dppm ligand and a chloride anion in a distorted octa\u00adhedral IrC2N2PCl arrangement. The N donor atoms of the ppy ligands are mutually trans while the C atoms are cis. Intra\u00admolecular aromatic \u03c0\u2013\u03c0 stacking between the phenyl rings of ppy and dppm, and C\u2014H\u22efCl inter\u00adactions are observed. In the crystal, C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 contacts link the mol\u00adecules into a three-dimensional network. A Hirshfeld surface analysis was carried out to further qu\u00adantify the inter\u00admolecular inter\u00adactions, and indicated that H\u22efH contacts (63.9%) dominate the packing.The title Ir The bond lengths of Ir1\u2014N1, Ir1\u2014N2, Ir1\u2014C11 and Ir1\u2014C22 are 2.051\u2005(2), 2.062\u2005(2), 2.004\u2005(3) and 2.032\u2005(3)\u2005\u00c5, respectively. As expected, the averaged Ir\u2013C and Ir\u2014N bond lengths are much shorter than the Ir\u2014Cl and Ir\u2014P bonds, based on the sizes of the different species.The asymmetric unit of (I)2(dppm)]PF6 e.g., Hao et al., 20192(dppm)](PF6) iridium(III) are reported to be 2.503\u2005(19) trans bond angles deviate from the ideal 180\u00b0 [170.97\u2005(9)\u2013175.37\u2005(8)\u00b0], similar to related compounds methane (dppm) often occurs as a bidentate ligand (Cg5\u22efCg7 = 3.621\u2005(1)\u2005\u00c5 and between the phenyl rings of the dppm mol\u00adecule (C29\u2013C34 and C36\u2013C41), Cg8\u22efCg9 = 3.997\u2005(1)\u2005\u00c5 \u2005\u00c5], C30\u2014H30\u22efCl1 [C\u22efCl = 3.664\u2005(4)\u2005\u00c5] and C35\u2014H35A\u22efCl1 [C35\u22efCl = 3.460\u2005(3)\u2005\u00c5] \u2005\u00c5 Fig.\u00a02. Three w\u00c5] Fig.\u00a03 are obse\u22ef\u03c0 (ring) inter\u00adactions are found in the crystal packing  of the C17\u2013C22 phenyl ring (H3\u22efCg6 = 2.83\u2005\u00c5). In addition, C\u2014H\u22ef\u03c0(ring) inter\u00adactions are also found between the dppm phenyl rings of neighbouring mol\u00adecules: C26\u2014H26 \u22efCg10 , C38\u2014H38\u22efCg10 (H38\u22efCg10 = 2.81\u2005\u00c5) and C40\u2014H40\u22efCg8 (H40\u22efCg8 = 2.95\u2005\u00c5). In addition, pairwise inter\u00admolecular hydrogen bonds are observed between C14\u2014H14 of the pyridine ring of the ppy ring and Cl1  with the functions de and di, which are the distances from an indicated area on the Hirshfeld surface to the nearest atoms outside and inside the surface, respectively. The white, red, and blue areas on the dnorm-mapped Hirshfeld surfaces show inter\u00admolecular contacts that are equal to, shorter than, and longer than the sum of their van der Waals (vdW) radii, respectively. A pair of inter\u00admolecular contacts are shown as red spots on the Hirshfeld surface close to the Cl1 atom of the adjoining mol\u00adecule and the H14 atom of the associated pyridine ring. The spots indicate hydrogen-bond donor-to-acceptor inter\u00adactions of C14\u2014H14\u22efCl1 and vice versa  while Fig.\u00a06b)\u2013(d) depict the contacts of the H\u22efH (63.9%), C\u22efH/H\u22efC (29.5%) and H\u22efCl/Cl\u22efH (4.4%) inter\u00adactions, respectively.Additional insights into the weak inter\u00admolecular contacts in the crystal packing of (I)sa Fig.\u00a05. The relSciFinder ]+; dppm = bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane bidentate ligand. However, none of the remaining publications describe a monomeric IrIII complex similar to the title compound. The seven hits include the octa\u00adhedral crystal structures of IrIII complexes with a bis\u00ad(2-phenyl\u00adpyridine)\u00adiridium(III) backbone and ancillary ligands of both N-donor, P-donor and O-donor ligands. There are a tris-complex of Ir(ppy)3 ]; dppel = 1,2-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)ethyl\u00adene, [Ir(ppy)2(dppp)]; dppp = 1,3-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)propane and [Ir(ppy)2(dppe)]; dppe = 1,2-bis\u00ad(diphenylphosphan\u00adyl) ethane] ]PF6, [Ir(dfppy)2(P^N)]PF6 and [Ir(dfmppy)2(P^N)]PF6 where P^N = 2-[(di\u00adphenyl\u00adphos\u00adphan\u00adyl) meth\u00adyl]pyridine, dfppy = 2-pyri\u00addine and dfmppy = 2--4-methyl\u00adpyridine ]PF6    and refined as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021000955/hb7961sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021000955/hb7961Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021000955/hb7961Isup3.molSupporting information file. DOI: 2058995CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, generating  22H15N3O4, is built up from a central imidazopyridine ring system connected to a nitroso group, a phenyl ring and a 2-oxo-2-phenyl\u00adethyl acetate group. The imidazo pyridine ring system is almost planar (r.m.s. deviation = 0.017\u2005\u00c5) and forms dihedral angles of 22.74\u2005(5) and 45.37\u2005(5)\u00b0, respectively, with the phenyl ring and the 2-oxo-2-phenyl\u00adethyl acetate group. In the crystal, the mol\u00adecules are linked into chains parallel to the b axis by C\u2014H\u22efO hydrogen bonds, generating R21 (5) and R44 (28) graph-set motifs. The chains are further linked into a three-dimensional network by C\u2014H\u22ef\u03c0 and \u03c0-stacking inter\u00adactions. The inter\u00admolecular inter\u00adactions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most important contributions for the crystal packing are from H\u22efH (36.2%), H\u22efC/C\u22efH (20.5%), H\u22efO/O\u22efH (20.0%), C\u22efO/O\u22efC (6.5%), C\u22efN/N\u22efC (6.2%), H\u22efN/N\u22efH (4.5%) and C\u22efC (4.3%) inter\u00adactions.The title compound, C N-heterocycles as the core structure, including imidazopyridine and its derivatives, which are used in medicinal chemistry Numerous drugs contain a] pyridine ring system is planar with an r.m.s deviation of 0.017\u2005\u00c5 and a maximum deviation of 0.028\u2005(1)\u2005\u00c5 for atom C11. The mean plane through the fused ring system makes dihedral angles of 22.74\u2005(5) and 45.37\u2005(5)\u00b0 with the phenyl ring (C1\u2013C6) and the 2-oxo-2-phenyl\u00adethyl acetate group (C14\u2013C22), respectively. The dihedral angle between the two aromatic rings (C1\u2013C6 and C17\u2013C22) is 59.63\u2005(5)\u00b0. The mol\u00adecular conformation is stabilized by two weak intra\u00admolecular C9\u2014H9\u22efO1 and C1\u2014H1\u22efN1 hydrogen bonds, generating S(6) ring motifs (Table\u00a01The mol\u00adecular structure of (I)s Table\u00a01.iii and C10\u2014H10\u22efO2iii hydrogen bonds, forming chains that propagate parallel to the b axis and enclose A\u22efO4i and C15\u2014H15B\u22efO1ii hydrogen bonds with Cg4iv inter\u00adaction (Cg4 is the centroid of the C17\u2013C22 phenyl ring) as well as \u03c0\u2013\u03c0 stacking inter\u00adactions involving the centroids (Cg1 and Cg2) of the N2/C13/N3/C7\u2013C8 and N2/C9\u2013C13 rings with a centroid-to-centroid distance Cg1\u22efCg2  of 3.5750\u2005(9)\u2005\u00c5 and a slippage of 0.685\u2005\u00c5 N-acetamide carbonoimido\u00adyl]phenol \u00b0. In TUQCEP, C21H17N3O, the fused ring system is almost planar (r.m.s. deviation = 0.031\u2005\u00c5) and forms dihedral angles of 64.97\u2005(7) and 18.52\u2005(6)\u00b0 with the phenyl ring and the (imino\u00admeth\u00adyl)phenol group, respectively. In its crystal, mol\u00adecules are linked by pairs of C\u2014H\u22ef\u03c0 inter\u00adactions into centrosymmetric dimeric units, which are further connected by O\u2014H\u22efN hydrogen bonds, forming layers parallel to (101).A search of the Cambridge Structural Database  to 1.2371 (blue) a.u. . The shape-index map of the title mol\u00adecule was generated in the range \u22121 to 1\u2005\u00c5 , revealing the presence of red and blue triangles that are indicative of the presence of \u03c0\u2013\u03c0 stacking inter\u00adactions. The curvedness map of the title complex was generated in the range \u22124.0 to 4.0\u2005\u00c5  and shows flat surface patches characteristic of planar stacking. The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efO/O\u22efC, C\u22efN/N\u22efC, H\u22efN/N\u22efH and C\u22efC inter\u00adactions in Fig.\u00a04a\u2013g, respectively. The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a05a, with those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efO/O\u22efC, C\u22efN/N\u22efC, H\u22efN/N\u22efH and C\u22efC contacts associated with their relative contributions to the Hirshfeld surface in Fig.\u00a05b\u2013h, respectively. The most important inter\u00admolecular inter\u00adaction is H\u22efH, contributing 36.2% to the overall crystal packing . H\u22efC/C\u22efH contacts, with a 20.5% contribution to the Hirshfeld surface, indicate the presence of the weak C\u2014H\u22ef\u03c0 inter\u00adaction . H\u22efO/O\u22efH contacts arising from inter\u00admolecular C\u2014H\u22efO hydrogen bonding make a 20.0% contribution to the Hirshfeld surface and are represented by a pair of sharp spikes in the region de + di \u223c2.34\u2005\u00c5 . The C\u22efC contacts are a measure of \u03c0\u2013\u03c0 stacking inter\u00adactions and contribute 4.3% of the Hirshfeld surface . The contributions of the other contacts to the Hirshfeld surface are C\u22efO/O\u22efC of 6.5%, C\u22efN/N\u22efC of 6.2% and H\u22efN/N\u22efH of 4.5%.Hirshfeld surface analysis was used to qu\u00adantify the inter\u00admolecular contacts of the title compound, using u. Fig.\u00a03a. The s\u2005\u00c5 Fig.\u00a03b, revea\u2005\u00c5 Fig.\u00a03c and shng Fig.\u00a05b. H\u22efC/Cn Table\u00a01. Two paint Fig.\u00a05c. H\u22efO/O\u2005\u00c5 Fig.\u00a05d. The Cce Fig.\u00a05h. The ca]pyridine-8-carboxyl\u00adate  in acetic acid (50\u2005ml), sodium nitrite  was added at room temperature. The resulting precipitate was washed with water and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined di\u00adchloro\u00admethane extracts were dried over anhydrous sodium sulfate and filtered. The remaining solution was concentrated under reduced pressure. The residue was purified chromatographically on a neutral alumina gel column using di\u00adchloro\u00admethane as eluent. Single crystals were obtained by slow evaporation of a di\u00adchloro\u00admethane solution at room temperature (yield 80%).To a solution of 2-oxo-2-phenyl\u00adethyl 2-phenyl\u00adimidazo, C\u2014H = 0.93\u2005\u00c5 for aromatic [Uiso(H) = 1.2Ueq(C)] and C\u2014H = 0.98\u2005\u00c5 for methine [Uiso(H) = 1.2Ueq(C)] H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022001517/wm5632sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001517/wm5632Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022001517/wm5632Isup3.cmlSupporting information file. DOI: 2106558CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif.The title compound is a Schiff base that exists in the phenol\u2013imine tautomeric form. The mol\u00adecular structure is stabilized by an O\u2014H\u22efN hydrogen bond, forming an  24H24N2O4, was synthesized by the inter\u00adaction of 2-hy\u00addroxy-3-meth\u00adoxy benzaldehyde and 1,4-benzene dimethanamine in ethanol, and crystallizes in the monoclinic space group P21/n with Z\u2032 = 0.5. The mol\u00adecule is not planar, the 1,4-di\u00adethyl\u00adbenzene and the phenol rings are twisted with respect to each other, making a dihedral angle of 74.27\u2005(5)\u00b0. The mol\u00adecular structure is stabilized by an O\u2014H\u22efN hydrogen bond, forming an S(6) ring motif. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, resulting in the formation of sheets parallel to the bc plane. A Hirshfeld surface analysis was undertaken to investigate the various inter\u00admolecular contacts controlling the supra\u00admolecular topology, suggesting the H\u22efO (18%) contacts to be the most significant inter\u00adactions, whereas the H\u22efH (50.5%) and C\u22efH (24.3%) inter\u00adactions are less significant.The Schiff base compound, C There is an intra\u00admolecular O2\u2014H2\u22efN1 hydrogen bond (Table\u00a01S(6) ring motif and also induces the phenol ring and the Schiff base to be nearly coplanar, as indicated by the C6\u2014C8\u2014N1\u2014C9 torsion angle of 178.54\u2005(13)\u00b0. The mol\u00adecule is non-planar, the 1,4-di\u00adethyl\u00adbenzene ring being inclined to the phenol ring by 74.27\u2005(5)\u00b0. The C7\u2014C6\u2014C8\u2014N1 torsion angle [3.8\u2005(2)\u00b0] further supports the co-planarity of the phenol ring and the Schiff base. The C7\u2014O2 distance is 1.3438\u2005(17)\u2005\u00c5, which is close to normal values reported for single C\u2014O bonds in phenols and salicyl\u00adidene\u00adamines  moiety revealed some related structures. The most similar structures are 1,4-bis\u00ad(2-pyridyl\u00admethyl\u00adene\u00adamino\u00admeth\u00adyl)benzene benzene  ring motif as in the title compound. The length of intra\u00admolecular O\u2014H\u22efN hydrogen bond in OCAPAK is especially short [1.65\u2005(2)\u2005\u00c5] compared to that in the title compound [1.789\u2005(15)\u2005\u00c5].A search of the Cambridge Structural Database  using CrystalExplorer17  to 1.404 a.u. (blue). The packing of mol\u00adecules is mainly dependent on H\u22efH (50.5%) and C\u22efH (24.3%) inter\u00adactions and the significant C\u2014H\u22efO inter\u00adactions (18%). Blue regions in the dnorm map indicate inter\u00admolecular inter\u00adactions with distances longer than van der Waals radius sum of the inter\u00adacting elements  of 2-hy\u00addroxy-3-meth\u00adoxy benzaldehyde was dissolved in 20\u2005mL of ethanol and mixed with 0.0100\u2005g (0.074\u2005mmol) of 1,4-benzene dimethanamine dissolved in 20\u2005mL of ethanol Fig.\u00a04. The reaUiso(H) = 1.5Ueq(O) and a distance restraint. The C-bound H atoms were positioned geometrically  and refined using a riding model, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021013347/jq2011sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013347/jq2011Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013347/jq2011Isup3.cmlSupporting information file. DOI: 2128953CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the organic dication and perchlorate anions are linked through N\u2014H\u22efO, C\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming a three-dimensional network.In the title salt, C 20H42N42+\u00b72ClO4\u2212, has been determined using synchrotron radiation at 220\u2005(2)\u2005K. The structure determination reveals that protonation has occurred at diagonally opposite amine N atoms. The asymmetric unit comprises one half of the organic dication, which lies about a center of inversion, and one perchlorate anion. The macrocyclic dication adopts the most stable endodentate trans-III conformation. The crystal structure is stabilized by intra\u00admolecular N\u2014H\u22efN, and inter\u00admolecular N\u2014H\u22efO and C\u2013H\u22efO hydrogen bonds involving the macrocycle N\u2014H and C\u2014H groups as donors and the O atoms of perchlorate anions as acceptors, giving rise to a three-dimensional network.The crystal structure of the title salt, C The macrocycle is basic and readily captures two or four protons to form the [C20H42N4]2+ dication or the [C20H44N4]4+ tetra\u00adcation in which all of the N\u2014H bonds are generally available for hydrogen-bond formation ](NO3)2\u00b73H2O, [Cu(C20H40N4)](NO3)2, [Cu(C20H40N4)](ClO4)2 and [Cu(C20H40N4)(H2O)2](BF4)2\u00b72H2O were reported together with [Zn(C20H40N4)(OCOCH3)2]. In these structures, the copper(II) or zinc(II) cations have tetra\u00adgonally distorted octa\u00adhedral environments with the four N atoms of the macrocyclic ligand in equatorial positions and the O atoms of the counter-anions, water mol\u00adecules or acetato ligands in axial positions \u00b72(C11H10O) \u00b72(NO2OH) \u00b72MeOH 2, (I)We report here the preparation of a new dicationic compound, [Canti with respect to the macrocyclic plane as a result of the mol\u00adecular inversion symmetry. The [C20H42N4]2+ dication adopts an endodentate conformation and trans-III configuration along the center of the macrocyclic cavity. The endo conformation of the dication may be due to the intra\u00admolecular N\u2014H\u22efN hydrogen-bonding inter\u00adaction. Within the centrosymmetric diprotonated amine unit, the C\u2014C and N\u2014C bond lengths range from 1.5173\u2005(18) to 1.5368\u2005(18)\u2005\u00c5 and from 1.4795\u2005(16) to 1.5044\u2005(16)\u2005\u00c5, respectively. The range of N\u2014C\u2014C and C\u2014N\u2014C angles is 108.89\u2005(11) to 113.50\u2005(11)\u00b0 and 113.46\u2005(11) to 114.61\u2005(11)\u00b0, respectively. The bond lengths and angles within the dication are comparable to those found in the free ligand or other cations in (C20H40N4)\u00b72C11H10O \u00b72MeOH 3}(CN)3]2\u00b72H2O\u00b72MeOH \u2005\u00c5] and N1\u2014C3 [1.4795\u2005(16)\u2005\u00c5] are slightly shorter than N2\u2014C8 [1.5044\u2005(16)\u2005\u00c5] and N2\u2014C9 [1.4952\u2005(18)\u2005\u00c5]. Each of the two hydrogen atoms of N2 and N2\u2032  is involved in hydrogen bonding with both of the two remaining nitro\u00adgen atoms (Table\u00a014\u2212 anion vary from 1.4218\u2005(19) to 1.4529\u2005(16)\u2005\u00c5, and the O\u2014Cl\u2014O angles vary from 106.45\u2005(10) to 110.51\u2005(12)\u00b0. The distorted geometry of the ClO4\u2212 anion undoubtedly results from its involvement in hydrogen-bonding inter\u00adactions with the organic cation.An ellipsoid plot of the mol\u00adecular components in (I)s Table\u00a01. The int4\u2212 anions are connected to the [C20H42N4]2+ dication by N\u2014H\u22efO hydrogen bonds. The macrocyclic dication is linked to a neighboring ClO4\u2212 anion through a very weak C\u2014H\u22efO hydrogen bond. The extensive array of these contacts generates a three-dimensional network structure , [C20H42N4]2+ or [C20H44N4]4+. The crystal structures of (C20H40N4)\u00b72C11H10O \u00b72MeOH  were used as provided. All chemicals were reagent grade and used without further purification. As a starting material, macrocycle 3,14-dimethyl-2,6,13,17-tetra\u00adaza\u00adtri\u00adcyclo\u00addocosane, L, was prepared according to a published procedure  was suspended in methanol (20\u2005mL) and the pH was adjusted to 3.0 with 0.5 M HClO4. The mixture was stirred magnetically for 30\u2005min and the resulting solution was filtered. The neat filtrate was allowed to stand for one week to give block-like colorless crystals of (I)Commercially available A and H2B) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C\u2014H distances of 0.97\u20130.98\u2005\u00c5 and an N\u2014H distance of 0.99\u2005\u00c5, and with Uiso(H) values of 1.5 and 1.2 times, respectively, that of the parent atoms. The one N-bound H atom (H1N1) of the amine was assigned based on a difference-Fourier map, and a Uiso(H) value of 1.5Ueq(N1).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021004278/vm2247sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021004278/vm2247Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004278/vm2247Isup3.cmlSupporting information file. DOI: 2079010CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked by C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds into strips, which are connected by F\u22efF contacts into layers. a]pyridine core in the mol\u00adecule of the title compound, C10H7F3N2O, is planar within 0.004\u2005(1)\u2005\u00c5. In the crystal, the mol\u00adecules are linked by pairs of C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming strips. These strips are connected by the F\u22efF contacts into layers, which are further joined by \u03c0\u2013\u03c0 stacking inter\u00adactions. The Hirshfeld surface analysis and fingerprint plots reveal that mol\u00adecular packing is governed by F\u22efH/H\u22efF (31.6%), H\u22efH (16.8%), C\u22efH/H\u22efC (13.8%) and O\u22efH/H\u22efO (8.5%) contacts.The bicyclic imidazo[1,2- The C2\u2014C1\u2014C8\u2014C9 and N2\u2014C1\u2014C8\u2014O1 torsion angles of 1.04\u2005(18) and 1.14\u2005(19)\u00b0, respectively, show that the ethanone group lies near the plane of the bicycle. The bond lengths N1\u2014C2, C2\u2014C1 and C1\u2014C8 of 1.3367\u2005(16), 1.3987\u2005(16) and 1.4247\u2005(16)\u2005\u00c5, respectively, indicate strong \u03c0-conjugation in the N1\u2013O1 chain.In the mol\u00adecule of the title compound Fig.\u00a01, the fusCg1\u22efCg1; Cg1 is the centroid of the imidazole ring].In the crystal, the mol\u00adecules are linked by pairs of C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds into strips elongated along the [210] direction Figs. 2. These ss Figs. 3. The lays Figs. 3 and \u03c0\u2013\u03c0 Crystal Explorer 17 imidazopyridin-3-amine imidazopyridin-3-amine  ring motif. In the crystal, a short H\u22efH contact links adjacent mol\u00adecules into centrosymmetric dimers. The dimers are joined by weak C\u2014H\u22ef\u03c0 and slipped \u03c0\u2013\u03c0 stacking inter\u00adactions, forming layers parallel to (110), which are connected into a three-dimensional network by short Br\u22efH contacts. In the crystal of PILGAV01, N\u2014H\u22efN hydrogen bonds link the mol\u00adecules into [010] chains. The cohesion of the crystal structure of DABTEI is ensured by C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming layers parallel to the ac plane. In ZAPJAD, the supra\u00admolecular structure is defined by two kinds of inter\u00admolecular hydrogen bonds. Pairs of N\u2014H\u22efN hydrogen bonds link the mol\u00adecules into centrosymmetric dimers and N\u2014H\u22efO hydrogen bonds link the dimers into tubular chains running along the a-axis direction. In the crystal of ULEGOI, mol\u00adecules are linked into chains through pairs of C\u2014H\u22efN inter\u00adactions, forming a axis.The most closely related compounds containing a similar imidazo+.A mixture of (Uiso(H) = 1.2Ueq(C) for CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021012676/yk2161sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021012676/yk2161Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021012676/yk2161Isup3.cmlSupporting information file. DOI: 2124974CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E)-2-benzyl-1,3-di\u00adphenyl\u00adiso\u00adthio\u00aduronium iodide, was prepared by the reaction of 1,3-di\u00adphenyl\u00adthio\u00adurea and benzyl iodide. In the crystal, N\u2014H\u22efI hydrogen bonds link the components into [100] chains.The title compound, a salt form of \u00b0 and electrons are delocalized over the N+= C\u2014N skeleton. The dihedral angle between the aromatic rings attached to the N atoms is 40.60\u2005(9)\u00b0. In the crystal, N\u2014H\u22efI hydrogen bonds link the components into [100] chains.In the title mol\u00adecular salt, C R\u2013S\u2013C\u2013(NHR)2+ moiety have been investigated as their hydrogen\u2013bonding motifs for mol\u00adecular recognition of anions \u00admethyl\u00adene]benzenaminium and toluyl units are linked to the sulfur atom as a thio\u00adether. The C7\u2014S1 and C8\u2014S1 bond lengths are 1.823\u2005(2) and 1.751\u2005(2)\u2005\u00c5, respectively, and the C\u2014S\u2014C bond angle is 101.66\u2005(9)\u00b0. The conformation of C1 and C8 about the C7\u2014S1 bond is gauche [C1\u2014C7\u2014S1\u2014C8 = 49.53\u2005(16)\u00b0]. The C\u2014S\u2014C bond angle in the title compound is somewhat smaller than that for di-p-tolyl sulfide \u00admethyl\u00adene]benz\u00aden\u00adaminium moiety of the title cation, the \u03c0-electrons of the iminium double bond are delocalized over the N1\u2014C6\u2014N2 skeleton .The title compound, CI\u2212 Fig.\u00a01, is a moIn the crystal, the cations and anions are linked by almost linear N\u2014H\u22efI hydrogen bonds Fig.\u00a02, generatvia CCDC Access Structures, November 2021; Groom et al., 2016N-[(phenyl\u00adamino)\u00admethyl\u00adene]benzenaminium but the compound most similar to the title compound is S-benzyl\u00adiso\u00adthio\u00aduronium chloride , to give a the title compound as a yellow solid . A solution of iso\u00adthio\u00aduronium iodide in methanol was slowly evap\u00adorated at room temperature to give crystals of the title compound: m.p. 442\u2013443\u2005K; 1H NMR : \u03b4 7.21\u20137.39 , \u03b4 4.45 ; HR TOF\u2013MS for C20H18N2S: calculated 318.1186 (M+), found 318.1185 (M+).1,3-Di\u00adphenyl\u00adthio\u00adurea (4.4\u2005mmol) was added to a solution of benzyl iodide (13.2\u2005mmol) in dry di\u00adchloro\u00admethane at room temperature. The reaction mixture was then stirred for 24\u2005h and concentrated Uiso(H) = 1.2Ueq(carrier).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021013086/hb7997sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013086/hb7997Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013086/hb7997Isup3.cmlSupporting information file. DOI: 2127354CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The parallel-aligned adtp4\u2212 ligands with an alternately reversed arrangement further link adjacent CoII ribbons into (010) layers, which are assembled into a three-dimensional supra\u00admolecular architecture via inter\u00admolecular hydrogen bonds.The title compound, {[Co 2(C12H7NO8)(H2O)2]\u00b71.6H2O}n comprises two CoII ions, which are coordinated by fully deprotonated 2-aminodi\u00adacetic terephthalic acid (adtp4\u2013) and terminal water mol\u00adecules in distorted octa\u00adhedral N1O5 and O6 coordination environments. The title compound features tetra\u00adnuclear CoII units bridged by \u03ba3O:O:O\u2032- and \u03ba3O:O,O\u2032-carboxyl\u00adate groups, which are joined into ribbons via syn\u2013anti carboxyl\u00adate bridges. The parallel adtp4\u2013 ligands with an alternately reversed arrangement further link adjacent CoII ribbons into (010) layers, which are assembled into a three-dimensional supra\u00admolecular network via inter\u00admolecular hydrogen bonds. The disordered water solvent mol\u00adecules are situated in channels parallel to [100]. Magnetic measurements and analyses reveal that the title compound displays anti\u00adferromagnetic behaviour. The purity of the title compound was characterized by X-ray powder diffraction.The asymmetric unit of the polymeric title compound {[Co The crystal structure, power X-ray diffraction pattern and magnetism of (I) were also studied in detail.Our previous studies have focused on the construction of CPs based on semi-rigid multi\u00adcarb\u00adoxy\u00adlic acids with the aminodi\u00adacetate moiety such as 2-aminodi\u00adacetic terephthalic acid (HI) comprises two CoII ions, one adtp4\u2013 ligand, two terminal water ligands and 1.6 disordered solvent water mol\u00adecules. Regarding the adtp4\u2013 ligand, one carboxyl\u00adate group  of the aminodi\u00adacetate moiety adopts a \u03ba3-O:O:O\u2032 coordination mode and the other one  employs a syn\u2013anti bidentate bridging fashion, whereas the carboxyl\u00adate group in the ortho-position  coordinates in a \u03ba3-O:O,O\u2032 mode and that in the meta-position  binds to one CoII ion in monodentate fashion (see Scheme). As shown in Fig.\u00a011O5 coordination set for Co1 and an O6 set for Co2. The adip4\u2013 ligand chelates Co1 with the amino nitro\u00adgen atom (N1) and carboxyl\u00adate oxygen atoms  from the aminodi\u00adacetate moiety and its ortho-positioned carbox\u00adylate group. The residual cis-related sites are occupied by one meta-positioned carboxyl\u00adate oxygen atom (O4ii) and one aminodi\u00adacetate oxygen atom (O7i) from two other adip4\u2013 ligands (for symmetry codes refer to Table\u00a01ortho-positioned carboxyl\u00adate group (O1iii and O2iii) from another adip4\u2013 ligand chelates Co2, two cis-related positions of which are occupied by two aminodi\u00adacetate oxygen atoms (O8iv and O6) from two different adip4\u2013 ligands. The remaining two cis-related sites of Co2 are occupied by two terminal water ligands (O9 and O10). The length of the Co\u2014N bond is 2.241\u2005(3)\u2005\u00c5 and the Co\u2014O distances are between 1.992\u2005(3) and 2.362\u2005(3)\u2005\u00c5, which are all in the expected ranges. As shown in Fig.\u00a024\u2013 ligands bridge two pairs of CoII ions  into a tetra\u00adnuclear unit with their \u03ba3O:O:O\u2032-carboxyl\u00adate groups from the aminodi\u00adacetate moieties and ortho-positioned \u03ba3O:O,O\u2032-carboxyl\u00adate groups  from \u03ba3O:O:O\u2032-carboxyl\u00adate groups doubly bridge Co1 and Co1ii into a dinuclear unit. The dinuclear unit is further joined with two equivalent Co2i and Co2iii atoms via \u03ba3O:O:O\u2032-carboxyl\u00adate groups and \u03bc2-oxygen bridges (O1 and O1i) from \u03ba3O:O,O\u2032-carboxyl\u00adate groups. Adjacent tetra\u00adnuclear units are linked into a ribbon via double syn\u2013anti bridging carboxyl\u00adate groups from the aminodi\u00adacetate moieties. The closest Co1\u22efCo2 and Co1\u22efCo1 distances in the ribbon are 3.7074\u2005(8) and 3.5762\u2005(8)\u2005\u00c5, respectively. Parallel-aligned adtp4\u2013 ligands with an alternately reversed arrangement bind adjacent CoII ribbons into a layer extending parallel to (010)  Fig.\u00a03.I) are assembled into a three-dimensional supra\u00admolecular network via inter\u00admolecular hydrogen bonds O9\u2014H9A\u22efO3v and O9\u2014H9B\u22efO2vi (Table\u00a02The (010) layers of (i Table\u00a02. The pos\u03c7M) of (I) were measured in the range 2\u2013300\u2005K under 1000 Oe. The \u03c7M, \u03c7M\u22121 and \u03c7MT versus T plots are shown in Fig.\u00a05\u03c7MT at 300\u2005K is 5.43\u2005cm3\u2005K\u2005mol\u22121, which is much larger than the expected spin-only value (3.75\u2005cm3\u2005K\u2005mol\u22121) of two isolated CoII ions with g = 2.0, S = 3/2, which may be due to the contribution of the incompletely quenched orbital magnetic moment. As the temperature decreases, the \u03c7MT value decreases slowly between 300 and 50\u2005K and then it descends more steeply to the minimum value of 0.51\u2005cm3\u2005K\u2005mol\u22121 at 2\u2005K. The curve clearly indicates that the dominant anti\u00adferromagnetic coupling is operating. The temperature dependence of \u03c7M\u22121 follows the Curie\u2013Weiss law, and the linear fit by the equation 1/\u03c7M = (T\u00a0\u2212\u00a0\u03b8)/C gives C = 5.76\u2005cm\u22123 K mol\u22121 and \u03b8 = \u221221.99\u2005K, which is consistent with an anti\u00adferromagnetic behaviour.The variable-temperature magnetic susceptibilities . The other two CoII complexes are discrete coordination mol\u00adecules (H2O)6]\u00b75H2O}n, has been synthesized, which consists of parallel stacked zigzag chains in which CoII cations are linked together through \u03bc3-adtp4\u2212 anions.A search of the Cambridge Structural Database  of Co(NO3)2\u00b76H2O and 5.0\u2005ml of CH3CN, then transferred into a 25.0\u2005ml Teflon-lined stainless steel autoclave. The autoclave was sealed, heated to 393\u2005K and held at that temperature for 72\u2005h. The autoclave was allowed to cool to 303\u2005K within 24\u2005h. Plate-like pink crystals of (I) were collected in 66% yield based on H4adtp. Analysis calculated (%) for C12Co2N1O11.6H14.2 (Mr = 475.90): C 30.29, H 3.01, N, 2.94; found: C 30.18, H 3.15, N 3.06. Selected IR data : 3389 (s), 1631 (s), 1570 (m), 1405 (s), 1373 (s), 1319 (b), 1111 (b), 780 (b), 712 (b).HI) was confirmed by powder X-ray diffraction analysis . The peak positions of the experimental PXRD patterns are in good agreement with those simulated on basis of the present single-crystal X-ray data, indicating that a pure phase was obtained.The phase purity of compound (Uiso(H) = 1.5 Ueq(O). Other hydrogen atoms were placed at geometrically calculated positions and treated as riding, with Csp2\u2014H = 0.93\u2005\u00c5, Csp3\u2014H = 0.97\u2005\u00c5 and Uiso(H) = 1.2 Ueq(C). H atoms of O11, O12, O13 and O14 are not included in the model but were taken into account in the overall formula.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021008355/wm5615sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021008355/wm5615Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021008355/wm5615sup4.tifFigure S1 The simulated and experimental PXRD patterns for compound (I). DOI: 2063394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of a ciprofloxacin salt with 2,6-di\u00adhydroxy\u00adbenzoic acid and a ciprofloxacin hydro\u00adchloride salt co-crystal with 3,5-di\u00adhydroxy\u00adbenzoic acid are reported. 17H19FN3O3+\u00b7C7H5O4\u2212, (I), and ciprofloxacin hydro\u00adchloride\u20133,5-di\u00adhydroxy\u00adbenzoic\u2013water (1/1/1), C17H19FN3O3+\u00b7Cl\u2212\u00b7C7H6O4\u00b7H2O, (II), were determined. In (I) and (II), the ciprofloxacin cations are connected via head-to-tail N\u2014H\u22efO hydrogen bonding. Both structures show an alternating layered arrangement between ciprofloxacin and di\u00adhydroxy\u00adbenzoic acid.The crystal structure of two multi-component crystals of ciprofloxacin [systematic name: 1-cyclo\u00adpropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)quinoline-3-carb\u00ad\u00adoxy\u00adlic acid], a fluoro\u00adquinolone anti\u00adbiotic, namely, ciprofloxacin 2,6-di\u00adhydroxy\u00adbenzoate salt, C The formation of multi-component crystals, Ka of 1.30  and 1.325\u2005(3)\u2005\u00c5 indicate that it exists as the neutral carb\u00adoxy\u00adlic form. However, in 2,6HBA, the C\u2013O distances are very similar i.e., 1.263\u2005(4) and 1.267\u2005(3)\u2005\u00c5 due to resonance stabilization in the carboxyl\u00adate anion on Fig.\u00a01. The C\u2014OP1 space group despite the lack of a chiral centre. The asymmetric unit comprises one ciprofloxacin cation, one chloride anion and one 3,5HBA mol\u00adecule, as shown in Fig.\u00a02Ka of 4.04  and 1.314\u2005(4)\u2005\u00c5, respectively, also confirm the neutral state of this moiety. On the other hand, the piperazinyl group is protonated. Hence, compound (II)Compound (II)A\u22efF1 hydrogen bonding (Tables 1Compounds (I) Tables 1 and 2 \u25b8.i.e. N3\u2014H3B\u22efO4, N3\u2014H3B\u22efO5, and N3\u2014H3A\u22efO6, form an infinite chain structure along the a-axis direction a-axis, centrosymmetric pairs of ciprofloxacin mol\u00adecules are stacked by \u03c0\u2013\u03c0 inter\u00adactions. The distance between the centroids of symmetry-related C4\u2013C9 rings is 3.4986\u2005(11)\u2005\u00c5. This arrangement leads to the formation of a columnar packing arrangement. Inter\u00adestingly, a similar packing feature was observed in the 1.75 hydrate of ciprofloxacin salicylate n Table\u00a01. The chaA\u22efO1 hydrogen bonds (Table\u00a02a). Inter\u00adestingly, compound (II)b).The supra\u00admolecular features of compound (II)s Table\u00a02, formings Table\u00a02a. Interet al., 2019et al., 2020et al., 2020et al., 2020et al., 2014et al., 2016Several crystal structures of ciprofloxacin salts with benzoic acid derivatives have been reported, including salts with salicylic acid Uiso) were fixed to 1.2Ueq of the parent carbon or nitro\u00adgen atom and 1.5Ueq for hydroxyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022001177/dx2042sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022001177/dx2042Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001177/dx2042IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022001177/dx2042Isup4.cmlSupporting information file. DOI: 2098049, 2098403CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N,N-di\u00admethyl\u00adformamide monosolvate was found to crystallize in the monoclinic space group P21/c. The crystal structure of this compound is stabilized by N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds, as well as \u03c0\u2013\u03c0 stacking.9-Amino\u00adacridinium chloride  N,N-di\u00admethyl\u00adformamide monosolvate, C13H11N2+Cl\u2212\u00b7C3H7NO, crystallizes in the monoclinic space group P21/c. The salt was crystallized from N,N-di\u00admethyl\u00adformamide. The asymmetric unit consists of two C13H11N2+Cl\u2212 formula units. The 9-amino\u00adacridinium (9-AA) mol\u00adecules are protonated with the proton on the N atom of the central ring. This N atom is connected to an N,N-di\u00admethyl\u00adformamide mol\u00adecule by a hydrogen bond. The H atoms of the amino groups create short contacts with two chloride ions. The 9-AA cations in adjacent layers are oriented in an anti\u00adparallel manner. The mol\u00adecules are linked via a network of multidirectional \u03c0\u2013\u03c0 inter\u00adactions between the 9-AA rings, and the whole lattice is additionally stabilized by electrostatic inter\u00adactions between ions.9-Amino\u00adacridinium chloride  These bond lengths are characteristic for a C=N double bond that can originate from tautomerism of the cation, as shown on the scheme.The amino groups for two 9-amino\u00adacridine mol\u00adecules do not readily add a proton. The state of ionization is confirmed by both the H-atom positions (located from the difference map) and by the hydrogen bonding as shown in Table\u00a01et al., 1960The acridine moieties are nearly planar in the crystalline phase with atoms N2, C1, N1 and N5, C17 and N4 arranged almost linearly (N2\u22efC1\u2014N1 = 176\u00b0 and N5\u22efC17\u2014N4 = 180\u00b0). The dihedral angle between the two outer fused rings is 3.39\u2005(14)\u00b0 for the mol\u00adecule containing N2, while the corresponding angle in the mol\u00adecule containing N5 is 1.18\u2005(15)\u00b0. The second value is comparable with that found for acridine , which stack perpendicularly to the c axis. There are two types of 9-AA fused rings in the crystal structure, which results in the propagation of layers in a zigzag manner along b-axis direction .The packing of the mol\u00adecules in the crystal is illustrated in Fig.\u00a02on Fig.\u00a02.A, attached to N2 and N5, form hydrogen bonds to N,N-di\u00admethyl\u00adformamide atoms, O1 and O2, with d(N\u22efO) = 2.723\u2005(5)\u20132.740\u2005(5)\u2005\u00c5, N\u2014H\u22efO = 175-176\u00b0. The chloride ions are linked via N\u2014H\u22efCl hydrogen bonds , forming di\u00admers  = 3.608\u2005(5)\u20133.688\u2005(4)\u2005\u00c5 and C\u2014H\u22efCl = 163-172\u00b0]  to 4.2236\u2005(3)\u2005\u00c5. On the other hand, only the two aromatic rings of the acridine B mol\u00adecules participate in \u03c0\u2013\u03c0 inter\u00adactions, with adjacent acridine skeletons rotated in-plane with respect to one another. The centroid\u2013centroid distances vary from 3.6514\u2005(3) to 4.7445\u2005(5)\u2005\u00c5.Adjacent acridine skeletons are linked nt Fig.\u00a03. All of et al., 2016et al., 1974bP21/c space group with an 9-AA cation and a 3-chloro\u00adbenzoate anion in the asymmetric unit and the crystal structure features N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions. Inversely oriented cations and anions form a tetra\u00admer; these ions are linked via N(amino)\u2014H\u22efO (carb\u00adoxy) hydrogen bonds, forming a ring motif. 9-Amino\u00adacridinium 3-chloro\u00adbenzoate  was dissolved in N,N-di\u00admethyl\u00adformamide (4\u2005ml) under heating at 418\u2005K until the 9-AA\u00b7HCl had fully dissolved. The solution was left to cool to 280\u2005K. Single crystals were obtained after 2 days.9-Amino\u00adacridinium hydro\u00adchloride  = 1.2Ueq(C) for aromatic hydrogens and the C\u2014H group and C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for the CH3 group. A rotating model was used for the methyl group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021011816/dx2038sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021011816/dx2038Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021011816/dx2038Isup3.cmlSupporting information file. DOI: 2120699CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This tiara-shaped hexa\u00admer crystallizing in the triclinic space group P4 centers, which are inter\u00adconnected through twelve \u03bc2-bridging benzyl thiol\u00adate groups. The Pd\u22efPd contacts range from 3.0892\u2005(2) to 3.1609\u2005(2)\u2005\u00c5 and can be considered as weakly bonding. The unit cell of Pd6 contains also a co-crystallized anthracene-9,10-dione mol\u00adecule.The first title compound, C R)(H)\u2013S  unit can either be synthesized by nucleophilic substitution of geminal dihalides X\u2013C(R)(H)\u2013X by thiol\u00adates RS\u2212 \u00admeth\u00adyl]anthracenes with AgI salts 2], ] compounds is dominated by chelate complexes in which open-chain di\u00adthio\u00adether or macrocyclic polythio\u00adether ligands form five- or six-membered rings such as  ] ], in which the thia\u00admacrocycle forms a strained four-membered chelate ring 4][ClO4]2, the strained chelate complexes [M(PhSCH2SPh)4](ClO4)2  are formed bis\u00ad(benzyl\u00adsulfane)-S,S\u2032)] was not formed according to the NMR data. Instead, a crystallographic study of a yellow\u2013orange crystal revealed the formation of a cyclic hexa\u00adnuclear thiol\u00adate-bridged cluster [Pd6(\u03bc2-SCH2Ph)12], Pd6. It is well known that thio\u00adacetals can be cleaved by soft HgII ions yielding aldehydes or other oxygenated products. One example is the HgIII-promoted deprotection of 3,5-bis\u00adBODIPYs, in which cleavage of a di\u00adthio\u00adacetal function to aldehyde groups occurs (benz\u00adyl)sulfane with ceric ammonium nitrate 2] with 2.1 equivalents of benzyl mercaptan in CH2Cl2 solution. However, the isolation of Pd6 was hampered by the co-crystallization of important amounts of the eight-membered cluster Pd8 [Pd8(\u03bc2-SCH2Ph)16], having a structure similar to that of [Pd8(\u03bc2-SPr)16] SBz] (SUNMAQ)  and 2-[bis\u00ad(benzyl\u00adsulfan\u00adyl)meth\u00adyl]-6-meth\u00adoxy\u00adphenol [107.76\u2005(10)\u00b0], but considerably less than in [BzSCH2SBz] [117.33\u2005(7)\u00b0]. The phenyl rings of the benzyl groups and that of the anthracene unit form dihedral angles of 49.21\u2005(4) and 58.79\u2005(5)\u00b0.Compound L1 with [PdCl2(PhCN)2] shown in Fig.\u00a036(\u03bc2-SPr)12] 12] 12] 12] 12] 12] has been reported 12] is that of the phenyl\u00adethane\u00adthiol\u00adate-decorated nanocluster [Pd6(\u03bc2-SCH2CH2Ph)12]  to 3.1609\u2005(2)\u2005\u00c5. The mean Pd\u22efPd separation of 3.1213\u2005(2)\u2005\u00c5 is quite similar to that of the other derivatives and may be considered as weakly bonding \u2005\u00c5 is close to those of the other [Pd6(\u03bc2-SR)12] analogues. The S\u2014Pd\u2014S bridge angles vary within the range 81.033\u2005(16)\u201399.246\u2005(16)\u00b0. The twelve sulfur atoms form two S6 hexa\u00adgons parallel to the central Pd6 ring from both sides, conferring finally a tiara-like shape to the Pd6S12 scaffold.The core of Note that the crystal structure of anthracene-9,10-dione  has already been the object of several crystallographic studies and is therefore not commented herein  distance of 2.519\u2005(18)\u2005\u00c5, the C14\u2014H14\u22efC24 distance of 2.741\u2005(18)\u2005\u00c5 and the C1\u2014H1B\u22efC9 distance of 2.847\u2005(16)\u2005\u00c5 are short enough to be considered as weak inter\u00admolecular inter\u00adactions . The red spots on the surface indicate the close contacts to adjacent mol\u00adecules. There are three areas of red spots which can be classified as C\u2014H\u22ef\u03c0 inter\u00adactions. The first and most important inter\u00adaction is the C\u2014H\u22ef\u03c0 contact of one of the phenyl\u00admethane\u00adthiol\u00adate substituents to the anthracene scaffold of a neighboring mol\u00adecule (C14\u2014H14\u22efC24). Furthermore, there are significant inter\u00adactions of the anthracene unit to an adjacent anthracene unit (C21\u2014H21\u22efC16/17/29). Then, there is also a weak C\u2014H\u22ef\u03c0 contact of two phenyl\u00admethane\u00adthiol\u00adate substituents (C1\u2014H1B\u22efC9). The contributions of the different types of inter\u00admolecular inter\u00adactions are shown in the two-dimensional fingerprint plots in Fig.\u00a08b and 6c illustrate the Hirshfeld surface mapped over the shape-index and the curvedness. The shape-index shows large red regions of concave curvature for the anthracene motif, whereas the C\u2014H-donors shows opposite curvature.A Hirshfeld surface analysis methyl-3,5-di\u00adnitro\u00adthio\u00adbenzoate 2 revealed only three similar structures, namely 2,6,10,14,19,24-hexa-p-benz-4,8,12,16,17,21,22,26-octa\u00adthia\u00adtri\u00adcyclo\u00adhexa\u00adcosa\u00adphane benzene clathrate 2(PMe3)2] 2ethane)] 2propane)] 2(bis\u00ad(di\u00adphenyl\u00adphosphino)methane)Cl2] 12] clusters have found applications as precursors for the preparation of monodisperse PdS nanoparticles 12] mol\u00adecules are inter\u00adconnected in the solid state by hydrogen bonds through the hy\u00addroxy groups of the thiol\u00adate ligands, thus generating an infinite three-dimensional supra\u00admolecular network 12] has been prepared and probed as a macrocyclic host to include an AgI ion as guest . Crystals suitable for single-crystal X-ray crystallography were grown by slow diffusion of hexane into a di\u00adchloro\u00admethane solution of L1, m.p. 438\u2013440\u2005K. 1H NMR : 9.03 , 8.39 , 8.00 , 7.95 , 7.55\u20137.47 , ddd , 7.28\u20137.22 , 7.14\u20137.09 , 6.91 , 5.94 , 3.79 , 3.55 . 13C{1H} NMR  138.34 (C16), 132.50 (C17), 131.46 (Cq), 131.36 (Cq), 130.28 (Cq), 129.58 (CHAr), 129.56 (C21), 129.47 (C25), 129.13 (Cq), 128.96 (CHAr), 128.84 (C23), 127.75 (C18), 127.53 (CHAr), 126.63 (C26), 125.61 (C19), 125.12 (C20), 124.91 (C27), 122.99 (C28), 45.02 (S2CH), 37.89 (SCH2). IR (ATR) cm \u22121: 3050 and 3025 (C\u2014H Ar), 2998, 2948 and 2906 , 1589, 1519 (C=C), 696 (C\u2014S).9-Anthracenecarboxaldehyde  and benzyl mercaptan  were suspended in conc. HCl (2\u2005ml) and allowed to stir at room temperature. After 2\u2005h, the reaction mixture was neutralized with aqueous NaHCO2(PhCN)2Reaction of L1 with PdCl: L1  and PdCl2(PhCN)2  were dissolved in 5\u2005ml of di\u00adchloro\u00admethane and allowed to stir at room temperature for 30 minutes. During the reaction, a red solution was obtained, which was kept in refrigerator overnight yielding yellow crystals of 9-anthraldehyde along with yellow\u2013orange co-crystals of the  cluster, Pd6. 1H NMR ): 8.92\u20136.86 , 3.61 , 3.58 .Uiso(H) = 1.2Ueq(C). Hydrogen atoms H1B, H14 and H21 for L1 were located in the difference-Fourier map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021006113/hb7976sup1.cifCrystal structure: contains datablock(s) mo_b0159_0m, mo_b0283_0m, New_Global_Publ_Block. DOI: 10.1107/S2056989021006113/hb7976mo_b0159_0msup2.hklStructure factors: contains datablock(s) mo_b0159_0m. DOI: 10.1107/S2056989021006113/hb7976mo_b0283_0msup3.hklStructure factors: contains datablock(s) mo_b0283_0m. DOI: 2089413, 2089412CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Preoperative pulmonary function testing is mandatory for non-small cell lung cancer (NSCLC) surgery. The predicted postoperative FEV1 (ppoFEV1) is used for further risk stratification. We compared the ppoFEV1 with the postoperative FEV1 (postFEV1) in order to improve the calculation of the ppoFEV1.87 patients voluntarily received an FEV1 assessment 1\u00a0year after surgery. ppoFEV1 was calculated according to the Brunelli calculation. Baseline characteristics and surgical procedure were compared in a uni- and multivariate analysis between different accuracy levels of the ppoFEV1. Parameters which remained significant in the multinominal regression analysis were evaluated for a modification of the ppoFEV1 calculation.p\u2009=\u20090.01), packyears , younger age , and patients undergoing pneumectomy . For the customized ppoFEV1 we excluded pneumonectomies. For patients\u2009<\u200960\u00a0years, an additional lung segment was added to the calculation. ppoFEV1\u2009=\u2009preFEV1\u2009\u00d7\u2009Independent factors for a more inaccurate ppoFEV1 were preoperative active smoking (odds ratio (OR) 4.1, confidence interval (CI) 3.6\u20136.41; We were able to enhance the predictability of the ppoFEV1 with modifications. The modified ppoFEV1 (1.828\u00a0l\u2009\u00b1\u20090.479\u00a0l) closely approximates the postFEV1 of 1.823\u00a0l\u2009\u00b1\u20090.476\u00a0l, (0.27%) while the original ppoFEV1 calculation is at 1.78\u00a0l\u2009\u00b1\u20090.53 (2.19%). However, if patients require pneumectomy, more complex techniques to determine the ppoFEV1 should be included to stratify risk.The online version contains supplementary material available at 10.1007/s00408-021-00464-4. Anatomical lung resection is the gold standard for the treatment of early-stage non-small cell lung cancer (NSCLC) . PulmonaAll relevant patient data were taken from the electronic hospital information system of our institute. 87 patients voluntarily presented to our out-patient department 1 year after surgery for a routine surgical check-up which included a pulmonary function test. We included all patients who received a postFEV1 in our analysis.The ppoFEV1 is calculated based on the preoperative FEV1 (preFEV1), the number of functional lung segments resected (y), and the total number of functional segments available at time of resection (z). PpoFEV1\u2009=\u2009preFEV1\u2009\u00d7\u20091 \u2212 entclass1pt{minimamentclasspt{minimaAfter calculating the ppoFEV1, we compared our results with the postFEV1 1\u00a0year after surgery.We determined accuracy levels and classified the deviation of the ppoFEV1 in relation to the postFEV1. In order to reflect the greatest differences, we defined the accuracy level of\u2009\u00b1\u20092% as most accurate, the accuracy level of\u2009\u00b1\u200910% as moderately accurate, and the accuracy level of\u2009\u00b1\u2009\u2009>\u200910% as inaccurate. We performed a subgroup analysis excluding the ppoFEV1\u2009\u00b1\u20092% from the ppoFEV1\u2009\u00b1\u200910%, in order to prevent counting ppoFEV1\u2009\u00b1\u20092% patients twice. These patients were defined as ppoFEV1\u2009\u00b1\u200910%\u2009>\u2009\u2009\u00b1\u20092%. We analyzed baseline characteristics and surgical procedures which eventually resulted in the most accurate- or inaccurate ppoFEV1 with univariate and multivariate analyses.\u03c72 or Fisher\u2019s exact test. Continuous parameters were expressed as mean \u00b1 standard deviation (SD) and were analyzed by an unpaired Student t test. p-value <0.05 was considered statistically significant. Statistical analysis was performed using the SPSS statistical software package .In cases where univariate analysis showed significant differences, we performed a multinominal regression analysis for further evaluation. Multinomial differences are described by odds ratio (OR) and 95% confidence interval (CI). Categorical variables were analyzed using Pearson\u2019s Significant multinominal parameters were included in our customizing process. The primary objective of this customization was to determine baseline characteristics or surgical procedures which could be included in the calculation in order to improve the ppoFEV1.The customizing process is explained in the results part. The formulas calculated by us are the following.For patients\u2009<\u200960\u00a0years, an additional lung segment is added to the calculation ppoFEV1\u2009=\u2009preFEV1\u2009\u00d7\u2009A total of 464 patients underwent anatomical pulmonary resections since 2012 at our institution. 87 (18.8%) patients presented voluntarily for a postoperative check-up and a redo assessment of their pulmonary function 1 year after surgery. We classified patients into categories according to how accurately the ppoFEV1 predicted the postFEV1. The ppoFEV1 of 79% patients showed moderate accuracy of\u2009\u00b1\u200910%. 24% of patients were most accurately predicted with a\u2009\u00b1\u20092% deviation. Calculated values exceeded\u2009>\u2009\u2009\u00b1\u200910% in 21% of patients. 51 (45%) patients showed a ppoFEV1\u2009\u00b1\u200910%\u2009>\u2009\u2009\u00b1\u20092% accuracy level. The mean preFEV1 of the cohort was 2.34 l (l)\u2009\u00b1\u20090.61\u00a0l and the mean postFEV1 was 1.82\u00a0l\u2009\u00b1\u20090.47\u00a0l, respectively. Calculation of the ppoFEV1 yielded 1.78\u00a0l\u2009\u00b1\u20090.53\u00a0l (2.19%).p\u2009=\u20090.01).The baseline characteristics according to the predictive accuracy level are presented in Tables p\u2009=\u20090.05). The preoperative DLCO% (preDLCO%) of patients with ppoFEV1\u2009\u00b1\u20092% showed a significantly higher value (87.4\u2009\u00b1\u200917.7) than in ppoFEV1\u2009\u00b1\u200910\u2009>\u2009\u2009\u00b1\u20092% patients (77.3\u2009\u00b1\u200919.9) (p\u2009=\u20090.05). The postDLCO however did not differ between\u2009\u00b1\u20092% and\u2009\u00b1\u200910\u2009>\u2009\u2009\u00b1\u20092%. 74.7% of patients were active smokers at the time of surgery (active smoking: smoking in 3\u00a0months prior to surgery). Active smoking did not differ between ppoFEV1\u2009\u00b1\u20092% and ppoFEV1\u2009\u00b1\u200910%\u2009>\u2009\u2009\u00b1\u20092%. 100% of ppoFEV1\u2009>\u2009\u2009\u00b1\u200910% patients were active smokers compared to 71.0% of ppoFEV1\u2009\u00b1\u200910% . Patients with ppoFEV1\u2009>\u2009\u2009\u00b1\u200910% smoked significantly more than ppoFEV1\u2009\u00b1\u200910% patients (61.4\u2009\u00b1\u200919.1 vs. 41.2\u2009\u00b1\u200924.5 p\u2009=\u20090.002). Heavy smoking is defined as\u2009>\u200930 packyears [p\u2009=\u20090.001).The distribution of age in relation of the ppoFEV1 is shown in Fig.\u00a0 77.3\u2009\u00b1\u20091.9 . However, younger age , active smoking , packyears , and heavy smoking (>\u200930 packyears)  were independent factors for a more inaccurate ppoFEV1.We carried out a multinominal regression analysis for further evaluation of significant results from the univariate analysis (included in Tables p\u2009=\u20090.05). The right lower lobe was resected less often in patients with ppoFEV1\u2009\u00b1\u20092% . Patients with ppoFEV1\u2009\u00b1\u20092% never underwent pneumectomy (0 vs. 3.0%) or bilobectomy (0% vs. 6.0%). The most inaccurate FEV1\u2009>\u2009\u2009\u00b1\u200910% was significantly more frequent in patients undergoing pneumectomy   . Pneumectomy on the other was an independent factor for ppoFEV1\u2009>\u2009\u2009\u00b1\u200915% in the multivariate analysis  \u2009<\u200960\u00a0years and (3) active heavy smokers we used the original calculation as the modifications canceled each other.To improve the accuracy of the ppoFEV1, we tried to keep the method as simple as possible.In the following section we give two computational examples with the preFEV1 of two patients explaining our customized ppoFEV1.ppoFEV1\u2009=\u2009preFEV1 x preFEV1\u2009=\u20092.67\u00a0l; postFEV1\u2009=\u20092.04\u00a0l; ppoFEV1 2.25\u00a0lCalculation method: 2.67\u00a0l\u2009\u00d7\u20091\u2009\u2212\u2009Customized method: 2.67\u00a0l\u2009\u00d7\u20091\u2009\u2212\u2009Patient undergoing an upper right lobe resection\u2009<\u200960\u00a0years:ppoFEV1\u2009=\u2009PreFEV1 \u00d7 Calculation method: 1.77 \u00d7 Customized method: 1.77 \u00d7 Patient undergoing a lower left lobe resection heavy smoker:The mean postFEV1 was 1.823\u00a0l\u2009\u00b1\u20090.476\u00a0l. By customizing the ppoFEV1 the calculation was more accurate (1.828\u00a0l\u2009\u00b1\u20090.479\u00a0l) (0.27%) compared to the original ppoFEV1 (1.78\u00a0l\u2009\u00b1\u20090.53\u00a0l) (2.19%). In addition, customization also led to a redistribution of the accuracy levels we classified Below is the link to the electronic supplementary material."}
{"text": "The manganese(II) centers of each structure are six-coordinate with a distorted octa\u00adhedral geometry. Although the bis\u00ad(quinolin-2-ylmeth\u00adyl)ethanamine ligands differ only by a methyl group, the structure of one complex is dimeric with bridging acetate ligands and exhibits a  4O:O\u2032-bis\u00ad{manganese(II)} bis\u00ad(tetra\u00adphen\u00adyl\u00adborate) di\u00adchloro\u00admethane 1.45-solvate, [Mn2(C23O2)2(C23H23N3O)2](C24H20B)\u00b71.45CH2Cl2 or [Mn(DQMEA)(\u03bc-OAc)2Mn(DQMEA)](BPh4)2\u00b71.45CH2Cl2 or [1](BPh4)2\u00b71.45CH2Cl2, and (acetato-\u03baO)(methanol-\u03baO)manganese(II) tetra\u00adphenyl\u00adborate methanol monosolvate, [Mn(CH3COO)(C22H21N3O)(CH3OH)](C24H20B)\u00b7CH3OH or [Mn(DQEA)(OAc)(CH3OH)]BPh4\u00b7CH3OH or [2]BPh4\u00b7CH3OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to MnII ions. In the asymmetric unit, compound [1](BPh4)2\u00b7(CH2Cl2)1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitro\u00adgen, the nitro\u00adgen atom of each quinoline group, and the meth\u00adoxy-oxygen of the tetra\u00addentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric MnII centers have a distorted, octa\u00adhedral geometry in which the quinoline nitro\u00adgen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each MnII center, a coordinated acetate oxygen participates in C\u2014H\u22efO hydrogen-bonding inter\u00adactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak \u03c0\u2013\u03c0 stacking inter\u00adactions and inter\u00admolecular cation\u2013anion inter\u00adactions stabilize the crystal packing. In the asymmetric unit, compound [2]BPh4\u00b7CH3OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitro\u00adgen, the nitro\u00adgen atom of each quinoline group, and the alcohol oxygen of the tetra\u00addentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the MnII center in [2]BPh4\u00b7CH3OH is also a distorted octa\u00adhedron, but the quinoline nitro\u00adgen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O\u2014H\u22efO) and quinolyl (C\u2014H\u22efO and N\u2014H\u22efO) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of inter\u00admolecular O3\u2014H3\u22efO2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and inter\u00admolecular cation\u2013anion inter\u00adactions contribute to the crystal packing.Structural analyses of the compounds di-\u03bc-acetato-\u03ba These compounds are prepared in a two-step reaction (see reaction scheme) in which mangan\u00adese(II) acetate is reacted with either DQMEA or DQEA in methanol, followed by anion exchange with sodium tetra\u00adphenyl\u00adborate. The resulting complexes demonstrate how minor alterations in ligand structure can result in significant differences in the complex structure.We have recently begun to study Mn[1](BPh4)2\u00b7(CH2Cl2)1.45 crystallizes in the triclinic space group P2Mn(DQMEA)]2+ cation, [1]  in the same octa\u00adhedral plane and the meth\u00adoxy oxygen (O1) located perpendicular to this nitro\u00adgen plane. This configuration of the DQMEA ligand results in the quinoline groups binding MnIItrans to each other, and in coplanarity of their rings. Hydrogen-bonding inter\u00adactions between quinolyl hydrogens and an acetate oxygen, C\u2014H\u22efO, further stabilize this trans configuration  and 75.56\u2005(5)\u00b0, respectively, which are significantly reduced from 90\u00b0 (Table\u00a01trans N1\u2014Mn1\u2014N3 angle of 148.35\u2005(5)\u00b0. Likewise, the bond angle formed by cis coordination of the meth\u00adoxy oxygen of DQMEA and central nitro\u00adgen, N2\u2014Mn1\u2014O1 is 75.32\u2005(5)\u00b0. The remaining trans bond angles, O2\u2014Mn1\u2014N2 and O31\u2014Mn1\u2014O1 are 157.89\u2005(5) and 163.58\u2005(5)\u00b0, respectively. The Mn\u2014O and Mn\u2014N bond lengths for the neutral DQMEA ligand fall in the range 2.27\u20132.36\u2005\u00c5, which is typical of manganese(II) complexes  and 2.0908\u2005(14)\u2005\u00c5, are significantly shorter.Compound P Fig.\u00a01. The str1] Fig.\u00a02 balancedn Table\u00a03. Oxygens\u00b0 Table\u00a01. This re[2]BPh4\u00b7CH3OH crystallizes in the monoclinic space group P21/c. The structure of this compound consists of the [Mn(DQEA)(OAc)(CH3OH)]+ monocation, [2], tetra\u00adphenyl borate counter-ion, and a methanol solvent mol\u00adecule  and 73.81\u2005(5)\u00b0, respectively \u00b0. The remaining trans bond angles, O1\u2014Mn1\u2014N1 and N2\u2014Mn1\u2014O4 are 175.54\u2005(6) and 161.38\u2005(6)\u00b0, respectively.The compound le Fig.\u00a03. The MnIy Table\u00a02. The alccis coordination of DQEA to Mn(II) in [2] may result from a hydrogen-bonding network involving the alcohol and quinolyl groups of DQEA and the acetate ligand, O\u2014H\u22efO and C\u2014H\u22efO 2\u00b7(CH2Cl2)1.45, no classical inter\u00admolecular hydrogen bonding inter\u00adactions were found. The crystal packing  of a quinoline group . In addition, a network of weak C\u2014H\u22ef\u03c0  inter\u00admolecular cation\u2013anion inter\u00adactions  inter\u00admolecular cation\u2013anion inter\u00adactions  compounds described herein have not been reported previously. We have previously reported the structure of a mononuclear copper(II) complex with DQMEA ethanamine (DQMEA). In a 250\u2005ml round-bottom flask, 5\u2005g (23\u2005mmol) of 2-chlormethyl\u00adquinoline hydro\u00adchloride was dissolved in 10\u2005ml of H2O and cooled to 273\u2005K in an ice bath. A solution of 1.9\u2005g (47\u2005mmol) of NaOH in 10\u2005ml of H2O was added dropwise with stirring. Following this, a solution of 0.9\u2005g (12\u2005mmol) of 2-meth\u00adoxy\u00adethyl\u00adamine in 10\u2005ml of CH2Cl2 was added. The reaction mixture was then removed from the ice bath, and brought to reflux for 7 days. The mixture was then cooled to room temperature, and the CH2Cl2 layer was separated, washed twice with brine, and dried over anhydrous sodium sulfate. The solution was then filtered, and the filtrate was chromatographed on alumina  eluting with 20:1 CH2Cl2/methanol. Fractions were collected that produced a single spot by TLC on alumina plates  with an RF value of 0.33. Rotary evaporation of these fractions gave 2.4\u2005g (58%) of a light-yellow solid. 1H NMR  \u03b4 2.87 , 3.30 , 3.54 , 4.06 , 7.48 , 7.65 , 7.75 , 8.01 , 8.10 .2-Hy\u00addroxy-N,N-bis\u00ad(quinolin-2-ylmeth\u00adyl)ethanamine (DQEA). In a 100\u2005ml round-bottom flask, 2.5\u2005g (12\u2005mmol) of 2-chlormethyl\u00adquinoline hydro\u00adchloride was dissolved in 10\u2005ml of H2O and cooled to 273\u2005K in an ice bath. A solution of 0.95\u2005g (24\u2005mmol) of NaOH in 10\u2005ml of H2O was added dropwise with stirring. Following this, a solution of 0.36\u2005g (6.0\u2005mmol) of ethano\u00adlamine in 10\u2005ml of CH2Cl2 was added. The reaction mixture was then removed from the ice bath, and brought to reflux for 7 days. The mixture was then cooled to room temperature, and the CH2Cl2 layer was separated, washed twice with brine, and dried over anhydrous sodium sulfate. The solution was then filtered, and the filtrate was chromatographed on alumina  eluting with 100:1 CH2Cl2/methanol. Fractions were collected that produced a single spot by TLC on alumina plates  with an RF value of 0.33. Rotary evaporation of these fractions gave 0.70\u2005g (20%) of a light-yellow solid. 1H NMR  \u03b4 3.02 , 3.54 , 4.17 , 7.51 , 7.74 , 8.07 .2Mn(DQMEA)](BPh4)2BPh4\u00b7CH3OH(BPh4)2\u00b7(CH2Cl2)1.45 and [2]BPh4\u00b7CH3OH are summarized in Table\u00a05[1](BPh4)2\u00b7(CH2Cl2)1.45, all H atoms were positioned geometrically and refined using a riding model: C\u2014H = 0.93\u20130.99\u2005\u00c5, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). Idealized methyl groups were refined as rotating groups. A solvate methyl\u00adene chloride mol\u00adecule was refined as threefold disordered. All C\u2014Cl bond distances were restrained to be the same within a standard deviation of 0.02\u2005\u00c5. Uij components of ADPs were restrained to be similar to each other . Occupancies were not constrained to unity and refined to 0.401\u2005(3), 0.234\u2005(4) and 0.090\u2005(4). In [2]BPh4\u00b7CH3OH, the ethanol group of C21, C22 and O3 was found to be disordered. Bond distances and angles of major and minor moiety were restrained to be similar to each other . Uij components of ADPs were restrained to be similar to each other . The hy\u00addroxy H atoms  were located in a difference-Fourier map and refined with the distance restraint O\u2014H = 0.8\u2005(2)\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O). C-bound H atoms were positioned geometrically and refined as riding: C\u2014H = 0.95\u20130.99\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). Idealized methyl groups were refined as rotating groups. An idealized tetra\u00adhedral OH group was also refined as a rotating group: O1S(H1S).Crystal data, data collection and structure refinement details for 10.1107/S2056989021009786/zl5024sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989021009786/zl50241sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989021009786/zl50242sup3.hklStructure factors: contains datablock(s) 2. DOI: 2110882, 2110881CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Nature Communications 10.1038/s41467-021-21863-4, published online 12 March 2021.Correction to: 2\u03c0\u22121\u2212\u03c3m2\u03c4\u22121 . The correct form of the equation is: D\u2009=\u2009(M2\u03c0\u22121\u2212\u03c3m2)\u03c4\u22121.The original version of this Article contained an error in the Methods, section \u2018Single-particle tracking photoactivated localization microscopy (sptPALM)\u2019, where an equation incorrectly read: D\u2009=\u2009MThis has been corrected in both the PDF and HTML versions of the Article."}
{"text": "Embryo implantation into the uterus is a crucial step for human reproduction. A hypothesis has been proposed that the molecular circuit invented by trophoblasts for invasive embryo implantation during evolution might be misused by cancer cells to promote malignancy. Unfortunately, our current understanding of the molecular mechanism underlying embryo implantation is far from complete.Here we used the mouse as an animal model and generated a single-cell transcriptomic atlas of the embryo implantation site of mouse uterus at the invasion phase of embryo implantation on gestational day 6. We revealed 23 distinct cell clusters, including 5 stromal cell clusters, 2 epithelial cell clusters, 1 smooth muscle cell cluster, 2 pericyte clusters, 4 endothelial cell clusters, and 9 immune cell clusters. Through data analysis, we identified differentially expression changes in all uterine cell types upon embryo implantation. By integrated with single-cell RNA-seq data from E5.5 embryos, we predicted cell\u2013cell crosstalk between trophoblasts and uterine cell types.Our study provides a valuable resource for understanding of the molecular mechanism of embryo implantation.The online version contains supplementary material available at 10.1186/s13578-022-00749-y. Embryo implantation in humans is interstitial. It consists of the following three phases: embryo apposition, attachment, and invasion. Immediately after apposition and attachment to endometrial epithelium, the blastocyst penetrates through the epithelium, followed by the basal lamina, and invades into the stroma . It has Due to ethical restrictions and experimental difficulties, in vivo analysis of embryo implantation heavily relies on mice . SlightlIn the present study, by using the-state-of-the-art single-cell RNA-seq approach , we resoAdult CD-1 mice of the SPF grade were used in this study. All mice were caged under light-controlled conditions (14\u00a0h/10\u00a0h light/dark cycles) with free access to regular food and water. Female mice were mated with fertile males and success of mating was confirmed the next morning by the presence of a vaginal plug. The day of the vaginal plug was denoted as gestation day 1 (GD1). On GD6, the implantation sites and inter-implantation sites (served as a control) were collected separately. All animal procedures were approved by the Institutional Animal Care and Use Committee of South China Agricultural University .The total RNAs from uterine tissues were extracted with the TRIzol reagent (Invitrogen). RNA-seq libraries were generated by using the TruSeq RNA sample preparation kit (Illumina) and sequenced on an Illumina HiSeq 2500 system. Using UCSC mm10 mouse genome as reference, raw data were analyzed using TopHat v2.0.4  and CuffSingle-cell suspension was prepared as described previously , 17. BriThe final concentration of single-cell suspension was adjusted to 1000 cells/\u03bcl and a volume of 15\u00a0\u00b5l was loaded into one channel of the ChromiumTM Single Cell B Chip , aiming at recovering 8000\u201310,000 cells. The Chromium Single Cell 3' Library & Gel Bead Kit v3  was used for single-cell bar-coding, cDNA synthesis and library preparation, following the manufacturer's instructions provided as the Single Cell 3' Reagent Kits User Guide Version 3. Library sequencing was performed on an Illumina novaseq 6000 system configured with the paired-end 150-bp protocol at a sequencing depth of approximately 400 million reads.Raw data bcl files from the Illumina NovaSeq 6000 platform were converted to fastq files using the bcl2fastq tool (v2.19.0.316). These fastq files were aligned to the mm10 mouse reference genome by using the CellRanger software . The resulting gene counts matrix was analyzed with the R package Seurat (v3.1.3) . Cell wiMonocle2 package v2.18.0  was usedGene ontology (GO) analysis was performed as described previously . GO termPathway enrichment analysis was conducted by using the Metascape v7.4 online tools . The sigThe CellChat v1.1.0 software  was usedTo create a cell-type resolved map of mouse uterus at the invasion phase of embryo implantation, we performed single-cell RNA-seq analysis Fig.\u00a0A. The imUnsupervised clustering analysis revealed 23 distinct cell clusters for all cells from IIS and IS combined  [+Nkg7\u2212Cd3e+Mki67+), T cells  [+Cd79a+Ms4a1+) [+Adgre1+) [+Adgre1+Mki67+), dendritic cells  [+Itgax+Mki67+) and plasmacytoid dendritic cells  [Hormone-responsive cells included epithelial cells expressing Epcam and Krt19  Fig.\u00a02CC2C, stro7+Cd3e\u2212) , prolife7\u2212Cd3e+) , B cells+Ms4a1+) , macrophAdgre1+) , prolife+Itgax+) , prolifeiglech+) .Finally, we aimed to discover novel markers for each cell type. We selected genes that were expressed significantly higher in the cell type of interest than the other cell types by Wilcoxon rank sum test. A complete list of these marker genes was presented in Additional file \u201311), developmental processes (P\u2009=\u20091.10\u2009\u00d7\u200910\u20134), cell organization and biogenesis (P\u2009=\u20093.27\u2009\u00d7\u200910\u20134), stress response (P\u2009=\u20094.88\u2009\u00d7\u200910\u20134) and protein metabolism (P\u2009=\u20093.87\u2009\u00d7\u200910\u20132). Gene set 2 with 352 genes were decreased in S3 compared to its intermediate S2p. These genes were enriched in DNA metabolism (P\u2009=\u20091.00\u2009\u00d7\u200910\u201311), cell cycle and proliferation (P\u2009=\u20091.00\u2009\u00d7\u200910\u201311), cell organization and biogenesis (P\u2009=\u20092.59\u2009\u00d7\u200910\u201311) and protein metabolism (P\u2009=\u20093.97\u2009\u00d7\u200910\u20133). Gene set 3 of 300 genes were S2-specific. Based on GO, enriched terms were protein metabolism (P\u2009=\u20093.39\u2009\u00d7\u200910\u201311), developmental processes (P\u2009=\u20096.05\u2009\u00d7\u200910\u20138) and cell cycle & proliferation (P\u2009=\u20098.09\u2009\u00d7\u200910\u20133). Gene set 4 of 729 genes were unchanged or increased in S3 compared to its intermediate S2p. Enriched GO terms were protein metabolism (P\u2009=\u20092.49\u2009\u00d7\u200910\u20138), RNA metabolism (P\u2009=\u20093.23\u2009\u00d7\u200910\u20137), DNA metabolism (P\u2009=\u20094.42\u2009\u00d7\u200910\u20135), transport (P\u2009=\u20091.96\u2009\u00d7\u200910\u20133) cell organization and biogenesis (P\u2009=\u20092.90\u2009\u00d7\u200910\u20135), and cell cycle and proliferation (P\u2009=\u20094.91\u2009\u00d7\u200910\u20133).In our single-cell RNA-seq data, we identified 5 clusters of stromal cells: S1 , S1p , S2 , S2p  and S3 . We selected signature genes for each cell cluster by using Wilcoxon rank sum test. After the removal of redundancy, we identified a total of 1784 signature genes  were examined. We found that PDZ expressed pan-stromal cell markers Pgr, Esr1 and Hoxa11, as well as the superficial stromal cell marker Hand2. Additionally, PDZ expressed decidualization marker Wnt4, but not Prl8a2 . PDZ cea were exaTo further reveal the relationship between these 5 stromal cell clusters, pseudotime trajectory analysis was conducted. Cells were arranged in a pseudotime manner with a pedigree reconstruction algorithm for biological processes based on transcriptional similarity. We found 2 paths of interest: (1) primary decidual zone formation, i.e. S2-\u2009>\u2009S2p/S3; and (2) secondary decidual zone formation, i.e. S1-\u2009>\u2009S1p , PI3K-Akt signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u201318), Regulation of actin cytoskeleton (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20139), Rap1 signaling pathway (FDR\u2009=\u20091.58\u2009\u00d7\u200910\u20136), Ras signaling pathway (FDR\u2009=\u20097.94\u2009\u00d7\u200910\u20135), MAPK signaling pathway (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20134), Phospholipase D signaling pathway (FDR\u2009=\u20097.94\u2009\u00d7\u200910\u20133) and Cytokine-cytokine receptor interaction (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20132)  and TGC. We found a total of 20 ligand-receptor interaction pairs Fig.\u00a0F. Based FDR\u2009=\u20097.9\u2009\u00d7\u200910\u20135, 2 test was employed to assess the significance of difference between two groups. By using the criteria of P\u2009<\u20090.05 and fold change\u2009>\u20092, we found that the proportion of S1 was unchanged, whereas the proportion of S2 significantly decreased in IS compared to IIS. Meanwhile, S1p and S2p were almost exclusively detected in IS , PI3K-Akt signaling pathway (FDR\u2009=\u20092.00\u2009\u00d7\u200910\u20139), Regulation of actin cytoskeleton (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20139), Hippo signaling pathway (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20139), ECM-receptor interaction (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20138), Rap1 signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u20136), MAPK (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20136), Wnt signaling pathway (FDR\u2009=\u20092.00\u2009\u00d7\u200910\u20135), Ras signaling pathway (FDR\u2009=\u20092.00\u2009\u00d7\u200910\u20135), mTOR signaling pathway (FDR\u2009=\u20092.51\u2009\u00d7\u200910\u20135), TGF-beta signaling pathway (FDR\u2009=\u20092.51\u2009\u00d7\u200910\u20135), Endocytosis (FDR\u2009=\u20096.31\u2009\u00d7\u200910\u20135) and Phagosome (FDR\u2009=\u20097.94\u2009\u00d7\u200910\u20133)  on S1 and S2, we used the CellChat software to predict the ligand-receptor interactions. Only secreted factors from PDZ were considered. We found a total of 35 ligand-receptor interaction pairs Fig.\u00a0A. PathwaFDR\u2009=\u20093.1\u2009\u00d7\u200910\u20139, By using the criteria of P\u2009<\u20090.05 and fold change\u2009>\u20092, we found that the proportion of NKp, Mp and DCp were significantly increased at IS compared IIS Fig.\u00a0A. Using \u20137), PI3K-Akt signaling pathway (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20136), MAPK signaling pathway (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20134), Endocytosis (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20134), ECM-receptor interaction (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20134), TGF-beta signaling pathway (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20134), Rap1 signaling pathway (FDR\u2009=\u20097.94\u2009\u00d7\u200910\u20134), Hippo signaling pathway (FDR\u2009=\u20092.51\u2009\u00d7\u200910\u20133), Regulation of actin cytoskeleton (FDR\u2009=\u20097.94\u2009\u00d7\u200910\u20133), Toll-like receptor signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u20132), Ras signaling pathway (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20132), Natural killer cell mediated cytotoxicity (FDR\u2009=\u20091.58\u2009\u00d7\u200910\u20132), Jak-STAT signaling pathway (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20132) and NOD-like receptor signaling pathway (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20132)  and immune cells  using the CellChat software. We found a total of 26 ligand-receptor interaction pairs Fig.\u00a0A. PathwaFDR\u2009=\u20093.9\u2009\u00d7\u200910\u20134, By using the criteria of P\u2009<\u20090.05 and fold change\u2009>\u20092, we found that the proportions of both VEC and LEC were significantly decreased in IS compared to IIS, which is in line with the fact that PDZ is avascular \u201344. Inte\u201323), Rap1 signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u201316), Ras signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u201314), Cytokine-cytokine receptor interaction (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u201314), HIF-1 signaling pathway (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20137), Hippo signaling pathway (FDR\u2009=\u20091.00\u2009\u00d7\u200910\u20136), Endocytosis (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20136), Regulation of actin cytoskeleton (FDR\u2009=\u20096.31\u2009\u00d7\u200910\u20136), mTOR signaling pathway (FDR\u2009=\u20091.58\u2009\u00d7\u200910\u20135), MAPK signaling pathway (FDR\u2009=\u20091.58\u2009\u00d7\u200910\u20135), ECM-receptor interaction (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20134), TGF-beta signaling pathway (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20134), NOD-like receptor signaling pathway (FDR\u2009=\u20095.01\u2009\u00d7\u200910\u20133), Toll-like receptor signaling pathway (FDR\u2009=\u20091.26\u2009\u00d7\u200910\u20132), AMPK signaling pathway (FDR\u2009=\u20092.00\u2009\u00d7\u200910\u20132), Wnt signaling pathway (FDR\u2009=\u20093.16\u2009\u00d7\u200910\u20132) and Jak-STAT signaling pathway (FDR\u2009=\u20093.98\u2009\u00d7\u200910\u20132)  and VEC/LEC. We found a total of 34 ligand-receptor interaction pairs Fig.\u00a0A. PathwaEmbryo implantation is a crucial step for human embryo implantation. Previously, we performed single-cell RNA analysis of the mouse uterus during the apposition phase and attachment phase of embryo implantation on gestational days (GD) 4\u20135 , 17. HerIn order to accommodate embryo implantation, an important change in mouse uterus is the formation of primary decidual zone (PDZ). The first sign of PDZ formation occurs on the afternoon of GD5. PDZ is fully established by GD6 \u201347. In tThe trophectoderm (TE) of mouse embryo is created by the end of the pre-implantation period. After implantation, TE develops into two different types, polar TE and mural TE. Polar TE differentiates into extraembryonic ectoderm (ExE) and ectoplacental cone (EPC), while mural TE differentiates into trophoblast giant cells (TGC). TGC cells are in closest contact to the uterus during embryo implantation . Thus, tBesides the emergence of PDZ, by comparing IS with IIS, we found apparent cell type abundance changes upon embryo implantation. In particular, the proliferating subsets of S1, S2, NK, M, DC and VEC were significantly increased. There were also massive gene expression changes in these cell types. Considering spatial relationships between cell types, uterine cell types other than PDZ are unable to directly communicate with embryonic cells during embryo implantation. Therefore, these changes were likely caused by PDZ indirectly via secreted signaling. Indeed, we found that many soluble factors from PDZ, such as Wnt4, Wnt5a and Wnt6, might have an influence on S1 and S2 cells. Wnt4 is most abundant in the decidual cells. In uterus-specific Wnt4 knockout mice, the embryos were able to attach to the uterine luminal epithelium, but they failed to successfully invade into the uterine stroma . During In conclusion, this study provided a comprehensive single-cell transcriptome atlas for mouse uterus at the invasion phase of embryo implantation. Our data present a valuable resource for deciphering the molecular mechanism underlying embryo implantation.Additional file 1: Table S1. The complete list of novel and known marker genes for each cell type.Additional file 2: Table S2. The complete list of signature genes for stromal cell clusters.Additional file 3: Table S3. The complete list of differentially expressed genes in IS compared to IIS for all cell types (logFC\u2009>\u20090.25 and P\u2009<\u20090.05)."}
{"text": "Cadia purpurea roots were investigated herein for the first time. The phytochemical study led to the isolation of two compounds, di-(2-methylheptyl) phthalate (1) and 13-O-pyrrolecarboxyl lupanine (2), from methanol roots extract of C. purpurea. The antibacterial activity results revealed that the n-hexane extract presented a better inhibitory value (13.8\u2009\u00b1\u20090.0\u2009mm) followed by chloroform (11.1\u2009\u00b1\u20090.4\u2009mm) and chloroform\u2009:\u2009methanol (1\u2009:\u20091) (10.7\u2009\u00b1\u20090.1\u2009mm) extracts against E. coli at the maximum dose of 100\u2009mg/mL. While, methanolic and ethanolic extracts displayed a mild activity against same bacterium at same dose. The methicillin resistant S. aureus was found with almost total resistance to all extracts up to the 100\u2009mg/mL. The chloroform\u2009:\u2009methanol (1\u2009:\u20091), chloroform, and n-hexane extracts recorded inhibition zone values  better than chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm at 30\u2009\u03bcg dose) against P. aeruginosa. The alcoholic extracts also exhibited an activity better than chloramphenicol up to 25\u2009mg/mL against same bacterium. Compound 2 produced a comparable inhibition value (9.6\u2009\u00b1\u20090.0\u2009mm to 18.5\u2009\u00b1\u20090.0\u2009mm) to that of chloramphenicol (21.5\u2009\u00b1\u20090.3\u2009mm) against E. coli at doses up to 1.0\u2009mg/mL; whereas, compound 1 showed a slight activity (7.1\u2009\u00b1\u20090.1\u2009mm\u201310.3\u2009\u00b1\u20090.0\u2009mm). Both compounds were found generally inactive against S. aureus, while they provided an activity better than chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm) against P. aeruginosa with inhibition zones ranging from 7.1\u2009\u00b1\u20090.0\u2009mm to 9.0\u2009\u00b1\u20090.1\u2009mm for compound 1 and 7.2\u2009\u00b1\u20090.0\u2009mm to 10.6\u2009\u00b1\u20090.0\u2009mm for compound 2. Ethanolic and methanolic extracts exhibited a better DPPH radical scavenging activity  and strong ferric ion reducing power  at a concentration of 500\u2009\u03bcg/mL compared to the other extracts. Compound 1 also possessed a better anti-DPPH trapping activity  than compound 2 . The compounds, however, indicated a weak ferric ion reduction power even at higher amount. In general, the observed antibacterial and antioxidant activities of isolated compounds and extracts were found to be dose-dependent. Conducting further biochemical investigations on all parts of this plant could provide opportunities of finding extra alkaloidal compounds and other phthalate derivatives with better biological activity.Phytochemicals and antibacterial and antioxidant activities of  Cadia purpurea (Fabaceae) is a shrub which inhabits rift valley escarpment and bush land, commonly in altitudes about 1300\u20132700\u2009m. In Ethiopia. it is found in Tigray, Welo, Shewa, Hararge, and Bale regions. C. purpurea is also distributed in Eritrea, Yemen, Oman, North Somalia, and North Kenya + at m/z of 390 was showed which is compatible with the molecular composition of C24H38O4, 149.0 (100%), 167 (30.31%), 57.1 (16.65%), 71.1 (11.57%), and 279.1 (10.71%).Compound 1H NMR spectrum, a methylene proton signal at \u03b4H 4.22\u20134.24 , integrated to four protons, was observed. Besides, proton signals at \u03b4H 0.96\u20130.98  and 0.91\u20130.94  integrated each to six protons were shown implying that there were four methyl groups, in which the first two (C-8\u2032/8\u2033-CH3) were attached to sp3 methine carbons (C-2\u2032/2\u2033), while the latter two (C-7\u2032/7\u2033-CH3) were found to be terminals affixed to sp3 methylene carbons (C-6\u2032/6\u2033). The presence of two symmetric sp3 methine groups was also confirmed by the proton signal at \u03b4H 1.58\u20131.71  in the 1H NMR spectrum. Other eight symmetric methylene protons were appeared at \u03b4H 1.30\u20131.36 as multiplet integrated to a total of sixteen protons. Furthermore, two proton signals (integrated to two protons each) in the low field region at \u03b4H 7.72\u20137.74  and 7.62\u20137.64  were indicative of four symmetric aryl protons having the same coupling pattern. From 13C and DEPT-135 NMR spectra, twelve intense carbon peaks were clearly shown, which ascribed to twenty-four carbon numbers indicating that there is a symmetry in compound 1. For instance, the presence of a quaternary carbon signal at \u03b4 167.9 (C-7/8) and methylene carbon signal at \u03b4 67.7 (C-1\u2032/1\u2033) confirmed the occurrence of two symmetric aryl ester carbonyl groups. The 13C and DEPT-135 spectra also further supported this by showing eight symmetric carbons, i.e., six aromatic carbons at \u03b4 132.2 , 128.5 (C-2/5), and 131.0 (C-3/4). In addition, the occurrence of two carbon signals in the far right side of the 13C spectrum at \u03b4 10.1 and 13.1 indicated that there were four equivalence methyl groups, C-8\u2032/8\u2033-CH3 (attached to C-2/'2\u2033 at \u03b4 38.8), and terminal C-7\u2032/7\u2033-CH3 (affixed to C-6\u2032/6\u2033 at \u03b4 22.7). Moreover, other four symmetric methylene carbon peaks were observed at \u03b4 23.6 (C-3\u2032/3\u2033), 28.7 (C-4\u2032/4\u2033), 30.2 (C-5\u2032/5\u2033), and 22.7 (C-6\u2032/6\u2033). In the resulted IR spectrum, the absence of a sharp intense hydroxyl peak at its absorption region and the presence of a peak at the carbonyl functional group region (1727\u2009cm\u22121) along with the absorption bands of 1282 and 745\u2009cm\u22121, which were due to the ester C=O, C-O and -CH stretches of aromatic protons, respectively, directed that compound 1 exhibits a diester of phthalic acid. Based on the above discussed spectral data (1 was deduced as di-(2-methylheptyl) phthalate (1. Eventhough di-(2-methylheptyl) phthalate is a member of the phthalate groups, unlike to other phthalate esters, it is not a petrochemical and plasticizer. Most of the phthalates and their derivatives are petrochemicals which have been used as plasticizers in chemical industry to improve the plasticity and flexibility of the industrial products +  was observed, 246.2 (100%), 134.05 (29.86%), 112.0 (weak), and 94.0 (weak).Compound 51\u2013154o  along with a methylene carbon signal at the aliphatic region  in the 13C spectrum. Besides, the relatively deshielded multiplet  and triplet  proton signals indicate the presence of methine groups attached to heteroatoms , as also reported elsewhere [\u03b4H 1\u20133\u2009ppm). From the 13C and DEPT-135 spectra, fifteen clear carbon signals were shown which represent a quaternary carbonyl carbon of the amide group at \u03b4 172.8 (C-2), nine sp3 methylene carbons at \u03b4 32.3 (C-3), 18.9 (C-4), 25.6 (C-5), 26.7 (C-8), 46.6 (C-10), 35.4 (C-12), 49.4 (C-15), 27.7 (C-14), and 51.2 (C-17), and five sp3 methine carbons appeared at \u03b4 60.7 (C-6), 33.9 (C-7), 32.2 (C-9), 57.9 (C-11), and 67.7 (C-13). Generally, the abovementioned proton and carbon signals were complementary and characteristics of lupanine skeleton. Besides, the absorption bands shown at 1616 and 2918\u20132855\u2009cm\u22121 in the IR spectrum, which belong to the amide carbonyl group (lactam C=O) and -CH stretch of the trans-quinolizidine, respectively, highlighted that compound 2 exhibits a lupanine skeleton. As also reported elsewhere [2 which was assured by three doublets of doublet proton signals occurred at \u03b4H 7.01 , 6.21\u20136.23 , and 6.90\u20136.92  assigned to the three olefinic methine protons of the pyrrolecarboxyl unit. Their corresponding carbon peaks appeared at \u03b4 123.5 (C-4\u2032), 109.4 (C-5\u2032) and 115.6 (C-6\u2032). In the DEPT-135 spectrum, the two quaternary carbon signals shown at \u03b4 122.2 and 161.7 belong to C-2\u2032 and the carbonyl carbon (C-1\u2032), respectively, of the substituent. Also, the carbonyl (C=O) and secondary -NH groups of the esterified pyrrolecarboxyl moiety showed absorption bands in the wavenumbers (cm\u22121) of 1692 and 3342 (broad), respectively, in the IR spectrum. This esterified pyrrolecarboxyl unit was incorporated to the lupanine skeleton of compound 2 at C-13 which was identified by the relatively deshielded carbon signal at \u03b4 67.7 (C-13) and triplet proton signal of H-13 at \u03b4H 5.19\u20135.21 . The detailed spectral information obtained of compound 2 is given in 2 was characterized as 13-O-pyrrolecarboxyl lupanine  extracts were found effective against E. coli (>7\u2009mm inhibition zone) at all tested concentrations with the maximum inhibition diameters of 13.8\u2009\u00b1\u20090.0\u2009mm, 11.1\u2009\u00b1\u20090.0\u2009mm, and 10.7\u2009\u00b1\u20090.1\u2009mm, respectively, recorded at the maximal concentration of 100\u2009mg/mL, which were slightly comparable to chloramphenicol (24.5\u2009\u00b1\u20090.3\u2009mm at 30\u2009\u03bcg dose). The remaining lower concentrations, 50\u2009mg/mL, 25\u2009mg/mL, and 12.5\u2009mg/mL, of these extracts also produced an activity with corresponding inhibition zone values of 10.2\u2009\u00b1\u20090.4\u2009mm, 9.3\u2009\u00b1\u20090.0\u2009mm, and 8.7\u2009\u00b1\u20090.0\u2009mm recorded by n-hexane extract, 9.6\u2009\u00b1\u20090.3\u2009mm, 8.3\u2009\u00b1\u20090.0\u2009mm, and 7.2\u2009\u00b1\u20090.0\u2009mm recorded by chloroform extract, and 9.0\u2009\u00b1\u20090.3\u2009mm, 7.2\u2009\u00b1\u20090.0\u2009mm, and 7.0\u2009\u00b1\u20090.0\u2009mm recorded by chloroform/methanol (1\u2009:\u20091) extract. Interestingly, both the alcoholic extracts experienced a lesser activity against E. coli at concentrations of 100\u2009mg/mL and 50\u2009mg/mL with respective inhibitory values of 9.6\u2009\u00b1\u20090.1\u2009mm and 8.3\u2009\u00b1\u20090.1\u2009mm for the methanol extract and 8.0\u2009\u00b1\u20090.0\u2009mm and 7.6\u2009\u00b1\u20090.0\u2009mm for the ethanol extract, while no inhibited area was visible at the remaining concentrations of the extracts. The Gram-positive S. aureus strain was found to be susceptible only to the n-hexane and methanol extracts up to the 25\u2009mg/mL dose with measured inhibited area ranging from 7.6\u2009\u00b1\u20090.0\u2009mm to 10.2\u2009\u00b1\u20090.5\u2009mm and 7.3\u2009\u00b1\u20090.0\u2009mm to 8.7\u2009\u00b1\u20090.0\u2009mm, respectively. Whereas, completely no cleared zone was observed at the minimal concentration (12.5\u2009mg/mL) of these extracts. Also, all tested concentrations of chloroform, chloroform/methanol (1\u2009:\u20091), and ethanol extracts showed a totally zero zone of inhibition against S. aureus. On the other hand, the chloroform/methanol (1\u2009:\u20091) extract exerted a positive action on the growth of P. aeruginosa bacterium at all tested dilutions with measured cleared area of 10.0\u2009\u00b1\u20090.1\u2009mm at 100\u2009mg/mL, 9.7\u2009\u00b1\u20090.1\u2009mm at 50\u2009mg/mL, 8.4\u2009\u00b1\u20090.2\u2009mm at 25\u2009mg/mL, and 8.0\u2009\u00b1\u20090.0\u2009mm at 12.5\u2009mg/mL. The chloroform and n-hexane extracts also made an attempt to inhibit some area of P. aeruginosa growth at all concentrations by providing measured values of 7.7\u2009\u00b1\u20090.0 mm\u20139.8\u2009\u00b1\u20090.1\u2009mm and 7.3\u2009\u00b1\u20090.0 mm\u20138.9\u2009\u00b1\u20090.2\u2009mm, respectively. However, the methanolic and ethanolic extracts scored a slightly lower inhibitory values  against P. aeruginosa at the doses up to 25\u2009mg/mL, but a nil inhibition zone at the least concentration (12.5\u2009mg/mL). To summarize, a better activity against E. coli, especially at the higher concentrations (100\u2009mg/mL and 50\u2009mg/mL), was noted in the nonalcoholic extracts though it looked like less as compared to chloramphenicol (24.5\u2009\u00b1\u20090.3\u2009mm at dose of 30\u2009\u03bcg). Whereas, the inhibitory action indicated by almost all extracts against S. aureus at all concentrations was noted weak in reference to chloramphenicol (18.8\u2009\u00b1\u20090.4\u2009mm). To the contrary, the inhibition zone values, scored by the extracts against P. aeruginosa, were found even better than that of chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm).2 presented better inhibitory activity than compound 1 against E. coli with greater zone of inhibition of 18.5\u2009\u00b1\u20090.0\u2009mm recorded at the higher concentration of 1.0\u2009mg/mL, which was comparable to chloramphenicol (21.5\u2009\u00b1\u20090.3\u2009mm at dose of 30\u2009\u03bcg). The remaining concentrations, 0.5\u2009mg/mL, 0.3\u2009mg/mL, 0.1\u2009mg/mL, and 0.05\u2009mg/mL, of compound 2 also produced an activity against same bacterium with respective mean inhibition values of 16.2\u2009\u00b1\u20090.0\u2009mm, 13.8\u2009\u00b1\u20090.0\u2009mm, 10.0\u2009\u00b1\u20090.0\u2009mm, and 9.6\u2009\u00b1\u20090.0\u2009mm. Compound 1 displayed a moderate activity against E. coli at all concentrations (>7\u2009mm) with inhibition zones laid in the range of 7.2\u2009\u00b1\u20090.1 mm\u201310.3\u2009\u00b1\u20090.0\u2009mm. Whereas, against S. aureus, compound 1 showed a minor inhibitory effect only at concentrations of 1.0\u2009mg/mL (9.1\u2009\u00b1\u20090.1\u2009mm) and 0.5\u2009mg/mL (8.4\u2009\u00b1\u20090.0\u2009mm), but a zero effect at the remaining concentrations. Compound 2 was found totally inactive against S. aureus at all concentrations with nil inhibition zone values. However, the two compounds possessed an activity stronger than the chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm) against P. aeruginosa bacterium almost at all dilutions, that is, compound 2 produced mean inhibition zone values ranging from 7.2\u2009\u00b1\u20090.6\u2009mm to 10.6\u2009\u00b1\u20090.0\u2009mm and that of compound 1 was found between 7.1\u2009\u00b1\u20090.0\u2009mm and 9.0\u2009\u00b1\u20090.1\u2009mm. 2 provided a notable activity against E. coli, especially at the higher concentration, which resulted in an inhibition value close to that of chloramphenicol; whereas, compound 1 was found with lesser activity as compared with compound 2 and chloramphenicol. However, against the methicillin resistant S. aureus strain, both compounds exhibited a negligible activity up to 1.0\u2009mg/mL in comparison to the chloramphenicol antibiotic (18.8\u2009\u00b1\u20090.4\u2009mm at the dose of 30\u2009\u03bcg). But, surprisingly, chloramphenicol had faced strong and unprecedented resistant from P. aeruginosa bacterium which led to even a smaller inhibition zone value (7.2\u2009\u00b1\u20090.6\u2009mm) than that of the compounds. Overall, the resulted inhibitory potential of the extracts and isolated compounds examined herein was found slightly comparable against E. coli, very weak against S. aureus, and stronger against P. aeruginosa in reference to the standard antibiotic drug, chloramphenicol (at 30\u2009\u03bcg dose). In fact, it is difficult to exactly compare the antimicrobial potency of extracts and/or isolates directly with synthesized standard antibiotics like chloramphenicol for similar doses, since there are huge differences between them in terms of chemical polarity, structural patterns, and others.As given in 1 and 2 of Cadia purpurea roots was evaluated against DPPH free radical and ferric ion oxidation. Six various dilutions  of each extract and compound, including ascorbic acid, were prepared from their respective stock solutions (1\u2009mg/mL). Each solution was subjected to the UV-Vis spectrophotometer to measure their absorbance against DPPH radical and ferric reducing power at 517 and 700\u2009nm, respectively. Resulted values of duplicates were expressed as mean\u2009\u00b1\u2009standard deviation.In vitro antioxidant potential of four extracts  and two isolated compounds DPPH free radical scavenging activity: the DPPH free radical scavenging potential of extracts and isolated compounds was determined compared to ascorbic acid (AA). The obtained result showed that activity of the extracts and compounds against DPPH radical was dose-dependent, in which the DPPH scavenging activity percentage was directly correlated with concentrations .50 values of 12.9 and 16.03\u2009\u03bcg/mL at 500\u2009\u03bcg/mL concentration. The chloroform and chloroform/methanol (1\u2009:\u20091) extracts provided the comparatively lesser anti-DPPH activity percentage of 77.07\u2009\u00b1\u20090.00  and of 79.38\u2009\u00b1\u20090.16 (26.14\u2009\u03bcg/mL of IC50) at same concentration. In reference to the observed anti-DPPH potency of ascorbic acid  at 500\u2009\u03bcg/mL, however, the inhibitory activity against the free radical of the tested extracts was found to be weak.As given in 1 presented a greater anti-DPPH activity percentage of 82.69\u2009\u00b1\u20090.11 at concentration of 500\u2009\u03bcg/mL with an IC50 value of 7.99\u2009\u03bcg/mL. The quinolizidine alkaloid compound 2 exhibited the smaller scavenging percentage value   for same concentration.Of the compounds evaluated, compound 4\u2009\u03bcg/mL) . Here, t3+) ion into its ferrous (Fe2+) of extracts and isolates was known by first observing a change in color of the reaction solutions from yellow to green and then measuring the absorbance at 700\u2009nm [Ferric reducing antioxidant power examination: the potential of reducing ferric  at same amount  toward DNA gyraseB protein of E. coli selected from the Protein Data Bank (PDB ID: 6F86). The docking analysis result  is observed in compound 2 which is comparable with that of ciprofloxacin . As shown in 2 makes three H-bond interactions with Thr-165 via water, Gly-77, and Ile-78 residual amino acids. Besides, this compound coordinates to Pro-79 including a Van der Walls interaction with Asp-73. The hydrophobic and \u03c0-anion binding ability of compound 1 with Ile-78 and Glu-50 binding pockets, respectively, is the only drug-likeness indicator of the compound in comparison to ciprofloxacin. Whereas, the ciprofloxacin-like property of compound 2 is recognized only via the formation of a H-bond with Thr-165 active binding site of 6F86.Isolated compounds s result  revealed1) and 13-O-pyrrolecarboxyl lupanine (2), were isolated from methanolic extract of Cadia purpurea roots for the first time. In vitro antibacterial and antioxidant activities of isolated compounds and crude extracts were also evaluated, and the results showed that n-hexane, chloroform, and chloroform/methanol (1\u2009:\u20091) extracts were found effective against E. coli at all tested concentrations with the maximum inhibition diameters of 13.8\u2009\u00b1\u20090.0\u2009mm, 11.1\u2009\u00b1\u20090.0\u2009mm, and 10.7\u2009\u00b1\u20090.1\u2009mm, respectively, recorded at the maximal concentration of 100\u2009mg/mL, which were slightly comparable to chloramphenicol (24.5\u2009\u00b1\u20090.3\u2009mm at 30\u2009\u03bcg dose). The methanolic and ethanolic extracts, however, experienced a smaller activity against E. coli merely at concentrations of 100\u2009mg/mL and 50\u2009mg/mL with respective inhibitory values of 9.6\u2009\u00b1\u20090.1\u2009mm and 8.3\u2009\u00b1\u20090.1\u2009mm, and 8.0\u2009\u00b1\u20090.0\u2009mm and 7.6\u2009\u00b1\u20090.0\u2009mm. The methicillin resistant S. aureus strain was found to be sensitive only to the n-hexane and methanol extracts up to the 25\u2009mg/mL dose with measured inhibited area ranging from 7.6\u2009\u00b1\u20090.0\u2009mm to 10.2\u2009\u00b1\u20090.5\u2009mm, and 7.3\u2009\u00b1\u20090.0\u2009mm to 8.7\u2009\u00b1\u20090.0\u2009mm, respectively. Whereas the chloroform, chloroform/methanol (1\u2009:\u20091), and ethanol extracts did not indicate any sign of activity against S. aureus even at the higher concentration of 100\u2009mg/mL. On the other hand, the chloroform/methanol (1\u2009:\u20091) extract exerted an inhibitory action on the growth of P. aeruginosa bacterium at all tested dilutions with measured clear area of 8.0\u2009\u00b1\u20090.0\u2009mm\u201310.0\u2009\u00b1\u20090.1\u2009mm. The chloroform and n-hexane extracts also attempted to inhibit some growth of P. aeruginosa at all concentrations with corresponding measured values of 7.7\u2009\u00b1\u20090.0\u2009mm\u20139.8\u2009\u00b1\u20090.1\u2009mm and 7.3\u2009\u00b1\u20090.0\u2009mm\u20138.9\u2009\u00b1\u20090.2\u2009mm. However, the methanolic and ethanolic extracts scored a slightly lower inhibitory values  against P. aeruginosa up to 25\u2009mg/mL concentration. Compound 2 presented a better inhibitory effect against E. coli than compound 1 with a comparable inhibition value (18.5\u2009\u00b1\u20090.0\u2009mm) to chloramphenicol (21.5\u2009\u00b1\u20090.3\u2009mm at dose of 30\u2009\u03bcg) recorded at the higher concentration of 1.0\u2009mg/mL. This compound 2 also produced an activity on same bacterium at the concentrations of 0.5\u2009mg/mL, 0.3\u2009mg/mL, 0.1\u2009mg/mL, and 0.05\u2009mg/mL with zone of inhibition values ranging between 9.6\u2009\u00b1\u20090.0\u2009mm and 16.2\u2009\u00b1\u20090.0\u2009mm. Compound 1 displayed a moderate activity (>7\u2009mm) against E. coli at all concentrations with inhibition zones laid in the range of 7.2\u2009\u00b1\u20090.1\u2009mm\u201310.3\u2009\u00b1\u20090.0\u2009mm. Whereas, against S. aureus, compound 1 showed a minor inhibitory effect only at concentrations of 1.0\u2009mg/mL (9.1\u2009\u00b1\u20090.1\u2009mm) and 0.5\u2009mg/mL (8.4\u2009\u00b1\u20090.0\u2009mm) and compound 2 was found totally inactive at all concentrations. The two compounds, however, possessed an activity stronger than the chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm) against P. aeruginosa bacterium almost at all dilutions with mean inhibition zone values ranging from 7.2\u2009\u00b1\u20090.6\u2009mm to 10.6\u2009\u00b1\u20090.0\u2009mm of compound 2 and 7.1\u2009\u00b1\u20090.0\u2009mm to 9.0\u2009\u00b1\u20090.1\u2009mm of compound 1. The obtained antibacterial result generally revealed that nonalcoholic extracts were noted with a better activity against E. coli, especially at the higher concentrations (100\u2009mg/mL and 50\u2009mg/mL), though they seemed like weak compared to the chloramphenicol (24.5\u2009\u00b1\u20090.3\u2009mm at dose of 30\u2009\u03bcg). Compound 2 also provided a notable activity against E. coli, especially at the higher concentration, which resulted in an inhibition value close to that of chloramphenicol (21.5\u2009\u00b1\u20090.3\u2009mm); whereas, compound 1 was found with weaker activity as compared with compound 2 and chloramphenicol. On the other hand, against the methicillin resistant S. aureus strain, both compounds and all the extracts exhibited a negligible activity up to the higher dosage in reference to the chloramphenicol antibiotic (18.8\u2009\u00b1\u20090.4\u2009mm). On the contrary, the inhibition zone values, scored by the extracts and compounds against P. aeruginosa, were found even better than that of chloramphenicol (7.2\u2009\u00b1\u20090.6\u2009mm). Regarding the antioxidant potency, ethanolic and methanolic extracts exhibited a better DPPH radical scavenging activity  at concentration of 500\u2009\u03bcg/mL, whereas the chloroform and chloroform/methanol (1\u2009:\u20091) extracts were observed weak with IC50 values of 27.52 and 26.14\u2009\u03bcg/mL. Comparatively strong ferric ion reducing power was also shown in the alcoholic extracts with 0.810\u2009\u00b1\u20090.001 absorbance of methanol and 0.788\u2009\u00b1\u20090.000 of ethanol at the maximum amount (500\u2009\u03bcg/mL). Compound 1 indicated a promising trapping potential against DPPH radical , while compound 2 recorded a higher IC50 value (58.34\u2009\u03bcg/mL) at concentration of 500\u2009\u03bcg/mL. However, at same dosage, the isolated compounds indicated a weak power of ferric ion reduction with recorded absorbance of 0.761\u2009\u00b1\u20090.002 by compound 1 and 0.458\u2009\u00b1\u20090.001 of compound 2. The molecular docking result revealed that compound 1 shows two hydrophobic (with Ile-78 and Ile-94), a \u03c0-anion (with Glu-50) and Van der Walls interactions with some amino residues of E. coli gyraseB; whereas, compound 2 makes three H-bond interactions with Thr-165, Gly-77, and Ile-78 in addition to the Van der Walls interaction with Asp-73. In conclusion, the present findings indicated that the resulted antibacterial inhibitory potential of the extracts and isolated compounds was found slightly active against E. coli, very weak against S. aureus, and stronger against P. aeruginosa as compared to chloramphenicol (at 30\u2009\u03bcg dose); and the entire antibacterial and antioxidant activities of tested analytes were noted as dose-dependent. Besides, since other quinolizidine alkaloids (similar to compound 2) were also reported from the leaves of Ethiopian Cadia purpurea, conducting further biochemical investigations on all parts of the plant could provide opportunities of finding additional alkaloidal compounds and other phthalates with powerful biological activities.In this study, two compounds, di-(2-methylheptyl) phthalate ("}
{"text": "Paratylenchus spp., are relatively small nematodes that can feed on a wide range of host plants. The morphological identification of this nematode is greatly hampered by their small size and variable characters. This study provides the first report of Paratylenchus lepidus from Vietnam with a combination of morphological and molecular characterizations. The 28S rDNA phylogenetic tree of the genus and the first COI mtDNA barcode of this species are also provided.The pin nematodes,  Paratylenchus  is commonly known as pin nematodes that are ectoparasites and can be frequently found at high density in perennial plants, hop gardens, orchards, or forest trees  Kuntze) in Vietnam. Nematodes were extracted using the modified Baermann tray method (COI mtDNA gene were amplified using D2A/D3B (5\u2032\u2013ACAAGTACCGTGGGGAAAGTTG\u20133\u2032/5\u2032\u2013TCGGAAGGAACCAGCTACTA\u20133\u2032) (www.geneious.com). The best fit model was chosen using Mega 7 and phylogenetic analysis was done following Nguyen et al. (2019c).Soil and root samples were collected from the rhizosphere of green tea (y method . After tACTA\u20133\u2032)  and JB3/n\u2009=\u200920 (\u2640\u2640): L\u2009=\u2009340\u2009\u00b1\u200920 (307-371) \u00b5m, a\u2009=\u200925\u2009\u00b1\u20091 (22-27), b\u2009=\u20094.1\u2009\u00b1\u20090.3 (3.7-4.6), c\u2009=\u200911.5\u2009\u00b1\u20091.4 (9.8-13.8), c\u2032\u2009=\u20093.5\u2009\u00b1\u20090.4 (3.0-4.1), V%\u2009=\u200982\u2009\u00b1\u20091 (81-84), Lip height\u2009=\u20092.7\u2009\u00b1\u20090.5 (1.9-3.6) \u00b5m, Lip width\u2009=\u20094.9\u2009\u00b1\u20090.5 (4.2-5.9) \u00b5m, Stylet\u2009=\u200925\u2009\u00b1\u20091 (24-27) \u00b5m, Median bulb length\u2009=\u200915.2\u2009\u00b1\u20092 (12.8-18.0) \u00b5m, Median bulb width\u2009=\u20096.9\u2009\u00b1\u20090.6 (5.9-7.7) \u00b5m, SE pore\u2009=\u200975\u2009\u00b1\u20094 (67-81) \u00b5m, Pharynx\u2009=\u200984\u2009\u00b1\u20093 (79-91) \u00b5m, Body width\u2009=\u200913.8\u2009\u00b1\u20090.4 (13.3-14.5) \u00b5m, Vulval body diam.\u2009=\u200912.2\u2009\u00b1\u20090.4 (11.3-12.6) \u00b5m, Anal body diam.\u2009=\u20098.5\u2009\u00b1\u20090.4 (7.9-9.5) \u00b5m, Tail length\u2009=\u200930\u2009\u00b1\u20093 (26-35) \u00b5m.Paratylenchus lepidus is characterized by having a slender body, curved ventrally; lateral field with four incisures; lip region weakly sclerotized, continuous to body contour; median bulb elongate with a distinct valve; isthmus slender, surrounded by nerve ring; basal bulb pyriform; secretory-excretory pore located at level of basal bulb to pharyngo-intestinal junction; hemizonid located just anterior to secretory-excretory pore; gonad monodelphic, post uterine sac absent; vulval lips not protruding but having prominent advulval \ufb02ap; tail curved ventrally with a finely rounded to bluntly pointed terminus  was 99.7% similar (2\u2009bp difference) to the sequence of P. lepidus from GenBank (accession number: MK886692). The phylogenetic tree based on 28S rDNA sequences showed that the sequence of P.\u00a0lepidus from Vietnam was placed together with the sequence of P. lepidus from GenBank (100% PP) (COI mtDNA sequence of P. lepidus from Vietnam (418\u2009bp long) was also obtained and submitted to GenBank under the accession number MT828831.The 28S rDNA sequence of 100% PP) . A COI mP. lepidus from green tea in Vietnam is in agreement with the description of the type population (P. lepidus in Vietnam. The first COI mtDNA sequence of P. lepidus is also provided to serve as a molecular barcode for molecular identification of Paratylenchus species in the future.Morphology of pulation  with smapulation . In this"}
{"text": "Two copper(II) cations are situated in distorted square-pyramidal environment, while two copper(II) cations are located in a slightly square-planar geometry. One bridging acetate group acting in an \u03b71:\u03b71-\u03bc2-mode connects two copper(II) ions, while another bridging acetate group connects three copper(II) ions in an \u03b71:-\u03b72\u2013\u03bc3-mode.In the title Schiff base tetra\u00adnuclear copper(II) complex, two discrete environments are present in the structure: CuNO 3-acetato)(\u03bc2-acetato)\u00adbis\u00adethyl\u00adidene]amino}\u00adpropan-2-olato)tetra\u00adcopper(II) monohydrate, [Cu4(C19H19N2O3)2(CH3CO2)2]\u00b7H2O, corresponds to a non-symmetric tetra\u00adnuclear copper complex. The complex exhibits one ligand mol\u00adecule that connects two copper CuII metal centres via its ethano\u00adlato oxygen anion acting in a \u03bc2-mode and one ligand mol\u00adecule that connects three copper CuII metal centres via its ethano\u00adlato oxygen anion acting in a \u03bc3-mode. One bridging acetate group acting in an \u03b71:\u03b71-\u03bc2-mode connects two copper(II) ions while another bridging acetate group connects three copper(II) ions in an \u03b71:-\u03b72-\u03bc3-mode. A chair-like Cu3O3 structure is generated in which the two CuO4N units are connected by one \u03bc2-O ethano\u00adlate oxygen atom. These two units are connected respectively to the CuO3N unit via one \u03bc3-O ethano\u00adlate oxygen atom and one \u03bc2-O atom from an acetate group. The \u03bc3-O atom also connects one of the CuO4N units and the CuO3N unit to another CuO3N unit, which is out of the chair-like structure. Each of the two penta\u00adcoordinated CuII cations has a distorted NO4 square-pyramidal environment. The geometry of each of the two CuNO3 units is best described as a slightly square-planar environment. A series of intra\u00admolecular O\u2014H\u22efO hydrogen bonds is observed. In the crystal, the units are connected by inter\u00admolecular C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, thus forming sheets parallel to the ac planeThe title mol\u00adecular structure, namely, (\u03bc Mixing H3L and hydrated copper acetate yielded a tetra\u00adnuclear complex formulated as [Cu4L2(CH3CO2)2]\u00b7H2O in which the ligand acts in its tri-deprotonated \u22123L form. In the tetra\u00adnuclear complex, one of the \u22123L anions acts in \u03bc2-mode, connecting the two penta\u00adcoordinated CuII cations. The second \u22123L anion acts in \u03bc3 mode, connecting the two tetra\u00adcoordinated CuII cations and one of the penta\u00adcoordinated CuII cations. The second penta\u00adcoordinated CuII cation is connected to the two tetra\u00adcoordinated CuII cations via an acetate group acting in \u03b71:\u03b72-\u03bc3 mode. Additionally, the two penta\u00adcoordinated CuII cations are connected by an acetate group acting in \u03b71:\u03b71-\u03bc2 mode. For each ligand, the azomethine nitro\u00adgen atom and the phenolate oxygen atom of one arm are both linked to one CuII cation while the corresponding atoms of the other arm are bonded to another CuII cation. No phenolate oxygen atom acts in bridging mode. In one ligand the ethano\u00adlate oxygen atom bridges the two penta\u00adcoordinated CuII cations, and in the second ligand the ethano\u00adlate oxygen atom bridges the two tetra\u00adcoordinated CuII cations and one penta\u00adcoordinated CuII cation. The two \u22123L ligands are coordinated differently in hexa\u00addentate  and hepta\u00addentate  fashions. Four five-membered CuOCCN rings and four six-membered CuOCCCN rings are formed upon the coordination of the ligand mol\u00adecules. In the tetra\u00adnuclear complex, two discrete CuO4N and CuO3N units are observed.\u03c4 parameter  around the metal ion are \u03c4 = 0.1103 for Cu1 and \u03c4 = 0.1887 for Cu2. For Cu1 and Cu2, the basal planes are occupied by one phenolate oxygen anion, one azomethine nitro\u00adgen atom, one ethano\u00adlate oxygen atom and one oxygen atom from the \u03b71:\u03b71-\u03bc2 acetate group, the apical position being occupied by an ethano\u00adlate oxygen atom from a second ligand mol\u00adecule for Cu1 and an oxygen atom from the \u03b71:\u03b72-\u03bc3 acetate group for Cu2. The atoms forming the basal plane for Cu1  are almost coplanar (r.m.s. deviation = 0.1088\u2005\u00c5) and the Cu1 atom is displaced toward the O5 atom, which occupies the apical position, by 0.0545\u2005(2)\u2005\u00c5. The Cu1\u2014O5 distance of 2.749\u2005(3)\u2005\u00c5 is longer than the distances between Cu1 and the atoms in the basal plane , as expected for a Jahn\u2013Teller distortion \u201395.10\u2005(14)\u00b0 and 169.71\u2005(16)\u2013176.33\u2005(14)\u00b0, respectively. The atoms forming the basal plane for Cu2  are less coplanar than those around Cu1 (r.m.s. deviation = 0.2086\u2005\u00c5) and the Cu2 atom is displaced toward the O8 atom, which occupies the apical position, by 0.0808\u2005(1)\u2005\u00c5. The from Cu2\u2014O8 distance of 2.703\u2005(4)\u2005\u00c5 is longer than those to atoms in the equatorial plane . As observed for Cu1, Jahn\u2013Teller distortion \u201396.89\u2005(14)\u00b0 and 161.66\u2005(15)\u2013173.00\u2005(15)\u00b0, respectively. The bond lengths involving the \u03bc2-bridging ethano\u00adlato oxygen atom and the copper cations are asymmetrical: Cu1\u2014O2 = 1.916\u2005(3)\u2005\u00c5 and Cu2\u2014O2 = 1.920\u2005(3)\u2005\u00c5. The distances between the \u03bc3-bridging ethano\u00adlato oxygen atom and the copper cations are very different: Cu1\u2014O5 = 2.749\u2005(3)\u2005\u00c5, Cu3\u2014O5 = 1.907\u2005(3)\u2005\u00c5 and Cu4\u2014O5 = 1.921\u2005(3)\u2005\u00c5. The copper cations Cu3 and Cu4 are coordinated by one ethano\u00adlato oxygen anion, one phenoxo oxygen anion, one azomethine nitro\u00adgen atom of the ligand and one oxygen atom of a \u03b71:\u03b72-\u03bc3 acetate group (O8 for Cu3 and O7 for Cu4). The Cu3\u2014O4 [1.873\u2005(3)\u2005\u00c5], Cu3\u2014O5 [1.907\u2005(3)\u2005\u00c5], Cu3\u2014N3 [1.947\u2005(4)\u2005\u00c5], Cu3\u2014O8 [1.957\u2005(3)\u2005\u00c5], Cu4\u2014O6 [1.869\u2005(3)\u2005\u00c5], Cu4\u2014O5 [1.921\u2005(3)\u2005\u00c5], Cu4\u2014N4 [1.962\u2005(4)\u2005\u00c5] and Cu4\u2014O7 [1.955\u2005(3)\u2005\u00c5] distances are in close proximity to values reported for copper(II) complexes with analogous Schiff base ligands  and 0.1801 (Cu4) suggested distorted square-planar geometries. For the two copper cations the cisoid angles are in the ranges 86.17\u2005(14)\u201393.29\u2005(15)\u00b0 for Cu3 and 84.04\u2005(14)\u201396.93\u2005(14)\u00b0 for Cu4 and the transoid angles are O4\u2014Cu3\u2014O5 = 177.07\u2005(15)\u00b0, O8\u2014Cu3\u2014N3 = 173.28\u2005(15)\u00b0, O6\u2014Cu4\u2014O5 = 170.48\u2005(14)\u00b0 and O7\u2014Cu3\u2014N4 = 164.11\u2005(15)\u00b0. The C\u2014N bonds are in the range 1.291\u2005(6)\u20131.300\u2005(6)\u2005\u00c5, indicative of double-bond character and the presence of the imino groups in the two ligands.Atoms Cu1 and Cu2 are penta\u00adcoordinated and their environments can be best described as slightly distorted square-pyramidal. The Addison phenoxo are observed ethyl\u00adidene)]-2-hy\u00addroxy\u00adpro\u00adpane-1,3-di\u00adamine is widely used in coordination chemistry. The current release of the CSD ethyl\u00adidene)]-2-hy\u00addroxy\u00adpropane-1,3-di\u00adamine (HL3) was prepared from 1-(2-hy\u00addroxy\u00adphen\u00adyl)ethanone and 2-hy\u00addroxy\u00adpropane-1,3-di\u00adamine in a 2:1 ratio in ethanol according to a slight modification of a literature method : 3538 (OH), 3268 (OH), 1605 (C=N), 1538 (C=C), 1528 (C=C), 1455 (C=C), 1247 (C\u2014O), 1043, 760. Analysis calculated for C19H22N2O3: C, 69.92; H, 6.79; N, 8.58. Found: C, 69.90; H, 6.76; N, 8.56%.The ligand 3CO2)2\u00b7(H2O)  in 5\u2005mL of ethanol was added to a solution of H3L  in 10\u2005mL of ethanol at room temperature. The initial yellow solution immediately turned deep green and was stirred for 30\u2005min before being filtered. The filtrate was kept at 298\u2005K. After one week, light-green crystals suitable for X-ray diffraction were collected and formulated as [Cu4L2(CH3CO2)2]\u00b7H2O. FT\u2013IR : 3404, 1601, 1532, 1332, 1299, 895, 760. Analysis calculated for C42H46Cu4N4O11: C, 48.64; H, 4.47; N, 5.40. Found: C, 48.60; H, 4.49; N, 5.44%.A solution of Cu were geometrically optimized  and refined using a riding model (AFIX instructions) with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for CH3 and OH groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022002225/ex2053sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022002225/ex2053Isup3.hklStructure factors: contains datablock(s) I. DOI: 2154581CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A precise crystal-structure analysis using a neutron diffractometer with high-power neutron sources at the J-PARC facility has been performed on non-deuterated triglycine sulfate at 20\u2005K and 298\u2005K and a new double-potential-well disorder model for the O\u2014H\u22efO hydrogen bond in the 298\u2005K structure is proposed. 2H6NO2+\u00b7SO42\u2212\u00b7C2H5NO2 (or C6H17N3O10S), non-deuterated triglycine sulfate (HTGS) at 20\u2005K and 298\u2005K were undertaken using time-of-flight neutron diffraction data. At 20\u2005K for the O\u2014H\u22efO hydrogen bond between the glycinium cation and the zwitterionic, unprotonated glycine mol\u00adecule that is associated with the ferroelectric behaviour of HTGS, O\u2014H = 1.070\u2005(3), H\u22efO = 1.408\u2005(3) [\u03b4 = 0.338\u2005(4)], O\u22efO = 2.4777\u2005(15)\u2005\u00c5 and O\u2014H\u22efO = 179.0\u2005(4)\u00b0, which is in good agreement with previous studies. Two reasonable structures for the same three atoms were refined for the 298\u2005K dataset. One is a single-minimum potential-energy model, with O\u2014H = 1.090\u2005(12), H\u22efO = 1.361\u2005(12) [\u03b4 = 0.271\u2005(17)], O\u22efO = 2.450\u2005(7)\u2005\u00c5 and O\u2014H\u22efO = 179.2\u2005(10)\u00b0, having the H atom with a large ellipticity along the bond path between the O atoms. The other is a double-minimum potential-energy model having two H atom sites with occupancies of 0.876\u2005(8) and 0.124\u2005(8): for the major occupancy component, O\u2014H = 1.065\u2005(12), H\u22efO = 1.387\u2005(12), O\u22efO = 2.451\u2005(7)\u2005\u00c5 and O\u2014H\u22efO = 178.2\u2005(11)\u00b0 and for the minor component, O\u2014H = 1.06\u2005(4), H\u22efO = 1.41\u2005(4), O\u22efO = 2.451\u2005(7)\u2005\u00c5 and O\u2014H\u22efO = 166\u2005(2)\u00b0. These models did not show any significant differences in R factors. In addition, the unit-cell parameters and other structural parameters of HTGS did not show any major differences compared to those of partially deuterated TGS and fully deuterated TGS for both 20\u2005K and 298\u2005K.Precise single-crystal structure analyses of the title compound, bis\u00ad(glycinium) sulfate\u2013glycine (1/1), 2C The authors also proposed a hydrogen-bonding scheme and pointed out that the hydrogen atom that lies between the oxygen atom of the carboxyl group in the glycine III cation (GIII) and the O atom in the glycine II mol\u00adecule (GII) plays a crucial role in the dipole reversal. Many structural studies on TGS have subsequently been conducted (see Database survey): most of them were X-ray diffraction studies, but some of them were neutron diffraction studies. The atomic coordinates of non-deuterated TGS , including those of the hydrogen atoms at room temperature, were first revealed using single-crystal neutron diffraction  group in each glycine mol\u00adecule and those in sulfuric acid mol\u00adecules at 40\u2005K and 180\u2005K , where deuterium replaced the H atoms except for the hydrogen atoms of the methyl\u00adene , all the hydrogen atoms in the glycine mol\u00adecules and sulfuric acid mol\u00adecules are substituted by deuterium atoms: the crystal structures did not show major changes between 20\u2005K and 295\u2005K  exist as monoprotonated C2H6NO2+ glycinium ions. The most significant feature of these glycine/glycinium species are the N\u2014C\u2014C\u2014O(H) torsion angles \u00b0 for N11\u2014C17\u2014C19\u2014O7, \u22121.5\u2005(1)\u00b0 for N14\u2014C15\u2014C18\u2014O10 and \u22121.4\u2005(1)\u00b0 for N21\u2014C20\u2014C16\u2014O2. The sulfate ion shows its expected tetra\u00adhedral shape with bond distances of 1.480\u2005(2)\u2005\u00c5 (S1\u2014O4), 1.470\u2005(2)\u2005\u00c5 (S1\u2014O5), 1.477\u2005(2)\u2005\u00c5 (S1\u2014O6) and 1.472\u2005(2)\u2005\u00c5 (S1\u2014O8) and bond angles of 110.3\u2005(1)\u00b0 (O4\u2014S1\u2014O5), 107.9\u2005(1)\u00b0 (O4\u2014S1\u2014O6), 108.7\u2005(1)\u00b0 (O4\u2014S1\u2014O8), 109.7\u2005(1)\u00b0 (O5\u2014S1\u2014O6), 110.6\u2005(1)\u00b0 (O5\u2014S1\u2014O8) and 109.7\u2005(1)\u00b0 (O6\u2014S1\u2014O8). The slight differences among these distances and angles may arise because of the different hydrogen bonds accepted by these O atoms. Numerous N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds (see supporting information) are formed between the glycine or glycinium species and the sulfate ions; four N\u2014H\u22efO hydrogen bonds and one O\u2014H\u22efO hydrogen bond are formed by GI, five N\u2014H\u22efO hydrogen bonds are formed by GII and five N\u2014H\u22efO hydrogen bonds with the sulfate ion and one O\u2014H\u22efO hydrogen bond to the glycine mol\u00adecule is formed by GIII.The refined structures at 20\u2005K are shown in Figs. 1i  bond lengths for HTGS, DTGS and FDTGS at low temperature are listed in Table\u00a01et al. 1997The lattice constants and the key O15\u2014H15\u22efO3B amino group [refined site occupancies = 0.874\u2005(8):0.126\u2005(8)] in the GI cation and the O\u2014H\u22efO association for GIII and GII. Two models were refined considering the H atom between O15 in GIII and O3 in GII. For one model (298\u2005K model 1), the H15 atom was refined with a large ellipticity along the bond path between O15 and O3 as a single minimum potential energy structure [Fig.\u00a05a)]. A double-minimum potential-energy structure could be deduced because the distance between O15 and O3i  did not increase with an increase in the temperature; thus for the other model (298\u2005K model 2), a pair of hydrogen atoms were refined along the bond path between O15 and O3i, the double-minimum potential structure [Fig.\u00a05b)].The refined structures at 298\u2005K are shown in Figs. 3i hydrogen bond at 298\u2005K are summarized in Table\u00a02i in GII. On the other hand, the distance between O15 and H15 [1.090\u2005(12)\u2005\u00c5] is almost the same as that at 20\u2005K despite there being no distance restraint for the H15\u22efO3i separation. Therefore, the mixed structure (model 2) of the major ferroelectric phase and minor paraelectric phase is strongly suggested, because the occupancies of N11 and N11B and H15 and H3i are related by symmetry.The key parameters for the O15\u2014H15\u22efO3et al., 1997The unit-cell parameters and bond lengths for HTGS, DTGS, and FDTGS at 298\u2005K are listed in Table\u00a02TC for FDTGS increased by approximately 12\u2005K compared to HTGS. Choudhury & Chitra (2008B (12%); this occupancy ratio is in excellent agreement with the results in this study. For the hydrogen atom between the oxygen atom of the carboxyl group in GIII and that in the GII, the O\u22efO distance was 2.470\u2005(9)\u2005\u00c5, and the H atom was approximately 0.241\u2005\u00c5 closer to the GIII O atom than that in GII. They concluded that the structure of HTGS at room temperature has a single minimum potential energy in the O\u2014H\u22efO hydrogen-bond path between GIII and GII. In this study, two reasonable structures were refined as a single-minimum potential-energy model and a double-minimum model without any significant differences. Therefore, we conclude that there is a significant possibility of a double-minimum potential-energy model for HTGS at 298\u2005K.In the previous studies using single-crystal neutron diffraction, Kay & Kleinberg 1973 proposeditra 2008 proposedsupporting information) and no additional inter\u00admolecular inter\u00adactions were found. Therefore, the 20\u2005K and 298\u2005K structures form essentially the structural motif of a three-dimensional network of N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds between glycinium cations, glycine mol\u00adecules and sulfate ions.Hydrogen bonds in the refined structures were consistent with those reported previously ; TGLYSU15  and sulfuric acid  was added to 50\u2005ml of water in a 100\u2005ml beaker. They were dissolved by heating at \u223c313\u2005K with a 300 r.p.m. magnetic stirrer. After completely dissolving them, plastic films were double-wrapped around the beaker, and some holes were knocked in the films to evaporate the water slowly. The beaker was left to stand at \u223c293\u2005K. HTGS was crystallized after approximately a month, and then the solution was filtered. The collected crystals were dried in a desiccator at \u223c293\u2005K.et al., 2016x, y, \u03bb) were measured in 16 different orientations for each dataset. The measurement time was 1.5\u2005h for one orientation; the raw data were processed using STARGazer  slice maps and merged TOF profiles.Crystal data, data collection, and structural refinement details are summarized in Table\u00a03SHELXL2018  between O15 and O3 to minimize the model dependence. A nuclear density distribution  global, 20K, 298KModel1, 298KModel2. DOI: 10.1107/S2056989022000858/hb800420Ksup2.hklStructure factors: contains datablock(s) 20K. DOI: Click here for additional data file.10.1107/S2056989022000858/hb800420Ksup5.cmlSupporting information file. DOI: 10.1107/S2056989022000858/hb8004298KModel1sup3.hklStructure factors: contains datablock(s) 298KModel1. DOI: Click here for additional data file.10.1107/S2056989022000858/hb8004298KModel1sup6.cmlSupporting information file. DOI: 10.1107/S2056989022000858/hb8004298KModel2sup4.hklStructure factors: contains datablock(s) 298KModel2. DOI: Click here for additional data file.10.1107/S2056989022000858/hb8004298KModel2sup7.cmlSupporting information file. DOI: 2144164, 2144163, 2144162CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing of the title compound features C\u2014H\u22efO hydrogen bonds, C\u2014F\u22ef\u03c0 inter\u00adactions, aromatic \u03c0\u2013\u03c0 stacking and short Br\u22efO contacts. 14H8Br2FN3O2, the nitro-substituted benzene ring and the 4-fluoro\u00adphenyl ring form a dihedral angle of 65.73\u2005(7)\u00b0. In the crystal, mol\u00adecules are linked into chains by C\u2014H\u22efO hydrogen bonds running parallel to the c-axis direction. The crystal packing is consolidated by C\u2014F\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions, and short Br\u22efO [2.9828\u2005(13)\u2005\u00c5] contacts are observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H\u22efH (17.4%), O\u22efH/H\u22efO (16.3%), Br\u22efH/H\u22efBr (15.5%), Br\u22efC/C\u22efBr (10.1%) and F\u22efH/H\u22efF (8.1%) contacts.In the title compound, C R\u2014N=N\u2014R\u2032, where R and R\u2032 can be either aryl, hetrocycle or alkyl functional groups. They find many applications such as mol\u00adecular switches, optical data storage, anti\u00admicrobial agent, colour-changing materials, non-linear optics, mol\u00adecular recognition, dye-sensitized solar cells, liquid crystals, catalysis, etc. \u00b0. All of the other bond lengths and angles in the title compound are similar to those in the related azo compounds reported in the Database survey.As shown in Fig.\u00a01Cg1 = 3.4095\u2005(12)\u2005\u00c5; C\u2014F\u22efCg1 = 136.95\u2005(9)\u00b0] inter\u00adactions and weak aromatic \u03c0\u2013\u03c0 stacking [Cg2\u22efCg2 = 3.9694\u2005(9)\u2005\u00c5], where Cg1 and Cg2 are the centroids of the C3\u2013C8 and C9\u2013C14 rings, respectively  = 2.9828\u2005(13)\u2005\u00c5; van der Waals contact distance = 3.37\u2005\u00c5] are observed.In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into chains propagating parallel to the c axis Table\u00a01. The cryly Fig.\u00a02. In addiCrystalExplorer17  and those delineated into H\u22efH, O\u22efH/H\u22efO, Br\u22efH/H\u22efBr, Br\u22efC/C\u22efBr and F\u22efH/H\u22efF contacts . In the Br\u22efH/H\u22efBr fingerprint plot, there are two symmetrical wings with de + di \u2243 2.85\u2005\u00c5 and they contribute 15.5% to the Hirshfeld surface . The pair of characteristic wings in the fingerprint plot delin\u00adeated into Br\u22efC/C\u22efBr contacts , have the tips at de + di \u2243 3.80\u2005\u00c5, while for F\u22efH/H\u22efF contacts , they have the tips at de + di \u2243 2.60\u2005\u00c5. The remaining contributions from the other different inter\u00adatomic contacts to the Hirshfeld surfaces are listed in Table\u00a03et al., 2015The overall two-dimensional fingerprint plot Fig.\u00a04a and thce Fig.\u00a04c. In thce Fig.\u00a04d. The pet al., 2016E)-1--2-phenyl\u00addiazene unit gave 26 hits. Seven compounds are closely related to the title compound, viz. CSD refcode GUPHIL (I)       , mol\u00adecules are linked into inversion dimers via short halogen\u2013halogen contacts [Cl1\u22efCl1 = 3.3763\u2005(9)\u2005\u00c5 C16\u2014Cl1\u22efCl1 = 141.47\u2005(7)\u00b0] compared to the van der Waals radius sum of 3.50\u2005\u00c5 for two chlorine atoms. No other directional contacts could be identified and the shortest aromatic-ring-centroid separation is greater than 5.25\u2005\u00c5. In the crystals of (II) and (III), the aromatic rings form dihedral angles of 64.1\u2005(2) and 60.9\u2005(2)\u00b0, respectively. Mol\u00adecules are linked through weak X\u22efCl contacts [X = Cl for (II) and Br for (III)], C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets lying parallel to the ab plane. In the crystal of (IV), the planes of the benzene rings make a dihedral angle of 56.13\u2005(13)\u00b0. Mol\u00adecules are stacked in columns along the a-axis direction via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In (V), the benzene rings form a dihedral angle of 63.29\u2005(8)\u00b0. Mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In the crystals of (VI) and (VII), the dihedral angles between the aromatic rings are 60.31\u2005(14) and 56.18\u2005(12) \u00b0, respectively. In (VI) C\u2014H\u22efN and short Cl\u22efCl contacts are observed and in (VII), C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short Cl\u22efO contacts occur.In the crystal of (E)-1-(4-fluoro\u00adphen\u00adyl)-2-(2-nitro\u00adbenzyl\u00adidene)hydrazine (1\u2005mmol), tetra\u00admethyl\u00adethylenedi\u00adamine (TMEDA) , CuCl  and CBr4 (4.5\u2005mmol). After 1\u20133h  the reaction mixture was poured into a \u223c0.01 M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005ml). The combined organic phase was washed with water (3 \u00d7 50\u2005ml), brine (30\u2005ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Light-orange solid (52%); m.p. 377\u2005K. Analysis calculated for C14H8Br2FN3O2 (M = 429.04): C 39.19, H 1.88, N 9.79; found: C 39.14, H 1.87, N 9.73%. 1H NMR  \u03b4 7.86\u20137.14 . 13C NMR  \u03b4 165.02, 163.23, 163.01, 149.72, 133.01, 132.10, 129.70, 124.98, 124.87, 124.80, 124.29, 116.07, 115.91, 86.88. ESI\u2013MS: m/z: 430.02 [M + H]+.A 20\u2005ml screw-neck vial was charged with DMSO (10\u2005ml), (Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698902200278X/hb8012sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902200278X/hb8012Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902200278X/hb8012Isup3.cmlSupporting information file. DOI: 2158375CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Five new bis\u00ad(aryl\u00adamide)\u00addichlorido\u00adzinc(II) complexes have been prepared and characterized. All of the complexes contain hydrogen bonds between the amide N\u2014H group and the amide carbonyl oxygen atoms or the chlorine atoms, forming extended networks. O)di\u00adchlorido\u00adzinc(II), [ZnCl2(C7H7NO)2], di\u00adchlor\u00adido\u00adbis\u00ad(2-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], di\u00adchlorido\u00adbis\u00ad(3-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], di\u00adchlorido\u00adbis\u00ad(4-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], and di\u00adchlorido\u00adbis\u00ad(4-hy\u00addroxy\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C7H7NO2)2]. All of the complexes contain hydrogen bonds between the amide N\u2014H group and the amide carbonyl oxygen atoms or the chlorine atoms, forming extended networks.Ionic co-crystals are co-crystals between organic mol\u00adecules and inorganic salt coformers. Co-crystals of pharmaceuticals are of inter\u00adest to help control polymorph formation and potentially improve stability and other physical properties. We describe the preparation, crystal structures, and hydrogen bonding of five different 2:1 benzamide or tolu\u00adamide/zinc(II) chloride co-crystal salts, namely, bis\u00ad(benzamide-\u03ba All five complexes are 2:1 O-bonded aryl amide:ZnCl2 complexes with approximately tetra\u00adhedral zinc(II) centers. The complexes crystallize in five different space groups and form hydrogen-bonding inter\u00adactions between the amide N\u2014H groups and either an amide oxygen or a zinc-bound chlorido ligand.Five new zinc complexes, (1), bis\u00ad(benzamide-\u03baO)di\u00adchlorido\u00adzinc(II), [ZnCl2(C7H7NO)2], crystallizes in the P21/n space group with two independent mol\u00adecules in the asymmetric unit and displays one N\u2014H\u22efO and one N\u2014H\u22efCl intra\u00admolecular hydrogen bond in each mol\u00adecule , di\u00adchlorido\u00adbis\u00ad(2-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], displays two intra\u00admolecular N\u2014H\u22efCl hydrogen bonds to one chlorine atom (see Table\u00a02P21 space group. Compound (3), di\u00adchlorido\u00adbis\u00ad(3-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], crystallizes in the C2/c space group with the zinc atom lying on the twofold axis  does not form any intra\u00admolecular hydrogen bonds. Compound (4), di\u00adchlorido\u00adbis\u00ad(4-methyl\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C8H9NO)2], crystallizes in the P21/c space group and compound (5), di\u00adchlorido\u00adbis\u00ad(4-hy\u00addroxy\u00adbenzamide-\u03baO)zinc(II), [ZnCl2(C7H7NO2)2], crystallizes in the Cc space group and both compounds form two intra\u00admolecular hydrogen bonds, one N\u2014H\u22efO and one N\u2014H\u22efCl, similar to the inter\u00adactions found in compound (1)  found in a search of the CSD  forms four N\u2014H\u22efCl inter\u00admolecular hydrogen bonds (two from each independent mol\u00adecule), forming an extended network as shown in Fig.\u00a062) also utilizes N\u2014H bonds in hydrogen-bonding inter\u00adactions, two intra\u00admolecular and two inter\u00admolecular, to form layers within the structure   forms two N\u2014H\u22efCl inter\u00admolecular contacts in addition to the two intra\u00admolecular hydrogen bonds, resulting in a complex set of layers that run perpendicular to the b axis  results in the greatest number of hydrogen bonds among this set of complexes, as shown in Fig.\u00a010Each compound displays a unique hydrogen-bonding network, consisting primarily of N\u2014H\u22efO and N\u2014H\u22efCl inter\u00adactions, summarized in Table\u00a011), (3), and (5) form \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of the benzamide or tolu\u00adamide groups as summarized in Table\u00a072) or (4).Compounds . The similar di\u00adchlorido\u00adbis\u00ad(dmf)zinc(II)  has also been reported. Edwards et al. , the latter of which undergoes a reversible phase transition at 228\u2005K 2 where X = Cl, Br, I . As part of a larger study, Smirnov et al. , thio\u00adacetamide (VUCTOD), and benzamide (VUCVAR).A number of zinc(II) iodide complexes, ZnI al. 2009 have alset al. , one water molecule, and two chlorido ligands. In the second form (CCDC 2010264), the zinc bonds to one nefiracetam molecule through the \u03b3-lactam and to a second via the amide carbonyl, forming a cyclic zinc dimer.Three structural studies have prepared zinc(II)chloride complexes with pharmaceutically relevant mol\u00adecules. Sultana  al. 2016 prepared al. 2020 describe1) through (5) were prepared by dissolution of the respective components in various solvents  followed by slow evaporation. In a typical preparation, a 1:1 stoichiometric ratio of benzamide (0.1352\u2005g) and zinc(II) chloride (0.1336\u2005g) was dissolved in approximately 5\u2005mL of a 50:50 v:v ratio of water and ethanol. Slow evaporation of the resulting solution produced single crystals of compound (1).All reagents were used as received from the manufacturer. Compounds  = 1.2Ueq(C) (aromatic) or Uiso(H) = 1.5Ueq(C) (meth\u00adyl). All amide H-atom positions were refined with N\u2014H distances restrained to 0.88\u2005(2)\u2005\u00c5 and Uiso(H) = 1.5Ueq(N). The hydroxyl H-atom positions in compound (5) were refined with O\u2014H distances restrained to 0.84\u2005(2)\u2005\u00c5 and Uiso(H) = 1.5Ueq(N).All carbon-bonded H atoms were placed in idealized positions using a riding model with aromatic C\u2014H = 0.95\u2005\u00c5, methyl C\u2014H = 0.98\u2005\u00c5 and 1) was refined as a pseudo-merohedral twin  with a twin law of (0 0 \u22121 0 \u22121 0 \u22121 0 0) , corresponding to a twofold rotation about the [10Compound (3) was modeled as a disordered methyl group with each set of hydrogen atoms rotated by 60\u00b0 (AFIX 127). The disorder was identified from multiple peaks near C8 in the difference map. The refined occupancies of the two hydrogen atom sets were 0.54\u2005(2):0.46\u2005(2).The methyl group in compound  global, 1, 2, 3, 4, 5. DOI: 10.1107/S2056989021008264/zl50231sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50231sup7.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50232sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50232sup8.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50233sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50233sup9.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50234sup10.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50234sup5.hklStructure factors: contains datablock(s) 4. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50235sup11.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50235sup6.hklStructure factors: contains datablock(s) 5. DOI: 2102513, 2102512, 2102511, 2102510, 2102509CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II featuring piano-stool geometries and supported by tri\u00adaryl\u00adphosphine ligands, showing the effects of para substitution on supra\u00admolecular structure and allowing comparison to the large class of previously reported acetyl complexes.Solid-state structures are presented for three propionyl complexes of Mo para substituents, namely, dicarbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)propion\u00adyl(tri\u00adphenyl\u00adphosphane-\u03baP)molybdenum(II), [Mo(C5H5)(C3H5O)(C18H15P)(CO)2], (1), dicarbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)propion\u00adyl[tris\u00ad(4-fluoro\u00adphen\u00adyl)phosphane-\u03baP]molybdenum(II), [Mo(C5H5)(C3H5O)(C18H12F3P)(CO)2], (2), and dicarbon\u00adyl(\u03b75-cyclo\u00adpenta\u00addien\u00adyl)propion\u00adyl[tris\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)phosphane-\u03baP]molybdenum(II) dichloromethane solvate, [Mo(C5H5)(C3H5O)(C21H21O3P)(CO)2]\u00b7CH2Cl2, (3), have been prepared from the corresponding ethyl complexes via phosphine-induced migratory insertion. These complexes exhibit four-legged piano-stool geom\u00adetries with mol\u00adecular structures quite similar to each other and to related acetyl complexes. The extended structures of the three complexes differ somewhat, with the para substituent of the tri\u00adaryl\u00adphosphine of (2) (fluoro) or (3) (meth\u00adoxy) engaging in non-classical C\u2014H\u22efF or C\u2014H\u22efO hydrogen-bonding inter\u00adactions. The structure of (3) exhibits modest disorder in the position of one Cl atom of the di\u00adchloro\u00admethane solvent, which was modeled with two sites showing approximately equivalent occupancies [0.532\u2005(15) and 0.478\u2005(15)].Three cyclo\u00adpenta\u00addienylmolybdenum(II) propionyl complexes featuring tri\u00adaryl\u00adphosphine ligands with different  Although substitution of phosphine aryl groups with electron-withdrawing or -donating groups minimally affects local structure, the supra\u00admolecular organization is substanti\u00adally affected by non-classical hydrogen-bonding to the fluoro and meth\u00adoxy groups in (2) and (3), respectively.We were inter\u00adested in extending earlier studies to higher-order alkyl groups at molybdenum, and in this report we describe the synthesis and solid-state structures of related Mo1), (2), and (3) are illustrated in Figs. 1trans-disposed carbonyl ligands. As previously observed for most related acetyl complexes, the acyl C=O points up toward the Cp ring. In the case of (1), this phenomenon could be rationalized by presence of short C4\u2014H4A\u22efO1 (2.672\u2005\u00c5) and C4\u2014H4B\u22efO2 (2.639\u2005\u00c5) contacts involving the carbonyl ligands that are enabled when the acyl points up. However, the variation of the Mo1\u2014C3\u2014C4\u2014C5 torsion angle across the series  argues against the general importance of such an inter\u00adaction.The mol\u00adecular structures of (1), (2), and (3) are presented in Tables 12) crystallized with two nearly equivalent mol\u00adecules in the asymmetric unit, so geometric parameters are presented for both. In general, the three complexes are nearly identical, as might be expected based on the dominant role of sterics in determining structure and the fact that the steric profiles of the three tri\u00adaryl\u00adphosphine ligands are identical. The Mo\u2014P bond length in (2) [2.4692\u2005(4)\u2005\u00c5 (avg)] is slightly shorter than in (1) or (3) , which may be related to stronger \u03c0-backbonding to the tris\u00ad(4-fluoro\u00adphen\u00adyl)phosphine ligand. Stronger backbonding is supported by the observation by infrared spectroscopy of slightly higher-energy carbonyl stretching vibrations for (2) [\u03bd(CO)avg = 1897\u2005cm\u22121] compared with (1) and (3) . Geometric parameters for all complexes are quite similar to those for the related tri\u00adphenyl\u00adphosphine-supported CpMo acetyl complex , (2), and (3) in their mol\u00adecular structures, the para substituent of the tri\u00adaryl\u00adphosphine ligand  plays an important role in determining the extended structure. The extended structure of (1) is dominated by non-classical C\u2014H\u22efO inter\u00adactions involving its carbonyl ligands. A short C\u2014H\u22efO inter\u00adaction between O2 and H12 of a phenyl ring (2.36\u2005\u00c5) joins mol\u00adecules of (1) into centrosymmetrical dimers that are organized into chains along [010] by inter\u00admolecular C15\u2014H15\u22efCg4  and intra\u00admolecular O2\u22efCg4 (3.295\u2005\u00c5) inter\u00adactions  features two nearly equivalent mol\u00adecules in the asymmetric unit exhibiting a non-classical C\u2014H\u22efO inter\u00adaction between O6 of a propionyl ligand and H15 from a phenyl ring (2.59\u2005\u00c5) and a C\u2014H\u22efF close contact between F3 and H53 (2.60\u2005\u00c5). These pairs of mol\u00adecules are joined into chains along [001] by C34\u2014H34\u22efO1 hydrogen bonding .The tris\u00ad(4-fluoro\u00adphen\u00adyl)phosphine-supported derivative (1), complex (3) is joined into centrosymmetrical dimers by a C\u2014H\u22efO inter\u00adaction involving a carbonyl ligand . This further set of inter\u00adactions involving meth\u00adoxy groups, as well as important close contacts involving the di\u00adchloro\u00admethane solvent, are depicted in Fig.\u00a09Like complex (CO)2(PR3)(COR). The trans-dicarbonyl structure, as observed for (1)\u2013(3), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis CpMo(CO). This compound was prepared by modification of the method used of Gladysz et al.  was dissolved in THF (10\u2005ml). Sodium tri\u00adethyl\u00adborohydride  was added dropwise by syringe with vigorous stirring, leading to an immediate color change from purple to green\u2013yellow with evolution of H2 gas. The reaction was allowed to proceed with stirring for 20\u2005min, and an excess of iodo\u00adethane  was added dropwise with stirring and the reaction was allowed to proceed for 6\u2005h. Volatiles were removed in vacuo to afford a yellow\u2013brown film that was stored at 238\u2005K for 1 week. The solid was extracted with pentane (4 \u00d7 10\u2005ml) and filtered through a 1\u2005cm pad of activated alumina to afford a yellow solution, and removal of solvent in vacuo afforded 3(CH2CH3)CpMo(CO) as a pure yellow powder . 1H NMR : \u03b4 5.28 , 1.72 , 1.45 . 13C{1H} NMR : \u03b4 239.9 (Mo\u2014CO), 227.8 (Mo\u2014CO), 93.0 (Cp ring), 20.4 (Mo\u2014CH2CH3) \u22123.7 (Mo\u2014CH2CH3). IR  \u03bd(CO): 2015, 1921 (split). al. 1979, as prev al. 1979 and Anst al. 2020. In a 202(PPh3)(COCH2CH3) (1)CpMo(CO). In an inert-atmos\u00adphere glove box, CpMo(CO)3(CH2CH3)  and tri\u00adphenyl\u00adphosphine  were dissolved in aceto\u00adnitrile (5\u2005ml) in a 20\u2005ml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, during which time a bright-yellow precip\u00aditate formed. The yellow solid was isolated by filtration and washed with pentane (2 \u00d7 5\u2005ml), then dried in vacuo to afford pure 1. Yellow crystals of 1 suitable for X-ray diffraction were obtained from a concentrated di\u00adchloro\u00admethane solution by vapor cross diffusion with pentane at 238\u2005K. 1H NMR : \u03b4 7.50\u20137.30 , 5.00 , 3.03 CH2CH3), 0.90 CH2CH3). 13C{1H} NMR : \u03b4 267.7 , 238.8 , 135.7 , 133.2 , 130.5 , 128.6 , 96.7 (Cp ring), 58.1 (Mo\u2014COCH2CH3), 10.1 (Mo\u2014COCH2CH3). 31P{1H} NMR : \u03b4 68.4 (s). IR  \u03bd(CO): 1935, 1851, 1614 (acet\u00adyl).2(P(4-FPh)3)(COCH2CH3) (2)CpMo(CO). In an inert-atmosphere glove box, CpMo(CO)3(CH2CH3)  and tris\u00ad(4-fluoro\u00adphen\u00adyl)phosphine  were dissolved in aceto\u00adnitrile (5\u2005ml) in a 20\u2005ml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, causing a color change to orange, but without formation of any precipitate. Solvent was removed in vacuo, causing precipitation of a yellow solid that was isolated by filtration and washed with pentane (2 \u00d7 3\u2005ml) to afford the desired product 2 . Yellow crystals of 2 suitable for X-ray diffraction were obtained from a concentrated di\u00adchloro\u00admethane solution by vapor cross diffusion with pentane at 238\u2005K. 1H NMR : \u03b4 7.41\u20137.30 , 7.14 , 4.90 , 2.99 CH2CH3), 0.90 CH2CH3). 13C{1H} NMR : \u03b4 265.4 , 238.2 , 164.0 , 135.0 , 131.3 , 116.0 , 96.5 (Cp ring), 58.2 (Mo\u2014COCH2CH3), 10.9 (Mo\u2014COCH2CH3). 31P{1H} NMR : \u03b4 68.5 (s). IR  \u03bd(CO): 1938, 1856, 1620 (acet\u00adyl).2(P(4-MeOPh)3)(COCH2CH3) (3)CpMo(CO). In an inert-atmosphere glove box, CpMo(CO)3(CH2CH3)  and tris\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)phosphine  were dissolved in aceto\u00adnitrile (5\u2005ml) in a 20 nml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, causing precipitation of 3 as a pure yellow powder that was isolated by filtration. Crystals of 3 suitable for X-ray diffraction were obtained from a concentrated di\u00adchloro\u00admethane solution by vapor cross diffusion with pentane at 238\u2005K. 1H NMR : \u03b4 7.37\u20137.23 , 7.14 , 4.99 , 3.03 CH2CH3), 0.89 CH2CH3). 13C{1H} NMR : \u03b4 268.6 , 239.2 , 161.1 (C\u2014OCH3 of phosphine), 134.6 , 127.4 , 114.0 , 96.6 (Cp ring), 58.0 (Mo\u2014COCH2CH3), 10.1 (Mo\u2014COCH2CH3). 31P{1H} NMR : \u03b4 62.3 (s). IR  \u03bd(CO): 1933, 1847, 1605 (acet\u00adyl).Uiso(H) = k\u00d7Ueq(C), k = 1.2 for cyclo\u00adpenta\u00addienyl, phenyl, and methyl\u00adene groups and 1.5 for methyl groups. Methyl group H atoms were allowed to rotate in order to find the best rotameric conformation.Crystal data, data collection and structure refinement details are summarized in Table\u00a071); seven for (2); five for (3)] are missing from these high-quality data sets due to the arrangement of the instrument with a conservatively sized beam stop. The large number of reflections in the data sets (and the Fourier-transform relationship of intensities to atoms) ensures that no particular bias has been introduced.A small number of intense low-angle reflections .The structure of  global, 1, 2, 3. DOI: 10.1107/S2056989021008008/jq20081sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20081sup5.cdxSupporting information file. DOI: 10.1107/S2056989021008008/jq20082sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20082sup6.cdxSupporting information file. DOI: 10.1107/S2056989021008008/jq20083sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20083sup7.cdxSupporting information file. DOI: 2101246, 2101245, 2101244CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The \u03b2-tubulin blot in Figure\u00a05B (middle panel) was inadvertently taken from Figure\u00a05F (MEK1 blot in the third panel) while preparing the figures. The amended Figure\u00a05B (middle panel) here shows the correct \u03b2-tubulin blot."}
{"text": "In the title compound,the two pyridine side arms are not coplanar, with the terminal pyridine rings subtending a dihedral angle of 26.45\u2005(6)\u00b0. In the crystal, hydrogen bonds, inter\u00admolecular C\u2014H\u22efCl contacts and a weak C\u2014H\u22efO inter\u00adaction connect the mol\u00adecule with neighbouring chloride counter-anions and lattice water mol\u00adecules. The crystal packing also features by \u03c0\u2013\u03c0 inter\u00adactions. 19H23N52+\u00b72Cl\u2212\u00b72H2O, the two pyridine side arms are not coplanar, with the terminal pyridine rings subtending a dihedral angle of 26.45\u2005(6)\u00b0. In the crystal, hydrogen bonds, inter\u00admolecular C\u2014H\u22efCl contacts and a weak C\u2014H\u22efO inter\u00adaction connect the mol\u00adecule with neighbouring chloride counter-anions and lattice water mol\u00adecules. The crystal packing also features by \u03c0\u2013\u03c0 inter\u00adactions with centroid-centroid distances of 3.4864\u2005(12) and 3.5129\u2005(13)\u2005\u00c5.In the title compound, C Bond leIn the crystal, there are inter\u00admolecular hydrogen bonds Table\u00a01 and C\u2014H\u22efa-axis direction with a Cg1\u22efCg2  centroid\u2013centroid distance of 3.4864\u2005(12)\u2005\u00c5, a perpendicular distance from the centroid Cg1 to the plane of the other ring of 3.2472\u2005(8)\u2005\u00c5 and a slippage between the centroids of 1.100\u2005\u00c5. Similarly, the second \u03c0\u2013\u03c0 stacking inter\u00adaction has a Cg3\u22efCg3 centroid-centroid distance of 3.5129\u2005(13)\u2005\u00c5, a perpendicular distance from the centroid Cg3 to the plane of the other ring of 3.2177\u2005(8)\u2005\u00c5 and a slippage between the centroids of 1.410\u2005\u00c5. Cg1, Cg2 and Cg3 are the centroids of N1/C8\u2013C12, N3/C1\u2013C5 and N5/C15\u2013C19 pyridine rings, respectively pyridine-2,6-dicarboxamide meth\u00adyl]pyridine-2,6-dicarboxamide hemihydrate methan\u00adam\u00adinium] dichloride dihydrate compound was obtained following the procedure previously reported in the literature (tos\u00adyl)amino]\u00admeth\u00adyl}pyridine, which could be isolated after chromatography bis\u00ad[Slow diffusion between toluene and a wet di\u00adchloro\u00admethane solution of the brown oil set aside at room temperature gave colourless needles of the title compound suitable for X-ray diffraction within five days.Uiso(H) = 1.2Ueq(C). For two similar N\u2014H distances, a restraint was applied to make them approximately equal with an effective standard deviation of 0.02\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698902101183X/tx2045sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902101183X/tx2045Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902101183X/tx2045Isup3.cmlSupporting information file. DOI: 2120892CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Z configuration. In the crystal, the mol\u00adecules are linked by weak C\u2014H\u22ef\u03c0 hydrogen bonds and very weak \u03c0\u2013\u03c0 stacking inter\u00adactions.The title Schiff base exists in the enol\u2013imine tautomeric form and adopts a  16H17NO, is a Schiff base that exists in the enol\u2013imine tautomeric form and adopts a Z configuration. The mol\u00adecule is non-planar, with the twisted rings making a dihedral angle of 39.92\u2005(4)\u00b0. The intra\u00admolecular O\u2014H\u22efN hydrogen bond forms an S(6) ring motif. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions and very weak \u03c0-\u03c0 stacking inter\u00adactions also help to consolidate the crystal packing. A Hirshfeld surface analysis was performed to investigate the contributions of different inter\u00admolecular contacts within the supra\u00admolecular structure. The major contributions are from H\u22efH (65%), C\u22efH (19.2%) and O\u22efH (6.6%) inter\u00adactions.The title compound, C These compounds can be easily synthesized by condensation of a primary aliphatic or aromatic amine with an aldehyde or ketone in different solvent media and they can easily be purified, since the amount of by-products is negligible  ring motif. The C1\u2014O1 [1.353\u2005(2)\u2005\u00c5] and C7\u2014N1 [1.282\u2005(2)\u2005\u00c5] bond distances indicate their single- and double-bond characters, respectively, being consistent with the phenol\u2013imine tautomeric form.The title compound crystallizes in the phenol\u2013imine tautomeric form with an le Fig.\u00a01, which iA\u22ef\u03c0 (C9\u2013C14) inter\u00adactions  = 4.0220\u2005(9)\u2005\u00c5] lead to additional stabilization of the crystal packing. A view of the crystal packing parallel to the bc plane is shown in Fig.\u00a02In the crystal, mol\u00adecules are linked by C16\u2014H16s Table\u00a01, and veret al., 2016Z)-2-{[imino]\u00admeth\u00adyl}-4-methyl\u00adphenol unit, revealed ten hits where this fragment adopts the enol\u2013imine tautomeric form. The imine bond length (N1\u2014C7) in the title compound is the same within standard uncertainties as the corresponding bond lengths in the structures of 2-(di\u00adphenyl\u00admeth\u00adyl)-6-[(mesityl\u00adimino)\u00admeth\u00adyl]-4-methyl\u00adphenol -N,N\u2032-bis\u00ad-5,5\u2032,6,6\u2032,7,7\u2032,8,8\u2032-octa\u00adhydro-1,1\u2032-binaphthyl-2,2\u2032-di\u00adamine \u00admeth\u00adyl]phen\u00ado\u00adlato}tetra\u00adhydro\u00adfuran\u00admagnesium imino]\u00admeth\u00adyl}phenol  to 1.1632\u2005\u00c5 (blue) . In Figs. 2normd and ed surfaces represent the C\u2014H\u22efCg inter\u00adactions. The most important inter\u00adaction is H\u22efH, contributing 65% to the overall crystal packing, which is illustrated in the 2D fingerprint -2-{[imino]\u00admeth\u00adyl}-4-methyl\u00adphenol was synthesized by condensation of 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde and 2,4-di\u00admethyl\u00adaniline  = 1.5Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model with C\u2014H = 0.93 and Uiso(H) = 1.2Ueq(C) for sp2-hybridized C atoms and with C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021010215/yk2157sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010215/yk2157Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021010215/yk2157Isup3.cmlSupporting information file. DOI: 2113562CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Their structures with absolute configurations were elucidated by extensive spectroscopic methods. Compounds 1\u20133 showed antibacterial activity against four strains with MIC values in a range of 16\u2013128\u00a0\u03bcg/mL.Five previously undescribed guanacastane diterpenoids, namely psathyrellins A\u2013E (The online version contains supplementary material available at 10.1007/s13659-021-00316-x. Psathyrella candolleana (Psathyrellaceae) is a small agaric usually found in the vicinity of recently dead hardwood trees. It has a wide distribution on lawns or pastures in Europe and North America. Previous pharmacological studies indicated that the extracts of P. candolleana showed a marked anticlastogenic effect against DNA damage + . The UV data at 282\u00a0nm suggested a conjugated system in 2. The 1D and 2D NMR spectra revealed similar patterns to those of 1 except that one more double bond in 2. In the HMBC spectrum, correlations from \u03b4H 1.11  to \u03b4C 142.8  and 158.6 , from \u03b4H 6.99  to C-1 and \u03b4C 158.6 , and from \u03b4H 1.74  to C-3 and \u03b4C 131.5  suggested that three double bonds were distributed at C-12/C-13, C-1/C-2, and C-3/C-4, respectively. Detailed analysis of 2D NMR data suggested that the other parts of 2 were the same to those of 1. A single crystal X-ray diffraction not only proved the planar structure, but also determined the absolute configuration of 1 as shown in Fig.\u00a0Psathyrellin B (3) was isolated as a yellow oil. The molecular formula was determined as C20H28O5 on the basis of HRESIMS data at m/z 349.20093 [M\u2009+\u2009H]+ . All NMR data suggested that 3 was structurally similar to that of 2  was isolated as a yellow oil. The molecular formula was determined as C22H28O6 on the basis of HRESIMS data at m/z 411.17749 [M\u2009+\u2009Na]+ . All spectroscopic data of 4 were similar to those of 2 excepted two additional carbons at \u03b4C 20.8 (q) and 172.8 (s) in 4 that were easily assigned as an O-acetyl moiety. The HMBC correlations from \u03b4H 4.40 and 4.30 to \u03b4C 172.8 (s) and from \u03b4H 1.27  to \u03b4C 32.3 , 67.1  suggested that the O-acetyl moiety should be placed at C-19. Detailed analysis of 2D NMR data suggested that the other parts of 4 were the same to those of 2. The CD spectrum almost showed the same curve to that of 2, indicating the absolute configuration of the main backbone in 4 to be the same to that of 2  was isolated as a yellow oil. The molecular formula was determined as C22H28O5 on the basis of HRESIMS data at m/z 373.20084 [M\u2009+\u2009H]+ . According to analysis of 1D and 2D NMR data, compound 5 was easily identified as a 19-O-acetyl derivative of 2, which was also similar to 4. The only difference was that the hydroxymethine of C-6 in 4 was reduced into a methylene at \u03b4C 34.5  in 5, as supported by the HMBC correlation from H-6 to C-5 and the 1H\u20131H COSY data between H-6 and H-7. The CD spectrum almost indicated the same curve to that of 2, indicating the absolute configuration of the backbone in 5 to be the same to that of 2  and a Dionex UltiMate 3000 RSLC UPLC system. Silica gel (200\u2013300 mesh and 500\u2013800 mesh), RP-18 gel (40\u201375\u00a0\u00b5m) and Sephadex LH-20 were used for column chromatography (CC). Preparative HPLC was performed on an Agilent 1260 liquid chromatography system with a Zorbax SB-C18  column, a Daicel chiral column  and a DAD detector.Optical rotations were measured on a Rudolph Autopol IV polarimeter. UV spectra were obtained on a UH5300 UV\u2013VIS Double Beam Spectrophotometer. IR spectra were obtained by using a Shimadzu Fourier Transform Infrared spectrometer with KBr pellets. NMR spectra were acquired with a Bruker Avance III 600 instrument. CD spectra were recorded with an Applied Photophysics Chirascan-Plus spectrometer. High resolution electrospray ionization mass spectra (HRESIMS) were recorded on a LC\u2013MS system consisting of a Q Exactive\u2122 Orbitrap mass spectrometer with an ESI ion source used in ultra-high resolution mode  was deposited at School of Pharmaceutical Sciences, South-Central University for Nationalities. The strains were cultured in PDA and stored at \u2212\u00a04\u00a0\u00b0C. Culture medium was composed of glucose (5%), pork pepton (0.15%), yeast (0.5%), KH2PO4 (0.05%) and MgSO4 (0.05%). Initial pH was adjusted to 6.0, the fermentation was first carried out on an erlenmeyer flask for 6\u00a0days till the mycelium biomass reached to the maximum. Then it was transferred to rice medium at 24\u00a0\u00b0C in dark culture for 40\u00a0days. The rice medium in each 250\u00a0mL-Erlenmeyer flask was composed of rice (50\u00a0g) and water (50\u00a0mL). A total of 180 bottles were used in this study.Fruiting bodies of 2CO (from 20:1 to 1:1) to afford eight fractions A\u2013H. Fraction C (3.8\u00a0g) was isolated by CC over silica gel using PE/Me2CO (6/1) to give subfractions C1\u2013C6. Compound 1 was deposited from fraction C4 as colorless crystals . Fraction E (4\u00a0g) was first isolated by silica gel CC (200\u2013300 mesh) eluted with PE/Me2CO (5/1) to give five subfractions E1-E5. Fraction E2 (800\u00a0mg) was further isolated by CC using RP-C18 silica gel (MeOH/H2O from 6/4 to 9/1) to give subfractions E2a-E2e. HPLC preparation (MeCN/H2O from 7/3 to 8/2 in 20\u00a0min) on fraction E2d (82\u00a0mg) afforded compounds 3 \u2009=\u200912.1\u00a0min; purity 90%), 4 , and 2 . Fraction E2e (70\u00a0mg) was separated by CC over Sephadex LH-20 (MeOH) to give a mixture. The mixture was subjected to HPLC (MeCN/H2O from 7/3 to 8/2 in 20\u00a0min) to give compound 5 .The rice fermentation (9\u00a0kg) was extracted four times with EtOAc. The organic layer was evaporated to give a crude extract (90\u00a0g). The extract was subjected to silica gel CC (200\u2013300 mesh) eluted with a gradient solvent system of petroleum ether (PE)/Me\u03b1]D15 \u2013 208.1 ; UV (MeOH) \u03bbmax (log \u03b5) 192 (3.36), 244 (3.18) nm; IR (KBr) \u03bdmax 3421, 3349, 2829, 1710, 1702, 1640, 1462, 1038\u00a0cm\u22121; 1H (600\u00a0MHz) and 13C NMR (150\u00a0MHz) data (methanol-d4), see Table m/z 333.20584 [M\u2009+\u2009H]+ .Colorless crystals (MeOH); [\u03b1]D15 \u2013 239.2 ; UV (H2O) \u03bbmax (log \u03b5) 190 (3.34), 252 (3.20), 282 (2.86) nm; ECD (MeOH) \u03bbmax\u00a0(\u0394\u03b5) 223 (+49), 251 (+45), 287 (\u201339), 339 (\u201327) nm;\u00a0IR (KBr) \u03bdmax 3432, 3346, 2910, 1711, 1706, 1642, 1446, 1036\u00a0cm\u22121; 1H (600\u00a0MHz) and 13C NMR (150\u00a0MHz) data (methanol-d4), see Table m/z 331.19031 [M\u2009+\u2009H]+ .Colorless crystals (MeOH); [\u03b1]D15 \u2013 182.9 ;\u00a0ECD (MeOH) \u03bbmax\u00a0(\u0394\u03b5) 209\u00a0(\u201333), 224\u00a0(+26), 287 (\u201329), 341\u00a0(\u20138) nm; 1H (600\u00a0MHz) and 13C NMR (150\u00a0MHz) data (methanol-d4), see Table m/z 349.20093 [M\u2009+\u2009H]+ .Yellow oil; [\u03b1]D15 \u2013 221.9 ; ECD (MeOH) \u03bbmax\u00a0(\u0394\u03b5) 222\u00a0(+20), 243 (+22), 287 (\u201315), 338\u00a0(\u201312) nm;\u00a01H (600\u00a0MHz) and 13C NMR (150\u00a0MHz) data (methanol-d4), see Table m/z 411.17749 [M\u2009+\u2009Na]+ .Yellow oil; [\u03b1]D15 \u2013 292.4 ;\u00a0ECD (MeOH) \u03bbmax\u00a0(\u0394\u03b5) 221\u00a0(+27), 242\u00a0(+31), 290\u00a0(\u201324), 338\u00a0(\u201318) nm; 1H (600\u00a0MHz) and 13C NMR (150\u00a0MHz) data (methanol-d4), see Table m/z 373.20084 [M\u2009+\u2009H]+ .Yellow oil; . The final wR(F2) values were 0.0799 [I\u2009>\u20092\u03c3(I)]. The final R1 values were 0.0307 . The final wR(F2) values were 0.0800 . The goodness of fit on F2 was 1.056. Flack parameter\u2009=\u20090.05(3). CCDC: 2068966 (www.ccdc.cam.ac.uk).C20H26O4, M\u2009=\u2009330.41, a\u2009=\u20098.0026(8) \u00c5, b\u2009=\u20098.3729(9) \u00c5, c\u2009=\u200914.4078(15) \u00c5, \u03b1\u2009=\u200990.00\u00b0, \u03b2\u2009=\u2009105.783(3)\u00b0, \u03b3\u2009=\u200990.00\u00b0, V\u2009=\u2009929.00(17) \u00c53, T\u2009=\u2009150.(2) K, space group P1211, Z\u2009=\u20092, \u03bc(CuK\u03b1)\u2009=\u20091.54178\u00a0mm\u22121, 12059 reflections measured, 3552 independent reflections (Rint\u2009=\u20090.0456). The final R1 values were 0.0559 [I\u2009>\u20092\u03c3(I)]. The final R1 values were 0.0415 . The final wR(F2) values were 0.1156 . The goodness of fit on F2 was 1.092. Flack parameter\u2009=\u2009\u2212\u00a00.12(14). CCDC: 2068967 (www.ccdc.cam.ac.uk).CEscherichia coli ATCC25922, Staphylococcus aureus subsp. aureus ATCC29213, Salmonella enterica subsp. enterica ATCC14028, Pseudomonas aeruginosa ATCC27853 were purchased from China General Microbiological Culture Collection Center, (CGMCC). All these strains were cultured in Mueller Hinton broth (MHB)  at 37\u00a0\u00b0C overnight with shaking (200\u00a0rpm). A sample of each culture was then diluted 40-fold in fresh MHB broth and incubated with shaking (200\u00a0rpm) at 37\u00a0\u00b0C for 2.5\u00a0h. The resultant mid-log phase cultures were diluted to a concentration of 5\u2009\u00d7\u2009105\u00a0CFU/mL, then 50\u00a0mL was added to each well of the compound-containing plates. The minimum inhibition concentration (MIC) was determined by measuring bacterial growth after 24\u00a0h on performing 1:2 serial dilutions of each compound ranging from 1 to 128\u00a0\u03bcg/mL. Chloramphenicol was used as a positive control.The tested bacteria strains Supplementary file1 (PDF 2820 KB)Supplementary file2 (CIF 1031 KB)Supplementary file3 (CIF 379 KB)Below is the link to the electronic supplementary material."}
{"text": "In the crystal, the mol\u00adecules are assembled into two-dimensional layers  33H28N2O4, comprises an indole unit (A), an iso\u00adquinoline moiety (B) and a benzene ring (C). The dihedral angles between these groups are A/B = 57.47\u2005(1), A/C = 18.48\u2005(1) and B/C = 57.97\u2005(1) \u00b0. The ethyl acrylate group at the 2-position is nearly co-planar with the indole unit [3.81\u2005(2)\u00b0], while that at the 7-position is distinctly non-coplanar [52.64\u2005(1)\u00b0]. Intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the indole unit and benzene ring help to establish the clip-shaped conformation of the mol\u00adecule. In the crystal, the mol\u00adecules are assembled into two-dimensional layers via C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions. Hirshfeld surface analysis illustrates that the greatest contributions are from H\u22efH (63.2%), C\u22efH/H\u22efC (15.4%) and O\u22efH/H\u22efO (14.8%) contacts. The terminal C2H5 group of one of the ethyl acrylate side chains is disordered over two positions of equal occupancy.The mol\u00adecule of title compound, C The benzene ring is almost parallel to the indole unit and hence intra\u00admol\u00adecular \u03c0\u2013\u03c0 inter\u00adactions  are observed within the layers  to 1.7889 (blue) a.u. -diacrylate -8-phen\u00adyliso\u00adquinoline (0.20\u2005mmol), Pd(OPiv)2 , L quinoline; 11.3\u2005mg, 20\u2005mol%], CuO  and Cu(OTf)2  and the tube was purged with O2 three times, followed by addition of ethyl acrylate (1.0\u2005mmol) and anhydrous DCE . The formed mixture was stirred at 353\u2005K under Ar for 24\u2005h as monitored by TLC. The solution was then cooled to room temperature, and the solvent was removed under vacuum. The crude product was purified by column chromatography on silica gel to afford the pure product (55% yield). The recrystallization of the title compound in methanol afforded yellow block-shaped crystals. The synthesis is shown in Fig.\u00a06To a 10\u2005mL Schlenk tube was added indole substrate 1-(1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). Atoms C32 and C33 were refined as disordered over two partially occupied positions of equal occupancy.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021007829/zn2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021007829/zn2008Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007829/zn2008Isup3.cmlSupporting information file. DOI: 2100362CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-020-76496-2, published online 11 November 2020Correction to: Ca,L, SR Ca2+\u00a0content and Ca2+\u00a0transient measurements\u2019.This Article contains errors in the Results section under subheading \u2018The I2+\u00a0content and found that SR Ca2+\u00a0content was significantly increased in the trained group compared to controls (\u2212\u20091.84\u2009\u00b1\u20090.4 (pA*s)/pF vs \u2212\u20091.25\u2009\u00b1\u20090.5 (pA*s)/pF n\u2009=\u20098/5 and 8/4, respectively,\u00a0p\u2009<\u20090.05; Fig. 6b).\u201d\u201cWe analyzed the integral of caffeine-induced NCX currents as an indicator of the SR Cashould read:2+\u00a0content and found that SR Ca2+\u00a0content was significantly increased in the trained group compared to controls (\u2212\u20091.84\u2009\u00b1\u20090.4 (pA*s)/pF vs \u2212\u20091.25\u2009\u00b1\u20090.5 (pA*s)/pF n\u2009=\u20098/5 and 8/5, respectively,\u00a0p\u2009<\u20090.05; Fig. 6b).\u201d\u201cWe analyzed the integral of caffeine-induced NCX currents as an indicator of the SR CaSecondly, this Article contains an error in Figure\u00a06 where the experimental numbers of the control columns are incorrect (8/4) in panel (b). The correct Figure 6 appears below as Figure"}
{"text": "The asymmetric unit contains one-half of the formula unit of the title compound. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions, and short inter\u00admolecular Cl\u22efO and Cl\u22efCl contacts, forming a three-dimensional network. 24H16Cl12N2O4, is generated by a crystallographic inversion centre at the midpoint of the central C\u2014C bond. A kink in the mol\u00adecule is defined by a torsion angle of \u2212169.86\u2005(15)\u00b0 about this central bond of the alkyl bridge. The pyrrolidine ring is essentially planar [max. deviation = 0.014\u2005(1)\u2005\u00c5]. The cyclo\u00adhexane ring has a boat conformation, while both cyclo\u00adpentane rings adopt an envelope conformation. In the crystal structure, mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions, and short inter\u00admolecular Cl\u22efO and Cl\u22efCl contacts, forming a three-dimensional network.The mol\u00adecule of the title compound, C N-heterocyclic compounds are of inter\u00adest in the fields of synthetic organic chemistry, coordination chemistry and medicinal chemistry because of their important biological properties -4,5,6,7,8,8-hexa\u00adchloro-2-{6-hex\u00adyl}-3a,4,7,7a-tetra\u00adhydro-1H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione, which provides multiple iner\u00admolecular non-covalent inter\u00adactions.QT = 0.9300\u2005(14)\u2005\u00c5, \u03b8 = 89.99\u2005(9)\u00b0, \u03c6 = 59.37\u2005(9)\u00b0], while both the cyclo\u00adpentane rings (C2\u2013C6 and C3\u2013C5/C8/C9) adopt an envelope conformation  with the C4 atom bearing the di\u00adchloro\u00admethane group as the flap.The mol\u00adecule of the title compound is generated by a crystallographic inversion centre at the midpoint of the central C\u2014C bond. A kink in the mol\u00adecule is defined by the C10\u2014C11\u2013C12\u2014C12_a torsion angle of \u2212169.86\u2005(15)\u00b0 about this central bond of the alkyl bridge Fig.\u00a01. The pyrIn the crystal structure, mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions Table\u00a01, and shoCrystal Explorer 17.5 , Cl\u22efCl , O\u22efH/H\u22efO , Cl\u22efO/O\u22efCl  and H\u22efH  inter\u00adactions. The remaining other weak inter\u00adactions (contribution percentages) are Cl\u22efC/C\u22efCl (3.2%), Cl\u22efN/N\u22efCl (1.4%) and C\u22efH/H\u22efC (0.2%).In order to visualize the inter\u00admolecular inter\u00adactions Table\u00a02 in the cet al., 2016H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione -2-(perfluoro\u00adpyridin-4-yl)-3a,4,7,7a-tetra\u00adhydro-1H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione -2-[(perfluoro\u00adpyridin-4-yl)\u00adoxy]-3a,4,7,7a-tetra\u00adhydro-1H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione \u00b0 with the 3,4-di\u00admeth\u00adoxy\u00adphenyl ring, which are attached to each other by an extended N\u2014CHIn the crystal of QOVCAH, the cyclo\u00adhexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51\u2005(7)\u00b0. The mol\u00adecular structure is stabilized by a short intra\u00admolecular C\u2014H\u22efO contact. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming chains propagating along [100]. The chains are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming slabs parallel to (001).PA and B, in the asymmetric unit, and MOJGAW in the monoclinic space group P21/n with one mol\u00adecule per asymmetric unit. The synthesis of both compounds is conducted using endo starting materials, and the same configuration is observed in the resulting crystal structures. In MOJFUP, steric inter\u00adactions between the ortho-fluorine atoms and the carbonyl oxygen atoms prevents free rotation about the nitro\u00adgen\u2013ipso-carbon bond, which is evidenced by separate 19F NMR peaks in solution for the ortho-F atoms. In mol\u00adecule A, the 2,3,5,6-tetra\u00adfluoro\u00adpyridine plane is rotated by 58.05\u2005(5)\u00b0 relative to the pyrrolidine plane and the corresponding dihedral angle for mol\u00adecule B is 61.65\u2005(7)\u00b0. The addition of an oxygen atom between N and C in the bridge between the ring systems in MOJGAW alleviates this steric restriction and only one 19F NMR peak in solution is observed for the ortho-F atoms; even so, the dihedral angle between the 2,3,5,6-tetra\u00adfluoro\u00adpyridine and pyrrolidine planes in the crystal of MOJGAW of 84.01\u2005(5)\u00b0 is larger than that found in MOJFUP.The compound MOJFUP crystallizes in the triclinic space group The main directional inter\u00adactions in the crystal structures of MOJFUP and MOJGAW are of the type C\u2014H\u22efO, C\u2014H\u22efF, C\u2014O\u22ef\u03c0, and C\u2014F\u22ef\u03c0. In both compounds, weak hydrogen-bonding inter\u00adactions are observed for the hydrogen atom(s) \u03b1 to the carbonyl groups  and the olefinic hydrogen atoms . A weak inter\u00adaction is also observed for a bridge hydrogen atom in MOJGAW, C\u2014H\u22efF. The packing is further aided by \u03c0-inter\u00adactions with the pyridine ring in MOJGAW.R,4R,7R,7aS)-4,5,6,7,8,8-hexa\u00adchloro-3a,4,7,7a-tetra\u00adhydro-4,7-methano\u00adisobenzo\u00adfuran-1,3-dione were added 0.12\u2005mL (1\u2005mmol) of hexane-1,6-di\u00adamine and 25\u2005mL of di\u00admethyl\u00adformamide, and the mixture was stirred for 6\u2005h at 373\u2005K. Then, the reaction mixture was cooled to room temperature and poured into cold water. The obtained precipitate was filtered off, washed with water, recrystallized from chloro\u00adform and dried under vacuum. Yellow powder, yield 92%, m.p 404\u2013405\u2005K (decomp.). Analysis calculated for C24H16Cl12N2O4 (Mr = 821.80): C 35.08, H 1.96, N 3.41%; found: C 35.03, H 2.00, N 3.35%. ESI\u2013MS: m/z: 822.9 [Mr\u00a0+\u00a0H]+. 1H NMR (300.130\u2005MHz) in acetone-d6, inter\u00adnal TMS, \u03b4 (ppm): 1.29\u20133.43 , 3.86 . 13C{1H} NMR . \u03b4: 25.8 (2CH2), 27.2 (2CH2), 39.3 (4C\u2013H), 52.0 (2CH2), 79.3 (4CCl), 104.4 (2CCl2), 130.9 (2ClC=CCl) and 170.2 (4C=O). Off-white prismatic crystals suitable for X-ray analysis were obtained by slow evaporation of a chloro\u00adform\u2013hexane  mixture.To 741\u2005mg (2\u2005mmol) of (3aUiso(H) = 1.2Ueq(C). Two reflections (100 and 002), affected by the incident beam-stop, and owing to poor agreement between observed and calculated intensities, two outliers (136 and 118) were omitted in the final cycles of refinement. Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021006952/vm2251sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021006952/vm2251Isup2.hklStructure factors: contains datablock(s) I. DOI: 2094787CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the free base of the ubiquitous neurotransmitter serotonin is reported for the first time. H-indol-5-ol], C10H12N2O, has one mol\u00adecule in the asymmetric unit. The conformation of the ethyl\u00adamino side chain is gauche\u2013gauche . In the crystal, the mol\u00adecules are linked into a three-dimensional network by N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.The title compound, serotonin or 5-hy\u00addroxy\u00adtryptamine (5-HT) [systematic name: 3-(2-amino\u00adeth\u00adyl)-1 The ethyl\u00adamino arm itself turns back toward the indole ring with a C8\u2014C9\u2014C10\u2014N2 torsion angle of \u221261.9\u2005(2)\u00b0.Serotonin or 5-hy\u00addroxy\u00adtryptamine (5-HT) is an indolamine with a 5-hy\u00addroxy substitution. In the solid state, serotonin crystallizes with one mol\u00adecule in the asymmetric unit Fig.\u00a01 in the cA\u22efO1 hydrogen bonds. Half of the amine H atoms link to the hy\u00addroxy groups of nearby mol\u00adecules through N2\u2014H2B\u22efO1 hydrogen bonds. There are no observed \u03c0\u2013\u03c0 stacking inter\u00adactions. Fig.\u00a02In the crystal, the serotonin mol\u00adecules are linked by a series of hydrogen bonds that produce a three-dimensional network in the solid state. The hy\u00addroxy groups form hydrogen bonds to the amine N atoms on an adjacent serotonin mol\u00adecules forming O1\u2014H1\u22efN2 hydrogen bonds. The indole N atoms form hydrogen bonds to the hy\u00addroxy groups of adjacent serotonin mol\u00adecules through N1\u2014H110H13N2O+ cationic form. These include the creatine sulfate monohydrate .A, H2A and H2B were found from a difference-Fourier map and were refined isotropically, using DFIX restraints with an N\u2014H(indole) distance of 0.87\u2005(1)\u2005\u00c5, N\u2014H(amine) distances of 0.90\u2005(1)\u2005\u00c5, and an O\u2014H distance of 0.86\u2005(1)\u2005\u00c5. Isotropic displacement parameters were set to 1.2 Ueq of the parent nitro\u00adgen atoms and 1.5 Ueq of the parent oxygen atom. All other hydrogen atoms were placed in calculated positions with C\u2014H = 0.93\u2005\u00c5 (sp2) or 0.97\u2005\u00c5 (sp3). Isotropic displacement parameters were set to 1.2 Ueq of the parent carbon atoms. The absolute structure of the crystal chosen for data collection was indeterminate in the present refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022002559/hb8014sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022002559/hb8014Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022002559/hb8014Isup3.cmlSupporting information file. DOI: 2156646CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-[2-(4-fluoro-3-phen\u00adoxy\u00adbenzo\u00adyl)hydrazinecarbo\u00adthio\u00adyl]benzamide and its 4-meth\u00adoxy derivative highlights the significance of strong and weak hydrogen bonds. The difference in the contributions of atom\u2013atom contacts obtained from Hirshfeld surface analysis and fingerprint plots helps in distinguishing the variations in the crystal packing of the two compounds.Crystal structure analysis of  N-[2-(4-fluoro-3-phen\u00adoxy\u00adbenzo\u00adyl)hydrazinecarbo\u00adthio\u00adyl]benzamide, C21H16FN3O3S, crystallizes in the monoclinic centrosymmetric space group P21/c and its mol\u00adecular conformation is stabilized via an intra\u00admolecular N\u2014H\u22efO hydrogen bond. The corresponding para-meth\u00adoxy derivative, namely, N-[2-(4-fluoro-3-phen\u00adoxy\u00adbenzo\u00adyl)hydrazinecarbo\u00adthio\u00adyl]-4-meth\u00adoxy\u00adbenzamide, C22H18FN3O4S, crystallizes in the monoclinic centrosymmetric space group C2/c. The supra\u00admolecular network mainly comprises N\u2014H\u22efO, N\u2014H\u22efS and C\u2014H\u22efO hydrogen bonds, which contribute towards the formation of the crystal structures for the two mol\u00adecules. The different inter\u00admolecular inter\u00adactions have been further analysed using Hirshfeld surface analysis and fingerprint plots.The compound  R\u2013(C=O)\u2013NH\u2013NH\u2013(C=S)\u2013R\u2032 and find application in the synthesis of five- and six-membered heterocyclic compounds hydrazinecarbo\u00adthio\u00adyl]benzamide (A1) and N-[2-(4-fluoro-3-phen\u00adoxy\u00adbenzo\u00adyl)hydrazinecarbo\u00adthio\u00adyl]-4-meth\u00adoxy\u00adbenzamide (A2) in the current study. The mol\u00adecular conformations have been studied with respect to the various flexible bonds and the occurrence of various inter\u00admolecular inter\u00adactions that contribute towards the stability of the mol\u00adecules in the crystalline lattice has been investigated in detail via an investigation of the crystal packing and qu\u00adanti\u00adtative insights from Hirshfeld surface analysis.Substituted thio\u00adsemicarbazides (TSCs) constitute an important class of organic compounds with the general formula P21/c space group and A2 crystallizes in the centrosymmetric monoclinic C2/c space group. The mol\u00adecular structure comprises one fluoro-substituted phen\u00adoxy\u00adbenzoyl ring, a rigid and planar (C=O)\u2014NH\u2014NH\u2014(C=S) moiety and a benzamide ring. The bond lengths and bond angles are in accordance with the magnitudes in the literature. The mol\u00adecular conformations of A1 , the N2\u22efO3 distance being 2.555\u2005(2) and 2.589\u2005(4)\u2005\u00c5 in A1 and A2, respectively. The mol\u00adecular structure possesses four conformational degrees of freedom due to the free rotation with respect to the N1\u2014N2, C7\u2014O1, O1\u2014C1 and C15\u2014C16 single bonds. The torsion angles C13\u2014N1\u2014N2\u2014C14, C8\u2014C7\u2014O1\u2014C1, C7\u2014O1\u2014C1\u2014C2 and N3\u2014C15\u2014C16\u2014C21 are 163.27\u2005(16)/-143.5\u2005(4)\u00b0, 97.3\u2005(2)/149.6\u2005(5)\u00b0, 167.18\u2005(18)/148.1\u2005(4)\u00b0 and \u2212160.26\u2005(15)/-174.7\u2005(3)\u00b0 in A1/A2, respectively.Compound A1 crystallizes in the centrosymmetric monoclinic A1 Fig.\u00a01 and A2 , [3.384\u2005(4)\u2005\u00c5, 174.9\u2005(1)\u00b0, \u2212x\u00a0+\u00a01, y\u00a0+\u00a01, \u2212z\u00a0+\u00a0In the crystal structure of A1, the mol\u00adecules are primarily assembled through the presence of N3\u2014H3s Table\u00a01, formingnt Fig.\u00a03. AdjacenA2 Fig.\u00a04 primarilA2 Fig.\u00a04, formingng Fig.\u00a04. Inter\u00admet al., 2016A search for the di\u00adbenzoyl\u00adthio\u00adsemicarbazide skeleton, Ph\u2013(C=O)\u2013NH\u2013NH\u2013(C=S)\u2013NH\u2013(C=O)\u2013Ph was carried out in the Cambridge Structural Database , and A2, Fig.\u00a05b) and 5(c), show the important hydrogen bonds. The red and blue spots correspond to inter\u00admolecular inter\u00adactions that are less or greater than the sum of the van der Waals radii. The fingerprint plots depict the individual contributions of the different inter\u00adactions. The fingerprint plots for A1/A2  = 1.2Ueq or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021001900/dj2021sup1.cifCrystal structure: contains datablock(s) A1, A2. DOI: 10.1107/S2056989021001900/dj2021A1sup2.hklStructure factors: contains datablock(s) A1. DOI: 10.1107/S2056989021001900/dj2021A2sup3.hklStructure factors: contains datablock(s) A2. DOI: Click here for additional data file.10.1107/S2056989021001900/dj2021A1sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021001900/dj2021A2sup5.cmlSupporting information file. DOI: 2063226, 2063225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Their physicochemical properties can be modulated by an appropriate choice of N\u2010substituents and counteranion. Tested against a panel of human cancer cell lines, the complexes were shown to possess promising antiproliferative activity and to circumvent multidrug resistance. Interestingly, most derivatives also retained a significant cytotoxic activity against human cancer 3D cell cultures. Among them, the complex with R=4\u2010C6H4OMe and R\u2019=Me emerged as the best performer of the series, being on average about six times more active against cancer cells than a noncancerous cell line, and displayed IC50 values comparable to those of cisplatin in 3D cell cultures. Mechanistic studies revealed the ability of the complexes to release carbon monoxide and to act as oxidative stress inducers in cancer cells.A straightforward two\u2010step procedure via single CO removal allows the conversion of commercial [Fe A class of cationic diiron complexes containing a variable bridging iminium ligand displays promising antiproliferative activity towards a panel of 2D and 3D cancer cell lines, and a selectivity not correlated to a different degree of uptake in cancerous and noncancerous cells. The mode of action appears to be mainly related to the interference with cell redox processes , initiated by intracellular CO release. Remarkably, 3D cell culture studies constitute an excellent base for more advanced in\u2005vivo cancer research, surpassing the traditional assays on monolayer cultures;To the best of our knowledge, the present 3D investigation is one of the first ones ever reported on iron compounds. The proposed diiron complexes combine within a cationic structure two Cp rings, three carbonyls and a variable bridging aminocarbyne ligand, the latter tuning the water solubility, the lipophilicity and the activity. Several experiments aimed to clarify the mechanism of action of the complexes will be discussed.1A\u2013H were prepared by the thermal substitution reaction of the corresponding isocyanides with a slight molar excess of [Fe2Cp2(CO)4] in acetonitrile.2\u20135]+ 2} core, connected to a further CO and an aminocarbyne group occupying the two bridging sites. Along this series of complexes, the C(4)\u2010N(1) distance does not significantly vary, indicating a substantial double\u2010bond character which accounts for the complementary description of the bridging ligand as iminium (see below).New compounds were fully characterized by elemental analysis, IR and multinuclear NMR spectroscopy. In addition, the structures of ACF3SO3, 2C]+ was calculated and compared to that of the parent compound cis\u20101C with a bridging cyclohexyl\u2010isocyanide ligand (CNCy). DFT\u2010optimized structures and relevant bonding parameters are reported in Table\u2005S1 and Figure\u2005S1. In 1C, the (\u03bc\u2010C)\u2212N Mayer bond order (b.o.)iPr instead of CNCy].2\u2009C]+. The nature of the nitrogen substituents has a negligible influence, and for instance the corresponding b.o. is 1.54 in the case of [2A]+, the related bond length being consistent with the crystallographic characterization of [2A]CF3SO3 + as an almost perfect aminocarbyne\u2010iminium hybrid structure } ligands in dimetal complexes is not clearly defined in the literature, therefore we performed a DFT study to shed light on this point. The representative structure of C+ was ca2Cp2Cl(CO)(\u03bc\u2010CO){\u03bc\u2010CNMe(Cy)}], 6 . Based on a comparison of the 1H NMR and IR spectra with data available in the literature for similar compounds,6 exists in CDCl3 solution as a nearly equimolar mixture of two isomers, maintaining the cis\u2010geometry of the Cp ligands  and differing in the orientation of the N\u2010substituents with respect to the chloride (E/Z isomers). This feature suggests that the (\u03bc\u2010C)\u2212N bond in the neutral 6 still holds a substantial double bond character. The X\u2010ray structure of the E isomer was determined and is shown in Figure\u2005S2, although the low quality of the crystals prevents a detailed discussion of bonding parameters.Then, in order to clarify the possible effect of the net ionic charge of the complex, we also synthesized and characterized the novel neutral derivative +, with only a slight decrease of the (\u03bc\u2010C)\u2212N bond order (from 1.58 to 1.52). It is interesting to note that the bond length of the bridging carbonyl in 6 is very close to that in 1C (1.187 vs. 1.188\u2005\u00c5), highlighting that the isocyanide/CO and aminocarbyne/Cl combinations supply very similar electron densities for back\u2010donation to the diiron framework.In agreement with the NMR evidence, DFT outcomes indicate that 2Cl2 solution), the vibrations due to the terminal carbonyl ligands occur in the ranges 2018\u20132028 (anti\u2010symmetric stretching) and 1985\u20131996\u2005cm\u22121 (symmetric stretching), while the band related to the bridging carbonyl is found at 1833\u20131853\u2005cm\u22121. Moreover, the absorption attributed to the carbyne\u2010N bond falls in between 1530 to 1602\u2005cm\u22121, the higher values being associated to the N\u2010substituents with higher electron\u2010donor ability. The 1H and 13C NMR spectra  display one set of resonances, ascribable to a single isomeric form featuring the Cp ligands in mutual cis position, as found in the X\u2010ray structures and confirmed by 1H NOE experiments in the case of [4G]+ . Two resonances for the Cp and terminal CO ligands are distinguishable in the unsymmetrical complexes, due to hampered rotation around the partially double C\u2212N bond (see above); accordingly, such resonances coincide in the complexes [2F]+ and [5H]+, displaying two identical N groups. In the 13C NMR spectra, the bridging {CN} unit is detected at low fields , as it is typical for bridging aminocarbynes.[2B]+ features a 31P NMR resonance at 17\u2005ppm for the phosphonato group, and the 13C signal for the carbyne appears as a doublet (3JCP ca. 6\u2005Hz).Salient spectroscopic features of all complexes are summarized in Table\u2005S2, and NMR and IR spectra are supplied in Figures\u2005S3\u2013S32. In the IR spectra (CH2C]CF3SO3 and [2C]Cl in chlorinated solvents are ascribable to the presence of ion pairs (or higher aggregates);1H NMR spectra in protic polar solvents (D2O and CD3OD), where ion pairs are practically absent.Small differences between the spectroscopic data of Cl. The octanol/water partition coefficients (log\u2009Pow) were measured by a UV/Vis method and fall in between 0 and \u22121, reflecting an amphiphilic or slightly hydrophilic character. An exception is represented by [2B]BF4, wherein the marked hydrophilicity imparted by the diethylphosphonato does not appear sufficiently balanced (log\u2009Pow<\u22121.5). Conversely, those complexes with aromatic groups  are less soluble in water and display increased affinity for n\u2010octanol (log\u2009Pow\u22480). The diiron compounds are inert in aqueous solution at room temperature, and undergo a slow degradation at 37\u2009\u00b0C. Under such conditions, a variable amount  of the starting material was detected by 1H NMR in D2O or D2O/CD3OD mixtures after 72\u2005h.2C]CF3SO3 solution) was separated and identified as \u03b3\u2010Fe2O3 by Raman analysis. In addition, headspace GC analyses performed on 5\u2009% MeOH aqueous solutions of the compounds maintained at 37\u2009\u00b0C allowed the identification and quantitation of the carbon monoxide released over a 48\u2005h period (Table\u2005S4). These facts indicate that the thermal degradation process in aqueous solution leads to the progressive disassembly of the organometallic scaffold.II ions was previously associated to their cytotoxicity,A detailed study on the behaviour of a selection of the diiron complexes in aqueous media was undertaken. Experimental procedures are provided in the Experimental Section and in the Supporting Information, with data collected in Tables\u20051H NMR. Notably, a considerable fraction  of the starting material was detected at the end of the experiment, with a limited formation of an orange\u2010brown precipitate analogous to that described above.Next, the stability of the diiron compounds in a cell culture medium (DMEM) solution at 37\u2009\u00b0C, over a shorter time range (24\u2005h), was assessed by 2\u20133]+ was the methylated derivative, which was also checked by HPLC separation . The expected diiron counterparts, that is, 1A\u2013H, could not be detected possibly due to their water insolubility. The [lysozyme+Me+] to [lysozyme] ratios, calculated on extracted ion chromatograms after protein peak reconstruction, are reported in Table\u2005N\u2010methyl groups  did not react with lysozyme. Methylation is a common post\u2010translational modification of protein/enzymes (methyltransferase enzymes) but it has also been observed as a result of the interaction of proteins with various electrophiles.To gain insights into the reactivity of the diiron compounds with possible biomolecular targets, we selected lysozyme, a small model protein often used to test interactions with metal compounds. Figure\u2005S1. The ex2A]+, [2C\u2013E]+, [3F\u2013G]+, [5H]+  and [2B]+, [4G]+  were tested for their cytotoxic potential by means of the MTT assay, as reported in the Experimental Section. The most convenient counter anion in terms of preparation and handling/storage was chosen in each case; in particular, [2C]CF3SO3 was included in the study, while [2C]Cl was excluded, being highly moisture sensitive and thus affecting the accuracy of the weighting operation. The in\u2010house human cancer cell line panel contains examples of ovarian (2008), colon (HCT\u201015), pancreatic (PSN\u20101), and breast (MCF\u20107) cancers as well as of melanoma (A375). Cisplatin was used as a reference and tested under the same experimental conditions. The cytotoxicity parameters, expressed in terms of IC50 obtained after 72\u2005h of exposure, are listed in Table\u20052B]BF4 and [3F]CF3SO3 did not impact cell viability , whereas the other compounds elicited IC50 values in the micromolar range. Despite all cytotoxic complexes showed an average in\u2005vitro antitumor potential lower than that of cisplatin, [2C]CF3SO3 and [2D]CF3SO3 proved to be the most effective derivatives, with average IC50 values of 17.4 and 16.6\u2005\u03bcM , and showed a similar pattern of response over the five tested cell lines. In particular, [2D]CF3SO3 exhibits a comparable activity with respect to cisplatin against HCT\u201015, PSN\u20101 and MCF\u20107 cells.The diiron complexes [[3F\u2013G]+, H+ . Overall, it appears that slight structural variations on the iminium group may have a notable impact on the activity of the cations, although not obvious: for instance, [2D]CF3SO3 and [2E]CF3SO3 differ from each other in the nature and the position of peripheral arene substituents and display almost identical log\u2009Pow values, notwithstanding the former is significantly more cytotoxic and selective than the latter.As one of the main drawbacks of chemotherapeutics is the toxic effect toward noncancerous cells, we measured the cytotoxicity of tested complexes against a noncancerous cell line (HEK293) and calculated the selectivity index . All complexes exhibited activity levels very similar on both sensitive (MCF\u20107) and multi\u2010drug resistant (MCF\u20107ADR) cell lines; interestingly, the resistance factor (RF) values Table\u2005 range fr2D]CF3SO3 (log\u2009Pow=\u22120.25) together with the less active/selective [2E]CF3SO3 (log\u2009Pow=\u22120.27) and [3G]CF3SO3 (log\u2009Pow=+0.29), to be assessed for their accumulation in human pancreatic PSN\u20101 cancer cells and in untransformed HEK293 cells. Thus, cells were treated for 24\u2005h with equimolar concentrations (50\u2005\u03bcM) of the tested compounds. The cellular iron levels were quantified by means of GF\u2010AAS analysis, and the results, expressed as \u03bcg Fe per 106 cells, are shown in Figure\u20053G]CF3SO3 was ineffective in entering human cells, while both [2D]CF3SO3 and [2E]CF3SO3 were able to induce cellular iron accumulation, and no significant differences in the ability to enter cells were evidenced for the two complexes. Considering the log\u2009Pow values, the obtained outcomes highlight that the hydrophilic complexes [2D]CF3SO3 and [2E]CF3SO3 are significantly more effective in entering cells compared to the more lipophilic one [3G]CF3SO3. In addition, both [2D]CF3SO3 and [2E]CF3SO3 led to major iron accumulation in untransformed cells with respect to pancreatic cancer cells. Intriguingly, these findings attest that their selectivity towards cancer cells with respect to untransformed ones cannot be attributable to their different ability to cross cellular plasmalemma and to enter human cells, and the reason of their preferential activity against cancer cells might be dependent on their ability to interfere with a cancer specific target.In order to correlate the cytotoxic potential to the ability of the newly developed complexes to enter cells, we performed uptake experiments. To this purpose, we selected the most promising compound CF3SO3 and [3F]CF3SO3 were ineffective against cancer cells spheroids, whereas [2D]CF3SO3 was the most effective complex among the series, thus indicating its ability to better penetrate the spheroid and reach the hypoxic core. It is noteworthy that [2D]CF3SO3 exhibited a level of activity either comparable (PSN\u20101 cells) or even superior (2008 cells) to that of cisplatin.The remarkable cell\u2010killing effect observed in 2D cultured cells prompted us to evaluate the in\u2005vitro antitumor activity of the complexes on 3D cell cultures. Differently from 2D monolayer culture, 3D spheroid cell culture systems comprise cancer cells in various cell growth stages. Consequently, the multicellular cancer spheroid model is recognized to better reflect the tumour mass in\u2005vivo regarding drug permeation, cell interactions, gene expression, hypoxia and nutrient gradients with respect to monolayer cell cultures, making 3D models more predictive than conventional 2D monolayer cultures in screening antitumor drugs.50 ratio related to 3D and 2D experiments ranging from 2 to 5 for both cell lines; in particular, this ratio is approximately 2 for the cytotoxic diiron complexes against the 2008\u2005cell line, while the corresponding value for cisplatin is 26. Note that a substantial drop of antiproliferative activity has been often recognized for potential anticancer metal drugs in 3D cell cultures compared to the corresponding 2D ones, highlighting the need for a combination of both models for screening of compounds.An important aspect of the collected data is that only a limited decrease of activity is observed with the cytotoxic compounds, the IC2C]CF3SO3 and [2D]CF3SO3 to release carbon monoxide inside PSN\u20101 pancreatic cancer cells and HEK293 noncancer cells. A fluorometric test was conducted over a short time interval (30\u2005min) by means of a CO sensing dye (L)(\u03bc\u2010CO){\u03bc\u2010CNR(Me)}]0/+.CF3SO3 and [2D]CF3SO3 determined a substantial increase in cellular ROS production, in a time\u2010dependent manner  oxides has been recognized from water solution, see above). Otherwise, based on previous voltammetric measurements on [2E\u2013F]CF3SO3,2\u20133]+, some contribution to ROS might be provided by the partial generation of the neutral products 1A\u2013H upon CH3+ elimination (see above); in principle, the absence of a net positive charge in 1A\u2013H might favour the oxidation of these complexes or their possible derivatives in the cells.Iron is a redox active metal that can generate ROS in cells via the Fenton reaction, thus inducing cellular damage and ultimately leading to cell death.r Figure\u2005A. Remark3 Figure\u2005B. The ti2C]CF3SO3 and [2D]CF3SO3 to target TrxR both in cell\u2010free experiments and in cells. The two complexes showed a similar pattern of response, being completely ineffective in hampering TrxR in cell\u2010free experiment (data not shown) but elicited a substantial inhibition of the selenoenzyme in human pancreatic PSN\u20101 cancer cells . On the other hand, TrxR inhibition might also be consistent with the capacity of the complexes to methylate specific substrates, as we have assessed for lysozyme. Actually, it was previously described that several alkylating agents are able to selectively modify the redox active Cys or Sec of TrxR, thus causing irreversible inhibition.It has recently emerged that the redox stress induced by some iron complexes might also be attributed to their ability to inhibit the selenoenzyme thioredoxin reductase (TrxR). In particular, Rigobello and co\u2010workers reported the capacity of a ferrocenyl diphenol and of a Tamoxifen\u2010like ferrocifen to target and hamper TrxR activity.s Figure\u2005. In part2Cp2(CO)4]. They have ideal properties for a potential anticancer drug, such as the presence of a nontoxic metal element, appreciable water solubility and amphiphilicity, and stability in aqueous media.2D]CF3SO3, with a 4\u2010methoxy phenyl substituent on the bridging hydrocarbyl ligand, was revealed to be the most promising and exhibited a noteworthy selectivity toward cancer cell lines compared to noncancerous cells. According to cellular\u2010uptake experiments, such selectivity is not correlated to a different ability to enter cancerous or noncancerous cells. Remarkably, the cytotoxicity profile of the complexes does not substantially decrease in 3D cell cultures, in contrast to what has often been observed in the literature upon comparison of 2D/3D studies on various transition metal compounds. Interestingly, the activity exhibited by [2D]CF3SO3 in the ovarian cancer cell 3D model was even superior to that of cisplatin. Experiments on selected complexes outlined their power to behave as carbon monoxide\u2010releasing molecules (CORMs) inside cells, to unbalance cellular redox homeostasis and to alkylate biological targets. The preferential CO release in cancer cells with respect to untransformed cells could, at least in part, be consistent with the ability to target TrxR. Actually, it is well known that the Trx system is overexpressed in cancer cells, and has been recognized as a tumour\u2010specific target for the development of selective anticancer agents. In summary, we suggest that a simple diiron platform might offer an arsenal of tools not available for widely investigated ferrocenes, paving the way for the development of iron\u2010based drugs with optimized features. Further biochemical and biophysical studies will be performed to clarify in more detail the mechanism of action of this new class of organometallic anticancer candidates.We have described a synthetic strategy to obtain a family of diiron carbonyl complexes containing a bridging aminocarbyne/iminium hybrid ligand from the readily available [FeGeneral experimental details: [Fe2Cp2(CO)4] (99\u2009%) was purchased from Strem Chemicals, other reactants and solvents were obtained from Alfa Aesar, Merck, Apollo Scientific or TCI Chemicals and were of the highest purity available. Isocyanides were stored at 4\u2009\u00b0C or \u221220\u2009\u00b0C and used as received; contaminated labware was treated with bleach. Methyl triflate was stored under N2 at 4\u2009\u00b0C; allyl iodide and triethyloxonium tetrafluoroborate (1\u2005M solution in CH2Cl2) were stored under N2 at \u221220\u2009\u00b0C. Compounds [1A\u2013H]2D\u2013F]CF3SO3X , [2C]Cl, [5H]CF3SO3 (hygroscopic) and 6 were stored under N2; all other Fe compounds being air\u2010 and moisture\u2010stable in the solid state. NMR spectra were recorded at 25\u2009\u00b0C on a Bruker Avance II DRX400 instrument equipped with a BBFO broadband probe. Chemical shifts (expressed in parts per million) are referenced to the residual solvent peaks1H, 13C) or to external standards46 . In [D6]DMSO/D2O mixtures, 1H chemical shifts are referenced to the [D5]DMSO signal as in pure [D6]DMSO (\u03b4/ppm=2.50); in D2O/CD3OD mixtures, 1H chemical shifts are referenced to the CD3OD residual peak as CH3OH in pure D2O (\u03b4/ppm=3.34). 1H and 13C spectra were assigned with the assistance of 1H{31P}, 13C DEPT 135, 1H,1H COSY, 1H\u201013C gs\u2010HSQC and 1H\u201013C gs\u2010HMBC experiments.3 stored in the dark over Na2CO3 was used for NMR analysis. IR spectra of solid samples (650\u20134000\u2005cm\u22121) were recorded on a Perkin Elmer Spectrum One FTIR spectrometer, equipped with a UATR sampling accessory; IR spectra of solutions were recorded using a CaF2 liquid transmission cell (2300\u20131500\u2005cm\u22121) on a Perkin Elmer Spectrum 100 FTIR spectrometer. UV/Vis spectra (250\u2013800\u2005nm) were recorded on a Ultraspec 2100 Pro spectrophotometer using PMMA cuvettes (1\u2005cm path length). IR and UV/Vis spectra were processed with Spectragryph software.2Cp2(CO)3(CNR)], [1A[Fe\u2013H].General procedure. In a 250\u2005mL round\u2010bottom flask equipped with a reflux condenser under N2, the selected isocyanide, or its solution in MeCN , was added dropwise to a suspension of [Fe2Cp2(CO)4] (1.6\u2005equiv) in anhydrous MeCN (80\u2013100\u2005mL). Alkyl isocyanides: the mixture was heated at reflux (T\u2265100\u2009\u00b0C) for 8\u2005h, then stirred at room temperature for additional 14\u2005h. Aryl isocyanides: the mixture was stirred at room temperature for 14\u2005h then heated at reflux (T\u2265100\u2009\u00b0C) for 1\u20133\u2005h. Next, conversion was checked by IR and the dark red\u2010brown suspension was dried under vacuum (40\u2009\u00b0C). The resulting solid, consisting of a mixture of [Fe2Cp2(CO)4] and [Fe2Cp2(CO)3(CNR)], was directly used in the following alkylation procedure without any purification.2Cp2(CO)2(\u03bc\u2010CO){\u03bc\u2010CNMe(1H\u2010indol\u20106\u2010yl)}]CF3SO3, [2A]CF3SO3CF3SO3 is soluble in MeCN, THF, MeOH, CH2Cl2, less soluble in CH2Cl2, CHCl3, insoluble in Et2O, toluene and water. X\u2010ray quality crystals of [2A]CF3SO3 were obtained from an acetone solution layered with Et2O and settled aside at \u221220\u2009\u00b0C. Anal. calcd. for C25H21F3Fe2N2O6S: C 46.47, H 3.28, N 4.34; found: C 46.09, H 3.28, N 4.34. IR (solid state): \u03bd\u02dc/cm\u22121=3330w\u2010br (\u03bdNH), 3114w, 2004\u2005s (\u03bdCO), 1985\u2005s (\u03bdCO), 1833\u2005s (\u03bd\u03bc\u2010CO), 1583w\u2010sh, 1555\u2005m, 1540\u2005m (\u03bdCN), 1475w, 1458w, 1433w, 1420w, 1397\u2005m, 1361w, 1345w, 1323w, 1290\u20131276\u2005m, 1244\u2005s (\u03bdSO3), 1223\u2005s (\u03bdSO3), 1154\u2005s (\u03bdSO3), 1107\u2005m\u2010sh, 1067w, 1028\u2005s, 1016\u2005s\u2010sh, 1002\u2005m\u2010sh, 942w, 931w, 893w, 875w, 860\u2005m, 845\u2005m, 817w, 797\u2005m, 772\u2005s, 756w\u2010sh, 743\u2005m\u2010sh, 728\u2005m. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2022\u2005s (\u03bdCO), 1992\u2005m\u2010sh (\u03bdCO), 1836\u2005s (\u03bd\u03bc\u2010CO), 1554\u2005m, 1542\u2005m (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2023\u2005s (\u03bdCO), 1991\u2005m\u2010sh (\u03bdCO), 1836\u2005s (\u03bd\u03bc\u2010CO), 1554\u2005m, 1542\u2005m\u2010sh (\u03bdCN). 1H NMR (CD3CN): \u03b4/ppm=9.78 , 7.85 , 7.70 , 7.48 , 7.37 , 6.67\u22126.62 ; 5.39, 4.65 , 4.53 . 13C{1H} NMR (CD3CN): \u03b4/ppm=324.9 (CN), 255.9 (\u03bc\u2010CO); 209.8, 209.2 (CO); 144.6 (C2), 136.3 (C5), 129.1 (C8), 128.8 (C6), 118.8 (C3), 117.3 (C9), 113.8 (C4), 103.5 (C7); 91.2, 91.0 (Cp); 58.5 (C1). 19F{1H} NMR (CD3CN): \u03b4/ppm=\u221279.3. 1H NMR (CDCl3): \u03b4/ppm=9.57 , 8.0\u20137.0 , , 7.42\u20137.39 , 6.60 ; 5.41, 4.63 ; 4.56 .In a 150\u2005mL Schlenk tube under N3SO3[2B]CF. In a 150\u2005mL Schlenk tube under N2, CF3SO3Me  was added dropwise to a dark red solution of 1B (1.38\u2005mmol) in anhydrous CH2Cl2 (40\u2005mL) under stirring. Therefore, the mixture was stirred at room temperature for 7\u2005h and conversion was checked by IR (CH2Cl2). Next, the solution was moved on top of an alumina column . Impurities were eluted with neat CH2Cl2, THF and MeCN, then a red band containing the title product was eluted with MeCN/MeOH . Volatiles were removed under vacuum (40\u2009\u00b0C), affording a red, highly hygroscopic solid. Yield: quantitative. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2028\u2005s (\u03bdCO), 1997w\u2010sh (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO). 1H NMR (CDCl3): \u03b4/ppm=5.32 , 5.23 , 4.93 , 4.38 , 4.23\u20134.10 , 1.30 . 19F{1H} NMR (CDCl3): \u03b4/ppm=\u221278.2. 31P{1H} NMR (CDCl3): \u03b4/ppm=17.3.4[2B]BF. In a 500\u2005mL round bottom flask, [2B]CF3SO3 was suspended in water (100\u2005mL) with vigorous stirring until completely dissolved then treated with NaBF4 (500\u2005mg). The red solution was extracted with CH2Cl2 (3\u00d720\u2005mL) and the combined organic fractions were dried under vacuum. The residue was suspended in water and the ion exchange procedure with NaBF4 was repeated (\u00d73); 19F{1H} NMR analysis of the final CH2Cl2 solution indicated the complete removal of CF3SO3\u2212 anions. Therefore, volatiles were removed under vacuum; the residue was dissolved in CH2Cl2 and filtered over celite. A red foamy hygroscopic solid, obtained upon volatiles removal without heating, was dried under vacuum and stored under N2. Yield: 751\u2005mg, 90\u2009% (with respect to 1B). Compound [2B]BF4 is soluble in MeOH, MeCN, CH2Cl2, CHCl3, water, insoluble in Et2O and hexane. Anal. calcd. for C20H25BF4Fe2NO6P: C 39.71, H 4.17, N 2.31; found: C 39.20, H 4.25, N 2.26. IR (solid state): \u03bd\u02dc/cm\u22121=3117w, 2987w, 2938w, 2913w, 2875w, 2012\u2005s (\u03bdCO), 1986\u2005s\u2010sh (\u03bdCO), 1823\u2005s (\u03bd\u03bc\u2010CO), 1568\u2005m (\u03bdCN), 1479w, 1446w, 1435w, 1421w, 1399\u2005m, 1370w\u2010sh, 1297\u20131286w, 1254\u2005m, 1225\u2005m\u2010sh, 1180w, 1163w, 1075\u2005m\u2010sh, 1033\u2005s\u2010sh (\u03bdBF4), 1008\u2005s, 973\u2005s, 951\u2005s\u2010sh, 904\u2005m, 864\u2005m\u2010sh, 851\u2005m, 837\u2005m\u2010sh, 780s, 745\u2005s, 710\u2005m\u2010sh. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2028\u2005s (\u03bdCO), 1996w (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1574w (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2026\u2005s (\u03bdCO), 1994w (\u03bdCO), 1838\u2005m (\u03bd\u03bc\u2010CO), 1569w (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=5.29 , 5.15 , 4.93 , 4.35 , 4.24\u20134.10 , 1.30 . No changes were observed in the 1H spectrum after 14\u2005h at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=323.7 , 254.7 (\u03bc\u2010CO); 207.4, 207.1 (CO); 90.3, 90.1 (Cp); 63.3 (C3), 62.5 , 53.2 (C1), 16.4 . 19F{1H} NMR (CDCl3): \u03b4/ppm=\u2010151.9 (10BF4), \u2212152.0 (11BF4). 31P{1H} NMR (CDCl3): \u03b4/ppm=17.3.3SO3[2C]CF. In a 500\u2005mL round bottom Schlenk flask under N2, CF3SO3Me  was added dropwise to a dark red suspension of 1C (22.5\u2005mmol) in anhydrous CH2Cl2 (100\u2005mL) under stirring. Therefore, the mixture was stirred at room temperature for 4\u2005h and the conversion was checked by IR (CH2Cl2). Next, the dark red solution was moved on top of an alumina column . Impurities were eluted with neat CH2Cl2 and THF, then a red band containing [2C]CF3SO3 was eluted with MeCN/MeOH . A red band, containing a minor fraction of [2C]Cl, was collected using MeOH as eluent. Volatiles were removed under vacuum from the MeCN/MeOH solution and residue was triturated in Et2O. The suspension was stirred at room temperature for a few h then filtered. The resulting red solid was washed with toluene, Et2O and dried under vacuum (40\u2009\u00b0C). Yield: 11.44\u2005g, 85\u2009%. Compound [2C]CF3SO3 is soluble in MeCN, MeOH, CH2Cl2, CHCl3, less soluble in water, poorly soluble in toluene, insoluble in Et2O, hexane. X\u2010ray\u2010quality crystals of [2C]CF3SO3 were obtained from a CH2Cl2 solution layered with heptane and settled aside at \u221220\u2009\u00b0C. Anal. calcd. for C22H24F3Fe2NO6S: C 44.10, H 4.04, N, 2.34; found: C 44.47, H 4.04, N, 2.34. IR (solid state): \u03bd\u02dc/cm\u22121=3102w, 2937w, 2862w, 2185w, 2146w, 2006\u2005s (\u03bdCO), 1982\u2005s\u2010sh (\u03bdCO), 1822\u2005s (\u03bd\u03bc\u2010CO), 1565\u2005m (\u03bdCN), 1544\u2005m\u2010sh, 1452w, 1435w, 1421w, 1402w, 1366w, 1352w, 1321w, 1272\u2005s\u2010sh, 1257\u2005s (\u03bdSO3), 1223\u2005s\u2010sh (\u03bdSO3), 1150s (\u03bdSO3), 1056\u2005m, 1029\u2005s, 990\u2005m, 864\u2005m, 854\u2005m, 796\u2005s, 746\u2005s. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2020s (\u03bdCO), 1988w\u2010sh (\u03bdCO), 1835\u2005m (\u03bd\u03bc\u2010CO), 1567w (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2021\u2005s (\u03bdCO), 1988w\u2010sh (\u03bdCO), 1835\u2005m (\u03bd\u03bc\u2010CO), 1568w (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=5.36, 5.27 ; 4.68 , 4.06 , 2.81 , 2.15 , 2.03\u20131.94 , 1.86\u20131.72 , 1.53\u20131.35 , 1.34\u20131.20 . No changes were observed in the 1H spectrum after 14\u2005h at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=316.4 (CN), 255.3 (\u03bc\u2010CO); 208.5, 207.6 (CO); 90.3, 90.1 (Cp); 79.8 (C2), 46.8 (C1), 31.2 (C5), 30.7 (C4), 26.1 (C3), 26.0 (C6), 25.1 (C7). 19F{1H} NMR (CDCl3): \u03b4/ppm=\u221278.2. 1H NMR (CD3OD): \u03b4/ppm=5.40, 5.36 , 4.07 , 2.41 , 2.17\u20132.07, 2.03\u20131.91, 1.85\u20131.50, 1.42\u20131.32 .[2C]Cl. Compound [2C]CF3SO3  was dissolved in MeOH (2\u2005mL) then moved on top of an Amberlyst 15 column . NaCF3SO3 was eluted with neat MeOH then a red band containing [2C]+ was eluted with NaCl\u2010saturated MeOH. Volatiles were removed under vacuum and the residue was suspended in MeCN. The suspension was filtered over celite; the filtrate was checked for absence of CF3SO3\u2212 by 19F NMR then dried under vacuum (40\u2009\u00b0C). The resulting red, hygroscopic solid was stored under N2. Yield: 83\u2005mg, 93\u2009%. Compound [2C]Cl shows the same solubility pattern as the triflate salt. X\u2010ray quality crystals of [2C]Cl\u2009\u22c5\u20092.34H2O were obtained from a CH2Cl2 solution layered with hexane and settled aside at \u221220\u2009\u00b0C. Anal. calcd. for C21H24ClFe2NO3: C 51.94, H 4.98, N 2.88; found: C 51.99, H 5.02, N 2.83. IR (solid state): \u03bd\u02dc/cm\u22121=3376\u2005m\u2010br* (\u03bdOH), 3098\u20133059w, 2933\u2005m, 2858w, 2180\u20132160w, 1997\u2005s (\u03bdCO), 1969\u2005s\u2010sh (\u03bdCO), 1811\u2005s (\u03bd\u03bc\u2010CO), 1662w, 1631w, 1565\u2005s (\u03bdCN), 1543\u2005m, 1450\u2005m, 1434w, 1419\u2005m, 1400\u2005m, 1350w, 1319w, 1263w\u2010sh, 1249w, 1173w, 1154w, 1054\u2005m, 1026w, 1015w, 990\u2005m, 924w\u2010sh, 893w\u2010sh, 852\u2005m, 795\u2005s, 746\u2005s, 729\u2005s\u2010sh. *Due to moisture. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2018\u2005s (\u03bdCO), 1985w\u2010sh (\u03bdCO), 1833\u2005m (\u03bd\u03bc\u2010CO), 1569w (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2020s (\u03bdCO), 1987w\u2010sh (\u03bdCO), 1834\u2005m (\u03bd\u03bc\u2010CO), 1568w (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=5.51, 5.39 ; 4.75\u20134.66 , 4.14 , 3.16 , 2.15 , 2.03\u20131.93 , 1.84\u20131.72 , 1.51\u20131.35 , 1.33\u20131.23 . No changes were observed in the 1H spectrum after 24\u2005h at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=316.2 (CN), 255.8 (\u03bc\u2010CO); 208.7, 207.8 (CO); 90.7, 90.3 (Cp); 79.7 (C2), 47.1 (C1), 31.3 (C5), 31.0 (C4), 26.1 (C3), 26.0 (C6), 25.2 (C7). 35Cl NMR (CDCl3): \u03b4/ppm=7.61 (\u0394\u03bd1/2=266\u2005Hz).2, CF3SO3Me  was added dropwise to a dark red solution of 1B (4.63\u2005mmol) in anhydrous CH2Cl2 (40\u2005mL) under stirring. The mixture was stirred at room temperature for 5.5\u2005h then moved on top of an alumina column . Impurities were eluted with CH2Cl2 and CH2Cl2/THF , then a red band containing [2D]CF3SO3 was eluted with neat MeCN. Volatiles were removed under vacuum (40\u2009\u00b0C) to afford a red foamy solid. Yield: 2.446\u2005g, 85\u2009%. Compound [2D]CF3SO3 is soluble in MeCN, MeOH, CH2Cl2, CHCl3, water, insoluble in Et2O and hexane. X\u2010ray quality crystals of [2D]CF3SO3 were obtained from a CHCl3 solution layered with hexane and settled aside at \u221220\u2009\u00b0C. Anal. calcd. for C23H20F3Fe2NO7S: C 44.33, H 3.24, N 2.25; found: C 43.92, H 3.31, N 2.17. IR (solid state): \u03bd\u02dc/cm\u22121=3113w, 3091w, 2946w, 2849w, 2011\u2005s (\u03bdCO), 1978\u2005s (\u03bdCO), 1821\u2005s (\u03bd\u03bc\u2010CO), 1608w, 1563\u2005m, 1539\u2005m (\u03bdCN), 1506\u2005s, 1468w, 1449w, 1433w, 1420w, 1395\u2005m, 1304w\u2010sh, 1278\u2005s, 1251\u2005s (\u03bdSO3), 1224\u2005s\u2010sh (\u03bdSO3), 1176\u2005m\u2010sh, 1146\u2005s (\u03bdSO3), 1117\u2005m\u2010sh, 1108\u2005m, 1067w, 1028\u2005s, 890w, 855\u2005s, 825w\u2010sh, 773\u2005s, 756\u2005m\u2010sh, 736w, 702\u2005s. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2021\u2005s (\u03bdCO), 1989w (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1607w, 1562w, 1540w (\u03bdCN), 1507\u2005m. IR (MeCN): \u03bd\u02dc/cm\u22121=2024\u2005s (\u03bdCO), 1991w (\u03bdCO), 1837\u2005m (\u03bd\u03bc\u2010CO), 1610w, 1563w, 1539w (\u03bdCN), 1508w. 1H NMR (CDCl3): \u03b4/ppm=8.3\u20137.6 , 7.10 ; 5.43, 4.78 ; 4.54 , 3.90 . 19F{1H} NMR (CDCl3): \u03b4/ppm=\u221278.1.The title compound was prepared with minor modifications of the literature procedure.[3F]I. The preparation of the title compound was optimized with respect to the literature .2, allyl iodide  was added dropwise to a dark red solution of 1F (1.54\u2005mmol) in anhydrous MeCN (30\u2005mL) under vigorous stirring. The mixture was stirred for 4.5\u2005h under protection from the light and conversion was checked by IR (MeCN). Next, the dark red solution was moved on top of an alumina column . Impurities were eluted with neat Et2O, THF and MeCN, then a red band containing the title product was eluted with MeCN/MeOH . Volatiles were removed under vacuum (40\u2009\u00b0C) and the residue was triturated in Et2O. The suspension was stirred at room temperature then filtered. The resulting red solid was washed with Et2O and dried under vacuum (40\u2009\u00b0C). Yield: 646\u2005mg, 78\u2009%. Compound [3F]I is soluble in MeOH, CH2Cl2, CHCl3, poorly soluble in water, insoluble in Et2O, hexane. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2021\u2005s (\u03bdCO), 1989w (\u03bdCO), 1835\u2005m (\u03bd\u03bc\u2010CO), 1585w (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=6.09\u20135.97 , 5.53\u20135.46 ; 5.45, 5.53 ; 5.17\u20135.11 , 4.25 .3SO3[3F]CF. In a 50\u2005mL round bottom flask, a solution of Ag(CF3SO3)  in MeCN (5\u2005mL) was added to a dark red suspension of [3F]I  in MeCN (6\u2005mL) at 0\u2009\u00b0C. The mixture stirred at 0\u2009\u00b0C for 2.5\u2005h while maintaining the system under protection from the light. The resulting suspension (dark red solution+yellow AgI precipitate) was filtered over celite. Volatiles were removed under vacuum from the filtrate solution and the residue was triturated in a Et2O/toluene mixture. The suspension was stirred at room temperature for a few h, then filtered. The resulting red solid was washed with toluene, Et2O and dried under vacuum (40\u2009\u00b0C). Yield: 928\u2005mg, 94\u2009%. Compound [3F]CF3SO3 is soluble in MeCN, acetone, MeOH, water, less soluble in CH2Cl2 > CHCl3, poorly soluble in toluene, insoluble in Et2O. Anal. calcd. for C19H18F3Fe2NO6S: C 40.96, H, 3.26, N, 2.51; found: C 41.20, H, 3.20, N, 2.72. IR (solid state): \u03bd\u02dc/cm\u22121=3106w, 2213w, 2178w, 2012\u2005s (\u03bdCO), 1988\u2005s (\u03bdCO), 1813\u2005s (\u03bd\u03bc\u2010CO), 1644w, 1581\u2005m (\u03bdCN), 1435w, 1416w, 1395w, 1261\u2005s (\u03bdSO3), 1243\u2005s\u2010sh, 1222\u2005m\u2010sh (\u03bdSO3), 1169\u2005s (\u03bdSO3), 1050\u2005m, 1028\u2005s, 989w\u2010sh, 931\u2005m, 888\u2005m, 854\u2005m, 758\u2005s, 666\u2005m. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2022\u2005s (\u03bdCO), 1990w (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1584\u2005m (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2023\u2005s (\u03bdCO), 1990w (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1582\u2005m (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=5.98 , 5.50\u20135.45 ; 5.34, 5.32 ; 5.30\u20135.23 , 5.15\u20135.08 , 4.17 . No changes were observed in the 1H spectrum after 14\u2005h at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=318.1 (CN), 255.3 (\u03bc\u2010CO); 208.1, 207.8 (CO), 130.2 (C3), 122.2 (C4), 121.0 ; 90.20, 90.16 (Cp); 70.6 (C2), 51.3 (C1). 19F{1H} NMR (CDCl3): \u03b4/ppm=\u221278.2. 1H NMR ([D6]acetone): \u03b4/ppm=6.33\u20136.19 , 5.62 ; 5.58, 5.54 ; 5.41\u20135.16 , 4.28 .2, methyl iodide  was added to a dark red solution of 1G (0.48\u2005mmol) in anhydrous MeCN (8\u2005mL). The mixture was stirred for 2.5\u2005h and conversion was checked by IR (MeCN). Next, the dark red solution was moved on top of an alumina column . Impurities were eluted with neat CH2Cl2 and THF, then a red band containing the title product was eluted with THF/MeOH . Next, volatiles were removed under vacuum and the residue was dissolved in CH2Cl2. The suspension was filtered over celite and the filtrate was taken to dryness under vacuum (40\u2009\u00b0C), affording a dark red solid. Yield: 208\u2005mg, 69\u2009%. A considerable decrease in yield and purity was observed for reactions carried out in refluxing CHCl3 or in MeCN at lower temperatures. Anal. calcd. for C25H20Fe2INO3: C 48.35, H 3.25, N 2.56; found: C 48.20, H 3.15, N 2.49. Compound [3G]I is soluble in MeOH, CH2Cl2, CHCl3, sparingly soluble in water, insoluble in hexane. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2021\u2005s (\u03bdCO), 1989\u2005m\u2010sh (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1564w, 1545w, 1538w (\u03bdCN). 1H NMR (CDCl3): \u03b4/ppm=8.10 , 7.98\u22127.95 , 7.94\u22127.77 , 7.66\u22127.52 , 7.55\u22127.47  (C10H7); 5.62, 4.82 ; 4.75 .In a 25\u2005mL Schlenk tube under N2, [Et3O]BF4 , was added dropwise to a dark red solution of 1G (0.724\u2005mmol) in anhydrous MeCN (30\u2005mL) at 0\u2009\u00b0C under vigorous stirring. Therefore, the mixture was stirred for 3\u2005h, while allowing to reach room temperature. Next, conversion was checked by IR (MeCN) then volatiles were removed under vacuum. The residue was dissolved in a small volume of THF then moved on top of an alumina column . Impurities were eluted with neat Et2O and THF, then a red band containing the title product was eluted with MeCN/MeOH . Volatiles were removed under vacuum (40\u2009\u00b0C) and the residue was triturated in Et2O. The suspension was stirred at room temperature for a few h then filtered. The resulting dark red solid was washed with Et2O and dried under vacuum (40\u2009\u00b0C). Yield: 284\u2005mg, 66\u2009%. A considerable decrease in yield and purity was observed for reactions carried out in CH2Cl2 or in MeCN at room temperature. Compound [4G]BF4 is soluble in MeOH, MeCN, CH2Cl2, CHCl3, poorly soluble in Et2O, insoluble in water. Anal. calcd. for C26H22BF4Fe2NO3: C 52.49, H 3.72, N 2.35; found: C 52.11, H 3.67, N 2.30. IR (solid state): \u03bd\u02dc/cm\u22121=3116w, 3060w, 2979w, 2937w, 2160w\u2010br, 2007\u2005s (\u03bdCO), 1937\u2005s\u2010sh (\u03bdCO), 1836\u2005s (\u03bd\u03bc\u2010CO), 1596w, 1532\u2005s (\u03bdCN), 1506\u2005m\u2010sh, 1458w, 1434w, 1421w, 1381w, 1360w, 1341w, 1275w, 1247w, 1211w, 1179w, 1134w, 1075\u2005s\u2010sh, 1049\u2005s\u2010br, 1033\u2005s (\u03bdBF4), 1014\u2005s\u2010sh, 963w, 935w, 865w, 850w, 825w, 808\u2005m, 745\u2005s, 707\u2005m, 657\u2005m. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2021\u2005s (\u03bdCO), 1989w (\u03bdCO), 1836\u2005m (\u03bd\u03bc\u2010CO), 1538w (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=2023\u2005s (\u03bdCO), 1990w (\u03bdCO), 1837\u2005m (\u03bd\u03bc\u2010CO), 1537w (\u03bdCN). 1H NMR ([D6]acetone): \u03b4/ppm=8.7\u20138.3 , 8.30 , 8.16\u20138.09 , 8.1\u20137.7 , 7.75\u20137.70 , 5.68 , 5.19 , 4.87 , 1.51 . No changes were observed in the 1H spectrum after 14\u2005h at room temperature. 13C{1H} ([D6]acetone): \u03b4/ppm=325.2 (CN), 255.2 (\u03bc\u2010CO); 210.1, 209.8 (CO); 146.1 (C3); 134.3, 133.9 (C6+C11); 131.4 (C5); 129.5, 129.0 (C7+C10); 128.8, 128.6 (C8+C9); 126.3, 125.1 (C4+C12); 91.7, 91.2 (Cp); 66.8 (C1), 14.4 (C2). 19F{1H} NMR ([D6]acetone): \u03b4/ppm=\u2212151.0 (10BF4), \u2212151.1 (11BF4). 1H NMR (CDCl3): \u03b4/ppm=8.5\u20137.8 , 7.70\u20137.60 , 7.60\u20137.48 , 5.44 , 5.20\u20135.05 , 4.95 , 4.65 , 1.44 . 13C{1H} NMR (CDCl3): \u03b4/ppm=323.2 (br), 254.9, 209.2 (br), 208.4, ca. 145 (br); 133 (br), 132.9 (br); 130.1 (m), 128.1, 127.9, 126\u2013125 (m\u2010br), 124.0, 120.5, 117.1, 90.6, 90.3, 66 (br), 14.0. 19F{1H} NMR (CDCl3): \u03b4/ppm=\u2212150.9, \u2212151.0. The cis orientation of the Cp ligands in [4G]BF4 was ascertained by 1H NOE experiment in CDCl3. Thus, irradiation of one Cp resonance (\u03b4H 5.44 or 4.65\u2005ppm) evidenced a NOE interaction with the other.In a 150\u2005mL Schlenk tube under N[5H]Br. In a 100\u2005mL Schlenk tube under N2, benzyl bromide  was added dropwise to a dark red solution of 1H (1.58\u2005mmol) in anhydrous MeCN (50\u2005mL) under vigorous stirring at 60\u2009\u00b0C. The mixture was stirred at reflux for 1.5\u2005h and conversion was checked by IR (MeCN). Next, the dark red solution was moved on top of an alumina column . Impurities were eluted with neat CH2Cl2, THF and MeCN, then a red band containing the title product was eluted with MeCN/MeOH . Volatiles were removed under vacuum (40\u2009\u00b0C), affording a red solid. Yield: 892\u2005mg, 92\u2009%. Compound [5H]Br is soluble in CH2Cl2, CHCl3, THF, iPrOH, poorly soluble in toluene, EtOAc, insoluble in Et2O. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2020s (\u03bdCO), 1988w (\u03bdCO), 1837\u2005m (\u03bd\u03bc\u2010CO), 1550w (\u03bdCN), 1534w. 1H NMR (CDCl3): \u03b4/ppm=7.48 , 7.40 , 7.30\u20137.26 , 5.69 , 5.56 , 5.52 .3SO3[5H]CF. In a 50\u2005mL round bottom flask, a solution of Ag(CF3SO3)  in MeCN (5\u2005mL) was added to a dark red solution of [5H]I  in MeCN (40\u2005mL) at 0\u2009\u00b0C. The mixture was stirred at 0\u2009\u00b0C for 1.5\u2005h while maintaining the system under protection from the light. The resulting suspension  was filtered over celite and the filtrate solution was dried under vacuum. The residue was treated with hexane (10\u2005mL) then Et2O (50\u2005mL) and settled aside for 30\u2005min. Therefore, the solution was discarded and the washing procedure was repeated (x 2). The resulting red solid was dried under vacuum (40\u2009\u00b0C) and stored under N2 (slightly hygroscopic). Yield: 1076\u2005mg, 93\u2009%. Compound [5H]CF3SO3 is soluble in MeCN, acetone, MeOH, CH2Cl2, poorly soluble in Et2O, toluene, water and insoluble in hexane. Anal. calcd. for C29H24F3Fe2NO6S: C 50.98, H, 3.54, N, 2.05; found: C 50.59, H, 3.58, N, 2.26. IR (solid state): \u03bd\u02dc/cm\u22121=3106w, 3070\u20133230w, 2166w, 2013\u2005s (\u03bdCO), 1985\u2005s\u2010sh (\u03bdCO), 1827\u2005s (\u03bd\u03bc\u2010CO), 1588w, 1549\u2005m (\u03bdCN), 1533\u2005m, 1497w, 1454w, 1433w, 1420w, 1352w, 1260s (\u03bdSO3), 1223\u2005s\u2010sh (\u03bdSO3), 1153\u2005s (\u03bdSO3), 1096w, 1079w, 1029\u2005s, 858\u2005m, 767\u2005s, 737\u2005m\u2010sh, 698\u2005s. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=2023\u2005s (\u03bdCO), 1991\u2005m (\u03bdCO), 1840\u2005m (\u03bd\u03bc\u2010CO), 1550w (\u03bdCN), 1534w. IR (MeCN): \u03bd\u02dc/cm\u22121=2023\u2005s (\u03bdCO), 1990w (\u03bdCO), 1839\u2005m (\u03bd\u03bc\u2010CO), 1552w (\u03bdCN), 1538w. 1H NMR (CDCl3): \u03b4/ppm=7.50\u20137.44 , 7.44\u20137.39 , 7.20 , 5.66 , 5.50 , 5.40 . No changes were observed in the 1H spectrum after 2\u2005days at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=324.4 (CN), 253.7 (\u03bc\u2010CO), 208.2 (CO), 132.1 (C2), 129.9 (C4), 129.4 (C5), 127.8 (C3), 121.1 , 90.6 (Cp), 68.9 (C1). 19F{1H} NMR (CDCl3): \u03b4/ppm=\u221278.1\u2005ppm.2, a red suspension of [2C]CF3SO3 , Me3NO\u2009\u22c5\u20092H2O  and LiCl  in acetone (8\u2005mL) was stirred at reflux for 5\u2005h. Conversion was checked by IR (acetone) then volatiles were removed under vacuum. The brown residue was suspended in CH2Cl2 and moved on top of an alumina column , under N2. Impurities were eluted with CH2Cl2 then a brown band containing the title product was eluted with THF. The eluate was dried under vacuum and the residue was suspended hexane. The suspension was filtered; the resulting brown solid was washed with hexane and dried under vacuum (40\u2009\u00b0C). Yield: 55\u2005mg, 70\u2009%. A related one\u2010pot reaction with [2C]CF3SO3/Me3NO\u2009\u22c5\u20092H2O (1.6\u2005equiv)/NaCl (3.6\u2005equiv) in deaerated MeOH (8\u2005mL) at 40\u2009\u00b0C overnight gave 6 in 43\u2009% yield. A two\u2010step procedure comprising the [2C]CF3SO3/Me3NO\u2009\u22c5\u20092H2O (1\u2005equiv) reaction in MeCN at room temperature followed by LiCl (3.0\u2005equiv) in refluxing acetone for 3\u2005h gave 6 in 54\u2009% yield. Compound 6 is soluble in CH2Cl2, CHCl3, scarcely soluble in MeOH, insoluble in Et2O and hydrocarbons. Crystals of 6 for X\u2010ray analysis were obtained from a CHCl3 solution layered with pentane and settled aside at \u221220\u2009\u00b0C. IR (CH2Cl2): \u03bd\u02dc/cm\u22121=1977\u2005s (\u03bdCO), 1798\u2005s (\u03bd\u03bc\u2010CO), 1537\u2005m (\u03bdCN). IR (MeCN): \u03bd\u02dc/cm\u22121=1971\u2005s (\u03bdCO), 1795\u2005m (\u03bd\u03bc\u2010CO), 1539w (\u03bdCN). IR (solid state): \u03bd\u02dc/cm\u22121=3104w, 3070w, 1939\u2005s (\u03bdCO), 1782\u2005s (\u03bd\u03bc\u2010CO), 1558w\u2010sh, 1536\u2005s (\u03bdCN), 1456w, 1447w, 1419w, 1394\u2005m, 1360w, 1346w, 1317w, 1251w, 1182w, 1153w, 1116w, 1062\u2005m, 1016w, 1001w, 993\u2005m, 857w\u2010sh, 838\u2005m, 814\u2005m, 800s, 757\u2005s. 1H/13C NMR: mixture of isomers in 3\u2009:\u20092 ratio (1H CDCl3). Signals attributable to the minor isomer are italicized. 1H NMR (CDCl3): \u03b4/ppm=6.09, 5.01 ; 4.72, 4.70 ; 4.64, 4.62 ; 4.53, 4.05 ; 2.59, 2.37 ; 2.28\u20132.06, 1.98\u20131.69, 1.42\u20131.24 . No change in the 1H NMR spectrum was observed after 14\u2005h at room temperature. 13C{1H} NMR (CDCl3): \u03b4/ppm=334.8, 334.5 (CN); 268.1, 267.5 (\u03bc\u2010CO); 212.5, 211.9 (CO); 86.8, 86.6 (Cp); 86.4, 86.3 (Cp\u2019); 76.6, 75.4 (C2\u2010H); 44.4, 43.6 (C1\u2010H), 32.5, 32.1 (C3\u2010H); 32.3, 30.6, 26.3, 26.2, 26.0, 25.6, 25.6, 25.5 (C3\u2019\u2010H+C4\u2010H+C5\u2010H).In a 25\u2005mL Schlenk tube under N2A]CF3SO3, [2C]Cl\u2009\u22c5\u20092.34H2O, [2C]CF3SO3, [2D]CF3SO3 and 6 are reported in Table\u2005K\u03b1 radiation. The structures were solved by direct methods and refined by full\u2010matrix least\u2010squares based on all data using F2.2A]CF3SO3 which was located in the Fourier map and refined isotropically using the 1.2\u2010fold isoU of the parent N(2) atom. The H2O molecules of [2C]Cl\u2009\u22c5\u20092.34H2O are disordered and it was not possible to locate the hydrogen atoms. All non\u2010hydrogen atoms were refined with anisotropic displacement parameters. The crystals of 6 display a low quality, allowing the full determination of the overall connectivity and geometry of the complex, while the bonding parameters cannot be discussed in detail.Crystal data and collection details for BF4, [2C]Cl and [3F]CF3SO3 an inverse procedure was followed, starting from a solution of the compound in octanol\u2010saturated water. The partition coefficient was calculated as Pow=(A0aq\u2212Afaq)/Afaqwhere A0aqand Afaqare the absorbance in the aqueous phase before and after partition with the organic phase, respectively. The wavelength of the maximum absorption of each compound (320\u2013390\u2005nm range) was used for UV/Vis quantitation. The procedure was repeated three times for each sample (from the same stock solution); results are given as mean \u00b1 standard deviation  and cell culture mediumStability in water  in MeOH (0.50\u2005mL) then diluting with H2O up to 10.0\u2005mL total volume (5\u2009% v/v MeOH). Next, 3.20\u2005mL of the solution (nFe ca. 6\u2009\u22c5\u200910\u22123\u2005mmol) and a 7x2\u2005mm stir bar were transferred into a 4\u2010mL screw top vial (1.72\u2005mL neat gas phase volume). The mixture was sealed with a screw cap with a PTFE/silicone septum and heated at 37\u2009\u00b0C for 24\u2005h under stirring. Afterwards, the headspace was sampled with a gas tight microsyringe (250\u2005mL) and analysed by GC\u2010TCD. Therefore, the vial was vented, sealed and heated for further 24\u2005h, and GC\u2010TCD analysis was repeated. The amount of released CO  was calculated based on a calibration curve obtained from analyses of known air/CO mixtures (1\u201310\u2009% v/v), and the number of equivalents released over a 24\u2005h period refers to the initial amount of compound (eqCO=nCO/nFe). The residual amount of starting diiron complex after 48\u2005h was calculated by assuming the release of 3 equivalents of CO per mole and the total amount of CO released. The procedure was repeated three times for each sample (from the same stock solution); results are given as mean \u00b1 standard deviation (Table\u2005S4).4OAc (1.25\u00d710\u22122\u2005M)cFe2=1\u00d710\u22123\u2005M) were prepared by dissolving the selected compound in DMSO (0.25\u2005mL) or MeOH , then diluting with HPLC water up to 5.0\u2005mL total volume. Next, aliquots of the Fe (0.50\u2005mL) and lysozyme (2.0\u2005mL) stock solutions were mixed and the final solution  was kept at 37\u2009\u00b0C for 24\u2005h. The resulting suspensions were centrifuged  to separate the orange\u2010brown precipitate. A blank solution (lysozyme only) was prepared and treated by the same procedure. Next, samples were diluted 1\u2009:\u200920 (v/v) with a water/MeCN  solution containing 1\u2009% formic acid and analysed by HPLC\u2010MS and flow injection MS. For HPLC analyses, elution was conducted with a MeCN/water linear gradient (90\u2009:\u200910 to 5\u2009:\u200995 v/v over 60\u2005min), containing 0.05\u2009% trifluoroacetic acid. The following compounds were identified by their MS pattern: [2A]+ (tR=18.0\u2005min), [2B]+ (tR=13.8\u2005min), [2C]+ (tR=18.8\u2005min), [2D]+ (tR=17.0\u2005min), [2E]+ (tR=18.3\u2005min), [2F]+ (tR=9.7\u2005min), [3F]+ (tR=13.1\u2005min), [4G]+ (tR=23.0\u2005min), [5H]+ (tR=24.3\u2005min), lysozyme\u2010CH3 (tR=21.0\u2005min), lysozyme (tR=21.6\u2005min). In all cases, the starting organometallic cation was identified as the major Fe\u2010containing compound in solution. Protein peaks pattern were obtained following peak reconstruction. Peak integrals for lysozyme and methyl lysozyme were calculated from the extracted ion chromatograms from the flow injection MS analysis  was stored at 4\u2009\u00b0C as received. A stock solution was prepared by dissolving the powder protein (125\u2005\u03bcM) and NH2B]BF4, [2C]CF3SO3, [2D]CF3SO3 and [3F]CF3SO3 were dissolved in water while the other compounds were dissolved in the minimum DMSO amount prior to cell culture testing. A calculated amount of the stock drug DMSO solution was added to the cell culture media to reach a final maximum DMSO concentration of 0.5\u2009%, which had no effects on cell viability.Compounds , cisplatin and ImmunoPure Cell cultures. Human colon (HCT\u201015), pancreatic (PSN\u20101) and breast (MCF\u20107) carcinoma cell lines along with human melanoma cells (A375) were obtained from American Type Culture Collection . Embryonic kidney HEK293 cells were obtained from the European Collection of Cell Cultures . Human ovarian 2008 cancer cells were kindly provided by Prof. G. Marverti . MCF\u20107 ADR cells were kindly provided by Prof. N. Colabufo . Cell lines were maintained in the logarithmic phase at 37\u2009\u00b0C in a 5\u2009% CO2 atmosphere using the following culture media containing 10\u2009% fetal calf serum , antibiotics (50\u2005units/mL penicillin and 50\u2005\u03bcg/mL streptomycin) and 2\u2005mM l\u2010glutamine: i) RPMI\u20101640 medium  for PSN\u20101, 2008, HCT\u201015, MCF\u20107 and MCF\u20107 ADR cells; ii) DMEM for A375 and HEK293 cells.Spheroid cultures. Spheroid cultures were obtained by seeding 2.5\u00d7103 cells/well in round bottom non\u2010tissue culture treated 96 well\u2010plate  in phenol red free RPMI\u20101640 medium , containing 10\u2009% FCS and supplemented with 20\u2009% methyl cellulose stock solution.MTT assay. The growth inhibitory effect towards tumour cells was evaluated by means of MTT assay as previously described.3 cells/well, dependent upon the growth characteristics of the cell line, were seeded in 96\u2010well microplates in growth medium (100 \u03bcL). After 24\u2005h, the medium was removed and replaced with a fresh one containing the compound to be studied at the appropriate concentration. Triplicate cultures were established for each treatment. After 24 or 72\u2005h, each well was treated with 10 \u03bcL of a 5\u2005mg/mL MTT saline solution, and following 5\u2005h of incubation, 100 \u03bcL of a sodium dodecyl sulfate (SDS) solution in HCl 0.01\u2005M were added. After an overnight incubation, cell growth inhibition was detected by measuring the absorbance of each well at 570\u2005nm using a Bio\u2010Rad 680 microplate reader. Mean absorbance for each drug dose was expressed as a percentage of the control untreated well absorbance and plotted against drug concentration. IC50 values, the drug concentrations that reduce the mean absorbance at 570\u2005nm to 50\u2009% of those in the untreated control wells, were calculated by the four\u2010parameter logistic (4\u2010PL) model. Evaluation was based on means from at least four independent experiments.Acid phosphatase (APH) assay. An APH modified assay was used for determining cell viability in 3D spheroids, as previously described.50 values were calculated with a four\u2010parameter logistic (4\u2010PL) model. All the values are the means \u00b1 SD of not less than four independent experiments.Mitochondrial membrane potential (\u0394\u03a8). The \u0394\u03a8 was assayed using the Mito\u2010ID\u00ae Membrane Potential Kit according to the manufacturer's instructions  as previously described.3 per well) were seeded in 96\u2010well plates; after 24\u2005h, cells were washed with PBS and loaded with Mito\u2010ID detection reagent for 30\u2005min at 37\u2009\u00b0C in the dark. Afterwards, cells were incubated with increasing concentrations of tested complexes. Fluorescence intensity was estimated using a VICTOR X3  plate reader at \u03bbex=490 and \u03bbem=590\u2005nm. Antimycin (3\u2005\u03bcM) was used as positive control.ROS production. The production of ROS was measured in PSN\u20101 cells (104 per well) grown for 24\u2005h in a 96\u2010well plate in RPMI medium without phenol red (Merck). Cells were then washed with PBS and loaded with 10\u2005\u03bcM 5\u2010(and\u20106)\u2010chloromethyl\u20102\u2032,7\u2032\u2010dichlorodihydrofluorescein diacetate acetyl ester  for 25\u2005min, in the dark. Afterwards, cells were washed with PBS and incubated with increasing concentrations of tested compounds. Fluorescence increase was estimated by using \u03bbex=485\u2005nm and \u03bbem=527\u2005nm in a VICTOR X3 (PerkinElmer) plate reader. Antimycin , a potent inhibitor of Complex III in the electron transport chain, was used as positive control.Intracellular CO release. PSN\u20101\u2005cell (1\u00d7104) were seeded in 96\u2010well plates. After 24\u2005h, cells were treated with 20\u2005\u03bcM of tested complexes or CORM\u2010401 (Merck) for 15\u2005min at 37\u2009\u00b0C and followed by 30\u2005min incubation with a fluorescent probe BioTracker Carbon Monoxide Probe 1 Live Cell Dye\u00ae (Merck). The intracellular fluorescence, indicative of CO accumulation in cells, was quantified using a VICTOR X3 (PerkinElmer) plate reader.Cellular uptake. PSN\u20101 and HEK293 cells (3\u00d7106) were seeded in 75\u2005cm2 flasks in growth medium (20\u2005mL). After overnight incubation, the medium was replaced and the cells were treated with tested compounds for 24\u2005h. Cell monolayers were washed twice with cold PBS, harvested and counted. Samples were than subjected to three freezing/thawing cycles at \u221280\u2009\u00b0C, and then vigorously vortexed. The samples were treated with highly pure nitric acid  and transferred into a microwave Teflon vessel. Subsequently, samples were submitted to standard procedures using a speed wave MWS\u20103 Berghof instrument . After cooling, each mineralized sample was analysed for iron using a Varian AA Duo graphite furnace atomic absorption spectrometer (Varian) at the wavelength of 248.3\u2005nm. The calibration curve was obtained using known concentrations of standard solutions purchased from Sigma Chemical Co.Statistical analysis. All values are the means \u00b1 SD of no less than three measurements starting from three different cell cultures. Multiple comparisons were made by ANOVA followed by the Tukey\u2010Kramer multiple comparison test , using GraphPad software.50 values after 24\u2005h of incubation; MS spectra from lysozyme interaction experiments. Deposition numbers 2A]CF3SO3), 2045778 (for [2C]CF3SO3), 2045777 (for [2C]Cl), 2045780 (for [2D]CF3SO3) and 2045781 (for 6)2045779  should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The mol\u00adecular and crystal structure of a ferrocenyl derivative with an undecyl-1,11-diol chain on one cyclo\u00adpenta\u00addienyl ring is reported: O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) contacts occur in the extended structure. 5H5)(C16H27O2)], comprises an \u03b1,\u03c9-diol-substituted undecyl chain with a ferrocenyl substituent at at one terminus. The alkane chain is inclined to the substituted ring of the ferrocene grouping by 84.22\u2005(13)\u00b0. The ferrocene rings are almost eclipsed and parallel. The crystal structure features O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 contacts that stack the mol\u00adecules along the c-axis direction. A Hirshfeld surface analysis reveals that H\u22efH inter\u00adactions (83.2%) dominate the surface contacts.The racemic title compound, [Fe(C It was synthesized to provide a ferrocenyl-substituted diol for the preparation of polyesters with regular pendant electroactive groups. Similar ferrocenyl neo-pentyl diol-derived terephthalate polymers have been shown to display inter\u00adesting electrochemical properties  using LiAlH4. Enanti\u00adomeric selection of the individual chiral forms should be possible using more complex synthetic methodology (C16H27O2)], comprises a ferrocene unit that carries a well-ordered undecane chain (atoms C11\u2013C21) with hydroxyl substituents at the 1 and 11 positions along the chain \u00b0 between them. The C11 undecyl chain in 1 is conformationally extended with the typical anti\u00adperiplanar \u2005\u00c5. The C1\u2013C5 and C6\u2013C10 cyclo\u00adpenta\u00addienyl rings of the ferrocenyl group are approximately 3\u00b0 from being eclipsed and are almost coplanar with a dihedral angle of 1.7\u2005(2)\u00b0 between them; the separation of the ring centroids is is 3.298\u2005(2)\u2005\u00c5.The title compound, , 1.7\u20131.3 . 13C NMR (CDCl3): 94.7 (Fc ipso), 69.7 (\u2013CHOH\u2013), 68.3 (Cp), 67.9, 67.7, 67.3, 65.2 (Fc\u2014C\u03b1 & \u03b2), 63.2 (\u2013CH2OH), 38.3, 32.9, 29.6, 29.6, 29.5, 29.5, 26.1, 25.8 (\u2013CH2\u2013). UV\u2013vis (CH2Cl2): 325 (90), 440 (110) nm (\u025b).The title compound iso(H) = 1.5 Ueq(O). All H-atoms bound to C were refined using a riding model with C\u2014H = 0.95\u20131.00\u2005\u00c5 and Uiso(H) = 1.2Ueq(C). Despite repeated attempts to grow crystals of better quality, the crystals obtained were weakly diffracting and the extent of diffraction observed is poor with sin\u2005(\u03b8max)/\u03bb = 0.544 (2\u03b8max = 44.5\u00b0). Despite this, the structure solved and refined adequately.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902101358X/hb8007sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902101358X/hb8007Isup2.hklStructure factors: contains datablock(s) I. DOI: 2130725CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, dimeric C\u2014H\u22efO hydrogen bonds connect pairs of cations, producing two  30H28NO2+\u00b7CF3O3S\u2212, the four tetra\u00adhydro\u00adfuran rings adopt envelope conformations. In the crystal, pairs of cations are linked by dimeric C\u2014H\u22efO hydrogen bonds, forming two R22(6) ring motifs parallel to the (001) plane. The cations and anions are connected by further C\u2014H\u22efO hydrogen bonds, forming a three-dimensional network structure. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (47.6%), C\u22efH/H\u22efC (20.6%), O\u22efH/H\u22efO (18.0%) and F\u22efH/H\u22efF (9.9%) inter\u00adactions.In the cation of the title salt, C The mol\u00adecular conformation of the cation is stabilized by weak intra\u00admolecular C21\u2014H21B\u22efO12 and C21\u2014H21B\u22efO13 contacts (Table\u00a01B/C11C/C3A/C3) in the cation exhibits a chair conformation . The benzene ring (C7A/C8\u2013C11/C11A) fused with the central tetra\u00adhydro\u00adfuran ring makes dihedral angles of 53.43\u2005(5) and 58.64\u2005(5)\u00b0, respectively, with the C22\u2013C27 and C32\u2013C37 phenyl rings of the benzyl groups attached to the N atom. These phenyl rings make a dihedral angle of 73.81\u2005(5)\u00b0 with each other.In the cation  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01], forming two et al., 1995A\u22efO1i, C6\u2014H6A\u22efO12ii, C6A\u2014H6AA\u22efO3ii, C7\u2014H7A\u22efO13ii, C31\u2014H31A\u22efO2i and C9\u2014H9A\u22efCg10iii hydrogen bonds, forming a three-dimensional network  inter\u00adactions constitute the primary factor in the crystal packing, with C\u22efH/H\u22efC , O\u22efH/H\u22efO  and F\u22efH/H\u22efF  inter\u00adactions constituting the next stronger contributions. Numerical values of these inter\u00adactions together with other percentage contributions of weaker inter\u00adactions are compiled in Table\u00a03The inter\u00admolecular inter\u00adactions Table\u00a02 were qu\u00ad\u22efC Fig.\u00a08c, O\u22efH/H\u22efO Fig.\u00a08d and F\u22ef\u22efF Fig.\u00a08e inter\u00adet al., 2016viz. IQOTOA  and ac plane. Additionally, C\u2014H\u22efO hydrogen bonds form a C(6) chain, linking the mol\u00adecules along the b-axis direction. In the crystal of ERIVIL, mol\u00adecules are connected into b axis. In MIGTIG, the mol\u00adecules are linked only by weak van der Waals inter\u00adactions.IQOTOA, OMUTAU and OMEMAX each crystallize with two mol\u00adecules in the asymmetric unit. In the crystal, mol\u00adecule pairs generate centrosymmetric rings with -2,2-Dibenzyl-2,3,6a,11c-tetra\u00adhydro-1H,6H,7H-3a,6:7,11b-di\u00adepoxy\u00addibenzoisoquinolin-2-ium tri\u00adfluoro\u00admethane\u00adsulfonate (1)3CN (20\u2005ml). Then an equivalent of 2-(tri\u00admethyl\u00adsil\u00adyl)phenyl tri\u00adfluoro\u00admethane\u00adsulfonate  was added to the solution under an argon atmosphere. The mixture was refluxed for 4\u2005h . After one more portion of 2-(tri\u00admethyl\u00adsil\u00adyl)phenyl tri\u00adfluoro\u00admethane\u00adsulfonate  and CsF  had been added to the mixture, all procedures were repeated. After the mixture was cooled to room temperature, the CsF was filtered off through a thin layer of SiO2, and the resulting solution was concentrated under reduced pressure. The residue (yellow oil) turned out to be a multicomponent mixture. It was separated using column chromatography on silica gel. The least mobile fraction represented the target product, 1. In addition, two by-products 2 (12%) and 3 (17%) were isolated. Single crystals of 1 were obtained by slow crystallization from ethyl acetate.Cesium fluoride (CsF)  was added to benzyl\u00adbis\u00ad(furan-2-ylmeth\u00adyl)amine (0.0022\u2005mol) dissolved in dry CHUiso(H) = 1.2Ueq(C). Five reflections  I. DOI: 10.1107/S2056989021010173/wm5617Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the title mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efN, C\u2014H\u22efCl, C\u2014H\u22ef\u03c0 contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions. A Hirshfeld surface analysis was undertaken to qu\u00adantify the inter\u00admolecular inter\u00adactions. 24H20ClNO2, the mean planes of 4-chloro\u00adphenyl, 2-methyl\u00adphenyl and phenyl\u00adene rings make dihedral angles of 62.8\u2005(2), 65.1\u2005(3) and 15.1\u2005(2)\u00b0, respectively, with the 5-methyl-1,2-oxazole ring. In the crystal, mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efN, C\u2014H\u22efCl, C\u2014H\u22ef\u03c0 contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions between the phenyl\u00adene groups. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efH (48.7%), H\u22efC/C\u22efH (22.2%), Cl\u22efH/H\u22efCl (8.8%), H\u22efO/O\u22efH (8.2%) and H\u22efN/N\u22efH (5.1%) inter\u00adactions.In the title compound, C SCXD has thus become an essential tool for drug development to unambiguously determine the three-dimensional structures of mol\u00adecules, which eventually paves the way for rapid development of new mol\u00adecules  = 3.958\u2005(2)\u2005\u00c5]  to 1.5787\u2005\u00c5 (blue)  Fig.\u00a04.dnorm values on the surface, correspond to the C\u2014H\u22efN (C17\u2014H17A\u22efN1), C\u2014H\u22efCl (C8\u2014Cl1\u22efH1C\u2014C1) and C\u2014H\u22ef\u03c0 (C6\u2014H6\u22efphenyl\u00adene) inter\u00adactions  shows the total two-dimensional fingerprint plot providing information on the major and minor percentage contributions of the inter\u00adatomic contacts to the Hirshfeld surface of the title compound. The blue colour refers to the frequency of occurrence of the  pair and the grey colour is the outline of the full fingerprint  show that the H\u22efH contacts clearly make the most significant contribution to the Hirshfeld surface (48.7%). The H\u22efC/C\u22efH, Cl\u22efH/H\u22efCl, H\u22efO/O\u22efH and H\u22efN/N\u22efH contacts contribute 22.2, 8.8, 8.2 and 5.1%, respectively . The remaining weaker contacts are listed in Table\u00a03Fig.\u00a06ly Fig.\u00a06c\u2013f. Theet al., 2015The large number of H\u22efH, H\u22efC/C\u22efH, Cl\u22efH/H\u22efCl, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions play the major roles in the crystal packing (Hathwar E)-2- (di\u00admethyl\u00adamino)\u00adethen\u00adyl]-1,2-oxazole-4- carboxyl\u00adate , whereas in mol\u00adecule B, it points back towards the benzene ring [C\u2014C\u2014C=O = 17.9\u2005(4)\u00b0]. The dihedral angles between the oxazole and benzene rings are also somewhat different . Each mol\u00adecule features an intra\u00admolecular C\u2014H\u22efO inter\u00adaction, which closes an S(6) ring. In the crystal, the B mol\u00adecules are linked into C(12) chains along the c-axis direction by weak C\u2014H\u22efCl inter\u00adactions. In the crystal of (II), the components are linked by O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, where the water mol\u00adecule acts as both an H-atom donor and an acceptor, into a tape along the a-axis direction with an In compound (I)N-hy\u00addroxy-4-[(2-methyl\u00adbenz\u00adyl)\u00adoxy]benzimidoyl chloride  in diethyl ether (6\u2005ml) was added Et3N . The resulting mixture was stirred for 2\u2005h in an ice bath, and the precipitate formed was filtered off. The filtrate was evaporated under vacuum to obtain the aryl\u00adnitriloxide inter\u00admediate.Step 1: To a solution of 2SO4, filtered and evaporated to dryness. The crude product was purified by automated-flash chromatography on silica gel (12\u2005g) eluting with a gradient of 0 to 40% EtOAc in hexane. The obtained pure product was recrystallized from methanol. Crystals for structural study were obtained by slow cooling of the solution, yield 77%, m.p. 387.2\u2013388.6\u2005K.Step 2: To a solution of NaH  in dry THF (4\u2005ml), 4-chloro\u00adphenyl\u00adacetone  was added dropwise, and stirred for 1\u2005h under a nitro\u00adgen atmosphere in an ice bath. At the end of the period, the aryl\u00adnitriloxide inter\u00admediate was dissolved in dry THF (4\u2005ml), and was added to the reaction mixture, then stirred at room temperature overnight. Upon completion of the reaction, aqueous ammonium chloride solution was added, and the product was extracted with EtOAc (2 \u00d7 50\u2005mL). The combined organic extracts were dried over anhydrous Na1H NMR : \u03b4 2.29 , 2.39 , 5.07 , 7.05 , 7.15\u20137.25 , 7.27 , 7.38 , 7.47 .13C NMR : \u03b4 11.21, 18.42, 67.98, 113.96, 114.97, 120.84, 125.77, 128.15, 128.59, 128.86, 129.43, 130.12, 131.44, 132.57, 134.58, 136.64, 159.49, 160.09, 166.93. HRMS (m/z): [M + H]+ calculated for C24H21ClNO2: 390.1261; found: 390.1263.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). In the final refinement, three outliers  I. DOI: 10.1107/S2056989021002383/yk2147Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021002383/yk2147Isup3.cmlSupporting information file. DOI: 2067449CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This study was designed to identify the fluid spaces that are most changed during ultrafiltration (UF) according to intradialytic blood pressure (BP) difference. BP data were collected five times . Intradialytic BP difference was calculated as the highest minus lowest of these BP measurements. Intradialytic systolic BP (SBP) difference over 20\u2009mm Hg and diastolic BP (DBP) difference over 10\u2009mm Hg were defined as wide intradialytic SBP difference (SYS-W) and DBP difference (DIA-W), respectively. We measured the various fluid spaces before HD and 1\u20134\u2009h of HD, and 30\u2009min after HD using a portable, whole-body bioimpedance spectroscopy (BIS). In this study, 85 prevalent patients aged over 18\u2009years with a fixed dry weight , undergoing HD had participated. 1) Mean relative reduction of extracellular water (ECW) was significantly higher in SYS-W than in narrow intradialytic SBP difference (SYS-N) patients from 1\u2009h to 30\u2009min after HD. 2) Mean relative reduction of intracellular water (ICW) was significantly lower in DIA-W than in narrow intradialytic DBP difference (DIA-N) patients from 1\u2009h to 30\u2009min after HD. 3) ECW of patients with SYS-W was significantly lower than that of patients with SYS-N. Patients with SYS-W have the characteristics of fluid shifts in which reduction of ECW was steeper than patients with SYS-N whereas fluid shifts of ICW were lower in patients with DIA-W than patients with DIA-N. A recent large, retrospective cohort study observed first-year mortality to be higher in HD patients with BP variability than in those with stable BP, independent of the absolute BP level, suggesting that BP variability is associated with worse outcomes at all levels of BP . The majvs. intracellular [IC]) source of fluid shifts during the UF procedure and the relative ratio of these compartments during conventional renal replacement therapy in patients with asymptomatic intradialytic BP variability. An authoritative journal accepted the definition of BP variability by the difference between the highest and lowest BP during each session , patients with a history of ischemic or hemorrhagic stroke, or heart disease including atrial fibrillation  < 45% by 2-D echocardiography); those with peripheral arterial occlusive disease, such as gangrene, and amputees; and those with infection or hemiplegia were excluded. Some of the patient\u2019s characteristics are given in 2 hollow fiber poly-sulfone membranes, blood flow rates of 250\u2013280\u2009mL/min, and a dialysate flow rate of 500\u2009mL/min, using the Fresenius 5008S machine . The mean UF volume was 2457.65\u2009\u00b1\u2009947.73\u2009mL, and treatment time was 4\u2009h. The dialysis fluid contained 138 mEq/L sodium, 2 mEq/L potassium, 2.5 mEq/L calcium, 1.0 mEq/L magnesium, 108.5 mEq/L chloride, 35 mEq/L bicarbonate, and 99.1\u2009mg/dL glucose, and the temperature was maintained at 36\u2009\u00b0C.All patients underwent high-flux HD thrice weekly with a bicarbonate buffer for 4\u2009h, using 1.0\u20131.4-mBP data were collected five times (before HD and 1\u20134\u2009h of HD), and the highest and lowest measurements were identified. Intradialytic BP difference was calculated as the highest minus lowest BP measurements of each dialysis session . Intradiurea) in liters (L). The BCM determines resistance and reactance at 50 discrete frequencies from 3 to 1000\u2009kHz. ECW and ICW resistance are obtained on the basis of a Cole model [BCM measurement has been recommended that subjects should be resting in a supine position for at least 5\u2009min, before the BCM-measurement is started, such that fluid volume equilibration has taken place . We measle model . Using tle model .Because of the small number of patients, normal distribution was tested using a single sample Kolmogorov\u2013Smirnov analysis. Continuous variables are expressed as mean\u2009\u00b1\u2009SD or median (range) according to normal distribution of data. Categorical variables are expressed as percentage (%). Between-group differences were assessed for significance using a Student t-test for normal distribution, Mann\u2013Whitney U tests for skewed distribution, or Chi-Square test for categorical variables. Statistical analyses were performed using SPSS software version 14.0 .The study included a total of 85 patients undergoing HD (vintage of 70.98\u2009\u00b1\u200959.47\u2009months), 46 (54.12%) men with a mean age of 65.38\u2009\u00b1\u200912.45\u2009years. Here, 44 (51.76%) patients had diabetes mellitus and 50 (58.82%) patients had hypertension. The anti-hypertensive medications administered by the patients included angiotensin-converting enzyme inhibitor by nine patients (10.59%), angiotensin II receptor blocker by 18 patients (21.18%), calcium channel blocker by 30 patients (35.29%), alpha blocker by three patients (3.53%), beta-blocker by 21 patients (24.71%), diuretic by seven patients (8.24%), and other anti-hypertensive medications by 2 patient (2.35%). In 62 (72.94%) or 35 (41.17%) of the patients on HD, phosphorus binders or active vitamin D metabolites  were administered, respectively. Other variables are summarized in vs. 0.984\u2009\u00b1\u20090.027; 2\u2009h, 0.988\u2009\u00b1\u20090.047 vs. 0.975\u2009\u00b1\u20090.034; 3\u2009h, 0.970\u2009\u00b1\u20090.032 vs. 0.958\u2009\u00b1\u20090.032; 4\u2009h, 0.960\u2009\u00b1\u20090.035 vs. 0.948\u2009\u00b1\u20090.035, 30\u2009min after HD; 0.955\u2009\u00b1\u20090.029 vs. 0.941\u2009\u00b1\u20090.032, respectively)  .vs. 0.977\u2009\u00b1\u20090.019*; 2\u2009h, 0.966\u2009\u00b1\u20090.027 vs. 0.952\u2009\u00b1\u20090.026*; 3\u2009h, 0.942\u2009\u00b1\u20090.032 vs. 0.924\u2009\u00b1\u20090.033*; 4\u2009h, 0.923\u2009\u00b1\u20090.037 vs. 0.901\u2009\u00b1\u20090.038*, 30\u2009min after HD; 0.916\u2009\u00b1\u20090.038 vs. 0.895\u2009\u00b1\u20090.042*, respectively, *p\u2009<\u2009.05)  .vs. 0.991\u2009\u00b1\u20090.052; 2\u2009h, 1.008\u2009\u00b1\u20090.081 vs. 0.996\u2009\u00b1\u20090.064; 3\u2009h, 0.996\u2009\u00b1\u20090.047 vs. 0.989\u2009\u00b1\u20090.054; 4\u2009h, 0.997\u2009\u00b1\u20090.044 vs. 0.991\u2009\u00b1\u20090.058, 30\u2009min after HD; 0.992\u2009\u00b1\u20090.038 vs. 0.987\u2009\u00b1\u20090.049, respectively)  .vs. 0.986\u2009\u00b1\u20090.024; 2\u2009h, 0.971\u2009\u00b1\u20090.025 vs. 0.982\u2009\u00b1\u20090.040; 3\u2009h, 0.955\u2009\u00b1\u20090.027 vs. 0.964\u2009\u00b1\u20090.036; 4\u2009h, 0.945\u2009\u00b1\u20090.034 vs. 0.953\u2009\u00b1\u20090.036, 30\u2009min after HD; 0.938\u2009\u00b1\u20090.026 vs. 0.947\u2009\u00b1\u20090.036, respectively)  .vs. 0.975\u2009\u00b1\u20090.021; 2\u2009h, 0.959\u2009\u00b1\u20090.021 vs. 0.953\u2009\u00b1\u20090.030; 3\u2009h, 0.932\u2009\u00b1\u20090.027 vs. 0.926\u2009\u00b1\u20090.038; 4\u2009h, 0.910\u2009\u00b1\u20090.035 vs. 0.905\u2009\u00b1\u20090.042, 30\u2009min after HD; 0.901\u2009\u00b1\u20090.036 vs. 0.898\u2009\u00b1\u20090.046, respectively)  .vs. 0.997\u2009\u00b1\u20090.049*; 2\u2009h, 0.982\u2009\u00b1\u20090.043 vs. 1.009\u2009\u00b1\u20090.073*; 3\u2009h, 0.977\u2009\u00b1\u20090.045 vs. 1.001\u2009\u00b1\u20090.053*; 4\u2009h, 0.980\u2009\u00b1\u20090.056 vs. 0.999\u2009\u00b1\u20090.050*, 30\u2009min after HD; 0.975\u2009\u00b1\u20090.040 vs. 0.995\u2009\u00b1\u20090.050, respectively, *p\u2009<\u2009.05)  .vs. 0.993\u2009\u00b1\u20090.021; 2\u2009h, 0.977\u2009\u00b1\u20090.021 vs. 0.977\u2009\u00b1\u20090.016; 3\u2009h, 0.965\u2009\u00b1\u20090.024 vs. 0.966\u2009\u00b1\u20090.029; 4\u2009h, 0.953\u2009\u00b1\u20090.020 vs. 0.953\u2009\u00b1\u20090.025, 30\u2009min after HD; 0.950\u2009\u00b1\u20090.021 vs. 0.950\u2009\u00b1\u20090.030, respectively)  .vs. 0.977\u2009\u00b1\u20090.019*; 2\u2009h, 0.969\u2009\u00b1\u20090.014 vs. 0.949\u2009\u00b1\u20090.026*; 3\u2009h, 0.946\u2009\u00b1\u20090.018 vs. 0.923\u2009\u00b1\u20090.034*; 4\u2009h, 0.924\u2009\u00b1\u20090.018 vs. 0.904\u2009\u00b1\u20090.038*, 30\u2009min after HD; 0.922\u2009\u00b1\u20090.019 vs. 0.885\u2009\u00b1\u20090.043*, respectively, *p\u2009<\u2009.05)  .vs. 1.014\u2009\u00b1\u20090.050*; 2\u2009h, 0.983\u2009\u00b1\u20090.039 vs. 1.010\u2009\u00b1\u20090.034*; 3\u2009h, 0.982\u2009\u00b1\u20090.042 vs. 1.015\u2009\u00b1\u20090.037*; 4\u2009h, 0.982\u2009\u00b1\u20090.034 vs. 1.012\u2009\u00b1\u20090.038*, 30\u2009min after HD; 0.984\u2009\u00b1\u20090.036 vs. 1.010\u2009\u00b1\u20090.039*, respectively, *p\u2009<\u2009.05)  .urea, TBW, ICW, and E/I ratio were no significant difference between the groups  weight, UFV, Ve groups .The main findings of our study are 1) changes in the ECW of patients with wide intradialytic SBP difference were significantly steeper than those of patients with narrow intradialytic SBP difference from 1\u2009h to 30\u2009min after HD. 2) there were no significant fluid shifts in the ICW of patients with wide intradialytic DBP difference, whereas that of patients with narrow intradialytic DBP difference was significantly decreased from 1\u2009h to 30\u2009min after HD. 3) ECW of patients with wide intradialytic SBP difference was significantly lower than that of patients with narrow intradialytic SBP difference.The results of the study suggest that maintenance of intradialytic SBP stability is dependent on the amount of ECW reduction during HD and that DBP stability is associated with the shifts of ICW. That is because there was no difference in the changes of TBW, whereas the difference in ECW or ICW changes could be observed between patients with narrow SBP difference and wide SBP difference, between patients with narrow DBP difference and wide DBP difference during HD, respectively. This phenomenon has been confirmed from patients with narrow intradialytic SBP/DBP difference, once again. In particular, ICW in patients with narrow intradialytic SBP/DBP difference showed a significant decrease, whereas that in patients with wide intradialytic SBP/DBP difference demonstrated no significant reduction of ICW from 1\u2009h of HD compared to the start of HD. The above changes were continued until 30\u2009min after HD without further reduction or increase. This indicates that the amount of shifts of ICW to ECW may affect the maintenance of SBP and DBP stability in situations where ECW is continuously reduced after HD. Thus, in contrast to a previous report , fluid rA recently introduced equipment called a BCM utilizes a well-established technical solution to assess the absolute volume of the body fluid distribution  using 50 multiple, discrete frequencies from 3 to 1000\u2009kHz . DespiteThe clinical dilemmas and prognostic uncertainties exist in a patient with asymptomatic intradialytic BP falls, elevations, and fluctuations compared to overt intradialytic BP abnormalities such as IDH or IH. This absence of associated symptoms contributes to the tendency to regard asymptomatic BP fluctuations as \u2018normal\u2019 BP. However, there is a possibility that aberrant, asymptomatic intradialytic BP changes induce harmful effects to HD patients. Thus, our study was designed to evaluate factors that may influence the fluid shifts in asymptomatic patents with intradialytic BP falls. But, there were no significant differences between the hydration status, presence of DM, age, sex, HT medication, HD vintage, and fluid distribution index. Only we found that ECW of patients with wide intradialytic SBP difference was significantly lower than that of patients with narrow intradialytic SBP difference. Unfortunately, it would be difficult to explain the exact meaning of our results. Nevertheless, further study should be needed to elucidate the changes of IVF and ISF absolute values and relevant factors in asymptomatic patients with wide intradialytic BP difference.per se and a relation between a larger decline in ECW and BP is to be expected. If we repeated the analysis with additional BP variability metrics such as the BP residual in a random-effects model [This study had some limitations. First, we used intradialytic BP difference as an index of BP fluctuation instead of other intradialytic BP variability index, such as standard deviation, absolute value of the difference between successive BP measurements and BP residual. However, this reflects more the BP drop during HD than the variability ts model , we thouPatients with wide intradialytic SBP difference have the characteristics of fluid shifts in which reduction of ECW was steeper than patients with narrow intradialytic SBP difference whereas fluid shifts of ICW were lower in patients with wide intradialytic DBP difference than patients with narrow intradialytic DBP difference. This phenomenon has been confirmed from patients with narrow intradialytic SBP/DBP difference."}
{"text": "Scientific Reports 10.1038/s41598-021-85129-1, published online 10 March 2021Correction to: The original version of this Article contained errors.Author Fatih Semerci was incorrectly given as Faith Semerci.In addition, in the Introduction,\u201cThe NSC-6 Ab, which produced the most robust staining of NPCs, corresponded to Brain-Associated Signal Protein 1 (BASP1), a protein not previously described in NPCs.\u201dnow reads:\u201cThe NSC-6 Ab, which produced the most robust staining of NPCs, corresponded to Brain-Abundant, membrane-attached Signal Protein 1 (BASP1), a protein not previously described in NPCs.\u201dIn the Results section, under subheading \u201cNSC-6 stains mouse and human NPCs\u201d,\u201cIn addition, we derived human neuroprogenitor cells (hNPCs) from inducible pluripotent stem cells (iPSCs) obtained from a healthy adult and stained them with NSC-6.\u201dnow reads:\u201cIn addition, we derived human neuroprogenitor cells (hNPCs) from induced pluripotent stem cells (iPSCs) obtained from a healthy adult and stained them with NSC-6.\u201dUnder the subheading \u201cNSC-6-labeled BASP1 is regulated temporally in the mammalian brain\u201d,\u201cConsistent with the data obtained in mice, our results show high BASP1 expression in the hippocampus, the brainstem, and the spinal cord .\u201dnow reads:\u201cConsistent with the data obtained in mice, our results show high BASP1 expression in the human hippocampus, the brainstem, and the spinal cord .\u201dIn the Materials and methods section, under subheading \u201cEmbryonic neurosphere culture and hybridoma production\u201d,5\u00a0cells/10\u00a0ml of proliferation media containing Neurocult Basal Media (STEM CELL TECHNOLOGIES), 10% Proliferation Supplement (STEM CELL TECHNOLOGIES), 20\u00a0ng/ml EGF and FGF (SIGMA) and 1% antibiotic\u2013antimycotic (GIBCO).\u201d\u201cWhole brains from C57/BL6 embryonic day 12 (E12) mice were dissected, digested with collagenase  for 2\u00a0h at 37\u00a0\u00b0C, filtered twice through 0.4\u00a0\u03bcm filters and plated at 3\u2009\u00d7\u200910now reads:5\u00a0cells/10\u00a0ml of proliferation media containing Neurocult Basal Media (STEM CELL TECHNOLOGIES), 10% Proliferation Supplement (STEM CELL TECHNOLOGIES), 20\u00a0ng/ml EGF and FGF (SIGMA) and 1% antibiotic\u2013antimycotic (GIBCO).\u201d\u201cWhole brains from C57/BL6 embryonic day 12 (E12) mice were dissected, digested with collagenase  for 2\u00a0h at 37\u00a0\u00b0C, filtered twice through 40\u00a0\u03bcm filters and plated at 3\u2009\u00d7\u200910Under subheading \u201cTwo-dimensional electrophoresis\u201d,50.\u201d\u201cBriefly, IPG strips  were passively equilibrated under mineral oil for 18\u00a0h at 23\u00a0\u00b0C with 90\u00a0\u00b5g of solubilized protein in 200\u00a0\u00b5l STnow reads:50.\u201d\u201cBriefly, IPG strips  were passively equilibrated under mineral oil for 18\u00a0h at 23\u00a0\u00b0C with 90\u00a0\u00b5g of solubilized protein in 200\u00a0\u00b5l STUnder the subheading \u201cNeurosphere culture from adult brain SVZ\u201d,\u201c3\u00a0ml of Trypsin inhibitor (from glycine max) was added and gently mixed and the tissue suspension was passed through 0.7\u00a0\u03bcm pore size filter followed by centrifuge at 700\u00a0rpm for 5\u00a0min. The supernatant was removed and the pellet was resuspended in the NSC culture media .\u201dnow reads:\u201c3\u00a0ml of Trypsin inhibitor (from glycine max) was added and gently mixed and the tissue suspension was passed through 70\u00a0\u03bcm pore size filter followed by centrifuge at 700\u00a0rpm for 5\u00a0min. The supernatant was removed and the pellet was resuspended in the NSC culture media .\u201dUnder the subheading, \u201cHuman brain organoids and hNPCs\u201d,\u201cSpecifically, iPSCs colonies were first dissociated into single cells (D0) with Accutase (SIGMA-ALDRICH) and 1.5 million cells seeded per well of an AggreWell00 plate (STEM CELL TECHNOLOGIES) in a medium containing KnockOut DMEM, 20% KnockOut Serum Replacement, 1% penicillin and streptomycin (P/S) solution, 0.5X GlutaMAX, 1\u00d7 MEM Non-Essential Amino Acids , 5\u00a0\u00b5M Dorsomorphin (PEPROTECH), 10\u00a0\u00b5M SB431542 (PEPROTECH), 100\u00a0\u00b5M 2-Mercaptoethanol (SIGMA), and 10\u00a0\u00b5M Y-27632 (TOCRIS).\u201dnow reads:\u201cSpecifically, iPSCs colonies were first dissociated into single cells (D0) with Accutase (SIGMA-ALDRICH) and 1.5 million cells seeded per well of an AggreWell800 plate (STEM CELL TECHNOLOGIES) in a medium containing KnockOut DMEM, 20% KnockOut Serum Replacement, 1% penicillin and streptomycin (P/S) solution, 0.5X GlutaMAX, 1\u00d7 MEM Non-Essential Amino Acids , 5\u00a0\u00b5M Dorsomorphin (PEPROTECH), 10\u00a0\u00b5M SB431542 (PEPROTECH), 100\u00a0\u00b5M 2-Mercaptoethanol (SIGMA), and 10\u00a0\u00b5M Y-27632 (TOCRIS).\u201dLastly, Reference 11 was incorrectly given as:Front. Biol. (Beijing)\u00a011, 151\u2013167 (2016).Semerci, F. & Maleic-Savatic, M. Transgenic mouse models for studying adult neurogenesis.\u00a0The correct reference is listed below:Front. Biol. (Beijing)\u00a011, 151\u2013167 (2016).Semerci, F. & Maletic-Savatic, M. Transgenic mouse models for studying adult neurogenesis.\u00a0The original Article has been corrected."}
{"text": "The title mol\u00adecule adopts a conformation with the two phenyl substituents disposed on opposite sides of the mean plane of the iso\u00adquinoline unit. In the crystal, corrugated layers of mol\u00adecules are formed by N\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) inter\u00adactions. These layers are connected by C\u2014H\u22efO contacts. 29H29N3O4S, adopts a conformation with the two phenyl substituents disposed on opposite sides of the mean plane of the iso\u00adquinoline unit. In the crystal, corrugated layers of mol\u00adecules are formed by N\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22efS hydrogen bonds together with C\u2014H\u22ef\u03c0(ring) inter\u00adactions. These layers are connected by C\u2014H\u22efO contacts. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (45.2%), C\u22efH/H\u22efC (20.2%), O\u22efH/H\u22efO (15.8%) and N\u22efH/H\u22efN (11.0%) inter\u00adactions.The title mol\u00adecule, C In AKIVUO, a layer structure with the layers parallel to . In POPYEB, mol\u00adecules are packed in a herringbone manner parallel to (103) and (10via weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) inter\u00adactions. In ENOCIU, various C\u2014H\u22ef\u03c0 and C\u2014H\u22efO bonds link the mol\u00adecules together. In NIWPAL, the mol\u00adecules are linked by N\u2014H\u22efO inter\u00admolecular hydrogen bonds involving the sulfonamide function to form an infinite two-dimensional network parallel to (001).In the crystal of NAQRIJ, dimers are formed through complementary sets of inversion-related O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, which are further connected into zigzag chains by pairwise C\u2014H\u22efN inter\u00adactions that also form inversion dimers. In KUGLIK, the heterocyclic amines are alternately connected by hydrogen bonds thus forming syndiotactic polymeric chains. The hydrogen-bonding network of water mol\u00adecules forms planes parallel to (100). In the crystal of DUSVIZ, mol\u00adecules are linked H)-thione (10\u2005mmol), N-(phen\u00adyl)-2-chloro\u00adacetamide (10\u2005mmol) and sodium acetate trihydrate  in ethanol (100\u2005ml) was heated under reflux for 1\u2005h. The reaction mixture was allowed to stand at room temperature overnight. The precipitate that formed was collected and recrystallized from ethanol giving colourless crystals of the title compound, m.p.: 508\u2013510\u2005K, yield 84%. Its IR spectrum showed characteristic absorption bands at 3474\u2005cm\u22121 (OH); 3311\u2005cm\u22121 (NH); 3023\u2005cm\u22121 (C-H aromatic); 2910, 2956\u2005cm\u22121 ; 1800, 1900\u2005cm\u22121 (overtones of phenyl group); 2220\u2005cm\u22121 (C\u2261N) and 1694\u2005cm\u22121 (C=O). Its 1H NMR  spectrum exhibited the following signals: \u03b4 10.21 , 7.48\u20137.49 ; 7.22\u20137.25 ; 6.97\u20137.00 ; 6.89\u20136.91 ; 6.75\u20136.77 ; 4.84 ; 4.41\u20134.43 ; 4.04\u20134.11 ; 3.66 ; 3.20\u20133.24 ; 2.83\u20132.85 ; 2.81\u20132.84 ; 2.08 ; 1.86  and 1.21 .A mixture of 7-acetyl-4-cyano-1,6-dimethyl-6-hy\u00addroxy-8-(4-meth\u00adoxy\u00adphen\u00adyl)-5,6,7,8-tetra\u00adhydro\u00adiso\u00adquinoline-3 I, global. DOI: 10.1107/S2056989021005430/yk2151Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021005430/yk2151Isup3.cmlSupporting information file. DOI: 2085564CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Three crystal structures from the reaction of 2,6-di\u00admethyl\u00adphenyl isocyanide with bis\u00ad(anthracene)ferrate(\u22121) are presented. 2]1+ (thf is tetra\u00adhydro\u00adfuran) salt of bis\u00ad(anthracene)ferrate(\u22121), or [Fe(C14H10)2]\u2212, with 2,6-di\u00admethyl\u00adphenyl isocyan\u00adide (CNX\u00adyl) in thf resulted in the formation of two new iron isocyanide complexes, namely, [-anthracene]tris\u00adiron, [Fe(C14H10)(C9H9N)3] or [Fe(CNX\u00adyl)3], and {5,6-bis\u00ad-3--1,2,7-tris\u00ad[imino]-3-azoniahept-3-ene-1,4,7-triido}tris\u00adiron tetra\u00adhydro\u00adfuran disolvate, [Fe(C54H56N6)(C9H9N)3]\u00b72C4H8O or [Fe(C54H56N6)(CNX\u00adyl)3]\u00b72C4H8O, which were characterized by single-crystal X-ray diffraction. The former is likely an inter\u00admediate along the path to the known homoleptic [Fe(CNX\u00adyl)5], while the latter contains a tridentate ligand that is formed from the \u2018coupling\u2019 of six CNXyl ligands. A third crystal structure from this reaction, (7-methyl\u00adindol-1-ido-\u03baN)potassium, [K(C9H8N)(C12H24O6)] or [K(C9H8N)(18-crown-6)], contains a 7-methyl\u00adindol-1-ide anion, in which one CNXyl ligand has shed a proton during its reductive cyclization.The reaction of the [K(18-crown-6)(thf) On this basis, the corresponding reaction with CNXyl in tetra\u00adhydro\u00adfuran, thf, was examined to determine whether the unknown [Fe2(CNX\u00adyl)8]2\u2212 could be accessed. Bis(anthracene)ferrate(\u22121) was also reacted with excess CNXyl in the presence of one equivalent of a reducing agent to see whether the previously reported monometallic [Fe(CNX\u00adyl)4]2\u2212 5] cobaltate(\u22121) has been shown to be an excellent source of spin-paired atomic Co(\u22121) anions in substitution reactions in which both anthracene ferrate(\u22121) with excess CNXyl in THF. First an aliquot was taken from the reaction mixture early on and placed in a 243\u2005K freezer until orange blocks were observed. A single crystal X-ray diffraction experiment revealed these to be [Fe(C14H10)(CNX\u00adyl)3] 1 iron(0). However, the related carbonyl, [Fe(C14H10)(CO)3], has been known for more than 50 years (CNX\u00adyl)3] 2 6X]+ (many variations on R and X) by Zn in the presence of water generated a bis\u00adacetyl\u00adene ligand with protonated nitro\u00adgen atoms (C9H8N)] 3 ]. The hydrogen atom lost during the reduction and cyclization that forms e.g., four), intra\u00adctable tars resulted. It should be noted, however, that this equation is only speculative and requires further investigation for confirmation.Inter\u00adestingly, in support of this equation, when less than eight equivalents of CNXyl were employed (Equation (1)2][Fe(C14H10)2] + 8 CNXyl \u2192 0.5 [Fe(CNX\u00adyl)5] + 0.5 [Fe(C54H56N6)(CNX\u00adyl)3] + [K(18-crown-6)(C9H8N)] portion of a trinuclear mol\u00adecule, 97.5\u00b0 3], 97.7\u00b0 3], 97.9\u00b0  bond lengths  \u03c0\u2013\u03c0 inter\u00adactions  \u03c0\u2013\u03c0 inter\u00adaction between phenyl rings C56\u2013C61 and C65\u2013C70 [Fe(C14H10)2] and CNXyl were prepared according to previously reported procedures 2]  in thf  was added CNXyl  in thf . The reaction mixture was warmed slowly to room temperature. A solution IR spectrum showed no anionic species, but a broad peak with shoulders that matched the well-known [Fe(CNX\u00adyl)5]  were identified as 2 by X-ray diffraction. IR spectroscopy on the crystals (Nujol mull) gave \u03bdCN = 2110w and 2055vs cm\u22121. The filter cake  was redissolved in THF and layered with pentane, which resulted in crystals of 3 as determined by a single crystal X-ray experiment. No characterization beyond what is presented above was performed.To a deep-orange solution of . The 18-crown-6 macrocycle is also disordered in a similarly lopsided component ratio; the eight largest residual peaks are the two peaks near the K atom and those for six O atoms of the minor component of disorder. However, the data-to-parameter ratio drops below eight if this disorder is modeled. Thus only the anion disorder was modeled.In 2, bond lengths were restrained toward ideal values and anisotropic displacement parameters were additionally restrained toward the expected motion relative to bond direction.To model the various disordered species, analogous bond lengths and angles were restrained to be similar and anisotropic displacement parameters for proximal atoms were restrained to be similar. For the THF solvent mol\u00adecules in 1 were refined freely to confirm their nature and better describe their true positions. In 2, H7 was also refined freely. All other H atoms were placed geometrically and treated as riding atoms. For 1 and 3 (173\u2005K), methyl\u00adene, C\u2014H = 0.99\u2005\u00c5, aromatic/sp2, C\u2014H = 0.95\u2005\u00c5, with Uiso(H) = 1.2Ueq(C), and methyl, C\u2014H = 0.98\u2005\u00c5, with Uiso(H) = 1.5Ueq(C). For 2 (293\u2005K), methyl\u00adene, C\u2014H = 0.97\u2005\u00c5, aromatic/sp2, C\u2014H = 0.93\u2005\u00c5, N\u2014H = 0.86\u2005\u00c5, with Uiso(H) = 1.2Ueq(C), and methyl, C\u2014H = 0.96\u2005\u00c5, with Uiso(H) = 1.5Ueq(C).The H atoms on the metal-coordinating carbon atoms (C1\u2013C4) of 1 the maximum residual peak of 0.36\u2005e\u2212 \u00c5\u22123 and the deepest hole of \u22120.35\u2005e\u2212 \u00c5\u22123 are found 0.97 and 0.53\u2005\u00c5 from atoms C2 and Fe1, respectively.For 2 the maximum residual peak of 0.38\u2005e\u2212 \u00c5\u22123 and the deepest hole of \u22120.18\u2005e\u2212 \u00c5\u22123 are found 0.81 and 0.39\u2005\u00c5 from atoms H15 and C14, respectively.For 3 the maximum residual peak of 0.58\u2005e\u2212 \u00c5\u22123 and the deepest hole of \u22120.23\u2005e\u2212 \u00c5\u22123 are found 1.15 and 1.25\u2005\u00c5 from atoms C15 and K1, respectively. The peak is part of the minor component of disorder of the 18-crown-6 ring, which was not modeled (see above).For 10.1107/S205698902101313X/yz2014sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S205698902101313X/yz20141sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698902101313X/yz20142sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S205698902101313X/yz20143sup4.hklStructure factors: contains datablock(s) 3. DOI: 2127598, 2127597, 2127596CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-021-85972-2, published online 22 March 2021Correction to: The original version of this Article contained an error in Figure\u00a03 where the labels in panel D were incorrect. As a result,\u201cmg/ml\u201dnow reads:\u201cmg/kg\u201dAdditionally,\u201c\u03bcg/ml\u201dnow reads:\u201cmg/kg\u201dFurthermore, in the legend of Figure 3,A) 20\u00a0\u03bcm; in (B) 50\u00a0\u03bcm\u201d\u201cScale bar in (now reads:B) 20\u00a0\u03bcm; in (D) 50\u00a0\u03bcm\u201d\u201cScale bar in (The original Figure"}
{"text": "Intracerebral hemorrhage (ICH) can induce intensively oxidative stress, neuroinflammation, and brain cell apoptosis. However, currently, there is no highly effective treatment available. Puerarin (PUE) possesses excellent neuroprotective effects by suppressing the NF\u2010\u03baB pathway and activating the PI3K/Akt signal, but its role and related mechanisms in ICH\u2010induced early brain injury (EBI) remain unclear. In this study, we intended to observe the effects of PUE and molecular mechanisms on ICH\u2010induced EBI. ICH was induced in rats by collagenase IV injection. PUE was intraperitoneally administrated alone or with simultaneously intracerebroventricular injection of LY294002 . Neurological deficiency, histological impairment, brain edema, hematoma volume, blood\u2013brain barrier destruction, and brain cell apoptosis were evaluated. Western blot, immunohistochemistry staining, reactive oxygen species (ROS) measurement, and enzyme\u2010linked immunosorbent assay were performed. PUE administration at 50\u00a0mg/kg and 100\u00a0mg/kg could significantly reduce ICH\u2010induced neurological deficits and EBI. Moreover, PUE could notably restrain ICH\u2010induced upregulation of the NF\u2010\u03baB pathway, pro\u2010inflammatory cytokines, ROS level, and apoptotic pathway and activate the PI3K/Akt signal. However, LY294002 delivery could efficaciously weaken these neuroprotective effects of PUE. Overall, PUE could attenuate ICH\u2010induced behavioral defects and EBI possibly by PI3K/Akt signal stimulation\u2010mediated inhibition of the NF\u2010\u03baB pathway, and this made PUE a potential candidate as a promising therapeutic option for ICH\u2010induced EBI. The research protocol and animal care were authorized by the Southern Medical University Ethics Committee and were performed according to the National Institutes of Health guidelines on care and use of animals.2.2Supplementary materials, respectively   solution of PUE  (100\u00a0mg/ml) was prepared. The rats were injected intraperitoneally with either PUE at 50\u00a0mg/kg and 100\u00a0mg/kg, or just DMSO solution 30\u00a0min before modeling and at the time points of 30\u00a0min, 6\u00a0h, 12\u00a0h, 24\u00a0h, and 48\u00a0h after ICH. We selected the dosages and administration route based on previous studies, and intraperitoneal injection of PUE at 50\u00a0mg/kg and 100\u00a0mg/kg could both produce significantly neuroprotective effects.2.5The modified neurological severity score (mNSS) scale was applied to estimate the neurobehavioral deficiency at 24\u00a0h and 72\u00a0h following ICH, which was executed by two experienced researchers who were blinded to animal groups.2.6Paraffin sections of rat brains were made, as previously described.2.7H&E staining was performed as our previous method.2.8V\u00a0=\u00a0T1*S1\u00a0+\u00a0T2*S2 + \u2026 + Tn*Sn .Hematoma volume was assessed as previously reported with some modifications.2.9M1\u2212M2)]/M1*100% .Brain water content (BWC) was measured by the wet/dry weight method, as previously described.2.10Evans blue (EB) dye  was applied to assess the disruption of the blood\u2013brain barrier (BBB), as reported previously.2.11+ cells were counted in a blinded manner.At 24\u00a0h and 72\u00a0h after ICH, the brain samples were obtained and paraffin sections were prepared. TUNEL staining was performed with an In Situ Cell Death Detection Kit  as our previous method.2.122O2 for 10\u00a0min and antigen blocking with 5% bovine serum albumin for 20\u00a0min, the samples underwent overnighted co\u2010incubation at 4\u00b0C with the following primary antibodies: cleaved caspase\u20103 , Ser536p\u2010NF\u2010\u03baB p65 , NF\u2010\u03baB p65  , 3\u2010nitrotyrosine (3\u2010NT) , and 8\u2010hydroxyguanosine (8\u2010OHdG) . Then, the brain slices were orderly incubated with corresponding secondary antibodies and horseradish peroxidase\u2013streptavidin for 20\u00a0min. After further reaction with 3, 3\u2010diaminobenzidine and being counterstained with hematoxylin, representative IHC images were obtained using a microscope .IHC staining was performed as previously reported.2.13Ser536p\u2010NF\u2010\u03baB p65 (Cat. No.: #3033), NF\u2010\u03baB p65 (Cat. No.: #8242), Ser473p\u2010Akt (Cat. No.: #4060), Akt (Cat. No.: #9272), Bax (Cat. No.: #2772), cleaved caspase\u20103 (Cat. No.: #9664) , Bcl\u20102 , Tyr607p\u2010PI3K , and PI3K . \u03b2\u2010actin  and Lamin A  were employed as the internal reference. WB protein bands were quantified by ImageJ software . Protein expression levels were indicated by the ratio of interest protein bands to that of \u03b2\u2010actin or Lamin A bands.Western blot (WB) was carried out as our previous method.2.14At 24\u00a0h after ICH, the brain samples were collected and used to detect pro\u2010inflammatory cytokine levels using a Rat TNF\u2010\u03b1 ELISA Kit (Cat. No.: SEA133Ra), Rat IL\u20101\u03b2 ELISA Kit (Cat. No.: SEA563Ra), and Rat IL\u20106 ELISA Kit (Cat. No.: SEA079Ra)  as our previous method.2.15The reactive oxygen species (ROS) level was detected using a ROS assay kit  at 24\u00a0h after ICH.2.16P\u2010value was statistically significant when <0.05.All data were expressed as means\u00a0\u00b1\u00a0standard deviation (SD). Data analyses were conducted with SPSS 19.0 , and related diagrams were prepared with GraphPad Prism 5 . All data were analyzed using the Shapiro\u2013Wilk and Levene tests. If data satisfy normal distribution and homogeneity of variance, one\u2010way analysis of variance (ANOVA) was considered, and then the least significant difference (LSD) test was applied to compare the difference among multiple experimental groups; conversely, for unsatisfied data, Dunnett's T3 test was adopted. The 33.1P\u00a0<\u00a0.001) and 72\u00a0h (P\u00a0<\u00a0.001)  and 100\u00a0mg/kg , yet the beneficial effects of two treatment dosages were not significantly different  . The schedule of research, including ICH induction of rats, treatments with different agents , and corresponding experimental assessments, is shown Fig. . The mNS) Figure\u00a0 after IC) Figure\u00a0. Analogo) Figure\u00a0 and 72\u00a0h) Figure\u00a0 followin3.2P\u00a0<\u00a0.001, 24\u00a0h; P\u00a0<\u00a0.01, 72\u00a0h)  and 100\u00a0mg/kg  could significantly reduce an ICH\u2010induced increase in BWC   . Besides, PUE (100\u00a0mg/kg) also could notably repress ICH\u2010induced EB dye extravasation    Figure\u00a0. Extrava) Figure\u00a0, and PUE) Figure\u00a0. Similar) Figure\u00a0.3.3P\u00a0<.001, 24\u00a0h and 72\u00a0h)  and 100\u00a0mg/kg  could markedly reduce the ICH\u2010induced increase in TUNEL+ cells. However, the effects of PUE at 50\u00a0mg/kg and 100\u00a0mg/kg had no statistical difference    after ICH   Figure\u00a0. Treatme) Figure\u00a0. Typical) Figure\u00a0. PUE cou) Figure\u00a0. BesidesH Figure\u00a0. Consist) Figure\u00a0.3.4P\u00a0<\u00a0.001), p\u2010NF\u2010\u03baB p65 (P\u00a0<\u00a0.05), and nuclear NF\u2010\u03baB p65 (P\u00a0<\u00a0.05)       Figure\u00a0,E,G,H, a) Figure\u00a0 at 24\u00a0h ) Figure\u00a0. Similar) Figure\u00a0, p\u2010NF\u2010\u03baB) Figure\u00a0, and nuc) Figure\u00a0 and sign) Figure\u00a0.3.5P\u00a0<\u00a0.001)  at 24\u00a0h after ICH   at 24\u00a0h following ICH as well   could significantly upregulate the expression levels of PI3K  Figure\u00a0 and p\u2010AkH Figure\u00a0. Similar) Figure\u00a0 and p\u2010Akl Figure\u00a0. However) Figure\u00a0.3.6P\u00a0<.001) and 100\u00a0mg/kg (P\u00a0<\u00a0.001) could significantly increase the expression level of Bcl\u20102 at 24\u00a0h after ICH  and that of cleaved caspase\u20103  at 24\u00a0h following ICH  are shown Figure\u00a0. The resH Figure\u00a0. MoreoveH Figure\u00a0. TypicalH Figure\u00a0.3.7+ and 8\u2010OHdG+ cells are shown        Figure\u00a0 and 8\u2010OH) Figure\u00a0. Moreove) Figure\u00a0, and PUE) Figure\u00a0 and 100\u00a0) Figure\u00a0, yet the) Figure\u00a0.3.8P\u00a0<\u00a0.001)         notably increased  Figure\u00a0,H, and P) Figure\u00a0, IL\u20101\u03b2  Figure\u00a0, and IL\u2010) Figure\u00a0. Similar) Figure\u00a0, IL\u20101\u03b2  Figure\u00a0, and IL\u2010) Figure\u00a0 were all) Figure\u00a0,H.3.9P\u00a0<\u00a0.05)   was used to ulteriorly explore the protective mechanisms of PUE in ICH\u2010induced EBI, and the acquired results indicated that LY294002 could markedly weaken the beneficial effects of PUE on ICH\u2010induced behavioral deficiency indicated by increasing the mNSS scores  Figure\u00a0 and BBB ) Figure\u00a0 at 24\u00a0h 3.10P\u00a0<\u00a0.05)      Figure\u00a0, and p\u2010A) Figure\u00a0 proteins) Figure\u00a0 and p\u2010NF) Figure\u00a0 at 24\u00a0h 4Increasing evidence has shown that OS and neuroinflammation are incredibly crucial for ICH\u2010induced EBI, which is characterized by massive brain cell apoptosis.Research studies have confirmed that activation of NFthe \u2010\u03baB signal pathway widely exists in various kinds of CNS damages, including ischemic stroke,Stimulation of the PI3K/Akt signal has also been reported by different groups that it could notably mitigate acute CNS disorder\u2010induced brain injury, including ICH 21H20O9], chemical structure \u20107\u2010hydroxy\u20103\u2010(4\u2010hydroxyphenyl)\u20104H\u20101\u2010benzopyran\u20104\u2010one, Ce Figure\u00a0, belongsPuerarin is also well\u2010confirmed to produce various beneficial effects by activation of the PI3K/Akt signal pathway. A recent report has exhibited that PUE could ameliorate OS\u2010induced neurodegeneration by stimulating the PI3K/Akt signal after TBI, and the specific inhibitor of the PI3K/Akt signaling pathway LY294002 could markedly reduce PUE\u2019s protective effects.Research studies have suggested that the PI3K/Akt signal is the powerful upstream regulator of the NF\u2010\u03baB pathway.Some potential limitations deserve special attention in our study. First, PUE can generate multiple beneficial effects by manipulation of different signal pathways, but we primarily focused on PI3K/Akt signal activation\u2010mediated suppression of the NF\u2010\u03baB pathway. Hence, PUE may exert neuroprotective effects by other signal pathways such as the Nrf2 signaling pathway Overall, our results have indicated that PUE could notably improve ICH\u2010induced EBI and neurological deficiency, and related mechanisms might be involved in the suppression of NF\u2010\u03baB signal pathway activation\u2010induced brain injury partly by the triggering of PI3K/Akt signal pathway\u2010mediated neuroprotection. Our findings might provide a promising therapeutic selection for ICH\u2010induced EBI.All authors listed in this manuscript declared that no any conflicts of interest existed.Jun Zeng: Conceptualization ; Data curation ; Formal analysis ; Investigation ; Methodology ; Software ; Validation ; Visualization ; Writing\u2010original draft . Shizhong Zheng: Conceptualization ; Data curation ; Formal analysis ; Investigation ; Methodology ; Software ; Validation ; Visualization ; Writing\u2010original draft . Yizhao Chen: Conceptualization ; Data curation ; Funding acquisition (lead); Project administration (lead); Resources (lead); Supervision (lead); Writing\u2010review & editing (lead). Yaoming Qu: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Jiayu Xie: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Enhui Hong: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Hongzhu Lv: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Rui Ding: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Liang Feng: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting). Zhichong Xie: Formal analysis (supporting); Investigation (supporting); Methodology (supporting); Software (supporting); Visualization (supporting); Writing\u2010review & editing (supporting).Fig. S1.Click here for additional data file.Fig. S2.Click here for additional data file.Fig. S3.Click here for additional data file.Fig. S4.Click here for additional data file.Fig. S5.Click here for additional data file.Fig. S6.Click here for additional data file.Supplementary MaterialClick here for additional data file."}
{"text": "II atom has a distorted square-pyramidal coordination environment. The mol\u00adecular structure exhibits an intra\u00admolecular O\u2014H\u22efN hydrogen bond. In the crystal, the mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efBr hydrogen bonds, generating ribbon structures. These ribbons are linked though inter\u00admolecular C\u2014H\u22efBr hydrogen bonds, forming a two-dimensional network sheet.In the title compound, the Zn 2(C22H19ClN4O)], the ZnII atom adopts a distorted square-pyramidal coordination geometry, formed by two bromido ligands and three N atoms of the bis\u00ad(pyridin-2-ylmeth\u00adyl)amine moiety in the penta\u00addentate ligand containing quinolinol. The ZnII atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a Br atom. The O and N atoms of the quinolinol moiety in the ligand are not coordinated to the ZnII atom. An intra\u00admolecular O\u2014H\u22efN hydrogen bond, generating an S(5) ring motif, stabilizes the mol\u00adecular structure. In the crystal, the mol\u00adecules are linked by inter\u00admolecular C\u2014H\u22efBr hydrogen bonds, generating ribbon structures containing alternating R22(22) and R22(14) rings. These ribbons are linked through an inter\u00admolecular C\u2014H\u22efBr hydrogen bond, forming a two-dimensional network sheet.In the title compound, [ZnBr Its derivatives are utilized as chemosensors for detecting ZnII at low concentration in biological samples  bromide. Here, the crystal structure of the respective title compound is reported.8-Quinolinol (Hq) is a notable bidentate ligand and an excellent analytical reagent for the determination of the concentration and separation of metal ions  and three N atoms  of the dpa moiety in HClqdpa forming the ZnBr2(dpa) unit. The Hq moiety of the penta\u00addentate ligand (HClqdpa) is not coordinated to the ZnII center. The five-coordinate geometry parameter, \u03c4 = (\u03b2\u00a0\u2212\u00a0\u03b1)/60, derived from the two largest angles (\u03b1 < \u03b2) in a structure has ideal values of 0 for square-pyramidal and of 1 for trigonal\u2013bipyramidal geometry \u2005\u00c5 above the mean basal plane (Br2/N8/N7/N9) of the square-based pyramid. The dpa moiety is meridionally bound to the ZnII atom. The apical position is occupied by the Br1 atom with the apical bond being slightly elongated to 2.4419\u2005(4)\u2005\u00c5 compared to the equatorial Br2\u2014Zn3 bond length of 2.4085\u2005(4)\u2005\u00c5. The Zn\u2014N bond lengths in the title compound are 2.1455\u2005(18) and 2.1497\u2005(18)\u2005\u00c5 for the pyridyl atoms , and 2.2670\u2005(18)\u2005\u00c5 for the tertiary atom N7. In comparison, the Zn\u2014N bond lengths in the crystal structure of a related complex with a mesityl methyl\u00adene-appended dpa derivative are 2.093\u2005(3), 2.066\u2005(3), and 2.521\u2005(3)\u2005\u00c5  ring motif  1\u00a0\u2212\u00a0x, \u2212y, \u2212z]  1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]  x\u00a0+\u00a01, y\u00a0\u2212\u00a01, z] (Table\u00a01C(6) chain motif running along  Table\u00a01, forming] Table\u00a01, which ffs Fig.\u00a02. In the ] Table\u00a01, forming0] Fig.\u00a03. The rib] Fig.\u00a03.et al., 2016ConQuest amino]\u00admethyl fragment as ligand gave 517 hits, and among those, eight hits with two bromido ligands. Of these eight analogues, three structures are complexes with dpa bearing a tertiary N donor atom directly bound to an aromatic moiety , the tertiary N atoms are bound to aliphatic carbon atoms as in the title complex. Four of these five closely related structures exhibit square-pyramidal geometries with dpa being meridionally coordinated meth\u00adyl]propan-2-amine}\u00addibromido\u00adzinc(II) . Of these, six structures (three compounds) are ion-pairs between tetra\u00adchlorido\u00adzincate(II) and an 8-hy\u00addroxy\u00adquinolin-1-ium (H2q+) derivative, for example, (H2q)2[ZnCl4]  and quinolin-8-lato derivatives, e.g. 8-hy\u00addroxy-2-methyl\u00adquinolino\u00adlinium di\u00adiodo\u00ad(2-methyl\u00aduinolin-8-lato)zinc(II)  tris\u00ad(4-nitro\u00adphenol) bis\u00adzinc(II) dihydrate zinc(II) trihydrate amino]\u00admethyl at the 2-position of Hq or respective derivatives, gave three hits  was dissolved in 15\u2005mL of hot aceto\u00adnitrile. Then a solution of zinc(II) bromide  in 15\u2005mL of hot aceto\u00adnitrile was added to the ligand solution. The mixture was stirred for 20\u2005min at 333\u2005K. After removal of the solvent at room temperature in air for one week, colorless crystals of the title compound were obtained . Analysis calculated for CUiso(H) = 1.2Ueq(C). One outlier reflex (002) was omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989022001530/yz2016sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989022001530/yz2016Isup2.hklStructure factors: contains datablock(s) I. DOI: 2150991CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Heterodera microulae sp. n., was isolated from the roots and rhizosphere soil of Microula sikkimensis in China. Morphologically, the new species is characterized by lemon-shaped body with an extruded neck and obtuse vulval cone. The vulval cone of the new species appeared to be ambifenestrate without bullae and a weak underbridge. The second-stage juveniles have a longer body length with four lateral lines, strong stylets with rounded and flat stylet knobs, tail with a comparatively longer hyaline area, and a sharp terminus. The phylogenetic analyses based on ITS-rDNA, D2-D3 of 28S rDNA, and COI sequences revealed that the new species formed a separate clade from other Heterodera species in Goettingiana group, which further support the unique status of H.\u00a0microulae sp. n. Therefore, it is described herein as a new species of genus Heterodera; additionally, the present study provided the first record of Goettingiana group in Gansu Province, China.A new cyst-forming nematode,  Heterodera was erected by Schmidt (1871) and currently contains about 80 species  units are good candidate genes for molecular taxonomic and phylogenetic studies  were recovered from hatched eggs and kept in water suspension until further use  and AB28 (5\u2032-ATATGCTTAAGTTCAGCGGGT-3\u2032) (COI gene was amplified using primers Het-coxiF (5\u2032-TAGTTGATCGTAATTTTAATGG-3\u2032) and Het-coxiR (5\u2032-CCTAAAACATAATGAAAATGWGC-3\u2032) . Three sets of primers  were used in the PCR analyses to amplify sequences of the ITS, D2-D3 expansion segments of 28S, and GGGT-3\u2032) . The 28SGGGT-3\u2032) . FinallyGWGC-3\u2032) . PCR conCOI gene) were compared with known sequences of Heterodera using BLASTn homology search program. Outgroup taxa for phylogenetic analyses were selected based on the previously published studies (http://tree.bio.ed.ac.uk/software/figtree/)  . The speHeterodera microulae sp. n. It is lemon-shaped with an obtuse vulval cone, neck extruding, and cuticle thick with an irregular zig-zag pattern. The color was white to pale to medium brown; remnants of the subcrystalline layer were rarely present. The egg sac was usually absent , 3B, C. The female was lemon-shaped, pearl white, or pale yellow in color. It was rarely rounded with a protruding neck and vulva, the subcrystalline layer was present, and the egg sac absent . There wThe body was straight or slightly curved ventrally after heat treatment . The lipBody hyaline without any markings was presented; juveniles folded six times .The male was not found.Holotype and paratype material  were deposited in the nematode collection of the Department of Plant Protection, Biocontrol Engineering Laboratory of Crop Diseases and Pests of Gansu Province, Lanzhou, China.Heterodera microulae sp. n. was collected from the roots and rhizosphere soil of Microula sikkimensis Hemsl.  in Tianzhu county of Gansu Province, China. The geographical position is N 37\u00b011\u203246\u2033; E 102\u00b047\u20326\u2033. This site was located in continental highland with the vegetation type of meadow grassland and the soil is composed of chernozems. The climatic parameters of the site include 450\u2009mm of average rainfall and an approximate \u22122 air temperature.The species is named after the host of its isolation.Heterodera microulae sp. n. is characterized by having lemon-shaped cysts that have protruding necks and obtuse vulval cones. The cysts are 414 to 543-\u00b5m long and 305 to 456-\u00b5m wide having ambifenestrate vulval cone and bullae are absent. Females are white in color with a subcrystalline layer. Second-stage juveniles are straight or slightly curved ventrally with four incisures in the lateral field. The juveniles are 506 to 628-\u00b5m long having strong stylets with well-developed rounded stylet knobs, genital primordium situated at 59 to 62% of body length, and tail 49 to 61-\u00b5m long with a hyaline portion of 24 to 33\u2009\u00b5m. Eggs are hyaline without any markings; juveniles inside the eggs form sixfold.Goettingiana group of Heterodera; currently, the group contains seven valid species, viz, Heterodera goettingiana , absence of bullae (vs few), weak underbridge (vs 117\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 486\u2009\u00b5m), stylet knobs rounded and flat or slightly concave anteriorly vs smoothly rounded to slightly hook-shaped with a recurved anterior surface, longer distance of median bulb from the anterior end (MB) (86\u2009\u00b5m vs 70\u2009\u00b5m), shorter excretory pore distance from the anterior end (114\u2009\u00b5m vs 158\u2009\u00b5m), and shorter length of hyaline tail portion (29\u2009\u00b5m vs 37\u2009\u00b5m).The new species differs from H. carotae by having a bigger size of cysts (495\u2009\u00d7\u2009384\u2009\u00b5m vs 408\u2009\u00d7\u2009309\u2009\u00b5m), shorter vulval slit length (39\u2009\u00b5m vs 47\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 422\u2009\u00b5m), stylet knobs rounded and flat or slightly concave anteriorly vs concave anterior face, higher MB value (86\u2009\u00b5m vs 66\u2009\u00b5m), longer excretory pore distance from the anterior end (114\u2009\u00b5m vs 99\u2009\u00b5m), and longer tail length (57\u2009\u00b5m vs 52\u2009\u00b5m).The new species is differentiated from H. cruciferae by having a bigger size of cysts (495\u2009\u00d7\u2009384\u2009\u00b5m vs 429\u2009\u00d7\u2009333\u2009\u00b5m), slightly shorter fenestral length (31\u2009\u00b5m vs 34\u2009\u00b5m), shorter vulval length (39\u2009\u00b5m vs 45\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 431\u2009\u00b5m), higher MB value (86\u2009\u00b5m vs 68\u2009\u00b5m), longer excretory pore distance from the anterior end (114\u2009\u00b5m vs 101\u2009\u00b5m), longer tail length (57\u2009\u00b5m vs 50\u2009\u00b5m), and longer length of hyaline tail portion (29\u2009\u00b5m vs 25\u2009\u00b5m).The new species differs from H. persica by a shorter fenestral length (31\u2009\u00b5m vs 47\u2009\u00b5m), absence of bullae (vs present), shorter vulval slit length (39\u2009\u00b5m vs 49\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 440\u2009\u00b5m), stylet knobs , longer stylet (26\u2009\u00b5m vs 23\u2009\u00b5m), higher MB value (86\u2009\u00b5m vs 70\u2009\u00b5m), longer excretory pore distance from the anterior end (114\u2009\u00b5m vs 103\u2009\u00b5m), longer tail length (57\u2009\u00b5m vs 47\u2009\u00b5m), and longer length of hyaline tail portion (29\u2009\u00b5m vs 24\u2009\u00b5m).The new species differs from H. urticae, the new species has a smaller size of cysts (495\u2009\u00d7\u2009384\u2009\u00b5m vs 492\u2009\u00d7\u2009435\u2009\u00b5m), vulval cone obtrusive (vs unobtrusive) and absence of egg sac (vs presence), shorter fenestral length (31\u2009\u00b5m vs 38\u2009\u00b5m), shorter vulval slit length (39\u2009\u00b5m vs 46\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 541\u2009\u00b5m), shorter DGO (8\u2009\u00b5m vs 5\u2009\u00b5m), and shorter excretory pore distance from the anterior end (114\u2009\u00b5m vs 130\u2009\u00b5m).Compared with H. circeae having a smaller size of cysts (495\u2009\u00d7\u2009384\u2009\u00b5m vs 555\u2009\u00d7\u2009397\u2009\u00b5m), a shorter fenestral length (31\u2009\u00b5m vs 43\u2009\u00b5m), vulval slit length (39\u2009\u00b5m vs 48\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 434\u2009\u00b5m), stylet knobs (rounded and slightly sloping posteriorly vs rounded and flat or slightly concave anteriorly), higher MB value (86\u2009\u00b5m vs 70\u2009\u00b5m), longer excretory pore distance from the anterior end (114\u2009\u00b5m vs 101\u2009\u00b5m), longer tail length (57\u2009\u00b5m vs 52\u2009\u00b5m), and longer length of hyaline tail portion (29\u2009\u00b5m vs 26\u2009\u00b5m).The new species differs from H. scutellariae, having smaller cysts (495\u2009\u00d7\u2009384\u2009\u00b5m vs 560\u2009\u00d7\u2009424\u2009\u00b5m), by a shorter fenestral length (31\u2009\u00b5m vs 35\u2009\u00b5m), vulval slit length (39\u2009\u00b5m vs 43\u2009\u00b5m), longer J2s body length (568\u2009\u00b5m vs 408\u2009\u00b5m), higher MB value (86\u2009\u00b5m vs 62\u2009\u00b5m), longer excretory pore distance from the anterior end (114\u2009\u00b5m vs 89\u2009\u00b5m), longer tail length (57\u2009\u00b5m vs 47\u2009\u00b5m), and longer length of hyaline tail portion (29\u2009\u00b5m vs 25\u2009\u00b5m).The new species differs from H. microulae sp. n. with other valid species of Goettingiana group are listed in Additionally, comparative morphological and morphometric characters of H. microulae sp. n. sequences of D2-D3 region of 28\u2009S (734\u2009bp), ITS (993\u2009bp), and COI (415\u2009bp) gene were obtained and submitted to the GenBank.The H. microulae sp. n. showed 97.09% (19-bp difference), 97.66 to 98.49% (11-17-bp difference), 98.38% (9-bp difference), 98.62% (9-bp difference), 98.45% (11-bp difference), and 99.86 to 100% (0-1-bp difference) sequence identities with H. goettingiana (DQ328697), H. carotae (KX463292 and KX463293), H. cruciferae (KP114546), H. urticae (DQ328696), Heterodera sp. RH-2010 (GU456692) from Iran, and Heterodera sp. DP-2010 (HM560856 and HM560855) from Qinghai, China, respectively. The Bayesian phylogenetic tree of the D2-D3 of 28S gene  from Qinghai, China and forms a 100% supported clade.The D2-D3 of 28S-rRNA sequence (accession no. MT573436) of 28S gene  represenH. microulae sp. n. with other Goettingiana group species is as follows: 0.20% (2-bp difference), 0.4 to 0.5% (4-bp difference), 3.02% (29-bp difference), 5.01% (48-bp difference), 5.11% (49-bp difference), 7.45% (72-bp difference), 6.77 to 6.95% (67-68-bp difference), 6.29 to 7.25% (66-70-bp difference), and 7.41 to 8% (74-77-bp difference) for Heterodera sp. DP-2010 (HM560761), H. goettingiana , H. persica (AF498377), H. scutellariae (AY368995), H. circeae (AY368994), H. urticae (AF274412), H. carotae , H. cruciferae , and H. goettingiana , respectively. The Bayesian phylogenetic tree of the ITS gene  clustered with H. persica (AF498377), H. scutellariae (AY368994), H. circeae (AY368995), Heterodera sp. DP-2010 (HM560791), and H. goettingiana  from Qinghai, China with high-probability support (pp\u2009=\u200991%). It is also noted that sequences of H.\u00a0goettingiana  from Qinghai, China, clustered outside with other H. goettingiana  subclades and should be considered a misidentification. However, H. microulae sp. n. (MT573437) is clustered with H. sp. DP-2010 (HM560791) and H. goettingiana  from Qinghai, China, with 100% support. It is also noted that H. microulae sp. n. (MT573437) clustered with two Chinese populations of Heterodera species  with 100% support.The ITS-rDNA sequence (accession no. MT573437) divergence of ITS gene  represenCOI gene sequence of H. microulae sp. n. showed 87.21 to 89.53% (differing from 36 to 44\u2009bp), 88.19% (differing from 43\u2009bp), 88.67 to 88.92% (differing from 46 to 47\u2009bp), and 88.67 to 89.40% (differing from 44 to 47\u2009bp), sequence identities with H. goettingiana (KY129829-KY129831), H. urticae (MK093155 and MK093156), H. cruciferae (MG563230 and MG563234), and H. carotae , respectively. The Bayesian phylogenetic tree of the COI gene  and Subbotin et al. (2001) used J2\u2019s lateral field characters and host preferences to separate Heterodera species into different groups . The key morphological characters of the Goettingiana group include lemon-shaped cysts having a protruding neck, ambifenestration, and absence of bullae ; some species may have an egg sac, vulval slit length\u2009>\u200935\u2009\u00b5m, a thin vulval bridge, fenestral length (30-45\u2009\u00b5m), and a weak underbridge. There were second-stage juveniles with body length\u2009>\u2009400\u2009\u00b5m, stylet length\u2009>\u200920\u2009\u00b5m, tail length\u2009>\u200945\u2009\u00b5m, hyaline tail portion\u2009>\u200920\u2009\u00b5m, and lateral field with four lines  and H. goettingiana (HM370423 and HM370425) from Qinghai, China, formed a well-supported molecular clade with the H. microulae sp. n. Moreover, the nucleotide differences of these sequences with our new species sequences are also very low (2-4-bp difference for ITS and 0-1\u2009bp for 28S). Previously, H. goettingiana (HM370423 and HM370425) from Qinghai, China, might be a case of misidentification. Based on our phylogenetic and sequence analysis results, we regard Heterodera sp. DP-2010  and H. goettingiana (HM370423 and HM370425) as H. microulae sp. n.Phylogenetically, it is evident that Heterodera microulae sp. n. is isolated from Microula sikkimensis, it is a biennial herbaceous plant that grows in forests, meadows, and forest edges at altitudes of 2,200 to 4,700\u2009m, and it is widely distributed in South and East Asian countries  are growing in the same locality. Therefore, host-suitability tests of H. microulae sp. n. are an open research field to investigate the damage potential of this species.The present study described a new species found in the rhizosphere of"}
{"text": "The structure of the racemic form of the diuretic drug trichlorme\u00adthia\u00adzide was determined from laboratory X-ray powder diffraction data: the extended structure features an intricate combination of N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 and C\u2014Cl\u22ef\u03c0 inter\u00adactions. RS)-trichlorme\u00adthia\u00adzide , C8H8Cl3N3O4S2 (RS-TCMZ), a diuretic drug used in the treatment of oedema and hypertension, was determined from laboratory X-ray powder diffraction data using DASH [David et al. . Energy framework calculations confirm the major contribution of electrostatic inter\u00adactions (Eelec) to the total energy (Etot). A comparison with the structure of S-TCMZ is also presented.The structure of racemic ( al. 2006. J. Applelho 2018. J. Appl H-1\u03bb6,2,4-benzo\u00adthia\u00addi\u00adazine-7-sulfonamide (C8H8Cl3N3O4S2), is a diuretic drug derived from thia\u00adzide, the precursor of a classic family of diuretic compounds, discovered in the 1950s. The first approved drug of this class, chloro\u00adthia\u00adzide, was marketed under the trade name Diuril in 1958 , systematic name 6-chloro-3-(di\u00adchloro\u00admeth\u00adyl)-1,1-dioxo-3,4-di\u00adhydro-2Mogul geometry check  exhibits a conformation that could be described as distorted half-chair to distorted envelope at N3  and equatorial  conformations. The almost planar benzosulfonamide ring (ring B) makes an angle of 8.2\u2005(2)\u00b0 with the best plane through the thia\u00adzide ring. The mol\u00adecule is oriented almost parallel to the a-axis as indicated by a 3.11\u2005(8)\u00b0 angle \u00b0].The asymmetric unit contains one TCMZ mol\u00adecule Fig.\u00a01: the steS-configuration in racemic TCMZ with the mol\u00adecule of the S-enanti\u00adomer in KIKCUD. When flexibility is allowed in the superposition , the r.m.s.d. deviation is 0.070 and the maximum deviation (max. D) is 0.146\u2005\u00c5. Without flexibility, the values for r.m.s.d. and max. D are 0.785 and 2.763\u2005\u00c5, respectively . The difference between the two conformations lies in the orientation of the sulfonamide group and leads to differences in the hydrogen-bonding patterns between the two compounds as discussed below.Fig.\u00a02on Fig.\u00a02a, the rly Fig.\u00a02b. The dIntra\u00admolecular hydrogen bondsRS-TCMZ \u2005\u00c5 and a D\u2014H\u22efA angle of 106.9\u2005(5)\u00b0. A second intra\u00admolecular hydrogen bond occurs between C7\u2014H7 and O4 . The third contact, N3\u2014H3A\u22efCl3, has geometric parameters 2.767\u2005(8)\u2005\u00c5 and 102.1\u2005(5)\u00b0. The three hydrogen bonds can all be represented by the graph-set symbol S(5) .Three different intra\u00admolecular hydrogen bonds are present in MZ Fig.\u00a03b.Inter\u00admolecular hydrogen bondsRS-TCMZ is very rich and relevant geometric parameters are summarized in Table\u00a01a, an A as the donated H  alternate with a motif , occur between mol\u00adecules related by the symmetry operation \u2212x, 2\u00a0\u2212\u00a0y, \u2212z . At the same time, the original mol\u00adecule inter\u00adacts via a C\u2014Cl\u22ef\u03c0 contact of 3.761\u2005(5)\u2005\u00c5 with another mol\u00adecule related by symmetry operation 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z . The mol\u00adecules are arranged as head-to-tail dimers producing chains along [101] as depicted in Fig.\u00a05c. In contrast, in the structure of S-TCMZ only C\u2014Cl\u22ef\u03c0 inter\u00adactions are observed (Table\u00a01d = 3.456\u2005(2)\u2005\u00c5] than in RS-TCMZ.In addition, \u03c0\u2013\u03c0 and C\u2014Cl\u22ef\u03c0 inter\u00adactions , which form columns along the b-axis. These columns are further connected by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds .The structure of ns Fig.\u00a06c, whichds Fig.\u00a06d.et al., 2016S-trichlorme\u00adthia\u00adzide  shows that they correspond to the same phase. It is worth mentioning that a broader search of the CSD resulted in 100 structures related to TCMZ, among them chloro\u00adthia\u00adzide and hydro\u00adchloro\u00adthia\u00adzide, their polymorphs, derivatives, solvates, and co-crystals.A search in the Cambridge Structural Database -Trichlorme\u00adthia\u00adzide was kindly provided by Tecnoqu\u00edmicas . Based on the FT\u2013IR spectra and the quality of the preliminary diffraction patterns, the present study was carried out on the sample as it was received. Crystallization experiments in different solvents, in search of possible polymorphs, are underway in our laboratories.\u2005\u00c5, b = 8.8919\u2005(9)\u2005\u00c5, c = 9.720\u2005(2)\u2005\u00c5, \u03b1 = 91.30\u2005(1)\u00b0, \u03b2 = 106.07\u2005(2)\u00b0, \u03b3 = 97.19\u2005(1)\u00b0, V = 693.4\u2005(2)\u2005\u00c53. The de Wolf , respectively. A reduced-cell search in the CSD  using GRACE  analysis for this mol\u00adecule. The HBP analysis was carried out with supporting information.The HBP tool provides an insight into the expected intra- and inter\u00admolecular hydrogen bonds in the structures. For the analysis, the donor atoms considered were N1 (sulfonamide), N2 (secondary amine) and N3 (next to the sulfonyl group). The acceptors were Cl1 (aryl chloride), Cl2/Cl3 , N2 (secondary amine), O1/O2 (sulfonamide), and O3/O4 (sulfon\u00adyl). The area under the receiver operating characteristics (ROC) curve was 0.863, indicating good statistical discrimination in the analysis. The results of the calculations are presented in the B\u22efCl1 (0.60). This hydrogen bond is observed only in the S-enanti\u00adomer. The intra\u00admolecular inter\u00adaction involving N3\u2014H3A\u22efCl3, observed in the two structures, has the second highest propensity value (0.48).The intra\u00admolecular hydrogen bond with the highest propensity is N1\u2014H1B\u22efO3 and N1\u2014H1A\u22efO4) have the highest propensities (0.69). They are present in the structure of RS-TCMZ (motifs II and III). However, only one of them (N1\u2014H1A\u22efO4) is present in the S-enanti\u00adomer. The next two inter\u00adactions with highest propensities (0.68) are between the H and O atoms of the sulfonamide groups of two neighboring mol\u00adecules. One of them (N1\u2014H1B\u22efO2) is observed only in the S-enanti\u00adomer.Regarding the inter\u00admolecular inter\u00adactions, two hydrogen bonds involving the hydrogen atoms bonded to the nitro\u00adgen of the sulfonamide group and the two oxygen atoms of the sulfonyl group (N1\u2014H1A) and for the secondary amine (N2\u2014H2A) with the sulfonyl O atoms , which are not present in either structure. However, N3\u2014H3A\u22efO1 and N3\u2014H3A\u22efO2 contacts with 0.42 propensities are displayed in S-TCMZ and RS-TCMZ (motifs I and IV), respectively. In addition, the hydrogen bond N2\u2014H2A\u22efO1 is present in RS-TCMZ (motifs V and VI) but not in S-TCMZ. The hydrogen bond N2\u2014H2A\u22efN1 was not predicted because the N1 atom was not considered an acceptor. The hydrogen-bond patterns found in the two structures are consistent with the hydrogen-bond propensity analysis results. Every donor and acceptor in RS-TCMZ and in S-TCMZ has a hydrogen-bond coordination with a high likelihood. Figure S2 of the additional supporting information shows the putative landscape for trichlorme\u00adthia\u00adzide. The two structures fall in the high propensity and hydrogen-bond coordination zone.The CSD statistics predicts hydrogen bonds for the sulfonyl nitro\u00adgen atom  with 36.0 and 16.9%, respectively. The next inter\u00adaction, O\u22efCl, is slightly less important in RS-TCMZ than in S-TCMZ (8.7% versus 9.6%). The remaining inter\u00adactions differ in order of importance. For example, the H\u22efH inter\u00adaction is more important (8.5%) in RS-TCMZ than in S-TCMZ (7.2%). It is worth noting that the fingerprint plot delineated into the H\u22efH inter\u00adaction for RS-TCMZ shows a tip at de + di = 2.20\u2005\u00c5, which is less than 2 times the van der Waals radii of hydrogen. In contrast, in S-TCMZ this inter\u00adaction is dispersed over a range of de + di values. Weaker inter\u00adactions such as \u03c0\u2013\u03c0 contacts are present only in racemic TCMZ and they represent 1.8% of the contribution to the Hirshfeld surface. The Cl\u22ef\u03c0 inter\u00adaction is more important in S-TCMZ, contributing 9.1% in contrast to RS-TCMZ where it represents 2.8%. This is the result of two inter\u00adactions in the S-enanti\u00adomer that lead to layers parallel to the ab plane. In RS-TCMZ, the Cl\u22ef\u03c0 inter\u00adactions alternate with \u03c0\u2013\u03c0 contacts to produce chains nearly along [101]. Another inter\u00adesting feature is displayed by the H\u22efN contacts. There is a lower degree of directionality and strength of this inter\u00adaction in RS-TCMZ (2.1%) than in S-TCMZ (3.3%) as a result of the additional N2\u2014H2A\u22efN1 inter\u00adaction in the latter.Fig.\u00a08ts Fig.\u00a08m\u20138x witEele), dispersive (Edis), and total energies (Etot) for the inter\u00admolecular inter\u00adactions in RS-TCMZ and S-TCMZ were calculated with CrystalExplorer21  and dispersive  components are similar although their contributions are quite different. They result in an offset tile arrangement for Etot when viewed down the b-axis direction . In the structure of S-TCMZ, Eele and Edis make similar contributions to Etot and their topology is similar . The pattern viewed down the b-axis direction resembles a herringbone arrangement .As depicted in Fig.\u00a09on Fig.\u00a09c. In thar Fig.\u00a09d and 9ent Fig.\u00a09f.supporting information). The stretches for the secondary N\u2014H grouping of the sulfonamide group appear at 3387 and 3322\u2005cm\u22121 followed by the stretching bands of the S\u2014N\u2014H and N\u2014H groups of the amine on the di\u00adhydro\u00adthia\u00addiazine at 3281 and 3232\u2005cm\u22121, respectively. The stretches of the Csp2\u2014H (3150\u20133100\u2005cm\u22121) and Csp3\u2014H (3000\u20132900\u2005cm\u22121) bonds are observed as weak bands. The Csp2\u2014Csp2 stretch of the aromatic ring appears at 1596\u2005cm\u22121 while the C\u2014N and S\u2014N stretches overlap at 1351 and 1332\u2005cm\u22121. The stretches of the two S=O groups appear as strong absorptions at 1176 and 1157\u2005cm\u22121. Table S2 summarizes the assignment of the most important absorptions for RS-TCMZ.The FT\u2013IR spectrum shows the absorption bands expected for TCMZ  recorded indicates the material is stable up to 240\u00b0C. A series of weight loss events occur from 240\u00b0C to 450\u00b0C. A 24.2% weight loss (2.270\u2005mg) between 245 and 301\u00b0C coincides with the first two transitions in the DSC . The endotherm at 281.1\u00b0C (\u0394H = 81.19\u2005J\u2005g\u22121) is associated with melting of the material. This transition is followed by an exotherm with peak temperature 287.9\u00b0C (\u0394H = 103.70\u2005J\u2005g\u22121). The TGA curve shows two continuous weight loss processes at 302\u2013384\u00b0C  and 384\u2013448\u00b0C , associated with ill-defined transitions in the DSC. The total weight loss due to decomposition is 49.6%.The TGA curve  TCMZ, I. DOI: 10.1107/S2056989021013633/hb7999Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013633/hb7999Isup3.molSupporting information file. DOI: 10.1107/S2056989021013633/hb7999sup4.pdfPowder pattern superposition, Hydrogen bond propensity analysis, Hirshfeld surface, energy frameworks calculations, FT-IR, and TGA/DSC. DOI: Click here for additional data file.10.1107/S2056989021013633/hb7999Isup5.cmlSupporting information file. DOI: 2034096, 2034096CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are connected by N\u2014H\u22efO hydrogen-bond pairs along the b-axis direction as dimers with R22(8) and R22(14) ring motifs and as ribbons formed by inter\u00admolecular C\u2014H\u22efN hydrogen bonds. There are weak van der Waals inter\u00adactions between the ribbons. The most important contributions to the surface contacts are from H\u22efH (34.9%), O\u22efH/H\u22efO (19.2%), C\u22efH/H\u22efC (11.9%), Cl\u22efH/H\u22efCl (10.7%) and N\u22efH/H\u22efN (10.4%) inter\u00adactions, as concluded from a Hirshfeld surface analysis.The mol\u00adecular conformation of the title compound, C The planes of the 2,3-di\u00adhydro-1H-indole ring system and the 4H-pyran ring are approximately perpendicular to each other, subtending a dihedral angle of 84.52\u2005(5)\u00b0. The C5\u2014C6\u2014C11\u2014Cl1, C6\u2014C5\u2014C8\u2014O2, C6\u2014C5\u2014C8\u2014O3, C5\u2014C8\u2014O3\u2014C9 and C8\u2014O3\u2014C9\u2014C10 torsion angles are \u2212103.28\u2005(13), \u221229.78\u2005(18), 150.69\u2005(11), 178.03\u2005(10) and \u2212169.29\u2005(12)\u00b0, respectively. An intra\u00admolecular C11\u2014H11B\u22efO2 contact stabilizes the mol\u00adecular conformation of the title compound  ring motif  inter\u00adactions are the major factor in the crystal packing with O\u22efH/H\u22efO , C\u22efH/H\u22efC , Cl\u22efH/H\u22efCl  and N\u22efH/H\u22efN  inter\u00adactions representing the next highest contributions. Other weak inter\u00adactions (contribution percent\u00adages) are O\u22efN/N\u22efO (2.3%), O\u22efC/C\u22efO (2.1%), N\u22efC/C\u22efN (2.1%), Cl\u22efN/N\u22efCl (1.7%), Cl\u22efO/O\u22efCl (1.4%), C\u22efC (1.0%), N\u22efN (0.7%), O\u22efO (0.6%), Cl\u22efC/C\u22efCl (0.6%) and Cl\u22efCl (0.3%).Fig.\u00a07et al., 2016H-pyran-3-carbo\u00adnitrile as the main skeleton revealed the presence of three structures, ethyl 6-amino-2-(chloro\u00admeth\u00adyl)-5-cyano-4-(o-tol\u00adyl)-4H-pyran-3-carb\u00adoxyl\u00adate  and C(8). Combination of these primary motifs leads to a secondary In the crystal of HIRNUS, the six-membered pyran ring adopts a near-boat conformation. The crystal structure features two intra\u00admolecular C\u2014H\u22efO inter\u00adactions and the crystal packing is stabilized by inter\u00admolecular N\u2014H\u22efO hydrogen bonds. These lead to two primary motifs, In the crystal of JEGWEX, a potential precursor for fluoro\u00adquinoline synthesis, the pyran ring is nearly planar, with the most outlying atoms displaced from the best-plane fit through all non-H atoms by 0.163\u2005(2) and 0.118\u2005(2)\u2005\u00c5. The mol\u00adecules are arranged in layers oriented parallel to the (011) plane. In addition, the mol\u00adecules are linked by a weak C\u2014H\u22efO hydrogen bond, which gives rise to chains with base vector [111].QT = 0.085\u2005(7)\u2005\u00c5, \u03b8 = 84\u2005(5)\u00b0 and \u03c6 = 154\u2005(5)\u00b0. In the crystal, mol\u00adecules are linked as dimers by pairs of N\u2014H\u22efO hydrogen bonds, forming ribbons along the b-axis direction. These ribbons are connected by weak van der Waals inter\u00adactions, stabilizing the mol\u00adecular packing.In WIMBEC, the pyran ring exhibits a near-boat conformation with puckering parameters et al., 2015et al., 2018The title compound was synthesized using previously reported procedures , N2\u2014H2A = 0.843\u2005(19) and N2\u2014H2B = 0.889\u2005(18)\u2005\u00c5], but their isotropic displacement parameters were constrained to take a value of 1.2Ueq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C\u2014H = 0.95 (aromatic), 0.99 (methyl\u00adene) and 0.98\u2005\u00c5 (meth\u00adyl), with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others. Four reflections, 0 0 1, 0 1 0, 1 0 0 and 1 2 0, affected by the incident beam-stop and owing to poor agreement between observed and calculated intensities, and five outliers, Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021006459/vm2250sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021006459/vm2250Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021006459/vm2250Isup3.cmlSupporting information file. DOI: 2091350CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular complex is based on the heterobimetallic AgI\u2014VV fragment {AgI2(VVO2F2)2(tr)4} supported by four 1,2,4-triazole ligands [4-benzyl-]. The triazole functional group demonstrates homo- and heterometallic connectivity (Ag\u2014Ag and Ag\u2014V) of the metal centers through the [\u2013NN\u2013] double and single bridges, respectively. The vanadium atom possesses a distorted trigonal\u2013bipyramidal coordination environment [VO2F2N] with the Reedijk structural parameter \u03c4 = 0.59. In the crystal, C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds as well as C\u2014H\u22ef\u03c0 contacts are observed involving the organic ligands and the vanadium oxofluoride anions. A Hirshfeld surface analysis of the hydrogen-bonding inter\u00adactions is also described.The crystal structure of the title compound, [Ag The 1,2,4-triazole heterocycle, as a functional group, demonstrates a favorable coordination affinity towards AgI cations, connecting them into polynuclear units 2(tr)4} SBUs with bi-1,2,4-triazole ligands with different geometries 2(2Phtr-CH)4] (I), which has the ligand 4-benzyl- (tr-CH2Ph).There is considerable inter\u00adest in the chemistry of organic\u2013inorganic hybrids, including the vanadium oxide\u2013fluoride (VOF) matrix, which is motivated by the numerous potential applications in catalysis, magnetism, optics, I crystallizes in the monoclinic space group P21/c. Its asymmetric unit contains one AgI cation, one [VVO2F2]\u2212 anion and two organic ligands (tr-CH2Ph), which, after inversion across a center of symmetry, form the mol\u00adecular tetra\u00adnuclear cluster {AgI2(VVO2F2)2(tr-CH2Ph)4} \u2005\u00c5; symmetry code (i) \u2212x, \u2212y\u00a0+\u00a01, \u2212z], while the other two link Ag and V centers [the Ag\u22efV distance is 3.8044\u2005(6)\u2005\u00c5]. Thus, the coordination environment of the AgI cation can be described as [AgN3O] with typical Ag\u2014N(triazole) bond lengths [in the range of 2.197\u2005(2) \u2013 2.390\u2005(3)\u2005\u00c5] and a slightly elongated Ag\u2014O bond [2.562\u2005(2)\u2005\u00c5]  and 1.8330\u2005(18)\u2005\u00c5], two short V\u2014O [1.632\u2005(2) and 1.660\u2005(2)\u2005\u00c5] and elongated V\u2014N [2.203\u2005(2)\u2005\u00c5] bonds \u2005\u00c5, symmetry code (v) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z] hydrogen-bond contacts. The other triazole group, which provides the heterometallic Ag\u2013V linkage, forms bifurcated C\u2014H\u22efO and C\u2014H\u22efF contacts with vanadium oxofluoride anions of neighboring mol\u00adecular complexes. Additionally, methyl\u00adene \u2013CH2\u2013 fragments show directed C\u2014H\u22efO and C\u2014H\u22efF contacts to the VOF fragments. The phenyl rings are here oriented towards each other in an edge-to-face C\u2014H\u22ef\u03c0 inter\u00adaction mode.Since the organic ligand contains a hydro\u00adphobic benzyl tail, the crystal structure of s Figs.\u00a02. The cenet al., 2004CrystalExplorer17  to 1.385 (blue) a.u. visualizes the set of shortest inter\u00admolecular contacts  contacts  suggests the dominant role of the hydrogen-bond inter\u00adactions. The strongest ones  have a similar nature and they are reflected by pairs of spikes pointing to the lower left of the plot. However, the contribution from the contacts with F-atom acceptors is higher (15.6% for F\u22efH/H\u22efF and 11.6% for O\u22efH/H\u22efO) and they are also essentially shorter, as indicated by different lengths of the spikes (the shortest contacts are F\u22efH = 2.0 and O\u22efH = 2.2\u2005\u00c5). One may suppose that the preferable sites for hydrogen bonding of the vanadium oxofluoride groups are the F atoms. This is consistent with the results of Hirshfeld analysis for the [VOF5]2\u2212 anion 4,4\u2032-bis\u00ad salt  with the polarized methyl\u00adene H atoms. There are no mutual \u03c0\u2013\u03c0 inter\u00adactions involving phenyl rings, which are responsible for larger fractions of the C\u22efC contacts in the case of polycyclic species  and C\u22efH/H\u22efC (22.2%) contacts, which appear as pairs of nearly identical, very diffuse and short features (N\u22efH = 2.9 and C\u22efH = 2.9\u2005\u00c5). Both of them correspond to edge-to-face stacking or C\u2014H\u22efet al., 2016H-1,2,4-triazol-4-yl) and it revealed five hits for coordination compounds based on this ligand. There are no examples of AgI compounds, only two FeII complexes [FAYQAA  ligand.A structure survey was carried out in the Cambridge Structural Database  (tr-CH2Ph) was synthesized by refluxing benzyl\u00adamine  and di\u00admethyl\u00adformamide azine  in the presence of toluene\u00adsulfonic acid monohydrate  as a catalyst in DMF (30.0\u2005ml).4-Benzyl-, tr-CH2Ph , V2O5  and 5\u2005mL of water with aqueous HF  was added into a Teflon vessel. Then the components were heated at 423\u2005K for 24\u2005h and slowly cooled to room temperature over 50\u2005h, yielding light-yellow prisms of I .Compound 2C6H5 linkage and similarity restraints applied to the closely separated contributions of C12 and C12A, C13 and C13A. H atoms were positioned geometrically and refined as riding, with C\u2014H = 0.93\u2005\u00c5 (CH) and 0.97\u2005\u00c5 (CH2) and with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989022001712/dj2039sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001712/dj2039Isup2.hklStructure factors: contains datablock(s) I. DOI: 2151864CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The pyran ring is modestly non-planar while the tetra\u00adhydro\u00addiazepine ring adopts a boat conformation. In the crystal, N\u2014H\u22efO hydrogen bonds and slipped \u03c0\u2013\u03c0 stacking inter\u00adactions build a three-dimensional network structure. S,E)-3-diazepin-2-yl\u00adidene]-6-methyl-2H-pyran-2,4(3H)-dione}, C19H16N2O4, is constructed from a benzodiazepine ring system linked to furan and pendant di\u00adhydro\u00adpyran rings, where the benzene and furan rings are oriented at a dihedral angle of 48.7\u2005(2)\u00b0. The pyran ring is modestly non-planar [largest deviation of 0.029\u2005(4)\u2005\u00c5 from the least-squares plane] while the tetra\u00adhydro\u00addiazepine ring adopts a boat conformation. The rotational orientation of the pendant di\u00adhydro\u00adpyran ring is partially determined by an intra\u00admolecular N\u2014HDiazp\u22efODhydp (Diazp = diazepine and Dhydp = di\u00adhydro\u00adpyran) hydrogen bond. In the crystal, layers of mol\u00adecules parallel to the bc plane are formed by N\u2014HDiazp\u22efODhydp hydrogen bonds and slipped \u03c0\u2013\u03c0 stacking inter\u00adactions. The layers are connected by additional slipped \u03c0\u2013\u03c0 stacking inter\u00adactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (46.8%), H\u22efO/O\u22efH (23.5%) and H\u22efC/C\u22efH (15.8%) inter\u00adactions, indicating that van der Waals inter\u00adactions are the dominant forces in the crystal packing. Computational chemistry indicates that in the crystal the N\u2014H\u22efO hydrogen-bond energy is 57.5\u2005kJ\u2005mol\u22121.The title compound {systematic name: ( In the seven-membered ring, N1 and N2 are displaced from the C1\u2013C6 plane by 0.159\u2005(6) and 0.158\u2005(6)\u2005\u00c5, respectively, in the direction away from C8  = 0.915\u2005(4)\u2005\u00c5, Q(3) = 0.187\u2005(4)\u2005\u00c5, \u03c6(2) = 38.9\u2005(2)\u00b0 and \u03c6(3) = 156.3\u2005(12)\u00b0 [total puckering amplitude Q = 0.933\u2005(4)\u2005\u00c5]. This ring adopts a boat conformation. The mean plane of the O1/C10\u2013C14 ring is inclined to that of the C1\u2013C6 ring by 34.8\u2005(1)\u00b0, while the C1\u2013C6 and O4/C16\u2013C19 rings make a dihedral angle of 48.7\u2005(2)\u00b0. The orientation of the O1/C10\u2013C14 ring is partially determined by an intra\u00admolecular N1\u2014H1\u22efO2 hydrogen bond  hydrogen bonds  distance = 3.690\u2005(2)\u2005\u00c5, slippage = 1.47\u2005\u00c5] , the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter or longer than the van der Waals radii, respectively , while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the \u03c0\u2013\u03c0 stacking by the presence of adjacent red and blue triangles. Fig.\u00a04c clearly suggests that there are \u03c0\u2013\u03c0 inter\u00adactions in (I)a, and those delineated into H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH, C\u22efC, H\u22efN/N\u22efH, C\u22ef O/O\u22efC and O\u22efO contacts  have tips at de + di = 2.95\u2005\u00c5. The C\u22efC contacts  have an arrow-shaped distribution of points with its tip at de = di = 1.65\u2005\u00c5. The H\u22efN/N\u22efH contacts  have tips at de + di = 2.78\u2005\u00c5. Finally, the C\u22efO/O\u22efC  and O\u22efO  contacts  appear with tips at de + di = 3.50\u2005\u00c5 and de = di = 1.73\u2005\u00c5, respectively.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of (I)rm Fig.\u00a04a, the wH Table\u00a02 contributs Fig.\u00a05d, 15.8%ts Fig.\u00a05e, 7.4% ts Fig.\u00a05f, 2.8% \u22efC Fig.\u00a05g and O\u22ef\u22efO Fig.\u00a05h contacdnorm plotted onto the surface are shown for the H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH and C\u22efC inter\u00adactions in Fig.\u00a06a\u2013d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efO/O\u22efH, and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions play the major role in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  as \u221232.6 (Eele), \u22127.4 (Epol), \u221260.8 (Edis), 57.3 (Erep) and \u221257.5 (Etot).The inter\u00admolecular inter\u00adaction energies were calculated using the CE\u2013B3LYP/6\u201331G energy model available in et al., 2016Hbenzo[b] diazepines substituted at the 2- and 4-positions gave a substantial number of hits with seven deemed closely similar to the title mol\u00adecule C6H3 and R\u2032 = 6- methyl-2H-pyran-2,4-(3H)-dione as well as R = 6-methyl-2H- pyran-2,4-(3H)-dione and R\u2032 = 3-BrC6H4  to 0.957\u2005(2)\u2005\u00c5 . The dihedral angles between the mean planes of the benzo rings and those of the ring-containing substituents on the seven-membered ring vary considerably, likely due to packing considerations as the steric bulk of these groups differ markedly.A search of the Cambridge Structural Database \u00adeth\u00adyl]-4-hy\u00addroxy-6-methyl\u00adpyran-2-one (4\u2005mmol) in ethanol (40\u2005ml) were added 1.5 equivalents of furan-2-carboxaldehyde and four drops of tri\u00adfluoro\u00adacetic acid (TFA). The mixture was refluxed for 3\u2005h. Cooling to room temperature induced the precipitation of a yellow solid, which was filtered off, and then washed with 20\u2005ml of cold ethanol. Crystals suitable for X-ray analysis were obtained by recrystallization of the bulk from ethanol solution to afford colourless crystals (yield: 75%).CELL_NOW  was used for the final refinement. Hydrogen atoms attached to carbon were included as riding contributions in idealized positions (C\u2014H = 0.95\u20130.99\u2005\u00c5) with Uiso(H) = 1.2\u20131.5Ueq(C). Those attached to nitro\u00adgen were restrained to a target bond length of 0.91\u2005\u00c5 using the DFIX instruction in SHELXL. The displacement ellipsoids of the O1/C10\u2013C14 ring suggest a possible slight disorder in this group, but it does not appear large enough to model with alternate locations of the atoms.Crystal, data collection and refinement details are presented in Table\u00a0310.1107/S2056989021007441/wm5612sup1.cifCrystal structure: contains datablock(s) I, global. DOI: Click here for additional data file.10.1107/S2056989021007441/wm5612Isup3.cdxSupporting information file. DOI: 10.1107/S2056989021007441/wm5612Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007441/wm5612Isup4.cmlSupporting information file. DOI: 2097593CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-020-68370-y, published online 21 August 2020Correction to: This Article contains a typographical error in the Results section under subheading \u2018Mechanical properties\u2019 where,\u201cThe compressive strength of the scaffolds calculated as the maximum compression force divided by the cross-sectional area of tested specimen, was 87.4\u2009\u00b1\u200922.1 and 6.5\u2009\u00b1\u20090.8\u00a0MPa for ATE-G3 and Repros (BCP) scaffolds, respectively.\u201dshould read:\u201cThe compressive strength of the scaffolds calculated as the maximum compression force divided by the cross-sectional area of tested specimen, was 8.7\u2009\u00b1\u20092.2 and 6.5\u2009\u00b1\u20090.8\u00a0MPa for ATE-G3 and Repros (BCP) scaffolds, respectively.\u201d"}
{"text": "The daily life of Chronic obstructive pulmonary disease (COPD) patients is characterised not only by chronic respiratory symptoms but also by exercise intolerance due to their breathlessness. Proper diagnosis and management of this disease consequently includes evaluation of exercise tolerance , frequenAn observational study was performed with inclusion of seventy one men with moderate COPD (FEV1 54.6\u2009\u00b1\u20097.1%); age 63.8\u2009\u00b1\u20093.1 yrs; weight, 71.2\u2009\u00b1\u20098.3\u2009kg; height, 169.0\u2009\u00b1\u20098.1\u2009cm constituted the COPD group (COPDG), and 150 healthy subjects, age 64.2\u2009\u00b1\u20095.8 yrs; weight, 76.2\u2009\u00b1\u200911.3\u2009kg; height, 169.8\u2009\u00b1\u20097.5\u2009cm, were included as the healthy group \u2013 HG. The physical parameters assessed were strength, aerobic endurance, flexibility and agility/balance, by the Fullerton\u2019s functional fitness tests. The health status was evaluated through the Medical Outcomes 36-item Short Form Health Survey (SF-36) questionnaire. The study was approved by the Ethics Committee of the Garcia de Orta Hospital and all participants gave their informed consent.p\u2009<\u2009.05) between COPDG and HG groups for the following variables all expressed in mean\u2009\u00b1\u2009SD: body mass index, 25.9\u2009\u00b1\u20093 vs 27.7\u2009\u00b1\u20094.1\u2009kg.m2; 30-second chair stand 14.1\u2009\u00b1\u20091.7 vs. 18.2\u2009\u00b1\u20091.9 times; arm curl 15.7\u2009\u00b1\u20092.8 vs. 18.8\u2009\u00b1\u20094.9 times; 6-minute walk 498.8\u2009\u00b1\u200958.3 vs. 589.7\u2009\u00b1\u200988.6 m; 8-foot up-and-go 4.7\u2009\u00b1\u20090.8 vs. 5.1\u2009\u00b1\u20091\u2009sec; chair sit-and-reach 0.81\u2009\u00b1\u20099.9 vs. \u22127.1\u2009\u00b1\u200910.6\u2009cm respectively and no differences were observed for the back scratch test . In health status DPOCG presented a significant decrease (p\u2009<\u2009.05) on perception of all domains of SF-36, except on body pain.The values of the functional fitness test were significantly different (In this study COPD patients have lower levels of functional capacity compared to healthy subjects. However, they were able to perform short tasks with higher speed. This trend was also evident in other study where COPD patients performed short term activities faster than healthy persons . Limitat"}
{"text": "In Xu et al.,p value\u00a0<\u00a00.05 vs. NC group; NC: negative control). F, Overexpression of lncRNA\u2010CASC7 increased the expression of IL\u201011 in H9C2 cellsFIGURE 9: lncRNA\u2010CASC7 suppressed the expression of miR\u201030c in H9C2 cells (*Supplementary MaterialClick here for additional data file."}
{"text": "A series of platinum(II) complexes with differently substituted iminomethyl groups were synthesized, and their photophysical properties were examined in solution, in the crystalline, and in the PMMA film\u2010dispersed state, respectively (PMMA=poly(methyl methacrylate)). These complexes showed structure\u2010dependent emission spectra, in which the color of the luminescence in the crystalline state varied over a range of about 40\u2005nm depending on the specific bowl\u2010shaped molecular structure. The chiral complexes with \u2010 and \u2010configurations were found to have structure\u2010dependent chiroptical properties both in solution and the PMMA film\u2010dispersed state such that the intensity of circular dichroism (CD) and circularly polarized luminescence (CPL) were enhanced with bulky cyclic substituents at the nitrogen atoms. A theoretical study using density functional theory (DFT) and time\u2010dependent (TD)\u2010DFT calculations revealed that the enhancement of chiroptical responses is due to the amplification of the magnetic dipole moment caused by the distortion of the square planar geometry.The relationship between the coordination geometry and photophysical properties of  Chiral platium(II)\u00a0complexes exhibit structure\u2010dependent chiroptical properties in dilute solution and in the poly(methyl methacrylate) film\u2010dispersed state. DFT and TD\u2010DFT calculations of the structures and electronic configurations revealed that the enhancement of the chiroptical responses is due to the distortion of the square planar geometry. Complexes \u2010 and \u20101\u2009a\u2013e were successfully characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy , infrared (IR) spectroscopy, and high\u2010resolution mass spectrometry (HRMS). The same treatment with the racemic ligand yielded a mixture of rac\u2010/\u20101\u2009a and meso\u2010\u20101\u2009a (ca. 1\u2009:\u20091). Recrystallization from CH2Cl2/n\u2010hexane gave enriched \u20101\u2009a in 46\u2009% diastereomeric excess. Repeated crystallization from CH2Cl2/n\u2010hexane yielded pure crystals of \u20101\u2009a. From the mother liquor of the first recrystallization, enriched /\u20101\u2009a in 6\u2009% diastereomeric excess was obtained. Crystallization of the enriched /\u20101\u2009a from CH2Cl2/n\u2010hexane several times afforded pure crystals of /\u20101\u2009a.A series of chiral 1\u2009a\u2013e were obtained by recrystallization from CH2Cl2/n\u2010hexane and employed in single\u2010crystal X\u2010ray diffraction (XRD) analysis. Details of the crystal data and the structure refinement are presented in Table\u2005S1 (Supporting Information), including analysis of the intermolecular interactions . ORTEPS,S)\u20101\u2009a, /\u20101\u2009a, \u20101\u2009a, \u20101\u2009b\u2013d, and \u20101\u2009e are shown in Figures\u2005\u03d5) and bowl angles \u03b8 between the mean planes of the naphthalene rings are provided to express the degree of distortion of the coordination planes.Single crystals of platinum complexes S,S)\u20101\u2009a, /\u20101\u2009a, and \u20101\u2009a are shown in Figures\u2005S,S)\u20101\u2009a has a bowl configuration (\u03b8=49.6\u00b0), and the two methyl groups have a syn\u2010orientation \u20101\u2009a in the spiro\u2010chelate rings has a positive value of 7.94\u00b0. Hence, \u20101\u2009a has a  configuration in the crystal. These structural data correspond well with the previously reported palladium(II) complex.R,R)/\u20101\u2009a have an envelope form with a \u03d5 angle of \u22122.64\u00b0 . Therefore, \u20101\u2009a in /\u20101\u2009a has a  configuration in the crystal, whilst \u20101\u2009a in the enantiopure crystal showed the opposite \u039b configuration. \u20101\u2009a adopts a step configuration with C2 symmetry, and the two methyl groups in \u20101\u2009a take an anti\u2010orientation .The molecular structures of \u20101\u2009b\u2013d and \u20101\u2009e are shown in Figures\u2005S,S)\u20101\u2009b adopts the bowl configuration (\u03b8=19.2\u00b0) with anti\u2010orientation between the phenyl groups \u20101\u2009c are in anti\u2010orientation, and the structure can be described as a distorted bowl\u2010configuration with a low bowl angle (\u03b8=3.56\u00b0) \u20101\u2009d has a bowl\u2010configuration with \u03b8=48.2\u00b0 as the bowl angle and a \u039b configuration with a positive value of \u03d5=1.30\u00b0 \u20101\u2009e adopts the step configuration (\u03b8=5.14\u00b0) with an anti\u2010orientation between the methyl groups \u2010 and \u20101\u2009a\u2013e were recorded in solution and in the PMMA (PMMA=poly(methyl methacrylate) film\u2010dispersed state at room temperature \u20101\u2009a\u2013d exhibited a strong negative Cotton effect at approximately 420\u2005nm, which can be assigned to a mixture of intra\u2010ligand charge transfer (1ILCT) and metal\u2010to\u2010ligand charge transfer (1MLCT) from the UV/Vis spectra showing a mixture of 1ILCT and 1MLCT bands around 370\u2013500\u2005nm observed under the same measurement conditions \u20101\u2009e showed a comparably weak negative Cotton effect in the same region, although it has almost the same UV/Vis spectrum as \u20101\u2009a\u2013d. The gabs (=\u0394\u03f5/\u03f5) values around the absorption maxima in the low energy region are \u22120.0026 (422\u2005nm) for \u20101\u2009a, \u22120.0023 (422\u2005nm) for \u20101\u2009b, \u22120.0030 (417\u2005nm) for \u20101\u2009c, \u22120.0025 (418\u2005nm) for \u20101\u2009d, and \u22120.00088 (410\u2005nm) for \u20101\u2009e, respectively. These results indicate that the bulkiness of the substituents at the nitrogen atoms exert a strong influence on the chiral properties of 1 even in the diluted solution state.Circular dichroism (CD) spectra of \u20101\u2009d (\u03bbmax=589\u2005nm) with the bulkiest 1\u2010naphthyl substituent at the nitrogen atoms compared to those of \u20101\u2009a\u2013c \u20101\u2009a, 601\u2005nm for \u20101\u2009b, and 602\u2005nm for \u20101\u2009c, respectively). In contrast, a bathochromic shift was observed for \u20101\u2009e (\u03bbmax=608\u2005nm) with the less bulky alkyl substituents at the nitrogen atoms. These results indicate that the bulkiness of the substituents at the nitrogen atoms affects the d\u2010\u03c0 conjugation of the coordination platform in dilute solution.All the complexes exhibited orange to red luminescence under UV excitation at room temperature in solution, crystalline, and PMMA film\u2010dispersed state, respectively . The photophysical data of complexes S,S)\u20101\u2009a\u2013e was more remarkable in the crystalline state. Figure\u2005S,S)\u20101\u2009a\u2013e in the crystalline state, where the emission peak maxima clearly changes depending on the substituent at the nitrogen atoms \u20101\u2009a, 623\u2005nm for \u20101\u2009b, 605, 628\u2005nm for \u20101\u2009c, 605\u2005nm for \u20101\u2009d, and 632\u2005nm for \u20101\u2009e).The change in the emission color of /\u20101\u2009a and \u20101\u2009a showed bathochromic emission patterns that were different from that of enantiopure crystals \u20101\u2009a . XRD analysis showed that the maximum emission wavelength (\u03bbmax) in the crystalline state of complexes 1 was negatively correlated with the bowl angle . Therefore, we assume that bowl\u2010shaped structures exert a strong influence on the d\u2010\u03c0 conjugation of 1, resulting in a change in the emission color in the crystalline state.It is noteworthy that the crystals of (I) and total luminescence (I) spectra measured for \u2010 and \u20101\u2009a\u2013e in the PMMA film\u2010dispersed state at 298\u2005K are shown in Figures\u2005R,R)\u2010 and \u20101\u2009a\u2013d exhibit mirror\u2010image positive and negative signals around 570\u2013590\u2005nm, which are corresponding to the emission maxima (\u03bbmax) observed in their total emission spectra taken under the same measurement conditions  for \u20101\u2009a, \u22120.0011 (575\u2005nm) for \u20101\u2009b, \u22120.0036 (590\u2005nm) for \u20101\u2009c, and \u22120.0018 (575\u2005nm) for \u20101\u2009d, respectively. It should be noted that \u2010 and \u20101\u2009e did not exhibit detectable CPL signals , which indicates that circularly polarized luminescence was induced by introduction of bulky substituents at the nitrogen atoms.The circularly polarized luminescence \u20101\u2009a\u2013e in an isolated system were estimated using DFT  calculations on the basis of the X\u2010ray structures. The optimized structures of \u20101\u2009a\u2013e are shown in Figure\u2005\u03d5) are 0.90\u00b0 for 1\u2009a, 0.78\u00b0 for 1\u2009b, 0.29\u00b0 for 1\u2009c, 1.39\u00b0 for 1\u2009d, and 0.20\u00b0 for 1\u2009e, indicating that the substituents on the nitrogen atoms distort the coordination geometry which induces \u039b chirality. In addition, \u20101\u2009a\u2013d have a bowl\u2010configuration with similar bowl angles \u03b8, while \u20101\u2009e has a step\u2010configuration with a small \u03b8 value. These structural differences are expected to affect the chiroptical properties in solution and in the PMMA film\u2010dispersed state.In order to clarify the structure\u2010dependence of the photophysical properties of the series of platinum complexes S,S)\u20101\u2009a\u2013e and their eigenvalues were estimated by using DFT  calculations on the basis of the optimized structure in the ground state. The HOMOs of all complexes are principally Pt(dzx)\u2013ligand (\u03c0) hybrids, whereas the LUMOs are in the ligand (\u03c0*)  states is the HOMO\u2010to\u2010LUMO transition, which implies that the present emission is principally attributable to a mixture of MLCT/ILCT. The S0\u2013T1 transition energies were calculated to be 2.17\u2005eV (570\u2005nm) for 1\u2009a, 2.18\u2005eV (568\u2005nm) for 1\u2009b, 2.19\u2005eV (567\u2005nm) for 1\u2009c, 2.21\u2005eV (561\u2005nm) for 1\u2009d, and 2.14\u2005eV (579\u2005nm) for 1\u2009e, which is consistent with the hypsochromic and bathochromic shift of the emission peak maxima for 1\u2009d and 1\u2009e in CH2Cl2  calculations  (Table\u2005S2). The major consequence of the electronic configuration of the S 2.17\u2005eV 70\u2005nm forS,S)\u20101\u2009a\u2013e using TD\u2010DFT calculations . The validity of the calculation was confirmed by comparison between theoretical and experimental CD spectra of \u20101\u2009a\u2013e /(|\u03bce|2+|\u03bcm|2), where |\u03bce|, |\u03bcm|, and \u03b8e,m are the electric transition dipole moments, magnetic transition dipole moments, and the angles between two vectors \u03bce and \u03bcm, respectively. , corresponding chiral ligands (0.58\u2005mmol), and K2CO3 (1.5\u2005mmol) in toluene/DMSO (20/5\u2005mL) was warmed at 80\u2009\u00b0C for 16\u2005h. The red reaction mixture was added to water (30\u2005mL) and extracted with EtOAc (20\u2005mL\u00d73). The organic layers were dried over Na2SO4 and evaporated in vacuo. The residue was washed with cold methanol to give the complexes. Suitable crystals for the X\u2010ray analysis were prepared by recrystallization from CH2Cl2/n\u2010hexane.transN\u2010Bis[1\u2010[(1\u2010phenylethyl)imino]methyl\u20102\u2010naphthalenolato\u2010,OR]\u2010platinum(II) \u2010 and \u20101\u2009a): Orange crystals (38\u2009%); m.p. 230\u2009\u00b0C (decomp); IR (KBr): \u03bd=1616\u2005cm\u22121 (N=C); 1H NMR  \u03b4=8.64 , 7.67 , 7.64 , 7.59 , 7.44 , 7.39\u20137.32 , 7.19 , 7.10 , 6.36 , 1.93\u2005ppm ; 13C\u2005NMR  \u03b4=163.03, 152.69, 142.30, 134.00, 133.82, 128.80, 128.73, 128.12, 127.71, 127.39, 127.33, 123.23, 122.48, 119.16, 111.65, 58.53, 21.76\u2005ppm; HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 742.2092, found 742.2094; Anal. Calcd for C38H32N2O2Pt: C, 61.37; H, 4.34; N, 3.77. Found: C, 61.21; H, 4.33; N, 3.65. \u20101\u2009a: [\u03b1]D25=\u2212166 .transN\u2010Bis[1\u2010[(1\u2010phenylpropyl)imino]methyl\u20102\u2010naphthalenolato\u2010,OR]\u2010platinum(II) \u2010 and \u20101\u2009b): Orange crystals (36\u2009%); m.p. 254\u2009\u00b0C (decomp); IR (KBr): \u03bd=1614\u2005cm\u22121 (N=C); 1H NMR  \u03b4=8.66 , 7.69 , 7.66 , 7.57 , 7.45\u20137.32 , 7.20 , 7.14 , 6.10 , 2.53\u20132.23 , 1.18\u2005ppm ; 13C\u2005NMR  \u03b4=162.80, 152.47, 140.52, 133.94, 133.91, 128.88, 128.75, 127.79, 127.37, 127.33, 123.20, 122.44, 119.17, 111.62, 64.51, 28.64, 11,70\u2005ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C40H37N2O2195Pt: 772.2501, found 772.2513; Anal. calcd for C40H36N2O2Pt: C, 62.25; H, 4.70; N, 3.63. Found: C, 62.25; H, 4.67; N, 3.68. \u20101\u2009b: [\u03b1]D25=\u2212231 .transN\u2010Bis[1\u2010[(1\u2010cyclohexylethyl)imino]methyl\u20102\u2010naphthalenolato\u2010,OR]platinum(II) \u2010 and \u20101\u2009c): Orange crystals (23\u2009%); m.p. 278\u2009\u00b0C (decomp); IR (KBr): \u03bd=1616\u2005cm\u22121 (N=C); 1H NMR  \u03b4=8.63 , 7.81 , 7.70 , 7.51 , 7.25 , 7.10 , 4.72 , 2.08\u20131.65 , 1.50 , 1.35\u20131.15\u2005ppm ; 13C\u2005NMR  \u03b4=163.01, 150.76, 133.98, 133.61, 128.83, 127.39, 127.30, 123.20, 122.39, 119.30, 111.74, 61.77, 43.98, 30.43, 28.64, 26.51, 26.29, 26.23, 18.72 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C38H45N2O2195Pt: 756.3127, found 756.3149; Anal. calcd for C38H44N2O2Pt\u2009\u22c5\u20091/2CH2Cl2: C, 57.92; H, 5.68; N, 3.51. Found: C, 57.83; H, 5.19; N, 3.39. \u20101\u2009c: [\u03b1]D25=\u2212153 transN\u2010Bis[1\u2010[ethyl)imino]methyl\u20102\u2010naphthalenolato\u2010,OR]platinum(II) \u2010 and \u20101\u2009d): Orange crystals (48\u2009%); m.p. >300\u2009\u00b0C; IR (KBr): \u03bd=1615\u2005cm\u22121 (N=C); 1H NMR  \u03b4=8.75\u20138.72 , 8.65 , 7.96 , 7.92\u20137.87 , 7.67 , 7.60 , 7.57 , 7.52\u20137.46 , 7.22 , 7.13\u20137.09 , 6.99 , 2.14\u2005ppm ; 13C\u2005NMR  \u03b4=163.19, 151.27, 137.26, 134.27, 133.93, 133.76, 131.76, 129.23, 128.61, 128.53, 127.28, 127.22, 127.17, 126.08, 125.55, 125.12, 124.87, 123.09, 122.37, 119.01, 111.81, 55.67, 22.64\u2005ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C46H37N2O2195Pt: 844.2501, found 844.2479; Anal. calcd for C46H36N2O2Pt\u2009\u22c5\u2009CH2Cl2: C, 60.78; H, 4.12; N, 3.02. Found: C, 60.79; H, 4.33; N, 2.83. \u20101\u2009d: [\u03b1]D25=\u2212243 .transN\u2010Bis[1\u2010[(1\u2010methyllpropyl)imino]methyl\u20102\u2010naphthalenolato\u2010,OR]platinum(II) \u2010 and \u20101\u2009e): Orange crystals (34\u2009%); m.p. 264\u2009\u00b0C (decomp); IR (KBr): \u03bd=1608\u2005cm\u22121 (N=C); 1H NMR  \u03b4=8.72 , 7.83 , 7.70\u20137.68 , 7.50 , 7.26\u20137.23 , 7.10 , 4.88\u20134.81 , 2.15\u20132.06 , 1.85\u20131.76 , 1.54 , 1.09 ppm ; 13C\u2005NMR  \u03b4=163.02, 150.11, 133.95, 133.67, 128.83, 127.41, 127.29, 123.18, 122.41, 119.24, 111.71, 58.46, 31.10, 21.46, 11.02 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C30H33N2O2195Pt: 648.2187, found 648.2185. \u20101\u2009e: [\u03b1]D25=\u221227 .RPreparation of /(S)\u2010 and imino]\u2010methyl\u20102\u2010naphthalenolato\u2010N),OR]platinum(II) /(S)\u20101\u2009a and \u20101\u2009a: A solution of [PtCl2(CH3CN)2] , 2\u2009a , and K2CO3  in toluene/DMSO (20/5\u2005mL) was warmed at 80\u2009\u00b0C for 16\u2005h. The dark red reaction mixture was added to water (30\u2005mL) and extracted with EtOAc (20\u2005mL\u00d73). After evaporation of the solvent, the residue was washed with cold methanol to give a mixture of \u20101\u2009a and /\u20101\u2009a (51\u2009:\u200949 ratio) in 50\u2009% (213\u2005mg) yield. From the first recrystallization of CH2Cl2/n\u2010hexane, the filtrate gave a \u20101\u2009a enriched powder (46\u2009% de). Pure \u20101\u2009a  was obtained by recrystallization of CH2Cl2/n\u2010hexane after several times, crystals of which were suitable for X\u2010ray analysis. After evaporation of the first mother liquor, a /\u20101\u2009a enriched orange powder (6\u2009% de) was obtained. Pure /\u20101\u2009a  was obtained by recrystallization of CH2Cl2/n\u2010hexane after several times, crystals of which were suitable for X\u2010ray analysis. Pure crystals of /\u20101\u2009a were prepared by crystallization of an 1\u2009:\u20091 mixture of \u20101\u2009a and \u20101\u2009a in CH2Cl2/n\u2010hexane.R\u20101\u2009a: m.p. 265\u2009\u00b0C (decomp); IR (KBr): 1606\u2005cm\u22121 (N=C). 1H NMR : \u03b4=8.64 , 7.67 , 7.64 , 7.61 , 7.45 , 7.39\u20137.34 , 7.19 , 7.10 , 6.36 , 1.90\u2005ppm . 13C\u2005NMR : \u03b4=163.03, 152.68, 142.26, 134.00, 133.83, 128.83, 128.74, 128.17, 127.73, 127.39, 127.33, 123.21, 122.48, 119.16, 111.65, 58.69, 21.76\u2005ppm. HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 745.2184, found 745.2147.R,R)/\u20101\u2009a The NMR and IR spectra corresponded well with the data of \u2010 and \u20101\u2009a. HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 745.2184, found 745.2156.X\u2010Ray Crystallography: Crystals suitable for XRD studies were analyzed using a Rigaku RAXIS\u2010RAPID imaging plate diffractometer using Mo\u2010K\u03b1 radiation  and a Rigaku XtaLAB mini2 benchtop X\u2010ray crystallography system equipped with a Mo rotating\u2010anode X\u2010ray generator with monochromated Mo\u2010K\u03b1 radiation (\u03bb=0.71073\u2005\u00c5). The molecular structures and packings in crystals \u20101\u2009a\u2013d, \u20101\u2009e, /\u20101\u2009a, and \u20101\u2009a were solved by direct methods and refined using the full\u2010matrix least\u2010squares method. In subsequent refinements, the function \u03a3\u03c9(Fo2\u2212Fc2)2 was minimized, where Fo and Fc are the observed and calculated structure factor amplitudes, respectively. The positions of non\u2010hydrogen atoms were found from difference Fourier electron density maps and refined anisotropically. All calculations were performed using the Crystal Structure crystallographic or CrysAlisPro program software package, and illustrations were drawn by using ORTEP.S,S)\u20101a), 1918308 /\u20101a), 1918309 \u20101a), 1918310 \u20101b), 1918311 \u20101c), 1918312 \u20101d), 2119929 \u20101e)1918306 ) and singlet\u2013triplet (E(Tn)) transition energies were estimated by time\u2010dependent (TD) DFT calculation .The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efS hydrogen bonds, forming a two-dimensional supra\u00admolecular architecture. 3H5OS2)2(C6H16N2)] or [Hg(C3H5OS2)2(tmeda)] , has a distorted tetra\u00adhedral geometry. The HgII ion is coordinated to two N atoms of the N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethylenedi\u00adamine ligand and two S atoms from two ethylxanthate xanthate ligands. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efS hydrogen bonds, forming a two-dimensional supra\u00admolecular architecture in the ab plane. The most important contributions for the crystal packing are from H\u22efH (59.3%), S\u22efH (27.4%) and O\u22efH (7.5%) inter\u00adactions.The title four-coordinate mononuclear complex, [Hg(C The bond lengths and angles of the HgN2S2 coordination units correspond to those in the structures of mixed-ligand HgII coordination compounds (see Database survey). The C1\u2014O1 and C2\u2014O1 bond lengths are 1.355\u2005(11) to 1.460\u2005(12)\u2005\u00c5, respectively, although all of the C\u2014O bonds show single-bond character. In the {S2C} section of the xanthate ligands, the C1\u2014S1 distance is 1.727\u2005(9)\u2005\u00c5, which is typical of a single bond, whereas the C1=S2 distance of 1.633\u2005(10)\u2005\u00c5 is typical of a carbon-to-sulfur double bond. The C\u2014N and C\u2014C bond lengths in the N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethylenedi\u00adamine ligand are normal 2(tmeda)].In the crystal, there is a weak inter\u00admolecular hydrogen bonding Table\u00a02 between et al., 201614H26O2S4)]n 2(C6H16N2)] (C9H13NS)2](PF6)2 (C6H16N2)] ] 2  in ethanol (10\u2005mL) under stirring. The formed precipitate was filtered off, washed with water and air-dried. The precipitate was suspended in hot ethanol (10\u2005mL) and tetra\u00admethyl\u00adethylenedi\u00adamine  was added under stirring. The colour changed to dark brown. The precipitate was filtered off and dried and then recrystallized from ethanol. Brown rods were formed.Potassium ethylxanthate  in hot ethanol (10\u2005mL) was added to a hot solution of Hg(CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all othersCrystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021010549/ey2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010549/ey2008Isup2.hklStructure factors: contains datablock(s) I. DOI: 2115100CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The sheets are associated through additional C\u2014H\u22ef\u03c0(ring) inter\u00adactions.The conformation of the title compound is partially determined by a strong, intra\u00admolecular O\u2014H\u22efO hydrogen bond. In the crystal, C\u2014H\u22efO hydrogen bonds link the mol\u00adecules, forming chains along the  13H11NO2, is partially determined by a strong, intra\u00admolecular O\u2014H\u22efO hydrogen bond. The crystal packing consists of strongly corrugated layers parallel to the ac plane and associated through C\u2014H\u22ef\u03c0(ring) inter\u00adactions. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H\u22efH (44.1%), C\u22efH/H\u22efC (29.4%) and O\u22efH/H\u22efO (17.3%) contacts.The conformation of the title compound, C They show anti\u00adfungal  is 1.94\u2005(12) \u00b0. The torsion angles C2\u2014C1\u2014C7\u2014N1, C1\u2014C7\u2014N1\u2014C8, C1\u2014C7\u2014N1\u2014O2, C7\u2014N1\u2014C8\u2014C9 and O2\u2014N1\u2014C8\u2013C-9 are \u221230.2\u2005(3), \u2212179.7\u2005(2), \u22120.4\u2005(3), 27.3\u2005(3) and \u2212152.0\u2005(2)\u00b0, respectively. The conformation of the title compound is partially determined by a strong, intra\u00admolecular O1\u2014H1\u22efO2 hydrogen bond -N-[methanimine]-N-oxido -1,2-bis\u00ad(3-bromo\u00adphen\u00adyl)diazene 1-oxide -N-benzyl\u00adidene-1-phenyl\u00admethanamine oxide hydrogen peroxide solvate -N-(2-chloro\u00adbenzyl\u00adidene)aniline N-oxide \u00b0] and the phenyl and benzene rings are trans-oriented around the C=N bond. The phenyl and benzene rings make a dihedral angle of 56.99\u2005(2)\u00b0.In the crystal of DEPVOM, (101) layers are generated by C\u2014H\u22efO hydrogen bonds coupled with C\u2014H\u22ef\u03c0(ring) and offset \u03c0\u2013\u03c0 stacking inter\u00adactions. In the crystal of SIYHAK01, C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds together with offset \u03c0\u2013\u03c0 inter\u00adactions stack the mol\u00adecules along the Z)-(2-Hy\u00addroxy\u00adphen\u00adyl)methyl\u00adidene]benzenimine N-oxide (nitrone) was prepared according to the reported procedures  = 1.5Ueq(O). The C-bound H atoms were positioned geometrically, with C\u2014H = 0.95\u2005\u00c5, and constrained to ride on their parent atoms, withUiso(H) = 1.2Ueq(C). Attempts to determine the absolute structure did not produce a definitive result, viz.: Flack x = 0.2\u2005(3) by classical fit to all intensities 0.30\u2005(14) from 611 selected quotients (Parsons\u2019 method). A round of TWIN/BASF refinement gave BASF = 0.2\u2005(4) with no improvement in the model.Crystal and refinement details are presented in Table\u00a0410.1107/S2056989021004813/ey2006sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021004813/ey2006Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004813/ey2006Isup3.cmlSupporting information file. DOI: 2082055CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In addition, the mononuclear Dy and Tb complexes [{(thf)2Li(NtBu)2S(tBuN)2LnCl2(thf)2]  show slow magnetic relaxation under applied dc fields.Lanthanide ions are particularly well\u2010suited for the design of single\u2010molecule magnets owing to their large unquenched orbital angular momentum and strong spin\u2010orbit coupling that gives rise to high magnetic anisotropy. Such nanoscopic bar magnets can potentially revolutionize high\u2010density information storage and processing technologies, if blocking temperatures can be increased substantially. Exploring non\u2010classical ligand scaffolds with the aim to boost the barriers to spin\u2010relaxation are prerequisite. Here, the synthesis, crystallographic and magnetic characterization of a series of each isomorphous mono\u2010 and dinuclear lanthanide  complexes comprising tetraimido sulfate ligands are presented. The dinuclear Dy complex [{(thf) The first series of isomorphous lanthanide Gd to Er complexes containing the tetraimido sulfate ligand renders these compounds compelling to be investigated for their single\u2010molecule magnet behaviour. The displayed Dy dimer shows slow magnetic relaxation at zero field. The monomeric Tb and Dy complexes show field\u2010induced single\u2010molecule magnet behaviour. The ligand holds great potential for higher blocking systems, that is, removal of chloride ions, lithium transmetalation and promotion of the magnetic communication between the metal ions. S\u2010alkyltriimidosulfonates [RS(NR)3]\u2212  and in the triimidosulfonic acid MeS(NtBu)2NHtBu the sum of all three S\u2212N bond lengths is constant at 4.70(2)\u2005\u00c5.[3]2\u2212 it was later also found in the tetraimido sulfates [S(NR)4]2\u2212.tBu)]\u2212 ligand in [Co{(NtBu)3SMe}2], ,tBu)4]2\u2212 anion.[Single\u2010molecule magnets (SMMs)4Li2(NtBu)4S] with the appropriate lanthanide(III) chloride in thf yields after extraction and crystallization from toluene the binuclear lanthanide(III) compounds [{(thf)2Li(NtBu)2S(tBuN)2LnCl2}2\u2009\u22c5\u2009ClLi(thf)2] 1\u2009a\u2013e with a: Ln=Gd, b: Tb, c: Dy, d: Ho, e: Er 2Li(NtBu)2S(tBuN)2LnCl2(thf)2] 2\u2009a\u2013e  in good yields and purity. Instead, 2\u2009c was also isolated upon layering the reaction mixture with n\u2010pentane. However, since the crystallization parameters for this reaction are very tedious to control and the final product is insoluble in thf the derivatives rather precipitate than crystallize. Therefore, we concentrated on the optimization of the synthetic route to give the \u03bc\u2010LiCl\u2010bridged dimers 1\u2009a\u2013e. They crystallize in the monoclinic space group C2/c with half a molecule and half a toluene molecule in the asymmetric unit 42\u2212, the S\u2212N bond distances for all metal complexes are almost identical. Nevertheless, it should be stated that the av. S\u2212N1/N2 distances from the lithium coordinating nitrogen atoms of 1.567\u2005\u00c5 are significantly shorter than the S\u2212N3/N4 distances of 1.626\u2005\u00c5 to the lanthanide\u2010coordinated nitrogen atoms. That mirrors the two opposite coordination sites of the tetrahedral ligand which are unsymmetrically coordinated by a lithium ion at the site with shorter S\u2212N bonds and the lanthanide(III) ion at the opposite site. The triply positive charged lanthanides obviously are in much stronger demand of the negatively charged nitrogen atoms, for their part taking advantage of the electropositive central sulfur atom. A stronger demand of the negatively charged nitrogen atoms causes a longer distance between the nitrogen and the positively charged sulfur. The reduced lanthanide radii are also displayed in the reduction of the Ln1\u22c5\u22c5\u22c5Ln1A distances that ranges from 3.835\u2005\u00c5 in 1\u2009a to 3.752\u2005\u00c5 in 1\u2009e. Interestingly, the reduced radii have the opposite effect on the N1\u2212Ln1\u2212N2 angles increasing from 60.91\u00b0 in 1\u2009a to 62.24\u00b0 in 1\u2009e. Even though all Cl\u2212Ln\u2212Cl angles for one specific metal are different, they remain almost identical when proceeding from one lanthanide cation to the next. The same is valid for the N\u2212S1\u2212N angles. A comparable coordination is found in a series of rare earth metal complexes with \u03b2\u2010diketiminato ligands. Substitution at the nitrogen position with 2,6\u2010dimethylphenyl,1\u2009c with 2.726\u2005\u00c5. The same is valid for the Dy\u2212N bond lengths of 2.313\u2005\u00c5 and 2.270\u2005\u00c5, respectively.We found these dimeric complexes, dissolved in small amounts of thf to recrystallize within hours at room temperature, forming the mononuclear lanthanide(III) compounds  3\u2009b could be isolated from toluene . All Tb\u2212Cl distances are similar, although the terbium atoms in 3\u2009b are fourfold chlorine coordinated and those in 1\u2009b and 2\u2009b only two\u2010fold. With the rising nuclearity in 3\u2009b the Tb\u039bTb distance increases to 4.307\u2005\u00c5 compared to 3.831\u2005\u00c5 in 1\u2009b. The acute N1\u2212Tb\u2212N2 bite angles of 61.22\u00b0 (1\u2009b), 60.67\u00b0 (2\u2009b), and 61.10\u00b0 (3\u2009b) differ only marginally. The same is valid for the N1\u2212S1\u2212N2 ligand angles at the Tb side of 91.47\u00b0 (1\u2009b), 92.77\u00b0 (2\u2009b) and 92.60\u00b0 (3\u2009b).Tetranuclear 1\u2009a\u2013e and 2\u2009b\u2013c in the temperature range 2\u2013300\u2005K at 0.1, 0.5 and 1 T fields  are in good agreement with the expected values  for two non\u2010interacting triply positive lanthanide atoms. As the temperature is decreased to 15\u2005K, \u03c7MT undergoes a gradual decline and decreases below that temperature rapidly to reach at 2\u2005K a minimum value of 10.24, 8.99, 9.57, 9.14, and 6.46\u2005cm3K/mol for 1\u2009a\u2013e, respectively. Such downturn in \u03c7MT can be generally assigned to the Zeeman effect and/or weak intermolecular interactions. Notably, the decline in \u03c7MT is much more pronounced for 1\u2009e and can potentially be ascribed to quite anisotropic trivalent erbium atoms in this ligand environment compared to the lighter lanthanide analogs. By contrast, \u03c7MT only decreases more noticeably below 10\u2005K for 1\u2009a hinting at the presence of very weak antiferromagnetic coupling. Due to the half\u2010filled f\u2010electron valence shell (4f7), trivalent gadolinium ions offer the possibility to determine the magnetic exchange interaction precisely. Fitting the dc data of 1\u2009a to a spin\u2010only Hamiltonian \u0124=\u22122J\u015cGd(1)+\u22122J\u015cGd(2) where J is the intramolecular coupling constant and \u015c the spin operator for each paramagnetic center yielded a coupling constant of J=\u22120.045(1)\u2005cm\u22121 which is indicative of weak antiferromagnetic interaction between the GdIII ions. The magnitude of the coupling between the lanthanide ions via superexchange is typically very weak as is the case for the parent compound 1\u2009a and comparable to various chloride\u2010bridged complexes or other bridges leading to superexchange pathways in bimetallic gadolinium complexes. was synthesized according to literature known procedure.All experiments were performed under inert gas conditions in N2Li(NtBu)2S(tBuN)2LnCl2}2General synthesis for [{(thf)\u20092] 1\u2009a\u22c5\u2009ClLi(thf)\u2013e: A mixture of [(thf)4Li2(NtBu)4S]  and LnCl3 (0.8080\u2005mmol) is dissolved in thf (20\u2005mL) at ambient temperature. After stirring for 1 d the reaction mixture is concentrated under reduced pressure (7\u2005mL), filtered and subsequently, the solvent is removed under reduced pressure. The residue is dissolved in toluene (5\u2005mL) and the solution is filtered. Crystal growth of 1\u2009a\u2013e starts within several minutes to hours at ambient temperature. For a complete crystallization, the mixture is stored at \u221234\u2009\u00b0C yielding colorless crystals suitable for X\u2010ray analysis after several days. The solvent is removed, and the crystalline product is washed with n\u2010pentane (2\u00d72\u2005mL). 1\u2009a: Yield: 266.9\u2005mg (40\u2009%); elemental analysis calcd (%) for C56H120Cl5Gd2Li3N8O6S2(C7H8): C 45.30, H 7.72, N 6.71, S 3.84; found: C 42.91, H 6.92, N 6.51, S 4.47. 1\u2009b: Yield: 304.6\u2005mg (45\u2009%); elemental analysis calcd (%) for C56H120Cl5Tb2Li3N8O6 S2(C7H8): C 45.21, H 7.71, N 6.69, S 3.84; found: C 43.64, H 7.87, N 6.88, S 4.80. 1\u2009c: Yield: 281.5\u2005mg (41\u2009%); elemental analysis calcd (%) for C56H120Cl5Dy2Li3N8O6S2(C7H8): C 45.02, H 7.68, N 6.67, S 3.91; found: C 42.63, H 7.62, N 6.61, S 4.14. 1\u2009d: Yield: 137.1\u2005mg (20\u2009%); elemental analysis calcd (%) for C56H120Cl5Ho2Li3N8O6S2(C7H8): C 44.89, H 7.65, N 6.65, S 3.80; found: C 41.27, H 7.06, N 6.71, S 3.92. 1\u2009e: Yield: 113.8\u2005mg (17\u2009%); elemental analysis calcd (%) for C56H120Cl5Er2Li3N8O6S2(C7H8): C 44.76, H 7.60, N 6.63, S 3.79; found: C 42.67, H 7.60, N 7.14, S 5.08.2Li(NtBu)2S(tBuN)2LnCl2(thf)2] 2\u2009aGeneral synthesis for [{(thf)\u2013e: [{(thf)2Li(NtBu)2S(tBuN)2LnCl2}2\u2009\u22c5\u2009ClLi(thf)2] (1\u2009a\u2013e) (150.0\u2005mg) is dissolved in thf (3\u2005mL) and filtered. Crystallization of 2\u2009a\u2013e starts within hours at ambient temperature where upon the mixture is stored at \u221234\u2009\u00b0C to improve the yield. The target compound is isolated and washed with n\u2010pentane (2\u00d71\u2005mL) yielding crystals suitable for X\u2010ray analysis. 2\u2009a: color: colorless; Yield: 98.3\u2005mg (65\u2009%); elemental analysis calcd (%) for C32H68Cl2GdLiN4O4S: C 45.75, H 8.16, N 6.67, S 3.82; found: C 45.82, H 8.59, N 6.54, S 4.01. 2\u2009b: color: colorless; Yield: 99.6\u2005mg (66\u2009%); elemental analysis calcd (%) for C32H68Cl2TbLiN4O4S: C 45.66, H 8.14, N 6.66, S 3.81; found: C 45.98, H 8.66, N 6.50, S 4.34. 2\u2009c: color: colorless; Yield: 105.2\u2005mg (70\u2009%); elemental analysis calcd (%) for C32H68Cl2DyLiN4O4S: C 45.47, H 8.11, N 6.63, S 3.79; found: C 46.58, H 8.71, N 6.44, S 4.77. 2\u2009d: color: pale orange; Yield: 115.5\u2005mg (77\u2009%); elemental analysis calcd (%) for C32H68Cl2HoLiN4O4S: C 45.34, H 8.09, N 6.61, S 3.78; found: C 45.89, H 8.50, N 6.38, S 3.90. 2\u2009e: color: light pink; here, only 100.0\u2005mg of 2\u2009e were used (1\u2009e); Yield: 74.6\u2005mg (74\u2009%); elemental analysis calcd (%) for C32H68Cl2ErLiN4O4S: C 45.21, H 8.06, N 6.59, S 3.77; found: C 45.55, H 8.61, N 6.35, S 4.13.Crystallographic data: Single crystals were selected under cooling using the X\u2010Temp2 device.2 using SHELXL1\u2009a); 2069110 (1\u2009b), 2069111 (1\u2009c), 2069112 (1\u2009d), 2069113 (1\u2009e), 2069114 (2\u2009a); 2069115 (2\u2009b), 2069116 (2\u2009c), 2069117 (2\u2009d), 2069118 (2\u2009e), 2069119 (3\u2009b)2069109 2Li(NtBu)2S(tBuN)2LnCl2}2\u2009\u22c5\u2009ClLi(thf)2] 1\u2009a\u2013e, with a: Ln=Gd, b: Tb, c: Dy, d: Ho, e: Er and species [{(thf)2Li(NtBu)2S (tBuN)2LnCl2(thf)2] 2\u2009a\u2013e  were prepared by loading crushed crystalline samples into tubes in an argon glove\u2010box. Sufficient liquid eicosane (at 60\u2009\u00b0C) was added to saturate and cover the samples to prevent crystallite torquing and provide good thermal contact between the sample and the bath. Tubes were sealed air\u2010tight before transferred to the magnetometer. Magnetic susceptibility measurements were collected using a Quantum Design MPMSXL SQUID magnetometer and Quantum Design MPMS3 SQUID magnetometer, respectively. DC susceptibility data measurements were performed at temperatures ranging from 2 to 300\u2005K for 1\u2009a\u2013e and 2\u2009b\u2013e, using applied fields of 0.1, 0.5 and 1\u2005T. Ac magnetic susceptibility data measurements were performed using a 3.6 (MPMSXL) and 4\u2005Oe (MPMS3) switching field, respectively. All data were corrected for diamagnetic contributions from the eicosane and core diamagnetism estimated using Pascal's constants.\u03c7\u2032 and \u03c7\u2032\u2032 in terms of frequency, constant temperature susceptibility (\u03c7T), adiabatic susceptibility (\u03c7S), relaxation time (\u03c4), and a variable representing the distribution of relaxation times (\u03b1).The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file."}
{"text": "Cell Discovery (2021) 7:103Correction to: 10.1038/s41421-021-00341-7, Published online 31 October 20211, we missed some errors while proofreading the manuscript for the publication. The statistical values in Abstract and Results sections were inconsistent with those in Table FMR1NB, Pmeta\u2009=\u20097.61\u2009\u00d7\u200910\u22129, OR\u2009=\u20091.31; rs7259428, 19q12, ZNF536, Pmeta\u2009=\u20098.20\u2009\u00d7\u200910\u221215, OR\u2009=\u20090.65) showing consistent association with male sexual orientation.\u201d On page 2, the second column, the lines 28\u201335 should be \u201cAll four SNPs showed consistent association in the independent validation samples, and two SNPs reached a genome-wide significance level (P\u2009<\u20095\u2009\u00d7\u200910\u22128) after meta-analysis, including SNP rs7259428 on chromosome 19q12 (located in ZNF536, P\u2009=\u20098.20\u2009\u00d7\u200910\u221215, OR\u2009=\u20090.65; Fig. 1e and Table FMR1NB, P\u2009=\u20097.61\u2009\u00d7\u200910\u22129, OR\u2009=\u20091.31; Fig. 1d and Table ZNF356\u2019 should be \u2018ZNF536\u2019. The corrected version of the Table In the initial published version of this article"}
{"text": "Four copper(II) cations are situated in a distorted square-pyramidal environment, while two copper(II) cations are located in a slightly square-planar geometry. Three of the copper(II) cations occupy three vertices of an open cubane Cu3O4.In the title Schiff base hexa\u00adnuclear copper(II) complex, two discrete environments are present in the structure: CuNO 3-1,3-bis\u00ad{[1-(2-oxidophen\u00adyl)ethyl\u00adidene]amino}\u00adpropan-2-olato)-\u03bc3-hydroxido-dinitrato\u00adhexa\u00adcopper(II) ethanol tris\u00adolvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]\u00b73C2H5OH, corres\u00adponds to a non-symmetric hexa\u00adnuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually inter\u00adconnected, two by two, via three phenolato oxygen anions acting in a \u03bc2-mode. These three copper cations are inter\u00adconnected in a \u03bc3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two \u03bc2-O anions from phenolate groups and one \u03bc3-O atom from a hy\u00addroxy anion. Each of the three penta\u00adcoordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is inter\u00adconnected with another CuII cation via one enolate O atom in \u03bc2-mode, yielding one CuNO4 unit and two CuNO3 units. The penta\u00adcoordinated CuII atom has a distorted square-pyramidal environment while the two tetra\u00adcoordinated copper(II) cations are situated in a square-planar environment. A series of intra\u00admolecular O\u2014H\u22efO hydrogen bonds are observed. In the crystal, the units are connected two by two by inter\u00admolecular C\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, thus forming sheets parallel to the ac plane.The title mol\u00adecular structure, namely, di\u00adaqua\u00adtris\u00ad(\u03bc That their structures present symmetrical or asymmetrical pendant arms and bear donor atoms is an asset widely exploited in coordination chemistry. The presence of donor sites on aliphatic or aromatic arms has made it possible to prepare a wide variety of compounds with various structures and inter\u00adesting physical and chemical properties. 1,3-Di\u00adamino\u00adpropan-2-ol, which has three donor sites, is a good precursor for the synthesis of ligands with several cavities that can act as chelating agents and/or as bridging ligands ethyl\u00adidene]}-2-hy\u00addroxy\u00adpro\u00adpane-1,3-di\u00adamine (H3L). The reaction of ligand H3L with copper nitrate yielded a complex in which the ligand reacted in tri-deprotonated form as L3\u2212. The coordination complex is formulated as [Cu6L3(NO3)2(OH)(H2O)2]\u00b73(EtOH) (I)II cations. The two imino nitro\u00adgen atoms of the ligand are coordinated to two different Cu cations. One of the phenolato O atoms bridges two copper cations, while the second phenolato O atom is coordinated to a third copper cation. The third copper cation is bridged to the central copper cation via the enolato oxygen anion. The tri-deprotonated ligand coordinates in a hepta\u00addentate mode , thus forming four fused chelate rings (two five-membered and two six-membered). Two discrete environments are observed in the structure: CuNO4 and CuNO3. The coordination environments for Cu1, Cu3, Cu5 and Cu6 are best described as square-pyramidal, as shown by the Addison \u03c4 parameter calculated from the largest angles (Table\u00a01W) of the basal coordination plane are almost coplanar and the Cu6 cation is displaced toward the apical atom (O201) by 0.0963\u2005(9)\u2005\u00c5. The cissoid angles are in the range 86.12\u2005(9)\u201394.66\u2005(9)\u00b0 while the transoid angles are 171.23\u2005(9) and 174.18\u2005(9)\u00b0. In the basal plane, the Cu6\u2014N6 [1.942\u2005(2)\u2005\u00c5] and the Cu6\u2014Oligand distances [1.935\u2005(2) and 1.863\u2005(2)\u2005\u00c5] are shorter than the distance of Cu6\u2014O2W [2.028\u2005(2)\u2005\u00c5]. The distance between the copper and the nitrato oxygen anion [Cu6\u2014O14B = 2.45\u2005(2)\u2005\u00c5] in the apical position is longer than the distances to the atoms in the equatorial plane because of Jahn\u2013Teller distortion, which is typical for copper(II) d9 atoms ethanone and 1,3-di\u00adamino\u00adpropan-2-ol in a 2:1 ratio in ethanol yielded the ligand s Table\u00a01 around C3O4 open cube, the basal planes are occupied by one imino nitro\u00adgen atom, one phenolate oxygen anion, one enolato oxygen anion from the same ligand mol\u00adecule and the O atom of the hy\u00addroxy oxygen anion that connects the three copper cations. The copper cations situated on the corners of the open cube are connected by two \u03bc2-Ophenolato and one \u03bc3-Ohy\u00addroxy atoms. In each case, the apical position is occupied by one phenolate oxygen anion from another ligand. The donor atoms of the basal coordination planes of Cu1, Cu3 and Cu5 centres are situated almost in the same plane and the copper cations are displaced from the corresponding apical positions  and O\u2014Cu\u2014O [72.34\u2005(7)\u201386.17\u2005(8)\u00b0] angles, which deviate severely from the ideal value of 90\u00b0 expected for a perfect cube. The atoms defining the three sides of the open cube are almost coplanar  and are irregular with edges of different lengths, i.e. for Cu1/O1/Cu5/O10 these are O1\u2014Cu1 = 1.877\u2005(2)\u2005\u00c5, O10\u2014Cu1 = 2.004\u2005(2)\u2005\u00c5, O1\u2014Cu5 = 2.453\u2005(2)\u2005\u00c5 and O10\u2014Cu5 = 1.978\u2005(2)\u2005\u00c5. Additionally, the dihedral angles values of 78.11\u2005(6), 75.77\u2005(5) and 77.57\u2005(5)\u00b0 between the sides, two by two, confirm the distortion of the open cube. The bond lengths involving the bridging phenolate oxygen anions and the copper cations are asymmetrical: O1\u2014Cu1 = 1.877\u2005(2)\u2005\u00c5 and O1\u2014Cu5 = 2. 453\u2005(2)\u2005\u00c5; O4\u2014Cu1 = 2.389\u2005(2)\u2005\u00c5 and O4\u2014Cu3 = 1.896\u2005(2); and O7\u2014Cu5 = 1.889\u2005(2)\u2005\u00c5 and O7\u2014Cu3 = 2.365\u2005(2)\u2005\u00c5. The distances of the \u03bc3-bridging O atom to the copper cations are slightly different: O10\u2014Cu1 = 2.005\u2005(2)\u2005\u00c5, O10\u2014Cu5 = 1.978\u2005(2)\u2005\u00c5 and O10\u2014Cu3 = 2.004\u2005(2)\u2005\u00c5. The axial bond lengths are longer than the equatorial bond lengths as a result of the Jahn\u2013Teller distortion . The three copper cations are placed at the vertices of an almost isosceles triangle with distances values of 3.1801\u2005(4)\u2005\u00c5 (Cu1\u2014Cu5), 3.1823\u2005(4)\u2005\u00c5 (Cu3\u2014Cu5) and 3.2140\u2005(5)\u2005\u00c5 (Cu1\u2014Cu3) and angle values of 60.68\u2005(1)\u00b0 (Cu1\u2014Cu5\u2014Cu3), 59.69\u2005(1)\u00b0 (Cu5\u2014Cu1\u2014Cu3) and 59.62\u2005(1)\u00b0 (Cu1\u2014Cu3\u2014Cu5).For Cu1, Cu3 and Cu5, which are situated on the vertices of the CuW/O6. The \u03c44 \u201394.26\u2005(10)\u00b0] and the transoid angles are 171.59\u2005(9) and 174.77\u2005(10)\u00b0. The Cu4 cation is coordinated by one enolato oxygen anion (O5), one phenoxo oxygen anion (O6), one azomethine nitro\u00adgen atom (N4) of the ligand, and one O atom from a coordinated water mol\u00adecule. The distances of Cu4 to the coordinated atoms from the ligand  are comparable with those involving Cu2. The Cu4\u2014O1W distance value of 1.961\u2005(2)\u2005\u00c5 is similar to those reported for square-planar copper(II) complexes \u201395.34\u2005(9)\u00b0 and the transoid angles are 171.10\u2005(9) and 173.69\u2005(9)\u00b0. The double-bond character of the C\u2014N bonds [overall values 1.286\u2005(3)\u20131.295\u2005(3)\u2005\u00c5] is indicative of the presence of the imino groups in the three ligands.For the Cu2 and Cu4 centres, the coordination environments can be best described as slightly distorted square planar with r.m.s. deviations from planarity of 0.0601\u2005\u00c5 for Cu2/O2/N2/O3/O11 and 0.0909\u2005\u00c5 for Cu4/N4/O5/O1water\u2014H\u22efOethanol and Owater\u2014H\u22efOnitrate) and C\u2014H\u22efO (Cphenolate\u2014H\u22efOnitrate)   Fig.\u00a02. The comne Fig.\u00a03. The cooN,N\u2032-bis\u00ad[(1-(2-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene)]-2-hy\u00addroxy\u00adpropane-1,3-di\u00adamine has been widely used in coordination chemistry. The current release of the CSD ethyl\u00adidene]}-2-hy\u00addroxy\u00adpropane-1,3-di\u00adamine (HL3), which was prepared according to a literature method : 3538 (OH), 3268 (OH), 1605 (C=N), 1538 (C=C), 1528 (C=C), 1455 (C=C), 1247 (C\u2014O), 1043, 760. Analysis calculated for C19H22N2O3: C, 69.92; H, 6.79; N, 8.58. Found: C, 69.90; H, 6.76; N, 8.56%. A solution of Cu(NO3)2\u00b73H2O  in 5\u2005mL of ethanol was added to a solution of H3L  in 10\u2005mL of ethanol at room temperature. The initial yellow solution immediately turned dark green and was stirred for 30\u2005min. The mixture was filtered, and the filtrate was kept at 298\u2005K. After one week, light-green crystals suitable for X-ray diffraction were collected and formulated as [Cu6L3(NO3)2(OH)(H2O)2]\u00b73EtOH. FT\u2013IR : 1625, 1600, 1540, 1446, 1382, 1304, 1258, 1180, 1120, 1007, 895, 760. Analysis calculated for C63H80Cu6N8O21: C, 45.40; H, 4.84; N, 6.72. Found: C, 45.38; H, 4.82; N, 6.74%.Reaction of 1-(2-hy\u00addroxy\u00adphen\u00adyl)ethanone and 2-hy\u00addroxy\u00adpropane-1,3-di\u00adamine in a 2:1 ratio in ethanol yielded the ligand 2, CH3 groups, hydroxyl groups of ethanol mol\u00adecules and water mol\u00adecules) were geometrically optimized  and refined as riding with Uiso(H) = 1.2Ueq(C) (1.5 for CH3 and OH groups).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021005570/ex2045sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021005570/ex2045Isup2.hklStructure factors: contains datablock(s) I. DOI: 2086932CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound comprises two independent mol\u00adecules that mainly differ in the orientation of the phenyl ring to the rest of the mol\u00adecule. 16H13N3OS, comprises two mol\u00adecules (A and B) with similar conformations that differ mainly in the orientation of the phenyl group relative to the rest of the mol\u00adecule, as expressed by the Cthio\u00adamide\u2014Nthio\u00adamide\u2014Cphen\u00adyl\u2014Cphen\u00adyl torsion angle of 49.3\u2005(3)\u00b0 for mol\u00adecule A and of 5.4\u2005(3)\u00b0 for mol\u00adecule B. In the crystal, two inter\u00admolecular N\u2014H\u22efN hydrogen bonds lead to the formation of a dimer with R22(10) graph-set notation. A Hirshfeld surface analysis revealed that H\u22efH inter\u00adactions are the most important inter\u00admolecular inter\u00adactions, contributing 40.9% to the Hirshfeld surface.The asymmetric unit of the title compound, C The presence of bifunctional properties in thio\u00adamides, resulting from the presence of nitro\u00adgen and sulfur atoms, and their participation in reactions as electrophilic or nucleophilic reagents can lead to the formation of different heterocyclic compounds. Several review articles have been published on the syntheses, physico-chemical properties and applications of thio\u00adamides  and 49.3\u2005(3)\u00b0, respectively, in mol\u00adecule A and 83.78\u2005(19) and 5.4\u2005(3)\u00b0 in mol\u00adecule B. As a result, there are differences in the intra\u00admolecular distances between the sulfur and hydrogen atoms in mol\u00adecules A and B. In mol\u00adecule A, the contacts S1A\u22efH9AB and S1A\u22efH13A are 2.873 and 2.897\u2005\u00c5 whereas the corresponding distances in mol\u00adecule B are 3.054 and 2.578\u2005\u00c5. The phenyl and pyrimidine rings in both mol\u00adecules are essentially coplanar, with r.m.s. deviations of 0.0225 and 0.0119\u2005\u00c5 for mol\u00adecule A and B, respectively. Fig.\u00a02The title compound crystallizes with two mol\u00adecules, it Fig.\u00a01. In mol\u00adA and B form a dimer with an A inter\u00adacts with mol\u00adecule B by a C\u2014H\u22ef \u03c0 inter\u00adaction . Other weak C7A\u2014H7A\u22efO1B, C7A\u2014H7A \u22efO1B, C7B\u2014H7B\u22efO1A, C9A\u2014H9AB\u22efS1A and C13B\u2014H13B\u22efS1B hydrogen bonds link adjacent dimers, forming supra\u00admolecular layers expanding parallel to (010)  Fig.\u00a04. The ovell Fig.\u00a05.CrystalExplorer17.5  whereby H\u22efH contacts are responsible for the largest contribution (40.9%) to the Hirshfeld surface. C\u22efH/H\u22efC contribute 23.7%, S\u22efH/H\u22efS contacts 10.7%, N\u22efH/H\u22efN contacts 8.1% and O\u22efH/H\u22efO contacts 7.0% to the total Hirshfeld surface. The contributions of further contacts are only minor and amount to C\u22efC (4.0%), S\u22efC/C\u22efS (1.9%), N\u22efC/C\u22efN (1.2%), S\u22efS (1.0%), S\u22efC/C\u22efS (0.6%), O\u22efN/N\u22efO (0.2%) and O\u22efC/C\u22efO (0.1%).A Hirshfeld surface (HS) analysis -one moiety with a similar planar conformation as that in the title structure: AFOCIJ  and 4\u2005ml of dimethyl sulfoxide were injected into a round-bottomed flask with a volume of 100\u2005ml. Then the reaction flask was heated to 403\u2005K for 6\u2005h. After the end of the reaction, the flask was cooled and 40\u2005ml of an aqueous sodium hydroxide solution were added. The resulting mixture was filtered, then added to a dilute solution of sulfuric acid (pH 6). The formed precipitate was filtered off and recrystallized in methanol. In total, 0.5\u2005g (64.0%) of the product were obtained, m.p. 481\u2013483\u2005K.0.435\u2005g (0.0025\u2005mol) of 2,3-di\u00admethyl\u00adquinazoline-4-one, 0.465\u2005g (0.005\u2005mol) of aniline, 0.24\u2005g (0.0075\u2005mol) of sulfur, 0.05\u2005g of sodium sulfide (NaUiso(H) = 1.5Ueq(Cmeth\u00adyl) and 1.2Ueq(C), respectively. H atoms bonded to nitro\u00adgen were located in a difference-Fourier map, and their positional and isotropic displacement parameters were freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021013116/wm5629sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013116/wm5629Isup3.cmlSupporting information file. DOI: 10.1107/S2056989021013116/wm5629Isup3.hklStructure factors: contains datablock(s) I. DOI: 2127513CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two similar mol\u00adecules make up the asymmetric unit of the title compound. The crystal structure features short C\u2014H\u22efCl and C\u2014H\u22efO contacts and C\u2014H\u22ef\u03c0 and van der Waals inter\u00adactions. 16H14Cl2N2O, comprises two similar mol\u00adecules, A and B, in which the dihedral angles between the two aromatic rings are 70.1\u2005(3) and 73.2\u2005(2)\u00b0, respectively. The crystal structure features short C\u2014H\u22efCl and C\u2014H\u22efO contacts and C\u2014H\u22ef\u03c0 and van der Waals inter\u00adactions. The title compound was refined as a two-component non-merohedral twin, BASF 0.1076\u2005(5). The Hirshfeld surface analysis and two-dimensional fingerprint plots show that H\u22efH , Cl\u22efH/H\u22efCl  and C\u22efH/H\u22efC  inter\u00adactions are the most important contributors to the crystal packing.The asymmetric unit of the title compound, C In mol\u00adecule A, the N2/N1/C2/C1/Cl1/Cl2 moiety is approximately planar, with a maximum deviation of 0.110\u2005(2)\u2005\u00c5, and makes dihedral angles of 1.2\u2005(2) and 71.3\u2005(2)\u00b0, respectively, with the C3\u2013C8 and C10\u2013C15 rings. In mol\u00adecule B, the N4/N3/C18/C17/Cl3/Cl4 moiety is approximately planar with a maximum deviation of 0.046\u2005(6)\u2005\u00c5, and makes dihedral angles of 9.57\u2005(18) and 75.94\u2005(19)\u00b0, respectively, with the C19\u2013C24 and C26\u2013C31 rings.There are two comparable mol\u00adecules A (with Cl1) and B (with Cl3) in the asymmetric unit of the title compound Fig.\u00a01. The dihvia C\u2014H\u22efCl short contacts, yielding supra\u00admolecular chains along the b-axis direction. Adjacent chains are linked by C\u2014H\u22efO contacts, generating a two-dimensional array parallel to the bc plane . The Cl\u22efH/H\u22efCl inter\u00adactions appear as two symmetrical broad wings with de + di = 2.70\u2005\u00c5 and contribute 24.6% to the Hirshfeld surface for mol\u00adecule A, and with de + di = 2.70\u2005\u00c5 and contribute 26.7% to the Hirshfeld surface for mol\u00adecule B . The pair of characteristic wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts  have the tips at de + di = 2.80\u2005\u00c5 for mol\u00adecule A and at de + di = 2.85\u2005\u00c5 for mol\u00adecule B. The remaining contributions for both mol\u00adecules A and B are from N\u22efH/H\u22efN, O\u22efH/H\u22efO, N\u22efC/C\u22efN, Cl\u22efO/O\u22efCl, Cl\u22efC/C\u22efCl, C\u22efC, Cl\u22efN/N\u22efCl, O\u22efC/C\u22efO and Cl\u22efCl contacts, which are less than 4.6% and have a negligible effect on the packing. The percentage contributions of all inter\u00adactions are listed in Table\u00a03A and B can be attributed to the different mol\u00adecular environments of the A and B mol\u00adecules in the crystal structure.The overall two-dimensional fingerprint plot and those delineated into H\u22efH, Cl\u22efH/H\u22efCl and C\u22efH/H\u22efC contacts in mol\u00adecules ng Fig.\u00a06b. The C B Fig.\u00a06c. The pet al., 2016E)-1--2-phenyl\u00addiazene unit resulted in 27 hits. Eight compounds are closely related to the title compound, viz. 4-{2,2-di\u00adchloro-1-[diazen\u00adyl]ethen\u00adyl}-N,N-di\u00admethyl\u00adaniline \u2005\u00c5]. In DULTAI, the dihedral angle between the two aromatic rings is 64.12\u2005(14)\u00b0. The crystal structure is stabilized by a short C\u2014H\u22efCl contact, C\u2014Cl\u22ef\u03c0 and van der Waals inter\u00adactions. In HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9\u2005(2) and 64.1\u2005(2)\u00b0, respectively. In the crystals, mol\u00adecules are linked through weak X\u22efCl contacts (X = Br for HONBOE and Cl for HONBUK), C\u2014H\u22efCl and C\u2014Cl\u22ef\u03c0 inter\u00adactions into sheets parallel to the ab plane. Additional van der Waals inter\u00adactions consolidate the three-dimensional packing. In HODQAV, the benzene rings make a dihedral angle of 56.13\u2005(13)\u00b0. Mol\u00adecules are stacked in columns along the a-axis direction via weak C\u2014H\u22efCl hydrogen bonds and face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions. The crystal packing is further consolidated by short Cl\u22efCl contacts. In XIZREG, the benzene rings form a dihedral angle of 63.29\u2005(8)\u00b0 and the mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C\u2014Cl\u22ef\u03c0, C\u2014F\u22ef\u03c0 and N\u2014O\u22ef\u03c0 inter\u00adactions. In the crystals of LEQXIR and LEQXOX, the dihedral angles between the aromatic rings are 56.18\u2005(12) and 60.31\u2005(14)\u00b0, respectively. In LEQXIR, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and short C\u2014Cl\u22efO contacts occur and in LEQXOX, C\u2014H\u22efN and short Cl\u22efCl contacts are observed.In GUPHIL, the benzene rings subtend a dihedral angle of 77.07\u2005(10)\u00b0. In the crystal, mol\u00adecules are associated into inversion dimers et al., 2021et al., 2018Z)-1-(4-meth\u00adoxy\u00adphen\u00adyl)-2-(4-methyl\u00adbenzyl\u00adid\u00adene)hydrazine , tetra\u00admethyl\u00adethylenedi\u00adamine , CuCl  and CCl4 . After 1\u20133\u2005h , the reaction mixture was poured into a 0.01\u2005M solution of HCl , and extracted with di\u00adchloro\u00admethane (3 \u00d7 20\u2005mL). The combined organic phase was washed with water (3 \u00d7 50\u2005mL) and brine (30\u2005mL), dried over anhydrous Na2SO4 and concentrated in vacuo by a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and di\u00adchloro\u00admethane (3/1\u20131/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Colorless solid (65%); m.p. 355\u2005K. Analysis calculated for C16H14Cl2N2O: C 59.83, H 4.39, N 8.72; found: C 59.78, H 4.32, N 8.69%. 1H NMR  \u03b4 7.79 , 7.26 , 7.10 , 6.95 , 3.88 , 2.42 . 13C NMR  \u03b4 162.48, 148.12, 147.82, 138.47, 129.90, 129.76, 129.41, 128.85, 125.23, 114.14, 55.58 and 21.48. ESI\u2013MS: m/z: 322.14 [M\u00a0+\u00a0H]+.The title compound was synthesized according to a reported method (Mukhtarova Uiso(H) = 1.2 or 1.5Ueq(C). Owing to poor agreement between observed and calculated intensities, eight outliers  I. DOI: 10.1107/S2056989021008756/zn2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021008756/zn2009Isup3.cmlSupporting information file. DOI: 1984582CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Cellular stress has been associated with inflammation, yet precise underlying mechanisms remain elusive. In this study, various unrelated stress inducers were employed to screen for sensors linking altered cellular homeostasis and inflammation. We identified the intracellular pattern recognition receptors NOD1/2, which sense bacterial peptidoglycans, as general stress sensors detecting perturbations of cellular homeostasis. NOD1/2 activation upon such perturbations required generation of the endogenous metabolite sphingosine\u20101\u2010phosphate (S1P). Unlike peptidoglycan sensing via the leucine\u2010rich repeats domain, cytosolic S1P directly bound to the nucleotide binding domains of NOD1/2, triggering NF\u2010\u03baB activation and inflammatory responses. In sum, we unveiled a hitherto unknown role of NOD1/2 in surveillance of cellular homeostasis through sensing of the cytosolic metabolite S1P. We propose S1P, an endogenous metabolite, as a novel NOD1/2 activator and NOD1/2 as molecular hubs integrating bacterial and metabolic cues. Intracellular pattern recognition receptors NOD1/2, best known as sensor of bacterial peptidoglycans, can also be directly activated by signaling lipid sphingosine\u20101\u2010phosphate accumulating upon perturbed cellular homeostasis, thus linking general stress to inflammatory responses. Altogether, we established that sphingolipid metabolism governs inflammation triggered by cellular stress and identified a central role for S1P in triggering NOD1/2\u2010dependent inflammation upon stress induction.IL6 and IL8 expression and production correlated with NOD1/2 expression, without considerable differences of cell death in association with NOD1 or NOD2 expression  upon perturbation of cellular homeostasis were compromised in both Nod1/2 dKO and Rip2 KO cells  and NOD1/2 double knockout (dKO). NF\u2010\u03baB luciferase assays confirmed that perturbation of cellular homeostasis induced NF\u2010\u03baB activation, while NF\u2010\u03baB activation and  dKO Fig\u00a0. Consistlls Figs . AccordiMDMs Fig\u00a0C and D. et al,et al,et al,ACER1/2, SMPD3,SPHK1 and other key enzymes involved in sphingolipid metabolism  encode the sphingosine kinase  resulted in lower IL8 production upon Shigella infection, suggesting the involvement of S1P in Shigella\u2010induced NF\u2010\u03baB activation  were employed for two reasons: (i) Sphingolipid metabolism in cancer cells is dysregulated  or neutral sphingomyelinase (GW4869), uncovering that S1P is mainly produced via the hydrolysis pathway upon ER stress , S1PR2 (JTE013), S1PR1 and S1PR3 (VPC23019), and S1PR4 (CYM50358), as well as the general S1PR inhibitor FTY720 or blocking GPCR signaling by pertussis toxin, were employed. All inhibitors failed to block IL6 production by cytosolic S1P  with the S1P molecule using AutoDock  domain of human NOD1 is critical for the interaction with S1P  or caspase recruitment domain (CARD)\u2010containing proteins, resembling inflammasomes in vertebrates  and B6N.129S6\u2010Sphk2tm1Rlp/J (Sphk2\u2212/\u2212) mice were originally obtained from the Jackson Laboratory . These mice were maintained under specific pathogen\u2010free (SPF) conditions at the Max Planck Institute for Infection Biology in Berlin, Germany. 6\u2010 to 15\u2010week\u2010old female mice were employed for the experiments.B6N.129S6\u2010Sphk1et al,NLRP3\u2010GFP  was obtained from Addgene. NOD1\u2010 or NOD2\u2010related plasmids were constructed as described , anti\u2010GFP , anti\u2010GFP , anti\u2010RIP2 , anti\u2010SPHK2 , anti\u2010phospho\u2010p38 , anti\u2010phospho\u2010JNK , anti\u2010phospho\u2010ERK1/2 , anti\u2010phospho\u2010p65 , and anti\u2010NOD1 .l\u2010glutamine , 10\u00a0mM HEPES buffer , pH 7.2\u20107.5, and 50\u00a0\u00b5M 2\u2010mercaptoethanol . To differentiate THP\u20101 into macrophage\u2010like cells, THP\u20101 cells were stimulated with 50\u00a0ng/ml phorbol 12\u2010myristate 13\u2010acetate  for 24\u00a0h and then incubated with fresh medium for another 48\u00a0h. HEK293T WT and HEK293T NOD1/2 dKO cells were generated as described  were obtained from tibial and femural bones and generated with DMEM containing 20% L929 cell supernatant, 10% FBS, 5% heat\u2010inactivated horse serum, 1\u00a0mM sodium pyruvate, and 2\u00a0mM l\u2010glutamine. For BMDM stimulation experiments, BMDMs were treated with IFN\u2010\u03b3 (20\u00a0ng/ml) overnight before stimulation.The human monocytic cell line THP\u20101 was obtained from the American Type Culture Collection  and maintained in RPMI 1640  with 10% (v:v) heat\u2010inactivated fetal bovine serum , 1\u00a0mM sodium pyruvate , 2\u00a0mM ueous one solution reagent (Promega) according to the manufacturer\u2019s instructions. Cell viability upon various stimulations was normalized to corresponding controls.Cell viability assays were performed with CellTiter 96 AQShigella flexneri M90T afaE .NOD1/2 KO NF\u2010\u03baB reporter cells were seeded in 96\u2010well plates and stimulated with various stressors for 8\u00a0h. Then, cells were lysed in lysis buffer (Thermo Fisher Scientific) and luciferase activities were determined with firefly luciferase glow kit (Thermo Fisher Scientific) according to the manufacturer\u2019s instructions. Luciferase activities were normalized to the amount of protein determined with Coomassie Plus kit (Thermo Fisher Scientific). Fold inductions were calculated against normalized luciferase activities of corresponding controls.HEK293T WT and 6 cells were treated with indicated stimuli for 2\u00a0h. After washing twice with Dulbecco's phosphate\u2010buffered saline (DPBS) without calcium and magnesium, cells were collected and suspended in 300\u00a0\u00b5l of DPBS. Afterward, cells were transferred into 1.5\u2010ml Eppendorf tubes precooled at \u221280\u00b0C. The lipidomic analysis was performed by Lipotype GmbH. For analysis of sphingosine\u2010related metabolites, 3\u00a0\u00d7\u00a0106 cells were seeded in Lumox 50 dishes and treated with indicated stimuli for 2\u00a0h. After washing twice with 0.9% NaCl preconditioned at 37\u00b0C, the membrane of Lumox dishes was placed into tubes precooled at \u221280\u00b0C. 600\u00a0\u00b5l of quenching solution (dichloromethane/ethanol) was added into each tube. The measurement was performed by Metanomics Health GmbH.For lipidomic profiling, 1\u00a0\u00d7\u00a0102, 0.1% SDS, 1X PhosSTOP, 1X Protease inhibitor cocktail without EDTA). Protein concentration was measured by BCA assay kit (Thermo Fisher) and diluted with delipidized serum to 1\u00a0\u00b5g/\u00b5l. Then, the diluted samples were added into S1P ELISA plates according to the instructions.Quantification of S1P abundances in cell lysates was performed with S1P ELISA kit  according to the manufacturer\u2019s instructions with some modifications. Human neonatal dermal fibroblasts were grown in DMEM full medium. For each condition, 2x T75 flask cells were required. After 4\u2010h stimulation with various stressors, cells were washed with PBS and collected in lysis buffer  in a Bio\u2010Plex 200 system according to the manufacturer\u2019s instructions.The mutagenesis was performed with Q5\u00ae site\u2010directed mutagenesis kit  according to the manufacturer's instructions. The primers used in this study were as follows: NOD1 E157A F: 5\u2032\u2010GCTGCTGGAGgcgATCTACATGG\u20103\u2032, NOD1 E157A R: 5\u2032\u2010AGCTCCTCCTTCTGGGCA\u20103\u2032, NOD1 D161A F: 5\u2032\u2010GATCTACATGgcgACCATCATGGAGCTGG\u20103\u2032, NOD1 D161A R: 5\u2032\u2010TCCTCCAGCAGCAGCTCC\u20103\u2032, NOD1 D203A F: 5\u2032\u2010CATCCTGGGTgcgGCTGGGGTGG\u20103\u2032, D203A R: 5\u2032\u2010AAGATGGTCTCACCCTGC\u20103\u2032, L218A F: 5\u2032\u2010GCTGCAGAGCgcgTGGGCCACGG\u20103\u2032, L218A R: 5\u2032\u2010CGCTGTAGCAGCATGGAC\u20103\u2032, R237A F: 5\u2032\u2010CTTTCGCTGCgcgATGTTCAGCTG\u20103\u2032, R237A R: 5\u2032\u2010TGGAAGAAGAATTTGACC\u20103\u2032, H257A F: 5\u2032\u2010GCTCTTCAAGgcgTACTGCTACCCAGAGCGG\u20103\u2032, H257A R: 5\u2032\u2010AGGTCCTGCAGACACAGC\u20103\u2032, E267A F: 5\u2032\u2010GGACCCCGAGgcgGTGTTTGCCT\u20103\u2032, E267A R: 5\u2032\u2010CGCTCTGGGTAGCAGTAGTG\u20103\u2032, H290A F: 5\u2032\u2010GGACGAGCTGgcgTCGGACTTGGACC\u20103\u2032, H290A R: 5\u2032\u2010AGGCCATCGAAGGTGAAG\u20103\u2032, E306A F: 5\u2032\u2010CTGCCCCTGGgcgCCTGCCCACC\u20103\u2032, E306A R: 5\u2032\u2010GAGCTGTCAGGCACGCGGC\u20103\u2032, K324A F: 5\u2032\u2010GAAGCTGCTCgcgGGGGCTAGCAAG\u20103\u2032, K324A R: 5\u2032\u2010CCACTGAGCAGGTTGGCC\u20103\u2032, K328A F: 5\u2032\u2010GGGGGCTAGCgcgCTGCTCACAG\u20103\u2032, K328A R: 5\u2032\u2010TTGAGCAGCTTCCCACTG\u20103\u2032, R340A F: 5\u2032\u2010CGAGGTCCCGgcgCAGTTCCTGCGGAAG\u20103\u2032, R340A R: 5\u2032\u2010ATGCCTGTGCGGGCTGTG\u20103\u2032, R344A F: 5\u2032\u2010CCAGTTCCTGgcgAAGAAGGTGCTTCTCCGG\u20103\u2032, R344A R: 5\u2032\u2010CGCGGGACCTCGATGCCT\u20103\u2032, R350A F: 5\u2032\u2010GGTGCTTCTCgcgGGCTTCTCCC\u20103\u2032, R350A R: 5\u2032\u2010TTCTTCCGCAGGAACTGG\u20103\u2032, D372A F: 5\u2032\u2010GGCCCTGCAGgcgCGCCTGCTGA\u20103\u2032, D372A R: 5\u2032\u2010CGCTCGGGGAACATCCTC\u20103\u2032, R373A F: 5\u2032\u2010CCTGCAGGACgcgCTGCTGAGCCAGCTG\u20103\u2032, R373A R: 5\u2032\u2010GCCCGCTCGGGGAACATC\u20103\u2032, R399A F: 5\u2032\u2010GATCATCTTCgcgTGCTTCCAGCACTTCC\u20103\u2032, R399A R: 5\u2032\u2010CAGCAGAAGAGGGGCACA\u20103\u2032, D423A F: 5\u2032\u2010GACCCTGACAgcgGTCTTCCTCCTGGTC\u20103\u2032, D423A R: 5\u2032\u2010ATCGTGCAGTCGGGCAGC\u20103\u2032, R435A F: 5\u2032\u20105\u2032\u2010CCATCTGAACgcgATGCAGCCCAGC\u20103\u2032, R435A R: 5\u2032\u2010ACCTCAGTGACCAGGAGG\u20103\u2032, Q484A F: 5\u2032\u2010GGAGGAGGTGgcgGCCTCCGGGC\u20103\u2032, Q484A R: 5\u2032\u2010TGGGTGAAGACAAAGAGGCTC\u20103\u2032, L495A F: 5\u2032\u2010AGACATGCAGgcgGGCTTCCTGCGG\u20103\u2032, L495A R: 5\u2032\u2010CTCTCCTGCAGCCCGGAG\u20103\u2032, E514A F: 5\u2032\u2010GCAGTCCTATgcgTTTTTCCACCTCACCCTCCAGG\u20103\u2032, E514A R: 5\u2032\u2010TGGTCACCCCCGGGGCCC\u20103\u2032, H517A F: 5\u2032\u2010TGAGTTTTTCgcgCTCACCCTCCAGGCCTTCTTTAC\u20103\u2032, H517A R: 5\u2032\u2010TAGGACTGCTGGTCACCC\u20103\u2032, L540A F: 5\u2032\u2010CACTCAGGAGgcgCTCAGGTTCTTCCAGG\u20103\u2032, L540A R: 5\u2032\u2010CCCACCCTGTCGTCCAGC\u20103\u2032, F544A F: 5\u2032\u2010GCTCAGGTTCgcgCAGGAGTGGATGCCC\u20103\u2032, and F544A R: 5\u2032\u2010AGCTCCTGAGTGCCCACC\u20103\u2032.2+, 1\u00a0mM ATP). To elute the proteins, the agarose was mixed with 2\u00a0ml elution buffer  for 1\u00a0min and the eluted proteins were immediately neutralized with 0.2\u00a0ml of 1\u00a0M Tris, pH 10.5.HeLa NOD1 or NOD2 cells from 20 T175 flasks were collected and lysed with 5\u00a0ml lysis buffer . The lysates were incubated with 2\u00a0ml GFP\u2010Trap agarose at 4\u00b0C for 4\u00a0h. The agarose was collected with Poly\u2010Prep columns by gravity flow. Afterward, the agarose was sequentially washed with 50\u00a0ml wash buffer I  and 50\u00a0ml wash buffer II . To remove heat shock proteins, columns were further washed with 50\u00a0ml wash buffer III  and treated with doxycycline overnight to induce NOD1\u2010GFP or NOD2\u2010GFP expression. Afterward, cells were stimulated with S1P\u2010TAMRA (20\u00a0\u00b5M) in the presence of digitonin (5\u00a0\u00b5g/ml) for 2\u00a0h. Then, cells were fixed with 4% (v:v) paraformaldehyde in PBS, pH 7.4 for 10\u00a0min at room temperature (RT). After washing twice with PBS, cells were incubated with 50\u00a0mM glycine in PBS, pH 7.4 for 10\u00a0min and permeabilized with 0.05% saponin , 1% BSA in PBS for 10\u00a0min. Rabbit anti\u2010GFP antibody (ChromoTek) and Alex Fluor 647\u2010conjugated goad anti\u2010rabbit antibody (Thermo Fisher Scientific) were diluted in PBS and incubated for 1\u00a0h at room temperature. The super resolution imaging was performed with Nanoimager S (Oxford Nanoimaging). For single particle tracking in live cells, Nanoimager S was pre\u2010warmed at 37\u00b0C. HeLa inducible NOD1\u2010GFP or NOD2\u2010GFP cells were stimulated with S1P\u2010TAMRA (20\u00a0\u00b5M) in the presence of digitonin (5\u00a0\u00b5g/ml) for 30\u00a0min. Medium was then replaced with fresh DMEM without phenol red. Live imaging was performed with Nanoimager S at acquisition speed of 100fps.GAPDH), and fold changes were calculated against corresponding controls. qRT\u2013PCR data were representative of at least three independent experiments, with at least 2 technical replicates per experiment. The sequences of primers used in this study were as follows: hGAPDH F: 5\u2032\u2010GGAGCGAGATCCCTCCAAAAT\u20103\u2032, hGAPDH R: 5\u2032\u2010GGCTGTTGTCATACTTCTCATGG\u20103\u2032, hIL6 F: 5\u2032\u2010ACTCACCTCTTCAGAACGAATTG\u20103\u2032, hIL6 R: 5\u2032\u2010CCATCTTTGGAAGGTTCAGGTTG\u20103\u2032, hIL8 F: 5\u2032\u2010TTTTGCCAAGGAGTGCTAAAGA\u20103\u2032, hIL8 R: 5\u2032\u2010AACCCTCTGCACCCAGTTTTC\u20103\u2032, mGAPDH F: 5\u2032\u2010AGGTCGGTGTGAACGGATTTG\u20103\u2032, mGAPDH R: 5\u2032\u2010TGTAGACCATGTAGTTGAGGTCA\u20103\u2032, mIL6 F: 5\u2032\u2010TAGTCCTTCCTACCCCAATTTCC\u20103\u2032, mIL\u20106 F: 5\u2032\u2010TTGGTCCTTAGCCACTCCTTC\u20103\u2032, hS1PR1 F: 5\u2032\u2010TTCCACCGACCCATGTACTAT\u20103\u2032, hS1PR1 R: 5\u2032\u2010GCGAGGAGACTGAACACGG\u20103\u2032, hS1PR2 F: 5\u2032\u2010CTAGCCAGTTCTGAAAGC\u20103\u2032, hS1PR2 R: 5\u2032\u2010ACAGAGGATGACGATGAAG\u20103\u2032, hS1PR3 F: 5\u2032\u2010GAGGAGCCCTTTTTCAAC\u20103\u2032, hS1PR3 R: 5\u2032\u2010TCATTTCAAAGGGAAGCG\u20103\u2032, hS1PR4 F: 5\u2032\u2010GACGCTGGGTCTACTATTGCC\u20103\u2032, hS1PR4 R: 5\u2032\u2010CCTCCCGTAGGAACCACTG\u20103\u2032, hS1PR5 F: 5\u2032\u2010AGGAAGCTCAGTTCACAG\u20103\u2032, and hS1PR5 R: 5\u2032\u2010GATTCTCTAGCACGATGAAG\u20103\u2032.Total RNA was isolated with TRIzol reagent, as described by the manufacturer (Invitrogen). RNA (1\u00a0\u03bcg) was used to generate cDNA via the iScript cDNA Synthesis Kit (Bio\u2010Rad), and qRT\u2013PCR was performed using Power SYBR Green Master Mix (Applied Biosystems) in a StepOne Plus thermocycler (Applied Biosystems). The average threshold cycle (Ct) of quadruplicate reactions was employed for all subsequent calculations using the \u0394\u0394Ct method. Gene expression was normalized to glyceraldehyde\u20103\u2010phosphate dehydrogenase . Data represent fold changes (2\u2212\u0394\u0394CT) in transcripts relative to the appropriate internal control (DMSO). Data were generated from 2 technical replicates and at least three independent experiments. TaqMan probes are listed in Table\u00a0Gene expression was analyzed simultaneously with the 96.96 Dynamic Array Integrated Fluidic Circuits from Fluidigm as previously described  following the manufacturer\u2019s protocol using glycogen as co\u2010precipitant. Quality control and quantification of total RNA was analyzed using an Agilent 2100 Bioanalyzer (Agilent Technologies) and a NanoDrop 1000 UV\u2013Vis spectrophotometer (Thermo Fisher Scientific). Microarray experiments were performed as single\u2010color hybridization. Total RNA was amplified and labeled with the Low Input Quick\u2010Amp Labeling Kit (Agilent Technologies). In brief, mRNA was reverse\u2010transcribed and amplified using an oligo\u2010dT\u2010T7 promoter primer and labeled with cyanine 3\u2010CTP. After precipitation, purification, and quantification, 0.75\u00a0\u03bcg labeled cRNA was fragmented and hybridized to custom whole genome human 8\u00a0\u00d7\u00a060K multipack microarrays (Agilent\u2010048908) according to the supplier\u2019s protocol (Agilent Technologies). Scanning of microarrays was performed with 3\u00a0\u03bcm resolution (8x60K) using a G2565CA high\u2010resolution laser microarray scanner (Agilent Technologies). Microarray image data were processed with the Image Analysis/Feature Extraction software G2567AA v. A.11.5.1.1 (Agilent Technologies) using default settings and the GE1_1105_Oct12 extraction protocol. Expression data were analyzed using R scripts. The data were quantile\u2010normalized between arrays, and batch effect of purification state was removed by ComBat  overnight at 4\u00b0C. Afterward, agaroses were washed twice with PBS and boiled with sample buffer for SDS\u2013PAGE. For lipid\u2010coated beads IP, lipid\u2010coated beads were incubated with supernatants for 2\u00a0h at room temperature and then washed with lysis buffer for three times and boiled with sample buffer for SDS\u2013PAGE.HeLa NOD1 or NOD2 cells were grown overnight and afterward treated with doxycycline overnight to induce NOD1 or NOD2 expression. Cells of one 10\u2010cm dish were lysed with 500\u00a0\u00b5l of lysis buffer  supplemented with protease inhibitors  on ice for 20\u00a0min. Lysates were centrifuged at 16,000\u00a0\u00d7\u00a0g for 10\u00a0min, supernatants were heated with SDS sample buffer at 95\u00b0C for 10\u00a0min. Proteins were separated on 4\u201315% SDS gels  and transferred onto nitrocellulose membranes. The membranes were incubated with primary antibodies at 4\u00b0C overnight and secondary antibodies at RT for 1\u00a0h, respectively. All antibodies were diluted in PBS supplemented with 0.1% Tween\u201020  and 5% BSA. Membranes were developed with ECL detection Kit  and exposed with ChemiDoc (Bio\u2010Rad). The antibody against ACTB/\u03b2\u2010actin was used as loading control.Cells were lysed in RIPA buffer supplemented with protease inhibitor cocktail and PhosSTOP  on ice for 10\u00a0min. After centrifugation at 16,000\u00a0\u00d7\u00a0Kd values.Binding of NOD1, NOD2, GFP, or NLRP3\u2010GFP to different ligands was measured by microscale thermophoresis (MST). 20\u00a0nM GFP or GFP\u2010tagged proteins in MST buffer  was incubated with different concentrations of ligands. Immediately, samples were loaded into standard glass capillaries (NanoTemper) and thermophoresis analysis was performed on a NanoTemper Monolith NT.115 instrument  at 22\u00b0C. A laser on\u2010time of 30\u00a0s and a laser off\u2010time of 5\u00a0s were used. The experiment was performed in triplicates, and the MST curves were fitted using NT analysis software to obtain the et al,et al,et al,et al,AutoDock Tools  was satisfied. The system was first minimized with the restraints  on the solute (includes the protein and ligand) followed by another round of free minimization. The systems were heated from 0 to 300\u00a0K  on the protein and ligand in 100\u00a0ps. Then, the unrestrained systems were equilibrated for 1\u00a0ns with Langevin thermostat in the NPT (P\u00a0=\u00a01\u00a0atm and T\u00a0=\u00a0300\u00a0K) ensemble  with Holm\u2013Sidak post hoc test and ANOVA test of linear mixed model for fix effect of main factors were performed. A two\u2010tailed P value of <\u00a00.05 was considered to be significant.Statistical analysis was performed with GraphPad Prism v7.03 . Normal distribution has been evaluated with the Shapiro\u2013Wilk test using GraphPad Prism. To determine statistical significance among investigated groups, Student\u2019s GP, AD, and SHEK conceived and designed the study, analyzed the data, and wrote the manuscript. GP designed and performed most of the experiments. JZ, JW, and H\u2010JM conducted microarray and data analysis. LH performed molecular docking. MD performed molecular dynamic simulation. PM\u2010A generated knockdown cells. PS participated in the mouse experiments. LL performed Fluidigm gene expression analysis. TAK provided cell lines, plasmids, and conceptual discussions. KE and CA generated HeLa inducible GFP, NOD1\u2010GFP, and NOD2\u2010GFP cells. HS performed Shigella infection experiments. NN, YD, MP, and IGB helped with the experiments. All the coauthors commented on the manuscript.The authors declare thet they have no conflict of interest.AppendixClick here for additional data file.Expanded View Figures PDFClick here for additional data file.Source Data for Expanded View and AppendixClick here for additional data file.Review Process FileClick here for additional data file.Source Data for Figure 4Click here for additional data file.Source Data for Figure 5Click here for additional data file."}
{"text": "In complex 1 the Re\u2014Re bond lengths [2.9767\u2005(3)\u20133.0133\u2005(2)\u2005\u00c5] are close to double the covalent Re radii (1.51\u2005\u00c5). The palladium\u2013rhenium carbonyl cluster 2 has not been structurally characterized previously; the Pd\u2014Re bond lengths [2.7582\u2005(2)\u20132.7796\u2005(2)\u2005\u00c5] are about 0.1\u2005\u00c5 shorter than the sum of the covalent Pd and Re radii (1.39\u00a0+\u00a01.51 = 2.90\u2005\u00c5). One carbene ligand and a diethyl ether mol\u00adecule are disordered over two positions with occupancy ratios of 0.5:0.5 and 0.625\u2005(15):0.375\u2005(15) in 1. An unidentified solvent is present in compound 2. The given chemical formula and other crystal data do not take into account the unknown solvent mol\u00adecule(s). The SQUEEZE routine [Spek  and rhenium (Re) led to the isolation and crystallographic characterization of tetra\u00adkis\u00adpalladium(II) hexa\u00addeca\u00adcarbonyl\u00adtetra\u00adrhenium diethyl ether disolvate, [Pd(CSpek 2015. Acta Cr Two other products, tri\u00adphenyl\u00adphosphine oxide and the known complex Re2(CO)8(PPh3)2  and rhenium (Re) have important applications in alkane reforming, industrial chemical production, hydro\u00addechlorination and biomass conversion  cation with four coordinated N-heterocyclic carbenes (NHC) lying on a twofold rotoinversion axis, and one [Re4(CO)16] anion. The geometry around the Pd atom is square-planar with one carbene unit being disordered. The C\u2014Pd\u2014C angles range from 86.9\u2005(4) to 97.7\u2005(4)\u00b0. The cluster anion lying on the inversion center has a perfectly flat rhombus geometry with the shortest Re\u2014Re bond [2.9767\u2005(3)\u2005\u00c5] corresponding to the short diagonal. The other four Re\u2014Re bond lengths [3.001\u2005(2)\u20133.0132\u2005(2)\u2005\u00c5] are also close to double the covalent Re radii \u20132.7796\u2005(2)\u2005\u00c5] are close to the sum of the covalent Pd and Re radii (1.39\u00a0+\u00a01.51 = 2.90\u2005\u00c5). In comparison, the Pd\u2014Re bond lengths in the PdRe4(CO)16(\u03bc-SbPh2)2(\u03bc-H)2 cluster \u201390.135\u2005(6)\u00b0 and the Pd\u2014Pd bond lengths are 2.9678\u2005(2)\u20132.99\u2005(2)\u2005\u00c5].The displacement ellipsoid plot of 1, each cation is surrounded by six anions and vice versa palladium(II) diiodide 16]2\u2212 anion, which is also found in the compound reported here. A search of the CSD found two closely related cluster compounds, viz. bis\u00ad(tetra\u00adethyl\u00adammo\u00adnium) hexa\u00addeca\u00adcarbonyl-tetra\u00adrhenium \u00adhexa\u00addeca\u00adcarbonyl\u00adtetra\u00adrhenium 4  was added to a toluene\u2013aceto\u00adnitrile mixture  and 1,3-di\u00admethyl\u00adimidazolium-2-carboxyl\u00adate . The reaction mixture was refluxed for 1.5\u2005h, then Re2(CO)10  was added, the solution turned dark red and the solvents were removed in vacuo. The solid was washed with benzene (3 \u00d7 5\u2005ml) and recrystallized from an aceto\u00adnitrile\u2013di\u00adethyl\u00adether mixture. X-ray quality crystals of Pd(IMe)4Re4(CO)16\u00b72C4H10O  were grown from a di\u00adchloro\u00admethane\u2013di\u00adethyl\u00adether mixture at 277\u2005K. 1HNMR : 3.41 , 7.37 . 13C{H} NMR : 36.9 , 123.5 , 168.0 , 197.7 (CO), 198.7 (CO), 201.1 (CO), 218.6 (CO) IR : 3152 , 1998 (vw), 1974 (vw), 1955 (m), 1927 (vw), 1912 (vw), 1881 , 1858 (vw), 1575 (vw), 1465 (w), 1400 (vw), 1332 (vw), 1229 (m), 1131 (vw), 1083 (vw), 1013 (vw), 845 (vw), 736 (s), 701 (vw), 681 (m), 600 (w), 577 (s), 560 (vw), 508 (vw), 496 (vw), 464 (w), 436 (vw), 411 (w).Under a nitro\u00adgen atmosphere, Pd(PPh4Re2(PPh3)4(m-CO)8(CO)2 suitable for X-ray diffraction analysis were obtained from a yellow benzene solution, after several days, by slow ether diffusion into a concentrated solution of benzene at 277\u2005K. IR : 3850 (vw), 3054 , 2955 , 1986 (s), 1821 , 1585 (vw), 1571 (vw), 1515 (vw), 1477 (w), 1434 (m), 1307 (vw), 1263 (vw), 1236 , 1182 (vw), 1159 (vw), 1119 (vw), 1092 (m), 1071 (vw), 1026 (vw), 997 (w), 907 (vw), 846 (vw), 741 (m), 690 (vs), 618 (vw), 565 (w), 541 (vw), 496 (m), 412 (vw).A few crystals of Pd2(CO)8(PPh3)2  were also isolated from this crystallization.Tri\u00adphenyl\u00adphosphine oxide  and Resp2), 0.98\u2005\u00c5 (meth\u00adyl) and 0.99\u2005\u00c5 (methyl\u00adene), with common isotropic temperature factors for all hydrogen atoms of the aromatic rings and methyl groups. SADI restraints on bond lengths and DELU restraints on anisotropic thermal parameters were used to model the disordered carbene ligand and diethyl ether mol\u00adecule over two positions. For the refinement of 2, four reflections  global, 1, 2. DOI: 10.1107/S2056989021009270/tx20411sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989021009270/tx20412sup3.hklStructure factors: contains datablock(s) 2. DOI: 2108168, 2108167CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds connect these dimers to form a three-dimensional network. In addition, C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions help to stabilize the packing.In the crystal, strong C\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds form dimers with  19H17N3O2, adopts a screw-boat conformation. In the crystal, strong C\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds form dimers with R22(14) and R22(12) ring motifs, respectively, between consecutive mol\u00adecules along the c-axis direction. Inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds connect these dimers, forming a three-dimensional network. C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions contribute to the stabilization of the mol\u00adecular packing. A Hirshfeld surface analysis indicates that the contributions from the most prevalent inter\u00adactions are H\u22efH (47.1%), C\u22efH/H\u22efC (20.9%), O\u22efH/H\u22efO (15.3%) and N\u22efH/H\u22efN (11.4%).The central tetra\u00adhydro\u00adpyridine ring of the title compound, C The C7\u2013C12 phenyl ring, which is attached to N1, is in an equatorial position and makes a dihedral angle of 54.43\u2005(9)\u00b0 with the mean plane of the tetra\u00adhydro\u00adpyridine ring. The C13\u2013C18 meth\u00adoxy\u00adphenyl ring, which is attached to C4, is in an axial position. The dihedral angle between the C7\u2013C12 phenyl and C13\u2013C18 meth\u00adoxy\u00adphenyl rings is 68.61\u2005(10)\u00b0.The title compound Fig.\u00a01 crystallC\u22efN2 hydrogen bonds  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; (v) \u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0Cg3 is the centroid of the C13\u2013C18 meth\u00adoxy\u00adphenyl ring; Table\u00a01Cg2\u22efCg2iii = 3.8918\u2005(15)\u2005\u00c5 and slippage = 1.551\u2005\u00c5; Cg2 is the centroid of the C7\u2013C12 phenyl ring] contribute to the stabilization of the mol\u00adecular packing  to 1.8469 (blue) a.u. The dnorm mapping indicates that strong hydrogen-bonding inter\u00adactions, such as N\u2014H\u22efN, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds , followed by C\u22efH/H\u22efC , O\u22efH/H\u22efO  and N\u22efH/H\u22efN . The percentage contributions of the C\u22efC, C\u22efN/N\u22efC and N\u22efN contacts are negligible, at 3.1, 1.4 and 0.8%, respectively. The predominance of H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO and N\u22efH/H\u22efN contacts indicate that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing -6-oxo-1-phenyl-1,4,5,6-tetra\u00adhydro\u00adpyridine-3-carbo\u00adnitrile (I)  -2-(pyridin-2-yl)ethen\u00adyl]-1,4,5,6-tetra\u00adhydro\u00adpyridine-3-carboxyl\u00adate (III)   crystallizes in the monoclinic space group Pc with Z = 4, and with two mol\u00adecules, A and B, in the asymmetric unit. These mol\u00adecules are stereoisomers with an R,R absolute configuration at C3 and C4 in mol\u00adecule A, whereas the corresponding atoms in B, C23 and C24, have an S configuration. In both mol\u00adecules, the conformation of the central di\u00adhydro\u00adpyridine ring is close to screw-boat. The mol\u00adecular conformation is stabilized by N\u2014H\u22efO hydrogen bonds, forming a dimer with an c-axis direction. Furthermore C\u2014Br\u22ef\u03c0 and C=O\u22ef\u03c0 stacking inter\u00adactions between these ribbons contribute to the stabilization of the mol\u00adecular packing.Compound (II) crystallizes in the monoclinic space group P21/c with Z = 4 and the asymmetric unit comprises one mol\u00adecule. The central tetra\u00adhydro\u00adpyridine ring is almost planar with a maximum deviation of 0.074\u2005(3)\u2005\u00c5 for C4. The phenyl and di\u00adchloro\u00adphenyl rings are at an angle of 21.28\u2005(15)\u00b0. They form dihedral angles of 86.10\u2005(15) and 87.17\u2005(14)\u00b0, respectively, with the central tetra\u00adhydro\u00adpyridine ring. A strong intra\u00admolecular O2\u2014H2\u22efO1 hydrogen bond stabilizes the mol\u00adecular conformation of the mol\u00adecule, creating an S(6) ring motif. In the crystal, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, and N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network.Compound (III) , the cis configuration of the pyridinyl-vinyl fragment is stabilized by a strong intra\u00admolecular N\u2014H\u22efN hydrogen bond. The phenyl and pyridine rings are inclined to one another by 77.3\u2005(1)\u00b0. In the crystal, inversion dimers are present via pairs of C\u2014H\u22efO hydrogen bonds and are further linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions.In mol\u00adecule (IV) , the mol\u00adecules form dimers by means of a pair of N\u2014H\u22efO hydrogen bonds. The 2(1H)-pyridone ring displays a screw-boat conformation.For compound (To a solution of 2-(4-meth\u00adoxy\u00adbenzyl\u00adidene)malono\u00adnitrile  and acetoacetanilide  in methanol (25\u2005mL), 3-4 drops of piperidine were added and the mixture was stirred at 328\u2013333\u2005K for 10\u2005min and was kept at room temperature for 48\u2005h. Then 15\u2005mL of methanol were removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from ethanol/water (1:1) solution .1H NMR : 2.80 ; 3.19 ; 3.82 ; 3.93 ; 5.85 ; 7.15\u20137.58 . 13C NMR : 36.06 (CH\u2014Ar), 40.42 (CH2), 53.78 (OCH3), 59.05 (Cquat.), 112.89 (2CHar), 121.21 (CN), 128.61 (CHar.), 128.88 (2CHar.), 130.44 (2CHar.), 130.51 (2CHar.), 136.06 (Car. quat.), 137.02 (Car. quat.), 154.59 (Car. quat.), 155.18 (Cquat.), 168.82 (N\u2014C=O).C = 0.91\u2005(2) and N3\u2014H3D = 0.91\u2005(2)\u2005\u00c5 with Uiso(H) = 1.2Ueq(N)]. C-bound H atoms were positioned geometrically, with C\u2014H = 0.95\u20131.00\u2005\u00c5, and were refined with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698902200175X/vm2260sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902200175X/vm2260Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902200175X/vm2260Isup3.cmlSupporting information file. DOI: 2152191CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This compound exists in the crystal phase as a methanol solvate.The mol\u00adecular and crystal structures of the title compound, C 36H37ClN4O7\u00b7CH3OH, which crystallizes as a methanol solvate, may possess biological activity, which is inherent for a natural peptide or protein. In the crystal, mol\u00adecules of the title compound form hydrogen-bonded tetra\u00admers with the solvate mol\u00adecules acting as bridges as a result of the O\u2014H\u22efO and N\u2014H\u22efO inter\u00admolecular hydrogen bonds. Hirshfeld surface analysis was used to study the different types of inter\u00admolecular inter\u00adactions whose contributions are: H\u22efH = 53.8%, O\u22efH/H\u22efO = 19.0%, C\u22efH/H\u22efC = 14.8%, Cl\u22efH/H\u22efCl = 5.3%, N\u22efH/H\u22efN = 3.2%.The title compound, C The target product contains a heterocyclic core bound to peptidomimetics, compounds that mimic a natural peptide or protein and which may have high biological activity. The pyrrolone fragment is also a privileged motif because of its biological activities, namely anti\u00adbacterial  with the populations of A:B in a 0.303\u2005(10):0.697\u2005(10) ratio. All atoms of the partially saturated five-membered heterocycle are in the same plane with an accuracy of 0.008\u2005\u00c5. The N2\u2014C4 bond length of 1.380\u2005(3)\u2005\u00c5 and the C8\u2014N2\u2014C4\u2014N1 torsion angle of 2.2\u2005(4)\u00b0 indicate conjugation between the \u03c0-systems of the partially saturated and oxazole cycles. The para-chloro\u00adphenyl substituent is located in the pseudo-equatorial position and is turned in relation to the C7\u2014C8 endocyclic bond [C6\u2014C7\u2014C8\u2014C9 = \u2212120.9\u2005(3)\u00b0 and C7\u2014C8\u2014C9\u2014C10 = 60.9\u2005(3)\u00b0]. The C16(=O4)\u2014N3 carb\u00adamide group is located in the -ac position in relation to the C6\u2014C7 endocyclic bond [C6\u2014C7\u2014C15\u2014C16 = \u2212107.2\u2005(3)\u00b0], and the C16=O4 carbonyl group is slightly non-coplanar to the C7\u2014C15 bond [C7\u2014C15\u2014C16\u2014O4 = 22.5\u2005(4)\u00b0]. The para-meth\u00adoxy\u00adphenyl substituent at the nitro\u00adgen atom is turned almost orthogonally to the plane of the carbamide group [C16\u2014N3\u2014C17\u2014C22 = \u221299.5\u2005(3)\u00b0]. The para-meth\u00adoxy\u00adphenyl substituent at the carbon atom is located in a position inter\u00admediate between sp and \u2212sc and is also rotated almost orthogonally to the plane of the carbamide group . In both para-meth\u00adoxy\u00adphenyl substituents, the meth\u00adoxy group is coplanar with the plane of the aromatic ring  despite the steric repulsion between the methyl group and the aromatic ring atoms . The substituent at the C24 atom is located in the \u2212sc position relative to the N3\u2014C16 bond [C32\u2014C24\u2014N3\u2014C16 = \u221278.1\u2005(3)\u00b0] and the C32\u2014O6 carbonyl group is slightly non-coplanar to the N3\u2014C24 bond [O6\u2014C32\u2014C24\u2014N3 = \u221227.8\u2005(3)\u00b0]. The tert-butyl substituent is located in anti\u00adperplanar position to the C32\u2014C24 bond [C33\u2014N4\u2014C32\u2014C24 = 172.9\u2005(2)\u00b0].The title compound crystallizes as a methanol solvate Fig.\u00a01. The metA\u22efO8A, O3\u2014H8B\u22efO8B, O8A\u2014H8A\u22efO4 and O8B\u2013H8B\u22efO4 inter\u00admolecular hydrogen bonds . The highest contribution is from H\u22efH contacts (53.8%), while these made by the O\u22efH/H\u22efO (19.0%) and C\u22efH/H\u22efC (14.8%) inter\u00adactions are similar . The contributions of Cl\u22efH/H\u22efCl (5.3%) and N\u22efH/H\u22efN (3.2%) inter\u00adactions  are very small.In the two-dimensional fingerprint plots the pair of sharp spikes indicate strong hydrogen bonds and short contacts in the crystal structure Fig.\u00a04a. The har Fig.\u00a04c, 4d. Tns Fig.\u00a04e, 4f aret al., 2016et al., 2019et al., 2018et al., 2003bet al., 2011et al., 2013et al., 2017et al., 2003aet al., 2011et al., 2009et al., 2015et al., 2005et al., 2019et al., 2019et al., 2008et al., 2016et al., 2018et al., 1991et al., 2006et al., 1990et al., 2016et al., 2001et al., 2019et al., 2004et al., 2014A search of the Cambridge Structural Database  (0.5\u2005mmol) and 4-meth\u00adoxy\u00adbenzaldehyde (2) (0.5\u2005mmol) were dissolved in methanol (4\u2005mL) and stirred for 0.5\u2005h. Then, 2-acetic acid (1) (0.5\u2005mmol) and tert-butyl\u00adisocyanide (4) (0.5\u2005mmol) were added consistently and the reaction mixture was stirred for 24\u2005h at 319\u2005K. The mixture was allowed to stand overnight. The crystal precipitate was filtered off and dried. The reaction scheme is shown in Fig.\u00a054-Meth\u00adoxy\u00adaniline (Uiso(H) = 1.5Ueq for methyl and hydroxyl groups and with Car\u2014H = 0.93\u2005\u00c5, Csp3\u2014H = 0.97\u2005\u00c5, N\u2014H = 0.89\u2005\u00c5 Uiso(H) = 1.2Ueq for all other hydrogen atoms. The solvent molecule is disordered over two positions (A and B) in a 0.303\u2005(10):0.697\u2005(10) occupancy ratio. Csp3\u2014O bonds were refined with fixed length of 1.413\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989021011312/zq2268sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021011312/zq2268Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021011312/zq2268Isup3.cmlSupporting information file. DOI: 2118094CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compounds feature O\u2014H\u22efO carb\u00adoxy\u00adlic-acid inversion dimers and N\u2014H\u22efN chains in their extended structures. 11H11N3O3, (I), and C10H10N2O2, (II), are commercially available and were crystallized from ethyl acetate solution. The dihedral angle between the pyrazole and phenyl rings in (I) is 52.34\u2005(7)\u00b0 and the equivalent angle between the isoxazole and phenyl rings in (II) is 7.30\u2005(13)\u00b0. In the crystal of (I), the mol\u00adecules form carb\u00adoxy\u00adlic acid inversion dimers with an R(8) ring motif via pairwise O\u2014H\u22efO hydrogen bonds. In the crystal of (II), the mol\u00adecules are linked via N\u2014H\u22efN hydrogen bonds forming chains propagating along [010] with a C(5) motif. A weak N\u2014H\u22ef\u03c0 inter\u00adaction also features in the packing of (II). Hirshfeld surface analysis was used to explore the inter\u00admolecular contacts in the crystals of both title compounds: the most important contacts for (I) are H\u22efH (41.5%) and O\u22efH/H\u22efO (22.4%). For (II), the most significant contact percentages are H\u22efH (36.1%) followed by C\u22efH/H\u22efC (31.3%).The title compounds, C The C3\u2014N3 distance of 1.353\u2005(2)\u2005\u00c5 is typical for an amino group bound to an aromatic ring. The carb\u00adoxy\u00adlic carbon\u2013oxygen distances are 1.255\u2005(2) and 1.316\u2005(2) for C4\u2014O2 and C4\u2014O1, respectively, indicating that the former bond may be affected by the intra\u00admolecular N\u2014H\u22efO hydrogen bond.The mol\u00adecular structure of compound (I)d Table\u00a01. This boif Fig.\u00a01 with an Database survey section). The C3\u2014N2 distance is 1.350\u2005(5)\u2005\u00c5 and is typical of an amino group bound to an aromatic ring.The mol\u00adecular structure of compound (II)via the O1\u2014H1\u22efO2i  link to generate an R(8) loop with O\u22efO = 2.649\u2005(2)\u2005\u00c5, see Table\u00a01via \u03c0\u2013\u03c0 inter\u00adactions, notably weak stacking inter\u00adactions between the 4-meth\u00adoxy\u00adphenyl rings  along the a-axis direction.In the extended structure of (I)b-axis direction via the N2\u2014H2A\u22efN1i hydrogen bond , C6\u2014H6\u22efCg1iii (2.86\u2005\u00c5) and C9\u2014H9\u22efCg2ii (2.86\u2005\u00c5) . Analysis of the two-dimensional fingerprint plots indicates that the H\u22efH (36.1%) inter\u00adactions are the major factor in the crystal packing with C\u22efH/H\u22efC (31.3%) contacts making the next highest contribution. The percentage contributions of other weak inter\u00adactions are: O\u22efH/H\u22efO (17.3%) and N\u22efH/ H\u22efN (12.1%). Figures showing the shape-index surface for each compound and the overall fingerprint plots are included in the supporting information.Fig.\u00a06et al., 2016et al., 1974et al., 2007N-4-dimethyl-N-[3-{4-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]-1,2-oxazol-5-yl}benzene-1-sulfonamide -1,2-oxazole -5-nitro-4,5-di\u00adhydro-1H-pyrazole-4-carboxyl\u00adate Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). In order to ensure a chemically meaningful O\u2014H distance in (I)Uiso(H) = 1.5Ueq(O). In (I)Uiso(H) = 1.5Ueq(N). The absolute structure of (II)Crystal data, data collection, and structure refinement details are summarized in Table\u00a0310.1107/S2056989022001827/hb8013sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022001827/hb8013Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001827/hb8013IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022001827/hb8013Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022001827/hb8013IIsup5.cmlSupporting information file. DOI: 10.1107/S2056989022001827/hb8013sup6.pdfShape-index and fingerprint plots for compounds (I) and (II). DOI: 2152583, 2152582CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Neighbouring (C 12H15N2)2[ZnCl4], is a salt with two symmetrically independent, essentially planar heterocyclic cations and a slightly distorted tetra\u00adhedral chloro\u00adzincate dianion. N\u2014H\u22efCl hydrogen bonds link these ionic constituents into a discrete aggregate, which comprises one formula unit. The effect of hydrogen bonding is reflected in the minor distortions of the [ZnCl4]2\u2212 moiety: distances between the cation and chlorido ligands engaged in classical hydrogen bonds are significantly longer than the others. Secondary inter\u00adactions comprise C\u2014H\u22ef\u03c0 hydrogen bonding and weak \u03c0\u2013\u03c0 stacking. A Hirshfeld surface analysis indicates that the most abundant contacts in packing stem from H\u22efH (47.8%) and Cl\u22efH/H\u22efCl (29.3%) inter\u00adactions.The title compound, (C Mackinlaya sp.  tetra\u00adchlorido\u00adzincate, an inter\u00admediate in the synthesis of mackinazolinone, using high-resolution diffraction data and Hirshfeld surface analysis.Tricyclic quinazolines are counted among the most exciting quinazoline alkaloids. Specifically, the alkaloid mackinazoline was isolated from P21/n space group, with two [C12H15N2]+ cations and a [ZnCl4]2\u2212 counter-anion in the asymmetric unit  are essentially coplanar, with r.m.s. deviations of 0.0437 and 0.0168\u2005\u00c5 for mol\u00adecules A and B, respectively. The remaining atoms of the third ring are significantly displaced above the opposite faces of these planes with deviations of 0.3877\u2005(12)\u2005\u00c5 for C10A and 0.3831\u2005(11)\u2005\u00c5 for C11A in residue A and 0.4705\u2005(11)\u2005\u00c5 for C10B and 0.2495\u2005(11)\u2005\u00c5 for C11B in residue B. Fig.\u00a02The title compound crystallizes in the it Fig.\u00a01. The benA and N1B, respectively, and the acquired positive charge is delocalized within the \u2013N\u2013C\u2013N\u2013 moiety in the ring, where the N1A\u2014C2A and N1B\u2014C2B bonds are only slightly longer than C2A\u2014N3A and C2B\u2014N3B  fragment (see Table S1 in the supporting information).However, these C\u2014N bond lengths are shorter than those in the related tricyclic protonated  and the very favourable ratio between observations and variables (100:1) in our diffraction data result in small standard uncertainties for atomic coordinates and derived geometric parameters and allow to discuss more subtle details. The most acute angle of 103.33\u2005(11)\u00b0 within the tetra\u00adchlorido\u00adzincate dianion  graph-set motif \u2005\u00c5] and involves an inter\u00adaction between the electron-rich equatorial region of the halogen atom and the ring atom attached to two N-atom neighbours, most probably the most electron-deficient atom in the heterocycle. These contacts link anions and cations into a three-dimensional network. Weak \u03c0\u2013\u03c0 stacking inter\u00adactions occur between pyrimidine  and benzene  rings of anti\u00adparallel pairs of cations and involve contact distances of Cg1\u22efCg3  = 3.6225\u2005(5)\u2005\u00c5 (slippage 0.857\u2005\u00c5) and of Cg7\u22efCg9  = 3.6246\u2005(7)\u2005\u00c5 (slippage 0.994\u2005\u00c5).The crystal packing is further stabilized by inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions Table\u00a02 and addiCrystalExplorer17.5  analysis  in Fig.\u00a06ly Fig.\u00a06. Minor cet al., 20164]2\u2212 anions. They are associated with refcodes PODLUP  of 2,3-tetra\u00admethyl\u00adenquinazoline-4-one Fig.\u00a07 were plaUiso(H) = 1.2Ueq(C). H atoms bonded to nitro\u00adgen were located in a difference-Fourier map, and their positional and isotropic displacement parameters were freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989021004989/jq2006sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021004989/jq2006Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004989/jq2006sup4.docxSupporting information file. DOI: 2082994CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both polymorphs are monoclinic and the [Rh(\u03bc-I)(COD)]2 mol\u00adecules in each case possess C2v symmetry. However, the core geometry of the butterfly-shaped Rh2I2 core differs substanti\u00adally. In the C2/c polymorph, the core geometry of [Rh(\u03bc-I)(COD)]2B is bent, with a hinge angle of 96.13\u2005(8)\u00b0 and a Rh\u22efRh distance of 2.9612\u2005(11)\u2005\u00c5. The P21/c polymorph features a more planar [Rh(\u03bc-I)(COD)]2P core geometry, with a hinge angle of 145.69\u2005(9)\u00b0 and a Rh\u22efRh distance of 3.7646\u2005(5)\u2005\u00c5.The solid-state structure of di-\u03bc-iodido-bis\u00ad{rhodium(I)}, [Rh M(\u03bc-X)(COD)]2,  are ubiquitous synthons for Rh and Ir catalysts. As a representative example, [Rh(COD)(DPEphos)]BF4 catalyzes the hydro\u00adamination of vinyl\u00adarenes with anti-Markovnikov selectivity, and is prepared via the reaction of [Rh(\u03bc-Cl)(COD)]2 with two equivalents of AgBF4 and two equivalents of DPEphos (COD)]2 , all compounds have been structurally characterized with the notable exception of [Rh(\u03bc-I)(COD)]2 (COD)]2 containing dimers with significantly different structural features. X-ray diffraction of the dark-orange crystals revealed that [Rh(\u03bc-I)(COD)]2 crystallized in the monoclinic C2/c space group in this polymorph. The mol\u00adecular structure of [Rh(\u03bc-I)(COD)]2B exhibited a C2v-symmetric geometry featuring a bent Rh2I2 diamond core (COD)]2 and [Rh(\u03bc-Br)(COD)]2, which both exhibit more planar Rh2X2 cores with hinge angles of 169.08\u2005(6) and 148.74\u2005(7)\u00b0 and Rh\u22efRh distances of 3.5169\u2005(6) and 3.5648\u2005(14)\u2005\u00c5, respectively (COD)]2 re Fig.\u00a01. The hin2, this time crystallizing in the monoclinic P21/c space group. The geometry of the dirhodium dimer in the P21/c polymorph [Rh(\u03bc-I)(COD)]2P differs significantly from the C2/c polymorph [Rh(\u03bc-I)(COD)]2B. The Rh2I2 core geometry of [Rh(\u03bc-I)(COD)]2P is more planar, with a hinge angle of 145.69\u2005(9)\u00b0 and a Rh\u22efRh distance of 3.7646\u2005(5)\u2005\u00c5 (COD)]2 and [Rh(\u03bc-Br)(COD)]2 (COD)]\u2005\u00c5 Fig.\u00a02. The mol\u22121) between planar and bent [Rh(\u03bc-X)(L)2]2 geometries (COD)]2B but not [Rh(\u03bc-Cl)(COD)]2 and [Rh(\u03bc-Br)(COD)]2 (COD)]2.A previous theoretical study found relatively small energetic differences  and 2.6975\u2005(7)\u2005\u00c5]. The four Rh\u2014I distances in [Rh(\u03bc-I)(COD)]2P are slightly less symmetric: the bonds between I2 and the two Rh centers [2.6833\u2005(4) and 2.6738\u2005(4)\u2005\u00c5] are slightly shorter than those associated with I1 [2.6998\u2005(4) and 2.7061\u2005(4)\u2005\u00c5]. Similarly, the Rh\u2014C distances in [Rh(\u03bc-I)(COD)]2B are more symmetric, ranging from 2.115\u2005(6) to 2.122\u2005(6)\u2005\u00c5, while the Rh\u2014C distances in [Rh(\u03bc-I)(COD)]2P range from 2.117\u2005(4) to 2.131\u2005(4)\u2005\u00c5. The average Rh\u2014C distance in the bent and planar structures are similar to the average Rh\u2014C distances reported for the [Rh(\u03bc-Cl)(COD)]2 and [Rh(\u03bc-Br)(COD)]2 analogues (COD)]2P  are considerably longer than the average Rh\u2014Br and Rh\u2014Cl distances in [Rh(\u03bc-Br)(COD)]2 and [Rh(\u03bc-Cl)(COD)]2 .There is no meaningful difference between the two independent Rh\u2014I distances in [Rh(\u03bc-I)(COD)]2 are attributed to differences in crystal packing and weak inter\u00adatomic forces. The bent and planar geometries are likely similar in energy. Stabilization of the bent geometry in [Rh(\u03bc-I)(COD)]2B arises from intra\u00admolecular dispersion forces between the C\u2014H bonds of the cyclo\u00adocta\u00addiene ligands on the two Rh centers within each mol\u00adecule. Indeed there are four close C\u2014H\u22efH\u2014C contacts  between the alkene and methyl\u00adene hydrogen atoms made possible by the bent geometry (COD)]2P are two Rh\u22efH\u2014C contacts in the apical positions of Rh2  = 2.67\u2005\u00c5; Rh2\u22efH3A = 2.93\u2005\u00c5) that could, at best, be labeled as weak inter\u00admolecular agostic inter\u00adactions  than the bent C2/c polymorph (2.597\u2005g\u2005cm\u22123), indicative of tighter crystal packing.The structural differences between the dimers in the two polymorphs of [Rh(\u03bc-I)(COD)]ry Fig.\u00a03. In the ns Fig.\u00a04. Consist2 was prepared according to the procedure described by J. A. Hlina et al.  was added to toluene (5\u2005mL) and tri\u00admethyl\u00adsilyl iodide . The reaction mixture turned dark red and rust-colored crystals precipitated from the solution. The solid was isolated, washed with hexa\u00adnes and dried in vacuo to yield the final product [Rh(\u03bc-I)(COD)]2 as a red\u2013brown crystalline solid . X-ray quality crystals were grown from a concentrated solution of toluene at 236\u2005K, resulting in crystals with two different morphologies. 1H NMR (C6D6): 1.15\u20131.28 , 1.90\u20132.05 , 4.62\u20134.70 . A single species was observed by 1H NMR spectroscopy and the 1H NMR spectrum did not contain any broad features indicative of dynamic behavior or inter\u00adconversion between the two isomers in solution.[Rh(\u03bc-I)(COD)] al. 2017. Under aSHELXT) produced a complete phasing model for refinement. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares (SHELXL2018). All carbon-bonded methyl\u00adene hydrogen atoms were placed using a riding model. Their positions were constrained relative to their parent atom using the appropriate HFIX command in SHELXL2018. All carbon-bonded methine hydrogen atoms were located in the difference map. Their C\u2014H distances were restrained to a target value of 1.00\u2005(2)\u2005\u00c5. For all H atoms, displacement parameter Uiso(H) values were set to 1.2 times Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S205698902100743X/zl5015sup1.cifCrystal structure: contains datablock(s) global, B, P. DOI: 10.1107/S205698902100743X/zl5015Bsup2.hklStructure factors: contains datablock(s) B. DOI: 10.1107/S205698902100743X/zl5015Psup3.hklStructure factors: contains datablock(s) P. DOI: 2097568, 2097567CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Saccharomyces cerevisiae is its ability to perform simultaneous respiration and fermentation at high growth rate even under fully aerobic conditions. In the present work, this Crabtree effect called phenomenon was investigated in detail by comparative 13C metabolic flux analysis of S. cerevisiae growing under purely oxidative, respiro-fermentative and predominantly fermentative conditions.One of the most fascinating properties of the biotechnologically important organism S. cerevisiae exhibited a by-pass of pyruvate dehydrogenase in all physiological regimes. During oxidative growth this by-pass was mainly provided via pyruvate decarboxylase, acetaldehyde dehydrogenase, acetyl-CoA synthase and transport of acetyl-CoA into the mitochondrion. During fermentative growth this route, however, was saturated due to limited enzyme capacity. Under these conditions the cells exhibited high carbon flux through a chain of reactions involving pyruvate carboxylase, the oxaloacetate transporter and malic enzyme. During purely oxidative growth the PPP alone was sufficient to completely supply NADPH for anabolism. During fermentation, it provided only 60 % of the required NADPH.The metabolic shift from oxidative to fermentative growth was accompanied by complex changes of carbon flux throughout the whole central metabolism. This involved a flux redirection from the pentose phosphate pathway (PPP) towards glycolysis, an increased flux through pyruvate carboxylase, the fermentative pathways and malic enzyme, a flux decrease through the TCA cycle, and a partial relocation of alanine biosynthesis from the mitochondrion to the cytosol. S. cerevisiae possesses different metabolic by-passes to channel carbon into the mitochondrion. This involves the conversion of cytosolic pyruvate either into acetyl CoA or oxaloacetate followed by intercompartmental transport of these metabolites. During oxidative growth mainly the NAD specific isoforms of acetaldehyde dehydrogenase and isocitrate dehydrogenase catalyze the corresponding reactions in S. cerevisiae, whereas NADPH supply under fermentative conditions involves significant contribution of sources other than the PPP such as e. g. NADPH specific acetaldehyde dehydrogenase or isocitrate dehydrogenase.We conclude that, in order to overcome the limited capacity of pyruvate dehydrogenase,  S. cerevisiae is an important biotechnological organism e.g. for production of ethanol [S. cerevisiae is able to perform simultaneous respiration and fermentation at high growth rates even under fully aerobic conditions [S. cerevisiae by a shift from biomass formation towards fermentative products at increased dilution rates [13C metabolic flux analysis which allows the quantification of in vivo activity of pathways and reactions [S. cerevisiae and related yeast strains [S. cerevisiae by quantifying metabolic fluxes through the underlying reactions in the central metabolism at these different physiological states. For this purpose chemostat cultures with [1-13C] glucose as substrate were grown at different growth rates under aerobic glucose-limited conditions to metabolic and isotopic steady-state. The use of a continuous culture hereby allowed the precise adjustment of the physiological state of the cells, i.e. the relative activity of the fermentative pathways.The budding yeast  ethanol , recombi ethanol , antibio ethanol  or bioma ethanol . Additio ethanol ,6. This nditions ,8. This on rates . Despiteon rates -12, a clon rates ,14. The on rates ,16. A poeactions -19. In r strains -27. In t-1 and 0.45 h-1 , mixed respiro-fermentative (0.30 h-1), and mainly fermentative metabolism (0.40 h-1) were selected for the flux studies. The resulting ethanol yield under these conditions was 0.0, 0.5, and 1.1 mol ethanol (mol glucose)-1, respectively. The stoichiometric data obtained from the 13C cultures agreed well with the corresponding values from the initially performed cultivations  The metabolic shift had a strong effect on the flux partitioning between glycolysis and PPP. Whereas, at purely oxidative metabolism, the major carbon flux was channeled into the PPP, the opposite was observed for fermentative metabolism. The data of the present work together with previous flux studies of t Figure . A simil 0.4 h-1 . The red 0.4 h-1 . Due to S. cerevisiae  glucose . Cultivations were performed in a continuously operated bioreactor  with a culture volume of 100 ml at 30\u00b0C and 500 rpm. The aeration rate was kept at 100 mL/min by a mass flow controller . Composition of inlet and exhaust gas was determined on-line by mass spectrometry as described previously  was obtained. Enzymatic test-kits were used for quantification of glucose, glycerol, acetate  and ethanol  in the supernatant. Concentrations of 2-oxoglutarate, pyruvate, succinate, and fumarate in the supernatant were analyzed by HPLC [S. cerevisiae was quantified by HPLC [i.e. the quantification of the yield coefficients, was 3.7 % (biomass yield), 4.0 % (ethanol yield), 9.3 % (acetate yield) and 11.3 % (glycerol yield).Optical density (OD by HPLC  after hy0) to the fully 13C labeled (xn) variant could be measured with good signal intensity and accuracy  is shown in Figure S. cerevisiae [The metabolic network of revisiae . For glyrevisiae ,46 was t1 - \u03bd2 - \u03bd3 + \u03bd4 - \u03bd5 = 0 \u00a0\u00a0\u00a0 (1)Glucose 6-phosphate: \u03bd3 - \u03bd4 - \u03bd6 + \u03bd8 - \u03bd9 + \u03bd10 - \u03bd11 = 0 \u00a0\u00a0\u00a0 (2)Fructose 6-phosphate: \u03bd2 - \u03bd7 - \u03bd8 + \u03bd9 - 2\u03bd12 + 2\u03bd13 = 0 \u00a0\u00a0\u00a0 (3)Pentose phosphate: \u03bd8 + \u03bd9 + \u03bd10 - \u03bd11 - \u03bd14 = 0 \u00a0\u00a0\u00a0 (4)Erythrose 4-phosphate: - \u03bd12 - \u03bd13 - \u03bd10 + \u03bd11 - \u03bd5 = 0 \u00a0\u00a0\u00a0 (5)Sedoheptulose 7-phosphate: \u03bd6 - \u03bd10 + \u03bd11 + \u03bd8 - \u03bd9 + \u03bd12 - \u03bd13 + \u03bd16 - \u03bd17 - \u03bd18 = 0 \u00a0\u00a0\u00a0 (6)Glyceraldehyde 3-phosphate: \u03bd6 - \u03bd15 - \u03bd16 = 0 \u00a0\u00a0\u00a0 (7)Dihydroxyacetone-phosphate: \u03bd17 - \u03bd19 - \u03bd20 - \u03bd24 = 0 \u00a0\u00a0\u00a0 (8)3-Phosphoglycerate: \u03bd20 - \u03bd21 - \u03bd22 = 0 \u00a0\u00a0\u00a0 (9)Serine: \u03bd22 - \u03bd23 + \u03bd29 = 0 \u00a0\u00a0\u00a0 (10)Glycine: \u03bd28 - \u03bd29 - \u03bd30 = 0 \u00a0\u00a0\u00a0 (11)Threonine: \u03bd24 - \u03bd25 - \u03bd26 = 0 \u00a0\u00a0\u00a0 (12)Phosphoenolpyruvate: \u03bdcyt: \u03bd26 - \u03bd27 - \u03bd32 - \u03bd33 - \u03bd34 = 0 \u00a0\u00a0\u00a0 (13)Pyruvate32 - \u03bd37 - \u03bd38 = 0 \u00a0\u00a0\u00a0 (14)Acetaldehyde: \u03bd38 - \u03bd39 - \u03bd40 = 0 \u00a0\u00a0\u00a0 (15)Acetate: \u03bdcyt: \u03bd40 - \u03bd41 - \u03bd47 + \u03bd48 = 0 \u00a0\u00a0\u00a0 (16)Acetyl CoAcyt: \u03bd33 - \u03bd42 = 0 \u00a0\u00a0\u00a0 (17)Alaninecyt: \u03bd27 - \u03bd28 - \u03bd31 - \u03bd35 + \u03bd36 = 0 \u00a0\u00a0\u00a0 (18)Oxaloacetatemit: \u03bd34 - \u03bd43 - \u03bd44 + \u03bd50 - \u03bd51 = 0 \u00a0\u00a0\u00a0 (19)Pyruvatemit: \u03bd43 - \u03bd45 = 0 \u00a0\u00a0\u00a0 (20)Alaninemit: \u03bd44 - \u03bd46 + \u03bd47 - \u03bd48 - \u03bd49 = 0 \u00a0\u00a0\u00a0 (21)Acetyl CoA49 - \u03bd52 - \u03bd53 = 0 \u00a0\u00a0\u00a0 (22)2-Oxoglutarate: \u03bd53 - \u03bd54 + \u03bd55 = 0 \u00a0\u00a0\u00a0 (23)Succinate: \u03bdmit: \u03bd35 - \u03bd36 - \u03bd49 - \u03bd50 + \u03bd54 - \u03bd55 = 0 \u00a0\u00a0\u00a0 (24)Oxaloacetate/MalateS. cerevisiae was considered  combining metabolite balancing and isotopomer modeling. The performed approach utilized metabolite balancing  during each optimization step considering stoichiometric data on anabolic demand for biomass precursors Table  and prod13C tracer studies and all analytics involved.OF carried out the experimental work including the chemostat cultivations, the S. cerevisiae, the software implementation, the calculation of carbon fluxes, and the statistical analysis. He drafted and composed the manuscript.CW designed the study and carried out all computational work involving the construction of the metabolic network model of Both authors read and approved the final manuscript."}
{"text": "CENP\u2010A nucleosomes. Centromere maintenance during the cell cycle requires HJURP\u2010mediated CENP\u2010A deposition, a process regulated by the Mis18 complex (Mis18\u03b1/Mis18\u03b2/Mis18BP1). Spatial and temporal regulation of Mis18 complex assembly is crucial for its centromere association and function. Here, we provide the molecular basis for the assembly and regulation of the Mis18 complex. We show that the N\u2010terminal region of Mis18BP1 spanning amino acid residues 20\u2013130 directly interacts with Mis18\u03b1/\u03b2 to form the Mis18 complex. Within Mis18\u03b1/\u03b2, the Mis18\u03b1 MeDiY domain can directly interact with Mis18BP1. Mis18\u03b1/\u03b2 forms a hetero\u2010hexamer with 4 Mis18\u03b1 and 2 Mis18\u03b2. However, only two copies of Mis18BP1 interact with Mis18\u03b1/\u03b2 to form a hetero\u2010octameric assembly, highlighting the role of Mis18 oligomerization in limiting the number of Mis18BP1 within the Mis18 complex. Furthermore, we demonstrate the involvement of consensus Cdk1 phosphorylation sites on Mis18 complex assembly and thus provide a rationale for cell cycle\u2010regulated timing of Mis18 assembly and CENP\u2010A deposition.The centromere, a chromosomal locus that acts as a microtubule attachment site, is epigenetically specified by the enrichment of  Equal and identical distribution of chromosomes to each daughter cell during cell division is essential for maintaining genome integrity. A central player regulating this process is the kinetochore, a large proteinaceous structure assembled at a specialized region of the chromosome called the centromere Schizosaccharomyces pombe); however, the molecular mechanisms by which it is achieved share considerable similarity In most eukaryotes, the centromeric chromatin is epigenetically defined by the enrichment of nucleosomes containing the histone H3 variant CENP\u2010A S. pombe and humans The Mis18 proteins contain two structurally distinct domains , both of which can self\u2010oligomerize. Previously, we and others have shown that oligomerization of Mis18 proteins is required for their centromere association and function both in 20\u2013130), binds Mis18\u03b1/\u03b2 hetero\u2010oligomer via the Mis18\u03b1/\u03b2 MeDiY hetero\u2010dimer to form the Mis18 complex. Characterization of the oligomeric structures of the Mis18 subcomplexes revealed that the Mis18\u03b1/\u03b2 complex is a hetero\u2010hexamer with four copies of Mis18\u03b1 and two copies of Mis18\u03b2, while the Mis18 holo\u2010complex is a hetero\u2010octamer with two additional copies of Mis18BP1. We identify two conserved consensus Cdk1 phosphorylation sites (T40 and S110) within Mis18BP120\u2013130 and show that phospho\u2010mimicking mutations of these residues disrupt Mis18 complex formation. This explains the molecular basis for Cdk1\u2010mediated timing of Mis18 assembly and CENP\u2010A deposition.Here, we show that Mis18BP1, through its highly conserved N\u2010terminal region comprising amino acids 20\u2013130  integrated in a chromosome arm fl) as well as two different N\u2010terminal fragments: mCherry\u2010Mis18BP120\u2013130 and mCherry\u2010Mis18BP1336\u2013483 (covering the SANTA domain) to the tethering site. Mis18\u03b1 tethered to the ectopic alphoidtetO array recruited Mis18BP1fl and Mis18BP120\u2013130 more robustly compared to the Mis18BP1336\u2013483  and SANT (residues 878\u2013927) domains Figs A. It has\u2013130 Fig B. These 20\u2013130 can directly interact with Mis18\u03b1/\u03b2 in vitro, individually purified recombinant proteins (Mis18\u03b1/\u03b2 and Mis18BP120\u2013130) were analyzed using size\u2010exclusion chromatography (SEC) before and after complex formation. While Mis18\u03b1/\u03b2 and Mis18BP120\u2013130 eluted at 11.0 and 15.7 ml, respectively, the complex containing Mis18\u03b1/\u03b2 and Mis18BP120\u2013130 eluted at 10.9 ml  and a C\u2010terminal \u03b1\u2010helical domain  and Mis18BP120\u2013130 (12.7 kDa) migrate similarly in the SDS\u2013PAGE . While His\u2010GFP\u2010Mis18\u03b1MeDiY on its own eluted at 13.8 ml, the His\u2010GFP\u2010Mis18\u03b1MeDiY/Mis18BP120\u2013130 complex eluted at 13.3 ml  showed that they elute at distinct elution volumes, 13.9 and 12.2 ml, respectively, demonstrating a lack of interaction . Consistent with the SEC analysis shown in Figs MeDiY could bind Mis18BP120\u2013130. His\u2010GFP\u2010Mis18\u03b2MeDiY failed to interact with Mis18BP120\u2013130 even under a low ionic strength condition . The measured MW of the untagged Mis18\u03b1/\u03b2 complex was 151.2 \u00b1 2.9 kDa  and correlated well with the calculated MW of a hetero\u2010hexamer , it is almost impossible to accurately determine the subunit stoichiometry within the Mis18 hetero\u2010hexamer. Hence, we introduced a noticeable size variation by purifying His\u2010GFP\u2010Mis18\u03b1 in a complex with His\u2010Mis18\u03b2. Interestingly, the measured MW of His\u2010GFP\u2010Mis18\u03b1/His\u2010Mis18\u03b2 complex was 287.2 \u00b1 5.5 kDa, matching the calculated MW of a hetero\u2010hexamer containing four copies of His\u2010GFP\u2010Mis18\u03b1 and two copies of His\u2010Mis18\u03b2  and His\u2010MBP\u2010Mis18\u03b2C\u2010term (Mis18\u03b2 184\u2010end), we reconstituted the C\u2010terminal helical assembly and analyzed their composition using SEC\u2010MALS  by SEC\u2010MALS (175.4 \u00b1 3.3 kDa) is in agreement with the calculated MW of a hetero\u2010octamer containing a Mis18\u03b1/\u03b2 hetero\u2010hexamer plus two copies of Mis18BP120\u2013130  matches the calculated MW  at the MeDiY dimeric interface of Mis18\u03b1/\u03b2 and L136A/Y152A/C167A/S169K (Mis18\u03b1PocketM) in the putative substrate\u2010binding pocket using a S. pombe\u2010based homology\u2010modeled structure , His\u2010GFP\u2010Mis18\u03b1DimerM/His\u2010Mis18\u03b2 (Mis18\u03b1DimerM/\u03b2), and His\u2010GFP\u2010Mis18\u03b1PocketM/His\u2010Mis18\u03b2 (Mis18\u03b1PocketM/\u03b2) complexes using a Ni\u2010NTA pull\u2010down assay. While Mis18\u03b1wt/\u03b2 and Mis18\u03b1PocketM/\u03b2 interacted with Mis18BP120\u2013130, Mis18\u03b1DimerM/\u03b2 failed to do so efficiently . This strengthens the notion that the Mis18\u03b1/\u03b2 hetero\u2010trimer is the core oligomeric unit formed through the interactions of the C\u2010terminal helices which then assemble into a hetero\u2010hexamer via the MeDiY\u2010dimerization interface  or in combination (Mis18BP120\u2013130 T40E/S110D), on Mis18 complex formation using SEC. Both Mis18BP120\u2013130 T40E and Mis18BP120\u2013130 S110D interacted with Mis18\u03b1/\u03b2. However, Mis18BP120\u2013130 T40E/S110D failed to form a complex with Mis18\u03b1/\u03b2  was recruited by TetR\u2010eYFP\u2010Mis18\u03b1 to the array throughout the cell cycle. Consistent with this, recombinantly purified Mis18BP120\u2013130 T40A/S110A interacted with Mis18\u03b1/\u03b2 as analyzed by SEC . While mutating both these amino acid residues to phospho\u2010mimicking residues completely abolished the ability of Mis18BP1 to bind Mis18\u03b1/\u03b2 in vitro and in vivo, individual phospho\u2010mimic mutants (T40E or S110D) failed do so efficiently. This suggests that Mis18BP1 binds Mis18\u03b1/\u03b2 possibly via a bipartite binding mode. Overall, our findings together with the recent independent study by Pan et alThe temporal regulation of Mis18 complex formation defines the timing of HJURP\u2010mediated CENP\u2010A deposition essential for centromere inheritance and function imer Fig A. HoweveMeDiY, Mis18\u03b1C\u2010term, Mis18\u03b2, Mis18\u03b2MeDiY, and Mis18\u03b2C\u2010term were amplified from codon\u2010optimized sequences (GeneArt) while Mis18BP120\u2013130 was amplified from a human cDNA library . Amplifications were then cloned into pET His6 msfGFP TEV, pET His6 TEV, pET His6 Sumo TEV, pET His6 MBP TEV, pGEX\u20106P\u20101 , pEC\u2010K\u20103C\u2010His\u2010GST, and pEC\u2010K\u20103C\u2010His LIC vectors. pET His6 msfGFP TEV (9GFP Addgene plasmid # 48287), pET His6 TEV (9B Addgene plasmid # 48284), pET His6 Sumo TEV (14S Addgene plasmid # 48291), and pET His6 MBP TEV (9C Addgene Plasmid #48286) were a gift from Scott Gradia.Human Mis18\u03b1, Mis18\u03b1DimerM; V82E/Y176D) and putative substrate\u2010binding pocket mutant  and Mis18BP1 mutants, Mis18BP120\u2013130 T40E, Mis18BP120\u2013130 S110D, Mis18BP120\u2013130 T40E/S110D, and Mis18BP120\u2013130 T40A/S110A were generated following the Quikchange site\u2010directed mutagenesis protocol (Stratagene).Mis18\u03b1 MeDiY dimer\u2010disrupting mutant (Mis18\u03b1E. coli BL21 gold grown in LB media. Cultures were induced with 0.35 mM IPTG at 18\u00b0C overnight. Cell lysis was carried out by sonicating cells re\u2010suspended in a lysis buffer containing 20 mM Tris (pH 8.0), 250 mM NaCl (or 500 mM for Mis18BP120\u2013130), 35 mM imidazole, and 2 mM \u03b2ME. Lysis buffer was supplemented with 10 \u03bcg/ml DNase, 1 mM PMSF, and cOmplete . Proteins were purified from the clarified lysates by affinity chromatography using a 5 ml HisTrap HP column . The protein\u2010bound resin was washed with lysis buffer, followed by a buffer containing 20 mM Tris (pH 8.0), 1 M NaCl, 50 mM KCl, 10 mM MgCl2, 2 mM ATP, 35 mM imidazole, 2 mM \u03b2ME, and with a final lysis buffer wash. Proteins were eluted using a lysis buffer supplemented with 500 mM imidazole and dialyzed overnight into 20 mM Tris (pH 8.0), 75\u2013100 mM NaCl, and 2 mM DTT. All proteins were subjected to anion exchange chromatography using the HiTrap Q column . Appropriate fractions were pooled, concentrated, and injected into a Superdex 200 increase 10/300 or Superdex 75 10/300 column  equilibrated with 20 mM Tris (pH 8.0), 100\u2013250 mM NaCl, and 2 mM DTT. Fractions were analyzed on SDS\u2013PAGE and stained with Coomassie blue.Proteins were expressed, either individually or together with their binding partners, using 20\u2013130 and made up to 200 \u03bcl with buffer before incubated for 30 min at 4\u00b0C with 60\u2013120 \u03bcl of slurry that had been equilibrated in buffer. Beads were then washed four times with 1 ml of buffer, and bound protein was eluted by boiling in SDS\u2013PAGE loading dye before being analyzed by SDS\u2013PAGE.Ni\u2010NTA pull\u2010down assay was performed in 20 mM Tris (pH 8.0), 75\u2013500 mM NaCl, 10% glycerol, 0.5% NP\u201040, 35 mM imidazole, and 2 mM \u03b2ME. Proteins were mixed with two times molar excess of Mis18BP1280 nm were analyzed by a homo\u2010polymer model  using the following parameters for: \u2202A280 nm/\u2202c = 0.97 AU ml mg\u22121 (Mis18\u03b1/\u03b2 complex), 0.86 AU ml mg\u22121 (His\u2010GFP\u2010Mis18\u03b1/His\u2010Mis18\u03b2 and His\u2010Mis18\u03b1/His\u2010GFP\u2010Mis18\u03b2), 0.82 AU ml mg\u22121 (Mis18\u03b1/Mis18\u03b2/Mis18BP120\u2013130), 0.71 AU ml mg\u22121 (Mis18\u03b1/Mis18\u03b2/His\u2010Sumo\u2010Mis18BP120\u2013130), 1.10 AU ml mg\u22121 (His\u2010GFP\u2010Mis18\u03b1C\u2010term/His\u2010MBPMis18\u03b2C\u2010term), 0.86 AU ml mg\u22121 (His\u2010GFP\u2010Mis18\u03b12M/His\u2010Mis18\u03b2), \u2202n/\u2202c = 0.185 ml g\u22121, and buffer RI value of 1.335. The mean standard error in the mass accuracy determined for a range of protein\u2013protein complexes spanning the mass range of 6\u2013600 kDa is \u00b11.9%.Size\u2010exclusion chromatography  coupled to UV, static light scattering, and refractive index detection  was used to determine the absolute molecular mass of proteins and protein complexes in solution. Injections of 100 \u03bcl of about 1 mg/ml material were run on a Superdex 200 10/300 GL  size\u2010exclusion column pre\u2010equilibrated in 50 mM HEPES (pH 8.0), 150 mM NaCl, and 1 mM TCEP at 22\u00b0C with a flow rate of 0.5 ml/min. Light scattering, refractive index (RI), and Afl, Mis18BP120\u2013130, and Mis18BP1336\u2013483 were amplified from a human cDNA library  and cloned into the pCDNA3\u2010mCherry or \u2010mCerulean LIC cloning vectors . Mis18\u03b1 was cloned into the TetR\u2010eYFP\u2010IRES\u2010Puro vector. Mutant constructs, TetR\u2010eYFP\u2010Mis18\u03b1DimerM, mCherry\u2010Mis18BP120\u2013130 T40E, mCherry\u2010Mis18BP120\u2013130 S110D, mCherry\u2010Mis18BP120\u2013130 T40E/S110D, and mCherry\u2010Mis18BP120\u2013130 T40A/S110A, were generated using the Quikchange mutagenesis protocol (Stratagene).Human Mis18\u03b2, Mis18BP1tetO array) integrated in a chromosome arm, was maintained in DMEM (Gibco) supplemented with 5% fetal bovine serum (Biowest) and penicillin/streptomycin (Gibco). Cells were grown at 37\u00b0C and 5% CO2. Transfections were performed in parallel with XtremeGene\u20109 (Roche) following manufacturer's instructions. Briefly, 24 h after plating, cells grown in 12\u2010well plates were incubated with transfection complexes containing: 0.25 \u03bcg of each vector, 100 \u03bcl of Opti\u2010MEM (Invitrogen), and 3 \u03bcl of XtremeGene\u20109 reagent for 36 h.The HeLa 3\u20108 overexpressing CENP\u2010A\u2010SNAP integration cell line, containing a synthetic \u03b1\u2010satellite  DNA array integration with tetO sites  for 5 min at room temperature and blocked with permeabilization buffer containing 3% BSA for 1 h at 37\u00b0C. Mouse anti\u2010CENP\u2010A  and Cy\u20105\u2010conjugated donkey anti\u2010mouse secondary antibody (Jackson Immunoresearch) were used for centromere staining.z\u2010stacks were deconvolved using SoftWorx and analyzed using ImageJ software . For CENP\u2010A signal quantification, a custom\u2010made macro in ImageJ modified from Bodor et alTetO array  was determined for every z\u2010section within a 7\u2010square pixel box. The mean signal intensity in the array was obtained and the background subtracted using the minimum intensity values within the section. The average intensity of the CENP\u2010A signal from endogenous centromeres was used to normalize. At least three biological independent experiments were performed for each assay.Micrographs were acquired in the Centre Optical Instrumentation Laboratory on a DeltaVision Elite system (Applied Precision) using an inverted Olympus IX\u201071 stand, with an Olympus UPlanSApo 100\u00d7 oil immersion objective  1.4) and a Lumencor light source. Camera (Photometrics Cool Snap HQ), shutter and stage were controlled through SoftWorx (Applied Precision). The 0.2\u2010\u03bcm\u2010spaced AAJ conceived the project. FS, BM\u2010P, MAA, OM, AAJ, and WCE designed experiments. FS, BM\u2010P, MAA, MAW, and OM performed experiments and analyzed data. FS, BM\u2010P, MAA, OM, WCE, and AAJ wrote the manuscript.The authors declare that they have no conflict of interest.Expanded View Figures PDFClick here for additional data file.Review Process FileClick here for additional data file."}
{"text": "The crystal structure of 2-(5-bromo\u00adthio\u00adphen-2-yl)aceto\u00adnitrile, previously reported as a liquid, has short centrosymmetric Type I Br\u22efBr halogen inter\u00adactions. 6H4BrNS, crystallizes in the space group P21/n with one complete mol\u00adecule in the asymmetric unit. The non-H atoms are nearly planar (r.m.s for non-H atoms = 0.071\u2005\u00c5), with the nitrile group oriented anti\u00adperiplanar with respect to the thio\u00adphene S atom. Inter\u00admolecular Type I centrosymmetric Br\u22efBr halogen inter\u00adactions are present at a distance of 3.582\u2005(1)\u2005\u00c5 and with a C\u2014Br\u22efBr angle of 140.7\u2005(1)\u00b0. Additional weaker C\u2014H\u22efN, C\u2014H\u22efS, and S\u22ef\u03c0 inter\u00adactions are also present. A Hirshfeld analysis indicates Br\u22efBr inter\u00adactions comprise only 1.9% of all the inter\u00adatomic contacts.The title compound, C The large number of reflections in the data sets (and the Fourier-transform relationship of intensities to atoms) ensures that no particular bias was thereby introduced.10.1107/S2056989018000968/dx2004sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018000968/dx2004Isup2.hklStructure factors: contains datablock(s) I. DOI: 1817195CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the two structures, short cationic tris\u00adtannatoxanes (C 3(CH3)9(OH)2(H2O)2][Sn(CH3)3(CHO2)2] (1) and [Sn3(CH3)9(OH)2]Cl\u00b7H2O (2), are partially condensed products of hydrolysed tri\u00admethyl\u00adtin chloride. In the structures of 1 and 2, short cationic tris\u00adtannatoxanes (C9H29O2Sn3) are bridged by a diformatotri\u00admethyl\u00adtin anion or a chloride anion, respectively. Hydrogen bridges are present and supposedly stabilize these structures against further polymerization to the known polymeric tri\u00admethyl\u00adtin hydroxide. Especially noteworthy is that the formate present in this structure was formed from atmospheric CO2.The title compounds, [Sn Therefore, the activation of CO2 plays an important role in today\u2019s research. It is already known that CO2 is activated by electroreduction of different metals \u00b0 while in 2 it is 135.30\u2005(17)\u00b0. In the chloride structure 2, a change in two further angles is noticed. The O1\u2014Sn1\u2014Cl1 angle [177.58\u2005(10)\u00b0] and the O2\u2014Sn3\u2014Cl1\u2032 angle [175.5\u2005(12)\u00b0] decreases  and the chloride anion.In the crystal structures, no polymeric Sn\u2013O structures were formed, as found in the tri\u00admethyl\u00adtin hydroxide. The short tri\u00admethyl\u00adtin hydroxide chain has a positive and the chloride or bisformatostannate a negative charge. In the structure of via hydrogen bonds. In structure 1 , thus forming a two-dimensional network. Additionally, hydrogen bonds between these sheets form a two-dimensional network along the bc plane (O4\u22efH1\u2014O1).As described, both structures are inter\u00admolecularly linked  1 Fig.\u00a03, the for2 \u2005\u00c5], one by a Cl1\u22efH1i\u2014O1i hydrogen bond [3.251\u2005(4)\u2005\u00c5]. A fourth hydrogen bond, Cl1\u22efH3ii\u2014O3ii [3.068\u2005(5)\u2005\u00c5], results in a distorted tetra\u00adhedral environment. Thus, a three-dimensional network of hydrogen bridges is formed. The inter\u00adactions between Sn\u2013Cl differ due to steric repulsion of the C2 and C7iii methyl groups. The van der Waals radius of a methyl group is 2\u2005\u00c5 \u00b0 for Sn1\u2014Cl1\u2014Sn2 and 179.2\u2005(2)\u00b0 for O1\u2014Sn1\u2014Cl1 were observed  = 1.5Ueq(Cmeth\u00adyl). The CH3 hydrogen atoms were allowed to rotate but not to tip. Due to point group symmetry 2 of both the cation and anion in 1, with the twofold rotation axis running through the respective central Sn atom and one of the methyl groups, the latter is equally disordered over two positions.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016014912/su5326sup1.cifCrystal structure: contains datablock(s) Global, 1, 2. DOI: 10.1107/S2056989016014912/su53261sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989016014912/su53262sup3.hklStructure factors: contains datablock(s) 2. DOI: 1505529, 1505528CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two new crystal structures of eight- and ten-membered cyclic bis\u00adanisyl\u00adphosphono\u00adthioyl disulfanes have been determined and these are compared to the structures of their ferrocenyl analogues. 5,5\u03bb5-dioxadi\u00adthiadi\u00adphospho\u00adcane-2,5-di\u00adthione, C16H18O4P2S4, and 2,5-bis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)-1,6,3,4,2\u03bb5,5\u03bb5-dioxadi\u00adthia\u00addiphosphecane-2,5-di\u00adthione, C18H22O4P2S4, have been determined and compared to structures of the ferrocenyl analogues. The eight-membered rings have similar conformations (TBC) but the ten-membered macrocycles are differently puckered. Structural parameters of the relevant SPSSPS motif have been analysed and are discussed in detail. Compound 1 was refined as an inversion twin and 2 was refined as a two-component rotational twin.Two new crystal structures of eight- and ten-membered cyclic bis\u00adanisyl\u00adphosphono\u00adthioyl disulfanes, namely 2,5-bis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)-1,6,3,4,2\u03bb Lawesson reagent LR P(S)SH and Fc(RO)P(S)SH, obtained in a simple reaction between LR or fLR and alcohols, are of considerable inter\u00adest because they form a plethora of structurally inter\u00adesting chelate complexes with metal ions S]e.g. eight-membered 1a  acid derivatives and among them the unique eight-, nine- and ten-membered cyclic bis\u00adanisyl\u00adphosphono\u00adthioyl disulfanes . The related ferrocenyl compound 1a crystallizes in space group C2/c with non-typical three and half independent mol\u00adecules in the asymmetric unit (Z = 28), which complicates comparisons.Views of mol\u00adecular structures and atom-labeling scheme for 2 forms a monoclinic crystalline phase obeying P21/c space-group symmetry with one mol\u00adecule in the asymmetric unit and Z = 4. The related ferrocenyl structure 2a crystallizes in space group PCompound trans arrangement, i.e. above and below the macrocycle ring plane for all compounds 1\u20132a, which is also typical for all open-chain bis\u00adphospho\u00adrothioyl disulfanes studied previously , 2.0704\u2005(10), 2.0685\u2005(10), 2.0711\u2005(15)\u2005\u00c5 for 1a; 2.074\u2005(3)\u2005\u00c5 for 2 and 2.0788\u2005(9)\u2005\u00c5 for 2a. They are longer than the typical S\u2014S bond lengths for known diorganyl disulfanes RSSR [2.05\u2005(3)\u2005\u00c5]. The observed S\u2014S bond elongation in 1\u20132a may be correlated with the PSSP torsion angles  are shorter than the endocyclic P\u2014S bonds (ca 2.10\u2005\u00c5).The S\u2014S bond lengths have values of 2.068\u2005(2)\u2005\u00c5 for 1\u20132a adopt a distorted tetra\u00adhedral geometry, where the C\u2014P=S angles deviated the most (116.1\u2013118.5\u00b0) from the ideal tetra\u00adhedral angle. This is obviously due to the steric effects of the anisyl and ferrocenyl substituents. On the other hand, it is worthy to note that the O\u2014P\u2013S bond angles in 1\u20132a (107\u2013108\u00b0) are not distorted, probably due to minimal conformational strain present in those medium-sized heterocycles. Moreover, both the P=S and aromatic anisyl groups in 1 are almost perfectly coplanar (unlike P=S and the cyclopentadienyl ring in 1a), which provides energetically favorable conjugation [torsion angle S2\u2014P1\u2014C10\u2014C15 = \u22123.8\u2005(4)\u00b0 in 1vs 35.75\u2005(3)\u00b0 for the equivalent angle in a selected representative mol\u00adecule with Fe7 in 1a]. The other related independent torsion angles in 1a are \u221231.\u2005(3), \u221233.9\u2005(3), \u221227.0\u2005(3), \u221228.7\u2005(3), 34.8\u2005(3), 35.7\u2005(3)\u00b0, for Fe1\u2013Fe6, respectively.All phospho\u00adrus atoms in 1 is the most symmetric with the lowest PSSP torsion [\u221293.68\u2005(8)\u00b0] and shows only a moderate deviation from a right angle. The PSSP torsion angles in 1a  are 6\u20138\u00b0 wider than in 1. Notably, ten-membered disulfanes have even wider PSSP torsion angles and the difference between them is smaller, \u2212112.89\u2005(11) and 114.9\u2005(4)\u00b0, for 2 and 2a, respectively.It is well recognised that PSSP torsion is a characteristic feature of all disulfanes as a class of organic compounds. The structure of X (X = O or S) can be found in the structures of 1 and 2 , 4.2670\u2005(9), 4.2652\u2005(9) or 4.261\u2005(1)\u2005\u00c5 (for different independent mol\u00adecules in 1a) for eight-membered rings, to 4.614\u2005(2) in 2 and 4.604\u2005(1)\u2005\u00c5 in 2a for the ten-membered rings.The transannular P\u22efP distances are very similar within the same ring size and increase, from 4.3331\u2005(17)\u2005\u00c5 in 1 and 1a was recognised by PLATON \u2005\u00c5. The anisyl substituents may have inhibited this kind of inter\u00adaction.The strongest inter\u00admolecular hydrogen-bonding inter\u00adaction in 2 are mainly based on the anisyl methoxyl CH3O oxygen atoms O3 and O4 and the P=S sulfur atom S3 as acceptors. Hydrogen-bond donors are the anisyl ortho-hydrogen atoms or methyl\u00adene hydrogen atoms. Moreover, some C\u2014H..\u03c0. inter\u00adactions may play some role in the system, e.g. C16\u2014H16A\u22efring(C20\u2013C25), see Fig.\u00a05Inter\u00admolecular inter\u00adactions in et al., 2016et al., 2015et al., 2017et al., 2004et al., 1991et al., 1993Bisphosphono\u00adthioyl disulfanes represent a rather rare class of compounds  solvent system.Eight- and ten-membered cyclic bis\u00adanisyl\u00adphosphono\u00adthioyl disulfanes 2,5-Bis(4-meth\u00adoxy\u00adphen\u00adyl)-1,6,3,4,2,5-dioxadi\u00adthiadi\u00adphos\u00adpho\u00adcane 2,5-di\u00adthione, 1M.p. 441-443\u2005K.2,5-Bis(4-meth\u00adoxy\u00adphen\u00adyl)-1,6,3,4,2,5-dioxadi\u00adthia\u00addiphos\u00adphecane 2,5-di\u00adthione, 2Yield: 65%, m.p. 415\u2013417\u2005K.1H NMR (CDCl3): 2.20 , 2.25 , 3.89 , 4.37 , 4.89 , 7.01 , 7.87 .13C NMR: 27.21 , 55.46 (s), 67.08 , 114.03 , 125.41 , 132.89 , 163.09 (s).31P{1H} NMR (CDCl3): 89.19 (3JPP = 4\u2005Hz)18H22O4P2S4: 492.0. Found: 492.9 [M+H]+.MS calculated for C1 was refined as an inversion twin with contribution of the second domain equal to 0.45\u2005(17). This explains the ambiguous Flack parameter and is not surprising since we started from achiral substrates. Structure 2 was refined as a two-component rotational twin with twin law: {2 (Q1\u2013Q3 ca 2e \u00c53), which are close to sulfur atoms , may stem from conformational flexibility of the ring. Note: the structure of 1 was determined at room temperature (due to a failure of our CryoStream unit) not at 120\u2005K as for 2 but we believe it did not influence the qualitative conclusions drawn from the results.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018001068/zp2026sup1.cifCrystal structure: contains datablock(s) 2, global, 1. DOI: 10.1107/S2056989018001068/zp20261sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018001068/zp20262sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989018001068/zp20261sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018001068/zp20262sup5.cmlSupporting information file. DOI: 1558043, 719124CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, a pheno\u00adthia\u00adzine moiety is linked to a planar carbazole unit (r.m.s. deviation = 0.029\u2005\u00c5) by a C\u2014C single bond. Their mean planes are inclined to one another by 27.28\u2005(5)\u00b0, and the pheno\u00adthia\u00adzine moiety possesses a typical butterfly structure with a fold angle of 27.36\u2005(9)\u00b0 between the two benzene rings. 29H24N2OS, contains a pheno\u00adthia\u00adzine moiety linked to a planar carbazole unit (r.m.s. deviation = 0.029\u2005\u00c5) by a C\u2014C single bond. The pheno\u00adthia\u00adzine moiety possesses a typical non-planar butterfly structure with a fold angle of 27.36\u2005(9)\u00b0 between the two benzene rings. The dihedral angle between the mean planes of the carbazole and pheno\u00adthia\u00adzine units is 27.28\u2005(5)\u00b0. In the crystal, mol\u00adecules stack in pairs along the c-axis direction, linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.797\u2005(1)\u2005\u00c5]. There are C\u2014H\u22ef\u03c0 inter\u00adactions present linking these dimers to form a three-dimensional structure.The title compound, C The fold angle of 27.36\u2005(9)\u00b0 between the two benzene rings of this moiety compares well with the values reported for similar compounds \u2005\u00c5, inter\u00adplanar distance = 3.5133\u2005(8)\u2005\u00c5, slippage = 1.439\u2005\u00c5, Cg5 is the centroid of the C15\u2013C20 ring; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a02]. There are also C\u2013H\u22ef\u03c0 inter\u00adactions present linking these dimers to form a three-dimensional structure -10H-pheno\u00adthia\u00adzine-3-carbaldehyde , 9-ethyl-9H-carbazole-3-boronic acid pinnacol ester , Pd(PPh3)4  and K2CO3  under high vacuum was added a mixture of toluene:water (2:1). The resulting mixture was heated to reflux under an N2 atmos\u00adphere for ca 24\u2005h. On completion of the reaction (monitored by TLC), it was quenched by addition of saturated double-distilled H2O and extracted with di\u00adchloro\u00admethane. The organic phases were collected and washed with brine and dried over anhydrous Na2SO4 and then concentrated. The product was purified by column chromatography on silica gel using ethyl acetate:n-hexane  as eluent, to give the title compound as a pale-yellow crystalline solid (yield 80%). It was characterized by 1H NMR, 13C NMR, IR and ESI\u2013MASS. Brown block-like crystals of the title compound were obtained by slow evaporation at room temperature of a solution in di\u00adchloro\u00admethane and aceto\u00adnitrile (1:1 v/v).To a mixture of 7-bromo-10-ethyl-10Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017005540/su5357sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017005540/su5357Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005540/su5357Isup3.cmlSupporting information file. DOI: 1543611CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming chains propagating along the  14H15NO4S, the di\u00adhydro\u00adthia\u00adzine ring adopts a distorted sofa conformation with the S atom displaced from the mean plane through the N and C ring atoms by 0.767\u2005(1)\u2005\u00c5. The allyl substituent (C\u2014C=C) is inclined to this mean plane by 78.5\u2005(7)\u00b0 and the acetate group [C(=O)\u2014O\u2014C] by 66.5\u2005(3)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions forming chains propagating along the a-axis direction.In the title compound, C The allyl substituent (C\u2014C=C) is inclined to this mean plane by 78.5\u2005(7)\u00b0 and the acetate group (O=C\u2014O\u2014C) by 66.5\u2005(3)\u00b0. Atom N1 has a planar configuration, the sum of the bond angles being 359.1\u00b0.The mol\u00adecular structure of the title compound, A\u22efC5 = 2.47\u2005\u00c5 in this fragment [the sum of the van der Waals radii \u00b0]. The allyl group is orthogonal to the benzo\u00adthia\u00adzine fragment plane while the terminal double bond is synperiplanar to the N1\u2014C12 bond . The steric repulsion between the allyl substituent and the aromatic cycle (short intra\u00admolecular contacts H2\u22efC12 = 2.77\u2005\u00c5 and H12A\u22efC2 = 2.83\u2005\u00c5) results in the elongation of the C1\u2014N1 bond [1.411\u2005(5)\u2005\u00c5], compared with the mean value of 1.371\u2005\u00c5  of K2CO3 and the mixture was stirred for 30\u2005min. Allyl bromide  was then added and the mixture was stirred for a further 30\u2005min at 298\u2005K. It was then diluted with cold water and acidified with dilute HCl to pH 4. It was extracted with CH2Cl2 (3 \u00d7 10\u2005ml). The organic extracts were combined and the solvent removed by distillation (at reduced pressure at the end). The residue was dissolved in 20\u2005ml of hot methanol and filtered over charcoal. The resulting solution was then placed in a freezer (253\u2005K) for 24\u2005h, after which crystals of the title compound were harvested .The synthesis of the title compound, Uiso = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016015978/su5329sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989016015978/su5329Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016015978/su5329Isup3.cmlSupporting information file. DOI: 1508990CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in the title complex, [Cd(C10H14N2O)2(C8H4NO2)2(H2O)2], is located on an inversion centre and is coordinated by an N2O4 donor set from pairs of water, 4-cyano\u00adbenzoate and N,N-di\u00adethyl\u00adnicotinamide ligands.The Cd 10H14N2O)2(C8H4NO2)2(H2O)2], is centrosymmetric and contains two water mol\u00adecules, two 4-cyanobenzoate (CB) ligands and two di\u00adethyl\u00adnicotinamide (DENA) ligands. All the ligands are coordinated to the CdII atom in a monodentate mode. The four nearest O atoms around the CdII atom form a slightly distorted square-planar arrangement, with the distorted octa\u00adhedral coordination sphere being completed by the two pyridine N atoms of the DENA ligands at distances of 2.3336\u2005(13)\u2005\u00c5. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 8.75\u2005(16)\u00b0, while the benzene and pyridine rings are oriented at a dihedral angle of 57.83\u2005(5)\u00b0. The water mol\u00adecules exhibit both intra\u00admolecular  and inter\u00admolecular  O\u2014H\u22efO hydrogen bonds. The latter lead to the formation of supra\u00admolecular chains propagating along [110].The mononuclear title cadmium complex, [Cd(C N,N\u2032-di\u00adethyl\u00adnicotinamide (DENA) is an important respiratory stimulant 2(C7H4ClO2)2(H2O)2] 2(H2O)2]  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Pellagra patients show unusually high serum and urinary copper levels  and DENA ligands, namely trans-di\u00adaqua\u00adbis\u00ad(4-cyano\u00adbenzoato-\u03baO)bis\u00adcadmium, [Cd(CB)2(DENA)2(H2O)2], and report herein its crystal structure.The structure\u2013function\u2013coordination relationships of the aryl\u00adcarboxyl\u00adate ion in CdII atom located on an inversion centre, one CB ligand, one DENA ligand as well as one water mol\u00adecule, all ligands coordinating to the CdII atom in a monodentate mode   of the two symmetry-related monodentate CB anions and water O atoms (O4 and O4i) form a slightly distorted square-planar arrangement around the Cd1 atom, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of two DENA ligands \u2005\u00c5]; the Cd\u2014N bond length is the longest with 2.3336\u2005(13)\u2005\u00c5 in the CdO4N2 octa\u00adhedron. The Cd1 atom lies 0.7558\u2005(1)\u2005\u00c5 below the planar (O1/O2/C1) carboxyl\u00adate group. The O\u2014Cd\u2014O and O\u2014Cd\u2014N bond angles range from 87.54\u2005(5) to 92.46\u2005(5)\u00b0. In the carboxyl\u00adate groups, the C\u2014O bonds of the coordinating O atoms [C1\u2014O1 = 1.244\u2005(2)\u2005\u00c5 and C1\u2014O2 = 1.259\u2005(2)\u2005\u00c5] are 0.015\u2005(2)\u2005\u00c5 longer than those of the non-coordinating ones, indicating delocalized bonding arrangements rather than localized single and double bonds. The dihedral angle between the carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene (C2\u2013C7) ring is 8.75\u2005(16)\u00b0, while the benzene and pyridine (N1/C9\u2013C13) rings are oriented at a dihedral angle of 57.83\u2005(5)\u00b0.The two carboxyl\u00adate O atoms  hydrogen bonds (Table\u00a01S(6) hydrogen-bonding motifs  hydrogen bonds  in H2O (50\u2005ml) and di\u00adethyl\u00adnicotinamide  in H2O (10\u2005ml) with sodium 4-cyano\u00adbenzoate  in H2O (100\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.The title compound was prepared by the reaction of CdSO2O) were located in a difference Fourier map and were refined freely. The C-bound H atoms were positioned geometrically with C\u2014H = 0.93, 0.97 and 0.96\u2005\u00c5, for aromatic, methyl\u00adene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic and methyl\u00adene H-atoms.Experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016018247/wm5339sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016018247/wm5339Isup2.hklStructure factors: contains datablock(s) I. DOI: 1517222CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound comprises one cafenstrole ligand mol\u00adecule and one silver nitrate ion. The coordination bonds between silver and oxygen atoms allow a continuous one-dimensional coordination polymer structure along [001]. The three-dimensional architecture is stabilized by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide), a triazole herbicide, leads to the title coordination polymer, [Ag(NO3)(C16H22N4O3S)]n, whose asymmetric unit comprises one cafenstrole ligand mol\u00adecule, one AgI atom and one nitrate ion. The AgI atom, with a distorted trigonal\u2013pyramidal environment, is coordinated by one nitro\u00adgen atom of a triazole ring, two oxygen atoms of a nitrate ion and one oxygen atom of a neighboring nitrate ion. The coordination bonds between silver and oxygen atoms give rise to a one-dimensional (1D) coordination polymer structure along [001]. The dihedral angle between the planes of the triazole and benzene rings is 87.13\u2005(11)\u00b0. In the crystal, the coordination polymer is stabilized by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in a three-dimensional architecture.The reaction of silver nitrate and cafenstrole ( L; Kang et al., 2015et al., 2001et al., 2013et al., 2014Recently, we have reported the crystal structure of the ligand cafenstrole  [Ag1\u2014N1 = 2.250\u2005(3)\u2005\u00c5] and three oxygen atoms  . The Ag1, O5, N1, and O5i atoms form a slightly distorted triangular basal plane with bond angles O5\u2014Ag1\u2014O5i = 106.52\u2005(5), O5\u2014Ag1\u2014N1 = 118.75\u2005(11) and O5i\u2014Ag1\u2014N1 = 134.63\u2005(11)\u00b0. The apex atom, O4, deviates considerably from the normal to the basal plane, as indicated by the O4\u2014Ag1\u2014N1 bond angle of 149.66\u2005(10)\u00b0. Other bond angles are 48.93\u2005(10) and 67.18\u2005(10)\u00b0 for O4\u2014Ag1\u2014O5 and O4\u2014Ag1\u2014O5i, respectively. One oxygen atom of the nitrate ion (O6) is not bound to the AgI ion, whereas the other two oxygen atoms of the nitrate ion (O4 and O5) are bound to the AgI ion. One of the bound O atoms (O5) links neighbouring AgI ion ions, thus forming a 1D polymer along [001]. The triazole plane is rotated about the S1\u2013C10 axis in the opposite direction in comparison with free cafenstrol  \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, z\u00a0+\u00a01 symmetry, resulting in a 1D chain along [001]  inter\u00adactions , was determined by Min et al. 2(NO3)(C12H8N2)]\u00b72C12H8N2, has a polymeric chain structure, where nitrate ions show similar coordination bonds compared to those in the title compound, but with AgI ions replaced by with PrIII atoms   in methanol (5\u2005mL). The ligand was purchased from the Dr Ehrenstorfer GmbH Company. Single crystals suitable for X-ray crystallography were obtained by slow evaporation of the solvent at room temperature after one week.The title compound was prepared from a mixed solution of the cafenstrole ligand  in acetone (5\u2005mL) and Ag(NOd(C\u2014H) = 0.98\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for methyl group, d(C\u2014H) = 0.99\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for Csp3\u2014H and d(C\u2014H) = 0.95\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for aromatic C\u2014H.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016016662/vn2117sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016016662/vn2117Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510357CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 28177; 10.1038/srep28177 published online: 07052016; updated: 10102016.In this Article the legend for Figure 5 is incomplete.2+ in cytosol was measured using Fura-2 and Ca2+ in ER was measured using FRET-based probe D1ER cameleon in the basal state and after thapsigargin stimulation (100\u2009nM for 1000\u2009sec). Representative Ca2+ measurements in cytosol and ER (left panel). Quantitative ER Ca2+ levels of the average value prior to thapsigargin stimulation  and the minimum value after addition of thapsigargin (Tg(+)) (right panel). Data are means\u2009\u00b1\u2009SEM, n\u2009=\u200943 for control, n\u2009=\u200950 for IRS1KO, and n\u2009=\u200940 for IRS2KO \u03b2-cells. *P\u2009<\u20090.05, **P\u2009<\u20090.01\u201d.\u201cCaShould read:2+ in cytosol was measured using Fura-2 and Ca2+ in ER was measured using FRET-based probe D1ER cameleon in the basal state and after thapsigargin stimulation (100\u2009nM for 1000\u2009sec). Representative Ca2+ measurements in cytosol and ER (left panel). Quantitative ER Ca2+ levels of the average value prior to thapsigargin stimulation  and the minimum value after addition of thapsigargin (Tg(+)) (right panel). Data are means\u2009\u00b1\u2009SEM, n\u2009=\u200943 for control, n\u2009=\u200950 for IRS1KO, and n\u2009=\u200940 for IRS2KO \u03b2-cells. *P\u2009<\u20090.05, **P\u2009<\u20090.01. (b) Immunoblot of SERCA2 and \u03b2-actin in control \u03b2-cells, IRS1KO \u03b2-cells, and IRS2KO \u03b2-cells incubated with vehicle or thapsigargin (100\u2009nM) for 8\u2009h. Data are means\u2009\u00b1\u2009SEM, n\u2009=\u20094. *P\u2009<\u20090.05\u201d.\u201c(a) Ca"}
{"text": "The structures of three bicyclic carbohydrates derivatives containing cyclo\u00adbutanone or cyclo\u00adlactame beside the pyran\u00adose ring are reported and the conformation and configuration established. R,3R,4R,5R,6S)-4,5-bis\u00ad(acet\u00adyloxy)-7-oxo-2-oxabi\u00adcyclo[4.2.0]octan-3-yl]methyl acetate, C14H18O8, (I), [-5-acet\u00adyloxy-7-hy\u00addroxy\u00adimino-2-oxobi\u00adcyclo\u00ad[4.2.0]octan-4-yl acetate, C11H15NO6, (II), and pyrrol-5-yl]methyl acetate, C14H19NO8, (III), are stable bicyclic carbohydrate derivatives. They can easily be synthesized in a few steps from commercially available glycals. As a result of the ring strain from the four-membered rings in (I) and (II), the conformations of the carbohydrates deviate strongly from the ideal chair form. Compound (II) occurs in the boat form. In the five-membered lactam (III), on the other hand, the carbohydrate adopts an almost ideal chair conformation. As a result of the distortion of the sugar rings, the configurations of the three bicyclic carbohydrate derivatives could not be determined from their NMR coupling constants. From our three crystal structure determinations, we were able to establish for the first time the absolute configurations of all new stereocenters of the carbohydrate rings.The title compounds, [(1 The conformation of the pyran\u00adose rings deviates from the ideal chair. The puckering amplitudes and smallest displacement parameters for mol\u00adecules A and B are q = 0.467\u2005(2)/0.473\u2005(3)\u2005\u00c5, \u03b8 = 151.9\u2005(4)/150.7\u2005(4)\u00b0 and \u03c6 = 114.1\u2005(6)/114.3\u2005(6)\u00b0. The main feature is the absolute configuration of the new stereocenters being 1R and 6S. Surprisingly, the acet\u00adyloxy substituents are positioned axially, in contrast to the usual d-gluco arrangement. Obviously the cyclo\u00adbutanone ring, with its bis\u00adectional positioned (C1\u2014C8) and axial bonds (C6\u2014C7) \u2013 in relation to the pyran\u00adose ring \u2013 enforces a flipping of the chair from 4C1 into 1C4. The cyclo\u00adbutane ring is almost planar [maximum deviation from the best plane of C7 = 0.0762\u2005(15)\u2005\u00c5 in A and 0.0815\u2005(15)\u2005\u00c5 in B] and can be described by the dihedral angles, forming by folding along the C6\u22efC8 and C1\u22efC7 line, between the planes C1\u2013C6\u2013C8/C6\u2013C7\u2013C8  and C1\u2013C6\u2013C7/C1\u2013C7\u2013C8 . The deviation of the carbonyl O atoms (O8A/O8B) from the mean plane of the pyran ring are 0.253\u2005(5) and 0.303\u2005(6)\u2005\u00c5 in mol\u00adecules A and B, respectively. The dihedral angles between the pyran\u00adose rings and the cyclo\u00adbutane rings are 61.3\u2005(1) and 62.1\u2005(1)\u00b0 for mol\u00adecules A and B, respectively. Four non-classical intra\u00admolecular hydrogen bonds for each of the both mol\u00adecules can be observed A is disordered . Mol\u00adecules A, B and C mainly differ in the torsion angles C10\u2014O4\u2014C5\u2014C6  and O4\u2014C5\u2014C6\u2014C1  of the acet\u00adyloxy substituents in the 5-position /0.763\u2005(3)/0.75\u2005(3)\u2005\u00c5, \u03b8 = 90.9\u2005(6)/91.0\u2005(2)/91\u2005(2)\u00b0 and \u03c6 = 12.6\u2005(6)/12.7\u2005(2)/28\u2005(3)\u00b0 for mol\u00adecules A, B and C, and not the usual chair conformation. This arrangement is caused by the cyclo\u00adbutane ring with the C1\u2014C8 and C6\u2014C7 bonds, which are bis\u00adectional related to the arabinose ring. The absolute configuration on the stereocenters of the shared ring atoms is C1S and C6R. The cyclo\u00adbutane rings are almost planar with maximum deviations from the best plane of 0.045\u2005(3)\u2005\u00c5 (C7A), 0.039\u2005(1)\u2005\u00c5 (C7B) and 0.072\u2005(12)\u2005\u00c5 (C7C). The nitro\u00adgen atoms deviate marginally from these planes [N1A \u22120.224\u2005(9)\u2005\u00c5, N1B 0.199\u2005(4)\u2005\u00c5, N1C 0.30\u2005(4)\u2005\u00c5. The dihedral angles within the four-membered rings between C1/C6/C8 and C6/C7/C8 are 9.4\u2005(5)\u00b0 (A), 8.2\u2005(2)\u00b0, (B) and 15\u2005(2)\u00b0 (C), and between C1/C6/C7 and C1/C7/C8 they are 9.0\u2005(5)\u00b0 (A), 7.9\u2005(3)\u00b0 (B) and 14\u2005(2)\u00b0 (C). The hydroxyl group of the oxime substit\u00aduent can adopt two different configurations. Mol\u00adecule B exhibits an E configuration. For disordered mol\u00adecules A and C, the E/Z ratio of the isomers is 0.802\u2005(7):0.198\u2005(7). Thus, the major component (A) is E configured, with the hydroxyl group pointing away from the six-membered ring. In the minor Z isomer (C), the hydroxyl group exhibits a sterically unfavourable inter\u00adaction with the carbohydrate ring. An intra\u00admolecular hydrogen bond between C5A/C5C and O5A is observed on Fig.\u00a02. The pyred Fig.\u00a02.S configured. The six-membered and the five-membered rings are fused in the cis configuration. The C3a\u2014C3 bond is axial and the C7a\u2014N1 bond is bis\u00adectionally positioned with respect to the pyran\u00adose ring. The pyran\u00adose ring exhibits a strongly distorted chair conformation, with puckering parameters q = 0.555\u2005(3)\u2005\u00c5, \u03b8 = 20.4\u2005(3)\u00b0 and \u03c6 = 267.9\u2005(9)\u00b0. The usual d-gluco configuration in the chair form 4C1 is found, in contrast to (I)Compound (III)A mol\u00adecules are hydrogen-bonded via C4A\u2014H4A\u22efO3Ai inter\u00adactions screwing around the b-axis direction . The A and B mol\u00adecules are linked by two further hydrogen bonds (C10B\u2014H104\u22efO8Aii and C10B\u2014H106\u22efO7Aii).The crystal packing of (I)on Fig.\u00a04. BetweenA mol\u00adecules are in an alternating arrangement with those consisting only of B mol\u00adecules, both screwing along the b-axis direction on Fig.\u00a05. In contvia weak C\u2014H\u22efO hydrogen bonds running along the a-axis direction. The chains formed this way are connected in a pairwise fashion by strong N1\u2014H1A\u22efO8 bonds along c et al.  was synthesized from tri-O-acetyl-d-glucal, commercially available or obtained by the procedure of Ferrier  in dry diethyl ether (30\u2005mL) at room temperature over 30\u2005min under an N2 atmosphere. After completion of the reaction (TLC control), zinc dust  was added at 273\u2005K. Acetic acid (13\u2005mL) was added within 10\u2005min and the reaction mixture was stirred for 60\u2005min. The reaction mixture was diluted with diethyl ether (60\u2005mL) and the insoluble materials were filtered off through Celite, which was washed with diethyl ether (5 \u00d7 50\u2005mL) and methanol (50\u2005mL). The filtrate was extracted with (3 \u00d7 100\u2005mL) water. The organic layer was dried over MgSO4 and concentrated in vacuo. The resulting residue was purified by column chromatography (hexa\u00adne/ethyl acetate 5:1) to afford pure cyclo\u00adbutanone (I)rier 1965. Tri\u00adchlOxime (II) was synthesized from di-O-acetyl-d-arabinal, obtained by the procedure of Ferrier  the corresponding cyclo\u00adbutanone was synthesized as described above and isolated by column chromatography (hexa\u00adne/ethyl acetate 5:1) in 83% yield. 242\u2005mg (1.0\u2005mmol) of this cyclo\u00adbutanone was dissolved in ethanol (2\u2005mL) and then added to a solution of sodium acetate  and hydroxyl\u00adamine hydro\u00adchloride  in water (2\u2005mL). The reaction mixture was stirred at 327\u2005K for 2\u2005h and then for 1\u2005h at room temperature. The reaction mixture was washed with water (30\u2005mL) and extracted with CH2Cl2 (3 \u00d7 50\u2005mL). The organic layers were combined, dried over MgSO4, filtered and concentrated in vacuo. The oxime (II)rier 1965. StartinLactam (III) was synthesized from cyclo\u00adbutanone (I)2Cl2 (3 \u00d7 50\u2005mL). The organic layers were combined, dried over MgSO4, filtered and concentrated in vacuo. Thionyl chloride  was added to a solution of the crude oxime in 1,4-dioxane (4\u2005mL), and stirred for 10\u2005min at room temperature. The reaction was quenched with saturated aqueous NaHCO3 (50\u2005mL), and extracted with EtOAc (3 \u00d7 100\u2005mL). The organic extracts were washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by column chromatography (hexa\u00adne/ethyl acetate 1:4) to afford the lactam in analytically pure form . Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of (III)A, caused by flipping of the N\u2014OH group. That disorder also causes disorder of the nearby ring atoms. Therefore the ring atoms of both the five- and six-membered rings were included in the disorder (but the OAc groups were left out). The geometry of the minor component was restrained to be similar to that of the major one with SAME, SADI and SIMU 0.01 restraints. The refinement of the occupation factors revealed an occupation ratio of 0.802\u2005(7)/0.198\u2005(7) for the two disordered components  = 1.2Ueq(C) with the exception of methyl hydrogen atoms, which were placed in their expected positions with HFIX 137 and refined with Uiso(H) = 1.5Ueq(C). For the minor disordered component in compound (II)2 groups (HFIX 13 and 23) and 0.83\u2005\u00c5 for OH groups (HFIX 147), and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). Crystal data, data collection and structure refinement details are summarized in Table\u00a04In compound (II)10.1107/S2056989016018727/zl2684sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989016018727/zl2684Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016018727/zl2684IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989016018727/zl2684IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989016018727/zl2684Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016018727/zl2684IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016018727/zl2684IIIsup7.cmlSupporting information file. DOI: 1518715, 1518714, 1518713CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both tungsten atoms have a slightly distorted octa\u00adhedral coordination.In the title complex two W(CO) 2P:P\u2032]bis\u00ad[penta\u00adcarbonyl\u00adtungsten(0)], [W2(C26H24P2)(CO)10], consists of two W(CO)5 moieties bridged by a bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)ethane (dppe) ligand. The W0 atom has a slightly distorted octa\u00adhedral coordination environment consisting of 5 carbonyl ligands and one P atom from the bridging dppe ligand with the nearest W0 atom 5.625\u2005(5)\u2005\u00c5 away. The complex resides on a center of symmetry.The centrosymmetric title complex, [\u03bc-ethane-1,2-diylbis(di\u00adphenyl\u00adphosphane)-\u03ba Dickson et al. (19892P(CH2)nPPh2 , finding that the predominate product in the reactions of n = 2 and 5 is the bridged complex (OC)5W[\u03bc-Ph2P(CH2)n]PPh2)W(CO)5, whereas when n = 4 it was reported the chelated product is favored (W(CO)4[\u03bc-Ph2P(CH2)4PPh2]. Tan et al. W(CO)5 )5 Fig.\u00a01 consists5W(\u03bc-dppe)W(CO)5 are bridged by a diphosphine approximately along the c axis and the mol\u00adecules themselves are stacked along the a axis. No significant van der Waals-type inter\u00adactions such as C\u2014H\u22ef\u03c0 or \u03c0\u2013\u03c0 contacts between adjacent mol\u00adecules are observed.The two tungsten atoms in each of the mol\u00adecules (OC)5W[\u03bc-Ph2P(CH2)5PPh2]W(CO)5 W(CO)5 2PPh2]Mo(CO)5 5PPh2]Cr(CO)5 5(NH2C6H5)  and dppe  to produce a golden yellow solution. After two\u2005h, methanol was added to precipitate a yellow solid. The precipitate was collected and washed with methanol (3 x 20\u2005mL). The resulting yellow solid was recrystallized from a 1:5 mixture of di\u00adchloro\u00admethane:methanol at 253\u2005K.All synthesis and crystallization procedures were carried out using standard Schlenk techniques. Di\u00adchloro\u00admethane was added to a mixture of W(CO)Crystal data, data collection, and structure refinement details are summarized in Table\u00a0110.1107/S2056989016013670/vn2114sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016013670/vn2114Isup2.hklStructure factors: contains datablock(s) I. DOI: 1500991CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "O\u2014H\u22efN hydrogen bonds link mol\u00adecules into a supra\u00admolecular chain along  21H28N4O, consists of two unique mol\u00adecules linked by an O\u2014H\u22efN hydrogen bond. The conformation of both C=N bonds is E and the azomethine functional groups lie close to the plane of their associated benzene rings in each of the independent mol\u00adecules. The dihedral angles between the two benzene rings are 83.14\u2005(4) and 75.45\u2005(4)\u00b0. The plane of the one of the N(CH3)2 units is twisted away from the benzene ring by 18.8\u2005(2)\u00b0, indicating loss of conjugation between the lone electron pair and the benzene ring. In the crystal structure, O\u2014H\u22efN hydrogen bonds together with C\u2014H\u22efO hydrogen bonds link neighbouring supra\u00admolecular dimers into a three-dimensional network.The asymmetric unit of the title compound, C Crystal structures of Schiff bases derived from substituted benzaldehydes and 1,3-di\u00adamino\u00adpropan-2-ol have been reported earlier  is shown in Fig.\u00a02A and N2 positions can be described by the torsion angles N2A\u2014C5A\u2014C51A\u2014C56A [\u22129.9\u2005(11) in mol\u00adecule A] and N2\u2014C5\u2014C51\u2014C56 [\u221214.9\u2005(11)\u00b0 in mol\u00adecule B]. The two outer aromatic rings (C11\u2013C16 and C51\u2013C56) are inclined to one another by 83.14\u2005(4)\u00b0 in mol\u00adecule A and 75.45\u2005(4)\u00b0 in mol\u00adecule B.The title compound crystallizes with two unique mol\u00adecules in the asymmetric unit. The conformers, labeled et al., 2016bA and 1.271\u2005(8) and 1.269\u2005(8)\u2005\u00c5 in mol\u00adecule B] and the corresponding inter\u00adnal angles at the nitro\u00adgen atom [C1A\u2014N1A\u2014C2A = 117.7\u2005(6) and C5A\u2014N2A\u2014C4A = 117.7\u2005(6) in mol\u00adecule A and C1\u2014N1\u2014C2 = 117.5\u2005(6) and C5\u2014N2\u2014C4 = 117.6\u2005(6) in mol\u00adecule B] also agree with those reported in the literature for similar compounds \u00b0 and C4A\u2014N2A\u2014C5A\u2014C51A = 179.9\u2005(6)\u00b0 in mol\u00adecule A and C2\u2014N1\u2014C1\u2014C11 = 178.6\u2005(6)\u00b0 and C4\u2014N2\u2014C5\u2014C51 = 177.0\u2005(6) in mol\u00adecule B.Bond distances and angles in the benzene rings are not unusual and compare well, both between the two independent mol\u00adecules and with those observed in related systems \u00b0 and C57\u2014N4\u2014C54\u2014C53 = \u22122.9\u2005(11)\u00b0 and with dihedral angles between the NMe2 plane and the benzene ring of 0.57\u2005(2) and 4.60\u2005(2)\u00b0, respectively, whilst in mol\u00adecule A the corresponding torsional angles C17A\u2014N3A\u2014C14A\u2014C13A and C57A\u2014N4A\u2014C54A\u2014C53A are 2.2\u2005(11) and 8.3\u2005(10)\u00b0, respectively. The dihedral angles between the two di\u00admethyl\u00adamino groups (N3A and N4A) and the benzene rings are 5.09\u2005(22) and 18.8\u2005(2)\u00b0 respectively, indicating that the lone electron pair of the N4A atom may not be completely conjugated with the benzene ring (C51A\u2013C56A).The two di\u00admethyl\u00adamino substituents in mol\u00adecule A\u2014H1A and the nitro\u00adgen N2 (Table\u00a01C(5) chains running along the a axis \u2005\u00c5] between O12 Table\u00a01, the twois Fig.\u00a03. The chas Table\u00a01.et al., 2016N,N\u2032-[bis\u00ad]bis\u00ad(4-methyl\u00adbenzene\u00adsulfonamide) -(2-chloro\u00adbenzyl\u00adidene)amino]\u00adpropan-2-ol  = 1.5Ueq(O). The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C\u2014H) = 0.95\u2005\u00c5 for aromatic and azomethine atoms, d(C\u2014H) = 0.98\u2005\u00c5 for methyl, d(C\u2014H) = 0.99\u2005\u00c5 for methyl\u00adene, d(C\u2014H) = 1.00\u2005\u00c5 for tertiary CH. The Uiso(H) values were constrained to 1.5Ueq(Cmeth\u00adyl) or 1.2Ueq(C) for the remaining H atoms. The structure shows signs of a superstructure. The two mol\u00adecules are related by a translation of 1/2 along the a axis. However, if the structure is refined in a cell with the a axis halved, the displacement parameters of one NMe2 group and some of the C atoms of the phenyl ring to which this group is attached are significantly enlarged  I. DOI: 10.1107/S2056989017006429/sj5528Isup2.hklStructure factors: contains datablock(s) I. DOI: 1547455CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III(DMC) acetyl\u00adide complexes that take on a pseudo-octa\u00adhedral symmetry and can be synthesized under weak-base conditions.The crystal structures presented herein consist of two positively charged Co III(DMC) . Chlorido\u00ad(phenyl\u00adethyn\u00adyl)cobalt(III) chloride\u2013aceto\u00adnitrile\u2013methanol (1/1/1), [Co(C8H5)Cl(C12H28N4)]Cl\u00b7CH3CN\u00b7CH3OH, 1, and bis\u00ad(phenyl\u00adethyn\u00adyl)cobalt(III) tri\u00adfluoro\u00admethane\u00adsulfonate\u2013di\u00adchloro\u00admethane (2/1), [Co(C8H5)2(C12H28N4)]2(CF3SO3)2\u00b7CH2Cl2, 2, were prepared under weak-base conditions in satisfactory yields. Single-crystal X-ray diffraction studies revealed that both 1 and 2 adopt a pseudo-octa\u00adhedral symmetry in which the Cl\u2014Co\u2014C angles of 1 and C\u2014Co\u2014C of 2 range from 177.7\u2005(2) to 178.0\u2005(2)\u00b0 and from 177.67\u2005(9) to 179.67\u2005(9)\u00b0, respectively. In both structures, the CoIII metal center is coordinated in the equatorial plane by four N atoms, in which the N\u2014Co\u2014N angles range from 85.6\u2005(3) to 94.4\u2005(3)\u00b0. The structure of 1 features two crystallographically independent mol\u00adecules in its triclinic cell (Z\u2032 = 2), which are related to each other by pseudo-monoclinic symmetry. The crystal investigated was twinned by a symmetry operator of the approximate double-volume C-centered cell , with a refined twin ratio of 0.798\u2005(3) to 0.202\u2005(3). Both methanol solvent mol\u00adecules in 1 are disordered, the major occupancy rates refined to 0.643\u2005(16) and 0.357\u2005(16). Compound 2 also contains two mol\u00adecules in the asymmetric unit, together with two tri\u00adfluoro\u00admethane\u00adsulfonate anions  and a disordered di\u00adchloro\u00admethane [occupancy values of 0.545\u2005(12) and 0.455\u2005(12)].Reported in this contribution are the synthesis and crystal structures of new mono- and bis-phenyl\u00adacetyl\u00adides based on Co Inter\u00ade1 crystallizes in PIII(DMC)(C2Ph)(Cl)]+ cation, a chloride counter-ion, and one aceto\u00adnitrile and methanol solvate mol\u00adecule, for a total composition of C20H33ClCoN4\u00b7C2H3N\u00b7CH4O\u00b7Cl. The two unique moieties, labeled A and B, are related by a pseudo-glide plane (see the Supra\u00admolecular features section for a more detailed discussion), and a common atom-naming scheme was used for the contents of the two unique halves of the structure. Both methanol mol\u00adecules are disordered, with a common refined occupancy ratio of 0.643\u2005(16):0.357\u2005(16).Compound 2 crystallizes in P21, Fig.\u00a021, 2 also features two unique cations and anions in its asymmetric unit, but they are not related by any crystallographic pseudo-symmetry. Each complex cation [CoIII(DMC)(C2Ph)2]+ is paired with a triflate anion. The asymmetric unit is completed by a single methyl\u00adene chloride solvate mol\u00adecule, yielding a formula of 2(C28H38CoN4)\u00b72(CF3O3S)\u00b7CH2Cl2. One of the triflate anions as well as the methyl\u00adene chloride mol\u00adecule were refined as disordered, with occupancy rates of 0.503\u2005(22) and 0.545\u2005(12) for the major components.Compound 1 and 2 are similar  and 178.0\u2005(2)\u00b0] and C\u2014Co\u2014C [177.67\u2005(9) and 179.67\u2005(9)\u00b0] units are close to normal to the equatorial plane created by the coordinated amines of the macrocyclic ligand, confirming octa\u00adhedral geometries. The C\u2014Co\u2014N and Cl\u2014Co\u2014N angles are all tightly clustered around 90\u00b0. The actual values range from 87.1\u2005(1) to 92.9\u2005(1)\u00b0 \u2013CH2\u2013CH2\u2013N connections  to 174.2\u2005(2)\u00b0, with the latter extreme value belonging to one of the Co\u2014C\u2261C units of 1 are as expected for this class of compounds and compare well to values observed by Shores for the cyclam macrocyclic counterpart of 1. \u2005\u00c5 avg.] relative to compound 1. This effect is a result of the stronger \u03c0-donation from phenyl\u00adacetyl\u00adide compared to chloride. The C\u2014C and C\u2261C bond lengths of the phenyl\u00adacetyl\u00adene ligands fall in the expected region for single and triple bonds respectively. The acetyl\u00adides in compound 2 show a slightly cumulenic character with elongated C\u2261C and shortened C\u2014C bond lengths with respect to compound 1, as was also seen by Shores and coworkers  and 1.905\u2005(7)\u2005\u00c5] for compound C-centered unit cell with parameters a = 34.721, b = 9.690, c = 15.668\u2005\u00c5, and \u03b2 = 93.41\u00b0. The \u03b1 and \u03b3 angles in the monoclinic cell deviate substanti\u00adally from 90\u00b0, being 88.97 and 89.52\u00b0 when not constrained during data integration. In the crystal structure, the monoclinic pseudo-symmetry manifests itself by the presence of a pseudo b-glide operation along the a-axis of the triclinic cell, Fig.\u00a03A and B, of the surrounding chloride anions and solvate mol\u00adecules and of a second cation. The pseudo-glide symmetry is mostly obeyed by the constituents of the asymmetric unit; the root-mean-square deviation for one overlaid pair of A and B cations is 0.138\u2005\u00c5. For the surrounding solvate mol\u00adecules, for the chloride anions and neighboring cations this is no longer the case. This can especially be seen for a second cation shown in Fig.\u00a04SHELXL) resulted in a twinning ratio of 0.798\u2005(3):0.202\u2005(3), and R1 does increase by 2.6% if twinning is ignored during structure refinement.The structure of the chlorine salt exhibits monoclinic pseudo-symmetry, emulating a double-volume a and c-axes, are shown in Figs. 5Overlays of a larger segment of the lattice, along the 1 of the mono\u00adacetyl\u00adide, the ammonium N\u2014H units of the macrocycle form N\u2014H\u22efN hydrogen bonds with the aceto\u00adnitrile nitro\u00adgen atom, N\u2014H\u22efO hydrogen bonds to the methanol oxygen, and N\u2014H\u22efCl hydrogen bonds to both the inter\u00adstitial chloride anions as well as the cobalt-bound chlorine. The chloride anions are also acceptors for O\u2014H\u22efCl hydrogen bonds originating from the disordered methanol mol\u00adecules and for a series of weaker C\u2014H\u22efCl hydrogen bonds from macrocyclic carbon atoms. The type and number of hydrogen bonds is essentially the same between the two halves of the structure related by pseudo-symmetry, but the exact metrics and numbers are slightly modulated. The N\u2014H\u22efN, N\u2014H\u22efO, and N\u2014H\u22efCl hydrogen bonds, when combined, connect the cations, anions and solvate mol\u00adecules into ribbons that extend infinitely along the b-axis and are perpendicular to the a-axis, and exactly one unit cell thick in the a- and c-axis directions , and their strength varies substanti\u00adally between the ion pairs. The first of the two cations, involving nitro\u00adgen atoms N1 through N4, features each two N\u2014H\u22efO and N\u2014H\u22efF hydrogen bonds (not counting duplicates from triflate disorder), Fig.\u00a09In the triflate salt ns Fig.\u00a08. The twoIII(DMC)Cl2]Cl was synthesized according to literature procedures (C2Ph)Cl]Cl (1). [CoIII(DMC)Cl2]Cl  was dissolved in 40\u2005mL of methanol. Phenyl\u00adacetyl\u00adene  and Et3N  were added and the solution was refluxed overnight. Solvent was removed via rotary evaporation, and the solid was loaded onto a silica gel plug and eluted with CH3OH/EtOAc  as a red fraction. The desired product was recrystallized from ether\u2013methanol to afford 170\u2005mg of a coral solid (73% based on [CoIII(DMC)Cl2]Cl). Single crystals were grown from slow diffusion of ether into a methanol solution of 1.Preparation of [CoIII(DMC)(C2Ph)Cl]Cl (1). ESI\u2013MS: [M]+, 423.0. 1H NMR : 7.55\u20137.41 , 7.37\u20137.25 , 7.25\u20137.15 , 5.36 , 4.23 , 3.21\u20132.46 , 1.93\u20131.84 , 1.53\u20131.48 , 1.30 . Visible spectra, \u03bbmax : 256 , 493\u2005(101); IR (cm\u22121): C\u2261C: 2122 (m).Data for [CoIII(DMC)(C2Ph)2]OTf (2). Compound 1  and AgOTf  were dissolved in 50\u2005mL of CH3CN and refluxed for 48\u2005h. The precipitate that formed was filtered out, and 3.1\u2005mL (22\u2005mmol) of Et3N and 0.20\u2005mL (1.8\u2005mmol) of phenyl\u00adacetyl\u00adene were added and the solution was refluxed for 48\u2005h. The solution was purified over a silica gel plug and the product eluted with CH3OH/EtOAc . A pale-yellow fraction was collected and recrystallized from ether\u2013methanol to afford 102\u2005mg of a yellow solid (47% based on 1). Single crystals were grown from slow diffusion of n-hexa\u00adnes into a CH3OH/CH2Cl\u00ad2  solution of 2.Preparation of [CoIII(DMC)(C2Ph)2]OTf (2). ESI\u2013MS: [M]+, 489.0. 1H NMR : 7.58\u20137.42 , 7.36\u20137.24 , 7.22\u20137.13 , 4.90 , 3.84 , 3.30\u20133.01 , 2.81\u20132.78 , 2.68\u20132.63 , 2.50\u20132.43 , 1.83 , 1.38 , 1.27 . Visible spectra, \u03bbmax : 271 , 464 (64.5); IR (cm\u22121): C\u2261C: 2102 (m).Data for  direction in reciprocal space . Application of the twin matrix 1 0 0, 0 The structure of compound 1, each methanol group was refined with two-component disorder with a shared occupancy ratio for the two sites. The C\u2014O bond lengths were restrained to 1.427\u2005(20)\u2005\u00c5. Each minor occupancy component was restrained to be similar the respective major occupancy component . The Uij components for atoms within 2.0\u2005\u00c5 were restrained to be similar . The alcohol hydrogen atom to neighboring chloride distances were restrained based on hydrogen-bonding considerations. Subject to these conditions, the occupancy rates refined to 0.643\u2005(16) and 0.357\u2005(16).In the structure of compound 2, the S1 triflate anion was refined with two-component disorder. Each moiety was restrained to have a similar geometry as the S2 triflate anion . The Uij components for disordered atoms within 2.0\u2005\u00c5 were restrained to be similar . Subject to these conditions, the occupancy factors refined to 0.503\u2005(22) and 0.497\u2005(22). The di\u00adchloro\u00admethane mol\u00adecule was refined with two-component disorder. The minor occupancy component was restrained to have a similar geometry as the major occupancy component . The Uij components for atoms within 2.0\u2005\u00c5 were restrained to be similar . Subject to these conditions, the occupancy factors refined to 0.545\u2005(12) and 0.455\u2005(12).In the structure of compound 10.1107/S2056989018003997/vm2209sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989018003997/vm22091sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018003997/vm22092sup3.hklStructure factors: contains datablock(s) 2. DOI: 1828222, 1828221CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R,R,SFc,SFc)-[Fe2(C5H5)2(C38H36BrNP2)]\u00b7Br\u00b7CH2Cl2 has been determined by X-ray single-crystal diffraction.The absolute structure of -[Fe2(C5H5)2(C38H35NP2)] (1), single crystals of the di\u00adchloro\u00admethane monosolvate of the Br\u2212 salt of the protonated ligand 1H+ were obtained serendipitously, i.e. [Fe2(C5H5)2(C38H36NP2)]Br\u00b7CH2Cl2. The crystal structure of 1H\u00b7Br\u00b7CH2Cl2 was determined by single-crystal X-ray diffraction. The mean bond lengths in the ferrocene units are Fe\u2014C = 2.049\u2005(3)\u2005\u00c5 and C\u2014C = 1.422\u2005(4)\u2005\u00c5 within the cyclo\u00adpenta\u00addienyl rings. The mean C\u2014N bond length is 1.523\u2005(4)\u2005\u00c5. The inter\u00adplanar angle between the two connected cyclo\u00adpenta\u00addienyl rings is 49.2\u2005(2)\u00b0. One ferrocene moiety adopts a staggered conformation, whereas the other is between staggered and eclipsed. The Br\u2212 ions and the CH2Cl2 mol\u00adecules are located in channels extending along <100>. One ammonium H atom forms a hydrogen bond with the Br\u2212 ion [H\u22efBr = 2.32\u2005(4)\u2005\u00c5 and C\u2014H\u22efBr = 172\u2005(3)\u00b0]. The second ammonium H atom is not involved in hydrogen bonding.During the synthesis of an FeBr Ammonium H atoms were found in difference Fourier maps and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016020417/pk2595sup1.cifCrystal structure: contains datablock(s) I, general. DOI: 10.1107/S2056989016020417/pk2595Isup2.hklStructure factors: contains datablock(s) I. DOI: 1524191CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The hig\u201d should be replaced with \u201c50 values of H2O2 were found for cell pretreated with 50\u2009\u03bcg/mL BJLN (89.95\u2009\u03bcM) and 100\u2009\u03bcg/mL MR219 (143.90\u2009\u03bcM) extracts when compared to negative control (271.00\u2009\u03bcM) Significant decrements in the IC1.00\u2009\u03bcM) . The hig.\u201dIn addition, in the \u201cResults\u201d (Section 3.3), the text reading \u201cAn incorrect version of \u03bcg/mL) (grey dotted line) was incorrectly plotted. The correct version of the figure is as shown below with the corrected fourth datum point for MR219 (50\u2009\u03bcg/mL) (grey dotted line).Accordingly,"}
{"text": "In the crystal, the ASP anions are linked  14H16NO+\u00b7C4H6NO4\u2212\u00b7H2O, crystallizes as a monohydrate. The 1,2-di\u00adphenyl\u00adethyl group in the cation has a cis conformation, and the aspartic acid anion is in the zwitterionic form. In the crystal, the ASP anions are linked via N\u2014H\u22efO hydrogen bonds to form a 21 helix along the b-axis direction. The helices are linked by the ADE cations via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming layers parallel to the bc plane. There are channels in the layers that are occupied by water mol\u00adecules, which link to both the anions and cations via Owater\u2014H\u22efO and N\u2014H\u22efOwater hydrogen bonds. There are also C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions present within the layers.The title diastereomeric salt, formed between 2-amino-1,2-di\u00adphenyl\u00adethanol (ADE) and aspartic acid (ASP), C The optical separation of ASP with cis-ADE was introduced without chemical modification. The crystal structure of the title mol\u00adecular salt, formed between l-(S)-ASP and -cis-ADE, is reported herein.The production of chiral compounds has great importance in the pharmaceutical industry, and diastereomeric salt separation is still widely applied in the process. A synthetic optical resolving agent, chiral 2-amino-1,2-di\u00adphenyl\u00adethanol (ADE)  is 48.71\u2005(9)\u00b0 and the torsion angle O1A\u2014C1A\u2014C2A\u2014N1A is \u221265.0\u2005(2)\u00b0. The hy\u00addroxy group adopts a gauche conformation [O1A\u2014C1A\u2014C2A\u2014C9A = 60.1\u2005(2)\u00b0] with respect to phenyl ring B. Thus, the tweezer-like motif is twisted with respect to the phenyl groups. This arrangement is similar to that found in racemic cis-ADE -ASP crystallizes as a deprotonated zwitterion. The succinate group adopts a cis conformation [C1B\u2014C2B\u2014C3B\u2014C4B = \u221253.0\u2005(2)\u00b0], which is the motif commonly found in l-ASP salts; for example l-His\u00b7l-ASP monohydrate  and 1.4\u2005(3)\u00b0, respectively.S)-ASP anions correlated with crystallographic symmetry are linked via N1B\u2014H1B3\u22efO4Bii [2.868\u2005(2)\u2005\u00c5] hydrogen bonds into C(6) chains to form a right-handed 12-helix along the b-axis direction -cis-ADE cations via N\u2014H\u22efO hydrogen bonds [N1A\u2014H1A2\u22efO1B = 2.862\u2005(2)\u2005\u00c5 and N1A\u2014H1A1\u22efO4Biii = 2.742\u2005(3)\u2005\u00c5] and O\u2014H\u22efO hydrogen bonds [O1A\u2014H1O1\u22efO2Bi = 2.752\u2005(2)\u2005\u00c5], forming layers parallel to the bc plane \u2005\u00c5 and O1C\u2014H1OA\u22efO1Biv = 2.840\u2005(2)\u2005\u00c5] and N\u2014H\u22efOwater hydrogen bonds [N1B\u2014H1B2\u22efO1C = 2.938\u2005(2)\u2005\u00c5 and N1A\u2014H1A3\u22efO1C = 2.926\u2005(3)\u2005\u00c5], shown in Fig.\u00a04a-axis direction.In the crystal, the -cis-2-Amino-1,2-di\u00adphenyl\u00adethanol (ADE) and aspartic acid (ASP) were purchased from Sigma\u2013Aldrich Co. Ltd. The title mol\u00adecular salt was obtained from an aqueous ethanol solution of racemic-ASP and -cis-ADE in a 2:1 molar ratio, heated to 333\u2005K under stirring. On slow cooling to ambient temperature and slow evaporation of the solvent, colourless rod-shaped crystals were obtained. = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017015729/su5398sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017015729/su5398Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017015729/su5398Isup3.cmlSupporting information file. DOI: 1582706CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule has an almost planar geometry (r.m.s. deviation = 0.012\u2005\u00c5), and its mol\u00adecular structure is stabilized by an intra\u00admolecular secondary Se\u22efO inter\u00adaction of 2.353\u2005(3)\u2005\u00c5, closing a four-membered N\u2014C\u2014Se\u22efO ring. The title compound represents the first monomeric organoselenenyl chloride stabilized intra\u00admolecularly by an inter\u00adaction of this type. The non-valent attractive Se\u22efO inter\u00adaction results in a substantial distortion of the geometry of the ipso-carbon atom. The endo-cyclic N\u2014C\u2014Se [102.1\u2005(3)\u00b0] and exo-cyclic C\u2014C\u2014Se [136.9\u2005(3)\u00b0] bond angles deviate significantly from the ideal value of 120\u00b0 for an sp2-hybridized carbon atom, the former bond angle being much smaller than the latter. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming zigzag chains propagating along [010]. The chains, which stack along the a-axis direction, are linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.960\u2005(3)\u2005\u00c5], forming corrugated sheets parallel to the ab plane.The title compound, C RSeX  play an important role in modern organic synthesis and are used as reagents for the functionalization of many classes of compounds, including organoselenium compounds with a broad spectrum of biologi\u00adcal activities \u00b0] and exo-cyclic C3\u2014C2\u2014Se1 [136.9\u2005(3)\u00b0] bond angles deviate significantly from the ideal value of 120\u00b0 for an sp2-hybridized carbon atom, the former angle being much smaller than the latter. The title compound represents the first monomeric organoselenenyl chloride stabilized intra\u00admolecularly by an inter\u00adaction of this type. Previously, the analogous stabilization of monomeric organoselenenyl chlorides by intra\u00admolecular secondary Se\u22efS \u2005\u00c5, Cg is the centroid of the N1/C2\u2013C6 ring, inter\u00adplanar distances = 3.590\u2005(2)\u2005\u00c5, slippages = 1.671\u2005\u00c5, symmetry codes: (i) x\u00a0\u2212\u00a01, y, z; (ii) x\u00a0+\u00a01, y, z].In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds Table\u00a01, forminget al.  of the title compound. Colourless prismatic crystals of the title compound were obtained after recrystallization of the crude product from di\u00adchloro\u00admethane (m.p. 433\u2013435\u2005K). IR , \u03bd 1617, 1462, 1423, 1254, 1151, 836, 748, 621. 1H NMR : \u03b4 = 8.28 ; 7.52 ; 7.43 ; 7.30 . Analysis calculated for C5H4ClNOSe: C 24.81; H 1.93; N 6.72. Found: 24.43; H 1.83; N 6.65.The synthesis of the title compound is illustrated in Fig.\u00a03 2010ab,c \u25b8. A Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016018946/su5337sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016018946/su5337Isup2.hklStructure factors: contains datablock(s) I. DOI: 1519449CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 1:1 co-crystal comprising two fused-ring mol\u00adecules features significant hydrogen bonding between the 1,8-di\u00adhydroxy\u00adanthra\u00adquinone coformers with the main links between the resulting dimeric aggregates and the bromo\u00adnaphtho\u00adquinone coformer being of the type C\u2014H\u22efO. 10H5BrO2\u00b7C14H8O4 , features one mol\u00adecule of each coformer. The 2-bromo\u00adnaphtho\u00adquinone mol\u00adecule is almost planar . The 1,8-di\u00adhydroxy\u00adanthra\u00adquinone mol\u00adecule is planar (r.m.s. deviation for the 18 non-H atoms is 0.022\u2005\u00c5) and features two intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bonds. Dimeric aggregates of 1,8-di\u00adhydroxy\u00adanthra\u00adquinone mol\u00adecules assemble through weak inter\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bonds. The mol\u00adecular packing comprises stacks of mol\u00adecules of 2-bromo\u00adnaphtho\u00adquinone and dimeric assembles of 1,8-di\u00adhydroxy\u00adanthra\u00adquinone with the shortest \u03c0\u2013\u03c0 contact within a stack of 3.5760\u2005(9)\u2005\u00c5 occurring between the different rings of 2-bromo\u00adnaphtho\u00adquinone mol\u00adecules. The analysis of the Hirshfeld surface reveals the importance of the inter\u00adactions just indicated but, also the contribution of additional C\u2014H\u22efO contacts as well as C=O\u22ef\u03c0 inter\u00adactions to the mol\u00adecular packing.The asymmetric unit of the title co-crystal, C The six carbon atoms comprising the cyclo\u00adhexa-2,5-diene-1,4-dione ring of the naphtho\u00adquinone mol\u00adecule are not strictly planar with the r.m.s. deviation being 0.030\u2005\u00c5; the maximum deviations are 0.025\u2005(1) and \u22120.031\u2005(2)\u2005\u00c5 for the C4a and C4 atoms, respectively. The appended Br1, O1 and O4 atoms lie, respectively, 0.077\u2005(1), 0.078\u2005(1) and \u22120.117\u2005(1)\u2005\u00c5 out of the plane with the Br1 atom lying to one side of the ring and the carbonyl-O atoms to the other. Overall, the r.m.s. deviation for the best plane defined by the 13 non-H atoms comprising the naphtho\u00adquinone mol\u00adecule is 0.060\u2005\u00c5, with the maximum deviations being 0.093\u2005(1)\u2005\u00c5 for atom Br1 and \u22120.099\u2005(1)\u2005\u00c5 for the O4 atom, again with these atoms lying to opposite sides of the plane. With respect to the anthra\u00adquinone mol\u00adecule, the r.m.s. deviation for the 18 non-H atoms is 0.022\u2005\u00c5 with the maximum deviations being 0.039\u2005(2)\u2005\u00c5 for C(13) and 0.026\u2005(1)\u2005\u00c5 for the C19 and C23 atoms. As seen from Fig.\u00a01b, the hy\u00addroxy-H atoms are orientated to be proximate to the centrally located carbonyl-O atom to form intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen-bonds, Table\u00a01The mol\u00adecular structures of the constituents of (I)a, is connected by a centrosymmetric planar, eight-membered {\u22efHO\u22efO\u22efH}2 synthon which incorporates two transannular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bonds. The dimeric aggregates stack along the b axis being surrounded by two columns of similar dimeric aggregates and six columns comprising naphtho\u00adquinone mol\u00adecules, Fig.\u00a02b. Connections between columns, leading to a three-dimensional architecture, are of the type sp2-C\u2014H\u22efO(carbon\u00adyl) and involve all the remaining carbonyl-O atoms with the O atom of the naphtho\u00adquinone-C4=O4 moiety forming two such contacts, Table\u00a01i.e. between the  and  rings with the inter-centroid separation being 3.5760\u2005(9)\u2005\u00c5 and the angle of inclination being 1.64\u2005(7)\u00b0 for symmetry operation x, \u22121\u00a0+\u00a0y, z. The closest comparable inter\u00adaction within the stack of anthra\u00adquinone mol\u00adecules is 4.1013\u2005(9)\u2005\u00c5, i.e. between (C15\u2013C21) and (C19\u2013C24) rings; angle of inclination = 0.65\u2005(7)\u00b0 for symmetry operation: x, \u22121\u00a0+\u00a0y, z.In addition to the intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen-bonds in the anthra\u00adquinone mol\u00adecule, both hy\u00addroxy-H atoms from weaker inter\u00admolecular hydrogen-bonds with a centrosymmetrically related mol\u00adecule indicating each hy\u00addroxy-H atom is bifurcated, Table\u00a01et al., 2016et al., 2016dnorm, Figs. 3The Hirshfeld surface analysis of title 1:1 co-crystal, (I)dnorm in Fig.\u00a03a. On the Hirshfeld surface mapped over the calculated electrostatic potential, the respective donors and acceptors appear as the blue  and red regions  in Fig.\u00a05a. The presence of faint-red spots near carbon atoms C11, C19, Fig.\u00a03a, and near the atoms C15 and C20, Fig.\u00a03b, also indicate the links between mol\u00adecules through short inter-atomic C\u22efC contacts, Table\u00a02a. Links between the coformers involving their carbonyl-C4=O4 and C20=O20 groups through short inter\u00adatomic C\u22efO/O\u22efC contacts, Table\u00a02b and 4b. This is also illustrated by the black dashed lines on the Hirshfeld surface mapped over electrostatic potential in Fig.\u00a06b. The donors and acceptors of inter\u00admolecular C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions can be viewed as bright-red spots having labels \u20183\u2019\u2013\u20185\u2019 in Figs. 3b and 4a, labelled with \u20186\u2019. The immediate environments about reference anthra\u00adquinone and naphtho\u00adquinone mol\u00adecules within shape-index-mapped Hirshfeld surfaces highlighting inter\u00admolecular O\u2014H\u22efO, C\u2014H\u22efO, \u03c0\u2013\u03c0 stacking and C\u2014O\u22ef\u03c0 inter\u00adactions influential on the packing are illustrated in Figs. 7The donors and acceptors of inter\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen-bonds between anthra\u00adquinone mol\u00adecules are viewed as bright-red spots labelled with \u20181\u2019 and \u20182\u2019 on the Hirshfeld surfaces mapped over a. The plots delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC, C\u22efC and C\u22efO/O\u22efC contacts  atoms are viewed as a pair of short spikes at de\u00a0+\u00a0di\u00a0\u223c\u00a02.4\u2005\u00c5 in the donor and acceptor regions of their respective plots in Fig.\u00a09c. The points corresponding to anthra\u00adquinone-C15\u2014H15\u22efO4(carbon\u00adyl) inter\u00adactions and other short inter\u00adatomic O\u22efH contacts, Table\u00a02The donors and acceptors of the naphtho\u00adquinone-H3 and anthra\u00adquinone-O20(carbon\u00adyl) atoms are viewed as a thin, long spike at de\u00a0+\u00a0di\u00a0<\u00a02.9\u2005\u00c5, i.e. less than sum of their van der Waals radii, in the fingerprint plot delineated into C\u22efH/H\u22efC contacts for anthra\u00adquinone, Fig.\u00a09d, are indicative of short inter\u00adatomic C\u22efH contacts, Table\u00a02e, having high density at around de\u00a0=\u00a0di\u00a0\u223c\u00a01.8\u2005\u00c5. The parabolic distribution of points with the peak at de\u00a0=\u00a0di\u00a0\u223c\u00a01.6\u2005\u00c5 in the plot for the anthra\u00adquinone coformer, Fig.\u00a09e, indicates links between these mol\u00adecules through short inter\u00adatomic C\u22efC contacts along the b axis. The presence of C\u22efC contacts in (I)A pair of short peaks at f, results from short, inter-atomic C\u22efO/O\u22efC contacts whereas the 11.9% contribution from C\u22efO/O\u22efC contacts for the anthra\u00adquinone mol\u00adecule has a contribution from C=O\u22ef\u03c0 inter\u00adactions involving carbony-O19 and -O20 atoms and  and  rings, Table\u00a04f.The 3.9% contribution from C\u22efO/O\u22efC contacts to the Hirshfeld surface for the naphtho\u00adquinone mol\u00adecule, Fig.\u00a09Although the naphtho\u00adquinone-bromide substituent makes a notable contribution to the Hirshfeld surface, Table\u00a03et al., 2016cf. 0.060\u2005\u00c5 in (I)et al., 2008i.e. a 3:1 co-crystal with acetic acid 2Cl2/hexane (1:1 v/v) and a single, yellow fraction was collected. After evaporation of the solvent under reduced pressure, a yellow solid was obtained. This was recrystallized from ethyl acetate solution to give small orange\u2013red crystals with yields of 78\u201385% based upon the qu\u00adantity of 1,8-di\u00adhydroxy\u00adanthra\u00adquinone initially used. Notably, the substrates 2-bromo\u00adnaphtho\u00adquinone and 1,8-di\u00adhydroxy\u00adanthra\u00adquinone could not be chromatographically distinguished as they ran with equivalent Rf\u2019s in a wide range of solvents and solvent mixtures. NMR spectra (1H and 13C) were consistent with a one to one mixture of the same components as there was no deviation of chemical shifts in comparison to the spectra of the individual components. A sample of the co-crystal material had a well defined melting point of 413\u2013414\u2005K, which is inter\u00admediate between the melting points of the pure components 2-bromo\u00adnaphtho\u00adquinone, 405\u2013406\u2005K Uiso(H) set to 1.2Ueq(C). The O-bound H atoms were located from a difference map but refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017005667/wm5383sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017005667/wm5383Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005667/wm5383Isup3.cmlSupporting information file. DOI: 1543933CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom is surrounded by three \u03bc3-iodide anions and one S atom, while the other is coordinated by three \u03bc3-iodide ions an O atom. In the crystal, there are inter\u00admolecular C\u2014H\u22efI hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions between ligands. The packing generates a two-dimensional brick-wall structure.The structure of the title copper(I) coordination polymer is reported. One Cu H)-one  in aceto\u00adnitrile/di\u00adchloro\u00admethane results in a crystalline coordination polymer, namely poly[bis\u00ad{\u03bc2-1-[2-(cyclo\u00adhexyl\u00adsulfan\u00adyl)eth\u00adyl]pyridin-2(1H)-one}tetra-\u03bc3-iodido\u00adtetra\u00adcopper(I)], [Cu4I4L2]n. The asymmetric unit comprises two ligand mol\u00adecules, four copper(I) ions and four iodide ions. Inter\u00adestingly, the O atoms are bound to the soft copper(I) ions. The stair-step clusters of Cu and I atoms in the asymmetric unit are linked repeatedly, giving rise to infinite chains along [100]. Neighbouring infinite chains are linked through the L mol\u00adecules, forming a two-dimensional brick-wall structure. These two-dimensional networks are stacked alternately along [001]. Additionally, there are inter\u00admolecular C\u2014H\u22efI hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions between the ligands.The reaction of copper(I) iodide with 1-[2-(cyclo\u00adhexyl\u00adsulfan\u00adyl)eth\u00adyl]pyridin-2(1 CuI\u2014O bonds have been reported previously in copper(I) coordination polymers with phosphine ligands  complexes have been studied continuously over several decades because of their potential applications as sensors, catalysts, and gas storage materials  ions, four \u03bc3-iodide ions, and two L ligands as shown in Fig.\u00a01A (identified by S1) and LB (identified by S2), the pyridyl and cyclo\u00adhexyl rings are in anti and gauche conformations with torsion angles of \u2212154.7\u2005(6)\u00b0 [C6\u2014S1\u2014C7\u2014C8] and 62.3\u2005(7)\u00b0 [C19\u2014S2\u2014C20\u2014C21], respectively. All of the CuI atoms (Cu1\u2013Cu4) have distorted tetra\u00adhedral coordination geometries. The Cu1 and Cu2 atoms are bound by three \u03bc3-iodide anions and one S atom, while Cu3 and Cu4 are coordinated by three \u03bc3-iodide ions and one O atom. The ranges of inter\u00adatomic distances in the title compound are 2.7082\u2005(15)\u20132.7444\u2005(14)\u2005\u00c5, 2.297\u2005(2)\u20132.314\u2005(2)\u2005\u00c5, 2.6210\u2005(12)\u20132.7230\u2005(12)\u2005\u00c5, and 2.071\u2005(6)\u20132.087\u2005(6)\u2005\u00c5 for Cu\u2014Cu, Cu\u2014S, Cu\u2014I, and Cu\u2014O, respectively  as shown in Fig.\u00a02A\u22efI4ii, C12\u2014H12\u22efI1iii and C21\u2014H21B\u22efI3iv  hydrogen bonds between ligands. Red dashed lines display inter\u00admolecular C5\u2014H5A\u22efCg1v [H\u22efCg1=3.00\u2005\u00c5] inter\u00adactions between the ligands  complexes of N/S mixed donor atom ligands have been reported (Jeon Synthesis of 1-[2-(cyclo\u00adhexyl\u00adsulfan\u00adyl)eth\u00adyl]pyridin-2(1H)-one (L)2SO4, and evaporated to give a crude oil. Column chromatography , Rf = 0.28) : 7.28 , 6.52 , 6.11 , 4.01 , 2.85 , 2.51 , 2.00\u20131.13 ; 13C NMR : 161.33, 140.03, 139.52, 119.40, 104.86, 49.21, 42.48, 33.15 27.71, 25.44, 25.29.Thionyl chloride  was added dropwise to 2-(cyclo\u00adhexyl\u00adthio)\u00adethanol  in chloro\u00adform. The mixture was stirred under reflux for 1\u2005h then cooled to 253\u2005K. Chloro\u00adform was removed, yielding crude 2-chloro\u00adethyl\u00adcyclo\u00adhexyl\u00adsulfide. 2-Hy\u00addroxy\u00adpyridine  and potassium hydroxide  were dissolved in 10\u2005ml of tetra\u00adhydro\u00adfuran and 5\u2005ml of water, and then the solution was added dropwise to the crude chloride. The solution was refluxed for 24\u2005h and cooled. The crude product was extracted by di\u00adchloro\u00admethane. The di\u00adchloro\u00admethane layer was dried with anhydrous Na4I4Preparation of [CuL2]nL  was allowed to mix with an aceto\u00adnitrile (5\u2005ml) solution of CuI . The colourless precipitate was filtered and washed with a diethyl ether/aceto\u00adnitrile (5/1 v/v) solution. Single crystals suitable for X-ray analysis were obtained by slow evaporation of di\u00adchloro\u00admethane from the reaction mixture.A di\u00adchloro\u00admethane (5\u2005ml) solution of Uiso(H) = 1.2Ueq(C) for aromatic C\u2014H groups, C\u2014H = 0.99\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for CH2 groups, and C\u2014H = 1.00\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for Csp3\u2014H groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017015377/sj5538sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017015377/sj5538Isup2.hklStructure factors: contains datablock(s) I. DOI: 1581394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound was isolated as a by-product from a reaction incorporating 2,4,6-tri\u00admethyl\u00adbenzoic acid under basic conditions. 20H22O3, was formed in the reaction between 2,4,6-tri\u00admethyl\u00adbenzoic acid and N,N-diiso\u00adpropyl\u00adethyl\u00adamine in the presence of 1,3-di\u00adchloro-1,3-bis\u00ad(di\u00admethyl\u00adamino)\u00adpropenium hydrogen dichloride, and was recrystallized from diethyl ether solution. It is the first exclusively alkyl-substituted benzoic anhydride to have been structurally characterized. The asymmetric unit consists of a half mol\u00adecule, the other half of which is generated by twofold rotation symmetry; the dihedral angle between the symmetry-related aromatic rings is 54.97\u2005(3)\u00b0. The geometric parameters of the aromatic ring are typical of those for 2,4,6-tri\u00admethyl\u00adphenyl substituted groups. The C=O and C\u2014O bond lengths are 1.1934\u2005(12) and 1.3958\u2005(11)\u2005\u00c5, respectively, and the angle between these three atoms (O=C\u2014O) is 121.24\u2005(9)\u00b0. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. The packing features wavy chains that extend parallel to [001].The title compound, C The C1\u2014C2 distance is normal for an sp2\u2013sp2 bond, with a length of 1.4873\u2005(13)\u2005\u00c5. The second half of the mol\u00adecule, which is generated by rotation about the twofold axis passing through O1 , forms a dihedral angle of 54.97\u2005(3)\u00b0 between the equivalent aromatic rings. If the planes of the two overlapping CO2 groups are chosen instead, the dihedral angle becomes 59.30\u2005(11)\u00b0. The C\u2014C bonds in the aromatic ring are not all statistically equivalent. Unsurprisingly, the longest C\u2014C bonds in the ring are adjacent to the electron-withdrawing anhydride group, C2\u2014C3 [1.4032\u2005(13)\u2005\u00c5] and C2\u2014C7 [1.4059\u2005(13)\u2005\u00c5]. The remaining C\u2014C bonds are statistically equivalent, averaging 1.3942\u2005(8)\u2005\u00c5. All of the C\u2014CH3 bond lengths are statistically equivalent with an average length of 1.5102\u2005(8)\u2005\u00c5.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01a axis, forms wavy chains that run parallel to the c-axis direction  and H6 (2.39\u2005\u00c5 to H10A), and the designated methyl H atoms, which close five-membered rings in the mol\u00adecule.There are short intra\u00admolecular contacts between the aromatic H atoms H4  were added to a chloroform solution (25\u2005ml) of 1,3-di\u00adchloro-1,3-bis\u00ad(di\u00admethyl\u00adamino)\u00adpropenium hydrogen dichloride , which had been prepared following the known literature method  and then isolated via vacuum filtration. The off-white solid was further purified by recrystallization through slow evaporation of a saturated diethyl ether solution. After 3\u2005h, clear and colourless thin plate-like crystals were obtained . Elemental analysis, calculated for C20H22O3 (%): C\u00a077.39, H 7.14, N 0.00; found (%): C 77.26, H 7.13, N 0.01. The 1H and 13C{1H} NMR and IR spectroscopic data for the title compound are identical to those previously reported  = 1.2 or 1.5Ueq(C).Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989017014670/hb7710sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017014670/hb7710Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017014670/hb7710Isup3.cmlSupporting information file. DOI: 1579203CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in the title compound is seven-coordinate, being bound to two pyridine N atoms, one amine N atom and four O atoms to form a distorted penta\u00adgonal\u2013bipyramidal environment. Each dipyridyl-type ligand links the CoII atoms into polymeric zigzag chains, which are connected via inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions and N/C\u2014H\u22efO hydrogen bonds.The Co 3)2L]n, L = N-(pyridine-2-ylmeth\u00adyl)pyridine-3-amine (C11H11N3), contains one CoII centre, two nitrate anions and one L ligand in which the Cpy\u2014C\u2014N\u2014Cpy moiety adopts a trans conformation with a torsion angle of \u2212173.1\u2005(3)\u2005\u00c5. The coordination geometry of the CoII atom is a distorted penta\u00adgonal bipyramid. One amine N atom from the L ligand and four O atoms from two \u03b72-nitrato ligands form the basal plane and two pyridyl N atoms from two symmetry-related L ligands occupy the apical positions [N\u2014Co\u2014N = 171.86\u2005(11)\u00b0]. The displacement of the central CoII atom from the basal plane (r.m.s. deviation = 0.085\u2005\u00c5) is 0.1491\u2005(12)\u2005\u00c5. Each bidentate nitrate group is bonded asymmetrically to the cobalt atom in an chelating fashion. The CoII ions are linked by the L ligands to form a zigzag chain propagating along the c-axis direction. Within the zigzag chain, C\u2014H\u22efO hydrogen bonds between the ligands and the nitrate anions are observed. Adjacent zigzag chains are connected via inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.844\u2005(2)\u2005\u00c5] between the pyridine rings together with N/C\u2014H\u22efO hydrogen bonds.The asymmetric unit of the title compound, [Co(NO Herein, we report its crystal structure, which is the first example of a CoII complex with an N-(pyridine-2-ylmeth\u00adyl)pyridine-3-amine ligand.Over the past few decades, the continuous efforts have been devoted to the design and development of metal\u2013organic frameworks (MOFs) obtained by linking transition metal centers with several organic bridging ligands. In particular, rigid or flexible dipyridyl-type ligands have been widely used to construct MOFs with attractive structures and potential applications in materials chemistry \u00b0; symmetry code: (i) x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0II atom is displaced by 0.1491\u2005(12)\u2005\u00c5 from the basal plane (r.m.s. deviation = 0.085\u2005\u00c5). The Co\u2014N distances in apical positions  are slightly shorter than that of the basal [Co1\u2014N2 = 2.191\u2005(3)\u2005\u00c5]. The largest deviations from the NO4 basal plane around the cobalt center involve the angles O2\u2014Co1\u2014O3 [55.81\u2005(11)\u00b0] and N2\u2014Co1\u2014O5 [84.19\u2005(9)\u00b0]. This distortion may reflect the narrow bite angles of the bidentate nitrate ions.The asymmetric unit of the title compound comprises one Co\u00a0] Fig.\u00a01. The cenL ligand adopts a stretched trans conformation with the C5\u2014C6\u2014N2\u2014C7 torsion angle being \u2212173.1\u2005(3)\u2005\u00c5. The terminal pyridine rings of the L ligand are nearly perpendic\u00adular to each other, with the dihedral angle between their mean planes being 76.74\u2005(12)\u00b0. Each bidentate nitrate group is bonded asymmetrically to the cobalt atom . Each L ligand is bridged by the CoII ions, forming \u2013(Co-L)n\u2013 zigzag chains propagating along the c-axis direction \u2005\u00c5; Cg1 is the centroid of the N1/C1\u2013C5 ring; symmetry code: (ii) \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01] between the pyridine rings and C\u2014H\u22efO hydrogen bonds between pyridyl H atoms and nitrate O atoms  are HgII complexes and seven  of them are AgI complexes. The remaining one is a ZnII complex (DUVPER). There are no metal complexes that are similar to the structure of the CoII complex described above. Therefore, the title compound is the first example of a CoII complex with an L ligand.A search of the Cambridge Structural Database 2\u00b76H2O in the molar ratio 1:1.The d(N\u2014H) = 0.96\u2005\u00c5]. All other H atoms were positioned geometrically and refined as riding, with d(C\u2014H) = 0.93\u2005\u00c5 for Csp2\u2014H and 0.97\u2005\u00c5 for methyl\u00adene C\u2014H. For all H atoms, Uiso(H) = 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901701475X/nk2241sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901701475X/nk2241Isup2.hklStructure factors: contains datablock(s) I. DOI: 1579473CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structure of a coumarin ester stabilized by C\u2014H\u22efO hydrogen bonds and C=O\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions has been studied by X-ray diffraction, Hirshfeld surface analysis and quantum chemical calculations. 16H9FO4, (I), the benzene ring is oriented at an acute angle of 59.03\u2005(15)\u00b0 relative to the coumarin plane (r.m.s deviation = 0.009\u2005\u00c5). This conformation of (I) is stabilized by an intra\u00admolecular C\u2014H\u22efO hydrogen bond, which closes a five-membering ring. In the crystal, mol\u00adecules of (I) form infinite zigzag chains along the b-axis direction, linked by C\u2014H\u22efO hydrogen bonds. Furthermore, the crystal structure is supported by \u03c0\u2013\u03c0 stacking inter\u00adactions between neighbouring pyrone and benzene or coumarin rings [centroid\u2013centroid distances in the range 3.5758\u2005(18)\u20133.6115\u2005(16)\u2005\u00c5], as well as C=O\u22ef\u03c0 inter\u00adactions [O\u22efcentroid distances in the range 3.266\u2005(3)\u20133.567\u2005(3)\u2005\u00c5]. The theoretical data for (I) obtained from quantum chemical calculations are in good agreement with the observed structure, although the calculated C\u2014O\u2014C\u2014C torsion angle between the coumarin fragment and the benzene ring (73.7\u00b0) is somewhat larger than the experimental value [63.4\u2005(4)\u00b0]. Hirshfeld surface analysis has been used to confirm and qu\u00adantify the supra\u00admolecular inter\u00adactions.In the title compound, C They also form the core of several mol\u00adecules of pharmaceutical importance. Coumarin and its derivatives have been reported to serve as anti-bacterial (Basanagouda S(5) ring motif arises from the intra\u00admolecular C16\u2014H16\u22efO3 hydrogen bond d Table\u00a01, and gend Table\u00a01. The couC(4) chains along the [010] direction  = 3.336\u2005(5)\u2005\u00c5] and C1=O2\u22ef\u03c0 inter\u00adactions are present . The resulting supra\u00admolecular aggregation is completed by the presence of \u03c0\u2013\u03c0 stacking between the pyrone and C4\u2013C9 benzene rings or coumarin ring systems  = 3.5758\u2005(18), Cg1\u22efCg4  = 3.6116\u2005(16), Cg2\u22efCg4  = 3.6047\u2005(16)\u2005\u00c5, where Cg2 is the centroid of the C4\u2013C9 benzene ring] are less than 3.8\u2005\u00c5, the maximum regarded as suitable for an effective \u03c0\u2013\u03c0 inter\u00adaction  on ring J and distances between Cg(I) and perpendicular projection of Cg(J) on ring I (slippage) are summarized in Table\u00a02In the crystal, the C2\u2014H2\u22efO2 hydrogen bond links mol\u00adecules into infinite zigzag on Fig.\u00a02. In addims Fig.\u00a03. The cenet al., 2016et al., 1982et al., 1985et al., 2011et al., 2014meta-substituted coumarin esters  to 1.20\u2005\u00c5 (blue) with the program CrystalExplorer 3.1 dnorm highlights several red spots showing distances shorter than the sum of the van der Waals radii. These dominant inter\u00adactions correspond to inter\u00admolecular C\u2014H\u22efO hydrogen bonds, C8\u22efC5 , O\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions between the surface and the neighbouring environment. The mapping also shows white or pale-red spots with distances almost equal to the sum of the van der Waals radii and blue regions with distances longer than the sum of the van der Waals radii. The surfaces are shown as transparent to allow visualization of the mol\u00adecule  as predicted by the X-ray study. The most significant contrib\u00adution to the Hirshfeld surface (27.7%) is from H\u22efO/O\u22efH contacts, which appear on the left-side as blue spikes with the tip at de + di = 2.4\u2005\u00c5, top and bottom . As expected in organic compounds, the H\u22efH contacts are important with a 24.5% contribution to Hirshfeld surface; these appear in the central region of the FP with a central blue tip spike at de = di = 1.10\u2005\u00c5  whereas the F\u22efH/H\u22efF contacts with a contribution to the Hirshfeld surface of 11.4% are indicated by the distribution of points around a pair of wings at de + did). The C\u22efH/H\u22efC plot (16.2%) reveals information on the inter\u00admolecular hydrogen bonds . Other visible spots in the Hirshfeld surfaces indicate the C\u22efO/O\u22efC, O\u22efO, F\u22efF and C\u22efF/F\u22efC contacts, which contribute only 6.6, 1.3, 1.2 and 1.1%, respectively .Mol\u00adecular Hirshfeld surfaces and the associated two-dimensional fingerprint plots of (I)le Fig.\u00a04. In the le Fig.\u00a04, the adjns Fig.\u00a06a as preom Fig.\u00a06b. As ex\u2005\u00c5 Fig.\u00a06c wherea\u2005\u00c5 Fig.\u00a06d. The Cds Fig.\u00a06e. Otherly Fig.\u00a06f\u20136i.++G basis set. The crystal structure in the solid state was used as the starting structure for the calculations. The DFT calculations were performed with the GAUSSIAN09 program package 4. The resulting precipitate (crude product) was filtered off with suction, washed with petroleum ether and recrystallized from acetone. Pale-yellow crystals of (I)To a solution of 4-fluoro\u00adbenzoyl chloride  in dried tetra\u00adhydro\u00adfuran (40\u2005mL) was added dried tri\u00adethyl\u00adamine  and 7-hy\u00addroxy\u00adcoumarin  by small portions over 30\u2005min. The mixture was then refluxed for 4\u2005h and poured into 40\u2005mL of chloro\u00adform. The solution was acidified with diluted hydro\u00adchloric acid until the pH was 2\u20133. The organic layer was extracted, washed with water to neutrality, dried over MgSOUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901800614X/kq2021sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901800614X/kq2021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901800614X/kq2021Isup3.cmlSupporting information file. DOI: 1834035CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the anion, the carboxyl\u00adate group is twisted away from the attached benzene ring by 84.9\u2005(2)\u00b0. The CoII atom is coordinated by two TMB anions and two water mol\u00adecules in the basal plane, while another water mol\u00adecule bridges the CoII atoms in the axial directions, forming polymeric chains running along [001]. The coordination environment for the CoII cation is a slightly distorted octa\u00adhedron. The coordinating and bridging water mol\u00adecules link to the carboxyl\u00adate groups via intra- and inter\u00admolecular O\u2014H\u22efO hydrogen bonds, enclosing S(6) ring motifs, while the coordinating, bridging and non-coordinating water mol\u00adecules link to the carboxyl\u00adate groups and the coordinating water mol\u00adecules link to the non-coordinating water mol\u00adecules via O\u2014H\u22efO hydrogen bonds, enclosing R22(8) and R33(8) ring motifs. Weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions may further stabilize the crystal structure.The asymmetric unit of the title one-dimensional polymeric compound, {[Co(C The Co1 atom lies 0.2077\u2005(1)\u2005\u00c5 above the carboxyl\u00adate (O1/O2/C1) group, which makes a dihedral angle of 84.9\u2005(2)\u00b0 with the adjacent benzene (C2\u2013C7) ring.The two carboxyl\u00adate O atoms  hydrogen bonds (Table\u00a01S(6) ring motifs  hydrogen bonds \u00adbenzoato-1\u03baO]mang\u00adanese(II)]-\u03bc-aqua]\u00addihydrate], {[Mn(C11H14NO2)2(H2O)3]\u00b72(H2O)}n, (II), \u00adbenzoate (DEAB) anions and two water mol\u00adecules in the basal plane, while another water mol\u00adecule bridges the Mn atoms in the axial directions, forming polymeric chains as in the title compound, (I)In the crystal structure of a similar complex, catena-\u00b72H2O}n, , {[Mn(C10H11O2)2(H2O)3]\u00b72H2O}n, (VIII), which had previously been reported by Chen et al.  anions and two water mol\u00adecules in the basal plane, while another water mol\u00adecule bridges the MnII cations in the axial directions, forming polymeric chains as in the title compound, (I)We also solved the crystal structure of  al. 2007. In ii distance [4.045\u2005(15)\u2005\u00c5] across the chain \u00b0] in (I)M\u2014ObrdW\u2014M  bond angles increase, while the M\u2014ObrdW bond lengths decrease with increasing atomic number, Z, of the transition metal(II) atoms and the M\u22efM distances across the polymeric chains are almost the same, independent of the type of anion coordinating to the metal(II) atoms.The Co1\u22efCo1in Fig.\u00a02 and the 4\u00b77H2O  with sodium 2,4,6-tri\u00admethyl\u00adbenzoate  in H2O (150\u2005ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for eight weeks, giving pink single crystals . FT\u2013IR: 3630, 3405, 3209, 2286, 2069, 1612, 1535, 1446, 1400, 1181, 1114, 1031, 893, 857, 827, 758, 690, 615, 570, 490, 478, 401.The title compound was prepared by the reaction of CoSOSHELXL). Bond lengths and angles for water mol\u00adecules are: O3\u2014H31 = 0.806\u2005(19), O3\u2014H32 = 0.818\u2005(18), O4\u2014H41 = 0.827\u2005(18), O5\u2014H51 = 0.812\u2005(10), O5\u2014H52 = 0.820\u2005(10)\u2005\u00c5 and H31\u2014O3\u2014H32 = 107\u2005(4) and H51\u2014O5\u2014H52 = 107\u2005(4)\u00b0 The C-bound H atoms were positioned geometrically with C\u2014H = 0.93 and 0.96\u2005\u00c5 for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic H atoms. The maximum and minimum electron densities were found 0.89\u2005\u00c5 and 0.82\u2005\u00c5 from Co1. The high residual electron density value of 2.178\u2005e\u2005\u00c5\u22121 may be due to the poor quality of the crystal.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989017005564/pj2043sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017005564/pj2043Isup2.hklStructure factors: contains datablock(s) I. DOI: 1543701CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A linear SP coordination geometry for the gold atom is found in the title structure, which also features a short intra\u00admolecular Au\u22efO inter\u00adaction, in contrast to a Au\u22ef\u03c0 inter\u00adaction found in the first polymorph. 9H9N2O3S)(C21H21P)], is a second monoclinic polymorph (space group P21/c) that complements a previously reported Cc polymorph [Broker & Tiekink \u2005\u00c5], in contrast to the aryl ring in the original polymorph. In the crystal, linear supra\u00admolecular chains along the a-axis direction mediated by C\u2013H\u22ef\u03c0 and nitro-O\u22ef\u03c0 inter\u00adactions are found. These pack with no directional inter\u00adactions between them. The analysis of the Hirshfeld surfaces for both forms of [Au(C9H9N3O3S)(C21H21P)] indicates quite distinctive inter\u00adaction profiles relating to the differences in inter\u00admolecular contacts found in their respective crystals.The title phosphanegold(I) thiol\u00adate compound, [Au(Ckink 2008. Acta Cr R3PAu[SC(OR\u2032)=NR\u2032\u2032], for R, R\u2032 = alkyl, aryl and R\u2032\u2032 = aryl, have proven to exhibit exciting biological activities. For example, compounds of the type Ph3PAu[SC(OR)=NPh], R = Me, Et and i-Pr, induce G2/M cell cycle arrest in HT-29 cancer cells and exhibit tolerable toxicity based on experiments on zebrafish  thiol\u00adates of the general formula R3PAu[SC(OR\u2032)=NR\u2032\u2032] display an intra\u00admolecular Au\u22efO inter\u00adaction. In an exercise in crystal engineering, it was argued that by moderating the electronic properties of the phosphane-bound and thiol\u00adate-N-bound groups, it was possible to direct a change in conformation so that an intra\u00admolecular Au\u22ef\u03c0(ar\u00adyl) inter\u00adaction formed instead of the Au\u22efO contact =NPh], that was originally reported in a form with an intra\u00admolecular Au\u22efO inter\u00adaction =NC6H4NO2-4] is reported which was reported originally in space group Cc with a Au\u22ef\u03c0(ar\u00adyl) inter\u00adaction 3PAu[SC(OEt)=NC6H4NO2-4], (I)Cc form, (II).Referring the conformation shown in the Scheme, most structures having the formula S atom. These bond-length conclusions are vindicated by a comparison of the bond lengths found in the uncoordinated mol\u00adecule, i.e. EtOC(=S)N(H)C6H4NO2-4 Cc polymorph The central S1, O1, N1 and C1 atoms of the thiol\u00adate ligand are strictly (r.m.s. deviation of the fitted atoms = 0.0008\u2005\u00c5) planar. The plane through the nitro\u00adbenzene ligand is orthogonal to the former plane, forming a dihedral angle of 89.67\u2005(12)\u00b0. Finally, the nitro group is essentially co-planar with the ring to which it is connected, forming a dihedral angle of 4.7\u2005(4)\u00b0.Crystal Explorer a-axis direction, Fig.\u00a03a. These are sustained by a combination of nitro\u00adbenzene-C\u2014H\u22ef\u03c0(tol\u00adyl) inter\u00adactions as well as nitro-O\u22ef\u03c0(tol\u00adyl) contacts, Fig.\u00a03b. For the latter, the nitro group lies over the ring, with the two residues being almost parallel, forming a dihedral angle = 7.4\u2005(2)\u00b0. While comparatively rare, the latter inter\u00adactions have been discussed in the crystallographic literature dnorm for forms (I)a indicate the significance of short inter-atomic C\u22efO/O\u22efC contacts, Table\u00a04a, b, and the dnorm-mapped surface for (II), Fig.\u00a05c, are consistent with (I)a. The inter\u00admolecular nitro-O\u22ef\u03c0 inter\u00adaction involving both nitro\u00adbenzene-O2 and O3 atoms with the same symmetrically located tolyl ring (C17\u2013C22) are viewed as two adjoining blue and bright-orange regions in Fig.\u00a05b. The short inter-atomic S\u22efH/H\u22efS, C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts influential in the structure of (II) are highlighted with black, red and yellow dashed lines, respectively, in Fig.5c.It is clearly evident from the Hirshfeld surfaces mapped over a, it is apparent that the different orientations of the thiol\u00adate ligands significantly impact upon the observed features in the plots. This is also visible from the fingerprints delineated into H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO and S\u22efH/H\u22efS contacts c, wherein the half-arrows in (I)de + di \u223c\u20052.8\u2005\u00c5 and 2.9\u2005\u00c5, respectively, arise as the result of distinctive inter\u00admolecular inter\u00adactions in the two forms: the former has a C\u2014H\u22ef\u03c0 contact while the latter has short inter-atomic C\u22efH/H\u22efC contacts, Fig.\u00a05c and Table\u00a04b and Table\u00a04c and d, reflects the different types of inter-atomic contacts they form. In the respective plots for the form (I)de + di\u2005\u223c2.7\u2005\u00c5 in the O\u22efH/H\u22efO delineated and the knife-edge tips at de + di\u2005\u223c2.9\u2005\u00c5 in the S\u22efH/H\u22efS delineated fingerprint plots for (II) are the result of short inter-atomic O\u22efH/H\u22efO and S\u22efH/H\u22efS contacts, Table\u00a04The distinctive features of fingerprint plot delineated into C\u22efH/H\u22efC contacts, Fig.\u00a062)CH2(Ph2)PAuCl. In the original form, intra\u00admolecular Au\u22efAu inter\u00adactions [3.34\u2005\u00c5] were observed CH2(Ph2)PAuCl imply that Au\u22ef\u03c0(ar\u00adyl) inter\u00adactions provide comparable energies of stabilization to their crystal structures. Indeed, computational chemistry on the polymorphic system Ph3PAu[SC(OEt)=NPh] suggested the form with the intra\u00admolecular Au\u22ef\u03c0(ar\u00adyl) contact was more than 5\u2005kcal\u2005\u2005mol\u22121 stable than the form with the intra\u00admolecular Au\u22efO contact =N]2 indicated that each Au\u22ef\u03c0(ar\u00adyl) inter\u00adaction in the centrosymmetric mol\u00adecule was more stable by more than 12\u2005kcal\u2005mol\u22121 than each putative Au\u22efO contact  inter\u00adactions can be seen in the polymorphic structures of ClAuP solution of (I)1H NMR (\u03b4): thiol\u00adate: 7.92 , 6.89 , 4.34 , 1.35 . Phosphane: 7.32\u20137.22 , 2.40 . 13C NMR (\u03b4): Thiol\u00adate: 165.7 , 157.5 , 142.6 , 124.8 , 122.5 , 64.5 , 14.5 . Phosphane: 142.2 , 133.9 , 129.8 , 126.4 , 21.4 .The title compound (I)Uiso(H) set to 1.2\u20131.5Ueq(C). The maximum and minimum residual electron density peaks of 1.16 and 0.78\u2005e\u2005\u00c5\u22123, respectively, were located 0.81 and 1.28\u2005\u00c5 from the Au atom. Owing to inter\u00adference from the beam-stop, the (011) reflection was omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989017012865/hb7703sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017012865/hb7703Isup2.hklStructure factors: contains datablock(s) I. DOI: 1573275CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the protonated piperazine ring adopts a chair conformation while the indole ring plane is nearly perpendicular to the benzo\u00adfuran ring system. 26H28N5O2+\u00b7Cl\u2212\u00b7CH3OH {systematic name: 4-(2-carbamoyl-1-benzo\u00adfuran-5-yl)-1-[4-(5-cyano-1H-indol-3-yl)but\u00adyl]piperazin-1-ium chloride methanol monosolvate}, the protonated piperazine ring adopts a chair conformation. The indole ring plane is nearly perpendicular to the benzo\u00adfuran ring system, with a dihedral angle of 85.77\u2005(2)\u00b0. In the crystal, the organic cations, Cl\u2212 anions and methanol solvent mol\u00adecules are linked by classical N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonds, and weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions into a three-dimensional supra\u00admolecular architecture.In the title compound, C Major depression disorder (MDD) currently ranks as the world\u2019s fourth greatest cause of illness and is expected to rank second by the year 2020 according to WHO studies  with properties that are most similar to those of citalopram, escitalopram (levapro), fluoveline, proxetin, and sertraline. The new drug differs from its predecessors by also acting as a partial agonist at serotonergic 5-HT\u2212 anion and one methanol mol\u00adecule le Fig.\u00a01.et al., 2011n-butyl linker to the piperazine ring. The conformation of the butyl chain is of some inter\u00adest. Three C atoms of the butyl group  are coplanar with atom C9 of the indole, as confirmed by the C9\u2014C10\u2014C11\u2014C12 torsion angle of 179.2\u2005(2)\u00b0, meanwhile atoms C11, C12 and C13 are coplanar with piperazine atom N3. A dihedral angle of 80.9\u2005(2)\u00b0 is formed between the mean planes of N3/C11\u2013C13 and C9\u2013C12. The dihedral angle between the C9\u2013C12 mean plane and the indole plane is 10.0\u2005(2)\u00b0. The second piperazine N atom, N4, is bonded to the benzo\u00adfuran ring. The formamide group is almost coplanar with the connected benzo\u00adfuran ring, making a dihedral angle of 2.53\u2005(2)\u00b0. The indole ring is almost perpendicular to the benzo\u00adfuran ring, as indicated by the dihedral angle of 85.77\u2005(2)\u00b0 between them.The expected proton transfer from hydro\u00adchloric acid to atom N3 of piperazine occurs; the H atom on the piperazine N3 atom was located unequivocally in the electron-density map. The six-membered piperazine ring adopts a chair conformation. The electron-withdrawing cyano group at position 5 on the indole is twisted out of the mean plane of the indole unit, as indicated by the relevant torsion angles N1\u2014C1\u2014C2\u2014C7 and N1\u2014C1\u2014C2\u2014C3 . The conformation of the cyano group is similar to that of other drugs containing nitrile groups, such as bicalutamide and Febuxostat  1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z] hydrogen bonds  1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z] and N3\u2014H3A\u22efCl1 link another two neighbouring cations and the Cl\u2212 anion into a mol\u00adecular sheet. As a result, 28-membered rings with the graph-set motif In the crystal, N3\u2014H3s Table\u00a01, connected Fig.\u00a02.Vilazodone hydro\u00adchloride was supplied by Hangzhou HEZE pharmaceutical Technology Co., Ltd. It was recrystallized from methanol solution, giving single crystals suitable for X-ray diffraction.Uiso(H) = 1.2Ueq(N). All other H atoms were placed in calculated positions with O\u2014H = 0.82, N\u2014H = 0.86 and C\u2014H = 0.93\u20130.98\u2005\u00c5, and included in the refinement in a riding model with Uiso(H) = 1.2 or 1.5Ueq(carrier atom).Experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016017734/xu5894sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016017734/xu5894Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016017734/xu5894Isup3.cmlSupporting information file. DOI: 1439516CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The characteristic structural feature of a new two-dimensional Zn coordination polymer is an infinite polymeric layer parallel to the crystallographic (132) plane. 2-4,4\u2032-bis\u00ad[meth\u00adyl]biphenyl-\u03ba2N4:N4\u2032}bis\u00ad(nitrato-\u03baO)zinc(II)], [Zn(NO3)2(C18H16N6)2]n, is a two-dimensional zinc coordination polymer constructed from 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The ZnII cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl ligands, forming a distorted octa\u00adhedral {ZnN4O2} coordination geometry. The linear 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl ligand links two ZnII cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C\u2014H\u22efO, C\u2014H\u22efN, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions, resulting in a three-dimensional supra\u00admolecular architecture.The title compound, poly[bis\u00ad{\u03bc H-1,2,4-triazol-1-ylmeth\u00adyl)benzene benzene benzene benzene meth\u00adyl]-1,1\u2032-biphenyl meth\u00adyl]biphenyl-\u03ba2N4:N4\u2032}bis\u00ad(nitrato-\u03baO)zinc], [Zn(NO3)2(C18H16N6)2]n, was synthesized under hydro\u00adthermal conditions by the reaction of Zn(NO3)2\u00b76H2O and 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl at 313\u2005K for 48\u2005h. We report here its crystal structure and its elemental analysis.Over the past few decades, the self-assembly of coordination polymers (CPs) or metal\u2013organic frameworks (MOFs) based on metal ions or clusters and organic ligands has attracted much attention, owing to their intriguing mol\u00adecular topologies and potential applications. Multidentate ligands derived from 1,2,4-triazole that contain an aromatic core have been used for this purpose, examples being 1,4-bis\u00admeth\u00adyl]-1,1\u2032-biphenyl ligand.The title complex crystallizes in the triclinic space group II cation exhibits a slightly distorted octa\u00adhedral {ZnN4O2} coordination geometry and is coordinated by four N atoms  from four symmetry-related organic ligands and two O atoms (O3 and O3i) from two symmetry-related nitrate groups meth\u00adyl]-1,1\u2032-biphenyl ligands and two nitrate anions, and each organic ligand in turn connects two ZnII cations to generate a two-dimensional layer parallel to the crystallographic (132) plane. The organic ligand adopts a cis,cis substituent conformation. The two distinct Zn\u22efZn distances are 18.397\u2005(3) and 18.964\u2005(3)\u2005\u00c5 meth\u00adyl]-1,1\u2032-biphenyl ligand lie nearly in one plane [dihedral angle = 0.00\u2005(2)\u00b0]. The two triazole groups of the 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl ligand are inclined to the plane of the central biphenyl groups, with dihedral angles of 80.050\u2005(2) (C1/C2/N1/N2/N3) and 85.511\u2005(2)\u00b0 (C10/C11/N4/N5/N6). Four adjacent ZnII cations are connected by four linear organic ligands and form a 72-membered macrocyclic ring in the above-mentioned two-dimensional layer \u2005\u00c5 and C12\u2014H12\u22efCg2iii = 3.5252\u2005(7)\u2005\u00c5; Cg1 and Cg2 are the centroids of the triazole (C1/C2/N1/N2/N3) and phenyl (C4\u2013C9) rings, respectively; symmetry codes: (ii) 2\u00a0\u2212\u00a0x, \u2212y, \u2212z; (iii) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z] contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions [Cg1\u22efCg1ii\u00a0= 3.6296\u2005(10)\u2005\u00c5]. These interactions, together with the covalent inter\u00adactions in the infinite two-dimensional polymeric-like layer, make up a three-dimensional supra\u00admolecular structure.Neighbouring layers are linked to each other by by weak interactions Table\u00a01, includiet al., 2016H-1,2,4-triazol-1-yl)meth\u00adyl]-1,1\u2032-biphenyl moiety gave eight hits. Seven of them are con\u00adstructed by 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl units and different carboxyl\u00adate ligands. One example is a chain structure based on Zn and 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl 2\u00b76H2O (0.1\u2005mmol), 4,4\u2032-bis\u00ad[meth\u00adyl]-1,1\u2032-biphenyl (0.1\u2005mmol) and water (6\u2005ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413\u2005K for 72\u2005h. After cooling to room temperature, colourless block-shaped crystals  suitable for X-ray analysis were obtained. Elemental analysis calculated for C36H32N14O6Zn: C 52.59, H 3.92, N 23.85%; found: C 52.23, H 3.74, N 23.49%.Zn(NOUiso(H) = 1.2Ueq(C) for other H atoms. Atoms O1 and O2 of the nitrate group are disordered over two orientations, with occupancies of 0.511\u2005(11) and 0.489\u2005(11), and were refined through the use of SADI, RIGU and SIMU commands.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017012452/vn2130sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017012452/vn2130Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017012452/vn2130Isup3.molSupporting information file. DOI: 1564369CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The H atom of the oxime moiety is equally disordered over two positions, giving rise to two equivalent hydrogen bonds between adjacent mol\u00adecules. 14H13NO2, is a commercially available material and can be used as a multidentate ligand. The mol\u00adecule of the asymmetric unit has an R configuration, while the corresponding S-configured mol\u00adecule of the racemic mixture is generated by a crystallographic centre of symmetry. Both hy\u00addroxy groups  are involved in hydrogen bonding, leading to the formation of chains extending parallel to [001].The title compound, C E)-2-hy\u00addroxy-1,2-diphenyl-ethan-1-one oxime, C14H13NO2, is commercially available and can be used as a multidentate ligand for which many trivial names such as cuprone or alpha-benzoin, and abbreviations including AboH2, BzoxH2, are in use. Used for a long time for the determination of manganese or copper in steel  compounds, we obtained high-quality single crystals of the title compound which we have used for structure determination by X-ray diffraction.The title compound (C2/c with eight mol\u00adecules in the unit cell and one mol\u00adecule in the asymmetric unit. As the compound possesses an asymmetric carbon atom (C2), the mol\u00adecule of the asymmetric unit has an R-configuration while the corresponding S-configured mol\u00adecule of the racemic mixture is generated by a crystallographic centre of symmetry. Both mol\u00adecules also show the E configuration at the N=C double bond of the oxime moiety  and sp2 (C1) hybridized C atoms. As a consequence of the different hybridization states, however, the bonds of these two carbon atoms to their phenyl groups are slightly different: 1.512\u2005(2)\u2005\u00c5 for C2 and 1.484\u2005(2)\u2005\u00c5 for C1, respectively. The hy\u00addroxy group attached to C2 shows a C\u2014O bond length of 1.425\u2005(2)\u2005\u00c5, which also lies in the normal range (1.421\u20131.433\u2005\u00c5) of a C2\u2013CH\u2013OH group \u2005\u00c5] of the N=C double bond Table\u00a01 is consiet al., 1987ar\u2014Car. The mean value of the endocyclic bond angles within the phenyl rings is 120.0\u2005(5)\u00b0 with minima at the ipso carbon atoms C11 [118.3\u2005(1)\u00b0] and C21 [119.1\u2005(1)\u00b0]. The phenyl rings form an inter\u00adplanar angle of 80.72\u2005(5)\u00b0.The two phenyl groups exhibit a mean C\u2014C bond length of 1.387\u2005(5)\u2005\u00c5 [variation: 1.374\u2005(3)\u20131.398\u2005(2)\u2005\u00c5], in excellent agreement with the literature value (Allen ii = 2.829\u2005(2)\u2005\u00c5, \u2329O2\u2014H3\u22efO2ii = 164\u00b0; symmetry code: (ii) = \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a01] and a twofold rotation axis [O2\u22efO2iii = 2.806\u2005(2)\u2005\u00c5, \u2329O2\u2014H4\u22efO1iii = 175\u00b0; symmetry code (iii) = \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0i = 2.805\u2005(2)\u2005\u00c5, \u2329O1\u2014H1\u22ef N1i = 144\u00b0; symmetry code: (i) = \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0The mol\u00adecule possesses two hy\u00addroxy groups which, in principle, can act as donors and acceptors for hydrogen bonding while the N atom of the oxime moiety can only act as an acceptor atom in the formation of hydrogen bonds. In fact, the crystal packing Fig.\u00a02 with itses Fig.\u00a04. The two\u03b1-benzoinoxime was refluxed with di-n-butyl\u00adtin oxide, C8H18OSn, in ethanol for 2.5\u2005h. Single crystals of the title compound suitable for X-ray diffraction were obtained from the ethano\u00adlic solution layered with n-hexane.In a typical experiment, sp3-hybridized and 0.95\u2005\u00c5 for aromatic H atoms, and with Uiso(H) = 1.2Ueq(C). The H atoms of the two hy\u00addroxy groups were modelled with a common O\u2014H distance of 0.96\u2005\u00c5 before they were fixed and allowed to ride on the corresponding oxygen atom with Uiso(H) = 1.2Ueq(O). Disorder of the hy\u00addroxy group attached to C2 was taken into account reducing the site occupancy of both H atoms to one-half. This suggestion was confirmed by difference-Fourier maps that clearly showed both positions.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017008866/wm5397sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017008866/wm5397Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008866/wm5397Isup3.cmlSupporting information file. DOI: 1556039CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N,N\u2010bisamide pincer ligand (ONO3\u2212) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element\u2013hydrogen bonds , both the phosphorus(III), P(ONO) (1\u2009a), and arsenic(III), As(ONO) (1\u2009b), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1\u2009a and 1\u2009b with KOtBu or KNPh2 afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([(tBuO)Pn(ONO)]\u2212 (Pn=P (2\u2009a), As (2\u2009b)) and [(Ph2N)Pn(ONO)]\u2212 (Pn=P (3\u2009a), As (3\u2009b)). Compound 2\u2009a can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(ONO) (4\u2009a) and (tBuO)BzP(ONO) (5\u2009a), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1\u2009a and 1\u2009b, giving rise to cationic species that can be rationalised as either ammonium salts or as amine\u2010stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}]+ (Pn=P (6\u2009a), As (6\u2009b)) and [Pn{ON(Me)O}]+ (Pn=P (7\u2009a), As (7\u2009b)). Reaction of 1\u2009a with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) (8\u2009a), whereas the analogous reaction with 1\u2009b results in the addition of HCl across one of the As\u2212O bonds to afford ClAs{(H)ONO} (8\u2009b). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of 7\u2009a/7\u2009b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn=P (9\u2009a), As (9\u2009b)). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of 1\u2009a towards small molecules, such as ammonia and water.The ambiphilic nature of geometrically constrained Group\u200515 complexes bearing the  Over the last decade significant advances have been made in the development of main\u2010group species that are capable of activating small molecules.More recently, geometrically constrained compounds based on phosphorus(III) have also received significant attention in this field. Studies by Arduengo,N,N\u2010bisamide ligand (P(ONO); 1\u2009a).1\u2009a exclusively reacts with nucleophilic species with protic E\u2212H bonds, whereas non\u2010nucleophilic substrates, even those with polar E\u2212H bonds, such as phenylsilane, fail to react. These observations seemed to indicate that the nucleophilic association of the substrate is necessary prior to any further reactivity taking place. This prompted us to explore the reactivity of 1\u2009a towards both nucleophiles and electrophiles in an effort to gain a better understanding of the reaction dynamics. These results, and analogous studies on the heavier arsenic(III) analogue (1\u2009b), are reported herein.We recently reported a phosphorus(III) compound bearing the 1\u2009a exhibits a bent geometry in the solid state with moderate pyramidalisation at both the phosphorus and nitrogen atoms (\u03a3angles(P)=296.1\u00b0; \u03a3angles(N)=331.6\u00b0), in contrast with planar compound A. Theoretical calculations at the density functional theory (DFT) level revealed that the pyramidal sC isomer (or electromorph to use the term coined by Arduengo) is the most stable, but relatively close in energy to the Cv2 symmetric species (within 4\u2005kJ\u2009mol\u22121). This energetic difference is within the error of the calculations, and it is worth noting that different computational analyses  actually suggest that the planar structure is lower in energy than the sC isomer . Therefore, it is highly likely that, in solution, there is a dynamic, and concerted, pyramidal inversion at the phosphorus and nitrogen atoms resulting in a wing\u2010like \"flapping\" of the ligand backbone. The calculations also revealed that, regardless of the symmetry adopted by 1\u2009a, there is an empty, energetically accessible orbital that is largely based on the phosphorus atom, which has anti\u2010bonding character with respect to the P\u2212N and P\u2212O bonds. It is also worth noting that the P\u2212N bond in 1\u2009a is significantly polarised, with computed Hirshfeld charges of 0.394 and \u22120.171 on the phosphorus and nitrogen atoms, respectively. These observations prompted us to explore the reactivity of 1\u2009a, and its heavier arsenic analogue (1\u2009b), towards nucleophiles in order to establish whether they associate with the phosphorus/arsenic atom.As previously reported, 1\u2009b can be prepared following a similar synthetic methodology to that previously reported for its lighter congener. Reaction of the protonated ligand, N,N\u2010bisamine, H3ONO, with AsCl3 in the presence of three molar equivalents of triethylamine, affords 1\u2009b quantitatively, as evidenced by 1H and 13C{1H} NMR spectroscopy. The 1H\u2005NMR spectrum of 1\u2009b in C6D6 reveals two equal intensity aromatic resonances at 8.39 and 7.51\u2005ppm as well as two singlets at 1.71 and 1.46\u2005ppm arising from the tert\u2010butyl groups. Cooling of a concentrated pentane solution afforded bright red\u2010orange crystals of the compound in good to high yields.The arsenic\u2010containing species 1\u2009b ) of 329.1\u00b0. The sum of bond angles around the nitrogen centre, 359.9\u00b0, is significantly greater than for the lighter phosphorus\u2010containing analogue (331.6\u00b0). The As\u2212O bond lengths (1.933(4) and 1.933(4)\u2005\u00c5) are slightly elongated when compared to the expected values for single bonds (1.84\u20131.85\u2005\u00c5).1\u2009b are closely related to the planar 10\u2010As\u20103 compound 5\u2010aza\u20102,8\u2010dioxa\u2010l\u2010arsabicyclo[3.3.0]octa\u20102,4,6\u2010triene previously reported by Arduengo and co\u2010workers (As\u2212N: 1.839(3)\u2005\u00c5; As\u2212O: 1.955(3) and 1.998(3)\u2005\u00c5; \u03a3angles(As)=320.7\u00b0).1\u2009b and that determined crystallographically. Interestingly, attempts to optimise the sC isomer of 1\u2009b ultimately converge to the planar (Cv2) isomer, indicating that in contrast to its phosphorus\u2010containing analogue, the sC geometry of 1\u2009b is not a minimum on the potential energy hypersurface.The structure of b Figure\u2005 exhibits1\u2009a and 1\u2009b was explored towards a number of nucleophilic species. In a preliminary report we demonstrated that 1\u2009a reacts with nucleophiles with polarised element\u2013hydrogen bonds (NH3 and H2O) to give rise to five coordinate phosphorus(V) compounds. By contrast, no reaction is observed between 1\u2009b and ammonia, whereas hydrolysis does take place but gives rise to complex reaction mixtures and does not result in any arsenic(V)\u2010containing compounds. Our calculations reveal that this is largely a thermodynamic phenomenon. The reaction between NH3 and 1\u2009a is exothermic by 90\u2005kJ\u2009mol\u22121, whereas the same reaction between NH3 and 1\u2009b is thermodynamically uphill by 86\u2005kJ\u2009mol\u22121. This difference in reactivity can be attributed to the increased stabilisation of the \u201cinert pair\u201d on descending Group\u200515.The reactivity of 1\u2009a or 1\u2009b with neutral nucleophiles, such as pyridine or PPh3. In contrast, anionic nucleophiles do react with both compounds associating with the pnictogen centre. In a typical reaction, the geometrically constrained complexes were reacted with one equivalent of KNu (Nu=OtBu or NPh2) in the presence of a cation sequestering agent  or 4,7,13,16,21,24\u2010hexaoxa\u20101,10\u2010diazabicyclo[8.8.8]hexacosane ) to aid crystallisation. These reactions yielded the anionic complexes [(tBuO)Pn(ONO)]\u2212 (Pn=P (2\u2009a) and As (2\u2009b)) and [(Ph2N)Pn(ONO)]\u2212 (Pn=P (3\u2009a) and As (3\u2009b)) as pictured in Scheme\u2005No reaction is observed for either 1\u2009a were monitored by 31P\u2005NMR spectroscopy and show quantitative conversion to the desired products, which were observed as singlet resonances at 85.5 and 66.3\u2005ppm for 2\u2009a and 3\u2009a, respectively. These resonances are shifted upfield with respect to 1\u2009a (168.6\u2005ppm), due to the enhanced electron density on the phosphorus centre. Similarly the 1H\u2005NMR spectra of both compounds display the requisite number of resonances for a symmetrical N,N\u2010bisamide ligand backbone and for the nucleophilic substituents. Reactions involving 1\u2009b similarly give rise to products in which both of the 3,5\u2010di\u2010tert\u2010butyl\u20102\u2010phenolate arms of the ligand backbone are equivalent as evidenced by 1H and 13C{1H} NMR spectroscopy.Reactions involving 2\u2009a), 0.0365\u2005\u00c5 (2\u2009b) 0.0019\u2005\u00c5 (3\u2009a) and 0.0150\u2005\u00c5 (3\u2009b)) with the nucleophile orthogonal to the Pn(ONO) core. The planarity of the ligand backbone is also evident in the sum of bond angles around the nitrogen atoms . These structures are consistent with lone\u2010pair donation from the nucleophile into the lowest unoccupied molecular orbital (LUMO) of 1\u2009a and 2\u2009a. DFT calculations reveal that the most significant atomic orbital contribution to this orbital comes from the pnictogen atom p orbital that is perpendicular to the plane of the molecule . The LUMO of 1\u2009a and 2\u2009a are also notably p\u03c0\u2013p\u03c0 antibonding with respect to the Pn\u2212N and Pn\u2212O bonds.The structures of all four novel anionic complexes were determined by single\u2010crystal X\u2010ray diffraction Figures\u2005 and 4. TN,N\u2010bisamide ligand. This significant weakening of the Pn\u2212O bonds strongly suggests that on coordination of a nucleophile, the aryloxide functionalities are susceptible to electrophilic attack. This was probed by reacting 2\u2009a and 2\u2009b with a pyridinium trifluoromethanesulfonate and benzyl bromide (BzBr).Upon coordination of an anionic nucleophile there is a significant elongation of the Pn\u2212O bonds while the Pn\u2212N bonds remain very similar to those of the parent compound  or benzyl bromide afforded the trigonal bipyramidal compounds (tBuO)HP(ONO) (4\u2009a) and (tBuO)BzP(ONO) (5\u2009a), respectively  to the E\u2212H activation products that were obtained by reaction of 1\u2009a with H2O and NH3. In fact, compound 4\u2009a can be readily accessed by direct reaction of 1\u2009a with HOtBu. The reactions proceeded rapidly (before the 31P\u2005NMR spectra of the reaction mixtures were recorded) at room temperature affording the compounds in quantitative yields. Consequently, we were unable to ascertain whether electrophilic association of the proton or benzyl functionalities involved the ligand backbone prior to migration of the functional group to the phosphorus centre.Reactions of [K][OTf] (Pn=P (6\u2009a), As (6\u2009b)) and [Pn{ON(Me)O}][OTf] (Pn=P (7\u2009a), As (7\u2009b)) after heating or sonicating the mixtures .31P\u2005NMR spectra of the reactions involving 1\u2009a reveal broad resonances, with evidence of weak or non\u2010existent P\u2212H coupling, at 155.5 (2JP\u2010H=12\u2005Hz) and 149.4\u2005ppm for 6\u2009a and 7\u2009a, respectively (cf. 168.6\u2005ppm for 1\u2009a), indicating that the electrophilic groups do not associate directly with the phosphorus(III) centre. The 1H\u2005NMR spectra of all four compounds are consistent with two equivalent aryloxide functionalities, which suggest functionalisation at the amide nitrogen atom. The 1H\u2005NMR resonances for the proton\u2010 and methyl\u2010group\u2010functionalised nitrogen atoms were observed at 14.27 and 3.72\u2005ppm for 6\u2009a and 7\u2009a, respectively. Similarly, reactions involving 1\u2009b also reveal clean conversion to the products and the 1H\u2005NMR resonances of the electrophiles associated with the nitrogen atom were observed at 11.64 and 3.41\u2005ppm for 6\u2009b and 7\u2009b, respectively.In a typical reaction, one molar equivalent of EOTf  was added to a solution of either 6\u2009a an additional molecule of HOTf. The most striking aspect of the structures is that protonation/methylation has taken place at the nitrogen centre, as evidenced by NMR spectroscopy. All four complexes adopt a distorted tetrahedral geometry around the nitrogen atom and exhibit a significant elongation of the N\u2010Pn bonds (N\u2212P: 1.926(2) and 1.955(2)\u2005\u00c5 for 6\u2009a and 7\u2009a, respectively; N\u2010As: 2.028(2) and 2.127(1)\u2005\u00c5 for 6\u2009b and 7\u2009b, respectively) relative to 1\u2009a (1.757(1)\u2005\u00c5) and 1\u2009b (1.862(3)\u2005\u00c5). The Pn\u2212O bonds experience a moderate contraction on protonation/methylation in the case of the phosphorus containing compounds (0.03\u2005\u00c5), but a much more dramatic contraction (0.13\u2005\u00c5) for the arsenic analogues, which is linked to a change from the planar geometry of 1\u2009b to the bent (sC) geometry of both 6\u2009b and 7\u2009b. This geometric change allows for the aryloxide substituents to get closer to the arsenic centre as the pseudo\u2010axial arrangement of the oxygen atoms in the 10\u2010Pn\u20103 structure of 1\u2009b is lost on functionalisation of the ligand backbone.The structures of all four novel cationic complexes were determined by single\u2010crystal X\u2010ray diffraction Figures\u2005 and 7. T6\u2009a: 2.790(2) and 2.898(1)\u2005\u00c5, 6\u2009b: 2.745(2)\u2005\u00c5, 7\u2009a: 2.760(2) 7\u2009b: 2.226(1)\u2005\u00c5) indicating a significant degree of positive charge accumulating on the pnictogen centres on functionalisation of the ligand backbone. This is corroborated by DFT calculations which show a large Hirshfeld charges on the pnictogen atoms relative to nitrogen . Thus, all four complexes can be thought of as base\u2010stabilised phosphenium or arsenium ions. This bonding formulation has previously been proposed for related phosphorus\u2010containing compounds.Interestingly, all four species exhibit close contacts between the pnictogen(III) centre and trifluoromethanesulfonate anions (1\u2009a reacts with HOTf to afford a phosphorus(III) compound with a protonated ligand backbone (6\u2009a), the analogous reaction with an acid that has a more nucleophilic counter\u2010anion, such as HCl, affords the phosphorus(V) species HPCl(ONO) (8\u2009a). This difference in reactivity suggests that mechanistically, a sufficiently strong nucleophile is required to afford the formal phosphorus(V) oxidative addition product. Reaction of 6\u2009a with KOtBu, affords 4\u2009a, suggesting that nucleophilic association of the anionic \u2212OtBu moiety with the phosphorus centre induces proton migration from the ligand backbone. Similarly, reaction of 6\u2009a with tetradodecylammonium chloride cleanly affords 8\u2009a and the corresponding ammonium trifluoromethane sulfonate salt. Conversely, reactions of 8\u2009a with one equivalent of trimethylsilyl trifluoromethane sulfonate show evidence for the formation of 6\u2009a, although full conversion was not observed at room temperature with such stoichiometric loadings.It is interesting to note that while 1\u2009b. This is borne out in the reactivity of 1\u2009b towards HCl. Whereas 1\u2009a reacts with HCl to afford 8\u2009a, the reaction of 1\u2009b with one molar equivalent of HCl results in the addition of the acid across one of the As\u2212O bonds resulting in the arsenic(III) compound AsCl{(H)ONO} (8\u2009b). This was evident from the 1H\u2005NMR spectra of these reaction mixtures which reveal the presence of two inequivalent arms of N,N\u2010bisamide pincer ligand on protonation.In the aforementioned studies we have established the relative inaccessibility of the arsenic(V) oxidation state for 8\u2009a and 8\u2009b were both determined by single\u2010crystal X\u2010ray diffraction  complexes we have studied to date, the structure of 8\u2009b clearly shows a trigonal pyramidal arsenic(III) centre in which one of the tert\u2010butyl\u20102\u2010phenolate ligand arms has been protonated and is consequently no longer coordinated to the arsenic centre. The bond metric data for 8\u2009a are similar to the other phosphorus(V) compounds reported. The P\u2212O bond lengths to the N,N\u2010bisamide ligand, 1.661(4) and 1.653(4)\u2005\u00c5, are slightly shorter than those observed for the aforementioned phosphorus(V) compounds (4\u2009a: 1.688(1) and 1.681(1); 5\u2009a: 1.721(1) and 1.732(1)\u2005\u00c5). The same is also true of the P\u2212N interatomic distance which is 1.699(5)\u2005\u00c5 in 8\u2009a, and 1.720(1) and 1.717(1)\u2005\u00c5 in 4\u2009a and 5\u2009a, respectively. The P\u2212Cl bond length is 1.918(2)\u2005\u00c5.The structures of 8\u2009b reveals a trigonal pyramidal geometry about the arsenic(III) centre (\u03a3angles(As)=284.8\u00b0; \u03a3angles(N)=355.6\u00b0) with a relatively obtuse N1\u2010As1\u2010Cl1 angle due to the steric repulsion of the chloride with the free arm of the N,N\u2010bisamide ligand. The As\u2212N and As\u2212O distances, 1.839(2) and 1.783(2)\u2005\u00c5, respectively, are notably shorter than those observed for 1\u2009b (As\u2212N: 1.862(3) and As\u2212O: 1.933(4)\u2005\u00c5), presumably due to the relaxation of steric strain and the loss of As\u2212N multiple bond character on bending the ligand backbone. It is worth noting that the As\u2212N bond in 8\u2009b is still very short and indicative of some multiple bond character.The structure of 6\u2009a with KOtBu result in the association of the tert\u2010butoxide anion with the phosphorus(III) centre and migration of the ligand proton to afford the phosphorus(V) product 4\u2009a . The facility with which the proton of the ligand backbone migrates prompted us to carry out related studies with the methylated species 7\u2009a and 7\u2009b. We hypothesised that methyl migration would not occur and that, consequently novel complexes in which both the nitrogen atom of the N,N\u2010bisamide ligand, and the heavier pnictogen centers could be functionalised.As mentioned previously, reactions of 7\u2009a or 7\u2009b were treated with one molar equivalent of potassium tert\u2010butoxide. These reactions were found to quantitively afford novel complexes bearing a symmetrical ligand environment and an additional tert\u2010butoxide functionality , two resonances arising from the ligand tert\u2010butoxide groups and a doublet due to the methyl group of the ligand backbone. Comparable spectroscopic data were recorded for the arsenic\u2010containing analogue, 9\u2009b, although this sample could not be isolated as a compositionally pure compound due to its relative instability and tendency to decompose.In a typical reaction, 9\u2009a was characterised by single\u2010crystal X\u2010ray crystallography =285.2\u00b0; \u03a3angles(N)=345.7\u00b0). That being said, the sum of bond angles around the nitrogen atom is strongly indicative of increased planarity, which we believe to arise due to the lone\u2010pair\u2013lone\u2010pair repulsion arising between the nitrogen and phosphorus centres. The amine and phosphine like character of these centres is evident in the long P\u22c5\u22c5\u22c5N interatomic distance, 2.573(2)\u2005\u00c5, which is notably longer than that observed for 6\u2009a and 7\u2009a, 1.926(2) and 1.955(2)\u2005\u00c5, respectively, and is clearly indicative of the lack of a bonding interaction between the phosphorus and nitrogen centres. The P\u2212O bonds range from 1.627(1) to 1.665(1)\u2005\u00c5 and are consistent with bond lengths reported for other phosphites.2\u2010hybridised carbon atom compared to an sp3\u2010hybridised species \u0394r=(0.03\u2005\u00c5).Compound 1\u2009a) and As(ONO) (1\u2009b) towards ionic nucleophiles and electrophiles. These studies show that anionic nucleophiles readily associate with the pnictogen(III) centres in both complexes, suggesting that such an association may play an important role in the mechanism for the bond activation of NH3 and H2O by 1\u2009a. Our studies also reveal that while phosphorus(V) compounds are readily accessible by sequential reactions involving 1\u2009a, the corresponding arsenic(V) compounds cannot be synthesised from the heavier analogue 1\u2009b.We have explored the reactivity of the geometrically constrained Group\u200515 complexes P(ONO) (\u2212). When a more nucleophilic counter\u2010anion is employed (such as Cl\u2212) these reactions result in the generation of a phosphorus(V) compound by proton migration from the ligand backbone to the phosphorus centre. As with previous studies, the analogous arsenic(V) compound was found to be inaccessible.Reactions involving charged electrophilic substrates give rise to pnictogen(III) compounds in which the electrophile associates with the nitrogen atom of the ligand backbone. Interestingly, when the electrophile in question is a proton, it will associate with the nitrogen atom of the ligand backbone only in the presence of a weakly coordinating counteranion . 1H, 13C, 31P, 19F\u2005NMR spectra were recorded at room temperature using a Bruker AVIII 500\u2005MHz or Bruker AVIII HD NanoBay 400\u2005MHz NMR Spectrometer. 1H and 13C{1H} spectra are reported relative to tetramethylsilane (TMS) and were referenced to the most downfield residual solvent resonance (1H\u2005NMR spectroscopy: 7.26\u2005ppm (CDCl3), 7.16\u2005ppm (C6D6), 5.32\u2005pm (CD2Cl2) and 3.58\u2005ppm ([D8]THF); 13C{1H} NMR spectroscopy: 77.16\u2005ppm (CDCl3), 128.06\u2005ppm (C6D6), 53.84\u2005ppm (CD2Cl2) and 67.21\u2005ppm ([D8]THF)). 31P\u2005NMR chemical shifts were externally referenced to an 85\u2009% solution of H3PO4 (aq). 19F\u2005NMR chemical shifts were externally referenced to CF3COOH. Elemental analyses were performed by Elemental analysis Ltd (Devon). EI/CI mass spectra were obtained on neat samples using a Waters GCT Time of Flight Mass Spectrometer with a temperature programmed solids probe inlet, or an Agilent 7200 Accurate\u2010Mass Q\u2010TOF GCMS with a SIM Direct Inlet probe. ESI mass spectra were obtained from DMF solutions using a Waters LCT time\u2010of\u2010flight mass spectrometer with a Z\u2010spray source .Solvents and reagents: Hexane , pentane  and toluene  were dried using an MBraun SPS\u2010800 solvent system, THF  was dried over a potassium metal/benzophenone mixture and pyridine was distilled from CaH2. C6D6  was dried and stored over activated 3\u2005\u00c5 molecular sieves. CDCl3 , CD2Cl2  and [D8]THF  were each dried over CaH2 and stored over activated 3\u2005\u00c5 molecular sieves. H3ONO and KNPh2 were synthesised according to a previously reported synthetic procedure.3  was distilled from CaH2 prior to use. AsCl3 , KOtBu , 4,7,13,16,21,24\u2010hexaoxa\u20101,10\u2010diazabicyclo\u2010hexacosane , [PyH][OTf] , HOTf , MeOTf , benzyl bromide  and HCl  were used as received.Synthesis of As(ONO) (1\u2009b): H3ONO  was dissolved in toluene (10\u2005mL). AsCl3  was added to the stirred solution followed by NEt3 , yielding a dark orange solution and white precipitate. The mixture was stirred at room temperature for 3\u2005h. All volatiles were removed under a dynamic vacuum and the product was extracted in pentane (3\u00d710\u2005mL). Removal of volatiles in vacuo yielded 1\u2009b as a dark orange solid. Crystals suitable for single\u2010crystal X\u2010ray diffraction analysis were grown from a concentrated pentane solution at \u221230\u2009\u00b0C. Yield: 880\u2005mg (75\u2009%); elemental analysis calcd (%) for C28H40AsNO2: C 67.59, H 8.10, N 2.82; found: C 67.15, H 8.09, N 2.93; EI MS: m/z calcd for C28H40AsNO2: 497.2275; found: 497.2272; m/z calcd for C27H37AsNO2: 482.2040; found: 482.1898. 1H\u2005NMR : \u03b4=8.39 , 7.51 , 1.71 , 1.46\u2005ppm . 13C{1H} NMR : \u03b4=154.0 (Ar), 142.3 (Ar), 137.2 (Ar), 135.9 (Ar), 119.9 (Ar), 111.3 (Ar), 35.7 (C(CH3)3), 35.1 (C(CH3)3), 32.0 (C(CH3)3), 30.0\u2005ppm (C(CH3)3).tBuO)P(ONO)] ([K(18\u2010crown\u20106)][2\u2009a])Synthesis of [K(18\u2010crown\u20106)] ([K(18\u2010crown\u20106)][2\u2009b])Synthesis of [K(18\u2010crown\u20106)]\u2212: 570.29; found: 569.64; m/z calcd C28H40AsNO3 513.22; found: 513.61; 1H\u2005NMR : \u03b4=7.54 , 6.56 , 3.38 , 1.44 , 1.33 , 1.26\u2005ppm . 13C{1H} NMR : \u03b4=152.6 (Ar), 135.8 (Ar), 133.5 (Ar), 130.4 (Ar), 111.6 (Ar), 107.4 (Ar), 71.2 (OC(CH3)3), 70.8 (18\u2010crown\u20106), 35.3 (C(CH3)3), 34.9 (C(CH3)3), 32.8 (C(CH3)3), 32.8 (OC(CH3)3), 30.4\u2005ppm 3).2N)P(ONO)] ([K(18\u2010crown\u20106)][3\u2009a])Synthesis of [K(18\u2010crown\u20106)][(Ph: A preparative synthesis of [K(18\u2010crown\u20106)][3\u2009a] was not possible due to extremely high sensitivity of the product, which upon manipulation readily decomposes to [(Ph2N)HP(ONO)]. However, evidence for the formation of 3\u2009a can be observed by NMR tube scale reactions. In a typical reaction, 1\u2009a , KNPh2\u22c5THF0.15  and 18\u2010crown\u20106  were added to an NMR tube equipped with a J.\u2005Young airtight tap and the mixture dissolved in [D8]THF to give a pale yellow solution. 1H\u2005NMR : \u03b4=7.07 , 6.90\u20136.85 , 6.79\u20136.73 , 6.52\u20136.47 , 6.51 , 3.49 , 1.28 , 1.26\u2005ppm ; 13C{1H} NMR : \u03b4=151.2 , 149.4 , 135.0 (Ar), 134.8 , 129.8 , 127.6 , 125.5 , 120.0 , 112.4 (Ar), 106.7 , 70.8 , 34.9 (C(CH3)3), 24.8 (C(CH3)3), 32.5 (C(CH3)3), 30.2\u2005ppm (C(CH3)3); 31P\u2005NMR : \u03b4=66.3\u2005ppm (s); 31P{1H} NMR : \u03b4=66.3\u2005ppm (s).2N)As(ONO)] ([K(18\u2010crown\u20106)][3\u2009b])Synthesis of [K]\u2212) 513.24; found: 513.97; 1H\u2005NMR : \u03b4=7.17 , 6.76\u20136.70 , 6.50 , 6.46\u20136.41 , 3.46 , 3.43\u20133.41 , 2.46\u20132.43 , 1.36 , 1.27\u2005ppm ; 13C{1H} NMR : \u03b4=152.2 (Ar), 150.5 (NPh2), 135.8 (Ar), 134.1 (Ar), 130.6 (Ar), 127.9 (NPh2), 124.5 , 119.4 , 111.8 (Ar), 107.5 (Ar), 71.0 , 68.2 , 54.5 , 35.2 (C(CH3)3), 34.8 (C(CH3)3), 32.6 (C(CH3)3), 30.3\u2005ppm (C(CH3)3).tBuO)HP(ONO) (4\u2009a)Synthesis of  and KOtBu  were dissolved in THF (3\u2005mL) at room temperature. The yellow solution was stirred for 15\u2005min after which a solution of pyridinium triflate  in THF (2\u2005mL) was added, giving rise to a colourless solution and white precipitate. After stirring for 30\u2005min all volatiles were removed in vacuo and the product extracted into toluene (5\u2005mL). The solution was filtered through a cannula, concentrated to approximately 0.5\u2005mL and then cooled to 5\u2009\u00b0C for a week, yielding large colourless block crystals of 4\u2009a. The product was isolated by filtration. Yield: 145\u2005mg (83\u2009%); elemental analysis calcd (%) for C32H50NO3P: C 72.83, H 9.55, N 2.65; found: C 72.92, H 9.62, N 2.75. EI MS: m/z calcd for C32H50NO3P: 528.3607; found: 528.3600 m/z calcd for C28H43NO3P: 472.2981; found: 472.2968; m/z calcd for C28H41NO2P: 454.2875; found: 454.2852; 1H\u2005NMR : \u03b4=8.16 , 7.80 , 7.22 , 1.64 , 1.42 , 1.19\u2005ppm ; 1H{31P} NMR : \u03b4=8.16\u2005ppm , all other resonances the same as above; 13C{1H} NMR : \u03b4=143.0 (Ar), 141.0 , 132.7 , 129.5 , 115.4 (Ar), 106.7 , 80.0 3), 35.0 (C(CH3)3), 34.8 (C(CH3)3), 32.0 (C(CH3)3), 30.3 3), 30.2 (C(CH3)3). 31P\u2005NMR : \u03b4=\u221238.7\u2005ppm ; 31P{1H} NMR : \u03b4=\u221238.7\u2005ppm (s).tBuO)BzP(ONO) (5\u2009a)Synthesis of  and KOtBu  were dissolved in THF (5\u2005mL) and stirred until all solid material had dissolved. Benzyl bromide  was added, resulting in the formation of a white precipitate of KBr. The slurry was stirred for 30\u2005min and then all volatiles were removed in vacuo. The product was extracted into hexane and filtered through a cannula. The solution was concentrated under a dynamic vacuum and cooled to \u221230\u2009\u00b0C, yielding a crop of colourless crystals which were isolated by filtration. Yield: 101\u2005mg (74\u2009%); elemental analysis calcd (%) for C39H56NO3P: C 75.82, H 9.14, N 2.27; found: C 76.32, H 9.25, N 2.34; CI MS (NH3 carrier gas):\u00a0m/z calcd C35H45NO2P\u22c5NH4: 562.3688; found: 562.3479; 1H\u2005NMR : \u03b4=7.88 , 7.32\u20137.27 ), 7.22 , 6.96\u20136.90 ), 6.85\u20136.79 ), 3.78 ), 1.61 , 1.38 , 1.15\u2005ppm ; 1H{31P} NMR : 3.78\u2005ppm ) all other resonances as above; 13C{1H} NMR : \u03b4=142.9 , 141.7 (Ar), 134.8 ), 131.8 , 130.0 ), 128.8 , 128.5 ), 126.5 ), 116.1 (Ar), 106.7 , 80.6 3), 47.2 , 35.0 (C(CH3)3), 34.7 (C(CH3)3), 32.0 (C(CH3)3), 30.4 3), 30.3\u2005ppm (C(CH3)3); 31P\u2005NMR : \u03b4=\u221220.2\u2005ppm ; 31P{1H} NMR : \u03b4=\u221220.2\u2005ppm (s).Synthesis of [P{ON(H)O}][OTf] ([6\u2009a]OTf): Compound 1\u2009a (360\u2005mg 0.794\u2005mmol) was suspended in hexane (5\u2005mL) and HOTf  was added, affording a colourless solution. The reaction mixture was sonicated for 15\u2005min causing precipitation of a white solid. The solid was isolated by filtration. Yield: 325\u2005mg (68\u2009%); elemental analysis calcd (%) for C29H41F3NO5PS\u22c5HCF3O3S: C 47.81, H 5.62, N 1.86; found: C 47.78, H 5.66, N 2.02. CI MS (NH3 carrier gas): m/z calcd for C28H41NO2P\u22c5NH4: 472.3219; found: 472.3002; 1H\u2005NMR : \u03b4=14.27 , 7.88 , 7.41 , 1.38 , 1.33\u2005ppm ; 13C{1H} NMR : \u03b4=149.9 (Ar), 147.0 , 138.2 (Ar), 128.9 (Ar), 126.3 (Ar), 116.5 (Ar), 35.6 (C(CH3)3), 35.4 (C(CH3)3), 31.4 (C(CH3)3), 29.4\u2005ppm (C(CH3)3); 31P\u2005NMR : \u03b4=155.5\u2005ppm ; 31P{1H} NMR : \u03b4=155.5\u2005ppm ; 19F\u2005NMR : \u03b4=\u221278.6\u2005ppm.Synthesis of [As{ON(H)O}][OTf] ([6\u2009b]OTf): Compound 1\u2009b  was dissolved in hexane (5\u2005mL) and HOTf  was added, resulting in a pale pink solution and the formation of a white precipitate. The mixture was stirred at room temperature for 15\u2005min after which the solid was isolated by filtration. Yield: 64\u2005mg (46\u2009%); elemental analysis calcd (%) for C28H41AsF3NO5S: C 53.78, H 6.38, N 2.16; found: C 54.33, H 6.80, N 2.21. CI MS (CH4 carrier gas): m/z calcd for C28H41AsNO2: 498.2353; found: 498.2426; m/z calcd C27H37AsNO2: 482.2027; found: 482.2133; 1H\u2005NMR : \u03b4=11.64 , 7.84 , 7.25 , 1.36 , 1.23\u2005ppm . 13C{1H} NMR : \u03b4=151.8 (Ar), 145.5 (Ar), 137.9 (Ar), 131.3 (Ar), 124.5 (Ar), 117.7 (Ar), 35.2 (C(CH3)3), 34.9 (C(CH3)3), 31.4 (C(CH3)3), 29.3\u2005ppm (C(CH3)3); 19F{1H} NMR : \u03b4=\u221278.3\u2005ppm.Synthesis of [P{ON(Me)O}][OTf] ([7\u2009a]OTf): Compound 1\u2009a  was dissolved in toluene (5\u2005mL) and MeOTf  was added. The solution was heated at 70\u2009\u00b0C for 24\u2005h resulting in the growth of colourless needle\u2010shaped crystals. The supernatant was removed by cannula filtration and the crystals washed with toluene (3\u00d75\u2005mL) and dried in vacuo. Yield: 85\u2005mg (60\u2009%); elemental analysis calcd (%) for C30H43F3NO5PS: C 58.33, H 7.02, N 2.27; found: C 58.50, H 7.10, N 2.35; CI MS (NH3 carrier gas): m/z calcd for C29H43NO2P\u22c5NH4: 486.3375; found: 486.3151; 1H\u2005NMR : \u03b4=7.60 , 7.39 , 3.72 , 1.39 , 1.33\u2005ppm ; 1H{31P} NMR : \u03b4=3.72\u2005ppm  all other resonances as above; 13C{1H} NMR : \u03b4=149.3 (Ar), 147.0 , 139.2 (Ar), 134.0 , 126.0 (Ar), 114.8 (Ar), 47.6 , 35.6 (C(CH3)3), 35.5 (C(CH3)3), 31.5 (C(CH3)3), 29.4\u2005ppm (C(CH3)3); 31P\u2005NMR : \u03b4=149.4\u2005ppm (br\u2009s); 31P{1H} NMR : \u03b4=149.4\u2005ppm (br\u2009s); 19F\u2005NMR : \u03b4 \u221278.7\u2005ppm.Synthesis of [As{ON(Me)O}][OTf] ([7\u2009b]OTf): Compound 1\u2009b  was dissolved in toluene (15\u2005mL) and MeOTf  was added to the solution, which was stirred at 80\u2009\u00b0C for three days, resulting in the precipitation of a white/pink solid. The solid was isolated by filtration and dried in vacuo. Yield: 733\u2005mg (78\u2009%); elemental analysis calcd (%) for C30H43AsF3NO5S: C 54.46, H 6.55, N 2.12; found C 54.40, H 6.48, N 2.28; EI MS: m/z calcd for C29H43AsNO2\u22c5CF3O3S: 661.2030; found: 661.2022; m/z calcd for C29H43AsNO2: 512.2528; found: 512.2510; 1H\u2005NMR : \u03b4=7.31 , 7.28 , 3.41 , 1.40 , 1.31\u2005ppm ; 13C{1H} NMR : \u03b4=149.4 (Ar), 145.6 (Ar), 139.7 (Ar), 135.0 (Ar), 124.5 (Ar), 114.8 (Ar), 46.2 (NCH3), 35.5 (C(CH3)3), 34.9 (C(CH3)3), 31.6 (C(CH3)3), 29.4\u2005ppm (C(CH3)3); 19F\u2005NMR : \u03b4=\u221277.9\u2005ppm (br\u2009s).Synthesis of HPCl(ONO) (8\u2009a): Compound 1\u2009a  was dissolved in Et2O (5\u2005mL) and HCl  was added. The colourless solution was stirred for 30\u2005min after which all volatiles were removed in vacuo. The colourless solid was extracted into hot hexane (3\u2005mL) and the solution filtered. Colourless crystals of 8\u2009a grew upon standing at room temperature, which were isolated by filtration. A further crop could be isolated by concentrating the mother liquor. Yield: 139\u2005mg (64\u2009%); elemental analysis calcd (%) for C28H41ClNO2P: C 68.63, H 8.43, N 2.86; found: C 68.86, H 8.49, N 2.92; 1H\u2005NMR : \u03b4=8.97 , 7.66 , 7.13 , 1.45 , 1.41\u2005ppm ; 1H{31P} NMR : \u03b4=8.97\u2005ppm , all other resonances as above; 13C{1H} NMR : \u03b4=144.2 (Ar), 139.4 , 133.9 , 126.4 , 116.6 (Ar), 106.4 , 34.6 (C(CH3)3), 34.1 (C(CH3)3), 31.1 (C(CH3)3), 29.0\u2005ppm (C(CH3)3); 31P\u2005NMR : \u03b4=\u221231.3\u2005ppm ; 31P{1H} NMR : \u03b4=\u221231.3\u2005ppm (s).Synthesis of AsCl(HONO) (8\u2009b): Compound 1\u2009b  was dissolved in THF (5\u2005mL). HCl  was added turning the solution pale yellow. The mixture was stirred at room temperature for 15\u2005min and then concentrated in vacuo to 0.5\u2005mL promoting the growth of colourless block crystals of the product. These were isolated by filtration. Yield: 155\u2005mg (69\u2009%); elemental analysis calcd (%) for C28H41AsClNO2: C 62.98, H 7.74, N 2.62; found: C 62.64, H 7.74, N 2.96; 1H\u2005NMR : \u03b4=7.53 , 7.41 , 7.19 , 6.69 , 5.48 , 1.63 , 1.57 , 1.27 , 1.16\u2005ppm ; 13C{1H} NMR : \u03b4=149.7 (Ar), 147.9 (Ar), 146.1 (Ar), 143.5 (Ar), 137.4 (Ar), 137.2 (Ar), 136.7 (Ar), 124.6 (Ar), 124.0 (Ar), 123.6 (Ar), 116.5 (Ar), 108.5 (Ar), 35.6 (C(CH3)3), 35.1 (C(CH3)3), 34.8 (C(CH3)3), 34.6 (C(CH3)3), 31.7 (C(CH3)3), 31.6 (C(CH3)3), 30.0 (C(CH3)3), 29.8\u2005ppm (C(CH3)3).tBuO)P{ON(Me)O} (9\u2009a)Synthesis of  and KOtBu  were dissolved in THF (3\u2005mL) at \u221278\u2009\u00b0C and the reaction mixture was allowed to warm to room temperature. After one hour all volatiles were removed in vacuo. The product was extracted with hexane (3\u2005mL) and the solution was concentrated under a dynamic vacuum and cooled to 5\u2009\u00b0C, resulting in the formation of a colourless microcrystalline solid. Crystals suitable for X\u2010ray diffraction studies were grown from a concentrated hexane solution at room temperature. Yield: 72\u2005mg (50\u2009%); elemental analysis calcd (%) for C33H52NO3P: C 73.16, H 9.68, N 2.59; found: C 73.04, H 9.48, N 2.68. CI MS (NH3 carrier gas): m/z calcd for C29H44NO3P\u22c5H: 486.3137; found: 486.3140; m/z calcd for C29H43NO2P: 468.3026; found: 468.3051; 1H\u2005NMR : \u03b4=7.40 , 7.31 , 2.89 , 1.57  1.57 , 1.25\u2005ppm ; 13C{1H} NMR : \u03b4=149.7 , 144.6 (Ar), 139.3 (Ar), 138.9 , 121.5 (Ar), 118.6 (Ar), 75.7 3), 42.5 , 35.5 (C(CH3)3), 34.7 (C(CH3)3), 31.8 (OC(CH3)3), 31.7 (C(CH3)3), 30.1\u2005ppm (C(CH3)3); 31P\u2005NMR  \u03b4=142.8\u2005ppm (s); 31P{1H} NMR  \u03b4=142.8\u2005ppm (s).tBuO)As{ON(Me)O} (9\u2009b)Synthesis of  was dissolved in THF (5\u2005mL) and cooled to \u221278\u2009\u00b0C. A solution of KOtBu  in THF (5\u2005mL) was then added dropwise. The reaction mixture was stirred at \u221278\u2009\u00b0C for 30\u2005mins, then 30\u2005mins at room temperature. All volatiles were removed in vacuo and the product was extracted with hexane (5\u2005mL) and filtered via cannula. The solution was concentrated under a dynamic vacuum yielding a crude sample of 9\u2009b as a white solid. Isolation of 9\u2009b from other impurities has not been possible, although characterisation data confirms the presence of the expected product. EI MS: m/z calcd for C33H53AsNO3: 586.3241; found: 586.3140; m/z calcd for C29H44AsNO3 [(HO)As{ON(Me)O}]: 529.2537; found: 529.2534; m/z calcd for C29H43AsNO2 [As{ON(Me)O}]: 512.2510\u2009; found: 512.2500; 1H\u2005NMR : \u03b4=7.40 , 7.32 , 2.62 , 1.59  1.54 , 1.28\u2005ppm ; 13C{1H} NMR : \u03b4=151.4 (Ar), 142.9 (Ar), 139.0 (Ar), 137.9 (Ar), 121.9 (Ar), 118.0 (Ar), 73.6 (OC(CH3)3), 43.0 (NCH3), 35.7 (C(CH3)3), 34.6 (C(CH3)3), 33.1 (OC(CH3)3), 31.7 (C(CH3)3), 30.1\u2005ppm (C(CH3)3).X\u2010ray diffraction: Single\u2010crystal X\u2010ray diffraction data were collected using an Oxford Diffraction Supernova dual\u2010source diffractometer equipped with a 135\u2005mm Atlas CCD area detector. Crystals were selected under Paratone\u2010N oil, mounted on micromount loops and quench\u2010cooled using an Oxford Cryosystems open flow N2 cooling device.\u03bb=1.5418\u2005\u00c5; Oxford Diffraction Supernova). Data were processed using the CrysAlisPro package, including unit cell parameter refinement and inter\u2010frame scaling (which was carried out using SCALE3 ABSPACK within CrysAlisPro).F2 using the SHELXL 2013\u20134 package.CCDC\u20051489274 (1\u2009b), 1489275 ][2\u2009a]\u22c51.5\u2009toluene), 1489276 ([K(18\u2010crown\u20106)][2\u2009b]\u22c5THF), 1489277 ([K(18\u2010crown\u20106)][3\u2009a]\u22c50.5\u2009toluene\u22c50.5\u2009pentane), 1489278 ][3\u2009b]), 1489279 (4\u2009a), 1489280 (5\u2009a), 1489281 ([6\u2009a][OTf]\u22c5HOTf), 1489282 ([6\u2009b][OTf]\u22c50.5\u2009hexane), 1489283 ([7\u2009a][OTf]), 1489284 ([7\u2009b][OTf]), 1489285 (8\u2009a), 1489286 (8\u2009b), and 1489287 (9\u2009a) contain the supplementary crystallographic data. These data can be obtained free of charge by The Cambridge Crystallographic Data Centre.DFT calculations: All geometry optimisations were performed using the Amsterdam Density Functional package (ADF2014.01).As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Except for van der Waals forces, there are no significant inter\u00admolecular inter\u00adactions in the crystal.The mol\u00adecular structure of the title titanium(IV) half-sandwich complex, [Ti(\u03b7 Structural details based on the results of X-ray diffraction and of density functional theory calculations at the M06-2X level support the formulation of these complexes as non-classical mono\u00adaza\u00adbutadiene complexes. However, the follow-up chemistry with various multiple bond substrates of the complexes with formulae [(\u03b75-Cp#)Ti(\u03b74-C21H19N)(Cl)]  shows a hidden \u03b72-imine reactivity to five-membered titanacycles Ti(\u03b74-C21H19N)(Cl)] with the dialkyl-substituted lithium amide LiN(Me)Cy, the formation of a titanadi\u00adhydro\u00adpyrrole is observed as a result of the 1,3-H-shift in the five-membered ring system in addition to the salt metathesis reaction Ti(\u03b74-C21H19N)(C12H10N), 1, synthesized by the reaction of [(\u03b75-Cp*)Ti(\u03b74-C21H19N)(Cl)] with the diaryl-substituted lithium amide LiNPh2. Compound 1 maintains the \u03b74-coordination mode of the ketimine ligand.Here we report the synthesis and crystal structure of the title compound (\u03b71 for which the \u03b74-coordination mode of the ketimine ligand is clearly confirmed. The N1\u2014C17 bond length [1.383\u2005(3)\u2005\u00c5] is significantly elongated compared to the free ketimine   in contrast to the well-balanced C\u2014-C distances in the C18\u2013C23 aromatic ring system (\u2243 1.39\u2005\u00c5). The central titanium(IV) atom is fourfold coordinated in a considerably distorted tetra\u00adhedral coordination environment, with N1\u2014Ti1\u2014N2 and N1\u2014Ti1\u2014C30 bond angles of 110.42\u2005(9) and 84.23\u2005(9)\u00b0, respectively. The Ti1\u2014N1 bond length [1.963\u2005(2)\u2005\u00c5] is shorter than the Ti1\u2014N2 bond length [2.009\u2005(2)\u2005\u00c5] and indicates weak \u03c0p\u2013\u03c0d electron donor inter\u00adactions. The Ti1\u2014C30 bond length [2.259\u2005(3)\u2005\u00c5] as well as the fold angle of the central five-membered ring system (60.6\u00b0) are similar to those in other reported mono\u00adaza\u00adbutadiene complexes /2 \u2013 (Ti1\u2014N1 + Ti1\u2014C30)/2] = 0.386\u2005\u00c5 Ti(\u03b74-C21H19N)(Cl)] and lithium diphenyl amide were prepared according to published procedures Ti(\u03b74-C21H19N)(Cl)]  and lithium diphenyl amide  were dissolved in 12\u2005ml of tetra\u00adhydro\u00adfuran. After stirring the reaction mixture for 16\u2005h at room temperature, the solvent was evaporated in a vacuum. The residue was dissolved in 12\u2005ml of toluene, filtered, and the precipitate of LiCl was washed with toluene (2 \u00d710\u2005ml). The combined filtrates were evaporated in a vacuum and the residue was recrystallized from n-hexane to yield complex 1 as dark-red prisms in 15% crystalline yield.[ I. DOI: 10.1107/S2056989017017455/wm5424Isup2.hklStructure factors: contains datablock(s) I. DOI: 1589353CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A and B) with similar conformations. In the crystal, they are arranged alternately, forming \u2013A\u2013B\u2013A\u2013B\u2013 chains linked by N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds, which extend along the a-axis direction.The asymmetric unit of the title carbamate, contains two independent mol\u00adecules . The di\u00admethyl\u00adphenyl ring, the phenyl ring and the central carbamate N\u2014C(=O)\u2014O group are not coplanar. In mol\u00adecule A, the di\u00admethyl\u00adphenyl and phenyl rings are inclined to the carbamate group mean plane by 27.71\u2005(13) and 71.70\u2005(4)\u00b0, respectively, and to one another by 84.53\u2005(13)\u00b0. The corresponding dihedral angles in mol\u00adecule B are 34.33\u2005(11), 66.32\u2005(13) and 85.48\u2005(12)\u00b0, respectively. In the crystal, the A and B mol\u00adecules are arranged alternately linked through N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds, forming \u2013A\u2013B\u2013A\u2013B\u2013 chains, which extend along [100]. Within the chains and linking neighbouring chains there are C\u2014H\u22ef\u03c0 inter\u00adactions present, forming columns along the a-axis direction. The columns are linked by offset \u03c0\u2013\u03c0 stacking inter\u00adactions, forming a three-dimensional network [shortest centroid\u2013centroid distance = 3.606\u2005(1)\u2005\u00c5].The asymmetric unit of the title compound, C In mol\u00adecule A, the di\u00admethyl\u00adphenyl ring (C1\u2013C6) makes a dihedral angle of 84.53\u2005(13)\u00b0 with the phenyl ring (C10\u2013C15), and in mol\u00adecule B the di\u00admethyl\u00adphenyl ring (C16\u2013C21) makes a dihedral angle of 85.48\u2005(12)\u00b0 with the phenyl ring (C25\u2013C30). In mol\u00adecule A, the aryl rings (C1\u2013C6 and C10\u2013C15) are inclined to the the mean plane of the carbamate N1\u2014C9(=O2)\u2014O1 unit by 27.71\u2005(13) and 71.70\u2005(14)\u00b0, respectively. In mol\u00adecule B, rings C16\u2013C21 and C25\u2013C39 are inclined to the the mean plane of the carbamate N2\u2014C24(=O24)\u2014O13 unit by 34.33\u2005(11) and 66.32\u2005(13)\u00b0, respectively. The C9\u2014N1 and C24\u2014N2 distances are 1.336\u2005(3) and 1.335\u2005(3)\u2005\u00c5, respectively, indicating partial double-bond character in the carbamate unit.The asymmetric unit of the title compound, Fig.\u00a01A\u2013B\u2013A\u2013B\u2013 chains, propagating along the a-axis direction . These inter\u00adactions form columns along the a-axis direction, which are linked by offset \u03c0\u2013\u03c0 stacking inter\u00adactions , forming a three-dimensional network, as illustrated in Fig.\u00a04Cg1\u22efCg1iii = 3.738\u2005(2)\u2005\u00c5, inter\u00adplanar distance = 3.521\u2005(1)\u2005\u00c5, slippage = 1.257\u2005\u00c5; Cg3\u22efCg3iv = 3.606\u2005(1)\u2005\u00c5, inter\u00adplanar distance = 3.462\u2005(1)\u2005\u00c5, slippage = 1.007\u2005\u00c5; Cg1 and Cg3 are the centroids of the C1\u2013C6 and C16\u2013C21 rings, respectively; symmetry codes: (iii) \u2212x\u00a0+\u00a03, \u2212y, \u2212z\u00a0+\u00a01; (iv) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].In the crystal, N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds link the mol\u00adecules to form \u2013n Table\u00a01. Within ns Fig.\u00a03b, formiet al., 2016Pna21 polymorphs of phenyl phenyl\u00adcarbamate itself, viz. YEHPOQ  and 85.5\u2005(1)\u00b0, respectively, in mol\u00adecules A and B of the title compound.A search of the Cambridge Structural Database  of 3,5 dimethyl aniline dissolved in 100\u2005ml of dry THF was added a calculated 5% excess of phenyl\u00adchloro\u00adforamate in 50\u2005ml of dry THF. The addition rate was such that it took 1.5\u2005h for complete transfer. After the addition was complete, stirring was continued overnight. Excess THF was removed under vacuum at room temperature. The crude product was extracted with ethyl acetate (3 \u00d7 100\u2005ml), and then the organic layer was dried over anhydrous sodium sulfate. Removing the solvent under vacuum at room temperature, yielded a light-yellow product which was dried under vacuum to constant weight. Yellow block-like crystals were obtained by slow evaporation of an ethyl acetate solution at room temperature (yield 99%).Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for the H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017006922/su5370sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017006922/su5370Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006922/su5370Isup3.cmlSupporting information file. DOI: 1548793CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Supra\u00admolecular layers in the bc plane sustained by C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions feature in the crystal.The title mol\u00adecule has a approximately coplanar relationship between the methyl\u00adidenehydrazinecarbodi\u00adthio\u00adate (C 16H17N3S2 (systematic name: (Z)-{[(benzyl\u00adsulfan\u00adyl)methane\u00adthio\u00adyl]amino}[1-(6-methyl\u00adpyridin-2-yl)ethyl\u00adidene]amine), the central methyl\u00adidenehydrazinecarbodi\u00adthio\u00adate (C2N2S2) core is almost planar (r.m.s. deviation = 0.0111\u2005\u00c5) and forms dihedral angles of 71.67\u2005(3)\u00b0 with the approximately orthogonally inclined thio\u00adester phenyl ring, and 7.16\u2005(7)\u00b0 with the approximately coplanar substituted pyridyl ring. The latter arrangement and the Z configuration about the imine-C=N bond allows for the formation of an intra\u00admolecular hydrazine-N\u2014H\u22efN(pyrid\u00adyl) hydrogen bond that closes an S(6) loop. In the crystal, phenyl-C\u2014H\u22efS(thione), methyl\u00adene-C\u2014H\u22ef\u03c0(pyrid\u00adyl), methyl\u00adene- and phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) contacts connect mol\u00adecules into supra\u00admolecular layers propagating in the bc plane; the layers stack along the a axis with no directional inter\u00adactions between them. The analysis of the Hirshfeld surface indicates the relative importance of an intra\u00adlayer phenyl-H\u22efH(pyrid\u00adyl) contact upon the mol\u00adecular packing.In the title di\u00adthio\u00adcarbazate ester, C Different ligands can be obtained by introducing different organic substituents, which causes variation in their biological properties, although they may differ only slightly in their mol\u00adecular structures  and 7.16\u2005(7)\u00b0, respectively, indicating nearly orthogonal and co-planar dispositions, respectively; the dihedral angle between the outer rings is 65.79\u2005(4)\u00b0. The configuration about the imine-C9=N2 bond [1.2924\u2005(18)\u2005\u00c5] is Z, resulting in the hydrazine-N1\u2014H hydrogen atom being directed towards the pyridyl-N3 atom, enabling the formation of an inter\u00admolecular amine-N1\u2014H\u22efN3(pyrid\u00adyl) hydrogen bond that closes an S(6) loop, Table\u00a01syn with the thione-S1 atom and at the same time is orientated to the opposite side of the mol\u00adecule to the imine-bound methyl group.The mol\u00adecular structure of (I)b-axis direction, and a number of C\u2014H\u22ef\u03c0 contacts, i.e. methyl\u00adene-C2\u2014H\u22ef\u03c0(pyrid\u00adyl), phenyl-C7\u2014H\u22ef\u03c0(phen\u00adyl) and methyl-C10\u2014H\u22ef\u03c0(phen\u00adyl), as detailed in Table\u00a01bc plane, Fig.\u00a02a. Layers stack along the a axis with no directional inter\u00adactions between them, Fig.\u00a02b.The participation of the hydrazine-N1\u2014H hydrogen and pyridyl-N3 atoms in the intra\u00admolecular N\u2014H\u22efN hydrogen bond precludes their participation in inter\u00admolecular inter\u00adactions. The mol\u00adecular packing features weak phenyl-C8\u2014H\u22efS2(thione) inter\u00adactions, leading to chains along the et al., 2017dnorm in Fig.\u00a03a (labelled as \u20181\u2019). The presence of the weak inter\u00admolecular C\u2014H\u22efS contact involving the phenyl-C8 and thione-S2 atoms is evident from the diminutive red spots near these atoms in Fig.\u00a03b (labelled as \u20183\u2019) characterize the short surface C\u22efH/H\u22efC contacts and indicate the relative importance of this particular C\u2014H\u22ef\u03c0 contact compared with the other two C\u2014H\u22ef\u03c0 contacts summarized in Table\u00a01i.e. \u03c0\u22efH\u2014C, containing \u03c0-bond acceptors, on the Hirshfeld surface mapped with the shape-index property are illustrated in Fig.\u00a05The Hirshfeld surfaces calculated for (I)a, and those delineated  indicate the significant influence of the short inter\u00adatomic phenyl-H\u22efH(pyrid\u00adyl) contacts in the crystal mentioned above. The inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions discussed earlier are characterized by short inter\u00adatomic C\u22efH/H\u22efC contacts  and pyridyl  rings on the Hirshfeld surface mapped over the electrostatic potential in Fig.\u00a04de + di \u223c 2.8\u2005\u00c5 in Fig.\u00a06d. The inter\u00adatomic N\u22efH/H\u22efN contacts do not represent directional inter\u00adactions as the inter\u00adatomic separations are greater than sum of their van der Waals radii as evident from Fig.\u00a06e. Similarly, the other surface contacts summarized in Table\u00a03The overall two-dimensional fingerprint plot for (I)ts Fig.\u00a06b indicas Table\u00a02 and theiChemical context, there is sustained inter\u00adest in this class of compound and this is reflected by the observation there are four closely related structures available for comparison, varying in the S-bound group and substitution in the 2-pyridyl ring. In common with (I)Z-configuration is noted about the imine bond allowing for the formation of an intra\u00admolecular hydrazine-N\u2014H\u22efN(pyrid\u00adyl) hydrogen bond  hydrogen bonds and eight-membered {\u22efHNCS}2 synthons.As mentioned in the S-Benzyl\u00addithio\u00adcarbazate (SBDTC) was prepared according to the method published by Ali & Tarafder (1977\u22121): 2921 \u03bd(N\u2014H), 1560 \u03bd(C=N), 1055 \u03bd(N\u2014N), 881 \u03bd(CSS).All chemicals were of analytical grade and were used without any further purification. fder 1977. PotassiUiso(H) set to 1.2\u20131.5Ueq(C). The nitro\u00adgen-bound H atom was located in a difference Fourier map, but was refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018001330/hb7730sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018001330/hb7730Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018001330/hb7730Isup3.cmlSupporting information file. DOI: 1818384CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 5FC ring forms a dihedral angle of 19.97\u2005(11)\u00b0 with the ring of the picrate (PA\u2212) anion. In the crystal, the 5FC+ cation inter\u00adacts with the PA\u2212 anion through three-centre N\u2014H\u22efO hydrogen bonds, forming two conjoined rings having R21(6) and R12(6) motifs, and is extended by N\u2014H\u22efO hydrogen bonds and C\u2014H\u22efO inter\u00adactions into a two-dimensional sheet structure lying parallel to (001). Also present in the crystal structure are weak C\u2014F\u22ef\u03c0 inter\u00adactions.In the crystal structure of the title compound, 5-fluoro\u00adcytosinium picrate, C New solid forms of pharmaceuticals are designed using the crystal engineering approach. These engineered solids have technological and legal importance. Among the inter\u00admolecular inter\u00adactions, hydrogen bonding is the master key for mol\u00adecular recognition in biological systems because of its strength and directionality  and one picrate anion (PA\u2212)  anion, the nitro groups lie variously out of the parent benzene ring, with torsion angles C9\u2014C8\u2014N5\u2014O4, C9\u2014C10\u2014N6\u2014O7 and C11\u2014C12\u2014N7\u2014O9 of 166.2\u2005(2), \u2212171.7\u2005(2) and 147.2\u2005(2)\u00b0, respectively.The asymmetric unit contains one 5-fluoro\u00adcytosinium cation (5FC\u2212) Fig.\u00a01. The 5-f+ cation inter\u00adact with atoms O3 and O9 of the picrate anion through three-centre N\u2014H\u22efO hydrogen bonds, forming two fused-ring motifs with graph-sets + cation acts as a three-centre donor and the O3 atom of the PA\u2212 anion acts as a three-centre acceptor. This type of inter\u00adaction has also been reported in the crystal structures of 2-amino-4,6-di\u00admethyl\u00adpyrimidinium picrate  Fig.\u00a01. One of g Table\u00a01. A similii atom and the amino group of the 5FC+ cation are connected through an N\u2014H\u22efO hydrogen bond, forming a two-dimensional supra\u00admolecular network lying parallel to (001) \u2005\u00c5; C\u2014F\u22efCg = 88.34\u2005(12)\u00b0, where Cg is the centroid of the N1\u2013C6 ring; symmetry code: (iv) \u2212x, \u2212y, \u2212z\u00a0+\u00a01]. A similar angle [90.5\u2005(2)\u00b0] has been reported for a C\u2014F\u22efCg inter\u00adaction in an acridinium tri\u00adfluoro\u00admethane sulfonate compound  Fig.\u00a02. Also pr1) Fig.\u00a02 between et al., 1982et al., 2013et al., 2012et al., 2014et al., 2001et al., 2014et al., 2016et al., 2006et al., 2009et al., 1995et al., 2004et al., 2004The crystal structures of 5-fluoro\u00adcytosine monohydrates (Louis A hot aqueous solution of 5-fluoro\u00adcytosine (32\u2005mg) and picric acid (57\u2005mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed to 353\u2005K wrong symmetry description - inversion centre in central benzene ring over a water bath for half an hour and kept for slow evaporation. After a week, colourless prismatic crystals were obtained.Uiso(H) = 1.2Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901700216X/zs2375sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901700216X/zs2375Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901700216X/zs2375Isup3.cmlSupporting information file. DOI: 1531927CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the crystal of the title compound contains two rivaroxaban mol\u00adecules with different conformations. 19H18ClN3O5, contains two rivaroxaban mol\u00adecules with different conformations; the C\u2014C\u2014N\u2014C torsion angles between the oxazolidine and thio\u00adphene rings are \u2212171.1\u2005(7) and \u2212106.8\u2005(9)\u00b0 in the two independent mol\u00adecules. In the crystal, classical N\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular architecture.The asymmetric unit of the crystal of the title compound (common name rivaroxaban), C At present, the incidence of thromboic disease is extremely high; this is mainly caused by vascular endothelial injury, increased blood coagulation, increased platelet number and decreased anti\u00adcoagulant activity  and \u2212106.8\u2005(9)\u00b0, respectively \u2005\u00c5 for the O2A atom], whereas the oxazolidine ring of mol\u00adecule B displays an envelope conformation with atom C8B as the flap. The morpholine rings of the two mol\u00adecules display similar twisted boat conformations. Atoms O4 and C17 deviate from the C16/N3/C19/C18 mean plane by 0.230\u2005(2) and 0.517\u2005(2)\u2005\u00c5, respectively, in mol\u00adecule A and by 0.290\u2005(2) and 0.489\u2005(2)\u2005\u00c5 in mol\u00adecule B.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01y Table\u00a01. The oxaA and B into dimers, and weak C\u2014H\u22efO hydrogen bonds link the dimers to form a three-dimensional supra\u00admolecular architecture . The O\u22efH/H\u22efO inter\u00adactions (22.4%), which are the most significant inter\u00admolecular inter\u00adactions and link the mol\u00adecular dimers into infinite chains along the b axis, appear as two obvious spikes . At the top left (di < de) and bottom right (di > de) of the fingerprint plot, there are characteristic \u2018wings\u2019 that are identified resulting from the C\u22efH/H\u22efC inter\u00adactions (18.7%) shown in Fig.\u00a03d.The light-red spots on the Hirshfeld surface are the results of N\u2014H\u22efO, C\u2014H\u22efO and C\u2014Cl\u22efO inter\u00adactions Fig.\u00a03. The H\u22efHes Fig.\u00a03c. At thThe crude product was supplied by the Zhejiang Huadong Pharmaceutical Co., Ltd. It was recrystallized from methanol solution, giving colourless crystals suitable for X-ray diffraction.A and H1B were found in difference-Fourier maps, but placed in calculated positions with N\u2014H = 0.86\u2005\u00c5 and refined as riding with Uiso(H) = 1.2Ueq(N). All other H atoms were placed in calculated positions with C\u2014H = 0.93\u20130.98\u2005\u00c5 and included in the refinement in a riding model, with Uiso(H) = 1.2 or 1.5Ueq(carrier atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017017819/xu5913sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017017819/xu5913Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017017819/xu5913Isup3.cmlSupporting information file. DOI: 1810879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of (I), supra\u00admolecular layers parallel to (10-1) are sustained by methyl\u00adene-C\u2014H\u22efO(meth\u00adoxy) inter\u00adactions, while in (II), centrosymmetric dimers are formed via pairwise weak phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) contacts.The coordination geometry in ( 4H9)2(C7H14NO2S2)2], (I), and [Sn(C6H5)3(C5H10NOS2)], (II), are described. Both structures feature asymmetrically bound di\u00adthio\u00adcarbamate ligands leading to a skew-trapezoidal bipyramidal geometry for the metal atom in (I) and a distorted tetra\u00adhedral geometry in (II). The complete mol\u00adecule of (I) is generated by a crystallographic twofold axis (Sn site symmetry 2). In the crystal of (I), mol\u00adecules self-assemble into a supra\u00admolecular array parallel to (10-1) via methyl\u00adene-C\u2014H\u22efO(meth\u00adoxy) inter\u00adactions. In the crystal of (II), supra\u00admolecular dimers are formed via pairs of weak phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) contacts. In each of (I) and (II), the specified assemblies connect into a three-dimensional architecture without directional inter\u00adactions between them. Hirshfeld surface analyses confirm the importance of H\u22efH contacts in the mol\u00adecular packing of each of (I) and (II), and in the case of (I), highlight the importance of short meth\u00adoxy-H\u22efH(but\u00adyl) contacts between layers.The crystal and mol\u00adecular structures of the two title organotin di\u00adthio\u00adcarbamate compounds, [Sn(C The coordination environment is completed by two \u03b1-carbon atoms of the n-butyl substituents. The resultant C2S4 donor set defines a skew-trapezoidal bipyramidal geometry with the tin-bound organic substituents lying over the weaker Sn\u2014S2 bonds, which subtend an angle at the tin atom approximately 50\u00b0 wider than that subtended by the S1 atoms, Table\u00a012CN residue and have very similar conformations, as seen in the values of the C1\u2014N1\u2014C2\u2014C3, N1\u2014C2\u2014C3\u2014O1 and C2\u2014C3\u2014O1\u2014C4 torsion angles of \u221294.1\u2005(4), \u221267.4\u2005(4) and \u2212177.1\u2005(3)\u00b0, indicating that \u2212 anti-clinal, \u2212 syn-clinal and \u2212 anti-periplanar descriptors, respectively, are in effect. For the O2-meth\u00adoxy\u00adethyl group, the equivalent torsion angles are \u221282.0\u2005(4), \u221270.3\u2005(4) and \u2212169.1\u2005(3)\u00b0. The independent n-butyl substituent has an all-trans (+ anti-periplanar) conformation, as seen in the values of the Sn\u2014C8\u2014C9\u2014C10 and C8\u2014C9\u2014C10\u2014 C11 torsion angles of 172.9\u2005(2) and 176.3\u2005(3)\u00b0, respectively.The tin atom in (I)b, lies on a general position and has a quite distinct coordination geometry owing to the presence of three tin-bound phenyl groups. As for (I)cf. (I)i.e. nearly 0.07\u2005\u00c5, Table\u00a02cf. (I)3S2 donor set approximates a trigonal\u2013bipyramidal geometry with the value of \u03c4, an indicator of a five-coordinate coordination geometry, being 0.61, cf. 1.0 for an ideal trigonal bipyramid and 0.0 for an ideal square pyramid \u00b0, for S1\u2014Sn\u2014C11, to 119.09\u2005(7)\u00b0, for S1\u2014Sn\u2014C31. The C21\u2014Sn\u2014C31 angle, at 115.55\u2005(10)\u00b0, is wider by 10\u00b0 than the other C\u2014Sn\u2014C angles, a result correlated with the close approach of the S2 atom. The 2-meth\u00adoxy\u00adethyl group has a very similar conformation to the O1-meth\u00adoxy\u00adethyl group in (I)The mol\u00adecule in (II)b so that a supra\u00admolecular array is formed parallel to PLATON et al., 2017The Hirshfeld surface calculations for the organotin derivatives (I)A and H6B atoms lying on both the sides of twofold symmetry axis on the Hirshfeld surfaces mapped over dnorm for (I)a and b represent the dominant inter\u00admolecular C\u2014H\u22efO contacts, Table\u00a03B and butyl-H8A atoms in Fig.\u00a04c indicate the significant influence of intra-layer H\u22efH contacts, Table\u00a05a and b, the donors and acceptors are represented with blue and red regions around the respective atoms corresponding to positive and negative potentials, respectively.The bright-red spots near each of the meth\u00adoxy-O1 and -O2, and methyl\u00adene-H4dnorm for (II)c are due to polarization of charges near the respective functional groups and do not represent any significant inter\u00adaction in the crystal. The weak inter\u00admolecular C\u2014H\u22ef\u03c0 contact and intra-layer inter\u00adatomic H\u22efH contacts et al., 2007de + di \u223c 2.0\u2005\u00c5 and the distribution of points with greater density in  range \u223c1.0 to 1.2\u2005\u00c5 for (I)a, and a small peak at de + di \u223c 2.2\u2005\u00c5 with relatively few points at de + di < 2.4\u2005\u00c5 for (II)b. The fingerprint plot delineated into O\u22efH/H\u22efO contacts for (I)a, characterizes inter\u00admolecular C\u2014H\u22efO inter\u00adactions as the pair of forceps-like tips at de + di \u223c 2.5\u2005\u00c5. A low percentage contribution due to O\u22efH/H\u22efO contacts is noted for (II)i.e. 29.1%, contribution from C\u22efH/H\u22efC contacts to the Hirshfeld surfaces of (II)de + di \u223c 2.8\u2005\u00c5 and the distribution of points around de + di \u223c 2.9\u2005\u00c5 in both the wings of its delineated fingerprint plot, Fig.\u20057bi.e. de + di > 3.0\u2005\u00c5, Fig.\u00a07The overall two-dimensional fingerprint plots for (I)R\u2032\u2032xSn(S2CNRR\u2032)x4\u2013, can adopt a variety of coordination geometries, especially for x = 2 2Sn[S2CN(CH3)CH2CH2OCH3]2 . Carbon, hydrogen, nitro\u00adgen and sulfur analyses were performed on a Leco CHNS-932 Elemental Analyzer. The IR spectra were obtained on a Perkin Elmer Spectrum GX from 4000 to 400\u2005cmSynthesis of (I) bis\u00ad(2-meth\u00adoxy\u00adeth\u00adyl)amine  dissolved in ethanol (30\u2005ml) was stirred for 30\u2005min. Then, carbon di\u00adsulfide  in cold ethanol was added and the resulting mixture was stirred for 2\u2005h. A 25% ammonia solution (1\u20132\u2005ml) was added to generate basic conditions. Then, di-n-butyl\u00adtin(IV) dichloride  dissolved in ethanol (20\u201330\u2005ml) was added dropwise into the solution and stirring was continued for 2\u2005h. All reactions were carried out at 277\u2005K. The precipitate that formed was dried and collected. Colourless prisms were harvested from the slow evaporation of its chloro\u00adform:ethanol (2:1 v/v) solution. Yield: 72%. M.p. 341\u2013342\u2005K. Elemental analysis: calculated (%): C 40.68, H 7.14, N 4.31, S 19.75. Found (%): C 41.76, H 6.07, N 4.91, S 19.25. IR (KBr cm\u22121): 1487 \u03bd(C\u2014N), 992 \u03bd(C\u2014S), 544 \u03bd(Sn\u2014C), 386 \u03bd(Sn\u2014S). 1H NMR (CDCl3): \u03b4 4.13 ; 3.70 ; 3.35 ; 1.45\u20132.05 , 0.94 . 13C NMR (CDCl3): \u03b4 201.52 (NCS2); 70.07 (O\u2014CH2); 55.59 (N\u2014CH2); 59.01 (O\u2014CH3); 34.26 Sn\u2014CH2; 28.55 Sn\u2014CH2CH2; 26.41 Sn\u2014CH2CH2CH2; 13.87 CH2CH3. 119Sn NMR (CDCl3): \u03b4 \u2212335.5.Synthesis of (II) The synthesis of (II)v/v) solution. Yield: 78%. M.p. 366-367\u2005K. Elemental analysis: calculated (%): C 53.71, H 4.89, N 2.72, S 12.47. Found (%): C 54.28, H 5.26, N 2.73, S 12.5. IR (KBr cm\u22121): 1477 \u03bd(C\u2014N), 997 \u03bd(C\u2014S), 527 \u03bd(Sn\u2014C), 451 \u03bd(Sn\u2014S). 1H NMR (CDCl3): \u03b4 7.41\u20137.82 ; 4.05 ; 3.71 ; 3.51 ; 3.38 . 13C NMR (CDCl3): \u03b4 196.97 (NCS2); 128.25\u2013142.28 (C-aromatic); 70.09 (O\u2014CH2); 59.06 (N\u2014CH2); 58.10 (O\u2014CH3); 45.81 (N\u2014CH3);. 119Sn NMR (CDCl3): \u03b4 \u2212183.8.Uiso(H) set to 1.2\u20131.5Ueq(C). For (I)\u22123, respectively, were located 0.88 and 1.03\u2005\u00c5 from the S1 and Sn atoms, respectively. For (II)\u22123, respectively, were located 0.96 and 0.76\u2005\u00c5 from the Sn atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989018001901/hb7731sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018001901/hb7731Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018001901/hb7731IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1821129, 1821128CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Tumor necrosis factor-\u03b1 has been proven an effective anticancer agent in preclinical studies. However, the translation of TNF\u03b1 from research to clinic has been blocked by significant systemic toxicity and limited efficacy at maximal tolerated dose, which need urgently to be solved.2+ was assessed by Fura-2 in HCC cells. After changing cytosolic Ca2+ level by using agonists or inhibitors, cell apoptosis was detected by flow cytometry. We also detected the effect of ionomycin or parvalbumin on the anti-tumor activity of TNF\u03b1 in a mice model. Lastly, we studied the roles of cytosolic Ca2+ in the mitochondrial-dependent intrinsic apoptosis pathway.The level of cytosolic Ca2+ influx into cytoplasm through transient receptor potential channel in HCC cells. Both cytosolic Ca2+ scavenger and Ca2+-binding protein PV effectively desensitized hepatocellular carcinoma cells to TNF\u03b1, whereas combination ionomycin or 1,4,5-inositol triphosphate significantly sensitized HCC cells to TNF\u03b1, indicating that the increased level of cytosolic Ca2+ was positively correlated with the TNF\u03b1-induced cell apoptosis in vitro. In a nude mice xenograft model, our data revealed that TNF\u03b1 combined with ionomycin remarkably synergized the anti-tumor effect of TNF\u03b1. Furthermore, we found that TNF\u03b1-mediated extracellular Ca2+ influx accelerated TNF\u03b1-induced extrinsic apoptosis through activating calpain/IAP/caspase3 pathway.Here, we demonstrated that TNF\u03b1 induced extracellular Ca2+ influx to enhance cell apoptosis and suggests that increasing the level of cytosolic Ca2+ might be an alternative strategy to improve the pro-apoptotic activity of TNF\u03b1 in HCC cells, although suitable chemical or biological reagents need to be further tested.Our study provides the evidence supporting a novel mechanism by which TNF\u03b1 induces extracellular CaThe online version of this article (10.1186/s13046-018-0714-6) contains supplementary material, which is available to authorized users. TNF\u03b1 is a 23KD type II transmembrane protein, which is arranged in stable homotrimers. It is primarily produced by macrophages and a variety of other cells, including NK cells, T lymphocytes, smooth muscle cells, fibroblasts and others . Many pr2+, as a common signal transduction factor, has played many important roles in the process of cell division, growth, and death c after TNF\u03b1 treatment in HCC cells. We further found that either Ca2+ scavengers or PV reduced the percentage of TNF\u03b1-induced apoptotic HCC cells  and IP3  were used to rapidly elevate [Ca2+]c as described previously [2+]c in HLF and QSG-7701 cells after TNF\u03b1 treatment  treatment  only  plays critical roles in TNF\u03b1-induced extrinsic apoptotic pathway c level using fluorescent probe Fura-2/AM in SNU739 and HLF cells with treatment as indicated. BAPTA-AM: 10\u00a0\u03bcM. (b) Cell apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated before TNF\u03b1 (100\u00a0ng/mL) stimulation. BAPTA-AM: 10\u00a0\u03bcM. (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in HCC cells with treatment as indicated. EV: cells transfected with the empty vector; PV-OE: cells stably forced expressing Parvalbumin protein. (d) Apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. (e) Western Blot analysis for Parvalbumin expression in SNU739 and HLF cells with treatment as indicated. (f) Cell apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. CAI: 10\u00a0\u03bcM; SKF96365: 100\u00a0\u03bcM. (g) Cell apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. siTRPM7: siRNA against TRPM7; si Ctrl: negative control siRNA. Data were shown as mean\u2009\u00b1\u2009SD. All experiments were performed at least three times. * P\u2009<\u20090.05; ** P\u2009<\u20090.01. (ZIP 1986\u00a0kb)Additional file 4:Figure S3. Cytosolic Ca2+ sensitized HCC cells to TNF\u03b1-induced apoptosis. (a) Apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. (b) and (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in HLF and QSG-7701 cells with treatment as indicated. TNF\u03b1 (50\u00a0ng/mL)\u2009+\u2009Iono: 50\u00a0ng/mL TNF\u03b1 combined with 1\u00a0\u03bcM ionomycin, TNF\u03b1 (100\u00a0ng/mL)\u2009+\u2009Iono: 100\u00a0ng/mL TNF\u03b1 combined with 1\u00a0\u03bcM ionomycin, TNF\u03b1 (200\u00a0ng/mL)\u2009+\u2009Iono: 200\u00a0ng/mL TNF\u03b1 combined with 1\u00a0\u03bcM ionomycin. TNF\u03b1 (50\u00a0ng/mL)\u2009+\u2009IP3: 50\u00a0ng/mL TNF\u03b1 combined with 10\u00a0\u03bcM IP3; TNF\u03b1 (100\u00a0ng/mL)\u2009+\u2009IP3: 100\u00a0ng/mL TNF\u03b1 combined with 10\u00a0\u03bcM IP3; TNF\u03b1 (200\u00a0ng/mL)\u2009+\u2009IP3: 200\u00a0ng/mL TNF\u03b1 combined with 10\u00a0\u03bcM IP3; (d)-(f) Apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. Data were shown as mean\u2009\u00b1\u2009SD. All experiments were performed at least three times. * P\u2009<\u20090.05; ** P\u2009<\u20090.01. (ZIP 2448\u00a0kb)Additional file 5:Figure S4. The level of extracellular calcium influx is positively correlated with TNF\u03b1-mediated apoptosis. (a) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in 10 kinds of HCC cells with treatment as indicated. (b) Apoptosis analysis by flow cytometry 24\u00a0h after treatment as indicated. All experiments were performed at least three times. (ZIP 2184\u00a0kb)Additional file 6:Figure S5. The role of TNF\u03b1-mediated Ca2+ influx in normal hepatic cells. (a) and (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in QSG-7701 cells with treatment as indicated. TNF\u03b1: 100\u00a0ng/mL; siTRPM7: siRNA target TRPM7. (b) qRT-PCR and western blot analysis of TRPM7 mRNA and protein expression levels in QSG-7701 cells transfected with siRNA as indicated. (d) Analysis of Calpain activity after TNF\u03b1 stimulation for 4\u00a0h in QSG-7701 cells with treatment as indicated. Data were shown as mean\u2009\u00b1\u2009SD. All experiments were performed at least three times. * P\u2009<\u20090.05; ** P\u2009<\u20090.01. (JPEG 664\u00a0kb)"}
{"text": "A new mononuclear cobalt(III) complex that has two thiol\u00adate and one thio\u00adether donor atoms is reported. I3CoIII2 complex, [Ag3{Co(L)}2]3+ [L3\u2013 = N(CH2NHCH2CH2S\u2212)3], in which two tris\u00ad(thiol\u00adate)-type mononuclear CoIII units ([Co(L)]) are bridged by three AgI ions through S atoms, with iodo\u00admethane (CH3I) gave a new CoIII mononuclear complex, [Co(LMe2)]2+ [LMe2\u2212 = N(CH2NHCH2CH2S\u2212)(CH2NHCH2CH2SCH3)2], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF6\u2212 anions to form the title compound, [Co(LMe2)](PF6)2. In the [Co(LMe2)]2+ cation, two of three thiol\u00adate groups in [Co(L)] are methyl\u00adated while one thiol\u00adate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe2)]2+, only a pair of enanti\u00adomers {\u039bRR- and \u0394SS-[Co(LMe2)]2+} are selectively formed. In the crystal, the complex cations and the PF\u00ad6\u2212 anions are connected through weak N\u2014H\u22efF, C\u2014H\u22efF and C\u2014H\u22efS hydrogen bonds into a three-dimensional structure. Two F atoms in one PF6 anion are disordered over two sets of sites with refined occupancies of 0.61\u2005(4) and 0.39\u2005(4) and two F atoms in the other PF6\u2212 anion are disordered over two sets of sites with occupancies of 0.5.Treatment of an S-bridged penta\u00adnuclear Ag R1S\u2212) bound to a transition metal center readily react with alkyl halides (R2X) to form a transition metal complex with thio\u00adether groups (R1SR2). Since the resulting thio\u00adether S atoms generally turn to be asymmetric , the alkyl\u00adated species are an inter\u00adesting research target of coordination stereochemistry. Among a variety of alkyl halides, iodo\u00admethane (CH3I) is one of the most common alkyl\u00adation reagent because of its high reactivity and simple mol\u00adecular structure. For example, the reaction of a mono(thiol\u00adate)-type CoIII mononuclear complex, [Co(aet)(en)2]2+ , with iodo\u00admethane selectively produces the corresponding mono(thio\u00adether)-type complex, [Co(mtea)(en)2]3+ (mtea = NH2CH2CH2SCH3) 2], is also easily converted to the corres\u00adponding bis\u00ad(thio\u00adether)-type complex, [Ni(mtea)2]2+, by treating with iodo\u00admethane. Unlike mono(thiol\u00adate)- or bis\u00ad(thiol\u00adate)-type complexes, tris\u00ad(thiol\u00adate)-type complexes have been found to show different reactivity toward iodo\u00admethane. That is, the reaction of a tris\u00ad(thiol\u00adate)-type mononuclear rhodium(III) complex, fac(S)-[Rh(aet)3], with iodo\u00admethane afforded a unique di\u00admethyl\u00adated mono(thiol\u00adate)bis\u00ad(thio\u00adether)-type complex, fac(S)-[Rh(aet)(mtea)2]2+, whereas the mono\u00admethyl\u00adated bis\u00ad(thiol\u00adate)mono(thio\u00adether)-type and tri\u00admethyl\u00adated tris\u00ad(thio\u00adether)-type species were little formed -[Rh(aet)(mtea)2]2+. However, the lack of crystallographic analytical data for fac(S)-[Rh(aet)(mtea)2]2+ prevented the further study on the stereochemistry of the di\u00adalkyl\u00adated complex.It has long been recognized that thiol\u00adate groups ]2}3+ [L3\u2013 = N(CH2NHCH2CH2S\u2212)3] ], are linearly linked by three AgI ions, reacts with iodo\u00admethane to give a mono(thiol\u00adate)bis\u00ad(thio\u00adether)-type complex, [Co(LMe2)]2+ [LMe2\u2212 = N(CH2NHCH2CH2S\u2212)(CH2NHCH2CH2SCH3)2]. It is noteworthy that the complex was crystallized as a hexa\u00adfluorido\u00adphosphate salt, [Co(LMe2)](PF6)2, and its mol\u00adecular structure was fully determined by single-crystal X-ray diffraction analysis. As far as we know, this is the first crystallographic characterization of a cobalt(III) complex that has two thio\u00adether and one thiol\u00adate donor groups. In addition, this is a unique example of a direct conversion of a thiol\u00adate-bridged multinuclear complex to a mononuclear thio\u00adether complex by alkyl\u00adation reaction. Treatment of the thiol\u00adate-bridged penta\u00adnuclear complex {Ag3[Co(L)]2}3+ with excess iodo\u00admethane in water gave a greenish-brown suspension. After removing the insoluble solid by filtration, the purple\u2013brown filtrate was purified by a cation\u2013exchange column (SP-Sephadex C-25). The product was isolated as purple\u2013brown crystals by adding a hexa\u00adfluorido\u00adphosphate anion. The geometrical parameters and stereoisomerism of the title compound based on the X-ray analysis, together with the spectroscopic data, are described in this paper.In the course of our continuing study of the alkyl\u00adation reaction of metal complexes with amino\u00adthiol\u00adate ligands (Okamoto LMe2)]2+, and four PF6\u2212 anions in the asymmetric unit ] moiety were methyl\u00adated to form [Co(LMe2)]2+. No apparent difference was observed among the Co\u2014S bond lengths for thiol\u00adate S atoms (Sthiol\u00adate) [2.2384\u2005(13)\u20132.2478\u2005(11)\u2005\u00c5] and those for thio\u00adether S atoms (Sthio\u00adether) [2.2190\u2005(13)\u20132.2599\u2005(11)\u2005\u00c5] in [Co(LMe2)]2+. However, the Co\u2014N bonds trans to Sthiol\u00adate [2.061\u2005(4)\u20132.062\u2005(3)\u2005\u00c5] are ca 0.05\u2005\u00c5 longer than the Co\u2014N bonds trans to Sthio\u00adether [2.004\u2005(4)\u20132.020\u2005(4)\u2005\u00c5]. The difference is reasonably explained by the decrease of the trans influence due to the alkyl\u00adation on S atoms. As a result of the steric repulsion between the methyl groups on the S atoms, the S\u2014Co\u2014S angles in [Co(LMe2)]2+ deviate considerably from 90\u00b0 [86.58\u2005(4)\u201395.07\u2005(4)\u00b0].X-ray structural analysis revealed that there are two crystallographically independent yet essentially the same complex cations,  units. Considering the absolute configurations of the cobalt(III) atom (\u0394 and \u039b) and the two asymmetric sulfur atoms (R and S), four pairs of diastereomers, \u0394SS/\u039bRR, \u0394SR/\u039bRS, \u0394RS/\u039bSR and \u0394RR/\u039bSS, are possible for [Co(LMe2)]2+. However, the asymmetric unit of this crystal contains two \u039bRR isomers. As indicated by the space group C2/c, the title crystal is a racemic compound consisting of a pair of enanti\u00adomers, \u039bRR and \u0394SS. This result is consistent with the observation that the 13C{1H} NMR spectrum of the title compound in DMSO-d6 exhibits a total of 10 sharp singlet signals, assignable to the C1 symmetrical \u039bRR and \u0394SS isomers of [Co(LMe2)]2+ ]2+ in the crystal, two of three N,S-chelate rings have a gauche form with the lel (\u03bb for \u0394 and \u03b4 for \u039b) conformation, while one has a gauche form with the ob (\u03bb for \u039b and \u03b4 for \u0394) conformation.Each Co2+ Fig.\u00a02. For botLMe2)]2+. This complex was obtained by the unprecedented direct conversion of a thiol\u00adate-bridged AgI3CoIII2 penta\u00adnuclear complex by alkyl\u00adation reaction using iodo\u00admethane. The selective formation of the \u039bRR and \u0394SS isomers of [Co(LMe2)]2+ observed in the crystal structure is consistent with the result of 13C{1H} NMR. The findings reported herein will provide insight into the synthesis and structures of coordination compounds containing both thiol\u00adate and thio\u00adether donor groups.In summary, we report here the first example of a crystallographically characterized mono(thiol\u00adate)bis\u00ad(thio\u00adether)-type mononuclear cobalt(III) complex, [Co]2}(NO3)3\u00b74H2O  in 100\u2005ml of water was added CH3I . The mixture was stirred at room temperature for 1.5 days in the dark. After removing a brown powder (200\u2005mg) by filtration, the purple\u2013brown filtrate was poured onto an SP-Sephadex C-25 column . First, a purple band was eluted with 0.05\u2005M aqueous NaCl. Then, a purple\u2013brown band of [Co(LMe2)]2+ was eluted with 0.15\u2005M aqueous NaCl. To the concentrated purple\u2013brown eluate was added 1.0\u2005M aqueous NH4PF6 (5\u2005ml) and the solution was allowed to stand at room temperature for 20\u2005d. The resulting dark purple\u2013brown block crystals of the title compound were collected by filtration. Yield: 0.08\u2005g (29%). Single crystals suitable for X-ray analysis were obtained by recrystallization from water by adding 1.0 M aqueous NH4PF6. Analysis: calculated for [Co(LMe2)](PF6)2: C 20.01, H 4.12, N 8.48%; found: C 20.25, H 4.06, N 8.51%. 13C{1H} NMR (DMSO-d6): \u03b4 17.40, 18.05, 28.97, 37.20, 47.82, 49.42, 58.22, 64.39, 67.05, 67.50. One of the 13C signals overlaps with the signal from solvent. IR: 3266.8(m), 3029.6(w), 1432.8(m), 1245.8(w), 1158.0(w), 1113.7(w), 1034.6(w), 955.5(m), 839.8(s), 558.3(s).To a dark-purple solution of {Ag2) or 0.98\u2005\u00c5 (CH3)] and refined as riding with Uiso(H) = 1.2Ueq(C) for CH2 and Uiso(H) = 1.5Ueq(C) for CH3. All H atoms bound to N atoms were refined with bond-length restraints [N\u2014H = 0.90\u2005(2)\u2005\u00c5] and with Uiso(H) = 1.2Ueq(N). Two F atoms in one PF6 anion are disordered over two positions (F25A/F25B and F26A/F26B) with refined occupancies of 0.61\u2005(4) and 0.39\u2005(4). Two F atoms in another PF6 anion are also disordered over two positions  with site occupancies of 0.5. Reflections  I. DOI: 10.1107/S2056989017005229/is5473Isup2.hklStructure factors: contains datablock(s) I. DOI: 1542478CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The 1,3-di\u00admethyl\u00adurea mol\u00adecules are also hydrogen bonded to sulfate O atoms, and project outwards from the ribbon parallel to the b axis.The packing is centred on bis\u00ad(piperidinium) sulfate ribbons parallel to the  5H12N+\u00b7SO42\u2212\u00b72C3H8N2S, the C=S groups of the two independent 1,3-di\u00admethyl\u00adurea mol\u00adecules and the sulfur atom of the anion lie on twofold axes. The packing is centred on bis\u00ad(piperidinium) sulfate ribbons parallel to the c axis; the cations are hydrogen bonded to the sulfate by N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions. The 1,3-di\u00admethyl\u00adurea mol\u00adecules are also hydrogen bonded to sulfate O atoms, and project outwards from the ribbon parallel to the b axis.In the title compound, 2C We have published two reports on adducts of dioxane and morpholine with various methyl\u00adthio\u00adureas , so that the methyl groups are cis, with Cmeth\u00adyl\u2014N\u2014C=S torsion angles are close to zero [C11\u2014N1\u2014C1\u2014S1 = 0.9\u2005(2)\u00b0 and S2\u2014C2\u2014N2\u2014C21 = \u22122.05\u2005(17)\u00b0]. Free 1,3-DMT crystallizes with four independent mol\u00adecules, each of which has one NH group cis and one trans to C=S, but the structure is severely disordered  sulfate and 1,3-DMT Fig.\u00a01, with thc axis in the region x, y \u2243 1/2  sulfate ribbons parallel to the /2 Fig.\u00a02 and also2 Table\u00a01. Each pa2 Table\u00a01 and 3 \u25b8;et al., 2016trans geometry for both NH functions, but the 1:2 adduct between 1,4-dioxane and 1,3-DMT  hydrogensulfate sulfate  1,3-DMT were dissolved in 2\u2005mL piperidine. The solution was overlayered with diethyl ether. Colourless needles formed overnight.y, Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017004820/hg5484sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017004820/hg5484Isup2.hklStructure factors: contains datablock(s) I. DOI: 1540583CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The aryl\u00adoxo magnesiate complex anion is binuclear with each Mg2O4 complex unit inversion-related and bridged through the two tridentate chelating phenolate O-donors of the ligand. The complex centres have a distorted tetra\u00adhedral stereochemistry [Mg\u2014O range 1.8796\u2005(17)\u20132.0005\u2005(16)\u2005\u00c5] and an Mg\u22efMg separation of 2.9430\u2005(14)\u2005\u00c5]. The LiO4 coodination sphere of the cation comprises four THF O-donor atoms and has a slightly distorted tetra\u00adhedral conformation [Li\u2014O range 1.899\u2005(5)\u2013 1.953\u2005(5)\u2005\u00c5]. In the crystal, a number of stabilizing intra-anion C\u2014H\u22efO hydrogen-bonding inter\u00adactions are present but no inter-species associations are found.The title ion-association metal complex, [Li(C The structure of this novel heterobimetallic complex, in an ion-association mode, is reported herein.Magnesium complexes  of the two chelating phenolate groups . The stereochemistry about each four-coordinated Mg atom is distorted tetra\u00adhedral with Mg\u2014O(Ar) in the range 1.8796\u2005(17)\u20132.0005\u2005(16)\u2005\u00c5 \u2013 1.953\u2005(5)\u2005\u00c5. Within the binuclear complex anion there are six stabilizing intra-ion methyl C\u2014H\u22efO hydrogen-bonding inter\u00adactions methane  and nBuLi  was stirred in THF (20\u2005mL) at 273\u2005K under an N2 atmosphere for 2\u2005h. MgEt2  was gently added to the solution. After stirring at 298\u2005K for 6\u2005h, the solution was filtered through celite. The filtrate was concentrated to ca 10\u2005mL and cooled to 273\u2005K to furnish colourless crystals, suitable for the X-ray analysis. Yield: 0.46\u2005g (49%).A solution of tris\u00ad, or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017008337/zs2380sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017008337/zs2380Isup2.hklStructure factors: contains datablock(s) I. DOI: 1554461CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-pyrazol-5(4H)-one and its structural characterization by synchrotron single-crystal X-ray diffraction are reported.A synthetic approach to the new zinc complex based on amino\u00admethyl\u00adene derivative of 1-phenyl-3-methyl-4-[(quinolyl-3-yl)imino\u00admeth\u00adyl]-1 20H15N4O)2]\u00b72.5CH3OH, I, was synthesized via the reaction of zinc acetate with the respective ligand and isolated as a methanol solvate, i.e., as 3OHI\u00b72.5CH. The crystal structure is triclinic (space group P-1), with two complex mol\u00adecules (A and B) and five methanol solvent mol\u00adecules in the asymmetric unit. One of the five methanol solvent mol\u00adecules is disordered over two sets of sites, with an occupancy ratio of 0.75:0.25. Mol\u00adecules A and B are conformers and distinguished by the conformations of the bidentate 1-phenyl-3-methyl-4-[(quinolin-3-yl)imino\u00admeth\u00adyl]-1H-pyrazol-5-olate ligands. In both mol\u00adecules, the zinc cations have distorted tetra\u00adhedral coordination spheres, binding the monoanionic ligands through the pyrazolo\u00adlate O and imine N atoms. The two ligands adopt slightly different conformations in terms of the orientation of the terminal phenyl and quinoline substituents with respect to the central pyrazolo\u00adlate moiety. The mol\u00adecular geometries of A and B are supported by intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds. In the crystal of I, mol\u00adecules form dimers both by secondary inter\u00admolecular Zn\u22efO [3.140\u2005(2)\u20133.553\u2005(3)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions. The dimers are linked by inter\u00admolecular hydrogen bonds through the solvent methanol mol\u00adecules into a three-dimensional network.The title compound, [Zn(C ComplexA and B in I are four-coordinated by two monoanionic O,N-chelating ligands, which bind to the cation through pyrazolo\u00adlate O and imine N atoms. The coordination sphere around each zinc cation can be described as distorted tetra\u00adhedral , with dihedral angles between the planar six-membered chelating rings  of 82.97\u2005(7) and 84.52\u2005(7)\u00b0 for mol\u00adecules A and B, respectively.The zinc cations of A and B of I adopt different conformations. The main difference pertains to the twist angles of the terminal phenyl and quinoline substituents relative to the central imino\u00admethyl-1H-pyrazol-5-olate fragment. In mol\u00adecule A  and 8.24\u2005(11)\u00b0 for the phenyl groups, and 27.47\u2005(10) and 26.08\u2005(6)\u00b0 for the quinoline substituents. Thus, one of the two 1-phenyl-3-methyl-4-[(quinolin-3-yl)imino\u00admeth\u00adyl]-1H-pyrazol-5-olate ligands in mol\u00adecule B is flattened, while one of the two pyrazolo\u00adlate ligands in mol\u00adecule A is substanti\u00adally twisted \u2005\u00c5, Zn1\u22efO4 = 3.279\u2005(3)\u2005\u00c5, Zn2\u22efO1 = 3.553\u2005(3)\u2005\u00c5 and Zn2\u22efO2 = 3.140\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions between the O2/N5/N6/N7/C21\u2013C24 and O4/N13/N14/N15/C61\u2013C64 imino-methyl-pyrazolo\u00adnate fragments {the shortest distances are N6\u22efC63 [3.083\u2005(3)\u2005\u00c5], C21\u22efC62 [3.210\u2005(4)\u2005\u00c5], C24\u22efC64 [3.216\u2005(4)\u2005\u00c5], C21\u22efC61 [3.261\u2005(3)\u2005\u00c5], N14\u22efC23 [3.293\u2005(4)\u2005\u00c5], C22\u22efC61 [3.297\u2005(4)\u2005\u00c5], N6\u22efC62 [3.319\u2005(3)\u2005\u00c5] and N14\u22efC22 [3.362\u2005(3)\u2005\u00c5]}, as well as phenyl and pyridine rings  , where Cg3vii is the centroid of the C69vii\u2013C74vii benzene ring; symmetry code: (vii) \u2212x, \u2212y, \u2212z\u00a0+\u00a01] and \u03c0\u2013\u03c0 stacking inter\u00adactions {the shortest distances are between the C75\u2013C80 and C75viii\u2013C80viii phenyl rings [C75\u22efC79viii = 3.196\u2005(4)\u2005\u00c5 and C80\u22efC80viii = 3.279\u2005(4)\u2005\u00c5]; symmetry code: (viii) \u2212x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01}, as well as C\u2014H\u22efO and N\u22efH\u2014O hydrogen bonds involving the solvent methanol mol\u00adecules : 1664 \u03bd(C=O), 1627 \u03b4(NH). 1H NMR : \u03b4 2.31 , 7.08\u20138.03 , 8.52 , 8.89 , 11.46 . UV\u2013vis spectrum (nm): 232, 254, 358. PL spectrum (nm): \u03bbPL = 454, 534, \u03bbex = 450\u2005nm. Quantum yield of PL \u03c6 = 0.002. Analysis calculated for C20H16N4O: C 73.15, H 4.91, N 17.06%; found: C 73.25, H 5.10, N 17.18%.A solution containing 1.44\u2005g (0.01\u2005mol) of 3-amino\u00adquinoline in 10\u2005ml of toluene was added to a solution of 2.02\u2005g (0.01\u2005mol) of 1-phenyl-3-methyl-4-formyl\u00adpyrazol-5-one in 20\u2005ml of toluene. The mixture was refluxed for 3\u2005h with a Dean\u2013Stark trap until water stripping was completed. Subsequently, two-thirds of the total volume was distilled off on a rotary evaporator. The precipitate which formed was filtered off and recrystallized from ethanol to give light-yellow crystals . FT\u2013IR in KBr  in 20\u2005ml of the same solvent  mixture and dried at 423\u2005K, resulting in a yellow crystalline powder . FT\u2013IR : 1608 \u03bd(C=N). 1H NMR : \u03b4 2.25 , 6.99\u20138.92 , 8.46 . UV\u2013vis (nm): 360, 340, 304. PL (nm): \u03bbPL = 478, \u03bbex = 450\u2005nm. Analysis calculated for C40H30N8O2Zn: C 66.72, H 4.20, N 15.56%; found: C 66.78, H 4.25, N 15.64, Zn 9.11%.A hot solution of 0.22\u2005g of zinc acetate dihydrate (1\u2005mmol) in 20\u2005ml of methanol was added to hot solutions of nt Fig.\u00a05. The reaCrystal data, data collection and structure refinement details are summarized in Table\u00a02Scala program  using a Rayonix SX165 CCD detector. A total of 360 images were collected using an oscillation range of 1.0\u00b0  and corrected for absorption using the The data completeness of 97.8% is caused by the low (triclinic) crystal symmetry. It is very difficult to get a high data completeness for this symmetry using the \u03c6 scan mode only (\u2018Belok\u2019 beamline limitation), even though we have run two different crystal orientations.I/\u03c3 statistics for high-angle reflections, we selected an exposure time so as to admit a minor fraction of intensity overloads in the low-angle part of the detector. These low-angle reflections have imprecisely measured intensities and thus were excluded from the final steps of refinement. (ii) In the present set-up of the synchrotron diffractometer, the low-temperature device eclipses a small region of the 2D detector near the high-angle limit. This small shadowed region has not been masked during integration of the diffraction frames, which erroneously resulted in zero intensity of some reflections. (iii) The quality of the single crystal chosen for the diffraction experiment was not perfect. Some systematic differences between the calculated and observed intensities are probably caused by extinction and defects present in the crystal specimen.A rather large number of reflections have been omitted from refinement due to the following reasons. (i) In order to achieve better Uiso(H) = 1.5Ueq(O)]. All other H atoms were placed in calculated positions, with C\u2014H = 0.95\u20130.98\u2005\u00c5, and refined in a riding mode, with fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for the CH3 groups and 1.2Ueq(C) for the other groups]. Disorder over two sets of sites was observed for one methanol solvent mol\u00adecule (atoms O7\u2013C83). In the last cycles of refinement, the occupancy ratio was fixed at 0.75:0.25 and each of the non-H atoms was modelled with a common displacement ellipsoid.The H atoms of the hy\u00addroxy groups were localized from difference Fourier maps and included in a riding mode, with fixed displacement parameters [10.1107/S2056989017010441/wm5401sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017010441/wm5401Isup2.hklStructure factors: contains datablock(s) I. DOI: 1562057CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(4-chloro\u00adbenzene\u00adsulfon\u00adyl)glycinyl hydrazide with 4-nitro\u00adbenzaldehyde gives the N,N-di\u00admethyl\u00adformamide monosolvated N-acyl\u00adhydrazone derivative, (E)-N-{2-[2-(4-nitro\u00adbenzyl\u00adidene)- hydrazine-1-yl]-2-oxoeth\u00adyl}-4-\u03c7hloro\u00adbenzene\u00adsulfonamide. Rings of Reaction of  15H13ClN4O5S\u00b7C3H7NO, contains one mol\u00adecule each of the Schiff base and the solvent di\u00admethyl\u00adformamide. The hydrazone group adopts an E configuration about the C=N bond. The dihedral angle between the two aromatic rings is 86.58\u2005(2)\u00b0. In the crystal, pairs of N\u2014H\u22efO hydrogen bonds between centrosymmetrically related mol\u00adecules generates rings with an R22(10) graph-set motif. The dimers are further linked via N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, leading to the formation of R33(11) ring motifs. C\u2014H\u22ef\u03c0 inter\u00adactions are also observed. The inter\u00admolecular inter\u00adactions in the crystal structure were qu\u00adanti\u00adfied and analysed using Hirshfeld surface analysis, which indicates that the most significant contacts in packing are O\u22efH/H\u22efO (31.3%), followed by H\u22efH (25.4%) and C\u22efH/H\u22efC (13.0%).The asymmetric unit of the title compound, C The acidity of the C\u2014H donor group determines the strength of C\u2014H\u22efO inter\u00adactions -4-chloro-N-{2-[2-(4-nitro\u00adbenzyl\u00adidene)hydrazin-1-yl]-2-oxoeth\u00adyl}benzene\u00adsulfonamide N,N-di\u00admethyl\u00adformamide monosolvate.Supra\u00admolecular chemistry is based upon non-covalent inter\u00adactions such as hydrogen bonding, \u03c0\u2013\u03c0 stacking and van der Waals inter\u00adactions  and 1.274\u2005(6)\u2005\u00c5, respectively, confirm their double-bond character. The C8\u2014N2 and N2\u2014N3 bond distances  are shorter than normal bond lengths as a result of delocalization of the \u03c0-electron density. The mol\u00adecule is twisted at N1\u2014C7 with an S1\u2014N1\u2014C7\u2014C8 torsion angle of 166.5\u2005(4)\u00b0. The other central part of the mol\u00adecule is almost linear with C7\u2014C8\u2014N2\u2014N3, C8\u2014N2\u2014N3\u2014C9 and N2\u2014N3\u2014C9\u2014C10 torsion angles of \u22121.6\u2005(7), \u2212179.7\u2005(5) and 177.9\u2005(4)\u00b0, respectively. The orientations of the sulfonamide group with respect to the attached phenyl ring is given by the torsion angles of C2\u2014C1\u2014S1\u2014N1 = 98.1\u2005(5)\u00b0 and C6\u2014C1\u2014S1\u2014N1 = \u221280.2\u2005(5)\u00b0, while that of the hydrazone group with the attached phenyl ring by the torsion angles of C11\u2014C10\u2014C9\u2014N3 = 1.6\u2005(8)\u00b0 and C15\u2014C10\u2014C9\u2014N3 = \u2212177.4\u2005(5)\u00b0. The dihedral angle between the sulfonyl benzene ring and the mean plane through the SO2\u2014NH\u2014CH2\u2014CO segment is 82.653\u2005(18)\u00b0, while that between the C10\u2013C15 phenyl ring and the mean plane through the C9\u2014N3\u2014N2\u2014CO segment is 4.44\u2005(3)\u00b0. The dihedral angle between the two aromatic rings is 86.58\u2005(2)\u00b0. The C1\u2013C6 and C10\u2013C15 benzene rings are inclined to the mean plane of the central part of the hydrazone mol\u00adecule  by 86.4\u2005(3) and 4.5\u2005(3)\u00b0, respectively.The asymmetric unit of the title compound Fig.\u00a01 containsvia N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, generating rings with an via N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, leading to the formation of B) and the sulfonyl oxygen atom (O2) forming c axis, and the other involving an aromatic C\u2014H (H14) and the nitro O4 atom, giving rise to inversion dimers with an E)-4-methyl-N-{2-[2-(4-nitro\u00adbenz\u00adyl\u00adidene)hydrazin-1-yl]-2-oxoeth\u00adyl}benzene\u00adsulfonamide N,N-di\u00admeth\u00adyl\u00adform\u00adamide monosolvate  to analyse the close contacts in the title compound. The electrostatic potentials were calculated using TONTO  surface resolution with the 3D dnorm surfaces mapped over a fixed colour scale of \u22120.5849 to 1.3948. The curvedness was mapped in the colour range of \u22124.0 to 0.4. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree\u2013Fock level theory over a range \u00b10.1au.dnorm . The H\u22efH inter\u00adactions appear as the largest region of the fingerprint plot with a high concentration in the middle region, shown in light blue, at de = di \u223c1.4\u2005\u00c5  with an overall contribution to the Hirshfeld surfaces of 25.4%. The C\u22efH contacts, which refer to C\u2014H\u22ef\u03c0 inter\u00adactions, contribute 13.0% of the Hirshfeld surfaces. The presence of C\u2014H\u22ef\u03c0 inter\u00adactions is indicated by the appearance of two broad spikes having almost same de + di 3.1\u2005\u00c5. The C\u22efC contacts contribute 4.5% of the Hirshfeld surfaces, featuring two successive triangles with a minimum (de + di) distance of \u223c3.5\u2005\u00c5, which is greater than van der Waals separation, confirming the absence of \u03c0\u2013\u03c0 stacking inter\u00adactions. This is also evident from the absence of flat regions in the Hirshfeld surface mapped over curvedness glycine (L1) obtained was crystallized from aqueous ethanol. Sulfuric acid (0.5\u2005ml) was added to L1 (0.02\u2005mol) dissolved in ethanol (30\u2005ml) and the mixture was refluxed. The reaction mixture was monitored by TLC at regular inter\u00advals. After completion of the reaction, the reaction mixture was concentrated to remove the excess ethanol. The product, N-(4-chloro\u00adbenzene\u00adsulfon\u00adyl)glycine ethyl ester (L2) obtained was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone. The pure L2 (0.01\u2005mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10\u2005ml) in 30\u2005ml ethanol and the mixture was refluxed for 6\u2005h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-chloro\u00adbenzene\u00adsulfon\u00adyl)glycinyl hydrazide (L3). A mixture of L3 (0.01\u2005mol) and 4-nitro\u00adbenzaldehyde (0.01\u2005mol) in anhydrous methanol (30\u2005ml) and two drops of glacial acetic acid was refluxed for 8h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to a constant melting point from methanol (493\u2013496\u2005K).4-Chloro\u00adbenzene\u00adsulfonyl chloride (0.01\u2005mol) was added to glycine (0.02\u2005mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373\u2005K for 6\u2005h, left overnight at room temperature, then filtered and treated with dilute hydro\u00adchloric acid. The solid \u22121 for the stretching bands of N\u2014H, C=O, C=N, S=O asymmetric and S=O symmetric, respectively. 1H NMR : 3.68, 4.17 , 7.62\u20137.67 , 7.80\u20137.94 , 8.24\u20138.29 , 8.02 , 8.14 , 11.73, 11.75 . 13C NMR : 43.26, 44.42, 123.94, 127.85, 128.53, 129.19, 137.23, 139.77, 141.47, 144.68, 147.75, 164.52, 169.34. Plate-like yellow single crystals of the title compound suitable for X-ray analysis were grown from its DMF solution by slow evaporation of the solvent.The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3250.1, 1685.8, 1587.4, 1342.5 and 1166.9\u2005cmUeq or 1.5Ueq(C) for methyl H atoms.. The amino H atoms were freely refined with the N\u2014H distances restrained to 0.86\u2005(2)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901800292X/rz5227sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901800292X/rz5227Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901800292X/rz5227Isup3.cmlSupporting information file. DOI: 1433601CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The metal atom of the title compound is four coordinated. The asymmetrically appended Cl atom and a widely spread \u03c0-conjugated system of the complex mol\u00adecule construct the supra\u00admolecular structures of a hydrogen-bonded chain and a \u03c0\u2013\u03c0 inter\u00adacted column. 20H14ClN3O)], with an asymmetrically chloride-appended Schiff base ligand has been synthesized and structurally characterized at 100\u2005K. In the compound, the central nickel(II) ion has a square-planar coordination geometry with N3O donors of the \u03c0-conjugated tetra\u00addentate Schiff base ligand. In the crystal, the complexes are connected into an inversion dimer via an Ni\u22efNi inter\u00adaction [3.1753\u2005(5)\u2005\u00c5] and a pair of \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.8416\u2005(16)\u2005\u00c5]. The dimers are linked via a C\u2014H\u22efCl hydrogen bond, forming a chain along the c-axis direction. The dimer chains inter\u00adact with each other through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.8736\u2005(16)\u2005\u00c5], forming a layer expanding parallel to the ac plane.The title complex, [Ni(C Up to now, a large number of salen derivatives have been prepared and used for complexation in the expectation of a wide range of features such as catalytic ability, magnetic, dielectric and luminescence properties and so on  complex using an asymmetrically chloride-appended tetra\u00addentate Schiff base ligand.Metal complexes with a tetra\u00addentate Schiff base ligand as represented by H3O type asymmetrical ligand was reported by Ghorai & Mukherjee  complex with a similar Nrjee 2014.3O donor set including one phenolate O atom, two imine N atoms and one amino N atom of the tetra\u00addentate Schiff base ligand  atom is in a square-planar coordination with an asymmetrical coordination environment formed by the Nnd Fig.\u00a01. The Ni\u2014et al., 1996c axis \u2005\u00c5] and a pair of \u03c0\u2013\u03c0 inter\u00adactions between the C1\u2013C6 and C15\u2013C20 benzene rings [centroid\u2013centroid distance = 3.8415\u2005(16)\u2005\u00c5]. Such dimerization caused by an Ni\u22efNi inter\u00adaction has also been observed in symmetric Ni compounds  of Ni(CH3COO)2\u00b74H2O  was added to the solution and stirred for 1\u2005h. The resulting solution was allowed to stand for a few days, during which time dark-purple block-shaped crystals precipitated. They were collected by suction filtration and dried in air to give single crystals of the title compound suitable for X-ray diffraction.The tetra\u00addentate Schiff base ligand was prepared by the reaction of 2-amino\u00adbenzaldehyde  = 1.5Ueq(N). Other H atoms were treated as riding with C\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017004613/is5472sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017004613/is5472Isup2.hklStructure factors: contains datablock(s) I. DOI: 1539785CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure of the insecticide fipronil is reported. In the crystal, N\u2014H\u22efN, N\u2014H\u22efO, C\u2014H\u22efF hydrogen bonds, C\u2014N\u22ef\u03c0 and C\u2014Cl\u22ef\u03c0 inter\u00adactions link adjacent mol\u00adecules, forming a three-dimensional network. In addition, there are short F\u22efF inter\u00adactions present. 12H4Cl2F6N4OS {systematic name: 5-amino-1--4-[(tri\u00adfluoro\u00admethane)sulfinyl]-1H-pyrazole-3-carbo\u00adnitrile}, is a member of the phenyl\u00adpyrazole group of acaricides, and one of the phenyl\u00adpyrazole group of insecticides. The dihedral angle between the planes of the pyrazole and benzene rings is 89.03\u2005(9)\u00b0. The fluorine atoms of the tri\u00adfluoro\u00admethyl substituent on the benzene ring are disordered over two sets of sites, with occupancy ratios 0.620\u2005(15):0.380\u2005(15). In the crystal, C\u2014N\u22ef\u03c0 inter\u00adactions [N\u22efring centroid = 3.607\u2005(4)\u2005\u00c5] together with N\u2014H\u22efN and C\u2014H\u22efF hydrogen bonds form a looped chain structure along [10The title compound, C It is an insecticide with extended use in the control of many agricultural vermin. Fipronil contains a tri\u00adfluoro\u00admethyl\u00adsulfinyl substituent that is not present in any other agrochemicals and this is thought to contribute to its remarkable potency in the field \u2005\u00c5; Cg1 is the centroid of the C5\u2013C10 ring; symmetry code: (iii) \u2212x, y, \u2212z], together with N3\u2014H3A\u22efN4i and C9\u2014H9\u22efF2i hydrogen bonds, forming looped chains along  (red dashed lines), link adjacent chains, resulting in a two-dimensional network parallel to the (10B\u22efO1ii hydrogen bonds (black dashed lines) combine with these contacts to generate a three-dimensional network structure \u2005\u00c5] and F3\u22efF6\u2032vi [2.855\u2005(12)\u2005\u00c5] inter\u00adactions are also present .In the crystal, mol\u00adecules are linked by C12\u2014N4\u22ef0] Fig.\u00a02. Inversine Fig.\u00a03. Finallyre Fig.\u00a04. Short Fet al., 2005et al., 2013II, CdII, ZnII and MnII complexes using fipronil as a ligand are known -methyl\u00adidene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one  = 0.88\u2005\u00c5, Uiso = 1.2Ueq(C) for the N\u2014H group, d(C\u2014H) = 0.95\u2005\u00c5, Uiso = 1.2Ueq(C) for aromatic C\u2014H. Atoms F4\u2013F6 of the CF3 substituent are disordered over two sets of sites. Their occupancies refined to 0.620\u2005(15) and 0.380\u2005(15).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901701310X/sj5534sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901701310X/sj5534Isup2.hklStructure factors: contains datablock(s) I. DOI: 1574261CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title compound consists of discrete octa\u00adhedral complexes that are linked by inter\u00admolecular O\u2014H\u22efS, C\u2014H\u22efCl, C\u2014H\u22efS and C\u2014H\u22efCl hydrogen bonding. 2(C5H4ClN)2(H2O)2], consists of one nickel(II) cation that is located on a center of inversion and one thio\u00adcyanate anion, one water mol\u00adecule and one 2-chloro\u00adpyridine ligand all occupying general positions. The NiII cation is octa\u00adhedrally coordinated by two terminal N-bound thio\u00adcyanato ligands, two aqua ligands and two N-bound 2-chloro\u00adpyridine ligands into discrete complexes. Individual complexes are linked by inter\u00admolecular O\u2014H\u22efS and O\u2014H\u22efCl hydrogen-bonding inter\u00adactions into a layered network extending parallel to the bc plane. Weak inter\u00adactions of types C\u2014H\u22efS and C\u2014H\u22efCl consolidate the crystal packing.The asymmetric unit of the title compound, [Ni(NCS) The cation is located on a center of inversion whereas all ligands are located on general positions. The NiII cation is coordinated by two terminal N-bound inorganic anionic ligands, two water mol\u00adecules and two 2-chloro\u00adpyridine ligands that are coordinated via the pyridine N atom in an all-trans configuration on Fig.\u00a01. As expeb axis \u00b76H2O and 2-chloro\u00adpyridine were purchased from Alfa Aesar. Ni(NCS)2 was synthesized by stirring 17.5\u2005g Ba(NCS)2\u00b73H2O (57\u2005mmol) with 15.0\u2005g Ni(SO4)\u00b76H2O (57\u2005mmol) in 500\u2005ml water. The green residue was filtered off and the filtrate was dried using a rotary evaporator. The homogeneity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 26.2\u2005mg Ni(NCS)2 (0.15\u2005mmol) with 56.0\u2005\u00b5l 2-chloro\u00adpyridine (0.6\u2005mmol) in ethanol (1.0\u2005ml) after a few days.Ba(NCS)Uiso(H) = 1.2Ueq(C). The OH H atoms were located in a difference map, and their bond lengths constrained to 0.82\u2005\u00c5, with Uiso(H) = 1.5Ueq(O).Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989016015218/wm5326sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326Isup2.hklStructure factors: contains datablock(s) I. DOI: 1506903CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One of the two n-pentyl side chains was refined as disordered over two sets of sites, with occupancies of 0.733\u2005(18) and 0.267\u2005(18). The geometry around the HgII atom in the [HgCl4]2\u2212 anion is distorted tetra\u00adhedral, with bond angles ranging from 98.16\u2005(3) to 120.68\u2005(3)\u00b0. In the [HgCl4]2\u2212 anion, there are two short Hg\u2014Cl bonds [2.4120\u2005(9) and 2.4171\u2005(11)\u2005\u00c5], one inter\u00admediate Hg\u2014Cl bond [2.4716\u2005(12)\u2005\u00c5] and one long Hg\u2014Cl bond [2.6579\u2005(13)\u2005\u00c5] for the Cl atom involved in a trifurcated hydrogen bond as an acceptor, including two N\u2014H\u22efCl\u22efH\u2014N interactions as well as one C\u2014H\u22efCl inter\u00adaction. There are several C\u2014H\u22efCl inter\u00adactions, with C\u22efCl distances ranging from 3.492\u2005(3) to 3.796\u2005(3)\u2005\u00c5. These link the cations and anions into a zigzag chain along the c-axis direction. In addition, there are Cl\u22efCl halogen bonds, as well as \u03c0\u2013\u03c0 inter\u00adactions, with centroid-to-centroid distances of 3.4765\u2005(18)\u2005\u00c5, which link one of the two benzimidazole moieties into dimeric units.In the title salt, (C H-benzo[d]imidazol-2-yl)benzene have been well explored. This ligand is an ideal candidate for metalation due to the presence of two N atoms and one C atom, which bind tightly with metal atoms . Reports of structurally related complex have been published recently -2-(di\u00adchloro\u00adstiban\u00adyl)-1,3-phenyl\u00adene)bis\u00ad(1-pentyl-1H-benzimidazole) (2) from (4-(tert-but\u00adyl)-2,6-bis\u00ad(1-pentyl-1H-benzimidazol-2-yl)phen\u00adyl)mercury(II) chloride; [C34H41N4HgCl] (1) using SbCl3 in dry 1,4-dioxane via transmetallation. Related reactions  to 120.68\u2005(3)\u00b0. In the [HgCl4]2\u2212 anion, there are two short Hg\u2014Cl bonds , one inter\u00admediate Hg\u2014Cl bond  and one long Hg\u2014Cl bond  for the Cl atom involved in a trifurcated bond as an acceptor including two N\u2014H\u22efCl\u22efH\u2014N interactions as well as one C\u2014H\u22efCl inter\u00adaction , \u2212175.0\u2005(15), 179.7\u2005(15), and \u2212178.1\u2005(9)\u00b0, respectively, while for C30\u2013C34 they are C23\u2014N3\u2014C30\u2014C31, N3\u2014C30\u2014C31\u2014C32, C30\u2014C31\u2014C32\u2014C33, and C31\u2014C32\u2014C33\u2014C34 . Thus the first side chain is in an all-trans conformation while the second side chain has adopted a conformation where it curls up at the end.In the ligand, the dihedral angles between the benzimidazole moieties and central phenyl ring are 40.60\u2005(9) and 38.08\u2005(10)\u00b0, while the angle between them is 36.04\u2005(6)\u00b0. One of the pentyl substituents was refined as disordered over two sets of sites, with occupancies of 0.733\u2005(18)/0.267\u2005(18). The two pentyl side chains have adopted different conformations  and this is illustrated by their torsion angles. For C8c-axis direction, as shown in Fig.\u00a03x, \u2212y, 2\u00a0\u2212\u00a0z) with centroid-to-centroid distances of 3.477\u2005(2)\u2005\u00c5.In addition to the inter-ionic hydrogen bonds mentioned above, there are several C\u2014H\u22efCl inter\u00adactions with C\u22efCl distances ranging from 3.492\u2005(3) to 3.796\u2005(3)\u2005\u00c5 (see Table1). These link the cations and anions into a zigzag chain in the n-hexyl rather than n-pentyl side chains  for salts containing both the benzimidazole moiety as well as the tetra\u00adchlorido\u00admercurate(II) anion gave eight hits, including a closely related ligand with 1  in dry 1,4-dioxane was added SbCl3  at room temperature. The reaction mixture was refluxed for 6\u2005h under an inert atmosphere of N2 and filtered through Whatman filter paper. When the solvent was evaporated, a white-colored precipitate was obtained and purified by washing with hexane. The compound was dried under vacuum. Colourless block-shaped single crystals were obtained from MeOH at room temperature, yield 64% (0.120\u2005g).The reaction scheme is shown in Fig.\u00a011H NMR : \u03b4 8.13 , 7.91 , 7.82 , 7.49\u20137.45 , 4.43 , 1.74 , 1.43 , 1.14 , 0.72 . 13C NMR : 153.1, 151.4, 137.9, 134.7, 129.4, 128.5, 128.2, 124.7, 124.5, 117.8, 112.6, 45.1, 35.5, 31.3, 29.1, 28.5, 21.9, 14.1.n-pentyl side chains was refined as disordered over two sets of sites, with occupancies of 0.733\u2005(18) and 0.267\u2005(18) and both conformers were constrained to have similar metrical parameters using the SAME command in SHELXL2016. H atoms were positioned geometrically and refined as riding: N\u2014H = 0.88\u2005\u00c5 with Uiso(H) = 1.2Ueq(N); C\u2014H = 0.95\u20130.98\u2005\u00c5 with 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017004303/zl2697sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004303/zl2697Isup2.hklStructure factors: contains datablock(s) I. DOI: 1538746CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "CD4+NKG2D+ T cells are associated with tumour, infection and autoimmune diseases. Some CD4+NKG2D+ T cells secrete IFN\u2010\u03b3 and TNF\u2010\u03b1 to promote inflammation, but others produce TGF\u2010\u03b2 and FasL to facilitate tumour evasion. Here, murine CD4+NKG2D+ T cells were further classified into NK1.1\u2212CD4+NKG2D+ and NK1.1+CD4+NKG2D+ subpopulations. The frequency of NK1.1\u2212CD4+NKG2D+ cells decreased in inflamed colons, whereas more NK1.1+CD4+NKG2D+ cells infiltrated into colons of mice with DSS\u2010induced colitis. NK1.1\u2212CD4+NKG2D+ cells expressed TGF\u2010\u03b2 and FasL without secreting IFN\u2010\u03b3, IL\u201021 and IL\u201017 and displayed no cytotoxicity. The adoptive transfer of NK1.1\u2212CD4+NKG2D+ cells suppressed DSS\u2010induced colitis largely dependent on TGF\u2010\u03b2. NK1.1\u2212CD4+NKG2D+ cells did not expressed Foxp3, CD223 (LAG\u20103) and GITR. The subpopulation was distinct from NK1.1+CD4+NKG2D+ cells in terms of surface markers and RNA transcription. NK1.1\u2212CD4+NKG2D+ cells also differed from Th2 or Th17 cells because the former did not express GATA\u20103 and ROR\u2010\u03b3t. Thus, NK1.1\u2212CD4+NKG2D+ cells exhibited immune regulatory functions, and this T cell subset could be developed to suppress inflammation in clinics. Ligands of human NKG2D include MHC class I chain\u2010related protein A/B (MICA/MICB) and UL16\u2010binding proteins (ULBPs). Mouse NKG2D ligands include retinoic acid early induced transcript\u20101 , H60 and murine ULBP\u2010like transcript 1 (MULT\u20101) + T cells. NKG2D in association with its adaptor molecules, namely DAP10 or DAP12, transduces signalling by the activation of phosphatidylinositol 3\u2010kinase (PI3K), resulting in cell activation, survival, cytoskeletal rearrangement and release of cytokines and cytotoxic granules NKG2D is an activating receptor expressed on natural killer (NK) cells, CD8+ NKG2D+ T cells are associated with inflammatory diseases, such as rheumatoid arthritis (RA) + NKG2D+ T cells + NK2D+ T cells exhibit Th1\u2010like properties in tissues because of the produced IFN\u2010\u03b3, TNF\u2010\u03b1 and cytolytic granules. IL\u201015 of the microenvironment either in cis or in trans form contributes to the induction of CD4+ NKG2D+ T cell subset CD4+ NKG2D+ T cell population, which is associated in regulatory activities, is normally found in healthy individuals; CD4+ NKG2D+ T cell population is inversely correlated with disease severity in patients with juvenile\u2010onset systemic lupus, suggesting that CD4+ NKG2D+ T cells acts in regulation rather than inflammation + NKG2D+ T cells with regulatory activity is largely dependent on FasL and TGF\u2010\u03b2; hence, this T cell subset features an immunosuppressive property CD4+ NKG2D+ T cell population significantly increased in RAE\u20101\u03b5 transgenic mice, whose RAE\u20101\u03b5 expression was controlled by the CD86 promoter. CD4+ NKG2D+ T cells produced TGF\u2010\u03b2 to down\u2010regulate NKG2D expression on NK cells, whereas Foxp3 was not expressed in the cytoplasm + NKG2D+ T cells are associated with colitis induced by dextran sodium sulphate (DSS) in mice. Furthermore, whether the subsets of CD4+ NKG2D+ T cells with distinct function could be discriminated by additional cell markers remains unclear. Results show that the frequency of NK1.1\u2212 CD4+ NKG2D+ T cells in colon is negatively correlated with colitis induced by DSS, and NK1.1\u2212 CD4+ NKG2D+ T cell differs from NK1.1+ CD4+ NKG2D+ T cells in terms of cell membrane markers and transcriptional RNAs.The number of mouse CD4The following antibodies were obtained from Biolegend  or eBioscience : CD3 (17A2), \u03b3\u03b4 (GL3), CD8 (53.67), CD4 (GK1.5), NK1.1 (PK136), NKG2D (CX5), CD107a (1D4B), IFN\u2010\u03b3 (XMG1.2), NKp46 (29A1.4), NKG2A (16A11), Ly49D (4E5), Ly49H (3D10), TGF\u2010\u03b2 (TW7\u201016B4), FasL (MFL3), IL\u201010 (JES5\u201016E3), IL\u201017 (eBio17B7), CD62L (MEL\u201014), CD44 (IM7), granzyme B (NG2B), perforin (eBioOMAK\u2010D), CD25 (PC61.5), Foxp3 (FJK\u201016S), GITR (YGITR 765), CTLA\u20104 (UC10\u20104B9), CD39 (24DMS1), CD69 (LG.3A10), CCR9 (CW\u20101.2), CD28 (E18), T\u2010bet (4B10), GATA\u20103 (16E10A23) and ROR\u2010\u03b3t (AFKJS\u20109), neutralized TGF\u2010\u03b2 antibody (1D11) and RAE\u20101\u03b5 mAb (205001). C57BL/6 and pCD86\u2010RAE\u20101 transgenic mice n\u00a0=\u00a05). All mice were weighed every day. To assess the extent of colitis, loss in bodyweight , stool consistency  and blood in the stool  were monitored daily by trained individuals blinded to the treatment groups. Disease activity scores are calculated using the total score, which ranged from 0 to 12. The mice were killed on day 8, and the spleens and intestinal tissues were removed for ex\u00a0vivo analysis. All experimental protocols were approved by the Institutional Animal Care and Use Committee of Yangzhou University.Colitis was induced by administration of DSS  to drinking water for 7\u00a0days . The tissues were dissected longitudinally, washed completely and cut into smaller pieces. The tissues were then predigested by Hanks\u2019 balanced salt solution (HBSS) with 5\u00a0mM EDTA and 1\u00a0mM DTT at 37\u00b0C for 20\u00a0min. Mixed cell solution was passed through a nylon filter (100\u00a0\u03bcm) and then digested in PBS containing collagenase D (0.5\u00a0g/L), DNase I (0.5\u00a0g/L) and dispase II (3\u00a0g/L) for another 20\u00a0min. The cell suspension was centrifuged, suspended and washed with RPMI 1640 three times. The mixed cells were supplemented with 35% Percoll and then centrifuged to isolate mononuclear cells. Finally, the mononuclear cells were washed with PBS for further study.Cytokine production was determined using an intracellular staining kit (eBioscience). Lymphocytes were cultured with PMA (200\u00a0ng/ml)/ionomycin (2\u00a0\u03bcg/ml) in the presence of brefeldin A (10\u00a0\u03bcg/ml) for 4\u00a0hrs at 37\u00b0C. At the end of the incubation period, the cells were pre\u2010stained with antibody against surface markers. The cells were fixed, permeabilized, stained with cytokine or isotype antibody and analysed by flow cytometry. Lymphocytes were also permeabilized in referenced buffer and incubated with antibodies against Foxp3, T\u2010bet, GATA\u20103 or ROR\u2010\u03b3t.Mouse tissues were embedded in OCT and frozen instantly in liquid nitrogen for cryostat sections. After fixation, the sections were blocked with donkey serum and stained with goat antimouse RAE\u20101\u03b5 antibody . The sections were washed and stained with Alexa\u2010546 labelled donkey anti\u2010goat as secondary antibody. The sections were covered with DAPI . Fluorescence was detected using Eclipse E600  microscope and analysed using NIS\u2010Elements software .\u2212 CD4+ cells from pCD86\u2010RAE\u20101 transgenic mice were negatively isolated using a CD4+ T cell isolation kit. The cells were stained with PE\u2010antimouse NKG2D antibody and magnetic\u2010labelled anti\u2010PE antibody sequentially. The sorted CD4+ NKG2D+ T cells (5\u00a0\u00d7\u00a0105) were injected into the tail vein of DSS\u2010 or PBS\u2010treated mice (n\u00a0=\u00a05) on days 1, 3 and 5. On day 7, the mice were killed to obtain mononuclear colon cells and spleens. Frequencies of CD4+ NKG2D+ T cells were analysed using flow cytometry gated on 7\u2010AAD\u2212 CD45+ NK1.1\u2212 cells.Splenic NK1.1\u2212 CD4+ NKG2D+ and NK1.1+ CD4+ NKG2D+ cells of normal C57BL/6 mice were sorted using flow cytometry. The sorted cells were lysed in TRIzol reagent  and reverse\u2010transcribed into complementary DNAs. The DNA profiles were detected by GeneChip\u00ae Mouse Transcriptome Assay 1.0  in Shanghai GIMIX Information Technology Company. Data were analysed by GCBI online software.Splenic NK1.1\u2212 CD45+ CD4+ NKG2D+ cells were analysed. The frequency of CD4+ NKG2D+ cells was significantly down\u2010regulated in the local inflamed colons of DSS\u2010treated mice   and CTLA\u20104, but expressed CD39 at low levels  profiles were analysed by gene chips. A total of 161 mRNA genes  + NKG2D+ cells was determined by costimulation of the MHC II molecule and NKG2D ligand \u2212 CD4+ NKG2D+ cell after coligation of TCR and NKG2D are still being studied.CD4+ NKG2D+ T cells was observed in patients with rheumatoid arthritis + NKG2D+ T cells were negative in grade 1 cervical intraepithelial neoplasia and melanoma patients treated with sorafenib + NKG2D+ T cells of patients with Crohn's disease. Th17 and Th1 represent 30%\u00a0\u00b1\u00a017% and 12%\u00a0\u00b1\u00a05%, respectively, of the lamina propria CD4+ NKG2D+ population + CD4+ NKG2D+ cells produced IFN\u2010\u03b3, IL\u201017 and IL\u201021, indicating that the NK1.1+ CD4+ NKG2D+ subset may resemble human CD161+ CD4+ NKG2D+ cells involved with inflammation The pro\u2010inflammatory role of CD4\u2212 CD4+ NKG2D+ cells showed distinctive markers from NK1.1+ CD4+ NKG2D+ cells. NKp46 \u2212 CD4+ NKG2D+ cells. Given that IL\u201015 stimulations can program T cells to express NK cell markers, such as NKp46 and NKG2A \u2212 CD4+ NKG2D+ cells may not depend on IL\u201015 alone. Induction of the subset in\u00a0vitro requires coligations of TCR and NKG2D. Naturally occurring regulatory CD4+ NKG2D+ cells were also found in humans \u2212 CD4+ NKG2D+ cells could be produced in thymus innately or induced outside.NK1.1\u2212 CD4+ NKG2D+ cells into the colon with colitis decreased, whereas the frequency of NK1.1\u2212 CD4+ NKG2D+ cells in the spleen of mice was enhanced. Under inflammatory conditions, NK1.1\u2212 CD4+ NKG2D+ cells would be redistributed because of the local environment. NK1.1\u2212 CD4+ NKG2D+ T cells expressed low levels of CD39 \u2212 CD4+ NKG2D+ T cells exhibit potential to migrate into colon tissues. The retention of NK1.1\u2212 CD4+ NKG2D+ T cells in spleens partly resulted from the enhanced expression level of NKG2D ligands of splenic macrophages or DCs under the DSS\u2010induced inflammatory situations. Macrophages or DCs would up\u2010regulate NKG2D ligand expression when they are stimulated by Toll\u2010like receptor ligand \u2212 CD4+ NKG2D+ T cells, because pCD86\u2010RAE\u20101 transgenic mice showed higher expression levels of RAE\u20101 in the colons after DSS treatment than those of the wild mice.The infiltration of NK1.1+ NKG2D+ T cells were further categorized into NK1.1\u2212 CD4+ NKG2D+ T and NK1.1+ CD4+ NKG2D+ T subsets. NK1.1\u2212 CD4+ NKG2D+ T cells suppressed colitis induced by DSS in mice via production of TGF\u2010\u03b2. Regulatory NK1.1\u2212 CD4+ NKG2D+ T cells differ from conventional CD4+ CD25+ Foxp3+ cells and do not have features of NK1.1+ CD4+ NKG2D+ T cells in both phenotype and RNA transcription. This article provides biological features of regulatory NK1.1\u2212 CD4+ NKG2D+ T cells of mice and indicated that NK1.1\u2212 CD4+ NKG2D+ T cells may be used for treatment of inflammation\u2010associated diseases.In conclusion, CD4All authors have declared there are no financial conflicts of interest with regard to this work.Figure\u00a0S1 Detection of colonic T and NK cells of mice treated by DSS or PBS.Figure\u00a0S2 Detection of splenic T and NK cells of mice treated by DSS or PBS.Figure\u00a0S3 Detection of splenic CD3+ \u0263\u03b4\u2212 NK1.1+ CD4+ NKG2D+ T of mice treated by DSS or PBS.Figure\u00a0S4 Expression of Foxp3 in splenic NK1.1\u2212CD4+NKG2D+ Foxp3+ cells of CD86\u2010transgenic or wild type mice treated by DSS.Figure\u00a0S5 Production of IFN\u2010\u0263, IL\u201017, and IL\u201021 by NK1.1+ CD4+NKG2D+ cells of mice treated by DSS or PBS.Figure\u00a0S6 Membrane TGF\u2010\u03b2 on NK1.1\u2212CD4+NKG2D+ cells of spleens from mice treated by DSS or PBS.Click here for additional data file."}
{"text": "EXE) treats estrogen receptor positive (ER+) breast cancer in postmenopausal women by inhibiting the estrogen\u2010synthesizing cytochrome P450 CYP19A1. Variability in the severity and incidence of side effects as well as overall drug efficacy may be partially explained by genetic factors, including nonsynonymous variation in CYP19A1, also known as aromatase. The present study identified phase I EXE metabolites in human liver microsomes (HLM) and investigated mechanisms that may alter the extent of systemic estrogen deprivation in EXE\u2010treated women with breast cancer, including whether functional polymorphisms in aromatase cause differential inhibition by EXE and whether EXE metabolites possess anti\u2010aromatase activity. The potency of EXE and ten of its derivatives was measured with HEK293\u2010overexpressed wild type aromatase (CYP19A1*1) using a rapid novel UPLC tandem mass spectrometry method. Of the ten compounds assayed, five were poor inhibitors (IC50\u00a0\u02c3\u00a050\u00a0\u03bcmol/L) of wild type aromatase while five others, including the major metabolite, 17\u03b2\u2010dihydroexemestane (17\u03b2\u2010DHE), exhibited moderate potency, with IC50 values ranging between 1.2 and 7.1\u00a0\u03bcmol/L. The anti\u2010aromatase activity of EXE was also tested with two common allozymes, aromataseThr201Met (CYP19A1*3) and aromataseArg264Cys (CYP19A1*4). Differential inhibition of variant aromatase is unlikely to account for variable clinical outcomes as EXE\u2010mediated inhibition of aromataseThr201Met (IC50\u00a0=\u00a00.86\u00a0\u00b1 0.12\u00a0\u03bcmol/L) and aromataseArg264Cys (IC50\u00a0=\u00a01.7\u00a0\u00b1\u00a00.65\u00a0\u03bcmol/L) did not significantly differ from wild type (IC50\u00a0=\u00a00.92\u00a0\u00b1\u00a00.17\u00a0\u03bcmol/L). Although less potent than the parent drug, these results suggest that active metabolites may contribute to the therapeutic mechanism of EXE.Exemestane ( A key p\u03b2\u2010DHE as a major metabolite in human plasma has been unequivocally confirmed in studies of postmenopausal women taking EXE   . Corning  and Integrated DNA Technologies  manufactured the NADPH regeneration system and oligonucleotide primers, respectively. A QuikChange II Site\u2010Directed Mutagenesis Kit was purchased from Agilent  to produce aromatase variant overexpression vectors. The HEK293 cell line was procured from ATCC . G418, penicillin/streptomycin, fetal bovine serum, Opti\u2010MEM, and DMEM supplemented with 4.5\u00a0g/L glucose, 110\u00a0mg/L sodium pyruvate, and L\u2010glutamine was purchased from Invitrogen  along with an XCell electrophoresis system. Lipofectamine 2000, PVDF membranes, Pierce BCA protein assay kit, SuperSignal West Femto Maximum Sensitivity Substrate, sodium dodecyl sulfate (SDS), glycine, tris base, ammonium persulfate (APS), goat anti\u2010rabbit HRP\u2010conjugated antibody (cat. No. 31466), and tetramethylethylenediamine (TEMED) were also purchased from Thermo Fisher Scientific. Nonfat dry milk was prepared by BioRad . Sigma\u2010Aldrich  supplied Ponceau staining solution, Tween 20, acrylamide/bis\u2010acrylamide solution, 2\u2010mercaptoethanol, estrone, androstenedione substrate, and estrone\u20102,3,4\u201013C3. Rabbit monoclonal anti\u2010aromatase antibody (cat. no. ab124776) was purchased from Abcam .Hangzhou DayangChem Co.  supplied the androgens boldenone, testosterone, and 4\u2010andostene\u20103,17\u2010dione for the synthesis of EXE and its analogs. Tokyo Chemical Industry Co. , Thermo Fisher Scientific , and Sigma\u2010Aldrich  produced all other reagents (ACS grade or higher) needed for synthesis. Steroid purification required silica columns  and thin\u2010layer chromatography plates . LC/MS grade methanol, acetonitrile, and formic acid was purchased from Thermo Fisher Scientific. XenoTech  supplied pooled mixed gender human liver microsomes . Previous studies provide detailed descriptions of the synthesis, purification, and NMR\u2010based identity verification of each compound  in a chilled Beckman L7\u201065 ultracentrifuge , resuspended in PBS, and stored at \u221280\u00b0C. The relative expression of aromatase was quantitated in triplicate by subjecting 20\u00a0\u03bcg of protein from each overexpressing cell line to SDS\u2010PAGE in a 10% tris\u2010glycine polyacrylamide gel. Following transfer to PVDF for 90\u00a0min at 30\u00a0V, the membrane was blocked overnight at 4\u00b0C in 5% nonfat dry milk, washed for 30\u00a0min in 0.1% Tween, and probed overnight with anti\u2010aromatase primary antibody (1:2500). The next day, the membrane was again washed for 30\u00a0min, and probed with HRP\u2010conjugated goat anti\u2010rabbit antibody (1:7500) for 1\u00a0h at ambient temperature. Following another 30\u00a0min wash, the blot was incubated with SuperSignal West Femto Maximum Sensitivity Substrate per the manufacturer instructions and imaged on a ChemiDoc Imager . Image J software  was used to measure band density while Ponceau staining was used to validate even loading between lanes.Stable overexpression of wild type aromatase in HEK293 was driven by a pcDNA3.1/V5\u2010His\u2010TOPO mammalian expression vector as previously described , 5\u00a0\u03bcmol/L androstenedione, a NADPH regeneration system , and 15\u00a0\u03bcg of microsomes from HEK293 overexpressing wild type or variant aromatase were individually incubated with varying concentrations of each steroid. The\u00a0steroid concentrations used for anti\u2010aromatase activity\u00a0assays\u00a0are as follows: EXE (0.05\u201015\u00a0\u03bcmol/L), 17\u03b2\u2010DHE (0.05\u201330 \u03bcmol/L), 17\u03b1\u2010DHE (100\u00a0\u03bcmol/L), 6\u03b1\u2010spirooxiranandrosta\u20101,4\u2010diene\u20103,17\u2010dione (0.05\u201330\u00a0\u03bcmol/L), 6\u03b2\u2010spirooxiranandrosta\u20101,4\u2010diene\u20103,17\u2010dione (0.05\u201340\u00a0\u03bcmol/L), 6\u03b1\u2010methylandrosta\u20101,4,6\u2010triene\u20103,17\u2010dione (0.5\u201330\u00a0\u03bcmol/L), 6\u03b1\u2010methylandrosta\u20101,4\u2010diene\u20103,17\u2010dione (0.2\u201330\u00a0\u03bcmol/L), 6\u2010hydroxymethylandrosta\u20101,4,6\u2010triene\u20103,17\u2010dione (2.5\u2013300\u00a0\u03bcmol/L), 17\u03b2\u2010hydroxy\u20106\u2010hydroxymethylandrosta\u20101,4,6\u2010triene\u20103\u2010one (100\u00a0\u03bcmol/L), 6\u03b1/\u03b2\u2010hydroxy\u20106\u03b1/\u03b2\u2010hydroxymethylandrosta\u20101,4\u2010diene\u20103,17\u2010dione (100\u00a0\u03bcmol/L), and 6\u03b1/\u03b2,17\u03b2\u2010Dihydroxy\u20106\u03b1/\u03b2\u2010hydroxymethylandrosta\u20101,4\u2010diene\u20103\u2010one (100\u00a0\u03bcmol/L). Organic solvent comprised <1% of the total volume of each enzymatic incubation, which proceeded at 37\u00b0C for 2\u00a0h. Reactions were terminated with 50\u00a0\u03bcl of ice cold acetonitrile and centrifuged at 4\u00b0C for 15\u00a0min at 13,200g. Supernatants were collected and spiked with 50\u00a0ng of estrone\u20102,3,4\u201013C3 as an internal standard. An incubation with microsomes derived from non\u2010transfected HEK293 was also performed to serve as a negative control. Aromatization catalyzed by wild\u2010type or variant aromatase was likewise monitored in the presence of vehicle rather than EXE or compounds from the reference library to reflect maximal uninhibited estrone formation. Estrone was measured using a novel 6\u2010min direct detection UPLC/MS/MS method on the Waters Acquity platform using m/z transitions 271.17\u2192133.09 as a marker for estrone and 274.15\u2192162 for estrone\u20102,3,4\u201013C3. Mobile phase (57% methanol in 0.1% formic acid) was infused isocratically from 0 to 4\u00a0min at a flow rate of 0.4\u00a0mL/min. The column was then washed with methanol for 1\u00a0min followed by 1\u00a0min of re\u2010equilibration with mobile phase. Cone and collision voltages were set at 35\u00a0V and 20\u00a0V respectively. Dwell time for both compounds was 0.1\u00a0sec. IC50 values from incubations with wild\u2010type aromatase were calculated for each compound in GraphPad Prism 6 . One\u2010way ANOVA was used to compare the IC50 value for EXE incubated with wild type aromatase with IC50 values for EXE incubated with overexpressed aromatase allozymes.Per 50\u2010\u03bcl incubation containing 50\u00a0\u03bcg of HLM in PBS (pH 7.4), 400\u00a0\u03bcmol/L EXE, and an NADPH regeneration system was placed in a 37\u00b0C water bath for 4\u00a0h before termination with 50\u00a0\u03bcL of cold acetonitrile. After a 15\u2010min refrigerated centrifugation at 13,200g, the supernatant was examined for phase I EXE metabolites. A 10\u2010min UPLC method was used to separate and detect EXE and the ten other reference compounds through multiple reaction monitoring with positive mode electrospray ionization on a Waters ACQUITY UPLC/MS/MS system . The 1.7\u00a0\u03bcm ACQUITY UPLC BEH C18 column  used for these analyses was protected by a 0.2\u00a0\u03bcm in\u2010line filter. The UPLC gradient conditions used have previously been described  and its major metabolite 17\u03b2\u2010DHE (IC50\u00a0=\u00a04.3\u00a0\u00b1\u00a00.56\u00a0\u03bcmol/L) were potent and moderate inhibitors of aromatase respectively. These results agree with an earlier study which found that 17\u03b2\u2010DHE was approximately 2.6\u2010fold less potent than EXE , exhibiting nearly 5\u2010fold more potency than its 6\u03b2 stereoisomer (IC50\u00a0=\u00a05.7\u00a0\u00b1\u00a01.6\u00a0\u03bcmol/L). 17\u03b1\u2010DHE and three additional compounds exhibited negligible aromatase inhibition with IC50 values exceeding 100\u00a0\u03bcmol/L  than EXE in the present study, a large difference in potency also observed by Buzzetti et\u00a0al. (50\u00a0=\u00a03.3\u20137.1\u00a0\u03bcmol/L). In keeping with the observations of Buzzetti et\u00a0al.  between wild type enzyme (0.92\u00a0\u00b1\u00a00.17\u00a0\u03bcmol/L), aromataseThr201Met (0.86\u00a0\u00b1 0.12\u00a0\u03bcmol/L), and aromataseArg264Cys (0.97\u00a0\u00b1 0.09\u00a0\u03bcmol/L) in AAA assays normalized for relative aromatase expression (Fig.\u00a0ICion Fig.\u00a0. The preion Fig.\u00a0. One stuion Fig.\u00a0.\u03b2\u2010DHE, 6\u2010HME, 6\u03b1/\u03b2\u2010hydroxy\u20106\u03b1/\u03b2\u2010hydroxy\u2010methylandrosta\u20101,4\u2010diene\u20103,17\u2010dione, and 6\u03b1/\u03b2,17\u03b2\u2010dihydroxy\u20106\u03b1/\u03b2\u2010hydroxymethyl\u2010androsta\u20101,4\u2010diene\u20103\u2010one were identified in incubations of EXE with pooled human liver microsomes through comparison to reference compounds (Fig.\u00a0\u03b2\u2010DHE\u2010glucuronide produced by UGT2B17 (Sun et\u00a0al. \u03b2\u2010DHE is not only the predominant EXE metabolite formed in human liver microsomes, but also capable of inhibiting aromatase with moderate potency suggesting that it may make clinically relevant contributions to the overall response to EXE in women with ER+ breast cancer (Platt et\u00a0al. 17nds Fig.\u00a0 detectedParticipated in research design: Peterson and Lazarus. Conducted experiments: Peterson. Contributed new reagents or analytic tools: Xia, Chen, and Peterson. Performed data analysis: Peterson. Wrote or contributed to the writing of the manuscript: Peterson, Chen, Xia, and Lazarus.None declared."}
{"text": "The structure of this complex was obtained by X-ray diffraction and supported by DFT calculations.The title compound, [Cu(dppaS 24H20NP2S2)(C18H15P)2]\u00b7CH2Cl2 or [Cu(dppaS2)(PPh3)2]\u00b7CH2Cl2, is a neutral mononuclear copper(I) complex bearing an N,N-bis\u00ad(di\u00adphenyl\u00adphospho\u00adrothio\u00adyl)amidate (dppaS2\u2212) ligand and two tri\u00adphenyl\u00adphosphane ligands. The molecular structure shows that the two S atoms of the dppaS2\u2212 ligand [Cu\u2014S = 2.3462\u2005(9) and 2.3484\u2005(9)\u2005\u00c5] and the two P atoms of the two tri\u00adphenyl\u00adphosphane ligands [Cu\u2014P = 2.3167\u2005(9) and 2.2969\u2005(9)\u2005\u00c5] coordinate to the copper(I) atom, resulting in a tetra\u00adhedral coordination geometry. The crystallographically observed mol\u00adecular structure is compared to the results of DFT calculations.The title compound, [Cu(C Several years ago, we reported some emissive copper(I) complexes bearing diphosphane di\u00adsulfide (PPh3)2] bearing the anionic diphos\u00adphane di\u00adsulfide ligand N,N-bis\u00ad(di\u00adphenyl\u00adphospho\u00adrothio\u00adyl)amidate (dppaS2\u2212) and two tri\u00adphenyl\u00adphosphane ligands.Copper(I) complexes have been studied actively because of the abundance of the metal ore and their inter\u00adesting lumin\u00adescent properties (Costa 2)(PPh3)2] shows that the two sulfur atoms of the dppaS2\u2212 ligand and the two phospho\u00adrus atoms of the two tri\u00adphenyl\u00adphosphane ligands coordinate to the copper atom, resulting in a tetra\u00adhedral coordination geometry  and 2.3484\u2005(9)\u2005\u00c5, and those between the copper atom and the phospho\u00adrus atoms of the tri\u00adphenyl\u00adphosphane ligands are Cu\u2014P = 2.3167\u2005(9) and 2.2969\u2005(9)\u2005\u00c5. The diphosphine di\u00adsulfide ligand forms a six-membered ring adopting a boat conformation. The bond order of the P6\u2014S2 and P7\u2014S3 bonds are considered to be slightly smaller than two because the lengths of the bonds are considerably longer than general P=S (= 1.91\u2005\u00c5) bond lengths amine (HdppaS2)  and potassium tert-butoxide . Tri\u00adphenyl\u00adphosphane  and [Cu(CH3CN)4]PF6  were then added to the reaction solution. After the solution had been stirred for one\u2005h at room temperature, a white powder (KPF6) precipitated. The mixture was then filtered. The solution was added to ethanol (20\u2005ml) and the resulting colorless crystals were obtained by filtration. Yield 256\u2005mg (82%). Analysis found: C, 69.43; H, 4.85; N, 1.36%. Calculated for [Cu(dppaS2)(PPh3)2], C60H50NS2P4Cu: C, 69.51; H, 4.86; N, 1.35%. 31P{1H} NMR  34.6 , \u22122.5 . Broadening of the 31P signals of the phospho\u00adrus atoms directly coordinating to the copper atom, which has a large quadrupole moment, has frequently been observed  = 1.2Ueq(C) for methyl\u00adene groups, and 0.95\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for aromatic groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017009380/im2478sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017009380/im2478Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017009380/im2478Isup3.molSupporting information file. DOI: 1557968CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The isomeric title compounds both display three-dimensional supra\u00admolecular architectures arising from N\u2014H\u22efO, C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions. N-[(2-nitro\u00adphen\u00adyl)sulfon\u00adyl]benzamide, (I), and 4-bromo-N-[(4-nitro\u00adphen\u00adyl)sulfon\u00adyl]benzamide, (II), are described (mol\u00adecular formula = C13H9BrN2O5S in each case). The asymmetric unit of (I) contains two independent mol\u00adecules [(IA) and (IB)], while that of (II) contains one mol\u00adecule. The benzoic acid aromatic ring of mol\u00adecule (IA) is disordered due to rotation about the Car\u2014C(=O) bond over two orientations in a 0.525\u2005(9):0.475\u2005(9) ratio. The dihedral angle between the benzene rings is 85.9\u2005(3)\u00b0 in (IA) and 65.22\u2005(19)\u00b0 in (IB), while in (II), the corresponding value is 56.7\u2005(7)\u00b0. In the crystals of (I) and (II), N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions generate three-dimensional networks.The syntheses and crystal structures of the isomeric 4-bromo- N-(aryl\u00adsulfon\u00adyl)aryl\u00adamides have received much attention as they constitute an important class of drugs for treating Alzheimer\u2019s disease -aryl\u00adamides are known to be potent anti-tumour agents against a broad spectrum of human tumour xenografts  in mice aryl\u00adamides aryl\u00adamides  and (IB), while that of (II)A) and (IB), the ortho-nitro substitution on the benzene\u00adsulfonyl ring is syn to the N\u2014H bond in the central \u2013C\u2014SO2\u2014N\u2014C(O)\u2013 segment  is disordered due to rotation about the Car\u2014C(=O) bond over two orientations in a 0.525\u2005(9):0.475\u2005(9) ratio, which are inclined to each other by 45.5\u2005(4)\u00b0. The nitro groups in both the A and B mol\u00adecules of (I)A) is 56.3\u2005(4)\u00b0, while in (IB), the torsion angle C14\u2014C15\u2014N4\u2014O9 is 35.6\u2005(5)\u00b0, whereas in (II)A), 65.22\u2005(19)\u00b0 in (IB) and 56.7\u2005(7)\u00b0 in (II)S(7) motif.The asymmetric unit of (I)nt Fig.\u00a01. The benN1\u22efO6 and N3\u2014HN3\u22efO4 \u2005\u00c5]. Further, C10\u2014H10B\u22ef\u03c01 [where \u03c01 is the nitro\u00adbenzene ring of mol\u00adecule (IB)] and C12\u2014H12A\u22ef\u03c02 [\u03c02 is the bromo\u00adbenzene ring of mol\u00adecule (IA)] extend the zigzag sheets into a three-dimensional architecture, which is consolidated by several aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions .The crystal structure of (I)4 Table\u00a01 between es Fig.\u00a03. The A +s Table\u00a01. A dimers Table\u00a01 and the N1\u22efO3 hydrogen bonds forming C(4) chains along [100] (Table\u00a02C(5) chains. The mol\u00adecules of neighbouring chains are inter\u00adlinked via C3\u2014H3\u22efO4 and C12\u2014H12\u22efO4 inter\u00adactions (i.e. O4 acts as a double acceptor) and thus, a zigzag sheet propagates in the ac plane (Table\u00a02C(13) and C(5) chains, respectively, along [001]. Mol\u00adecules in adjacent layers are linked via C9\u2014H9\u22efO2 and C10\u2014H10\u22efO1 inter\u00adactions that form C(7) and C(8) chains propagating along the b-axis direction, and thus a three-dimensional network is obtained. A short O5\u22efBr1 [3.173\u2005(4)\u2005\u00c5] contact is observed.The crystal structure of (II)] Table\u00a02: these c] Table\u00a02 forming e Table\u00a02. The C12et al., 2016N-benzoyl\u00adbenzene\u00adsulfonamide Uiso = 1.2Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017001578/hb7646sup1.cifCrystal structure: contains datablock(s) I, II, shelx. DOI: 10.1107/S2056989017001578/hb7646Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017001578/hb7646IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017001578/hb7646Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017001578/hb7646IIsup5.cmlSupporting information file. DOI: 1530208, 1530207CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of tetra\u00adiso\u00adbutyl\u00adthiuram di\u00adsulfide reveals a \u221285.81\u2005(1)\u00b0 C\u2014S\u2014C\u2014S torsion angle and multiple intra- and inter\u00admolecular S\u22efC\u2014H close contacts. 18H36N2S4, crystallizes in a general position in the triclinic space group P-1 but shows pseudo-C2 symmetry about the di\u00adsulfide bond. The C\u2014S\u2014S\u2014C torsion angle [\u221285.81\u2005(2)\u00b0] and the dihedral angle between the two NCS2 mean planes [85.91\u2005(5)\u00b0] are within the range observed for this compound type. Multiple intra- and inter\u00admolecular S\u22efH\u2014C close contacts appear to play a role in assisting the specific conformation of the pendant isobutyl groups and the packing arrangement of mol\u00adecules within the cell. Tetra\u00adiso\u00adbutyl\u00adthiuram di\u00adsulfide mol\u00adecules of one optical configuration form sheets in the plane of the a and b axes. Inversion centers exist between adjoining sheets, which stack along the c axis and alternate in the handedness of their constituent mol\u00adecules.Tetra\u00adkis(2-methyl\u00adprop\u00adyl)thio\u00adper\u00adoxy\u00addicarbonic di\u00adamide, or tetra\u00adiso\u00adbutyl\u00adthiuram di\u00adsulfide, C N,N,N\u2032,N\u2032-Tetra\u00adalkyl\u00adthio\u00adper\u00adoxy\u00addicarbonic di\u00adamides, com\u00admon\u00adly called tetra\u00adthiuram di\u00adsulfides, comprise a class of organosulfur compounds with applications that are both diverse and long-standing. Tetra\u00admethyl\u00adthiuram di\u00adsulfide, known by the commercial name thiram, is broadly useful both as a fungicide 2] that was more complex than anti\u00adcipated, even considering the hindered rotation about the \u2212S2\u2013CNiBu2 bond thio\u00adper\u00adoxy\u00addicarbonic di\u00adamide (tetra\u00adiso\u00adbutyl\u00adthiuram di\u00adsulfide) itself does not show evidence of such intra\u00admolecular inter\u00adaction, several recent studies of tetra\u00adthiuram di\u00adsulfides have suggested such inter\u00adactions in the crystalline state . Despite the lack of strict C2 symmetry, tetra\u00adiso\u00adbutyl\u00adthiuram di\u00adsulfide is nevertheless chiral. The image in Fig.\u00a01a presents the mol\u00adecule with a left-handed configuration to the core \u2013H2CNC(S)S\u2013SC(S)NCH2\u2013 portion. If Fig.\u00a01a were to be viewed from above, along the pseudo C2 axis that bis\u00adects the S3\u2014S4 bond, the C1\u2014S1 and C2\u2014S2 thione bonds would project forward and backward, respectively, from the plane of the paper and thereby define a left-handed propeller. The right-handed counterpart is necessarily the other occupant of the unit cell, as required by the racemic space group. Among the structurally characterized thiuram di\u00adsulfides, crystallographically imposed C2 symmetry is also common \u2005\u00c5, while the thione C=S bonds are essentially identical at 1.642\u2005(3) and 1.643\u2005(3)\u2005\u00c5. The C1\u2014S3\u2014S4\u2014C2 torsion angle, \u03c4, is \u221285.81\u2005(2)\u00b0 and, as is typical of tetra\u00adthiuram di\u00adsulfides, very similar in magnitude to the angle of 85.91\u2005(5)\u00b0 between the mean planes defined by the Sb and shown in Table\u00a01D\u2014H\u22efA angles are closer to 90\u00b0 than to 180\u00b0 , 3.810\u2005(3)\u2005\u00c5]. The geometric parameters for both these intra\u00admolecular and inter\u00admolecular S\u22efC\u2013H contacts fall within the range defined as consistent with a weak D\u2014H\u22efA inter\u00adaction  and the dihedral angle (\u03b8) between Set al., 20092Cl2 solution. 1H NMR : 3.83 , 2.39 , 0.98 , 0.87 .The synthesis procedure employed was that described by Kapanda 2) or 1.5 times (for \u2013CH3) those of the carbon atoms to which they were attached. The C\u2014H distances assumed were 1.00, 0.99, and 0.98\u2005\u00c5 for the \u2013CH\u2013, \u2013CH2, and \u2013CH3 types of hydrogen atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017015158/lh5851sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017015158/lh5851Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017015158/lh5851Isup3.cmlSupporting information file. DOI: 1580550CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Solvents are the source of the protons at the ylidic C atom.Reaction of BI 3 with carbodi\u00adphospho\u00adrane, C(PPh3)2, gives a mixture of the dicationic compounds, methyl\u00adenebis(tri\u00adphenyl\u00adphospho\u00adnium) diiodide di\u00adchloro\u00admethane disolvate, C37H32P22+\u00b72I\u2212\u00b72CH2Cl2 or [Ph3PCH2PPh3]I2\u00b72CH2Cl2 (I), methyl\u00adenebis(tri\u00adphenyl\u00adphospho\u00adnium) bis\u00ad(tetra\u00adiodo\u00adborate), C37H32P22+\u00b72BI4\u2212 or [Ph3PCH2PPh3](BI4)2 (II). Solvents are the source of the protons at the ylidic C atom. The P\u2014C\u2014P angle is 124.1\u2005(2)\u00b0 for (I) and 121.7\u2005(3)\u00b0 for (II), while the two P\u2014C bond lengths are 1.804\u2005(4) and 1.807\u2005(5)\u2005\u00c5 in (I), and 1.817\u2005(5) and 1.829\u2005(5)\u2005\u00c5 in (II). In the crystal of (I), the protons of the central P\u2014CH2\u2014P C atom exhibit weak C\u2014H\u22efI hydrogen bonds with the respective anions. The anions in turn are linked to the di\u00adchloro\u00admethane solvent mol\u00adecules by C\u2014H\u22efI hydrogen bonds. In the crystal of (II), one of the BI4\u2212 anions is linked to a phenyl H atom via a weak C\u2014H\u22efI hydrogen bond.Reaction of BI The volume of the resulting solution was reduced to ca 3\u2005ml and layered with ca 5\u2005ml of hexane. A crop of crystals formed in a few days .(PhUiso(H) = 1.2Ueq(C). For both compounds, a small number of reflections were affected by the beam stop and were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017010295/su5375sup1.cifCrystal structure: contains datablock(s) Global, II, I. DOI: 10.1107/S2056989017010295/su5375Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017010295/su5375IIsup4.hklStructure factors: contains datablock(s) II. DOI: 1533031, 1552112CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The compound comprises an octa\u00adhedral homoleptic Me2SO-solvated cobalt(II) cation and a tetra\u00adhedral cobaltate(II) anion attached to three chloro ligands and one quinoline moiety.Anhydrous cobalt(II) chloride reacts with quinoline (C 2SO) or quinoline (C9H7N). The title compound, [Co(C2H6OS)6][CoCl3(C9H7N)]2, is a cobalt salt in which the metal ion is complexed to both Me2SO and quinoline. In particular, we observed that anhydrous cobalt(II) chloride reacts with quinoline in Me2SO to form a salt that is to be formulated as [CoII(Me2SO)6]2+{[CoIICl3quinoline]2\u2212}. The CoII atom in the cation portion of this mol\u00adecule lies on a inversion center and is bound to the O atoms of six Me2SO moieties in an octa\u00adhedral configuration, while the CoII atom in the anion is attached to three chloride ligands and one quinoline moiety in a tetra\u00adhedral arrangement.There are few reports that describe crystal structures of compounds containing cobalt complexed to either dimethyl sulfoxide (Me A closely related complex, [Co(Me2SO)6][CoCl4], contains a cobalt cation that is similarly surrounded by six oxygen atoms in a slightly distorted octa\u00adhedral configuration with Co\u2014O distances between 2.06\u2005(1) and 2.10\u2005(1)\u2005\u00c5, with a mean Co\u2014O distance of 2.08\u00c5  bond angles in the title complex are close to 90\u00b0, ranging from 86.29\u2005(7) to 93.71\u2005(7)\u00b0, compared to 87.9\u2005(5) to 90.8\u2005(4)\u00b0 in [Co(Me2SO)6][CoCl4] 6][CoCl4] also showed some distortion with Co\u2014Cl distances ranging from 2.265\u2005(6) to 2.305\u2005(7)\u2005\u00c5, giving an average Co\u2014Cl distance of 2.284\u2005(6)\u2005\u00c5, and the Cl\u2014Co\u2014Cl angles ranging from 107.1\u2005(2) to 112.4\u2005(2)\u00b0 6][CoCl4] were ascribed to disorder, as indicated by the high anisotropic motion  to 2.2534\u2005(10)\u2005\u00c5, with an average Co\u2014Cl distance of 2.252\u2005\u00c5, while the Co\u2014N distance is 2.054\u2005(3)\u2005\u00c5. The Cl\u2014Co\u2014Cl angles range from 108.21\u2005(5) to 114.26\u2005(4)\u00b0, giving an average of 110.98\u00b0, and the average N\u2014Co\u2014Cl angle is 107.88\u00b0 [range 107.09\u2005(9) to 108.80\u2005(8)\u00b0], indicating that while the anion is close to tetra\u00adhedral, there is some distortion. Inter\u00adestingly, the [CoCl4 index that is reported and discussed elsewhere ]/141, where \u03b1 and \u03b2 represent the two largest angles; a \u03c44 value of 1.00 indicates an idealized tetra\u00adhedral geometry, whereas a value of 0.00 indicates an idealized square-planar geometry. In the title complex, \u03b1 = 114.26\u2005(4)\u00b0 and \u03b2 = 110.46\u2005(4)\u00b0, such that \u03c44 is 0.96, which indicates very little deviation from a tetra\u00adhedral geometry. For comparison, \u03c44 for the [CoCl4]2\u2212 anion in [Co(Me2SO)6][CoCl4] is 0.98 6]2+ and [CoIICl3quinoline]\u2212 ions, with the exception of very weak C\u2014H\u22efCl interactions. The distances between the Cl and the carbon atoms of the methyl groups of the Me2SO ligands are, for example, Cl1\u22efC32\u2014S3  [3.525\u2005(3)\u2005\u00c5], Cl1\u22efC31\u2014S3  [3.736\u2005(4)\u2005\u00c5], Cl2\u22efC22\u2014S2  [3.633\u2005(4)\u2005\u00c5], Cl2\u22efC21\u2014S2  [3.770\u2005(4)\u2005\u00c5], Cl3\u22efC12\u2014S1  [3.638\u2005(4)\u2005\u00c5] and Cl3\u22efC32\u2014S3  [3.819\u2005(4)\u2005\u00c5] and are comparable to the sum of the van der Waals radii of Cl and CH3 of 3.80\u2005\u00c5 6][CoCl4] complex as discussed above 6][CoCl4] 6][CoCl4], there are a few other examples of cobalt complexes solvated by Me2SO that are listed in the Cambridge Database 6][ClO4]2, one of which possesses Co\u2014O distances in the range 2.0833\u2005(17)\u20132.0934\u2005(15)\u2005\u00c5, giving a mean Co\u2014O distance of 2.088\u2005(5)\u2005\u00c5, with O\u2014Co\u2014O (cis) angles between 90.11\u2005(6) and 92.31\u2005(6)\u00b0  angles between 85.26\u2005(7) and 93.67\u2005(8)\u00b0 6][SnCl6], both the cobalt and tin metal ions display an octa\u00adhedral environments, with the Co\u2014O bond lengths reported between 2.093\u2005(4) and 2.113\u2005(5)\u2005\u00c5  angles vary between 89.0\u2005(2) and 90.0\u2005(2)\u00b0 6][NO3]3 is also known and possesses six equivalent Co\u2014O bond lengths of 2.005\u2005(2)\u2005\u00c5, which are shorter than the values in the CoII complexes (Me2SO-S)(C2H5OH)]\u00b7C2H5OH (acv = a\u00adcyclo\u00advir)  is rare, there are some notable examples. For example, the compound bis\u00ad(dimethyl sulfoxide)\u00adhydridobis(tri\u00adphenyl\u00adphosphane)cobalt(I), [CoH(C18H15P)2(Me2SO)2], contains CoI coordinating a hydride anion, two phosphine ligands and two Me2SO moieties that are bound through the sulfur atom in a distorted trigonal\u2013bipyramidal structure -porphyrinato)-cobalt(III) bis\u00ad(dimethyl sulfoxide-\u03baS)-porph\u00adyr\u00adinato)cobalt(III) bis\u00ad(hexa\u00adfluoro\u00adanti\u00admonate) dimethyl sulfoxide solvate 2]\u2212 of the title compound is 2.037\u2005(5)\u2005\u00c5 while the Co\u2013Cl bond lengths are 2.2517\u2005(10)\u20132.2534\u2005(10)\u2005\u00c5, and the Cl\u2014Co\u2014Cl and Cl\u2014Co\u2014N angles range between 108.21\u2005(5) and 114.26\u2005(4)\u00b0, and 107.09\u2005(9) and 108.80\u2005(8)\u00b0, respectively. For comparison, the Co\u2014N bond lengths in the CoIICl2(quinoline)2 complex are 2.061\u2005(3) and 2.037\u2005(5)\u2005\u00c5 and the Co\u2014Cl bond lengths are 2.246\u2005(2) and 2.241\u2005(1)\u2005\u00c5  in Me2SO (20\u2005mL) and refluxed for one\u2005h. After cooling down, the mixture was transferred to a beaker and placed in a desiccator containing anhydrous calcium chloride pellets (4\u201320 mesh) to crystallize over a period of four months. Deep-blue crystals of [Co(Me2SO)6]2+{[CoCl3quinoline]2}\u2212 suitable for X-ray diffraction were obtained from this process of slow evaporation. Notably, when the reaction between anhydrous cobalt(II) chloride and quinoline is conducted in EtOH, rather than Me2SO, the previously reported [CoIICl2(quinoline)2] complex is obtained  chloride  was mixed with quinoline, CUiso(H) = 1.2Ueq(Csp2) or 1.5Ueq(Csp3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989018001652/lh5868sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018001652/lh5868Isup2.hklStructure factors: contains datablock(s) I. DOI: 1820336CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The synthesis and structural determination of bis\u00adsulfone tetra\u00ad(nitrate) monohydrate is reported. The crystal structure features N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonds and \u03c0\u2013\u03c0 inter\u00adactions. 12H14N2O2S2+\u00b74NO3\u2212\u00b7H2O {alternative name: bis[bis\u00ad sulfone] tetra\u00adnitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03\u2005(18) and 69.69\u2005(19)\u00b0. In the crystal, mixed cation\u2013anion\u2013water mol\u00adecule layers lying parallel to the (001) plane are formed through N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions and these layers are further extended into an overall three-dimensional supra\u00admolecular network structure. Inter-ring \u03c0\u2013\u03c0 inter\u00adactions are also present [minimum ring centroid separation = 3.693\u2005(3)\u2005\u00c5].In the title compound, the hydrated tetra\u00ad(nitrate) salt of dapsone , 2C Ka ca 2), is a drug that has been used to treat a diversity of diseases including tuberculosis, leprosy, malaria and AIDS-related pneumonia , a very weak Lewis base anilinium 2-carb\u00adoxy-4,6-di\u00adnitro\u00adphen\u00adolate monohydrate has been reported sulfone cations (A and B), four nitrate anions and one water mol\u00adecule (O1W) in the asymmetric unit  (Aa) and (N1/C7\u2013C12) (Ab)] and cation B [defined by (N3/C13\u2013C18) (Ba) and (N4/ C19\u2013C24) (Bb)] are 70.03\u2005(18) and 69.69\u2005(19)\u00b0, respectively. As expected the anilinium groups are planar with maximum r.m.s. deviations of 0.0044, 0.0120, 0.0114 and 0.0072\u2005\u00c5, respectively.The title compound crystallizes in the ortho\u00adrhom\u00adbic space group it Fig.\u00a01. The di\u00advi and nitro O12vii acceptors. The two cations A and B are associated through \u03c0\u2013\u03c0 inter\u00adactions [ring centroid separation CgAb\u22efCgBai = 3.693\u2005(3)\u2005\u00c5 [symmetry code: (i) \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a0a-axis direction  bond motif  motifs 3\u00b79H2O  in EtOH (2\u2005ml) was added dropwise to 4,4\u2032-di\u00adamino\u00addiphenyl sulfone  in EtOH (5\u2005ml), with continuous stirring at room temperature for 72\u2005h. Slow evaporation of this solution yielded yellow crystals suitable for X-ray analysis within 5\u2005d.Fe(NOUiso(H) = 1.2Ueq(C). All N\u2014H atoms were located by difference methods but were subsequently restrained in the refinement with N\u2014H = 0.89\u2005\u00c5 and Uiso = 1.2Ueq(N). The H atoms of the water mol\u00adecule were also located in a Fourier map and were allowed to ride with a restrained O\u2014H bond length = 0.85\u2005(1)\u2005\u00c5 and H\u22efH = 1.39\u2005(2)\u2005\u00c5 and Uiso(H) = 1.5 Ueq(O). Although not of relevance in this achiral compound, the Flack absolute structure parameter  I. DOI: 10.1107/S2056989017014803/zs2390Isup2.hklStructure factors: contains datablock(s) I. DOI: 1579678CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Their structures and absolute configurations were unambiguously established by a combination of NMR and MS analysis and electronic circular dichroism (ECD)\u00a0evidence. Callisalignenes H (2) and I (3) have a rare sec-butyl moiety at C-7. Meroterpenoids 1\u20133 exhibited cytotoxicity against HCT116 cells with IC50 values of 8.51\u00a0\u00b1\u00a01.8, 9.12\u00a0\u00b1\u00a00.3, and 16.33\u00a0\u00b1\u00a03.3\u00a0\u03bcM, respectively.Callisalignenes G\u2013I  contains supplementary material, which is available to authorized users. Callistemon (Myrtaceae) are evergreen shrubs or small trees native to Australia and have been popularly cultivated in southern China as ornamental species with bottle brush inflorescence. Recently, acylphloroglucinols and their derivatives, including adducts of a phloroglucinol moiety coupled with its derivative or a terpenoid unit, have been extensively\u00a0obtained from this genus . Further analysis of its experimental and calculated ECD spectra -4.Besides the three new meroterpenoids, two known compounds were identified as (\u2013)-callistenone F (4)  and vimiS. aureus, E. coli, and P. aeruginosa) and three fungal strains . None of them showed antimicrobial effects (MIC\u00a0>250\u00a0\u03bcg/mL). Additionally, cytotoxicities of 1\u20135 against six human cancer cells  were also conducted\u00a0and the results were summarized in Table 1\u20133 exhibited cytotoxicity against HCT116 cells with IC50 values of 8.51\u00a0\u00b1\u00a01.8, 9.12\u00a0\u00b1\u00a00.3, and 16.33\u00a0\u00b1\u00a03.3\u00a0\u03bcM, respectively, compared to that of positive control . Moreover, 1 and 3 displayed cytotoxicity against A549 cells with IC50 values of 12.85\u00a0\u00b1\u00a08.2 and 10.03\u00a0\u00b1\u00a03.2\u00a0\u03bcM , respectively.All the isolates were evaluated for their antimicrobial effects toward three bacterial (cts MIC\u00a0>50\u00a0\u03bcg/mL.\u03b4) were expressed in ppm with reference to the solvent signals, and coupling constant (J) values were reported in Hz. HRESIMS data were measured using an Agilent 1290 UPLC/6540 Q-TOF mass spectrometer. Sephadex LH-20 , Si gel , and RP-18  were used for column chromatography (CC). Semi-preparative HPLC was performed on an Agilent 1260 instrument with a ZORBAX SB-C18 column . Fractions were monitored by Si gel GF254  or RP-18 F254  plates. Spots were visualized under UV light and by spraying with 10% H2SO4 in EtOH followed by heating.Optical rotations were measured on a Jasco P-1020 polarimeter. UV spectra were recorded on a Shimadzu UV2401 PC spectrophotometer. IR spectra were determined on Bruker FT-IR Tensor-27 infrared spectrophotometer with KBr discs. ECD spectra were recorded on an Applied Photophysics spectropolarimeter. 1D and 2D NMR spectra were recorded on Bruker AV 600 or 800\u00a0MHz spectrometers using TMS as an internal standard. Chemical shifts . A voucher specimen (HY0025) was deposited in the State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences.Twigs and leaves of C. salignus (10.0\u00a0kg) were percolated with petroleum ether (PE) at room temperature three times  and then filtered. After removal of solvent under reduced pressure, the crude extract (130\u00a0g) was subjected to silica gel CC, eluted with PE-EtOAc  to yield five fractions A\u2013E. Fraction A (25\u00a0g) was applied to Sephadex LH-20 column  to give A3 (3\u00a0g), which was further separated on an RP-18 column and eluted with a gradient of MeCN\u2013H2O  to obtain five subfractions (A3-1\u2013A3-5). Subfraction A3-4 (225\u00a0mg) was subsequently purified by semi-preparative HPLC with MeCN\u2013H2O  as mobile phase to afford 1 (5\u00a0mg), 2 (4\u00a0mg), 3 (8\u00a0mg), and 5 (35\u00a0mg). Similarly, fraction C (42\u00a0g) was separated by Sephadex LH-20 column  to give three subfraction (C1\u2013C3). After repeated purification by RP-18 column with MeCN\u2013H2O , 4 (18\u00a0mg) was obtained from C2 (0.5\u00a0g).Air-dried and powdered twigs and leaves of \u03b1] +188.3 ; UV (MeOH) \u03bbmax (log \u03b5) 265 (4.18) nm; CD (MeOH) 265 (\u0394 \u03b5 + 36.23), 306 (\u0394\u03b5 \u22127.57) nm; IR (KBr) vmax 3440, 2932, 1721, 1651, 1469, 1248\u00a0cm\u20131; 1H and 13C NMR data, see Table\u00a0m/z 409.2714 [M\u00a0+\u00a0Na]+ .Colorless gum; [\u03b1] \u2212221.4 ; UV (MeOH) \u03bbmax (log \u03b5) 266 (4.20) nm; CD (MeOH) 267 (\u0394\u03b5 \u221231.35), 309 (\u0394\u03b5 + 4.11) nm; IR (KBr) vmax 3439, 2930, 1720, 1649, 1467, 1247\u00a0cm\u22121; 1H and 13C NMR data, see Table\u00a0m/z 409.2708 [M\u00a0+\u00a0Na]+ .Colorless gum; [\u03b1] +164.7 ; UV (MeOH) \u03bbmax (log \u03b5) 267 (4.24) nm; CD (MeOH) 267 (\u0394\u03b5 +27.50), 306 (\u0394\u03b5 \u22126.02) nm; IR (KBr) vmax 3428, 2962, 1718, 1651, 1467, 1384, 1174\u22121; 1H and 13C NMR data, see Table\u00a0m/z 387.2899 [M\u00a0+\u00a0H]+ .Colorless gum; [\u03b1] \u2212133.0 ; CD (MeOH) 235 (\u0394\u03b5 +5.45), 248 (\u0394\u03b5 +1.77), 286 (\u0394\u03b5 +15.10), 317 (\u0394\u03b5 \u221213.95) nm.Colorless gum; [The conformations generated by the MM2 force field in Chem-Bio3D software overlaid with key correlations observed in the ROESY spectrum were subjected to semi-empirical PM3 quantum mechanical geometry optimizations using the Gaussian 09 program . The cor1\u20135 were carried out against three bacterial strains  and three fungal strains  using the antimicrobial susceptibility assay [The antimicrobial activities compounds ty assay . The comAll the compounds were evaluated for their cytotoxicities against six tumor cell lines, including HCT116 , Huh7 (human hepatoma cell line), Hela , CCRF-CEM (human acute lymphocytic leukemia cell line), DU145 (human prostatic cancer cell line), and A549 (human lung cancer cell line), by MTT assay in 96-well plates [Supplementary material 1 (DOCX 12178\u00a0kb)Below is the link to the electronic supplementary material."}
{"text": "L3Phen (where L\u2212 is the sulfonyl\u00adamido\u00adphosphate (SAPh)-type ligand N-{bis\u00ad[meth\u00adyl(phen\u00adyl)amino]\u00adphosphor\u00adyl}benzene\u00adsulfonamidate, C6H5SO2NHPO[N(CH3)C6H5]2 has been synthesized and its crystal structure determined.A lanthanum(III) complex with formula La 20H21N3O3PS)3(C12H8N2)] is created by one LaIII ion, three deprotonated N-{bis\u00ad[meth\u00adyl(phen\u00adyl)amino]\u00adphosphor\u00adyl}benzene\u00adsulfonamidate (L\u2212) ligands and one 1,10-phenanthroline (Phen) mol\u00adecule. Each LaIII ion is eight-coordinated (6O+2N) by three phosphoryl O atoms, three sulfonyl O atoms of three L\u2212 ligands and two N atoms of the chelating Phen ligand, leading to the formation of six- and five-membered metallacycles, respectively. The lanthanum coordination polyhedron has a bicapped trigonal\u2013prismatic geometry. \u2018Sandwich-like\u2019 intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions are observed between the 1,10-phenanthroline ligand and two benzene rings of two different L\u2212 ligands. The phenyl rings of L\u2212 that are not involved in the stacking inter\u00adactions show minor positional disorder. Mol\u00adecules form layers parallel to the (010) plane due to weak C\u2014H\u22efO inter\u00admolecular hydrogen bonds. Unidentified highly disordered solvate mol\u00adecules that occupy ca 400\u2005\u00c53 large voids have been omitted from the refinement model.The asymmetric unit of [La(C These types of compounds were first synthesized by Kirsanov , containing the functional fragment C(O)NHP(O), because of their properties as extractants (OMe)2] amido\u00adphosphate [(Me)PhSO2NHP(O)(OMe)2] and dimethyl 2-naphthyl\u00adsulfonyl\u00adamido\u00adphosphate [(C10H7)SO2NHP(O)(OMe)2] indicate that the ligand first excited singlet state plays a dominant role in intra\u00admolecular energy transfer processes in these Ln complexes amido\u00adphosphate [PhSON-(meth\u00adyl(phenyl\u00adamino)\u00adphosphor\u00adyl)benzene\u00adsulfon\u00adamide (HL) [PhSO2NHP(O)(N(Me)Ph)2] with the general formula 3PhenLa(L).Knowledge of the crystal structure is an essential part of understanding the luminescent properties of these types of lanthanide complexes. In this paper we would therefore like to report the mol\u00adecular and crystal structure of a lanthanum coordination compound based on the amidic type SAPh ligand 3PhenLa(L) crystallizes with one mol\u00adecule in the asymmetric unit  bond lengths [2.516\u2005(2)\u20132.541\u2005(2)\u2005\u00c5] are all longer than those of their La\u2014O(P) counterparts [2.424\u2005(2)\u20132.463\u2005(2)\u2005\u00c5], with mean values of 2.435 and 2.456\u2005\u00c5, respectively. The mean average of all La\u2014O bond lengths is 2.476\u2005\u00c5. The La\u2014N distances are with 2.699\u2005(3) and 2.700\u2005(3)\u2005\u00c5  shorter than those previously obtained for a 1,10-phenanthrolinate lanthanum (III) complex with hexa\u00adfluoro\u00adacetyl\u00adacetonate \u20131.474\u2005(2)\u2005\u00c5 and 1.491\u2005(2)\u20131.494\u2005(2)\u2005\u00c5 in their expected ranges. The mean values are 1.468 and 1.492\u2005\u00c5, respectively. The corresponding bond lengths in the related neutral ligands are around 1.42\u2005\u00c5 (Moroz A) and La1\u2013O3\u2013P3\u2013N3\u2013S3\u2013O9 (B) rings both adopt twist-boat conformations  are 0.78 and 0.41\u2005\u00c5, respectively. The deviations of the La1 and O3 atoms from the mean plane through the remaining atoms of B (r.m.s.deviation = 0.06\u2005\u00c5) are 0.9 and 0.88\u2005\u00c5, respectively. The La1\u2013O2\u2013P2\u2013N2\u2013S2\u2013O7 (C) ring adopts a flattened half-chair conformation . The deviation of the La1 atom from the mean plane carried through the remaining atoms of ring C (r.m.s.deviation 0.02\u2005\u00c5) is 0.36 \u2005\u00c5.The six-membered metallocyclic rings with the chelate (O)PNS(O) fragments are all non-planar. The La1\u2013O1\u2013P1\u2013N1\u2013S1\u2013O1  similar to that of the Tb(Pip)3(Phen) mixed-ligand complex with 2,2,2-tri\u00adchloro-N-(dipiperidin-1-yl-phosphor\u00adyl)acetamide, HPip \u22efC69(\u03c0) of the 1,10-phenanthroline mol\u00adecule inter\u00adacts with the C41(\u03c0)\u22efC46(\u03c0) phenyl ring at the sulfonyl group from another ligand , and with the C8(\u03c0)\u22efC13(\u03c0) ring at the phosphoryl group from the other ligand . A similar intra\u00admolecular organization was described previously for related compounds (Beloso 3PhenLa(L) mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds .In the crystal phase, the s Table\u00a01, formings Table\u00a01. There aet al., 2016N-(bis\u00ad(di\u00adamino)\u00adphosphor\u00adyl)sulfonamide fragments yielded five hits, with only one metal complex structure with a neodymium metal atom among them --erbium(III) phospho\u00adramidato-2O6 environment yielded 20 hits, with average La\u2014O and La\u2014N bond lengths of 2.476 and 2.693\u2005\u00c5, respectively. 11 complex structures with different lanthanoid metals (Ln) containing Ln\u2013O\u2013P\u2013N\u2013S\u2013O metallocycles were found in the database, all with octa\u00adcoordinated metal atoms. Most of those metallacyclic rings are non-planar with mean deviations of the O and N atoms of 0.329 and 0.434\u2005\u00c5, respectively.A search for octa\u00adcoordinated La complexes with an LaN1H and 31P NMR spectra in DMSO-d6 solutions were recorded on a Varian 400 NMR spectrometer at room temperature. 1H chemical shifts were determined relative to the inter\u00adnal standard TMS whereas 31P chemical shifts were determined relative to 85% H3PO4 as an external standard. Infrared (FTIR) spectra were recorded on a Perkin\u2013Elmer Spectrum BX spectrometer using KBr pellets. The resolution of the FTIR spectra is 1\u2005cm\u22121.Sulfonyl\u00adamido\u00adphosphate ligandN-(meth\u00adyl(phenyl\u00adamino)\u00adphosphor\u00adyl)benzene\u00adsulfonamide (HL) was synthesized via a three-step procedure based on the Kirsanov reaction  \u03b4 2.95 , 7.05 , 7.14 , 7.21 , 7.56 , 7.65 , 7.91 .\u22121): 3062 , 2948 , 2780 , 2705 , 2655 , 1594 , 1495 (s), 1446 (m), 1400 (m), 1330 , 1279 (m), 1220 , 1168 , 1084 (m), 1069 (m), 1028 (m), 920 , 887 (ws), 765 (s), 758 (s), 723 (m), 696 (s), 685 (s), 602 (m), 573 (m), 558 (m), 551 (m), 542 (m), 508 (s), 490 (m), 442 (w).IR  was prepared by the reaction between equimolar amounts of sodium methano\u00adlate  and HL  in an methanol medium (20\u2005ml). The mixture was heated with magnetic stirring at 337\u2005K for 10\u2005min. The resulting solution was evaporated and the fine crystalline powder was isolated (yield 83%) and washed with 2-propanol. Dry product NaL was used for the preparation of the complexes. 1H NMR  \u03b4 3.46 , 3.48 , 7.26 , 7.53 , 7.6 , 7.77 . 31P NMR  \u03b4 54.01.The sodium salt (\u22121): 3068 , 2944 , 2704 , 2660 , 1581 , 1490 (s), 1410 , 1263 , 1271 (m), 1173 , 1165 , 1080 (m), 1031 (m), 891 , 2943 , 2704 , 2660 , 1564 , 1490 (s), 1413 , 1252 , 1243  + \u03bd(C\u2014C)], 1270 (m), 1164 , 1165 , 1082 (m), 1030 (m), 990 , 892 [ws, \u03bd, 763 (s), 747 (s), 720 (m), 678 (s), 682 (s), 564 (m), 547 (m), 534 (m), 502 (s), 485 (m), 427 (w).IR  = xUeq(C), where x = 1.5 for methyl H and 1.2 for all other H atoms. A rotating-group model was applied for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a02A and B with refined occupancies of 0.50\u2005(3) for both disorder components. The phenyl rings C15\u2013C20, C21\u2013C26 were refined as disordered over two positions with refined occupancies of 0.555\u2005(17) and 0.445\u2005(17), respectively. The bond lenghts C21A\u2014C22A, C22A\u2014C23A, C23A\u2014C24A, C24A\u2014C25A, C25A\u2014C26A, C26A\u2014C21A, C21\u2014C22, C22\u2014C23, C23\u2014C24, C24\u2014C25, C25\u2014C26 and C26\u2014C21 were restrained to have a value of 1.38\u2005(1)\u2005\u00c5 (using a DFIX restraint). The ring carbon atoms C21A, C26A, C25A, C24A, C23A, C22A as well as C21, C22, C23, C24, C25, C26 were restrained to have planar geometries . Anisotropic parameters of all C atoms of disordered rings were restrained to have approximately similar values to within 0.01\u2005\u00c52 (using a SIMU restraint).Phenyl ring C1\u2013C6 was refined as disordered over two positions 3. Satisfactory results (R1 = 5.01%) were obtained modeling disordered C and O atoms, but very large displacement parameters for them were observed. The SQUEEZE procedure  per cell. However, the difference in R1 values for the structures with and without the SQUEEZE procedure implemented was rather small (0.5%). In the final refinement, the isolated peaks in the solvent-accessible voids were ignored.During the refinement, several small isolated electron-density peaks were located in solvent-accessible voids that were believed to be solvent mol\u00adecules. The largest residual electron peak accounted to 0.66\u2005e\u2005\u00c510.1107/S2056989017008970/zl2701sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: Click here for additional data file.10.1107/S2056989017008970/zl2701Isup4.cdxSupporting information file. DOI: 10.1107/S2056989017008970/zl2701Isup6.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017008970/zl2701sup5.txthkl-file. DOI: 1556367CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the two indole ring systems are approximately perpendicular to one another, making a dihedral angle of 80.9\u2005(5)\u00b0. In the crystal, pairs of N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into inversion dimers and these are further linked by N\u2014H\u22efO and hydrogen bonds and short Cl\u2014Cl contacts into supra\u00admolecular chains. 29H24Cl2N2O4, the mean planes of the two indole ring systems (r.m.s. deviations = 0.1249 and 0.0075\u2005\u00c5) are approximately perpendic\u00adular to one another, with a dihedral angle of 80.9\u2005(5)\u00b0 between them. The benzene ring is inclined to the mean planes of the two indole ring systems by 76.1\u2005(3) and 78.3\u2005(4)\u00b0. Weak intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions affect the mol\u00adecular conformation. In the crystal, pairs of N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into inversion dimers which are further linked into supra\u00admolecular chains by N\u2014H\u22efO hydrogen bonds and short Cl\u2014Cl contacts.In the title compound, C C11\u2014H11A\u22efCl1 and short Cl2\u22efCl2 contacts [Cl2\u22efCl2 = 3.467\u2005(2)\u2005\u00c5] bridge these chains and form sheets of mol\u00adecules parallel to bis\u00ad(1H-indole-2-carboxyl\u00adate)     was dissolved in 20\u2005ml ethanol; commercially available 2,4-di\u00adchloro\u00adbenzalde\u00adhyde  was added and the mixture was heated to reflux temperature. Concentrated HCl (0.5\u2005ml) was added and the reaction was left for 1\u2005h. After cooling, the white product was filtered off and washed thoroughly with ethanol. The reaction was monitored with TLC (AcOEt:hexane = 1:3). Colourless block-like crystals of the title compound suitable for X-ray analysis were obtained in 92% yield by slow evaporation of an ethanol solution.Uiso(H) = xUeq, where x = 1.5 for methyl H atoms and 1.2 for all others.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017015730/sj5539sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017015730/sj5539Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017015730/sj5539Isup3.cmlSupporting information file. DOI: 1582719CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Crystal structures of hydrogen-bonded 1:2 compounds of chloranilic acid with 2-pyridone, 3-hy\u00addroxy\u00adpyridine and 4-hyroxypyridine have been determined at 120\u2005K. In each crystal structure, the acid and base mol\u00adecules are linked by short O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. 5H5NO\u00b7C6H2Cl2O4, (I), bis\u00ad(3-hy\u00addroxy\u00adpyridinium) chloranilate, 2C5H6NO+\u00b7C6Cl2O42\u2212, (II), and bis\u00ad(4-hy\u00addroxy\u00adpyridinium) chloranilate, 2C5H6NO+\u00b7C6Cl2O42\u2212, (III), have been determined at 120\u2005K. In the crystal of (I), the base mol\u00adecule is in the lactam form and no acid\u2013base inter\u00adaction involving H-atom transfer is observed. The acid mol\u00adecule lies on an inversion centre and the asymmetric unit consists of one half-mol\u00adecule of chloranilic acid and one 2-pyridone mol\u00adecule, which are linked via a short O\u2014H\u22efO hydrogen bond. 2-Pyridone mol\u00adecules form a head-to-head dimer via a pair of N\u2014H\u22efO hydrogen bonds, resulting in a tape structure along [201]. In the crystals of (II) and (III), acid\u2013base inter\u00adactions involving H-atom transfer are observed and the divalent cations lie on an inversion centre. The asymmetric unit of (II) consists of one half of a chloranilate anion and one 3-hy\u00addroxy\u00adpyridinium cation, while that of (III) comprises two independent halves of anions and two 4-hy\u00addroxy\u00adpyridinium cations. The primary inter\u00admolecular inter\u00adaction in (II) is a bifurcated O\u2014H\u22ef hydrogen bond between the cation and the anion. The hydrogen-bonded units are further linked via N\u2014H\u22efO hydrogen bonds, forming a layer parallel to the bc plane. In (III), one anion is surrounded by four cations via O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, while the other is surrounded by four cations via N\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds. These inter\u00adactions link the cations and the anions into a layer parallel to (301).The crystal structures of the 1:2 compounds of chloranilic acid  with 2-pyridone, 3-hy\u00addroxy\u00adpyridine and 4-hyroxypyridine, namely, bis\u00ad(2-pyridone) chloranilic acid, 2C A weak C\u2014H\u22efCl inter\u00adaction formed between the acid and base mol\u00adecules ii; symmetry code as in Table\u00a02bc plane \u2005\u00c5; symmetry code: (vi) \u2212x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a0In the crystal of (II)ne Fig.\u00a07. Adjacenvia weak C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions et al., 2016et al., 2010et al., 2016et al., 2009aet al., 2009bA search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(O or N). C-bound H atoms were positioned geometrically (C\u2014H = 0.95\u2005\u00c5) and were treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017013536/lh5855sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989017013536/lh5855Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013536/lh5855IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017013536/lh5855IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1575722, 1575721, 1575720CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The synthesis, characterization and structural analysis of triphenylphosphoniummethylenetrifluoroborate are presented. 19H17BF3P {alternative name: triphen\u00adyl[(tri\u00adfluoro\u00adboran\u00adyl)meth\u00adyl]phosphanium}, was formed by the reaction of tri\u00adphenyl\u00adphosphine with potassium iodo\u00admethyl\u00adtri\u00adfluoro\u00adborate. The mol\u00adecule features a nearly staggered conformation along the P\u2014C bond and a less than staggered conformation along the C\u2014B bond. In the crystal, weak C\u2014H\u22efF hydrogen bonds between the meta-phenyl C\u2014H groups and the tri\u00adfluoro\u00adborate B\u2014F groups form chains of R22(16) rings along [100]. These chains are are further stabilized by weak C\u2014H\u22ef\u03c0 inter\u00adactions. A weak intra\u00admolecular C\u2014H\u22efF hydrogen bond is also observed.The title compound, C Additionally, they may be used to produce organodihaloboranes (RBX2)  with boron trifluoride di\u00adethyl\u00adetherate (BF3-OEt2) yields triphen\u00adyl[(tri\u00adfluoro\u00adboran\u00adyl)meth\u00adyl]phosphonium (Ph3PCH2BF3). We have synthesized Ph3PCH2BF3via an alternate route, by reacting tri\u00adphenyl\u00adphosphine (PPh3) with potassium iodo\u00admethyl\u00adtri\u00adfluoro\u00adborate (ICH2BF3K) in 45% yield.Alkyl\u00adtri\u00adphenyl\u00adphospho\u00adnium (PhDatabase survey). Phospho\u00adnium tri\u00adfluoro\u00adborates have been shown to enhance the hydrolytic stability of the RBF3 moiety  ring \u00b0] and a less staggered conformation along the C1\u2014B1 bond [F2\u2014B1\u2014C1\u2014P1 torsion angle = 158.3\u2005(2)\u00b0].The mol\u00adecular structure of the title compound is shown in Fig.\u00a01g Table\u00a01. The molet al., 19873sp hybridized. The methyl\u00adene carbon is predominantly 3sp hybridized, but has a distorted tetra\u00adhedral geometry with a P1\u2014C1\u2014B1 angle of 119.7\u2005(2)\u00b0.The B-F bond lengths fall within normal ranges for organotri\u00adfluoro\u00adborate compounds. The methyl\u00adene C\u2014P bond length [1.787\u2005(4)\u2005\u00c5] and the C\u2014B bond length [1.636\u2005(4)\u2005\u00c5] also fall within the normal range for similar compounds  and the resulting solid was dissolved in a minimal amount of acetone and the product was precipitated with water and collected by filtration, to afford a white solid  X-ray quality crystals were grown by slow diffusion of pentane into a solution of the title compound dissolved in di\u00adchloro\u00admethane.Potassium iodo\u00admethyl\u00adtri\u00adfluoro\u00adborate  and tri\u00adphenyl\u00adphosphine  were combined in a pressure flask containing a stir bar under nitro\u00adgen, and anhydrous THF (25.0\u2005mL) was added. The flask was sealed and heated to 343\u2005K for 18\u2005h. The reaction was cooled to room temperature and the solvent was removed 1H NMR  \u03b4 (ppm): 7.66 , 7.56 , 2.07 . 13C NMR  \u03b4 (ppm): 133.7 , 133.5 , 129.6  123.2  (C\u2014B not observed). 11B NMR  \u03b4 (ppm): 2.49 . 19F NMR  \u03b4 (ppm): \u2212138.9 . FTIR : 3070, 2960, 1587, 1484, 1438, 1146, 1104, 1025, 994, 969, 824, 754, 725, 691, 511, 497.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017009884/lh5846sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017009884/lh5846Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017009884/lh5846Isup3.cmlSupporting information file. DOI: 1560028CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure of the title imidazole derivative is reported. The structure is stabilized by an extensive O\u2014H\u22efN, C\u2014H\u22efO/Cl and C\u2014H\u22ef\u03c0(ring) hydrogen-bonding network. 24H21ClN2O, crystallizes with two unique mol\u00adecules in the asymmetric unit. In each mol\u00adecule, the central imidazole ring is substituted at the 2-, 4- and 5-positions by benzene rings. The 2-substituted ring carries a Cl atom at the 4-position. One of the imidazole N atoms in each mol\u00adecule has a propan-2-ol substituent. In the crystal, a series of O\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds, augmented by several C\u2014H\u22ef\u03c0(ring) inter\u00adactions, generate a three-dimensional network of mol\u00adecules stacked along the a-axis direction.The title compound, C Each moO\u22efN23 hydrogen bonds supported by C242\u2014H242\u22efO112 contacts combine with O212\u2014H22O\u22efN13 hydrogen bonds to link alternate type 1 and 2 mol\u00adecules in a head-to-tail fashion, forming C(7) chains along b, Fig.\u00a04C(12) chains along the a-axis direction, Fig.\u00a05Cg5 and C255\u2014H255\u22efCg1 contacts combine with C113\u2014H11D\u22efCg6, C213\u2014H21D\u22efCg2 and two C\u2014H\u22efO hydrogen bonds, Table\u00a01c axis, Fig.\u00a063 across the unit cell. This large void is unexpected as no solvent appeared and the final difference map was reasonably flat . The mol\u00adecules stack in an orderly fashion along each of the three principal crystallographic axes and the voids are clearly visible in views of the overall packing along these directions, see for example Fig.\u00a07O112\u2013H12et al., 2016H-imidazol-2-yl]benzoic acid . All other H atoms were refined using a riding model with d(C\u2014H) = 0.95\u2005\u00c5, Uiso = 1.2Ueq(C) for aromatic, 1.00\u2005\u00c5 for methine and 0.99\u2005\u00c5 for CH2 H atoms, all with Uiso = 1.2Ueq(C) and 0.98\u2005\u00c5, Uiso = 1.5Ueq(C) for CH3 H atoms. Seven reflections with Fo >>> Fc, were omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016019332/hg5480sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016019332/hg5480Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016019332/hg5480Isup3.cmlSupporting information file. DOI: 1520559CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In (I), the di\u00adthio\u00adcarbamate ligand coordinates the SnIV atom in an asymmetric manner, leading to a highly distorted trigonal\u2013bipyramidal coordination geometry defined by a C3S2 donor set with the weakly bound S atom approximately trans to one of the ipso-C atoms. A similar structure is found in (II), but the di\u00adthio\u00adcarbamate ligand coordinates in an even more asymmetric fashion. The packing in (I) features supra\u00admolecular chains along the c axis sustained by C\u2014H\u22ef\u03c0 inter\u00adactions; chains pack with no directional inter\u00adactions between them. In (II), supra\u00admolecular layers are formed, similarly sustained by C\u2014H\u22ef\u03c0 inter\u00adactions; these stack along the b axis. An analysis of the Hirshfeld surfaces for (I) and (II) confirms the presence of the C\u2014H\u22ef\u03c0 inter\u00adactions but also reveals the overall dominance of H\u22efH contacts in the respective crystals.The crystal and mol\u00adecular structures of two tri\u00adphenyl\u00adtin di\u00adthio\u00adcarbamates, [Sn(C RSn(S2CNRR\u2032)n4\u2013 where R, R\u2032 = alkyl, aryl, most relate to their biological activities and their usefulness as mol\u00adecular, single-source precursors for the formation of tin sulfide nanoparticles 3Sn[S2CN(Ben)CH2CH2Ph] (I)6H5)3Sn[S2CN(CH2CH2OMe)2] (II)Among the varied motivations for investigating organotin di\u00adthio\u00adcarbamate compounds, long and Sn\u2014Sshort bond lengths, of 0.42\u2005\u00c5. This asymmetry is reflected in the relatively large disparity in the associated C\u2014S bond lengths with the bond involving the tightly bound S1 atom being significantly longer than the bond involving the S2 atom, Table\u00a01i.e. from a narrow 92.98\u2005(4)\u00b0 for S1\u2014Sn\u2014C17 to a wide 124.31\u2005(4)\u00b0 for S1\u2014Sn\u2014C29. The wide angle is due to the close approach to the tin atom of S2. Further, the Sn\u2014C17 bond length is systematically longer than the other Sn\u2014C bond lengths, an observation ascribed to the C17 atom being approximately trans to the incoming S2 atom, Table\u00a013S2 donor set. The geometry is not ideal with the value of \u03c4 of 0.57, cf. \u03c4 values of 0.0 and 1.0 for ideal square\u2013pyramidal and trigonal\u2013bipyramidal geometries, respectively cf. 0.06\u2005\u00c5 for (I)trans to the S2 atom, is the longest of all six Sn\u2014C bonds in (I)i.e. 90.94\u2005(4)\u00b0 for S1\u2014Sn\u2014C14 to 119.54\u2005(5)\u00b0 for C8\u2014Sn\u2014C20, is slightly narrower at less than 30\u00b0. The value of \u03c4 computes to 0.58, i.e. virtually identical to that in (I)The mol\u00adecular structure of (II)PLATON ac plane, Fig.\u00a04a. The layers stack along the b axis without directional inter\u00adactions between them, Fig.\u00a04b.Even though there are oxygen atoms in the mol\u00adecule of (II)Crystal Explorer di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the inter\u00admolecular inter\u00adactions through the mapping of dnorm. The combination of de and di in the form of two-dimensional fingerprint plots dnorm (not shown). The curvature of the Hirshfeld surfaces around the phenyl rings participating as acceptors in the C\u2014H\u22ef\u03c0 contacts determine the strength of these inter\u00adactions in the crystal packing. In the structure of (I)i.e. with the H13 and H23 hydrogen atoms. The other C\u2014H\u22ef\u03c0 contact involves methyl-H7C atom as the donor and phenyl (C8\u2013C13) ring as the acceptor. The shape-indexed Hirshfeld surfaces highlighting the C\u2014H\u22ef\u03c0 contacts are shown in Fig.\u00a07The different shapes of Hirshfeld surfaces for mol\u00adecules (I)et al., 2007a\u2013d, respectively; their relative contributions are summarized in Table\u00a04de, di) ranges, i.e. between 1.2 and 2.6\u2005\u00c5, the densities and the areas of their distributions are different. It is evident from the data in Table\u00a04b that these contacts make the most significant contribution to the Hirshfeld surfaces of both (I)b), all the points are situated at the  distances greater than or equal to their van der Waals separations i.e. 2 x 1.2\u2005\u00c5, hence there is no propensity to form such inter\u00admolecular contacts. The peak at  distances slightly less than van der Waals separations in the fingerprint plot for (II)A\u22efH5Ai = 2.36\u2005\u00c5; symmetry code: (i) \u2212x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. In the fingerprint plot delineated into C\u22efH/H\u22efC contacts for (I)c, the 32.9% contribution to the Hirshfeld surface and the symmetrical distribution of points showing bending of the pattern at (de + di)min \u223c2.8\u2005\u00c5 is the result of short inter\u00adatomic C\u22efH/H\u22efC contacts . In the structure of (II)i.e. 24.4%, an observation ascribed to the presence of only C\u2014H\u22ef\u03c0 contacts in the mol\u00adecular packing, with no other short inter-atomic contacts. The negligible contribution from C\u22efC contacts to the Hirshfeld surfaces indicate that despite the presence of three Sn-bound phenyl rings in the structures of both (I)d, show that crowded geometries around the tin atoms prevent the sulfur atoms from forming such inter\u00admolecular contacts although these contacts have significant contributions to their respective Hirshfeld surfaces, Table\u00a04et al., 2016The overall two-dimensional fingerprint plots for (I)et al., 2016R/R\u2032 substituents. For example, the \u2212S2CN(Ben)CH2CH2Ph anion in (I)2CN(Ben)CH2CH2Ph]2 2 anion, as in (II)et al., 2009et al., 2010According to a search of the Cambridge Structural Database  features the shortest Sn\u2014S bond length of the series at 2.429\u2005(3)\u2005\u00c5  of 0.74\u2005\u00c5, is found in the structure of Ph3Sn(4-nitro\u00adphenyl\u00adpiperazine-1-di\u00adthio\u00adcarbamate) , having \u0394(Sn\u2014S) of 0.42\u2005\u00c5 Reflecting the inter\u00adest in organotin di\u00adthio\u00adcarbamates, there are approximately 40 examples of tri\u00adphenyl\u00adtin di\u00adthio\u00adcarbamate structures in the CSD, all of which present the same basic structural motif as described herein for (I)N-Benzyl-2-phenyl\u00adethyl\u00adamine (2\u2005mmol) dissolved in ethanol (10\u2005ml) was stirred for 30\u2005min in an ice-bath. 25% ammonia (1\u20132\u2005ml) was added to generate a basic solution. After that, a cold ethano\u00adlic solution of carbon di\u00adsulfide (2\u2005mmol) was added to the solution followed by stirring for about 2\u2005h. Then, tri\u00adphenyl\u00adtin(IV) chloride (2\u2005mmol) dissolved in ethanol (30\u2005ml) was added drop wise into the solution followed by further stirring for 2\u2005h. The precipitate that formed was filtered off and washed with cold ethanol a few times to remove impurities. Finally, the precipitate was dried in a desiccator. Recrystallization was achieved by dissolv\u00ading the compound in a chloro\u00adform and ethanol mixture (1:1 v/v): this solution was allowed to slowly evaporate at room temperature yielding colourless slabs of (I)34H31NS2Sn requires: C, 64.2; H, 4.9; N, 2.2; S, 10.1. IR (cm\u22121): 1476 \u03bd(C\u2014N), 1021 \u03bd(C\u2014S), 502 \u03bd(Sn\u2014C), 448 \u03bd(Sn\u2014S). 1H NMR (CDCl3): 7.44\u20137.86 , 7.16\u20137.39 , 5.03 , 3.96 , 3.04 . 13C{1H} NMR (CDCl3): \u03b4 197.8 (S2C), 126.7\u2013142.3 (Ar), 59.8 (CH2Ben), 56.4 (NCH2CH2), 32.8 (NCH2CH2). 119Sn{1H} NMR (CDCl3): \u2212180.2.Synthesis of (I)N-benzyl-2-phenyl\u00adethyl\u00adamine. Recrystallization was from chloro\u00adform solution to yield colourless slabs. M.p.: 366\u2013367\u2005K. Yield: 89%. Analysis: found C, 54.4; H, 4.4; N, 2.9; S, 12.1. C25H29NO2S2 Sn requires: C, 53.8; H, 5.2; N, 2.5; S, 11.5. IR (cm\u22121): 1470 \u03bd(C\u2014N), 994 \u03bd(C\u2014S), 559 \u03bd(Sn\u2014C), 425 \u03bd(Sn\u2014S). 1H NMR (CDCl3): 7.40\u20137.74 , 4.13 , 3.72 , 3.35 . 13C{1H} NMR (CDCl3): \u03b4 197.3 (S2C), 128.6\u2013142.4 (Ar), 70.0 (OCH2), 59.0 (NCH2), 57.1 (CH3). 119Sn{1H} NMR (CDCl3): \u2212185.0.Compound (II)Uiso(H) set to 1.2\u20131.5Ueq(C). In the refinement of (II)Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016014985/hb7618sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016014985/hb7618Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016014985/hb7618IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1505733, 1505732CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E. The packing features amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds, leading to centrosymmetric aggregates, as well as C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, which significantly influence the packing.An intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond is found in the disubstituted amino\u00adurea residue; the conformations about the imine and ethyl\u00adene double bonds are  23H21N3O2, is constructed about an almost planar disubstituted amino\u00adurea residue (r.m.s. deviation = 0.0201\u2005\u00c5), which features an intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond. In the \u2018all-trans\u2019 chain connecting this to the terminal meth\u00adoxy\u00adbenzene residue, the conformation about each of the imine and ethyl\u00adene double bonds is E. In the crystal, amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds connect centrosymmetrically related mol\u00adecules into dimeric aggregates, which also incorporate ethyl\u00adene-C\u2014H\u22efO(amide) inter\u00adactions. The dimers are linked by amine\u2013phenyl-C\u2014H\u22ef\u03c0(imine\u2013phen\u00adyl) and meth\u00adoxy\u00adbenzene-C\u2014H\u22ef\u03c0(amine\u2013phen\u00adyl) inter\u00adactions to generate a three-dimensional network. The importance of C\u2014H\u22ef\u03c0 inter\u00adactions in the mol\u00adecular packing is reflected in the relatively high contributions made by C\u22efH/H\u22efC contacts to the Hirshfeld surface, i.e. 31.6%.The title compound, C These compounds have attracted much attention due to their diverse pharmacological and biological activities 3O = 0.0201\u2005\u00c5), owing in part to an intra\u00admolecular amine-N\u2014H\u22efN(imine) hydrogen bond, Table\u00a013O plane, forming a dihedral angle of 46.88\u2005(4)\u00b0. The imine/ethyl\u00adene sequence of bonds, i.e. N3=C8\u2014C9=C10\u2014C11, has an all-trans conformation but the N3\u2014C8\u2014C9\u2014C10 and C8\u2014C9\u2014C10\u2014C11 torsion angles of 154.62\u2005(12) and \u2212169.19\u2005(11)\u00b0, respectively, indicate some twisting in this residue, especially about the C8\u2014C9 bond; the conformation about each of the double bonds is E. The imine-bound phenyl ring forms a dihedral angle of 63.30\u2005(7)\u00b0 with the C4N atoms of the imine/ethyl\u00adene sequence, and the corresponding angle for the terminal meth\u00adoxy\u00adbenzene ring is significantly less, at 8.29\u2005(13)\u00b0. The meth\u00adoxy group is twisted out of the plane of the ring to which it is connected as seen in the value of the C17\u2014O18\u2014C14\u2014C15 torsion angle of 15.55\u2005(17)\u00b0.The mol\u00adecular structure of (I)2, Table\u00a01a, as well as meth\u00adoxy-C\u2014H\u22ef\u03c0(amine-phen\u00adyl) contacts, Table\u00a01via amine-phenyl-C\u2014H\u22ef\u03c0(imine-phen\u00adyl) and meth\u00adoxy-benzene-C\u2014H\u22ef\u03c0(amine-phen\u00adyl) inter\u00adactions, Fig.\u00a02b.The most notable feature of the mol\u00adecular packing of (I)et al., 2017N and carbonyl-O1 atoms on the Hirshfeld surface mapped over dnorm in Fig.\u00a03a. The appearance of diminutive red spots near the N3 and C17 atoms, Fig.\u00a03a, and the tiny faint-red spots near the C9 and H82 atoms in Fig.\u00a03b, indicate the influence of short inter\u00adatomic N3\u22efC17 and C9\u22efH82 contacts, Table\u00a02a, the concave region around the imine-phenyl ring on one side and the biconcave region around the amine-phenyl ring indicate their involvement in one and two C\u2014H\u22ef\u03c0 contacts, respectively. The short inter\u00adatomic O\u22efH/H\u22efO contacts s Table\u00a03 as well a, and those delineated into H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO and N\u22efH/H\u22efN contacts c, which is due to the presence of a significant number of C\u2014H\u22ef\u03c0 inter\u00adactions involving the imine- and amine-phenyl rings, as well as short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a03c. The pair of forceps-like long tips at de + di = 2.1\u2005\u00c5 in the fingerprint plot delineated into O\u22efH/H\u22efO contacts, Fig.\u00a06d, reflect the presence the N\u2014H\u22efO hydrogen bond; the pair of spikes corresponding to the C\u2014H\u22efO contacts and the points related to short inter\u00adatomic O\u22efH/H\u22efO contacts, Table\u00a02e, as their inter\u00adatomic distances are greater than their van der Waals separations, they do not make a specific contribution to the mol\u00adecular packing. The participation of the methyl-C17 atom in two close inter\u00adatomic contacts, Table\u00a02A and H17B atoms so are not surface contacts. Finally, the small contributions from other inter\u00adatomic contacts summarized in Table\u00a03The C\u22efH/H\u22efC contacts in the crystal make the second largest contribution, et al., 2016et al., 2005E-conformations about the two analogous double bonds in the mol\u00adecule. However, there is considerable twisting about the equivalent bonds to C8\u2014C9 in (I)i.e. the N\u2014C\u2014C\u2014C torsion angles are 130.3\u2005(6) and 136.0\u2005(6)\u00b0, cf. 154.62\u2005(12)\u00b0 in (I)The title compound was prepared from the de\u00adhydrogenation reaction of 4-phenyl\u00adsemicarbazide and 4-meth\u00adoxy\u00adchalcone. A search of the Cambridge Structural Database , m.p. 407\u2005K. IR (cm\u22121): 3336 \u03bd(N\u2014H), 1679 \u03bd(C=O), 1526 \u03bd(C=N), 1242 \u03bd(C\u2014N), 1025 \u03bd(C=S). MS (m/z): 371.25 [M+1]+.Analytical grade reagents were used as procured without further purification. 4-Phenyl\u00adsemicarbazide  and 4-meth\u00adoxy\u00adchalcone  were dissolved separately in hot absolute ethanol (30\u2005ml) and mixed with stirring. A few drops of concentrated hydro\u00adchloric acid were added as a catalyst. The reaction mixture was heated and stirred for about 20\u2005min., then stirred for a further 30\u2005min. at room temperature. The resulting yellow precipitate was filtered, washed with cold ethanol and dried Uiso(H) set to 1.2\u20131.5Ueq(C). The nitro\u00adgen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017014128/hb7709sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989017014128/hb7709Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017014128/hb7709Isup3.cmlSupporting information file. DOI: 1577439CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "IV atom in [Sn(C7H6F)2Cl2(C2H6OS)2] is located on a centre of inversion so the resulting donor C2Cl2O2 donor set is all-trans. The three-dimensional mol\u00adecular packing is sustained by C\u2014H\u22efF, C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions.The octa\u00adhedrally coordinated Sn IV atom in the title diorganotin compound, [Sn(C7H6F)2Cl2(C2H6OS)2], is located on a centre of inversion, resulting in the C2Cl2O2 donor set having an all-trans disposition of like atoms. The coordination geometry approximates an octa\u00adhedron. The crystal features C\u2014H\u22efF, C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions, giving rise to a three-dimensional network. The respective influences of the Cl\u22efH/H\u22efCl and F\u22efH/H\u22efF contacts to the mol\u00adecular packing are clearly evident from the analysis of the Hirshfeld surface.The Sn The SnIV atom is coordinated by monodentate ligands, i.e. chloride, sulfoxide-O and methyl\u00adene-C atoms. From symmetry, each donor is trans to a like atom resulting in an all-trans-C2Cl2O2 donor set about the SnIV atom. The donor set defines a distorted octa\u00adhedral geometry owing, in part, to the disparate Sn\u2014donor atom bond lengths, Table\u00a01IV atom differ relatively little from the ideal octa\u00adhedral angles with the maximum deviation of ca 6\u00b0 noted for the C1\u2014Sn\u2014O1 angle, Table\u00a01The mol\u00adecular structure of (I)bc plane, Fig.\u00a02a. Layers are connected along the a axis by phenyl-C3\u2014H\u22efF1 and methyl-C9\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions to consolidate the mol\u00adecular packing, Fig.\u00a02b.The mol\u00adecular packing in (I)et al., 2016dnorm in Fig.\u00a03B and a pair near Cl1 in Fig.\u00a03dnorm- and shape-index-mapped Hirshfeld surfaces highlighting the various C\u2014H\u22efCl, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions are illustrated in Fig.\u00a05a\u2013c, respectively.The Hirshfeld surface analysis on the structure of (I)et al., 2007a\u2013f, respectively, and their relative contributions to the Hirshfeld surfaces are summarized in Table\u00a04b, that although these contacts have the greatest contribution, i.e. 45.7%, to the Hirshfeld surface, the dispersion forces acting between them keep these atoms at the distances greater than the sum of their van der Waals radii, hence they do not contribute significantly to the mol\u00adecular packing. The comparatively greater contribution of F\u22efH/H\u22efF contacts to the Hirshfeld surface cf. Cl\u22efH/H\u22efCl contacts, Table\u00a04c. The forceps-like distribution of points in the plot with tips at de + di \u223c2.8\u2005\u00c5 result from the bifurcated C\u2014H\u22efCl inter\u00adactions, and points at positions less than the sum of their van der Waals radii are ascribed to the short inter\u00adatomic Cl\u22efH/H\u22efCl contacts, the green appearance due to high density of inter\u00adactions. Similarly, a pair of short spikes at de + di \u223c2.5\u2005\u00c5 in the fingerprint plot delineated into F\u22efH/H\u22efF contacts, Fig.\u00a06d, are indicative of inter\u00admolecular C\u2014H\u22efF inter\u00adactions with the short inter\u00adatomic F\u22efH/H\u22efF contacts merged within the fingerprint plot. It is important to note from the fingerprint plot delineated into C\u22efH/H\u22efC contacts, Fig.\u00a06e, that even though their inter\u00adatomic distances are equal to or greater than the sum of their van der Waals radii, i.e. 2.9\u2005\u00c5, the 12.8% contribution from these to the Hirshfeld surfaces are indicative of the presence of C\u2014H\u22ef\u03c0 inter\u00adactions in the structure. This is also justified from the presence of short inter\u00adatomic C\u22efC contacts, Fig.\u00a05c and Table\u00a03f, and the small contributions from the other contacts listed in Table\u00a02The overall two-dimensional fingerprint plot and those delineated into H\u22efH, Cl\u22efH/H\u22efCl, F\u22efH/H\u22efF, C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts (McKinnon R2SnX2(DMSO)2 in the crystallographic literature 2 compound tin dichloride was prepared in accordance with the literature method   and tri\u00adethyl\u00adamine  in ethyl acetate (25\u2005ml) was added to di(p-fluoro\u00adbenz\u00adyl)tin dichloride  in ethyl acetate (10\u2005ml). The resulting mixture was stirred and refluxed for 4\u2005h. The filtrate was evaporated until a dark-orange precipitate was obtained. The precipitate was dissolved in DMSO-d6 solution in a NMR tube for 1H NMR spectroscopic characterization. After the analysis, the tube was set aside for a month and colourless crystals of (I)\u22121): 1595(m) \u03bd(C=C), 1504(s) \u03bd(S=O), 1161(m), 578(w), 508(m) \u03bd(Sn\u2014O). 1H NMR (in CDCl3): 6.90\u20137.11, 7.35\u20137.40 , 3.11 , 2.17 .Uiso(H) set to 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989017005072/wm5381sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017005072/wm5381Isup2.hklStructure factors: contains datablock(s) I. DOI: 1541712CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structures of the centrosymmetric naphthoxazine derivative is reported. In the absence of hydrogen-bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions, the crystal structure is stabilized by short C\u2014H\u22ef\u03c0 contacts. 26H24N2O2, the oxazine moiety is fused to a naphthalene ring system. The asymmetric unit consists of one half of the mol\u00adecule, which lies about an inversion centre. The C atoms of the ethyl\u00adene spacer group adopt an anti\u00adperiplanar arrangement. The oxazine ring adopts a half-chair conformation. In the crystal, supra\u00admolecular chains running along the b axis are formed via short C\u2014H\u22ef\u03c0 contacts. The crystal studied was a non-merohedral twin with a fractional contribution of 0.168\u2005(2) of the minor twin component.In the title compound, C Evaporation at room temperature afforded the title compound in 73% yield after recrystallization.The oxazine moiety is well known as a building block for high-performance phenolic resins, which are of great inter\u00adest in industry due to their superior mechanical and physical properties together with unusually high thermal resistance \u2005\u00c5, \u03b8 = 51.5\u2005(4)\u00b0, \u03c6 = 86.6\u2005(4)\u00b0, and the ethyl\u00adene spacer group adopts an anti\u00adperiplanar arrangement as observed in 3,3\u2032-bis\u00ad  1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. However, unlike the related structures, which crystallized in monoclinic space groups with one mol\u00adecule in the asymmetric unit .In general terms, the structure of the title compound Fig.\u00a01 is similet al., 2007et al., 2015The aromatic C\u2014C bonds of naphthalene ring system have a narrow range of distances [from 1.365\u2005(5) to 1.431\u2005(4)\u2005\u00c5]. The central C5\u2014C10 bond at 1.415\u2005(4)\u2005\u00c5 is, however, shorter by 0.014\u2005\u00c5 than those in related structures  set to 1.2Ueq of the parent atom. The crystal was a non-merohedral twin with a fractional contribution of 0.168\u2005(2) of the minor twin component.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017006673/sj5529sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017006673/sj5529Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006673/sj5529Isup3.cmlSupporting information file. DOI: 1547729CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex, the divalent Ni ion occupies a crystallographically imposed centre of symmetry and is coordinated by two O atoms from the carboxyl\u00adate groups of two 2,4,6-tri\u00admethyl\u00adbenzoate ligands, two N atoms from the pyridyl groups of two isonicotinamide ligands and two water mol\u00adecules in a slightly distorted octa\u00adhedral geometry. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H\u22efH (59.8%), O\u22efH/H\u22efO (20.2%) and C\u22efH/H\u22efC (13.7%) inter\u00adactions.In the title Ni II complex, [Ni(C10H11O2)2(C6H6N2O)2(H2O)2]\u00b72H2O, the divalent Ni ion occupies a crystallographically imposed centre of symmetry and is coordinated by two O atoms from the carboxyl\u00adate groups of two 2,4,6-tri\u00admethyl\u00adbenzoate (TMB) ligands [Ni\u2014O = 2.0438\u2005(12)\u2005\u00c5], two N atoms from the pyridyl groups of two isonicotinamide (INA) ligands [Ni\u2014N = 2.1506\u2005(15)\u2005\u00c5] and two water mol\u00adecules [Ni\u2014O = 2.0438\u2005(12)\u2005\u00c5] in a slightly distorted octa\u00adhedral geometry. The coordinating water mol\u00adecules are hydrogen bonded to the non-coordinating carboxyl\u00adate O atom of the TMB ligand [O\u22efO = 2.593\u2005(3)\u2005\u00c5], enclosing an S(6) hydrogen-bonding motif. Two solvent water mol\u00adecules are also present in the formula unit. In the crystal, a network of inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds link the complexes into a three-dimensional array. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H\u22efH (59.8%), O\u22efH/H\u22efO (20.2%) and C\u22efH/H\u22efC (13.7%) inter\u00adactions.In the title Ni A deficiency in this vitamin leads to loss of copper from the body, giving rise to a condition known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels  carboxyl\u00adates are diverse and include one-dimensional (Guseinov 7H4ClO2)2(C6H6N2O)2(H2O)2]  \u00b72(H2O)    \u00b72H2O, and report its mol\u00adecular and crystal structures, along with a Hirshfeld surface analysis.The structures of a number of mononuclear complexes of divalent transition-metal ions with both nicotinamide (NA) and benzoic acid derivatives as ligands have been previously reported and include   hydrogen bonds (Table\u00a01The asymmetric unit of the mononuclear title compound (I)er Fig.\u00a01. In the z] Fig.\u00a01. The nons Table\u00a01. Intra\u00adms Table\u00a01 link H as Table\u00a01.A (C2\u2013C7), ring by 78.80\u2005(14)\u00b0, while the benzene and pyridine, B (N1/C11\u2013C15), rings are oriented at a dihedral angle of 24.33\u2005(6)\u00b0.The near equalities of the C1\u2014O1 [1.242\u2005(2)\u2005\u00c5] and C1\u2014O2 [1.260\u2005(2)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2\u2014C1\u2014O1 bond angle [124.52\u2005(17)\u00b0] is comparable the corresponding values of 124.4\u2005(2)\u00b0 in (II), 124.67\u2005(14)\u00b0 in (III), 124.22\u2005(11)\u00b0 in (IV), 125.71\u2005(10)\u00b0 in (V), 126.0\u2005(3)\u00b0 in (VI) and 120.47\u2005(15) and 123.17\u2005(15)\u00b0 in (VII), where the benzoate ions also coordinate the metal atoms monodentately. The Ni1 atom lies 0.3523\u2005(1)\u2005\u00c5 below the planar (O1/O2/C1) carboxyl\u00adate group. In the TMB anion, the carboxyl\u00adate group is twisted away from the attached benzene, coordW\u22efOnoncoordW, O\u2014HnoncoordW\u22efOc, N\u2014HINA\u22efOnoncoordW and N\u2014HINA\u22efOINA (INA = isonicotinamide and noncoordW = non-coordinating water) hydrogen bonds . The presence of these inter\u00adactions may also be shown by the Hirshfeld surface mapped as a function of curvedness  in H2O (50\u2005ml) and isonicotinamide  in H2O (25\u2005ml) with sodium 2,4,6-tri\u00admethyl\u00adbenzoate  in H2O (150\u2005ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for nine weeks and gave green single crystals . Combustion analysis: found; C, 54.70, H, 6.24; N, 8.13%. Calculated: C32H42N4NiO10 C, 54.80; H, 6.04; N, 7.99%. FT\u2013IR: 3354, 3197, 2235, 1949, 1855, 1698, 1934, 1612, 1557, 1415, 1226, 1182, 1148, 1115, 1096, 1066, 1041, 1017, 985, 885, 855, 792, 772, 747, 682, 660, 638, 615, 520, 443\u2005cm \u22121.The title compound was prepared by mixing solutions of NiSO2 groups and water mol\u00adecules were located in difference Fourier maps and refined freely. The C-bound H atoms were positioned geometrically with C\u2014H = 0.93 and 0.96\u2005\u00c5 for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic H atoms. The maximum and minimum residual density peaks were found at 0.83 and 0.78\u2005\u00c5 from atoms O1 and O4, respectively.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S205698901701060X/cq2020sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901701060X/cq2020Isup2.hklStructure factors: contains datablock(s) I. DOI: 1562879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Inter\u00admolecular N\u2014H\u22efO and C \u2014H\u22efO hydrogen bonds connect centrosymmetrically related mol\u00adecules into dimers, forming rings of a axis into a columnar arrangement.The title Schiff base mol\u00adecule displays a  16H16N4O5S\u00b7C3H7NO, displays a trans conformation with respect to the C=N double bond. The C\u2014N and N\u2014N bonds are relatively short compared to their normal bond lengths, indicating some degree of delocalization in the mol\u00adecule. The mol\u00adecule is bent at the S atom, with an S\u2014N\u2014C\u2014C torsion angle of 164.48\u2005(11)\u00b0. The dihedral angle between the two aromatic rings is 84.594\u2005(7)\u00b0. Inter\u00admolecular N\u2014H\u22efO and C \u2014H\u22efO hydrogen bonds connect centrosymmetrically related mol\u00adecules into dimers forming rings of R33(11) and R22(10) graph-set motif stacked along the a axis into a columnar arrangement. The mol\u00adecular columns are further linked into a three-dimensional network by C\u2014H\u22ef\u03c0 inter\u00adactions.The mol\u00adecule of the title Schiff base compound, C N-(p-toluene\u00adsulfon\u00adyl)amino acids have been studied extensively for their biological and medicinal activities -4-methyl-N-{2-[2-(4-nitro\u00adbenzyl\u00adidene)hydrazin-1-yl]-2-oxoeth\u00adyl}benzene\u00adsulfonamide N,N-di\u00admethyl\u00adformamide monosolvate.Hydrazones possess a wide variety of biological activities which include anti-inflammatory, analgesic, anti\u00adconvulsant, anti\u00adtuberculous, anti\u00adtumor, anti-HIV and anti\u00admicrobial activity. Hydrazones and their derivatives which can be prepared easily are stable and crystalline in nature. These characteristics have made them suitable compounds in recent times for drug design, ligands for metal complexes and for heterocyclic synthesis. Thus, hydrazones derived from syn to each other. The C8\u2014O3 and C9\u2014N3 bond lengths of 1.219\u2005(2) and 1.274\u2005(2)\u2005\u00c5, respectively, confirm their significant double-bond characters. Further, the C8\u2014N2 and N2\u2014N3 bond lengths of 1.354\u2005(2) and 1.3723\u2005(18)\u2005\u00c5, respectively, also indicate a significant delocalization of \u03c0-electron density over the hydrazone portion of the mol\u00adecule. The mol\u00adecule is bent at the S atom, with an S1\u2014N1\u2014C7\u2014C8 torsion angle of 164.48\u2005(11)\u00b0. The sulfonamide bond exists in a synclinal conformation, with a C\u2014S\u2014N\u2014C torsion angle of \u221278.2\u2005(1)\u00b0, which is the most preferred conformation for aromatic sulfon\u00adamides \u00b0 and C6\u2014C1\u2014S1\u2014N1 = 98.87\u2005(16)\u00b0, while that of the hydrazone group with the attached 4-nitrobenzene ring is given by the torsion angles C11\u2014C10\u2014C9\u2014N3 = 1.6\u2005(2)\u00b0 and C15\u2014C10\u2014C9\u2014N3 = \u2212177.27\u2005(15)\u00b0, respectively. The dihedral angle between the C1\u2013C6 sulfonyl benzene ring and the mean plane through the SO2\u2014NH\u2014CH2\u2014CO segment is 81.452\u2005(6)\u00b0, while that between the C10\u2013C15 benzene ring and the plane through the C9\u2014N3\u2014N2\u2014CO group is 4.296\u2005(10)\u00b0. The dihedral angle between the two aromatic rings is 84.594\u2005(7)\u00b0. The central part of the title compound, between atoms N1 and C9, is nearly planar with an extended chain conformation. The two benzene rings, i.e. C1\u2013C6 and C10\u2013C15, are inclined to the mean plane of the central spacer unit  by 85.59\u2005(8) and 4.35\u2005(8)\u00b0, respectively.The title compound crystallizes as a di\u00admethyl\u00adformamide (DMF) monosolvate with one mol\u00adecule each of the Schiff base and solvent in the asymmetric unit Fig.\u00a01, and twoa axis by C\u2014H\u22efO hydrogen bonds involving aromatic C3 and sulfonyl O3 atoms -N-{2-[2-(4-methyl\u00adbenzyl\u00adidene)hydrazin-1-yl]-2-oxoeth\u00adyl}-p-toluene\u00adsulfonamide, (II) E)-N-{2-[2-(4-Nitro\u00adbenzyl\u00adidene)hydrazine-1-yl]-2-oxoeth\u00adyl}-4-methyl\u00adbenzene\u00adsulfonamide N,N-di\u00admethyl\u00adformamide mono\u00adsolvate was prepared as follows: p-toluene\u00adsulfonyl chloride (0.01\u2005mol) was added to glycine (0.02\u2005mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373\u2005K for 6\u2005h, left overnight at room temperature, then filtered and treated with dilute hydro\u00adchloric acid. The solid N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycine (L1) obtained was crystallized from aqueous ethanol. Sulfuric acid (0.5\u2005ml) was added to L1 (0.02\u2005mol) dissolved in ethanol (30\u2005ml) and the mixture was refluxed. The reaction mixture was monitored by thin-layer chromatography (TLC) at regular inter\u00advals. After completion of the reaction, the reaction mixture was concentrated to remove excess ethanol. The product, N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycine ethyl ester (L2), was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone. Pure L2 (0.01\u2005mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10\u2005ml) in 30\u2005ml ethanol and the mixture was refluxed for 6\u2005h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-methyl\u00adbenzene\u00adsulfon\u00adyl)glycinyl hydrazide (L3). A mixture of L3 (0.01\u2005mol) and p-nitro\u00adbenzaldehyde (0.01\u2005mol) in anhydrous methanol (30\u2005ml) and two drops of glacial acetic acid was refluxed for 8\u2005h. After cooling, the precipitated (E)-N-{2-[2-(4-nitro\u00adben\u00adzyl\u00adidene)hydrazine-1-yl]-2-oxoeth\u00adyl}-4-methyl\u00adbenzene\u00adsul\u00adfon\u00adamide was collected by vacuum filtration, washed with cold methanol, dried and recrystallized to constant melting point from methanol (522\u2013523\u2005K). The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3236.6, 1687.7, 1587.4, 1338.6 and 1163.1\u2005cm\u22121 for the stretching bands of N\u2014H, C=O, C=N, S=O asymmetric and S=O symmetric, respectively. The characteristic 1H and 13C NMR specta of the title compound are as follows. 1H NMR , 3.61, 4.10 , 7.36\u20137.39 , 7.72\u20137.74 , 7.86 , 8.23\u20138.27 , 7.93 , 8.02 , 11.74 . 13C NMR : \u03b4 20.91, 43.20, 44.55, 123.94, 126.60, 127.81, 129.48, 137.48, 140.24, 141.40, 142.64, 144.62, 147.73, 164.64, 169.44. Prism-like colourless single crystals of the title compound employed in the X-ray diffraction study were grown from a DMF solution by slow evaporation of the solvent. or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017014669/rz5222sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017014669/rz5222Isup2.hklStructure factors: contains datablock(s) I. DOI: 1433602CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III(CO)(C(dppm)2-\u03ba3P,C,P\u2032)ClH]Cl and Cl2 have been determined. Both complexes show a slightly distorted octa\u00adhedral coordinated IrIII centre. The PCP pincer ligand system is arranged in a meridional manner.The crystal structures of [Ir et al. meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}methane-\u03ba3P,C,P\u2032)carbonyl\u00adchlorido\u00adhydridoiridium(III) chloride di\u00adchloro\u00admethane tris\u00adolvate, Cl\u00b73CH2Cl2 (1) and the closely related (bis\u00ad{[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}methanide(1+)-\u03ba3P,C,P\u2032)carbonyl\u00adchlorido\u00adhy\u00addridoirid\u00adium(III) dichloride\u2013hydro\u00adchloric acid\u2013water (1/2/5.5), Cl}2 (2), have been designed and both complexes show a slightly distorted octa\u00adhedral coordinated IrIII centre. The PCP pincer ligand system is arranged in a meridional manner, the CO ligand is located trans to the central PCP carbon and a hydride and chloride are located perpendicular above and below the P2C2 plane. With an Ir\u2014CCDP distance of 2.157\u2005(5)\u2005\u00c5, an Ir\u2014CO distance of 1.891\u2005(6)\u2005\u00c5 and a quite short C\u2014O distance of 1.117\u2005(7)\u2005\u00c5, complex 1 presents a strong carbonyl bond. Complex 2, the corresponding CH acid of 1, shows an additionally attached proton at the carbodi\u00adphospho\u00adrane carbon atom located anti\u00adperiplanar to the hydride of the metal centre. In comparison with complex 1, the Ir\u2014CCDP distance of 2.207\u2005(3)\u2005\u00c5 is lengthened and the Ir\u2014C\u2014O values indicate a weaker trans influence of the central carbodi\u00adphospho\u00adrane carbon atom.After the successful creation of the newly designed PCP carbodi\u00adphospho\u00adrane (CDP) ligand [Reitsamer  al. 2012. Dalton  al. 2007. Chem. C Consequently, this central atom disposes of two lone-electron pairs and is able to inter\u00adact with one or two Lewis acids  functionality and can be described as a naked carbon atom or as a divalent carbon(0) atom in an excited singlet (12]Cl enters an oxidative addition reaction with Vaska\u2019s compound [IrI(CO)Cl(PPh3)2], forming the iridium PCP pincer CDP complex Cl (1) (see reaction scheme). During this reaction sequence, the central carbon atom is deprotonated, becomes neutral and coordin\u00adates the iridium transition metal. Treatment of complex 1 with hydro\u00adchloric acid leads to the protonation of the central carbon atom and consequently to the formation of the conjugate CH acid of 1, the Cl2 complex 2 1 (C(dppm)2-\u03ba3P,C,P\u2032)ClH]+ monocation and the chloride counter-ion. The iridium transition metal centre exhibits an octa\u00adhedral ligand system, formed by a meridional arranged C(dppm)2, relative to the C1 atom, a trans-coordinated carbonyl unit, and a chlorido and hydrido ligand located perpendicular to the meridional plane or more precisely trans to each other. The P1\u2014Ir1\u2014P4 angle of 170.69\u2005(5)\u00b0 indicates a small deviation from the octa\u00adhedral geometry and this value is larger compared to many related Iridium PCP pincer complexes. The environment of the CDP carbon atom C1 is strictly planar  < Csp3]. Consequently, the Ir1\u2014C1 separation of 2.157\u2005(5)\u2005\u00c5 indicates an sp3 hybridization of the carbodiphosphorane carbon atom, which is substantiated by the data collected in Table\u00a01B] and 2.62\u2005\u00c5 [Cl2\u22efH3B] illustrate the location within the van der Waals radii. These C\u2014H\u22efX inter\u00adactions are a common feature of complexes containing dppm or related ligands ] and 2.47\u2005\u00c5 [Cl2\u22efH6B].Complex 1 Fig.\u00a01 crystall2 comprises two Cl2 complex mol\u00adecules (CH(dppm)2-\u03ba3P,C,P\u2032)ClH]2+ dication stabilized by two chloride counter-ions. Overall, complex 2 represents the conjugate CH acid of the Cl complex (1). The carbodi\u00adphospho\u00adrane carbon atom additionally coordinates a second Lewis acid, the proton H1, which adopts an anti-periplanar conformation relative to the hydrido ligand H11. As a consequence, atom C1 forms a distorted tetra\u00adhedron with the directly coordinated atoms (sum of angles = 344.3\u00b0). In comparison with complex 1, the values of the angles P2\u2014C1\u2013Ir1 and P3\u2014C1\u2014Ir1 are significantly reduced, whereas the P2\u2014C1\u2014P3 angles differs to a lesser extent (Table\u00a021 [2.157\u2005(5)\u2005\u00c5], as has also been observed in other carbodi\u00adphospho\u00adrane complexes ], 2.89\u2005\u00c5 [H2B\u22efCl7] and 2.57\u2005\u00c5 [H3B\u22efCl5].The asymmetric unit of es Fig.\u00a02, four mot Table\u00a02. The coos Table\u00a04 between 1, there are inter\u00adactions  = 2.62\u2005\u00c5] with distances shorter than the sum of the van der Waals radii. Such C\u2014H\u22efX inter\u00adactions are a common feature of complexes containing dppm or related ligands  = 2.59\u2005\u00c5 and H5B\u22efCl2 = 2.47\u2005\u00c5].In s Table\u00a03 between 2, C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions ], 2.89\u2005\u00c5 [H2B\u22efCl7] and 2.57\u2005\u00c5 [H3B\u22efCl5]. A network of different inter\u00adactions occurs between the two independent complex mol\u00adecules. The water and hydro\u00adchloric acid solvent mol\u00adecules form hydrogen bonds with the chloride ligands or counter-ions and the hydrogen atoms of the complex mol\u00adecules, respectively.In s Table\u00a04 occur be2) using standard Schlenk techniques. The 1H, 13C and 31P NMR spectra were recorded on a Bruker DPX 300 NMR spectrometer and were referenced against the 13C/1H solvent peaks of the solvents chloro\u00adform, methanol or the external 85% H3PO4 standard, respectively. The phospho\u00adrus atoms in the NMR data are labelled as in Figs. 1All preparations were carried out under an inert atmosphere (N2-Synthesis of Cl (1): A mixture of 19.5\u2005mg of Vaska\u2019s complex (0.025\u2005mmol), 20.4\u2005mg of [CH(dppm)2]Cl (0.025\u2005mmol)  was stirred at ambient temperature for 15\u2005min. The solvent was evaporated in vacuo and the residue was digested with a mixture of CH2Cl2 (0.1\u2005ml) and ethyl acetate (0.7\u2005ml). The solid was separated and washed twice with ethyl acetate (0.6\u2005ml). Single crystals were grown by slow evaporation of a solution in CH2Cl2. 31P {1H} NMR (CHCl3): \u03b4 31.9 , \u03b4 8.2 (P1/P4); 13C {1H} NMR (CDCl3): \u03b4 \u22124.4  = 4); 1H NMR (CDCl3): \u03b4 \u221216.7 .2-Synthesis of Cl2 (2): 19.5\u2005mg of Vaska\u2019s complex (0.025\u2005mmol) and 20.4\u2005mg of [CH(dppm)2]Cl (0.025\u2005mmol) . The mixture was stirred at ambient temperature for 15\u2005min. After addition of 0.1\u2005ml of hydro\u00adchloric acid (10\u2005mol\u2005L\u22121), the product crystallized upon standing for a day. 31P {1H} NMR (CHCl3/MeOH): \u03b4 45.3 , \u03b4 1.7 (P1/P4); 13C {1H} NMR (CDCl3): \u03b4 9.1  = 38, 1JC1H1 = 122); 1H NMR (CDCl3/MeOH): \u03b4 \u221218.9 .1 resulted in the location of the hydride hydrogen atom. The bond length was restrained to a distance of 1.6\u2005\u00c5 and a fixed isotropic displacement parameter of 1.5Ueq of iridium was applied. The hydrido ligand of complex 2 was also detected and refined isotropically without the use of bond restraints. Furthermore, the proton of the CDP carbon atom was spotted and refined with bond restraints of 0.98\u2005\u00c5. The hydrogen atoms of the water and solvent mol\u00adecules could only be partially detected and were omitted. A determination of a 1:1 positional disorder of one water mol\u00adecule (O4 and O4A) and one HCl or chloride (Cl10 and Cl1A) was possible. Eight chloride positions can be detected, which are occupied by a total of four chlorides and four hydro\u00adchloric acid units. The hydrogen-atom positions of the phenyl subunits and methyl\u00adene groups were refined with calculated positions (C\u2014H = 0.94 and 0.98\u2005\u00c5) using a riding model with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a052 are related to each other by the presence of a pseudo-symmetry centre. A halving of the c axis and consequently the changing of the monoclinic setting from P21/n to P21/c allows the consideration of one formula unit of 2. A closer observation of the sections of the reciprocal lattice along c* (l = 2n\u00a0+\u00a01) at different values of l results in the presence of frequent weak reflections. Consequently, an inter\u00adpretation of this system as three-dimensional network between two complex mol\u00adecules, four hydro\u00adchloric acid units and eleven water mol\u00adecules allows the involvement of these weak, but clearly existing reflections, and establishes the possibility of the distinction of the chloride and oxygen positions.The two complex mol\u00adecules of 10.1107/S2056989018004905/eb2007sup1.cifCrystal structure: contains datablock(s) global, complex1, complex2. DOI: 10.1107/S2056989018004905/eb2007complex1sup2.hklStructure factors: contains datablock(s) complex1. DOI: 10.1107/S2056989018004905/eb2007complex2sup3.hklStructure factors: contains datablock(s) complex2. DOI: 1577807, 1577808CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure is stabilized by N/C\u2014H\u22efO hydrogen bond, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions with weak \u03c0\u2013\u03c0 inter\u00adactions contacts to form a three-dimensional architecture.The title compound, C 18H22FN5O8S, is used as a herbicide (pyrimidinyl\u00adsulfonyl\u00adurea herbicide). The dihedral angle between the mean planes of the pyridine and pyrimidine rings is 86.90\u2005(7)\u00b0. In the crystal, N/C\u2014H\u22efO hydrogen bonds, C\u2014H\u22efF and C\u2014H\u22ef\u03c0 inter\u00adactions link adjacent mol\u00adecules, forming a chain along [020]. A further two C\u2014H\u22efO hydrogen bonds together with weak \u03c0\u2013\u03c0 inter\u00adactions [ring centroid separation = 3.7584\u2005(12)\u2005\u00c5] further aggregate the structure into a three-dimensional architecture.The title compound, {systematic name: 1-[3-carbamo\u00adyl]amino}\u00adsulfon\u00adyl)pyridin-2-yl]-2-fluoro\u00adpropyl 2-meth\u00adoxy\u00adacetate}, C DOI: 10.1107/S2056989017012737/hg5495Isup2.hklStructure factors: contains datablock(s) I. DOI: 1572854CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound, a bromo derivative of pyran\u00adocoumarin, possesses photobiological activity. It was formed by bromination of seselin by using NBS in MeOH at room temperature. In the crystal, mol\u00adecules are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions and weak C\u2014H\u22efO inter\u00adactions, forming layers parallel to (001). 15H14Br2O4 chromen-2(8H)-one], is a pyran\u00adocoumarin derivative formed by the bromination of seselin, which is a naturally occurring angular pyran\u00adocoumarin isolated from the Indian herb Trachyspermum stictocarpum. In the mol\u00adecule, the benzo\u00adpyran ring system is essentially planar, with a maximum deviation of 0.044\u2005(2)\u2005\u00c5 for the O atom. The di\u00adhydro\u00adpyran ring is in a half-chair conformation and the four essentially planar atoms of this ring form a dihedral angle of 4.6\u2005(2)\u00b0 with the benzo\u00adpyran ring system. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds, forming chains propagating along [010]. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances of 3.902\u2005(2) and 3.908\u2005(2)\u2005\u00c5, link the hydrogen-bonded chains into layers parallel to (001).The title compound, C The di\u00adhydro\u00adpyran ring C1\u2013C5/O1 is in a half-chair conformation and atoms C2 and C3 deviate by \u22120.385\u2005(4) and 0.280\u2005(4)\u2005\u00c5 from the plane through the other four essentially planar atoms (mean deviation 0.003\u2005\u00c5), which makes a dihedral angle of 4.6\u2005(2)\u00b0 with the benzo\u00adpyran ring system. The relative stereochemistry at atoms C3 and C4 is R/S and S/R.The title mol\u00adecule Fig.\u00a01 is compoCg1\u22efCg1 of 3.902\u2005(2)\u2005\u00c5 and Cg1\u22efCg2 of 3.908\u2005(2)\u2005\u00c5 where Cg1 and Cg2 are the centroids of the C1/C5/C6/C10\u2013C12 and O2/C6\u2013C10 rings, respectively, link the hydrogen-bonded chains, forming layers parallel (001)  Fig.\u00a03.et al., 2016et al., 2006A search of the Cambridge Structural Database  from ethyl acetate:hexane (1:4) at room temperature by slow evaporation of the solvents. NMR analysis: 1H NMR data : \u03b4H 8.02 , 7.32 , 6.82 , 5.36 , 4.26 , 3.56 , 1.50 , 1.54 .The title compound is a colourless solid substance formed on bromination of the naturally occurring seseline isolated from the methanol extract of iso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017006132/lh5842sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017006132/lh5842Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006132/lh5842Isup3.cmlSupporting information file. DOI: 1545541CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure of zwitterionic 2-{[meth\u00adyl]carbamo\u00adyl}benzoate hemihydrate is reported. The crystal structure is stabilized by a variety of hydrogen bonds and offset \u03c0\u2013\u03c0 stacking inter\u00adactions. 15H15N3O3\u00b70.5H2O, comprises two 2-{[meth\u00adyl]carbamo\u00adyl}benzoate zwitterions (A and B) and a water mol\u00adecule. The dihedral angles between the pyridine and phenyl rings in the zwitterions are 53.69\u2005(10) and 73.56\u2005(11)\u00b0 in A and B, respectively. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO, O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) hydrogen bonds into a three-dimensional network. The crystal structure also features \u03c0\u2013\u03c0 inter\u00adactions involving the centroids of the pyridine and phenyl rings [centroid\u2013centroid distances = 3.5618\u2005(12)\u2005\u00c5 in A and 3.8182\u2005(14)\u2005\u00c5 in B].The asymmetric unit of the title compound, C The study and synthesis of new zwitterions is therefore important in the search for new biomedical applications  and a cocrystallized water mol\u00adecule, as shown in Fig.\u00a012\u2014Car single bond [1.38\u2005(3)\u2005\u00c5], but are similar to those found in related compounds with an N+=C double bond \u2005\u00c5 and C15A\u2014O2A = 1.257\u2005(3)\u2005\u00c5] in mol\u00adecule A, with comparable values in mol\u00adecule B, are similar to values found in other deprotonated carboxyl\u00adate groups meth\u00adyl]carbamo\u00adyl}benzoate zwitterions  \u2005\u00c5, where Cg3 and Cg4 are the centroids of the N1A/C1A\u2013C5A and C9A\u2013C14A rings]  Fig.\u00a04. The crys] Fig.\u00a05. An overet al., 2016N-[2-eth\u00adyl]phthalamic acid tetra\u00adhydrate phthalamic acid -2-[(1-phenyl\u00adeth\u00adyl)carbamo\u00adyl]benzoate  -1-phenyl\u00adethanaminium 2-{carbamo\u00adyl}benzoate -4H-1\u03bb2-pyridine as the skeleton gave 15 hits, although none of these were zwitterionic derivatives comparable to the title compound. Of these, only three had aromatic rings in the cation in addition to the imino\u00adpoyridine unit phthalimide and 0.01\u2005mol of 4-amino-3-methyl\u00adpyridine in 10\u2005ml of di\u00admethyl\u00adformamide with a catalytic amount of potassium carbonate. The mixture was stirred in a 50\u2005ml round-bottomed flask at room temperature for about 3\u2005h. The progress of the reaction was monitored by thin-layer chromatography and the mixture was poured into cold water once the reaction was complete. The resulting precipitate was filtered off, washed successively with distilled water, and recrystallized from acetone solution by slow evaporation to obtain colourless block-shaped single crystals.The title compound was obtained unexpectedly from the reaction of 0.01\u2005mol of W were fixed at 0.86\u2005\u00c5, the H\u22efH distance was fixed at 1.34\u2005\u00c5 and the H atoms were refined with a riding model . The C-bound H atoms were positioned geometrically using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C) . A rotating-group model was applied to the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017007836/sj5531sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017007836/sj5531Isup2.hklStructure factors: contains datablock(s) I. DOI: 1552520CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "High resolution mass spectrometry (HRMS) was used to monitor library composition and establish conditions under which equilibria were established.Dynamic combinatorial chemistry (DCC) represents an approach, whereby traditional supramolecular scaffolds used for protein surface recognition might be exploited to achieve selective high affinity target recognition. Synthesis, in situ screening and amplification under selection pressure allows the generation of ligands, which bear different moieties capable of making multivalent non\u2010covalent interactions with target proteins. Generic tetracarboxyphenyl porphyrin scaffolds bearing four hydrazide moieties have been used to form dynamic combinatorial libraries (DCLs) using aniline\u2010catalyzed reversible hydrazone exchange reactions, in 10\u2009% DMSO, 5 m The use of different amino acids was intended to allow improved scaffold solubility and to investigate the role of functionality proximal to the hydrazone linker in terms of influencing exchange rate.A tetraphenylporphyrin scaffold was chosen as a multivalent hydrazone scaffold. This choice was motivated by the ready accessibility of commercial porphyrins with a sufficient number of points at which a hydrazide linker could be introduced, and the established utility of porphyrins in protein surface recognition.1\u20133aaaa were achieved by direct coupling of protected amino acid hydrazides with tetracarboxyphenylporphyrin, using PyBOP, to generate protected hydrazide porphyrins 4\u20136. Hydrazone scaffolds 1\u20133aaaa ready for DCC studies bearing a simple phenyl hydrazone at each exchangeable bond were obtained from the corresponding protected hydrazides 4\u20136 by TFA deprotection followed by reaction with benzaldehyde 7.Attempts to synthesise tetracarboxyhydrzidophenylporphyrin resulted in analytically intractable products (see Supporting information). Subsequent efforts centred on the introduction of an amino acid spacer between the porphyrin scaffold and the labile hydrazone linker. Initial synthesis using a glycine spacer resulted in formation of an insoluble product (see Supporting information). Therefore amino acid spacers containing groups to aid scaffold solubility, serine, aspartic acid and glutamic acid, were used. The introduction of the acid functionalities was also envisioned to aid the hydrazone exchange chemistry necessary during the DCL generation, through intramolecular proton transfer effects as has been observed in recent work from the Kool group.1\u20133aaaa, with three different aldehydes: 4\u2010carboxybenzaldehyde 8, 4\u2010methyl ester benzaldehyde 9 and 2,4\u2010dimethoxybenzaldehyde 10  was used to follow hydrazone exchange. Preliminary efforts to employ HPLC to monitor library distribution indicated that identification of gradients to separate closely related products would be challenging, and in the context of a screening workflow, HRMS represents a method to establish compound identity and qualitative changes in library composition in response to template. Hydrazone exchanges were performed with the three different porphyrin scaffolds 2aaaa with 8), hydrazone exchange was observed within 24 h, and could be visualised by HRMS  to 8, at first increasing then decreasing. The products of successive hydrazone exchanges  then followed in succession.Considering one of these systems,  , with a shift to a greater number of hydrazone exchanges observed (see Supporting information).Having established effective exchange of the benzaldehyde moiety for another aldehyde it was necessary to assess the extent to which a thermodynamic rather than kinetic distribution of products was obtained. The speciation of porphyrins reacted with 25 equivalents of aldehyde for 24 h followed by addition of a further 25 equivalents of the same aldehyde and reaction for 24 h was monitored. Using 1\u20133aaaa were carried out using two aldehydes simultaneously to generate a DCL . Flash column chromatography was performed using silica gel 60 (0.043\u20130.063 mm VWR or Sigma Aldrich) or alumina (Brockman I from Sigma Aldrich), unless otherwise stated silica gel was used and pressure was applied by means of head bellows.Thin layer (silica) chromatography was performed using Merck Kiesegel 60 F1H NMR spectra were obtained on Bruker DPX 300 (300 MHz) Avance 500 (500 MHz) or DRX500 (500 MHz) spectrometers and referenced to either residual non\u2010deuterated solvent peaks or tetramethylsilane. 13C spectra were recorded on a Bruker DPX 300 (75 MHz) Bruker or an Avance 500 (126 MHz) and referenced to the solvent peak. 1H spectra are reported as follows: 1H NMR : \u03b4 = ppm to 2 d.p. . Chemical shifts are quoted in ppm with signal splitting recorded as singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), broad (br). Coupling constants, J, are measured to the nearest 0.1 Hz. Similarly, 13C spectra are reported as follows: \u03b4 : \u03b4 ppm to one decimal place. Infrared spectra were recorded on a Perkin\u2013Elmer Fourier\u2010Transfer spectrometer. Spectra were analysed neat and structurally important absorptions are quoted. Absorption maxima (\u03bd\u0303max=) are quoted in wavenumbers (cm \u20131). HPLC LC\u2010MS were recorded on a Bruker HCT ultra under electrospray ionisation (ESI) conditions. High resolution mass spectra were recorded on a Bruker Daltonics micrOTOF Premier Mass Spectrometer, under positive ESI conditions unless otherwise stated.tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201017\u2010{4\u2010[((1S)\u20102\u2010(tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)\u2010N\u2010((1S)\u20102\u2010(tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}ethyl)benzamide (4):4\u2010\u20102\u2010, PyBOP , tert\u2010butyl 2\u2010(2\u2010amino\u20103\u2010tert\u2010butoxypropanoyl)hydrazinecarboxylate,  and diisopropylethylamine  in anhydrous dimethylformamide (5 mL) were stirred under a nitrogen atmosphere for 18 h. The reaction mixture was then diluted with ethyl acetate (50 mL) and washed with saturated sodium hydrogen carbonate solution (50 mL), 1 m hydrochloric acid (50 mL) and brine (3\u2009\u00d7\u200950 mL). The organic phase was dried (sodium sulphate) and concentrated to yield the crude product as a purple solid. This was purified by flash column chromatography (1:1 ethyl acetate/dichloromethane then ethyl acetate) to yield the product as a purple solid . 1H NMR : \u03b4 = 1.29 , 1.45 , 3.51\u20133.63 , 4.07 , 4.83 , 6.40\u20136.57 , 8.15 , 8.21 , 8.40 , 8.73  ppm. 13C NMR : \u03b4 = 26.8, 27.5, 38.4, 53.3, 61.6, 74.0, 80.8, 106.6, 119.3, 125.8, 133.4, 134.4, 145.2, 156.2, 168.4, 170.8 ppm. IR (solid state): \u03bd\u0303 = 3251 (N\u2013H), 1696 (C=O carbamate), 1645 (C=O amide) cm\u20131. ESI\u2010MS m/z found 1820.9402 [M + 2H]+, [C96H124N16O20]+ calcd. 1820.9178.N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201017\u2010{4\u2010[((1S)\u20102\u2010hydroxy\u20101\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)\u2010N\u2010((1S)\u20102\u2010hydroxy\u20101\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}ethyl)benzamide (1aaaa):4\u2010\u20102\u2010hydroxy\u20101\u2010{4  in trifluoroacetic acid (4.5 mL), water (0.25 mL) and triisopropylsilane (0.25 mL) was stirred for 6 h. The solution was then concentrated to yield the deprotected hydrazide as a green solid (complete deprotection was confirmed by HRMS). The green solid was then redissolved in water (2 mL) and acetonitrile (2 mL) and benzaldehyde (2 drops) was added, the mixture was then stirred for 30 min. The precipitate was isolated and washed with water and acetonitrile to yield the product as a dark purple solid . 1H NMR : \u03b4 = 1.67 , 3.94 , 4.76 , 5.63 , 7.51 , 7.63 , 7.75 , 7.95 , 8.12 , 8.39 , 8.84 , 8.91 , 11.56 , 11.73  (cis and trans hydrazone isomers observed in 1:1 ratio). IR (solid state): \u03bd\u0303 = 3212 (N\u2013H), 1633 (C=O amide), 1608 (C=N) cm\u20131. ESI\u2010MS m/z found 1547.5750 [M + H]+, [C88H75N16O12]+: calcd. 1547.5340.tert\u2010Butyl (3S)\u20103\u2010{[4\u2010\u20103\u2010(tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}\u20103\u2010oxopropyl)carbamoyl]phenyl}\u201017\u2010{4\u2010[((1S)\u20103\u2010(tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}\u20103\u2010oxopropyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)phenyl]formamido}\u20103\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}propanoate (5): Tetracarboxyphenylporphyrin , PyBOP , (S)\u2010tert\u2010butyl 2\u2010(2\u2010amino\u20104\u2010tert\u2010butoxy\u20104\u2010oxobutanoyl)hydrazinecarboxylate,  and anhydrous diisopropylethylamine  in anhydrous dimethylformamide (5 mL) were stirred under a nitrogen atmosphere for 18 h. The reaction mixture was then diluted with ethyl acetate (50 mL) and washed with saturated sodium hydrogen carbonate solution (50 mL), 1 m hydrochloric acid (50 mL) and brine (3\u2009\u00d7\u200950 mL). The organic phase was dried (sodium sulphate) and concentrated to yield the crude product as a purple solid. This was purified by flash column chromatography (1:1 ethyl acetate/dichloromethane then ethyl acetate) to yield the product as a purple solid . 1H NMR : \u03b4 = 1.53 , 1.55 , 2.95 , 3.10 , 5.30 , 5.45 , 8.21 , 8.27 , 8.73 , 9.02 . 13C NMR : \u03b4 = 27.4, 27.6, 37.2, 49.3, 80.9, 81.5, 119.3, 125.9, 133.2, 134.4, 145.4, 149.5, 156.3, 168.4, 170.2, 171.3, 185.1 ppm. IR (solid state): \u03bd\u0303 = 3275 (N\u2013H), 1723 (C=O ester), 1711 (C=O carbamate), 1647 (C=O amide) cm\u20131. ESI\u2010MS m/z found 1931.9891 [M + H]+, [C100H123N16O24]+: calcd. 1931.8896.N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201017\u2010{4\u2010[((1S)\u20102\u2010carboxy\u20101\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)phenyl]formamido}\u20133\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}propanoic Acid (2aaaa):3(S)\u20103\u2010{+, [C92H75N16O16]+: calcd. 1659.5547.tert\u2010Butyl (4S)\u20104\u2010{[4\u2010\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}\u20104\u2010oxobutyl)carbamoyl]phenyl}\u201017\u2010{4\u2010[((1S)\u20104\u2010(tert\u2010butoxy)\u20101\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}\u20104\u2010oxobutyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)phenyl]formamido}\u20104\u2010{N\u2032\u2010[(tert\u2010butoxy)carbonyl]hydrazinecarbonyl}butanoate (6): {4\u2010+, [C104H131N16O24]+: calcd. 1987.9522.N\u2032\u2010[(1E)\u2010phenylmethylidenehydrazinecarbonyl]propyl}carbamoyl)phenyl]\u201017\u2010{4\u2010[((1S)\u20103\u2010carboxy\u20101\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}propyl)carbamoyl]phenyl}\u201021,22,23,24\u2010tetraazapentacyclotetracosa\u20101,3(24),4,6,8,10,12,14,16(22),17,19\u2010undecaen\u20102\u2010yl)phenyl]formamido}\u20104\u2010{N\u2032\u2010[(1E)\u2010phenylmethylidene]hydrazinecarbonyl}butanoic Acid (3aaaa):(4S)\u20104\u2010{4\u2010+, [C96H83N16O16]+: calcd. 1715.6173.Hydrazone Exchange Studies: Hydrazone exchange reactions were carried out in HPLC vials and were followed using high resolution mass spectrometry on a Bruker Daltonics micrOTOF Premier Mass Spectrometer, using 10 \u00b5L injections and summing the masses over a range of 1.0 to 3.0 min. The intensity of the maximum peak for each of the successive hydrazone exchanges was taken and the percentage associated with each of the porphyrin peaks calculated.1\u20133aaaa were made up to 5 mm concentration in DMSO and were stored in plastic Eppendorf tubes. 1 m stocks of catalyst (11 and 12) and aldehydes  were made up in DMSO.Hydrazone functionalised porphyrins 1\u20133aaaa in DMSO was added to a solution of the aldehyde and catalyst to give a total concentration of 10\u2009% DMSO in 5 mm ammonium acetate buffer, pH 6.75, to a final porphyrin concentration of 100 \u00b5m and stated concentrations of other components. For time courses, mass spectra were obtained at appropriates time points . For measurements at single time points, mass spectra were obtained after 24 h incubation. For pre\u2010incubated samples, the pre\u2010incubated mixture was left for 24 h, and a mass spectrum obtained, prior to addition of further components.In all exchange reactions the hydrazone functionalised porphyrin Supporting InformationClick here for additional data file."}
{"text": "The asymmetric unit of the title compound consists of one and a half bis\u00adchalcone mol\u00adecules. In the crystal, mol\u00adecules are linked into a three-dimensional network by C\u2014H\u22efF and C\u2014H\u22efO hydrogen bonds, some of the C\u2014H\u22efF links being unusually short (< 2.20\u2005\u00c5). Hirshfeld surface analyses are presented and discussed. 24H14F4O2, comprises of one and a half mol\u00adecules; the half-mol\u00adecule is completed by crystallographic inversion symmetry. In the crystal, mol\u00adecules are linked into a three-dimensional network by C\u2014H\u22efF and C\u2014H\u22efO hydrogen bonds. Some of the C\u2014H\u22efF links are unusually short (< 2.20\u2005\u00c5). Hirshfeld surface analyses  for the title compound are presented and discussed.The asymmetric unit of the title compound, C They consist of two aromatic rings joined by a three-carbon-atom unsat\u00adurated carbonyl system (\u2013CH=CH\u2014CO\u2013). Bischalcones with the general formula Ar\u2014CH=CH\u2014CO\u2014CH=CH\u2014Ar  A, the carbonyl groups form similar torsion angles with the 2,4-di\u00adfluoro\u00adphenyl ring  and the olefinic double bond . Conversely, the torsion angles between the olefinic double bond and the central benzene ring are slightly different . This leads to slight differences in the dihedral angles between the terminal 2,4-di\u00adfluoro\u00adphenyl and the central benzene rings [7.91\u2005(2)\u00b0 for C1A\u2013C6A and 6.28\u2005(2)\u00b0 for C19A\u2013C24A]. In mol\u00adecule B, both torsion angles \u03c41 and \u03c43 are comparable to those in mol\u00adecule A . However, mol\u00adecule B is slightly closer to planar than mol\u00adecule A, as its central and terminal rings subtend a dihedral angle of 5.49\u2005(2)\u00b0. This might arise from the lower torsion angle between the olefinic double bond and the central benzene ring [O1B\u2014C7B\u2014C8B\u2014C9B = 0.9\u2005(6)\u00b0]. Selected torsion and dihedral angles are listed in Table\u00a01et al., 2005The asymmetric unit of (I)B) Fig.\u00a01. The molA\u2014H8A\u22efF1A, C17A\u2014H17A\u22efF3A and C8B\u2014H8B\u22efF1B hydrogen bonds generates an S(6) ring motif s Table\u00a01 generates Table\u00a02. As the er Fig.\u00a02. Atom F2et al., 2004CrystalExplorer 3.1  and outside (de) of the Hirshfeld surface analyze the inter\u00admolecular inter\u00adaction via the mapping of dnorm. In a dnorm surface, any inter\u00admolecular inter\u00adactions will appear as a red spot.The Hirshfeld surface analyses . Similarly, the C\u2014H\u22efF inter\u00adactions are identified by red spots near the F2A atom in mol\u00adecule A . As illustrated in Fig.\u00a05de and di diagonal axes represent the overall two-dimensional FP and those delineated into F\u22efH/H\u22efF, H\u22efH and O\u22efH/H\u22efO contacts, respectively. The most significant inter\u00admolecular inter\u00adactions are the reciprocal F\u22efH/H\u22efF inter\u00adactions (30.1%), which appear as two sharp symmetric spikes in FP maps with a prominent long spike at de + di \u2243 2.3\u2005\u00c5 . The H\u22efH inter\u00adactions appear in the central region of the FP with ed = id \u2243 2.4\u2005\u00c5 and contribute 29.0% to the Hirshfeld surface  whereas two symmetrical narrow pointed wings corresponding to the O\u22efH/H\u22efO inter\u00adactions with 12.7% contribution appear at diagonal axes of de + di \u2243 2.4\u2005\u00c5 . The percentage contributions for other inter\u00admolecular contacts are less than 10% in the Hirshfeld surface mapping .Dark-red spots that are close to atoms O1ds Fig.\u00a04a. Simil A Fig.\u00a04b. As il\u2005\u00c5 Fig.\u00a05b. The Hce Fig.\u00a05c wherea\u2005\u00c5 Fig.\u00a05d. The pet al., 2016E)-1-(4-fluoro\u00adphen\u00adyl)-3-phenyl\u00adprop-2-en-1-one as the main skeleton revealed the presence of seven structures containing the chalcone moiety with different substituent similar to the title compounds in this study. These structures are 4\u2032-fluoro\u00adchalcone -3-[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]-1-(4fluoro\u00adphen\u00adyl)prop-2-en-1-one -3-(4-chloro\u00adphen\u00adyl)-1-(4-fluoro\u00adphen\u00adyl)prop-2-en-1-one  phen\u00adyl]prop-2-en-1-ones -1-(4-fluoro\u00adphen\u00adyl)-3-(4-methyl\u00adphen\u00adyl)prop-2-en-1-one  in methanol (20\u2005ml) was mixed with 2,4-di\u00adfluoro\u00adaceto\u00adphenone (0.02\u2005mol) in methanol (20\u2005ml) in the presence of NaOH. The reaction mixtures were stirred for about 5\u20136\u2005h at room temperature. The resultant crude products were filtered, washed successively with distilled water and recrystallized from ethanol solution to get the title compound. Yellow blocks of (I)-3,3\u2032-bis\u00adprop-2-en-1-one), C Solvent for growing crystals: mixture of chloro\u00adform and aceto\u00adnitrile (1:1 v/v); yield 85%, m.p. 447\u2013449\u2005K; FT\u2013IR (ATR (solid) cm\u22121): 3101 , 1600 , 1593, 1420 , 1229 ; 1H NMR : \u03b4 7.969\u20137.922 , 7.818\u20137.787 , 7.697 , 7.059\u20137.022 , 6.969\u20136.935 ; 13C NMR : 187.00 (C7), 143.62 (C9), 136.83 (C2), 133.11 (C10), 133.03 (C5), 129.14 , 126.18 (C6), 126.12 (C8) 112.47, 112.27 (C3), 105.01, 104.81 (C1), 104.59 (C4).Uiso(H) = 1.2Ueq(C) for H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901701564X/hb7696sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901701564X/hb7696Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901701564X/hb7696Isup3.cmlSupporting information file. DOI: 1449628CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound, tetra\u00adhydro\u00adseselin (THS), a hydrogenated product of the angular pyran\u00adocoumarin seselin, possesses photo-biological activity against different kinds of inflammatory skin diseases such as atopic dermatitis and pigment disorders like vitiligo and psoriasis. 14H16O3, a pyran\u00adocoumarin chromen-2-one] obtained from the hydrogenation of seselin in the presence of Pd/C in MeOH at room temperature, the dihedral angle between the central benzene ring and the best planes of the outer fused ring systems are 6.20\u2005(7) and 10.02\u2005(8)\u00b0. In the crystal, mol\u00adecules show only very weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions.In the title compound, tetra\u00adhydro\u00adseselin, C HL60 and A431, has been observed  cyclo\u00adaddition] and diadducts [(4\u00a0+\u00a02) cyclo\u00adaddition]  and 178.73\u2005(14)\u00b0, respectively, indicating that these rings are coplanar. The destruction of photo-biological activity and change of conformation of the pyran rings of the title mol\u00adecule is considered to be due to the loss of the double bonds in seselin.In the title compound, the three different fused rings comprising the mol\u00adecule Fig.\u00a01, are thei (ring) [3.221\u2005(2)\u2005\u00c5] and methyl\u00adene C9\u2014H\u22efO3i (carbon\u00adyl) [3.412\u2005(2)\u2005\u00c5] inter\u00adactions  and methyl\u00adene C8\u2014H\u22efO3ii (carbon\u00adyl) [3.593\u2005(3)\u2005\u00c5] inter\u00adactions -[1]-benzo\u00adpyran-7-one; bromo\u00adhydroxy-seselin  = 1.2Ueq(C). Those on methyl groups were allowed to ride with C\u2014H = 0.96\u2005\u00c5 and with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S205698901700932X/zs2379sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901700932X/zs2379Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901700932X/zs2379Isup3.cmlSupporting information file. DOI: 1557474CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds play an important role in the crystal packing, resulting in the formation of mol\u00adecular sheets parallel to the bc plane.The mol\u00adecules of C 15H14N2O3, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit that differ in the orientation of the 3-meth\u00adoxy\u00adphenyl group with respect to the methyl\u00adidenebenzohydrazide unit. The dihedral angles between the two benzene rings are 24.02\u2005(10) and 29.30\u2005(9)\u00b0 in mol\u00adecules A and B, respectively. In mol\u00adecule A, the meth\u00adoxy group is twisted slightly relative to its bound benzene ring, with a Cmeth\u00adyl\u2014O\u2014C\u2014C torsion angle of 14.2\u2005(3)\u00b0, whereas it is almost co-planar in mol\u00adecule B, where the corresponding angle is \u22122.4\u2005(3)\u00b0. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds, as well as by weak C\u2014H\u22efO inter\u00adactions, forming sheets parallel to the bc plane. The N\u2014H\u22efO hydrogen bond and weak C\u2014H\u22efO inter\u00adaction link different mol\u00adecules (A\u22efB) whereas both O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds link like mol\u00adecules (A\u22efA) and (B\u22efB). Pairs of inversion-related B mol\u00adecules are stacked approximately along the a axis by \u03c0\u2013\u03c0 inter\u00adactions in which the distance between the centroids of the 3-meth\u00adoxy\u00adphenyl rings is 3.5388\u2005(12)\u2005\u00c5. The B mol\u00adecules also participate in weak C\u2014H\u22ef\u03c0 inter\u00adactions between the 4-hy\u00addroxy\u00adphenyl and the 3-meth\u00adoxy\u00adphenyl rings.The title compound, C Various derivatives of benzohydrazide have been reported to possess a range of biological properties, including anti\u00adbacterial -4-hy\u00addroxy-N\u2032-(3-hy\u00addroxy-4-meth\u00adoxy\u00adbenzyl\u00adidene)benzohydrazide -4-hy\u00addroxy-N\u2032-benzohydrazide A and B, of the title benzohydrazide derivative, C15H14N2O3, in the asymmetric unit of (I)A and B, respectively. The mol\u00adecules exist in the trans-conformation with respect to the C8=N2 bond [1.275\u2005(2)\u2005\u00c5 in mol\u00adecule A and 1.271\u2005(2)\u2005\u00c5 in mol\u00adecule B] and the torsion angle N1\u2014N2\u2014C8\u2014C9 = \u2212178.14\u2005(16)\u00b0 in mol\u00adecule A and \u2212177.69\u2005(16)\u00b0 in mol\u00adecule B. Five atoms  of the central fragment are approximately coplanar, having r.m.s. deviations of 0.0179\u2005(2)\u2005\u00c5 in mol\u00adecule A and 0.0327\u2005(2)\u2005\u00c5 in mol\u00adecule B. The mean plane through this central fragment makes dihedral angles of 23.87\u2005(11) and 0.20\u2005(12)\u00b0 with the planes of the 4-hy\u00addroxy\u00adphenyl and 3-meth\u00adoxy\u00adphenyl rings, respectively, in mol\u00adecule A. The corresponding values are 22.58\u2005(11) and 11.04\u2005(11) \u00b0 in mol\u00adecule B. In mol\u00adecule A, the meth\u00adoxy group is slightly twisted from the attached benzene ring [C15\u2014O3\u2014C11\u2014C10 = 14.2\u2005(3)\u00b0] whereas it is essentially coplanar in mol\u00adecule B [where the corresponding torsion angle is \u22122.4\u2005(3)\u00b0]. The bond distances agree with literature values and are comparable with those in related structures  whereas the O2A\u2014H2A\u22efN2Aiii and O2A\u2014H2A\u22efO1Aiii hydrogen bonds link equivalent A mol\u00adecules, and O2B\u2014H2B\u22efN2Bii and O2B\u2014H2B\u22efO1Bii hydrogen bonds link equivalent B mol\u00adecules. Stacking of planes of mol\u00adecules in the a-axis direction involves \u03c0\u2013\u03c0 inter\u00adactions between B mol\u00adecules with Cg\u22efCgvi distance of 3.5388\u2005(12)\u2005\u00c5. A weak C\u2014H\u22ef\u03c0 inter\u00adaction (C3B\u2014H3B\u22efCgv) between the 4-hy\u00addroxy\u00adphenyl ring and the 3-meth\u00adoxy\u00adphenyl ring of symmetry-related B mol\u00adecules is also present  x, y, \u2212z; (iii) x, y, \u2212z; (iv) x, 1\u00a0+\u00a0y, z; (v) \u2212x, \u2212y, z; (vi) 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z; Cg is the centroid of the C9B\u2013C14B ring].In the crystal Fig.\u00a02, the molnt Fig.\u00a03 [symmetret al., 2011et al., 2011et al., 2012Chemical context section.A search of SciFinder  in ethanol (10\u2005ml) and 3-meth\u00adoxy\u00adbenzaldehyde  in ethanol (10\u2005ml) were mixed, stirred and refluxed for 5\u2005h. The resulting mixture was then cooled to room temperature. The white precipitate that formed was filtered. Colorless block-shaped single crystals of (I)3OH) \u03bbmax (log\u220a): 212 (5.51), 302 (5.61)\u2005nm; FT\u2013IR (KBr) \u03bd: 3158, 2834, 1648, 1607, 1509\u2005cm\u22121; 1H NMR  \u03b4: 11.65 , 10.15 , 8.39 , 7.80 , 7.27 , 7.25 , 7.37 , 7.00 , 6.86 , 3.81  p.p.m.UV\u2013Vis N\u2032-benzyl\u00adidenebenzohydrazide skeleton by showing the characteristic signals of an amine (N=CH) at 8.39  and an amide (N\u2014H) at 11.65  p.p.m.The UV\u2013Vis spectrum of (I)et al.  = 0.85 or 0.87\u2005\u00c5; d(O\u2014H) = 0.82\u2005\u00c5; d(C\u2014H) = 0.93\u2005\u00c5 for aromatic and CH; and 0.96\u2005\u00c5 for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl and hydroxyl H atoms, and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016013268/pk2585sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016013268/pk2585Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013268/pk2585Isup3.cmlSupporting information file. DOI: 1499671CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E conformation about the C=C bond, and the quinoline ring system and the benzene ring are inclined to one another by 29.22\u2005(7)\u00b0.The title 8-hy\u00addroxy\u00adquinoline derivative has an  19H15NO3, was synthesized by a Perkin reaction of 2-methyl-8-hy\u00addroxy\u00adquinoline and 4-formyl-2-methyl\u00adbenzoate in acetic anhydride under a nitro\u00adgen atmosphere. The mol\u00adecule has an E conformation about the C=C bond, and the quinoline ring system and the benzene ring are inclined to one another by 29.22\u2005(7)\u00b0. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond in the 8-hy\u00addroxy\u00adquinoline moiety. In the crystal, mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(28) ring motif. The dimers are linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming sheets parallel to plane (10-1).The title compound, C The C11\u2014C10 and C6\u2014C9 bond lengths are 1.463\u2005(2) and 1.466\u2005(2)\u2005\u00c5, respectively. These distances are shorter than the standard length of a C\u2014C single bond (ca 1.5\u2005\u00c5) because of the conjugate system formed by the C9=C10 bond and the aromatic systems. The quinoline ring system and the benzene ring are inclined to one another by 29.22\u2005(7)\u00b0.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01In the crystal, mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming inversion dimers with an f Table\u00a01. The dimet al., 2016E conformation about the C=C bond, and in the crystal they also form inversion dimers. They include 2-{2-[4-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]vin\u00adyl}quinolin-8-ol  = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901601210X/su5312sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901601210X/su5312Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901601210X/su5312Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S205698901601210X/su5312Isup4.cmlSupporting information file. DOI: 859030CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom in the title methanol solvate is coordinated octa\u00adhedrally by two N atoms of the chelating organic ligand, one Br atom and three facially configured carbonyl ligands. Hydrogen bonds between the complex and methanol solvent mol\u00adecules lead to a layered arrangement in the structure.The Re 16H16N4O3)(CO)3]\u00b7CH3OH, the ReI atom adopts a distorted octa\u00adhedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5--3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in axial positions. Conventional hydrogen bonds including the methanol solvent mol\u00adecules assemble the complex mol\u00adecules through mutual N\u2014H\u22efO\u2014H\u22efBr links [N\u22efO = 2.703\u2005(3)\u2005\u00c5 and O\u22efBr = 3.255\u2005(2)\u2005\u00c5] into centrosymmetric dimers, whereas weaker C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds [C\u22efO = 3.215\u2005(3)\u20133.390\u2005(4)\u2005\u00c5 and C\u22efBr = 3.927\u2005(3)\u2005\u00c5] connect the dimers into double layers parallel to the (111) plane.In the title compound, [ReBr(C The two N atoms and two carbonyl C atoms define the equatorial plane, while the octa\u00adhedral coordination sphere is completed by the third carbonyl C atom and the Br atom [Re\u2014Br = 2.6222\u2005(3)\u2005\u00c5] in axial positions. The CO ligands are almost linearly coordinated, with O\u2014C\u2014Re bond angles of 178.2\u2005(3), 177.8\u2005(3) and 177.8\u2005(3)\u00b0. The C\u2014Re\u2014C bond angles between carbonyl C atoms are 90.6\u2005(1), 90.2\u2005(1) and 88.7\u2005(1)\u00b0, close to ideal values, whereas the cis equatorial bite angle of the chelating ligand (N1\u2014Re1\u2014N4) is 73.42\u2005(8)\u00b0.The three carbonyl ligands bonded to the ReL)(CO)3] . However, this situation is unlikely to be a consequence of slipped \u03c0\u2013\u03c0 inter\u00adactions, since the corresponding slippage angle exceeds 56\u00b0 and the inter\u00adcentroid distance is as long as Cg(C6\u2013C10/N4)\u22efCg(C4/C5/N1\u2013N3)v = 4.090\u2005(3)\u2005\u00c5 . Although such weak inter\u00adactions are characteristic of related metal\u2013carbonyl structures  in benzene (30\u2005ml). The mixture was refluxed for 4\u2005h under a stream of argon and then allowed to cool to room temperature. The yellow product was collected by suction filtration, washed with hexane and dried . Crystals suitable for X-ray diffraction were obtained by slow diffusion of hexane into a methanol\u2013di\u00adchloro\u00admethane solution of the complex. IR : \u03bdas(CO) 2028 (s), \u03bds(CO) 1894 (s). 1H NMR : \u03b4 9.02 , 8.39 , 8.35 , 7.75 , 7.44 , 3.93 .Penta\u00adcarbonyl\u00adrhenium(I) bromide  was mixed with 5--3-(pyridin-2-yl)-1Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq otherwise. The O-bound H atom of the methanol solvent mol\u00adecule was found from a difference map and was refined with O\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017003371/wm5372sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017003371/wm5372Isup2.hklStructure factors: contains datablock(s) I. DOI: 1535292CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Graphene plasmonics has become a highlighted research area due to the outstanding properties of deep-subwavelength plasmon excitation, long relaxation time, and electro-optical tunability. Although the giant conductivity of a graphene layer enables the low-dimensional confinement of light, the atomic scale of the layer thickness is severely mismatched with optical mode sizes, which impedes the efficient tuning of graphene plasmon modes from the degraded light-graphene overlap. Inspired by gap plasmon modes in noble metals, here we propose low-dimensional hybrid graphene gap plasmon waves for large light-graphene overlap factor. We show that gap plasmon waves exhibit improved in-plane and out-of-plane field concentrations on graphene compared to those of edge or wire-like graphene plasmons. By adjusting the chemical property of the graphene layer, efficient and linear modulation of hybrid graphene gap plasmon modes is also achieved. Our results provide potential opportunities to low-dimensional graphene plasmonic devices with strong tunability. In the context of light-matter interactions, the concentration of electromagnetic fields on materials is a critical issue for the performance of tunable optical devices, such as photodetectors3678Due to its two-dimensional (2D) structure with extremely large conductivity from the massless Dirac point111314161719212223242126272931Here, we focus on low-dimensional waveguide systems for the improved light-graphene overlap factor. We firstly reveal the existence of hybrid graphene gap plasmon (H-GGP) modes the field profile of which is strongly confined inside the graphene gap between metallic and dielectric graphene layers. We demonstrate that the H-GGP mode has larger field concentration on graphene layers than those of edge33w (the sheet conductivity \u03c3(G) where Im{\u03c3(G)}\u2009<\u20090) is inserted in-between semi-infinite metallic domain M (Im{\u03c3(M)}\u2009>\u20090) and dielectric domain D (Im{\u03c3(D)}\u2009<\u20090). The gap region G satisfies the condition of Im{\u03c3(D)}\u2009<\u2009Im{\u03c3(G)}\u2009<\u20090, as the analogy of plasmonic gap modes in noble metals8212627\u03bc(x). \u03bc-dependency of the graphene conductivity calculated by Kubo formula1121f\u2009=\u2009\u03c9/2\u03c0\u2009=\u200920\u2009THz, charged particle scattering rate8\u03a9(M))\u22121\u2009>\u20090.6 and 0.5\u2009<\u2009(\u03a9(D))\u22121\u2009<\u2009(\u03a9(G))\u22121\u2009<\u20090.6, where \u03a9\u22121\u2009=\u2009\u03bc/(\u210f\u03c9) is the normalized chemical potential.We consider the 2D metal-gap-dielectric waveguide system composed of three distinct graphene domains ; a dielew\u2009=\u20095\u2009nm, (\u03a9(M))\u22121\u2009=\u20094, (\u03a9(G))\u22121\u2009=\u20090.54, and (\u03a9(D))\u22121\u2009=\u20090.5002). In the numerical analysis, the graphene is considered as the film\u03b4\u2009=\u20090.2\u2009nm and the relative bulk permittivity of \u03b5g(\u03c9)\u2009=\u20091\u2009+\u2009j\u03c3g(\u03c9)/(\u03c9\u03b50\u03b4), where \u03c3g is sheet conductivity of graphene obtained from Kubo formula33\u03c3~\u2009\u2212\u2009\u03c3 for all z) have improved confinement compared to that of the GEP mode with much stronger structural asymmetry |\u2009\u226a\u2009|\u03c3| and |\u03c3|\u2009=\u2009|\u03c3| for z\u2009\u2260\u20090), H-GGP exhibits more confined transverse (Ex) field on the gap region than that of the 1D-SPP mode, as similar to the difference between gap plasmons and surface plasmons in noble metals8Im{\u03c3(G)}\u00b7Ex(G)~Im{\u03c3(D)}\u00b7Ex(D), deriving the enhancement of Ex(G) from the condition of Im{\u03c3(D)}\u2009<\u2009Im{\u03c3(G)}\u2009<\u20090. For the practical realization, we also note that H-GGP modes can be obtained at any finite temperatures when the conductivity of each domain satisfies the condition of Im{\u03c3(D)}\u2009<\u2009Im{\u03c3(G)}\u2009<\u20090\u2009<\u2009Im{\u03c3(M)}, as shown in f\u2009=\u2009100\u2009THz.w\u2009=\u20090) corresponds to the \u03c3(M)\u2009\u2212\u2009\u03c3(D) 1D-SPP system with the effective mode indexneff\u2009=\u2009Re{q}/k0 \u2248 2\u00b7(3/2)1/2\u00b7\u03b5\u03b50\u00b7c/(Im{\u03c3(M)}\u2009+\u2009Im{\u03c3(D)}), while the H-GGP system with infinite w is converged to the \u03c3(M)\u2009\u2212\u2009\u03c3(G) 1D-SPP system. The effective mode index (de index  and the de index  of the Hw case is converged to that of the \u03c3(M)\u2009\u2212\u2009\u03c3(G) 1D-SPP system, smaller w cases exhibit the intensity profiles focused of the graphene gap. Such a distinct in-plane intensity distribution imposes the unique property on out-of-plane confinement, in terms of the light-graphene overlap factor \u03c1\u2009=\u2009\u222b\u222bgraphene|E|2\u00b7dS/\u222b\u222b|E|2\u00b7dS: the concentration of electromagnetic fields on graphene. \u03c1 as a function of the gap width w, which demonstrates the improved light-graphene overlap for the structures with apparent field concentration on the gap (0\u2009<\u2009w\u2009<\u200940\u2009nm). We note that the H-GGP mode acquires much higher field concentration on the graphene layer (\u03c1\u2009=\u20092.07\u2009\u00d7\u200910\u22123 at w\u2009=\u20095\u2009nm), when compared to those of 1D-SPP modes (\u03c3(M)\u2009\u2212\u2009\u03c3(D) system of \u03c1\u2009=\u20091.81\u2009\u00d7\u200910\u22123 and \u03c3(M)\u2009\u2212\u2009\u03c3(G) system of \u03c1\u2009=\u20091.70\u2009\u00d7\u200910\u22123) and the GEP mode (\u03c1\u2009=\u20090.728\u2009\u00d7\u200910\u22123).Most importantly, there exist differentiated features of the H-GGP mode when compared to 1D-SPP modes, as shown in \u03a9(M))\u22121\u2009=\u20094\u2009+\u2009\u0394\u03a9\u22121, (\u03a9(G))\u22121\u2009=\u20090.54\u2009+\u2009\u0394\u03a9\u22121, and (\u03a9(D))\u22121\u2009=\u20090.5002\u2009+\u2009\u0394\u03a9\u22121, with the spatially global (wmax modulation width) modulation range. As seen, the effective mode index of the H-GGP mode can be controlled with an order of smaller modulation of \u0394\u03a9\u22121 when compared to the GEP mode. The H-GGP mode also provides more efficient regime of \u0394\u03a9\u22121 for controlling effective index compared to 1D-SPP modes (\u0394\u03a9\u22121\u2009\u2264\u20090.015). Such improved efficiency is more apparent for the case of the finite modulation region for \u0394\u03a9\u22121 (dotted lines in wmax modulation width around the graphene gap), due to the improved transverse localization of the H-GGP mode  will be required for increasing excitation efficiency, for example, by applying adiabatic procedure or matched layers.We demonstrated the existence of low-dimensional gap plasmon modes on graphene, which supports large light-graphene overlap factor. The system with spatially-varying chemical potential (or doping level) for H-GGP modes can be realized by several existing schemes such as electric field bias332137How to cite this article: Kim, Y. et al. Low-dimensional gap plasmons for enhanced light-graphene interactions. Sci. Rep.7, 43333; doi: 10.1038/srep43333 (2017).Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations."}
{"text": "In the crystal, supra\u00admolecular layers sustained by C\u2014H\u22efO, \u03c0\u2013\u03c0, C\u2014H\u22ef\u03c0(arene) and C\u2014H\u22ef\u03c0(chelate ring) inter\u00adactions are formed.A highly distorted penta\u00adcoordinated C 3)2(C28H32N2O4)], features a distorted SnC2NO2 coordination geometry almost inter\u00admediate between ideal trigonal\u2013bipyramidal and square-pyramidal. The dianionic Schiff base ligand coordinates in a tridentate fashion via two alkoxide O and hydrazinyl N atoms; an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(hydrazin\u00adyl) hydrogen bond is noted. The alk\u00adoxy chain has an all-trans conformation, and to the first approximation, the mol\u00adecule has local mirror symmetry relating the two Sn-bound methyl groups. Supra\u00admolecular layers sustained by imine-C\u2014H\u22efO(hy\u00addroxy), \u03c0\u2013\u03c0 [between dec\u00adyloxy-substituted benzene rings with an inter-centroid separation of 3.7724\u2005(13)\u2005\u00c5], C\u2014H\u22ef\u03c0(arene) and C\u2014H\u22ef\u03c0(chelate ring) inter\u00adactions are formed in the crystal; layers stack along the c axis with no directional inter\u00adactions between them. The presence of C\u2014H\u22ef\u03c0(chelate ring) inter\u00adactions in the crystal is clearly evident from an analysis of the calculated Hirshfeld surface.The title diorganotin compound, [Sn(CH The bond lengths involving the nitro\u00adgen atoms comprising the backbone of the chelate rings suggest some conjugation, i.e. N1\u2014C1, N1\u2014N2 and N2\u2014C12 are 1.317\u2005(3), 1.397\u2005(2) and 1.303\u2005(3)\u2005\u00c5, respectively. The 10 atoms of the fused-ring system appended to the five-membered chelate ring make a dihedral angle of 2.01\u2005(3)\u00b0 with the chelate ring, a conformation allowing the formation of an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(hydrazin\u00adyl) hydrogen bond to close an S(6) loop, Table\u00a02trans conformation with the range of torsion angles being \u2212174.96\u2005(18)\u00b0, for C21\u2014C22\u2014C23\u2014C24, to 179.79\u2005(19)\u00b0, for C25\u2014C26\u2014C27\u2014C28. Indeed, the r.m.s. deviation for the least-squares plane through all non-hydrogen atoms except the Sn-bound methyl groups is relatively small at 0.1179\u2005\u00c5, with maximum deviations being for the terminal methyl group of the alk\u00adoxy chain, i.e. 0.296\u2005(2)\u2005\u00c5, and a central methyl\u00adene-C22 atom, i.e. 0.194\u2005(2)\u2005\u00c5. Hence, to a first approximation, the mol\u00adecule has mirror symmetry, relating the two Sn-bound methyl groups.The five-membered, SnON3N2CH}2 synthon is formed, which encapsulates two six-membered {\u22efHOC3N} synthons formed by the intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(hydrazin\u00adyl) hydrogen bonding mentioned above, Fig.\u00a02a. Centrosymmetrically related dimeric aggregates are linked via \u03c0\u2013\u03c0 inter\u00adactions between dec\u00adyloxy-substituted benzene rings . The remaining inter\u00adactions are of the type C\u2014H\u22ef\u03c0 and involve methyl\u00adene-C\u2014H exclusively. While two of the inter\u00adactions have benzene rings as acceptors, the other two have chelate rings as acceptors, i.e. are of the type C\u2014H\u22ef\u03c0(chelate), a phenomenon gaining increasing attention  hydrogen bond, the hy\u00addroxy-O atom accepts an inter\u00adaction from a centrosymmetrically-related imine-H atom, Table\u00a02et al., 2017dnorm, in the range \u22120.053 to + 1.621 au, Fig.\u00a033N2CH}2 synthon as discussed in the previous section; these are also viewed as blue and red regions near the H and O atoms on the Hirshfeld surface mapped over electrostatic potential (over the range \u00b1 0.075 au), Fig.\u00a04de mapped Hirshfeld surface, Fig.\u00a05A\u22ef\u03c0(C13\u2013C18) contacts at 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z and their reciprocal contacts, i.e. \u03c0\u22efH\u2014C, are represented with blue and white dotted lines, respectively, in Fig.\u00a06a. The other C\u2014H\u22ef\u03c0 contacts involving benzene rings and \u03c0\u2013\u03c0 stacking inter\u00adactions at 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z are illustrated in Fig.\u00a06b.The Hirshfeld surface analysis for (I)et al., 2007a\u2013f; their relative contributions are summarized qu\u00adanti\u00adtatively in Table\u00a03i.e. 97.0%.The overall two-dimensional fingerprint plot and those delineated into H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO, N\u22efH/H\u22efN and C\u22efC contacts  inter\u00adactions, Table\u00a02c and e, as their ring centroids  benzene rings, and appears as an arrow-like distribution of points around de\u00a0=\u00a0di\u00a0\u223c\u00a01.9\u2005\u00c5 in Fig.\u00a07f. The other contacts, having low percentage contribution to the surface, are likely to have a negligible effect on the mol\u00adecular packing.A pair of very short peaks at et al., 2016Chemical context). Two di\u00admethyl\u00adtin structures are available with identical ligands apart from having a substituent in the 5-position, i.e. chloride According to a search of the crystallographic literature -3-hy\u00addroxy-2-napthohydrazide  and tri\u00adethyl\u00adamine  in ethyl acetate (25\u2005ml) were added to di\u00admethyl\u00adtin dichloride  in ethyl acetate (10\u2005ml). The resulting mixture was stirred and refluxed for 3\u2005h. The filtrate was evaporated until a precipitate was obtained. The precipitate was recrystallized from di\u00adchloro\u00admethane:di\u00admethyl\u00adformamide (1:1), and yellow prismatic crystals suitable for X-ray crystallographic studies were obtained from the slow evaporation of the filtrate. Yield: 0.366\u2005g, 60%; M.p.: 507\u2013508\u2005K. IR (cm\u22121): 3162(br), 1633(s), 1597(s), 1169(s) cm\u22121. 1H NMR (in DMSO-d6): \u03b4 11.34 , 8.57 , 6.25\u20136.40, 7.07\u20137.20 , 8.47 , 3.96 , 1.28-1.82 , 0.91, , 0.89 .Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen-bound H atom was located in a difference Fourier map but was refined with a distance restraint of O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O). The maximum and minimum residual electron density peaks of 0.80 and 1.32\u2005e\u2005\u00c5\u22123 were located 0.42 and 0.83\u2005\u00c5, respectively, from the H23B and Sn atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017002365/hb7655sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989017002365/hb7655Isup2.hklStructure factors: contains datablock(s) I. DOI: 1532445CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The reaction of manganese dichloride and iron dichloride with the ligand 5,6-bis\u00ad(pyridin-2-yl)pyrazine-2,3-di\u00adcarb\u00adoxy\u00adlic acid leads to the formation of isotypic binuclear complexes which have a cage-like structure. 4N1,O2,N6:O3;\u03ba4O3:N1,O2,N6-bis\u00ad[di\u00adaqua\u00admanganese(II)] tetra\u00adhydrate, [Mn2(C16H8N4O4)2(H2O)4]\u00b74H2O, (I), and bis\u00ad-\u03ba4N1,O2,N6:O3;\u03ba4O3:N1,O2,N6-bis\u00ad[di\u00adaqua\u00adiron(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]\u00b74H2O, (II), are, respectively, the mangan\u00adese(II) and iron(II) complexes of the ligand 5,6-bis\u00ad(pyridin-2-yl)-pyrazine-2,3-di\u00adcarb\u00adoxy\u00adlic acid. The complete mol\u00adecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxyl\u00adate O atoms, one of which is bridging, and two water O atoms. The metal atoms have MN2O4 coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds involving the coordinating water mol\u00adecules, forming chains along [100]. These chains are linked by O\u2014H\u22efO hydrogen bonds involving the non-coordinating water mol\u00adecules, forming layers parallel to (011). The layers are linked by pairs of C\u2014H\u22efO hydrogen bonds and offset \u03c0\u2013\u03c0 inter\u00adactions, so forming a hydrogen-bonded three-dimensional framework.The title isotypic complexes, bis\u00ad-\u03ba On exposure to air, this compound loses the solvent of crystallization and four water mol\u00adecules, transforming into a polymeric two-dimensional network structure pyrazine-2,3-di\u00adcarb\u00adoxy\u00adlic acid , and by two carboxyl\u00adate O atoms, O1 and O3i . Hence, the ligand coordinates to the metal atoms in a tridentate  and a monodentate (O) manner. Atom O3 is bridg\u00ading, so leading to the formation of a cage-like complex situated about a centre of inversion; illustrated in Fig.\u00a03II complex, (II)ica 6.58\u2005\u00c5, while the Fe1\u22efFe1i distance is ca 6.50\u2005\u00c5. Selected bond lengths and angles for compounds (I)The complete mol\u00adecules of complexes (I)pyrazine, Mn1\u2014N1, bond length is 2.242\u2005(3)\u2005\u00c5, which is shorter than the Mn\u2014Npyridine, Mn1\u2014N3, bond length of 2.311\u2005(3)\u2005\u00c5. The Mn1\u2014Owater bond lengths [2.141\u2005(3) and 2.148\u2005(3)\u2005\u00c5] are similar to the Mn\u2014Ocarboxyl\u00adate, Mn1\u2014O3i, bond length of 2.139\u2005(2)\u2005\u00c5, while distance Mn1\u2014O1 is longer at 2.228\u2005(2)\u2005\u00c5.In complex (I)II two-dimensional coordination polymer involving ligand 2LH, mentioned above. The Fe\u2014Npyrazine bond length, Fe1\u2014N1, is 2.126\u2005(2)\u2005\u00c5, which is slightly shorter than the Fe\u2014Npyridine, Fe1\u2014N3, bond length of 2.205\u2005(3)\u2005\u00c5. The Fe1\u2014Owater bond lengths [2.115\u2005(2) and 2.066\u2005(2)\u2005\u00c5] are similar to the Fe1\u2014Ocarboxyl\u00adate bond lengths [2.131\u2005(2) and 2.139\u2005(2)\u2005\u00c5].In complex (II)W,O3i in the equatorial plane and atoms O2W and N1 in the apical positions with an O2W\u2014Mn1\u2014N1 bond angle of 163.62\u2005(11) \u00b0 (Table\u00a01W\u2014Fe1\u2014N1 bond angle of 165.15\u2005(10)\u00b0 (Table\u00a02viz. 57.28\u2005(17)\u00b0.The geometry of the sixfold coordinated metal atoms can best be described as a distorted octa\u00adhedron, with atoms O1,N3,O1\u00b0 Table\u00a01, and an \u00b0 Table\u00a02. The cooW and O2W), forming chains along [100]; illustrated in Fig.\u00a04W and O4W), forming layers parallel to the bc plane, as illustrated in Fig.\u00a05Cg\u22efCgii = 3.671\u2005(4)\u2005\u00c5 in (I)Cg is the centroid of the ring N3/C5\u2013C9; symmetry code: (ii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01], link the layers, forming a three-dimensional framework; illus\u00adtrated in Fig.\u00a06Details of the hydrogen-bonding inter\u00adactions in the crystals of both compounds, are given in Table\u00a03fs Fig.\u00a05. Pairs oet al., 20162LH, and its dimethyl ester, gave eight hits. Some of these structures have been mentioned in the Chemical context above. In the case of (I)N,N,O) and monodentate (O) manner. This coordination mode of 2LH is the same as that observed in the CdII two-dimensional coordination polymer  has been reported previously pyrazine-2,3-di\u00adcarb\u00adoxy\u00adlic acid (Synthesis of compound (I): 2LH  was added in solid form to an aqueous solution (15\u2005ml) of MnCl2\u00b74H2O . The yellow solution immediately obtained was stirred for 10\u2005min at room temperature, filtered and the filtrate allowed to slowly evaporate. After two weeks orange\u2013yellow rod-like crystals were obtained. They were separated by filtration and dried in air . Selected IR bands : \u03bd 3226, 3080(w), 1636(s), 1598(vs), 1545(w), 1475(m), 1440(m), 1410(w), 1366(s), 1348(s), 1301(w), 1275(w), 1170(m), 1126(m), 1007(w), 954(w), 850(w), 790(m), 562(m).Synthesis of compound (II): A degassed aqueous solution (20\u2005ml) of 2LH  was treated with FeCl2\u00b74H2O . The violet solution immediately obtained was stirred under N2 at 343\u2005K for 1\u2005h, filtered and the filtrate allowed to slowly evaporate. After two months deep-violet block-like crystals were obtained. They were separated by filtration and air dried . Precipitation of small amounts of iron(III) hydroxide accompanied the formation of the crystals. Selected IR bands : \u03bd 3477, 3291, 3078(w), 1640(s), 1593(vs), 1545(w), 1475(m), 1440(m), 1405(w), 1359(m), 1300(w), 1286(w), 1269(w), 1172(m), 1124(m), 1008(w), 954(w), 847(w), 789(m), 772(w), 677(w), 565(m), 549(w), 494(m) %.Uiso(H) = 1.2Ueq(C). Intensity data for (I)Rint = 0, and as no suitable \u03c8-scans could be measured no absorption correction was applied. For compound (II)Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016014055/pj2034sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989016014055/pj2034Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016014055/pj2034IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1502352, 1502351CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Single-molecule magnet (SMM) properties of these four complexes were observed\u00a0to be dependent on the ROH lattice solvent molecule. There is an interesting magneto-structural correlation: the larger the R group, the higher the energy barrier. For the first time, the\u00a0solvatomagnetic effect is\u00a0used for the\u00a0continuous fine adjustment\u00a0of the energy barrier of 0D molecular nanomagnets. Additionally, [Cu3Dy2(H3L)2(OAc)2(hfac)4]\u22192MeOH (5), an\u00a0analogue of [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192MeOH (1), is also reported for comparison.Solvents play important roles in our lives, they are also of interest in molecular materials, especially for molecular magnets. The solvatomagnetic effect is generally used for trigger and/or regulation of magnetic properties in molecule-based\u00a0systems, however, molecular nanomagnets showing solvatomagnetic effects are very difficult to obtain. Here we report four 3d-4f heterometallic cluster complexes containing ROH lattice solvent molecules, [Cu The solvatomagnetic effect is very interesting because solvent molecules can be used for trigger and/or regulation of magnetic properties while the molecular magnetic structure is always maintained. Therefore, molecular magnets showing solvatomagnetic effects can be used as molecule devices, molecular switches and/or molecular sensors. Naturally, solvatomagnetic effects are\u00a0often found\u00a0in porous metal-organic frameworks (MOFs) in which solvent molecules are guest molecules9, while low-dimensional systems with solvatomagnetic effects are more difficult to obtain due to the\u00a0lack of pores. Recently, we found a chain-like azido-bridged manganese(III) coordination polymer showing both solvatomagnetic effect and spin-glass behaviour10. In studies of single molecule magnets (SMMs)11, we also hope to explore SMM systems with solvatomagnetic effects. However, it is a great challenging task because most SMMs\u00a0reported are concentrated on zero-dimensional (0 D) cluster or mononuclear systems.Solvents, especially water, are critical to the origins of life, and they have penetrated into all aspects of human life. Besides as reaction mediums and extracting agents, chemical solvents are also of interest in molecular materials. For example, in the field of molecular magnets they can\u00a0be utilized as the\u00a0terminal ligand to complete the coordination configuration17; and the energy barrier leading to magnetic bistability and slow magnetic relaxation is a pivotal parameter. Therefore, except enhancing the relaxation energy barrier and increasing the blocking temperature21, tuning the relaxation energy barrier is another important target in the molecular nanomagnet field26. Surprisingly, systematic studies\u00a0of SMMs with the same magnetic structure are\u00a0still rare, however, some factors such as the\u00a0electron-withdrawing effect27, the\u00a0electrostatic potential of the key coordination atom28 have been observed to be able to modulate SMMs\u2019 energy barriers recently. Regarding structures and magnetic properties may be affected by a small change of circumstance, solvent molecules may also be used to adjust SMMs\u2019 properties. To the best of our knowledge, a direct correlation between energy barriers and different lattice solvent molecules of 0D molecular nanomagnets has never been documented, though a 3D Dy(III) MOF-type SMM was found to show an obvious solvatomagnetic effect in 201529, and guest-dependent single-ion magnet behaviours were observed in a 2D cobalt(II) coordination polymer\u00a0in 201630. Herein we describe the lattice-solvent effect of ROH molecules  on the energy barrier of 0D SMMs with the same magnetic structure [Cu3Tb2(H3L)2(OAc)2(hfac)4] {H6L\u2009=\u20091,3-Bis[tris(hydroxymethyl)methylamino]propane, Fig.\u00a0\u2212\u2009=\u2009hexafluoroacetylacetonate}. Fine adjustment of the energy barrier  in this [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system was achieved by changing the\u00a0ROH lattice solvent molecule. A similar [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMM system was also studied, but only the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4]\u22192MeOH (5) was successfully\u00a0solved; complex 5 also exhibits slow magnetic relaxation under zero dc field, with the energy barrier of 30.0\u2009K, a relatively high value for reported relaxation barriers of the Cu-Dy heterometallic SMMs.It is well known that SMMs are of great potential for technological applications in high-density information storage, quantum computing and spintronics6L), an universal ligand due to flexible polydentate coordination sites, has been used to bind\u00a0not only 3d transition metal ions32 but also 4\u2009f lanthanide metal ions33. Furthermore, it can also be utilized to construct 3d-4f heterometallic complexes34. Recently, Murrie et al. reported a series of 3d-4f complexes formulated as {Ln2Cu3(H3L)2Xn} 35; they found that changing\u00a0the auxiliary ligand OAc\u2212 through\u00a0NO3\u2212 may lead to a remarkable improvement of the energy barrier of {Tb2Cu3(H3L)2Xn} (X\u2009=\u2009OAc\u2212 and NO3\u2212) complexes, which suggests that the anion co-ligand has\u00a0a great impact on the energy barrier of {Tb2Cu3(H3L)2Xn} SMMs. In the recent process of pursuing new SMMs, we observed that using Ln(OAc)(hfac)2(H2O)2 as the lanthanide (III) salt source may lead mixed co-ligands OAc\u2212 and hfac\u2212 into 3d-4f heterometallic clusters effectively36. Therefore, we adopted this synthesis strategy to obtain the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM with different ROH lattice solvent molecules , in which not only the OAc\u2212 anion but also the hfac\u2212 anion are co-ligands. Notably, our synthetic procedures were\u00a0completed at room temperature rather than at 60\u2009\u00b0C used by Murrie group35. Products\u00a0using methanol, ethanol and isopropyl alcohol as reaction solvents were [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192MeOH (1), [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192EtOH (2) and [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192iso-C3H7OH (3), respectively; while [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192H2O (4) was quantitatively transformed from complex 1 by taking place of methanol molecules with water molecules. In order to yield [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMMs with larger ROH lattice solvent molecules, other ROH solvents such as isobutyl alcohol, n-butyl alcohol and isoamyl alcohol were also used instead of methanol for 1, but no any crystalline products could be obtained. Furthermore, the [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMM system was also explored, but only the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4]\u22192MeOH (5) was successfully\u00a0solved, the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMMs with other lattice solvent molecules  could not be obtained due to the severe\u00a0twinning phenomenon.Bis-tris propane (H3Tb2(H3L)2(OAc)2(hfac)4]\u22192ROH SMMs have the main structure [Cu3Tb2(H3L)2(OAc)2(hfac)4] 2(OAc)2(hfac)4]\u22192MeOH (1) is chose to be described in detail. In the main structure [Cu3Tb2(H3L)2(OAc)2(hfac)4], a {Cu3(H3L)2} linear unit is formed through bridging two terminal {Cu(H3L)}\u2212 fragments using\u00a0a central Cu2+ ion, then two Tb3+ ions link to this {Cu3(H3L)2} linear unit in the opposite direction, in which each Tb3+ ion connects with the central Cu2+ ion and one external Cu2+ ion through sharing one \u03bc3-O atom\u00a0and one \u03bc-O atom from one H3L3\u2212 ligand, and one \u03bc3-O atom from the other H3L3\u2212 ligand 2Xn}35. The eight-coordinate sphere of each Tb3+ ion is finally completed by two hfac\u2212 anions and one OAc\u2212 anion. Shape software37 was adopted to calculate the Tb(III) coordination polyhedron, giving a triangular dodecahedron as the most likely configuration for complex 1, and the deviation value from the ideal D2d symmetry is 1.015  coordination polyhedra of complexes 2\u20134 using Shape software37 are listed in Tables\u00a0All  SMM system.The direct current (dc) variable-temperature magnetic susceptibility\u00a0of complexes eld Fig.\u00a0. The roo 24.91\u2009cm\u2009K mol\u22121,\u03c7\u2032, Fig.\u00a0\u03c7\u2032\u2032, Fig.\u00a01\u20134 are frequency-dependent in zero dc field, indicating slow magnetic relaxation typical for SMMs. Such thermally induced relaxation was fitted with the Arrhenius law, \u03c4\u2009=\u2009\u03c40exp(Ueff/kT), extracting Ueff/k values of 30.0(0.4) K for 1, 32.4(0.2) K for 2, 33.1(0.7) K for 3 and 25.7(0.2) K for 4 as well as \u03c40 values of 3.7(0.2)\u2009\u00d7\u200910\u22128 s for 1, 6.2(0.1)\u2009\u00d7\u200910\u22129 s for 2, 2.6(0.3)\u2009\u00d7\u200910\u22128 s for 3 and 2.3(0.1)\u2009\u00d7\u200910\u22128 s for 4 13. A comparison of the effective barrier value for complexes 1\u20134 with the R group of the ROH lattice solvent molecules  reveals an important magneto-structural correlation for this [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system: The larger the R group in ROH, the higher the energy barrier of the [Cu3Tb2(H3L)2(OAc)2(hfac)4]\u22192ROH SMM 2[Tb2Cu3(H3L)2(NO3)7(CH3OH)2](NO3) (36\u2009K)35; the Ueff/k value of 1 is also remarkable, which is comparable with that of [Cu22Tb2(N3)6]\u00b72CH3OH  38. In many cases44, a dc field is necessary for 3d-4f heterometallic complexes to display magnetic relaxation because of the\u00a0obvious quantum-tunnelling effects.The solvatomagnetic effect could also be detected by alternating current (ac) magnetic susceptibility investigations. Both the in-phase \u03c7\u2032, Fig.\u00a0, SI and r 4 Fig.\u00a0. All fouSMM Fig.\u00a0. It is n3Tb2(H3L)2Xn] system is not because of single-ion behaviours, and both the Cu\u00b7\u00b7\u00b7Cu and Cu\u00b7\u00b7\u00b7Tb ferromagnetic interactions maybe quench the tunnel splitting, which are similar to acting as an internal applied field, inducing to zero-field SMM behaviours35. Nevertheless, the difference of the Tb3+ coordination configurations has\u00a0influence on the SMM characteristics35. Owing to great difficulty for theoretical calculation and comparison of the Cu\u00b7\u00b7\u00b7Cu and Cu\u00b7\u00b7\u00b7Tb ferromagnetic couplings35, we tried to make a magneto-structural correlation for complexes 1\u20134 using the deviation value from the ideal D2d symmetry of the\u00a0biaugmented trigonal prism for the Tb3+ ion and the intermolecular distance as two main structural parameters. As shown in Table\u00a03+ ions is\u00a0closer to the biaugmented trigonal prism from 1 to 3, the corresponding energy barrier value becomes larger from 1 to 3, indicating the biaugmented trigonal prism configuration in the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system is the dominant configuration; but 4 is a bit unusual, its deviation value (1.735) is comparable with that of 1 (1.756), which suggests that\u00a0other structural factors such as intermolecular distances need to be considered; as shown in Table\u00a0central\u2026Cucentral separation), the higher the energy barrier; which is in line with the magneto-structural correlation using the R group itself, because larger ROH lattice solvent molecules may enhance intermolecular distances correspondingly.Simplified theoretical investigations by Murrie group suggested that the magnetic bistability in the (NO3)35, and the ferromagnetic coupling obviously exists between the Cu2+ ion and the Dy3+ ion as well as among the Cu2+ ions, similar to that observed in [Gd2Cu3(H3L)2(CH3COO)6]\u00b7THF\u00b73H2O by Murrie group35.The l\u22121 Fig.\u00a0, which i5 are similar to those of complexes 1\u20134. Under zero dc field, the appearance of frequency-dependent \u03c7\u2032  K and \u03c40\u2009=\u20099.7(0.1)\u2009\u00d7\u200910\u22129 s 2{Dy2Cu3(H3L)2(NO3)7(CH3OH)2](NO3) [23.9(0.1) K], whose \u03c7\u2033 signals even do not appear peaks in zero dc field35. Notably, this Ueff/k value is the third high value for the Cu-Dy heterometallic SMMs, after 47\u2009K of [{Dy(hfac)3}2{Cu(dpk)2}] (dpk\u2212\u2009=\u2009di-2-pyridyl ketoximate)48 and 41.6\u2009K of [Cu4Dy4(vanox)6(Hvanox)2(NO3)4(\u03bc-HOMe)2]\u00b76MeOH 49. Furthermore, this Ueff/k value is remarkable larger than those of the Cu-Dy heterometallic SMMs with higher nucleus (<20\u2009K)51. Additionally, the parameter \u03a6 value of 0.16 for 5 supports the SMM nature too.The magnetization dynamics of compound  \u03c7\u2032 Fig.\u00a0, SI and als Fig.\u00a0 indicate9 s Fig.\u00a0. The ene5 revealed that the \u03c7\u2033 signals of 5 are temperature-dependent methylamino]propane ligand (H6L). The ROH lattice solvent molecules  in the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system have great influences on the energy barrier; the larger the R group, the higher the energy barrier. We predict that the larger ROH molecule may enlarge the intermolecular distance and can help to change the coordination configuration of the Ln(III) ions through the hydrogen bonding interaction between the ROH lattice solvent molecule and the [Cu3Tb2(H3L)2(OAc)2(hfac)4] main-structural molecule. Our work demonstrates that solvatomagnetic effects can be used to\u00a0continuously fine-tune energy barriers in\u00a0SMMs. The discovery is bound to have significances in enhancing and turning energy barriers of molecular nanomagnets via chemical methods such as using lattice-solvent effects.In summary, a mixed OAcThe elemental analyses were measured on a Vario ELIII elemental analyser. The magnetic susceptibility measurements were carried out on a Quantum Design MPMS-XL5 SQUID magnetometer, and diamagnetic corrections were calculated from Pascal\u2019s constants of all components.6L (0.25\u2009mmol) and Cu(ClO4)2\u00b76H2O (0.375\u2009mmol) in 20\u2009mL of MeOH, was added Tb(OAc)(hfac)2(H2O)2 (0.15\u2009mmol), a blue solution was formed after being stirred for 10\u2009min; Et3N (0.75\u2009mmol) was then added dropwise, the resultant solution was stirred for 3\u2009h at room temperature and turned violet. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 1 week. Yield (25%). Anal. Calcd (%) for C48H64Cu3F24N4O26Tb2 (1) C 27.75; H 3.11; N 2.70. Found: C 27.80; H 3.14; N 2.67.To a mixture of H1 was followed, but using ethanol instead of methanol. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 10 days. Yield (27%). Anal. Calcd (%) for C50H68Cu3F24N4O26Tb2 (2): C 28.52; H 3.26; N 2.66. Found: C 28.55; H 3.29; N 2.63.The same synthetic procedure for complex 1 was followed, but using isopropyl alcohol instead of methanol. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 15 days. Yield (22%). Anal. Calcd (%) for C52H72Cu3F24N4O26Tb2 (3): C 29.27; H 3.40; N 2.63. Found: C 29.23; H 3.43; N 2.60.The same synthetic procedure for complex 1 was kept at 60\u2009\u00b0C for 6\u2009h, and then exposed on air for 24\u2009h. Violet plate-like X-ray quality crystals of 4 were obtained quantitatively. Anal. Calcd (%) for C46H60Cu3F24N4O26Tb2 (4): C 26.96; H 2.95; N 2.73. Found: C 27.02; H 2.99; N 2.69.Complex 1 was followed, but using Dy(OAc)(hfac)2(H2O)2 instead of Tb(OAc)(hfac)2(H2O)2. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 1 week. Yield (28%). Anal. Calcd (%) for C48H64Cu3Dy2F24N4O26 (5): C 27.66; H 3.09; N 2.69. Found: C 27.69; H 3.11; N 2.67.The same synthetic procedure for complex 3 of 1, 0.178\u2009\u00d7\u20090.063\u2009\u00d7\u20090.024\u2009mm3 of 2, 0.183\u2009\u00d7\u20090.125\u2009\u00d7\u20090.031\u2009mm3 of 3, 0.108\u2009\u00d7\u20090.067\u2009\u00d7\u20090.025\u2009mm3 of 4, and 0.134\u2009\u00d7\u20090.125\u2009\u00d7\u20090.027\u2009mm3 of 5 was picked out to mount on a Bruker SMART APEX-CCD diffractometer with Mo-K\u03b1 radiation (\u03bb\u2009=\u20090.71073\u2009\u00c5) for data collection at 173(2) K. Empirical absorption corrections from \u03c6 and \u03c9 scan were applied. Cell parameters were calculated by the global refinement of the positions of all collected reflections for five complexes. The structures were solved by direct methods and refined by a full matrix least-squares technique based on F2 using with the SHELX-2014 program package. All hydrogen atoms were set in calculated positions and refined as riding atoms, and all non-hydrogen atoms were refined anisotropically. CCDC 1574978\u20131574982 contain the supplementary crystallographic data, which can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.A single crystal with dimensions 0.261\u2009\u00d7\u20090.093\u2009\u00d7\u20090.025\u2009mm1: P\u22121, a\u2009=\u200910.086(2)\u2009\u00c5, b\u2009=\u200912.463(3)\u2009\u00c5, c\u2009=\u200915.594(3)\u2009\u00c5, \u03b1\u2009=\u2009104.67(3)\u00b0, \u03b2\u2009=\u200994.07(3)\u00b0, \u03b3\u2009=\u2009108.97(3)\u00b0, V\u2009=\u20091767.9(7)\u2009\u00c53, Mr\u2009=\u20092077.49, Dc\u2009=\u20091.951\u2009g\u2009cm\u22123, Z\u2009=\u20091, R1\u2009=\u20090.0366 (I\u2009>\u20092\u03c3(I)), wR2\u2009=\u20090.0878 (I\u2009>\u20092\u03c3(I)), S\u2009=\u20091.080.Crystal data for 2: P\u22121, a\u2009=\u200910.243(2)\u2009\u00c5, b\u2009=\u200912.469(3)\u2009\u00c5, c\u2009=\u200915.602(3)\u2009\u00c5, \u03b1\u2009=\u2009101.71(3)\u00b0, \u03b2\u2009=\u200996.50(3)\u00b0, \u03b3\u2009=\u2009110.00(3)\u00b0, V\u2009=\u20091797.2(6)\u2009\u00c53, Mr\u2009=\u20092105.54, Dc\u2009=\u20091.945\u2009g\u2009cm\u22123, Z\u2009=\u20091, R1\u2009=\u20090.0498 (I\u2009>\u20092\u03c3(I)), wR2\u2009=\u20090.1085 (I\u2009>\u20092\u03c3(I)), S\u2009=\u20091.122.Crystal data for 3: P\u22121, a\u2009=\u200910.309(2)\u2009\u00c5, b\u2009=\u200912.473(3)\u2009\u00c5, c\u2009=\u200915.677(3)\u2009\u00c5, \u03b1\u2009=\u2009101.80(3)\u00b0, \u03b2\u2009=\u200996.96(3)\u00b0, \u03b3\u2009=\u2009110.19(3)\u00b0, V\u2009=\u20091811.4(7)\u2009\u00c53, Mr\u2009=\u20092133.58, Dc\u2009=\u20091.956\u2009g\u2009cm\u22123, Z\u2009=\u20091, R1\u2009=\u20090.0345 (I\u2009>\u20092\u03c3(I)), wR2\u2009=\u20090.0797 (I\u2009>\u20092\u03c3(I)), S\u2009=\u20091.084.Crystal data for 4: P\u22121, a\u2009=\u200910.042(2)\u2009\u00c5, b\u2009=\u200912.480(3)\u2009\u00c5, c\u2009=\u200915.819(3)\u2009\u00c5, \u03b1\u2009=\u2009107.08(3)\u00b0, \u03b2\u2009=\u200999.23(3)\u00b0, \u03b3\u2009=\u2009109.83(3)\u00b0, V\u2009=\u20091706.2(7)\u2009\u00c53, Mr\u2009=\u20092049.44, Dc\u2009=\u20091.995\u2009g\u2009cm\u22123, Z\u2009=\u20091, R1\u2009=\u20090.0488 (I\u2009>\u20092\u03c3(I)), wR2\u2009=\u20090.0945 (I\u2009>\u20092\u03c3(I)), S\u2009=\u20091.153.Crystal data for 5: P\u22121, a\u2009=\u200910.085(2)\u2009\u00c5, b\u2009=\u200912.427(3)\u2009\u00c5, c\u2009=\u200915.581(3)\u2009\u00c5, \u03b1\u2009=\u2009104.59(3)\u00b0, \u03b2\u2009=\u200994.21(3)\u00b0, \u03b3\u2009=\u2009108.86(3)\u00b0, V\u2009=\u20091762.5(7)\u2009\u00c53, Mr\u2009=\u20092084.65, Dc\u2009=\u20091.964\u2009g\u2009cm\u22123, Z\u2009=\u20091, R1\u2009=\u20090.0321 (I\u2009>\u20092\u03c3(I)), wR2\u2009=\u20090.0762 (I\u2009>\u20092\u03c3(I)), S\u2009=\u20091.074.Crystal data for Supplementary Information"}
{"text": "Only a weak directional inter\u00adaction of the C\u2014H\u22efO type combines mol\u00adecules in infinite chains running along the  23H26O5 or CH2=C(CH3)\u2014C(O)O\u2014C6H4\u2014O(O)C\u2014C6H4\u2014OC6H13, has been determined. The mol\u00adecule is non-planar and the dihedral angle between the phenyl rings is 50.72\u2005(4)\u00b0. The crystal packing differs from those typical for mesogenic compounds. Only a weak directional inter\u00adaction of the C\u2014H\u22efO type combines mol\u00adecules in endless chains running along the a axis.The structure of the title compound, C The structural studies of these compounds are of great inter\u00adest as these investigations make it possible to clarify the structure of the mesophase and propose a mechanism of phase transitions in a crystal-mesophase-isotropic system.Phenyl\u00adbenzoates bearing a rather long aliphatic substituent at the benzene ring are potentially mesogenic compounds. On melting, these compounds often form smectic or nematic phases. Cases where these compounds exhibit a monotropic mesomorphism, IIICr 367.7\u2005K Iso 350.6\u2005K IICr 349.9\u2005K ICr.In this work we performed an X-ray structural determination and DSC study of the title compound. According to DSC the compound is non\u2013mesomorphic, exhibiting three solid-state modifications: viz. benzene rings C8\u2013C13 (plane I) and C2\u2013C7 (plane II), ester groups C2/C1/O1/O2 (plane III) and O4/O5/C20/C21 (plane IV) and the hex\u00adyloxy group O3/C14\u2013C19 (plane V). The dihedral angles between the planes I/II, II/III, II/V, I/III and I/IV are 50.72\u2005(4), 4.84\u2005(5), 7.05\u2005(3), 52.82\u2005(4) and 55.50\u2005(5)\u00b0, respectively. According to the CSD Groom et al., 2016nHn+12 (n > 4), this substituent has an extended structure and its plane is nearly coplanar with the plane of the corresponding benzene ring.The unit cell contains one independent mol\u00adecule whose structure is shown in Fig.\u00a01et al., 2009et al., 2012et al., 2009n--n\u2032-tolyidines  related mol\u00adecules may be considered to be weak hydrogen bonds  I. DOI: 10.1107/S2056989017008568/rk2436Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008568/rk2436Isup3.cmlSupporting information file. DOI: 1554948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule is V-shaped and possesses mirror symmetry; the mirror bis\u00adects the central benzene ring. There are two intra\u00admolecular O\u2014H\u22efN hydrogen bonds present forming S(6) ring motifs.The title Schiff base compound was synthesized  34H28N2O4, is generated by mirror symmetry, with the mirror bis\u00adecting the central benzene ring. It was synthesized via the condensation reaction of 1,2-di\u00adamine\u00adbenzene with 4-benz\u00adyloxy-2-hy\u00addroxy\u00adbenzaldehyde. The mol\u00adecule is V-shaped and there are two intra\u00admolecular O\u2014H\u22efN hydrogen bonds present forming S(6) ring motifs. The configuration about the C=N imine bonds is E. The central benzene ring makes dihedral angles of 41.9\u2005(2) and 43.6\u2005(2)\u00b0 with the phenol ring and the outer benz\u00adyloxy ring, respectively. The latter two rings are inclined to each other by 84.4\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers lying parallel to the ab plane. The Hirshfeld surface analysis and the two-dimensional fingerprint plots confirm the predominance of these inter\u00adactions in the crystal structure. The anti\u00adoxidant capacity of the compound was determined by the cupric reducing anti\u00adoxidant capacity (CUPRAC) process.The whole mol\u00adecule of the title Schiff base compound, C In view of this inter\u00adest we have synthesized the title compound, (I)1H NMR NMR spectrum reveals the presence of an imino group (N=CH) in the range \u03b4 = 8.5\u20138.7 p.p.m. The anti\u00adoxidant capacity of the compound was determined by the cupric reducing anti\u00adoxidant capacity (CUPRAC) process.Schiff base derivatives are a biologically versatile class of compounds possessing diverse activities, such as anti-oxidant (Haribabu viz. bonds C1\u2014C1i and C3\u2014C3i . In the mol\u00adecule there are two intra\u00admolecular O\u2014H\u22efN hydrogen bonds present (Table\u00a01S(6) ring motifs as shown in Fig.\u00a01E and the C4=N1 bond length is 1.278\u2005(6)\u2005\u00c5. The C3\u2014N1=C4 bond angles are less than 120\u00b0 [118.9\u2005(4)\u00b0], and the imine group has a C3\u2014N1\u2014C4\u2014C5 torsion angle of \u2212176.8\u2005(4)\u00b0. The mol\u00adecule is V-shaped and the two arms are non-planar; the central benzene ring forms dihedral angles of 41.9\u2005(2) and 43.6\u2005(2)\u00b0 with the phenol ring (C5-C10) and the outer benz\u00adyloxy ring (C12\u2013C17), respectively. The latter two rings are almost normal to each other, with a dihedral angle of 84.4\u2005(2)\u00b0.The mol\u00adecular structure of compound (I)t Table\u00a01, which fIn the crystal of (I)et al., 2007CrystalExplorer17  and H\u22efC/C\u22efH at 34.6% , followed by the H\u22efO/O\u22efH inter\u00adactions at 13.6% .The Hirshfeld surface analysis ]diphenol ethanol solvate (II) ]diphenol (III)  ring motifs.A search of the Cambridge Structural Database  the phenol rings are inclined to the central benzene ring by 53.9\u2005(3) and 4.0\u2005(2)\u00b0 and to each other by 49.9\u2005(2)\u00b0. In (III) the corresponding dihedral angles are 48.12\u2005(8), 21.44\u2005(8) and 47.70\u2005(8)\u00b0, while in (V) the corresponding dihedral angles are 58.29\u2005(12), 2.20\u2005(12) and 57.60\u2005(12)\u00b0. In compound (IV), that possesses twofold rotational symmetry with the twofold axis bis\u00adecting the central benzene ring, the phenol rings are inclined to the central benzene ring by 82.30\u2005(5)\u00b0 and to each other by 63.76\u2005(5)\u00b0. In the title compound, which possesses mirror symmetry, the corresponding dihedral angles are 41.9\u2005(2) and 68.9\u2005(2)\u00b0.o-phenyl\u00adenebis(nitrilo\u00admethyl\u00adidyne)]diphenolato)nickel(II) dihydrate methylyl\u00adidene]}di\u00adbenzene-1,3-diolato-\u03baO3)copper(II) methanol solvate II-Nc] (CUPRAC) method Nc2\u2013Cu+2 complex. Indeed, in the presence of an anti\u00adoxidant agent, the copper\u2013neocuproene complex is reduced and this reaction is qu\u00adanti\u00adfied spectrophotometrically at a wavelength of 450\u2005nm.The anti\u00adoxidant activity profile of the synthesized compound (I)0.50 = 15.03 \u00b1 1.50 for a 4\u2005mg dosage, compared to the results for buthylated toluene (BHT) [A0.50 = 8.97 \u00b1 3.94], used as a positive control (see Table\u00a02p < 0.05).According to the cupric ion reducing anti\u00adoxidant capacity assay, the title compound displayed activity with variable potency in all tested concentrations, because the percentage (%) inhibition in the CUPRAC assay is good [Ain vacuo. The residue was recrystallized from ethanol, yielding yellow block-like crystals of the title compound on slow evaporation of the solvent. The purity of the compound was characterized by its NMR spectrum . The azomethine proton appears in the 8.5\u20138.7 p.p.m. range, while the imine bond is characterized in the 13C RMN spectrum with the imine C and OH signals in the range 162.23\u2013163.34 p.p.m. 1H NMR: \u03b4 = 6.5\u20137.6 , \u03b4 = 13.7 , \u03b4 = 5.1 . 13C NMR: 70.15, 120.33, 127.30, 127.64, 128.26, 128.75, 142.32, 162.23, 163.33, 163.34.1,2-Di\u00adamine\u00adbenzene (0.027\u2005g) and 4-benz\u00adyloxy-2-hy\u00addroxy\u00adbenzaldehyde (0.1141\u2005g) in ethanol (15\u2005ml) were refluxed for 1\u2005h, then the solvent was evaporated Uiso(H) = 1.5Ueq(O). The C-bound H atoms were positioned geometrically (C\u2013H = 0.93\u20130.97\u2005\u00c5) and refined as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018005832/su5438sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989018005832/su5438Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018005832/su5438Isup3.cmlSupporting information file. DOI: 1837095CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure of the title Schiff base derivative is reported. The crystal packing depends on O\u2014H\u22efN hydrogen-bonds, augmented by C\u2014H\u22ef\u03c0 inter\u00adactions. 17H18N2O, the central carbon atom with the OH substituent and one of the (E)-benzyl\u00adidene\u00adamino substituents are disordered over two sets of sites with occupancies of 0.851\u2005(4) and 0.149\u2005(4). The relative positions of the two disorder components is equivalent to a rotation of approximately 60\u00b0 about the C\u2014N single bond. In the crystal, the mol\u00adecules are held together by O\u2014H\u22efN hydrogen bonds, forming simple C(5) chains along the b-axis direction. In addition, pairs of the chains are further aggregated by weak C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, C To gain more insight into the structural and spectroscopic properties of this potentially polydentate ligand, we report herein the mol\u00adecular structure of the title compound.During the last decades, inter\u00adest in Schiff bases and their complexes has been constant due to their extensive use for industrial purposes and also for their broad range of biological activities :0.149\u2005(4). The difference between the two conformers is reflected in the relative arrangement of the central spacer units. In the major disorder component, the torsion angle C3\u2014C4\u2014N2\u2014C5 is \u2212158.7\u2005(2)\u00b0 whereas the corresponding angle C3\u2032\u2014C4\u2032\u2014N2\u2032\u2014C5\u2032 in the minor component is \u221293.3\u2005(14)\u00b0. This translates to a rotation of approximately 60\u00b0 about the C4\u2014N2 bond. In the second, fully ordered, (E)-benzyl\u00adidene\u00adamino substituent, the equivalent torsion angles C1\u2014N1\u2014C2\u2014C3 and C1\u2014N1\u2014C2\u2014C3\u2032 are \u2212102.03\u2005(18)\u00b0 and \u221279.8\u2005(8)\u00b0, respectively.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01synclinal (-sc) alignment of the hydroxyl and imine nitro\u00adgen atoms around the N(imine)\u2014C\u2014C\u2014O(hydrox\u00adyl) bond  indicate a slight loss of the sp2 character. The N1=C1 azomethine group is essentially co-planar with the attached benzene ring with an N1\u2014C1\u2014C11\u2014C12 torsion angle being 2.0\u2005(5)\u00b0. In contrast, in the disordered (E)-benzyl\u00adidene\u00adamino substituent, the corresponding torsion angles N2\u2014C5\u2014C21\u2014C22 and N2\u2032\u2014C5\u2032\u2014C21\u2032\u2014C22\u2032 are \u221217.6\u2005(6) and 21\u2005(4)\u00b0 for the major and minor disorder components, respectively. All these data suggest that the difference between these (E)-benzyl\u00adidene\u00adamino substituents may result from some loss of conjugation between the phenyl ring and its azomethine substituent in the disordered branch of the mol\u00adecule.The N1=C1 and N2=C5 distances in the mol\u00adecule are 1.270\u2005(2) and 1.259\u2005(3)\u2005\u00c5, respectively, consistent with C=N double bonding. The C1\u2014N1\u2014C2 bond angle of 118.61\u2005(15)\u00b0 confirms the C(5) chains along the b-axis direction. In addition, pairs of the chains are linked by weak C24\u2014H24\u22efCg1 inter\u00adactions bis\u00ad] bis\u00ad(4-methyl\u00adbenzene\u00adsulfonamide) -(2-chloro\u00adbenzyl\u00adidene)amino]\u00adpropan-2-ol -(4-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adpropan-2-ol  = 0.95\u2005\u00c5 for aromatic and azomethine atoms, d(C\u2014H) = 0.99\u2005\u00c5 for methyl\u00adene and d(C\u2014H) = 1.00\u2005\u00c5 for C3\u2014H3. The Uiso(H) values were constrained to 1.2Ueq(C). The C3/C4/N2/C5/C21\u2013C26 segment of the mol\u00adecule is disordered over two sets of sites with a refined occupancy ratio of 0.851\u2005(4):0.149\u2005(4).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017004741/sj5523sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004741/sj5523Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004741/sj5523Isup3.cmlSupporting information file. DOI: 1540296CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Mecp2ZFN\u0394/y rats display respiratory abnormalities early in development.Post-publication, the authors discovered a scale factor error of 5 affecting volumetric readings from the whole-body plethysmography chamber used for juvenile male rats (PND 21-28) in this study (Buxco PLY3211). As such, reported tidal volume (TV) and minute ventilation (MV) data are erroneously high for this group. This change does not affect the interpretation of this data as the scale factor change is applicable to both groups being compared. The below figure shows the corrected graphical representation of juvenile male rats' TV and MV readings . All numerical values have been reduced by a factor of 5 to correct for the recognized instrument error. The text of the results section has been updated online to reflect this numerical correction and should be as follows:Mecp2ZFN\u0394/y rats exhibited abnormal breathing compared to WTs . Juvenile WTs breathed at a rate of 126.6\u2009\u00b1\u20095.3 BPM, which is comparable to respiratory rates of similarly aged Sprague-Dawley rats (46); however, age-matched Mecp2ZFN\u0394/y rats breathed at a rate of only 100.1\u2009\u00b1\u20094.7 BPM . The reduction in frequency was due to both an increase in inspiratory time (Ti) (0.20\u2009\u00b1\u20090.01\u2009s WT vs. 0.25\u2009\u00b1\u20090.01\u2009s Mecp2ZFN\u0394/y)  and expiratory time (Te) (0.28\u2009\u00b1\u20090.01\u2009s WT vs. 0.37\u2009\u00b1\u20090.03\u2009s Mecp2ZFN\u0394/y) . Despite these changes in respiratory frequency, juvenile Mecp2ZFN\u0394/y males exhibit an otherwise normal tidal volume (9.1\u2009\u00b1\u2009.6\u2009ml/kg WT vs. 10.6\u2009\u00b1\u2009.6\u2009ml/kg Mecp2ZFN\u0394/y) , minute ventilation (1151.6\u2009\u00b1\u200985.0\u2009ml/min/kg WT vs. 1073.7\u2009\u00b1\u2009101.1\u2009ml/min/kg Mecp2ZFN\u0394/y) , a relatively stable respiratory cycle (irregularity score\u2009=\u20095.0\u2009\u00b1\u20090.6\u2009WT vs. 5.1\u2009\u00b1\u20090.6 Mecp2ZFN\u0394/y) , and a similar number of spontaneous apneas , but of a shorter duration compared to controls  .Respiratory activity was measured in juvenile male (PND 21-28), adult male (PND 40+), and aged (18 month) female rats by whole-body plethysmography. We found that under control conditions (awake and breathing room air) juvenile"}
{"text": "In the mol\u00adecule, the hydroxyl substituent is bound intra\u00admolecularly to the aldehyde group at the ortho position.Wavy layers of mol\u00adecules are formed in the crystal structure of 5-methyl\u00adsalicyl\u00adaldehyde due to weak C\u2014H\u22efO inter\u00adactions between methyl groups and the aromatic ring system. Mol\u00adecules form columns in which the methyl groups are oriented in opposite directions layer-by-layer along cell axis  5-MSA; systematic name 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde), C8H8O2, was discovered to be a textbook example of the drastic structural changes caused by just a few weak C\u2014H\u22efO inter\u00adactions due to the additional methyl\u00adation of the aromatic ring compared to salicyl\u00adaldehyde SA. This weak inter\u00admolecular hydrogen bonding is observed between aromatic or methyl carbon donor atoms and hydroxyl or aldehyde acceptor oxygen atoms with d(D\u22efA) = 3.4801\u2005(18) and 3.499\u2005(11)\u2005\u00c5. The mol\u00adecule shows a distorted geometry of the aromatic ring with elongated bonds in the vicinity of substituted aldehyde and hydroxyl carbon atoms. The methyl hydrogen atoms are disordered over two sets of sites with occupancies of 0.69\u2005(2) and 0.31\u2005(2).The crystal structure of 5-methyl\u00adsalicyl\u00adaldehyde ( Its crystal structure is reported herein and compared to the unsubstituted form of salicyl\u00adaldehyde (SA)  apart from van der Waals inter\u00adactions. Three C\u2014H\u22efO inter\u00adactions are present between either aromatic or methyl C atoms and aldehyde or alcohol oxygen atoms: two close to 3.5\u2005\u00c5 with C10\u22efO8 = 3.499\u2005(2)\u2005\u00c5 and C5\u22efO8 = 3.4801\u2005(18)\u2005\u00c5 and corresponding C\u2014H\u22efO angles of 152 and 149.3\u2005(13)\u00b0, respectively. The third and shortest inter\u00adaction, has a C6\u22efO9 distance of 3.4053\u2005(18)\u2005\u00c5 and an angle of 138.7\u2005(12)\u00b0  = 3.7539\u2005(11) and 4.7456\u2005(13)\u2005\u00c5, respectively. This results in a deviation from the usually expected herringbone or completely planar arrangement of planar mol\u00adecules. Wavy layers of mol\u00adecules are formed instead, whereby the 5-MSA mol\u00adecules form columns in which the methyl groups are oriented in opposite directions layer-by-layer along the a axis  at positions H10A, H10B, H10C and 0.31\u2005(2) at positions H10D, H10E, H10F. They were included at idealized positions riding on the parent carbon atom, with isotropic displacement parameters iUso(H) = 1.5Ueq(CH3). Refinement of the corresponding site-occupation factors of the methyl-group hydrogen atoms was carried out using a free variable so that their sum is unity. All other hydrogen atoms were located individually in a difference-Fourier map and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017000238/lh5831sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017000238/lh5831Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017000238/lh5831Isup3.cmlSupporting information file. DOI: 1525796CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecule has an {Na2O6(\u03bc-O)2} core with two bridging carbonyl O atoms and two hydroxamate O atoms of two mono-deprotonated residues of N-hy\u00addroxy\u00adpicolinamide, while two neutral N-hy\u00addroxy\u00adpicolinamide mol\u00adecules are coordinated in a monodentate manner to each sodium ion via the carbonyl O atoms [the Na\u2014O distances range from 2.3044\u2005(2) to 2.3716\u2005(2)\u2005\u00c5]. The penta\u00adcoordinated sodium ion exhibits a distorted trigonal\u2013pyramidal coordination polyhedron. In the crystal, the coordination dimers are linked into chains along the c axis via N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds; the chains are linked into a two-dimensional framework parallel to (100) via weak C\u2014H\u22efO and \u03c0\u2013\u03c0 stacking inter\u00adactions.The title compound, [Na Coordination of the \u03bc-O carbonyl and hydroxamate O atoms of the same anion lead to the formation of five-membered chelate rings [Na1\u2014O6i = 2.3716\u2005(14)\u2005\u00c5 and O5i\u2014Na\u2014O6i = 70.26\u2005(5)\u00b0]. Two neutral N-hy\u00addroxy\u00adpicolinamide mol\u00adecules coordinate in a monodentate manner to each sodium ion via the carbonyl O atoms [Na1\u2014O1 = 2.3300\u2005(16)\u2005\u00c5 and Na1\u2014O3 = 2.3225\u2005(15)\u2005\u00c5]. As a result, each penta\u00adcoordinated sodium ion reveals a distorted trigonal\u2013pyramidal coordination polyhedron \u2005\u00c5 and the deviation of the O\u2014Na\u2014O angles from ideal values are up to 23.47\u2005(5)\u00b0. The Na\u2014O bond lengths are in the range 2.3044\u2005(14)\u20142.3716\u2005(14)\u2005\u00c5, which is common for penta\u00adcoordinated sodium cations 2 core is virtually planar and approaches a square [the O\u2014Na\u2014O angles are 86.43\u2005(5) and 93.57\u2005(5)\u00b0].The mol\u00adecular structure of title compound is shown in Fig.\u00a01N-hy\u00addroxy\u00adpicolinamide act as donors . The nearly coplanar pyridine rings of two neutral mol\u00adecules of N-hy\u00addroxy\u00adpicolinamide coordinating to the same sodium ion reveal intra\u00admolecular stacking inter\u00adactions in unusual \u2018head-to-head\u2019 manner .The deprotonated hydroxamate atom O6 acts as an acceptor of two hydrogen bonds Table\u00a01 in whichN-hy\u00addroxy\u00adpicolinamide residue adopts a strongly flattened conformation with a dihedral angle of only 0.6\u2005(2)\u00b0 between the hydroxamic group and the pyridine ring. At the same time, the corresponding dihedral angles in both neutral N-hy\u00addroxy\u00adpicolinamide mol\u00adecules are noticeably greater [17.5\u2005(2) and 8.9\u2005(2)\u00b0], indicating a deviation of the hydroxamic group from the plane of pyridine rings. The configuration about the hydroxamic C\u2014N bond is Z and that about the C\u2014C bond between the pyridine and hydroxamic groups is E for both the neutral and deprotonated hydroxamates. Intra\u00admolecular N\u2014H\u22efN attractive contacts between the hydroxamate group and the nitro\u00adgen atom of pyridine ring [2.25\u2005(2)\u20132.35\u2005(3)\u2005\u00c5] are present in both the neutral and deprotonated N-hy\u00addroxy\u00adpicolinamide mol\u00adecules  and N1\u2014H1\u22efN6 hydrogen bonds supported by a pair of weak non-classical C17\u2014H17\u22efN2 hydrogen bonds  hydrogen bond and \u03c0\u2013\u03c0 stacking between the N4/C7\u2013C11 pyridine ring and the deprotonated O5/C18/N5/O6 hydroxamic group . Inter\u00admolecular \u03c0\u2013\u03c0 stacking between the same deprotonated hydroxamic group and the N2/C1\u2013C5 pyridine ring  links the frameworks into a three-dimensional structure.In the crystal Fig.\u00a02, the dims Table\u00a01. The chaet al., 2016N-hy\u00addroxy\u00adpicolinamide revealed the crystal structures of over 20 compounds, mostly belonging to the metallacrown (MC) family. In particular, heterometallic copper(II) 15-metallacrown-5 complexes with encapsulated GdIII and EuIII ions ,picHA-4](OTf)1.25(OH)0.75 ,picHA-4]2(OH)3(py)2 ,picHA-4]2\u00b7\u00b7(pyridine)8\u00b7(triflate)3 2(OAc)4(DMF)2 collapsed metallacrown complex has been struct\u00adurally characterized  with sodium hydrogen carbonate . Colorless crystals suitable for X-ray diffraction were obtained from the resulting aqueous solution by slow evaporation at ambient temperature within 48\u2005h (yield 78%).The title compound was obtained by the reaction of Uiso = 1.2Ueq(C), and H atoms of the N\u2014H and O\u2014H groups were refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016019095/xu5895sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016019095/xu5895Isup2.hklStructure factors: contains datablock(s) I. DOI: 1520114CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The HCO3\u2212 transport across the luminal membrane has been proposed to be mediated by SLC26A Cl\u2212\u2013HCO3\u2212 exchangers. To examine the electrophysiological properties of Cl\u2212\u2013HCO3\u2212 exchangers, we directly measured HCO3\u2212 conductance in the luminal membrane of the interlobular pancreatic duct cells from guinea pigs using an inside-out patch-clamp technique. Intracellular HCO3\u2212 increased the HCO3\u2212 conductance with a half-maximal effective concentration value of approximately 30\u00a0mM. The selectivity sequence based on permeability ratios was SCN\u2212 (1.4)\u2009>\u2009Cl\u2212 (1.2)\u2009=\u2009gluconate (1.1)\u2009=\u2009I\u2212 (1.1)\u2009=\u2009HCO3\u2212 (1.0)\u2009>\u2009methanesulfonate (0.6). The sequence of the relative conductance was HCO3\u2212 (1.0)\u2009>\u2009SCN\u2212 (0.7)\u2009=\u2009I\u2212 (0.7)\u2009>\u2009Cl\u2212 (0.5)\u2009=\u2009gluconate (0.4)\u2009>\u2009methanesulfonate (0.2). The current dependent on intracellular HCO3\u2212 was reduced by replacement of extracellular Cl\u2212 with gluconate or by H2DIDS, an inhibitor of Cl\u2212\u2013HCO3\u2212 exchangers. RT-PCR analysis revealed that the interlobular and main ducts expressed all SLC26A family members except Slc26a5 and Slc26a8. SLC26A1, SLC26A4, SLC26A6, and SLC26A10 were found to be localized to the luminal membrane of the guinea pig pancreatic duct by immunohistochemistry. These results demonstrate that these SLC26A Cl\u2212\u2013HCO3\u2212 exchangers may mediate the electrogenic HCO3\u2212 transport through the luminal membrane and may be involved in pancreatic secretion in guinea pig ducts.The pancreatic duct epithelium secretes the HCO However, ducts secrete a HCO3\u2212-rich fluid, which is dependent on the presence of CO2/HCO3\u2212-buffer, and that neutralizes acid chyme in the duodenum [3\u2212 transport involves Cl\u2212\u2013HCO3\u2212 exchangers that operate in parallel with cAMP-activated Cl\u2212 channels [cystic fibrosis transmembrane conductance regulator (CFTR)] and Ca2+-activated Cl\u2212 channels, such as TMEM16A/ANO1, on the luminal membranes of duct cells -5-thiazolidinylidene]methyl]benzoic acid  and 2-methyl-8-(phenylmethoxy)imidazopyridine-3-acetonitrile  were dissolved in DMSO at a 1000-fold concentration for application. The current was recorded in the inside-out configuration using the EPC 800 patch-clamp amplifier (HEKA). The amplifier was driven by Clampex 9 (Axon) in order to allow the delivery of a voltage-ramp protocol with concomitant digitization of the current. The membrane potential was generally held at 0\u00a0mV, and the command voltage was varied from \u2212\u200980 to +\u200980\u00a0mV over a duration of 800\u00a0ms every 10\u00a0s.Standard patch-clamp techniques were used. Patch pipettes, pulled from capillaries of hard borosilicate glass , had a resistance of 5\u20137\u00a0M\u03a9 when filled with a standard Taq DNA Polymerase (Promega). The amplification parameters used were as follows: 1 cycle at 50\u00a0\u00b0C for 30\u00a0min and 1 cycle at 95\u00a0\u00b0C for 15\u00a0min, followed by 40\u00a0cycles at 94\u00a0\u00b0C for 30\u00a0s, 57\u00a0\u00b0C for 30\u00a0s, 72\u00a0\u00b0C for 30\u00a0s, and 1 cycle at 72\u00a0\u00b0C for 10\u00a0min. The transcripts were subsequently verified by agarose gel electrophoresis.RNA was extracted from the interlobular (outside diameter of 50\u2013150\u00a0\u03bcm) and main ducts (outside diameter of around 500\u00a0\u03bcm) from three independent guinea pigs using the RNeasy Plus Micro kit with DNase I (Qiagen). RT-PCR analysis was performed using the OneStep RT-PCR kit (Qiagen) with primers designed to recognize different types of transporters (Table n\u2009=\u20093) in accordance with protocols approved by the Animal Experimentation Committee, Kansai Medical University. The guinea pigs were anesthetized with isoflurane and a mixture of medetomidine (0.5\u00a0mg/kg body weight), midazolam (5.0\u00a0mg/kg b.w.), and butorphanol (2.5\u00a0mg/kg b.w.), and perfused transcardially with 4% paraformaldehyde. The pancreas was fixed with 4% paraformaldehyde in PBS for 24\u00a0h, embedded in paraffin, and sectioned. Detailed methods for immunohistochemistry were described previously [Immunolocalization was performed on the guinea pig pancreas. The pancreas was obtained from female Hartley guinea pigs  on ice for 30\u00a0min, and then centrifuged. The pellet was solubilized in lysis buffer containing urea (9\u00a0M), Triton X-100 2%), dithiothreitol (1%), and lithium dodecyl sulfate (2%). The samples (30\u00a0\u03bcg/lane protein) were fractionated on SDS polyacrylamide gel (7.5%), electroblotted to PVDF membranes (Merck Millipore), blocked with skim milk (1%), and reacted with anti-SLC26A4, anti-SLC26A6, or anti-SLC26A10 antibodies  or Student\u2019s paired I\u2013V) relationships in the presence of intracellular HCO3\u2212 at different concentrations . As we used the standard NMDG-Cl pipette solution and the bathing solution containing KHCO3, the inward current was due to HCO3\u2212 efflux through the luminal membrane. The inward conductance determined from the linear section of the I\u2013V relationships (from \u2212\u200980 to \u2212\u200960\u00a0mV) increased with intracellular HCO3\u2212 concentration  value for the effects of HCO3\u2212 and Hill coefficient were 31.5\u2009\u00b1\u20095.1\u00a0mM and 3.5\u2009\u00b1\u20090.4 (n\u2009=\u20095), respectively. We also measured inward HCO3\u2212 currents in the bathing solution containing 130\u00a0mM NaHCO3. The inward conductance increased to 2.04\u2009\u00b1\u20090.95\u00a0nS in NaHCO3 from 0.34\u2009\u00b1\u20090.08\u00a0nS in NaCl . Thus, there was a minor contribution of K+ conductance under unstimulated conditions.We recorded macroscopic currents from excised inside-out patches from the luminal membrane of the interlobular pancreatic duct cells of guinea pigs under unstimulated conditions. Figure 3\u2212 in the intracellular bathing solution with other monovalent anions. Figure I\u2013V relations recorded in the inside-out configuration with the standard NMDG-Cl pipette solution. In experiments where HCO3\u2212 in the bath was replaced with Cl\u2212 or gluconate (glc\u2212), the reversal potential did not change, but inward conductance significantly decreased from 1.30\u2009\u00b1\u20090.09\u00a0nS in HCO3\u2212 to 0.64\u2009\u00b1\u20090.13\u00a0nS in Cl\u2212  and from 1.69\u2009\u00b1\u20090.08\u00a0nS in HCO3\u2212 to 0.72\u2009\u00b1\u20090.14\u00a0nS in glc\u2212 . Replacement of HCO3\u2212 with methanesulfonate (MES\u2212) shifted the reversal potential in a negative direction, indicating it was less permeable than HCO3\u2212, and the inward conductance significantly decreased from 2.56\u2009\u00b1\u20090.73\u00a0nS in HCO3\u2212 to 0.73\u2009\u00b1\u20090.36\u00a0nS in MES\u2212 . Replacement of HCO3\u2212 with thiocyanate (SCN\u2212) slightly shifted the reversal potential in a positive direction, but the inward conductance had little change . Finally, replacement of HCO3\u2212 with iodide (I\u2212) did not cause a marked difference in the reversal potential or the inward conductance . We calculated the permeability ratio (PX/PHCO3) from the shift in the reversal potential (\u0394Vrev) when anion X is substituted for internal HCO3\u2212 [\u2212 (1.41\u2009\u00b1\u20090.15)\u2009>\u2009Cl\u2212 (1.18\u2009\u00b1\u20090.14)\u2009=\u2009glc\u2212 (1.07\u2009\u00b1\u20090.03)\u2009=\u2009I\u2212 (1.06\u2009\u00b1\u20090.06)\u2009=\u2009HCO3\u2212 (1.00)\u2009>\u2009MES\u2212 (0.65\u2009\u00b1\u20090.11) (n\u2009=\u20095\u20136). The sequence of the relative inward conductance determined from \u2212\u200980 to \u2212\u200960\u00a0mV was HCO3\u2212 (1.00)\u2009>\u2009SCN\u2212 (0.69\u2009\u00b1\u20090.10)\u2009=\u2009I\u2212 (0.66\u2009\u00b1\u20090.09)\u2009>\u2009Cl\u2212 (0.48\u2009\u00b1\u20090.08)\u2009=\u2009glc\u2212 (0.43\u2009\u00b1\u20090.09)\u2009>\u2009MES\u2212 (0.26\u2009\u00b1\u20090.06) (n\u2009=\u20095\u20136).Ion selectivity of the bicarbonate conductance was examined by replacing 130\u00a0mM HCO\u2212\u2013HCO3\u2212 exchangers on the apical membrane of interlobular pancreatic ducts of the guinea pig, Ishiguro and colleagues replaced Cl\u2212 with gluconate in the lumen [\u2212. With the control intracellular solution,Erev was \u2212\u200946.6\u2009\u00b1\u20094.5\u00a0mV with a standard NMDG-Cl pipette solution  and \u2212\u200963.6\u2009\u00b1\u20093.9\u00a0mV with gluconate-rich pipette solution , demonstrating a significant difference (ANOVA). We also compared the inward HCO3\u2212 conductance with gluconate-rich and standard NMDG-Cl pipette solutions  than with standard NMDG-Cl pipette solutions (1.30\u2009\u00b1\u20090.09\u00a0nS) . Additionally, as described in the previous section, the inward conductance significantly decreased when HCO3\u2212 in the bath was replaced with Cl\u2212, indicating that there was a minor contribution from Cl\u2212-dependent current  intracellularly while recording macroscopic currents from excised inside-out patches with the control bicarbonate internal and the standard NMDG-Cl pipette solutions. To exclude the possibility of the contamination of CFTR Cl\u2212 conductance, we included 20\u00a0\u03bcM CFTRinh-172, an inhibitor of CFTR Cl\u2212 channels, in the pipette solution. H2DIDS applied intracellularly significantly decreased inward HCO3\u2212 conductance from 1.57\u2009\u00b1\u20090.55 to 0.86\u2009\u00b1\u20090.37\u00a0nS . We also tested 30\u00a0\u03bcM Sch28080, a H+\u2013K+-pump inhibitor, but did not observe any inhibitory effects on the inward HCO3\u2212 conductance . These results further support that the HCO3\u2212 conductance occurs through Cl\u2212\u2013HCO3\u2212 exchangers.Previous studies reported that Clstilbene , 43. For2+ signaling pathways play a role in fluid secretion. As CFTR Cl\u2212 channels were regulated by intracellular cAMP [n\u2009=\u200913). The addition of 1\u00a0mM cAMP further increased the inward conductance to 14.8\u2009\u00b1\u20095.57\u00a0nS (n\u2009=\u20094). cAMP also activated the marked outward conductance, which was attributed to Cl\u2212 influx, most likely through CFTR Cl\u2212 channels. Therefore, we tested the effects of intracellular ATP-Mg and cAMP with the pipette solution including CFTRinh-172 at 20\u00a0\u03bcM. In the presence of CFTRinh-172, application of intracellular 2\u00a0mM ATP-Mg and 1\u00a0mM cAMP had little effect on the conductance in either direction . These results indicate that intracellular ATP and cAMP may not directly regulate Cl\u2212\u2013HCO3\u2212 exchangers, but instead regulate CFTR Cl\u2212 channels on the luminal membrane of duct cells. Additionally, 1\u00a0\u03bcM free Ca2+ added to the intracellular solution did not affect the inward HCO3\u2212 conductance , suggesting that intracellular Ca2+ does not regulate Cl\u2212\u2013HCO3\u2212 exchangers directly.In pancreatic duct cells, cAMP and Calar cAMP , 8, 29 alar cAMP , we test\u2212\u2013HCO3\u2212 exchangers [Slc26a3 and Slc26a6 [n\u2009=\u20093 animals) and main ducts , along with GAPDH and a duct marker of carbonic anhydrase II (CA2). We also screened all primer sets from the total RNA of the kidney as a positive control . The molecular mass values corresponded to those of human SLC26A proteins (~\u2009100\u00a0kDa), which were N-glycosylated, expressed in HEK-293 cells [We next performed western blot analysis to examine the expression of SLC26A protein in the guinea pig pancreatic ducts. We detected SLC26A6 (~\u2009107\u00a0kDa), SLC26A1 ~\u200978\u00a0kDa), SLC26A4 (~\u2009136\u00a0kDa), and SLC26A10 (~\u2009108\u00a0kDa) in the lysates of the isolated ducts  of 160 and 80\u00a0\u03bcM, respectively [\u2212\u2013HCO3\u2212 exchangers from not only the outside but also from the inside of the cell membrane.We found that Hane Fig. . A previectively . It is l3\u2212 conductance through the luminal membrane is mediated by Cl\u2212\u2013HCO3\u2212 exchangers under physiological HCO3\u2212 concentrations in pancreatic duct cells. Our findings suggest that SLC26A1, SLC26A4, SLC26A6, and SLC26A10 may be involved in the HCO3\u2212 transport through the luminal membrane. The SLC26A family may also play a role in pH homeostasis in the pancreatic lumen and duct cells. The direct measurement of the HCO3\u2212 current from the interlobular duct and its functional characterization helps to propose a useful model for HCO3\u2212 secretion from the pancreatic duct epithelia (Fig.\u00a0In conclusion, we used the patch-clamp technique in the inside-out configuration and demonstrated that the HCOlia Fig.\u00a0.Fig. 9Mo"}
{"text": "II cations are bridged by S atoms from the N,N-di\u00adallyl\u00adldi\u00adthio\u00adcarbamate ligands.The characteristic feature of this cadmium(II) complex is the formation of a dimeric bridged structure where the two Cd 2(C7H10NS2)4], is a neutral dinuclear cadmium(II) complex bearing four bis N,N-di\u00adallyl\u00addi\u00adthio\u00adcarbamate ligands coordinating to two CdII cations. In each of the monomeric subunits, there are four S atoms of two di\u00adthio\u00adcarbamate ligands  that coordinate to one CdII atom in a bidentate mode. The dimers are located over an inversion centre bridged by two additional bridging Cd\u2014S bonds [2.6021\u2005(3)\u2005\u00c5], leading to a substantial distortion of the geometry of the monomeric subunit from the expected square-planar geometry. The five-coordinate environment around each of the CdII ions in the dimer is best described as substanti\u00adally tetra\u00adgonally distorted square pyramidal. The di\u00adthio\u00adcarbamate groups are themselves planar and are also coplanar with the CdII ions. The negative charge on these groups is delocalized by resonance across the S atoms bound to the CdII cation. This delocalization of the \u03c0 electrons in the di\u00adthio\u00adcarbamate groups also extends to the C\u2014N bonds as they reveal significant double bond character [C\u2014N = 1.3213\u2005(16) and 1.3333\u2005(15)\u2005\u00c5].The title compound, [Cd This common feature has been ascribed to the effect of aggregated species, which they adopt in the solid state, resulting from equal numbers of \u03bc2-tridentate and bidentate (chelating) ligands cadmium compounds have the advantage of having stability similar to that of the zinc complexes, but more favourable stability when compared to the mercury complexes. Cadmium di\u00adthio\u00adcarbamate complexes have been widely used as single-source precursors for CdS nanoparticles and thin films, which have application as non-linear optical materials  to 2.8016\u2005(3)\u2005\u00c5 and to a fifth S atom at a distance of 2.6021\u2005(3)\u2005\u00c5; these distances are similar to other complexes found to have been published previously (see Section 4: Database survey). A full geometry check carried out with the Mogul Geometry Check tool  \u2013x\u00a0+\u00a02, \u2013y, \u2013z\u00a0+\u00a01]. This means that each bridging S atom simultaneously occupies an equatorial coordination site on one CdII ion and an apical site on the other CdII ion to form an edge-shared tetra\u00adgonal\u2013pyramidal geometry. The CdII ion deviates from the S11\u2014S12\u2014S22\u2014S21 mean plane by 0.704016\u2005(17)\u2005\u00c5 towards S12i. The bridging network Cd1\u2014S12\u2014Cd1i\u2014S12i is completely planar since it lies over the inversion centre with a Cd1\u22efCd1i separation distance of 3.60987\u2005(8)\u2005\u00c5 and S12\u2014Cd1\u2014S12i and Cd1\u2014S12\u2014Cd1i angles of 96.257\u2005(9) and 83.743\u2005(9)\u00b0, respectively. There is substantial distortion of the geometry of the monomeric subunit from the expected square-planar geometry. Deviations from the standard 90\u00b0 angles are evident in the angles of S11\u2014Cd1\u2014S21 [108.203\u2005(11)\u00b0]; S22\u2014Cd1\u2014S21 [70.264\u2005(10)\u00b0]; S22\u2014Cd1\u2014S12 [96.950\u2005(10)\u00b0] and S11\u2014Cd1\u2014S12 [67.486\u2005(10)\u00b0]. Deviations in the standard 180\u00b0 angles are evident in the angles of S11\u2014Cd1\u2014S22 [143.705\u2005(13)\u00b0] and S21\u2014Cd1\u2014S12 [152.651\u2005(11)\u00b0]. The Cd1\u2014S12\u2014Cd1i\u2014S12i and S11\u2014S12\u2014S22\u2014S21 mean planes form a dihedral (twist) angle of 84.6228\u2005(18)\u00b0. The di\u00adthio\u00adcarbamate groups are planar and each group of the monomeric subunit is coplanar with the CdII ion (r.m.s. deviation is 0.010\u2005\u00c5). The mean plane consisting of atoms Cd1, S11, N1, C11, S12 and the mean plane consisting of atoms Cd1, S22, N2, C21, S21 have a plane-normal-to-plane-normal angle of 37.0291\u2005(10)\u00b0; a centroid-to-centroid distance of 4.45354\u2005(8)\u2005\u00c5; a plane-to-plane shift of 4.22298\u2005(8)\u2005\u00c5 and a plane-to-plane torsion (twist) angle of 8.0304\u2005(12)\u00b0.The coordination environment of the Cdry Fig.\u00a01. The CdIII cation. On the opposite side of the CdII ion, both S\u2014C bonds have approximately the same length, where S21\u2014C21 and S22\u2014C21 bond lengths are 1.7224\u2005(12) and 1.7263\u2005(12)\u2005\u00c5, respectively, suggesting that the double bond of the di\u00adthio\u00adcarbamate is spread over the S\u2014C\u2014S bond via resonance. A possible explanation for this may be because of the fact that atom S12 serves as the bridging S atom in the complex. Also, the N1\u2014C11 and N2\u2014C21 distances  are shorter compared to the other N\u2014C distances indicating considerable double-bond character. The vinyl substituents are also planar and are at an angle of 91.6049\u2005(14)\u00b0 from the di\u00adthio\u00adcarbamate plane and at an angle of 150.9196\u2005(6)\u00b0 from the vinyl group directly opposite from it. This scenario is comparable with the other structures surveyed in the literature (see Section 4: Database survey). All highlighted and discussed geometrical parameters describing the coordination environment are given in Table\u00a01The S12\u2014C11 bond length [1.7532\u2005(13)\u2005\u00c5] is longer than the adjacent S11\u2014C11 bond length [1.7162\u2005(13)\u2005\u00c5] suggesting that this bond has more double bond character in the di\u00adthio\u00adcarbamate portion that coordinates to the CdPThe space group of the crystal is et al., 2016N,N-diallyl side chain, the side-chains substituents are di-n-propyl [CSD refodes BEHNOR   in ethanol (10\u2005ml) was added to a solution of sodium N,N-diallyl di\u00adthio\u00adcarbamate  in ethanol (10\u2005ml), and the resulting suspension was stirred for 45\u2005min at room temperature. This solution was then filtered, and rinsed several times with distilled water  has been published previously  = 1.2 Ueq(C) for methyl\u00adene groups and C\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.2 Ueq(C) for all vinyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017011616/zl2710sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017011616/zl2710Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011616/zl2710Isup3.molSupporting information file. DOI: 899314CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2032-amino\u00adpyridine-2-carboximidamide (C6H8N4), 1, and N\u2032-{[1-(pyridin-2-yl)ethyl\u00adidene]amino}\u00adpyridine-2-carboximidamide (C13H13N5), 2, mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN hydrogen-bonding inter\u00adactions, forming a two-dimensional network in 1 and a chain in 2.In the crystal structures of  N\u2032-amino\u00adpyridine-2-carboximidamide (C6H8N4), 1, and N\u2032-{[1-(pyridin-2-yl)ethyl\u00adidene]amino}\u00adpyridine-2-carboximidamide (C13H13N5), 2, are described. The non-H atoms in compound 1 are nearly planar (r.m.s. deviation from planarity = 0.0108\u2005\u00c5), while 2 is twisted about the central N\u2014N bond by 17.8\u2005(2)\u00b0. Both mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN hydrogen-bonding inter\u00adactions; 1 forms a two-dimensional hydrogen-bonding network and for 2 the network is a one-dimensional chain. The bond lengths of these mol\u00adecules are similar to those in other literature reports of azine and di\u00adimine systems.The crystal structures of  RC(=NH)NHNH2 is accomplished by the action of hydrazine on the corresponding thio\u00adamide, imido ether or nitrile  of the heterocyclic ligand  and 0.24\u2005(6)\u2005\u00c5 out of the mean plane of non-hydrogen atoms. For H4A and H4B, the deviation is even greater at 0.37\u2005(5) and 0.54\u2005(5)\u2005\u00c5 from the mean plane. Rotation of the non-planar NH2 group, particularly for N4, facilitates hydrogen bonding to other mol\u00adecules. The N\u2014N single bond length in 1 [1.424\u2005(5)\u2005\u00c5] is slightly shorter than that in the free hydrazine (1.449\u2005\u00c5).The mol\u00adecular structure of 2 is shown in Fig.\u00a02The mol\u00adecular structure of E,E conformation, suggesting conjugation throughout the \u03c0 systems. The C6\u2014N2\u2014N3 and C8\u2014N3\u2014N2 angles of 115.5\u2005(2)\u00b0 and 110.57\u2005(19)\u00b0, respectively are significantly below the ideal sp2 value of 120\u00b0, a consequence of the repulsion between the nitro\u00adgen lone pair and the adjacent bonds. The C6\u2014N2\u2014N3\u2014C8 torsion angle is \u2212162.2\u2005(2)\u00b0. This large deviation from planarity has two consequences. First, there is a loss of conjugation between the imine bonds across the azine bond, reflected in the shorter imine bond length. The torsion also leads to a shorter N2\u2014N3 bond length [1.408\u2005(3)\u2005\u00c5] compared to that observed for 1 [1.424\u2005(5)\u2005\u00c5]. Finally, a short intra\u00admolecular contact between N3i and H4B, 2.42\u2005(3)\u2005\u00c5, may add a favorable electrostatic contribution to the stability of this conformation. Notably, there is minimal change in the bond lengths within the ligands when a first row transition metal ion is bound. When the ligand chelates to a metal ion through both N3 and N5, only the bond length C8\u2014N4 changes significantly, becoming shorter on binding.The bond lengths indicate that within the central chain of the mol\u00adecule, the C6\u2014N2 and C8\u2014N3 linkages have largely double-bond character. The azine linkages are in the 1 in each unit cell and these are related by the screw axis. Curiously, N1 does not act as a hydrogen-bond acceptor. H2A is also not involved with the formation of any (short) classical hydrogen bonds. H2B forms a hydrogen bond to N4i . This is augmented by the longer hydrogen bond N4\u2014H4B\u22efN4i. N4\u2014H4A forms a hydrogen bond to N3ii . These three sets of hydrogen bonds  1/2 \u2013 x, 1 \u2013 y, z \u2013 1/2] is present and this knits the mol\u00adecules of 2 together to form hydrogen-bonded chains along the [001] direction, as shown in Fig.\u00a04The classical hydrogen bonding Table\u00a02 in 2 is N\u2032-aminopyridine-2-carboximidamide and related mol\u00adecules, see Case et al. (1965N\u2032-{[1-(pyridin-2-yl)ethylidene]amino}pyridine-2-carboximidamide and analogues, see Gokhale et al. ethyl\u00adidene]amino}\u00adpyridine-2-carboximid\u00adamide is depicted in Fig.\u00a05The synthesis of N\u2032-Amino\u00adpyridine-2-carboximidamide (1) was prepared by an analogy of the procedure published by Case (1965N\u2032-{[1-(Pyridin-2-yl)ethyl\u00adidene]amino}\u00adpyridine-2-carboximid\u00adamide (2) was synthesized by an analogy of the procedure published by Gokhale et al.  to 0.99\u2005(3)\u2005\u00c5. The other hydrogen atoms attached to formally single-bonded nitro\u00adgen atoms were freely refined subject to sensible distance and angle restraints. The N\u2014H distances lie in the range 0.94\u2005(3)-0.95\u2005(3)\u2005\u00c5.For compound 2, hydrogen atoms were placed using a riding model .For compound 10.1107/S2056989017008416/nk2236sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989017008416/nk22361sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989017008416/nk22361sup4.cdxSupporting information file. DOI: 10.1107/S2056989017008416/nk22362sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989017008416/nk22362sup5.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017008416/nk22361sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017008416/nk22362sup7.cmlSupporting information file. DOI: 1554569, 1554568CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Molecules containing multiple bonds between atoms\u2014most often in the form of olefins\u2014are ubiquitous in nature, commerce, and science, and as such have a huge impact on everyday life. Given their prominence, over the last few decades, frequent attempts have been made to perturb the structure and reactivity of multiply-bound species through bending and twisting. However, only modest success has been achieved in the quest to completely twist double bonds in order to homolytically cleave the associated \u03c0 bond. Here, we present the isolation of double-bond-containing species based on boron, as well as their fully twisted diradical congeners, by the incorporation of attached groups with different electronic properties. The compounds comprise a structurally authenticated set of diamagnetic multiply-bound and diradical singly-bound congeners of the same class of compound. Attempts to bend and twist multiple bonds in order to alter their reactivities have thus far been met with only modest success. Here, Braunschweig and colleagues isolate double-bond-containing boron-based species and their 90\u00b0-twisted diradical analogs, thanks to their stabilization with Lewis basic units. Having one degree of electronic unsaturation more than relatively inert alkanes, olefins are the simplest and most earth-abundant hydrocarbons that show reactivity under ambient conditions, leading to their widespread industrial use as well as their implication in questions related to the origins of life4. Olefins are molecules that contain a double bond between two carbon atoms consisting of one bond of \u03c3 symmetry and one of \u03c0 symmetry  olefin by 90\u00b0 would completely break its \u03c0 bond, presumably leading to a triplet diradical  due to their necessarily twisted geometry.The \u03c0 orbital of olefins requires the parallel alignment of two carbon cal Fig.\u00a0, right a18. Beyond carbon\u2013carbon double bonds, sterically hindered heavier olefin analogs such as disilenes (of the form R2Si\u2009=\u2009SiR2) also withstand significant twisting of the double bond (up to 55\u00b0)23. In a key 2015 study, Sekiguchi and coworkers reported that one of these disilenes (Si2(SiMetBu2)4) was able to thermally populate a triplet state by twisting of the  Si=Si bond above 77\u2009\u00b0C. This diradical compound was characterized by electron paramagnetic resonance (EPR) spectroscopy and calculated to have an average SiSiSiSi dihedral angle of 75.2\u00b0; however, its structure could not be authenticated experimentally22. This work remains the forefront of chemists\u2019 efforts to isolate the diradical products of twisting element\u2013element double bonds.It is thus unsurprising that efforts to isolate \u201ctwisted olefin\u201d compounds have resulted in only partial success: isolation of diamagnetic, incompletely twisted structures 27, as well as their 90\u00b0-twisted diradical congeners 2 imidazol-2-ylidene) led to new 11B NMR signals to higher field of that of the triply-bound precursor (\u03b4B 39)24, signifying the formation of three new products, 1a\u2013c  or purple  solids with 11B NMR signals  in a similar range to those of known doubly NHC-stabilized diborenes (\u03b4B 18\u201328)27, but significantly more downfield than those of two previously observed diboratellurirenium cations (cyclo-[Te(R)B(NHC)B(NHC)]+) prepared by the analogous reactions of B2(IDip)2 with diphenylditelluride (\u03b4B 0)35. Single-crystal X-ray diffraction confirmed the trans-diborene nature of 1a\u2013c, all three molecules displaying effectively planar LRB=BRL double bond units \u2009\u00c5; 1b: avg. 1.568(6)\u2009\u00c5; 1c: avg. 1.565(5)\u2009\u00c5).Simple room-temperature (RT) addition of either equal amounts or slight excesses of dibutyldisulfide, diphenyldisulfide, or diphenyldiselenide to solutions of the triple-bond-containing diboryne species Ba\u2013c Fig.\u00a0, top. Afits Fig.\u00a0, top, an2(IDip)2 (B2(CAAC)2; CAAC\u2009=\u20091--3,3,5,5-tetramethylpyrrolidin-2-ylidene)36. However, to our surprise, all three reaction mixtures became very dark, and all attempts to obtain NMR spectra from the mixtures gave either silent spectra or exceptionally broad signals well outside the normal diamagnetic chemical shift ranges. Solvent extraction and recrystallization provided the black solids 2a\u2013c \u00b0; 2b: 100.9(1)\u00b0; 2c: 99.7(2)\u00b0), and long, single B\u2013B bonds (2a: 1.728(2)\u2009\u00c5; 2b: 1.713(2)\u2009\u00c5; 2c: 1.700(4)\u2009\u00c5). On either side of the midpoint of the molecules, the N-C-B-S/Se units are near-planar, with relatively small N-C-B-S/Se torsion angles (2a: 1.7(2)\u00b0, 14.6(2)\u00b0; 2b: 17.4(2)\u00b0, 1.5(2)\u00b0; 2c: 18.7(3)\u00b0, 0.1(4)\u00b0) suggesting significant \u03c0-electron delocalization over this portion of the molecule. The B-S/Se distances of 2a\u2013c (d(B\u2013S): 1.84\u20131.86\u2009\u00c5; d(B\u2013Se): 1.99\u20132.00\u2009\u00c5) were found to be slightly shorter than those of 1a\u2013c (d(B\u2013S): 1.88\u20131.92\u2009\u00c5; d(B\u2013Se): 2.01\u20132.06\u2009\u00c5), and the B\u2013C distances of 2a\u2013c (1.53\u20131.55\u2009\u00c5) are likewise shorter than those of 1a\u2013c (1.57\u20131.62\u2009\u00c5).We also attempted the analogous addition of dibutyldisulfide, diphenyldisulfide, or diphenyldiselenide to solutions of a more cumulenic CAAC analog of Ba\u2013c Fig.\u00a0, bottom.2a\u2013c, the apparent absence of B\u2013B multiple bonding, and the inability to procure NMR data of the compounds suggested that they may be captodatively stabilized30 triplet diradicals, each with two push\u2013pull systems involving the \u03c0-donating S/Se atom and the \u03c0-accepting CAAC carbene carbon atom \u2013B(\u2022)RL; Fig.\u00a02a\u2013c are reminiscent of our related neutral monoradical species [DurB(Cl)(CAAC)]\u2022 reported in 201431. In order to confirm the diradical nature of 2a\u2013c, we performed EPR spectroscopy on 2a\u2013c in frozen 2-methyltetrahydrofuran glass. While we observed an intense half-field transition for 2a and 2b  due to dipole interaction, indicating that the spin system in question is a triplet state. Analysis of the spectra yields estimates of the ZFS parameters , the axial parts of which correspond to interspin distances of 4.5 and 4.4\u2009\u00c5 (assuming point dipole approximation), respectively. These distances are significantly longer than the ca. 1.70\u20131.73\u2009\u00c5 boron\u2013boron distances found by X-ray crystallography, and match better the distance between the two CAAC carbene carbon atoms . Thus, the two unpaired electrons must be significantly delocalized into the substituents, most likely toward the carbene carbon atoms, which is in line with that expected by the captodative effect of the \u03c0-donor nitrogen and \u03c0-acceptor boron atoms.The significantly greater delocalization in the C-B-S/Se portion of  2b Fig.\u00a0\u201316, only2a, temperature-dependent magnetic measurements were performed on a solid sample  lower than the singlet state. The exchange coupling determined from solid-state SQUID measurements is also reflected to some degree in the temperature-dependence of the signal intensities observed in the solution-state EPR spectra of 2a  and single B\u2013B bond character in 2a\u2013c . Figure\u00a01a\u2013c and diradicals 2a\u2013c. The former, as exemplified by 1a, possess highest occupied molecular orbitals , with lower but roughly equivalent spin density on the B (0.18 and 0.23 e) and N (0.21 and 0.22 e) atoms.Density functional theory (DFT) calculations for diamagnetic diborenes  2a Fig.\u00a0 show tha2a. The overestimation may result from the need for multi-reference approaches38 to describe the singlet and triplet states on equal footing. Because 2a is too large for such costly approaches, we investigated the error of the DFT approaches for a smaller model system , the values obtained with DFT range from \u20134 to \u201328\u2009kcal\u2009mol\u20131. The MN12-L/6\u2013311G approach used to estimate the S\u2013T gap of the full system 2a overestimates the stability of the triplet state by about 6\u20137\u2009kcal\u2009mol\u20131. Transferring this error to the predictions of the MN12L41/6\u2013311G43 approach for the full system 2a , a near-zero S\u2013T gap results, which is in line with the measured value.While DFT computations and experiment agree in terms of geometry and the energetic order of the singlet and triplet states, the DFT computations considerably overestimate the size of the singlet\u2013triplet gap (S\u2013T gap) of compound 2a\u2013c also distinguishes these diradicals from diborenes 1a\u2013c , as previously observed for related diborenes44. In contrast, diradicals 2a\u2013c show less-facile oxidation events, with additional reduction waves, in line with the presence of the more \u03c0-accepting CAAC ligands. It should also be noted that variable-temperature NMR experiments suggest that the diamagnetic diborenes 1 and the diradical species 2 do not convert to their alternative conformations upon heating to 80\u2009\u00b0C.The electrochemical behavior of 1a\u2013c and their twisted congeners 2a\u2013c marks the first isolation and structural authentication of diamagnetic, multiply-bound molecules and their diradical, single-bond congeners, products of formal homolysis of the central multiple bond. Crystallographic, EPR spectroscopic, magnetic and theoretical studies confirm that 2a\u2013c are diradical species. Spectroscopic and computational studies also confirm the substantial energy differences between the singlet and triplet states of the molecules, with the singlet states being favored in 1a\u2013c and the triplet states in 2a\u2013c.The synthesis of diborenes 1H: 500.13\u2009MHz, 11B: 160.46\u2009MHz, 13C{1H}: 125.76\u2009MHz) at RT. Chemical shifts (\u03b4) are given in ppm and internally referenced to the carbon nuclei (13C{1H}) or residual protons (1H) of the solvent. 11B NMR spectra were referenced to the external standard [BF3\u00b7OEt2]. Microanalyses  were performed on an Elementar vario MICRO cube elemental analyzer. Melting points were determined with a Mettler Toledo 823e DSC in sealed ampules with a ramp rate of 10\u2009\u00b0C\u2009min\u22121. UV/vis absorption spectra 2(SBu)2, (1a): Dibutyldisulfide  was added dropwise to a stirred solution of B2(IDip)2  in pentane (10\u2009mL). The mixture was stirred for 18\u2009h at RT and all volatiles were removed in vacuo. The dark green residue was dried in vacuo at 80\u2009\u00b0C for 2\u2009h to remove the excess dibutyldisulfide, extracted with 5\u2009mL pentane, and crystallized from a slowly evaporating hexane/ether solution. The crystalline material was washed with pentane (2\u2009\u00d7\u20091\u2009mL) yielding 73.4\u2009mg  of pure 1a as a green solid. 1H NMR : \u03b4\u2009=\u20097.19\u20137.14 , 7.04 , 7.02 , 6.36 , 3.02 , 1.74 , 1.23 , 1.17\u20131.05 , 0.98 , 0.88 . 13C NMR  \u03b4\u2009=\u2009176.8 (CNHC), 147.0 (Cq), 139.2 (Cq), 129.1 (CHAryl), 124.4 (CHAryl), 123.8 (CHNHC), 43.1 (SBu-CH2), 34.9 (SBu-CH2), 29.1 (CHiPr), 26.2 (iPr-CH3), 24.3 (iPr-CH3) 24.0 (SBu-CH2), 14.7 (SBu-CH3). 11B NMR : \u03b4\u2009=\u200930 (s) ppm. Elemental analysis calculated for C62H90B2N4S2[+hexane]: C 76.81%, H 9.86%, N 5.27%, S 6.03%; found: C 76.86%, H 9.63%, N 5.62%, S 5.82%.Synthesis of B2(IDip)2(SPh)2, (1b): B2IDip2  and diphenyldisulfide  were dissolved in benzene (10\u2009mL) and stirred for 14\u2009h. The solvent was evaporated and the residue was extracted with pentane (2\u2009\u00d7\u20095\u2009mL). The pentane phase was removed under vacuum giving pure 1b  as a purple solid. Suitable crystals for X-ray diffraction were obtained by slow evaporation of a pentane solution. Decomp.: 221\u2009\u00b0C. 1H NMR : \u03b4\u2009=\u20097.04 , 6.91 , 6.85 , 6.79 , 6.29 , 3.20 , 1.05 , 0.97  ppm. 13C NMR  \u03b4\u2009=\u2009174.7 (Cq), 148.8 (Cq), 146.3 (Cq), 137.6 (Cq), 129.3 (CHAryl), 128.9 (CHAryl), 127.7 (CHAryl), 124.2 (CHAryl), 124.0 (CHNHC), 120.1 (CHAryl), 28.9 (CHiPr), 26.6 (iPr-CH3), 22.7 (iPr-CH3) ppm. 11B NMR : \u03b4\u2009=\u200925 (s) ppm. Elemental analysis calculated for C66H82B2N4S2: C 77.94%, H 8.13%, N 5.51%, S 6.30%; found: C 78.12%, H 8.26%, N 5.58%, S 6.25%.Synthesis of B2(IDip)2(SePh)2, (1c): A solution of B2IDip2  and 1,2-diphenyldiselenide  in benzene (10\u2009mL) was stirred for 14\u2009h. After the solvent was removed, the residue was extracted with pentane (2\u2009\u00d7\u20095\u2009mL). The solvent was evaporated under vacuum giving pure 1c  as a purple solid. Suitable crystals for X-ray diffraction were obtained by slow evaporation of a pentane solution. Decomp.: 128\u2009\u00b0C. 1H NMR : \u03b4\u2009=\u20097.05 , 6.96 , 6.93 , 6.88 , 6.76 , 6.33 , 3.29 , 1.02 , 0.98  ppm. 13C NMR  \u03b4\u2009=\u2009174.7 (Cq) 146.5 (Cq), 143.2 (Cq), 137.53 (Cq), 137.52 (Cq), 131.3 (CHAryl), 129.5 (CHAryl), 127.7 (CHAryl), 124.3 (CHAryl), 124.1 (CHNHC), 121.3 (CHAryl), 29.0 (CHiPr), 26.7 (iPr-CH3), 22.8 (iPr-CH3) ppm. 11B NMR : \u03b4\u2009=\u200922 (s) ppm. 77Se NMR : \u03b4\u2009=\u2009175.6\u2009ppm. Elemental analysis calculated for C66H82B2N4Se2: C 71.36%, H 7.44%, N 5.04%; found: C 70.68%, H 7.66%, N 4.66%.Synthesis of B2(CAAC)2(SBu)2, (2a): Dibutyl disulfide  was added dropwise to a stirred solution of B2(CAAC)2  in pentane (20\u2009mL) at \u201340\u2009\u00b0C. The mixture was stirred for 24\u2009h at RT and all volatiles were removed in vacuo. The dark yellow solid was dried in vacuo, dissolved in hexane (10\u2009mL), and black crystals were obtained by slow evaporation of the solvent. The crystalline material was washed with pentane (2\u2009\u00d7\u20091\u2009mL) yielding 291\u2009mg  of pure 2a as a black solid. Elemental analysis calculated for C48H80B2N2S2: C 74.78%, H 10.46%, N 3.63%, S 8.32%; found: C 75.15%, H 10.37%, N 3.70%, S 8.01%.Synthesis of B2(CAAC)2(SPh)2, (2b): Pentane (20\u2009mL at \u201340\u2009\u00b0C) was added to a mixture of B2(CAAC)2  and diphenyl disulfide . The mixture was stirred for 3\u2009h at RT, filtered and the residual solid was washed with pentane (3\u2009\u00d7\u20095\u2009mL). The brown solid was dried in vacuo, dissolved in benzene (10\u2009mL), and black crystals were obtained by slow evaporation of the solvent. The crystalline material was washed with pentane (2\u2009\u00d7\u20091\u2009mL) yielding 53.4\u2009mg  of pure 2b as a black solid. Decomp.: 138\u2009\u00b0C. Elemental analysis calculated for C52H72B2N2S2: C 77.02%, H 8.95%, N 3.45%, S 7.91%; found: C 77.57%, H 8.97%, N 3.36%, S 7.58%.Synthesis of B2(CAAC)2(SePh)2, (2c): Pentane (20\u2009mL at \u201340\u2009\u00b0C) was added to a mixture of B2(CAAC)2  and diphenyl diselenide . The mixture was stirred for 3\u2009h at RT, filtered and the residual solid was washed with pentane (2\u2009\u00d7\u20095\u2009mL). The brown solid was dried in vacuo, dissolved in benzene (10\u2009mL), and black crystals were obtained by slow evaporation of the solvent. The crystalline material was washed with pentane (2\u2009\u00d7\u20091\u2009mL) yielding 36.2\u2009mg  of pure 2c as a black solid. Decomp.: 191\u2009\u00b0C. Elemental analysis calculated for C52H72B2N2Se2: C 69.04%, H 8.02%, N 3.10%; found: C 69.24%, H 7.95%, N 2.74%.45. The EPR spectra of 2a and 2b show an intense half-field signal but only partially resolved zero-field splittings with no visible hyperfine structure. Attempts to improve the resolution by lowering the concentration or changing the solvent were not successful. For 2c, no clear sign of a triplet ground state could be obtained.EPR measurements at the X-band (9.4\u2009GHz) were carried out using a Bruker ELEXSYS E580 CW EPR spectrometer equipped with an Oxford Instruments helium cryostat (ESR900) and a MercuryiTC temperature controller. The spectral simulations were performed using MATLAB 8.6.0.267246 (R2015b) and the EasySpin 5.1.9 toolboxVycor tip, serving as the reference electrode. Formal redox potentials are referenced to the ferrocene/ferrocenium ([Cp2Fe]+/0) redox couple by using ferrocene as an internal standard. Tetrabutylammonium hexafluorophosphate ([Bu4N][PF6]) was employed as the supporting electrolyte. Compensation for resistive losses (iR drop) was employed for all measurements.Cyclic voltammetry experiments were performed using a Gamry Instruments Reference 600 potentiostat. A standard three-electrode cell configuration was employed using a platinum disk working electrode, a platinum wire counter electrode, and a silver wire, separated by a 2IDip2(SBu)2 (1a), B2IDip2(SPh)2 (1b), B2IDip2(SePh)2 (1c), and B2CAAC2(SBu)2 (2a) were collected on a Bruker X8-APEX II diffractometer with a CCD area detector and multi-layer mirror-monochromated MoK\u03b1 radiation. The structure was solved using the intrinsic phasing method (ShelXT)46, refined with the ShelXL\u00a0program47, and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factor calculations. All hydrogen atoms were assigned to idealized geometric positions.The crystal data of BCrystal data for B2IDip2(SBu)2(1a): The displacement parameters of atoms C63\u2013C74 were restrained to the same value with similarity restraint SIMU. C68H104B2N4S2, Mr\u2009=\u20091063.29, green block, 0.294\u2009\u00d7\u20090.257\u2009\u00d7\u20090.125\u2009mm3, monoclinic space group P21/c, a\u2009=\u200914.423(5)\u2009\u00c5, b\u2009=\u200912.522(5)\u2009\u00c5, c\u2009=\u200936.640(17)\u2009\u00c5, \u03b2\u2009=\u200996.25(3)\u00b0, V\u2009=\u20096578(5)\u2009\u00c53, Z\u2009=\u20094, \u03c1calcd\u2009=\u20091.074\u2009g\u2009cm\u20133, \u03bc\u2009=\u20090.122\u2009mm\u20131, F(000)\u2009=\u20092328, T\u2009=\u2009103(2)\u2009K, R1\u2009=\u20090.0980, wR2\u2009=\u20090.1550, 13420 independent reflections [2\u03b8\u2009\u2264\u200952.744\u00b0], and 768 parameters. CCDC-1567701.Crystal data for B2IDip2(SPh)2(1b): C66H82B2N4S2, Mr\u2009=\u20091017.09, red block, 0.25\u2009\u00d7\u20090.14\u2009\u00d7\u20090.05\u2009mm3, monoclinic space group P21/c, a\u2009=\u200922.2980(16)\u2009\u00c5, b\u2009=\u200924.4556(17)\u2009\u00c5, c\u2009=\u200942.972(3)\u2009\u00c5, \u03b2\u2009=\u200991.133(2)\u00b0, V\u2009=\u200923428(3)\u2009\u00c53, Z\u2009=\u200916, \u03c1calcd\u2009=\u20091.153\u2009g\u2009cm\u22123, \u03bc\u2009=\u20090.134\u2009mm\u20131, F(000)\u2009=\u20098768, T\u2009=\u2009100(2)\u2009K, R1\u2009=\u20090.1465, wR2\u2009=\u20090.1925, 48137 independent reflections [2\u03b8\u2009\u2264\u200952.746\u00b0], and 2730 parameters. CCDC-1567705.Crystal data for B2IDip2(SePh)2(1c): C66H82B2N4Se2, Mr\u2009=\u20091110.89, red block, 0.35\u2009\u00d7\u20090.15\u2009\u00d7\u20090.08\u2009mm3, monoclinic space group P21/c, a\u2009=\u200922.4904(11)\u2009\u00c5, b\u2009=\u200924.4964(13)\u2009\u00c5, c\u2009=\u200943.042(2)\u2009\u00c5, \u03b2\u2009=\u200991.335(2)\u00b0, V\u2009=\u200923707(2)\u2009\u00c53, Z\u2009=\u200916, \u03c1calcd\u2009=\u20091.245\u2009g\u2009cm\u20133, \u03bc\u2009=\u20091.291\u2009mm\u20131, F(000)\u2009=\u20099344, T\u2009=\u2009100(2)\u2009K, R1\u2009=\u20090.0804, wR2\u2009=\u20090.0917, 48482 independent reflections [2\u03b8\u2009\u2264\u200952.744\u00b0], and 2729 parameters. CCDC-1567706.Crystal data for B2CAAC2(SBu)2(2a): C51H87B2N2S2, Mr\u2009=\u2009813.96, orange block, 0.335\u2009\u00d7\u20090.257\u2009\u00d7\u20090.112\u2009mm3, triclinic space group Pa\u2009=\u200910.383(5)\u2009\u00c5, b\u2009=\u200914.048(9)\u2009\u00c5, c\u2009=\u200917.857(8)\u2009\u00c5, \u03b1\u2009=\u200975.299(15)\u00b0, \u03b2\u2009=\u200984.42(3)\u00b0, \u03b3\u2009=\u200977.545(19)\u00b0, V\u2009=\u20092458(2)\u2009\u00c53, Z\u2009=\u20092, \u03c1calcd\u2009=\u20091.100\u2009g\u2009cm\u20133, \u03bc\u2009=\u20090.143\u2009mm\u20131, F(000)\u2009=\u2009898, T\u2009=\u2009100(2)\u2009K, R1\u2009=\u20090.0532, wR2\u2009=\u20090.1087, 10053 independent reflections [2\u03b8\u2009\u2264\u200952.744\u00b0], and 533 parameters. CCDC-1567703.2CAAC2(SPh)2 (2b) and B2CAAC2(SePh)2 (2c) were collected on a Bruker D8 Quest diffractometer with a CMOS area detector and multi-layer mirror-monochromated MoK\u03b1 radiation. The structure was solved using the intrinsic phasing method (ShelXT)46, refined with the ShelXLprogram47, and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factor calculations. All hydrogen atoms were assigned to idealized geometric positions.The crystal data of BCrystal data for B2CAAC2(SPh)2(2b): C52H72B2N2S2, Mr\u2009=\u2009810.85, orange block, 0.173\u2009\u00d7\u20090.161\u2009\u00d7\u20090.122\u2009mm3, monoclinic space group P21/n, a\u2009=\u20099.9798(15)\u2009\u00c5, b\u2009=\u200918.647(4)\u2009\u00c5, c\u2009=\u200924.919(5)\u2009\u00c5, \u03b2\u2009=\u200997.909(15)\u00b0, V\u2009=\u20094593.2(15)\u2009\u00c53, Z\u2009=\u20094, \u03c1calcd\u2009=\u20091.173\u2009g\u2009cm\u20133, \u03bc\u2009=\u20090.153\u2009mm\u20131, F(000)\u2009=\u20091760, T\u2009=\u2009100(2)\u2009K, R1\u2009=\u20090.0422, wR2\u2009=\u20090.0961, 9368 independent reflections [2\u03b8\u2009\u2264\u200952.746\u00b0], and 539 parameters. CCDC-1567702.Crystal data for B2CAAC2(SePh)2(2c): C52H72B2N2Se2, Mr\u2009=\u2009904.65, orange block, 0.061\u2009\u00d7\u20090.055\u2009\u00d7\u20090.025\u2009mm3, monoclinic space group P21/n, a\u2009=\u200910.060(7)\u2009\u00c5, b\u2009=\u200918.707(7)\u2009\u00c5, c\u2009=\u200924.857(14)\u2009\u00c5, \u03b2\u2009=\u200998.86(3)\u00b0, V\u2009=\u20094622(5)\u2009\u00c53, Z\u2009=\u20094, \u03c1calcd\u2009=\u20091.300\u2009g\u2009cm\u20133, \u03bc\u2009=\u20091.637\u2009mm\u20131, F(000)\u2009=\u20091904, T\u2009=\u2009100(2)\u2009K, R1\u2009=\u20090.0628, wR2\u2009=\u20090.0784, 9321 independent reflections [2\u03b8\u2009\u2264\u200952.746\u00b0], and 539 parameters. CCDC-1567704.48, B3LYP51, and BP8652 levels in conjunction with the def2-SVP53 basis set. The structures were characterized as minima by frequency calculation. The NBO54 analyses were carried out at the M05-2X/def2-SVP level  calculations were carried out on diamagnetic diborenes 1a\u2013c and the diradicals 2a\u2013c in their singlet and triplet states  whereas the triplet states of 2a-c are always more stable than the singlet states  43 approach to optimize the geometry of the lowest-lying singlet and triplet states of 2a. Both optimizations were started from the X-ray structure of the triplet ground state. The computed singlet geometry does not represent the global minimum of the singlet potential energy surface, which possesses a nearly planar CCAAC-B-B-CCAAC orientation. However, only the local minimum lying near the triplet equilibrium structure will not be populated in the measurements because the global minimum of the singlet state is separated from the triplet equilibrium geometry by high-energy barriers. For the computed geometries , the MN12L/6\u2013311G approach predicts an S\u2013T gap of about \u20136.4\u2009kcal\u2009mol\u20131 (triplet below singlet state).To obtain an estimate of the inaccuracies of DFT approaches, we first used the MN12L2a\u02b9 in which we replaced the bulky substituents as indicated in Supplementary Figure\u00a02a systems to include the influence of steric effects on the geometry. The model system 2a\u02b9 contains all essential binding ingredients of 2a but is sufficiently small to perform high-level NEVPT240/def2-TZVP benchmark calculations for the S\u2013T gap. To compare the predicted S\u2013T gaps, we performed single-point calculations employing the geometries described above.To enable high-level multi-reference approaches, we then created a closely related model system \u22121 to nearly \u201329\u2009kcal\u2009mol\u22121, showing that such DFT calculations have to be handled with care.The results are summarized in Supplementary Table\u00a0Cartesian coordinates for all of the calculated compounds are given in Supplementary Table\u00a02a were carried out with a Quantum-Design MPMS-XL-5 SQUID magnetometer equipped with a 5-Tesla magnet in the range from 295 to 2.0\u2009K at a magnetic field of 0.5\u2009T. The powdered sample was contained in a Teflon bucket and fixed in a non-magnetic sample holder. Each raw data file for the measured magnetic moment was corrected for the diamagnetic contribution of the Teflon bucket according to Mdia(bucket)\u2009=\u2009\u03c7g\u2009\u00d7\u2009m\u2009\u00d7\u2009H, with an experimentally obtained gram susceptibility of the Teflon bucket. The molar susceptibility data were corrected for the diamagnetic contribution using Pascal\u2019s constants56. Experimental data were modeled with the julX program57 using a fitting procedure to the spin Hamiltonian \u20136\u2009cm3\u2009mol\u20131) and some weak intermolecular interactions (\u20130.12\u2009K). The latter were considered in a mean field approach by using a Weiss temperature \u039858. The Weiss temperature \u0398 (defined as \u0398\u2009=\u2009zJinterS(S\u2009+\u20091)/3k) relates to intermolecular interactions zJinter, where Jinter is the interaction parameter between two nearest neighbor magnetic centers, k is the Boltzmann constant (0.695\u2009cm\u20131\u2009K\u20131), and z is the number of nearest neighbors.Temperature-dependent magnetic susceptibility measurements for http://www.ccdc.cam.ac.uk/data_request/cif.The data that support the findings of this study are available from the corresponding author on reasonable request. The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers 1567701\u20131567706. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via Supplementary Information(PDF 4825 kb)Peer Review File(PDF 139 kb)Description of Additional Supplementary Files(PDF 166 kb)Supplementary Data 1(XLSX 196 kb)"}
{"text": "Scientific Reports7: Article number: 44813; 10.1038/srep44813 published online: 03202017; updated: 09202017.The original version of this Article contained typographical errors in the Abstract.6 (dielectric loss ~5\u2009\u00d7\u200910\u22127) at high powers, degrading to 7\u2009\u00d7\u200910\u22125  and g-factor of 1.995\u2009\u00b1\u20090.008\u201d.\u201cWhispering Gallery Mode (WGM) analysis revealed large Quality Factors of order 2\u2009\u00d7\u200910now reads:6 (dielectric loss ~5\u2009\u00d7\u200910\u22127) at high powers, degrading to 7\u2009\u00d7\u2009105 (dielectric loss ~1.4\u2009\u00d7\u200910\u22126) at single photon energy. A very low-loss narrow line width paramagnetic spin flip transition was detected with extreme sensitivity in 28Si, with very small concentration below 1011\u2009cm\u22123 (less than 10 parts per trillion) and g-factor of 1.995\u2009\u00b1\u20090.008\u201d.\u201cWhispering Gallery Mode (WGM) analysis revealed large Quality Factors of order 2\u2009\u00d7\u200910This has now been corrected in the PDF and HTML versions of the Article."}
{"text": "II with the bridging ligand bis\u00ad(pyridin-3-ylmeth\u00adyl)sulfane afforded a one-dimensional zigzag chain polymeric structure, with the charge balanced by two coordinated chloride anions. C\u2014H\u22efCl hydrogen bonds and Hg\u2014Cl\u22ef\u03c0 inter\u00adactions, together with C\u2014H\u22ef\u03c0 hydrogen bonds, stabilize the crystal structure.The reaction of Hg L, C12H12N2S) in methanol afforded the title crystalline coordination polymer catena-poly[[di\u00adchlorido\u00admercury(II)]-\u03bc-bis\u00ad(pyridin-3-ylmeth\u00adyl)sulfane-\u03ba2N:N\u2032], [HgCl2L]n. The asymmetric unit consists of one HgII cation, one L ligand and two chloride anions. Each HgII ion is coordinated by two pyridine N atoms from separate L ligands and two chloride anions. The metal adopts a highly distorted tetra\u00adhedral geometry, with bond angles about the central atom in the range 97.69\u2005(12)\u2013153.86\u2005(7)\u00b0. Each L ligand bridges two HgII ions, forming an infinite \u2013(Hg\u2013L)n\u2013 zigzag chain along the b axis, with an Hg\u22efHg separation of 10.3997\u2005(8)\u2005\u00c5. In the crystal, adjacent chains are connected by inter\u00admolecular C\u2014H\u22efCl hydrogen bonds, together with Hg\u2014Cl\u22ef\u03c0 inter\u00adactions [chloride-to-centroid distance = 3.902\u2005(3)\u2005\u00c5], that form between a chloride anion and the one of the pyridine rings of L, generating a two-dimensional layer extending parallel to (101). These layers are further linked by inter\u00admolecular C\u2014H\u22ef\u03c0 hydrogen bonds, forming a three-dimensional supra\u00admolecular network.The reaction of mercury(II) chloride with bis\u00ad(pyridin-3-ylmeth\u00adyl)sulfane ( The flexibility, length and coordinating ability of the spacer ligands exert strong influences on the formation of coordination polymers and their resulting diverse topologies (Zheng L), and has reported its AgI and CoII coordination polymers  chloride with L sulfane sulfane, C12H12N2S. The asymmetric unit comprises one HgII cation, one L ligand and two chloride anions. The HgII ion is four-coordinated, binding to two Cl anions and two pyridine N atoms from two separate symmetry-related L ligands, forming a highly distorted tetra\u00adhedral geometry \u2005\u00c5. In the L ligand, the dihedral angle between the two terminal pyridine rings is 78.52\u2005(18)\u00b0, and the flexible thio\u00adether moiety [C4\u2013C6\u2013S1\u2013C7\u2013C8] shows a bent arrangement with a gauche--anti configuration . The conformation of the L ligand, along with its Npy\u2014Hg\u2014Npy coordination angle [98.39\u2005(16)\u00b0], may induce the zigzag topology of the chain.Fig.\u00a01ry Fig.\u00a01, with thry Fig.\u00a01. The S aon Fig.\u00a02. The sepet al., 2009L with Cl2\u22efCg1iv = 3.902\u2005(3)\u2005\u00c5 and Hg1\u2014Cl2\u22efCg1iv = 77.21\u2005(6)\u00b0 , generating layers extending parallel to (101). Neighboring layers are linked by C2\u2014H2\u22efCg2 hydrogen bonds  gave three hits. Two   of the L ligand adopts a bent arrangement that is similar to that of the HgII polymer described here. However, the title compound displays a zigzag topology and is the first example of an HgII coordination polymer with the ligand L.A search of the Cambridge Structural Database  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901701619X/sj5541sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901701619X/sj5541Isup2.hklStructure factors: contains datablock(s) I. DOI: 1584773CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E)-4-meth\u00adoxy\u00adbenzyl\u00adidene\u00adamino]\u00adpropan-2-ol, mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds into C(5) supra\u00admolecular chains propagating along the a-axis direction.In the crystal of 1,3-bis\u00ad[\u00b0. In the crystal, O\u2014H\u22efN hydrogen bonds link the mol\u00adecules into infinite C(5) chains propagating along the a-axis direction. The packing of these chains is consolidated by C\u2014H\u22efO inter\u00adactions and C\u2014H\u22ef\u03c0 short contacts, forming a three-dimensional network.The title Schiff base, C The N1=C1 and N2=C5 distances of 1.265\u2005(4) and 1.271\u2005(4)\u2005\u00c5, respectively, are consistent with C=N double bonding. The bond angles of 117.0\u2005(3) and 117.7\u2005(3)\u00b0 around the N1 and N2 atoms confirm their sp2 character. The slight differences between N=C distances and C\u2014N=C angles are due to the significant effect of the hydrogen bond on the geometric parameters of the nitro\u00adgen atom (N2) involved in the inter\u00admolecular hydrogen bond (see below).The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01The N1\u2014C2\u2014C3\u2014C4 torsion angle is \u221264.4\u2005(4)\u00b0 and the C2\u2014C3\u2014C4\u2014N2 torsion angle is 175.0\u2005(3)\u00b0. The O1\u2014C3\u2014C4\u2014N2 torsion angle is \u221265.3\u2005(3)\u00b0, which has a significant role to play in the hydrogen-bonding pattern in the crystal of the title compound (see below). The two meth\u00adoxy substituents are essentially coplanar with their bound benzene rings with torsion angles C17\u2014O2\u2014C14\u2014C13 = 169.3\u2005(3)\u00b0 and C27\u2014O3\u2014C24\u2014C23 = \u2212172.2\u2005(3)\u00b0.C(5) chains extending along the a-axis direction. The chains are further linked to neighbouring chains through a pair of weak C\u2014H\u22efO hydrogen bonds (Table\u00a01Cg (\u03c0\u2013ring) inter\u00adactions  = 0.95\u2005\u00c5 for aromatic and azomethine atoms, d(C\u2014H) = 0.99\u2005\u00c5 for methyl\u00adene, d(C\u2014H) = 1.00\u2005\u00c5 for C3\u2014H3 and 0.98\u2005\u00c5 for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups. The absolute structure of the crystal chosen for data collection was indeterminate in the present refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016016947/hb7623sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016016947/hb7623Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016016947/hb7623Isup3.cmlSupporting information file. DOI: 1511139CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The synthesis and structural determination of a nickel(II) complex where the two nickel cations in the asymmetric unit each are coordinated by two tridentate, potentially redox non-innocent bis-imino\u00adpyridyl ligands are reported. N}eth\u00adyl)pyridine-\u03baN]nickel(II) dichloride\u2013di\u00adchloro\u00admethane\u2013water (1/2/2), [Ni(C25H29N5)2]Cl2\u00b72CH2Cl2\u00b72H2O, represents a nickel(II) bis\u00ad(pyridine di\u00adimine) complex with electron-donating di\u00admethyl\u00adamino\u00adphenyl substituents. The complex crystallizes as a water/di\u00adchloro\u00admethane solvate with Z\u2032 = 2, thus the asymmetric unit consists of two NiII complex cations, four chloride anions, four adventitious water and four di\u00adchloro\u00admethane solvent mol\u00adecules. Around each octa\u00adhedrally coordinated NiII cation, one pendant phenyl group on each of the two ligands has an intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction with the pyridine ring of the other chelating ligand. In the crystal, pairs of water mol\u00adecules are hydrogen bonded to pairs of chlorine atoms. The di\u00adchloro\u00admethane solvent mol\u00adecules are likewise hydrogen bonded to the chloride anions.The solvated title compound, bis\u00adimino-\u03ba A solution of 2,6-di\u00adacetyl\u00adpyridine , 4-(di\u00admethyl\u00adamino)\u00adaniline  and formic acid (1\u2005ml) was prepared in toluene (100\u2005ml) under nitro\u00adgen atmosphere and then stirred for 12\u2005h on mol\u00adecular sieves. The reaction mixture was filtered and extracted with excess di\u00adchloro\u00admethane, then the amount of solvent was reduced in vacuo. The crude yellow product was then washed with cold methanol, followed by diethyl ether and filtered producing a pure bright-yellow solid . 1H NMR : \u03b4 8.4\u20138.2 , 7.9\u20137.8 , 6.8  3.0 , 2.5 . MS (ESI): 400.4 m/z [C25H29N5]H+.Synthesis of [bis-\u00adeth\u00adyl)pyridine)\u00adnickel(II)] chloride. A solution of the PDI-DMA ligand  and nickel(II) chloride  was prepared in THF (15\u2005ml) under nitro\u00adgen atmosphere, then stirred for 12\u2005h. The solution was filtered and extracted with di\u00adchloro\u00admethane. The solvent was removed in vacuo yielding a dark reddish-brown solid . X-ray diffraction quality crystals were isolated as red\u2013brown blocks by vapor diffusion of hexa\u00adnes into a saturated solution of the product and di\u00adchloro\u00admethane. The complex was NMR silent (paramagnetic). MS (ESI): m/z 855.5 [C50H57N10Ni]+.Uiso(H) = 1.2 \u00d7, 1.2 \u00d7 or 1.5 \u00d7 Ueq(C) for aromatic, methyl\u00adene and methyl H atoms, successively. Water H atoms were initially located from a difference Fourier map and included in their initially observed positions and allowed to ride with the position of the parent oxygen atom. Displacement parameters of the hydrogen atom were freely refined. Two reflections  I. DOI: 10.1107/S2056989017010088/wm5402Isup2.hklStructure factors: contains datablock(s) I. DOI: 1560729CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A combined single-crystal X-ray diffraction and NMR crystallography study of a 1:1 cocrystal of two fungicides, namely di\u00adthia\u00adnon and pyrimethanil, is presented. Specifically, the role of hydrogen bonding and C\u2014H\u22ef\u03c0 and S\u22efO inter\u00admolecular inter\u00adactions is qu\u00adanti\u00adtatively investigated. H,10H-naphtho\u00addithiine-2,3-dicarbo\u00adnitrile\u20134,6-dimethyl-N-phenyl\u00adpyrimidin-2-amine (1/1), C14H4N2O2S2\u00b7C12H13N2]. Following an NMR crystallography approach, experimental solid-state magic angle spinning (MAS) NMR spectra are presented together with GIPAW (gauge-including projector augmented wave) calculations of NMR chemical shieldings. Specifically, experimental 1H and 13C chemical shifts are determined from two-dimensional 1H\u201313C MAS NMR correlation spectra recorded with short and longer contact times so as to probe one-bond C\u2014H connectivities and longer-range C\u22efH proximities, whereas H\u22efH proximities are identified in a 1H double-quantum (DQ) MAS NMR spectrum. The performing of separate GIPAW calculations for the full periodic crystal structure and for isolated mol\u00adecules allows the determination of the change in chemical shift upon going from an isolated mol\u00adecule to the full crystal structure. For the 1H NMR chemical shifts, changes of 3.6 and 2.0\u2005ppm correspond to inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonding, while changes of \u22122.7 and \u22121.5\u2005ppm are due to ring current effects associated with C\u2014H\u22ef\u03c0 inter\u00adactions. Even though there is a close inter\u00admolecular S\u22efO distance of 3.10\u2005\u00c5, it is of note that the mol\u00adecule-to-crystal chemical shifts for the involved sulfur or oxygen nuclei are small.A single-crystal X-ray diffraction structure of a 1:1 cocrystal of two fungicides, namely di\u00adthia\u00adnon (DI) and pyrimethanil (PM), is reported [systematic name: 5,10-dioxo-5 While this is an established procedure in the development of new active pharmaceutical ingredients, where it is used to increase the solubility and bioavailability  NMR with calculation of NMR parameters, is finding important application to moderately sized organic mol\u00adecules  were mixed thoroughly in a 1:1 molar ratio (0.5\u2005g of pyrimethanil) and kept at 323\u2005K under agitation. After a couple of hours, the powdery product had changed to a dark-olive-green colour.The DI\u2013PM cocrystal was prepared according to method VII in point [0041] of Sowa  al. 2013, i.e. drUiso(H) = 1.2\u20131.5Ueq(parent)], after which the positions were refined with riding constraints  MAS experiments were performed on a Bruker Avance III spectrometer operating at 1H and 13C Larmor frequencies of 600 and 150.9\u2005MHz, respectively, using a 1.3\u2005mm HXY (1H MAS) or a 4\u2005mm HX (13C CP MAS) Bruker probe. In all cases, a 1H 90\u00b0 pulse duration of 2.5\u2005\u00b5s was used. 2D 1H\u201313C HETCOR experiments were performed on a Bruker Avance III spectrometer, using a 4\u2005mm HXY probe in double-resonance mode. In the HETCOR pulse sequence, the following phase cycling was employed: 1H 90\u00b0 pulse (90\u00b0 270\u00b0), 13C 180\u00b0 pulse (2{0\u00b0} 2{180\u00b0}), 13C CP contact pulse (4{0\u00b0} 4{180\u00b0} 4{90\u00b0} 4{270\u00b0}), receiver (0\u00b0 180\u00b0 0\u00b0 180\u00b0 180\u00b0 0\u00b0 180\u00b0 0\u00b0 90\u00b0 270\u00b0 90\u00b0 270\u00b0 270\u00b0 90\u00b0 270\u00b0 90\u00b0). For CP, a 70 to 100% ramp  were relaxed and periodic boundary conditions were applied. The space group P21/n was preserved. All distances and angles stated in the main text of this article are for the geometry-optimized crystal structure. Note also that the geometry optimization within CASTEP causes a relabelling of the atoms \u2013 in this article, we use the CASTEP numbering; see Fig. S1 in the Supporting information for a comparison with the numbering employed in the crystallographic CIF file. The GIPAW method , a chain of mol\u00adecules is held together by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds (between DI and PM mol\u00adecules) and by putative S\u22efO inter\u00adactions  and 1(c), respectively. As can be seen from the representation along the crystallographic a axis in Fig.\u00a01c), the packing is based on assemblies of blocks of four mol\u00adecules; four mol\u00adecules (PM\u2013DI\u2013DI\u2013PM) are arranged in a layer , forming a block that is perpendicular to an adjacent block of four mol\u00adecules, thus building up the \u2018zigzag\u2019 arrangement.The single-crystal X-ray diffraction structure of the DI\u2013PM cocrystal is schematically represented in Fig.\u00a01er Fig.\u00a01a, formi13C CP MAS NMR 1D spectrum  of the DI\u2013PM cocrystal, together with three stick spectra  that represent 13C chemical shifts calculated using the GIPAW method for the DI\u2013PM crystal structure. Specifically, the calculated 13C chemical shifts are presented in three groups according to whether they correspond to direct one-bond C\u2014H connectivities  or nonprotonated C atoms . The distinction between Figs.\u00a02c) and 2(d) corresponds to whether cross peaks corresponding to a longer-range C\u22efH proximity are observed in 1H\u201313C 2D correlation spectra  and 3(b) present 1H NMR spectra of the DI\u2013PM cocrystal recorded at a fast MAS frequency of 60\u2005kHz; specifically, a one-pulse one-dimensional spectrum in Fig.\u00a03a), together with vertical lines corresponding to calculated (GIPAW) 1H chemical shifts, as well as a 2D DQ spectrum in Fig.\u00a03b). In addition, Fig.\u00a03c) presents a 1H\u201313C 2D correlation spectrum of the DI\u2013PM cocrystal; note that this spectrum has been rotated through 90\u00b0 from its usual representation such that the direct (13C) dimension is vertical. In this way, it is possible to directly compare  1H chemical shifts of peaks in the 1H\u201313C  and 1H DQ 2D  and 1H 1D  spectra. Two separate spectral regions are presented in Fig.\u00a03c) corresponding to (top) the methyl resonances at a 13C chemical shift close to 25\u2005ppm and (bottom) the aromatic CH resonances with 13C chemical shifts between 110 and 140\u2005ppm.Figs.\u00a033C Fig.\u00a03c and 1H2D Fig.\u00a03b and 1H1D Fig.\u00a03a spectr1H\u201313C correlation spectrum in Fig.\u00a03c) was recorded using a short CP contact time of 100\u2005\u00b5s to transfer magnetization from 1H to 13C, such that cross peaks correspond to one-bond C\u2014H connectivities. The spreading of the resonances into two dimensions in Fig.\u00a03c) allows the identification of two and ten resolved cross peaks for the CH3 and aromatic CH groups, respectively. The value of such a 1H\u201313C correlation spectrum in resolving and assigning the experimental 1H chemical shifts is thus evident. Table\u00a0213C chemical shifts . For directly bonded C\u2014H connectivities, H-atom labels and calculated (GIPAW) and experimental 1H chemical shifts are presented in normal font.The 1H\u201313C correlation spectra recorded with three different CP contact times of 100\u2005\u00b5s , 500\u2005\u00b5s  and 1\u2005ms ; Fig.\u00a04a) is a copy of Fig.\u00a03c), but presented in the normal orientation, i.e. with the direct (13C) dimension horizontal. It is evident that additional cross peaks are observed for longer CP contact times \u2013 these correspond to longer-range C\u22efH proximities , 160.1 (atom C63) and 168.2\u2005ppm (atoms C64 and C67); these all correspond to intra\u00admolecular proximities within the di\u00adthia\u00adnon mol\u00adecule, i.e. C57 with H17 , H21  and H29 , C63 with H29 , C64 and C67 with H25  and CH3 protons . Of most inter\u00adest is the  cross peak, which thus enables the determination of the NH 1H chemical shift.Fig.\u00a04\u00b5s Fig.\u00a04a, 500\u2005\u00b5\u00b5s Fig.\u00a04b and 1\u2005ms Fig.\u00a04c; Fig.\u00a01H chemical shifts assigned, let us re-examine the 1H DQ MAS spectrum in Fig.\u00a03b). In such a spectrum, cross peaks are observed in the DQ dimension at the sum of the two single-quantum (SQ) frequencies if there is a close proximity . Consider the two lowest-ppm aromatic CH protons H25 (4.0\u2005ppm) and H2 (6.2\u2005ppm) for which distinct 1H resonances are resolved in the 1H SQ dimension. For H25, the only DQ peak is at 4.0\u00a0+\u00a02.0 = 6.0\u2005ppm with the CH3 protons, since H25 is sandwiched between two methyl-group substituents on the PM mol\u00adecule. For H2, there is a DQ peak at 6.2\u00a0+\u00a07.5 = 13.7\u2005ppm corresponding to the intra\u00admolecular H\u22efH proximity with the neighbouring H1  and H3  DI aromatic CH protons, as well as a DQ peak at 6.2\u00a0+\u00a02.0 = 8.2\u2005ppm due to inter\u00admolecular proximities to the PM CH3 H atoms . Considering the high-ppm region, DQ cross peaks for the overlapping PI NH H29 (9.1\u2005ppm) and aromatic CH H17 (9.1\u2005ppm) resonances are observed at 9.1\u00a0+\u00a07.7 = 16.8\u2005ppm for intra\u00admolecular H29\u22efH21 (2.21\u2005\u00c5) and H17\u22efH18 (2.50\u2005\u00c5) proximities, as well as at 9.1\u00a0+\u00a02.0 = 11.1\u2005ppm for inter\u00admolecular proximities to PM methyl-group protons (closest distances of H17\u22efH26 = 2.48\u2005\u00c5 and H29\u22efH24 = 2.64\u2005\u00c5). For the other overlapping CH aromatic resonances, cross peaks due to intra\u00admolecular proximities with other CH aromatic resonances, as well as inter\u00admolecular proximities to the methyl protons, are also observed.With all the 1H\u201313C correlation spectra presented in Fig.\u00a0413C and 1H chemical shifts. Specifically, in Fig.\u00a04a), red crosses correspond to direct C\u2014H one-bond connectivities (C\u2014H distances under 1.2\u2005\u00c5), while in Figs.\u00a04b) and 4(c), red crosses are presented for C\u2014H proximities between 1.2 and 2.2\u2005\u00c5 , and between 2.2 and 3.0\u2005\u00c5 . We comment here on the level of agreement between experimental and calculated (GIPAW) chemical shifts. Starting with a consideration of the aromatic CH moieties ; this corresponds to the established observation that the discrepancy is within 1% of the chemical shift range . For the 1H chemical shifts, while most are within the usual 0.3\u2005ppm, some exhibit slightly larger discrepancies, notably 0.6\u2005ppm for atoms H17 and H25.In the \u2005\u00c5 Fig.\u00a04b, and b\u2005\u00c5 Fig.\u00a04c. We co3 groups , whereas the calculated 13C chemical shifts are both 8.5\u2005ppm lower than the experimental values, although the experimental difference in 13C chemical shifts between atoms C65 and C68 of 1.8\u2005ppm is reproduced by the calculation (difference of 1.9\u2005ppm). The explanation for this is well known, namely, the gradient of a plot of experimental 13C chemical shifts against calculated shielding deviates slightly from \u22121 , where the calculated 1H chemical shift of 10.5\u2005ppm is 1.4\u2005ppm higher than the experimental value of 9.1\u2005ppm. Such a large difference is explained by a known temperature dependence  for hydrogen-bonded protons  atom that is involved in an inter\u00admolecular N\u2014H\u22efO hydrogen bond to atom O1 . Inter\u00adestingly, \u0394\u03b4crystal\u2013mol\u00adecule = 2.0\u2005ppm for the aromatic CH H21 atom, for which Fig.\u00a01a) identifies an inter\u00admolecular C\u2014H\u22efO so-called weak hydrogen-bonding  and H2 (\u22121.6\u2005ppm); as shown in Fig.\u00a051H chemical shift are a consequence of ring current effects associated with the proton pointing towards the centre of a six-membered aromatic ring of a nearby PM mol\u00adecule in a C\u2014H\u22ef\u03c0 inter\u00adaction, as has been noted previously in a number of other cases   global, I. DOI: 10.1107/S2053229617000870/df3006Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2053229617000870/df3006sup2.txtCASTEP cif output. DOI: 10.1107/S2053229617000870/df3006sup4.txtmagres file. DOI: 10.1107/S2053229617000870/df3006sup5.pdfAdditional Tables  13C chemical shift values) and a Figure showing the difference in the numbering schemes between the crystallographic data and the output of the GIPAW (CASTEP) calculations. DOI: 1507863CCDC reference:"}
{"text": "Podanthus mitiqui, is reported and the stereochemical features established.The structure of erioflorin, a germacrane sesquiterpene lactone isolated from  19H24O6 cyclo\u00addeca\u00adfuran-9-yl methacrylate], is a tricyclic germacrane sesquiterpene lactone, which was isolated from Podanthus mitiqui (L.). The compound crystallizes in the space group P212121, and its mol\u00adecular structure consists of a methacrylic ester of a ten-membered ring sesquiterpenoid annelated with an epoxide and a butyrolactone. The structure is stabilized by one intramolecular C\u2014H\u22efO hydrogen bond. An O\u2014H\u22efO hydrogen bond and further C\u2014H\u22efO interactions can be observed in the packing.The title compound, erioflorin, C Podanthus mitiqui (Lindl)  is an endemic plant of the Central Zone of Chile. It is an evergreen shrub that can reach up to two meters in height; its flowers are yellow or orange\u2013yellow globose inflorescences. Previous chemical investigations of extracts isolated from the stems and leaves of Podanthus mitiqui revealed the presence of sesquiterpene lactones with a germacrane framework such as ovatifolin, de\u00adacetyl\u00adovatifolin and arturin \u2005\u00c5 and smallest displacement parameters \u03c6 of 23.2\u2005(8), 252.2\u2005(3) and 346.1\u2005(2)\u00b0. The maximum deviation from the mean plane is 0.589\u2005(3)\u2005\u00c5 (C3). The C\u2014C bond lengths range from 1.474\u2005(5) to 1.557\u2005(4)\u2005\u00c5. The Z-configured double bond is located between C4 and C5 with a bond length of 1.326\u2005(4)\u2005\u00c5. Some bond angles differ notably from ideal values due to the ring strain, such as C3\u2014C4\u2014C5 and C4\u2014C5\u2014C6 . The bond angles within the ten-membered ring including Csp3 atoms range from 112.0\u2005(3)\u00b0 to 125.7\u2005(3)\u00b0. The ten-membered and the five-membered rings are trans-fused. The lactone ring shows a closed puckering on C6-C7 (twisted). The puckering amplitude and the smallest displacement parameter of the five-membered ring are q = 0.192\u2005(3)\u2005\u00c5 and \u03c6 = 58.7\u2005(9)\u00b0. With respect to the lactone ring, H6 and H7 are equatorially oriented, whereas the C6\u2014C5 and the C7\u2014C8 bonds are axial. The maximum deviations of the substituents from the best plane are 0.065\u2005(6)\u2005\u00c5 (O4) and \u22120.323\u2005(6)\u2005\u00c5 (C13). The 1,10-ep\u00adoxy ring is trans-fused. The C8 side chain is \u03b2 oriented as well as the C10 methyl group, whereas the C4 methyl group is \u03b1. The methacrylate substituent deviates from the planarity by twisting about C16\u2014C17 [torsion angle O5\u2014C16\u2014C17\u2014C19 = 28.4\u2005(5)\u00b0]. The structure is closely related to that of di\u00adhydro\u00adheliangine mono\u00adchlorido acetate , eriophyllin-B  and eriophyllin-C , which were also isolated from Eriophyllum confertiflorum  to 0.805\u2005(3)\u2005\u00c5, yielding a total puckering amplitude ii, running along the c-axis direction is formed via the hydroxyl group and the lactone oxo group , approximately between the a and b axes (C7\u2014H7\u22efO1i) and along b (C13\u2014H13B\u22efO6iii). Non-hydrogen inter\u00admolecular contacts are found between O2 and O4iv . The unit cell contains no residual solvent-accessible voids.The crystal structure features infinite chains connected by hydrogen bonds. A strong O\u2014H\u22efO hydrogen bond, namely O2\u2014H2\u22efO4up Fig.\u00a02. Furtheret al. . Aerial parts (9.6\u2005kg) were powdered and extracted by maceration with ethyl acetate for 3\u2005d. The organic layer was evaporated in vacuo giving a crude product (250\u2005g) which was further purified by column chromatography, giving a primary fractioning of 11 fractions (F1\u2013F11) by using increasing polarity from hexane to ethyl acetate. F-8 (6\u2005g) was further purified by column chromatography  giving a white solid, which was recrystallized from EtOc, affording colourless crystals suitable for X-ray diffraction analysis. M.p. (from methanol): 499\u2013500\u2005K. For further physical data  for erioflorin, see Torrance et al. , C\u2014H = 0.98\u2005\u00c5 (\u2013CH2), C\u2014H = 0.99\u2005\u00c5, (\u2013CH), C\u2014H = 0.94\u2005\u00c5 (=CH2), and Uiso(H) = 1.5Ueq(CH3) and Uiso(H) = 1.2Uiso, with the exception of the O\u2014H hydrogen atom, which was refined freely, but with Uiso(H) = 1.5Uiso(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017001700/zl2693sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017001700/zl2693Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017001700/zl2693Isup3.cmlSupporting information file. DOI: 1530526CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "As a result of the presence of these ordered species, the framework changes its symmetry from P4/mmm to P21/c. The 4,4\u2032-bi\u00adpyridine guest mol\u00adecules form chains inside the 6.5 \u00d7 6.9\u2005\u00c5 pores parallel to [100] in which the mol\u00adecules inter\u00adact through \u03c0\u2013\u03c0 stacking. Ordered water mol\u00adecules form infinite hydrogen-bonded chains inside a second pore system (1.6 \u00d7 5.3\u2005\u00c5 free aperture) perpendicular to the 4,4\u2032-bi\u00adpyridine channels.The coordination polymer {[Cu(SiF These inter\u00adconnected pores are filled with two other 4,4\u2032-bi\u00adpyridine mol\u00adecules and five water mol\u00adecules  and this may be related to the fact that, in the present compound, guest mol\u00adecules fill the pores and inter\u00adact significantly with the framework atoms (see below).The 2D coordination grids are stacked along the [100] direction through the SiFs Figs. 3 and 4 \u25b8.62\u2212 show some variations : 45.29\u2005(7)\u00b0; bipy(N37\u2013N43): 30.31\u2005(7)\u00b0]. Whereas the 4,4\u2032-bi\u00adpyridine mol\u00adecules belonging to the coordination network are rather rigid between the metal atoms , the adsorbed 4,4\u2032-bi\u00adpyridine mol\u00adecules display significantly larger atomic displacement parameters [Ueq = 0.025\u2005(5)\u2005\u00c52].Four of the five water mol\u00adecules (O49 to O52) form infinite es Fig.\u00a05. The fifes Fig.\u00a05. The 4,4es Fig.\u00a05, and arees Fig.\u00a05; these iet al., 20166)(C10H8N2)2]n coordination polymer framework [CSD refcodes: GORWUF 2]\u00b78H2O}n undergoes a structural conversion when immersed in water, leading to an inter\u00adpenetrated network where SiF62\u2212 anions are shifted out of the coordination sphere of copper ions and are replaced by water mol\u00adecules [CSD refcodes: AFEHOI  of hydrated copper(II) tetra\u00adfluorido\u00adborate  was added to a refluxing aceto\u00adnitrile solution (5\u2005cm3) of 4,4\u2032-bi\u00adpyridine . After filtration, Et2O vapor was diffused into the mother liquor for seven days, and then the solvent was allowed to evaporate very slowly. A mixture of blue and violet crystals was obtained; whereas the diffraction spots of the blue crystals could not be properly indexed, the violet crystals were of very good quality and led to the structure reported on herein.An aqueous solution (5\u2005cmUiso(H) = 1.2Uiso(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989016016686/vn2118sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016016686/vn2118Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510381CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(5) ring motif. In the crystals of both compounds, mol\u00adecules are linked by pairs of N\u2014H\u22efS hydrogen bonds, forming dimers with In the title compounds, the thio\u00adsemicarbazone group adopts an extended conformation, and there is a short N\u2014H\u22efN contact present forming an  11H13N3O2S, (I), and C16H15N3O2S, (II), the thio\u00adsemicarbazone group adopts an extended conformation. The acetate ester (I) crystallizes with two independent mol\u00adecules in the asymmetric unit. In the benzoate ester (II), the planes of the two aryl rings are inclined to one another by 46.70\u2005(7)\u00b0. In both compounds, there is a short intra\u00admolecular N\u2014H\u22efN contact present, forming an S(5) ring motif. In the crystals of both compounds, mol\u00adecules are linked via pairs of N\u2014H\u22efS hydrogen bonds, forming dimers with R22(8) ring motifs. The dimers are linked by N\u2014H\u22efS and N\u2014H\u22efO hydrogen bonds, forming slabs parallel to (01-1). In (I), there are N\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions present within the slabs, while in (II), there are only N\u2014H\u22ef\u03c0 inter\u00adactions present.In the title compounds, C They display anti\u00adproliferative activity on different tumors cell lines and have been a common feature of all compounds with carcinogenic potency. A strong correlation has been found between tumor growth rate and the ribonucleoside diphos\u00adphate reductase (RDR) enzyme  ring motif \u00b0 in mol\u00adecule B of compound (I)] and S1\u2014C16\u2014N2\u2014N1 [172.2\u2005(1)\u00b0 in compound (II)]. In compound (I)A and B, respectively]. The bond lengths C11A\u2014S1A [1.692\u2005(2)\u2005\u00c5] and C11B\u2014S1B [1.680\u2005(2)\u2005\u00c5] in (I)et al., 2016syn-periplanar to C5 [C5\u2014C6\u2014C7\u2014O1 = \u221215.8\u2005(2) \u00b0] and anti-periplanar to C1 [C1\u2014C6\u2014C7\u2014O1 = 160.7\u2005(1) \u00b0]. The dihedral angle between the benzene rings in compound (II)The mol\u00adecular structure of compounds (I)f Figs. 1 and 2 \u25b8.A\u2013B dimers with an In the crystal of (I)In the crystal of (II)f Table\u00a02. As in tet al., 2016E)-4-(N-carbamo\u00adthioyl\u00adethane\u00adhydrazono\u00adyl)phenyl 4-methyl\u00adbenzoate : Thio\u00adsemicarbazide  was added to 50\u2005ml of an ethano\u00adlic solution of the 4-acetyl phenyl acetate (0.01\u2005mol) for (I)Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016018983/su5323sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989016018983/su5323Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016018983/su5323IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1519492, 1519491CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif. In the crystal, mol\u00adecules are linked by N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds forming chains propagating along the a-axis direction.The title isonicotinohydrazide derivative is planar, with an r.m.s. deviation for the fitted non-H atoms of 0.062\u2005\u00c5, and an intra\u00admolecular O\u2014H\u22efN hydrogen bond with an  13H10FN3O2, the mol\u00adecule has an E conformation with respect to the C=N bond of the hydrazone bridge. The dihedral angle between the isonicotinoyl and fluoro\u00adphenol moieties is 4.03\u2005(4)\u00b0, and an intra\u00admolecular O\u2014H\u22efN hydrogen bond generates an S(6) ring motif. In the crystal, mol\u00adecules are linked by N\u2014H\u22efN and C\u2014H\u22efN hydrogen bonds, forming chains propagating along the a-axis direction. The chains are linked by C\u2014H\u22efO hydrogen bonds, resulting in the formation of layers lying parallel to the ab plane. The crystal structure also features \u03c0\u2013\u03c0 inter\u00adactions [centroid-to-centroid distance = 3.6887\u2005(8)\u2005\u00c5].In the title compound, C The C6\u2014N2 and C7\u2014N3 bond lengths differ by 0.08\u2005\u00c5 hence; these two bonds are formally double and single bonds, respectively. The mol\u00adecule deviates slightly from planarity with an r.m.s deviation for the fitted non-hydrogen atoms of 0.062\u2005\u00c5. There is an intra\u00admolecular O2\u2014H2O\u22efN3 hydrogen bond with an S(6) ring motif present in the pyridine carboxamide moiety, and the pyridine ring (N1/C1\u2013C5) is approximately coplanar with the amide group (C6(=O1)N2) [dihedral angle = 8.25\u2005(6)\u00b0]. The isonicotinoyl moiety (N1/C1\u2013C6/O1/N2) is inclined to the fluoro\u00adphenol moiety (C8-C13/O2/F1) by 4.03\u2005(4)\u00b0.The mol\u00adecular structure of the title compound, with atom labelling, is presented in Fig.\u00a01N\u22efN1i and C4\u2014H4\u22efN1i hydrogen bonds \u2005\u00c5; Cg1 and Cg2 are the centroids of the pyridine (N1/C1\u2013C5) and phenyl (C8\u2013C13) rings, respectively; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].In the crystal, mol\u00adecules are linked by bifurcated-acceptor N2\u2014H2s Table\u00a01, leadinget al., 2016E)-N-(2-hy\u00addroxy\u00adbenzyl\u00adidene)isonicotinohydrazide skeleton revealed 86 hits. They include the isotypic crystal structures with bromide  d 6.94 , 7.32 , 7.44 , 7.85 , 8.70 , 8.81 , 11.40 , 12.39 . HR\u2013MS (ES+) C13H11FN3O2 requires 260.0835 [M\u00a0+\u00a0H]+; found 260.0830.Isonicotinic acid hydrazide  and 3-fluoro\u00adsalicyl\u00adaldehyde  were suspended in a 1:1 mixture of water and ethanol (6\u2005ml). The reaction mixture was stirred at 363\u2005K for 24\u2005h and formation of a precipitate was observed. The reaction mixture was allowed to cool to room temperature and then filtered. The isolated solid was washed with water to give the product as a white solid . Colourless rod-like crystals, suitable for X-ray diffraction analysis, were grown by slow evaporation of a solution in methanol of the title compound. Uiso(H) = 1.5Ueq(O) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017009926/su5379sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017009926/su5379Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017009926/su5379Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017009926/su5379Isup4.cmlSupporting information file. DOI: 1560196CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Cngb1 locus-encoded \u03b2-subunit of rod cGMP-gated cation channel and associated glutamic acid rich proteins (GARPs) are required for phototransduction, disk morphogenesis, and rod structural integrity. To probe individual protein structure/function of the GARPs, we have characterized several transgenic mouse lines selectively restoring GARPs on a Cngb1 knockout (X1\u2212/\u2212) mouse background. Optical coherence tomography (OCT), light and transmission electron microscopy (TEM), and electroretinography (ERG) were used to analyze 6 genotypes including WT at three and ten weeks postnatal. Comparison of aligned histology/OCT images demonstrated that GARP2 accelerates the rate of degeneration. ERG results are consistent with the structural analyses showing the greatest attenuation of function when GARP2 is present. Even 100-fold or more overexpression of GARP1 could not accelerate degeneration as rapidly as GARP2, and when co-expressed GARP1 attenuated the structural and functional deficits elicited by GARP2. These results indicate that the GARPs are not fully interchangeable and thus, likely have separate and distinct functions in the photoreceptor. We also present a uniform murine OCT layer naming nomenclature system that is consistent with human retina layer designations to standardize murine OCT, which will facilitate data evaluation across different laboratories.The  The \u03b2-subunit and GARP2 have critical roles in phototransduction, disk morphogenesis, and maintenance of outer segment structural integrity1314Cngb1 locus, these proteins are identical in sequence for 318 amino acids. GARPs are intrinsically disordered proteins161615202215In the rod photoreceptor, the CNG channel is a heterotetramer composed of three \u03b1- and one \u03b2-subunits which are arranged around a central pore781011\u2212/\u2212), results in loss of function by one month, nearly undetectable levels of CNG \u03b1-subunit by two months, and retina degeneration by four months\u2212/\u2212) also results in loss of structure and function, including disruption of disk/plasma membrane interactions\u2212/\u2212 mice occurs 4\u20135 months earlier and the levels of the CNG \u03b1-subunit are significantly lower than in X1\u2212/\u2212 mice. To further dissect individual protein structure/function of the GARPs in rods, we have characterized several new transgenic mouse models, which selectively restore the absent GARP proteins to the X1\u2212/\u2212 mouse retina. Additionally, we present a system for murine optical coherence tomography (OCT) layer designation, that conforms with recently published human OCT guidelinesKnockout of the CNG channel \u03b2-subunit, while leaving GARPs intact  and ten weeks (0.042\u2009mm\u2009\u00b1\u20090.01), but no change in FRT. Consistent with progressive retinal degeneration in X26\u2212/\u2212 mice, OCT analysis of transgenic mice showed significant reduction in ONL thickness (from 0.052\u2009mm\u2009\u00b1\u20090.01 to 0.033\u2009mm\u2009\u00b1\u20090.01) and FRT (from 0.215\u2009mm\u2009\u00b1\u20090.02 to 0.182\u2009mm\u2009\u00b1\u20090.01) over time. The effects of overexpression of G1 on the X1\u2212/\u2212 background were also assessed. X1\u2212/\u2212 G1Tg showed reduction in ONL thickness between three (0.052\u2009mm\u2009\u00b1\u20090.01) and ten weeks (0.038\u2009mm\u2009\u00b1\u20090.02), but no change in FRT. X1\u2212/\u2212 G2Tg showed a reduction in ONL thickness between three (0.051\u2009mm\u2009\u00b1\u20090.01) and ten weeks (0.019\u2009mm\u2009\u00b1\u20090.01), as well as a reduction in FRT (from 0.205\u2009mm\u2009\u00b1\u20090.02 to 0.163\u2009mm\u2009\u00b1\u20090.02). X1\u2212/\u2212 G1Tg G2Tg also showed a reduction in ONL thickness between three (0.050\u2009mm\u2009\u00b1\u20090.01) and ten weeks (0.028\u2009mm\u2009\u00b1\u20090.01), as well as a reduction in FRT (from 0.214\u2009mm\u2009\u00b1\u20090.01 to 0.176\u2009mm\u2009\u00b1\u20090.02). All of the genotypes except WT showed a reduction in ONL thickness over time. However, neither X1\u2212/\u2212 or X1\u2212/\u2212G1Tg showed a reduction in FRT, as was observed for all other genotypes.To assess the effects of the transgene alleles on retinal degeneration in X1en weeks  and 4 in\u2212/\u2212 (0.212\u2009mm\u2009\u00b1\u20090.01), X1\u2212/\u2212 G1Tg (0.207\u2009mm\u2009\u00b1\u20090.02), X26\u2212/\u2212 (0.215\u2009mm\u2009\u00b1\u20090.02), X1\u2212/\u2212 G2Tg (0.205\u2009mm\u2009\u00b1\u20090.02), and X1\u2212/\u2212 G1Tg G2Tg (0.214\u2009mm\u2009\u00b1\u20090.01) all showed reduced FRT compared to WT (0.227\u2009mm\u2009\u00b1\u20090.02). At ten weeks X1\u2212/\u2212  and X26\u2212/\u2212  retinas showed reduced ONL and FRT thickness compared to WT . X26\u2212/\u2212 (0.033\u2009mm\u2009\u00b1\u20090.01) retinas showed reduced ONL thickness compared to X1\u2212/\u2212 (0.042\u2009mm\u2009\u00b1\u20090.01) and X1\u2212/\u2212 G1Tg (0.038\u2009mm\u2009\u00b1\u20090.02). X1\u2212/\u2212 G1Tg (0.038\u2009mm\u2009\u00b1\u20090.02) showed reduced ONL thickness compared to WT (0.051\u2009mm\u2009\u00b1\u20090.01) and X1\u2212/\u2212 (0.042\u2009mm\u2009\u00b1\u20090.01), as well as reduced FRT (0.205\u2009mm\u2009\u00b1\u20090.02) compared to WT (0.218\u2009mm\u2009\u00b1\u20090.02). X1\u2212/\u2212 G2Tg (0.019\u2009mm\u2009\u00b1\u20090.01) showed reduced ONL thickness compared to WT (0.051\u2009mm\u2009\u00b1\u20090.01), X1\u2212/\u2212 (0.042\u2009mm\u2009\u00b1\u20090.01), X26\u2212/\u2212 (0.033\u2009mm\u2009\u00b1\u20090.01), X1\u2212/\u2212 G1Tg (0.038\u2009mm\u2009\u00b1\u20090.02) and X1\u2212/\u2212 G1Tg G2Tg (0.028\u2009mm\u2009\u00b1\u20090.01), as well as reduced FRT (0.163\u2009mm\u2009\u00b1\u20090.02) compared to WT (0.218\u2009mm\u2009\u00b1\u20090.02), X26\u2212/\u2212 (0.182\u2009mm\u2009\u00b1\u20090.01) and X1\u2212/\u2212 G1Tg (0.205\u2009mm\u2009\u00b1\u20090.02). X1\u2212/\u2212 G1Tg G2Tg (0.028\u2009mm\u2009\u00b1\u20090.01) showed reduced ONL thickness compared to WT (0.051\u2009mm\u2009\u00b1\u20090.01), X1\u2212/\u2212 (0.042\u2009mm\u2009\u00b1\u20090.01), X26\u2212/\u2212 (0.033\u2009mm\u2009\u00b1\u20090.01), and X1\u2212/\u2212 G1Tg (0.038\u2009mm\u2009\u00b1\u20090.02), as well as reduced FRT (0.176\u2009mm\u2009\u00b1\u20090.02) compared to WT (0.218\u2009mm\u2009\u00b1\u20090.02) and X1\u2212/\u2212 G1Tg (0.205\u2009mm\u2009\u00b1\u20090.02). Genotypes expressing GARP2 in the absence of \u03b2-subunit  had significant reduction in ONL thickness compared to those that did not express GARP2 (X1\u2212/\u2212 and X1\u2212/\u2212 G1Tg) or expressed GARP2 and \u03b2-subunit (WT).OCT also revealed between group differences in ONL thickness and FRT at each time point . At thre\u2212/\u2212, X26\u2212/\u2212 and X1\u2212/\u2212 G1Tg than in WT (p\u2009<\u20090.001). ONL thinned more rapidly in X1\u2212/\u2212 G2Tg than in WT, X1\u2212/\u2212, X26\u2212/\u2212, X1\u2212/\u2212 G1Tg, or X1\u2212/\u2212 G1Tg G2Tg. ONL thinned more rapidly in X1\u2212/\u2212 G1Tg G2Tg than in WT, X1\u2212/\u2212, or X1\u2212/\u2212 G1Tg. Therefore, the greatest rate of ONL thinning is in X1\u2212/\u2212 G2Tg. There is ONL thinning in X1\u2212/\u2212 G1Tg, but at a much slower rate than in X1\u2212/\u2212 G2Tg. Expression of both GARP1 and GARP2 in X1\u2212/\u2212 G1Tg G2Tg shows a slower rate of ONL thinning than X1\u2212/\u2212 G2Tg, but faster than X1\u2212/\u2212 G1Tg. Thus, in order of decreasing rates of thinning, the comparative rate of thinning per genotype is X1\u2212/\u2212 G2\u2009>\u2009X1\u2212/\u2212 G1Tg G2Tg\u2009>\u2009X26\u2212/\u2212\u2009>\u2009X1\u2212/\u2212 G1Tg\u2009>\u2009X1\u2212/\u2212\u2009>\u2009WT. The only difference between X26\u2212/\u2212 and X1\u2212/\u2212 G1Tg G2Tg, is that the latter expresses more GARP1 than the former. This indicates that co-expression of GARP2 along with increased GARP1 (X1\u2212/\u2212 G1Tg G2Tg) results in increased rates of thinning. However, increased expression of GARP1 without GARP2 (X1\u2212/\u2212 G1Tg) has a lower rate of thinning than endogenous expression of GARP1 with GARP2 (X26\u2212/\u2212), suggesting that GARP2 expression has the strongest effect on the rate of thinning.The rate of thinning over time was compared between groups, a measurement of the interaction between time and genotype . In gene\u2212/\u2212 and X26\u2212/\u2212 than in WT or X1\u2212/\u2212 G1Tg. The rate of FRT thinning is greater in X1\u2212/\u2212 G2Tg than WT or X1\u2212/\u2212 G1Tg. Finally, the rate of FRT thinning is greater in X1\u2212/\u2212 G1Tg G2Tg than WT or X1\u2212/\u2212 G1Tg. Considering all genotypes, the rate of thinning from fastest to slowest is X1\u2212/\u2212 G2Tg, X1\u2212/\u2212 G1Tg G2Tg, X1\u2212/\u2212, and X26\u2212/\u2212\u2009>\u2009X1\u2212/\u2212 G1Tg and WT. The only genotype that did not have faster FRT thinning than WT was X1\u2212/\u2212 G1Tg.The rate of FRT thinning  is great\u2212/\u2212, 0.039\u2009mm\u2009\u00b1\u20090.005 for X26\u2212/\u2212, 0.040\u2009mm\u2009\u00b1\u20090.003 for X1\u2212/\u2212 G1Tg, 0.042\u2009mm\u2009\u00b1\u20090.003 for X1\u2212/\u2212 G2Tg and 0.037\u2009mm\u2009\u00b1\u20090.003 for X1\u2212/\u2212 G1Tg G2Tg. At ten weeks WT ONL is 0.036\u2009mm\u2009\u00b1\u20090.002, compared to 0.032\u2009mm\u2009\u00b1\u20090.003 for X1\u2212/\u2212, 0.026\u2009mm\u2009\u00b1\u20090.003 for X26\u2212/\u2212, 0.029\u2009\u00b1\u20090.004 for X1\u2212/\u2212 G1Tg, 0.021\u2009mm\u2009\u00b1\u20090.002 for X1\u2212/\u2212 G1Tg G2Tg, and 0.025\u2009mm\u2009\u00b1\u20090.004 for X1\u2212/\u2212 G2. Similarly to OCT results, there was a significant within group difference between 3 and 10 weeks for all genotypes except WT and X1\u2212/\u2212. While OCT results did show a significant thinning for X1\u2212/\u2212 between 3 and 10 weeks, this was the smallest difference and the least statistically significant change of all of the genotypes. Additionally, there were between group differences for ONL thickness at 10 weeks. OCT results showed a significant thinning in ONL at 10 weeks in X26\u2212/\u2212, X1\u2212/\u2212 G1Tg G2Tg, and X1\u2212/\u2212 G2Tg retinas compared to WT. However, histology measurements showed a significant thinning in ONL at 10 weeks for all genotypes compared to WT. At 3 weeks, WT FRT is 0.182\u2009mm\u2009\u00b1\u20090.006, compared to 0.179\u2009mm\u2009\u00b1\u20090.005 for X1\u2212/\u2212, 0.245\u2009mm\u2009\u00b1\u20090.025 for X26\u2212/\u2212, 0.233\u2009mm\u2009\u00b1\u20090.013 for X1\u2212/\u2212 G1Tg, 0.220\u2009mm\u2009\u00b1\u20090.012 for X1\u2212/\u2212 G2Tg, and 0.200\u2009mm\u2009\u00b1\u20090.012 for X1\u2212/\u2212 G1Tg G2Tg. At 10 weeks, WT FRT is 0.205\u2009mm\u2009\u00b1\u20090.010, compared to 0.197\u2009mm\u2009\u00b1\u20090.014 for X1\u2212/\u2212, 0.190\u2009mm\u2009\u00b1\u20090.013 for X26\u2212/\u2212, 0.179\u2009mm\u2009\u00b1\u20090.011 for X1\u2212/\u2212 G1Tg, 0.201\u2009mm\u2009\u00b1\u20090.020 for X1\u2212/\u2212 G2Tg, and 0.155\u2009mm\u2009\u00b1\u20090.006 for X1\u2212/\u2212 G1Tg G2Tg. While OCT results only showed a significant FRT thinning over time in WT, X26\u2212/\u2212, X1\u2212/\u2212 G2Tg, and X1\u2212/\u2212 G1Tg G2Tg, histology measurements showed significant FRT thinning over time in all genotypes. OCT results at 10 weeks showed a significantly thinner FRT for X26\u2212/\u2212, X1\u2212/\u2212 G1Tg, X1\u2212/\u2212 G1Tg G2Tg, and X1\u2212/\u2212 G2Tg compared to WT. Similar results were observed for histology measurements, except histology did not show a difference in FRT between WT and X26\u2212/\u2212 retinas. Overall, histology measurements of ONL and FRT confirmed OCT observations. In addition, histology also showed that photoreceptor outer segments are less uniform and more disorganized in X1\u2212/\u2212, X1\u2212/\u2212 G1Tg and X1\u2212/\u2212 G1Tg G2Tg. Photoreceptor outer segments are almost completely lost in X1\u2212/\u2212 G2Tg at 10 weeks. At 10 weeks, GARP2 accelerates thinning; however GARP1 does not affect the rate of thinning and partially counteracts the effect of GARP2 in the X1\u2212/\u2212 G1Tg G2Tg hybrid.To validate OCT results, histologic analysis was performed on each genotype at three and ten weeks . At thre\u2212/\u2212, X1\u2212/\u2212 G1Tg, X1\u2212/\u2212 G2Tg, and X1\u2212/\u2212 G1Tg G2Tg retinas  images revealed structural changes as early as three weeks in X1 retinas . In WT, Cngb1) at 1 month postnatal , without the N-Cngb1 primary antibody showed no signal in any genotype.Because there is an ongoing degeneration it could not be assumed that the transgene expressed GARPs are properly localizing in photoreceptors. Therefore, we determined the localization of GARPs in WT and the transgenic animals. Using an antibody that recognizes the N-terminus of the \u03b2-subunit and GARPs . When GARP1 is overexpressed without GARP2 (X1\u2212/\u2212G1Tg) or co-expressed with GARP2 (X1\u2212/\u2212G1TgG2Tg) it was readily apparent. GARP2 was easily detected in WT, X1\u2212/\u2212G2Tg, X1\u2212/\u2212G1TgG2Tg, and X26\u2212/\u2212 mice. Protein expression is shown as the percent of GARP2 expression in WT retina  in X1\u2212/\u2212G1Tg mice and 215% (\u00b126%) in X1\u2212/\u2212G1TgG2Tg mice. GARP2 was expressed at 42% (\u00b125%) in X1\u2212/\u2212G2Tg mice, 204% (\u00b172%) in X1\u2212/\u2212G1TgG2Tg mice, and 18% (\u00b112%) in X26\u2212/\u2212 mice. Despite a 30% increase in GARP1 expression in X1\u2212/\u2212G1TgG2Tg compared to X1\u2212/\u2212G1Tg mice, this difference was not statistically significant. However, there was significantly lower expression of GARP2 in X1\u2212/\u2212G2Tg and X26\u2212/\u2212 mice compared to X1\u2212/\u2212G1TgG2Tg mice. Despite a 20% increase in GARP2 expression in X1\u2212/\u2212G2Tg mice compared to X26\u2212/\u2212 mice, this difference was not statistically significant.To compare proteins levels of channel \u03b2-subunit, GARP1, and GARP2 in the various genotypes, automated capillary-based Western analysis was performed, using an internal standard for normalization. Similar to previously published resultsT retina , lane WTT retina . While G2 flash were significantly higher than X1\u2212/\u2212 , X26\u2212/\u2212 , X1\u2212/\u2212 G1Tg , X1\u2212/\u2212 G1Tg G2Tg  and X1\u2212/\u2212 G2Tg . In addition, the X1\u2212/\u2212 a-wave was significantly higher than X1\u2212/\u2212 G2Tg, and the b-wave was significantly higher than X1\u2212/\u2212 G2Tg and X1\u2212/\u2212 G1Tg G2Tg. At 10 weeks , X26\u2212/\u2212 , X1\u2212/\u2212 G1Tg , X1\u2212/\u2212 G1Tg G2Tg  and X1\u2212/\u2212 G2Tg . These data are consistent with a negative effect of GARP2 on rod function in the absence of the \u03b2-subunit. Scotopic responses were also measured at lower intensities (0.0001\u201310\u2009cd*s/m2) and showed similar results as the saturating 25\u2009cd*s/m2 flash .Using the mouse OCT nomenclature described in \u2212/\u2212 G2Tg mice. Co-expression of GARP1 and GARP2 on the X1\u2212/\u2212 reduced this attenuation, but it was still greater than the attenuation observed in X1\u2212/\u2212 G1Tg. These results provide further evidence that the negative effect of GARP2 is dominant over GARP1, and suggests a possible interaction between GARP1 and GARP2. This also further supports the conclusion that GARP2, in the absence of the \u03b2-subunit, drives functional and structural decline in the retina. Finally, coupled with the structural data, this also suggests GARP1 and GARP2 have distinct functions in the rods.As expected, photoreceptor (a-wave) and bipolar cell function (b-wave), measured via ERG, were reduced in all genotypes compared to WT. In addition, photoreceptor and bipolar cell function (attenuated a- and b-waves in ERG) were consistent with OCT findings, with the greatest attenuation in X1\u2212/\u2212 background which increased the GARP1 levels to approximately endogenous levels of GARP2 expression. A GARP2 transgene (at endogenous levels of protein when expressed on a WT background) was also crossed onto the X1\u2212/\u2212 background. In addition, the two GARP expressing animals were then crossed to enable examination of expression of the two transgenes in the absence of the CNG \u03b2-subunit. Finally, endogenous GARP1 and GARP2 were both expressed in the X26\u2212/\u2212 mouse which only lacks the CNG \u03b2-subunit. If the two proteins have identical function one would expect identical phenotypes when expressed in various genetic backgrounds where phenotypes are discernible. Furthermore, one would expect the co-expression of both GARPs to further accelerate the thinning. The ONL in X26\u2212/\u2212 mice thins more slowly than in X1\u2212/\u2212 G2Tg.In WT mice, GARP1 is 20-fold less abundant than GARP2 and four-fold less than the CNG \u03b2-subunit\u2212/\u2212, X26\u2212/\u2212, and a G2 overexpression mouse131419\u2212/\u2212, and the G2 overexpression mouse, GARP/\u03b2-subunit expression is confined to the OS with variable OPL signal. Unsurprisingly, GARP/\u03b2-subunit expression is absent in the X1\u2212/\u2212 mouse. GARP expression in the X1\u2212/\u2212 G1Tg, X1\u2212/\u2212 G2Tg, and X1\u2212/\u2212 G1Tg G2Tg mice was confined primarily to the OS, with minimal expression in the IS and variable signal in OPL. This shows that the transgene, even when overexpressed, primarily localizes to the OS.Previous studies have examined GARP/\u03b2-subunit expression in WT, X1\u2212/\u2212 mice is ~18% of the endogenous GARP2 expression, while GARP2 expression in X1\u2212/\u2212 G2Tg mice is ~42%. This higher level of GARP2 expression could explain why the ONL in X26\u2212/\u2212 mice thins more slowly than in X1\u2212/\u2212 G2Tg. Crossing the X1\u2212/\u2212 G1Tg (185% of WT GARP2 expression) and X1\u2212/\u2212 G2Tg (42% of WT GARP2 expression) mice results in offspring that express GARP2 at ~200% of WT GARP2 levels. X1\u2212/\u2212 G1Tg mice do not have significantly faster ONL thinning than X26\u2212/\u2212, but the X1\u2212/\u2212 G1Tg G2Tg mice (with the 200% increases in GARP2 expression) do have significantly faster rates of thinning than X26\u2212/\u2212 mice. However, the increased GARP2 expression in X1\u2212/\u2212 G1Tg G2Tg is not enough to increase the rate of thinning compared to X1\u2212/\u2212 G2Tg mice, which have lower levels of GARP2. Thus, the presence of GARP1 must be slowing the rate of thinning. This also indicates differing roles for GARP1 and GARP2 and the possibility that increased expression of GARP1 is somehow involved in increasing expression of GARP2. Taken together, our results lead us to conclude that GARP1 and GARP2 are not interchangeable as they do not produce identical phenotypes, nor are they additive in effect, and thus these proteins may have distinct and separate roles in the rod photoreceptor.Total GARP2 protein expression in X26\u2212/\u2212\u2212/\u2212One possible mechanism for the acceleration of degeneration in our GARP transgenic mice could be inhibition of \u03b1-subunit transport (in the absence of the \u03b2-subunit) from IS to OS which is consistent with the significantly lower \u03b1-subunit levels found in X26\u2212/\u2212)\u2212/\u2212)Tg, 100-fold overexpressed) using a 4.4\u2009kb opsin promoter, mouse protamine poly-A construct generated by replacing the PDE6 \u03b3-subunit insertTg, construct shown in \u2212/\u2212 G1Tg G2Tg mice carrying both alleles were generated by crossing G1Tg and G2Tg transgenic mice on a homozygous X1\u2212/\u2212 background and identifying the presence of both alleles by PCR genotyping (see below). All animal lines were made congenic on a C57BL/6J background. All animal use protocols were approved by the University of Alabama at Birmingham (UAB) Institutional Animal Care and Use Committee and are consistent with the Association for Research in Vision and Ophthalmology guidelines for the use of animals in research. All animals were maintained on a standard 12/12-hour light/dark cycle, fed standard rodent chow, and housed with standard rodent bedding.An exon 1, 2 and predicted promoter Cngb1 knockout null allele  in digestion buffer consisting of 5\u2009mM EDTA, 200\u2009mM NaCl, 100\u2009mM Tris-HCl, and 0.2% SDS. Tails were digested overnight at 55\u2009\u00b0C. 100% ethanol was added to the lysate, which was then centrifuged at 16,000\u2009\u00d7\u2009g for thirty minutes, washed with 70% ethanol, centrifuged at 16,000\u2009\u00d7\u2009g for twenty minutes, and then the DNA pellet was dissolved in TE buffer, pH 8.0. PCR was performed using the following cycling parameters: 94\u2009\u00b0C denaturation, five minutes, for one cycle; thirty five cycles of 94\u2009\u00b0C, thirty seconds; for GARP1, 58\u2009\u00b0C, thirty seconds; for GARP2, 62\u2009\u00b0C, forty five seconds; 72\u2009\u00b0C, fifty seconds; and one cycle of 72\u2009\u00b0C for seven minutes. Primers sequences for X26TM 1.4 software  rectangular volume scan of 1.4\u2009mm diameter with one thousand A-scans/B-scan, one hundred B-scans/volume, and one frame/B-scan or (scan parameter two) rectangular volume scan of 1.6\u2009mm in diameter with one thousand A-scans/B-scan, three B-scans/volume, and forty eight frames/B-scan. The one thousand A-scan frames collected in parameter two were averaged to reduce noise and increase signal. These averaged images were then converted to bmp files. To determine the ONL thickness, the difference in distance between the outer plexiform layer (OPL) and the external limiting membrane (ELM) was calculated. To determine the FRT, the difference in distance between the inner limiting membrane (ILM) and retinal pigment epithelium (RPE) was calculated. Measurements of ONL thickness and FRT were performed with Bioptigen Diver 2.4 software on retinal OCT images, captured using scan parameter one, of three week and ten week old mice at eight equidistant eccentricities  was performed to visualize the posterior segment in living mice. The Bioptigen OCT instrument has a transverse resolution of 2.5\u2009\u03bcm and an axial resolution of 1.6\u2009\u03bcm. Animals were anesthetized with intraperitoneal injection of ketamine/xylazine  at 100\u2009mg/kg and 10\u2009mg/kg body weight, respectively. Pupils were dilated using 1% tropicamide  and 0.5% proparacaine , and artificial tears  were applied frequently, with saline wash throughout to maintain corneal clarity. Scans were captured with the beam centered on the optic nerve. Both horizontal and vertical linear scans were obtained with Bioptigen InVivoVuericities , in one ricities . ONL thiricities  were takLinear regression mixed models were used to assess ONL and FRT in five groups representing each transgenic line and WT mice. Linear regression mixed models were used to account for the within-animal correlation that occurs when multiple observations are taken from the same subject. First, we examined whether the mean ONL and FRT across the entire retina differed within each transgenic line group over time (three weeks vs. ten weeks). T-tests were also used to examine this association at each eccentricity . Next, we examined whether there were any between-group differences at each time point. Finally, a statistical interaction term was added to the model to assess if the changes over time differed by transgenic group. Separate linear mixed models were used to assess mean ONL and mean FRT. For five of the animals, data was collected from the same animal at both time points. Therefore, two separate analyses were employed to account for the paired nature of these measurements. First, data collected at ten weeks was treated as independent observations from those collected at time three. Second, the analyses were re-run excluding data collected at ten weeks for just those five animals. In both approaches, the pattern of results was similar. The results from the first analysis are presented; however, differences in results are noted where applicable. Adjustment of p-values for multiple comparisons was not performed. P-values\u2009<\u20090.05 were considered statistically significant.Cngb1; QEPPEPKDPPKPPGC) (1:50)Morphologic analysis was performed as previously describedCngb1; QEPPEPKDPPKPPGC) was used (1:500) to detect expression of the \u03b2-subunit and GARP2. N-Cngb1 was generated in rabbit and affinity purified . Data analysis was performed using the Compass Software (ProteinSimple) and quantitation was determined by normalizing the area under the curve of the \u03b2-subunit and GARP2 peaks by the area under the curve of the ProteinSimple internal standard peak. Representative computer generated electerophoretic images were generated by the Compass Software. Images shown contain information from capillaries run over multiple trials. The computer generated electrophoretic images displayed larger product size than is normally observed for these proteins. The very low pI of the proteins is likely the basis for the altered migration, which is even more pronounced in the capillary than is observed in an acrylamide gelWestern analysis on blots for GARP1 were performed as previously described2 and 25\u2009cd*s/m2 were delivered through a Ganzfeld dome on an Ocuscience ERG  instrument manufactured for functional analysis of animal eyes. ERG data, including time/response and waveforms, were viewed using proprietary ERGView 4.860\u2009A software and analyzed after extraction into Microsoft Excel 2013 (ver. 15.0.4763.1003). Standard t-tests were used to analyze differences in the maximum saturating a- and b-wave response (\u03bcV) between genotypes at each light intensity.Scotopic ERG responses were measured at 6 different intensities of light in each genotype at 3 weeks and 10 weeks of age. Mice to be used for full-field ERG analysis were dark adapted overnight, sedated with 3% isoflurane in a closed chamber, and anesthesia was maintained at 2% via a certified isoflurane vaporizer . Eyes were anesthetized with proparacaine drops  and pupils dilated with topical phenylephrine HCL and tropicamide . Only eyes receiving light stimuli were dilated. Methylcellulose 2.5%  was applied to the corneal surface as well as to the contact lens placed on top of the silver-embedded recording electrode. The reference and ground electrodes were stainless steel subdermal needles placed in the cheek and lower back, respectively. During recordings the equipment and animal were enclosed in a Faraday cage and body temperature maintained at 37\u2009\u00b0C by a digital heating pad placed under the animal. Defined light pulses between 0.1\u2009cd*s/mHow to cite this article: DeRamus, M. L. et al. GARP2 accelerates retinal degeneration in rod cGMP-gated cation channel \u03b2-subunit knockout mice. Sci. Rep.7, 42545; doi: 10.1038/srep42545 (2017).Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations."}
{"text": "The di\u00adhydro\u00adpyrimidine ring adopts a twist-boat conformation while the quinone ring is slightly non-planar. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. In addition, a short inter\u00admolecular S\u22efN contact occurs. 24H18N2O4S, crystallizes in the ortho\u00adrhom\u00adbic P212121 space group, indicating the existence of only one enanti\u00adomer with an S configuration of the chiral center in the crystal phase. The di\u00adhydro\u00adpyrimidine ring adopts a twist-boat conformation while the quinone ring is slightly non-planar. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. In addition, a short inter\u00admolecular S\u22efN contact of 3.250\u2005(3)\u2005\u00c5 indicates an inter\u00adaction between the S atom and the \u03c0-system of the thia\u00adzole ring.The title compound, C It was expected that the reaction would proceed with substitution of one or both chlorine atoms and the formation of a thia\u00adzole ring in the product 3  compounds that can be modified easily depending on the starting materials used during the reaction  and 0.458\u2005(2)\u2005\u00c5, respectively. Such a conformation is common for 1,6-di\u00adhydro\u00adaromatic heterocycles  and \u2212160.5\u2005(3)\u00b0, respectively].The di\u00adhydro\u00adpyrimidine ring adopts a twist-boat conformation with puckering parameters  contact of 3.250\u2005(3)\u2005\u00c5  indicates an inter\u00adaction between the S atom and the \u03c0-system of the thia\u00adzole ring  was added to a solution of 2,3-di\u00adchloro\u00adnaphthalene-1,4-dione  in DMF (20\u2005mL) and the mixture was kept under reflux for 3\u2005h. After that, the reaction mixture was cooled, and the precipitated solid product was filtered off and purified via recrystallization from MeOH:DMF:H2O (2:2:1) to give product 3 in the form of dark-red crystals in 78% yield (0.35\u2005g), m.p. 520.3\u2013 522.0\u2005K.Ethyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetra\u00adhydro\u00adpyrim\u00adid\u00adine-5-carboxyl\u00adate Uiso(H) = nUeq(C) .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018000117/zq2240sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018000117/zq2240Isup2.hklStructure factors: contains datablock(s) I. DOI: 1814348CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "EXE) is an endocrine therapy commonly used by postmenopausal women with hormone\u2010responsive breast cancer due to its potency in inhibiting aromatase\u2010catalyzed estrogen synthesis. Preliminary in\u00a0vitro studies sought to identify phase I EXE metabolites and hepatic cytochrome P450s (CYP450s) that participate in EXE biotransformation. Phase I metabolites were identified by incubating EXE with HEK293\u2010overexpressed CYP450s. CYP450s 1A2, 2C8, 2C9, 2C19, 2D6, 3A4, and 3A5 produce 17\u03b2\u2010dihydroexemestane (17\u03b2\u2010DHE), an active major metabolite, as well as two inactive metabolites. 17\u03b2\u2010DHE formation in pooled human liver microsomes subjected to isoform\u2010specific CYP450 inhibition was also monitored using tandem mass spectrometry. 17\u03b2\u2010DHE production in human liver microsomes was unaffected by isoform\u2010specific inhibition of CYP450s 2A6, 2B6, and 2E1 but decreased 12\u201339% following inhibition of drug\u2010metabolizing enzymes from CYP450 subfamilies 1A, 2C, 2D, and 3A. These results suggest that redundancy exists in the EXE metabolic pathway with multiple hepatic CYP450s catalyzing 17\u03b2\u2010DHE formation in\u00a0vitro. To further expand the knowledge of phase I EXE metabolism, the impact of CYP450 genetic variation on 17\u03b2\u2010DHE formation was assessed via enzyme kinetic parameters. Affinity for EXE substrate and enzyme catalytic velocity were calculated for hepatic wild\u2010type CYP450s and their common nonsynonymous variants by monitoring the reduction of EXE to 17\u03b2\u2010DHE. Several functional polymorphisms in xenobiotic\u2010metabolizing CYP450s 1A2, 2C8, 2C9, and 2D6 resulted in deviant enzymatic activity relative to wild\u2010type enzyme. Thus, it is possible that functional polymorphisms in EXE\u2010metabolizing CYP450s contribute to inter\u2010individual variability in patient outcomes by mediating overall exposure to the drug and its active metabolite, 17\u03b2\u2010DHE.Exemestane ( Overall, glucuronidation (Vmax/KM) of 17\u03b2\u2010DHE in the HLM panel was 36\u2010fold lower in UGT2B17\u2010null homozygotes (*2/*2) compared to wild\u2010type homozygotes (*1/*1) , such as the CYP450s, can lead to genotype\u2010dependent variability in clinical responses for certain drugs , Tokyo Chemical Industry Co.  or Sigma\u2010Aldrich . Thin\u2010layer chromatography plates and silica columns used to purify the synthesized steroids were purchased from Bonna\u2010Agela Technologies Inc.  and Yamazen Corp. , respectively. Variant CYP450 overexpression vectors were made using a QuikChange II Site\u2010Directed Mutagenesis Kit from Agilent , as well as oligonucleotides manufactured by Integrated DNA Technologies . Negative control baculosomes, SuperScript II First\u2010Strand Synthesis System for RT\u2010PCR, cell culture medium, fetal bovine serum, penicillin/streptomycin, and G418 were acquired from Invitrogen . Choice\u2010Taq polymerase was purchased from Denville Scientific . LC/MS grade organic solvents, tris base, glycine, tetramethylethylenediamine (TEMED), ammonium persulfate (APS), sodium dodecyl sulfate (SDS), SuperSignal West Femto Maximum Sensitivity Substrate, Lipofectamine 2000, oligo(dT) primer, Pierce BCA protein assay kit, PVDF membranes, and monoclonal HRP\u2010conjugated V5 epitope antibody  were procured from Thermo Fisher Scientific . Nonfat dry milk used as a blocking agent for Western blotting was prepared by BioRad . The nicotinamide adenine dinucleotide phosphate (NADPH) regeneration system included in kinetic assays was purchased from Corning . Ampicillin, dithiothreitol (DTT), Tween 20, and acrylamide/bis\u2010acrylamide solution were acquired from Sigma\u2010Aldrich . Pooled mixed gender liver microsomes from 50 human donors were obtained from XenoTech . The ethnic composition of the pooled hepatic microsomes was 84% Caucasian, 8% Hispanic, 6% African American, and 2% Asian. (\u2010)\u2010N\u20103\u2010benzylphenobarbital (NBP) is a product of Cypex Ltd , whereas all other compounds used for CYP450 isoform\u2010specific inhibition were obtained from Sigma\u2010Aldrich.EXE and its phase I metabolites were synthesized at Washington State University using previously published protocols  Variation Viewer . Search 20 was used to prime reverse transcription of pooled hepatic total RNA from five human donors (Penn State Cancer Institute Biorepository). The resultant first\u2010strand cDNA was further amplified using CYP450 isoform\u2010specific primers and Taq polymerase. cDNA encoding wild\u2010type CYP450s 1A2, 2C8, 2C9, 2C19, 2D6, 3A4, or 3A5 was introduced into the pcDNA3.1/V5\u2010His\u2010TOPO expression vector for stable overexpression in mammalian cells. CYP2D6*2 and CYP2C19*1B cDNA were also amplified from pooled human liver RNA. Additional constitutive overexpression vectors encoding nonsynonymous variants with MAF > 0.01 were produced for CYP450s 1A2, 2C8, 2C9, 2C19, and 3A4 via site\u2010directed mutagenesis (SDM) using wild\u2010type plasmid as template. Two common CYP2D6 haplotypes were likewise derived from the CYP2D6*2 overexpression vector through SDM. Oligonucleotide pairs used to amplify wild\u2010type CYP450 cDNA or prime mutagenesis are detailed in Data Oligo(dT)\u03bcg/mL G418 selective pressure in DMEM supplemented with 4.5\u00a0g/L glucose, l\u2010glutamine, 110\u00a0mg/L sodium pyruvate, 10% FBS, and penicillin/streptomycin. Data Each expression vector was transformed into chemically competent BL21. Transformants were then grown overnight on ampicillin selection plates at 37\u00b0C. Sanger sequencing was used for sequence confirmation prior to transfecting HEK293 with overexpression plasmids using Lipofectamine 2000 per the manufacturer instructions. Transfected HEK293 were grown for at least 3\u00a0weeks under 700\u00a0\u03bcL reaction contained 2.5\u00a0mmol/L EXE substrate, 3\u00a0\u03bcL NADPH regeneration system, and 20\u00a0\u03bcg of microsomal protein from a wild\u2010type CYP450\u2010overexpressing HEK293 cell line in phosphate\u2010buffered saline (PBS), pH 7.4. Similar incubations were conducted to assess background activity of endogenous metabolizing enzymes in non\u2010transfected HEK293, as well as commercially available negative control baculosomes. These incubations included 100\u00a0\u03bcM EXE, 50\u00a0\u03bcg of microsomes, or 50\u00a0\u03bcg of baculosomes in addition to PBS, pH7.4, and an NADPH regeneration system. Enzymatic incubations were terminated with 50\u00a0\u03bcL of ice\u2010cold acetonitrile before centrifugation at 13,200g for 15\u00a0min at 4\u00b0C. The resulting supernatant was analyzed by ultra\u2010pressure liquid chromatography paired with tandem mass spectrometry (UPLC/MS/MS) on a Waters ACQUITY platform configured with a 0.2\u00a0\u03bcm inline filter preceding a 1.7\u00a0\u03bcm ACQUITY UPLC BEH C18 column . The UPLC gradient used to separate EXE and its phase I metabolites has been described previously , 17\u03b1\u2010DHE (m/z 299.14 \u2192 135.07), 17\u03b2\u2010DHE (m/z 299.20 \u2192 135.13), and 6\u2010HME (m/z 312.89 \u2192 158.98). 0.01\u00a0sec dwell time was optimal for all four compounds, whereas 25\u00a0V of collision energy was used for EXE and 6\u2010HME. 20\u00a0V of collision energy was used for 17\u03b1\u2010 and 17\u03b2\u2010DHE. An additional non\u2010targeted screening for phase I EXE metabolites was performed using UPLC/MS to detect positively charged molecular ions with m/z ranging from 100 to 450. The identity of all metabolites observed was verified by comparing the observed retention times and m/z with those of purified standards.CYP450\u2010derived phase I EXE metabolites were identified in 45\u2010min incubations performed at 37\u00b0C. Each 50\u2010\u03b2\u2010DHE production was measured in 45\u2010min incubations at 37\u00b0C in PBS, pH 7.4 with varying concentrations of EXE (25\u20132500\u00a0\u03bcmol/L). Each reaction included 20\u00a0\u03bcg of microsomal protein from CYP450\u2010overexpressing HEK293, as well as an NADPH regeneration system. The chosen incubation length and protein concentration fell within the linear range of EXE reduction velocity curves for the seven wild\u2010type CYP450s assayed (data not shown). Cold acetonitrile (50\u00a0\u03bcl) was used to terminate each reaction. After centrifugation for 15\u00a0min at 4\u00b0C at 13,200g, 17\u03b2\u2010DHE formation was monitored in the supernatant according to a previously established UPLC/MS/MS method and quantitated against a standard curve constructed of known 17\u03b2\u2010DHE concentrations . Furafylline (1\u00a0\u03bcmol/L) was used to inhibit CYP1A2, whereas 0.5\u00a0\u03bcmol/L tranylcypromine (TCP) and 10\u00a0\u03bcmol/L thioTEPA inhibited CYPs 2A6 and 2B6, respectively. Other compounds used to systematically inhibit hepatic CYP450s included 0.5\u00a0\u03bcmol/L montelukast (CYP2C8 inhibitor), 1\u00a0\u03bcmol/L sulfaphenazole (CYP2C9 inhibitor), 0.5\u00a0\u03bcmol/L NBP (CYP2C19), 1\u00a0\u03bcmol/L quinidine (CYP2D6 inhibitor), 5\u00a0\u03bcmol/L clomethiazole (CYP2E1 inhibitor), and 1\u00a0\u03bcmol/L ketoconazole (CYP3A inhibitor). Initial dosages were selected from the literature and then further titrated to determine the lowest dose producing maximum isoform\u2010specific inhibition  and analyzed by UPLC/MS/MS using the aforementioned method. A negative control reaction was run in parallel and received ethanol vehicle rather than inhibitor. Organic solvent constituted less than 1% of each incubation.Reduction of EXE to 17KM and relative Vmax values were calculated in GraphPad Prism 6 according to the Michaelis\u2013Menten equation\u00a0. Vmax is expressed as pmol\u00a0min\u22121\u00a0mg\u22121 and was normalized to total protein content to account for differences in CYP450 expression between cell lines as determined by Western blot analysis. Two\u2010sided unpaired t\u2010tests were used to compare the wild\u2010type catalytic activity of CYP450s 1A2 and 3A4 to their respective variants. Wild\u2010type CYP450s 2C8, 2C9, 2C19, and 2D6 were compared to their nonsynonymous variants using one\u2010way ANOVA supplemented with Dunnett's multiple comparison test. In all instances, the threshold for statistical significance was set at a two\u2010tailed P\u00a0<\u00a00.05. The percent change in 17\u03b2\u2010DHE formation associated with each inhibitor in pooled HLM was likewise calculated in GraphPad Prism 6. An uninhibited reaction receiving vehicle was considered maximum catalytic activity for the purposes of comparison. All experimental results represent triplicate assays performed independently.\u03b2\u2010DHE. Low levels of 6\u2010HME and 17\u03b1\u2010DHE formation were observed for all CYPs studied. In all cases, formation of the 17\u03b1\u2010dihydroexemestane (17\u03b1\u2010DHE) and 6\u2010hydroxymethylandrosta\u20101,4,6\u2010triene\u20103,17\u2010dione (6\u2010HME) metabolites exceeded the minimum threshold of detection. No EXE metabolite formation was observed in incubations using microsomes from the parent HEK293 cell line  followed by CYP2C8 (KM\u00a0=\u00a00.66\u00a0\u00b1\u00a00.10\u00a0mmol/L), CYP3A5 (KM\u00a0=\u00a00.69\u00a0\u00b1 0.18\u00a0mmol/L), CYP1A2 (KM\u00a0=\u00a00.74\u00a0\u00b1\u00a00.5\u00a0mmol/L), and CYP3A4 (KM\u00a0=\u00a00.83\u00a0\u00b1\u00a00.16\u00a0mmol/L) . CYP1A2 catalyzed 17\u03b2\u2010DHE production at a rate of 61\u00a0\u00b1\u00a017\u00a0pmol\u00a0min\u22121\u00a0mg \u22121 followed by CYP2C19 (51\u00a0\u00b1\u00a08\u00a0pmol\u00a0min\u22121\u00a0mg \u22121) and CYP2D6 (49\u00a0\u00b1\u00a03\u00a0pmol\u00a0min\u22121\u00a0mg \u22121). Catalytic velocities for CYP450s 3A4 and 3A5 were not significantly different (39\u00a0\u00b1\u00a07 and 36\u00a0\u00b1\u00a04\u00a0pmol\u00a0min\u22121\u00a0mg \u22121). Intrinsic clearance (Vmax/KM) was calculated for each wild\u2010type enzyme as an indication of its overall catalytic activity against EXE. CYP2C8 exhibited the highest intrinsic clearance value (194\u00a0nL\u00a0min\u22121\u00a0mg\u22121) followed by CYP2D6 (86\u00a0nL\u00a0min\u22121\u00a0mg\u22121), CYP1A2 (82\u00a0nL\u00a0min\u22121\u00a0mg\u22121), CYP2C19 (55\u00a0nL\u00a0min\u22121\u00a0mg\u22121), CYP3A5 (52\u00a0nL\u00a0min\u22121 mg\u22121), and CYP3A4 (47\u00a0nL\u00a0min\u22121\u00a0mg\u22121). In addition to having the slowest rate of EXE reduction, CYP2C9 also exhibited the lowest overall catalytic activity against EXE substrate (27\u00a0nL\u00a0min\u22121\u00a0mg\u22121).Representative kinetic curves of 17In all, 23 nonsynonymous polymorphisms with MAF\u00a0>\u00a00.01 were detected using the NCBI Variation Viewer to search for common variants in hepatic CYP450s involved in xenobiotic metabolism. Four polymorphisms of interest were identified for CYP2C9. Two variants were gleaned for CYP2C19, whereas a single variant was reported for both CYP450s 1A2 and 3A4. No variants matching the search criteria were listed for CYP3A5. Variation Viewer search filters returned four common single nucleotide polymorphisms (SNPs) in CYP2C8. In the present study, two of the CYP2C8 polymorphisms were investigated as a single haplotype (CYP2C8*3). In all, 11 nonsynonymous polymorphisms occur in CYP2D6 at > 1%. Although CYP2D6 is notoriously polymorphic, only a handful of common haplotypes are associated with clinically relevant alterations in drug metabolism Zhou . For thiVmax was comparable between wild\u2010type CYP1A2 and CYP1A2Ser298Arg, the variant enzyme exhibited significantly increased affinity for EXE with KM values of 0.74\u00a0\u00b1\u00a00.5 and 0.59\u00a0\u00b1\u00a00.2\u00a0mmol/L, respectively. No notable differences were observed in affinity between wild\u2010type CYP450s 2C8, 2C9, 2C19, or 3A4 and their respective variants (Table\u00a0KM\u00a0=\u00a00.95\u00a0\u00b10.10\u00a0mmol/L) and CYP2D6*10 (KM\u00a0= 1.04\u00a0\u00b1\u00a00.01\u00a0mmol/L) were both associated with decreased affinity relative to wild\u2010type CYP2D6 (KM\u00a0=\u00a00.57 \u00b1\u00a00.03\u00a0mmol/L). The CYP2C8*2 and CYP2C8*4 polymorphisms were associated with 2.2 and 1.7\u2010fold increases in velocity of EXE reduction compared to wild\u2010type. CYP2C9*8 and CYP2C9*9 variants were likewise associated with increased rates of 17\u03b2\u2010DHE formation (Vmax\u00a0=\u00a073\u00a0\u00b1\u00a013 and 116\u00a0\u00b1\u00a013 versus 26\u00a0\u00b1\u00a00.6 pmol min\u22121\u00a0mg\u22121 for wild\u2010type). The Vmax for EXE reduction by CYP2D6*2 (23\u00a0\u00b1\u00a00.6\u00a0pmol\u00a0min\u22121\u00a0mg \u22121) is 53% lower than that of wild\u2010type CYP2D6 (49\u00a0\u00b1\u00a03 pmol\u00a0min\u22121\u00a0mg \u22121). Vmax values were comparable between CYP2C19 and its variants CYP2C19Ile331Val and CYP2C19Glu92Asp. No significant difference in Vmax was observed between wild\u2010type CYP3A4 and CYP3A4Arg162Gln .Although \u03b2\u2010DHE production . Similar results were obtained when either thioTEPA or clomethiazole were included to chemically inhibit CYP2B6 (112.5\u00a0\u00b1\u00a08.3% control activity) or CYP2E1 (97.3\u00a0\u00b1\u00a05.3% control activity), respectively. Inhibition of CYP2D6 decreased EXE reduction by 27%, whereas furafylline\u2010induced CYP1A2 inhibition reduced formation of the active 17\u03b2\u2010DHE metabolite by 19%.In incubations of EXE with pooled mixed gender HLMs, inhibition of CYP3A isoforms with ketoconazole resulted in a 39% decrease in 17ion Fig.\u00a0. Isoform\u03b2\u2010DHE represents a major metabolic pathway for this commonly prescribed aromatase inhibitor . CYPs 3A4 and 3A5 exhibited intermediate intrinsic clearance values in the present study , but the literature indicates that CYP3A isoforms are well expressed in the liver comprising 30% of total CYP450 content and accounting for nearly 55% of xenobiotic metabolism (Chang and Kam \u22121\u00a0mg\u22121) was second only to that of CYP2C8 (194\u00a0nL\u00a0min\u22121\u00a0mg\u22121) in kinetic assays. CYP2D6 is estimated to account for 30% of drug metabolism despite constituting only 2% of total hepatic CYP450 content (Chang and Kam INT\u00a0=\u00a082\u00a0nL\u00a0min\u22121\u00a0mg\u22121), accounts for only 2% of overall CYP450\u2010mediated xenobiotic metabolism in human liver  in the presence of the isoform\u2010specific inhibitor ketoconazole suggests that CYP3As are the major hepatic CYP450s responsible for EXE reduction in human liver microsomes  in the present study. CYP1A1 expression, in turn, is low in human liver diminishing the likelihood that it is a key participant in phase I EXE metabolism . Despite its high incidence in African populations (MAF\u00a0=\u00a00.0893), a three\u2010dimensional structure examining conformational changes in CYP1A2 arising from arginine substitution is currently unavailable , CYP2C8Arg139Lys,Lys399Arg (*3), and CYP2C8Ile264Met (*4) are comparable to wild\u2010type CYP2C8 in affinity for EXE substrate in\u00a0vitro. Kaspera et\u00a0al.  and 6\u2010hydroxyl\u2010 (M\u201023) cerivastatin metabolites. Although E.\u00a0coli\u2010expressed CYP2C8*2 yielded individual Vmax values similar to wild\u2010type CYP2C8 for M\u20101 and M\u201023 formation, a 53% increase in the sum of cerivastatin metabolite clearance was noted . Kaspera et\u00a0al.  and CYP2C9Ile359Leu (*3) were similar to those of wild\u2010type CYP2C9. The CYP2C9*2 and *3 polymorphisms are relatively common (MAF\u00a0>\u00a00.01) in South Asian, European, and Hispanic populations (see Data Arg150His (*8) and CYP2C9His251Arg (*9) polymorphic protein reduced EXE to 17\u03b2\u2010DHE 2.8\u2010 and 4.5\u2010fold faster than wild\u2010type CYP2C9, respectively. The CYP2C9*8 allele also increased clearance of the antidiabetic tolbutamide in\u00a0vitro  relative to wild\u2010type CYP2D6 due to significant decreases in affinity and 17\u03b2\u2010DHE formation rate. Sakuyama et\u00a0al.  increased the KM value for EXE substrate by 82% causing a 56% decrease in clearance compared to CYP2D6*1. CYP2D6*10 is highly prevalent in Asians and has previously been associated with decreased catalytic activity in\u00a0vitro  is common in individuals of African heritage and is likewise considered a reduced function allele  and production of the major active metabolite 17\u03b2\u2010DHE (Vmax) indicate that EXE metabolism by common allelic variants of CYP2C19 and CYP3A4 is comparable to that of their respective wild\u2010type CYP450s. The neutral effect of the CYP2C19Ile331Val (*1B) polymorphism on EXE reduction confirms prior observations of equivalent catalytic activity for the CYP2C19*1A and *1B alleles  did not directly impact 17\u03b2\u2010DHE formation, it cosegregates with approximately 20% of CYP2C19*2 poor metabolizing alleles in Caucasians  polymorphism does not appreciably impact EXE metabolism. However, kinetic studies of the variant enzyme with additional substrates are needed to confirm its overall effect on CYP3A4 activity.Kinetic parameters measuring substrate affinity (\u03b1\u2010DHE, as well as the active metabolite 17\u03b2\u2010DHE. Earlier studies suggested that 17\u03b2\u2010DHE may partially determine overall drug exposure by acting as an androgen agonist, contributing to estrogen blockade through aromatase inhibition, and by serving as a gateway to phase II conjugation and excretion (Ariazi et\u00a0al. \u03b2\u2010DHE formation or clearance may contribute to inter\u2010individual variation in the overall therapeutic efficacy of EXE by altering a major metabolic pathway. This possibility is bolstered by the observation that three of the variant CYP450s included in this study had altered affinity for EXE substrate leading to differential 17\u03b2\u2010DHE production while five variants had deviant catalytic rates of EXE reduction. To our knowledge, this is the first study to report the impact of common nonsynonymous polymorphisms in CYP450s on EXE reduction to its 17\u03b2\u2010DHE metabolite. A previous in\u00a0vitro study demonstrated the capacity of genetic variation to alter EXE metabolism by the cytosolic ketosteroid reductases CBR1 and AKR1C1\u20104 (Platt et\u00a0al. The present in\u00a0vitro study augments existing pharmaceutical knowledge by examining the role of hepatic CYP450s in the metabolism of EXE, a widely used endocrine therapy for hormone\u2010responsive breast cancer. Qualitative enzymatic incubations with EXE confirm that multiple hepatic monoxygenases from CYP450 families 1, 2, and 3 catalyze the production of 6\u2010HME, 17There are no conflicts of interest.Data S1. Digital Content 1.doc.Click here for additional data file.Data S2. Digital Content 2.doc.Click here for additional data file.Data S3. Digital Content 3.doc.Click here for additional data file.Data S4. Digital Content 4.doc.Click here for additional data file."}
{"text": "The title crystal is a co-crystal with the 1,8-naphthyridine derivative crystallizing with one mol\u00adecule of succinimide per formula unit. In the crystal, the two mol\u00adecules are mutually linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds. The packing is consolidated by C\u2014H\u22ef hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions. 17H13Br2N3O\u00b7C4H5NO2, is a co-crystal of N-benzamide and pyrrolidine-2,5-dione (succinimide). The benzamide mol\u00adecule exhibits pseudo-mirror symmetry, with an r.m.s. deviation of the non-H atoms of 0.09\u2005\u00c5 (except for the two Br atoms). The angle between the least-squares planes of the two mol\u00adecules is 26.2\u2005(2)\u00b0. In the crystal, the two mol\u00adecules are mutually linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds. The packing is consolidated by C\u2014H\u22ef hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions.The title compound, C The naphthyridine ring system makes a dihedral angle of 2.2\u2005(2)\u00b0 with the benzene ring and is oriented at an angle of 26.2\u2005(2)\u00b0 relative to the succinimide. The conformation of the C=O and the N\u2014H bonds of the amide segment are anti to one another, similar to that reported for benzamide moiety in N-{4-[(6-chloro\u00adpyridin-3-yl)-meth\u00adoxy]phen\u00adyl}-2,6-di\u00adfluoro\u00adbenzamide \u2005\u00c5 , forming a three-dimensional supra\u00admolecular network N\u2014H\u22efN bond bifurcated Table\u00a01. In the rk Fig.\u00a03.et al., 2016et al., 2013In the Cambridge Structural Database benzamide  were added to an dry aceto\u00adnitrile (30\u2005ml) solution under nitro\u00adgen atmosphere. The mixture was refluxed at room temperature in the presence of light with a 250\u2005W infrared lamp for 4\u2005h. Excess solvent was removed and the crude product was purified by column chromatography using di\u00adchloro\u00admethane/methanol (120:1) as the mobile phase to give a light-yellow powder . Crystals suitable for X-ray analysis were obtained by slow diffusion of a di\u00adchloro\u00admethane solution at ambient temperature. Several cycles of purification by chromatography were used to reduce the amount of succinimide.Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for all other H atoms, and with N\u2014H = 0.86\u2005\u00c5, Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016019034/wm5334sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016019034/wm5334Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016019034/wm5334Isup3.cmlSupporting information file. DOI: 1519551CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atoms within N2S2 donor sets because of the presence of chelating thio\u00adsemicarbazone anions. Supra\u00admolecular chains are found in the crystal owing to the formation of thio\u00adamide-N\u2014H\u22efS(thione) hydrogen bonds and eight-membered thio\u00adamide {\u22efHNCS}2 synthons.The title thio\u00adsemicarbazone compound features tetra\u00adhedrally coordinated Zn II complex, [Zn(C19H20N3OS)2] {systematic name: bis\u00ad[(N-ethyl-N\u2032-{(Z)-[(2E)-3-(4-meth\u00adoxy\u00adphen\u00adyl)-1-phenyl\u00adprop-2-en-1-yl\u00adidene]amino}\u00adcarb\u00adam\u00adim\u00adid\u00ado\u00adyl)sulfanido]zinc(II)}, features a tetra\u00adhedrally coordinated ZnII ion within an N2S2 donor set provided by two N,S-chelating thio\u00adsemicarbazone anions. The resulting five-membered Zn,C,N2,S chelate rings adopt different conformations, i.e. almost planar and an envelope with the Zn atom being the flap atom. The configuration about the imine bond within the chelate ring is Z but those about the exocyclic imine and ethyl\u00adene bonds are E. In the crystal, supra\u00admolecular [100] chains mediated by thio\u00adamide-N\u2014H\u22efS(thione) hydrogen bonds and eight-membered thio\u00adamide {\u22efHNCS}2 synthons are observed. A range of inter\u00adactions, including C\u2014H\u22efO, C\u2014H\u22ef\u03c0, C\u2014H\u22ef\u03c0(chelate ring) and \u03c0(meth\u00adoxy\u00adbenzene)\u2014\u03c0(chelate ring) consolidate the packing. The Hirshfeld surface analysis performed on the title complex also indicates the influence of the inter\u00adactions involving the chelate rings upon the packing along with the more conventional contacts.The title Zn R1R2C=N\u2014N(R3)\u2014C(=S)NR4R5 for R1\u20135 = H/alk\u00adyl/aryl, are numerous and multi-functional. Their preparation is often facile, being formed from the condensation reaction between an aldehyde (or a ketone) with the amine group of a thio\u00adsemicarbazide precursor. In the same way, the diversity in ligand construction ensures a rich coord\u00adination chemistry \u00b0 for the S1\u2014Zn\u2014N3 chelate angle to 127.92\u2005(4)\u00b0 for S1\u2014Zn\u2014S2. The assignment of four-coordinate geometries can be qu\u00adanti\u00adfied by comparing the calculated value of \u03c44, in this case 0.74, with the ideal values for an ideal tetra\u00adhedron, i.e. 1.00, and perfect square-planar geometry, i.e. 0.00 2 chelate rings, and these adopt different conformations. Whereas, the  ring is almost planar (r.m.s. deviation = 0.0325\u2005\u00c5), the  chelate ring is best described as an envelope with the Zn atom lying 0.205\u2005(5)\u2005\u00c5 out of the plane of the remaining four atoms (r.m.s. deviation = 0.0011\u2005\u00c5). The dihedral angle between the mean planes through the chelate rings is 79.68\u2005(8)\u00b0. To a first approximation, the thio\u00adsemicarbazone ligands comprise two planar regions. Thus, the non-hydrogen, non-phenyl atoms of the atoms of the S1-ligand define one plane (r.m.s. deviation = 0.1910\u2005\u00c5), which forms a dihedral angle of 54.53\u2005(8)\u00b0 with the (C14\u2013C19) ring, consistent with a near perpendicular relationship. The comparable values for the S2-ligand are 0.2800\u2005\u00c5 and 75.09\u2005(11)\u00b0, respectively.The mode of the coordination of the thio\u00adsemicarbazone ligands leads to the formation of five-membered ZnSCNc-axis direction sustained by eight-membered thio\u00adamide {\u22efHNCS}2 synthons, Fig.\u00a02a and Table\u00a02b, it is evident that two rows of mol\u00adecules, each with a right-angle topology, are connected by N\u2014H\u22efS(thione) hydrogen bonds. Centrosymmetrically related right angles are connected into a supra\u00admolecular tube, Fig.\u00a02c, via imine-phenyl-C\u2014H\u22efO(meth\u00adoxy), imine-phenyl-C\u2014H\u22ef\u03c0(imine-phen\u00adyl) and imine-phenyl-C\u2014H\u22ef\u03c0(meth\u00adoxy\u00adbenzene) inter\u00adactions, Table\u00a02et al., 2014et al., 2016v with a ring centroid\u2013ring centroid separation of 3.778\u2005(2)\u2005\u00c5 and angle of inclination = 15.04\u2005(17)\u00b0 for symmetry operation (v): 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. A review has appeared very recently on the topic of \u03c0(chelate ring)\u2013\u03c0(arene) and \u03c0(chelate ring)\u2013\u03c0(chelate ring) inter\u00adactions where it was suggested that inter\u00adactions of the former type provide comparable energies of stabilization to mol\u00adecular packing as do weak conventional hydrogen bonds  ring and between ethyl\u00adene-C24\u2014H and the  ring, Table\u00a02a. The donors and acceptors of the inter\u00admolecular N\u2014H\u22efS and C\u2014H\u22efO inter\u00adactions are also viewed as blue and red regions about respective atoms in the images of Fig.\u00a04a and b, respectively.The Hirshfeld surfaces calculated for (I)a, and those delineated into H\u22efH, C\u22efH/H\u22efC, S\u22efH/H\u22efS and O\u22efH/H\u22efO contacts de + di \u223c\u20052.1\u2005\u00c5 in Fig.\u00a06a is due to a short inter\u00adatomic H\u22efH contact  are also reflected from the small but important contribution from C\u22efN/N\u22efC and C\u22efS/S\u22efC contacts, Table\u00a04The overall two dimensional fingerprint plot for (I)t Table\u00a03 and the N\u2032-{(E)--amino}-N-ethyl\u00adcarbamimido\u00adthio\u00adato-\u03ba2N\u2032,S)zinc(II) mol\u00adecule, which differs from (I)et al., 20172S2 coordination geometries are found with values of \u03c44 of 0.70 and 0.74 for the two independent mol\u00adecules comprising the asymmetric unit. Indeed, in the publication describing this structure =NN=CR\u2032R\u2032\u2032]2 and all structures adopt the same basic structural motif as described herein for (I)The most relevant structure available for comparison is that of the recently described bis\u00ad was dissolved in hot absolute ethanol (30\u2005ml), which was added to a solution of Zn(CH3COO)2\u00b72H2O  in hot absolute ethanol (40\u2005ml). The mixture was heated and stirred for about 10\u2005min, followed by stirring for 1\u2005h at room temperature. The yellow precipitate obtained was filtered, washed with cold ethanol and dried in vacuo. Single crystals were grown at room temperature from the slow evaporation of the title compound in a mixed solvent system containing di\u00admethyl\u00adformamide and aceto\u00adnitrile . IR (cm\u22121): 3351 \u03bd(N\u2014H), 1597 \u03bd(C=N), 1009 \u03bd(N\u2014N), 420 \u03bd(M\u2014N), 362 \u03bd(M\u2014S).Analytical grade reagents were used as procured and without further purification. 4-Ethyl-3-thio\u00adsemicarbazide  and 4-meth\u00adoxy\u00adchalcone  were dissolved separately in hot absolute ethanol (30\u2005ml) and mixed while stirring. About five drops of concentrated hydro\u00adchloric acid were added to the mixture to catalyse the reaction. The reaction mixture was heated and stirred for about 20\u2005min, and stirring was continued for another 30\u2005min at room temperature. The resulting yellow precipitate, 4-meth\u00adoxy\u00adchalcone-4-ethyl-3-thio\u00adsemicarbazone, was filtered off, washed with cold absolute ethanol and dried Uiso(H) set to 1.2\u20131.5Ueq(C). The nitro\u00adgen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N). The maximum and minimum residual electron density peaks of 1.10 and 0.59\u2005e\u2005\u00c5\u22123, respectively, are located 1.04 and 0.71\u2005\u00c5 from the Zn atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989018000282/hb7725sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018000282/hb7725Isup2.hklStructure factors: contains datablock(s) I. DOI: 1814817CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion is coordinated by two pyridine N atoms from two symmetry-related unsymmetrical dipyridyl ligands and two chloride anions in a highly distorted tetra\u00adhedral geometry. Each unsymmetrical dipyridyl ligand links two HgII ions into polymeric zigzag chains. In the crystal, the chains are linked into a three-dimensional supra\u00admolecular network by inter\u00admolecular N/C\u2014H\u22efCl hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions. Weak C\u2014Cl\u22ef\u03c0 inter\u00adactions and Cl\u22efCl contacts between the network and the solvent chloro\u00adform mol\u00adecules are also observed.In the title compound, each Hg LCl2]\u00b70.5CHCl3}n (L = N-(pyridin-4-ylmeth\u00adyl)pyridin-3-amine, C11H11N3), contains one HgII ion, one bridging L ligand, two chloride ligands and a chloro\u00adform solvent mol\u00adecule with half-occupancy that is disordered about a crystallographic twofold rotation axis. Each HgII ion is coordinated by two pyridine N atoms from two symmetry-related L ligands and two chloride anions in a highly distorted tetra\u00adhedral geometry with bond angles falling in the range 99.05\u2005(17)\u2013142.96\u2005(7)\u00b0. Each L ligand bridges two HgII ions, forming polymeric zigzag chains propagating in [010]. In the crystal, the chains are linked by inter\u00admolecular N/C\u2014H\u22efCl hydrogen bonds together with weak C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in the formation of a three-dimensional supra\u00admolecular network, which is further stabilized by C\u2014Cl\u22ef\u03c0 inter\u00adactions between the solvent chloro\u00adform mol\u00adecules and the pyridine rings of L [chloride-to-centroid distances = 3.442\u2005(11) and 3.626\u2005(13)\u2005\u00c5]. In addition, weak Cl\u22efCl contacts [3.320\u2005(5)\u2005\u00c5] between the chloro\u00adform solvent mol\u00adecules and the coordinating chloride anions are also observed.The asymmetric unit of the title compound, {[Hg The solvent mol\u00adecule is disordered over two orientations of equal occupancy about the crystallographic twofold rotation axis. As shown in Fig.\u00a01II ion is highly distorted tetra\u00adhedral with two coordination sites being occupied by two pyridine N atoms from two symmetry-related L ligands. The geometry of the HgII ion is completed by the coordination of two chloride ions. The tetra\u00adhedral angles around the HgII ion fall in the range of 99.05\u2005(17)\u2013142.96\u2005(7)\u00b0 \u2005\u00c5. In the L ligand, the Cpy\u2014N\u2014C\u2014Cpy torsion angle is \u221270.9\u2005(7)\u00b0 while the dihedral angle between two terminal pyridine ring planes is 85.0\u2005(2)\u00b0. The conformation of the L ligand, along with the the Npy\u2014Hg\u2014Npy coordination angle [99.05\u2005(17)\u00b0], may induce the zigzag topology of the chain.Each is Fig.\u00a02. The sepbc plane \u2005\u00c5, C12\u2014Cl4\u22efCg2 = 170.7\u2005(8)\u00b0, Cl5\u22efCg2iv = 3.626\u2005(13)\u2005\u00c5 and C12\u2014Cl5\u22efCg2iv 144.1\u2005(8)\u00b0  are observed.In the crystal, adjacent zigzag chains are linked by inter\u00admolecular N\u2014H\u22efCl hydrogen bonds and weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions Table\u00a02, forminge Figs. 2 and 3 \u25b8.L ligand was synthesized according to a literature method  = 0.93\u2005\u00c5 for Csp2\u2014H, 0.97\u2005\u00c5 for methyl\u00adene C\u2014H, 0.98\u2005\u00c5 for methine C\u2014H, and 0.86\u2005\u00c5 for amine N\u2014H, and were refined as riding with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016015310/sj5509sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016015310/sj5509Isup2.hklStructure factors: contains datablock(s) I. DOI: 1507232CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These findings provide additional understanding of the NBC series and will aid in the development of these NLRP3 inhibitors as tool compounds or therapeutic candidates for sterile inflammatory diseases.The NLRP3 inflammasome is an important regulator of the sterile inflammatory response, and its activation by host\u2010derived sterile molecules leads to the intracellular activation of caspase\u20101, processing of the pro\u2010inflammatory cytokines interleukin\u20101\u03b2 (IL\u20101\u03b2)/IL\u201018, and pyroptotic cell death. Inappropriate activation of NLRP3 drives a chronic inflammatory response and is implicated in several non\u2010communicable diseases, including gout, atherosclerosis, type\u2005II diabetes and Alzheimer's disease. In this study, we report the design, synthesis and biological evaluation of novel boron compounds (NBCs) as NLRP3 inflammasome inhibitors. Structure\u2013activity relationships (SAR) show that 4\u2010fluoro substituents on the phenyl rings retain NLRP3 inhibitory activity, whereas more steric and lipophilic substituents diminish activity. Loss of inhibitory activity is also observed if the CCl Sterile inflammation is a host\u2010driven immune response to injury in the absence of infection.NLRP3 gene causes spontaneous IL\u20101\u03b2 release in patients with cryopyrin\u2010associated periodic syndrome (CAPS) diseases that are characterised by fever, rashes and extensive joint pain.IL\u20101\u03b2 and NLRP3 activation are well characterised in a number of non\u2010communicable diseases involving sterile inflammation including gout,Given the critical role of NLRP3 and IL\u20101\u03b2 in human disease,A number of small molecule inhibitors of the NLRP3 inflammasome have been previously described.1), BC23 (2) and NBC6  group. However, the impact of phenyl ring substitutions on IL\u20101\u03b2 release was not assessed. Additionally, the presence of the CCl3 group significantly contributes to the high lipophilicity of these oxazaborine inhibitors, limiting their drug\u2010likeness.We recently reported on the discovery of new boron\u2010based small molecules as potent NLRP3 inhibitors.2) and NBC6 (3), in addition to seeking alternative bioisosteres of the CCl3 group in the search for new NLRP3 inhibitors with improved potency and drug\u2010like properties.Here we explored structure\u2013activity relationships (SAR) of phenyl ring substitutions based on the known NLRP3 inhibitors BC23  with magnesium turnings or isopropylmagnesium chloride (iPrMgCl), followed by treatment with one molar equivalent of trimethyl borate (B(OMe)3) to afford symmetrical borinic acids (5).4 (when X=MgBr), such as p\u2010tolylmagnesium bromide, with a stoichiometric quantity of phenylboronic acid pinacol ester (7) to give the asymmetric borinic acid (6).Using the Topliss scheme for aromatic substituents,5 and 6 were then reacted with either (Z)\u20102\u2010acetyl\u20103\u2010amino\u20104,4,4\u2010trichlorobut\u20102\u2010enamide or (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010oneThe synthesised borinic acids m,AN0128, a known borinic acid picolinate ester prepared by Anacor Pharmaceuticals, was also synthesised in a two\u2010step method according to the reported procedure  and NBC6 (3) were then designed where the CCl3 group was replaced with the bioisosteric trifluoromethyl (CF3) group  to give analogues NBC41 and NBC42  to prime the cells and induce expression of pro\u2010IL\u20101\u03b2. The primed cells were then incubated with vehicle (0.5\u2009% DMSO) or inhibitor (10\u2005\u03bcm) for 15 minutes before the NLRP3 inflammasome activator nigericin  was added to cells. Supernatants were removed and IL\u20101\u03b2 levels were analysed by ELISA. Nigericin induced release of IL\u20101\u03b2 and this was inhibited by our parent molecule BC23 as expected  had minimal effect on inhibitory activity  and 4\u2010CH3 (NBC38) derivatives all inhibited IL\u20101\u03b2 release to a similar extent. This observation is further supported by the significantly decreased activities of 3,4\u2010Cl2 (NBC39) and 3\u2010Cl,4\u2010Me (NBC40) derivatives which possess additional substitutions around the phenyl rings. In contrast, there was an observed correlation between increasing lipophilicity and decreasing inhibitory activity across the BC23 series (NBC35 < NBC36 \u2248NBC37 \u2248NBC38 < NBC39). These observations were also in agreement across the NBC6 series, where the disubstituted\u2010p\u2010tolyl analogue NBC32 had slightly lower IL\u20101\u03b2 inhibitory activity than the monosubstituted\u2010p\u2010tolyl analogue NBC33 and parent compound NBC6 in THP\u20101 cells . These results suggest that aryl ring substitution, particularly with more steric and lipophilic substituents, is unlikely to enhance the activity of the NBCs.We initially tested the effect of modifying the phenyl rings of NBCs on their ability to inhibit NLRP3 inflammasome\u2010dependent release of IL\u20101\u03b2 from macrophages. Immortalised bone marrow derived macrophages (iBMDMs) were treated with LPS (1\u2005\u03bcg\u2009mLIt was surprising to note the lack of inhibitory activity of AN0128 in the IL\u20101\u03b2 release assay given its known anti\u2010inflammatory effects against IL\u20101\u03b2 and TNF\u2010\u03b1.3 group had been replaced with the bioisosteric trifluoromethyl (CF3) group  and NBC42  were ineffective under these conditions . Therefore these initial studies suggest that the CCl3 group is not labile under these reaction conditions. It was noted that during these experiments, nucleophiles were found to attack the boron atom and undergo decomplexation. For example, BC23 cleanly hydrolyses into diphenylborinic acid and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one in 9:1 [D6]DMSO/D2O solvent at 37\u2009\u00b0C with a half\u2010life of \u224824\u2005h, as monitored by 1H\u2005NMR spectroscopy .Given that the CClThe NLRP3 inflammasome is a multi\u2010molecular protein complex that is critical for inflammatory responses. Its formation leads to activation of caspase\u20101, which cleaves and activates IL\u20101\u03b2.3 group.3 group is key to inhibitory activity. These discoveries provide new insight into the activity of the NBC series and will aid future development of the NBC molecules as inflammasome inhibitors.We recently published the NBC series of NLRP3 inflammasome inhibitors reporting that key features required for bioactivity were the oxazaborine ring and CClGeneral: (Z)\u20104\u2010Amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one and (Z)\u20102\u2010acetyl\u20103\u2010amino\u20104,4,4\u2010trichlorobut\u20102\u2010enamide intermediates were prepared as previously described.1H, 13C, 11B and 19F\u2005NMR spectra were recorded on a Bruker Avance 400 or 300\u2005MHz spectrometer. Chemical shifts (\u03b4) are defined in parts per million (ppm). 1H\u2005NMR spectra were referenced to tetramethylsilane  or residual undeuterated solvent . 13C\u2005NMR spectra were referenced to residual undeuterated solvent  as an internal reference. 11B\u2005NMR chemical shifts were referenced to external reference BF3\u22c5OEt2 (\u03b4=0.0\u2005ppm). 19F\u2005NMR chemical shifts were referenced using the deuterium lock signal of the solvent. ESI and APCI mass spectrometry was carried out on a Waters Acquity UPLC system connected to a Waters SQD2 mass spectrometer. Accurate mass determination was carried out on a Thermo Exactive Plus EMR Orbitrap LC\u2013MS system. Molecular ion peaks are defined as mass/charge (m/z) ratios. Infrared spectroscopy was recorded on a JASCO FT/IR\u20104100 spectrophotometer using the Spectra Manager\u2005II (JASCO) software package. Melting points were measuring using a Stuart SMP10 melting point apparatus. Lyophilisation was carried out using a Christ alpha1\u20104 plus freeze dryer equipped with an Edwards vacuum pump. Microwave irradiation was carried out on a Biotage Initiator Classic microwave using 2\u20135\u2005mL Biotage glass vials. Analytical thin\u2010layer chromatography (TLC) was performed using silica gel 60 on aluminium sheets coated with F254 indicator. All spots were visualised with KMnO4 or ultraviolet light using a MV Mineralight lamp (254/365) UVGL\u201058. Flash column chromatography was performed using silica gel with particle size 40\u201363\u2005\u03bcm. Evaporation of solvents was conducted on a B\u00fcchi Rotavapor R\u2010200.p\u2010tolylborinic acid (5\u2009a)Di\u2010: To an oven\u2010dried Schlenk flask under N2 was added p\u2010tolylmagnesium bromide  in anhydrous THF (5\u2005mL). B(OMe)3  was added dropwise to the reaction mixture and stirred at room temperature for 3\u2005h. HCl  was then added and stirred for 30\u2005min to quench the reaction. The reaction mixture was extracted with EtOAc (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo. The crude product was then purified by flash column chromatography  to give 5\u2009a as a colourless oil . 1H\u2005NMR : \u03b4=7.63 ), 7.18 ), 5.65 , 2.33\u2005ppm ; 13C\u2005NMR : \u03b4=141.2 (B\u2010Ar(p)), 134.8 (B\u2010Ar(o)), 128.7 (B\u2010Ar(m)), 21.7\u2005ppm (CH3), B\u2010Ar(i) quaternary signal not observed.p\u2010tolyl)\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC32)5\u2010Acetyl\u20106\u2010amino\u20102,2\u2010bis(: (Z)\u20102\u2010Acetyl\u20103\u2010amino\u20104,4,4\u2010trichlorobut\u20102\u2010enamide  was added to a solution of 5\u2009a  in anhydrous THF (5\u2005mL). The mixture was stirred at 50\u2009\u00b0C under N2 for 16\u2005h. The mixture was concentrated in\u2005vacuo and purified by flash column chromatography . The collected fractions were combined, evaporated in\u2005vacuo and stirred in cold n\u2010hexane (15\u2005mL) for 30\u2005min. The precipitate was then filtered and dried under vacuum to give NBC32 as a yellow solid ; mp: 145\u2013148\u2009\u00b0C (dec); 1H\u2005NMR : \u03b4=9.23 , 7.58 C=C), 7.29 ), 7.12 ), 5.92 , 2.34 , 2.32\u2005ppm ; 13C\u2005NMR : \u03b4=198.1 (CH3CO), 169.2 (CONH2), 165.5 (Cl3C(NH)C=C), 156.1 (B\u2010Ar(i)), 136.2 (B\u2010Ar(p)), 132.0 (B\u2010Ar(o)), 128.2 (B\u2010Ar(m)), 97.9 (Cl3C(NH)C=C), 94.5 (CCl3), 34.0 (CH3CO), 21.3\u2005ppm (CH3); IR (neat): \u03bd\u02dc=3388 (N\u2212H), 3313 (N\u2212H), 1644 (C=O), 1608 , 1561\u2005cm\u22121 (C=C\u2010NH); MS(ES\u2212) (m/z): 434.2 \u2212, 435.2 \u2212, 436.2 \u2212, 437.2 \u2212, 438.2 \u2212, 439.2 \u2212; MS(ES+) (m/z): 344.1 +, 345.0 +, 346.0 +, 347.0 +, 349.1 +, 439.1 +; HRMS(ES+) (m/z): [M+H]+ calcd for C20H2111B35Cl3N2O2, 437.0756; found, 437.0738, error: 4.1\u2005ppm.p\u2010tolyl)borinic acid (6\u2009a)(Phenyl) in anhydrous THF (5\u2005mL). Phenylboronic acid pinacol ester  in anhydrous THF (5\u2005mL) was added dropwise to the reaction mixture and stirred at room temperature for 3\u2005h. HCl  was then added and stirred for 30\u2005min to quench the reaction. The reaction mixture was extracted with EtOAc (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo. The crude product was then purified by flash column chromatography  to give 6\u2009a as a colourless oil . 1H\u2005NMR : \u03b4=7.72 ), 7.64 ), 7.32\u20137.47 ), 7.19 ), 5.74 , 2.33\u2005ppm ; 13C\u2005NMR : \u03b4=141.4 (B\u2010Ar(p)), 135.0 (B\u2010Ph(o)), 134.6 (B\u2010Ar(o)), 130.9 (B\u2010Ph(p)), 128.8 (B\u2010Ar(m)), 127.9 (B\u2010Ph(m)), 21.7\u2005ppm (CH3), B\u2010Ar(i) and B\u2010Ph(i) quaternary signals not observed; MS(ES\u2212) (m/z): 195.1 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C13H1211BO, 195.0987; found, 195.0973, error: 7.2\u2005ppm.p\u2010tolyl)\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC33)5\u2010Acetyl\u20106\u2010amino\u20102\u2010(phenyl)\u20102\u2010(: (Z)\u20102\u2010Acetyl\u20103\u2010amino\u20104,4,4\u2010trichlorobut\u20102\u2010enamide  was added to a solution of 6\u2009a  in anhydrous THF (5\u2005mL). The mixture was stirred at 50\u2009\u00b0C under N2 for 16\u2005h. The mixture was concentrated in\u2005vacuo and purified by flash column chromatography . The collected fractions were combined, evaporated in\u2005vacuo and stirred in cold n\u2010hexane (15\u2005mL) for 30\u2005min. The precipitate was then filtered and dried under vacuum to give NBC33 as a yellow solid ; mp: 141\u2013143\u2009\u00b0C; 1H\u2005NMR : \u03b4=9.25 , 7.59 C=C), 7.40 ), 7.23\u20137.34  & B\u2010Ar(o)), 7.12 ), 5.94 , 2.34 , 2.31\u2005ppm ; 13C\u2005NMR : \u03b4=192.8 (CH3CO), 163.9 (Cl3C(NH)C=C), 160.3 (CONH2), 131.1 (B\u2010Ar(p)), 126.8 (B\u2010Ph(o)), 126.6 (B\u2010Ar(o)), 123.0 (B\u2010Ar(m)), 122.1 (B\u2010Ph(m)), 121.5 (B\u2010Ph(p)), 92.7 (Cl3C(NH)C=C), 89.2 (CCl3), 28.7 (CH3CO), 16.0\u2005ppm (CH3), B\u2010Ar(i) and B\u2010Ph(i) quaternary signals not observed; MS(ES\u2212) (m/z): 420.2 \u2212, 421.1 \u2212, 422.2 \u2212, 423.2 \u2212, 424.1 \u2212, 425.1 \u2212; HRMS(ES+) (m/z): [M+H]+ calcd for C19H1911B35Cl3N2O2, 423.0600; found, 423.0605, error: 1.2\u2005ppm.General procedure for synthesis of 2,2\u2010bisaryl\u20101,3,2\u2010oxazaborines: Using an adapted procedure,2 was added magnesium turnings (2.2\u2005equiv), anhydrous THF (5\u2005mL) and a small crystal of I2. The reaction was stirred at 40\u2009\u00b0C for 30\u2005min until complete decolourisation. A solution of aryl bromide (2\u2005equiv) and B(OMe)3 (1\u2005equiv) in anhydrous THF (5\u2005mL) was then added dropwise to the reaction mixture and then stirred for an additional 3\u2005h at 40\u2009\u00b0C. After cooling to room temperature, 1\u2009m HCl (10\u2005mL) was added and stirred for 30\u2005min to quench the reaction. The reaction mixture was extracted with EtOAc (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo to give the corresponding crude bisarylborinic acid, typically as a solid. (Z)\u20104\u2010Amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one (1.5\u2005equiv) was then added to crude bisarylborinic acid (1\u2005equiv) in anhydrous THF (5\u2005mL). The reaction was stirred at 50\u2009\u00b0C for 16\u2005h under N2. The reaction mixture was concentrated and purified by flash column chromatography using the indicated solvent system. Collected fractions were evaporated in\u2005vacuo and stirred in the minimum amount of cold n\u2010hexane for 30\u2005min to induce precipitation. The precipitate was then filtered and dried under vacuum to give the corresponding oxazaborine product. Percentage yields are reported over two steps.2,2\u2010Bis(4\u2010fluorophenyl)\u20106\u2010methyl\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC35): EtOAc/n\u2010hexane, 1:9. Reaction scale: B(OMe)3 , 1\u2010bromo\u20104\u2010fluorobenzene  and magnesium turnings  gives bis(4\u2010fluorophenyl)borinic acid . Bis(4\u2010fluorophenyl)borinic acid  and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one  gives NBC35 as a yellow solid ; mp: 130\u2013131\u2009\u00b0C; 1H\u2005NMR : \u03b4=7.31 ), 7.00 ), 5.83 C=CH), 2.25\u2005ppm , NH signal is overlapping with triplet at 7.31\u2005ppm; 13C\u2005NMR : \u03b4=186.5 (CH3CO), 166.1 (Cl3C(NH)C=CH), 162.6 ), 133.4 ), 114.4 ), 92.8 (CCl3), 92.0 (Cl3C(NH)C=CH), 24.9\u2005ppm (CH3CO), B\u2010Ar(i) quaternary signal not observed; 11B{1H}\u2005NMR : \u03b4=4.11\u2005ppm; 19F{1H}\u2005NMR : \u03b4=\u2212116.1\u2005ppm; MS(ES\u2212) (m/z): 399.1 \u2212, 400.1 \u2212, 401.1 \u2212, 402.1 \u2212, 403.1 \u2212, 404.1 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C17H1211B35Cl319F2NO, 400.0051; found, 400.0048, error: 0.7\u2005ppm.2,2\u2010Bis(4\u2010chlorophenyl)\u20106\u2010methyl\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC36): EtOAc/n\u2010hexane, 1:9. Reaction scale: B(OMe)3 , 1\u2010bromo\u20104\u2010chlorobenzene  and magnesium turnings  gives bis(4\u2010chlorophenyl)borinic acid . Bis(4\u2010chlorophenyl)borinic acid  and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one  gives NBC36 as a yellow solid ; mp: 106\u2013107\u2009\u00b0C; 1H\u2005NMR : \u03b4=7.25 , 7.19 ), 5.76 C=CH), 2.18\u2005ppm ; 13C\u2005NMR : \u03b4=186.7 (CH3CO), 166.3 (Cl3C(NH)C=CH), 133.2 (B\u2010Ar(o)), 133.1 (B\u2010Ar(p)), 127.8 (B\u2010Ar(m)), 92.7 (CCl3), 92.2 (Cl3C(NH)C=CH), 24.8\u2005ppm (CH3CO), B\u2010Ar(i) quaternary signal not observed; 11B{1H}\u2005NMR : \u03b4=3.82\u2005ppm; MS(ES\u2212) (m/z): 431.0 \u2212, 432.0 \u2212, 433.0 \u2212, 434.0 \u2212, 435.0 \u2212, 436.0 \u2212, 437.0 \u2212, 438.0 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C17H1211B35Cl5NO, 431.9460; found, 431.9460, error: 0.0\u2005ppm.6\u2010Methyl\u20104\u2010(trichloromethyl)\u20102,2\u2010bis(4\u2010(trifluoromethyl)phenyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC37): EtOAc/n\u2010hexane, 1:19. Reaction scale: B(OMe)3 , 4\u2010bromobenzotrifluoride  and magnesium turnings  gives bis(4\u2010trifluorophenyl)borinic acid . Bis(4\u2010trifluorophenyl)borinic acid  and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one  gives NBC37 as a yellow solid ; mp: 103\u2013105\u2009\u00b0C; 1H\u2005NMR : \u03b4=7.56 ), 7.46 ), 7.41 , 5.89 C=CH), 2.30\u2005ppm ; 13C\u2005NMR : \u03b4=187.1 (CH3CO), 166.7 (Cl3C(NH)C=CH), 131.8 (B\u2010Ar(o)), 129.2 ), 124.7 , 124.4 ), 92.7 (Cl3C(NH)C=CH), 24.8\u2005ppm (CH3CO), B\u2010Ar(i) and CCl3 quaternary signals not observed; 11B{1H}\u2005NMR : \u03b4=3.56\u2005ppm; 19F{1H}\u2005NMR : \u03b4=\u221262.4\u2005ppm; MS(ES\u2212) (m/z): 499.1 \u2212, 500.1 \u2212, 501.1 \u2212, 502.1 \u2212, 503.1 \u2212, 504.1 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C19H1211B35Cl319F6NO, 499.9987; found, 499.9990, error: 0.6\u2005ppm.2,2\u2010Bis(4\u2010methylphenyl)\u20106\u2010methyl\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC38): EtOAc/n\u2010hexane, 1:19. Reaction scale: B(OMe)3 , 4\u2010bromotoluene  and magnesium turnings  gives bis(4\u2010methylphenyl)borinic acid . Bis(4\u2010methylphenyl)borinic acid  and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one  gives NBC38 as a yellow solid ; mp: 105\u2013107\u2009\u00b0C; 1H\u2005NMR : \u03b4=7.41 , 7.28 ), 7.13 ), 5.77 C=CH), 2.34 , 2.23\u2005ppm ; 13C\u2005NMR : \u03b4=186.2 (CH3CO), 136.3 (B\u2010Ar(p)), 131.9 (B\u2010Ar(o)), 128.4 (B\u2010Ar(m)), 91.5 (Cl3C(NH)C=CH), 24.9 (CH3CO), 21.5\u2005ppm (CH3), B\u2010Ar(i) and Cl3C(NH)C=CH quaternary signals not observed; 11B{1H}\u2005NMR : \u03b4=4.61\u2005ppm; MS(ES\u2212) (m/z): 392.1 \u2212, 393.1 \u2212, 394.1 \u2212, 395.1 \u2212, 396.1 \u2212; MS(ES+) (m/z): 301.2 +, 302.1 +, 303.1 +, 304.1 +, 305.1 +, 306.0 +; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C19H1811B35Cl3NO, 392.0553; found, 392.0555, error: 0.6\u2005ppm.2,2\u2010Bis\u20106\u2010methyl\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC39): EtOAc/n\u2010hexane, 1:19. Reaction scale: B(OMe)3 , 4\u2010bromo\u20101,2\u2010dichlorobenzene  and magnesium turnings  gives bisborinic acid . Bisborinic acid  and (Z)\u20104\u2010amino\u20105,5,5\u2010trichloropent\u20103\u2010en\u20102\u2010one  gives NBC39 as a cream solid ; mp: 109\u2013110\u2009\u00b0C; 1H\u2005NMR : \u03b4=7.37 , 7.36 , 7.10 , 5.88 C=CH), 2.28\u2005ppm , NH signal is observed but overlapping with CHCl3 at 7.26\u2005ppm; 13C\u2005NMR : \u03b4=187.1 (CH3CO), 166.7 (Cl3C(NH)C=CH), 133.5 (B\u2010Ar\u2010C6), 132.1 (B\u2010Ar\u2010C3), 131.1 (B\u2010Ar\u2010C4), 130.9 (B\u2010Ar\u2010C2), 129.9 (B\u2010Ar\u2010C5), 92.8 (Cl3C(NH)C=CH), 92.5 (CCl3), 24.9\u2005ppm (CH3CO), B\u2010Ar\u2010C1 quaternary signal not observed; 11B{1H}\u2005NMR : \u03b4=3.10\u2005ppm; MS(ES\u2212) (m/z): 499.9 \u2212, 500.9 \u2212, 501.9 \u2212, 502.9 \u2212, 503.9 \u2212, 504.9 \u2212, 505.9 \u2212, 506.9 \u2212, 507.9 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C17H1011B35Cl7NO, 499.8681; found, 499.8681, error: 0.0\u2005ppm.5\u2010Acetyl\u20106\u2010amino\u20102,2\u2010bis(3\u2010chloro\u20104\u2010methylphenyl)\u20104\u2010(trichloromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC40): Using an adapted procedure,iPrMgCl  was added dropwise to a solution of 2\u2010chloro\u20104\u2010iodotoluene  in anhydrous THF (5\u2005mL) in an oven\u2010dried Schlenk flask under N2. The reaction was stirred at 0\u2009\u00b0C for 5\u2005h. B(OMe)3  was then added and the reaction mixture was stirred overnight allowing to warm to room temperature. HCl  was added and the reaction mixture was extracted with EtOAc (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo to give crude bis(3\u2010chloro\u20104\u2010methylphenyl)borinic acid as a cream solid in quantitative yield. To a portion of this intermediate  in anhydrous THF (5\u2005mL) was added (Z)\u20102\u2010acetyl\u20103\u2010amino\u20104,4,4\u2010trichlorobut\u20102\u2010enamide . The reaction was stirred at 50\u2009\u00b0C for 16\u2005h under N2. The reaction mixture was concentrated and purified by flash column chromatography . Collected fractions were evaporated in\u2005vacuo and stirred in the minimum amount of cold n\u2010hexane for 30\u2005min to induce precipitation. The precipitate was then filtered and dried under vacuum to give NBC40 as a white solid ; mp: 147\u2013148\u2009\u00b0C; 1H\u2005NMR : \u03b4=11.22 C=C), 7.38 , 7.18 , 7.10 , 6.16 , 5.89 , 2.32 , 2.26\u2005ppm ; MS(ES\u2212) (m/z): 502.1 \u2212, 503.1 \u2212, 504.1 \u2212, 505.1 \u2212, 506.1 \u2212, 507.1 \u2212, 508.1 \u2212, 509.1 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C20H1711B35Cl5N2O2, 502.9831; found, 502.9833, error: 0.4\u2005ppm.3\u2010Hydroxypyridine\u20102\u2010carbonyloxy\u2010bis(3\u2010chloro\u20104\u2010methylphenyl) borane (AN0128): Prepared according to a previously published method.iPrMgCl  was added dropwise to a solution of 2\u2010chloro\u20104\u2010iodotoluene  in anhydrous THF (5\u2005mL) in an oven\u2010dried Schlenk flask under N2. The reaction was stirred at 0\u2009\u00b0C for 5\u2005h. B(OMe)3  was then added and the reaction mixture was stirred overnight allowing to warm to room temperature. HCl  was then added and the reaction mixture was extracted with EtOAc (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo to give crude bis(3\u2010chloro\u20104\u2010methylphenyl)borinic acid as a cream solid in quantitative yield. A portion of this intermediate  was dissolved in EtOH (5\u2005mL) and heated at reflux. 3\u2010Hydroxypicolinic acid  was added in portions to the hot solution and after the last addition, the reaction mixture was stirred at reflux for 15\u2005min. The reaction was then cooled, resulting in the precipitation of product from the solution. The reaction mixture was partially concentrated and the precipitate was re\u2010crystallised in EtOH to give AN0128 as a white solid ; mp: 166\u2013167\u2009\u00b0C (lit.: 165.0\u2013166.5\u2009\u00b0C)1H\u2005NMR : \u03b4=12.17 , 8.58 , 7.93 , 7.22 , 7.20 , 7.11 , 2.27\u2005ppm ; 13C\u2005NMR : \u03b4=162.2 (COO), 156.2 (Py\u2010C9), 134.2 (Py\u2010C8), 134.0 (Py\u2010C12), 133.0 (B\u2010Ar\u2010C4), 132.1 (B\u2010Ar\u2010C3), 131.9 (B\u2010Ar\u2010C6), 131.5 (Py\u2010C11), 130.7 (B\u2010Ar\u2010C5), 130.5 (B\u2010Ar\u2010C2), 127.5 (Py\u2010C10), 19.4\u2005ppm (CH3), B\u2010Ar\u2010C1 quaternary signal not observed; 11B{1H}\u2005NMR : \u03b4=6.76\u2005ppm; MS(ES\u2212) (m/z): 397.1 \u2212, 398.1 \u2212, 399.1 \u2212, 400.1 \u2212, 401.1 \u2212; HRMS(ES\u2212) (m/z): [M\u2212H]\u2212 calcd for C20H1511B35Cl2NO3, 398.0528; found, 398.0526, error: 0.5\u2005ppm. All data were in agreement with literature values.3\u2010pentane\u20102,4\u2010dione (8): Using a previously reported procedure,3CN was slowly generated by dropwise addition of a solution of trifluoroacetic anhydride  in anhydrous pyridine (40\u2005mL) to a solution of trifluoroacetamide  in anhydrous pyridine (20\u2005mL) under N2 in a three\u2010neck round\u2010bottom flask equipped with a N2 gas inlet and gas outlet. The gas outlet was connected to a two\u2010neck round\u2010bottom flask containing a solution of acetylacetone  and Zn(acac)2  in anhydrous CH2Cl2 (10\u2005mL) that was equipped with a dry ice condenser connected to a bubbler outlet. CF3CN was bubbled into the stirring solution at room temperature for several hours until complete consumption of the trifluoroacetic anhydride solution. The reaction was further stirred at room temperature for 16\u2005h. The reaction mixture was extracted with CH2Cl2 (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo to give 8 as a white solid . 1H\u2005NMR : \u03b4=2.46 , 2.18\u2005ppm ; 13C\u2005NMR : \u03b4=202.1 (CH3CO), 196.4 (CH3CO), 145.7 C=C), 120.2 , 112.8 (F3C(NH2)C=C), 32.2 , 29.2\u2005ppm (CH3CO); 19F{1H}\u2005NMR : \u03b4=\u221266.4\u2005ppm. All data were in agreement with literature values.Z)\u20104\u2010Amino\u20105,5,5\u2010trifluoropent\u20103\u2010en\u20102\u2010one (10) was dissolved in EtOH (10\u2005mL) and a saturated solution of K2CO3 (20\u2005mL) was added. The reaction was stirred at 50\u2009\u00b0C for 24\u2005h. The reaction mixture was then extracted with CHCl3 (3\u00d710\u2005mL), washed with brine (1\u00d710\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo. The crude mixture was purified by flash column chromatography  to give 10 as an orange solid . 1H\u2005NMR : \u03b4=5.52 C=CH), 2.18\u2005ppm ; 13C\u2005NMR : \u03b4=199.6 (CH3CO), 147.1 C=CH), 120.4 , 94.1 C=CH), 30.5\u2005ppm (CH3CO); 19F{1H}\u2005NMR : \u03b4=\u221271.8\u2005ppm. All data were in agreement with literature values.6\u2010Methyl\u20102,2\u2010diphenyl\u20104\u2010(trifluoromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC41): Using an adapted procedure,10  was added to a solution of DPBA  in anhydrous THF (5\u2005mL). The reaction mixture was stirred at 50\u2009\u00b0C under Ar for 16\u2005h. The reaction mixture was then concentrated and purified by flash column chromatography  to give NBC41 as a yellow solid ; mp: 96\u201397\u2009\u00b0C (lit.: 99\u2013100\u2009\u00b0C);1H\u2005NMR : \u03b4=7.14\u20137.31 , 6.95 , 5.44 C=CH), 2.17\u2005ppm ; 13C\u2005NMR : \u03b4=188.3 (CH3CO), 156.7 C=CH), 131.8 (B\u2010Ph(o)), 127.6 (B\u2010Ph(m)), 127.1 (B\u2010Ph(p)), 118.8 , 91.6 (F3C(NH)C=CH), 24.9\u2005ppm (CH3CO); 11B{1H}\u2005NMR : \u03b4=4.37\u2005ppm; 19F{1H}\u2005NMR : \u03b4=\u221272.9\u2005ppm; MS(ES\u2212) (m/z): 316.11 \u2212; MS(ES+) (m/z): 340.11 +; HRMS(ES\u2212) (m/z): [M+Na]\u2212 calcd for C17H1511BF3NO, 340.1091; found, 340.1085, error: 1.8\u2005ppm. All data were in agreement with literature values.Z)\u20102\u2010Acetyl\u20103\u2010amino\u20104,4,4\u2010trifluorobut\u20102\u2010enamide (9) in anhydrous pyridine (40\u2005mL) to a solution of trifluoroacetamide  in anhydrous pyridine (20\u2005mL) under N2 in a three\u2010neck round\u2010bottom flask equipped with a N2 gas inlet and gas outlet. The gas outlet was connected to a two\u2010neck round\u2010bottom flask containing a solution of acetoacetamide  and Zn(acac)2  in anhydrous CH2Cl2 (10\u2005mL) that was equipped with a dry ice condenser connected to a bubbler outlet. CF3CN was bubbled into the stirring solution at room temperature for several hours until complete consumption of the trifluoroacetic anhydride solution. The reaction was further stirred at room temperature for 16\u2005h. The reaction mixture was extracted with EtOAc (5\u00d750\u2005mL), washed with brine (3\u00d750\u2005mL), dried over MgSO4, filtered and evaporated in\u2005vacuo. Et2O (10\u2005mL) was added to induce precipitation and the precipitate was filtered, washed with additional Et2O and dried to give 9 as a white solid ; mp: 192\u2013193\u2009\u00b0C; 1H\u2005NMR : \u03b4=9.06 , 7.75 , 7.40 , 2.18\u2005ppm ; 13C\u2005NMR : \u03b4=196.5 (CH3CO), 168.3 (CONH2), 144.9 C=C), 120.3 , 107.0 (F3C(NH2)C=C), 28.0\u2005ppm (CH3CO); 19F{1H}\u2005NMR : \u03b4=\u221265.4\u2005ppm; MS(ES\u2212) (m/z): 195.04 \u2212; MS(ES+) (m/z): 219.03 +; HRMS(ES\u2212) (m/z): [M+Na]\u2212 calcd for C6H7F3N2O2, 219.0352; found, 219.0346, error: 2.7\u2005ppm.5\u2010Acetyl\u20106\u2010amino\u20102,2\u2010diphenyl\u20104\u2010(trifluoromethyl)\u20102,3\u2010dihydro\u20101,3,2\u2010oxazaborinin\u20101\u2010ium\u20102\u2010uide (NBC42): 9  was added to a solution of DPBA  in anhydrous THF (5\u2005mL). The reaction mixture was stirred at 50\u2009\u00b0C under Ar for 16\u2005h. The reaction mixture was then concentrated and purified by flash column chromatography . The collected fractions were combined, evaporated in\u2005vacuo and precipitated in n\u2010hexane (10\u2005mL) to give NBC42 as a white solid ; mp: 118\u2013120\u2009\u00b0C; 1H\u2005NMR : \u03b4=10.05 , 7.22\u20137.36 , 6.17 , 2.26\u2005ppm ; 13C\u2005NMR : \u03b4=196.3 (CH3CO), 169.8 (CONH2), 156.7 C=C), 131.8 (B\u2010Ar(o)), 127.5 (B\u2010Ar(m)), 127.0 (B\u2010Ar(p)), 119.4 , 97.2 (F3C(NH)C=C), 30.5\u2005ppm , B\u2010Ar(i) quaternary signal not observed; 11B{1H}\u2005NMR : \u03b4=2.55\u2005ppm; 19F{1H}\u2005NMR : \u03b4=\u221265.1\u2005ppm; MS(ES\u2212) (m/z): 227.0 \u2212, 359.1 \u2212, 523.3 \u2212; MS(ES+) (m/z): 219.0 +, 399.1 +, 219.0 +, 563.2 +; HRMS(ES+) (m/z): [M+H]+ calcd for C18H1711BF3N2O2, 361.1330; found, 361.1338, error: 2.3\u2005ppm.Cell culture: Immortalised murine bone marrow\u2010derived macrophages (iBMDMs) were cultured in DMEM, 10\u2009% fetal bovine serum (FBS), 100\u2005U\u2009mL\u22121 penicillin and 100\u2005\u03bcg\u2009mL\u22121 streptomycin (PenStrep). Cells were seeded overnight at 0.75\u00d7106 cells per mL and then stimulated with LPS , and then incubated with vehicle (0.5\u2009% DMSO) or drug as indicated (10\u2005\u03bcm) for 15\u2005min before activation of NLRP3 using nigericin . IL\u20101\u03b2 release was measured by a specific ELISA (R&D systems).Data presentation and statistical analysis: Data are presented as mean values \u00b1 standard error of the mean (SEM) of at least three separate experiments. Statistical analyses performed were one\u2010way analysis of variance (ANOVA) with Dunnett's multiple comparisons test post hoc. Accepted levels of significance were *p<0.05, ***p<0.001. Statistical analyses were carried out using GraphPad Prism.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Hydrogen bonding through the water mol\u00adecules gives two-dimensional sheets lying parallel to (100).The present paper describes the synthesis and crystal structure of a cobalt(II) isobutyrate dihydrate, based on a slightly distorted CoO 3)2CO2}2(H2O)]\u00b7H2O}n, the Co2+ ion is hexa\u00adcoordinated in a slightly distorted octa\u00adhedral coordination environment defined by two O atoms from two bridging water mol\u00adecules and four O atoms from four bridging carboxyl\u00adate ligands. The carboxyl\u00adates adopt two different coordination modes, \u03bc-(\u03ba2O:O\u2032) and \u03bc-(\u03ba2O:O), forming a one-dimensional polymeric chain extending along [010]. The intra-chain cobalt\u22efcobalt separation is 3.2029\u2005(2)\u2005\u00c5. The polymeric chains are linked by hydrogen bonds involving the water mol\u00adecules of solvation, giving a two-dimensional network structure lying parallel to (100).In the title cobalt(II) coordination polymer with isobutyrate ligands, {[Co{CH(CH Oligo- and polynuclear cobalt carboxyl\u00adates in turn have attracted great attention because of their utilization in homogeneous oxidation catalysis 2CO2}2(H2O)]\u00b7H2O}n, (I)As a part of our ongoing studies on these compounds, we describe here synthesis and crystal structure of the title compound, {[Co{CH(CH2+ cation coordinated by four O atoms from four bridging isobutyrate ligands and two O atoms from two bridging water mol\u00adecules (O1W) in a distorted octa\u00adhedral coordination. A water mol\u00adecule of solvation (O2W) is also present \u2013110.31\u2005(2)\u00b0. This data correlates with the angles and the distances in cobalt(II) acetate dihydrate which has a similar structure nt Fig.\u00a01. The Co\u2014nt Fig.\u00a01 and the \u221e[Co(H2O)((CH3)2CHCOO)2] composition, extending along [010]  and \u03bc-(\u03ba2O:O). The C\u2014O bond lengths of the first group (involving O1A and O2A) have close values [1.2755\u2005(10) and 1.2533\u2005(10)\u2005\u00c5], whereas those of the second group (involving O1B and O2B) have a more striking difference [1.2878\u2005(9) and 1.2510\u2005(11)\u2005\u00c5]. The carboxyl\u00adate O2B atom of the second group forms an inter-unit hydrogen bond with the bridging water mol\u00adecule [O1W\u2014H\u22efO2Bi = 2.6206\u2005(9)\u2005\u00c5] 0] Fig.\u00a02. The Co\u22ef\u00c5] Fig.\u00a02.W) by a system of hydrogen bonds, forming a sheet structure arranged parallel to (100)  Table\u00a02. Only weet al., 2016\u221e[Co(RCOO)2(H2O)]: acetate  was added. The reaction mixture was period\u00adically stirred in an ultrasonic bath at room temperature until the liberation of carbon dioxide ceased. The unreacted CoCO3\u00b76H2O was removed by filtration, and the filtrate was allowed to stand at room temperature for slow evaporation. Red single crystals of (I)The title compound was synthesized using a similar procedure as for the synthesis of the analogous carboxyl\u00adates cobalt(II) propionate dihydrate (Fischer Uiso(H) set to 1.5Ueq(O). Other hydrogen atoms were placed in calculated positions and refined using a riding model with d(C\u2014H) = 0.98\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for the tertiary carbon atoms and d(C\u2014H) = 0.96\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017001360/zs2371sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 1529830CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C=O\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions also occur. Hirshfeld surface analysis was used to confirm and qu\u00adantify the supra\u00admolecular inter\u00adactions.The structure of a coumarin ester is reported and compared with the results of a quantum chemical calculation. In the crystal, inter\u00admolecular C\u2014H\u22efO contacts generate an infinite C(6) chain along the  20H18O4, the benzoate ring is oriented at an acute angle of 33.10\u2005(12)\u00b0 with respect to the planar (r.m.s deviation = 0.016\u2005\u00c5) coumarin ring system. An intra\u00admolecular C\u2014H\u22efO hydrogen bond closes an S(6) ring motif. In the crystal, C\u2014H\u22efO contacts generate infinite C(6) chains along the b-axis direction. Also present are \u03c0\u2013\u03c0 stacking inter\u00adactions between neighbouring pyrone and benzene rings [centroid\u2013centroid distance = 3.7034\u2005(18)\u2005\u00c5] and C=O\u22ef\u03c0 inter\u00adactions [O\u22efcentroid = 3.760\u2005(3)\u2005\u00c5]. The data obtained from quantum chemical calculations performed on the title compound are in good agreement with the observed structure, although the calculated C\u2014O\u2014C\u2014C torsion angle between the coumarin ring system and the benzoate ring (129.1\u00b0) is somewhat lower than the observed value [141.3\u2005(3)\u00b0]. Hirshfeld surface analysis has been used to confirm and qu\u00adantify the supra\u00admolecular inter\u00adactions.In the title compound, C Coumarin and its derivatives have been reported to serve as anti-bacterial  ring motif arises from an intra\u00admolecular C6\u2014H6\u22efO4 hydrogen bond, and generates a pseudo-tricyclic ring system em Fig.\u00a01. The couc-axis direction, as shown in Fig.\u00a03B = 2.38\u2005\u00c5] is found at a distance shorter than the sum of the van der Waals radii. An unusual C10=O4\u22ef\u03c0 inter\u00adaction , is also present. The resulting supra\u00admolecular aggregation is completed by the presence of \u03c0\u2013\u03c0 stacking  = 3.7035\u2005(18) and Cg3\u22efCg1  = 3.7034\u2005(18)\u2005\u00c5, where Cg1 and Cg3 are the centroids of the pyrone and the C11\u2013C16 benzene rings, respectively] that are less than 3.8\u2005\u00c5, the maximum regarded as suitable for an effective \u03c0\u2013\u03c0 inter\u00adaction  and 3.6143\u2005(13)\u2005\u00c5, respectively, and the distances between Cg1 and a perpendicular projection of Cg3 on ring 1 (slippage) are 0.726 and 0.807\u00c5, respectively.In the crystal, two types of inter\u00admolecular hydrogen-bonding inter\u00adactions are present Table\u00a01. The C8\u2014ng Fig.\u00a04 between et al., 2016et al.,1982et al., 1985et al., 2011et al., 2014meta-substituted coumarin esters dnorm surfaces mapped over a fixed colour scale of \u22120.39 (red) to 1.4\u2005\u00c5 (blue) with the program CrystalExplorer 3.1 dnorm highlights six red spots showing distances shorter than the sum of the van der Waals radii. These dominant inter\u00adactions correspond to inter\u00admolecular C\u2014H\u22efO hydrogen bonds, O\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions between the surface and the neighbouring environment. The mapping also shows white spots with distances equal to the sum of the van der Waals radii and blue regions with distances longer than the sum of the van der Waals radii. The surfaces are transparent to allow visualization of the mol\u00adecule , as shown by the X-ray study. The most significant contribution to the Hirshfeld surface (46.8%) is from H\u22efH contacts, which appear in the central region of the FP . H\u22efO/O\u22efH inter\u00adactions with a 24.1% contribution appear as blue spikes in Fig.\u00a06c and show the presence of O\u22efH contacts, whereas the C\u22efH/H\u22efC plot (17.3%) gives information about inter\u00admolecular hydrogen bonds . Other visible spots in the Hirshfeld surfaces show C\u22efO/O\u22efC and O\u22efO contacts, which contribute only 4.0 and 1.0%, respectively .Mol\u00adecular Hirshfeld surfaces of 2-oxo-2le Fig.\u00a05. Furtherns Fig.\u00a06a, as shFP Fig.\u00a06b. H\u22efO/Ods Fig.\u00a06d. Otherly Fig.\u00a06e and 6f++G basis set. The crystal structure in the solid state was used as the starting structure for the calculations. The DFT calculations are performed with the GAUSSIAN09 program package tert-butyl\u00adbenzoyl chloride  in dry tetra\u00adhydro\u00adfuran (30 to 40\u2005ml), was added dry tri\u00admethyl\u00adamine  and 7-hy\u00addroxy\u00adcoumarin  in small portions over 30\u2005min. The mixture was then refluxed for four\u2005h and poured into 40\u2005ml of chloro\u00adform. The solution was acidified with diluted hydro\u00adchloric acid until the pH was 2\u20133. The organic layer was extracted, washed with water to neutrality, dried over MgSO4 and the solvent removed. The resulting precipitate (crude product) was filtered off with suction, washed with petroleum ether and recrystallized from chloro\u00adform. Colourless crystals of the title compound were obtained in a good yield: 90%; m.p. 406\u2013408\u2005K.To a solution of 4-Uiso(H) constrained to 1.2 (aromatic) or 1.5 (meth\u00adyl) times Ueq(C) of the respective parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018004188/sj5549sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018004188/sj5549Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018004188/sj5549Isup3.cmlSupporting information file. DOI: 1828991CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "ASBTapical sodium\u2010dependent bile acid transporterBAbile acidBSEPbile salt export pumpCAcancer antigenCDCAchenodeoxycholic acidCholcholesterolCol1\u03b1, collagen 1\u03b1; COX2cyclooxygenase 2eNOSendothelial NO synthaseET1endothelin 1FAfatty acidFFAfree fatty acidFGFfibroblast growth factorFGFRFGF receptorFXRfarnesoid X receptorHCChepatocellular carcinomaHDLhigh\u2010density lipoproteinIFNinterferonIGF1Rinsulin\u2010like growth factor 1 receptorILinterleukiniNOSinducible NO synthaseKCKupffer cellLDLlow\u2010density lipoproteinLDLrLDL receptorLp(a), lipoprotein a; LSECliver sinusoidal endothelial cellMCP1monocyte chemoattractant protein 1MDRmultidrug resistanceMMPmatrix metalloproteinaseNAFLDnonalcoholic fatty liver diseaseNASHnonalcoholic steatohepatitisNF\u03baBnuclear factor kappa BNOnitric oxideNTCPsodium/taurocholate cotransporting polypeptidePLphospholipidsSR\u2010BIscavenger receptor class B type 1p\u2010STAT3phosphorylated signal transducer and activator of transcription 3TGtriglycerideTGFtransforming growth factorTIMPtissue inhibitor of metalloproteinaseTJtight junctionTNFtumor necrosis factorVCAMvascular cell adhesion moleculeVLDLvery low\u2010density lipoproteinZO\u20101zona occludens 1."}
{"text": "Offset \u03c0\u2013\u03c0 inter\u00adactions are also present.The title hydrated salt, C 10H12N3O3S+\u00b7Cl\u2212\u00b7H2O, the benzimidazolium ring system is almost planar (r.m.s. deviation = 0.006\u2005\u00c5) and the nitro group is inclined at an angle of 4.86\u2005(9)\u00b0 to this plane. In the crystal, C\u2014H\u22efO hydrogen bonds form centrosymmetric R22(20) dimers and these are further aggregated through N\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds involving the water mol\u00adecules and chloride anions. Aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are also found between two parallel benzene rings or the benzene and imidazolium rings, with centroid\u2013centroid distances of 3.5246\u2005(9) and 3.7756\u2005(9)\u2005\u00c5, respectively. Analysis of the bond lengths and comparison with related compounds show that the nitro substituent is not involved in conjugation with the adjacent \u03c0-system and hence has no effect on the charge distribution of the heterocyclic ring.In the cation of the title hydrated molecular salt, C The centroid\u2013centroid separations are less than 3.8\u2005\u00c5, the maximum regarded as suitable for an effective \u03c0\u2013\u03c0 inter\u00adaction  in dimethyl sulfoxide (DMSO) (10\u2005ml). The reaction mixture was agitated for 5\u2005h at room temperature. 50\u2005ml of water was then added to the reaction mixture, and the products were extracted with di\u00adchloro\u00admethane (3 \u00d7 50\u2005ml). The combined organic extracts were washed with ammonium chloride solution (10\u2005g of ammonium chloride in 100\u2005ml of water), dried over Na2SO4, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel . The resulting powder was dissolved in di\u00adchloro\u00admethane and after three days, yellow crystals suitable for single-crystal X-ray diffraction analysis were obtained in 72% yield with a melting point of 425\u2005K.2-Chloro\u00adethanol  and potassium carbonate  were added to 2-methyl\u00adthio-5-nitro-11H NMR  \u03b4(p.p.m.): 2.7 ; 3 ; 3.7 ; 4.3 ; 5 ; 7.5\u20138.5 .13C  \u03b4 (p.p.m.): 114.28 (CH3); 47 (CH2O); 59 (CH2N); 106.56; 110.03; 112.87; 117.13; 136.38; 147.37; 155.52 ; 162.23 (C=N).Uiso(H) were refined with O\u2014H distances restrained to be 0.82\u2005\u00c5 with a standard deviation of 0.02\u2005\u00c5. Other H atoms were placed in calculated positions  and refined using a riding-model approximation with Uiso(H) constrained to 1.2  or 1.5  times Ueq of the respective parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016013657/sj5502sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016013657/sj5502Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013657/sj5502Isup3.cmlSupporting information file. DOI: 1500918CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Mol\u00adecules (I) and (II) are nearly planar, while mol\u00adecule (III) is not planar. In compounds (I) and (II), mol\u00adecules are linked into chain by C\u2014H\u22ef\u03c0 inter\u00adactions. In compound (III), mol\u00adecules are linked by a pair of C\u2014H\u22efO hydrogen bonds, forming inversion dimers. Weak C\u2014Br\u22ef\u03c0 inter\u00adactions are present in (III). viz. (E)-1-[4-(4-bromo\u00adbut\u00adoxy)\u00adphen\u00adyl]-3-phenyl\u00adprop-2-en-1-one, C19H19BrO2, (I), (E)-1-[4-(4-bromo\u00adbut\u00adoxy)\u00adphen\u00adyl]-3-(4-meth\u00adoxy\u00adphen\u00adyl)prop-2-en-1-one, C20H21BrO3, (II), and (E)-1-[4-(4-bromo\u00adbut\u00adoxy)\u00adphen\u00adyl]-3-prop-2-en-1-one, C21H23BrO4, (III), are reported. In all mol\u00adecules, the conformation of the keto group with respect to the olefinic bond is s-cis. Mol\u00adecules of (I) and (II) are nearly planar, while mol\u00adecule (III) is not planar. In the crystal of compounds (I) and (II), mol\u00adecules are linked into chains parallel to the c axis by C\u2014H\u22ef\u03c0 inter\u00adactions. In the crystal of compound (III), mol\u00adecules are linked by a pairs of C\u2014H\u22efO hydrogen bonds, forming inversion dimers. Weak C\u2014Br\u22ef\u03c0 inter\u00adactions are also observed in (III).The crystal structures of three chalcones with a bromo-substituted but\u00adoxy side chain,  D\u2014\u03c0\u22efA type mol\u00adecule. When the electron-rich groups are located on the 4 and/or 4\u2032 positions, the electron flow follows a \u039b-shaped path, and therefore the mol\u00adecule is called a \u039b-shaped mol\u00adecule  anti-tumor activity  connected by an enone moiety with a bromo\u00adbut\u00adoxy side chain attached at the 4-position of one of the phenyl rings. In mol\u00adecule (I)B. All of them crystallize in the monoclinic space group P21/c with Z = 4. All three mol\u00adecules adopt an s-cis conformation about the central olefinic C12=C13 bond with O2\u2014C11\u2014C12\u2014C13 torsion angles of \u22123.2\u2005(4), \u22121.6\u2005(5) and \u221221.5\u2005(4)\u00b0, respectively, and the hydrogen atoms of the central enone groups are trans-arranged with respect to the C12=C13 double bond. Mol\u00adecules (I)A and B are 3.10\u2005(13), 5.34\u2005(11)\u00b0 in compound (I)et al., 2007B with torsion angles of \u22123.3\u2005(4)\u00b0 (C20\u2014O3\u2014C17\u2014C16) in mol\u00adecule (II)The mol\u00adecular structures of the title compounds (I)A with a C6\u2014C5\u2014O1\u2014C4 torsion angle of 179.7\u2005(3)\u00b0.In compounds (I)et al., 2003In compounds (I)et al., 1995et al., 2013et al., 2005via atom H2A of ring A and the centroid of ring B of a symmetry-related mol\u00adecule (Table\u00a01c axis. In compound (II)c axis by two C\u2014H\u22ef\u03c0 inter\u00adactions involving the C2 and C3 carbon atoms via atoms H2B and H3A of ring A and the centroid of ring B of two symmetry-related mol\u00adecules (Table\u00a02The packing for mol\u00adecules (I)e Table\u00a01, formings Table\u00a02.A via atom H10 and the O3 oxygen atom \u2005\u00c5; Cg is the centroid of ring B; symmetry code: (ii) 1\u00a0\u2212\u00a0x, \u2212y, z] having a \u2018face-on\u2019 geometry m Table\u00a03. In addiet al., 2016A search of the Cambridge Structural Database  with benzaldehyde (1 equiv.) for compound (I)2Cl2 (3 \u00d7 100\u2005ml). The organic layers were separated, washed with brine (1 \u00d7 150\u2005ml), dried over anhydrous Na2SO4 and evaporated to give the crude bromo compounds, which were purified by column chromatography (SiO2) using a mixture of hexa\u00adne/CHCl3 (9:2 v/v) as eluent to afford yellow solids. The compounds were recrystallized by slow evaporation of chloro\u00adform solutions.Mixtures of chalcone (1 equiv.), 1,4-di\u00adbromo\u00adbutane (1.2 equiv.) and anhydrous potassium carbonate (2 equiv.) in dry acetone (40\u2005mL) were then stirred at 333\u2005K for 12\u2005h. After completion of reactions, the solvents were evaporated under reduced pressure and the residues extracted with CHUiso(H) values were set to 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017010052/rz5217sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989017010052/rz5217Isup5.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017010052/rz5217IIsup6.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017010052/rz5217IIIsup7.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989017010052/rz5217Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017010052/rz5217IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017010052/rz5217IIIsup7.cmlSupporting information file. DOI: 1545201, 1545200, 1545196CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Proc. R. Soc. A472, 20160062 (Published online May 4 2016) (doi:10.1098/rspa.2016.0062)K is symmetrical with respect to \u03b7. More generally they should be replaced by periodic boundary conditions on \u2014\u2003The Neumann boundary conditions (3.6), (3.9), (3.26), (A\u200911), (A\u200915), (A\u200922), (A\u200927) and (A\u200931) are applicable only when \u2014\u2003Equation (4.25) should read\u2014\u2003Equations (4.26) and (4.27) should read\u2014\u2003The two lines following equation (4.30) should read:\u03a9+ with \u0393, and \u03a9+ with \u0393, with both where \u2014\u2003The line following equation (4.33) should read:\u03a9\u2212 with \u0393, andwhere \u2014\u2003Equation (A\u200918) should read:"}
{"text": "III ions (each with site symmetry 2..) in the title compound have a distorted octa\u00adhedral coordination environment with four N atoms of a cyclam ligands and two chloride ions or one oxalate bidentate ligand in a cis position whereby the cyclam ligands adopt a cis-V conformation. The crystal packing is stabilized by extensive hydrogen-bonding inter\u00adactions among the cyclam N\u2013H groups, the Cl ligands, and O atoms of the oxalate and ClO4\u2212 anions.Two Cr 2(C10H24N4)][Cr(C2O4)(C10H24N4)](ClO4)2 , there are two independent halves of the [CrCl2(cyclam)]+ and [Cr(ox)(cyclam)]+ cations, and one perchlorate anion. In the complex cations, which are completed by application of twofold rotation symmetry, the CrIII ions are coordinated by the four N atoms of a cyclam ligand, and by two chloride ions or one oxalate bidentate ligand in a cis arrangement, displaying an overall distorted octa\u00adhedral coordination environment. The Cr\u2014N(cyclam) bond lengths are in the range of 2.075\u2005(5) to 2.096\u2005(4)\u2005\u00c5 while the Cr\u2014Cl and Cr\u2014O(ox) bond lengths are 2.3358\u2005(14) and 1.956\u2005(4)\u2005\u00c5, respectively. Both cyclam moieties adopt the cis-V conformation. The slightly distorted tetra\u00adhedral ClO4\u2212 anion remains outside the coordination sphere. The supra\u00admolecular architecture includes N\u2014H\u22efO and N\u2014H\u22efCl hydrogen bonding between cyclam NH donor groups, O atoms of the oxalate ligand or ClO4\u2212 anions and one Cl ligand as acceptors, leading to a three-dimensional network structure.In the asymmetric unit of the title compound, [CrCl Each cyclam moiety exhibits point group symmetry ..2 and can be described as being in the cis-V (anti\u2013anti) conformation 2(cyclam)]ClO4 [2.069\u2005(3)\u20132.103\u2005(3)\u2005\u00c5] 2(cyclam)]NO2 [2.0874\u2005(16)\u20132.0916\u2005(15)\u2005\u00c5] 2\u00b70.5H2O [2.070\u2005(5)\u20132.089\u2005(5)\u2005\u00c5] 2(cyclam)]NCS [2.0851\u2005(14)\u20132.0897\u2005(14)\u2005\u00c5] 2(cyclam)]ClO4 [2.046\u2005(2)\u20132.060\u2005(2)\u2005\u00c5] 2(cyclam)]BF4 [2.064\u2005(4)\u20132.073\u2005(4)\u2005\u00c5] 2(cyclam)][ZnCl4]Cl\u00b7H2O [2.0501\u2005(15)\u20132.0615\u2005(15)\u2005\u00c5] 2(cyclam)]ClO4 [2.058\u2005(4)\u20132.064\u2005(4)\u2005\u00c5] 2]2ZnCl4 2(Me2tn)2]ClO4\u00b72H2O 2(Me2tn)2]SCN\u00b70.5H2O F2]ClO4 \u2005\u00c5 for the oxalate ligand is close to the mean of 1.959\u2005(4)\u2005\u00c5 found in [Cr(ox)(cyclam)]ClO4 \u2005\u00c5 is comparable to those found in cis-[CrCl2(cyclam)]ClO4 [2.331\u2005(2)\u2005\u00c5] ]ClO4 [2.3157\u2005(7)\u2005\u00c5] 2]2ZnCl4 [2.3112\u2005(6)\u2005\u00c5] 2]Cl [2.3253\u2005(7)\u2005\u00c5] \u00b0, while the Cl1B\u2014Cr1B\u2014ClBi angle is 89.11\u2005(9)\u00b0 [symmetry code: (i) \u2013x\u00a0+\u00a0y\u00a0+\u00a0z]. The folded angles of the cyclam in [CrCl2(cyclam)]+ and [Cr(ox)(cyclam)]+ cations are 93.7\u2005(2) and 97.5\u2005(2)\u00b0, respectively. The significant distortion of the octa\u00adhedral coordination sphere and the larger folded angle in the [Cr(ox)(cyclam)] + cation seem to arise from the small bite angle of the oxalato ligand. The tetra\u00adhedral ClO4\u2212 anion remains outside the coordination sphere of two CrIII ions. It is distorted due to its involvement in hydrogen-bonding inter\u00adactions. Cl\u2014O bond lengths range from 1.426\u2005(5) to 1.443\u2005(5)\u2005\u00c5 and the O\u2014Cl\u2014O angles from 107.8\u2005(4)\u2013111.0\u2005(3)\u00b0.The asymmetric unit contains two halves of the [CrClon Fig.\u00a01. In eachon Fig.\u00a01. The Cr\u2014+ cation while N\u2014H\u22efO and N\u2014H\u22efCl contacts inter\u00adconnect two [Cr(ox)(cyclam)]+ and one cis-[CrCl2(cyclam)]+ cation (cyclam)]n Table\u00a01 and 3 \u25b8.et al., 2016cis-[CrL2(C10H24N4)]+ unit. The crystal structure of cis-[CrCl2(cyclam)]ClO4 2(cyclam)]ClO4 2(cyclam)](ClO4)Cl2 2)(cyclam)]NO2 2\u00b70.5H2O 2(cyclam)]NCS ][Cr(ox)(cyclam)]2+ with any anion has been deposited.A search of the Cambridge Structural Database ]ClO4 and [Cr(ox)(cyclam)]ClO4, were prepared according to literature methods ][Cr(ox)(cyclam)](ClO4)2, was prepared by mixing concentrated equimolar aqueous solutions of the two starting compounds. A saturated solution of NaClO4 was added to the resulting solution for crystallization, and allowed to stand at room temperature for two days to give needle-like orange crystals of (I)The free ligand cyclam was purchased from Fluka and used as provided. All chemicals were reagent grade materials and were used without further purification. The starting materials, Uiso(H) values of 1.2Ueq of the parent atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016014134/wm5323sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016014134/wm5323Isup2.hklStructure factors: contains datablock(s) I. DOI: 1502530CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Secondary Sn\u22efS inter\u00adactions lead to centrosymmetric dimeric aggregates in the crystal.In (CH 3)2(C5H8NOS2)2], has the SnIV atom bound by two methyl groups which lie over the weaker Sn\u2014S bonds formed by two asymmetrically chelating di\u00adthio\u00adcarbamate ligands so that the coordination geometry is skew-trapezoidal bipyramidal. The most prominent feature of the mol\u00adecular packing are secondary Sn\u22efS inter\u00adactions [Sn\u22efS = 3.5654\u2005(7)\u2005\u00c5] that lead to centrosymmetric dimers. These are connected into a three-dimensional architecture via methyl\u00adene-C\u2014H\u22efS and methyl-C\u2014H\u22efO(morpholino) inter\u00adactions. The Sn\u22efS inter\u00adactions are clearly evident in the Hirshfeld surface analysis of the title compound along with a number of other inter\u00admolecular contacts.The title compound, [Sn(CH Fewer examples are known for five-coordinate, trigonal\u2013bipyramidal species, e.g. (t-Bu)2Sn(S2CNMe2)2 in which one di\u00adthio\u00adcarbamate ligand is monodentate CH2CH2]2Sn(S2CNMe)2 where the carbonyl-O atom of one Sn-bound organic substituent is also coordinating the tin atom 2 structures as the strong chelating ability of the di\u00adthio\u00adcarbamate ligand reduces the Lewis acidity of the tin atom. However, in (I)Both binary tin and organotin di\u00adthio\u00adcarbamates, IV atom in the title compound (I)R2Sn(S2CNRR\u2019)2 mol\u00adecules, i.e. skew-trapezoidal bipyramidal rather than octa\u00adhedral  \u2212 d\u00b0 at the tin atom. The angle subtended at the tin atom by the strongly bound sulfur atoms of 85.878\u2005(19)\u00b0 is significantly less than that formed by the weakly bound sulfur atoms, i.e. 143.066\u2005(18)\u00b0, and is largely responsible for the formation of the skew-trapezoidal plane about the tin atom.The Sna, where two long edges of the translationally displaced trapezoidal planes approach each other to form the inter\u00adactions. Here, Sn\u22efS4i is 3.5654\u2005(7)\u2005\u00c5, which is approximately 0.4\u2005\u00c5 shorter than the sum of the van der Waals radii of Sn and S of 3.97\u2005\u00c5 , Table\u00a02b.An inter\u00adesting feature of the mol\u00adecular packing in (I)et al., 2017dnorm in Fig.\u00a03a indicate the formation of the supra\u00admolecular dimer through secondary Sn\u22efS contacts. On the Hirshfeld surface mapped over electrostatic potential in Fig.\u00a04a. The pair of bright-red spots appearing near the methyl-H12C and morpholine-O1 atoms in Fig.\u00a03b represent the respective donor and acceptor atoms of the C12\u2014H\u22efO1 inter\u00adaction. The comparatively weaker methyl\u00adene-C10\u2014H\u22efS1 inter\u00adaction is viewed as a pair of faint-red spots near these atoms in Fig.\u00a03b. It is important to note from the immediate environments about a reference mol\u00adecule within dnorm-mapped Hirshfeld surfaces highlighting inter\u00admolecular inter\u00adactions in Fig.\u00a05The Hirshfeld surfaces calculated on the structure of (I)a, and those delineated into H\u22efH, S\u22efH/H\u22efS, O\u22efH/H\u22efO, C\u22efH/H\u22efC, N\u22efH/H\u22efN, Sn\u22efS/S\u22efSn and S\u22efS contacts 2. Of these, 12 feature secondary Sn\u22efS inter\u00adactions which, with (I)R2Sn(S2CNRR\u2019)2 structures have Sn\u22efS secondary inter\u00adactions. Selected geometric details for the 13 structures are collated in Table\u00a05A, is a dimeric aggregate disposed about a centre of inversion, as is in (I)i.e. nine. This motif is illustrated in Fig.\u00a07a for (PhCH2)2Sn(S2CNEt2)2 CH2C6H4N-4)2  ligands and self-assemble into supra\u00admolecular chains. In {Me2SnS2CN(CH2Ph)CH2CH2(PhCH2)NCS2SnMe2}2 CH2CH2(PhCH2)NCS2SnMe2}2, where there are two independent, centrosymmetric mol\u00adecules in the asymmetric unit. Here, the resulting supra\u00admolecular chain is twisted \u22121): 1465(s), 1423(s) \u03bd(C\u2014N), 1222(s) \u03bd(C\u2014O), 1110(m), 994(s) \u03bd(C\u2014S), 541(m) \u03bd(Sn\u2014C) cm\u22121. 1H NMR (CDCl3): 4.18 , 3.77 , 1.54 .Sodium morpholine\u00addithio\u00adcarbamate (prepared from the reaction between carbon di\u00adsulfide and morpholine (Merck) in the presence of sodium hydroxide; 1.0\u2005mmol, 0.185\u2005g) in methanol (20\u2005ml) was added to di\u00admethyl\u00adtin dichloride  in methanol (10\u2005ml). The resulting mixture was stirred and refluxed for 2\u2005h. The filtrate was evaporated until an off-white precipitate was obtained. The precipitate was recrystallized from methanol solution by slow evaporation to yield colourless prisms. Yield: 0.305\u2005g, 64.4%; m.p.: 448\u2005K. IR (cmUiso(H) set to 1.2\u20131.5Ueq(C). Owing to poor agreement, one reflection, i.e.  I, global. DOI: 10.1107/S2056989017006855/hb7675Isup2.hklStructure factors: contains datablock(s) I. DOI: 1548414CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Diabetic neuropathy is the most common complication of diabetes. The idea of alterations in energy metabolism in diabetes is emerging. The biogenic antioxidant R(+)-thioctic acid has been successfully used in the treatment of diabetic polyneuropathic (DPN) patients.  The effects of R(+)-thioctic acid  administration were evaluated in 12 DPN patients at baseline and at 15, 30, 60, and 120 administration days throughout the assessment of oxidative stress (OxS); ROS production rate by electron paramagnetic resonance (EPR) technique; and oxidative damage biomarkers (thiobarbituric acid reactive substances (TBARS) and protein carbonyls (PC)), electroneurography (ENG) and visual analogue scale. p < 0.05) at 30 and 60 days. ROS production rate up to \u221216%; TBARS (\u221231%), PC (\u221238%), and TAC up to +48%. Motor nerve conduction velocity in SPE and ulnar nerves (+22% and +16%) and sensor conduction velocity in sural and median nerves (+22% and +5%). Patients reported a general wellness sensation improvement (+35%) at 30 days: lower limb pain sensation (\u221240%) and upper limbs (\u221223%).  Supplementation induced significant changes ( The results strongly indicate that an increased antioxidant capacity plays an important role in OxS, nerve conduction velocity, pain, and general wellness improvement. Nevertheless, the effects of the antioxidant compound were found positive up to 60 days. Then, a hormesis effect was observed. Novelty of the research would be a challenge for investigators to carefully address issues, including dose range factors, appropriate administration time, and targeting population to counteract possible \u201cboomerang effects.\u201d The great number of monitored parameters would firmly stress these conclusions. Type 2 diabetes mellitus (type 2 DM) is the most common form of diabetes, accounting for 90\u201395% of patients in developed countries: in 2030, up to 438 million people affected by type 2 DM have been estimated by recent studies .Type 2 DM is a metabolic disorder, formerly known as non-insulin-dependent diabetes mellitus or adult-onset diabetes, resulting from a combination of insulin resistance and inadequate insulin secretion .Long-term and serious complications of diabetes develop gradually; they can eventually be disabling or even life-threatening . One of 2\u2022\u2212), hydroxyl (HO\u2022), peroxyl (RO2\u2212\u2022), and hydroperoxyl (HRO2\u2212\u2022\u2212) and nonradical species, such as hydrogen peroxide (H2O2) and hydrochloric acid (HOCl)  is also reported in the text. Sample size calculation to determine the minimum number of subjects for adequate study power was made by using the Freeware G\u2217Power software (http://www.psycho.uni-duesseldorf.de/abteilungen/aap/gpower3/). At 80% power, the calculated sample size was of 11 subjects, slightly lower than the subject's population recruited in the present study.All data were presented as mean\u2009\u00b1\u2009SD and were analysed using repeated Shapiro-Wilks 2, blood pressure, heart rate, and pharmacological therapy did not show any significant difference. At T0, the biochemical parameters and the haematological indices resulted in the reference ranges as follows: erythrocyte indices: RBCs: 4.63\u2009\u00b1\u20090.48 106/mm3, HGB: 14.04\u2009\u00b1\u20091.16\u2009g/dL, HCT: 41.46\u2009\u00b1\u20093.52%, MCV: 89.83\u2009\u00b1\u20092.60\u2009\u03bcm3, MCH: 30.44\u2009\u00b1\u20091.04\u2009pg, MCHC: 33.89\u2009\u00b1\u20090.47\u2009g/dL, and RDW: 13.78\u2009\u00b1\u20090.95%; leukocyte indices: WBCs: 6.58\u2009\u00b1\u20091.60 103/mm3, %LYM 27.65\u2009\u00b1\u20096.87, %MON 8.95\u2009\u00b1\u20092.62, %GRA 58.94\u2009\u00b1\u20098.88, #LYM: 1.89\u2009\u00b1\u20090.83 103/mm3, #MON: 0.56\u2009\u00b1\u20090.10 103/mm3, and #GRA 3.81\u2009\u00b1\u20090.80 103/mm3; platelet indices: PLT: 219.75\u2009\u00b1\u200951.01 103/mm3 and MPV: 9.50\u2009\u00b1\u20090.92\u2009\u03bcm3; S-lactate dehydrogenase ((LDH): 327.63\u2009\u00b1\u200977.55\u2009U/L); S-creatinine (0.86\u2009\u00b1\u20090.32\u2009\u03bcmol/L); C-reactive protein ((CRP): 0.23\u2009\u00b1\u20090.33\u2009mg/L). By contrast, haemoglobin A1c ((HbA1c): 6.93\u2009\u00b1\u20090.69%) and glycaemic index ((GI): 165.77\u2009\u00b1\u200932.34\u2009mg/dL) resulted strong increases with respect to the normal range.During the supplementation period of R(+)-thioctic acid and for the whole duration of the study, subjects' weight, BMI, SaOAll biochemical and haematological parameters, monitored at T3, T4, T6, and T8, did not show any statistically significant differences with respect to the basal T0 level.However, the glycaemic index followed a trend parallel to OxS, showing an 8% decrease at T4 and a 26% increase at T6, slowly returning to the basal level after the wash out time period.\u03bcmol\u00b7min\u22121) measured at the different times (T0\u2013T8) in type II DN patients' capillary blood and plasma. The ROS production rate data calculated at any time and the statistically significant differences between times of measurements are shown in Figures Capillary blood (A):T0 (2.14\u2009\u00b1\u20090.21) versus T1 (1.97\u2009\u00b1\u20090.25), T2 (1.77\u2009\u00b1\u20090.31), T3 (1.79\u2009\u00b1\u20090.21), and T6 (2.33\u2009\u00b1\u20090.28); T1 (1.97\u2009\u00b1\u20090.25) versus T6 (2.33\u2009\u00b1\u20090.28), T7 (2.19\u2009\u00b1\u20090.20), and T8 (2.16\u2009\u00b1\u20090.20); T2 (1.77\u2009\u00b1\u20090.31) versus T5 (2.24\u2009\u00b1\u20090.12) and T6 (2.33\u2009\u00b1\u20090.28); T3 (1.79\u2009\u00b1\u20090.21) versus T5 (2.24\u2009\u00b1\u20090.12), T6 (2.33\u2009\u00b1\u20090.28), T7 (2.19\u2009\u00b1\u20090.20), and T8 (2.16\u2009\u00b1\u20090.20).in Plasma (B):T0 (0.20\u2009\u00b1\u20090.03) versus T6 (0.27\u2009\u00b1\u20090.04); T2 (0.19\u2009\u00b1\u20090.03) versus T6 (0.27\u2009\u00b1\u20090.04); T3 (0.18\u2009\u00b1\u20090.03) versus T5 (0.22\u2009\u00b1\u20090.02), T6 (0.27\u2009\u00b1\u20090.04), and T7 (0.22\u2009\u00b1\u20090.02); T4 (0.22\u2009\u00b1\u20090.02) versus T6 (0.27\u2009\u00b1\u20090.04); T5 (0.22\u2009\u00b1\u20090.02) versus T6 (0.27\u2009\u00b1\u20090.04); T6 (0.27\u2009\u00b1\u20090.04) versus T7 (0.22\u2009\u00b1\u20090.02) and T8 (0.21\u2009\u00b1\u20090.02).The antioxidant supplementation of R(+)-thioctic acid induced EPR detectable changes in the ROS production levels (\u03bcM) and PC (nmol\u00b7mg\u22121 protein) concentration data measured at any time and the statistically significant differences between times of measurements are shown in Figures At the same time, the antioxidant supplementation induced changes in the investigated oxidative markers. TBARS (TBARS (A):T2 (14.37\u2009\u00b1\u20094.68) versus T6 (19.02\u2009\u00b1\u20095.60) and T7 (17.82\u2009\u00b1\u20094.93); T3 (12.38\u2009\u00b1\u20094.51) versus T6 (19.02\u2009\u00b1\u20095.60) and T7 (17.82\u2009\u00b1\u20094.93); T4 (11.57\u2009\u00b1\u20093.49) versus T6 (19.02\u2009\u00b1\u20095.60) and T7 (17.82\u2009\u00b1\u20094.93).PC (B):T0 (1.75\u2009\u00b1\u20090.62) versus T2 (1.39\u2009\u00b1\u20090.60), T3 (1.63\u2009\u00b1\u20090.46), T4 (1.08\u2009\u00b1\u20090.46), and T5 (1.56\u2009\u00b1\u20090.59); T2 (1.39\u2009\u00b1\u20090.60) versus T6 (1.99\u2009\u00b1\u20090.65), T7 (1.90\u2009\u00b1\u20090.60), and T8 (1.77\u2009\u00b1\u20090.59); T3 (1.63\u2009\u00b1\u20090.46) versus T6 (1.99\u2009\u00b1\u20090.65), T7 (1.90\u2009\u00b1\u20090.60), and T8 (1.77\u2009\u00b1\u20090.59); T4 (1.08\u2009\u00b1\u20090.46) versus T5 (1.56\u2009\u00b1\u20090.59), T6 (1.99\u2009\u00b1\u20090.65), T7 (1.90\u2009\u00b1\u20090.60), and T8 (1.77\u2009\u00b1\u20090.59); T5 (1.56\u2009\u00b1\u20090.59) versus T6 (1.99\u2009\u00b1\u20090.65).More specifically, the differences between brackets in the Figure are as follows:Finally, the antioxidant capacity in plasma, TAC (mM) concentration data measured at any time, and the statistically significant differences between times of measurements are reported in More specifically, the differences between brackets in the Figure are as follows:T0 (1.42\u2009\u00b1\u20090.38) versus T5 (2.21\u2009\u00b1\u20090.19) and T6 (2.36\u2009\u00b1\u20090.15); T2 (1.72\u2009\u00b1\u20090.17) versus T5 (2.21\u2009\u00b1\u20090.19) and T6 (2.36\u2009\u00b1\u20090.15); T3 (1.85\u2009\u00b1\u20090.18) versus T5 (2.21\u2009\u00b1\u20090.19) and T6 (2.36\u2009\u00b1\u20090.15); T4 (2.10\u2009\u00b1\u20090.19) versus T6 (2.36\u2009\u00b1\u20090.15) and T8 (1.59\u2009\u00b1\u20090.18); T5 (2.21\u2009\u00b1\u20090.19) versus T8 (1.59\u2009\u00b1\u20090.18); T6 (2.36\u2009\u00b1\u20090.15) versus T7 (1.80\u2009\u00b1\u20090.21) and T8 (1.59\u2009\u00b1\u20090.18).In the patient group examined in the present study, the four item symptom DNS score resulted as follows: neuropathic pain: 100% (12 patients); paraesthesia: 58% (7 patients); unsteadiness in walking: 8% (1 pz); numbness in the legs or feet: 0%. Therefore, a score (\u00b1SD) of 1.6\u2009\u00b1\u20090.65, positive for PNP, was calculated. ENG abnormalities were monitored in all patients. Changes in signal amplitude (mV) and distal latency (m/s) in sensory and motor nerves at T0, T3, T4, T6, and T8 were observed (data not shown).R(+)-thioctic acid supplementation induced changes in motor (MNCV m/s) and sensitive (SNCV m/s) conduction velocities see  calculatMNCV (m/s) in ulnar nerve increased significantly at :T3 (53.62\u2009\u00b1\u20096.48) versus T0 (48.06\u2009\u00b1\u20095.58); T3 versus T6 (49.52\u2009\u00b1\u20094.98) and T8 (48.28\u2009\u00b1\u20095.36);superficial peroneal nerve (SPE) MNCV (m/s) increased significantly at :T3 (46.68\u2009\u00b1\u20096.42) and T4 (46.70\u2009\u00b1\u20096.43) versus T0 (38.30\u2009\u00b1\u20095.53).SNCV (m/s) in median wrist-elbow changed significantly at :T0 (52.38\u2009\u00b1\u20094.89) versus T3 (58.76\u2009\u00b1\u20093.24); T3 (58.76\u2009\u00b1\u20093.24) versus T6 (59.16\u2009\u00b1\u20093.90) and T8 (53.60\u2009\u00b1\u20095.96); T6 (59.16\u2009\u00b1\u20093.90) versus T8 (53.60\u2009\u00b1\u20095.96).SNCV (m/s) in sural nerve changed significantly  at T0  (a), TBARS  (b), and PC concentration data  (c) and ROS production in plasma versus TBARS  (d), PC  (e), and glycaemic values  (f) are also displayed.In particular, ROS production in capillary blood versus ROS in plasma . In particular, multiple sources of OxS in diabetes can be found, including nonenzymatic , enzymatic , and mitochondrial pathways , 38. Hyp\u03b1-lipoic acid, evening primrose oil (EPO), or sunflower oil was found to decrease plasma lipid levels and risk factors [\u03b1-lipoic acid on oxidative stress parameters are reported in the literature: increased super oxide dismutase (SOD) and subsequent reduction of H2O2 by catalase [Dietary supplementation with  factors . The poscatalase , 42.2\u2212) levels [Direct evidence of OxS in diabetes was previously provided by the measurement of oxidative stress markers, such as plasma and urinary F2-isoprostane, as well as plasma and tissue nitrotyrosine and superoxide anion radicals (O\u2022) levels , 44.Starting from these considerations, the present study aimed at investigating the effects produced by antioxidant supplementation -thioctic acid, 1.6\u2009g/die) and after the wash out period (two months) on diabetic neuropathic patients throughout ROS production measurement by adopting an innovative EPR method.The study protocol was sketched in As observed in As a matter of fact, in all patients at T0 that is just before the antioxidant supply , a high degree of oxidative damage, as confirmed by the high ROS production rate concentration values, was measured in both capillary blood and plasma.Indeed, the acute effects, \u201cone shot\u201d of R(+)-thioctic acid supplementation in differently aged healthy subjects, were previously reported . A decreIndeed, the results of the present study conducted on diabetic patients, homogeneous for age and physical characteristics see  and concp < 0.01) and kept decreasing at T3  and T4  of daily supplementation. According to the ROS decrease, also, TBARS and PC levels significantly (p < 0.01) decreased at T3 (\u221226 and \u221239%) and T4 (\u221231% and 38%), respectively  increased as shown by the increase of ROS production in capillary blood  and plasma , when compared to the basal level  increased : the OxS values significantly , then returning slowly towards the baseline during the wash out and the periods without administration even if at a slightly higher level . This figure was found also for the ROS production and oxidative damage markers -thioctic acid on ROS production and oxidative damage markers, as well as on motor and sensory nerve conduction velocities see  and 3. TThe role played by OxS in nerve damage has been extensively studied in experiments carried out in an animal model  and moreDiabetic neuropathies are diabetes mellitus-associated disorders probably ascribable to different causes; some of them are not yet well elucidated and in particular how prolonged exposure to high blood glucose levels can produce nerve damage.\u03b1-lipoic acid on nerve functions. In fact, \u03b1-lipoic acid has been shown to improve motor nerve conduction velocity in experimental diabetic neuropathy and to protect peripheral nerves from ischemia in rats [Motor nerve (MNCV) and sensory nerve (SNCV) conduction velocities resulted in the primary endpoints for studying the therapeutic effectiveness of  in rats .Evidence related to changes in nerve conduction velocity after thioctic acid administration was observed primarily in experimental models \u201360.The conduction velocities (m/s) of the sensory component of ulnar and sural nerves in diabetic subjects affected with neuropathy were previously found significantly lower than those measured in diabetics without neuropathy as well as nondiabetic subjects . In well\u03b1-lipoic acid (600\u2009mg/die). This molecule is known to interact with many glucose-converting enzymes, fatty acids, and other energy sources in ATP. In the present study, nerve conduction significantly increased at T3 and T4 (30\u201360 supplementation days): MNCV: +16-17% in ulnar and external sciatic-popliteal (SPE) nerves; SNCV: +12-13% in median and about +16% in sural nerves.Again, the literature data  reportedIndeed, in human studies to date, a great number of studies targeting \u201cthioctic acid\u201d and \u201cdiabetes mellitus\u201d have been published, from which only a few randomized control trials in humans are distinguished in terms of DPN treatment with thioctic acid. We are well aware that nerve conduction velocity cannot be used to monitor changes in oxidative stress; nonetheless, the data of the present study suggested us that the hormesis effect described above could be hypothesized for MNCV and SNCV too: the beneficial effects on nerve conduction were lost after long antioxidant administration time period (T6 and over), almost returning to the pretreatment (T0) conduction velocity values see .VAS is a suitable method to measure pain/pain relief and general wellness. In the present study, in all patients, a regression of the subjective pain sensation as well as a general wellness improvement was reported under R(+)-thioctic acid treatment mainly at T3 and T4 , followed by an improvement of about the 50% after 30\u201360\u2009days of treatment , then returning to the basal level after the wash out period. At the same time, at T3-T4, the general wellness sensation was found to improve at about +35% as well.Side effects, like stomachache and nausea, were reported, but mild or moderate, since no patients interrupted the supplementation for this reason.Side effects as a consequence of alpha-lipoic acid oral administration were previously reported by Ziegler et al. . DespiteA significantly higher dose protocol was followed in the present study (1.6\u2009g/die): patients referred stomachache and nausea mainly at T2-T3 and T5-T6, the symptoms returning to normal after the wash out period see .Nevertheless, during the supplementation time course, patients reported an improvement of the general wellness sensation mainly at T3-T4: in particular, pain at the lower limbs and feet  duration of the treatment, no significant differences were found in the haematological parameters all over the supplementation duration.p < 0.01) linear correlation was found at every time between the ROS production mean values in capillary blood and ROS production in plasma (R2 = 0.76), TBARS (R2 = 0.60), and PC (R2 = 0.79)  relationships were found at every time between ROS production mean values in plasma and TBARS (R2 = 0.58), PC (R2 = 0.66), and glycaemic levels (R2 = 0.54)  was large enough to ensure an adequate study power, as determined by the Freeware G\u2217Power software (see paragraph 2.7). In fact, as already pointed out, at 80% power, the calculated sample size was 11 subjects. However, the population recruited for the study is certainly well below the number of participants standardly recruited for a clinical trial. As a matter of fact, the present study has to be considered as a pilot test. The research concerns the use of an antioxidant substance, the R(+)-thioctic acid, whose acute effects were previously tested on healthy subjects by some of us. In type II diabetic patients, the pilot test study consisted in a very long administration time and the wash out period. Despite the long administration time, none of the patients interrupted the trail so that the results could be obtained at each time from the whole subject sample. It is worth noting the great number of monitored parameters joining oxidative stress by using innovative instruments (EPR) applied by a mini-invasive technique and electroneurography investigations, together with the homogeneity of the assessed results, supported and strengthened by the significance of the correlations -thioctic acid 1.6\u2009mg administration was shown to produce EPR detectable changes in ROS formation as measured in capillary blood and plasma and related oxidative damage parameters with consequent positive effects on nerve conduction velocity too. The findings of the present study strongly indicated that an increased antioxidant capacity plays an important role in the improvement of OxS, nerve conduction velocity, pain, and general wellness. Nevertheless, at the same time, the results of the study showed that the safety effects of an exogenous antioxidant compound were positive up to 60 administration days. After this period, a hormesis effect was observed. Therefore, the novelty of the conducted research would be a challenge for investigators to carefully address issues, including dose range factors, as well as appropriate administration time and targeting population to counteract possible \u201cboomerang effects\u201d of the treatment. The great number of parameters monitored in this study would firmly stress these conclusions."}
{"text": "Scientific Reports6: Article number: 3157410.1038/srep31574; published online: 08172016; updated: 02172017\u20134\u2009\u03bc W cm\u22122, at 4.5\u2009cm) illuminated the surface of the polymer samples\u201d.This Article contains an error in the Methods section. \u201cTwo 30\u2009W UVC lamps  illuminated the surface of the polymer samples\u201d.\u201cTwo 30\u2009W UVC lamps (253.7\u2009nm, irradiance of 0.01\u2009W\u2009cm"}
{"text": "I atom in the mol\u00adecular structure of the title compound exhibits a distorted tetra\u00adhedral coordination sphere, defined by two N atoms of the chelating ligand, one N atom of the aceto\u00adnitrile ligand and one iodide ligand.The Cu 2H3N)(C26H24N2)], the CuI ion has a distorted tetra\u00adhedral coordination environment, defined by two N atoms of the chelating 2--6-[imino]\u00adpyridine ligand, one N atom of an aceto\u00adnitrile ligand and one iodide ligand. Within the complex, there are weak intra\u00admolecular C\u2014H\u22efN hydrogen bonds, while weak inter\u00admolecular C\u2014H\u22efI inter\u00adactions between complex mol\u00adecules, help to facilitate a three-dimensional network.In the mononuclear title complex, [CuI(C The two N atoms of the bidentate ligand chelate to CuI with similar Cu\u2014N bond lengths . A comparable N,N\u2032-binding has been observed in related structures with bis\u00ad[2-(2-pyrid\u00adyl)eth\u00adyl]amine ligands \u2005\u00c5. The N2\u2014Cu1\u2014N1 bite angle of the chelating ligand is 78.86\u2005(18)\u00b0, while the N3\u2014Cu\u2014I angle between the monodentate aceto\u00adnitrile and iodide ligands is closer to tetra\u00adhedral, 112.74\u2005(15)\u00b0. The naphthyl ring system is inclined by 58.20\u2005(17)\u00b0 to the central N=C(CH3)\u2014pyridine moiety, whereas the tri\u00admethyl\u00adphenyl ring is almost perpendicular to the latter, at 84.8\u2005(3)\u00b0. Within the complex, an intra\u00admolecular C\u2014H\u22efN hydrogen-bonding inter\u00adaction is present, stabil\u00adizing the mol\u00adecular conformation \u2005\u00c5, 152\u00b0; symmetry code: (i) x, y\u00a0\u2212\u00a01, z] and a H atom of the aceto\u00adnitrile methyl group  link the complex mol\u00adecules, forming a three-dimensional network  was synthesized according to a modified literature procedure  in 5\u2005ml of aceto\u00adnitrile. The mixture was stirred at room temperature for 24\u2005h before evaporating the volatiles. The residue was extracted with n-hexane (5 \u00d7 3\u2005ml). The extracts were combined and the solvent removed under reduced pressure to give a red solid which was recrystallized from aceto\u00adnitrile solution. Yield: 54%. M.p. >253\u2005K (decomp). 1H NMR : \u03b4 1.88 , 1.97 , 2.16 , 2.20 , 6.84 , 7.39 , 7.45 , 7.51 , 7.73 , 7.81 , 7.87 , 8.04 . IR \u03bdmax (solid)/cm\u22121 1620 (C=Nimine), 1555 (C=Npy). ESI MS: m/z 428 [M\u2013I\u2013MeCN]+.A solution of 0.0262\u2005g of CuI (0.137\u2005mmol) in 5\u2005ml of aceto\u00adnitrile was mixed with a solution of 0.05\u2005g of Uiso(H) = 1.2Ueq(C) for H atoms on Csp2 and 0.98\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for H atoms on Csp3.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016018685/wm5341sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016018685/wm5341Isup2.hklStructure factors: contains datablock(s) I. DOI: 1518571CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion is completed by the ligation of two N atoms of two piperazinium ions. In the crystal, a network of N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds leads to the formation of a three-dimensional supra\u00admolecular structure.In the title compound, two thio\u00adsulfate ions coordinate to the zinc(II) ion through the terminal S atoms. The tetra\u00adhedral coordination around the Zn 4H11N2)2(S2O3)2]\u00b72H2O, two thio\u00adsulfate ions coordinate to the zinc(II) atom through the terminal S atoms. The tetra\u00adhedral coordination around the ZnII ion is completed by ligating to two N atoms of two piperazinium ions. The remaining two N atoms of the piperazinium ions are diprotonated and do not coordinate to the metal centre. In the crystal, however, they are involved in N\u2014H\u22efOwater and N\u2014H\u22efOsulfato hydrogen bonds. Together, a series of N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, involving the O atoms of the thio\u00adsulfate ions and the water mol\u00adecules as acceptors and the hydrogen atoms of the piperazinium ions and the water mol\u00adecules as donors, form a three-dimensional supra\u00admolecuar structure. Within this framework there are a number of intra- and inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efS contacts present.In the title compound, [Zn(C Recently, Natarajan and co-workers  and two nitro\u00adgen atoms from the piperazinium ions (N1 and N3), in an approximately tetra\u00adhedral geometry . The Zn\u2014S bond lengths are 2.2927\u2005(4)\u2005\u00c5 for Zn1\u2014S1 and 2.3324\u2005(4)\u2005\u00c5 for Zn1\u2014S3. The Zn\u2014N bond lengths are 2.0879\u2005(13)\u2005\u00c5 for Zn1\u2014N1 and 2.0727\u2005(12)\u2005\u00c5 for Zn1\u2014N3. The N/S\u2014Zn1\u2014S/N bond angles lie in the range 101.24\u2005(4) to 116.79\u2005(2)\u00b0, confirming the tetra\u00adhedral nature of the zinc ions. Within the two thio\u00adsulfate ligands, the S\u2014S bond lengths are 2.0511\u2005(5)\u2005\u00c5 for S1\u2014S2 and 2.0332\u2005(5)\u2005\u00c5 for S3\u2014S4. The S\u2014O bond lengths vary from 1.4437\u2005(14) to 1.4623\u2005(13)\u2005\u00c5, while the O\u2014S\u2014O angles vary from 104.53\u2005(5) to 112.85\u2005(10)\u00b0, which is indicative of a fairly regular tetra\u00adhedral arrangement. In the mol\u00adecular unit, the two thio\u00adsulfate units are bonded to the zinc(II) ion only through the terminal S atoms, and the oxygen atoms are uncoordinated. In addition, only one nitro\u00adgen atom of each piperazinium ion is bonded to the zinc(II) ion, the second being diprotonated in each case.The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01The supra\u00admolecular architecture Fig.\u00a02 arises fet al., 2016et al. zinc(II) hemihydrate (CSD refcode: WEHTOT). The thio\u00adsulfate ligand is coordinated to the zinc ions through S and O atoms, forming octa\u00adhedral zinc centres. In addition, a zinc\u2013thio\u00adsulfate complex containing both one-dimensional cationic and anionic chains has been reported by the same authors, viz. catena-[tetra\u00adaqua\u00adzinc(II) bis\u00adbis\u00ad(thio\u00adsulfato-\u03baS)dizinc(II) dihydrate]  (IJUWER), catena-[(\u03bc-thio\u00adsulfato)\u00adzinc] (IJU\u00adWIV), and catena-[bis\u00ad\u00adbis\u00ad(\u03bc-thio\u00adsulfato)\u00addizinc dihydrate] (IJUWOB) and catena-[bis\u00ad\u00adbis\u00ad(\u03bc-thio\u00adsulfato)\u00addizinc (\u03bc-thio\u00adsulfato)\u00adzinc trihydrate] (IJUWUH).Karthik & Natarajan 2016 have recet al., 1996et al., 2001et al., 2004A number of mol\u00adecular cadmium\u2013thio\u00adsulfate and manganese\u2013thio\u00adsulfate structures have been reported by Baggio and co-workers (thio\u00adsulfato)cadmium (CSD refcode: ORUJOC), which was reported recently, was isolated in the presence of the aliphatic amine 1,3-di\u00adamino\u00adpropane 2\u00b76H2O  was dissolved in 5\u2005ml distilled water. Then (NH4)2S2O3  was added to the solution, which was stirred for 15\u2005min. Piperazine  was dissolved separately in distilled water (5\u2005ml) and the solution poured into the initial reaction mixture until the pH was 8. The resulting solution was left undisturbed and after 1 week, colourless block-shaped crystals were obtained. The product was filtered and washed with cold water. The yield was approximately 85% based on Zn metal. Elemental analysis calculated for C8H26N4O8S4Zn: C 19.20, H 5.24, N 11.20%; found: C 19.27, H 5.29, N 11.16%.Zn = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018000555/cq2022sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018000555/cq2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 1571150CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-017-03589-w, published online 12 June 2017Correction to: The original version of this Article contained a typographical error in the Abstract.9/L)\u2009\u00d7\u2009AST(U/L).\u201d\u201cThe formula of the mFIB-4 index is 10\u2009\u00d7\u2009Age(years)\u2009\u00d7\u2009AST(U/L)/Platelet count(10now reads:9/L)\u2009\u00d7\u2009ALT(U/L).\u201d\u201cThe formula of the mFIB-4 index is 10\u2009\u00d7\u2009Age(years)\u2009\u00d7\u2009AST(U/L)/Platelet count(10This has now been corrected in the PDF and HTML versions of the Article."}
{"text": "Crystal structures of hydrogen-bonded 1:2 dihydrate compounds of chloranilic acid with 2-carb\u00adoxy\u00adpyridine (I) and 2-carb\u00adoxy\u00adquinoline (II) have been determined at 180 and 200\u2005K, respectively. The base mol\u00adecule in (I) is disordered over cationic and twitterionic states, while that in (II) is in a twitterionic form. In each crystal, the three components are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming a layer structure. 6H5.5NO20.5+\u00b7C6HCl2O4\u2212\u00b72H2O, (I), has been determined at 180\u2005K, and the structure of the 1:2 dihydrate compound of chloranilic acid with 2-carb\u00adoxy\u00adquinoline , namely, 2C10H7NO2\u00b7C6H2Cl2O4\u00b72H2O, (II), has been redetermined at 200\u2005K. This determination presents a higher precision crystal structure than the previously published structure [Marfo-Owusu & Thompson  was analysed as a disordered structure over two states, viz. salt and co-crystal. The salt is bis\u00ad(2-carb\u00adoxy\u00adpyridinium) chloranilate dihydrate, 2C6H6NO2+\u00b7C6Cl2O42\u2212\u00b72H2O, and the co-crystal is bis\u00ad(pyridinium-2-carboxyl\u00adate) chloranilic acid dihydrate, 2C6H5NO2\u00b7C6H2Cl2O4\u00b72H2O, including zwitterionic 2-carb\u00adoxy\u00adpyridine. In both salt and co-crystal, the water mol\u00adecule links the chloranilic acid and 2-carb\u00adoxy\u00adpyridine mol\u00adecules through O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. The 2-carb\u00adoxy\u00adpyridine mol\u00adecules are connected into a head-to-head inversion dimer by a short O\u2014H\u22efO hydrogen bond, in which the H atom is disordered over two positions. Compound (II) is a 1:2 dihydrate co-crystal of chloranilic acid and zwitterionic 2-carb\u00adoxy\u00adquinoline. The water mol\u00adecule links the chloranilic acid and 2-carb\u00adoxy\u00adquinoline mol\u00adecules through O\u2014H\u22efO hydrogen bonds. The 2-carb\u00adoxy\u00adquinoline mol\u00adecules are connected into a head-to-tail inversion dimer by a pair of N\u2014H\u22efO hydrogen bonds.The crystal structure of the 1:2 dihydrate compound of chloranilic acid  with 2-carb\u00adoxy\u00adpyridine , namely, 2Cpson 2014. X-ray S The pyridine rings are also stacked along the b axis through a \u03c0\u2013\u03c0 inter\u00adaction [centroid\u2013centroid distance = 3.6851\u2005(7)\u2005\u00c5 and inter\u00adplanar spacing = 3.4787\u2005(5)\u2005\u00c5]. Between the layers, a short Cl\u22efCl contact is observed [Cl1\u22efCl1v = 3.3717\u2005(5)\u2005\u00c5; symmetry code: (v) \u2212x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a0In the crystal of compound (I)ne Fig.\u00a04. In the via a pair of N\u2014H\u22efO hydrogen bonds \u2005\u00c5. The water mol\u00adecule links the stacked base mol\u00adecules related by translation along a via O\u2014H\u22efO hydrogen bonds [O5\u2014H3\u22efO4 and O5\u2014H4\u22efO4ii; Table\u00a02via O\u2014H\u22efO hydrogen bonds, forming a layer structure parallel to et al., 2016A search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(O). For the water H atoms, distant restraints of H\u22efH = 1.37\u2005(4)\u2005\u00c5 were also applied. C-bound H atoms were positioned geometrically (C\u2014H = 0.95\u2005\u00c5) and were treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a03Uiso(H) = 1.2Ueq(C).All H atoms in compound (II)10.1107/S2056989017015997/lh5860sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989017015997/lh5860Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017015997/lh5860IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017015997/lh5860IIsup4.cmlSupporting information file. DOI: 1583721, 1583720CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "DNGR\u20101 is receptor expressed by certain dendritic cell (DC) subsets and by DC precursors in mouse. It possesses a C\u2010type lectin\u2010like domain (CTLD) followed by a poorly characterized neck region coupled to a transmembrane region and short intracellular tail. The CTLD of DNGR\u20101 binds F\u2010actin exposed by dead cell corpses and causes the receptor to signal and potentiate cross\u2010presentation of dead cell\u2010associated antigens by DCs. Here, we describe a conformational change that occurs in the neck region of DNGR\u20101 in a pH\u2010 and ionic strength\u2010dependent manner and that controls cross\u2010presentation of dead cell\u2010associated antigens. We identify residues in the neck region that, when mutated, lock DNGR\u20101 in one of the two conformational states to potentiate cross\u2010presentation. In contrast, we show that chimeric proteins in which the neck region of DNGR\u20101 is replaced by that of unrelated C\u2010type lectin receptors fail to promote cross\u2010presentation. Our results suggest that the neck region of DNGR\u20101 is an integral receptor component that senses receptor progression through the endocytic pathway and has evolved to maximize extraction of antigens from cell corpses, coupling DNGR\u20101 function to its cellular localization. Bufferlong mouse DNGR\u20101 ECD to mildly denaturing (Laemmli buffer) or strongly denaturing (8\u00a0M urea) conditions in the presence of DTT and analyzed the samples by SDS\u2013PAGE and Western blot. As predicted, strongly denaturing conditions almost completely abolished the ability of DNGR\u20101 to resist reduction, while under weakly denaturing conditions the reduction\u2010insensitive dimers could be observed. In the absence of reducing agents, the protein maintained its dimeric status regardless of the denaturing conditions  to induce the reduction\u2010resistant state, dialyzed the protein back into PBS, and tested its reduction sensitivity. As expected, we observed reduction\u2010resistant dimers under mildly acidic conditions , all the proteins were readily reducible while, when subjected to weakly acidic conditions (pH 6.1), they showed increased resistance to reduction Fig\u00a0B. These We expressed a chimeric ECD, in which the neck region of DNGR\u20101 was fused to the CTLD of another C\u2010type lectin receptor, dectin\u20101 Fig\u00a0A. Dectinlong mouse and human DNGR\u20101 isoforms under neutral (PBS) or mildly acidic (MES pH 6.1) conditions, and observed almost perfect overlap between the two . Far\u2010UV CD spectra reflect the secondary structure content of the protein while near\u2010UV CD signals derive from the three aromatic residues  and, in some cases, from disulfide bonds, and reflect protein tertiary structure  conditions , suggesting that the part of the neck region involved in the process is conserved between the two. In order to pinpoint its location, we genetically removed overlapping blocks of 10\u201311 amino acids from the conserved part of the neck [K57\u2013L66 (\u03941), L64\u2013I73 (\u03942), L72\u2013L82 (\u03943), N81\u2013T90 (\u03944), R87\u2013A96 (\u03945), and Q95\u2013S104 (\u03946)  resulted in an ECD protein that behaved like the \u03944 mutant in that it formed type\u20102 dimers in neutral conditions   overnight and measured the extent of T\u2010cell reactivation by assessing the amount of IFN\u2010\u03b3 that accumulated in the culture medium. Consistent with previous data . pH\u2010induced conformational changes have been reported for other proteins and are often mediated by protonation of one or more histidines stabilizing forces in the same range as electrostatic repulsion, they can contribute to, and perhaps even be sufficient for, pH\u2010sensitive conformational rearrangements . Thus, other parts of DNGR\u20101 are also involved in determining the ability of the receptor to promote cross\u2010presentation of dead cell\u2010associated antigens.long mouse, K57\u2013I238 for short mouse, and K57\u2013V241 for the human isoform) or mouse dectin\u20101 (R71\u2013L244) was inserted into the p3xFLAG\u2010CMV\u20109 expression vector (Sigma\u2010Aldrich) and all the constructs were verified by sequencing. The proteins were expressed by transient transfection in 239F cells, as described previously  and following primers: C94S: 5\u2032\u2010CCATGCATGATCCAATTAGGAAGGCATGTTTCCTTGCTGTCCAGGGTCTG\u20103\u2032, \u03941: 5\u2032\u2010CAAGGATGACGATGACAAGCTTGCGGCCGCGGAGCAGCAGGAAAGACTCATCCAACAGGAC\u20103\u2032, \u03942: 5\u2032\u2010CGGCCGCGAAGTTCTTCCAGGTATCCTCTCAACAGGACACAGCATTGGTGAACCTTACAC\u20103\u2032, \u03943: 5\u2032\u2010CCTCTCTTGTCTTGGAGCAGCAGGAAAGAACACAGTGGCAGAGGAAATACACACTGGAATACTGCC\u20103\u2032, \u03943A: 5\u2032\u2010GGTATCCTCTCTTGTCTTGGAGCAGCAGGAAAGAGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCACACAGTGGCAGAGGAAATACACACTGGAATACTGCCAAGCC\u20103\u2032, \u03944: 5\u2032\u2010GGAAAGACTCATCCAACAGGACACAGCATTGGTGCTGGAATACTGCCAAGCCTTACTGCAGAGATCTCTCC\u20103\u2032, \u03944A: 5\u2032\u2010GCAGGAAAGACTCATCCAACAGGACACAGCATTGGTGGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCCTGGAATACTGCCAAGCCTTACTGCAGAG\u20103\u2032, \u03945: 5\u2032\u2010GACACAGCATTGGTGAACCTTACACAGTGGCAGTTACTGCAGAGATCTCTCCATTCAGGCAC\u20103\u2032, \u03946: 5\u2032\u2010CAGTGGCAGAGGAAATACACACTGGAATACTGCGGCACAGATGCTTCTACTGGACCAG\u20103\u2032, \u03946A: 5\u2032\u2010GTGAACCTTACACAGTGGCAGAGGAAATACACACTGGAATACTGCGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCGGCACAGATGCTTCTACTGGACCAGTTCTTCTGAC\u20103\u2032.long mouse DNGR\u20101 (K57\u2013T130) with 5\u2032 and 3\u2032 sequences complementary to regions of the p3xFLAG\u2010CMV\u20109 plasmid and dectin\u20101, respectively, was amplified in a PCR with Phusion Hot Start II polymerase (Thermo Scientific), using the following primers: 5\u2032\u2010GCTGGGTGCCCTAGCATTTTGGAAGTTCTTCCAGGTATCCTCTCTTG\u20103\u2032 and 5\u2032\u2010CCATGCATGATCCAATTAGGAAGGCATGTTTCCTTGCTGTCCAGGGTCTG\u20103\u2032 and a DNGR\u20101\u2010coding plasmid as a template, and then used in a modified reaction with QuikChange Lightning kit (Agilent Technologies) as per manufacturer's instructions with p3xFLAG\u2010CMV\u20109 plasmid containing dectin\u20101 ECD sequence as a template. For generation of chimeric DNGR\u20101 proteins with the neck region of CD69 or Ly49, \u201cmegaprimers\u201d covering the entire neck region of appropriate proteins were generated using the following primers: 5\u2032\u2010GTTAGCAACGTCCATTTTCTTGGGCATCGGCAAGTACAATTGCCCAGGCTTG\u20103\u2032 and 5\u2032\u2010GTGGACAAGGGCTGCAGTCACTACCAGCAACATGGTGGTCAGATG\u20103\u2032 for CD69 and 5\u2032\u2010GTTAGCAACGTCCATTTTCTTGGGCATCAACATTTTTCAGAATAGTCAACAAAATCATGAACTGCAGG\u20103\u2032 and 5\u2032\u2010GTGGACAAGGGCTGCAGTCACTACCTTCAAAACCTCTGCCTGTGTGCTGTGAGG\u20103\u2032 for Ly49. cDNA generated from total splenic mRNA of a C57BL/6 and a CBA/J mouse, respectively, was used as templates. \u201cMegaprimers\u201d were then used in a modified reaction with QuikChange Lightning kit (Agilent Technologies) as per manufacturer's instructions with pFB\u2010IRES GFP plasmid containing the entire sequence of DNGR\u20101 as a template.For the chimeric DNGR\u20101:dectin\u20101 protein, a \u201cmegaprimer\u201d covering the whole neck region of Samples for SDS\u2013PAGE were prepared in 6\u00d7 Laemmli buffer (60% (v/v) glycerol, 150\u00a0mg/ml SDS, 0.75\u00a0mg/ml bromophenol blue in 75\u00a0mM Tris\u2013HCl pH 6.8) under reducing (+100\u00a0mM DTT) or non\u2010reducing conditions unless otherwise stated. Separation was carried out using 4\u201320% Mini\u2010PROTEAN TGX precast gels (Bio\u2010Rad). Proteins were transferred onto Immobilon P membrane (Merck Millipore) using wet transfer, the membrane was blocked in 5% milk in PBS + 0.05% Tween\u201020, and ECD proteins were detected using HRP\u2010conjugated M2 anti\u2010FLAG antibody (Sigma\u2010Aldrich). Full\u2010length DNGR\u20101 was detected using anti\u2010DNGR\u20101 antibody (clone 397) followed by HRP\u2010conjugated polyclonal anti\u2010rat antibody (IgG (H+L); Stratatech).long DNGR\u20101 ECD was concentrated to 7\u00a0mg/ml and, immediately before analysis, diluted into PBS or 10\u00a0mM MES pH 6.1 to final concentration 170\u00a0\u03bcg/ml. Human DNGR\u20101 ECD was concentrated to 1.4\u00a0mg/ml and immediately before analysis diluted into PBS or 10\u00a0mM MES pH 6.1 to final concentration 140\u00a0\u03bcg/ml. Far\u2010UV CD spectra (260\u2013195\u00a0nm) were recorded at 20\u00b0C in 1\u00a0mm fused silica cuvettes using a Jasco J\u2010815 spectropolarimeter fitted with a cell holder temperature controlled by a CDF\u2010426S Peltier unit. The spectra were typically recorded with 0.1\u2010nm resolution and baseline corrected by subtraction of the appropriate buffer spectrum. CD intensities are presented as the CD absorption coefficient calculated on a mean residue weight basis (\u0394\u03b5MRW). Secondary structure content was estimated using methods originally described by Sreerama and Woody  were recorded at 20\u00b0C in 10\u00a0mm fused silica cuvettes. Near\u2010UV CD intensities are presented on a molecular weight basis (\u0394\u03b5M).For far\u2010UV CD, mouse et\u00a0al, et\u00a0al, 2) and polymerized in F\u2010buffer . Polymerized actin was stabilized with 5\u00a0\u03bcM phalloidin (Life Technologies) and spotted onto nitrocellulose membrane (Whatman) in twofold dilution series. The membrane was blocked in 5% milk in PBS + 0.05% Tween\u201020 overnight and incubated with protein supernatants diluted into appropriate buffers at equal concentrations. Binding of all proteins was detected using HRP\u2010conjugated M2 anti\u2010FLAG antibody (Sigma\u2010Aldrich) and revealed using SuperSignal West Pico Chemiluminescent Substrate (Thermo Scientific) or Luminata Forte Western HRP Substrate (Merck Millipore).Dot blot assay was performed as described previously  supplemented with \u03b2\u2010ME and 10% heat\u2010inactivated fetal calf serum (FCS) at 37\u00b0C and 5% CO2. 293F cells were grown in FreeStyle 293 Expression Medium (Gibco) at 37\u00b0C, 8% CO2, and with constant shaking on an orbital shaker at 120\u00a0rpm. 293FT cells were grown in DMEM medium (Gibco) supplemented with 10% heat\u2010inactivated fetal calf serum (FCS) at 37\u00b0C and 10% CO2.Phoenix, B3Z\u2010Syk , VSV\u2010G envelope protein\u2010coding plasmid, and a pFB plasmid coding for the desired protein. On days 1, 2, and 3 post\u2010transfection, the pseudotyped virus\u2010containing culture medium was recovered, filtered, supplemented with 8\u00a0\u03bcg/ml polybrene (Sigma\u2010Aldrich), and immediately applied to target cells. The plate was centrifuged for 90\u00a0min at 2,500\u00a0\u00d7\u00a0g at room temperature and left in the incubator for a further 90\u00a0min. After the incubation, the medium was exchanged for fresh complete IMDM medium. On day 5, selection medium containing 0.5\u00a0\u03bcg/ml puromycin was applied. Surviving cells after 1\u00a0week of selection were expanded and transduced in an identical manner as described above with lentivirus generated in 293FT cells transfected with a mixture of Lipofectamine 2000, psPax2, pMD2.G, and pLX\u2010sgRNA plasmids. Successfully transduced cells were selected in medium containing 5\u00a0\u03bcg/ml blasticidin. Surviving cells after 1\u00a0week of selection were expanded and Cas\u20109 expression was induced by addition of 1\u00a0\u03bcg/ml doxycycline to the culture medium for 3\u00a0weeks. Cells that lost DNGR\u20101 expression were then purified by FACS sorting. The sequence of sgRNA used was as follows: CTGAACATTTGCTAGGGGAT. pCW\u2010Cas9 and pLX\u2010sgRNA plasmids were a gift from Eric Lander & David Sabatini (Addgene plasmids #50661 and #50662), pMD2.G and psPAX2 plasmids were a gift from Didier Trono (Addgene plasmids #12259 and #12260).293FT cells were transfected by a mixture of Lipofectamine 2000 (Thermo Fisher Scientific), psPax2, pMD2.G, and pCW\u2010Cas9 plasmids. Lentivirus\u2010containing culture medium was recovered on days 1, 2, and 3 post\u2010transfection, filtered, diluted 1:9, supplemented with 8\u00a0\u03bcg/ml polybrene (Sigma\u2010Aldrich), and immediately applied to MuTu cells. The plate was centrifuged for 90\u00a0min at 2,500\u00a0\u00d7\u00a0et\u00a0al, 2 for 45\u00a0min. After the incubation, the cells were harvested, washed in ice\u2010cold PBS + 5\u00a0mM EDTA, and fixed in 4% PFA. After fixation, the cells were washed in FACS buffer  and surface\u2010stained with PE\u2010conjugated anti\u2010DNGR\u20101 antibody (clone 1F6). Staining was analyzed using LSR Fortessa Flow cytometer (BD Biosciences). Data analysis was performed in FlowJo 9.8.5 software (TreeStar).Internalization assay was described previously  293T cells at the indicated ratios, or in wells coated with anti\u2010DNGR\u20101 antibody (clone 7H11) or in medium alone in a 96\u2010well plate. LacZ activity after incubation overnight at 37\u00b0C and 5% CO2 was determined by lysing the cells in CPRG (Roche) containing buffer and measuring OD595 with OD655 as a reference at multiple time points.B3Z\u2010Syk reporter assay was described previously  and left overnight to undergo secondary necrosis. Cell corpses were harvested, washed once in full RPMI1640 medium, and plated at indicated ratios with 6\u00a0\u00d7\u00a0104 MuTu cells per well in a U\u2010bottom 96\u2010well plate. After a 4\u2010h incubation at 37\u00b0C and 5% CO2, 3\u00a0\u00d7\u00a0104 pre\u2010activated OT\u2010I T cells (see below) were added to each well and incubated at 37\u00b0C and 5% CO2 overnight. Next morning, the plate was freeze\u2013thawed once, and total amount of IFN\u2010\u03b3 in the supernatants was determined by ELISA.Ovalbumin\u2010expressing mouse embryonic fibroblasts (bm1 T OVA MEFs; Sancho \u2212/\u2212 mice were bred at The Francis Crick Institute under specific pathogen\u2010free conditions in accordance with the national and institutional guidelines for animal care and approval by The Francis Crick Institute Animal Ethics Committee and by the Home Office, UK. Spleen and lymph nodes from one OT\u2010I Rag1\u2212/\u2212 mouse were homogenized into a single cell suspension. Cells were plated at 1\u00a0\u00d7\u00a0105 per ml in complete RPMI1640 medium supplemented with 0.1\u00a0nM SIINFEKL peptide. On day 3 of culture, IL\u20102 was added to a final concentration of 25\u00a0U/ml. CD8+ T cells were MACS\u2010enriched on day 5 and used immediately.OT\u2010I Rag1PH designed the study, performed and analyzed experiments, and wrote the manuscript. OS provided technical assistance, contributed to the design of experiments, and performed some of the experiments shown in Fig\u00a0The authors declare that they have no conflict of interest.Review Process FileClick here for additional data file.Source Data for Figure\u00a01Click here for additional data file.Source Data for Figure\u00a02Click here for additional data file.Source Data for Figure\u00a03Click here for additional data file.Source Data for Figure\u00a04Click here for additional data file.Source Data for Figure\u00a06Click here for additional data file."}
{"text": "The title structure consists of 3-amino\u00adpyridinium cations and 1\u2032-carb\u00adoxy\u00adferrocene-1-carboxyl\u00adate monoanions held together by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds. 5H7N2)[Fe(C6H4O2)(C6H5O2)], consists of 3-amino\u00adpyridinium cations and 1\u2032-carb\u00adoxy\u00adferrocene-1-carboxyl\u00adate monoanions. The ferrocenyl moiety of the anion adopts a typical sandwich structure, with Fe\u2014C distances in the range 2.0270\u2005(15)\u20132.0568\u2005(17)\u2005\u00c5. The anion possesses an eclipsed conformation, with the torsion angle \u03c6 (Csubst\u2014Cpcent\u2014Cpcent\u2014 Csubst) equal to 66.0\u00b0. The conformations of other 1\u2032-carb\u00adoxy\u00adferrocene-1-carboxyl\u00adate monoanions are compared and analyzed on the basis of literature data.The structure of the title salt, (C The C16\u2014O bond lengths within the carboxyl\u00adate anion are almost equal [1.2604\u2005(19) and 1.2636\u2005(19)\u2005\u00c5], whereas, in contrast, they differ greatly within the carb\u00adoxy\u00adlic acid group, with C26=O22\u00a0= 1.2128\u2005(19)\u2005\u00c5 and C26\u2014O21 = 1.326\u2005(2)\u2005\u00c5, the latter involving the OH group. The planes of the cyclo\u00adpenta\u00addienyl (Cp) rings are almost parallel to the planes of the corresponding carb\u00adoxy/carboxyl\u00adate groups, with O\u2014C\u2014C\u2014C torsion angles less than 13\u00b0. The conformation of 1,1\u2032-disubstituted ferrocenes is described by the torsion angle Csubst\u2014Cpcent\u2014Cpcent\u2014Csubst, where Csubst stands for a ferrocene C atom with an additional bonding partner and Cpcent for the centre of gravity of the C atoms of the ring; this angle is hereafter referred to as \u03c6. In (1), the anion possesses an eclipsed conformation with \u03c6 = 66.0\u00b0   consists of one 3-amino\u00adpyridinium cation and one 1\u2032-carb\u00adoxy\u00adferrocene-1-carboxyl\u00adate monoanion Fig.\u00a01. In the \u00b0) Fig.\u00a02.\u2212O2C hydrogen bonds of medium\u2013strong-to-weak nature and of CO2H\u22ef\u2212O2C hydrogen bonds of strong nature  by charge-supported NH\u22efe Table\u00a02.et al., 20162C-\u03b75-C5H4)Fe(\u03b75-C5H4-CO2\u2212) units from 14 crystallographically independent monoanions. Among these 14 fragments, three adopt a trans-staggered conformation, with m = 5  was added dropwise to 1,1\u2032-di\u00adacetyl\u00adferrocene  under stirring at a temperature of 317\u2013320\u2005K. The solution was stirred at this temperature for 2\u2005h. Three more 25\u2005ml portions of NaOCl solution were added every 2\u2005h. The reaction mixture was filtered and acidified to a pH of 1.1 with 10% hydro\u00adchloric acid and cooled to 277\u2005K overnight. The yellow precipitate which formed was filtered off and recrystallized from ethanol to give an orange microcrystalline powder .Ferrocene-1,1\u2032-di\u00adcarb\u00adoxy\u00adlic acid  was dissolved in methanol and mixed with a methano\u00adlic solution of 3-amino\u00adpyridine . The reaction mixture was filtered and subjected to slow evaporation at room temperature to give orange crystals of the title salt.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017007058/wm5388sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007058/wm5388Isup2.hklStructure factors: contains datablock(s) I. DOI: 1444115CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E configuration with respect to the azomethine bond, and one nitrate anion.The title aroyl hydrazone Schiff base salt, consists of one mol\u00adecular cation in the keto tautomeric form, adopting an  13H12N3O2+\u00b7N O3\u2212, consists of one mol\u00adecular cation in the keto tautomeric form, adopting an E configuration with respect to the azomethine bond, and one nitrate anion. The two units are linked via an N\u2014H\u22efO hydrogen bond. The mol\u00adecule overall is non-planar, with the pyridinium and benzene rings being inclined to each other by 4.21\u2005(4)\u00b0. In the crystal, cations and anions are linked via inter\u00admolecular O\u2014H\u22efO and bifurcated N\u2014H\u22efO hydrogen bonds, forming a two-dimensional network parallel to (101). These networks are further linked by C\u2014H\u22efO hydrogen bonds, forming slabs parallel to (101). The slabs are linked by offset \u03c0\u2013\u03c0 inter\u00adactions, involving the benzene and pyridinium rings of adjacent slabs [inter\u00adcentroid distance = 3.610\u2005(2)\u2005\u00c5], forming a three-dimensional structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efO/O\u22efH (45.1%), H\u22efH (19.3%), H\u22efC/C\u22efH (14.5%), H\u22efN/N\u22efH (7.9%) and C\u22efC (6.0%) inter\u00adactions.The asymmetric unit of the title aroyl hydrazone Schiff base salt, C The orgE, where torsion angle N1\u2014N2\u2014C8\u2014C9 is \u2212177.58\u2005(14)\u00b0. On the other hand, torsion angles N2\u2014N1\u2014C7\u2014C5 and C8\u2014N2\u2014N1\u2014C7 are \u2212179.66\u2005(13) and \u2212178.09\u2005(15)\u00b0, respectively, and the benzene (C1\u2013C6) and pyridinium (N3/C9\u2013C13) rings are oriented at a dihedral angle of 4.21\u2005(4)\u00b0, probably due to the steric inter\u00adactions between the hydrogen atoms (Table\u00a02The configuration at the N2=C8 [1.276\u2005(2)\u2005\u00c5] bond is s Table\u00a02. Thus, tHydr\u22efOHydrz, N\u2014HPym\u22efON and bifurcated N\u2014HHydrz\u22efON  hydrogen bonds ] link adjacent layers, forming slabs parallel to (101); see Fig.\u00a03Cg1 is the centroid of atoms C1\u2013C6) and pyridinium (Cg2 is the centroid of atoms N3/C9\u2013C13) rings of adjacent slabs has an inter\u00adcentroid Cg1\u22efCg2 distance of 3.610\u2005(2)\u2005\u00c5, while \u03b1 is 4.2\u2005(1)\u00b0, and the inter\u00adplanar distances are 3.263\u2005(7) and 3.366\u2005(7)\u2005\u00c5, with an offset distance of 1.303\u2005\u00c5.Hydrogen bonding and van der Waals contacts are the dominant inter\u00adactions in the crystal packing. In the crystal, O\u2014Hs Table\u00a01 link theCrystal Explorer 17.5 , the 19.3% contribution to the overall crystal packing is reflected as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule. The single spike in the centre at de = di = 1.2\u2005\u00c5 in Fig.\u00a05c is due to the short inter\u00adatomic H \u22ef H contacts  and C\u22efO/O\u22efC  contacts in the structure with 3.4% and 1.9% contributions to the HS have nearly symmetrical distributions of points, with the scattered points of low densities.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title aroyl hydrazone Schiff base salt, a Hirshfeld surface (HS) analysis 2\u00b74H2O  and 4-[(4-hy\u00addroxybenzo\u00adyl)hydrazonemeth\u00adyl]pyridin  in ethanol by using a branched-tube method : 3526 m, \u03bd(OH); 1375 m, \u03bd(N\u2014O); 1644 s, \u03bd(C=N); 1501 s, \u03bd(N=O); 1105 s, \u03bd(NN).The title compound was prepared by the reaction of Cd(NOUiso(H) = 1.2Ueq(C). The highest residual electron density was found 2.48\u2005\u00c5 from atom H1.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018002141/su5422sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002141/su5422Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018002141/su5422Isup3.cmlSupporting information file. DOI: 1822116CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two new salts \u2013 2,6-di\u00adamino-4-chloro\u00adpyrimidin-1-ium 5-chloro\u00adsalicylate and bis\u00ad naphthalene-1,5-di\u00adsulfonate \u2013 have been synthesized and characterized by single-crystal X-ray diffraction. The supra\u00admolecular inter\u00adactions such as hydrogen bonding, halogen bonding, C\u2014Cl\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions are investigated for these crystal structures. 4H6ClN4+\u00b7C7H4ClO3\u2212, (I), and bis\u00ad naphthalene-1,5-di-sulfonate, 2C4H6ClN4+\u00b7C10H6O6S22\u2212, (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both compounds, the N atom of the pyrimidine group in between the amino substituents is protonated and the pyrimidinium cation forms a pair of N\u2014H\u22efO hydrogen bonds with the carboxyl\u00adate/sulfonate ion, leading to a robust R22(8) motif (supra\u00admolecular heterosynthon). In compound (I), a self-complementary base pairing involving the other pyrimidinium ring nitro\u00adgen atom and one of the amino groups via a pair of N\u2014H\u22efN hydrogen bonds [R22(8) homosynthon] is also present. In compound (II), the crystallographic inversion centre coincides with the inversion centre of the naphthalene-1,5-di\u00adsulfonate ion and all the sulfonate O atoms are hydrogen-bond acceptors, generating fused-ring motifs and a quadruple DDAA array. A halogen-bond (Cl\u22efCl) inter\u00adaction is present in (I) with a distance and angle of 3.3505\u2005(12)\u2005\u00c5 and 151.37\u2005(10)\u00b0, respectively. In addition, a C\u2014Cl\u22ef\u03c0 inter\u00adaction and a \u03c0\u2013\u03c0 inter\u00adaction in (I) and a \u03c0\u2013\u03c0 inter\u00adaction in (II) further stabilize these crystal structures.The crystals of two new salts, 2,6-di\u00adamino-4-chloro\u00adpyrimidin-1-ium 5-chloro\u00adsalicylate, C The pyrimidine group offers two protonation sites (the two ring nitro\u00adgens) and the site of protonation depends on the nature of the substituents. Tautomerism of the pyrimidinium cation has also been reported recently via two N\u2014H\u22efO bonds (Table\u00a01S(6) motif (involving the carboxyl group and the phenolic \u2013OH) observed in salicylates/salicylic acid is also present  hydrogen bonds forming an et al., 2014et al., 2012aet al., 2012bvia a Cl\u22efCl inter\u00adaction \u2005\u00c5; symmetry code: x, \u22121\u00a0+\u00a0y, z; Cg1 and Cg2 are the centroids of the N1/C2/N3/C4/C5/C6 and C8\u2013C13 rings, respectively] and C\u2014Cl\u22ef\u03c0 inter\u00adactions  s Table\u00a01 forming et al., 1995et al., 2007et al., 2001et al., 2002et al., 2003et al., 2007et al., 2007via N\u2014H\u22efO bonds. Weak \u03c0\u2013\u03c0 stacking inter\u00adactions  is also present 8) Fig.\u00a05. This tynt Fig.\u00a06.et al., 2014et al., 2017H-benzimidazole-3-ium) naphthalene-1,5-di\u00adsulfonate Uiso(H) = kUeq, where k = 1.5 for hy\u00addroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018001196/zl2723sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989018001196/zl2723Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018001196/zl2723IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018001196/zl2723Isup4.cmlSupporting information file. DOI: 1817972, 1817971CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title Schiff base compound is considerably non-planar, with the outer phenol and pyridine rings being inclined to each other by 70.21\u2005(3)\u00b0. 19H17N3O, the configuration about the C=N bond is E. The mol\u00adecule is non-planar, with the phenolic and pyridine rings being inclined to the central benzene ring by 56.59\u2005(4) and 15.13\u2005(14)\u00b0, respectively. In the crystal, mol\u00adecules are linked by pairs of O\u2014H\u22efN hydrogen bonds, forming inversion dimers. The dimers are connected to neighbouring dimers by N\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to the bc plane. The layers are linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.779\u2005(2)\u2005\u00c5], forming a three-dimensional supra\u00admolecular structure. Quantum chemical calculations of the mol\u00adecule are in good agreement with the solid-state structure.In the title Schiff base compound, C The configuration about the C14=N2 bond is E, with a C11\u2014N2\u2014C14\u2014C15 torsion angle of 176.40\u2005(2)\u00b0. The C7\u2014N1\u2014C8 angle is 123.43\u2005(1)\u00b0 and the C7\u2014N1\u2014H1A\u2014C8 fragment is approximately planar; the amine N1 atom exhibits a geometry what is typical for an sp2 rather than an sp3 atom. Bond angles C11\u2014N2\u2014C14 and C15\u2014N3\u2014C19 are also near 120\u00b0 , and the imine group has a torsion angle C11\u2014N2\u2014C14\u2014C15 of 176.40\u2005(2)\u00b0.The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01bc plane \u2005\u00c5; Cg is the centroid of the N3/C15\u2013C19 ring; inter\u00adplanar distance = 3.462\u2005(1)\u2005\u00c5 and slippage = 1.516\u2005\u00c5; symmetry code (iii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01].In the crystal, pairs of O\u2014H\u22efN hydrogen bonds link the mol\u00adecules to form inversion dimers, with an f Table\u00a01. The dimf Table\u00a01 and C\u2014H\u22eff Table\u00a01, formingne Fig.\u00a03. The slaet al., 2016i.e. N-(2-pyridyl\u00admethyl\u00adene)benzene-1,4-di\u00adamine \u00b0 and the N atoms are also trans to each another. This is in contrast to the situation in the metal complexes of EXOQAK, e.g. di\u00adchloro\u00ad{N-[(pyridin-2-yl)methyl\u00adene]benz\u00adene-1,4-di\u00adamine}\u00adzinc(II)  level  and lowest unoccupied orbitals (LUMO) are named frontier orbitals (FMOs). The LUMO and HOMO orbital energy parameters are considerably answerable for the charge transfer, chemical reactivity and kinetic/thermodynamic stability of a mol\u00adecule 1. The DFT study of the title compound revealed that the HOMO and LUMO are localized in the plane extending from the whole phenol ring to the pyridine ring and electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels are shown in Fig.\u00a04The title compound was prepared from an equimolar mixture of 4-amino\u00adphenyl\u00adamino\u00admethyl\u00adphenol  and pyridine-2-carbaldehyde  in (50\u2005ml) methanol. The yellow reaction mixture was stirred for 3\u2005h at room temperature and solvent was evaporated to 5\u2005ml. The resulting yellow solid was isolated by filtration, washed successively with a cold water and methanol mixture (10\u2005ml) and hexane (20\u2005ml). The compound was recrystallized from hot methanol, giving yellow plate-like crystals. Finally, the yellow solid was dried in a vacuum desiccator .max nm : 258 , 383 . IR : \u03bd(C=N) 1625, \u03bd(N\u2014H) 3265.Spectroscopic data: UV\u2013Vis (MeOH): \u03bb1H NMR : \u03b4 8.6 , 7.4 , 7.8 , 8.0 , 8.5 , 6.7 , 6.6 , 4.1 , 7.1 , 7.2 , 9.3 (\u2013OH), 6.5 (NH).m/z [M + H]+ calculated for C19H17N3O: 304.1444; found: 304.1455.HRMS (ESI) ca 40% of the data can be considered to be observed; hence the large value for Rint of 0.122. The N\u2014H and O\u2014H H atoms were located in difference Fourier maps. The OH H atom was freely refined, while during refinement, the N- and C-bound H atoms were included in calculated positions and treated as riding, with N\u2014H = 0.86\u2005\u00c5 and C\u2014H = 0.93\u2005\u00c5, and Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018003043/su5421sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018003043/su5421Isup2.hklStructure factors: contains datablock(s) I. DOI: 1542988CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two independent copper(II) cations with coordination numbers of 4 and 6 are bridged by dianionic salicylate anions into chains extending parallel [001]. O\u2014H\u22efO hydrogen-bonding inter\u00adactions involving both the coordinating and the lattice water mol\u00adecules result in the formation of a three-dimensional network. 2(C7H4O3)2(H2O)2]\u00b72H2O}n, contains two copper(II) cations in special positions (one on a twofold rotation axis and one on an inversion centre) and the the salicylate ligand in its dianionic form. By four- and six-coordinate metal coordination, chains are formed parallel to [001], which are extended by O\u2014H\u22efO hydrogen bonding into sheets extending parallel to (100). These sheets are weakly connected by O\u2014H\u22efO hydrogen bonding via the non-coordinating lattice water mol\u00adecules into a three-dimensional network.The title compound, {[Cu Cu2 is four-coordinated in a square-planar configuration with donor atoms O2 of the carboxyl\u00adate and O3 of the deprotonated hy\u00addroxy group. The two pairs of Cu\u2014O distances are 1.905\u2005(2)\u2005\u00c5 and are the shortest in the present structure (Table\u00a01i and the O4\u2014Cu1\u2014O4i angles . This allows the five atoms Cu1, O1, O4, O1i and O4i to deviate significantly from planarity. The sum of the cis angles is 382.8\u2005(3)\u00b0 and the dihedral angle between the O1\u2014Cu1\u2014O1i/O4\u2014Cu1\u2014O4i planes is 49.86\u2005(14)\u00b0. If one decides to consider Cu1 as four-coordinated, the coordination environment is consequently best described as halfway between square-planar and tetra\u00adhedral with approximate Dd2 symmetry \u00b72H2O \u2005\u00c5 from the least-squares plane. This small deviation involves the carboxyl\u00adate group with torsion angles of \u22123.4\u2005(5) \u00b0 for C7\u2014C2\u2014C1\u2014O1 and \u22122.5\u2005(6) \u00b0 for C3\u2014C2\u2014C1\u2014O2. The C\u2014OH bond length of 1.359\u2005(2)\u2005\u00c5 in CuO Table\u00a01. One of x = 0.25 and z = 0.25, which is the inter\u00adsection of two glide planes. By symmetry, there are four channels per unit cell with a volume of 59\u2005\u00c53 each, as calculated with the PLATON software TOPOS 0.55\u2005g (4\u2005mmol) salicylic acid were suspended in 8\u2005ml water. With a concentrated NaOH solution the pH value was adjusted to approximately 5. A solution of 0.5\u2005g (2\u2005mmol) copper(II) sulfate penta\u00adhydrate in 10\u2005ml water was added. Crystals appeared after a few days of standing. From the unit-cell determinations it became clear that the mixture of crystals contained at least three species: colourless salicylic acid, green CuCrystal data, data collection and structure refinement details are summarized in Table\u00a03ca 2\u00b0 rotation about hkl =  I, global. DOI: 10.1107/S2056989017000883/wm5360Isup2.hklStructure factors: contains datablock(s) I. DOI: 1528159CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the 1,3-dioxane ring has an envelope conformation. In the crystal, classical O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link mol\u00adecules into a sheet structure, and a weak inter\u00admolecular C\u2014H\u22efCl inter\u00adaction extends the sheet structure into a three-dimensional network. 10H14Cl3NO5, the five-membered dioxolane ring adopts an envelope conformation with the C atom bonded to the butenoate side chain as the flap. It deviates from the mean plane of the other atoms in the ring by 0.446\u2005(6)\u2005\u00c5. In the crystal, mol\u00adecules are connected by O\u2014H\u22efO hydrogen bonds into helical chains running along the b-axis direction. The chains are linked into a sheet structure parallel to (001) by an N\u2014H\u22efO hydrogen bond. These classical hydrogen bonds enclose an R44(24) graph-set motif in the sheet structure. Furthermore, a weak inter\u00admolecular C\u2014H\u22efCl inter\u00adaction expands the sheet structures into a three-dimensional network.In the title compound, C On the basis of this concept, we have explored the utilization of cyclic ortho\u00adamides, prepared from allylic diol and triol with known conditions  = 0.285\u2005(4)\u2005\u00c5 and \u03c6(2) = 296.7\u2005(8)\u00b0]. The C=C and C=O double bonds of the unsat\u00adurated ester are slightly skewed with torsion angle C13=C14\u2014C16=O18 being of 8.4\u2005(6)\u00b0. There is a weak intra\u00admolecular N6\u2014H6A\u22efCl1 inter\u00adaction present  graph-set motif  graph-set motif  short contact of 3.076\u2005(3)\u2005\u00c5 is also observed.In the crystal, a classical O\u2014H\u22efO hydrogen bond , related to the title compound  has not yet been reported.In the Cambridge Structural Database , one derivative , and one derivative . The amino H atoms were refined as adopting an sp2 configuration for WEKWOY and WAXBEE, while they were refined assuming an sp3 configuration of the N atom for LIBHIO and LAGMAK, as in the present study. Each N\u2014H bond of the amino group in LIBHIO is mostly eclipsed by the neighbouring C\u2014Cl bonds of the tri\u00adchloro\u00admethyl group, whereas those in the title compound are slightly tilted \u2005\u00c5; N6\u2014H6A\u22efCl1 = 115\u2005(3)\u00b0] in the title compound . HRMS (ESI) m/z calculated for C10H15Cl3NO5+ [M + H]+: 334.0016; found: 334.0016.The title compound was afforded from Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C) for other C-bound H atoms. The hy\u00addroxy H atom was placed, guided by difference-Fourier maps, with O\u2014H = 0.84\u2005\u00c5 and refined with Uiso(H) = 1.5Ueq(O). The amino H atoms were placed, guided by difference-Fourier maps, and were refined with distance restraints of N\u2014H = 0.86\u2005(2)\u2005\u00c5 and H\u22efH = 1.40\u2005(2)\u2005\u00c5, with Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017008283/su5377sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017008283/su5377Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008283/su5377Isup3.cmlSupporting information file. DOI: 1554119CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 3745510.1038/srep37455; published online: 11222016; updated: 05042017This Article contains errors. The position of the mutation p.(R91W); (V172D) was incorrectly calculated, taking as a starting point the beginning of cDNA rather than the start codon. The correct position of the mutation is c.[271C\u2009>\u2009T]; [515T\u2009>\u2009A]. As a result of this the following changes in the Article are made:The legend of Figure 3 is incorrect,\u201c(C) c.[325C\u2009>\u2009T]; [569T\u2009>\u2009A] (RPE65)\u201dshould read:\u201c(C) c.[271C\u2009>\u2009T]; [515T\u2009>\u2009A] (RPE65)\u201d.In Table 3 for the family ID F7, the DNA mutation should read \u2018c.[271C\u2009>\u2009T]; [515T\u2009>\u2009A]\u2019.In Figure 5 for family F7 \u2018RPE65, c.325C\u2009>\u2009T; 569T\u2009>\u2009A; p.R91W; V172D\u2019 should read \u2018RPE65, c.271C\u2009>\u2009T; 515T\u2009>\u2009A; p.R91W; V172D\u2019. The correct Figure 5 appears below as In the Results section under the subheading \u2018Mutation analysis\u2019,\u201cThe second mutation was identified in family F7 and was a new compound heterozygous mutations c.[325C\u2009>\u2009T]; [569T\u2009>\u2009A] resulting in p.(R91W); (V172D) \u201d.should read:\u201cThe second mutation was identified in family F7 and was a new compound heterozygous mutations c.[271C\u2009>\u2009T]; [515T\u2009>\u2009A] resulting in p.(R91W); (V172D) \u201d."}
{"text": "In the crystal, mol\u00adecules are linked by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, forming chains propagating along [101].In the title boronic acid derivative, the mean plane of the \u2013B(OH) 7H6BNO2, the mean plane of the \u2013B(OH)2 group is twisted by 21.28\u2005(6)\u00b0 relative to the cyano\u00adphenyl ring mean plane. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds, forming chains propagating along the [101] direction. Offset \u03c0\u2013\u03c0 and B\u22ef\u03c0 stacking inter\u00adactions link the chains, forming a three-dimensional network. Hirshfeld surface analysis shows that van der Waals inter\u00adactions constitute a further major contribution to the inter\u00admolecular inter\u00adactions, with H\u22efH contacts accounting for 25.8% of the surface.In the title compound, C However, the \u2013B(OH)2 moiety contains two O\u2014H hydrogen-bond donors and can, thus, form two O\u2014H\u22efX hydrogen bonds and adopt different conformations . This enables the generation of hydrogen-bonding networks with increased dimensionality (one to three dimensions) in the solid state , alcohols (\u2013OH) and pyridines, which are based on mol\u00adecular recognition processes 2 mean plane is twisted by 21.28\u2005(6)\u00b0 relative to the cyano\u00adphenyl ring mean plane. This torsion disables intra\u00admolecular C\u2014H\u22efO hydrogen bonding between the oxygen atom of the exo-oriented B\u2014OH function and weakens the B\u2014C \u03c0\u2013\u03c0 bonding inter\u00adactions A; graph set B; graph set C; graph set a, Table\u00a01et al., 2017i, C2\u22efN1ii and O2\u22efN1ii separations in motifs A, B and C are 2.796\u2005(1), 3.452\u2005(2) and 2.909\u2005(2)\u2005\u00c5, respectively \u2005\u00c5, see Table\u00a01Cg\u22efCgiv = 3.8064\u2005(8) \u00c5; slippage 1.38\u2005\u00c5; symmetry code (iv) = \u22121\u00a0+\u00a0x, y, z] and \u03b72-type B\u22ef\u03c0 contacts with B\u22efC distances of 3.595\u2005(2) and 3.673\u2005(2)\u2005\u00c5 . Similar inter\u00adactions are also depicted in mol\u00adecular crystals formed between 1,4-benzene\u00addiboronic acid and aromatic amine N-oxides y Table\u00a01, and are\u2005\u00c5 Fig.\u00a03c. SimilCrystalExplorer  and the shape-index (\u22121.0 to 1.0\u2005\u00c5). In the dnorm map, the vivid red spots in the Hirshfeld surface are due to short normalized O\u22efH and N\u22efH distances corresponding to O\u2014H\u22efO and O\u2014H\u22efN inter\u00adactions. The white spots represent the contacts resulting from C\u2014H\u22efN hydrogen bonding . On the shape-index surface for compound (I)2 group behaves simultaneously as a donor and an acceptor, meanwhile the \u2013C\u2261N group is an acceptor only. The occurrence of offset \u03c0\u2013\u03c0 inter\u00adactions is indicated by adjacent red and blue triangles .Hirshfeld surfaces and fingerprint plots were generated for (I)ng Fig.\u00a04a. On thes Fig.\u00a04b.et al., 2007The two-dimensional fingerprint plots qu\u00adantify the contributions of each type of non-covalent inter\u00adaction to the Hirshfeld surface  in 5\u2005ml of ethanol was heated to reflux for 15\u2005min. The solution was left to evaporate slowly at room temperature, giving after one week colorless crystals suitable for single-crystal X-ray diffraction analysis.Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018003146/su5425sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989018003146/su5425Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018003146/su5425Isup3.cmlSupporting information file. DOI: 1825335CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the indazole ring system is oriented at dihedral angles of 25.04\u2005(4) and 5.10\u2005(4)\u00b0 o the furan and benzene rings, respectively 20H16Cl2N2O2, the indazole ring system is approximately planar [maximum deviation = 0.033\u2005(1)\u2005\u00c5], its mean plane is oriented at dihedral angles of 25.04\u2005(4) and 5.10\u2005(4)\u00b0 to the furan and benzene rings, respectively. In the crystal, pairs of C\u2014Hind\u22efObo (ind = indazole and bo = benz\u00adyloxy) hydrogen bonds link the mol\u00adecules into centrosymmetric dimers with graph-set motif R22(12). Weak C\u2014H\u22ef\u03c0 inter\u00adactions is also observed. Aromatic \u03c0\u2013\u03c0 stacking between the benzene and the pyrazole rings from neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.8894\u2005(7)\u2005\u00c5] further consolidates the crystal packing.In the title compound, C Its mean plane is oriented with respect to the furan  and benzene  rings at dihedral angles of A/B = 25.04\u2005(4) and B/C = 5.10\u2005(4)\u00b0. The dihedral angle between the furan and benzene rings is 20.21\u2005(5)\u00b0. Atom C6 is \u22120.054\u2005(1)\u2005\u00c5 from the indazole ring plane, while atom C1 is 0.038\u2005(1)\u2005\u00c5 from the furan ring plane. Atoms Cl1, Cl2 and C14 are displaced by \u22120.0430\u2005(3), 0.0233\u2005(4) and \u22120.016\u2005(1)\u2005\u00c5, respectively, to the benzene ring plane.In the mol\u00adecule of the title compound, Fig.\u00a01, the bonind\u22ef Obo (ind = indazole and bo = benz\u00adyloxy) hydrogen bonds \u2005\u00c5; symmetry code: (i) 2\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, \u2212 z; Cg3 and Cg4 are the centroids of rings C (C15\u2013C20) and D (N1/N2/C7/C8/C13)].In the crystal, pairs of C\u2014Hs Table\u00a01, enclosirs Fig.\u00a02, which aon Fig.\u00a03. Weak C\u2014on Fig.\u00a03 occur. \u03c0H-indazol-2-yl)ethanol with NaH and 2,5-dichlorobenzyl bromide. NaH  was added in small fractions to a solution of alcohol  in DMF (3\u20134\u2005ml). Then, 2,5-dichlorobenzyl bromide  was added portionwise. The mixture was stirred at room temperature for 3\u2005h, and the excess hydride was decomposed with a small amount of methyl alcohol. After evaporation to dryness under reduced pressure, a small amount of water was added and extracted with methyl\u00adene chloride. The organic layer was separated, dried over anhydrous sodium sulfate, and then evaporated to dryness. The crude residue was purified by chromatography on a silica-gel column using a hexa\u00adne\u2013ethyl acetate mixture (10:1) as eluent. The ether was recrystallized from 2-propanol solution to obtain colourless crystals suitable for X-ray analysis .The title compound was synthesized by the reaction of 1-(furan-2-yl)-2-(2Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016013827/xu5891sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013827/xu5891Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013827/xu5891Isup3.cmlSupporting information file. DOI: 1501341CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif in the title compound. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds with a C(4) chain motif, and also by C\u2014H\u22ef\u03c0 inter\u00adactions. The chains are linked by \u03c0\u2013\u03c0 inter\u00adactions, forming a sheet parallel to the bc plane.There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond forming an  15H18N2O3, the coumarin ring is essentially planar, with an r.m.s. deviation of 0.012\u2005\u00c5. An intra\u00admolecular O\u2014H\u22efN hydrogen bond forms an S(6) ring motif. The piperazine ring adopts a chair conformation. In the crystal, a C\u2014H\u22efO hydrogen bond generates a C(4) chain motif running along the c axis. The chain structure is stabilized by a C\u2014H\u22ef\u03c0 inter\u00adaction. The chains are linked by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance of 3.5745\u2005(11)\u2005\u00c5], forming a sheet structure parallel to the bc plane.In the title compound, C H-chromen-2-one) derivatives have wide applications in diverse areas such as pharmaceuticals  ring motif \u2005\u00c5, \u03b8 = 1.9\u2005(2)\u00b0 and \u03c6 = 22\u2005(7)\u00b0. The C16\u2014N4\u2014C15\u2014C14 and C19\u2014N4\u2014C15\u2014C14 torsion angles are \u221278.8\u2005(2) and 158.52\u2005(16)\u00b0, respectively. The bond lengths and angles of the title compound are normal and agree with those values in other Mannich bases of 7-hy\u00addroxy\u00adcoumarin  chain motif running parallel to the c axis. A C\u2014H\u22ef\u03c0 inter\u00adaction \u2005\u00c5, inter-planar distance = 3.404\u2005\u00c5 and slippage = 1.090\u2005\u00c5; symmetry code: (iii) \u2212x, \u2212y, \u2212z\u00a0+\u00a01], forming a supra\u00admolecular sheet parallel to the bc plane.In the crystal, mol\u00adecules are linked by a C\u2014H\u22efO hydrogen bond -l-alanine : [M + H]+, 275.1. Analysis calculated for C15H18N2O3: C 65.68, H 6.61, N 10.21%; found: C 65.40, H 6.45, N 10.06%.The title compound was prepared by modification of the reported procedure (Mazzei Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016017217/is5461sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016017217/is5461Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016017217/is5461Isup3.cmlSupporting information file. DOI: 1511659CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound comprises a central pyromellitic di\u00adimide moiety with terminal decyl groups, with potential applications as an acaricide, insecticide and mematicide. 30H44N2O4 iso\u00adindole-1,3,5,7-tetra\u00adone], consists of a central pyromellitic di\u00adimide moiety with terminal decyl groups at the N-atom positions. The centre of the mol\u00adecule lies on a crystallographic inversion centre so the asymmetric unit contains one half-mol\u00adecule. The mol\u00adecule exhibits a rod-shaped conformation, like other similar compounds of this type, the distance between the ends of terminal decyl groups being 32.45\u2005\u00c5. The packing is dominated by a lamellar arrangement of the mol\u00adecules, which is reinforced by C\u2014H\u22efO hydrogen bonds and C\u2014O\u22ef\u03c0 inter\u00adactions, forming a classic herringbone structure. The mol\u00adecular structure is consistent with the theoretical calculations performed by density functional theory (DFT).The title compound, C In addition, a reversible anti to syn transition was achieved by agitating in mixed organic solvents  x, \u2212y\u00a0+\u00a0z\u00a0\u2212\u00a0ii\u22efCg1 (Cg1 is the centroid of the N1/C1\u2013C4 ring) inter\u00adactions [O\u22ef\u03c0 = 3.272\u2005(1)\u2005\u00c5; symmetry code: (ii) x, \u2212y\u00a0+\u00a0z\u00a0+\u00a0bc plane : d = 8.27 , 3.74 , 1.70 , 1.32 , 0.88 A mixture of pyromellitic dianhydride  and decyl amine  in toluene (10\u2005ml) and dimethyl sulfoxide (6\u2005ml) was heated at 453\u2005K with stirring for 5\u2005h. Upon cooling to room temperature, an off-white crude solid was filtered and washed with water, methanol and ether. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a di\u00adchloro\u00admethane solution of the title compound. d(C\u2014H) = 0.95\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for aromatic C\u2014H, d(C\u2014H) = 0.99\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for Csp3\u2014H, d(C\u2014H) = 0.98\u2005\u00c5, Uiso = 1.5Ueq(C) for methyl group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017006867/hb7674sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017006867/hb7674Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006867/hb7674Isup3.cmlSupporting information file. DOI: 1548456CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 3762710.1038/srep37627; published online: 11222016; updated: 04052017This Article contains an error in the labelling of Figure 4D, where the panel labels \u2018\u03b1CD3\u2019 and \u2018\u03b1CD3\u2009+\u2009OFS\u2019 are inverted. The correct"}
{"text": "Both complexes display a bent metallocene unit, the metal centre is coordinated in a distorted tetra\u00adhedral geometry.The crystal structures of two  ansa-titanocene tri\u00adfluoro\u00admethane\u00adsulfonate complexes bearing the Me2Si(C5Me4)2 ligand are reported, namely [di\u00admethylbis\u00ad(\u03b75-tetra\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl)silane]titanium(III) toluene monosolvate, [Ti(CF3O3S)(C20H30Si)]\u00b7C7H8, 1, and chlorido\u00ad[di\u00admethyl\u00adbis\u00ad(\u03b75-tetra\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl)silane](tri\u00adfluoro\u00admethane\u00adsulfonato-\u03baO)titanium(IV), [Ti(CF3O3S)(C20H30Si)Cl], 2. Both complexes display a bent metallocene unit, the metal atom being coordinated in a distorted tetra\u00adhedral geometry, with the tri\u00adfluoro\u00admethane\u00adsulfonate anion acting as a bidentate or monodentate ligand in 1 and 2, respectively. In 1, weak \u03c0\u2013\u03c0 stacking inter\u00adactions involving the toluene solvent mol\u00adecules [centroid-to-centroid distance = 3.9491\u2005(11)\u2005\u00c5] are observed.The crystal structures of two  Photolysis of the latter results in a photoreduction and elimination of the OH ligand to give a TiIII tri\u00adfluoro\u00admethane\u00adsulfonate complex. Several cycles of this synthetic model scheme for water splitting can be passed Ti].Variation of the 2Si(C5Me4)2Ti(OTf)]\u00b7C7H8 (1) and [Me2Si(C5Me4)2Ti(OTf)Cl] (2), respectively. Both metal complexes exhibit distorted tetra\u00adhedral coordination geometries and show the typical bent metallocene moiety.Figs. 11 crystallizes with one mol\u00adecule of toluene in the asymmetric unit. The crystal structure of 1 confirms the bidentate binding mode of the tri\u00adfluoro\u00admethane\u00adsulfonate ligand, which is in contrast to other complexes bearing different metallocene units 2]2Nd(\u03baO-OTf) 3]2Ce , B: 2.058\u2005(2)\u2005\u00c5].However, this binding mode is known for group 4 complexes \u2005\u00c5, which is slightly shorter compared to the bis\u00ad(penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl) compound Cp*2Ti(Cl)(OTf) .Titanocene(IV) complexes with a tri\u00adfluoro\u00admethane\u00adsulfonate ligand in a \u03ba al. 1994; Taw et  al. 2003; Deacon  al. 2006; Kessler al. 2011 and Gode al. 2015. The cry1, weak \u03c0\u2013\u03c0 stacking inter\u00adactions were observed between two neighbouring toluene solvent mol\u00adecules along the a axis [distance between ring centroids 3.9491\u2005(11)\u2005\u00c5 and ring slippage of 1.985\u2005\u00c5].For 2Si(C5Me4)2Ti(\u03b72-Me3SiC2SiMe3) was prepared according to a published procedure 2Ti(\u03b72-Me3SiC2SiMe3)  and Yb(OTf)3  were dissolved in 30\u2005ml of toluene and heated at 333\u2005K overnight, resulting in a colour change from dark yellow to green. All volatiles were removed in vacuo and the residue was again dissolved in toluene. The solution was filtered and the solvent was evaporated in vacuum to yield complex 1 as a dark-green powder. Single crystals suitable for an X-ray analysis were obtained from a saturated toluene solution at 195\u2005K.Synthesis of 2: In an experiment which aimed at the synthesis of the above TiIII tri\u00adfluoro\u00admethane\u00adsulfonate complex 1, a batch of the alkyne complex Me2Si(C5Me4)2Ti(\u03b72-Me3SiC2SiMe3) was used that contained significant amounts of the monochloride complex Me2Si(C5Me4)2TiCl, which was formed by incomplete reduction of the dichloride complex Me2Si(C5Me4)2TiCl2 during synthesis of the alkyne complex. Reaction of the monochloride complex with Yb(OTf)3 yields the ansa-titanocene(IV) chloride tri\u00adfluoro\u00admethane\u00adsulfonate complex 2. Single crystals suitable for an X-ray analysis were obtained from a saturated toluene solution by slow cooling from 353\u2005K to room temperature.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989016018363/rz5199sup1.cifCrystal structure: contains datablock(s) 1, 2, New_Global_Publ_Block. DOI: 10.1107/S2056989016018363/rz51991sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989016018363/rz51992sup3.hklStructure factors: contains datablock(s) 2. DOI: 1517524, 1517523CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the original publication  one authIncorrect author name:C\u00e9line ChaleurCorrect author name:C\u00e9line Chauleur"}
{"text": "II complex is centrosymmetric and the mol\u00adecules are linked by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds into the three-dimensional supra\u00admolecular network.The Mn 10H11O2)2(C10H14N2O)2(H2O)2], the MnII cation is located on an inversion centre. The four O atoms form a slightly distorted square-planar arrangement around the MnII cation, and the distorted octa\u00adhedral coordination is completed by two pyridine N atoms at distances of 2.3289\u2005(15)\u2005\u00c5. The dihedral angle between the planar carboxyl\u00adate group and the adjacent benzene ring is 87.73\u2005(16)\u00b0, while the benzene and pyridine rings are oriented at a dihedral angle of 43.03\u2005(8)\u00b0. In the crystal, the water mol\u00adecules are involved in both intra\u00admolecular (to the non-coordinating carboxyl\u00adate O atom) and inter\u00admolecular (to the amide carbonyl O atom) O\u2014H\u22efO hydrogen bonds. The latter lead to the formation of layers parallel to (100). These layers are further linked via weak C\u2014H\u22efO hydrogen bonds, resulting in a three-dimensional supra\u00admolecular network. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (70.0%), H\u22efO/O\u22efH (15.5%) and H\u22efC/C\u22efH (14.0%) inter\u00adactions. One of the ethyl groups of the di\u00adethyl\u00adnicotinamide ligand is disordered over two sets of sites, with an occupancy ratio of 0.282\u2005(10):0.718\u2005(10).In the title centrosymmetric complex, [Mn(C N,N-Di\u00adethyl\u00adnicotinamide (DENA) is an important respiratory stimulant 2(DENA)2(H2O)2]  and some benzoic acid derivatives as ligands, e.g. [Zn(NA)2(C7H5O3)2] \u00b7H2O      , was synthesized and its crystal structure is reported on herein.The structure\u2013function\u2013coordination relationships of the aryl\u00adcarboxyl\u00adate ion in MnII cation located on an inversion centre, one 2,4,6-tri\u00admethyl\u00adbenzoate (TMB) anion and one N,N-di\u00adethyl\u00adnicotinamide (DENA) mol\u00adecule together with the one water mol\u00adecule, with all ligands coordinating to the MnII cation in a monodentate manner  of the two symmetry-related TMB anions and the two symmetry-related water O atoms (O4 and O4i) at distances of 2.0999\u2005(14) and 2.2230\u2005(15)\u2005\u00c5, respectively, to form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two pyridine N atoms (N1 and N1i) at distances of 2.3289\u2005(15)\u2005\u00c5 of the two symmetry-related DENA ligands in the axial positions  \u2005\u00c5]. The Mn\u2014N bond length [2.3289\u2005(15)\u2005\u00c5] is the longest one in the MnO4N2 octa\u00adhedron. The Mn1 atom lies 0.0697\u2005(1)\u2005\u00c5 above the planar (O1/O2/C1) carboxyl\u00adate group. The O2\u2014C1\u2014O1 bond angle [125.5\u2005(2)\u00b0] seems to be significantly increased than that present in a free acid [122.2\u00b0], in which the O2\u2014C1\u2014O1 bond angle may be compared with the corresponding values of 123.5\u2005(2) and 120.4\u2005(2)\u00b0 in (II), 119.2\u2005(3) and 123.8\u2005(2)\u00b0 in (III), 123.86\u2005(13) and 118.49\u2005(14)\u00b0 in (IV), 125.11\u2005(13) and 124.80\u2005(14)\u00b0 in (V) and 126.65\u2005(14)\u00b0 in (VI), where the benzoate ions are coordinated to the metal atoms only bidentately in (V), only monodentately in (VI) and both monodentately and bidentately in (II), (III) and (IV). The O\u2014Mn\u2014O and O\u2013Mn\u2014N bond angles  deviate slightly from ideal values, with same average values of 90.00\u2005(6)\u00b0.The near equalities of the C1\u2014O1 [1.254\u2005(3)\u2005\u00c5] and C1\u2014O2 [1.243\u2005(3)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Mn\u2014O bond lengths [2.2230\u2005(15)\u2005\u00c5] for water oxygen atoms are by A (C2\u2013C7) ring is 87.73\u2005(16)\u00b0, while the benzene A and pyridine B (N1/C11\u2013C15) rings are oriented at a dihedral angle of A/B = 43.03\u2005(8)\u00b0.The dihedral angle between the planar carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene w\u22efOc  hydrogen bonds (Table\u00a01S(6) ring motif  hydrogen bonds  and C\u2014HDENA\u22efODENA hdyrogen bonds  analysis  in H2O (100\u2005ml) and N,N-di\u00adethyl\u00adnicotinamide  in H2O (10\u2005ml) with sodium 2,4,6-tri\u00admethyl\u00adbenzoate  in H2O (150\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving colourless single crystals.The title compound was prepared by the reaction of MnSOUiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for other H atoms. The disordered ethyl group  was refined over two sets of sites with distance restraints and SIMU and DELU restraints  I, global. DOI: 10.1107/S2056989018003377/xu5920Isup2.hklStructure factors: contains datablock(s) I. DOI: 1826038CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The current redetermination confirms the previous structure report, but with considerably higher precision and accuracy. 3)2(C5H7O2)2] or SnMe2(acac)2, from CCD data recorded at 100\u2005K basically confirms the previous study based on integrated film data recorded at room temperature [Miller & Schlemper  > 6.7694\u2005(4)\u2005\u00c5]. The mol\u00adecule belongs to point group iC with the SnIV atom on a centre of inversion. The SnIV atom shows a slightly distorted octa\u00adhedral coordination sphere with the methyl groups in trans positions and a Sn\u2014C bond length of 2.115\u2005(2)\u2005\u00c5 which may serve as a standard value for an Sn\u2014CH3 bond of an octa\u00adhedrally coordinated SnIV atom. The Sn\u2014O bonds involving the two carbonyl groups of the acetyl\u00adacetonate ligand are of equal length [2.180\u2005(1) and 2.183\u2005(1)\u2005\u00c5], as are the C=O [1.273\u2005(1) and 1.274\u2005(1)\u2005\u00c5] and C\u2014C bond lengths [1.393\u2005(2) and 1.400\u2005(2)\u2005\u00c5]. The acetyl\u00adacetonate ligand deviates considerably from planarity, with a dihedral angle of 5.57\u2005(9)\u00b0 between the least-squares planes of the two acetone moieties. The four O atoms of the two symmetry-related acetyl\u00adacetonate ligands are arranged in a nearly quadratic rectangle. Weak C\u2014H\u22efO inter\u00adactions consolidate the crystal packing.The redetermination of the title compound, [Sn(CHmper 1972. Inorg.  Moreover, the title compound is an excellent candidate for the determination of the Sn\u2014CMe bond length as another reference in case the SnIV atom is in a well-defined octa\u00adhedral coordination. The precise measurement of this Sn\u2014C distance therefore should supplement the observations of Britton  and the constitution of the asymmetric unit comprising half a formula unit with the Sn atom at a crystallographic centre of inversion [Wyckhoff symbol: b]. As we performed the X-ray measurement at 100\u2005K, the unit-cell volume is somewhat smaller in comparison with the original room-temperature data which is mainly caused by a considerable change of the a axis from 7.12\u2005(1) to 6.7694\u2005(4)\u2005\u00c5 while changes of all other lattice parameters  show a normal temperature-dependent shrinkage.The redetermination of the crystal structure of the title compound confirms the former results obtained by Miller & Schlemper 1973 with restrans position \u00b0. The four O atoms of the two symmetry-related acetyl\u00adacetonate ligands around the Sn atom form a planar rectangle with similar edge lengths [O1\u22efO2 = 2.975\u2005(1)/O1\u22efO1 = 3.191\u2005(1)\u2005\u00c5], and almost right angles [89.9\u2005(1)\u00b0 at O1 and 90.1\u2005(1)\u00b0 at O2]. This plane is nearly perpendicular to the axis through the two methyl groups [deviation: 0.44\u2005(2)\u00b0] but constitutes a dihedral angle of 10.2\u2005(1)\u00b0 with the least-squares plane through the two carbonyl groups of the acetyl\u00adacetonate ligand   x, y, 1\u00a0+\u00a0z; (ii) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y,1\u00a0\u2212\u00a0z; (iii) x, y, z; (iv) x, \u2212y, z]  2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] for each oxygen atom. In summary, the inter\u00admolecular contacts result in a columnar arrangement of the mol\u00adecules parallel to the a axis . The crystals are stable in air.The synthesis of the title compound by refluxing a suspension of di\u00admethyl\u00adtin oxide, Mebias 1965. Single 1H NMR , nJ [Hz]): \u03b4(CH3\u2014Sn) = 0.58, 2J(1H\u2014119/117Sn) = 100.6/97.1; \u03b4(CH3)acac = 1.96; \u03b4(CH)acac = 5.31 ], nJ [Hz]): \u03b4(CH3\u2014Sn) = 7.75, 1J(13C\u2014119/117Sn = 973.7/930.4), \u03b4(CH3)acac = 27.94, \u03b4(CH)acac = 100.09, \u03b4(C=O)acac = 190.75 ]: 3010 w, 2920 w,1562 s, 1512 s, 1436 m, 1361 s,bd, 1256 m, 1203 m, 1015 m, 925 m, 803 m, 781 m, 655 m, 572 m, 552 m ]: 3092 w, 2999 w, 2920 s, 2708 w, 1574 w, 1427 w, 1366 m, 1263 m, 1206 m, 1194 m, 1021 w, 927 m, 668 m, 567 m, 512 s, 415 m, 220 m, 130 m 94 m, 68 m , and 0.95\u2005\u00c5 (\u2013CH\u2013) and with Uiso(H) = 1.2 and 1.5Ueq(C), respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017003206/wm5370sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017003206/wm5370Isup2.hklStructure factors: contains datablock(s) I. DOI: 1534819CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Ti and Al(Ga), and in a \u03bc2 manner.The mol\u00adecular structures of two isotypic titanium(III) complexes bearing an tri\u00admethyl\u00adaluminium or -gallium motif are reported. In both compounds, two methyl groups coordinate to the metal atoms,  EMe3 unit  with two \u03bc2-coordinating methyl groups, namely [\u03bc-1(\u03b75)-(adamantan-1-yl-2\u03baC1)cycylo\u00adpenta\u00addien\u00adyl]di-\u03bc2-methyl-methyl-2\u03baC-[1(\u03b75)-penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl]aluminiumtitanium(III), [AlTi(CH3)3(C10H15)(C15H18)], and [\u03bc-1(\u03b75)-(adamantan-1-yl-2\u03baC1)cycylo\u00adpenta\u00addien\u00adyl]di-\u03bc2-methyl-methyl-2\u03baC-[1(\u03b75)-penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl]galliumtitanium(III), [GaTi(CH3)3(C10H15)(C15H18)], are reported. Reacting a dinuclear nitro\u00adgen-bridged low-valent titanium(III) complex with the Lewis acids AlMe3 or GaMe3 results in the loss of mol\u00adecular di\u00adnitro\u00adgen and the formation of two monomeric titanocene(III) fragments bearing two \u03bc2-bridging methyl groups. Single crystal X-ray diffraction reveals the formation of a new E\u2014C bond involving the penta\u00adfulvene ligand while the bridging and terminal methyl groups remain intact.The isotypic crystal structures of two titanocene complexes containing an  The crystal packing Fig.\u00a03 appears et al., 20053 and GaMe3 solutions were purchased from Sigma Aldrich and used as received. Solvents were dried according to standard procedures over Na/K alloy with benzo\u00adphenone as indicator and distilled under a nitro\u00adgen atmosphere.All reactions were carried out under a dry nitro\u00adgen atmosphere using Schlenk techniques or in a glove box. The starting titanium complex was prepared according to a published procedure (Scherer Synthesis of 1:\u03b75-penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl)(\u03b75:\u03b71-adamantylidene\u00adpenta\u00adfulvene)titanium]-\u03bc2,\u03b71,\u03b71-di\u00adnitro\u00adgen  was dissolved in toluene and AlMe3  was added. The colour of the solution changed from blue to green, after 48\u2005h the volume had reduced to 5\u2005ml and another 5\u2005ml of n-hexane were added. Crystals suitable for X-ray diffraction separated after 48\u2005h directly from the mother liquor.Bis[(Synthesis of 2:\u03b75-penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl)(\u03b75:\u03b71-adamantylidene\u00adpenta\u00adfulvene)titanium]-\u03bc2,\u03b71,\u03b71-di\u00adnitro\u00adgen  was dissolved in toluene and GaMe3  was added. The former blue solution turned brown and was stored at 233\u2005K. After 10 days, brown\u2013green crystals suitable for X-ray diffraction separated from the mother liquor.Bis[(Uiso(H) = 1.2Ueq(C); H atoms of all methyl groups were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989017004856/wm5378sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989017004856/wm53781sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989017004856/wm53782sup3.hklStructure factors: contains datablock(s) 2. DOI: 1540662, 1540661CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A mol\u00adecular docking calculation of the title compound with the neuraminidase enzyme was carried out.In the title chalcone-thio\u00adphene derivative, the dihedral angle between the aromatic and the thio\u00adphene rings is 11.4\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO and C\u2014H\u22efS weak inter\u00adactions along [100], forming rings of  15H15NOS, whose mol\u00adecular structure matches the asymmetric unit. The mol\u00adecule is not planar, the dihedral angle between the aromatic and the thio\u00adphene rings being 11.4\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO and weak C\u2014H\u22efS inter\u00adactions along [100], forming 22R(8) rings, and by weak C\u2014H\u22efO inter\u00adactions along [010], forming chains with a C(6) graph-set motif. In addition, mol\u00adecules are connected into centrosymmetric dimers by weak C\u2014H\u22ef\u03c0 inter\u00adactions, as indicated by the Hirshfeld surface analysis. The most important contributions for the crystal structure are the H\u22efH (46.50%) and H\u22efC (23.40%) inter\u00adactions. The crystal packing resembles a herringbone arrangement when viewed along [100]. A mol\u00adecular docking calculation of the title compound with the neuraminidase enzyme was carried out. The enzyme shows (ASN263)N\u2014H\u22efO, (PRO245)C\u2014H\u22efCg(thio\u00adphene ring) and (AGR287)C\u2014H\u22efN inter\u00admolecular inter\u00adactions with the title compound. The crystal structure was refined as a two-component twin with a fractional contribution to the minor domain of 0.0181\u2005(8).The equimolar reaction between 4-(di\u00admethyl\u00adamino)\u00adbenzaldehyde and 2-acetyl\u00adthio\u00adphene in basic ethano\u00adlic solution yields the title compound, C The 22R(8) rings are the subunits of the periodic arrangement along [100] and one very weak H7\u22efH2i contact is also observed [H\u22efH = 2.26\u2005\u00c5]. The mol\u00adecular units are also linked by very weak C15\u2014H15\u22efO1ii links into chains along [010] with a C(6) graph-set motif  and di (x axis) values are the closest external and inter\u00adnal distances  from given points on the Hirshfeld surface contacts N\u2014H\u22efO1 (d = 1.796), (PRO245)C\u2014H\u22efCg(thio\u00adphene ring) (d = 2.829) and (AGR287)C\u2014H\u22efN1 (d = 2.620)  contact is observed in the structure inter\u00adpretation, by the centrosymmetric dimeric arrangement of the mol\u00adecules  Fig.\u00a08. More des Figs.\u00a03 and 9 \u25b8,sp2-hybridized C atoms of the main fragment, and the weak inter\u00admolecular inter\u00adactions, e.g. H\u22efH, H\u22efC or \u03c0\u2013\u03c0 contacts. One example for comparison with the title compound is the crystal structure of the compound 3-(4-methyl\u00adphen\u00adyl)-1-(3-thien\u00adyl)-2-propen-1-one  and for the above-mentioned 3-thienyl derivative, along [001] .Chalcone-thio\u00adphene derivatives have some mol\u00adecular structural features in common, namely the nearly planar geometry, as a result of the 1] Fig.\u00a09b.et al., 2016All starting materials are commercially available and were used without further purification. The synthesis of the title compound was adapted from a previously reported procedure  = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups. The crystal was refined as a two-component twin {twin law: two-axis (001) [105], BASF = 0.0181\u2005(8)}.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017003437/rz5205sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017003437/rz5205Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017003437/rz5205sup3.pdfSUPPORTING INFORMATION FOR THE EVALUATION OF THE CRYSTAL STRUCTURE OF (2E)-3-[4-(DIMETHYLAMINO)PHENYL]-1-(THIOPHEN-2-YL)PROP-2-EN-1-ONE AND THE NEURAMINIDASE ENZYME. DOI: Click here for additional data file.10.1107/S2056989017003437/rz5205Isup4.cmlSupporting information file. DOI: 1535563CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, a di\u00adspiro\u00ad-2,5\u2032\u2032-dione, C\u2014H\u22efO hydrogen bonding predominates, linking mol\u00adecules to form chains propagating along [100]. 32H26ClN3O2, the cyclo\u00adhexa\u00adnone ring of the iso\u00adquinoline unit has a distorted envelope conformation, with the methyl\u00adene C atom adjacent to the spiro C atom as the flap. The central 1-methyl\u00adpyrrolidine ring has an envelope conformation with the N atom as the flap. The mean planes of the indolin-2-one ring system, the chloro\u00adbenzene ring and the iso\u00adquinoline ring system are inclined to the mean plane of the central 1-methyl\u00adpyrrolidine ring by 87.95\u2005(11), 71.01\u2005(12) and 88.81\u2005(10)\u00b0, respectively. There are two short C\u2014H\u22efO intra\u00admolecular contacts present. In the crystal, mol\u00adecules are linked via C\u2014H\u22ef O hydrogen bonds, forming chains along the a-axis direction. The NH H atom is involved in a weak N\u2014H\u22efO hydrogen bond with the same carbonyl O atom. There are no further significant inter\u00admolecular contacts present. The largest contribution to the overall Hirshfeld surface of 52.3% is due to H\u2014H contacts.In the title di\u00adspiro compound, C The pyridine ring (N3/C32\u2013C36) has a shallow twist-boat conformation . Their mean planes are inclined to each other by 14.06\u2005(10)\u00b0, and the phenyl ring (C51\u2013C56) is inclined to the pyridine ring mean plane by 22.35\u2005(12)\u00b0.The mol\u00adecular structure of the title mol\u00adecule is shown in Fig.\u00a01Q = 0.094\u2005(2)\u2005\u00c5, \u03b8 = 92.3\u2005(13)\u00b0, \u03c6 = 84.5\u2005(13)\u00b0]. The mean planes of the indolin-2-one ring system, the chloro\u00adbenzene (C41\u2013C46) ring and the iso\u00adquinoline (N3/C3/C31\u2013C38) ring system are inclined to the mean plane of the central 1-methyl\u00adpyrrolidine (N1/C2\u2013C5) ring by 87.95\u2005(11), 71.01\u2005(12) and 88.81\u2005(10)\u00b0, respectively. The sum of the bond angles around atoms N1 and N2 are 333.6 and 358.6\u00b0, respectively, indicating a pyramidal geometry and sp3 hybridization.In the indolin-2-one ring system (N2/C2/C21\u2013C27), the benzene (C21\u2013C26) and pyrrolidine (N2/C2/C21/C26/C27) rings make a dihedral angle of 2.45\u2005(12)\u00b0, while the keto atom O1 deviates from the attached pyrrolidine ring by 0.043\u2005(1)\u2005\u00c5. The 1-methyl\u00adpyrrole ring (N1/C2\u2013C5) has an envelope conformation with atom N1 as the flap -1,2\u2032\u2032(1\u2032\u2032H)-dione methanol solvate -dione chloro\u00adform solvate . The relative contributions of the other different inter\u00admolecular inter\u00adactions to the Hirshfeld surface in descending order are: C\u22efH/H\u22efC (23.3%), O\u22efH/H\u22efO (8.5%), Cl\u22efH/H\u22efCl (8.4%), N\u22efH/H\u22efN (4.1%) and there is only a very small contribution from other contacts, i.e. 3.1%, in the structure. This illustrates that the N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions contribute significantly to the crystal packing of the title compound.The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a05E)-6-(2-chloro\u00adbenzyl\u00adidene)-2-phenyl-7,8-di\u00adhydro\u00adquinolin-5(6H)-one (L) in 94% yield (m.p. 323\u2013324\u2005K). A mixture of isatin (1.1\u2005mmol) and sarcosine (1.1\u2005mmol) was taken in 10\u2005ml of aceto\u00adnitrile in a 50\u2005ml round-bottom flask and heated to reflux for 2\u2005h. Then 1\u2005mmol of L was added to the above reaction mixture and reflux was continued for a further 14\u2005h. After completion of the reaction, as evident from TLC, the solvent was removed under reduced pressure and the residue washed with ice-cold water (50\u2005ml). The crude product was purified by column chromatography using a 90:10 (v/v) petroleum ether\u2013ethyl acetate mixture to obtain the pure product . Colourless block-like crystals were obtained by slow evaporation of a solution in ethyl acetate.An equimolar mixture of 2-phenyl-5,6,7,8-tetra\u00adhydro-5-quinolinone and 2-chloro\u00adbenzaldehyde was dissolved in 10\u2005ml of ethanol followed by the addition of 0.5 equiv. of potassium hydroxide. The mixture was stirred for 1\u2005h at ambient temperature and the precipitate formed was filtered and dried to obtain pure (Uiso = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018005455/su5434sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018005455/su5434Isup2.hklStructure factors: contains datablock(s) I. DOI: 1835595CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "For example, conventional \u03b1\u03b2 T cells develop from DP cells after partial-agonist T cell receptor (TCR) interactions with self-peptide/MHC, whereas unconventional \u03b1\u03b2 T cells, such as TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) intraepithelial lymphocytes (IELs), require full-agonist TCR interactions. Despite this, DP cells appear homogeneous, and it remains unclear how distinct TCR signalling instructs distinct developmental outcomes. Moreover, whether TCR signals at earlier stages of development, for example in CD4(\u2212)CD8(\u2212) double negative (DN) cells, impact on later fate decisions is presently unknown. Here, we assess four strains of mice that display altered TCR signal strength in DN cells, which correlates with altered generation of unconventional TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs. FVB/n mice  and mice with altered preTCR\u03b1 (pT\u03b1) expression, both displayed weaker TCR signalling in DN cells, an inefficient DN-to-DP transition, and reduced contribution of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs to gut epithelium. Conversely, TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development was favoured in mice with increased TCR signal strength in DN cells. Collectively, these data suggest TCR signal strength in DN cells directly impacts on subsequent DP cell differentiation, fundamentally altering the potential of thymocyte progenitors to adopt conventional versus unconventional T cell fates.CD4 Gut IELs display anti-microbial and anti-inflammatory properties and are central to the control of intestinal epithelial homeostasis2. A large proportion of gut IELs express TCR\u03b1\u03b2, and can be further characterized by expression of CD8\u03b1\u03b2 or CD8\u03b1\u03b1 dimers3. TCR\u03b1\u03b2(+)CD8\u03b1\u03b2(+) IELs are termed \u201cconventional\u201d, closely sharing gene expression signatures with CD8\u03b1\u03b2(+) T cells from secondary lymphoid organs5. By contrast, \u201cunconventional\u201d TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs do not require priming in lymphoid structures, appear restricted to the gut epithelium, and display gene expression signatures more similar to \u03b3\u03b4 T cells5.T cell receptor-expressing intraepithelial lymphocytes (IELs) are epithelial-resident T cells found at numerous body locations(+)CD8\u03b1\u03b1(+) IELs develop extra-thymically in gut lymphoid structures known as cryptopatches6. However, TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs are severely reduced in athymic nude mice, and fate-mapping experiments suggested they traverse the CD4(+)CD8(+) double positive (DP) stage in the thymus7. Further work implicated agonist self-peptide-mediated selection through TCR\u03b1\u03b2 at the DP stage8, and identified pre- and post-selection progenitor subsets9. Nonetheless, it remains unclear how \u201cstrong\u201d TCR-agonist signals in DP cells instruct positive selection of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs instead of driving negative selection. Indeed, unconventional TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs were recently found to express TCRs that had been \u201crecycled\u201d from strong negatively selecting signals10.Initial studies suggested that unconventional TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development, the DP stage is not the first in which TCR signalling occurs. DP cells arise from CD4(\u2212)CD8(\u2212) double negative (DN) cells in a process known as \u201c\u03b2-selection\u201d that is mediated by signalling through the preTCR (rearranged TCR\u03b2 paired with invariant pT\u03b1)11. PreTCR signalling is generally considered weak, due to very low surface preTCR expression12. By contrast, stronger signalling in DN cells, for example by TCR\u03b3\u03b4, is less efficient at generating DP cells; instead driving cells to a \u03b3\u03b4 T cell fate14.Although TCR\u03b1\u03b2 signalling at the DP stage appears critical for TCR\u03b1\u03b215. Although TCR signal strength in DN cells clearly affects the efficient induction of these processes, it is presently unclear whether it also affects the future fate of the DP cells that are generated. Here, we begin to investigate this idea in the context of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development. We show that FVB/n wild type (WT) mice have a much reduced TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL compartment when compared with WT C57BL/6 animals, that correlates with weaker preTCR signalling at the \u03b2-selection checkpoint. Indeed, by reducing preTCR signal strength in pT\u03b1-transgenic animals we re-capitulate this relative absence of gut TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs. By contrast, in two mouse models in which TCR signal strength is greater in DN cells by forced expression of TCR\u03b1\u03b2, increased generation of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs was observed. Thus, these data provide evidence that TCR signal strength at the DN-to-DP transition directly influences the efficiency of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development.Successful transition through the \u03b2-selection checkpoint results in cell survival, extensive proliferation, and significant differentiation, events that may be mechanistically linked(+)CD8\u03b1\u03b1(+) IELs in the small intestine CD8\u03b1\u03b2(+) IELs was increased in FVB/n mice, and TCR\u03b3\u03b4(+) IELs were comparable between the two strains CD8\u03b1\u03b1(+) IELs are thought to develop in the thymus from cells that are CD4(lo)CD8(lo)TCR\u03b4(\u2212)TCR\u03b2(+)CD5(hi)CD69(+)PD-1(+)CD122(+) CD8(+) double positive (DP) cells16, that in turn are generated when the preTCR (rearranged TCR\u03b2 paired with invariant pre-T\u03b1) drives CD44(\u2212)CD25(+) DN3 cells to CD44(\u2212)CD25(\u2212) DN4 cells (and then on to the DP stage) in a process called \u03b2-selection11. C57BL/6 mice had an expected DN3-to-DN4 ratio of ~1.5, consistent with a normal transition through the \u03b2-selection checkpoint . Moreover, DN3 cells from FVB/n mice had significantly elevated surface expression of CD25, a signatory feature of inefficient progression through the DN-to-DP transition11 CD8\u03b1\u03b1(+) IEL compartment compared with C57BL/6 animals, also display inefficient developmental progression through thymic stages that lead to generation of unconventional IEL progenitors.We had noted that FVB/n wild type (WT) mice, in comparison with C57BL/6 WT mice, had significantly reduced unconventional TCR\u03b1\u03b2ine Fig.\u00a0 . By conins Fig.\u00a0. Unconvells Fig.\u00a0. IEL proint Fig.\u00a0. Howevern11 Fig.\u00a0. Thus, F(+)CD8\u03b1\u03b1(+) IEL development, we first assessed components of the preTCR. Intracellular TCR\u03b2 levels in DN3 cells appeared comparable between FVB/n and C57BL/6 animals , than C57BL/6 mice  of CD71(+)i.c.TCR\u03b2(+) proliferating DN3 cells18 CD8\u03b1\u03b1(+) IELs in FVB/n mice.To investigate the inefficient DN3-to-DN4 transition in FVB/n mice that appeared to correlate with reduced unconventional TCR\u03b1\u03b2als Fig.\u00a0. For pT\u03b1ice Fig.\u00a0. It was s18 Fig.\u00a0, that exs18 Fig.\u00a0, a recog(+)CD8\u03b1\u03b1(+) IELs are linked, we generated mice in which only a weakly signalling pT\u03b1a-containing preTCR could be formed. pT\u03b1-intron-1 was removed from the full pT\u03b1 genomic locus (to prevent splicing to pT\u03b1b), in a 50\u2009kb bacterial artificial chromosome (BAC), that was then used to generate pT\u03b1a-only BAC transgenic mice on a pT\u03b1\u2212/\u2212 (C57BL/6) background  DN3 cells displayed markedly less CD5, indicative of weaker TCR signalling CD8\u03b1\u03b1(+) IELs in the small intestine CD8\u03b1\u03b2(+) IELs and TCR\u03b3\u03b4(+) IELs were present in normal proportions CD8\u03b1\u03b1(+) IELs.To test the idea that weaker signalling at the \u03b2-selection checkpoint and reduced generation of unconventional TCR\u03b1\u03b2ls, Fig.\u00a0. Consistls, Fig.\u00a0, with a als Fig.\u00a0. Moreove WT Fig.\u00a0, while ning Fig.\u00a0. Importaine Fig.\u00a0 . By con(+)CD8\u03b1\u03b1(+) IELs. To test this idea further, we sought to increase TCR signalling in DN cells to ascertain if this would conversely increase unconventional TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development. TCR\u03b1\u03b2 transgenic (tg) mice aberrantly express TCR\u03b1\u03b2 complexes that signal strongly at the \u03b2-selection checkpoint. Indeed, as well as driving DN cells to the DP stage, this strong TCR signalling is also thought to divert some DN progenitors to the \u03b3\u03b4 lineage22. OT-II mice (C57BL/6 background), express an ovalbumin-specific MHC-II-restricted V\u03b12(+)V\u03b25(+) transgenic TCR\u03b1\u03b223. V\u03b12(+) (i.e. largely tg-TCR(+)) DN3 cells from OT-II mice express much higher levels of CD5 than V\u03b12(\u2212) DN3 cells, indicative of stronger TCR signalling  DN cells from OT-II mice traverse the \u03b2-selection checkpoint efficiently CD8\u03b1\u03b1(+) IELs was observed, notably inverting the TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL-to-TCR\u03b1\u03b2(+)CD8\u03b1\u03b2(+) IEL ratio  rearrange early TCR\u03b1 (and TCR\u03b2). Compared with pT\u03b1\u2212/\u2212 mice, TCR\u03b4\u2212/\u2212. pT\u03b1\u2212/\u2212 mice had an increased population of DN4 cells, the majority of which robustly expressed TCR\u03b2 CD8\u03b1\u03b1(+) IELs was observed, again inverting the TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL-to-TCR\u03b1\u03b2(+)CD8\u03b1\u03b2(+) IEL ratio CD8\u03b1\u03b1(+) IEL development.TCR-tg mice express a single TCR\u03b1/TCR\u03b2 combination that may have unusual signalling characteristics. Thus, to extend these studies, we took advantage of a little-known feature of TCR\u03b4CR\u03b2 Fig.\u00a0. Unlike als Fig.\u00a0. Moreoveing Fig.\u00a0. Thus, \u03b2tio Fig.\u00a0. Collect(+)CD8\u03b1\u03b1(+) intraepithelial lymphocytes have long been debated. Initially, the recognition that TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs, but not TCR\u03b1\u03b2(+)CD8\u03b1\u03b2(+) IELs, were present in athymic mice led to suggestion of their extra-thymic generation in gut lymphoid structures called cryptopatches (CPs)6. Indeed, CPs were shown to contain CD25(+)IL-7R\u03b1(+)c-kit(+) progenitors that could reconstitute the T cell compartments of irradiated T cell-deficient animals26. Nonetheless, that athymic mice have only 5\u201310% of the total TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs of euthymic mice conversely argued for a predominately thymic origin. The thymic generation of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs was further supported by fate mapping experiments in which a GFP marker was activated by ROR\u03b3t-promoter-driven Cre protein7. ROR\u03b3t is expressed in thymic DP cells but not in their DN precursors. As all \u03b3\u03b4 T cells develop from DN cells, TCR\u03b3\u03b4(+) IELs were GFP(\u2212). By contrast, TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs were GFP(+), suggesting their development through a DP stage7.The developmental origins of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs use \u201cforbidden\u201d TCR\u03b2 chains that were purged from the conventional TCR\u03b1\u03b2(+) T cell pool by superantigen-driven negative selection of DP cells in the thymus27. Nonetheless, despite evidence of \u201cTCR-agonist-selection\u201d28, identifying the thymic stages through which TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL progenitors progress has proven more problematic. Cheroutre and colleagues described a minor subset of CD8\u03b1\u03b1(+) DP cells that appeared to develop as TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs if exposed to TCR-agonist signals9. Somewhat surprisingly, these \u201ctriple positive\u201d (TP) cells then shut off CD4, CD8\u03b1 and CD8\u03b2 to become TCR\u03b1\u03b2(+)CD5(+) DN cells, before re-expressing CD8\u03b1\u03b1(+) in the gut epithelium possibly under the influence of TGF\u03b229. By contrast, the stages that precede the TP stage are less clear. As too are the reasons why TP cells survive TCR-agonist signals, rather than dying as DP cells do during TCR-agonist-driven negative selection. It is conceivable that TP cells have already entered an unconventional IEL developmental pathway, and are thus cell-intrinsically distinct from DP cells that allow them to survive agonist signals. In this regard, RhoH30, and TGF\u03b2 signalling29, have been implicated in differential thymic development of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs versus conventional T cell subsets. Nonetheless, how unconventional IEL progenitors could adopt such a distinct gene expression profile by the TP stage, and indeed how TP cells are even generated, had not been previously elucidated.It was also recognized early that TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs; stronger TCR signalling in DN cells, as judged by CD5 surface levels and the efficiency of the DN-to-DP transition, appearing to favour TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL generation. As TP cells, like DP cells, are presumably derived from DN precursors as a result of (pre)TCR signalling, we speculate that stronger signalling at the DN stage favours TP generation. Unfortunately, we were unable to formally test this idea, as CD8\u03b1\u03b1-specific antibodies are not available and TL-tetramer staining did not work in our hands9. Nonetheless in this regard, peripheral CD4(+) cells do upregulate CD8\u03b1\u03b1 when activated through TCR\u03b1\u03b2 (by cross-linking antibodies) in the presence of TGF\u03b229, the absence of which has been correlated with reduced generation of TCR\u03b1\u03b2(+)CD5(+) IEL precursors29.In this study, we have shown that modulation of TCR signal strength at the thymic DN stage fundamentally impacts on the development of TCR\u03b1\u03b2(+)) DP cells conflicts with the notion that such signals are required for commitment to the \u03b3\u03b4 T cell lineage14. Indeed, premature expression of TCR\u03b1 in DN cells of TCR\u03b1\u03b2 transgenic mice was shown to promote differentiation of CD4(\u2212)CD8(\u2212)TCR\u03b1\u03b2(+) cells with \u03b3\u03b4 T cell-like properties22. Nonetheless, many of these studies also reported increased numbers of TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IELs, and made obvious but perhaps incorrect links between these DN TCR\u03b1\u03b2(+) cells and IEL development31. However, these \u201c\u03b3\u03b4-wannabie\u201d cells do not traverse the DP stage (unlike bone fide IEL progenitors), and do not rearrange their endogenous TCR\u03b1 chains20; something obviously required for TCR\u03b1\u03b2(+) IEL development. By way of explanation, our data now suggest that in TCR\u03b1\u03b2(+) transgenic mice at least some DN cells will transition to the DP stage as a result of stronger transgenic-TCR signalling. This could boost the TP cell to conventional DP cell ratio, which in turn would favour increased TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development.At first glance, invoking strong TCR signals in DN cells to drive generation of CD8\u03b1\u03b1(+) IELs.Finally, what would normally provide the stronger TCR signals in DN cells to drive TP generation in the absence of prematurely expressed transgenic TCR\u03b1\u03b2? TCR\u03b1 is reported to rearrange in a small fraction of WT DN cells(+)CD8\u03b1\u03b1(+) IELs. Stronger signalling favours TCR\u03b1\u03b2(+)CD8\u03b1\u03b1(+) IEL development. By contrast, weaker signalling favours a greater contribution from conventional TCR\u03b1\u03b2(+)CD8\u03b1\u03b2(+) IELs that are likely differentiated from na\u00efve conventional CD8\u03b1\u03b2(+) T cells in the gut-associated lymphoid tissue.In sum, our findings shed new light on the early thymic stages of unconventional IEL development. We demonstrate that TCR signal strength in DN cells at the \u03b2-selection checkpoint significantly influences the development of unconventional TCR\u03b1\u03b2All experimental protocols were performed in, and approved by, The Blizard Institute, Bart\u2019s and The London School of Medicine, Queen Mary University of London.C57BL/6 and FVB/n mice were purchased from Charles River Laboratories. All mice were 6\u201312 weeks old. Mice were bred and maintained in specific pathogen-free animal facilities at Queen Mary University of London. All experiments were performed in compliance with relevant laws and institutional guidelines and were approved by a local ethics committee.http://recombineering.ncifcrf.gov)33. In brief, a pT\u03b1 locus-containing BAC (BMQ452P20) was purchased from www.ensemble.org. A GalK cassette was first amplified from a GalK plasmid using primers that contained 50\u2009bp homology with sections of pT\u03b1 intron-1;BAC-transgenic mice were generated by the recombineering technique  in fluorescence-activated cell sorting (FACS) buffer  containing; 2% heat-inactivated fetal calf serum (FCS) (Life technologies); and 5\u2009mM ethylenediaminetetraacetic acid (EDTA) (Life technologies)). For spleen, red blood cells were removed by gradient centrifiguation at 1600rpm for 25\u2009min using 4\u2009mL of Lymphocyte Separation Medium (Fischer). For IEL preparations, faecal material was flushed from lumen of small intestine with ice-cold PBS using a gavage needle. Fatty tissues, vasculature and Peyer\u2019s patches were removed, followed by longitudinal opening and 60\u2009min agitation in RPMI-1640 10% Newborn calf serum (NCS) (Life technologies) with 5\u2009mM EDTA (Life technologies) at 37\u2009\u00b0C. Cells were subsequently passed through an autoclaved column containing 0.7\u2009g of nylon wool , equilibrated with RPMI-1640 with 38\u2009mM HEPES (Life technologies). IELs were enriched on a discontinuous Percoll gradient (40%/80% isotonic Percoll), before use and stained as described below.Fluorochrome-conjugated antibodies (eBioscience or BD) were; CD3\u03b5 (145-2C11), CD4 (RM4-5), CD8\u03b1 (53\u20136.7), CD25 (PC61), CD44 (IM7), TCR\u03b4 (GL3), TCR\u03b2 (H57\u2013597), CD8\u03b2 (H35\u201317.2), CD5 (53\u20137.3), CD69 (H1.2F3), V\u03b12 (B20.1), CD117 (2B8), B220 (RA3\u20136B2). For surface staining, cells were Fc-blocked  and stained with antibodies in FACS buffer  for 30\u2009mins. Cells were then washed twice with FACS buffer using a centrifugation speed of 300\u2009g for 5\u2009mins. After staining, cells were resuspended in FACS buffer containing 0.5\u2009\u03bcg/ml DAPI (Life technologies) for dead cell exclusion. For intracellular staining, cells were first stained for extracellular markers and subsequently fixed and permeabilized using the eBioscience intracellular flow kit according to the manufacturer\u2019s protocol. The corresponding isotype control was used as a negative control. Samples were acquired using an LSR-II and analysed using Flow Jo v10.Total RNA was extracted using the RNeasy Mini kit (QIAGEN) according to the manufacturer\u2019s instructions. Concentration and purity was determined using the NanoDrop ND-1000 spectrophotometer (Thermo Scientific). Total RNA was reverse-transcribed into cDNA using the High-Capacity RNA-to-cDNA\u2122 Kit (life technologies). Quantitative real-time PCR was performed using the power SYBR green PCR Master mix (life technologies) on the 7500 real-time PCR system (life technologies). Primers were designed manually and recognised intron/exon boundaries;aFwd: 5\u2032-GGCTCTACCATCAGGCATCGC-3\u2032;pT\u03b1aRev: 5\u2032-GGTGGTTTGCCTGGTCCTCG-3\u2032;pT\u03b1bFwd: 5\u2032-GCTCTACCATCAGGGGGAATCTTC-3\u2032;pT\u03b1bRev: 5\u2032-CGGGGGGACACAGCGG-3\u2032.pT\u03b1All samples were run in triplicate and expression was normalised against the housekeeping gene GAPDH. Analysis of PCR results was performed on 7500 real-time software v2.0.6 (life technologies).Cells were individually FAC-sorted into 96 well-plates containing 10\u2009\u03bcl of reverse transcription mix , 30U MMLV-RT reverse\u00a0transcriptase (life Technologies), 1% BSA and 0.5\u2009\u03bcM of the following primers;pT\u03b1geneF: 5\u2032-TAGGACATGGCTGCTGCTGC-3\u2032;pT\u03b1geneR: 5\u2032-TCCCACCCACAGAATTTGGAC-3\u2032.2 (NEB) and 0.25\u2009mM of the pT\u03b1geneF and pT\u03b1geneR primers. The second round PCR was performed using 2.0\u2009\u03bcl of the PCR product generated by the first-round PCR and consisted of a 3\u2009min denaturation step followed by 25 cycles of amplification  in a PCR mix containing 6.5U of Taq polymerase, 1.6\u2009mM MgCl2, 0.25\u2009mM dNTPs, and 0.25\u2009mM of the following primers;Plates were incubated for 2hr at 37\u2009\u00b0C in a thermocycler (Biorad) and the reaction was stopped by 10\u2009min incubation at 70\u2009\u00b0C. Two rounds of PCR were then carried out on the cDNA. The first round of PCR consisted of denaturation at 94\u2009\u00b0C, followed by 34 cycles of amplification  in a PCR mix containing 7.5U of Taq polymerase (NEB), 0.25\u2009mM dNTPs (NEB), 1.6\u2009mM MgClaF: 5\u2032-GCTCTACCATCAGGCATCGC-3\u2032;pT\u03b1aR: 5\u2032-CTCCAGCTGTCAGGGGAATC-3\u2032;pT\u03b1bF: 5\u2032-GCTCTACCATCAGGGGAATCTTC-3\u2032;pT\u03b1bR: 5\u2032-GCAGGTACTGTGGCTGAGC-3\u2032.pT\u03b1PCR products were run on a ReadyAgarose 96 Plus gel (Biorad) and PCR products were sequenced for validation.Data are presented as mean\u2009\u00b1\u2009s.d. A student\u2019s t-test was used to assess statistical significance between groups. A difference was considered significant if p\u2009<\u20090.05.Supplementary Figures"}
{"text": "It has been highlighted that the original article , publishChanges:A labeling error in Table\u00a0[Without DPN n\u2009=\u2009607 (100%)] was replaced by (Yes n\u2009=\u2009396).[With DPN n\u2009=\u2009396 (100%)] was replaced by (No n\u2009=\u2009607).[Age group (year): (mean\u2009\u00b1\u2009SD)] was replaced by [Age (year)], and the mean age was removed from the table.2): (mean\u2009\u00b1\u2009SD)] was replaced by [Body mass index (kg/m2)] and the mean BMI was removed.[Body mass index (BMI) (kg/m[Duration of diabetes (year): (mean\u2009\u00b1\u2009SD)] was replaced by [Duration of diabetes (year)] and the mean duration was removed.SBP mmHg (mean\u2009\u00b1\u2009SD) DBP mmHg (mean\u2009\u00b1\u2009SD) was removed.All these were removed TC (mean\u2009\u00b1\u2009SD), LDL (mean\u2009\u00b1\u2009SD), HDL (mean\u2009\u00b1\u2009SD).[HbA1C (%): (mean\u2009\u00b1\u2009SD)] was replaced by [HbA1c (%)], and the mean HbA1c was removed from the table."}
{"text": "Their crystal structures exhibits alternating inorganic and organic stacking sheets or layers in (II), with Cl 6H22N4)[SnCl6]Cl2\u00b72H2O, (I), and 1,4-bis\u00ad(2-ammonio\u00adeth\u00adyl)piperazin-1,4-diium hexa\u00adchlorido\u00adstannate (IV) dichloride dihydrate, (C8H24N4)[SnCl6]Cl2\u00b72H2O, (II), have been synthesized from the same starting materials. In each case both the cations and anions are located about inversion centers. Their crystal structures exhibits alternating inorganic and organic stacking sheets in (I) and layers in (II), with Cl\u2212 ions and water mol\u00adecules occupying the space in between. The cohesion of the three-dimensional frameworks are governed by N\u2014H\u22efCl, N\u2014H\u22efO, C\u2014H\u22efCl and O\u2014H\u22efCl hydrogen bonds. Hirshfeld surface analysis of both crystal structures indicates that the H\u22efCl/Cl\u22efH contacts exert an important influence on the stabilization of the packing.Two new organic\u2013inorganic hybrid compounds, tri\u00adethyl\u00adene\u00adtetra\u00adammonium hexa\u00adchlorido\u00adstannate (IV) dichloride dihydrate, (C Piperazine derivatives are relatively more volatile than the corresponding linear polyethyl\u00adene amines  and other branched or cyclic TETA, with close boiling points, such as tris-(2-amino\u00adeth\u00adyl)amine), 1,4-bis\u00ad(2-amino\u00adeth\u00adyl)piperazine, (Bis AEP), and 2 salt. Under very mild reaction conditions, we believe that (Bis AEP) is present as an impurity in commercial TETA based on the fact that rearrangement reactions of aliphatic chelating polyamines require high pressure and temperature 4+ cation, one half of an inorganic [SnCl6]2- dianion, one Cl\u2212 ion and one mol\u00adecule of water  dianion [SnCl6]2\u2212, lying on a centre of inversion, exhibits a nearly perfect octa\u00adhedral coordination sphere with Sn\u2014Cl bond lengths ranging from 2.4114\u2005(6) to 2.4469\u2005(6)\u2005\u00c5 and Cl\u2014Sn\u2014Cl bond angles between 88.94\u2005(2) and 91.06\u2005(2)\u00b0.The asymmetric unit of (I)er Fig.\u00a01. The 2\u2212dianion lying on a centre of inversion  to 2.4331\u2005(6)\u2005\u00c5 and Cl\u2014Sn\u2014Cl bond angles ranging from 88.55\u2005(2) to 91.45\u2005(2)\u00b0 for the cis angles [180\u00b0 for trans angles]. The organic part is totally protonated and the piperazinium portion adopts a chair conformation, with both ammonio\u00adethyl groups being in equatorial positions.The asymmetric unit of compound (II)on Fig.\u00a02. The [Bi4+ and inorganic [SnCl6]2\u2212 sheets extending along the a-axis direction. The organic cations in adjacent chains are oriented in opposite directions, forming anti\u00adparallel sheets. The isolated chloride ions Cl\u2212 and the water mol\u00adecules are located in the otherwise empty space between the sheets ts Fig.\u00a03.W and C\u2014H\u22efCl hydrogen-bonding inter\u00adactions (Table\u00a013+ group as well as the NH2+ group of [TETA]4+ act as hydrogen-bond donors. The D\u22efA distances for the NH3+ group range from 2.980\u2005(4) to 3.255\u2005(3)\u2005\u00c5, while D\u22efA distances of 3.026\u2005(2) to 3.452\u2005(2)\u2005\u00c5 are found for the NH2+ group. The water mol\u00adecules play an important role in stabilizing the crystal packing of (I)\u2212 anions and [SnCl6]2\u2212 dianions via O1W\u2014H1W\u22efCl4 and O1W\u2013-H2W\u22efCl2 hydrogen bonds with a H\u22efCl distances of 2.60\u2005(5) and 2.82\u2005(5)\u2005\u00c5, respectively. Additionally, by playing the role of acceptors, the water mol\u00adecules link the inorganic moieties with the organic cations through N1+\u2014H1B\u22efO1W and N1+\u2014H1C\u22efO1W charge-assisted hydrogen bonds with H\u22efO distances of 2.09 and 2.25\u2005\u00c5, respectively.The crystal packing of (I)s Table\u00a01. The NH34+ cations, are joined to their adjacent water mol\u00adecules through strong OW\u2014H\u22efCl hydrogen bonds, leading to a hydrogen-bonding pattern with a +\u2014H1B\u22efO1W and C6\u2014H5B\u22efCl4 hydrogen bonds, promote the formation of sheets of cations aligned parallel to the  to 3.431\u2005(2)\u2005\u00c5 and the C\u22efCl distances of 3.715\u2005(3)\u2005\u00c5.In (II)e Table\u00a02. These sCrystalExplorer software In compounds (I)et al., 2016i.e. tri\u00adethyl\u00adene\u00adtetra\u00adminium bis\u00ad(sulfate) monohydrate, (C6H22N4)SO4\u00b7H2O (III), and bis\u00ad(2-ammonio\u00adeth\u00adyl)piperazin-1,4-ium tetra\u00adperchlorate tetra\u00adhydrate, (C8H24N4)4ClO4\u00b74H2O (IV), have been reported  and tetra\u00adethyl\u00adene\u00adtetra\u00adamine in an HCl-acidified medium with a stoichiometric ratio of 1:1 was refluxed for one\u2005h at 343\u2005K for (I)All chemicals were used without further purificationUiso(H) = 1.2Ueq. H atoms of the water mol\u00adecule were located in a difference-Fourier map and refined with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018001044/tx2003sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 1817660, 1817659CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The planar deca\u00adchloro\u00adcyclo\u00adpenta\u00adsilane rings in the title compounds are coordinated by two chloride ions to generate inverse-sandwich complexes. n-butyl\u00adammonium) dichloride deca\u00adchloro\u00adcyclo\u00adpenta\u00adsilane di\u00adchloro\u00admethane disolvate, 2C16H36N+\u00b72Cl\u2212\u00b7Si5Cl10\u00b72CH2Cl2, (I), and bis\u00ad(tetra\u00adethyl\u00adammonium) dichloride deca\u00adchloro\u00adcyclo\u00adpenta\u00adsilane di\u00adchloro\u00admethane disolvate, 2C8H20N+\u00b72Cl\u2212\u00b7Si5Cl10\u00b72CH2Cl2, (II), both of which crystallize with discrete cations, anions, and solvent mol\u00adecules. In (I), the complete deca\u00adchloro\u00adcyclo\u00adpenta\u00adsilane ring is generated by a crystallographic twofold rotation axis. In (II), one cation is located on a general position and the other two are disordered about centres of inversion. These are the first structures featuring the structural motif of a five-membered cyclo\u00adpenta\u00adsilane ring coordinated from both sides by a chloride ion. The extended structures of (I) and (II) feature numerous C\u2014H\u22efCl inter\u00adactions. In (II), the N atoms are located on centres of inversion and as a result, the ethyl\u00adene chains are disordered over equally occupied orientations.We have determined the crystal structures of two deca\u00adchloro\u00adcyclo\u00adpenta\u00adsilanes, namely bis\u00ad(tetra- The distances of the chloride ions to the Si atoms  show that the chloride ions are located almost exactly above the centroid of the ring 2[Si5Cl12] (R = nBu or Et)  could be harvested after storage of the reaction solution for one week at 195\u2005K in 89% and 93% yield, respectively. Both adducts are stable in the solid phase under inert conditions. However, in solution a rapid transformation of [nBu4N]2[Si5Cl12] to [nBu4N]2[Si6Cl14] and [nBu4N]2[Si7Cl16] , while [Et4N]2[Si5Cl12] is not soluble. For comparison, a 29Si CP/MAS NMR spectrum of single crystals of [nBu4N]2[Si5Cl12] was recorded .The addition of a solution of [t) Fig.\u00a04. Crystal6] Fig.\u00a05 can be ometh\u00adyl\u2014H = 0.98\u2005\u00c5 or Cmethyl\u00adene\u2014H = 0.99\u2005\u00c5 and with Uiso(H) = 1.5Ueq(Cmeth\u00adyl) or 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a04The Cl atoms of the di\u00adchloro\u00admethane solvent mol\u00adecule in (I)10.1107/S2056989017016310/hb7717sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017016310/hb7717Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017016310/hb7717IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017016310/hb7717sup4.pdfFig. S1. 29Si NMR spectra. DOI: 10.1107/S2056989017016310/hb7717sup5.pdfFig. S2. 29Si CP/MAS NMR spectrum. DOI: 1585194, 1585193CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N,N\u2032,N\u2032\u2032-donating imine ligand led to a mononuclear compound, the N,N\u2032,O-donating imine ligand produced a binuclear metal complex.It is shown that tridentate imine ligands can control the nuclearity of copper(II) complexes based on the donor atoms present in the ligand. While the  N,N\u2032,N\u2032\u2032-donating imine ligand led to a mononuclear compound, namely di\u00adchlorido\u00adcopper(II) monohydrate, [CuCl2(C10H15N3)]\u00b7H2O, 1, while the N,N\u2032,O-donating imine ligand produced a binuclear metal complex, namely \u03bc2-chlorido-di\u00adchlorido\u00ad(\u03bc2-2-{[2-(di\u00admethyl\u00adamino)\u00adethyl]imino\u00admethyl}phenolato)\u00addicopper(II) 0.11-hydrate, [Cu2(C11H15N2O)Cl3(C4H12N2)]\u00b70.11H2O, 2. The structure of 2 is a remarkable example of a binuclear copper(II) complex containing a single substituted 2-imino\u00admethyl\u00adphenolate ligand that has two copper(II) sites in square-pyramidal coordination.It is demonstrated here that tridentate imine ligands can control the nuclearity of copper(II) complexes based on the donor atoms present in the ligand. The  Imines represent an inter\u00adesting class of ligands because they can be easily synthesized and fine-tuned to the desired application by introducing extra donor atoms or groups with the desired steric properties into the side chains. A limited number of binuclear copper(II) compounds containing substituted 2-imino\u00admethyl\u00adphenole ligands have been reported in the literature  sites of haemocyanin  and binuclear (2) copper(II) complexes with tridentate imine-containing ligands obtained by a one-pot synthetic method. The nuclearity of the complexes was shown to be directed by the different donor atoms present in the imine ligand.We describe here the crystal structures of mononuclear . The CuII cation is displaced from the least-squares plane defined by the four coordinating atoms of the square base  by 0.334\u2005\u00c5. The bond lengths to these atoms are: Cu\u2014N1 = 2.060\u2005(2), Cu\u2014N2 = 1.978\u2005(2), Cu\u2014N3 = 2.058\u2005(2) and Cu\u2014Cl2 = 2.2639\u2005(8)\u2005\u00c5; the Cu\u2014Cl bond length to the apical Cl1 atom that completes the first coordination sphere is considerably longer, at 2.5013\u2005(8)\u2005\u00c5. In order to assess the coordination geometry of copper(II) more qu\u00adanti\u00adtatively, the \u03c45 index as defined by Addison et al.  cations, both in a square-pyramidal coordination environment . The presence of the phenolate group in the structure of the imine ligand directs the reaction with copper(II) cations to form a binuclear coordination compound, in contrast with the mononuclear species 1 obtained when a pyridine group is present in the ligand. Atoms Cu1 and Cu2 in 2 are displaced from the least-squares plane defined by the four coordinating atoms of the square base  by 0.299 and 0.170\u2005\u00c5, respectively. The distances from the central copper(II) cations to these ligating atoms are: Cu1\u2014N1 = 2.068\u2005(2), Cu1\u2014N2 = 1.959\u2005(2), Cu1\u2014O1 = 1.968\u2005(1) and Cu1\u2014Cl2 = 2.2958\u2005(5)\u2005\u00c5; Cu2\u2014N3 = 2.021\u2005(2), Cu2\u2014N4 = 2.040\u2005(2), Cu2\u2014Cl3 = 2.2501\u2005(5) and Cu2\u2014O1 = 2.004\u2005(1)\u2005\u00c5. The two Cu\u2014Cl distances to the apical Cl atoms are likewise longer, Cu1\u2014Cl1 = 2.5476\u2005(5)\u2005\u00c5 and Cu2\u2014Cl2 = 2.5938\u2005(5)\u2005\u00c5. The Cu\u22efCu distance within the binuclear complex is 3.2525\u2005(5)\u2005\u00c5. In compound 2, the \u03c45 index for Cu1 is 0.294 and for Cu2 0.260, indicating more distorted square-pyramidal coordination environments for both central copper(II) cations.The binuclear compound nt Fig.\u00a02a. The p2, a solvent-accessible void of 42\u2005\u00c53 was detected by a PLATON analysis  distance of 3.393\u2005(2)\u2005\u00c5 . The partly occupied water mol\u00adecule participates in a hydrogen bond with the \u03bc2-bridging Cl2 ligand \u00adphenolate ligand were considered as analogues of 2. A total of 12 hits were found as analogues of 1, while 11 hits were found for analogues of 2, including both mono- and bis\u00ad(imino\u00admethyl)\u00adphenolate ligands. Averages of selected bond lengths  and the statistical analysis module in Mercury (Version 3.9)  compounds 1 is associated with the nonhydrated analogue , Cu\u2014N2 = 2.104\u2005(2) and Cu\u2014N3 = 2.236\u2005(2)\u2005\u00c5, and almost identical Cu\u2014Cl1 = 2.2573\u2005(5) and Cu\u2014Cl2 = 2.22561\u2005(6)\u2005\u00c5 distances. The CuII cation is displaced from the mean plane defined by the four coordinating atoms of the square base by 0.622\u2005\u00c5. While for 1 \u03c45 = 0.0593, for the structure of TAWMEK \u03c45 = 0.302. The differences in the coordination environment of copper(II) probably arise as a consequence of the presence of the hydrogen-bonded network established between the chloride ligands and the water mol\u00adecules in the crystal structure of 1. The coordination spheres around the CuII cations in 1 and TAWMEK are compared in Fig.\u00a04The closest relation to 2, the search returned only two examples of binuclear CuII complexes containing a single \u03bc2-(mono\u00adimino\u00admethyl)\u00adphenolate ligand [VAMJIE  complex with a single \u03bc2-(mono\u00adimino\u00admethyl)\u00adphenolate ligand that has two CuII co\u00adordination sites in square-pyramidal environments. The co\u00adordination spheres around the two CuII cations in 2 and UFATEB are compared in Fig.\u00a04Regarding the binuclear compound N,N-di\u00admethyl\u00adethylene\u00addi\u00adamine, pyridine-2-carbox\u00adaldehyde and salicyl\u00adaldehyde were purchased from Sigma\u2013Aldrich and used without further purification.Copper(II) chloride dihydrate was purchased from Vetec (Brazil). 1, C10H15Cl2CuN3\u00b7H2O, was obtained as follows. In a 10\u2005ml beaker, N,N-di\u00admethyl\u00adethylene\u00addi\u00adamine  was combined with pyridine-2-carbox\u00adaldehyde  in methanol (200\u2005\u00b5l). The reaction was carried out at room temperature for 24\u2005h. Afterwards, solid CuCl2\u00b72H2O  was added to the reaction mixture. A polycrystalline green compound was obtained, filtered off and washed with small amounts of cold methanol. Elemental analysis was performed on a Perkin\u2013Elmer CHNS-O 2400. Analysis, calculated for C10H15Cl2CuN3\u00b7H2O: C 36.4, H 5.2, N 12.7%; found: C 36.8, H 4.8, N 13.0%. The supernatant was transferred to an amber flask and green crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation.Compound 2 (C15H27Cl3Cu2N4O\u00b70.11H2O) was obtained following the same synthetic procedure as used for 1, but replacing pyridine-2-carbox\u00adaldehyde by salicyl\u00adaldehyde (11\u2005\u00b5l). Green needle-like crystals of 2 were obtained by slow evaporation of the supernatant. Since only a few crystals were obtained, no further analytical data were acquired.Compound 2) or 0.95\u2005\u00c5 (CH), with Uiso(H) = 1.2Ueq(C), and C\u2014H = 0.98\u2005\u00c5 (CH3) and Uiso(H) = 1.5Ueq(C). For structure 1, the H atoms of the water mol\u00adecule were refined with an O\u2014H distance restraint of 0.82\u2005(1)\u2005\u00c5 and a H\u22efH separation of 1.29\u2005(2)\u2005\u00c5, and with Uiso(H) = 1.5Ueq(O). For structure 2, the H atoms of the amine functionality (H3A and H3B) were refined freely. The occupancy of the partly occupied water solvent mol\u00adecule was refined to a value of 0.11\u2005(1); for this mol\u00adecule, H atoms were not located and they were not considered in the final model.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017013652/wm5417sup1.cifCrystal structure: contains datablock(s) global, 2, 1. DOI: 10.1107/S2056989017013652/wm54171sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989017013652/wm54172sup3.hklStructure factors: contains datablock(s) 2. DOI: 1576100, 1576099CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-tetra\u00adzol-1-olate) dianion.In energetic materials, the crystal density is an important parameter that affects the performance of the material. When making ionic energetic materials, the choice of counter-ion can have detrimental or beneficial effects on the packing, and therefore the density, of the resulting energetic crystal. Presented herein are a series of five ionic energetic crystals, all containing the 5,5\u2032-bis\u00ad(1 H-tetra\u00adzol-1-olate), with the following cations: hydrazinium (1) (2N2H5+\u00b7C6N12O42\u2212), hydroxyl\u00adammonium (2) 2NH4O+\u00b7C6N12O42\u2212 , di\u00admethyl\u00adammonium (3) (2C2H8N+\u00b7C6N12O42\u2212), 5-amino-1H-tetra\u00adzol-4-ium (4) (2CH4N5+\u00b7C6N12O42\u2212\u00b74H2O), and amino\u00adguanidinium (5) (2CH7N4+\u00b7C6N12O42\u2212). Both the supra\u00admolecular inter\u00adactions and the sterics of the cation play a role in the density of the resulting crystals, which range from 1.544 to 1.873 Mg\u2005m\u22121. In 5, the tetra\u00adzolate ring is disordered over two positions [occupancy ratio 0.907\u2005(5):0.093\u2005(5)] due to a 180\u00b0 rotation in the terminal tetra\u00adzole rings.In energetic materials, the crystal density is an important parameter that affects the performance of the material. When making ionic energetic materials, the choice of counter-ion can have detrimental or beneficial effects on the packing, and therefore the density, of the resulting energetic crystal. Presented herein are a series of five ionic energetic crystals, all containing the dianion 5,5\u2032-bis\u00ad(1 As a result of the variety of cation structures and inter\u00admolecular inter\u00adactions, each exhibits subtly different crystal packing, which affects the resulting density. The mol\u00adecule of inter\u00adest, however, only exhibits minor changes in bond distances depending on the cation.One of the critical parameters directly related to the performance of an energetic material, specifically its detonation velocity, is the density of the material (Ma H-tetra\u00adzol-1-olate), is comprised of four penta\u00adnuclear rings, with two 1,2,4-oxa\u00addiazole rings linked together through the 5-position carbon atom, and the tetra\u00adzol-1-olate rings linked at the 5-position carbon atom to each 1,2,4-oxa\u00addiazole ring at the 3-position carbon.The primary mol\u00adecule, 5,5\u2032-bis\u00ad%] in which one tetra\u00adzolate is flipped by 180\u00b0. The N4\u2014C5\u2014C6\u2014N10 torsion angles for 1 [174.25\u2005(13)\u00b0], 4 , and 5  show only slight deflections from coplanar, while in 2 [168.63\u2005(15)\u00b0], the deflection is more pronounced. In structure 3, the N4\u2014C5\u2014C6\u2014N10 dihedral angle is 2.38\u2005(19)\u00b0, showing only a slight deviation from coplanarity, despite the proximity of the two electronegative oxygen atoms.In each structure, the oxa\u00addiazole oxygen atoms are on opposite sides. For 4 Fig.\u00a04, with thet al., 1987et al., 1987In all five structures, the tetra\u00adzolate C\u2014N and N\u2014N bond distances  suggest a delocalized aromatic system rather than discrete single and double bonds \u2005\u00c5 matches the distance of 1.45\u2005\u00c5 seen in hydrazinium chloride \u2005\u00c5 matches the distance of 1.41\u2005\u00c5 seen for hydroxyl\u00adammonium perchlorate  and 1.4780\u2005(17)\u2005\u00c5 are consistent, albeit on the low side, with those reported for di\u00adalkyl\u00adammonium ions, on average 1.494\u2005(16)\u2005\u00c5 ]: C\u2014Namino, 1.320\u2005(2) and 1.314\u2005(2)\u2005\u00c5 (1.308\u2005\u00c5); C\u2014Nring, 1.334\u2005(2) to 1.338\u2005(2)\u2005\u00c5 (1.334 to 1.342\u2005\u00c5); C\u2014N(H)\u2014N=N, 1.357\u2005(2) to 1.366\u2005(2)\u2005\u00c5 (1.363 to 1.366\u2005\u00c5); N(H)\u2014N=N\u2014N(H), 1.272\u2005(2) and 1.269\u2005(2)\u2005\u00c5 ]: C\u2014NH2, 1.309\u2005(3) and 1.320\u2005(3)\u2005\u00c5 (1.312 and 1.320\u2005\u00c5); C\u2014N(H)(NH2), 1.337\u2005(3)\u2005\u00c5 (1.328\u2005\u00c5); and N(H)\u2014NH2, 1.420\u2005(3)\u2005\u00c5 bis\u00ad(1H-tetra\u00adzol-1-olate) (dianion) with the N2\u2014N3 bond of one dianion over the tetra\u00adzolate ring of the dianion in the neighboring column . Hydrazinium ions occupy the gaps between neighboring coplanar dianions along the b-axis, above the plane of the mol\u00adecules. One hydrazinium forms a hydrogen-bonded network linking the neighboring intra\u00adsheet dianions through the tetra\u00adzolate oxygen, tetra\u00adzolate N4 atom, and the NH3 portion of hydrazinium. Additionally, hydrogen bonds form between the NH2 portion of hydrazin\u00adium, the tetra\u00adzolate oxygen atom, and the tetra\u00adzolate N3 atom of neighboring dianions. An additional hydrogen bond connects the NH3 of one hydrazinium with the NH2 portion of the symmetry-related hydrazinium ion  and 4.01\u2005(2)\u2005\u00c5. The tetra\u00adzolate oxygen atom forms an anion\u2013\u03c0 inter\u00adaction with the oxa\u00addiazole ring of a neighboring dianion, with an O1-to-centroidC6/O7/N8/C9/N10 close contact of 2.98\u2005(2)\u2005\u00c5 at an O1\u2013centroidC6/O7/N8/C9/N10\u2013O7 angle of 92.3\u2005(2)\u00b0 . Additionally, the opposing columns are staggered with respect to one another. The hydroxyl\u00adammonium cations occupy the space formed where three dianion columns meet, above the dianion planes. The arrangement of the dianions in the peaks and troughs of the packing is dictated by the hydrogen bonds between the hydroxyl\u00adammonium hydroxyl group and the tetra\u00adzolate oxygen atom, and those between the hydroxyl\u00adammonium NH3 group and O1, N2, and N4 of three symmetry-related dianions \u2005\u00c5, centroidN1\u2013N4/C5\u2013centroidC6/O7/N8/C9/N10\u2013O7 angle, 80\u2005(2)\u00b0] inter\u00adaction between the tetra\u00adzolate and oxa\u00addiazole rings. Additionally, the tetra\u00adzolate oxygen atom does not participate in an anion\u2013\u03c0 inter\u00adaction with the oxa\u00addiazole ring due to the stronger \u03c0\u2013\u03c0 inter\u00adaction. The oxa\u00addiazole rings of neighboring dianions are far apart, at a centroidC6/O7/N8/C9/N10\u2013centroidC6/O7/N8/C9/N10 distance of 4.26\u2005(2)\u2005\u00c5 and a centroidC6/O7/N8/C9/N10\u2013centroidC6/O7/N8/C9/N10\u2013N10 angle of 50\u2005(2)\u00b0, suggesting minimal \u03c0\u2013\u03c0 inter\u00adaction.Structure ns Fig.\u00a07a. Addit3, space group Pa), with the dianion stacked in a staggered arrangement, with the tetra\u00adzolate ring of one dianion over the central oxa\u00addiazole\u2013oxa\u00addiazole C\u2014C bond of the dianions above and below. The oxa\u00addiazole ring resides over the tetra\u00adzolate\u2013oxa\u00addiazole C\u2014C bond in the dianions above and below. The void space between the dianion columns is occupied by di\u00admethyl\u00adammonium ions, located within the plane of the mol\u00adecules in an up\u2013down arrangement. Two di\u00admethyl\u00adammonium ions are positioned between the sheets, forming hydrogen bonds between the NH2 group and the tetra\u00adzolate oxygen atoms of dianions in neighboring sheets  and 3.99\u2005(2)\u2005\u00c5 (the latter distance to the inversion-related oxa\u00addiazole of the same dianion).Structure rn Fig.\u00a08a, with 4, space group P21/c, packs in the sheet-like pattern consisting of extended sheets containing the dianion, cations, and incorporated water . The 5-amino-1H-tetra\u00adzol-4-ium cations and water mol\u00adecules surround each dianion, isolating the dianion from other dianions within the sheets. Between the sheets, the dianion only inter\u00adacts with another dianion via one terminal tetra\u00adzolate ring, with the oxygen atom of the tetra\u00adzolate over the C\u2014C bond between the tetra\u00adzolate and oxa\u00addiazole rings. Within each sheet, there is extensive hydrogen bonding between the dianions, 5-amino-1H-tetra\u00adzol-4-ium, and incorporated water mol\u00adecules, isolating the dianions from one another in the sheet plane \u2005\u00c5 [N\u2013-centroidN1\u2013N4/C5\u2013centroidN1\u2013N4/C5 angle 62.0\u2005(2)\u00b0]. The C11-oxa\u00addiazole engages in a \u03c0\u2013\u03c0 inter\u00adaction with its symmetry equivalent as well, at a centroidC11/N12/O13/C14/N15\u2013centroidC11/N12/O13/C14/N15 distance of 3.93\u2005(2)\u2005\u00c5 . A \u03c0\u2013\u03c0 inter\u00adaction is also seen between the N30-tetra\u00adzolium ring and its symmetry equivalent, at a centroidC29/N30\u2013N33\u2013centroidC29/N30\u2013N33 distance of 3.69\u2005(2)\u2005\u00c5 . Additionally, there are two anion\u2013\u03c0 inter\u00adactions, the first between O21 and the N1-tetra\u00adzolate of a neighboring dianion, and the second between O21 and the C6-oxa\u00addiazole, with an O21\u2013centroidN1\u2013N4/C5 distance of 3.33\u2005(2)\u2005\u00c5 [O21\u2013centroidN1\u2013N4/C5\u2013N2 angle 95.8\u2005(2)\u00b0] and O21\u2013centroidC6/O7/N8/C9/N10 3.02\u2005(2)\u2005\u00c5 [O21\u2013centroidC6/O7/N8/C9/N10\u2013C6 angle 76.3\u2005(2)\u00b0].Structure er Fig.\u00a09a. The 55, space group P21/n, packs in a mixing pattern, with columns containing stacked sheets consisting of the dianion coplanar with two amino\u00adguanidinium cations . Neighboring columns of sheets are rotated by 67\u00b0 with respect to one another as a result of the hydrogen bonding of the amino group of the cation with the oxygen atom of a neighboring oxa\u00addiazole ring. In fact, it is the hydrogen-bonding inter\u00adaction between the amino group of the amino\u00adguanidinium cation and the oxygen atom of the oxa\u00addiazole that directs the mixing-type packing seen in the crystal structure. The planar portion of the amino\u00adguanidinium cation inter\u00adacts via hydrogen bonds from the unsubstituted guanidinium amines to the tetra\u00adzolate oxygen atom, oxa\u00addiazole N8, and symmetry-related oxa\u00addiazole N10 atoms of one dianion, and to the tetra\u00adzolate N2 atom of a neighboring dianion \u2005\u00c5 [centroidC6/O7/N8/C9/N10\u2013centroidA\u2013N4A/C5AN1\u2013N1A angle 65.4\u2005(2)\u00b0].Structure s Fig.\u00a010a. Neigh3 < 6 < 1 < 5 < 2. Unsurprisingly, the di\u00admethyl\u00adammonium, with minimal hydrogen bonding, non-inter\u00adacting substituents, and a poor steric match for the dianion, is the least dense of the structures shown. Amino\u00adguandinium, despite significant hydrogen bonding, exhibits a lower density as well, likely due to the directionality of the hydrogen-bond donors, which directs packing of the dianions into less efficient arrangements. Hydrazinium benefits from extensive hydrogen bonding, but the orientation of the hydrazinium directs the dianions into slightly less efficient packing than the hydroxyl\u00adammonium cation, preventing the staggering of the columns that allows for improved space occupation. The 5-amino-1H-tetra\u00adzol-4-ium cation, with the second-highest density, packs very efficiently, in extended sheets with extensive hydrogen bonding, losing out to the hydroxyl\u00adammonium cation likely only due to the included water mol\u00adecules needed to fill in gaps between the dianions and cations. Hydroxyl\u00adammonium exhibits the most efficient, highest-density packing due to the directing influence and strong hydrogen-bond donating ability of the hydroxyl group, which forms a short hydrogen bond and directs the columns into a staggered arrangement, fitting the dianions slightly closer together at the point where neighboring columns meet. The range of densities, from 1.544 to 1.873\u2005g\u2005cm\u22121, shows the significant effect that matching the hydrogen-bonding abilities and sterics of the counter-ion to the primary energetic ion has on efficient packing and, by extension, the expected performance of these ionic energetics.As demonstrated above, it is the hydrogen-bonding networks that establish the crystal packing exhibited in each example, with \u03c0\u2013\u03c0 and anion\u2013\u03c0 inter\u00adactions occurring if packing allows. As shown in Table\u00a06et al., 2016H-tetra\u00adzol-1-olate). A search using 5-[3-]-1H-tetra\u00adzolate also yields no results. Searching for the ring fragments separately yielded 443 structures for 1,2,4-oxa\u00addiazole and 127 structures for tetra\u00adzol-1-olate. The closest structures to those presented herein are dimers between similar ring fragments. A search for each of the cations yields the following results: 196 structures containing hydrazinium, 99 structures containing hydroxyl\u00adammonium, 1,583 structures containing di\u00admethyl\u00adammonium, 2,230 structures containing ammonium, 17 structures containing 5-amino-1H-tetra\u00adzol-4-ium, and 130 structures containing amino\u00adguanidinium.A search of the CSD -5,5\u2032-di\u00adchloroxime (6) and 5,5\u2032--5,5\u2032-di\u00adyl)bis\u00ad(1-hy\u00addroxy\u00adtetra\u00adzole) (7), have been described previously  was added to a 20\u2005ml vial with water (1.5\u2005ml) and a stir bar. Hydrazine hydrate  was added to the reaction mixture and heated until dissolved. Stirring was discontinued, the stir bar was removed, and the solution was allowed to cool slowly providing crystals of 1.Compound 3: In a round-bottom flask, fitted with a drying tube, was suspended chloroxime 6  in di\u00admethyl\u00adformamide (DMF) , which was then cooled in an ice\u2013water bath. Sodium azide  was added in portions with stirring, and the reaction was allowed to warm to room temperature. Additional DMF (10\u2005ml) was added to the creamy mixture, and after 1.5\u2005h, the solids went into solution. At this point, complete formation of the di\u00adazidoxime was assumed, and cyclization to 1 proceeded as follows. A 1:1 mixture of diethyl ether/dioxane was added to the reaction mixture , and the solution was cooled to 273\u2005K with an ice bath. HBr or Cl2 gas was bubbled into the reaction at which time the temperature increased to 298\u2005K. Gas was added until the reaction temperature returned to approximately 278\u2005K, and the vessel was then stoppered and allowed to stir for 22\u2005h. The voluminous, white precipitate that formed (hygroscopic di\u00admethyl\u00adamonium bromide) was separated by vacuum filtration, and the filtrate was allowed to evaporate from a crystallizing dish. Upon evaporation, a white solid (3) in a yellow oil remained. The solid was separated from the oil by vacuum filtration (535\u2005mg). 3 was crystallized by heating in minimal water and slow cooling.Compound 4: Dihydrate 7  was added to a 20\u2005ml vial with water (1.5\u2005ml) and a stir bar. 5-Amino\u00adtetra\u00adzole  was added to the mixture, which was then heated with stirring until dissolved. Stirring was discontinued, the stir bar was removed, and the solution was allowed to cool slowly providing crystals of 4.Compound 5: Dihydrate 7  was added to a 20\u2005ml vial with water (1.5\u2005ml) and a stir bar. Amino\u00adguanidinium H2CO3  was added to the mixture, which was then heated with stirring until dissolved. During dissolution, gas evolved, the solution became clear, followed by the formation of a tan\u2005precipitate. Heating was continued until complete dissolution, followed the removal of the stir bar, and slow cooling to provide crystals of 5.Compound 5, the tetra\u00adzolate ring  is disordered over two positons (A and B) due to a 180\u00b0 rotation in the terminal tetra\u00adzole rings. The disorder has the relative ratio of 90.7\u2005(5):9.3\u2005(5). CCDC deposition numbers are as follows: 1, CCDC 1567779; 2, CCDC 1567780; 3, CCDC 1567783; 4, CCDC 1567784; 5, CCDC 1567804.Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S205698901800364X/pk2606sup1.cifCrystal structure: contains datablock(s) global, 1, 2, 3, 4, 5. DOI: 10.1107/S205698901800364X/pk26061sup9.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698901800364X/pk26062sup10.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S205698901800364X/pk26063sup15.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S205698901800364X/pk26064sup20.hklStructure factors: contains datablock(s) 4. DOI: 10.1107/S205698901800364X/pk26065sup8.hklStructure factors: contains datablock(s) 5. DOI: Click here for additional data file.10.1107/S205698901800364X/pk26061sup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901800364X/pk26062sup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901800364X/pk26063sup9.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901800364X/pk26064sup10.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901800364X/pk26065sup11.cmlSupporting information file. DOI: 1567804, 1567784, 1567783, 1567780, 1567779CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex with a heterocyclic pyrazole ligand, a potential candidate for metal catalysts, are reported. The CuII atom is coordinated by three O atoms and two N atoms, provided by a tridentate pyridine-2,6-di\u00adcarboxyl\u00adate, one pyrazole and one water ligand, forming a slightly distorted square-pyramidal geometry.The synthesis and crystal structure of tridentate pyridine-2,6-di\u00adcarboxyl\u00adate Cu 7H3NO4)(C3H4N2)(H2O)]\u00b72H2O, the CuII atom is coordinated by three O atoms and two N atoms, provided by a tridentate pyridine-2,6-di\u00adcarboxyl\u00adate (pdc), one pyrazole and one water ligand, forming a slightly distorted square-pyramidal geometry [range of O\u2014Cu\u2014O and O\u2014Cu\u2014N bond angles = 79.55\u2005(8)\u2013166.22\u2005(10)\u00b0]. The water mol\u00adecule is positioned at the apical position. In the crystal, the complex mol\u00adecule and the two crystallographically independent non-coordinating water mol\u00adecules are linked into a supra\u00admolecular layer structure parallel to the ab plane via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds.In the title compound, [Cu(C H-pyrazol-1-yl)meth\u00adyl]pyridine are known to be catalysts of polyethyl\u00adene polymerization meth\u00adyl]pyridine was oxidized to pyridine-2,6-di\u00adcarboxyl\u00adate (pdc) by metal nitrate , pyrazole and water ligands. The coordination geometry around the CuII atom is a distorted square pyramid as indicated by the \u03c4 value of 0.113  and two oxygen atoms (O9 and O12 from pdc). The plane including the CuII atom is almost planar, with an r.m.s. deviation of 0.0847\u2005\u00c5 from the corresponding least-squares plane defined by the five constituent atoms. The pyrazole ring is twisted by 66.61\u2005(10)\u00b0 from the basal plane. The apical Cu1\u2014O19 bond length of 2.217\u2005(2)\u2005\u00c5 is much longer than those of the basal Cu\u2014O lengths [Cu1\u2014O9 = 2.026\u2005(2)\u2005\u00c5 and Cu1\u2014O12 = 2.058\u2005(2)\u2005\u00c5].The mol\u00adecular structure of the title compound is shown in Fig.\u00a01B\u22efO21, O20\u2014H20B\u22efO13 and O20\u2014H20A\u22efO10iii; symmetry code as in Table\u00a01A\u22efO20iv and O21\u2014H21B\u22efO20v; Table\u00a01i and O19\u2014H19A\u22efO9ii; Table\u00a01ab plane meth\u00adyl]pyridine  in aceto\u00adnitrile (5\u2005ml) in a high-pressure vessel. After sealing the high-pressure vessel, the resulting solution was stirred for three days at 403\u2005K. The precipitate formed was removed by filtration, and the filtrate was washed with aceto\u00adnitrile and di\u00adchloro\u00admethane to get a dark-green powder. Single crystals of the title compound were obtained from its aqueous solution by slow evaporation of the solvent at 333\u2005K within five days.A solution of copper nitrate trihydrate  in aceto\u00adnitrile (5\u2005ml) was added to a solution of 2,6-bis\u00ad[(1Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017016231/is5480sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017016231/is5480Isup2.hklStructure factors: contains datablock(s) I. DOI: 1584872CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation, located on a twofold rotation axis, is coordinated by two 2,4,6-tri\u00admethyl\u00adbenzoate anions, two nicotinamide ligands and a water mol\u00adecule in a distorted penta\u00adgonal\u2013bipyramidal geometry.The Cd 10H11O2)2(C6H6N2O)2(H2O)], contains one half of the complex mol\u00adecule, with the CdII cation and the coordinated water O atom residing on a twofold rotation axis. The CdII cation is coordinated in a bidentate manner to the carboxyl\u00adate O atoms of the two symmetry-related 2,4,6-tri\u00admethyl\u00adbenzoate (TMB) anions and to the water O atom at distances of 2.297\u2005(2), 2.527\u2005(2) and 2.306\u2005(3)\u2005\u00c5 to form a distorted penta\u00adgonal arrangement, while the distorted penta\u00adgonal\u2013bipyramidal coordin\u00adation sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371\u2005(3)\u2005\u00c5 in the axial positions. In the crystal, mol\u00adecules are linked via inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds with R22(12), R33(8), R33(14), R33(16), R33(20), R33(22), R44(22), R55(16), R66(16) and R66(18) ring motifs, forming a three-dimensional architecture. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are H\u22efH (56.9%), H\u22efC/C\u22efH (21.3%) and H\u22efO/O\u22efH (19.0%) inter\u00adactions.The asymmetric unit of the title complex, [Cd(C A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels 2(C6H6N2O)2]  \u00b7H2O   , O1\u2014Cd1\u2014O2 [53.63\u2005(7)\u00b0], O1i\u2014Cd1\u2014O2i [53.63\u2005(7)\u00b0], O2\u2014Cd1\u2014O4 [84.47\u2005(5)\u00b0] and O2i\u2014Cd1\u2014O4 [84.47\u2005(5)\u00b0] in the basal plane around CdII cation is 363.77\u00b0 . This confirms the presence of the CdII cation with a small deviation from the basal plane. The distorted penta\u00adgonal\u2013bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371\u2005(3)\u2005\u00c5 in the axial positions \u00b0 in (II), 59.02\u2005(8)\u00b0 in (IV), 58.45\u2005(9)\u00b0 in (V) and 60.70\u2005(4)\u00b0 in (VI). In the TMB anion, the carboxyl\u00adate group is twisted away from the attached benzene ring, A (C2\u2013C7), ring by 60.94\u2005(18)\u00b0, while the benzene and pyridine rings [pyridine = B (N1/C11\u2013C15)], are oriented at a dihedral angle of 50.32\u2005(11)\u00b0. The four-membered ring D (Cd1/O1/O2/C1) is nearly planar with a maximum deviation of 0.0029\u2005(30)\u2005\u00c5 (for C1) from the mean plane, and it is oriented at dihedral angles of 60.98\u2005(11) and 81.91\u2005(7)\u00b0, with respect to the A and B rings.The near equalities of the C1\u2014O1 [1.249\u2005(4)\u2005\u00c5] and C1\u2014O2 [1.253\u2005(3)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2\u2014C1\u2014O1 bond angle [121.7\u2005(3)\u00b0] seems to be slightly decreased than that present in a free acid [122.2\u00b0]. The O2\u2014C1\u2014O1 bond angle may be compared with the corresponding values of 123.5\u2005(2) and 120.4\u2005(2)\u00b0 in (II), 125.2\u2005(5)\u00b0 in (III), 119.2\u2005(3) and 123.8\u2005(2)\u00b0 in (IV), 123.6\u2005(3) and 119.4\u2005(3)\u00b0 in (V) and 123.86\u2005(13) and 118.49\u2005(14)\u00b0 in (VI), where the benzoate ions are coordinated to the metal atoms only monodentately in (III), and both monodentately and bidentately in (II), (IV), (V) and (VI). The Cd1 atom lies 0.0192\u2005(1)\u2005\u00c5 above of the planar (O1/O2/C1) carboxyl\u00adate group. The O1\u2014Cd1\u2014O2 angle is 53.63\u2005(7)\u00b0. The corresponding O\u2014via inter\u00admolecular N\u2014HNA\u22efONA, N\u2014HNA\u22efOC, O\u2014HW\u22efONA and C\u2014HTMB\u22efOC  hydrogen bonds  analysis  in water (50\u2005ml) and nicotinamide  in water (25\u2005ml) with sodium 2,4,6-tri\u00admethyl\u00adbenzoate  in water (150\u2005ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for six weeks, giving colourless single crystals . Combustion analysis: found; C, 57.07, H, 5.67, N, 7.92%. Calculated: C32H36CdN4O7 C, 57.42; H, 5.43, N, 8.34%. FT\u2013IR: 3390, 3122, 2921, 1669, 1619, 1539, 1445, 1399, 1113, 1038, 847, 731, 641\u2005cm\u22121.The title compound was prepared by the reaction of 3CdSO2 group and of the water mol\u00adecule were located in difference-Fourier maps and refined freely. The C-bound H atoms were positioned geometrically with C\u2014H = 0.93 and 0.96\u2005\u00c5 for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018001494/xu5916sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018001494/xu5916Isup2.hklStructure factors: contains datablock(s) I. DOI: 1818756CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Individual mol\u00adecules are stacked along the b-axis direction. The cohesion in the crystal structure is accomplished by C\u2014H\u22efF hydrogen bonds and additional off-set \u03c0\u2013\u03c0 inter\u00adactions , leading to the formation of a three-dimensional supra\u00admolecular network.The mol\u00adecule of the title 1,8-naphthyridine-BF The individual F\u2014B bond length is 1.364\u2005(5)\u2005\u00c5 and the Br\u2014C bond length 1.940\u2005(4)\u2005\u00c5. Compared with the mol\u00adecular structure of a related compound \u2005\u00c5, inter\u00adplanar distance = 3.6085\u2005(1)\u2005\u00c5, slippage = 0.472\u2005\u00c5; Cg2 is the centroid of the N2/C3\u2013C6/C11 ring; symmetry code: (i) \u2212x, \u2212y, 2\u00a0\u2212\u00a0z] ethanimidato](di\u00adfluoro)\u00adborate  was added dropwise to an ice-cooled solution of 2,6-lutidine (1\u2005ml) and N-acetamide  in anhydrous CH2Cl2 (80\u2005ml) under a nitro\u00adgen atmosphere. After the mixture had been stirred for 24\u2005h under ambient temperature, the reaction was quenched with 20\u2005ml distilled water. The aqueous layer was extracted with CH2Cl2 (3 \u00d7 50\u2005ml); the organic layer was dried with anhydrous Na2SO4 and the solvent removed under reduced pressure. The residue was purified by silica gel chromatography using CH2Cl2 as eluent to give the pure product as a bright white powder . Yellow crystals of the title compound were obtained from its CH2Cl2 solution by slow evaporation at room temperature.BFUiso(H) = 1.2Ueq(C) for aromatic and Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016016704/wm5325sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016016704/wm5325Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016016704/wm5325Isup3.cmlSupporting information file. DOI: 1510400CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II\u2013NaI metal\u2013organic framework has been synthesized and the X-ray structure has been reported.A novel three-dimensional bimetallic Cd 2(C8H4O4)2(C3H7NO)(H2O)2]n or [CdNa22(DMF)(H2O)2]n, is a new CdII\u2013NaI heterobimetallic coordination polymer. The asymmetric unit consists of one CdII atom, two NaI atoms, two 1,3-bdc ligands, two coordinated water mol\u00adecules and one coordinated DMF mol\u00adecule. The CdII atom exhibits a seven-coordinate geometry, while the NaI atoms can be considered to be penta\u00adcoordinate. The metal ions and their symmetry-related equivalents are connected via chelating\u2013bridging carboxyl\u00adate groups of the 1,3-bdc ligands to generate a three-dimensional framework. In the crystal, there are classical O\u2014H\u22efO hydrogen bonds involving the coordinated water mol\u00adecules and the 1,3-bdc carboxyl\u00adate groups and \u03c0\u2013\u03c0 stacking between the benzene rings of the 1,3-bdc ligands present within the frameworks.The title compound, [CdNa Studies incorporating alkaline metal ions into d10-MOFs with one type of bridging ligand to construct novel heterobimetallic d10-alkaline metal ion MOFs have been undertaken ] where 1,2,4-btc = benzene-1,2,4-tri\u00adcarboxyl\u00adate 3\u00b7(DMF)2\u00b7(m-H2O)2] where 1,4-bdcH2 = benzene-1,4-di\u00adcarb\u00adoxy\u00adlic acid 2]} where 1,3-bdcH2 = benzene-1,3-di\u00adcarb\u00adoxy\u00adlic acid 2]\u00b72H2O where OH-1,3-bdcH2 = 5-hy\u00addroxy\u00adbenzene-1,3-di\u00adcarb\u00adoxy\u00adlic acid 6(H2O)8] where ntcH3 = 5-nitro\u00adbenzene-1,2,3-tri\u00adcarb\u00adoxy\u00adlic acid , we explored mixed sources of ZnII/CdII\u2013NaI with this ligand. The expected products are prepared by using a direct synthetic method, mixing metal nitrate salts, 1,3-bdcH2 and NaOH (mole ratio 1:1:2) in water, methanol and DMF solvents. However, only the CdII\u2013NaI MOF product has been successfully synthesized. As part of our ongoing studies on this complex, we describe here the synthesis and crystal structure of a novel three-dimensional heterobimetallic CdII\u2013NaI MOF, [CdNa22(DMF)(H2O)2]n (I).Porous coordination polymers or metal\u2013organic frameworks (MOFs) constructed from I) crystallizes in the tetra\u00adgonal crystal system with polar P43 space group. The asymmetric unit of (I) consists of one CdII ion, two crystallographically independent Na(I) ions, two 1,3-bdc ligands, two coordinated water mol\u00adecules and one DMF mol\u00adecules, as shown in Fig.\u00a01II ion is coordinated by seven carboxyl\u00adate oxygen atoms from four different 1,3-bdc ligands with the Cd\u2014O bond distances range between 2.301\u2005(3) and 2.555\u2005(3)\u2005\u00c5 (Table\u00a01I). The 1,3-bdc mol\u00adecule is fully deprotonated and coordinated to the CdII and NaI ions in a \u03bc5-coordination mode, creating a one-dimensional heterobimetallic chain running parallel to the c axis, Fig.\u00a03a- and b-axis directions, generating a three-dimensional framework structure as shown in Fig.\u00a04The title compound (\u00c5 Table\u00a01. The Na1I), classical O\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are observed and these inter\u00adactions presumably help to stabilize the frameworks. All water mol\u00adecules are shown to act as O\u2014H\u22efO hydrogen-bond donors towards the carboxyl\u00adate groups of the 1,3-bdc ligands (Table\u00a02Cg1\u22efCg2i distance of 3.588\u2005(3)\u2005\u00c5 and a dihedral angle of 3.8\u2005(4)\u00b0 .In the crystal of (s Table\u00a02. The \u03c0\u2013\u03c0I), only the three-dimensional coordination framework {[CdNa2]\u00b7[NH2(CH3)2]} has been reported 2 mol\u00adecules. In comparison, compound (I) contains coordinated H2O and DMF mol\u00adecules projecting into the framework channels. Other related three-dimensional heterobimetallic d10\u2013NaI coordination frameworks containing benzene\u00adpolycarboxyl\u00adate ligands have been published, such as [CdNa2(H2O)2]\u00b72H2O where OH-1,3-bdcH2 = 5-hy\u00addroxy-benzene-1,3-di\u00adcarb\u00adoxy\u00adlic acid 3\u00b7(DMF)2\u00b7(m-H2O)2] where 1,4-bdcH2 = benzene-1,4-di\u00adcarb\u00adoxy\u00adlic acid 6(H2O)8] where ntcH3 = 5-nitro\u00adbenzene-1,2,3-tri\u00adcarb\u00adoxy\u00adlic acid  and NaOH (2.0\u2005mmol) in 10\u2005mL of distilled water was slowly dropped to a methano\u00adlic solution (10\u2005ml) of Cd(NO3)2\u00b74H2O (1.0\u2005mmol). The reaction mixture was stirred at 333\u2005K for 30\u2005min and allowed to cool to room temperature and then filtered. The filtrate was allowed to stand to slowly evaporate at ambient temperature. Colorless block-shaped crystals suitable for single crystal X-ray diffraction were obtained after three days (76% yield based on Cd).A mixture solution of 1,3-bdcHUiso(H) = 1.2Ueq(C). The coordinated DMF mol\u00adecule was found to be disordered with two sets of sites with a refined occupancy ratio of 0.382\u2005(10) and 0.618\u2005(10).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017013871/pj2046sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017013871/pj2046Isup2.hklStructure factors: contains datablock(s) I. DOI: 1576543CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Despite a growing appreciation of \u03b3\u03b4 T\u00a0cell contributions to numerous immune responses, the mechanisms that underpin their thymic development remain poorly understood. Here, using precursor/product relationships, we identify thymic stages in two distinct developmental pathways that generate \u03b3\u03b4 T\u00a0cells pre-committed to subsequent secretion of either IL-17A or IFN\u03b3. Importantly, this framework for tracking \u03b3\u03b4 T\u00a0cell development has permitted definitive assessment of TCR\u03b3\u03b4 signal strength in commitment to \u03b3\u03b4 T\u00a0cell effector fate; increased TCR\u03b3\u03b4 signal strength profoundly prohibited the development of all IL-17A-secreting \u03b3\u03b4 T\u00a0cells, regardless of V\u03b3 usage, but promoted the development of \u03b3\u03b4 progenitors along the IFN\u03b3 pathway. This clarifies the recently debated role of TCR\u03b3\u03b4 signal strength in commitment to distinct \u03b3\u03b4 T\u00a0cell effector fates and proposes an alternate methodology for the study of \u03b3\u03b4 T\u00a0cell development.  \u2022CD44 and CD45RB identify two distinct thymic \u03b3\u03b4 T\u00a0cell developmental pathways\u2022Cytokine-secretion-independent identification of effector fate-committed \u03b3\u03b4 T\u00a0cells\u2022Sizable numbers of IL-17A-committed \u03b3\u03b4 T\u00a0cells express V\u03b31 and V\u03b32/3 chains\u2022Increased TCR\u03b3\u03b4 signal strength prohibits development of IL-17A-secreting \u03b3\u03b4 T\u00a0cells Sumaria et\u00a0al. identify distinct thymic pathways that generate murine \u03b3\u03b4 T\u00a0cells pre-committed to the secretion of IL-17A or IFN\u03b3. This permits assessment of TCR\u03b3\u03b4 signal strength in thymic commitment to \u03b3\u03b4 T\u00a0cell effector fate; increased TCR\u03b3\u03b4 signal strength profoundly prohibits development of all IL-17A-secreting \u03b3\u03b4 T\u00a0cells. Anti-tu\u2212CD8\u2212 double-negative (DN) 2 cells (rather than DN3 cells) (+ cells) may inherently require certain transcription factors   was suggested to promote commitment to an IFN\u03b3-secreting fate , with we3 cells) . And cer Sox-13) . ClearlyThere is presently no accepted approach for stage-wise assessment of thymic \u03b3\u03b4 T\u00a0cell development. Indeed, although studies have analyzed V\u03b3 usage , acquisi\u2212 cells that expressed high CD44 but not CD45RB were committed to IL-17A secretion, but did not make IFN\u03b3, whereas cells that had upregulated CD45RB had potential to secrete IFN\u03b3 but not IL-17A  that re-capitulates thymic T\u00a0cell development in\u00a0vitro and is suited to studying \u03b3\u03b4 T\u00a0cell development that occurs predominantly in the perinatal period. Indeed, E15 thymic lobes cultured for 7\u00a0days generate \u03b3\u03b4 T\u00a0cell subsets similar to those observed ex\u00a0vivo -purified the four CD24 d cells C. Sortedectively C and 2D.products C and 2D,+ and V\u03b36+ cells being linked to IL-17A production, with V\u03b31+ and V\u03b35+ cells linked to IFN\u03b3  expression in V\u03b36+ cells  cells of making IL-17A  express T-bet but not ROR\u03b3t. Interestingly, our CD44/CD45RB plots show overlap with CD44/Ly-6C plots suggested to identify naive-like and memory-like peripheral \u03b3\u03b4 T\u00a0cell subsets  supports a model in which commitment to an IL-17A- or IFN\u03b3-secreting fate, with initial expression of corresponding \u201cmaster\u201d transcriptional regulators . These observations suggest thymic commitment of \u03b3\u03b4 progenitors to distinct effector fates is distinguishable  from actual capacity to secrete cytokine.Importantly, our analyses identify two thymic pathways of\u00a0functional \u03b3\u03b4 T\u00a0cell differentiation that diverge from a common\u00a0CD24gulators , spans a+V\u03b41+ cells in the presence of Skint1  \u03b3\u03b4 T\u00a0cells in SKG mice that have severely reduced Zap-70 activity  effects of increased TCR\u03b3\u03b4 signal strength mediated by anti-TCR\u03b4 antibody. Thus, activation of the ERK/MAP kinase pathway by strong TCR\u03b3\u03b4 signaling is a key limiter of progression to an IL-17A-secreting fate. As mentioned above, such strong signaling may reflect engagement of TCR ligand, as supported by complete segregation, in the prenatal thymus, of V\u03b35 pathway . Howeverignaling  that depnsidered . These iAdditional details are available in C57BL/6 (B6) mice were purchased from Charles River Laboratories. All mice\u00a0were fetal (E14\u2013E17), neonatal (1\u20133\u00a0days), post-natal (4\u20138\u00a0days), or\u00a0adult\u00a0. All experiments involving animals were performed in full compliance with UK Home Office regulations and institutional guidelines.Thymic lobes from B6 mice were cultured on Nuclepore membrane filter discs (Whatman) in complete RPMI-1640 medium plus 10% fetal calf serum (FCS) for 7\u201314\u00a0days.OP9-DL1 cells were provided by J.C. Z\u00faniga-Pfl\u00fccker (University of Toronto).For detection of V\u03b35V\u03b41 and V\u03b36V\u03b41, cells were pre-stained with GL3 followed by 17D1. For i.c. cytokine staining (eBioscience), cells were stimulated with 50\u00a0ng/ml phorbol 12-myristate 13-acetate  and 1\u00a0\u03bcg/ml ionomycin (Sigma) for 4\u00a0hr at 37\u00b0C. Acquisition was performed with an LSR-II or a Canto II (BD). Analysis was performed using FlowJo (Tree Star).GraphPad Prism software was used to analyze data, which are presented as mean \u00b1 SD. Two-tailed Student\u2019s unpaired t test was used when only two groups were compared, and one-way ANOVA with Tukey\u2019s test was used for multiple comparisons. Significance was determined at p \u2264 0.05.N.S. and C.L.G. performed experiments. N.S. and D.J.P. analyzed the data. B.S.-S. and D.J.P. designed the study. D.J.P. and N.S. wrote the paper."}
{"text": "III and DyIII with the ligand 2,6-di\u00adacetyl\u00adpyridine bis\u00ad(benzoyl\u00adhydrazone) have been synthesized and structurally characterized.Two isotypic complexes of Tb Ln(DAPBH2)(CH3OH)(H2O)3]Cl3\u00b72CH3OH , are isotypic. The central lanthanide ions are nine-coordinate, being ligated by three N and two O atoms from the penta\u00addentate DAPBH2 ligand, and four O atoms from the coordinated methanol mol\u00adecule and three coordinated water mol\u00adecules. The coordination geometry of the lanthanide ion is a distorted capped square anti\u00adprism. In the crystals, the various components are linked by O\u2014H\u22efCl, N\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds, forming three-dimensional supra\u00admolecular frameworks. Within the frameworks, there are C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds and offset \u03c0\u2013\u03c0 inter\u00adactions (inter\u00adcentroid distance ca 3.81\u2005\u00c5).The title lanthanide complexes, [ The bond distances for the DyIII complex are slightly shorter than those of the TbIII complex as a result of the lanthanide contraction effect. The DAPBH2 ligand is approximately planar, and the LnIII ion lies out of the mean plane (O1/N2/N3/N4/O2) by a distance of 0.5754\u2005(3)\u2005\u00c5 for the TbIII complex and 0.5702\u2005(3)\u2005\u00c5 for the DyIII complex. The coordination of the DAPBH2 ligand to the lanthanide ion shows a bent arrangement . These coordination features are similar to those reported for the dysprosium DAPBH2 nitrate complex \u2005\u00c5, \u03b1 = 3.8\u2005(1)\u00b0, inter\u00adplanar distance = 3.483\u2005(1)\u2005\u00c5, slippages = 1.77 and 1.55\u2005\u00c5; Cg2 and Cg3 are the centroids of C2\u2013C7 and C18\u2013C23 rings, respectively, symmetry codes: (a) x, y\u00a0\u2212\u00a01, z; (b) x, y\u00a0+\u00a01, z]. The layers are linked by O\u2014H\u22efO, O\u2014H\u22efCl and N\u2014H\u22efCl hydrogen bonds, forming a three-dimensional supra\u00admolecular framework, which is reinforced by a series of C\u2014H\u22efCl and C\u2014H\u22efO hydrogen bonds , 2,6-di\u00adacetyl\u00adpyridine , and benzoyl\u00adhydrazine  was refluxed for 2\u2005h. The resulting mixture was filtered. Vapour diffusion of diethyl ether into the filtrate afforded colourless plate-like crystals of the TbIII complex . The synthetic procedure for the DyIII complex is similar, starting from dysprosium chloride (yield 43%).A methanol solution (15\u2005ml) of TbClIII complex was restrained to 0.82\u2005\u00c5. Other hydrogen atoms were generated geometrically and refined with a riding model: N\u2014H = 0.88\u2005\u00c5, C\u2013H = 0.95\u20130.98\u2005\u00c5 with Uiso(H) = 1.5Ueq and 1.2 Ueq for other H atoms.Crystal data, data collection, and structure refinement details are summarized in Table\u00a0410.1107/S2056989018004103/su5429sup1.cifCrystal structure: contains datablock(s) TbDAPBH2, DyDAPBH2, global. DOI: 10.1107/S2056989018004103/su5429TbDAPBH2sup2.hklStructure factors: contains datablock(s) TbDAPBH2. DOI: 10.1107/S2056989018004103/su5429DyDAPBH2sup3.hklStructure factors: contains datablock(s) DyDAPBH2. DOI: 1828810, 1828809CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The organic mol\u00adecule is twisted with a near orthogonal relationship between the outer rings [dihedral angle = 71.79\u2005(6)\u00b0]. Supra\u00admolecular ribbons sustained by hydrogen bonding feature in the mol\u00adecular packing. 14H12BrN3O2\u00b7H2O {systematic name: N\u2032-[(1E)-1-(5-bromo-2-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene]pyridine-4-carbohydrazide monohydrate}, the central CN2O region of the organic mol\u00adecule is planar and the conformation about the imine-C=N bond is E. While an intra\u00admolecular hy\u00addroxy-O\u2014H\u22efN(imine) hydrogen bond is evident, the dihedral angle between the central residue and the benzene rings is 48.99\u2005(9)\u00b0. Overall, the mol\u00adecule is twisted, as seen in the dihedral angle of 71.79\u2005(6)\u00b0 between the outer rings. In the crystal, hydrogen-bonding inter\u00adactions, i.e. hydrazide-N\u2014H\u22efO(water), water-O\u2014H\u22efO(carbon\u00adyl) and water-O\u2014H\u22efN(pyrid\u00adyl), lead to supra\u00admolecular ribbons along the a-axis direction. Connections between these, leading to a three-dimensional architecture, are mediated by Br\u22efBr halogen bonding [3.5366\u2005(3)\u2005\u00c5], pyridyl-C\u2014H\u22efO(carbon\u00adyl) as well as weak \u03c0\u2013\u03c0 inter\u00adactions [inter-centroid separation between benzene rings = 3.9315\u2005(12)\u2005\u00c5]. The Hirshfeld surface analysis reveals the importance of hydrogen atoms in the supra\u00admolecular connectivity as well as the influence of the Br\u22efBr halogen bonding.In the title isonicotinohydrazide hydrate, C Recent inter\u00adest in the coordination of hydrazide Schiff base ligands arises owing to the presence of electron-donating nitro\u00adgen and oxygen atoms, allowing these to act as a multidentate ligands, and in some cases, function as supra\u00admolecular building blocks in their mol\u00adecular assemblies \u00b0], N2\u2014N1\u2014C1\u2014C10 [179.59\u2005(15)\u00b0] and C1\u2014N1\u2014N2\u2014C2 [171.14\u2005(18)\u00b0] torsion angles is consistent with an all-trans relationship in the central chain and a small twist about the N1\u2014N2 bond. The conformation about the imine-C2=N2 bond [1.292\u2005(2)\u2005\u00c5] is E. An intra\u00admolecular hy\u00addroxy-O1\u2014H\u22efN2(imine) hydrogen bond is noted, Table\u00a01The mol\u00adecular structures of the constituents of (I)a-axis direction and mediated by hydrogen-bonding inter\u00adactions. In essence, the water mol\u00adecule provides links between three organic mol\u00adecules via hydrazide-N\u2014H\u22efO(water), water-O\u2014H\u22efO(carbon\u00adyl) and water-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds, Table\u00a014O}2 synthons as shown in Fig.\u00a02a. Lateral connections between ribbons are via halogen bonding of the type Br\u22efBr. Here, the Br\u22efBri separation is 3.5366\u2005(3)\u2005\u00c5 . The C7\u2014Br\u22efBri angle is 156.56\u2005(5)\u00b0, and, being disposed about a centre of inversion, the C7\u2014Br\u22efBri\u2014C7i torsion angle is constrained by symmetry to 180\u00b0. The geometric characteristics indicate the Br\u22efBri halogen bond is classified as a type I halogen bond  within the surface near the water-O1W atoms as well as the blue regions  about the water-H1W and H2W atoms, which correspond to the acceptor and donors of the hydrogen bonds, respectively. Similarly, the other donor and acceptor atoms participating in the more significant inter\u00admolecular inter\u00adactions are viewed as the blue and red regions, respectively, in Fig.\u00a03dnorm in Fig.\u00a04b also highlight the significant contribution of Br\u22efBr and C\u22efC contacts to the mol\u00adecular packing. The presence of faint-red spots near the pyridyl-N3, C13 and H13 atoms and the carbonyl-O1 atom indicate their contributions to short inter\u00adatomic C\u22efN/N\u22efC contacts  and shape-index-  mapped Hirshfeld surfaces highlighting the various short inter\u00adatomic contacts influential on the mol\u00adecular packing are illustrated in Fig.\u00a05a, C\u22efC and C\u22efN/N\u22efC contacts, Fig.\u00a05b, and Br\u22efBr and Br\u22efH/H\u22efBr contacts, Fig.\u00a05c, identify their roles in consolidating the packing in the crystal.The analysis of the Hirshfeld surface for (I)s Table\u00a02 and compm- Fig.\u00a05a and b x- Fig.\u00a05c mappeda, and those delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC, Br\u22efH/H\u22efBr, N\u22efH/H\u22efN, C\u22efC, Br\u22efBr and C\u22efN/N\u22efC contacts  hydrogen bonds are seen on the dnorm-mapped Hirshfeld surface in Fig.\u00a04b). The conformational relationship between each of the pyridyl and benzene rings to the central planar region make these residues available for forming C\u22efH/H\u22efC contacts. The significant contribution of 17.9% from C\u22efH/H\u22efC contacts results from the short inter\u00adatomic contacts listed in Table\u00a02d with the pair of peaks at de\u00a0+\u00a0di\u00a0\u223c\u00a02.8\u2005\u00c5; these short inter\u00adatomic contacts are illustrated in Fig.\u00a05a. A forceps-like fingerprint plot corresponding to Br\u22efH/H\u22efBr contacts in Fig.\u00a06e with its tips at de\u00a0+\u00a0di\u00a0\u223c\u00a03.0\u2005\u00c5 represents the influence of the halogen\u22efhydrogen inter\u00adactions in the mol\u00adecular packing. Along with Br\u22efH/H\u22efBr contacts, Table\u00a02via Br\u22efBr contacts, as evident in Fig.\u00a06h as a very thin line beginning at de\u00a0+\u00a0di\u00a0\u223c\u00a03.5\u2005\u00c5. The contributions from other inter\u00adatomic contacts involving the bromide atom have negligible effect on the crystal stability because their inter\u00adatomic distances are much greater than sum of their respective van der Waals radii. The small but notable contributions from the C\u22efC and C\u22efN/N\u22efC contacts to the Hirshfeld surface, Table\u00a02g, a spear-shaped distribution of points with the tip at de\u00a0+\u00a0di\u00a0\u223c\u00a03.2\u2005\u00c5 and an adjacent arrow-like distribution of points at de\u00a0=\u00a0di\u00a0\u223c\u00a01.9\u2005\u00c5 result, respectively, from inter\u00adatomic C\u22efC contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions involving the C3\u2013C8 ring. The short inter\u00adatomic C\u22efN/N\u22efC contacts involving the pyridyl-C13 and N3 atoms, Fig.\u00a05b, are reflected in a pair of small peaks at de\u00a0+\u00a0di\u00a0\u223c\u00a03.2\u2005\u00c5 in Fig.\u00a06i. The small contributions from other inter\u00adatomic contacts listed in Table\u00a02The overall two-dimensional fingerprint plot, Fig.\u00a06et al., 2016et al., 2014cf. the near to orthogonal relationship in (I)The most closely related structure to (I)\u22121. The 1H NMR spectrum was recorded at room temperature in CDCl3 solution on a Jeol ECA 400\u2005MHz FT\u2013NMR spectrometer.All chemicals and solvents were used as purchased without purification, and all reactions were carried out under ambient conditions. The melting point was determined using an Electrothermal digital melting-point apparatus and was uncorrected. The IR spectrum for the compound was obtained on a Perkin Elmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer from 4000 to 400\u2005cmn-butyl\u00adtin dichloride  in methanol (10\u2005ml). The resulting mixture was stirred and refluxed for 3\u2005h. A cloudy orange solution was obtained and the mixture was filtered. The filtrate was allowed to stand at room temperature and yellow crystals, suitable for X-ray crystallographic studies, were obtained after the slow evaporation. The yellow crystals were found to be a side-product from the reaction mixture. Yield: 0.112\u2005g, 34%; M.p. 501\u2005K. IR (cm\u22121): 3158(br), 1666(s), 1548(s), 1152 (m), 964(s) cm\u22121. 1H NMR (in CDCl3): 11.20 , 8.73-8.82, 7.92-8.20, 6.80-6.99 , 4.82 , 4.10 , 3.13 .1-(5-Bromo-2-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene]iso\u00adnicotino\u00adhydra\u00adzide  and tri\u00adethyl\u00adamine  in methanol (25\u2005ml) were added to di-Uiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017004790/hb7669sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017004790/hb7669Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004790/hb7669Isup3.cmlSupporting information file. DOI: 1540550CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is an epimer of natural tetra\u00adcyclic isosaxorumamide. The di\u00adhydro\u00adfuran\u00adone, oxolane, azepane and pyrrolidine rings adopt planar, twist, twist-chair and envelope forms, respectively. In the crystal, O\u2014H\u22efO hydrogen bonds connect the water and main mol\u00adecules into a tape structure, which is further expanded into a three-dimensional network by C\u2014H\u22efO inter\u00adactions. 17H23NO4\u00b7H2O, is an epimer of the natural tetra\u00adcyclic alkaloid isosaxorumamide which consists of a fused 5\u20137\u20135 tricyclic core and a di\u00adhydro\u00adfuran\u00adone substituent. The terminal di\u00adhydro\u00adfuran ring is essentially planar with a maximum deviation of 0.0273\u2005(14)\u2005\u00c5 from the mean plane and oxolane, azepane and pyrrolidine rings in the tricyclic ring system adopt twist, twist-chair and envelope forms, respectively. In the crystal, the amide and water mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming a tape structure running along the b-axis direction. The tapes are further connected by C\u2014H\u22efO inter\u00adactions into a three-dimensional architecture.The title compound, C Stemona alkaloids isolated from the root of Stemona Saxorum  = 0.350\u2005(3)\u2005\u00c5 and \u03c6(2) = 271.0\u2005(4)\u00b0. Atoms C8 and C9 deviate from the plane through the other three atoms by 0.309\u2005(6) and \u22120.271\u2005(6)\u2005\u00c5, respectively. The central seven-membered azepane ring (N1/C2\u2013C5/C9/C10), which is trans-fused to the oxolane ring, adopts a twist-chair form with puckering parameters of Q = 0.796\u2005(2), Q(2) = 0.472\u2005(2)\u2005\u00c5, \u03c6(2) = 195.0\u2005(3)\u00b0, Q(3) = 0.641\u2005(2)\u2005\u00c5 and \u03c6(3) = 246.7\u2005(2)\u00b0. The pyrrolidine ring (N1/C10\u2013C13) fused to the azepane ring adopts an envelope form with puckering parameters of Q(2) = 0.300\u2005(3)\u2005\u00c5 and \u03c6(2) = 251.1\u2005(5)\u00b0. The flap atom C11 deviates from the mean plane through the other four atoms by 0.473\u2005(4)\u2005\u00c5. The amide moiety (N1/C2/C10/C13/O14) is planar, and atoms N1 and O14 deviate from the mean plane through the other three atoms by 0.028\u2005(2) and \u22120.035\u2005(4)\u2005\u00c5, respectively.The asymmetric unit of the title compound is shown in Fig.\u00a02W\u2014H1WA\u22efO14i and O1W\u2014H1WB\u22efO14ii; symmetry codes as in Table\u00a01b-axis direction. A C\u2014H\u22efO inter\u00adaction  graph-set motif. Furthermore, a weak C\u2014H\u22efO inter\u00adaction , i.e. the fused tricyclic core related to the title compound , with CSD refcodes VATJAC , with refcodes PROTMI  is the natural alkaloid (\u2013)-stemo\u00adamide, which is a -7,13-dione derivative of (a), and XATFOP (space group P21/n) is its racemate.In the Cambridge Structural Database . HRMS (ESI) m/z calculated for C17H24NO4+ [M + H]+: 306.1705; found: 306.1703.The title compound was afforded in a synthetic study of saxorumamide and isosaxorumamide, from ethyl 4-bromo\u00adbutano\u00adate and a siloxypyrrole analogue (Yoritate Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). Water H atoms were located in a difference-Fourier map, and then refined freely with Uiso(H) = 1.5Ueq(O), and with distance restraints of O\u2014H = 0.84\u2005(2)\u2005\u00c5 and H\u22efH = 1.33\u2005(4)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018004425/is5494sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018004425/is5494Isup2.hklStructure factors: contains datablock(s) I. DOI: 1830268CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(2-iodo\u00adphen\u00adyl)acetamide into twofold inter\u00adwoven sheets, and the mol\u00adecules of 2-(4-chloro\u00adphen\u00adyl)-N-(pyrazin-2-yl)acetamide are linked into complex sheets built solely from hydrogen bonds.A combination of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds together with C\u2014Cl\u22ef\u03c0(arene) and C\u2014I\u22ef\u03c0(arene) inter\u00adactions links the mol\u00adecules of 2-(4-chloro\u00adphen\u00adyl)- N-(2-iodo\u00adphen\u00adyl)acetamide, C14H11ClINO, mol\u00adecules are linked by a combination of N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds to form a C(4)C(4)[R21(7)] chain of rings and chains of this type are linked by a combination of C\u2014Cl\u22ef\u03c0(arene) and C\u2014I\u22ef\u03c0(arene) inter\u00adactions to form deeply puckered twofold inter\u00adwoven sheets. In the crystal of 2-(4-chloro\u00adphen\u00adyl)-N-(pyrazin-2-yl)acetamide, C12H10ClN3O, mol\u00adecules are linked into complex sheets by N\u2014H\u22efN, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, and by C\u2014H\u22ef\u03c0(arene) inter\u00adactions.In the crystal of 2-(4-chloro\u00adphen\u00adyl)- R1CH2CONHR2, where R1 and R2 are aromatic or hetero-aromatic substituents, are of inter\u00adest as they have some resemblance to benzyl penicillins ca 0.01\u2005\u00c5, indicating that this ring is fully aromatic.In the pyrazine ring of compound (II)C(4)C(4) direction  x, y, z, where Cg1 represents the centroid of the C11\u2013C16] ring, I\u22efCg 3.7977\u2005(14), C\u22efCg 5.082\u2005(3)\u2005\u00c5 and C\u2014I\u22efCg 116.34\u2005(8)\u00b0; for C24\u2014Cl24\u22efCg2ii , Cl\u22efCg 3.4557\u2005(8), C\u22efCg 4.504\u2005(3)\u2005\u00c5 and C\u2014Cl\u22efCg 116.19\u2005(11)\u00b0. The metrics of the C\u2014Cl\u22efCg inter\u00adaction are well within the normal range, as deduced using database analysis on Fig.\u00a03. There ion Fig.\u00a03, lying won Fig.\u00a03. The dimi 3.058\u2005(2)\u2005\u00c5 and C12\u2014I12\u22efO1i 170.88\u2005(8)\u00b0  which complements the C\u2014Cl\u22efCg contact. The I\u22efO distance here is significantly shorter than the sum of the van der Waals radii, 3.56\u2005\u00c5 C(5) for the group of 428 very weak reflections having Fc/Fc(max) in the range 0.000 < Fc/Fc(max) < 0.008.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016012512/su5316sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989016012512/su5316Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016012512/su5316IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016012512/su5316Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016012512/su5316IIsup5.cmlSupporting information file. DOI: 1497360, 1497359CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N,S-chelating hydrazinecarbodi\u00adthio\u00adate ligands provide a trans-N2S2 donor set and a distorted square-planar geometry for the NiII atom. In the crystal, a three-dimensional network is sustained by C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions.Two  19H21N2S2)2], is generated by the application of a centre of inversion. The NiII atom is N,S-chelated by two hydrazinecarbodi\u00adthio\u00adate ligands, which provide a trans-N2S2 donor set that defines a distorted square-planar geometry. The conformation of the five-membered chelate ring is an envelope with the NiII atom being the flap atom. In the crystal, p-tolyl-C\u2014H\u22ef\u03c0(benzene-iPr), iPr-C\u2014H\u22ef\u03c0(p-tol\u00adyl) and \u03c0\u2013\u03c0 inter\u00adactions [between p-tolyl rings with inter-centroid distance = 3.8051\u2005(12)\u2005\u00c5] help to consolidate the three-dimensional architecture. The analysis of the Hirshfeld surface confirms the importance of H-atom contacts in establishing the packing.The complete mol\u00adecule of the title hydrazine carbodi\u00adthio\u00adate complex, [Ni(C S-R-di\u00adthio\u00adcarbazate (R = meth\u00adyl/benz\u00adyl/methyl\u00adbenz\u00adyl) and heterocyclic aldehydes or ketones have received much attention in recent years owing to their cytotoxicity S,N-chelating hydrazinecarbodi\u00adthio\u00adate anions. From symmetry, the resulting N2S2 donor set has like atoms trans, and the square-planar coordination geometry is strictly planar. Distortions from the ideal geometry are related to the deviations of angles subtended at nickel by the donor atoms, Table\u00a01i.e. \u2212165.61\u2005(17)\u00b0. Despite being involved in a formal bond to the NiII atom, the C1\u2014S1 bond length of 1.7296\u2005(19)\u2005\u00c5 is still significantly shorter than those formed by the S2 atom, i.e. C1\u2014S2 = 1.7479\u2005(18)\u2005\u00c5 and C12\u2014S2 = 1.824\u2005(2)\u2005\u00c5.The Ni2S2 donor set does not extend to the five-membered chelate ring, which has an envelope conformation with the nickel atom lying 0.465\u2005(2)\u2005\u00c5 above the least-squares plane through the remaining atoms [r.m.s. deviation = 0.0016\u2005\u00c5]. The sequence of C1=N1, N1\u2014N2 and N2=C2 bond lengths of 1.294\u2005(2), 1.408\u2005(2) and 1.300\u2005(2)\u2005\u00c5, respectively, suggests limited conjugation across this residue. Each of the benzene rings of the S- and N-bound substituents is twisted with respect to the least-squares plane through the chelate ring. Thus, a nearly orthogonal relationship exists between the chelate and p-tolyl rings, with the dihedral angle being 89.72\u2005(5)\u00b0. Less dramatic is the twist of the iPr-substituted ring with the dihedral angle being 13.83\u2005(9)\u00b0. The dihedral angle between the aromatic rings is 84.31\u2005(6)\u00b0.The planarity of the Ni.e. the S1 and N1 atoms, are involved in intra\u00admolecular inter\u00adactions, Table\u00a02i.e. p-tolyl-C\u2014H\u22ef\u03c0(iPr-benzene) and iPr-benzene-C\u2014H\u22ef\u03c0(p-tol\u00adyl) contacts, Table\u00a02p-tolyl rings self-associate via face-to-face, \u03c0\u2013\u03c0, inter\u00adactions , indicating the p-tolyl ring participates in two distinct inter\u00adactions. The result of the supra\u00admolecular association is the formation of a three-dimensional architecture, Fig.\u00a02The two sites potentially available for hydrogen bonding in (I)et al., 2017dnorm (not shown) clearly indicates the absence of conventional hydrogen bonding in the crystal. The donors and acceptors of C\u2014H\u22ef\u03c0 inter\u00adactions, involving atoms of each of the iPr-benzene and p-tolyl rings, are viewed as blue and light-red regions and correspond to the respective positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (over the range \u00b1 0.025 au), Fig.\u00a03iPr-benzene and p-tolyl rings on the Hirshfeld surface mapped over de, Fig.\u00a04i.e. \u03c0\u22efH\u2014C contacts, between iPr\u2013H11B and the p-tolyl ring are represented by red and white dotted lines, respectively in Fig.\u00a05a; the blue dotted lines in Fig.\u00a05a represent \u03c0\u2013\u03c0 stacking between p-tolyl rings at \u2212x, \u22121\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. The other C\u2014H\u22ef\u03c0 contacts involving p-tolyl-H17 and iPr-benzene rings are illustrated in Fig.\u00a05b.The Hirshfeld surface analysis for (I)et al., 2007a\u2013f. From the qu\u00adanti\u00adtative summary of the relative contributions of the various inter\u00adatomic contacts given in Table\u00a03i.e. 95.3%. In the fingerprint plot delineated into H\u22efH contacts. Fig.\u00a06b, the points are distributed in the major part of the plot, but they do not make significant contributions to the mol\u00adecular packing as their inter\u00adatomic separations are greater than sum of their van der Waals radii, i.e. de\u00a0+\u00a0di\u00a0>\u00a02.4\u2005\u00c5. The presence of short inter\u00adatomic C\u22efH/H\u22efC contacts, see Table\u00a04i.e. 22.2%. This is consistent with the fingerprint plot, Fig.\u00a06c, where the short inter\u00adatomic C\u22efH/H\u22efC contacts appear as a pair of small peaks at de\u00a0+\u00a0di\u00a0\u223c\u00a02.8\u2005\u00c5 and also as the blue regions around the participating hydrogen atoms, namely H5 and H10B, on the Hirshfeld surface mapped over electrostatic potential, Fig.\u00a03d and e, indicate meaningful contributions to the Hirshfeld surface, Table\u00a03i.e. 2.1%, but recognizable contribution from C\u22efC contacts to the Hirshfeld surface is ascribed to \u03c0\u2013\u03c0 stacking inter\u00adactions between symmetry-related p-tolyl rings, and appear as an arrow-like distribution of points around de\u00a0=\u00a0di\u00a01.9\u2005\u00c5 in Fig.\u00a06f. The other contacts have low percentage contributions to the surface and are likely to have negligible effects on the mol\u00adecular packing, Table\u00a03The overall two-dimensional fingerprint plot and those delineated into H\u22efH, C\u22efH/H\u22efC, S\u22efH/H\u22efS and N\u22efH/H\u22efN and C\u22efC contacts , with a formal link between the two imine functionalities, the cis-N2S2 arrangement is imposed by the geometric requirements of the bis\u00ad(di\u00adthio\u00adcarbazate) di-anion  di\u00adthio\u00adcarbazate complexes in the crystallographic literature (Groom S-4-methyl\u00adbenzyl\u00addithio\u00adcarbazate (S4MDTC) precursor was synthesized by following a procedure adapted from the literature : 1589, \u03bd(C=N); 997, \u03bd(N\u2014N); 823, \u03bd(C=S).The synthesized Schiff base  was dissolved in hot aceto\u00adnitrile (50\u2005ml) and added to nickel(II) acetate tetra\u00adhydrate  in an ethano\u00adlic solution (30\u2005ml). The mixture was heated and stirred to reduce the volume of the solution. Precipitation occurred once the mixture cooled to room temperature. The precipitate then was filtered and dried over silica gel. The complex was recrystallized from its methanol solution. Brown prismatic crystals were formed from the filtrate after being left to stand for a month. The crystals were filtered and washed with absolute ethanol at room temperature. Yield: 70%. M.p.: 479\u2013480\u2005K. Elemental composition calculated for CUiso(H) set to 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017002419/hb7658sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017002419/hb7658Isup2.hklStructure factors: contains datablock(s) I. DOI: 1532446CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A growing body of evidence suggests that metabolic syndrome is associated with endocrine disorders including thyroid dysfunction. Thyroid dysfunction in metabolic syndrome patients may further add to cardiovascular disease risk thereby increasing mortality. This study was done to assess thyroid function in metabolic syndrome patients and evaluate its relationship with the components of metabolic syndrome.A cross sectional study was carried out among 169 metabolic syndrome patients at B P Koirala Institute of Health Sciences, Dharan, Nepal. Anthropometric measurements  and blood pressure were taken. Fasting blood samples were analysed to measure glucose, triglyceride, high density lipoprotein (HDL) cholesterol and thyroid hormones .n\u2009=\u200954) metabolic syndrome patients. Subclinical hypothyroidism (26.6\u00a0%) was the major thyroid dysfunction followed by overt hypothyroidism (3.5\u00a0%) and subclinical hyperthyroidism (1.7\u00a0%). Thyroid dysfunction was much common in females  than males  but not statistically significant (p\u2009=\u20090.068). The relative risk of having thyroid dysfunction in females was 1.525 (CI: 0.983\u20132.368) as compared to males. Significant differences (p\u2009=\u20090.001) were observed in waist circumference between patients with and without thyroid dysfunction and HDL cholesterol which had significant negative correlation with thyroid stimulating hormone.Thyroid dysfunction was seen in 31.9\u00a0% . Metabolic syndrome constitutes a cluster of risk factors characterized by hypertension, atherogenic dyslipidemia, hyperglycemia, prothrombotic and proinflammatory conditions . This clThyroid dysfunction, prominently subclinical hypothyroidism has been observed more frequently in metabolic syndrome patients than general population . Both meThere is evidence that thyroid function may need to be assessed in patients with metabolic syndrome who are also at higher risk for CVD. Thyroid dysfunction is common in Nepal, and the prevalence of diabetes mellitus and metabolic syndrome has been rising steadily. Reports suggest that 20.7\u00a0% of the Nepalese population have metabolic syndrome based on National Cholesterol Education Program (NCEP) criteria , 9. HoweIn this study, we assessed thyroid function and examined the association between components of metabolic syndrome and thyroid function in Nepalese population with metabolic syndrome.A cross-sectional study was conducted among metabolic syndrome patients at the department of biochemistry of B P Koirala Institute of Health Sciences (BPKIHS), Dharan, Nepal from September 2013 to September 2014. One hundred sixty nine metabolic syndrome patients aged \u226520\u00a0years were selected from the hospital during the study period. The sample size was calculated by taking prevalence of thyroid dysfunction as 15\u00a0% (approximate) in this region. Metabolic syndrome was diagnosed based on modified Asian NCEP-ATP III panel criteria . The excMetabolic syndrome patients were considered to have thyroid dysfunction if patients thyroid hormones level fell outside the reference range (free T3 (4.0\u20138.3 pmol/L), free T4 (9.0\u201320.0 pmol/L) and TSH level (0.25\u20135 mIU/L)). Patients were said to be euthyroid if all thyroid hormone levels fell within reference range. Overt hypothyroidism was defined as TSH\u2009>\u20095 mIU/L and free T3\u2009<\u20094.0 pmol/L and free T4\u2009<\u20099.0 pmol/L. Subclinical hypothyroidism was considered if TSH\u2009>\u20095 mIU/L and free T3 and free T4 within reference range. Subclinical hyperthyroidism was defined as TSH\u2009<\u20090.25 mIU/L and free T3 and free T4 within reference range. The data generated from study was analyzed using SPSS version 11.0. Continuous variables were expressed as mean\u2009\u00b1\u2009SD values. Independent sample t test and one way ANOVA was applied for continuous variables and chi square test for categorical variables at 95\u00a0% confidence interval. Pearson correlation coefficients were calculated to find relationship between the components of metabolic syndrome and thyroid profile parameters at 95\u00a0% confidence interval. Relative risk with 95\u00a0% confidence interval (CI) was used to assess the risk factors for thyroid dysfunction in metabolic syndrome.n\u2009=\u200996) males and 43.2\u00a0% (n\u2009=\u200973) females, with mean age of 47\u2009\u00b1\u200912.5\u00a0years. Height, weight, body mass index (BMI), waist circumference, systolic BP and diastolic BP were 157.4\u2009\u00b1\u20098\u00a0cm, 70.7\u2009\u00b1\u20097.9 Kg, 28.6\u2009\u00b1\u20093.3 Kg/m2, 102.5\u2009\u00b1\u20096.7\u00a0cm, 129.3\u2009\u00b1\u200913.6\u00a0mmHg and 84.9\u2009\u00b1\u200911.5\u00a0mmHg respectively. Similarly, levels of biochemical parameters; fasting blood glucose, triglyceride, HDL cholesterol, free T3, free T4 and TSH were 126.2\u2009\u00b1\u200950.4\u00a0mg/dL, 198.2\u2009\u00b1\u200990.8\u00a0mg/dL, 49.9\u2009\u00b1\u200915.3\u00a0mg/dL, 5.1\u2009\u00b1\u20091.0 pmol/L, 12.0\u2009\u00b1\u20092.9 pmol/L and 4.2\u2009\u00b1\u20093.4 mIU/L respectively. Thyroid dysfunction was found in 31.9\u00a0% (n\u2009=\u200954) patients. Subclinical hypothyroidism (26.6\u00a0%) was the major thyroid dysfunction followed by overt hypothyroidism (3.5\u00a0%) and subclinical hyperthyroidism (1.7\u00a0%). Components of metabolic syndrome according to thyroid dysfunction type are shown in Table\u00a0n\u2009=\u200929) than males 26\u00a0% (n\u2009=\u200925) but not statistically significant (p\u2009=\u20090.068). Among males, 23 had subclinical hypothyroidism, 1 had overt hypothyroidism and 1 had subclinical hyperthyroidism. Similarly among females, 22 had subclinical hypothyroidism, 5 had overt hypothyroidism and 2 had subclinical hyperthyroidism. The relative risk of having thyroid dysfunction in females was 1.525  as compared to males. When metabolic syndrome parameters were compared between the patients subgroups (with TSH\u2009<\u20095 mIU/L and TSH\u2009\u2265\u20095 mIU/L), then systolic BP, diastolic BP, waist circumference, blood glucose, triglyceride and HDL cholesterol were 129.7\u2009\u00b1\u200912.6\u00a0mmHg versus 128.4\u2009\u00b1\u200916\u00a0mmHg; p\u2009=\u20090.602, 85.3\u2009\u00b1\u200911\u00a0mmHg versus 84\u2009\u00b1\u200912.8\u00a0mmHg; p\u2009=\u20090.513, 103.4\u2009\u00b1\u20096.6\u00a0cm versus 100.5\u2009\u00b1\u20096.6\u00a0cm; p\u2009=\u20090.008, 125.2\u2009\u00b1\u200953.2\u00a0mg/dL versus 128.6\u2009\u00b1\u200943.7\u00a0mg/dL; p\u2009=\u20090.692, 189.7\u2009\u00b1\u200975.5\u00a0mg/dL versus 217.9\u2009\u00b1\u2009117.6\u00a0mg/dL; p\u2009=\u20090.119 and 51\u2009\u00b1\u200916.8\u00a0mg/dL versus 47.4\u2009\u00b1\u200911\u00a0mg/dL; p\u2009=\u20090.103 respectively. Correlation between the components of metabolic syndrome and TSH and free T4 is shown in Table\u00a0p\u2009=\u20090.037) and free T4  and weak positive correlation with TSH .The study population consisted of 56.8\u00a0%  between patients with and without thyroid dysfunction, and HDL cholesterol had significant negative association with TSH level, however, other components of metabolic syndrome had no significant relationships with thyroid dysfunction. Thyroid hormones affect lipid metabolism and thus the components of metabolic syndrome, and there is positive relation between TSH and LDL cholesterol, whereas negative relation between TSH and HDL cholesterol [The correlation between subclinical hypothyroidism and metabolic syndrome and its components varies in different studies and seems to be influenced by age, gender and race of study participants . In the lesterol . Our finlesterol . There alesterol . In a stlesterol . Howeverlesterol .2), had higher triglyceride levels, and an increased likelihood of having metabolic syndrome [In the present study, we observed negative association of BMI with free T3 and free T4 and weak positive correlation with TSH. In a study in Germany, euthyroid subjects with TSH in the upper normal range (2.5\u20134.5\u00a0mU/L) were more obese ."}
{"text": "Elaeodendron trichotomum (Turcz.) Lundell is reported.The crystal structure of the triterpene lactone ochraceolide A (3-oxolup-20\u2005(29)-en-30,21\u03b1-olide) isolated from  30H44O3 indeno\u00adfuran-3,11(2H)-dione], is a triterpene lactone, which was isolated from di\u00adchloro\u00admethane extract of Elaeodendron trichotomum (Turcz.) Lundell (celastraceae) stem bark. The compound has a lupane skeleton and consists of four fused six-membered rings and two five-membered rings. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds into a three-dimensional network. The configuration of ochraceolide A was proposed based on analogue compounds which belong to the lupane type.The title compound, C Kokoona ochracea (Elm.) Merril stem bark  with an ED50 of 6.0\u2005\u00b5M; and hormone-dependent breast cancer with an ED50 of 9.9\u2005\u00b5M  isolated from Hippocratea celastroides K.  Lundell stem bark is reported and the crystal structure described.Ochraceolides A\u2013E are a group of cytotoxic lupane \u03b3-lactones isolated from the Celastraceae family. Ochraceolide A was firstly isolated from P212121 with one mol\u00adecule in the asymmetric unit  and two five-membered rings (E and F). The cyclo\u00adhexane rings are trans-fused and in standard chair conformations. The cyclo\u00adpentane (C17\u2013C19/C21/C22) ring is trans-fused to the triterpene D ring and exhibits an envelope conformation [Q = 0.451\u2005(4)\u2005\u00c5 and \u03b8 = 356.7\u2005(5)\u00b0] with the puckered C17 atom having the maximum deviation of 0.285\u2005(4)\u2005\u00c5. The \u03b1-methyl\u00adene \u03b3-lactone is cis-fused at C19\u2013C21 to the cyclo\u00adpentane E ring and is essentially planar with a maximum deviation of 0.006\u2005(4)\u2005\u00c5 for atom C19. The torsion angle C20\u2014C19\u2014C21\u2014O2 is 0.8\u2005(4)\u00b0 and the weighted average absolute inter\u00adnal torsion angle for the lactone ring is 0.7\u2005(2)\u00b0The title compound has a lupane skeleton and crystallizes in the ortho\u00adrhom\u00adbic space group it Fig.\u00a01. The triA rings of adjacent mol\u00adecules inter\u00adact through two hydrogen bonds (C2\u2014H2A\u22efO2 and C24\u2014H24A\u22efO3) in a head-to-tail arrangement, forming chains along [001]. These chains are further connected through a weak hydrogen bond between the oxygen of the ketone group (O1) and a methyl\u00adene group on the C ring (C12), forming an overall three-dimensional network.In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds Table\u00a01. The lacet al., 2016H-cyclo\u00adpenta\u00ad[b]furan-2,5(3H)-dione  Lundell was collected from Chunchucmil, Yucat\u00e1n, M\u00e9xico . A voucher specimen (JTun2328) was deposited at the Herbarium Alfredo Barrera Mar\u00edn, Universidad Aut\u00f3noma de Yucat\u00e1n, M\u00e9xico. Dried and milled stem bark (2100\u2005g) was exhaustively extracted by di\u00adchloro\u00admethane using a Soxhlet extraction apparatus to yield 184.2\u2005g of crude extract. A portion of the extract (100\u2005g) was chromatographed on silica gel (40\u201360\u2005\u00b5m) using a gradient elution with n-hexa\u00adne\u2013ethyl acetate (10\u2013100% ethyl acetate), to obtain 44 fractions. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of the mixture of solvents present in fractions 7\u201310 at room temperature.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017012816/lh4023sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017012816/lh4023Isup2.hklStructure factors: contains datablock(s) I. DOI: 1573017CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-chromen-2-one), the 4-hy\u00addroxy-3-meth\u00adoxy\u00adphenyl-substituted derivative of dicoumarol, was deprotonated by the addition of tri\u00adethyl\u00adamine, yielding the respective ammonium salt which was crystallized from a methanol solution. The deprotonated dicoumarol derivative exhibits an intra\u00admolecular negative charge-assisted hydrogen bond between the deprotonated and non-deprotonated alcohol functions of the coumarol substituents.3,3\u2032-[(3-Meth\u00adoxy-4-hy\u00addroxy\u00adphen\u00adyl)methanedi\u00adyl]bis\u00ad(4-hy\u00addroxy-2 H-chromen-2-one) and tri\u00adethyl\u00adamine in methanol yielded the title compound tri\u00adethyl\u00adammonium 3-[(4-hy\u00addroxy-3-meth\u00adoxy\u00adphen\u00adyl)(4-hy\u00addroxy-2-oxo-2H-chromen-3-yl)meth\u00adyl]-2-oxo-2H-chromen-4-olate, C6H16N+\u00b7C26H17O8\u2212 or (NHEt3)+(C26H17O8)\u2212, which crystallized directly from its methano\u00adlic mother liquor. The non-deprotonated coumarol substituent shares its H atom with the deprotonated coumarolate substituent in a short negative charge-assisted hydrogen bond in which the freely refined H atom is moved from its parent O atom towards the acceptor O atom, elongating the covalent O\u2014H bond to 1.18\u2005(3)\u2005\u00c5. The respective H atom can therefore be described as being shared by two alcohol O atoms, culminating in the formation of an eight-membered ring.The reaction between 3,3\u2032-[(3-meth\u00adoxy-4-hy\u00addroxy\u00adphen\u00adyl)methanedi\u00adyl]bis\u00ad(4-hy\u00addroxy-2 The distance of the freely refined hydrogen atom to its parent atom O3 is elong\u00adated to 1.18\u2005(3)\u2005\u00c5, while the H\u22efA hydrogen-bond length to O6 is rather short at only 1.24\u2005(3)\u2005\u00c5. This inter\u00adaction is therefore the second shortest such \u2013CAHB overall and the shortest intra\u00admolecular one. In the three related deprotonated dicoumarols, the D\u22efA distances range from 2.423\u2005\u00c5 . The distances between the alcohol oxygen atoms and bound carbon atoms are 1.3005\u2005(16)\u2005\u00c5 (O3\u2014C10) and 1.2939\u2005(17)\u2005\u00c5 (O6\u2014C19); i.e. both very similar and both significantly shorter than those reported for non-deprotonated derivatives, which range from 1.331 to 1.338\u2005\u00c5  with D\u22efA = 2.7727\u2005(19)\u2005\u00c5 and D-\u2013H\u22efA = 164.5\u2005(18)\u00b0.The ammonium hydrogen atom, which was refined freely, exhibits a hydrogen bond to the carbonyl oxygen atom of the deprotonated coumarol substituent , C11\u2014C1\u2014C20 = 114.44\u2005(12), C2\u2014C1\u2014C20 = 110.79\u2005(11)\u00b0] are slightly widened compared to the ideal tetra\u00adhedral value. As this is most pronounced for the angle involving the two coumarin substit\u00aduents, it is most likely based on steric strain. The bond lengths involving the two pyran oxygen atoms  are similar as observed previously, indicating conjugation between the six-membered rings in the two benzo\u00adpyran systems  in a stacking fashion are observed, O\u22efO1(\u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0D\u22efA = 2.4139\u2005(15)\u2005\u00c5] and as acceptor [O8\u22efH27B\u2014C27(\u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a0D\u22efA = 3.257\u2005(2)\u2005\u00c5] in a non-classical hydrogen bond from an amine methyl group  and the non-classical donation towards O8 [C27\u2014H27B\u22efO8(\u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a0D\u22efA = 3.257\u2005(2) (19)\u2005\u00c5]. Supported by the hydrogen bond with the carbonyl oxygen atom O1 as acceptor [O1\u22efH8O\u2014O8(\u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a0D\u22efA = 2.6488\u2005(16)\u2005\u00c5], these inter\u00adactions form infinite flat chains with \u2018up and down\u2019-pointing benzo\u00adpyrane moieties protruding along b  bridges the adjacent cation and anion by hydrogen bonding as a classical donor bis\u00ad(4-hy\u00addroxy-2H-chromen-2-one) was carried out by adding 1\u2005mL of tri\u00adethyl\u00adamine to its methano\u00adlic solution. The resulting transparent yellowish solution was left standing overnight to grow transparent crystals of tri\u00adethyl\u00adammonium 3-[(4-hy\u00addroxy-3-meth\u00adoxy\u00adphen\u00adyl)(4-hy\u00addroxy-2-oxo-2H-chromen-3-yl)meth\u00adyl]-2-oxo-2H-chromen-4-olate.3,3\u2032-[(3-Meth\u00adoxy-4-hy\u00addroxy\u00adphen\u00adyl)methanedi\u00adyl]bis\u00ad(4-hy\u00addroxy-2Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a02PLATON   I. DOI: 10.1107/S2056989018001561/lh5866Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018001561/lh5866Isup3.cmlSupporting information file. DOI: 1818945CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Individual ions and the solvating water mol\u00adecule assemble into dimeric units located around crystallographic inversion centers  8H13N)(C17H14P)]Cl\u00b7H2O, assemble into dimeric units located around crystallographic inversion centers via N\u2014H\u22efCl and O\u2014H\u22efCl hydrogen bonds. These discrete fragments are further inter\u00adconnected into chains by C\u2014H\u22efO inter\u00adactions. The disubstituted ferrocene core in the {[1\u2032-(di\u00adphenyl\u00adphosphino)ferrocen\u00adyl]meth\u00adyl}di\u00admethyl\u00adammonium cation has an approximate synclinal eclipsed conformation and is tilted by 3.40\u2005(11)\u00b0.Individual ions and the solvating water mol\u00adecule constituting the structure of the title compound, [Fe(C The phosphine substituent at the other cyclo\u00adpenta\u00addienyl ring is oriented so that one of its pivotal P\u2014C(Ph) bonds lies nearly in the plane of the bonding five-membered ring C6\u2013C10, while the other is roughly parallel with the axis of the ferrocene unit. The angle at which the P\u2014C18 bond inter\u00adsects the C6\u2013C10 plane is 13.17\u2005(10)\u00b0, whereas the angle subtended by the P\u2014C12 bond and the Cg1\u22efCg2 line is only 8.68\u2005(5)\u00b0.The protonated amino\u00admethyl chain is directed away from the ferrocene core, with the angle between the C1\u2014N bond and the axis of the ferrocene unit, 2PfcCH2NHMe2]+ cation in the structure of the title compound is involved in an N\u2014H\u22efCl hydrogen bond to a proximal chloride anion 2Cl2(H2O)2} around the crystallographic inversion centers. These discrete units are further inter\u00adlinked into chains along the a axis via the weaker C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions, as shown in Fig.\u00a02Each X, where X = Cl and ClO4 3SO3  was dissolved in acetic acid (10\u2005mL) and the solution was evaporated under reduced pressure. After this procedure was repeated twice using chloro\u00adform as a solvent, the residue was dissolved in a minimum amount of hot ethyl acetate. The solution was filtered and layered with hexane. Crystallization by liquid-phase diffusion over several days afforded orange crystals of the title compound. The yield was not determined.The \u2018amine\u2019 Ph25H27FeNP]Cl\u00b7H2O (481.76\u2005g\u2005mol\u22121): C 62.32, H 6.07, N 2.91%. Found: C 62.23, H 5.91, N 2.79%. ESI MS: m/z 383 ([Ph2PfcCH2]+), 428 ([Ph2PfcCH2NMe2 + H]+)Analysis calculated for [CUiso(H) set to 1.2Ueq of their bonding atom. Hydrogen atoms bonded to carbons were included in their theoretical positions and refined as riding atoms with Uiso(H) = 1.2Ueq(C).Relevant crystallographic data and structure refinement parameters are summarized in Table\u00a0210.1107/S2056989017013408/im2484sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017013408/im2484Isup3.hklStructure factors: contains datablock(s) I. DOI: 1575391CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound provides the first crystal structure of an \u03b1-alkenyl oxa\u00adthia\u00adzolone ring. 10H7NO2S, provides the first structure of an \u03b1-alkenyl oxa\u00adthia\u00adzolone ring. The phenyl ring and the oxa\u00adthia\u00adzolone groups make dihedral angles of 0.3\u2005(3) and \u22122.8\u2005(3)\u00b0, respectively, with the plane of the central alkene group; the dihedral angle between the rings is 2.68\u2005(8)\u00b0. A careful consideration of bond lengths provides insight into the electronic structure and reactivity of the title compound. In the crystal, extended \u03c0-stacking is observed parallel to the a-axis direction, consisting of cofacial head-to-tail dimeric units [centroid\u2013centroid distance of 3.6191\u2005(11)\u2005\u00c5]. These dimeric units are separated by a slightly longer centroid\u2013centroid distance of 3.8383\u2005(12)\u2005\u00c5, generating infinite stacks of mol\u00adecules.The title compound, C In addition, the C1\u2014S1 bond [1.7379\u2005(18)\u2005\u00c5] is slightly shorter than the statistical average for mol\u00adecules of this type (1.75\u00b10.02\u2005\u00c5). Thus the pattern of bonding within the heterocycle is consistent with the Krayuskin conjugation model, leading to the hypothesis that deca\u00adrbonylation of this derivative should occur with milder conditions than observed for heterocycles substituted with saturated substituents.The title compound Fig.\u00a01 is the fThe atoms in the ring of the oxa\u00adthia\u00adzolone heterocycle form bond angles that sum to 540.0\u00b0 consistent with a planar ring . The torsion angles O1\u2014C2\u2014C3\u2014C4 [\u22122.8\u2005(3)\u00b0] and C3\u2014C4\u2014C5\u2014C6 [\u2212179.81\u2005(17)\u00b0] confirm a near planarity of the mol\u00adecule favorable for conjugation between the \u03c0-systems of the two rings and the central alkene.et al., 2002et al., 1989et al., 1999et al., 2002The planarity, bond lengths and angles in the styryl fragment are comparable with previously reported values .There are eleven crystal structures of oxa\u00adthia\u00adzolone derivatives reported in the literature  \u03bbmax (log \u220a) : 228\u2005nm (4.21), 307\u2005nm (4.52).The title compound was prepared following literature methods  I. DOI: 10.1107/S2056989017011264/hb7694Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011264/hb7694Isup3.cmlSupporting information file. DOI: 1565845CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Please note that column heights and error bars in the original figures and data in the ESM tables are correct and statistical tests are valid. These corrections do not affect any results or conclusions in this article.Unfortunately, the original version of Figs.\u00a04, 5 and 6b in the article  containen numbers are as follows:The correct http://media.springernature.com/full/springer-static/image/art%3A10.1186%2Fs13550-016-0218-3/MediaObjects/13550_2016_218_Fig4_HTML.gif): \u2018HCT116\u2019 (IC) n\u2009=\u20098; \u2018A549\u2019 (WWU) n\u2009=\u20097; \u2018HCT116\u2019 (WMIC) n\u2009=\u20093; \u2018H1975\u2019 (AZ) n\u2009=\u20096.Figure\u00a04 : \u2018ONU (AZ)\u2019 n\u2009=\u20096; \u2018H1975 in ONU (AZ)\u2019 n\u2009=\u20096; \u2018A431 in ONU (AZ)\u2019 n\u2009=\u20096.Figure\u00a05 : \u2018PC9\u2019 n\u2009=\u200913.Figure\u00a06b ("}
{"text": "The title compounds are differing only by the position of the chlorine atom in the benzene ring. The mol\u00adecular structures are very similar, except for the relative position of the hy\u00addroxy\u00adphenyl rings. 23H21ClN2O2, differ from each other only by the position of the Cl atom on the corresponding benzene ring: meta relative to the central sp3 C atom for (I) and para for (II). In (I), the hy\u00addroxy\u00adphenyl rings are almost parallel, the dihedral angle between the mean planes being 9.2\u2005(2)\u00b0, but in (II), the relative position of the ring is different, characterized by a dihedral angle of 48.5\u2005(1)\u00b0. Compound (I) features intra\u00admolecular O\u2014H\u22efN and inter\u00admolecular C\u2014H\u22efO hydrogen bonds, while in (II), intra\u00admolecular O\u2014H\u22efN, C\u2014H\u22efN hydrogen bonds and weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are observed. Compound (I) was refined as an inversion twin.The title compounds, C Recent reports on a single-crystal study , C15(S). The chloro\u00adphenyl group is almost planar with atom Cl1 deviating by 0.013\u2005(1)\u2005\u00c5 from the ring in (I)The mol\u00adecular structure of the title compounds, (I)In compounds (I)C(9) chains propagating along [010]; see Fig.\u00a04C(11) chains propagating along the ab plane of the unit cell; see Fig.\u00a05In the crystal of (I)E)-({1-(3-chloro\u00adphen\u00adyl)-2-[(E)-(2-hy\u00addroxy\u00adbenzyl\u00adidene)amino]\u00adprop\u00adyl}imino)\u00admeth\u00adyl]phenol was achieved by the condensation of salicyl\u00adaldehyde (0.02\u2005mol) and 1-(3-chloro\u00adphen\u00adyl)propane-1,2-di\u00adamine (0.01\u2005mol) in ethanol . The completion of the reaction was monitored by TLC. The obtained yellow solid was purified by recrystallization from ethanol. Single crystals suitable for X-ray analysis were obtained by slow evaporation from ethanol. The above procedure was repeated with 1-(4-chloro\u00adphen\u00adyl)propane-1,2-di\u00adamine (0.01\u2005mol) instead of 1-(3-chloro\u00adphen\u00adyl)propane-1,2-di\u00adamine to synthesise 2-[(1E)-({1-(4-chloro\u00adphen\u00adyl)-2-[(E)-(2-hy\u00addroxy\u00adbenzyl\u00adidene)amino]\u00adprop\u00adyl}imino)\u00admeth\u00adyl]phenol.The synthesis of the salen ligand 2-[(1Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Pairs of O\u2014H bond distances were restrained to 0.82\u2005(1)\u2005\u00c5. Compound (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017016292/zq2239sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017016292/zq2239Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017016292/zq2239IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1412946, 1412945CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E conformation with respect to the C=N bond, and a dihedral angle of 14.54\u2005(11)\u00b0 between the benzene ring and the mean plane of the N\u2014N\u2014C(N)=S hydrazinecarbo\u00adthio\u00adamide unit.The mol\u00adecule of the title Schiff base, has an  8H8BrN3OS\u00b7C2H6OS, which crystallizes as a di\u00admethyl sulfoxide (DMSO) monosolvate, displays an E configuration with respect to the C=N bond, with a dihedral angle of 14.54\u2005(11)\u00b0 between the benzene ring and the mean plane of the N\u2014N\u2014C(N)=S unit. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds, forming chains propagating along the b-axis direction. Within the chains there are R23(11) ring motifs, which are reinforced by C\u2014H\u22efODMSO hydrogen bonds enclosing secondary R12(6) and R23(9) loops. The chains are linked by O\u2014Hhydrox\u00adyl\u22efS hydrogen bonds, forming layers parallel to (011). Inversion-related layers are linked by short Br\u22efBr inter\u00adactions [3.5585\u2005(5)\u2005\u00c5], forming slabs parallel to (011). The inter\u00admolecular inter\u00adactions have been investigated using Hirshfeld surface studies and two-dimensional fingerprint plots. The crystal structure of the unsolvated form of the title compound has been reported previously , and its solid-state structure is compared with that of the title solvated form.The mol\u00adecule of the title Schiff base, C Schiff bases are nitro\u00adgen-containing active organic compounds that play a vital role in enzymatic reactions involving inter\u00adaction of an enzyme with a carbonyl group of a substrate \u00b0 between the benzene ring and the mean plane of the N1/N2/C8/N3/S1 unit. The C8\u2014-S1 bond distance of 1.698\u2005(2)\u2005\u00c5 is close to that expected for a C=S bond -2-thio\u00adsemicarbazone and (E)-2-[(1H-indol-3-yl)methyl\u00adene]thio\u00adsemicarbazone -1-[4-(di\u00admethyl\u00adamino)\u00adbenzyl\u00adidene]thio\u00adsemicarbazide  ring motif. Comparing the two mol\u00adecules, as shown in the structural overlay of Fig.\u00a02ca. 180\u00b0 with respect to that in the unsolvated form of the mol\u00adecule. The bond lengths and bond angles of the two mol\u00adecules are similar. In the title compound, the dihedral angle between the benzene ring and the mean plane of the N\u2014N\u2014C(N)=S hydrazinecarbo\u00adthio\u00adamide unit is 14.54\u2005(11)\u00b0 compared to ca 7.05\u00b0 in the unsolvated phase. Kargar et al. ; see Fig.\u00a04x, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01) inter\u00adactions of 3.5585\u2005(5)\u2005\u00c5, forming slabs parallel to (011), as illustrated in Fig.\u00a05In the crystal, the Schiff base hydrazone is hydrogen bonded , S\u22efH/H\u22efS (18.8%), O\u22efH/H\u22efO (13.3%), Br\u22efH/H\u22efBr (11.6), C\u22efH/H\u22efC (8.8%), N\u22efH/H\u22efN (3.4%), C\u22efC (2.8%), Br\u22efN/N\u22efBr (2.0%), Br\u22efBr (1.5%), Br\u22efO/O\u22efBr (1.1%), Br\u22efC/C\u22efBr (1.1%), C\u22efN/N\u22efC (1.0%), S\u22efS (0.7%), S\u22efN/N\u22efS (0.6%) and S\u22efC/C\u22efS (0.2%), as shown in the two-dimensional fingerprint plots in Fig.\u00a07The three-dimensional et al., 2016viz. 5-bromo-2-hy\u00addroxy\u00adbenzaldehyde thio\u00adsemicarbazone -2-(2-hy\u00addroxy\u00adbenzyl\u00adidene)hydrazine\u00adcarbo\u00adthio\u00adamide hydrate] have been reported at 100\u2005K (UJIPIN) and 203\u2005K (UJIPOT and UJIPUZ) by Monfared et al. \u00b0 in the title compound.A search of the Cambridge Structural Database  of thio\u00adsemicarbazide  and a hot ethano\u00adlic solution of 5-bromo\u00adsalicyl\u00adaldehyde . The solution was then cooled and kept at room temperature. The precipitate that formed was filtered off and recrystallized from di\u00admethyl sulfoxide. Colourless block-like crystals, suitable for the X-ray analysis, were obtained in a few days on slow evaporation of the solvent.Uiso(H) = 1.5Ueq and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018000233/su5414sup1.cifCrystal structure: contains datablock(s) global, I, 1. DOI: 10.1107/S2056989018000233/su5414Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018000233/su5414Isup3.cmlSupporting information file. DOI: 1587285CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 37272; 10.1038/srep37272 published online: 11172016; updated: 03072017.In the methods section, under the subheading \u2018Human Fetal Brain Atlas Dataset\u201950\u201d.\u201cGenerally, this dataset includes T2 templates and tissue probability maps  for ages between 23\u201337 weeks of gestation. To create the 4D probabilistic atlas, 142 T2-weighted fast-spin echo images are acquired on 3\u2009T Philips Intera system with MR sequence parameters TR\u2009=\u20091712\u2009ms, TE\u2009=\u2009160\u2009ms, flip angle 90\u00b0 and voxel sizes 0.86\u2009\u00d7\u20090.86\u2009\u00d7\u20091\u2009mm. The atlas construction is described in detail elsewhereshould read:et al.50\u201d.\u201cT2 weighted MR images from 80 fetuses with normal brain appearances were used to create the 4D atlas. The age range at the time of scan was 21.7 to 38.7 weeks gestational age (GA), with mean and standard deviation of 29.6\u2009\u00b1\u20094.6 weeks. The images were acquired on 1.5 T Philips Achieva system with the following parameters: T2 weighted single shot Fast Spin Echo (ssFSE) TR\u2009=\u200915000\u2009ms, TE\u2009=\u2009160\u2009ms, flip angle\u2009=\u200990\u00b0 and voxel size\u2009=\u20091.25\u2009\u00d7\u20091.25\u2009\u00d7\u20092.5\u2009mm. For each subject multiple stacks of images  were acquired in approximately transverse, sagittal and coronal planes and the data reconstructed into a single 3D brain volume using the slice-to-volume reconstruction method. The reconstruction voxel size was 1.18\u2009\u00d7\u20091.18\u2009\u00d7\u20091.18\u2009mm. More details can be found in studies from Serag In addition, reference 50 was listed incorrectly. The correct reference appears below:et al. Construction of a consistent high-definition spatio-temporal atlas of the developing brain using adaptive kernel regression. NeuroImage59, 2255\u20132265 (2012).Serag, A."}
{"text": "This packing motif still enables significant \u03c0\u2013\u03c0 inter\u00adactions between two pyridyl groups, and may result from the close proximity of the tetra\u00adfluorido\u00adborate ions to the platinum(II) complexes, resulting in intra\u00admolecular H\u22efF distances between 2.156 and 2.573\u2005\u00c5.The crystal structure of a platinum(II) supra\u00admolecular building block, [Pt(dbbpy)(NCCH The solubility and apt geometry of the (dbbpy)platinum(II) complex make it a desirable building block for coordination-driven self-assembly of homo-metallic PtCl2 mol\u00adecule: one with Pt\u2014N distances of 2.013\u2005(2) and 2.011\u2005(2)\u2005\u00c5 and a 79.79\u2005(6)\u00b0 N\u2014Pt\u2014N angle Pt(OH2)2](OTf)2 Pt(NCCH3)(Ph)] [BAr\u20194], containing a Pt\u2014N distance of 2.000\u2005(4)\u2005\u00c5, located trans to the aceto\u00adnitrile, while the phenyl ligand causes an elongation to 2.092\u2005(4)\u2005\u00c5 for the other Pt\u2014N bond  and 1.995\u2005(4)\u2005\u00c5, respectively, with a bond angle of 80.5\u2005(2)\u00b0. These are shorter than those affected by the stronger Day, 2009, and theDay, 2009. The Pt\u20142 2](OTf)2 (Ph)][BAr\u20324] phenyl; McKeown et al., 2011et al., 2003tert-butly groups for the (dbbpy)Pt(NCCH3)2 cation and its corresponding dimer  are at an angle of 10.82\u00b0], both of which accommodate the bulky tert-butyl groups of the dbbpy ligands. The intra\u00admolecular Pt\u2014Pt distance is quite long at 4.5123\u2005(3)\u2005\u00c5, yet the pyridyl rings of the dbbpy are positioned for \u03c0\u2013\u03c0 inter\u00adactions with distances between 3.616\u2005(5)\u2005\u00c5 (N1\u22efN1i) and 4.032\u2005(7)\u2005\u00c5 (C4\u22efC4i)  occurring between the two rings 2](OTf)2 2](ClO4)2  compounds containing the bulky dbbpy ligand pack as head-to-tail dimers, such as the aforementioned (dbbpy)PtClDay, 2009, [Pt(SO3CF3)2 4](BF4)2 Cl3)2](BF4)2[Pt(dbbpy) of Pt(dbbpy)Cl2, and 164\u2005mg (0.8425\u2005mmol) of AgBF4 was refluxed under stirring until a yellow solution formed. The solution was isolated, via cannula, from the AgCl precipitate and condensed under reduced pressure until \u223c5\u2005mL of orange solution remained. This was combined with 25\u2005ml of Et2O and the resulting precipitate was washed with 3 \u00d7 20\u2005mL Et2O to give 206.9\u2005mg (83.8% yield) of product. UV\u2013vis \u03bbmax (\u220a Lmol\u22121cm\u22121): 211 (4.6 \u00d7 104), 249 (4.2 \u00d7 104), 306 (2.0 \u00d7 104), 319 (2.4 \u00d7 104) and 346 (6.0 \u00d7 103) nm.Yellow crystals of the title compound were grown from liquid diffusion of hexa\u00adnes into a dilute acetone solution.Uiso(H) = 1.2Ueq(CH) or Uiso(H) = 1.2Ueq(CH3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018005923/jj2198sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018005923/jj2198Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018005923/jj2198Isup3.molSupporting information file. DOI: 1837532CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A step-like conformation about the pyranyl ring is found for the mol\u00adecular structure of the title compound. The three-dimensional packing is sustained by \u03c0\u2013\u03c0, C\u2014Cl\u22ef\u03c0 and C\u2014H\u22efO inter\u00adactions. 19H13ClO3Se {systematic name: 2-[(4-chloro\u00adphen\u00adyl)selan\u00adyl]-2H,3H,4H,5H,6H-naphtho\u00adpyran-5,6-dione}, has the substituted 2-pyranyl ring in a half-chair conformation with the methyl\u00adene-C atom bound to the methine-C atom being the flap atom. The dihedral angle between the two aromatic regions of the mol\u00adecule is 9.96\u2005(9)\u00b0 and indicates a step-like conformation. An intra\u00admolecular Se\u22efO inter\u00adaction of 2.8122\u2005(13)\u2005\u00c5 is noted. In the crystal, \u03c0\u2013\u03c0 contacts between naphthyl rings [inter-centroid distance = 3.7213\u2005(12)\u2005\u00c5] and between naphthyl and chloro\u00adbenzene rings [inter-centroid distance = 3.7715\u2005(13)\u2005\u00c5], along with C\u2014Cl\u22ef\u03c0(chloro\u00adbenzene) contacts, lead to supra\u00admolecular layers parallel to the ab plane, which are connected into a three-dimensional architecture via methyl\u00adene-C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions. The contributions of these and other weak contacts to the Hirshfeld surface is described.The title organoselenium compound, C It exhibits biological activities in the context of cancer  can be isolated from the bark of the lapacho tree found in Central and South American countries Compounds of the bio-essential element selenium, found in amino acids such as seleno\u00adcysteine and seleno\u00admethio\u00adnine, are known to hold potential as pharmaceutical agents i.e. Cg(C2\u2013C4/C9\u2013C11)\u22efCg(C3\u2013C8)i = 3.7213\u2005(12)\u2005\u00c5 for an angle of inclination = 0.72\u2005(9)\u00b0 and symmetry operation (i) \u2212x, \u2212y, \u2212z. Two types of inter\u00adactions connect centrosymmetric aggregates into a supra\u00admolecular layer parallel to the ab plane . Thus, \u03c0\u2013\u03c0 inter\u00adactions between naphthyl and chloro\u00adbenzene rings are formed,  along with C\u2014Cl\u22ef\u03c0(chloro\u00adbenzene) contacts between centrosymmetrically related rings (Table\u00a01b).In the mol\u00adecular packing of (I)ne Fig.\u00a02a. Thus,s Table\u00a01. Connects Table\u00a01 to consos Table\u00a01b.et al., 2016dnorm in Fig.\u00a03dnorm-mapped Hirshfeld surface confirms the absence of conventional hydrogen bonds in the structure except for a weak C\u2014H\u22efO inter\u00adaction as given in Table\u00a01The Hirshfeld surfaces calculated on the structure of (I)a) and those delineated into H\u22efH, O\u22efH/H\u22efO, Cl\u22efH/H\u22efCl, C\u22efC, C\u22efH/H\u22efC, C\u22efCl/Cl\u22efC and Cl\u22efO/O\u22efCl contacts de + di \u223c2.3\u2005\u00c5 in Fig.\u00a06b is the result of a short inter\u00adatomic H\u22efH contact ; the points arising from the short inter\u00adatomic O\u22efH contacts are merged in the plot.The overall two-dimensional fingerprint plot Fig.\u00a06a and tht Table\u00a02. The intot Fig.\u00a06c; the pe, characterizes the two \u03c0\u2013\u03c0 stacking inter\u00adactions, one between inversion-related naphthyl rings, and the other between the chloro\u00adbenzene and (C2\u2013C4/C9\u2013C11) rings as the two overlapping triangular regions at around de = di \u223c1.8 and 1.9\u2005\u00c5, respectively, having green points in the overlapping portion. The presence of these two \u03c0\u2013\u03c0 stacking inter\u00adactions is also seen in the flat regions around the participating rings labelled with 1, 2 and 3 in the Hirshfeld surface mapped over curvedness in Fig.\u00a07The fingerprint plot delineated into C\u22efC contacts, Fig.\u00a06i.e. 3.0%, contribution from C\u22efCl/Cl\u22efC contacts  to the Hirshfeld surface is the result of its involvement in a C\u2014Cl\u22ef\u03c0 contact formed between symmetry-related chloro\u00adbenzene atoms . Its presence is also clear from the fingerprint plot delineated into Cl\u22efH/H\u22efCl , and Cl\u22efO/O\u22efCl contacts . The contribution from C\u22efH/H\u22efC contacts  and other contacts (Table\u00a03The chlorine atom on the benzene (C14\u2013C19) ring makes a useful contribution to the mol\u00adecular packing. The small, ts Fig.\u00a06g to thems Fig.\u00a05c. Its pCl Fig.\u00a06d, and Cts Fig.\u00a06h. The cts Fig.\u00a06f and ots Table\u00a03, includiet al., 2016i.e. (II)  as eluent to afford \u03b1-lapachone and \u03b2-lapachone (I)Referring to the reaction scheme, in a double-necked flask equipped with a magnetic bar and reflux condenser, under a nitro\u00adgen atmosphere, lawsone , paraformaldehyde , the vinyl selenide  and the ionic liquid 1-butyl-3-methyl\u00adimidazolium chloride, [Bmim]Cl  were added over 1,4-dioxane (2\u2005ml). The reaction mixture was heated at 383\u2005K and stirred over 2\u2005h. The reaction mixture was cooled and diluted with di\u00adchloro\u00admethane (100\u2005ml) and then washed with water (3 \u00d7 50\u2005ml). The organic phase was dried over NaUiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017007605/wm5392sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017007605/wm5392Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017007605/wm5392Isup3.cmlSupporting information file. DOI: 1551641CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The B\u2014H groups exhibit an intra\u00admolecular close contact with a C\u2014H group of the pyridine ring, which may be evidence of electrostatic attraction between the hydridic B\u2014H and the electropositive aromatic C\u2014H.The asymmetric unit contains two independent mol\u00adecules, which exhibit coplanar, mostly  14H19BN2O, contains two independent mol\u00adecules in the asymmetric unit. Both molecules exhibit coplanar, mostly sp2-hybridized meth\u00adoxy and di\u00admethyl\u00adamino substituents on their respective aromatic rings, consistent with \u03c0-donation into the aromatic systems. The B\u2014H groups exhibit an intra\u00admolecular close contact with a C\u2014H group of the pyridine ring, which may be evidence of electrostatic attraction between the hydridic B\u2014H and the electropositive aromatic C\u2014H. There appears to be weak C\u2014H\u22ef\u03c0(arene) inter\u00adactions between two of the H atoms of an amino\u00admethyl group and the meth\u00adoxy-substituted benzene ring of the other independent mol\u00adecule, and another C\u2014H\u22ef\u03c0 (arene) inter\u00adaction between one of the pyridine ring H atoms and the same benzene ring.The title compound [systematic name: 4-(di\u00admethyl\u00adamino)\u00adpyridine\u20134-meth\u00adoxy\u00adphenyl\u00adborane (1/1)], C RBH2) have been the focus of chemical research for over fifty years, most notably for their use in the indispensable hydro\u00adboration reaction, which permits reduction of olefins, carbonyl compounds and others  and C1\u2032\u2014B1\u2032\u2014N1\u2032 = 111.0\u2005(1)\u00b0] . The B1\u2014C1 and B1\u2032\u2014C1\u2032 distances  are consistent with a formal C\u2014B single bond. The oxygen atom of both meth\u00adoxy groups appears to be mostly 2sp hybridized, [C7\u2014O1\u2014C4 = 117.3\u2005(1) and C7\u2032\u2014O1\u2032\u2014C4\u2032 = 117.4\u2005(1)\u00b0] and is close to coplanar with the phenyl ring [torsion angles C7\u2014O1\u2014C4\u2014C3 = \u22127.4\u2005(2) and C7\u2032\u2014O1\u2032\u2014C4\u2032\u2014C3\u2032 = \u22127.1\u2005(2)\u00b0], consistent with \u03c0-donation into the phenyl ring.The asymmetric unit contains two independent mol\u00adecules Figs. 1 and 2 \u25b8 2sp hybridized [torsion angles C13\u2014N2\u2014C10 = 121.0\u2005(1)\u00b0 and C13\u2032\u2014N2\u2032\u2014C10\u2032 = 122.2\u2005(1)\u00b0] and is close to coplanar [torsion angles C13\u2014N2\u2014C10\u2014C11 = 2.4\u2005(2) and C13\u2032\u2014N2\u2032\u2014C10\u2032\u2014C11\u2032 = 3.4\u2005(1)\u00b0] consistent with \u03c0-donation into the pyridine ring.The geometries of the 4-(dimethylamino)pyridine (DMAP) fragment of both mol\u00adecules is similar to other structures of DMAP\u2013borane adducts. The nitro\u00adgen atom of the di\u00admethyl\u00adamino fragment appears to be Database survey). Inter\u00adestingly, the B\u2014H atoms exhibit intra\u00admolecular close contacts with the C\u2014H atoms of the pyridine ring [H12\u22efH2B = 2.26\u2005(3) and H12\u2032\u22efH2B\u2032 = 2.27\u2005(3)\u2005\u00c5] and are close to coplanar [torsion angles H2B\u2014B1\u2014N1\u2014C12 = 4(1) and H2B\u2014B1\u2014N1\u2014C12 = 16\u2005(1)\u00b0], which may be evidence of electrostatic inter\u00adactions between the hydridic B\u2014H atoms and electropositive aromatic C\u2014H atoms, and is observed in other DMAP\u2013borane adducts (see Database Survey). The planes of the pyridine rings and the benzene rings are almost normal to one another [the dihedral angle between the C1\u2013C6 and C8\u2013C12/N1 rings is 73.14\u2005(7)\u00b0 and that between the C1\u2032\u2013C6\u2032 and C8\u2032\u2013C12\u2032/N1\u2032 rings is 74.15\u2005(7)\u00b0]. Perhaps the most significant difference between the two mol\u00adecules is the 9.0\u00b0 difference in the torsion angle about the B\u2014N bond [C1\u2014B1\u2014N1\u2014C8 = \u221263.9\u2005(2) while C1\u2032\u2014B1\u2032\u2014N1\u2032\u2014C8\u2032 = \u221272.9\u2005(2)\u00b0]  and 1.595\u2005(2)\u2005\u00c5, respectively] are consistent with formal N\u2014B single bonds, and are within the range observed for other DMAP\u2013borane adducts  inter\u00adactions between two of the hydrogen atoms of the amino\u00admethyl group and the meth\u00adoxy\u00adphenyl group of a neighboring mol\u00adecule  inter\u00adactions described in the previous section  yielded four structures: UTOZEJ , followed by extraction with anhydrous di\u00adchloro\u00admethane (4\u2005mL). The extract was filtered through a 0.45\u2005\u00b5m PTFE syringe filter. The solvent was again removed in vacuo to afford a white solid . Crystals suitable for X-ray diffraction were grown by diffusion of pentane into a concentrated solution of the title compound in anhydrous di\u00adchloro\u00admethane.In a nitro\u00adgen-filled glove box, sodium 4-meth\u00adoxy\u00adphenyl\u00adborohydride  and 4-di\u00admethyl\u00adamino\u00adpyridine  were combined in a 20\u2005mL vial containing a stir bar and dissolved in anhydrous THF (4\u2005mL). The solution was cooled to 247\u2005K in the freezer and chloro\u00adtri\u00admethyl\u00adsilane  was added dropwise 1H NMR  \u03b4 (ppm): 8.12 , 7.23 , 6.80 , 6.52 , 3.78 , 3.11 . 13C NMR  \u03b4 (ppm): 157.3, 154.9, 146.7, 145.0 (br s), 134.5, 122.9, 106.5, 55.0, 39.5. 11B NMR  \u03b4 (ppm): \u22125.0 . FTIR : 3012, 2952, 2923, 2853, 2610, 2346, 2288, 2227, 1634, 1548, 1442, 1418, 1392, 1237, 1223, 1161, 1076, 1031, 811, 797, 548, 515.Uiso(H) = 1.5Ueq(C-methyl) and 1.2eq(C) for other H atoms. The B-bound H atoms were located in a difference-Fourier map and freely refined. Methyl H atoms were refined without restrictions on rotation around the C\u2014C bonds, HFIX 138 in SHELXL  I. DOI: 10.1107/S2056989017015171/lh5853Isup2.hklStructure factors: contains datablock(s) I. DOI: 1580559CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The configuration about each double bond in the N\u2014N=C\u2014C=C chain is E; the chain has an all trans conformation. In the crystal, N\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into a three-dimensional network.The title di\u00adthio\u00adcarbazate ester has approximate mirror symmetry with the putative plane bis\u00adecting the \u2013CH 18H18N2S2 [systematic name: (E)-4-methyl\u00adbenzyl 2-[(E)-3-phenyl\u00adallyl\u00adidene]hydrazinecarbodi\u00adthio\u00adate, comprises an almost planar central CN2S2 residue [r.m.s. deviation = 0.0131\u2005\u00c5]. The methyl\u00adene(tolyl-4) group forms a dihedral angle of 72.25\u2005(4)\u00b0 with the best plane through the remaining non-hydrogen atoms [r.m.s. deviation = 0.0586\u2005\u00c5] so the mol\u00adecule approximates mirror symmetry with the 4-tolyl group bis\u00adected by the plane. The configuration about both double bonds in the N\u2014N=C\u2014C=C chain is E; the chain has an all trans conformation. In the crystal, eight-membered centrosymmetric thio\u00adamide synthons, {\u22efHNCS}2, are formed via N\u2014H\u22efS(thione) hydrogen bonds. Connections between the dimers via C\u2014H\u22ef\u03c0 inter\u00adactions lead to a three-dimensional architecture. A Hirshfeld surface analysis shows that (I) possesses an inter\u00adaction profile similar to that of a closely related analogue with an S-bound benzyl substituent, (II). Computational chemistry indicates the dimeric species of (II) connected via N\u2014H\u22efS hydrogen bonds is about 0.94 kcal mol\u22121 more stable than that in (I).The title di\u00adthio\u00adcarbazate ester (I), C The dihedral angles between the central group and the S2- and N2-bound substituents are 71.65\u2005(4) and 7.08\u2005(8)\u00b0, respectively. The dihedral angle between the outer groups is 72.33\u2005(4)\u00b0 and is indicative of an approximately orthogonal relationship. Indeed, the r.m.s. deviation of all non-hydrogen atom in (I)2(tolyl-4) residue is 0.0586\u2005\u00c5, and the angle between this plane and that through the CH2(tolyl-4) residue is 72.25\u2005(4)\u00b0. The 1,4-carbon atoms of the 4-tolyl ring lie on the approximate mirror plane defined by the rest of the mol\u00adecule with the remaining pairs of ring atoms being related across the putative plane.The mol\u00adecular structure of (I)E in each case. This implies the N1\u2014N2=C2\u2014C3=C4 sequence has an all trans conformation as seen in the N1\u2014N2\u2014C2\u2014C3, N2\u2014C2\u2014C3\u2014C4 and C2\u2014C3\u2014C4\u2014C5 torsion angles of 177.41\u2005(13), \u2212178.70\u2005(15) and 178.23\u2005(15)\u00b0, respectively. The C1\u2014S2 [1.7455\u2005(16)\u2005\u00c5] and, especially, C11\u2014S2 [1.8233\u2005(16)\u2005\u00c5] bond lengths are considerably longer than the C1\u2014S1 bond [1.6752\u2005(16)\u2005\u00c5] consistent with considerable thione character in the latter. This is borne out also by the observation that the angles about the C1 atom involving S1 are wider, by over 7\u00b0, i.e. S1\u2014C1\u2014S2 = 125.20\u2005(10)\u00b0 and N1\u2014C1\u2014S1 121.06\u2005(12)\u00b0, cf. N1\u2014C1\u2014S2 of 113.74\u2005(11)\u00b0.The configuration about the C2=N2 imine [1.284\u2005(2)\u2005\u00c5] and C3=C4 ethene [1.339\u2005(2)\u2005\u00c5] bonds is Computational chemistry calculations.Further discussion on the mol\u00adecular geometry of (I)2 mediated by N\u2014H\u22efS(thione) hydrogen bonds, Fig.\u00a02a and Table\u00a01b, via methyl\u00adene-C\u2014H\u22ef\u03c0(tol\u00adyl), tolyl-C\u2014H\u22ef\u03c0(phen\u00adyl) and phenyl-C\u2014H\u22ef\u03c0(tol\u00adyl) inter\u00adactions, Table\u00a01bc plane and these are linked by the N\u2014H\u22efS hydrogen bonds.The most prominent feature of the mol\u00adecular packing is the formation of an eight-membered, centrosymmetric thio\u00adamide synthon, {\u22efHNCS}et al., 20082(tolyl-4) group, that might be regarded as the \u2018parent\u2019 compound, hereafter referred to as (II). While detailed discussion on the comparison of their mol\u00adecular geometries and computational modelling are given in Computational chemistry calculations, the present section focuses upon the study of inter\u00admolecular inter\u00adactions formed by (I)et al., 2016The most closely related compound in the crystallographic literature is one with a benzyl substituent at the S2 atom (Tarafder ca 25.4% for (I)ca 17.5 and 16.9%], N\u22efH/H\u22efN [ca 5.6 and 5.5%] as well as other minor inter\u00adactions including N\u22efC/C\u22efN, S\u22efC/C\u22efS and S\u22efN/N\u22efS, which constitute less than 5% of the overall contacts.Both (I)divs de at the inter\u00advals of 0.01\u2005\u00c5 reveals that (I)a,. Specifically, the decomposed fingerprint plot of H\u22efH for (I)de + di contact distance of 1.96\u2005\u00c5 which is approximately 0.43\u2005\u00c5 (17%) shorter cf. 2.36\u2005\u00c5 for (II), Fig.\u00a04b. Both (I)c, at approximately 2.7\u2005\u00c5, which is slightly shorter than the van der Waals radii of 2.9\u2005\u00c5. The decomposed fingerprint plots of S\u22efH/H\u22efS  and N\u22efH/H\u22efN contacts  for (I)cf. (II), in which the difference is merely 0.04\u2005\u00c5 (1.7%). Similarly, the S\u22efH/ H\u22efS contacts of both (I)cf. the sum of their van der Waals radii by 0.53 and 0.58\u2005\u00c5, respectively (21.5 and 24.0%). As a result, those contacts display intense red spots on their Hirshfeld surface, Fig.\u00a04d.A detailed comparison of the two-dimensional fingerprint plots of \u22efS Fig.\u00a04d and N\u22efts Fig.\u00a04e for , exhibits a greater mol\u00adecular volume and surface area, and is slightly less globular. This results in a lower surface-to-volume ratio and density for (I)In view of the close structural similarity between (I)et al., 2016As mentioned in the previous section, the \u2018parent\u2019 compound represents the most closely related analogue to (I)GaussView5  and pre-optimized using a semi empirical method (PM6) with a precise self-consistent field criterion. Subsequently, the geometries were further optimized at B3LYP/6-311+G without imposing symmetry constraints. A frequency analysis was performed on each optimized structure using the same level of theory and basis set to validate that each structure was indeed the local minimum structure with no imaginary frequency. All calculations were performed using the Gaussian09 software package ca 0.02 and 0.03\u2005\u00c5, respectively. In the chain, the C1\u2014N1 bond lengths have lengthened by ca 0.03\u2005\u00c5, a difference accompanied by a contraction in the N1\u2014N2 bond length by about the same amount. Minor differences are also noted in bond angles with widening of S1\u2014C1\u2014S2 and the angles subtended at the nitro\u00adgen atoms by 2\u20133\u00b0 with similar contractions in the C1\u2014S1\u2014C11 and S1\u2014C1\u2014N1 angles.The results, as shown from the superposition of the experimental structure and theoretical model of (I)d,p) basis set. It has been demonstrated that the long-range corrected hybrid method can greatly reduce self-inter\u00adaction errors  was obtained upon the correction of basis set superposition error (BSSE) by counterpoise correction. All calculations were performed in gas phase using Gaussian09 software EBSSEint) of \u221212.92 and \u221213.86 kcal mol\u22121, respectively. The range is approximately 3.89 to 5.23 kcal mol\u22121 less than the energy computed for a pair of thio\u00adurea dimers at the RIMP2/cc-pVDZ and cc-pVTZ levels of theory  is lower in energy  cf. (I)cf. (I)The dimeric species of (I)et al., 2010S-4-methyl\u00adbenzyl\u00addithio\u00adcarbazate  was dissolved in hot aceto\u00adnitrile (100\u2005ml) and added to an equimolar amount of cinnamaldehyde  in absolute ethanol (20\u2005ml). The mixture was heated for about 2\u2005h and was then allowed to stand overnight. The pale-brown crystals that formed were filtered and washed with absolute ethanol at room temperature. Yield: 70%. M.p. 463\u2013466\u2005K. Analysis: Calculated for C18H18N2S2: C, 66.22; H, 5.56; N, 8.58. Found: C, 65.87; H, 5.77; N, 9.00%. FT\u2013IR : 3102, \u03bd(N\u2014H); 1613, \u03bd(C=N); 1021, \u03bd(N\u2014N); 749, \u03bd(CSS).The following procedure was adapted from the literature (Ravoof Uiso(H) set to 1.2\u20131.5Ueq(C). The nitro\u00adgen-bound H atom was located in a difference-Fourier map but was refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017003991/hb7666sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017003991/hb7666Isup2.hklStructure factors: contains datablock(s) I. DOI: 1537500CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III defined by an N4O3 donor set. The packing features supra\u00admolecular layers sustained by C\u2014H\u22efO, C\u2014H\u22ef\u03c0(ar\u00adyl) and C\u2014Cl\u22ef\u03c0(ar\u00adyl) inter\u00adactions.The title compound features an amine-N-capped octa\u00adhedral coordination geometry for Yb III atom in the title complex, [Yb(C27H24Cl3N4O3)] }tris\u00ad(4-chloro\u00adphenolato)ytterbium(III)], is coordinated by a trinegative, hepta\u00addentate ligand and exists within an N4O3 donor set, which defines a capped octa\u00adhedral geometry whereby the amine N atom caps the triangular face defined by the three imine N atoms. The packing features supra\u00admolecular layers that stack along the a axis, sustained by a combination of aryl-C\u2014H\u22efO, imine-C\u2014H\u22efO, methyl\u00adene-C\u2014H\u22ef\u03c0(ar\u00adyl) and end-on C\u2014Cl\u22ef\u03c0(ar\u00adyl) inter\u00adactions. A Hirshfeld surface analysis points to the major contributions of C\u22efH/ H\u22efC and Cl\u22efH/H\u22efCl inter\u00adactions  to the overall surface but the Cl\u22efH contacts are at distances greater than the sum of their van der Waals radii.The Yb Being large and having seven potential donor atoms, these ligands are capable of coordinating lanthanides even if the atomic sizes of lanthanides are greater in comparison to their transition metal counterparts Despite being less studied than transition metal complexes, the crystal chemistry of lanthanides is rich and diverse as their complexes can display various coordination numbers and geometries that are not readily predicted \u00b0, indicating a parallel disposition. There is a range in the Yb\u2014O bond lengths, i.e. >0.02\u2005\u00c5, with the shortest Yb\u2014O1 bond being trans to the most loosely bound imine-N4 atom, and the longest Yb\u2014O2 bond being trans to most tightly held imine-N2 atom, Table\u00a01The mol\u00adecular structure of (I)b axis, Fig.\u00a02a. These are reinforced by methyl\u00adene-C\u2014H\u22ef\u03c0(ar\u00adyl) contacts, also shown in Fig.\u00a02a. Chains are connected into supra\u00admolecular layers in the bc plane by end-on C\u2014Cl\u22ef\u03c0(ar\u00adyl) inter\u00adactions, Fig.\u00a02b. Layers stack along the a axis with no directional inter\u00adactions between them, Fig.\u00a02c dnorm contact distances within the range of \u22120.18 to 1.65\u2005\u00c5 through calculation of the inter\u00adnal (di) and external (de) distances of a particular Hirshfeld surface point to its nearest nucleus a shows a butterfish-like two-dimensional fingerprint plot for (I)ca 26 and 5%, respectively, of the overall inter\u00adactions in the crystal, with de + di distances of \u223c2.54\u2005\u00c5 and \u223c2.43\u2005\u00c5, respectively, Fig.\u00a03b and 3c. As seen from the images of Fig.\u00a04d. Finally, the Cl\u22efH/H\u22efCl inter\u00adactions appear as the third most dominant inter\u00adaction, right after H\u22efH and C\u22efH/H\u22efC, with an overall contribution of ca 24% to the Hirshfeld surface, despite the fact that these inter\u00adactions are considered weak with contact distances greater than the sum of van der Waals radii. However, as seen from Fig.\u00a03e, these inter\u00adactions are responsible for the appearance of the tails of the \u2018butterfish-shape\u2019.The Hirshfeld surface analysis was performed on (I)III complex has been the subject of two independent determinations  structures are available for comparison where the ligand is identical to that in (I)i.e. P21/n, for Ln = Sm  bond lengths. The only anomalous parameter might be the length of the Gd\u2014N(amine) bond, i.e. 2.737\u2005(8)\u2005\u00c5, the relatively high standard uncertainty value notwithstanding.A wider range of lanthanide : 1628 (s) \u03bd(C=N), 1517 (m), 1449 (m), 1392 (m) \u03bd(\u2013O\u2014C=C\u2013), 1158 (m) \u03bd(C\u2014O\u2014C). Analysis calculated for C27H24Cl3N4O3Yb: C, 44.31; H, 3.31; N, 7.66%. Found: C, 44.63; H, 3.12; N, 7.92%.The Schiff base ligand, tris\u00ad{[amino]\u00adeth\u00adyl}amine (Kanesato Uiso(H) set to 1.2Ueq(C). Owing to poor agreement, one reflection, i.e. (7 0 4), was omitted from the final cycles of refinement. The maximum and minimum residual electron density peaks of 1.65 and 0.45\u2005e\u2005\u00c5\u22123, respectively, were located 0.84 and 1.51\u2005\u00c5 from the Yb and N2 atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989016013748/hb7612sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013748/hb7612Isup2.hklStructure factors: contains datablock(s) I. DOI: 1501230CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "O:O\u2032-bridged dinuclear unit which is extended through N-atom donors of the pyrimidine ligand into a two-dimensional layered structureThe coordination polymeric silver(I)\u2013diclofenac complex including pyrimidine is based on a centrosymmetric carboxyl\u00adate  14H11Cl2NO2) (diclH) and pyrimidine (pym), namely poly[{\u03bc2-2-[2-phen\u00adyl]acetato-\u03ba2O:O\u2032}(\u03bc2-pyrimidine-\u03ba2N1:N3)silver(I)], [Ag(C14H10Cl2NO2)(C4H4N2)]n or [Ag(\u03bc-dicl)(\u03bc-pym)]n, the very distorted tetra\u00adhedral AgN2O2 coordination centres comprise two N-atom donors from bridging pym ligands [Ag\u2014N = 2.381\u2005(3) and 2.412\u2005(3)\u2005\u00c5] and two carboxyl\u00adate O-atom donors from dicl ligands [Ag\u2014O = 2.279\u2005(2) and 2.280\u2005(2)\u2005\u00c5], which bridge Ag atoms, giving a centrosymmetric dinuclear units with a short Ag\u22efAg separation [2.8931\u2005(5)\u2005\u00c5]. Within the units are short intra\u00adligand C\u2014Cl\u22ef\u03c0(pym) inter\u00adactions [3.6409\u2005(15)\u2005\u00c5]. The units are linked through the bridging N atoms of the pym ligand into a two-dimensional sheet\u2013polymer structure lying parallel to (100) and stabilized by inter-ring \u03c0\u2013\u03c0 inter\u00adactions between the pym ligands [Cg\u22efCg = 3.4199\u2005(17)\u2005\u00c5]. Additional inter-unit C\u2014H\u22efO and C\u2014H\u22efCg hydrogen-bonding inter\u00adactions between the sheets give an overall three-dimensional structure.In the title mixed-ligand silver(I) coordination polymeric complex with the non-steroidal anti-inflammatory drug diclofenac (C These studies have shown that short Ag\u22efAg separations are one of the most important factors for the manifestation of such properties  from separate dicl ligands and two nitro\u00adgen atoms /141\u00b0}, where \u03b1 and \u03b2 are the largest angles around the metal atom) is 0.732 and indicates substantial deviation from ideal tetra\u00adhedral geometry 2(\u03bc-pym)2]n n 2] units \u2005\u00c5] is significantly shorter than the sum of the van der Waals radii for two silver atoms (3.44\u2005\u00c5), indicating weak inter\u00adactions between adjacent AgI ions, forming an [Ag2(COO)2] units. If coexisting strong argentophilic Ag1\u22efAg1i inter\u00adactions are considered as coordinative, it could be reasoned that the coordination around Ag1 is slightly distorted trigonal\u2013bipyramidal [the structural distortion index tau (\u03c4) was calculated to be 0.06] ds Fig.\u00a01. The dists Fig.\u00a02. Within 2-1N,N-bridging ligand between neighboring [Ag2(COO)2] units, leading to the formation of a two-dimensional coordination polymer, extending along (100) 2] units, which comprise eight-membered rings, can be defined as the nodes of the structure. Connection of the four different pym ligands to these nodes provides continuity of the structure  Fig.\u00a04. In othere Fig.\u00a04.carbox\u00adyl hydrogen-bonding inter\u00adaction [2.971\u2005(3)\u2005\u00c5] \u00b0, the conformation of the ligand being stabilized by an intra\u00admolecular N1\u2014H1\u22efO2] Table\u00a02.iii hydrogen-bonding inter\u00adaction stabilizes the crystal packing (Table\u00a02Cg6iv inter\u00adaction to a pym ring [3.983\u2005\u00c5] and a strong \u03c0\u2013\u03c0 stacking inter\u00adaction between aromatic rings of the pym ligands , shown in Fig.\u00a03In the crystal, a C16\u2014H16\u22efO1g Table\u00a02. In addi3) of AgNO3  with stirring. A white suspension with a white precipitate formed and the addition of aceto\u00adnitrile (10\u2005cm3) to this resulted in a clear solution which was left to stand for slow evaporation in darkness at room temperature. Single crystals of (I)All reactions were performed with commercially available reagents and used without further purification. Solid sodium 2-phenyl\u00adacetate (Nadicl)  and pyrimidine  were added to an aqueous solution  in the frequency range 4000\u2013600\u2005cmas) and symmetric (\u03c5s) vibrations of the carboxyl\u00adate group. The difference between the asymmetric and symmetric carboxyl\u00adate stretching [\u0394\u03bd = \u03c5as(COO\u2212) - \u03c5s(COO\u2212)] is often used to correlate the infrared spectra of metal carboxyl\u00adate structures. When \u0394\u03bd < 200\u2005cm\u22121, the carboxyl\u00adate groups of the complexes can be considered bidentate  = 1.2Ueq(C). The N-bound H atom was located in a difference-Fourier map but was also allowed to ride in the refinement with Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989016014730/zs2370sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016014730/zs2370Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016014730/zs2370sup3.tifSupporting information file. DOI: 1500646CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports7: Article number: 45206; 10.1038/srep45206 published online: 05302017; updated: 12222017.This Article contains errors. In the legend of Figure 1,a) Spectral flux per bunch through an on-axis 1\u2009mm2 area delivered by Beamline ID19 in the four bunch mode (40\u2009mA storage ring current), including 2.8\u2009mm diamond and 1.4\u2009mm aluminium filtering. The total flux was 1.2\u2009\u00d7\u2009109 photons s\u22121 mm\u22122 on-axis.\u201d\u201c(should read:a) Spectral flux per bunch through an on-axis 1\u2009mm2 area delivered by Beamline ID19 in the four bunch mode (40\u2009mA storage ring current), including 2.8\u2009mm diamond and 1.4\u2009mm aluminium filtering. The total flux was 4\u2009\u00d7\u2009107 photons/bunch/mm2 on-axis.\u201d\u201c delivered per bunch (150\u2009ps duration23) on Beamline ID19 in the four bunch mode.\u201d\u201cFigure 1(a) shows the calculated on-axis spectral X-ray flux (1.2\u2009\u00d7\u200910should read:7 photons/bunch/mm2 on-axis) delivered per bunch (150\u2009ps duration23) on Beamline ID19 in the four bunch mode.\u201d\u201cFigure 1(a) shows the calculated on-axis spectral X-ray flux (4\u2009\u00d7\u200910In the Discussion section,\u201cThe time at which the leading lateral release waves reached the shock front on-axis in the PC-PC and Cu-PC loadings were estimated to be 3.30\u2009\u03bcs and 2.53\u2009\u03bcs, respectively.\u201dshould read:\u201cThe times at which the leading lateral release waves reached the shock front on-axis in the PC-PC and Cu-PC loadings were estimated to be 2.3 \u03bcs and 1.9 \u03bcs, respectively.\u201d"}
{"text": "Scientific Reports7: Article number: 42192; 10.1038/srep42192 published online: 02082017; updated: 01292018.This Article contains an error in Figure 2. For CYP3A5 *3\u2009=\u2009AG without hypertension,\u201cN\u2009=\u200931 Dose\u2009=\u20093.73\u201dshould read:\u201cN\u2009=\u200931 Dose\u2009=\u20094.13\u201dThe correct Figure 2 appears below as"}
{"text": "The packing features C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions.With both chelating and \u03bc 2(C8H8NS2)4], is a centrosymmetric dimer with both chelating and \u03bc2-tridentate di\u00adthio\u00adcarbamate ligands. The resulting S5 donor set defines a CdII coordination geometry inter\u00admediate between square-pyramidal and trigonal\u2013bipyramidal, but tending towards the former. The packing features C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions, which generate a three-dimensional network. The influence of these inter\u00adactions, along with intra-dimer \u03c0\u2013\u03c0 inter\u00adactions between chelate rings, has been investigated by an analysis of the Hirshfeld surface.The title compound, [Cd The S3 di\u00adthio\u00adcarbamate ligand is strictly chelating, with \u0394(Cd\u2014S) = 0.08\u2005\u00c5. Reflecting the symmetric modes of coordination of the di\u00adthio\u00adcarbamate ligands, the C\u2014S bond lengths are equal within 5\u03c3 (Table\u00a01The centrosymmetric binuclear mol\u00adecule of (I)\u03c3 Table\u00a01.5 donor set defines a highly distorted penta\u00adcoordinate geometry, with the major distortions due to the disparate Cd\u2014S bond lengths and the acute angles subtended at the CdII atom by the chelating ligands \u00b0. A measure of the distortion of a coordination geometry from the ideal square-pyramidal and trigonal\u2013bipyramidal geometries is given by the value of \u03c4 or Fig.\u00a02.et al., 2016dnorm in the range \u22120.055 to 1.371 au  and 5(b), respectively, and again highlight the influence of C\u2014H\u22efS inter\u00adactions, short C10\u22efC15 contacts and C\u2014H\u22ef\u03c0 inter\u00adactions involving phenyl rings (atoms C3\u2013C8) as the acceptor. Thus, the C\u2014H\u22efS inter\u00adactions involving the phenyl-ring C4, C5 and H5 atoms with S1 are shown with black dashed lines in Fig.\u00a05a); the red dashed lines indicate short inter\u00adatomic C\u22efC contacts .The Hirshfeld surface analysis for (I)au Fig.\u00a03, the briau Fig.\u00a03. The donau Fig.\u00a03 give risau Fig.\u00a03. The imms Table\u00a03. The C\u2014Het al., 2007a)\u2013(e); their relative contributions to the Hirshfeld surface are summarized qu\u00adanti\u00adtatively in Table\u00a04b) that H\u22efH contacts do not exert much influence on the mol\u00adecular packing, as their inter\u00adatomic distances are greater than the sum of their van der Waals radii, i.e. de + di > 2.8\u2005\u00c5. A pair of peaks appearing in the fingerprint plot delineated into S\u22efH/H\u22efS contacts at de + di \u223c 2.8\u2005\u00c5  arise from the C5\u2014H5\u22efS1 inter\u00adaction; the weaker C4\u22efH4\u22efS1 inter\u00adaction and short inter\u00adatomic H\u22efS/S\u22efH contacts involving the S3 atom  indicate the significance of these contacts through the presence of C\u2014H\u22ef\u03c0 inter\u00adactions and short inter\u00adatomic C\u22efH/H\u22efC contacts in the crystal. A pair of green lines within the forceps also indicates the influence of these contacts. Finally, an arrow-shaped distribution of green points in the centre in the plot corresponding to S\u22efS contacts , together with the contribution from Cd\u22efS/S\u22efCd contacts to the Hirshfeld surface (Table\u00a04Cg\u22efCg = 3.6117\u2005(11)\u2005\u00c5; symmetry code: \u2212x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. The small contributions from Cd\u22efH/H\u22efCd and N\u22efH/H\u22efN contacts \u22121. 1H and 13C NMR spectra were recorded at room temperature in DMSO-d6 solution on a Jeol ECA 400\u2005MHz FT\u2013NMR spectrometer.All chemicals and solvents were used as purchased without purification, and all reactions were carried out under ambient conditions. The melting point was determined using an Electrothermal digital melting-point apparatus and was uncorrected. The IR spectrum was obtained on a PerkinElmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer from 4000 to 400\u2005cm\u22121): 1491 (m) [\u03bd(C\u2014N)], 1160 (m), 964 (s) [\u03bd(C\u2014S)] cm\u22121. 1H NMR: \u03b4 7.26\u20137.42 , 2.05 . 13C NMR: \u03b4 46.6 (Me) 125.6, 128.4, 129.6, 147.9 (aromatic C), 207.8 (CS2).Sodium methyl\u00adphenyl\u00addithio\u00adcarbamate  in methanol (25\u2005ml) was added to cadmium chloride  in methanol (10\u2005ml). The resulting mixture was stirred and refluxed for 2\u2005h. The filtrate was evaporated until an off-white precipitate was obtained, which was recrystallized in methanol. Slow evaporation of the filtrate yielded colourless crystals of the title compound . IR (cmUiso(H) values set at 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017002705/hb7659sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017002705/hb7659Isup2.hklStructure factors: contains datablock(s) I. DOI: 1533246CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Prunus domestica ssp. domestica), six colorless non\u2010fluorescent chlorophyll catabolites (NCCs) were characterized, named Pd\u2010NCCs. In addition, several minor NCC fractions were tentatively classified. The structure of the most polar one of the NCCs, named Pd\u2010NCC\u201032, featured an unprecedented twofold glycosidation pattern. Three of the NCCs are also functionalized at their 32\u2010position by a glucopyranosyl group. In addition, two of these glycosidated NCCs carry a dihydroxyethyl group at their 18\u2010position. In the polar Pd\u2010NCC\u201032, the latter group is further glycosidated at the terminal 182\u2010position. Four other major Pd\u2010NCCs and one minor Pd\u2010NCC were identified with five NCCs from higher plants known to belong to the \u2018epi\u2019\u2010series. In addition, tentative structures were derived for two minor fractions, classified as yellow chlorophyll catabolites, which represented  oxidation products of two of the observed Pd\u2010NCCs. The chlorophyll catabolites in leaves of plum feature the same basic structural pattern as those found in leaves of apple and pear trees.In cold extracts of senescent leaves of the plum tree ( Hv\u2010NCC\u20101 from senescent leaves of barley (Hordeum vulgare).Hv\u2010NCC\u20101 as a 1\u2010formyl\u201019\u2010oxobilin\u2010type linear tetrapyrrolepFCCs), with species\u2010dependent configuration of their formation.pFCCs are rapidly hydroxylated to 32\u2010OH\u2010pFCC (probably still in the chloroplast).Fig.\u00a0About 25\u00a0years ago, chlorophyll (Chl) breakdown and the appearance of the fall colors were still a stunning mystery.Table\u00a0In the meantime, NCCs have been found in extracts of senescent leaves of a range of plants,Fig.\u00a0However, as was recognized recently, Chl\u2010breakdown \u2018branches out\u2019, and furnishes \u20181,19\u2010dioxobilin\u2010type\u2019 Chl\u2010catabolites (DCCs)Prunus domestica ssp. domestica). As shown below, Chl\u2010breakdown in senescent leaves of this fruit tree follows the \u2018PaO/phyllobilin\u2019 pathway of Chl\u2010breakdown.epi\u2010type\u2019. In addition, in the extracts several YCCs were also found.In the context of investigations of Chl\u2010catabolites in domestic agricultural plants, we have studied the nature of such phyllobilins in stone fruit and report here our work on the Chl\u2010catabolites in leaves of the plum tree (Prunus domestica) and frozen for storage. Five major and nine minor colorless NCCs were provisionally identified in extracts of senescent leaves of plum trees on the basis of their characteristic UV\u2010absorbance properties, using analytical HPLC , as first reported in the spectrum of Hv\u2010NCC\u20101.Yellow senescent and green leaves were collected from plum trees , analyzed by UV/VIS\u2010spectroscopy first  and of Hv\u2010NCC\u20101R)\u2010configuration at the stereogenic C(10).For spectroscopic analysis of the most abundant NCCs in the leaves of Pd\u2010NCC\u201032 (1) displayed a strong signal at m/z 1025.3839, corresponding to C47H62N4NaO20+  and establishing the molecular formula as C47H62N4O20. Likewise, a positive\u2010ion\u2010mode ESI\u2010MS spectrumFig.\u00a0pseudo\u2010molecular ion [M\u00a0+\u00a0H]+ at m/z 1003.1, also consistent with the molecular formula of C47H62N4O20. Characteristic fragment ions at m/z 841.2, 684.1 and 679.2 were also detected, which indicated the loss of a sugar moiety (C6H10O5) from [M\u00a0+\u00a0H]+,D  in CD3OD at 10\u00a0\u00b0C ) at low field, four Me group singlets at high field and a singlet for the methyl ester group at 3.75\u00a0ppm. The typical signals for a peripheral vinyl group were not observed. From 1H,13C\u2010heteronuclear (HSQC and HMBC) and 1H,1H\u2010homonuclear NMR\u2010correlations (COSY and ROESY) of Pd\u2010NCC\u201032 (1) in CD3OD, assignment of the signals of 47 H\u2010atoms and 45 13C\u2010nuclei could be achieved  (4.17\u00a0ppm) and H\u2013C(1\u2033) (4.33\u00a0ppm), as well as H\u2013C(2\u2032) (3.17\u00a0ppm) and H\u2013C(2\u2033) (3.21\u00a0ppm), the chemical shifts of the pairs of signals differed significantly . Chemical shifts and doublet nature (J\u00a0=\u00a07.8\u00a0Hz) of H\u2013C(1\u2032) and H\u2013C(1\u2033) indicated \u03b2\u2010anomeric attachment of both sugar moieties, as observed earlier for the 32\u2010glucopyranoside moieties of NCCs.1H\u2010 and 13C\u2010chemical shifts of Pd\u2010NCC\u201032 (1) with those of the known NCCs with a peripheral glucopyranosyl group at C(32).1H,13C\u2010HMBCs from H\u2013C(1\u2032) with C(32) and from H\u2013C(1\u2033) with C(182) established the attachment of one sugar moiety at each one of the terminal C\u2010atoms of the Et side chain at C(3) (ring A) and of the 1,2\u2010dihydroxyethyl group at C(18) (ring D). The 1H\u2010 and 13C\u2010chemical shifts at the positions C(182) and C(32) were also consistent with an attached peripheral sugar substituent. However, as with other 1,2\u2010dihydroxyethyl substituted NCCs,1 the configuration at C(182) remains unknown.In a 600\u00a0MHz Pd\u2010NCC fractions , Pd\u2010NCC\u201040 (3), Pd\u2010NCC\u201056 (4), Pd\u2010NCC\u201060 (5), and Pd\u2010NCC\u201071 (6) were also isolated and purified by HPLC. A positive\u2010ion\u2010mode ESI\u2010MS spectrum of Pd\u2010NCC\u201060 (5) showed a pseudo\u2010molecular ion [M\u00a0+\u00a0H]+ at m/z 645.2, consistent with the molecular formula of C35H40N4O8. Characteristic fragment ion peaks were visible at m/z 613.2 and 522.1, corresponding to the loss of MeOH and the loss of ring D from [M\u00a0+\u00a0H]+. The same molecular formula and fragmentation is known for the major NCC from Cercidiphyllum japonicum (Cj\u2010NCC\u20101),epi\u2019\u2010configuration at C(16).Pd\u2010NCC\u201060 (5) and Cj\u2010NCC\u20101 were separately analyzed by analytical HPLC, as well as a 1:1 mixture of both in a co\u2010injection   of Pd\u2010NCC\u201060 (5). Consistent with their origin from a common \u2018primary\u2019 FCC,epi\u2010pFCC, the other colorless Pd\u2010NCCs were also deduced to belong to the epi\u2010series.Five other tion see , Fig.\u00a010Pd\u2010NCC\u201056 (4) was determined as C41H50N4O13 by ESI mass spectrometry, which furnished a base peak [M\u00a0+\u00a0H]+ at m/z 807.2. Fragment\u2010ions at m/z 775.3, 684.2 and 645.2 corresponded to the loss, alternatively, of MeOH, of ring D and of a hexose moiety from [M\u00a0+\u00a0H]+. These data indicate the presence of one hexopyranose moiety at the HO\u2013C(32) group of ring A of Pd\u2010NCC\u201056 (4) and a vinyl group at C(18) of ring D. This indicates a common chemical constitution of 4 and of Nr\u2010NCC\u20102Fig.\u00a0The molecular formula of Pd\u2010NCC\u201040 (3) could be deduced tentatively as C35H42N4O10 by ESI mass spectrometry, which showed the experimental base peak [M\u00a0+\u00a0H]+ at m/z 679.2. In the mass spectra, characteristic fragment\u2010ion peaks at m/z 647.2 and 522.1 were also detected, which corresponded to the loss of MeOH and to the loss of ring D (from [M\u00a0+\u00a0H]+). Accordingly, the catabolite Pd\u2010NCC\u201040 (3)  indicated a pseudo\u2010molecular ion at m/z 841.2, consistent with the molecular formula of C41H52N4O15. The fragments at m/z 809.3, 684.2, 679.2 and 522.1 indicated the loss of MeOH, the loss of ring D, the loss of a sugar moiety and the loss of ring D and a sugar moiety. Thus, the catabolite 2 carries a sugar substituent at the C(3) hydroxyethyl side chain (ring A) and a 1,2\u2010dihydroxyethyl group at C(18) (ring D). According to their fragmentation pattern,Pd\u2010NCC\u201035 (2)  was determined as C35H40N4O7 with a pseudo\u2010molecular ion at m/z 629.2. Fragments at m/z 597.2 and 506 indicate the loss of MeOH and ring D. Pseudo\u2010molecular ion and fragment\u2010ions are consistent with a chemical constitution of 6, as previously found for Cj\u2010NCC\u20102  and of Cj\u2010NCC\u20102 was supported by a common retention time of 6 and Cj\u2010NCC\u20102 in a HPLC co\u2010injection experiment.The molecular formula of Pd\u2010NCC\u201054) by LC/ESI\u2010MS revealed a pseudo\u2010molecular ion at m/z 661.2 ([M\u00a0+\u00a0H]+), consistent with the molecular formula of C35H40N4O9. We suspected Pd\u2010NCC\u201054 as product of the formal addition of an O\u2010atom to Pd\u2010NCC\u201060 (5) from an endogenous oxidation process. Indeed, as shown recently,2O may eliminate easily, resulting in corresponding YCCs.Pd\u2010YCC\u201067, which showed mass spectral data (pseudo\u2010molecular ion with m/z 643.2) consistent with its formation as the formal product of an oxidative dehydrogenation of Pd\u2010NCC\u201060 (5). A further minor fraction, classified as YCC from a prominent absorption maximum near 420\u00a0nm, was also subjected further to ESI\u2010MS analysis. The latter data suggested Pd\u2010YCC\u201061 (m/z 805.1) to represent a YCC derived from oxidation of the glucosylated Pd\u2010NCC\u201056 (4). When extracts were prepared after storage of senescent leaves of the plum tree at room temperature for 7\u00a0min, an increase of the content of both YCCs (Pd\u2010YCC\u201061 and Pd\u2010YCC\u201067) was observed, as well as the formation of 15\u2010OH\u2010Pd\u2010NCC\u201060, identified by comparison with its analogue from the established oxidation of Cj\u2010NCC\u20101.Pd\u2010NCC\u201054. Clearly, work\u2010up and preparation of extracts of cold senescent leaves need to be done swiftly, in order to avoid oxidation artefacts.Analysis of a minor NCC (tentatively named Prunus domestica ssp. domestica) were shown to contain a range of NCCs, two YCCs, and, in traces, a PiCC, all members of the \u2018type I\u2019 phyllobilin family. In spite of the absence of DCCs,Pd\u2010NCC\u201032 (1) showed a previously unknown structure and is functionalized with two glycopyranose moieties on the \u2018distant\u2019 pyrrole rings A and D. The structure of Pd\u2010NCC\u201032 (1) also provided the first (indirect) evidence for enzymatic glycosidation of an FCC at the 182\u2010position .Pd\u2010NCC\u201060 (5) and Pd\u2010NCC\u201071 (6) with corresponding Cj\u2010NCCs, indicated the plum NCCs to belong to the C(16)\u2010epi series, as well.Fig.\u00a0Extracts of naturally senescent leaves of the plum tree , LC/MS gradient grade MeOH from or VWR , and AcONH4, puriss. p.a., from Fluka . KH2PO4, puriss. p.a., K3PO4 dibasic\u2010anh., puriss. p.a., and hexane were from Sigma\u2013Aldrich . Sand was from J. T. Baker , Sep\u2010Pak\u00aeC18 cartridges (1 and 5\u00a0g) were from Waters Associates. pH Values were measured with a WTW SenTix 21 electrode connected to a WTW pH525 digital pH meter.HPLC grade MeOH was purchased from HPLC. Dionex Summit HPLC system with manual sampler, P680 pump, online degasser and diode array detector, 1.35\u00a0ml or 200\u00a0\u03bcl injection loop. Data were collected and processed with Chromeleon V6.70.i) Anal. HPLC. Kinetex 00G\u20104601\u2010E0\u20105u\u2010C18\u2010100A 250\u00a0\u00d7\u00a04.6\u00a0mm i.d. column at 20\u00a0\u00b0C protected with a Phenomenex AJ0\u20104287 C18 4\u00a0\u00d7\u00a03.0\u00a0mm i.d. pre\u2010column was used with a flow rate of 0.5\u00a0ml\u00a0min\u22121. Solvent A: 50mm aq. potassium phosphate buffer (pH 7.0), solvent B: MeOH, solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a090\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a060, 80:20:0 to 40:60:0; 60\u00a0\u2013\u00a080, 40:60:0 to 0:100:0; 80\u00a0\u2013\u00a085, 0:100:0; 85\u00a0\u2013\u00a087, 0:100:0 to 0:20:80; 87\u00a0\u2013\u00a090, 0:20:80 to 80:20:0.ii) Semi\u2010prep. HPLC (90\u00a0min run). 00G\u20104252\u2010NO Luna 5u C18(2) 100A 250\u00a0\u00d7\u00a010\u00a0mm i.d. column at 20\u00a0\u00b0C protected with a Phenomenex AJ0\u20107220 250\u00a0\u00d7\u00a010\u00a0mm i.d. pre\u2010column was used with a flow rate as a function of time: 0\u00a0\u2013\u00a05\u00a0min: 1\u00a0\u2013\u00a04\u00a0ml\u00a0min\u22121; 5\u00a0\u2013\u00a090\u00a0min: 4\u00a0ml\u00a0min\u22121. Solvent A: 4mm aq. AcONH4, solvent B: MeOH with AcONH4 (c\u00a0=\u00a04mm), solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a090\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a060, 80:20:0 to 40:60:0; 60\u00a0\u2013\u00a080, 40:60:0 to 0:100:0; 80\u00a0\u2013\u00a085, 0:100:0; 85\u00a0\u2013\u00a087, 0:100:0 to 0:20:80; 87\u00a0\u2013\u00a090, 0:20:80 to 80:20:0.iii) Semi\u2010prep. HPLC (70\u00a0min run). 00G\u20104252\u2010NO Luna 5u C18(2) 100A 250\u00a0\u00d7\u00a010\u00a0mm i.d. column at 20\u00a0\u00b0C protected with a Phenomenex AJ0\u20107220/1 C18 250\u00a0\u00d7\u00a010\u00a0mm i.d. pre\u2010column was used with a flow rate as a function of time: 0\u00a0\u2013\u00a05\u00a0min: 1\u00a0\u2013\u00a04\u00a0ml\u00a0min\u22121; 5\u00a0\u2013\u00a070\u00a0min: 4\u00a0ml\u00a0min\u22121. Solvent A: 50mm aq. potassium phosphate buffer (pH 7.0), solvent B: MeOH, solvent C: H2O; solvent composition (A/B/C) as function of time (0\u00a0\u2013\u00a070\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a050, 80:20:0 to 47.3:52.7:0; 50\u00a0\u2013\u00a055, 47.3:52.7:0 to 0:52.7:47.3; 55\u00a0\u2013\u00a060, 0:52.7:47.3 to 0:100:0; 60\u00a0\u2013\u00a065, 0:100:0; 65\u00a0\u2013\u00a067, 0:100:0 to 0:20:80; 67\u00a0\u2013\u00a070, 0:20:80 to 80:20:0.LC/MS. i) Pre\u2010Purifcation of Minor Fractions Pd\u2010NCC\u201054 and Pd\u2010NCC\u201071 on an anal. HPLC. Minor catabolite fractions were first purified by HPLC  according to following procedure: 3\u00a0\u2013\u00a04\u00a0g of leaf material were ground in mortar and pestle under liquid N2 with addition of ca. 1\u00a0g of sand, a tip of a spatula of CaCO3 and 4\u00a0\u2013\u00a05\u00a0ml of MeOH. The mixture was centrifuged  and the supernatants were stored at \u221280\u00a0\u00b0C until use. An aliquot of the supernatant was centrifuged (1\u00a0min at 7200\u00a0g), diluted (1:1 v/v) with aq. potassium phosphate buffer  and centrifuged again . In total 300\u00a0\u03bcl (3\u00a0\u00d7\u00a0100\u00a0\u03bcl) of the supernatant were purified on the anal. HPLC  at a flow rate of 0.5\u00a0ml\u00a0min\u22121 using 50mm aq. K3PO4 as solvent A and MeOH as solvent B , and desired fractions were collected and combined.ii) LC/MS Analysis of minor fractions of the collected HPLC fractions were analyzed on an LC/MS system  using AcONH4 buffer  and MeOH  as eluents . Twenty microliter of the collected catabolite fraction were injected and analyzed at a flow rate of 0.5\u00a0ml\u00a0min\u22121 .Spectroscopy. UV/VIS Spectra: Agilent Technologies Cary 60 spectrophotometer; \u03bbmax (nm) (rel. \u03b5). CD Spectra: Jasco J715, \u03bbmax and \u03bbmin (nm), \u0394\u03b5. 1H\u2010 and 13C\u2010NMR: Bruker 600\u00a0MHz Avance II+ (\u03b4(C1HD2OD) 3.31\u00a0ppm, and \u03b4(13CD3OD) 49.0\u00a0ppm, \u03b4 in ppm,J in Hz. Mass Spectrometry: Finnigan LCQ Classic, electrospray ionization (ESI) source, positive\u2010ion mode,Senescent plum tree leaves were harvested in November 2013 from a commercial orchard in Aldino (South Tyrol). They were immediately frozen in a freezer (\u221280\u00a0\u00b0C) and transported in a cold box (\u221220\u00a0\u00b0C) to Innsbruck, where they were stored cold (\u221280\u00a0\u00b0C).2) was frozen in liquid N2, grounded in a mortar and extracted with 1\u00a0ml of MeOH. The resulting suspension was centrifuged for 3\u00a0min at 13,000\u00a0g. Five hundred microliter of the MeOH supernatant were diluted with 2\u00a0ml of 50mm aq. potassium phosphate buffer (pH 7.0). After centrifugation for 3\u00a0min at 13,000\u00a0g, 200\u00a0\u03bcl of the extract was analyzed by HPLC . Yellow\u2010greenish senescent plum tree leaves (18.7\u00a0g) were frozen in liquid N2, pulverized to a fine powder and extracted with 60\u00a0ml of MeOH. The suspension was centrifuged for 5\u00a0min at 4000\u00a0g. Forty\u2010two milliliter of the supernatant were diluted with 168\u00a0ml of 50mm aq. potassium phosphate buffer (pH 7.0). After centrifugation for 5\u00a0min at 4000\u00a0g, the soln. was extracted two times with hexane. The MeOH extract was diluted with 300\u00a0ml of 50mm potassium phosphate buffer (pH 7.0) and applied to a pre\u2010conditioned 5\u00a0g SepPak cartridge. This was washed with 35\u00a0ml of H2O and the NCC\u2010containing fraction was eluted with 30\u00a0ml of MeOH. The solvents were removed by using a rotary evaporator. The residue was dissolved in 1\u00a0ml of MeOH and 4\u00a0ml of 50mm aq. potassium phosphate buffer (pH 7.0) using an ultrasonic bath. After centrifugation for 3\u00a0min at 13,000\u00a0g, the sample was divided in four aliquots and applied to semi\u2010prep. HPLC; injection volume, 1.25\u00a0ml; flow rate, 0\u00a0\u2013\u00a05\u00a0min: 1\u00a0\u2013\u00a04\u00a0ml\u00a0min\u22121, 5\u00a0\u2013\u00a090\u00a0min: 4\u00a0ml\u00a0min\u22121; solvent A: 4mm aq. AcONH4, solvent B: MeOH with AcONH4 (c\u00a0=\u00a04mm), solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a090\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a060, 80:20:0 to 40:60:0; 60\u00a0\u2013\u00a080, 40:60:0 to 0:100:0; 80\u00a0\u2013\u00a085, 0:100:0; 85\u00a0\u2013\u00a087, 0:100:0 to 0:20:80; 87\u00a0\u2013\u00a090, 0:20:80 to 80:20:0. Fractions containing Pd\u2010NCC\u201032 (1) of five consecutive semi\u2010prep. HPLC runs were collected and dried under reduced pressure. The residue was dissolved in 200\u00a0\u03bcl of MeOH and 800\u00a0\u03bcl of 50mm aq. potassium phosphate buffer (pH 7.0) and re\u2010purified by semi\u2010prep. HPLC; injection volume, 1.00\u00a0ml; flow rate, 0\u00a0\u2013\u00a05\u00a0min: 1\u00a0\u2013\u00a04\u00a0ml\u00a0min\u22121, 5\u00a0\u2013\u00a070\u00a0min: 4\u00a0ml\u00a0min\u22121; solvent A: 50mm aq. potassium phosphate buffer (pH 7.0), solvent B: MeOH, solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a070\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a050, 80:20:0 to 47.3:52.7:0; 50\u00a0\u2013\u00a055, 47.3:52.7:0 to 0:52.7:47.3; 55\u00a0\u2013\u00a060, 0:52.7:47.3 to 0:100:0; 60\u00a0\u2013\u00a065, 0:100:0; 65\u00a0\u2013\u00a067, 0:100:0 to 0:20:80; 67\u00a0\u2013\u00a070, 0:20:80 to 80:20:0. The fraction containing Pd\u2010NCC\u201032 (1) was collected between and diluted with 20\u00a0ml of 50mm aq. potassium phosphate buffer (pH 7.0). For de\u2010salting, the aq. soln. was applied to a pre\u2010conditioned 5\u00a0g SepPak cartridge, washed with 15\u00a0ml of H2O and eluted with 5\u00a0ml of MeOH. After removal of the solvents using a rotary evaporator, the sample was dried under high vacuum and a uniform sample of 0.29\u00a0mg of Pd\u2010NCC\u201032 (1) was obtained.Isolation of Raw Pd\u2010NCCs for Structural Analysis. 12 anal. extracts were prepared, combined and diluted with 95\u00a0ml of 50mm aq. potassium phosphate buffer (pH 7.0). This was applied to a pre\u2010conditioned 5\u00a0g SepPak cartridge, washed with 30\u00a0ml of H2O and the NCC\u2010containing fraction was eluted with 30\u00a0ml of MeOH. The fraction was dried under reduced pressure and the precipitate was dissolved in 400\u00a0\u03bcl of MeOH and 1.6\u00a0ml of 4mm aq. AcONH4. After centrifugation for 3\u00a0min at 13,000\u00a0g, the sample was divided in two aliquots and applied to semi\u2010prep. HPLC; injection volume, 1.00\u00a0ml; flow rate, 0\u00a0\u2013\u00a05\u00a0min: 1\u00a0\u2013\u00a04\u00a0ml\u00a0min\u22121, 5\u00a0\u2013\u00a090\u00a0min: 4\u00a0ml\u00a0min\u22121; solvent A: 4mm aq. AcONH4, solvent B: MeOH with AcONH4 (c\u00a0=\u00a04mm), solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a090\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a060, 80:20:0 to 40:60:0; 60\u00a0\u2013\u00a080, 40:60:0 to 0:100:0; 80\u00a0\u2013\u00a085, 0:100:0; 85\u00a0\u2013\u00a087, 0:100:0 to 0:20:80; 87\u00a0\u2013\u00a090, 0:20:80 to 80:20:0. The fractions containing Pd\u2010NCC\u201032 (1), Pd\u2010NCC\u201035 (2), Pd\u2010NCC\u201040 (3), Pd\u2010NCC\u201056 (4) and Pd\u2010NCC\u201060 (5) were collected and to obtain pure samples from all fractions an anal. HPLC run with AcONH4 had to be performed; injection volume, 200\u00a0\u03bcl; flow rate, 0.5\u00a0ml\u00a0min\u22121; solvent A: 4mm aq. AcONH4, solvent B: MeOH with AcONH4 (c\u00a0=\u00a04mm), solvent C: H2O; solvent composition (A/B/C) as a function of time (0\u00a0\u2013\u00a090\u00a0min): 0\u00a0\u2013\u00a05, 80:20:0; 5\u00a0\u2013\u00a060, 80:20:0 to 40:60:0; 60\u00a0\u2013\u00a080, 40:60:0 to 0:100:0; 80\u00a0\u2013\u00a085, 0:100:0; 85\u00a0\u2013\u00a087, 0:100:0 to 0:20:80; 87\u00a0\u2013\u00a090, 0:20:80 to 80:20:0. In each anal. HPLC run, the desired catabolite was collected.Pd\u2010NCC\u201032 (1). tR\u00a0=\u00a032.6\u00a0min. UV/VIS : 244sh (0.83), 314 (1.00) : 226 (8), 249 (\u22123), 263 (\u22123), 283 (\u22128), 319 (1). 1H\u2010NMR : 1.92 ); 2.08 ); 2.12 ); 2.23 ); 2.26\u00a0\u2013\u00a02.30 ); 2.31\u00a0\u2013\u00a02.35 ); 2.37\u00a0\u2013\u00a02.41 ); 2.60\u00a0\u2013\u00a02.65 , Ha\u2013C(121)); 2.71\u00a0\u2013\u00a02.77 ); 2.91 ); 3.17 ); 3.21 ); 3.24\u00a0\u2013\u00a03.28 , H\u2013C(4\u2033), H\u2013C(5\u2032), H\u2013C(5\u2033)); 3.33\u00a0\u2013\u00a03.39 , H\u2013C(3\u2032), H\u2013C(3\u2033)); 3.62\u00a0\u2013\u00a03.69 , Ha\u2013C(6\u2033), Hb\u2013C(32)); 3.71 ); 3.75 ); 3.83\u00a0\u2013\u00a03.87 , Hb\u2013C(6\u2033)); 3.96\u00a0\u2013\u00a04.01 , Hb\u2013C(182)); 4.02\u00a0\u2013\u00a04.09 , Hb\u2013C(5)); 4.17 ); 4.33 ); 4.77 ); 4.87 ); 9.32 ). 13C\u2010NMR : 8.4 (C(21)); 9.1 (C(71)); 9.1 (C(131)); 12.5 (C(171)); 22.0 (C(121)); 23.6 (C(5)); 24.8 (C(31)); 29.7 (C(15)); 36.9 (C(10)); 39.6 (C(122)); 52.7 (C(85)); 62.1 (C(6\u2032)); 62.1 (C(6\u2033)); 62.5 (C(16)); 66.6 (C(181)); 67.7 (C(82)); 70.3 (C(32)); 71.1 (C(4\u2032)); 71.1 (C(4\u2033)); 73.2 (C(182)); 74.8 (C(2\u2032)); 74.8 (C(2\u2033)); 77.7 (C(3\u2032)); 77.7 (C(3\u2033)); 77.7 (C(5\u2032)); 77.7 (C(5\u2033)); 103.9 (C(1\u2032)); 103.9 (C(1\u2033)); 112.2 (C(7)); 114.8 (C(13)); 120.0 (C(3)); 120.0 (C(12)); 124.2 (C(11)); 124.2 (C(14)); 125.6 (C(8)); 128.5 (C(1)); 133.9 (C(6)); 134.0 (C(2)); 139.6 (C(4)); 159.3 (C(17)); 130.2 (C(18)); 161.5 (C(9)); 171.4 (C(83)); 174.8 (C(19)); 177.2 (C(20)). ESI\u2010MS: 1079.2 ; 1063.3 ; 1047.3 ; 1041.3 ; 1025.3 ; 1005.1 (20), 1004.1 (53), 1003.1 ; 987.3 (7); 879.3 ; 863.4 ; 841.2 ; 827.3 (4); 684.1 ; 679.2 .see Fig.\u00a0. CD (MeOPd\u2010NCC\u201035 (2). tR\u00a0=\u00a035.5\u00a0min. UV/VIS (4mm aq. AcONH4/MeOH 63:37): 284 (0.75), 316 (1.00). ESI\u2010MS: 879.3 ; 863.3 ; 843.2 (15), 842.2 (47), 841.2 ; 825.3 (6); 809.3 ; 684.2 ; 679.2 ; 522.1 .Pd\u2010NCC\u201040 (3). tR\u00a0=\u00a040.6\u00a0min. UV/VIS (4mm aq. AcONH4/MeOH 59:41): 278 (0.78), 316 (1.00). ESI\u2010MS: 755.1 ; 739.2 ; 717.3 ; 701.3 ; 681.2 (10), 680.1 (40), 679.2 ; 647.2 ; 522.1 .Pd\u2010NCC\u201054. UV/VIS (4mm aq. AcONH4/MeOH 40:60): 316\u00a0nm. ESI\u2010MS: 699.2 ; 678.2 ; 663 (4), 662 (32), 661.2 ; 629.3 .Pd\u2010NCC\u201056 (4). tR\u00a0=\u00a056.4\u00a0min. UV/VIS (4mm aq. AcONH4/MeOH 47:53): 316\u00a0nm. ESI\u2010MS: 845.3 ; 829.3 ; 809.2 (15), 808.2 (46), 807.2 ; 775.3 ; 684.2 ; 645.2 .Pd\u2010NCC\u201060 (5). tR\u00a0=\u00a060.0\u00a0min. UV/VIS (4mm aq. AcONH4/MeOH 44:56): 315 (1.00). ESI\u2010MS: 683.2 ; 667.3 ; 647.2 (11), 646.2 (39), 645.2 ; 613.2 ; 522.1 .Pd\u2010NCC\u201060 (5) and Cj\u2010NCC\u20101Pd\u2010NCC\u201060 (5), of Cj\u2010NCC\u20101, as well as a 1:1 mixture of both were analyzed by anal. HPLC . tR\u00a0=\u00a070.7\u00a0min. UV/VIS (50mm aq. potassium phosphate buffer (pH 7.0)/MeOH 20:80): 239sh (1.00), 316 (0.87). ESI\u2010MS: 667.1 ; 631 (2), 630 (35), 629.2 ; 597.2 ; 506 . Provisional identification of Pd\u2010NCC\u201071 (6) with Cj\u2010NCC\u20102Pd\u2010NCC\u201071 (6), a separate sample of purified Cj\u2010NCC\u20102, as well as a mixture of both were analyzed by anal. HPLC.Pd\u2010YCC\u201061. tR\u00a0=\u00a061.3\u00a0min. UV/VIS (50mm aq. potassium phosphate buffer (pH 7.0)/MeOH 40:60): 246 (0.73), 313 (1.00), 429 (1.77). ESI\u2010MS: 881.1 ; 865.3 ; 843.1 ; 827.3 ; 807.2 (17), 806.1 (48), 805.1 ; 796.6 (16); 774.4 (26); 756.3 (17); 700.3 (15); 643.1 ; 611.3 .Pd\u2010YCC\u201067. tR\u00a0=\u00a067.1\u00a0min. UV/VIS (50mm aq. potassium phosphate buffer (pH 7.0)/MeOH) 25:75): 247 (0.74), 316 (1.00), 428 (1.29). ESI\u2010MS: 719.1 ; 703.2 ; 681.1 ; 665.3 ; 645.2 (11), 644.2 (40), 643.2 ; 611.2 .Pd\u2010PiCC\u201075. tR\u00a0=\u00a075.0\u00a0min. UV/VIS (50mm aq. potassium phosphate buffer (pH 7.0)/MeOH 1:9): 314 (0.75), 525 (1.00).Pd\u2010PiCC\u201075 (in an extract of a plum tree leaf) and of a purified sample of Cj\u2010PiCCProvisional identification of"}
{"text": "Glycosylation of the immunoglobulin G (IgG)-Fc tail is required for binding to Fc-gamma receptors (Fc\u03b3Rs) and complement-component C1q. A variety of IgG1-glycoforms is detected in human sera. Several groups have found global or antigen-specific skewing of IgG glycosylation, for example in autoimmune diseases, viral infections, and alloimmune reactions. The IgG glycoprofiles seem to correlate with disease outcome. Additionally, IgG-glycan composition contributes significantly to Ig-based therapies, as for example IVIg in autoimmune diseases and therapeutic antibodies for cancer treatment. The effect of the different glycan modifications, especially of fucosylation, has been studied before. However, the contribution of the 20 individual IgG glycoforms, in which the combined effect of all 4 modifications, to the IgG function has never been investigated. Here, we combined six glyco-engineering methods to generate all 20 major human IgG1-glycoforms and screened their functional capacity for Fc\u03b3R and complement activity. Bisection had no effect on Fc\u03b3R or C1q-binding, and sialylation had no- or little effect on Fc\u03b3R binding. We confirmed that hypo-fucosylation of IgG1 increased binding to Fc\u03b3RIIIa and Fc\u03b3RIIIb by ~17-fold, but in addition we showed that this effect could be further increased to ~40-fold for Fc\u03b3RIIIa upon simultaneous hypo-fucosylation and hyper-galactosylation, resulting in enhanced NK cell-mediated antibody-dependent cellular cytotoxicity. Moreover, elevated galactosylation and sialylation significantly increased (independent of fucosylation) C1q-binding, downstream complement deposition, and cytotoxicity. In conclusion, fucosylation and galactosylation are primary mediators of functional changes in IgG for Fc\u03b3R- and complement-mediated effector functions, respectively, with galactose having an auxiliary role for Fc\u03b3RIII-mediated functions. This knowledge could be used not only for glycan profiling of clinically important (antigen-specific) IgG but also to optimize therapeutic antibody applications. The importance of the biological properties of antibodies to specifically engage a target of choice and activate complement and Fc gamma receptors (Fc\u03b3R) on immune cells  is curreThis fucose residue is part of a conserved glycan on asparagine 297 in the Fc domain of immunoglobulin G (IgG). This glycan is important for the quaternary structure of the Fc part, since its removal abrogates binding of Fc\u03b3R and C1q and hence the antibody\u2019s effector functions , 11. ThiN-acetylglycosamines and mannoses and can be found in human serum with variable levels of core fucose, bisecting N-acetylglycosamine, galactose, and terminal sialic acids  or RBCs. NK cell isolation was only performed with blood from well-genotyped donors who do not express Fc\u03b3RIIc  to excluEscherichia coli strain DH5\u03b1 was used for recombinant DNA work. Restriction endonucleases, DNA modification enzymes were obtained from Thermo Fisher Scientific . Oligonucleotides were obtained from Geneart (Thermo Fisher Scientific) or Integrated DNA Technologies .Variable (V) genes for anti-human RhD (anti-D clone 19A10) heavy and light chain were sequenced from a single human B cell from a hyper immunized donor . A singll-fucose (2FF)  or 1\u2009mM 2-deoxy-2-fluoro-d-galactose (2FG) (Carbosynth), respectively, was added to the cell suspension 4\u2009h post transfection. To increase bisecting GlcNAc, 1% pEE6.4\u2009+\u2009GNTIII encoding mannosyl -glycoprotein beta-1,4-N-acetylglucosaminyltransferase (GNTIII) enzyme was co-transfected with 99% IgG1-\u03ba HC\u2009+\u2009LC vector. To increase galactose, 1% pEE6.4\u2009+\u2009B4GALT1 encoding \u03b2-1,4-galactosyltransferase 1 (B4GALT1) enzyme was co-transfected with 99% IgG1 vector and 5\u2009mM d-galactose  was added to the cell suspension 1\u2009h before transfection. To increase sialylation, the level of galactosylation must also be elevated as sialic acid is the terminal sugar group with galactose residues as substrate. Thus, 1% pEE6.4\u2009+\u2009B4GALT1 and 2.5% pEE14.4\u2009+\u2009STGALT encoding \u03b2-galactoside alpha-2,6-sialyltransferase 1 (ST6GALT) were both co-transfected 96.5% IgG1 vector and 5\u2009mM d-galactose was added to the cell suspension 1\u2009h before transfection. To further increase sialylation, in vitro sialylation (ivs) was performed on the purified in vivo sialylated IgG created using the previous method. Recombinant human \u03b1-2,6-sialyltransferase  and cytidine-5\u2032-monophospho-N-acetylneuraminic acid (CMP-NANA) (Roche) were incubated at 37\u00b0C for 24\u2009h with purified IgG1 with already in vivo enhanced galactose and sialic acid (as described above), after incubation samples were re-purified with protein A, as described previously (IgG1 production in human embryonic kidney (HEK) F cells and purification using protein A affinity chromatography was performed as described previously by Kruijssen et al.  Glyco-eneviously , 34.via a CaptiveSpray source with a NanoBooster . The latter enriched the N2 flow (3\u2009l/min) with CH3CN (pressure 0.2\u2009bar), resulting in increased sensitivity. The samples were ionized in positive ion mode at 1,100\u2009V. The Maxis Impact quadrupole-TOF\u2013MS  was used as detector. MS1 spectra were collected at a frequency of 1\u2009Hz with a scan range of m/z 550\u20131,800. The mass spectrometric data were calibrated internally in DataAnalysis 4.0  using a list of known IgG glycopeptide masses. MSConvert (Proteowizard 3.0) (m/z window of \u00b10.2 and within a time window of \u00b115\u2009s surrounding the retention time) was extracted using the in-house developed 3D Max Xtractor software tool. If above a signal:background ratio of 3, the background-subtracted area of the first three isotopic peaks of each glycopeptide in both 2+, 3+, and 4+ charge state were summed, and this summed value was then divided by the total summed value of all IgG1 glycopeptides to arrive at a percentage for each glycopeptide. From these percentages, we calculated several derived traits using the following formulas: fucosylation (H3N3F1\u2009+\u2009H4N3F1\u2009+\u2009H5N3F1\u2009+\u2009H6N3F1\u2009+\u2009G0F\u2009+\u2009G1F\u2009+\u2009G2F\u2009+\u2009H6N4F1\u2009+\u2009G0FN\u2009+\u2009G1FN\u2009+\u2009G2FN\u2009+\u2009H6N5F1\u2009+\u2009H4N3F1S1\u2009+\u2009H5N3F1S1\u2009+\u2009H6N3F1S1\u2009+\u2009G1FS\u2009+\u2009G2FS\u2009+\u2009H6N4F1S1\u2009+\u2009G2FS2\u2009+\u2009G1FNS\u2009+\u2009G2FNS\u2009+\u2009H6N5F1S1\u2009+\u2009G2FNS2), bisection (H6N4F1\u2009+\u2009G0FN\u2009+\u2009G1FN\u2009+\u2009G2FN\u2009+\u2009H6N5F1\u2009+\u2009H6N4F1S1\u2009+\u2009G1FNS\u2009+\u2009G2FNS\u2009+\u2009H6N5F1S1\u2009+\u2009G2FNS2\u2009+\u2009H6N4\u2009+\u2009G0N\u2009+\u2009G1N\u2009+\u2009G2N\u2009+\u2009H6N5\u2009+\u2009H6N4S1\u2009+\u2009G1NS\u2009+\u2009G2NS\u2009+\u2009H6N5S1\u2009+\u2009G2NS2), galactosylation [(H4N3F1\u2009+\u2009H5N3F1\u2009+\u2009G1F\u2009+\u2009H6N4F1\u2009+\u2009G1FN\u2009+\u2009H6N5F1\u2009+\u2009H4N3F1S1\u2009+\u2009H5N3F1S1\u2009+\u2009H6N3F1S1\u2009+\u2009G1FS\u2009+\u2009H6N4F1S1\u2009+\u2009G1FNS\u2009+\u2009H6N5F1S1\u2009+\u2009H4N3\u2009+\u2009H5N3\u2009+\u2009H6N3\u2009+\u2009G1\u2009+\u2009H6N4\u2009+\u2009G1N\u2009+\u2009H6N5\u2009+\u2009H4N3S1\u2009+\u2009H5N3S1\u2009+\u2009H6N3S1\u2009+\u2009G1S\u2009+\u2009H6N4S1\u2009+\u2009G1NS\u2009+\u2009H6N5S1) * 0.5\u2009+\u2009G2F\u2009+\u2009G2FN\u2009+\u2009G2FS\u2009+\u2009G2FS2\u2009+\u2009G2FNS\u2009+\u2009G2FNS2\u2009+\u2009G2\u2009+\u2009G2N\u2009+\u2009G2S\u2009+\u2009G2S2\u2009+\u2009G2NS\u2009+\u2009G2NS2], sialylation [(H4N3F1S1\u2009+\u2009H5N3F1S1\u2009+\u2009H6N3F1S1\u2009+\u2009G1FS\u2009+\u2009G2FS\u2009+\u2009H6N4F1S1\u2009+\u2009G1FNS\u2009+\u2009G2FNS\u2009+\u2009H6N5F1S1\u2009+\u2009H4N3S1\u2009+\u2009H5N3S1\u2009+\u2009H6N3S1\u2009+\u2009G1S\u2009+\u2009G2S\u2009+\u2009H6N4S1\u2009+\u2009G1NS\u2009+\u2009G2NS\u2009+\u2009H6N5S1) * 0.5\u2009+\u2009G2FS2\u2009+\u2009G2FNS2\u2009+\u2009G2S2\u2009+\u2009G2NS2], hybrid-types (H5N3F1\u2009+\u2009H6N3F1\u2009+\u2009H6N4F1\u2009+\u2009H6N5F1\u2009+\u2009H5N3F1S1\u2009+\u2009H6N3F1S1\u2009+\u2009H6N4F1S1\u2009+\u2009H6N5F1S1\u2009+\u2009H5N3\u2009+\u2009H6N3\u2009+\u2009H6N4\u2009+\u2009H6N5\u2009+\u2009H5N3S1\u2009+\u2009H6N3S1\u2009+\u2009H6N4S1\u2009+\u2009H6N5S1), and high-mannose (H5N2\u2009+\u2009H6N2\u2009+\u2009H7N2\u2009+\u2009H8N2\u2009+\u2009H9N2). For some of the minor hybrid-type glycans, it could not be determined conclusively whether a galactose or a bisecting N-acetylglucosamine was present, so an educated guess was made based on structural knowledge .Immunoglobulin G-Fc glycan composition of produced IgG1 was determined by mass spectrometry as described previously by Dekkers et al.  Trypsin-ard 3.0)  was usedard 3.0)  was usedProtein A purified IgG was analyzed for monomeric and dimeric IgG on a Superdex 200 10/300 gel filtration column  connected to an \u00c4kta explorer  HPLC system at RT with a flow rate of 0.5\u2009ml/min and PBS as running buffer. Elution profiles were obtained by recording the absorbance at 215\u2009nm.Human Fc\u03b3R constructs  for surface plasmon resonance (SPR) analysis were obtained from Sino biological . To further include all human Fc\u03b3Rs, a fusion Fc\u2013Fc\u03b3R construct composed of the extracellular domain of the Fc\u03b3RIIIb in both allotypes followed by a Fc domain was created. To create the fusion Fc\u2013Fc\u03b3RIIIb constructs the amino acid code of the extracellular domain of either Fc\u03b3RIIIb of NA1 allotype or Fc\u03b3RIIIb NA2 allotype  NCBI re. For bioKD) was done using an equilibrium analysis by linear intrapolation to Rmax\u2009=\u2009500  at 109\u2009cells/ml. An amount of 105 erythrocytes were incubated with NK cells for 2\u2009h at 37\u00b0C in a 2:1 ratio in Iscove\u2019s modified dulbecco\u2019s medium  supplemented with 10% fetal calf serum  and anti-D IgG1-glycoforms at a total volume of 100\u2009\u00b5l. To determine 100% lysis, 2.5% saponine  was added to RBC in control wells and spontaneous lysis (sp) was determined by incubation of RBC without NK cells. Supernatants were collected and released 51Cr was quantified in a Packard Cobra II Auto-Gamma Counter Model D5005 (PerkinElmer). Percentage cytotoxicity was determined by the following formula: NK cells were isolated from Ficoll-Plaque\u2122-Plus  gradient obtained PBMCs by a CD56 magnetic-activated cell separation isolation kit , according to manufacturer\u2019s description. D\u2009+\u2009RBCs were isolated and labeled with radioactive chromium  and incubated 30\u2009min at RT. To remove unbound TNBS, the solution was dialyzed  using a dialysis cassette  for 1.5\u2009h at RT against PBS and additionally overnight at 4\u00b0C to obtain HSA-TNP.A 2.4-mM 2,4,6-trinitrobenzenesulfonic acid (TNBS) (Sigma-Aldrich) solution was added to 20\u2009mg human serum albumin (HSA) diluted to 20\u2009mg/ml  in 0.2\u2009M NA+/+/plx {veronalbuffer \u2009+\u200910\u2009mM CaCl2 (Merck)\u2009+\u20092\u2009mM MgCl2 (Merck)\u2009+\u20090.1% poloxamer} for 1\u2009h at RT. When C1q was blocked, 10\u2009min prior to addition of serum to the ELISA plate, anti-C1q-85 blocking antibody  and the reaction was stopped with the addition of 100\u2009\u00b5l 2\u2009M H2SO4 (Merck). The optical density (OD) was measured at A450\u2009nm using a plate reader .To coat, maxisorp plates  were incubated o/n at RT with 20\u2009\u00b5g/ml HSA-TNP in PBS. The plates were washed 5\u00d7 with PBS\u2009+\u20090.1% tween-20 (Sigma-Aldrich) (wash buffer) using an ELISA washer . All following washing steps were done similarly. The IgG samples were diluted in 100\u2009\u00b5l PBS/plx [PBS\u2009+\u20090.1% poloxamer ] per well and incubated for 1.5\u2009h at RT. The plates were washed and incubated with 100\u2009\u00b5l 1:35 serum pool in VBantibody  was addeti-C1q-2 , 0.5\u2009\u00b5g/ti-C1q-2 , 0.6\u2009\u00b5g/ti-C1q-2 , or 1\u2009\u00b5gThe results were analyzed with a parallel line assay in Microsoft Office Excel . We asse+ RBCs obtained from heparinized blood were mixed with 350\u2009\u00b5l 0.313\u2009mM TNBS in 0.15\u2009M Na2HPO4, pH 8.8 and incubated for 10\u2009min at RT. TNPylated RBCs were centrifuged for 2\u2009min at 350\u2009\u00d7\u2009g and washed two times with PBS. RBC were resuspended into VBG+/+ [VB+/+\u2009+\u20090.05% w/v gelatin (Sigma-Aldrich)]. Anti-TNP IgG1 was serially diluted in VBG\u2212/\u2212 . In round bottom plates to a final volume of 100\u2009\u00b5l we combined the diluted IgG1, 10% serum, ~4.5\u2009\u00d7\u2009106 RBC, and a glass bead  to ensure mixing of the solution during incubation . This amount of RBC was taken to ensure the 100% absorbance between 1.8 and 2.2 delta (\u0394) A412\u2013A690\u2009nm. The plates were incubated for 90\u2009min at 37\u00b0C while shaking at 150\u2009rpm . After incubation, 1.25% w/v saponine was supplemented to the 100% control wells, 100\u2009\u00b5l VBG\u2212/\u2212 was added to all wells and the plates were centrifuged for 2\u2009min at 350\u2009\u00d7\u2009g. Subsequently, 150\u2009\u00b5l of supernatant was transferred into a separate plate and OD was measured at \u0394 A412\u2013A690\u2009nm using a plate reader. The percentage of lysed cells was calculated as follows: 50) for each replicate of the different glycoforms using a non-linear fit for normalized response with a variable slope and combined these to an average EC50.Fifty microliters of washed, packed, Dp\u2009<\u20090.05 using two-tailed tests.Statistical analyses were performed using GraphPad Prism version 6.00 for Windows . The level of significance was set at x-axis legend, Figures N-acetylglucosaminyltransferase III (GntIII) to increase bisection \u2014but this was only observed in samples with low starting-levels of galactosylation   Figure , 47, 48.) Figure , with boKD of more than twofold from unmodified IgG to be potentially meaningful changes and within the scope of the SPR method, using a simplified 1:1 Langmuir model that does not fully represent the actual interaction which is more complicated  and subsequent C4b deposition was titrated by serial dilution . All glycovariants of anti-TNP bound TNP-HSA equally well , but C1q binding and C4b deposition differed profoundly for the different glycoforms . The relative C1q binding and C4b deposition were then calculated Figures A and witWe have previously created an orthogonal set of glyco-engineering tools  which weOf the Fc\u03b3Rs, we only observed an effect of glycosylation on binding to the Fc\u03b3RIII-family of receptors, both Fc\u03b3RIIIa and Fc\u03b3RIIIb and their allotypes, which confirms and expands recent studies using a limited set of glycovariants presented here , 30. IncThe enhanced binding of galactosylated and afucosylated IgG was slightly weakened by addition of sialic acid, but only if a bisecting GlcNAc was present. A similar negative effect of sialylation has previously been observed for mouse Fc\u03b3R by Ravetch and colleagues . ImportaIn vitro, this has been found result in stronger functional efficacy for the V158-variant  . In vitr-variant \u201357. In vlearance . It shoulearance . We alsolearance , 62, 63.Importantly, the observed changes in Fc\u03b3RIIIa-binding due to glycosylation reliably translated into functional NK cell-mediated ADCC lysis of RBC. For Fc\u03b3RIIIa and Fc\u03b3RIIIb it was known that absence of IgG-Fc core-fucosylation increases the affinity of interaction due to a glycan\u2013glycan interaction between the Fc glycan and the N162-glycan uniquely found in the Fc\u03b3RIII family . Our appThe possible effect of the Fc-glycans on complement activity, has until now remained enigmatic. It has been proposed for a long time that agalactosylated IgG activates complement more efficiently through the lectin pathway (MBL) . To our Low galactosylation level in total IgG generally correlates with disease severity of several autoimmune diseases, such as rheumatoid arthritis and multiple sclerosis , 14. WhiIn summary, we show here that a set of glyco-engineering techniques we recently developed  can be cPeripheral blood from anonymous, healthy volunteers was obtained with informed, written consent of all subjects, in accordance with Dutch regulations. This study was approved by the Sanquin Ethical Advisory Board in accordance with the Declaration of Helsinki.GD, TK, DW, TR, MW, and GV designed the research. GD, AB, DW, TR, MW, and GV designed the experiments. GD, LT, RP, AB, MdB, CK, SL-T, RV, and YM performed the experiments. GD, RP, AB, MdB, CK, TR, TK, MW, and GV analyzed data, GD and GV wrote the manuscript. All authors contributed to and approved the final manuscript.The authors declare that this study received funding from Sanquin Bloedvoorziening, a not-for-profit organization. The funder was not involved in the study design or collection, analysis, or interpretation of the data."}
{"text": "The fused oxazine ring adopts an approximately half-chair conformation. The two benzoxazine rings are oriented anti to one another around the central C\u2014C bond. The dominant inter\u00admolecular inter\u00adaction in the crystal structure is a C\u2014H\u22efF hydrogen bond between the F atoms and the axial H atoms of the OCH2N methyl\u00adene group in the oxazine rings of neighbouring mol\u00adecules. C\u2014H\u22ef\u03c0 contacts further stabilize the crystal packing.The title fluorinated bis\u00adbenzoxazine, C Bond lengths in the benzoxazine moiety in (I)et al., 2012abThe mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01Q = 0.4913\u2005(15)\u2005\u00c5, and \u03b8 = 52.03\u2005(17)\u00b0 and \u03c6 = 98.3\u2005(2)\u00b0, with C2 and N1 displaced from the mean plane by \u22120.299\u2005(2) and 0.331\u2005(1)\u2005\u00c5, respectively. The C1\u2014C1A bond is in an axial position with a C5\u2014N1\u2014C1\u2014C1A torsion angle of 75.45\u2005(18)\u00b0. The two benzoxazine rings are oriented anti to one another about the central C1\u2014C1A bond, with an N1\u2014C1\u2014C1A\u2014N1A torsion angle of 180.0\u2005(2)\u00b0.The fused six-membered heterocyclic rings exist in an approximately half-chair conformation, characterized by a puckering amplitude A\u22efF1 hydrogen bonds  and 3.577\u2005(2)\u2005\u00c5 and with C\u2014H\u22efCg angles of 126 and 129\u00b0, respectively.The packing of title compound is dominated by C2\u2014H2s Table\u00a01, that cos Table\u00a01, as indiH-1,3-benzoxazine)   monohydrate  bis set to 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016015243/sj5506sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015243/sj5506Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016015243/sj5506Isup3.cmlSupporting information file. DOI: 1507056CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structure of the title squarate salt is reported. Classical N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds combine with weak C\u2014O\u22ef\u03c0(ring) and \u03c0\u2013\u03c0 contacts to stabilize the crystal packing. 6H10N22+\u00b72C4HO4\u2212, comprises two hydrogen squarate  anions and a 2-(aza\u00adniumylmeth\u00adyl)pyridinium dication. The squaric acid mol\u00adecules each donate an H atom to the N atoms of the pyridine ring and the amino\u00admethyl units of a 2-(amino\u00admeth\u00adyl)pyridine mol\u00adecule, forming the 1:2 salt. The Hsq\u2212 anions are linked by strong O\u2014H\u22efO hydrogen bonds and an N\u2014H\u22efO hydrogen bond links the 2-(aza\u00adniumylmeth\u00adyl)pyridinium cation to one of the squaric acid anions. The crystal structure features additional N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 stacking and unusual weak C\u2014O\u22ef\u03c0(ring) inter\u00adactions.The asymmetric unit of the title compound, C It can be found in three forms: uncharged H2sq, the Hsq\u2212 monoanion and the sq2\u2212 dianion. The mono- and dianions are often produced following deprotonation by amines  electron donors of one or two lone pairs of electrons. Recently, we reported the synthesis and characterization of the same organo\u00adammonium squarate as the title compound but as a hydrate in the triclinic space group PP21/c.Hydrogen bonding is the most common way of generating supra\u00admolecular organic systems in crystal engineering and mol\u00adecular recognition. Hydrogen-bonded systems generated from organic cations and anions are of special inter\u00adest as they would be expected to form stronger hydrogen bonds than those in neutral mol\u00adecules \u2005\u00c5] hydrogen bond  pyridine forms a salt with two squaric acid mol\u00adecules and each mol\u00adecule of the acid loses one proton. One of these is transferred to the N atom of the pyridine ring, generating the 4-(amino\u00admeth\u00adyl)morpholinium mono-cation. The other from the second acid mol\u00adecule is engaged in the formation of a homo-conjugated hydrogen squarate anion nd Fig.\u00a01. The elend Fig.\u00a01. ConsideCg1, Cg2 and Cg3. The dihedral angles between the mean plane of ring 1 and those of rings 2 and 3 are 18.818\u2005(8) and 31.564\u2005(6)\u00b0, respectively. The dihedral angle between the two squarate anions is 29.19\u2005(1)\u00b0. The angles between the C\u2014C bonds in the Hsq\u2212 anions are close to 90\u00b0, with the oxygen atoms directed almost along the diagonals.N1/C1\u2013C5, C7\u2013C10 and C11\u2013C14 are defined as rings 1, 2 and 3, respectively, with centroids \u2212 ion has one C\u2014O bond (C11\u2014O5) at 1.3023\u2005(17)\u2005\u00c5, which is significantly longer than a normal single C\u2014O bond. This most likely reflects the involvement in the negative charge-assisted hydrogen bonding mentioned earlier. At 1.3000\u2005(15)\u2005\u00c5, the C10\u2014O4 bond is similarly extended. The remaining C\u2014O bonds in both rings display a similar pattern with one obvious C=O double bond in each ring  and the others of inter\u00admediate length in the range 1.2356\u2005(16) to 1.2658\u2005(15)\u2005\u00c5, indicating some delocalization occurring in both rings.The C\u2014C distances in the planar squarate ring systems reflect partial double-bond character for C9\u2014C10, C7\u2014C10, C11\u2014C12 and C11\u2014C14 with distances of 1.4291\u2005(17), 1.4357\u2005(16), 1.4139\u2005(17) and 1.4465\u2005(18)\u2005\u00c5, respectively. In contrast C7\u2014C8, C8\u2014C9, C12\u2014C13 and C13\u2014C14 display more single-bond character with distances of 1.4886\u2005(17), 1.4929\u2005(17), 1.4802\u2005(18) and 1.5141\u2005(17)\u2005\u00c5, respectively. The HsqA\u22efO3 [2.4583\u2005(14)\u2005\u00c5] related to the proton-sharing inter\u00adaction discussed earlier. This pair of anions is further linked to the 2-(aza\u00adniumylmeth\u00adyl)pyridinium dication by an N1\u2014H1A\u22efO1 hydrogen bond, Fig.\u00a01A\u22efO3, N2\u2014H2B\u22efO2i and N2\u2014H2B\u22efO5i hydrogen bonds form rings with an C\u22efO6i and N2\u2014H2B\u22efO5i hydrogen bonds combine to form C\u22efO6i, and N2\u2014H2A\u22efO8ii and homonuclear O4\u2014H4A\u22efO6iii and O5\u2014H5A\u22efO3 hydrogen bonds generate a larger Cg2ii, C7\u2014O1\u22efCg3iv and C13\u2014O7\u22efCg2v inter\u00adactions reinforced by \u03c0\u2013\u03c0 stacking inter\u00adactions. These latter contacts  also contribute to the stabilization of the crystal packing  and 2-(amino\u00admeth\u00adyl)pyridine  were dissolved in water (25\u2005cm3) to obtain a mixture in the molar ratio 2:1 and the solution was heated to 323\u2005K in a temperature-controlled bath and stirred for one\u2005h. The reaction mixture was then slowly cooled to room temperature. The crystals formed were filtered and washed with 10\u2005cm3 of methanol, and dried in air.All chemical reagents were analytical grade commercial products. The solvent was purified by conventional methods. Squaric acid (HUiso(H) = 1.2Ueq(C). The NH3 group (N\u2014H = 0.89\u2005\u00c5) was also allowed to ride in the refinement with Uiso(H) = 1.5Ueq(N). The O-bound H atoms and N1-bound H atom were located in a difference-Fourier map and refined with Uiso(H) = 1.2Ueq(O) and Uiso(H) = 1.5Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017004376/sj5524sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004376/sj5524Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004376/sj5524Isup3.cmlSupporting information file. DOI: 1538918CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The macrocyclic title compound crystallizes as a dihydrate with a 12-membered inner ring system. Hydrogen bonds involving the lattice water mol\u00adecules link the components into a three-dimensional network system. 21H40N4\u00b72H2O, has been determined from synchrotron X-ray radiation data. The asymmetric unit comprises one 12-membered macropolycycle and two lattice water mol\u00adecules. The macropolycycle contains two cyclo\u00adhexane rings and one 1,3-di\u00adaza\u00adcyclo\u00adhexane ring, all in chair conformations. The C\u2014N and C\u2014C bond lengths are in the ranges 1.4526\u2005(16)\u20131.4786\u2005(17) and 1.517\u2005(2)\u20131.5414\u2005(17)\u2005\u00c5, respectively. One intra\u00admolecular N\u2014H\u22efN hydrogen bond helps to stabilize the mol\u00adecular conformation while medium-strength inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds involving the lattice water mol\u00adecules connect the components into a three-dimensional network.The structure of the title compound, C The two methyl substituents of the C10 and C20 atoms are on the same side with respect to the macrocyclic plane of the four N atoms \u20131.4786\u2005(17)\u2005\u00c5 and 1.517\u2005(2)\u20131.5414\u2005(17)\u2005\u00c5 for the C\u2014N and C\u2014C bonds, respectively. The N1\u2014C20 distance is the longest C\u2014N distance, presumably as a consequence of the methyl group on the C20 atom and the N\u22efH\u2014O hydrogen bond involving N1. The bond angles within the six-membered 1,3-di\u00adaza\u00adcyclo\u00adhexane ring, N2\u2014C7\u2014N3, C7\u2014N2\u2014C8, and C7\u2014N3\u2014C10, are 109.89\u2005(10), 109.60\u2005(10), and 108.08\u2005(9)\u00b0, respectively. All other C\u2014N, C\u2014C, and C\u2014H bond lengths and corresponding angles are in the normal range for such compounds  unit, viz. the crystal structure of [Cr(L2)(H2O)](ClO4)2\u00b73H2O docosane (L1) was synthesized according to a literature protocol  in H2O (40\u2005mL) was rapidly added 37% formaldehyde  at room temperature. The reaction mixture was refluxed for 3\u2005h. After cooling, the resultant white solid was filtered, washed with water, and dried. The crude product of L2\u00b72H2O, (I)2O (1:2 v/v) solution to give colourless crystals suitable for X-ray analysis.Commercially available (Sigma\u2013Aldrich) 1,2-cyclo\u00adhexa\u00adnedi\u00adamine was used as provided. All other chemicals were reagent grade and used without further purification. The starting material, 3,14-dimethyl-2,6,13,17-tetra\u00adaza\u00adtri\u00adcyclo(16.4.0Uiso(H) values of 1.5 and 1.2 Ueq of the parent atoms, respectively. N- and O-bound H atoms were assigned based on a difference Fourier map, and were refined with distance restraints of 0.91\u2005(4) and 0.88\u2005(2)\u2005\u00c5 (using DFIX and DANG commands), respectively, and with Uiso(H) values of 1.2Ueq of the parent atoms.Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989017002444/wm5364sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002444/wm5364Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017002444/wm5364Isup3.cmlSupporting information file. DOI: 1532347CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N6-benzoyl\u00adadenine (BA) and one mol\u00adecule of 4-hy\u00addroxy\u00adbenzoic acid (HBA). The N6-benzoyl\u00adadenine (BA) has an N(7)\u2014H tautomeric form with non-protonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intra\u00admolecular N\u2014H\u22efO hydrogen bond on the Hoogsteen face of the purine ring. The primary robust via N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.The asymmetric unit of the title co-crystal contains one mol\u00adecule of  12H9N5O\u00b7C7H6O3, contains one mol\u00adecule of N6-benzoyl\u00adadenine (BA) and one mol\u00adecule of 4-hy\u00addroxy\u00adbenzoic acid (HBA). The N6-benzoyl\u00adadenine (BA) has an N(7)\u2014H tautomeric form with nonprotonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intra\u00admolecular N\u2014H\u22efO hydrogen bond between the carbonyl (C=O) group and the N(7)\u2014H hydrogen on the Hoogsteen face of the purine ring, forming a graph-set S(7) ring motif. The primary robust R22(8) ring motif is formed in the Watson\u2013Crick face via N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds . Weak inter\u00adactions, such as, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 are also observed in this crystal structure.The asymmetric unit of the title co-crystal, C N6-derivatives have plant hormone (kinetin) (Tr). They also offer a variety of hydrogen-bonding donor and acceptor sites  mol\u00adecule and one 4-hy\u00addroxy\u00adbenzoic acid (HBA) mol\u00adecule \u2014H tautomeric form with non-protonated N1, N3 and N9 atoms. In the crystal structures of N6-benzoyl\u00adadenine  and N6-benzoyl adenine-dl-tartaric acid (1:1)    ring motif in the Hoogsteen face. In contrast, it may be noted that in the crystal structure of N6-benzyl\u00adadenine, (where no intra\u00admolecular hydrogen bond is present) the N6-substituent is syn to N1 and distal to N7 and the adenine moiety exists in the N(9)\u2014H tautomeric form le Fig.\u00a01. The bond Table\u00a01 with an via N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds involving the carboxyl group of HBA. The N7 atom is a bifurcated donor and the carbonyl oxygen atom acts as a double acceptor for the N\u2014H\u22efO hydrogen bonds. Inversion-related BA mol\u00adecules form dimers through an array of hydrogen bonds, generating ring motifs, and these dimers are doubly bridged by inversion-related HBA mol\u00adecules  supra\u00admolecular ring is formed along the c-axis direction. A weak C8\u2014H8\u22ef\u03c0 inter\u00adaction is also present. Further consolidation of the structure is provided by homo and hetero \u03c0\u2013\u03c0 stacking inter\u00adactions   and N6-benzoyl\u00adadenine\u2013dl-tartaric acid (1:1)    and 4-hy\u00addroxy\u00adbenzoic acid (35\u2005mg) in an equimolar ratio in a total volume of 30\u2005mL. The mixture was warmed over a water bath for 30\u2005min, filtered, and left aside for a few days. Colourless plate-shaped crystals were collected from the mother solution following slow cooling at room temperature.The title co-crystal was prepared by mixing a hot ethanol solution of Uiso(H) = kUeq, where k = 1.5 for hy\u00addroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017002171/hg5481sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002171/hg5481Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017002171/hg5481Isup3.cmlSupporting information file. DOI: 1531929CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title zwitterion exists in the iminium/phenoxide form. The mol\u00adecule is twisted around the N\u2014C(benzene) bond with the C=N\u2014C\u2014C torsion angle being 39.42\u2005(8)\u00b0. In the crystal, a zigzag supra\u00admolecular chain is sustained by charge-assisted hy\u00addroxy-O\u2014H\u22efO(phenoxide) hydrogen bonding. 17H13NO2 (systematic name: 1-{(1E)-[(4-hy\u00addroxy\u00adphen\u00adyl)iminium\u00adyl]meth\u00adyl}naphthalen-2-olate), features an intra\u00admolecular charge-assisted N+\u2014H\u22efO\u2212 hydrogen bond. A twist in the mol\u00adecule is evident around the N\u2014C(hy\u00addroxy\u00adbenzene) bond [C\u2014N\u2014C\u2014C torsion angle = 39.42\u2005(8)\u00b0] and is reflected in the dihedral angle of 39.42\u2005(8)\u00b0 formed between the aromatic regions of the mol\u00adecule. In the crystal, zigzag supra\u00admolecular chains along the a axis are formed by charge-assisted hy\u00addroxy-O\u2014H\u22efO(phenoxide) hydrogen bonding. These are connected into a layer in the ab plane by charge-assisted hy\u00addroxy\u00adbenzene-C\u2014H\u22efO(phenoxide) inter\u00adactions and \u03c0\u2013\u03c0 contacts [inter-centroid distance between naphthyl-C6 rings = 3.4905\u2005(12)\u2005\u00c5]. Layers stack along the c axis with no specific inter\u00adactions between them. The Hirshfeld surface analysis points to the significance C\u22efH contacts between layers.The title zwitterion, C The dihedral angle between the two aromatic regions is 39.42\u2005(8)\u00b0. The coplanar relationship between the imine and naphthyl residues is stabilized by an intra\u00admolecular charge-assisted N+\u2014H\u22efO\u2212 hydrogen bond, Table\u00a01The mol\u00adecular structure of (I)a axis mediated by hy\u00addroxy-O\u2014H\u22efO(phenoxide) charge-assisted hydrogen bonding, Fig.\u00a02a and Table\u00a01ab plane by charge-assisted hy\u00addroxy\u00adbenzene-C\u2014H\u22efO(phenoxide) inter\u00adactions, Table\u00a01i = 3.4905\u2005(12)\u2005\u00c5 and angle of inclination = 2.68\u2005(8)\u00b0 , Fig.\u00a02b. Layers stack along the c axis with no directional inter\u00adactions between them, Fig.\u00a02c.The most prominent feature of the mol\u00adecular packing is the formation of a zigzag (glide symmetry) supra\u00admolecular chain along the et al., 2017dnorm, Fig.\u00a03The Hirshfeld surface was calculated for (I)a, and those delineated into H\u22efH, C\u22efH/H\u22efC, O\u22efH/H\u22efO and C\u22efC contacts  and -(C12\u2013C17) rings through the arrow-shaped distribution with the green points spread about de = di = 1.8\u2005\u00c5. The small contributions from other inter\u00adatomic contacts summarized in Table\u00a03The overall two-dimensional fingerprint plot, Fig.\u00a06et al., 2016i.e. (I)\u00b70.5EtOH  and 1.2943\u2005(19)\u2005\u00c5. By contrast to (I)viz. a P21/c form with Z\u2032 = 2 \u00b0 for the C2/c form. Finally, a deprotonated form of (I)et al., 2007The most closely related structure to (I)v/v) by slow evaporation.4-Hy\u00addroxy\u00adaniline  was added to a solution of 2-hy\u00addroxy-1-napthaldehyde  in ethanol (25\u2005ml). The resulting mixture was refluxed at 333\u2005K and stirred for 2.5\u2005h. The reaction mixture was cooled to room temperature and the resulting orange precipitate was filtered off and washed with cold ethanol to obtain the pure product in 65% yield. Crystals of (I)Uiso(H) values set at 1.2Ueq(C). The O- and N-bound H atoms were located in a difference Fourier map, but were refined with distance restraints of O\u2014H = 0.82\u00b10.01\u2005\u00c5 and N\u2014H = 0.86\u00b10.01\u2005\u00c5, and with Uiso(H) values set at 1.5Ueq(O) and 1.2Ueq(N), respectively. To confirm the positions of the acidic-H atoms, a separate refinement was conducted whereby no distance restraints were applied resulting in O\u2014H and N\u2014H bond lengths of 0.93\u2005(2) and 1.00\u2005(3)\u2005\u00c5, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698901701458X/ex2001sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901701458X/ex2001Isup2.hklStructure factors: contains datablock(s) I. DOI: 1429885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II centre via the thiol\u00adate S and imine N atoms in each of the two independent mol\u00adecules comprising the asymmetric unit, leading to N2S2 donor sets and distorted tetra\u00adhedal geometries. The crystal features zigzag chains of mol\u00adecules sustained by N\u2014H\u22efN and amine-N\u2014H\u22efS hydrogen bonds.The title thio\u00adsemicarbazonate complex has the ligands coordinating the Zn II complex, [Zn(C18H18N3S)2], (I), features two independent but chemically equivalent mol\u00adecules in the asymmetric unit. In each, the thio\u00adsemicarbazonate monoanion coordinates the ZnII atom via the thiol\u00adate-S and imine-N atoms, with the resulting N2S2 donor set defining a distorted tetra\u00adhedral geometry. The five-membered ZnSCN2 chelate rings adopt distinct conformations in each independent mol\u00adecule, i.e. one ring is almost planar while the other is twisted about the Zn\u2014S bond. In the crystal, the two mol\u00adecules comprising the asymmetric unit are linked by amine-N\u2014H\u22efN(imine) and amine-N\u2014H\u22efS(thiol\u00adate) hydrogen bonds via an eight-membered heterosynthon, {\u22efHNCN\u22efHNCS}. The dimeric aggregates are further consolidated by benzene-C\u2014H\u22efS(thiol\u00adate) inter\u00adactions and are linked into a zigzag supra\u00admolecular chain along the c axis via amine-N\u2014H\u22efS(thiol\u00adate) hydrogen bonds. The chains are connected into a three-dimensional architecture via phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) and \u03c0\u2013\u03c0 inter\u00adactions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873\u2005(11)\u2005\u00c5]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different inter\u00adactions formed by the independent mol\u00adecules in the crystal and the impact of the \u03c0\u2013\u03c0 inter\u00adactions between chelate and phenyl rings.The title Zn The similarity in bond lengths extends to the angles subtended at the ZnII atoms which, for the Zn1-containing mol\u00adecule range from 87.00\u2005(5)\u00b0 for S2\u2014Zn1\u2014N6, to 134.00\u2005(5)\u00b0 for S2\u2014Zn1\u2014N3, i.e. a range of 47\u00b0; the acute angle is associated with the chelate angle. A slightly narrower range is noted for the Zn2-containing mol\u00adecule, i.e. 85.99\u2005(5)\u00b0 for S3\u2014Zn2\u2014N9, to 131.29\u2005(5)\u00b0 for S3\u2014Zn2\u2014N12, i.e. about 45\u00b0. The assignment of four-coordinate geometries can be qu\u00adanti\u00adfied by the values of \u03c44, which range from 1.00 for an ideal tetra\u00adhedron to 0.00 for perfect square-planar geometry E, as are the conformations about the ethyl\u00adene bonds, Table\u00a01Two independent mol\u00adecules comprise the asymmetric unit of (I)II atoms to form five-membered ZnSCN2 rings. The chelate rings adopt different conformations in each independent mol\u00adecule. For the Zn1-containing mol\u00adecule, the Zn1/S1/C1/N2/N3 ring is almost planar (r.m.s. deviation = 0.005\u2005\u00c5) but the Zn1/S2/C19/N5/N6 ring is twisted about the Zn1\u2014S2 bond. A similar situation pertains to the Zn2-containing mol\u00adecule where there is a small twist about the Zn2\u2014S3 bond in the Zn2/S3/C37/N8/N9 ring and the Zn2/S4/C55/N11/N12 ring is planar to within an r.m.s. deviation of 0.008\u2005\u00c5. To a first approximation, for each thio\u00adsemicarbazone ligand, all atoms but the terminal ethyl and central phenyl rings lie in a plane. This is qu\u00adanti\u00adfied in the dihedral angle between each five-membered chelate ring and the central and terminal rings of the prop-2-en-1-yl\u00adidene substituent, as summarized in Table\u00a02The thio\u00adsemicarbazone ligands chelate the ZnCrystal Explorer a and Table\u00a04c axis via additional amine-N\u2014H\u22efS(thiol\u00adate) hydrogen-bonds, Fig.\u00a03b. Chains are connected via \u03c0\u2013\u03c0 inter\u00adactions occurring between Zn2-containing mol\u00adecules, involving chelate rings, comprising the Zn2/S4/C55/N11/N12 atoms and phenyl (C61\u2013C66) rings. Precedents for chelate/arene ring inter\u00adactions have been established in the literature  involving residues of the Zn1-containing mol\u00adecule exclusively, Table\u00a04c.The most prominent feature of the mol\u00adecular packing is the formation of an eight-membered heterosynthon, {\u22efHNCN\u22efHNCS}, mediated by amine-N\u2014H\u22efN(imine) and amine-N\u2014H\u22efS(thiol\u00adate) hydrogen-bonds which occur between the two mol\u00adecules comprising the asymmetric unit, Fig.\u00a03et al., 2016dnorm in Fig.\u00a04a and e, the bright-red spots near the amine-H1N, H7N, H10N, imime-N2 and thiol\u00adate-S2 and S3 atoms indicate their participation in N\u2014H\u22efN and N\u2014H\u22efS bonds between the two independent mol\u00adecules. In the views of the Hirshfeld surfaces mapped over electrostatic potential for the Zn1-mol\u00adecule in Fig.\u00a04b and c, and for the Zn2-mol\u00adecule in Fig.\u00a04f and g, the hydrogen-bond donors and acceptors are represented by blue and red regions, respectively. Greater insight into inter\u00admolecular inter\u00adactions in the crystal can be obtained by modifying the mapping range for dnorm, as shown in Fig.\u00a04d and h, which reveals additional characteristic spots on the surface. A pair of red spots near amine-HN4 and near phenyl-C7 and C8 in Fig.\u00a04d indicate the presence of short inter-atomic C\u22efH/H\u22efC contacts in the crystal, see Table\u00a05a and e, respectively. The immediate environments about the Zn1- and Zn2-mol\u00adecules within shape-index-mapped Hirshfeld surfaces highlighting hydrogen-bonding and C\u2014H\u22ef\u03c0 inter\u00adactions are illustrated in Fig.\u00a05a and 5b while the C\u2014H\u22ef\u03c0 and their reciprocal, i.e. \u03c0\u22efH\u2014C, contacts involving phenyl-C8 and C32 atoms as donors and phenyl (C31\u2013C36 and C13\u2013C18) rings as acceptors are shown in Fig.\u00a05c.The Hirshfeld surface calculations of (I)i.e. (I)a. In addition, the fingerprint plots delineated into H\u22efH, S\u22efH/H\u22efS, N\u22efH/H\u22efN, C\u22efH/H\u22efC,C\u22efN/N\u22efC and C\u22efC contacts  rings of Zn2-mol\u00adecules is evident from the presence of short inter-atomic Zn\u22efC/C\u22efZn contacts, Table\u00a05c, these contacts are reflected by a pair of points with an S-shaped distribution at around de + di \u223c1.9 to 2.1\u2005\u00c5. This \u03c0\u2013\u03c0 stacking is also apparent from the small but effective contributions from Zn\u22efC/C\u22efZn and C\u22efN/N\u22efC contacts to the Hirshfeld surface of the Zn2-mol\u00adecule, Table\u00a06The presence of a short inter-atomic C\u22efS contact between the thiol\u00adate-S3 and phenyl-C66 atoms is evident from the typical H-shaped plot in Fig.\u00a07et al., 2016i.e. of general formula Zn[SC(NHR)=NN=CR\u2032R\u2032\u2032]2 reflecting the inter\u00adest in this class of compound. All of the structures resemble the mol\u00adecular geometry described above for (I)i.e. R\u2032 = R\u2032\u2032 = Me for the R = Ph compound thio\u00adsemi\u00adcarbazide , was used without further purification and was dissolved in heated absolute ethanol (50\u2005ml). Zn(CH3COO)2\u00b72H2O  was dissolved separately in heated absolute ethanol (30\u2005ml) and then added into an ethano\u00adlic N-ethyl-N-thio\u00adsemicarbazide solution. The mixture was heated and stirred for about 10 mins, followed by stirring for 1\u2005h at room temperature. The obtained yellow precipitate was filtered, washed with cold ethanol and dried in vacuo. Single crystals were grown at room temperature from the slow evaporation of a solution of di\u00admethyl\u00adformamide and aceto\u00adnitrile (1:1 v/v 20\u2005ml).Analytical grade reagents were used as procured without further purification. Equimolar qu\u00adanti\u00adties of 4-ethyl-3-thio\u00adsemicarbazide  and 1,3-di\u00adphenyl\u00adprop-2-en-1-one  were dissolved in heated absolute ethanol (30\u2005ml) separately and the mixtures were mixed with stirring. About five drops of concentrated hydro\u00adchloric acid were added to the mixture to catalyse the reaction. The reaction mixture was kept under heating and stirring for about 10 mins, followed by stirring for 1\u2005h at room temperature. The resulting yellow precipitate was filtered off, washed with chilled absolute ethanol and dried Uiso(H) set to 1.2\u20131.5Ueq(C). The nitro\u00adgen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989017008064/hb7684sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017008064/hb7684Isup2.hklStructure factors: contains datablock(s) I. DOI: 1553218CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the centrosymmetric title compound features short N\u2014H\u22ef\u03c0 inter\u00adactions. 8H8N2, is generated by a crystallographic center of symmetry. In the crystal, short N\u2014H\u22ef\u03c0 [H\u22ef\u03c0 = 2.499\u2005(19)\u2005\u00c5] inter\u00adactions link the mol\u00adecules into a herringbone structure.The complete mol\u00adecule of the title compound, C The double bonds C1=C2 and C3=C4 in (I)versus the double-bond length in pyrrole of 1.357\u2005\u00c5. The shortening of the C2\u2014C3 bond and the lengthening of the adjacent C=C double bonds in (I)The complete mol\u00adecule of (I)1 screw axis is 2.499\u2005(19)\u2005\u00c5 \u00c5 Table\u00a01. A surveet al., 2015et al., 1997There are very few examples of similar compounds available in the literature. Most bi\u00adpyrroles have carbonyl groups as substituents on the pyrrole ring in which the N\u2014H group forms hydrogen bonds with the oxygen atom of the carbonyl (Okawara 230\u2005\u00b5l (3.3\u2005mmol) of pyrrole was added to di\u00adchloro\u00admethane (10\u2005ml), degassed and cooled to 195\u2005K. Tri\u00admethyl\u00adsilyl bromide  and phenyl iodine trifluoracetic acid  were added quickly to the cooled reaction. The mixture was stirred for 1\u2005h then extracted with a saturated sodium bicarbonate solution and purified by column chromatography with a penta\u00adne/ethyl acetate (1:1) solution. Colourless blocks of (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017013433/hb7692sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017013433/hb7692Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013433/hb7692sup3.pdfSurvey of the Cambridge Database NH-pi bond lengths. DOI: 1575394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound has a \u2018banana\u2019 shape, with the dihedral angle formed by the outer rings being 8.30\u2005(7)\u00b0. In the crystal, the three-dimensional architecture features nitro\u00adbenzene-C\u2014H\u22efO(carbon\u00adyl), pyrrole-C\u2014H\u22efO(nitro), \u03c0(pyrrole)\u2014\u03c0(nitro\u00adbenzene) and nitro-O\u22ef\u03c0(pyrrole) inter\u00adactions. 12H12N2O4, the di\u00adhydro\u00adpyrrole ring is almost planar (r.m.s. deviation = 0.0049\u2005\u00c5) and is nearly coplanar with the adjacent C2O2 residue [dihedral angle = 4.56\u2005(9)\u00b0], which links to the 4-nitro\u00adbenzene substituent [dihedral angle = 4.58\u2005(8)\u00b0]. The mol\u00adecule is concave, with the outer rings lying to the same side of the central C2O2 residue and being inclined to each other [dihedral angle = 8.30\u2005(7)\u00b0]. In the crystal, supra\u00admolecular layers parallel to (10-5) are sustained by nitro\u00adbenzene-C\u2014H\u22efO(carbon\u00adyl) and pyrrole-C\u2014H\u22efO(nitro) inter\u00adactions. The layers are connected into a three-dimensional architecture by \u03c0(pyrrole)\u2013\u03c0(nitro\u00adbenzene) stacking [inter-centroid separation = 3.7414\u2005(10)\u2005\u00c5] and nitro-O\u22ef\u03c0(pyrrole) inter\u00adactions.In the title compound, C The planarity extends to the 4-nitro\u00adbenzene ring, with the dihedral angle between the C2O2 and C6 planes being 4.58\u2005(8)\u00b0. However, the mol\u00adecule is not planar but rather is curved as the outer rings lie to the same side of the central C2O2 residue; the dihedral angle = 8.30\u2005(7)\u00b0. To a first approximation, the nitro group is co-planar with the benzene ring to which is connected, as seen in the value of the O4\u2014N2\u2014C10\u2014C9 torsion angle of 173.50\u2005(15)\u00b0.The mol\u00adecular structure of (I)3OCO}2 synthons. The dimeric aggregates are connected into a supra\u00admolecular layer via pyrrole-C4\u2014H\u22efO3(nitro) inter\u00adactions. The layers lie parallel to \u2013\u03c0(C7\u2013C12)i stacking inter\u00adactions occur between pyrrole and nitro\u00adbenzene rings: inter-centroid separation = 3.7414\u2005(10)\u2005\u00c5 and angle of inclination = 7.99\u2005(9)\u00b0 for symmetry code: (i): x, \u2212y, z. The other inter\u00adactions between layers are of the type nitro-O4\u22ef\u03c0, Table\u00a01et al., 2008b.The mol\u00adecular packing of (I)et al., 2017The Hirshfeld surface calculations for (I)dnorm in Fig.\u00a03B and ester-C5 atoms, respectively, Fig.\u00a04a. The other short inter\u00adatomic C\u22efH/H\u22efC contacts between the nitro\u00adbenzene-H11 and pyrrole-C2 and C3 atoms  contacts is highlighted in Fig.\u00a04b, showing the Hirshfeld surface mapped over the electrostatic potential.In addition to the bright-red spots on the Hirshfeld surface mapped over s Table\u00a02 are intret al., 2007a\u2013d, respectively, and the percentage contribution from the identified inter\u00adatomic contacts to the Hirshfeld surface are summarized in Table\u00a03i.e. 39.0%, contribution from H\u22efH contacts to the overall surface is due to the involvement of many hydrogen atoms in directional inter\u00admolecular inter\u00adactions, e.g. C\u2014H\u22efO, \u03c0 (Tables 1b). Conversely, the relatively significant contribution of 33.8% from O\u22efH/H\u22efO contacts to the Hirshfeld surface is consistent with this observation. The fingerprint plot delineated into O\u22efH/H\u22efO contacts  features a pair of green aligned points within the pair of spikes with their tips at de + di \u223c2.3\u2005\u00c5 superimposed upon a distribution blue points characterizing inter\u00admolecular C\u2014H\u22efO inter\u00adactions. The short inter\u00adatomic C\u22efH/H\u22efC contacts in the inter- and intra-layer regions are represented by the two pairs of short forceps-like spikes at de + di \u223c2.8 and 2.9\u2005\u00c5, respectively, in Fig.\u00a05d. The small but discernible contributions from inter\u00adatomic C\u22efC and C\u22efN/N\u22efC contacts 2 Di\u00adhydro\u00adpyrrole rings as found in (I)M solution, 10.56\u2005mmol) in dry toluene was then added. The bath was removed and the solution stirred for 2\u2005h at room temperature. Subsequently, the flask was immersed for 20\u2005min in an oil bath preheated to 393\u2013403\u2005K with a reflux condenser. The solution was concentrated in a rotary evaporator and the residue was purified by flash column chromatography on silica gel, using a mixture of EtOAc/n-hexane (1:4) as the eluent. The yield of (I)2Cl2 solution.A solution of (4-nitro\u00adphen\u00adyl)methyl 2-hy\u00addroxy\u00adpyrrolidine-1-carboxyl\u00adate  in toluene (100\u2005ml) was cooled to 273\u2005K in an ice/water bath. Under an atmosphere of nitro\u00adgen, 2,4-lutidine  was added to this solution. The solution was stirred for 15\u2005min at 273\u2005K. A tri\u00adfluoro\u00adacetic anhydride (TFAA) solution : \u03b4 8.21 , 7.54 , 6.80 and 6.68 , 5.35 , 5.03 , 3.71 , 2.46 . 13C NMR : \u03b4 = 152.3 (CO2R), 151.5 (CO2R), 147.8 (C4\u2032), 144.9 (C1\u2032), 129.8 (C2), 129.2 (C2), 128.4 (C2\u2032 and C6\u2032), 128.3 (C2\u2032 and C6\u2032), 123.9 (C3\u2032 and C5\u2032), 109.4 (C3), 65.8 (CH2), 65.6 (CH2), 45.8 (C5), 45.4 (C5), 30.1 (C4), 29.0 (C4). ESI\u2013MS (m/z) calculated for C12H12N2O4 248.07971, found 248.07876.Spectroscopic characterization. Uiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018002451/hb7736sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002451/hb7736Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018002451/hb7736Isup3.cmlSupporting information file. DOI: 1823263CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the 1:2 co-crystalline adducts are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions. 3,8]undecano (TATU) with 4-chloro-3,5-di\u00admethyl\u00adphenol led to the formation of the title co-crystal, C7H14N4\u00b72C8H9ClO. The asymmetric unit contains one aminal cage mol\u00adecule and two phenol mol\u00adecules linked via two O\u2014H\u22efN hydrogen bonds. In the aminal cage, the N\u2013CH2\u2013CH2\u2013N unit is slightly distorted from a syn periplanar geometry. Aromatic \u03c0\u2013\u03c0 stacking between the benzene rings from two different neighbouring phenol mol\u00adecules [centroid\u2013centroid distance = 4.0570\u2005(11)\u2005\u00c5] consolidates the crystal packing.Solvent-free treatment of 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00ad[4.3.1.1 Nitro\u00adgCg8\u22efCg9i = 4.0570\u2005(11); symmetry code: (i) x, y, Cgz; 8 and Cg9 are the centroids of the C11\u201316 and C21\u2013C26 rings, respectively] and the benzene ring planes are inclined to one another by 0.58\u2005(9)\u00b0. These additional contacts link the three-membered co-crystal units into chains approximately parallel to undecane hydro\u00adquinone   and 4-chloro-3,5-di\u00admethyl\u00adphenol  was ground using a mortar and pestle at room temperature for 15\u2005min. Completion of the reaction was monitored by TLC. The mixture was recrystallized from n-hexane solution to obtain colourless crystals suitable for X-ray analysis, m.p. = 375\u2013376\u2005K. (yield: 63%).A mixture of 1,3,6,8-tetra\u00adaza\u00adtri\u00adcyclo\u00ad[4.3.1.1Uiso(H) set to 1.2Ueq of the parent atom. The hydroxyl H atoms were refined freely.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016016650/sj5512sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016016650/sj5512Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510356CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation is five-coordinated in a distorted trigonal\u2013bipyramidal geometry. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (58.4%), H\u22efC/C\u22efH (20.3%) and H\u22efO/O\u22efH (18.3%) inter\u00adactions.In the title Zn complex, the Zn 10H11O2)2(C6H6N2O)2(H2O)], contains one half of the complex mol\u00adecule, and the ZnII cation and the water O atom lie on a twofold rotation axis. The ZnII cation is coordinated by two carboxyl\u00adate O atoms of the two symmetry-related 2,4,6-tri\u00admethyl\u00adbenzoate (TMB) anions and by the water O atom at distances of 2.0311\u2005(16) and 2.076\u2005(2)\u2005\u00c5 to form a slightly distorted trigonal\u2013planar arrangement, while the distorted trigonal\u2013bipyramidal coordination sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.2066\u2005(19)\u2005\u00c5 in the axial positions. In the crystal, mol\u00adecules are linked via inter\u00admolecular N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds with R22(12), R33(10) and R33(16) ring motifs, forming a double-column structure running along the c-axis direction. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (58.4%), H\u22efC/C\u22efH (20.3%) and H\u22efO/O\u22efH (18.3%) inter\u00adactions.The asymmetric unit of the title complex, [Zn(C A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels 2(C6H6N2O)2]  \u00b7H2O     (I)The transition metal complexes with ligands of biochemical inter\u00adest as imidazole and some II cation (site symmetry 2), one 2,4,6-tri\u00admethyl\u00adbenzoate (TMB) anion and one nicotinamide (NA) mol\u00adecule together with one water mol\u00adecule (point group symmetry 2), all ligands coordinating in a monodentate manner  1\u00a0\u2212\u00a0x, y, z] of the two symmetry-related monodentate TMB anions and the coordinating water O atom (O4) are at distances of 2.0311\u2005(16) and 2.076\u2005(2)\u2005\u00c5, respectively, around the Zn1 atom and form a slightly distorted triangular planar arrangement. The sum of the bond angles O2\u2014Zn1\u2014O2i [95.38\u2005(9)\u00b0], O2\u2014Zn1\u2014O4 [132.31\u2005(5)\u00b0] and O2\u2014Zn1\u2014O4i [132.31\u2005(5)\u00b0] in the basal plane around ZnII cation is 360\u00b0. This confirms the presence of the ZnII cation with very slight deviation from the basal plane. The slightly distorted trigonal\u2013bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of the two symmetry-related monodentate NA ligands at distances of 2.2066\u2005(19)\u2005\u00c5 in the axial positions. The index of trigonality \u03c4  and C1\u2014O2 [1.259\u2005(3)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements rather than localized single and double bonds. The O2\u2014C1\u2014O1 bond angle [121.8\u2005(2)\u00b0] seems to be slightly decreased than that present in a free acid [122.2\u00b0], in which the O2\u2014C1\u2014O1 bond angle may be compared with the corresponding values of 123.5\u2005(2) and 120.4\u2005(2)\u00b0 in (II), 125.2\u2005(5)\u00b0 in (III), 119.2\u2005(3) and 123.8\u2005(2)\u00b0 in (IV), 123.6\u2005(3) and 119.4\u2005(3)\u00b0 in (V), 124.4\u2005(2)\u00b0 in (VI) and 124.3\u2005(2)\u00b0 in (VII), where the benzoate ions coordinate to the metal atoms only monodentately in (III), (VI) and (VII), and both monodentately and bidentately in (II), (IV) and (V). The Zn1 atom lies 0.0817\u2005(1)\u2005\u00c5 above of the planar (O1/O2/C1) carboxyl\u00adate group. In the TMB anion, the carboxyl\u00adate group is twisted away from the attached benzene C2\u2013C7 ring by 61.32\u2005(14)\u00b0, while the benzene ring and the pyridine N1/C11\u2013C15 ring are oriented at a dihedral angle of 81.90\u2005(8)\u00b0.2 group links to the non-coordinating carboxyl\u00adate and NA oxygen atoms via inter\u00admolecular N\u2014H\u22efO hydrogen bonds, and the water mol\u00adecule links to the NA oxygen atoms via inter\u00admolecular O\u2014H\u22efO hydrogen bonds , the 18.3% contribution to the HS arises from the inter\u00admolecular O\u2014H\u22efO hydrogen bonding and is viewed as pair of spikes with the tip at de + di \u223c1.9\u2005\u00c5. The short H\u22efO/O\u22efH contacts are masked by strong O\u2014H\u22efO hydrogen bonding in this plot. The H\u22efN/N\u22efH contacts in the structure with 1.9% contribution to the HS has a symmetrical distribution of points with the tips at de + di \u223c2.8\u2005\u00c5 arising from the short inter\u00adatomic H\u22efN/N\u22efH contact . The HSs mapped over shape-index, curvedness and those with the function dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions are shown in Figs. s1\u2013s3 in the Supporting Information.A Hirshfeld surface (HS) analysis  in H2O (50\u2005ml) and nicotinamide  in H2O (25\u2005ml) with sodium 2,4,6-tri\u00admethyl\u00adbenzoate  in H2O (150\u2005ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for ten weeks, giving colourless single crystals . FT\u2013IR: 3396, 3111, 2953, 2919, 2740, 2321, 1947, 1693, 1665, 1621, 1601, 1584, 1445, 1397, 1199, 1113, 1047, 860, 839, 797, 731, 647, 614, 545, 559\u2005cm\u22121.The title compound was prepared by the reaction of ZnSO2 group were also located in a difference Fourier map and the positions were refined with Uiso(H) = 1.5Ueq(N). The C-bound H atoms were positioned geometrically with C\u2014H = 0.93 and 0.96\u2005\u00c5 for aromatic and methyl H-atoms, respectively, and refined as riding with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989017011690/is5478sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017011690/is5478Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017011690/is5478sup3.pdfHirsfeld surface plotted over shape-index. DOI: 10.1107/S2056989017011690/is5478sup4.pdfHirshfeld surface plotted over curvedness. DOI: 10.1107/S2056989017011690/is5478sup5.pdfHirshfeld surfaces plotted over dnorm. DOI: 1567723CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the isomeric title compounds, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bond, and C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions build different supra\u00admolecular architectures. 14H13Cl2NO2S, namely 3,5-di\u00adchloro-N--benzene\u00adsulfonamide (I), 3,5-di\u00adchloro-N-benzene\u00adsulfonamide (II) and 3,5-di\u00adchloro-N-benzene\u00adsulfonamide (III) are described. The mol\u00adecules of all the three compounds are U-shaped with the two aromatic rings inclined at 41.3\u2005(6)\u00b0 in (I), 42.1\u2005(2)\u00b0 in (II) and 54.4\u2005(3)\u00b0 in (III). The mol\u00adecular conformation of (II) is stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions. The crystal structure of (I) features N\u2014H\u22efO hydrogen-bonded R22(8) loops inter\u00adconnected via C(7) chains of C\u2014H\u22efO inter\u00adactions, forming a three-dimensional architecture. The structure also features \u03c0\u2013\u03c0 inter\u00adactions [Cg\u22efCg = 3.6970\u2005(14)\u2005\u00c5]. In (II), N\u2014H\u22efO hydrogen-bonded R22(8) loops are inter\u00adconnected via \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.606\u2005(3)\u2005\u00c5] to form a one-dimensional architecture running parallel to the a axis. In (III), adjacent C(4) chains of N\u2014H\u22efO hydrogen-bonded mol\u00adecules running parallel to [010] are connected via C\u2014H\u22ef\u03c0 inter\u00adactions, forming sheets parallel to the ab plane. Neighbouring sheets are linked via offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.8303\u2005(16)\u2005\u00c5] to form a three-dimensional architecture.The crystal structures of three isomeric compounds of formula C The structure also features \u03c0\u2013\u03c0 inter\u00adactions involving the benzene\u00adsulfonyl ring and the aniline ring as illustrated in Fig.\u00a04Cg1\u22efCg2iii = 3.6970\u2005(14)\u2005\u00c5; Cg1 and Cg2 are the centroids of the C1\u2013C6 and C7\u2013C12 rings, respectively; symmetry code: (iii) x, \u2212y, z].The crystal structure of (I)ps Fig.\u00a04. The (8)i hydrogen-bonded via \u03c0\u2013\u03c0 inter\u00adactions involving inversion-related benzene\u00adsulfonyl rings, forming a one-dimensional architecture running parallel to the a axis, as shown in Fig.\u00a05Cg1\u22efCg1ii = 3.606\u2005(3)\u2005\u00c5; Cg1 is the centroid of the C1\u2013C6 ring; symmetry code: (ii) 2\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, \u2212z].In (II)ps Fig.\u00a05 are connvia N1\u2014H1\u22efO1i hydrogen bonds  chains running parallel to [010]. Adjacent chains are connected by C14\u2014H14B\u22ef\u03c0 inter\u00adactions involving the aniline ring, forming two-dimensional sheets parallel to the ab plane. Neighbouring sheets are further linked via offset \u03c0\u2013\u03c0 inter\u00adactions involving inversion-related benzene\u00adsulfonyl rings, forming a three dimensional architecture as as illustrated in Fig.\u00a07Cg1\u22efCg1i = 3.8303\u2005(16)\u2005\u00c5, inter\u00adplanar distance = 3.3874\u2005(11)\u2005\u00c5, slippage 1.788\u2005(3)\u2005\u00c5; Cg1 is the centroid of the C1\u2013C6 ring; symmetry code: (iii) 1\u00a0\u2212\u00a0x, \u2212y, \u2212z].In the crystal structure of (III)ds Fig.\u00a06 to form N-(substitutedphen\u00adyl)-benzene\u00adsulfon\u00adamides, namely 3,5-di\u00adchloro-N-(4-methyl\u00adphen\u00adyl)benzene\u00adsulfonamide [Shakuntala, Naveen et al., 2017N-benzene\u00adsulfonamide [Shak\u00aduntala, Lokanath et al., 2017via N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, whereas in (V) the three-dimensional supra\u00admolecular architecture is built through N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, Cl\u22efCl contacts and \u03c0\u2013\u03c0 inter\u00adactions.Two 3,5-di\u00adchloro-et al., 2015The title compounds were prepared according to a literature method (Rodrigues Uiso(H) = 1.2 or 1.5Ueq(C). A rotating model was applied to the methyl groups. To improve considerably the values of R1, wR2, and S (goodness-of-fit), a low-angle reflection partially obscured by the beam-stop (100) was omitted from the final refinement of (III)Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017005230/rz5211sup1.cifCrystal structure: contains datablock(s) I, II, III, shelx. DOI: 10.1107/S2056989017005230/rz5211Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017005230/rz5211IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017005230/rz5211IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017005230/rz5211IIIsup7.cmlSupporting information file. DOI: 1542706, 1542704, 1542705CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C(6) helical chain running along the [100] direction.In the two independent mol\u00adecules in the asymmetric unit of the title compound, the cyclo\u00adhexane rings adopt a chair conformation, while the oxane rings are also puckered. In the crystal, O\u2014H\u22ef O hydrogen bonds connect adjacent mol\u00adecules, forming a  20H34O2, contains two crystallographically independent mol\u00adecules (1 and 2) with similar conformations. In both mol\u00adecules, the cyclo\u00adhexane rings adopt a chair conformation, while the oxane rings are also puckered. In the crystal, O\u2014H\u22efO hydrogen bonds connect adjacent mol\u00adecules, forming C(6) helical chains located around a 21 screw axis and running along the crystallographic a axis. The packing of these chains is governed only by van der Waals inter\u00adactions. Semi-empirical PM3 quantum chemical calculations are in a satisfactory agreement with the structural results of the X-ray structure analysis. The absolute structure was indeterminate in the present experiment.The asymmetric unit of the title compound, C Sideritis genus belonging to the Lamiaceae family is represented by more than 150 species in the world \u2005\u00c5, \u03b8 = 0.0\u2005(3), \u03c6 = 270\u2005(81)\u00b0 and QT = 0.584\u2005(3)\u2005\u00c5, \u03b8 = 4.4\u2005(3), \u03c6 = 59\u2005(4)\u00b0, respectively. The oxane ring (O2/C11/C12/C15\u2013C17) is also puckered, with puckering parameters QT = 0.551\u2005(3)\u2005\u00c5, \u03b8 = 12.1\u2005(3) and \u03c6 = 133.5\u2005(16)\u00b0. The equivalent rings in mol\u00adecule 2  have as puckering parameters QT = 0.534\u2005(3)\u2005\u00c5, \u03b8 = 1.9\u2005(3), \u03c6 = 296\u2005(11)\u00b0, QT = 0.583\u2005(3)\u2005\u00c5, \u03b8 = 5.0\u2005(3), \u03c6 = 72\u2005(3)\u00b0 and QT = 0.554\u2005(3)\u2005\u00c5, \u03b8 = 11.9\u2005(3), \u03c6 = 127.2\u2005(15)\u00b0, respectively. Bond lengths and angles are within normal range, comparable with each other and with those reported for similar structures in the literature  helical chains located around a 21 screw axis running along the crystallographic a axis  is a semi-empirical method for the quantum calculation of the mol\u00adecular electronic structure in computational chemistry. It is based on the neglect of differential diatomic overlap integral approximation. The semi-empirical PM3 parameterization used in the MOPAC program is widely used to derive charges, dipole moments and bond lengths. The computed quantum chemical descriptors include bond lengths, bond angles, torsion angles, atom charges, HOMO and LUMO energy levels, dipole moment, polarizability, etc. In the present case, the geometry of the mol\u00adecule of the title compound was calculated with a semi-empirical PM3 method , with the sole exception of the angles in the meth\u00adoxy groups. This may be ascribed to the steric inter\u00adactions between adjacent mol\u00adecules in the crystal structure.\u22121 flow rate. 16 fractions, each of which was 150\u2005mL, were collected. Similar fractions were combined according to the TLC profile. Further purification was carried out with silica gel column chromatography to isolate the title compound. Colourless prisms were recrystallized from ethanol solution.The aerial part of the plant material (5\u2005g) was extracted with ethyl acetate (3 \u00d7 20\u2005mL). After removal of the solvent by rotary evaporator, the extract was subjected to column chromatography (2.5 \u00d7 70\u2005cm); sephadex LH-20 (50\u2005g) was used as a stationary phase and methanol was used as a mobile phase with a 0.25\u2005ml\u2005minUiso fixed at 1.5 times Ueq(O). H atoms bound to carbon were positioned geometrically and allowed to ride on their parent atoms with Uiso = 1.2Ueq(C)  and with Uiso = 1.5Ueq(C) (C\u2014H = 0.96\u2005\u00c5) for methyl H atoms. The absolute structure was indeterminate in the present experiment.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016013864/bg2593sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016013864/bg2593Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016013864/bg2593sup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016013864/bg2593sup4.tifSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016013864/bg2593Isup5.cmlSupporting information file. DOI: 1501445CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecular and crystal structure of the title imidazole derivative is reported. The structure features an extensive O\u2014H\u22efN, C\u2014H\u22efO/N and C\u2014H\u22ef\u03c0(ring) hydrogen-bonding network. 24H21N3O3, crystallizes with two unique but closely r.m.s. overlay fit = 0.215\u2005\u00c5) comparable mol\u00adecules (1 and 2) in the asymmetric unit of the triclinic unit cell. In molecule 1, the dihedral angles between the central imidazlole ring and the benzene-ring substituents are 42.51\u2005(9), 45.41\u2005(9) and 56.92\u2005(8)\u00b0, respectively. Comparable data for molecule 2 are 39.36\u2005(10), 34.45\u2005(11) and 60.34\u2005(8)\u00b0, respectively. The rings at the 2-positions carry p-nitro substituents that subtend dihedral angles of 12.9\u2005(4)\u00b0 in mol\u00adecule 1 and 11.7\u2005(4)\u00b0 in mol\u00adecule 2 to their respective benzene ring planes. The imidazole rings also have propan-2-ol substituents on the 1-N atoms, which adopt extended conformations for the N\u2014C\u2014C\u2014C chains. In the crystal, classical O\u2014H\u22efN hydrogen bonds combine with C\u2014H\u22efO, C\u2014H\u22efN and C\u2014H\u22ef\u03c0(ring) hydrogen bonds and stack the molecules along the a-axis direction.The title compound, C The benzene rings are inclined to the imidazole ring plane at angles of 42.51\u2005(9) and 39.36\u2005(10)\u00b0 for C121\u2013C126 and C221\u2013C226, 45.41\u2005(9) and 34.45\u2005(11)\u00b0 for C141\u2013C146 and C241\u2013C246 and 56.92\u2005(8) and 60.34\u2005(8) for C151\u2013C156 and C251\u2013C256, values that further attest to the close similarities between the structures of the two unique mol\u00adecules. Bond lengths and angles in the two mol\u00adecules are also similar and compare well with those found in comparable mol\u00adecules with iso\u00adpropanol substituents at the 1-position  chains along the b-axis direction, Fig.\u00a03c, in this case head-to-head, due to C153\u2014H153\u22efCg5 and C255\u2014H255\u22efCg1 contacts  combined with C152\u2014H152\u22efO212, C153\u2014H153\u22efN21 and C256\u2014H256\u22efO112 hydrogen bonds, Fig.\u00a04via C243\u2014H243\u22efO23 hydrogen bonds, forming C(13) chains along a, Fig.\u00a05a. Overall, these numerous contacts generate layers of molecules of (I)a-axis direction, Fig.\u00a06In the crystal, classical O112\u2014H11et al., 20162 substituent on N1 are reasonably common with 43 entries. However, restricting the search to compounds with iso\u00adpropanol substituents on N1 reduces the hits to three reports of our work to produce compounds with 4-benzoic acid . All other atoms were refined using a riding model with d(C\u2014H) = 0.95\u2005\u00c5 for aromatic, 1.00\u2005\u00c5 for methine and 0.98\u2005\u00c5 for CH2 atoms, all with Uiso(H) = 1.2Ueq(C). For methyl H atoms d(C\u2014H) = 0.98\u2005\u00c5 and Uiso(H) = 1.5Ueq(C). One low angle reflection with Fo << Fc that may have been affected by the beamstop was omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017011057/hg5491sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017011057/hg5491Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011057/hg5491Isup3.cmlSupporting information file. DOI: 1565059CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I atom in the title compound is two-coordinate, being bound to two pyridine N atoms from two N-(pyridin-3-ylmeth\u00adyl)pyridin-3-amine ligands in a slightly distorted linear fashion. Each AgI ion bridges the dipyridyl-type ligands to form polymeric zigzag chains. The chains are connected via Ag\u22efAg and \u03c0\u2013\u03c0 inter\u00adactions, forming a corrugated layer parallel to ]PF6\u00b72CH3CN or {[AgL]\u00b7PF6\u00b72CH3CN}n, L = N-(pyridin-3-ylmeth\u00adyl)pyridin-3-amine, comprises one AgI atom, one L ligand, two aceto\u00adnitrile solvent mol\u00adecules and one PF6\u2212 anion disordered over two orientations in a 0.567\u2005(11):0.433\u2005(11) ratio. Each AgI atom is coordinated by two pyridine N atoms from two L ligands in a slightly distorted linear coordination geometry [N\u2014Ag\u2014N = 170.55\u2005(8)\u00b0]. Each L ligand bridges two AgI ions, resulting in the formation of a zigzag chain propagating along the [101] direction. In the crystal, Ag\u22efAg contacts [3.3023\u2005(5)\u2005\u00c5] and inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.5922\u2005(15)\u2005\u00c5] between the pyridine rings link these chains into a corrugated layer parallel to the \u2005\u00c5] between the layer and the inter\u00adcalated guests and between the inter\u00adcalated guests, forming a three-dimensional supra\u00admolecular network.The asymmetric unit in the title compound, [Ag(C The silver(I) atom is coordinated by two pyridine N atoms (N1 and N2) from two symmetry-related L ligands, leading to the formation of an infinite zigzag chain propagating along the [101] direction. Thus, the AgI atom is two-coordinated in a slightly distorted linear coordination geometry . All other H atoms were positioned geometrically and refined as riding: C\u2014H = 0.95\u2005\u00c5 for Csp2\u2014H, 0.99\u2005\u00c5 for methyl\u00adene C\u2014H and 0.98\u2005\u00c5 for methyl C\u2014H with Uiso(H) = 1.5Ueq (C-meth\u00adyl) and 1.2Ueq(C) for other C-bound H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017013421/su5393sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017013421/su5393Isup2.hklStructure factors: contains datablock(s) I. DOI: 1575393CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The di\u00adthio\u00adcarbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C2S4 donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn\u2014S bonds. Supra\u00admolecular chains aligned along the a-axis direction and sustained by methyl\u00adene-C\u2014H\u22efS(weakly coordinating) inter\u00adactions feature in the mol\u00adecular packing. A Hirshfeld surface analysis reveals the dominance of H\u22efH contacts in the crystal.The complete mol\u00adecule of the title compound, [Sn(C R2Sn(S2CNRR\u2032)2 is diverse with coordination geometries ranging from five, as in trigonal bipyramid (t-Bu)2Sn(S2CNMe2)2 2 Me]2, with a di\u00adthio\u00adcarbamate ligand with dissimilar substituents, was found to be octa\u00adhedral but, Ph2Sn[S2CN(CH2CH2OMe)2]2, with the di\u00adthio\u00adcarbamate ligand having similar substituents, was skew trapezoidal bipyramidal Me]2, (I)via an analysis of the Hirshfeld surface.The structural chemistry of mol\u00adecules with the general formula n-butyl groups lying on the plane, Fig.\u00a01i.e. the difference between the Sn\u2014Slong and Sn\u2014Sshort distances, being ca 0.39\u2005\u00c5, Table\u00a01n-butyl groups. The four S atoms are co-planar and define a skewed trapezoidal plane, and the \u03b1-C atoms are disposed over the weaker Sn\u2014S bonds so that the C2S4 donor set defines a skew trapezoidal bipyramidal geometry.The asymmetric unit of (I)a-axis direction, Fig.\u00a02a and Table\u00a02b. In order to ascertain more information of the nature of inter\u00adactions between mol\u00adecules, the mol\u00adecular packing and its Hirshfeld surface was analysed, as discussed in Hirshfeld surface analysis.The only notable contacts identified in the mol\u00adecular packing are methyl\u00adene-C\u2014H\u22efS(weakly coordinating) inter\u00adactions that assemble mol\u00adecules into linear supra\u00admolecular chains propagating along the et al., 2016dnorm, in the range \u22120.298 to +1.346 au, in Fig.\u00a03C and H13B of the disordered methyl groups, i.e. deviating from mirror symmetry, indicate their participation in specific inter\u00admolecular H\u22efH inter\u00adactions. In the crystal, these lead to a supra\u00admolecular chain along the c axis. The presence of this di\u00adhydrogen inter\u00adaction, resulting from disparate charges on respective hydrogen atoms, can also be viewed by the different curvatures and electrostatic potentials around these atoms on the Hirshfeld surface mapped over the electrostatic potential in the range \u22120.082 to +0.163 au, Fig.\u00a04dnorm, highlighting the inter\u00admolecular C\u2014H\u22efS and H\u22efH inter\u00adactions.The Hirshfeld surface analysis for (I)a, and those delineated  region, Fig.\u00a06a and b, show the dominance of these inter\u00adactions in the mol\u00adecular packing. The peak in the plot corresponding to a second short inter\u00adatomic H\u22efH contact, i.e. between methyl-H2B and methyl\u00adene-H10A, Table\u00a04B\u22efH13B inter\u00adaction. The di\u00adhydrogen H\u22efH bonding also results in short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a04de + di \u223c 2.8\u2005\u00c5 in the delineated fingerprint plot, Fig.\u00a06c; the other inter\u00adatomic short C\u22efH/H\u22efC contact is merged within the plot. The presence of the weak C\u2014H\u22efS inter\u00adactions, Table\u00a02d, and is evident as a pair of broad peaks at de + di \u223c 2.9\u2005\u00c5. The fingerprint plots delineated into O\u22efH/H\u22efO and N\u22efH/H\u22efN contacts, Fig.\u00a06e and f, contribute in a minor fashion to the Hirshfeld surface and their characteristic points are longer than their respective van der Waals separations, i.e. longer than 2.72 and 2.75\u2005\u00c5, respectively, and hence it is likely they do not make any significant contribution to the mol\u00adecular packing.In the fingerprint plot delineated into H\u22efH contacts, Fig.\u00a06b) that that H atoms adopt positions as far apart from each other as possible rather than participate in \u2018non-bonded steric repulsion\u2019 et al., 2016n-Bu2Sn(S2CNRR\u2019)2. One structure, i.e. R = R\u2032 = i-Pr , seven, i.e. R = Me, R\u2032 = n-Bu Me2 piperazine 2.The inter\u00adest in organotin di\u00adthio\u00adcarbamates is reflected in the relatively large number of crystal structures available in the crystallographic literature (Groom n-Bu2Sn(S2CNRR\u2032)2 is that they all conform to the same structural motif as adopted for (I)short bond lengths in these structures span a relatively narrow range of 2.51 to 2.55\u2005\u00c5 and cluster around 2.53\u2005\u00c5. As might be anti\u00adcipated, a wider range is exhibited by the Sn\u2014Slong bonds, i.e. 2.83 to 3.08\u2005\u00c5 and these cluster around 2.96\u2005\u00c5. Given the range of Sn\u2014Sshort bond lengths is 0.04\u2005\u00c5 and that for Sn\u2014Slong is 0.25\u2005\u00c5, the observation that differences between the average values of Sn\u2014Sshort and Sn\u2014Slong span a range of 0.43\u2005\u00c5 indicates no specific correlations exist between Sn\u2014Sshort and Sn\u2014Slong bond lengths. The Sshort\u2014Sn\u2014Sshort, Slong\u2014Sn\u2014Slong and C\u2014Sn\u2014C angles cluster around 83, 147 and 136\u00b0, respectively. However, these angles span ranges of 8\u00b0 (range: 80 to 88\u00b0), 10\u00b0 (140 to 151\u00b0) and 18\u00b0 (127 to 145\u00b0), respectively. The disparity in the S\u2014Sn\u2014S angles is as expected from the adopted coordination geometry. While, generally, the Slong\u2014Sn\u2014Slong angles are wider than the C\u2014Sn\u2014C angles, there are three exceptional structures, namely R = R\u2032 = Et 2 structural motif does not translate to the diphenyl analogues, i.e. Ph2Sn(S2CNRR\u2032)2. Of the 19 structures conforming to this general formula, seven resemble the skew trapezoidal bipyramidal motif with the majority, i.e. twelve, having a cis-disposition of the tin-bound phenyl substituents. In this context, it is noteworthy that all structures of the general formula Sn(S2CNRR\u2032)2X2, where X = halide, are invariably cis-S4X2 octa\u00adhedral 2 compounds.The homogeneity in the ca 277\u2005K) for 30\u2005min. 25% Ammonia solution (ca 2\u2005ml) was added to make the solution basic. Then, a cold ethanol solution of carbon di\u00adsulfide (10\u2005mmol) was added to the solution followed by stirring for about 2\u2005h. Next, di-n-butyl\u00adtin(IV) dichloride (5\u2005mmol), dissolved in ethanol (30\u2005ml), was added to the solution which was further stirred for 2\u2005h. The precipitate that formed was filtered and then washed three times with cold ethanol to remove any impurities. The precipitate was then dried in a dessicator. The compound was crystallized in a mixture of chloro\u00adform and ethanol (1:2 v/v) at room temperature to give colourless slabs. Yield: 66%, m.p. 333\u2013336\u2005K. Analysis. Found C, 40.3; H, 7.3; N, 5.0; S, 22.8. C18H38N2O2S4Sn requires: C, 38.5; H, 6.8; N, 5.0; S, 23.7. IR (cm\u22121): 1490 \u03bd(C\u2014N), 991 \u03bd(C\u2014S), 553 \u03bd(Sn\u2014C), 420 \u03bd(Sn\u2014S). 1H NMR (CDCl3): 7.40\u20137.74 , 4.07 , 3.71 , 3.46 , 3.40 , 2.04 , 1.92 , 1.44 , 0.98 . 13C{1H} NMR (CDCl3): \u03b4 201.2 (S2C), 70.1 (OCH2), 59.1 (NCH2), 56.6 (OCH3), 44.5 (NCH3), 34.3 (SnCH2), 28.6 (SnCH2CH2), 26.5 (CH2CH3), 13.9 (CH2CH3). 119Sn{1H} NMR (CDCl3): 338.6.(2-Meth\u00adoxy\u00adeth\u00adyl)methyl\u00adamine (10\u2005mmol) dissolved in ethanol (30\u2005ml) was stirred in an ice bath (Uiso(H) set to 1.2\u20131.5Ueq(C). The mol\u00adecule has crystallographic mirror symmetry with the Sn atom and n-butyl-C atoms lying on the plane. The terminal CH2CH3 residue of each n-butyl group is statistically disordered across this plane. Owing to poor agreement, three reflections, i.e. (172), (124) and (155), were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989017001098/hb7654sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017001098/hb7654Isup2.hklStructure factors: contains datablock(s) I. DOI: 1528948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the complex mol\u00adecules inter\u00adact with the caffeine mol\u00adecules through O\u2014H\u22efN, O\u2014H\u22efO, C\u2013H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions.In the structure of the title compound, , [Co(NCS)2(H2O)4]\u00b72C8H10N4O2\u00b74H2O, the cobalt(II) cation lies on an inversion centre and is coordinated in a slightly distorted octa\u00adhedral geometry by the oxygen atoms of four water mol\u00adecules and two N atoms of two trans-arranged thio\u00adcyanate anions. In the crystal, the complex mol\u00adecules inter\u00adact with the caffeine mol\u00adecules through O\u2014H\u22efN, O\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid-to-centroid distance = 3.4715\u2005(5)\u2005\u00c5], forming layers parallel to the ab plane, which are further connected into a three-dimensional network by O\u2014H\u22efO and O\u2014H\u22efS hydrogen bonds involving the non-coordinating water mol\u00adecules.In the structure of the title compound [systematic name: tetra\u00adaqua\u00adbis\u00ad(thio\u00adcyanato-\u03ba The cobalt(II) cation lies on an inversion centre and displays a trans-arranged octa\u00adhedral coordination geometry provided by the N atoms of two thio\u00adcyanate anions and four O atoms of coordinating water mol\u00adecules. The Co1\u2014N15 [2.0981\u2005(8)\u2005\u00c5] and Co1\u2014O18 [2.0981\u2005(7)\u2005\u00c5] bond lengths are equal within standard uncertainties and significantly longer than the Co1\u2013O19 bond length [2.0732\u2005(7)\u2005\u00c5], and therefore the CoN2O4 octa\u00adhedron is slightly axially compressed. This structural feature is typical for related compounds \u2005\u00c5; Cg is the centroid of the N3/N7/C4/C6/C8/C9 ring; symmetry code: (i) 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z; Fig.\u00a02In the crystal, each complex mol\u00adecule inter\u00adacts with four neighboring caffeine mol\u00adecules through classical O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds Table\u00a01 involvin2\u00b76H2O  in 5\u2005ml of water and caffeine  in 10\u2005ml of ethanol was added to a solution of potassium thio\u00adcyanate  in 5\u2005ml of water. Single crystals of the title compound suitable for X-ray analysis were grown after several months by slow evaporation of the solvent at room temperature.In a glass tube, a solution of CoClUiso(H) set at 1.2\u20131.5 times of the Ueq of the parent atom, after which the positions were refined with riding constraints  global, I. DOI: 10.1107/S2056989017008180/rz5216Isup2.hklStructure factors: contains datablock(s) I. DOI: 1553654CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this study, we investigated the proliferation and activation of lung \u03b3\u03b4 T cell subsets, specifically the IL-17 and IFN\u03b3 production by them following Cm lung infection. Our results found that five \u03b3\u03b4 T cell subsets, V\u03b31+ T, V\u03b32+ T, V\u03b34+ T, V\u03b35+ T, and V\u03b36+ T, expressed in lungs of na\u00efve mice, while Cm lung infection mainly induced the proliferation and activation of V\u03b34+ T cells at day 3 p.i., following V\u03b31+ T cells at day 7 p.i. Cytokine detection showed that Cm lung infection induced IFN\u03b3 secretion firstly by V\u03b34+ T cells at very early stage (day 3) and changed to V\u03b31+ T cells at midstage (day 7). Furthermore, V\u03b34+ T cell is the main \u03b3\u03b4 T cell subset that secretes IL-17 at the very early stage of Cm lung infection and V\u03b31+ T cell did not secrete IL-17 during the infection. These findings provide in vivo evidence that V\u03b34+T cells are the major IL-17 and IFN\u03b3-producing \u03b3\u03b4 T cell subsets at the early period of Cm lung infection.Our previous studies showed that  C. pneumoniae causes respiratory diseases like bronchitis, sinusitis, and pneumonia, whereas C. trachomatis is a major cause of ocular and sexually transmitted diseases  and 2\u2009mg/ml collagenase type XI ) for 60\u2009min at 37\u00b0C and added 2\u2009mM EDTA 5\u2009min before incubation finished. Then the cell population was purified by mixing with 35% Percoll (Sigma-Aldrich) and centrifuged for 20\u2009min at 750\u2009g, followed by lysis of erythrocytes with ammonium chloride-potassium (ACK) lysis buffer . The cells were washed twice using RPMI 1640 with 2% fetal calf serum and resuspended in complete RPMI 1640 medium (containing 10% FBS) for further experiment.Lung mononuclear cells were prepared as described previously . Briefly\u03b3 transcripts, total RNA was extracted from frozen lung tissues using Trizol agent (Invitrogen) according to the manufacturer's instruction. The isolated total RNA was reversely transcribed into cDNA (TaKaRa). Special primers for V\u03b31, V\u03b32, V\u03b34, V\u03b35, V\u03b36, and V\u03b37 were used to amplify cDNA. And \u03b2-actin, a housekeeping gene, was used as a control. The primers used in the PCR analysis were as follows: V\u03b31 (320\u2009bp), forward: 5\u2032-ACACAGCTATACATTGGTAC-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; V\u03b32 (270\u2009bp), forward: 5\u2032-CGGCAAAAAACAAATCAACAG-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; V\u03b34 (310\u2009bp), forward: 5\u2032-TGTCCTTGCAACCCCTACCC-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; V\u03b35 (300\u2009bp), forward: 5\u2032-TGTGCACTGGTACCAACTGA-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; V\u03b36 (300\u2009bp), forward: 5\u2032-TGTGCACTGGTACCAACTGA-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; V\u03b37 (380\u2009bp), forward: 5\u2032-AAGCTAGAGGGGTCCTCTGC-3\u2032, reverse: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032; \u03b2-actin (582\u2009bp), forward: 5\u2032-CTTATGGAGATTTGTTTCAGC-3\u2032, reverse: 5\u2032-ATGAGGTAGTCMGTCAGGT-3\u2032. The products were electrophoresed in 1% agarose gel containing Gel-Red (0.01%). The bands were visualized and photographed by automatic gel imaging system and were analyzed for density on Image J software.To analyze the expressions of TCR V\u03b3\u03b4, anti-CD69, anti-TCRV\u03b31, anti-TCRV\u03b34, and isotype control Abs for 30\u2009min on ice for surface marker analysis. For intracellular cytokine analysis, single cell suspensions were stimulated with PMA (50\u2009ng/ml)/ionomycin (1\u2009\u03bcg/ml) (Sigma) for 6 hours at 37\u00b0C in the presence of 20\u2009mg/ml brefeldin A (Sigma). After the stimulation, cells were washed with FACS buffer twice and incubated with Fc receptor (FcR) block antibodies  for 15\u2009min on ice to block nonspecific staining. Surface markers  were stained first. The cells were then fixed with 4% w/v paraformaldehyde in PBS and permeabilized with permeabilization buffer , subsequently stained with anti-IFN\u03b3, IL-17, or corresponding isotype control Abs (eBioscience). The raw data were collected using FACS CantoII flow cytometer (BD Biosciences) and were analyzed using Flowjo 6.0 software.Lung mononuclear cells were aseptically prepared from mice at different time points postinfection and incubated with anti-CD3, anti-TCRt-test were used to determine statistical significance among groups. IFUs of Cm were converted to logarithmic values and analyzed using ANOVA. The value of p < 0.05 was considered as a statistically significant difference.One-way analysis of variance (ANOVA) and unpaired \u03b3\u03b4 T cells are the vital components of the innate immune system and play important roles in the early responses to pathogens. Our previous studies have shown that \u03b3\u03b4 T cells are the major producer of IL-17A in the very early stages of infection and depletion of \u03b3\u03b4 T cells by administration of mAb (GL3) against TCR\u03b3\u03b4 i.n. exists more body weight loss following Cm lung infection. The results here keep consistent with our previous studies that the percentage and absolute number of lung \u03b3\u03b4 T cells significantly increased at day 3 postinfection (p.i.) and reached to the highest level at day 7 p.i. Even though the percentage of \u03b3\u03b4 T cells reduced to baseline levels, the absolute number of \u03b3\u03b4 T cells still kept in a relatively higher level . All these results implicated that \u03b3\u03b4 T cells contribute to the IFN\u03b3 and IL-17 production and reduce morbidity during Cm infection, but its role in bacterial clearance is rather limited. Figures . CD69 wa Figures . TCR\u03b4\u2212/\u2212o 6 p.i. ; howeverfference . Further\u03b3\u03b4 T cells are heterogeneous population that can be subdivided based on the expression of specific V\u03b3 and V\u03b4 TCR chains. Although we already demonstrated the importance of \u03b3\u03b4 T cell in the early protection against Cm lung infection, this did not prove that \u03b3\u03b4 T cell subpopulation actually contributes to the \u03b3\u03b4 T cell-mediated early protection. To investigate this, we first analyzed the \u03b3\u03b4 T cell subsets in lungs of naive mice. Our results by using RT-PCR detection showed that there are more than five subpopulations, V\u03b31+ T, V\u03b32+ T, V\u03b34+ T, V\u03b35+ T, and V\u03b36+ T but not V\u03b37+ T cells; in lungs of naive mice, the expression intensity of mRNA is V\u03b32\u2009>\u2009V\u03b34\u2009>\u2009V\u03b31\u2009>\u2009V\u03b36\u2009>\u2009V\u03b35  while V\u03b31 T cells at midstage p.i. (day 7)  against TCR\u03b3\u03b4 i.n. exists more body weight loss following Cm lung infection, which suggested that \u03b3\u03b4 T cells played a protective role in mice Chlamydia lung infection [\u03b4\u2212/\u2212 mice in this paper. It is worth mentioning that \u03b3\u03b4 T cell is the highest producer of IL-17A but the protection conferred by IL-17A is mainly mediated by Th17 cells following Cm infection. Therefore, the protective role of early production of IL-17 and IFN\u03b3 by V\u03b34+ T and V\u03b31+ T cells is not essential but supplementary in clearance of Chlamydia. In our present study using Cm infection model, it was found that V\u03b34+ T cells were the major source of IL-17 in the early stage, and V\u03b31+ T cells did not secrete IL-17. Similarly, Listeria monocytogenes also induces \u03b3\u03b4 T cells, especially V\u03b34+ T and V\u03b36+ T cells, and secretes IL-17 in infected liver, but more than 60 percent of the IL-17 are produced by V\u03b36+ T cell, which have fast kinetic response characteristics [\u03b31+ \u03b3\u03b4 T-cell reactivity which dominantly produces IL-17. Furthermore, with anti-CD3 antibody and virus-LPS stimulation in vitro, V\u03b31+ T cells dramatically produced IL-17, while only IL-10+ V\u03b34+ T cells existed [\u03b3\u03b4 T cell in varieties of pathogen infections are not always the same pattern, while these data suggest increased numbers of \u03b3\u03b4 T cells with cytokine-producing potential during immune response; any role for \u03b3\u03b4 T cell-derived cytokines in various model remains to be defined.The effector functions of le genes . IL-17-pfections , 36, 37.nfection . These reristics . However existed . Unlike \u03b34-\u03b3\u03b4 T cell subsets which is not identified during Cm infection. Interestingly, in our model, V\u03b36+ cells also present to proliferate following the Cm infection at the middle stage, which might be an important IL-17-producing cell after the early infection stage. IL-17+ V\u03b36+ T cells promote cancer cell growth by mobilizing peritoneal macrophages in the mice model of ovarian cancer [Listeria monocytogenes, more than 60 percent of the IL-17 are produced by V\u03b36+ T cell in infected liver, which have fast kinetic response characteristics [\u03b36+ T cell because it is reported that V\u03b36+ cells are the major \u03b3\u03b4 T cell population in reproductive tract but not in lungs [\u03b3 and IL-17 may be partially secreted by V\u03b36+ T cells apart from V\u03b31+ T and V\u03b34+ T cells during Cm infection.Notably, there are still a small number of IL-17-producing-Vn cancer . In Listeristics . In thisin lungs . But it \u03b31+ T and V\u03b34+ T cells are the major proliferative cell subsets of \u03b3\u03b4 T cell during Cm lung infection in mice. Moreover, V\u03b34+ T cells are the major IL-17 and IFN\u03b3-producing \u03b3\u03b4 T cell subsets at the early period of Cm lung infection. The findings in the present study provide new insights into the mechanisms bridging innate and adaptive immunity during lung chlamydial infections, which may have implications in developing effective chlamydial vaccines and in the understanding of host defense mechanisms in other lung infections.In conclusion, our data show that V"}
{"text": "C(4) along [100] and and There are two mol\u00adecules in the asymmetric unit of the title compound, one of them being disordered over the methyl group. The mol\u00adecules are linked by weak H\u22efS inter\u00adactions into chains with graph-set motifs  13H17N3S, one of them being disordered over the methyl group [site-occupancy ratio = 0.705\u2005(5):0.295\u2005(5)]. The maximum r.m.s. deviations from the mean plane of the non-H atoms for the tetra\u00adlone fragments amount to 0.4572\u2005(17) and 0.4558\u2005(15)\u2005\u00c5. The N\u2014N\u2014C\u2014N fragments are not planar and torsion angles are \u22129.4\u2005(2) and 8.3\u2005(2)\u00b0. In the crystal, the mol\u00adecules are linked by weak N\u2014H\u22efS inter\u00adactions into chains along [100] with graph-set motif C(4) and connected by weak N\u2014H\u22efS and C\u2014H\u22efS inter\u00adactions, forming R21(10) rings. The Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are the H\u22efH (64.20%), H\u22efS (12.60%) and H\u22efC (12.00%) inter\u00adactions. The crystal packing resembles a herringbone arrangement when viewed along [001].There are two crystallographically independent mol\u00adecules in the asymmetric unit of the title compound, C In the 1940s it was reported that in in vitro assays, the thio\u00adsemicarbazone turned out to be very effective against tuberculosis. In contrast, the related oxygen-containing semicarbazones did not shown biological activity in the same assays, so that the sulfur atom in the mol\u00adecular structure is essential for Mycobacterium tuberculosis growth inhibition, a true milestone in the thio\u00adsemi\u00adcarbazone pharmacological research :0.295\u2005(5) with ed Fig.\u00a01.For the first mol\u00adecule, the C1/C2/C5/C10 atoms are essentially planar and atoms C3 and C4 deviate by 0.564\u2005(2) and \u22120.142\u2005(2)\u2005\u00c5, respectively, from this plane. For the second, the C14/C15/C18/C23 atoms are essentially planar while atoms C16 and C17 deviate from the plane by \u22120.534\u2005(2) and 0.201\u2005(2)\u2005\u00c5, respectively.In addition, the N1\u2014N2\u2014C11\u2014N3 and N4\u2014N5\u2014C24\u2014N6 torsion angles are 9.4\u2005(2)\u00b0 and 8.3\u2005(2)\u00b0. The dihedral angle between the tetra\u00adlone fragments of the two mol\u00adecules within the asymmetric unit is 85.51\u2005(02)\u00b0.i inter\u00adactions into chains along [100]. The S1\u2013C11\u2013N3\u2013H12 and S2\u2013C24\u2013N6\u2013H29 fragments are the subunits of the periodic arrangement, with graph-set motif C(4). In addition, the mol\u00adecules are linked by C9\u2014H10\u22efS2 and C22\u2014H27\u22efS1i inter\u00adactions building rings with graph-set motif D\u2014H\u22efS inter\u00adactions  and di (x axis) values are the closest external and inter\u00adnal distances (in \u00c5) from given points on the Hirshfeld surface contacts hydrazinecarbo\u00adthio\u00adamide, the mol\u00ad\u00adecules are linked into chains by N\u2014H\u22efS hydrogen bonds (H\u22efS distances = 2.45 and 2.71\u2005\u00c5) and the H\u22efS contribution for the cohesion of the structure amounts to 19.20% . This kind of arrangement, the one-dimensional hydrogen-bonded polymer, is possible due to the unsubstituted amine, which increases the possibilities for inter\u00admolecular hydrogen bonding hydrazinecarbo\u00adthio\u00adamide, one H atom of the amine group is substituted by one methyl group. The N\u2014H\u22efS hydrogen bonds are weaker in comparison with the first structure (H\u22efS distances = 3.03 and 3.29\u2005\u00c5), the H\u22efS contribution for the cohesion of the structure amounts to 15.80% and the dimensionality of the structure is preserved with mol\u00adecules linked into chains . The disorder over the mol\u00adecules in the asymmetric unit was not considered and the calculations were performed using atoms of the major occupancy component hydrazinecarbo\u00adthio\u00adamide, the mol\u00adecules are also linked by N\u2014H\u22efS hydrogen bonds, but not into hydrogen-bonded polymers (H\u22efS distance = 2.70\u2005\u00c5). The phenyl rings linked to the amino groups change the mol\u00adecular arrangement due to steric effects: the mol\u00adecules build dimers and the H\u22efS contribution to the crystal packing amounts to 13.00%  . Thus, there is a relationship between the mol\u00adecular assembly, the geometry of the H\u22efS inter\u00adactions and their contribution to the crystal structures  and two positions will be possible for the terminal CH3\u2013group. The C25 and C26 atoms were fixed with restraints (SADI command) and had to be split over two positions. The occupancy factor for C25A and C26A is 0.705\u2005(5) and for C25B and C26B it is 0.295\u2005(5). H atoms were located in difference maps but were positioned with idealized geometry and were refined with isotropic displacement parameters using a riding model (HFIX command) with Uiso(H) = 1.2Ueq(secondary C atoms) , Uiso(H) = 1.5 Ueq (C\u2014H = 0.98\u2005\u00c5) and Uiso(H) = 1.2 Ueq(N) (N\u2014H = 0.88\u2005\u00c5). Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017001311/lh5835sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989017001311/lh5835Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017001311/lh5835Isup3.cmlSupporting information file. DOI: 1529622CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "By contrast, analogous syntheses from o\u2010xylene and m\u2010xylene as the solvent yield the solvent\u2010free coordination polymer [Ag4(O2CCF3)4(phen)2] (2). Toluene, p\u2010xylene and benzene have been successfully used in mixed\u2010arene syntheses to template the formation of coordination polymers 1\u22c5phen\u22c5arene, which incorporate o\u2010 or m\u2010xylene. The selectivity of 1\u22c5phen\u22c5arene for the arene guests was determined, through pairwise competition experiments, to be p\u2010xylene>toluene\u2248benzene>o\u2010xylene>m\u2010xylene. The largest selectivity coefficient was determined as 14.2 for p\u2010xylene:m\u2010xylene and the smallest was 1.0 for toluene:benzene.The coordination polymers [Ag Materials that are porous on the molecular scale have been in use for many years in applications involving molecular separation. Fixed\u2010pore materials, exemplified by zeolites and related inorganic porous materials,4{O2C(CF2)2CF3}4(phen)2(arene)n]\u22c5m\u2009(arene) (phen=phenazine) and examined the role of these guests in templating solid\u2010state transformations.o\u2010xylene, m\u2010xylene and p\u2010xylene by the coordination polymer [Ag4(O2CCF3)4(phen)3] (1) during its self\u2010assembly from the solution phase. This results in the crystalline materials [Ag4(O2CCF3)4(phen)3]\u22c5phen\u22c5arene (1\u22c5phen\u22c5arene), in which the arenes act as co\u2010guests alongside non\u2010coordinated phenazine. Specifically, we are able to establish the selectivity of the coordination polymer for each of the five arenes by determination of the pairwise selectivity coefficients, and are able to determine the potential of this material in separation of structurally similar arenes by recycling of the encapsulation process.We have developed a class of 1D coordination polymers based on silver(I) perfluoroalkylcarboxylate dimer units linked through diimine ligands, such as substituted pyrazine or phenazine  is important commercially due to the large scale on which such compounds are synthesised for use as precursors in the chemical industry, combined with the non\u2010regiospecific manner in which alkylarenes, such as xylenes, are synthesised. Their similarity in physical properties  makes conventional methods of separation, such as distillation, a difficult and not very cost\u2010effective approach.p\u2010xylene or benzene resulted in exclusive formation of the corresponding arene\u2010guest\u2010containing 1D coordination polymer [Ag4(O2CCF3)4(phen)3]\u22c5phen\u22c5arene (1\u22c5phen\u22c5arene). Phase purity was confirmed by elemental analysis and Pawley fitting of the corresponding X\u2010ray powder patterns. Crystal structures of [Ag4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009(toluene) (1\u22c5phen\u22c5tol), [Ag4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009(p\u2010xylene) (1\u22c5phen\u22c5pxyl) and [Ag4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009C6H6 (1\u22c5phen\u22c5benz) were determined by single\u2010crystal X\u2010ray diffraction 4(L)3]  described in our previous work.1\u22c5phen\u22c5arene material additional non\u2010coordinated phenazine molecules are included as guests, situated between each of the doubly\u2010bridging phenazine linkers in a \u03c0\u2010stacked manner. Two equivalents of the arene used as solvent are also present as guests per repeat unit of the polymer. These molecules  are \u03c0\u2010stacked on both sides of the electron\u2010deficient central ring of the singly\u2010bridging phenazine ligands. The arenes are crystallographically ordered and each arene molecule is related to another by a centre of symmetry located in the centre of those phenazine ligands  trifluoroacetate in methanol onto a solution of phenazine dissolved in either toluene, o\u2010 and m\u2010xylene, however, did not yield the analogous 1D coordination polymer. Rather, these syntheses led exclusively to the 2D coordination polymer [Ag4(O2CCF3)4(phen)2] (2), which excludes the xylene guests. This more densely\u2010packed phase is propagated in one dimension by an extended arrangement of silver perfluoroacetate units that employ both the anti and syn lone pairs on the carboxylate oxygen in coordination to AgI centres,Analogous syntheses conducted using p\u2010xylene and benzene) were included in the self\u2010assembly of 1\u22c5phen\u22c5arene, the selectivity of this inclusion process was examined by means of pairwise competition experiments between the three arenes. This was achieved by conducting the assembly of 1\u22c5phen\u22c5arene in the presence of a 1:1 mixture (by volume) of two of the three possible pairs of arenes. Pawley fitting of X\u2010ray powder diffraction confirmed the formation of 1\u22c5phen\u22c5arene, along with a very small amount of 2.6]DMSO, and studying the resulting solution by 1H\u2005NMR spectroscopy and gas chromatography (GC). These data and their analyses are presented in full in the Supporting Information. Pairwise selectivity constants, KA:B were determined from the corresponding inclusion experiments \u22c5phen\u22c52\u2009(toluene) (1\u22c5phen\u22c5tol)\u22c5phen\u22c52\u2009(p\u2010xylene) (1\u22c5phen\u22c5pxyl)\u22c5phen\u22c52\u2009C6H6 (1\u22c5phen\u22c5benz)\u22c5phen\u22c52\u2009{(toluene)0.73\u22c5(p\u2010xylene)0.27} (1\u22c5phen\u22c5 tol\u22c5pxyl)\u22c5phen\u22c52\u2009{(toluene)0.49\u22c5(p\u2010xylene)0.51} (1\u22c5phen\u22c5 tol\u22c5pxyl)\u22c5phen\u22c52\u2009{(toluene)0.38\u22c5(p\u2010xylene)0.62} (1\u22c5phen\u22c5 tol\u22c5pxyl)\u22c5phen\u22c52\u2009{(toluene)0.30\u22c5(p\u2010xylene)0.70} (1\u22c5phen\u22c5 tol\u22c5pxyl)\u22c5phen\u22c52\u2009{(toluene)0.14\u22c5(p\u2010xylene)0.86} (1\u22c5phen\u22c5 tol\u22c5pxyl)\u22c5phen\u22c52\u2009{(toluene)0.46\u22c5(C6H6)0.54} (1\u22c5phen\u22c5tol\u22c5 benz)\u22c5phen\u22c52\u2009{(p\u2010xylene)0.58\u22c5(C6H6)0.42} (1\u22c5phen\u22c5 pxyl\u22c5benz)\u22c5phen\u22c52\u2009{(C6H6)0.81\u22c5(o\u2010xylene)0.19} (1\u22c5phen\u22c5 C6H6\u22c5oxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) benzene:o\u2010xylene (8\u2005mL). Yield 40\u2009% .4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009{(C6H6)0.91\u22c5(m\u2010xylene)0.09} (1\u22c5phen\u22c5C6H6\u22c5mxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) benzene:m\u2010xylene (8\u2005mL) . Yield 40\u2009% .4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009{(toluene)0.84\u22c5(o\u2010xylene)0.16} (1\u22c5phen\u22c5 tol\u22c5oxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) toluene:o\u2010xylene (8\u2005mL). Yield 33\u2009% .4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009{(toluene)0.91\u22c5(m\u2010xylene)0.09} (1\u22c5phen\u22c5tol\u22c5mxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) toluene:m\u2010xylene (8\u2005mL). Yield 32\u2009% .4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009{(p\u2010xylene)0.90\u22c5(o\u2010xylene)0.10} (1\u22c5phen\u22c5pxyl\u22c5oxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) p\u2010xylene:o\u2010xylene (8\u2005mL). Yield 42\u2009% .4(O2CCF3)4(phen)3]\u22c5phen\u22c52\u2009{(p\u2010xylene)0.96\u22c5(m\u2010xylene)0.04} (1\u22c5phen\u22c5pxyl\u22c5mxyl)[Ag: A 0.05\u2009m solution of AgO2CCF3  in methanol (8\u2005mL) was layered on to a 0.05\u2009m solution of phenazine  in 1:1 (v/v) p\u2010xylene:m\u2010xylene (8\u2005mL). Yield 45\u2009% .2(O2CCF3)2(phen)] (2)DMSO, then filtered through cotton wool. 1H\u2005NMR spectra were measured on a Bruker AV 400\u2005MHz spectrometer. The NMR spectra can be found in the Supporting Information, Section 4. The NMR spectra were analysed using the Bruker TOPSPIN 3.1 programme. Methyl peaks for mixed xylene systems, which did not show complete baseline separation, were deconvoluted using the mixed\u2010line descriptor (mixed Lawrencian & Gaussian) deconvolution function in TOPSPIN.Gas chromatography: The solutions used for 1H\u2005NMR were transferred to glass vials using crimped caps, and then analysed using a PerkinElmer Autosystem GC with an AlltechTM HeliflexTM AT\u20101 capillary column (L\u00d7I.D. 30\u2005m\u00d70.32\u2005mm\u00d7df 5.00\u2005\u03bcm), heating from 40 to 200\u2009\u00b0C at 10\u2009\u00b0C min\u22121. Expected guest retention times were found to be 9.9\u2005min (benzene), 12.7\u2005min (toluene), 15.1\u2005min (p\u2010xylene), 15.2\u2005min (m\u2010xylene\u2010indistinguishable from p\u2010xylene) and 15.7\u2005min (o\u2010xylene). Relative content of guests was determined by direct comparison of chromatogram peak areas. The gas chromatograms can be found in the Supporting Information.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "In their respective crystals, hydrogen bonding leads to dimeric aggregates in the former (O\u2014H\u22efS) and supra\u00admolecular chains in the latter .Highly-distorted five-coordinate NS 5H10NS2)2(C5H5NO)], (I), and [Zn(C4H8NOS2)2(C5H5NO)], (II), are NS4 donor sets derived from N-bound hy\u00addroxy\u00adpyridyl ligands and asymmetrically chelating di\u00adthio\u00adcarbamate ligands. The resulting coordination geometries are highly distorted, being inter\u00admediate between square pyramidal and trigonal bipyramidal for both independent mol\u00adecules comprising the asymmetric unit of (I), and significantly closer towards square pyramidal in (II). The key feature of the mol\u00adecular packing in (I) is the formation of centrosymmetric, dimeric aggregates sustained by pairs of hy\u00addroxy-O\u2014H\u22efS(di\u00adthio\u00adcarbamate) hydrogen bonds. The aggregates are connected into a three-dimensional architecture by methyl\u00adene-C\u2014H\u22efO(hy\u00addroxy) and methyl-C\u2014H\u22ef\u03c0(chelate) inter\u00adactions. With greater hydrogen-bonding potential, supra\u00admolecular chains along the c axis are formed in the crystal of (II), sustained by hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds, with ethyl\u00adhydroxy and pyridyl\u00adhydroxy groups as the donors, along with ethyl\u00adhydroxy-O\u2014H\u22efS(di\u00adthio\u00adcarbamate) hydrogen bonds. Chains are connected into layers in the ac plane by methyl\u00adene-C\u2014H\u22ef\u03c0(chelate) inter\u00adactions and these stack along the b axis, with no directional inter\u00adactions between them. An analysis of the Hirshfeld surfaces clearly distinguished the independent mol\u00adecules of (I) and reveals the importance of the C\u2014H\u22ef\u03c0(chelate) inter\u00adactions in the packing of both (I) and (II).The common feature of the mol\u00adecular structures of the title compounds, [Zn(C Zn(S2CNEt2)2]2(bpe)\u00b7bpe 2]2(bpe)}n, for R = Et and n-Bu 2]2(bpe) S2CN(+)RR\u2032, with two formally negatively charged sulfur atoms, which makes di\u00adthio\u00adcarbamate a very effective chelating agent, thereby decreasing the Lewis acidity of the zinc atom.The structures of binary zinc bis\u00ad(di\u00adthio\u00adcarbamates) are always zero-dimensional (i.e using di\u00adthio\u00adcarbamate anions of the type \u2212S2CN(R)CH2CH2OH. This influence is seen in the recent report of the structures of Zn[S2CN(R)CH2CH2OH]2 for R = i-Pr and CH2CH2OH 2 CH2CH2OH]2, in the case when R = CH2CH2OH, isolated as a 1:1 hydrate, leads to supra\u00admolecular ladders and these extend in two dimensions via water-O\u2014H\u22efS(di\u00adthio\u00adcarbamate) hydrogen bonds. When R = i-Pr, layers are sustained by hy\u00addroxy-O\u2014H\u22efS hydrogen bonds 2 has been complexed with 3-hy\u00addroxy\u00adpyridine (pyOH) to yield two 1:1 complexes. Quite different aggregation patterns are observed when R = R\u2032 = Et (I)R = i-Pr and R\u2032 = CH2CH2OH (II)An approach to increase the supra\u00admolecular aggregation in the crystal structures of zinc di\u00adthio\u00adcarbamates has been to introduce hydrogen bonding functionality into the ligands, 2CNEt2)2(pyOH) comprise the asymmetric unit of (I)a, the ZnII atom is chelated by two di\u00adthio\u00adcarbamate ligands and one nitro\u00adgen atom derived from the monodentate pyOH ligand. The S1-di\u00adthio\u00adcarbamate ligand chelates the zinc atom forming quite different Zn\u2014S bond lengths compared with the S3-di\u00adthio\u00adcarbamate ligand. This is qu\u00adanti\u00adfied in the values of \u0394(Zn\u2014S), being the difference between the Zn\u2014Slong and Zn\u2014Sshort bond lengths, Table\u00a01i.e. 0.43 and 0.15\u2005\u00c5, respectively. The Zn1\u2014N3 bond length is significantly shorter than the Zn\u2014S bonds. The NS4 coordination geometry is highly distorted as seen in the value of \u03c4 of 0.48  and, especially, the Sl\u2014Zn\u2014Sl (l = long) bond angles, Table\u00a01b, is quite similar to that just described for the Zn1 atom. The values of \u0394(Zn\u2014S) of 0.21 and 0.25\u2005\u00c5 are inter\u00admediate to those for the Zn1-mol\u00adecule. Even so, the differences in the Zn\u2014S bond lengths in both mol\u00adecules are not that great with this observation reflected in the closeness of the C\u2014S bond lengths, Table\u00a01cf. the Zn1-mol\u00adecule.Two independent mol\u00adecules of Zn(S2CN(Me)CH2CH2OH]2(pyOH), is shown in Fig.\u00a02The mol\u00adecular structure of (II)Overlay diagrams of the three mol\u00adecules in (I)via a 14-membered {\u22efHOC2NZnS}2 synthon, Fig.\u00a04a and Table\u00a02x, y, z. The aggregates are further stabilized by pyOH-C\u2014H\u22ef\u03c0 inter\u00adactions where the \u03c0-system is a chelate ring. Such C\u2014H\u22ef\u03c0(chelate) inter\u00adactions are increasingly being recognized as being important in the supra\u00admolecular chemistry of metal 1,1-di\u00adthiol\u00adates  but with methyl-H atoms as the donors, Fig.\u00a04b. The connections between layers along the c direction are of the type methyl\u00adene-C\u2014H\u22efO(hy\u00addroxy), Fig.\u00a04c.The key feature of the mol\u00adecular packing of (I)a, these hydrogen bonds lead to a centrosymmetric 22-membered {\u22efSZnSCNC2OH\u22efOH}2 synthon. On either side of these synthons, the pyOH hy\u00addroxy group hydrogen bonds to the O2-hy\u00addroxy atom and through symmetry, a centrosymmetric 24-membered {\u22efOC2NCSZnNC2OH}2 synthon is formed, highlighted as \u20182\u2019 in Fig.\u00a05a. Alternating synthons generate a supra\u00admolecular chain aligned along the c axis. Methyl\u00adene-C\u2014H\u22ef\u03c0(chelate) inter\u00adactions link mol\u00adecules into dimeric units, Fig.\u00a05b. The combination of the aforementioned inter\u00adactions lead to supra\u00admolecular layers that stack along the b axis with no directional inter\u00adactions between them, Fig.\u00a05c.The addition of greater hydrogen-bonding potential in (II)et al., 2016dnorm in the range \u22120.2 to + 1.3 au for the Zn1- and Zn2-containing mol\u00adecules of (I)O and -H2O, and di\u00adthio\u00adcarbamate-S2 and S8 atoms represent the donors and acceptors of the O\u2014H\u22efS hydrogen bonds; these are viewed as blue and red regions on the Hirshfeld surfaces mapped over electrostatic potential (mapped over the range \u22120.07 to +0.10 au), Fig.\u00a07b and 6c are due to comparatively weaker inter\u00admolecular C\u2014H\u22efO inter\u00adactions. The intra-dimer \u03c0\u2013\u03c0 stacking inter\u00adaction between the pyOH rings, Fig.\u00a04a, is evident through the appearance of faint-red spots near the arene-C13 and C26 atoms of the rings, Fig.\u00a06a and 6b, forming a close inter\u00adatomic C\u22efC contact, Table\u00a04a\u2013c, characterize the influence of the C\u2014H\u22ef\u03c0(chelate) inter\u00adactions; in Fig.\u00a07The Hirshfeld surface analysis for (I)dnorm, Fig.\u00a09a and 9b, and result in the blue and red regions corres\u00adponding to positive and negative potential on the Hirshfeld surface mapped over electrostatic potential (mapped over the range \u22120.12 to +0.18 au), Fig.\u00a09c. The faint-red spots near the S4, C8, C9 and H2B atoms in Fig.\u00a09a and 9b indicate their involvement in short inter\u00adatomic S\u22efS, C\u22efC and C\u22efH/H\u22efC contacts, Table\u00a04a illustrates the immediate environment about a reference mol\u00adecule within Hirshfeld surfaces mapped over electrostatic potential and highlights the O\u2014H\u22efO hydrogen bonds. The C\u2014H\u22ef\u03c0(chelate) and its reciprocal contact, i.e. \u03c0\u2014H\u22efC, and short inter\u00adatomic S\u22efS, C\u22efC and C\u22efH/H\u22efC contacts, with labels 3\u20136, are shown in Fig.\u00a010b.The presence of peripheral hy\u00addroxy groups participating in the O\u2014H\u22efO hydrogen bonds in the structure of (II)a. The respective plots delineated into H\u22efH, O\u22efH/H\u22efO, S\u22efH/H\u22efS, C\u22efH/H\u22efC, C\u22efC and S\u22efS contacts The overall two-dimensional fingerprint plot for individual Zn1- and Zn2-containing mol\u00adecules, overall (I)b, show different distributions of points in the individ\u00adual plots for Zn1- and Zn2-mol\u00adecules. This, as well as their different percentage contributions to the Hirshfeld surface, Table\u00a05de, di) distances shorter than their van der Waals separations, corresponding to short inter\u00adatomic H\u22efH contacts, Table\u00a04The fingerprint plots delineated into H\u22efH contacts for (I)c, also exhibit slightly different profiles for the independent mol\u00adecules. The respective peaks at de + di \u223c 2.7\u2005\u00c5 and \u223c 2.6\u2005\u00c5 correspond to donors (upper region) and the acceptors (lower region) for the Zn1-mol\u00adecule, whereas these appear as a pair of peaks at the same de + di \u223c 2.6\u2005\u00c5 distance for the Zn2-mol\u00adecule. This is likely due to the inter\u00adacting oxygen and hydrogen atoms for the Zn1-mol\u00adecule being at their van der Waals separation in the donor region, i.e. at 2.72\u2005\u00c5, while in the acceptor region the peak corresponds to a short inter\u00adatomic O\u22efH contact, Table\u00a04de + di \u223c 2.6\u2005\u00c5.The fingerprint plots delineated into O\u22efH/H\u22efO contacts, Fig.\u00a011de + di distances in the fingerprint plots delineated into S\u22efH/H\u22efS contacts, Fig.\u00a011d, for the Zn1- and Zn2-mol\u00adecules result from different hy\u00addroxy-O\u2014H\u22efS(di\u00adthio\u00adcarbamate) hydrogen bonds. The tips at de + di \u223c 2.4\u2005\u00c5 in the donor region of the plot for the Zn1-mol\u00adecule and in the acceptor region for the Zn2-mol\u00adecule are due to the formation of O\u2014H\u22efS hydrogen bonds between the hy\u00addroxy-O1 and di\u00adthio\u00adcarbamate-S8 atoms; the other hydrogen bond, involving the O2 and S2 atoms, gives rise to tips at de + di \u223c 2.3\u2005\u00c5 in the respective donor and acceptor regions of the plots, Fig.\u00a011d. The plot for the overall structure results from the superimposition of individual plots and shows the symmetric distribution of points as a pair of long spikes having tips at de + di \u223c 2.3\u2005\u00c5. The short inter\u00adatomic S\u22efH/H\u22efS contacts in the crystal of (I)de + di \u223c 3.0\u2005\u00c5 in the respective plots.The pair of spikes with their tips at different e, have the same shape with tips at de + di \u223c 2.7\u2005\u00c5 which are due to the short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a04i.e. 1.8%, but recognizable contribution to the Hirshfeld surface and appear as an arrow-like distribution of points around de = di = 1.8\u2005\u00c5 in Fig.\u00a011f. As indicated in Fig.\u00a011g, S\u22efS contacts do not figure prominently in the mol\u00adecular packing of (I)Almost the same percentage contribution from C\u22efH/H\u22efC contacts to the overall surface is made by the Zn1- and Zn2-mol\u00adecules, Table\u00a05b, a pair of very thin spikes having their tips at de + di \u223c 2.3\u2005\u00c5 indicate the presence of short inter\u00adatomic H\u22efH contacts between hy\u00addroxy-H1O and -H2O atoms, Table\u00a04O and H3O atoms, Table\u00a04cf. (I)de + di \u223c 1.8\u2005\u00c5, Fig.\u00a011c. The tips corresponding to the O1\u22efH6A contact, Table\u00a04The corresponding two-dimensional fingerprint plots for (II)i.e. 22.2 and 22.7%, respectively, reflect the O\u2014H\u22efS hydrogen bonds and additional S\u22efH contacts resulting in tips at de + di \u223c 2.9\u2005\u00c5 in Fig.\u00a011d and Table\u00a04de + di \u223c 2.6\u2005\u00c5 in the plot, Fig.\u00a011e, results from the C\u2014H\u22ef\u03c0(chelate) and short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a04f, as the pair of tips at de + di \u223c1.7\u2005\u00c5. Finally, a cone-shaped distribution of points with a 3.8% contribution to the surface from S\u22efS contacts having a vertex at de = di \u223c 1.7\u2005\u00c5 in the fingerprint plot, Fig.\u00a011g, results from short inter\u00adatomic contacts between S4 atoms, Table\u00a04The S\u22efH/H\u22efS contacts with the nearly same contribution to the surface of (II)Chemical context, the presence of hydroxy\u00adethyl groups in zinc di\u00adthio\u00adcarbamates leads to a higher degree of recognizable supra\u00admolecular aggregation owing to hydrogen bonding, usually of the type hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) but, sometimes also of the type hy\u00addroxy-O\u2014H\u22efS(di\u00adthio\u00adcarbamate) 2]2}2, the usual dimeric motif is evident but these self-assemble via strong hydrogen bonding into three-dimensional architectures in both of the polymorphs characterized thus far, with the difference between the structures being the topology of supra\u00admolecular layers, i.e. flattened CH2CH2OH]2}2, the reduced hydrogen bonding leads to supra\u00admolecular chains CH2CH2OH)2]2}2L, where L is (3-pyrid\u00adyl)CH2N(H)C(=O)C(=O)N(H)CH2(3-pyrid\u00adyl). However, hydrogen bonding of the type hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) links the mol\u00adecules into inter-woven double chains 2, N,N\u2032-bis\u00ad(pyridin-3-ylmeth\u00adyl)ethane\u00addithiodi\u00adamide : \u03bd(C=N) 1482 ; \u03bd(C\u2014S) 987 (s). 1H NMR : \u03b4 9.91 , 8.20\u20138.00 , 7.30\u20137.10 , 3.82 ; 1.22 .Synthesis of (I)2N(Me)CH2CH2OH]2 and 3-hy\u00addroxy pyridine were dissolved in a MeOH/EtOH (1:1 v/v) solution. Solvent diffusion of hexane into this solution led to the formation of colourless crystals. FT\u2013IR (cm\u22121): \u03bd(C=N) 1480 (s); \u03bd(C\u2014S) 1002 (s). 1H NMR : \u03b4 9.91 , 8.20\u20138.00 , 7.30\u20137.10 , 4.91 ; 3.90 ; 3.70 ; 3.41 .Synthesis of (II)Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen-bound H-atoms were located in difference Fourier maps but were refined with a distance restraint of O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S205698901601728X/hb7628sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S205698901601728X/hb7628Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901601728X/hb7628IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1511865, 1511864CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A similar reaction of SnCl4 with 2 equiv. of Li[o-(C2H10B10)C(NiPr)(NHiPr)] unexpectedly afforded the known solvated penta\u00adchlorido\u00adstannate(IV) salt [Li(THF)4][SnCl5(THF)] as the main reaction product. Small amounts of the new chlorido-tin(IV) bis\u00ad(carboranylamidinate) bischloridotin(IV), SnIVCl[o-(C2H10B10)C(NiPr)(NHiPr)][o-(C2H10B10)C(NiPr)2] (2), were isolated as a by-product. Single-crystal X-ray structure analysis revealed a \u03baC,\u03baN-chelating coordination of the carboranylamidinate ligands in both 1 and 2. The Sn atom in 1 adopts a pseudo-trigonal\u2013bipyramidal coordination under participation of a stereoactive lone pair. In 2, a trigonal\u2013bipyramidal coordination of Sn is completed by a chlorido ligand.Reaction of 2 equiv. of the lithium carboranylamidinate Li[ RC(NR\u2032)2]\u2212 are the nitro\u00adgen analogs of carboxyl\u00adate anions. These versatile N,N\u2032-chelating ligands form stable coordination compounds with nearly every metallic element in the Periodic Table. In view of this rich coordination chemistry, amidinate ligands are frequently regarded as \u2018steric cyclo\u00adpenta\u00addienyl equivalents\u2019. Metal complexes comprising amidinato ligands are readily available by insertion of the 1,3-diorganocarbodi\u00adimide, R\u2013-N=C=N\u2014R, into an M\u2014C bond of an organometallic precursor compound. Another common synthetic route involves salt metathetical reactions between lithium amidinates and metal halides 2]\u2212 is the fact that the substituents R and R\u2032 attached to the N\u2013C\u2013N unit can be varied in many ways. With R = ortho-C2H11B10 (\u2018ortho-carboran\u00adyl\u2019) we introduced a sterically demanding and chemically versatile moiety in the backbone of the amidinate ligand. Carboranes are of tremendous scientific and technological inter\u00adest due to their various applications ever since their discovery in the 1960\u2032s. These applications include the synthesis of polymers and ceramics, catalysts, radiopharmaceuticals and non-linear optics, as well as the BNCT (= boron neutron capture therapy) technique C(NiPr)(NHiPr)]\u2212 (= [HiLPr]\u2212) was synthesized in our lab in 2010 by in situ li\u00adthia\u00adtion of the parent o-carborane, ortho-C2H12B10 (= ortho-dicarba-closo-dodeca\u00adborane), followed by treatment with 1 equiv. of N,N\u2032-diiso\u00adpropyl\u00adcarbodi\u00adimide , a proton is formally shifted from the carborane C atom to the amidinate unit, resulting in an amidine moiety that usually acts as a monodentate donor functionality as shown in Fig.\u00a02a.A key advantage of the amidinate anions [RL]2\u2013, whose favored coordination mode is still \u03baC,\u03baN . Derivatives of Si, P, Ge, SnII, SnIV, FeII and FeIII, RhI and IrI containing this ligand system have been prepared by double li\u00adthia\u00adtion of the parent ortho-carboranyl\u00adamidine followed by treatment with appropriate element chloride precursors C(NCy)(NHCy)]2  and SnIVCl[o-(C2H10B10)C(NiPr)(NHiPr)][o-(C2H10B10)C(NiPr)2] . Compound 2 is the first carboranylamidinate complex containing both mono- and dianionic carboranylamidinate ligands in a single mol\u00adecule.Among the known carboranylamidinate complexes are only very few compounds with more than one carboranylamidinate ligand per metal atom, and these are exclusively of the type ortho-carboranylamidinate precursors Li[HLCy] and Li[HiLPr] were readily available following a published procedure by reaction of the mono-li\u00adthia\u00adted o-carborane Li-o-C2B10H11 with a stoichiometric amount of the carbodi\u00adimides iPrN=C=NiPr or CyN=C=NCy, respectively, in THF  as colorless, block-like single crystals after recrystallization from toluene. The low isolated yield of ca 20% can be traced back to the very high solubility of 1 even in non-polar organic solvents. In addition to the X-ray diffraction study, compound 1 was also characterized through elemental analysis and the usual set of spectroscopic methods. In the IR spectrum, a characteristic \u03bd(NH) band at 3423\u2005cm\u22121 confirmed the presence of monoanionic [HLCy]\u2212 ligands. The NH functionalities were also observed in the 1H NMR spectrum through a broad singlet at \u03b4 4.50 ppm. A single 119Sn NMR resonance at \u03b4 \u221246 ppm was in agreement with the formation of a single Sn-containing species. The mass spectrum of 1 showed the mol\u00adecular ion at m/z 818 with 27% relative intensity.The mono-li\u00adthio-4 with 2 equiv. of Li[HiLPr] was carried out with the aim of synthesizing the hitherto unknown tin(IV) bis\u00ad(carboranylamidinate) Sn[iLPr]2. Cooling of the reaction mixture afforded a fairly large amount of well-formed, colorless crystals, which turned out to be the known solvated penta\u00adchlorido\u00adstannate(IV) salt [Li(THF)4][SnCl5(THF)]. This compound was first prepared and structurally characterized by Junk & Leary (2000ca 5% isolated yield) of the unexpected tin(IV) carboranylamidinate SnCl[iLPr][HiLPr] (2) could be obtained. The X-ray crystal structure determination of 2 revealed the presence of the first complex containing both a mono- and a dianionic carboranylamidinate ligand in one mol\u00adecule. As in 1, the IR spectrum of 2 showed a characteristic \u03bd(NH) band at 3410\u2005cm\u22121. Elemental analysis and a single resonance in the 119Sn NMR spectrum (\u03b4 290 ppm) confirmed the purity of 2. In the mass spectrum, the mol\u00adecular ion was observed at m/z 692 with 47% relative intensity.A similar reaction of SnCleary 2000. From th1 and 2 are illustrated in Figs.\u20053\u03baC,\u03baN-chelating mode. In the tin(II) complex Sn[HLCy]2 (1), the coordination of the metal atom can be described as pseudo-trigonal\u2013bipyramidal, with the two N atoms defining the axial positions [N1\u2014Sn\u2014N3 157.76\u2005(4)\u00b0]. The two Sn-C bonds are situated in the equatorial plane [C3\u2014Sn\u2014C18 100.12\u2005(5)\u00b0], together with the stereoactive lone pair at Sn. The bite angles of the [HLCy]\u2212 ligands are 72.01\u2005(5)\u00b0 (N1\u2014Sn\u2014C3) and 73.27\u2005(5)\u00b0 (N3\u2014Sn\u2014C18). The coordination geometry of the Sn atom therefore resembles that in the related tin(II) bis\u00ad(carboranylamidinate) Sn[HLiPr]2 . These values are in the same range as those observed in the isopropyl substituted analogue Sn[HiLPr]2 .The molecular structures of the title compounds iPr][HiLPr] (2) is structurally closely related to 1, as the Sn atom exhibits a trigonal\u2013bipyramidal coordination with the two amidinate N atoms in the axial positions . The lone pair at Sn is formally replaced by a chlorido ligand, which is almost perpendicular to the Sn\u2014N bonds . The Sn\u2014C bond lengths are 2.160\u2005(3)\u2005\u00c5 (Sn\u2014C2) and 2.154\u2005(3)\u2005\u00c5 (Sn\u2014C11) and therefore considerably shorter than in compound 1. This finding can be traced back to the higher oxidation number of the Sn atom. Similar Sn\u2014C bond lengths have been observed in the related tin(IV) derivatives SnCl3[HiLPr] [Sn\u2014C 2.132\u2005(3)\u2005\u00c5] and SnCl2[iLPr](THF) \u2212 ligands and deprotonated [iLPr]2\u2013 ligands are virtually equal, the Sn\u2014C(carborane) bond is obviously not noteworthily influenced by the bonding situation within the amidinate moiety. In contrast, in 2 the Sn\u2014N contact to the deprotonated carboranylamidinate ligand  is considerably shorter than that to the protonated ligand . As has been discussed previously, the M\u2014N contact in [iLPr]2\u2013 complexes can be regarded as a distinct single bond, while the M\u2014N contact in [HiLPr]\u2212 complexes should be described as a secondary coordinative inter\u00adaction \u2005\u00c5, SnCl2[iLPr](THF): Sn\u2014N 205.0\u2005(2)\u2005\u00c5; Harmgarth et al., 2017The tin(IV) complex SnCl are clearly in the range of double bonds, while the C\u2014N bonds to the protonated N atoms  can be regarded as single bonds. These values are consistent with those observed in other tin complexes with [HLR]\u2212 ligands (e.g. Sn[HLiPr]2: C=N(Sn) 1.287\u2005(3), C\u2014N(H) 1.347\u2005(4)\u2005\u00c5; Dr\u00f6se et al., 20103[HiLPr]: C=N(Sn) 1.288\u2005(4), C\u2014N(H) 1.339\u2005(4)\u2005\u00c5; Harmgarth et al. 20172, however the difference is less pronounced in this case . The \u03c0 electron density within the amidinate group in the [iLPr]2\u2013 ligand in 2 is clearly inverted, resulting in a long C\u2014N(Sn) bond [C3\u2014N1 1.372\u2005(4)\u2005\u00c5] and a short C=N bond to the non-coordinated N atom [C3\u2014N2 1.269\u2005(5)\u2005\u00c5]. Similar values have been obtained in SnCl2[iLPr](THF) \u2212 and [RL]2\u2013 ligands always display a typical \u03baC,\u03baN-chelating mode, this may explain why the formation of the complex SnCl[iLPr][HiLPr] (2) is preferred over a homoleptic complex Sn[iLPr]2, where the Sn atom would be tetra\u00adhedrally coordinated. Nonetheless, the example of SnCl2[iLPr](THF)  (solv. = solvent) might exist.In summarizing the results reported here, in tin carboranylamidinates a trigonal\u2013bipyramidal \u2005\u00c5] and between isopropyl groups in 2 [C5\u22efC15 3.670\u2005(7)\u2005\u00c5], respectively. In both compounds, the free N\u2014H groups are not involved in hydrogen bonding.In both aFor reviews on amidinate complexes, see: Collins 2011\u2019 Edelmanet al.  spectrometer in THF-d8 at 295\u2005(2)\u2005K. 1H and 13C NMR shifts are referenced to Si(CH3)4, 119Sn shifts to Sn(CH3)4 (each \u03b4 = 0 ppm). IR spectra were measured on a Bruker Vertex V70 spectrometer equipped with a diamond ATR unit, electron impact mass spectra on a MAT95 spectrometer with an ionization energy of 70\u2005eV. Elemental analyses  were performed using a VARIO EL cube apparatus.All operations were performed under an argon atmosphere using standard Schlenk techniques. THF and toluene were distilled from sodium/benzo\u00adphenone under argon. NMR spectra were recorded on a Bruker DPX400 (Cy]2 (1): oPreparation of Sn was treated in situ with SnCl2  and then stirred for 24\u2005h. The solvent was subsequently removed in vacuo, the solid residue extracted with toluene (40\u2005mL) and the insoluble matter filtered off. The filtrate was concentrated to a total volume of ca 10\u2005mL. Cooling to 278\u2005K for 2\u2005d afforded colorless, block-like single-crystals of 1. Yield: 0.58\u2005g (20%). Analysis calculated for C30H66B20N4Sn, M = 817.81\u2005g\u2005mol\u22121: C 44.06, H 8.13, N 6.85%. Found: 43.66, H 8.00, N 6.25%. IR: \u03bd 3423 w (\u03bd NH), 2935 m (\u03bd CH2), 2854 m (\u03bd CH2), 2560 m (\u03bd BH), 1623 m (\u03bd C=N), 1448 m (\u03b4 CH2) cm\u22121. 1H NMR \u2005K): \u03b4 4.50 , 3.24 , 1.70\u20132.80 , 1.08\u20131.98  ppm. 13C NMR \u2005K): \u03b4 143.0 (NCN), 80.3 (C\u2014Sn), 77.0 (C\u2014CN2), 54.6 (CH Cy), 34.8 (CH2 Cy), 25.7 (CH2 Cy), 25.4 (CH2 Cy), 25.1 (CH2 Cy), 25.0 (CH2 Cy) ppm. 119Sn NMR \u2005K): \u03b4 \u221246 ppm. MS: m/z (%) 818\u2005(27) [M]+, 467\u2005(19) [C15H32B10N2Sn]+, 350\u2005(24) [C15H32B10N2]+, 269\u2005(100) [C9H23B10N2]+, 143\u2005(54) [C2H10B10]+.iPr] (2):Preparation of SnCl[L][SnCl5(THF)]. Yield: 2.13\u2005g. In addition to the IR data reported by Junk & Leary (20007Li and 119Sn) data. 7Li NMR \u2005K): \u03b4 = \u22120.76 ppm. 119Sn NMR \u2005K): \u03b4 = \u2212641 ppm. Concentration of the mother liquid to ca. 10\u2005ml followed by cooling again to 278\u2005K for several days afforded 0.13\u2005g (5%) of 2 as colorless, plate-like single-crystals. Analysis calculated for C18H49B20ClN4Sn, M = 692.00\u2005g\u2005mol\u22121: C 31.24, H 7.14, N 5.12%. Found: 31.02, H 6.88, N 4.98%. IR: \u03bd 3410 w (\u03bd NH), 2964 m, 2930 w , 2616 m, 2569 s (\u03bd BH), 1628 m, 1596 vs (\u03bd C=N), 1461 m, 1372 m  cm\u22121. 1H NMR \u2005K): \u03b4 5.56 , 4.33\u20134.39 , 3.30\u20133.42 , 1.7\u20133.2 , 1.23\u20131.56 , 0.96\u20131.05  ppm. 13C NMR \u2005K): \u03b4 140.6 (NCN), 139.1 (NCN), 74.4 (C\u2014CN2), 73.2 (C\u2014CN2), 69.8 (C\u2014Sn), 52.0 (CH iPr), 48.3 (CH iPr), 25.5 (CH3), 23.1 (CH3) ppm. 119Sn NMR \u2005K): \u03b4 290 ppm. MS: m/z (%) 692\u2005(49) [M]+, 656\u2005(76) [C18H49B20N4Sn]+, 423\u2005(48) [C9H24B10ClN2Sn]+, 388\u2005(82) [C9H24B10N2Sn]+, 211\u2005(100) [C5H13B10N2]+, 171\u2005(18) [C3H10B10N]+.eary 2000, the com3 groups in 2 were allowed to rotate freely around the C\u2014C vector, the corresponding C\u2014H distances were constrained to 0.98\u2005\u00c5. C\u2014H distances within CH2 groups were constrained to 0.99\u2005\u00c5, C\u2014H distances within CH groups to 1.00\u2005\u00c5. H atoms attached to B and N atoms were located in the difference-Fourier map, B\u2014H distances were restrained to 1.12\u2005(2)\u2005\u00c5 and N\u2014H distances to 0.88\u2005(2)\u2005\u00c5. The Uiso(H) values were set at 1.5Ueq(C) for the methyl groups in 2, and at 1.2Ueq(X)  in all other cases. For 1, the reflections (100) and  compound_1, compound_2. DOI: 10.1107/S2056989017012671/zl2714compound_1sup2.hklStructure factors: contains datablock(s) compound_1. DOI: 10.1107/S2056989017012671/zl2714compound_2sup3.hklStructure factors: contains datablock(s) compound_2. DOI: 1565456, 1565455CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atoms are bridged by two carboxyl\u00adate anions.The crystal structure of a dinuclear tetra\u00adcarboxyl\u00adate complex of manganese(II) is reported wherein the Mn 2(C7H4NO4)4(C6H7N)4] or [Mn2(\u03bc-NBz)2(\u03ba2-NBz)2(4-Mepy)4], where NBz is 4-nitro\u00adbenzoate and 4-Mepy is 4-methyl\u00adpyridine, is a centrosymmetric dinuclear complex in which the MnII atoms are bridged by two NBz ligands with Mn\u22efMn = 4.1324\u2005(4)\u2005\u00c5. The MnII atom in this dimeric species is present in a distorted octa\u00adhedral environment with the four coordinating O atoms forming the equatorial plane and the two pyridyl N atoms occupying the axial sites. An important structural feature of the dimeric complex is that each of the bridging carboxyl\u00adate ligands binds to the metal ions in an asymmetric fashion involving bent and linear Mn\u2014O\u2014C units. The crystal packing is consolidated by C\u2014H\u22efO and C\u2014H\u22ef\u03c0 interactions.The title compound, [Mn While the former are in the range 56.95\u2005(4)\u2013150.77\u2005(4)\u00b0, the latter are in the range 88.02\u2005(5)\u201394.59\u2005(5)\u00b0.The highly distorted nature of the MnOIn the title compound, the carboxyl \u2013COO and \u2013NOO planes of the chelating NBz anion deviate slightly from the phenyl ring plane, forming dihedral angles of 2.6\u2005(3) and 23.6\u2005(4)\u00b0, respectively. According to Kaduk 2000 and KaduI2 and \u2013CO2 groups of the NBz ligand act as hydrogen acceptors (Table\u00a02D\u22efA separations for these weak contacts are in the range of 3.161\u2005(2) to 3.369\u2005(2)\u2005\u00c5, the <C\u2014H\u22efO angles are generally lower than 130\u00b0, except in one case where a hydrogen bond with a greater D\u22efA separation of 3.369\u2005(2)\u2005\u00c5 forms has an angle of 172\u00b0. In addition, inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions involving the pyridyl ring \u03c0 system of the 4-Mepy ligand link the complex mol\u00adecules into chains along the a axis 2(\u03ba2-O2CR)2L4] in Table\u00a03I2(\u03bc-OBz)2(\u03ba2-OBz)2(py)4] , NaNBz  and 4-Mepy  was stirred mechanically in water (20\u2005ml) at room temperature for 4\u2005h. The yellow precipitate that appeared was washed thoroughly with water and then with methanol before being dried in a vacuum desiccator over fused CaCl2. Yield: 2.58\u2005g (85% based on Mn). Light-yellow transparent crystals of I4\u00b7H2O (0.5\u2005mmol) containing 4-Mepy (1\u2005mmol) in methanol/water (1:1 v/v). Analysis calculated for C48H36N8O16Mn2: C, 52.84%; H, 3.30%; N, 10.27%; found: C, 52.04%; H, 3.02%; N, 9.8%; \u03bceff (295\u2005K)/Mn = 5.36 BM.A mixture of MnSOI2(\u03bc-OBz)2(\u03ba2-OBz)2(py)4]  set at 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989016015589/vn2116sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015589/vn2116Isup2.hklStructure factors: contains datablock(s) I. DOI: 1508004CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A new 4-thia\u00adzolidinone derivative has been obtained from the cyclization reaction of 4-methyl-3-thio\u00adsemicarbazone and dimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate (DMAD). 16H21N3O3S, was obtained from the cyclization reaction of 4-methyl-3-thio\u00adsemicarbazone and dimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate (DMAD). The cyclo\u00adhexyl\u00adidene ring has an envelope conformation with the stereogenic centre C atom as the flap. Its mean plane makes a dihedral angle of 56.23\u2005(9)\u00b0 with the thia\u00adzolidine ring mean plane. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds forming chains propagating in the [001] direction. Within the chains there are offset \u03c0\u2013\u03c0 inter\u00adactions between the thia\u00adzolidine rings of inversion-related mol\u00adecules [centroid\u2013centroid distance = 3.703\u2005(1)\u2005\u00c5]. The chains are linked by further C\u2014H\u22efO hydrogen bonds, forming slabs parallel to the ac plane.The new title 4-thia\u00adzolidinone derivative, C Its mean plane makes a dihedral angle of 56.0\u2005(1)\u00b0 with the mean plane of the cyclo\u00adhexyl\u00adidene ring (C8-C13). The meth\u00adoxy\u00adcarbonyl group (C1/O2/O3/C2) is also twisted slightly with respect to plane A, their mean planes being inclined to one another by 11.2\u2005(2)\u00b0. The six-membered cyclo\u00adhexyl\u00adidene ring has an envelope conformation with atom C8 as the flap: puckering parameters are Q = 0.494\u2005(2)\u2005\u00c5, \u03b8 = 129.8\u2005(2)\u00b0 and \u03c6 = 180.8\u2005(3)\u00b0. The C7=N3 and N2=C6 bond lengths are 1.282\u2005(2) and 1.278\u2005(2)\u2005\u00c5, respectively, consistent with C=N double bonding. The C6\u2014N2\u2014N3\u2014C7, C4\u2014C3\u2014C2\u2014O3 and C3\u2014C2\u2014O3\u2014C1 torsion angles are 175.5\u2005(2), \u2212172.4\u2005(2) and 172.5\u2005(2)\u00b0, respectively.The title compound ts Fig.\u00a02. The comi hydrogen bonds, forming chains propagating along [001]; see Table\u00a01Cg1\u22efCg1 = 3.703\u2005(1)\u2005\u00c5,where Cg1 is the centroid of the S1/N1/C4\u2013C6 ring, inter\u00adplanar distance = 3.468\u2005(1)\u2005\u00c5, slippage = 1.298\u2005\u00c5]. The chains are linked by further C\u2014H\u22efO hydrogen bonds, forming slabs lying parallel to the ac plane -4-oxo-3-phenyl-1,3-thia\u00adzolidin-2-yl\u00adidene]ethane\u00adhydrazono\u00adyl}phen\u00adyl)amino]\u00adbut-2-enedioate \u00b0 in the title compound, 172.1\u2005(2)\u00b0 in AGOMUG, \u2212178.9\u2005(2) and \u2212165.5\u2005(2)\u00b0 in NIPPAF and \u2212167.4\u2005(5)\u00b0 in RIMDIC.A comparison of the main C\u2014N, N\u2014N, C\u2014S bond lengths in the title compound and the structures extracted from the CSD shows a good correlation. The C=N\u2014N=C torsion angles indicate that in each case the four atoms are nearly planar, 2SO4 and then evaporated under reduced pressure. The obtained residue was chromatographed on a silica gel column using hexane as eluent, to give compound 3 . Yellow prismatic crystals were obtained from a petroleum ether solution, by slow evaporation of the solvent at room temperature.To a solution of 4-methyl-3-thio\u00adsemicarbazone  in ethanol (15\u2005ml) was added dimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate (DMAD) . The mixture was stirred under reflux for 1\u2005h, leading to the corresponding thia\u00adzolidinone. After cooling, the mixture was extracted with ethyl acetate (3 \u00d7 20\u2005ml). The organic layer was washed with water, dried on anhydrous NaUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017014311/su5396sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017014311/su5396Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017014311/su5396Isup3.cmlSupporting information file. DOI: 1577993CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The di\u00adthio\u00adcarbamate moiety displays a unique coordination mode, comprising a \u2018side-on\u2019 \u03c0-coordinated K+ cation besides a commonly \u03c3-chelated K+ cation. By bridging coordination of the CSS group, COO group and water mol\u00adecules, the K+ cations are linked into a two-dimensional coordination polymer extending parallel to the ab plane. These layers are again inter\u00adconnected by O\u2014H\u22efS hydrogen bonds.The mol\u00adecular and crystal structure of the  Giovagnini et al., 2005et al., 2006et al., 2012l-proline-derived potassium salt K2(SSC\u2013NC4H7\u2013COO). This compound crystallizes from aqueous solution as a trihydrate, which has been structurally characterized in the course of this work.Natural amino acids react readily with carbon di\u00adsulfide in an alkaline environment to give di\u00adthio\u00adcarbamate-functionalized carboxyl\u00adates. Since the first report on a series of barium salts in the 1950s \u00b73H2O, crystallized as colourless plates in the ortho\u00adrhom\u00adbic space group P212121, with one formula moiety in the asymmetric unit  and the remaining two H2O mol\u00adecules are coordinating in a \u03bc-bridging mode (O4 and O5). The K\u2014S distances at the \u03c3-chelated K+ cation (K2) are 3.2176\u2005(8) and 3.2650\u2005(9)\u2005\u00c5, while the K\u2014S separations at the \u03c0-coordinated K+ cation (K1) are significantly longer at 3.2956\u2005(9) and 3.4463\u2005(8)\u2005\u00c5. The coordination mode of the di\u00adthio\u00adcarbamate group in the title compound : \u03b4 1.89\u20131.98 , 2.24 , 3.75 , 3.83 , 4.72 . 13C NMR : \u03b4 24.6 (4-CH2), 31.5 (3-CH2), 55.7 (5-CH2), 69.5 (2-CH), 179.9 (COO), 205.8 (CSS).A slight excess of carbon di\u00adsulfide  was added to a solution of Uiso(H) = 1.2Ueq(C). C\u2014H distances within the CH2 groups were constrained to 0.99\u2005\u00c5 and that within the CH group to 1.00\u2005\u00c5. The water H-atom sites were located in difference Fourier maps and refined using restraints on the O\u2014H distance [target value = 0.84\u2005(2)\u2005\u00c5]. The corresponding Uiso(H) values were set at 1.5Ueq(O). The reflection (002) disagreed strongly with the structural model and was therefore omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017011999/zl2712sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017011999/zl2712Isup2.hklStructure factors: contains datablock(s) I. DOI: 1569563CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The herbicide penoxsulam crystallizes with two independent mol\u00adecules in the asymmetric unit. The crystal structure is stabilized by C\u2014F\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions that combine with C\u2014H\u22efF and C\u2014H O hydrogen bonds and weak inter\u00admolecular F\u22efF short contacts to form a three-dimensional network. 16H14F5N5O5S [systematic name: 2--N--6-(tri\u00adfluoro\u00admeth\u00adyl)benzene\u00adsulfonamide], is used as a herbicide. The asymmetric unit of this structure comprises two independent mol\u00adecules, A and B. The dihedral angles between the ring planes of the triazolo\u00adpyrimidine ring systems and the benzene rings are 68.84\u2005(7)\u00b0 for A and 68.05\u2005(6)\u00b0 for B. In the crystal, weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid separations of 3.4456\u2005(17) and 3.5289\u2005(15)\u2005\u00c5 and C\u2014F\u22ef\u03c0 [3.5335\u2005(17)\u2005\u00c5 and 107.92\u2005(13)\u00b0] contacts link adjacent mol\u00adecules into chains along [001]. C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds link type B mol\u00adecules into chains parallel to (100). Additional C\u2014H\u22efF hydrogen bonds together with short F\u22efF contacts further aggregate the structure into a three-dimensional network.The title compound, C The compound inhibits the synthesis of acetolactate and targets the biosynthesis of branch-chained amino acids, a metabolic pathway found in plants, fungi, and microorganisms. Acetolactate synthase (ALS) inhibitors are present in most effective herbicides. They are used in agriculture because they show a broad weed control spectrum, crop selectivity, are safe to humans, and can be applied at relatively low usage rates \u00b0 in B. All bond lengths and bond angles are normal and comparable to those observed in similar crystal structures for triazolo\u00adpyrimidine , and type B with Cg2\u22efCg2vi = 3.5289\u2005(15)\u2005\u00c5 . These combine with C25\u2014F9\u22efCg3vii inter\u00adactions involving the C3\u2013C8 benzene ring to form chains along [001]  and 2.794\u2005(2)\u2005\u00c5] together with C1\u2014H1A\u22efF10i, C16\u2014H16C\u22efF3ii, C18\u2014H18\u22efF10iii and C32\u2014H32C\u22efF8iv hydrogen bonds generate a three-dimensional network with mol\u00adecules stacked along the a-axis direction benzoate -one  = 0.88\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for the N\u2014H group, d(C\u2014H) = 0.95\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for aromatic C\u2014H, d(C\u2014H) = 0.98\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for methyl group, d(C\u2014H) = 0.99\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for Csp3\u2014H, and d(C\u2014H) = 1.00\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for Csp3\u2014H.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017011458/sj5532sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017011458/sj5532Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011458/sj5532Isup3.cmlSupporting information file. DOI: 1566461CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Adoptive immunotherapy is gaining momentum to fight malignancies, whereby \u03b3\u03b4 T cells have received recent attention as an alternative cell source as to natural killer cells and \u03b1\u03b2 T cells. The advent of \u03b3\u03b4 T cells is largely due to their ability to recognize and target tumor cells using both innate characteristic and T cell receptor (TCR)-mediated mechanisms, their capacity to enhance the generation of antigen-specific T cell responses, and their potential to be used in an autologous or allogeneic setting.In this study, we explored the beneficial effect of the immunostimulatory cytokine interleukin (IL)-15 on purified \u03b3\u03b4 T cells and its use as a stimulatory signal in the ex vivo expansion of \u03b3\u03b4 T cells for adoptive transfer. The expansion protocol was validated both with immune cells of healthy individuals and acute myeloid leukemia patients.We report that the addition of IL-15 to \u03b3\u03b4 T cell cultures results in a more activated phenotype, a higher proliferative capacity, a more pronounced T helper 1 polarization, and an increased cytotoxic capacity of \u03b3\u03b4 T cells. Moreover \u03b3\u03b4 T cell expansion starting with peripheral blood mononuclear cells from healthy individuals and acute myeloid leukemia patients is boosted in the presence of IL-15, whereby the antitumor properties of the \u03b3\u03b4 T cells are strengthened as well.Our results support the rationale to explore the use of IL-15 in clinical adoptive therapy protocols exploiting \u03b3\u03b4 T cells. Cellular immunotherapy for cancer is a rapidly evolving field, endeavoring to deal with common relapse or resistance to conventional treatments. Herewith, most interesting are the \u03b3\u03b4 T cells, a T cell subset possessing a combination of innate and adaptive immune cell traits . ActivatAmong the various tumor targets of \u03b3\u03b4 T cells , we focu\u03b3\u03b4 T cells can be expanded, using combinations of cytokines and phosphoantigens ) or aminobisphosphonates  . The incLimitations on the use of IL-2, relating to among other its toxicity, invigorate the investment in exploring other cytokines of the IL-2 family  . IL-15 iThese results stressed the need for a detailed characterization of the sheer effect of IL-15 on untouched and isolated \u03b3\u03b4 T cells. The latter will be discussed in the first part of this paper, followed by the translation of the results into a \u03b3\u03b4 T cell expansion protocol for adoptive transfer.6 cells/mL) were cultured for 5\u00a0days in Iscove\u2019s Modified Dulbecco\u2019s Medium , supplemented with 10\u00a0% fetal bovine serum , IPP , and IL-2  or IL-15 . The Burkitt\u2019s lymphoma tumor cell line Daudi was kindly provided to us by the laboratory of Prof. Kris Thielemans , and the multiple myeloma cell line U266 was a gift from Prof. Wilfred Germeraad .This study was approved by the Ethics Committee of the Antwerp University Hospital  under the reference number B300201419756. Experiments were performed using buffy coats derived from healthy volunteer whole blood donations  and blood samples from patients with AML obtained from the hematological division of the UZA (Table\u00a0\u00ae Fixable Aqua Stain (Life Technologies), CD56-PE (Becton Dickinson (BD); Erembodegem, Belgium), CD3-PerCP-Cy5.5 (BD), and \u03b3\u03b4 T cell receptor (TCR)-APC (Miltenyi) and analyzed using a FACSAria II cytometer (BD). \u03b3\u03b4 T cell proliferation was assessed by quantifying the percentage of proliferating (CFSE-diluted) cells within the viable (LIVE/DEAD\u2212) CD3+\u03b3\u03b4TCR+ gate.To test the ability of IL-2 and IL-15, in combination with IPP, to induce \u03b3\u03b4 T cell proliferation, a 5,6-carboxyfluorescein diacetate succinimidyl ester  flow cytometry-based proliferation assay was performed with isolated \u03b3\u03b4 T cells. Unstimulated CFSE-labeled \u03b3\u03b4 T cells served as negative control. After 5\u00a0days, cells were stained with LIVE/DEAD6 cells/mL. Cell cultures were maintained at a cell density of 0.5\u20132\u2009\u00d7\u2009106 cells/mL and were replenished every 2 to 3\u00a0days by adding IL-2/IL-15-supplemented medium. Phenotypic and functional assays were performed on cells harvested at least 14\u00a0days after first stimulations.PBMC were resuspended in Roswell Park Memorial Institute (RPMI) supplemented with 10\u00a0% heat-inactivated human AB serum , zoledronate , IL-2 (100\u00a0IU/mL), and/or IL-15 (100\u00a0IU/mL) at a final concentration of 1\u2009\u00d7\u200910\u00ae Fixable Aqua Stain was used to distinguish viable from non-viable cells. Data were acquired on a FACSAria II flow cytometer (BD). Corresponding species- and isotype-matched antibodies were used as controls.Freshly isolated and 5-day proliferated \u03b3\u03b4 T cells were membrane-stained with the following monoclonal antibodies; \u03b3\u03b4 TCR-FITC (Miltenyi), CD56-PE (BD), CD69-PE (BD), and HLA-DR-PE (BD). Propidium iodide  was added to exclude dead cells from phenotypic analysis. Data acquisition was performed on a FACScan multiparametric flow cytometer (BD). Phenotypic characterization of \u03b3\u03b4 T cells was examined pre- and post-expansion, using CD27-FITC (BD), CD69-FITC (BD), CD56-PE (BD), CD80-PE (BD), CD45RA-PE-Cy7 (BD), CD28-PerCP-Cy5.5 (BD), CD16-PB (BD), CD86-V450 (BD), \u03b3\u03b4 TCR-APC (Miltenyi), and HLA-DR-APC-H7 (BD). Live/Dead\u03b3\u03b4 T cell cultures were set up as described above. After 5\u00a0days of proliferation, cell-free supernatants were harvested and stored at \u221220\u00a0\u00b0C before analysis. Samples were assessed by using enzyme-linked immunosorbent assay (ELISA) for the presence of TGF-\u03b2  and by using electrochemiluminescence immunoassay , Rockville, MD, USA) for the presence of IFN-\u03b3, TNF-\u03b1, IL-5, IL-10, and IL-17. Cytokine measurements were also performed on supernatant of \u03b3\u03b4 T cell cultures stimulated for an additional 4\u00a0h with the tumor cell lines Daudi and U266 at an effector-to-target (E:T) ratio of 5:1.6 cells/mL) and incubated for 3\u00a0h at 37\u00a0\u00b0C/5\u00a0% CO2. \u03b3\u03b4 T cells were then washed and incubated with Live/Dead\u00ae Fixable Aqua Stain, CD3-PerCP-Cy5.5 (BD) and \u03b3\u03b4 TCR-APC (Miltenyi) for 30\u00a0min at 4\u00a0\u00b0C. Subsequently, cells were fixed and permeabilized, using the Foxp3/Transcription Factor Staining Buffer Set (eBioscience), according to the manufacturer\u2019s instructions. Intracellular staining antibodies  or the corresponding isotype control were added and allowed to bind for 1\u00a0h at 4\u00a0\u00b0C.After 14\u00a0days of \u03b3\u03b4 T cell expansion, IFN-\u03b3 and TNF-\u03b1 production was measured using a flow cytometric-based intracellular staining assay. Measurements were also performed after an additional hour of stimulation with Daudi or U266 cells (E:T ratio\u2009=\u20095:1). Brefeldin A  was added to the different conditions (1\u2009\u00d7\u200910\u2212/PI\u2212) cells within the PKH67+ tumor cell population using the following equation: % killing\u2009=\u2009100\u2009\u2212\u2009[(% viable tumor cells with \u03b3\u03b4 T cells/% viable tumor cells without \u03b3\u03b4 T cells)\u2009\u00d7\u2009100].A flow cytometry-based lysis assay was performed in order to determine the killing activity of \u03b3\u03b4 T cells against the tumor cell lines Daudi and U266. Tumor cells were labeled prior to co-culture with PKH67 Green Fluorescent Cell Linker dye (Sigma-Aldrich), according to the manufacturer\u2019s protocol, and subsequently co-cultured with \u03b3\u03b4 T cells at different E:T ratios . After 4\u00a0h, cells were acquired on a FACSAria II flow cytometer following staining with annexin V-APC (BD) and PI. Killing was calculated based on the percentages of viable . GraphPad Prism software  was used for statistical calculations and artwork. Shapiro-Wilk normality test was performed to ascertain the distribution of the data. 6 and 2.18\u2009\u00b1\u20090.31 x106 \u03b3\u03b4 T cells, respectively. Furthermore, exposure of human peripheral blood \u03b3\u03b4 T cells to IL-15+IPP resulted in an improved activated phenotype. Surface expression of CD69 augmented from 1.63\u2009\u00b1\u20090.52\u00a0%  to 15.85\u2009\u00b1\u20093.80\u00a0% (IL-2+IPP) and 26.55\u2009\u00b1\u20093.83\u00a0% (IL-15+IPP), and HLA-DR expression went up from 12.16\u2009\u00b1\u20092.36\u00a0%  to 64.58\u2009\u00b1\u20095.63\u00a0% (IL-2+IPP) and 63.93\u2009\u00b1\u20097.63\u00a0% (IL-15+IPP). Notably, CD56 expression was significantly higher on IL-15+IPP stimulated \u03b3\u03b4 T cells (38.34\u2009\u00b1\u20094.83\u00a0%) than on unstimulated (19.20\u2009\u00b1\u20094.49\u00a0%) and on IL-2+IPP stimulated \u03b3\u03b4 T cells (28.14\u2009\u00b1\u20094.73\u00a0%).Stimulation of \u03b1\u03b2 T cell proliferation is a characteristic of both IL-2 and IL-15. To assess their effect on \u03b3\u03b4 T cells, in combination with IPP, a 5-day proliferation assay was performed using isolated \u03b3\u03b4 T cells  between both \u03b3\u03b4 T cell types. After 5\u00a0days, \u03b3\u03b4 T cell cultures were harvested and exposed to Daudi or U266 tumor cells, to verify their antitumor activity, including cytokine secretion . Next, it should be noted that in contrast to the 100\u00a0% success rate of \u03b3\u03b4 T cell expansion , a clear effect was detected Fig.\u00a0. Despite culture , 34) staAt culture initiation (day 0) and termination day 14\u201315), we subjected the \u03b3\u03b4 T cell cultures to immunophenotyping. Whereas the four distinct effector/memory states were nearly evenly represented in terms of percentages by circulating \u03b3\u03b4 T cells of healthy donors at day 0, with a small preponderance for the na\u00efve and central memory phenotype, the vast majority of expanded cells were effector memory \u03b3\u03b4 T cells and to a lesser extent central memory \u03b3\u03b4 T cells , as compared to IL-2+zoledronate (1.49\u2009\u00b1\u20090.43\u00a0%) Fig.\u00a0. This mon\u2009=\u20093) and IL-2+15+zoledronate (n\u2009=\u20095) expansion protocols. For U266 killing, percentages of 24.89\u2009\u00b1\u20093.51 and 35.19\u2009\u00b1\u20094.96\u00a0% were true. Finally, for some AML patients e.g., patient A, cytotoxic capacity is highly dependent on the target cell line  and myeloid DCs, including our IL-15 DCs, feature cytotoxic activity, in addition to serving classical DC functions [When looking in detail at the phenotype of cultured \u03b3\u03b4 T cells, two findings stand out from our results. First, incubation with IL-15+IPP led to a significant upregulation of CD56 relative to IL-2+IPP stimulated and unstimulated \u03b3\u03b4 T cells. In addition to the stringent association of CD56 with NK cells, CD56 has also been detected on other lymphoid cells, including \u03b3\u03b4 T cells and activated CD8 T cells \u201355. Moreunctions , 57\u201359. unctions . This fu\u2212/\u2212 knockout mice only produced small amounts of IFN-\u03b3 upon stimulation and showed significantly lower cytotoxicity against target cells as compared to wild-type mice [In view of the functionality of \u03b3\u03b4 T cells, our experiments clearly show that IL-15, in comparison with IL-2, has a superior Th1 polarizing effect on \u03b3\u03b4 T cells and markedly strengthens the \u03b3\u03b4 T cell cytotoxic capacity. These results are supported by in vivo data where intestinal \u03b3\u03b4 T cells of IL-15ype mice . This inype mice . In addiype mice . Althougype mice . All theype mice .Taken together, we have demonstrated that the addition of immunostimulatory cytokine IL-15 to in vitro \u03b3\u03b4 T cell cultures, derived from both AML patients and healthy blood donors, resulted in a more activated phenotype and significantly increased the antitumor functions of \u03b3\u03b4 T cells. This was manifested in a higher yield of expanded \u03b3\u03b4 T cells, a more pronounced Th1 polarization and an increased cytotoxic capacity, all desirable characteristics for their further use in adoptive immunotherapy. Therefore, our results strengthen the rationale to explore the use of IL-15 in clinical adoptive therapy protocols."}
{"text": "II cation is N,O,O\u2032,O\u2032\u2032-chelated by a 2,2\u2032-[N-(phenyl\u00adphospho\u00adrylmeth\u00adyl)aza\u00adnedi\u00adyl]di\u00adacetate dianion and coordinated by two 1H-benzo[d]triazole mol\u00adecules in a slight distorted octa\u00adhedral coordination.In the mol\u00adecule, the Co 11H12NO6P)(C6H5N3)2]\u00b7C6H5N3, the 2,2\u2032-[N-(phenyl\u00adphospho\u00adrylmethyl-\u03baO)aza\u00adnedi\u00adyl]di\u00adacetate dianion N,O,O\u2032,O\u2032\u2032-chelates the CoII cation and two 1H-benzo[d]triazole mol\u00adecules coordinate to the CoII cation to complete the slightly distorted octa\u00adhedral coordination. In the crystal, classical O\u2014H\u22efO, N\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22efN hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular architecture. \u03c0\u2013\u03c0 stacking between the triazole and benzene rings and between the benzene rings is also observed in the crystal.In the title compound, [Co(C Research of its potential applications  of this and analogous complexes is currently being undertaken.In addition to their biological activities, amino\u00adphosphinic acids are also attracting inter\u00adest in many areas such as the construction industry, aerospace and electronics for their excellent flame retardancy to polymeric materials phosphor\u00adyl]meth\u00adyl}aza\u00adnedi\u00adyl)di\u00adacetate dianion and coordin\u00adates two 1H-benzo[d]triazole mol\u00adecules in a slightly distorted octa\u00adhedral coordination  and refluxed for 1\u2005h under a nitro\u00adgen atmosphere. 50\u2005ml of formaldehyde in hydro\u00adchloric acid (37%) was added dropwise under vigorous stirring, and the temperature was maintained at 378\u2013383\u2005K for 4\u2005h. This solution was then concentrated under reduced pressure and allowed to cool to room temperature. 100\u2005ml of acetone was added, and the white precipitate of 2,2\u2032-({[(phen\u00adyl)phosphor\u00adyl]meth\u00adyl}aza\u00adnedi\u00adyl)di\u00adacetic acid was collected by filtration. Colourless crystals of the title compound were obtained as follows: 2.38\u2005g CoCl2\u00b76H2O (0.01\u2005mol) and 3.57\u2005g 1H-benzo[d]triazole (0.03\u2005mol) were added to a stirred hydro\u00adchloric acid solution , then 3.24\u2005g of 2,2\u2032-({[(phen\u00adyl)phosphor\u00adyl]meth\u00adyl}aza\u00adnedi\u00adyl)di\u00adacetic acid (0.01\u2005mol) were added in one portion. The mixture was stirred for 1\u2005h, then filtered and left undisturbed. Single crystals were obtained by slow evaporation of the reaction mixture after several days.Phenyl\u00adphosphinic acid  and iminodi\u00adacetic acid  were dissolved in hydro\u00adchloric acid (6\u20052 groups) were positioned geometrically and refined using a riding model with Uiso(H) = 1.2Ueq(C). The carboxyl H atom was refined as rotating group with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017015079/xu5906sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017015079/xu5906Isup3.hklStructure factors: contains datablock(s) I. DOI: 1573300CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title mol\u00adecular salt features N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions; Hirshfeld surface analysis and fingerprint plots are reported. 5H8N3)2[CoCl4], the cations are protonated at their pyridine N atoms and the anion is an almost regular tetra\u00adhedron. The crystal structure consists of alternating inorganic layers, built from tetra\u00adchlorido\u00adcobaltate anions, and organic layers formed by protonated cations of 2,6-di\u00adamino\u00adpyridinium. The crystal packing is governed by C/N\u2014H\u22efCl hydrogen-bonding inter\u00adactions between the organic and the inorganic ions and Cl\u22efCl inter\u00adactions. Moreover, the cations show a \u03c0\u2013\u03c0 stacking inter\u00adaction [inter\u00adcentroid distance = 3.763\u2005(2)\u2005\u00c5]. The prevalence of these inter\u00adactions is illustrated by an analysis of the three-dimensional Hirshfeld surface and by two-dimensional fingerprint plots.In the title mol\u00adecular salt, (C These data are in agreement with those found in related compounds  = 0.004 and \u0394I(Cl\u2014Co\u2014Cl) = 0.0019] show a slight distortion of the tetra\u00adhedra. The inter\u00adanionic Cl\u22efCl contact distances between the nearest neighbor tetra\u00adhedra are 3.986\u2005(2)\u2005\u00c5 along the a axis and 3.889\u2005(2)\u2005\u00c5 along the c axis ns Fig.\u00a01. The geois Fig.\u00a02, compareet al., 2015Pyridinium cations always possess an expanded angle of C\u2014N\u2014C in comparison with the parent pyridine 2[MBr4]  2[CoBr4] ns Fig.\u00a03, which iThe construction of the three-dimensional architecture is consolidated by N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds Table\u00a01, generatfs Fig.\u00a04.et al., 2017As can be seen from Fig.\u00a05CrystalExplorer  , H\u22efH  and C\u22efH/H\u22efC .The fingerprint plots of (I)et al., 20123 and surface area in the order of 648\u2005\u00c52. With the porosity, the calculated void volume of (I)e.g. N\u2014H\u22efCl and C\u2014H\u22efCl.Fig.\u00a092\u00b76H2O (molar ratio 1:1) were dissolved in 10\u2005ml of methanol; 3\u2005ml of hydro\u00adchloric acid (37%) was added dropwise to the mixture and the resulting blue solution was put aside for crystallization at room temperature. After two weeks, blue crystals of (I)2,6-di\u00adamino\u00adpyridine and CoClCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018003171/hb7732sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018003171/hb7732Isup2.hklStructure factors: contains datablock(s) I. DOI: 1588020CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Erratum to:Perspect Med Educ (2015) 4:308\u2013313DOI\u00a010.1007/s40037-015-0220-x\u22124 rather than 5.89\u00a0\u00d7 10\u22123. The exponent is correctly reported in the body text (page 311).In the version of the article originally published online, there was an error in Table\u00a03 (page 312). The B\u00a0coefficient for the variable \u201cAnki\u201d should be 5.89\u00a0\u00d7 10"}
{"text": "In the title compound, C\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking combine to generate a three-dimensional network. A Hirshfeld surface analysis is presented. 18H20N2O7, the dihedral angle between the aromatic rings is 7.28\u2005(7)\u00b0 and the almost planar conformation of the mol\u00adecule is supported by an intra\u00admolecular O\u2014H\u22efO hydrogen bond, which closes an S(6) ring. In the crystal, weak C\u2014H\u22efO hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking link the mol\u00adecules into a three-dimensional network. A Hirshfeld surface analysis showed that the major contribution to the inter\u00admolecular inter\u00adactions are van der Waals inter\u00adactions (H\u22efH contacts), accounting for 48.4% of the surface.In the title compound, C An intra\u00admolecular O\u2014H\u22efO hydrogen bond (Table\u00a01S(6) ring and a C\u2014H\u22efO inter\u00adaction is also observed. A Mogul geometry check found that all the bond lengths and angles are within typical ranges on Fig.\u00a01; the C10d Table\u00a01 closes aC\u22efO7ii hydrogen bonds [C\u22efO = 3.3694\u2005(19)\u2005\u00c5], which generate B\u22efO6i hydrogen bond [C\u22efO = 3.341\u2005(3)\u2005\u00c5]. In addition, weak and very weak \u03c0\u2013\u03c0 inter\u00adactions  between benzene and pyrimidine rings  occur -trione -trione  I. DOI: 10.1107/S2056989017010374/hb7681Isup2.hklStructure factors: contains datablock(s) I. DOI: 1562022CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, a naphthalene derivative, the cyclo\u00adhexa-1,3-diene ring of the 1,2-di\u00adhydro\u00adnaphthalene ring system adopts a half-chair conformation. The mean plane of the 1,2-di\u00adhydro\u00adnapthalene ring system make dihedral angles of 86.23\u2005(6) and 64.80\u2005(7)\u00b0 with two phenyl rings. In the crystal, the mol\u00adecules are linked by C\u2014H\u22efO, inter\u00adactions and further stabilized by C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions. 26H20O5, a 1,2-di\u00adhydro\u00adnaphthalene derivative, the cyclo\u00adhexa-1,3-diene ring of the 1,2-di\u00adhydro\u00adnaphthalene ring system adopts a half-chair conformation. The mean plane of the 1,2-di\u00adhydro\u00adnapthalene ring system makes dihedral angles of 86.23\u2005(6) and 64.80\u2005(7)\u00b0 with two phenyl rings. The carbonyl O atom attached to the di\u00adhydro\u00adnaphthalene ring system deviates from the mean plane of the 1,2-di\u00adhydro\u00adnaphthalene ring system by 0.618\u2005(1)\u2005\u00c5. In the crystal, the mol\u00adecules are linked into layers parallel to the bc plane via two kinds of C\u2014H\u22efO inter\u00adactions, one of which forms a C(10) chain motif running along the c-axis direction and the other forms an R22(6) ring motif. Adjacent layers are further connected by C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6318\u2005(9)\u2005\u00c5].In the title compound, C \u00c5, q3 = 0.1461\u2005(14)\u2005\u00c5, \u03c62 = 155.9\u2005(3)\u00b0 and \u03b8 = 64.7\u2005(2)\u00b0 and \u0394Cs = 4.41\u2005(19). The dihedral angle between the C1\u2013C6 and C5\u2013C10 rings is 10.15\u2005(6)\u00b0. The C11\u2013C16 phenyl ring is almost perpendicular to the 1,2-di\u00adhydro\u00adnaphthalene C1\u2013C10 ring system with a dihedral angle of 83.83\u2005(7)\u00b0 between them. The other phenyl ring (C21\u2013C26) makes dihedral angles of 64.80\u2005(7) and 29.06\u2005(8)\u00b0 with the mean plane of C1\u2013C10 ring system and the C11\u2013C16 phenyl ring, respectively. Atom O1 of the carbonyl group deviates from the mean plane of the 1,2-di\u00adhydro\u00adnaphthalene ring system by 0.647\u2005(1)\u2005\u00c5.In the title compound Fig.\u00a01, the 1,2via C\u2014H\u22efO hydrogen bonds  zigzag chains running along the c-axis direction \u2005\u00c5, inter\u00adplanar distance = 3.343\u2005(1)\u2005\u00c5 and offset distance = 1.419\u2005(1)\u2005\u00c5; symmetry code: (iii) \u2212x, 1\u00a0\u2212\u00a0y, \u2212z; Cg1 and Cg3 are the centroids of the C1\u2013C6 and C11\u2013C16 rings, respectively].In the crystal, the mol\u00adecules are linked on Fig.\u00a02. In addiif Fig.\u00a03, forming3\u00b7OEt2  was added and the reaction mixture was stirred at room temperature for 5\u2005min. Removal of solvent followed by column chromatographic purification  gave the title compound as a colourless solid . Single crystals suitable for X-ray diffraction were prepared by slow evaporation of an ethyl acetate solution of the title compound at room temperature (m.p. = 454\u2013456\u2005K).To a solution of 1,3-di\u00adphenyl\u00adisobenzo\u00adfuran  in dry di\u00adchloro\u00admethane, dimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate  was added and the reaction mixture was stirred at room temperature for 1\u2005h. Removal of solvent followed by column chromatographic purification  afforded isobenzo\u00adfuran\u00addimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate adduct as a colourless solid . To a solution of the adduct  in dry di\u00adchloro\u00admethane, BFUiso(H) = 1.2Ueq(aryl C) and 1.5Ueq(methyl C), allowing for free rotation of the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018002360/is5487sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002360/is5487Isup2.hklStructure factors: contains datablock(s) I. DOI: 1823056CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A new co-crystal of piroxicam and gentisic acid has been characterized, in which the ratio of piroxicam  to gentisic acid is 2:1. N-(pyridin-2-yl)-2H-1\u03bb6,2-benzo\u00adthia\u00adzine-3-carboxamide\u20132-\u00adpyridin-1-ium\u20132,5-di\u00adhydroxy\u00adbenzoic acid, 2C15H13N3O4S\u00b7C7H6O4] has been synthesized using a microfluidic platform and initially identified using Raman spectroscopy. In the co-crystal, one piroxicam mol\u00adecule is in its neutral form and an intra\u00admolecular O\u2014H\u22efO hydrogen bond is observed. The other piroxicam mol\u00adecule is zwitterionic (proton transfer from the OH group to the pyridine N atom) and two intra\u00admolecular N\u2014H\u22efO hydrogen bonds occur. The gentisic acid mol\u00adecule shows whole-mol\u00adecule disorder over two sets of sites in a 0.809\u2005(2):0.191\u2005(2) ratio. In the crystal, extensive hydrogen bonding between the components forms layers propagating in the ab plane.A new 2:1 co-crystal of piroxicam and gentisic acid [systematic name: 4-hy\u00addroxy-1,1-dioxo- In the S2 mol\u00adecule, free rotation about the C\u2014C bond (C1 and C10) allows a second zwitterionic conformation in which intra\u00admolecular hydrogen bonds exist between the amine proton H2 and the enolate oxygen atom O4 [H\u22efA = 1.85\u2005(2)\u2005\u00c5] and the pyridinium proton H3 and the amide oxygen atom O3 [H\u22efA = 2.19\u2005(2)\u2005\u00c5]. Further details of the hydrogen bonding are provided in Table\u00a01The asymmetric unit of this co-crystal consists of two piroxicam mol\u00adecules and one gentisic acid mol\u00adecule, with all atoms residing on general positions Fig.\u00a01. One of A = 1.89\u2005(3)\u2005\u00c5]. The major orientation also participates in inter\u00admolecular hydrogen bonding. The minor orientation of the gentisic acid mol\u00adecule also displays intra\u00admolecular hydrogen bonding between the O11B hydroxide substituent and the O9B oxygen atom of the carb\u00adoxy\u00adlic acid (H\u22efA = 1.89\u2005\u00c5) but does not participate in inter\u00admolecular hydrogen bonding.The gentisic acid mol\u00adecule shows whole mol\u00adecule disorder over two orientations rotated by approximately 180\u00b0 in the plane of the aromatic ring with site occupancies of 0.809\u2005(2):0.191\u2005(2). The major orientation participates in intra\u00admolecular hydrogen bonding between the O11 hydroxide substituent of the benzene ring and the O9 oxygen atom of the carb\u00adoxy\u00adlic acid [H\u22efa-axis direction . The non-zwitterionic form of piroxicam accepts hydrogen bonds from the gentisic acid via O\u2014H\u22efN bonds between the carb\u00adoxy\u00adlic acid and the pyridine ring of piroxicam [H\u22efA = 1.74\u2005(3)\u2005\u00c5] as well as N\u2014H\u22efO bonds between the carbonyl oxygen atom of gentisic acid and the amine nitro\u00adgen atom of piroxicam [H\u22efA = 2.25\u2005(2)\u2005\u00c5]. The zwitterionic form of piroxicam accepts hydrogen bonds from the gentisic acid via O\u2014H\u22efO bonds between the 5-hy\u00addroxy substituent of gentisic acid and the enolate oxygen atom of piroxicam [H\u22efA = 1.94\u2005(3)\u2005\u00c5]. The repeat units are linked together by N\u2014H\u22efO bonds between the pyridinium nitro\u00adgen atoms and the amide oxygen atoms of the zwitterionic form of piroxicam [H\u22efA = 2.19\u2005(2)\u2005\u00c5].The repeating motif of the hexa\u00admeric unit is formed by one gentisic acid mol\u00adecule hydrogen bonded to two piroxicam mol\u00adecules, one of each conformation (M). The resulting solution was introduced into a microfluidic platform. The microfluidic platform was a 6 \u00d7 6 array of single microwells (\u223c100\u2005nl)  and gentisic acid (>=98.0%) were used as purchased from Sigma\u2013Aldrich . Aceto\u00adnitrile (>=99.9%) was used as purchased from Fisher Scientific . A 1:2 molar ratio of piroxicam:gentisic acid was dissolved in aceto\u00adnitrile. The concentration of piroxicam in aceto\u00adnitrile was near saturation  I. DOI: 10.1107/S2056989016017321/hb7625Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016017321/hb7625Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016017321/hb7625Isup4.cmlSupporting information file. DOI: 1512430CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Mol\u00adecules are connected into a three-dimensional architecture by O\u2014H\u22efO,N hydrogen bonding.A distorted octa\u00adhedral NS 6H12NOS2)2(C12H10N4)]2\u00b72H2O, comprises a CdII atom, two di\u00adthio\u00adcarbamate (dtc) anions, a monodentate 3-pyridine\u00adaldazine ligand and a lattice water mol\u00adecule. The binuclear mol\u00adecule is constructed by the application of inversion symmetry. One dtc ligand simultaneously chelates one cadmium atom and bridges the centrosymmetric mate, while the other dtc ligand is chelating only. This leads to a centrosymmetric [Cd(dtc)2]2 core to which are appended two 3-pyridine\u00adaldazine ligands. The resulting NS5 donor set is based on an octa\u00adhedron. The three-dimensional mol\u00adecular packing is sustained by hydroxyl-O\u2014H(hydrox\u00adyl) and water-O\u2014H\u22efO(hydrox\u00adyl) hydrogen bonding, leading to supra\u00admolecular layers parallel to (101) which are connected by water-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonding; additional C\u2014H\u22efO, S \u03c0(chelate ring) inter\u00adactions are also evident. The retention of the central [Cd(dtc)2]2 core upon adduct formation is unprecedented in the structural chemistry of the zinc-triad di\u00adthio\u00adcarbamates.The asymmetric unit in the title binuclear compound, [Cd(C The overwhelming majority of structures are binuclear, [Cd(S2CNRR\u2032)2]2, arising from equal numbers of \u03bc2-tridentate and bidentate (chelating) ligands furan-2-ylmeth\u00adyl]2}3 2]n CH2CH2OH]2}n CH2CH(OMe)2]2}n CH2CH2OH]2}n species 2 is reacted with bases, e.g. pyridyl-donors, the original aggregate is disrupted in that no dtc links are retained between cadmium atoms. Thus, when archetypal, binuclear [Cd(S2CNEt2)2]2 ethyl\u00adene ethane CH2CH2OH)]2}2 and 3-pyridine\u00adaldazine were isolated and shown by X-ray crystallography that despite having one potentially bidentate bi-pyridyl ligand per Cd[S2CN(iPr)CH2CH2OH)]2 unit, the central binuclear core CH2CH2OH)]2 entity, a 3-pyridine\u00adaldazine ligand and one water mol\u00adecule of solvation. One di\u00adthio\u00adcarbamate (dtc) ligand coordinates in a chelating mode forming very similar Cd\u2014S bond lengths, i.e. the difference between the Cd\u2014Sshort and Cd\u2014Slong bond lengths is only 0.033\u2005\u00c5; this equivalence is reflected in the equivalence in the associated C1\u2014S1, S2 bond lengths, Table\u00a01bridging bond lengths are close to being equal, differing by only 0.010\u2005\u00c5, and are longer by ca 0.1\u2005\u00c5 than the non-bridging Cd\u2014S4 bond length, Table\u00a01anti disposition about both imine bonds, i.e. C18=N4 = 1.283\u2005(3)\u2005\u00c5 and C19=N5 = 1.277\u2005(3)\u2005\u00c5; the central, azo bond is 1.415\u2005(2)\u2005\u00c5. The pyridyl-N atoms are also anti but there are twists in the 3-pyridine\u00adaldazine mol\u00adecule, as seen in the value of the dihedral angle between the two pyridyl rings of 22.78\u2005(12)\u00b0.The mol\u00adecular structure of the binuclear title compound, isolated as a dihydrate, is shown in Fig.\u00a01hy\u00addroxy\u2014H\u22efOhy\u00addroxy\u2014H\u22efOwater\u2014H}n chains are formed as shown in Fig.\u00a02a. The water mol\u00adecules also form water-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds on either side of the supra\u00admolecular layers sustained by O\u2014H\u22efO hydrogen bonds, Fig.\u00a02b. The pendent pyridyl-N atoms of Fig.\u00a02b are coordinating to cadmium atoms of successive layers so that a three-dimensional architecture results. Globally, and as seen from Fig.\u00a032CN(iPr)CH2CH2OH)]2}2 and 3-pyridine\u00adaldazine with the key links between them being hydrogen and coordinate bonding. Within this framework stabilized primarily by hydrogen-bonding inter\u00adactions, there are some second tier inter\u00adactions worthy of comment  inter\u00adactions are present  angle is 178\u00b0, in the inter-layer region, Table\u00a02Significant O\u2014H\u22efO hydrogen bonding is found in the mol\u00adecular packing of the binuclear title compound as would be expected from the chemical composition. Thus, mol\u00adecules are assembled into layers approximately parallel to (101) by hy\u00addroxy-O\u2014H\u22efO(hydrox\u00adyl) and hy\u00addroxy-O\u2014H\u22efO(water) hydrogen bonds as detailed in Table\u00a02et al., 20162-bridging 3-pyridine\u00adaldazine such as in the two most relevant compounds to the present study, namely {Cd[S2P(O-iPr)2]2}n 2]2}n 2]22\u00b7H2O}n (OH2)2]\u00b72ClO4}n . A good number of zinc and mercury binary di\u00adthio\u00adcarbamates are also known to adopt related binuclear [M(S2CNRR\u2019)2]2 aggregates owing to the presence of equal numbers of \u03bc2-tridentate and chelating ligands 2(hmta)]2, where hmta is hexa\u00admethyl\u00adene\u00adtetra\u00admine, for which an analogous centrosymmetric core and NS5 donor set as in the title compound was observed 2]2 cores in the structural chemistry of metal xanthates CH2CH2OH)]2  and 3-pyridine\u00adaldazine  were dissolved in 1-propanol (15\u2005ml). The solution was carefully covered with hexa\u00adnes. Yellow blocks were obtained via slow diffusion of hexa\u00adnes into the 1-propanol solution over two weeks. m.p. 389\u2013391\u2005K. IR (cm\u22121): 1449 (m) \u03bd(C=N), 1173 (s) \u03bd(C\u2014S). 1H NMR: \u03b4 9.04 , 8.81 , 8.72 , 8.29 , 7.56 , 5.22 , 4.83 , 3.74 , 3.68 , 1.18 . TGA: three steps, corresponding to loss of water , loss of the 3-pyridine\u00adaldazine ligand , and decomposition down to cadmium sulfide .Cd[SUiso(H) set at 1.2\u20131.5Ueq(C). The oxygen-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set at 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016012214/wm5312sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016012214/wm5312Isup2.hklStructure factors: contains datablock(s) I. DOI: 1496352CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Acta Cryst. E71, o125-o126. The motivation for this redetermination follows from negligence of important features of the difference electron-density maps as well as from wrongly applied constraints, which significantly affect the structural model. The corrections affect mainly the positions of the H atoms involved in the hydrogen bonds (centered on the primary amine group for which the H atom turned out to be disordered over two positions about the centre of an N\u22efH\u22efO hydrogen bond) and the methyl group, which is disordered and has now been remodelled.The title structure, 4-amino\u00adbenzoic acid 4-methyl\u00adpyridine/4-methyl\u00adpyridinium 4-amino\u00adbenzoate 0.58/0.42, has been redetermined from the data published by Kumar  6H7N\u00b7C7H7NO2)\u00b70.42(C6H8N+\u00b7C7H6NO2\u2212), has been redetermined from the data published by Kumar et al. \u2005\u00c5], while the H atoms of the primary amine group account more realistically for the hydrogen-bond pattern after the removal of the positional constraints. All the O\u2014H\u22efN or N\u2014H\u22efO hydrogen bonds which are present in the title structure are of moderate strength.The title structure, 4-amino\u00adbenzoic acid 4-methyl\u00adpyridine/4-methyl\u00adpyridinium 4-amino\u00adbenzoate 0.58/0.42, 0.58(C al. 2015. Acta Cr Figs. 1et al.  = 1.2Ueq(Nprimary/secondary amine).In the course of recalculation of suspect structures that were retrieved from the CSD, the structure determination of the title structure by Kumar  al. 2015, CSD refet al., 2006et al.  (H1x) and 0.42(7) (H1y)  Figs. 1 and 2 \u25b8.x\u22efN2iii/O1\u22efH1yiii\u2014N2iii  is quite long for an O\u22efN hydrogen bond with a disordered bridging hydrogen atom, i.e. for a hydrogen atom the substantial part of its electron density is situated along the connecting line between the donor/acceptor atoms as happens in O1\u2014H1x\u22efN2iii/O1\u22efH1yiii\u2014N2iii of the title structure x hydrogen trioxo\u00adfluoro\u00adphosphate(1\u2212)x monohydrate/2,4,6-tri\u00adamino\u00adpyrimidinium(2+)x)(1\u2013 trioxo\u00adfluoro\u00adphosphate(2\u2212)x) \u2212 pKa(acid) is close to 0 , or ionized, forming a salt  x\u00a0+\u00a01, y, z\u00a0+\u00a01] with a bridging hydrogen atom disordered over two positions (H1x and H1yiii) forms a finite D(3) pattern  \u2212x\u00a0+\u00a01, \u2212y, z\u00a0\u2212\u00a0a--N1\u2013H1b and atom O2iv /\u03c3(i) < 0.6}. The indicators of the refinement of such a model were substanti\u00adally higher: Robs = 0.0503, Rwobs = 0.1035, Rall = 0.0930, Rwall = 0.1119. The condition for the observed diffractions was I/\u03c3(I) > 3, cf. Table\u00a02It is worthwhile mentioning that the recalculation of the original model with 10.1107/S2056989017013226/su5390sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017013226/su5390Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017013226/su5390Isup3.cmlSupporting information file. DOI: 1574686CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The packing of the title compound features short C\u2014I\u22efN contacts. 18H18I2N2O2, consists of one half-mol\u00adecule, completed by the application of inversion symmetry. The mol\u00adecule adopts the typical structure for this class of bis-benxozazines, characterized by an anti orientation of the two benzoxazine rings around the central C\u2014C bond. The oxazinic ring adopts a half-chair conformation. In the crystal, mol\u00adecules are linked by C\u2014I\u22efN short contacts [I\u22efN = 3.378\u2005(2)\u2005\u00c5], generating layers lying parallel to the bc plane.The asymmetric unit of the title compound, C So, an iodine functional bis-1,3-benzoxazine, namely 3,3\u2032-bis\u00ad has been synthesized in high yield and purity.As the electrophilic character of the substituents affects the stability both of the reaction inter\u00admediates and the benzoxazine ring  bond \u2005\u00c5, \u03b8 =129.6\u2005(2)\u00b0, \u03c6 = 283.6\u2005(3)\u00b0: with respect to the plane formed by O1/C3/C4/C5, the deviations of C2 and N1 are 0.301\u2005(3) and \u22120.320\u2005(3)\u2005\u00c5, respectively. The observed C\u2014O bond length [1.376\u2005(3)\u2005\u00c5] is in a good agreement with the related p-fluoro and p-bromo structures . Moreover, the C2\u2014N1\u2014C1 [112.6\u2005(2)\u00b0] and C5\u2014N1\u2014C1 [113.0\u2005(2)\u00b0] angles are larger than the mean value of sp3 hybridization in ammonia  ,  monohydrate   set to 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017005047/hb7668sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017005047/hb7668Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005047/hb7668Isup3.cmlSupporting information file. DOI: 1541561CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atoms in {Zn[S2CN(R)CH2CH2OH]2(pyridine)\u00b7pyridine}, for R = Me (I) and Et (II), are coordinated non-symmetrically by two di\u00adthio\u00adcarbamate ligands and by a pyridine ligand, resulting in an NS4 donor set that defines a distorted geometry in each case; the non-coordinating pyridine mol\u00adecules are connected with the Zn-containing mol\u00adecules via O\u2014H\u22efN(pyridine) hydrogen bonds. The mol\u00adecular packing features significant (hy\u00addroxy)O\u2014H\u22efO(hy\u00addroxy) hydrogen bonding, in each case leading to supra\u00admolecular chains with zigzag (I) or helical (II) arrangements.The Zn 4H8NOS2)2(C5H5N)]\u00b7C5H5N (I) and [Zn(C5H10NOS2)2(C5H5N)]\u00b7C5H5N (II), which differ by having di\u00adthio\u00adcarbamate N-bound methyl (I) and ethyl (II) groups, is the coordination of each ZnII atom by two non-symmetrically chelating di\u00adthio\u00adcarbamate ligands and by a pyridine ligand; in each case, the non-coordinating pyridine mol\u00adecule is connected to the Zn-containing mol\u00adecule via a (hy\u00addroxy)O\u2014H\u22efN(pyridine) hydrogen bond. The resulting NS4 coordination geometry is closer to a square-pyramid than a trigonal bipyramid in the case of (I), but almost inter\u00admediate between the two extremes in (II). The mol\u00adecular packing features (hy\u00addroxy)O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds, leading to supra\u00admolecular chains with a zigzag arrangement along [10-1] (I) or a helical arrangement along [010] (II). In (I), \u03c0\u2013\u03c0 [inter-centroid distances = 3.4738\u2005(10) and 3.4848\u2005(10)\u2005\u00c5] between coordinating and non-coordinating pyridine mol\u00adecules lead to stacks comprising alternating rings along the a axis. In (II), weaker \u03c0\u2013\u03c0 contacts occur between centrosymmetrically related pairs of coordinating pyridine mol\u00adecules [inter-centroid separation = 3.9815\u2005(14)\u2005\u00c5]. Further inter\u00adactions, including C\u2014H\u22ef\u03c0(chelate) inter\u00adactions in (I), lead to a three-dimensional architecture in each case.The common structural feature of the title compounds, [Zn(C While many similarities are apparent in their coordination propensities ethyl\u00adene (bpe). With Zn(S2COEt)2, a 1:1 compound can be prepared which crystallography shows to be a one-dimensional coordination polymer with a zigzag arrangement  group only the dimeric aggregate [Zn(S2COCy)2]2(bpe) could be isolated 2]2, in that 1:1 one-dimensional coordination polymers can be formed with bpe when R = i-Pr  di\u00adthio\u00adcarbamates of bpe, where only binuclear species, [Zn(S2CNR2)2]2(bpe), have been isolated, e.g. R = Me CH2CH2OH 2]2, where the dimeric aggregate, mediated by Zn\u2014S bridges, self-assembles into a three-dimensional architecture based on hydrogen bonding CH2CH2OH]2}2(bipy), which allows for the construction of a doubly inter\u00adpenetrated architecture. When the bridge is pyrazine, the three-dimensional architecture is sustained by (hy\u00addroxy)O\u2014H\u22efO(hy\u00addroxy) hydrogen bonding exclusively CH2N(H)C(=O)C(=O)N(H)CH2(3-pyrid\u00adyl), i.e. LH2, the dimeric {Zn[S2CN(Me)CH2CH2OH)2]2}2(LH2) aggregates are inter\u00adwoven into supra\u00admolecular chains sustained by hydrogen bonding CH2CH2OH]2(pyridine)\u00b7pyridine} for R = Me (I)In order to overcome the reluctance of zinc(II) di\u00adthio\u00adcarbamates to generate extended supra\u00admolecular architectures, the di\u00adthio\u00adcarbamate ligands can be functionalized with hydrogen-bonding potential, 2CN(R)CH2CH2OH]2(pyridine)\u00b7.pyridine}, for R = Me (I)long - Zn\u2014Sshort. For the S1-di\u00adthio\u00adcarbamate ligand, \u0394Zn\u2014S = 0.23\u2005\u00c5, but this decreases to 0.17\u2005\u00c5 for the S3-ligand. From the data in Table\u00a01\u03c4, which ranges from 0.0 to 1.0\u00b0 for ideal square-pyramidal to trigonal-bipyramidal, respectively \u03c4 is 0.56, indicating a small tendency towards trigonal\u2013bipyramidal, certainly when compared with the coordination geometry for (I)i.e. 166.375\u2005(19)\u00b0. As for (I)etc. The solvent mol\u00adecule in (II)via a hydrogen bond.To a first approximation the structure of (II)2CN(R)CH2CH2OH]2 mol\u00adecules in (I)Despite the relatively close agreement between the coord\u00adination geometries of the Zn. A view of the unit-cell contents is shown in Fig.\u00a04b. As for (I)In the crystal of (II)e.g. as anti-cancer agents 2(pyridine), which was motivated by the desire to destroy the binuclear structure observed for the binary di\u00adthio\u00adcarbamate compound to form a lighter (i.e. lower mol\u00adecular weight) species to facilitate chemical vapour deposition studies 2(pyridine) species. More sophisticated monodentate nitro\u00adgen-donor adducts are also known, such as substituted pyridines, e.g. 3-hy\u00addroxy\u00adpyridine 2CNEt2)2(pyridine) adduct has also been characterized as a mono-pyridine solvate CH2CH2OH]2, R = Me and Et, precursors were prepared as per established procedures CH2CH2OH]2, R = Me and Et (50\u2005mg), was dissolved in pyridine (10\u2005ml) and carefully layered with hexa\u00adnes (10\u2005ml). Crystals were harvested directly from solution and mounted immediately onto the diffractometer to avoid loss of pyridine.The Zn[SUiso(H) set to 1.2\u20131.5Ueq(C). The O-bound H atoms were located in difference-Fourier maps but were refined with a distance restraint of O\u2014H = 0.84\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O). For (I)\u22123, respectively, were located 1.03 and 1.02\u2005\u00c5 from the Zn atom. For (II)\u22123, respectively, were located 1.02 and 0.61\u2005\u00c5 from the Zn atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017010568/wm5406sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017010568/wm5406Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017010568/wm5406IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1562767, 1562766CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The bridging mode of the organic ligands leads to the formation of a polymeric layer structure parallel to the ab plane.The zinc cation in the structure has a N 8H4O6S)(C10H8N2S)(H2O)]\u00b70.26H2O}n, is characterized by a layered arrangement parallel to the ab plane. The zinc cation is five-coordinated in a slightly distorted trigonal\u2013bipyramidal coordination environment defined by two pyridine ligands, two carboxyl\u00adate groups of two thio\u00adphene di\u00adcarboxyl\u00adate ligands, and by one water mol\u00adecule. The ethyl\u00adene bridge in the dioxine ligand is disordered over two sets of sites [occupancy ratio 0.624\u2005(9):0.376\u2005(9)]. Several hydrogen-bonding inter\u00adactions of the types O\u2014H\u22efO, C\u2014H\u22efO, C\u2014H\u22efS and C\u2014H\u22efN ensure the cohesion within the crystal structure.The crystal structure of the title polymer, {[Zn(C The equatorial Zn1\u2014N1 bond length is 2.1131\u2005(18)\u2005\u00c5, while the axial Zn1\u2014N2 bond is longer, 2.2107\u2005(18)\u2005\u00c5. Similarly, the two equatorial Zn1\u2014O  bond lengths, ranging from 1.9835\u2005(15) to 2.0285\u2005(15)\u2005\u00c5, are shorter than the axial Zn1\u2014O7 bond of 2.1375\u2005(17)\u2005\u00c5. These are typical values, numerical details of which are given in Table\u00a01In the crystal structure of (1), the zinc ion is coordinated by four organic ligands and one water mol\u00adecule, giving rise to a slightly distorted trigonal\u2013bipyramidal coordination environment. Two nitro\u00adgen atoms are delivered by two symmetry-related pyridine ligands, two oxygen atoms of two carboxyl groups stem from two symmetry-related thio\u00adphene carboxyl\u00adate ligands, and one O atom from the aqua ligand Fig.\u00a01. In the ab plane  to the coordinating O5 atom of the carboxyl group. Another (pyridine)C\u2014H group (C18\u2014H18A) is hydrogen-bonded to the disordered O8 atom of the lattice water mol\u00adecule. Three O\u2014H\u22efO inter\u00adactions are present between the coordinating water mol\u00adecule to either the carboxyl group oxygen atoms or the dioxine oxygen atom in the thio\u00adphene derivative with D\u22efA distances ranging between 2.733\u2005(2) and 3.123\u2005(2)\u2005\u00c5 and corresponding O\u2014H\u22efO angles of 135\u2005(2) and 159\u2005(2)\u00b0. Numerous other C\u2014H\u22efO inter\u00adactions are present between the disordered dioxine C\u2014H groups and a carboxyl O atom (O6) or the lattice water atom O8. Other C\u2014H\u22efO inter\u00adactions involve pyridyl C\u2014H groups and the carboxyl O3 atom. In addition, one C\u2014H\u22efS inter\u00adaction and one C\u2014H\u22efN inter\u00adaction are found between pyridyl C\u2014H groups and the sulfane S1 atom or the pyridyl N1 atom C\u2014H group   was prepared as reported , H2ttdc , 4,4\u2032-di\u00adthiodi\u00adpyridine , 5\u2005ml di\u00admethyl\u00adformamide and 3\u2005ml water was mixed and heated at 353\u2005K for 3 days. After cooling, 0.17\u2005g light-yellow crystals were collected in a yield of 32%.2,3-Di\u00adhydro\u00adthieno could not be retrieved from difference maps and thus were not part of the model. Two carbon atoms of the dioxine moiety are disordered over two sets of sites and were refined in two parts (C3\u2013C4/C3A\u2013C4A) with a refined occupancy ratio of 0.624\u2005(9)/0.376\u2005(9). Soft restraints  were applied on the disordered atoms to keep their geometries and atomic displacement parameters reasonable.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017002031/wm5363sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002031/wm5363Isup2.hklStructure factors: contains datablock(s) I. DOI: 1528425CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this paper, we report the discovery of a \u201creciprocal\u201d carbonyl-carbonyl interaction with substantial back and forth n\u2192\u03c0* and \u03c0\u2192\u03c0* electron delocalization between neighboring carbonyl groups. We have carried out experimental studies, analyses of crystallographic databases and theoretical calculations to show the presence of this interaction in both small molecules and proteins. In proteins, these interactions are primarily found in polyproline II (PPII) helices. As PPII are the most abundant secondary structures in unfolded proteins, we propose that these local interactions may have implications in protein folding.Carbonyl-carbonyl  \u03c0* non covalent interactions affect the structure and stability of small molecules and proteins. Here, the authors carry out experimental studies, analyses of crystallographic databases and theoretical calculations to describe an additional type of carbonyl-carbonyl interaction.Carbonyl-carbonyl  Intermolecular noncovalent interactions of varying magnitude are also responsible for the existence of different states of matter4. Carbonyl-carbonyl (C\u2550O\u00b7\u00b7\u00b7C\u2550O) n\u2192\u03c0* interactions where one of the lone pairs (n) on the oxygen atom of a carbonyl group is delocalized over the antibonding \u03c0* orbital of a nearby carbonyl C\u2550O bond (\u03c0*C\u2550O) along the B\u00fcrgi-Dunitz trajectory5 (\u2220O\u00b7\u00b7\u00b7C\u2009\u2550\u2009O\u2009~\u2009109\u00b0) have attracted a great deal of attention in recent years11. Previous studies have shown that C\u2550O\u00b7\u00b7\u00b7C\u2550O n\u2192\u03c0* interactions not only influence geometries of important small molecules15 but also play crucial roles in determining the three dimensional structures of polyesters16, peptides17, peptoids21 and proteins25. C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions between the side-chain and backbone carbonyl groups of Asp, Asn, Glu, and Gln were also observed in the high-resolution crystal structures of proteins27. C\u2550O\u00b7\u00b7\u00b7C\u2550O n\u2192\u03c0* interaction is characterized by a short O\u00b7\u00b7\u00b7C\u2550O distance (d) of less than 3.22\u2009\u00c5 [the sum of van der Waals radii of carbon and oxygen atom28], bond angle \u2220O\u00b7\u00b7\u00b7C\u2550O (\u03b8) of ~109\u00b0 and the pyramidality  of the acceptor carbon atom towards the donor oxygen atom29. Direct spectroscopic evidence for n\u2192\u03c0* interaction was recently reported by using gas-phase infrared spectroscopy30.Nature effectively uses combinations of weak noncovalent interactions in the functional forms of various biologically important molecules such as nucleic acids and proteinsn\u2192\u03c0* interaction both donor and acceptor C\u2550O bonds will be polarized, which will make the acceptor carbonyl oxygen atom a better electron donor and the donor carbonyl carbon atom a better electron acceptor. The acceptor carbonyl oxygen, therefore, can donate electrons to another nearby carbonyl carbon either to form a sequential chain of O\u00b7\u00b7\u00b7C contacts 16 and proteins22, reciprocal n\u2192\u03c0* interactions remained unexplored. Allen and coworkers reported anti-parallel arrangements of carbonyl groups in ketone dimers that were bound together by two intermolecular C\u2550O\u00b7\u00b7\u00b7C\u2550O short contacts of dipolar nature31. Maccallum et al reported a similar geometrical arrangement of carbonyl groups in right-twisted \u03b2-strands and observed two chemically distinct dipolar C\u2550O\u00b7\u00b7\u00b7C\u2550O short contacts32. However, these C\u2550O\u00b7\u00b7\u00b7C\u2550O short contacts were considerably longer than the sum of van der Waals radii of C and O atoms.We anticipated that due to cts Fig.\u00a0 or it caons Fig.\u00a0. Althougn\u2192\u03c0* interactions should lead to back and forth donations between the carbonyl pairs. Based on our hypothesis, we discovered the presence of \u201creciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions\u201d both in small molecules and proteins. To establish the existence of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions, we designed and synthesized model compounds and carried out X-ray crystallographic and theoretical studies. Further, we carried out Cambridge Structural Database (CSD)33 and Protein Data Bank (PDB)34 analyses to show that these interactions are widely present in small molecules and proteins. In proteins, these interactions are primarily found in random coils and turn regions. Based on our observations we propose that reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions may be a key local interaction that restricts the number of conformers of unfolded proteins and may have a role in protein folding.In this paper, we hypothesized that the polarization of the carbonyl groups by n\u2192\u03c0* interactions, we have synthesized N,N\u02b9-diacylhydrazines 1-8 having various substituents on either side of the carbonyl groups  crystallized in nonplanar form with the carbonyl groups oriented almost orthogonal to each other  , the two carbonyl groups stay far apart. The crystallographic distances d1 and d2  show no evidence of n\u2192\u03c0* interaction , an increase in the acceptor ability of the carbonyl CO-II is expected, which should increase n\u2192\u03c0* interaction from the oxygen atom of CO-I to the \u03c0*C\u2550O orbital of CO-II. However, the inductive electron withdrawal of Cl can be negated by the electron donation from the Cl lone pairs into the antibonding orbitals (\u03c3* and \u03c0*) of the adjacent carbonyl group (CO-II). In compound 4, we observed such electron delocalizations from the Cl lone pairs to both \u03c3* and \u03c0* orbitals of the C=O bonds of CO-II group, which contributed 0.67\u2009kcal\u2009mol\u22121 to the stabilization  and presence of NBO second order perturbation energy . As can be anticipated, the nature of the two atoms/groups between the interacting carbonyl groups plays a key role in keeping the two carbonyl groups non coplanar and provides them the conformation required for reciprocal interactions th amino acid residue is defined as d1. The distance between the carbonyl oxygen of (i\u2009+\u20091)th residue and carbonyl carbon of ith residue is defined as d2. The corresponding \u2220O\u00b7\u00b7\u00b7C\u2550O angles are defined as \u03b81 and \u03b82, respectively  deviates significantly from the B\u00fcrgi-Dunitz trajectory  studied here show that shorter distances d1 and d2\u2009\u2264\u20093.2\u2009\u00c5 fall within the tail of the full distribution  less than 10%, out of which 2184 showed the presence of reciprocal interactions in them. The PDB protein structures ranked by the number of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions present in them are included in Supplementary Data\u00a0nge Fig.\u00a0. The angory Fig.\u00a0. These o22, Bartlett et al reported one-sided n\u2192\u03c0* interactions with d\u2009\u2264\u20093.20\u2009\u00c5 and 99o\u2009\u2264\u2009\u03b8\u2009\u2264\u2009119o. As we have applied the same distance (d\u2009\u2264\u20093.20\u2009\u00c5) and resolution (<1.6\u2009\u00c5) criteria, the reciprocal interactions observed here for angles 99o\u2009\u2264\u2009\u03b81, \u03b82\u2009\u2264\u2009119o would be observed as one-sided n\u2192\u03c0* interactions by using the criteria of Bartlett et al. As can be seen from Fig.\u00a0\u03b81 and \u03b82 in the range of 99\u00b0\u2013119\u00b0  is a very small percentage (6.5%) of the total number of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions that are being reported here. This indicates that reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions are novel and distinct from one-sided n\u2192\u03c0* interactions reported previously.In a previous study1 and d2\u2009\u2264\u20093.20\u2009\u00c5) that covers the complete range of observed \u2220O\u00b7\u00b7\u00b7C\u2009=\u2009O angle (\u03b8) (70\u2013110\u00b0) clearly showed the presence of reciprocal n\u2192\u03c0* interactions , \u03c0\u2192\u03c0* interactions were observed for \u03b81 and \u03b82 values <90\u00b0 also (Table\u00a0n\u2192\u03c0* and two \u03c0\u2192\u03c0* interactions) could be substantial to protein stabilization. Based on the NBO calculations at B3LYP/6-311\u2009+\u2009G level, we observed that reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions contribute 0.27\u20134.41\u2009kcal\u2009mol\u22121  to the stabilization of proteins per amino acid pair  . Secondary structure analyses using Stride38 show that reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions have considerable abundance in random coils (~20%) and turn regions (10%) of proteins but negligible presence in \u03b1-helices (0.35%)  : ]. We have confirmed this by plotting the \u03c6, \u03c8 angles of residues in the random coil regions having reciprocal interactions  Table\u00a0. This isons Fig.\u00a0. This isn\u2192\u03c0* interactions are twisted  of the central two amino acids do not participate in any inter-residue hydrogen bonding. Therefore, we assume that these residues may participate in local reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions either between themselves or with their other neighbors, which should compensate for the lack hydrogen bonding interactions in them. A careful examination of the orientations of the carbonyl groups in various common \u03b2-turns indicated that reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interaction may be feasible between the first and the second residues of type I\u02b9 and II \u03b2-turns due to the favorable orientations of the two carbonyl groups but likely to be unfavoured in type I and II\u02b9 \u03b2-turns. In fact, analysis of the 10 protein crystal structures discussed above show that most of the reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interaction pairs found in \u03b2-turns were type II, followed by type IV (Supplementary Table\u00a0n\u2192\u03c0* interactions in \u03b1-helices and \u03b2-sheets22 (Pro\u2009>\u2009Gly\u2009>\u2009Ala). Analysis of distribution of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions among the amino acid pairs in various proteins reveals that Pro\u2013Pro is the most abundant pair  show a strong correlation  against the stabilization energies due to n\u2192\u03c0* interactions [NBO second order perturbation energies E1n\u2192\u03c0*)( and E2n\u2192\u03c0*)(] reported in Tables\u00a0En\u2192\u03c0*)( for n\u2192\u03c0* interactions decreases with an increase in the O\u00b7\u00b7\u00b7C (d) in synthetic molecules 1\u20138, molecules taken from CSD and interacting amino acid pairs obtained from PDB (Tables\u00a0n\u2192\u03c0* [En\u2192\u03c0*)(] and \u03c0\u2192\u03c0* [E\u03c0\u2192\u03c0*)(] interaction energies reported in Tables\u00a0n\u2192\u03c0* interactions increases charge on donor oxygen lone pair (nO) and depletes it on acceptor carbonyl \u03c0*C\u2550O orbital, which correlate well with the strength of O\u00b7\u00b7\u00b7C distances  between two dipoles could be used to understand the dipolar nature of interaction between them. As we know, antiparallel (T\u2009~\u2009180\u00b0) dipoles attract and parallel dipoles (T\u2009~\u20090\u00b0) repel each other whereas two orthogonal dipoles (T\u2009~\u200990\u00b0) have net zero dipolar interaction. In case of reciprocal interaction, the C\u2009=\u2009O\u00b7\u00b7\u00b7C\u2009=\u2009O torsion angles show an orientational preference [C\u2550O\u00b7\u00b7\u00b7C\u2550O torsion angle falls in 60\u00b0 to 90\u00b0 (or \u221260\u00b0 to \u221290\u00b0) range] as a consequence of the simultaneous restrictions on d1 and d2 (\u22643.2\u2009\u00c5). However, the values of the C\u2550O\u00b7\u00b7\u00b7C\u2550O torsion angles (~90\u00b0) suggest that there would be almost net zero interaction between the dipoles, eliminating the possibility of strong dipolar interactions. Therefore, we conclude that orbital delocalization is the major driving force for the stabilization of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions. An elaborate energy decomposition analysis may be required for the accurate deconvolution of various factors contributing to the stabilization of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O short contacts.The nature of C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions has been debated in the literature. While some consider them on Figs.\u00a0. In Fig.B Tables\u00a0. The ovenO) and \u03c0*C\u2550O orbital is weak. This weak donation from the first carbonyl group to the second is compensated by a back donation from the second carbonyl group to the first. In many cases, reciprocal \u03c0\u2192\u03c0* interactions were also observed along with reciprocal n\u2192\u03c0* interactions and their overall contributions to the stabilization of molecules having reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O short contacts could be significant. In proteins, C\u2550O\u00b7\u00b7\u00b7C\u2550O n\u2192\u03c0* interactions are present in all types of secondary structures. While one-sided n\u2192\u03c0* interactions are prevalent in \u03b1-helices23, reciprocal interactions are abundant in PPII helices and turn regions. Prevalence of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions in PPII helices and turn regions of proteins suggests a possible role for these interactions in protein folding. Further, the presence of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions in distorted \u03b1-helices and twisted \u03b2-sheets suggests that these interactions could stabilize secondary structures that deviate from their regular geometries. The reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions present at the interface of two different types of secondary structures could also help in stabilizing the strained amino acid residues that are present at these interfaces. In future, it would be interesting to investigate the ability of amino acid pairs having high propensity to get involved in reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions to stabilize PPII helices and \u03b2-turns. It would also be interesting to investigate if some non-peptidic fragments obtained from the CSD search having strong reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions could be used to stabilize PPII conformation or design peptide-turns. Finally, an energy decomposition analysis would provide better understanding of the forces that contributes to the stabilization of reciprocal C\u2550O\u00b7\u00b7\u00b7C\u2550O interactions.We conclude that reciprocal carbonyl-carbonyl interactions exist both in small organic molecules and proteins. However, due to geometrical constraints associated with such interactions, the approach of the donor oxygen atoms to the acceptor carbon atoms deviates significantly from the B\u00fcrgi-Dunitz trajectory, and therefore, electron delocalization between the oxygen lone pair . Details of the crystallization conditions are given in Supplementary Table\u00a0Single crystals of compounds 1\u20138 were determined by measuring X-ray intensity data. Bruker D8Venture APEX 342 single crystal home source X-ray diffractometer equipped with CMOS PHOTON 100 detector and Monochromated microfocus sources Mo K\u03b1 radiation (\u03bb\u2009=\u20090.71073\u2009\u00c5) were used for data collection in phi (\u03d5) and omega (\u03c9) scan strategy at room temperature (298\u2009K). The data was processed using SAINT43 and absorption correction was done using SADABS44 implemented in APEX 3. For structure solution XSHELL program based on SHELX45 was used. The non-hydrogen atoms were refined anisotropically and located in successive difference Fourier syntheses. The hydrogen atoms were fixed to neutron bond length using appropriate HFIX commands. ORTEP diagrams of compounds 1\u20138 (CCDC 1486577- 1486584) is provided in Supplementary Fig.\u00a05 crystallized with a water molecule in the asymmetric unit. However, for clarity we have not shown the water molecule in its ORTEP diagram. Compound 7 has disorder at chlorine atom; the occupancy of disordered chlorine atom namely Cl1A and Cl1B was refined using the PART command. Similar ADP restraint SIMU46 and rigid bond restraint DELU46 was applied to stabilize the anisotropic refinement. SADI46 instruction was used to restrain the distance to equal. The anisotropic displacement parameter for disordered chlorine atom was fixed using EADP46 constraint.Single crystal structures of compound 33 (CSD version 5.21 Nov. 2015) using Conquest47 (version 1.18) program. The fragment chosen for the search is shown in Supplementary Fig.\u00a0X is indicative for any atom. Only unique matching fragments were taken and the fragment was chosen in such a way that there are at least two carbonyl groups irrespective of their nature. Distances d1 (O2\u2013C5) and d2 (O6\u2013C1) are restricted to \u22643.2\u2009\u00c5. Angles [O2\u2013C5\u2013O6 (\u03b81) and O6\u2013C1\u2013O2 (\u03b82)] and dihedral angles (C1\u2013O2\u2013C5\u2013O6 and C5\u2013O6\u2013C1\u2013O2) were printed without any restriction. Only crystalline, non-ionic and non-polymeric organic molecules having no disorder and error with R factor\u2009\u2264\u20095% having at least three covalent bond separations between the carbonyl groups were considered in this search.Intramolecular C\u2550O\u00b7\u00b7\u00b7C\u2550O noncovalent interactions were searched and structural data were retrieved from Cambridge Structural Database34 using a search criterion of resolution <1.6\u2009\u00c5 with redundancy (pairwise sequence identity) less than 10%, downloaded on 19 January 2016. Out of 2269 proteins, 2184 showed the reciprocal n\u2192\u03c0* interaction. For proteins existing in polymeric form or for proteins containing amino acids in more than one conformation, Chain A and conformation A were chosen, except for 57 proteins where chain A is absent. Distance d1 is defined as distance between the ith amide oxygen to the subsequent (i\u2009+\u20091)th amide carbon, while d2 is defined as distance between the (i\u2009+\u20091)th amide oxygen to the ith amide carbon .A subset of 2269 protein was culled out from RCSB PDB48. The Hartree-Fock (HF)49 and the hybrid Becke 3-Lee-Yang-Parr (B3LYP)51 exchange correlation functional with 6-311\u2009+\u2009G  basis set were used for the calculations. Natural bond orbital (NBO)35 analyses were performed on the crystal geometries of the synthetic molecules and small organic molecules obtained from CSD search. For proteins, the coordinates of the interacting amino acid residue pair were extracted using PyMOL52. The \u03b1-carbons of the amino acid residues adjacent to N and C termini of the amino acid pair were also included, so as to mimic a dipeptide with N and C termini capped with N(CO)Me and (CO)NMe, respectively. Finally, hydrogen atoms were added to the structure using PyMOL ( and E\u03c0\u2192\u03c0*) level of theory.All the calculations were performed by using Gaussian09 suite of quantum chemistry programswww.ccdc.cam.ac.uk/.The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files, and also are available from the corresponding author upon reasonable request. X-ray crystallographic data for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number CCDC 1486577-1486584. These data can be obtained free of charge from the CCDC via Supplementary InformationSupplementary Data 1Supplementary Data 2Supplementary Data 3Supplementary Data 4Supplementary Data 5Supplementary Data 6Supplementary Data 7Supplementary Data 8Supplementary Data 9Peer Review File"}
{"text": "Only one enanti\u00adomer was observed crystallographically, resulting from the combination of (S)-sec-butyl\u00adamine with l-tartaric acid.The title hydrated mol\u00adecular salt was prepared by deprotonation of enanti\u00adopure  4H12N+\u00b7C4H5O6\u2212\u00b7H2O, was prepared by deprotonation of enanti\u00adopure l-tartaric acid with racemic sec-butyl\u00adamine in water. Only one enanti\u00adomer was observed crystallographically, resulting from the combination of (S)-sec-butyl\u00adamine with l-tartaric acid. The sec-butyl\u00adammonium moiety is disordered over two conformations related by rotation around the CH\u2013CH2 bond; the refined occupancy ratio is 0.68\u2005(1):0.32\u2005(1). In the crystal, mol\u00adecules are linked through a network of O\u2014H\u22efO and N\u2014H\u22efO hydrogen-bonding inter\u00adactions, between the ammonium H atoms, the tartrate hy\u00addroxy H atoms, and the inter\u00adstitial water, forming a three-dimensional supra\u00admolecular structure.The title hydrated mol\u00adecular salt, C Since enanti\u00adomers have identical physical properties, they cannot be separated by standard physical means such as distillation, crystallization, or chromatography. One common method to overcome this issue is to convert the racemic compound into a mixture of diastereomers through reaction with an enanti\u00adopure component -sec-butyl ammonium cation, the l-tartrate anion, and one mol\u00adecule of water in the asymmetric unit. The Flack parameter [\u20132.7\u2005(8)] was not of use in determining the absolute configuration of the sec-butyl\u00adamine in the crystal. The absolute configuration of the (S)-sec-butyl ammonium cation is therefore based on the known absolute configuration of the l-tartaric acid used during compound preparation. The final structure is disordered, with the sec-butyl ammonium moiety taking on two different rotamers about the C2\u2013C3 axis [refined occupancy ratio is 0.68\u2005(1):0.32\u2005(1)]. The major component takes on a conformation where the C4 methyl group and N9 ammonium are in a gauche relationship , while the minor component places the C4A methyl group anti\u00adperiplanar to the N9A ammonium . The C\u2014C bond lengths in the amine and tartrate units average 1.523\u2005(11)\u2005\u00c5 [1.516\u2005(22)\u2005\u00c5 for the minor component of the disorder] and 1.532\u2005(5)\u2005\u00c5, respectively. The C\u2014N bonds of the two components of the disorder average 1.498\u2005(17)\u2005\u00c5. The tartrate C\u2014OH bonds average 1.411\u2005(4)\u2005\u00c5, while the C\u2014O bonds of the carboxyl moieties average 1.257\u2005(4)\u2005\u00c5 for the one involved in hydrogen bonding with the amine, and 1.258\u2005(4)\u2005\u00c5 for the other. An intra\u00admolecular hydrogen bond [2.00\u2005(3)\u2005\u00c5] occurs with O12 acting as a hydrogen-bond donor to O11.The mol\u00adecular structure of the title hydrated mol\u00adecular salt is shown in Fig.\u00a01ip Fig.\u00a01a, whileum Fig.\u00a01b. The CA atom of the sec-butyl ammonium cation acts as a hydrogen-bond donor to O11 of the tartrate anion [1.89\u2005(2)\u2005\u00c5], and the tartrate O13 donates a hydrogen bond to O16 of water [1.83\u2005(3)\u2005\u00c5]. The water in turn acts as a hydrogen-bond donor to O10 [2.01\u2005(3)\u2005\u00c5] and O15 [1.93\u2005(4)\u2005\u00c5] of two adjacent symmetry-related mol\u00adecules. Three additional hydrogen bonds are formed from N9, with N9\u2014H9B donating to O12 of an adjacent mol\u00adecule [1.97\u2005(3)\u2005\u00c5], and N9\u2014H9C donating to both O13 [2.16\u2005(4)\u2005\u00c5] and O15 [2.20\u2005(4)\u2005\u00c5] of a second adjacent mol\u00adecule. Finally, O14 donates a hydrogen bond to O10 of an additional symmetry-related mol\u00adecule [1.58\u2005(5)\u2005\u00c5]. A view of the crystal packing reveals the amine, tartrate, and water mol\u00adecules form columns when viewed down the c axis  was added to 40\u2005ml of water and stirred to ensure homogeneity. While stirring, l-tartaric acid  was slowly added. The solution was covered and allowed to stand at ambient temperature. After 24\u2005h, crystal formation was evident. The crystallization process was allowed to continue undisturbed for one week, at which point a crystal for diffraction analysis was selected directly from the reaction mixture without further purification or isolation. The crystals can be isolated by vacuum filtration to yield a white crystalline solid .The title compound was prepared Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The sec-butyl ammonium moiety displays a twofold disorder arising from two different rotamers being present that is best described as a 0.68\u2005(1):0.32\u2005(1) ratio of the two possible conformations. In the final cycles of refinement SAME restraints were applied to the two components of the disordered sec-butyl ammonium moiety and DFIX restraints were applied to the N\u2014H bonds [N\u2014H = 0.91\u2005(2)\u2005\u00c5] and the ammonium H\u22efH distances [H\u22efH = 1.50\u2005(2)\u2005\u00c5], to improve the refinement and geometry.Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989017005448/su5364sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017005448/su5364Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005448/su5364Isup3.cmlSupporting information file. DOI: 1543331CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl\u00adate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the CdII atoms are bridged by the carboxyl\u00adate O atoms of two symmetry-related NB anions, thus completing the distorted N2O5 penta\u00adgonal\u2013bipyramidal coordination sphere of each CdII atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02\u2005(7) and 5.76\u2005(9)\u00b0, respectively. In the crystal, C\u2014H\u22efN hydrogen bonds link the mol\u00adecules, enclosing R22(26) ring motifs, in which they are further linked via C\u2014H\u22efO hydrogen bonds, resulting in a three-dimensional network. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions between parallel benzene rings and between parallel pyridine rings of adjacent mol\u00adecules , as well as a weak C\u2014H\u22ef\u03c0 inter\u00adaction, may further stabilize the crystal structure.The asymmetric unit of the title compound, [Cd The two CPy ligands are monodentate (through the pyridine N atoms), while both NB anions act as bidentate ligands through their carboxyl\u00adate O atoms  and its symmetry-related counterpart . Hence, this carboxyl\u00adate group not only chelates to one CdII atom but also bridges two CdII atoms , one chelating NB anion (O1 and O2) and two 3-cyano\u00adpyridine (CPy) ligands (N3 and N5), resulting in a distorted penta\u00adgonal\u2013bipyramidal environment. The five carboxyl\u00adate O atoms  of the three NB anions around the CdII atom form a distorted penta\u00adgonal arrangement, with an average Cd1\u2014O bond length of 2.42\u2005\u00c5 (Table\u00a01i separation in the binuclear mol\u00adecule is 3.9360\u2005(15)\u2005\u00c5 and is comparable to the corresponding M\u2014M distances  in the structurally related transition metal(II) complexes . The metal atoms are bridged by two NA ligand N and O atoms in (III), (V) and (VI), while they are bridged by two carboxyl\u00adate O atoms in (IV).The asymmetric unit of the title complex contains one Cdms Fig.\u00a01. The cenms Fig.\u00a02. Thus, e\u00c5 Table\u00a01. The dis\u00c5 Table\u00a01 and 2 \u25b8.M\u2014O  angles are 60.92\u2005(12)\u00b0 in (II), 53.50\u2005(14)\u00b0 in (IV), 57.61\u2005(8)\u00b0 in (V), and 54.22\u2005(4) and 53.32\u2005(5)\u00b0 in (VI). The dihedral angles between the planar carboxyl\u00adate groups (O1/O2/C1 and O5/O6/C8) and the adjacent benzene [A (C2\u2013C7) and B (C9\u2013C14)] rings in the title structure are 17.18\u2005(13) and 3.36\u2005(12)\u00b0, respectively, while the benzene (A and B) and pyridine [C (N3/C15\u2013C19) and D (N5/C21\u2013C25)] rings are oriented at dihedral angles of A/B = 10.02\u2005(7)\u00b0, A/C = 72.70\u2005(7)\u00b0, A/D = 74.72\u2005(7)\u00b0, B/C = 82.28\u2005(7)\u00b0, B/D = 84.54\u2005(8)\u00b0 and C/D = 5.76\u2005(9)\u00b0.The near equalities of the C1\u2014O1 [1.264\u2005(3)\u2005\u00c5], C1\u2014O2 [1.241\u2005(3)\u2005\u00c5], C8\u2014O5 [1.256\u2005(3)\u2005\u00c5] and C8\u2014O6 [1.253\u2005(3)\u2005\u00c5] bonds in the carboxyl\u00adate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O1\u2014Cd1\u2014O2 and O5\u2014Cd1\u2014O6 bite angles are reduced to 54.33\u2005(5) and 53.47\u2005(5)\u00b0, respectively. The corresponding O\u2014cpy\u22efOc (cpy = cyano\u00adpyridine and c = carboxyl\u00adate) and C\u2014Hnb\u22efOc (nb = nitro\u00adbenzoate) hydrogen bonds  hydrogen bonds (Table\u00a02Cg1\u2013Cg2i and Cg3\u2013Cg4ii  may further stabilize the structure, with centroid\u2013centroid distances of 3.885\u2005(1) and 3.712\u2005(1)\u2005\u00c5, respectively. A weak C\u2014H\u22ef\u03c0 inter\u00adaction  = 1.2Ueq(C). The maximum and minimum electron densities were found at 1.43 and 0.80\u2005\u00c5 from atoms O2 and Cd1, respectively.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a034\u00b78H2O  in H2O (50\u2005ml) and 3-cyano\u00adpyridine  in H2O (50\u2005ml) with sodium 3-nitro\u00adbenzoate  in H2O (100\u2005ml) at 333\u2005K. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colourless single crystals.The title compound was prepared by the reaction of 3CdSO10.1107/S2056989017002675/wm5366sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017002675/wm5366Isup2.hklStructure factors: contains datablock(s) I. DOI: 1533101CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The Zn-containing units are connected into a one-dimensional coordination polymer (zigzag topology) propagating in the [010] direction, with one di\u00adthio\u00adcarbamate ligand bridging in a \u03bc2-\u03ba3 mode, employing one pyridyl N and both di\u00adthio\u00adcarbamate S atoms, while the other is \u03ba2-chelating. In each case, the resultant ZnNS4 coordination geometry approximates a square pyramid, with the pyridyl N atom in the apical position. In the crystal, the chains are linked into a three-dimensional architecture by methyl- and pyridyl-C\u2014H\u22efS, methyl\u00adene-C\u2014H\u22efN(pyrid\u00adyl) and pyridyl-C\u2014H\u22ef\u03c0(ZnS2C) inter\u00adactions. The connection between the chain and the 4-methyl\u00adpyridine solvent mol\u00adecule is of the type pyridyl-C\u2014H\u22efN(4-methyl\u00adpyridine).The title compound, {[Zn(C Thus, a two-dimensional architecture is found in centrosymmetric {Zn[S2CN(Et)CH2py]2 residues, shown in Fig.\u00a01i.e. \u0394(Zn\u2014S) = [Zn\u2014S(long) \u2212 Zn\u2014S(short)], for the S1-di\u00adthio\u00adcarbamate ligand of 0.32\u2005\u00c5 is greater than the value of 0.10\u2005\u00c5 for the S3-di\u00adthio\u00adcarbamate ligand. For the Zn2-mol\u00adecule, these differences diminish to 0.23 and 0.09\u2005\u00c5 for the S5- and S7-di\u00adthio\u00adcarbamate ligands, respectively. The similarity of the structures is emphasized in the overlay diagram of Fig.\u00a022-\u03ba3 mode, chelating one ZnII cation and simultaneously bridging another via the pyridyl N atom. It is noted that it is the di\u00adthio\u00adcarbamate ligand that forms the more equivalent Zn\u2014S bond lengths in each residue that forms the bridging inter\u00adactions. The resultant coordination geometry for each ZnII cation is based on an NS4 donor set.The asymmetric unit of (I)et al., 1984i.e. S1\u2013S4 (r.m.s. deviation = 0.1721\u2005\u00c5), in the direction of the pyridyl N6 atom. For the Zn2-mol\u00adecule, the deviation of the Zn2 cation from the S4 plane is 0.6018\u2005(6)\u2005\u00c5 and the r.m.s. deviation through the S5\u2013S8 atoms is 0.1273\u2005\u00c5.For five-coordinate species, the value computed for \u03c4 is a useful indicator of the adopted coordination geometry, with the values of \u03c4 ranging from 0 to 1 for ideal square-pyramidal and trigonal\u2013bipyramidal geometries, respectively 2CN(Et)CH2py]2\u00b73-methyl\u00adpyridine}n, which was also isolated from an experiment attempting to coordinate isomeric methyl\u00adpyridines to the heavy element \u2212[S2CN(Et)CH2py], found in (I)2CN(Et)CH2py]2\u00b73-methyl\u00adpyridine}n  salt CH2py]2, for R = Me, nBu and Ph  inter\u00adaction of 2.98\u2005\u00c5 between the two mol\u00adecules comprising the asymmetric unit. This result is consistent with surveys of diorganotin bis\u00ad(di\u00adthio\u00adcarbamate)s in general 2, a recent survey indicated that secondary bonding inter\u00adactions occur in only 10% of their crystal structures CH2py]2 (generated from the reaction of Zn(NO3)2\u00b7H2O and \u2212[S2CN(Et)CH2py]) from 4-picoline. Suitable single crystals formed upon slow evaporation of the solvent (m.p. 337\u2013339\u2005K).The title compound was isolated from the recrystallization of Zn{[SUiso(H) values set at 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017010179/hb7691sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017010179/hb7691Isup2.hklStructure factors: contains datablock(s) I. DOI: 1561011CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A distinctive O\u2014H\u22efN-based synthon is present. Cl\u22efCl and \u03c0\u2013\u03c0 stacking inter\u00adactions further stabilize the crystal structure, forming a two-dimensional network parallel to the bc plane.The asymmetric unit of the title compound, 2C In recent years, the physicochemical properties of active pharmaceutical ingredients have been improved widely with the use of co-crystals via O\u2014H\u22efN hydrogen-bonding inter\u00adactions between (O1\u2014H1) of the carboxyl group and the nitro\u00adgen (N1) of BPY \u2005\u00c5, C3\u2014Cl1\u22efCl1iii = 151.71\u2005(1)\u00b0; symmetry code: (iii) 1\u00a0\u2212\u00a0x, y, z] \u2005\u00c5; Cg1 is the centroid of the N1/C6/C7/C8/C9/C10 ring; symmetry code: (ii) 1\u00a0\u2212\u00a0x, 2\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z]. The perpendicular distance between two parallel mol\u00adecules is 3.4812\u2005(15)\u2005\u00c5. This weak inter\u00adaction holds the hydrogen-bonded chains together, supporting a two-dimensional supra\u00admolecular network parallel to the bc plane, as seen in Fig.\u00a023TPC and BPY are inter\u00adconnected Y Table\u00a01. This O\u2014et al., 2001N,N\u2032-dioxide-3-hy\u00addroxy-2-naphthoic acid (1/2) , 10\u2005ml of a hot methano\u00adlic solution of BPY  was added. The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week, clear yellow plates were obtained. The crystal used for X-ray diffraction data collection was cut from a larger crystal.Uiso(H) = 1.2Ueq(C). The carb\u00adoxy\u00adlic acid hydrogen atom was freely refined, including its isotropic displacement parameter.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016013724/hg5476sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016013724/hg5476Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013724/hg5476Isup3.cmlSupporting information file. DOI: 1501060CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Its reaction with copper chloride lead to the formation of a copper(II) paddle-wheel structure.Tranexamic acid is an anti\u00adfibrinolytic amino acid that exists as a zwitterion [ trans-4-(amino\u00admeth\u00adyl)cyclo\u00adhexane-1-carb\u00adoxy\u00adlic acid], is an anti\u00adfibrinolytic amino acid that exists as a zwitterion [trans-4-(ammonio\u00admeth\u00adyl)cyclo\u00adhexane-1-carboxyl\u00adate] in the solid state. Its reaction with copper chloride leads to the formation of a compound with a copper(II) paddle-wheel structure that crystallizes as a hexa\u00adhydrate, [Cu2Cl2(C8H15NO2)4]2+\u00b72Cl\u2212\u00b76H2O. The asymmetric unit is composed of a copper(II) cation, two zwitterionic tranexamic acid units, a coordinating Cl\u2212 anion and a free Cl\u2212 anion, together with three water mol\u00adecules of crystallization. The whole structure is generated by inversion symmetry, with the Cu\u22efCu axle of the paddle-wheel dication being located about a center of symmetry. The cyclo\u00adhexane rings of the zwitterionic tranexamic acid units have chair conformations. The carboxyl\u00adate groups that bridge the two copper(II) cations are inclined to one another by 88.4\u2005(8)\u00b0. The copper(II) cation is ligated by four carboxyl\u00adate O atoms in the equatorial plane and by a Cl\u2212 ion in the axial position. Hence, it has a fivefold O4Cl coordination sphere with a perfect square-pyramidal geometry and a \u03c45 index of zero. In the crystal, the paddle-wheel dications are linked by a series of N\u2014H\u22efCl hydrogen bonds, involving the coordinating and free Cl\u2212 ions, forming a three-dimensional network. This network is strengthened by a series of N\u2014H\u22efOwater, Owater\u2014H\u22efCl and Owater\u2014H\u22efO hydrogen bonds.Tranexamic acid [systematic name:  It has important anti\u00adfibrinolytic activity and is used extensively in both trauma and normal surgery to prevent excessive blood loss \u2005\u00c5; symmetry code (i): \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01] of the paddle-wheel being located about a center of symmetry. Selected bond lengths and angles in the paddle-wheel dication are given in Table\u00a01\u2212 ion, Cl1, in the axial position. The Cu\u2014O distances vary from 1.950\u2005(4) to 1.991\u2005(3)\u2005\u00c5, with a longer Cu1\u2014Cl1 axial distance of 2.499\u2005(1)\u2005\u00c5 (Table\u00a01i), has a perfect square-pyramidal coordination sphere with a \u03c45 index of 0.0 \u2005\u00c5, \u03b8 = 176.3\u2005(6)\u00b0, \u03c6 = 358\u2005(13)\u00b0, and for ring C10\u2013C15 are Q = 0.568\u2005(6)\u2005\u00c5, \u03b8 = 6.0\u2005(6)\u00b0, \u03c6 = 137\u2005(6)\u00b0. The carboxyl\u00adate groups (C1/O1/O2 and C9/O3/O4) are inclined to the mean planes of the four planar atoms of the respective cyclo\u00adhexane rings (C3/C4/C6/C7 and C11/C12/C14/C15) by 67.5\u2005(6) and 85.8\u2005(7)\u00b0, while they are inclined to one another by 88.4\u2005(8)\u00b0. The ammonio\u00admethyl units, C5/C8/N1 and C13/C16/N2, are inclined to the mean planes of the four planar atoms of the respective cyclo\u00adhexane rings (C3/C4/C6/C7 and C11/C12/C14/C15) by 34.9\u2005(6) and 47.5\u2005(6)\u00b0.The conformations of the two zwitterionic tranexamic acid units differ slightly. The cyclo\u00adhexane rings (C2\u2013C7 and C10\u2013C15) have chair conformations; puckering parameters for ring C2\u2013C7 are 3+ groups of the zwitterionic tranexamic acid units and the coordinating and free Cl\u2013 ions are linked by a series of N\u2014H\u22efCl hydrogen bonds forming a three-dimensional framework  and the hydro\u00adchloride of the cis-isomer (CHCAHC) were reported in 1966 , viz. tranexamic acid  is inclined to the mean plane of the four planar atoms of the cyclo\u00adhexane ring by 48.9\u2005(2)\u00b0, compared to 67.5\u2005(6) and 85.8\u2005(7)\u00b0 in the title compound. The plane of the ammonio\u00admethyl unit (Car\u2014C\u2014N) is inclined to the same mean plane of the four planar atoms of the cyclo\u00adhexane ring by 37.4\u2005(2)\u00b0, compared to 34.9\u2005(6) and 47.5\u2005(6)\u00b0 in the title compound. Hence, on complexation the cyclo\u00adhexane rings are rotated about the Ccarboxyl\u00adate\u2014Ccyclo\u00adhexa\u00adne bonds (C1\u2014C2 and C9\u2014C10), most probably to minimize steric hindrance.A search of the Cambridge Structural Database . The Cu\u22efCu distances vary from ca 2.63 to 2.84\u2005\u00c5, with the carboxyl\u00adate groups being inclined to one another by ca 84.65\u201390\u00b0, and the Cu\u2014Cl distances varying from ca 2.41 to 2.49\u2005\u00c5. The values observed for the title compound fall within these limits . In all 13 compounds the copper atoms have perfect square-pyramidal geometry, with \u03c45 = 0.0.In the CSD over 1500 copper(II) paddle-wheel structures have been deposited. There are only 13 compounds in which the axial position is occupied by a Cl2\u00b72H2O  in 20\u2005ml of aceto\u00adnitrile at ambient temperature and the mixture was stirred for 30\u2005min. The green solution obtained was filtered and the filtrate kept undisturbed at room temperature for slow evaporation. After five days green plate-like crystals of the title compound were obtained.Tranexamic acid  dissolved in 10\u2005ml of deionized water was added dropwise to a transparent blue solution of CuClUiso(H) = 1.5Ueq(O). The ammonium H atoms and the C-bound H atoms were included in calculated positions and treated as riding: N\u2014H = 0.91\u2005\u00c5, C-H = 0.99\u20131.00\u2005\u00c5 with Uiso(H) = 1.5Ueq(N-ammonium) and 1.2Ueq(C) for other H atoms. In the final difference-Fourier map the residual density peaks  are located at a distance of 1.2 and 0.9\u2005\u00c5, respectively, from the copper atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017012543/wm5416sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017012543/wm5416Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012543/wm5416sup3.pdfCSD search of axially Cl- ligated Cu-Cu paddle-wheel structures. DOI: 1571897CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Interleukin 17-producing \u03b3\u03b4 T (\u03b3\u03b4T17) cells have unconventional trafficking characteristics, residing in mucocutaneous tissues but also homing into inflamed tissues via circulation. Despite being fundamental to \u03b3\u03b4T17-driven early protective immunity and exacerbation of autoimmunity and cancer, migratory cues controlling \u03b3\u03b4T17 cell positioning in barrier tissues and recruitment to inflammatory sites are still unclear. Here we show that \u03b3\u03b4T17 cells constitutively express chemokine receptors CCR6 and CCR2. While CCR6 recruits resting \u03b3\u03b4T17 cells to the dermis, CCR2 drives rapid \u03b3\u03b4T17 cell recruitment to inflamed tissues during autoimmunity, cancer and infection. Downregulation of CCR6 by IRF4 and BATF upon \u03b3\u03b4T17 activation is required for optimal recruitment of \u03b3\u03b4T17 cells to inflamed tissue by preventing their sequestration into uninflamed dermis. These findings establish a lymphocyte trafficking model whereby a hierarchy of homing signals is prioritized by dynamic receptor expression to drive both tissue surveillance and rapid recruitment of \u03b3\u03b4T17 cells to inflammatory lesions. IL-17-producing \u03b3\u03b4 T (\u03b3\u03b4T17) cells position in barrier tissues but also home to inflammatory sites. How this trafficking is regulated is unclear. Here the authors show that the dynamic expression of chemokine receptors CCR2 and CCR6 differentiates \u03b3\u03b4T17 cell trafficking patterns at homeostasis and in inflammatory scenarios. In models of autoimmunity, cancer and infection, activation-induced downregulation of CCR6 releases \u03b3\u03b4T17 cells from their homeostatic immunosurveillance trafficking circuit through the skin and circulation, which then enhances their CCR2-dependent homing to inflamed tissue. Therefore, the dynamic interplay between CCR6 and CCR2 expression defines \u03b3\u03b4T17 cell trafficking patterns between resting and activated states.\u2212CCR2+ phenotype marking the encephalitogenic granulocyte\u2013macrophage colony-stimulating factor/interferon-\u03b3-producing population221Il17aCre \u00d7 Rosa26eYFP mice, where Il17a expression drives permanent marking of cells with eYFP\u2212CD44hi phenotype, characteristic of \u03b3\u03b4T17 cells (+ and V\u03b36+ \u03b3\u03b4T17 cell subsets as distinguished by both V\u03b34 expression and CD3/T-cell receptor (TCR) expression level, as previously reported (\u2018CD3bright staining')ex vivo chemotaxis (\u2212CCR2+) were prominent in lung and gut-associated tissues  (Ccr2-deficiency inhibited \u03b3\u03b4T17 cell recruitment to the CNS at both onset and peak disease (Ccr6 and Ccr2 (Ccr6\u2212/\u2212Ccr2\u2212/\u2212) did not further affect \u03b3\u03b4T17 cell infiltration in either model  . CCR2-dres (LNs) . Similar disease , time po disease . CCR2 aper model .Ccr2\u2212/\u2212Ccr6\u2212/\u2212 mice exhibited enhanced tumour growth, while Ccr2\u2212/\u2212 and Ccr2\u2212/\u2212Ccr6\u2212/\u2212 mice had decreased EAE severity  and Ccr2\u2212/\u2212 \u03b3\u03b4T17 cells were co-transferred into B16 melanoma-bearing recipients. While donor \u03b3\u03b4T17 cells recovered from spleen retained the input ratio, Ccr2\u2212/\u2212 \u03b3\u03b4T17 cells did not migrate efficiently to tumours. This observation was true for both V\u03b34+ and V\u03b36+ subsets  than WT at 72\u2009h post-infection , a population previously reported to produce IL-17 and distinct from TCRhi dendritic epidermal T cellslo cells were entirely marked by eYFP in Il17aCre \u00d7 Rosa26eYFP mice, despite negligible IL-17A production following ex vivo restimulation (Ccr6-deficiency reduced the number of both V\u03b34+ and V\u03b34\u2212 (V\u03b36+) \u03b3\u03b4Tlo cells, although the ratio was skewed slightly towards V\u03b36+ cells  was highly expressed in resting \u03b3\u03b4T17 cells but was downregulated by 24\u2009h of activation. Batf and Prdm1 (Blimp1) were rapidly upregulated by 24\u2009h, while Irf8 and Irf4 were upregulated by 48\u2009h, although Irf4 was already present in resting \u03b3\u03b4T17 cells. Expression of Eomes and Tbx21 (T-bet) at rest or following activation was minimal  mice were bred at the University of Adelaide animal facility. Irf4\u2212/\u2212, Irf8\u2212/\u2212, Batf\u2212/\u2212 and LckCrePrdm1fl/fl mice were bred at the WEHI animal facility. Mice were age- and gender-matched and used at 6\u201314 weeks of age. Experiments were conducted with approval of the University of Adelaide Animal Ethics Committee.C57Bl/6 (WT) and Ly5.1 mice were purchased from Animal Resource Centre  or bred at the University of Adelaide animal facility. 35\u201355 (GL Biochem) in phosphate-buffered saline (PBS) emulsified 1:1 in complete Freund's adjuvant, coupled with i.p. injection of 300\u2009ng Pertussis toxin (Sapphire Bioscience) on days 0 and 2. Mice were analysed at clinical scores of 0.5 (onset) and 2\u20133 (peak) in wild type (WT) mice, where scoring criteria were: 0.5 tremor, 1 partially limp tail, 2 fully limp tail, 2.25 unable to right, 2.5 sprawled hindlimbs, 2.75 one hindlimb paralysed, 3 both hindlimbs paralysed, 3.5 one forelimb paralysed. B16.F10 melanoma cells  were cultured in RPMI 1640 containing 10% fetal calf serum (FCS) and 5 \u00d7 104 cells were injected subcutaneously into mice at four sites. S. pneumoniae EF3030 was grown to a D600 of 0.18 in nutrient broth with 10% horse serum at 37\u2009\u00b0C 5% CO2 and stored at \u221280\u2009\u00b0C. Stocks were defrosted and 1 \u00d7 106 colony-forming units were delivered intranasally. Bacterial load was determined by serial dilution of concentrated NW onto blood agar with 5\u2009\u03bcg\u2009ml\u22121 gentamicin (Sigma).Mice were immunized for chronic EAE by subcutaneous injection of 100\u2009\u03bcg of MOGg. The following digestions were performed at 37\u2009\u00b0C with 30U\u2009ml\u22121 DNase (Sigma). Epidermis and dermis from ears or shaved trunk skin were separated by incubation in 0.375% tryspin for 2\u2009h at 37\u2009\u00b0C, and then digested separately with 85\u2009\u03bcg\u2009ml\u22121 Liberase TM (Roche) for 1\u2009h. Tumours and perfused lungs were digested in 2\u2009mg\u2009ml\u22121 collagenase (Sigma) for 1\u2009h. NP tissue between the nose tip and eyes was dissected following removal of nasal-associated lymphoid tissue, digested with 2\u2009mg\u2009ml\u22121 collagenase for 1.5\u2009h and separated by a 40/80% Percoll gradient at 600g. Livers were pressed through 70\u2009\u03bcm filters and then lymphocytes were isolated by a 37.5% Percoll gradient at 850g. Flushed and longitudinally opened small intestine free of Peyer's patches was washed in PBS then incubated in 5\u2009mM EDTA for 40\u2009min at 37\u2009\u00b0C to remove epithelium, before remaining lamina propria was digested with 0.5\u2009mg\u2009ml\u22121 collagenase for 1.5\u2009h at 37\u2009\u00b0C and separated over a 40/80% Percoll gradient at 1,000g to isolate lamina propria lymphocytes. Peritoneal exudate cells were collected by 3 \u00d7 1\u2009ml PBS washes.Single-cell suspensions were prepared from lymphoid organs by pressing through 70\u2009\u03bcm filters. Peripheral blood was collected into heparinized Vacutainer tubes (BD). Red blood cells were lysed as required. CNS from PBS-perfused mice was pressed through 70\u2009\u03bcm filters and then separated over a 30/70% Percoll (GE) gradient at 5006 lymphocytes per well using antibodies and other reagents detailed in \u22121 PMA (Life Technologies), 1\u2009nM ionomycin (Life Technologies) and 1/1,500 GolgiStop (BD) for 4\u2009h at 37\u2009\u00b0C. Cells were washed in PBS and stained with Near Infrared fixable dye diluted 1/1,000 (Life Technologies) for 15\u2009min at room temperature. Cells were then washed with FACS buffer  and blocked with mouse \u03b3-globulin (m\u03b3g) (200\u2009\u03bcg\u2009ml\u22121) for 5\u2009min at room temperature. All subsequent steps were incubated at 4\u2009\u00b0C. For purified antibodies, cells were stained with purified antibody for 20\u201360\u2009min, washed in FACS buffer, stained with secondary antibody in m\u03b3g (200\u2009\u03bcg\u2009ml\u22121) and normal mouse serum (NMS) (1%) for 20\u2009min, washed in FACS buffer and blocked with rat \u03b3-globulin for 15\u2009min. Cells were stained with directly conjugated and biotinylated antibodies for 20\u2009min. In the case of biotinylated antibodies, cells were then washed in FACS buffer and stained with streptavidin for 15\u2009min. Cells were then washed in PBS 0.04% azide. For intracellular cytokine staining, cells were incubated in Cytofix/Cytoperm (BD) for 20\u2009min, washed in Permwash (BD) and stained with intracellular directly conjugated antibodies for 20\u2009min. For transcription factor staining, cells were incubated in Foxp3 kit perm buffer (eBioscience) for 30\u2009min to overnight, and then washed in Foxp3 kit permwash (eBioscience). Cells were then stained with directly conjugated \u03b1-transcription factor antibodies in NMS (2%) and normal rat serum (2%), and then washed in PBS 0.04% azide. All stains were washed in PBS 0.04% azide, resuspended in PBS 1% paraformaldehyde and stored at 4\u2009\u00b0C in the dark.Single-cell suspensions were stained in 96-well round- or v-bottom plates (Corning) at 2 \u00d7 10Ccr2\u2212/\u2212 \u03b3\u03b4T17 cells. CCR2 and CCR6 gating was determined by relevant isotype controls. For measurement of fluorescence intensity, relevant isotype control geometric mean fluorescence intensity was subtracted from raw geometric mean fluorescence intensity value. For in vivo proliferation analysis, mice were given 2\u2009mg BrdU i.p. and then drinking water with 0.8\u2009mg\u2009ml\u22121 BrdU 2% glucose. Following restimulation and surface staining, cells were permeabilized, DNase-treated and stained with \u03b1-BrdU (BD) according to the manufacturer's instructions. For in vitro proliferation analysis, cells were labelled with Cell Proliferation Dye (eBioscience) according to the manufacturer's instructions. Flow cytometry was acquired on a BD LSR II or FACSAria and analysed with FlowJo (Treestar). Gating strategies are detailed in Specificity of \u03b1-CCR2 was confirmed by negative staining on 6 cells per ml in RPMI 1640 containing 10% FCS, antibiotics, 1 \u00d7 Glutamax (Gibco), 10\u2009mM HEPES (SA Pathology), 1\u2009mM sodium pyruvate, 54 pM \u03b2-mercaptoethanol and 1 \u00d7 non-essential amino acids (Gibco) with 5\u2009ng\u2009ml\u22121 recombinant (r)IL-23 (eBioscience), 5\u2009ng\u2009ml\u22121 rIL-1\u03b2 (Miltenyi Biotec) and 10\u2009\u03bcg\u2009ml\u22121 \u03b1-IFN-\u03b3 (BioXCell) in 96-well round-bottom plates coated with 1\u2009\u03bcg\u2009ml\u22121 \u03b1-TCR-\u03b3\u03b4  for 3 days. Cells were washed and re-seeded on fresh plastic at 1 \u00d7 106 cells per ml for a further 3 days as above without TCR-\u03b3\u03b4 stimulation. Cells were then washed and re-seeded in 20\u2009ng\u2009ml\u22121 rIL-7 (Peprotech) and 10\u2009\u03bcg\u2009ml\u22121 \u03b1-IFN-\u03b3 for a further 3 days. pMIG, pMIG-Rorc and pMIG-Ccr6 (cloned from mouse Ccr6 cDNA) were transfected into EcoPack 2 293 cells  with Lipofectamine 2000 (ThermoFisher), and supernatant collected after 48\u2009h. \u03b3\u03b4T17 cells at days 4 and 5 of culture were centrifuged at 2,500\u2009r.p.m. (30\u2009\u00b0C for 1.5\u2009h) in supernatant with 8\u2009\u03bcg\u2009ml\u22121 polybrene (Sigma) in flat-bottom 96 well trays before being returned to culture.Pooled spleen and LN cells were cultured at 1 \u00d7 10Ccr2\u2212/\u2212 and Ccr6tg trafficking experiments, 1\u20132 \u00d7 106 each of in vitro-expanded F1 (CD45.1+CD45.2+) and Ccr2\u2212/\u2212(CD45.2+), or transduced control and Ccr6tg \u03b3\u03b4T17 cells (F1 or WT), were mixed and transferred i.v. into Ly5.1 (CD45.1+) recipient mice d5 post-challenge with B16 melanoma, d8\u201310 post EAE induction or 24\u2009h post-S. pneumoniae infection. \u03b3\u03b4T17 cell infiltration of target organs was analysed 24\u201348\u2009h post-transfer, and CD45 congenic ratios were normalized to input sample. For S. pneumoniae Tcrd\u2212/\u2212 reconstitution, in vitro-expanded WT and Ccr2\u2212/\u2212 \u03b3\u03b4T17 cells were further purified by MACS (Miltenyi Biotec) before 3 \u00d7 106 cells were transferred into separate Tcrd\u2212/\u2212 hosts 24\u2009h prior to infection. For na\u00efve dermis trafficking experiments, 5\u201310 \u00d7 107 fresh WT or Ccr6\u2212/\u2212 lymphocytes or 3 \u00d7 107 72\u2009h IL-23/IL-1\u03b2-stimulated WT lymphocytes were transferred into separate unimmunized Ly5.1 mice and analysed 36\u2009h later. Number of recovered cells was normalized to number of \u03b3\u03b4T17 cells transferred.For Tumour and NP supernatants from digested samples and supernatants from filtered CNS were supplemented with protease inhibitors (Sigma) and stored at \u221280\u2009\u00b0C. Mouse CCL2 Duoset ELISA (R&D) was conducted according to the manufacturer's instructions.Il17aCre \u00d7 Rose26eYFP mice were enriched by MACS using mouse TCR\u03b3\u03b4+ isolation kit , and then sorted using a BD FACSAria. Na\u00efve CD4+ T cells were sorted from WT splenocytes, and skin stromal populations were sorted from digested epidermal and dermal suspensions from WT mice. Sorting strategies are detailed in \u2212(CT target\u2013CT reference) where reference was Rplp0.\u03b3\u03b4 T cells from 6 splenocytes or 2 \u00d7 105in vitro-expanded \u03b3\u03b4T17 cells were loaded into the upper chambers and plates were incubated at 37\u2009\u00b0C for 3\u2009h. Lower wells were harvested and stained for flow cytometry. CountBrite beads (Invitrogen) were added to samples prior to acquisition to normalize event counts. Chemotaxis index was calculated as number of gated events divided by number in 0 chemokine control.Splenocytes were rested in complete RPMI for 3\u20134\u2009h at 37\u2009\u00b0C, washed and suspended in chemotaxis buffer . \u03b3\u03b4T17 cells from culture were washed and suspended in chemotaxis buffer. CCL2 or CCL20 (from the late Prof. Ian Clark-Lewis) were diluted in chemotaxis buffer and loaded into the lower chambers of 96-well 5\u2009\u03bcm pore transwell plates (Corning). 2 \u00d7 10L-glutamine, \u03b2-mercaptoethanol) at 2.5 \u00d7 106 cells per ml with 10\u2009ng\u2009ml\u22121 rIL-23 (eBioscience), 10\u2009ng\u2009ml\u22121 rIL-1\u03b2 (Miltenyi Biotec), 20\u2009ng\u2009ml\u22121 rIL-7 (Peprotech), 10\u2009ng\u2009ml\u22121 rIL-12 (R&D), 10\u2009ng\u2009ml\u22121 rIL-18 (R&D) and/or with pre-coating in 1\u2009\u03bcg\u2009ml\u22121 \u03b1-TCR-\u03b3\u03b4 (Biolegend) for up to 72\u2009h at 37\u2009\u00b0C. For mitomycin C pre-treatment, cells were first incubated with 10\u2009\u03bcg\u2009ml\u22121 mitomycin C (Sigma) in complete IMDM at 2 \u00d7 107 cells per ml for 2\u2009h at 37\u2009\u00b0C before extensive washing.Splenocytes were cultured in complete IMDM .Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.Supplementary Figures and Supplementary Tables"}
{"text": "In the crystal, N\u2014H\u22efO, O\u2014H\u22efO and N\u2014H\u22efF hydrogen bonds and weak \u03c0\u2013\u03c0 inter\u00adactions connect chains of mol\u00adecules into a three-dimensional network.The title compound {systematic name: 2-[\u00adoxy]acetic acid}, C 7H5Cl2FN2O3, the mean plane of the carb\u00adoxy\u00adlic acid substituent and the pyridyl ring plane subtend a dihedral angle of 77.5\u2005(1)\u00b0. In the crystal, pairs of O\u2014H\u22efO hydrogen bonds form inversion dimers with R22(8) ring motifs. These are extended into chains along [011] by N\u2014H\u22efF hydrogen bonds. In addition, inter\u00admolecular N\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 inter\u00adactions [ring centroid separation = 3.4602\u2005(9)\u2005\u00c5] connect these chains into a three-dimensional network.In the title pyridine herbicide {systematic name: 2-[\u00adoxy]acetic acid}, C It is widely used on cereal crops, olive trees and fallow croplands to control broad-leaf weeds \u2005\u00c5; symmetry code: (iv) \u2212x, \u2212y\u00a0+\u00a02, \u2212z], resulting in a three-dimensional network structure  = 0.84\u2005\u00c5, Uiso = 1.5Ueq(C) for the O\u2014H group, d(N\u2014H) = 0.88\u2005\u00c5, Uiso = 1.2Ueq(C) for the amine group, and d(C\u2014H) = 0.99\u2005\u00c5, Uiso = 1.2Ueq(C) for the CH2 group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016018533/sj5515sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016018533/sj5515Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016018533/sj5515Isup3.cmlSupporting information file. DOI: 1518035CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystals of both compounds, mol\u00adecules are linked  30H18N2O5S, (I), and C27H18N2O4S2, (II), are carbazole derivatives with a phenyl\u00adsulfonyl group and a nitro\u00adphenyl group attached to the carbazole moiety in identical positions in both mol\u00adecules. A benzo\u00adfuran ring system in (I) and a methyl\u00adthio\u00adphene ring in (II) are fused with the respective carbazole moieties on the same sides. The mean plane of the carbazole ring system makes a dihedral angle of 3.17\u2005(7)\u00b0 with the benzo\u00adfuran ring system in (I) and a dihedral angle of 3.39\u2005(11)\u00b0 with the methyl\u00adthio\u00adphene ring in (II), implying that both fused units are essentially planar. The mean planes of the carbazole ring systems in both the compounds are almost orthogonal to the respective nitro-substituted phenyl rings, making dihedral angles of 75.64\u2005(10) and 77.63\u2005(12)\u00b0 in compounds (I) and (II), respectively. In (I), the phenyl\u00adsulfonyl ring system is positionally disordered with a refined occupancy ratio of 0.63\u2005(2):0.37\u2005(2). In both compounds, the mol\u00adecular structures are stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds, generating S(6) ring motifs with the sulfone group O atoms. In the crystal of compound (I), mol\u00adecules are linked by pairs of C\u2014H\u22efO hydrogen bonds, which generate R22(18) inversion dimers, and inter\u00adconnected by C(14) chains running along the c-axis direction, whereas in compound (II), the C\u2014H\u22efO hydrogen bonds generate R43(37) ring motifs. In the crystals of both compounds, C\u2014H\u22efO hydrogen-bonded sheets are formed lying parallel to (10-1). In addition, C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.7158\u2005(14)\u2005\u00c5 in (I) and 3.9040\u2005(15)\u2005\u00c5 in (II)] are also present in the crystals of both compounds.The title compounds, C Carbazole derivatives exhibit various biological activities such as anti\u00adtumor 2 groups are inclined to the benzene ring (C19\u2013C24) to which they are attached by 9.8\u2005(4)\u00b0 in (I)The mean planes of the carbazole ring systems make dihedral angles of 3.17\u2005(7) and 3.39\u2005(11)\u00b0, respectively, with the benzo\u00adfuran ring in (I)sp2 bond lengths are longer than the mean value of 1.355\u2005(14)\u2005\u00c5 for N\u2014C bond lengths  ring motifs with the sulfone oxygen atoms (Tables 1The sums of the bond angles around atom N1 are 349.58\u00b0 in (I) Tables 1 and 2 \u25b8.via pairs of C20\u2014H20\u22efO2ii hydrogen bonds  chains. These inter\u00adactions result in the formation of sheets parallel to  = 3.7158\u2005(14)\u2005\u00c5, inter\u00adplanar distance = 3.472\u2005(1)\u2005\u00c5, slippage = 1.324\u2005(11)\u2005\u00c5; Cg4 is the centroid of the C7\u2013C12 ring]; see Table\u00a01In the crystal of compound (I)s Table\u00a01, formingi and C14\u2014H14\u22efOii4 hydrogen bonds  = 3.9040\u2005(15)\u2005\u00c5, inter\u00adplanar distance = 3.791\u2005(1)\u2005\u00c5, slippage 0.932\u2005\u00c5; Cg4 is the centroid of the C7\u2013C12, ring]; see Table\u00a02In the crystal of compound (II)s Table\u00a02, which rfs Fig.\u00a04. The cryrs Fig.\u00a05, which aet al., 2016H-[1] benzo\u00adfuran\u00adcarbazole and 47 hits for 9-(phenyl\u00adsulfon\u00adyl)-9H-carbazole. However, the compound 7-phenyl\u00adsulfonyl-7H-benzo\u00adfuran\u00adcarbazole H-thienocarbazole et al., 2011A search of Cambridge Structural Database : A solution of [3-(4-nitro\u00adbenzo\u00adyl)-1-(phenyl\u00adsulfon\u00adyl)-1H-indol-2-yl]methyl pivalate , anhydrous SnCl4  and benzo\u00adfuran  in dry DCE (10\u2005ml) was stirred at room temperature under nitro\u00adgen for 3\u2005h. After completion of the reaction (monitored by TLC), it was poured into ice\u2013water (100\u2005ml). The organic layer was separated and the aqueous layer was extracted with DCM (2 \u00d7 20\u2005ml). The combined extract was washed with water (3 \u00d7 50ml) and dried (Na2SO4). Removal of the solvent by column chromatographic purification  yielded compound (I)Compound (II): A solution of [3-(4-nitro\u00adbenzo\u00adyl)-1-(phenyl\u00adsulfon\u00adyl)-H-indol-2-yl]methyl pivalate , anhydrous SnCl4  and 2-methyl\u00adthio\u00adphene  in dry DCE (10\u2005ml) was stirred at room temperature under nitro\u00adgen atmosphere for 3\u2005h. After the completion of the reaction (monitored by TLC), it was poured into ice\u2013water (100\u2005ml), the organic layer was separated and the aqueous layer was extracted with DCM (2 \u00d7 20ml). The combined extract was washed with water (3 \u00d7 50\u2005ml) and dried (Na2SO4). Removal of the solvent by column chromatographic purification  yielded compound (II)Uiso(H)= 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. In compound (I)SHELXL97; Sheldrick, 2008Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989016016996/su5333sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016016996/su5333Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016016996/su5333IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016016996/su5333Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016016996/su5333IIsup5.cmlSupporting information file. DOI: 1473995CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II cation displays a distorted octa\u00adhedral geometry coordinated by four pyridine N atoms from four individual ligands and two O atoms from two monodentate nitrate anions. Two symmetry-related ligands are connected by two symmetry-related CoII cations, forming a 20-membered cyclic dimer. These cyclic dimers are connected to each other by sharing CoII atoms, forming a looped chain. In the crystal, adjacent looped chains are connected by inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions and C\u2014H\u22ef\u03c0 and C\u2014H\u22efO hydrogen bonds, resulting in the formation of a three-dimensional supra\u00admolecular architecture.The reaction of cobalt(II) nitrate with bis\u00ad(pyridin-3-ylmeth\u00adyl)sulfane ligand, afforded a one-dimensional looped polymeric chain. The Co 3)2(C12H12N2S)2]n, contains a bis\u00ad(pyridin-3-ylmeth\u00adyl)sulfane (L) ligand, an NO3\u2212 anion and half a CoII cation, which lies on an inversion centre. The CoII cation is six-coordinated, being bound to four pyridine N atoms from four symmetry-related L ligands. The remaining coordination sites are occupied by two O atoms from two symmetry-related nitrate anions in a monodentate manner. Thus, the CoII centre adopts a distorted octa\u00adhedral geometry. Two symmetry-related L ligands are connected by two symmetry-related CoII cations, forming a 20-membered cyclic dimer, in which the CoII atoms are separated by 10.2922\u2005(7)\u2005\u00c5. The cyclic dimers are connected to each other by sharing CoII atoms, giving rise to the formation of an infinite looped chain propagating along the [101] direction. Inter\u00admolecular C\u2014H\u22ef\u03c0 (H\u22efring centroid = 2.89\u2005\u00c5) inter\u00adactions between one pair of corresponding L ligands and C\u2014H\u22efO hydrogen bonds between the L ligands and the nitrate anions occur in the looped chain. In the crystal, adjacent looped chains are connected by inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.8859\u2005(14)\u2005\u00c5] and C\u2014H\u22ef\u03c0 hydrogen bonds (H\u22efring centroid = 2.65\u2005\u00c5), leading to the formation of layers parallel to (101). These layers are further connected through C\u2014H\u22efO hydrogen bonds between the layers, resulting in the formation of a three-dimensional supra\u00admolecular architecture.The asymmetric unit of the title compound, [Co(NO The CoII cation is coordinated by four pyridine N atoms from four symmetry-related L ligands. In addition, the CoII cation binds to two O atoms of two symmetry-related monodentate nitrate anions, forming a distorted octa\u00adhedral CoN4O2 coordination. Selected bond lengths and angles around the Co1 atom are listed in Table\u00a01II centre are tilted by 70.75\u2005(7)\u00b0 with respect to each other \u2005\u00c5. The cyclic dimers are connected by sharing CoII atoms, leading to the formation of an infinite looped chain propagating along the [101] direction. An inter\u00admolecular C7\u2014H7B\u22ef Cg2i inter\u00adactions  between one pair of corresponding L ligands and several C\u2014H\u22efO hydrogen bonds between the L ligands and the NO3\u2212 anions (Table\u00a02Two symmetry-related s Table\u00a02 contribuCg1\u22efCg1ii = 3.8859\u2005(14)\u2005\u00c5; yellow dashed lines in Fig.\u00a02Cg1 is the centroid of atoms N1/C1\u2013C5; symmetry code: (ii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01] together with inter\u00admolecular C6\u2014H6A\u22efCg2iii hydrogen bonds , generating layers parallel to (101). Neighboring layers are packed by C1\u2014H1\u22efO3iv hydrogen bonds  between pyridine H atoms and nitro\u00adgen O atoms, resulting in the formation of a three-dimensional supra\u00admolecular architecture.Adjacent looped chains in the structure are connected by inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between the N1-pyridine rings [L ligand was synthesized according to a literature method  solution of the L ligand with Co(NO3)2\u00b76H2O in a 2:1 molar ratio.The sp2\u2014H and 0.97\u2005\u00c5 for methyl\u00adene C\u2014H with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017014980/hg5499sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017014980/hg5499Isup2.hklStructure factors: contains datablock(s) I. DOI: 1580230CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound consists of an di\u00adethyl\u00adammonium\u2013aniline\u00adsulfonate ion pair and a zwitterionic aniliniumsulfonate mol\u00adecule. 4H12N+\u00b7C6H6NO3S\u2212\u00b7C6H7NO3S, consists of an ion pair and a zwitterionic neutral mol\u00adecule. The cation adopts an extended conformation [C\u2014C\u2014N\u2014C torsion angles = 177.1\u2005(3) and \u2212178.4\u2005(3)\u00b0]. In the crystal, the components are linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, generating a three-dimensional network, which is consolidated by weak C\u2014H\u22efO inter\u00adactions.The title compound, C The bi-layers are then linked through N1\u2014H1NA\u22efO2, N1\u2014H1NB\u22efO5 and N1\u2014H1NB\u22efO6 hydrogen bonds, yielding a three-dimensional network  inter\u00adactions consolidate the packing in the crystal . Examination of the packing reveals layers of diethyl ammonium cation sandwiched between bi-layers of aniline sulfate moieties. The key hydrogen bonds establishing the three-dimensional array are the contacts to sulfonate oxygen atoms and the N2\u22efN3 aniline inter\u00adactions. All amine hydrogen atoms form good hydrogen-bond contacts to neighboring hydrogen-bond acceptor atoms.The zwitterionic aniliniumsulfonate and the aniline\u00adsulfonate anion are connected through N2\u2014H2s Table\u00a01 giving srk Fig.\u00a02. Some weet al., 2016et al., 2008A search of the Cambridge Structural Database    I. DOI: 10.1107/S2056989016018041/hb7622Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016018041/hb7622Isup3.cmlSupporting information file. DOI: 1515845CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-hy\u00addroxy\u00adquinoline-2-carboxamide mol\u00adecule has a nearly planar structure [maximum deviation = 0.062\u2005(1)\u2005\u00c5] and only the hy\u00addroxy H atom deviates from the mol\u00adecule plane.The  10H8N2O2\u00b7H2O, consists of an N-hy\u00addroxy\u00adquinoline-2-carboxamide mol\u00adecule in the keto tautomeric form and a water mol\u00adecule connected through an O\u2014H\u22efO hydrogen bond. The N-hy\u00addroxy\u00adquinoline-2-carboxamide mol\u00adecule has a nearly planar structure [maximum deviation = 0.062\u2005(1)\u2005\u00c5] and only the hy\u00addroxy H atom deviates significantly from the mol\u00adecule plane. In the crystal, \u03c0\u2013\u03c0 stacking between the aromatic rings [inter\u00adcentroid distance = 3.887\u2005(1)\u2005\u00c5] and inter\u00admolecular O\u2014H\u22efO hydrogen bonds organize the crystal components into columns extending along the b-axis direction.The title compound, C The carbonyl group possesses a Z conformation against the N1 atom of the quinoline moiety and E conformation against the hy\u00addroxy oxygen atom [torsion angles O2\u2014N2\u2014C10\u2014O1 = 0.8\u2005(2)\u00b0 and N1\u2014C9\u2014C10\u2014O1\u00a0\u2212177.33\u2005(14)\u00b0]. The N-hy\u00addroxy\u00adquinoline-2-carboxamide mol\u00adecule has an almost planar structure (non-hydrogen atoms are planar to within 0.03\u2005\u00c5). Only the H atom of the OH group deviates significantly from the mol\u00adecular plane: the C\u2014N\u2014O\u2014H torsion angle of \u221275.1\u2005(13)\u00b0 is defined by the O\u2014H\u22efO hydrogen bond between hy\u00addroxy group and the water mol\u00adecule. The C\u2014N and C\u2014C bond lengths in the quinoline moiety are typical for 2-substituted pyridine derivatives \u2005\u00c5, inter\u00adcentroid distance 3.887\u2005(1)\u2005\u00c5, displacement 1.846\u2005(1)\u2005\u00c5]. These columns are linked pairwise by the O\u2014H\u22efO hydrogen bonds  global, I. DOI: 10.1107/S2056989017005618/xu5902Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005618/xu5902Isup3.cmlSupporting information file. DOI: 1543825CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The persence of C\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions in the crystals lead to dimeric aggregates in (I) and supra\u00admolecular chains (II).The metal coordination geometry in each of the title mol\u00adecules, [Sn(C viz. [Sn(C6H5)3(C8H16NS2)], (I), and [Sn(C6H5)3(C10H12NS2)], (II), are described. The di\u00adthio\u00adcarbamate ligand in each mol\u00adecule coordinates in an asymmetric fashion resulting in heavily distorted tetra\u00adhedral C3S coordin\u00adation geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The mol\u00adecular packing in both compounds features C\u2014H\u22ef\u03c0(Sn-phen\u00adyl) inter\u00adactions. In (I), the donors are Sn-phenyl-C\u2014H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C\u2014H and methyl-C\u2014H groups leading to supra\u00admolecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional inter\u00adactions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H\u22efH, C\u22efH/H\u22efC and S\u22efH/H\u22efS contacts on the respective Hirshfeld surface.The crystal and mol\u00adecular structures of two tri\u00adphenyl\u00adtin di\u00adthio\u00adcarbamate compounds,  A key inter\u00adest in di\u00adthio\u00adcarbamate compounds of both transition metals and main-group elements relates to their biological activity 3Sn[S2CN(Me)Hex] (I)6H5)3Sn[S2CN(CH3)CH2CH2Ph] (II)A vast array of different di\u00adthio\u00adcarbamate anions, a, is coordinated by three ipso-carbon atoms along with a di\u00adthio\u00adcarbamate ligand. As seen from Table\u00a01long \u2013 Sn\u2014Sshort) being 0.64\u2005\u00c5. This asymmetry is confirmed in the differences in the C\u2014S bond lengths with the C1\u2014S1 bond associated with the short Sn\u2014S1 contact, at 1.761\u2005(4)\u2005\u00c5, being significantly longer than the C1\u2014S2 bond, i.e. 1.688\u2005(4)\u2005\u00c5, involving the weakly bound S2 atom. If the S2 atom is ignored, the coordination geometry about the tin atom is distorted C3S tetra\u00adhedral with the range of angles being 90.00\u2005(11)\u00b0, for S1\u2014Sn\u2014C31, to 121.53\u2005(10)\u00b0, for S1\u2014Sn\u2014C11. The wide angle clearly reflects the influence of the close approach of the S2 atom, Fig.\u00a01a and Table\u00a013S2 donor set is almost perfectly inter\u00admediate between ideal square-pyramidal (SP) and trigonal\u2013bipyramidal (TP). This is qu\u00adanti\u00adfied in the value of \u03c4 = 0.52, which compares with the ideal values for SP and TP geometries of \u03c4 = 0.0 and 1.0, respectively , 178.5\u2005(4) and 178.9\u2005(5)\u00b0, respectively, indicate + anti-periplanar descriptors but, that of C5\u2014C6\u2014C7\u2014C8, i.e. \u221266.4\u2005(8)\u00b0, indicative of a \u2212 syn-clinal disposition.The tin atom in (I)b, resembles closely that described for (I)3S2 description pertains, the value of \u03c4 = 0.60 indicates a distortion towards TP. The phenyl\u00adethyl chain is kinked as seen in the N1\u2014C3\u2014C4\u2014C5 and C3\u2014C4\u2014C5\u2014C6 torsion angles of \u2212175.8\u2005(3) and 91.9\u2005(5)\u00b0, respectively.The mol\u00adecular structure of (II)a. Such cooperative C\u2014H\u22ef\u03c0(phen\u00adyl) embraces have been described for many phenyl-rich systems and in instances where six phenyl rings of two residues associate by edge-to-face inter\u00adactions, i.e. a six-fold embrace, the energies of stabilization can resemble or even exceed that provided by strong conventional hydrogen bonding PLATON et al., 2017i.e. n-hexyl in the former and phenyl\u00adethyl in the latter. These differences are readily discerned from the differently shaped Hirshfeld surfaces mapped over dnorm for (I)The Hirshfeld surface calculations for the tri\u00adphenyl\u00adtin di\u00adthio\u00adcarbamate derivatives (I)a reflect the presence of a weak C\u2014H\u22ef\u03c0 inter\u00adaction, as summarized in Table\u00a04C and n-hexyl atoms C7 and H7B are indicative of the short inter\u00adatomic H\u22efH and C\u22efH/H\u22efC contacts involving these atoms, as listed in Table\u00a04cf. (I)dnorm in Fig.\u00a05B and phenyl-C11 together with the pair of faint-red spots near the methyl-H2B and phenyl-C16 atoms in Fig.\u00a05a. The influence of other short inter\u00adatomic C\u22efH/H\u22efC contacts summarized in Table\u00a04a,b. The involvement of different atoms in the inter\u00admolecular inter\u00adactions in the crystals of (I)The faint-red spots near the phenyl-C33 and H26 atoms in Fig.\u00a04a, also highlight the different mol\u00adecular environments for the two mol\u00adecules. The significant contributions from H\u22efH, C\u22efH/H\u22efC and S\u22efH/H\u22efS contacts to the Hirshfeld surfaces of both (I)C and n-hexyl-H7B atoms in (I)de + di \u223c2.0\u2005\u00c5 in the delineated plot A and phenyl-H7, H9 and H23 atoms in comparatively weaker short inter\u00adatomic H\u22efH contacts, Table\u00a04de + di \u223c2.6\u2005\u00c5 in the fingerprint plot delineated into C\u22efH/H\u22efC contacts for (I)c, is the result of a short inter\u00adatomic contact between phenyl-C32 and -H23 atoms while the points corresponding to other short inter\u00adatomic contacts are merged within the plot. The presence of a pair of twin forceps-like tips at de\u00a0+\u00a0di \u223c\u00a02.7\u2005\u00c5 in the C\u22efH/H\u22efC delineated plot for (II)c, also indicates the involvement of methyl-H2A and -H2B, and phenyl-C7, -C8, -C11, -C16 and -C35 atoms in short inter\u00adatomic contacts, Table\u00a04d, that the pair of spikes at de\u00a0+\u00a0di \u223c 3.0\u2005\u00c5 for (I)de\u00a0+\u00a0di > 3.1\u2005\u00c5 for (II)The distinct distribution of points in the overall two-dimensional fingerprint plots for (I)et al., 2016N-hexyl-N-methyl\u00addithio\u00adcarbamate ligand reported in (I)i.e. dtcI, has been reported in the crystal structures of Ph2Sn(dtcI)2  compound, i.e. Hg(dtcII)3  in the Cambridge Structural Database short bond length is 2.47\u2005\u00c5 and the average Sn\u2014Slong bond length is 3.04\u2005\u00c5. This gives rise to an average \u0394(Sn\u2014S) of 0.57\u2005\u00c5. These values indicate the structures of (I)long are generally longer than usually observed. An analysis of the available crystallographic data showed the shortest Sn\u2014S1 bond length occurred in the structure of Ph3Sn(S2CNEt2) SnPh3  2} ; 26.39 [N\u2014(CH2)3CH2]; 22.6 [N\u2014CH2)4CH2]; 14.06 (hex\u00adyl\u2014CH3). 119Sn NMR (CDCl3): \u2212187.56.Synthesis of tri\u00adphenyl\u00adtin(IV)N-methyl-N-phenylethyl\u00addithio\u00adcarbamate (II) compound (II)N-methyl-N-phenylethyl\u00adamine  in place of N-hexyl-N-methyl\u00adamine. Recrystallization was achieved by dissolving the compound in a chloro\u00adform/ethanol mixture (1:2 v/v). Yield: 67%, m.p. 387.5\u2013388.3\u2005K. Elemental analysis: calculated (%): C 60.0, H 4.9, N 2.5, S 11.4. Found (%): C 57.9, H 5.3, N 2.8, S 11.2. IR (KBr cm\u22121): 1452 \u03bd(C\u2014N), 977 \u03bd(C\u2014S), 502 \u03bd(Sn\u2014C), 488 \u03bd(Sn\u2014S). 1H NMR (CDCl3): \u03b4 7.43\u20137.77 ; 7.24\u20137.35 ; 4.06 ; 3.36 ; 3.09 . 13C NMR (CDCl3): \u03b4 196.61 (NCS2); 126.8\u2013142.3 (C-aromatic); 60.25 (NCH2); 44.59 (NCH2CH2); 33.12 (N\u2014CH3). 119Sn NMR (CDCl3) = \u2212183.84.Uiso(H) set to 1.2\u20131.5Ueq(C). For (I)\u22123, respectively, are located 0.95 and 0.86\u2005\u00c5 from the Sn atom. For (II)\u22123, respectively, are located 0.96 and 0.68\u2005\u00c5 from the C11 and Sn atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989018005133/hb7745sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018005133/hb7745Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005133/hb7745IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1833664, 1833663CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The cation and anion of the title salt are linked by an O\u2014H\u22efN hydrogen bond and a C\u2014H\u22efO inter\u00adaction, resulting in a high viscosity and a crystallization temperature slightly lower than ambient temperature. 3H8NO+\u00b7C2F6NO4S2\u2212, has ortho\u00adrhom\u00adbic (P212121) symmetry; the amino H atom of bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amine (HNTf2) was transferred to the basic O atom of di\u00admethyl\u00adformamide (DMF) when the ionic liquid components were mixed. The structure displays an O\u2014H\u22efN hydrogen bond, which links the cation to the anion, which is reinforced by a non-conventional C\u2014H\u22efO inter\u00adaction, generating an R22(7) loop. A further very weak C\u2014H\u22efO inter\u00adaction generates an [001] chain.At 100\u2005K, the title mol\u00adecular salt, C The N2\u2014C4\u2014O5 angle does not deviate from the expected 120\u00b0 of an sp2-hybridized carbon atom [120.37\u2005(11)\u00b0]. The bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amide anion features S1\u2014N1 and S2\u2014N1 bond distances of 1.6035\u2005(11) and 1.5947\u2005(11)\u2005\u00c5, respectively.The asymmetric unit consists of one bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amide anion and one di\u00admethyl\u00adformamidium cation Fig.\u00a01: when thThe ion pair features two hydrogen bonds Table\u00a01. One is A CSD search  found no structures that have the same ion pairing. Some structures feature the same bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfon\u00adyl)amide anion but different cations, which are usually metal complexes.2 (I)et al., 2014A literature procedure was followed to synthesize [(DMF)H]NTfUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The methyl groups were refined as rotating groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016012251/hb7586sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016012251/hb7586Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016012251/hb7586Isup3.cmlSupporting information file. DOI: 1496417CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, dications, anions and solvent water mol\u00adecules are connected via N/C/O\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network.In the title salt, C N,N-bis\u00ad(pyridin-4-ylmeth\u00adyl)cyclo\u00adhexane-1,4-di\u00adamine with hydro\u00adchloric acid in ethanol led to the formation of the title salt, C18H26N42+\u00b72Cl\u2212\u00b72H2O, which lies about a crystallographic inversion center at the center of the cyclo\u00adhexyl ring. The asymmetric unit therefore comprises one half of the N,N-bis\u00ad(pyridin-4-ylmeth\u00adyl)cyclo\u00adhexane-1,4-di\u00adammonium dication, a chloride anion, and a solvent water mol\u00adecule. In the dication, the two trans-(4-pyridine)\u2013CH2\u2013NH2\u2013 moieties occupy equatorial sites at the 1- and 4-positions of the central cyclo\u00adhexyl ring, which is in a chair conformation. The terminal pyridine ring is tilted by 27.98\u2005(5)\u00b0 with respect to the mean plane of the central cyclo\u00adhexyl moiety (r.m.s. deviation = 0.2379\u2005\u00c5). In the crystal, dications, anions, and solvent water mol\u00adecules are connected via N/C/O\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds together with C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional network.Treatment of  The terminal pyridine ring is tilted by 27.98\u2005(5)\u00b0 with respect to the mean plane through the central cyclo\u00adhexyl moiety (r.m.s. deviation = 0.2379\u2005\u00c5). The distance between the two terminal pyridine nitro\u00adgen atoms in the dication is 15.864\u2005(2)\u2005\u00c5. This is slightly shorter than the N\u22efN separation [15.970\u2005(3)\u2005\u00c5] in the dication ligand of a one-dimensional zigzag-like CoII coordination polymer built up from alternate CoII ions and the dication of the title salt cyclo\u00adhexane-1,4-di\u00adamine, synthesized according to a literature method  = 0.95\u2005\u00c5 for Csp2\u2014H, 0.99\u2005\u00c5 for methyl\u00adene, 1.00\u2005\u00c5 for methine H atoms, and were refined as riding with Uiso(H) = 1.2Ueq(C). The N- and O-bound H atoms involved in hydrogen bonding were located in difference Fourier maps and refined freely .Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016014626/sj5507sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016014626/sj5507Isup2.hklStructure factors: contains datablock(s) I. DOI: 1504428CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both mol\u00adecules adopt the ladder structure typical for this class of dimeric tetra\u00adorganodistannoxane di\u00adcarboxyl\u00adates. A nearly linear very short C\u2014H\u22efO contact gives rise to a chain-like arrangement of mol\u00adecules in the [111] directionThe asymmetric unit of [{Sn(C 4H9)2(C6H5COO)}2O]2, consists of two half molecules, completed by application of inversion symmetry. Both mol\u00adecules adopt a ladder structure typical for this class of dimeric tetra\u00adorganodistannoxane di\u00adcarboxyl\u00adates characterized by a centrosymmetric four-membered (Sn\u2014O)2 ring of rhomboidal shape that is extended on both sides by folded six-membered Sn\u2014O\u2014C rings. To a first approximation, both kinds of Sn atoms (Sni and Sno) are trigonal\u2013bipyramidally coordinated. The bond angles between the n-butyl groups are widened [135.64\u2005(7)\u2013146.20\u2005(7)\u00b0] in comparison with an ideal trigonal bipyramid. Sn\u2014O bond lengths within the {R2SnO3} coordination sphere depend strongly on the position of the corresponding O atom \u2013 axial (ax) or equatorial (eq) \u2013 as well as on the functionality of the carboxyl\u00adate groups which exhibit \u03bc2 (\u2013COOi) and \u03bc1 (\u2013COOo) coordination modes, respectively. In summary, the following sequence of distances [mean values] is found: d(Sno\u2014O\u03bc3)eq [2.024\u2005(2)\u2005\u00c5] < d(Sni\u2014O\u03bc3)eq [2.044\u2005(2)\u2005\u00c5] < d(Sni\u2014O\u03bc3)ax [2.158\u2005(6)\u2005\u00c5] < d(Sno\u2014O\u03bc1-carb)ax [2.182\u2005(6)\u2005\u00c5] < d(Sni\u2014O\u03bc2-carb)ax [2.250\u2005(2)\u2005\u00c5] \u2243 d(Sno\u2014O2-carb\u03bc)ax [2.247\u2005(12)\u2005\u00c5]. The n-butyl groups adopt an anti\u2013anti conformation with exception of two disordered outer n-butyl groups of the second mol\u00adecule which exhibit gauche\u2013anti and anti\u2013gauche conformations. Weak intra\u00admolecular Sn\u22efO inter\u00adactions between the different O atoms of the outer carboxyl groups with the inner, as well as outer, Sn atoms give rise to a strongly distorted octa\u00adhedral coordination at these Sn atoms. Inter\u00admolecular inter\u00adactions between the individual mol\u00adecules are restricted to van der Waals and O\u22efH\u2014C inter\u00adactions of which a nearly linear very short C\u2014H\u22efO contact between the H atom of the phenyl group of one of the mol\u00adecules with the outer non-coordinating C=O group of the other molecule is the most prominent. It gives rise to a chain-like arrangement of the mol\u00adecules along [111]. The two n-butyl groups attached to the outer Sn atom of one mol\u00adecule are disordered over two sets of sites with occupancies of 0.806\u2005(3)/0.194\u2005(3) and 0.702\u2005(3)/0.298\u2005(3).The asymmetric unit of the title compound, [{Sn(C The disorder of the two n-butyl groups was managed by a split model with site occupancies of 0.806\u2005(3)/0.194\u2005(3) and 0.702\u2005(3)/0.298\u2005(3). No further consideration will be made for the structural parameters of those n-butyl groups. It is noteworthy, however, that this disorder is caused by the conformational flexibility of the n-butyl group which adopts \u2013 in the case of the major/minor components \u2013 a gauche\u2013anti/anti\u2013gauche and anti-gauche/anti\u2013gauche conformation with respect to the Sn\u2014C\u03b1\u2014C\u03b2\u2014C\u03b3 and C\u03b1\u2014C\u03b2\u2014C\u03b3\u2014C\u03b4 torsion angles . This conformation of the disordered n-butyl groups is in contrast to the conformation of all other n-butyl groups of both dimers, which show exclusively an anti\u2013anti conformation . Structural parameters mean = 1.521\u2005(6)\u2005\u00c5, \u2329(C\u2014C\u03b2/\u03b3\u2014C)mean = 112.6\u2005(11)\u00b0 while bond angles at C\u03b1 range from 112.5\u2005(1) to 123.1\u2005(1)\u00b0. Sn\u2014C distances are in the range of 2.127\u2005(2)\u20132.134\u2005(2)\u2005\u00c5, mean value 2.130\u2005(3)\u2005\u00c5.The title compound Fig.\u00a01 crystallry Fig.\u00a01. With thes Fig.\u00a02b,c. Thion Fig.\u00a02a. Strucs Table\u00a01 within tladder structure typical for this class of tetra\u00adorganodistannoxane di\u00adcarboxyl\u00adates  and two outer (Sno) tin atoms are \u2013 to a first approximation \u2013 fivefold, trigonal\u2013bipyramidally coordinated and linked together via two \u03bc2-coordinating oxygen atoms (Oi) and two chelating (\u2013COOi) carboxyl\u00adate groups. The structure is completed by two monodentate carboxyl\u00adate groups (\u2013COOo) attached to the outer tin atoms /75.78\u2005(5)\u00b0] angles at tin and obtuse ones [104.10\u2005(5)/104.22\u2005(5)\u00b0] at oxygen. Its rhomboidal shape with different Sn\u2014O distances results from the position of the \u03bc3-oxygen atom (O1/O3) within the trigonal\u2013bipyramidal coordination sphere of the inner tin atoms (Sn1/Sn3): bonds where the O atom is in an equatorial (eq) position are significantly shorter [2.042\u2005(1)/2.046\u2005(1)\u2005\u00c5] than those where the O atom is in an axial (ax) position [2.164\u2005(1)/2.152\u2005(1)\u2005\u00c5]. The second axially positioned Sn\u2014O bond at the inner tin atoms is even longer [2.251\u2005(1)/2.248\u2005(1)\u2005\u00c5] as it results from a coordinative bond of the oxygen atom (O11/O31) of the \u03bc2-benzoate ligand (\u2013COOi). In contrast to the prediction of the VSEPR concept, the bond angle between both equatorially positioned n-butyl groups is widened to 146.20\u2005(7)/141.73\u2005(7)\u00b0.The central, planar and centrosymmetric four-membered (Sn\u2013O)d(Sno\u2014O\u03bc3)eq [2.027\u2005(1)/2.022\u2005(1)\u2005\u00c5] < d(Sno\u2014O\u03bc1-carb)ax [2.175\u2005(1)/2.188\u2005(1)\u2005\u00c5] < d(Sno\u2014O\u03bc2-carb)ax [2.260\u2005(1)/2.235\u2005(1)\u2005\u00c5]. Bond angles between the n-butyl groups at the tin atoms are 142.49\u2005(7) and 135.64\u2005(7)\u00b0.The conformation of the outer, six-membered Sn\u2013O\u2013C rings is defined by an angle of 19.9\u2005(1)/23.4\u2005(1)\u00b0 between the O\u2013C\u2013O plane and the Sn\u2013O\u2013Sn plane Fig.\u00a04. In caseo), the C\u2014O bonds are of different strengths: the short, strong one [1.232\u2005(2)/1.222\u2005(3)\u2005\u00c5] indicates a localized C=O double bond whereas the long, weak one [1.307\u2005(2)/1.306\u2005(3)\u2005\u00c5] of the Sn-coordinating oxygen atom indicates a localized C\u2014O single bond. In the case of the bridging benzoate groups (\u2013COOi) both C\u2014O bonds are of almost equal lengths , in accordance with a delocalized \u03c0-system. In the two benzoate ligands, the carboxyl\u00adate groups and the phenyl groups are not co-planar, but are inclined to each other at angles of 15.1\u2005(2), 14.8\u2005(3)/3.9\u2005(3) and 17.3\u2005(1)\u00b0.The different coordination modes of both benzoate ligands are reflected in different C\u2014O bond lengths: in the case of the monodentate carboxyl\u00adate group (\u2013COOd(Sn\u22efO) = 2.7857\u2005(2)/2.7141\u2005(2)\u2005\u00c5] of the \u03bc1-O atoms (O21/O41) of the outer carboxyl\u00adate groups with the inner tin atoms (Sn1/Sn3), while those of the \u03bc0-O atoms (O22/O42) of the outer carboxyl\u00adate groups with the outer tin atoms (Sn2/Sn4) are still longer [2.8901\u2005(2)/2.9883\u2005(2)\u2005\u00c5]. Taking these weak inter\u00adactions into account, both kinds of Sn atoms adopt a strongly distorted octa\u00adhedral coordination. All bonding features (except the last ones) of the two mol\u00adecules are summarized in Fig.\u00a05n-butyl groups relative to the Sn\u2013O framework.Another characteristic feature of the mol\u00adecular structure comprises some additional, very weak inter\u00adactions [d(H\u22efO) = 2.487\u2005\u00c5], nearly linear [\u2329(C\u2014H\u22efO) = 172.6\u00b0] contact between the hydrogen atom H26 of a phenyl ring of mol\u00adecule 1 and the non-coordinating oxygen atom O42 of the second mol\u00adecule attracts attention as it leads to a chain-like arrangement of the two mol\u00adecules along [111] ]2O, have been extensively structurally characterized. The Cambridge Structural Database  while for the di\u00adcarboxyl\u00adates benzoic acid derivatives (90) are the most studied. Even for the combination of R = nBu and R\u2032 = benzoic acid derivatives not less than 67 structures are described, but from the parent compound with R\u2032 = PhCOO\u2212, only the structure of the methyl compound (R = Me) has been completely characterized }2O]2 was obtained from an equimolar mixture of 0.300\u2005g (1.2\u2005mmol) of n-di\u00adbutyl\u00adtin oxide with 0.147\u2005g (1.2\u2005mmol) of benzoic acid in ethanol under reflux for 3.5\u2005h. After removal of the solvent, single crystals were obtained by recrystallization of the solid from ethanol/n-hexane. and displacement parameters were taken from the chemically equivalent C atoms of the major occupancy component.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017001505/zl2692sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017001505/zl2692Isup2.hklStructure factors: contains datablock(s) I. DOI: 1530058CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the former, the 4-methyl\u00adbenzene ring substituent makes a dihedral angle of 71.40\u2005(9)\u00b0 with the mean plane of the naphthalene ring system, while the phenyl ring substituent in the latter makes a dihedral angle of 67.08\u2005(12)\u00b0 with the mean plane of the anthracene ring system.The title compounds, 6-, and C26H16S, (II), are benzo\u00adthio\u00adphene derivatives in which the benzo\u00adthio\u00adphene moiety is fused with a naphthalene ring system in (I), and with an anthracene ring system in (II). In (I), the mean plane of the benzo\u00adthio\u00adphene ring system makes a dihedral angle of 2.28\u2005(6)\u00b0 with the naphthalene ring system, and a dihedral angle of 1.28\u2005(6)\u00b0 with the anthracene ring system in (II), showing that the fused units are essentially planar. In (I), the 4-methyl\u00adbenzene ring substituent makes a dihedral angle of 71.40\u2005(9)\u00b0 with the naphthalene ring system, while the phenyl ring substituent in (II) makes a dihedral angle of 67.08\u2005(12)\u00b0 with the anthracene ring system. In the crystals of both compounds, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, leading to the formation of slabs parallel to (001) in (I) and to zigzag chains along [001] in (II). There are also offset \u03c0\u2013\u03c0 inter\u00adactions present within the slabs in (I). In the crystal of (II), they link the chains, forming sheets parallel to (010). The triclinic polymorph of compound (II) has been reported .The title compounds, Cal., 2012. J. Org. In the crystal of (II)Cg2\u22efCg4iii = 3.711\u2005(2)\u2005\u00c5, inter\u00adplanar distance = 3.479\u2005(1)\u2005\u00c5, slippage = 1.21\u2005\u00c5; Cg3\u22efCg4iii = 3.741\u2005(2)\u2005\u00c5, inter\u00adplanar distance = 3.443\u2005(1)\u2005\u00c5, slippage = 1.22\u2005\u00c5; Cg2, Cg3 and Cg4 are the centroids of rings C1\u2013C3/C10\u2013C12, C1/C12\u2013C16 and C4\u2013C9, respectively; symmetry code: (iii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].In the crystals of both compounds, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions benzo[b]naphtho\u00adthio\u00adphene b]thio\u00adphen-3-yl){2-[pivalo\u00adyloxy(p-tol\u00adyl) meth\u00adyl]phen\u00adyl}methyl pivalate as a viscous liquid. Dipivalate (benzo[b]thio\u00adphen-3-yl){2-[pivalo\u00adyloxy(p-to\u00adyl) meth\u00adyl]phen\u00adyl}methyl pivalate  upon inter\u00adaction with ZnBr2  followed by removal of solvent and column chromatographic purification  gave 6-(p-tol\u00adyl)benzo[b]naphtho\u00adthiophene as a pale-green solid . Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of (I)The reduction of the diketone (benzo\u00adthio\u00adphen-3-yl)[2-(4-methyl\u00adbenzo\u00adyl)phen\u00adyl]methanone  using sodium borohydride  followed by work-up gave the diol. Dipivaloylation of the diol  using pivaloyl chloride  and tri\u00adethyl\u00adamine  in the presence of a catalytic amount of DMAP (10\u2005mg) in dry DCM (20\u2005ml) led to the isolation of dipivalate (benzothio\u00adphen-2-yl)methanone  using sodium borohydride  followed by work-up gave the diol. Dipivaloylation of the diol  using pivaloyl chloride  and tri\u00adethyl\u00adamine  in the presence of a catalytic amount of DMAP (10\u2005mg) in dry DCM (20\u2005ml) led to the isolation of dipivalate {2-[phen\u00adylmeth\u00adyl]phen\u00adyl}methyl pivalate as a thick liquid. Dipivalate {2-[phen\u00adylmeth\u00adyl]phen\u00adyl}methyl pivalate  upon inter\u00adaction with ZnBr2  followed by removal of solvent and column chromatographic purification  gave a new ortho\u00adrhom\u00adbic polymorph of 7-phenyl\u00adanthrabenzo[d]thio\u00adphene  as a yellow solid. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the compound (II)The reduction of the diketone (2-benzoyl\u00adphen\u00adyl)(dibenzo[Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989016012937/lh5819sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016012937/lh5819Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016012937/lh5819IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016012937/lh5819Isup4.cmlSupporting information file. DOI: 1498519, 1498518CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The three mol\u00adecules have slightly varying overall conformations, all having trans conformations with respect to the C=N bond. In the crystal, the packing features N\u2014H\u22efN hydrogen bonds, which connect mol\u00adecules into chains extending along the c-axis direction, inter\u00adlinked by C\u2014H\u22ef\u03c0 inter\u00adactions (minimum H\u22efCg = 2.65\u2005\u00c5) into sheets lying parallel to (001).The title compound, C These are close to the literature value of 1.279\u2005\u00c5 for Csp2=Nsp2 bonds , 1.472\u2005(3) and 1.476\u2005(3)\u2005\u00c5, respectively. The comparative N1\u2014C16 bonds connecting the central benzene ring to the central C=N bond in A, B and C are 1.422\u2005(2), 1.419\u2005(2) and 1.420\u2005(2)\u2005\u00c5, respectively. The C14\u2014C15\u2014N1\u2014C16, torsion angles for the \u2013C\u2014C\u2014N\u2014C\u2013 bridge groups are \u2212178.47\u2005(17)\u00b0 (for A), \u2212176.35\u2005(17)\u00b0 (for B) and 178.31\u2005(17)\u00b0 (for C). The comparative dihedral angles between the anthracene ring system of the mol\u00adecule (defined by C1\u2013C14) and the benzene and phenyl rings (defined by C16\u2013C21 and C22\u2013C27) and between the benzene and phenyl rings, respectively, are 82.68\u2005(4), 73.76\u2005(5) and 25.63\u2005(11)\u00b0 in A, 80.10\u2005(4), 78.82\u2005(5) and 22.56\u2005(11)\u00b0 (in B) and 85.02\u2005(5), 81.66\u2005(5) and 16.25\u2005(11)\u00b0 (in C).The title compound, crystallizes with three independent mol\u00adecules  = 2.65\u2005\u00c5; C\u2014H\u22efCg = 154\u00b0], forming layers lying parallel to (001)  Fig.\u00a03.et al., 2016N-phenyl-p-phenyl\u00adenedi\u00adamine. Of these three compounds, N1-phenyl-N-4-(quinolin-2-yl\u00admethyl\u00adene)benzene-1,4-di\u00adamine {synonym: N-phenyl-4-[(quinolin-2-yl\u00admethyl\u00adene)amino]-aniline; WOJJIQ -(pyren-1-yl)-methyl\u00adidene]benzene-1,4-di\u00adamine  of 9-anthracenecarboxaldehyde in 5\u2005ml of absolute ethanol was added dropwise under stirring. The mixture was stirred for 10\u2005min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2h. The resulting yellow precipitate was recovered by filtration, washed several times with small portions of ice-cold ethanol and then with diethyl ether to give 140\u2005mg (87%) of the title compound. Dark-yellow block-like crystals suitable for X-ray analysis were obtained within 3 days by slow evaporation of a solution in MeOH.80\u2005mg (0.435\u2005mmol) of Uiso(H)= 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016020612/zs2373sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016020612/zs2373Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016020612/zs2373Isup3.cmlSupporting information file. DOI: 1524849CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The evolution of T1\u03c1 and of other endogenous contrast methods  in the first month after reperfused myocardial infarction (MI) is uncertain. We conducted a study of reperfused MI in pigs to serially monitor T1\u03c1, T2 and T1 relaxation, scar size and transmurality at 1 and 4\u00a0weeks post-MI.n\u2009=\u200910) and 4\u00a0weeks (n\u2009=\u20095). Semi-automatic FWHM  thresholding was used to assess scar size and transmurality and compared to histology. Relaxation times and contrast-to-noise ratio were compared in healthy and remote myocardium at 1 and 4\u00a0weeks. Linear regression and Bland-Altman was performed to compare infarct size and transmurality.Ten Yorkshire swine underwent 90\u00a0min of occlusion of the circumflex artery and reperfusion. T1\u03c1, T2 and native T1 maps and late gadolinium enhanced (LGE) cardiovascular magnetic resonance (CMR) data were collected at 1\u00a0week (T1\u2009=\u20097.0\u2009\u00b1\u20093.5 (1\u00a0week) and 6.9\u2009\u00b1\u20092.4 (4\u00a0week), CNRT1\u03c1\u2009=\u200912.0\u2009\u00b1\u20096.2 and 12.3\u2009\u00b1\u20093.2, and CNRT2\u2009=\u20098.0\u2009\u00b1\u20093.6 and 10.3\u2009\u00b1\u20095.8. Infarct size was not significantly different for T1\u03c1, T1 and T2 compared to LGE (p\u2009=\u20090.14) and significantly decreased from 1 to 4\u00a0weeks (p\u2009<\u20090.01). Individual infarct size changes were \u2206T1\u03c1\u2009=\u2009\u22123.8%, \u2206T1\u2009=\u2009\u22123.5% and \u2206LGE\u2009=\u2009\u22122.8% from 1 \u2013 4\u00a0weeks, but there was no observed change in infarct size for T2 or histologically.Relaxation time differences between infarcted and remote myocardial tissue were \u2206T1 (infarct-remote)\u2009=\u2009421.3\u2009\u00b1\u2009108.8 (1\u00a0week) and 480.0\u2009\u00b1\u200933.2\u00a0ms (4\u00a0week), \u2206T1\u03c1\u2009=\u200968.1\u2009\u00b1\u200911.6 and 74.3\u2009\u00b1\u200914.2, and \u2206T2\u2009=\u200951.0\u2009\u00b1\u200910.1 and 59.2\u2009\u00b1\u200911.4\u00a0ms. Contrast-to-noise ratio was CNRT1\u03c1 was highly correlated with alterations left ventricle (LV) pathology at 1 and 4\u00a0weeks post-MI and therefore it may be a useful method endogenous contrast imaging of infarction.The online version of this article (doi:10.1186/s12968-017-0332-z) contains supplementary material, which is available to authorized users. Ischemic heart disease is an enormous health and economic burden and the most common cause of death throughout the world . A devasT1\u03c1 (\u201cT-one-rho\u201d) CMR has recently emerged as an endogenous contrast method for quantitative imaging of myocardial injury \u201313. T1\u03c1 We conducted a serial study of reperfused infarction in pigs to monitor T1\u03c1 at 1 and 4\u00a0weeks post-MI. The objectives were to compare T1\u03c1 relaxation time changes in ischemic tissue with native T1, T2 and LGE and associate each with infarct size and transmurality. Finally, imaging results were correlated with fibrosis using histological data.n\u2009=\u200910) were procured for this study. During all procedures, sedation was induced with intramuscular ketamine, endotracheal intubation was performed, and the animal was maintained with a mixture of isoflurane 1-2% and oxygen with a ventilator tidal volume of 20\u00a0mL/kg . Anesthesia and animal temperature was closely monitored for the duration of surgical and imaging procedures to maintain a constant physiologic state. Arterial access was obtained at the carotid artery for measurement of intraventricular pressure . Venous access was obtained at the internal jugular veins for administration of medication. After each procedure, the animal was weaned from anesthesia and transported to the recovery room. Upon completion of the terminal CMR study, the animal was returned to the operating room for euthanasia and tissue harvest.Yorkshire swine (n\u2009=\u20095) and II, a 4-week terminal study (n\u2009=\u20095). Furthermore, five animals  underwent a baseline CMR immediately prior to coronary artery occlusion. The experimental model was chosen to emulate human post-percutaneous coronary intervention ischemia injury. All the animals of the 4\u00a0week group underwent both 1 and 4\u00a0week CMR. Figure\u00a0Ten pigs underwent 90\u00a0min of coronary artery occlusion and were randomized into two groups: group I, a 1-week post-MI terminal study  with 40\u00a0mT/m gradient and 12 channel RF receiver arrays. Intraventricular pressure was interfaced to physiological monitoring software and filtered to facilitate dual respiratory and cardiac gating . All 2D images were acquired in the short-axis during breath-holding and 3D with dual cardiac and respiratory gating. Breath-holding was performed by temporarily disabling the animal ventilator.x \u2013 SLy - 180y \u2013 SL-y - 90-x) [1\u2009=\u2009500\u00a0Hz, spatial resolution\u2009=\u20091.4\u2009\u00d7\u20091.4\u00a0mm2, slice thickness\u2009=\u20096\u00a0mm, flip angle\u2009=\u200970\u00b0, TE\u2009=\u20091.45\u00a0ms, TR\u2009=\u20092.9\u00a0ms, NSeg\u2009=\u200955, bandwidth\u2009=\u2009900\u00a0Hz/pixel, linear k-space phase encoding ordering, parallel imaging with acceleration factor\u2009=\u20092, 34 reference k-space lines obtained in a separate heartbeat, and four heartbeats for T1 relaxation between shots. The T1\u03c1 amplitude was set at the highest available within scanner specific absorption rate limits (B1\u2009=\u2009500\u00a0Hz).2D T1\u03c1 single-shot balanced steady-state free precession (bSSFP) sequences were performed using a spin echo, spin lock (SL) T1\u03c1 pulse cluster (90 - 90-x) , 15. T1\u03c1x \u2013 180y \u2013 90-x) bSSFP sequence and 8 images were acquired with different contrast times TE\u2009=\u20092, 10, 18, 26, 34, 42, 50\u00a0ms using the same readout as with the T1\u03c1 images.2D T2 maps were obtained using a single-shot T2 prepared  . Other p2, slice thickness\u2009=\u20096\u00a0mm.Retrospective, short axis, multi-slice cine CMR was performed with a temporal resolution\u2009=\u200940\u00a0ms, flip angle\u2009=\u200970\u00b0, bandwidth\u2009=\u2009940\u00a0Hz/pixel, spatial resolution\u2009=\u20091.1\u2009\u00d7\u20091.1\u00a0mm2, flip angle\u2009=\u200950\u00b0, TE\u2009=\u20091.6\u00a0ms, TR\u2009=\u20093.2\u00a0ms. slice thickness\u2009=\u20092\u00a0mm, and parallel imaging acceleration factor\u2009=\u20092 [The animals received a 0.1\u00a0mmol/kg intravenous injection of gadolinium contrast for LGE imaging . Imaging was performed 10\u00a0minutes after injection of contrast agent using an inversion time (TI) scout sequence to determine the inversion time to null myocardial tissue signal. LGE CMR was obtained using a 3D multishot phase-sensitive inversion recovery (PSIR) bSSFP sequence at spatial resolution\u2009=\u20091.2\u2009\u00d7\u20091.2\u00a0mmctor\u2009=\u20092 .After ex vivo CMR, the heart was flash-frozen using liquid nitrogen in a 4.5\u00a0L cryogenic container . The heart was sectioned into uniformly thick short axis slices using a commercial-grade prosciutto slicer  obtaining slices of uniform thickness of approximately 2\u00a0mm to be matched to CMR studies. Slices were submerged in a PBS solution with 0.1\u00a0M triphenyl tetrazolium chloride (TTC) and incubated at 50\u00a0\u00b0 C for 15\u00a0min . Slices Cine CMR image series were used to calculate indexed LV mass (Mass), wall thickness (WT), end-diastolic volume (EDV), end-systolic volume (ESV), ejection fraction (EF) and cardiac output (CO). Epi- and endocardial contours were drawn manually at ED and ES (excluding papillary muscles) using standard techniques  , 20.For all images, scar size was assessed using full width at half maximum (FWHM) thresholding in a mid-LV slice with visible enhancement on LGE (QMass) . FWHM thScar transmurality was computed as the ratio of hyperintense (infarct) to non-enhanced myocardium (%) in a mid-ventricular short axis slice. The myocardium was divided into six circumferential wedges and transmurality was reported for anterolateral and posterolateral segments in which infarction was observed (two of six segments). Scar transmurality <5% in a segment was excluded as noise.Motion correction was used to align T1\u03c1 and T2 images using optical flow estimation of the image deformations . T1 and \u2206TX=TXinf\u2013TXrem and TXinf (TXrem) was the mean relaxation time in the infarcted (remote) tissue and \u03c3(TXrem) was the standard deviation of the relaxation times observed in remote myocardium [Contrast-to-noise ratio (CNR) was calculated for T1\u03c1, T2 and native T1:ocardium .t-test.Descriptive statistics were reported as mean\u2009\u00b1\u2009standard deviation (SD). Comparison of statistical means was performed using 2-way analysis of variance. Correlations were assessed with Pearson\u2019s r. Bland-Altman testing was performed to test for mean bias and variation between imaging methods . Pairwiss\u2009=\u200910) survived the 90\u00a0min ischemia and reperfusion study to their terminal CMR at 1 or 4\u00a0weeks. At 4\u00a0weeks post-MI, there was a 13.4\u2009\u00b1\u20095.4% reduction in EF compared to baseline and associated with a 22.7\u2009\u00b1\u20098.0\u00a0mL increase in ESV and a 24.2\u2009\u00b1\u200914.1\u00a0mL increase in EDV. End diastolic wall thickness decreased by 4.0% after 4\u00a0weeks (p\u2009<\u20090.05) and \u0394WT and \u0394LVEDV between baseline and 4\u00a0weeks were correlated . Additional details are reported in Table\u00a0All pigs s\u2009=\u20090 surviveHyperintense regions were observed at the lateral wall on all T1\u03c1, T2, and T1 maps and in LGE images at 1 and 4\u00a0weeks, consistent with ischemic injury to the circumflex coronary circulation  and 12.3\u2009\u00b1\u20093.2 (4\u00a0week), CNRT2\u2009=\u20098.0\u2009\u00b1\u20093.6 and 10.3\u2009\u00b1\u20095.8 and CNRT1\u2009=\u20097.0\u2009\u00b1\u20093.5 and 6.9\u2009\u00b1\u20092.4.As illustrated in Fig.\u00a0ss\u2009=\u20090.14) and, among animals who underwent both 1 and 4\u00a0week CMR, significantly decreased from 1 to 4\u00a0weeks (s\u2009<\u20090.01). Individual infarct size changes were \u0394T1\u03c1\u2009=\u2009\u22123.8%, \u0394T1\u2009=\u2009\u22123.5% and \u0394LGE\u2009=\u2009\u22122.8% from 1 to 4\u00a0weeks , good correlation for T1 and LGE  and poor correlation for T2 and LGE   and was unchanged from 1 to 4\u00a0weeks (p\u2009=\u20090.15).Infarct transmurality was not significantly different for T1\u03c1, T1 and T2 compared to LGE (p\u2009<\u20090.001), T1 and LGE  and moderate correspondence between T2 and LGE   T1\u03c1 values had higher relaxation time-dependent change than T2 and contrast-to-noise ratio compared to T1 and T2 in the infarcted myocardium; (2) there was a decrease in infarct size from 1 to 4\u00a0weeks on T1\u03c1, T1 and LGE CMR; and (3) T1\u03c1 infarct size was better correlated with LGE than T1 or T2 and that T2 in particular was poorly correlated. Improved infarct contrast-to-noise ratio on T1\u03c1 may explain the better correlation with LGE and histological infarct size and transmurality than T1 and T2.T1\u03c1 is increased in acute and chronic myocardial infarction , 11, 13,Furthermore, while T2 and native T1 are believed to be biomarkers for myocardial edema in the area-at-risk after acute MI , recent T2 had reduced correlation with LGE as compared to T1\u03c1 and T1, which may be partly explained by differences in the way post-infarction hemorrhage affects endogenous contrast. Degradation of hemoglobin byproducts in the hemorrhage in T2 and T2* CMR studies in patients and animals contribute to increased magnetic susceptibility-induced dephasing on CMR , 28. Acc1. As the amplitude B1 approaches zero, T1\u03c1 approaches T2 . In our comparison of T1\u03c1, T2 and T1, we used identical readout sequences to eliminate a major cause of measurement variation. In addition, we matched the time between adjacent T2 or T1\u03c1 preparations (4 heartbeats) and discarded the first scan because of variations in T1 recovery between preparations.Another reason for the poor T2 agreement with LGE is that different methods of preparation may give different T2, e.g. preparations with adiabatic refocusing pulses instead of a non-selective Hahn spin echo . The freInfarct size is expected to decrease from sub-acute to chronic post-infarction times . T1\u03c1, T1We found that T1\u03c1 and T1 infarct transmurality was correlated with LGE CMR at 1 and 4\u00a0week post-MI. However, differences in T1\u03c1 infarct transmurality might be explained by the varying acquisition times in the cardiac cycle. Although infarct size is not influenced by cardiac cycle, scar transmurality (derived from LGE CMR) has shown to vary between end-diastolic and end-systolic assessment . LGE MR T1\u03c1 CMR is increased in myocardial infarction compared to T2 and has improved contrast-to-noise ratio compared to T1 and T2. Infarct size and transmurality on T1\u03c1 and native T1 endogenous contrast was correlated with LGE CMR and thus may be useful as endogenous contrast CMR methods in ischemic patients who cannot receive contrast agents."}
{"text": "The 1:1, 2-methyl\u00adpyridium and 4-methyl\u00adpyridinium salts of the chiral 4-methyl\u00adbenzo\u00adyloxy-substituted succinic acid form, respectively one- and two-dimensional hydrogen-bonded crystal structures, 6H8N+\u00b7C20H17O8\u2212, comprises a 2-methyl\u00adpyridinium cation and a 2,3-bis\u00ad(4-methyl\u00adbenzo\u00adyloxy)succinate mono-anion while the salt (II), 2C6H8N+\u00b72C20H17O8\u2212\u00b75H2O, consists of a pair of 4-methyl\u00adpyridinium cations and 2,3-bis\u00ad(4-methyl\u00adbenzo\u00adyloxy)succinate mono-anions and five water mol\u00adecules of solvation in the asymmetric unit. In (I), the dihedral angle between the aromatic rings of the anion is 40.41\u2005(15)\u00b0, comparing with 43.0\u2005(3) and 85.7\u2005(2)\u00b0 in the conformationally dissimilar anion mol\u00adecules in (II). The pyridine ring of the cation in (I) is inclined at 23.64\u2005(16) and 42.69\u2005(17)\u00b0 to the two benzene moieties of the anion. In (II), these comparative values are 4.7\u2005(3), 43.5\u2005(3)\u00b0 and 43.5\u2005(3), 73.1\u2005(3)\u00b0 for the two associated cation and anion pairs. The crystal packing of (I) is stabilized by inter-ionic N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds as well as weak C\u2014H\u22ef\u03c0 inter\u00adactions, linking the ions into infinite chains along [100]. In the crystal packing of (II), the anions and cations are also linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds involving also the water mol\u00adecules, giving a two-dimensional network across (001). The crystal structure is also stabilized by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.The title salt (I), C A white precipitate was formed, which was dissolved in 30\u2005ml of water and then kept at room temperature for slow evaporation. After 2 months, crystals of (I)The title salts (I)Uiso = 1.5Ueq(methyl C or O) and Uiso = 1.2Ueq(aromatic and methyl\u00adene C). H atoms for NH and OH groups were located in difference-Fourier maps and refined with a distance restraint [N\u2014H = 0.86\u2005(1)\u2005\u00c5 or O\u2014H = 0.82\u2005(1)\u2005\u00c5]. The Flack absolute structure obtained for both structures  [(for (I)] and 0.6\u2005(3) [for (II)], for 1335 and 2690 quotients, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017012981/zs2388sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017012981/zs2388Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012981/zs2388IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017012981/zs2388Isup4.cmlSupporting information file. DOI: 1573939, 1573938CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal of the methyl\u00adphenyl compound, the mol\u00adecules are linked  28H24O6, (I), C34H22O5S, (II), and C27H20O3S2, (III), the cyclo\u00adhexa-1,3-diene rings of the 1,2-di\u00adhydro\u00adnaphthalene ring systems adopt half-chair, boat and half-chair conformations, respectively. The carbonyl O atoms attached to the di\u00adhydro\u00adnaphthalene ring systems are each significantly deviated from the mean plane of the 1,2-di\u00adhydro\u00adnaphthalene ring system, by 0.6162\u2005(12)\u2005\u00c5 in (I), 0.6016\u2005(16)\u2005\u00c5 in (II) and 0.515\u2005(3)\u2005\u00c5 in (III). The mean planes of the 1,2-di\u00adhydro\u00adnaphthalene ring systems make dihedral angles of 85.83\u2005(3), 88.19\u2005(3) and 81.67\u2005(8)\u00b0, respectively, with the methyl\u00adphenyl ring in (I), the pyrene ring in (II) and the phenyl ring in (III). In (I), the mol\u00adecular structure is stabilized by an intra\u00admolecular C\u2014H\u22efO hydrogen bond, generating an S(6) ring motif. In the crystal of (I), mol\u00adecules are linked by an inter\u00admolecular C\u2014H\u22efO hydrogen bond, which generates a C(8) zigzag chain running along [100]. Adjacent chains are further connected by C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6572\u2005(9)\u2005\u00c5], forming a double-chain structure. In the crystals of (II) and (III), mol\u00adecules are linked into chain structures by offset \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of 3.5349\u2005(12) and 3.8845\u2005(13)\u2005\u00c5 for (II) and 3.588\u2005(2)\u2005\u00c5 for (III). In (II) and (III), the thio\u00adphene rings are orientationally disordered over two sites, with occupancy ratios of 0.69:0.31 for (II), and 0.528\u2005(4):0.472\u2005(4) and 0.632\u2005(5):0.368\u2005(5) for (III).In the title 1-oxo-1,2-di\u00adhydro\u00adnaphthalene derivatives, C In (II)via C\u2014H\u22efO hydrogen bonds  zigzag chain along to [100]. Adjacent chains are further linked into a double-chain structure \u2005\u00c5, inter\u00adplanar distance = 3.443\u2005(1)\u2005\u00c5, slippage = 1.232\u2005\u00c5; Cg1 and Cg4 are the centroids of the C1\u2013C6 and C22\u2013C27 benzene rings, respectively].In the crystal of compound (I)re Fig.\u00a04 through Cg3\u22efCg6iii = 3.5349\u2005(12)\u2005\u00c5, inter\u00adplanar distance = 3.466\u2005(1)\u2005\u00c5; Cg3\u22efCg7iii = 3.8845\u2005(13)\u2005\u00c5, inter\u00adplanar distance = 3.468\u2005(1)\u2005\u00c5; Cg3, Cg6 and Cg7 are the centroids of the C1\u2013C6, C22\u2013C25/C33/C34 and C25\u2013C29/C34 benzene rings, respectively; symmetry code: (iii) \u2212x, 1/2-y, \u2212z; Fig.\u00a05Cg5\u22efCg7iv = 3.888\u2005(2)\u2005\u00c5, inter\u00adplanar distance = 3.632\u2005(1)\u2005\u00c5; Cg5 and Cg7 are the centroids of the benzene C1\u2013C6 and C22\u2013C27 rings, respectively; symmetry code: (iv) x, 3/2-y, z; Fig.\u00a06In the crystal of (II)Compound (I): To a stirred solution of 1-(4-meth\u00adoxy\u00adphen\u00adyl)-3-p-tolyl\u00adisobenzo\u00adfuran  in dry di\u00adchloro\u00admethane (DCM), dimethyl acetyl\u00adenedi\u00adcarboxyl\u00adate (DMAD)  was added and the reaction mixture was stirred at room temperature for 1\u2005h. Removal of the solvent was followed by column chromatographic purification  gave the isobenzo\u00adfuran\u2013DMAD adduct as a colorless solid . To a stirred solution of isobenzo\u00adfuran\u2013DMAD adduct  in dry DCM, BF3\u00b7OEt2  was added and the reaction mixture was stirred at room temperature for 5\u2005min. Removal of the solvent followed by column chromatographic purification  gave compound (I)Compound (II): To a stirred solution of 1-(pyren-1-yl)-3-(thio\u00adphen-2-yl)isobenzo\u00adfuran  in dry DCM (10\u2005ml), DMAD  was added and the reaction mixture was stirred at room temperature for 1\u2005h. To this, BF3\u00b7OEt2  was added and stirred at room temperature for 5\u2005min. Removal of the solvent followed by column chromatographic purification  afforded compound (II)Compound (III): To a solution of 1,3-di(thio\u00adphen-2-yl)isobenzo furan  in dry toluene (15\u2005ml), ethyl-3-phenyl\u00adpropiolate  was added and refluxed till the consumption of 1,3-di(thio\u00adphen-2-yl)isobenzo\u00adfuran (disappearance of fluorescent colour in 8\u2005h). After removal of toluene in vacuo, the crude adduct was dissolved in dry DCM (15\u2005ml), BF3\u00b7OEt2  was added and the reaction mixture was stirred for 10\u2005min at room temperature. Removal of the solvent was followed by column chromatographic purification  which afforded compound (III)Uiso(H) values were set to 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. In compound (II)SIMU and DELU) and bond length restraints (DFIX) with C\u2014S = 1.70\u2005(1)\u2005\u00c5, C\u2014C = 1.50\u2005(1)\u2005\u00c5 and C=C = 1.40\u2005(1)\u2005\u00c5 were applied to the disordered rings.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017000469/is5470sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989017000469/is5470Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017000469/is5470IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017000469/is5470IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470IIIsup7.cmlSupporting information file. DOI: 997379, 1438209, 1438503CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains two independent mol\u00adecules, which are linked by an O\u2014H\u22efO hydrogen bond. The dimers are further assembled into one-dimensional ladder like structure through O\u2014H\u22efF hydrogen bonds and stabilized by \u03c0\u2013\u03c0 inter\u00adactions. The ladders are further linked by C\u2014H\u22ef\u03c0 contacts. 2 complex, C12H12BF2N3O, contains two independent mol\u00adecules, which are linked by an O\u2014H\u22efO hydrogen bond. The dimers are further assembled into a one-dimensional ladder-like structure through O\u2014H\u22efF hydrogen bonds and stabilized by \u03c0\u2013\u03c0 inter\u00adactions. The ladders are further linked by C\u2014H\u22ef\u03c0 contacts.The asymmetric unit of the title azo\u00adpyrrole-BF Li et al. (20092\u2013azo\u00adpyrrole complexes as sensitizers for dye-sensitized solar cells (DSSCs) have been evaluated  and 1.382\u2005(3)\u2005\u00c5, respectively; Table\u00a01pyrrole bonds are shorter than the B\u2014Nazo bonds. The two N\u2014N bonds each adopt a trans conformation and at 1.318\u2005(3) and 1.312\u2005(3)\u2005\u00c5 are much longer than that in the structure of the free azo\u00adpyrrole ligand  = 3.544\u2005(1)\u2005\u00c5, Cg2\u22efCg3 = 3.617\u2005(1)\u2005\u00c5 and Cg3\u22efCg4 = 3.664\u2005(13)\u2005\u00c5; Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1\u2013C4, C7\u2013C12 and C19\u2013C24 rings, respectively]. The ladders assemble into a layer structure through C\u2014H\u22ef\u03c0 contacts  and 1.310\u2005(1)\u2005\u00c5] are comparable to those in the title compound.A search in the Cambridge Structural Database  and tri\u00adethyl\u00adamine (6\u2005mL) in dry di\u00adchloro\u00admethane (15\u2005mL) was slowly added boron trifluoride ethyl ether (2\u2005mL). The resulting solution was stirred for 40\u2005min, and then saturated potassium carbonate solution was added and stirred for 30 minutes. The resulting solution was extracted with ethyl acetate (10\u2005mL \u00d7 3) and evaporated under vacuum to dryness. The residue was purified by column chromatography, eluting with ethyl acetate and petroleum ether (v/v = 1:14), to give a dark-green product, m.p. = 405\u2005K. Yield 65%. 1H NMR : \u03b4 10.118 , 7.548\u20137.526 , 6.920\u20136.897, 6.342 , 2.371, 2.314 . Suitable crystals for X-ray diffraction analysis were obtained by the slow evaporation of an CHCl3/CH3OH solution of the title compound.To a solution of 2-(4-hy\u00addroxy\u00adlphenyl\u00adazo)-3,5-dimethyl-1-Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018006229/ex2007sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018006229/ex2007Isup2.hklStructure factors: contains datablock(s) I. DOI: 1839158CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two mol\u00adecules are linked into dimers by a combination of Hg\u22efHg [Hg\u22efHg = 3.6153\u2005(3)\u2005\u00c5] and C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions.The structure of C 3N,C1,N\u2032}[bromido/chlorido\u00ad(0.30/0.70)]mercury(II)\u2013{2,6-bis\u00ad[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]phenyl-\u03ba3N,C1,N\u2032}[bromido/chlorido\u00ad(0.24/0.76)]mer\u00adcury(II) (1/1), [HgBr0.30Cl0.70(C12H19N2)]\u00b7[HgBr0.24Cl0.76(C12H19N2)], there are two mol\u00adecules in the asymmetric unit of formula LHgX {L = 2,6-bis\u00ad[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]phenyl and X = Cl/Br}. In each mol\u00adecule, the halide site is mixed Cl/Br, with occupancies of 0.699\u2005(7):0.301\u2005(7) and 0.763\u2005(7):0.237\u2005(7), respectively. The two mol\u00adecules are linked into dimers by a combination of Hg\u22efHg [Hg\u22efHg = 3.6153\u2005(3)\u2005\u00c5] and C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 inter\u00adactions.In the mol\u00adecular structure of the title compound, {2,6-bis\u00ad[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]phenyl-\u03ba R2Hg and RHgX  have received considerable attention in the last three decades, mainly related to the search for versatile reagents in controlled transmetallation reactions :0.237\u2005(7) in mol\u00adecule B. In these moieties, there are two coordination spheres around each Hg atom \u2005\u00c5 is significantly smaller than the sum of the van der Waals radii for Hg\u22efHg 2 dimer at 3.41\u2005\u00c5 \u00admeth\u00adyl]-6-[(di\u00admethyl\u00adamino)\u00admeth\u00adyl]benzene}, which is a dimer linked by Hg2Br2 units, with one di\u00admethyl\u00adamino arm of each ligand coordinated to an Hg atom, and where there are no Hg\u22efHg inter\u00adactions present /2.867\u2005(6)\u2005\u00c5] are significantly shorter than the sum of the van der Waals radii for Hg and N [\u03a3rvdW  = 3.53\u2005\u00c5]. However, these values are slightly longer than related organo\u00admercury(II) compounds with one pendant arm of 2.65\u2005(1), 2.725\u2005(4) and 2.647\u2005(2)\u2005\u00c5 \u2005\u00c5, which is significantly smaller than the sum of the van der Waals radii for Hg\u22efHg 2C6H3Br], 1, was prepared according to the procedure given by van Koten and co-workers  was employed instead of 2.2 equivalents to quench with 2-bromo-1,3-bis\u00ad(bromo\u00admeth\u00adyl)benzene. This afforded a yellow oil which was purified by vacuum distillation to give a colorless oil in 70% yield. n-BuLi  was added dropwise via syringe to the solution of 1  in dry Et2O (15\u2005ml) under an inert atmosphere at 273\u2005K. After 30\u2005min, the color of the reaction mixture changed from colorless to pale yellow. To this, a solution of HgCl2  in dry THF (10\u2005ml) was added. The whole mixture was stirred for 5\u2005h at 273\u2005K and then allowed to warm slowly to room temperature. Then reaction mixture was filtered and the filtrate evaporated to dryness and the resulting precipitate extracted with hexane. The workup afforded a white precipitate of 2 . Colorless crystals of 2 suitable for single-crystal diffraction analysis were obtained by slow diffusion of hexane into CHCl3 at room temperature.The precursor 1H NMR: \u03b4 7.15 , 7.07 , 3.45 , 2.21 . 13C NMR: \u03b4 144.90, 128.36, 128.10, 66.01, 44.85. 199Hg NMR: \u03b4 \u2212930. Analysis calculated for C12H19ClHgN2: C 33.73, H 4.48, N 6.56%; found: C 32.55, H 5.10, N 5.26%. ESI\u2013MS (positive mode): [M + H]+m/z = 429.1005 (observed), 429.1015 .Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C-bound H atoms. There are two mol\u00adecules in the asymmetric unit and in each the halide site is occupied by a mix or Cl and Br, with refined occupancies of 0.699\u2005(7):0.301\u2005(7) and 0.763\u2005(7):0.237\u2005(7), respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989017014682/hg5496sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017014682/hg5496Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510433CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, pairs of mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming inversion dimers with graph-set notation  16H13Cl2N3O3S2, the thio\u00adphene ring is disordered in a 0.762\u2005(3):0.238\u2005(3) ratio by an approximate 180\u00b0 rotation of the ring around the S\u2014C bond linking the ring to the sulfonyl unit. The di\u00adchloro\u00adbenzene group is also disordered over two sets of sites with the same occupancy ratio. The mol\u00adecular conformation is stabilized by intra\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efN hydrogen bonds, forming rings with graph-set notation S(5). In the crystal, pairs of mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming inversion dimers with graph-set notation R22(8) and R12(11), which are connected by C\u2014H\u22efO hydrogen-bonding inter\u00adactions into ribbons parallel to (100). The ribbons are further connected into a three-dimensional network by C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions between benzene and thio\u00adphene rings, with centroid-to-centroid distances of 3.865\u2005(2), 3.867\u2005(7) and 3.853\u2005(2)\u2005\u00c5. Hirshfeld surface analysis has been used to confirm and qu\u00adantify the supra\u00admolecular inter\u00adactions.In the title compound, C The mol\u00adecular conformation is stabilized by intra\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efN hydrogen bonds (Table\u00a01S(5).In the mol\u00adecule of the title compound Fig.\u00a01, the dihs Table\u00a01, formingCg1\u22efCg1v, 3.867\u2005(7)\u2005\u00c5 for Cg2\u22efCg2v and 3.853\u2005(2)\u2005\u00c5 for Cg4\u22efCg4vi where Cg1, Cg2 and Cg4 are the centroids of the thio\u00adphene ring B, the thio\u00adphene ring B\u2032 and the benzene ring C .In the crystal, pairs of mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds Table\u00a01 and 3 \u25b8,CrystalExplorer17.5  and external (revdw) atom of the surface:The inter\u00admolecular distance information on the surface can be condensed into a two-dimensional histogram of dnorm= (di \u2212 rivdw)/rivdw + (de \u2212 revdw)/ervdw.dnorm surfaces mapped over a fixed colour scale of \u22121.9033 (red) to 1.1934 (blue). In the fingerprint plots  correspond to C\u22efCl (1.3%), N\u22efC (1.3%) and other less important inter\u00adactions (<1%). C\u22efC contacts correspond to inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions. The occurrence of non-high inter\u00adaction rates can be attributed to the fact that the small disordered portion of the mol\u00adecule is not considered.The mol\u00adecular Hirshfeld surfaces were obtained using a standard (high) surface resolution with the three-dimentional trans-rac-methyl 4-methyl\u00adbenzene\u00adsulfonate thio\u00adphen-2-yl]-1,3,4-oxa\u00addiazole  thio\u00adphen-2-yl]-1,3,4-oxa\u00addiazole  in di\u00adchloro\u00admethane (DCM) were added 2-thio\u00adphene\u00adsulfonamide , 1-ethyl-3-(3-di\u00admethyl\u00adamino-prop\u00adyl)carbodi\u00adimide  and 4-dimethyl-amino\u00adpyridine , and the resulting mixture was stirred overnight at room temperature. Upon completion of the reaction, the reaction mixture was partitioned between DCM and water. The collected organic layer was dried over anhydrous Na2SO4, filtered and evaporated to give the crude compound, which was purified with automated-flash chromatography . The obtained product was recrystallized from hexane and ethyl acetate (4:1), m.p. 464.8\u2013465.3\u2005K. 1H NMR (CDCl3): \u03b4 2.24 , 5.33 , 6.64 , 7.12 , 7.21 , 7.45 , 7.69 , 7.97 , 9.29 ; 13C NMR (CDCl3): 11.2, 50.5, 107.6, 127.3, 127.9, 129.1, 129.6, 131.7, 132.9, 133.8, 134.8, 135.1, 139.2, 142.0, 143.5, 158.4. HRMS m/z calculated for C16H13Cl2N3O3S2 [M + H]+ 429.9854; found: 429.9857.To a solution of methyl 1--5-methyl-1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl group. The nitro\u00adgen-bound H atom (H1N) was located in a difference-Fourier map and refined with the constraint N1\u2014H1N = 0.84\u2005(3)\u2005\u00c5 and Uiso(H) = 1.2Ueq(N). The thio\u00adphene ring is rotationally disordered by approximately 180\u00b0 over two positions, the ratio of refined occupancies being 0.762\u2005(3):0.238\u2005(3). The di\u00adchloro\u00adbenzene group of the title compound is also disordered over two sets of sites with the same occupancy ratio. The disordered dicholoro\u00adbenzene groups (C: C11\u2013C16 and C\u2032: C11A\u2013C16A) were refined as rigid hexa\u00adgons with bond lengths of 1.39\u2005\u00c5. The displacement ellipsoids for the corresponding carbon atoms in the disordered dicholoro\u00adbenzene groups were constrained by using the EADP command. Six outliers  global, I. DOI: 10.1107/S2056989018006242/rz5232Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018006242/rz5232Isup4.cmlSupporting information file. DOI: 10.1107/S2056989018006242/rz5232sup4.pdfCheckcif Report. DOI: 1839201CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title compound contains two independent mol\u00adecules with very similar conformations. Each mol\u00adecule is built up from a ferrocene unit substituted in the 1 and 1\u2032 positions by a protected sulfur di\u00adphenyl\u00adphosphine and by a di\u00admethyl\u00adhydrazine fragment. 8H11N2)(C17H14PS)], contains two independent mol\u00adecules (A and B) with very similar conformations. Each mol\u00adecule is built up from a ferrocene unit substituted in the 1 and 1\u2032 positions by a protected sulfur di\u00adphenyl\u00adphosphine and by a di\u00admethyl\u00adhydrazine, \u2013C(H)=N\u2014N(CH3)2, fragment. The two independent mol\u00adecules are linked by a C\u2014H\u22efN hydrogen bond. In the crystal, the A\u2013B dimer is linked by a pair of C\u2014H\u22efS hydrogen bonds, forming a centrosymmetric four-mol\u00adecule arrangement. These units are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming a supra\u00admolecular three-dimensional structure.The asymmetric unit of the title compound, [Fe(C The two independent mol\u00adecules are linked by a C\u2014H\u22efN hydrogen bond (Table\u00a02A view of the mol\u00adecular structures of the two independent mol\u00adecules (d Table\u00a02.A and 9.4\u2005(1)\u00b0 for mol\u00adecule B. However, the Cp rings are roughly parallel to each other with a dihedral angle of 1.46\u2005(12)\u00b0 for mol\u00adecule A and 1.85\u2005(12)\u00b0 for mol\u00adecule B. The protected di\u00adphenyl\u00adphosphine and the di\u00admethyl\u00adhydrazine units are approximately trans with respect to the ferrocenyl moiety: the torsion angle P1\u2014C11\u2014C16\u2014C161 and P2\u2014C21\u2014C26\u2014C261 are ca 140.4\u00b0 and ca 141.0\u00b0, respectively.In both mol\u00adecules, the two Cp rings are between eclipsed and staggered conformations, with a twist angle \u03c4 of 5.2\u2005(2)\u00b0 for mol\u00adecule endo towards the FeII ion, by \u22120.7330\u2005(6)\u2005\u00c5 (mol\u00adecule A) and 0.6986\u2005(6)\u2005\u00c5 (mol\u00adecule B) from the Cp ring plane, whereas the phospho\u00adrus atom lies in this plane, displaced by 0.0114\u2005(5) and \u22120.0603\u2005(4)\u2005\u00c5 for mol\u00adecules A and B, respectively. This arrangement, with the protected sulfur atom endo towards the FeII ion and the P atom roughly coplanar with the Cp ring, is quite common in related compounds . The geometry within the hydrazine moiety =N\u2014N(CH3)2 fragments the C=N bond lengths, which vary from 1.270\u2005(5) to 1.287\u2005(4)\u2005\u00c5, and the N\u2014N bond lengths, which vary from 1.367\u2005(4) to 1.382\u2005(5)\u2005\u00c5, are similar to those in the title compound  to 0.952\u2005(1)\u2005\u00c5. The corresponding distances for compound 3 fall within these ranges .In ZEQSOD and ZEQSOD02, the P atom is roughly in the Cp ring plane, with deviations from the mean plane ranging from 0.009\u2005(1) to 0.035\u2005(1)\u2005\u00c5, whereas the S atom is 3, is illustrated in Fig.\u00a012), 200\u2005mg (1.66\u2005mmol) of anhydrous magnesium sulfate MgSO4 and 5\u2005ml of anhydrous di\u00adchloro\u00admethane. To the red suspension, 100\u2005ml of N,N-di\u00admethyl\u00adhydrazine  was added using a syringe. The reaction mixture was then stirred at room temperature overnight. The crude material obtained was purified by flash chromatography on silica gel to yield 41\u2005mg of compound 3 as a brown solid (yield = 57%). Orange needle-like crystals of 3 were obtained by slow evaporation of a solution in pentane.The synthesis of the title compound, 1H NMR : \u03b4 (p.p.m.): 7.77\u20137.71 , 7.49\u20137.41 , 6.93 , 4.57 , 4.49 , 4.36 , 4.20 , 2.79 . 31P NMR : \u03b4 (p.p.m.): 41.6.Spectroscopic data: Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018000440/su5416sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018000440/su5416Isup2.hklStructure factors: contains datablock(s) I. DOI: 1815294CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Hyperlipidemia, a major pathological condition associated with disrupted lipid levels and physiological redox homeostasis. The excessive release of reactive oxygen species (ROS) leads to enhanced lipid peroxidation, aggravated atherosclerosis and oxidative stress. Integration of natural antioxidant blends in alone or with conventional treatments can alleviate these issues synergistically contributing least side effects. Published literature reported the efficacy of natural antioxidants as individual and in combinations in various conditions but less data is available on their evaluation in low dose ratio blends particularly in hypercholesterolemic diet.n\u2009=\u20096) weighing 1.2\u20131.6\u00a0kg, supplemented with high cholesterol diet (400\u00a0mg/kg) for 12\u00a0weeks were used in the experiment. Antioxidants were administered individual high (100\u00a0mg/kg) and in low dose combinations . Student\u2019s t test and one way analysis of variance (ANOVA) followed by Dunnet\u2019s test were used as statistical tools for evaluation.Antihyperlipidemic effects of selected natural antioxidants; the phenolic oligomeric proanthocyanidins (OPC) and pterostilbene (PT) with niacin (NA) were investigated in current study. Their effects on lipid profile, lipid peroxidation and their aptitude to establish redox state between oxidants and antioxidants in body were evaluated in high cholesterol diet fed animal model. Male albino rabbits (p >0.001) observed in 50:30:20 ratios of OPC, NA and PT, compared to individual therapies 37 and 18\u00a0% max respectively. Moreover the results were also in close proximity with the statin therapy .The results showed synergistic effects of low dose antioxidant blends. Therapies retarded elevation in blood lipid levels, lipid peroxidation and blood antioxidant depletion and consequently contributed in reestablishing redox homeostasis. The LDL/HDL ratio and atherogenic index were suppressed significantly in blend therapies with maximum effects of 59.3 and 25\u00a0% (This study provides an evidence for natural antioxidants blends superiority over individual therapy in chronic diseases like hyperlipidemia. Such therapies in human equivalent doses can help in mitigating chronic illnesses in general populations. Their oxidation leads to severe endothelial cell injury and atherosclerosis [Hyperlipidemia is a major pathological condition associated with mortality and disability in both developed and developing countries . Chronicclerosis \u20136. The sclerosis . Howeverclerosis . The antclerosis , 10. In clerosis , 11, 12.clerosis \u201316.Natural antioxidants were evaluated in individual and in combinations for lipid lowering and free radical scavenging properties and were found effective in depressing the disease progression \u201322. In cOligomeric proanthocyanidins (OPC) is a polyphenolic compound belongs to flavonoids class, widely distributed in plants and posses potent antioxidant  and lipit test was applied to evaluate the difference statistically. Lipid profiles are calculated as mean\u2009\u00b1\u2009SEM (n\u2009=\u20096) along with p-values in Table\u00a0Acute rise in lipid profiles were observed in rabbits administered with cholesterol for 2\u00a0weeks compared to healthy group. Almost two to four time rise was observed in every parameter. Student\u2019s p <0.001), 20.26\u2009\u00b1\u20090.94 (p <0.001) and 19.19\u2009\u00b1\u20090.91 (p <0.01) and AI values 0.893\u2009\u00b1\u20090.033 (p <0.01), 0.896\u2009\u00b1\u20090.053 (p <0.01), 0.971\u2009\u00b1\u20090.073 (p <0.05) respectively. The atorvastatin therapy showed 14.0\u2009\u00b1\u20090.99 (p <0.001) and 0.785\u2009\u00b1\u20090.061 (p <0.001) compared to disease control 30.50\u2009\u00b1\u20090.69, 1.096\u2009\u00b1\u20090.040. In combination therapies the results were even more significant and synergism were observed by improving blood lipid profile depending on dose ratio in particular combination. Among combinations of OPC with NA the 70:30 ratio delivered significant effects by suppressing LDL/HDL ratio to 15.36\u2009\u00b1\u20090.98 (p <0.001) while differ nonsignificantly from other two ratios 16.77\u2009\u00b1\u20090.69 (p <0.001) and 17.33\u2009\u00b1\u20090.75 (p <0.001). AI was significantly reduced to 0.843\u2009\u00b1\u20090.041 (p <0.001), 0.837\u2009\u00b1\u20090.045 (p <0.001) and 0.887\u2009\u00b1\u20090.037 (p <0.01) in 70:30, 30:70 and 50:50 respectively. Similarly in OPC with PT combinations all the ratios provided significant effects compared to disease control but no significant differences were observed between the groups. The LDL/HDL and AI were 14.60\u2009\u00b1\u20090.98 (p <0.001) and 0.851\u2009\u00b1\u20090.041 (p <0.001) in 70:30 ratio, 15.19\u2009\u00b1\u20090.42 (p <0.001), 0.929\u2009\u00b1\u20090.057 (p <0.05) in 30:70 and 16.33\u2009\u00b1\u20090.75 (p <0.001), 0.906\u2009\u00b1\u20090.037 (p <0.01) in 50:50 respectively. In NA and PT, the 70:30 and 50:50 combinations induced similar effects on LDL/HDL ratios 15.16\u2009\u00b1\u20090.89 and 15.16\u2009\u00b1\u20090.84 (p <0.001) respectively, while comparing AI values results were more profound in 70:30 (0.858\u2009\u00b1\u20090.053) (p <0.001) compared to other groups 0.919\u2009\u00b1\u20090.037 (p <0.05) and 0.868\u2009\u00b1\u20090.037 (p <0.01) respectively. In general the two drug combinations showed synergism, evident from significant outcome however differ less from one another [Single drug therapies showed significant effects in reducing lipid levels, confirmed by LDL/HDL ratio and atherogenic index (AI). The OPC, NA and PT maintained LDL/HDL ratios by 19.49\u2009\u00b1\u20090.87 (p <0.001) comparable with the statin outcome 52.66, 26.28\u00a0% (p <0.001) respectively. Though there were minor differences among the groups but differ significantly from the disease control. The high dose single drug therapies suppressed LDL/HDL by 37\u00a0% and AI by 18.5\u00a0% maximum, which are much less as compared to low dose blend therapies confirmed the superiority of combinational therapies. Lipid profiles in mean\u2009\u00b1\u2009SEM and %change in blood lipids at 95\u00a0% confidence interval are summarized in Tables\u00a0The ratios with optimum lipid lowering effects in above therapies were subsequently molded in to three drug combinations to evaluate the extent of synergism of antioxidants acting through various mechanisms. The antioxidant with highest ratio (70\u00a0%) was reduced by 20\u00a0mg and this amount was replaced with third candidate. All three drug combinations showed more significant results as compared to two drug combinations. Most significant effects were observed in 50:30:20 ratio of OPC, NA and PT which suppressed LDL/HDL ratio by 59.3\u00a0% and AI by 25\u00a0%  respectively in combination therapies compared to disease control 19.30\u2009\u00b1\u20091.18, 3.01\u2009\u00b1\u20090.28 and 3.73\u2009\u00b1\u20090.412\u00a0\u03bcmol/L. Although in individual therapies the raised levels of methionine, GSH and NAC (24.73\u2009\u00b1\u20091.04\u00a0\u03bcmol/L (p <0.05), 3.38\u2009\u00b1\u20090.42\u00a0\u03bcmol/L (p <0.01) and 3.86\u2009\u00b1\u20090.404\u00a0\u03bcmol/L (p <0.05)) were less significant compared to combination therapies. The all-trans retinoic acid showed opposite results and increased parallel with the lipid levels from 1.80\u2009\u00b1\u20090.10\u00a0\u03bcmol/L (blank control) to 4.48\u2009\u00b1\u20090.24\u00a0\u03bcmol/L (disease control) while in treatment groups its elevation was retarded down to 3.26\u2009\u00b1\u20090.12\u00a0\u03bcmol/L (p <0.001) max; observed on 70:30 ratio of OPC and PT.Significant up-regulation was observed in levels of methionine, GSH and NAC upto 35.08\u2009\u00b1\u20091.60, 3.82\u2009\u00b1\u20090.47 and 4.21\u2009\u00b1\u20090.425\u00a0\u03bcmol/L (p <0.01) among individual therapies and more in combinational therapies ranging 2.51\u2009\u00b1\u20090.092 to 3.40\u2009\u00b1\u20090.097 (p <0.001), compared to disease control 2.12\u2009\u00b1\u20090.058. Homocysteine level was significantly controlled down to 10.09\u2009\u00b1\u20091.39\u00a0\u03bcmol/L (p <0.01), although nonsignificant variations were observed among treatment groups. Almost half of groups delivered nonsignificant effects on ascorbic acid levels with maximum effect of 5.29\u2009\u00b1\u20090.51\u00a0\u03bcmol/L (p <0.001) observed in 50:30:20 ratio of OPC, NA and PT compared to disease control 4.90\u2009\u00b1\u20090.59\u00a0\u03bcmol/L. The natural antioxidants were able to correct the antioxidant levels in blood and are more effective when used in blend therapies rather than individual as summarized in mean\u2009\u00b1\u2009SEM in Tables\u00a0The improvement in GSH/GSSG ratios was significant in OPC (2.83\u2009\u00b1\u20090.065)  (\u226599\u00a0% pure). Cholesterol kit; TC, TG and HDL (Human diagnostics GmbH Germany). Oligomeric proanthocyanidins (OPC) , pterostilbene (PT)  (\u226599\u00a0% pure) and niacin (NA) (Scharlau Chemie SA) (\u226598\u00a0% pure).HPLC system  linked with a DECADE II Electrochemical Detector , HPLC column Discovery HS C18 RP chromatographic column . Lambda-25 UV/Visible spectrophotometer (Perkin Elmer). Centrifuge machine (Centurion scientific Ltd) and Incubator (Incucell Med Center GmbH Germany) were used in the analysis.n\u2009=\u20096. Three groups were treated with OPC, PT and NA individually in 100\u00a0mg/kg doses along with cholesterol doses. In 09 groups, low dose combinatorial blends of all the three drugs in 30:70, 50:50 and 70:30 ratios were administered and most effective combination in each two drug combinations was further incorporated in three drug combinations  were used in the experiment. The experimental protocol for our study was approved by ethical committee of Department of Pharmacy University of Peshawar under reference number: 04/EC-15/Pharm. After 7\u00a0days of acclimatization in animal house and bio assay center, hyperlipidemia was developed according to the previous reported protocol . AnimalsPlasma lipid profiling was performed on commercial kits. Base line levels were recorded and samples were taken at every 2\u00a0weeks interval after overnight fasting to evaluate the effect of therapies on blood lipid levels sequentially. Total cholesterol (TC), teiglyceride (TG) and high density lipoproteins (HDL-C) were calculated enzymatically, while low density lipoproteins (LDL-C), very low density lipoproteins (VLDL-C) and atherogenic index (AI) were calculated according to the following formulae \u201365.1\\doctrans retinol (ATR) were determined simultaneously using HPLC-UV [Serum levels of water soluble thiol antioxidants; glutathione (GSH) its oxidized form (GSSG), GSH/GSSG ratio, cystine, cysteine (cys), Homocysteine (Hcy), methionine (meth), N-acetylcysteine (NAC) long with ascorbic acid (AA) and lipid peroxidation were determined simultaneously at the end of study using RP-HPLC- electro chemical detection (ECD) method . Fat sol HPLC-UV .t test for pair analysis and one way analysis of variance (ANOVA) followed by Dunnett\u2019s test for comparison of lipid lowering effect in all treatment groups with respect to the disease control (with no treatment). Data is presented in mean\u2009\u00b1\u2009standard error of mean (SEM) at level of significance p <0.05\u00a0%.Data analysis was performed by applying student\u2019s"}
{"text": "II complex containing an \u03c3-dimerized TCNQ\u2013TCNQ unit is presented, with a C\u2014C bond length of 1.653\u2005(11)\u2005\u00c5. In addition, the \u03c3-dimerized TCNQ\u2013TCNQ unit (refined 75% occupancy) is disordered, forming also a less populated pair of TCNQ mol\u00adecules (25% occupancy) with tightly \u03c0-stacked di\u00adcyano\u00admethanide groups.The first example of an Ni 3)2, 2,2\u2032-bipyridine (bpy) and LiTCNQ  in a 1:3:2 molar ratio yielded single crystals of bis\u00ad[tris\u00adnickel(II)] bis\u00ad bi hexa\u00adhydrate, [Ni(C10H8N2)3]2(C24H8N8)(C12H4N4)2\u00b76H2O or [Ni(bpy)3]2(TCNQ\u2013TCNQ)(TCNQ)2\u00b76H2O. The crystal structure comprises [Ni(bpy)3]2+ complex cations, two centrosymmetric crystallographically independent TCNQ\u00b7\u2212 anion radicals with \u03c0-stacked exo groups, and an additional dimeric TCNQ\u2013TCNQ unit which comprises 75.3\u2005(9)% of a \u03c3-dimerized (TCNQ\u2013TCNQ)2\u2212 dianion and 24.7\u2005(9)% of two TCNQ\u00b7\u2212 anion radicals with tightly \u03c0-stacked exo groups. The title complex represents the first example of an NiII complex containing a \u03c3-dimerized (TCNQ\u2013TCNQ)2\u2212 dianion. Disordered solvent water mol\u00adecules present in the crystal structure participate in hydrogen-bonding inter\u00adactions.Crystallization from an aqueous methanol system composed of Ni(NO Several complexes of NiII-containing TCNQ species have been reported previously, e.g. [Ni(terpy)2](TCNQ)2  with non-coordinating \u03c0-dimerized anion radicals  with \u03c3-coordinating anion radicals 4\u00b7(CH3)2CO was reported, along with the results of its crystal structure analysis 3]2(TCNQ\u2013TCNQ)(TCNQ)2\u00b76H2O (1) and report here its crystal structure.In the quest for new promising mol\u00adecular magnetic materials besides the complexes of 31, comprises two [Ni(bpy)3]2+ complex cations, a centrosymmetric TCNQ\u2013TCNQ dimeric unit, two centrosymmetric crystallographically independent TCNQ\u00b7\u2212 anion radicals, and three crystallographically independent disordered solvent water mol\u00adecules 8]\u00b76H2O :0.247\u2005(9)  1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 2\u00a0\u2212\u00a0z] dimerization bond length is 1.653\u2005(11)\u2005\u00c5 and this value is within the usual range (see Database survey section). At the same time, this value is longer than a usual single C\u2014C bond and, consequently, the corresponding bond angles around the C37A atom range from 105.6\u2005(4) to 113.6\u2005(3)\u00b0, displaying significant deviations from the ideal tetra\u00adhedral angle. In the less populated pair of anion radicals within TCNQA, the distance between the C37B atom and its symmetry-related counterpart C37Biii is 3.06\u2005(2)\u2005\u00c5; the inter\u00adplanar distance between the least-squares plane P1 formed by atoms C31B, C37B, C38B and C39B and the least-squares plane P2 formed by their symmetry-related counterparts through a centre of symmetry at  is 3.03\u2005\u00c5. The distance of the C37iii atom from the plane P1 is 2.90\u2005\u00c5 and the slippage between atoms C37B and C37Biii is 0.98\u2005\u00c5. These geometric parameters suggest a very strong \u03c0-inter\u00adaction between the less populated pair of anion radicals in TCNQA, and they are pre-positioned for \u03c3-dimerization with little structural rearrangement required upon formation of the covalent bond. This could be seen as an indication of \u03c3-bond formation in the solid state upon crystallization rather than pre-formation of the \u03c3-dimers in solution.The unit cell of the title complex, s Figs. 1 \u25b8 \u25b8 \u25b8\u00b7\u2212 anion radicals, TCNQB and TCNQC, in the crystal structure of 1 \u2019 by Ballester et al. (1999Biii and N10vii  is, however, much longer than for the \u2018front-end\u2019 di\u00adcyano\u00admethanide group. It is outside the usually observed range for strong \u03c0-stacking inter\u00adactions in analogous systems  1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] and the second shortest contact is 3.479\u2005(4)\u2005\u00c5 between atoms C46 and C53ii; the latter distance is already somewhat longer due to the noncoplanarity of the two anion radicals. These observed distances are at the upper border for stacking arrangements reported for similar compounds  hydrogen-bonded bridges involving TCNQA dianions and TCNQC anion radicals, yielding a supra\u00admolecular layer within the bc plane  form an additional hydrogen-bonded bridging path, N\u22efH\u2014O2A\u22efH\u2014O3B\u2014H\u22efO1B\u2014H\u22efN, between the supra\u00admolecular layers. On the other hand, the least-occupied position (O2B) of water mol\u00adecule O2 seems to be hydrogen bonded only to the nitrile N atom and so partially occupies the void in the structure in alternation with its symmetry-related atom O2Bxi  (bipy)]\u00b7p-xy (TCNQ\u2013TCNQ)] \u2005\u00c5, which is in line with the observed range in the published crystal structures.A search of the CSD (Groom 3)2\u00b76H2O  and bpy  in methanol (2\u2005ml) at the same temperature. The dark-green solution that resulted was immediately enclosed in a 5\u2005ml vial and cooled to room temperature (8.75\u2005K\u2005h\u22121) in a programmable drying oven. The dark-green crystalline solid that resulted was filtered off, washed with a small amount of methanol and ether, and dried in air. The solid was mainly of microcrystalline character, with a few single crystals suitable for X-ray study (yield 63%). IR : 3341 (m), 3382 (m), 3074 (vw), 3033 (vw), 2200 (s), 2175 (vs), 2152ssh, 1598 (m), 1581 (s), 1504 (s), 1471 (m), 1441 (m), 1359 (s), 1182 (m), 1020 (w), 987 (w), 826 (w), 779 (m), 765 (m), 737 (w), 653 (w), 483 (w). CNH : C 65.54/67.00, H 3.87/3.98, N 19.81/19.80.A solution of LiTCNQ  in methanol (2\u2005ml) heated to 323\u2005K was added dropwise to a mixture of Ni2\u2212 dianion is positionally disordered  were considered to be exactly one half, while the refined site-occupation factors for atoms O2A and O2B are 0.908\u2005(3) and 0.092\u2005(3), respectively. Some of the water H atoms were resolved in difference maps and all H-atom positions were refined assuming idealized geometric parameters of O\u2014H = 0.85\u2005(1)\u2005\u00c5 and H\u22efH = 1.344\u2005(1)\u2005\u00c5. For the H atoms of the O2B water mol\u00adecule (the least-occupied water mol\u00adecule), a riding model was used. The Uiso parameters for water H atoms were set at 1.5 times the Ueq value of the parent O atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016019162/zl2686sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016019162/zl2686Isup2.hklStructure factors: contains datablock(s) I. DOI: 1520298CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, complex and DMF solvate mol\u00adecules build up a one-dimensional hydrogen-bonded polymer along [010].The homoleptic nickel\u2013thio\u00adsemicarbazonate complex shows structural features including an unusual  II acetate tetra\u00adhydrate with 4-methyl-2-hydrazinecarbo\u00adthio\u00adamide in a 2:1 molar ratio and recrystallization from di\u00admethyl\u00adformamide yielded the title compound, [Ni(C12H14N3S)2]\u00b7C3H7NO. The ligands act as monoanionic \u03ba2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono\u00adthio\u00adsemicarbazone complexes. Intra\u00admolecular H\u22efNi trans-inter\u00adactions are observed [H\u22efNi distances are 2.50 and 2.57\u2005\u00c5] and thus anagostic inter\u00adactions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H\u22efH (66.6%), H\u22efS (12.3%) and H\u22efC (10.9%) inter\u00adactions. In the crystal, the complex mol\u00adecules are linked by di\u00admethyl\u00adformamide solvent mol\u00adecules through N\u2014H\u22efO inter\u00adactions into one-dimensional hydrogen-bonded polymers along [010].The reaction of Ni The hydrazinic H atom can be easily removed and the negative charge is then delocalized over the C\u2014N\u2014N\u2014C\u2014S backbone, which enables chemical bonding with many different metal ions hydrazinecarbothi\u00adamide as ligand \u2005\u00c5 for C3 and of 0.3685\u2005(15)\u2005\u00c5 for C15. The two ligands are deprotonated with the negative charge delocalized over the C\u2014N\u2014N\u2014C\u2014S entity, as suggested by their inter\u00admediate bond lengths and supported by the sp2-hybridization for C1, C13, N1, C11, C23 and N4. The imine and thio\u00adamide C\u2014N distances indicate considerable double-bond character, while the C\u2014S distance is consistent with mainly single-bond character. The change of the bond lengths is a key feature to distinguish free, i.e. non-coordinating, and coordinating thio\u00adsemicarbazones. For the title compound these distances  are C1\u2014N1 = 1.306\u2005(2), N1\u2014N2 = 1.408\u2005(2), N2\u2014C11 = 1.307\u2005(2) and C11\u2014S1 = 1.752\u2005(2) for one ligand and C13\u2014N4 = 1.303\u2005(2), N4\u2014N5 = 1.409\u2005(2), N5\u2014C23 = 1.303\u2005(2) and C23\u2014S2 = 1.7573\u2005(19) for the other one.One mol\u00adecule of the title complex and one di\u00admethyl\u00adformamide solvate comprise the asymmetric unit. The Nids Fig.\u00a01. The maxcis coordination mode, which is rather uncommon for mono-thio\u00adsemicarbazone ligands, as well as two positioned trans H\u22efNi anagostic inter\u00adactions  \u2212x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a0In the crystal, the coordination entities are linked by DMF solvate mol\u00adecules through N\u2014H\u22efO inter\u00adactions. The DMF-oxygen atoms are hydrogen-bond acceptors, forming a bridg\u00ading structure between two N\u2014H\u22efO arrangements: N6\u2014H6\u22efO1 and N3\u2014H3\u22efO10] Fig.\u00a03. Additio0] Fig.\u00a03.et al., 2012de (y axis) and di (x axis) values are the closest external and inter\u00adnal distances  from given points on the Hirshfeld surface contacts -4-phenyl-hydrazine\u00adcarbo\u00adthio\u00adamidate-\u03ba2N1,S)}nickel(II) monohydrate bis\u00ad(tetra\u00adhydro\u00adfurane) solvate  = 1.2Ueq(C and N) for the sp2\u2013hybridized DMF C atom, the aromatic and the secondary C atoms, and for all N atoms, and with Uiso(H) = 1.5Ueq(C) for the methyl C atoms. The bond lengths  are: C\u2014H = 0.99 for \u2013CH2\u2013 fragments, C\u2014H = 0.98 for CH3\u2013 fragments, C\u2014H = 0.95 for aromatic groups and the sp2-hybridized DMF C atom; N\u2014H = 0.88 for all N atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017007198/wm5389sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007198/wm5389Isup2.hklStructure factors: contains datablock(s) I. DOI: 1550129CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title benzoyl\u00adthio\u00adurea derivative (MPiCB), the piperidine ring has a chair conformation and its mean plane is inclined to the 4-meth\u00adoxy\u00adbenzene ring by 63.0\u2005(3)\u00b0. 14H18N2O2S, the piperidine ring has a chair conformation. Its mean plane is twisted with respect to the 4-meth\u00adoxy\u00adbenzoyl ring, with a dihedral angle of 63.0\u2005(3)\u00b0. The central N\u2014C(=S)\u2014N(H)\u2014C(=O) bridge is twisted with an N\u2014C\u2014N\u2014C torsion angle of 74.8\u2005(6)\u00b0. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming chains along the c-axis direction. Adjacent chains are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to the ac plane. The layers are linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.927\u2005(3)\u2005\u00c5], forming a supra\u00admolecular three-dimensional structure.In the title compound, C The central N\u2014C(=S)\u2014N(H)\u2014C(=O) bridge is twisted with an N2\u2014C8\u2014N1\u2014C7 torsion angle of 74.8\u2005(6)\u00b0. The meth\u00adoxy group lies in the plane of the benzene ring, with the C14\u2014O2\u2014C4\u2014C3 torsion angle being 180.0\u2005(4)\u00b0.The mol\u00adecular structure of the title compound, MPiCB, is illustrated in Fig.\u00a01c-axis direction (Table\u00a01ac plane (Table\u00a01Cg\u22efCgi = 3.927\u2005(3)\u2005\u00c5; Cg is the centroid of the C1\u2013C6 ring; inter\u00adplanar distance = 3.517\u2005(2)\u2005\u00c5; slippage = 1.747\u2005\u00c5; symmetry code: (i) \u2212x, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a02].In the crystal of MPiCB, neighbouring mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming chains along the n Table\u00a01. Adjacene Table\u00a01. The layet al., 2016N-(carbono\u00adthio\u00adyl)benzamide skeleton gave 37 hits. Two compounds are of particular inter\u00adest, namely 4-meth\u00adoxy-N-(pyrrolidin-1-ylcarbono\u00adthio\u00adyl)benzamide -3,4,5-tri\u00admeth\u00adoxy\u00adbenz\u00adamide benzamide  was added slowly to ammonium thio\u00adcyanate (0.01\u2005mol) in acetone and the mixture was stirred for 30\u2005min at room temperature. A white precipitate of ammonium chloride was filtered off and the filtrate was cooled in an ice bath (278\u2013283\u2005K) for about 15\u2005min. A cold solution (278\u2013283\u2005K) of piperidine (0.01\u2005mol) in acetone was added to the benzoyl iso\u00adthio\u00adcyanate and the mixture was left for 3\u2005h at room temperature. A yellowish precipitate was formed, filtered and washed with cold water to give pale-yellow crystals .3) 2900, \u03bd(C=O) 1609, \u03bd(C\u2014Cbenzene) 1460, \u03bd(C\u2014Ostretching) 1327 and v(C=S) 1252\u2005cm\u22121. The 1H NMR spectrum exhibits the H(N) group at 8.35\u2005Hz, while the 13C NMR signal of the C=S and C=O groups appear at 174.66 and 163.19\u2005Hz, respectively.The infrared spectrum of MPiCB shows the characteristic signals for \u03bd(NH) 3300, \u03bd(O\u2014CHUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017013317/su4162sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017013317/su4162Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017013317/su4162Isup3.cmlSupporting information file. DOI: 1575129CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds into supra\u00admolecular chains propagating along the [110] direction.In the crystal, the title centrosymmetric Zn 8H4NO2)2(C10H14N2O)2(H2O)2], the ZnII cation, located on an inversion centre, is coordinated by two water mol\u00adecules, two 4-cyano\u00adbenzoate (CB) anions and two di\u00adethyl\u00adnicotinamide (DENA) ligands in a distorted N2O4 octa\u00adhedral geometry. In the mol\u00adecule, the dihedral angle between the planar carboxyl\u00adate group and the adjacent benzene ring is 9.50\u2005(14)\u00b0, while the benzene and pyridine rings are oriented at a dihedral angle of 56.99\u2005(5)\u00b0. The water mol\u00adecules exhibit both an intra\u00admolecular hydrogen bond  and an inter\u00admolecular hydrogen bond ; the latter lead to the formation of supra\u00admolecular chains propagating along the [110] direction.In the title complex, [Zn(C N,N-di\u00adethyl\u00adnicotinamide (DENA) is an important respiratory stimulant 2(C7H4ClO2)2(H2O)2] 2(C10H14N2O)2(H2O)2]  is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels  and DENA ligands, namely trans-di\u00adaqua\u00adbis\u00ad(4-cyano\u00adbenzoato-\u03baO)bis\u00adzinc(II), [Zn(DENA)2(CB)2(H2O)2], and report herein its crystal structure.The structure-function\u2013coordination relationships of the aryl\u00adcarboxyl\u00adate ion in ZnII atom located on an inversion centre, one 4-cyano\u00adbenzoate (CB) ligand, one N,N-di\u00adethyl\u00adnicotinamide (DENA) ligand and one water mol\u00adecule, all ligands coordinating to the ZnII atom in a monodentate manner  of the two symmetry-related monodentate CB anions and the two symmetry-related water O atoms (O4 and O4i) around the Zn1 atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination sphere is completed by the two pyridine N atoms (N2 and N2i) of the two symmetry-related monodentate DENA ligands in the axial positions  \u2005\u00c5 below the planar (O1/O2/C1) carboxyl\u00adate group. The O\u2014Zn\u2014O and O\u2013Zn\u2014N bond angles range from 87.64\u2005(5) to 92.36\u2005(5)\u00b0.In the carboxyl\u00adate groups, the C\u2014O bonds for coordinating O atoms are 0.0148\u2005(19)\u2005\u00c5 longer than those of the non-coordinating ones [C1\u2014O1 = 1.2436\u2005(19)\u2005\u00c5 and C1\u2014O2 = 1.2584\u2005(18)\u2005\u00c5], indicating delocalized bonding arrangements rather than localized single and double bonds. The Zn\u2014O bond lengths are 2.1503\u2005(11)\u2005\u00c5 (for water O atoms) and 2.0842\u2005(10)\u2005\u00c5 (for benzoate O atoms) and the Zn\u2014N bond length is 2.1501\u2005(11)\u2005\u00c5, the Zn\u2014O bond lengths for water oxygen atoms are The dihedral angle between the planar carboxyl\u00adate group (O1/O2/C1) and the adjacent benzene ring (C2\u2013C7) is 9.50\u2005(14)\u00b0, while the benzene and pyridine (N2/C9\u2013C14) rings are oriented at a dihedral angle of 56.99\u2005(5)\u00b0.w\u22efOc  hydrogen bonds (Table\u00a01S(6) hydrogen-bonding motifs  hydrogen bonds  in H2O (50\u2005ml) and di\u00adethyl\u00adnicotinamide  in H2O (10\u2005ml) with sodium 4-cyano\u00adbenzoate  in H2O (100\u2005ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving translucent intense colourless single crystals.The title compound was prepared by the reaction of ZnSO2O) were located in a difference Fourier map and were refined freely. The C-bound H atoms were positioned geometrically with C\u2014H = 0.93, 0.97 and 0.96\u2005\u00c5, for aromatic, methyl\u00adene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k \u00d7 Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic and methyl\u00adene H atoms.The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0210.1107/S2056989016013815/xu5890sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013815/xu5890Isup2.hklStructure factors: contains datablock(s) I. DOI: 1501337CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, there are only weak C\u2014H\u22efO hydrogen bonds and offset \u03c0\u2013\u03c0 inter\u00adactions present.The whole mol\u00adecule of the title di\u00adaryl\u00adcarbonate is generated by mirror symmetry, the mirror bis\u00adecting the central benzene ring, and the carbonate groups adopt an  20H14O6, is generated by mirror symmetry, the mirror bis\u00adecting the central benzene ring. The carbonate groups adopt an s-cis-s-cis conformation, with torsion angles of 58.7\u2005(2) and 116.32\u2005(15)\u00b0. The crystal structure of 1,3-phenyl\u00adene bis\u00ad(phenyl carbonate) contains no strong hydrogen bonds, though weak C\u2014H\u22efO and offset \u03c0\u2013\u03c0 inter\u00adactions are observed, forming layers parallel to the ac plane.The whole mol\u00adecule of the title compound, C We surmise this compound formed through a combination of inter\u00admolecular \u2018self-alcoholysis\u2019 reactions leading to a carb\u00adamate inter\u00admediate  structure reported herein was identified as an unexpected side product from the attempted recrystallization of 1- and 116.32\u2005(15)\u00b0, respectively. The 1,3-substitution of the central aromatic ring imparts the mol\u00adecule with a bent or \u2018U-shape\u2019 conformation and a significant net dipole moment.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01a-axis direction are related by glide symmetry and assemble into polar chains \u2005\u00c5, inter\u00adplanar distance = 3.438\u2005(1)\u2005\u00c5, with a slippage of 1.669\u2005\u00c5 ; Cg2\u22efCg2iii,iv = 3.822\u2005(1)\u2005\u00c5, inter\u00adplanar distance = 3.398\u2005(1)\u2005\u00c5, with a slippage of 1.749\u2005\u00c5 , C\u2014O bond lengths fall within 1.310 and 1.387\u2005\u00c5 [average: 1.343\u2005(9)\u2005\u00c5], and O\u2014C\u2014O angles average 106\u2005(1)\u00b0. However, torsion angles about the C\u2014O\u2014C\u2014Carom bonds are extremely variable.A search of the Cambridge Structural Database  was identified in this search, 4,4\u2032-iso\u00adpropyl\u00adidenediphenyl-bis\u00ad(phenyl\u00adcarbonate) -3-phenyl\u00adurea was filtered, dried, and recrystallized in assorted organic solvents . Slow evaporation of an ethano\u00adlic solution in a 1 dram vial, capped with pierced lids, yielded large colorless plates of 1,3-phenyl\u00adene bis\u00ad(phenyl carbonate). Needle-like crystals identified within the same vials corresponded to 1-(m-phenol)-3-phenyl\u00adurea. The appearance of 1,3-phenyl\u00adene bis\u00ad(phenyl carbonate) crystals was not consistent across multiple recrystallization experiments, suggesting that select impurities and/or longer, delayed evaporation methods that favor non-equilibrium products may be needed to obtain this material.Equimolar amounts of 3-amino\u00adphenol and phenyl iso\u00adcyanate were added to benzene under nitro\u00adgen and stirred for 24\u2005h. A white precipitate identified as 1-(Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017016772/su5407sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017016772/su5407Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017016772/su5407Isup3.cmlSupporting information file. DOI: 1586885CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Intra\u00admolecular amine-N\u2014H\u22efN(imine) and hy\u00addroxy-O\u2014H\u22efO(meth\u00adoxy) hydrogen bonds are noted. In the mol\u00adecular packing, amide-N\u2014H\u22efO(amide), hydroxyl-O\u2014H\u22efN(imine) and phenyl\u00adamine-N\u2014H\u22efO(meth\u00adoxy) hydrogen bonding leads to layers in the  A and B) comprise the asymmetric unit of the title compound, C18H21N3O3. The urea moiety is disubstituted with one amine being linked to a phenyl ring, which is twisted out of the plane of the CN2O urea core [dihedral angles = 25.57\u2005(11) (A) and 29.13\u2005(10)\u00b0 (B)]. The second amine is connected to an imine (E conformation), which is linked in turn to an ethane bridge that links a disubstituted benzene ring. Intra\u00admolecular amine-N\u2014H\u22efN(imine) and hydroxyl-O\u2014H\u22efO(meth\u00adoxy) hydrogen bonds close S(5) loops in each case. The mol\u00adecules have twisted conformations with the dihedral angles between the outer rings being 38.64\u2005(81) (A) and 48.55\u2005(7)\u00b0 (B). In the crystal, amide-N\u2014H\u22efO(amide) hydrogen bonds link the mol\u00adecules A and B via an eight-membered {\u22efHNCO}2 synthon. Further associations between mol\u00adecules, leading to supra\u00admolecular layers in the ac plane, are hydrogen bonds of the type hydroxyl-O\u2014H\u22efN(imine) and phenyl\u00adamine-N\u2014H\u22efO(meth\u00adoxy). Connections between layers, leading to a three-dimensional architecture, comprise benzene-C\u2014H\u22efO(hy\u00addroxy) inter\u00adactions. A detailed analysis of the calculated Hirshfeld surfaces shows mol\u00adecules A and B participate in very similar inter\u00admolecular inter\u00adactions and that any variations relate to conformational differences between the mol\u00adecules.Two independent mol\u00adecules ( They have attracted considerable attention due to their wide spectrum of bio\u00adlogical activities, including anti-convulsant B]. The phenyl ring is inclined to this plane, forming a dihedral angle of 25.57\u2005(11)\u00b0 [29.13\u2005(10)\u00b0 for mol\u00adecule B]. Intra\u00admolecular N\u2014H\u22efN hydrogen bonds are found within the urea residues, Table\u00a01B]. As a result, the mol\u00adecule is twisted with the terminal rings inclined to each other, forming a (C2\u2013C7)/(C11\u2013C16) dihedral angle of 38.64\u2005(8)\u00b0 [(C20\u2013C25)/(C29\u2013C34) = 48.55\u2005(7)\u00b0 for B]. The latter represents the major difference between mol\u00adecules A and B, as illustrated in the overlay diagram shown in Fig.\u00a02E in each mol\u00adecule. Finally, each of the meth\u00adoxy substituents is twisted out of the plane of the ring to which it is bonded [C18\u2014O2\u2014C13\u2014C12 = 11.7\u2005(3) and C36\u2014O5\u2014C31\u2014C30 = \u221216.5\u2005(3)\u00b0].Two independent mol\u00adecules, a. The two mol\u00adecules comprising the asymmetric unit associate via an eight-membered amide synthon, {\u22efOCNH}2. The hy\u00addroxy-O\u2014H groups at each end of the dimeric aggregate hydrogen bond to an imine-N atom of the other independent mol\u00adecule. The hydroxyl-O3\u2014H\u22efN6(imine) inter\u00adaction is incorporated within a 10-membered {\u22efHOC2O\u22efHNCNN} heterosynthon owing to the formation of a relatively weak phenyl\u00adamine-N4\u2014H\u22efO2(meth\u00adoxy) hydrogen bond. The putative phenyl\u00adamine-N1\u2014H\u22efO5(meth\u00adoxy) hydrogen bond is beyond the standard limits . The most obvious connections between the supra\u00admolecular layers are of the type benzene-C\u2014H\u22efO(hydrox\u00adyl), which occur between centrosymmetrically related O6-benzene rings. A view of the unit-cell contents highlighting the stacking of layers is shown in Fig.\u00a03c. Other C\u2014H\u22efO and several C\u2014H\u22ef\u03c0 inter\u00adactions occur in the crystal but within the layers stabilized by hydrogen bonding. These and other weak inter\u00adactions are discussed in more detail in Analysis of the Hirshfeld surface i.e. mol\u00adecules A and B, and for overall (I)et al., 2017The Hirshfeld surface was calculated for the individual O1- and O4-mol\u00adecules in (I)O and H6O, and imine-N3 and N6 atoms on the Hirshfeld surfaces mapped over dnorm shown with labels \u20181\u2019 and \u20182\u2019 in Fig.\u00a04N and H5N, and amide-O1 and O4 atoms, i.e. \u20183\u2019 and \u20184\u2019 in Fig.\u00a04dnorm-mapped Hirshfeld surfaces with labels \u20185\u20137\u2019 in Fig.\u00a04The bright-red spots appearing near the hydroxyl-H3a and C24 in Fig.\u00a04b, of the independent mol\u00adecules, respectively, reflect short inter\u00adatomic edge-to-edge C\u22efC contacts, Table\u00a02i.e. 0.1%, to the Hirshfeld surface owing to the absence of \u03c0\u2013\u03c0 stacking between aromatic rings in the crystal, Table\u00a03A, H18A, C28, C6, C33 and C24 atoms in the images of Fig.\u00a04A and H18B atoms, Fig.\u00a04a, and O5, C35, H22 and H36C atoms, Fig.\u00a04b, indicate the contributions from the additional short inter\u00adatomic C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts, Table\u00a02The presence of diminutive red spots viewed near phenyl atoms C6 in Fig.\u00a04On the Hirshfeld surfaces mapped over the electrostatic potential for the independent mol\u00adecules of (I)et al., 2007i.e. the twisting of the meth\u00adoxy substituents on the respective benzene rings and the inclination of these benzene rings with respect to the ethane bridges.It is clear from the overall two-dimensional fingerprint plots for each independent mol\u00adecule and for the entire asymmetric unit of (I)A and B have almost the same percentage contribution to their respective Hirshfeld surfaces, Table\u00a03A and B. The single short peaks at de + di \u223c 2.1\u2005\u00c5 in the delineated plots for both the mol\u00adecules indicate the involvement of hydrogen atoms of both in short inter\u00adatomic H\u22efH contacts, Table\u00a02de + di \u223c 2.0\u2005\u00c5 (inner region) and at \u223c 2.2\u2005\u00c5 (outer region) in the fingerprint plots delineated into O\u22efH/H\u22efO and N\u22efH/H\u22efN contacts, respectively. The forceps-like distribution of points linked with the donor spike for mol\u00adecule A and the acceptor spike for mol\u00adecule B at de + di \u223c 2.5\u2005\u00c5 in the fingerprint plots delineated into O\u22efH/H\u22efO contacts are due to weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions and the short inter\u00adatomic contacts summarized in Table\u00a02de + di \u223c 2.6\u2005\u00c5 in the acceptor and donor regions of fingerprint plots delineated into C\u22efH/H\u22efC contacts for mol\u00adecules A and B, respectively, represent the involvement of these atoms in the short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a02de + di \u223c 2.7\u2005\u00c5 in the donor and acceptor regions of mol\u00adecules A and B, respectively. The other C\u22efO/O\u22efC, O\u22efO and C\u22efC inter\u00adatomic contacts summarized in Table\u00a03The fingerprint plot delineated into H\u22efH contacts for mol\u00adecules et al., 2016et al., 1980et al., 1980et al., 2011et al., 2014et al., 2014There are no direct precedents for the structure of (I)in vacuo; yield: 75%. Light-yellow prisms of (I)v/v 20\u2005ml). IR (cm\u22121): 3201 \u03bd(N\u2014H), 1670 \u03bd(C=N), 1213 \u03bd(C\u2014N), 1026 \u03bd(C=O). MS m/z: 327.25 [M+1]+Analytical grade reagents were used as procured without further purification. 4-Phenyl\u00adsemicarbazide  and vanillylacetone  were dissolved sep\u00adarately in hot absolute ethanol (30\u2005ml) and mixed with stirring. The reaction mixture was heated and stirred for 20\u2005min., then stirred for another 30\u2005min. at room temperature. The resulting white precipitate was filtered off, washed with cold absolute ethanol and dried Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located in a difference-Fourier map but were refined with distance restraints of O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N), respectively. The maximum and minimum residual electron density peaks of 0.60 and 0.26\u2005e\u2005\u00c5\u22123, respectively, were located 0.95 and 0.75\u2005\u00c5 from atoms H10A and H36A, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989017017273/hb7720sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017017273/hb7720Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017017273/hb7720Isup3.cmlSupporting information file. DOI: 926756CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports6: Article number: 3657910.1038/srep36579; published online: 11152016; updated: 05042017This Article contains errors. In the legend of Figure 1,\u22121\u201d\u201c1.25\u2009cGy\u2009minshould read:\u22121\u201d.\u201c1.25\u2009Gy\u2009minIn addition, in the Methods section under subheading \u2018Animals and Radiation Exposure\u2019,\u22121\u201d\u201cFor serial tissue analysis, age and sex-matched C57BL/6J and C57L/J mice at 10\u201312 weeks of age were irradiated to the whole lung with a single dose of 15\u2009Gy of 320\u2009kVp X-rays at a dose rate of 1.25\u2009cGy\u2009minshould read:\u22121\u201d\u201cFor serial tissue analysis, age and sex-matched C57BL/6J and C57L/J mice at 10\u201312 weeks of age were irradiated to the whole lung with a single dose of 15\u2009Gy of 320\u2009kVp X-rays at a dose rate of 1.25\u2009Gy\u2009min"}
{"text": "In the crystal, N+(C)\u2014H\u22efCl\u2212 hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions lead to the formation of a three-dimensional supra\u00admolecular network.The title salt, C 18H26N42+\u00b72Cl\u2212, was obtained by the protonation of N,N-bis\u00ad(pyridin-4-ylmeth\u00adyl)cyclo\u00adhexane-1,4-di\u00adamine with hydro\u00adchloric acid in ethanol. The asymmetric unit consists of one half of an N,N-bis\u00ad(pyridin-3-ylmeth\u00adyl)cyclo\u00adhexane-1,4-di\u00adammonium dication, with a crystallographic inversion centre located at the centre of the cyclo\u00adhexyl ring, and a chloride anion. The central cyclo\u00adhexyl ring in the dication adopts a chair conformation. The two trans-(4-pyridine)\u2013CH2\u2013NH2\u2013 moieties at the 1- and 4-positions of the central cyclo\u00adhexyl ring occupy equatorial sites. The terminal pyridine ring is tilted by 53.72\u2005(6)\u00b0 with respect to the mean plane of the central cyclo\u00adhexyl ring (r.m.s. deviation = 0.2413\u2005\u00c5). In the crystal, N+\u2014H\u22efCl\u2212 hydrogen bonds between the dications and the chloride anions, and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings of the dications afford a two-dimensional sheet extending parallel to the ab plane. These sheets are further connected through weak C\u2014H\u22efCl\u2212 hydrogen bonds, resulting in the formation of a three-dimensional supra\u00admolecular network.The title salt, C In the dication, the central cyclo\u00adhexyl ring displays a chair conformation and the two trans-(4-pyridine)\u2013CH2\u2013NH2\u2013 moieties occupy equatorial sites at the 1- and 4-positions of the central cyclo\u00adhexyl ring. The terminal pyridine ring is tilted by 53.72\u2005(6)\u00b0 with respect to the mean plane of the cyclo\u00adhexyl ring (r.m.s. deviation = 0.2413\u2005\u00c5). This tilting angle is larger than that [27.98\u2005(5)\u00b0] of the similar dication with 4-pyridine rings as the terminal groups \u2005\u00c5] between the pyridine rings cyclo\u00adhexane-1,4-diaminium)cobalt(II) penta\u00adnitrate methanol solvate] cyclo\u00adhexane-1,4-di\u00adamine, prepared according to a literature method  = 0.95\u2005\u00c5 for Csp2\u2014H, 0.99\u2005\u00c5 for methyl\u00adene, 1.00\u2005\u00c5 for methine H atoms] and were refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atoms involved in hydrogen bonds were located in difference Fourier maps and refined freely [N\u2014H = 0.891\u2005(15) and 0.876\u2005(16)\u2005\u00c5].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989016017205/hg5479sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016017205/hg5479Isup2.hklStructure factors: contains datablock(s) I. DOI: 1511616CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "ATP\u2010sensitive P2X7 receptor activates the NLRP3 inflammasome and is a key component of the innate immune system. We used a fluid\u2010resuscitated rat model of fecal peritonitis and acute kidney injury (AKI) to investigate the contribution of this purinergic receptor to renal dysfunction in sepsis. Six and 24\u00a0h time\u2010points were chosen to represent early and established sepsis, respectively. A selective P2X7 receptor antagonist (A\u2010438079) dissolved in dimethyl sulfoxide (DMSO) was infused 2\u00a0h following induction of sepsis. Compared with sham\u2010operated animals, septic animals had significant increases in heart rate (\u22121(\u22124 to 8)% vs. 21(12\u201326)%; P\u00a0=\u00a00.003), fever (37.4(37.2\u201337.6)\u00b0C vs. 38.6(38.2\u201339.0)\u00b0C; P\u00a0=\u00a00.0009), and falls in serum albumin (29(27\u201330)g/L vs. 26(24\u201328); P\u00a0=\u00a00.0242). Serum IL\u20101\u03b2 (0(0\u201310)(pg/mL) vs. 1671(1445\u201333778)(pg/mL); P\u00a0<\u00a00.001) and renal IL\u20101\u03b2 (86(50\u2013102)pg/mg protein vs. 200 (147\u2013248)pg/mg protein; P\u00a0=\u00a00.0031) were significantly elevated in septic compared with sham\u2010operated animals at 6\u00a0h. Serum creatinine was elevated in septic animals compared with sham\u2010operated animals at 24\u00a0h (23(22\u201325) \u03bcmol/L vs. 28 (25\u201330)\u03bcmol/L; P\u00a0=\u00a00.0321). Renal IL\u20101\u03b2 levels were significantly lower in A\u2010438079\u2010treated animals compared with untreated animals at 6\u00a0h (70(55\u2013128)pg/mg protein vs. 200(147\u2013248)pg/mg protein; P\u00a0=\u00a00.021). At 24\u00a0h, compared with untreated animals, A\u2010438079\u2010treated animals had more rapid resolution of tachycardia (22(13\u201336)% vs. \u22121(\u22126 to 7)%; P\u00a0=\u00a00.019) and fever (39.0(38.6\u201339.1)\u00b0C vs. 38.2(37.6\u201338.7)\u00b0C; P\u00a0<\u00a00.024), higher serum albumin (23(21\u201325)g/L vs. (27(25\u201328)g/L); P\u00a0=\u00a00.006), lower arterial lactate (3.2(2.5\u20134.3)mmol/L vs. 1.4(0.9\u20131.8)mmol/L; P\u00a0=\u00a00.037), and lower serum creatinine concentrations (28(25\u201330)\u03bcmol/L vs. 22(17\u201327)\u03bcmol/L; P\u00a0=\u00a00.019). P2X7A treatment ameliorates the systemic inflammatory response and renal dysfunction in this clinically relevant model of sepsis\u2010related AKI.Sepsis is a major clinical problem associated with significant organ dysfunction and high mortality. The  Sepsis is a common and serious global health issue, accounting for 20% of all admissions to intensive care units (ICU), and is the leading cause of death in noncardiac ICUs  mice subjected to cecal ligation and puncture have an attenuated inflammatory response and reduced lung injury compared with wild\u2010type mice  , P2X7 receptor contributes to renal injury in sepsis through an inflammatory response with local production of cytokines. We aimed to define the expression of this receptor within the kidney, and its relationship with cytokine production, and renal function; we sought to assess effects of P2X7 antagonism in a rat model of sepsis\u2010induced AKI. The primary objective of this study was to evaluate the effect of a selective P2X7 antagonist (A\u2010438079) in preventing renal dysfunction (as defined by an elevated serum creatinine) in an experimental model of sepsis.We hypothesized that upregulation of the ATP\u2010sensitive P2XAll animal experiments were performed under a Home Office Project License (PPL 70/7029) and local UCL Ethics Committee approval.7 receptor antagonist (A\u2010438079) dissolved in DMSO. Details on monocyte isolation from male Wistar rats are detailed in the supplementary data. Monocytes require priming with LPS  prior to release of IL\u20101\u03b2 by co\u2010stimulation with ATP . The duration of LPS\u2010priming is variable, although 4\u00a0h has been shown to be adequate   was kindly donated by Abbvie . Based on previously published data and personal communication with Abbvie, the pharmacokinetic profile of A\u2010438079 was determined. A\u2010438079 blocked BzATP (10\u00a0\u03bcmol/L)\u2013mediated changes in intracellular Ca++ concentrations at rat P2X7 receptors but not at other P2 receptors  would achieve therapeutic levels in serum. We therefore administered a dose of 10\u00a0\u03bcg/kg. The antagonist was given as a single bolus to achieve a peak (therapeutic) concentration, followed by 4\u00d7 the dose  for the first half\u2010life, followed by 2\u00d7 the dose for the second half life, followed by 10\u00a0\u03bcg/(kg\u00b7h) thereafter.Unpublished data from Abbvie Pharmaceuticals demonstrates that the half\u2010life of intravenous A\u2010438079 is 0.69\u00a0h (41\u00a0min). An intravenous dose of 10\u00a0\u03bcmol/L, the pH at room temperature fell to 2.2, and at 38\u00b0C was 1.6. Dimethylsulfoxide (DMSO) was therefore selected as a drug solvent. Due to its amphipathic properties, DMSO is an effective solvent for water\u2010insoluble compounds and is a hydrogen\u2010bound disrupter. As such it is a commonly used solvent for many drugs in pharmacological studies. This is a commonly used drug solvent, however, itself has biological activity  weighing 300\u2013375\u00a0g were used throughout. All experiments were performed in accordance with relevant guidelines and regulations and are detailed in the supplementary data and our characterization manuscript  initially comprised sham\u2010operated and untreated septic animals at both 6\u00a0h and 24\u00a0h time points, and DMSO\u00a0\u00b1\u00a0A\u2010438079 treatment at 6\u00a0h and 24\u00a0h. On review of the results, we undertook further studies where twice the dose of A\u2010438079 was administered.Experimental groups .DuoSet ELISA kits  were used according to the manufacturer's instructions. The antibody supplied in the IL\u20101\u03b2 in sham and septic animals at 24\u00a0h. Details of methods for Western blot are included in the supplementary data.Protein was extracted and estimated from whole kidney tissue. Four animals were randomly selected from each of the sham and sepsis groups, for analysis. Kidney homogenate were assessed for expression of Caspase\u20101, and IL\u20101The number of antagonist\u2010treated animals and placebo\u2010treated controls was calculated based on previous laboratory experience. We regarded a 20% change in a tested variable as an important biological effect. The study was designed to have a power of 90% and a significance level of 5%. At least 6 replicate animals per group per time point.U test was used for comparison of continuous variables between 2 groups. A P\u00a0<\u00a00.05 was taken as statistically significant.Graphpad Prism  was used for statistical analyses and graphs. All data were regarded as nonparametric due to small sample sizes (6\u201312 per group). Continuous variables are presented as median (interquartile range). Data were analyzed in prospectively defined groups. All 6\u00a0h experiments were analyzed as a predefined group, as were all 24\u00a0h experiments. For comparison of continuous variables between more than two groups, Kruskal\u2013Wallis test with post hoc Dunn's test is used. Mann\u2013Whitney \u03b2 production (P\u00a0=\u00a00.029). Addition of 2% DMSO significantly inhibited the release of IL\u20101\u03b2 (P\u00a0=\u00a00.025). Addition of 10\u00a0\u03bcmol/L A\u2010438079 had no added effect on the reduction in IL\u20101\u03b2 release. 5\u00a0\u03bcmol/L brilliant blue G (BBG) had a significant inhibitory effect on monocyte IL\u20101\u03b2 release (P\u00a0=\u00a00.029)  stimulation of cultured monocytes resulted in significant IL\u20101P\u00a0=\u00a00.003), fever (37.4(37.2\u201337.6)\u00b0C vs. 38.6(38.2\u201339.0)\u00b0C; P\u00a0=\u00a00.0009), and falls in serum albumin (29(27\u201330)g/L vs. 26(24\u201328); P\u00a0=\u00a00.0242). Serum IL\u20101\u03b2 (0(0\u201310)(pg/mL) vs. 1671(1445\u201333778)(pg/mL); P\u00a0<\u00a00.001) and renal IL\u20101\u03b2 (86(50\u2013102)pg/mg protein vs. 200 (147\u2013248)pg/mg protein; P\u00a0=\u00a00.0031) were significantly elevated in septic compared with sham\u2010operated animals at 6\u00a0h. Serum creatinine, however, remained unchanged at 6\u00a0h (25(23\u201327)\u03bcmol/L vs. 23(21\u201328) \u03bcmol/L; P\u00a0=\u00a00.9155) in sham\u2010operated compared with septic animals.Clinical, biochemical, and cytokine changes in the septic model are detailed in our characterization manuscript , fever (37.5(37.4\u201337.8)\u00b0C vs. 39.0(38.6\u201339.1)\u00b0C; P\u00a0=\u00a00.0002), and fall in serum albumin (30(29\u201331)g/L vs. 23(21\u201325)g/L; P\u00a0=\u00a00.0003). Serum IL\u20101\u03b2 (0(0\u201310)(pg/mL) vs. 1463(927\u20132541)(pg/mL); P\u00a0<\u00a00.001) remains significantly elevated in septic compared with sham\u2010operated animals at 24\u00a0h although renal IL\u20101 \u03b2 levels were similar (168(154\u2013176)pg/mg protein vs. 186(149\u2013280)pg/mg protein; P\u00a0=\u00a00.053). Serum creatinine was significantly elevated in septic animals compared with sham\u2010operated animals at 24\u00a0h (23(22\u201325)\u03bcmol/L vs. 28 (25\u201330)\u03bcmol/L; P\u00a0=\u00a00.0321).At 24\u00a0h, septic animals had persistent changes of systemic inflammation Table\u00a0, Fig.\u00a02.7 on immunohistochemistry: there was minimal constitutive P2X7 expression limited to distal tubular epithelial cells   protein expression in septic animals compared with sham\u2010operated animals  vs. 1.35(1.25\u20131.37); \u03bcmol/L did not result in any clinical or biochemical differences between untreated and A\u2010438079\u2010treated septic animals (data not shown). We therefore undertook further studies where twice the dose of A\u2010438079 was administered.Initial in\u00a0vivo experiments targeting a peak concentration of 3\u00a0\u03b2 and between treated and untreated animals pg/mg protein vs. 200(147\u2013248)pg/mg protein; P\u00a0=\u00a00.021). Arterial lactate concentration was different between DMSO\u2010treated and untreated animals (1.0 (0.9\u20131.0)mmol/L vs. 1.2(1.0\u20131.3)mmol/L; P\u00a0=\u00a00.033), although remained within the normal clinical range in all groups of animals.At 6\u00a0h there was no difference among the groups in core temperature, change in heart rate, serum creatinine, or serum IL\u20101ls Table\u00a0. Renal IP\u00a0=\u00a00.019) and fever (39.0(38.6\u201339.1)\u00b0C vs. 38.2(37.6\u201338.7)\u00b0C; P\u00a0<\u00a00.024), higher serum albumin (23(21\u201325)g/L vs. (27(25\u201328)g/L); P\u00a0=\u00a00.006), lower arterial lactate (3.2(2.5\u20134.3)mmol/L vs. 1.4(0.9\u20131.8)mmol/L; P\u00a0=\u00a00.037), and lower serum creatinine concentrations (28(25\u201330)\u03bcmol/L vs. 22(17\u201327)\u03bcmol/L; P\u00a0=\u00a00.019).At 24\u00a0h, there were a number of significant differences between A\u2010438079 treated animals and untreated septic animals Table\u00a0, Fig.\u00a02.P\u00a0=\u00a00.016), and lower arterial lactate (2.2 (2.1\u20132.2)mmol/L vs. 1.4(0.9\u20131.8)mmol/L; P\u00a0=\u00a00.001). Serum IL\u20101\u03b2 and renal IL\u20101\u03b2 were similar in A\u2010438079\u2010treated, DMSO\u2010treated, and untreated animals at 24\u00a0h.At 24\u00a0h, compared with DMSO\u2010treated animals, A\u2010438079\u2010treated animals had higher serum albumin (24(22\u201325)g/L vs. 27(25\u201328)g/L; 7 and IL\u20101\u03b2, are expressed de novo within the renal tubular epithelial cells in this septic model. This is consistent with published data showing that LPS\u2010primed Madin\u2013Darby canine kidney (MDCK) renal tubular epithelial cells express Toll\u2010like receptor 4, NLRP3, caspase\u20101, and IL\u20101\u03b2 mRNA , though P2X7 activation accelerates mature IL\u20101\u03b2 release from monocytes  levels of IL\u20101\u03b2 \u2010producing Escherichia coli had markedly lower survival, higher cytokine levels (including IL\u20101\u03b2), and activated intravascular coagulation compared with wildtype mice  transplanted with wild\u2010type kidneys were protected from LPS\u2010induced AKI, whereas wild\u2010type mice transplanted with C3H/HeJ kidneys developed severe LPS\u2010induced AKI. This suggests that TLR4 expression in circulating cells propagates injury in septic AKI, rather than intra\u2010renal TLR4 , with better perfusion to organs including the kidney, rather than specific actions over the renal\u2010inflammasome activation.The changes found in animals treated with the P2X\u03b2 measurement, which does not allow localization to specific cell types. Immunohistochemistry would enable localization of these cytokines. Although insights into renal expression of the inflammasome and P2X7 in sepsis have been demonstrated, the expression of the P2X7 in other organs and on immune cells also needs to be evaluated.ELISAs were performed on whole kidney homogenate for IL\u2010\u03b2 and tubular cell P2X7 expression by 6\u00a0h and 24\u00a0h, respectively. Treatment with A\u2010438079 after the onset of sepsis abrogated the rise in serum creatinine at 24\u00a0h with reduced renal IL\u20101\u03b2 expression early. In addition, A\u2010438079 treatment reduced fever, improved resolution of tachycardia, increased serum albumin concentration and reduced lactate at 24\u00a0h. Given these encouraging results in an in\u00a0vivo model of sepsis that is relevant to human disease, further studies targeting P2X7 in sepsis are warranted.We demonstrate a number of strengths of our experimental model relevant to potential therapeutics in sepsis. Sepsis is associated with an increase in renal IL\u20101All animal experiments were performed under a Home Office Project License (PPL 70/7029) and local University College London Ethics Committee approval.7 antagonist (A\u2010438079). FWKT has received research project grants from AstraZeneca Limited, Baxter Biosciences, Boehringer Ingelheim, and MedImmune. He has consultancy agreements with Rigel Pharmaceuticals, Novartis and Baxter Biosciences.Materials: Abbvie pharmaceuticals  have provided the selective P2XData S1. Supplementary data.Click here for additional data file."}
{"text": "Scientific Reports6: Article number: 18631; 10.1038/srep18631 published online: 01112016; updated: 09012016.In this Article and Supplementary Information file, some instances of \u20180.001M PBS\u2019 and \u20180.01M PBS\u2019 are incorrectly written as \u20180.01M PBS\u2019 and \u20180.1M PBS\u2019 respectively. With the exception of the following:In the Materials and Methods section, under subheading \u2018Specimen Preparation\u2019,\u201cFixed samples were incubated in A4P0 hydrogel monomer solution (4% acrylamide in 0.1\u2009M PBS) supplemented with 0.25% of the photoinitiator 2,2\u2032-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride  overnight at 4\u2009\u00b0C\u201d.should read:\u201cFixed samples were incubated in A4P0 hydrogel monomer solution (4% acrylamide in 0.001\u2009M PBS) supplemented with 0.25% of the photoinitiator 2,2\u2032-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride  overnight at 4\u2009\u00b0C\u201d.Under subheading \u2018ACT Reagents\u2019,A4P0 solution, Forty ml of 40% acrylamide was added to 360\u2009ml dH2O to prepare 400\u2009ml of the hydrogel monomer solution (A4P0)\u201d.\u201cshould read:A4P0 solution, Forty ml of 40% acrylamide was added to 360\u2009ml 0.001M PBS to prepare 400\u2009ml of the hydrogel monomer solution (A4P0)\u201d.\u201cUnder subheading \u2018Whole-body and Organ ACT Protocol,\u201cHigher sodium concentrations in the clearing solution (0.03\u2009M and 0.1\u2009M PBS) ameliorated tissue swelling but resulted in tissue thinning (data not shown)\u201d.should read:\u201cHigher sodium concentrations in the clearing solution (0.003\u2009M and 0.01\u2009M PBS) ameliorated tissue swelling but resulted in tissue thinning (data not shown)\u201d.\u201cThe head was freed from subcutaneous skin and hair and washed several times with 0.1\u2009M PBS.should read:\u201cThe head was freed from subcutaneous skin and hair and washed several times with 0.001\u2009M PBS\u201d.In the Supplementary Information file, under subheading \u2018\u2019Hydrogel monomer infusion & polymerization,\u201c1. Prepare the A4P0 hydrogel monomer solution.Take 40\u2009ml of 4% acrylamide in 0.1\u2009M PBS solution and add 100\u2009mg of VA-044 Initiator to make a final concentration of 0.25%\u201d.should read:\u201c1. Prepare the A4P0 hydrogel monomer solution.Take 40\u2009ml of 4% acrylamide in 0.001\u2009M PBS solution and add 100\u2009mg of VA-044 Initiator to make a final concentration of 0.25%\u201d.Under the subheading \u2018Immunolabeling ACT-processed brain tissue\u2019,\u201c1. Wash samples in 0.1\u2009M PBS for 3\u20135\u2009hours and change the buffer every hour\u201d.should read:\u201c1. Wash samples in 0.001\u2009M PBS for 3\u20135\u2009hours and change the buffer every hour\u201d.\u201c3. Wash samples in 0.1\u2009M PBS for 3\u20135\u2009hours, and change buffer every hour\u201d.should read:\u201c3. Wash samples in 0.001\u2009M PBS for 3\u20135\u2009hours, and change buffer every hour\u201d."}
{"text": "The title salt forms a racemate due to disorder of the hy\u00addroxy group [occupancy ratio 0.738\u2005(3):0.262\u2005(3)] at the stereogenic C atom. 13H22NO3+\u00b7C7H5O2\u2212, comprises one salbutamol cation {sys\u00adtematic name: 4-[2-(tert-butyl\u00adaza\u00adnium\u00adyl)-1-hy\u00addroxy\u00adeth\u00adyl]-2-(hy\u00addroxy\u00admeth\u00adyl)phenol} and a benzoate anion. The cation shows disorder of the hy\u00addroxy group [occupancy ratio 0.738\u2005(3):0.262\u2005(3)] at the stereogenic C atom. The non-planar benzoate anion [the dihedral angle between the benzene ring and the carboxyl group is 11.30\u2005(8)\u00b0] is linked to the salbutamol cation by a medium-strength O\u2014H\u22efO hydrogen bond. Other inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds of weaker nature give rise to [001] chains.The title salt, C The bond lengths of the carboxyl\u00adate group of the BA\u2212 anion, C20\u2014O4 and C20\u2014O5, are 1.2617\u2005(15) and 1.2604\u2005(15)\u2005\u00c5, respectively. The slight difference may be caused by the role of O4 as an acceptor atom of the O3\u2014H3\u22efO4 hydrogen bond with one of the hy\u00addroxy groups of +SAL. The +SAL cation also has an intra\u00admolecular hydrogen bond between the two hy\u00addroxy functions (O1\u2014H1\u22efO3), forming an S(6) ring motif \u00b0. There is some disorder at the stereogenic centre (C8) of the +SAL cation, but the space group is centrosymmetric and the +SAL cation is racemic.The +SAL cation is connected to the \u2212BA anion via a medium-strength O3\u2014H3\u22efO4 hydrogen bond  was determined  and benzoic acid  were added to 10\u2005ml methanol and stirred for 3\u2005h. The solvent was then evaporated at room temperature to yield salbutamol benzoate. After recrystallization from water, pure crystals were again dissolved in ethanol and the solution filtered. The neat filtrate was evaporated slowly to give colourless block-like single crystals of salbutamol benzoate.Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H)\u00a0= 1.2Ueq(C) for all other H atoms. The H atoms of the NH2 group and the hy\u00addroxy group  were also constrained to ideal values and allowed to ride in the refinement, with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989017011513/wm5403sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017011513/wm5403Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017011513/wm5403Isup3.cmlSupporting information file. DOI: 1482124CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The chemical modifications in terms of changes in substituents in the title compounds have not affected the type nor strength of two defining inter\u00admolecular inter\u00adactions present in both crystal structures. 28H26N2O2, (I), and C27H22BrClN2O2, (II), differ in their substituents, viz.4-methyl\u00adphenyl and benzoyl rings in (I) replaced by 2-chloro\u00adphenyl and 4- bromo\u00adbenzoyl, respectively, in (II). A significant difference between the two mol\u00adecules is found in the deviation of the benzoyl O atom from the least-squares plane of the ring to which it is attached , a fact which may be attributed to the different participation of the benzoyl O atoms as acceptors in their inter\u00admolecular C\u2014H\u22efO inter\u00adactions. The chemical modifications in (I) and (II) do not seem to affect the type nor strength of the inter\u00admolecular N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds responsible for the two crystal structures, such that the aggregation of mol\u00adecules appears similar in spite of the mol\u00adecular changes.The two title compounds, C Indole, a pharmacologically significant nucleus, is known for anti-inflammatory viz. N2\u2013C9\u2013C10\u2013C11\u2013C12 and N2\u2013C2\u2013C14\u2013C13\u2013C12 are, respectively, Q = 0.362\u2005(4)\u2005\u00c5, \u03c6 = 264.4\u2005(5)\u00b0 indicating a twist about C10\u2013C11, and Q = 0.408\u2005(3)\u2005\u00c5, \u03c6=67.9\u2005(4)\u00b0 conforming to an envelope on C14. The corresponding values in (II)Q = 0.378\u2005(3)\u2005\u00c5, \u03c6 = 82.4\u2005(4)\u00b0 and Q = 0.423\u2005(3)\u2005\u00c5, \u03c6 = 251.4\u2005(3)\u00b0, may differ slightly from those in (I)Q of the fused eight-membered pyrrolizine and the nine-membered indolone ring systems are respectively, 0.727\u2005(3) and 0.129\u2005(3)\u2005\u00c5 in (I)Mol\u00adecular diagrams of (I)In both compounds, the spiro-fused ring systems tend to be rigid by remaining nearly perpendicular to each other, whereas the remaining substituted rings appear to be more \u2018compromising\u2019 towards hydrogen-bonding requirements, irrespective of their intra- or inter\u00admolecular nature. As an example, the free rotation of the benzoyl group in (II)A significant difference between the two structures is observed in the deviation of benzoyl atom O2 from the least-squares plane of the C15\u2013C21 atoms: 0.593\u2005(4) in (I)etc, these mol\u00adecular modifications do not seem to affect the type nor strength of the two relevant N\u2014H\u22efN and C\u2014H\u22efO inter\u00admolecular hydrogen bonds defining the crystal structures (Tables 1x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a0dO\u22efBr= 3.192\u2005(2)\u2005\u00c5] is present in structure (II)Even if the differences in the substituents produce differences in lattice types, space group, cell metrics,  Tables 1 and 2 \u25b8,et al., 2016et al., 1998A search of the Cambridge Structural Database -1-phenyl-3-(p-tol\u00adyl)prop-2-en-1-one (0.4\u2005mmol) [for the synthesis of (II)E)-1-(4-bromo\u00adphen\u00adyl)-3-(2-chloro\u00adphen\u00adyl)prop-2-en-1-one (0.4\u2005mmol)], isatin (0.4\u2005mmol) and l-proline (0.4\u2005mmol), which was dissolved in 5\u2005ml of methanol, and 1\u2005mol% of CMPTC  was added and stirred at reflux temperature until the completion of reaction as indicated by TLC. After this step, the mixture was poured onto ice; the precipitate was filtered and recrystallized from ethanol solution, to get the pure product without column chromatography.The synthesis of (I)Uiso(H) set at 1.2\u20131.5Ueq(C). Compound (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989016016741/bg2594sup1.cifCrystal structure: contains datablock(s) I, II, c1. DOI: 1503430, 1503429CCDC references: crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ethyl\u00adeneglycol ligand forms a non-planar metallacyclic ring by chelating the Ru atom via the O atoms. The O\u22efO distances of 2.554\u2005(2) and 2.568\u2005(2)\u2005\u00c5 are indicative of hydrogen bonding between coordinated ethyl\u00adeneglycol and outer-sphere trifluoro\u00admethane\u00adsulfonate fragments. The crystal packing is stabilized by ionic forces and several CH3\u22ef\u00b7F (2.585 and 2.640\u2005\u00c5) and CH3\u22efO inter\u00adactions  between the penta\u00admethyl\u00adcyclo\u00adpenta\u00addienyl ligand and trifluoro\u00admethane\u00adsulfonate anion. There is noticeable short inter\u00admolecular contact [2.9039\u2005(16)\u2005\u00c5], between an O atom of the SO3 group and a C atom of the penta\u00admethyl\u00adcyclo\u00adpenta\u00addienyl ligand.The title compound, [Ru(C DOI: 10.1107/S1600536807067426/bg2160Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Cu2(C8H7O2)4(C9H7N)2], the two Cu cations are bridged by four carboxyl\u00adate groups of the phenyl\u00adacetate anions; each Cu cation is further coordinated by an isoquinoline ligand to complete the distorted CuO4N square-pyramidal geometry. The Cu cation is displaced by 0.2092\u2005(8)\u2005\u00c5 from the basal plane formed by the four O atoms. Within the dinuclear mol\u00adecule, the Cu\u22efCu separation is 2.6453\u2005(6)\u2005\u00c5. Although a parallel, overlapped arrangement of isoquinoline ligands exists in the crystal structure; the longer face-to-face distance of 3.667\u2005(5)\u2005\u00c5 suggests there is no \u03c0\u2013\u03c0 stacking between isoquinoline ring systems.In the title centrosymmetric binuclear Cu DOI: 10.1107/S1600536809048697/ng2685Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the cation, the FeCo2 triangle is symmetrically capped on one face by an S atom and on the other by a C atom linked to a methyl trithio\u00adcarbonate residue that bridges the Fe\u2014C bond. Each Co atom carries a cyclo\u00adpenta\u00addienyl ligand while the Fe atom coordinates to one carbonyl and one triphenyl\u00adphosphine ligand. In the crystal structure, the cation is linked to the anion by a number of weak non-classical C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds and weak S\u22efO (3.317\u2005\u00c5) and S\u22efF (3.198\u2005\u00c5) inter\u00adactions. The structure is further stabilized by additional inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efF and O\u22efO (2.942\u2005\u00c5) contacts, together with an unusual S\u22ef\u03c0(Cp) inter\u00adaction (S\u22efcentroid distance = 3.385\u2005\u00c5), generating an extended network.The asymmetric unit of the title compound, [FeCo DOI: 10.1107/S1600536808008970/hb2713Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The initial reactant of CuI was oxidized to CuII. The asymmetric unit contains two independent complex mol\u00adecules, two I\u2212 ions and one water molecule. Each CuII atom is coordinated by two O atoms from a 4-methyl\u00adbenzoate ligand and four N atoms from two 2,2\u2032-bipyridine ligands, displaying a distorted octa\u00adhedral geometry. The structure involves O\u2014H\u22efI hydrogen bonds between the water mol\u00adecule and iodide ions and \u03c0\u2013\u03c0 stacking inter\u00adactions between the benzene and pyridyl rings [centroid\u2013centroid distance = 3.79\u2005(1)\u2005\u00c5] and between the pyridyl rings [centroid\u2013centroid distance = 3.87\u2005(1)\u2005\u00c5].The title compound, [Cu(C DOI: 10.1107/S1600536808024252/hy2148Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The N and O donor atoms are mutually cis. The dihedral angle between two benzene rings of the ligand is 38.86\u2005(8)\u00b0. There are also three solvent water mol\u00adecules, two of which lie across different crystallographic twofold rotation axes; one of these is partially occupied with a refined occupancy factor of 0.570\u2005(7). The water mol\u00adecules are linked together as tetra\u00admers in R               2               2(8) ring motifs, which also connect two neighbouring mol\u00adecules of the complex through a network of O\u2014H\u22efO hydrogen bonds. The crystal structure is further stabilized by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, which link neighbouring mol\u00adecules into extended chains along the b axis. Other inter\u00adesting features of the crystal structure are the short inter\u00admolecular C\u22efC [3.204\u2005(3)\u20133.365\u2005(3)\u2005\u00c5] and the C\u22efO [3.199\u2005(2)\u20133.205\u2005(2)\u2005\u00c5] contacts which are shorter than the sum of the van der Waals radii of these atoms.In the title complex, [Ni(C DOI: 10.1107/S1600536809014500/sj2621Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, O\u2014H\u22efO hydrogen bonds between the coordinated water mol\u00adecules and uncoordinated carboxyl\u00adate O atoms, and weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 4.105\u2005(2)\u2005\u00c5] between the benzene and pyrazine rings lead to a three-dimensional supra\u00admolecular network.In the title compound, [Co(C DOI: 10.1107/S1600536810037906/hy2354Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A supra\u00admolecular network is formed via inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions. \u03c0\u2013\u03c0 stacking inter\u00adactions between neighboring pyridine rings are also present, the centroid\u2014centroid distance being 3.808\u2005(2)\u2005\u00c5.In the title complex, [Cu(C DOI: 10.1107/S1600536810035555/pv2323Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both MnIII centers are in a distorted octa\u00adhedral geometry with the N2O2 donor atoms of the tetra\u00addentate Schiff base dianion in the equatorial plane. The axial positions in the coordination environment of one MnIII complex are occupied by a chloride ion and a water mol\u00adecule, but a methanol mol\u00adecule replaces the water mol\u00adecule in the other complex. The coordinated water mol\u00adecule takes part in an O\u2014H\u22efCl hydrogen bond between the two MnIII complexes. In the crystal structure, O\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into infinite one-dimensional chains along the [100] direction. The crystal structure is stabilized by O\u2014H\u22efCl hydrogen bonds together with weak C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions. A C\u2014H\u22ef\u03c0 inter\u00adaction is also observed in the crystal structure.The asymmetric unit of the title complex, [Mn(C Cl(H2O)][Mn(C28H30N2O2)Cl(CH4O)] = 0.057                           wR(F                           2) = 0.147                           S = 1.03                           10108 reflections653 parametersH-atom parameters constrainedmax = 0.56 e \u00c5\u22123                        \u0394\u03c1min = \u22120.52 e \u00c5\u22123                        \u0394\u03c1                                 APEX2 (Bruker, 2005APEX2; data reduction: SAINT (Bruker, 2005SHELXTL (Sheldrick, 2008SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003Data collection: 10.1107/S1600536808006818/sj2472sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006818/sj2472Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the anion, the GaIII ion is coordinated by four O atoms [Ga\u2014O = 1.9706\u2005(16)\u20132.0494\u2005(15)\u2005\u00c5] and two N atoms [Ga\u2014N = 1.9660\u2005(18) and 1.9709\u2005(17)\u2005\u00c5] from two pydc ligands in a distorted octa\u00adhedral geometry. The crystal structure exhibits inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances of 3.5359\u2005(13) and 3.6550\u2005(14)\u2005\u00c5].The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536808029140/cv2438Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The O atoms of two 4-pyridone ligands bridge two symmetrically related AgNO3 units, forming a dimer, with an Ag\u22efAg separation of 3.680\u2005(2)\u2005\u00c5. Neighbouring dimers are linked into an infinite chain through weak Ag\u22efO inter\u00adactions [2.765\u2005(2)\u2005\u00c5], Ag\u22efAg inter\u00adactions [3.1511\u2005(4)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.623\u2005(4)\u2005\u00c5]. N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds assemble these chains into a three-dimensional network.In the title complex, [Ag(NO DOI: 10.1107/S1600536809019138/hy2199Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both Ag+ cations show a distorted square-pyramidal coordination. Ag1 is bonded to two water molecules, one L N atom, one N atom and one carboxylate O atom from a neighbouring L, whereas Ag2 is surrounded by two L N atoms, two L carboxylate O atoms and one bridging water molecule. O\u2014H\u22efO hydrogen-bonding inter\u00adactions involving water clusters and carboxyl\u00adate O atoms link the mol\u00adecules into a three-dimensional supra\u00admolecular architecture, which is further consolidated by weak C\u2014H\u22efO inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance 3.643\u2005(5)\u2005\u00c5].In the title silver(I) coordination polymer, {[Ag DOI: 10.1107/S160053680802984X/kj2095Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the two ligands, the pyridyl rings form dihedral angles of 21.0\u2005(1) and 15.5\u2005(1)\u00b0. The crystal packing exhibits an extensive network of O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions proved by short distances of 3.650\u2005(1) and 3.732\u2005(2)\u2005\u00c5 between the centroids of pyridyl rings of neighbouring mol\u00adecules.In the title compound, [Cu(C DOI: 10.1107/S1600536809009453/cv2529Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds. A weak C\u2014H\u22ef\u03c0 inter\u00adaction also occurs.In the title compound, C DOI: 10.1107/S1600536809055391/jj2016Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The OH group of the 2-hydroxy\u00adbenzoate anion is disordered over two positions with site-occupancy factors of 0.5. The asymmetric unit is completed with by an uncoordinated half-mol\u00adecule of dmphen, disordered about a crystallographic twofold axis. In the crystal structure, mol\u00adecules are linked into a two-dimensional framework by O\u2014H\u22efN, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds. The packing of the structure is further stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions involving dmphen mol\u00adecules, with centroid\u2013centroid separations of 3.8027\u2005(3) and 3.6319\u2005(3)\u2005\u00c5.In the asymmetric unit of the title complex, [Mn(C DOI: 10.1107/S1600536809000981/bh2207Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a weak \u03c0\u2013\u03c0 stacking inter\u00adaction between symmetry-related triazolyl rings with a centroid\u2013centroid distance of 3.802\u2005(4)\u2005\u00c5 and a perpendicular distance of 3.413\u2005\u00c5 between the rings.In the title complex, [Zn(C DOI: 10.1107/S160053680903877X/bt5062Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each NiII ion has a distorted square-pyramidal environment, with the basal plane formed by three O [Ni\u2014O = 1.9290\u2005(16)\u20131.9588\u2005(10)\u2005\u00c5] and one N [Ni\u2014N = 1.9828\u2005(18)\u2005\u00c5] atoms and the apical position occupied by the water mol\u00adecule [Ni\u2014O = 2.2643\u2005(11)\u2005\u00c5]. The water mol\u00adecules are involved in the formation of O\u2014H\u22efO hydrogen bonds.In the title compound, {[Ni DOI: 10.1107/S1600536808031619/cv2458Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II compound, [Zn2(C12H9O3)4(H2O)2], is centrosymmetric. Each Zn atom is coordinated by two bridging 2-naphthoxyacetate anions, one terminal 2-naphth\u00adoxy\u00adacetate anion and one water mol\u00adecule in a distorted ZnO4 tetra\u00adhedral geometry. The naphthalene system of the bridging ligand is nearly perpendicular to the naphthalene of the terminal ligand, with a dihedral angle of 78.26\u2005(6)\u00b0. Within the binuclear mol\u00adecule the Zn\u22efZn separation is 3.815\u2005(5)\u2005\u00c5. In the crystal structure, inter\u00admolecular O\u2014H\u22efO hydrogen bonding between the water mol\u00adecule and carboxyl\u00adate groups helps to stabilize the crystal structure.The title binuclear Zn DOI: 10.1107/S1600536809013750/xu2494Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "III compound, [In2(SO4)3(C12H8N2)2(H2O)2]\u00b72H2O, each InIII cation is coordinated by a 1,10-phenanthroline (phen) ligand, a water mol\u00adecule and three sulfate O atoms in a distorted InN2O4 octa\u00adhedral geometry. Three sulfate anions bridge two InIII cations, forming the dinuclear entities. O\u2014H\u22efO and weak C\u2014H\u22efO hydrogen bonding is observed in the crystal structure. The crystal structure is further consolidated by \u03c0\u2013\u03c0 stacking between nearly parallel phen ring systems [dihedral angle = 4.2\u2005(4)\u00b0], the centroid\u2013centroid distance between benzene rings of adjacent phen ligands being 3.528\u2005(9)\u2005\u00c5.In the title dinuclear In DOI: 10.1107/S1600536810036330/xu5026Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one copper cation to which two acetate units bind asymmetrically; one of the Cu\u2014O distances is rather long [2.740\u2005(2)\u2005\u00c5], almost at the limit of coordination. These Cu\u2014O bonds define an equatorial plane to which the Cu\u2014N bonds to the INA ligands are almost perpendicular, the Cu\u2014N vectors subtending angles of 2.4\u2005(1) and 2.3\u2005(1)\u00b0 to the normal to the plane. The metal coordination geometry can be described as a slightly distorted trigonal bipyramid if the extremely weak Cu\u2014O bond is disregarded, or as a highly distorted square bipyramid if it is not. The double acetate bridge between the copper ions is not coplanar with the CuO4 equatorial planes, the dihedral angle between the (O\u2014C\u2014O)2 and O\u2014Cu\u2014O groups being 34.3\u2005(1)\u00b0, resulting in a sofa-like conformation for the 8-member bridging loop. In the crystal, N\u2014H\u22efO hydrogen bonds occur, some of which generate a head-to tail-linkage between INA units, giving raise to chains along [101]; the remaining ones make inter-chain contacts, defining a three-dimensional network. There are in addition a number of C\u2014H\u22efO bonds involving aromatic H atoms. Probably due to steric hindrance, the aromatic rings are not involved in significant \u03c0\u22ef\u03c0 inter\u00adactions.The title centrosymmetric bimetallic complex, [Cu For coo al. 2003. For a c al. 2007.       2(C2H3O2)4(C6H6N2O)4] = 0.039                           wR(F                           2) = 0.099                           S = 1.08                           3736 reflections244 parametersH-atom parameters constrainedmax = 0.36 e \u00c5\u22123                        \u0394\u03c1min = \u22120.43 e \u00c5\u22123                        \u0394\u03c1                                 MSC/AFC Diffractometer Control Software  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL-NT (Sheldrick, 2008SHELXTL-NT and PLATON (Spek, 2009Data collection: 10.1107/S1600536810004393/hb5326sup1.cif            Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810004393/hb5326Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances 3.572\u2005(1) and 3.671\u2005(1)\u2005\u00c5 together with C\u2014H\u22efBr hydrogen bonds.The title compound, [CdBr DOI: 10.1107/S1600536809020352/sj2628Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Longer Cu\u22efO contacts [2.680\u2005(2)\u2005\u00c5] complete an approximate square-based pyramidal coordination geometry around CuII, forming a dimeric complex across a centre of inversion. The dimeric complexes form stacks along the a axis, with Cu\u22efO contacts of 3.332\u2005(2)\u2005\u00c5 between them. The Na+ cations and perchlorate anions lie on twofold rotation axes between the stacks. The former are coordinated by two disordered water mol\u00adecules , and form Na\u22efO contacts of 3.698\u2005(3)\u2005\u00c5 to the perchlorate anions and Na\u22ef\u03c0 contacts to neighbouring salicylideneglycinate ligands [shortest Na\u22efC = 3.516\u2005(3)\u2005\u00c5].In the title compound, [Na(H DOI: 10.1107/S1600536808039561/bi2318Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "N-heterocycle in the title centrosymmetric dinuclear compound, [Ag2(NO3)2(C8H15N3)2], bridges two metal atoms through its imino N atoms. The N\u2014Ag\u2014N skeleton is bent [N\u2014Ag\u2014N = 127.2\u2005(3)\u00b0]; as one of two O atoms of the nitrate anion is nearly coplanar with this N\u2014Ag\u2014N skeleton [Ag\u2014O = 2.63\u2005(1)\u2005\u00c5], the coordination geometry around the AgI atom is regarded as trigonal-planar. One of the two isopropyl groups is disordered over two positions in respect of the methyl groups in a 1:1 ratio. In the crystal structure, inter\u00admolecular N\u2014H\u22efO hydrogen bonding is observed between the nitrate groups and triazole ligands.The neutral  DOI: 10.1107/S1600536809028384/xu2560Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions with a centroid\u2013centroid distance of 3.6136\u2005(16)\u2005\u00c5.In the title mononuclear zinc(II) complex, [Zn(C DOI: 10.1107/S1600536809033893/rk2159Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds link the cations, anions and water mol\u00adecules into a three-dimensional supra\u00admolecular structure. The crystal packing also exhibits inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings of the anions with a centroid\u2013centroid distance of 3.604\u2005(2)\u2005\u00c5.The asymmetric unit of the title compound, [Mg(H DOI: 10.1107/S160053680904344X/cv2632Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2-amino\u00adethyl group has a coiled conformation with an N\u2014C\u2014C\u2014NH2 torsion angle of 53.6\u2005(4)\u00b0. In the crystal structure, inter\u00admolecular N\u2014H\u22efN and weak C\u2014H\u22efO hydrogen bonds link mol\u00adecules into chains along [001].In the title compound, C DOI: 10.1107/S160053680901962X/lh2821Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Zn\u2014Br bond lengths range from 2.400\u2005(2) to 2.408\u2005(3)\u2005\u00c5 and the Br\u2014Zn\u2014Br angles range from 108.14\u2005(6) to 115.15\u2005(15)\u00b0. In the crystal structure, the [ZnBr4]2\u2212 anion is connected to two cations through N\u2014H\u22efBr and H2C\u2014H\u22efBr hydrogen bonds, forming two-dimensional cation\u2013anion\u2013cation layers normal to the b axis. No significant Br\u22efBr inter\u00adactions [the shortest being 4.423\u2005(4)\u2005\u00c5] are observed in the structure.In the crystal structure of the title compound, (C DOI: 10.1107/S1600536809015219/at2771Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Edge-to-face C\u2014H\u22ef\u03c0 inter\u00adactions exist between mol\u00adecules, with a dihedral angle of 37.8\u2005(1)\u00b0 between the benzene ring planes and a shortest H\u22efcentroid distance of 3.62\u2005(5)\u2005\u00c5.In the title compound, [ZnCl DOI: 10.1107/S1600536808037860/bi2311Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atoms in each complex adopt a distorted square-pyramidal coordination geometry being penta\u00adcoordinated by one N and two O atoms of 4-hydroxy\u00adpyridine-2,6-dicarboxyl\u00adate anions and two N atoms of 2,9-dimethyl-1,10-phenanthroline (dmp) molecules. In the crystal structure, there are O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and five \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances in the range 3.620\u2005(1)\u20133.712\u2005(1)\u2005\u00c5. In addition, a C\u2014H\u22ef\u03c0 inter\u00adaction between a heterocyclic ring of dmp is observed to reinforce the crystal cohesion.In the title complex, [Cu(C DOI: 10.1107/S1600536809021588/pv2164Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "These components are inter\u00adconnected in the crystal structure by an extensive network of O\u2014H\u22efO, N\u2014H\u22efO, C\u2014H\u22efO, O\u2014H\u22efN, O\u2014H\u22efCl, N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds. The shortest inter\u00admolecular inter\u00adaction is realized between the cation and anion . C\u2014H\u22efO inter\u00adactions also play a important role in the inter\u00adconnection of the cations.The asymmetric unit of the title compound, (C DOI: 10.1107/S160053681000615X/rk2191Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex mol\u00adecule, the two benzimidazole planes are twisted, making a dihedral angle of 55.93\u2005(11)\u00b0. The three-dimensional framework is organized by inter\u00admolecular N\u2014H\u22efO hydrogen bonding and O\u2014H\u22efO inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions between adjacent benzimidazole rings [centroid\u2013centroid distance = 3.586\u2005(3)\u2005\u00c5].In the title compound, [Zn(C DOI: 10.1107/S1600536810015631/kp2256Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efN inter\u00adactions link the monomeric units into a two-dimensional hydrogen-bonded  network, which is extended to a three-dimensional supra\u00admolecular aggregate via \u03c0\u22ef\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances 3.809\u2005(3) and 3.499\u2005(3)\u2005 \u00c5].In the mol\u00adecular structure of the centrosymmetric mononuclear complex [Ni(2-bpt) DOI: 10.1107/S1600536809012598/hg2489Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.698\u2005(4)\u2005\u00c5], and by C\u2014H\u22ef\u03c0 inter\u00adactions between a methyl\u00adene H atom of the butyl group and the benzene ring of the benzofuran system. Additionally, the crystal structure exhibits weak inter\u00admolecular C\u2014H\u22efO contacts. The butyl group is disordered over two positions, with site-occupancy factors, from refinement, of 0.720\u2005(8) and 0.280\u2005(8).In the title compound, C DOI: 10.1107/S1600536808043985/tk2347Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "This compound is composed of an anionic complex, [Cr(pydc)2]\u2212, protonated 4,4\u2032-bipyridine as a counter-ion, +, and four uncoordinated water mol\u00adecules. The anion is a six-coordinate complex with a distorted octa\u00adhedral geometry around the CrIII atom, formed by two tridentate pyridine-2,6-dicarboxyl\u00adate, pydc2\u2212, groups. Inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, and C\u2014O\u22ef\u03c0 stacking inter\u00adactions (with distances of 3.3390\u2005(13) and 3.4575\u2005(13)\u2005\u00c5) connect the various components into a supra\u00admolecular structure.The title compound, (C DOI: 10.1107/S1600536808006594/om2216Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Fe2S2 unit exhibits a butterfly conformation and the ferrocenyldiphenyl\u00adphosphine ligand is trans to the Fe\u2014Fe bond. The Fe\u2014Fe distance of 2.5160\u2005(8)\u2005\u00c5 is longer than found in related model structures. Intra\u00admolecular C\u2014H\u22efS and inter\u00admolecular C\u2014H\u22efO hydrogen bonds are observed.The title compound, [Fe DOI: 10.1107/S1600536808032698/ci2685Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The water mol\u00adecules and the 1-(4-chloro\u00adphen\u00adyl)piperazine-1,4-diium cations inter\u00adact with the [ZnCl4]2\u2212 anions through O\u2014H\u22efCl, N\u2014H\u22efCl, N\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds (five simple and one bifurcated). Inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions are present between adjacent aromatic rings of 1-(4-chloro\u00adphenyl)\u00adpiperazine-1,4-diium cations (the centroid\u2013centroid distance is 3.453\u2005\u00c5).In the crystal structure of the title compound, (C DOI: 10.1107/S1600536808016590/bg2190Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each Au atom is in a square-planar environment coordinated by diphenyl\u00adphosphanide and 2,6-diphenyl\u00adpyridine ligands. There are weak \u03c0\u2013\u03c0 stacking inter\u00adactions between neighbouring mol\u00adecules (the inter\u00adplanar separations between two neighbouring dpp units are 3.40 and 3.57\u2005\u00c5). The intra\u00admolecular Au\u22efAu separation is 3.788\u2005(5)\u2005\u00c5. The crystal structure shows weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds involving an O atom of the perchlorate counter-ion and the N atom of the acetonitrile solvent mol\u00adecule, respectively.The title complex, [Au DOI: 10.1107/S1600536808024537/bx2152Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The structure contains infinite chains of ZnCl2 units connected by the bifunctional thia\u00addiazole ligands, with ZnII adopting a distorted tetra\u00adhedral coordination geometry. The dihedral angle between the two pyridyl rings in each ligand is 34.3\u2005(1)\u00b0, and the dihedral angles between the thia\u00addiazole ring and the two pyridyl rings are 18.3\u2005(2) and 16.1\u2005(2)\u00b0. The shortest Zn\u22efZn distance within each polymeric chain is 11.862\u2005(3)\u2005\u00c5, while the shortest inter\u00adchain Zn\u22efZn distance is 7.057\u2005(3)\u2005\u00c5.The title compound, [ZnCl DOI: 10.1107/S1600536808001967/bi2274Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the anion, the S\u2014O bond [1.551\u2005(2)\u2005\u00c5] involving the O atom bearing the acid H atom is longer than the other three S\u2014O bonds, which range from 1.437\u2005(1) to 1.454\u2005(1)\u2005\u00c5.The crystal structure of the title salt, C DOI: 10.1107/S1600536809048533/xu2677Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Intra\u00admolecular C\u2014H\u22efO hydrogen bonds result in the formation of two planar and two non-planar five-membered rings; the latter adopt envelope conformations. There are weak \u03c0\u2013\u03c0 inter\u00adactions between aromatic rings, with centroid-to-centroid distances of 3.796\u2005(2) and 4.171\u2005(2)\u2005\u00c5. There is also a single C\u2014Cl\u22ef\u03c0 inter\u00adaction .In the mol\u00adecule of the title compound, [Sn(C DOI: 10.1107/S1600536808018321/hk2473Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ni\u2014O(phenolate) bond [1.9750\u2005(16)\u2005\u00c5] is shorter than the Ni\u2014O(carbon\u00adyl) bond [2.0840\u2005(16)\u2005\u00c5] and the Ni\u2014N bonds (mean 2.120\u2005\u00c5).In the title compound, [Ni(C DOI: 10.1107/S1600536808023489/is2292Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "I atom in the salt, [Ag(C4H6N2)2]NO3\u00b72H2O, shows a nearly linear coordination [N\u2014Ag\u2014N = 178.26\u2005(7)\u00b0]. The cation, anion and water mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds into a layer motif extending parallel to (101).The Ag DOI: 10.1107/S1600536809045838/bt5122Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The HfO8 coordination polyhedron shows a slightly distorted Archimedean square anti-prismatic coordination with average Hf\u2014O, C\u2014O, C\u2014CMe distances of 2.19\u2005(2), 1.26\u2005(2) and 1.49\u2005(2)\u2005\u00c5, respectively, and an O\u2014Hf\u2014O bite angle of 75.3\u2005(5)\u00b0. Weak O\u2014H\u22efO hydrogen bonding inter\u00adactions are observed between one of the bridging hydr\u00adoxy groups and the disordered solvent mol\u00adecule.The binuclear title compound, [Hf DOI: 10.1107/S1600536809041658/wm2265Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cl ligands are trans to each other, with a Cl\u2014Pt\u2014Cl angle of 178.83\u2005(8)\u00b0. The pyridine ring forms a dihedral angle of 48.8\u2005(2)\u00b0 with the planar PtCl2SN unit. Within the mol\u00adecule, the distance between Pt atoms is 20.262\u2005(5)\u2005\u00c5 and the N\u22efN separation between the terminal pyridyl rings is 16.23\u2005(1)\u00c5.The title dinuclear platinum compound, [Pt DOI: 10.1107/S1600536808024914/gk2157Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Mol\u00adecules are connected into layers in the ac plane via extensive C\u2014H\u22efCl contacts as each Cl atom forms two such inter\u00adactions. Contacts between the layers are of the type C=O\u22ef\u03c0 [O\u22efcentroid distance = 3.110\u2005(8)\u2005\u00c5].In the title compound, [HgCl DOI: 10.1107/S1600536809049289/hy2254Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The CuII atom is coordinated by one tridentate N-salicylideneglycinate Schiff base ligand, one 4-methyl\u00adquinoline ligand and one water mol\u00adecule, leading to a slightly distorted square-pyramidal N2O3 geometry. In the crystal structure, the mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds into linear chains in the [100] direction. The structure is further stabilized by inter\u00admolecular C\u2014H\u22efO inter\u00adactions and C\u22efC contacts with C\u22efC = 3.3058\u2005(2), 3.3636\u2005(2) and 3.3946\u2005(2)\u2005\u00c5.The title complex, [Cu(C DOI: 10.1107/S1600536807067852/tk2236Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Co(C8H5O3)2(C10H14N2O)2(H2O)2], the metal centre is located on an inversion center and is coordinated by two 4-formyl\u00adbenzoate (FOB), two diethyl\u00adnicotinamide (DENA) ligands and two water mol\u00adecules in a slightly distorted CoO4N2 octa\u00adhedral geometry. In the crystal structure, O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into infinite chains. \u03c0\u2013\u03c0 contacts between the parallel pyridine rings of neighboring DENA ligands [centroid\u2013centroid distance = 3.652\u2005(3)\u2005\u00c5] further stabilize the crystal structure.In the crystal structure of the title Co DOI: 10.1107/S1600536809008265/xu2489Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A Cu\u22efCu separation of 3.2281\u2005(3)\u2005\u00c5 is observed. The in-plane Cu\u2014Ophenolate distance [1.9342\u2005(8)\u2005\u00c5] is shorter than the axial distance [2.252\u2005(8)\u2005\u00c5]. The Cu\u2014Namine and Cu\u2014Npy distances are similar . The Cu\u2014Nthio\u00adcyanate distance [1.9678\u2005(11)\u2005\u00c5] is in the range found for Cu\u2014N distances in previously determined structures containing coordinated thio\u00adcyanate anions. There is an inter\u00admolecular hydrogen bond between the amine H atom and the S atom of a coordinated thio\u00adcyanate anion.The centrosymmetric binuclear complex, [Cu DOI: 10.1107/S1600536809031742/kp2227Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the structure, the ZrIV atom is nine-coordinated by three (pydc)2\u2212 groups, resulting in an anionic complex which is balanced by two (tataH)+ cations. One of the NH2 groups shows positional disorder, with site occupation factors of 0.60 and 0.40. There are four uncoordinated water mol\u00adecules  (one of which is disordered with occupation factors of 0.70 and 0.30) in the crystal structure. Several inter\u00admolecular inter\u00adactions, including O\u2014H\u22efO, O\u2014H\u22efN, N\u2014H\u22efO, N\u2014H\u22efN, C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, a C\u2014O\u22ef\u03c0 inter\u00adaction , and \u03c0\u2013\u03c0 stacking [with centroid\u2013centroid distances of 3.694\u2005(2) and 3.802\u2005(2)\u2005\u00c5] are also present.The title compound, (C DOI: 10.1107/S1600536808029887/om2259Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The hydroxonium hydrate (H5O2)+, also known as the Zundel cation, resides on a twofold rotation axis. The O\u2014H distance is 1.274\u2005(14)\u2005\u00c5, the O\u22efO distance is 2.518\u2005(5)\u2005\u00c5, and the O\u2014H\u2014O angle is 162\u2005(8)\u00b0. One of the melamine H+ cations, the uncoordinated pydcH2, and two water mol\u00adecules also reside on crystallographic twofold axes. The CuII atom has a tetra\u00adgonally distorted octa\u00adhedral coordination environment. The structure features extensive hydrogen bonding, with 21 distinct inter\u00adactions. There is also a centrosymmetric C=O\u22ef\u03c0 inter\u00adaction with an O\u22efcentroid distance of 3.288\u2005(3)\u2005\u00c5. The structure is similar to a mixed-valence manganese(II/III) structure but shows inter\u00adesting differences in the metal-atom coordination. One of the water molecules is equally disordered with respect to a twofold axis.The reaction of copper(II) nitrate hexa\u00adhydrate with pyridine-2,6-dicarboxylic acid (pydcH DOI: 10.1107/S1600536809000828/gw2056Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions. In addition, the crystal structure exhibits a Br\u22ef\u03c0 inter\u00adaction of 3.551\u2005(3)\u2005\u00c5 between the Br atom and the centroid of the benzene ring of an adjacent mol\u00adecule.In the title compound, C DOI: 10.1107/S1600536809008101/zl2184Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2,5-dimethyl\u00adpyrazine 1,4-dioxide ligand, which also lies on an inversion center, acts as a bridging ligand, linking symmetry-related CoII ions [Co\u22efCo = 8.669\u2005(3)\u2005\u00c5] and forming one-dimensional chains along the b axis. In the crystal structure, these chains are linked by inter\u00admolecular aqua\u2013perchlorate O\u2014H\u22efO hydrogen bonds, forming two-dimensional layers which are in turn connected into a three-dimensional network via \u03c0\u2013\u03c0 stacking inter\u00adactions between quinoline rings, with a centroid\u2013centroid distance of 3.580\u2005(3)\u2005\u00c5. An intermolecular O\u2014H\u22efCl inter\u00adaction is also present.In the title complex, {[Co(C DOI: 10.1107/S1600536810008895/lh5007Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The AgI ion is linearly coordinated by two dipyrazin-2-ylamine ligands through two pyrazine N atoms. (ClO4               \u2212)\u22ef\u03c0(pyrazine) [O\u22efcentroid distances of 3.612\u2005(3) and 3.664\u2005(1)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.518\u2005(2)\u2005\u00c5] as well as O\u2014H\u22efO and N\u2014H\u22efO hydrogen-bonds assemble the chains into a three-dimensional supra\u00admolecular aggregation. In the title complex, {[Ag(C DOI: 10.1107/S1600536809037532/bg2275Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, inversion-related mol\u00adecules are linked into dimers by O\u2014H\u22efO hydrogen bonds. The packing is further stabilized by \u03c0\u2013\u03c0 inter\u00adactions involving the benzene rings of the dmphen and hydroxy\u00adbenzoate units, with centroid\u2013centroid distances of 3.4930\u2005(14) or 3.5727\u2005(14)\u2005\u00c5.In the title compound, [Cu(C DOI: 10.1107/S1600536808034788/ci2692Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The HgII atoms show a typical linear geometry to a C atom of the benzene ring and to a Cl atom. A benzene C and the azomethine N atom chelate the HgII atoms with weak intra\u00admolecular Hg\u22efN bonding distances of 2.735\u2005(3) and 2.739\u2005(3)\u2005\u00c5, respectively. The resulting five-membered metallacycles are nearly coplanar with the benzene rings [dihedral angles = 0.9\u2005(1) and 0.7\u2005(1)\u00b0], while the pyridine rings make dihedral angles with the benzene units of 58.17\u2005(1) and 56.58\u2005(1)\u00b0. In the crystal structure, the HgII complexes are linked by hydr\u00adoxy donor and pyridine acceptor groups into chains along [010]. The water mol\u00adecules connect the complexes through inter\u00admolecular O\u2014H\u22efOcarbon\u00adyl bonds in the a-axis direction, and the azomethine H atoms donate towards the water O atoms, forming a three-dimensional network of inter\u00admolecular O\u2014H\u22efN, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds.The asymmetric unit of the title compound, [Hg(C Cl]\u00b7H2O = 0.021                           wR(F                           2) = 0.046                           S = 1.05                           5658 reflections381 parametersH-atom parameters constrainedmax = 0.52 e \u00c5\u22123                        \u0394\u03c1min = \u22120.83 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL (Sheldrick, 2008SHELXTL and PLATON (Spek, 2009Data collection: 10.1107/S1600536809023824/si2184sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023824/si2184Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Mn3+ ions are bridged by anionic pyridine-2-carboxyl\u00adate (pic) ligands, thereby forming a chain-like structure along the c axis, and are six-coordinated in a distorted octa\u00adhedral environment by two O atoms of the two different carboxyl\u00adate groups, two O atoms of two water mol\u00adecules and two Br atoms. The complex displays inter\u00admolecular O\u2014H\u22efBr, O\u2014H\u22efN, O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonding. There may also be inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent pyridine rings, with a centroid\u2013centroid distance of 3.993\u2005(8)\u2005\u00c5.The asymmetric unit of the title compound, [MnBr DOI: 10.1107/S160053680902844X/im2127Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecular conformation is stabilized by weak intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds. The crystal structure features weak C\u2014H\u22ef\u03c0 inter\u00adactions.In the title mol\u00adecule, C DOI: 10.1107/S1600536809037830/is2462Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, a combination of close contacts formed via Ag\u22efN inter\u00adactions [Ag\u22efN = 3.098\u2005(2) and 3.261\u2005(2)\u2005\u00c5] from symmetry-related mol\u00adecules and inter\u00admolecular N\u2014H\u22efO hydrogen bonds between CF3CO2               \u2212 anions and the hydrazone groups of two ligands give rise to chains. Furthermore, there are Ag\u22efO inter\u00adactions with a separation of 2.765\u2005(2)\u2005\u00c5 between chains. The F atoms of the CF3CO2               \u2212 anion are disordered over two sites with refined occupancies of 0.593\u2005(5) and 0.407\u2005(5).In the title compound, [Ag(C DOI: 10.1107/S1600536809029183/lh2867Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ansa-molybdocene [C2Me4(\u03b75-C5H4)2]Mo unit has a typical bent-sandwich metallocene structure with an inter-ring angle of 127.98\u2005(8)\u00b0. The Mo atom in the bridging (\u03bc2-O)(\u03bc3-O)2MoO2 group has a distorted trigonal\u2013bipyramidal coordination. The Mo\u2014(\u03bc3-O) and Mo\u2014(\u03bc2-O) bond distances inside the units  are slightly longer than the Mo\u2014(\u03bc3-O) bond distance between the units [1.9986\u2005(14)\u2005\u00c5]. The solvent water mol\u00adecules together with complex O atoms form a network of O\u2014H\u22efO hydrogen bonds.The title compound, [Mo DOI: 10.1107/S1600536808031668/hb2806Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It is composed of a planar r.m.s. deviation (0.0012\u2005\u00c5) tetra\u00adzole ring which is nearly coplanar with the benzene ring, the dihedral angle being 2.67\u2005(9)\u00b0. In the crystal, symmetry-related mol\u00adecules are linked by inter\u00admolecular N\u2014H\u22efN hydrogen bonds. The mol\u00adecules stack along [100] with a \u03c0\u22ef\u03c0 inter\u00adaction involving the phenyl and tetra\u00adzole rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.5639\u2005(15)\u2005\u00c5]. The H atom of the N\u2014H group is disordered over two sites of equal occupancy. The methyl H atoms were modelled as disordered over two sets of sites of equal occupancy rotated by 60\u00b0 with respect to each other.The title compound, C DOI: 10.1107/S1600536809036411/su2134Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2], is centrosymmetric with the Ni atom located on an inversion centre. The mol\u00adecule contains two 2-chloro\u00adbenzoate (CB) and two nicotinamide (NA) ligands and two water mol\u00adecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 29.48\u2005(16)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 83.16\u2005(5)\u00b0. In the crystal structure, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into infinite chains. \u03c0\u2013\u03c0 Contacts between the benzene and pyridine rings [centroid\u2013centroid distance = 3.952\u2005(1)\u2005\u00c5] may further stabilize the crystal structure. There is also a C\u2014H\u22ef\u03c0 inter\u00adaction.The title Ni DOI: 10.1107/S1600536809011209/xu2501Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure stabilized by three different inter\u00admolecular non-classical C\u2014H\u22efO hydrogen bonds. The crystal structure also exhibits aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of adjacent benzofuran ring systems [centroid\u2013centroid distance = 3.688\u2005(2)\u2005\u00c5]In the title compound, C DOI: 10.1107/S1600536809037003/bq2158Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angles between the benzimidazole ring system and the phenyl rings in each of the benzyl\u00adbenzimidazole units are 78.56\u2005(12), 81.68\u2005(11), 75.76\u2005(10) and 85.78\u2005(9)\u00b0. In the crystal structure, there are weak but significant inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances of 3.685\u2005(1) and 3.978\u2005(1)\u2005\u00c5.In the title compound, [Zn(C DOI: 10.1107/S1600536809022296/lh2840Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The thia\u00addiazole rings are oriented at a dihedral angle of 84.87\u2005(4)\u00b0. Intra\u00admolecular N\u2014H\u22efCl inter\u00adactions result in the formation of two six-membered rings having envelope and planar conformations. In the crystal structure, inter\u00admolecular N\u2014H\u22efN and N\u2014H\u22efCl inter\u00adactions link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 contacts between thia\u00addiazole rings [centroid\u2013centroid distance = 3.602\u2005(1)\u2005\u00c5] may further stabilize the structure.In the title compound, [ZnCl DOI: 10.1107/S1600536809032073/hk2748Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It is an example of a new type of tropolone derivative that has not been characterized via solid-state methods. Weak intra\u00admolecular C\u2014H\u22efN and inter\u00admolecular C\u2014H\u22efO hydrogen bonds, and \u03c0\u2013\u03c0 stacking inter\u00adactions between the tropolone rings [centroid\u2013centroid distance = 3.590\u2005(8)\u2005\u00c5] are observed in the crystal structure.In the title compound, [Rh(C DOI: 10.1107/S160053680803780X/hy2163Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the ferrocene unit, the substituted (Cps) and unsubstituted (Cp) cyclo\u00adpenta\u00addienyl rings are eclipsed and almost parallel [Cps\u2014Fe\u2014Cps angle = 176.1\u2005(2)\u00b0]. The mol\u00adecule is linked into an S(5) motif via intra\u00admolecular C\u2014H\u22efO hydrogen bonds. The mol\u00adecules are arranged into a three-dimensional framework by five inter\u00admolecular C\u2014H\u22efO hydrogen bonds and one inter\u00admolecular C\u2014H\u22ef\u03c0(Cps) inter\u00adaction.In the title compound, [Fe(C DOI: 10.1107/S1600536808025518/pv2096Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each PZDC2\u2212 dianion serves as a spacer, connecting adjacent metal atoms into a polymeric chain structure parallel to the b axis. The chain motif is consolidated into a three-dimensional supra\u00admolecular network by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 aromatic stacking inter\u00adactions involving adjacent DPPZ ligands and PZDC2\u2212 dianions with centroid\u2013centroid separations of 3.522\u2005(6) and 3.732\u2005(8)\u2005\u00c5, respectively.In the title compound, [Zn(C DOI: 10.1107/S1600536808022824/rz2235Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex, the two MnIII ions are bridged by two O atoms from two symmetry-related N,N\u2032-bis\u00ad-1,2-diimino\u00adbenzene dianionic ligands with the longer Mn\u2014O distance of 2.703\u2005(3)\u2005\u00c5, thus each Mn ion is six-coordinated by two N and three O atoms from the two dianionic ligands and one capping Cl atom in a distorted octa\u00adhedral environment. The crystal structure displays inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent benzene rings, with a shortest centroid\u2013centroid distance of 3.673\u2005(2)\u2005\u00c5, and inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22ef Cl and C\u2014H\u22ef Br hydrogen bonds.The asymmetric unit of the title compound, [Mn DOI: 10.1107/S1600536810003247/xu2722Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each CuII atom is coordinated by two O atoms and one N atom from the tridentate ligand L               2\u2212 [LH2 = (E)-2--2-(4-hydroxy\u00adphenyl)acetic acid] and the O atom of a dimethyl\u00adformamide mol\u00adecule to give a slightly distorted square-planar geometry. The two unique mol\u00adecules form a dimer through weak C\u2014H\u22efO hydrogen bonds. In the dimer, the Cu\u22efCu distance is 3.712\u2005(1)\u2005\u00c5. In the crystal structure, mol\u00adecules form a one-dimensional chain through C\u2014H\u22efO hydrogen bonds. These are further aggregated into a three-dimensional network by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds.In the title complex, [Cu(C DOI: 10.1107/S1600536808007915/sj2468Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are two intra\u00admolecular N\u2014H\u22efBr hydrogen bonds completing twisted six-membered rings with R(6) motifs. The dihedral angles between the aromatic rings in the ligands are 62.11\u2005(13) and 85.73\u2005(13)\u00b0. In the crystal, components are linked by N\u2014H\u22efO, O\u2014H\u22efS and O\u2014H\u22ef\u03c0 inter\u00adactions. There also exist \u03c0\u2013\u03c0 inter\u00adactions with a distance of 3.876\u2005(2)\u2005\u00c5 between the centroids of benzene rings of two different ligands. Together, the inter\u00admolecular inter\u00adactions lead to a three-dimensional network.In the title compound, [CuBr(C DOI: 10.1107/S1600536809026038/hb5021Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "All hydroxyl groups act as donors and acceptors in hydrogen bonding and the mol\u00adecule is involved in ten inter\u00admolecular O\u2014H\u22efO inter\u00adactions [O\u22efO = 2.672\u2005(5)\u20132.776\u2005(4)\u2005\u00c5] with eight neighbouring mol\u00adecules. Two independent O\u2014H\u22efO\u2014H\u22ef helices extending along the z axis are found in this structure.The mol\u00adecule of the title compound, C DOI: 10.1107/S1600536809000397/gk2181Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It contains a half-sandwich complex of ruthenium with a three-legged piano-stool geometry, with Ru\u2014P = 2.3585\u2005(4) and 2.3312\u2005(4)\u2005\u00c5, and Ru\u2014N = 2.0422\u2005(15)\u2005\u00c5\u2005as the legs. The CF3SO3               \u2212 anion is anchored in the crystal lattice by C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds, with C\u22efF,O distances starting at 3.125\u2005(2)\u2005\u00c5.The title compound, [Ru(C DOI: 10.1107/S1600536809038720/ez2188Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The slightly distorted octa\u00adhedral environment of the Ru center is formed by four P atoms [Ru\u2014P = 2.4417\u2005(6) and 2.4544\u2005(6)\u2005\u00c5] from two different -TangPhos ligands  and two Cl atoms [Ru\u2014Cl = 2.4267\u2005(5)\u2005\u00c5].In the title compound, [RuCl DOI: 10.1107/S1600536808008301/cv2390Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "At the core of the structure is an Li2O2 four-membered ring. The structure is centrosymmetric with an inversion centre midway between two Li atoms. Inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions between the 2-methyl\u00adpyridine rings exist [centroid\u2013centroid distance = 3.6312\u2005(16)\u2005\u00c5].The title compound, [Li DOI: 10.1107/S1600536808042748/gw2055Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Ni(C7H4BrO2)2(C6H6N2O)2(H2O)2], is centrosymmetric. It contains two 2-bromo\u00adbenzoate (BB) ligands, two nicotinamide (NA) ligands and two water mol\u00adecules, all of them being monodentate. The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 30.81\u2005(17)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 84.66\u2005(6)\u00b0. In the crystal structure, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a supra\u00admolecular structure. A weak C\u2014H\u22ef\u03c0 inter\u00adaction is also found.The title Ni DOI: 10.1107/S1600536809021710/xu2538Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII ion is coordinated by two N atoms [Cu\u2014N = 1.960\u2005(4)\u2005\u00c5] and two O atoms [Cu\u2014O = 1.908\u2005(4)\u2005\u00c5] from the tetra\u00addentate Schiff base ligand and by one O atom [Cu\u2014O = 2.324\u2005(6)\u2005\u00c5] of the methanol molecule in a square-pyramidal geometry. In the crystal structure, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link complex mol\u00adecules into extended chains along [001].In the title compound, [Cu(C DOI: 10.1107/S1600536809011179/lh2794Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II compound, [Ni(C8H5O3)2(C10H14N2O)2(H2O)2], the central NiII atom is coordinated by two O atoms from two 4-formyl\u00adbenzoate (FOB) ligands, two O atoms from two water mol\u00adecules and two N atoms from two diethyl\u00adnicotinamide (DENA) ligands. The coordination geometry is slightly distorted octa\u00adhedral, with four O atoms in the equatorial plane and two N atoms in axial positions. Intra\u00admolecular O\u2014H\u22efO hydrogen bonds are observed. In the crystal structure, mol\u00adecules are linked into chains along the a axis by inter\u00admolecular O\u2014H\u22efO hydrogen bonds. The structure is further stabilized by \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings of DENA units, with a centroid\u2013centroid distance of 3.668\u2005(2)\u2005\u00c5.In the title centrosymmetric mononuclear Ni DOI: 10.1107/S1600536809006345/ci2769Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An uncoordinated dmphen and an uncoordinated water mol\u00adecule cocrystallized with each complex mol\u00adecule. Intra- and inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds are also present between the coordinated 3-HBA and water mol\u00adecules and the uncoordinated dmphen and water mol\u00adecules in the crystal. The packing of the structure is further stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions involving dmphen mol\u00adecules, with a centroid\u2013centroid separation of 3.705\u2005(3)\u2005\u00c5.In the title compound, [Mn(C DOI: 10.1107/S1600536809025926/pv2157Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two TbIII ions are linked by four bridging benzoate ions, with a Tb\u22efTb distance of 3.9280\u2005(6)\u2005\u00c5. Additionally, each TbIII ion is coordinated by one phenanthroline heterocycle and a bidentate benzoate ion. The irregular nine-coordinated geometry of the TbIII ion is composed of seven O and two N atoms. The mol\u00adecular structure is stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds. In the crystal structure, mol\u00adecules are linked into chains along the a axis by inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The crystal structure is further stabilized by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. Weak \u03c0\u2013\u03c0 inter\u00adactions are also observed [centroid\u2013centroid distances = 3.6275\u2005(14)\u20133.6604\u2005(14)\u2005\u00c5].The asymmetric unit of the title complex, [Tb For rel al. 1999, 2002 \u25b6;2(C7H5O2)6(C12H8N2)2]\u00b72C7H6O2                         = 0.018                           wR(F                           2) = 0.101                           S = 1.20                           11944 reflections460 parametersH-atom parameters constrainedmax = 1.41 e \u00c5\u22123                        \u0394\u03c1min = \u22122.25 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXTL (Sheldrick, 2008SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009Data collection: 10.1107/S1600536810016788/rz2444sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016788/rz2444Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II ion in the title complex, [HgCl2(C13H12N2)], adopts a distorted tetra\u00adhedral geometry being coordinated by two Cl anions and by two N atoms of the benz\u00adyl(2-pyridyl\u00admethyl\u00adene)amine ligand. The Cl\u2014Hg\u2014Cl plane is twisted at 70.1\u2005(1)\u00b0 from the mean plane of the chelate ring. In the crystal structure, inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.793\u2005(3)\u2005\u00c5] between the aromatic rings link the mol\u00adecules into zigzag chains extending along [010].The Hg DOI: 10.1107/S1600536810035889/cv2760Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of PMB ions acts as a bidentate ligand while the other and the two INA are monodentate ligands. An O\u2014H\u22efO hydrogen bond links the uncoordinated water mol\u00adecule to the carboxyl groups of the complex. The dihedral angles between the carboxyl groups and the adjacent benzene rings are 10.28\u2005(11) and 21.24\u2005(9)\u00b0, while the two benzene rings and the two pyridine rings are oriented at dihedral angles of 6.90\u2005(4) and 88.64\u2005(4)\u00b0, respectively. In the crystal structure, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a supra\u00admolecular structure. A \u03c0\u2013\u03c0 contact between the benzene rings [centroid\u2013centroid distance = 3.911\u2005(1)\u2005\u00c5] may further stabilize the crystal structure. Weak C\u2014H\u22ef\u03c0 inter\u00adactions involving the pyridine rings also occur in the crystal structure.In the crystal structure of the title compound, [Cd(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)]\u00b7H2O = 0.020                           wR(F                           2) = 0.053                           S = 1.14                           7154 reflections404 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.56 e \u00c5\u22123                        \u0394\u03c1min = \u22120.38 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810008366/xu2732sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008366/xu2732Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The xanthene ring system is essentially planar, with an average deviation of 0.020\u2005\u00c5, and the substituent benzene ring forms a dihedral angle of 85.89\u2005(2)\u00b0 with it. The Sn\u2014Cl distances are in the range 2.4237\u2005(3)\u20132.4454\u2005(3)\u2005\u00c5. There are N\u2014H\u22efCl hydrogen bonds between SnCl6               2\u2212 ions and rhodamine 6G cations as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between rhodamine 6G cations (inter\u00adplanar distance of 3.827\u2005\u00c5).In the title compound, bis({6-ethylamino-10-[2-(methoxycarbonyl)phenyl]-2,7-dimethylxanthen-3-ylidene}ethanaminium) hexachloridotin(IV) acetonitrile disolvate, (C DOI: 10.1107/S1600536807066287/pv2056Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Sn atom is coordinated by one N [Sn\u2014N = 2.187\u2005(3)\u2005\u00c5], two O [Sn\u2014O = 2.123\u2005(3) and 2.174\u2005(3)\u2005\u00c5] and two C [Sn\u2014C = 2.096\u2005(4) and 2.101\u2005(4)\u2005\u00c5] atoms in a distorted trigonal-bipyramidal geometry. The crystal packing exhibits weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds, which link the mol\u00adecules into centrosymmetric dimers with an Sn\u22efSn separation of 4.330\u2005(6)\u2005\u00c5, and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance of 3.690\u2005(5)\u2005\u00c5 between the benzene rings of neighbouring mol\u00adecules].In the title mol\u00adecule, [Sn(CH DOI: 10.1107/S1600536808040786/cv2482Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular \u03c0\u2013\u03c0 stacking between parallel pyridine rings [face-to-face distance 3.32\u2005(4)\u2005\u00c5] and C\u2014H\u22efBr and C\u2014H\u22efO hydrogen-bonding interactions are present in the crystal structure.In the mol\u00adecule of the title compound, [ZnBr DOI: 10.1107/S1600536810017551/xu2761Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each AgI ion is coordinated by two N atoms from two different isonicotinate ligands. The crystal structure exhibits a two-dimensional heterometallic polymeric layer. O\u2014H\u22efO hydrogen bonds involving the coordinated and uncoordinated water mol\u00adecules and intra\u00adlayer \u03c0\u2013\u03c0 inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.571\u2005(2) and 3.569\u2005(2)\u2005\u00c5] are observed. Each layer inter\u00adacts with two neighboring ones via Ag\u22efO(H2O) contacts and inter\u00adlayer \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.479\u2005(3) to 3.530\u2005(3)\u2005\u00c5], leading to a three-dimensional supra\u00admolecular network.In the title complex, {[Ag DOI: 10.1107/S1600536809042342/hy2237Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Ni(C8H7O2)2(C6H6N2O)2(H2O)2], is centrosymmetric with the Ni atom located on an inversion center. The mol\u00adecule contains two 4-methyl\u00adbenzoate (PMB) and two nicotinamide (NA) ligands and two coordinated water mol\u00adecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 26.15\u2005(10)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 87.81\u2005(4)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. The \u03c0\u2013\u03c0 contact between the benzene rings [centroid\u2013centroid distance = 3.896\u2005(1)\u2005\u00c5] may further stabilize the crystal structure. A weak C\u2014H\u22ef\u03c0 inter\u00adaction involving the pyridine ring also occurs.The title Ni N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.030                           wR(F                           2) = 0.068                           S = 1.05                           3390 reflections204 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.48 e \u00c5\u22123                        \u0394\u03c1min = \u22120.50 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810007385/xu2730sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007385/xu2730Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the Br atoms is disordered over two sites [site-occupancy factors = 0.51\u2005(6) and 0.49\u2005(6)]. The N\u2014C\u2014N angles in the cations are 110.7\u2005(6) and 111.4\u2005(7)\u00b0. In the crystal packing, a supra\u00admolecular chain is formed via both weak inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 aromatic ring stacking inter\u00adactions [centroid\u2013centroid separation = 3.803\u2005(1)\u2005\u00c5].In the title compound, (C DOI: 10.1107/S1600536809047461/zs2017Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The compound consists of an anionic complex, a doubly protonated propane-1,3-diamine as a counter-ion and 3.5 uncoord\u00adinated water mol\u00adecules. The coordination polyhedron around the ZnII atom is distorted octa\u00adhedral, defined by four O atoms and two N atoms from two Hchel  ligands. In the crystal structure, O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds along with \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.473\u2005(2)\u2005\u00c5] are observed to reinforce the crystal cohesion.The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536809041634/hy2228Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two intra\u00admolecular O\u2014H\u22efO hydrogen bonds stabilize the conformation of the anion. The polymeric three-dimensional supra\u00admolecular architecture is formed via coordination inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions involving centrosymmetrically related pyrone rings, with a centroid\u2013centroid separation of 3.513\u2005(2)\u2005\u00c5.In the polymeric title compound, [K(C DOI: 10.1107/S1600536808041779/rz2268Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "This unit coordinates to a CaII cation in an O,O\u2032,O\u2032\u2032-tridentate fashion, generating a distorted CaCo3O4 cubane-type cluster. The Ca\u2014\u03bc3-O distances [2.429\u2005(5)\u20132.572\u2005(6)\u2005\u00c5] are much longer than the Co\u2014\u03bc3\u2014O bonds [1.895\u2005(5)\u20131.941\u2005(5)\u2005\u00c5]. The CaII cation is also coord\u00adinated by five water mol\u00adecules with Ca\u2014O distances in the range 2.355\u2005(6)\u20132.543\u2005(6)\u2005\u00c5. There are three additional uncoordinated water mol\u00adecules in the asymmetric unit, the occupancy of which refined to 0.54\u2005(3). In H2O (or D2O), the title complex hydrolyses to Ca2+               aq cations and [Co3(ida)3(\u03bc2-OH)3(\u03bc3-O)]2\u2212 anions. In the title compound, [CaCo DOI: 10.1107/S1600536810010998/sj2753Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII ion is located on a crystallographic twofold rotation axis and assumes a distorted tetra\u00adhedral ZnN2O2 coordination geometry. Mol\u00adecules are linked by an inter\u00admolecular O\u2014H\u22efO hydrogen bond and \u03c0\u2013\u03c0 stacking inter\u00adactions between pyridine rings [centroid\u2013centroid speparation 3.594\u2005(1)\u2005\u00c5].The title complex, [Zn(C DOI: 10.1107/S1600536809027147/bx2223Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In ligand L, the imidazole and triazole rings form a dihedral angle of 74.25\u2005(8)\u00b0. Mol\u00adecules are assembled into a three-dimensional structure via inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efN hydrogen-bonds, and \u03c0\u2013\u03c0 inter\u00adactions with a short distance of 3.665\u2005(2)\u2005\u00c5 between the centroids of the imidazole and triazole rings of neighbouring mol\u00adecules.In the title compound, [Mn(C DOI: 10.1107/S1600536810012626/cv2709Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The tridentate function of each ligand is completed by two N atoms coordinated to the two CuII atoms [Cu\u2014N = 1.933\u2005(2)\u2005\u00c5]. The separation distance of two CuII atoms in a cluster is 2.988\u2005(1)\u2005\u00c5. The dihedral angle between the six-membered chelate rings is 2.13\u2005(9)\u00b0. The perchlorate counter-anion is disordered over two sites in a 0.58\u2005(10):0.42\u2005(10) ratio.The title complex, [Cu DOI: 10.1107/S1600536810008512/kp2237Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The \u2013OH substituent only results in weak C\u2014H\u22efO weak inter\u00adactions between one of cyclo\u00adpenta\u00addienyl (Cp) ring H atoms and the O atom of a neighbouring mol\u00adecule with a distance of 3.308\u2005(3)\u2005\u00c5 between the donor and acceptor atoms. The inter\u00adplanar angle between the Cp and benzene rings is 13.0\u2005(4)\u00b0. There are also weak O\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions involving the unsubstituted Cp and the benzene ring, respectively.The title compound, [Fe(C DOI: 10.1107/S1600536808039524/dn2401Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angles between meso-substituted chloro\u00adphenyl rings and the basic tetra\u00adpyrrolic ring are 82.66\u2005(9), 82.16\u2005(7), 83.97\u2005(11) and 76.87\u2005(8)\u00b0. In one of the phosphine ligands, the two terminal methyl groups are disordered over two positions with refined site-occupancy ratios of 0.70\u2005(7):0.30\u2005(7) and 0.66\u2005(2):0.34\u2005(2). In the crystal structure, mol\u00adecules are linked together along the a axis by inter\u00admolecular C\u2014H\u22efCl inter\u00adactions. The crystal structure is further stabilized by intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions and inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the mol\u00adecule of the title compound, [Co(C DOI: 10.1107/S1600536809019163/at2788Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, there is a \u03c0\u2013\u03c0 stacking inter\u00adaction involving a pyrazole ring and a symmetry-related pyridine ring with a centroid\u2013centroid distance of 3.578\u2005(3)\u2005\u00c5.In the title complex, [Cd(NCS) DOI: 10.1107/S1600536809039920/lh2919Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A twofold rotation axis passes through the Mg atom. In the crystal structure, the cations and anions are linked by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.804\u2005(2)\u2005\u00c5] into layers parallel to the ac plane.In the mononuclear title complex, [Mg(C DOI: 10.1107/S1600536808022150/im2068Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The torsion angles for the Te\u2014Re\u2014Te\u2014Re sequence of atoms are 19.29\u2005(18) and 16.54\u2005(16)\u00b0 in the two mol\u00adecules. Thus, the Re\u2014Te four-membered rings in the two mol\u00adecules deviate significantly from planarity. Two intra\u00admolecular C\u2014H\u22efO inter\u00adactions occur in one of the mol\u00adecules. Te\u2014Te [4.0551\u2005(10)\u2005\u00c5] inter\u00adactions between the two mol\u00adecules and weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions stabilize the crystal packing.The title compound, [Re DOI: 10.1107/S1600536810014297/sj2772Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the two phenyl rings is 48.14\u2005(6)\u00b0. In the crystal structure, inter\u00admolecular N\u2014H\u22efO hydrogen bonds link mol\u00adecules into centrosymmetric dimers. These dimers are, in turn, linked into a two-dimensional network via weak N\u2014H\u22ef\u03c0(arene) inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances of 3.6937\u2005(11)\u2005\u00c5.The crystal structure determination of the title compound, C DOI: 10.1107/S1600536809046133/sj2668Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "N2OS and N2O2, each exhibiting a distorted square-planar geometry. \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings of neighbouring complexes [centroid\u2013centroid distance = 3.856\u2005(5)\u2005\u00c5] link pairs of mol\u00adecules into centrosymmetric dimers, which are further packed into stacks along the b axis with relatively short Cu\u22efCu separations of 3.482\u2005(1)\u2005\u00c5. Weak inter\u00admolecular C\u2014H\u22efN hydrogen bonds help to consolidate the crystal packing.In the title dinuclear complex, [Cu DOI: 10.1107/S1600536809040951/cv2616Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each independent [FeIII(mnt)2]\u2212 unit forms a centrosymmetric dimer supported by two inter\u00admonomer FeIII\u2014S bonds [Fe\u2014S = 2.4715\u2005(9) and 2.4452\u2005(9)\u2005\u00c5]. In the crystal structure, the dimers form one-dimensional \u03c0\u2013\u03c0 stacks along the a axis, with an inter\u00adplanar separation of 3.38\u2005(6)\u2005\u00c5.The title compound, [Fe(C DOI: 10.1107/S1600536808036805/lh2727Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance 3.501\u2005(3)\u2005\u00c5]. As well as the cation, two anions and two dimethyl\u00adformamide solvent mol\u00adecules, the asymmetric unit also contains an ethanol solvent molecule with 0.25 occupancy.In the title compound, [Ni(C DOI: 10.1107/S1600536809021163/lh2826Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom is coordinated by two pydc dianions acting as tridentate ligands, and forming five-membered chelate rings with copper(II) as the central atom. The CuII atom is surrounded by four O atoms in the equatorial plane and two pyridine N atoms in axial positions, resulting in a distorted octa\u00adhedral coordination geometry. In the crystal, there are two types of O\u2014H\u22efO and N\u2014H\u22efO hydrogen-bonding synthons linking the anionic and cationic fragments and the water mol\u00adecules, namely R               4               4(16), and R               4               2(8). There are also weak C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 stacking inter\u00adactions [the shortest centroid\u2013centroid distance is 3.350\u2005(2)\u2005\u00c5], and a C\u2014O\u22ef\u03c0 inter\u00adaction [O\u22efcentroid distance = 3.564\u2005(2)\u2005\u00c5], which connect the various components into a three-dimensional network.The asymmetric unit of the title compound, (C DOI: 10.1107/S160053681003059X/vm2038Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII atoms are bridged by the PZDC dianions, forming an infinite one-dimensional chain running along the b axis. Adjacent chains pack together through \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separations = 3.498\u2005(4) and 3.528\u2005(4)\u2005\u00c5], and O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds involving the water mol\u00adecule complete the structure.In the title compound, [Co(C DOI: 10.1107/S1600536808027177/hb2775Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The most important bond distances include Pd\u2014P of 2.380\u2005(2)\u2005\u00c5 and Pd\u2014Br of 2.515\u2005(2)\u2005\u00c5. Weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.949\u2005(6)\u2005\u00c5] are present via crystallographic inversion centres, resulting in a one-dimensional supra\u00admolecular architecture.The title compound, [PdBr DOI: 10.1107/S1600536808030845/si2114Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Bi\u2014S and S\u2014P bond lengths are in the ranges 2.7694\u2005(18)\u20132.8391\u2005(17) and 2.019\u2005(2)\u20132.035\u2005(2)\u2005\u00c5, respectively. The crystal structure is consolidated by C\u2014H\u22efS hydrogen bonds. Intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions also play a role in stabilizing the mol\u00adecules.The title compound, [Bi(C DOI: 10.1107/S1600536810015618/wm2334Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Cu2Cl4(C24H21N5O4)2], was synthesized by the reaction of CuCl2\u00b72H2O with the tripodal ligand 2,2\u2032-diphthalimide (L). Each of the CuII ions is coordinated by two N atoms from the ligand, two bridging Cl atoms and one terminal Cl atom. The CuII coordination can be best be described as a transition state between four- and five-coordination, since one of the bridging Cl atoms has a much longer Cu\u2014Cl bond distance [2.7069\u2005(13)\u2005\u00c5] than the other [2.2630\u2005(12)\u2005\u00c5]. In addition, the Cu\u22efCu distance is 3.622\u2005(1)\u2005\u00c5. The three-dimensional structrure is generated by N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.658\u2005(4) and 4.020\u2005(4)\u2005\u00c5].The centrosymmetric dinuclear Cu DOI: 10.1107/S1600536809045565/kp2236Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Cu2+ and the Cl\u2212 ion are imposed by a twofold rotation axiss which also bisects the equally disordered benzoate anion. In the crystal, the mol\u00adecules are assembled into chains along [010] by C\u2014H\u22efCl, O\u2014H\u22efCl and C\u2014H\u22efO hydrogen-bonding inter\u00adactions. The resulting chains are further connected into two-dimensional supra\u00admolecular layers parallel to [100] by inter\u00adchain \u03c0\u22ef\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.823\u2005(5)\u2005\u00c5] between the phenanthroline ligands and the benzoic acid mol\u00adecules, and by C\u2014H\u22efO hydrogen-bonding inter\u00adactions. Strong \u03c0\u22ef\u03c0 stacking inter\u00adactions between adjacent phenantroline ligands [3.548\u2005(4)\u2005\u00c5] assemble the layers into a three-dimensional supra\u00admolecular architecture.In the title complex, [Cu(C DOI: 10.1107/S1600536810011487/zq2032Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The phenyl ring is nearly perpendicular to the plane of the tricyclic naphthofuran system [81.77\u2005(6)\u00b0] and is tilted slightly towards it. The 4-bromo\u00adphenyl ring is rotated out of the naphthofuran plane by a dihedral angle of 31.12\u2005(4)\u00b0. In the crystal structure, non-classical inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efBr hydrogen bonds are observed. The crystal structure also exhibits aromatic \u03c0\u2013\u03c0 inter\u00adactions between the furan ring and the central benzene ring of the adjacent naphthofuran system [centroid\u2013centroid distance = 3.768\u2005(3)\u2005\u00c5]. In addition, inter\u00admolecular C\u2014Br\u22ef\u03c0 inter\u00adactions [3.866\u2005(2)\u2005\u00c5] between the Br atom and the phenyl ring of the phenyl\u00adsulfinyl substituent are present.In the title compound, C DOI: 10.1107/S1600536809029250/im2130Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each Ag atom is connected by one bridging 4,4\u2032-bipyridine [Ag\u2014N = 2.177\u2005(4)\u00c5] and a terminal dicyanamide [Ag\u2014N = 2.108\u2005(4)\u2005\u00c5]. The Ag\u2014Ag interactions play a key role in constructing a unique neutral polymeric chain.In the title compound, [Ag DOI: 10.1107/S1600536809050491/pv2240Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal structure, inter\u00admolecular N\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into centrosymmetric dimers. There is a \u03c0\u2013\u03c0 contact between the pyridine rings [centroid\u2013centroid distance = 3.896\u2005(5)\u2005\u00c5].In the mol\u00adecule of the title compound, [HgCl DOI: 10.1107/S1600536808040294/hk2588Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions between a methyl H atom of the methyl\u00adsulfinyl group and the benzene ring of the benzofuran system, and by an I\u22efO halogen bond of 3.173\u2005(3)\u2005\u00c5 and a nearly linear C\u2014I\u22efO angle of 171.7\u2005(1)\u00b0. In addition, the crystal structure exhibits weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The O atom of the carbonyl group and the butyl chain are both disordered over two positions with site-occupancy factors from refinement of 0.55\u2005(4) and 0.45\u2005(4) (for the O atom), and 0.76\u2005(2) and 0.24\u2005(2) (for the butyl group).In the title compound, C DOI: 10.1107/S1600536809000208/hg2458Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link two CuL mol\u00adecules and four solvent mol\u00adecules into a centrosymmetric cluster. The crystal packing exhibits short inter\u00admolecular C\u22efC contacts of 3.185\u2005(4) and 3.232\u2005(4)\u2005\u00c5.In the title compound, [Cu(C DOI: 10.1107/S1600536809053720/cv2670Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure exhibits inter\u00admolecular O\u2014H\u22efO hydrogen bonds, short Cl\u22efCl contacts [3.334\u2005(1)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance 3.621\u2005(11)\u2005\u00c5].In the title complex, [Cu(C DOI: 10.1107/S1600536808000044/cv2370Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The values of the bond angles at the Zn atom are in the range 99.4\u2005(1) to 113.2\u2005(1)\u00b0. The presence of O\u2014H\u22efO and O\u2014H\u22efBr intra\u00admolecular hydrogen bonds can explain the difference between the two Zn\u2014O [1.961\u2005(3)/2.015\u2005(3)\u2005\u00c5] and the two Zn\u2014Br [2.350\u2005(1)/2.378\u2005(1)\u2005\u00c5] bond lengths. The crystal structure is governed by C\u2014H\u22efO, C\u2014H\u22efBr and Zn\u2014Br\u22efCg(\u03c0-ring) inter\u00adactions.In the title compound, [ZnBr DOI: 10.1107/S1600536808016838/dn2351Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The oxycarbene group is nearly planar, with the phenyl ring twisted by an angle of 39.1\u2005(2)\u00b0 with respect to this plane. One of the cyclo\u00adpenta\u00addienyl rings undergoes an offset face-to-face \u03c0\u2013\u03c0 inter\u00adaction [3.544\u2005(6)\u2005\u00c5] with the symmetry-related cyclo\u00adpenta\u00addienyl ring of a neighbouring mol\u00adecule.The title compound, [TiW(C DOI: 10.1107/S1600536808036465/at2672Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two cyclo\u00adpenta\u00addienyl (Cp) rings are parallel to each other in both mol\u00adecules, forming dihedral angles of 2.3\u2005(3) and 1.0\u2005(3)\u00b0, respectively, and adopt an eclipsed conformation. The mean plane of the semicarbazone group is twisted slightly away from the attached Cp ring in both mol\u00adecules, the dihedral angles between the mean plane and the Cp ring being 15.3\u2005(2) and 10.8\u2005(2)\u00b0. The ethyl group in mol\u00adecule A is coplanar with the mean plane of the semicarbazone group [C\u2014N\u2014C\u2014C torsion angle = \u2212175.2\u2005(4)\u00b0], whereas it is nearly perpendicular in mol\u00adecule B [C\u2014N\u2014C\u2014C torsion angle = 84.8\u2005(6)\u00b0]. In the crystal structure, inter\u00admolecular N\u2014H\u22efS hydrogen bonds link the mol\u00adecules into dimers. These dimers are further linked into chains via inter\u00admolecular C\u2014H\u22efS hydrogen bonds. The crystal studied was a non-merohedral twin with a refined ratio of the twin components of 0.265\u2005(2):0.735\u2005(2).The asymmetric unit of title compound, [Fe(C DOI: 10.1107/S1600536810018209/rz2450Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The [Fe(H2O)6]2+ octa\u00adhedron has point symmetry 3(CO)3]\u2212 anion has point symmetry 1 and mean bond lengths of Fe\u2014Br = 2.455\u2005(5)\u2005\u00c5 and Fe\u2014C = 1.809\u2005(2)\u2005\u00c5. The cation and anion complexes are mutually linked via O\u2014H\u22efBr hydrogen bonds with O\u22efBr distances of 3.340\u2005(3) to 3.388\u2005(3)\u2005\u00c5.In the title compound, [Fe(H DOI: 10.1107/S1600536809036198/om2275Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Co(C9H10NO2)2(C10H14N2O)2(H2O)2], is centrosymmetric. It contains two dimethyl\u00adamino\u00adbenzoate (DMAB) and two diethyl\u00adnicotinamide (DENA) ligands and two water mol\u00adecules, all of them being monodentate. The four O atoms in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of DENA ligands with the Co\u2014N distance of 2.1519\u2005(11)\u2005\u00c5 in the axial positions. The Co atom is displaced out of the least-squares plane of the carboxyl\u00adate group by \u22120.781\u2005(1)\u2005\u00c5. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 5.05\u2005(7)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 71.48\u2005(5)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. Two weak C\u2014H\u22ef\u03c0 inter\u00adactions are also present.The title Co DOI: 10.1107/S1600536809030980/xu2578Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two pyridine-2,6-dicarboxyl\u00adate (pydc) ligands are bound to the NiII ion, giving an NiN2O4 bonded set. The coordination geometry around the NiII atom is distorted octa\u00adhedral. There are two types of robust O\u2014H\u22efO hydrogen-bond synthons, namely R               6               6(24) and R               2               4(8), which link the complex anions and water mol\u00adecules to each other. N\u2014H\u22efO hydrogen bonds connect the stacks of anions and cations in the structure. Other inter\u00admolecular inter\u00adactions, including weak C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 [shortest centroid\u2013centroid distance = 3.336\u2005(7)\u2005\u00c5] and C\u2014O\u22ef\u03c0 [O\u22efcentroid distance = 3.562\u2005(10)\u2005\u00c5] inter\u00adactions, connect the various components.The title compound, (C DOI: 10.1107/S1600536810016776/hy2305Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The average Hf\u2014O and Hf\u2014N distances are 2.096\u2005(3) and 2.398\u2005(3)\u2005\u00c5, respectively, and the average O\u2014Hf\u2014N bite angle is 70.99\u2005(11)\u00b0. The crystal packing is controlled by \u03c0\u2013\u03c0 inter\u00adactions between quinoline ligands of neighbouring mol\u00adecules and hydrogen-bonding inter\u00adactions. The inter\u00adplanar distances vary between 3.138\u2005(1) and 3.208\u2005(2)\u2005\u00c5, while the centroid\u2013centroid distances range from 3.576\u2005(1) to 4.074\u2005(1)\u2005\u00c5.In the title compound, [Hf(C DOI: 10.1107/S1600536809043244/bg2301Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Both RuIII atoms are octa\u00adhedrally coordinated by four chloride ligands in the equatorial plane and by two DMSO mol\u00adecules in apical positions within a RuCl4S2 donor set. The Na atom is surrounded by three chloride anions and three O atoms derived from three DMSO mol\u00adecules, with the resulting Cl3O3 donor set defining an octa\u00adhedron. The crystal structure is further stabilized by inter\u00adatomic inter\u00adactions of the types C\u22efCl [C\u2014Cl = 3.284\u2005(2)\u2005\u00c5], C\u2014H\u22efCl [C\u22efCl = 3.903\u2005(3)\u2005\u00c5] and C\u2014H\u22efO [C\u22efO = 3.376\u2005(3)\u2005\u00c5].The structure of the title compound, [NaRuCl DOI: 10.1107/S1600536810007063/tk2632Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bpbda ligand, lying on an inversion center, bridges two CuI centres into a Z-shaped complex. Intra\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the dipyridophenazine ligand and the benzene ring of the bpbda ligand are observed [centroid\u2013centroid distance = 3.459\u2005(3)\u2005\u00c5]. The crystal structure also involves inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the dipyridophenazine ligands [centroid\u2013centroid distance = 3.506\u2005(3)\u2005\u00c5], which lead to a one-dimensional supra\u00admolecular structure.In the centrosymmetric dinuclear title compound, [Cu DOI: 10.1107/S1600536809031754/hy2208Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The distorted octa\u00adhedral environment of MnII is defined by two N atoms [Mn\u2014N = 2.217\u2005(4) and 2.132\u2005(5)\u2005\u00c5] and one O atom [Mn\u2014O 2.305\u2005(4)\u2005\u00c5]. There are inter\u00admolecular O\u2014H\u22efS hydrogen bonds and inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent (2-pyrid\u00adyl)methano\u00adlate ligands [centroid\u2013centroid distance = 3.5569\u2005(7)\u2005\u00c5], leading to a chain structure running along [100].In the title complex, [Mn(NCS) DOI: 10.1107/S1600536810034483/bg2365Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure contains a CoII ion surrounded by the L               2\u2212 ligand in a slightly distorted square-planar fashion. Inter\u00admolecular C\u2014H\u22efO hydrogen-bonding contacts between the dichloro\u00admethane solvent mol\u00adecules and the meth\u00adoxy or carboxyl\u00adate O atoms are observed in the crystal structure. The planar complex mol\u00adecules stack through inversion related \u03c0\u2013\u03c0 inter\u00adactions between the six-membered rings of the vanillalimine half ligands. The distance between centroids is 3.498\u2005(2)\u2005\u00c5 and the perpendicular distance is 3.345\u2005\u00c5. A partial stacking is observed with a centroid\u2013centroid distance of 3.830\u2005(2)\u2005\u00c5, a perpendicular distance of 3.350\u2005\u00c5 and a slippage of 1.856\u2005\u00c5.The title compound, [Co(C DOI: 10.1107/S160053680900083X/si2147Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.655\u2005(3)\u2005\u00c5] and by three inter\u00admolecular C\u2014H\u22efO non-classical hydrogen bonds.The title compound, C DOI: 10.1107/S1600536809008460/rk2133Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal atoms display a distorted tetragonal-pyramidal coordination geometry, and are linked by two \u03bc               2- and two 3\u03bc-hydroxo groups, assuming a chair-like conformation for the Cu4O2 core. In the crystal, the complex mol\u00adecules are linked into a three-dimensional network by inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efCl, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid separations of 3.724\u2005(2) and 3.767\u2005(3)\u2005\u00c5.The tetra\u00adnuclear copper(II) title complex, [Cu DOI: 10.1107/S160053680804381X/rz2280Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The structure displays O\u2014H\u22efO hydrogen bonding and inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between 1,10-phenantroline ligands [inter\u00adplanar distance of 3.448\u2005(5)\u2005\u00c5]. In the structure of the title complex, [Cu(C DOI: 10.1107/S1600536809011659/gk2199Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Three chloridoaluminate groups and a hexa\u00admethyl\u00adbenzene mol\u00adecule are bound to the central lanthanum(III) ion, forming a distorted penta\u00adgonal bipyramid with the \u03b76-coordinated arene located at the apical position. The hexa\u00admethyl\u00adbenzene ligand disordered between two orientations in a 1:1 ratio is also involved in parallel-slipped \u03c0\u2013\u03c0 stacking inter\u00admolecular inter\u00adactions with a benzene solvent mol\u00adecule [centroid\u2013centroid distance 3.612\u2005(4)\u2005\u00c5].In the title compound, [Al DOI: 10.1107/S1600536809004899/cv2516Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules inter\u00adact via aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separation = 3.6741\u2005(18)\u2005\u00c5].In the title compound, [Pt(CH DOI: 10.1107/S1600536809055470/hb5294Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, inter\u00admolecular O\u2014H\u22efCl hydrogen bonds link the mol\u00adecules into a chain structure along [010]. There is a \u03c0\u2013\u03c0 contact between the pyridine rings [centroid\u2013centroid distance = 3.824\u2005(5)\u2005\u00c5].The Ni atom in the title compound, [NiCl DOI: 10.1107/S1600536808043961/at2700Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal ion is coordinated via the thia\u00adzole nitro\u00adgen, imine nitro\u00adgen and thione sulfur atoms from each thio\u00adsemicarbazone ligand, and two coordinating units lie almost perpendicular to each other give dihedral angle = 81.89\u2005(1)\u00b0]. One thio\u00adsemicarbazone unit is found to bind a chloride anion through two hydrogen bonds, while the other is linked with the disordered crystal water molecule. Two mol\u00adecules are connected to each other through an inter\u00admolecular N\u2014H\u22efS inter\u00adaction, forming a centrosymmetric dimer. Dimers are linked into sheets by \u03c0\u2013\u03c0 stacking of two phenyl rings [shortest C\u22efC distance = 4.041\u2005(3)\u2005\u00c5].In the title compound, [Ni(C DOI: 10.1107/S1600536810013280/br2143Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The nitrate ion inter\u00adacts with the copper center [Cu1\u22efO3 = 2.579\u2005(4)\u2005\u00c5]. In the crystal, the cations, anions and water mol\u00adecules are linked by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.In the title mononuclear complex, [Cu(C DOI: 10.1107/S1600536809052350/zq2021Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The diethyl ether mol\u00adecule is located in a cavity provided by four O atoms of the ligand with weak C\u2014H\u22efO inter\u00adactions, generating two short O\u22efO contact distances [2.766\u2005(3) and 2.745\u2005(3)\u2005\u00c5] between the diethyl ether mol\u00adecule and the ligand. The crystal structure is stabilized by the weak C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions between the naphthyl ring system and the benzene ring [centroid\u2013centroid distance = 3.657\u2005(5)\u2005\u00c5] and between the two naphthyl ring systems [centroid\u2013centroid distance = 4.305\u2005(2)\u2005\u00c5].In the title complex, [Co(C For rel al. 1984; Marzill al. 1985; \u00c1lvarez al. 2002. For hyd al. 2002. For non al. 2002; De Ange al. 1996. For the al. 2008.       26H20N2O4)(NCS)]\u00b7C4H10O\u00b7CH2Cl2                         = 0.075                           wR(F                           2) = 0.136                           S = 1.21                           7241 reflections397 parametersH-atom parameters constrainedmax = 0.69 e \u00c5\u22123                        \u0394\u03c1min = \u22120.60 e \u00c5\u22123                        \u0394\u03c1                                 CrystalClear (Rigaku, 2001CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2007SIR97 (Altomare et al., 1999SHELXL97 (Sheldrick, 2008SHELXL97; software used to prepare material for publication: CrystalStructure.Data collection: 10.1107/S1600536809000841/is2372sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000841/is2372Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "\u00c5]. In the crystal, mol\u00adecules are connected into supra\u00admolecular chains via \u03c0\u2013\u03c0 inter\u00adactions formed by the pyridine rings [centroid\u2013centroid distance = 3.552\u2005(3)\u2005\u00c5] and these are connected into a two-dimensional array in the ac plane by C\u2014H\u22ef\u03c0 contacts. One of the tert-butyl groups is disordered over two orientations in a 0.734\u2005(6):0.266\u2005(6) ratio.The structure of the dinuclear title complex, [Cu al. 2006. Acta Cr DOI: 10.1107/S1600536810015060/hb5416Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The planar imidazole ring system [maximum deviation = 0.012\u2005(3)\u2005\u00c5] is oriented at a dihedral angle of 6.08\u2005(5)\u00b0 with respect to the protonated pyridine ring. An O\u2014H\u22efCl inter\u00adaction links the water mol\u00adecule to the dianion. In the crystal structure, inter\u00admolecular O\u2014H\u22efCl, N\u2014H\u22efO and N\u2014H\u22efCl inter\u00adactions link the mol\u00adecules into a three-dimensional network.In the title compound, (C DOI: 10.1107/S1600536809024568/hk2717Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a \u03c0\u2013\u03c0 contact between the pyridine rings [centroid\u2013centroid distance = 3.9758\u2005(5)\u2005\u00c5].In the mol\u00adecule of the title compound, [HgCl DOI: 10.1107/S1600536808032777/hk2551Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII atom is bonded by two O atoms of the bidentate chelating sulfate ligand and four N atoms of the two chelating 2,2\u2032-bipyridine ligands. The Zn\u2014N bond distances range from 2.1287\u2005(17) to 2.1452\u2005(17)\u2005\u00c5 and the Zn\u2014O bond distance is 2.1811\u2005(15)\u2005\u00c5. The two chelating NCCN groups subtend a dihedral angle of 81.1\u2005(1)\u00b0. In the crystal structure, the [ZnSO4(C10H8N2)2] and C2H6O2 units are connected by inter\u00admolecular O\u2014H\u22efO hydrogen bonding, which leads to additional stabilization of the structure.The title compound, [Zn(SO DOI: 10.1107/S1600536809055433/bq2188Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, combined with weak (lone pair)\u22ef\u03c0 [O\u22efcentroid distance = 3.401\u2005(4)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distance = 3.975\u2005(3)\u2005\u00c5] inter\u00adactions, stabilize the three-dimensional supra\u00admolecular network.In the title compound, [Ag(NH DOI: 10.1107/S1600536810007725/hy2282Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two pyridine rings in each 2,2\u2032-bipyridine ligand form dihedral angles of 10.75\u2005(12) and 4.28\u2005(13)\u00b0. The crystal packing is stabilized by inter\u00adionic C\u2014H\u22efO hydrogen bonds, C\u2014H\u22ef\u03c0 inter\u00adactions and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances of 3.616\u2005(7)\u2005\u00c5.In the cation of the title compound, [CoCl(C DOI: 10.1107/S1600536809049034/rz2393Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The [Zn2Cl6(C8H4O4)]4\u2212 anions lie on centres of inversion and comprise two ZnCl3 groups bridged by benzene-1,4-dicarboxyl\u00adate. In addition to N\u2014H\u22efCl and N\u2014H\u22efO hydrogen bonds between the cations and anions, solvent water mol\u00adecules form O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds to give a three-dimensional network.The title compound, (C DOI: 10.1107/S1600536808033011/bi2304Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2-pyridinium cations are linked to these chains through pyridinium\u2013water N\u2014H\u22efO hydrogen bonds and a two-dimensional network is formed through water bridges between sulfonate and 2-nitro O atoms, while the structure also has weak cation\u2013anion \u03c0\u2013\u03c0 aromatic ring inter\u00adactions [minimum ring centroid separation = 3.8441\u2005(13)\u2005\u00c5].In the structure of the title salt, 2C DOI: 10.1107/S1600536810014819/ng2763Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the indole ring system, the benzene and pyrrole rings are nearly coplanar, forming a dihedral angle of 1.95\u2005(8)\u00b0. The cyclo\u00adhexenone ring has an envelope conformation. In the crystal structure, pairs of strong N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into centrosymmetric dimers with R               2               2(10) ring motifs. \u03c0\u2013\u03c0 contacts between parallel pyrrole rings [centroid\u2013centroid distance = 3.776\u2005(2)\u2005\u00c5] may further stabilize the structure. A weak C\u2014H\u22ef\u03c0 inter\u00adaction is also observed.The title compound, C DOI: 10.1107/S160053680902385X/xu2543Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both the stibine and arsine ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three stibine-substituted phenyl rings make dihedral angles of 84.3\u2005(3), 80.4\u2005(3) and 70.5\u2005(3)\u00b0 with each other. The dihedral angles between the two phenyl rings are 85.9\u2005(3) and 75.2\u2005(3)\u00b0 for the two diphenyl\u00adarsine groups. In the crystal packing, mol\u00adecules are linked into chains down the c axis via inter\u00admolecular C\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions further stabilize the crystal structure.In the title  DOI: 10.1107/S1600536809049927/sj2682Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two terminal C atoms of one allyl group are disordered over two sites of equal occupancy. The crystal structure is stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions, the centroid\u2013centroid distance between nearly parallel [dihedral angle = 19.82\u2005(4)\u00b0] benzene and imidazole rings being 3.7885\u2005(15)\u2005\u00c5.In the title compound, C DOI: 10.1107/S1600536810007890/xu2721Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular O\u2014H\u22ef and O\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid separation = 3.5535\u2005(13)\u2005\u00c5] link the mol\u00adecules into chains.In the title complex, [Mn(C DOI: 10.1107/S1600536809052659/hb5265Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "ZnN2O3 and ZnO5. All eight ZnII centers adopt a distorted square-pyramidal coordination; four ZnII ions have the N2O2 tetra\u00addentate Schiff base ligand bound in a basal plane and the coordinated water mol\u00adecule occupying the apical site, while the remaing four ZnII ions are bound by five O atoms from three Schiff base ligands. In the crystal structure, ZnII complex mol\u00adecules, coordinated and uncoord\u00adinated water mol\u00adecules and dimethyl sulfoxide mol\u00adecules are linked via O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional framework.The asymmetric unit of the title compound, tetra\u00adaqua\u00adtetrakis\u00ad{\u03bc II coordination complexes, see: Basak et al. 2007et al. 4(H2O)4]\u00b74C2H6OS\u00b72H2O = 0.050                           wR(F                           2) = 0.138                           S = 1.02                           5851 reflections314 parameters6 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.67 e \u00c5\u22123                        \u0394\u03c1min = \u22121.34 e \u00c5\u22123                        \u0394\u03c1                                 APEX2 (Bruker, 2005APEX2; data reduction: SAINT (Bruker, 2005SHELXTL (Sheldrick, 2008SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003Data collection: 10.1107/S1600536808017340/ci2611sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017340/ci2611Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one-half of the whole mol\u00adecule, and there is an inversion center at the mid-point of the Cu\u22efCu bond. The octa\u00adhedral coordination of each Cu atom, with four O atoms in the equatorial plane, is completed by the N atom of the 6-methyl\u00adquinoline mol\u00adecule [Cu\u2014N = 2.212\u2005(2)\u2005\u00c5] and by another Cu atom [Cu\u22efCu = 2.6939\u2005(13)\u2005\u00c5]. The Cu atom lies 0.234\u2005\u00c5 out of the plane of the four O atoms. The molecular packing is stabilized by one intramolecular C\u2014H\u22efO as well as C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 interactions.In the title compound, [Cu DOI: 10.1107/S1600536808016516/bx2146Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angles between the central benzene ring and the two outer rings are 7.62\u2005(16) and 9.78\u2005(17)\u00b0. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions with a centroid\u2013centroid distance of 3.8218\u2005(19)\u2005\u00c5.In the title Schiff base complex, [Ni(C DOI: 10.1107/S1600536810035890/su2210Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It is further extended to a two-dimensional layer structure by hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-centroid distances of 3.560\u2005(2) and 3.666\u2005(2)\u2005\u00c5]. There is a C4 water chain in the structure whose repeat unit contains four water mol\u00adecules with O\u22efO distances in the range 2.748\u2005(3)\u20132.795\u2005(4)\u2005\u00c5. One of the two H atoms of each water of hydration is statistically distributed over two positions with equal occupancy.The title complex, {[Cd(C DOI: 10.1107/S1600536808037203/pv2111Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Hydrogen bonding O\u2014H\u22efO between water molecules and between water anions as well as \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances between phen rings = 3.38\u2005(7) and 3.40\u2005(5)\u2005\u00c5] are responsible for the supra\u00admolecular assembly.In the title compound, [Cu(CHO DOI: 10.1107/S1600536808035320/pk2125Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the anionic polymer, the Mn2+ ions are bridged by the pyridine\u00adcarboxyl\u00adate (pic) anion ligand, forming a chain structure along the c axis. The Mn2+ ion is six-coordinated in a distorted octa\u00adhedral environment by one N atom of the pyridine ring, two O atoms of the two carboxyl\u00adate groups, one O atom of the water mol\u00adecule and two Br atoms. The compound displays inter\u00admolecular N\u2014H\u22efO, N\u2014H\u22efBr, O\u2014H\u22efBr and O\u2014H\u22efO hydrogen bonding. There may also be inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between adjacent pyridine rings, with a centroid\u2013centroid distance of 3.992\u2005(4)\u2005\u00c5.The asymmetric unit of the title compound, {(C DOI: 10.1107/S1600536809016316/cs2117Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "These polymeric chains generate microchannels extending along [100], and these cavities are occupied by discrete tetra\u00addeca\u00admeric water clusters, which inter\u00adact with their surroundings and finally furnish the three-dimensional supra\u00admolecular network via 15 O\u2014H\u22efO, one O\u2014H\u22efS, two O\u2014H\u22efN and six N\u2014H\u22efO classical hydrogen bonds. 4,4-Bipyridine acts as an inserting component and hydrogen-bond acceptor, and it is a nonplanar mol\u00adecule with a dihedral angle of 33.12\u2005(13)\u00b0 between the pyridine rings. Owing to the numerous classical hydrogen bonds, the observed weak inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions can be neglected with regard to stabilizing the network.In the title compound, {[La DOI: 10.1107/S1600536808031450/si2111Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a \u03c0\u2013\u03c0 stacking inter\u00adaction between the five-membered ring containing the Cu atom and a pyridine ring of a neighboring complex [centroid\u2013centroid distance = 3.567\u2005(2)\u2005\u00c5 and a perpendicular distance of 3.394\u2005\u00c5]. The crystal structure also contains inter\u00admolecular N\u2014H\u22efO, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, linking cations and anions. In addition, there is a short inter\u00admolecular contact [2.784\u2005(6)\u2005\u00c5] between an O atom of the coordinated nitrate group and its symmetry-related atom.In the title mononuclear complex, [Cu(NO DOI: 10.1107/S1600536808015523/wn2264Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atoms in the crystal structure of the title compound, (C2H10N2)[HgBr4]\u00b7H2O, are tetra\u00adhedrally coordinated by four Br atoms and the resulting [HgBr4]2\u2212 ions are inter\u00adconnected to the [NH3\u2014CH2\u2014CH2\u2014NH3]2+ ions and water mol\u00adecules by N\u2014H\u22efBr and O\u2014H\u22efBr bonds, forming a three-dimensional network. N\u2014H\u22efO inter\u00adactions are also present. The observed three different Hg\u2014Br distances of 2.5597\u2005(6), 2.6862\u2005(8) and 2.6923\u2005(8)\u2005\u00c5 in the tetra\u00adbromo\u00admercurate unit are due to the connection of Br atoms to different numbers of H atoms. The Hg, O and two Br atoms are located on a crystallographic mirror plane. The cation has The Hg DOI: 10.1107/S160053680902772X/bt5004Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The diimine ligand is equatorial and is bonded to the Re centre in an N,N\u2032-bidentate chelating fashion, with a bite angle of 77.7\u2005(2)\u00b0. The dihedral angle between the two benzene rings is 88.7\u2005(6)\u00b0. In the crystal structure, there are F\u22efO [2.856\u2005(9)\u2005\u00c5], Cl\u22efC [3.150\u2005(8)\u2005\u00c5] and O\u22efC [2.984\u2005(10)\u2005\u00c5] contacts which are shorter than the sum of the van der Waals radii for these atoms. In addition, symmetry-related mol\u00adecules are linked via inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efBr and the F\u22efO inter\u00adactions into one-dimensional chains extending along the a axis. The crystal structure is further stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.571\u2005(5)\u2005\u00c5].In the title compound, [ReBr(C DOI: 10.1107/S1600536809001044/lh2753Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The compound is a seven-coordinate binuclear polymeric complex with distorted penta\u00adgonal bipyramidal geometry around CdII [Cd\u2014O = 2.247\u2005(4)\u20132.474\u2005(3)\u2005\u00c5]. In the binuclear monomeric units, the central atoms join together by O atoms of two bridging tridentate (hypydc)2\u2212 ligands, and the polymer propagates via two bridging water mol\u00adecules that link each CdII centre of one monomer to the adjacent neighbour. Propane-1,3-diamine (pn) does not appear in the product but plays a role as a base. Inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, and \u03c0\u2013\u03c0 stacking inter\u00adactions, with distances of 3.725\u2005(3) and 3.766\u2005(3)\u2005\u00c5, connect the various components.The title polymeric compound, {[Cd DOI: 10.1107/S1600536808030869/om2258Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CdII atom shows a distorted octa\u00adhedral environment, with four N atoms from two chelating 2,2\u2032-bipyridine ligands forming the equatorial plane and two sulfonate O atoms from two 9,10-dioxoanthracene-1,5-disulfonate anions occupying the apical positions. Weak C\u2014H\u22efO hydrogen-bonding contacts and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.6920\u2005(12) and 3.7095\u2005(12)\u2005\u00c5] connect the complex mol\u00adecules into a three-dimensional supra\u00admolecular framework.The title complex, [Cd(C DOI: 10.1107/S1600536809046881/si2219Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The NiII atom is coordinated by two N atoms [Ni\u2014N = 1.839\u2005(2)\u2005\u00c5] and two O atoms [Ni\u2014O = 1.8253\u2005(19)\u2005\u00c5] in an approximately square-planar geometry. In the crystal structure, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a chain along [001].The monomeric title nickel(II) complex of a salicylaldimine, [Ni(C DOI: 10.1107/S160053680904063X/ds2006Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu\u22efCu separation is 2.5912\u2005(4)\u2005\u00c5. In the crystal, the mol\u00adecules are linked into polymeric chains propagating in [001] by inter\u00admolecular O\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Cu DOI: 10.1107/S1600536810013322/bq2206Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The conformation of the dimer is stabilized by inter\u00admolecular C\u2014H\u22efO hydrogen bonds and by \u03c0\u2013\u03c0 aromatic stacking inter\u00adactions involving the pyridine and benzene rings with centroid\u2013centroid separations of 3.624\u2005(3)\u2005\u00c5.The dinuclear title complex, [Cu DOI: 10.1107/S1600536809053665/rz2402Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII atom is coordinated by four O and two N atoms from two pydc ligands in a distorted octa\u00adhedral environment. The structure also contains three uncoordinated water mol\u00adecules. Extensive inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.565\u2005(14) and 3.425\u2005(14)\u2005\u00c5] and O\u22ef\u03c0 inter\u00adactions [O\u22efcentroid distance = 3.480\u2005(2)\u2005\u00c5] connect the various components in the crystal structure.The title compound, (C DOI: 10.1107/S1600536809021837/hy2201Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the aromatic rings in the ligand is 8.70\u2005(16)\u00b0. The S atom is disordered over two positions in a 0.901\u2005(6):0.099\u2005(6) ratio. In the crystal, mol\u00adecules inter\u00adact by way of \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separation = 3.720\u2005(2)\u2005\u00c5].In the title compound, [Cu(C DOI: 10.1107/S1600536810014212/hb5406Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ni ion is coordinated by two N [Ni\u2014N = 1.8462\u2005(18)\u2005\u00c5] and two O [Ni\u2014O = 1.8645\u2005(14)\u2005\u00c5] atoms in a distorted square-planar geometry. The water mol\u00adecule and the Ni complex mol\u00adecule are paired via O\u2014H\u22efO hydrogen bonds.In the title compound, [Ni(C DOI: 10.1107/S1600536808039822/cv2487Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Short centroid\u2013centroid distances [3.762\u2005(5) and 3.867\u2005(5)\u2005\u00c5] between the aromatic rings of neighbouring cations suggest the existence of \u03c0\u2013\u03c0 inter\u00adactions. Inter\u00admolecular O\u2014H\u22efBr hydrogen bonds and weak C\u2014H\u22efO and C\u2014H\u22efBr inter\u00adactions consolidate the crystal packing.In the title compound, [CuBr(C DOI: 10.1107/S1600536809048995/cv2644Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Pairs of complex mol\u00adecules related by inversion centers are organized into dimers via pairs of Pb\u22efO inter\u00adactions [3.185\u2005(2)\u2005\u00c5] and stacking interactions between 2,2\u2032-bipyridine and 4-methyl\u00adbenzoate ligands, with a mean distance between their planes of 3.491\u2005\u00c5.In the title compound, [Pb(C DOI: 10.1107/S1600536810005544/gk2256Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The NiII atom lies on an inversion centre and is coordinated by four S atoms of O,O\u2032-diphenethyl dithio\u00adphosphate mol\u00adecules and two N atoms of 4-methyl\u00adpyridine mol\u00adecules. Important geometric data include Ni\u2014N = 2.100\u2005(3)\u2005\u00c5, and Ni\u2014S = 2.5101\u2005(10) and 2.4772\u2005(11)\u2005\u00c5.The title complex, [Ni(C DOI: 10.1107/S1600536808020898/dn2365Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An offset face-to-face \u03c0\u2013\u03c0 stacking inter\u00adaction [centroid\u2013centroid distance = 3.674(4)\u2005\u00c5] and N\u2014H\u22efN and N\u2014H\u22efO hydrogen-bonding inter\u00adactions give rise to a one-dimensional supra\u00admolecular structure in the solid state.In the centrosymmetric title compound, [Ni(C DOI: 10.1107/S1600536808001116/pk2081Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One pair of phenyl rings attached to the two different P atoms are almost parallel, as are the other pair [dihedral angles = 8.7\u2005(5) and 8.9\u2005(5)\u00b0]. The planes of the two cyclo\u00adpenta\u00addienyl rings are inclined by 26.8\u2005(7)\u00b0 with respect to each other. The carbonyl groups at each Fe atom are almost perpendicular [C\u2014Fe\u2014C = 92.6\u2005(6) and 94.3\u2005(5)\u00b0].The title compound, [Fe DOI: 10.1107/S1600536808014931/bq2081Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination geometry is distorted tetra\u00adhedral, with Sn\u2014C bond lengths in the range 2.133\u2005(6)\u20132.188\u2005(6)\u2005\u00c5 and with an Sn\u2014S bond length of 2.4516\u2005(19)\u2005\u00c5. The nonbonded S atom of the piperidine\u00addithio\u00adcarboxyl\u00adate anion makes an Sn\u22efS contact of 3.174\u2005(3)\u2005\u00c5.In the title compound, [Sn(C DOI: 10.1107/S1600536808021909/bi2291Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ni atom lies on a crystallographic twofold rotation axis. The asymmetric unit contains one half-mol\u00adecule of the complex and a water mol\u00adecule. An inter\u00admolecular O\u2014H\u22efO hydrogen bond forms a four-membered ring, producing an R               1               2(4) ring motif involving a bifurcated hydrogen bond to the phenolate O atoms of the complex mol\u00adecule. In the crystal structure, mol\u00adecules are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances in the range 3.5750\u2005(11)\u20133.7750\u2005(11)\u2005\u00c5. As a result of the twofold symmetry, the central benzene ring makes the same dihedral angle of 15.75\u2005(9)\u00b0 with the two outer benzene rings. The dihedral angle between the two hydroxy\u00adphenyl rings is 13.16\u2005(5)\u00b0. In the crystal structure, mol\u00adecules are linked into infinite one-dimensional chains by directed four-membered O\u2014H\u22efO\u2014H inter\u00adactions along the c axis and are further connected by C\u2014H\u22efO and \u03c0\u2013\u03c0 stacking into a three-dimensional network. An inter\u00adesting feature of the crystal structure is the short Ni\u22efO, O\u22efO and N\u22efN inter\u00adactions which are shorter than the sum of the van der Waals radii of the relevant atoms. The crystal structure is stabilized by inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and by \u03c0\u2013\u03c0 stacking inter\u00adactions.In the title complex, [Ni(C DOI: 10.1107/S1600536808026093/pk2114Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Weak inter\u00admolecular C\u2014H\u22efBr hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.763\u2005(5) and 3.835\u2005(6)\u2005\u00c5] contribute to crystal-packing effects.In the title compound, [ZnBr DOI: 10.1107/S1600536810035658/jj2041Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The MgII ion is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms from coordinated water mol\u00adecules in a distorted octa\u00adhedral geometry. Inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings [shortest centroid\u2013centroid separation = 3.527\u2005(2)\u2005\u00c5] link the cations, anions and 1,10-phenanthroline solvent mol\u00adecules into a hydrogen-bonded cluster.In the title compound, [Mg(C DOI: 10.1107/S1600536809030128/cv2597Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, the carboxyl groups are involved in inter\u00admolecular O\u2014H\u22efO hydrogen bonds, which link the mol\u00adecules into centrosymmetric dimers. These dimers are further packed into stacks along the c axis by weak C\u2014H\u22ef\u03c0 inter\u00adactions. In addition, the stacked mol\u00adecules exhibit a Br\u22efS inter\u00adaction of 3.4787\u2005(7)\u2005\u00c5.The title compound, C DOI: 10.1107/S1600536809005376/fj2195Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Intra\u00admolecular C\u2014H\u22efO inter\u00adactions occur. The mol\u00adecules are connected by inter\u00admolecular N\u2014H\u22efO, N\u2014H\u22efN and C\u2014H\u22efO hydrogen-bonding inter\u00adactions and C\u2014H\u22ef\u03c0 stacking inter\u00adactions, forming a three-dimensional supra\u00admolecular frameworkIn the title compound, [Sb(C DOI: 10.1107/S1600536809043578/gk2233Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the anion, four distorted [MoO6] octa\u00adhedra are connected via edge-sharing, forming an [Mo4O13]2\u2212 building block, composed of Mo\u2014O(t), Mo\u2014O(\u03bc2), Mo\u2014O(\u03bc3) and Mo\u2014O(\u03bc4) units, with Mo\u2014O distances ranging from 1.6858\u2005(15) to 2.4785\u2005(13)\u2005\u00c5. The \u03b3-type [Mo8O26]4\u2212 anion is completed by crystallographic inversion symmetry and is linked into an infinite chain along [100] by corner-sharing. The anionic chains and the cations are joined by N\u2014H\u22efO hydrogen bonds, generating layers extending parallel to (001).In the title compound, {(C DOI: 10.1107/S1600536810010111/wm2312Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two benzothia\u00adzole-2-thiol\u00adate ligands chelate via their thia\u00adzole N and thiol\u00adate S atoms while the methyl 2-(2-amino\u00adthia\u00adzol-4-yl)-2-(methoxy\u00adimino)acetate also acts as a chelate ligand binding through the thia\u00adzole and imino N atoms. Intra\u00admolecular N\u2014H\u22efN, C\u2014H\u22efN and C\u2014H\u22efO inter\u00adactions contribute to the mol\u00adecular conformation. In the crystal structure, inter\u00admolecular N\u2014H\u22efO hydrogen bonds produce R               1               2(6) rings and generate chains along the c axis. An extensive one-dimensional supra\u00admolecular network of N\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions is responsible for the crystal structure stabilization.In the title compound, [Ni(C DOI: 10.1107/S1600536810015072/sj2774Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The other Sn atom also has a distorted trigonal bipyramidal geometry, being coordinated by two O atoms of two carboxyl\u00adate anions, one bridging O atom and two butyl groups. An inter\u00adesting feature of the crystal structure is the short Sn\u22efO [2.756\u2005(4)\u2005\u00c5] and O\u22efO [2.608\u2005(3)\u2005\u00c5] inter\u00adactions. The \u2013BrCH2\u2014CHBr\u2013 segments of the two carboxyl\u00adate anions are disordered over two positions [site occupancies of 0.60\u2005(1)/0.40\u2005(1) and 0.53\u2005(2)/0.47\u2005(2)]. Weak non-directional C\u2014H\u22efO inter\u00adactions lead to the formation of infinte chains along the a axis; other weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are also present.In the centrosymmetric tetra\u00adnuclear title complex, [Sn DOI: 10.1107/S1600536808037513/ng2514Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, aromatic \u03c0\u2013\u03c0 stacking occurs [centroid\u2013centroid distances 3.7630\u2005(14) and 3.7269\u2005(15)\u2005\u00c5], as well as an extensive O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding networkIn the title compound, [Co(C DOI: 10.1107/S1600536808019843/hb2753Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In athymic rats, \u03b3/\u03b4 T-cells expressing intracellular \u03b2 proteinare present but at a lower frequency than in euthymic controls, suggesting that in the thymus,more \u03b3/\u03b4 T-cell precursors pass through a stage where functional \u03b2 rearrangement hasoccurred than in extrathymic sites. Analysis of TCR expression in purified transitory immatureCD4-8+ (iCD8SP) thymocytes and their spontaneously developing CD4+8+ (DP) progenyshowed that TCR\u03b3 mRNA is expressed in iCD8SP cells but not in their immediate DPprogeny that reinitiate RAG-1 transcription and commence \u03b1/\u03b2TCR expression. We concludethat rat \u03b3/\u03b4 T cells can separate from the \u03b1/\u03b2 lineage after TCR\u03b2 expression, but not afterentry into the DP compartment.The relationship between \u03b1/\u03b2 and \u03b3/\u03b4 T-cell lineages was studied in rats using RT-PCR analysisof TCR\u03b2 transcripts in \u03b3/\u03b4 T-cell hybridomas and an intracellular staining technique todetect TCR\u03b2 protein in primary \u03b3/\u03b4 T-cells. We report the presence of functional TCR\u03b2 transcriptsin 2/9 \u03b3/\u03b4 T-cell hybridomas. About 15 % of peripheral \u03b3/\u03b4 T-cells and thymocytes alsoexpress TCR\u03b2 protein, giving a minimum estimate for successful Tcrb rearrangement basedon"}
{"text": "The two CdII ions are connected by two tridentate bridging 2-hydroxy\u00adbenzoate anions. Each CdII ion is seven-coordinated by five O atoms from three 2-hydroxy\u00adbenzoate ligands and two N atoms from 1,10-phenanthroline. The 2-hydroxy\u00adbenzoate mol\u00adecules adopt two kinds of coordination mode, bidentate chelating and tridentate bridging\u2013chelating. Intra\u00admolecular hydrogen bonds between hydr\u00adoxy and carboxyl\u00adate groups from 2-hydroxy\u00adbenzoate groups and \u03c0\u2013\u03c0 stacking interactions between parallel 1,10-phenanthroline ligands [centroid\u2013centroid distances = 3.707\u2005(3) and 3.842\u2005(3)\u2005\u00c5] are observed. Furthermore, adjacent benzene rings from 2-hydroxy\u00adbenzoate ligands are involved in \u03c0\u2013\u03c0 inter\u00adactions with inter\u00adplanar distances of 3.642\u2005(3)\u2005\u00c5, thereby forming a chain along the a axis direction.The dinuclear title compound, [Cd DOI: 10.1107/S1600536808033886/zl2145Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each PtII center is coordinated by the amine groups of two (1-adamantylmeth\u00adyl)amine ligands and two Cl atoms in a cis-square-planar arrangement. The PtII centers lie slightly outside [0.031\u2005(4) and 0.038\u2005(4)\u2005\u00c5] the coordination planes. The N\u2014Pt\u2014N and Cl\u2014Pt\u2014Cl angles [92.1\u2005(4)\u201392.30\u2005(11)\u00b0] are slightly more open than the N\u2014Pt\u2014Cl angles [87.3\u2005(3)\u201388.3\u2005(3)\u00b0]. N\u2014H\u22efO and N\u2014H\u22efCl inter\u00admolecular hydrogen bonds are observed, forming two discrete pairs of complexes and solvent mol\u00adecules.The asymmetric unit of the title compound {systematic name:  DOI: 10.1107/S1600536809037982/hy2221Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The carboxyl\u00adate groups are approximately coplanar with the thio\u00adphene ring [dihedral angle = 4.0\u2005(1)\u00b0] and the Sn\u2014O bond distance of 2.058\u2005(4)\u2005\u00c5 is comparable to that in related organotin carboxyl\u00adates.Mol\u00adecules of the title compound, [Sn DOI: 10.1107/S1600536809020273/bi2371Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement with an average Ni\u2014O bond length of 2.079\u2005\u00c5, and the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the nicotinamide (NA) ligands in the axial positions. The dihedral angle between the carboxyl group and the attached benzene ring is 28.28\u2005(11)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 8.31\u2005(4)\u00b0. In the crystal structure, O\u2014H\u22efO, N\u2014H\u22efO, C\u2014H\u22efO, and C\u2014H\u22efF hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 Contacts between the pyridine and benzene rings [centroid\u2013centroid distance = 3.626\u2005(1)\u2005\u00c5] may further stabilize the crystal structure. The 2-fluoro\u00adbenzoate anion is disordered over two orientations, with an occupancy ratio of 0.85:0.15.The asymmetric unit of the title complex, [Ni(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(H2O)4](C7H4FO2)2                         = 0.026                           wR(F                           2) = 0.071                           S = 1.04                           3339 reflections221 parameters7 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.55 e \u00c5\u22123                        \u0394\u03c1min = \u22120.70 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536809040392/xu2610sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809040392/xu2610Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Since assay constraints limited the data at lower doses, conventional analysis was not feasible and a \u2018population approach\u2019 was used. Bound concentrations were best described by a biexponential model and further analyses revealed a small influence of dose or weight on V1 but no identifiable effects of age, body surface area, renal or hepatic function. The final model was: clearance (Q) 0.194 l h\u22121; central compartment volume (V1) 4.48 \u00d7 (1+0.00074 \u00d7 dose (mg)) l; peripheral compartment volume (V2) 7.94 l; intercompartmental clearance 0.685 l h\u22121. Distribution and elimination half-lives had median estimates of 2.7 h and 49 h respectively. Free doxorubicin was present at most sampling times with concentrations around 1000 times lower than bound doxorubicin values. Data were best described using a biexponential model and the following parameters were estimated: apparent clearance 180 l h\u22121; apparent V1 (l) 1450 \u00d7 (1+0.0013 \u00d7 dose (mg)), apparent V2 (l) 21 300 \u00d7 (1\u20130.0013 \u00d7 dose (mg)) \u00d7 (1+2.95 \u00d7 height (m)) and apparent Q 6950 l h\u22121. Distribution and elimination half-lives were 0.13 h and 85 h respectively. \u00a9 1999 Cancer Research CampaignDoxorubicin pharmacokinetics were determined in 33 patients with solid tumours who received intravenous doses of 20\u2013320 mg m"}
{"text": "The structure contains [Mn(C10H8N2)(H2O)4]2+ cations with the MnII atoms lying on a centres of inversion and bridged into a linear chain along the a axis by 4,4\u2032-bipy ligands, surrounded by HL               \u2212 anions and uncoordinated water mol\u00adecules. Extensive O\u2014H\u22efO hydrogen-bonding and weak \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.7572 \u2005(3)\u2005\u00c5] between the constituents lead to the formation of a three-dimensional supra\u00admolecular network.The title compound, {[Mn(C DOI: 10.1107/S1600536809028360/at2846Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Adjacent silver complexes are primarily linked together by Ag\u22efN inter\u00adactions, with Ag\u22efN separations of 2.877\u2005(2) and 3.314\u2005(2)\u2005\u00c5. On the other hand, one CF3SO3               \u2212 anion inter\u00adacts with hydrazone groups of two neighbouring ligands via N\u2014H\u22efO hydrogen bonds. These weak inter\u00admolecular inter\u00adactions contribute to the formation of supra\u00admolecular chains. In addition, there are Ag\u22efO inter\u00adactions [2.787\u2005(2)\u2005\u00c5] between Ag and O atoms from adjacent chains.In the title compound, [Ag(C DOI: 10.1107/S1600536809039579/bh2248Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atoms in the two independent mol\u00adecules of the title compound, [Cu(C7H5O3)2(C14H12N2)], are each coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) mol\u00adecule and two monodentate 2-hydroxy\u00adbenzoate anions in a distorted tetra\u00adhedral geometry. The crystal packing is stabilized by intra\u00admolecular hydrogen bonding and \u03c0\u2013\u03c0 inter\u00adactions between the dmphen rings of neighboring mol\u00adecules, with distances between their ring planes of 3.5670\u2005(4) and 3.5181\u2005(9)\u2005\u00c5.The Cu DOI: 10.1107/S1600536808036283/hg2438Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The L ligands are coordinated to the HoIII ions in three modes: chelating, bridging and bridging\u2013tridentate. Intra\u00admolecular C\u2014H\u22efO inter\u00adactions occur. The crystal packing is stabilized by inter\u00admolecular C\u2014H\u22efO inter\u00adactions and weak aromatic \u03c0\u2013\u03c0 inter\u00adactions between phen mol\u00adecules and the aromatic rings of the L ligands [centroid\u2013centroid distance = 3.821\u2005(2)\u2005\u00c5].In the centrosymmetric title compound, [Ho DOI: 10.1107/S1600536810036408/pv2299Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The PdII cation is situated on an inversion centre and exhibits an almost square-planar coordination by the S atoms of the TU ligands. The complex cations are connected through the thio\u00adcyanate ions via N\u2014H\u22efN [2.922\u2005(3)\u20133.056\u2005(3)\u2005\u00c5] and N\u2014H\u22efS [3.369\u2005(2)\u20133.645\u2005(2)\u2005\u00c5] hydrogen bonds.The title compound, [Pd(CH DOI: 10.1107/S160053680801088X/wm2176Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, the deca\u00advanadate [V10O28]6\u2212 anion 3}2(\u03bc-H2O)2]2+ units. Inter\u00adconnection of these aquasodium-ion-sandwiched deca\u00advanadates to chains parallel to [001] is effected by \u03bc-[{Na(H2O)3}2(\u03bc-H2O)2]2+ units, bridging adjacent deca\u00advanadates via O=V. The structure is consolidated by an extensive network of  O\u2014H\u22efO hydrogen bonds.The title compound, {[Na(H DOI: 10.1107/S1600536810010251/br2141Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing exhibits inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions evidenced by relatively short distances [3.525\u2005(5)\u20133.937\u2005(6)\u2005\u00c5] between the centroids of the six-membered rings of neighbouring mol\u00adecules.In the title compound, [Cd(C DOI: 10.1107/S1600536807067918/cv2375Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both the phosphine and arsine ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine-substituted phenyl rings make dihedral angles of 87.36\u2005(10), 81.96\u2005(10) and 73.37\u2005(11)\u00b0 with each other. The dihedral angles between the two phenyl rings are 88.08\u2005(12) and 80.15\u2005(10)\u00b0 for the two diphenyl\u00adphosphino groups. In the crystal packing, the mol\u00adecules are linked together as dimers via inter\u00admolecular C\u2014H\u22efO hydrogen bonds. These dimers are stacked down b axis. Inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6383\u2005(13)\u2005\u00c5] further stabilize the crystal structure.In the title  DOI: 10.1107/S1600536809046704/sj2670Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "In the crystal structure, each RuII ion is coordinated by two Cl [Ru\u2014Cl = 2.4308\u2005(7) and 2.4139\u2005(7)\u2005\u00c5], two N [Ru\u2014N = 2.016\u2005(2) and 2.003\u2005(2)\u2005\u00c5], and two P [Ru\u2014P\u00a0= 2.3688\u2005(7) and 2.3887\u2005(7)\u2005\u00c5] atoms in a distorted octa\u00adhedral geometry. Packing inter\u00adactions include typical C\u2014H\u22ef\u03c0 contacts involving phenyl groups as well as weak hydrogen bonds between CH3CN methyl H atoms and Cl or solvent CH3CN N atoms.The title compound, [RuCl DOI: 10.1107/S1600536807065968/ci2537Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The tetra\u00adfluorido\u00adborate anions link the mononuclear cations through inter\u00admolecular C\u2014H\u22efF hydrogen-bonding inter\u00adactions, forming an infinite tape structure along [110]. Other weak inter\u00adactions occur: \u03c0\u2013\u03c0 stacking with centroid\u2013centroid distances of 3.820\u2005(2) and 3.898\u2005(1)\u2005\u00c5 between pyridyl rings and 3.610\u2005(2) and 3.926\u2005(2)\u2005\u00c5 between pyrazinyl rings as well as F\u22ef\u03c0 contacts involving the tetra\u00adfluorido\u00adborate anions and pyrazine rings [F\u22efcentroid = 2.999\u2005(3)\u2005\u00c5]; these combine with the hydrogen-bonding inter\u00adactions to link the mononuclear cations into a three-dimensional supra\u00admolecular architecture.In the title mononuclear complex, [Ag(C DOI: 10.1107/S1600536810035178/bg2359Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The central AgI ion is coordinated by two different N atoms in the aromatic rings of the ligands, with an N\u2014Ag\u2014N angle of 173.9\u2005(2)\u00b0. The crystal structure is composed of two complexed cations and stabilized by an inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efN hydrogen-bond network and there is \u03c0\u2013\u03c0 stacking of the aromatic rings [inter\u00adplanar distance 3.651\u2005(10)\u2005\u00c5].Colourless crystals of the title compound, [Ag(C DOI: 10.1107/S1600536809035181/jh2100Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, centrosymmetric dimers are formed through \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.624\u2005(2)\u2005\u00c5] between the substituted ferrocene ring and the three fused rings of the naphthalic anhydride unit. Pairs of dimers are held together by further naphthalene\u2013naphthalene \u03c0\u2013\u03c0 interactions [distance between parallel mean planes 3.45\u2005(3)\u2005\u00c5]. Each dimer inter\u00adacts with four neighbouring dimers in a herringbone fashion through C\u2014H\u22ef\u03c0 inter\u00adactions, so forming a two-dimensional sheet-like structure.In the structure of the title compound, [Fe(C DOI: 10.1107/S1600536808007393/su2047Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Mo\u2014Mo distance is 2.5732\u2005(4)\u2005\u00c5. The perpendicular distances of the Mo atoms from the C7 planes are 1.5827\u2005(8) and 1.5814\u2005(8)\u2005\u00c5, with individual Mo\u2014C bond lengths in the range 2.261\u2005(2)\u20132.2789\u2005(14)\u2005\u00c5. Mo\u2014H distances range from 1.77\u2005(3) to 1.85\u2005(4)\u2005\u00c5, with Mo\u2014H\u2014Mo angles of 89\u2005(2) and 92\u2005(1)\u00b0.In the title compound, [Mo DOI: 10.1107/S1600536808042244/bt2832Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII(TPP) complex exhibits a nearly planar conformation of the porphyrinate core [maximum deviation = 0.069\u2005(2)\u2005\u00c5] with an average Co\u2014N distance of 1.971\u2005(4)\u2005\u00c5. The distance between the Co atom and the closest O atom of the 18-crown-6 mol\u00adecule is 2.533\u2005(2)\u2005\u00c5, indicating a short non-bonded contact between the Co atom and the crown ether mol\u00adecule. An ethyl\u00adene group of the 18-crown-6 mol\u00adecule is disordered over two sites with occupancies of 0.565\u2005(7) and 0.435\u2005(7).The asymmetric unit of the title compound, [Co(C DOI: 10.1107/S1600536810012080/pv2268Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle formed by the pyridine and benzene rings is 74.61\u2005(5)\u00b0. Intra\u00admolecular C\u2014H\u22efO hydrogen bonds are present. The crystal structure is stabilized by weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions involving neighbouring pyridine rings [centroid\u2013centroid distance = 3.853\u2005(2)\u2005\u00c5].In the mononuclear title complex, [Cu(C DOI: 10.1107/S1600536809029523/rz2354Isup2.hkl            Structure factors: contains datablocks I. DOI:"}
{"text": "In the crystal structure, there is a weak \u03c0\u2013\u03c0 stacking inter\u00adaction between adjacent 1,10-phenanthroline rings, with a pyridine centroid\u2013centroid distance of 3.6620\u2005(15)\u2005\u00c5.In the title complex, [Zn(NCS) DOI: 10.1107/S1600536808011793/lh2603Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing is stabilized by \u03c0\u2013\u03c0 ; C\u2014H\u22ef\u03c0\u22eftolyl ring inter\u00adactions are also present.In the mol\u00adecule of the title compound, C DOI: 10.1107/S1600536808023222/dn2368Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized via inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine and benzene rings of neighboring phen ligands .In the title mononuclear complex, [Cu(C DOI: 10.1107/S1600536809053483/hy2263Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The N\u2014Ni\u2014N angle is 78.64\u2005(8)\u00b0. Weak but significant \u03c0\u2013\u03c0 stacking inter\u00adactions exist between the pyridine rings with a centroid\u2013centroid distance of 3.652\u2005(8)\u2005\u00c5. In addition, four O atoms of the two carboxyl groups form hydrogen bonds with both coordinated and uncoordinated water mol\u00adecules, forming an infinite three-dimensional network.In the title compound, [Ni(C DOI: 10.1107/S1600536809035910/ng2636Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The uncoordinated water mol\u00adecules are involved in O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, which contribute to the formation of a three-dimensional supra\u00admolecular structure, along with \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances of 3.5313\u2005(13) and 3.6028\u2005(11)\u2005\u00c5 between the pyridine rings of neighbouring dianions].In the title compound, (C DOI: 10.1107/S1600536808029395/cv2442Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu\u2014Cu distance is 2.6458\u2005(4)\u2005\u00c5. In the crystal structure, the dinuclear units are linked into a three-dimensional network by O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds. One of the Cl atoms is disordered over two positions with occupancies of 0.650\u2005(2) and 0.350\u2005(2).In the title binuclear copper(II) complex, [Cu DOI: 10.1107/S1600536808041986/ci2732Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An intra\u00admolecular C\u2014H\u22efO inter\u00adaction forms an S(7) ring motif. The dihedral angles between the benzoate group and the other three phenyl rings are 76.94\u2005(8), 66.82\u2005(8) and 42.34\u2005(9)\u00b0. The crystal structure is further stabilized by inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Sn(C DOI: 10.1107/S1600536808036337/kp2195Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by weak non-classical inter\u00admolecular C\u2014H\u22efO hydrogen-bond inter\u00adactions. The crystal structure also exhibits aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions between furan/benzene and benzene/benzene rings of adjacent benzofuran ring systems [centroid\u2013centroid distances = 3.8258\u2005(9) and 3.8794\u2005(9)\u2005\u00c5] and a weak inter\u00admolecular C\u2014H\u22ef\u03c0 ring inter\u00adaction.In the title compound, C DOI: 10.1107/S1600536809030451/jj2003Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure exhibits aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.643\u2005(2)\u2005\u00c5] and nonclassical C\u2014H\u22efO hydrogen bonds.In the title compound, C DOI: 10.1107/S1600536809020613/cv2569Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "All six 4-methoxy\u00adbenzoate ligands act in a bidentate mode, two coordinating to one Tb center each and the other four bridging two Tb centers [Tb\u22efTb separation = 4.3144\u2005(6)\u2005\u00c5]. In the crystal, inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings of 1,10-phenanthroline and 4-methoxy\u00adbenzoate ligands [centroid\u2013centroid distance = 3.742\u2005(9)\u2005\u00c5] link two mol\u00adecules into a centrosymmetric dimer. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds help to consolidate the crystal packing.In the title dinuclear complex, [Tb DOI: 10.1107/S1600536809037751/cv2614Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four O atoms in the equatorial plane around the CoII ion form a slightly distorted square-planar arrangement with an average Co\u2014O bond length of 2.086\u2005\u00c5; the slightly distorted octa\u00adhedral coordination is completed by the two N atoms of the isonicotinamide (INA) ligands at a slightly longer distance [2.1603\u2005(14)\u2005\u00c5] in the axial positions. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 5.93\u2005(13)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 3.09\u2005(6)\u00b0. In the crystal structure, O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 Contacts between the benzene and pyridine rings [centroid\u2013centroid distance = 3.758\u2005(1)\u2005\u00c5] may further stabilize the crystal structure.The asymmetric unit of the crystal structure of the title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(H2O)4](C8H5O3)2\u00b72H2O = 0.034                           wR(F                           2) = 0.074                           S = 0.98                           3780 reflections236 parameters9 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.36 e \u00c5\u22123                        \u0394\u03c1min = \u22120.41 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008Mercury (Macrae et al., 2006WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536809033200/xu2594sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033200/xu2594Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The anion is a six-coordinate complex with a distorted octa\u00adhedral geometry around the FeIII atom. A wide range of non-covalent inter\u00adactions, i.e. O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds, ion pairing, C\u2014O\u22ef\u03c0 [3.431\u2005(2)\u2005\u00c5] and C\u2014H\u22ef\u03c0 stacking inter\u00adactions result in the formation of a three-dimensional network structure.In the title compound, (C DOI: 10.1107/S1600536810008597/su2166Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each Cu atom is coordinated by a bidentate chelating 2,2\u2032-bipyridine ligand. A bridging cyanide anion links the two Cu units to form a binuclear unit. Adjacent binuclear units are connected by a thio\u00adcyanate anion into a one-dimensional helical chain along [010]. The cyanide anion is disordered, with each site occupied by both C and N atoms in an occupancy ratio of 0.61\u2005(5):0.39\u2005(5). The S atom of the thio\u00adcyanate anion is also disordered over two sites, with occupancy factors of 0.61\u2005(3) and 0.39\u2005(3). There are \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl rings of neighbouring chains [centroid\u2013centroid distance = 3.82\u2005(1)\u2005\u00c5].The title compound, [Cu DOI: 10.1107/S1600536808037756/hy2162Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Numerous weak C\u2014H\u22efCl hydrogen bonds between [AuCl4]\u2212 and the 1,3-benzothia\u00adzolium units form layers comprised of 24-membered rings in which hydrogen-bonded tetra\u00adhydro\u00adfuran (THF) solvent mol\u00adecules are accommodated. C\u2014H\u22efCl inter\u00adactions between THF and [AuCl4]\u2212 from adjacent layers result in bilayers. These are further stabilized by \u03c0\u2013\u03c0 inter\u00adactions between the thia\u00adzole and benzene rings [centroid\u2013centroid distance = 3.971\u2005(3)\u2005\u00c5], resulting in the formation of a three-dimensional supra\u00admolecular assembly.In the crystal structure of the title ionic compound (C DOI: 10.1107/S1600536809003572/ng2541Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu and Pd atoms are both located on centers of symmetry in an alternating array of [Cu(N-Eten)2]2+ (N-Eten = N-ethyl\u00adethylenediamine) and [Pd(CN)4]2\u2212 units. The Pd\u2014C distances of 1.991\u2005(3) and 1.992\u2005(3)\u2005\u00c5 are inter\u00admediate values compared with the analogous NiII and PtII complexes [Akitsu & Einaga \u2005\u00c5 is noticeably longer than the equatorial distances [Cu\u2014NH2 = 2.007\u2005(2) and Cu\u2014NHC2H5 = 2.050\u2005(2)\u2005\u00c5]. There are interchain hybrogen bonds, with N(\u2014H)\u22efN = 3.099(4)\u2005\u00c5.The title compound, [CuPd(CN)naga 2007. Inorg.  DOI: 10.1107/S160053680900885X/bg2245Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "This results in a distorted cis-ZnO2N4 octa\u00adhedral coordination geometry for the metal ion. In the crystal, mol\u00adecules are expanded into a three-dimensional supra\u00admolecular motif via O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22ef hydrogen bonds. In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions between the aromatic rings of the polycyclic ligands consolidate the sturcture [shortest centroid\u2013centroid distance = 3.501\u2005(2)\u2005\u00c5].In the title compound, [Zn(C DOI: 10.1107/S1600536809039154/hb5120Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The three phosphine-substituted benzene rings make dihedral angles of 77.7\u2005(3), 84.4\u2005(3) and 77.4\u2005(3)\u00b0 with each other. Two of the three F atoms are disordered over two positions, with refined site occupancies of 0.591\u2005(11):0.409\u2005(11) and 0.730\u2005(12):0.270\u2005(12). In the crystal structure, mol\u00adecules are linked into a three-dimensional network by inter\u00admolecular C\u2014H\u22efCl and C\u2014H\u22efF hydrogen bonds.In the title gold complex, [AuCl(C DOI: 10.1107/S1600536810034896/fj2329Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZnII atoms are four-coordinated in distorted tetra\u00adhedral configurations by two N atoms from 5,5\u2032-dimethyl-2,2\u2032-bipyridine and two terminal Cl atoms. In the crystal structure, inter\u00admolecular C\u2014H\u22efCl hydrogen bonds link the mol\u00adecules. There are C\u2014H\u22ef\u03c0 contacts between the methyl groups and the pyridine and five-membered rings containing ZnII atoms; \u03c0\u2013\u03c0 contacts also exist between the pyridine rings [centroid\u2013centroid distances = 3.665\u2005(5) and 3.674\u2005(5)\u2005\u00c5].The asymmetric unit of the title compound, [ZnCl DOI: 10.1107/S1600536808027104/hk2517Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the complex, the two cyclo\u00adpenta\u00addienyl (Cp) rings are almost parallel with a dihedral angle of 1.36\u2005(8)\u00b0, and are separated by a centroid\u2013centroid distance of 3.299\u2005(2)\u2005\u00c5. In the crystal, adjacent mol\u00adecules are linked into a one-dimensional supra\u00admolecular structure via weak C\u2014H\u22ef\u03c0 inter\u00adactions between the Cp ring H atom and the Cp ring.The title compound, [Fe(C DOI: 10.1107/S1600536810005155/hy2280Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The ZrIV centre is in a distorted tetra\u00adhedral environment defined by two Cp rings of chelating organic ligands and two Br anions. Two five-membered rings form a dihedral angle of 59.7\u2005(2)\u00b0. Unequal Zr\u2014C bonds [2.471\u2005(3)\u20132.556\u2005(3)\u2005\u00c5] in the mol\u00adecule indicate that the inter\u00adaction of the central metal with the [(C5H4)2SiMe2]2\u2212 ligand contains noticeable \u03b73-allyl and \u03b72-olefin contributions.The title mol\u00adecule, [ZrBr DOI: 10.1107/S1600536808040713/cv2494Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ru\u2014Cl distances are 2.4161\u2005(7) and 2.4317\u2005(7)\u2005\u00c5, the Ru\u2014O distance is 2.1540\u2005(19)\u2005\u00c5, and the Ru\u2014S distances are in the range 2.2254\u2005(8)\u20132.2657\u2005(7)\u2005\u00c5, with the shortest being that trans to the aqua ligand. The coordinated water mol\u00adecule forms inter\u00admolecular hydrogen bonds with Cl and sulfoxide O atoms.The title mol\u00adecule, [RuCl DOI: 10.1107/S1600536809000439/pv2128Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The almost planar thio\u00adpyrano\u00adindole\u00adthione ring system  makes a dihedral angle of 80.70\u2005(8)\u00b0 with the p-tolyl ring. In the crystal, mol\u00adecules are connected via C\u2014H\u22efO hydrogen bonds into two chains along the b axis. These chains are connected via \u03c0\u2013\u03c0 inter\u00adactions between symmetry-related thio\u00adpyrano\u00adindole\u00adthione ring systems [centroid\u2013centroid distance = 3.588\u2005(1)\u2005\u00c5].The title compound, C DOI: 10.1107/S1600536810038201/bt5362Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Mol\u00adecules are linked by C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and by \u03c0\u2013\u03c0 inter\u00adactions with inter\u00adplanar distances of 3.2661\u2005(6) and 3.2775\u2005(6)\u2005\u00c5.In the title compound, C DOI: 10.1107/S160053680803941X/fj2169Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each [CuBr4]2\u2212 anion is connected non-symmetrically to four surrounding cations through N\u2014H\u22efX (pyridine and amine proton) hydrogen bonds, forming chains of the ladder-type running parallel to the crystallographic b axis. These layers are further connected by means of offset face-to-face inter\u00adactions , giving a three-dimensional network. Cation \u03c0\u2013\u03c0 stacking [centroid separations of 3.69\u2005(9) and 3.71\u2005(1)\u2005\u00c5] and Br\u22efaryl inter\u00adactions [3.72\u2005(2) and 4.04\u2005(6)\u2005\u00c5] are present in the crystal structure. There are no inter\u00admolecular Br\u22efBr inter\u00adactions.In the crystal structure of the title compound, (C DOI: 10.1107/S1600536808010647/at2561Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, the cations and anions are linked by N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds, forming a layer network parallel to the ac plane. Weak \u03c0\u2013\u03c0 inter\u00adactions between adjacent pyridine rings with a centroid\u2013centroid distance of 3.589\u2005(2)\u2005\u00c5 are also present.In the dication of the title salt, C DOI: 10.1107/S1600536809038689/ng2649Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecule contains an inversion center in the middle of the Ge4O2 ring which is in a chair conformation. The Ge\u2014Ge bond distance is 2.4418\u2005(5)\u2005\u00c5 and the Ge\u2014O bond distances are 1.790\u2005(2) and 1.785\u2005(2)\u2005\u00c5. The torsion angles within the Ge4O2 ring are \u221256.7\u2005(1) and 56.1\u2005(1)\u00b0 for the Ge\u2014Ge\u2014O\u2014Ge angles and \u221243.9\u2005(1)\u00b0 for the O\u2014Ge\u2014Ge\u2014O angle.The title compound, C DOI: 10.1107/S1600536809032012/lh2875Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The compound displays intra\u00admolecular C\u2014H\u22efCl hydrogen bonds and pairs of complex mol\u00adecules are connected by inter\u00admolecular C\u2014H\u22efCl hydrogen bonds. Inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are present between the pyridine rings of the ligand, the shortest centroid\u2013centroid distance being 4.096\u2005(3)\u2005\u00c5. As a result of the electronic nature of the chelate ring, it is possible to create \u03c0\u2013\u03c0 inter\u00adactions to its symmetry-related counterpart [3.720\u2005(2)\u2005\u00c5] and also with a pyridine ring [3.570\u2005(3)\u2005\u00c5] of the bipy unit. The present structure is a redetermination of a previous structure [Vicente et al. (1997In the title compound, [PdCl al. 1997. Private X            2(bipy)] (X = Cl or Br), see: Maekawa et al. ]\u00b7CH2Cl2                         = 0.044                           wR(F                           2) = 0.097                           S = 1.05                           2862 reflections203 parametersAll H-atom parameters refinedmax = 0.56 e \u00c5\u22123                        \u0394\u03c1min = \u22120.69 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 (Farrugia, 1997PLATON (Spek, 2009SHELXL97.Data collection: 10.1107/S1600536809016262/kp2220sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016262/kp2220Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, 2-amino-3-(1H-indol-3-yl)propionic acid mol\u00adecules and pyridine-2,4-dicarb\u00adoxylic acid mol\u00adecules are linked through strong inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming layers parallel to (100). The layers are linked through the ethanol mol\u00adecules via somewhat weaker inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming thus a three-dimensional network. Weak C\u2014H\u22efO and N\u2014H\u22efN hydrogen bonding and \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings are also present.In the title compound, C DOI: 10.1107/S1600536810014017/fb2190Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between the 1,10-phenanthroline ligands and 5-chloro\u00adsalicylate ligands, with a centroid\u2013centroid distance between neighbouring aromatic rings of 3.730\u2005(1)\u2005\u00c5.In the title complex, [Cd(C DOI: 10.1107/S1600536808015687/wn2261Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The seven donor atoms of the (pydc)2\u2212 groups and the hydroxido ligands form a distorted penta\u00adgonal\u2013bipyramidal arrangement around the SbIII/SbV centers. C\u2014H\u22ef\u03c0 stacking inter\u00adactions between CH groups of the complex dianion and the aromatic rings of the + cations, with a distance of 2.89\u2005\u00c5, are observed. In the crystal structure, a wide range of noncovalent inter\u00adactions, consisting of O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds [D\u22efA ranging from 2.722\u2005(2) to 3.137\u2005(3)\u2005\u00c5], ion pairing, \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distance of 3.4363\u2005(13)\u2005\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions, connect the various components into a supra\u00admolecular structure.The reaction of anti\u00admony(III) chloride, 4,4\u2032-bipyridine  and pyridine-2,6-dicarboxylic acid (pydcH DOI: 10.1107/S1600536808001372/su2034Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "All three bidentate ligands have coordinating ring systems that are almost coplanar [inter\u00adplanar angles = 1.7\u2005(1)\u20133.8\u2005(2)\u00b0]. The vinyl\u00adbenzyl group is disordered over two positions with occupations of 0.653\u2005(4) and 0.347\u2005(4). The methanol solvent mol\u00adecule is involved in a classical O\u2014H\u22efN hydrogen bond to a triazole N atom.In the title compound, [Ir(C DOI: 10.1107/S1600536809052726/tk2595Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The torsion angle for the Te\u2014Re\u2014Te\u2014Re sequence of atoms is 17.06\u2005(3)\u00b0. The crystal structure is stabilized by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. In addition, there are Te\u22efTe distances [4.0392\u2005(12)\u2005\u00c5] and O\u22efO distances [2.902\u2005(19)\u2005\u00c5] which are shorter than the sum of the van der Waals radii for these atoms. A short inter\u00admolecular lone pair\u22ef\u03c0 distance [C\u00a0O\u22efCg = 3.31\u2005(2)\u2005\u00c5] is also observed.In the title complex, [Re DOI: 10.1107/S1600536810012389/lh5009Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 inter\u00adactions, with centroid\u2013centroid distances of 3.765\u2005(5) and 3.896\u2005(5)\u2005\u00c5 between the phenyl ring and the benzene ring of the chromene unit of neighbouring mol\u00adecules. In addition, the stacked mol\u00adecules exhibit inter- and intra\u00admolecular O\u2014H\u22efO hydrogen bonds, including the uncoordinated water mol\u00adecules.In the title compound, [Ca(C DOI: 10.1107/S1600536808037586/lx2072Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two EuIII ions are linked by four bridging benzoate ions, with an Eu\u22efEu distance of 3.96041\u2005(12)\u2005\u00c5. Each EuIII ion is coordinated by one phenanthroline heterocycle and a bidentate benzoate ion. The irregular nine-coordinated geometry of the metal ion is composed of seven O and two N atoms. The mol\u00adecular structure is stabilized by intra\u00admolecular C\u2014H\u22efO hydrogen bonds. In the crystal structure, mol\u00adecules are linked into chains by inter\u00admolecular C\u2014H\u22efO hydrogen bonds along the a axis. The crystal structure is further stabilized by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. Weak \u03c0\u2013\u03c0 inter\u00adactions are also observed [centroid\u2013centroid distances = 3.6962\u2005(10)\u20133.6963\u2005(10)\u2005\u00c5].The asymmetric unit of the title complex, [Eu For rel al. 1999, 2002 \u25b6;2(C7H5O2)6(C12H8N2)2]\u00b72C7H6O2                         = 0.020                           wR(F                           2) = 0.050                           S = 1.04                           12557 reflections464 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.62 e \u00c5\u22123                        \u0394\u03c1min = \u22120.44 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXTL (Sheldrick, 2008SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009Data collection: 10.1107/S1600536810015229/rz2435sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015229/rz2435Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "All intramolecular distances and angles are similar for the two structures. This applies also for the intermolecular forces, consisting of O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 interactions [with centroid\u2013centroid distances of 3.428\u2005(2) and 3.579\u2005(2)\u2005\u00c5], that lead to a cohesion of the structure.The title compound, (C DOI: 10.1107/S1600536809022053/pv2161Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The main geometric parameters are Pt\u2014N = 1.960\u2005(5)\u2005\u00c5, and Pt\u2014Cl = 2.3177\u2005(12) and 2.3196\u2005(12)\u2005\u00c5. The N\u00a0C bond is a typical triple bond [1.137\u2005(7)\u2005\u00c5]. The Pt\u2014N\u00a0C\u2014C unit is almost linear, with Pt\u2014N\u2014C and N\u2014C\u2014C angles of 174.6\u2005(4) and 177.1\u2005(6)\u00b0, respectively.In the title compound, [PtCl DOI: 10.1107/S1600536809016535/pv2142Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, inter\u00admolecular bifurcated N\u2014H\u22ef hydrogen bonds connect the mol\u00adecules into chains propagating along [100]. Adjacent chains inter\u00adact by strong aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions, with a centroid\u2013centroid distance of 3.483\u2005(2)\u2005\u00c5.In the title compound, [Pb(NO DOI: 10.1107/S1600536808041317/hb2871Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The conformations of the two crystallographically independent mol\u00adecules are slightly different: in A, the Cu\u22efCu separation is 4.174\u2005(9)\u2005\u00c5 and the dihedral angle between the triazole and phenyl rings is 74.23\u2005(11)\u00b0; these values are 4.137\u2005(9)\u2005\u00c5 and 68.58\u2005(13)\u00b0, respectively, in B. In each mol\u00adecule, the copper(II) ions have a distorted trigonal\u2013bipyramidal coordination geometry with a CuCl2NN\u2032N\u2032\u2032 chromophore. The crystal packing exhibits weak inter\u00admolecular C\u2014H\u22efCl inter\u00adactions.The asymmetric unit of the title compound, [Cu DOI: 10.1107/S160053680804035X/cv2472Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The K\u22efO distances range from 2.8416\u2005(8) to 3.0025\u2005(8)\u2005\u00c5, and the two K\u22efN distances are 2.7441\u2005(11) and 2.7654\u2005(11)\u2005\u00c5. The K cation is displaced by 0.8437\u2005(4)\u2005\u00c5 from the best plane through the six O atoms. The latter plane is almost perpendicular to the plane of the pyrazolate ring [dihedral angle 83.93\u2005(3)\u00b0].The asymmetric unit of the title compound, [K(C DOI: 10.1107/S1600536808043237/rz2281Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The other Sn atom has a bent R               2Sn skeleton [C\u2014Sn\u2014C = 144.0\u2005(1)\u00b0], but the geometry is best regarded as being a trans-C2SnO4 octa\u00adhedron as the Sn\u2013O(single bond) inter\u00adaction is shorter [Sn\u2014O = 2.674\u2005(1)\u2005\u00c5].In the centrosymmetric tetra\u00adnuclear title compound, [Sn DOI: 10.1107/S1600536808023787/tk2287Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both the phosphine and arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. All three cyclo\u00adhexane rings are disordered over two positions with site occupancies of 0.628\u2005(6) and 0.372\u2005(6). The mean planes of these three phosphine-substituted cyclo\u00adhexane rings make dihedral angles of 53.0\u2005(8), 68.3\u2005(6) and 89.9\u2005(7)\u00b0 (major components), and 46.7\u2005(14), 41.3\u2005(11) and 75.8\u2005(10)\u00b0 (minor components) with each other. The dihedral angles between the two phenyl rings are 85.0\u2005(2) and 88.1\u2005(2)\u00b0 for the two diphenyl\u00adarsino groups. Two cyclo\u00adhexane rings adopt a chair conformation whereas the other adopts a slightly twisted chair conformation for the major components; these conformations are similiar for the minor components. Intra\u00admolecular C\u2014H\u22efO hydrogen bonds stabilize the mol\u00adecular structure. In the crystal packing, the mol\u00adecules are linked together into chains via inter\u00admolecular C\u2014H\u22efO hydrogen bonds down the a axis. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions further stabilize the crystal structure.In the title  DOI: 10.1107/S1600536809047977/sj2677Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is stabilized by a combination of weak \u03c0\u2013\u03c0 stacking inter\u00adactions between symmetry-related 1,10-phenanthroline ligands [centroi\u2013centroid distance between benzene rings = 3.5936\u2005(18)\u2005\u00c5] and weak O\u2014H\u22efS, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds between methanol and complex mol\u00adecules.In the title complex, [Ni(NCS) DOI: 10.1107/S1600536808011811/lh2613Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each DyIII ion is coordinated by six O atoms and two N atoms from two pyridine-2,6-dicarboxyl\u00adate and two 6-carboxy\u00adpicolinate ligands, displaying a bicapped trigonal-prismatic geometry. The average Dy\u2014O bond distance is 2.40\u2005\u00c5, some 0.1\u00c5 longer than the corresponding Ho\u2014O distance in the isotypic holmium complex. Adjacent DyIII ions are linked by the pyridine-2,6-dicarboxyl\u00adate ligands, forming a layer in (100). These layers are further connected by \u03c0\u2013\u03c0 stacking inter\u00adactions between neighboring pyridyl rings [centroid\u2013centroid distance = 3.827\u2005(3)\u2005\u00c5] and C\u2014H\u22efO hydrogen-bonding inter\u00adactions, assembling a three-dimensional supra\u00admolecular network. Within each layer, there are other \u03c0\u2013\u03c0 stacking inter\u00adactions between neighboring pyridyl rings [centroid\u2013centroid distance = 3.501\u2005(2)\u2005\u00c5] and O\u2014H\u22efO and C\u2014H\u22efO hydrogen-bonding inter\u00adactions, which further stabilize the structure.In the title complex, [Dy(C DOI: 10.1107/S1600536809039075/sj2654Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are stacked alternately in opposite orientations, forming a one-dimensional column parallel to [110]. The primary inter\u00adactions between mol\u00adecules comprising the columns are of the S\u22efS type [3.554\u2005(1)\u2005\u00c5]. Inter\u00adactions between columns are of the S\u22efS type [3.411\u2005(1) along b and 3.444\u2005(1)\u2005\u00c5 along c], as well as S\u22efI contacts [3.435\u2005(2)\u2005\u00c5].The mol\u00adecular framework of the title compound, C DOI: 10.1107/S1600536809044493/tk2559Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "These units are connected via the carboxyl\u00adate O atoms and water mol\u00adecules, building polymeric layers parallel to (100). In the crystal structure, non-covalent inter\u00adactions consisting of O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.862\u2005(17) and 3.749\u2005(17)\u2005\u00c5] connect the various components, forming a three-dimensional structure.In the title polymeric complex, [Sr(C DOI: 10.1107/S160053680902683X/pv2167Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each CuI atom is tetra\u00adhedrally coordinated by three I atoms and one N atom of an benzyl\u00addimethyl\u00adamine ligand. Each I atom acts as a \u03bc3-ligand, linking three CuI atoms. The Cu\u2014I bond distances vary between 2.6328\u2005(7) and 2.7121\u2005(6)\u2005\u00c5, while the Cu\u2014N bond distances vary between 2.107\u2005(3) and 2.122\u2005(3)\u2005\u00c5.The title compound, [Cu DOI: 10.1107/S1600536809026208/fj2223Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII atom exhibits a six-coordinated distorted octa\u00adhedral geometry with two N atoms from the phenanthroline ligand [Cu\u2014N 2.007\u2005(2)\u2005\u00c5] and four O atoms from two 3,4-dimethoxy\u00adbenzoate ligands [Cu\u2014O 1.950\u2005(1) and 2.524\u2005(1)\u2005\u00c5]. The difference in Cu\u2014O bond distances indicates a strong Jahn\u2013Teller effect. In the crystal, C\u2014H\u22ef\u03c0 inter\u00adactions result in chains of mol\u00adecules along the c axis.The asymmetric unit of the title compound, [Cu(C DOI: 10.1107/S1600536809052234/ez2194Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The phenyl rings are rotated out of the benzofuran planes, making dihedral angles of 43.38\u2005(7) and 56.13\u2005(6)\u00b0 in the two mol\u00adecules. The carboxyl groups are involved in inversion-related inter\u00admolecular O\u2014H\u22efO hydrogen bonds, which link the mol\u00adecules into centrosymmetric dimers. These dimers are further packed into stacks along the b axis by weak non-classical inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The crystal structure also exhibits inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions, and two aromatic \u03c0\u2013\u03c0 inter\u00adactions between the furan rings of neighbouring benzofuran systems; the centroid\u2013centroid distances are 3.500\u2005(3) and 3.605\u2005(3)\u2005\u00c5.The title compound, C DOI: 10.1107/S160053680903253X/nk2002Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Cu atom is five-coordinated in a distorted trigonal-bipyramidal geometry by two phen mol\u00adecules and one bromide ligand, which coordinates in the equatorial plane at a distance of 2.5228\u2005(4)\u2005\u00c5 and lying along with the Cu and the amide N atoms on a twofold rotation axis. The two axial Cu\u2014N distances [1.9926\u2005(15)\u2005\u00c5] are slightly shorter than the two equatorial Cu\u2014N bonds [2.0979\u2005(15)\u2005\u00c5]. The structure is stabilized by a weak C\u2014H\u22efN hydrogen bond, with a cyanide N atom of the dicyanamide ligand as an acceptor, and \u03c0\u2013\u03c0 inter\u00adactions between nearly parallel phenyl and pyridine rings of two adjacent phen mol\u00adecules [centroid\u2013centroid distance = 3.589\u2005(1)\u2005\u00c5], and between \u03c0 electrons of the dicyanamide anion and the pyridine ring .The title compound, [CuBr(C For pen al. 1984. For a d al. 1984. For ref al. 1984.       12H8N2)2]C2N3                         = 0.021                           wR(F                           2) = 0.062                           S = 1.06                           2182 reflections160 parametersH-atom parameters constrainedmax = 0.29 e \u00c5\u22123                        \u0394\u03c1min = \u22120.43 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis CCD  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008DIAMOND (Brandenburg, 2001SHELXL97.Data collection: 10.1107/S1600536810037979/kp2274sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037979/kp2274Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The C\u2014P bond lengths are 1.8824\u2005(19) and 1.8991\u2005(19)\u2005\u00c5. The P\u2014C\u2014P angle of 109.69\u2005(9)\u00b0 is essentially equal to the expected value of 109.5\u00b0 for a tetra\u00adhedral C atom. Although the C(methine)\u2014P\u2014C(aromatic) bond angles range from 102.67\u2005(9) to 107.04\u2005(9)\u00b0, the C(aromatic)\u2014P\u2014C(aromatic) bond angles of 96.72\u2005(9) and 97.29\u2005(9)\u00b0 are significantly smaller. The steric demands of the o-tolyl groups cause deviations from the bond lengths and angles reported for its phenyl analog.The complete molecule of title compound, C DOI: 10.1107/S1600536809032942/ng2629Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A water mol\u00adecule cocrystallizes with the coordination compound and may be held in the crystal by O\u2014H\u22efO hydrogen bonds. Heteroatomic \u03c0\u2013\u03c0 ring inter\u00adactions may be present between symmetry-related complexes, with centroid\u2013centroid distances of 3.5661\u2005(8)\u2005\u00c5.In the title complex, [Co(C DOI: 10.1107/S1600536809021540/cs2106Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Adjacent stacked mol\u00adecules exhibit a carbon\u00adyl\u2013carbonyl inter\u00adaction [3.295\u2005(2)\u2005\u00c5]. The O atom of the methyl\u00adsulfinyl group is disordered over two positions with site-occupancy factors of 0.9 and 0.1.Mol\u00adecules of title compound, C DOI: 10.1107/S1600536808034466/ng2503Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Each CrIII atom is hexa\u00adcoordinated by four O and two N atoms from two (hypydc)2\u2212 fragments, which act as tridentate ligands, in a distorted octa\u00adhedral geometry. The O\u2014Cr\u2014O\u2014C torsion angles between the two planes of the (hypydc)2\u2212 fragments [\u221299.81\u2005(17) and 97.77\u2005(17)\u00b0] indicate that these two units are almost perpendicular to one another. In the crystal structure, extensive O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds with D\u22efA distances ranging from 2.560\u2005(2) to 3.279\u2005(3)\u2005\u00c5, ion pairing, C\u2014O\u22ef\u03c0 [O\u22ef\u03c0 = 3.166\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions between (hypydc)2\u2212 and (pydaH)+ rings [with a centroid\u2013centroid distance of 3.3353\u2005(14)\u2005\u00c5] contribute to the formation of a three-dimensional supra\u00admolecular structure.The reaction of chromium(III) nitrate hexa\u00adhydrate, pyridine-2,6-diamine and 4-hydroxy\u00adpyridine-2,6-dicarboxylic acid in a 1:2:2 molar ratio in aqueous solution resulted in the formation of the title compound, (C DOI: 10.1107/S1600536808027347/ym2072Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one mol\u00adecule of the complex and half a water solvent mol\u00adecule. The solvent water mol\u00adecule lies on a crystallographic twofold rotation axis. An inter\u00admolecular O\u2014H\u22efO hydrogen bond forms an R               2               1(4) ring motif involving a bifurcated hydrogen bond to the phenolate O atoms of the complex. In the crystal structure, mol\u00adecules are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances in the range 3.5310\u2005(11)\u20133.7905\u2005(12)\u2005\u00c5, forming extended chains along the b axis. In addition, there are Ni\u22efNi and Ni\u22efN inter\u00adactions  which are shorter than the sum of the van der Waals radii of the relevant atoms. Further stabilization of the crystal structure is attained by weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title complex, [Ni(C DOI: 10.1107/S1600536808023362/lh2663Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit of the title compound comprises one-half of the complex mol\u00adecule and one of the water mol\u00adecules of crystallization. The water H atoms form bifurcated O\u2014H\u22ef hydrogen bonds with the O atoms of the phenolato and eth\u00adoxy groups with R               1               2(5) and R               1               2(6) ring motifs. The dihedral angle between the central benzene ring and the two outer benzene rings are 4.07\u2005(11) and 3.99\u2005(12)\u00b0. The dihedral angle between the two O\u2013Ni\u2013N coordination planes is only 0.77\u2005(11)\u00b0. In the crystal structure, the mol\u00adecules are linked together into extended chains along the c axis by inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions. An inter\u00adesting feature of the crystal structure is a short inter\u00admolecular C \u22ef C [3.355\u2005(3)\u2005\u00c5] contact, which is shorter than the sum of the van der Waals radii. The crystal structure may be further stabilized by inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances in the range 3.5758\u2005(13)\u20133.6337\u2005(13)\u2005\u00c5]. In the title complex, [Ni(C DOI: 10.1107/S1600536809012641/cs2114Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, centrosymmetric dimers are formed though O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds; \u03c0\u2013\u03c0 stacking inter\u00adactions, with a centroid\u2013centroid distance of 3.796\u2005(2)\u2005\u00c5, are also found.In the title compound, [Ni(C DOI: 10.1107/S1600536808022939/lh2644Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the cation, the Cu2+ ion is coordinated by four N atoms from two bidentate 2,2\u2032-bipyridine mol\u00adecules and an N atom from an isothio\u00adcyanate anion, resulting in a distorted CuN5 pyramidal configuration. The crystal structure is stabilized by weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, and weak \u03c0\u2013\u03c0 inter\u00adactions between 2,2\u2032-bipyridine rings [centroid\u2013centroid distance = 3.908\u2005(4)\u2005\u00c5]. The perchlorate counteranion is disordered over two positions in a 0.66:0.34 ratio.The asymmetric unit of title compound, [Cu(NCS)(C DOI: 10.1107/S1600536809031067/at2856Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Ca2+ ions are bridged by 2-chloronicotinate groups and exhibit an eight-coordination by six carboxylate O atoms of four different 2-chloronicotinate ligands and two O atoms of water molecules. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds result in the formation of a supra\u00admolecular network structure. The \u03c0\u2013\u03c0 contacts between the 2-chloro\u00adnicotinate rings [centroid\u2013centroid distances = 3.875\u2005(3) and 3.701\u2005(3)\u2005\u00c5] may further stabilize the structure. The itle compound, [Ca(C DOI: 10.1107/S1600536808044267/hk2578Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The L ligands chelate the LaIII ion with strong La\u2014O(deprotonated phenolic) bonds [2.435\u2005(3)\u20132.464\u2005(3)\u2005\u00c5] and significantly longer La\u2014O(meth\u00adoxy) bonds [2.801\u2005(3)\u20132.831\u2005(3)\u2005\u00c5]. The La\u2014N bond lengths range from 2.541\u2005(4) to 2.605\u2005(4)\u2005\u00c5.In the title compound, [La(NCS) DOI: 10.1107/S1600536809049113/pv2228Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The two rings are almost parallel and are eclipsed and ordered. The conjugated substituent is slightly twisted with respect to the cyclo\u00adpenta\u00addiene ring. The crystal structure contains four inter\u00admolecular C\u2014H\u22efO hydrogen-bonds in the range 3.324\u2005(3)\u20133.539\u2005(3)\u2005\u00c5 and one \u03c0(aryl ring)\u2013\u03c0 (Cp ring) stacking inter\u00adaction with a ring\u2013centroid distance of 3.894\u2005(2)\u2005\u00c5.In the title compound, [Fe(C DOI: 10.1107/S1600536808027815/om2257Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The plane containing the thio\u00adcarbonyl and carbonyl groups subtends dihedral angles of 48.19\u2005(3) and 87.51\u2005(3)\u00b0 with the planes formed by the 3-chloro and 2,6-dichloro\u00adphenyl rings, respectively; the dihedral angle between the two benzene ring planes is 45.32\u2005(3)\u00b0. An intra\u00admolecular N\u2014H\u22efO hydrogen bond stabilizes the mol\u00adecular conformation and the mol\u00adecules form inter\u00admolecular N\u2014H\u22efS and N\u2014H\u22efO hydrogen bonds, generating a sheet along the a axis.The structure of the title compound, C DOI: 10.1107/S1600536808043444/pv2127Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "One of the Cp rings is disordered over two positions with occupancies of 0.55 and 0.45. The dihedral angle between the substituted Cp rings is 56.1\u2005(5)\u00b0 and the two phenyl rings are orientated at a dihedral angle of 41.7\u2005(4)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efS, N\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds link the mol\u00adecules into chains along the b axis. The structure is further consolidated by O\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Fe DOI: 10.1107/S1600536809046078/ci2959Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Intra\u00admolecular N\u2014H\u22efO hydrogen bonds occur. The crystal packing exhibits weak inter\u00admolecular C\u2014H\u22efS hydrogen bonds, \u03c0\u2013\u03c0 inter\u00adactions with a distance of 3.904\u2005(7)\u2005\u00c5 between the centroids of the aromatic rings, and voids of 101\u2005\u00c53.In the title compound, [Nd(NCS) DOI: 10.1107/S1600536809053124/cv2653Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The trinuclear mol\u00adecules, with an intramolecular Cu\u22efCu separation of 6.313\u2005(3)\u2005\u00c5, are linked to each other, forming a chain through O\u2014H\u22efO and O\u2014H\u22efBr hydrogen bonds involving the half-occupied water mol\u00adecule. Futhermore, weak C\u2014H\u22efO inter\u00adactions link the chains to form a supra\u00admolecular network.The title complex, [Cu DOI: 10.1107/S1600536809014263/dn2446Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The phenyl ring makes a dihedral angle of 83.64\u2005(4)\u00b0 with the mean plane of the 5,6-(methyl\u00adene\u00addi\u00adoxy)\u00adbenzo\u00adfuran fragment. The crystal structure is stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions between a benzene H atom of the 5,6-(methyl\u00adene\u00addi\u00adoxy)\u00adbenzo\u00adfuran unit and the phenyl ring of the phenyl\u00adsulfonyl substituent. Additionally, the crystal structure exhibits inter- and intra\u00admolecular C\u2014H\u22efO inter\u00adactions.The title compound, C DOI: 10.1107/S160053680800980X/bh2167Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are two uncoord\u00adinated water mol\u00adecules in the structure. The asymmetric unit of the compound has two different coordination types  of ZnII in the crystal structure that are bridged to each other via one hypydc2\u2212 group . A variety of inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds involving water mol\u00adecules, cations and anions, and also a weak \u03c0\u2013\u03c0 inter\u00adaction [3.798\u2005(1)\u2005\u00c5], are responsible for extending the structure into a three-dimensional network.The title compound, (CH DOI: 10.1107/S1600536808003930/om2211Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The four nearest O atoms around each CuII ion form a distorted square-planar arrangement, and the distorted square-pyramidal coordination is completed by the pyridine N atom of the isonicotinamide (INA) ligand. Each CuII ion is displaced by 0.2633\u2005(1)\u2005\u00c5 from the plane of the four O atoms, with an average Cu\u2014O distance of 1.974\u2005(2)\u2005\u00c5. The dihedral angles between carboxyl\u00adate groups and the adjacent benzene rings are 7.88\u2005(19) and 9.68\u2005(10)\u00b0, while the benzene rings are oriented at a dihedral angle of 85.90\u2005(9)\u00b0. The pyridine ring is oriented at dihedral angles of 8.59\u2005(7) and 83.89\u2005(9)\u00b0 with respect to the benzene rings. In the crystal structure, inter\u00admolecular N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 contacts between the benzene rings and between the pyridine and benzene rings,  may further stabilize the crystal structure.In the title centrosymmetric binuclear complex, [Cu N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 4(C6H6N2O)2] = 0.043                           wR(F                           2) = 0.087                           S = 1.01                           5101 reflections281 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.47 e \u00c5\u22123                        \u0394\u03c1min = \u22120.70 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810006513/xu2729sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810006513/xu2729Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecule is centrosymmetric; the pairs of equivalent ligands coordinate trans to each other in a distorted octa\u00adhedral geometry. Intra\u00admolecular C\u2014H\u22efO bonds lying in the equatorial plane stabilize the mol\u00adecule. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, creating a three-dimensional supra\u00admolecular structure. \u03c0\u2013\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions are also observed. The dihedral angle and centroid-to-centroid distance between the pyridine ring (A) and the benzene ring (B               i) of a symmetrically related mol\u00adecule  are 1.27\u2005(11)\u00b0 and 3.974\u2005(2)\u2005\u00c5, respectively. For the C\u2014H\u22ef\u03c0 inter\u00adactions, the relevant distances and angles are: C\u22efCg[A               ii] = 3.643\u2005(2)\u2005\u00c5, H\u22efCg[A               ii] = 2.750\u2005(2)\u2005\u00c5 and C\u2014H\u22efCg[A               ii] = 155\u2005(1)\u00b0 .The title compound, [Mn(C II complexes with the quinoline-2 carboxyl\u00adate ligand, see: Okabe &Koizumi 2(CH4O)2] = 0.034                           wR(F                           2) = 0.089                           S = 0.98                           1924 reflections146 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.37 e \u00c5\u22123                        \u0394\u03c1min = \u22120.31 e \u00c5\u22123                        \u0394\u03c1                                 CrysAlis CCD  used to solve structure: SHELXTL-NT (Sheldrick, 2008SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.Data collection: 10.1107/S1600536808031905/su2065sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031905/su2065Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The environment around the Ho atom can be described as a distorted bicapped square anti\u00adprism. Two phenanthroline ligands form a dihedral angle of 43.72\u2005(13)\u00b0. Short inter\u00admolecular distances between the centroids of the six-membered rings [3.6887\u2005(14)\u20133.8374\u2005(16)\u2005\u00c5] indicate the existence of \u03c0\u2013\u03c0 inter\u00adactions, which link the mol\u00adecules into stacks extended in the [10In the title compound, [Ho(NO DOI: 10.1107/S1600536808020655/cv2423Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Zn(C9H10NO2)2(C6H6N2O)(H2O)2], contains two 4-(dimethyl\u00adamino)benzoate (DMAB) ligands, one isonicotinamide (INA) ligand and two water mol\u00adecules; one of the DMAB ions acts as a bidentate ligand while the other and INA are monodentate ligands. The four O atoms in the equatorial plane around the Zn atom form a distorted square-planar arrangement, while the distorted octa\u00adhedral coordination is completed by the N atom of the INA ligand and the O atom of the water mol\u00adecule in the axial positions. Intra\u00admolecular C\u2014H\u22efO hydrogen bonding results in the formation of a six-membered ring adopting an envelope conformation. The dihedral angle between the carboxyl groups and the adjacent benzene rings are 4.87\u2005(16) and 2.2\u2005(2)\u00b0, while the two benzene rings are oriented at a dihedral angle of 65.13\u2005(8)\u00b0. The dihedral angle between the benzene and pyridine rings are 11.47\u2005(7) and 74.83\u2005(8)\u00b0, respectively. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, O\u2014H\u22efN and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a supra\u00admolecular structure. \u03c0\u2013\u03c0 contacts between the pyridine and benzene rings and between the benzene rings  further stabilize the structure. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are also present.The mol\u00adecule of the title Zn DOI: 10.1107/S1600536809017620/xu2522Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordinated water mol\u00adecule is involved in inter\u00admolecular O\u2014H\u22efO hydrogen bonding, which links the complex mol\u00adecules into chains propagating along the c axis. Neighbouring chains inter\u00adact further via \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings of 1,10-phenanthroline fragments [centroid\u2013centroid distances = 3.726\u2005(4) and 3.750\u2005(4)\u2005\u00c5].The asymmetric unit of the title compound, [Cu(C DOI: 10.1107/S1600536809024428/cv2568Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 4-tolyl ring makes a dihedral angle of 70.96\u2005(6)\u00b0 with the plane of the naphthofuran fragment. The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances of 3.672\u2005(3) and 3.858\u2005(3)\u2005\u00c5 between the central benzene and furan rings, and between the brominated benzene and central benzene rings of the naphthofuran system of neighbouring mol\u00adecules, respectively. In addition, the stacked mol\u00adecules exhibit C\u2014H\u22ef\u03c0 and inter- and intra\u00admolecular C\u2014H\u22efO inter\u00adactions.The title compound, C DOI: 10.1107/S1600536808015286/at2569Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by inter\u00admolecular N\u2014H\u22efO and N\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions of the aromatic rings of the two ligands [inter\u00adplanar distance = 3.652\u2005(10)\u2005\u00c5]. The AgI atom shows a linear coordination [N\u2014Ag\u2014N = 174.6\u2005(1)\u00b0].Colourless crystals of the title mixed ligand complex, [Ag(C DOI: 10.1107/S1600536809035193/ng2621Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Co(C5H3N2O4)2(H2O)4]\u00b72H2O, the CoII ion is located on an inversion center and is coordinated by two orotate  anions and four water mol\u00adecules in a slightly distorted octa\u00adhedral geometry. The dihedral angle between the carboxyl\u00adate group and the attached orotate ring is 1.2\u2005(3)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. \u03c0\u2013\u03c0 contacts between the orotate rings [centroid\u2013centroid distances = 3.439\u2005(2) and 3.438\u2005(2)\u2005\u00c5] further stabilize the structure.In the title Co DOI: 10.1107/S1600536810015837/xu2754Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a \u03c0\u2013\u03c0 contact between pyridine rings of adjacent molecules [centroid\u2013centroid distance = 3.723\u2005(5)\u2005\u00c5].In the mol\u00adecule of the title compound, [HgI DOI: 10.1107/S160053680802953X/hk2531Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination geometry for Cd is distorted octa\u00adhedral based on a cis-N2S4 donor set. In the crystal structure, mol\u00adecules are connected into a supra\u00admolecular chain aligned along the a direction via C\u2014H\u22efS and C\u2014H\u22ef\u03c0 contacts, and by \u03c0\u2013\u03c0 contacts [centroid-to-centroid distance 3.5708\u2005(15)\u2005\u00c5]. The n-propyl groups are each disordered, one equally over two sites and the other with a site-occupancy factor of 0.618\u2005(8) for the major component. The dinuclear centrosymmetric title compound, [Cd DOI: 10.1107/S1600536808025889/ng2485Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both P atoms have a trigonal\u2013pyramidal conformation. There is a short intra\u00admolecular C\u2014H\u22efP contact with an H\u22efP distance of 2.56\u2005\u00c5. The hydr\u00adoxy group is involved in an intra\u00admolecular O\u2014H\u22ef\u03c0phen\u00adyl inter\u00adaction. The crystal packing shows five very weak inter\u00admolecular C\u2014H\u22ef\u03c0 contacts, with H\u22efCg distances between 3.26 and 3.39\u2005\u00c5 (Cg is the centroid of a phenyl or cyclo\u00adpenta\u00addienyl ring).The absolute configuration of the title compound, [Fe(C DOI: 10.1107/S1600536808038294/nc2123Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efO hydrogen bonds link neighbouring mol\u00adecules into a one-dimensional supra\u00admolecular structure with an R22(14) ring motif. This structure is further stabilized by \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent benzene rings [centroid\u2013centroid distance = 3.862\u2005(1)\u2005\u00c5].In the title centrosymmetric mononuclear copper(II) complex, [Cu(C DOI: 10.1107/S1600536809047989/hy2253Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efO hydrogen bonds form an eight-membered R               2               2(8) motif. The dihedral angle betwen two benzene rings is 36.34\u2005(9)\u00b0. There are inter\u00admolecular Cu\u22efBr [3.4566\u2005(5)\u2005\u00c5] and Cu\u22ef\u00b7N [3.569\u2005(3)\u2005\u00c5] contacts, which are significantly shorter than the sum of van der Waals radii of the relevant atoms. These inter\u00adactions, along with the inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid distances of 3.709\u2005(1) and 3.968\u2005(2)\u2005\u00c5] inter\u00adactions, link neighbouring mol\u00adecules into a one-dimensional infinite chain along the c axis.In the title compound, [Cu(C DOI: 10.1107/S1600536808036635/hy2161Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometries of the protonated amino\u00adpyridinium cations reveal amine\u2013imine tautomerism. The crystal packing is influenced by N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distances = 3.635\u2005(4) and 3.642\u2005(4)\u00b0].The title compound, (C DOI: 10.1107/S160053680904923X/kp2235Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The dihedral angle between the mean planes of the two aromatic rings is 6.16\u2005(6)\u00b0. In the crystal, pairs of inter\u00admolecular weak C\u2014H\u22efO hydrogen bonds link neighboring mol\u00adecules into a chain along the a axis. The crystal structure is further stabilized by two inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of 3.7252\u2005(13) and 3.8323\u2005(13)\u2005\u00c5.In the title Schiff base complex, [Ni(C DOI: 10.1107/S1600536810007373/bq2198Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two benzene rings are individually planar and make a dihedral angle of 53.90\u00b0. The crystal structure is stabilized by inter\u00admolecular N\u2014H\u22efN hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions (centroid\u2013centroid distance = 3.962\u2005\u00c5).In the mol\u00adecule of the title compound, C DOI: 10.1107/S1600536809013415/rk2138Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit comprises one complex mol\u00adecule and a water mol\u00adecule of crystallization. The water H atoms form bifurcated O\u2014H\u22ef inter\u00admolecular hydrogen bonds with the O atoms of the phenolate and eth\u00adoxy groups with 12(5)R and 12(6)R ring motifs, which may, in part, influence the mol\u00adecular configuration. The dihedral angle between the two O\u2014Cu\u2014N coordination planes is 31.02\u2005(6)\u00b0 and the dihedral angle between the two benzene rings is 34.98\u2005(7)\u00b0. In the crystal structure, mol\u00adecules are linked together by inter\u00admolecular C\u2014H\u22efO inter\u00adactions, forming extended chains along the a axis. The crystal structure is further stabilized by inter\u00admolecular C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 [centroid\u2013centroid = 3.5068\u2005(13)\u2005\u00c5] inter\u00adactions.In the title complex, [Cu(C DOI: 10.1107/S1600536809012859/kj2122Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by C\u2014H\u22efCl inter\u00adactions. There is inter\u00admolecular \u03c0\u2013\u03c0 stacking between adjacent phenanthroline ligands, with a centroid\u2013centroid distance of 3.151\u2005(3)\u2005\u00c5.In the crystal structure of the title complex, [Zn DOI: 10.1107/S1600536809014482/at2764Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The O atoms of the perchlorate anions are disordered with occupancies in the ratio 0.593\u2005(10):0.407\u2005(10). In the crystal, mol\u00adecules are stabilized by two N\u2014H\u22efO hydrogen bonds, forming zigzag chains along the a axis, which are further inter\u00adconnected by N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.50\u2005(1)\u2005\u00c5] into a three-dimensional network.In the cation of the title compound, [Mn(C DOI: 10.1107/S1600536809029195/tk2501Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII atom is located on an inversion center and is coordinated by six O atoms from two water mol\u00adecules and four \u03bc2-carboxyl\u00adate groups of 4-fluoro\u00adbenzoate anions, forming a distorted CoO6 octa\u00adhedron, with Co\u2014O bond lengths in the range 2.071\u2005(2)\u20132.130\u2005(2)\u2005\u00c5. All adjacent O\u2014Co\u2014O angles are in the range 84.78\u2005(6)\u201395.22\u2005(6)\u00b0 and opposite angles are 180.0\u00b0. Each \u03bc-carboxyl\u00adate group of the 4-fluoro\u00adbenzoate anions bridges two symmetry-related CoII atoms. Hydrogen-bonding inter\u00adactions of the coordinated water mol\u00adecules further connect the cobalt\u2013carboxyl\u00adate units, forming layers perpendicular to the a axis. The cobalt\u2013oxygen layers are encased in a sandwich-like fashion by layers of \u03c0-stacked 4-fluoro\u00adbenzoate anions. Within these layers the benzene rings of the 4-fluoro\u00adbenzoate anions are \u03c0-stacked, with centroid\u2013centroid distances of 3.432\u2005(4)\u2005\u00c5.The hydro\u00adthermal reaction of CoCO DOI: 10.1107/S1600536809014913/zl2189Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal packing exhibits \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings from neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.616\u2005(4)\u2005\u00c5] and weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title mol\u00adecule, C DOI: 10.1107/S1600536808000895/cv2379Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure exhibits four inter\u00admolecular non-classical C\u2014H\u22efO hydrogen bonds. In addition, the crystal structure contains aromatic \u03c0\u2013\u03c0 inter\u00adactions between the furan and benzene rings of adjacent mol\u00adecules [centroid\u2013centroid distance = 3.743\u2005(2)\u2005\u00c5], and two inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, C DOI: 10.1107/S1600536809025938/ez2175Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, the complex mol\u00adecules are linked into a three-dimensional network by inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, and \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid separations of 3.758\u2005(2) and 3.597\u2005(1)\u2005\u00c5.In the title compound, [Zn(C DOI: 10.1107/S1600536809009180/hy2185Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two N atoms and the Cl atom are in equatorial positions while the remaining two N atoms occupy apical sites, the equatorial Cu\u2014N bonds being significantly longer than the two apical Cu\u2014N bonds. The N=C\u2014O\u2014C torsion angles involving the four eth\u00adoxy groups are in the range 161.5\u2005(8) to 177.0\u2005(5)\u00b0. In the crystal structure, there are significant \u03c0\u2013\u03c0 stacking inter\u00adactions between inversion-related rings of phenanthroline groups with centroid\u2013centroid distances in the range 3.649\u2005(4)\u20133.790\u2005(4)\u2005\u00c5.In the title complex, [CuCl(C DOI: 10.1107/S160053680804138X/lh2739Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Weak \u03c0\u2013\u03c0 stacking inter\u00adactions, with centroid\u2013centroid distances of 3.862\u2005(2) and 3.887\u2005(5)\u2005\u00c5, and significant C\u2014H\u22ef\u03c0 inter\u00adactions help to stabilize the crystal structure. The atoms of the unique terminal 4-pyridine\u00adpropane group are disordered over two sites, the ratio of refined occpancies being 0.712\u2005(7):0.288\u2005(7).In the title compound, [Mn(C DOI: 10.1107/S1600536809009891/lh2780Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are two formula units in the asymmetric unit. Molecules are further assembled into a three-dimensional network through C\u2014H\u22efCl contacts, a Cu\u22efCl weak inter\u00adaction [3.161\u2005(2)\u2005\u00c5], O\u2014H\u22efO  and C\u2014H\u22efO hydrogen bonds. The three water mol\u00adecules of the asymmetric unit are distributed over five positions with one full and two approximately half occupancies, while a tyrosine side chain in one of the complex mol\u00adecules is disordered over two positions [occupancies 0.507\u2005(5) and 0.493\u2005(5)].In the title compound, [Cu(C DOI: 10.1107/S1600536808012038/cs2072Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordinated water mol\u00adecule acting as the bridging ligand is located on a twofold axes and the complex mol\u00adecule displays C               2 mol\u00adecular symmetry. The Fe\u22efFe separation in the binuclear complex is 3.490\u2005(3)\u2005\u00c5. The crystal structure is stabilized by hydrogen bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions .In the title binuclear complex, [Fe DOI: 10.1107/S1600536808014207/kp2167Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The three pyridine rings are approximately coplanar, with a maximum deviation of 0.03\u2005\u00c5 from the mean plane. The phen\u00adoxy substituent makes a dihedral angle of 18.1\u2005(2)\u00b0 with the central pyridine ring. The benzyl group has a C\u2014O\u2014C\u2014C torsion angle of 77.62\u2005(8)\u00b0 relative to the phen\u00adoxy ring. In the crystal, mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds.In the title compound, [Zn(CH DOI: 10.1107/S1600536809049502/wm2284Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "II ion in the title compound, [Zn(C15H14N10)(H2O)2](ClO4)2, lies on a centre of symmetry. The distorted N4O2 octa\u00adhedral coordination environment around the Zn atom is composed of two 1,3-bis\u00ad[5-(2-pyrid\u00adyl)-2H-tetra\u00adzol-2-yl]propane ligands (L1) and two water mol\u00adecules, coordinated in trans positions. The ligand acts as a typical bidentate chelating ligand through one of its 2-pyridyl-2H-tetra\u00adzole units, forming a five-membered Zn\u2014N\u2014C\u2014C\u2014N metallacycle with a small N\u2014Zn\u2014N bite angle [77.40\u2005(8)\u00b0]. The other 2-pyridyl-2H-tetra\u00adzole unit remains uncoordinated. The average Zn\u2014N distance (2.156\u2005\u00c5) is somewhat longer than the distance between the ZnII center and the aqua ligand [2.108\u2005(2)\u2005\u00c5]. The coordinated pyrid\u00adyl-tetra\u00adzoyl rings are quasi-coplanar, making a dihedral angle of 1.9\u2005(2)\u00b0, while the uncoordinated rings show a larger inter\u00adplanar angle of 21.3\u2005(2)\u00b0. The flexible propane spacer displays a zigzag chain. Inter\u00admolecular O\u2014H\u22efN and O\u2014H\u22efO inter\u00adactions result in two-dimensional polymeric structures parallel to (100). Two C atoms of the spacer are disordered over two positions, with site occupancy factors of ca 0.85 and 0.15.The Zn DOI: 10.1107/S1600536808006703/bg2168Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds into chains running along [010]. Adjacent chains are joined together by weak \u03c0\u2013\u03c0 inter\u00adactions between benzene rings [centroid\u2013centroid distance = 4.040\u2005(2)\u2005\u00c5].There are two mol\u00adecules in the asymmetric unit of the title compound, C DOI: 10.1107/S1600536810000139/fk2009Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "IV atom in the title compound, [Sn(C6H5)2(C18H11ClN2O3)], is O,N,O\u2032-chelated by the deprotonated Schiff base ligand and further bonded by two phenyl rings in a distorted cis-C2SnNO2 trigonal-bipyramidal geometry [C\u2014Sn\u2014C = 125.7\u2005(2)\u00b0]. The two phenyl rings are oriented at a dihedral angle of 55.2\u2005(3)\u00b0. Intra\u00admolecular O\u2014H\u22efN hydrogen bonding is present in the crystal structure.The Sn DOI: 10.1107/S1600536809050107/xu2687Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The crystal structure is stabilized by C\u2014H\u22efBr hydrogen bonds and inter\u00admolecular C\u2014Br\u22ef\u03c0 inter\u00adactions [C\u22ef\u03c0 = 3.57\u2005(1)\u2005\u00c5].In the title compound, [Sb(C DOI: 10.1107/S1600536808033783/lx2073Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An intra\u00admolecular O\u2014H\u22efO hydrogen bond occurs. In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mononuclear complexes into chains extending parallel to [010]. Furthermore, \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.5696\u2005(6)\u2005\u00c5] stabilize the crystal structuure. In the mononuclear title complex, [Ni(C DOI: 10.1107/S1600536810034252/bt5331Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is an intra\u00admolecular O\u2014H\u22efO hydrogen bond. Inter\u00admolecular C\u2014H\u22efO hydrogen bonds result in the formation of a three-dimensional network and \u03c0\u2013\u03c0 stacking inter\u00adactions [3.44\u20133.83\u2005\u00c5] are observed between symmetry-related rings of 2-methyl\u00adfuropyridine. Further inter\u00adactions in the crystal structure are a short Cl\u22efCl inter\u00adaction [3.384\u2005(2)\u00c5] and C\u2014H\u22ef\u03c0 inter\u00adactions between 2-methyl\u00adfuropyridine rings.In the title compound, [Cu(C DOI: 10.1107/S1600536808008404/om2220Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are significant differences between chemically equivalent coordination bond lengths. The crystal structure is stabilized by weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance 3.495\u2005(1)\u2005\u00c5]. In one of the anions one nitro group is rotationally disordered about the C\u2014N bond with refined occupancies of 0.524\u2005(8) and 0.476\u2005(8).In the title complex, [Co(C DOI: 10.1107/S1600536809035934/lh2889Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efO hydrogen-bonding inter\u00adactions lead to infinite chains, which are further self-assembled into a supra\u00admolecular network through inter\u00admolecular N\u2014H\u22efO hydrogen-bonding inter\u00adactions and \u03c0\u2013\u03c0 stacking [centroid\u2013centroid distance = 3.717\u2005(2)\u2005\u00c5].In the mononuclear title compound, [Ni(C DOI: 10.1107/S1600536808009471/ng2442Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The central 1,6-diazecine ring adopts the common chair conformation invariably found in the family of complexes bearing such ligands. The CuII atoms have an octa\u00adhedral geometry, with a very strong tetra\u00adgonal distortion due to the Jahn\u2013Teller effect. Axial sites are occupied by a nitrate ion and a water mol\u00adecule. The Cu\u22efCu separations [7.3580\u2005(9) and 7.3341\u2005(9)\u2005\u00c5] are compatible with a potential catecholase activity. Neighboring mol\u00adecules in the crystal structure are connected via O\u2014H\u22efO hydrogen bonds formed by water mol\u00adecules and carboxyl\u00adate O atoms. N\u2014H\u22efO hydrogen bonds are also present.The title compound, [Cu II complexes based on related bis\u00ad(amino\u00adimidazole) ligands, which were designed as models of the catechol oxidaze active site, see: Driessen et al. (NO3)2(H2O)4]\u00b73H2O = 0.030                           wR(F                           2) = 0.082                           S = 1.02                           6396 reflections433 parameters22 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.50 e \u00c5\u22123                        \u0394\u03c1min = \u22120.48 e \u00c5\u22123                        \u0394\u03c1                                 XSCANS  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008Mercury (Macrae et al., 2006SHELXL97.Data collection: 10.1107/S1600536808023969/hy2146sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023969/hy2146Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The C\u2014Al\u2014C angles range from 113.25\u2005(7) to 116.27\u2005(8)\u00b0, much larger than the O\u2014Al\u2014C angles, which range from 103.39\u2005(7) to 103.90\u2005(6)\u00b0. The tetra\u00adhydro\u00adfuran ring adopts an envelope conformation. The crystal packing is stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Al(C DOI: 10.1107/S1600536808032091/ci2683Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one PbII ion, two benzoate ligands and one water mol\u00adecule. The Pb\u2014O bond distances are in the range 2.494\u2005(4)\u20132.735\u2005(4)\u2005\u00c5. The Pb\u22efPb distance is 4.0683\u2005(4)\u2005\u00c5, indicating an insignificant metal\u2013metal inter\u00adaction. The PbII atom has a distorted penta\u00adgonal-bipyramidal geometry chelated by two carboxyl\u00adate O atoms. The Pb atoms are bridged through a coordinating water mol\u00adecule and two carboxyl\u00adate O atoms from another two benzoate ligands, giving an infinite three-dimensional supra\u00admolecular structure. O\u2014H\u22efO hydrogen-bonding inter\u00adactions involved the coordinating water and carboxyl\u00adate O atoms enhance the stability of the supra\u00admolecular arrangement.The reaction of lead(II) nitrate and benzoic acid in aqueous solution yields the title polymer, [Pb(C For rel al. 2007.       7H5O2)2(H2O)] = 0.034                           wR(F                           2) = 0.087                           S = 1.09                           2664 reflections181 parametersH-atom parameters constrainedmax = 3.35 e \u00c5\u22123                        \u0394\u03c1min = \u22121.31 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008SHELXTL (Sheldrick, 2008SHELXTL.Data collection: 10.1107/S1600536809028542/fj2238sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028542/fj2238Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecules are linked into chains running parallel to the b axis by inter\u00admolecular N\u2014H\u22efO hydrogen bonds and by \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.669\u2005(2)\u2005\u00c5] involving centrosymmetrically related imidazole rings.In the title mononuclear complex, [Cu(C DOI: 10.1107/S1600536808012440/rz2208Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A three-dimensional network is formed via inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazole and benzene rings of neighboring mol\u00adecules [centroid\u2013centroid distance = 3.856\u2005(2)\u2005\u00c5].In the title mononuclear complex, [Ni(C DOI: 10.1107/S1600536809005960/hy2181Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The strongest cation\u2013cation O\u2014H\u22efO hydrogen bond in the structure, together with other strong cation\u2013cation N\u2014H\u22efO hydrogen bonds, generates a succession of infinite chains of R               2               2(8) rings along the b axis. Additional cation\u2013cation C\u2014H\u22efO hydrogen bonds link these chains into two-dimensional layers formed by alternating R               4               4(24) and R               4               2(12) rings. Connections between these layers are provided by the strong cation\u2013anion N\u2014H\u22efO hydrogen bonds, as well as by one weak C\u2014H\u22efO inter\u00adaction, thus forming a three-dimensional network. Some of the cation\u2013anion N\u2014H\u22efO hydrogen bonds are bifurcated of the type D\u2014H\u22ef.In the title compound, C DOI: 10.1107/S1600536809031730/fb2157Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Au atom exists within a linear geometry defined by an S,P-donor set with a deviation from linearity [S\u2014Au\u2014P = 176.86\u2005(6)\u00b0] due to the close approach of the thio\u00adcarbamate O atom [Au\u22efO = 3.108\u2005(5)\u2005\u00c5]. The mol\u00adecule has a U-shaped geometry which facilitates the formation of an intra\u00admolecular Au\u22efAu inter\u00adaction [3.0231\u2005(5)\u2005\u00c5]. In the crystal, the presence of C\u2014H\u22efOnitro contacts leads to the formation of layers with substantial voids; these are occupied by the solvent mol\u00adecules of crystallization, which are held in place by C\u2014H\u22efS contacts. The dinuclear title mol\u00adecule, [Au For the al. 1993.       2Fe(C10H11N2O3S)2(C17H14P)2]\u00b72CHCl3                         = 0.045                           wR(F                           2) = 0.104                           S = 0.97                           7148 reflections357 parametersH-atom parameters constrainedmax = 2.08 e \u00c5\u22123                        \u0394\u03c1min = \u22120.74 e \u00c5\u22123                        \u0394\u03c1                                 SMART  used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992SHELXL97 (Sheldrick, 2008DIAMOND (Brandenburg, 2006SHELXL97.Data collection: 10.1107/S1600536809043864/hb5168sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043864/hb5168Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Pt atom has an octa\u00adhedral coordination. In the crystal structure, inter\u00admolecular N\u2014H\u22efCl and C\u2014H\u22efCl hydrogen bonds result in the formation of a supra\u00admolecular structure. There is a \u03c0\u2013\u03c0 contact between the pyridine rings [centroid\u2013centroid distance = 4.235\u2005(1)\u2005\u00c5].The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536808025257/hk2508Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angles between the carboxyl\u00adate groups and the adjacent benzene rings are 11.33\u2005(13) and 10.90\u2005(9)\u00b0 and the benzene rings are oriented at a dihedral angle of 67.88\u2005(6)\u00b0. The uncoordinated water mol\u00adecules link the carboxyl\u00adate groups and coordinated water mol\u00adecules via O\u2014H\u22efO hydrogen bonding. Weak C\u2014H\u22ef\u03c0 inter\u00adactions are also found in the crystal structure.In the crystal structure of the title complex, {[Mn(C DOI: 10.1107/S1600536809021060/xu2525Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The equatorial positions are occupied by two N atoms from a 1,10-phenanthroline ligand [Cu\u2014N = 1.994\u2005(3) and 2.027\u2005(3)\u2005\u00c5] and two O atoms from dichloro\u00adacetate ligands and a water mol\u00adecule [Cu\u2014O = 1.971\u2005(2) and 1.939\u2005(2)\u2005\u00c5]. One O atom from another dichloro\u00adacetate ligand occupies the apical positon [Cu\u2014O = 2.152\u2005(3)\u2005\u00c5]. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds link the mol\u00adecules into centrosymmetric dimers. The crystal packing also exhibits weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.734\u2005(2)\u2005\u00c5] and short inter\u00admolecular Cl\u22efCl contacts [3.306\u2005(2) and 3.278\u2005(2)\u2005\u00c5].In the title complex, [Cu(C DOI: 10.1107/S1600536808042578/cv2493Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.814\u2005(9)\u2005\u00c5], and possibly by weak C\u2014H\u22ef\u03c0 inter\u00adactions. In addition, the crystal structure exhibits three inter\u00admolecular C\u2014H\u22efO non-classical hydrogen bonds. The ethyl group bonded to carboxyl\u00adate O atom is disordered over two positions, with refined site-occupancy factors of 0.686\u2005(18) and 0.314\u2005(18).The title compound, C DOI: 10.1107/S1600536809009775/rk2134Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecular packing in the crystal is stabilized by inter\u00admolecular N\u2014H\u22efO inter\u00adactions, linking the mol\u00adecules into infinite chains along the c axis. In addition, there are weak C\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, C DOI: 10.1107/S1600536810009803/bt5217Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The thia\u00adzole ring forms dihedral angles of 83.7\u2005(2) and 34.4\u2005(2)\u00b0 with the benzene ring of the benzodioxole ring and the fused phenyl ring, respectively. The mol\u00adecular conformation is stabilized by an intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction. The crystal packing features inter\u00admolecular C\u2014H\u22efN, C\u2014H\u22efO hydrogen bonds and weak C\u2014H\u22ef\u03c0 inter\u00adactions.In the title compound, [Fe(C DOI: 10.1107/S160053681003638X/rz2480Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a \u03c0\u2013\u03c0 contact between the pyridine rings [centroid\u2013centroid distance = 3.775\u2005(6)\u2005\u00c5].In the mol\u00adecule of the title compound, [HgI DOI: 10.1107/S1600536808028791/hk2525Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is assembled via hydrogen-bonding inter\u00adactions of two kinds, N(pyridine/amine)\u2014H\u22efBr\u2014Sn, along with C\u2014Br\u22efBr\u2014Sn interactions [3.4925\u2005(19)\u2005\u00c5]. The cations are involved in \u03c0\u2013\u03c0 stacking, which adds an extra supra\u00admolecularity as it presents a strong case of offset-face-to-face motifs [centroid\u2013centroid distance = 3.577\u2005(3)\u2005\u00c5]. The inter\u00admolecular hydrogen bonds, short Br\u22efBr inter\u00adactions and \u03c0\u2013\u03c0 stacking result in the formation of a three-dimensional supra\u00admolecular architecture.The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536809015189/hk2669Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "L) and the title silver(I) complex, namely bis\u00ad[\u03bc-1--2-naphthol]bis\u00ad{[1--2-naphthol]silver(I)} dinitrate monohydrate, [Ag2(C13H10N4O)4](NO3)2\u00b7H2O, were synthesized. Each silver center in the dimeric complex (related by an inversion centre) is coordinated by two bridging L ligands and one additional L ligand in a monodentate fashion, exhibiting a distorted trigonal-planar coordination. The discrete dimers are further linked through O\u2014H\u22efO hydrogen bonds and weak \u03c0\u2013\u03c0 stacking inter\u00adactions [the shortest atom\u2013atom separation is ca 3.46\u2005\u00c5 between the parallel stacking pairs]. Intramolecular O\u2014H\u22efN hydrogen bonds are also present.The new ligand 1--2-naphthol ( DOI: 10.1107/S1600536809004760/wk2097Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "This compound is composed of an anionic complex, [Al(pydc)2]\u2212, a protonated 2,2\u2032-bipyridine mol\u00adecule as a counter-ion, +, and three uncoordinated water mol\u00adecules. The anion is a six-coordinate complex, with the AlIII atom in a distorted octa\u00adhedral geometry coordinated by two tridentate pyridine-2,6-dicarboxyl\u00adate groups. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO, N\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, \u03c0\u2013\u03c0 stacking between two aromatic rings [centroid\u2013centroid distance = 3.827\u2005(10)\u2005\u00c5], and C=O\u22ef\u03c0 stacking , connect the various components to form a supra\u00admolecular structure.The title compound, (C DOI: 10.1107/S1600536808015973/su2057Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "IV compound, [Sn4(C7H6Cl)8Cl2O2(OH)2], has site symmetry 2\u2212 and two OH\u2212 anions bridge four SnIV cations to form the tetra\u00adnuclear compound. The two independent SnIV cations assume SnO3C2 and SnO2C2Cl distorted trigonal-bipyramidal coordination geometries. Intra\u00admolecular O\u2014H\u22efCl hydrogen bonding is present in the structure. One Cl atom of a chloro\u00adbenzyl ligand is disordered over two sites with an occupancy ratio of 0.693\u2005(2):0.307\u2005(2).The title tetra\u00adnuclear Sn DOI: 10.1107/S1600536809045176/xu2652Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, mol\u00adecules are linked into centrosymmetric dimers by pairs of O\u2014H\u22efO hydrogen bonds, and the dimers are linked together by \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.8310\u2005(13)\u2005\u00c5] and C\u2014H\u22efO bonds.In the mol\u00adecule of the title compound, C DOI: 10.1107/S1600536809049721/fk2006Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The bond distances for Sn\u2014C, Sn\u2014N and Sn\u2014O are in the ranges 2.097\u2005(3)\u20132.098\u2005(3), 2.298\u2005(2)\u20132.623\u2005(2) and 2.157\u2005(2)\u20132.266\u2005(2)\u2005\u00c5, respectively. The mol\u00adecular structure of the monomeric compound is stabilized by three intra\u00admolecular C\u2014H\u22efO hydrogen bonds, all involving bipyridine C\u2014H groups.In the crystal structure of the title compound, [Sn(CH DOI: 10.1107/S1600536808006090/im2056Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecular structure features intra\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds. In the crystal structure, the complex mol\u00adecules are assembled into a two-dimensional supra\u00admolecular layer parallel to (011) via O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridyl and pyrazole rings [centroid\u2013centroid distances = 3.544\u2005(2) and 3.722\u2005(3)\u2005\u00c5].In the mononuclear title complex, [Cd(C DOI: 10.1107/S1600536810034616/hy2347Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There is a \u03c0\u2013\u03c0 stacking inter\u00adaction between the symmetry-related 1,10-phenanthroline ligands with a centroid\u2013centroid distance of 3.5578\u2005(16)\u2005\u00c5 and a perpendicular distance of 3.445\u2005(su?)\u2005\u00c5 between the relevant rings.In the title complex, [CdCl DOI: 10.1107/S1600536809032358/bt5029Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Two AgI ions are each bonded to two N atoms from two isonicotinate ligands in a linear or bow-like fashion [N\u2014Ag\u2014N angles = 178.6\u2005(2) and 147.1\u2005(2)\u00b0]. These metal ions are connected by the isonicotin\u00adate ligands into a layer parallel to (010). O\u2014H\u22efO hydrogen bonds donated by the coordinated and uncoordinated water mol\u00adecules and intra\u00adlayer \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.551\u2005(4) and 3.555\u2005(4)\u2005\u00c5] are observed. The layers inter\u00adact with each other by inter\u00adlayer Ag\u22efO(aqua) contacts [2.731\u2005(4)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.466\u2005(3) and 3.516\u2005(3)\u2005\u00c5], resulting in the formation of a three-dimensional supra\u00admolecular structure.In the title compound, {[Ag DOI: 10.1107/S1600536810035634/hy2346Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral angle between the planes of the phenanthridine ring systems is 69.92\u2005(3)\u00b0. An intra\u00admolecular C\u2014H\u22efCl inter\u00adaction results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32\u2005(3)\u00b0 with respect to the adjacent phenanthridine ring system. In the crystal structure, \u03c0\u2013\u03c0 contacts between the phenanthridine systems  may stabilize the structure. Two weak C\u2014H\u22ef\u03c0 inter\u00adactions are also found.In the mol\u00adecule of the title compound, [ZnCl DOI: 10.1107/S160053680901959X/hk2696Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex anion is approximately planar with a maximum deviation of 0.097\u2005(1)\u2005\u00c5. In the 1-(4-nitro\u00adbenz\u00adyl)-4-cyano\u00adpyridinium cation, the pyridine ring is twisted at a dihedral angle of 73.84\u2005(16)\u00b0 with respect to the benzene ring. \u03c0-\u03c0 stacking is observed between nearly parallel [dihedral angle = 4.71\u2005(7)\u00b0] dithiole and benzene rings, the centroid\u2013centroid distance being 3.791\u2005(2)\u2005\u00c5.In the title salt, (C DOI: 10.1107/S1600536810037426/xu5018Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "O\u2014H\u22efO and O\u2014H\u22efCl hydrogen bonds involving hydr\u00adoxy groups and one of coordinated Cl atoms link complexes in the crystal packing. There is a \u03c0\u2013\u03c0 stacking inter\u00adaction between adjacent 1,10-phenanthroline rings, with a distance of 3.675\u2005(2)\u2005\u00c5 between the centroids of the pyridine and benzene rings.In the title complex, [CdCl DOI: 10.1107/S1600536809037465/kp2226Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The RuII ion is chelated by a 10,11,12,13-tetra\u00adhydro\u00addipyridophenazine ligand and two 2,9-dimethyl-1,10-phenanthroline ligands in a distorted octa\u00adhedral geometry. The two uncoord\u00adinated water mol\u00adecules are disordered over five positions, with an occupancy factor of about 0.4 for each site. A supra\u00admolecular structure is formed by weak \u03c0\u2013\u03c0 inter\u00adactions between neighbouring mol\u00adecules, with centroid\u2013centroid distances of 3.618\u2005(2) and 3.749\u2005(2)\u2005\u00c5.The title compound, [Ru(C DOI: 10.1107/S1600536810002874/hy2273Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The combination of coordinative bonds, O\u2014H\u22efN and O\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.630\u2005(2)\u2005\u00c5] results in the stabilization of a supra\u00admolecular structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water mol\u00adecules at about 333\u2005K, then the anhydrous phase loses no further mass up to about 573\u2005K, above which decomposition occurs.The hydro\u00adthermal reaction of CoCl DOI: 10.1107/S1600536809030165/at2833Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complex cations are linked by hydrogen bonds between the carboxyl groups into a chain. The chains are further connected through C\u2014H\u22efO hydrogen bonds and a weak Ag\u22efO inter\u00adaction [2.757\u2005(8)\u2005\u00c5] into a layer. Another Ag\u22efO inter\u00adaction [2.899\u2005(2)\u2005\u00c5] and a C\u2014H\u22efO hydrogen bond connect the layers into a three-dimensional network.In the title compound, [Ag(C DOI: 10.1107/S1600536808044206/hy2176Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII center is coordinated by six H2O mol\u00adecules in a distorted octa\u00adhedral coordination environment. In the crystal structure, intra- and inter\u00admolecular O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds link the cations and anions into a three-dimensional network. \u03c0\u2013\u03c0 contacts between the tetra\u00adzole rings [centroid\u2013centroid distance = 3.346\u2005(1)\u2005\u00c5] may further stabilize the structure.The asymmetric unit of the title complex, [Co(H DOI: 10.1107/S1600536809028463/hk2740Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bridging carbonyl C\u2014C(=O)\u2014C plane makes dihedral angles of 45.55\u2005(6) and 28.62\u2005(7)\u00b0, respectively, with the naphthalene ring system and the benzene ring. Weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions stabilize the crystal packing.In the title compound, C DOI: 10.1107/S1600536810006859/bt5198Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The centrosymmetric complex cation involves intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.862\u2005(4)\u2005\u00c5] between the central pyridine and benzene rings. In the crystal structure, inter\u00admolecular C\u2014H\u22efO hydrogen bonds result in the formation of a supra\u00admolecular network.In the binuclear title complex, [Ag DOI: 10.1107/S1600536809046832/hy2238Isup2.hklStructure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:"}
{"text": "The Ni\u2014N bond distances range from 2.1061\u2005(18) to 2.1425\u2005(18)\u2005\u00c5. The Mo\u2014C and C\u2014N distances in the [Mo(CN)8] unit range from 2.154\u2005(2) to 2.174\u2005(2)\u2005\u00c5 and 1.149\u2005(3) to 1.156\u2005(3)\u2005\u00c5, respectively. The complex ions and water mol\u00adecules are linked by weak N\u2014H\u22efN/O and O\u2014H\u22efN/O hydrogen bonds into a three-demensional structure.In the title compound, [Ni(C DOI: 10.1107/S1600536809051964/pv2243Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two N atoms and two O atoms around the CuII atom are trans to each other, with an O\u2014Cu\u2014O bond angle of 177.00\u2005(9)\u00b0 and an N\u2014Cu\u2014N bond angle of 165.63\u2005(10)\u00b0. The average distances between the CuII atom and the coordinated O and N atoms are 1.905\u2005(2) and 1.995\u2005(2)\u00c5, respectively.In the title complex, [Cu(C DOI: 10.1107/S1600536810037888/rk2236Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II complex, [Ni(C9H10NO2)2(C10H14N2O)2(H2O)2], contains two dimethyl\u00adamino\u00adbenzoate (DMAB), two diethyl\u00adnicotinamide (DENA) ligands and two water mol\u00adecules, all of them monodentate. The four O atoms in the equatorial plane around the NiII atom form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the DENA ligands in axial positions. The NiII atom is displaced by 0.681\u2005(1)\u2005\u00c5 out of the least-squares plane of the carboxyl\u00adate group. The dihedral angle between the carboxyl\u00adate group and the adjacent benzene ring is 5.61\u2005(7)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 73.20\u2005(4)\u00b0. An intra\u00admolecular O\u2014H\u22efO hydrogen bond results in the formation of a six-membered ring with a twisted conformation. In the crystal structure, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link mol\u00adecules into a three-dimensional network. Two weak C\u2014H\u22ef\u03c0 inter\u00adactions are also present.The centrosymmetric title Ni N,N-diethyl\u00adnicotinamide, an important respiratory stimulant, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.029                           wR(F                           2) = 0.076                           S = 1.04                           4819 reflections253 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.47 e \u00c5\u22123                        \u0394\u03c1min = \u22120.41 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536809030098/xu2570sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030098/xu2570Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Pt\u2014P bond lengths of 2.2536\u2005(8) and 2.2513\u2005(8)\u2005\u00c5 and the Pt\u2014Cl bond lengths of 2.3750\u2005(8) and 2.3588\u2005(8)\u2005\u00c5 are normal. This crystal form is a polymorph of a structure reported previously .The title complex, [PtClasai 1976. Bull. C DOI: 10.1107/S1600536808000603/pv2062Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Neighboring CoII atoms are linked together by two Cl bridges, forming a dinuclear CoII complex with inversion symmetry. There are inter\u00admolecular O\u2014H\u22efCl hydrogen bonds and inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent bpy ligands [centroid\u2013centroid distance = 3.617\u2005(2)\u2005\u00c5] in the structure.The title complex, [Co DOI: 10.1107/S1600536809027846/at2843Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The complexes are assembled into a three-dimensional network via C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions. The mean inter\u00adplanar distance between adjacent phenanthroline ligands is 3.399\u2005(2)\u2005\u00c5.In the crystal structure of the title compound, [Zn(C DOI: 10.1107/S1600536808006004/is2271Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CoII cation is coordinated by two Cl\u2212 ions, one N atom from the 5-(4-pyridinio)tetra\u00adzolate zwitterion and three O atoms from three water mol\u00adecules in a distorted octa\u00adhedral geometry. In the crystal, mol\u00adecules are linked into a three-dimensional network by N\u2014H\u22efCl hydrogen bonds and O\u2014H\u22efO/N/Cl hydrogen bonds involv\u00ading both coordinated and uncoordinated water mol\u00adecules. Strong \u03c0\u2013\u03c0 stacking is present between parallel pyridinium and tetra\u00adzolate rings [centroid\u2013centroid distances = 3.411\u2005(2) and 3.436\u2005(2)\u2005\u00c5].The title compound, [CoCl DOI: 10.1107/S1600536809024337/ci2831Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Both the cationic and anionic portions of the starting proton-transfer compound are involved in the complexation. The NiII atom has a distorted octa\u00adhedral geometry and is hexa\u00adcoordinated by three O atoms and three N atoms from one phen fragment (as a bidentate ligand), one (pydc)2\u2212 unit (as a tridentate ligand) and one water mol\u00adecule. In the crystal structure, extensive O\u2014H\u22efO, O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds with D\u22efA distances ranging from 2.573\u2005(2) to 3.385\u2005(2)\u2005\u00c5, \u03c0\u2013\u03c0 inter\u00adactions between the phen ring systems  and inter\u00admolecular C\u2014O\u22ef\u03c0 inter\u00adactions  connect the various components together.The title compound, [Ni(C DOI: 10.1107/S1600536808039378/om2263Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The other NiII ion is also six-coordinated, by four other pyridine N atoms from four other amino\u00adpyridine ligands and two carbonate O atoms to complete a distorted octa\u00adhedral geometry. In the crystal structure, mol\u00adecules are linked into an infinite three-dimensional network by O\u2014H\u22efO, N\u2014H\u22efCl, N\u2014H\u22efO, O\u2014H\u22efN, C\u2014H\u22efO, C\u2014H\u22efN and C/N\u2014H\u22ef\u03c0 inter\u00adactions involving the pyridine rings.In the title compound, [Ni DOI: 10.1107/S1600536808033321/at2653Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The apical Cu\u2014O bond [2.3520\u2005(16)\u2005\u00c5] is much longer than the basal Cu\u2014O and Cu\u2014N bonds [1.9139\u2005(14)\u20132.0136\u2005(17)\u2005\u00c5]. The carboxyl\u00adate group bridges CuII atoms, forming a zigzag chain along the a axis.In the title compound, [Cu(C DOI: 10.1107/S1600536809037520/is2450Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The MoVI atom shows a distorted octa\u00adhedral environment, with the phenanthroline N atoms and the two oxide groups forming the equatorial plane and the F atoms occupying the apical positions. Weak C\u2014H\u22efO and C\u2014H\u22efF hydrogen-bonding contacts and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.662\u2005(1)\u2005\u00c5] connect the complex mol\u00adecules into a three-dimensional supra\u00admolecular framework.The title compound, [MoF DOI: 10.1107/S1600536809031626/si2192Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "A short intra\u00admolecular C\u2014H\u22ef\u03c0 interaction is observed involving a substituted \u03b75-C5H4 ring and an ortho H atom of the benzene ring on the opposite side of the mol\u00adecule. In the crystal structure, there are no classical hydrogen bonds: inter\u00adactions comprise a short C6\u2014H\u22ef\u03c0(C6) inter\u00adaction involving substituted benzene rings and two C\u2014H\u22efO=C inter\u00adactions per mol\u00adecule.The title compound, [Fe DOI: 10.1107/S1600536809006278/bg2237Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials: interactive version of Fig. 2            Enhanced figure:"}
{"text": "There is a mean deviation of 0.016\u2005(4)\u2005\u00c5 from the least-squares plane defined by the nine constituent benzofuran atoms. The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid\u2013centroid distance = 3.689\u2005(7)\u2005\u00c5]and by a weak C\u2014H\u22ef\u03c0 interaction between an H atom of the methylene group bonded to the carboxylate O atom and the benzene ring of an adjacent molecule. In addition, the crystal structure exhibits weak non-classical inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The chloro\u00adethyl group is disordered over two positions, with refined site-occupancy factors of 0.767\u2005(6) and 0.233\u2005(6).In the title compound, C DOI: 10.1107/S1600536809012847/sj2602Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular C\u2014H\u22efCl hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pyridine rings [centroid\u2013centroid distances = 3.788\u2005(1) and 3.957\u2005(1)\u2005\u00c5] are present in the crystal structure.In the title compound, [CoCl DOI: 10.1107/S1600536810036846/hy2353Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The terpyridyl motif in each fctpy ligand is coplanar, but the cyclo\u00adpenta\u00addienyl ring is twisted by 9.5\u2005(2)\u00b0 out of coplanarity with each central pyridine. The two cyclo\u00adpenta\u00addienyl rings of the ferrocenyl group are almost eclipsed with a deviation of 4.5\u2005(1)\u00b0. In addition, inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance 3.753\u2005(2)\u2005\u00c5] are present between the cyclo\u00adpenta\u00addienyl and outer pyridyl rings of the fctpy ligands. One of the perchlorate anions is equally disordered over two positions.In the title complex, [FeZn(C DOI: 10.1107/S1600536809023939/jh2081Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It differs from the first ortho\u00adrhom\u00adbic polymorph [Pan, Lin & Zheng  ligand. In the present structure, the Cu atom is shifted from the mean plane of the dmp ligand by only 0.005\u2005(1)\u2005\u00c5, compared with 0.318\u2005(6)\u2005\u00c5 in the ortho\u00adrhom\u00adbic form. Hydrogen-bonding and \u03c0\u2013\u03c0 stacking inter\u00adactions (mean inter\u00adplanar distance of 3.59\u2005\u00c5 in the title compound) in the two different polymorphs are both essential to the supra\u00admolecular assembly.A new monoclinic polymorphic form of the title compound, [Cu(HCOheng 2005. Z. Kris DOI: 10.1107/S1600536808022812/fj2128Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00admolecular O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding, as well as \u03c0\u2013\u03c0 stacking between parallel thia\u00adzole rings [centroid\u2013centroid distance 3.531\u2005(8)\u2005\u00c5], helps to stabilize the crystal structure.In the crystal structure of the title compound, [Ni(C DOI: 10.1107/S1600536809017978/xu2518Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Together the ligands create a slightly distorted square-planar cordination environment for the Rh(I) atom. There are three mol\u00adecules in the asymmetric unit and intra\u00admolecular P\u2014Rh\u2014P bite angles of 82.78\u2005(5), 82.97\u2005(6) and 83.09\u2005(5)\u00b0 are observed. The dihedral angles between the P\u2014Rh\u2014P and the X\u2014Rh\u2014X planes (X is the centroid of a double bond) are 14.7\u2005(1), 14.8\u2005(1) and 15.3\u2005(1)\u00b0. The structure exhibits disorder of one cyclo\u00adocta\u00addiene ligand as well as one BF4 anion.The title compound, [Rh(C DOI: 10.1107/S1600536810019859/im2198Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "It was synthesized from 2,4,6,8-tetra\u00adphenyl-3,7-diaza\u00adbicyclo\u00ad[3.3.1]nonan-9-one and was crystallized from a methanol\u2013ethanol solution over two years as a racemate. The C=N double bond [1.2868\u2005(15)\u2005\u00c5] is bent significantly out of the plane of the aromatic bicyclic ring system [N\u2014C\u2014C\u2014C = \u2212157.63\u2005(12)\u00b0] and out of the plane of the phenyl ring bonded at the 1-position [N\u2014C\u2014C\u2014C = 41.15\u2005(16)\u00b0].The title compound, C DOI: 10.1107/S1600536810013619/bt5246Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Intra\u00admolecular C\u2014H\u22efO hydrogen bonding and inter\u00admolecular \u03c0\u2013\u03c0 stacking between parallel pyridine rings [centroid\u2013centroid distance = 3.658\u2005(3)\u2005\u00c5] are present in the crystal structure.In the title compound, [CdI DOI: 10.1107/S1600536810012572/xu2734Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The anion is a six-coordinated complex with a distorted octa\u00adhedral geometry around the FeIII atom. Extensive inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, involving the complex anion, (pydaH)+ counter-ion and two uncoordinated water mol\u00adecules, and \u03c0\u2013\u03c0 [centroid-to-centroid distance 3.323\u2005(11)\u2005\u00c5] and C\u2014O\u22ef\u03c0 [O\u2013centroid distance 3.150\u2005(15)\u2005\u00c5] inter\u00adactions connect the various components into a supra\u00admolecular structure.The reaction of iron(II) sulfate hepta\u00adhydrate with the proton-transfer compound (pydaH)(hypydcH) (pyda = pyridine-2,6-diamine; hypydcH DOI: 10.1107/S1600536808029280/hy2152Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The pyrrolidine ring is almost perpendicular to the cyclo\u00adpenta\u00adnone ring, making a dihedral angle of 81.91\u2005(6)\u00b0. The mol\u00adecular conformation is stabilized by an intra\u00admolecular O\u2014H\u22efN hydrogen bond and C\u2014H\u22efO inter\u00adactions. The crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efO inter\u00adactions.In the title compound, [Fe(C DOI: 10.1107/S1600536809018583/bt2949Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CuII center has a distorted square-pyramidal coordination with three N atoms of the 4\u2032-ferrocenyl-2,2\u2032:6\u2032,2\u2032\u2032- terpyridine (fctpy) ligand and one 1,10-phenanthroline (phen) N atom in the basal plane and a second phen N atom in the apical position with an axial distance of 2.254\u2005(4)\u2005\u00c5. The disordered ClO4               \u2212 anion is weakly coordin\u00adated to the CuII ion with a Cu\u2014O distance of 2.766\u2005(11)\u2005\u00c5. The two cyclo\u00adpenta\u00addienyl rings of the ferrocenyl group are almost eclipsed with a deviation of 4.7\u2005(1) \u00b0, and are involved in inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions with the outer pyridyl rings of the fctpy ligands [centroid\u2013centroid distance = 3.759\u2005(2)\u2005\u00c5.].The title complex, [CuFe(C DOI: 10.1107/S1600536809020753/at2803Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bis\u00ad(diphenyl\u00adarsino)methane ligand bridges an Ru\u2014Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the phosphine and arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. With regard to the three phosphine-substituted rings, the benzyl ring makes dihedral angles of 41.0\u2005(3) and 43.9\u2005(3)\u00b0 with the other two benzene rings in mol\u00adecule A; these angles are 49.8\u2005(3) and 56.8\u2005(3)\u00b0 in mol\u00adecule B. The dihedral angles between the two benzene rings are 76.1\u2005(3) and 88.2\u2005(3)\u00b0 for the two diphenyl\u00adarsino groups in mol\u00adecule A and 71.3\u2005(3) and 78.1\u2005(3)\u00b0 in mol\u00adecule B. In the crystal packing, mol\u00adecules are linked into chains via inter\u00admolecular C\u2014H\u22efO hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions further stabilize the crystal structure.The asymmetric unit of the title  DOI: 10.1107/S1600536809053045/sj2709Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The average Ni\u2014N and Ni\u2014O bond lengths are 2.131\u2005(13) and 2.098\u2005(11)\u2005\u00c5, respectively. An intramolecular N\u2014H\u22efO inter\u00adaction occurs. Relatively weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions between the ligands and the ClO4               \u2212 ions result in a chain extending along the b axis.In the title complex, [Ni(CH DOI: 10.1107/S1600536810034446/pv2321Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The Co\u2014N bonds involving the thio\u00adcyanate ligands are significantly shorter than the other two Co\u2014N bonds. The atoms of one of the eth\u00adoxy groups are essentially coplanar with the phenanthroline ring [N=C\u2014O\u2014C = 178.8\u2005(4)\u00b0], while the other eth\u00adoxy group is slightly twisted from the phenanthroline ring plane [N=C\u2014O\u2014C = 167.2\u2005(4)\u00b0]. In the crystal structure, there is a weak \u03c0\u2013\u03c0 stacking inter\u00adaction between two symmetry-related phenanthroline rings with a centroid\u2013centroid distance of 3.706\u2005(4)\u2005\u00c5.In the title complex, [Co(NCS) DOI: 10.1107/S160053680803496X/lh2718Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The coordination bonds of the 4,4\u2032-substituted bipyridyl donors [Ru\u2014N = 2.038\u2005(3) and 2.051\u2005(3)\u2005\u00c5] are shorter than those of the 2,2\u2032-bipyridyl donors [Ru\u2014N1 = 2.065\u2005(3)\u20132.077\u2005(3)\u2005\u00c5], due to the electron-withdrawing effects of the substituents at the 4,4\u2032-positions. The angles between the pyridyl planes of the three bipyridyl ligands are 1.5\u2005(2), 6.3\u2005(3) and 8.7\u2005(2)\u00b0, respectively. The cations are connected by anions via N\u2014H\u22efF inter\u00adactions.In the title compound, [Ru(C DOI: 10.1107/S1600536809002360/kp2198Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The [ZnCl4]2\u2212 anions have a distorted tetra\u00adhedral geometry. The dihedral angles between the isoquinoline rings of the two cations are nearly equal [16.1\u2005(2) and 16.3\u2005(2)\u00b0]. In the crystal structure, the ordered linear formation is aggregated by weak inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions between neighboring isoquinoline pyridine rings with a centroid\u2013centroid distance of 3.779\u2005(4)\u2005\u00c5.The asymmetric unit of the title compound, (C DOI: 10.1107/S1600536809017693/bq2137Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometry of the resulting CuN2O4 coordination can be described as distorted octa\u00adhedral. The the two pydc2\u2212 fragments are almost perpendicular to one another [77.51\u2005(11)\u00b0]. To balance the charges, two centrosymmetric protonated butane-1,4-diammonium, (bdaH2)2+ cations are present. In the crystal structure, extensive O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds [D\u22efA = 2.720\u2005(2)\u20133.446\u2005(3)\u2005\u00c5], ion pairing, C\u2014O\u22ef\u03c0 [O\u22ef\u03c0 = 3.099\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 stacking inter\u00adactions between the pydc2\u2212 rings [centroid\u2013centroid distance = 3.5334\u2005(15)\u2005\u00c5] contribute to the formation of a three-dimensional supra\u00admolecular structure.In the title compound, (C DOI: 10.1107/S1600536808011938/su2053Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, N\u2014H\u22efO hydrogen bonds link mol\u00adecules in rows along a. Short inter\u00admolecular Cl\u22efCl inter\u00adactions [3.4225\u2005(5)\u2005\u00c5] link these rows into sheets in the ac plane. Additional weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions generate a three-dimensional network.In the title benzamide derivative, C DOI: 10.1107/S1600536808036313/sg2272Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The metal centre has a distorted octa\u00adhedral coordination with the monoanionic Schiff base ligand occupying one equatorial and two axial coordination positions. The separation between V atoms is 3.214\u2005(3)\u2005\u00c5. In the crystal structure, there are N\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 hydrogen bonds, and \u03c0\u2013\u03c0 inter\u00adactions.In the title dinuclear compound, [V DOI: 10.1107/S160053680801787X/xu2429Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by aromatic \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of neighbouring mol\u00adecules [centroid-to-centroid distance = 3.635\u2005(3)\u2005\u00c5], and by C\u2014H\u22ef\u03c0 inter\u00adactions between a propyl methyl\u00adene H atom and the furan ring of an adjacent mol\u00adecule. In addition, the crystal structure exhibits weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds.In the title compound, C DOI: 10.1107/S1600536809004735/gk2190Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Inter\u00adactions of the \u03c0\u2013\u03c0 type are absent between cations in the stacks [centroid\u2013centroid separation = 5.01\u2005(5)\u2005\u00c5]. Significant inter\u00admolecular Br\u2013aryl inter\u00adactions are present in the structure, especially an unusually short Br\u2013ring centroid inter\u00adaction of 3.78\u2005(1)\u2005\u00c5. The coordination geometry of the anion is approximately tetrahedral and a twofold rotation axis passes through the Co atom.In the crystal structure of the title compound, (C DOI: 10.1107/S160053680800439X/at2543Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2-fluoro\u00adbenzoate ligands bridge Pb atoms, giving rise to a one-dimensional chain structure extending along the [100] direction. The polymeric chains are connected via C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions, with an inter\u00adplanar distance of 3.46\u2005(1)\u2005\u00c5. An intramolecular O\u2014H\u22efF interaction is also present.In the title compound, [Pb DOI: 10.1107/S1600536808022678/hy2143Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "Face-to-face \u03c0-stacking inter\u00adactions between inversion-related pyridine rings with centroid\u2013centroid distances of 3.548\u2005(3) and 3.662\u2005(3)\u2005\u00c5 (perpendicular distances between the respective rings are 3.314 and 3.438\u2005\u00c5) are found. Inter\u00admolecular O\u2014H\u22efO hydrogen bonds between water mol\u00adecules and L ligands form R               5               3(10), R               6               5(14) and R               5               5(12) rings and also a centrosymmetric cage-like unit of water mol\u00adecules, which link eight adjacent NiII centers, forming a three-dimensional framework.In the title compound, [Ni(C DOI: 10.1107/S1600536809006515/si2152Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II atom of the title complex, [Cu(C17H15N2S2)2], lies on a twofold rotation axis, and is in a distorted tetra\u00adhedral geometry with the two bidentate N2S2 Schiff bases. In the crystal structure, the mol\u00adecules are inter\u00adconnected into chains along the c axis by weak C\u2014H\u22efS inter\u00admolecular inter\u00adactions. The crystal packing is further stabilized by C\u2014H\u22ef\u03c0 inter\u00adactions.The Cu DOI: 10.1107/S1600536808002262/ci2558Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The dihedral between the naphthalene ring system and the bridging carbonyl C\u2014C(=O)\u2014C plane is 54.68\u2005(6)\u00b0, far larger than that [12.54\u2005(7)\u00b0] between the phenyl group and the bridging carbonyl group. The nitro group and the phenyl ring are almost coplanar [O\u2014N\u2014C\u2014C torsion angle = 2.94\u2005(19)\u00b0]. In the crystal, mol\u00adecules are linked by C\u2014H\u22ef\u03c0 inter\u00adactions and the phenyl rings are involved in a centrosymmetric \u03c0\u2013\u03c0 inter\u00adaction with a perpendicular distance of 3.523\u2005\u00c5 and a lateral offset of 1.497\u2005\u00c5. In addition, weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds are formed between an H atom of one meth\u00adoxy group and a nearby carbonyl O atom.In the title compound, C DOI: 10.1107/S1600536810005398/fl2290Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The observed Pt\u2014I bond distances of 2.6094\u2005(5) and 2.6130\u2005(5)\u2005\u00c5 are in the expected range for PtI2 complexes. The C=C double bonds in the mol\u00adecule differ significantly [1.373\u2005(10) and 1.403\u2005(10)\u2005\u00c5]. As expected for a platinum(II) complex, the PtII atom is in a square-planar environment (\u03a3Pt\u03b1= 359.71\u00b0).The monoclinic title complex, [PtI DOI: 10.1107/S1600536809029997/bg2283Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The AgI atom is coordinated in an almost linear fashion by two pyridyl N atoms from two nicotinate ligands. The linear coordination is augmented by weak inter\u00adactions with three O atoms from one perchlorate anion, one uncoordinated water mol\u00adecule and one carboxyl\u00adate group. Two Pr atoms link two {Ag(nic)2}+ units into a ring, which is further extended into an infinite zigzag chain by sharing the Pr atoms. These chains are further connected into a three-dimensional network via weak Ag\u22efO inter\u00adactions, O\u2014H\u22efO hydrogen bonds, Ag\u22efAg inter\u00adactions [3.357\u2005(2)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl rings [centroid\u2013centroid distance = 3.685\u2005(4)\u2005\u00c5].In the title compound, {[Ag DOI: 10.1107/S1600536809001718/hy2177Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The bis\u00ad(diphenyl\u00adarsino)methane ligand bridges an Ru\u2014Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the phosphine and arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three phosphine-substituted benzene rings make dihedral angles of 73.5\u2005(3), 57.2\u2005(3) and 75.7\u2005(3)\u00b0 with each other in mol\u00adecule A, while these angles are 60.7\u2005(3), 86.8\u2005(3) and 54.9\u2005(3)\u00b0 in mol\u00adecule B. The dihedral angles between the two benzene rings are 87.3\u2005(3) and 89.6\u2005(3)\u00b0 for the two diphenyl\u00adarsino groups in mol\u00adecule A and 85.6\u2005(3) and 87.7\u2005(3)\u00b0 in mol\u00adecule B. In the crystal packing, the mol\u00adecules are linked into a three-dimensional framework via inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions furture stabilize the crystal structure. The crystal studied was an inversion twin, the refined ratio of twin components being 0.480\u2005(7):0.520\u2005(7).The asymmetric unit of the title  DOI: 10.1107/S1600536809053884/sj2702Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The benzofuran ring plane makes dihedral angles of 28.63\u2005(6) and 31.55\u2005(5)\u00b0 with the 4-fluoro\u00adphenyl and phenyl rings, respectively. Weak C\u2014H\u22efF and C\u2014H\u22efO hydrogen bonds and inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are present in the crystal structure. The title crystal was refined as an inversion twin with a 0.39\u2005(7):0.61\u2005(7) domain ratio.In the title mol\u00adecule, C DOI: 10.1107/S1600536810014613/fb2185Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains two PbII atoms, four MBA ligands and two water mol\u00adecules. Each PbII cation is hepta\u00adcoordinated and chelated by four carboxyl\u00adate O atoms from two MBA ligands. The Pb atoms are bridged through the carboxyl\u00adate O atoms from another two MBA ligands, leading to a central Pb2O2 core. The Pb\u2014O bond lengths are in the range 2.325\u2005(3)\u20132.757\u2005(4)\u2005\u00c5. The intra- and inter\u00addimer Pb\u22efPb distances are 4.2942\u2005(3) and 4.2283\u2005(3)\u2005\u00c5, respectively, indicating little direct metal\u2013metal inter\u00adaction. The coordinating water mol\u00adecules and carboxyl\u00adate O atoms are involved in extensive O\u2014H\u22efO hydrogen-bonding inter\u00adactions. The complex has an extended ladder-like chain structure and the chains are assembled by hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distance = 3.6246\u2005(3)\u2005\u00c5] into a three-dimensional supra\u00admolecular structure.The reaction of lead(II) acetate and 3-methyl\u00adbenzoic acid (MBA) in aqueous solution yielded the title polymer, [Pb(C DOI: 10.1107/S1600536809019771/fj2218Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "H)-thiolate anions in the asymmetric unit of the title compound, Na+\u00b7C2H2N3S2               \u2212\u00b72H2O, which are almost perpendicular to each other [dihedral angle = 84.64\u2005(6)\u00b0]. The two Na+ cations are in distorted fourfold coordinations by O atoms of the water molecules. The crystal structure is stabilized by N\u2014H\u22efS, O\u2014H\u22efN and O\u2014H\u22efS hydrogen bonds.There are two 5-amino-1,3,4-thia\u00addiazole-2(3 DOI: 10.1107/S1600536809051897/pk2208Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In addition to the usual inter\u00admolecular C\u2014H\u22efO hydrogen bonding, short intra\u00admolecular C\u2014H\u22efS contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid distance = 3.762\u2005(2)\u2005\u00c5] contribute to the crystal packing.In the title compound, C DOI: 10.1107/S1600536808007356/rk2081Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the crystal structure, inter\u00admolecular N\u2014H\u22efBr hydrogen bonds link the mol\u00adecules into centrosymmetric dimers. There are \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distances = 3.9662\u2005(5) and 3.9321\u2005(4)\u2005\u00c5]. There also exists a C\u2014H\u22ef\u03c0 contact between the pyridine CH group and a pyridine ring.In the mol\u00adecule of the title compound, [HgBr DOI: 10.1107/S1600536808038129/hk2575Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "An inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adaction between the pyridine rings [centroid\u2013centroid distance = 3.900\u2005(4)\u2005\u00c5] is observed. The CdII atom has a distorted tetra\u00adhedral coordination.In the cation of the title compound, (C DOI: 10.1107/S1600536808030092/is2330Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The centroid\u2013centroid distances of 3.809\u2005(2) and 3.680\u2005(2)\u2005\u00c5 between nearly parallel pyridine rings of the phen ligands and the benzene rings of dhba anions indicate that the dhba anions are involved in \u03c0\u2013\u03c0 stacking in the crystal structure. The face-to-face separation of 3.35\u2005(3)\u2005\u00c5 between parallel phen ring systems also suggests \u03c0\u2013\u03c0 stacking between adjacent complex mol\u00adecules. The crystal structure contains extensive O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonding.In the crystal structure of the title compound, [Cd(C DOI: 10.1107/S1600536808018126/rk2092Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by various \u03c0\u2013\u03c0 stacking inter\u00adactions in which the benzene ring, a pyridine ring and the five-membered CuN2C2 ring are involved. The centroid\u2013centroid distances range from 3.5631\u2005(15) to 3.5666\u2005(16)\u2005\u00c5.In the title mononuclear complex, [CuCl DOI: 10.1107/S160053680801948X/lh2647Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is composed of centrosymmetric dimers lying about inversion centres. Both independent Sn atoms adopt distorted trigonal-bipyramidal SnC2O3 coordination geometries with the basal planes consisting of two C-atoms from the methyl groups and a bridging O atom. The Sn\u2014C and Sn\u2014O bond lengths lie in the ranges 2.090\u2005(2)\u20132.104\u2005(3) and 2.0241\u2005(14)\u20132.2561\u2005(15)\u2005\u00c5, respectively. The central four-membered planar Sn2O2 ring [Sn\u22efSn distance = 3.2993\u2005(2)\u2005\u00c5] makes dihedral angles of 5.43\u2005(11) and 59.50\u2005(7)\u00b0 with the methyl\u00adphenyl groups, which are themselves oriented at a dihedral angle of 61.38\u2005(8)\u00b0. Besides weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions, the packing mainly features van der Waals forces between the mol\u00adecules.The title compound, [Sn DOI: 10.1107/S1600536810036512/wm2399Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one 4-methyl\u00adbenzoate anion, one nicotinamide (NA) ligand and one coordinated water mol\u00adecule. The four O atoms in the equatorial plane around the MnII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 9.01\u2005(7)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 42.44\u2005(5)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, and O\u2014H\u22ef\u03c0 and C\u2014H\u22ef\u03c0 inter\u00adactions link the mol\u00adecules into a two-dimensional network parallel to (001).In the mononuclear title complex, [Mn(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.035                           wR(F                           2) = 0.099                           S = 1.08                           3297 reflections204 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.73 e \u00c5\u22123                        \u0394\u03c1min = \u22120.38 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008ORTEP-3 for Windows (Farrugia, 1997WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810011815/ci5069sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011815/ci5069Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "In the absence of any strong hydrogen bonds, the structure results from a large number of competing weaker inter\u00adactions including Cl\u22efCl [3.4610\u2005(5)\u2005\u00c5] and C\u2014H\u22efCl contacts and both (aryl) C\u2014H\u22efBr and N+\u2014Csp               3\u2014H\u22efBr\u2212 cation\u2013anion inter\u00adactions.In the title compound, C DOI: 10.1107/S160053680902159X/jh2078Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The 2,6-dihydroxy\u00adbenzoic acid mol\u00adecule is disordered about an inversion center. The face-to-face separations of 3.540\u2005(11) and 3.429\u2005(8)\u2005\u00c5 between parallel phen ligands indicate the existence of \u03c0\u2013\u03c0 stacking between adjacent MnII complexes. Uncoordinated water mol\u00adecules are linked with complex and dihydroxy\u00adbenzoic acid mol\u00adecules via O\u2014H\u22efCl and O\u2014H\u22efO hydrogen bonds.In the crystal structure of the title compound, [MnCl DOI: 10.1107/S1600536808012427/ng2452Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The crystal structure is stabilized by N\u2014H\u22efO, N\u2014H\u22efN, O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds. In addition, weak \u03c0\u2013\u03c0 inter\u00adactions are observed between symmetry-related thia\u00addiazole ring systems .The title compound, C DOI: 10.1107/S1600536809021825/at2800Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The AgI atom is coordinated in an almost linear fashion by two pyridyl N atoms of two nic ligands. The linear coordination is augmented by weak inter\u00adactions with one O atom from a half-occupied ClO4               \u2212 anion and a water mol\u00adecule lying on a twofold axis. Two Ag(nic)2 units connect two La atoms, forming a cyclic unit. These units are further extended into an infinite zigzag chain. The chains are bridged by the disordered perchlorate ions via weak Ag\u2014O [2.678\u2005(2)\u2005\u00c5] inter\u00adactions. O\u2014H\u22efO hydrogen bonds, weak Ag\u22efAg [3.3340\u2005(15)\u2005\u00c5] inter\u00adactions and \u03c0\u2013\u03c0 inter\u00adactions between the pyridyl rings [centroid\u2013centroid distance = 3.656\u2005(2)\u2005\u00c5] lead to a three-dimensional network.In the title complex, [Ag DOI: 10.1107/S1600536809026130/hy2200Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The mol\u00adecule has a short intra\u00admolecular contact involving an aromatic H atom (Au\u22efH = 2.64\u2005\u00c5); two adjacent mol\u00adecules are linked by an Au\u22efHylid inter\u00adaction (Au\u22efH = 3.14\u2005\u00c5).The metal atom in the title ylid\u2013gold(I) adduct, [Au(C DOI: 10.1107/S160053680904152X/ng2660Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The geometry of the resulting NiN2O4 coordination can be described as distorted octa\u00adhedral. Considerable C=O\u22ef\u03c0 stacking inter\u00adactions are observed between the carboxyl\u00adate C=O groups and the pyridine rings of the (pydc)2\u2212 fragments, with O\u22ef\u03c0 distances of 3.1563\u2005(12) and 3.2523\u2005(12)\u2005\u00c5 and C=O\u22ef\u03c0 angles of 95.14\u2005(8) and 94.64\u2005(8)\u00b0. In the crystal structure, a wide range of non-covalent inter\u00adactions, consisting of hydrogen bonding , ion pairing, \u03c0\u2013\u03c0 [centroid-to-centroid distance = 3.4825\u2005(8)\u2005\u00c5] and C=O\u22ef\u03c0 stacking, connect the various components to form a supra\u00admolecular structure.The reaction of nickel(II) nitrate hexa\u00adhydrate, propane-1,2-diamine and pyridine-2,6-dicarboxylic acid in a 1:2:2 molar ratio in aqueous solution resulted in the formation of the title compound, (C DOI: 10.1107/S1600536808016309/su2054Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The CdII ion is hexa\u00adcoordinated by four carboxylate O atoms [Cd\u22efO = 2.280\u2005(2)\u20132.404\u2005(2)\u2005\u00c5] from two chelating 4-methoxy\u00adbenzoate anions, and two N atoms [Cd\u22efN = 2.313\u2005(2) and 2.332\u2005(2)\u2005\u00c5] from one chelating 2,2\u2032-dimethyl-3,3\u2032-(oxydiethyl\u00adene)bis\u00ad(1H-benzimidazole) ligand. In the crystal, mol\u00adecules are linked by a weak inter\u00admolecular C\u2014H\u22efO hydrogen bond and an inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction.The title complex, [Cd DOI: 10.1107/S1600536810009505/lx2137Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The structure is consolidated by inter\u00admolecular O\u2014H\u22efO hydrogen bonding, as well as by \u03c0\u2013\u03c0 stacking inter\u00adactions between adjacent naphthyl ring systems [centroid\u2013centroid distance between parallel naphthoate rings is 3.768\u2005(2)\u2005\u00c5].In the title mononuclear complex, [Mg(C DOI: 10.1107/S1600536808006351/ng2419Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "II\u2013HoIII complex ]diphenolato-1\u03ba4               O               1,O               1\u2032,O               6,O               6\u2032:2\u03ba4               O               1,N,N\u2032,O               1\u2032}trinitrato-1\u03ba6               O,O\u2032-holmium(III)nickel(II)), [HoNi(C20H22N2O4)(NO3)3], with the hexa\u00addentate Schiff base compartmental ligand N,N\u2032-bis\u00adethyl\u00adenediamine (H2               L), the Ho and Ni atoms are doubly bridged by two phenolate O atoms of the Schiff base ligand. The coordination of Ni is square-planar with the donor centers of two imine N atoms and two phenolate O atoms. The holmium(III) center has a tenfold \u00adcoordination environment of O atoms, involving the phenolate O atoms, two eth\u00adoxy O atoms and two O atoms each from the three nitrates. Weak C\u2014H\u22efO and O\u22efNi [3.383\u2005(4)\u2005\u00c5] inter\u00adactions generate a two-dimensional zigzag sheet.In the title heteronuclear Ni DOI: 10.1107/S1600536808013755/hg2401Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The asymmetric unit contains one 4-methyl\u00adbenzoate (PMB) anion, one N,N-diethyl\u00adnicotinamide (DENA) ligand and one coordinated water mol\u00adecule. The four O atoms in the equatorial plane around the CoII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa\u00adhedral coordination is completed by the two pyridine N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl\u00adate group and the attached benzene ring is 3.73\u2005(14)\u00b0, while the pyridine and benzene rings are oriented at a dihedral angle of 77.28\u2005(6)\u00b0. In the crystal structure, inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a two-dimensional network parallel to (001). The structure is further stabilized by \u03c0\u2013\u03c0 contacts between the pyridine rings [centroid\u2013centroid distance = 3.544\u2005(1)\u2005\u00c5] and weak C\u2014H\u22ef\u03c0 inter\u00adactions involving the benzene ring.In the centrosymmetric mononuclear title complex, [Co(C N,N-diethyl\u00adnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.038                           wR(F                           2) = 0.090                           S = 1.04                           4484 reflections234 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.86 e \u00c5\u22123                        \u0394\u03c1min = \u22120.55 e \u00c5\u22123                        \u0394\u03c1                                 APEX2  used to solve structure: SHELXS97 (Sheldrick, 2008SHELXL97 (Sheldrick, 2008et al., 2006WinGX (Farrugia, 1999PLATON (Spek, 2009Data collection: 10.1107/S1600536810013954/ci5076sup1.cif            Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013954/ci5076Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "There are three N-[(anthracen-9-yl)\u00admethyl\u00adene\u00adamino]\u00adthio\u00adureate ligands coordinated to the CoIII atom via three imine N and three thio\u00adamide S atoms. The Co\u2014S and Co\u2014N bond distances are in expected ranges . The endocyclic S\u2014Co\u2014N bond angles in the five-membered chelate rings range from 82.91\u2005(7) to 85.33\u2005(7)\u00b0. The structure contains four water mol\u00adecules which are disordered over 12 sites and link the complex mol\u00adecules into a three-dimensional network through N\u2014H\u22efO, O\u2014H\u22efO, O\u2014H\u22efN, and O\u2014H\u22efS hydrogen bonds.In the title complex, [Co(C DOI: 10.1107/S1600536808031425/pv2097Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "The two inversion-related CdII ions are separated by 3.9920\u2005(6)\u2005\u00c5 and are bridged by two O atoms from two nitrite ligands. There are two types of \u03c0\u2013\u03c0 stacking inter\u00adactions involving symmetry-related pyrazole rings, with centroid\u2013centroid distances of 3.445\u2005(2) and 3.431\u2005(2)\u2005\u00c5.In the title centrosymmetric binuclear complex, [Cd DOI: 10.1107/S1600536809039841/lh2917Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:"}
{"text": "AID). Upon germinal centre exit, B cells differentiate into antibody\u2010secreting plasma cells. Germinal centre maintenance and terminal fate choice require transcriptional reprogramming that associates with a substantial reconfiguration of DNA methylation patterns. Here we examine the role of ten\u2010eleven\u2010translocation (TET) proteins, enzymes that facilitate DNA demethylation and promote a permissive chromatin state by oxidizing 5\u2010methylcytosine, in antibody\u2010mediated immunity. Using a conditional gene ablation strategy, we show that TET2 and TET3 guide the transition of germinal centre B cells to antibody\u2010secreting plasma cells. Optimal AID expression requires TET function, and TET2 and TET3 double\u2010deficient germinal centre B cells show defects in CSR. However, TET2/TET3 double\u2010deficiency does not prevent the generation and selection of high\u2010affinity germinal centre B cells. Rather, combined TET2 and TET3 loss\u2010of\u2010function in germinal centre B cells favours C\u2010to\u2010T and G\u2010to\u2010A transition mutagenesis, a finding that may be of significance for understanding the aetiology of B\u2010cell lymphomas evolving in conditions of reduced TET function.Upon activation by antigen, B cells form germinal centres where they clonally expand and introduce affinity\u2010enhancing mutations into their B\u2010cell receptor genes. Somatic mutagenesis and class switch recombination (CSR) in germinal centre B cells are initiated by the activation\u2010induced cytidine deaminase . Loss of TET function favors C\u2010to\u2010T and G\u2010to\u2010A mutagenesis during somatic hypermutation, a finding of potential significance for understanding the etiology of B\u2010cell lymphomas.TET (ten\u2010eleven\u2010translocation) enzymes promote gene expression by catalyzing the oxidation of 5\u2010methylcytosine in DNA. TET deficiency has been linked to defects in embryonic development and enhanced risk of myeloid malignancies, including B\u2010cell lymphomas. Here, Verena Labi and colleagues show using a conditional gene ablation strategy that TET function is vital for humoral immunity  As compared to mature na\u00efve follicular (FO) B cells, TET2 and TET3 are substantially down\u2010regulated in antigen\u2010experienced GC B cells and plasma cells, a result in agreement with a recent report in human GC B cells During B\u2010cell development expression of both, TET2 Fig.\u00a0A and TETDependent on the mouse strain and animal facility, young mice lacking only TET2 or TET3 display no or only moderate B\u2010cell phenotypes at steady state in\u00a0vitro treatment of activated B cells with 5\u2010azacytidine augmented the appearance of plasmablasts in a division\u2010dependent manner B\u2010cell transit through the GC is accompanied by extensive DNA demethylation, focal methylation gains and an overall increased heterogeneity in DNA methylation patterns ;Tet2F/F;Tet3F/F mice in which physiologic germ\u2010line Cg1 transcription drives expression of the Cre\u2010recombinase Tet genes is expected in a majority of GC B cells upon IgG1\u2010priming. Of note, acute GC B cell\u2010specific Tet deletion circumvents indirect effects caused by extended TET\u2010deficiency during B\u2010cell development.Addressing the involvement of TET proteins in this process, we generated Cg1\u2010Crein\u00a0vitro induced GC (iGC) B cells First, we used a co\u2010culture system that allows the generation and exponential growth of Tet deletion is complete as indicated by qRT\u2010PCR analysis  conjugated to chicken gamma globulin (NP\u2010CGG). NP\u2010specific GC B cells that form in response to alum\u2010adjuvanted immunogens predominately switch to IgG1 ;Tet2F/F;Tet3F/F GC B cells, suggesting that these cells proliferate normally  and high\u2010affinity (NP1.7\u2010BSA) \u03b1\u2010NP IgG1 were decreased similarly, resulting in no significant skewing of the affinity ratio in Cg1\u2010Cre;Tet2F/F;Tet3F/F mice  ;Tet2F/F;Tet3F/F (54%) GC B\u2010cell clones  in PBS in a volume of 200\u00a0\u03bcL per mouse. Animal procedures were approved by the Austrian Federal Ministry of Education, Science and Research (BMWF: 66\u2010011/0106\u2010WF/3b/2015 and 66\u2010011/0031\u2010V/3b/2019).The Cg1\u2010Cre 4)2  in PBS] was mixed with a similar volume of 1\u00a0mg\u00b7mL\u22121 NP15\u2010CGG , and the pH was adjusted to 6.5\u20137.0 using 10\u00a0m NaOH . The precipitate was washed three times with PBS at 2348 g\u00a0for 15\u00a0s and finally resuspended in PBS to reach the initial volume of the Alum/NP\u2010CGG mixture.A freshly prepared 10% Alum solution  was generally used for cell preparation. Single\u2010cell suspensions were prepared by forcing murine spleen through 70\u00a0\u03bcB cells were enriched from splenic single\u2010cell suspensions using MagniSort Streptavidin Negative Selection Beads  as per manufacturer's instructions, and biotinylated antibodies against Ter119 , CD11b  and TCR\u03b2 .et\u00a0al. m l\u2010glutamine  and 100\u00a0U\u00b7mL\u22121\u00a0penicillin/100\u00a0\u03bcg\u00b7mL\u22121\u00a0streptomycin . 3\u00a0\u00d7\u00a0106 feeder cells per 10\u00a0cm plate were treated for 2\u00a0h with 10\u00a0\u03bcg\u00b7mL\u22121 mitomycin C  in 6\u00a0mL feeder cell medium. Following five repeated washing steps with PBS, 1.5\u00a0\u00d7\u00a0106 B cells/10\u00a0cm dish were plated on 40LB feeder cells in 40\u00a0mL B\u2010cell medium: DMEM supplemented with 10% (v/v) FBS, 2\u00a0mm l\u2010glutamine, 10\u00a0mm Hepes , 1\u00a0mm sodium pyruvate , 1\u00d7 nonessential amino acids , 100\u00a0U\u00b7mL\u22121\u00a0penicillin/100\u00a0\u03bcg\u00b7mL\u22121\u00a0streptomycin, 50\u00a0\u03bcm \u03b2\u2010mercapto\u2010ethanol  and 10\u00a0ng\u00b7mL\u22121 rIL\u20104 . On day 3, 30\u00a0mL of medium containing IL\u20104 were replaced. On day 4, iGC B cells were harvested and analysed. 1.5\u00a0\u00d7\u00a0106 iGC B cells were replated per 10\u00a0cm dish containing fresh mitomycin C\u2010treated 40LB feeder cells as detailed above, and cultivated in 40\u00a0mL of B\u2010cell medium containing either 10\u00a0ng\u00b7mL\u22121 rIL\u20104 or 10\u00a0ng\u00b7mL\u22121 rIL\u201021 . Thirty millilitre of medium containing the respective cytokines were replaced by fresh medium on day 7. The final analysis was conducted on day 8. Analyses (day 4 and 8) entailed collection of medium for ELISA and pellets for qRT\u2010PCR, cell counting (Trypan blue exclusion) and flow cytometric analysis. For analysis, iGC B cells were generally handled at room temperature and cultured at 37\u00a0\u00b0C in a humidified atmosphere containing 5% CO2.The iGC B cell culture was conducted as described by Nojima 2. Mitogenic stimuli were used as follows: 1\u00a0\u03bcg\u00b7mL\u22121 \u03b1\u2010CD40 , 25\u00a0ng\u00b7mL\u22121 IL\u20104 , 10\u00a0ng\u00b7mL\u22121 IL\u201021 (Peprotech 210\u201021), 20\u00a0mg\u00b7mL\u22121 lipopolysaccharide  and 25\u00a0ng\u00b7mL\u22121 IL\u20105 .Primary B cells were enriched from splenic single\u2010cell suspensions and cultivated in medium as described above for the iGC B\u2010cell culture at 37\u00a0\u00b0C in a humidified atmosphere containing 5% COin\u00a0vitro, B cells were labelled with 10\u00a0\u03bcm Cell Proliferation Dye eFluor 450  as per manufacturer's instructions and placed in culture.To determine cell proliferation in the presence of mitogens 2\u2010FITC , \u03b1CD25\u2010PE , \u03b1cKit\u2010APC , \u03b1CD1d\u2010PE , \u03b1CD23\u2010PE/Cy7 , \u03b1CD38\u2010FITC , \u03b1CD38\u2010APC , \u03b1CD38\u2010eFluor450 , \u03b1CD95\u2010PE , \u03b1CD95\u2010PE/Cy7 , \u03b1CXCR4\u2010APC , \u03b1CD86\u2010PE/Cy7 , \u03b1IgG1\u2010FITC , \u03b1IgG1\u2010PE , CD138\u2010PE  and CD138\u2010BV510 . NP24\u2010PE  was used to detect NP\u2010binding B cells. Data were acquired on an LSRII cytometer (BD Biosciences) and analysed using flowjo software . Nonsinglet events were excluded from analyses using FSC\u2010H/FSC\u2010W and SSC\u2010H/SSC\u2010W characteristics.Flow cytometry analysis has been performed as described in Ref. m EDTA). Cells were harvested by addition of B\u2010cell medium and vigorous pipetting.To collect iGC B cells from 10\u00a0cm dishes, 9/10 of the medium was gently removed, and the cells were incubated for 5\u00a0min at 37\u00a0\u00b0C in 3\u00a0mL harvest buffer  and surface digested for 4\u00a0min at 37\u00a0\u00b0C. To stop trypsin digestion, 3\u00a0mL of staining buffer (described above for flow cytometry) were added, the cells were pelleted at 1800\u00a0r.p.m. for 4\u00a0min and the supernatant was removed. The cells were transferred to a U\u2010bottom 96 well plate and dead cells were labelled with the Fixable Viability Dye eFluor 780  as per manufacturer's instructions. Subsequently, cells were fixed and processed using the active Caspase 3 staining kit  as per manufacturer's instructions. Before staining with the active Caspase 3 antibody, the iGC B cells were incubated with 1\u00a0\u03bcg\u00b7mL\u22121 of \u03b1CD16/32 Fc\u2010Block  in 25\u00a0\u03bcL perm/wash buffer for 10\u00a0min at 4\u00a0\u00b0C. Subsequently another 25\u00a0\u03bcL of \u03b1IgE\u2010bio  diluted in perm/wash buffer was added, the cells were further incubated for 15\u00a0min at 4\u00a0\u00b0C and washed with perm/wash buffer at 568\u00a0g\u00a0for 2\u00a0min. Next, the cells were incubated with 25\u00a0\u03bcL of antibody mix containing \u03b1IgM\u2010PeCy7 , \u03b1IgG1\u2010FITC , \u03b1CD19\u2010BV605  and Streptavidin\u2010APC  for 15\u00a0min at 4\u00a0\u00b0C. The cells were washed with perm/wash buffer at 2000\u00a0r.p.m. for 2\u00a0min and stained for active caspase 3 as per manufacturer's instructions.For CSR analysis, 5\u00a0\u00d7\u00a0105 iGC B cells were transferred to a U\u2010bottom 96 well plate and pelleted at 2000\u00a0r.p.m. for 2\u00a0min. Dead cells were labelled with the Fixable Viability Dye eFluor 780  as per manufacturer's instructions. Subsequently, cells were incubated with 1\u00a0\u03bcg\u00b7mL\u22121 of \u03b1CD16/32 Fc\u2010Block in 25\u00a0\u03bcL staining buffer (PBS/3%FBS) for 10\u00a0min. Next, 25\u00a0\u03bcL of staining buffer containing \u03b1CD19\u2010BV605  and \u03b1CD138\u2010BV421  was added. The cells were further incubated for 15\u00a0min, washed with 200\u00a0\u03bcL of staining buffer at 2000\u00a0r.p.m. for 2\u00a0min, and resuspended in 200\u00a0\u03bcL staining buffer for flow cytometry analysis.The processing of cells for plasmablast flow cytometry analysis was performed at room temperature in the dark. 5\u00a0\u00d7\u00a010flowjo software (Tree Star). Nonsinglet events were excluded from analyses using FSC\u2010H/FSC\u2010W and SSC\u2010H/SSC\u2010W characteristics.Data were acquired on an LSRII cytometer (BD Biosciences) and analysed using \u22121 of \u03b1CD16/32 Fc\u2010Block in 500\u00a0\u03bcL staining buffer (PBS/3%FBS) for 10\u00a0min, washed and stained for 20\u00a0min with antibodies in a volume of 500\u00a0\u03bcL staining buffer. The sorted cell subsets were defined as follows: Bone Marrow: pro B cells (B220loCD19+AA4.1+IgM\u2212CD25\u2212ckit+), large pre B cells (B220loCD19+AA4.1+IgM\u2212CD25+ckit\u2212FSChi), small pre B cells (B220loCD19+AA4.1+IgM\u2212CD25+ckit\u2212FSClo) and immature IgM+ B cells (B220loCD19+AA4.1+IgM+). Spleen: T1 B cells (CD19+B220+AA4.1+CD23\u2212IgMhi), T2 B cells (CD19+B220+AA4.1+CD23+IgMhi), FO B cells (CD19+B220+AA4.1\u2212CD1d+IgM+), MZ B cells (CD19+B220+AA4.1\u2212CD1dhiIgMhi), GC B cells (CD19+B220+CD138\u2212CD95hiCD38lo/\u2212), plasma cells/plasmablasts (B220\u2212/loCD138hi), DZ GC B cells (CD19+B220+CD138\u2212CD95hiCD38lo/\u2212CXCR4hiCD86lo) and LZ GC B cells (CD19+B220+CD138\u2212CD95hiCD38lo/\u2212CXCR4loCD86hi). For sorting B\u2010cell division cycles cells were harvested, filtered through 70\u00a0\u03bcm mesh filters  and resuspended in staining buffer.Cell sorting has been performed as described in Ref. Cell sorting was carried out on a FACS Aria III (BD Biosciences). Nonsinglet events were excluded from analyses based on characteristics of FSC\u2010H/FSC\u2010W and SSC\u2010H/SSC\u2010W.in\u00a0vitro\u2010cultivated B cells was isolated using Trizol reagent  as per manufacturer's instructions. DNA was removed using the RQ1 RNAse\u2010free DNase , and RNA was retrieved using GlycoBlue Coprecipitant  as per manufacturer's instructions. First\u2010strand cDNA was generated from 100\u00a0ng of total RNA using the iScript cDNA Synthesis Kit  and cDNA was amplified using the AceQ qPCR SYBR Green Master Mix  as per manufacturer's instructions. The qRT\u2010PCR was run on a StepOnePlus Real\u2010time PCR system  and melt curve analysis was performed for every run. The expression of individual mRNAs was normalized to HPRT with the following formula: fold induction\u00a0=\u00a02(\u2212\u0394Ct), where \u0394Ct=Ct(target)\u2212Ct(HPRT). The following primers were used: HPRT F: 5\u2032\u2010GTCATGCCGACCCGCAGTC\u20103\u2032, HPRT R: 5\u2032\u2010AGTCCATGAGGAATAAAC\u20103\u2032; TET2\u00a0F: 5\u2032\u2010GCCAGAAGCAAGAAACCAAG\u20103\u2032, TET2 R: 5\u2032\u2010TTGGAGCAATGACAGTAGCC\u20103\u2032; TET3\u00a0F: 5\u2032\u2010AAGAGTCTGCTGGACACACC\u20103\u2032, TET3 R: 5\u2032\u2010CTCCATGAGTTCCCGGATAG\u20103\u2032; AID F: 5\u2032\u2010GGACTTCGGCCACCTTC\u20103\u2032, AID R: 5\u2032\u2010CATCTCAGAAACTCAGCCACG\u20103\u2032. Ki67\u00a0F: 5\u2032\u2010GAACAGACTTGCTCTGGCCTAC\u20103\u2032, Ki67 R: 5\u2032\u2010 CTTCATAGGCATTCCCTCACTC\u20103\u2032.RNA from snap\u2010frozen cell pellets of FACS\u2010sorted B cells was isolated using the Quick\u2010RNA Micro Prep Kit  and DNase digestion as per manufacturer's instructions. RNA from snap\u2010frozen \u22121 capture antibody  was coated overnight onto 96\u2010well enzyme\u2010linked immunosorbent assay plates at 4\u00a0\u00b0C . Plates were washed three times with wash buffer (PBS containing 0.05% TWEEN 20), blocked with 100\u00a0\u03bcL per well 1% BSA in PBS for 4\u00a0h at room temperature and washed three more times with wash buffer. Subsequently, wells were incubated over night at 4\u00a0\u00b0C with 100\u00a0\u03bcL per well of mouse serum serially diluted 1\u00a0:\u00a04 in blocking buffer (range 1\u00a0:\u00a0800 to 1\u00a0:\u00a0160\u00a0000). Plates were washed three times with wash buffer and incubated with 100\u00a0\u03bcL per well of HRP\u2010conjugated \u03b1\u2010mouse IgG1  or HRP\u2010conjugated \u03b1\u2010mouse IgM  for 4\u00a0h at room temperature. For detection, 100\u00a0\u03bcL of ABTS substrate solution per well  was incubated for 20\u00a0min. Absorbance was measured at 405\u00a0nm using a microplate reader .For NP\u2010specific serum IgG1 and IgM titres, ELISA was performed as described in zeiss zen blue 2.5 lite software (Zeiss).IHC was performed on 7\u00a0\u03bcm sections of murine spleens as described in Ref. ;Tet2F/F;Tet3F/F mice. Briefly, IgG1+ GC B cells were FACS\u2010sorted (CD19+B220+CD138\u2212FashiCD38lo/\u2212IgG1+), pelleted and total RNA was isolated using the Quick\u2010RNA Micro Prep Kit  including the DNase digestion step as per manufacturer's instructions. First\u2010strand cDNA was generated from 100\u00a0ng of total RNA using the Promega GoScript Reverse transcription system  and a gene\u2010specific primer for the IgG1 locus: Cg1 5\u2032\u2010CATGGAGTTAGTTTGGGCAG\u20103\u2032. Subsequently, two rounds of semi\u2010nested PCRs were performed using the Herculase II Fusion DNA polymerase kit  as per manufacturer's instructions. Following each round of PCR, the gene product was run on an agarose gel and purified using the peqGold Gel extraction kit  as per manufacturer's instructions. For the first PCR, the following primers were used: V186.2 leader 5\u2032\u2010AGCTGTATCATGCTCTTCTTGGCA\u20103\u2032, Cg1 5\u2032\u2010CATGGAGTTAGTTTGGGCAG\u20103\u2032. For the second PCR, the following primers were used: V186.2 nested 5\u2032\u2010CATGCTCTTCTTGGCAGCAACAG\u20103\u2032, Cg1 5\u2032\u2010CATGGAGTTAGTTTGGGCAG\u20103\u2032. For cloning of VH186.2 segments, the pJet1.2 blunt vector was used and cleaved with EcoRV . The purified PCR products were ligated into the vector using T4 ligase  as per manufacturer's instructions. Using a standard transformation protocol, DH5\u03b1 bacteria were transformed with the bulk of ligated plasmids, spread onto LB Agar/ampicillin plates and incubated over night at 37\u00a0\u00b0C. For each of the six mice, >10 colonies were transferred into a PCR Master Mix , and the very same colonies were selected on new LB agar plates. For the colony PCR, the following primers were used: pJet1.2\u00a0F 5\u2032\u2010CGACTCACTATAGGGAGAGCGGC\u20103\u2032, pJet1.2 R 5\u2032\u2010AAGAACATCGATTTTCCATGGCAG\u20103\u2032. Cycle conditions were: 1 cycle: 95\u00a0\u00b0C for 1\u00a0min; 30 cycles: 95\u00a0\u00b0C for 15\u00a0s, 56\u00a0\u00b0C for 15\u00a0s, 72\u00a0\u00b0C for 45\u00a0s; 1 cycle: 72\u00a0\u00b0C for 3\u00a0min. The PCR products were loaded onto an agarose gel, and colonies with correct insertions were grown in 2\u00a0mL LB medium over night. Plasmid DNA was extracted using the Monarch Plasmid Miniprep Kit  as per manufacturer's instructions. Subsequently, Sanger sequencing was performed using the pJet1.2\u00a0F primer detailed above. Sequences were aligned to the VH186.2 germ line sequence using VBASE2 (http://www.vbase2.org/). Mutation data were only used if the entire sequence was intact, and only unique sequences were included in the analysis. According to these criteria, two sequences from Cg1\u2010Cre;Tet2F/F;Tet3F/F GC B cells had to be excluded.Somatic hypermutation analysis was performed according to Ref. graphpad prism 7 software  using Student's t test when comparing two groups, One\u2010way ANOVA and Tukey post hoc test when comparing multiple groups and Mann\u2013Whitney test for SHM analysis. The number of biological repetitions (n) is stated in each figure legend, and every experiment was performed at least twice. Differences between groups were considered statistically significant when P\u00a0<\u00a00.05. In figures, asterisks stand for: *P\u00a0<\u00a00.05; **P\u00a0<\u00a00.01; ***P\u00a0<\u00a00.001; ****P\u00a0<\u00a00.0001.Results are always shown as mean and standard deviation (SD). Graphs were plotted and statistical analysis was performed with The authors declare no conflict of interest.Conceptualization: VL; Methodology: VL; Investigation: KS, SM, SH, ED,\u00a0AA; Resources: VL, SH, ED, AV, KR; Writing \u2013 Original Draft: VL; Visualization: VL; Project Administration: VL; Funding Acquisition: VL."}
{"text": "One Cu atom is coordinated to the 2-eth\u00adoxy\u00adpyrazine mol\u00adecule and two bridging cyanide ligands, equally disordered over two sites. The second Cu atom is coordinated by two disordered over two sites bridging cyanide groups. Two copper\u2013cyanide chains are connected through Cu\u22efCu contact.The title compound, {[Cu(EtOpz)(CN) 4H3OC2H5N2)][Cu(CN)]}n, there are two Cu atoms with different coordination environments. One CuI ion is coordinated in a triangular coordination geometry by the N atom of the 2-eth\u00adoxy\u00adpyrazine mol\u00adecule and by two bridging cyanide ligands, equally disordered over two sites exchanging C and N atoms, thus forming polymeric chains parallel to the c axis. The other Cu atom is connected to two bridging cyanide groups disordered over two sites with an occupancy of 0.5 for each C and N atom, and forming an almost linear polymeric chain parallel to the b axis. In the crystal, the two types of chain, which are orthogonal to each other, are connected by cuprophilic Cu\u22efCu inter\u00adactions [2.7958\u2005(13)\u2005\u00c5], forming two-dimensional metal\u2013organic coordination layers parallel to the bc plane. The coordination framework is further stabilized by weak long-range (electrostatic type) C\u2014H\u22ef\u03c0 inter\u00adactions between cyano groups and 2-eth\u00adoxy\u00adpyrazine rings.In the asymmetric unit of the title coordination compound, {[Cu(CN)(C The Cu1 atom is coordinated to the N atom of a 2-eth\u00adoxy\u00adpyrazine mol\u00adecule [Cu1\u2014N5 = 2.090\u2005(4)\u2005\u00c5]. Two other coordination positions are occupied by bridging cyanide groups, which are equally disordered over two sites, exchanging C and N atoms [Cu1\u2014C1/N1 = 1.905\u2005(4)\u2005\u00c5 and Cu1\u2014C2/N2 = 1.888\u2005(4)\u2005\u00c5], thus forming an irregular triangular coordination geometry where the copper ion is displaced from the centre . The Cu2 atom is coordinated by two cyanide ligands, which are also disordered over two sites with an occupancy of 0.5 for each C and N atom  to form an almost linear chain [C4/N4iii\u2014Cu2\u2014C3/N3 = 170.5\u2005(2)\u00b0]. The two CuI centres are connected through a Cu\u22efCu inter\u00adaction [Cu1\u2014Cu2 = 2.7958\u2005(13)\u2005\u00c5] that could be inter\u00adpreted as a cuprophilic contact  inter\u00adconnected by Cu\u22efCu contacts and forming two-dimensional layers parallel to (100). The Cu\u22efCu contacts are almost perpendicular to the [Cu2(CN)] chains [C3/N3\u2014Cu2\u2014Cu1 = 89.8\u2005(2)\u00b0 and C4/N4iii\u2014Cu2\u2014Cu1 = 99.7\u2005(2)\u00b0]. At the same time, the Cu2 atom occupies an axial position with respect to the triangular [N(CN)2] coordination environment of Cu1 [C1/N1\u2014Cu1\u2014Cu2 = 70.6\u2005(2)\u00b0 and C2/N2\u2014Cu1\u2014Cu2 = 87.6\u2005(2)\u00b0]. The resulting metal\u2013organic coordination framework is additionally stabilized by weak long-range (electrostatic-type) C\u2014H\u22ef\u03c0 inter\u00adactions between cyanide groups and 2-eth\u00adoxy\u00adpyrazine rings \u2005\u00c5 are also observed .The crystal packing of the title compound Fig.\u00a02 consistset al., 2016catena-[penta\u00adkis\u00ad(\u03bc2-cyano)\u00adtris\u00ad(1-phenyl\u00adpiperazine)penta\u00adcopper] (PhPip) and (CuCN)3(PhPip), associated by Cu\u22efCu pairwise cuprophilic inter\u00adactions, with distances of 2.5586\u2005(10) and 2.6441\u2005(10)\u2005\u00c5. A search of the CSD for two C\u2014N\u2014Cu\u2014C\u2014N fragments with a defined Cu\u22efCu distance less than 2.8\u2005\u00c5 gave 80 hits, among which is an example close to the title structure, i.e.catena-[tetra\u00adkis\u00ad(\u03bc2-cyano)\u00adtetra\u00adcopper(I)]  and 2.9644\u2005(6)\u2005\u00c5.A search of the Cambridge Structural Database  in 1\u2005ml of H2O, the second layer was a H2O/EtOH mixture  and the third layer was a solution of 2-eth\u00adoxy\u00adpyrazine  in 0.5\u2005ml of EtOH. After two weeks, colourless block-shaped crystals had formed in the middle layer. The crystals were kept under the mother solution prior to measurement.Crystals of the title compound were obtained by slow diffusion within three layers in a 3\u2005ml glass tube. The first layer was a solution of K[Cu(CN)Uiso(H) = 1.2Ueq(C) for aromatic hydrogens, C\u2014H = 0.97\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for the CH2 group, and C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for the CH3 group. A rotating model was used for the methyl group. All cyano ligands are disordered over two sites with occupancies of 0.5. The coordinates of C and N atoms sharing the same sites and their displacement ellipsoids were constrained to be the same.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901901452X/rz5265sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901901452X/rz5265Isup2.hklStructure factors: contains datablock(s) I. DOI: 1961274, 1961274CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "DNA polymerase \u03b8 (Pol\u03b8) is a unique polymerase-helicase fusion protein that promotes microhomology-mediated end-joining (MMEJ) of DNA double-strand breaks (DSBs). How full-length human Pol\u03b8 performs MMEJ at the molecular level remains unknown. Using a biochemical approach, we find that the helicase is essential for Pol\u03b8 MMEJ of long ssDNA overhangs which model resected DSBs. Remarkably, Pol\u03b8 MMEJ of ssDNA overhangs requires polymerase-helicase attachment, but not the disordered central domain, and occurs independently of helicase ATPase activity. Using single-particle microscopy and biophysical methods, we find that polymerase-helicase attachment promotes multimeric gel-like Pol\u03b8 complexes that facilitate DNA accumulation, DNA synapsis, and MMEJ. We further find that the central domain regulates Pol\u03b8 multimerization and governs its DNA substrate requirements for MMEJ. These studies identify unexpected functions for the helicase and central domain and demonstrate the importance of polymerase-helicase tethering in MMEJ and the structural organization of Pol\u03b8. DNA polymerase \u03b8 is a polymerase-helicase essential for microhomology-mediated end-joining (MMEJ) or alternative end-joining of DNA. Here the authors use biochemical and biophysical methods to reveal how full-length human DNA polymerase \u03b8 performs MMEJ at the molecular level. MMEJ functions during S and G2 cell-cycle phases and therefore acts on 3\u2032 single-strand DNA (ssDNA) overhangs generated by 5\u2032\u20133\u2032 exonuclease resection of DSBs, similar to homologous recombination (HR) is a polymerase-helicase fusion protein Fig.\u00a0, that is(HR)Fig.\u00a07,8. The 11. Pol\u03b8-hel is related to HELQ/Hel308 helicases, which are involved in replication and repair13. Recent studies show that Pol\u03b8-hel unwinds short DNA in an ATP-dependent manner with 3\u2032-5\u2032 polarity, similar to HELQ/Hel30812. Pol\u03b8-hel also facilitates annealing of complementary ssDNA in an ATP-independent manner, and anneals RPA coated ssDNA by utilizing the energy of ATP14. Pol\u03b8-hel may also act as an anti-recombinase by counteracting RAD51 activity15. Pol\u03b8-pol is related to bacterial Pol I enzymes such as Klenow fragment, but contains an inactive 3\u2032\u20135\u2032 exonuclease domain16, and exhibits low fidelity DNA synthesis and translesion (TLS) synthesis activities21. The polymerase and helicase include unstructured motifs, and a disordered motif (loop 2) in Pol\u03b8-pol was shown to promote its ssDNA extension and MMEJ activities22.Pol\u03b8 consists of a super-family 2 helicase (Pol\u03b8-hel), a disordered central domain (Pol\u03b8-cen), and an A-family polymerase (Pol\u03b8-pol) Fig.\u00a01,10,11. 7, and that Pol\u03b8 competes with HR15. Wyatt et al. also demonstrated that the efficiency of cellular MMEJ is positively correlated with 3\u2032 ssDNA overhang length8. This report further demonstrated that Ku binds tightly to DNA ends with short 4 nt overhangs, but exhibits very low affinity for 70 nt overhangs8. This reveals a clear mechanistic difference between the respective substrate requirements for non-homologous end-joining (NHEJ) and MMEJ. How Pol\u03b8 functions on long ssDNA overhangs to promote MMEJ, however, remains unknown.The ssDNA overhangs that Pol\u03b8 functions on during MMEJ have become clearer in recent cellular studies. Wyatt et al. demonstrated that relatively long (\u2265\u200945\u201370\u2009nt) ssDNA overhangs promote MMEJ in cells Fig.\u00a0. This is2. Recent biochemical studies similarly show that Pol\u03b8-pol can perform MMEJ on short (\u2009<\u200912\u2009nt) ssDNA23. Although these studies provide insight into the activity of Pol\u03b8-pol, they fail to recapitulate MMEJ on DNA with longer (45\u201370\u2009nt) overhangs that support cellular MMEJ8. In vitro, Pol\u03b8-pol primarily performs snap-back replication on long ssDNA as a result of its intrastrand base-pairing activity22. For example, under physiological buffer conditions with Mg2+, Pol\u03b8-pol efficiently extends relatively long (\u2265\u200926\u2009nt) ssDNA by using the 5\u2032 portion of the ssDNA as a template in cis  overhangs in cellular studies8, we hypothesized that the helicase domain within full-length Pol\u03b8 (hereafter referred to as Pol\u03b8) promotes MMEJ by suppressing Pol\u03b8-pol intrastrand pairing. For instance, since Pol\u03b8-hel binds tightly to ssDNA and translocates along ssDNA with 3\u2032\u20135\u2032 directionality13, it may inhibit Pol\u03b8-pol intrastrand pairing by binding and/or translocating along ssDNA upstream from the polymerase in the context of the full-length protein  3\u2032 overhangs are required for MMEJ activity by the isolated polymerase domain (Pol\u03b8-pol)cis Fig.\u00a0. Consistcis Fig.\u00a02,22. Becein Fig.\u00a0.S. cerevisiae using a N-terminal 3xFLAG-tag  are equally deficient in MMEJ of long ssDNA  ssDNA overhangs to promote MMEJ in cells, we examined Pol\u03b8 MMEJ of long ssDNA (70\u2009nt and 100\u2009nt) which models substrates with long 3\u2032 overhangs Fig.\u00a0. We find23. On longer 26\u2009nt ssDNA with identical microhomology, Pol\u03b8-pol exclusively promotes ssDNAx byproducts  overhangs2, demonstrates it performs interstrand pairing without Pol\u03b8-hel. Pol\u03b8-pol, however, fails to perform efficient MMEJ of long ssDNA under various conditions  ssDNA which is almost entirely contained within its active site Fig.\u00a0, leftSu and 3E16cts Fig.\u00a0, right, cts Fig.\u00a0-4F. Unexcts Fig.\u00a0, yet is cts Fig.\u00a0. This sucts Fig.\u00a0 and 3E23\u2009nt ssDNA8. Consistent with this, we find that decreasing ssDNA length to 45\u2009nt while maintaining the same 6\u2009bp microhomology significantly reduces Pol\u03b8 MMEJ, yet, the full-length protein still shows significantly higher end-joining activity than Pol\u03b8-pol  would be extruded from the enzyme\u2019s DNA exit channel  conjugated ssDNA  linker in place of the central domain (Pol\u03b8\u0394cen) Fig.\u00a027. Pol\u03b8\u0394ity Fig.\u00a0, and is ity Fig.\u00a0. Remarkaity Fig.\u00a0. Togetheons Fig.\u00a0. Controlons Fig.\u00a0, right, ons Fig.\u00a0, and is pol Fig.\u00a0.2, and the addition of Pol\u03b8-hel in trans fails to stimulate Pol\u03b8-pol MMEJ of this substrate as expected  ssDNA compared to Pol\u03b8-pol Fig.\u00a0, we test16. Our previous studies demonstrate that Pol\u03b8-hel exhibits similar activities to the related helicase Hel308, such as ATP-dependent 3\u2032-5\u2032 directional ssDNA translocation activity12. Based on this polarity, Pol\u03b8-hel was modeled facing towards the 5\u2032 terminus. The model superimposes the ssDNA substrate from the Hel308 structure, in which the enzyme translocates along, onto Pol\u03b8-hel28. The primer strand from the Pol\u03b8-pol structure is also included with additional ssDNA linking the two substrates together, resulting in a long contiguous 31 nt ssDNA that is easily bound by the tethered enzymes. In this close configuration along ssDNA Pol\u03b8-pol and Pol\u03b8-hel fit well together and space is readily available for a long flexible linker (e.g. Pol\u03b8-cen). Although this model is speculative, it suggests bivalent ssDNA binding by the fusion protein which would be expected to be in the low nanomolar range.Because covalent attachment of Pol\u03b8-hel to Pol\u03b8-pol is the minimal requirement for stimulating Pol\u03b8-pol MMEJ on relatively long ssDNA substrates, this indicates close cooperation between these two domains on long ssDNA. To gain insight into how these linked enzymes cooperate, we modeled the structure of the minimal end-joining Pol\u03b8\u0394cen protein on long ssDNA which combines the crystal structures of Pol\u03b8-pol and Pol\u03b8-hel attached by a flexible linker Fig.\u00a013,16. Ou13, we further investigated the footprint of Pol\u03b8\u0394cen on partial ssDNA (pssDNA) of similar size  following incubation in MMEJ buffer conditions lacking dNTPs and BSA. Without ssDNA, 81% of Pol\u03b8 behaves as monomers and dimers, whereas 3% correspond to large (\u2009>\u20091000 \u00c5) multimers  connected by a flexible linker Fig.\u00a0. The sphely Fig.\u00a0. Despiteely Fig.\u00a0\u20138.Fig. 731. The highly irregular shape of the assemblies suggests that, rather than droplets, the proteins form extended percolating networks; moreover, the fact that they are catalytically active indicates that the assemblies are permeable to the solvent and, possibly, large solutes. Based on the computational and EM evidence, we surmise that Pol\u03b8, and especially Pol\u03b8\u0394cen, form large (\u2009>\u2009100\u2009nm) gel-like complexes similar to others reported33, which accumulate DNA due to the high local concentration and accessibility of the polymerase and helicase domains.Overall, there is a close match between the morphology of the simulated complexes and the EM images Fig.\u00a0. A peculUsing a structure function approach in vitro, we investigated how recombinant human full-length Pol\u03b8 promotes MMEJ. On short ssDNA and short 3\u2032 overhangs, Pol\u03b8-pol efficiently performs MMEJ due to its interstrand pairing activity Fig.\u00a0. Thus, PPol\u03b8-hel stimulates Pol\u03b8-pol end-joining independently from its ATPase function. This supports the notion that Pol\u03b8-hel upregulates Pol\u03b8-pol MMEJ on long overhangs by simply binding ssDNA 5\u2032 proximal to the polymerase where it suppresses unproductive intrastrand pairing and snap-back replication by Pol\u03b8-pol Fig.\u00a0. Pol\u03b8-he34.Pol\u03b8 is unable to perform MMEJ or ssDNAx on short (\u2264\u200926\u2009nt) ssDNA Fig.\u00a0. HoweverPol\u03b8 forms multimeric complexes upon binding DNA. Replacement of Pol\u03b8-cen with a short linker, however, results in multimerization of the enzyme into an extended gel-like phase, even without DNA. This suggests that Pol\u03b8-cen suppresses Pol\u03b8 oligomerization by masking protein-protein interactions. Pol\u03b8 DNA binding may alter the conformation of Pol\u03b8-cen which in turn enables Pol\u03b8 oligomerization via protein-protein interactions. Our imaging data demonstrate that Pol\u03b8 multimers facilitate DNA accumulation and MMEJ. In summary, this report reveals the importance of the unique polymerase-helicase architecture of Pol\u03b8 which is essential for MMEJ.32P radiolabeled ssDNA in buffer ; the reaction was initiated by the addition of the indicated Pol\u03b8 enzyme and was incubated for 45\u2009min or as indicated at 37\u2009\u00b0C. For analysis in nondenaturing gels, reactions were terminated by the addition of non-denaturing stop buffer  and incubated at 37\u2009\u00b0C for at least 15\u201320\u2009min. DNA was resolved in non-denaturing 11% or 12% polyacrylamide gels and analyzed by phosphorimager (Fujifilm FLA 7000). For time course experiments an aliquot of sample was removed from pooled reactions at the specified time point and transferred to tubes containing non-denaturing stop buffer. All quantified experiments were performed in triplicate and plotted with\u2009\u00b1\u2009s.d. Quantification was performed using ImageJ Gel Analysis. For XmaI digestion assays, after initial incubation with the indicated Pol\u03b8 enzyme the following buffer was added . 25 units of XmaI (New England Biolabs) was then added, as indicated, and incubated overnight at 37\u2009\u00b0C. The reaction was then stopped using non-denaturing stop buffer and resolved as above.10\u2009nM 5\u2032-32P radiolabeled pssDNA in buffer ; the reaction was initiated by the addition of the indicated Pol\u03b8 enzyme and incubated for 30\u2009min at 37\u2009\u00b0C. For analysis in denaturing gels, reactions were terminated by the addition of denaturing stop buffer (90% formamide and 50\u2009mM EDTA). DNA was resolved in denaturing 15% polyacrylamide gels and analyzed by phosphorimager (Fujifilm FLA 7000).10\u2009nM 5\u2032-32P) ATP and 100\u2009nM ssDNA (29 nt poly-dT) in buffer  at room temp for the indicated times. The reaction mixture was then spotted onto a TLC plate on PEI cellulose, which was developed in a buffer containing 1\u2009M acetic acid and 0.25\u2009M LiCl2 for 1.5\u2009h. Plates were dried, then visualized by phosphorimager (Fujifilm FLA 7000).The indicated amounts of proteins were incubated with 10\u2009\u03bcM ATP, 2\u2009\u03bcCi of (\u03b3-: 5\u2009nM 5\u2032-32P radiolabeled pssDNA (RP538/RP539) in buffer  was incubated with or without indicated Pol\u03b8 enzyme for 15\u2009min at 37\u2009\u00b0C. After initial incubation, 4 units of EcoRI were added as indicated and incubated for 10\u2009min at 37\u2009\u00b0C. Reactions were terminated by the addition of non-denaturing stop buffer  and incubated at 37\u2009\u00b0C for at least 15\u201320\u2009min. DNA was resolved in non-denaturing 15% polyacrylamide gels and analyzed by phosphorimager (Fujifilm FLA 7000).T5 exonuclease assay: 8\u2009nM 3\u2032-Cy3 ssDNA (RP540Cy3) in buffer  was mixed with 10\u2009nM Pol\u03b8\u0394cen or Pol\u03b8-pol and was preincubated for 10\u2009min at 37\u2009\u00b0C. After initial incubation, T5 Exonuclease (New England Biolabs) to a final concentration of 0.1\u2009U/ul or 0.5\u2009U/ul was added to the reactions as indicated and incubated for 15\u2009min at 37\u2009\u00b0C. Reactions were terminated by the addition of denaturing stop buffer (90% formamide and 50\u2009mM EDTA). DNA was resolved in denaturing 15% polyacrylamide gels and imaged at the Cy3 wavelength using FluorChem Q imager (Alpha Innotech). EcoRI endonuclease assay2, 2\u2009mM ATP, 30\u2009mM NaCl and 0.01% NP-40. Reactions comparing foci formation frequency were incubated for 10\u2009min at room temp before imaging, excluding time course reactions which were imaged as indicated. Cy3 foci were identified using a Leica DMi8 scanning confocal microscope with a 63x objective at the Cy3 emission wavelength. Random fields were collected for each condition and quantified using ImageJ particle analysis. Time course reactions were imaged at a single fixed field and quantified over time using ImageJ particle analysis of each individual frame. End-joining reactions performed with confocal imaging were performed as written with the addition of 20\u2009\u00b5M dNTPs. After confocal imaging, reactions were terminated by the addition of nondenaturing stop buffer  and incubated at 37\u2009\u00b0C for 20\u2009min. Reactions were resolved in non-denaturing 12% polyacrylamide gels and imaged at the Cy3 wavelength using FluorChem Q imager (Alpha Innotech).Glass bottom wells were coated with 30\u2009mg/ml BSA for 30\u2009min at room temp. For foci formation frequency comparisons 40\u2009nM of Cy3 labeled DNA (RP334Cy3) was incubated with 3\u2009nM of the indicated Pol\u03b8 enzyme. For Rad52 confocal experiments 100\u2009nM Cy3 labeled DNA (RP334Cy3) was incubated with the indicated amounts of Rad52. For time course confocal assays and end-joining confocal assays 15\u2009nM of the indicated Pol\u03b8 enzyme was incubated with 40\u2009nM DNA (RP344Cy3). Reactions were performed with 25\u2009mM Tris-HCl, pH 8.8, 1\u2009mM DTT, 0.1\u2009mg/ml BSA, 10% glycerol, 10\u2009mM MgCl2, 10% glycerol, 0.1\u2009mg/ml BSA, 1\u2009mM ATP, 30\u2009mM NaCl for at least 30\u2009min at room temp. Reactions contained 10\u2009nM FAM-conjugated ssDNA (RP316FAM5), and the indicated amounts of the indicated Pol\u03b8 enzyme. A Clariostar (BMG Labtech) plate reader was used to measure fluorescence anisotropy. All experiments were performed in triplicate, normalized, and plotted with\u2009\u00b1\u2009s.d.Binding reactions were performed at room temp in 25\u2009mM Tris\u2013HCl, pH 8.8, 1\u2009mM DTT, 0.01% NP-40, 10\u2009mM MgCl2, 10% glycerol, 0.1\u2009mg/ml BSA, 1\u2009mM ATP, 30\u2009mM NaCl for at least 1\u2009hr at room temp. Reactions contained 10\u2009nM each of RP540Cy3 and RP541Cy5 and the indicated Pol\u03b8 enzyme. A Clariostar (BMG Labtech) plate reader was used to measure FRET . All experiments were performed in triplicate, normalized, and plotted with\u2009\u00b1\u2009s.d.Binding reactions were performed at room temp in 25\u2009mM Tris-HCl, pH 8.8, 1\u2009mM DTT, 0.01% NP-40, 10\u2009mM MgCl2, 2\u2009mM ATP, 0.01% NP-40 and 1\u2009mM DTT. Incubations were carried out at 37\u2009\u00b0C for 30\u2009min and deposited onto freshly cleaved mica. After 15\u2009s the mica surface was washed with milli Q water and dried with a stream of filtered air. Images were obtained on a NanoScope IV SFM  operating in tapping mode in air with a type J scanner. Silicon Nanotips were from AppNano . Images were collected at 3\u2009\u03bcm\u2009\u00d7\u20093 \u03bcm and flattened to remove background slope using Nanoscope software. The size of proteins was measured from NanoScope images imported into IMAGE SXM 1.89 . Statistical analysis was done using QtiPlot (Version 0.9.8.9 svn 2288) and LibreOffice (Version: 5.1.6.2). The volume of proteins monomers, measured from SFM images of proteins deposited in 10\u2009mM Tris\u2013HCl, pH 8.8/100\u2009mM KCl, were 100\u2009nm3 for Pol\u03b8-hel and Pol\u03b8-pol, 210\u2009nm3 for Pol\u03b8\u0394cen and 320 nm3 for Pol\u03b8 and Pol\u03b8K121M. These values (\u2009\u00b1\u200950%) were used to normalize the volume of observed complexes. Quantification is presented as % of total proteins present in certain oligomeric state.Proteins (10\u2009nM) with or without ssDNA (20\u2009nM) were incubated in MMEJ buffer without dNTPs or BSA containing: 25\u2009mM Tris\u2013HCl, pH 8.8, 30\u2009mM NaCl or 100\u2009mM NaCl where indicated, 10\u2009mM MgCl2, 2\u2009mM ATP) at 37\u2009\u00b0C for 30\u2009min. Samples (4\u2009\u03bcl) were applied to glow discharged lacey carbon grids  and incubated for 2\u2009min at room temp. The grids were then washed with water three times followed by staining with 2% uranyl acetate for 10\u2009s. Excess staining was removed by filter paper. The grids were air dried and imaged in a FEI Tecnai BioTwin Spirit transmission electron microscopy at Penn State University Cryo-Electron Microscopy facility.Pol\u03b8 or Pol\u03b8\u0394cen (200\u2009nM) with or without ssDNA (2\u2009\u03bcM) was incubated in 40\u2009\u03bcl of MMEJ reaction buffer without dNTPs, BSA or detergent  or ATCC 208289/BJ5465 (a ura3-52 trp1 leu2-delta1 his3-delta200 pep4::HIS3 prb1-delta1.6\u2009R can1 GAL\u2009+\u2009), as previously described35. Colonies were picked and grown in SC-TRP with 2% raffinose at 30\u2009\u00b0C. Starter cultures were expanded and grown to an OD600 of 0.6\u20131.0. Expanded cultures were grown to an OD600 of 1.6\u20132, diluted with YPR to OD600 of 0.8\u20131.0 and induced as follows. Expression was induced by the addition of 2% galactose for 5\u2009hr at 30\u2009\u00b0C. Cells were harvested by centrifugation at 6,000\u2009rpm and washed with 50\u2009mM HEPES pH 8.0 and 1\u2009M Sorbitol then washed with lysis buffer . Cells were crushed in a freezer mill with liquid nitrogen. Frozen cell powder was stored at \u221280\u2009\u00b0C until purification. Frozen cell powder was thawed and resuspended in lysis buffer. The resuspended cell powder was centrifuged at 92,000\u2009g at 4\u2009\u00b0C for 30\u2009min. The clarified supernatant was re-centrifuged at 256,000\u2009\u00d7\u2009g at 4\u2009\u00b0C for 1\u2009h. The supernatant was collected. Anti-FLAG M2 resin was washed with 0.1\u2009M Glycine-HCl, pH 3.5; then with TBS buffer pH 7.4  then with lysis buffer by centrifugation at 1000\u2009rpm at 4\u2009\u00b0C for 5\u2009min. In total 5\u2009\u00b5g/ml 3xFLAG peptide (Sigma) and equilibrated anti-FLAG M2 resin (Sigma) were added to each tube and incubated at 4\u2009\u00b0C. The resin was settled by centrifugation at 1,000\u2009rpm at 4\u2009\u00b0C for 5\u2009min and flow-through was collected. The resin was washed with lysis buffer and then with wash buffer A . The resin was incubated in wash buffer A on ice for 15\u2009min, then the resin was settled by centrifugation at 1,000\u2009rpm at 4\u2009\u00b0C for 5\u2009min. The resin was then washed with wash buffer B . The resin was resuspended in elution buffer  with 500\u2009\u00b5g/ml 3xFLAG peptide (Sigma) at 4\u2009\u00b0C with rotation. A disposable 10\u2009ml polypropylene column (Thermo Fisher) was washed with TBS buffer, pH 7.4  and then with elution buffer. The resin was loaded to the column and elution fractions were collected. The elution was dialyzed against dialysis buffer  overnight at 4\u2009\u00b0C. Pol\u03b8, Pol\u03b8K121M and Pol\u03b8\u0394cen concentrations were determined by SDS gel analysis and by specific activity using Pol\u03b8-pol as a standard. Pol\u03b8, Pol\u03b8K121M and Pol\u03b8\u0394cen were stored in aliquots at \u221280\u2009\u00b0C.Pol\u03b8-pol, Pol\u03b8-hel and RPA were purified as describedTemplates are as follows: Figs.\u00a032P-5\u2032-radiolabeled with T4 polynucleotide kinase (New England Biolabs) and (\u03b3-32P) ATP (Perkin Elmer).\u00a0RP469D: CTGTCCTGCATGATG;RP486: CACTGTGAGCTTAGTCACATTTCATCATGCAGGACAG;RP344: CACTGTGAGCTTAGGGTTAGCCCGGG;RP348: CACTGTGAGCTTAGGGTTAGAGCCGG;SJB108: GTTCTTCGGTCTCGAGGTGACTACAAGGATGACGACGACAAGGGCACTGTGAGCTTAGGGTTAGCCCGGG;SJB116: CACTGTGAGCTTAGGGTTAGGCGGCTTGCAGAGCACAGAGGCCGCAGAATGTGCTCTAGATTCCGATGCTGACTTGCTGGGTATTATATGTGTGCCCGGG;RP514: GTTCTTCGGTCTCGAGGTGACTACAAGGATGACGACGACAAGGGCACTGTGAGCTTAGGGTTAGAAATTT;RP515: GTTCTTCGGTCTCGAGGTGACTACAAGGATGACGACGACAAGGGCACTGTGAGCTTAGGGTTAGCCGG;RP132: GACGTTGACTTAAAGTCTAACCTATAGGATACTTACAGCCATCGAGAGGGACACGGCGCATTCTCGAGCGTAC;RP132C: GCTCGAGAATGCGCCGTGTCCCTCTCGATGGCTGTAAGTATCCTATAGGTTAGACTTTAAGTCAACGTCGTAC;RP370: CACTGTGAGCTTAGGGTTAGGAATTC;RP316FAM5: /56-FAM/TTTTTTTTTTTTTTTTTTTTTTTTTTTTT;SJB123: GGTTAGCCCGGG;RP344Cy3: /5Cy3/TTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTT;RP343: CTAAGCTCACAGTG;SJB153: TATAATACCCAGCAAGTCAGCATC; SJB154: GGAATCTAGAGCACATTCTGCGGCC;SJB155: TCTGTGCTCTGCAAGCCGCCTAACC;SJB158: TATAATACCCAGCAAGTCAGCAT/3ddC/;SJB159: GGAATCTAGAGCACATTCTGCGGC/3ddC/;RP540Cy3: GCATATTCACTGTGAGCTTAGTGTTAGGACTCGG/3Cy3Sp/;RP541Cy5: GCATATTCACTGTGAGCTTAGTGTTACCGAGTCC/3Cy5Sp/;RP538: CGACAAGAGTCATGAATTCTTAGGGTTAGCCCGGG;RP539: CTAAGAATTCATGACTCTTGTCG;SJB089: CAATTCAGCAACTAATGTCATACCAGCTGAAGTTGGTGCAGAG;SJB090: CTCTGCACCAACTTCAGCTGGTATGACATTAGTTGCTGAATTG;SJB100: TTCTGCTAGCGGTGGTGGAGGAAGTGGAGGAGGCGGATCTGGTGGTGGCGGTAGCGGTTTTAAAGATAACTCTCCAATCTCAGATACTTC;SJB101: TCTTCTGCTAGCCATTTCAACCAAATCTTGTTGCAAG.Primer templates were 5\u2032- phosphorylated on the shorter strand with T4 polynucleotide kinase (New England Biolabs) and ATP. Primer templates were annealed by mixture of a ratio of 1:2 of short to long strands then boiling and slow cooling to room temp. DNA was 3xFLAG-Pol\u03b8 plasmid was derived from pRS424 (ATCC). Human Pol\u03b8 nucleotide sequence was optimized for yeast and synthesized as 2 gene fragments by GenScript. Yeast optimized gene fragments were cloned into pRS424 sequentially. 3xFLAG-Pol\u03b8K121M plasmid was derived from 3xFLAG-Pol\u03b8 plasmid by site-directed mutagenesis using primers (SJB089 and SJB090). 3xFLAG-Pol\u03b8\u0394cen was derived from 3xFLAG-Pol\u03b8 plasmid by molecular cloning with PCR primers (SJB100 and SJB101).Pol\u03b8, Pol\u03b8-pol, and Pol\u03b8\u0394cen were resolved by SDS/PAGE and transferred to a nitrocellulose membrane. The membrane was blocked with 5% milk in TBS with 0.1% Tween-20 and incubated with primary antibody against C-terminal portion of Pol\u03b8  in TBS/5% milk/0.1% Tween-20 for 1.5\u2009hr at room temp, followed by incubation with HRP-conjugated secondary antibody  for 1\u2009h at room temp. Bands were detected via chemiluminescence.13 and Pol\u03b8-pol 16. The Pol\u03b8-hel:ssDNA model was constructed by superposing Pol\u03b8-hel structure with the crystal structure of archaeal DNA helicase (Hel308):DNA complex28, and the strand in which Hel308 translocates on was included in the model. The template DNA in the Pol\u03b8-pol:DNA complex was removed and the 5\u2032 end of the primer DNA was connected to the 3\u2032-end of DNA in the Pol\u03b8-hel model. Pol\u03b8-hel was modeled facing upstream due to its 3\u2032\u22125\u2032 translocation activity.The Pol\u03b8\u0394cen:ssDNA model was constructed by using the previously determined crystal structures of human Pol\u03b8-hel 3 linker (L), see Supplementary Fig.\u00a0Pol\u03b8\u0394cen is modelled by two large spheres, representing the polymerase (P) and helicase (H) domains, connected by a short flexible polymer chain made by 6 beads, representing the (GGGGS)T\u2009=\u2009300\u2009K and with a potential energy V, composed by the following interaction terms.Each bead is governed by a Langevin equation of motion at temp VP-P(r)\u2009=\u2009VH-H(r)\u2009=\u2009\u03b5((\u03c3/r)12-(\u03c3/r)6), where \u03c3\u2009=\u20095.6\u2009nm is about twice the gyration radius of both P and H and \u03b5\u2009=\u200910KBT is the interaction strength. The potentials VP-P and VH-H are truncated at r\u2009=\u20098\u2009nm, which correspond to a cutoff distance of about 1.5\u2009nm from their potential minimum, situated at 21/6\u03c3. The distance 1.5\u2009nm corresponds roughly to the Debye screening length for this system.The interactions between polymerase-polymerase and helicase-helicase are attractive, and are modelled with a Lennard-Jones potential r\u2009=\u200921/6\u03c3.All other bead-bead interactions are instead only repulsive and modelled with a Lennard\u2013Jones potential truncated at the potential minimum VP-H(r)), \u03c3\u2009=\u20095.6\u2009nm and \u03b5\u2009=\u200910KBT. For linker-linker interactions (VL-L(r)), \u03c3\u2009=\u20091\u2009nm, corresponding to about 2.5 amino acids, and \u03b5\u2009=\u20091KBT. For polymerase-linker and helicase-linker (VP-L(r)\u2009=\u2009VH-L(r)) \u03c3\u2009=\u20093.3\u2009nm and \u03b5\u2009=\u200910KBT.\u03c3 and \u03b5 vary depending on the particle types. For polymerase-helicase interactions (VH\u2009=\u2009K(r-r0), where K\u2009=\u2009750 KBT/nm2 and r0\u2009=\u20091\u2009nm for linker-linker bonds and r0\u2009=\u20093.3\u2009nm for linker-helicase and linker-polymerase bonds.The connectivity between the beads of each Pol\u03b8\u2206cen model , and the size range of the simulation boxes allow to reproduce the local concentration, size and shape of multimers observed in the EM data.To generate the assemblies of varying size, we initialized the system with proteins randomly distributed at densities of about 1\u20133\u2009\u00d7\u200910BT and m\u2009=\u2009900\u2009Da. In simulation units, the integration timestep is dt\u2009=\u20090.01 and the friction coefficient is \u03b3\u2009=\u20090.5. The simulation box is bounded by repulsive walls with a repulsive truncated Lennard\u2013Jones potential, where the truncation is set at r\u2009=\u200921/6\u03c3. A typical simulation is long 5\u20136\u2009\u00d7\u2009106 time units.The simulations are carried out with the software LAMMPS with reduced units \u03c3\u2009=\u20091\u2009nm, \u03b5\u2009=\u20091KThe clusters generated by the self-assembly process have a peculiar elongated shape, which is also characteristic of the EM images. This structural feature is absent if the helicase-helicase or polymerase-polymerase attractive interactions are substituted with a truncated repulsive Lennard-Jones potential, see Supplementary Fig.\u00a0Further information on research design is available in the\u00a0Supplementary InformationPeer Review FileDescription of Additional Supplementary FilesSupplementary Movie 1Supplementary Movie 2Supplementary Movie 3Supplementary Movie 4Supplementary Movie 5Supplementary Movie 6Supplementary Movie 7Supplementary Movie 8Reporting SummarySource Data"}
{"text": "Nature Communications 10.1038/s41467-018-03728-5; published online: 10 April 2018Correction to: The originally published version of this article contained an error in the name of the author Fl\u00f3ra G\u00f6l\u00f6ncs\u00e9r, which was incorrectly given as Fl\u00f3ra G\u00f6r\u00f6ncs\u00e9r. This has now been corrected in both the PDF and HTML versions of the article."}
{"text": "In the title com\u00adpound, inter\u00admolecular C\u2014H\u22efO, O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. 13H14N2O3, the dihydropyridazine ring (r.m.s. deviation\u00a0= 0.166\u2005\u00c5) has a screw-boat conformation. The dihedral angle between its mean plane and the benzene ring is 0.77\u2005(12)\u00b0. In the crystal, inter\u00admolecular O\u2014H\u22efO hydrogen bonds generate C(5) chains and N\u2014H\u22efO hydrogen bonds produce R22(8) motifs. These types of inter\u00adactions lead to the formation of layers parallel to (12R24(8) motifs. Inter\u00admolecular inter\u00adactions were additionally investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots. The most significant contributions to the crystal packing are by H\u22efH (43.3%), H\u22efC/C\u22efH (19.3%), H\u22efO/H\u22efO (22.6%), C\u22efN/N\u22efC (3.0%) and H\u22efN/N\u22efH (5.8%) contacts. C\u2014H\u22ef\u03c0 inter\u00adactions and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions are not observed.In the title com\u00adpound, C This nitro\u00adgen heterocycle became a scaffold of choice for the development of potential drug candidates -6-(4-hy\u00addroxy-3-meth\u00adoxy\u00adstyr\u00adyl)-4,5-di\u00adhydro\u00adpyridazin-3(2H)-one, as well as an analysis of the Hirshfeld surfaces.In continuation of our studies related to mol\u00adecular structures and Hirshfeld surface analysis of new heterocyclic derivatives \u2005\u00c5 for the C3 atom; the C2 atom lies \u22120.177\u2005(3)\u2005\u00c5 out of the plane in the opposite direction relative to the C3 atom. The dihedral angle between the dihydropyridazine ring mean plane and the benzene ring (C7\u2013C12) is 0.77\u2005(12)\u00b0, indicating an almost planar conformation of the molecule favouring delocalization over the C4\u2014C5=C6\u2014C7 bridge.In the title mol\u00adecule Fig.\u00a01, the coni hydrogen bonds between the phenolic OH group and the carbonyl O atom of a neighbouring mol\u00adecule generate C(5) chains extending parallel to [101]. Likewise, N1\u2014H1\u22efO1ii hydrogen bonds between the N\u2014H function of the di\u00adhydro\u00adpyridazine ring and the carbonyl O atom generate centrosymmetric dimers with an A\u22efO2iii and C13\u2014H13C\u22efO2iv hydrogen bonds with In the crystal, mol\u00adecules are stacked in rows parallel to [100]. Notably, no significant C\u2014H\u22ef\u03c0 or \u03c0\u2013\u03c0 inter\u00adactions are observed. O2\u2014H2\u22efO1fs Fig.\u00a02.et al., 2016viz. 6-phenyl-4,5-di\u00adhydro\u00adpyridazin-3(2H)-one -(\u2212)-6-(4-amino\u00adphen\u00adyl)-5-methyl-4,5-di\u00adhydro\u00adpyridazin-3(2H)-one  to 2.2382\u2005a.u. (blue). The surfaces mapped over relevant inter\u00admolecular contacts are illustrated in Fig.\u00a03dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efN/N\u22efC and H\u22efN/N\u22efH inter\u00adactions in Figs.\u00a04a)\u2013(e), respectively. The overall two-dimensional fingerprint plot and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efN/N\u22efC and H\u22efN/N\u22efH contacts are illustrated in Figs.\u00a05a)\u2013(f), respectively. The largest inter\u00adaction is that of H\u22efH, contributing 43.3% to the overall crystal packing. H\u22efC/C\u22efH contacts add a 19.3% contribution to the Hirshfeld surface, with the tips at de + di \u223c 2.72\u2005\u00c5. H\u22efO/O\u22efH contacts make a 22.6% contribution to the Hirshfeld surface and are represented by a pair of sharp spikes in the region de + di\u00a0\u223c 2.70\u2005\u00c5 in the fingerprint plot. H\u22efO/O\u22efH inter\u00adactions arise from inter\u00admolecular O\u2014H\u22efO hydrogen bonding and C\u2014H\u22efO contacts. The contributions of the other contacts to the Hirshfeld surface are negligible, i.e. C\u22efN/N\u22efC of 3.0% and H\u22efN/N\u22efH of 5.8%.Hirshfeld surface analysis was used to qu\u00adantify the inter\u00admolecular inter\u00adactions of the title com\u00adpound, using To a solution of 6-(4-hy\u00addroxy-3-meth\u00adoxy\u00adphen\u00adyl)-4-oxohex-5-enoic acid  in 20\u2005ml of ethanol, an equimolar amount of hydrazine hydrate was added. The mixture was maintained under reflux until thin-layer chromatography (TLC) indicated the end of the reaction. After cooling, the precipitate which formed was filtered off, washed with ethanol and recrystallized from ethanol. Slow evaporation at room temperature led to the formation of single crystals of the title com\u00adpound.Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. The NH and OH hydrogens were located in a difference Fourier map and were constrained with N\u2014H = 0.86\u2005\u00c5 and Uiso(H) = 1.2Ueq(N), and O\u2014H = 0.86\u2005\u00c5 and Uiso(H) = 1.5Ueq(O), using a riding model.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019014130/wm5521sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019014130/wm5521Isup3.hklStructure factors: contains datablock(s) I. DOI: 1959568, 1959568CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-thio\u00adchromene (A) and 2-(2-bromo-5-fluoro\u00adphen\u00adyl)-7-meth\u00adoxy-3-nitro-2H-thio\u00adchromene (B) are described. In each crystal, the mol\u00adecules are linked by hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions.The synthesis and structure of 2-(2-bromo-5-fluoro\u00adphen\u00adyl)-8-eth\u00adoxy-3-nitro-2 H-thio\u00adchromene  and 2-(2-bromo-5-fluoro\u00adphen\u00adyl)-7-meth\u00adoxy-3-nitro-2H-thio\u00adchromene , were prepared via the condensation reaction between 2-mer\u00adcapto\u00adbenzaldehyde and nitro\u00adstyrene derivatives. In both com\u00adpounds, the thio\u00adchromene plane is almost perpendicular to the phenyl ring. In the structure of A, mol\u00adecules are assembled via \u03c0\u2013\u03c0 stacking and C\u2014H\u22efO and C\u2014F\u22ef\u03c0 inter\u00adactions. In the crystal packing of B, mol\u00adecules are linked by C\u2014H\u22efF, C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions.Two thio\u00adchromene com\u00adpounds containing Br and F atoms, namely 2-(2-bromo-5-fluoro\u00adphen\u00adyl)-8-eth\u00adoxy-3-nitro-2 H-Chromenes (or 2H-benzo\u00adpyrans) are heterocyclic com\u00adpounds found in many natural plants. This class of mol\u00adecules shows a wide variety of biological activities, such as anti\u00adcancer, anti-inflammation and anti-HIV  and 2-(2-bromo-5-fluoro\u00adphen\u00adyl)-7-meth\u00adoxy-3-nitro-2H-thio\u00adchromene (B). Crystal structure determination can help to understand the role of halogenated substituents in the biological activity of these com\u00adpounds.2A) crystallizes in the triclinic space group PB) crystallizes in the space group P21/c, both with one mol\u00adecule in the asymmetric unit \u00b0 with phenyl ring C1\u2013C6, while in B, this angle is 86.94\u2005(8)\u00b0, which indicates that the 2-bromo-5-fluoro\u00adphenyl ring is roughly perpendicular to the thio\u00adchromene plane. Both 2H-thio\u00adpyran rings have a screw-boat conformation, with atom C7 having the largest deviation from the best plane through atoms S1/C7\u2013C11 . The C\u2014S bond lengths are almost equal . The C11\u2014S1\u2014C7 bond angle is 102.5\u2005(2)\u00b0 in A and 100.47\u2005(9)\u00b0 in B. The N\u2014O bond lengths in com\u00adpound B [1.232\u2005(2) and 1.221\u2005(2)\u2005\u00c5] are slightly longer than those in com\u00adpound A [both 1.219\u2005(5)\u2005\u00c5]. The nitro group is situated in the thio\u00adchromene plane, as illustrated by the torsion angle O2\u2014N8\u2014C8\u2014C9 of 1.3\u2005(7)\u00b0 in A and 9.5\u2005(3)\u00b0 in B.Compound \u2005\u00c5; symmetry code: (i) \u2212x, \u2212y\u00a0+\u00a02, \u2212z; Cg3 is the centroid of the C10\u2013C15 ring]. Neighbouring dimers inter\u00adact through C\u2014F\u22ef\u03c0 and short Br1\u22efH5ii inter\u00adactions .In the crystal of s Table\u00a01 and \u03c0\u2013\u03c0 B, two mol\u00adecules form dimers through C\u2014H\u22efF hydrogen bonds (Table\u00a02c direction through \u03c0\u2013\u03c0 inter\u00adactions . Parallel chains inter\u00adact via C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions.In the crystal of com\u00adpound s Table\u00a02. These det al., 2016H-thio\u00adchromene derivatives, of which three contain halogen atoms [CSD refcodes IFOZIO  in toluene and the reaction mixture was stirred at room temperature for 2\u2005h. After com\u00adpletion of the reaction, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography on silica gel (yield 90%). Crystals suitable for single-crystal X-ray diffraction data collection were obtained by slow evaporation from an ethanol solution.To a round-bottomed flask was added 2-mercaptobenzaldehyde (1 equiv.), nitro\u00adstyrene (1 equiv.) and KUiso(H) = 1.2Ueq(C) for Csp2\u2014H and Uiso(H) = 1.5Ueq(C) for Csp3\u2014H. A rotating-group model was applied for methyl-group C17 in A and C16 in B.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019014178/vm2223sup1.cifCrystal structure: contains datablock(s) A, B, global. DOI: 10.1107/S2056989019014178/vm2223Asup8.hklStructure factors: contains datablock(s) A. DOI: 10.1107/S2056989019014178/vm2223Bsup9.hklStructure factors: contains datablock(s) B. DOI: Click here for additional data file.10.1107/S2056989019014178/vm2223Asup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019014178/vm2223Bsup5.cmlSupporting information file. DOI: 1950406, 1953121, 1950406, 1953121CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound has a nonplanar conformation. In the crystal, the anions are linked to the cations and the water mol\u00adecules by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a three-dimensional network. Face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed. 2H10N22+\u00b7C21H13N3O8S2\u2212\u00b72H2O, the planes of the phenyl rings and the benzene ring of the 5-nitro-2-oxido\u00adbenzene\u00adsulfonate group are inclined to one another by 44.42\u2005(11), 56.87\u2005(11) and 77.70\u2005(12)\u00b0. In the crystal, the anions are linked to the cations and the water mol\u00adecules by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a three-dimensional network. Furthermore, there are face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions between the centroids of one phenyl ring and the benzene ring of the 5-nitro-2-oxido\u00adbenzene\u00adsulfonate group [centroid\u2013centroid distance = 3.8382\u2005(13)\u2005\u00c5 and slippage = 1.841\u2005\u00c5]. A Hirshfeld surface analysis was conducted to verify the contributions of the different inter\u00admolecular inter\u00adactions.In the anion of the title hydrated salt, C DOI: 10.1107/S2056989018009118/qm2125Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018009118/qm2125Isup3.cmlSupporting information file. DOI: 1851087CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, inter\u00admolecular N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional supra\u00admolecular network. H-pyridazin-3-one derivative. The mol\u00adecule, C18H16N2O, is not planar; the benzene and pyridazine rings are twisted with respect to each other, making a dihedral angle of 11.47\u2005(2)\u00b0, and the toluene ring is nearly perpendicular to the pyridazine ring, with a dihedral angle of 89.624\u2005(1)\u00b0. The mol\u00adecular conformation is stabilized by weak intra\u00admolecular C\u2014H\u22efN contacts. In the crystal, pairs of N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into inversion dimers with an R22(8) ring motif. The inter\u00admolecular inter\u00adactions were investigated using Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots, revealing that the most important contributions for the crystal packing are from H\u22efH (56.6%), H\u22efC/C\u22efH (22.6%), O\u22efH/H\u22efO (10.0%) and N\u22efC/C\u22efN (3.5%) inter\u00adactions.In this paper, we describe the synthesis of a new di\u00adhydro-2 Pyridazinone is an important pharmacophore possessing a wide range of biological applications . Weak C\u2014H\u22efO hydrogen bonds and weak off-set \u03c0-stacking stabilize the packing. In the crystal, hydrogen bonds link the chains into a two-dimensional (2D) network parallel to (011) ], with a centroid-to-centroid distance of 3.8333\u2005(18)\u2005\u00c5 and a slippage of 1.460\u2005\u00c5 (Cg1 is the centroid of the C9\u2013C11/N1/N2 ring and Cg3 is the centroid of the C13\u2013C18 ring) .The mol\u00adecules are connected two-by-two through N1\u2014H1\u22efO1 hydrogen bonds Table\u00a02, with a g) Fig.\u00a02a.et al., 2016H)-one (see A in Schemep-tolyl\u00adpyridazin-3(2H)-one  to 1.4188\u2005a.u. (blue). The 3D dnorm surface of the title complex is illustrated in Figs.\u00a03a) and 4dnorm values on the surface correspond to the N\u2014H\u22efO inter\u00adactions  is due to short inter\u00adatomic H\u22efH contacts. In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions in the crystal, the pair of characteristic wings in the fingerprint plot representing H\u22efC/C\u22efH contacts (22.6% contribution to the HS) have a symmetrical distribution of points , with the tips at de\u00a0+ di = 2.797\u2005\u00c5. The O\u22efH  contacts contribute 10% to the HS and have a symmetrical distribution of points, with the tips at de + di = 1.853\u2005\u00c5. The contribution of the other contact to the Hirshfeld surface is N\u22efC/C\u22efN (3.5%). The Hirshfeld surface representations with the function dnorm plotted on the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efC and H\u22efN/N\u22efH inter\u00adactions in Figs.\u00a06et al., 2015The Hirshfeld surface analysis . The convex blue regions on the shape-index symbolize hydrogen-donor groups and the concave red regions symbolize hydrogen-acceptor groups. The \u03c0\u2013\u03c0 inter\u00adactions on the shape-index map of the Hirshfeld surface are generally indicated by adjacent red and blue triangles.A shape-index map of the title compound was generated in the range \u22121 to 1\u2005\u00c5 Fig.\u00a03b. The cc). This shows large regions of green indicating a relatively flat surface area (planar), while the blue regions indicate areas of curvature. The presence of \u03c0\u2013\u03c0 stacking inter\u00adactions is also evident in the flat regions around the rings on the Hirshfeld surface plotted over curvedness (see the Supra\u00admolecular features section above).A curvedness map of the title compound was generated in the range \u22124 to 0.4\u2005\u00c5 Fig.\u00a03c. This H)-one and  of 4-methyl\u00adbenz\u00adaldehyde in ethanol (30\u2005ml), sodium hydroxide  was added. The solvent was evaporated under vacuum and the residue was purified through silica-gel column chromatography using hexa\u00adne/ethyl acetate (7:3 v/v). Slow evaporation at room temperature leads to single crystals.To a solution  of 6-phenyl-4,5-di\u00adhydro\u00adpyridazin-3(2Uiso(H) = 1.5Ueq(C) for methyl, C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for methyl\u00adene, C\u2014H = 0.93\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for aromatic and C\u2014H = 0.98\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for methine H atoms. Crystal data, data collection and structure refinement details are summarized in Table\u00a03H atoms were fixed geometrically and treated as riding, with C\u2014H = 0.97\u2005\u00c5 and 10.1107/S2056989019011551/mw2146sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019011551/mw2146Isup3.hklStructure factors: contains datablock(s) I. DOI: 1947718CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-indene-1,3(2H)-dione (ID[1]) and (E)-2-{3-[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]allyl\u00adidene}-1H-indene-1,3(2H)-dione (ID[2]), with donor\u2013\u03c0-bridge\u2013acceptor structures, are almost planar for the mol\u00adecule with a short \u03c0-bridge (ID[1]) but less planar for the mol\u00adecule with a longer bridge (ID[2]).The title pull\u2013push chromophores, 2-[4-(di\u00admethyl\u00adamino)\u00adbenzyl\u00adidene]-1 H-indene-1,3(2H)-dione, C18H15NO2 (ID[1]) and (E)-2-{3-[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]allyl\u00adidene}-1H-indene-1,3(2H)-dione, C20H17NO2 (ID[2]), have donor\u2013\u03c0-bridge\u2013acceptor structures. The mol\u00adecule with the short \u03c0-bridge, ID[1], is almost planar while for the mol\u00adecule with a longer bridge, ID[2], is less planar. The benzene ring is inclined to the mean plane of the 2,3-di\u00adhydro-1H-indene unit by 3.19\u2005(4)\u00b0 in ID[1] and 13.06\u2005(8)\u00b0 in ID[2]. The structures of three polymorphs of compound ID[1] have been reported: the \u03b1-polymorph  is non-centrosymmetric (space group P21), which suggests potential NLO properties for this crystalline material. In both compounds, there is short intra\u00admolecular C\u2014H\u22efO contact present, enclosing an S(7) ring motif. In the crystal of ID[1], mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming layers parallel to the bc plane. In the crystal of ID[2], mol\u00adecules are liked by C\u2014H\u22efO hydrogen bonds to form 21 helices propagating along the b-axis direction. The mol\u00adecules in the helix are linked by offset \u03c0\u2013\u03c0 inter\u00adactions with, for example, a centroid\u2013centroid distance of 3.9664\u2005(13)\u2005\u00c5 (= b axis) separating the indene rings, and an offset of 1.869\u2005\u00c5. Spectroscopic and electrochemical measurements show the ability of these compounds to easily transfer electrons through the \u03c0-conjugated chain.The title pull\u2013push chromophores, 2-[4-(di\u00admethyl\u00adamino)\u00adbenzyl\u00adidene]-1kova 1978. Kristalkova 1980. Kristalkaya 1980. Kristal Applications of pull\u2013push chromophores include non-linear optics  are important in many areas of materials chemistry, especially organic electronics and optoelectronics. Applic\u00adations of pull\u2013push mol\u00adecules can be related to their properties such as intra\u00admolecular charge transfer and specific mol\u00adecular arrangements in the solid state. Intra\u00admolecular charge transfer from donor to acceptor The mol\u00adecular structures of ID[1] and ID[2] are illustrated in Fig.\u00a01et al., 2019Both mol\u00adecules have acceptor\u2013\u03c0-bridge\u2013donor structures. It was found, as in our previous studies  being inclined to the mean plane of the indene ring system (C1\u2013C9) by 3.19\u2005(4)\u00b0. In ID[2] the deviation from planarity is somewhat larger with the benzene ring (C10\u2013C15) being inclined to the mean plane of the indene ring system (C1\u2013C9) by 13.06\u2005(8)\u00b0; see further details in Table\u00a01Mol\u00adecules of ID[1] and ID[2] have significant dipole moments, which is very common for NLO chromophores. Because of this, mol\u00adecules have a trend to anti\u00adparallel packing, which is observed in the crystal structures of both ID[1] and ID[2].ca 84.47\u00b0 between them. The mol\u00adecules, which stack in an anti\u00adparallel or head-to-tail fashion, are linked by C\u2014H\u22efO hydrogen bonds \u2005\u00c5  separating the indene ring systems (C1\u2013C9), with an offset of 1.869\u2005\u00c5.In the crystal of ID[2], mol\u00adecules form stacks with parallel mol\u00adecular positions, and shifted positions of stacks extended along the on Fig.\u00a03. Here, ts Table\u00a03, forminget al., 2019Absorbance spectra were obtained for both ID[1] and ID[2] in chloro\u00adform and aceto\u00adnitrile. For donor\u2013acceptor polyenes, the dominating feature of the absorbance spectrum is the \u03c0\u2013\u03c0* transition that results from charge transfer from donor to acceptor. According to recent studies (Bogdanov a), however, when swept to \u22121.9\u2005V the reduction is only partly reversible . This represents the ability of the compound to \u2018easily\u2019 transfer electrons through the chain from donor towards acceptor.Donor\u2013acceptor polyenes can be characterized by electrochemical measurements to show their ability to transfer electrons. The voltammagrams Fig.\u00a05 demonstrle Fig.\u00a05b. This 2+/0  in di\u00adchloro\u00admethane with 0.1 nM Bu4NPF6). Measurements were recorded at 50\u2005mV\u2005s\u22121 using a BAS Potentiostat using a glassy carbon working electrode, Pt wire auxilliary electrode and a Ag/AgCl reference electrode.Note: cyclic voltammagrams of ID[1] were made against FeCpet al., 2016p-di\u00adethyl\u00adamino\u00adbenzyl\u00adidene)-1,3-indandione -dione -di\u00adone , 1.66\u2005(6)/1.49\u2005(9) and 5.71\u2005(9)\u00b0, for TELWEN, QENYEQ/QENYEQ01 and BIQYUY, respectively, compared to 3.19\u2005(4)\u00b0 in ID[1].A search of the Cambridge Structural Database , while in the \u03b3 polymorph it is acentric (space group Pna21). The crystal structure of ID[1] we obtained corresponds to the \u03b2 polymorph, i.e. the centrosymmetric modification MBYINO02. The dihedral angles between the benzene and indene rings for two independent mol\u00adecules in MBYINO are ca 4.35 and 7.79\u00b0, compared to ca 7.36\u00b0 in MBYINO01, and 3.54\u00b0 in MBYINO02 (cf. 3.19\u2005(4)\u00b0 in the present crystal structure analysis of ID[1]).Also, out of all 27 hits there are three hits, -dione \u00b0 in ID[2]. In ZIGPIR this dihedral angle is smaller at 8.6\u2005(3)\u00b0.A search of the CSD for the substructure of ID[2] yielded nine hits. Only two structures are similar to that of ID[2]. The first, 2-{3-[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]prop-2-yn-1-yl\u00adidene}-1et al., 2019For the synthesis of the title compounds, two aldehydes were used: 4-(di\u00admethyl\u00adamino)\u00adbenzaldehyde  and 4-(di\u00admethyl\u00adamino)\u00adcinnamaldehyde (A2), which was synthesized as described previously \u00adbenzyl\u00adidene]indane-1,3-dione (ID[1]): Aldehyde A1  and 1,3-indanedione  were suspended in 100\u2005ml of absolute ethanol. The mixture was gently heated until the solids had dissolved. After about 10\u2005min of stirring the dissolution was complete, and a red crystalline precipitate began forming on the walls of the flask. The reaction mixture was stirred vigorously overnight, and the resulting product was collected by filtration then washed with cold ethanol and hexa\u00adnes to give shiny dark-red crystals . ID[1] can be purified by recrystallization using numerous solvent systems , many of which afforded single crystals. 1H NMR  \u03b4 8.52 , 7.91\u20139.73 , 7.71 , 6.77 , 3.14  ppm. 13C NMR  \u03b4 191.6, 190.1, 154.5, 147.3, 142.7, 140.3, 138.2, 134.8, 134.5, 123.3, 122.7, 122.6, 122.2, 111.7, 40.3 ppm.Synthesis of (E)-2-{3-[4-(di\u00admethyl\u00adamino)\u00adphen\u00adyl]allyl\u00adidene}indane-1,3-dione (ID[2]): Aldehyde A2 , 1,3-indanedione  and piperidine  in ethanol (50\u2005ml) were mixed and treated as for the synthesis of ID[1]. The crude product obtained was collected by filtration and washed with cold ethanol before being recrystallized from ethanol to give incredibly shiny and thin purple actinic crystals . They were washed with hexane and dried under vacuum. 1H NMR  \u03b4 8.25 , 7.90\u20137.86 , 7.76\u20137.73 , 7.60 , 7.60 , 7.34 , 6.72 , 3.08  ppm.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Uiso(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S205698901901329X/su5515sup1.cifCrystal structure: contains datablock(s) ID1, ID2, Gobal. DOI: 10.1107/S205698901901329X/su5515ID1sup2.hklStructure factors: contains datablock(s) ID1. DOI: 10.1107/S205698901901329X/su5515ID2sup3.hklStructure factors: contains datablock(s) ID2. DOI: Click here for additional data file.10.1107/S205698901901329X/su5515ID1sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901901329X/su5515ID2sup5.cmlSupporting information file. DOI: 1956419, 1956418, 1956418, 1956419CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2010Methylation of lysyl residues is widely observed on histone proteins. Using isolated enzymes, we report mechanistic and structural studies on histone lysine demethylase (KDM)\u2010catalysed demethylation of N\u03b5\u2010methylated lysine 26 on histone 1 isotype 4 (H1.4). The results reveal that methylated H1.4K26 is a substrate for all members of the KDM4 subfamily and that KDM4A\u2010catalysed demethylation of H1.4K26me3 peptide is similarly efficient to that of H3K9me3. Crystallographic studies of an H1.4K26me3:KDM4A complex reveal a conserved binding geometry to that of H3K9me3. In the light of the high activity of the KDM4s on this mark, our results suggest JmjC KDM\u2010catalysed demethylation of H1.4K26 may be as prevalent as demethylation on the H3 tail and warrants further investigation in cells. Our findings reveal that demethylation of methylated lysyl residues in H1.4K26 peptide fragments is catalysed by all members of the human KDM4 subfamily of JmjC KDMs (KDM4A\u2010E), supporting previously reported cell\u2010based studies (predominantly with mouse enzymes) Escherichia coli . Sequences are given in Table\u00a0Peptides were produced as C\u2010terminal amides using a Liberty Blue automated microwave peptide synthesiser , using standard fluorenylmethyloxycarbonyl\u2010mediated solid\u2010phase chemistry and NovaPEG rink amide resin . Following synthesis, peptides were cleaved from the resin by incubation with trifluoroacetic acid/water/triisopropylsilane/dimethoxybenzene (92.5 : 2.5\u00a0:\u00a02.5\u00a0: 2.5) for 3\u00a0h followed by precipitation with ice\u2010cold diethyl ether. For kinetic experiments, lyophilised peptides were purified by reverse\u2010phase high\u2010performance liquid chromatography using a Vydac C18 column (Solvent A: 0.1% trifluoroacetic acid in Hm) were incubated with peptides  ammonium sulfate (10\u00a0\u03bcm), sodium ascorbate (100\u00a0\u03bcm) and 2\u2010oxoglutaric acid (200\u00a0\u03bcm). Reactions with KDM3A and KDM7A also contained 1\u00a0mm tris(2\u2010carboxyethyl)phosphine hydrochloride. No enzyme reactions were included as negative controls. Reactions were incubated for 1\u00a0h at 37\u00a0\u00b0C before being quenched with 1\u00a0:\u00a01 (v/v) methanol. Analysis was carried out by MALDI\u2010TOF MS , with demethylation observed as mass shifts of 14\u00a0Da.Recombinant proteins (1\u00a0\u03bc1H observation and were carried out as previously described m), 2OG (400\u00a0\u03bcm), H1.4(18\u201332)K26me3 peptide (400\u00a0\u03bcm), Fe(II) ammonium sulfate (100\u00a0\u03bcm) and ascorbate (1\u00a0mm) in 50\u00a0mm ammonium formate, pH 7.5, 500\u00a0mm NaCl in 10% v/v D2O) were prepared in a microcentrifuge tube , before being transferred to an NMR tube. The samples were then analysed over time using automated routines; each time\u2010point corresponded to one experiment accumulating 16 transients . The solvent resonance was depleted by excitation sculpting using a 180\u00b0 sinc pulse (duration\u00a0=\u00a02\u00a0ms) The NMR analyses employed a Bruker Avance III 700\u00a0MHz spectrometer with an inverse TCI cryoprobe optimised for +\u2010coupled) assay for quantification of the formaldehyde reaction byproduct, as previously described m HEPES, pH 7.5, 0.01% Tween\u201020, with addition of Fe(II) ammonium sulfate (10\u00a0\u03bcm), sodium ascorbate (100\u00a0\u03bcm), 2\u2010oxoglutarate (200\u00a0\u03bcm), NAD+ (500\u00a0\u03bcm), KDM4 enzymes  and FDH enzyme  in a 30\u2010\u03bcL volume in black 384\u2010well plates. Specific activities were measured using a 100\u2010\u03bcm peptide. For Michaelis\u2013Menten experiments, peptide concentrations were varied. Reactions were monitored using a PHERAstar FS plate reader  with 355\u00a0nm excitation and 460\u00a0nm emission. Kinetic parameters were calculated from the reaction rate during the initial linear phase of formaldehyde production, which were used to calculate specific activities or fitted to Michaelis\u2013Menten equations using graphpad prism .Kinetic parameters for KDM4 enzymes were determined by use of an FDH /NAD1\u2013359.Ni(II).H1.4(18\u201332)K26me3.NOG were obtained in sitting drops grown at 4\u00a0\u00b0C with a ratio of 1\u00a0:\u00a02 sample to well solution [0.1\u00a0m MIB buffer ] \u22121 KDM4A, 5\u00a0mm H1.4(18\u201332)K26me3, 5\u00a0mm NOG and 4\u00a0mm NiCl2. Crystals were cryoprotected with 25% glycerol then flash\u2010frozen in liquid N2. Data were collected using a single crystal at 100\u00a0K at the Diamond I04\u20101 MX beam line and were processed with HKL2000 http://www.rcsb.org/pdb/search/structidSearch.do?structureId=2OX0) and was refined by alternative cycles of CNS http://www.rcsb.org/pdb/search/structidSearch.do?structureId=6H8P.Co\u2010crystals of KDM4A).H1.418\u2013K26me3.NO2N\u2010TPVKKKARKSAGAAK\u2010CONH2), but containing either a N\u03b5\u2010tri\u2010, di\u2010 or monomethyllysine at K26 were synthesised  and fragment peptides Table\u00a0 37. Thresed Fig.\u00a0. Activitsed Fig.\u00a0. After iM4D Fig.\u00a0 15, 43. M4D Fig.\u00a0, low levM4D Fig.\u00a0.Given the activity observed with KDM4E and KDM7A, we decided to investigate the intra\u2010subfamily conservation of this demethylation activity. The demethylation activity of the other subfamily members (KDM4A\u2010D and KDM7B) was therefore screened. For all KDM4 subfamily members, we observed H1.4K26 demethylation activity similar to that already observed with KDM4E Table\u00a0; howeverN\u03b5\u2010Trimethylated H3K4 binds to the plant homeobox domain of KDM7B, targeting the N\u03b5\u2010dimethyllysine at H3K9 to the catalytic domain, and thus promoting demethylation di\u2010N\u03b5\u2010methyllysine at K26 and tri\u2010N\u03b5\u2010methyllysine at K21 K21me3K26me2) and the H1.4 peptides methylated only at K26 .K26 Fig.\u00a0, but no 1H NMR time course analyses with KDM4A and the trimethylated H1.4K26me3 peptide confirmed time\u2010dependent demethylation of the Kme3 residue  were determined for comparison \u2010coupled demethylation assay, which monitors the formation of NADH during FDH\u2010catalysed oxidation of formaldehyde son Figs\u00a0D, S14. T+ and FDH were analysed over time and kinetic parameters were determined by recording the initial reaction rates of NADH production  at varying peptide concentration. Similar experiments were carried out with H3K9me3 and H3K36me3 substrate peptides and the obtained values compared (Table\u00a0KM (32.3\u00a0\u00b1\u00a06.4\u00a0\u03bcm and 25.5\u00a0\u00b1\u00a04.9\u00a0\u03bcm respectively) and kcat (0.32\u00a0\u00b1\u00a00.049 s\u22121 and 0.31\u00a0\u00b1\u00a00.045 s\u22121 respectively) values. Demethylation\u00a0of the H3K36me3 peptide was the least efficient, with\u00a0higher KM (66.8\u00a0\u00b1\u00a05.4\u00a0\u03bcm) and lower kcat (0.12\u00a0\u00b1 0.004 s\u22121) values than with the other two peptides.Michaelis\u2013Menten kinetics were then conducted with KDM4A. Samples containing KDM4A, 2OG, ascorbate, H1.4K26me3 peptide, NADN\u2010oxalylglycine:H1.4K26me3 peptide complex was solved to a resolution of 1.98 \u00c5 (Note: Ni(II) was used for crystallisation in place of the catalytically relevant Fe(II) due to its oxidative stability; N\u2010oxalylglycine (NOG) is a 2OG mimetic inhibitor) Crystallographic analyses were undertaken to investigate the binding mode of trimethylated H1.4K26 in the KDM4A active site. An X\u2010ray crystal structure of a KDM4A:Ni(II):http://www.rcsb.org/pdb/search/structidSearch.do?structureId=2OQ6http://www.rcsb.org/pdb/search/structidSearch.do?structureId=2P5B\u2010 to C\u2010 directionality through the active site. The two residues N\u2010terminal to the trimethyllysine residue  adopt a similar conformation/orientation in all three structures, with backbone hydrogen bonds between KDM4A E169 and the peptide residues at the \u22121 and \u22122 positions  in its sequence. Thus, in the K36 peptide, the backbone carbonyl of the H3K36 to K37 amide bond is \u2018flipped\u2019 ~180\u00b0 compared to the analogous amide in the other two substrates :NOG:H3K9me3 peptide complex  than either H3K9me3 or H1.4K26me3, binds differently at the KDM4A active site N\u2010methylated substrate lysine for H3K9/H1.4K26 versus H3K36 K26me3 crystal structure.Fig.\u00a0S2. KDM4E catalyses lysine demethylation at H1.4K26.Fig.\u00a0S3. KDM2A does not catalyse lysine demethylation at H1.4K26 under the tested conditions.Fig.\u00a0S4. KDM3A does not catalyse lysine demethylation at H1.4K26 under the tested conditions.Fig.\u00a0S5. KDM5C does not catalyse lysine demethylation at H1.4K26 under the tested conditions.Fig.\u00a0S6. KDM6B does not catalyse lysine demethylation at H1.4K26 under the tested conditions.Fig.\u00a0S7. KDM7A catalyses lysine demethylation at H1.4K26.Fig.\u00a0S8. KDM4A catalyses lysine demethylation at H1.4K26.Fig.\u00a0S9. KDM4B catalyses lysine demethylation at H1.4K26.Fig.\u00a0S10. KDM4C catalyses lysine demethylation at H1.4K26.Fig.\u00a0S11. KDM4D catalyses lysine demethylation at H1.4K26.Fig.\u00a0S12. PHF8/KDM7B only catalyses lysine demethylation at H1.4K26 at high concentration.Fig.\u00a0S13. Analysis of KDM4A demethylation by 1H NMR.Fig.\u00a0S14. Specific activity determination for KDM4 enzymes.Table\u00a0S1. Peptide sequences used in this study.Table\u00a0S2. Crystallographic data processing and refinement statistics.Click here for additional data file."}
{"text": "Brmind\u22efODio, C\u2014HBrmind\u22efOEthy, C\u2014HChlethy\u22efODio and C\u2014HChlethy\u22efOChlethy  hydrogen bonds link the mol\u00adecules into a three-dimensional structure, enclosing The title compound consists of the 5-bromo\u00adindoline-2,3-dione unit linked by a 1-{2-[2-(2 chloro\u00adeth\u00adoxy)eth\u00adoxy]eth\u00adyl} moiety. In the crystal, inter\u00admolecular C\u2014H 14H15BrClNO4, consists of a 5-bromo\u00adindoline-2,3-dione unit linked to a 1-{2-[2-(2-chloro\u00adeth\u00adoxy)eth\u00adoxy]eth\u00adyl} moiety. In the crystal, a series of C\u2014H\u22efO hydrogen bonds link the molecules to form a supramolecular three-dimensional structure, enclosing R22(8), R22(12), R22(18) and R22(22) ring motifs. \u03c0\u2013\u03c0 contacts between the five-membered dione rings may further stabilize the structure, with a centroid\u2013centroid distance of 3.899\u2005(2)\u2005\u00c5. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (28.1%), H\u22efO/O\u22efH (23.5%), H\u22efBr/Br\u22efH (13.8%), H\u22efCl/Cl\u22efH (13.0%) and H\u22efC/C\u22efH (10.2%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/6-311G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2014LUMO behaviour was elucidated to determine the energy gap. The chloro\u00adeth\u00adoxy\u00adethoxyethyl side chain atoms are disordered over two sets of sites with an occupancy ratio of 0.665\u2005(8):0.335\u2005(6).The title compound, C They are very inter\u00adesting chemical compounds because of their potential applications in different fields. The most common heterocycles contain nitro\u00adgen and oxygen  and B (N1/C1/C6\u2013C8), are oriented at a dihedral angle of A/B = 2.78\u2005(6)\u00b0. Atoms Br1, O1 and C9 are at distances of 0.0415\u2005(4), 0.0464\u2005(8) and \u22120.0244\u2005(7)\u2005\u00c5, respectively, from the best plane of the bromo\u00adindoline unit. The 1-{2-[2-(2-chloro\u00adeth\u00adoxy)eth\u00adoxy]eth\u00adyl} moiety is oriented with respect to the bromo\u00adindoline unit by 77.7\u2005(2)\u00b0, as defined by the C10\u2014C9\u2014N1\u2014C1 torsion angle.The title compound, (I)Brmind\u22efODio, C\u2014HBrmind\u22efOEthy, C\u2014HChlethy\u22efODio and C\u2014HChlethy\u22efOChlethy  hydrogen bonds (Table\u00a01Cg1\u2014Cg1i , may further stabilize the structure, with a centroid\u2013centroid distance of 3.899\u2005(2)\u2005\u00c5. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (28.1%), H\u22efO/O\u22efH (23.5%), H\u22efBr/Br\u22efH (13.8%), H\u22efCl/Cl\u22efH (13.0%) and H\u22efC/C\u22efH (10.2%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.In the crystal, inter\u00admolecular C\u2014Hs Table\u00a01 link thefs Fig.\u00a02. \u03c0\u2013\u03c0 conCrystalExplorer17.5  and those delineated into H\u22efH, H\u22efO/O\u22efH, H\u22efBr/Br\u22efH, H\u22efCl/Cl\u22efH, H\u22efC/C\u22efH, O\u22efC/C\u22efO, C\u22efC and O\u22efCl/Cl\u22efO contacts \u2013(i), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH, contributing 28.1% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule with the tip at de = di \u223c1.08\u2005\u00c5, due to the short inter\u00adatomic H\u22efH contacts (Table\u00a02c), with a 23.5% contribution to the HS, arises from the H\u22efO/O\u22efH contacts  and H\u22efCl/Cl\u22efH  contacts, with 13.8 and 13.0% contributions to the HS, have nearly symmetrical distributions of points with the edges at de + di = 2.92 (for thin edge) and 3.20\u2005\u00c5 (for thick edge) and de + di = 2.78\u2005\u00c5, respectively, arising from the H\u22efBr/Br\u22efH and H\u22efCl/Cl\u22efH contacts (Table\u00a02f), a 10.2% contribution to the HS, arises from the H\u22efC/C\u22efH contacts , with a 4.0% contribution to the HS, arises from the O\u22efC/C\u22efO contacts , with a 2.6% contribution to the HS, have a nearly arrow-shaped distribution of points arising from the C\u22efC contacts  contacts, with a 1.1% contribution to the HS, have nearly symmetrical distributions of points with the edge at de + di = 3.50\u2005\u00c5.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis \u2013(e), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6-311G basis-set calculations  of the mol\u00adecule was about 6.5402\u2005eV, and the frontier mol\u00adecular orbital energies, i.e.EHOMO and ELUMO, were \u22127.4517 and \u22120.9115\u2005eV, respectively.The optimized structure of the title compound, (I)et al., 2010et al., 2010H-indole-2,3-dione  and di\u00admethyl\u00adformamide  in potassium carbonate  and tetra-n-butyl\u00adammonium bromide . The mixture was stirred at 353\u2005K for 48\u2005h. The reaction was controlled by CCM. The solution was filtered and the DMF was removed under vacuum. The product obtained was separated by chromatography on a column of silica gel with hexa\u00adne\u2013ethyl acetate (4:1 v/v) as eluent. The isolated solid was recrystallized from ethanol to afford red crystals .1,2-Bis(2-chloro\u00adeth\u00adoxy)ethane  was added dropwise to a solution of 5-bromo-1Uiso(H) = 1.2Ueq(C). During the refinement process, the disordered chloro\u00adeth\u00adoxy\u00adethoxyethyl side-chain atoms were refined with a major\u2013minor occupancy ratio of 0.665\u2005(8):0.335\u2005(6).The experimental details, including the crystal data, data collection and refinement, are summarized in Table\u00a0310.1107/S2056989019011617/lh5913sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019011617/lh5913Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019011617/lh5913Isup3.cdxSupporting information file. DOI: 1948316CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two first-row transition metal (Fe and Co) pyridine\u2013sulfate complexes are presented. The compounds demonstrate infinite chains of metal pyridine units connected by bridging sulfate anions. catena-poly[[tetra\u00adkis\u00ad(pyridine-\u03baN)iron(II)]-\u03bc-sulfato-\u03ba2O:O\u2032], [Fe(SO4)(C5H5N)4]n, (1), and catena-poly[[tetra\u00adkis\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba2O:O\u2032-[tetra\u00adkis\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba3O,O\u2032:O\u2032\u2032-[tris\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba2O:O\u2032], [Co3(SO4)3(C5H5N)11]n, (2), are reported. The iron compound (1) displays a polymeric structure, with infinite chains of FeII atoms adopting octa\u00adhedral N4O2 coordination environments that involve four pyridine ligands and two bridging sulfate ligands. The cobalt compound (2) displays a polymeric structure, with infinite chains of CoII atoms. Two of the three Co centers have an octa\u00adhedral N4O2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The third Co center has an octa\u00adhedral N3O3 coordination environment that involves three pyridine ligands, and two bridging sulfate ligands with one sulfate chelating the cobalt atom.The solid-state structures of two metal\u2013pyridine\u2013sulfate compounds, namely  The first reports of a pyridine\u2013sulfato\u2013metal complex were in the late 19th century  and the cobalt\u2013pyridine\u2013sulfate (2) complexes.Against this backdrop, our lab has recently begun to study the solid-state structures of transition-metal pyridine complexes. We have recently reported the structures of nickel, copper and zinc pyridine sulfates, which showed varying coordination geometries consistent with those predicted by crystal field theory (Roy 1), the asymmetric unit consists of two pyridine mol\u00adecules and one half of a sulfate anion coordinated to an iron atom sitting on an inversion center . When grown out, the iron displays an octa\u00adhedral coordination environment . There is a square-planar tetra\u00adpyridine iron unit, with FeN4 planarity enforced by the inversion. The octa\u00adhedral coordination is completed by two sulfate ions that bind trans to each other. The cis N\u2014Fe\u2014N angles have values of 86.44\u2005(4) and 93.56\u2005(4)\u00b0 and the cis O\u2014Fe\u2014N angles have values ranging from 88.12\u2005(4) to 91.88\u2005(4)\u00b0. The pyridine rings are rotated from the FeN4 plane by dihedral angles of 44.03\u2005(1) and 78.20\u2005(1)\u00b0. The 78.20\u2005(1)\u00b0 angle is constrained by two C\u2014H\u22efO inter\u00adactions with the trans sulfates , the asymmetric unit consists of three cobalt atoms, eleven coordinated pyridine mol\u00adecules, and three sulfate anions . There are three crystallographically independent cobalt atoms, with Co1  and Co2  displaying octa\u00adhedral N4O2 coordination environments, and Co3 showing an octa\u00adhedral N3O3 coordination environment .In the pink crystals of  to 93.21\u2005(9)\u00b0, and the O\u2014Co\u2014O angle is 174.62\u2005(9)\u00b0. The four pyridine rings are rotated from the CoN4 plane by dihedral angles of 37.51\u2005(1), 45.21\u2005(1), 56.40\u2005(1) and 56.92\u2005(1)\u00b0. Two of the rings form one C\u2014H\u22efO inter\u00adaction each with the sulfate oxygen atoms  to 93.19\u2005(9)\u00b0, and the O\u2014Co\u2014O angle is 175.16\u2005(9)\u00b0. The four pyridine rings are rotated from the CoN4 plane by dihedral angles of 55.37\u2005(1), 65.88\u2005(1), 67.08\u2005(1) and 68.07\u2005(1)\u00b0. Two of the rings are involved in two C\u2014H\u22efO inter\u00adactions each with the sulfate oxygen atoms  that form a CoO3 plane with a maximum deviation from planarity of 0.029\u2005\u00c5. The meridional CoN3 and CoO3 planes are rotated relative to one another by an angle of 88.93\u2005(1)\u00b0. The cis N\u2014Co\u2014N angles have values of 86.76\u2005(10) and 87.52\u2005(9)\u00b0. The chelating sulfate exhibits an O\u2014Co\u2014O bite angle of 65.36\u2005(7)\u00b0 and another cis O\u2014Co\u2014O angle of 88.63\u2005(8)\u00b0. The three pyridine rings are rotated from the CoN3 plane by dihedral angles of 31.855\u2005(2), 44.111\u2005(3) and 82.863\u2005(4)\u00b0. The 82.863\u2005(4)\u00b0 angle is constrained by two C\u2014H\u22efO inter\u00adactions with sulfate oxygen atoms , the FeII atoms are linked together into infinite chains along the [100] direction through the sulfate ligands via O\u2014S\u2014O bridges . Between each successive tetra\u00adpyridine iron unit are found parallel slipped \u03c0\u2013\u03c0 inter\u00adactions .In compound , the CoII atoms linked together into infinite chains along the [001] direction through the sulfate ligands . No \u03c0\u2013\u03c0 inter\u00adactions are observed in this crystal. There are two C\u2014H\u22efO inter\u00adactions between chains  that connect the chains in three dimensions  and steric effects could play significant roles in determining the observed coordination environments.In a report earlier this year, we presented the structures of the metal\u2013pyridine\u2013sulfates of nickel, copper and zinc. It was of note that these three structures exhibited different coordination geometries, consistent with the crystal field stabilization energies (CFSE) associated with their Approximately 25\u2005mg of each metal sulfate  were dissolved in pyridine  in a 20\u2005mL vial under an atmosphere of di\u00adnitro\u00adgen. In the cobalt case, 0.1\u2005mL of water was also added. The vials were heated to 353\u2005K for 24\u201348\u2005h, after which single crystals suitable for X-ray diffraction studies were isolated.SHELXL) by full-matrix least squares on F2. Hydrogen atoms were placed in calculated positions and then refined with a riding model with C\u2014H bond lengths of 0.95\u2005\u00c5 and with isotropic displacement parameters set to 1.20 Ueq of the parent C atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018007557/sj5556sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989018007557/sj55561sup4.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018007557/sj55562sup5.hklStructure factors: contains datablock(s) 2. DOI: 1844143, 1844142CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title structure has a square-planar coordination sphere around the copper(II) ion. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 hydrogen bonds and very weak \u03c0-stacking inter\u00adactions, forming a three-dimensional supra\u00admolecular architecture. 18H12F6N2O4)]\u00b70.5C6H6O2, the CuII ion has a square-planar coordination geometry, being ligated by two N and two O atoms of the tetra\u00addentate open-chain Schiff base ligand 6,6\u2032-{-bis\u00ad(methanylyl\u00adidene)}bis\u00ad[2-(tri\u00adfluoro\u00admeth\u00adoxy)phenol]. The crystal packing is stabilized by intra\u00admolecular O\u2014H\u22efO and inter\u00admolecular C\u2014H\u22efF, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 hydrogen bonds. In addition, weak \u03c0\u2013\u03c0 inter\u00adactions form a three-dimensional structure. Hirshfeld surface analysis and two-dimensional fingerprint plots were performed and created to analyze the inter\u00admolecular inter\u00adactions present in the crystal, indicating that the most important contributions for the crystal packing are from F\u22efH/H\u22efF (25.7%), H\u22efH (23.5%) and C\u22efH/H\u22efC (12.6%) inter\u00adactions.In the title com\u00adplex, [Cu(C In this study, we describe the crystal structure and Hirshfeld surface analysis of the title com\u00adpound, as determined by X-ray crystallographic analysis.In this study, a salen-type Schiff base has been synthesized from 2-hy\u00addroxy-5-(tri\u00adfluoro\u00admeth\u00adoxy)benzaldehyde with ethyl\u00adenedi\u00adamine by a condensation reaction. The synthesized Schiff base was used as an II ion chelated by a doubly deprotonated tetra\u00addentate Schiff base ligand and a hydrogen-bonded mol\u00adecule of hydro\u00adquinone. The Cu1 ion is coordinated by two imine N atoms (N6 and N7) and two phenoxo O atoms (O2 and O3) of the tetra\u00addentate Schiff base ligand 6,6\u2032-{-bis\u00ad(methanylyl\u00adidene)}bis\u00ad[2-(tri\u00adfluoro\u00admeth\u00adoxy)phenol] (L1). The hydro\u00adquinone mol\u00adecule is located on an inversion centre and is linked to neighbouring com\u00adplex cations via O\u2014H\u22efO hydrogen bonds. The bond lengths Cu1\u2014O2 and Cu1\u2014O3  and Cu1\u2014N1 and Cu1\u2014N2  are close to the values observed for related copper(II) com\u00adplexes reported in the literature  hydrogen bonds (Table\u00a02Cg2\u22efCg3 distance is 3.507\u2005(2)\u2005\u00c5, where Cg2 and Cg3 are the centroids of the Cu1/O2/C5/C6/C8/N2 and Cu1/O3/C17/C12/C11/N1 rings, respectively.The crystal packing of the title com\u00adpound is stabilized by inter\u00admolecular C\u2014H\u22efO, C\u2014H\u22efF and C\u2014H\u22efs Table\u00a02. In addis Table\u00a02. The Cg2CrystalExplorer17 . The blue, white and red colour conventions used for the dnorm-mapped Hirshfeld surfaces recognize the inter\u00adatomic contacts as longer, at van der Waals separations and short inter\u00adatomic contacts, respectively.The Hirshfeld surface analysis  pair with the full fingerprint plot outlined in gray. Fig.\u00a05a) shows the two-dimensional fingerprint plot of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. The most significant contribution to the Hirshfeld surface is from F\u22efH/H\u22efF contacts (25.7%) . Here, H\u22efH interactions are only the second most significant contribution to the total Hirshfeld surface (23.5%). In addition, C\u22efH/H\u22efC and O\u22efH/H\u22efO contacts contribute 12.6 and 11.2% to the Hirshfeld surface, respectively.A fingerprint plot delineated into specific inter\u00adatomic contacts contains information related to specific inter\u00admolecular inter\u00adactions. The blue colour refers to the frequency of occurrence of the (%) Fig.\u00a05b. Here,et al., 20163  and 1.929\u2005(5)\u2005\u00c5] fall within these limits. While the Cu1\u2014O3 and C1\u2014O2 bond length  are within and close to these limits, respectively, the Cu1\u2014O2 bond length is outside these limits, with a shorter value of 1.883\u2005(4)\u2005\u00c5.A search of the Cambridge Structural Database -bis\u00ad(methan\u00adylyl\u00adidene)}bis\u00ad[4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol] (H2L1) was syn\u00adthesized by condensation of 2-hy\u00addroxy-5-(tri\u00ad\u00adfluoro\u00admeth\u00adoxy)\u00adbenzaldehyde (0.0095\u2005mmol) and 1,2-ethane\u00addiamine (0.0095\u2005mmol) in ethanol under reflux for about 18\u2005h. The yellow product was washed with ether and dried at room temperature. 0.0080\u2005mmol\u2005H2L1 was dissolved in 20\u2005ml ethanol and 0.0080\u2005mmol Cu(CH3COO)2\u00b7H2O was dissolved in 20\u2005ml ethanol. The metal solution was added dropwise to the Schiff base solution and the resulting solution refluxed for about 6\u2005h. The product (CuL1) was washed with toluene and crystallized from ethanol at room temperature. 2,2\u2032-{-bis\u00ad(methanylyl\u00adidene)}bis\u00ad[4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol]copper(II) hydro\u00adquinone hemisolvate was obtained even after 0.0040\u2005mmol hydro\u00adquinone was added to 0.0040\u2005mmol CuL1 in 20\u2005ml ethanol and refluxed for about 6\u2005h. A purple crystal suitable for X-ray diffraction analysis was obtained from the reaction   Fig.\u00a06.Uiso(H)\u00a0= 1.2Ueq(C) for methyl\u00adene, C\u2014H = 0.93\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for aromatic, C\u2014H = 0.93\u2005\u00c5 and Uiso(H)\u00a0= 1.2Ueq(C) for methine, and O\u2014H = 0.82\u2005\u00c5 and Uiso(H) = 1.5Ueq(O) for hy\u00addroxy H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019014294/lh5932sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019014294/lh5932Isup2.hklStructure factors: contains datablock(s) I. DOI: 1900670, 1900670CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title Schiff base compound was obtained from a condensation reaction of 4-chloro-3-hy\u00addroxy\u00adbenzaldehyde and 2,4-di\u00adnitro\u00adphenyl\u00adhydrazine. The mol\u00adecule is almost planar with the dihedral angle between the benzene rings being 3.70\u2005(17)\u00b0. 13H9ClN4O5\u00b70.5CH3CN, crystallizes as an aceto\u00adnitrile hemisolvate; the solvent mol\u00adecule being located on a twofold rotation axis. The mol\u00adecule is nearly planar, with a dihedral angle between the two benzene rings of 3.7\u2005(2)\u00b0. The configuration about the C=N bond is E, and there is an intra\u00admolecular N\u2014H\u22efOnitro hydrogen bond present forming an S(6) ring motif. In the crystal, mol\u00adecules are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds, forming layers lying parallel to (10The title Schiff base compound, C These compounds show biological activities including anti\u00adbacterial, anti\u00adfungal, anti\u00adcancer and herbicidal activities  ring motif \u2005\u00c5, where Cg1 and Cg2 are the centroids of rings C1\u2013C6 and C8\u2013C13, respectively, \u03b1 = 3.70\u2005(17)\u00b0, \u03b2 = 27.9\u00b0, \u03b3 = 24.5\u00b0, inter\u00adplanar distances are 3.489\u2005(2) and 3.388\u2005(2)\u2005\u00c5, offset = 1.791\u2005\u00c5; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01. There are no other significant inter\u00admolecular contacts present in the crystal.In the crystal, mol\u00adecules are linked by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds Table\u00a01, formingGAUSSIAN09  level . 18 of these structures involve a halide substituent and 23 involve a hydroxyl substituent. Only one compound involves both a halide and an hydroxyl substituent and closely resembles the title compound, viz. 4-chloro-2-{[hydra\u00adzono]meth\u00adyl}phenol  ring motif. In fact, in all 71 structures (see supporting information) there is an intra\u00admolecular N\u2014H\u22efOnitro hydrogen bond present forming an S(6) ring motif, and in the majority of the compounds the two benzene rings are almost coplanar with the dihedral angle varying between ca 0 to 8\u00b0, with a few exceptions.A search of the Cambridge Structural Database  in ethanol (15\u2005ml) and 2,4-di\u00adnitro\u00adphenyl\u00adhydrazine  in ethanol (15\u2005ml). The reaction mixture was stirred for 5\u2005h under reflux. Orange plate-like crystals of the title compound were obtained by slow evaporation of a solution in ethanol .Uiso(H) = 1.5Ueq and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901900642X/su5496sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S205698901900642X/su5496Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901900642X/su5496sup3.pdfCSD search S1. DOI: Click here for additional data file.10.1107/S205698901900642X/su5496Isup4.cmlSupporting information file. DOI: 1912273CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title chalcone derivative is almost planar, with a dihedral angle of 7.0\u2005(2)\u00b0 between the 3,5-di\u00adchloro-2-hy\u00addroxy\u00adphenyl and 5-methyl\u00adfuran rings. 14H10Cl2O3, is almost planar, with a dihedral angle of 7.0\u2005(2) \u00b0 between the 3,5-di\u00adchloro-2-hy\u00addroxy\u00adphenyl and 5-methyl\u00adfuran rings. There is an intra\u00admolecular O\u2014H\u22efO hydrogen bond present forming an S(6) ring motif. In the crystal, mol\u00adecules are linked by bifurcated C\u2014H/H\u22efO hydrogen bonds, enclosing an R12(6) ring motif, forming a 21 helix propagating along the b-axis direction. The inter\u00admolecular inter\u00adactions were qu\u00adanti\u00adfied using Hirshfeld surface analysis.The title chalcone derivative, C They belong to the flavonoid family, which are basically found in fruits and vegetables -1--3-(5-methyl\u00adfuran-2-yl)prop-2-en-1-one.Chalcone derivatives are an important class of organic compounds comprising two aromatic rings connected via an unsaturated \u03b1,\u03b2 carbonyl system as shown in Fig.\u00a01S(6) ring motif (Table\u00a01anti-periplanar conformation described by the torsion angles C11\u2014C12\u2014C13\u2014Cl19 = \u2212179.1\u2005(3)\u00b0 and C13\u2014C14\u2014C15\u2014Cl18 = \u2212178.6\u2005(4)\u00b0, while methyl group at C2 of the furan ring is in a +anti-periplanar conformation [C5\u2014O1\u2014C2\u2014C6 = 178.3\u2005(4)\u00b0]. The bond lengths and angles in the title compound are similar to those observed for 3-(furan-2-yl)-1-(2-hy\u00addroxy\u00adphen\u00adyl)prop-2-en-1-one \u2005\u00c5, propagating along the b-axis direction  < 1.8\u2005\u00c5 (di is the distance of a point on the Hirshfeld surface to the nearest nucleus inside the surface while de is the distance of the nearest nucleus outside the surface). The H\u22efH contacts, with a contribution of 25.7%, are shown as blue dots spread in the middle region 1.18\u2005\u00c5 < (de + di) < 1.62\u2005\u00c5. The two sharp spikes observed at 1.04\u2005\u00c5 < (de + di) < 1.39\u2005\u00c5 are due to the presence of a pair of O\u22efH contacts making a 15.2% contribution. A pair of C\u22efH contacts are observed as characteristic wings in the region of 1.18\u2005\u00c5 < (de + di) < 1.6\u2005\u00c5 (13.0% contribution). C\u22efC, C\u22efCl and O\u22efC contacts make contributions of 7.9%, 5.2% and 3.8%, respectively.The two-dimensional fingerprint Fig.\u00a06 plots weet al., 2016et al., 2015et al., 2014et al., 2014S(6) ring motifs. The mol\u00adecules are all relatively planar with the dihedral angle between the furan and 2-hy\u00addroxy\u00adphenyl rings varying from ca 8.35\u00b0 in BOGVID, 0.20\u00b0 in KUDMON, and 10.90 and 2.56\u00b0 in the two independent mol\u00adecules of POJBAT. The only exception is POHZUJ, which possesses twofold rotation symmetry and has two [3-(2-fur\u00adyl)prop-2-en-1-one] units meta to each other; here the dihedral angle is ca 19.87\u00b0.A search of the Cambridge Structural Database -2-hy\u00addroxy\u00adethanone (5\u2005mmol) was dissolved in methanol (15\u2005ml) and was stirred with 5\u2005ml of sodium hydroxide solution for 30\u2005min at room temperature. To this mixture, 5-methyl\u00adfuran-2-carbaldehyde (5\u2005mmol) was added over 30\u2005min with stirring. Stirring at room temperature was then continued for 32\u2005h. On completion of the reaction, monitored by TLC, the mixture was quenched in ice\u2013water and acidified with dilute hydro\u00adchloric acid. The separated precipitate of the title compound was filtered off and recrystallized from methanol solution giving colourless block-like crystals.Uiso(H) = 1.2Ueq(C) for aromatic H atoms and C\u2014H = 0.96\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018012173/qm2127sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018012173/qm2127Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018012173/qm2127Isup3.cmlSupporting information file. DOI: 1852049CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "WC)], reverse Watson-Crick [A\u00b7T(wrWC)], Hoogsteen [A\u00b7T(wH)] and reverse Hoogsteen [A\u00b7T(wrH)] \u2013 act as intermediates of the intrapair mutagenic tautomerization of the T nucleobase owing to the novel tautomerisation pathways: A\u00b7T(wWC)\u2194A\u00b7T*(w\u22a5WC); A\u00b7T(wrWC)\u2194A\u00b7\u22a5rWC); A\u00b7T(wH)\u2194A\u00b7T*(w\u22a5H); A\u00b7T(wrH)\u2194A\u00b7\u22a5rH). All of them occur via the transition states as tight ion pairs \u00b7 with quasi-orthogonal geometry, which are stabilized by the participation of the strong (A)N6+H\u00b7\u00b7\u00b7O4\u2212/O2\u2212(T) and (A)N6+H\u00b7\u00b7\u00b7N3\u2212(T) H-bonds. Established tautomerizations proceed through a two-step mechanism of the protons moving in the opposite directions along the intermolecular H-bonds. Initially, proton moves from the N3H imino group of T to the N6H2 amino group of A and then subsequently from the protonated N6+H3 amino group of A to the O4/O2 oxygen atom of T, leading to the products \u2013 A\u00b7T*(w\u22a5WC), A\u00b7\u22a5rWC), A\u00b7T*(w\u22a5H), and A\u00b7\u22a5rH), which are substantially non-planar, conformationally-labile complexes. These mispairs are stabilized by the participation of the (A)N6H/N6H'\u00b7\u00b7\u00b7N3(T) and (T)O2H/O4H\u00b7\u00b7\u00b7N6(A) H-bonds, for which the pyramidalized amino group of A is their donor and acceptor. The Gibbs free energy of activation of these mutagenic tautomerizations lies in the range of 27.8\u201329.8 kcal\u00b7mol\u22121 at T = 298.15 K in the continuum with \u03b5 = 1.In this paper using quantum-mechanical (QM) calculations in combination with Bader's quantum theory of \u201cAtoms in Molecules\u201d (QTAIM) in the continuum with \u03b5 = 1, we have theoretically demonstrated for the first time that revealed recently highly-energetic conformers of the classical A\u00b7T DNA base pairs \u2013 Watson-Crick [A\u00b7T(w Protonated amino group N6+H3 of A for these TSs acts simultaneously as donor and acceptor of the H-bonding and has such spatial orientation, that its N6+H/N6+H\u2032 bond, which is not involved in the H-bonding with T, lies in the plane of the purine ring R, L (10.44), A\u00b7T*(w\u22a5H)R, L (14.69), A\u00b7\u22a5rWC)R, L (9.20) and A\u00b7\u22a5rH)R, L (13.75) kcal\u00b7mol\u22121 complexes (C1 symmetry), which are the products of these mutagenic tautomerizations, are stabilized by the two anti-parallel (T)O4H/O2H\u00b7\u00b7\u00b7\u00a0N6(A) (~5.5) and (A)N6H/N6H\u2032\u00b7\u00b7\u00b7\u00a0N3(T)  H-bonds R, L 0.44, A\u00b7T\u22a5WC)R, L 0.44, A\u00b7Tcys/trans mutual orientation of the N1H and N9H glycosydic bonds of the bases. At the mutagenic tautomeric transformations of the DNA bases some R/L structures transfer into the other L/R structures and vice versa  and \u22121) with low values of the imaginary frequencies provided in the brackets. At this, one-single intermolecular (T)O4H/O2H\u00b7\u00b7\u00b7\u00a0N6(A) H-bond between the O4H/O2H hydroxyl groups of T*/1s. In the case of TS2s, when T hangs over A, the (T)O4H/O2H\u00b7\u00b7\u00b7\u00a0N6(A) H-bond coexists together with attractive van der Waals contacts with significantly increased ellipticity \u2013 N3\u00b7\u00b7\u00b7\u00a0C6 and O2\u00b7\u00b7\u00b7\u00a0C4 in the case of 1s are the most energetically favorable (1.86 and 1.92) in comparison with the TS2s  (Table Two of these tautomerization reactions are controlled by the TSs \u2013 vice versa. In these cases TSs \u2013 \u22121) and \u22121) are characterized by the considerably higher values of imaginary frequencies  and stabilized by two antiparallel (T)O4/O2H\u00b7\u00b7\u00b7\u00a0N6(A) and (A)N6H/N6H\u2032\u00b7\u00b7\u00b7\u00a0N3(T) H-bonds, the first of which is significantly stronger, then the other one  contribute only a part of the electron energy of the monomer interactions R,L\u2194 A\u00b7T*(w\u22a5H)R,L and A\u00b7T*O2(*O2(w\u22a5rH)R,L, tautomerizations indicating the close structural relationship between tautomerization the classical A\u00b7T(WC) and A\u00b7T(H) DNA base pairs, on the one hand, and A\u00b7T(rWC) and A\u00b7T(rH), on the other hand ], reverse Watson-Crick [A\u00b7T(wrWC)], Hoogsteen [A\u00b7T(wH)] and reverse Hoogsteen [A\u00b7T(wrH)], which have been analyzed in details in our previous paper \u2194A\u00b7T*(w\u22a5WC), A\u00b7T(wrWC)\u2194A\u00b7\u22a5rWC), A\u00b7T(wH)\u2194A\u00b7T*(w\u22a5H), A\u00b7T(wrH)\u2194A\u00b7\u22a5rH) \u2013 proceed through the stepwise proton transfer via the TSs as tight A+\u00b7T\u2212 ion pairs, which Gibbs free energy of activation lies in the range of 27.79\u201329.83 kcal\u00b7mol\u22121 at T = 298.15 K, thus creating the substantially non-planar, conformationally-labile complexes \u2013 A\u00b7T*(w\u22a5WC), A\u00b7\u22a5rWC), A\u00b7T*(w\u22a5H) and A\u00b7\u22a5rH). Furthermore, formed complexes involving mutagenic T*/*(w\u22a5WC)\u2194A\u00b7T*(w\u22a5H) and A\u00b7\u22a5rWC)\u2194A\u00b7\u22a5rH).Here we have shed light on the revealed for the first time physico-chemical mechanism of the intrapair mutagenic tautomerization of the T DNA base within the novel highly-energetic conformers of the classical A\u00b7T DNA base pairs \u2013 Watson-Crick [A\u00b7T(wOB, study conception and design, acquisition of data, drafting of manuscript analysis and interpretation of data, performance of calculations, discussion of the obtained data, preparation of the numerical data for Tables, graphical materials for Figures and text of the manuscript. KT, preparation of the numerical data for Tables and graphical materials for Figures, preparation of the text of the manuscript. AD, analysis and preparation of the current literature survey, discussion of the strategy of the current investigation, analysis of the obtained numerical data, discussion of the obtained data, preparation of the numerical data for Tables, graphical materials for Figures and text of the manuscript. DH, study conception, critical revision of manuscript, proposition of the task of the investigation, discussion of the obtained data, preparation of the text of the manuscript. All authors were involved in the proofreading of the final version of the manuscript.The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest."}
{"text": "The proposed approach permits the selection of hydrolases belonging to different families and active towards different substrates. Moreover, the ester group of the substrate used for the selection, at least partly, determined the specificity of the selected enzymes.A high\u2010throughput method (\u2265\u00a010 Enzyme\u2010based organic synthesis constantly needs innovative, diverse and robust biocatalysts  construction of metagenomic libraries, and subsequent functional screening  or by using tributyrin\u2010supplemented agar plates \u2010 and (S)\u2010enantiomers has been used as a substrate in the bond\u2010breaking reaction that generates a growth\u2010promoting energy source and a growth\u2010inhibiting compound  and were omitted from the further analysis. The plasmid DNA from the remaining clones was isolated, and the fragments obtained after restriction digestion were analysed by sequencing to exclude the redundancy. Hence, 30 clones were chosen for further analysis.The metagenomic DNA isolated from different soil samples was partially digested with several restriction endonucleases, and the fragmented DNA was used for the construction of metagenomics libraries. In total, 19 libraries  were tesBioinformatics analysis showed that the selected clones exhibiting esterase activity contained ORFs with medium 31%) to high (100%) sequence identity to proteins found in the databases (Table\u00a0% to highN\u2010acyltransferase superfamily (SSF55729) (1 hit) and one DUF998 family protein  revealed that the enzyme 1315H may be a transmembrane protein without any predictable function.The phylogenetic analysis of the selected hydrolases showed that the enzymes represent very diverse groups of proteins Fig.\u00a0. Most ofein Fig.\u00a0. All ideein Fig.\u00a0 and wereein Fig.\u00a0. Two estThus, a functional selection of metagenomic libraries revealed enzymes from very diverse protein families, including several hits that, based on bioinformatics, could not be annotated as hydrolases active towards esters.E.\u00a0coli strain BL21 (DE3) was transformed with the recombinant plasmids and used for the expression of the recombinant proteins. In total, 27 recombinant proteins were purified by Ni\u2010NTA chromatography  esters: acetate, butyrate, valerate, decanoate, palmitate and stearate. All hydrolases were active towards the short\u2010chain esters pNP\u2010acetate and pNP\u2010butyrate, most of them used pNP\u2010valerate, but only a few of them hydrolyzed pNP\u2010decanoate  exhibited a very weak activity against this ester. Six enzymes MO101T, SVG3, GRU1, PLA1, 3T and 33T3 exhibited a strong preference for pNP\u2010acetate as the substrate  forming the halos indicative of the hydrolysis were screened. Tb7_1T (MH423281) encoded the group \u03b2\u2010lactamases protein, and Tb10_7T (MH423280) was most similar to ABhydrolases. Neither of the two clones was capable of growing on compound 1 or 2 as a uridine source. Tb7\u20101T was not further analysed because of its insolubility. The purified protein Tb10_7 was not only active towards pNP esters  and two  esterases preferred S\u20101\u2010phenylethyl hexanoate and S\u20101\u2010phenylethyl benzoate respectively. No esterase was enantioselective towards R\u20101\u2010phenylethyl hexanoate or benzoate. Furthermore, to analyse the promiscuity of the selected esterases, several amides were tested as substrates. Consequently, three esterases were found to hydrolyze acetanilide, and 18 were active towards nitrocefin  and the uridine auxotroph mutant \u0394pyrFEC of E.\u00a0coli allows for a functional selection of novel ester hydrolases from metagenomic libraries. Evidently, the selection method presented here is highly complementary to traditional approaches and is applicable for allowing the discovery of novel esterases with different structural and catalytic characteristics. Compared with the known methods, the proposed selection system has many advantages: (i) it is a HTS method that allows for a rapid (1\u20134\u00a0days) processing of large (meta)genome libraries  with low number of false positives, ii) depending on the selection media used, it permits the functional selection of hydrolases belonging to different protein families, (iii) it is flexible since, by using different substrates, for example, esters of the fatty acids of different lengths or bulky carboxylic acids, it allows the identification of enzymes with desired properties, (iv) it would be suitable for the selection of regioselective esterases if the appropriate substrate was used, (v) it allows the identification of novel proteins that previously have not been known as the ester\u2010hydrolysing enzymes or cannot be screened using, for example, a tributyrin method, (vi) the appropriate uridine auxotrophs are available for a wide spectra of microbial hosts, including extremophiles and yeasts or can be easily constructed, for example, using 5\u2010fluororotic acid selection  Assay Reagent and HisPur\u2122 Ni\u2010NTA spin column were purchased from Thermo Fisher Scientific, Rockford, IL. pET21a Vector was purchased from Novagen . Nutrient medium were purchased Roth, Germany. pNP\u2010acyl esters, tributyrin, \u03b2\u2010d\u2010glucose pentaacetate, \u03b2\u2010d\u2010galactose pentaacetate, and uridine were purchased from Sigma\u2010Aldrich. \u2018ZR Soil Microbe DNA MidiPrep\u2122\u2019 was purchased from Zymo Research, Freiburg, Germany. Nitrocefin was purchased from Oxoid, UK. 3\u2032\u2010O\u2010benzoyl\u20102\u2032\u2010deoxyuridine were purchased from Carbosynth, UK. 3\u2032\u2010O\u2010acetyl\u20102\u2032\u2010deoxyuridine, 3\u2032\u2010O\u2010acetyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deoxycytidine, 3\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deocytidine, and 5\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deocytidine were purchased from Jena Bioscience, Jena, Germany.Restriction endonucleases, HindIII, BamHI, PstI, Phusion DNA polymerase, aLICator\u2122 LIC Cloning and Expression System Kit 3, PageRulerO\u2010acetyluridine and 2\u2032,3\u2032,5\u2032\u2010hexanoyluridine were prepared by adapting and modifying methods reported in the literature and evaporated under reduced pressure. The residue was purified by column chromatography  to afford 2\u2032,3\u2032,5\u2032\u2010O\u2010triacetyluridine (1.45\u00a0g (95%) as a white solid. UV (CH3OH) \u03bbmax 257\u00a0nm. MS (ESI+): m/z 371.10 [M+H]+, 369.10 [M\u2212H]\u2212. 1H\u2010NMR (DMSO\u2010d6): \u03b4\u00a0=\u00a02.11 , 2.13 , 2.15 , 4.36 , 5.35 , 5.81 , 6.05 , 7.41 , 9.69 . 13C\u2010NMR (DMSO\u2010d6): \u03b4\u00a0=\u00a020.41, 20.51, 20.77, 63.18, 70.20, 72.72, 79.92, 87.46, 103.44, 139.36, 150.35, 163.00, 168.75, 169.67, 170.18. The NMR spectra were consistent with reported previously  and sodium acetate  was heated for 20\u00a0min at 90\u00b0C. Then uridine  was added to the hot solution and stirred for 1\u00a0h. After the reaction was completed (TLC), the mixture was quenched with sodium bicarbonate and extracted with chloroform. The organic phase was dried  and N,N\u2010dimethylpyridin\u20104\u2010amine  were added. The reaction mixture was stirred for 3\u00a0h at room temperature. After the reaction was completed (TLC), the formed precipitate of N,N\u2032\u2010dicyclohexylurea was filtered, and the filtrate was concentrated under reduced pressure. The residue was treated with acetonitrile and the mixture of mono\u2010, di\u2010 and tri\u2010O\u2010hexanoyluridines precipitated as a white solid. The precipitate was filtered, dried to afford 0.5\u00a0g of hexanoyluridines. HPLC\u2010MS analysis indicated that the mixture consisted of 7% of mono\u2010O\u2010hexanoyluridine, 21% of di\u2010O\u2010hexanoyluridine and 72% of tri\u2010O\u2010hexanoyluridine. UV (CH3OH) \u03bbmax 256\u00a0nm. MS (ESI+): m/z 341.00 [M\u2212H]\u2212, 439.05 [M\u2212H]\u2212, 537.10 [M\u2212H].To a stirred mixture of uridine  and triethylamine  in 1,4\u2010dioxane (10\u00a0ml) hexanoic acid , R)\u20101\u2010phenylethanol or (S)\u20101\u2010phenylethanol  and DMAP  were dissolved in acetic anhydride  and heated for 30\u00a0min at 55\u00b0C. The reaction mixture was monitored by thin\u2010layer chromatography . After the reaction was completed, the formed acetic acid was evaporated under reduced pressure. The residue was purified by column chromatography . After removal of solvents in vacuum, the desired products were obtained as colourless oils.Enantiomerically pure (Rf\u00a0=\u00a00.68 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a01.57 , 2.10 ; 5.92 , 7.27\u20137.44 . 13C NMR (CDCl3): \u03b4\u00a0=\u00a021.37, 22.22, 72.32, 126.11, 127.88, 128.51, 141.69, 170.34.Yield 261\u00a0mg (97%), colourless oil, Rf\u00a0=\u00a00.69 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a01.57 , 2.10 ; 5.91 , 7.27\u20137.44 . 13C NMR (CDCl3): \u03b4\u00a0 = \u00a021.37, 22.22, 72.32, 126.10, 127.88, 128.51, 141.69, 170.35.Yield 219\u00a0mg (81%), colourless oil, (R)\u20101\u2010phenylethyl acetate reported in literature \u20101\u2010phenylethanol or (S)\u20101\u2010phenylethanol  and triethylamine  were dissolved in dichloromethane (2\u00a0ml). After the solution was cooled to an ice bath, benzoyl chloride  was added, and the reaction mixture was stirred for 1\u00a0h at ambient temperature. After the reaction was completed (TLC), the solvent was evaporated under reduced pressure. The residue was purified by column chromatography . The solvents were removed in vacuum, and the desired products were obtained as colourless oils.Enantiomerically pure (Rf\u00a0=\u00a00.75 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a01.71 , 6.17 , 7.31\u20137.52 , 8.10\u20138.16 . 13C NMR (CDCl3): \u03b4\u00a0=\u00a022.45, 72.94, 126.07, 127.92, 128.36, 128.58, 129.67, 130.54, 132.95, 141.81,165.84.Yield 184\u00a0mg (50%), colourless oil, Rf\u00a0=\u00a00.76 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a01.71 , 6.17 , 7.31\u20137.53 , 8.09\u20138.15 . 13C NMR (CDCl3): \u03b4\u00a0=\u00a022.44, 72.93, 126.07, 127.92, 128.36, 128.57, 129.67, 130.55, 132.95, 141.81,165.84.Yield 360\u00a0mg (97%), colourless oil, 1H NMR spectrum was consistent with spectrum of 1\u2010phenylethyl benzoate racemic ester reported previously \u20101\u2010phenylethanol or (S)\u20101\u2010phenylethanol , hexanoic acid , DCC  and DMAP  were dissolved in 10\u00a0ml of dichloromethane and stirred for 3\u00a0h at ambient temperature. After the reaction was completed (TLC), the formed precipitate was filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography . After removal of solvents in vacuum, the desired products were obtained as colourless oils.Enantiomerically pure (Rf\u00a0=\u00a00.82 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a00.91 , 1.25\u20131.42 , 1.56 , 1.61\u20131.70 , 2.33\u20132.38 , 5.93 , 7.28\u20137.41 . 13C\u2010NMR (CDCl3): \u03b4\u00a0=\u00a013.91, 22.28, 22.32, 24.67, 31.27, 34.60, 72.01, 126.07, 127.79, 128.47, 141.88, 173.11.Yield 288\u00a0mg (80%), colourless oil, Rf\u00a0=\u00a00.82 (CHCl3).1H NMR (CDCl3): \u03b4\u00a0=\u00a00.91 , 1.27\u20131.40 , 1.56 , 1.61\u20131.70 , 2.32\u20132.38 , 5.93 , 7.28\u20137.42 . 13C\u2010NMR (CDCl3): \u03b4\u00a0 = \u00a013.91, 22.28, 22.32, 24.67, 31.27, 34.60, 72.01, 126.07, 127.79, 128.47, 141.88, 173.11.Yield 272\u00a0mg (75%), colourless oil, et\u00a0al., NMR spectra were consistent with spectra of 1\u2010phenylethyl hexanoate racemic ester reported in literature  supplemented with the appropriate antibiotics , 1\u00a0mM IPTG and 1\u00a0mM X\u2010gal. Ten to twenty of individual white colonies\u2010forming clones were randomly chosen for plasmid DNA isolation by Thermo Scientific\u2122 GeneJET Plasmid Miniprep Kit (Thermo Fisher Scientific) and analysis of the length of the insert. The remaining undiluted mixture of the cells was spread on LB agar ) supplemented with 40\u00a0\u03bcg\u00a0ml\u22121 kanamycin and 100\u00a0\u03bcg\u00a0ml\u22121 ampicillin. After cultivation for 14\u201316\u00a0h, a biomass was scraped from agar, and total plasmid DNA was isolated by Thermo Scientific\u2122 GeneJET Plasmid Midiprep Kit (Thermo Fisher Scientific). The obtained DNA mixture (a metagenomics library) was stored at \u201320\u00b0C and used for a further transformation of the E.\u00a0coli DH10B \u0394pyrFEC::Km cells.Metagenomic libraries were constructed from soil and sediment samples using a pUC19 vector . For DNA\u22121 Na2HPO4 15\u00a0g\u00a0l\u22121 KH2PO4, 5\u00a0g\u00a0l\u22121 NH4Cl, 2.5\u00a0g\u00a0l\u22121 NaCl, 2% (w/v) glucose, 0.2% Casamino acid, 1\u00a0mM IPTG) containing 100\u00a0\u03bcg\u00a0ml\u22121 ampicillin and 40\u00a0\u03bcg\u00a0ml\u22121 kanamycin, 0.02\u00a0mg\u00a0ml\u22121 2\u2032,3\u2032,5\u2032\u2010O\u2010acetyluridine (1) or 2\u2032,3\u2032,5\u2032\u2010O\u2010hexanoyluridine (2) as the sole source of uridine, allowing only the growth of recombinants that can complement the uridine auxotrophy of the E.\u00a0coli DH10B \u0394pyrFEC::Km strain by hydrolysing the uridine esters.The clones exhibiting acetylesterase activity were identified on a MD medium . For further analysis the ORFs encoding putative hydrolases were chosen. When homology search did not predict a hydrolase, the deletion analysis to obtain the truncated variants of the plasmid and the functional reselection on the appropriate substrate was carried out. To confirm that the hits encoded the enzymes with an esterolytic activity, the selected genes were PCR\u2010amplified, and the resulting fragments were ligated into pET21a or pLATE31 expression vectors. Phylogenetic analysis was conducted using the Maximum Likelihood Tree routine of mega 7 software. and using the following sequencing primers: M13F\u2010pUC (5\u2032\u2010GTTTTCCCAGTCACGAC\u20103\u2032), M13R\u2010pUC (5\u2032\u2010CAGGAAACAGCTATGAC\u20103\u2032), T7 Promoter (5\u2032\u2010 TAATACGACTCACTATAGGG\u20103\u2032), T7 terminator (5\u2032\u2010TAATACGACTCACTATAGGG\u20103\u2032) or LIC Reverse Sequencing primer, 24\u2010mer (5\u2032\u2010GAGCGGATAACAATTTCACACAGG\u20103\u2032). Some individual clones contained more than one ORF in each DNA fragment. ORFs were analysed by using the Unipro UGENE program, and homology search was conducted using the Blast server (E.\u00a0coli cells transformed with recombinant plasmids were cultivated on LB agar supplemented with 100\u00a0\u03bcg\u00a0ml ampicillin.The genes of the selected enzymes were amplified with Phusion DNA polymerase using primers . MetagenE.\u00a0coli strain BL21 (DE3). E.\u00a0coli cells were grown in 20\u00a0ml BHI (Brain\u2010Heart\u2010Infusion Broth) medium containing ampicillin (100\u00a0mg\u00a0ml) at 37\u00b0C with aeration. Protein expression was induced by adding 0.5\u00a0\u03bcM IPTG at 0.6\u20131 OD600, and cells were grown for a further 4\u201318\u00a0h at 30\u00b0C. Cells expressing 12T and 3T were grown at 23\u00b0C after induction to increase protein solubility. Wet cell biomass from 20\u00a0ml culture broth were suspended in 5\u201310\u00a0ml of buffer A  and disrupted by sonication for 2.5\u00a0min. A lysate was cleared by centrifugation at 15\u00a0000\u00a0\u00d7\u00a0g for 4\u00a0min. Cleared lysate was applied to 0.2\u00a0ml HisPur\u2122 Ni\u2010NTA spin column (equilibrated with the buffer A). The column was washed with the buffer A, and the proteins were eluted with buffer A containing 300\u00a0mM imidazole. The active fractions were combined and dialyzed against the buffer B , at 25\u00b0C. All the purification procedures were performed at room temperature.The recombinant proteins were overexpressed in The concentration of protein was determined using Pierce\u2122 Coomassie Plus (Bradford) Assay Reagent by Standard Microplate Protocol. Proteins were analysed by sodium dodecyl sulfate polyacrylamide gel electrophoresis  according to Laemmli. Gels were developed in Coomassie Brilliant Blue G\u2010250 dye, scanned in 16 bit format and quantified by GelAnalyser program. Each sample contained 2\u00a0\u03bcg of total protein. Quantities of impurities and target proteins were estimated using calibration curve generated from known amounts of BSA: 0.125, 0.25 and 0.5\u00a0\u03bcg per band. The purity of analysed protein was calculated as the ratio between quantity of target protein and quantity of all proteins.et\u00a0al., et\u00a0al., \u03b5\u00a0=\u00a012.3\u00a0M\u22121\u00a0cm\u22121) per minute. Enzyme activity was tested against different pNP\u2010acyl esters .The activity of esterase were assayed by incubating the enzyme with 1\u00a0mM pNP\u2010substrate (from 10\u00a0mM stock in DMSO) in 50\u00a0mM potassium phosphate, pH 7.5, buffer at a 37\u00b0C for 10\u00a0min in 100\u00a0\u03bcl reaction volume. 5\u2013300\u00a0ng of protein, depending on the enzyme specificity for the substrate, were present into the reaction mixture. The absorbtion of the reaction mixture at 405\u00a0nm was measured against enzyme\u2010free blank to compensate for the substrate auto\u2010hydrolysis , pentaacetylglucose or pentaacetylgalactose (from 100\u00a0mM stock in acetone), 3\u2032\u2010O\u2010acetyl\u20102\u2032\u2010deoxyuridine, 3\u2032\u2010O\u2010acetyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deoxycytidine, 3\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deocytidine, and 5\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deocytidine (100\u00a0mM stock in DMSO). The total reaction mix volume was 100\u00a0\u03bcl. Reaction mixture was incubated at room temperature up to 5\u00a0h. A change of colour from red to yellow indicated the hydrolysis of esters , 1\u00a0\u03bcl enzyme (0.1\u20134.6\u00a0\u03bcg/reaction) and 10\u00a0mM substrate: d\u2010glucose pentaacetate, \u03b2\u2010d\u2010 galactose pentaacetate (from 100\u00a0mM stock in acetone), 3\u2032\u2010O\u2010benzoyl\u20102\u2032deoxyuridine (10\u00a0mg\u00a0ml\u22121 stock in DMF), 3\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032deocytidine and 5\u2032\u2010O\u2010levulinyl\u2010N4\u2010benzoyl\u20102\u2032\u2010deocytidine (from 100\u00a0mM stock in DMSO). The total reaction mix volume was 20\u00a0\u03bcl. Reaction mixture was incubated at 30\u00b0C temperature up to 3\u00a0h. Thin\u2010layer chromatography (TLC) was conducted on the Merck silica gel 60F254 plates, using the dichloromethane and methanol (9:1) mixture of solvents. \u03b2\u2010d\u2010glucose pentaacetate and \u03b2\u2010d\u2010 galactose pentaacetate were visualized by anisaldehide stain . The plate was developed by heating on a hot plate. Synthetic nucleosides were exposing to UV light.A hydrolytic activity was assayed in reaction mixture containing 45\u00a0mM potassium phosphate buffer, pH 7.5, 1\u00a0\u03bcl enzyme (0.1\u20134.6\u00a0\u03bcg/reaction) and 10\u00a0mM substrate: \u03b2\u2010There are no conflicts to declare.Table\u00a0S1. Metagenomic libraries used in this work.Table\u00a0S2. Primers used for amplification of genes of selected hydrolases.Table\u00a0S3. Predicted signal peptide sequences identified in the selected esterases by bioinformatics.Fig.\u00a0S1. Selected clones on MD medium, MD+ compound 1, MD+compound 2 and MD+uridine after 2\u00a0days of incubation at 37\u00b0C.Fig.\u00a0S2. The alignment was performed by ClustalW software.Fig.\u00a0S3. Analysis of the purified esterases by SDS\u2010PAGE.Fig.\u00a0S4. LB medium with tributyrin plates after 2\u00a0days of incubation at 37\u00b0C.Scheme\u00a0S1. Synthesis of optically active esters (3\u20138).Click here for additional data file."}
{"text": "I ion is coordinated by two heterocyclic N atoms from two ligands in a linear configuration, forming a discrete coordination complex. There is an O\u2014H\u22efO hydrogen bond between 2-tza\u2212 and 2tzaH of adjacent complexes. The hydrogen atom is shared between the two oxygen atoms.The Ag 4H2NO2S)(C4H3NO2S)] or [Ag(2-Htza)(2-tza)] is reported . The AgI ion is coordinated by two heterocyclic N atoms from two ligands in a linear configuration, forming a discrete coordination complex. There is an O\u2014H\u22efO hydrogen bond between 2-tza\u2212 and 2tzaH of adjacent complexes. The hydrogen atom is shared between the two oxygen atoms. This inter\u00adaction produces a hydrogen-bonded tape parallel to the [110] direction, which is augmented through inter\u00admolecular C\u2014H\u22efO hydrogen-bonding inter\u00adactions between the bound thia\u00adzole groups. There is a further rather long Ag\u22efO inter\u00adaction  that assembles these tapes into columns, between which there are C\u2014H\u22ef\u03c0 inter\u00adactions, leading to the formation of a three-dimensional supra\u00admolecular architecture.The linear two-coordinate silver (I) complex [Ag(C The whole mol\u00adecular structure can be generated by an inversion centre; the AgI atom is located at the 2a Wyckoff position (I centre shows a linear coordin\u00adation with two 2-tza ligands coordinating through the heterocyclic N atoms with an Ag\u2014N bond length of 2.1463\u2005(14)\u2005\u00c5. Statistically one of these ligands has an appended carb\u00adoxy\u00adlic acid and the other a carboxyl\u00adate. A rather long Ag\u22efO2 inter\u00adaction is also observed with the distance of 2.8401\u2005(13)\u2005\u00c5. This is significantly larger than the mean value [2.54\u2005(11)\u2005\u00c5] of the Ag\u22efO=C distances in the Cambridge Database (2-tza\u2212). The carboxyl\u00adate is located close to a second symmetry-equivalent carboxyl\u00adate generated by the symmetry operation 1\u00a0\u2212\u00a0x, \u2212y, 1\u00a0\u2212\u00a0z. Statistically, one of these two groups is protonated. The close approach facilitates the formation of a linear hydrogen bond between them  of an adjacent discrete mol\u00adecule (Table\u00a01a). This tape is inclined at an angle of 55.278\u2005(19)\u00b0 with the (001) plane. Each tape is connected through an Ag\u22efO1 inter\u00adaction [d(Ag\u22efO1) = 2.9606\u2005(14)\u2005\u00c5], generating columns of complex mol\u00adecules along the [100] direction . These columns are further linked via C\u2014H\u22ef\u03c0 inter\u00adactions between the thia\u00adzole rings  and 2-Htza  were dissolved in 5.0\u2005mL of deionized water in a small vial (ca 16\u2005mm in diameter). The vial was left undisturbed at ambient temperature for three days during which colourless block-shaped crystals of the title compound crystallized and were isolated for X-ray data collection.AgNOUiso(H) = 1.5Ueq(O). The C-bound H atoms were refined isotropically, with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019000124/nk2248sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019000124/nk2248Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000124/nk2248Isup3.molSupporting information file. DOI: 1888609CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Polynitrile anions are known for their ability to combine with transition metals and co-ligands to form ternary systems. Here we report on the crystal structure of tris\u00ad(2\u20132\u2032-bi\u00adpyridine)\u00adcobalt(II) bis\u00ad. 10H8N2)3](C9H5N4O)2, the tris\u00ad\u00adcobalt(II) dication lies across a twofold rotation axes in the space group C2/c. The N atoms of the three bi\u00adpyridine ligands form a distorted octa\u00adhedron around the cobalt ion. All the N atoms of the polynitrile 1,1,3,3-tetra\u00adcyano-2-eth\u00adoxy\u00adpropenide anions participate in C\u2014H\u22efN hydrogen bonds ensuring crystal cohesion and forming a three-dimensional structure. The structure is further stabilized by C\u2014H\u22ef\u03c0(cation) and anion\u22ef\u03c0(cation) inter\u00adactions.In the title compound, [Co(C The cobalt ion is ligated by the N atoms of the 2,2\u2032-bi\u00adpyridine ligands forming a slightly distorted octa\u00adhedral coordination sphere; the Co1\u2014N bond lengths vary from 2.122\u2005(3) to 2.148\u2005(3)\u2005\u00c5. In the bpy  unit, the pyridine rings are inclined to each other by 10.40\u2005(16)\u00b0, while in the other bpy unit (involving atom N3) bis\u00adected by a twofold rotation axis the pyridine rings are coplanar. The observed distortion of the CoIIcoordination sphere is probably the consequence of the hydrogen bonding between the [Co(C10H8N2)3]2+ cation and the flexible tcnoet\u2212 anion (see Supra\u00admolecular features).The asymmetric unit of the title compound (I)\u2212 anion, the six central C\u2014C distances within the anion range from 1.382\u2005(4) to 1.429\u2005(5)\u2005\u00c5 while the C\u2261N distances vary from 1.138\u2005(4) to 1.151\u2005(4)\u2005\u00c5 \u00b0.In the tcnoet\u00c5 Table\u00a01. As obseThe crystal packing of (I)\u2212 anions linked by eight C\u2014H\u22efN hydrogen bonds as shown in Fig.\u00a03\u2212 anions are doubly connected to the cationic units  via C8\u2014H8\u22efN7iii; C11i\u2014H11i\u22efN6iii and their symmetric C8i\u2014H8i\u22efN7iv; C11\u2014H11\u22efN6iv. Four tcnoet\u2212 anions are linked to atoms N4 and N5  via C7\u2014H7\u22efN4iv, C2\u2014H2\u22efN5v, C7i\u2014H7i\u22efN4ii and C2i\u2014H2i\u22efN5vii. One of the anions plays the role of a donor in the structural linkage. Indeed, one tcnoet\u2212 anion is linked by an N\u22efH\u2014C inter\u00adaction to the same [Co(C10H8N2)3]2+ unit (via N6\u22efH11iii\u2014C11iii and N7\u22efC8ii\u2014H8ii) and to two other cationic units by N4\u22efH7i\u2014C7i and N5\u22efH2iv\u2014C2iv inter\u00adactions. This environment where the negative charge is delocalized over the central propenide unit as well as into the cyano groups is illustrated in Fig.\u00a04The cations are surrounded by six tcnoetB\u22efCg1vi; see Table\u00a02Cg2; see Table\u00a02The crystal structure of (I)et al., 2016\u2212 anion associated with an organic cation to form a salt-like compound  the water mol\u00adecule links the tcnoet\u2212 anion and the iron aggregate via O\u2014H\u22efN hydrogen bonds, forming chains, whereas in (I)ca 28.1\u00b0 compared to 31.7\u2005(3)\u00b0 in (I)A search in the Cambridge Structural Database , 2,2-bi\u00adpyridine  and K(tcnoet)  in water\u2013ethanol . This mixture was sealed in a Teflon-lined autoclave and held at 423\u2005K for three days, and then cooled to ambient temperature at a rate of 10\u2005K\u2005h\u22121 (yield: 54%). Colourless plate-like crystals of the title compound were selected directly from the synthesized product.The title compound was synthesized solvothermally under autogenous pressure from a mixture of CoNOUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018018261/su5465sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018018261/su5465Isup2.hklStructure factors: contains datablock(s) I. DOI: 1887084CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "GBA) is a lysosomal \u03b2\u2010glucosidase\u2010degrading glucosylceramide. Its deficiency causes Gaucher disease (GD), a common lysosomal storage disorder. Carrying a genetic abnormality in GBA constitutes at present the largest genetic risk factor for Parkinson's disease (PD). Conduritol B epoxide (CBE), a mechanism\u2010based irreversible inhibitor of GBA, is used to generate cell and animal models for investigations on GD and PD. However, CBE may have additional glycosidase targets besides GBA. Here, we present the first in\u00a0vivo target engagement study for CBE, employing a suite of activity\u2010based probes to visualize catalytic pocket occupancy of candidate off\u2010target glycosidases. Only at significantly higher CBE concentrations, nonlysosomal glucosylceramidase (GBA2) and lysosomal \u03b1\u2010glucosidase were identified as major off\u2010targets in cells and zebrafish larvae. A tight, but acceptable window for selective inhibition of GBA in the brain of mice was observed. On the other hand, cyclophellitol, a closer glucose mimic, was found to inactivate with equal affinity GBA and GBA2 and therefore is not suitable to generate genuine GD\u2010like models.Glucocerebrosidase (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/45.html), nonlysosomal \u03b2\u2010glucocerebrosidase (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/45.html); cytosolic \u03b2\u2010glucosidase (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/21.html); \u03b1\u2010glucosidases (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/20.html); \u03b2\u2010glucuronidase (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/31.html).Glucocerebrosidase ( In\u00a0vivo target engagement of mechanism\u2010based glucocerebrosidase (GBA) inhibitors\u2014conduritol B epoxide (CBE) and cyclophellitol (CP)\u2014were examined in cultured cells, zebrafish larvae and mice by competitive activity\u2010based protein profiling (ABPP). This method utilizes suicide fluorescent enzyme reporter molecules to assess active site occupancy of target glycosidases by inhibitors. The in\u00a0vivo targets of CBE and CP and their selectivity towards GBA were revealed. ABPactivity\u2010based probeABPPactivity\u2010based protein profilingCBEconduritol B epoxideCPcyclophellitoldpfdays postfertilizationGBAglucocerebrosidaseGDGaucher diseaseGlcSphglucosylsphingosinePDParkinson's diseasehttp://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/45.html) is a retaining \u03b2\u2010glucosidase that degrades the glycosphingolipid, glucosylceramide. Inherited deficiencyof GBA is the cause of autosomal recessive Gaucher disease (GD) The lysosomal enzyme glucocerebrosidase  Fig.\u00a0A 7, 8, 9m to 100\u00a0mm CBE for 2\u00a0h up to 60\u00a0days \u22121 body weight during 2\u00a0h up to 36\u00a0days in\u00a0vitro inhibition of retaining \u03b1\u2010glucosidases (http://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/20.html) in\u00a0vitroin\u00a0situhttp://www.chem.qmul.ac.uk/iubmb/enzyme/EC3/2/1/45.html), and inhibition of the lysosomal \u03b2\u2010glucuronidase  in mice in\u00a0vivo towards GBA2 and other glycosidases is unknown.A major advantage of CBE's pharmacological use in cultured cells and mice is its tunability: the extent of GBA inactivation can be adjusted by variation in the inhibitor concentration and/or exposure time in\u00a0vivo selectivity of CBE and CP in cells and animal models. We envisioned that besides the traditional enzymatic assays employing fluorogenic substrates, activity\u2010based probes (ABPs) could be superior tools for this study. Unlike enzymatic substrate assays, which do not easily distinguish similar enzymatic activities such as GBA vs GBA2, ABPs would allow direct and unambiguous visualization of respective target glycosidases that are not occupied/inactivated by CBE or CP at the active site pocket. Cravatt and coworkers and van der Stelt and colleagues earlier used ABPs directed towards proteases and lipases in a competitive activity\u2010based protein profiling (ABPP) approach to identify in\u00a0vivo target engagement of small compounds 3\u20136). Here, we report a detailed in\u00a0vivo target engagement study for CBE and CP. Through parallel application of both the competitive ABPP method and enzymatic assay in lysates of cultured cells, zebrafish (Danio rerio) larvae, and brains of mice treated in\u00a0vivo with a relevant range of concentrations of CBE or CP, we have systematically assessed their in\u00a0vivo off\u2010targets and selectivity windows for GBA.Our aim was to systematically study the 3 and 4) 1 and CP 2 with a competitive ABPP method by which the irreversible occupancy of the catalytic nucleophile of GBA by the inhibitors during preincubation is assessed. As a validation, competition of ABP labelling by CBE and CP was compared to the loss of GBA activity measured using 3.75\u00a0mm 4\u2010methylumbelliferyl\u2010\u03b2\u2010glucoside as substrate 4c was quantified by SDS/PAGE and fluorescence scanning. IC50 values (concentrations of inhibitor yielding a 50% reduction of ABP 4c labelling) were determined and found to be 26.6\u00a0\u03bcm at 30\u00a0min CBE preincubation, and 2.30\u00a0\u03bcm at 180\u00a0min preincubation  and GBA2 (110\u00a0kDa) following SDS/PAGE analysis. First, we studied HEK293T cells expressing GBA2. Cells were exposed for 24\u00a0h to different concentrations of CBE (0.1\u00a0\u03bcm\u201310\u00a0mm) after which the residual amount of GBA, GBA2, GAA, GANAB and GUSB in cell lysates that can still be labelled with the appropriate ABPs , GBA2 (IC50\u00a0=\u00a0315\u00a0\u03bcm), GAA (IC50\u00a0=\u00a0249\u00a0\u03bcm), GANAB (IC50\u00a0=\u00a02900\u00a0\u03bcm) and GUSB (IC50\u00a0= 857\u00a0\u03bcm). , GBA2 (IC50 =272\u00a0\u03bcm), GAA (IC50 = 309\u00a0\u03bcm), GANAB (IC50 = 1580\u00a0\u03bcm) and GUSB (IC50 = 607\u00a0\u03bcm)  for their possible inactivation by CBE. At the highest concentration of CBE (10\u00a0mm) tested, no significant loss of activity was observed for any of these additional lysosomal enzymes  and lysosomal \u03b2\u2010glucuronidase GUSB. For each of these enzymes, ABPs have been designed, and enzymatic activity assays with fluorogenic substrates established and GBA2 10\u00a0kDa fotive GBA 8\u201366\u00a0kDa m\u2013100\u00a0mm) in the egg water for 5\u00a0days. The larvae were collected, lysed and analysed by the competitive ABPP method. Exposure to 100\u00a0mm CBE was found to reduce ABP labelling of all five glycosidases , GBA2 (IC50 = 890\u00a0\u03bcm), GAA (IC50 = 9550\u00a0\u03bcm), GANAB (IC50 = 4700\u00a0\u03bcm) and GUSB (IC50 = 6470\u00a0\u03bcm)  except for \u03b2\u2010galactosidase (IC50 = 11.2\u00a0mm) and \u03b1\u2010galactosidase (IC50 = 22.5\u00a0mm)  to CBE  Table\u00a0. Thus, im) Table\u00a0, Fig.\u00a07.in\u00a0vivo targets of CBE in brain of mice treated daily from day 8 to either day 25 with 37.5\u00a0mg CBE\u00b7kg\u22121 body weight or to day 14 with 100\u00a0mg CBE\u00b7kg\u22121 body weight \u22121 body weight  for 24\u00a0h. IC50 values of CP for blocking ABP labelling were 0.063\u00a0\u03bcm for GBA and 0.154\u00a0\u03bcm for GBA2   Fig.\u00a0A. As detm) also comparably competed GBA and GBA2 labelling, but not that of GUSB, GAA and GANAB  4m ABP 4c. We therefore generated HEK293T cells overexpressing GBA3 to study the inhibitor sensitivity of the enzyme. In these cells we could measure the in\u00a0vivo interaction of CBE and CP with GBA3 by ABP detection (ABP 4c)  by acid ceramidase\u2010mediated conversion of accumulating GlcCer in lysosomes m CBE; sixfold increase at 10\u00a0\u03bcm CP)  and in zebrafish larvae . Thus, a selective window for in\u00a0vivo GBA inactivation by CBE exists   Fig.\u00a0. ImportaOur investigation also revealed that CP is a more potent GBA inactivator. However, CP inhibits GBA2 on a par with GBA in both cultured cells and zebrafish larvae Table\u00a0, and the2 (fibroblasts) or 7% CO2 (HEK293T). Zebrafish (Danio rerio) were handled and maintained according to standard protocols (zfin.org). Adult zebrafish were housed at a density of 40 per tank, with a cycle of 14\u00a0h of light and 10\u00a0h of darkness. Adults, embryos and larvae were kept at a constant temperature of 28.5\u00a0\u00b0C. Embryos and larvae were raised in egg water . Synchronized wild\u2010type ABTL zebrafish embryos were acquired after mating of single male and female couples (both > 3\u00a0months old). Frozen brain samples from wild\u2010type and CBE\u2010treated mice were obtained from a previous study Cyclophellitol (CP) and the ABPs were synthesized as described earlier  CO2 HEK23T. Zebram citric acid\u2014Na2HPO4, 0.1% (w/v) bovine serum albumin) for a period of 30\u00a0min to 2\u00a0h. After stopping the substrate reaction with 200\u00a0\u03bcL 1M NaOH\u2010glycine (pH 10.3), 4MU\u2010emitted fluorescence was measured with a fluorimeter LS55  using \u03bbEX 366\u00a0nm and \u03bbEM 445\u00a0nm prism 7.0  by the [inhibitor] vs response\u2014various slope (four parameters) method to obtain IC50 values. The substrate mixtures used for each enzyme are listed as follows: GBA, 3.75\u00a0mm 4MU\u2010\u03b2\u2010D\u2010glucopyranoside  at pH 5.2, supplemented with 0.2% (w/v) sodium taurocholate and 0.1% (v/v) Triton X\u2010100, and 25\u00a0nm N\u2010(5\u2010adamantane\u20101\u2010yl\u2010methoxy\u2010pentyl)\u2010deoxynojirimycin (AMP\u2010DNM), a GBA2\u2010specific inhibitor m 4MU\u2010\u03b2\u2010D\u2010glucopyranoside at pH 5.8, with pre\u2010incubation with 1\u00a0\u03bcm ABP 3a for 30\u00a0min to specifically inhibit GBA activity; \u03b1\u2010glucosidases, 3\u00a0mm 4MU\u2010\u03b1\u2010D\u2010glucopyranoside at pH 4.0 (GAA) or at 7.0 (GANAB), GUSB, 2\u00a0mm 4MU\u2010\u03b2\u2010D\u2010glucuronide at pH 5.0; \u03b1\u2010galactosidases, 2\u00a0mm 4MU\u2010\u03b1\u2010D\u2010galactopyranoside at pH 4.6; \u03b2\u2010galactosidases, 1\u00a0mm 4MU\u2010\u03b2\u2010D\u2010galactopyranoside at pH 4.3 with 0.2\u00a0M NaCl; \u03b1\u2010mannosidases, 10\u00a0mm 4MU\u2010\u03b1\u2010D\u2010mannopyranoside at pH 4.0; \u03b2\u2010mannosidases, 2\u00a0mm 4MU\u2010\u03b2\u2010D\u2010mannopyranoside (Glycosynth) at pH 4.2; \u03b2\u2010hexosaminidase HexA, 5\u00a0mm 4MU\u2010\u03b2\u2010D\u20106\u2010sulpho\u20102\u2010acetamido\u20102\u2010deoxy\u2010glucopyranoside at pH 4.4; \u03b2\u2010hexosaminidases HexA/B, 5\u00a0mm 4MU\u2010\u03b2\u2010N\u2010acetyl\u2010glucosaminide at pH 4.5; \u03b1\u2010N\u2010acetyl\u2010galactosaminidase, 1\u00a0mm 4MU\u2010\u03b1\u2010N\u2010acetyl\u2010galactosaminide at pH 4.5; \u03b1\u2010L\u2010fucosidase, 1\u00a0mm 4MU\u2010\u03b1\u2010L\u2010fucopyranoside at pH 5.0, \u03b1\u2010L\u2010iduronidase, 2\u00a0mm 4MU\u2010\u03b1\u2010L\u2010iduronide (Glycosynth) at pH 4.0; GBA3, 3.75\u00a0mm 4MU\u2010\u03b2\u2010D\u2010glucopyranoside at pH 6.0.All assays were performed in 96\u2010well plates at 37\u00a0\u00b0C for human, zebrafish and mice material. Samples were diluted with McIlvaine buffer to a final volume of 25\u00a0\u03bcL, at pH appropriate for each enzyme. Assays were performed by incubating the samples with 100\u00a0\u03bcL 4MU\u2010 (4\u2010methylumbelliferyl\u2010) substrates diluted in McIlvaine buffer  Triton\u2010100, 0.2% (w/v) sodium taurocholate), or labelled together with GBA2 using 200\u00a0nm \u03b2\u2010aziridine ABP 4c at pH 5.5. GBA2 was labelled with 200\u00a0nm \u03b2\u2010aziridine ABP 4a, 4b or 4c. The \u03b1\u2010glucosidases GAA and GANAB were first preincubated with 200\u00a0nm ABP 4a for 30\u00a0min (pH 4.0 for GAA and pH 7.0 for GANAB), followed by labelling with 500\u00a0nm ABP 6a or 6c at pH 4.0 or 7.0. The \u03b2\u2010glucuronidase GUSB was preincubated with 200\u00a0nm ABP 4a for 30\u00a0min, followed by labelling with 200\u00a0nm \u03b2\u2010aziridine ABP 5c. After ABP incubation, proteins were denatured by boiling the samples with 5\u00d7 Laemmli buffer (50% (v/v) 1\u00a0M Tris\u2010HCl, pH 6.8, 50% (v/v) 100% glycerol, 10% (w/v) DTT, 10% (w/v) SDS, 0.01% (w/v) bromophenol blue) for 5\u00a0min at 98\u00a0\u00b0C, and separated by electrophoresis on 7.5% or 10% (w/v) SDS/PAGE gels running continuously at 90\u00a0V and curve\u2010fitted using prism 7.0 (GraphPad Software). After fluorescence scanning, SDS/PAGE gels were stained for total protein with Coomassie G250 and scanned on a ChemiDoc MP imager .Residual active, not irreversibly inhibited glycosidases were labelled with excess fluorescent ABPs in the optimum McIlvaine buffer, if not otherwise stated (see above). ABP labelling was performed at 37\u00a0\u00b0C for 30\u00a0min for all materials, in\u00a0a total sample volume of 20\u201340\u00a0\u03bcL and 0.5\u20131% DMSO concentration. GBA was labelled with 200\u00a0ny at 90\u00a0V, 37, 38.50 measurements using enzymatic assay, 3.16\u00a0ng (53 fmole) of rGBA was prepared in 12.5\u00a0\u03bcL McIlvaine buffer  supplemented with 0.1% (v/v) Triton X\u2010100, and 0.2% (w/v) sodium taurocholate, and incubated with 12.5\u00a0\u03bcL of inhibitors (CBE or CP) diluted in McIlvaine buffer at 37\u00a0\u00b0C for various time periods. Residual activity of rGBA was measured as described in previous section. For assessing the occupancy of active site pocket by the inhibitors using ABP labelling, the same amount of rGBA was prepared in 10\u00a0\u03bcL of the same McIlvaine buffer, incubated firstly with 2.5\u00a0\u03bcL inhibitor dilutions prepared in McIlvaine buffer at 37\u00a0\u00b0C for various time periods, then with 2.5\u00a0\u03bcL ABP dilutions prepared in McIlvaine buffer; detection of ABP\u2010labelled rGBA follows the procedures described in the previous section.For ICm) or CP (0.001\u201310\u00a0\u03bcm) for 24\u00a0h at 37\u00a0\u00b0C. In addition, confluent human fibroblasts were similarly treated in 15\u2010cm dishes for 2, 24 and 72\u00a0h. For lysis, cells were washed three times with PBS, subsequently lysed by scraping in potassium phosphate buffer , aliquoted and stored at \u221280\u00a0\u00b0C. After determination of the protein concentration, lysates containing equal protein amount  were adjusted to 12\u00a0\u03bcL with potassium phosphate buffer and subjected to residual activity measurements using enzymatic assay  or ABP detection . For in\u00a0vivo ABP labelling, HEK293T cells expressing GBA2 were incubated with culture medium containing CBE (0.015\u201315\u00a0000\u00a0\u03bcm) or CP (0.001\u201310\u00a0\u03bcm) for 24\u00a0h. Medium was removed and cells were incubated for 4\u00a0h with culture medium containing a mixture of 200\u00a0nm ABP 4b, 1\u00a0\u03bcm ABP 5c and 500\u00a0nm ABP 6c, or with DMSO only (negative control). Lysates were prepared and measured for protein concentration as described above, and samples containing 60\u00a0\u03bcg total protein  were subjected to ABP detection .Confluent HEK293T stably expressing human GBA2 were cultured in 12\u2010well plates in triplicates with(out) CBE , or CP (0.001\u2013100\u00a0\u03bcm) for 120\u00a0h at 28.5\u00a0\u00b0C. Per condition, n = 48 embryos were used. At 120\u00a0h (5 dpf), larvae were collected, rinsed three times with egg water, fully aspirated, snap\u2010frozen in liquid nitrogen and stored at \u221280\u00a0\u00b0C until homogenization in 200\u00a0\u03bcL 25\u00a0mm potassium phosphate buffer per 48 individual. Lysis was conducted by sonication with a Polytron PT 1300D sonicator  on ice at 20% power for 3\u00a0s, and repeated three times. Samples containing 20\u201345\u00a0\u03bcg total protein were subjected to ABP detection or enzymatic assay.Adult zebrafish were not sacrificed for this study; all experiments were performed on embryos/larvae before the free\u2010feeding stage  and did not fall under animal experimentation law according to the EU Animal Protection Directive 2010/63/EU. For \u22121 body weight, or PBS, from day 8 until day of sacrifice  as previously described m potassium phosphate buffer (4\u00d7 volume/wet tissue weight) with 1.0\u00a0mm glass beads using a Fastprep\u201024 instrument  set at 6\u00a0m\u00b7s\u22121 for 20\u00a0s, repeated three times, while chilling samples on ice for 2\u00a0min between separate runs. Crude lysates were isolated from the glass beads by pipetting into sterile Safe\u2010Lock Eppendorf tubes. Homogenates were measured for protein concentration, aliquoted and snap\u2010frozen in liquid nitrogen. Samples containing 50\u00a0\u03bcg total protein were subjected to ABP detection or enzymatic assay. Two\u2010tailed unpaired t\u2010test was performed in prism 7.0 software (GraphPad Software) to derive statistical significance, where P\u00a0<\u00a00.05 was considered significant.Brain hemispheres were obtained from mice injected daily with CBE at either 37.5\u00a0mg or 100\u00a0mg\u00b7kgm ABP 4c at pH 6.0. For enzymatic assay, lysates were separated from GBA2 and GBA by centrifugation (16\u00a0000\u00a0g for 10\u00a0min at 4\u00a0\u00b0C) and incubation of the resulting supernatant with 20\u00a0\u03bcL concanavalin A sepharose beads (Sigma\u2010Aldrich) in 200\u00a0\u03bcL of binding buffer  for 1\u00a0h at 4\u00a0\u00b0C on a rotor. Next,\u00a0beads were removed from the supernatant by centrifugation. Five microlitres of the supernatant was added with 20\u00a0\u03bcL McIlvaine buffer (pH 6.0), and subjected to enzymatic assays for GBA3 activity. Measured activity was\u00a0normalized with the corresponding protein concentration of each sample, and data were processed as earlier described.HEK293T cells expressing human GBA3 were cultured, treated (triplicate sets) and lysed in an identical setup as described with GBA2\u2010expressing HEK293T cells. Lysates (12\u00a0\u03bcg protein) were subjected to ABP detection using 200\u00a0nm) or CP (0.01\u201310\u00a0\u03bcm)) for 112\u00a0h at 28\u00a0\u00b0C. Thereafter, zebrafish larvae were washed three times with egg water, and collected in clean screw\u2010cap Eppendorf tubes (three tubes of three larvae per inhibitor concentration). Lipids were extracted and measured according to methods described previously 13C\u2010GlcSph \u22121 in methanol (MeOH), 480\u00a0\u03bcL MeOH and 250\u00a0\u03bcL CHCl3 were added to the sample, stirred, incubated for 30\u00a0min at RT, sonicated (5\u00a0\u00d7\u00a01\u00a0min in sonication water bath) and centrifuged for 10\u00a0min at 15\u00a0700\u00a0g. Supernatant was collected in a clean tube, 250\u00a0\u03bcL CHCl3 and 450\u00a0\u03bcL 100\u00a0mm formate buffer (pH 3.2) were added. The sample was stirred and centrifuged, the upper phase was transferred to a clean tube. The lower phase was extracted with 500\u00a0\u03bcL MeOH and 500\u00a0\u03bcL formate buffer. The upper phases were pooled and taken to dryness in a vacuum concentrator at 45\u00a0\u00b0C. The residue was extracted with 700\u00a0\u03bcL butanol and 700\u00a0\u03bcL water, stirred and centrifuged. The upper phase (butanol phase) was dried and the residue was dissolved in 100\u00a0\u03bcL MeOH. Ten microlitres of this sample was injected to the LC\u2010MS for lipid measurement. Two\u2010tailed unpaired t\u2010test was performed in Prism 7.0 software (GraphPad Software) to derive statistical significance, where P\u00a0<\u00a00.05 was considered significant.Zebrafish embryos at 8\u00a0h postfertilization were seeded in 12\u2010well plates  and treated with CBE (10\u20131000\u00a0\u03bcThere are no conflicts of interest declared.CLK, WWK and IZ performed the experiments; LTL, AV, AHF, AHM and HPS provided essential materials. CLK, WWK, and MM analysed the data. WWK and MM helped to write the manuscript. CLK, JMFGA and MA wrote the manuscript. AHF, HSO and MA revised the manuscript. HSO and JMFGA conceived and designed the study."}
{"text": "III ion is nine-coordinated in a distorted tricapped trigonal\u2013prismatic geometry by three oxygen atoms and three nitro\u00adgen atoms from three benzhydrazide (bzz) ligands, one oxygen atom from the isophthalate (itp2\u2212) ligand, and two oxygen atoms from coordinated water mol\u00adecules. The crystal structure features extensive hydrogen bonding as well as C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions.The first benzohydrazide complex of a lanthanide is reported. The Sm 8H4O4)(C7H8N2O)3(H2O)2]NO3, systematic name di\u00adaqua\u00adtris\u00adsamarium(III) nitrate, the SmIII ion is nine-coordinated in a distorted tricapped trigonal\u2013prismatic geometry by three oxygen atoms and three nitro\u00adgen atoms from three benzhydrazide (bzz) ligands, one oxygen atom from the isophthalate (itp2\u2212) ligand, and two oxygen atoms from coordinated water mol\u00adecules. The nitrate group is disordered over two sets of sites with occupancy factors of 0.310\u2005(17) and 0.690\u2005(17). In the crystal, adjacent mol\u00adecules are linked into chains via pairs of O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds between the carboxyl\u00adate acceptor and the coordinated water and amine NH2 donors. Mol\u00adecules are further stacked by \u03c0\u2013\u03c0 inter\u00adactions involving the benzene ring of the itp2\u2212 ligands, forming double chains that extend in the b-axis direction. These double chains are further linked into a three-dimensional supra\u00admolecular network via hydrogen bonds  between the complex mol\u00adecule and the nitrate groups along with C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions involving the benzene rings of the bzz and itp2\u2212 ligands.The first benzohydrazide complex of a lanthanide is reported. In the title compound, [Sm(C Distinct from transition metal centers, lanthanide ions often demonstrate high and variable coordination numbers as well as diverse coordination geometries, which can lead to versatile structures and topologies  ligands, one completely deprotonated isophthalate (itp2\u2212) ligand, two coordinated water mol\u00adecules, and one disordered NO3\u2212 ion. The hydrazide group of the bzz ligand adopts a bidentate \u03bc2-\u03b71:\u03b71 chelating coordination mode, whereas the carboxyl\u00adate groups of the fully deprotonated itp2\u2212 ligand display a \u03bc1-\u03b71:\u03b70 monodentate coordination fashion. The SmIII ion is nine-coordinated by three oxygen atoms  and three nitro\u00adgen atoms  of three different bzz ligands, one oxygen atom (O4) from the completely deprotonated itp2\u2212 ligand, and other two oxygen atoms  from the coordinated water mol\u00adecules. The central metal SmIII atom can be described as having a distorted tricapped trigonal\u2013prismatic geometry, Fig.\u00a02III complexes \u2005\u00c5 and a dihedral angle = 0.0\u2005(2)\u00b0  , and the bzz and itp2\u2212 ligands , are also observed, which help further to stabilize the crystal structure.As can be seen in Fig.\u00a03s Table\u00a01 involvinet al., 2016et al., 1971et al., 2003et al., 2011et al., 2009A search of the Cambridge Structural Database 3\u00b76H2O , bzz , H2itp , and H2O (4\u2005ml) was sealed in a 15\u2005ml Teflon-lined steel autoclave and heated at 373\u2005K for 24\u2005h. The mixture was cooled to room temperature and light-yellow block-shaped crystals of the title compound were obtained in 79% yield . Analysis calculated (%) for C29H32N7O12Sm (1376.80): C 42.43; H 3.93; N 11.94%. Found: C 42.46; H 3.96; N 11.90%.A mixture of Sm(NOUiso(H) = 1.2Ueq(C). The H atoms bonded to O and N atoms were located in a difference-Fourier map, but were refined with distance restraints of O\u2014H = 0.84 \u00b1 0.01\u2005\u00c5 and N\u2014H = 0.88 \u00b1 0.01\u2005\u00c5, and with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The nitrate group is disordered over two sets of sites, with occupancy factors of 0.310\u2005(17) and 0.690\u2005(17).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018015360/pj2059sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018015360/pj2059Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018015360/pj2059Isup3.cdxSupporting information file. DOI: 1876239CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S,3S)-2-amino-3-methyl\u00adpenta\u00adnoic acid, l-isoleucine C6H13NO2, crystallizes in the monoclinic space group P21 with four independent mol\u00adecules in the asymmetric unit. In the crystal, N\u2013H\u22efO hydrogen bonds link two pairs of independent mol\u00adecules and their symmetry-related counterparts to form two types of layers stacked in an anti-parallel manner parallel to (001). The hydro\u00adphobic aliphatic isopropyl groups protrude from these layers.A new polymorph of -2-amino-3-methyl\u00adpenta\u00adnoic acid, l-isoleucine C6H13NO2, crystallizes in the monoclinic space group P21 with four independent mol\u00adecules in the asymmetric unit. The mol\u00adecules are zwitterions. In the crystal, N\u2014H\u22efO hydrogen bonds link two pairs of independent mol\u00adecules and their symmetry-related counterparts to form two types of layers stacked in an anti-parallel manner parallel to (001). The hydro\u00adphobic aliphatic isopropyl groups protrude from these layers.A new polymorph of (2 S,3S)-2-Amino-3-methyl\u00adpenta\u00adnoic acid, known as l-isoleucine (l-Ile), is one of the 20 amino acids common in animal proteins and required for normal functioning in humans. l-Ile is classified as a hydro\u00adphobic amino acid and is one of the two common amino acids that has a chiral side chain. l-Ile is essential for human muscle tissue recovery after exercise, along with Valine and Leucine.\u00b0, N1\u2014C2\u2014C3\u2014C4 = \u2212155.4\u2005(3)\u00b0 and N3\u2014C14\u2014C15\u2014C18 = 78.1\u2005(4)\u00b0, N3\u2014C14\u2014C15\u2014C16 = \u2212155.8\u2005(3)\u00b0. The other two mol\u00adecules are of conformer type II with the torsion angles N2\u2014C8\u2014C9\u2014C12 = 178.6\u2005(4)\u00b0, N2\u2014C8\u2014C9\u2014C10 = \u221256.9\u2005(5)\u00b0 and N4\u2014C20\u2014C21\u2014C24 = 179.1\u2005(4)\u00b0, N4\u2014C20\u2014C21\u2014C22 = \u221256.8\u2005(5)\u00b0. Furthermore, there is a minor conformational variance between all the four independent mol\u00adecules, as illus\u00adtrated by the torsion angles of the iso-propyl side chains: C6\u2014C3\u2014C4\u2014C5 = \u221256.6\u2005(5)\u00b0, C12\u2014C9\u2014C10\u2014C11 = \u221251.6\u2005(6)\u00b0, C18\u2014C15\u2014C16\u2014C17 = \u221258.9\u2005(5)\u00b0 and C24\u2014C21\u2014C22\u2014C23 = \u221253.2\u2005(6)\u00b0.The existence of another chiral center in the side chain allows for conformational differences. Each l-Ile is embedded inside the layers while the side chains are oriented away, creating a hydro\u00adphobic surface. However, this hydrogen-bonding network has directionality along the polar b axis and specifically parallel to (001)  was dissolved in water  by heating to 353\u2005K, with constant stirring until total dissolution. The hot solution was then filtered through cotton wool into glass crystallization dishes, which were covered with filter paper in order to allow slow evaporation, placed in a heating bath. Colorless crystal chunks, suitable for X-ray crystallographic analysis were obtained. The absolute configuration of the title compound is already known.Single crystals of Uiso(H) = 1.2Ueq(C) or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018006126/lh5872sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018006126/lh5872Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018006126/lh5872Isup3.cmlSupporting information file. DOI: 1838774CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II di\u00adthio\u00adcarbazate complex features a square-planar trans-N2S2 donor set for the metal atom 2], features a trans-N2S2 donor set as a result of the CuII atom being located on a crystallographic centre of inversion and being coordinated by thiol\u00adate-S and imine-N atoms derived from two di\u00adthio\u00adcarbazate anions. The resulting geometry is distorted square-planar. In the crystal, \u03c0(chelate ring)\u2013\u03c0(fur\u00adyl) [inter-centroid separation = 3.6950\u2005(14)\u2005\u00c5 and angle of inclination = 5.33\u2005(13)\u00b0] and phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions sustain supra\u00admolecular layers lying parallel to (Cg(fur\u00adyl) contacts (Cu\u22efCg = 3.74\u2005\u00c5) were also found. Inter\u00adaction energy calculations suggest the contacts between mol\u00adecules are largely dispersive in nature.The title Cu The conformation about the endocylic imine bond is Z, as a result of chelation, whereas the exocyclic imine bond has an E conformation.The mol\u00adecular structure of (I)s Table\u00a01. The res2CS chelate rings. While the r.m.s. deviation for the five atoms is relatively small at 0.0453\u2005\u00c5, suggesting a near planar ring, a better description for the conformation is that of an envelope with the copper atom being the flap atom. In this description, the r.m.s. deviation of the S1, N1, N2 and N3 atoms of the ring is 0.0002\u2005\u00c5, with the Cu atom lying 0.199\u2005(3)\u2005\u00c5 out of the plane. The dihedral angle between the best plane through the chelate ring and the 2-furyl ring is 5.33\u2005(18)\u00b0 indicating an essentially co-planar relationship. By contrast, the dihedral between the chelate and phenyl rings is 86.75\u2005(7)\u00b0, indicative of an orthogonal relationship. Finally, the dihedral angle between the peripheral organic rings is 81.42\u2005(9)\u00b0.The bidentate mode of the coordination of the di\u00adthio\u00adcarbazate ligand leads to the formation of five-membered CuNet al., 2008II in (I)ca 10\u00b0 in (I)ca 5\u00b0, changes consistent with the reorganization of \u03c0-electron density from the C1\u2014S1 to C1\u2014N1 bonds in (I)The structure of the acid form of the anion in (I)a). The association between mol\u00adecules is of the type \u03c0(chelate ring)\u2013\u03c0(fur\u00adyl) whereby the inter-centroid Cg\u2013Cgi separation is 3.6950\u2005(14)\u2005\u00c5 with angle of inclination = 5.33\u2005(13)\u00b0; symmetry operation (i) x, \u22121\u00a0+\u00a0y, z. Such \u03c0\u2013\u03c0 inter\u00adactions between chelate rings and aromatic rings are well documented in the literature, especially for sterically unencumbered square-planar complexes and can impart significant energies of stabilization to the mol\u00adecular packing , Table\u00a02b). Details of the weak inter\u00admolecular contacts connecting layers are given in the analysis of the calculated Hirshfeld surfaces below.The most prominent feature of the mol\u00adecular packing is the formation of supra\u00admolecular layers lying parallel to a), and those delineated into H\u22efH, C\u22efH/H\u22efC, S\u22efH/H\u22efS and C\u22efC contacts are illustrated in Fig.\u00a06b)\u2013(e), respectively; the percentage contribution from all the identified inter\u00adatomic contacts to the Hirshfeld surface are summarized qu\u00adanti\u00adtatively in Table\u00a04The overall two-dimensional fingerprint plot, Fig.\u00a06de + di \u223c2.1\u2005\u00c5 in the fingerprint plot delineated into H\u22efH contacts in Fig.\u00a06b), represents the short inter-layer H\u22efH contact involving phenyl-H8 atoms, Table\u00a03de + di \u223c2.7\u2005\u00c5 in the respective delineated fingerprint plot of Fig.\u00a06c) and Table\u00a03d), the short inter\u00adatomic contact involving the S-benzyl atoms, Table\u00a03de + di < 3.0\u2005\u00c5, i.e. at the sum of van der Waals radii. The distribution of points in the fingerprint plot delineated into C\u22efC contacts, Fig.\u00a06e), forming triangular tip at de + di \u223c3.3\u2005\u00c5 is due to the presence of such short inter\u00adatomic contacts summarized in Table\u00a03The conical tip appearing at Crystal Explorer , polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep). The energies were obtained using the wave function calculated at the HF/STO-3G level theory. The strength and nature of the inter\u00admolecular inter\u00adactions are summarized qu\u00adanti\u00adtatively in Table\u00a05x, \u22121\u00a0+\u00a0y, z in Table\u00a05Cg(fur\u00adyl) = 3.74\u2005\u00c5], \u03c0(chelate)\u2013\u03c0(fur\u00adyl), C\u22efC and S\u22efH/H\u22efS inter\u00adactions. Among these inter\u00adactions, the short inter\u00adatomic S\u22efH/H\u22efS contact contributes to the electrostatic component while the others to the dispersion component of the energies. Even though the inter-centroid distance between symmetry-related phenyl (C3\u2013C8) rings are greater than 4.0\u2005\u00c5  and the inter\u00adatomic S\u22efH distance is greater than sum of their van der Waal radii , they possess greater inter\u00adaction energies compared to inter\u00admolecular phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) and short inter\u00adatomic H\u22efH contacts, as summarized in Table\u00a05b-axis direction in Fig.\u00a07Eele, Edisp and Etot, respectively; the radius of the cylinder is proportional to the magnitude of inter\u00adaction energy. It is clearly evident from the energy frameworks shown in Fig.\u00a07Utilizing et al., 2016e.g. substituents carrying pyridyl or phenoxide, neutral mol\u00adecules only and non-solvated structures yielded 24 analogues to (I)trans-N2S2 square-planar geom\u00adetry as in (I)2)5Me]=NN=CC6H4OMe-4}2]2 arising from inter\u00admolecular Cu\u22efS inter\u00adactions between centrosymmetrically related trans-N2S2 square-planar geometries  was synthesized following a procedure adapted from a previous report : 3089 (w) \u03bd(N\u2014H), 1609 (m) \u03bd(C=N), 1016 (s) \u03bd(N\u2014N), 763 (s), \u03bd(C=S).26H22CuN4O2S4: C, 50.84; H, 3.61; N, 9.12; Cu, 10.34. Found; C, 50.49; H, 3.45; N, 8.77; Cu, 10.81. FTIR : 1593 (m), \u03bd(C=N), 964 (s), \u03bd(N\u2014N), 760 (s), \u03bd(C\u2014S).Synthesis of (I)Uiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989019006145/hb7822sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019006145/hb7822Isup2.hklStructure factors: contains datablock(s) I. DOI: 1913482CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1\u2010Ln) for all the heavier Ln from Gd\u2013Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5\u2010\u03ba1\u2010F)B(C6F5)3}]  are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2\u2010Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1\u2010Sm) is isolated, which like heavier 1\u2010Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1\u2010Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.As the dysprosocenium complex [Dy(Cp Herein, we extend these studies to the lighter, larger Ln to define the characteristic features of analogous [Ln(Cpttt)2]+ cations across the Ln series. We find that for the largest members of the 1\u2010Ln series one meta\u2010F of the [B(C6F5)4]\u2212 anion coordinates to the exposed equatorial site in the solid state, giving [Ln(Cpttt)2{(C6F5\u2010\u03ba1\u2010F)B(C6F5)3}] . However, smaller SmIII yields an isolated cation, [Sm(Cpttt)2][B(C6F5)4] (1\u2010Sm), which is structurally analogous to the heavier members of the series. We were unable to complete the series with the Eu analogue 1\u2010Eu as the stability associated with the +2 oxidation statettt)2(X)]  precursors.We previously reported that the bulky ion [BC6F4]\u2212 provi1\u2010Ln ,ttt)2{(C6F5\u2010\u03ba1\u2010F)B(C6F5)3}]  and [Sm(Cpttt)2][B(C6F5)4] (1\u2010Sm) were all synthesised by the reactions of [Ln(Cpttt)2(Cl)]  with [H(SiEt3)2][B(C6F5)4]3)2][B(C6F5)4] was selected as a reagent for Ln metallocenium cation formation as: (i)\u2005it is soluble in benzene, hence strongly coordinating O\u2010donor solvents can be avoided; (ii)\u2005there is a significant enthalpic effect due to formation of a strong Si\u2212Cl bond, and (iii)\u2005there is an additional entropic effect arising from two reactant species giving three product species. Complexes 1\u2010Ln  were crystallised from dichloromethane (DCM) layered with hexane and became more temperature\u2010sensitive as soon as DCM was added; thus, these complexes were stored at \u221225\u2009\u00b0C and measurements were performed below \u221225\u2009\u00b0C. Despite repeated efforts we were unable to recrystallise 1\u2010Ln  from DCM/hexane; we later found that these complexes dissolved in hot toluene and could be recrystallised and stored at room temperature.According to previously published synthetic methods for the synthesis of 2\u2010Ln were synthesized from LnCl3 and two equivalents of KCpttt by modification of the synthesis of 2\u2010Pr and 2\u2010Nd from the parent LnCl3 and NaCpttt (Scheme\u20053 with NaCpttt gives [Eu(Cpttt)2], with elimination of half an equivalent of (Cpttt)2 via reductive coupling.ttt)2(F)] by the oxidation of [Eu(Cpttt)2]2][PF6]5 and [Fe(Cp)2]. However, this did not occur and instead we obtained [{Eu(Cpttt)(\u03bc\u2010PF6\u2010\u03ba4\u2010F)(THF)}2] (3) in 60\u2009% yield, along with several crystals of (Cpttt)2 (4), presumably due to the contamination of the EuII starting material with THF solvates, such as [Eu(Cpttt)2(THF)] or [Eu(Cpttt)(I)(THF)x]n, and subsequent ligand scrambling. Therefore, Eu is the only Ln apart from radioactive Pm that we were unable to access via these anion abstraction procedures. Crystalline yields for 2\u2010Ln are similar (46\u201352\u2009%) except for 2\u2010La, which was isolated in 31\u2009% yield. For 1\u2010Ln, the crystalline yields were dependent upon the solvent system; yields were significantly higher when crystallised from toluene (67\u2009% for 1\u2010La and 69\u2009% for 1\u2010Sm) compared to those crystallised from DCM layered with hexane (21\u201359\u2009%).The precursors t Scheme\u2005.19 This 1\u2010Ln and 2\u2010Ln were generally in excellent agreement with expected values, although low carbon values, likely due to carbide formation from incomplete combustion, were consistently obtained in some cases. In spite of this, the bulk purity of 1\u2010Ln was indicated by the consistency of other analytical data with their formulations (see below). Complex 1\u2010Sm contains the largest LnIII ion in a Ln metallocenium cation with no equatorial interactions to be isolated to date. The most appropriate explanation for the structural change for the largest LnIII cations is a simple argument based on ionic radii, with the two Cpttt rings offering a sufficient amount of steric protection around the smaller SmIII ion III ions are large enough to accommodate a further interaction .R ligands and the weakly coordinating anion.Elemental analysis results obtained for 1H\u2005NMR spectra were recorded from \u2212350 to +350\u2005ppm for 1\u2010Ln and 2\u2010Ln 4]\u2212 anions in 1\u2010Ln were observed by 11B{1H} and 19F{1H}\u2005NMR spectroscopy (see Supporting Information). In the case of 1\u2010La, we could also employ 13C{19F}\u2005NMR spectroscopy to characterise the [B(C6F5)4]\u2212 anion: the expected four aromatic resonances were located at 124.26 (ipso\u2010), 136.91 (m\u2010), 138.79 (p\u2010) and 148.71\u2005ppm (o\u2010); the signal for the ipso\u2010carbon is a quartet from coupling with 11B (1JBC=51.8\u2005Hz). Signals in the 11B{1H} NMR spectra of 1\u2010Ln were observed between \u221220 and \u221216\u2005ppm, and three peaks were observed in the 19F{1H}\u2005NMR spectra, corresponding to meta\u2010, para\u2010 and ortho\u2010F. In the 19F{1H}\u2005NMR spectrum of 1\u2010Sm, the para\u2010F signal is a triplet from coupling to two adjacent meta\u2010F atoms (JFF=20.4\u2005Hz), but this is a singlet for 1\u2010La, presumably due to broadening by quadrupolar 139La (I=7/2). The 11B and 19F\u2005NMR spectra of [Sc(Cp*)2{(C6F5\u2010\u03ba2\u2010F)B(C6F5)3}]2{(\u03bc\u2010C6F5\u2010\u03ba1\u2010F)2B(C6F5)2}]2 1\u2010Ln (Ln=Gd\u2013Lu).6F5)4]\u2212 anions in light 1\u2010Ln are only weakly bound in solution, and dissociate to give isolated [Ln(Cpttt)2]+ cations, as evidenced by the symmetry of 19F\u2005NMR spectra.19F\u2005NMR studies of 1\u2010La in C7D8, but the spectra were unchanged down to 218\u2005K. Finally, the paramagnetism of 3 precluded assignment of its 1H, 13C, 19F and 31P\u2005NMR spectra.1\u2010Ln, 2\u2010Ln, 3 and 4 were determined by single crystal XRD 2]+ cation of 1\u2010Sm exhibits identical structural features with 1\u2010Dy,meta\u2010fluorine of one of the C6F5 rings of the [B(C6F5)4]\u2212 anion. In all cases, the [Ln(Cpttt)2]+ fragments exhibit bent geometries and the Cpcentroid\u22c5\u22c5\u22c5Ln\u22c5\u22c5\u22c5Cpcentroid angles for 1\u2010Ln are closer to linearity than the corresponding precursors 2\u2010Ln. In the cases of 1\u2010Sm and the late Ln metallocenium cations in 1\u2010Ln ,centroid\u22c5\u22c5\u22c5Ln\u22c5\u22c5\u22c5Cpcentroid angles are significantly more linear than the [Ln(Cpttt)2]+ fragments in early 1\u2010Ln  which have Ln\u22c5\u22c5\u22c5F interactions . Two nearly eclipsed \u03b75\u2010Cpttt rings coordinate to the LnIII centres in all 1\u2010Ln.centroid distances decrease regularly across the Ln series .1\u2010Sm, two equatorial electrostatic Ln\u22c5\u22c5\u22c5C interactions with carbon atoms from a tBu group were observed , with a C\u22c5\u22c5\u22c5Ln\u22c5\u22c5\u22c5C angle of 147.56(11)\u00b0; this feature has been noted for the heavier Lns previously.1\u2010Ln , Ln\u22c5\u22c5\u22c5F distances were observed between 2.679(9)\u2005\u00c5 (1\u2010La) to 2.632(4)\u2005\u00c5 (1\u2010Nd); similar contacts between LnCpR2 fragments and [B(C6F5)4]\u2212 anions have previously been seen for [Sc(Cp*)2{(C6F5\u2010\u03ba2\u2010F)B(C6F5)3}]2{(\u03bc\u2010C6F5\u2010\u03ba1\u2010F)2B(C6F5)2}]2 .2]+ fragments are bridged by two [B(C6F5)4]\u2212 anions to give a total of four meta\u2010F\u22c5\u22c5\u22c5Ln interactions, but in the Sc example a single C6F5 ring binds to one ScIII centre via both a meta\u2010 and a para\u2010F atom. The shortest Ln\u22c5\u22c5\u22c5F distance in 1\u2010Sm is 5.693(2)\u2005\u00c5, which indicates that Ln\u22c5\u22c5\u22c5F interactions are only observed for the 1\u2010Ln series when the LnIII ionic radius is larger than a critical value, when the bis\u2010Cpttt framework no longer provides sufficient coverage to prevent equatorial interactions with [B(C6F5)4]\u2212 anions.The solid\u2010state structures of to 149.48\u00b0; late L1\u2010Ln and 2\u2010Ln were obtained as microcrystalline powders , owing to the 4I9/2\u21924G5/2 transitions;1\u2010Sm shows absorptions at \u03bd\u02dcmax=11\u2009400\u2005cm\u22121 (\u03f5=20\u2005mol\u22121 dm3\u2005cm\u22121) and 8400\u2005cm\u22121 (\u03f5=50\u2005mol\u22121\u2009dm\u22123\u2009cm\u22121), which likely arise from 6H5/2\u21926F11/2, 6F7/2 transitions, respectively.2\u2010Nd and 2\u2010Sm.The electronic spectra of 1\u2010Ln and 2\u2010Ln using MOLCAS 8.0Complete active space self\u2010consistent field spin\u2010orbit (CASSCF\u2010SO) calculations were performed on unoptimized XRD structures of Jm projections of the total angular momentum J, but can also be defined as an effective S=1/2 state. With this definition, the S=1/2 states have an effective g\u2010matrix describing the magnetic anisotropy owing to the varying Jm composition of each doublet. The 3\u00d73 g\u2010matrix can always be diagonalised to yield three principal g\u2010values and their corresponding orientations in the molecular frame; here we define the principal g\u2010values such that g1<g2<g3. While the choice of quantisation axis for the CF is irrelevant for any physical observable, it defines how each state is decomposed into linear combinations of Jm projections . In the case of pure Jm states (Jm>1/2), g1=g2=0 and g3=2JmJg where Jg is the Land\u00e9 g\u2010factor of the J multiplet of the LnIII ion. In the general case of mixed Jm states it is useful to define <Jz>, the expectation value of the Jz operator which measures the projection of J on the quantisation axis, to understand the magnetic nature of the states; in the limiting case of a pure Jm state, <Jz>=Jm.In the case of Kramers ions with an odd number of unpaired electrons, there will always be two\u2010fold electronic degeneracy in zero magnetic field, irrespective of a low\u2010symmetry CF. Each of these Kramers doublets is a linear combination of 1\u2010Ce , and is thus well\u2010described as Jm=\u00b15/2 when the CF is quantised along the g3 direction 4]\u2212 anion (Table\u2005S18), showing only a marginal increase in axiality. For 2\u2010Ce however, while the ground doublet is also Jm=\u00b15/2 with the CF defined along the Cpttt\u2013Cpttt direction , the first excited state is almost isotropic and the most excited state also resembles the Jm=\u00b15/2 state when the CF is quantised along the \u201cpseudo\u2010C3\u201d direction perpendicular to both the Cpttt\u2013Cpttt direction and the Ce\u2013Cl vector ; this demonstrates that the Cl\u2212 anion is competing with the Cpttt ligands and has a significant influence on the CF.For Ce Table\u2005 we obser1\u2010Sm , this makes 1\u2010Sm the antithesis of an SMM with the Jm=\u00b11/2, \u00b13/2 and \u00b15/2 doublets in ascending energy , yet when the CF is quantised along this direction there is strong mixing between Jm=\u00b11/2 and \u00b13/2 owing to the competition between the Cpttt and Cl\u2212 ligands (Table\u2005S29). For both 1\u2010Sm and 2\u2010Sm the g\u2010values are much reduced from those expected for an isolated 6H5/2 multiplet; this is due to considerable J\u2010mixing with the low\u2010lying 6H7/2 and 6H9/2 multiplets, rendering a CF model in the basis of a pure J=5/2 state an inaccurate representation of the wavefunction.The electronic structure of Sm Table\u2005, like 1\u2010y Figure\u2005 and S28.III the situation is less clear than for CeIII and SmIII because the magnitude of the quadrupolar terms in the expansion of the Jm electron densities are smaller than for the other LnIII ions,Jm states by the low symmetry CF is more severe. For 1\u2010Nd the two lowest lying doublets are 86\u2009% Jm=\u00b19/2 and 86\u2009% Jm=\u00b17/2, respectively, when the CF is quantised along the Cpttt\u2010Cpttt direction (Table\u2005S25), however the subsequent excited states are quite mixed and the highest\u2010energy doublet is 86\u2009% Jm=\u00b19/2 when the CF is quantised along the \u201cpseudo\u2010C3\u201d direction . Removal of the counterion reduces the axiality of the most excited state (Table\u2005S26), however this does not change the overall picture of the electronic structure. This suggests that it is the bent arrangement of the Cpttt rings, and not the influence of the [B(C6F5)4]\u2212 counterion, that forces the magnetic anisotropy of the most excited state to be perpendicular to that of the ground state, further highlighting the minimal electronic influence of the bulky anion. The electronic structure of 2\u2010Nd is generally similar to that of 1\u2010Nd, however the mixing is more severe (Table\u2005S27) and is not discussed further.For Ndpseudo\u2010doublets that are well described as pure Jm functions and a singlet state corresponding to Jm=0; the departure from axiality determines the degree to which the pseudo\u2010doublets are split into singlets. For pseudo\u2010doublets only a single principal g\u2010value can be defined and the other two are zero (note that this does not necessarily indicate a pure Jm state); thus, <Jz> is a useful indicator for non\u2010Kramers ions.In the case of non\u2010Kramers ions, the action of a low\u2010symmetry CF can completely remove the degeneracy of the electronic states, although it does not have to do so (e.g. in high symmetry environments). In the case of a near\u2010axial CF, there will be a number of 1\u2010Pr . Removal of the counterion in the CASSCF\u2010SO calculations for 1\u2010Pr results in larger energy gaps between the CF states and reduces the splitting within the pseudo\u2010doublets at higher energies, but generally does not have a large effect on the electronic structure (Table\u2005S22). For 2\u2010Pr, with an extra competitive element in the CF (the Cl\u2212 ion), the resulting electronic structure is nearly all singlets (Table\u2005S23), and application of a small magnetic field is inconsequential (Table\u2005S24).The situation for Pr Table\u2005 is similn Tables\u2005 and S20,III, NdIII and SmIII) of 1\u2010Ln and 2\u2010Ln. We note generally that the intensities of the signals are very weak, however that there is excellent agreement between experiment and theory , however the latter is apparently too weak or is broadened beyond detection.To experimentally probe the nature of the ground states, we have performed cryogenic electron paramagnetic resonance (EPR) spectroscopy on the Kramers ion analogues , however the data for 2\u2010Pr decrease rapidly at lower temperatures, and those for 1\u2010Pr decrease slowly below 20\u2005K. For 2\u2010Pr this is due to a singlet ground state, which is confirmed by magnetisation measurements  and CASSCF\u2010SO calculations (Table\u2005S23), but for 1\u2010Pr the experimental decrease is much more substantial than predicted by CASSCF\u2010SO, suggesting that the calculations have underestimated the splitting within the ground pseudo\u2010doublet on the order of a few cm\u22121 (Table\u2005S20). Generally, these magnetic data are in good agreement with CASSCF\u2010SO\u2010calculated electronic structures, however we note that due to the small magnetic moments of the light LnIII ions (where the SO coupling gives J=|L\u2212S| ground multiplets) the experimental data are sensitive to small errors in sample masses and diamagnetic corrections. The data for 1\u2010Sm and 2\u2010Sm are the most susceptible to this, as they feature not only the lowest magnetic moments, but also because they are highly sensitive to J mixing (see above) such that the calculations only reveal an approximate electronic structure.The \u03c7ttt)2]+ seriesIII analogues. Therefore, we investigated the Kramers ions with AC susceptibility studies to examine their magnetisation dynamics , giving an effective barrier of Ueff=51.2\u2005cm\u22121 with \u03c40=9.64\u00d710\u22128\u2005s; CASSCF\u2010SO predicts a first excited state at around 72\u2005cm\u22121, so this is not unreasonable. In all other cases a Raman mechanism is the best model for the data, and indeed is also a possible explanation for 2\u2010Nd. For both pairs of 1\u2010Ce vs. 2\u2010Ce and 1\u2010Nd vs. 2\u2010Nd, the Raman exponent is smaller for 1\u2010Ln than for 2\u2010Ln where the Cl\u2212 is bound, similar to the trend we have observed previously for the heavy Ln metallocenium cations (Table\u2005ttt)2]+ is responsible for lowered Raman exponents. However, the exponents for 1\u2010Ce and 1\u2010Nd are considerably larger than for 1\u2010Tb, 1\u2010Dy and 1\u2010Ho, which suggests that there could be an influence of the proximate [B(C6F5)4]\u2212 anion on the relaxation dynamics of these species.We were curious if the anomalous Raman exponents we observed previously for the heavy [Ln(Cpttt)2]+, with the exception of Eu and Pm. In the case of the early Ln (Ln=La\u2010Nd) the [B(C6F5)4]\u2212 counter\u2010ions weakly coordinate to the metal centre through a meta\u2010fluorine atom in the solid state, as the metals are large enough to incorporate this additional interaction; these equatorial interactions are absent in the solid state for the later Ln  analogues which contain smaller Ln centres. However, in the solution phase these interactions could not be detected by VT 19F\u2005NMR spectroscopy, indicating that isolated Ln metallocenium cations are present in fluid solution.ttt)2]+ for the early Ln suggests that the weak equatorial meta\u2010fluorine interaction has little effect on the axiality of these systems. Measurement of the relaxation dynamics shows a consistent picture across the [Ln(Cpttt)2]+ series, where the absence of monodentate ligands leads to lower Raman exponents than when they are present, indicating that this effect is a hallmark of all Ln metallocenium cations. We cannot rule out the influence of [B(C6F5)4]\u2212 on the relaxation dynamics of 1\u2010Ce and 1\u2010Nd, and suggest that the effect of weak equatorial donors on magnetic relaxation mechanisms may be explored in the future by using different CpR ligands and a range of weakly coordinating anions.We have completed a series of analogous Ln metallocenium cations benzene and [D8]toluene were dried by refluxing over K, and [D2]DCM was dried by refluxing over CaH2. NMR solvents were degassed by three freeze\u2010pump\u2010thaw cycles, and vacuum\u2010transferred before use. Anhydrous LnCl3 were purchased from Alfa Aesar and were used as received. KCpttt,3)2][B(C6F5)4]ttt)2]2\u2010Ln  were made by a modification of published procedures.1H (400 and 500\u2005MHz), 13C{1H} (100 and 125\u2005MHz), 13C{19F} (125\u2005MHz),11B{1H} (128 and 160\u2005MHz), and 19F{1H} (376\u2005MHz) NMR spectra were obtained on Avance III 400 or 500\u2005MHz spectrometers at 298\u2005K. UV/Vis/NIR spectroscopy was performed on samples in Youngs tap\u2010appended 10\u2005mm path length quartz cuvettes on an Agilent Technologies Cary Series UV/Vis/NIR spectrophotometer at 175\u20133300\u2005nm. ATR\u2010Fourier transform infrared (ATR\u2010FTIR) spectra were recorded as microcrystalline powders using a Bruker Tensor 27 spectrometer. Elemental analyses were performed by Mrs Anne Davies and Mr Martin Jennings at The University of Manchester School of Chemistry Microanalysis Service, Manchester, UK. General synthetic procedures for 1\u2010Ln and 2\u2010Ln are given below; full details are in the Supporting Information.ttt)2{(C6F5\u2010\u03ba1\u2010F)B(C6F5)3}] (La=La\u2010Nd), [Sm(Cpttt)2] [B(C6F5)4] (1\u2010Ln)[Ln(Cp: Benzene (15\u2005mL) was added to a mixture of [H(SiEt3)2][B(C6F5)4] (0.5\u20130.8\u2005mmol) and 2\u2010Ln (0.5\u20130.8\u2005mmol) at room temperature. The mixture was stirred for 16\u2005hours and a precipitate formed. The volatiles were removed in vacuo to give a powder, which was washed with hexane (10\u201315\u2005mL) and benzene (10\u201315\u2005mL). In some cases, the crude material was dissolved in DCM  at \u221278\u2009\u00b0C, and layered with 1\u20131.5\u2005equiv of hexane. Storage at \u221225\u2009\u00b0C overnight gave crystals of 1\u2010Ln . In other cases, the crude material was dissolved in hot toluene (5\u2005mL). Storage at room temperature gave 1\u2010Ln .1\u2010La: Colourless crystals . Anal. Calcd (%) for C58H58BF20La: C, 54.22; H, 4.55; Found: C, 52.22; H, 4.15. 1H\u2005NMR : \u03b4=1.38 3), 1.46 3), 6.26\u2005ppm . 11B{1H}\u2005NMR : \u03b4=\u221216.63\u2005ppm (s). 13C{1H}\u2005NMR : \u03b4=29.86 and 30.00 (C(CH3)3), 30.53 (C(CH3)3), 31.03 and 31.18 (C(CH3)3), 32.82 (C(CH3)3), 135.96 (Cp\u2010CH), 147.78 (Cp\u2010C), 149.70\u2005ppm (Cp\u2010C). 13C{19F}\u2005NMR : \u03b4=124.26 , 136.91 , 138.79 , 148.71\u2005ppm . 19F{1H}\u2005NMR : \u03b4=\u2212166.98 , \u2212162.89 , \u2212132.67\u2005ppm . The low solubility of 1\u2010La in [D6]benzene precluded assignment of 1H and 13C{1H}\u2005NMR spectra in this solvent. 11B{1H} NMR : \u03b4=\u221216.00\u2005ppm (s). 19F{1H}\u2005NMR : \u03b4=\u2212165.32 , \u2212160.90 , \u2212131.66\u2005ppm . FTIR : \u03bd\u02dc=2967 , 2874 (w), 2819 (w), 1643 (m), 1513 (s), 1459 (s), 1365 (m), 1273 (m), 1240 (m), 1087 (s), 977 (s), 924 (w), 828 (s), 773 (s), 756 (s), 683 (s), 660 (s), 609 (m), 574 (m), 470 (w), 440\u2005cm\u22121 (w).1\u2010Ce: Yellow crystals . Anal. Calcd (%) for C58H58BF20Ce\u22c51.5CH2Cl2: C, 50.56; H, 4.35; Found: C, 50.90; H, 4.18. \u03bceff : 2.12\u2005\u03bcB. 1H\u2005NMR : \u03b4=\u221213.26 3), \u22127.93\u2005ppm 3); no other signals observed. 11B{1H}\u2005NMR : \u03b4=\u221218.02\u2005ppm (s). The paramagnetism of 1\u2010Ce precluded assignment of its 13C{1H}\u2005NMR spectrum. 19F{1H}\u2005NMR : \u03b4=\u2212170.26 , \u2212164.33 , \u2212134.61\u2005ppm . FTIR : \u03bd\u02dc=2963 , 2871 (w), 2821 (w), 1643 (m), 1512 (s), 1459 (s), 1365 (m), 1273 (w), 1241 (w), 1087 (s), 976 (s), 924 (w), 867 (w), 830 (m), 773 (s), 756 (s), 683 (s), 660 (s), 609 (m), 574 (m), 441\u2005cm\u22121 (w).1\u2010Pr: Yellow crystals . Anal. Calcd (%) for C58H58BF20Pr\u22c52\u2009CH2Cl2: C, 49.47; H, 4.29; Found: C, 47.68; H, 4.27. \u03bceff : 2.70\u2005\u03bcB. The paramagnetism of 1\u2010Pr precluded assignment of its 1H and 13C{1H}\u2005NMR spectra. 11B{1H}\u2005NMR : \u03b4=\u221219.42\u2005ppm (s). 19F{1H}\u2005NMR : \u03b4=\u2212172.86 , \u2212166.16 , \u2212136.51\u2005ppm . FTIR : \u03bd\u02dc=2963 (m), 2909 (w), 2871 (w), 1643 (m), 1460 (s), 1365 (m), 1261 (s), 1242 (w), 1086 (s), 1021 (m), 977 (s), 798 (s), 774 (m), 755 (m), 683 (s), 660 (s), 609 (w), 573 (m), 473 (w), 441\u2005cm\u22121 (w).1\u2010Nd: Green crystals . Anal. Calcd (%) for C58H58BF20Nd\u22c52\u2009CH2Cl2: C, 49.36; H, 4.28; Found: C, 49.51; H, 4.17. \u03bceff : 3.42\u2005\u03bcB. 1H\u2005NMR : \u03b4=\u221217.88 3), \u221211.94\u2005ppm 3); no other signals observed. 11B{1H} NMR : \u03b4=\u221218.55\u2005ppm (s). The paramagnetism of 1\u2010Nd precluded assignment of its 13C{1H}\u2005NMR spectrum. 19F{1H}\u2005NMR : \u03b4=\u2212170.31 , \u2212164.92 , \u2212135.17\u2005ppm . FTIR : \u03bd\u02dc=2967 , 2875 (w), 2820 (w), 1643 (m), 1512 (s), 1460 (s), 1394 (w), 1365 (m), 1254 (w), 1241 (w), 1087 (s), 977 (s), 955 (w), 924 (w), 829 (m), 773 (s), 756 (s), 683 (s), 660 (s), 609 (w), 574 (m), 477 (w), 440\u2005cm\u22121 (w).1\u2010Sm: Red crystals . Anal. Calcd (%) for C58H58BF20Sm: C, 53.74; H, 4.51; Found: C, 53.88; H, 4.49. \u03bceff : 1.90\u2005\u03bcB. The paramagnetism of 1\u2010Sm precluded assignment of its 13C{1H} NMR spectrum. 1H\u2005NMR : \u03b4=\u22121.37 3), 19.69\u2005ppm ; no other signals observed. 11B{1H}\u2005NMR : \u03b4=\u221216.76\u2005ppm (s). 19F{1H}\u2005NMR : \u03b4=\u2212167.89 , \u2212163.76 , \u2212133.13\u2005ppm . 1H\u2005NMR : \u03b4=\u22122.58 3), \u22120.90 3), 18.80\u2005ppm . 11B{1H}\u2005NMR : \u03b4=\u221216.32\u2005ppm (s). 19F{1H}\u2005NMR : \u03b4=\u2212168.96 , \u2212162.02 , \u2212131.93\u2005ppm . FTIR : \u03bd\u02dc=2964 , 2872 (w), 2796 (w), 1642 (m), 1512 (s), 1459 (s), 1367 (m), 1276 (m), 1239 (m), 1083 (s), 977 (s), 843 (w), 806 (w), 774 (m), 756 (m), 735 (m), 683 (m), 661 (s), 611 (w), 574 (w), 466 (w), 449\u2005cm\u22121 (w).ttt)2(Cl)]  (2\u2010Ln)[Ln(Cp: THF (30\u2005mL) was added to a Teflon tap\u2010appended ampoule containing a pre\u2010cooled (\u221278\u2009\u00b0C) mixture of LnCl3 (2\u2005mmol) and KCpttt (4\u2005mmol). The reaction mixture was allowed to warm to room temperature and heated in an oil bath at 80\u2009\u00b0C for 16\u2005hours. The solvent was removed in vacuo and toluene (30\u2005mL) was added. The reaction mixture was heated in an oil bath at 120\u2009\u00b0C for 16\u2005hours. The resultant suspension was allowed to settle for 3\u2005hours and filtered. The solution was concentrated to 2\u2005mL and stored at 8\u2009\u00b0C to afford crystals of 2\u2010Ln.2\u2010La: Colourless crystals . Anal. Calcd (%) for C34H58LaCl: C, 63.69; H, 9.12; Found: C, 63.57; H, 9.30. 1H\u2005NMR : \u03b4=1.25 3), 1.52 3), 6.51\u2005ppm . 13C{1H}\u2005NMR : \u03b4=31.19 (C(CH3)3), 32.86 (C(CH3)3), 34.50 (C(CH3)3), 34.68 (C(CH3)3), 114.78 (Cp\u2010CH), 138.17 (Cp\u2010C), 139.58\u2005ppm (Cp\u2010C). FTIR : \u03bd\u02dc=2956 (s), 2904 (w), 2869 (w), 1461 (m), 1389 (m), 1361 (s), 1260 (s), 1241 (m), 1091 , 1016 (s), 866 (w), 797 (s), 678 (s), 590 (w), 566 (w), 551 (w), 436\u2005cm\u22121 (w).2\u2010Ce: Orange crystals . Anal. Calcd (%) for C34H58CeCl: C, 63.57; H, 9.10. Found: C, 63.60; H, 9.22. \u03bceff : 2.34\u2005\u03bcB. The paramagnetism of 2\u2010Ce precluded assignment of its 13C{1H} NMR spectrum. 1H\u2005NMR : \u03b4=\u221213.06 3), \u22122.53\u2005ppm 3); no other signals observed. FTIR : \u03bd\u02dc=2954 (s), 2904 (m), 2868 (w), 1460 (s), 1389 (s), 1358 (s), 1241 (s), 1165 (m), 1001 (s), 958 (m), 816 (s), 774 (s), 678 (s), 566 (w), 436\u2005cm\u22121 (s).2\u2010Pr: Pale green crystals . Anal. Calcd (%) for C34H58PrCl: C, 63.49; H, 9.09; Found: C, 63.37; H, 9.22. \u03bceff : 3.35\u2005\u03bcB. The paramagnetism of 2\u2010Pr precluded assignment of its 13C{1H}\u2005NMR spectrum. 1H\u2005NMR : \u03b4=\u221236.08 3), \u22127.74\u2005ppm 3); no other signals observed. FTIR : \u03bd\u02dc=2955 (s), 2905 (m), 2869 (w), 1460 (s), 1389 (s), 1359 (s), 1241 (s), 1166 (m), 1001 (s), 959 (m), 832 (m), 818 (s), 775 (s), 679 (s), 567 (m), 437\u2005cm\u22121 (s).2\u2010Nd: Blue crystals . Anal. Calcd (%) for C34H58NdCl: C, 63.16; H, 9.04; Found: C, 61.22; H, 9.02. The paramagnetism of 2\u2010Nd precluded assignment of its 13C{1H}\u2005NMR spectrum. \u03bceff : 3.55\u2005\u03bcB. 1H\u2005NMR : \u03b4=\u221218.95 3), \u22125.58\u2005ppm 3); no other signals observed FTIR : \u03bd\u02dc=2955 (s), 2907 (m), 2870 (w), 1460 (s), 1389 (s), 1358 (s), 1241 (s), 1166 (m), 1001 (s), 833 (s), 820 (s), 775 (s), 679 (s), 439\u2005cm\u22121 (s).2\u2010Sm: Yellow crystals . Anal. Calcd (%) for C34H58SmCl: C, 62.57; H, 8.96; Found: C, 60.93; H, 9.19. \u03bceff : 1.69\u2005\u03bcB. The paramagnetism of 2\u2010Sm precluded assignment of its 13C{1H}\u2005NMR spectrum. 1H\u2005NMR : \u03b4=\u22126.01 3), 0.55 3), 19.80\u2005ppm . FTIR : \u03bd\u02dc=2956 (s), 2905 (m), 2870 (w), 1460 (s), 1389 (s), 1356 (s), 1241 (s), 1221 (w), 1166 (s), 1000 (s), 959 (m), 836 (w), 824 (s), 776 (s), 679 (s), 591 (w), 438\u2005cm\u22121 (s).The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "Scientific Reports 10.1038/s41598-017-01160-1, published online 21 April 2017Correction to: This Article contains errors in the first column of Table\u00a0In addition, Table \u201coral 200\u2009mg preoperative\u201dshould read:\u201coral 200\u2009\u03bcg preoperative\u201d"}
{"text": "In salt(II), the anion consists of a 4-meth\u00adoxy\u00adbenzene\u00adsulfonate ion, and it crystallizes as a monohydrate.The title mol\u00adecular salts are stilbazole, or 4-styryl\u00adpyridine, derivatives in which the cation has a methyl group attached to the pyridine ring N atom and a diethyl amine group attached to the benzene ring. In salt (I), the cadmium atom of the [CdI 18H23N2)2[CdI4], (I), and C18H23N2+\u00b7C7H7O4S\u2212\u00b7H2O, (II), are stilbazole, or 4-styryl\u00adpyridine, derivatives. The cation, (E)-4-[4-(di\u00adethyl\u00adamino)\u00adstyr\u00adyl]-1-methyl\u00adpyridin-1-ium, has a methyl group attached to pyridine ring and a diethyl amine group attached to the benzene ring. The asymmetric unit of salt (I), comprises one cationic mol\u00adecule and half a CdI4 dianion. The Cd atom is situated on a twofold rotation axis and has a slightly distorted tetra\u00adhedral coordination sphere. In (II), the anion consists of a 4-meth\u00adoxy\u00adbenzene\u00adsulfonate and it crystallizes as a monohydrate. In both salts, the cations adopt an E configuration with respect to the C=C bond and the pyridine and benzene rings are inclined to each other by 10.7\u2005(4)\u00b0 in (I) and 4.6\u2005(2)\u00b0 in (II). In the crystals of both salts, the packing is consolidated by offset \u03c0\u2013\u03c0 stacking inter\u00adactions involving the pyridinium and benzene rings, with centroid\u2013centroid distances of 3.627\u2005(4)\u2005\u00c5 in (I) and 3.614\u2005(3)\u2005\u00c5 in (II). In the crystal of (II), a pair of 4-meth\u00adoxy\u00adbenzene\u00adsulfonate anions are bridged by Owater\u2014H\u22efOsulfonate hydrogen bonds, forming loops with an R24(8) motif. These four-membered units are then linked to the cations by a number of C\u2014H\u22efO hydrogen bonds, forming slabs lying parallel to the ab plane.The title mol\u00adecular salts, (C This shows that both compounds exhibit very good anti\u00adcancer activity, which implies that they may be suitable for biomedical applications.Stilbene-based compounds have been reported to possess a wide range of biological applications including anti\u00adbacterial (Chanawanno E)-4-[4-(di\u00adethyl\u00adamino)\u00adstyr\u00adyl]-1-methyl\u00adpyridin-1-ium. Their mol\u00adecular structures are illustrated in Fig.\u00a014]2\u2212 anion in the asymmetric unit, the cadmium atom being located on a twofold rotation axis. The cadmium atom is surrounded by four iodine atoms with a slightly distorted tetra\u00adhedral coordination sphere. In salt (II)E, with the C4\u2014C7=C8\u2014C9 torsion angle being 179.6\u2005(6) \u00b0 in (I)The title mol\u00adecular salts consist of the same cationic stilbazole derivative,  and benzene (C9\u2013C14) rings are 10.7\u2005(4) and 4.6\u2005(2)\u00b0 in (I)Cg2) and pyridine  rings .In the crystal of (I)water\u2014H\u22efOsulfonate hydrogen bonds, forming loops with an ab plane (Table\u00a01Cg2\u22efCg1ii = 3.614\u2005(3)\u2005\u00c5, \u03b1 = 4.6\u2005(2)\u00b0, \u03b2 = 15.5\u00b0, inter\u00adplanar distances are 3.425\u2005(2) and 3.484\u2005(2)\u2005\u00c5, offset = 0.963\u2005\u00c5, symmetry code: (ii) x\u00a0\u2212\u00a01, y, z].In the crystal of (II)f Table\u00a01. These fe Table\u00a01. Within et al., 2016et al., 2004ca 4.08\u00b0, while in the tetra\u00adphenyl\u00adborate salt A search of the Cambridge Structural Database \u00b0 in salt (II)p-toluene\u00adsulfonate anions via O\u2014H\u22efO hydrogen bonds, forming an There is only one salt reported with the title cation and a sulfonate anion, namely the Compound (I)E)-4-[4-(di\u00adethyl\u00adamino)\u00adstyr\u00adyl]-1-methyl-pyridinium-iodide  and cadmium iodide  were dissolved in a composite solvent, 2:1 ratio of aceto\u00adnitrile and double-distilled water. The mixture was stirred well at 343\u2005K and then allowed to cool naturally to room temperature. The solution was filtered and the filtrate left for the solvent to slowly evaporate at room temperature. After 3\u20134 weeks, dark-brown block-like crystals of compound (I)(Compound (II)E)-4-[4-(di\u00adethyl\u00adamino)\u00adstyr\u00adyl]-1-methyl\u00adpyridinium iodide  was mixed with sodium 4-meth\u00adoxy\u00adbenzene\u00adsulfonate  in distilled water and heated at 373\u2005K for 30\u2005min. The mixture immediately yielded a grey precipitate of sodium iodide. After stirring the mixture for 30\u2005min, the sodium iodide precipitate was removed. The filtrate was left to slowly evaporate and gave a deep-red solid. Red block-like crystals of compound (II)(Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for other H atoms. The rotation angles for the methyl groups were optimized by least-squares. In compound (II)d(O\u2014H) = 0.85\u2005\u00c5 and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details for salts (I)10.1107/S2056989018016808/su5462sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018016808/su5462Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018016808/su5462IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018016808/su5462IIsup4.cmlSupporting information file. DOI: 1589674, 1589675CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-(pyridin-2-ylmeth\u00adyl)benzamide derivative, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit, which differ essentially in the orientation of the pyridine ring with respect to the benzene ring, with the two rings being inclined to each other by 53.3\u2005(2) and 72.9\u2005(2)\u00b0 in mol\u00adecules A and B, respectively.The title  18H18F2N2O3, crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. They differ essentially in the orientation of the pyridine ring with respect to the benzene ring; these two rings are inclined to each other by 53.3\u2005(2)\u00b0 in mol\u00adecule A and by 72.9\u2005(2)\u00b0 in mol\u00adecule B. The 3-(cyclo\u00adpropyl\u00admeth\u00adoxy) side chain has an extended conformation in both mol\u00adecules. The two mol\u00adecules are linked by a pair of C\u2014H\u22efO hydrogen bonds and two C\u2014H\u22ef\u03c0 inter\u00adactions, forming an A\u2013B unit. In the crystal, this unit is linked by N\u2014H\u22efO hydrogen bonds, forming a zigzag \u2013A\u2013B\u2013A\u2013B\u2013 chain along [001]. The chains are linked by C\u2014H\u22efN and C\u2014H\u22efF hydrogen bonds to form layers parallel to the ac plane. Finally, the layers are linked by a third C\u2014H\u22ef\u03c0 inter\u00adaction, forming a three-dimensional structure. The major contributions to the Hirshfeld surface are those due to H\u22efH contacts (39.7%), followed by F\u22efH/H\u22efF contacts (19.2%).The title compound, C The dihedral angle between the benzamide ring and the pyridine ring is 53.3\u2005(2)\u00b0 in mol\u00adecule A and 72.9\u2005(2)\u00b0 in mol\u00adecule B. The cyclo\u00adpropane ring makes a dihedral angle of 57.7\u2005(5)\u00b0 with the benzene ring in mol\u00adecule A and 58.7\u2005(4)\u00b0 in mol\u00adecule B. The sum of the bond angles around atom N1 (359.9\u00b0) is in accordance with sp2 hybridization in both mol\u00adecules. The bond lengths and bond angles in both mol\u00adecules are comparable with those reported for a similar compound, 3-(cyclo\u00adpropyl\u00admeth\u00adoxy)-N--4-(di\u00adfluoro\u00admeth\u00adoxy) benzamide -4-(di\u00adfluoro\u00admeth\u00adoxy) benzamide  are very similar. Considering the low-temperature phase PEDWOM only, in each mol\u00adecule the benzene and pyridine rings are positioned almost perpendicular to each other, with dihedral angles of 88.38\u2005(14), 89.34\u2005(14) and 84.72\u2005(14)\u00b0, compared to 53.3\u2005(2) and 72.9\u2005(2)\u00b0 for mol\u00adecules A and B, respectively, in the title compound. In PEDWOM the cyclo\u00adpropane ring makes dihedral angles of 55.43\u2005(3), 49.6\u2005(3) and 50.9\u2005(3)\u00b0 with the corresponding benzene ring. These dihedral angles are very similar to those observed in the title structure [57.7\u2005(5)\u00b0 in mol\u00adecule A and 58.7\u2005(4)\u00b0 in mol\u00adecule B]. In the second compound, methyl 3-(cyclo\u00adpropyl\u00admeth\u00adoxy)-4-hy\u00addroxy\u00adbenzoate , followed by F\u22efH/ H\u22efF at 19.2% , C\u22efH/H\u22efC at 16.6% , O\u22efH/ H\u22efO at 14.0% , N\u22efH/H\u22efN at 6.8% . Hence, the H\u22efH and F\u22efH/H\u22efF inter\u00admolecular contacts are the most abundant in the crystal packing, and make the most significant contributions to the total Hirshfeld surfaces.The Hirshfeld surface analysis  in methanol were heated first to 393\u2005K for 2\u2005h in the presence of the inexpensive ionic liquid tetra\u00adbutyl\u00adammonium bromide (TBAB). The reaction was monitored by TLC, and on completion the reaction mixture was allowed to cool to room temperature, then filtered to remove the insoluble solids. The filtered solid was then washed with di\u00adchloro\u00admethane. Excess solvents were removed under reduced pressure and the obtained crude product was purified by crystallization using 1:1 ratio of chloro\u00adform and methanol. Colourless block-like crystals were obtained after two days.A mixture of 4-(di\u00adfluoro\u00admeth\u00adyl)-3-hy\u00addroxy\u00adbenzoic acid (2\u2005mmol), (chloro\u00admeth\u00adyl)cyclo\u00adpropane (2\u2005mmol) and 2-picolyl\u00adamine (3\u2005mmol) with PPhUiso(H) =1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The absolute structure of the mol\u00adecules in the crystal are unknown; the Flack parameter refined to 0.6\u2005(3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019012866/su5514sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019012866/su5514Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019012866/su5514Isup3.cmlSupporting information file. DOI: 1954107CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Though such interactions are commonly attributed to \u201csigma-hole\u201d-type electrostatic effects, we show that they exhibit profound similarities and analogies to the resonance-type 3-center, 4-electron (3c/4e) donor-acceptor interactions of hydrogen bonding, where classical-type \u201celectrostatics\u201d are known to play only a secondary modulating role. The general 3c/4e resonance perspective corresponds to a continuous range of interatomic A\u00b7\u00b7\u00b7B bond orders (bAB), spanning both the stronger \u201ccovalent\u201d interactions of the molecular domain  and the weaker interactions  that underlie supramolecular complexation phenomena. We show how a unified NBO/NRT-based description of hydrogen, halogen, pnicogen, and related bonding yields an improved predictive utility and intuitive understanding of empirical trends in binding energies, structural geometry, and other measurable properties that are expected to be manifested in all such supramolecular interaction phenomena.We employ a variety of natural bond orbital (NBO) and natural resonance theory (NRT) tools to comprehensively investigate the nature of halogen and pnicogen bonding interactions in RPH Recent computational ,2,3,4 annB\u2192\u03c3*AH donor\u2013acceptor interaction between the lone pair (nB) of the Lewis base B and the valence antibond (\u03c3*AH) of the Lewis acid A\u2014H. In natural resonance theory (NRT) [nB\u2192\u03c3*AH interaction represents resonance mixing between the parent natural Lewis structure (NLS) I and the secondary \u201ccharge\u2013transfer\u201d resonance structure II (with respective NRT weightings wI and wII):bAH, bBH bond orders are necessarily related by the characteristic \u201cbond conservation\u201d relationship [wI + wII = 1) for the composite resonance hybrid. Even in the absence of NRT bond order descriptors, the importance of NBO nB\u2192\u03c3*AH delocalization can be assessed by 2nd-order perturbative energy (\u0394E(2)n\u03c3*), intermolecular charge-transfer (Qn\u03c3*), or the deletion of this NBO interaction (\u0394E$DELn\u03c3*), as well as the variational recalculation of structure, energetics, and vibrational frequencies [In the case of hydrogen bonding, the primacy of short-range covalency forces is now widely recognized ,36,37,38ry (NRT) ,41,42,43rchanged . As recorchanged , the resrchanged ,47. In ttionship ,bAH + bquencies . In contquencies  that mos2\u00b7\u00b7\u00b7IF/FI  that exhibit a wide range of binding strengths. A smaller subset of such species was previously examined [In the present work, we take up the analogous covalency versus electrostatics questions for title complexes RPHexamined  with an examined .n-\u03c3* interaction) is strictly absent in uncorrelated Hartree\u2013Fock theory. Though an empirical dispersion correction [3PH2\u00b7\u00b7\u00b7IF (see Ebind). Such \u201ccorrections\u201d are not considered further in the present work. Note that we ignore the weaker effects of the London dispersion interaction , a pure rrection  is oftenE(2)n\u03c3*, charge\u2013transfer Qn\u03c3*, and $DEL-deletion \u0394E$DELn\u03c3* measures of donor\u2013acceptor attraction [E(pw)n\u03c3) of filled orbitals [In the following, we first describe the species, computational levels, and NBO/NRT methods to be employed. The latter include NBO \u0394traction , the cororbitals  that comorbitals . We then2\u00b7\u00b7\u00b7XY that included all possible  dihalogen species of the first four periodic rows. However, from a qualitative conceptual perspective, it soon became apparent that the properties of such complexes vary in a smooth and chemically reasonable fashion with dihalogen polarity, as maximized in the iodine\u2013fluorine (IF) species. Accordingly, we focus here on the \u201cpolar extremes\u201d of RPH2\u00b7\u00b7\u00b7IF versus RPH2\u00b7\u00b7\u00b7FI complexation, corresponding to opposed signs of any envisioned \u201cdipole\u2013dipole\u201d contributions to intermolecular binding. A direct comparison of these two extremes thereby allows one to recognize the important modulating influence of classical dipole\u2013dipole forces , while also verifying that resonance-type covalency forces yield robust supramolecular bonding even when the presumed classical electrostatic prerequisites for such complexation are profoundly violated. While the computational results presented here focus only on the extremal RPH2\u00b7\u00b7\u00b7IF versus RPH2\u00b7\u00b7\u00b7FI limits of this broader picture, the Our studies began with a larger data set of dihalogen complexes RPH2 monomers and LANL2DZ for dihalogen monomers of each complex. We employ simple B3LYP density functional methodology throughout this work, but alternative MP2 evaluations at different basis levels were also performed for comparison (see SI). All structures were optimized, and frequencies were computed to confirm equilibrium geometries corresponding to minimum energy points. The binding energy, \u0394Ebind = E(AB) \u2212 E(A) \u2212 E(B), was calculated as the direct energy difference between optimized dimer and relaxed monomers. All electronic structure calculations were performed with the Gaussian 16 program package [NBO 7.0 software [NBOPro@Jmol program [Though the conceptual picture we describe is insensitive to many details of the chosen computational method and basis set , the inc package . NBO/NRTsoftware , and bot program .2\u00b7\u00b7\u00b7IF and RPH2\u00b7\u00b7\u00b7FI species as obtained at the adopted \u201cB3LYP/mixed-PP\u201d level, showing the wide range of tuning by various R-substituents. Despite the fact that all complexes are appreciably bound , interesting structural contrasts are immediately evident between these two classes of species. Focusing first on the orientation angles (\u0398) in 2\u00b7\u00b7\u00b7IF species all maintain nearly linear P\u00b7\u00b7\u00b7IF alignment (\u0398PIF \u2248 180\u00b0) and a circa 120\u00b0 bend angle between RP and IF axes (\u0398RPI \u2248 120\u00b0). In contrast, the RPH2\u00b7\u00b7\u00b7FI species are noticeably tilted away from P\u00b7\u00b7\u00b7FI linearity (\u0398PFI \u2248 160\u00b0), instead adopting increasingly near-linear alignment with respect to RP and FI axes (\u0398RPF \u2248 170\u00b0). Such structural tendencies suggest that the principal underlying \u201clinearizing\u201d (H-bond-like) interaction differs in the two cases and that other RPH2\u00b7\u00b7\u00b7XY dihalogen species of intermediate polarity will likewise exhibit intermediate orientational preferences between these two competing tendencies. Indeed, this is the broader picture obtained from the full set  of optimized dihalogen structures, with the homopolar RPH2\u00b7\u00b7\u00b7X2 species forming the approximate \u201cdividing line\u201d between RPH2\u00b7\u00b7\u00b7IF-like versus RPH2\u00b7\u00b7\u00b7FI-like structural propensity. These structural features of RPH2\u00b7\u00b7\u00b7IF-like (\u201cP\u00b7\u00b7\u00b7IF\u201d) versus RPH2\u00b7\u00b7\u00b7FI-like (\u201cRP\u00b7\u00b7\u00b7F\u201d) complexes are also consistently exhibited at other theory levels, as shown in SI 2\u00b7\u00b7\u00b7IF versus RPH2\u00b7\u00b7\u00b7FI species for describing the full range of RPH2\u00b7\u00b7\u00b7XY complexation , including general consistency with previous MP2/aug-cc-pVTZ-level calculations.RP\u00b7\u00b7\u00b7F or RP\u00b7\u00b7\u00b7I  with increasing binding energy \u0394Ebind is also discernable in the details of the figure panels. From both Ebind with various R-substituents for the strongly bound complexes of the RPH2\u00b7\u00b7\u00b7IF type. The graph includes comparison values for the alternative theory levels given in IF with respect to the R-substituent . As shown in the figure, \u0394\u03bdIF is strongly red-shifted for the most strongly bound complexes, similar to the well-known spectroscopic signature of H-bonding. IF  between these experimentally observable quantities that confirms the similarity to H-bonding.ding. IF  versus \u0394F  to achieve the net binding energies displayed in Ebind binding affinity and RP\u00b7\u00b7\u00b7I separation in the deep sub-vdW region.Returning to the structural data of 2\u00b7\u00b7\u00b7IF and weak RPH2\u00b7\u00b7\u00b7FI complexes, the structural features hint at striking resemblances to familiar H-bonding phenomena, including deep sub-vdW penetration  and pronounced \u201clinearization\u201d tendency . We take up NBO/NRT investigation of these apparent similarities and bonding relationships in the following sections.The computed structural and binding characteristics noted above identify the propensities and patterns to be explained and provide helpful clues to the nature of the underlying attractive forces. Even the more weakly bound complexes of the P\u00b7\u00b7\u00b7FI type exhibit optimized P\u00b7\u00b7\u00b7F distances (2.1\u20132.6\u00c5) that lie significantly (>0.5\u00c5) inside vdW contact  donor\u2013acceptor interactions of the present species.As suggested in  above, an NBO/NRT analysis of B:\u00b7\u00b7\u00b7HA hydrogen-bonding phenomena reveals a host of characteristic correlations ,23,60 thanalysis ,62,63. Tanalysis ,66,67,682\u00b7\u00b7\u00b7IF complexes, the key feature of envisioned P\u00b7\u00b7\u00b7I\u2014F \u201chalogen bonding\u201d is the donor\u2013acceptor delocalization of electronic charge from an occupied donor NBO of P (lone pair nP) to the favorably polarized acceptor NBO (antibond \u03c3*IF) of the P\u00b7\u00b7\u00b7I\u2014F triad. For RPH2\u00b7\u00b7\u00b7FI complexes, where the nP-\u03c3*IF overlap is unfavorable, the analogous feature of envisioned F\u00b7\u00b7\u00b7P\u2014R \u201cpnicogen bonding\u201d is the donation from a fluorine lone pair (nF) to the proximal antibond (\u03c3*PR) of the phosphine monomer. Each such n\u2192\u03c3* delocalization can be alternatively quantified in terms of energetic (perturbative \u0394E(2)n\u03c3* or variational deletion \u0394E($DEL)n\u03c3*), charge transfer (Qn\u03c3*), or fractional NRT bond order (bP\u00b7\u00b7\u00b7I or bP\u00b7\u00b7\u00b7F) descriptors.The analogies of the preceding section suggest appropriate NBO/NRT descriptors for the corresponding \u00b7\u00b7\u00b7X\u2014 (\u201cX-ogen\u201d) species that can be similarly visualized in simple orbital overlap terms. For RPHEn\u03c3* stabilization energy associated with each type of delocalization in the strongly bound RPH2\u00b7\u00b7\u00b7IF species. The first two columns display 2nd-order perturbative \u0394E(2)n\u03c3* estimates for nP\u2192\u03c3*IF  and nI\u2192\u03c3*PR (\u201cpnicogen bond\u201d) contributions. The final two columns of E($DEL)n\u03c3* variational deletion estimates, obtained as the variational energy raising when the specific n\u2192\u03c3* NBO interaction is deleted from the total energy evaluation. The two estimates are seen to be in reasonable qualitative agreement for each interaction type. The \u0394E(2)n(P)\u2192\u03c3*(IF) values range from 19 to 37 kcal/mol (in the same order as \u0394Ebind), whereas \u0394E(2)n(I)\u2192\u03c3*(FI) is relatively negligible in each case, and a similar pattern is seen in the \u0394E($DEL)n\u03c3* values. We therefore expect that the stabilization energy of the nP\u2192\u03c3*IF interaction is the dominant attractive contribution to the structure and binding of RPH2\u00b7\u00b7\u00b7IF complexes, similar to the dominance of the nB\u2192\u03c3*AH interaction in H-bonding.2\u00b7\u00b7\u00b7FI species, the situation is more complex. Due to the unfavorable polarization of \u03c3*FI away from the nP lone pair, the single nP\u2192\u03c3*IF interaction that dominates bonding in RPH2\u00b7\u00b7\u00b7IF species becomes only one of several such competing contributions to net binding. Specifically, for the opposed F\u00b7\u00b7\u00b7P\u2014R (pnicogen bonding) motif, three possible nF lone pairs (one of sigma type and two of pi type) and three \u03c3*PY acceptors (one \u03c3*RP and two \u03c3*PH) are within proximal interaction range as potential contributors to a complex resonance mixture. A particular interaction such as nF(\u03c3)\u2192\u03c3*RP therefore represents only one of the nine related n\u2192\u03c3* interactions that may exert leverage on angular structure and binding energy. In such a case, only a more nuanced resonance-type description (see the discussion of NRT bond orders below) can describe the complete bonding picture that provides useful correlations with experimentally measurable properties. We therefore defer further discussion of RPH2\u00b7\u00b7\u00b7FI complexes to a later subsection.For the weakly bound RPHn\u2192\u03c3* interactions of halogen  or pnicogen (nI(\u03c0)\u2192\u03c3*RP, nI(\u03c3)\u2192\u03c3*RP; final two columns) types, with corresponding numerical \u0394E(2)n\u03c3* values  is much stronger than the \u201cedge-on\u201d (pi-type) overlap of \u03c3*RP with the in-plane iodine nI(\u03c0) (middle panel) or nI(\u03c3) (right panel) lone pairs, in accordance with the \u0394E(2)n\u03c3* values shown in each panel. Even a casual glance at the overall patterns of the orbital overlap in nP\u2192\u03c3*IF) rather than pnicogen-type (nI(\u03c0)\u2192\u03c3*RP, nI(\u03c3)\u2192\u03c3*RP) bonding throughout the RPH2\u00b7\u00b7\u00b7IF series, as numerically displayed in For example, in the three panels for CHEn\u03c3* stabilization energies of Ebind binding energies of En\u03c3 donor\u2013donor interaction. E(pw)n-\u03c3 for repulsive \u201csteric exchange energy\u201d [2\u00b7\u00b7\u00b7IF series. As shown in the panels, the two leading intermolecular repulsions refer to the nP-nI steric clash between lone pairs of proximal P and I atoms (left) and nP-\u03c3IF clash between a lone pair and bond of the halogen bond P\u00b7\u00b7\u00b7I\u2014F triad. However, weaker nI-\u03c3PR, nI-\u03c3PH clashes of the alternative pnicogen bond triads  also contribute to sub-vdW steric opposition, thereby further offsetting the apparently \u201cexcessive\u201d NBO estimate of donor\u2013acceptor attraction needed to achieve the final equilibrium geometry and net binding energy.Though the donor\u2013acceptor \u0394 energy\u201d  between nP, nI, and \u03c3IF NBOs (not shown) similarly serve to rationalize the trends in repulsive donor\u2013donor interactions n(P)\u2192\u03c3*(IF) evaluations of n\u2192\u03c3* donor\u2013acceptor strength in the equilibrium species (E($DEL)n(P)\u2192\u03c3*(IF) potential energy surface in which n\u2192\u03c3* delocalization is absent, as though nature (in accordance with common textbook presentations) failed to include such interactions.Still another widget from the NBO toolbox can be used to exhibit the profound effects of  species , one can2\u00b7\u00b7\u00b7IF dissociation, with the nP\u2192\u03c3*IF interaction deleted. Starting from the equilibrium values of the actual RPH2\u00b7\u00b7\u00b7IF species, the distance variables RP\u00b7\u00b7\u00b7I, RIF  were optimized to find the new binding energy (\u0394Ebind) and shifts  that describe the hypothetical \u201cresonance-free\u201d RPH2\u00b7\u00b7\u00b7IF that lacks nP\u2192\u03c3*IF donor\u2013acceptor attraction. From the resulting values, one sees that characteristic structural and energetic signatures of RPH2\u00b7\u00b7\u00b7IF bonding are lost when the nP\u2192\u03c3*IF interaction is \u201cturned off;\u201d the RPH2 and IF monomers retreat (by circa 1.3\u00c5) to beyond-vdW separation, the characteristic RIF elongation  from isolated monomer geometry essentially disappears, and the net binding energy drops precipitously (by >80%) to a remnant value that might plausibly be associated with residual \u201cdipole\u2013dipole\u201d forces. Note that the monomer dipole moments or other aspects of electron density distribution are scarcely altered in the $DEL-reoptimized geometry, and the \u201clost\u201d energy of nP\u2192\u03c3*IF stabilization is negligibly small  at the reoptimized separation distance. From the results of such $DEL-deletion calculations, one recognizes nP\u2192\u03c3*IF stabilization to be the unique \u201csmoking gun\u201d that is both necessary and sufficient to bring the supramolecular complex to the actual short-range geometry and other signatures of halogen bonding, which is in direct correspondence to the analogous nB\u2192\u03c3*HA role in H-bonding.n\u2192\u03c3* interactions lead to net binding against the essentially repulsive potential curve for hypothetical monomers that interact without benefit of resonance-type stabilization. 3PH2\u00b7\u00b7\u00b7IF dissociation, showing the potential curve for the fully interacting monomers . The \u201cmissing\u201d resonance-type (purely attractive) interactions are shown as the difference curve . The blue curve exhibits a feeble attractive well beyond vdW contact at RP\u00b7\u00b7\u00b7I \u2248 4.0\u00c5 (presumably due to \u201cdipole\u2013dipole\u201d attraction) but rises steeply as a repulsive steric wall in the sub-vdW region. Already in the region of the initial sub-vdW penetration, the red curve (n\u2192\u03c3* resonance attraction) has achieved sufficient stabilization to oppose thermal fluctuations  and yield significant sub-vdW binding in the black  curve down to RP\u00b7\u00b7\u00b7I \u2248 2.9 equilibrium separation. Inside this equilibrium distance, the intermolecular n-\u03c3 steric repulsion overcomes n-\u03c3* attraction to give the steeply repulsive inner wall of the full potential, resonance-shifted inside circa 2.5\u00c5. Where such nP-\u03c3IF versus nP-\u03c3*IF \u201ccross-over\u201d occurs will evidently depend on the polarization of the dihalogen bond and is therefore expected to shift to a progressively larger RP\u00b7\u00b7\u00b7I separation (and weakened \u0394Ebind) for other members of the dihalogen series, thereby appearing as a secondary \u201celectrostatic\u201d modulating effect on the overall halogen bonding phenomenon.Still another use of $DEL-deletion techniques is to prepare relaxed-scan potential curves that illustrate how intermolecular 2\u00b7\u00b7\u00b7IF species  tends to increase steadily with strength of RPH2\u00b7\u00b7\u00b7IF binding or net QCT. This trend reflects the expected dominance of the nP\u2192\u03c3*IF interaction, which is evidently enhanced . The combined effect of repolarization (iIF) and net charge transfer (QCT) is to give a somewhat irregular pattern to individual atomic charges qI, qF, but all such IF charge descriptors are seen to properly \u201cadd up,\u201d as they must according to the strict logic of a natural population analysis.city iIF ), compar2 monomer, the phosphorus charge qP reflects the still more complex effects of sigma-type induction versus intra- and intermolecular lone pair delocalizations. One can see in the table the evident effect of bonding the phosphorus to more electronegative oxygen (qP \u2248 0.73) or nitrogen (qP \u2248 0.45) rather than carbon (qP \u2248 0.3\u20130.4). However, also important in the present context is the intra- versus intermolecular competition for charge donation from the \u201cbusy\u201d phosphorus lone pair nP to various pi-type acceptor orbitals of the R-substituent  versus the intermolecular nP\u2192\u03c3*IF interaction of principal interest.In the RPHbAB}, which balance the nuances of multiple resonance structure contributions to give a single composite measure of A\u00b7\u00b7\u00b7B \u201cconnectivity.\u201d As described elsewhere [NBO 7.0 program [Perhaps the most useful and general descriptors of supramolecular bonding are NRT bond orders {lsewhere ,41,42,43lsewhere   versus the \u201cnoncovalent interaction\u201d (dots). Most surprising in these species are the non-vanishing bond orders for the \u201clong-bond\u201d [2\u00b7\u00b7\u00b7IF species, certain P^I long bonds achieve bond orders that rival or exceed those of familiar bP\u00b7\u00b7\u00b7F or bIF linkages .The first three columns of ng-bond\u201d ,77,78 inThe final two columns of E(2)n\u03c3*, \u0394E($DEL)n\u03c3*, Qn\u03c3*,...) intrinsically focus on orbitals of a specific n\u2192\u03c3* \u201cdelocalization\u201d from a specific Lewis structural bonding pattern. Such orbital-specific descriptors are valuable when a single \u201cparent\u201d Lewis structure and \u201cchild\u201d n\u2192\u03c3* delocalization clearly dominate quantum mechanical descriptions of the structural, energetic, and spectroscopic properties of the chosen system. However, for many chemical systems of interest (including the RPH2\u00b7\u00b7\u00b7FI species considered here), multiple n\u2192\u03c3* interactions come into play, corresponding to contributions of alternative resonance\u2013structural bonding patterns that may no longer be \u201cchild-like\u201d compared to a reference parent pattern. Such cases demand the more nuanced NRT descriptors such as interatomic bond orders {bAB} that balance the many possible orbital interactions contributing to the overall resonance hybrid.The principal NBO descriptors of donor\u2013acceptor interactions  makes them better adapted to describe empirical correlations with measurable properties. Well-known examples include bond order\u2013bond length (bAB-RAB) [n\u2192\u03c3* limit  as well as the more general correlations of NRT bond orders with experimentally measurable properties, spanning the full set of RPH2\u00b7\u00b7\u00b7IF/FI species considered in this work.As could be anticipated from the empirical origins of bond order descriptors in the pre-quantum mechanical conceptions of \u201cmesomerism\u201d theory , the \u201cavbAB-RAB) , bond orbAB-RAB) , and bonbAB-RAB)  relation2\u00b7\u00b7\u00b7IF series, in which the nP\u2192\u03c3*IF interaction plays a clearly dominant role, we first consider the mutual correlations of \u0394E(2)n\u03c3*, \u0394E($DEL)n\u03c3*, Qn\u03c3*, bP\u00b7\u00b7\u00b7I descriptors for this interaction. Taking perturbative \u0394E(2)n\u03c3* as the base descriptor for the group, we display (a) \u0394E(2)n\u03c3*-\u0394E($DEL)n\u03c3*, (b) \u0394E(2)n\u03c3*-Qn\u03c3*, and (c) \u0394E(2)n\u03c3*-bP\u00b7\u00b7\u00b7I correlation diagrams in successive panels (a)\u2013(c) of 2 correlation coefficients demonstrate the high quality of these mutual correlations: In the range 0.94\u20130.99 for NBO-specific descriptors, but slightly lower (0.94) for correlation with the NRT bond order bP\u00b7\u00b7\u00b7I (presumably due to the proper inclusion of secondary donor\u2013acceptor interactions with R-substituents that are present only in the latter). The results show that descriptors of this group could be chosen rather interchangeably for correlations with measurable experimental properties when a single donor\u2013acceptor interaction such as nP\u2192\u03c3*IF is clearly dominant.Starting with the RPHRP\u00b7\u00b7\u00b7I or RP\u00b7\u00b7\u00b7F, (b) intramolecular RIF, (c) binding energy \u0394Ebind, or (d) infrared stretching frequency \u03bdIF, we employed the NRT bond order bAB  as base descriptor in the correlation diagrams of 2\u00b7\u00b7\u00b7IF  and RPH2\u00b7\u00b7\u00b7FI (red: Multi-resonance) series. As examples of bond order\u00adbond length correlations, bP\u00b7\u00b7\u00b7X-RP\u00b7\u00b7\u00b7X correlations  for each series, with reasonably high correlations (|\u03c7|2 = 0.92) in each case. bIF-RIF correlation for the dihalogen monomer, with still higher correlation coefficients . As examples of bond order\u2013bond energy correlation, bP\u00b7\u00b7\u00b7X-\u0394Ebind correlations , with similar correlation coefficients (|\u03c7|2 = 0.94) in each series. Finally, as bond order\u2013bond frequency examples, bIF-\u0394\u03bdIF correlations, again with high correlation coefficients . All these correlations suggest the high predictive utility of NRT bond orders for both the tuning effects of R-substituents and the polarity variations of the various dihalogen monomers that govern the broad range of binding energies in these supramolecular species.For more general correlations with measurable experimental properties such as (a) intermolecular 2\u00b7\u00b7\u00b7IF/FI, R = CH3, OH, CF3, CN, NO2), focusing on the electronic origin of what might be identified as a \u201chalogen bond,\u201d \u201cpnicogen bond,\u201d or some combination of both. For this purpose, we employed a broad variety of natural bond orbital (NBO) and natural resonance theory (NRT) descriptors, searching for relationships to hydrogen bonding or other known forms of intermolecular attraction .We have computationally investigated the nature of supramolecular bonding in a series of R-substituted phosphine\u00b7\u00b7\u00b7dihalogen complexes  is the dominant feature of halogen-type  or pnicogen-type  bonding motifs, just as for the dominant nB\u2192\u03c3*HA interaction of B:\u00b7\u00b7\u00b7H\u2014A hydrogen bonding. We obtained evidence both for resonance-type \u201cbond conservation\u201d rules and the complete set of mutually consistent correlations of NBO/NRT descriptors with experimentally measurable properties of RPH2\u00b7\u00b7\u00b7IF/FI complexes that closely parallel those previously demonstrated for H-bonded complexes. We also demonstrate that the removal of n\u2192\u03c3* interactions obliterates the signature features of halogen/pnicogen bonding, whereas such features persist  even if envisioned \u201cdipole\u2013dipole\u201d contributions are reversed . Thus, our results establish that resonance-type n\u2192\u03c3* stabilization is both necessary and sufficient for the characteristic structural, energetic, and spectroscopic features of halogen or pnicogen bonding, as was previously demonstrated for H-bonding [Our results show that resonance-type \u201c-bonding ,23. The -bonding ,83. Conn-bonding .n\u2192\u03c3* \u201cfractional bonding\u201d will be found for chalcogen bonds, tetrel bonds, and all other such supramolecular bonding phenomena. Our conclusions thereby extend \u201cresonance covalency\u201d concepts to the entire supramolecular domain of sub-integer bond orders, challenging the common \u201celectrostatic\u201d assumptions that underlie current empirical force field modeling and textbook expositions of supramolecular chemistry. Based on these results, we anticipate that similar unique associations with resonance-type"}
{"text": "The title compound crystallizes with two independent mol\u00adecules in the asymmetric unit. They differ essentially in the orientation of the 4-meth\u00adoxy\u00adphenyl ring with respect to the pyridine ring of the quinoline moiety. 34H28ClN3O3S, contains two independent mol\u00adecules (A and B). They differ essentially in the orientation of the 4-meth\u00adoxy\u00adphenyl ring with respect to the pyridine ring of the quinoline moiety; this dihedral angle is 37.01\u2005(18)\u00b0 in mol\u00adecule A but only 7.06\u2005(17)\u00b0 in mol\u00adecule B. In both mol\u00adecules, the cyclo\u00adhexa\u00adnone ring of the iso\u00adquinoline unit has a half-chair conformation. In the pyrrolo\u00adthia\u00adzole ring system, the pyrrolo ring in mol\u00adecule A has a twisted conformation on the N\u2014C fused bond and an envelope conformation in mol\u00adecule B with the N atom as the flap. The thia\u00adzole rings of both mol\u00adecules have twisted conformations on the N\u2014C fused bond. In the crystal, the A mol\u00adecules are linked by pairs of N\u2014H\u22efO hydrogen bonds, forming inversion dimers with an R22(8) ring motif. These dimers are linked to the B mol\u00adecules by an N\u2014H\u22efN hydrogen bond and a series of C\u2014H\u22efO hydrogen bonds, forming layers lying parallel to the (101) plane. The layers are linked by C\u2014H\u22ef\u03c0 inter\u00adactions and offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.427\u2005(1)\u2005\u00c5], forming a supra\u00admolecular framework. The contribution to the scattering from a region of highly disordered solvent mol\u00adecules was removed with the SQUEEZE routine in PLATON [Spek (2015The asymmetric unit of the title compound, CSpek 2015. Acta Cr In mol\u00adecule A, the dihedral angle between the two rings is 37.01\u2005(18)\u00b0 compared to 7.06\u2005(17)\u00b0 in B. There is also a slight difference in the orientation of the 4-chloro\u00adphenyl ring with respect to the mean plane of the pyrrolo ring, viz. in mol\u00adecule A benzene ring C11A\u2013C16A is inclined to the mean plane of the pyrrol ring (N1A/C1A\u2013C4A) by 86.12\u2005(17)\u00b0, while in mol\u00adecule B the corresponding dihedral angle is 76.92\u2005(17)\u00b0.The mol\u00adecular structure of the two independent mol\u00adecules, A/C21A/C22A/C26A\u2013C28A) in molecule A and (C2B/C21B/C22B/C26B\u2013C28B) in B] of the iso\u00adquinoline unit adopts a half-chair conformation in mol\u00adecule A  and a distorted half-chair conformation in mol\u00adecule B , the benzene and pyrrolidine rings make dihedral angles of 3.65\u2005(3) and 3.67\u2005(3)\u00b0 in mol\u00adecules A and B, respectively, while the keto atoms, O2A in mol\u00adecule A and O2B in mol\u00adecule B, deviate from the attached pyrrolidine rings by 0.1116\u2005(1) and 0.0176\u2005(1)\u2005\u00c5, respectively.In the indolin-2-one ring systems -1,2\u2032\u2032(1\u2032\u2032H)-dione methanol solvate -dione chloro\u00adform solvate -6-(4-chloro\u00adbenzyl\u00adidene)-2-(4-meth\u00adoxy\u00adphen\u00adyl)-7,8-di\u00adhydro\u00adquino\u00adlin-5(6H)-one (1\u2005mmol) was added and the reaction mixture was allowed to reflux for a further 14\u2005h. After completion of the reaction, as evident from TLC, the solvent was removed under reduced pressure and the residue washed with ice-cold water (50\u2005ml). The crude product was purified by column chromatography using 90:10 (v/v) petroleum ether\u2013ethyl acetate mixtures to obtain the pure product. The product was dissolved in ethyl acetate and poured into a beaker, covered with perforated film and kept undisturbed. The solvent was allowed to evaporate slowly, yielding colourless block-like crystals after a period of seven days .A mixture of isatin (1.1\u2005mmol) and thia\u00adzolidine-4-carb\u00adoxy\u00adlic acid (1.1\u2005mmol) was taken in 10\u2005ml of aceto\u00adnitrile in a 50\u2005ml round bottom flask and heated to reflux for 2\u2005h. Then (Uiso = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The residual electron density was difficult to model and therefore, the SQUEEZE routine in PLATON  contains approximately 100 electrons  global, I. DOI: 10.1107/S2056989019000112/su5469Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019000112/su5469sup3.pdfCSD search. DOI: 1888600CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-chromen-4-yl)\u00adoxy]acetamide derivatives are described and the inter\u00admolecular contacts in the crystals analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.The crystal structures of two 2-[(2-oxo-2 H-chromen-4-yl)\u00adoxy]acet\u00adyl}piperazin-1-yl)acetamide, C17H19N3O5, (I), and N--2-[(2-oxo-2H-chromen-4-yl)\u00adoxy]acetamide, C20H19NO6, (II), are new coumarin derivatives. In compound (I), the six-membered piperazine adopts a chair conformation. The dihedral angles between the mean planes of the chromene ring and amide plane is 82.65\u2005(7)\u00b0 in (I) and 26.2\u2005(4)\u00b0 in (II). The dihedral angles between the mean planes of the chromene ring and the four planar C atoms of the piperazine ring in (I) and the benzene ring in (II) are 87.66\u2005(6) and 65.0\u2005(4)\u00b0, respectively. There are short intra\u00admolecular contacts in both mol\u00adecules forming S(5) ring motifs, viz. N\u2014H\u22efN and C\u2014H\u22efO in (I), and N\u2014H\u22efO and C\u2014H\u22efN in (II). In the crystals of both compounds, mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds, forming chains along  present within the layers. In the crystal of (II), there are only weak offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.981\u2005(6)\u2005\u00c5] present within the layers. The inter\u00admolecular contacts in the crystals of both compounds have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.The title compounds, 2-(4-{2-[(2-oxo-2 The synthesis, and pharmacological and other properties of coumarin derivatives have been studied and reviewed (Kumar Q = 0.561\u2005(2)\u2005\u00c5, \u03b8 = 0.67\u2005(2)\u00b0 and \u03c6 = 149\u2005(2)\u00b0], and is positioned anti with respect to the C\u2014N rotamer of the amide. Nevertheless, because the asymmetry of the chromene residue, the anti conformation can assume a cis or trans geometry with respect to the relative position of the carbonyl O atom of the carboxamide and the C10\u2014C11 and C16\u2014C17 bonds. Both compounds exhibit a cis relation between these bonds, as can be seen in Figs. 1S(5) ring motifs. In addition, the carbonyl oxygen atom O4 acts as the acceptor for a weak inter\u00adaction with a hydrogen bond of the exocyclic piperazine ring, forming a second S(5) ring motif in (I)S(5) ring motif in (II)The mol\u00adecular structures of compounds (I)The values of the dihedral angles between the mean planes of the planar chromene ring system  and the amide plane (C10/C11/O4/N1) are 82.65\u2005(7) and 26.2\u2005(4)\u00b0 in compounds (I)N-(substituted phen\u00adyl)-4H-chromene-2-carboxamides  and C(7) chains formed via the C10\u2014H10A\u22efO5iii and N3\u2014H3A\u22efO4i hydrogen bonds, respectively. A C\u2014H\u22ef\u03c0 inter\u00adaction is also present within the layer (Table\u00a01Cg2\u22efCg2iv = 3.691\u2005(1)\u2005\u00c5, inter\u00adplanar distance = 3.490\u2005(1)\u2005\u00c5, offset = 1.20\u2005\u00c5; Cg2 is the centroid of the O1/C1\u2013C9 ring; symmetry code: (iv) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01].In the crystal of (I)ne Fig.\u00a03. The C14r Table\u00a01. An offsi hydrogen bonds, forming chains along the [010] direction, see Fig.\u00a04ii, C5\u2014H5\u22efO4i and C15\u2014H15\u22efO4iii hydrogen bonds, forming layers parallel to the ab plane \u2005\u00c5, inter\u00adplanar distances = 3.638\u2005(4) and 3.508\u2005(4)\u2005\u00c5, offset 0 1.88\u2005\u00c5; Cg2 and Cg3 are the centroids of rings C1\u2013C6 and C13\u2013C18, respectively; symmetry code: (iv) \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a01].In the crystal of (II)ne Fig.\u00a04. Within et al., 2019et al., 2007CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of \u22120.544 (red) to 1.418 (blue) for compound (I)The Hirshfeld surfaces of compounds (I)b) and O\u22efH/H\u22efO at 35.3% , followed by the C\u22efH/H\u22efC contacts at 11.8% . For compound (II)b) and O\u22efH/H\u22efO at 32.4% , followed by the C\u22efH/H\u22efC contacts at 16.7% . In both compounds, the H\u22efH inter\u00admolecular contacts predominate, followed by the O\u22efH/H\u22efO contacts. However the C\u22efH/H\u22efC contacts are significantly different 11.8% cf. 16.7% for (I)The fingerprint plots are given in Figs. 83% Fig.\u00a08c, follo8% Fig.\u00a08d. For c4% Fig.\u00a09c, follo7% Fig.\u00a09d. In boet al., 2016H-chromen-4-yl)\u00adoxy]acetamide derivatives gave two hits. They include 2-[(2-oxo-2H-chromen-4-yl)\u00adoxy]-N-(1-phenyl\u00adeth\u00adyl)acetamide -2-[(2-oxo-2H-chromen-4-yl)\u00adoxy]prop\u00adan\u00ada\u00admide  structures gave 35 hits. They include four reports, CSD refcodes AMYROL [Kato, 1970et al., 1982et al., 1985et al., 2011et al., 2014et al., 2017meta-substituted coumarin esters cyclo\u00adpropyl sulfamate (Morin Compound (I) To a solution of 1 equiv. of 4-(2-(piperazine-1-yl)eth\u00adoxy)-2H-chromen-2-one (1.0\u2005g) in di\u00adchloro\u00admethane (10\u2005ml) at 273\u2013278\u2005K were added tri\u00adethyl\u00adamine  followed by iodo\u00adacetamide , and the reaction mixture was stirred at the same temperature for 1\u2005h. On completion of the reaction (monitored by TLC), the reaction mixture was diluted with di\u00adchloro\u00admethane and water (10\u2005ml). The organic layer was separated and washed with brine solution. It was then dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure giving compound (I)Compound (II)N,N-Diiso\u00adpropyl\u00adethyl\u00adamine  was added to a mixture of 2-(2-oxo-2H-chromen-4-yl\u00adoxy)acetic acid , 1-ethyl-3-(3-di\u00admethyl\u00adamino\u00adprop\u00adyl)carbodi\u00adimide , 1-hy\u00addroxy\u00adbenzotriazole hydrate , 2,4-di\u00admeth\u00adoxy\u00adbenzyl\u00adamine  in N,N-di\u00admethyl\u00adformamide (5\u2005ml) at 273\u2013278\u2005K. The temperature of the mixture was raised to ambient temperature and stirred for 8\u2005h. Progress of the reaction was monitored by TLC (mobile phase: ethyl acetate/hexa\u00adne). After completion of the reaction, the mixture was poured into ice\u2013water and compound (II)Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019003736/su5482sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989019003736/su5482Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019003736/su5482IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019003736/su5482Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019003736/su5482IIsup5.cmlSupporting information file. DOI: 1891497, 1891496CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of three salicyaldoxime compounds are discussed together with Hirshfeld surface and fingerprint analyses. 8H9NO2, 1, 2,4-di\u00adhydroxy\u00adbenzaldehyde oxime, C7H7NO3, 2, and 2-hy\u00addroxy-4-meth\u00adoxy\u00adbenzaldehyde oxime, C8H9NO3, 3, are discussed. In each compound, the hydroxyl groups are essentially coplanar with their attached phenyl group. The inter\u00adplanar angles between the C=N\u2014O moieties of the oxime unit and their attached phenyl rings are 0.08\u2005(9), 1.08\u2005(15) and 6.65\u2005(15)\u00b0 in 1, 2 and 3, respectively. In all three mol\u00adecules, the 2-hy\u00addroxy group forms an intra\u00admolecular O\u2014H\u22efN(oxime) hydrogen bond. In compound (1), inter\u00admolecular O\u2014H(oxime)\u22efO(hydrox\u00adyl) hydrogen bonds generate R22(14) dimers, related by inversion centres. In compound 2, inter\u00admolecular O\u2014H(oxime)\u22efO(4-hy\u00addroxy) hydrogen bonds generate C9 chains along the b-axis direction, while O\u2014H(4-hydrox\u00adyl)\u22efO(2-hydrox\u00adyl) inter\u00adactions form zigzag C6 spiral chains along the c-axis direction, generated by a screw axis at 1, y, 1/4: the combination of the two chains provides a bimolecular sheet running parallel to the b axis, which lies between 0\u20131/2 c and 1/2\u20131 c. In compound 3, similar C9 chains, along the b-axis direction are generated by O\u2014H(oxime)\u22efO(4-meth\u00adoxy) hydrogen bonds. Further weaker, C\u2014H\u22ef\u03c0 (in 1), \u03c0\u2013\u03c0 (in 2) and both C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions (in 3) further cement the three-dimensional structures. Hirshfeld surface and fingerprint analyses are discussed.The crystal structures of three salicyaldoxime compounds, namely 2-hy\u00addroxy-4-methyl\u00adbenzaldehyde oxime, C RCH=NOH, are found in many biologically active compounds  with different substituents in the 4-position, namely a methyl group, a hy\u00addroxy group and a meth\u00adoxy group, respectively, in compounds, 1, 2 and 3. A frequent finding for salicylaldoxime derivatives is the formation of inversion-related et al., 2016The compounds described herein are all salicylaldoxime derivatives  geometry. Bond angles and bond lengths in the phenyl and oxime fragments are all in the expected ranges.There are no unusual features in the mol\u00adecular structures. Compound 1 Fig.\u00a01 crystallt Figs. 2 and 3 \u25b8,1, the hydroxyl group is essentially coplanar with its attached phenyl group [displaced by 0.020\u2005(1)\u2005\u00c5], while the inter\u00adplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 0.08\u2005(9)\u00b0. In compound 2, the hydroxyl groups lie essentially within the phenyl ring plane [O atoms deviate by \u22120.003\u2005(1) and 0.006\u2005(1)\u2005\u00c5], while the inter\u00adplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 1.08\u2005(15)\u00b0. In compound 3, the inter\u00adplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 6.65\u2005(15)\u00b0.In compound In all three mol\u00adecules, an intra\u00admolecular O2\u2014H2\u22efN12 hydrogen bond Tables 1\u20133 \u25b8 \u25b8 f1, mol\u00adecules are linked by O13\u2014H13 \u22efO2 hydrogen bonds into inversion-related via the intra\u00admolecular hydrogen bond) dimers are linked into two-mol\u00adecule-wide chains, propagating in the a-axis direction by pairs of O13\u2014H13\u22efO13 hydrogen bonds, thereby creating ii hydrogen bond are rather long [2.611\u2005(16)\u2005\u00c5] with a small angle of 100.8\u2005(12)\u00b0. However, such data fits well with published findings for H2O2 rings: a recent CSD \u22efO4(4-hy\u00addroxy)ii hydrogen bonds, propagating in the direction of the b axis, see Fig.\u00a05C6 spiral chain formed from O4\u2014H4\u22efO2i hydrogen bonds, see Fig.\u00a06b axis which lies between 0\u2013\u00bd c and \u00bd\u20131 c. These sheets are further linked by moderately strong \u03c0\u2013\u03c0 stacking inter\u00adactions, involving all the phenyl rings in the sheet: the Cg\u22efCg separation is 3.7242\u2005(13)\u2005\u00c5 with a phenyl ring slippage of 1.586\u2005\u00c5. The lack of an 2 is apparent and results from the preferential inter\u00adaction of the oxime group with the 4-hydroxyl group rather than with the 2-hy\u00addroxy group.Compound 3, C9 chains are generated from O13\u2014H13\u22efO41(meth\u00adoxy)i hydrogen bonds, which propagate in the direction of the b axis, see Fig.\u00a072, but involving the meth\u00adoxy oxygen atom O41 involved instead of the hy\u00addroxy oxygen O4. Inter\u00adestingly, the parameters of the two hydrogen bonds in the chains of compound 2 and 3 are very similar. The chains in compound 3 are linked into a two-dimensional array by C11\u2014H11\u22efCg . The former hydrogen bond forms C9 chains, forming a corrugated ribbon which runs parallel to the a axis.In compound g Table\u00a03 and \u03c0\u2013\u03c0 CrystalExplorer3.1  of the formation of intra\u00admolecular O\u2014H\u22efNO(oxime) hydrogen bonds involv\u00ading the ortho hydroxyl group. In addition, this hydroxyl group is also most frequently involved in inter\u00admolecular inter\u00adactions producing inversion-related et al., 2003et al., 2006bR = 2-HO-5-MeOC6H3, producing a C5 chain from O\u2014H(oxime)\u22efO(2-hydrox\u00adyl) hydrogen bonds; Pfluger et al., 1978R = 2-HO-5-tBu-C6H3, producing a C5 chain from O\u2014H(oxime)\u22efO(2-hydrox\u00adyl) hydrogen bonds; White et al., 2015aR = 2-HO-3-Me-5-(piperin-1-yl-CH2)-C6H2, producing a C9 chain from O\u2014H(oxime)\u22efN(piperin\u00adyl) hydrogen bonds; White et al., 2015bR = 2-HO-3-(piperin-1-ylmeth\u00adyl)-5-tBu-C6H2, producing a C9 chain from O\u2014H(oxime)\u22efN(piperin\u00adyl) hydrogen bonds; Forgan et al., 2010A survey of the Cambridge Structural Database  and 2-HO-5-MeOC6H3CH=N\u2014OH  = 1.2\u20131.5Uiso(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989018013361/qm2128sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989018013361/qm21281sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018013361/qm21282sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989018013361/qm21283sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21281sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21282sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21283sup7.cmlSupporting information file. DOI: 1868656, 1868655, 1868654CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The correct citation is: M\u00e6kel\u00e6 MJ, Pfuhl G (2019) Deliberate reasoning is not affected by language. PLoS ONE 14(1): e0211428."}
{"text": "ER) stress shifts the unfolded protein response signaling from cell survival to cell death, although the switching mechanism remains unclear. Here, we report that mitochondrial ubiquitin ligase (MITOL/MARCH5) inhibits ER stress\u2010induced apoptosis through ubiquitylation of IRE1\u03b1 at the mitochondria\u2010associated ER membrane (MAM). MITOL promotes K63\u2010linked chain ubiquitination of IRE1\u03b1 at lysine 481 (K481), thereby preventing hyper\u2010oligomerization of IRE1\u03b1 and regulated IRE1\u03b1\u2010dependent decay (RIDD). Therefore, under ER stress, MITOL depletion or the IRE1\u03b1 mutant (K481R) allows for IRE1\u03b1 hyper\u2010oligomerization and enhances RIDD activity, resulting in apoptosis. Similarly, in the spinal cord of MITOL\u2010deficient mice, ER stress enhances RIDD activity and subsequent apoptosis. Notably, unresolved ER stress attenuates IRE1\u03b1 ubiquitylation, suggesting that this directs the apoptotic switch of IRE1\u03b1 signaling. Our findings suggest that mitochondria regulate cell fate under ER stress through IRE1\u03b1 ubiquitylation by MITOL at the MAM.Unresolved endoplasmic reticulum ( Various physiological and pathological changes require enhanced ER functions, such as protein folding, removal of unfolded proteins, and reduction of oxidative stress. An imbalance in ER homeostasis causes ER stress and triggers the unfolded protein response (UPR), which is initiated by three ER proteins, PERK, ATF6, and IRE1\u03b1. The UPR is involved in the recovery of ER homeostasis through ERAD and ER chaperones  and plays a central role in the lipid metabolism and Caet\u00a0al, et\u00a0al, et\u00a0al, et\u00a0al, We have previously identified mitochondrial ubiquitin ligase (MITOL/MARCH5) and demonstrated that MITOL ubiquitylates mitofusin 2 (Mfn2) and enhances its GTPase activity, resulting in the tethering between the ER and mitochondria rather than mitochondrial fusion  481 of IRE1\u03b1 by adding a K63\u2010linked polyubiquitin chain, which in turn suppresses the activity and oligomerization of IRE1\u03b1. Here, we provide evidence that MITOL can directly regulate IRE1\u03b1 through the MAM and thus play an important role in determining cell fate under ER stress.mitol/march5 gene \u2010inducible MITOL\u2010knockout MEFs by flanking two loxP sequences with exon 2 of the ells Fig\u00a0E\u2013G, sugg2+ in the ER was increased in MITOL\u2010KO MEFs  showed abnormal morphology of the ER but not of the mitochondria Fig\u00a0H and I. MEFs Fig\u00a0J. We firMEFs Fig\u00a0A. MITOL\u2010MEFs Fig\u00a0B. To furMEFs Fig\u00a0C. In conMEFs Fig\u00a0C. These et\u00a0al, ER stress has been shown to trigger apoptosis via mitochondrial permeability transition pore  was used to select the genomic sequence target in human MITOL (5\u02b9\u2010CCAAGCCCTACAGCAGATGC\u20103\u02b9). Oligo pairs encoding 20\u2010nt guide sequences were annealed and ligated into the plasmid pX330 (purchased from Addgene). HEK293 cells were transfected and MITOL\u2010KO clones selected by serial dilution.MEFs, HEK293, and COS\u20107 cells and HeLa cells were grown in Dulbecco's modified Eagle's medium (DMEM) supplemented with 10% fetal bovine serum (FBS) and penicillin/streptomycin. Cells were transfected with either Lipofectamine 3000 (Invitrogen) or RNAiMax (Invitrogen) according to the manufacturer's protocol. The following siRNAs were used: siIRE1\u03b1 #1: sense, 5\u02b9\u2010CGGGCUCCAUCAAGUGGACUUUAAATT\u20103\u02b9, antisense, 5\u02b9\u2010UUUAAAGUCCACUUGAUGGAGCCCGTT\u20103\u02b9; siIRE1\u03b1 #2: sense, 5\u02b9\u2010AAGAUGGACUGGCGGGAGATT\u20103\u02b9, antisense, 5\u02b9\u2010UCUCCCGCCAGUCCAUCUUTT\u20103\u02b9; siJNK1 #1: sense, 5\u02b9\u2010AAAGAAUGUCCUACCUUCUTT\u20103\u02b9, antisense, 5\u02b9\u2010AGAAGGUAGGACAUUCUUUTT\u20103\u02b9; and siJNK1 #2: sense, 5\u02b9\u2010GCAGAAGCAAACGUGACAACATT\u20103\u02b9, antisense, 5\u02b9\u2010UGUUGUCACGUUUGCUUCUGCTT\u20103\u02b9. siPACS2 and siMfn2 were described previously  was subjected to further separation by 30% Percoll gradient centrifugation at 95,000\u00a0\u00d7\u00a0g for 30\u00a0min at 4\u00b0C. A low\u2010density band (denoted as the MAM fraction) was purified. The pure mitochondrial fraction in the high\u2010density band was resuspended in HB and pelleted by centrifugation . Microsomes were pelleted from the mitochondrial supernatant by centrifugation at 100,000\u00a0\u00d7\u00a0g for 1\u00a0h. Cytosol was recovered as the supernatant from this centrifugation.Isolation of crude mitochondria or pure MAM was performed as described previously  and subjected to reverse transcription to cDNA using ReverTra Ace qPCR RT Kit (TOYOBO), following the manufacturer's protocol. PCR was performed using a THUNDERBIRD SYBR qPCR Mix (TOYOBO). The PCR conditions were as follows: 95\u00b0C for 1\u00a0min followed by 40 cycles at 95\u00b0C for 15\u00a0s, 60\u00b0C for 30\u00a0s, and 72\u00b0C for 60\u00a0s. RT\u2013PCR was performed using miScript SYBR Green PCR Kit and miScript Primer Assays (Qiagen).atf4: forward, 5\u02b9\u2010GGA CAGATTGGATGTTGGAGAAAATG\u20103\u02b9, reverse, 5\u02b9\u2010GGAGATGGCCAATTGGGTTCAC\u20103\u02b9; caspase\u20102: forward, 5\u02b9\u2010 CCACAGATGCTACGGAACA\u20103\u02b9, reverse, 5\u02b9\u2010 GCTGGTAGTGTGCCTGGTAA\u20103\u02b9; chop: forward, 5\u02b9\u2010CATACACCACCACACCTGAAAG\u20103\u02b9, reverse, 5\u02b9\u2010CCGTTTCCTAGTTCTTCCTTGC\u20103\u02b9; dr5: forward, 5\u02b9\u2010CTGTGCTACAGGCTGTCTTTG\u20103\u02b9, reverse, 5\u02b9\u2010GTACTGGCCTGCTAGACAG\u20103\u02b9; xbp1s: forward, 5\u02b9\u2010GTGTCAGAGTCCATGGGA\u20103\u02b9, reverse, 5\u02b9\u2010GAGTCCGCAGCAGGTG\u20103\u02b9; edem: forward, 5\u02b9\u2010AAGCCCTCTGGAACTTGCG\u20103\u02b9, reverse, 5\u02b9\u2010AACCCAATGGCCTGTCTGG\u20103\u02b9; Sec61: forward, 5\u02b9\u2010CTATTTCCAGGGCTTCCGAGT\u20103\u02b9, reverse, 5\u02b9\u2010AGGTGTTGTACTGGCCTCGGT\u20103\u02b9; herp: forward, 5\u02b9\u2010CATGTACCTGCACCACGTCG\u20103\u02b9, reverse, 5\u02b9\u2010GAGGACCACCATCATCCGG\u20103\u02b9; col6a1: forward, 5\u02b9\u2010TGCTCAACATGAAGCAGACC\u20103\u02b9, reverse, 5\u02b9\u2010TTGAGGGAGAAAGCTCTGGA\u20103\u02b9; blos1: forward, 5\u02b9\u2010CAAGGAGCTGCAGGAGAAGA\u20103\u02b9, reverse, 5\u02b9\u2010GCCTGGTTGAAGTTCTCCAC\u20103\u02b9; hgsnat: forward, 5\u02b9\u2010TCTCCGCTTTCTCCATTTTG\u20103\u02b9, reverse, 5\u02b9\u2010CGCATACACGTGGAAAGTCA\u20103\u02b9; pdgfrp: forward, 5\u02b9\u2010AACCCCCTTACAGCTGTCCT\u20103\u02b9, reverse, 5\u02b9\u2010TAATCCCGTCAGCATCTTCC\u20103\u02b9; txnip: forward, 5\u02b9\u2010TCAAGGGCCCCTGGGAACATC\u20103\u02b9, reverse, 5\u02b9\u2010GACACTGGTGCCATTAAGTCAG\u20103\u02b9; and gapdh: forward, 5\u02b9\u2010AACTTTGGCATTGTGGAAGG\u20103\u02b9, reverse, 5\u02b9\u2010GGATGCAGGGATGATGTTCT\u20103\u02b9. Primers for xbp1s were designed to amplify the region containing sequences removed by IRE1\u03b1.The following primers were used: g, the precipitate and supernatant were analyzed by immunoblotting.To extract cholesterol\u2010enriched lipid raft from MAM, 100\u00a0\u03bcg of crude mitochondria was incubated for 10\u00a0min with indicated final concentrations of digitonin on ice. After centrifugation at 8,000\u00a0\u00d7\u00a0g for 20\u00a0min at 4\u00b0C. The supernatant was subjected to immunoprecipitation using indicated antibodies. To evaluate the ubiquitylation level of proteins, cells were solubilized with RIPA lysis buffer  and centrifuged at 20,000\u00a0g for 20\u00a0min at 4\u00b0C. The supernatant was sonicated 10\u00a0s and subjected to immunoprecipitation using indicated antibodies.To examine the protein interaction, cells were solubilized with NP\u201040 lysis buffer  and centrifuged at 20,000\u00a02 following the manufacturer's protocol.Whole lysates were separated by SDS\u2013PAGE and transferred to the PVDF membranes (Millipore). The blots were probed with indicated antibodies, and protein bands on the blot were visualized by the enhanced chemiluminescence reagent (Millipore). Phos\u2010tag\u2010PAGE was performed using 7% SDS\u2013PAGE minigels containing 10\u00a0\u03bcM Phos\u2010tag (Wako) in the presence of 100\u00a0\u03bcM MnCl2, 4\u00a0mM ATP, 200\u00a0ng of E1 , 600\u00a0ng of UbcH5b (Biomol), and 5\u00a0\u03bcg of His\u2010Ub (Biomol) for 2\u00a0h at 30\u00b0C and then terminated with 3\u00a0\u00d7\u00a0SDS sample buffer.IRE1\u03b1\u2010FLAG and MITOL\u2010HA were purified from HEK293 cells by immunoprecipitation. The purified proteins were incubated with reaction buffer containing 50\u00a0mM Tris\u2013HCl, pH 7.4, 2\u00a0mM MgClet\u00a0al, To determine the specific domains required for the interaction between MITOL and IRE1\u03b1, GST\u2010fusion deletion mutants were prepared using glutathione high\u2010capacity magnetic agarose beads (Sigma) as described previously , and analyzed using an Olympus IX81 confocal fluorescence microscope. For classification of the morphology of mitochondrial network, four stacks of 0.2\u00a0\u03bcm were acquired for cells stained with anti\u2010Tom20 antibody using 60\u00d7 objective. Images were compiled and classified in a blinded manner as normal in which the majority of mitochondria were connected in the cell or abnormal in which many mitochondria exhibited the spherical structure or showed the disconnected network overall. For quantification of the morphology of the ER network, four stacks of 0.2\u00a0\u03bcm were acquired for cells transfected with mC\u2010Sec61\u03b2 using 60\u00d7 objective and classified in a blinded manner as normal morphology with reticular\u2010like ER network or abnormal morphology either with a more sheet\u2010like ER network overall or with at least three aggregated parts in the ER network. Percentages of cells with abnormal ER network in each condition were calculated from 50 cells in each independent experiment.In Situ Cell Death Detection Kit (Roche). For Nissl, staining was performed using 0.5% cresyl violet. The sections were observed using an All\u2010in\u2010One Fluorescence Microscope BZ\u20109000.Spinal cord was fixed with 10% formalin neutral buffer solution (Wako), and 5\u2010\u03bcm\u2010thick paraffin sections were prepared. TUNEL staining was performed using 2+ imaging was performed as described previously  and re\u2010fed with HBSS. G\u2010CEPIA1er signals of transfected cells were monitored per 500\u2010ms interval during 60\u00a0s. At 20\u00a0s after Ca2+ imaging started, these cells were co\u2010incubated with 5\u00a0\u03bcM ionomycin. The level of Ca2+ in the ER was obtained as \u0394F values, calculated from F0 minus Fmax. F0 values were obtained by the average intensity of G\u2010CEPIA1er in each cell before ionomycin treatment. Fmax was calculated from the average intensity of G\u2010CEPIA1er in each cell treated with ionomycin. The intensities of G\u2010CEPIA1er were measured using ImageJ.ER Caet\u00a0al, g for 20\u00a0min at 4\u00b0C. The supernatant was centrifuged at 250,000\u00a0g for 12\u00a0h at 4\u00b0C through 20\u201340% sucrose gradient , prepared freshly by progressively layering higher to lower density sucrose fractions in 5% increments. Each 4\u00a0ml gradient was divided evenly into 16 fractions (250\u00a0\u03bcl each), and then, aliquots of fractions 2\u201313 were analyzed by immunoblotting.Sucrose gradient assay was performed as described previously  in saline.MITOLAnnexin V\u2010FITC staining was performed with Annexin V\u2010FITC apoptosis detection kit (BioVision) according to the manufacturer's protocol. For the detection of mitochondrial depolarization, cells were incubated with 10\u00a0nM tetramethylrhodamine methyl ester (TMRM) for 30\u00a0min at 37\u00b0C and then washed with PBS. The fluorescence of TMRM was analyzed by flow cytometer (Becton Dickinson).Luciferase assay was performed with dual\u2010luciferase reporter assay system (Promega) according to the manufacturer's protocol.Cell viability and cell toxicity were monitored using the Cell Counting Kit\u20108 (Dojindo) and Cytotoxicity LDH Assay Kit\u2010WST (Dojindo), respectively, according to the manufacturer's protocol.t\u2010test. The number of independent experiments is shown as n.All results are expressed as mean\u00a0\u00b1\u00a0SD. Obtained data were compared between independent experiments using either two\u2010tailed Student's Flox/Flox mice and MITOL\u2010related MEFs. TI and TU generated IRE1\u03b1\u2010KO MEFs. TT, TF, and NM contributed to the understanding of MITOLnestin mice phenotype. KT and SY wrote the manuscript with contribution from RI.KT and SY designed and carried out the experiments. SN analyzed the data. AU carried out qRT\u2013PCR and cultured cell analysis with contribution from IS and NI. SI generated MITOLThe authors declare that they have no conflict of interest.Expanded View Figures PDFClick here for additional data file.Review Process FileClick here for additional data file."}
{"text": "The conformation of the title compound is discussed and compared to those of related structures. In the crystal, mol\u00adecules of the title compound are assembled into layers parallel to the  28H22N4O9, exhibits crystallographically imposed twofold rotational symmetry, with a dihedral angle of 66.0\u2005(2)\u00b0 between the planes of the two central benzene rings bounded to the central oxygen atom. The dihedral angle between the planes of the central benzene ring and the terminal phenol ring is 4.9\u2005(2)\u00b0. Each half of the mol\u00adecule exhibits an imine E configuration. An intra\u00admolecular O\u2014H\u22efN hydrogen bond is present. In the crystal, the mol\u00adecules are linked into layers parallel to the ab plane via C\u2014H\u22efO hydrogen bonds. The crystal studied was refined as a two-component pseudomerohedral twin.The mol\u00adecule of the title compound, C The dihedral angle between the benzene and 4-meth\u00adoxy-2-nitro\u00adphenol rings in the same half of the mol\u00adecules is 4.9\u2005(2)\u00b0, indicating an almost coplanar arrangement of the benzene and phenol rings. The sp2-hybridized character of atoms N1 and C7 is confirmed by the N1\u2014C7 [1.287\u2005(6)\u2005\u00c5] bond length and C7\u2014N1\u2014C8 [121.9\u2005(4)\u00b0] and N1\u2014C7\u2014C6 [121.7\u2005(4)\u00b0] bond angles \u00b0. In the mol\u00adecule, atom N1 of the imine moiety acts as a hydrogen-bond acceptor for the adjacent phenol group, forming an intra\u00admolecular O\u2014H\u22efN hydrogen bond with an S(6) ring motif -N,N\u2032-[oxybis]bis\u00ad(1-phenyl\u00admethanimine) moiety with different substituents were found. The reference moiety is illustrated in Fig.\u00a031R) together with the dihedral and torsion angles for oxybisbenzenyl moiety in these structures are tabulated in Table\u00a02viz. non-coplanar [dihedral 2 = 18.0\u201373.5\u00b0] and nearly coplanar [dihedral 2 = 4.8\u20139.9\u00b0]. In all of these structures, the imine C=N double bond adopts an E configuration with torsion angles corresponding to C6\u2014C7\u2014N1\u2014C8 in the range 172.9\u2013180.0\u00b0.In a search of the Cambridge Structure Database  C, 60.16; H, 3.93; N, 10; found: C, 59.04; H, 3.85; N, 9.90%. 1H NMR : \u03b4 10.23 , \u03b4 9.12 , \u03b4 7.69\u20137.21 , \u03b4 3.83 . 13C NMR : \u03b4 161.69 (C=N), \u03b4 156.21\u2013114.96 (C-aromatic), \u03b4 56.25 (OCH3). IR (KBr pellets \u03c5max/cm\u22121): 3441 \u03c5(OH), 3109 \u03c5, 2956 \u03c5(CH3), 1598 \u03c5(C=N), 1529 \u03c5, 1497 \u03c5, 1326 \u03c5, 1257 \u03c5, 1194 \u03c5, 1056 \u03c5(C\u2014N), 979 \u03c5.To a sample of 2-hy\u00addroxy-5-meth\u00adoxy-3-nitro\u00adbenzaldehyde  dissolved in 25.0\u2005mL of methanol, 0.20\u2005mL of glacial acetic acid were added, and the mixture was refluxed for 30\u2005min. A solution of 4,4\u2032-oxydianiline  in 20.0\u2005mL of methanol was added dropwise under stirring to the aldehyde solution. The resulting deep-red solution was refluxed for 4\u2005h with stirring. The reaction scheme is shown in Fig.\u00a04Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl group. The crystal investigated was refined as a two-component pseudomerohedral twin resulting from a 180\u00b0 rotation about the [001] reciprocal lattice direction, with a twin ratio of 0.977\u2005(3):0.023\u2005(3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019016852/rz5267sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019016852/rz5267Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016852/rz5267Isup3.cmlSupporting information file. DOI: 1445336CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure and supra\u00admolecular inter\u00adactions between a hy\u00addroxy-functionalized pillarene and 1-octa\u00adnamine guest mol\u00adecule, which forms an inter\u00adesting host\u2013guest system, are reported. 44H48O10\u00b7C8H19N\u00b7H2O. The guest compound is stabilized inside the cavity by hydrogen-bonding and C\u2014H\u22ef\u03c0 inter\u00adactions. The water mol\u00adecule in the asymmetric unit mediates the formation of a supra\u00admolecular dimer by hydrogen-bonding inter\u00adactions. These functionalized-pillararene hosts expand the possibility of exploring more supra\u00admolecular inter\u00adactions with various guest species.Co-crystallization of a monofunctionalized hy\u00addroxy pillar[5]arene with 1-octa\u00adnamine resulted in the formation of an inclusion complex where the alkyl chain is threaded in the macrocycle cavity, namely 1,2,3,4--5-(1-hy\u00addroxy-4-meth\u00adoxy)-pillar[5]arene\u20131-octa\u00adnamine\u2013water (1/1/1), C Unlike cone-shaped calixarene or resorcinarene-type structures, the pillararenes have a tabular cavity, which makes them inter\u00adesting mol\u00adecular hosts. It is well known that pillar[5]arenes exhibit an outstanding ability to selectively bind different kinds of guest mol\u00adecules and thus are valuable chemical entities in the areas of host\u2013guest systems and mol\u00adecular recognition . Furthermore, the OH\u2013 group in pillararenes could involve hydrogen bonding with guest mol\u00adecules and/or with neighboring pillararenes, which makes them valuable compounds in mol\u00adecular recognition and supra\u00admolecular chemistry. We have recently reported details of the host\u2013guest complexation between mono-hy\u00addroxy-pillar[5]arenes with long-chain alkyl alcohol guests . It was observed that the encapsulation characteristics of the pillar[5]arene was affected by the presence of the hy\u00addroxy group, resulting in the formation of a 1:2 complex with long-chain alkyl alcohols.The pillar[5]rene system having one hy\u00addroxy group is inter\u00adesting because this OH\u2013 function is susceptible for further chemical transformation (Al-Azemi et Pil-OH) and 1-octa\u00adnamine (2OctNH). The structural features and supra\u00admolecular host\u2013guest inter\u00adactions of this co-crystalline system (2Pil-OH\u00b7OctNH) has been addressed and discussed.In this work we report the crystal structure of the inclusion complex consisting of 1-(1-hy\u00addroxy-4-meth\u00adoxy)-2,3,4,5--pillar[5]arene  has a rigid three-dimensional macrocyclic architecture with a wide cavity having a penta\u00adgonal shape. The 1-octa\u00adnamine mol\u00adecule is threaded inside the pillararene cavity and one water is included in asymmetric unit, displaying strong hydrogen-bonding inter\u00adactions with the amino group of the guest mol\u00adecule inside the cavity and the hy\u00addroxy group on the pillararene system via O11\u2014H11A\u22efN1 and O11\u2014H11B\u22efO1 bonds respectively  \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01] and O11\u2014H11\u22efO1 hydrogen-bonding inter\u00adactions  x\u00a0\u2212\u00a01, y, z]. A weak C\u2014H\u22efO type pillararene\u2013pillararene inter\u00adaction is also observed .In the title inclusion complex, the water mol\u00adecule mediates the formation of supra\u00admolecular dimers through O1s Table\u00a01, as illuet al., 2018The synthesis of 1-(1-hy\u00addroxy-4-meth\u00adoxy)-2,3,4,5-pillar[5]arene has been reported previously  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018010034/dx2005sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018010034/dx2005Isup4.hklStructure factors: contains datablock(s) I. DOI: 1855261CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methyl\u00adphenyl bridging unit in opposite directions. The crystal packing features weak C\u2014H\u22efO hydrogen bonds. 31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methyl\u00adphenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO\u2013LUMO energy gap was found to be 2.99\u2005eV and indicates n\u2192\u03c0* and \u03c0\u2192\u03c0* transitions within the mol\u00adecule.The title compound, C Such modified oligonucleotides can be used to prepare and detect the sequence of fluoro\u00adgenic probes in DNA  rings, Fig.\u00a01O-dansyl groups on either side of a bridging methyl\u00adphenyl ring that is essentially planar. The S1\u2014O1\u2014C4\u2014C3 torsion angle is 72.98\u2005(16)\u00b0 with the methyl\u00adphenyl ring plane. The S1 sulfur atoms have distorted tetra\u00adhedral geometries, with an O2\u2014S1\u2014C6 bond angle of 109.18\u2005(8)\u00b0. The two naphthalene units in each dansyl group are inclined to one another at an angle of 52.29\u2005(6)\u00b0; however, no stacking of the naphthalene units is observed.The title compound crystallizes in the space group le Fig.\u00a01. The hydc-axis direction, Fig.\u00a02B\u2014O3 and C16\u2014H16C\u2014O2 contacts further link the mol\u00adecules into sheets in the ab plane, Fig.\u00a03a-axis direction, Fig.\u00a04In the crystal structure, the supra\u00admolecular packing is dominated by weak C\u2014H\u22efO hydrogen bonds, Table\u00a01GAUSSIAN09 program package  calculations were performed at the CAM-B3LYP/6-311G  level as implemented in the et al., 2016et al., 2015N-cyclo\u00addodecyl-5-(di\u00admethyl\u00adamino)\u00adnaphthalene-1-sulfonamide -5-(di\u00admethyl\u00adamino)\u00adnaphthalene-1-sulfonamide di \u00adnaphthalene-1-sulfonamido]\u00adphenyl 5-(di\u00admethyl\u00adamino)\u00adnaphthalene-1-sulfonate arene  complexes [5-(di\u00admethyl\u00adamino)\u00adnaphthalene-1-sulfonamido]\u00adbis\u00ad(tri\u00adphenyl\u00adphosphine)digold (UZEJAL) and [5-(di\u00admethyl\u00adamino)\u00adnaphthalene-1-sulfonamido]\u00adtris\u00ad(tri\u00adphenyl\u00adphosphine)trigold perchlorate (UZEJEP) (Cho 2 atmosphere for 24\u2005h. The solvent was removed with a rotary evaporator. The residue was added to water (15\u2005ml) and extracted with di\u00adchloro\u00admethane (3 \u00d7 25ml). The organic layer was dried with anhydrous Na2SO4 and the product was purified by column chromatography using CH2Cl2 as the eluent. The di\u00adchloro\u00admethane was slowly evaporated to afford a green solid in 65% yield. Light-green block-like crystals were grown in chloro\u00adform at room temperature.The title compound was synthesized by mixing 3,5-di\u00adhydroxy\u00adtoluene  and dansyl chloride  using potassium carbonate as a base in aceto\u00adnitrile solvent (40\u2005ml). The reaction mixture was heated at 363\u2005K and stirred under an Nd(C\u2014H) = 0.95\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for aromatic and d(C\u2014H) = 0.98\u2005\u00c5, Uiso(H) = 1.5Ueq(C) for methyl H atoms. As atom Cl lies on a twofold rotation axis, the H atoms of the Cl methyl group are disordered with occupancies fixed at 0.5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019009058/sj5573sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019009058/sj5573Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019009058/sj5573Isup3.cmlSupporting information file. DOI: 1535824CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions lead to the formation of a two-dimensional network structure parallel to (110). Hirshfeld surface analysis confirmed the inter\u00admolecular inter\u00adactions.The title compound was synthesized from naphthalene di\u00adimide and methyl\u00adthio\u00adpropi\u00adamine. The asymmetric unit consists of half of the total mol\u00adecule as the mol\u00adecule lies on an inversion center. Intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds cause the mol\u00adecule to have an  22H22N2O4S2, was synthesized by the reaction of 1,4,5,8-naphthalene\u00adtetra\u00adcarb\u00adoxy\u00adlic dianhydride with 3-(methyl\u00adsulfan\u00adyl)propyl\u00adamine. The whole mol\u00adecule is generated by an inversion operation of the asymmetric unit. This mol\u00adecule has an anti form with the terminal methyl\u00adthio\u00adpropyl groups above and below the aromatic di\u00adimide plane, where four intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds are present and the O\u22efH\u22efS angle is 100.8\u00b0. DFT calculations revealed slight differences between the solid state and gas phase structures. In the crystal, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds link the mol\u00adecules into chains along the [2ABAB sequence along the c-axis direction. Hirshfeld surface analysis shows that van der Waals inter\u00adactions make important contributions to the inter\u00admolecular contacts. The most important contacts found in the Hirshfeld surface analysis are H\u22efH (44.2%), H\u22efO/O\u22efH (18.2%), H\u22efC/C\u22efH (14.4%), and H\u22efS/S\u22efH (10.2%).The title compound, C The mols Table\u00a01. The terGAUSSIAN09 software package \u2005\u00c5; Cg1 and Cg2 are the centroids of the C6/C7/C7iii/C8iii/C10/C11iii and C6iv/C7iv/C7v/C8v/C10iv/C11v rings, respectively; symmetry codes: (iii) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z; (iv) \u2212x\u00a0+\u00a02, \u2212y, \u2212z; (v) x, y\u00a0\u2212\u00a01, z]. These \u03c0\u2013\u03c0 inter\u00adactions lead to a two-dimensional network structure parallel to the (001) plane  indicate the Hirshfeld surface analysis was performed using a\u2013e), which show the H\u22efH, H\u22efC/C\u22efH, H\u22efO/ O\u22efH, H\u22efN/N\u22efH, and H\u22efS/S\u22efH contacts. The relative contributions of the atomic contacts to the Hirshfeld surface are summarized in Table\u00a03The C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and \u03c0\u2013\u03c0 stacking inter\u00adactions are identified in the two-dimensional fingerprint plots Fig.\u00a07a\u2013e, whiA mixture of 1,4,5,8-naphthalene\u00adtetra\u00adcarb\u00adoxy\u00adlic dianhydride  and 3-(methyl\u00adsulfan\u00adyl)propyl\u00adamine  in toluene (5\u2005mL) and quinoline (15\u2005mL) was heated at 453\u2005K with stirring for 1h. Upon cooling to room temperature, a golden yellow crude solid was filtered off and washed with diethyl ether. A golden yellow powder was obtained. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a di\u00adchloro\u00admethane solution of the title compound.1H NMR : \u03b4 8.77 , 4.33 , 2.64 , 2.14 , 2.07 . 13C NMR : \u03b4 162.81, 130.99, 126.69, 126.57, 40.01, 31.61, 27.16 and 15.31. IR : 3344 (m); 3071 (m); 2916 (s); 2848 (s); 1999 (s); 1693 (s).et al., 2016et al., 2013n-alkyl groups are known with 2,7-di\u00adbutyl\u00adbenzo[lmn]phenanthroline-1,3,6,8-tetra\u00adone naphthalene-4,5,8,9-tetra\u00adcarb\u00adoxy\u00adlic acid di\u00adimide  = 0.95\u2005\u00c5, Uiso = 1.2Ueq(C) for aromatic, d(C\u2014H) = 0.99\u2005\u00c5, Uiso = 1.2Ueq(C) for methyl\u00adene, and d(C\u2014H) = 0.98\u2005\u00c5, Uiso = 1.5Ueq(C) for the methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019007771/sj5571sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989019007771/sj5571Isup2.hklStructure factors: contains datablock(s) I. DOI: 1919395CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III compounds is the octa\u00adhedral coordination of the IrIII atom by a PCP pincer complex, a C atom of a (eth\u00adoxy\u00adoxoethanyl\u00adidene)methane group and two variable ligands X  and Y .The common structural feature of the four title Ir 4P,C,C\u2032,P\u2032)chlorido\u00adhydridoiridium(III) chloride methyl\u00adene chloride 2.75-solvate (4), (bis\u00ad{[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methane-\u03ba4P,C,C\u2032,P\u2032)chlorido\u00ad(eth\u00adoxy\u00adoxoethanido)iridium(III) chloride\u2013methanol\u2013water (1/1/0.5) (5), (bis\u00ad{[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methane-\u03ba4P,C,C\u2032,P\u2032)di\u00adchlorido\u00adiridium(III) chloride\u2013methanol\u2013water (1/1/2) (6) and (bis\u00ad{[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methane-\u03ba4P,C,C\u2032,P\u2032)carbon\u00adyl(eth\u00adoxy\u00adoxoethanide)iridium(III) dichloride\u2013meth\u00adyl\u00adene chloride\u2013water (1/2/1.5) (7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl\u00b72.75CH2Cl2 (4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl\u00b7CH3OH\u00b70.5H2O (5), [Ir(C55H50O2P4)Cl2]Cl\u00b7CH3OH\u00b72H2O (6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2\u00b72CH2Cl2\u00b71.5H2O (7) is a central IrIII atom coordin\u00adated in a distorted octa\u00adhedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodi\u00adphospho\u00adrane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings . A cyclo\u00adpropane-like heterocycle is positioned approximately orthogonal (84.21\u201388.85\u00b0) to the equatorial plane, including an alkyl\u00adidene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetra\u00addentate way via three Lewis acid/base bonds and by an alkyl\u00adidene unit presenting strengthened inter\u00adactions. In all the crystal structures, (disordered) solvent mol\u00adecules are present in the voids of the packed mol\u00adecules that inter\u00adact with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.The common feature of the four iridium(III) salt complexes, (bis\u00ad{[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methane-\u03ba Nomura et al., 2011et al., 1998et al., 1991et al., 2005Carbodi\u00adphospho\u00adranes (CDP) in combination with transition metals initialize a huge variety of functionalities. As a result of the presence of two 2]Cl  atom, followed by deprotonation of the carbodi\u00adphospho\u00adrane carbon atom, the generation of a hydrido ligand caused by an oxidation of the iridium(I) atom and the formation of the Cl complex 1  an Cl2 precursor system (2) is generated in high yields (86%). Moreover, the preparation of complex 2 in a less polar solvent environment like chloro\u00adform/aceto\u00adnitrile or in a solvent mixture of methyl\u00adene chloride/aceto\u00adnitrile (v/v 5:1) is not possible and qu\u00adanti\u00adtatively results in the substitution of one phosphine moiety of the carbodi\u00adphospho\u00adrane functionality against the carbene CHCO2Et subunit. An Cl complex 3 is generated, offering a phospho\u00adrus ylide carbon backbone  to 333\u2005K for 2\u2005h benefits the ring-opening reaction of the PCCP pincer ligand system. Therefore, a reorganization of the ligand system is supported, resulting in the qu\u00adanti\u00adtative formation of complex 3. Furthermore, evaporation of the reaction mixture of complex 2 causes an exchange of the aceto\u00adnitrile solvent ligand with a chloride counter-ion and the creation of the desired Cl complex 4. If the starting materials Cl alkyl derivative 5. This reaction procedure is well known, and the mechanism of the inter\u00admolecular insertion reaction has been clarified via an inter\u00admediate carbene complex (dppm)2-\u03ba4P,C,C\u2032,P\u2032}Cl2]Cl complex 6. Besides, a replacement of the chlorido ligand of compound 5 by a carbonyl group is possible and results in the Cl2 complex 7.The stucture of this irid\u00adium(III) PCCP complex was completely determined by NMR spectroscopy and X-ray crystallography, but up to now crystallization attempts of the inter\u00admediates, 4\u20137.Here we report details of the syntheses and crystal structures of complexes 4, Cl, comprises of one formula unit of 4 and additionally of 2.75 mol\u00adecules of methyl\u00adene chloride solvent mol\u00adecules. The central iridium(III) transition metal is surrounded in a distorted octa\u00adhedral fashion by a PCCP pincer-like ligand system, and anionic chlorido and hydrido ligands (dppm)2-\u03ba4P,C,C\u2032,P\u2032] ligand coordinates the IrIII metal in a tetra\u00addentate fashion via two P and two C atoms under formation of two five-membered, dissimilar chelate rings  and one three membered heterocycle. The PCP ligand exhibits a meridional arrangement with the hydrido ligand completing the equatorial plane trans to the C1 carbodi\u00adphospho\u00adrane atom. A cyclo\u00adpropane-like chelate ring is positioned nearly normal (84.21\u00b0) to the equatorial plane, and a chlorido ligand is positioned trans to the alkyl\u00adidene carbon atom C4. The Ir\u2014C1 [2.273\u2005(4)\u2005\u00c5] and Ir\u2014C4 [2.072\u2005(5)\u2005\u00c5] distances differ significantly and consequently these values substanti\u00adate a strengthened inter\u00adaction between the iridium(III) metal and the alkyl\u00adidene carbon atom. The C1\u2014C4 separation [1.515\u2005(6)\u2005\u00c5] is slightly shorter in comparison to a typical C\u2014C single bond but, in general, very close to that of cyclo\u00adpropanes. However, in comparison with a cyclo\u00adpropane mol\u00adecule the C4\u2014Ir1\u2014C1 [40.5\u2005(2)\u00b0], C4\u2014C1\u2014Ir1 [62.6\u2005(2)\u00b0] and C1\u2014C4\u2014Ir1 [76.9\u2005(3)\u00b0] angles emphasise a significant distortion of the synthesized three-membered heterocycle. All mentioned geometric features of this strained Ir\u2014C1\u2014C4 metallacycle can be associated with the structural results of the Ru\u2014C\u2014C triangle reported by Zhang et al. (dppm)2-\u03ba4P,C,C\u2032,P\u2032}(CH2CO2Et)Cl]Cl, is defined by one complex 5, one half-occupied water mol\u00adecule and one disordered methanol solvent mol\u00adecule. In comparison with the structural features discussed in detail for compound 4, significant differences pertain only to the equatorial position trans to C1. Here the hydrido ligand in 4 is exchanged by an ethyl acetate unit (dppm)2-\u03ba4P,C,C\u2032,P\u2032}Cl2]Cl. In its crystalline form, besides one formula unit of 6, one solvent mol\u00adecule of MeOH and two water mol\u00adecules in total are present in the asymmetric unit. Overall, this PCCP derivative shows very similar structural characteristics (dppm)2-\u03ba4P,C,C\u2032,P\u2032}(CH2CO2Et)(CO)]Cl2  = 2.83\u2005\u00c5] exhibiting distances shorter than the sum of the van der Waals radii ], 2.91\u2005\u00c5 (H3A\u22efCl2) and 2.40\u2005\u00c5 (H3B\u22efO1)  Fig.\u00a07.6, the methyl\u00adene groups of the PCP unit and the chloride counter-ion and the solvent mol\u00adecules form C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions ], 2.66\u2005\u00c5 (H3B\u22efCl3) and 2.40\u2005\u00c5 [H6A\u22efO3 ] ] Fig.\u00a08.7, the chloride counter-ions inter\u00adact with both the PCP pincer ligand system and the solvent mol\u00adecules. The solvent mol\u00adecules also show inter\u00adactions with the iridium complex III{C(CHCO2Et)(dppm)2-Synthesis of Cl\u00b72.75CH2Cl2 (4)\u03ba: A mixture of [CH(dppm)2]Cl  and [IrCl(cod)]2  was solved in 0.1\u2005ml of MeCN. After a reaction time of one minute, a solution of ethyl diazo\u00adacetate  in MeOH (0.5\u2005ml) was added. 10\u2005min later, a deep yellow liquid was obtained. The volatiles were removed and the remaining solid was dissolved in methyl\u00adene chloride (0.6\u2005ml), leading to complex 4 in high yield . Single crystals of complex 4 were grown from a solvent mixture of n-hexane (1.2\u2005ml) and CH2Cl2 (0.2\u2005ml). 31P {1H} NMR (CHCl3): \u03b4 = 18.8 , 38.1 , 34.7 , 10.7  ppm; 1H NMR : \u03b4 = \u221215.2  ppm; 13C {1H} NMR (CDCl3): \u03b4 = 3.6  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl\u00b7CH3OH\u00b70.5 H2O (5):} was added to a solution of complex 4  in CH2Cl2 (0.6\u2005ml), and the reaction mixture was stirred for 30\u2005min. Complex 5  was formed qu\u00adanti\u00adtatively. Single crystals were obtained via slow evaporation of a 1:1methyl\u00adene chloride/methanol mixture. 31P {1H} NMR (CHCl3): \u03b4 = 0.3 , 40.6 , 36.4 , \u22124.4  ppm; 13C {1H} NMR (CDCl3): \u03b4 = 3.1  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl\u00b7CH3OH\u00b72H2O (6):}Cl A solution of complex 4  in CH2Cl2 (0.6\u2005ml) was treated with hydro\u00adchloric acid  and stirred vigorously for approximately 10\u2005min. The organic phase was separated and washed with water (0.5\u2005ml) three times in total. Complex 6  was formed almost qu\u00adanti\u00adtatively. Yellow single crystals were generated by slow evaporation of a 1:1 solvent mixture of MeCN and MeOH. 31P {1H} NMR (CHCl3): \u03b4 = \u22126.1 , 46.9 , 45.8 , \u221210.3  ppm; 13C {1H} NMR (CDCl3): \u03b4 = 3.8  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl2\u00b72CH2Cl2\u00b71.5H2O (7):} in CH2Cl2 was placed under an atmosphere of CO. After a reaction time of 1\u2005h, complex 7 had formed qu\u00adanti\u00adtatively . Single crystals were grown from a solution of methyl\u00adene chloride, covered with a small amount of ethyl acetate. 31P {1H} NMR (CH2Cl2): \u03b4 = \u22126.5 , 41.2 , 39.7 , \u221216.4  ppm; 13C {1H} NMR (CD2Cl2): \u03b4 = 16.1 , 172.8  ppm.Crystal data, data collection and structure refinement details are summarized in Table\u00a06Uiso(H) = 1.2Ueq(C) for phenyl and methyl\u00adene H atoms and 1.5Ueq(C) for methyl H atoms.Unless noted otherwise, H atoms in the four structures were placed geometrically and refined in the riding-model approximation with 4, the two hydrogen atoms bound to the central Ir1 atom and the C4 atom of the eth\u00adoxy\u00adoxoethanyl\u00adidene moiety were discernible from a difference-Fourier map. They were refined with bond-length restraints of 0.96\u2005\u00c5 (C4) and 1.60\u2005\u00c5 (Ir1) and with individual Uiso values. Three of the four methyl\u00adene chloride solvent mol\u00adecules are disordered. One solvent mol\u00adecule  shows half-occupation, one  is disordered around an inversion centre (occupancy 0.25) and for one  the Cl atoms show a positional disorder over two sites (ratio 0.7:0.3). All H atoms of the solvent mol\u00adecules were omitted from the final model.For compound 5 was poor. Hence, it was possible to collect reflections only up to 45\u00b0/2\u03b8. The H atom attached to the C4 position was treated as described above. The methanol  and water (O7) solvent mol\u00adecules are disordered around an inversion centre and were refined with half-occupation. H atoms of the disordered solvent mol\u00adecules were omitted from the model. Furthermore, one phenyl group shows a 1:1 positional disorder and was refined over two sets of sites . All atoms of the disordered phenyl ring were refined isotropically.The scattering power of the crystal of compound 6 and 7, the H atom attached to the C4 position was treated as described above. For 6, localization of the H atoms of the methanol and water solvent mol\u00adecules was not possible and hence they were omitted from the model. For 7, H atoms of water mol\u00adecule O6 were located from a difference-Fourier map and refined with bond-length restraints of 0.84\u2005\u00c5. The O7 atom of the other water mol\u00adecule was treated as being half-occupied, and its H atoms were omitted from the model. One methyl\u00adene chloride solvent mol\u00adecule  was refined over two sets of sites (ratio 0.65:0.35).In compounds 10.1107/S2056989018017024/wm5471sup1.cifCrystal structure: contains datablock(s) global, 4, 5, 6, 7. DOI: 10.1107/S2056989018017024/wm54714sup6.hklStructure factors: contains datablock(s) 4. DOI: 10.1107/S2056989018017024/wm54715sup7.hklStructure factors: contains datablock(s) 5. DOI: 10.1107/S2056989018017024/wm54716sup8.hklStructure factors: contains datablock(s) 6. DOI: 10.1107/S2056989018017024/wm54717sup9.hklStructure factors: contains datablock(s) 7. DOI: 1873392, 1873391, 1873390, 1873389CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This is comparable to very weak CH hydrogen bonding interactions and is in line with the weak interaction energies calculated  of typical charge neutral adducts such as [Me3N-CH3\u00b7\u00b7\u00b7OH2] (2a). The interaction energy is enhanced to \u2264\u20135 kcal\u00b7mol\u22121 when X is more electron withdrawing such as in [O2N-CH3\u00b7\u00b7O=Cdme] (20b) and to \u226418 kcal\u00b7mol\u22121 in cationic species like [Me3O+-CH3\u00b7\u00b7\u00b7OH2]+ (8a).A systematic evaluation of the CSD and the PDB in conjunction with DFT calculations reveal that non-covalent Carbon-bonding interactions with X\u2013CH The manner in which molecules interact with one another is largely determined by non-covalent interactions.c  So-calle3-hybridized C-atoms. Such interactions have been studied since about 2013  [3\u00b7\u00b7\u00b7OH2]   and [HO-3\u00b7\u00b7\u00b7OH2]  of \u22120.7 6\u201311a were computed as well and the most stable of these involved the Me3C+ carbocation in 6 (adducts with pentamethylated Carbon are unstable). The bonding interaction in 6b is largely covalent, as evidenced by the interaction energy of \u221282.4 kcal\u00b7mol\u22121, the large orbital contribution (55%), a dense bond critical point (18.4 \u00b7 102 a.u.) and a clear pyramidalization of the central C-atom (see 6a (Me3C+\u00b7\u00b7\u00b7O interaction) and 9 (with the least electronegative P) converged into an X\u2013CH3\u00b7\u00b7\u00b7O Carbon bonding geometry. This is illustrated for 8a and 11a in methylC and Owater with a bond density of 1.15 \u00b7 102 and 0.98 \u00b7 102 a.u. for 8a and 11a respectively. The bonding energies in 7\u201311a are mainly electrostatic in origin (~70%) and about \u22128 kcal\u00b7mol\u22121 for water and \u221215 kcal\u00b7mol\u22121 for dma. The most stable adducts in both series involved the most electronegative O (3.44) in Me3O+ (8). Two alternative configurations with N-methylpyridinium were also computed (12 and 13). In 12, the O points in between two CH hydrogens as is illustrated for 12a in 13 the O atom is located directly above the cationic N+. Both 12 and 13 are more stable than the Carbon bonding geometry found in 11, suggesting that hydrogen bonding interactions are most preferred. The interaction energies of Carbon bonding interaction with cationic species is similar to previous data of the adducts: [H3N+-CH3\u00b7\u00b7\u00b7OCH2] ; [3N+-CH3\u00b7\u00b7\u00b7OC(H)NH2] ; [2S+-CH3\u00b7\u00b7\u00b7OH2/NH3/OCH2] ; [2S+-CH3\u00b7\u00b7\u00b7various lone-pairs]   ; [3\u00b7\u00b7\u00b7C2H2] ; [3\u00b7\u00b7\u00b7C2H4/NH3/PH3] ; [3\u00b7\u00b7\u00b7C2H4/dma] ; [2N-CH3\u00b7\u00b7\u00b7dma]  [As the calculations with cationic species imply that electron withdrawing substituents amplify the Carbon bonding interaction, it was decided to compute adducts with small molecules that have an electron withdrawing group: Iodomethane (\u00b7mol\u22121); ,51,52,53\u00b7mol\u22121);  [Hlg-CH3\u00b7mol\u22121);  [NC-CH3\u00b7\u00b7mol\u22121); ,56 and [2-O in dma (adducts \u2018b\u2019) is consistently about twice as strong as the interaction with sp3-O in water (adducts \u2018a\u2019). This is in line with the larger amount of van der Waals overlap observed in the N(d\u2019) plots , to moderately weak  to fairly strong in the cationic adducts . \u0394E becomes smaller (more stable) in the order 2 < 14 < 16 < 18 < 20 < 7 < 8. Within this series, the orbital contribution remains constant at about 15\u201320%, while the electrostatic component increases from 30\u201335% in 2 to about 65% in 8. This implies that stronger Carbon bonding interactions are mainly driven by electrostatic interactions and that weaker such adducts are driven by dispersion. These computational results are consistent with recent literature reports [3 is strongly polarized  within a hemisphere of 5 \u00c5 basal radius (centered on C). It was found that X\u2013CH3\u00b7\u00b7\u00b7ElR interactions can be as directional as very weak hydrogen bonding interaction involving C\u2013H (Pmax \u2264 1.50) but not directional at all when X = C. Grouping of data with significant amounts of van der Waals overlap (up to ~30%) was observed in various sub-datasets in the region where the X\u2013CH3\u00b7\u00b7\u00b7ElR angle \u03b1 is 160\u00b0\u2013180\u00b0. These distributions were significantly shifted to shorter distances  in the case of cationic R3N+\u2013CH3\u00b7\u00b7\u00b7Owater/amide compared to charge-neutral R2N\u2013CH3\u00b7\u00b7\u00b7Owater/amide interactions.The CSD and the PDB were systematically evaluated for potential directional behavior of intermolecular non-covalent Carbon bonding interactions involving X\u2013CH3\u00b7\u00b7\u00b7O adducts with water and dimethylacetamide are very weak  and are often not the energy minima of the adducts . The interaction energies can be increased by deploying a more electron withdrawing X . Rendering X cationic leads to even more stable adducts  in 7, 8, 10 and 11). Carbon-bonding adducts with dimethylacetamide are consistently twice as stable as those with water. Energy decomposition analyses showed that increased stability is driven by electrostatics and atom-in-molecule analyses regularly gave a clear bond critical point involving the methyl C-atom.Model DFT calculations revealed that charge neutral X\u2013CH3 is electrostatically driven and can be significant. The interaction can even by mildly directional in the solid state (comparable to weak CH hydrogen bonding interactions), provided X is sufficiently electron withdrawing.It is thus concluded that this combined database / DFT study reaffirms that intermolecular non-covalent Carbon interactions with X\u2013CH"}
{"text": "I) and 1,2\u2010disila[9]crown\u20103 (II) with MgI2 yielded exclusively [MgI2] (1). The larger Ca2+ ion was then employed for cross\u2010coupling of I and II and yielded the complex [CaI2] (2). Cross\u2010coupling of I and 1,2,4,5\u2010tetrasila[9]crown\u20103 (III) with SrI2 enables the synthesis of the silicon\u2010dominant 1,2,4,5,10,11\u2010hexasila[15]crown\u20105 ether complex of SrI2 (3). Further, the compounds [SrI2] (4), [SrI2] (5), and [SrI2] (6) were obtained by coupling I, 1,2\u2010disila[12]crown\u20104 (IV) or 1,2\u2010disila\u2010benzo[12]crown\u20104 (V), respectively. Using various anions, the (cross\u2010)coupled ligands were also observed in an X\u2010ray structure within the mentioned complexes. These template\u2010assisted (cross\u2010)couplings of various ligands are the first of their kind and a novel method to obtain macrocycles and/or their metal complexes to be established. Further, the Si\u2212O bond activations presented herein might be of importance for silane or even organic functionalization.Alkaline earth metal iodides were used as templates for the synthesis of novel silicon\u2010based ligands. Siloxane moieties were (cross\u2010)coupled and ion\u2010specific, silicon\u2010rich crown ether analogues were obtained. The reaction of 1,2,7,8\u2010tetrasila[12]crown\u20104 coupled and ion specific, silicon\u2010rich crown ether analogues were obtained. The coupling of various ligands gives an outlook on Group\u20052 ion\u2010catalyzed macrocycle and/or silane syntheses. It is well known for crown ethers to form coordination compounds with metal centers across a wide range of the periodic table. These complexes are generally very stable and these polyethers as well as related systems such as cryptands, or in general, multidentate ligands, gained many fields of applications since their discovery in the mid\u2010sixties. The synthesis of such polyethers, however, is often not trivial because the molecules of the starting materials need to be brought into a suitable conformation for the formation of a specific (most often cyclic) product. The synthesis of these cyclic ethers is therefore mostly metal\u2010template assisted.Templates are known to provide a suitable coordination sphere for the starting materials, which favors the linkage to ring closure and allows obtaining cyclic ligand systems in much higher yields.\u03b4+ and metaln+ disturbs silyl ether bonding.n type .+ and Cs+ so far relucted silyl ether coordination.Most recently, both concepts\u2014covalency and ionicity\u2014were considered as harmonious models to understand the basicity of siloxanes. Regarding a covalent model, negative hyperconjugation interactions are described in the case p(O)\u2192\u03c3*(Si\u2212C).Apart from siloxane coordination chemistry, the metal\u22c5\u22c5\u22c5O\u2212Si interaction should also be put in context to Si\u2212O bond activation. From the perspective of Si\u2212O bond activation, weakening of Si\u2212O bonds is of considerable significance regarding the conversion of silicates to silanes. Especially dicatecholato\u2010silicate(IV) complexes are frequently used as precursors for either silane synthesis or functionalization of various organic molecules.2+ ion, we aimed at synthesizing a [15]crown\u20105 ether by cross\u2010coupling the ligands 1,2,7,8\u2010tetrasila[12]crown\u20104 (I) and 1,2\u2010disila[9]crown\u20103 (II). However, the reaction in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene heated at reflux failed (Scheme\u20052] (1) was obtained and, as can be seen from the molecular structure determined by single\u2010crystal X\u2010ray diffraction analysis (SC\u2010XRD), the moiety of crown ether I is large enough to bind Mg2+ I2] and the octahedral coordination towards Mg2+ is preferred.I with Mg2+ is present because the 29Si{1H}\u2005NMR chemical shift is observed at 22.8\u2005ppm and thus, a strong lowfield shift in comparison with I (\u03b4=10.8\u2005ppm)Starting with the Mgsizing a 5crown\u20105 2+ ion was described earlier and, as can be seen from various examples, seems to match perfectly.I and II with CaI2. After workup procedures two new signals in the 29Si{1H}\u2005NMR are observed at 19.6 and 19.9\u2005ppm. Crystallization of the reaction product 2 however, was unsuccessful from different solvents and temperatures also due to poor solubility. We therefore expanded the anion I\u2212 to I3\u2212 upon iodine addition. The compound [Ca(I3)2] (2\u2009a) then was crystallized and the molecular structure was determined by means of SC\u2010XRD  and 245.2(9)\u2005pm and compare well to the complex [CaOTf2] (OTf=CF3SO3\u2212).The fivefold, coplanar coordination by sila\u2010crown ligands towards the larger Ca2] (3) is another example of a cross\u2010coupling reaction in which an alkaline earth metal cation is used. 3 represents the first hybrid disila\u2010crown ether bearing more disilane than ethylene units. The even larger Sr2+ cation can be used as a convex template to cross\u2010couple I and 1,2,4,5\u2010tetrasila[9]crown\u20103 (III), which is accessible applying reaction conditions reported before.I and one equivalent of III. Due to three disilane units within the ligand framework, the Sr2+ cation fits well in the cavity of the obtained ligand. With 19.44, 19.27, and 13.32\u2005ppm, three resonances are observed in the 29Si{1H}\u2005NMR spectrum, all of which compare well to those of OSi\u22c5\u22c5\u22c5Sr2+ coordination compounds characterized before.3 could not be obtained, even after iodine addition. Hence, the Lewis acidic salt GaI3 was added as an acceptor for the iodide anion. It is notable, that also in 3\u2009a, the SiSi\u2212O\u2212SiSi fragment of the siloxane framework provides a small Si\u2010O\u2010Si angle, which measures 121.1(6)\u00b0. The OSi\u2212O\u2212Si\u22c5\u22c5\u22c5Sr2+ distance might be the longest O\u22c5\u22c5\u22c5Sr2+ distance observed in 3\u2009a, but the high basicity of siloxanes towards Group\u20052 ions is clearly emphasized.The synthesis of [SrI4)2] (3\u2009a) were obtained, which were analyzed through SC\u2010XRD  compare well to various complexes of Sr2+ and sila ligands, which were reported before.2+ cation as a template, we were able to observe reactions of other disila\u2010crown ethers as well. The small cavity of II does not allow for 1:1 complexation of Sr2+ and thus, a total of two equivalents of II react to form the 1,2,10,11\u2010tetrasila[18]crown\u20106 ether. [SrI2] (4) is obtained as a colorless powder and in solution, a resonance at 17.5\u2005ppm in the 29Si{1H}\u2005NMR spectrum was observed. Given that we were also experiencing problems with the crystallization of this compound, the X\u2010Ray structure could only be determined upon iodine addition. According to a reduced niggli formula, compound 1\u221e+ fragments to build infinite chains along [001] which is most likely the driving force for crystallization. The OSi\u22c5\u22c5\u22c5Sr2+ distances in 4\u2009a compare well to those in compound 3\u2009a and [SrI2].After several months, a few single crystals of [Sr(GaI4)2] \u2009a were o4 as an example. As drawn here, the sila\u2010ligand is polarized by the Lewis acid first, which makes it electrophilic and thus accessible for nucleophilic attack of I\u2212. Afterwards, the Si\u2212O bond is cleaved. Subsequently, the intermediate then has to cleave the second sila\u2010crown. At this point of the reaction, the alkaline earth metal ion acts as a convex template, in which the open\u2010chained ligand species is brought into a suitable conformation for ring closure, which is the final step of the presented reactions. We want to emphasize, that such a mechanism was also postulated by Harder in a past work.At this point, it is clear that (cross\u2010)coupling reactions are possible with different alkaline earth metal iodides. We tried to understand how the reaction works and the mechanism behind the formation of these unprecedented macrocycles, but unfortunately, we were unable to characterize any intermediate products by means of NMR spectroscopy or SC\u2010XRD. We can assure that heating at reflux is needed to cleave the smaller rings. Further, we can assure that the reaction does only occur if an iodide salt is employed. Other alkaline earth metal halides do not form these ligands. This lets us conclude that one key step in the formation of the (cross\u2010)coupling product has to be a nucleophilic substitution reaction. Furthermore, as evident from different works, we could convincingly show that the Si\u2212O bond is significantly weakened due to coordinating an alkaline earth metal ion. Thus, the Si\u2212O bond instead of the C\u2212O bond is cleaved, which is also represented by the herein obtained macrocycles. A proposed mechanism for the formation of the cross coupling products is depicted in Scheme\u20052 with the ligands 1,2\u2010disila[12]crown\u20104 (IV) and 1,2\u2010disila\u2010benzo[12]crown\u20104 (V) were performed. Both ligands are too small for Sr2+ and thus, template\u2010assisted ring opening yielded novel species by intermolecular coupling of the respective crown ether. The reaction of IV with SrI2 results in the formation of the first disilanyl\u2010bearing [24]crown\u20108 ether. [SrI2] (5) was obtained by coupling two equivalents of IV I2].29Si{1H}\u2005NMR resonance signal for 5 is observed at 15.2\u2005ppm. A split of this resonance at low temperature of 190\u2005K was not observed.Further reactions of SrIwn\u20108)I2]  was obta5 decomposes readily with only traces of moisture forming [SrI]I (EO7=heptaethylene glycol).Thus, the exchange between the coordinating disilane units is too fast on the NMR time scale and results in the described equivalency. At this point, it should be noted that the spectroscopic investigation of the compound is challenging. Compound 6) is more stable and was characterized by state\u2010of\u2010the\u2010art methods including SC\u2010XRD I]I  is more 6 was reacted with [222]cryptand and indeed we were able to obtain free ligand 1,2,13,14\u2010tetrasila\u2010dibenzo[24]crown\u20108 (7) after workup. The metal\u2010free ligand species was characterized by means of HR\u2010ESI MS as well as NMR spectroscopy. In HR\u2010ESI+ MS, m/z relations of 625.2502 [7+H]+ (100) as well as 647.2320 [7+Na]+ (100) were found. In addition, 29Si{1H}\u2005NMR spectroscopy revealed highfield chemical shift and a single resonance at 11.5\u2005ppm is found. This value compares well to the free ligand V and also to related metal\u2010free disila\u2010ligand systems.One of the remaining questions is of course whether it is possible to remove the metal center for possible use of such new ligand in coordination chemistry. We are currently investigating this subject, but are still at an early stage. To give an outlook, we performed exchange reactions. As an example, an excess of ted with 2cryptanda\u2010dibenzocrown\u20108 \u2010coupling reactions with BaI2+ ion is too small to cross\u2010couple small silicon\u2010based ligands, a cross\u2010coupling reaction was established with the larger Ca2+ and Sr2+ ions. Furthermore, the Sr2+ ion was used for coupling reactions of three different disila\u2010crown ethers. Barium as a template for coupling reaction, however, turned out to be unsuccessful. Although the organic [12]crown\u20104 is too small for the Mg2+ ion, the cavity of the disilane\u2010bearing analogue 1,2,7,8\u2010tetrasila[12]crown\u20104 (I) ether matches fine with the Mg2+ ion and the complex [MgI2] (1) was obtained. [CaI2] (2) and [SrI2] (3) were synthesized by cross\u2010coupling reaction of the small rings I and II for 2, and I and III for 3. The ligand in 3 represents the first crown ether with more disilane than ethylene units between the donor atoms. Finally, [SrI2] (4), [SrI2] (5) and [SrI]I (6) were characterized and obtained by template\u2010driven dimerization of II, IV, or V with SrI2. The ligand moieties observed in 2\u20136 cannot yet be synthesized by conventional silane chemistry and for this reason, the template\u2010assisted (cross\u2010)coupling of various ligands is an elegant way to obtain novel macrocycles and/or their metal complexes. Overall, this work gives an outlook on Group\u20052 ion\u2010catalyzed silane syntheses, especially due to the fact that first attempts showed that the metal ion can, in principle, be removed from a novel sila\u2010ether. We also hope that there will be a broader application of the presented Si\u2212O bond activations as a mean of molecule functionalization.In this study alkaline earth metal iodides were successfully used for the coupling reaction of different silicon\u2010based crown ether analogues to form novel ligand environments. The work presents Si\u2212O bond\u2010cleavage reactions driven by a macrocyclic effect due to metal\u2010template reaction of the respective silicon\u2010based ligands. Given that the Mg2 , CaI2 and SrI2 , BaI2  and GaI3  were finely ground and stored in a Mbraun glovebox under Ar. NMR spectra were recorded on a Bruker AV III HD 300\u2005MHz or AV III 500\u2005MHz spectrometer, respectively. Infrared (IR) spectra of the respective samples were measured using attenuated total reflectance (ATR) mode on the Bruker\u2010type spectrometer Alpha FT\u2010IR. ESI mass spectra were acquired with a LTQ\u2010FT Ultra mass spectrometer (Thermo Fischer Scientific) and LIFDI mass spectra were acquired on a JEOL AccuTOF\u2010GCv device. The resolution was set to 100.000. Elemental analysis was carried out on a Vario MicroCube. In case of complex\u20052 and 3, we were not able to obtain an accurate elemental analysis. This is probably due to the wax\u2010like, greasy characteristics of the compounds and/or formation of SiC during the measurement. The crown\u2010ethers I, II, IV, and V were synthesized according to literature\u2010known procedures.7 can only be obtained with major impurities of [222]crypt.All manipulations were carried out with rigorous exclusion of oxygen and moisture using basic Schlenk techniques establishing an inert\u2010gas atmosphere with a vacuum line. All solvents were dried and freshly distilled before use. The alkaline earth metal salts MgI3  were dissolved in THF (50\u2005mL). Subsequently, O(Si2Me4Cl)2n\u2010pentane (50\u2005mL) followed by filtration. Removing the solvent under reduced pressure yielded the crown ether as a colorless oil .Ethylene glycol  and NEt1H\u2005NMR : \u03b4=0.18 2), 0.20 2), 3.69\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=0.1 2), 2.8 2), 66.0\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=1.5 2), 11.4\u2005ppm 2). HR\u2010MS: ESI(+) m/z (%): 309.1196 [M+H]+ (100), 639.2143 [2\u2009m+Na]+ (100); IR: 2951 (m), 2896 (w), 2867 (w), 1457 (vw), 1388 (vw), 1247 (s), 1140 (m), 1089 (s), 1027 (s), 927 (m), 854 (m), 795 (s), 761 (vs.), 721 (m), 681 (m), 660 (m), 633 (m), 553 (m), 506 (vw), 487\u2005cm\u22121 (m).I  was dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (10\u2005mL). Subsequently, MgI2  was added. Stirring the mixture at 60\u2009\u00b0C for 90\u2005min gave a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (10\u2005mL) followed by filtration. After washing with n\u2010pentane (4\u2005mL), and drying in vacuo, 1 was obtained as a colorless powder . For single\u2010crystal growth, the powder was dissolved in DCM (4\u2005mL) and layered with n\u2010pentane (20\u2005mL). Single crystals were obtained overnight as colorless needles.Compound 1H\u2005NMR : \u03b4=0.59 2), 4.23\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=\u22120.46 2), 62.8\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=22.8\u2005ppm 2). MS: ESI(+) m/z (%): 503.0270 [M\u2212I]+ (15); IR: 2949 (vw), 2888 (vw), 1450 (w), 1398 (vw), 1369 (vw), 1247 (m), 1103 (m), 1056 (s), 1022 (s), 934 (vs.), 915 (s), 868 (m), 840 (m), 818 (s), 802 (s), 780 (vs.), 715 (s), 645 (m), 464\u2005cm\u22121 (m). CHN calcd for C12H32I2MgO4Si4\u22c5\u2009CH2Cl2 C, 21.81; H, 4.79. Found C, 21.66; H, 4.90.I  together with II  were dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (10\u2005mL). Subsequently, CaI2  was added. Heating the mixture at reflux for 90\u2005min resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with of DCM (10\u2005mL) followed by filtration. After washing with two portions of n\u2010pentane (4\u2005mL each), and drying in vacuo, 1 was obtained as a colorless powder . For single\u2010crystal growth, 2  and I2  were dissolved in DCM (4\u2005mL) and filtered. The filtrate was then layered with n\u2010pentane (20\u2005mL). A few brown platelets of 2\u2009a were obtained after more than two weeks at ambient temperature.Compound 1H\u2005NMR : \u03b4=0.47 , 0.48 , 3.95\u20134.03\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=\u22120.7 , \u22120.7 , 63.2 , 64.8 , 71.2\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=19.6 , 19.9\u2005ppm . MS: ESI(+) m/z (%): 419.1521 [M\u2212CaI2+Na]+ (100), 397.1705 [M\u2212CaI2+H]+ (5). IR: 2947 (m), 2881 (w), 1455 (vw), 1400 (vw), 1248 (s), 1057 (s), 1029 (s), 943 (s), 795 (s), 768 (vs.), 723 (s), 635 (m), 505\u2005cm\u22121 (vw).I  and III  were dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (10\u2005mL). Subsequently, SrI2  was added. Heating the mixture at reflux for 90\u2005min resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (10\u2005mL), followed by filtration. After washing with two portions of n\u2010pentane (4\u2005mL each) and drying in vacuo, 3 was obtained as a colorless, greasy solid . For single\u2010crystal growth, product 3  and GaI3  were dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (5\u2005mL). The suspension was stirred 30\u2005min and gently warmed to 60\u2009\u00b0C for 5\u2005min. The mixture was then freed of the solvent, extracted with DCM (3\u2005mL) and filtered. The filtrate was then concentrated until the saturation point was reached and stored at \u221232\u2009\u00b0C. A few colorless platelets of 3\u2009a were obtained after more than four weeks.Compounds 1H\u2005NMR : \u03b4=0.44 2), 0.47 2), 0.56 2), 3.96\u2005ppm ; 13C{1H}\u2005NMR \u03b4=\u22120.5 2), \u22120.5 2), 4.1 2), 65.3 , 65.4\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=13.3 2), 19.3 2), 19.4\u2005ppm 2). MS: ESI(+) m/z (%): 698.9902 [M\u2212I]+ (100), 507.1697 [M\u2212SrI2+Na]+ (30). IR: 2960 (w), 2879 (vw), 1456 (vw), 1400 (vw), 1369 (vw), 1258 (s), 1074 (s), 1024 (s), 951 (s), 894 (m), 851 (m), 794 (vs.), 769 (vs.), 712 (s), 634 (m), 557 (m), 497 (w), 448\u2005cm\u22121 (w).II  was dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (10\u2005mL). Subsequently SrI2  was added. Heating the mixture at reflux for 60\u2005min. resulted in a white suspension. Removing the solvent under reduced pressure gave a white precipitate which was extracted with DCM (20\u2005mL) followed by filtration. Upon washing with n\u2010pentane (5\u2005mL) and removal of the solvent, 4 was obtained as a pale white powder . For single crystal growth, product 4 (30\u2005mg 0.04\u2005mmol) and I2  were dissolved in DCM (4\u2005mL). Layering the solution with n\u2010pentane (20\u2005mL) yielded single crystals of 4\u2009a as brown blocks after three days.Compound 1H\u2005NMR : \u03b4=0.45 , 3.88 , 4.08\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=0.1 , 63.0 , 72.8\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=17.5\u2005ppm . MS: ESI(+) m/z (%): 264.0475 [M\u22122I]2+ (93), 447.2058 [M\u2212SrI2+Li]+ (3), 463.1797 [M\u2212SrI2+Na]+ (55), 479.1537 [M\u2212SrI2+K]+ (15), 655.0003 [M\u2212I]+ (16). IR: 2943 (w), 2880 (w), 1459 (w), 1398 (vw), 1353 (w), 1247 (m), 1069 (s), 1039 (s), 944 (s), 927 (s), 861 (s), 840 (s), 819 (s), 795 (s), 768 (vs.), 718 (s), 629 (m), 546 (w), 523\u2005cm\u22121 (w). CHN calcd for C16H40I2O6Si4Sr: C, 24.57; H, 5.15. Found: C, 25.42; H, 5.35.IV  was dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (15\u2005mL). Subsequently SrI2  was added. Heating the mixture at reflux for three hours resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (20\u2005mL), followed by filtration. The product 5 was then obtained as a colorless powder after removal of the solvent . For single\u2010crystal growth, the powder was dissolved in DCM (4\u2005mL) and layered with n\u2010pentane (20\u2005mL). Single crystals were obtained overnight as colorless needles.Compound 1H\u2005NMR : \u03b4=0.37 2), 3.94 , 3.95\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=\u22120.09 , 62.8 , 70.5 , 73.5\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=15.2\u2005ppm . MS: ESI(+) m/z (%): 551.2311 [M\u2212SrI2+Na]+ (82); IR: 2961 (m), 2943 (m), 2882 (w), 1454 (w), 1396 (w), 1366 (w), 1349 (w), 1302 (w), 1259 (s), 1091 (s), 1073 (s), 1039 (s), 1017 (s), 951 (s), 931 (s), 861 (m), 840 (m), 791 (vs.), 764 (s), 732 (s), 661 (s), 636 (m), 563 (w), 492 (w), 424\u2005cm\u22121 (w). CHN calcd for C20H48I2O8Si4Sr: C, 27.86; H, 5.67. Found: C, 27.60; H, 5.67.V  was dissolved in \u03b1,\u03b1,\u03b1\u2010trifluorotoluene (15\u2005mL). Subsequently, SrI2  was added. Heating the mixture at reflux for three hours resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (20\u2005mL) followed by filtration. The product 6 was then obtained as a colorless powder after removal of the solvent . For single\u2010crystal growth, the powder was dissolved in DCM (3\u2005mL) and layered with n\u2010pentane (20\u2005mL). Single crystals were obtained overnight as colorless platelets.Compound 1H\u2005NMR : \u03b4=0.45 , 4.15 , 4.42 , 7.02\u20137.16\u2005ppm ; 13C{1H}\u2005NMR : \u03b4=0.0 , 62.4 , 72.6 , 116.1 , 124.9 , 147.4\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4=19.8\u2005ppm . MS: ESI(+) m/z (%): 647.2311 [M\u2212SrI2+Na]+ (78), 839.0525 [M\u2212I]+ (35); IR: 2946 (w), 2885 (w), 1595 (w), 1500 (s), 1456 (m), 1400 (w), 1366 (w), 1250 (vs.), 1191 (m), 1161 (m), 1115 (m), 1063 (s), 934 (vs.), 916 (vs.), 862 (m), 837 (m), 817 (s), 774 (s), 750 (vs.), 734 (s), 711 (s), 630 (w), 605 (w), 533 (w), 516 (w), 484 (w), 456 (w), 422\u2005cm\u22121 (w). CHN calcd for C28H48I2O8Si4Sr\u22c50.5\u2009CH2Cl2: C, 33.93; H, 4.90. Found: C, 33.92; H, 4.68.6  was dissolved in DCM (10\u2005mL) and [222]cryptand  was added. The resulting suspension was stirred overnight to give a clear solution. The solvent was removed under reduced pressure to give an oily, greasy residue. Extracting with n\u2010pentane (10\u2005mL) and subsequent filtering of the suspension yielded a clear solution. Removing the solvent under reduced pressure gave a greasy crown ether\u2010[222]cryptand mixture (0.13\u2005g). [222]crypt contamination was more than 30\u2009%.Compound 1H\u2005NMR : \u03b4= 0.24 , 3.96\u20134.01 , 4.02\u20134.08 , 6.91\u2005ppm ; 13C{1H}\u2005NMR : \u03b4= 0.8 , 63.5 , 72.5 , 116.7 , 122.5 , 150.5\u2005ppm ; 29Si{1H}\u2005NMR : \u03b4= 11.5\u2005ppm . MS: HR\u2010ESI(+) m/z (%): 625.2502 [M+H]+ (100), 647.2320 [M+Na]+ (100). IR: 2945 (w), 2869 (w), 1593 (w), 1501 (s), 1452 (m), 1396 (w), 1370 (w), 1328 (w), 1247 (s), 1221 (m), 1124 (s), 1098 (s), 1053 (s), 948 (m), 923 (m), 823 (m), 790 (s), 763 (vs.), 740 (s), 631 (m), 450\u2005cm\u22121 (w).3\u2009a, 5), STOE IPDS2 , STOE IPDS2T (2\u2009a) or a STOE STADIVARI (4\u2009a) diffractometer, respectively. Measurements were performed at 100\u2005K with MoK\u03b1 (\u03bb=0.71073\u2005\u00c5) or CuK\u03b1 (\u03bb=1.54184\u2005\u00c5) radiation, graphite monochromatization or respective X\u2010ray optics. The structures were solved by direct methods and refinement with full\u2010matrix\u2010least\u2010squares against F2 using SHELXT and SHELXL on OLEX2 platform.3\u2009a and 6, we applied the SQUEEZE operation. A selection of respective crystal data is given below.Single\u2010crystal X\u2010ray diffraction experiments were carried out on a Bruker D8 Quest \u2005K, a=8.173(3), b=12.204(4), c=14.204(8)\u2005\u00c5; \u03b2=93.02(4)\u00b0, V=1414.8(11)\u2005\u00c53, \u03c1=1.680\u2005g\u2009cm\u22123, numerical absorption correction using STOE X\u2010AREA and X\u2010RED32.\u03bc=2.618\u2005mm\u22121, Tmin, Tmax=0.5303, 0.8053, 2\u0398 range 4.402\u201358.996\u00b0, reflections measured 21\u2009645, independent reflections 7891  0.0244, wR2  0.0590, GoF 1.047, \u0394\u03c1max, \u0394\u03c1min 1.27/\u22120.52\u2005e\u2009\u00c53.Crystal data of 2\u2009a: C14H36CaI6O5Si4, monoclinic, C2/c, Z=4, 100(2)\u2005K, a=11.408(3), b=12.970(2), c=25.570\u2005\u00c5; \u03b2=92.38(2)\u00b0, V=3484.7(16)\u2005\u00c53, \u03c1=2.284\u2005g\u2009cm\u22123, spherical absorption correction using STOE X\u2010AREA and LANA.\u03bc=5.654\u2005mm\u22121, Tmin, Tmax=0.1989, 0.4381, 2\u0398 range 3.458\u201350.994\u00b0, reflections measured 13\u2009999, independent reflections 3250 [R(int)=0.0924], 154 parameters, R\u2010index [I\u22652\u03c3(I)] 0.0548, wR2  0.1400, GoF 1.072, \u0394\u03c1max, \u0394\u03c1min 1.56/\u22120.91\u2005e\u2009\u00c53.Crystal data of 3\u2009a: C16H44Ga2I8O5Si6Sr, monoclinic, P21/c, Z=4, 100(2)\u2005K, a=23.3580(16), b=11.3585(7), c=20.6920(14)\u2005\u00c5; \u03b2=111.998(4)\u00b0, V=5090.2(6)\u2005\u00c53, \u03c1=2.254\u2005g\u2009cm\u22123, spherical absorption correction using STOE X\u2010AREA and LANA,\u03bc=7.110\u2005mm\u22121, Tmin, Tmax=0.4793, 0.7452, 2\u0398 range 4.232\u201350.738\u00b0, reflections measured 171\u2009072, independent reflections 9287 [R(int)=0.1514], 355 parameters, R\u2010index [I\u22652\u03c3(I)] 0.0675, wR2  0.1863, GoF 1.076, \u0394\u03c1max, \u0394\u03c1min 4.17/\u22121.57\u2005e\u2009\u00c53.Crystal data of 4\u2009a: C16H40I4O6Si4Sr, monoclinic, P21/c, Z=4, 100(2)\u2005K, a=12.0422(5), b=22.2125(6), c=12.8413(4)\u2005\u00c5; \u03b2=95.734(3)\u00b0, V=3417.7(2)\u2005\u00c53, \u03c1=2.014\u2005g\u2009cm\u22123, spherical absorption correction using STOE X\u2010AREA and LANA,\u03bc=32.123\u2005mm\u22121, Tmin, Tmax=0.212, 0.360, 2\u0398 range 7.378\u201350.994\u00b0, reflections measured 26\u2009969, independent reflections 6337 [R(int)=0.0854], 288 parameters, R\u2010index [I\u22652\u03c3(I)] 0.0391, wR2  0.0894, GoF 0.804, \u0394\u03c1max, \u0394\u03c1min 1.23/\u22121.51\u2005e\u2009\u00c53.Crystal data of 5: C20H48I2O8Si4Sr, triclinic, P\u20101, Z=2, 110(2)\u2005K, a=8.4870(4), b=14.9819(7), c=15.4929(7)\u2005\u00c5, \u03b1=105.457(2)\u00b0, \u03b2=102.187(2)\u00b0, \u03b3=99.376(2)\u00b0, V=1804.98(15)\u2005\u00c53, \u03c1=1.601\u2005g\u2009cm\u22123, multiscan absorption correction using SADABS2016[50],\u03bc=3.371\u2005mm\u22121, Tmin, Tmax=0.5094, 0.8894, 2\u0398 range 4.642\u201357.786\u00b0, reflections measured 54\u2009208, independent reflections 9456 [R(int)=0.0442], 365 parameters, R\u2010index [I\u22652\u03c3(I)] 0.0323, wR2  0.0540, GoF 1.034, \u0394\u03c1max, \u0394\u03c1min 1.21/\u22120.80\u2005e\u2009\u00c53.Crystal data of 6\u22c51.5DCM: C29.5H51Cl3I2O8Si4Sr, triclinic, P\u20101, Z=4, 100(2)\u2005K, a=11.9953(8)\u2005\u00c5, b=16.0514(12)\u2005\u00c5, c=24.936(2)\u2005\u00c5, \u03b1=76.567(6)\u00b0, \u03b2=85.494(6)\u00b0, \u03b3=86.477(6)\u00b0, V=4650.7(6)\u2005\u00c53, \u03c1=1.562\u2005g\u2009cm\u22123, numerical absorption correction using STOE X\u2010AREA and X\u2010RED32,\u03bc=2.801\u2005mm\u22121, Tmin, Tmax=0.5094, 0.8894, 2\u0398 range 4.642\u201357.786\u00b0, reflections measured 52\u2009818, refined as a two component twin, 901 parameters, R\u2010index [I\u22652\u03c3(I)] 0.0780, wR2  0.2325, GoF 0.871, \u0394\u03c1max, \u0394\u03c1min 2.32/\u22121.74\u2005e\u2009\u00c53.The authors declare no conflict of interest."}
{"text": "The mol\u00adecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. In the crystal, the mol\u00adecules are linked along the a-axis direction through van der Waals forces and by face-to-face \u03c0-stacking between the thio\u00adphene rings and between the benzene rings of neighbouring mol\u00adecules along the b axis into zigzag sheets lying parallel to the bc plane.The mol\u00adecular structure of the title compound consists of a 2,5-di\u00adchloro\u00adthio\u00adphene ring and a 2-chloro\u00adphenyl ring linked  13H7Cl3OS, consists of a 2,5- di\u00adchloro\u00adthio\u00adphene ring and a 2-chloro\u00adphenyl ring linked via a prop-2-en-1-one spacer. The dihedral angle between the 2,5-di\u00adchloro\u00adthio\u00adphene and 2-chloro\u00adphenyl rings is 9.69\u2005(12)\u00b0. The mol\u00adecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The mol\u00adecular conformation is stabilized by two intra\u00admolecular C\u2014H\u22efCl contacts and one intra\u00admolecular C\u2014H\u22efO contact, forming S(5)S(5)S(6) ring motifs. In the crystal, the mol\u00adecules are linked along the a-axis direction through van der Waals forces and along the b axis by face-to-face \u03c0-stacking between the thio\u00adphene rings and between the benzene rings of neighbouring mol\u00adecules, forming corrugated sheets lying parallel to the bc plane. The inter\u00admolecular inter\u00adactions in the crystal packing were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are Cl\u22efH/ H\u22efCl (28.6%), followed by C\u22efH/H\u22efC (11.9%), C\u22efC (11.1%), H\u22efH (11.0%), Cl\u22efCl (8.1%), O\u22efH/H\u22efO (8.0%) and S\u22efH/H\u22efS (6.6%).The mol\u00adecular structure of the title compound, C The mol\u00adecules are packed into corrugated sheets lying parallel to (011)  Figs. 2 and 3 \u25b8.CrystalExplorer ] with de + di \u2243 2.85\u2005\u00c5 . The C\u22efH/H\u22efC inter\u00adactions are shown in Fig.\u00a04c). The scattered points show the van der Waals contacts and \u03c0\u2013\u03c0 stacking inter\u00adactions. The inter\u00adatomic C\u22efC contacts appear as an arrow-shaped distribution of points in Fig.\u00a04d), with the vertex at de = di = 1.75\u2005\u00c5. The C\u22efC contacts reflect \u03c0\u2013\u03c0 inter\u00adactions between the aromatic rings. The H\u22efH inter\u00adactions are reflected in Fig.\u00a04e) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule. The split spike with the tip at de = di \u2243 1.3\u2005\u00c5 is due to the short inter\u00adatomic H\u22efH contacts. Cl\u22efCl contacts [Fig.\u00a04f)] are disfavoured when the number of H atoms on the mol\u00adecular surface is large because of competition with the more attractive H\u22efCl contacts. Cl\u22efCl contacts from a parallel alignment of C\u2014Cl bonds  may be indicated. They are known in the literature as type-I halogen\u2013halogen inter\u00adactions ] also have a symmetrical distribution of points, with two pairs of thin and thick edges at de + di \u2243 2.75\u2005\u00c5. The S\u22efH contacts shown in Fig.\u00a04h) are contracted to a much lesser degree.The C\u2014H\u22efCl inter\u00adactions appear as two distinct spikes in the fingerprint plot -3-(thio\u00adphen-2-yl)prop-2-en-1- one [(X); Yesilyurt et al., 2018E)-1-(2-amino\u00adphen\u00adyl)-3- (thio\u00adphen-2-yl)prop-2-en-1-one [(XI); Chantrapromma et al., 2013et al., 2018P1, while (III) and (IV) are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I)C(7) chains by means of C\u2014H\u22efO hydrogen bonds. In (V), there are again no hydrogen bonds nor any \u03c0\u2013\u03c0 stacking inter\u00adactions but in (VI), the mol\u00adecules are linked into C(5) chains by C\u2014H\u22efO hydrogen bonds. In each of compounds (I)\u2013(VI), the mol\u00adecular skeletons are close to planarity, and there are short halogen\u2013halogen contacts in the structures of compounds (II) and (V) and a short Br\u22efO contact in the structure of compound (VI). In (VII), the mol\u00adecule is non-planar, with a dihedral angle of 22.6\u2005(2)\u00b0 between the aromatic rings. The mol\u00adecules are linked by pairs of C\u2014H\u22ef\u03c0 inter\u00adactions, forming inversion dimers. There are no other significant inter\u00admolecular inter\u00adactions present. In (VIII), the mol\u00adecule is nearly planar, the dihedral angle between the thio\u00adphene and phenyl rings being 9.07\u2005(8)\u00b0. The mol\u00adecules are linked via weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, forming chains propagating along the c-axis direction. In (IX), the thienyl ring is not coplanar with the benzene ring, their planes forming a dihedral angle of 13.2\u2005(4)\u00b0. In the crystal, mol\u00adecules stack along the a-axis direction, with the inter\u00adplanar separation between the thienyl rings and between the benzene rings being 3.925\u2005(6)\u2005\u00c5. In (X), the thio\u00adphene ring forms a dihedral angle of 26.04\u2005(9)\u00b0 with the benzene ring. The mol\u00adecular conformation is stabilized by an O\u2014H\u22efN hydrogen bond. The mol\u00adecules are connected through C\u2014H\u22efO hydrogen bonds, forming wave-like layers parallel to the ab plane, which are further linked into a three-dimensional network by C\u2014H\u22ef\u03c0 inter\u00adactions. In (XI), the mol\u00adecule is almost planar with a dihedral angle of 3.73\u2005(8)\u00b0 between the phenyl and thio\u00adphene rings. An intra\u00admolecular N\u2014H\u22efO hydrogen bond generates an S(6) ring motif. Adjacent mol\u00adecules are linked into dimers in an anti-parallel face-to-face manner by pairs of C\u2014H\u22efO inter\u00adactions. Neighbouring dimers are further linked into chains along the c-axis direction by N\u2014H\u22efN hydrogen bonds. In (XII), the dihedral angle between the thio\u00adphene and benzene rings increases to12.24\u2005(15)\u00b0. The mol\u00adecular conformation is stabilized by intra\u00admolecular C\u2014H\u22efCl contacts, forming S(6) and S(5) ring motifs. In the crystal, the mol\u00adecules are linked through face-to-face \u03c0-stacking between the thio\u00adphene rings and the benzene rings of the mol\u00adecules into zigzag sheets lying parallel to the bc plane.The closest related compounds with the same skeleton and containing a similar bis-chalcone moiety to the title compound but with different substituents on the aromatic rings are:  = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018018066/qm2131sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018018066/qm2131Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018018066/qm2131Isup3.cmlSupporting information file. DOI: 1036796CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the adduct contains a neodymium(III) cation, three coordinated nitrate anions, four coordinated water mol\u00adecules and three uncoordinated neutraltriazine mol\u00adecules. The crystal structure consists of a three-dimensional supra\u00admolecular framework held together by a network of O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds between the coordinated water mol\u00adecules, nitrate ions and triazine mol\u00adecules. The uncoordinated neutral triazine moieties form N\u2014H\u22efN hydrogen bonds. Hirshfeld surface and fingerprint plots identify the major contributors to the inter\u00admolecular inter\u00adactions. 3)3(H2O)4]\u00b73C3H4N4, neodymium is ten-coordinate with a distorted bicapped square-anti\u00adprismatic geometry formed from six O atoms from three nitrate ions and four O atoms from four coordinated water mol\u00adecules. The structure also contains neutral 3-amino-1,2,4-triazine mol\u00adecules which are not coordinated to the central metal atom. The coordinated water mol\u00adecules and nitrate ions of adjacent complexes are linked by O\u2014H\u22efO hydrogen bonds to form cyclic R22(8) ring motifs, which in turn are further connected via hydrogen bonds to generate a sheet-like structure. The triazine mol\u00adecules are involved in a number of hydrogen-bonding inter\u00adactions: N\u2014H\u22efN and O\u2014H\u22efN inter\u00adactions to form R33(9) motifs and N\u2014H\u22efN inter\u00adactions to link the organic mol\u00adecules into chains. Weak C\u2014H\u22efO hydrogen bonds also occur between triazine mol\u00adecules and coordinated nitrate atoms. All these inter\u00admolecular contacts contribute to the stabilization of the three-dimensional supra\u00admolecular framework. Hirshfeld surface analysis shows that N\u22efH/H\u22efN and H\u22efH inter\u00adactions account for 42.9 and 20.6% of the surface, respectively.In the title compound, [Nd(NO All these inter\u00admolecular inter\u00adactions appear to play a significant role in stabilizing the crystal structure and result in the formation of a three-dimensional supra\u00admolecular framework  is based on the distances from the nearest atom inside (di) and outside (de) the surface. The three-dimensional dnorm surface of the title compound is shown in Fig.\u00a05dnorm values on the surface correspond to the N\u2014H\u22efN, N\u2014H\u22efO and O\u2014H\u22efO inter\u00adactions. Analysis of the two-dimensional fingerprint plots reveal that the H\u22efH (20.6%) and N\u22efH/H\u22efN (42.9%) inter\u00adactions are the highest contributors to the Hirshfeld surface. Smaller contributions come from O\u22efH/H\u22efO (13.3%) C\u22efH/H\u22efC (6.3%), N\u22efN (6.2%), C\u22efN/N\u22efC (4.6%), N\u22efO/O\u22efN (2.8%) and C\u22efO/O\u22efC (1.8%) inter\u00adactions -biscopper(II)] and KUCNEC [with bis\u00adhexa\u00adkis\u00adtricopper(II)] \u00adbis\u00ad\u00adcobalt]; Palion-Gazda et al., 2015catena-[bis\u00ad(\u03bc2-dicyanamido)\u00adbis\u00ad\u00adcobalt]; \u015ewitlicka-Olszewska et al., 2016A search of the Cambridge Structural Database 3\u00b76H2O (0.219g) (Alfa Aesar). Di\u00adchloro\u00admethane (5\u2005ml) was then added and the mixture refluxed for 7\u2005h at 353\u2005K. The resulting solution was then allowed to cool slowly to room temperature. After two weeks, brown-coloured crystals were obtained, m.p. = 378\u2005K.The title compound was prepared by adding a hot methano\u00adlic solution (20\u2005ml) of 3-amino-1,2,4-triazine (0.043g) (Aldrich) to a hot methano\u00adlic solution (20\u2005ml) of Nd(NOUiso(H) set to 1.2\u20131.5Ueq(C). The water and N-bound H atoms were located in difference-Fourier maps and refined with Uiso(H) = 1.2Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018011714/cq2026sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018011714/cq2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 1583097CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The conformations of the title compounds, (I) and (II), are very similar. The pyran rings adopt envelope conformations, the piperidine rings have chair conformations and the pyrrolidine rings adopt twist conformations. Intra- and inter\u00admolecular C\u2014H\u22efO hydrogen bonds occur. Compound (II) crystallizes with two independent mol\u00adecules in the asymmetric unit which are linked by C\u2014H\u22efO hydrogen bonds. 32H25ClN2O4 (I) and C33H28N2O5 (II), the six-membered pyran and piperidine rings adopt envelope and chair conformations, respectively. The five-membered pyrrolidine rings adopt twist conformations. Compound (II) crystallizes with two independent mol\u00adecules (A and B) in the asymmetric unit. In all three mol\u00adecules there is a C\u2014H\u22efO intra\u00admolecular hydrogen bond present enclosing an S(7) ring motif. In (I), both oxygen atoms of the nitro group are disordered, while in (II) the meth\u00adoxy\u00adbenzene group is disordered in mol\u00adecule B. The geometries were regularized by soft restraints. In the crystal of (I), mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming chains along [010]. The chains are linked by C\u2014H\u22efCl hydrogen bonds, forming layers parallel to (10A and B mol\u00adecules are linked via C\u2014H\u22efO hydrogen bonds, forming a square four-membered A\u2013B\u2013A\u2013B unit. These units are linked by a number of C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional supra\u00admolecular structure.In the title compounds, C The structural overlap of compound (I)B of compound (II)B of compound II (major component) on mol\u00adecule A is shown in Fig.\u00a05A and IIB) the pyran rings have envelope conformations with the methyl\u00adene C atom C21 as the flap. The piperidine rings adopt chair conformations, while the pyrrolidine rings adopt twist conformations on the N1\u2014C12 bond (N1A\u2014C12A in IIA and N1B\u2014C12B in IIB).The mol\u00adecular structure of compound (I)A and B of compound (II)A and 66.7\u2005(2) and 59.3\u2005(5)\u00b0 for mol\u00adecule B. The benzene rings (C27\u2013C32 and C14\u2014C19) are inclined to each other by 50.0\u2005(1)\u00b0 in (I)A and 71.6\u2005(2)\u00b0 in mol\u00adecule B of (II)A and 36.1\u2005(2)\u00b0 for mol\u00adecule B in (II)A and 13.1\u2005(2)\u00b0 in mol\u00adecule B of compound (II)A and 36.2\u2005(2)\u00b0 in mol\u00adecule B of compound (II)supporting information. The keto atom O1 deviates from the mean plane of the plane of the ace\u00adnaphthyl\u00adene ring system (C1\u2014C12) by 0.070\u2005(2)\u2005\u00c5 in (I)et al., 2013abThe mean plane of the five-membered pyrrolidine ring (N1/C12/C13/C21/C22) is inclined to the mean plane of the cyclo\u00adpen3\u2013en-1-one ring (C1/C2/C10\u2013C12) by 85.7\u2005(1)\u00b0 in compound (I)b-axis direction. The chains are linked by C\u2014H\u22efCl hydrogen bonds, forming layers parallel to the s Table\u00a02. These as Table\u00a02.et al., 2016H,6\u2032H,6b\u2032H-spiro\u00adindolizin]-2-one skeleton yielded two hits: namely 6-(4-meth\u00adoxy\u00adphen\u00adyl)-6a-nitro-6,6a,6b,7,8,9,10,12a-octa\u00adhydro\u00adspiro\u00adindolizine-12,3-indolin]-2-one  for (I)H-chromene (1\u2005mmol) for (II)To a solution of ace\u00adnaphtho\u00adquinone (1.0\u2005mmol) and piperidine-2-carb\u00adoxy\u00adlic acid (1.5\u2005mmol) in dry toluene, was added 2-(4-chloro\u00adphen\u00adyl)-3-nitro-2Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. In compound (I)B is disordered, as detectable from the large displacement parameters for the C and O atoms and short C\u2014C and C\u2014O bond lengths. This disorder over two positions was modelled and the site occupancies refined to 0.739\u2005(5) and 0.261\u2005(5). The geometry was regularized by soft restraints.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019000422/su5472sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: Click here for additional data file.10.1107/S2056989019000422/su5472Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019000422/su5472IIsup3.cmlSupporting information file. DOI: 10.1107/S2056989019000422/su5472sup4.pdfPuckering and asymmety parameters. DOI: 1024915, 1024235CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction to: Infect Agents Cancer (2019) 14:46https://doi.org/10.1186/s13027-019-0262-5The original publication of this article  containeErrors in original publication:\u201cFish notch1b/Human NOTCH2\u201d should be \u201cFish reck/Human RECK\u201cFish notch1b/Human NOTCH3\u201d should be \u201cFish srd5a1/Human SRD5A1\u201cFish notch1b/Human NOTCH4\u201d should be \u201cFish wnt7bb/ HumanWNT7B\u201d\u201cFish notch1b/Human NOTCH5\u201d should be \u201cFish pparg/Human PPARG\u201d"}
{"text": "Nature Communications 10.1038/s41467-019-12167-9, published online 19 September 2019.Correction to: S\u03bb(P)\u2009=\u20091.45, WP\u2009=\u20091.08 and W\u03c9\u2009=\u200932.3\u2019. The correct version reads \u2018S\u03bb(P)\u2009=\u20090.90, WP\u2009=\u20090.71 and W\u03c9\u2009=\u200925.3\u2019. Similarly in Fig.\u00a01b, the label at the top of the left panel incorrectly read \u2018S\u03bb(P)\u2009=\u20090.90, WP\u2009=\u20090.71 and W\u03c9\u2009=\u200925.3\u2019. The correct version reads \u2018S\u03bb(P)\u2009=\u20091.45, WP\u2009=\u20091.08 and W\u03c9\u2009=\u200932.3\u2019. This has been corrected in both the PDF and HTML versions of the Article.The original version of this Article contained errors in Fig.\u00a01. In Fig.\u00a01a, the label at the top of the left panel incorrectly read \u2018"}
{"text": "Correction to: Microbiomehttps://doi.org/10.1186/s40168-019-0643-4Following publication of the original article , the autPage 3, right column: Additional\u00a0file\u00a01: Table S1\u2009\u2192\u2009Table\u00a01.Page 4, right column: detail in Additional\u00a0file\u00a01: Table S1\u2009\u2192\u2009detail in Additional\u00a0file\u00a02: Supplementary results.Page 5, right column: Table\u00a02 \u2009\u2192\u2009Table\u00a02 .Page 12, left column: Additional\u00a0file\u00a01: Table S10\u2009\u2192\u2009Additional\u00a0file\u00a01: Table S11.Page 12, left column: Additional\u00a0file\u00a01: Table S12\u2009\u2192\u2009Additional\u00a0file\u00a05: Table S12.Description of additional files on Page 12 and 13:Table S10 and Table\u2009S12\u2192\u2009Table S12 and Table S10. Respectively.Additional file 5 Table S5\u2009\u2192\u2009Additional file 5: Table S12.Kim et al. [19]\u2009\u2192\u2009Kim et al. [21]"}
{"text": "In the crystal, the mol\u00adecules form zigzag stacks along the  15H12ClNO3, consists of a 1,2-di\u00adhydro\u00adquinoline-4-carb\u00adoxyl\u00adate unit with 2-chloro\u00adethyl and propynyl substituents, where the quinoline moiety is almost planar and the propynyl substituent is nearly perpendicular to its mean plane. In the crystal, the mol\u00adecules form zigzag stacks along the a-axis direction through slightly offset \u03c0-stacking inter\u00adactions between inversion-related quinoline moieties which are tied together by inter\u00admolecular C\u2014HPrpn\u00adyl\u22efOCarbx and C\u2014HChlethy\u22efOCarbx  hydrogen bonds. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (29.9%), H\u22efO/O\u22efH (21.4%), H\u22efC/C\u22ef H (19.4%), H\u22efCl/Cl\u22efH (16.3%) and C\u22efC (8.6%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, the C\u2014HPrpn\u00adyl\u22efOCarbx and C\u2014HChlethy\u22efOCarbx hydrogen bond energies are 67.1 and 61.7\u2005kJ\u2005mol\u22121, respectively. Density functional theory (DFT) optimized structures at the B3LYP/ 6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C We report herein on the synthesis and the mol\u00adecular and crystal structures of the title compound along with the Hirshfeld surface analysis and the inter\u00admolecular inter\u00adaction energies and the density functional theory (DFT) computational calculation carried out at the B3LYP/6\u2013311\u2005G level.The quinoline ring system is an important structural unit in naturally occurring quinoline alkaloids, therapeutics and synthetic analogues with inter\u00adesting biological activities. Quinolone derivatives possess a variety of pharmacological properties such as anti-bacterial (Hu A (C1\u2013C6) and B (N1/C1/C6\u2013C9), of the di\u00adhydro\u00adquinoline unit are oriented at a dihedral angle of 2.69\u2005(17)\u00b0. The mean plane through the di\u00adhydro\u00adquinoline unit is almost planar with a maximum deviation of 0.040\u2005(3)\u2005\u00c5 for atom N1, and the propynyl substituent is nearly perpendicular to that plane, the C6\u2014N1\u2014C10\u2014C11 torsion angle being \u221279.6\u2005(4)\u00b0. The carboxyl group is twisted out of coplanarity with the di\u00adhydro\u00adquinoline unit by a dihedral angle of 47.13\u2005(23)\u00b0; this is also indicated by the C1\u2014C9\u2014C13\u2014O2 torsion angle of \u221244.2\u2005(6)\u00b0.The title mol\u00adecule consists of a 1,2-di\u00adhydro\u00adquinoline-4-carboxyl\u00adate unit with 2-chloro\u00adethyl and propynyl substituents Fig.\u00a01. The cona-axis direction through slightly offset \u03c0-stacking inter\u00adactions between inversion-related quinoline moieties  hydrogen bonds, enclosing A (C1\u2013C6) and B (N1/C1/C6\u2013C9), of the di\u00adhydro\u00adquinoline unit, Cg2\u22efCg1i, Cg2\u22efCg1ii and Cg1\u22efCg1i , may further stabilize the structure.In the crystal, the mol\u00adecules form zigzag stacks along the es Fig.\u00a02. The stas Table\u00a01. The \u03c0\u2013\u03c0CrystalExplorer17.5  analysis  are viewed as a pair of spikes with the tips at de + di = 2.28\u2005\u00c5. In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions, the pairs of characteristic wings in Fig.\u00a07d arise from H\u22efC/C\u22efH contacts (19.4%) and are viewed as pairs of spikes with the tips at de + di = 2.65\u2005\u00c5 and 2.70\u2005\u00c5 for the thin and thick spikes, respectively. The scattered points in the pair of wings in the fingerprint plot delineated into H\u22efCl/Cl\u22efH  have a symmetrical distribution with the edges at de + di = 2.60\u2005\u00c5. The C\u22efC contacts, Fig.\u00a07f, have an arrow-shaped distribution of points with the tip at de = di = 1.72\u2005\u00c5. Finally, the characteristic tip and wings in the fingerprint plots delineated into C\u22efN/N\u22efC and O\u22efCl/Cl\u22efO contacts  have the tips at de = di = 1.73 and 3.70\u2005\u00c5, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a07H Table\u00a02, contribdnorm plotted onto the surface are shown for the H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH and H \u22ef Cl/Cl\u22efH inter\u00adactions in Fig.\u00a08a\u2013d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efO/O\u22efH, H \u22ef C/C\u22efH and H\u22efCl/Cl\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be \u221225.2 (Eele), \u22122.1 (Epol), \u221285.4 (Edis), 57.5 (Erep) and \u221267.1 (Etot) for the C\u2014HPrpn\u00adyl\u22efOCarbx hydrogen bond and \u221226.5 (Eele), \u22124.7 (Epol), \u221273.2 (Edis), 54.3 (Erep) and \u221261.7 (Etot) for the C\u2014HChlethy\u22efOCarbx hydrogen bond.The inter\u00admolecular inter\u00adaction energies were calculated using the CE\u2013B3LYP/6\u201331G energy model available in via density functional theory (DFT) using the standard B3LYP functional and 6\u2013311\u2005G basis-set calculations . The significance of \u03b7 and \u03c3 is to evaluate both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig.\u00a09E = ELUMO\u00a0\u2212\u00a0EHOMO] of the mol\u00adecule is 3.6984\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22126.3024 and \u22122.6040\u2005eV, respectively.The optimized structure of the title compound in the gas phase was generated theoretically et al., 2016et al., 2018abet al., 2019A non-alkyl\u00adated analogue, namely quinoline and its derivatives, has been reported  and TBAB . The reaction mixture was stirred at room temperature for 6\u2005h. After removal of the salts by filtration, the solvent was evaporated under reduced pressure and the resulting residue was dissolved in di\u00adchloro\u00admethane. The organic phase was dried with Na2SO4, and then concentrated under reduced pressure. The pure compound was obtained by column chromatography using hexa\u00adne/ethyl acetate (3/1) as eluent. The isolated solid was recrystallized from hexa\u00adne/ethyl acetate (3:1) to afford colourless crystals .To a solution of 2-chloro\u00adethyl 2-oxo-1,2-di\u00adhydro\u00adquinoline-4-carboxyl\u00adate  in DMF (10.00\u2005ml) were added propargyl bromide , K2 H atoms, respectively) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The largest peak and hole in the final difference map are +0.73\u2005e\u2005\u00c5\u22123 (1.00\u2005\u00c5 away from Cl1) and \u22120.35\u2005e\u2005\u00c5\u22123 (0.64\u2005\u00c5 away from C14), and are associated with the 2-chloro\u00adethyl\u00adcarb\u00adoxy group and may indicate a slight degree of disorder here but it was not considered serious enough to model.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019012283/lh5918sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019012283/lh5918Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019012283/lh5918Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019012283/lh5918Isup4.cmlSupporting information file. DOI: 1951439CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Quantum chemical calculations revealed details on the strength and geometrical requirements of these N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds, and a subsequent survey of the Protein Data Bank (PDB) based on these criteria suggested that numerous protein-ligand complexes contain such N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds. An ensuing experimental investigation into the G9a-like protein (GLP)-inhibitor complex demonstrated that N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds affect the activity of the inhibitors against the target enzyme. These results should provide the basis for the use of N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds in drug discovery.In the context of drug design, C-H\u00b7\u00b7\u00b7O hydrogen bonds have received little attention so far, mostly because they are considered weak relative to other noncovalent interactions such as O-H\u00b7\u00b7\u00b7O hydrogen bonds, \u03c0/\u03c0 interactions, and van der Waals interactions. Herein, we demonstrate the significance of hydrogen bonds between C-H groups adjacent to an ammonium cation and an oxygen atom (N Such interactions manifest between proteins and their ligands in many protein complexes registered on the Protein Data Bank (PDB). Accordingly, these interactions should always be considered when designing ligands for target proteins7.Noncovalent interactions, such as heteroatom-hydrogen bonds X-H\u00b7\u00b7\u00b7Y  and \u03c0/\u03c0 interactions play a critical role in the formation of protein-ligand complexes11. However, when the C-H group is activated by electron-withdrawing groups, e.g. C-H groups that are covalently bound to a cationic nitrogen atom (N+-C-H), C-H\u00b7\u00b7\u00b7O hydrogen bonds may become as strong as heteroatom-hydrogen bonds, which could be important for molecular recognition19. For example, N+-C-H\u00b7\u00b7\u00b7Y hydrogen bonds are likely to be involved in the substrate recognition of tetraalkylammonium-based catalysts21, and the ligand/substrate recognition in receptors/enzymes may be controlled by N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds , the latter are almost exhaustively protonated under physiological conditions (pH\u2009=\u20097\u20138). Accordingly, ligands bearing tetraalkylammonium or aliphatic amino groups could be recognized by the oxygen atoms of the proteins via N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds  theoretical research and criteria setting for N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds by quantum chemical calculations , propanoate (2), ethanol (3), and phenol (4) as hydrogen acceptor models for the protein peptide bond/Asn/Gln, Asp/Glu, Ser/Thr, and Tyr, respectively, and monomethylammonium (5), trimethylammonium (6) or N-methylpiperidium (7) as hydrogen donor models in protonated aliphatic amine-containing ligands. Geometry optimizations and single-point calculations were carried out at the M06-2X/6-311++G** level of theory26. The results of this computational study allowed us to establish selection criteria for N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds  analysis28 of 5 indicated that the positive charge is distributed over the H atoms , including those of the CH3 group, rather than being localized on the N atom (\u22120.688)  is more positive than that of monomethylamine  or ethane . These results suggest high potential for the N+-C-H group to act as a hydrogen donor in hydrogen bonds.Initially, we analyzed the electrical charges on the hydrogen donors of the NA1, B1 and C1, i.e., complexes of 1, 2, and 3 with 6, as well as that of complex D1, which consists of 4 and 7 in the gas phase , which suggests the formation of intermolecular hydrogen bonds between these atoms  or 2,2-dimethylpropane (11), and 7 in D1 is replaced with N-methylpiperidine (12) or methyl cyclohexane (13) , the C-H\u00b7\u00b7\u00b7O angle (\u03c8), the H\u00b7\u00b7\u00b7O=C/H\u00b7\u00b7\u00b7O-C angle (\u03be), and the H-elevation angle (\u03b8)30  were calculated  30 Figs\u00a0 and 5A. ant Fig.\u00a0. For H\u00b7\u00b7ted Fig.\u00a0, which ited Fig.\u00a0. The est7\u2009\u00c5 Fig.\u00a0. The dis\u2009\u00c5) Figs\u00a0 and 5B. A4 on the C-H\u00b7\u00b7\u00b7O angle (\u03c8). For 90\u00b0\u2009<\u2009\u03c8\u2009<\u2009180\u00b0, the interaction energy is relatively low   Figs\u00a0 and 5C. ses Fig.\u00a0, a simil80\u00b0 Figs\u00a0 and 5C. \u03be). Calculating the interaction energies, we discovered that these energies depend on the type of hydrogen acceptors. In the case of amide acceptors, i.e., for 105\u00b0\u2009<\u2009\u03be\u2009<\u2009180\u00b0, the interaction energies are low and the preferred angles are \u03be\u2009>\u2009135\u00b0  was permissible, and B4 exhibited a preference for \u03be\u2009>\u2009240\u00b0   Figs\u00a0. For car\u03b8). For \u03b8\u2009<\u200970\u00b0 (A4), \u03b8\u2009<\u200960\u00b0 (C4), and \u03b8\u2009<\u200975\u00b0 (D4), low interaction energies were calculated  and propanoate (2) are widely distributed  and phenol (4) is centered on the area where the plane bisecting the C-O-H angle intersects with the C-O-H plane  and H\u00b7\u00b7\u00b7O (dHO) bond distances  in the \u03be dataset, we observed 13 interactions with 105\u00b0\u2009<\u2009\u03be\u2009<\u2009135\u00b0. According to our calculations  and C-elevation (\u03d5) angles are subject to a certain degree of correlation , whereas contacts of carboxylate acceptors exhibited a wide distribution of these angles -inhibitor complex 14a . Relative to 14a, 14b significantly reduced the GLP-inhibitory activity (IC50\u2009=\u20090.664\u2009\u03bcM) in the 0.1\u20131\u2009\u03bcM concentration range. In the same concentration range, 14c showed a decreased GLP-inhibitory activity (IC50\u2009=\u20091.45\u2009\u03bcM) compared to 14a and 14b, while 14d did not show any GLP inhibition up to 3\u2009\u03bcM. The latter result should most likely be rationalized in terms of a lack in both electrostatic interactions and C-H\u00b7\u00b7\u00b7O hydrogen bonds between the ligand and GLP. Moreover, we determined the dissociation constant and thermodynamic parameters of 14a\u2013c by means of isothermal titration calorimetry (ITC). As shown in Supplementary Fig.\u00a014a\u2013c was distinctly dependent on the number of methyl group , which is consistent with the IC50 values of 14a\u2013c. The thermodynamic parameters were also dependent on the number of methyl group: the \u0394H values for dimethyl 14a, monomethyl 14b, and non-methyl 14c were \u221210.7\u2009kcal/mol, \u22128.58\u2009kcal/mol, and \u22127.04\u2009kcal/mol, respectively; the \u2212T\u0394S values for 14a, 14b, and 14c were 1.42\u2009kcal/mol, 0.10\u2009kcal/mol, and \u22121.19\u2009kcal/mol, respectively . It is well known that enthalpic forces such as hydrogen bond formation can decrease entropic forces by restricting the degrees of freedom of water molecules and protein conformation33. Based on this, there is a possibility that the methyl group of 14a and 14b reduced the \u0394H value by the conformational fixation of GLP through the formation of N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds, which resulted in reduction of the T\u0394S value by decreasing the degrees of freedom of water molecules and protein conformation, and the effect of enthalpy was larger than that of entropy. Taken together, the observed GLP-inhibitory activity, disassociation constant and thermodynamic parameters for 14a\u2013d strongly suggests that the N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds in the GLP-ligand complex are responsible for their GLP-inhibitory activity, although the effect might not be attributed exclusively to the N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds.To experimentally validate the importance of the N14a Fig.\u00a0, one of GLP Fig.\u00a0. In ordetom Fig.\u00a0. Compounely Fig.\u00a0. If the ity Fig.\u00a0. The par+-CH3 groups do not engage in N+-C-H\u00b7\u00b7\u00b7O hydrogen bonds with any protein-based oxygen atom. The X-ray crystal structure of tyrosine kinase with Ig and EGF homology domains-2 (tie-2) complexed to its inhibitor 15a indicates that the methylene group that is in conjugation with the aliphatic amino group forms an N+-C-H\u00b7\u00b7\u00b7O hydrogen bond, but the methyl groups do not 36, which is often used for long distance interactions, with the 6-311++G** basis set in the gas phase or in the water phase37. Structures were considered as minima in case of all harmonic frequencies being positive. All interaction energies were corrected for basis set superposition errors (BSSE) by the counterpoise procedure38. To gauge the accuracy of the M06-2X/6-311++G** level of theory, the thus obtained binding energies were compared to those obtained from MP2/aug-cc-pVTZ  C\u00b7\u00b7\u00b7O distance (dCO): <3.7\u2009\u00c527; (ii) H\u00b7\u00b7\u00b7O distance (dHO): <2.7 \u00c5; (iii) C-H\u00b7\u00b7\u00b7O angle (\u03c8): >90\u00b0 for the peptide bond/Asn/Gln and Asp/Glu acceptors, or >105\u00b0 for the Ser/Thr/Tyr acceptors; (iv) H\u00b7\u00b7\u00b7O=C angle (\u03be): >105\u00b0 for the peptide bond/Asn/Gln acceptors, >90\u00b0 for the Asp/Glu acceptors, or 105\u00b0\u2013150\u00b0 for the Ser/Thr/Tyr acceptors; (v) H\u00b7\u00b7\u00b7elevation angle (\u03b8): <70\u00b0 for the peptide bond/Asn/Gln acceptors, <80\u00b0 for the Asp/Glu acceptors; (vi) N+-C\u00b7\u00b7\u00b7O angle (\u03b1): 60\u00b0\u2013160\u00b0; (vii) C\u00b7\u00b7\u00b7O-C angle (\u03b2): >95\u00b0 for the peptide bond/Asn/Gln, >90\u00b0 for the Asp/Glu acceptors, or 95\u00b0\u2013160\u00b0 for the Ser/Thr/Tyr acceptors; (viii) C-elevation (\u03d5): <80\u00b0 for the peptide bond/Asn/Gln and <90\u00b0 for Asp/Glu. The H-elevation angle (\u03b8) was calculated according to sin\u03b8\u2009=\u2009sin\u03be\u2009\u00b7\u2009sin\u03c7, whereby \u03c7 refers to the average of the two corresponding dihedral angles H\u00b7\u00b7\u00b7O=C-O(N) and H\u00b7\u00b7\u00b7O=C-C. Similarly, the C-elevation angle (\u03d5) was calculated by sin\u03d5\u2009=\u2009sin\u03b2\u2009\u00b7\u2009sin\u03b4, whereby \u03b4 refers to the average of the two corresponding dihedral angles C\u00b7\u00b7\u00b7O=C-O(N) and C\u00b7\u00b7\u00b7O=C-C.All X-ray structures of proteins bound to amine-containing ligands were downloaded from the Protein Data Bank (PDB). To gain a better understanding of NThe GLP activity assay was carried out using a GLP Chemiluminescent Assay Kit . Microwells were rehydrated by adding 200\u2009\u03bcL of tris buffered saline with Tween 20  to every well, followed by incubation at room temperature for 45\u2009minutes. After removing TBS-T, the inhibitors were incubated in the presence of 2\u2009\u03bcM SAM and 40\u2009ng of GLP in the supplied buffer on the microwells of . After the enzymatic reaction, every well was washed three times with TBS-T (100\u2009\u03bcL) and blocked for 10\u2009min with blocking buffer. Then, 100\u2009\u03bcL of primary anti-body solution (1:400 dilution) were added to the microwells, followed by incubation (2\u2009h). The wells were probed with the primary antibody, washed three times with TBS-T (100\u2009\u03bcL), incubated  with sheep secondary anti-body (1:1000 diluted), and again washed three times with TBS-T (100\u2009\u03bcL). The chemiluminescence of the wells, to which detection reagents were added, was measured on a chemiluminescence reader (ARVO X3 Multilabel Plate Reader), and the values of % inhibition were calculated from the chemiluminescence readings of inhibited wells relative to those of control wells.\u22121. The heat of dilution of the ligand into the buffer measured independently was essentially similar to the heat signal obtained at the end of the titration; so the signal of the last injection was used as the background heat signal. The experimental data were analyzed using the MicroCal PEAQ-ITC Analysis software , and fitted using the one-site binding model. Values of \u0394G, KD, and \u2212T\u0394S were calculated using the thermodynamic relationships, \u0394G\u2009=\u2009\u2212RT lnKa, KD\u2009=\u20091/Ka, and \u0394G\u2009=\u2009\u0394H\u2009\u2212\u2009T\u0394S.A GLP recombinant protein solution  was concentrated by ultrafiltration and the buffer was replaced with test buffer . ITC measurements of GLP inhibitors binding to the GLP were recorded at 25\u2009\u00b0C using a MicroCal PEAQ-ITC microcalorimeter  in the test buffer. The titrations were performed using 10\u2009\u03bcM GLP solution in the sample cell and 100\u2009\u03bcM inhibitor solution in the syringe. A typical experiment consisted of 19 injections under the following parameters: one injection of 0.4\u2009\u03bcL followed by 18 injections of 2.0\u2009\u03bcL; 150\u2009s spacing between injections; 750\u2009rpm stirring speed; and reference power set to 5\u2009\u03bccal s2SO4 (1N). The absorbance at 450\u2009nm of the wells, to which detection reagents were added, was measured in a chemiluminescence reader (ARVO X3 Multilabel Plate Reader), and the values of % inhibition were calculated from the absorbance readings of inhibited wells relative to those of control wells.The tie-2 activity assay was carried out using human recombinant active enzyme  and Universal Tyrosine Kinase Assay Kit . The inhibitors  were incubated in the presence of 40\u2009mM ATP and 20\u2009ng of tie-2 in the supplied buffer including 5\u2009mM DTT on the microwells of the supplier . After the enzymatic reaction, the mixtures were removed from the wells and all wells were washed four times with phosphate buffered saline with Tween 20 . Then, the wells were blocked (30\u2009min) with blocking buffer, before 50\u2009\u03bcL of anti-phosphated Tyrosine-POD were added to the wells, and incubation was continued . The wells were probed, washed four times with PBS-T (100\u2009\u03bcL), and subsequently incubated with HRP substrate solution . Finally, the reaction was stopped by addition of aqueous HSupplementary Information"}
{"text": "Correction to: Biol Direct (2019) 14:14https://doi.org/10.1186/s13062-019-0247-8After publication of this article , the aut0 \u2013 f \u03c4R0 - f\u03b4\u03c42 ] + f \u03c4 [S(t) + \u03c4\u03b4] (t < 80 years), rather than C = exp (\u03c4 \u2212t/ [C0 \u2013 f \u03c4R0 -f\u03b4\u03c42] + f \u03c4 [S(t) + \u03c4\u03b4] (t < 80 years) in the previous publication.The first error is in the equation of the footnote 1. The correct equation should be: C = exp(-t/ \u03c4) [CThe second error is in the beginning of the third line from the bottom of the footnote currently reads dC/dt = S(t) - C/ \u03c4 whereas it should read dC/dt = f S(t) - C/ \u03c4.The last error is the year in the last sentence of the response to\u00a0Reviewer\u2019s report 2:\u00a0it should be 2018 rather than 1918."}
{"text": "NO2\u22ef\u03c0(N)NO2 inter\u00adaction.The title tetra\u00adnuclear cluster contains a tetra\u00adhedral arrangement of copper(II) ions bonded to a central oxygen atom. The extended structure shows short O\u22efN inter\u00adactions between the nitro groups of adjacent clusters, which are oriented perpendicular to each other in a manner that has previously been described as an O 4Cl6O(C6H9N3O3)4] or [Cu4Cl6O\u00ad(MET)4] [MET is 1-(2-hy\u00addroxy\u00adeth\u00adyl)-2-methyl-5-nitro-1H-imidazole or metronidazole], contains a tetra\u00adhedral arrangement of copper(II) ions. Each copper atom is also linked to the other three copper atoms in the tetra\u00adhedron via bridging chloride ions. A fifth coordination position on each metal atom is occupied by a nitro\u00adgen atom of the monodentate MET ligand. The result is a distorted CuCl3NO trigonal\u2013bipyramidal coordination polyhedron with the axial positions occupied by oxygen and nitro\u00adgen atoms. The extended structure displays O\u2014H\u22efO hydrogen bonding, as well as unusual short O\u22efN inter\u00adactions [2.775\u2005(4)\u2005\u00c5] between the nitro groups of adjacent clusters that are oriented perpendicular to each other. The scattering contribution of disordered water and methanol solvent mol\u00adecules was removed using the SQUEEZE procedure  in PLATON .The title tetra\u00adnuclear copper complex, [CuSpek 2015. Acta CrSpek 2009. Acta Cr In the title complex, \u03b1 = 110.80\u2005(9)\u00b0 and \u03b2 = 109.55\u2005(9)\u00b0, such that \u03c44 is 0.990, which indicates negligible deviation from a tetra\u00adhedral geometry for oxygen  to 2.4435\u2005(9)\u2005\u00c5 . Each copper atom is also bound to a nitro\u00adgen atom of a MET ligand. The Cu\u2014N lengths range from 1.949\u2005(2) to 1.972\u2005(3)\u2005\u00c5 . Thus, each copper atom sits within a trigonal\u2013bipyramidal arrangement, with the oxygen and nitro\u00adgen atoms forming the axial coordination points, and the bridging chloride ligands occupying the equatorial plane. The trigonal\u2013bipyramidal structure is somewhat distorted, as indicated by the fact that the O\u2014Cu\u2014N angles are less than 180\u00b0, ranging from 173.12\u2005(10) to 176.91\u2005(10)\u00b0 , and the Cl\u2014Cu\u2014Cl angles differ significantly from 120\u00b0, ranging from 109.97\u2005(3) to 134.02\u2005(3)\u00b0 . Furthermore, the O\u2014Cu\u2014Cl angles are all less than 90\u00b0, ranging from 83.33\u2005(6) to 86.13\u2005(6)\u00b0 , indicating that the equatorial chloride ligands are displaced slightly more towards the axial oxygen atom in the center of the mol\u00adecule, than towards the nitro\u00adgen-containing ligand in the opposite axial position.Each of the four copper atoms is linked to the other three copper atoms 5 geometry index is a general descriptor of five-coordinate mol\u00adecules and provides a way to determine the extent of distortion of a mol\u00adecule from trigonal bipyramidal to square pyramidal /60, where \u03b2\u00a0\u2212\u00a0\u03b1 is the difference between the two largest angles , 0.74 (Cu2), 0.84 (Cu3) and 0.73 (Cu4) for the five-coordinate copper centers, giving an average \u03c45 value of 0.74. The \u03c45 values obtained indicate that the copper-centered structures are closer to an idealized trigonal\u2013bipyramidal (1.00) than a square-pyramidal geometry (0.00).The \u03c4A and O21\u2014H21A probably form links to the disordered solvent mol\u00adecules removed with SQUEEZE . The most inter\u00adesting observation is the existence of short O\u22efN inter\u00adactions between the N13/O12/O13 and N33/O32/O33 nitro groups of adjacent clusters that are oriented perpendicular to each other, as illustrated in Fig.\u00a03NO2\u22ef\u03c0(N)NO2 inter\u00adaction 4] contains Cu\u2014X distances that are similar to those in [Cu4Cl6O(imidazole)4] 4] are 1.8960\u2005(18)\u20131.913\u2005(2)\u2005\u00c5, compared to 1.903\u2005(4)\u20131.924\u2005(4)\u2005\u00c5 for [Cu4Cl6O(imidazole)4]. Likewise, the Cu\u2014Cl distances in [Cu4Cl6O(MET)4] are 2.3579\u2005(10)\u20132.4435\u2005(9)\u2005\u00c5, compared to 2.374\u2005(2)\u20132.564\u2005(2)\u2005\u00c5 for [Cu4Cl6O(imidazole)4]. Moreover, the Cu\u2014N distances in [Cu4Cl6O(MET)4] are 1.949\u2005(2)\u20131.972\u2005(3)\u2005\u00c5, compared to 1.934\u2005(6)\u20131.961\u2005(6)\u2005\u00c5.The title compound [CuAnhydrous copper(I) chloride  was mixed with MET  in methanol (2\u2005ml) in a glass vial, forming a dark olive-colored solution. After allowing the solution to evaporate for eight days, gold-colored plates, suitable for X-ray diffraction, were obtained.Uiso(H) = 1.2Ueq(Csp2) or 1.5Ueq(Csp3). Atoms C34, C35 and O31 and their attached H atoms were modeled as disordered over two sets of sites in a 0.515\u2005(19):0.485\u2005(19) ratio. The structure contains two methanol mol\u00adecules and one water mol\u00adecule, but they are disordered and were removed by the SQUEEZE procedure in PLATON  only refer to the main mol\u00adecule.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019008570/hb7801sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019008570/hb7801Isup2.hklStructure factors: contains datablock(s) I. DOI: 1923275CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, 1,3-dioxolane and 1,3-dioxole rings adopt envelope forms, while amide moiety and benzene ring are essentially planar. An intra\u00admolecular O\u2014H\u22efO hydrogen bond supports the mol\u00adecular conformation, and inter\u00admolecular weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions connect the mol\u00adecules into sheet structure. 20H27NO6, the amide moiety is essentially planar, with a maximum deviation of 0.073\u2005(3)\u2005\u00c5, and one of the N-methyl groups shows rotational disorder. The five-membered 1,3-dioxolane ring adopts an envelope form, with the C atom bonded to the olefin side chain as the flap, which deviates from the mean plane through the other four atoms by 0.564\u2005(7)\u2005\u00c5. The 1,3-dioxole ring fused to the benzene ring adopts a flattened envelope form, with the C atom between the two O atoms as the flap, which deviates from the mean plane through the other four atoms by 0.215\u2005(7)\u2005\u00c5. The C\u2014C=C\u2014C olefin moiety is essentially planar and makes a dihedral angle of 87.1\u2005(3)\u00b0 with the benzene ring. An intra\u00admolecular O\u2014H\u22efO hydrogen bond supports the mol\u00adecular conformation, enclosing an S(11) graph-set motif. In the crystal, inter\u00admolecular C\u2014H\u22efO hydrogen bonding links the mol\u00adecules into a tape running along the b axis. Furthermore, other weak C\u2014H\u22efO hydrogen bonds and a C\u2014H\u22ef\u03c0 inter\u00adaction connect the tapes into a sheet structure parallel to (100).In the title compound, C These conversions are often carried out with protection of the contiguous diol  shows rotational disorder over two orientations, with refined occupancies of 0.54\u2005(8) and 0.46\u2005(8). The 1,3-dioxolane ring (C10/O11/C12/O13/C14) adopts an envelope form, with puckering parameters of Q(2) = 0.362\u2005(5)\u2005\u00c5 and \u03c6(2) = 40.6\u2005(7)\u00b0. The flap atom C10 deviates from the mean plane through the other four atoms by 0.564\u2005(7)\u2005\u00c5. The 1,3-dioxole ring (C23/C24/O25/C26/O27) in benzodioxole adopts a flattened envelope form, with puckering parameter of Q(2) = 0.135\u2005(5)\u2005\u00c5 and \u03c6(2) = 326\u2005(2)\u00b0. The flap atom C26 deviates from the mean plane through the other four atoms by 0.215\u2005(7)\u2005\u00c5. The olefin moiety (C7\u2014C8=C9\u2014C10) is essentially planar and makes a dihedral angle of 87.1\u2005(3)\u00b0 with the benzene ring (C19\u2013C24). An intra\u00admolecular O\u2014H\u22efO hydrogen bond  graph-set motif.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01i; symmetry code as in Table\u00a01b axis, with a C(3) graph-set motif. Furthermore, other weak C\u2014H\u22efO hydrogen bonds and a C\u2014H\u22ef\u03c0 inter\u00adaction , similar to the title compound , gives two entries with refcodes YERGUX , has yet been reported.On the other hand, searching the CSD for a structure with a combination of benzodioxole and oxymethyl\u00addioxolane components, . HRMS (ESI) m/z calculated for C20H27NO6Na+ [M + Na]+: 400.1736; found: 400.1731.The title compound was synthesized in two steps from 3,4-d-arabinose. The H atoms on one of the N-methyl groups (C4) are disordered; they were split into two sets of positions H4A\u2013C and H4D\u2013F, the refined occupancies being 0.54\u2005(8) and 0.46\u2005(8), respectively. C-bound H atoms were positioned geometrically, with C\u2014H = 0.95\u20131.00\u2005\u00c5, and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. The hy\u00addroxy H atom was placed in a difference map and treated as riding, with O\u2014H = 0.84\u2005\u00c5 and Uiso(H) = 1.5Ueq(O). One problematic reflection  global, I. DOI: 10.1107/S2056989018007132/is5496Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018007132/is5496Isup3.cmlSupporting information file. DOI: 1842600CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "These are packed via C\u2014H \u22efN and C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in a three-dimensional architecture with a tilted herringbone packing mode.The two independent mol\u00adecules in the asymmetric unit of the title compound are connected  14H12N4S, was synthesized by the condensation reaction of hydralazine and 2-acetyl\u00adthio\u00adphene and during the reaction, a proton transfer from the imino nitro\u00adgen atom to one of the endocylic nitro\u00adgen atoms occurred. The compound crystallizes in the monoclinic crystal system with two independent mol\u00adecules (mol\u00adecules 1 and 2) in the asymmetric unit. In each mol\u00adecule, there is a slight difference in the orientation of the thio\u00adphene ring with respect to phthalazine ring system, mol\u00adecule 1 showing a dihedral angle of 42.51\u2005(1)\u00b0 compared to 8.48\u2005(1)\u00b0 in mol\u00adecule 2. This implies an r.m.s deviation of 0.428\u2005(1)\u2005\u00c5 between the two mol\u00adecules for the 19 non-H atoms. The two independent mol\u00adecules are connected via two N\u2014H\u22efN hydrogen bonds, forming dimers which inter\u00adact by two bifurcated \u03c0\u2013\u03c0 stacking inter\u00adactions to build tetra\u00admeric motifs. The latter are packed in the ac plane via weak C\u2014H\u22ef\u03c0 inter\u00adactions and along the b axis via C\u2014H \u22efN and C\u2014H\u22ef\u03c0 inter\u00adactions. This results a three-dimensional architecture with a tilted herringbone packing mode.The title compound, C The lengths of the N4\u2014C9 and N4B\u2014C9B bonds of 1.294\u2005(2) and 1.296\u2005(2)\u2005\u00c5, respectively, are in agreement with that of an N=Csp2 bond (1.282 \u00b10.060)\u2005\u00c5 found in the CSD \u2005\u00c5] and N3B\u2014C8B [1.309\u2005(2)\u2005\u00c5] and the single-bond character of N3\u2014N4 [1.398\u2005(2)\u2005\u00c5] and N3B\u2014N4B [1.400\u2005(2)\u2005\u00c5]. Indeed, these values are in agreement with the bond lengths for C=N and N-N bonds  in the C=N\u2014N fragment with a cyclic carbon atom and acyclic nitro\u00adgen atoms for organic compounds in the CSD. Such a proton transfer has been reported in other hydrazinophthal\u00adazine derivatives  are in a planar conformation with a maximum deviation of 0.006\u2005(1)\u2005\u00c5 for S1 in mol\u00adecule 1 and of 0.003\u2005(1)\u2005\u00c5 for S1via two N\u2014H\u22efN hydrogen bonds .Mol\u00adecules 1 and 2 are linked on Fig.\u00a04 and in tns Fig.\u00a05. The reset al., 2016et al., 2007et al., 2014aA search of the Cambridge Structural Database  and hydralazine hydro\u00adchloride  in 20\u2005ml of methanol and 10\u2005ml of aqueous solution of sodium acetate  as buffering agent. The mixture was refluxed at 338\u2005K under stirring for four\u2005h. The product was left overnight to cool. The yellow precipitate was filtered off and washed several times with water and methanol, and finally crystallized from a mixture of DMF/methanol (2:1) as yellow crystals (in a yield of around 80%) suitable for single-crystal X-ray diffraction studies.Uiso(H)= 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019000732/lh5889sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000732/lh5889Isup2.cmlSupporting information file. DOI: 1891271CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R2\u2217 values for 1.5\u2009T and 3\u2009T are reversed. The corrected equation is as follows:In the article titled \u201cHepatic Iron Quantification on 3 Tesla (3\u2009T) Magnetic Resonance (MR): Technical Challenges and Solutions\u201d , there w"}
{"text": "II complex with a Schiff base ligand formed in situ from cyste\u00adamine (2-amino\u00adethane\u00adthiol) and o-vanillin is reported as well results of its anti\u00adbacterial activity screening.The crystal structure of a trinuclear Ni 3(C10H11NO2S)3]\u00b7C3H7NO, with a Schiff base ligand formed in situ from 2-amino\u00adethane\u00adthiol and o-vanillin crystallizes in the ortho\u00adrhom\u00adbic space group Pbca. Its asymmetric unit consists of one neutral Ni3L3 mol\u00adecule and one DMF solvent mol\u00adecule. The solid-state organization of the complex can be described as an insertion of the solvent mol\u00adecules within the crystallographically independent trinuclear NiII species. Several C\u2014H\u22ef\u03c0 edge-to-face inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions link the components in the crystal. A first example of a short inter\u00admolecular C\u2014H\u22efNi contact is found. Anti\u00adbacterial in vitro screening revealed that the title compound has anti\u00adbacterial activity, the best effect being against Acinetobacter baumannii.The title trinuclear nickel(II) complex, [Ni The deviation of the NiII atom from the NOS2 mean plane is 0.0927\u2005(14)\u2005\u00c5. Thus, the mol\u00adecule has a \u2018crown\u2019 or bowl shape with the Ni3S3 unit as its base in a distorted chair conformation. The torsion angles [between 78.49\u2005(5) and 84.79\u2005(5)\u00b0] deviate significantly from the ideal chair conformation for c-hexane which has torsion angles of 60\u00b0. For the Ni2 atom in this core, one additional short contact should be noted, C27\u2014H27C\u22efNi with an H\u22efNi distance of 2.58\u2005\u00c5. Thus, with this additional contact, the coordination geometry of the Ni2 atom is square pyramidal with heteroatom\u2014Ni2\u2014H27C bond angles in the range 78.0-95.1\u00b0.The coordination geometry around each Niet al., 2001et al., 1988Unlike in closely related compounds, the solvent mol\u00adecule is not encapsulated. The distances observed between the Ni atoms are within Ni1\u22efNi2 3.5706\u2005(4) and 3.6656\u2005(5)\u2005\u00c5. The intra\u00admolecular Ni\u2014S distances with the dianionic Schiff base ligand  are in the range 2.1888\u2005(12)\u20132.2036\u2005(13)\u2005\u00c5. They are slightly shorter than analogous ones with the bridging sulfur atom  of the neighboring ligand [2.2171\u2005(12)\u20132.2262\u2005(13)\u2005\u00c5]. These data are comparable with those previously reported for related structures  of 3.722\u2005(6)\u2005\u00c5 for connect the neighboring units . Several C\u2014H\u22efO and C\u2014H\u22ef\u03c0 edge-to-face inter\u00adactions imino\u00admeth\u00adyl]phenolato}trinickel and tris\u00ad(\u03bc2-2-(2-naph\u00adth\u00adyl\u00admeth\u00adoxy)-6-[{(2-sulfido\u00adeth\u00adyl)imino]\u00admeth\u00adyl}phenolato)trinickel(II) di\u00adchloro\u00admethane solvate, tris\u00ad(\u03bc2-2-(benz\u00adyloxy)-6-{[(2-sulfido\u00adeth\u00adyl)imino]\u00admeth\u00adyl}phenolato)tri\u00adnickel(II) di\u00adchloro\u00admethane solvate, tris\u00ad(\u03bc2-2-eth\u00adoxy-6-[{(2-sulfido\u00adeth\u00adyl)imino]\u00admeth\u00adyl}phenolato)trinickel(II) C60-fullerene dichloro\u00admethane solvate, tris\u00ad(\u03bc2-2-eth\u00adoxy-6-{[(2-sulfido\u00adeth\u00adyl)imino]\u00admeth\u00adyl}phenolato)trinickel(II) di\u00adchloro\u00admethane solv\u00adate  in ethanol (5\u2005ml) was added to the filtrate and stirred on air magnetically for 2\u2005h. Nickel acetate tetra\u00adhydrate  in ethanol (6\u2005ml) was added to the yellowish solution of the Schiff base formed in situ, and the resulting deep-brown solution was stirred magnetically and heated at 340\u2013347\u2005K for 1.5\u2005h resulting in a dark-colored precipitate. The product was isolated by filtration, washed with dry ii=PrOH and finally dried in vacuo. Crystals suitable for crystallographic study were grown from a saturated solution in DMF (deep-brown solution). The crystals were filtered off, washed with dry i-PrOH and finally dried at room temperature (yield: 47%).A solution of KOH  in a minimum amount of methanol (2\u20133\u2005ml) was added to a solution of 2-amino\u00adethane\u00adthiol hydro\u00adchloride  in methanol (5\u2005ml) and stirred in an ice bath for 10\u2005min. The white precipitate of solid KCl was removed by filtration and \u22121 indicating the formation of a Schiff base (\u2013H\u2014C=N\u2013)  (as well in CH3 groups of the solvent mol\u00adecule) and aromatic \u2013C=C\u2013 stretching vibrations. Other strong bands at 1228 and 1244\u2005cm\u22121 are due to the phenolic CO stretching  proton signal. The O\u2014CH3 protons peaks only appear at 3.92 ppm. The multiplets of the aromatic protons appear in the range 6.39\u20136.79 ppm with different multiplicity and coupling constants. The strong singlet at 3.39 ppm could be assigned to the aliphatic \u2013CH2\u2013CH2\u2013 protons according to its integral intensity. Signals from the DMF methyl protons appear at 2.94 and 2.78 ppm. Analysis calculated for for C33H40N4Ni3O7S3 (877.00): C, 45.20; H, 4.60; N, 6.39; found: C, 45.5; H, 4.77; N, 6.25.The IR spectrum of the title compound (as KBr pellets) is consistent with the above structural data. It displays the characteristic peak at 1610\u2005cmUiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a02in vitro screening of all test compounds was carried out against reference strains of bacteria  and clinical strains . The broth microdilution method was used according to the European Committee on Anti\u00admicrobial Susceptibility Testing (EUCAST). The results obtained indicate that the synthesized compound possesses a broad spectrum of activity against the tested microorganisms and shows relatively better activity against Gram-negative than Gram-positive bacteria. The title complex showed activity with lowest minimum inhibitory concentrations (MIC) values 312.5\u2005\u00b5g ml\u22121 against Gram-negative bacteria E. coli, K. pneumoniae and P. aeruginosa. The highest activity was against clinical strain A. baumannii - MIC = 156.2\u2005\u00b5g ml\u22121. The poorest activity of the complex was against clinical strain Staphylococcus aureus (MRSA). It is well known that A. baumannii is one of the most important nosocomial pathogens because of its longevity in the hospital environment and ability to resist various anti\u00admicrobial agents, such as resistance to broad-spectrum \u03b2-lactam anti\u00adbiotics by \u03b2-lactamases production  I. DOI: 10.1107/S2056989019004730/ex2019Isup2.hklStructure factors: contains datablock(s) I. DOI: 1865532CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title di\u00adepoxy\u00adphenalene derivative, two di\u00adhydro\u00adfuran and two tetra\u00adhydro\u00adfuran rings, as well as one cyclo\u00adhexane ring, are fused together with two methyl carboxyl\u00adate groups in positions 2- and 3-. In the crystal, two pairs of C\u2014H\u22efO hydrogen bonds link the mol\u00adecules to form inversion dimers, enclosing two  17H18O6, comprises a fused cyclic system containing four five-membered rings (two di\u00adhydro\u00adfuran and two tetra\u00adhydro\u00adfuran) and one six-membered ring (cyclo\u00adhexa\u00adne). The five-membered di\u00adhydro\u00adfuran and tetra\u00adhydro\u00adfuran rings adopt envelope conformations, and the six-membered cyclo\u00adhexane ring adopts a distorted chair conformation. Two methyl carboxyl\u00adate groups occupy adjacent positions (2- and 3-) on a tetra\u00adhydro\u00adfuran ring. In the crystal, two pairs of C\u2014H\u22efO hydrogen bonds link the mol\u00adecules to form inversion dimers, enclosing two R22(6) ring motifs, that stack along the a-axis direction and are arranged in layers parallel to the bc plane.The title di\u00adepoxy\u00adphenalene derivative, C Reactions totally depending on thermodynamic and kinetic control are infrequently found in the field of organic synthesis, at the same time such transformations are very perspective and attractive from a practical point of view since they allow the direction of the reaction to be changed radically by varying only one of the reaction parameters .et al., 2010et al., 2000et al., 1998et al., 1996et al., 2014et al., 1996et al., 2010et al., 2010et al., 1978The first example of kinetic/thermodynamic control in the course of the Diels\u2013Alder reaction was reported in 1948  into the \u2018domino-adduct\u2019 (2)  cyclo\u00adaddition in an inter\u00admediate, leading to the formation of the thermodynamically controlled \u2019domino-adduct\u2019 (2) in an almost qu\u00adanti\u00adtative yield.The present paper describes the uncommon thermal rearrangement of the \u2018 al. 2018 and Bori al. 2018; for ref al. 2018, Lautens al. 2018 and Domi al. 2000]. The tr2) is illustrated in Fig.\u00a01Q(2) = 0.5230\u2005(18)\u2005\u00c5 and \u03c6(2) = 178.1\u2005(2)\u00b0 for ring A, Q(2) = 0.5492\u2005(17)\u2005\u00c5 and \u03c6(2) = 182.3\u2005(2)\u00b0 for B, Q(2) = 0.5230\u2005(18)\u2005\u00c5 and \u03c6(2) = 1.0\u2005(2)\u00b0 for C, and Q(2) = 0.5303\u2005(17)\u2005\u00c5 and \u03c6(2) = 358.9\u2005(2)\u00b0 for D. The puckering parameters of the six-membered cyclo\u00adhexane ring (C1/C2/C10\u2013C13) are QT = 0.518\u2005(2)\u2005\u00c5, \u03b8 = 6.9\u2005(2)\u00b0 and \u03c6 = 178.2\u2005(18)\u00b0. In positions 2- and 3-, i.e. on atoms C8 and C9 . The contribution from the O\u22efH/H\u22efO contacts, corresponding to C\u2014H\u22efO inter\u00adactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bonding inter\u00adaction  and O\u22efO . The large number of H\u22efH and O\u22efH/H\u22efO inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  and (2), viz. 2-benzyl-6a,9b-bis\u00ad(tri\u00adfluoro\u00admeth\u00adyl)-2,3,6a,9b-tetra\u00adhydro-1H,6H,7H-3a,6:7,9a-di\u00adepoxy\u00adbenzo[de]iso\u00adquinoline -2--2,3-di\u00adhydro-1H,6H,7H-3a,6:7,9a-di\u00adepoxy\u00adbenzo[de]iso\u00adquinoline-3a1,6a-di\u00adcarboxyl\u00adate . C\u2014H\u22ef\u03c0 inter\u00adactions are also observed, together with intra\u00admolecular F\u22efF contacts. The asymmetric unit of HENLEU contains two independent mol\u00adecules. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds, forming columns along [010]. Likewise, C\u2014H\u22ef\u03c0 inter\u00adactions and F\u22efF intra\u00admolecular contacts are also present. In the crystal structure of LIRKAB, inter\u00admolecular C\u2014H\u22efO inter\u00adactions involving the O atoms of the carbonyl groups, the oxygen bridgehead atoms and the meth\u00adoxy O atoms, as well as C\u2014H\u22efF hydrogen bonds, define the crystal packing. These packing features lead to the formation of a supra\u00admolecular three-dimensional structure. C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions are not observed, but H\u22efH inter\u00adactions dominate in the packing. This situation is similar to that in the crystal of the title compound.2) is illustrated in the Scheme. Compound (1)  was dissolved in dry o-Me2C6H4 (15\u2005ml) and then heated under reflux for 4\u2005h at \u223c413\u2005K (thin-layer chromatography monitoring). The reaction mixture was cooled and the solvent removed under reduced pressure. The residue was purified by recrystallization from an EtOAc/hexane mixture (1:1 v/v) to give compound (2) as large colourless prismatic crystals . 1H NMR : \u03b4 6.43 , 6.27 , 5.09 , 4.88 , 3.78 , 3.73 , 2.23\u20132.17 , 2.00\u20131.88  1.71\u20131.68 . 13C NMR : \u03b4 164.7 (CO2Me), 162.6 (CO2Me), 150.6 (C-3), 143.8 (C-2), 140.8 (C-7), 138.5 (C-8), 89.3 (C-3a), 85.8 (C-6a), 81.3 (C-1), 80.5 (C-9), 52.2 (C-9a), 52.0 (2 \u00d7 CO2Me), 49.8 (C-9b), 26.7 (C-9), 25.0 (C-6), 17.2 (C-5). IR \u03bdmax/cm\u22121 (KBr): 1709, 1628, 1284, 1261. HRMS (ESI\u2013TOF): calculated for C17H18O6 [M + H]+ 318.1103; found 318.1125.The synthesis of the title compound (Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019003499/rz5253sup1.cifCrystal structure: contains datablock(s) 2, Global. DOI: 1902671CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, one mol\u00adecule inter\u00adacts with six neighbouring mol\u00adecules  17H14O, which is used as a sensitiser for thermal paper, has a twisted conformation with a dihedral angle of 48.71\u2005(12)\u00b0 between the phenyl ring and the naphthyl ring system. In the crystal, one mol\u00adecule inter\u00adacts with six neighbouring mol\u00adecules via inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions to form a herringbone mol\u00adecular arrangement.The title compound [systematic name: 2-(benz\u00adyloxy)naphthalene], C Herein, we report the crystal structure of 1 as fundamental data for the investigation of its influence on the solid-state physicochemical properties of the thermosensitive layer of the thermal paper.Thermal printing is a rapid and inexpensive printing technology widely used in commercial applications such as receipts, faxes and tickets  and the phenyl ring (C12\u2013C17) is 48.71\u2005(12)\u00b0. The related torsion angles for this dihedral angle are \u221244.9\u2005(3)\u00b0 (O1\u2014C11\u2014C12\u2014C17), 178.7\u2005(2)\u00b0 (C1\u2014O1\u2014C11\u2014C12) and \u22125.6\u2005(3)\u00b0 (C6\u2014C1\u2014O1\u2014C11).The title compound Fig.\u00a01 is a simvia inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions  = 1.2Ueq(C).The crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019000690/is5508sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019000690/is5508Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000690/is5508Isup3.cmlSupporting information file. DOI: 1890872CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The two benzene rings are twisted by angles of 79.14\u2005(7) and 19.02\u2005(14)\u00b0 in the two independent mol\u00adecules. In the crystal, amide\u2013amide inter\u00adactions link the mol\u00adecules into chains running along  17H16N4O6, contains two independent mol\u00adecules (A and B). The two benzene rings are twisted by an angle of 79.14\u2005(7)\u00b0 in mol\u00adecule A, whereas, in mol\u00adecule B, they are inclined by 19.02\u2005(14)\u00b0. The conformations of the mol\u00adecules are stabilized by intra\u00admolecular N\u2014H\u22efO hydrogen bonds between the amide nitro\u00adgen atom and the O atom of the ortho-nitro substituent on the phenyl ring, enclosing an S(6) ring motif. In the amide and aliphatic segments, all the N\u2014H, C=O and C\u2014H bonds are anti to each other. In the crystal, the A and B mol\u00adecules are linked by inter\u00admolecular amide-to-amide N\u2014H\u22efO hydrogen bonds, resulting in chains running along the b-axis direction. The inter\u00admolecular inter\u00adactions were analysed using Hirshfeld surface analysis. The two-dimensional fingerprint plots of the inter\u00admolecular contacts indicate that the major contributions are from H\u22efH and O\u22efH inter\u00adactions.The asymmetric unit of the title compound, C There has been a study on the influence of the length of the connecting chain on the anti\u00admalarial activity of bis\u00adquinolines  and \u2212161.9\u2005(3)\u00b0 for C2\u2014C1\u2014N1\u2014C7 and C19\u2014C18\u2014N5\u2014C24, respectively. In the other half, they are syn to the ortho-substituent as shown by the torsion angles of 48.6\u2005(4) and \u221250.6\u2005(4)\u00b0 for C13\u2014C12\u2014N2\u2014C11 and C30\u2014C29\u2014N6\u2014C28, respectively. The O1\u2014C7, O2\u2014C11, O7\u2014C24 and O8\u2014C28 bond lengths are 1.213\u2005(3), 1.224\u2005(3), 1.218\u2005(3) and 1.218\u2005(3)\u2005\u00c5, respectively, which indicate that the mol\u00adecules exist in their keto forms in the solid state. In mol\u00adecule A, the bis-amide group forms dihedral angles of 24.79\u2005(12) and 55.04\u2005(7)\u00b0 with the phenyl rings C1\u2013C6 and C12\u2013C17, respectively. In mol\u00adecule B, the plane of the amide group forms dihedral angles of 34.24\u2005(13) and 24.27\u2005(12)\u00b0 with the C18\u2013C23 and C29\u2013C34 phenyl rings, respectively, while the two benzene rings form a dihedral angle of 79.14\u2005(7) and 19.02\u2005(14)\u00b0 in mol\u00adecules A and B, respectively. The planes of mol\u00adecules A and B are almost coplanar with each other, as is evident from the dihedral angle of only 3.15\u2005(17)\u00b0 between phenyl rings C1\u2013C6 and C18\u2013C23.The asymmetric unit of the title compound (I)ortho-substituted nitro groups attached to the C1/C6 and C18/C23 phenyl rings form short intra\u00admolecular contacts, each of 2.01\u2005(3)\u2005\u00c5, with the nearest amide N atom, forming an N\u2014H\u22efO contact resulting in an S(6) hydrogen bonding motif.The O atoms of the b-axis direction. The oxygen atom of the amide C=O group in mol\u00adecule B forms a bifurcated hydrogen bond with the N\u2014H group of the amide unit and the C\u2014H group of the aliphatic chain of an adjacent mol\u00adecule. The C3\u2014H3 unit of the C1\u2013C6 ring of mol\u00adecule A forms a short inter\u00admolecular contact with the oxygen atom O5 belonging to the nitro group of the C12\u2013C17 phenyl ring of another A mol\u00adecule at position \u2212x, 1\u00a0\u2212\u00a0y, \u2212z. C\u2014H groups of the C12\u2013C17 and C29\u2013C34 phenyl rings form hydrogen bonds with the O atoms of the nitro groups of the C12/C17 and C29/C34 phenyl rings at \u2212x, \u2212y\u00a0+\u00a02, \u2212z\u00a0+\u00a01 and \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01, respectively. A packing diagram of the title compound is shown in Fig.\u00a03In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds Table\u00a01. An inteCrystalExplorer , with de + di \u223c 2.4\u2005\u00c5 . H\u22efH contacts represent the next largest contribution to the Hirshfeld surfaces (29.2%) and show a distinct pattern with a minimum value of de = di \u223c 1.2\u2005\u00c5 . O\u22efC/C\u22efO and N\u22efH/H\u22efN inter\u00adactions cover only 5.4%  and 3.4%  of the surface, respectively. Two triangles featuring the C\u22efC contacts contribute 3.2% to the Hirshfeld surfaces, with a minimum (de + di) distance of 3.5\u2005\u00c5 .In the two-dimensional fingerprint plot Fig.\u00a06, di is \u2005\u00c5 Fig.\u00a06b. H\u22efH c\u2005\u00c5 Fig.\u00a06c. O\u22efC/C4% Fig.\u00a06d and 3.4% Fig.\u00a06e of the\u2005\u00c5 Fig.\u00a06f.et al., 2010bcN,N\u2032-bis\u00ad(phen\u00adyl)suberamide . The purity of the compound was checked by TLC and it was characterized by IR spectroscopy. The characteristic absorptions were observed at 3334.9, 1693.5 and 1330.9\u2005cm\u22121 for N\u2014H, C=O and C\u2014N, respectively. 1H NMR : 1.93 to 2.00 , 2.48 , 7.95  , 7.28\u20137.33 , 7.63\u20137.70 , 7.82  , 10.24 . 13C NMR : 20.40, 35.19, 124.38, 124.65, 124.68, 131.71, 133.75, 141.36 and 170.82. Rod-shaped yellow single crystals of the title compound were obtained by slow evaporation of a DMF solution at room temperature.A mixture of glutaric acid (0.2\u2005mol) and thionyl chloride (1.0\u2005mol) was heated for half an hour at 363\u2005K. Then 2-nitro\u00adaniline (0.4\u2005mol) was added dropwise under stirring. The resultant mixture was stirred for 3\u2005h and left standing for 12\u2005h for the completion of the reaction. The product was added to crushed ice. The white precipitate obtained was washed thoroughly with water and then with saturated sodium bicarbonate solution and again with water. It was washed first with 2 Uiso(H) = 1.2Ueq(C). The H atoms of the NH groups were located in a difference map and later restrained to a distance of N\u2014H = 0.86\u2005(2)\u2005\u00c5. They were refined with Uiso(H) = 1.2 Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018013075/zl2738sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018013075/zl2738Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013075/zl2738Isup3.cmlSupporting information file. DOI: 1578746CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title 1:2 co-crystal has a half mol\u00adecule of twofold symmetric di\u00adthiodi\u00adbenzoic acid and a full mol\u00adecule of benzoic acid. These are connected into three-mol\u00adecule aggregates via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds. 14H10O4S2\u00b72C7H6O2, comprises half a mol\u00adecule of di\u00adthiodi\u00adbenzoic acid [systematic name: 2-[(2-carb\u00adoxy\u00adphen\u00adyl)disulfan\u00adyl]benzoic acid, DTBA], as the mol\u00adecule is located about a twofold axis of symmetry, and a mol\u00adecule of benzoic acid (BA). The DTBA mol\u00adecule is twisted about the di\u00adsulfide bond [the C\u2014S\u2014S\u2014C torsion angle is \u221283.19\u2005(8)\u00b0] resulting in a near perpendicular relationship between the benzene rings [dihedral angle = 71.19\u2005(4)\u00b0]. The carb\u00adoxy\u00adlic acid group is almost co-planar with the benzene ring to which it is bonded [dihedral angle = 4.82\u2005(12)\u00b0]. A similar near co-planar relationship pertains for the BA mol\u00adecule [dihedral angle = 3.65\u2005(15)\u00b0]. Three-mol\u00adecule aggregates are formed in the crystal whereby two BA mol\u00adecules are connected to a DTBA mol\u00adecule via hy\u00addroxy-O\u2014H\u22efO(hydroxy) hydrogen bonds and eight-membered {\u22efHOC=O}2 synthons. These are connected into a supra\u00admolecular layer in the ab plane through C\u2014H\u22efO inter\u00adactions. The inter\u00adactions between layers to consolidate the three-dimensional architecture are \u03c0\u2013\u03c0 stacking inter\u00adactions between DTBA and BA rings [inter-centroid separation = 3.8093\u2005(10)\u2005\u00c5] and parallel DTBA-hy\u00addroxy-O\u22ef\u03c0(BA) contacts [O\u22efring centroid separation = 3.9049\u2005(14)\u2005\u00c5]. The importance of the specified inter\u00adactions as well as other weaker contacts, e.g. \u03c0\u2013\u03c0 and C\u2014H\u22efS, are indicated in the analysis of the calculated Hirshfeld surface and inter\u00adaction energies.The asymmetric unit of the title 1:2 co-crystal, C Such oxidation of the original 2-thio\u00adbenzoic acid to DTBA is well known in co-crystallization studies i\u2014C3i torsion angle being \u221283.19\u2005(8)\u00b0; symmetry operation (i): 1\u00a0\u2212\u00a0x, y, z. This almost orthogonal disposition is also seen in the dihedral angle between the benzene rings of 71.19\u2005(4)\u00b0. The presence of a carb\u00adoxy\u00adlic acid group is readily confirmed by the disparity in the C1\u2014O1, O2 bond lengths, i.e. 1.317\u2005(2) and 1.229\u2005(2)\u2005\u00c5, respectively. This group is practically co-planar with the benzene ring to which it is bonded, as seen in the dihedral angle of 4.82\u2005(12)\u00b0. This co-planar arrangement allows for a significant intra\u00admolecular S\u2190O inter\u00adaction, i.e. S1\u22efO2 = 2.6712\u2005(12)\u2005\u00c5, as the carbonyl-O2 atom is orientated towards a di\u00adsulfide-S1 atom  and 1.233\u2005(2)\u2005\u00c5, respectively. As for the DTBA mol\u00adecule, the carb\u00adoxy\u00adlic acid group is close to co-planar with the benzene ring to which it is bound, forming a dihedral angle of 3.65\u2005(15)\u00b0.PLATON . The resultant three-mol\u00adecule aggregates are connected through DTBA-C\u2014H\u22efO3(hydroxyl-BA) and BA-C\u2014H\u22efO1(hydroxyl-DTBA) inter\u00adactions, to form non-symmetric, ten-membered {O\u22efHCCC}2 homo-synthons leading to supra\u00admolecular layers in the ab plane, Fig.\u00a02b). Owing to the nearly right-angle relationship between the rings in the DTBA mol\u00adecule, and the co-planarity between the carb\u00adoxy\u00adlic acid groups and the respective rings they are connected to, the layers also have a similar topology. Adjacent layers inter-digitate with other layers, on both sides, i.e. approximately orthogonally, as highlighted in Fig.\u00a02c). As illustrated in Fig.\u00a02d), the connections between layers are of two types and include \u03c0\u2013\u03c0 stacking inter\u00adactions between DTBA and BA rings with the inter-centroid (C2\u2013C7)\u22ef(C9\u2013C14)iv separation being 3.8093\u2005(10)\u2005\u00c5, an angle of inclination of 8.36\u2005(8)\u00b0 and an off-set of 1.40\u2005\u00c5 for symmetry operation (iv): 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. The second inter\u00adaction is a weak, parallel DTBA-hy\u00addroxy-O1\u22ef\u03c0(C9\u2013C14)ii contact with a O1\u22efring centroid(C9\u2013C14)v separation of 3.9049\u2005(14)\u2005\u00c5 and angle at O1 = 60.96\u2005(9)\u00b0 for symmetry operation (v): x, y, 1\u00a0\u2212\u00a0z.The geometric parameters characterizing the inter\u00adatomic contacts, as identified in dnorm) as well as calculation of the inter\u00adaction energies using CrystalExplorer  and external (de) distances to the nearest nucleus dnorm mapping of the three-mol\u00adecule aggregate is shown in Fig.\u00a03\u22121, Table\u00a02\u22121. The short \u03c0\u2013\u03c0 inter\u00adaction involving the DTBA and BA benzene rings, mentioned in Supra\u00admolecular features, has an inter\u00adaction energy of \u221221.7\u2005kJ\u2005mol\u22121, i.e. more stable than the C\u2014H\u22efO inter\u00adactions. The energy calculation reveals that such an inter\u00adaction is mainly dispersive in nature, cf Table\u00a02a) and (b), and the mol\u00adecular dimer sustained by \u03c0\u2013\u03c0 contacts in Fig.\u00a04c).The v separation of 4.4323\u2005(10)\u2005\u00c5, an angle of inclination of 8.36\u2005(8)\u00b0 and an off-set of 2.74\u2005\u00c5 for symmetry operation (v): x, y, 1\u00a0\u2212\u00a0z. In addition, a BA-benzene-C6\u2014H\u22efS contact (2.94\u2005\u00c5) is noted, Table\u00a02Other important but less significant contacts are noted through the Hirshfeld surface analysis such as a longer \u03c0\u2013\u03c0 inter\u00adaction between DTBA and BA rings with an inter-centroid (C2\u2013C7)\u22ef(C9\u2013C14)di and de contact distances at the inter\u00adval of 0.01\u2005\u00c5 , O\u22efH/H\u22efO , S\u22efH/H\u22efS  and other contacts (8.0%). Among these contacts, only the O\u22efH/ H\u22efO, C\u22efC and S\u22efH/ H\u22efS contacts are shorter than the respective sums of the van der Waals radii to result in meaningful inter\u00adactions in the crystal, i.e. O\u22efH, C\u22efC and S\u22efH = \u223c1.72, \u223c3.4 and \u223c3.0\u2005\u00c5, respectively.A qu\u00adanti\u00adtative analysis of the Hirshfeld surfaces was performed through the generation of two-dimensional fingerprint plots by combining the di + de distances except for the O\u22efH/H\u22efO inter\u00adactions. Thus, overall (I)i.e. 12.8 versus 12.3%. The apparent disparity arises as a result of the larger surface area to volume ratio for the DTBA mol\u00adecule as compared to the DTBA+BA aggregate when it is considered as a single entity, hence leading to greater exposure of the O\u22efH/H\u22efO contacts in DTBA within its surrounding inter\u00adacting environment. A smaller disparity is evident for the -S\u22efH-/-H\u22efS- contacts, in that the former constitutes about 6.3% in (I)A close inspection on the corresponding decomposed fingerprint plots of the individual DTBA and BA mol\u00adecules reveals similar compositions as well as a)\u2013(c), the crystal is significantly governed by electrostatic force owing to the strong O\u2014H\u22efO inter\u00adactions that result in an alternate V-shape energy topology across the b-axis direction. A relatively less significant, but essential dispersion contribution is also observed and arises from the \u03c0\u2013\u03c0 inter\u00adactions spanning all benzene rings. Overall, it can be concluded that these inter\u00adacting forces directed the assembly of the mol\u00adecules in (I)In order to study the overall topology of the energy distributions in the crystal of (I)Structural commentary, the DTBA mol\u00adecule is twisted about the central di\u00adsulfide bond, having a C\u2014S\u2014S\u2014C torsion angle of \u221283.19\u2005(8)\u00b0. A survey of the literature indicates that this is a common feature of such mol\u00adecules. A search of the Cambridge Structural Database ethene  solution of the ground mixture. M.p. 384.2\u2013385.6\u2005K. IR (cm\u22121): 3070 \u03bd(C\u2014H), 1677 \u03bd(C=O), 1584 \u03bd(C=C), 1415 \u03b4(C\u2014H), 706 \u03b4(C=C), 684 \u03b4(OCO).All chemicals were of reagent grade and used as received without purification. 2-Thio\u00adbenzoic acid  was mixed with benzoic acid  and ground for 15 minutes in the presence of a few drops of methanol. The procedure was repeated three times. Colourless blocks were obtained by carefully layering toluene (1\u2005ml) on an Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from difference-Fourier maps and refined without constraint.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018017097/hb7790sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018017097/hb7790Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017097/hb7790Isup3.cmlSupporting information file. DOI: 1882556CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Z\u2032 = 1 is reported and compared with first polymorph with Z\u2032 = 2.A second polymorph of 3-meth\u00adoxy\u00adbenzoic acid with  8H8O3, is described in the centrosymmetric monoclinic space group P21/c with Z\u2032 = 1 as compared to the first polymorph, which crystallizes with two conformers (Z\u2032 = 2) in the asymmetric unit in the same space group. In the crystal of the second polymorph, inversion dimers linked by O\u2014H\u22efO hydrogen bonds occur and these are linked into zigzag chains, propagating along the b-axis direction by C\u2014H\u22efO links. The crystal structure also features a weak \u03c0\u2013\u03c0 inter\u00adaction, with a centroid-to-centroid distance of 3.8018\u2005(6)\u2005\u00c5. The second polymorph of the title compound is less stable than the reported first polymorph, as indicated by its smaller calculated lattice energy.A new polymorphic form of the title compound, C Polymorph I\u03b1 crystallizes in the monoclinic space group P21/n with a = 13.8034\u2005(17)\u2005\u00c5, b = 5.0275\u2005(5)\u2005\u00c5, c = 21.446\u2005(3)\u2005\u00c5 and \u03b2 = 99.320\u2005(13)\u00b0 , which are connected into a homodimer through strong O\u2014H\u22efO hydrogen bonds. As described below, these two conformers (A and B) differ in the orientation of the meth\u00adoxy group and its relative position from the \u2014OH group. DFT calculations suggest that the A conformer of I\u03b1 is more energetically stable than the B conformer . The mol\u00adecule is almost planar with a maximum deviation of 0.107\u2005(1)\u2005\u00c5 at atom O1. The mol\u00adecules of I\u03b2 adopt a similar conformation (overlay r.m.s.d. = 0.052\u2005\u00c5) as compared to the conformer A of I\u03b1  of I\u03b2 is close to coplanar with the attached phenyl ring (C1\u2013C6) as indicated by the dihedral angle of 5.6\u2005(7)\u00b0. The C8\u2014O3\u2014C3\u2014C2 torsion angle of I\u03b2 is \u2212176.63\u2005(7)\u00b0 as compared to \u2212176.75\u2005(11) and \u22121.4\u2005(2)\u00b0 for conformers A and B, respectively, of I\u03b1.The asymmetric unit of I\u03b2 Fig.\u00a01 consistsb-axis direction. The [010] chains are stacked along the a axis into corrugated sheets parallel to the ab plane via weak \u03c0\u2013\u03c0 inter\u00adactions with a centroid-to-centroid distance of 3.8018\u2005(6)\u2005\u00c5  and slippage of 1.676\u2005\u00c5.In the crystal of I\u03b2, two inversion-related mol\u00adecules are joined into a homodimer with an ds Fig.\u00a02. The homdnorm and the two-dimensional fingerprint plots for I\u03b2 were generated using CrystalExplorer17.5 . The H\u22efH contact is the most populated contact and contributes 42.3% of the total inter\u00admolecular contacts, followed by H\u22efO/O\u22efH (32.9%), H\u22efC/C\u22efH (11.4%) and C\u22efC (8.1%) contacts .The Hirshfeld surfaces mapped with normalized contact distance rm Fig.\u00a03 correspots Fig.\u00a04. The tipPIXEL software  is larger than that of I\u03b2 (98.5\u2005kJ\u2005mol\u22121) and this comparison is in agreement with the report of Pereira Silva et al. , see: Parvez 1987 and Ette al. 1988. For the al. 1988, Colapie al. 1988, Fausto  al. 1997 and Hath al. 2011. For the al. 2014 and Pere al. 2015.Single crystals of I\u03b2 were obtained from an unsuccessful attempt of co-crystallization between 3-meth\u00adoxy\u00adbenzoic acid and hexa\u00admethyl\u00adene\u00adtetra\u00admine. Colourless plate-like crystals were obtained from slow evaporation of a methano\u00adlic mixture of 3-meth\u00adoxy\u00adbenzoic acid and hexa\u00admethyl\u00adene\u00adtetra\u00admine in equimolar ratio at room temperature.O2 = 1.01\u2005(2)\u2005\u00c5]. The remaining H atoms were positioned geometrically [C\u2014H = 0.95 and 0.98\u2005\u00c5] and refined using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating group model (AFIX 137) was applied to the methyl group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018016900/hb7789sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018016900/hb7789Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018016900/hb7789sup3.docxHirshfeld shape-index and curvedness Figures. DOI: Click here for additional data file.10.1107/S2056989018016900/hb7789Isup4.cmlSupporting information file. DOI: 1448794CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C5H7N2+\u00b7C6H7O7\u2212 (I) and 3C5H7N2+\u00b7C6H5O73\u2212 (II). Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carb\u00adoxy\u00adlic group of the acid, while in II all three carb\u00adoxy\u00adlic groups of the acid are deprotonated and the charges are compensated for by three 2-amino\u00adpyridinium cations.2-Amino\u00adpyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-amino\u00adpyridine citric acid salts,  viz. C5H7N2+\u00b7C6H7O7\u2212 (I) (systematic name: 2-amino\u00adpyridin-1-ium 3-carb\u00adoxy-2-carb\u00adoxy\u00admethyl-2-hy\u00addroxy\u00adpropano\u00adate), and 3C5H7N2+\u00b7C6H5O73\u2212 (II) . The supra\u00admolecular synthons present are analysed and their effect upon the crystal packing is presented in the context of crystal engineering. Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carb\u00adoxy\u00adlic group of citric acid, while in II all three carb\u00adoxy\u00adlic groups of the acid are deprotonated and the charges are compensated for by three 2-amino\u00adpyridinium cations. In both structures, a complex supra\u00admolecular three-dimensional architecture is formed. In I, the supra\u00admolecular aggregation results from Namino\u2014H\u22efOacid, Oacid\u22efH\u2014Oacid, Oalcohol\u2014H\u22efOacid, Namino\u2014H\u22efOalcohol, Npy\u2014H\u22efOalcohol and Car\u2014H\u22efOacid inter\u00adactions. The mol\u00adecular conformation of the citrate ion (CA3\u2212) in II is stabilized by an intra\u00admolecular Oalcohol\u2014H\u22efOacid hydrogen bond that encloses an S(6) ring motif. The complex three-dimensional structure of II features Namino\u2014H\u22efOacid, Npy\u2014H\u22efOacid and several Car\u2014H\u22efOacid hydrogen bonds. In the crystal of I, the common charge-assisted 2-amino\u00adpyridinium\u2013carboxyl\u00adate heterosynthon exhibited in many 2-amino\u00adpyridinium carboxyl\u00adates is not observed, instead chains of N\u2014H\u22efO hydrogen bonds and hetero O\u2014H\u22efO dimers are formed. In the crystal of II, the 2-amino\u00adpyridinium\u2013carboxyl\u00adate heterosynthon is sustained, while hetero O\u2014H\u22efO dimers are not observed. The crystal structures of both salts display a variety of hydrogen bonds as almost all of the hydrogen-bond donors and acceptors present are involved in hydrogen bonding.2-Amino\u00adpyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-amino\u00adpyridinium citrate salts,  Organic crystals, especially salts, are now considered as potential materials for optical applications because of their flexibility in mol\u00adecular design , whose structure is illustrated in Fig.\u00a01I have different conformations. In one of them (C5/O4/O5) the O\u2014H and C=O bonds are in a syn conformation while in the other (C3/O2/O3), they have an anti conformation  hydrogen bonds [acid(t1) = C3/O2/O3], viz. N2\u2014H2D\u22efO2 , 4.762 and 6.396 . Thus, an equimolar mixing of citric acid and 2-amino\u00adpyridine resulted in the formation of salt on Fig.\u00a01. In the 2 Table\u00a01.II, illustrated in Fig.\u00a023\u2212 [(C5H5O7)3\u2212], and three 2-AMP+ cations , wherein the pyridine N atom of each 2-AMP unit is protonated and all three carb\u00adoxy\u00adlic groups of the acid are deprotonated. This is supported by the observation that the C\u2014O bonds of all the three carb\u00adoxy\u00adlic groups have similar bond lengths, in the range 1.231\u2005(2)\u20131.266\u2005(2)\u2005\u00c5, which is an indication of the partial double-bond character of all of the C\u2014O bonds resulting from deprotonation. The mol\u00adecular conformation of the CA3\u2212 anion is stabilized by an intra\u00admolecular Oalcohol\u2014H\u22efOacid(t1) hydrogen bond, namely O1\u2014H1O\u22efO3, that closes an S(6) ring motif  hydrogen bond, namely N1\u2014H1B\u22efO6. The second cation, 2-AMP2, inter\u00adacts with the CA3\u2212 anion via a charge-assisted 2-amino\u00adpyridinium-carboxyl\u00adate amino\u2014H\u22efOacid(t1) (N3\u2014H3A\u22efO3) and Npy\u2014H\u22efOacid(t1) (N4\u2014H4\u22efO2) hydrogen bonds. The third cation, 2-AMP3, inter\u00adacts with the anion via a discrete Namino\u2014H\u22efOacid(c) hydrogen bond, namely N6\u2014H6B\u22efO7.In the asymmetric unit of salt I are given in Table\u00a01I, the cations and anions of adjacent units are inter\u00adconnected by a Car\u2014H\u22efOacid(t1) inter\u00adactions, viz. C9\u2014H9\u22efO3, while adjacent anions related by b-glide symmetry form chains running along the b-axis direction, consisting of an acid(c)\u22efH\u2014Oacid(t1) and Oalcohol\u2014H\u22efOacid(c) hydrogen bonds, namely O3\u2014H3\u22efO7i and O1\u2014H1\u22efO6i; see Fig.\u00a03+ and CA\u2212 ions further aggregate to form sheets parallel to the ac plane \u2014H\u22efOacid(c) hydrogen bonds, namely O4\u2014H4\u22efO6iii, running along the a-axis direction and linking the twofold-symmetry-related CA\u2212 anions (Table\u00a01+ ions via Namino\u2014H\u22efOacid(t1)=C hydrogen bonds, namely N2\u2014H2D\u22efO2, and an amino\u2014H\u22efOalcohol and Npy\u2014H\u22efOalcohol hydrogen bonds, N2\u2014H2C\u22efO1ii and N1\u2014H1A\u22efO1ii, respectively, is formed  hydrogen bond. The CA3\u2212 anion and the first 2-AMP+ cation (2-AMP1) form sheets lying parallel to the (101) plane . The sheet consists of alternating CA3\u2212 and 2-AMP+ ions, forming chains via C11\u2014H11\u22efO2iii inter\u00adactions, with adjacent anti-parallel chains linked by C10\u2014H10\u22efO2ii, N1\u2014H1A\u22efO7i, N1\u2014H1B\u22efO6, N2\u2014H2\u22efO7i and N2\u2014H2\u22efO1i hydrogen bonds (Table\u00a02+ ions (2-AMP2) propagate alternately along the a-axis direction to form ribbons  consisting of alternating A\u22efO3 and N4\u2014H4\u22efO2 hydrogen bonds (Table\u00a02B\u22efO4 and C13\u2014H13\u22efO6 hydrogen bonds (Table\u00a02+ ions (2-AMP3) are inter\u00adlinked to the adjacent citrate ions, forming ribbons of alternating i and N6\u2014H6A\u22efO5i hydrogen bonds . Adjacent ribbons are further inter\u00adconnected by N6\u2014H6B\u22efO7 hydrogen bonds to form corrugated sheets parallel to the ab plane (Table\u00a02b). Overall a complex supra\u00admolecular three-dimensional structure is formed.In the crystal of s Table\u00a02. Howeverne Fig.\u00a05a and 5bs Table\u00a02. On the ns Fig.\u00a06a consiss Table\u00a02 and (11)s Table\u00a02. Finallys Table\u00a02, and . The most common hydrogen bonds observed in these hydrated salts are Namine\u2014H\u22efOcitric, Namine\u2014H\u22efOwater and Owater\u2014H\u22efOcitric, forming different supra\u00admolecular architectures. In the absence of a water mol\u00adecule, the most common hydrogen bonds are Namine\u2014H\u22efOcitric and Ocitric\u2014H\u22efOcitric. However, the nature of these supra\u00admolecular synthons varies from one structure to another, depending on the nature of the organic cations.A survey of the Cambridge Structural Database . Single crystals of salt II were obtained from a similar procedure; an ethano\u00adlic solution (15\u2005ml) of citric acid  was mixed with an ethano\u00adlic solution (15\u2005ml) of 2-amino\u00adpyridine .A solution of citric acid  in ethanol (15\u2005ml) was added to an ethano\u00adlic solution (15\u2005ml) of 2-amino\u00adpyridine . The resulting solution was heated and the hot solution was filtered. Slow evaporation of the solution resulted in the formation of colourless prismatic crystals of salt I, the OH H atom (H1) was positioned geometrically and refined as riding: O\u2014H = 0.82\u2005\u00c5 with Uiso(H) = 1.5Ueq(O). In salt II, the OH H atom (H1O) was located in a difference-Fourier map and freely refined. In both salts, the other H atoms were positioned geometrically and refined as riding: N\u2014H = 0.86\u2005\u00c5, C\u2014H = 0.93\u20130.97\u2005\u00c5 with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018009787/su5449sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989018009787/su5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018009787/su5449IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018009787/su5449Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018009787/su5449IIsup5.cmlSupporting information file. DOI: 1854628, 1854627CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Deletional hereditary persistence of fetal hemoglobin (HPFH)/\u03b4\u03b2\u2010thalassemia and \u03b4\u2010thalassemia are rare inherited disorders which may complicate the diagnosis of \u03b2\u2010thalassemia. The aim of this study was to reveal the frequency of these two disorders in Southwestern China.2 levels were confirmed by \u03b4\u2010globin gene sequencing. Furthermore, the pathogenicity and construction of a selected \u03b4\u2010globin mutation were analyzed.A total of 33,596 subjects were enrolled for deletional HPFH/\u03b4\u03b2\u2010thalassemia, and positive individuals with high fetal hemoglobin (Hb F) level were diagnosed by multiplex ligation\u2010dependent probe amplification (MLPA). A total of 17,834 subjects were analyzed for mutations in the \u03b4\u2010globin gene. Positive samples with low Hb A2 \u22642.0%) were characterized by molecular analysis. \u03b4\u2010Globin gene mutation was found at a frequency of 0.49% in Yunnan. The pathogenicity and construction for a selected \u03b4\u2010globin mutation was predicted.A total of 92 suspected cases with Hb F \u22655.0% were further characterized by MLPA. Eight different deletional HPFH/\u03b4\u03b2\u2010thalassemia were observed at a frequency of 0.024%. In addition, 195 cases suspected to have a \u03b4\u2010globin gene mutation (Hb AScreening of these two disorders was analyzed in Southwestern China, which could define the molecular basis of these conditions in this population. Fetal hemoglobin (Hb F) is a minor hemoglobin that is composed of two \u03b1\u2010 and two \u03b3\u2010globin chains (\u03b12\u03b32). Hereditary persistence of fetal hemoglobin  is caused by mutations in the promoter of the \u03b3\u2010globin gene  . As summarized in Globin Gene Server home page (http://globin.cse.psu.edu/hbvar/menu.html), more than 50 deletional HPFH/\u03b4\u03b2\u2010thalassemias and 130 mutations in the \u03b4\u2010globin gene have been reported to date. However, few reports on deletional HPFH/\u03b4\u03b2\u2010thalassemia and mutations in the \u03b4\u2010globin gene in Chinese population have been investigated at the molecular level. The aim of this study was to determine the frequency of deletional HPFH/\u03b4\u03b2\u2010thalassemia mutations and \u03b4\u2010globin gene mutations in Yunnan population. Furthermore, we characterized a rare \u03b4\u2010globin gene mutation using a comprehensive clinical and structure\u2010function analysis. These findings are important for accurate thalassemia prenatal diagnosis, as well as for providing molecular insights into new mutations in \u03b4\u2010globin gene.Both deletional HPFH/\u03b4\u03b2\u2010thalassemia and \u03b4\u2010thalassemia mutations are related to different ethnic backgrounds  and (b) low levels of Hb A2 associated with a visible second Hb A2 fraction . Internal quality control of the hemoglobin analysis was performed using the control materials provided by the manufacturer. A total of 33,596 subjects  were screened for deletional HPFH/\u03b4\u03b2\u2010thalassemia using capillary electrophoresis from July 2014 to September 2016. Individuals showing Hb F \u22655.0% were considered to be carriers of deletional HPFH/\u03b4\u03b2\u2010thalassemia 0 thalassemia and Southeast Asia HPFH (SEA\u2010HPFH) deletion were identified by Gap\u2010PCR  was performed using multiplex ligation\u2010dependent probe amplification (MLPA) following the manufacturer's instructions . Two commonest deletional HPFH, Chinese 2.43.7 (NC_000016.9:g.223300_227103del), \u2010\u03b14.2 (NC_000016.9:g.219817_(223755_224074)del), \u2010\u2010SEA (NC_000016.9:g.215400_234700del), \u03b1CS\u03b1 , \u03b1WS\u03b1 , and \u03b1QS\u03b1 .Two fragments of the \u03b4\u2010globin gene (NG_000007.3) were amplified using the following primers: \u03b41\u2010F 5\u2032CTGAGTCAAGACACACATGACAG3\u2032, \u03b41\u2010R 5\u2032 TGGTATGCATAATTTGAGTTGTTG3\u2032; \u03b42\u2010F 5\u2032 AATATCCTGTCTTTCTCTCCCAAC3\u2032, \u03b42\u2010R 5\u2032 TAATTTCTGCTCTTTGGAGGTAG3\u2032   and SIFT (http://sift.jcvi.org)   were determined for the normal and mutant \u03b4\u2010globin variant (monomer) using the Isoelectric Point Calculator (IPC) /\u03b4\u03b2\u2010thalassemia, 165 positive samples were selected (Hb F \u22655.0%). Eight cases of deletional HPFH/\u03b4\u03b2\u2010thalassemia were found by MLPA Figure , with a 0 deletion). Two unrelated individuals (case 3 and case 4) showed a similar (\u03b4\u03b2)0\u2010deletion. A G\u03b3(A\u03b3\u03b4\u03b2)0\u2010deletion was found in case 5. Two unrelated individuals (cases 6 and case 7) had a G\u03b3(A\u03b3\u03b4\u03b2)0 deletion, and this was confirmed as Chinese G\u03b3(A\u03b3\u03b4\u03b2)0 thalassemia by Gap\u2010PCR. Furthermore, case 7 was a compound heterozygous for Chinese G\u03b3(A\u03b3\u03b4\u03b2)0 and IVS\u2010I\u20101 (G\u00a0>\u00a0T) (HBB:c.92\u00a0+\u00a01G>T). Case 8 showed a \u201cdiscontinuous\u201d (\u03b5\u03b3\u03b4\u03b2)0 deletion, where the size of the deletion ranged from OR51M1\u20101 probe to hemoglobin subunit beta (HBB)\u2010up probe; however, among this deletion region, the hemoglobin subunit gamma (HBG)2\u20133 and HBG1\u2010up probes detected a fragment. Therefore, this deletion was considered to be a \u201cdiscontinuous\u201d (\u03b5\u03b3\u03b4\u03b2)0 deletion, and its sequence was further confirmed by targeted next\u2010generation sequencing  or a second Hb A2 fraction, and were selected for further molecular diagnosis. Seven types of \u03b4\u2010globin mutations were found in 87 \u03b4\u2010thalassemia patients  mutation had Hb A2 values below 1.6% (Hb A2\u00a0\u2264\u00a01.6%). One sample was a compound heterozygote for \u221277 (T\u00a0>\u00a0C) and \u2010\u03b13.7 with Hb A2 value of 1.4% .The number of subjects for each Hb A3.312/L, Hb 13.8g/dl, MCV 91.0fl, MCH 30.3pg, RDW\u2010CV 13.1%, and MCHC 333g/L. The predicted pIs of the wild type and mutant type were 7.42 and 6.87 respectively  mutation was selected for further bioinformatics analysis. The proband was a 31\u2010year\u2010old Chinese woman. Her hematological characteristics were as follows: RBC 4.5\u00d710y Figure a. The Lyy Figure b. Polyphy Figure c. Howevey Figure d.2O atoms  and B cell CLL/lymphoma 11A (BCL11A) can modulate fetal\u2010to\u2010adult globin switching. Mutations in KLF1 can result in significantly boosted Hb F levels in normal individuals 0\u2010deletion, one case of G\u03b3(A\u03b3\u03b4\u03b2)0\u2010deletion, two cases of Chinese G\u03b3(A\u03b3\u03b4\u03b2)0 deletion, and one case of (\u03b5\u03b3\u03b4\u03b2)0\u2010deletion were identified. All eight samples had typical \u03b2\u2010thalassemia phenotypes with hypochromic and microcytic erythrocytes due to deletions in the \u03b2\u2010globin gene or promoter. Case 7 was a compound heterozygote for the Chinese G\u03b3(A\u03b3\u03b4\u03b2)0 deletion and IVS\u2010I\u20101 (G\u00a0>\u00a0T). As a result, this patient had typical \u03b2\u2010thalassemia intermedia symptoms with increased Hb F levels  should be regarded as the frequency of deletional HPFH/\u03b4\u03b2\u2010thalassemia but not \u03b2\u2010globin cluster deletions. Some \u03b2\u2010globin cluster deletions, such as the 118\u00a0kb Filipino deletion with a normal Hb F 1.7% cannot be screened by capillary electrophoresis . The individuals who have \u03b4\u2010globin gene mutations do not usually have clinical phenotypes because of the physiologically lower expression levels of the \u03b4\u2010globin gene  Lys\u00a0>\u00a0Asn, HBB:c.198G\u00a0>\u00a0T]. A previous study also had shown that those heterozygous for Hb J Sicilia had no clinically significant problems (Ricco et al., 2 with a slight subunit modification (Sen et al., 2 structure obviously and p.K65N mutation in \u03b4\u2010globin gene should be benign.The 3D models evaluated by SWISS\u2010MODEL and PyMol showed that the K65 was located in a helix near the periphery of the protein. Based on the results from SWISS\u2010MODEL and PyMol, we observed that K65 was not positioned in a complex or important interaction network. Therefore, the substitution of the Lys residue should not significantly disrupt the structure and function of Hb AIn conclusion, this is the first report on the frequency and spectrum of deletional HPFH/\u03b4\u03b2\u2010thalassemia and mutations in the \u03b4\u2010globin gene in a Southwestern Chinese population. Bioinformatic analysis of a rare mutation characterized the potential changes at the protein\u2010level. Our study will provide a guideline for genetic counseling and prenatal diagnosis.The author reports no conflict of interest in this work.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file."}
{"text": "The di\u00adhydro\u00adbenzo\u00addiazole moiety is not quite planar while the whole mol\u00adecule adopts a U-shaped conformation in which there is a close approach of the two benzyl groups. Chains of alternating mol\u00adecules and lattice water extending along the normal to (301) are formed by O\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds. 24H21N5O\u00b7H2O, the di\u00adhydro\u00adbenzo\u00addiazole moiety is not quite planar, while the whole mol\u00adecule adopts a U-shaped conformation in which there is a close approach of the two benzyl groups. In the crystal, chains of alternating mol\u00adecules and lattice water extending along [201] are formed by O\u2014HUncoordW\u22efODhyr and O\u2014HUncoordW\u22efNTrz  hydrogen bonds. The chains are connected into layers parallel to (010) by C\u2014HTrz\u22efOUncoordW hydrogen bonds with the di\u00adhydro\u00adbenzo\u00addiazole units in adjacent layers inter\u00adcalating to form head-to-tail \u03c0-stacking [centroid-to-centroid distance = 3.5694\u2005(11)\u2005\u00c5] inter\u00adactions between them, which generates the overall three-dimensional structure. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H\u22efH (52.1%), H\u22efC/C\u22efH (23.8%) and O\u22efH/H\u22efO (11.2%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.In the title mol\u00adecule, C The benzene ring D (C12\u2013C17) is inclined to the triazole ring C by 78.91\u2005(11)\u00b0 while the latter ring is inclined to the B ring by 64.70\u2005(11)\u00b0. The dihedral angle between the mean planes of the B and E (C19\u2013C24) rings is 87.67\u2005(8)\u00b0.The title mol\u00adecule, (I) C Fig.\u00a01. The di\u00adUncoordW\u22efODhyr and O\u2014HUncoordW\u22efNTrz  hydrogen bonds (Table\u00a01Trz\u22efOUncoordW hydrogen bonds (Table\u00a01Cg2\u22efCg1i = 3.5694\u2005(11)\u2005\u00c5 where Cg1 and Cg2 are the centroids of the A and B rings, respectively; symmetry code: (i) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a02; dihedral angle = 2.50\u2005(10)\u00b0] leads to the final three-dimensional structure  analysis , Fig.\u00a06c,, Fig.\u00a06d, have a symmetrical distribution with the edges at de + di = 1.85\u2005\u00c5. The H\u22efN/N\u22efN contacts, contributing 7.4% to the overall crystal packing, are shown in Fig.\u00a06e as widely scattered points with the tips at de + di = 2.56\u2005\u00c5. The C\u22efC contacts, Fig.\u00a06f, have an arrow-shaped distribution of points with the tip at de = di = 1.77\u2005\u00c5. Finally, the C\u22efN/N\u22efC inter\u00adactions (2.2%) are reflected in Fig.\u00a06g as tiny characteristic wings with the tips at de + di = 3.44\u2005\u00c5.The overall two-dimensional fingerprint plot, Fig.\u00a06n Table\u00a02 is H\u22efH, c,Table\u00a02 with tridnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions in Fig.\u00a07a\u2013d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are recorded in Table\u00a04H-1,2,3-triazol-4-yl)meth\u00adyl]-2,3-di\u00adhydro-1H-1,3-benzo\u00addiazol-2-one hydrate ring. The energy band gap [\u0394E = ELUMO - EHOMO] of the mol\u00adecule is 5.3468\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22126.1633 and \u22120.8166\u2005eV, respectively.The optimized structure of the title compound, (I)To a mixture of 3-methyl-1-(prop-2-yn\u00adyl)-3,4-di\u00adhydro\u00adquinoxalin-2(1H)-one (0.65\u2005mmol) in ethanol (20\u2005ml) was added 1-(azido\u00admeth\u00adyl)benzene (1.04\u2005mmol). The mixture was stirred under reflux for 24\u2005h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue obtained was purified by column chromatography on silica gel by using as eluent a mixture (hexa\u00adne/ethyl acetate: 9/1). The isolated solid product was recrystallized from ethanol to afford yellow crystals (yield: in 19%).Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table\u00a0510.1107/S2056989019016876/lh5940sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019016876/lh5940Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016876/lh5940Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019016876/lh5940Isup4.cmlSupporting information file. DOI: 1972575CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III complex compound with pentetic acid is reported. The complex mol\u00adecule is a zwitterion and the GaIII centre is bound in a slightly distorted octa\u00adhedral coordination sphere by two amine N atoms, three carboxyl\u00adate O atoms and one water O atom.The structure of a Ga III complex compound with pentetic acid, [Ga(C14H20N3O10)(H2O)]\u00b73H2O, the GaIII centre is bound in a slightly distorted octa\u00adhedral coordination sphere by two amine N atoms, three carboxyl\u00adate O atoms and one water O atom. The complex mol\u00adecule exists as a zwitterion. In the crystal, the complexes are linked to each other via O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming layers parallel to (001). Three uncoordinating water mol\u00adecules link the complex layers via O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming a three-dimensional network.In the title Ga A complex is easily formed between gallium and DTPA and it has a stability constant of 1023.32, which makes the complex stable against exchange with transferrin \u2005\u00c5]. The C\u2014O bond lengths coordinating to the GaIII atom vary little, with the shortest and longest bonds differing by only 0.019\u2005\u00c5 . The three trans angles, N1\u2014Ga1\u2014O1W, O1\u2014Ga1\u2014O5 and O3\u2014Ga1\u2014N2, are 174.57\u2005(16), 174.05\u2005(12) and 164.97\u2005(13)\u00b0, respectively. The O\u2014Ga\u2014O, O\u2014Ga\u2014N and N\u2014Ga\u2014N bite angles in the chelate rings deviate somewhat from 90\u00b0, ranging from 81.75\u2005(12) to 95.91\u2005(12)\u00b0.The complex mol\u00adecule (abbreviated as Ga-DTPA) is a zwitterion and has a slightly distorted octa\u00adhedral coordination geometry with one water and one amine in the axial positions, and three carboxyl\u00adate groups and one amine in the equatorial positions. The complex consists of three five-membered Ga/N/C/C/O chelate rings and one five-membered Ga/N/C/C/N chelate ring. The Ga\u2014N bonds [Ga1\u2014N1 = 2.081\u2005(4)\u2005\u00c5 and Ga1\u2014N2 = 2.156\u2005(3)\u2005\u00c5] are significantly longer than the Ga\u2014O bonds [Ga1\u2014O1 = 1.933\u2005(3)\u2005\u00c5, Ga1\u2014O3 = 1.925\u2005(3)\u2005\u00c5, Ga1\u2014O5 = 1.964\u2005(3)\u2005\u00c5 and Ga1\u2014O1a and b axes provided in Figs. 2via O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming a three-dimensional network.Packing depictions viewed along the et al., 2016In our survey of the Cambridge Structural Database  in acetate buffer (2\u2005mL) adjusted to pH = 4.2 was heated with stirring for dissolution. Gallium nitrate (39.9\u2005mg) was then added to the DTPA solution and the mixture was stirred for at least 10\u2005min at 353\u2005K. The solution was concentrated under ambient pressure at room temperature. When almost all of the solvent had evaporated, methanol was added dropwise to precipitate Ga-DTPA. The precipitate was collected on a 0.22\u2005\u00b5m polyamide filter and dried at room temperature. The obtained Ga-DTPA (1.30\u2005mg) was re-dissolved in ultra-pure water (1\u2005mL) and single crystals suitable for X-ray diffraction were obtained after four weeks by slow diffusion of tetra\u00adhydro\u00adfuran into the aqueous solution, as illustrated in Fig.\u00a04Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018009428/is5497sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009428/is5497Isup2.hklStructure factors: contains datablock(s) I. DOI: 1852608CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "T was isolated from laboratory tap water during a water quality assessment in University of Malaya, Malaysia. The strain was a Gram\u2010negative, rod\u2010shaped, nonmotile, and aerobic bacterium. Complete genome of P08T comprised of a 2,820,660\u00a0bp chromosome with a G\u00a0+\u00a0C content of 36.43%. Both 16S rRNA phylogeny and phylogenetic tree inferred from the core gene matrix demonstrated that P08T formed a hitherto unknown subline within the family Neisseriaceae. Ortho average nucleotide identity (OrthoANI) values and the percentage of conserved proteins (POCP) calculated from complete genome sequence indicated low relatedness between P08T and its phylogenetic neighbors. Respiratory quinone analysis revealed Q\u20108 as the only detectable quinone. The predominant cellular fatty acids were identified as C14:0, iso\u2010C15:0, and summed feature 3 (C16:1\u03c97c/C16:1\u03c96c). The polar lipids consisted of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine. All aspects of phenotypic and phylogenetic data suggested that strain P08T represents a novel genus within family Neisseriaceae, for which the name Aquella gen. nov. is proposed. The type species of the genus is Aquella oligotrophica sp. nov., and the type strain is P08T (=LMG 29629T =DSM 100970T).A bacterial strain designated as P08 After 3\u00a0days of incubation on R2A agar (BD Difco) at 37\u00b0C, bacteria isolation and purification were performed. The purified strain was routinely cultivated in R2A liquid medium, unless specified. Cells were preserved in 20% (v/v) glycerol at \u221280\u00b0C. The strain P08T has been deposited in the German Collection of Microorganisms and Cell Cultures  and the Belgium Coordinated Collections of Microorganisms .Strain P082.2T was extracted using the MasterPureTM DNA purification kit  following the manufacturer's protocol. Extracted genomic DNA was sheared and constructed into a template library according to the \u201cGuidelines for Preparing 20\u00a0kb SMRTbell\u2122 Templates.\u201d Genome sequencing was performed in 1 SMRT cell using the PacBio RS II single\u2010molecule real\u2010time (SMRT) sequencing technology . The reads were de novo assembled using the hierarchical genome assembly process (HGAP) algorithm version 2  version 2.10   analysis, the homologous clusters were determined using panX pan\u2010genome pipeline  , Luria\u2010Bertani agar (Merck), Pseudomonas agar (BD Difco), MacConkey agar (Merck), R2A agar (BD Difco), and trypticase soy agar (Merck), and the ability to grow in this media was recorded after incubation of 3\u00a0days at 37\u2009\u00b0C. Oxidase and catalase activities were examined with solutions of oxidase reagent (bioM\u00e9rieux) and 3% (v/v) hydrogen peroxide, respectively. The morphology of bacterial cells was observed using tabletop scanning electron microscopy . Cellular motility was tested by the hanging drop method , 0.1\u00a0M NaHCO3/0.1\u00a0M Na2CO3 (pH\u20099.0\u201310.0), and 0.05\u00a0M Na2HPO4/0.1\u00a0M NaOH. Growth on medium added with sodium chloride (NaCl) was determined in R2A medium supplemented with 0, 0.5, 1%\u20136%  (w/v) NaCl after 14\u00a0days of incubation at 37\u2009\u00b0C. Growth under anaerobic condition was determined by incubating strain P08T on R2A agar in the Oxoid AnaeroGen system.Growth of strain P08T was tested on R2A agar supplemented with casein , starch , cellulose , urease, Tweens 20, 40, 60, and 80 for hydrolysis activities, respectively  on R2A agar (BD Difco) plates. The disks (Oxoid) contained the following antibiotics: ampicillin (10\u00a0\u03bcg), ampicillin/sulbactam (20\u00a0\u03bcg), chloramphenicol (30\u00a0\u03bcg), gentamicin (10\u00a0\u03bcg), kanamycin (30\u00a0\u03bcg), nalidixic acid (30\u00a0\u03bcg), rifampicin (5\u00a0\u03bcg), penicillin G (10\u00a0\u03bcg), streptomycin (10\u00a0\u03bcg), sulfamethoxazole (23.75\u00a0\u03bcg) plus trimethoprim (1.25\u00a0\u03bcg), and tetracycline (30\u00a0\u03bcg). The effect of antibiotics on cell growth was assessed after incubation for 2\u00a0days at 37\u00b0C. The diameter of the antibiotic disks was 6\u00a0mm. The strain was considered susceptible when the diameter of the inhibition zone was>13\u00a0mm, intermediate at 10\u201312\u00a0mm, and resistant at <10\u00a0mm as described by Nokhal and Schlegel , and lesser to all validly described type strains, for instance Neisseria iguana NVSL 85737T (89.4%), Neisseria flavescens ATCC 13120T (89.3%), Paludibacterium paludis KBP\u201021T (89.3%), Uruburuella testudines 07_OD624T (89.3%), and Morococcus cerebrosus CIP 81.93T (89.3%) based on EzBioCloud similarity\u2010based search  phylogenetic tree based on 16S rRNA gene sequences. Strain P08T formed a branch clearly separated from the remaining genera from Neisseriaceae. As indicated in Figure T appeared to be more closely related to Neisseriaceae, compared to the type species of genus Prolinoborus, which have a questionable taxonomic status in Neisseriaceae  and JGI portal . Out of a total of 2,625 genes in the genome, 2,564 protein\u2010coding gene, 12 rRNAs, and 46 tRNAs were predicted from the chromosome by PGAP analysis  designation  algorithm version 2 . Intriguingly, strain P08T has the lowest G\u00a0+\u00a0C content among these genomes. The range of G\u00a0+\u00a0C contents ranged widely from the lowest 36.43% in strain P08T to the highest 68.30% in genome of Crenobacter luteus CN10 , iso\u2010C15:0 (36.2%), C16:0 (9.9%), summed feature 3 (C16:1\u03c97c/C16:1\u03c96c) (16.4%), and summed feature 8 (C18:1\u03c97c) (6.8%). Strain P08T exhibited a polar lipid profile consisting of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine  value suggested by Ludwig et al.  .14:0, iso\u2010C15:0, and summed feature 3 (C16:1\u03c97c/C16:1\u03c96c). The main polar lipids consist of uncharacterized aminolipid, phosphatidylglycerol, and phosphatidylethanolamine. The G\u00a0+\u00a0C content of the DNA of the type strain of the type species is 36.43\u00a0mol%. Based on 16S rRNA sequence analyses, P08T belongs to the Betaproteobacteria. The type species is Aquella oligotrophica P08T.Cells are Gram\u2010negative, aerobic, nonmotile, rod\u2010shaped. Cells are oxidase and catalase negative. Q\u20108 is the only quinone type. Major fatty acids (>10%) are C4.2Aquella oligotrophica .D\u2010galactopyranoside, 2\u2010nitrophenyl\u2010\u03b2\u2010D\u2010galactopyranoside, and sodium pyruvate. Negative reactions toward potassium nitrate, L\u2010tryptophane, D\u2010glucose, L\u2010arginine, urea, esculin, ferric citrate, gelatin (bovine origin), D\u2010glucose, L\u2010arabinose, D\u2010mannose, D\u2010mannitol, N\u2010acetyl\u2010glucosamine, D\u2010maltose, potassium gluconate, capric acid, malic acid, trisodium citrate, phenylacetic acid, L\u2010lysine, L\u2010ornithine, sodium thiosulfate, inositol, D\u2010sorbitol, L\u2010rhamnose, D\u2010sucrose, D\u2010melibiose, and amygdalin. Based on testing with API ZYM kit, C4 esterase, C8 esterase lipase, leucine arylamidase, acid phosphatase, naphthol\u2010AS\u2010BI\u2010phosphohydrolase, \u03b2\u2010galactosidase, and N\u2010acetyl\u2010\u03b2\u2010glucosaminidase activities are detected but negative for activities of C14 lipase, valine arylamidase, trypsin, \u03b1\u2010chymotrypsin, \u03b2\u2010glucuronidase, \u03b1\u2010glucosidase, \u03b2\u2010glucosidase, \u03b1\u2010mannosidase, and \u03b1\u2010fucosidase. Weak enzymatic activities of alkaline phosphatase, cystine arylamidase, and \u03b1\u2010galactosidase are detected. The major fatty acids (> 5%) are C14:0, iso\u2010C15:0, C16:0, summed feature 3 (C16:1\u03c97c/C16:1\u03c96c), and summed feature 8 (C18:1\u03c97c). The following compounds are utilized as sole carbon sources in the GEN III microplate: D\u2010galactose, D\u2010glucuronic acid, D\u2010mannose, glucuronamide, glycyl\u2010L\u2010proline, inosine, L\u2010alanine, L\u2010arginine, L\u2010aspartic acid, L\u2010glutamic acid, L\u2010serine, methyl pyruvate, N\u2010acetyl\u2010D\u2010glucosamine, \u03b1\u2010D\u2010glucose, and \u03b2\u2010hydroxy\u2010D,L\u2010butyric acid. All other substrates in the GEN III microplate are not utilized. Sensitive to ampicillin/sulbactam (20\u00a0\u03bcg), chloramphenicol (30\u00a0\u03bcg), nalidixic acid (30\u00a0\u03bcg), rifampicin (5\u00a0\u03bcg), sulfamethoxazole (23.75\u00a0\u03bcg) plus trimethoprim (1.25\u00a0\u03bcg), and tetracycline (30\u00a0\u03bcg).Exhibits the following properties in addition to those given in the genus description. Cell sizes range from 0.7\u20131.4\u00a0\u03bcm in length and 0.3\u20130.5\u00a0\u03bcm in width  was isolated from laboratory tap water collected at University of Malaya, Malaysia.The type strain The authors declare no conflict of interest.KGC supervised the project. LSL carried out the experiments. WSST and LSL wrote the manuscript with support from KGC, KOC, AP, KMG, KWH, and WFY. WSST and LSL analyzed the data.None required.\u00a0Click here for additional data file."}
{"text": "III complex with a Schiff base ligand formed in situ from cyste\u00adamine (2-amino\u00adethane\u00adthiol) and 5-bromo\u00adsalicyl\u00adaldehyde is reported.The crystal structure of novel binuclear Co III complex, [Co2(C9H8BrNOS)2(C18H16Br2N2O2S2)]\u00b7C3H7NO, with a Schiff base ligand formed in situ from cyste\u00adamine (2-amino\u00adethane\u00adthiol) and 5-bromo\u00adsalicyl\u00adaldehyde crystallizes in the space group P21. It was found that during the synthesis the ligand undergoes spontaneous oxidation, forming the new ligand H2L\u2032 having an S\u2014S bond. Thus, the asymmetric unit consists of one Co2(L)2(L\u2032) mol\u00adecule and one DMF solvent mol\u00adecule. Each CoIII ion has a slightly distorted octa\u00adhedral S2N2O2 coordination geometry. In the crystal, the components are linked into a three-dimensional network by several S\u22ef Br, C\u22ef Br, C\u2014H\u22efBr, short S\u22efC  contacts as well by weak C\u2014H\u22efO hydrogen bonds. The crystal studied was refined as an inversion twin.The title binuclear Co The synthesis, crystal structure and spectroscopic characterization are described herein.Schiff bases represent one of the most widely used organic compounds. The ability to construct novel ligand systems by means of condensation of a variety of readily available aldehydes and amine makes them and their metal complexes ideal candidates for the construction of novel polynuclear compounds as well for investigation of a large range of properties \u00b0 between the mean planes of atoms O3/N3/C19/C24/C25 and O4/N4/C28/C33/C34 around Co1, and 64.78\u2005(2)\u00b0 between the mean planes of atoms O2/N2/C15/C10/C16 and O1/N1/C1/C6/C7 around Co2. During the synthesis, the ligand is partially oxidized with the formation of a \u2013(CH2)2\u2013S\u2013S\u2013(CH2)2\u2013 bridge. Thus, in contrast to a closely related complex \u2005\u00c5. The Co\u2014S distances in the title complex are in the range 2.207\u2005(3)\u20132.289\u2005(3)\u2005\u00c5, which is generally comparable to the range 2.23\u20132.26\u2005\u00c5 observed for other thio\u00adether\u2013CoIII complexes published earlier  [3.596\u2005(2)\u2005\u00c5] and S\u22ef Br [3.364\u2005(2)\u2005\u00c5] contacts, which connect neighboring structural units into chains along [001]  are essentially shorter than the sum of the van der Waals radii for the atoms involved [S4\u22efC16 = 3.198\u2005(8)\u2005\u00c5] \u00adethane\u00adthiol\u00adato]-N-(3-thia\u00adpent-5-en\u00adyl)sali\u00adcylaldiminato-N,O)dicobalt(III) aceto\u00adnitrile solvate and [1,8-bis\u00ad-3,6-di\u00adthia\u00adocta\u00adne)cobalt(III) perchlor\u00adate with a di\u00adsulfide moiety . Analysis calculated for C39H39Br4Co2N5O5S4 (M = 1223.49): C,38.28; N, 5.72; H, 3.21%. Found: C, 38.31; N, 5.79; H, 3.28%. The compound is sparingly soluble in CH3CN and good in DMSO, DMF.A solution of KOH  in a minimum amount of methanol was added to a solution of 2-amino\u00adethanthiol hydro\u00adchloride  in methanol (5\u2005ml) and stirred in an ice bath for 10\u2005min. The white precipitate of solid KCl was removed by filtration and 5-bromo\u00adsalicyl\u00adaldehyde  in di\u00admethyl\u00adformamide (10\u2005ml) were added to the filtrate and stirred on air magnetically for 40\u2005min. Cobalt acetate  was added to the yellowish solution of the Schiff base formed \u22121 range shows the characteristic azomethine group (\u2013H\u2014C=N) peak at 1616\u2005cm\u22121, indicating the formation of the Schiff base. There are no bands assignable to \u03c5(O\u2014H), indicating the loss of the phenolic hydrogen of the free ligand. In addition, all the characteristic functional group peaks are present in the spectrum. Thus, signals in the 3000\u20133100\u2005cm\u22121 and 1600\u20131400\u2005cm\u22121 regions were assigned to the aromatic C\u2014H and C\u2014C stretches, and weak bands at 544\u2005cm\u22121 and 684\u2005cm\u22121 to the S\u2014S and C\u2014S stretches, respectively. The very strong bands at 1454\u2005cm\u22121 can be attributed to overlapped C\u2014H bending (scissoring) (in the CH3 groups of the solvent mol\u00adecule) and aromatic \u2013C=C stretching vibrations. Another strong band at 1310\u2005cm\u22121 can be assigned to C\u2014O vibrations.The IR spectrum of the title complex in the 4000\u2013400\u2005cm1H NMR spectra, obtained in DMSO-d6 at room temperature using TMS as the inter\u00adnal standard. It revealed an azomethine proton singlet at 8.099 ppm as well the increase in spectroscopic complexity in both the aromatic and aliphatic regions. 1H NMR, DMSO-d6, \u03b4 in ppm: \u2013CH=N, 8.099 (s); aromatic protons (C6H3): 7.94\u20136.52; aliphatic protons (\u2013SCH2CH2N=): 4.44 (m); solvent CH3: 2.96 (s), 2.8 (s). Unfortunately, it could not provide any indication of the dinuclear binding mode, which was revealed only by the X-ray structure determination.The structural assignment of the title compound was supplemented by its Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atom. The crystal studied was refined as an inversion twin with the ratio of the twin components refining to 0.436\u2005(12):0.564\u2005(12).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019007217/lh5903sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019007217/lh5903Isup2.hklStructure factors: contains datablock(s) I. DOI: 1916953CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is built up from the benzodiazepine ring system linked to the pyridyl and pendant di\u00adhydro\u00adpyran rings. In the crystal, N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds link the mol\u00adecules into a three-dimensional network. A weak C\u2014H \u22ef \u03c0 inter\u00adaction is also observed. 17H18N2O3, is constructed from a benzodiazepine ring system linked to a pendant di\u00adhydro\u00adpyran ring, where the benzene and pendant di\u00adhydro\u00adpyran rings are oriented at a dihedral angle of 15.14\u2005(4)\u00b0. Intra\u00admolecular N\u2014HDiazp\u22efODhydp and C\u2014HDiazp\u22efODhydp (Diazp = diazepine and Dhydp = di\u00adhydro\u00adpyran) hydrogen bonds link the seven-membered diazepine ring to the pendant di\u00adhydro\u00adpyran ring, enclosing S(6) ring motifs. In the crystal, N\u2014HDiazp\u22efODhydp hydrogen bonds link the mol\u00adecules into infinite chains along [10via C\u2014HBnz\u22efODhydp, C\u2014HDhydp\u22efODhydp and C\u2014HMth\u22efODhydp (Bnz = benzene and Mth = meth\u00adyl) hydrogen bonds, forming a three-dimensional network. The observed weak C\u2014HDiazp \u22ef \u03c0 inter\u00adaction may further stabilize the structure. Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (51.1%), H\u22efC/C\u22efH (25.3%) and H\u22efO/O\u22efH (20.3%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.The title compound, C Many members of this family are widely used as anti\u00adconvulsant, anti-anxiety, anti-seizure, analgesic, sedative, anti\u00addepressive and hypnotic or anti-inflammatory agents  \u2005\u00c5 (for atom C10), and is oriented at a dihedral angle of 15.14\u2005(4)\u00b0 with respect to the benzene (B: C4\u2013C9) ring. A puckering analysis of the seven-membered diazepine ring (A: N1/N2/C1\u2013C4/C9) gave the parameters QT = 0.6874\u2005(14), q2 = 0.5903\u2005(14), q3 = 0.3523\u2005(14)\u2005\u00c5, \u03c62 = 352.88\u2005(14), \u03c63 = 245.8\u2005(2)\u00b0. In ring A, the N1\u2014C1\u2014C2 [117.10\u2005(2)\u00b0], C1\u2014C2\u2014C3 [114.17\u2005(11)\u00b0], C3\u2014N2\u2014C4 [128.91\u2005(11)\u00b0], N2\u2014C4\u2014C9 [127.38\u2005(12)\u00b0], C4\u2014C9\u2014N1 [126.21\u2005(12)\u00b0] and C9\u2014N1\u2014C1 [130.71\u2005(12)\u00b0] bond angles are enlarged, while the C2\u2014C3\u2014N2 [108.97\u2005(11)\u00b0] bond angle is narrowed, when compared with the corresponding values in the seven-membered diazepine ring in the closely related compound, 3,4-di\u00adhydro-2--4-(4-pyridin-4-yl)-1,5-benzo- diazepine, (II), where the pendant di\u00adhydro\u00adpyran ring is not planar The title compound, (I)4) Fig.\u00a01. Ring C Diazp\u22efODhydp and C\u2014HDiazp\u22efODhydp (Diazp = diazepine and Dhydp = di\u00adhydro\u00adpyran) hydrogen bonds  ring motifs s Table\u00a01 link thefs Fig.\u00a01.Diazp\u22efODhydp hydrogen bonds  hydrogen bonds  analysis  and H\u22efN/N\u22efH  contacts in the structure contribute only 1.6 and 1.1%, respectively, to the HS. The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions in Fig.\u00a07a\u2013c, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a06s Table\u00a02. In the s Table\u00a02. There is Table\u00a01 as well s Table\u00a01 and is s\u22efO Fig.\u00a06e and H\u22ef\u22efH Fig.\u00a06f contacet al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  in ethanol (40\u2005ml) was refluxed for 1\u2005h. After cooling to room temperature, the colourless inter\u00admediate solid compound, a mono-Schiff base, was obtained in 70% yield. The inter\u00admediate  was refluxed in acetone (10\u2005ml) for 1h. After cooling, the crystals formed were filtered and dried (yield: 65%).A solution of de\u00adhydro\u00adacetic acid  and Uiso(H) = kUeq, where k = 1.5 for methyl H atoms and 1.2 for the other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019000689/lh5890sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019000689/lh5890Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000689/lh5890Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019000689/lh5890Isup4.cmlSupporting information file. DOI: 1890950CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two new forms of cobalt\u2013pyridine\u2013sulfate complexes are presented. The feature infinite chains of metal\u2013pyridine units connected by bridging sulfate anions, which are distinct from the only previously reported structure of a cobalt\u2013pyridine\u2013sulfate compound. catena-poly[[tetra\u00adkis\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba2O:O\u2032], [Co(SO4)(C5H5N)4]n, (1), and catena-poly[[tetra\u00adkis\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba3O:O\u2032,O\u2032\u2032-[bis\u00ad(pyridine-\u03baN)cobalt(II)]-\u03bc-sulfato-\u03ba3O,O\u2032:O\u2032\u2032]n, [Co2(SO4)2(C5H5N)6]n, (2), are reported. Compound (1) displays a polymeric structure, with infinite chains of CoII cations adopting octa\u00adhedral N4O2 coordination environments that involve four pyridine ligands and two bridging sulfate ions. Compound (2) is also polymeric with infinite chains of CoII cations. The first Co center has an octa\u00adhedral N4O2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The second Co center has an octa\u00adhedral N2O4 coordination environment that involves two pyridine ligands and two bridging sulfate ions that chelate the Co atom. The structure of (2) was refined as a two-component inversion twin.The solid-state structures of two cobalt\u2013pyridine\u2013sulfate compounds, namely  When grown out, the cobalt ion shows an octa\u00adhedral coordination environment . The equatorial positions of the octa\u00adhedron are occupied by four pyridine ligands in a square-planar arrangement. The CoN4 unit exhibits planarity enforced by symmetry, with cis N\u2014Co\u2014N angles of 86.45\u2005(6) and 93.55\u2005(6)\u00b0. To complete the octa\u00adhedron, the axial positions are occupied by two sulfate ions, with an inversion enforced O\u2014Co\u2014O angle of 180\u00b0 and cis O\u2014Co\u2014N angles of 88.87\u2005(6) and 91.67\u2005(6)\u00b0. The pyridine rings are rotated from the CoN4 plane by dihedral angles of 47.30\u2005(10) and 78.33\u2005(9)\u00b0. The 78.33\u2005(9)\u00b0 angles are constrained by two C\u2014H\u22efO inter\u00adactions between the ortho hydrogen atoms and the two trans sulfates  consists of two cobalt atoms, six coordinated pyridines and two sulfate anions . There are two crystallographically unique cobalt atoms, with Co1  displaying an octa\u00adhedral N4O2 coordination environment and Co2  exhibiting an octa\u00adhedral N2O4 coordination geometry.The asymmetric unit of the purple crystals of  to 93.18\u2005(12)\u00b0, and the trans O\u2014Co\u2014O angle is 173.43\u2005(12)\u00b0. The planes of the four pyridine rings are rotated from the equatorial CoN4 plane by dihedral angles of 58.6\u2005(2), 64.6\u2005(2), 65.6\u2005(2), and 73.1\u2005(2)\u00b0. Two of the rings show one C\u2014H\u22efO inter\u00adaction with an ortho hydrogen atom, one ring shows two C\u2014H\u22efO inter\u00adactions with two ortho hydrogen atoms, and the fourth ring shows no C\u2014H\u22efO inter\u00adactions \u00b0. The two sulfate ligands exhibit O\u2014Co\u2014O bite angles of 65.90\u2005(10) and 66.37\u2005(10)\u00b0. The other cis O\u2014Co\u2014O angles are 86.87\u2005(11), 98.98\u2005(11), and 102.84\u2005(11)\u00b0, and the six cis N\u2014Co\u2014O angles range from 92.49\u2005(12) to 98.33\u2005(13)\u00b0. Each pyridine ring is involved in ortho C\u2014H\u22efO inter\u00adactions  are linked together into infinite chains along the [001] direction through sulfate anions with O\u2014S\u2014O bridges . Between each successive tetra\u00adpyridine cobalt unit, there are parallel slipped \u03c0\u2013\u03c0 inter\u00adactions .The Cos Figs.\u00a03a, 4 \u25b8aII atoms in compound (2) are linked together into infinite chains along the [111] direction through the sulfate anions . The chain alternates between tetra\u00adpyridine cobalt units and di\u00adpyridine cobalt units. No \u03c0\u2013\u03c0 inter\u00adactions are observed in the crystal.The Cos Figs.\u00a03b, 4 \u25b8b3(SO4)3(C5H5N)11)]n, which was grown at a lower concentration of cobalt. This structure shows two successive octa\u00adhedral cobalt atoms with N4O2 coordination, where each atom is coordinated to four pyridines and two bridging sulfates. The third cobalt atom in the chain shows N3O3 coordination where three pyridines are bound and there are two sulfates bound, one of which is chelating to the cobalt  and (2). In compound (1), every cobalt atom possesses an octa\u00adhedral N4O2 coord\u00adin\u00adation. This complex is isostructural with the structure observed for the iron and nickel pyridine\u2013sulfate complexes , the cobalt atoms alternate between N4O2 coordination and N2O4 coordination. This tetra\u00adpyridine/bi\u00adpyridine alternation is similar to what is observed in the zinc\u2013pyridine\u2013sulfate structure, which alternates between octa\u00adhedral and tetra\u00adhedral zinc centers. In the case of cobalt, the bis\u00ad(pyridine) cobalt center is still octa\u00adhedral because the two coordinated sulfates both chelate to the cobalt. The end result is an infinite chain of octa\u00adhedral cobalt atoms, which is true in compound (1) and the previously reported cobalt\u2013pyridine\u2013sulfate complex. The methane\u00adsulfato complexes of cobalt (II) have also been reported as octa\u00adhedral tetra\u00adkis\u00ad(pyridine), [Co(SO3CH3)2(py)4], and octa\u00adhedral bis\u00ad(pyridine), [Co(SO3CH3)2(py)2], compounds, consistent with the two independent cobalt centers observed in (2) , 40\u2005mg of cobalt sulfate hepta\u00adhydrate (J. T. Baker) was dissolved in pyridine  and distilled water (100\u2005\u00b5L) in a 20\u2005mL vial. The vial was heated to 338\u2005K for 48\u2005h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.For compound (2), 48\u2005mg of cobalt sulfate hepta\u00adhydrate (J. T. Baker) was dissolved in pyridine  and distilled water (30\u2005\u00b5L) in a 20\u2005mL vial. The vial was heated to 358\u2005K for 48\u2005h, after which single crystals suitable for X-ray diffraction studies were isolated from the reaction mixture.For compound (SHELXL) by full-matrix least squares on F2. Hydrogen atoms were placed in calculated positions and then refined with a riding model with C\u2014H bond lengths of 0.95\u2005\u00c5 and with isotropic displacement parameters set to 1.20 Ueq of the parent C atom. The structre of (2) was refined as a two-component inversion twin, BASF = 0.165\u2005(13).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901901538X/sj5586sup1.cifCrystal structure: contains datablock(s) 1, 2, I. DOI: 10.1107/S205698901901538X/sj55861sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698901901538X/sj55862sup3.hklStructure factors: contains datablock(s) 2. DOI: 1965662, 1965663, 1965662, 1965663CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structures of the two isomeric hydrogen-bonded 1:1 co-crystals of 3-chloro-2-nitro\u00adbenzoic acid with 5-nitro\u00adquinoline and 6-nitro\u00adquinoline, and the 1:1 salt of 3-chloro-2-nitro\u00adbenzoic acid with 8-hy\u00addroxy\u00adqunoline have been determined at 190\u2005K. In each crystal, the acid and base mol\u00adecules are linked by a short O\u2014H\u22efN or N\u2014H\u22efO hydrogen bond. 7H4ClNO4\u00b7C9H6N2O2, the acid and base mol\u00adecules are held together by O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds. In compound (III), C9H8NO+\u00b7C7H3ClNO4\u2212, an acid\u2013base inter\u00adaction involving H-atom transfer occurs and the H atom is located at the N site of the base mol\u00adecule. In the crystal of (I), the hydrogen-bonded acid\u2013base units are linked by C\u2014H\u22efO hydrogen bonds, forming a tape structure along the b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C\u2014H\u22efO hydrogen bond, forming wide ribbons parallel to the (via \u03c0\u2013\u03c0 inter\u00adactions between the quinoline ring systems [centroid\u2013centroid distances = 3.4935\u2005(5)\u20133.7721\u2005(6)\u2005\u00c5], forming layers parallel to the ab plane. In the crystal of (II), the hydrogen-bonded acid\u2013base units are also linked into a tape structure along the b-axis direction via C\u2014H\u22efO hydrogen bonds. Inversion-related tapes are linked by further C\u2014H\u22efO hydrogen bonds to form wide ribbons parallel to the \u20133.9247\u2005(9)\u2005\u00c5], and the mol\u00adecular chains are linked into layers parallel to the ab plane through these inter\u00adactions.The structures of three compounds of 3-chloro-2-nitro\u00adbenzoic acid with 5-nitro\u00adquinoline, (I), 6-nitro\u00adquinoline, (II), and 8-hy\u00addroxy\u00adquinoline, (III), have been determined at 190\u2005K. In each of the two isomeric compounds, (I) and (II), C The \u0394pThe mol\u00adecular structure of (I)The mol\u00adecular structure of (II)+\u2014H\u22efO\u2212 hydrogen bond (Table\u00a03The mol\u00adecular structure of (III)d Table\u00a03. In the i and C14\u2014H14\u22efO5i; symmetry codes as in Table\u00a01b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C\u2014H\u22efO hydrogen bond (C13\u2014H13\u22efO6ii), forming wide ribbons parallel to the  \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a02].In the crystal of (I)ne Fig.\u00a04. These rne Fig.\u00a05. The cenb-axis direction via C\u2014H\u22efO hydrogen bonds  via weak \u03c0\u2013\u03c0 inter\u00adactions  \u2212x, \u2212y\u00a0+\u00a02, \u2212z; (v) x\u00a0\u2212\u00a01, y\u00a0+\u00a01, z; (vi) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01]. A pair of short O\u22efN contacts  between the nitro groups of the base mol\u00adecule are alsso observed.In the crystal of (II)ne Fig.\u00a06. The acins Fig.\u00a07, so formvia N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds \u2005\u00c5]; Cg1 and Cg3 are, respectively, the centroids of the C1\u2013C6 ring of the anion and the C11\u2013C16 ring of the cation. In addition to the \u03c0\u2013\u03c0 inter\u00adaction (Cg1\u22efCg3i), other \u03c0\u2013\u03c0 inter\u00adactions are observed; the centroid\u2013centroid distances are 3.5469\u2005(6), 3.8550\u2005(6) and 3.5133\u2005(6)\u2005\u00c5, respectively, for Cg1\u22efCg2iii, Cg1\u22efCg3iii and Cg1\u22efCg4iii, where Cg2 and Cg4 are the centroids of the N2/C8\u2013C11/C16 and N2/C8\u2013C16 rings of the cation, respectively  is observed between the layers.In the crystal of compound (III)on Fig.\u00a08. In the ns Fig.\u00a09, and theet al., 2016et al., 2002et al., 2018et al. , 2.561\u2005(1), 2.540\u2005(2)\u20132.571\u2005(2), 2.573\u2005(1) and 2.613\u2005(3)\u2005\u00c5, respectively. Furthermore, in the short hydrogen bonds of AJIWOG, CALJUW and NOVLAN, the H atom is disordered over two positions. On the other hand, the compounds (I)Ka values of 0.98, 1.42 and 3.02, respectively, show longer O\u22efN distances of 2.673\u2005(1), 2.631\u2005(1) and 2.636\u2005(1)\u2005\u00c5, which suggests that the \u0394pKa value is not an effective measure of hydrogen-bond strength in the 3-chloro-2-nitro\u00adbenzoic acid\u2013organic base system.A search of the Cambridge Structural Database , in which the O\u22efN distance of the N\u2014H\u22efO hydrogen bond is 2.644\u2005(3)\u2005\u00c5.A search for organic co-crystals/salts of 5-nitro\u00adquinoline showed six structures. Limiting the search to benzoic acid derivatives gave two hits, namely, 3-amino\u00adbenzoic acid\u20135-nitro\u00adquinoline (1/1) \u2013(III), were obtained by slow evaporation from aceto\u00adnitrile solutions of 3-chloro-2-nitro\u00adbenzoic acid with quinoline derivatives in a 1:1 molar ratio at room temperature [100\u2005ml aceto\u00adnitrile solution of 3-chloro-2-nitro\u00adbenzoic acid (0.39\u2005g) and 5-nitro\u00adquinoline (0.34\u2005g) for (I)O = 0.872\u2005(19)\u2005\u00c5 in (III)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019012799/lh5922sup1.cifCrystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S2056989019012799/lh5922Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012799/lh5922IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989019012799/lh5922IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1953605, 1953604, 1953603CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dimeric mol\u00adecules of the complexes crystallize together with water and methanol mol\u00adecules, with which they form a variety of weak and medium-strength hydrogen bonds.Oxalate-bridged, centrosymmetric binuclear complexes of gadolinium(III) and dysprosium(III) with hexa\u00addentate bbpen Ln(bbpen)Cl]  and potassium oxalate monohydrate in water/methanol produced the solvated centrosymmetric isostructural binuclear bis\u00ad{dilanthanide(III)}\u2013methanol\u2013water (1/4/4) complexes, [Ln2(C28H28N4O2)2(C2O4)]\u00b74CH3OH\u00b74H2O, with lanthanide(III) = gadolinium(III) (Ln = Gd) and dysprosium(III) (Ln = Dy), in high yields (ca 70%) directly from the reaction mixtures. In both complexes, the lanthanide ion is eight-coordinate and adopts a distorted square-anti\u00adprismatic coordination environment. The triclinic (PPLATON . These two new compounds are of inter\u00adest with respect to magnetic properties.The reaction between mononuclear [Spek 2015. Acta Cr The lanthanide cations assume square-anti\u00adprismatic coordination environments while the d-block metal is octa\u00adhedrally coordinated 2]+ complex had previously been employed to produce binuclear [Dy2(\u03bc-ox)(HBpz3)4]\u00b72CH3CN\u00b7CH2Cl2, this time with oxalate (ox2\u2013) as the bridging ligand. Direct current (DC) magnetic susceptibility measurements performed with this dimeric compound revealed the presence of an intra\u00admolecular ferromagnetic inter\u00adaction between the DyIII cations 3{Ln(bbpen)}3] -N,N\u2032-bis\u00ad(pyridin-2-ylmeth\u00adyl)ethyl\u00adenedi\u00adamine) via modular synthesis employing [Ln(bbpen)Cl] (LnIII = Gd or Dy) and K3[M(ox)3] (MIII = Cr or Co) as building blocks in a 3:1 proportion. The syntheses with gadolinium(III) and chromium(III) produced colourless crystals of the binuclear complex [{Gd(bbpen)}2(\u03bc-ox)]\u00b74CH3OH\u00b74H2O, as revealed by single crystal X-ray diffraction analysis. The formation of this dimer is explained by dissociation of [Cr(ox)3]3\u2013 into {Cr(ox)2(OH2)2}\u2212 and ox2\u2013 in aqueous solution +. Structural elucidation of this otherwise unexpected product prompted us to try and perform its targeted preparation with both gadolinium(III) and dysprosium(III) in good yields.In our research group, we first attempted to prepare heterometallic complexes of general formula [Ln(bbpen)}2(\u03bc-ox)] products [Ln = Gd (1) or Dy (2)], prepared from the direct reaction between [Ln(bbpen)Cl] and K2C2O4\u00b7H2O in water/methanol media.In this paper we report the rational synthesis and the crystal and mol\u00adecular structures of the two binuclear and solvated [{1 and 2 are isostructural and crystallize in the PLn2(\u03bc-ox)(bbpen)2] mol\u00adecules  or dysprosium(III) (2) are eight-coordinate; the [Ln(bbpen)]+ units are connected to one another by oxalate bridging in the usual bis\u00ad(bidentate) coordination mode. The ox2\u2013 ligand lies about an inversion centre. The coordination sphere of the lanthanide(III) ion is formed by an N4O2 donor set from the bbpen2\u2013 ligand and two oxygen atoms from the bridging oxalate. In 1 and 2 each metal cation has a distorted square-anti\u00adprismatic coordination environment  and 2.24\u2005\u00c5 (2). The non-bonding Dy\u22efDy distance in 2, 6.1488\u2005(17)\u2005\u00c5, is close to the analogous distance of 6.14\u2005\u00c5 in [Dy2(\u03bc-ox)(HBpz3)4]\u00b72CH3CN\u00b7CH2Cl2  \u2212x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] are also similar to those reported for the dysprosium(III)\u2013hydro\u00adtris(pirazolylborate) dimer mentioned above. The slightly decreased crystal volume of the Dy compound [1626.3\u2005(7)\u2005\u00c53] compared with that of the Gd compound [1633.7\u2005(3)\u2005\u00c53] is a perfect match with the smaller effective ionic radius of eight-coordinate DyIIIversus GdIII  product 2 gives rise to very similar results.Compounds es Fig.\u00a01 in whichnt Fig.\u00a02, as indiIn both structures, the hydrogen atoms from the crystallizing solvents (water and methanol) participate in an extensive three-dimensional hydrogen-bonding network that may be described as medium-strength inter\u00admolecular inter\u00adactions Tables 1 and 2 \u25b8.1 and 2. As seen in Fig.\u00a03W\u2014H\u22efO2iii \u2018bridge\u2019, as well as a symmetry-related chain on both sides of the plane formed by the metal and oxalate ions. The water mol\u00adecules in these chains also connect one dimer to another through weak C1\u2014H1B\u22efO1Wii inter\u00adactions  mol\u00adecules, half of which refine well and are depicted in Fig.\u00a03ns Fig.\u00a04 and 2 \u25b8.PLATON  for O\u22efO30. On the other hand, any possible inter\u00adaction involving the phenolate oxygen atoms would be very weak, with the shortest O\u22efO contact with the disordered solvents being longer than 4.0\u2005\u00c5.The other half of the solvent mol\u00adecules in the unit cell, the electron densities of which have been removed with the SQUEEZE routine in 2\u2013 and related ligands appear in the literature  complexes with bbpen al. 2005, and by  al. 2000.LnCl3\u00b76H2O (LnIII = Gd or Dy) and K2C2O4\u00b7H2O were purchased from Aldrich and used without purification. N,N\u2032-Bis(2-hy\u00addroxy\u00adbenz\u00adyl)-N,N\u2032-bis\u00ad(pyridin-2-ylmeth\u00adyl)ethyl\u00adene\u00addi\u00adamine (H2bbpen) Cl] precursors, with Ln = Gd or Dy ]\u00b74CH3OHSynthesis of [{Gd(bbpen)}\u00b72O (compound 1)4H2C2O4\u00b7H2O in 1.0\u2005ml of water was slowly added to a methanol solution of 61.1\u2005mg (0.0947\u2005mmol) of [Gd(bbpen)Cl]. The colourless reaction mixture was stirred at room temperature for ca 5\u2005min, and was then cooled down to 277\u2005K to give block-shaped colourless crystals after four days. These were isolated by filtration, washed with diethyl ether and dried. Total yield: 49.0\u2005mg (68.6%) based on the [{Gd(bbpen)}2(\u03bc\u2013ox)]\u00b74CH3OH\u00b74H2O formulation, compound 1. FTIR : 3362, 3198 ; 1655 ; 1590, 1568 , 1290 , 762 and 768 . Product 1 is soluble in aceto\u00adnitrile, 1,2-di\u00admeth\u00adoxy\u00adethane (dme), di\u00adchloro\u00admethane and tetra\u00adhydro\u00adfuran. Elemental analysis: calculated for 1 (C62H80Gd2N8O16) C 49.39, H 5.35, N 7.43%. Found: C 48.56, H 5.49, N 7.45%.A solution of 8.11\u2005mg (0.0440\u2005mmol) of K2(\u03bc\u2013ox)]\u00b74CH3OHSynthesis of \u00b74CH3OH\u00b74H2O formulation, compound 2. FTIR : 3363, 3198 , 1590 ; 1570 (m), 1481 (s), 1459 ; 1290 , 762 and 768 . The product solubility is similar to that described for 1. Elemental analysis: calculated for 2 (C62H80Dy2N8O16) C 49.04, H 5.31, N 7.38%. Found: C 49.02, H 5.71, N 7.56%.A mixture of 61.0\u2005mg (0.0938\u2005mmol) of [Dy(bbpen)Cl] in 9.0\u2005ml of methanol and 8.90\u2005mg (0.0483\u2005mmol) of K1 and 2 showed high susceptibility to the loss of the crystallization solvent mol\u00adecules once removed from the mother liquor. Hydrogen atoms in 1 and 2 were included in idealized positions with methyl, methyl\u00adene and aromatic C\u2014H distances set at 0.98, 0.99 and 0.95\u2005\u00c5, respectively, and O\u2014H at 0.84\u2005\u00c5 and refined as riding with Uiso(H) = 1.2\u20131.5Ueq. Hydrogen atoms on the water mol\u00adecules were located in difference-Fourier maps and were refined with distance restraints .Crystal data, data collection and structure refinement details for the two structures are summarized in Table\u00a03PLATON  1, 2. DOI: 10.1107/S2056989019002998/wm54891sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019002998/wm54892sup3.hklStructure factors: contains datablock(s) 2. DOI: 1899963, 1899964CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N-oxide and solvent mol\u00adecules are reported. The pyridine N--oxide, 2-methyl\u00adpyridine N-oxide, 3-methyl\u00adpyridine N-oxide, and 4-methyl\u00adpyridine N-oxide complexes all form similar structures with slight differences owing to the substituent group effects.The synthesis and crystal structures of four dimeric complexes composed of manganese(II) dibromide, a pyridine  N-oxides, viz. pyridine N-oxide (PNO), 2-methyl\u00adpyridine N-oxide (2MePNO), 3-methyl\u00adpyridine N-oxide (3MePNO), and 4-methyl\u00adpyridine N-oxide (4MePNO). The compounds are bis\u00ad(\u03bc-pyridine N-oxide)bis\u00ad[aqua\u00addibromido\u00ad(pyridine N-oxide)manganese(II)], [Mn2Br4(C5H5NO)4(H2O)2] (I), bis\u00ad(\u03bc-2-methyl\u00adpyridine N-oxide)bis\u00ad[di\u00adaqua\u00addibromido\u00admanganese(II)]\u20132-methyl\u00adpyridine N-oxide (1/2), [Mn2Br4(C6H7NO)2(H2O)4]\u00b72C6H7NO (II), bis\u00ad(\u03bc-3-methyl\u00adpyridine N-oxide)bis\u00ad[aqua\u00addibromido\u00ad(3-methyl\u00adpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(H2O)2] (III), and bis\u00ad(\u03bc-4-methyl\u00adpyridine N-oxide)bis\u00ad[di\u00adbromido\u00admethanol(4-methyl\u00adpyridine N-oxide)manganese(II)], [Mn2Br4(C6H7NO)4(CH3OH)2] (IV). All the compounds have one unique MnII atom and form a dimeric complex that contains two MnII atoms related by a crystallographic inversion center. Pseudo-octa\u00adhedral six-coordinate manganese(II) centers are found in all four compounds. All four compounds form dimers of Mn atoms bridged by the oxygen atom of the PNO ligand. Compounds I, II and III exhibit a bound water of solvation, whereas compound IV contains a bound methanol mol\u00adecule of solvation. Compounds I, III and IV exhibit the same arrangement of mol\u00adecules around each manganese atom, ligated by two bromide ions, oxygen atoms of two PNO ligands and one solvent mol\u00adecule, whereas in compound II each manganese atom is ligated by two bromide ions, one O atom of a PNO ligand and two water mol\u00adecules with a second PNO mol\u00adecule inter\u00adacting with the complex via hydrogen bonding through the bound water mol\u00adecules. All of the compounds form extended hydrogen-bonding networks, and compounds I, II, and IV exhibit offset \u03c0-stacking between PNO ligands of neighboring dimers.Four manganese(II) bromide coordination complexes have been prepared with four pyridine  N-oxides have inter\u00adesting binding modes that facilitate the growth of unique coordination structures. Their utility to facilitate organic oxotransfer reactions has been well documented over the years  and manganese(II) metal ions with a single bifunctional ligand containing an acetate and N-oxide moiety  dimeric complexes, using pyridine N-oxide (PNO) and its mono-methyl-substituted forms, 2-methyl\u00adpyridine N-oxide (2MePNO), 3-methyl\u00adpyridine N-oxide (3MePNO), and 4-methyl\u00adpyridine N-oxide (4MePNO). This was done to study the impact of substitution of the pyridine on the two- and three-dimensional solid-state structures, and to compare them to previous structures in which the bromide ions are replaced with chloride ions.Herein, we report the synthesis and solid-state structures of four pyridine General structural detailsN-oxide complexes form dimers consisting of two MnII atoms related by an inversion center; the dimer contains a six-coordinate metal center at each MnII ion with four donor oxygen atoms and two bromides. The Mn1\u22efMn1\u2032 dimer is bound trans by two \u03bc2-1,1-PNO ligands, and the octa\u00adhedral environment is completed by a water mol\u00adecule of hydration or a solvent mol\u00adecule, non-bridging PNO ligands, and bromide ions. The dimer is constructed from symmetry-related atoms and mol\u00adecules using a crystallographic inversion center of the space group (PP21/n). The mol\u00adecular structures of compounds I, II, III and IV are given in Figs. 1The pyridine Specific structural detailsI  and 2.235\u2005(2)\u2005\u00c5 for Mn1\u2014O1 and Mn1\u2014O1i, respectively, which is unremarkable for compounds of MnII and pyridine N-oxide \u2005\u00c5. The octa\u00adhedral geometry around the Mn atoms is significantly distorted with the O1\u2014Mn1\u2014O1i bond angle measuring 69.66\u2005(9)\u00b0; the other bond angles are within ca 9\u00b0 of 90\u00b0. These bond angles and bond lengths are similar to those for other MnII halide PNO structures \u2005\u00c5 .Compound I Fig.\u00a01 crystallII  and 2.321\u2005(2)\u2005\u00c5 for Mn1\u2014O1 and Mn1\u2014O1i, respectively. The two bound water mol\u00adecules have Mn\u2014O bond lengths of 2.237\u2005(3) and 2.157\u2005(3)\u2005\u00c5 for Mn1\u2014O3 and Mn1\u2014O4, respectively, and are similar to those reported previously \u2005\u00c5. Once again the octa\u00adhedral geometry around the Mn atoms is significantly distorted with the O1\u2014Mn1\u2014O1i bond angle measuring 74.40\u2005(9)\u00b0. The other bond angles are within ca 11\u00b0 of 90\u00b0. The dimer forms an intra\u00admolecular hydrogen bond between O3 and Br1i with a hydrogen-bond distance of 2.44\u2005(2)\u2005\u00c5 . In the asymmetric unit there is a second PNO mol\u00adecule inter\u00adacting with the complex via hydrogen bonding through the bound water mol\u00adecules  and 2.219\u2005(3)\u2005\u00c5 for Mn1\u2014O2 and Mn1\u2014O2i, respectively. The non-bridging Mn1\u2014O1 bond is 2.129\u2005(3)\u2005\u00c5, and the bound water Mn1\u2014O3 bond distance is 2.245\u2005(3)\u2005\u00c5. The bound bromide ions have bond distances of Mn1\u2014Br1 = 2.7237\u2005(7)\u2005\u00c5 and Mn1\u2014Br2 = 2.5687\u2005(7)\u2005\u00c5; again the difference in Mn\u2014Br bond distances can be attributed to the hydrogen-bonding inter\u00adactions that exist with Br1 but not with Br2 (Table\u00a03i distance is 3.6497\u2005(13)\u2005\u00c5. The octa\u00adhedral geometry around the Mn atoms is significantly distorted with the O2\u2014Mn1\u2014O2i bond angle measuring 69.05\u2005(11)\u00b0 the other bond angles are within ca 11\u00b0 of 90\u00b0. The dimer forms an intra\u00admolecular hydrogen bond between O3 and Br1ii with a hydrogen-bond distance of 2.55\u2005(2)\u2005\u00c5 .Compound II Fig.\u00a03 crystall2 Table\u00a03. The Mn1IV  and 2.230\u2005(3)\u2005\u00c5 for Mn1\u2014O2 and Mn1\u2014O2i, respectively. The non-bridging Mn1\u2014O1 bond is 2.116\u2005(3)\u2005\u00c5, and the bound methanol Mn1\u2014O3 bond distance is 2.225\u2005(3)\u2005\u00c5. The bound bromide ions have bond distances of Mn1\u2014Br1 = 2.7181\u2005(7)\u2005\u00c5 and Mn1\u2014Br2 2.5806\u2005(7)\u2005\u00c5, again the difference in Mn\u2014Br bond distance can be attributed to the hydrogen-bonding inter\u00adactions (Table\u00a04i distance is 3.61254\u2005(12)\u2005\u00c5. The octa\u00adhedral geometry around the Mn atoms is significantly distorted with the O2\u2014Mn1\u2014O2i bond angle measuring 70.77\u2005(11)\u00b0 the other bond angles are within 13\u00b0 of 90\u00b0. The dimer forms an intra\u00admolecular hydrogen bond between O3 and Br1i with a hydrogen-bond distance of 2.41\u2005(2)\u2005\u00c5 .Compound IV Fig.\u00a04 crystalls Table\u00a04. The Mn1I, the dimers are linked by Owater\u2014H\u22efBr hydrogen bonds, forming chains parallel to the [100] direction; see Table\u00a01ac plane \u2005\u00c5 and O4\u22efO2ii = 2.721\u2005(4)\u2005\u00c5 (Table\u00a02B\u22efBr1i with a distance of 2.44\u2005(2)\u2005\u00c5 , with an inter-centroid distance of the stacked aromatic rings of 3.516\u2005(4)\u2005\u00c5, so forming layers parallel to the ac plane \u2005\u00c5, with a significant centroid shift of 3.221\u2005(9)\u2005\u00c5 preventing \u03c0-stacking. Neighboring dimers are linked by O\u2014H\u22efBr hydrogen-bonds forming chains parallel to the a axis. There are two observed inter\u00adactions, O3\u2014H3A\u22efBr1i with a distance of 2.60\u2005(2)\u2005\u00c5 and O3\u2014H3B\u22efBr1ii with a distance of 2.55\u2005(2)\u2005\u00c5 . Five of these structures contain derivatives of pyridine N-oxides and one of them is a 4,4\u2032-dipyridal N,N\u2032-dioxide (H2O)]n, [MnCl2(2MPNO)(H2O)]n, and [MnCl2(3MPNO)(H2O)2]2 2(H2O)6I2]I2  bromide tetra\u00adhydrate  was dissolved in a minimal amount (20\u2005ml) of methanol. Two molar equivalents of pyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10\u2005min and the solvent was allowed to evaporate to produce X-ray quality crystals . Selected IR bands  3470 , 1471 (s), 1216 (s), 833 (s) 773 (m), 669 (m), 558 (m). Analysis calculated for C20H24N4Mn2Br4O6: C, 28.40; H, 2.86; N, 6.62%. Found: C, 28.13; H, 2.86; N, 6.50%.Compound II: Manganese(II) bromide tetra\u00adhydrate  was dissolved in a minimal amount (20\u2005ml) of methanol. Two molar equivalents of 2-methyl\u00adpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10\u2005min and the solvent was allowed to evaporate to produce X-ray quality crystals . Selected IR bands  3349 , 1600 (m), 1461 (s), 1195 (s) 842 (m), 772 (s), 557 (m). Analysis calculated for C24H36N4Mn2Br4O8: C, 30.73; H, 3.87; N, 5.97%. Found: C, 30.30; H, 3.62; N, 6.17%.Compound III: Manganese(II) bromide tetra\u00adhydrate  was dissolved in a minimal amount (20\u2005ml) of methanol. Two molar equivalents of 3-methyl\u00adpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10\u2005min and the solvent was allowed to evaporate to produce a powder . X-ray quality crystals were grown by recrystallizing a second time by slow evaporation from methanol. Selected IR bands  3373 , 1631 (s), 1492 (m), 1260 (m), 1163(s), 943 (m), 802 (m).Compound IV: Manganese(II) bromide tetra\u00adhydrate  was dissolved in a minimal amount (20\u2005ml) of methanol. Two molar equivalents of 4-methyl\u00adpyridine N-oxide  were also dissolved in methanol. The solutions were mixed and stirred for 10\u2005min and the solvent was allowed to evaporate to produce a powder . X-ray quality crystals were grown by recrystallizing a second time from methanol with a slower evaporation rate. Selected IR bands  3227 , 3004 (m), 1670 (m), 1494(s), 1213 (s), 852(s), 763(s).I and II have been reported analytically pure, whereas III and IV were not isolated analytically pure. The FT\u2013IR spectra of the four N-oxide complexes all exhibit broad absorbances in the 3500\u20133100\u2005cm\u22121 region characteristic of the \u03bd(O\u2014H) of the coordinated water or methanol mol\u00adecules. In addition, the \u03bd(N\u2014O) stretching frequency that is due to the N-oxide pyridyl moiety is observed in the region between 1260 and 1195\u2005cm\u22121, as noted previously \u2005\u00c5 and refined with Uiso(H) = 1.5Ueq(O). In compound IV, the hydroxyl H atom was located in a difference-Fourier map and refined with O\u2014H distance restrained to 0.85\u2005(1)\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O). All carbon-bound H atoms were positioned geometrically and refined as riding: C\u2014H = 0.95\u20130.98\u2005\u00c5 with Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019010557/su5505sup1.cifCrystal structure: contains datablock(s) Global, II, III, IV, I. DOI: 10.1107/S2056989019010557/su5505Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019010557/su5505IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989019010557/su5505IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989019010557/su5505IVsup5.hklStructure factors: contains datablock(s) IV. DOI: 1942967, 1942966, 1942965, 1942964CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title heterocyclic 1,3,4-oxa\u00addiazole derivatives differ from each other in the groups attached to the carbon atoms: a meth\u00adoxy\u00adphenyl ring and a benzo\u00adnitrile group in (I) and a chloro\u00adphenyl ring and an acetamide group in (II). 18H15N3O4 and C17H14ClN3O3, are heterocyclic 1,3,4-oxa\u00addiazole derivatives which differ from each other in the groups attached to the carbon atoms: a meth\u00adoxy\u00adphenyl ring and a benzo\u00adnitrile group in (I) and a chloro\u00adphenyl ring and an acetamide group in (II). Short intra\u00admolecular C\u2014H\u22efO hydrogen bonds occur in both mol\u00adecules. The crystal structure of (I) features C\u2014H\u22efN hydrogen bonds, while in the crystal structure of (II), N\u2014H\u22efN, C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds are observed.The title compounds, C Compounds containing a heterocyclic ring system are of great importance both medicinally and industrially S(5) ring motifs  and (II)s Figs. 1 and 2 \u25b8.B\u22efO3iii, Table\u00a01A\u22efN1i, Table\u00a01C(5) chains propagating along [010]  chains propagating in an anti-parallel manner along [110]. These C\u2014H\u22efN hydrogen bonds along with the C\u2014H\u22efO dimers form a closed cavity shape arrangement consisting of 26 atoms in the unit cell if Fig.\u00a04. Further0] Fig.\u00a05. There ill Fig.\u00a06. In addiC(10) chains, C\u2014H\u22efN hydrogen bonds forming C(8) chains and C\u2014H\u22efO inter\u00adactions forming C(15) chains ns Fig.\u00a07. All thed Table\u00a02. No \u03c0\u2013\u03c0 2CO3 (3\u2005mmol) in DMF (4\u2005mL), 2-(chloro\u00admeth\u00adyl)-5-(4-meth\u00adoxy\u00adphen\u00adyl)-1,3,4-oxa\u00addiazole and KI (0.5\u2005mmol). The reaction mixture was stirred at room temperature for about 2\u2005h until the starting material had been consumed (TLC monitoring), and then washed with cold water. The solid product was collected by filtration and dried under vacuum. The pure compound was further recrystallized from ethyl acetate/petroleum ether solution (v:v = 1:1).Compound (I)N-(4-hy\u00addroxy\u00adphen\u00adyl)acetamide (1mmol), K2CO3 (3\u2005mmol) in ACN (5mL), 2-(chloro\u00admeth\u00adyl)-5-(4-chloro\u00adphen\u00adyl)-1,3,4-oxa\u00addiazole and KI (0.5\u2005mmol). The reaction mixture was stirred under reflux condition for about 16\u2005h, until completion of the reaction (TLC monitoring), then it was diluted with ethyl acetate (30\u2005mL) and washed with saturated NaHCO3 and cold water. The organic layer was separated, dried over anhydrous Na2SO4 and concentrated under vacuum. The pure compound was further recrystallized from an ethyl acetate/petroleum ether solution (v:v = 1:1), giving colourless block-like crystals suitable for X-ray diffraction analysis.Compound (II)Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018016754/zq2243sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018016754/zq2243Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018016754/zq2243IIsup4.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018016754/zq2243Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018016754/zq2243IIsup5.cmlSupporting information file. DOI: 1881075, 1881074CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "K\u03b1 and Mo K\u03b1 radiation as part of a continuous crystallization study. In the crystal, chains along the a axis are formed via N\u2014H\u22efO hydrogen bonds between acetamide groups, as well as C\u2014H\u22efO inter\u00adactions. These chains arrange themselves into parallel running stacks which display weak C\u2014Cl\u22efO=Chalogen bonding as well as weak C\u2014H\u22ef\u03c0 inter\u00adactions.Two independent samples of the title compound were studied using Cu  N-(4-methylphenyl)prop\u00adan\u00adamide, C10H12ClNO, 1, were studied using Cu K\u03b1, 1a, and Mo K\u03b1, 1b, radiation as part of a continuous crystallization study. The mol\u00adecule crystallizes with disorder in the Cl/terminal methyl positions [occupancies for the major disorder component of 0.783\u2005(2) in 1a and and 0.768\u2005(2) in 1b] and exhibits N\u2014C bond lengths of 1.3448\u2005(19), 1.344\u2005(2)\u2005\u00c5, C=O bond lengths of 1.2233\u2005(18) and 1.2245\u2005(19)\u2005\u00c5 and an acetamide moiety C\u2014N\u2014C\u2014C torsion angle of 179.00\u2005(13), 178.97\u2005(14) \u00b0 for 1a and 1b, respectively. In the crystal, chains along the a axis are formed via N\u2014H\u22efO hydrogen bonds between acetamide groups, as well as C\u2014H\u22efO inter\u00adactions. These chains arrange themselves into parallel running stacks which display weak C\u2014Cl\u22efO=C halogen bonding as well as weak C\u2014H\u22ef\u03c0 inter\u00adactions.Two independent samples of the title compound, alternatively 2-chloro- The disorder occupancy is different in 1a, 1b and in IQOHOL, but to no great extent with the occupancy of the major component being 0.783\u2005(2) for 1a, 0.768\u2005(2) for 1b and for 0.899 IQOHOL.An overlay of the mol\u00adecular structures of i, see Tables 2et al., 20011.In the extended structure there is, as expected, a strong amide hydrogen bond, between the N\u2014H group and the ketone oxygen  and 2.8632\u2005(6)\u2005\u00c5 respectively)] The head-to-tail packing and the chelate hydrogen bonding allows an approximately linear arrangement of 1, forming ribbons propagating along the [100] direction, see Fig.\u00a031a and 1.71940\u2005(13)\u00b0 in 1b).There is also a weaker inter\u00adaction between the methine group and the ketone  and 1b, 3.1734\u2005(18)\u2005\u00c5 . A very weak example of a C\u2014H\u22ef\u03c0iii inter\u00adaction is also present in 1, with the methyl group C12 directed towards the centroid of ring C1\u2013C6  yielded several similar substituted phenyl\u00adacetamides: CLACTN  in toluene (50\u2005mL) and 40\u2005mL of aqueous NaOH  at 273\u2005K. After the addition was complete, the biphasic suspension was warmed to room temperature and stirred vigorously for 1\u2005h. The organic phase was separated, and the aqueous layer extracted with ethyl acetate (3 \u00d7 15\u2005mL). The organic layers were then combined, dried with Na2SO4, filtered and the solvent removed under vacuum. The resulting off-white solid was collected and washed with thoroughly with cold cyclo\u00adhexane . Single crystals for X-ray analysis were grown by slow evaporation of a toluene solution at room temperature. Spectroscopic data for the obtained product matched that reported in the literature  in toluene (30\u2005mL) was added dropwise (with extreme caution) to a vigorously stirred bi-phasic suspension of 1H NMR : \u03b4 8.21 , 7.42 , 7.15 , 4.54  2.13 , 1.83 . 13C NMR : \u03b4 166.9 134.4, 134.0, 129.1, 119.7, 55.9, 22.4, 20.5. MS (EI) m/z 197 [M]+, [12C10H1235Cl14N16O 197]. HRMS (EI) m/z Found: [M]+ 197.0604, [C10H12ClNO]+ requires 197.0607.1a and 1b, Cl1/Cl1a and C12/C12a were modelled as disordered over two positions using restraints  and constraints . The occupancy was allowed to refine with a population parameter of 1a = 0.783\u2005(2), and 1b = 0.768\u2005(2). The amide N\u2014H H atom was located in a difference-Fourier map and freely refined. H atoms bonded to carbon were placed with idealized geometry and refined using a riding model with C\u2014H = 0.95\u2005\u00c5 aromatic, C\u2014H = 0.90\u2005\u00c5 methine, with Uiso(H) = 1.2Ueq(C) and C\u2014H = 0.98\u2005\u00c5 methyl with Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018013889/ds2252sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989018013889/ds22521asup2.hklStructure factors: contains datablock(s) 1a. DOI: 10.1107/S2056989018013889/ds22521bsup3.hklStructure factors: contains datablock(s) 1b. DOI: Click here for additional data file.10.1107/S2056989018013889/ds22521asup4.cmlSupporting information file. DOI: 1870782, 1870781CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title sulfonamide, inter\u00admolecular N\u2014H\u22efO hydrogen bonds are present between sulfonamide groups, as well as offset \u03c0\u2013\u03c0 inter\u00adactions. 10H13NO2S, was synthesized by a nucleophilic substitution reaction between allyl amine and p-toluene\u00adsulfonyl chloride. The sulfonate S\u2014O bond lengths are 1.4282\u2005(17) and 1.4353\u2005(17)\u2005\u00c5, and the C\u2014N\u2014S\u2014C torsion angle involving the sulfonamide moiety is \u221261.0\u2005(2)\u00b0. In the crystal, centrosymmetric dimers of the title compound are present via inter\u00admolecular N\u2014H\u22efO hydrogen bonds between sulfonamide groups. These dimers are linked into ribbons along the c-axis direction through offset \u03c0\u2013\u03c0 inter\u00adactions.The title compound, C Centrosymmetric dimers of compound (I)i distance of 2.900\u2005(3)\u2005\u00c5 suggests inter\u00adactions of medium strength with a nearly linear N\u2014H\u22efO hydrogen bond of 174\u2005(3)\u00b0 \u2005\u00c5, with a slippage of 1.320\u2005\u00c5 and a plane-to-plane distance between phenyl rings of 3.600\u2005\u00c5 .Mol\u00adecules of the title compound are linked to one another \u00b0 Table\u00a01. These ds Figs. 3, 4 \u25b8. Thet al., 2016p-tolyl\u00adsulfonamides where there is a \u2013CH2\u2014C=C group bonded to the sulfonamide-N atom. The alkene group in these structures is a part of, for example, furan rings . The mixture was stirred at room temperature for 24\u2005h. Reaction completion was verified by using TLC analysis. The mixture was acidified to pH 2\u20133 using concentrated HCl. After dilution with 20\u2005ml of CH2Cl2, the organic phase was washed with H2O (3 \u00d7 20\u2005ml) and the aqueous layer was back-extracted with CH2Cl2 (20\u2005ml). The combined organic extracts were dried over anhydrous Na2SO4. After solvent evaporation, the residue was obtained as a yellow solid which was recrystallized in cold ethanol to afford pale-yellow crystals .Allyl\u00adamine  was added in 20\u2005ml of degassed di\u00adchloro\u00admethane. This was followed by the addition of pyridine . The resulting solution was stirred under an atmosphere of Nsp3\u2014H = 0.95\u20131.00\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for methine and methyl\u00adene groups, and Uiso(H) = 1.5Ueq(C) for methyl groups. The hydrogen atom bonded to the nitro\u00adgen atom (H1) was located using electron-density difference maps, and the N\u2014H bond length was restrained to 0.84\u00b10.01\u2005\u00c5 using the DFIX command as executed in SHELXL  I. DOI: 10.1107/S2056989018010290/wm5455Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018010290/wm5455Isup3.cmlSupporting information file. DOI: 1856234CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Z\u2032 = 1 is reported.A new monoclinic polymorph of 2,2\u2032-methyl\u00adenebis with  C2/c) of 2,2\u2032-methyl\u00adenebis, C17H10N2O4, is reported and compared to the previously reported triclinic polymorph (space group PZ\u2032 = 1). The mol\u00adecular conformations of the two polymorphs are very similar, as shown by the r.m.s. deviation of 0.368\u2005\u00c5 . The inter\u00admolecular inter\u00adactions of both polymorphs are described along with the Hirshfeld surface analysis, and the lattice energies are calculated.In this study, a new monoclinic polymorph (space group  N-heterocycles have been proven to exhibit significant biological and pharmaceutical activities, and have also been used as dyes and heat-resistant polymers in industry \u2005\u00c5, b = 9.5810\u2005(8)\u2005\u00c5, c = 10.2780\u2005(6)\u2005\u00c5, \u03b1 = 104.325\u2005(3)\u00b0, \u03b2 = 99.768\u2005(4)\u00b0, \u03b3 = 96.030\u2005(3)\u00b0, Z = 2, Z\u2032 = 1 and V = 712.23\u2005(11)\u2005\u00c53; Cambridge Structural Database  of 2,2\u2032-methyl\u00adenebis with Z\u2032 = 1 and compare its properties with those of 1\u03b1. According to the Online Dictionary of Crystallography, polymorphism is the phenomenon in which the same chemical compound exhibits different crystal structures  derivatives with five-membered \u03b1 and 1\u03b2  and 0.064\u2005(3)\u2005\u00c5 for 1\u03b2. There are two degrees of freedom to characterize the mol\u00adecular conformations of 1\u03b1 and 1\u03b2: these are the torsion angles C1\u2014N1\u2014C9\u2014N2  and N1\u2014C9\u2014N2\u2014C10 . Generally, the mol\u00adecule of 1\u03b2 deviates only slightly from that of 1\u03b1, as indicated by a r.m.s. deviation of 0.368\u2005\u00c5  \u00b0, which is smaller than that of 88.96\u2005(4)\u00b0 observed in polymorph 1\u03b1. The calculated density and Kitaigorodskii packing index  are slightly higher than those observed for 1\u03b1 (1.428 Mg\u2005m\u22123 and 69.0%).The asymmetric units of polymorphs 11\u03b2 Fig.\u00a01 each cons) Fig.\u00a02. The mea\u03b1 features weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 inter\u00adactions between neighboring phthalimide units. In the crystal structure of 1\u03b2  and between N1/C1/C2/C7/C8 and C11\u2013C16 rings  and 1\u03b2 ], respectively. The percentages of contribution of H\u22efC/C\u22efH, O\u22efC/C\u22efO and C\u22efC contacts to the Hirshfeld surface are 20.6, 3.3 and 8.9%, respectively, for 1\u03b1, and 20.8, 7.9 and 6.7%, respectively, for 1\u03b2 ]. The C\u22efC contacts appear as a unique \u2018triangle\u2019 focused at de \u2243 di \u2243 1.75\u2005\u00c5 [Fig.\u00a04f)]. The inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions are illustrated as unique patterns of red and blue \u2018triangles\u2019 on the shape-index surface  is slightly larger than for 1\u03b2 (128.5\u2005kJ\u2005mol\u22121), indicating that 1\u03b1 is slightly more stable than 1\u03b2 under ambient conditions.The C\u2014H bond lengths in 1\u03b2 were obtained from an unsuccessful synthesis of 2-{[(3-iodo\u00adpyridin-4-yl)amino]\u00admeth\u00adyl}isoindoline-1,3-dione by reacting N-(bromo\u00admeth\u00adyl)phthalimide (1\u2005mmol) and 4-amino-3-iodo\u00adpyridine (1\u2005mmol) in N,N-di\u00admethyl\u00adformamide (8\u2005ml) with the presence of a catalytic amount of anhydrous potassium carbonate. The reaction solution was stirred for about 2\u2005h at room temperature. Once the reaction was complete, the resultant mixture was poured into a beaker of ice-cooled water to obtain a precipitate  = 1.2Ueq(C).Crystal data, data collection and structure refinement details of 110.1107/S2056989018017425/jj2205sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018017425/jj2205Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017425/jj2205Isup3.cmlSupporting information file. DOI: 1884044CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is a salt formed by a hydrazinium (1+) cation and a hexa\u00adfluorido\u00adsilicate anion inter\u00adconnected by N\u2014H\u22efN and N\u2014H\u22efF hydrogen bonds. 2H5)2SiF6, the silicon atom at the centre of the slightly distorted SiF6 octa\u00adhedron [range of Si\u2014F distances = 1.6777\u2005(4)\u20131.7101\u2005(4)\u2005\u00c5] lies on a crystallographic inversion centre. In the crystal, the ions are connected by N\u2014H\u22efN and N\u2014H\u22efF hydrogen bonds; the former link the cations into [010] chains and the latter (some of which are bifurcated or trifurcated) link the ions into a three-dimensional network. The two-dimensional fingerprint plots show that F\u22efH/H\u22efF inter\u00adactions dominate the Hirshfeld surface (75.5%) followed by H\u22efH (13.6%) and N\u22efH/H\u22efN (8.4%) whereas F\u22efF (1.9%) and F\u22efN/N\u22efF (0.6%) have negligible percentages. The title compound is isostructural with its germanium-containing analogue.In the title inorganic mol\u00adecular salt, (N However, this compound was characterized by chemical analysis, vibrational spectroscopy and X-ray powder photography by Gantar & Rahten  to 1.7101\u2005(4)\u2005\u00c5. The minimum and maximum cis F\u2014S\u2014F angles are 89.26\u2005(2) and 90.74\u2005(2)\u00b0, respectively. The N\u2014N separation in the cation is 1.4416\u2005(8)\u2005\u00c5.Compound (I)6]2\u2212 anion inter\u00adacts with the (N2H5)+ cations through electrostatic attraction and accepts no fewer than ten simple, bifurcated or trifurcated N\u2014H\u22efF hydrogen bonds ds Fig.\u00a03. This reon Fig.\u00a04.et al., 2004CrystalExplorer package dnorm . In order to provide qu\u00adanti\u00adtative information on the contribution of the inter\u00admolecular inter\u00adactions to the crystal packing, the three-dimensional dnorm surface is resolved into two-dimensional fingerprint plots, generated based on de and di distance scales and illustrated in Fig.\u00a05a)\u2013(f) The F\u22efH/H\u22efF inter\u00adactions appear as distinct spikes in the fingerprint plot, and occupy the majority of the total Hirshfeld surface (75.5%) as illustrated in Fig.\u00a05a); the characteristic \u2018wingtip\u2019 features indicate the N\u2014H\u22efF hydrogen bonds. The H\u22efF inter\u00adaction are represented by a spike  at the bottom left (donor), whereas the F\u22efH inter\u00adactions are represented by a spike  at the bottom right (acceptor) of the fingerprint plot. The H\u22efH contacts appear in the middle of the scattered points; these contacts comprise 13.6% of the total Hirshfeld surface [Fig.\u00a05c)]. The N\u22efH contacts cover 8.4% of the total surface, as the third important contributor in the crystal packing, Fig.\u00a05d) while the F\u22efF and F\u22efN/N\u22efF contacts make negligible contributions of 1.9% [Fig.\u00a05e)] and 0.6% [Fig.\u00a05f)], respectively.The acceptor atoms in the inter\u00adactions are shown with negative electrostatic potentials (red regions), and donor atoms are shown with positive electrostatic potentials (blue regions). The N\u2014H\u22efF inter\u00adactions in the structure are apparent from the relatively bright red-spots on the Hirshfeld surface of (I)2H6SiF6, at room temperature, crystallizes in a pseudo-tetra\u00adgonal ortho\u00adrhom\u00adbic space group , with a = 7.605\u2005(1)\u2005\u00c5, b = 7.586\u2005(2)\u2005\u00c5 and c = 8.543\u2005(1)\u2005\u00c5  plane.Hydrazinium (2+) hexa\u00adfluorido\u00adsilicate, Net al., 19852H5)2GeF6 crystallizes in the monoclinic system, space group P21/n (Z = 2), with cell parameters a = 6.015\u2005(2)\u2005\u00c5, b = 5.249\u2005(1)\u2005\u00c5, c = 11.181\u2005(2)\u00c5 and \u03b2 = 100.15\u2005(2)\u00b0 and is clearly isostructural with (I)Hydrazinium (1+) hexa\u00adhalogenometallates were studied by Gantar and co-workers (Gantar 2H5)2TiF6 2TiF6  exhibit racemic twinning but are not isostructural with (I)2H5)2TiF6 consists of N2H5+ cations and two types of slightly distorted octa\u00adhedral (TiF6)2\u2212 anions. The N2H5+ cations and (TiF6)2\u2212 anions are linked via N\u2014H\u22efF and N\u2014H\u22efN hydrogen bonds, building a three-dimensional network. Two other isostructural hydrazinium (l+) hexa\u00adfluorido complexes, (N2H5)2ZrF6 and (N2H5)2HfF6, were prepared and characterized by chemical analysis, vibrational spectroscopy and X-ray powder diffraction .Fluoride complexes of titanium (IV) with ammonium cation derivatives include two hydrazinium hexa\u00adfluorido\u00adtitanates (IV), (N2H5)2SiF6 crystals in the form of colourless blocks were obtained by slow evaporation, at room temperature, of an aqueous solution containing stoichiometric amounts of hydrazine NH2NH2 and H2SiF6. The infrared spectrum was recorded in the range 450\u20134000\u2005cm\u22121 with a Vertex 70 FTIR spectrometer.Hydrazinium (1+) hexa\u00adfluorido\u00adsilicate (NUiso(H) = 1.2Ueq(N). The highest peak and the deepest hole in the final Fourier map are at 0.67\u2005\u00c5 from F3 and 0.0\u2005\u00c5 from Si1.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019012672/hb7850sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019012672/hb7850Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012672/hb7850sup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019012672/hb7850sup3.rtfSupporting information file. DOI: 1953037CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The syntheses and crystal structures of three cyclo\u00adtriphosphazenes, all with fluorinated ar\u00adyloxy side groups that generate different steric characteristics are reported. viz. hexa\u00adkis\u00ad(penta\u00adfluoro\u00adphen\u00adoxy)cyclo\u00adtriphosphazene, N3P3(OC6F5)6, 1, hexa\u00adkis\u00ad[4-(tri\u00adfluoro\u00admethyl)\u00adphen\u00adoxy]cyclo\u00adtriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexa\u00adkis\u00adcyclo\u00adtriphosphazene, N3P3[OC6H3(CF3)2]63, are reported. Specifically, each phospho\u00adrus atom bears either two penta\u00adfluoro\u00adphen\u00adoxy, 4-tri\u00adfluoro\u00admethyl\u00adphen\u00adoxy, or 3,5-tri\u00adfluoro\u00admethyl\u00adphen\u00adoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the \u2018flap atom\u2019 from the plane through the other ring atoms [0.308\u2005(5)\u2005\u00c5] is seen in 1, in a mol\u00adecule that is devoid of hydrogen atoms and which exhibits a \u2018wind-swept\u2019 look with all the aromatic rings displaced in the same direction. In 3 an intra\u00admolecular C\u2014H(aromatic)\u22efF inter\u00adaction is observed. All the \u2013CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C\u2014H\u22efF inter\u00adactions of two kinds: (a) linear chains, and (b) cyclic between mol\u00adecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic \u03c0\u2013\u03c0 stacking inter\u00adaction with its respective symmetry mate with slippage values of 2.2\u2005\u00c5 in 1 and 1.0\u2005\u00c5 in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.The syntheses and crystal structures of three cyclo\u00adtriphosphazenes, all with fluorinated ar\u00adyloxy side groups that generate different steric characteristics,  Cyclic organophosphazenes have a long history as representatives of inorganic heterocyclic rings, and are also the focus of arguments about reactivity and pseudoaromaticity in inorganic systems 6 (1), hexa\u00adkis\u00ad[4-(tri\u00adfluoro\u00admethyl)\u00adphenoxy]cyclo\u00adtriphosphazene N3P3[OC6H4(CF3)]6 (2) and hexa\u00adkis\u00ad6 (3) were synthesized by the reactions of hexa\u00adchloro\u00adcyclo\u00adtriphosphazene with the appropriate sodium fluoro-aryl\u00adoxides in THF or dioxane solvent. Forcing reaction conditions (boiling dioxane) were required for complete chlorine replacement in the case of the penta\u00adfluoro\u00adphen\u00adoxy derivative (1) presumably due to steric hindrance. The three compounds were characterized by NMR spectroscopy in addition to x-ray crystallography.As part of our ongoing work in this area, the three cyclo\u00adtriphosphazenes hexa\u00adkis\u00ad(penta\u00adfluoro\u00adphen\u00adoxy)cyclo\u00adtri\u00adphos\u00adphazene Npara-fluoro\u00adphen\u00adoxy groups, was reported by other investigators  is 0.308\u2005(5)\u2005\u00c5. A similar calculation in 2 shows atom P2 displaced by 0.232\u2005(4)\u2005\u00c5, and in 3 atom N3 is displaced the least, only by 0.205\u2005(4)\u2005\u00c5. In earlier structure reports: .The mol\u00adecular structure of ce Fig.\u00a04 with all1, hydrogen bonding is not feasible in that structure \u22efF type hydrogen bonds \u22efF hydrogen bonds \u2005\u00c5, slippage 1.013\u2005\u00c5].The packing diagram of s Table\u00a02, forminget al. 3, CSD refcode KAGKUY: Bullen, 19712)3, VARYES02: Singh et al., 20002)3\u00b7THF, GUHPII: Dietrich et al., 2000Earlier, we reported the crystal structures of a number of cyclo\u00adtriphosphazenes with spiro\u00adcyclic ar\u00adyloxy side groups cyclo\u00adtriphos\u00adpha\u00adzene (1):4, and concentrated to \u223c10\u2005ml by rotary evaporation. A small amount of hexa\u00adnes was added to the concentrated solution and it was chilled to 273\u2005K via an ice bath to yield colorless blocks of 1, which were filtered and rinsed with cold hexa\u00adnes then dried under vacuum.Sodium penta\u00adfluoro\u00adphenoxide was prepared by the treatment of penta\u00adfluoro\u00adphenol  with a suspension of NaH 60% dispersion in mineral oil  in 50\u2005ml of dioxane. The penta\u00adfluoro\u00adphenoxide was added to a stirred solution of hexa\u00adchloro\u00adcyclo\u00adtriphosphazene  and the mixture was heated at reflux for 3\u2005d. Dioxane was removed from the mixture by rotary evaporation and the residue was dissolved in 100\u2005ml di\u00adchloro\u00admethane. The solution was extracted with 3 \u00d7 100\u2005ml of deionized water, dried over MgSOSynthesis of hexa\u00adkis\u00ad(4-tri\u00adfluoro\u00admethyl\u00adphen\u00adoxy)cyclo\u00adtri\u00adphos\u00adphazene (2):1 to yield colorless cubes of 2.The aryl\u00adoxide was prepared by treatment of 4-tri\u00adfluoro\u00admethyl\u00adphenol  with a suspension of NaH [60% dispersion in mineral oil ] in 50\u2005ml of THF. To the stirred solution of 4-tri\u00adfluoro\u00admethyl\u00adphenoxide was added a solution of hexa\u00adchloro\u00adcyclo\u00adtriphosphazene  in 15\u2005ml of THF and the mixture was stirred at room temperature overnight. The purification steps of this compound were identical to those of compound Synthesis of hexa\u00adkis\u00adcyclo\u00adtriphosphazene (3):4 and the di\u00adchloro\u00admethane was removed by rotary evaporation to yield a colorless oil, which crystallized as colorless needles of 3 after standing for several hours. The crystals were rinsed with cold methanol and then dried under vacuum.A stirred suspension of NaH [60% dispersion in mineral oil ] in 25\u2005ml of THF was treated with liquid 3,5-bis-tri\u00adfluoro\u00admethyl\u00adphenol  by dropwise addition. The resulting aryl\u00adoxide solution was then added to a stirred solution of hexa\u00adchloro\u00adcyclo\u00adtriphosphazene  in 25\u2005ml of THF and the reaction mixture was stirred at room temperature overnight. The mixture was concentrated by rotary evaporation and the residue was dissolved in 40\u2005ml di\u00adchloro\u00admethane. The di\u00adchloro\u00admethane solution was washed with 40\u2005ml of deionized water, followed by 20\u2005ml of 5% HCl, and finally rinsed with 40\u2005ml of deionized water. The organic layer was dried over MgSO1\u20133 are as follows: 1: 31P 10.6 1 ppm (in chloro\u00adform-d); 19F \u2212153.52 , \u2212157.53 , \u2212161.79 ; 2: 31P 8.64 ppm (in chloro\u00adform-d); 1H 747, 706 (d 2H); 19F \u221262.79 (s); 3: 31P 7.71 ppm (in chloro\u00adform-d); 1H 7.74 (s 1H), 7.52 ; 19F \u221263.85 (s).The NMR data for 2 and 3 were placed geometrically (C\u2014H = 0.93\u2005\u00c5) and refined as riding on their parent atoms with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details for all three structures are summarized in Table\u00a0310.1107/S2056989019012933/hb7853sup1.cifCrystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S2056989019012933/hb78531sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989019012933/hb78531sup5.molSupporting information file. DOI: 10.1107/S2056989019012933/hb78532sup4.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989019012933/hb78532sup6.molSupporting information file. DOI: 10.1107/S2056989019012933/hb78533sup3.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989019012933/hb78533sup7.molSupporting information file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Enterobacteriaceae family were particularly most sensitive to new pipemidic acid derivatives. Synthesized compounds exhibited very strong activity towards Proteus mirabilis ATCC 12453, Salmonella typhimurium ATCC 14028 and Escherichia coli ATCC 25922. The minimum inhibitory concentrations of new pipemidic acid derivatives which inhibited the growth of these bacteria were 0.98\u20137.81\u00a0\u00b5g/ml, 0.98\u20137.81\u00a0\u00b5g/ml and 0.98\u20133.91\u00a0\u00b5g/ml, respectively. The antibacterial activity of newly synthesized pipemidic acid derivatives in many cases was far better than the activity of substances used as positive controls .This article describes the synthesis and antimicrobial activity evaluation of new pipemidic acid derivatives. New compounds were obtained on the basis of Mannich reaction of 4,5-disubstituted 1,2,4-triazole-3-thiones with pipemidic acid. Antimicrobial tests revealed high antibacterial activity of obtained derivatives. Gram-negative rods belonging to The online version of this article (10.1007/s12272-018-1025-3) contains supplementary material, which is available to authorized users. Microorganisms play a key role in the functioning of the environment but they are also a real threat to human life and health. The widespread diseases and infections caused by different bacteria and fungi have encourage the need for scientific research and advances in medicinal chemistry . The DMSO-d6 was used as solvent and TMS as the internal standard. Chemical shifts in this article are reported in ppm (\u03b4). The coupling constants (J) are presented in Hertz. The purity of obtained compounds and the progress of the reaction were determined by thin-layer chromatography (TLC) with the use of pre-coated aluminum sheet 60 F254 plates (Merck Co. USA), and CHCl3/C2H5OH  solvent system. The spots were identified by the exposure to the UV light at 254\u00a0nm. The elemental analysis of obtained compounds was carried out with the use of AMZ 851 CHX analyser . The results of elemental analysis  were within\u2009\u00b1\u20090.4% of the calculated values.The reagents and solvents used in this research were obtained from Merck Co.  and Sigma-Aldrich . Melting points were determined with the use of Fisher-Johns blocks melting point apparatus  and presented without correction. The 1 or 4-tert-butylbenzhydrazide\u20142, respectively) was dissolved in 10\u00a0ml of ethanol (96%). Then 0.0022\u00a0mol of appropriate isothiocyanate was added and heated under reflux for 3\u00a0h. Subsequently obtained solution was put to the refrigerator for 24\u00a0h. After that formed precipitate was filtered off and re-crystallized from ethanol. The procedure of this synthesis was based on our previous article  is presented in Supplementary Materials.Detailed physicochemical data of thiosemicarbazide derivatives (3\u201318) was dissolved in 5\u00a0ml of 2% sodium hydroxide solution and heated under reflux for 2\u00a0h. Subsequently, obtained solution was neutralized with diluted hydrochloric acid. Formed precipitate was filtered off and re-crystallized from ethanol.4,5-Disubstituted 1,2,4-triazole-3-thiones were synthesized with the use of the procedure from our earlier research  is presented in Supplementary Materials.Detailed physicochemical data of 4,5-disubstituted 1,2,4-triazole-3-thione derivatives (19\u201334) was added to the conical flask and dissolved with stirring in 5\u00a0ml of ethanol (96%). After that 200\u00a0\u00b5l of formaldehyde and 0.0033\u00a0mol of pipemidic acid was added to the flask. The content of the flask was stirred by magnetic stirrer for 1\u00a0h. Subsequently, 15\u00a0ml of distilled water was added to the flask. The precipitate which formed was filtered off and re-crystallized from methanol.In order to obtained new pipemidic acid derivatives we applied the Mannich reaction and the procedure reported by our group earlier  is presented in Supplementary Materials.Detailed physicochemical data of new pipemidic acid derivatives  (EUCAST discussion document E. Dis 5.1 The examined compounds 35\u201350) were obtained with the use of three step reaction scheme (Scheme\u00a03\u201318) were synthesized on the basis of condensation reaction of appropriate carboxylic acid hydrazides with various isothiocyanates. Subsequently, thiosemicarbazide derivatives (3\u201318) underwent cyclization reaction with the use of 2% sodium hydroxide solution, which afforded the 4,5-disubstituted 1,2,4-triazole-3-thione derivatives (19\u201334). Finally, 1,2,4-triazole-3-thione derivatives (19\u201334) were subjected to Mannich reaction with pipemidic acid to obtain new pipemidic acid derivatives (35\u201350). Chemical structure of all obtained compounds (3\u201350) was confirmed on the basis of spectral identification and elemental analysis.New pipemidic acid derivatives (e Scheme\u00a0. Firstly3\u201318), 1,2,4-triazoles-3-thiones (19\u201334) and pipemidic acid derivatives (35\u201350), were in vitro screened against references strains of bacteria and fungi. The results of antimicrobial assays are presented in the Tables\u00a0All synthesized compounds, including thiosemicarbazides 3\u20138, 1,2,4-3\u201318) defined as MIC  values against Gram-positive bacterial strains ranged from 3.91\u00a0\u00b5g/ml to 1000\u00a0\u00b5g/ml , against Gram-negative bacterial strains ranged from 500\u00a0\u00b5g/ml to 1000\u00a0\u00b5g/ml (MBC\u2009=\u2009>\u20091000\u00a0\u00b5g/ml). The MIC values against reference fungi were MIC\u2009=\u2009250\u20131000\u00a0\u00b5g/ml   were within the range of 500\u20131000\u00a0\u00b5g/ml against Gram-positive bacterial strains (MBC\u2009=\u20091000 to >\u20091000\u00a0\u00b5g/ml), 1000\u00a0\u00b5g/ml against Gram-negative bacterial strains (MBC\u2009=\u2009>\u20091000\u00a0\u00b5g/ml) and 250\u20131000\u00a0\u00b5g/ml for fungal strains (MBC\u2009=\u20091000 to >\u20091000\u00a0\u00b5g/ml)  ranged from 3.91 to 1000\u00a0\u00b5g/ml against Gram-positive bacteria (MBC\u2009=\u20093.91 to >\u20091000\u00a0\u00b5g/ml), 0.98\u2013125\u00a0\u00b5g/ml against Gram-negative bacteria (MBC\u2009=\u20090.98\u2013250\u00a0\u00b5g/ml) and 1000\u00a0\u00b5g/ml towards fungi belonging to Candida spp. (MBC\u2009=\u2009>\u20091000\u00a0\u00b5g/ml) , 4,5-disubstituted 1,2,4-triazoles-3-thiones (19\u201334) and pipemidic acid derivatives (35\u201350) in this research was confirmed on the basis of spectral (1H NMR and 13C NMR) and elemental analysis.The pathway for the synthesis of new pipemidic acid derivatives Scheme\u00a0 was desi3\u201318) showed three typical singlet signals at \u03b4 7.99\u201310.52\u00a0ppm, on the 1H NMR spectra, which correspond to three NH groups. Whereas on the 13C NMR spectra of this group of compounds (3\u201318), signals for carbonyl group (C=O) and thiocarbonyl group (C=S) were found at \u03b4 155.1\u2013159.5\u00a0ppm and around \u03b4 166.0\u00a0ppm, respectively.Thiosemicarbazide derivatives (19\u201334), on the 1H NMR spectra, singlet signal for NH group was noticed in the range of \u03b4 13.75\u201314.15\u00a0ppm. On the 13C NMR spectra the signal for thiocarbonyl group (C=S) of 1,2,4-triazole-3-thiones (19\u201334) was found at \u03b4 166.5\u2013169.3\u00a0ppm.In the case of 4,5-disubstituted 1,2,4-triazole-3-thione derivatives (1H NMR spectra of new pipemidic acid derivatives (35\u201350) showed characteristic singlet signal for CH2 group in the range of \u03b4 5.18\u20135.36\u00a0ppm, what confirmed common aminomethylation reaction of 1,2,4-triazole-3-thiones. Signals for other aliphatic and aromatic fragments of synthesized compounds on 1H NMR and 13C NMR were shown at expected shift range.The 35\u201350) and six compounds among 4,5-disubstituted 1,2,4-triazole derivatives (19\u201334) are new in the literature and their synthesis, physicochemical data and biological activity have not been reported so far.It is worth to mention that all sixteen synthesized pipemidic acid derivatives (3\u201318), especially compounds: 4\u201310, 12, 13, 15, 18, had no activity against all reference microorganisms  values, was 32 times better against M. luteus ATCC 10240 (MIC\u2009=\u20093.91\u00a0\u00b5g/ml) and two times better against B. cereus ATCC 10876 (MIC\u2009=\u20097.81\u00a0\u00b5g/ml) in comparison with the activity of pipemidic acid , used as positive control  and moderate or mild effect against other reference staphylococci and some Gram-negative rods (MIC\u2009=\u2009250\u20131000\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml). Moreover, the compounds 3, 11, 14 and 16 exhibited mild activity (MIC\u2009=\u20091000\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml) towards some Gram-positive bacteria. The substances 3 and 11 showed additional effect against Bordetella bronchiseptica ATCC 4617 (MIC\u2009=\u2009500\u20131000\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml)  , only a few, namely 19, 20, 21 and 34 exhibited moderate or mild antibacterial activity against some of reference microorganisms  . The remaining substances 22\u201333 were inactive towards bacteria and fungi from ATCC  were highly active against all reference bacteria (Table\u00a0Enterobacteriaceae family were particularly most sensitive to these compounds. All substances (35\u201350) showed bactericidal effect against them. These compounds exhibited very strong activity towards Proteus mirabilis ATCC 12453, Salmonella typhimurium ATCC 14028 and Escherichia coli ATCC 25922. The minimum concentrations of 35\u201350 compounds, which inhibited the growth of these bacteria were 0.98\u20137.81\u00a0\u00b5g/ml, 0.98\u20137.81\u00a0\u00b5g/ml and 0.98\u20133.91\u00a0\u00b5g/ml, respectively. Klebsiella pneumoniae ATCC 13883 was slightly less susceptible to these substances. The compounds 36, 37, 38, 44, 46 and 50 indicated very strong activity (MIC\u2009=\u2009MBC\u2009=\u20093.91\u20137.81\u00a0\u00b5g/ml), compounds 35, 39 and 45\u2014strong , while remaining compounds 40, 41, 42, 43, 47, 48, 49\u2014good activity (MIC\u2009=\u2009MBC\u2009=\u200931.25\u201362.5\u00a0\u00b5g/ml) towards reference K. pneumoniae ATCC 13883. In addition, all pipemidic acid derivatives (35\u201350) exhibited a similar good effect against Bordetella bronchiseptica ATCC 4617 and Pseudomonas aeruginosa ATCC 9027   towards B. bronchiseptica ATCC 4617 were two times better in case of compounds 36, 37, 45, 46 and 50 (MBC\u2009=\u200931.25\u00a0\u00b5g/ml). Against K. pneumoniae ATCC 13883, the compound 36 showed four times better activity (MIC\u2009=\u20093.91\u00a0\u00b5g/ml), compounds 37, 38, 44, 46, and 50 showed two times better activity (MIC\u2009=\u20097.81\u00a0\u00b5g/ml) than pipemidic acid (MIC\u2009=\u200915.62\u00a0\u00b5g/ml). The compounds 35 and 45 showed two times lower MBC values (MBC\u2009=\u200915.62\u00a0\u00b5g/ml) than pipemidic acid (MBC\u2009=\u200931.25\u00a0\u00b5g/ml) against this bacterium. In the case of the activity against P. mirabilis ATCC 12453 the MIC values for the compound 36 were two times lower (MIC\u2009=\u20090.98\u00a0\u00b5g/ml) and the MBC values for the compounds 35, 38, 46 were two times lower (MBC\u2009=\u20091.95\u00a0\u00b5g/ml) than such values for pipemidic acid . The activity of synthesized derivatives was also better than pipemidic acid towards Salmonella typhimurium ATCC 14028. The compounds 37 and 38 showed two times better activity on the basis of MIC values (MIC\u2009=\u20090.98\u00a0\u00b5g/ml) than pipemidic acid (MIC\u2009=\u20091.95\u00a0\u00b5g/ml) against this bacterium. The MBC values for compounds 35, 36, 45 and 46 (MBC\u2009=\u20091.95\u00a0\u00b5g/ml) were two times lower than for pipemidic acid used as positive control (MBC\u2009=\u20093.91\u00a0\u00b5g/ml). In addition to this, the MBC values for compounds 36, 37, 38, and 45 against E. coli ATCC 25922 (MBC\u2009=\u20090.98\u00a0\u00b5g/ml) were two times lower than for pipemidic acid (MBC\u2009=\u20091.95\u00a0\u00b5g/ml)  values of pipemidic acid derivatives 5\u201350 towa35-50 indicated also high activity towards Gram-positive bacteria but slightly weaker compared to Gram-negative microorganisms. Most of the substances showed very strong bactericidal or bacteriostatic effect against Bacillus subtilis ATCC 6633 with MIC\u2009=\u20093.91\u20137.81\u00a0\u00b5g/ml, MBC\u2009=\u20093.91\u2013250\u00a0\u00b5g/ml and MBC/MIC\u2009=\u20091\u201332. The other compounds 43 and 49 indicated good (MIC\u2009=\u2009MBC\u2009=\u200931.25\u00a0\u00b5g/ml) or strong (MIC\u2009=\u2009MBC\u2009=\u200915.62\u00a0\u00b5g/ml) bactericidal activity towards this bacterium. Bacillus cereus ATCC 10876 was slightly less sensitive to these substances. Among them the compound 37 showed very strong activity  against this bacterium. In turn, substances 35, 36, 38, 39, 41, 45, 46 and 50 had a strong activity , while compounds 40, 42, 43, 44, 47, 48 and 49\u2014good activity  (Table\u00a0The compounds 35\u201350) showed also good activity with bactericidal or bacteriostatic effect against microorganisms belonging to reference staphylococci: S. aureus ATCC 25923, S. aureus ATCC 6538 and S. epidermidis ATCC 12228 . Among them, compounds 36 and 50 showed strong bactericidal activity towards S. aureus ATCC 6538 , while compound 50\u2014very strong  and compounds 36 and 46\u2014strong activity  towards S. epidermidis ATCC 12228 (Table\u00a0Pipemidic acid derivatives 5\u201350 show35\u201350) showed only moderate activity towards Micrococcus luteus ATCC 10240 (MIC\u2009=\u2009250\u2013500\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml) and most of them except 39 and 47 against Staphylococcus aureus ATCC 43300 (MIC\u2009=\u2009250\u2013500\u00a0\u00b5g/ml and MBC\u2009=\u2009500 to >\u20091000\u00a0\u00b5g/ml). The compounds 39 and 47 indicated good (MIC\u2009=\u2009125\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml) or mild (MIC\u2009=\u20091000\u00a0\u00b5g/ml and MBC\u2009>\u20091000\u00a0\u00b5g/ml) activity, respectively against S. aureus ATCC 43300  was four times better and for the compounds 35, 37, 38, 44, 45, and 46 (MIC\u2009=\u200931.25\u00a0\u00b5g/ml) was two times better against S. aureus ATCC 6538 on the basis of MIC values. The compound 50 showed two times lower MIC values (MIC\u2009=\u20097.81\u00a0\u00b5g/ml) with bactericidal effect and the compounds 36 and 46 showed two times lower MBC values (MBC\u2009=\u200931.25\u00a0\u00b5g/ml) with bactericidal effect against S. epidermidis ATCC 12228 than pipemidic acid . The MBC values for the derivative 36 towards B. subtilis ATCC 6633 (MBC\u2009=\u20093.91\u00a0\u00b5g/ml) were two times lower than for pipemidic acid (MBC\u2009=\u20097.81\u00a0\u00b5g/ml). In the case of the activity against B. cereus ATCC 10876 the MIC values for the substance 37 were two times lower (MIC\u2009=\u20097.81\u00a0\u00b5g/ml) than for pipemidic acid (MIC\u2009=\u200915.62\u00a0\u00b5g/ml) (Table\u00a035\u201350) against B. cereus ATCC 10876 is especially important due to the fact that this bacterium is responsible for an increasing number of foodborne diseases in industrial countries as well as postoperative and posttraumatic wound infections , the activity of the compounds 35\u201350) indicated also moderate or mild activity towards reference fungi belonging to yeasts. Among them the compound 42 inhibited the growth of all Candida spp. (MIC\u2009=\u2009500\u20131000\u00a0\u00b5g/ml and MFC\u2009>\u20091000\u00a0\u00b5g/ml). In turn, substances 38, 41, 43 and 49 showed mild activity towards some of them (MIC\u2009=\u20091000\u00a0\u00b5g/ml and MFC\u2009>\u20091000\u00a0\u00b5g/ml). The remaining compounds were inactive against reference Candida spp. Below is the link to the electronic supplementary material."}
{"text": "C2v symmetry and crystallizes in the chiral space group P21.The planar achiral title compound has  10H10O4, was synthesized from tetra\u00admethyl-1,4-benzo\u00adquinone. In the crystal, the almost planar mol\u00adecule (r.m.s. deviation = 0.024\u2005\u00c5) forms intra\u00admolecular hydrogen bonds between the aldehyde and hy\u00addroxy groups and exhibits C2v symmetry. This achiral mol\u00adecule crystallizes in the chiral space group P21 with inter\u00admolecular O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonding and C\u2014H\u22ef\u03c0 and C=O\u22ef\u03c0 inter\u00adactions stabilizing the crystal packing.The title compound, C Furthermore, inhibition of nucleic acid biosynthesis and of the activities of coenzyme Q mediated enzyme systems are also known for related compounds composed of 3,6-dihy\u00addroxy-4,5-di\u00admethyl\u00adbenzene-1,2-dicarbaldehyde . The C\u2014C bond lengths of the methyl substituents are 1.511\u2005(2) and 1.508\u2005(2)\u2005\u00c5, the C\u2014O bond lengths of the hy\u00addroxy substituents are 1.354\u2005(2) and 1.350\u2005(2)\u2005\u00c5, and the C\u2014C bond lengths of the aldehyde substituents are 1.464\u2005(2) and 1.462\u2005(2)\u2005\u00c5. Two intra\u00admolecular O\u2014H\u22efH hydrogen bonds between the hy\u00addroxy and aldehyde functions are observed \u2005\u00c5 (Cg1 is the centroid of ring C1\u2013C6).The C8=O2 carbonyl group is stacked on top of the aromatic ring, with the O2\u22efB\u22efCg1 (3.131\u2005\u00c5) is also found  and 50% acetic acid (35\u2005ml) was added dropwise at 353\u2005K. After 10\u2005min, the reaction mixture was poured onto crushed ice (100\u2005g). The solution was filtered by vacuum filtration and a crude compound was obtained. The crude compound was dissolved in toluene and purified by silica column chromatography to afford 0.567\u2005g (yield 23.5%) of the title compound as a yellow solid . IR : 1633 (s), 3436 (m).A mixture of tetra\u00admethyl-1,4-benzo\u00adquinone  and concentrated piperidine  was stirred at room temperature for 35\u2005h. The mixture was evaporated and a white inter\u00admediate product was obtained. To a solution of the obtained inter\u00admediate product dissolved in acetic acid (18\u2005ml), a mixture of CrOUiso(H) = 1.5Ueq(C) for methyl H atoms, and C\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for the aldehyde H atoms]. O-bound H atoms were constrained using a riding model [O\u2014H = 0.84\u2005\u00c5 and Uiso(H)\u00a0= 1.5Ueq(O) for hy\u00addroxy H atoms].Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018012495/vm2211sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018012495/vm2211Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018012495/vm2211Isup3.cmlSupporting information file. DOI: 1865811CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The first of these has an unusually short N\u22efN separation of 2.616\u2005(2)\u2005\u00c5: refinement of different models against the present data set could not distinguish between a symmetrical hydrogen bond (H atom lying on the twofold axis and equidistant from the N atoms) or static or dynamic disorder models (i.e. N\u2014H\u22efN + N\u22efH\u2014N).In the crystal, two AcAP mol\u00adecules related by a crystallographic twofold axis link to H R*, 8S)-2-acetamidoocta\u00adhydro\u00adpyrrol\u00adizin-4-ium chloride\u2013N-[-hexa\u00adhydro-1H-pyrrolizin-2-yl)acetamide (1/1)], 2(C9H16N2O)\u00b7HCl or C9H17N2O+\u00b7Cl\u2212\u00b7C9H16N2O, arose as an unexpected product when 1-exo-acetamido\u00adpyrrolizidine  was dissolved in CHCl3. Within the AcAP pyrrolizidine group, the unsubstituted five-membered ring is disordered over two orientations in a 0.897\u2005(5):0.103\u2005(5) ratio. Two AcAP mol\u00adecules related by a crystallographic twofold axis link to H+ and Cl\u2212 ions lying on the rotation axis, thereby forming N\u2014H\u22efN and N\u2014H\u22efCl\u22efH\u2014N hydrogen bonds. The first of these has an unusually short N\u22efN separation of 2.616\u2005(2)\u2005\u00c5: refinement of different models against the present data set could not distinguish between a symmetrical hydrogen bond (H atom lying on the twofold axis and equidistant from the N atoms) or static or dynamic disorder models (i.e. N\u2014H\u22efN + N\u22efH\u2014N). Computational studies suggest that the disorder model is slightly more stable, but the energy difference is very small.The title compound [systematic name: (1 The \u2018flap\u2019 atoms, C2 and C6, for the substituted (C1\u2013C3/N4/C8) and unsubstituted (C5\u2013C8/N4) rings, respectively, are displaced from the mean plane of the four remaining atoms (C1/C3/N4/C8 and C7/C5/N4/C8) by 0.622(1) and 0.633(2)\u2005\u00c5, respectively. The dihedral angle between these mean planes is 56.07\u2005(9)\u00b0. The acetamide group is characteristically almost planar (r.m.s. deviation = 0.0181\u2005\u00c5), but twisted from the mean plane of C1/C8/N4/C3 by a dihedral angle of 70.56\u2005(7)\u00b0. Aside from an unusually short N\u2014H\u22efN hydrogen bond, which will be discussed in subsequent sections, all geometrical parameters are within their expected ranges  \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0dN\u22efN = 2.616\u2005(2)\u2005\u00c5 . Similarly, since the refined H+ position lies on the twofold axis and is equidistant from N4 and N4i, the refined N\u22efH inter\u00adatomic distance appears unusually long at 1.3080\u2005(12)\u2005\u00c5. The whole hydrogen-bonded ensemble makes an N\u22efN4i hydrogen bond, a difference-Fourier map , statically disordered  or dynamically disordered . Alternative strategies for H4N inclusion in the model refined equally well , so we settled on the simplest approach, following the recommendations of F\u00e1bry . In addition to the strong N\u2014H\u22efN hydrogen bond, weaker N2\u2014H2\u2014Cl1\u2014H2i\u2014N2i inter\u00adactions link the twofold-related acetamide groups to the Cl\u2212 anion [N\u22efCl = 3.2263\u2005(11)\u2005\u00c5]. The twist of the twofold-related hydrogen-bonded pyrrolizidine moieties relative to each other, as defined by the torsion angle C8\u2014N4\u22efN4i\u2014C8i is \u221269.82\u2005(16)\u00b0. The almost planar acetamide group forms a dihedral angle with its twofold-related counterpart of 20.18\u2005(3)\u00b0. The only other intra\u00admolecular inter\u00adactions are van der Waals contacts. Estimates of the relative fractions of inter\u00admolecular contacts between individual atom types derived from a Hirshfeld-surface analysis using CrystalExplorer . The Cl\u2212 anion and the acetamide O atom each reside in pockets surrounded by hydrogen atoms, giving H\u22efCl/Cl\u22efH (16.2%) and H\u22efO/O\u22efH (12.4%), with the remainder being N\u22efH/H\u22efN and C\u22efH/H\u22efC contacts.The primary structural motif within crystals of 2AcAP\u00b7HCl consists of a pair of homochiral AcAP mol\u00adecules hydrogen bonded to H\u00c5 Table\u00a01, it is eap Fig.\u00a04 clearly \u00e1bry 2018. Nonetheet al., 2016et al., 2017A search of the Cambridge Structure Database -H-N(X)-C\u2032, where \u2018X\u2032 denotes \u2018any group\u2019, gave 45 hits. Rejection of cases where apparent close N\u22efN distances were due to disorder (four entries), and those in which the N-bound H atom was missing from the model (two entries), left 39 structures, of which three were duplicates. In the remaining 36 structures the N\u2014H\u22efN hydrogen bonds are intramol\u00adecular in 22 and intermol\u00adecular in 14. The closest N\u22efN separations occur in the intramol\u00adecular N\u2014H\u22efN hydrogen-bonded structures, the shortest being 2.419\u2005\u00c5 in EBOKOV \u2005\u00c5, although the difference is not significant, and well within the quoted precision estimate of BECHOG and the accuracy limits imposed by the spherical-atom scattering-factor approximation , and one unconstrained (B). The volume difference between these theoretical models  was negligible (Avol = 1918.85\u2005\u00c53versus Bvol = 1919.63\u2005\u00c53). In the symmetric model, the N\u2014H\u22efN hydrogen atom  is equidistant between the two nitro\u00adgen atoms (N\u2014H = 1.290\u2005\u00c5), whereas in model B the N\u2014H distances differ (N\u2014H = 1.194 and 1.406\u2005\u00c5). This is in agreement with the computed charge-density line profile of N\u2014H\u22efN in structure B, as shown in Fig.\u00a05B is calculated to be slightly more stable, but the energy difference (4.7\u2005meV per unit cell) is vanishingly small , both with and without symmetry constraints on charge density. In the case where symmetry constraints were absent, a small displacement (0.06\u2005\u00c5) was applied to the hydrogen atom in the N\u2014H\u22efN hydrogen bond to break symmetry in the initial geometry. The relaxations led to two structures, one with constrained twofold symmetry  with Perdew\u2013Burke\u2013Ernzerhof (PBE) exchange-correlation functional  calculations were carried out using the Vienna et al., 20143 in a 10\u2005ml round-bottom flask and allowing the solution to stand in a refrigerator for about a month.AcAP was synthesized and purified according to the published procedure (Pan RCH3), 0.99\u2005\u00c5 (R2CH2) and 1.00\u2005\u00c5 (R3CH). Following the advice of F\u00e1bry (2018N) was placed into difference-Fourier electron density and refined, albeit constrained to the twofold axis. An alternative model in which this H atom was allowed to ride at 50% occupancy on both N4 and N4i [symmetry code: (i) \u2212x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0N) was refined freely. Uiso(H) parameters for nitro\u00adgen-bound hydrogen atoms were refined, while for carbon-bound H atoms, Uiso(H) were set to values of either 1.2Ueq  or 1.5Ueq (RCH3) of the attached atom.Crystal data, data collection, and structure refinement details are given in Table\u00a02\u00e1bry 2018, the hyd\u2212 anion  were close (0.37 and 0.47\u2005\u00c5 respectively) to Cl1. Refinement of the anion as mixed Cl and Br gave an occupancy ratio of 0.934\u2005(2):0.066\u2005(2), a lower R-value (3.02%), and a flatter difference map (\u0394\u03c1 = 0.29/-0.19\u2005e\u2005\u00c5\u22123). However, the reaction included no known source of Br\u2212, so the mixed anion model was not retained.The refined displacement parameters for the ClSHELXL commands EXYZ and EADP) were used to fix overlapping fragments. Restraints were used to ensure the integrity of ill-defined or disordered groups . An alternative model using space group Cc (50:50 inversion twinned) was considered but rejected as it required hefty restraints and did not resolve the H4N atom ambiguity.To ensure satisfactory refinement for disordered groups in the structure, a combination of constraints and restraints were employed. The constraints  I. DOI: 10.1107/S2056989019016517/hb7870Isup2.hklStructure factors: contains datablock(s) I. DOI: 1970639CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) graph-set motifs, while C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions form S(5) graph-set motifs.The title compound is a novel halogen-substituted hydrazine derivative. Intra\u00admolecular N\u2014H\u22efO inter\u00adactions form  16H14BrN3O5, is a novel halogen (Br) substituted hydrazine derivative. The hydrazine derivatives were the group of compounds with the general structure, R1R2C=NNH2  results in an extended mol\u00adecular conformation. The dihedral angle between the 5-bromo-2-meth\u00adoxy\u00adphenyl ring and the nitrophenyl ring is 4.4\u2005(3)\u00b0. Intra\u00admolecular N\u2014H\u22efO inter\u00adactions form S(6) graph-set motifs, while C\u2014H\u22efO and C\u2014H\u22efN inter\u00adactions form S(5) graph-set motifs. Symmetry-related mol\u00adecules are linked by C\u2014H\u22efO inter\u00admolecular inter\u00adactions forming an R21(10) graph-set motif. There are nearly face-to-face directional specific \u03c0\u2013\u03c0 stacking inter\u00adactions between the centroids of the nitrophenyl ring and the benzene ring of the 5-bromo-2-meth\u00adoxy group [centroid\u2013centroid distance = 3.6121\u2005(5)\u2005\u00c5 and slippage = 1.115\u2005\u00c5], which also contributes to the mol\u00adecular packing. The Hirshfeld surface analysis was performed in order to visualize, explore and qu\u00adantify the inter\u00admolecular inter\u00adactions in the crystal lattice of the title compound.The title compound, C The central bridging moiety R2C=NNHR1 adopts an all-trans conformation about the C10\u2014C9, C9\u2014N3, N3\u2014N2 and N2\u2014C5 bonds, with torsion angles of 176.0\u2005(6), \u2212178.1\u2005(5), \u2212177.0\u2005(6) and 173.6\u2005(6)\u00b0, leading to an extended mol\u00adecular conformation, thereby causing the terminal bromo\u00admeth\u00adoxy\u00adphenyl ring and nitro\u00adphenyl\u00adring to occupy almost the same plane; the dihedral angle between the rings is 4.4\u2005(3)\u00b0.Fig.\u00a01x, y, z) and the benzene ring of the 5-bromo-2-meth\u00adoxy group  [centroid\u2013centroid distance = 3.6121\u2005(5)\u2005\u00c5 and slippage = 1.115\u2005\u00c5], which also contributes to the mol\u00adecular packing. The Br atom does not take part in any inter\u00adactions. The nearest Br\u22efC7, which are summarized in Table\u00a02et al., 2013et al., 2011Hirshfeld surface analysis serves as a powerful tool for gaining additional insight into inter\u00admolecular inter\u00adactions of mol\u00adecular crystals. The Hirshfeld surfaces are mapped with 2D fingerprint plots presented using et al., 2016et al., 2011et al. 2010et al. 2010et al., 2015et al., 1985et al., 2003A and B), 9.30\u2005(6)\u00b0, and 13.01\u2005(10) and 14.05\u2005(10)\u00b0 (in mol\u00adecules A and B), respectively, compared to 4.4\u2005(3)\u00b0 in the title compound. The crystal packing of the two compounds is significantly different. In AYSOD, N\u2014H groups do not form hydrogen bonds, in DUSBID, the mol\u00adecules are linked by N\u2014H\u22ef\u03c0 inter\u00adactions, and in DUSNUB, both mol\u00adecules form inversion dimers linked by pairs of N\u2014H\u22efO hydrogen bonds, thereby generating et al., 1995et al., 2013While searching for 2-phenyl\u00adhydrazine in the Cambridge Structural Database  with a slight excess of 5-bromo-2-meth\u00adoxy\u00adbenzaldehyde (0.215\u2005mg) in an acetic acid solution (10\u2005ml). The reaction mixture was refluxed for 8\u2005h. The solid product formed during reflux was filtered off, washed and dried over anhydrous calcium chloride in a vacuum desiccator (yield 75%). The final product was soluble in acetone, dimethyl sulfoxide (DMSO), di\u00admethyl\u00adformamide (DMF), methanol, ethanol and ethyl acetate, Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018011325/dx2007sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018011325/dx2007Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018011325/dx2007Isup3.cmlSupporting information file. DOI: 1860856CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S),18(R)\u2010EpETE and 17(R),18(S)\u2010EpETE. In this study, we demonstrated stereoselective differences of 17(S),18(R)\u2010EpETE and 17(R),18(S)\u2010EpETE in amelioration of skin contact hypersensitivity and found that anti\u2010inflammatory activity was detected in 17(S),18(R)\u2010EpETE, but not in 17(R),18(S)\u2010EpETE. In addition, we found that cytochrome P450 BM\u20103 derived from Bacillus megaterium stereoselectively converts EPA into 17(S),18(R)\u2010EpETE, which effectively inhibited the development of skin contact hypersensitivity by inhibiting neutrophil migration in a G protein\u2010coupled receptor 40\u2010dependent manner. These results suggest the new availability of a bacterial enzyme to produce a beneficial lipid mediator, 17(S),18(R)\u2010EpETE, in a stereoselective manner. Our findings highlight that bacterial enzymatic conversion of fatty acid is a promising strategy for mass production of bioactive lipid metabolites.Dietary intake of \u03c93 polyunsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid is beneficial for health control. We recently identified 17,18\u2010epoxyeicosatetraenoic acid  as a lipid metabolite endogenously generated from eicosapentaenoic acid that exhibits potent anti\u2010allergic and anti\u2010inflammatory properties. However, chemically synthesized 17,18\u2010EpETE is enantiomeric due to its epoxy group\u201417( One enantiomer may be responsible for the therapeutic effects, whereas the other enantiomer can be inactive or exert undesired effects. For example, 2(S)\u2010hydroxy oleic acid induces greater reduction in the tumor volume of lung cancer than does 2(R)\u2010hydroxy oleic acid.R),18(S)\u2010EpETE\u2014but not 17(S),18(R)\u2010EpETE\u2014has vasodilatory effects on arteries, again suggesting that chirality is important for determination of biological activity.The stereochemistry of oxidized fatty acids is a critical determinant of their biological activity. Indeed, 17,18\u2010EpETE is enantiomeric due to its epoxy groups\u201417(R)\u2010HEPE which plays important roles as a SPM and a precursor of resolvin E1 (RvE1) was shown to be generated by hydroxylation of EPA using Bacillus megaterium homogenates.B.\u00a0megaterium, catalyzed the epoxidation of unsaturated fatty acids and converted EPA into 17(S),18(R)\u2010EpETE in a stereoselective manner,Although 17,18\u2010EpETE is endogenously generated from EPA by cytochrome P450 (CYP), microorganisms also harbor various types of CYPs which catalyze a wide range of reactions including epoxidation and hydroxylation.Contact hypersensitivity is a commonly used mouse model of human allergic contact dermatitis, which includes sensitization and elicitation phases. In the sensitization phase, dendritic cells (DCs) migrate to the draining lymph nodes and activate T cells for the induction of memory\u2010type T cells. In the elicitation phase, on exposure to the same contact allergen as experienced during the sensitization phase, neutrophils and memory\u2010type T cells infiltrate the inflamed skin, where they produce pro\u2010inflammatory cytokines that lead to the development of skin swelling, rashes, and edema.S),18(R)\u2010EpETE produced by BM\u20103 (BM\u20103 17(S),18(R)\u2010EpETE) ameliorated CHS by inhibiting neutrophil migration into inflamed skin in a GPR40\u2010dependent manner. These findings reveal the activity of the 17(S),18(R)\u2010EpETE enantiomer and the availability of a bacterial enzyme that produces this bioactive lipid metabolite in a stereoselective manner.In this study, we found that 17(22.1Wild\u2010type (WT) C57BL/6J female mice  were purchased from SLC  and kept in a specific pathogen\u2010free animal facility at the National Institutes of Biomedical Innovation, Health and Nutrition (NIBIOHN) for at least 1\u00a0week before use in experiments. GPR40\u2010deficient mice have been described previously2.2S),18(R)\u2010EpETE and 17(R),18(S)\u2010EpETE ((\u00b1)17,18\u2010EpETE), a commercially available Cayman (\u00b1)17,18\u2010EpETE . In some experiments, mice were treated with stereoselective 17(S),18(R)\u2010EpETE (>99% enantiomeric excess) or 17(R),18(S)\u2010EpETE (>99% enantiomeric excess), which were purified from synthesized (\u00b1)17,18\u2010EpETE, or BM\u20103 17(S),18(R)\u2010EpETE. These lipids were injected intraperitoneally into mice by 100\u00a0ng/animal at 30\u00a0minutes before DNFB treatment. In some experiments, BM\u20103 17(S),18(R)\u2010EpETE were injected intraperitoneally into mice by 1\u00a0\u00b5g, 100\u00a0ng, or 10\u00a0ng/animal in order to evaluate dose response. We used 0.5% (vol/vol) ethanol dissolved in PBS  as a vehicle control.Contact hypersensitivity was induced as described previously.2.3The (\u00b1)17,18\u2010EpETE was prepared from EPA as described previously with some modifications.For purification of stereoselective 17,18\u2010EpETE, HPLC was performed using a CHIRALCEL OJ\u2010RH packed column . The isocratic mobile phase was a mixture of methanol (Wako) and water containing 0.1% (vol/vol) formic acid , which was pumped at a flow rate of 1.2\u00a0mL/min. The column was maintained at 30\u00b0C, and the eluent was monitored at a wavelength of 205\u00a0mm. As a control, commercially available Cayman (\u00b1)17,18\u2010EpETE was used for HPLC analysis.2.4E.\u00a0coli DH5\u03b1 (Nippon Gene), and transformed by heat shock at 42\u00b0C for 30\u00a0seconds. After the transformation, E. coli DH5\u03b1 was inoculated to modified LB agar medium  containing 25\u00a0\u03bcg/mL kanamycin sulfate (Wako) and cultured at 37\u00b0C for 18\u00a0hours. Modified LB agar medium was comprised of 1% (wt/vol) Difco select soytone , 0.5% (wt/vol) Bacto yeast extract , 1% (wt/vol) sodium chloride (Wako) and 1.5% (wt/vol) agar powder (Wako). The resultant colonies were picked and inoculated to modified LB liquid culture medium  containing 25\u00a0\u03bcg/mL kanamycin sulfate and cultured at 37\u00b0C for 18\u00a0hours. Modified LB liquid culture medium was comprised of 1% (wt/vol) Difco select soytone, 0.5% (wt/vol) Bacto yeast extract and 1% (wt/vol) sodium chloride. The plasmid DNA was extracted using QIAprep Spin Miniprep Kit (Qiagen) according to the manufacturer's instructions. In this way, pFusionF87V\u2010Km plasmid was constructed.BM3\u2010encoding pFusionF87V plasmid was ligated into pET\u201024d (+) (Merck) at KNC Laboratories .E.\u00a0coli DH5\u03b1 and transformed by heat shock at 42\u00b0C for 30\u00a0seconds. The recombinant E.\u00a0coli was inoculated to modified LB agar medium  containing 25\u00a0\u03bcg/mL kanamycin sulfate\u00a0and cultured at 37\u00b0C for 18\u00a0hours. The resultant colonies were inoculated to modified LB liquid culture medium  containing 25\u00a0\u00b5g/mL kanamycin sulfate and cultured at 37\u00b0C for 18\u00a0hours. The plasmid DNA was extracted using QIAprep Spin Miniprep Kit. In this way, pFusionBM3\u2010WT plasmid which has no mutation was constructed.We next used pFusionF87V\u2010Km plasmid as a template for construction of pFusionBM3\u2010WT plasmid to give rise to large amount of 17,18\u2010EpETE. The primers for inverse PCR were as follows: primer 1, 5'\u2010TTTACAAGCTGGACGCATGA\u20103' and primer 2, 5'\u2010TAACCCGTCTCCTGCAAAATCAC\u20103'. The fragments were self\u2010ligated using Ligation\u2010Convenience kit after phosphorylation of 5' ends by T4 polynucleotide kinase (Takara Bio). The resultant solution was suspended with ECOS Competent E.\u00a0coli BL21 (DE3) which is expression host strain, the pFusionBM3\u2010WT was suspended with ECOS Competent E.\u00a0coli BL21 (DE3) (Nippon Gene) and transformed by heat shock at 42\u00b0C for 30\u00a0seconds. After the transformation, E.\u00a0coli BL21 (DE3) was inoculated to modified LB agar medium  containing 25\u00a0\u03bcg/mL kanamycin sulfate and cultured at 37\u00b0C for 18\u00a0hours. The resultant colonies were inoculated to modified LB liquid culture medium  containing 25\u00a0\u00b5g/mL kanamycin sulfate and cultured at 28\u00b0C for 18\u00a0hours. The glycerol stock of pFusionBM3\u2010WT/BL21 (DE3) was made by mixing cultured solution and 50% (vol/vol) glycerol (Wako) in 2:1 (vol/vol) and stored at\u00a0\u221220\u00b0C.In order to carry pFusionBM3\u2010WT into 2.5Cultivation was performed at KNC Laboratories. For preculture, 100\u00a0\u00b5L of pFusionBM3\u2010WT/BL21 (DE3) glycerol stock was inoculated in 500\u00a0mL of modified LB liquid culture medium  containing 25\u00a0\u00b5g/mL kanamycin sulfate and cultured at 25\u00b0C for 22\u00a0hours with shaking at 120\u00a0rpm.D\u2010thiogalactopyranoside  and cultured at 20\u00b0C for 47\u00a0hours with ventilation rate of 75\u00a0L/min. 2\u00a0\u00d7\u00a0YT medium was comprised of 1.6% (wt/vol) Difco select soytone, 1% (wt/vol) Bacto yeast extract and 0.5% (wt/vol) sodium chloride. pH in culture was maintained at pH 7.0\u00a0\u00b1\u00a00.1 using 25% (vol/vol) ammonia solution (Wako) and 2\u00a0mol/L phosphoric acid (Wako), and dissolved oxygen was maintained at DO 1.5\u00a0\u00b1\u00a00.5\u00a0ppm by stirring.1 L of precultured liquid was added to 150 L of modified 2\u00a0\u00d7\u00a0YT medium  containing 25\u00a0\u00b5g/mL kanamycin sulfate, 80\u00a0\u00b5g/mL 5\u2010aminolevulinic acid (Wako), 100\u00a0\u00b5M ammonium iron (II) sulfate hexahydrate (Wako), 250\u00a0\u00b5mol/L isopropyl \u03b2\u20102.6Bioconversion of EPA into 17,18\u2010EpETE was performed at KNC Laboratories. 1.5 L of 1\u00a0mol/L EPA  was added to cultured medium and incubated at 20\u00b0C for 71.5\u00a0hours with ventilation rate of 20\u00a0L/min in order to convert EPA into 17,18\u2010EpETE. pH was maintained at pH 7.0\u00a0\u00b1\u00a00.1 using 25% (vol/vol) ammonia solution and 2\u00a0mol/L phosphoric acid, and dissolved oxygen was maintained at DO 1.5\u00a0\u00b1\u00a00.5\u00a0ppm by stirring.In order to stop reaction and kill bacteria, 35\u00a0L of ethanol (Wako) was added to reaction mixture and cultured at 20\u00b0C for 46\u00a0hours with ventilation rate of 20\u00a0L/min. pH was maintained at pH 7.0\u00a0\u00b1\u00a00.1 using 25% (vol/vol) ammonia solution and 2\u00a0mol/L phosphoric acid, and dissolved oxygen was maintained at DO 1.5\u00a0\u00b1\u00a00.5\u00a0ppm by stirring. In order to confirm whether the bacteria are dead, the reaction liquid was inoculated to modified LB agar medium  and cultured at 37\u00b0C for 18\u00a0hours, then we confirmed that the colonies were not formed.2.7S),18(R)\u2010EpETE was performed at KNC Laboratories. Fifteen kilograms of Diaion HP20  were added to 150 L of EPA reaction solution (20% (vol/vol) ethanol aqueous solution) and stirred for 1\u00a0hour to adsorb 17,18\u2010EpETE, which was confirmed by the analysis of the supernatant with HPLC Prominence System (Shimadzu). The condition of HPLC analysis is as follows: flow rate; 1.0\u00a0mL/min, column temperature; 40\u00b0C, UV wavelength; 205\u00a0nm, injection volume; 10\u00a0\u00b5L, column; C18 column , mobile phase; (A) 0.05% (vol/vol) formic acid aqueous solution and (B) acetonitrile. The eluent gradients were 45%\u201055% (vol/vol) B for 0\u201012\u00a0minutes, 55%\u201075% (vol/vol) B for 12\u201019\u00a0minutes, 75%\u2010100% (vol/vol) B for 19\u201020\u00a0minutes, 100% (vol/vol) B for 20\u201028\u00a0minutes, 100%\u201045% (vol/vol) B for 28\u201029\u00a0minutes, and 45% (vol/vol) B for 29\u201040\u00a0minutes. After the absorption of 17,18\u2010EpETE, HP20 was removed from the EPA reaction solution, and washed four times with purified water. Then, HP20 was soaked in 20% (vol/vol) ethanol aqueous solution and stored at 4\u00b0C.Purification of BM\u20103 17  ethanol aqueous solution containing 0.05% (vol/vol) acetic acid). This solution was charged to Inertsil ODS\u20103 column  that had been equilibrated with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid at 50\u00a0mL/min flow rate. After charged, the column was washed with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid, and eluted with 70% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid at 45\u00a0mL/min flow rate. The elution sample containing 17,18\u2010EpETE was stored at \u221280\u00b0C as a low purity sample .In order to obtain high purity sample, the low purity sample was charged to Inertsil ODS\u20103 column  that had been equilibrated with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid at 15\u00a0mL/min flow rate. After charged, the column was washed with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid, and eluted with 55% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid at 10\u00a0mL/min flow rate. The elution sample containing 17,18\u2010EpETE was stored at \u221280\u00b0C as a high purity sample .S),18(R)\u2010EpETE for biological assay.In order to replace the solvent to ethanol, the elution sample containing 17,18\u2010EpETE was diluted with Milli\u2010Q water containing acetic acid  ethanol aqueous solution containing 0.05% (vol/vol) acetic acid). The resultant solution was charged to Inertsil ODS\u20103 column  that had been equilibrated with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid at 15\u00a0mL/min flow rate. After charged, the column was washed with 20% (vol/vol) ethanol aqueous solution containing 0.05% (vol/vol) acetic acid, followed by washed with 20% (vol/vol) ethanol aqueous solution, and eluted with 100% (vol/vol) ethanol at 15\u00a0mL/min flow rate. The elution sample containing 17,18\u2010EpETE was stored at \u221280\u00b0C as a very high purity sample , and used as BM\u20103 17 staining, frozen tissue sections were stained in hematoxylin solution (Wako) for 10\u00a0minutes and washed with water for 30\u00a0minutes. Then, the sections were stained in 1% eosin Y solution (Wako) for 1\u00a0minute and dehydrated through increasing concentrations of ethanol . Finally, stained tissue sections were dehydrated in xylene  for 3\u00a0minutes and mounted in Permount .For immunohistologic analysis, frozen tissue sections were washed with PBS for 10\u00a0minutes and then blocked in 2% (vol/vol) newborn calf serum (Equitech\u2010Bio) in PBS for 30\u00a0minutes at room temperature in an incubation chamber (Cosmo Bio). Tissue sections were then incubated in an incubation chamber overnight at 4\u00b0C with fluorescein isothiocyanate\u2013anti\u2010Ly6G monoclonal antibody  in 2% (vol/vol) newborn calf serum in PBS. Then, samples were washed once for 5\u00a0minutes in 0.1% (vol/vol) Tween\u201020  in PBS and then in PBS only for 5\u00a0minutes. To visualize nuclei, tissue sections were stained with 4\u02b9,6\u2010diamidino\u20102\u2010phenylindole  for 10\u00a0minutes at room temperature in the incubation chamber. Finally, tissue sections were washed twice with PBS for 5\u00a0minutes each, and mounted in Fluoromount (Diagnostic BioSystems) and examined under a fluorescence microscope .2.9The isolation of cells from ear tissue and their flow cytometric analysis were performed as described previously.Cell suspensions were filtered using a cell strainer  and cells counted. Cells were stained using an anti\u2010CD16/32 monoclonal antibody  to avoid nonspecific staining, and dead cells were stained with 7\u2010aminoactinomycin D . The cells were further stained with the following antibodies: fluorescein isothiocyanate\u2013anti\u2010Ly6G , allophycocyanin\u2013Cy7\u2013anti\u2010CD11b , and BV421\u2013anti\u2010CD45 . Samples were analyzed using MACSQuant . Data were analyzed using FlowJo 9.9 software (TreeStar).2.105 cells) were suspended in HBSS  containing 0.2% bovine serum albumin (Sigma Aldrich) and allowed to adhere to fibronectin\u2010coated coverslips (Neuvitro) for 15\u00a0minutes at 37\u00b0C in a 5% CO2 incubator. Neutrophils were treated with either 1000, 100, 10, or 1\u00a0nmol/L of commercially available Cayman (\u00b1)17,18\u2010EpETE, BM\u20103 17(S),18(R)\u2010EpETE, 18\u2010HEPE , RvE1 , or 0.03% (vol/vol) ethanol (vehicle control) for 15\u00a0minutes and then stimulated with 1\u00a0\u03bcmol/L N\u2010formyl\u2010methionyl\u2010phenylalanine  or 100\u00a0nmol/L leukotriene B4  for 2\u00a0minutes at 37\u00b0C in a 5% CO2 incubator. Neutrophils were fixed in 4% paraformaldehyde , permeabilized using 0.5% (vol/vol) Triton X\u2010100  in PBS, and stained with 100\u00a0nmol/L Acti\u2010stain 488\u2013phalloidin (Cytoskeleton) for 30\u00a0minutes at room temperature. Finally, cell nuclei were stained by incubating neutrophils with 4\u02b9,6\u2010diamidino\u20102\u2010phenylindole for 30\u00a0seconds at room temperature. Images were obtained with Leica TCS SP8 confocal microscopy (Leica Microsystems).Neutrophils were purified from bone marrow as described previously.2.11Actin\u03b2 sense, 5'\u2010aaggccaaccgtgaaaagat\u20103'; Actin\u03b2 antisense, 5'\u2010gtggtacgaccagaggcatac\u20103'; interferon\u2010\u03b3 (Ifn\u2010\u03b3) sense, 5'\u2010atctggaggaactggcaaaa\u20103'; Ifn\u2010\u03b3 antisense, 5'\u2010ttcaagacttcaaagagtctgaggta\u20103'; interleukin (Il)\u201017 sense, 5'\u2010cagggagagcttcatctgtgt\u20103'; Il\u201017 antisense, 5'\u2010gctgagctttgagggatgat\u20103'; Cxcl1 sense, 5'\u2010gactccagccacactccaac\u20103'; Cxcl1 antisense, 5'\u2010tgacagcgcagctcattg\u20103'; Cxcl2 sense, 5'\u2010aaaatcatccaaaagatactgaacaa\u20103'; Cxcl2 antisense, 5'\u2010ctttggttcttccgttgagg\u20103'; Cxcl9 sense, 5'\u2010cttttcctcttgggcatcat\u20103'; Cxcl9 antisense, 5'\u2010gcatcgtgcattccttatca\u20103'; Cxcl10 sense, 5'\u2010gctgccgtcattttctgc\u20103'; Cxcl10 antisense, 5'\u2010tctcactggcccgtcatc\u20103'.Reverse transcription and quantitative PCR analysis were performed as described previously.2.12P\u00a0<\u00a00.05 was considered significant.Statistical significance was evaluated through one\u2010way ANOVA using Prism 3.03 software (GraphPad Software). A 33.1S),18(R)\u2010EpETE from 17(R),18(S)\u2010EpETE. In this issue, we first chemically synthesized a large amount of (\u00b1)17,18\u2010EpETE from EPA and found that, like commercially available Cayman (\u00b1)17,18\u2010EpETE, synthesized (\u00b1)17,18\u2010EpETE showed 2 peaks using HPLC system with chiral column. The bacterial enzyme BM\u20103 has been reported to stereoselectively convert EPA into 17(S),18(R)\u2010EpETE.S),18(R)\u2010EpETE was identical with the second peak of (\u00b1)17,18\u2010EpETE ,18(S)\u2010EpETE.We previously reported that commercially available Cayman (\u00b1)17,18\u2010EpETE showed potent anti\u2010allergic and anti\u2010inflammatory properties.3.2S),18(R)\u2010EpETE showed anti\u2010inflammatory activity in inhibiting ear swelling but 17(R),18(S)\u2010EpETE had little effect 17,18\u2010EpETE, 17,18(R)\u2010EpETE exerted anti\u2010inflammatory activity, we next examined whether 17(S),18(R)\u2010EpETE stereoselectively produced by BM\u20103 suppresses CHS. We found that BM\u20103 17(S),18(R)\u2010EpETE suppressed ear swelling ,18(R)\u2010EpETE decreased inflammation in the skin ,18(R)\u2010EpETE decreased the number of neutrophils in inflamed ears ,18(R)\u2010EpETE ,18(R)\u2010EpETE in CHS by evaluating ear swelling and neutrophil numbers. Both ear swelling and neutrophil numbers were decreased at the dose of 1\u00a0\u00b5g and 100\u00a0ng/animal, but the anti\u2010inflammatory effects were hardly observed at the dose of 10\u00a0ng/animal ,18(R)\u2010EpETE was shown to be effective at the dose more than 100\u00a0ng/animal.Given that 17,18(R)\u2010EpETE on pseudopod formation in neutrophils isolated from bone barrow. We found that fMLP\u2010induced pseudopod formation was inhibited by treatment with BM\u20103 17(S),18(R)\u2010EpETE ,18(R)\u2010EpETE was absent when the neutrophils were prepared from GPR40\u2010deficient mice. We also found that BM\u20103 17(S),18(R)\u2010EpETE inhibited LTB4\u2010induced pseudopod formation in a GPR40\u2010dependent manner ,18(R)\u2010EpETE treatment ,18(R)\u2010EpETE did not inhibit the expression of Ifn\u2010\u03b3 ,18(R)\u2010EpETE acts on neutrophil selectively.We next evaluated the inhibitory effect of BM\u20103 17,18(R)\u2010EpETE with EPA\u2010derived fatty acid metabolites, RvE1 and 18\u2010HEPE, for inhibition of pseudopod formation ,18(R)\u2010EpETE showed inhibitory effects at the dose of 10\u00a0nmol/L, while RvE1 and 18\u2010HEPE lost their activities. BM\u20103 17(S),18(R)\u2010EpETE also lost its activity at the dose of 1\u00a0nmol/L.We compared the effectiveness of BM\u20103 17,18(R)\u2010EpETE at the dose of 10\u00a0nmol/L, while RvE1 and 18\u2010HEPE showed inhibitory effects. Both RvE1 and 18\u2010HEPE lost its activity at the dose of 1\u00a0nmol/L. These results indicated that EPA\u2010derived bioactive lipid mediators of BM\u20103 17(S),18(R)\u2010EpETE, RvE1, and 18\u2010HEPE all possess anti\u2010inflammatory activity by inhibiting neutrophil pseudopod formation.In the case of LTB44, which is secreted by neutrophils, promotes secondary neutrophil migration.S),18(R)\u2010EpETE inhibited both fMLP\u2010 and LTB4\u2010induced pseudopod formation, and RvE1 and 18\u2010HEPE also inhibited both fMLP\u2010 and LTB4\u2010induced pseudopod formation. Consistent with these findings, a previous report showed that RvE1 and 18\u2010HEPE reduced neutrophil transmigration.4 receptor, BLT1.4\u2010induced pseudopod formation through BLT1 antagonistic activity in DC.S),18(R)\u2010EpETE inhibited neutrophil pseudopod formation by GPR40\u2010mediated pathway, while 18\u2010HEPE and RvE1 used ChemR23 and/or BLT1 as functional receptors.Actin polymerization and neutrophil migration are induced by different kinds of chemoattractants. The fMLP promotes primary neutrophil migration in response to bacterial infection, while LTBS)\u2010 and (R)\u2010thalidomide was introduced as a sedative medicine in the late 1950s, but it was withdrawn due to teratogenicity of (S)\u2010thalidomide, indicating the importance of stereoselective production of candidate medicines.S)\u2010 and (R)\u2010enantiomers of salbutamol exert different effects: the (R)\u2010enantiomer of salbutamol binds the B2\u2010adrenergic receptor with greater affinity than the (S)\u2010enantiomer and is responsible for salbutamol's bronchodilation activity.The use of single\u2010enantiomer medicines can potentially lead to simpler and more selective pharmacologic profiles, because the enantiomers of a chiral compound may differ significantly in their bioavailability.S),18(R)\u2010EpETE stereoselectively showed anti\u2010inflammatory activity in CHS. Conversely, it is reported that 17(R),18(S)\u2010EpETE\u2014but not 17(S),18(R)\u2010EpETE\u2014is a potent vasodilator and stimulates calcium\u2010activated potassium channels, which lead to the relaxation of rat cerebral artery vascular smooth muscle cells.S),18(R)\u2010EpETE\u2013GPR40 axis suppresses CHS, whereas the 17(R),18(S)\u2010EpETE\u2013calcium\u2010activated potassium\u2010channel axis achieves arterial relaxation.S),18(R)\u2010EpETE as a single\u2010enantiomer therapy might decrease the risk of side effects due to vasodilatory activity, such as a rapid decrease in blood pressure and increased skin redness.In this study, we found that BM\u20103 17(R),18(S)\u2010EpETE, whereas Cyp4f18 in mice and CYP2D6 in humans\u2014like BM\u20103\u2014selectively generate 17(S),18(R)\u2010EpETE.R),18(S)\u2010EpETE and 17(S),18(R)\u2010EpETE.We previously found that dietary linseed oil, which contains large amounts of \u03b1\u2010linolenic acid, a precursor of EPA and DHA, increases the amount of \u03c93 PUFA\u2010derived metabolites in the body.S),18(R)\u2010EpETE might reflect differences in CYP activity or expression level. For example, the expression level of Cyp1a2 is upregulated by the ligand\u2010activated transcription factor aromatic hydrocarbon receptor (AhR).R),18(S)\u2010EpETE might be modulated through diet.S),18(R)\u2010EpETE and 17(R),18(S)\u2010EpETE.CYPs harbor gene polymorphisms, which cause different enzymatic activities among individuals.Bacillus bacteria, including B.\u00a0megaterium, are used for the production of fermented foods, such as the soybean products natto and miso. Therefore, the production level of lipid metabolites likely is affected not only by the enzymes in the body but also by enzymes derived from microorganisms in fermented food, suggesting that the production levels of 17(S),18(R)\u2010EpETE could be increased by eating fermented foods containing Bacillus bacteria.B.\u00a0megaterium homogenate reportedly yields 17,18\u2010EpETE and 18\u2010HEPE, whereas BM\u20103 primarily catalyzes epoxidation and produces 17,18\u2010EpETE from EPA, thus suggesting that not only BM\u20103, various types of CYPs in B.\u00a0megaterium contribute to the production of 17,18\u2010EpETE and 18\u2010HEPE.Because microorganisms metabolize fatty acids, microorganisms can affect the lipid profile. In particular, microorganisms are used for the production of fermented foods, which may often contain abundant amounts of lipid metabolites. For example, S),18(R)\u2010EpETE can reduce CHS. The 17(S),18(R)\u2010EpETE\u2013GPR40 axis played a key role in the amelioration of CHS by inhibiting neutrophil migration. These results suggest that bacterial fermentation with BM\u20103 activity is a promising tool for the stereoselective mass\u2010production of 17(S),18(R)\u2010EpETE.In conclusion, the present study showed enzymatically produced 17(There are no conflict of interest to declare. AS, TN, and JK designed the research and wrote the paper. AS, TN, SK, SP, NM, MS, SM, EN, and JO performed experiments, analyzed data, and discussed the results. TH, PT, SH, KH, and KK provided technical help and discussed the results.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file."}
{"text": "Recently oxidative stress induced maladies have amplified owing to sedentary lifestyle and monotonous diet. Introduction of plant based biomolecules may be a suitable strategy to cope with the lipid peroxidation. In this context, black tea polyphenols (theaflavin & thearubigins) are in fame among the scientific community as cost effective therapeutic agents owing to their safety, economics, structural diversity and ability to modulate various lipid peroxidation responses by halting the expression of different metabolic targets.0 (control diet without supplementation), T1 , T2  & T3  for the period of 56\u00a0days. Alongside, a control study was also carried out for comparison by involving normal rats fed on arginine free diet. The body weight, lipid profile, glycemic responses, Renal function test, liver function test, antioxidant indices and hematological parameters were estimated at the termination of study.The mandate of present investigation was to first time check the synergism among the isolated theaflavins & thearubigins against lipid peroxidative indicators both in vitro and in vivo. Purposely, theaflavins and thearubigins were isolated from black tea through solvent partition methods by using different solvents  and time intervals  and subjected to in vitro characterization through different antioxidant indices to access the in vitro lipid peroxidation shooting effect of these bioactive moieties. Moreover, individual theaflavins contents also estimate through HPLC. For evaluation of in vivo antioxidant effect, renal malfunction was induced through arginine and forty rats were divided in four groups  and 04 types of diets were given i.e. TThe results indicated that theaflavins and thearubigins isolation was significantly affected by time of extraction and solvent. In this context, aqueous ethanol at 60\u00a0min extraction interval caused maximum extraction. Likewise, theaflavins isolate exhibited more antioxidant activity as compared to thearubigins. Moreover, the theaflavins and thearubigins based experimental diets imparted significant reduction in Lipid profile, glucose content, renal function tests and TBARS with enhancement in insulin, HDL and hematological parameters. In this context, theaflavin based diet caused maximum reduction in lipid profile and TBARS better as compared to thearubigins and theaflavins + thearubigins based. However, theaflavin+ thearubigins based diet caused highest glucose, urea & creatinine decline and maximum insulin increase & antioxidant indices as compared to other nutraceuticals.It was deduced that theaflavins & thearubigins have strong antioxidative potential both in in vitro as well as in vivo to tackle the menace associated with lipid peroxidation. Likewise, preventive role of theaflavin in lipid peroxidation is mainly attributed to its ability to cease the chain reaction. Apart from free radical scavenging and metal chelating abilities, theaflavin has potential to activate certain antioxidant enzymes like glutathione-S-transferase (GST), glutathione peroxidase (GPX), superoxide dismutase (SOD) and catalase (CAT) thereby reduces lipid peroxidation. Likewise, thearubigins or polymeric black tea polyphenols (PBPs) are the oxidative products of phenolics and their production accelerated after 75% conversion of catechins into flavan-3-ol molecules. They have ability to activate phase II enzymes by inducing transcriptional upregulation in lung and liver [Globally, therapeutic worth of tea has been established against numerous maladies. The health escalating perspectives of tea has been attributed to his distinguished polyphenols. Accordingly, theaflavins and thearubigins are the promising polyphenols belong to subclass flavanolos. They produced when fresh tea leaves undergo enzymatic fermentation triggered by polyphenol oxidase and catalase resulted in structural variations in catechins thus formed theaflavin and thearubigins \u20133. Strucnd liver .Chronic renal failure (CRF) is an irreversible loss to functioning nephrons resulting numerous disorders of blood vessels, glomeruli, tubules and renal interstitium . VariousThe mandate of current investigation to isolate the theafavins and thearubigins from black tea Qi-men variety by using different solvents and time intervals, in vitro characterization and preparation of nutraceutical intervention against renal malfunctioning in arginine induced liver damage rats.Black tea variety (Qi-Men) was procured from the National Tea Research Institute (NTRI), Shinkiari, Mansehra. The reagents  and standards were purchased from Merck  and Sigma-Aldrich . For efficacy trial, Male Sprague Dawley rats were housed in the Animal Room of Physiology department of GCUF. For biological assay, diagnostic kits were purchased from Sigma-Aldrich, Bioassay  and Cayman Chemicals .Theaflavin and thearubigins were extracted by using water, methanol and ethanol at 30, 60 and 90\u00a0min intervals and isolated by solvent partition method . Initial18 column , 10\u00a0\u03bcL sample through auto sampler (WISP Model 710) and column temperature 40\u00a0\u00b0C. The composition of mobile phase was acetonitrile, ethylacetate and 0.05% phosphoric acid in ratio of 21:3:76 with flow rate of 1\u00a0mL/min and using on UV/vis detector (model 481) and measurement wavelength was 278\u00a0nm.The isolated samples of theaflavins were characterized for their fractions through HPLC . The conditions for HPLC were CAntioxidant capacity of isolated theaflavin and thearubigins fractions were determined through antioxidant indices including total antioxidant activity, free radical scavenging activity and ferric reducing antioxidant power as following methods. For this purpose, the isolated fractions both from theaflavin and thearubigins were mixed in water, methanol and ethanol (1\u00a0mg/mL) to be further utilized in antioxidant indices estimation.V/vis Spectrophotometer (CECIL CE7200) against control and expressed results as mg gallic acid/100\u00a0g.Total phenolics of resultant isolates were estimated spectrophotometricaly using Folin-Ciocalteau method . Briefly\u03b2-carotene and linoleic acid assay was applied to measure the total antioxidant capacity . PurposeDPPH radical scavenging activity was measured according the procedure of . InitialThe FRAP test was performed according to the guidelines of . 0.5\u00a0mL Effect of isolated theaflavin and thearubigins fraction on glucose diffusion was assessed using glucose oxidase kit and 1.65\u00a0mM D-glucose solution .For biological assay, rats were divided in to four homogeneous groups fed on experimental diet. The common experimental diet was formulated using corn oil (10%), protein (10%), corn starch (64%), cellulose (10%), mineral (3%) vitamin mixture (1%) alongside arginine @ 2% for the induction of renal malfunctioning. For comparison a control study was also conducted by providing the normal diet (same composition except for arginine). However, common experimental diet from both studies further divided into four groups on the bases of addition of active ingredients, Diet 1 , Diet 2, (theaflavins supplementation @ 1\u00a0g), Diet 3, (Thearubigins supplementation @ 1\u00a0g) and Diet 4 . Afterwards All the ingredients were mixed then oven baked for 10\u00a0min. The dose was selected by carried out a 21\u00a0days safety trial (Data not included).n\u2009=\u20096 rats/dose). The treatments were given in both acute (single dose followed by a 48-h observation period) and sub-acute . The hematological analysis as well as general physical examination was carried out [In safety trial, rats were provided all the active ingredients orally @ of 250, 500, 1000, 1500, 2000 and 3000\u00a0mg/kg-bw  and relative humidity (55\u2009\u00b1\u20095%) along with 12\u00a0h light-dark period. At the initiation of study, some rats  were sacrificed to establish the baseline trend. For the induction of renal malfunctioning initially high arginine diet @ 2% was administrated for a period of 7 days. During that tenure urea and creatinine levels were observed to estimate the onset of renal malfunctioning. Afterwards when values of both test deviate 25% from normal then the original study was started. The study comprised of four groups of rats ten in each . Accordingly, four types of experimental diets were given i.e. T0 , T1, T2  and T3  by protocols of , high deGlucose concentration was estimated by GOD-PAP method by following the protocol of , howeverThe serum samples were also analyzed for urea by GLDH-method and creatinine by Jaffe-method using commercial kits  to assesGlutathione contents were assessed by adapting the guidelines as mentioned by . The reaLiver function tests including aspartate aminotransferase (AST), alanine aminotransferase (ALT) and alkaline phosphatase (ALP) were assessed. Levels of AST and ALT were measured by the dinitrophenylhydrazene (DNPH) method using Sigma Kits 59\u201350 and 58\u201350, respectively and ALP by Alkaline Phosphates\u2013DGKC method .Red blood cells indices including total red blood cells (TRBCs), hemoglobin (Hb), hematocrit (Hct) and mean corpuscular volume (MCV) were estimated. Likewise, white blood cell indices including monocytes, lymphocytes and neutrophils were measured by using Automatic Blood Analyzer  .Statistical program SAS  was utilized to analyze the data collected from this study. Two-way analysis of variance (ANOVA) was conducted to evaluate the effect of extraction time and solvent on polyphenol isolation. Moreover, One-way ANOVA were applied in efficacy trial and significance among the treatments were determined by applying LSD.p\u2009\u2265\u20090.001) and time (p\u2009\u2265\u20090.002), highest theaflavin (3.42\u2009\u00b1\u20090.27\u00a0g/100\u00a0g) were detected in ethanolic extract followed by methanol (2.77\u2009\u00b1\u20090.25\u00a0g/100\u00a0g) whilst water exhibited the lowest yield (2.32\u2009\u00b1\u20090.13\u00a0g/100\u00a0g). Similarly, solvent (p\u2009\u2265\u20090.001) & time (p\u2009\u2265\u20090.001) also imparted pronounced impact for thearubigins, highest in ethanol and minimum in water. Extraction efficiency was also influenced by time and maximum yield for theaflavins and thearubigins was obtained at 60\u00a0min 3.41\u2009\u00b1\u20090.17\u00a0g/100\u00a0g and 13.17\u2009\u00b1\u20090.59\u00a0g/100\u00a0g, respectively (Table\u00a0Means for extraction yield illuminated the significant effect of solvents p\u2009\u2265\u20090.00 and timep\u2009\u2265\u20090.001) and extraction time (p\u2009\u2265\u20090.0031) whilst their interactive effect showed non-significant trend (p\u2009\u2265\u20090.521). Means for TF1 indicated highest value (2.18\u2009\u00b1\u20090.06\u00a0mg/g) in ethanolic extract followed by methanol (1.96\u2009\u00b1\u20090.03\u00a0mg/g) and water (0.751\u2009\u00b1\u20090.001\u00a0mg/g). However, effect of time revealed maximum output (1.79\u2009\u00b1\u20090.006\u00a0mg/g) at 60\u00a0min and minimum (1.48\u2009\u00b1\u20090.001\u00a0mg/g) at 30\u00a0min. Likewise trend was observed for TF2A, TF2B & TF3, among the solvents highest ratio in ethanolic fractions and minimum in water and among time intervals maximum in 60\u00a0min and minimum in 30\u00a0min , \u00df-carotene (p\u2009\u2265\u20090.004) and FRAP (p\u2009\u2265\u20090.000) whilst non-significant differences (p\u2009\u2265\u20090.185) were observed for glucose diffusion. Means for DPPH in theaflavin and thearubigins indicated highest activity in ethanolic extract 83.27\u2009\u00b1\u20091.23 & 68.72\u2009\u00b1\u20093.61%, respectively followed by methanol and water. For the time factor, the highest DPPH activity of theaflavin was 82.69\u2009\u00b1\u20095.10% at 60\u00a0min whilst 78.03\u2009\u00b1\u20094.31 & 75.89\u2009\u00b1\u20093.92% at 90 and 30\u00a0min, respectively. Similarly, thearubigins also exhibited highest DPPH activity at 60\u00a0min  followed by the methanolic (89.96\u2009\u00b1\u20092.31%) and water extract (87.02\u2009\u00b1\u20093.12%). Likewise, in thearubigins the values for this parameter in respective extracts were 87.71\u2009\u00b1\u20096.12, 84.92\u2009\u00b1\u20096.42 and 83.02\u2009\u00b1\u20097.12%. Considering time factor, highest glucose diffusion was reported at 60\u00a0min for the both parameters (Table\u00a0p\u2009\u2265\u20090.001) of experimental diets on weight in both control and renal malfunctional rats and recorded values for weight in renal malfunctional rats at the termination of study were 213.10\u2009\u00b1\u20096.11 & 213.73\u2009\u00b1\u20098.12, 217.74\u2009\u00b1\u20095.61 & 220.52\u2009\u00b1\u20099.26 and 214.17\u2009\u00b1\u20094.25 & 215.73\u2009\u00b1\u20096.23\u00a0g/rat for T1 T2 and T3, respectively  effect on serum cholesterol level of rats, highest cholesterol level was observed in T0 (86.31\u2009\u00b1\u20094.63\u00a0mg/dL) that significantly reduced in T1 (81.14\u2009\u00b1\u20092.12\u00a0mg/dL) trailed by T3 (82.29\u2009\u00b1\u20094.25\u00a0mg/dL) and T2 (82.99\u2009\u00b1\u20095.63\u00a0mg/dL). In contrary, the tested diets imparted non-significant (p\u2009\u2265\u20090.091) enhancement in HDL levels of study animals. In this context, T0 drink consuming group exhibited least HDL value as 38.54\u2009\u00b1\u20092.36\u00a0mg/dL, respectively that elevated non-significantly to 39.70\u2009\u00b1\u20092.32, 38.92\u2009\u00b1\u20091.09 and 39.64\u2009\u00b1\u20091.56\u00a0mg/dL in T1, T2 and T3 groups, respectively. As for as LDL levels were concern, the tested diets caused momentous (p\u2009\u2265\u20090.000) decline on this trait. The maximum LDL was noticed in T0 that reduced substantially to in T1, T2 and T3, correspondingly. Triglycerides values for T0, T1, T2 and T3 differed non-momentously (p\u2009\u2265\u20090.128) i.e. 67.15\u2009\u00b1\u20094.20, 64.96\u2009\u00b1\u20095.15, 65.20\u2009\u00b1\u20094.12 and 65.13\u2009\u00b1\u20092.12\u00a0mg/dL (Table The prepared diets caused significant ( 86.31\u2009\u00b1\u2009.63\u00a0mg/dLp\u2009\u2265\u20090.000) impact of experimental diets on blood glucose levels of tested groups. In renal malfunctional rats, the highest glucose level 89.18\u2009\u00b1\u20096.14 in T0 group however, black tea polyphenols supplemented diets lowered the glucose value to 84.70\u2009\u00b1\u20096.13, 85.60\u2009\u00b1\u20093.20 and 83.98\u2009\u00b1\u20097.14\u00a0mg/dL in T1, T2 and T3 groups, correspondingly. Likewise, insulin also varied significantly (p\u2009\u2265\u20090.004) minimum insulin values 7.76\u2009\u00b1\u20090.22 \u03bcU/mL were observed in T0 whilst highest level 8.11\u2009\u00b1\u20090.12 \u03bcU/mL in T3 followed by 8.06\u2009\u00b1\u20090.41 \u03bcU/mL in T1 and 7.96\u2009\u00b1\u20090.52 \u03bcU/mL in T2  impact on these traits however, the diet supplemented with both theaflavin and thearubigins caused maximum effect in comparison with others. The highest urea level 37.83\u2009\u00b1\u20092.46 was recorded in T0 that suppressed to 33.44\u2009\u00b1\u20091.45, 34.09\u2009\u00b1\u20092.56 and 34.95\u2009\u00b1\u20092.91\u00a0mg/dL in T3, T1 and T2 groups. Likewise, highest creatinine level 1.15\u2009\u00b1\u20090.03\u00a0mg/dL was recorded in T0 group (control drink) that significantly suppressed to 1.04\u2009\u00b1\u20090.05\u00a0mg/dL in T3 (drink containing theaflavin+thearubigins), 1.08\u2009\u00b1\u20090.01\u00a0mg/dL in T1 (drink containing theaflavin) and 1.09\u2009\u00b1\u20090.02\u00a0mg/dL in T2 (drink containing thearubigins).The means in Table 0 group showed decreased glutathione content 43.12\u2009\u00b1\u20093.01\u00a0mg/L that momentously (p\u2009\u2265\u20090.001) enhanced to 46.19\u2009\u00b1\u20092.56, 44.91\u2009\u00b1\u20094.14 and 47.87\u2009\u00b1\u20094.12\u00a0mg/L in T1, T2 and T3 groups. Similar significant (p\u2009\u2265\u20090.000) effect of experimental diets was observed for MDA, the recorded values for this trait in T0 was 8.01\u2009\u00b1\u20090.21that differed significantly in T1, T2 and T3 by 6.78\u2009\u00b1\u20090.24, 7.55\u2009\u00b1\u20090.01 and 6.95\u2009\u00b1\u20090.4\u00a0mmol/L (Table T0 (49.06\u2009\u00b1\u20093.01\u00a0IU/L) was significantly ((p\u2009\u2265\u20090.001)) varied in T1 T2 and T3 groups with mean values 48.50\u2009\u00b1\u20092.42, 49.12\u2009\u00b1\u20092.13 and 46.38\u2009\u00b1\u20092.45\u00a0IU/L. Moreover, T0 group showed maximum AST level 105.27\u2009\u00b1\u20095.14\u00a0IU/Lthat reduced substantially ((p\u2009\u2265\u20090.002) in T1 (101.68\u2009\u00b1\u20099.12\u00a0IU/L), T2 (103.00\u2009\u00b1\u20099.02\u00a0IU/L) and T3 (109.01\u2009\u00b1\u20099.45\u00a0IU/L). Likewise, ALP level in T0 (196.89\u2009\u00b1\u200917.23\u00a0IU/L) was significantly ((p\u2009\u2265\u20090.001)) higher than that of T1 (177.89\u2009\u00b1\u200915.20\u00a0IU/L), T2 (180.90\u2009\u00b1\u200913.25\u00a0IU/L) and T3 (167.68\u2009\u00b1\u20099.62\u00a0IU/L).Mean values in Table 0, T1, T2 and T3, respectively. Mean Hb level in T0, T1, T2 and T3 were 10.88\u2009\u00b1\u20090.71, 11.15\u2009\u00b1\u20090.61, 10.98\u2009\u00b1\u20090.81 and 11.20\u2009\u00b1\u20090.71\u00a0g/L, respectively. Moreover, the recorded hematocrit value for T0 (36.79\u2009\u00b1\u20091.52%) was improved non-significantly in T1, T2 and T3 groups as 37.25\u2009\u00b1\u20092.71, 36.99\u2009\u00b1\u20092.12 and 37.03\u2009\u00b1\u20092.81%, respectively. Likewise, mean MCV values for T0, T1, T2 and T3 were 49.96\u2009\u00b1\u20092.48, 51.03\u2009\u00b1\u20093.82, 50.92\u2009\u00b1\u20093.97 and 51.65\u2009\u00b1\u20093.30\u00a0fl, respectively. Similarly, the mean WBCs in T0 were 17.29\u2009\u00b1\u20090.58 cells/nL that non-significantly decreased to 16.99\u2009\u00b1\u20090.49, 17.26\u2009\u00b1\u20090.65 and 16.85\u2009\u00b1\u20090.35 cells/nL, respectively in tested groups. Likewise, means for Neutrophils in T0, T1, T2, and T3 were 62.25\u2009\u00b1\u20091.28, 63.85\u2009\u00b1\u20092.82, 62.45\u2009\u00b1\u20093.25 and 64.63\u2009\u00b1\u20092.63%, respectively. Mean monocytes values for T0, T1, T2 and T3 groups were 5.29\u2009\u00b1\u20090.21, 5.35\u2009\u00b1\u20090.22, 5.41\u2009\u00b1\u20090.25 and 5.65\u2009\u00b1\u20090.63%, respectively. In study IV, values for Lymphocytes were 33.92\u2009\u00b1\u20091.21, 35.25\u2009\u00b1\u20091.82, 34.91\u2009\u00b1\u20091.25 and 35.29\u2009\u00b1\u20091.63% in T0, T1, T2 and T3 group, respectively  determination to enhance the authenticity of the results. Likewise, human efficacy trial for insulin sensitivity/resistance by different test like HOMA-insulin resistance, QUIKI, and Matsuda should be conducted to unveil the mechanistic concerns."}
{"text": "In the crystal, the disaccharide and water mol\u00adecules form layers parallel to the  13H24O9\u00b7H2O, a structural model for part of bacterial O-anti\u00adgen polysaccharides from Shigella flexneri and Escherichia coli, crystallizes with four independent disaccharide mol\u00adecules and four water mol\u00adecules in the asymmetric unit. The conformation at the glycosidic linkage joining the two rhamnosyl residues is described by the torsion angles \u03c6H of 39, 30, 37 and 37\u00b0, and \u03c8H of \u221232, \u221235, \u221231 and \u221232\u00b0, which are the major conformation region known to be populated in an aqueous solution. The hexo\u00adpyran\u00adose rings have the 1C4 chair conformation. In the crystal, the disaccharide and water mol\u00adecules are associated through O\u2014H\u22efO hydrogen bonds, forming a layer parallel to the bc plane. The layers stack along the a axis via hydro\u00adphobic inter\u00adactions between the methyl groups.The title compound, C Shigella flexneri , which are defined, respectively, by H1A\u2014C1A\u2014O2B\u2014C2B, C1A\u2014O2B\u2014C2B\u2014H2B and H1B\u2014C1B\u2014O7B\u2014C7B. These torsion angles are (I)H =39\u00b0, \u03c8H = \u221232\u00b0 and \u03c6H(C7) = 49\u00b0, (II) \u03c6H = 30\u00b0, \u03c8H \u221235\u00b0 and \u03c6H(C7) = 52\u00b0, (III) \u03c6H = 36\u00b0, \u03c8H = \u221231\u00b0 and \u03c6H(C7) = 51\u00b0, and (IV) \u03c6H = 37\u00b0, \u03c8H = \u221232\u00b0 and \u03c6H(C7) = 51\u00b0, where (I)\u2013(IV) correspond to the four independent disaccharide mol\u00adecules 1\u20134, respectively, in Fig.\u00a02H, \u03c8H and \u03c6H(C7) angles are 35\u2005(4), \u221233\u2005(2) and 51\u2005(1)\u00b0, respectively. The \u03c6H torsion angle is governed by the exo-anomeric effect and should be approximately 40\u00b0 for an \u03b1-l-sugar, which is also the case in the title rhamnose-containing disaccharide  mixture solution at ambient temperature.The title compound was synthesized according to the published procedures  and treated as riding with Uiso(H) = 1.2\u20131.5Ueq. The O\u2014H bond and H\u22efH distances in the water mol\u00adecules were restrained to 0.85\u2005(1) and 1.34\u2005(1)\u2005\u00c5, respectively. The orientation of each water mol\u00adecule was adjusted and restrained with additional DFIX commands using parameters derived from a solid state DFT optimization of the crystal structure.Crystal data, data collection and structural refinement details are summarized in Table\u00a0210.1107/S2056989019006935/is5512sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019006935/is5512Isup2.hklStructure factors: contains datablock(s) I. DOI: 1915954CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64\u2005(16)\u00b0. In the crystal, mol\u00adecules are linked by O\u2014-H\u22efO and N\u2014H\u22efO hydrogen bonds, forming chains along [010]. In addition, weak C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions further link the structure into a three-dimensional network.The title mol\u00adecule adopts an  17H12N2O3\u00b7H2O comprises two mol\u00adecules of (E)-3-(1H-indol-2-yl)-1-(4-nitro\u00adphen\u00adyl)prop-2-en-1-one and a water mol\u00adecule. The main mol\u00adecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64\u2005(16)\u00b0. In the crystal, mol\u00adecules are linked by O\u2014-H\u22efO and N\u2014H\u22efO hydrogen bonds, forming chains along [010]. In addition, weak C\u2014H\u22efO, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions further link the structure into a three-dimensional network. The optimized structure was generated theoretically via a density functional theory (DFT) approach at the B3LYP/6\u2013311\u2005G++ basis level and the HOMO\u2013LUMO behaviour was elucidated to determine the energy gap. The obtained values of 2.70\u2005eV  and 2.80\u2005eV (DFT) are desirable for optoelectronic applications. The inter\u00admolecular inter\u00adactions were qu\u00adanti\u00adfied and analysed using Hirshfeld surface analysis.The asymmetric unit of the title compound, 2C In addition, the chalcone bridge consists of two different double bonds, C=C and C=O, which contribute to the conjugation of charge transfer, leading to their excellent structural and spectroscopic properties  group as an acceptor group because the decrease of the resonance effect leads to substantial changes in \u03c0-electron delocalization in the ring  level, providing information about the geometry of the mol\u00adecule. The optimized structure is shown in Fig.\u00a01b. The geometrical parameters are mostly within normal ranges, the slight deviations from the experimental values are due to the fact that the optimization is performed in isolated conditions, whereas the crystal environment and hydrogen-bonding inter\u00adactions affect the results of the X-ray structure \u2005\u00c5] and C9=C10 [1.310\u2005(5)\u2005\u00c5] bonds. The compound is twisted about the C10\u2014C11 bond with C9\u2014C10\u2014C11\u2014O1 torsion angle of \u221221.9\u2005(6)\u00b0. The corres\u00adponding torsion angle obtained from the DFT study is 0.08\u00b0. In addition, the mol\u00adecule is twisted about the C11\u2014C12 bond with an O1\u2014C11\u2014C12\u2014C13 torsion angle of 167.7\u2005(4)\u00b0 . The differences between the experimental and calculated values show that the inter\u00admolecular hydrogen bond involving the water mol\u00adecule does not affect the planarity of the compound. A previous study  adopts an c). The enone group (O1/C9\u2013C11) with maximum deviation of 0.082\u2005(3)\u2005\u00c5 at C11 forms dihedral angles of 21.5\u2005(2) and 16.3\u2005(2)\u00b0 with the indole ring system and the nitro-substituted benzene ring, respectively.The overall conformation of the mol\u00adecule can be described by the dihedral angle formed by the indole ring system (N1/C1\u2013C8) and the nitro-substituted benzene (C12\u2013C17) ring with a value of 37.64\u2005(16)\u00b0 Fig.\u00a01c. The evia O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds involving the solvent water mol\u00adecule. The water mol\u00adecule is connected to the carbonyl group and indole ring system by inter\u00admolecular O1W\u2014H1OW\u22efO1i and N1\u2014H1A\u22efO1W hydrogen bonds . Furthermore, C9\u2014H9A\u22efCg1 inter\u00adactions  are observed along the a-axis direction, completing the three-dimensional structure. Two of the anti-parallel mol\u00adecules are linked by \u03c0\u2013\u03c0 stacking inter\u00adactions  involving the centroids (Cg2 and Cg3) of the C1\u2013C6 and C12\u2013C17 rings with a centroid\u2013centroid distance Cg2\u22efCg3  of 3.534\u2005(3)\u2005\u00c5. These \u03c0\u2013\u03c0 inter\u00adactions further stabilize the crystal structure.In the crystal, four symmetry-related mol\u00adecules are connected to each other s Table\u00a01, formingon Fig.\u00a02. In addis Table\u00a01 link thene Fig.\u00a03a. Furthns Fig.\u00a03a involvCrystalExplorer3.1  pair and the full fingerprint is outlined in grey  plots were generated with ds Fig.\u00a04. The finds Fig.\u00a04. The H\u22efHde in . With the shape-indexed mapping, the C\u2014H\u22ef\u03c0 inter\u00adactions can be observed as a bright-red spot identified with black arrows in Fig.\u00a06b. The blue spots near the ring represent the reciprocal C\u2014H\u22ef\u03c0 inter\u00adactions.The presence of the C\u2014H\u22ef\u03c0 inter\u00adactions can be seen in the pale-orange spot inside the circle of black arrows on the Hirshfeld surface mapped over in Fig.\u00a06a. With Eg) between the highest occupied mol\u00adecular orbital (HOMO) and lowest unoccupied mol\u00adecular orbital (LUMO) is a crucial factor in elucidating the mol\u00adecular electrical transport properties. In the present study, the HOMO and LUMO were computed at the DFT/B3LYP/6-311G++ theoretical level and the respective plots of the frontier mol\u00adecular orbital are illustrated in Fig.\u00a07et al., 2014et al., 2015et al., 2018Frontier mol\u00adecular orbital analysis is a vital tool in the development of mol\u00adecular electronic properties. The energy gap -3-(2-methyl\u00adphen\u00adyl)-1-(4-nitro\u00adphen\u00adyl)prop-2-en-1-one ethan\u00adone (0.5\u2005mmol) and indole-2-carboxaldehyde (0.5\u2005mmol) was dissolved in methanol (20\u2005mL). Sodium hydroxide (NaOH) solution was then added dropwise under vigorous stirring. The reaction mixture was stirred for 5\u20136\u2005h at room temperature. The final precipitate was filtered, washed with distilled water and recrystallized by slow evaporation from acetone solution to obtain orange plate-shaped crystals.The title compound was synthesized Uiso(H) = 1.2Ueq(C). The water O atom was refined with half-occupancy. The O- and N-bound H atoms were located from difference-Fourier maps and refined freely.Crystal data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018014329/lh5883sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018014329/lh5883Isup3.cmlSupporting information file. DOI: 1846181CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The mol\u00adecules are connected  N,N-di\u00admethyl\u00adformamide (1/1/1), C14H10O4S2\u00b7C7H5ClO2\u00b7C3H7NO, contains a mol\u00adecule each of 2,2\u2032-di\u00adthiodi\u00adbenzoic acid (DTBA), 2-chloro\u00adbenzoic acid (2CBA) and di\u00admethyl\u00adformamide (DMF). The DTBA mol\u00adecule is twisted [the C\u2014S\u2014S\u2014C torsion angle is 88.37\u2005(17)\u00b0] and each carb\u00adoxy\u00adlic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6\u2005(3) and 12.5\u2005(3)\u00b0]. A small twist is evident in the mol\u00adecule of 2CBA [CO2/C6 dihedral angle = 4.4\u2005(4)\u00b0]. In the crystal, the three mol\u00adecules are connected by hydrogen bonds with the two carb\u00adoxy\u00adlic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {\u22efHOCO}2 synthon, and the second carb\u00adoxy\u00adlic acid of DTBA linked to the DMF mol\u00adecule via a seven-membered {\u22efHOCO\u22efHCO} heterosynthon. The three-mol\u00adecule aggregates are connected into a supra\u00admolecular chain along the a axis via DTBA-C\u2014H\u22efO(hydroxyl-2CBA), 2CBA-C\u2014H\u22efO(hydroxyl-DTBA) and DTBA-C\u2014H\u22efS(DTBA) inter\u00adactions. Supra\u00admolecular layers in the ab plane are formed as the chains are linked via DMF-C\u2014H\u22efS(DTBA) contacts, and these inter-digitate along the c-axis direction without specific points of contact between them. A Hirshfeld surface analysis points to additional but, weak contacts to stabilize the three-dimensional architecture: DTBA-C=O\u22efH(phenyl-DTBA), 2CBA-Cl\u22efH(phenyl-DTBA), as well as a \u03c0\u2013\u03c0 contact between the delocalized eight-membered {\u22efHOC=O}2 carb\u00adoxy\u00adlic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.The asymmetric unit of the three-component title compound, 2,2\u2032-di\u00adthiodi\u00adbenzoic acid\u20132-chloro\u00adbenzoic acid\u2013 In this three-component crystal, one of the carb\u00adoxy\u00adlic acid groups of the DTBA mol\u00adecule forms hydrogen bonds to DMF rather than to 2CBA. Herein, the crystal and mol\u00adecular structures of the title co-crystal solvate are described along with an analysis of the calculated Hirshfeld surfaces and a computational chemistry study.Recent bibliographic reviews have highlighted the rich coord\u00adination chemistry based on ligands derived from 2-mercapto\u00adbenzoic acid (2-MBA) . The asymmetric unit comprises 2,2\u2032-di\u00adthiodi\u00adbenzoic acid (DTBA), 2-chloro\u00adbenzoic acid (2CBA) and a di\u00admethyl\u00adformamide (DMF) solvent mol\u00adecule in a stoichiometric 1:1:1 ratio, as illustrated in Fig.\u00a01The title compound, (I)et al., 2007As anti\u00adcipated, crystallography reveals that the original 2-mercapto\u00adbenzoic acid underwent oxidation to yield a mol\u00adecule of DTBA, with the benzoic acid moieties being bridged through a di\u00adsulfide bond [S1\u2014S2 = 2.053\u2005(1)\u2005\u00c5]. The presence of carb\u00adoxy\u00adlic acid groups is confirmed by the disparity in the bond lengths for C8\u2014O4, O3 [1.317\u2005(4) and 1.229\u2005(4)\u2005\u00c5] and C21\u2014O6, O5 [1.326\u2005(4) and 1.209\u2005(4)\u2005\u00c5]. Both carb\u00adoxy\u00adlic acid groups (O3\u2014C8\u2014O4 and O5\u2014C21\u2014O6) are slightly twisted from the benzene rings (C9/C14 and C15/C20) to which they are bonded with the corresponding dihedral angles being 7.6\u2005(3) and 12.5\u2005(3)\u00b0, respectively. The C14\u2014S1\u2014S2\u2014C15 torsion angle is 88.37\u2005(17)\u00b0, indicating an almost orthogonal disposition between the benzene rings. The carbonyl-O3 and O5 atoms are oriented towards the di\u00adsulfide-S1 and S2 atoms with S1\u22efO3 and S2\u22efO5 distances of 2.713\u2005(2) and 2.661\u2005(3)\u2005\u00c5, respectively, and are indicative of hypervalent S\u2190O inter\u00adactions  and 1.320\u2005(4), respectively. The carb\u00adoxy\u00adlic acid group is almost co-planar with the phenyl ring (C2\u2013C7) as seen in the dihedral angle of 4.4\u2005(4)\u00b0 between their planes. Similarly, co-planarity is also noted between the chloride atom and benzene ring plane with the r.m.s deviation from the least-squares plane through the seven non-hydrogen atoms being 0.027\u2005\u00c5.PLATON .The geometric parameters characterizing the inter\u00adatomic contacts in the crystal of (I)2 homosynthon, as well as discrete DTBA-C11\u2014H11\u22efS1(DTBA) inter\u00adactions. These lead to a supra\u00admolecular chain along the crystallographic a direction, as indicated in Fig.\u00a02b). Inter\u00adactions between the chains leading to a layer in the ab plane occur through DMF-C24\u2014H24C\u22efS2(DTBA) contacts, Fig.\u00a02c). The layers inter-digitate along the c-axis direction with only weak contacts between them as detailed in the next section.The resultant three-mol\u00adecule aggregates are connected by DTBA-C10\u2014H10\u22efO2(hydroxyl-2CBA) and 2CBA-C3\u2014H3\u22efO4(hydroxyl-DTBA) inter\u00adactions to form a non-symmetric, ten-membered {\u22efOCCCH}Crystal Explorer 17 dnorm maps of the respective mol\u00adecules in the aggregates are shown in Fig.\u00a03dnorm map signifying close contacts which origin\u00adate from DTBA-O\u2014H\u22efO(carbonyl-2CBA), DTBA-O\u2014H\u22efO(carbonyl-DMF), DTBA-C=O\u22efH(hydroxyl-2CBA) and DTBA-C=O\u22efH(DMF). Other red spots are observed through the dnorm map, albeit with relatively weak intensity. The contacts are consistent with those identified above except for some additional inter\u00adactions such as DTBA-C=O\u22efH(phenyl-DTBA), 2CBA-Cl\u22efH(phenyl-DTBA) as well as a \u03c0\u2013\u03c0 contact between the delocalized eight-membered {\u22efHOC=O}2 carb\u00adoxy\u00adlic dimer and the phenyl ring of 2CBA, Fig.\u00a03b). To validate the non-conventional \u03c0\u2013\u03c0 contact, the inter\u00adacting mol\u00adecules were subjected to electrostatic potential (ESP) mapping using Spartan\u201916  level of theory. The ESP mapping shows that the dimeric ring ranges from electropositive to neutral within the centre of the ring while the phenyl ring of 2CBA is mainly neutral indicating that the inter\u00adaction is mainly diffusive in nature, Fig.\u00a03c) and (d). As for the 2CBA and DMF mol\u00adecules, the corresponding dnorm maps (not shown) are reflective of their inter\u00adactions with the DTBA mol\u00adecule.The di + de \u223c2.20\u2005\u00c5), O\u22efH/H\u22efO , C\u22efH/H\u22efC , S\u22efH/H\u22efS , Cl\u22efH/H\u22efCl  and other contacts (14.0%). Almost all of these contacts are shorter than their corres\u00adponding sum van der Waals radii, with H\u22efH, O\u22efH, C\u22efH, S\u22efH and Cl\u22efH being \u223c2.4, \u223c2.72, \u223c2.9, \u223c3.0 and \u223c2.95\u2005\u00c5, respectively.The two-dimensional fingerprint plots were generated to qu\u00adantify the close contacts identified on the Hirshfeld surfaces. The overall fingerprint plot of (I)di + de contact distance of \u223c2.18 and \u223c2.24\u2005\u00c5 for DTBA and 2CBA, respectively. The O\u22efH/H\u22efO contacts are the second most dominant contact for the individual mol\u00adecules which lead to the distinctive spikes in the corresponding decomposed fingerprint plots with a contribution of 26.4% for DTBA and 22.2% for 2CBA. Further delin\u00adeation of the contact shows that DTBA possesses about 11.1% of -H\u22efO- and 15.3% -O\u22efH- compared to 2CBA with 10.9 and 11.2% of the equivalent contacts, both with approximately the same di + de contact distance of \u223c1.70\u2005\u00c5 for DTBA and \u223c1.62\u2005\u00c5 for 2CBA. Additional contacts for DTBA and 2CBA are respectively dominated by C\u22efH/H\u22efC , S\u22efH/H\u22efS  and Cl\u22efH/H\u22efCl . As for the DMF solvent mol\u00adecule, this exhibits a relatively different claw-like profile with several disproportional spikes observed in the fingerprint plot mainly owing to the asymmetric inter\u00adaction environment for the O\u22efH/ H\u22efO contact, in which the contribution of -O\u22efH- contact to the Hirshfeld surfaces is about 14.6% (di + de \u223c1.60\u2005\u00c5), while the -H\u22efO- contact is about 11.2% (di + de \u223c2.22\u2005\u00c5) that can be summed up to yield an overall 25.8%. The contribution of other short contacts is noted in decreasing order: H\u22efH , C\u22efH/ H\u22efC  and H\u22efS , respectively.The DTBA and 2CBA mol\u00adecules display similar fingerprint patterns having a claw-like profile in the respective full fingerprint plots, implying the existence of nearly identical inter\u00adactions between the mol\u00adecules which is expected considering the similarity of their mol\u00adecular structures. Detailed analysis of the decomposed fingerprint plots shows that H\u22efH is the most prevalent contact for the mol\u00adecules, with the percentage contribution to the overall contacts of 29.7 and 25.0% and minimum Crystal Explorer 17, Table\u00a02Eint) of \u221273.2\u2005kJ\u2005mol\u22121. This energy is about one and a half-fold greater than the second strongest inter\u00adaction that occurs between DTBA-DMF [DTBA-O\u2014H\u22efO(carbonyl-DMF)/ DTBA=O\u22efH\u2014C-(DMF)] with an Eint = \u221245.9\u2005kJ\u2005mol\u22121. The disparity in energy is likely due the replacement of one O\u2014H\u22efO hydrogen bond with a C\u2014H\u22efO inter\u00adaction in the latter inter\u00adaction.The energy calculations through 2 and the 2CBA-benzene ring gives an energy of \u221215.9\u2005kJ\u2005mol\u22121 which is considered weak in nature. This indicates the energy is mainly dominated by dispersive forces, Table\u00a02Eint for other inter\u00adactions present in the crystal were also calculated and the results are summarized as in Table\u00a02\u22121 which can be considered weak.On the other hand, the \u03c0\u2013\u03c0 inter\u00adaction between the hydrogen bond-mediated dimer of (DTBA)c-axis direction. A relatively weaker dispersion force co-exists along with the main energy framework due to \u03c0\u2013\u03c0 inter\u00adactions which help to sustain the overall mol\u00adecular packing of (I)The energy frameworks of (I)ba), in (II) the two DTBA mol\u00adecules (DTBA-IIa and DTBA-IIb) form hydrogen bonds with each other, to yield a non-symmetric homosynthon, and with the two remaining carb\u00adoxy\u00adlic acid groups being hydrogen bonded to two 3CBA mol\u00adecules to give rise to a four-mol\u00adecule aggregate.A structural analogue of (I)Mercury ca 12.4%) which is approximately 6% greater than 2CBA in (I)ca 6.3%).Both (I)et al., 2016et al., 20062 synthon in carb\u00adoxy\u00adlic acid structures, i.e. 33%, emphasizing that this particular synthon can be readily disrupted in the presence of competing synthons  solution of the ground mixture. M.p. 437.3\u2013438.9\u2005K. IR (cm\u22121): 3076 \u03bd(C\u2014H), 1678 \u03bd(C=O), 1473 \u03bd(C=C), 1426 \u03b4(C\u2014H), 736 \u03b4(C\u2014Cl).All chemical precursors were of reagent grade and used as received without further purification. 2-Mercapto\u00adbenzoic acid  was mixed with 2-chloro\u00adbenzoic acid  and ground for 15 mins in the presence of a few drops of methanol. The procedure was repeated three times. Colourless blocks were obtained through the careful layering of toluene (1\u2005ml) on an Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen-bound H atoms were located from difference Fourier maps and refined without constraint. Owing to poor agreement, one reflection, i.e. (4 2 2), was omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901900375X/hb7808sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901900375X/hb7808Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900375X/hb7808Isup3.cmlSupporting information file. DOI: 1903993CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the components are linked by Owater\u2014H\u22efN, N\u2014H\u22efOwater and N\u2014H\u22efN hydrogen bonds, forming chains along the [100] direction. The chains are linked by C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming layers parallel to the ab plane. Finally, the layers are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional structure.The asymmetric unit of the title compound contains two independent organic mol\u00adecules which differ primarily in the dihedral angle between the aromatic rings,  20H20N4O\u00b70.5H2O, contains two independent organic mol\u00adecules (1 and 2) and a water mol\u00adecule of crystallization. The two mol\u00adecules differ primarily in the dihedral angles between the aromatic rings, which are 7.79\u2005(7) and 29.89\u2005(7)\u00b0 in mol\u00adecules 1 and 2, respectively. In each mol\u00adecule there is intra\u00admolecular C\u2014H\u22efO hydrogen bond forming an S(6) ring motif. In mol\u00adecule 1 there is an intra\u00admolecular N\u2014H\u22ef\u03c0(pyrazole) inter\u00adaction and an intra\u00admolecular C\u2014H\u22ef\u03c0(pyrazole) inter\u00adaction present. Mol\u00adecule 1 is linked to mol\u00adecule 2 by a C\u2014H\u22ef\u03c0(benzene ring) inter\u00adaction. An intra\u00admolecular N\u2014H\u22efN hydrogen bond and an intra\u00admolecular C\u2014H\u22efN hydrogen bond are also present in mol\u00adecule 2. In the crystal, the three components are linked by Owater\u2014H\u22efN, N\u2014H\u22efOwater and N\u2014H\u22efN hydrogen bonds, forming chains along the [100] direction. The chains are linked by C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming layers parallel to the ab plane. Finally, the layers are linked by C\u2014H\u22ef\u03c0 inter\u00adactions, forming a three-dimensional structure.The asymmetric unit of the title compound, C We report herein on its crystal and mol\u00adecular structures along with the Hirshfeld surface analysis.Pyrazole derivatives are biologically active heterocyclic compounds  ring motif  and 1.3596\u2005(16)\u2005\u00c5, respectively.The pyrazole ring (N1/N2/C2\u2013C4) in mol\u00adecule 1 is inclined to the benzene rings (C7\u2013C12 and C14\u2013C19) by 70.83\u2005(8) and 76.79\u2005(8)\u00b0, respectively. The corresponding dihedral angles in mol\u00adecule 2, involving the N5/N6/C22\u2013C24 pyrazole ring and the C27\u2013C32 and C34\u2013C39 benzene rings, are 68.47\u2005(8) and 81.91\u2005(8)\u00b0, respectively. In both mol\u00adecules there is an intra\u00admolecular C\u2014H\u22efO hydrogen bond forming an if Fig.\u00a01. In the In mol\u00adecule 1, an intra\u00admolecular N\u2014H\u22ef\u03c0(pyrazole) inter\u00adaction and an intra\u00admolecular C\u2014H\u22ef\u03c0(pyrazole) inter\u00adaction are present Fig.\u00a01. Mol\u00adecuwater\u2014H\u22efN and N\u2014H\u22efOwater hydrogen bonds, and by N\u2014H\u22efN hydrogen bonds, forming chains propagating along the a-axis direction; see Fig.\u00a03ab plane \u00adphen\u00adyl]acetamides gave many hits. A search for the substructure [2-(benzyl\u00adidene\u00adamino)\u00adphen\u00adyl]acetamide gave 19 hits, some of which are metal complexes. The structures most similar to the title compound include: N-(2-{[(2-hy\u00addroxy\u00adphen\u00adyl)methyl\u00adidene]amino}\u00adphen\u00adyl)-2,2-di\u00admethyl\u00adpropanamide aniline -N-(o-nitro\u00adbenzil\u00adidene)aniline -N-(m-nitro\u00adbenzil\u00adidene)aniline \u00b0 for POSPET, 16.2\u2005(2)\u00b0 for RIHHOF, 41.81\u2005(14)\u00b0 for RIHHUL and 11.2\u2005(4)\u00b0 in RIHJAT. The dihedral angles between the aromatic rings in the title compound are 7.79\u2005(7) and 29.89\u2005(7)\u00b0 in mol\u00adecules 1 and 2, respectively.A search of the Cambridge Structural Database -1-(2-hy\u00addroxy\u00adphen\u00adyl)ethyl\u00adidene]amino}\u00adphen\u00adyl)-2-meth\u00adoxy\u00adacet\u00adamide amino]\u00adphen\u00adyl}acet\u00adamides gave an inter\u00adesting hit, namely that for CrystalExplorer17.5  to 1.583 (blue) \u00c5. Fig.\u00a06dnorm mapped on the Hirshfeld surface.The Hirshfeld surface analyse was carried out using a (H\u22efH) illustrates the two-dimensional fingerprint of the  points associated with hydrogen atoms. It is characterized by an end point that points to the origin and corresponds to id = ed = 1.08\u2005\u00c5, which indicates the presence of the H\u22efH contacts in this study (54%). Fig.\u00a08b (C\u22efH/H\u22efC) shows the contacts between the carbon atoms inside the surface and the hydrogen atoms outside the surface of Hirshfeld and vice versa (24%). The O\u22efH/H\u22efO (11.5%) plot shows two symmetrical wings on the left and right sides . The N\u22efH/H\u22efN inter\u00adactions (6.5%) are visualized in Fig.\u00a08d.Fig.\u00a07es Fig.\u00a08c. The NN-2-amino\u00adphenyl-5-methyl\u00adpyrazol-3-ylacetamide  with 4-methyl\u00adbenzaldehyde  in acetone (50\u2005ml) for 3\u2005h. The solvent was evaporated under vacuum, and then water was added. The precipitate formed was filtered under vacuum and purified through silica gel column chromatography using hexa\u00adne/ethyl acetate , yielding colourless rod-like crystals of the title compound (yield 63%).The title compound was prepared by stirring Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018017747/xu5954sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018017747/xu5954Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017747/xu5954Isup3.cmlSupporting information file. DOI: 1885214CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules form stacks along the [001] direction. The crystal packing is further stabilized by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22efCl and C\u2014H\u22ef\u03c0 contacts.The title compound, C 14H12ClNO3, is a Schiff base that exists in the keto\u2013enamine tautomeric form and adopts a Z configuration. In the crystal, the dihedral angle between the planes of the benzene rings is 5.34\u2005(15)\u00b0. The roughly planar geometry of the mol\u00adecule is stabilized by a strong intra\u00admolecular N\u2014H\u22efO hydrogen bond. In the crystal, pairs of centrosymmetrically related mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming R22(10) rings. Besides this, the mol\u00adecules form stacks along the [001] direction with C\u2014H\u22ef\u03c0 and C\u2014H\u22efCl contacts between the stacks. The inter\u00admolecular inter\u00adactions in the crystal were analysed using Hirshfeld surfaces. The most significant contribution to the crystal packing is from H\u22efH contacts (30.8%).The title compound, C Such compounds can exist in two tautomeric forms, viz. keto\u2013enamine (N\u2014H\u22efO) and phenol\u2013imine (N\u22efH\u2014O) . The whole mol\u00adecule is almost planar, with a dihedral angle of 5.34\u2005(15)\u00b0 between the benzene ring planes. The meth\u00adoxy C14 atom deviates from the plane of the C1\u2013C6 benzene ring by 0.038\u2005(4) \u00c5. The torsion angles C1\u2014C6\u2014N1\u2014C7 and N1\u2014C7\u2014C8\u2014C9 are 5.8\u2005(5) and \u22120.6\u2005(5)\u00b0, respectively. The planar mol\u00adecular conformation is stabilized by the intra\u00admolecular N1\u2014H2\u22efO2 hydrogen bond -(phenyl\u00adimino)\u00admeth\u00adyl]-benzene-1,2-diol fragment revealed eight hits where this fragment adopts the keto\u2013enamine tautomeric form and 21 hits where it exists as the phenol\u2013imine tautomer. Distinctive bond lengths  in the title structure are the same within standard uncertainties as the corresponding bond lengths in the structures of 2-hy\u00addroxy-6-[(2-meth\u00adoxy\u00adphen\u00adyl)amino\u00admethyl\u00adene]cyclo\u00adhexa-2,4-dienone imino\u00admeth\u00adyl]benzene-1,2-diol  and 5-chloro-2-meth\u00adoxy\u00adaniline , both in 15\u2005mL of ethanol, with subsequent stirring for 5\u2005h under reflux. Single crystals were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) for methyl H atoms. The O- and N-bound H atoms were located in a difference map and freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019002123/yk2119sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019002123/yk2119Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019002123/yk2119Isup3.cmlSupporting information file. DOI: 1886956CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Dear Editor,+ ROR\u2010gamma\u2010T+ innate lymphoid cell (ILC3) development.\u2212/\u2212 mice,The BTB\u2010ZF  proteins play essential roles in the development of the immune system.\u2212/\u2212 mouse. According to the surface maker expression by flow cytometry, D1 is a DN1\u2010like cell line, which is CD44+CD25\u2212IL\u20107R\u03b1+. We sorted double positive (DP), CD4 single positive (SP) and CD8SP thymocytes from wild\u2010type C57BL/6 and IL\u20107R\u03b1 mutant mice mentioned above \u2010dependent thymic cell line derived from a p53\u03b1+Figure\u00a0A. D1 cel+ cells to establish the stable cell line (Figure\u00a0hi thymocytes in ScanT mice was also higher than that of their wild\u2010type littermates, although the percentage of TCR\u03b2hi thymocytes in ScanT mice was severely reduced (Figure\u00a0Next we investigated the effect of Zbtb1 on IL\u20107R\u03b1 expression. We transduced the D1 cells with either retroviral vector Mir\u2010CTR or Zbtb1\u2010overexpressing retrovirus, and sorted the GFPe Figure\u00a0B. Consise Figure\u00a0C. Interee Figure\u00a0D. The ILd Figure\u00a0E.Altogether, our results suggest that Zbtb1 and IL\u20107R\u03b1 signalling can regulate each other during T\u2010cell development. IL\u20107R\u03b1 signalling negatively regulate Zbtb1, and vice versa. Detailed molecular mechanisms by which Zbtb1 regulate IL\u20107R\u03b1 expression in T cells are still under investigation.The authors confirm that there are no conflicts of interest.\u00a0Click here for additional data file."}
{"text": "Arising from M. A. Bakar et al. Nature Commun. 10.1038/s41467-017-00720-3 (2017)1 A number of X-ray studies have reported gold compounds with short AuI\u00b7\u00b7\u00b7H contacts, but solid spectroscopic evidence for AuI\u00b7\u00b7\u00b7H bonding has been missing.1 Notably, during the revision of this work, Bourissou et al.2 and Straka et al.3 have provided evidence of true intramolecular AuI\u00b7\u00b7\u00b7H hydrogen bonds in [Cl\u2013Au\u2013L]+ complexes, where L is a protonated N-heterocyclic carbene. The studied compounds feature intramolecular AuI\u00b7\u00b7\u00b7H+\u2013N bonds detected by means of NMR2 and infrared spectroscopies.3Hydrogen bonding to gold(I) and its effect on the structure and dynamics of molecules have been a matter of long debate.4 reported compound 1  NMR resonances at respective H(C) nuclei in 1 highly deshielded with respect to precursor 2  auride-like\u00b7\u00b7\u00b7hydrogen bonding interaction. In addition, computational analysis of NMR chemical shifts reveals that the deshielding effects at respective hydrogen nuclei are not directly related to Au\u00b7\u00b7\u00b7H\u2013C hydrogen bonding in 1. It is well known that interactions of hydrogen with transition metals compounds may influence the 1H NMR shifts in unexpected ways.5Here, we show that the Au1, which is one of the four Au\u00b7\u00b7\u00b7H\u2013C contacts in the molecule  as proposed in ref. 4. The calculated minimum Au\u00b7\u00b7\u00b7H distances (2.61\u20132.62\u2009\u00c5) are in excellent agreement with the reported ones (2.61\u20132.65\u2009\u00c5). To afford computational analysis of NMR chemical shifts9 (\u03b4), the P(Ph)2 groups in 1 and 2 were replaced by P(CH3)2 groups in model systems 1\u2032 and 2\u2032 .8 Notably, the absence of the bulky P(Ph)2 ligands causes rotation of the central phenyl groups away from the Au6 cluster. The Au\u00b7\u00b7\u00b7H distances increase from 2.6\u2009\u00c5 to 2.77\u2009\u00c5 and the Au\u2013H2\u2013C2 angles bend from 167\u00b0 to 144\u00b0 2 ligands that potentially stabilize the whole cluster via dispersion interactions among themselves.10 To avoid these undesirable changes in calculations, we fixed the core of 1 and 2 in optimization of 1\u2032 and 2\u2032 and only methyl groups were optimized.In the following, we analyze Au2\u00b7\u00b7\u00b7H2\u2013C2 contact in ule Fig.\u00a0. Computa1\u2032 shows a low ED (0.016 e.bohr\u22123) with positive Laplacian (0.037 e.bohr\u22125) at the line critical point (LCP) of Au2\u00b7\u00b7\u00b7H2 interaction. These values are\u00a0less than a half of those for reported Au\u00b7\u00b7\u00b7H+\u2013N bonds.6 Small electron exchange between Au2 and H2 of 0.07 e (e\u2009=\u2009electron) is consistent with a dispersive interaction.12 The direction of the charge transfer in Au2\u00b7\u00b7\u00b7H2 interaction is from Au2 to H2  in 1\u2032 have negative charge, about \u22120.15\u2009e  analysis of 13 analysis of 1\u2032 reveals a weak Au2\u00b7\u00b7\u00b7H2\u2013C2 interaction channel  is found between H2\u2013C2 and Au3 6p orbitals . This further points to a minimal stabilization effect of Au\u00b7\u00b7\u00b7H\u2013C bonding in 1.Extended transition state-natural orbitals for chemical valence (ETS-NOCV)als Fig.\u00a0. Notablyals Fig.\u00a0 is also 1H chemical shifts between 1 and 2 (1\u2032 and 2\u2032) are in excellent agreement with the experimental ones, for H2 \u03941\u20132\u2009=\u20094.4 ppm, \u03941\u2032\u22122\u2032\u2009=\u20093.6 ppm, and \u0394exp1\u20132\u2009=\u20094.4 ppm  arises from the diamagnetic part of the NMR chemical shift, \u0394\u03b4dia, which can be rationalized only by a depletion of electron density (ED) at the H2 nuclei. Molecular orbital (MO) analysis of \u0394\u03b4dia identifies that main part \u0394\u03b4dia (1.3 of 1.6 ppm) originates from four Au\u2013P \u03c0-back-bonding MOs  at H2, H4, and H6 nuclei4 given in brackets in Fig.\u00a0The calculated differences in 1\u2032\u22122\u2032 deshielding difference at H2 nuclei (2 ppm) is dominated by local Ramsey-type paramagnetic couplings15 between H2\u2013C2 \u03c3-bond  with C2 2py* in 1\u2032, which is not possible in 2\u2032, increases the MO\u2009\u2194\u2009MO* overlap in orbital magnetic couplings.16 This leads to the ~0.5 ppm larger paramagnetic deshielding at H2 in 1\u2032 in this particular coupling  in 2\u2032 contributes only by 0.2 ppm. An analogous mechanism is likely to be responsible also for the deshielding resonance at C2. The paramagnetic part of the \u0394ing Fig.\u00a0. Overall1 are an example of a weak  auride-like\u00b7\u00b7\u00b7hydrogen interaction, with small overall  stabilizing effect on the cluster structure. Instead, the stabilizing effect can be attributed to the dispersion interactions among the P(Ph)2 groups, as documented previously.10 Distinct \u03b4(1H) NMR deshielding of C\u2013H groups in contact with Au6 cluster in 1 as compared with the precursor 2 is due to (a) the differential ED at the H2 atom in 1 as compared to precursor 2, and (b) side-on orbital interactions between nearby Au3 atom and H\u2013C MOs that increase the efficiency of the local Ramsey-type deshielding paramagnetic couplings in molecule 1 as compared with corresponding couplings in precursor 2.We conclude that the short Au\u00b7\u00b7\u00b7H contacts in Supplementary Information"}
{"text": "It crystallizes in the non-centrosymmetric space group Pna21, with one mol\u00adecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(tri\u00adfluoro\u00admeth\u00adyl)phenyl and tetra\u00adzole], which are twisted by 76.8\u2005(1)\u00b0 relative to each other because of significant steric hindrance of the tri\u00adfluoro\u00admethyl group at the ortho position of the benzene ring. In the crystal, very weak C\u2014H\u22efN and C\u2014H\u22efF hydrogen bonds and aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions link the mol\u00adecules into a three-dimensional network. To further analyse the inter\u00admolecular inter\u00adactions, a Hirshfeld surface analysis, as well as inter\u00adaction energy calculations, were performed.The title compound, C Their biological properties, including anti\u00adviral, anti\u00adcancer, anti-tuberculosis, anti\u00adfungal and anti\u00adoxidant activities have been shown by numerous studies  \u03c0,\u03c3-complexes possessing non-linear optical properties 2(CF3SO3)2] 2]BF4 and [Cu(C11H9F3N4S)(NH2SO3)(MeOH)] based on 5-[(prop-2-en-1-yl)sulfan\u00adyl]-1-[2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]-1H-tetra\u00adzole (I)11H9F3N4S) have been reported recently 2]BF4 [dihedral angle = 78.0\u2005(1)\u00b0] and [Cu(C11H9F3N4S)(NH2SO3)(MeOH)] [85.5\u2005(1)\u00b0]  as well as calculation of the inter\u00adaction energies were performed using CrystalExplorer . Fingerprint plots were produced to show the inter\u00admolecular surface bond distances with the regions highlighted for C\u2014H\u22efF  and C\u2014H\u22efN  inter\u00adactions. The contribution to the surface area for H\u22efH contacts is 19.8%.To further analyse the inter\u00admolecular inter\u00adactions between the mol\u00adecules of (I)\u22efF Fig.\u00a05b and C\u2014\u22efN Fig.\u00a05c inter\u00adCrystalExplorer. The total inter\u00admolecular energy is the sum of energies of four main components, viz. electrostatic, polarization, dispersion and exchange-repulsion factors of 1.057, 0.740, 0.871 and 0.618, respectively  covers C\u2014H\u22efN and C\u2014H\u22efF inter\u00adactions with the neighbouring mol\u00adecule generated by the symmetry code \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, z\u00a0\u2212\u00a0\u22121 and are mainly dispersive in nature.The inter\u00adaction energies in (I)et al., 2016H-tetra\u00adzoles are known only as ligands in the structures of copper(I) and silver(I) \u03c0-complexes. In the crystal structures of bis\u00ad[\u03bc2-\u03b72-5--1-phenyl-1H-tetra\u00adzole]di\u00adaqua\u00addisilver bis(tetra\u00adfluoro\u00adborate) sulfan\u00adyl]-1H-tetra\u00adzole}di\u00adaquadicopper bis\u00ad(tetra\u00adfluoro\u00adborate) -5-[(prop-2-en-1-yl)sulfan\u00adyl]-1H-tetra\u00adzole}di\u00adaqua\u00addicopper bis\u00ad(tetra\u00adfluoro\u00adborate) ethanol solvate sulfan\u00adyl]-1-[2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]-1H-tetra\u00adzole}bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonato)\u00addicopper {\u03b72-1--5-[(prop-2-en-1-yl)sulfan\u00adyl]-1H-tetra\u00adzole}copper(I)} sulfanyl group is slightly elongated to 1.35\u20131.38\u2005\u00c5, in comparison with noncoordinated olefin bond value. The other S-substituted 1-phenyl-1H-tetra\u00adzole-5-thiol structures in the Cambridge Structural Database have different alkyl substit\u00aduents, such as 2-naphthyl benzene was distilled in vacuo.The title compound was synthesized from 2-(tri\u00adfluoro\u00admeth\u00adyl)aniline by a multi-step reaction. Commercially available 2-(tri\u00adfluoro\u00admeth\u00adyl)aniline  was dissolved in the minimum amount of benzene and treated with carbon di\u00adsulfide  and tri\u00adethyl\u00adamine . The solution was cooled to 273\u2005K and left for 5\u2005d. After complete precipitation of the tri\u00adethyl\u00adammonium di\u00adthio\u00adcarbamate salt, the solution was filtered. The solid was washed with anhydrous ether and air-dried for about 10\u2005min. The salt was then dissolved in about 7.5\u2005ml of chloro\u00adform, treated with 1.4\u2005ml of tri\u00adethyl\u00adamine and cooled to 273\u2005K. To this solution was added ethyl chloro\u00adformate  dropwise over a 15\u2005min period under intensive stirring. The resulting solution was stirred at 273\u2005K for 10\u2005min and allowed to warm to room temperature over 1\u2005h. The chloro\u00adform solution was washed with 3 3  and refluxed under intensive stirring until the suspension disappeared. The solution was cooled to room temperature and washed with TBME. The water fraction was separated and acidified with 3 M HCl (Caution! During the acidification beware of toxic HN3 gas). The sediment of 1-[2-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]-1H-tetra\u00adzole-5-thiol was separated by filtration and used for alkyl\u00adation without further purification.The obtained iso\u00adthio\u00adcyanate  was mixed with water (10\u2005ml) and NaNH-tetra\u00adzole-5-thiol  was dissolved in a solution of KOH  in ethanol (10\u2005ml). To the solution allyl bromide  was added and the mixture was heated at 323\u2005K for 1\u2005h. The solvent was removed in vacuo and to the residue was added water (5\u2005ml) and di\u00adchloro\u00admethane (10\u2005ml). The di\u00adchloro\u00admethane was separated and removed to give the title compound. Colourless blocks of (I)1-[2-(Tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]-11H , \u03b4, p.p.m. 8.03 , 7.98\u20137.88 , 7.71 , 5.94 , 5.36 , 5.18 , 3.98 . Analysis calculated for C11H9F3N4S: C, 46.15; H, 3.17; N, 19.57; S, 11.20; found: C, 45.97; H, 3.04; N, 19.49; S, 11.27.NMR Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019011459/hb7842sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019011459/hb7842Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019011459/hb7842Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019011459/hb7842Isup4.cmlSupporting information file. DOI: 1947200CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-imidazol-3-ium chloride (IOH\u00b7Cl) is a new imidazolium salt with a hy\u00addroxy functionality.The title compound, 1,3-bis\u00ad(4-hy\u00addroxy\u00adphen\u00adyl)-1 H-imidazol-3-ium chloride (IOH\u00b7Cl), C15H13N2O2+\u00b7Cl\u2212, is a new imidazolium salt with a hy\u00addroxy functionality. The synthesis of IOH\u00b7Cl was achieved in high yield via a two-step procedure involving a di\u00adaza\u00adbutadiene precursor followed by ring closure using tri\u00admethylchloro\u00adsilane and paraformaldehyde. The structure of IOH\u00b7Cl consists of a central planar imidazolium ring (r.m.s. deviation = 0.0015\u2005\u00c5), with out-of-plane phenolic side arms. The dihedral angles between the 4-hy\u00addroxy\u00adphenyl substituents and the imidazole ring are 55.27\u2005(7) and 48.85\u2005(11)\u00b0. In the crystal, O\u2014H\u22efCl hydrogen bonds connect the distal hy\u00addroxy groups and Cl\u2212 anions in adjacent asymmetric units, one related by inversion  and one by the n-glide  and ] counterparts, with inter\u00adplanar distances of 3.560\u2005(3) and 3.778\u2005(3)\u2005\u00c5. The only other noteworthy inter\u00admolecular inter\u00adaction is an O\u22efO (not hydrogen bonded) close contact of 2.999\u2005(3)\u2005\u00c5 between crystallographically different hy\u00addroxy O atoms on translationally adjacent mol\u00adecules .Imidazolium salts are common building blocks for functional materials and in the synthesis of N-heterocyclic carbene (NHC) as \u03c3-donor ligands for stable metal complexes. The title salt, 1,3-bis\u00ad(4-hy\u00addroxy\u00adphen\u00adyl)-1 NaOtBu and NaH)  represent a versatile class of ligand systems for metal-center activation or stabilization in modern organic synthesis (Arduengo para-phenol substituents (C4\u2013C9/O1 and C10\u2013C16/O2) bonded to the imidazolium N atoms [N1\u2014C4 = 1.442\u2005(3)\u2005\u00c5 and N2\u2014C10 = 1.441\u2005(3)\u2005\u00c5]. The phenol groups are out-of-plane, forming dihedral angles with the imidazolium ring of 55.27\u2005(7) and 48.85\u2005(11)\u00b0 for rings C4\u2013C9 and C10\u2013C15, respectively. The hy\u00addroxy H-atom coordinates were refined freely and are slightly out-of-plane of their respective phenolic groups; the torsion angles are 9.1\u2005(19)\u00b0 for C6\u2014C7\u2014O1\u2014H1O and 11\u2005(2)\u00b0 for C12\u2014C13\u2014O2\u2014H2O.In the structure of IOH\u00b7Cl Fig.\u00a02, there a\u2212 anion at  to two different IOH\u00b7Cl mol\u00adecules, one related by inversion and the other by the n-glide. These hydrogen bonds, viz. O1i\u2014H1Oi\u22efCl1 and O2ii\u2014H2Oii\u2014Cl1  and 21-screw [C3\u2014H3\u22efClv; symmetry code: (v) \u2212x\u00a0\u2212\u00a0y\u00a0+\u00a0z\u00a0+\u00a0b and Table\u00a01a\u2013f) qu\u00adantify the majority of inter\u00admolecular contacts as H\u22efH  and C\u22efH . In these diagrams, the O\u2014H\u22efCl hydrogen bonds are indicated by sharp diagonal jutting spikes , while C\u2014H\u22efO inter\u00adactions give less-pronounced spikes . C\u22efC contacts, which are all as a result of \u03c0\u2013\u03c0 stacking, account for 6.6% of the inter\u00admolecular contacts .The most prominent inter\u00admolecular inter\u00adactions in the crystals of IOH\u00b7Cl are O\u2014H\u22efCl hydrogen bonds. These link the Cls Table\u00a01. Short ces Fig.\u00a07d, whilees Fig.\u00a07e. C\u22efC cts Fig.\u00a07f.et al., 2016) on the three-ring fragment of the title compound yielded over 600 hits, ranging from similar simple salts to metal complexes containing analogous NHC frameworks. A search with H atoms bonded to the three carbons of the imidazole ring gave 180 hits. Of these, 28 had mesityl substituents, including IHOQUS , and the unsubstituted phenyl analog IPh\u00b7ClO4 -1,4-diazabutadiene (1)Synthesis of the precursor : to a round-bottomed flask charged with 15\u2005ml of methanol, 4-phenolaniline  was added and stirred until fully dissolved. Glyoxal  was added to the reaction solution with stirring. Upon addition of glyoxal solution, 40 wt.% in H2O, a brown precipitate formed and the solution turned orange. The reaction was further stirred at room temperature for 5\u2005h and the solid was vacuum filtered and washed with cold methanol . Step 2, Synthesis of IOH\u00b7Cl: ethyl acetate (10\u2005ml) was pre-heated to 343\u2005K. To the hot solution was added (1)  and paraformaldehyde . The reaction mixture was stirred until all of the paraformaldehyde had dissolved. To this was added a solution of tri\u00admethyl\u00adchloro\u00adsilane (TMSCl)  in ethyl acetate (0.15\u2005ml) dropwise over 5\u2005min while stirring. The solution was stirred for 2\u2005h and then placed in a refrigerator (275\u2005K) overnight. The precipitate was collected by vacuum filtration and washed with cold ethyl acetate and ether until the filtrate was colorless, yielding a dark-orange solid . Crystals were grown by slow evaporation of a concentrated solution in acetone.The overall reaction for the synthesis of the title compound is depicted in Fig.\u00a01Uiso(H) = 1.5Ueq(O). Carbon-bound H atoms were included in calculated positions and refined using a standard riding model, with C\u2014H = 0.95\u2005\u00c5 and Uiso(H) = 1.2Ueq(C). Refinement progress was checked using an R-tensor .Crystal data, data collection, and structure refinement details are given in Table\u00a0210.1107/S2056989019011058/su5504sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019011058/su5504Isup2.hklStructure factors: contains datablock(s) I. DOI: 1946122CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title compound, the heterocyclic portion of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit adopts a flattened-boat conformation, while the oxazolidine ring adopts an envelope conformation. The 2-carbon link to the oxazole ring is perpendicular to the best plane through the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit. In the crystal, the mol\u00adecules form stacks extending along the normal to (104) through \u03c0-stacking inter\u00adactions between the two carbonyl groups and inversion-related oxazole rings. Aromatic rings from neighbouring stacks inter\u00adcalate to form an overall layer structure. 20H16Cl2N2O3S, is built up from a di\u00adhydro\u00adbenzo\u00adthia\u00adzine moiety linked by \u2013CH\u2013 and \u2013C2H4\u2013 units to 2,4-di\u00adchloro\u00adphenyl and 2-oxo-1,3-oxazolidine substituents, where the oxazole ring and the heterocyclic portion of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit adopt envelope and flattened-boat conformations, respectively. The 2-carbon link to the oxazole ring is nearly perpendicular to the mean plane of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit. In the crystal, the mol\u00adecules form stacks extending along the normal to (104) with the aromatic rings from neighbouring stacks inter\u00adcalating to form an overall layer structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (28.4%), H\u22efCl/Cl\u22efH (19.3%), H\u22efO/O\u22efH (17.0%), H\u22efC/C\u22efH (14.5%) and C\u22efC (8.2%) inter\u00adactions. Weak hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2014LUMO behaviour was elucidated to determine the energy gap.The title compound, C A puckering analysis of the heterocyclic portion  of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit gave the parameters QT = 0.1206\u2005(14)\u2005\u00c5, q2 = 0.1190\u2005(14)\u2005\u00c5, q3 = \u22120.0174\u2005(16)\u2005\u00c5, \u03c6 = 178.2\u2005(8)\u00b0 and \u03b8 = 98.4\u2005(8)\u00b0, indicating a flattened-boat conformation. A similar analysis for the oxazolidine ring C (O2/N2/C11\u2013C13) yielded q2 = 0.1125\u2005(18)\u2005\u00c5 and \u03c62 = 45.7\u2005(9)\u00b0, indicating an envelope conformation with atom C12 at the flap position and at a distance of 0.175\u2005(2)\u2005\u00c5 from the best plane of the other four atoms. The C9/C10 chain C is essentially perpendicular to the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit, as indicated by the C6\u2014N1\u2014C9\u2014C10 torsion angle of 90.61\u2005(19)\u00b0. In the heterocyclic ring B, the C1\u2014S1\u2014C8 [104.29\u2005(8)\u00b0], S1\u2014C8\u2014C7 [121.39\u2005(12)\u00b0], C8\u2014C7\u2014N1 [120.77\u2005(14)\u00b0], C7\u2014N1\u2014C6 [126.86\u2005(14)\u00b0], C6\u2014C1\u2014S1 [123.97\u2005(13)\u00b0] and N1\u2014C6\u2014C1 [121.60\u2005(15)\u00b0] bond angles are enlarged compared with the corresponding values in the closely related compounds (2Z)-2-(4-chloro\u00adbenzyl\u00adidene)-4-[2-(2-oxooxazoliden-3-yl)eth\u00adyl]-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (II), -2-[(4-fluoro\u00adbenzyl\u00adidene]-4-(prop-2-yn-1-yl)-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (III), -4-[2-eth\u00adyl]-2(phenyl\u00admethyl\u00adidene)-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (IV), ly Fig.\u00a01. The benC ring at \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01  and between C13=O3 and the C ring at \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z   through \u03c0-stacking inter\u00adactions between C7=O1 and the ] Figs. 2 and 3 \u25b8.CrystalExplorer17.5  analysis  have a nearly symmetrical distribution of points, Fig.\u00a08c, with thin edges at de + di = 2.88\u2005\u00c5. The fingerprint plot delineated into H\u22efO/O\u22efH contacts (17.0%), Fig.\u00a08d, has a pair of characteristic wings with a pair of spikes with the tips at de + di = 2.48\u2005\u00c5. In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions, the pair of wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts (14.5%) have a nearly symmetrical distribution of points, Fig.\u00a08e, with thick edges at de + di \u223c2.66\u2005\u00c5. The C\u22efC contacts (8.2%), Fig.\u00a08f, have an arrow-shaped distribution of points with the tip at de = di \u223c1.68\u2005\u00c5. Finally, the H\u22efS/S\u22efH  and C\u22efCl/Cl\u22efC  contacts , and are seen as pairs of wide and thin spikes with the tips at de + di = 3.30 and 3.60\u2005\u00c5, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a08H Table\u00a01 contribu\u22efH Fig.\u00a08g and C\u22ef\u22efC Fig.\u00a08h contacdnorm plotted onto the surface are shown for the H\u22efH, H\u22efCl/Cl\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH, C\u22efC and H\u22efS/S\u22efH inter\u00adactions in Fig.\u00a09a\u2013f, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations -2-[methyl\u00adidene]-4-[2-eth\u00adyl]3,4-di\u00adhydro-2H-1,4- benzo\u00adthia\u00adzin-3-one ring. The energy band gap [\u0394E = ELUMO\u00a0\u2212\u00a0EHOMO] of the mol\u00adecule is about 3.42\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22125.44 and \u22122.02\u2005eV, respectively.The optimized structure of the title compound, (I)et al., 2016II -one , 2.20 equiv. of bis\u00ad(2-chloro\u00adeth\u00adyl)amine hydro\u00adchloride and 2.00 equiv. of potassium carbonate were added to a solution of (Z)-2--2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one (1.5\u2005mmol) in DMF (25\u2005ml). The mixture was stirred at 353\u2005K for 6\u2005h. After removal of salts by filtration, the solution was evaporated under reduced pressure and the residue obtained was dissolved in di\u00adchloro\u00admethane. The remaining salts were extracted with distilled water. The residue obtained was chromatographed on a silica gel column (eluent: ethyl acetate/hexa\u00adne: 3/2). The isolated solid was recrystallized from ethanol solution to afford colourless crystals [light yellow in CIF?] (yield: 67%).Tetra-Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019004250/lh5895sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019004250/lh5895Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019004250/lh5895Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019004250/lh5895Isup4.cmlSupporting information file. DOI: 1906476CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure determination of Na 10[Pd2Cl6](C4H9SO3)8\u00b74H2O, were obtained from a water/2-propanol solution of sodium n-butane\u00adsulfonate and sodium tetra\u00adchlorido\u00adpalladate(II). In the crystal, sodium n-butane\u00adsulfonate anions and water mol\u00adecules are arranged in an amphiphilic inverse bilayered cationic array represented by the formula {[Na10(C4H9SO3)8(H2O)4]2+}n. Within this lamellar array: (i) a hydro\u00adphilic layer region parallel to the bc plane is established by the Na+ cations, the H2O mol\u00adecules  and the O3S\u2013 groups of the sulfonate ions, and (ii) hydro\u00adphobic regions are present containing all the n-butyl groups in an almost parallel orientation, with the chain direction approximately perpendicular to the aforementioned hydro\u00adphilic layer. Unexpectedly, the flat centrosymmetric [Pd2Cl6]2\u2212 anion in the structure is placed between the butyl groups, within the hydro\u00adphobic regions, but due to its appropriate length primarily bonded to the hydro\u00adphilic \u2018inorganic\u2019 layer regions above and below the hydro\u00adphobic area via Pd\u2014Clt\u22efNa- and Pd\u2014Clt\u22efH\u2014O(H)\u2014Na-type  inter\u00adactions. In addition to these hydrogen-bonding inter\u00adactions, both aqua ligands are engaged in charge-supported S\u2014O\u22efH\u2014O hydrogen bonds of a motif characterized by the D43(9) graph-set descriptor within the hydro\u00adphilic region. The crystal structure of the title compound is the first reported for a metal n-butane\u00adsulfonate.In the course of crystal-engineering experiments, crystals of the hydrated title salt, Na In contrast to methane\u00adsulfonates (n = 1) and ethane\u00adsulfonates (n = 2), there is only rare structure information for the next higher homologues   chemistry.Sodium alkane\u00adsulfonates are artificial soaps (anionic tensides) with a widespread use  having the typical brown colour of palladium complexes with a square-planar coordination environment. According to the results of elemental analysis and vibrational spectroscopic investigations, hydrated sodium cations, n-butane\u00adsulfonate and hexa\u00adchlorido\u00addipalladate(II) anions are present in the solid. The crystal structure determination of this compound is the first of a metal n-butane\u00adsulfonate and eventually confirmed the composition Na10(C4H9SO3)8[Pd2Cl6]\u00b74H2O and a lamellar amphiphilic structure.In the investigation described herein, the incorporation of hexa\u00adchlorido\u00addipalladate(II) anions into the sodium n-butane\u00adsulfonate anions and, close to a center of inversion, one half of a hexa\u00adchlorido\u00addipalladate anion. The five Na+ cations are in quite different coordination environments . Bond lengths and angles of the n-butanesulfonate anions are as expected (see supplementary Tables). All these anions are found with an entirely anti-periplanar conformation of the alkyl groups, without any disorder. Altogether, n-butane\u00adsulfonate anions, Na+ cations and water mol\u00adecules form a tenside-like inverse bilayered cationic array, which can be described by the formula {[Na10(H2O)4(C4H9SO3)8]2+}n. In this arrangement, the layer-like regions are oriented parallel to the bc plane of the unit cell. As visualized by the blue and the red sections of the transparent background of Fig.\u00a03+ cations, the H2O mol\u00adecules serving as aqua ligands in \u03bc bridging mode coordination, and the O3S\u2013 groups of the sulfonate ions. With all the C4-chains in an approximately parallel orientation, the butyl groups are arranged on both sides of the hydro\u00adphilic region to complete the amphiphilic double layer with an inverse bilayer thickness according to unit-cell parameter a. The centrosymmetric [Pd2Cl6]2\u2212 anions in the structure of 1 are placed between the n-butyl groups within the hydro\u00adphobic regions. In a first view, this position seems to be unexpected; however, the length of the dipalladate(II) anion is appropriate to allow for pronounced bonding to the hydro\u00adphilic \u2018inorganic\u2019 layered regions above and below the hydro\u00adphobic area  and 2.3212\u2005(12)\u2005\u00c5]. These geometric parameters, as well as the Cl\u2014Pd\u2014Cl bond angles of 86.20\u2005(4) to 92.45\u2005(4)\u00b0 and the Pd\u2014\u03bc-Cl\u2014Pd angle of 93.80\u2005(4)\u00b0, are in good agreement with those found in Cs2[Pd2Cl6] : Na8(C4H9SO3)8\u00b7Na2Pd2Cl6\u00b74H2O. This choice takes into account that the Na\u2014Cl distance from the terminal chlorido ligand Cl2 of the hexa\u00adchlorido\u00addipalladate(II) anion to the sodium cation Na1 [2.8560\u2005(18)\u2005\u00c5] is close to the distances of 2.809\u2005(3) to 2.821\u2005(2)\u2005\u00c5 in Na2PdCl4  and 2.2800\u2005(10)\u2005\u00c5] are slightly shorter than the Pd\u2014+ cations , the two crystallographically independent water mol\u00adecules O1 and O2 in 1 are engaged in non-covalent bonding within the hydro\u00adphilic region (Table\u00a012Cl6]2\u2212 anion [D\u22efA distance = 3.127\u2005(3)\u2005\u00c5] and a charge-supported weak O\u2014H\u22efO type hydrogen bond to an O atom of a sulfonate anion containing S4 [D\u22efA = 2.879\u2005(4)\u2005\u00c5]. In contrast, the water mol\u00adecule containing O2 is engaged in two O\u2014H\u22efO type hydrogen bonds to sulfonate ions, one of moderate strength to an O atom of the sulfonate ion containing S4 [D\u22efA = 2.723\u2005(4)\u2005\u00c5] and a weak one to an O atom of the sulfonate ion containing S3 [D\u22efA = 2.884\u2005(4)\u2005\u00c5]. Pd\u2014Clterm\u22efH\u2014O(Na2)\u2014H\u22efO14(S4)\u22efH\u2014O(Na2)\u2014H\u22efO\u2014S is the entire path of hydrogen bonding described by the D34(9) graph-set descriptor  with n = 1\u20134 gave three hits, viz. the structures of sodium methane\u00adsulfonate  anion results in 46 entries. However, from a structural point of view, the role of the [Pd2Cl6]2\u2212 ion in 1 is completely different from the role of this species in all the other compounds. In addition to the reports on these compounds having organic components, there is one report on an inorganic ternary chloride containing the [Pd2Cl6]2\u2212 ion  of sodium n-butane\u00adsulfonate and 1.177\u2005g (4\u2005mmol) of sodium tetra\u00adchlorido\u00adpalladate(II). The evaporation temperature of the solution was adjusted to 288\u2005K with a thermostat. After three days, crystals suitable for X-ray crystal structure determination could be harvested . A single crystal was selected directly from the mother liquor. Raman spectroscopy was done with a Bruker MultiRAM spectrometer, equipped with a Nd:YAG laser (1064\u2005nm) and an InGaAs detector (4000\u201370\u2005cm\u22121): \u03bd(C\u2014H): 2969 (m), 2920 (s), 2872 (m); \u03b4s(C\u2014H): 1445 (w), 1412 (w); \u03b4as(C\u2014H): 1306 (w); \u03bdas(S\u2014O): 1071 (s); \u03bds(C\u2014S): 800 (m); \u03b4(S\u2014O): 551 (m), 536 (m); \u03bd(Pd\u2014Clterm): 343 (m), \u03bd(Pd\u2014\u03bc-Cl): 305 (s); \u03bd(Pd\u2014\u03bc-Cl): 273 (m). Band assignments were made according to Fujimori  and an universal ATR equipment: \u03bd(O\u2014H): 3503 (s), 3462 (sh), 3436 (s), 3367 (s); \u03bd(C\u2014H): 2967 (s), 2936 (s), 2872 (m); \u03b4(O\u2014H): 1662 (m), 1602 (m); \u03b4s(C\u2014H) 1465 (m), 1412 (w), 1378 (w), \u03b4as(C\u2014H): 1314 (w), 1286 (w); \u03bdas(C\u2014H): 1241 (w); \u03bds(S\u2014O): 1190 (s), 1166 (s); \u03bdas(S\u2014O): 1057 (s), 1044 (s); \u03bds(C\u2014S): 794 (m); \u03b4(S\u2014O): 555 (m), 534 (m); band assignment according to Fujimori (195932H80Cl6Na10O28Pd2S8 (1824.84\u2005g\u2005mol\u22121): C 21.06, H 4.42, S 14.06; found: C 20.78, H 4.49, S 12.98.Thin brown platelets of mori 1959 and Geri al. 1997. An IR smori 1959. A CHS a3 groups were allowed to rotate around the neighboring C\u2014C bonds. The Uiso(H) values were set to 1.5Ueq(Cmeth\u00adyl) and 1.2Ueq(Cmethyl\u00adene), respectively. H\u2014O distances of the water mol\u00adecules were restrained to 0.83\u2005(3)\u2005\u00c5.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019004201/wm5491sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019004201/wm5491Isup2.hklStructure factors: contains datablock(s) I. DOI: 1906335CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Furthermore, ADAM10 participates to spine shaping through the cleavage of adhesion molecules and its activity is under the control of synaptic plasticity events. In particular, long-term depression (LTD) promotes ADAM10 synaptic localization triggering its forward trafficking to the synapse, while long-term potentiation elicits ADAM10 internalization. Here, we show that a short-term in vitro exposure to A\u03b21\u201342 oligomers, at a concentration capable of inducing synaptic depression and spine loss, triggers an increase in ADAM10 synaptic localization in hippocampal neuronal cultures. However, the A\u03b21\u201342 oligomers-induced synaptic depression does not foster ADAM10 delivery to the synapse, as the physiological LTD, but impairs ADAM10 endocytosis. Moreover, A\u03b21\u201342 oligomers-induced inhibition of ADAM10 internalization requires neuronal activity and the activation of the NMDA receptors. These data suggest that, at the synaptic level, A\u03b21\u201342 oligomers trigger an aberrant plasticity mechanism according to which A\u03b21\u201342 oligomers can downregulate A\u03b2 generation through the modulation of ADAM10 synaptic availability. Moreover, the increased activity of ADAM10 towards its synaptic substrates could also affect the structural plasticity phenomena. Overall, these data shed new lights on the strict and complex relationship existing between synaptic activity and the primary mechanisms of AD pathogenesis.A disintegrin and metalloproteinase 10 (ADAM10) is a synaptic enzyme that has been previously shown to limit amyloid-\u03b2The online version of this article (10.1007/s12035-019-1583-5) contains supplementary material, which is available to authorized users. Then, to induce chemical LTD, we applied NMDA (20\u00a0\u03bcM) and glycine  for 3\u00a0min at room temperature in MgQuantification of Western Blot analysis was performed by means of computer-assisted imaging . The levels of the proteins were expressed as relative optical density (OD) measurements and normalized on tubulin. Values are expressed as mean \u00b1 S.E.M. of at least three independent experiments.t test  or, when appropriate, by using one-way ANOVA followed by Bonferroni\u2019s post hoc test or Kruskal-Wallis analysis of variance followed by Dunn\u2019s post hoc test.Co-localization analysis was performed using Zeiss AIM 4.2 software and spines analysis was performed with ImageJ software . For co-localization, and morphological analysis, cells were chosen randomly for quantification from 4 different coverslips (2\u20133 independent experiments), images were acquired using the same settings/exposure times, and at least 10 cells for each condition were analyzed. Statistical evaluations were performed by using 2-tailed Student\u2019s Suppl. Fig. 11\u201342 short exposure does not affect the expression and synaptic levels of GluN1, GluN2A, GluN2B and PSD-95. A) Quantitative analysis of Western Blot analysis of homogenate reported in Fig.42\u20131 70.59\u2009\u00b1\u200917.76%, oA\u03b21\u201342 109.3\u2009\u00b1\u200914.55%; GluN2A, CTRL 100\u2009\u00b1\u200924.25, A\u03b2 42\u20131 119.9\u2009\u00b1\u200934.25%, oA\u03b21\u201342 80.28\u2009\u00b1\u20098.62%; GluN2B, CTRL 100\u2009\u00b1\u200930.65%, A\u03b2 42\u20131 90.94\u2009\u00b1\u200916.17%, oA\u03b21\u201342 99.64\u2009\u00b1\u200945.05%; PSD-95, CTRL 100\u2009\u00b1\u200920.64%, A\u03b2 42\u20131 132.2\u2009\u00b1\u20096.41%, oA\u03b21\u201342 111\u2009\u00b1\u200928.41%; p\u2009>\u20090.05, one-way ANOVA, n\u2009=\u20095); B) Quantitative analysis of Western Blot analysis of TIF reported in Fig.42\u20131\u2009=\u200983.29\u2009\u00b1\u200932.03%, oA\u03b21\u201342 72.32\u2009\u00b1\u200913.9%; GluN2A CTRL 100\u2009\u00b1\u200916.60%, A\u03b242\u20131 106.9\u2009\u00b1\u200910.78%, oA\u03b21\u201342 104.9\u2009\u00b1\u200918.36%; GluN2B, CTRL 100\u2009\u00b1\u200925.43%, A\u03b242\u20131 117.3\u2009\u00b1\u200919.03, oA\u03b21\u201342 102.0\u2009\u00b1\u200914.97%; PSD-95, CTRL 100\u2009\u00b1\u20098.03, A\u03b242\u20131 106.2\u2009\u00b1\u20095.13, oA\u03b21\u201342 102\u2009\u00b1\u20095.84; p\u2009>\u20090.05, one-way ANOVA, n\u2009=\u20095). (PNG 43\u00a0kb)oA\u03b2High Resolution Image (TIF 130\u00a0kb)Suppl. Fig. 21\u201342 short exposure does not affect the synaptic localization of SAP97 and \u03b22-adaptin. A) Quantitative analysis of Western Blot analysis of SAP97 levels in TIF reported in Fig. 42\u20131 123.6\u2009\u00b1\u200929.07%, oA\u03b21\u201342 96.75\u2009\u00b1\u200921.64%; p\u2009>\u20090.05, one-way ANOVA, n\u2009=\u20095); B) Quantitative analysis of Western Blot analysis of \u03b22-adaptin in TIF reported in Fig.42\u20131\u2009=\u2009101.50\u2009\u00b1\u20099.20%, oA\u03b21\u201342 110.60\u2009\u00b1\u20098.35%; p\u2009>\u20090.05, one-way ANOVA, n\u2009=\u20095) (PNG 44\u00a0kb)oA\u03b2High Resolution Image (TIF 109\u00a0kb)Suppl. Fig. 31\u201342-induced increase in ADAM10 synaptic availability does not involve the activation of GluN2B-containing NMDA receptors. The presence of ifenprodil , an inhibitor of GluN2B-containing NMDA receptors, does not affect oA\u03b21\u201342-triggered augment in ADAM10 synaptic levels  (PNG 66\u00a0kb)oA\u03b2High Resolution Image (TIF 134\u00a0kb)"}
{"text": "In comparison with previous determinations, the present redetermination results in improved precision of the structural parameters.Sr 2PdO3  was carried out using high-quality single-crystal X-ray data. The Sr2PdO3 structure has been described previously in at least three reports [Wasel-Nielen & Hoppe  as reported previously. The structure consists of infinite chains of corner-sharing PdO4 plaquettes inter\u00adspersed by SrII atoms. A brief comparison of Sr2PdO3 with the related K2NiF4 structure type is given.The crystal structure redetermination of Sroppe 1970. Z. Anor Roy 1971. Adv. Ch al. 2002. J. Allo The PdII atom forms distorted PdO4 square planes, which are linked by sharing oxygen atoms in the trans-position to form infinite chains extending along the b-axis direction as shown in Fig.\u00a01j Wyckoff site having mm2 site symmetry. It is seven-coordinate in a monocapped trigonal\u2013prismatic fashion by oxygen with three different bond lengths  \u00d7 3.7887\u2005(2) \u00d7 3.9822\u2005(3)\u2005\u00c53 \u2005\u00c5] and five SrII atoms with one short [2.474\u2005(2)\u2005\u00c5] and four long distances [2.6668\u2005(2)\u2005\u00c5] \u2005\u00c5] and two PdII atoms [1.9911\u2005(2)\u2005\u00c5]  I. DOI: 10.1107/S2056989018017176/wm5474Isup2.hklStructure factors: contains datablock(s) I. DOI: 1882781CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Kip1 and p21Cip1, effectively canceled the accelerated activation of NF\u2010\u03baB, suggesting that oncogenic Ras\u2010induced cell cycle progression is essential for the hyperactivation of NF\u2010\u03baB. Furthermore, we found that Ras (G12V) augmented the transcriptional activation of NF\u2010\u03baB, and this activation required the p38 MAP kinase. We observed that a downstream kinase of p38 MAP kinase, MSK1, was activated by Ras (G12V) and catalyzed the phosphorylation of p65/RelA at Ser\u2010276, which is critical for its transcriptional activation. Significantly, phosphorylation of the p65/RelA subunit at Ser\u2010276 was elevated in patient samples of colorectal cancer harboring oncogenic mutations of the K\u2010Ras gene, and the expression levels of NF\u2010\u03baB target genes were drastically enhanced in several cancer tissues. These observations strongly suggest that oncogenic signal\u2010induced acceleration of NF\u2010\u03baB activation is caused by activation of the p38 MAP kinase\u2013MSK1 signaling axis and by cell cycle progression in cancer cells.It is well established that nuclear factor \u03baB (NF\u2010\u03baB) acts as one of the most important transcription factors for tumor initiation and progression, as it both protects cells from apoptotic/necrotic signals and accelerates angiogenesis and tumor metastasis, which is mediated via the expression of target genes. However, it has not yet been clarified how oncogenic signals accelerate the activation of NF\u2010\u03baB. In the current study, we utilized untransformed NIH\u20103T3 cells stably harboring a \u03baB\u2010driven luciferase gene to show that an oncogenic mutant of Ras GTPase augmented TNF\u03b1\u2010induced NF\u2010\u03baB activation. Notably, enforced expression of cyclin\u2010dependent kinase inhibitors, such as p27 CDKcyclin\u2010dependent kinaseCHXcycloheximideCOX\u20102cyclooxygenase 2CRCcolorectal cancerDMEMDulbecco's modified Eagle's mediumGAPGTPase\u2010activating proteinICAM\u20101intercellular adhesion molecule\u20101I\u03baB\u03b1inhibitor of \u03baB\u03b1MSK1/2mitogen and stress activated protein kinase 1/2NF\u2010\u03baBnuclear factor \u03baBNPMnucleophosminPI\u20103 kinasephosphatidylinositol\u20103 kinasePKAprotein kinase ARHDRel homology domainshRNAshort\u2010hairpin RNATNF\u03b1tumor necrosis factor \u03b1VEGFvascular endothelial growth factor1et al., Nuclear factor \u03baB (NF\u2010\u03baB) includes a family of transcription factors, which induce the expression of a number of target genes related to anti\u2010inflammation, development, and the apoptosis\u2010related responses  supplemented with 10% FBS, 2\u00a0m2.2Kip1, and p21Cip1 were amplified by PCR using PrimeSTAR GXL DNA polymerase  and inserted into EcoRI and XhoI sites of MSCV\u2010ires\u2010Puro retroviral vector.pBabePuro\u2010H\u2010Ras (G12V) was a kind gift from S. Lowe, Sloan Kettering Institute. pBabePuro\u2010B\u2010RAF (V600E) was a gift from W. Hahn (Addgene plasmid # 15269). cDNA of p16Ink4a, p272.3An anti\u2010FLAG antibody (M2) was purchased from Merck Millipore . Anti\u2010cyclin A (SC\u2010751), anti\u2010cyclin D1 (SC\u2010753), anti\u2010CDC2 (SC\u2010163), anti\u2010CDK4 (SC\u2010601), anti\u2010H\u2010Ras (SC\u2010520), and anti\u2010\u03b2\u2010actin (SC\u2010130301) antibodies were obtained from Santa Cruz Biotechnology . An anti\u2010phospho p65/RelA (S276) antibody was purchased from Rockland Immunochemicals . Anti\u2010MSK1 and anti\u2010MSK2 antibodies were purchased from Cell Signaling Technology  and BD Biosciences , respectively. TNF\u03b1 and PDGF were purchased from PeproTech . LY294002, U0126, SP600125, and SB203580 were obtained from FUJIFILM Wako Pure Chemical . NOX inhibitor, VAS2870, was purchased from Merck Millipore .2.46 cells per 60\u2010mm\u2010diameter culture dish) with helpers such as pE\u2010Eco and pGP (TAKARA\u2010Bio). Twenty\u2010four hours later, culture medium was replaced with 1.5\u00a0mL fresh culture medium. Secreted retroviruses were harvested every 4\u20136\u00a0h during 24\u201360\u00a0h post\u2010transfection, pooled, and stored on ice. Exponentially growing cells (1\u00a0\u00d7\u00a0105 cells per 60\u2010mm\u2010diameter culture dish) were infected several times at 2\u2010h intervals with 2\u00a0mL of virus\u2010containing conditioned medium with 1.0\u00a0\u00b5g\u00b7mL\u22121 polybrene (Merck Millipore). Twenty\u2010four hours later, the infected cells were cultured in completed medium including suitable concentrations of puromycin  for 3\u00a0days. Then, selected cells were utilized for the experiments.To obtain retroviruses, MSCV\u2010ires\u2010GFP or MSCV\u2010ires\u2010Puro encoding the cDNA of the indicated proteins was transfected into HEK293T cells  against murine MSK1/2 and human K\u2010Ras gene products were inserted into pSUPER\u2010retro\u2010puro retroviral plasmid . The sequences of oligonucleotides used for constructing the shRNA retroviral vector against each gene product were described as below: For sh\u2010mMSK1#1; GATCCCCGTGATTTACCAGAGAGAAATTCAAGAGATTTCTCTCTGGTAAATCACTTTTTA and AGCTTAAAAAGTGATTTACCAGAGAGAAATCTCTTGAATTTCTCTCTGGTAAATCACGGG, For sh\u2010mMSK1#2; GATCCCCGCCAATACTCAGAAAGAAATTCAAGAGATTTCTTTCTGAGTATTGGCTTTTTA and AGCTTAAAAAGCCAATACTCAGAAAGAAATCTCTTGAATTTCTTTCTGAGTATTGGCGGG, For sh\u2010MSK2#1; GATCCCCGCGGAGAGCTATTGGAACATTCAAGAGATGTTCCAATAGCTCTCCGCTTTTTA and AGCTTAAAAAGCGGAGAGCTATTGGAACATCTCTTGAATGTTCCAATAGCTCTCCGCGGG, For sh\u2010MSK2#2; GATCCCCGGGCATGAGGAGAAGGTGATTCAAGAGATCACCTTCTCCTCATGCCCTTTTTA and AGCTTAAAAAGGGCATGAGGAGAAGGTGATCTCTTGAATCACCTTCTCCTCATGCCCGGG, For sh\u2010K\u2010Ras#1; GATCCCCCGAATATGATCCAACAATATTCAAGAGATATTGTTGGATCATATTCGTTTTTA and AGCTTAAAAACGAATATGATCCAACAATATCTCTTGAATATTGTTGGATCATATTCGGGG, For sh\u2010K\u2010Ras#2; GATCCCCGGACGAATATGATCCAACATTCAAGAGATGTTGGATCATATTCGTCCTTTTTA and AGCTTAAAAAGGACGAATATGATCCAACATCTCTTGAATGTTGGATCATATTCGTCCGGG.Infection with retroviruses, including these shRNA, into NIH\u20103T3 cells was performed at the same time with a retrovirus harboring oncogenic Ras.2.6\u22121 TNF\u03b1 for 16\u00a0h. Cells were lysed with passive lysis buffer , and the activity of expressed luciferase was measured by using a Luciferase Assay kit (Promega). The specific activity of luciferase was calculated by normalizing with protein concentration of each cell lysate, and data were shown in the graph as relative amount. To observe the effect of each kinase inhibitor on the NF\u2010\u03baB activation, cells were treated with the inhibitors 15\u00a0min prior to stimulation with TNF\u03b1. To analyze the transcriptional activation of NF\u2010\u03baB, parental NIH\u20103T3 cells were transfected with pFR\u2010luciferase containing the sequence of a GAL4\u2010responsive element with the indicated combination of plasmids. Cells were cultured in serum\u2010free DMEM for 24\u00a0h, and then, the cells were harvested, and luciferase activity was assayed as described above.KF\u20108 cells infected with indicated retroviruses were re\u2010plated on a 24\u2010well plate and then cultured in serum\u2010starved medium for 24\u00a0h. Then, the cells were stimulated with 10\u00a0ng\u00b7mL2.7et al., m HEPES\u2013KOH pH7.5 including 1\u00a0\u03bcg\u00b7\u03bcL\u22121 poly\u2010dIdC for 30\u00a0min at 25\u00a0\u00b0C. Then, the binding mixtures were pulled down using streptavidin\u2010conjugated agarose . The samples were analyzed by immunoblotting analysis as described below.Nuclear extracts were prepared as reported previously  supplemented with protease inhibitors. FLAG\u2010MSK1 and FLAG\u2010PKAc were purified by immunoprecipitation using an M2 antibody attached to protein G\u2010sepharose , and they were utilized for in\u00a0vitro kinase assays. For these assays, purified kinases were incubated with 2\u00a0\u03bcg GST\u2010p65/RelA and 100\u00a0\u03bcm ATP for 30\u00a0min at 30\u00a0\u00b0C. The reaction was terminated by the addition of Laemmli sample buffer, and then, phosphorylated samples were resolved by SDS/PAGE and immunoblotting analysis with an anti\u2010phospho p65/RelA (S276) antibody .HEK293T cells were transfected with the indicated combinations of plasmids harboring cDNA of FLAG\u2010MSK1, FLAG\u2010PKAc, or H\u2010Ras (G12V). Twenty\u2010four hours later, the transfected cells were cultured in serum\u2010free DMEM for 24\u00a0h. Then, cells were harvested, and cell lysates were prepared with Nonidet P\u201040 (NP\u201040) lysis buffer (50\u00a0m2.9m sodium phosphate (pH 7.2), 150\u00a0mm NaCl, 3\u00a0mm MgCl2, 2\u00a0mm EDTA, 1% NP\u201040, 1% sodium deoxycholate, 0.2\u00a0U\u00b7mL\u22121 aprotinin, and phosphatase inhibitors] and briefly sonicated on ice. Then, debris were removed by sedimentation in a microcentrifuge at 16\u00a0400\u00a0g for 10\u00a0min, and cleared cell lysates were harvested and mixed with Laemmli sample buffer. Twenty\u2010five microgram of protein of whole cell lysates was loaded in each lane of an SDS\u2010polyacrylamide gel, and each protein was separated by the electrophoresis. Then, the separated proteins were transferred onto a polyvinylidene difluoride membrane (Merck Millipore). Proteins were visualized by immunoblotting analysis with the indicated antibodies and a chemical luminescence reagent, ECL . In some case such as the in\u00a0vitro kinase assay, cells were lysed with NP\u201040 lysis buffer as described above.For usual immunoblotting analysis, cells were lysed with RIPA buffer without SDS [10\u00a0m2.10m dNTPs, and 5\u00a0pmol oligo (dT)20 primer , and then, cDNA synthesis was performed for 60\u00a0min at 42\u00a0\u00b0C. The reaction was terminated by heating at 95\u00a0\u00b0C for 5\u00a0min and diluted with 80\u00a0\u03bcL TE buffer. One microlitre of synthesized cDNA was used for quantitative PCR in a 20\u00a0\u03bcL volume with the KAPA SYBR\u00ae FAST qPCR Kit , and the reaction was analyzed by a LightCycler 96 . The PCR primer sequences used are shown in Table Total RNA was extracted using TRIzol . To synthesize the single\u2010strand cDNA, 2\u00a0\u03bcg of total RNA was added into 20\u00a0\u03bcL reaction mixture including 100\u00a0units ReverTra Ace, 1\u00a0m2.114\u00a0cells per 35\u2010mm\u2010diameter dish, and grown for 2\u20133\u00a0weeks. The visible colonies showing a diameter of 1.0\u00a0mm or more were counted using nih imagej software, freely provided from Dr. Wayne Rasband in NIH (https://imagej.nih.gov/ij/), and results were shown in the graph.For the colony formation assay, infected NIH\u20103T3 cells were seeded onto soft agar at 1\u00a0\u00d7\u00a0102.12To detect K\u2010Ras mutations by quantitative PCR for the human colorectal tumor samples, and perform further experiments using them, we obtained informed consent forms from each patient. All experiments were undertaken with the understanding and written consent of each subject. The methodologies for experiments conformed to the standards set by the Declaration of Helsinki. The methodologies of current study were approved by the ethics committee in Jichi medical university.2.13et al., From tumor tissues of each patient, genomic DNA was extracted using a NucleoSpin Tissue XS Genomic DNA Purification kit  in accordance with the manufacturer's instructions. The prepared genomic DNA was utilized for quantitative PCR analysis to detect K\u2010Ras mutations. Hydrolysis probes were designed in accordance with a previous report  patients, and samples were fixed with formaldehyde. Among them, seven samples were selected for further analysis, because the tumor tissues in these samples harbored an oncogenic point mutation in exon 2 of the K\u2010Ras gene. The formalin\u2010fixed paraffin\u2010embedded sections were pretreated in a microwave oven for 15\u00a0min. First, H&E staining of each tumor tissue was performed to differentiate between tumor cell areas and normal tissues. Then, immunohistochemical staining was performed using anti\u2010p65/RelA or anti\u2010phospho p65/RelA (Ser\u2010276) as a primary antibody. As a secondary antibody, HRP\u2010conjugated anti\u2010rabbit IgG antibody (donkey) was used. Then, the sections were incubated with Envision  and stained with DAB  for the visualization of signals.2.15n\u00a0=\u00a03), and the results of calculations of independent t\u2010tests are shown.All experiments were performed individually three times, and representative data shown. In graphs, error bars indicate standard deviation  drastically enhanced the expression of cyclin A and cyclin D1, while the expression of p27Kip1 was markedly diminished.Previously, we established KF\u20108 cells, a subline of NIH\u20103T3 cells stably harboring \u03baB\u2010responsive elements\u2010driven luciferase gene  caused the hyperacceleration of NF\u2010\u03baB activation  on TNF\u2010\u03b1\u2010induced signal transduction pathways for NF\u2010\u03baB activation. As shown in Fig. V on TNF\u20103.3Ink4a but not p27Kip1 suppressed TNF\u03b1\u2010induced NF\u2010\u03baB activation in HEK293 and HeLa cells  and TNF\u03b1. Unexpectedly, we observed that the enforced expression of p16Ink4a could not inhibit the hyperactivation of NF\u2010\u03baB  is a marker protein in the nucleolus, and some studies reported that NPM antagonizes p19ARF  inhibitor p163.4m), U0126 (20\u00a0\u03bcm), and SP600125 (50\u00a0\u03bcm), slightly suppressed the hyperactivation of NF\u2010\u03baB, suggesting the partial involvement of the PI\u20103 kinase, ERK, and JNK pathways. Mitsushita et al. (m), an inhibitor for NOX1, exhibited slight inhibitory effect on NF\u2010\u03baB. Notably, treatment with 10\u00a0\u03bcm of SB203580, an inhibitor of p38 MAP kinase, exhibited drastic inhibitory effects on the oncogenic hyperactivation of NF\u2010\u03baB. These observations suggested the functional involvement of p38 MAP kinase in the H\u2010Ras (G12V)\u2010provoked oncogenic hyperactivation of NF\u2010\u03baB. As shown in Fig. m of SB203580 effectively suppressed the hyperactivation of NF\u2010\u03baB induced by co\u2010stimulation with B\u2010Raf (V600E) and TNF\u03b1  and MSK1, a downstream protein kinase of p38 MAP kinase, were reported to be protein kinases for the phosphorylation of p65/RelA at Ser\u2010276 , which catalyzes monomethylation of p65/RelA at Lys\u2010310 and suppresses the expression of NF\u2010\u03baB target genes. Additionally, several studies reported the importance of the phosphorylation of p65/RelA at Ser\u2010536 for the nuclear translocation or transcriptional activation of NF\u2010\u03baB  KF\u20108 cells were infected with control retroviruses or retroviruses harboring K\u2010Ras (G12V) or c\u2010Myc. After puromycin selection, cells were stimulated with 10 \u03bcg/ml TNFa for indicated periods. Then, cells were lysed, and the luciferase assay was performed. (B) Using KF\u20108 cells infected with control retroviruses or retroviruses harboring K\u2010Ras mutants including G12V, K117N and A146T, the luciferase assay was performed as shown in (A). In the graph, error bars\u00a0=\u00a0SD .Fig. S2. (A) HEK293T cells were transfected with a luciferase vector including \u03baB\u2010responsive element with/without FLAG\u2010PKAc, a catalytic subunit of PKA. Then, using the transfected cells, luciferase assays were performed. In graph, error bars indicate standard deviation , and the results of calculations of independent t\u2010tests are shown (*P\u00a0<\u00a00.005). (B) The expression of FLAG\u2010MSK1 and H\u2010Ras (G12V) in cells analyzed for in vitro kinase assay  was analyzed by immunoblotting analysis using antibodies against FLAG\u2010tag (M2) and H\u2010Ras. (C) KF\u20108 cells were infected with retroviruses harboring scrambled short\u2010hairpin RNA, sh\u2010MSK1 (1A or 1B) or sh\u2010MSK2 (2A or 2B). After puromycin selection, cells were lysed, and immunoblotting analysis was performed to evaluate the knockdown efficiency of MSK1 and MSK2. \u03b2\u2010actin was used as a loading control.Fig. S3. (A) NIH\u20103T3 cells were infected with indicated retroviruses as described in Figure 5B. After puromycin selection, cells (1 \u00d7 104 cells) were seeded on soft agar media in 35 mm dishes. After 3 weeks, the number of colonies were counted and shown in graph as shown in (B). In the graph, error bars\u00a0=\u00a0SD . In the photograph, 500 \u03bcm scale bar was shown.Fig. S4. SW620, a colorectal cancer\u2010derived cell line was transfected with siRNAs against both MSK1 and MSK2.Fig. S5. Genomic DNA was extracted from tumor tissues of 30 colorectal cancer patients (designated as T001 to T030).Fig. S6. Utilizing paired samples of tumor and normal tissues from K\u2010Ras (+) patients, immunohistochemical analyses were performed to detect total p65/RelA and phosphorylated p65/RelA (Ser276).Fig. S7. Total RNA was extracted from normal and tumor tissues from each patient harboring KRas mutations.Click here for additional data file.Table S1. Primers used in quantitative PCR for NF\u2010kB target genes.Click here for additional data file.Table S2. Primers used for genotyping of KRas gene.Click here for additional data file."}
{"text": "MecAAC (E=S (1); Se (2); Te (3); L=PhC(NtBu)2; MecAAC=C(CH2)(CMe2)2N\u20102,6\u2010iPr2C6H3)) were synthesized from the reactions of silylene\u2013phosphinidene LSi\u2212P\u2212MecAAC (A) with elemental chalcogens. All the compounds reported herein have been characterized by multinuclear NMR, elemental analyses, LIFDI\u2010MS, and single\u2010crystal X\u2010ray diffraction techniques. Furthermore, the regeneration of silylene\u2013phosphinidene (A) was achieved from the reactions of 2\u20133 with L\u2032Al (L\u2032=HC{(CMe)}2). Theoretical studies on chalcogen\u2010bonded silicon phosphinidenes indicate that the Si\u2212E  bond can be best represented as charge\u2010separated electron\u2010sharing \u03c3\u2010bonding interaction between [LSi\u2212P\u2212MecAAC]+ and E\u2212. The partial double\u2010bond character of Si\u2212E is attributed to significant hyperconjugative donation from the lone pair on E\u2212 to the Si\u2212N and Si\u2212P \u03c3*\u2010molecular orbitals.Chalcogen\u2010bonded silicon phosphinidenes LSi(E)\u2212P\u2212 A, Scheme\u2005B, Scheme\u2005C, Scheme\u2005CycAAC)SiCl2\u2192P\u2212Tip .CycAAC)SiCl2\u2192P\u2212Tip Si(P\u2212Tip)]2  reacts smoothly with elemental chalcogens to form the chalcogen\u2010bonded silicon phosphinidenes LSi(E)\u2212P\u2212MecAAC (E=S (1); Se (2); Te (3)).Phosphinidenes (R\u2212P) are phosphorus analogues of carbenes and nitrenes.2, which is the only example of a compound with a silicon\u2013chalcogen double bond and a phosphine functionality.MecAAC (E=S (1); Se (2); Te (3)) with phosphinidene functionality. Compounds 1\u20133 were characterized by single\u2010crystal X\u2010ray structural investigation and multinuclear NMR spectroscopy. An equimolar reaction of compound A with elemental sulfur and selenium at room temperature in toluene afforded compounds 1 and 2 in 68\u2009% and 75\u2009% yield, respectively \u2212P\u2212MecAAC (3) in 79\u2009% yield }2) at room temperature as well as at elevated temperature, but no chalcogen transfer occurred. Nonetheless, 2 and 3 react with L\u2032Al at 60\u2009\u00b0C, resulting in the formation of parent silylene\u2013phosphinidene ; Te ) with ph1\u20133 are thermally stable with melting points over 200\u2009\u00b0C, but they are sensitive towards moisture. They are fully characterized by NMR spectroscopy, elemental analyses, LIFDI\u2010MS, and X\u2010ray single\u2010crystal structure analysis. The 31P{1H}\u2005NMR spectra of 1\u20133 exhibit a singlet at \u03b4=+2.33, +9.37, and +21.67\u2005ppm, respectively, which are highfield shifted compared with the starting material, silylene\u2013phosphinidene (A). In the 29Si{1H}\u2005NMR spectra, 1\u20133 display doublets at \u03b4=+20.48 (1JSi\u2212P=107\u2005Hz), +16.96 (1JSi\u2212P=117\u2005Hz), and \u221210.94\u2005ppm (1JSi\u2212P=127\u2005Hz), respectively, due to the coupling with the phosphorus atom. The difference of the chemical shift between 1\u20133 and A in the 29Si{1H}\u2005NMR spectra is due to the different silicon oxidation states (+4 and +2). The 77Se{1H}\u2005NMR spectrum of 2 shows a doublet at \u03b4=\u2212286.13\u2005ppm (2JSe\u2212P=18\u2005Hz) due to the coupling with the phosphorus atom. For the same reason the 125Te{1H}\u2005NMR spectrum of 3 exhibits a doublet at \u03b4=\u2212835.45\u2005ppm (2JTe\u2212P=38\u2005Hz). The LIFDI mass spectra of 1\u20133 in toluene exhibit molecular\u2010ion peaks at 607.4, 655.3, and 705.4, respectively.Compounds 1\u20133 suitable for X\u2010ray structural analysis were obtained from toluene solution either at 0\u2009\u00b0C or at room temperature (for details see the Supporting Information). Compounds 1\u20133 crystallize in the monoclinic space group P21/c. All three structures are isostructural, whereas 1 and 2 are even isomorphous. Compound 3 crystallizes as a pseudo\u2010merohedral twin with two molecules in the asymmetric unit. As a representative for all the molecular structure of 1 is depicted in Figure\u20051, 2, and 3 are about 3\u2005pm shorter than in A 2}Si(S)N(SiMe3)2] and [{PhC(NtBu)2}Si(Se)N(SiMe3)2] (1.987(8) and 2.136(9)\u2005\u00c5, respectively).3 is similar to the one observed in [{PhC(NtBu)2}Si(Te)N(SiMe3)2], (2.3720(15)\u2005\u00c5).1\u20133 are well within the range of previous reported Si\u2212E double bond lengths.Single crystals of A as well as chalcogen\u2010bonded silicon phosphinidenes 1, 2, and 3.A is given in Figure\u2005S2.3a (Supporting Information). The ESP value in the direction of the lone pair at P  is slightly higher than that in the direction of the lone pair at Si . This indicates a slightly higher nucleophilicity of the first than the second (Table\u2005S2.1). The occupancy of the P (1.943\u2005e) and Si (1.925\u2005e) lone pair in A are well corroborated with ESP values (Table\u2005S2.2). This is in accordance with our previous theoretical study on silylene\u2013phosphinidenes.Quantum\u2010mechanical calculations were performed at the M06/def2\u2010TZVPP//BP86/def2\u2010SVP level of theory to understand the electronic structure and reactivity of silylene\u2013phosphinidene A, the reactions of silylene\u2013phosphinidene A with chalcogens result in silicon bonded chalcogens in the phosphinidenes 1, 2, and 3. To account for this observation, we have calculated the reaction energies for the formation of chalcogen\u2010bonded silicon phosphinidenes 1, 2, and 3 as well as hypothetical chalcogen\u2010bonded phosphorus phosphinidenes 1\u2032, 2\u2032, and 3\u2032 . All the reaction energies are exothermic, and the energies become more positive with the descent from sulfur to tellurium. The reaction energies for the formation of silicon\u2010bonded chalcogen phosphinidenes 1 (\u2212107.3), 2 (\u221288.2), and 3  are much higher than chalcogen\u2010bonded phosphorus phosphinidenes 1\u2032 (\u221277.0), 2\u2032 (\u221259.4), and 3\u2032 . Hence the formation of the P\u2212E bond is less favorable than the formation of a Si\u2212E bond. Note that our calculated reaction energies are comparable to the previously reported bond\u2010dissociation energies for Si=S (112.8), Si=Se (95.5), and Si=Te  bonds in CH3Si(=E)OH compounds  at the MP2/6\u2013311++G//MP2/6\u2013311+G level of theory.1\u20133, which is in accordance with the experimental observation that the regeneration of parent molecule A could not be achieved when 1 is treated with the L\u2032Al (L\u2032=HC{(CMe)}2) . The Si\u2212E bond lengths in 1 (2.019), 2 (2.160), and 3 (2.398\u2005\u00c5) in turn are close to those of previously reported Si=E double bond lengths.1 is comparable to those in the amidinate stabilized siladithiocarboxylate (2.030\u2005\u00c5),1\u20133 is in agreement with the Wiberg bond index of Si\u2212E bond , \u221236.1(2), and \u221232.0\u2005kcal\u2009mol\u22121 (3).The calculated geometrical parameters of 19), 2 2.0, and 3 MecAAC]+ and E\u2212. The second bonding interaction represents donor\u2013acceptor interaction between [LSi\u2212P\u2212MecAAC] and E. The best bonding representation is the one having the least value for orbital stabilization energy \u0394Eorb.Eorb for the charge separated electron sharing interaction in 1, 2, and 3 are \u2212215.8, \u2212189.1, and \u2212159.6\u2005kcal\u2009mol\u22121, respectively. The \u0394Eorb for the donor\u2013acceptor interaction in 1, 2, and 3 are \u2212265.2, \u2212214.7, and \u2212164.9\u2005kcal\u2009mol\u22121, respectively. Hence the best bonding description for the Si\u2212E bond in 1\u20133 is the charge\u2010separated electron\u2010sharing interaction between the fragments. However, the difference in the \u0394Eorb between the two bonding models in 3 is only 5.3\u2005kcal\u2009mol\u22121. Hence, the donor\u2013acceptor interaction also contributes towards the ground electronic structure of Si\u2212Te bond in 3.The EDA\u2010NOCV analysis was carried out to further shed light on the nature of the Si\u2212E bond. Two different bonding situations were analyzed, and the results are given in Table\u2005S2.5 (Supporting Information). The first bonding interaction represents charge separated electron\u2010sharing interaction between , wR2=0.0973 , res. density peaks: 0.324 to \u22120.251\u2005e\u2009\u00c5\u22123; Crystal data for 2: C35H54N3PSeSi, rM=654.83\u2005g\u2009mol\u22121, 0.351\u00d70.257\u00d70.145\u2005mm, monoclinic, P21/c, a=13.903(2), b=10.077(2), c=26.651(3)\u2005\u00c5, \u03b2=102.18(3)\u00b0, V=3649.8(11)\u2005\u00c53, Z=4, \u03bc (Mo K\u03b1)=1.131\u2005mm\u22121, \u03b8max=28.34\u00b0, 125\u2009128 reflections measured, 9105 independent (int=R0.0424), R1=0.0252 [I>2\u03c3(I)], wR2=0.0640 , res. density peaks: 0.406 to \u22120.182 e \u00c5\u22123; Crystal data for 3: C35H54N3PTeSi, rM=703.47\u2005g\u2009mol\u22121, 0.254\u00d70.119\u00d70.082\u2005mm, monoclinic, P21/c, a=35.937(3), b=9.237(2), c=23.498(3)\u2005\u00c5, \u03b2=109.09(2)\u00b0, V=7371(2)\u2005\u00c53, Z=8, \u03bc (Mo K\u03b1)=0.909\u2005mm\u22121, \u03b8max=25.32\u00b0, 120\u2009742 reflections measured, 13\u2009421 independent (int=R0.0522), R1=0.0259 [I>2\u03c3(I)], wR2=0.0500 , res. density peaks: 0.570 to \u22120.559\u2005e\u2009\u00c5\u22123.The datasets were collected on an Incoatec Mo Microsource1), 1891854 (2), and 1891855 (3)1891853  should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "II complex and a CuII open-cube complex were synthesized using the tridentate Schiff base ligand, {1-[1-(pyrid\u00adyl)(2-eth\u00adoxy\u00adethyl\u00adidene)]-2-[(pyridin-3-yl)carbon\u00adyl]}hydrazine and copper(II) acetate and their mol\u00adecular and crystal structures determined.A linear polymeric Cu II complexes [Cu(C14H13N4O2)Cl]n, I, and [Cu4(C8H10NO2)4Cl4]n, II, have been synthesized. In the structure of the mononuclear complex I, each ligand is coordinated to two metal centers. The basal plane around the CuII cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitro\u00adgen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitro\u00adgen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl inter\u00adactions, leading to a three-dimensional network structure. The tetra\u00adnuclear complex II lies about a crystallographic inversion centre and has one core in which two CuII metal centers are mutually inter\u00adconnected via two enolato oxygen atoms while the other two CuII cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which the two open-cube units, with seven vertices each, share a side composed of two CuII ions bridged by two enolato oxygen atoms acting in a \u03bc3-mode. The CuII atoms in each of the two CuO3NCl units are connected by one \u03bc2-O and two \u03bc3-O atoms from deprotonated hydroxyl groups and one chloride anion to the three other CuII centres. Each of the penta\u00adcoordinated CuII cations has a distorted NO3Cl square-pyramidal environment. The CuII atoms in each of the two CuO2NCl2 units are connected by \u03bc2-O and \u03bc3-O atoms from deprotonated alcohol hy\u00addroxy groups and one chloride anion to two other CuII ions. Each of the penta\u00adcoordinated CuII cations has a distorted NO2Cl2 square-pyramidal environment. In the crystal, a series of intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds are observed in each tetra\u00adnuclear monomeric unit, which is connected to four tetra\u00adnuclear monomeric units by inter\u00admolecular C\u2014H\u22efO hydrogen bonds, thus forming a planar two-dimensional structure in the (Two Cu It has been shown that the presence of metal ions promotes the hydrolysis of the ester function of the picolinic ester  ions. These ligands then coordinate to the copper(II) cations to yield the two complexes that are reported here.Picolinic acid esters methanol] and a condensation product [({1-[1-eth\u00adoxy-1-(pyridin-2-yl)methyl\u00adene]}-2-(oxonicotin\u00adyl))hydrazine]. It has been shown (Papaefsta\u00adthiou 14H13N4O2)]n, I, the repeat unit of which is shown in \u2005\u00c5, an O16 atom with a Cu1\u2014O16 distance of 1.9808\u2005(15)\u2005\u00c5 and the N11 and N22 atoms from the same ligand with a Cu\u2014N distances of 1.9437\u2005(17) and 2.0444\u2005(17)\u2005\u00c5 \u201379.40\u2005(7)\u00b0, which are slightly smaller than those found in similar compounds \u00b0 and 146.17\u2005(6)\u00b0 methano\u00adlate ligand coordinating to each Cu atom through its imine nitro\u00adgen atom and its alcoholate oxygen atom, forming five-membered chelate rings . Intra\u00admolecular C\u2014H\u22efO contacts are also found  \u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z\u00a0+\u00a0i, Cu2i atoms, \u03bc3-bridging atoms O26, O26i, a \u03bc2-bridging O15i atom and a \u03bc2-bridging Cl3 ion. The result is a is a distorted open-cube, defined as a distorted cube missing one corner. This can be seen by considering that the range of Cu\u2014O\u2014Cu angles is [99.76\u2005(6)\u2013102.98\u2005(6)\u00b0] and the Cu1\u2014Cl3\u2014Cu2i angle is 84.39\u2005(2)\u00b0. These differ extensively from the 90\u00b0 angles of an ideal cube. The two Cu3O3Cl open-cubes are joined by a perfectly rectangular side defined by the Cu1, O26, and Cui, O26i atoms. The values of the two different lengths of the edges of the rectangular sides are 2.4280\u2005(14) and 1.9684\u2005(13)\u2005\u00c5. The other faces of the two open-cubes are irregular with different distances i.e. Cu1\u2014O26i = 2.4280\u2005(14)\u2005\u00c5, Cu2\u2014O26 = 1.9707\u2005(14)\u2005\u00c5, Cu1\u2014Cl3 = 2.2181\u2005(6)\u2005\u00c5 and Cu2\u2014Cl3 = 2.8134\u2005(6)\u2005\u00c5. The Cu1 (Cu1i) atoms in each of the two CuO3NCl units are connected by one \u03bc2-O and two \u03bc3-O atoms from the deprotonated hydroxyl groups and one chloride ion to three other CuII cations. In the CuO2NCl2 units, the Cu2 (Cu2i) atoms are linked to one \u03bc2-O and one \u03bc3-O atoms from a deprotonated hydroxyl groups and one chloride ion to two other CuII cations with Cu1\u2014Cu2 and Cu1\u2014Cu2i distances of approximately 3.012 and 3.408\u2005\u00c5, respectively. These are in good agreement with literature values , 1.9684\u2005(13), 1.9707\u2005(14)\u2005\u00c5, respectively, while Cu1\u2014O15 and Cu2\u2014O15 are 1.9170\u2005(13) and 1.9324\u2005(13)\u2005\u00c5, respectively \u00b0], O26\u2014Cu1\u2014N10 [156.02\u2005(7)\u00b0], O26\u2014Cu2\u2014Cl4 [170.05\u2005(5)\u00b0] and O15\u2014Cu2\u2014N21 [157.61\u2005(7)\u00b0] \u00b0 are different from those of ideal cube. This bridging angle is also smaller than those reported for similar complexes 2Cl2](DMF) where qsalBr = 8-amino\u00adquinoline with 5-bromo-salicyl\u00adaldehyde . These contacts combine with the C\u2014H\u22efO hydrogen bonds to stack the mol\u00adecules in a three-dimensional network along the a-axis direction ]methyl\u00adenehydrazine yielded no hits, indicating that compound I is reasonably unique. However, a search for eth\u00adoxy(pyridin-2-yl)methano\u00adlate, the ligand found in II gave ten hits, although none of these was closely related to II. The matches included the CuII complexes HAXBEN meth\u00adyl]pyridin, has a central pyridine ring that is substituted by 1-eth\u00adoxy-1-hy\u00addroxy-1-(pyridin-2-yl)methyl fragments in the 2- and 6-positions.A search of the CSD database 2\u00b7H2O  in 5\u2005ml of ethanol was added at room temperature. The initial yellow solution immediately turned deep blue and was stirred under reflux for 2\u2005h. The mixture was filtered and the solution evaporated to near dryness. The solid was isolated by filtration and recrystallized from a minimum of ethanol. On standing for five days, two types of crystals suitable for X-ray analysis were formed, light-yellow blocks of I and light-green plates of II.To a solution of 2-pyridine carbaldehyde  in 30\u2005ml of ethanol was added a solution of nicotinic hydrazide  in 10\u2005ml of ethanol. The mixture was stirred for 5\u2005min. A solution of Cu: 2982, 1628, 1583, 1423, 1343, 1245, 941, 816, 630. For II: analysis calculated: C16H20N2Cl2O4Cu2: C, 38.26; H, 4.01; N, 5.58; Cl; 14.12. Found: C, 38.23; H, 3.98; N, 5.55; Cl; 14.08. IR : 2982, 1585, 1423, 1243, 1145, 940, 812.For d(C\u2014H) = 0.93\u2005\u00c5 for aromatic, d(C\u2014H) = 0.97\u2005\u00c5 for methyl\u00adene and d(C\u2014H) = 0.98\u2005\u00c5 for methine H atoms with Uiso(H) = 1.2Ueq(C) and d(C\u2014H) = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl H atoms. One reflection with Fo <<< Fc that was likely to have been affected by the beamstop was omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019008922/sj5575sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989019008922/sj5575Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019008922/sj5575IIsup5.hklStructure factors: contains datablock(s) II. DOI: 1935842, 1935841CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Hirshfeld surface analysis of both com\u00adpounds have been carried out.The mol\u00adecular and crystal structures of \u03bc-aqua-\u03ba 2O:O-di-\u03bc-di\u00adphenyl\u00adacetato-\u03ba4O:O\u2032-bis\u00ad[(di\u00adphenyl\u00adacetato-\u03baO)bis\u00ad(pyridine-\u03baN)nickel(II)], [Ni2(C14H11O2)4(C5H5N)4(H2O)] (1) and \u03bc-aqua-\u03ba2O:O-di-\u03bc-di\u00adphenyl\u00adacetato-\u03ba4O:O\u2032-bis\u00ad[(di\u00adphenyl\u00adacetato-\u03baO)nickel(II)]\u2013aceto\u00adnitrile\u2013di\u00adphenyl\u00adacetic acid (1/2.5/1), [Ni2(C14H11O2)4(C10H8N2)2(H2O)]\u00b72.5CH3CN\u00b7C14H12O2 (2), the com\u00adplex units are stabilized by a variety of intra- and inter\u00admolecular hydrogen bonds, as well as C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 contacts between the aromatic systems of the pyridine, dipyridyl and di\u00adphenyl\u00adacetate ligands. Despite the fact that the di\u00adphenyl\u00adacetate ligand is sterically bulky, this does not inter\u00adfere with the formation of the described aqua-bridged dimeric core, even with a 2,2\u2032-bi\u00adpyridine ligand, which has a strong chelating effect.In the crystal structures of the title com\u00adpounds, namely \u03bc-aqua-\u03ba They belong to the type of aqua-bridged dinickel(II) carboxyl\u00adates with the general formula [MII2(\u03bc-H2O)(\u03bc-O2CR)2(O2CR)2nL] (n = 4 in the case of a monodentate ligand or 2 in the case of bidentate coordination), well known since the 1970s  (for 1) or one 2,2\u2032-bi\u00adpyridine (Bipy) ligand (for 2) and one O atom from a bridging aqua ligand in an octa\u00adhedral geometry  and 3.4826\u2005(5)\u2005\u00c5 (for 2). Each monodentate coordinated di\u00adphenyl\u00adacetate ligand is involved in the formation of an intra\u00admolecular hydrogen bond with a bridging water mol\u00adecule. Hydrogen-bond geometries are specified in Tables 1In the title binuclear com\u00adplexes, y Figs. 1 and 2 \u25b8.1, mol\u00adecules are combined into pairs connected by a centre of symmetry using offset face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions, in which coordinated pyridine ligands of each com\u00adplex  are involved. These pairs, which result from the intermolecular hydrogen bonds between Py ligands and O atoms of carbonyl groups of di\u00adphenyl\u00adacetate ligands , form layered structures parallel to the (101) plane. The layers form a 3D supra\u00admolecular structure through inter\u00admolecular C\u2014H\u22ef\u03c0 contacts, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions between the phenyl substituents of di\u00adphenyl\u00adacetate ligands .In the crystal packing of com\u00adpound 2, each mol\u00adecule of the com\u00adplex is associated with two neighbouring mol\u00adecules via \u03c0\u2013\u03c0 stacking inter\u00adactions between Bipy ligands . As a result, polymer chains are formed along the , as well as N\u22efH inter\u00adactions involving aceto\u00adnitrile solvent mol\u00adecules .For com\u00adpound ds Fig.\u00a07. Other o1, close C\u22efC inter\u00adplanar contacts, responsible for \u03c0\u2013\u03c0 stacking inter\u00adactions between Bipy ligands, are displayed as patches of combined blue and red triangles on the surface over shape index  fragment and no binuclear structures were found. A survey of the CSD reveals 46 related structures of NiII carboxyl\u00adates with a similar structure fragment.A search in the Cambridge Structural Database , in aceto\u00adnitrile (40\u2005ml) was added to a solution of di\u00adphenyl\u00adacetic acid  in 10\u2005ml aceto\u00adnitrile. After full conversion of hellyerite, pyridine  was added and the solution was refluxed for 15\u2005min. The resulting pale-green\u2013blue solution was cooled to room temperature and filtered. After a few days, blue crystals of 1 were collected by filtration (yield \u223c70%).A suspension of synthetic hellyerite, NiCO2 was carried out in a similar manner to the synthesis of com\u00adpound 1, but 2,2\u2032-bi\u00adpyridine  was added instead of pyridine. The resulting blue solution was cooled to room temperature and filtered. After a few days, blue crystals of 2 were collected by filtration (yield \u223c60%).The synthesis of com\u00adpound Uiso(H) = 1.2Ueq(C) for the tertiary C atoms, C\u2014H = 0.93\u2005\u00c5 and Uiso(H) = 1.2Ueq(C) for aromatic C atoms, and C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019014063/su5519sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989019014063/su55191sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019014063/su55192sup3.hklStructure factors: contains datablock(s) 2. DOI: 1959435, 1959436, 1959435, 1959436CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Scientific Reports 10.1038/s41598-018-30356-2, published online 10 August 2018Correction to: This Article contains errors in the Methods under subheading \u2018IBV protection experiment 2\u2019.7 EID50 of rNDV and rNDV/codon optimized-S, respectively, via oculanasal route. Five chickens of group three were inoculated with 10 recommended doses of a commercial live attenuated Mass-type IBV vaccine via oculanasal route and chickens of group four were inoculated with PBS.\u201d\u201cA total of twenty 4-week-old SPF chickens were divided into four groups of five each. Five chickens of groups one and two were inoculated with 10should read:7 EID50 of rNDV/codon optimized-S and 10 recommended doses of a commercial live attenuated Mass-type IBV vaccine via oculanasal route, respectively. Chickens of group three were inoculated with PBS. Samples collected from five non-vaccinated SPF chickens involved in another IBV protection study also were used as control.\u201d\u201cA total of fifteen 4-week-old SPF chickens were divided into three groups of five each. Five chickens of groups one and two were inoculated with 10Furthermore, within the Methods under subheading \u2018Quantitative reverse transcription-polymerase chain reaction (RT-qPCR)\u2019\u201cForty cycles of PCR at 95\u2009\u00b0C for 10\u2009s (denaturation), 58\u2009\u00b0C for 20\u2009s , and 72\u2009\u00b0C for 30\u2009s (elongation) followed by melting curve analysis that consisted of 95\u2009\u00b0C for 5\u2009s and 65\u2009\u00b0C for 60\u2009s.\u201dshould read:\u201cThe thermal conditions of 50\u2009\u00b0C for 10\u2009min and 95\u2009\u00b0C for 10\u2009min, then forty-five cycles of PCR at 95\u2009\u00b0C for 10\u2009s (denaturation), 58\u2009\u00b0C for 20\u2009s  followed by 95\u2009\u00b0C for 5\u2009s and melting curve analysis that consisted of 65\u2009\u00b0C to 95\u2009\u00b0C for 5\u2009s was carried out to amplify the 150\u2009nt \u2013 N gene fragments.\u201d"}
{"text": "A new symmetrical thio\u00adcarbonohydrazone derivative with two similar benzoyl\u00adthio\u00adureido functional groups has been prepared and characterized. 18H18N4O2S2, which consists of two benzoyl\u00adthio\u00adureido moieties connected by an ethyl\u00adene chain. The asymmetric unit consists of one half of the mol\u00adecule, the complete mol\u00adecule being generated by crystallographic inversion symmetry. Both thio\u00adurea moieties are in a trans conformation. An intra\u00admolecular N\u2014H\u22efO hydrogen bond occurs. In the crystal, C\u2014H\u22efS and C\u2014H\u22efO hydrogen bonds link the molecules, forming layers parallel to the ac plane.The reaction of benzoyl chloride and ethyl\u00adendi\u00adamine in the presence of potassium thio\u00adcyanate yielded a white solid, C CuII, NiII and CoII) from acidic media. Thio\u00adurea derivatives have also been shown to possess anti\u00adbacterial, anti\u00adfungal, anti\u00adtubercular, anti\u00adthyroid and insecticidal properties \u2005\u00c5] and O1\u2014C3 [1.2209\u2005(16)\u2005\u00c5] distances indicate that these correspond to double bonds and are comparable to those observed for 1,2-bis\u00ad(N-benzoyl\u00adthio\u00adureido)benzene [1.6574\u2005(18)\u2005\u00c5 for S\u2014C and 1.222\u2005(2)\u2005\u00c5 for O7\u2014C16]  rings  plane. Mol\u00adecular layers running almost parallel to the ac plane are formed by inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efS inter\u00adactions \u2005\u00c5; Cg1 is the centroid of ring C4\u2013C9; symmetry code: (iv) \u2212x\u00a0+\u00a01, y\u00a0+\u00a0z\u00a0+\u00a0In the crystal, the mol\u00adecules, which feature an overall Z-form, have both halves roughly parallel to the s Table\u00a01. These let al., 2016et al., 2016trans with respect to the thiono S atom across the C\u2014N bond. The 1-benzoyl-3-ethyl\u00adthio\u00adurea fragment adopts a cis conformation with respect to the thiono S atom across the respective C\u2014N bond. Six structures in which the spacer is different from the spacer in the symmetrical bis\u00ad(thio\u00adureido) mol\u00adecule studied here appear in the literature. The angles between the phenyl rings are: 63.1\u00b0 for DAVHOZ  was added and a white solid appeared after a few minutes. The compound was filtered off, washed with 3 \u00d7 50\u2005ml of water and dried under vacuum. The solid product was washed with water and purified by recrystallization from an ethanol/di\u00adchloro\u00admethane mixture (1:1 v/v). 12.3\u2005g of the title compound were obtained (yield 88.5%). A small qu\u00adantity of powder was recrystallized from 5\u2005ml of DMF. Colourless single crystals suitable to XRD grew within six days.All purchased chemicals and solvents were of reagent grade and were used without further purification. Melting points were determined with a B\u00fcchi 570 melting-point apparatus and were uncorrected. To a mixture of 7.02\u2005g (72\u2005mmol) of potassium thio\u00adcyanate and 100\u2005ml of acetone was added dropwise a solution of 10.116\u2005g (72\u2005mmol) of benzoyl chloride in 50\u2005ml of acetone. The resulting mixture was stirred under reflux for 1\u2005h and cooled to room temperature. A solution of 2.2\u2005g (36.6\u2005mmol) of 1,2-ethyl\u00adenedi\u00adamine in 20\u2005ml of acetone was added. The yellow solution obtained was stirred at room temperature during 2\u2005h. Hydro\u00adchloric acid (0.1\u2005arH) or 0.97\u2005\u00c5 (CH2). The NH H atoms were located in a difference Fourier map and freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901900495X/vm2216sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901900495X/vm2216Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900495X/vm2216Isup3.cmlSupporting information file. DOI: 1909438CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Conventional hydrogen-bonding inter\u00adactions lead to supra\u00admolecular tapes in the crystal.The 4-pyridyl residues lie to either side of the central, planar C 14H14N4O2\u00b72C7H6O2, are described. The oxalamide mol\u00adecule has a (+)-anti\u00adperiplanar conformation with the 4-pyridyl residues lying to either side of the central, almost planar C2N2O2 chromophore (r.m.s. deviation = 0.0555\u2005\u00c5). The benzoic acid mol\u00adecules have equivalent, close to planar conformations [C6/CO2 dihedral angle = 6.33\u2005(14) and 3.43\u2005(10)\u00b0]. The formation of hy\u00addroxy-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds between the benzoic acid mol\u00adecules and the pyridyl residues of the di\u00adamide leads to a three-mol\u00adecule aggregate. Centrosymmetrically related aggregates assemble into a six-mol\u00adecule aggregate via amide-N\u2014H\u22efO(amide) hydrogen bonds through a 10-membered {\u22efHNC2O}2 synthon. These are linked into a supra\u00admolecular tape via amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds and 22-membered {\u22efHOCO\u22efNC4NH}2 synthons. The contacts between tapes to consolidate the three-dimensional architecture are of the type methyl\u00adene-C\u2014H\u22efO(amide) and pyridyl-C\u2014H\u22efO(carbon\u00adyl). These inter\u00adactions are largely electrostatic in nature. Additional non-covalent contacts are identified from an analysis of the calculated Hirshfeld surfaces.The crystal and mol\u00adecular structures of the title 1:2 co-crystal, C Indeed, in early studies on crystal engineering, the combination of bifunctional nLH2 with di\u00adcarb\u00adoxy\u00adlic acids such as bis\u00ad(carb\u00adoxy\u00admeth\u00adyl)oxalamide -antiperiplanar conformation where the 4-pyridyl residues lie to either side of the central C2N2O2 chromophore. The six atoms comprising the central residue are close to co-planar with their r.m.s. deviation equal to 0.0555\u2005\u00c5, with the maximum deviations to either side of the plane being 0.0719\u2005(5) and 0.0642\u2005(5)\u2005\u00c5 for the N2 and O2 atoms, respectively; the C6 and C9 atoms lie 0.1908\u2005(14) and 0.0621\u2005(14)\u2005\u00c5 out of and to one side of the plane (towards the N2 atom), respectively. The N1- and N4-pyridyl rings form dihedral angles of 86.00\u2005(3) and 83.34\u2005(2)\u00b0, respectively, with the plane through the C2N2O2 atoms, so are close to perpendicular to the central plane. The dihedral angle between the pyridyl rings is 33.60\u2005(5)\u00b0, indicating a splayed disposition as each pyridyl ring is folded away from the rest of the mol\u00adecule. The carbonyl groups are anti and the mol\u00adecule features intra\u00admolecular amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds that complete S(5) loops, Table\u00a01The mol\u00adecular structures of the three constituents comprising the crystallographic asymmetric unit of (I)2 group being 6.33\u2005(14) and 3.43\u2005(10)\u00b0 for the O3- and O5-benzoic acid mol\u00adecules, respectively. As expected, the C15\u2014O3(carbon\u00adyl) bond length of 1.2162\u2005(13)\u2005\u00c5 is significantly shorter than the C15\u2014O4(hy\u00addroxy) bond of 1.3197\u2005(13)\u2005\u00c5; the bonds of the O5-benzoic acid follow the same trend with C22\u2014O5 of 1.2237\u2005(13)\u2005\u00c5 compared with C22\u2014O6 of 1.3084\u2005(13)\u2005\u00c5.There are two independent benzoic acid mol\u00adecules in (I)via amide-N\u2014H\u22efO(amide) hydrogen bonding, which leads to a centrosymmetric ten-membered {\u22efHNC2O}2 synthon. The second amide forms an amide-N\u2014H\u22efO(carbon\u00adyl) bond with the result of that adjacent six-mol\u00adecule aggregates are connected into a supra\u00admolecular tape via 22-membered {\u22efHOCO\u22efNC4NH}2 synthons, Fig.\u00a02a). The other notable contact within the tape is a pyridyl-C\u2014H\u22efO(carbon\u00adyl) inter\u00adaction, which cooperates with a hy\u00addroxy-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bond to form a seven-membered {\u22efOCOH\u22efNCH} pseudo-heterosynthon; no analogous inter\u00adaction is noted for the O5-benzoic acid. The supra\u00admolecular tapes are aligned along the c-axis direction and have a linear topology.As anti\u00adcipated from the chemical composition, significant conventional hydrogen bonding is noted in the crystal of (I)i.e. methyl\u00adene-C\u2014H\u22efO(amide) and pyridyl-C\u2014H\u22efO(carbon\u00adyl), the latter involving both pyridyl rings and each carbonyl-O atom, Table\u00a01b).The connections between chains leading to a three-dimensional architecture are of the type C\u2014H\u22efO, Crystal Explorer 17  hydrogen bonds was used as the input for calculations. A list of the short inter\u00adatomic contacts discussed below is given in Table\u00a02dnorm surfaces, Fig.\u00a034LH2 and BA mol\u00adecules, hereafter BA-I for the O3-containing mol\u00adecule and BA-II for the O5-mol\u00adecule, which indicate the presence of close contacts with distances shorter than the sum of the respective van der Waals radii , benzoic acid-O6\u2014H6O\u22efN4(pyrid\u00adyl), amide-N2\u2014H2N\u22efO2(amide) and amide-N3\u2014H3N\u22efO5(carbon\u00adyl) hydrogen-bonding inter\u00adactions exhibit the most intense red spots on the dnorm surfaces, suggestive of strong inter\u00adactions.The program a) and (b) [in the order of moderate intensity (m) to weak intensity (w)] were identified for C6\u2014H6B\u22efO1 (m), C12\u2014H12\u22efO3 (m), C2\u2014H2\u22efO5 (m) and C1\u2014H1\u22efO3 (w), Table\u00a01m), C28\u2014H28\u22efO1 (w), C9\u2014H9B\u22efC17 (w), C9\u2014H9B\u22efO3 (w), C13\u2014H13\u22efC1 (w), C12\u22efC21 (w) and C8\u22efC26 (w), Table\u00a02PLATON  and (d).Other, relatively less intense red spots in Fig.\u00a034LH2, BA-I and BA-II mol\u00adecules through DFT-B3LYP/6-31G to further study the nature of the close contacts, Fig.\u00a04-\u2013H\u22efN and N\u2014H\u22efO hydrogen-bonding contacts that exhibited the most intense red spots on the dnorm map are highly electrostatic in nature, as evidenced from the intense electronegative (red) and electropositive (blue) regions on the Hirshfeld surfaces of the individual mol\u00adecules. Other regions are relatively pale, indicating the complementary role of the remaining contacts in sustaining the mol\u00adecular network in the crystal.The electrostatic potential mapping was performed on the individual i.e. the three-mol\u00adecule aggregate specified above, as well as its individual 4LH2, BA-I and BA-II components, Fig.\u00a054LH2 and benzoic acid in constructing the mol\u00adecular packing of the system, in contrast to the previously reported benzene monosolvate of 4LH2 i.e. the donor or acceptor atoms inter\u00adnal to the surface) and external  contacts. In contrast, for H\u22efC/C\u22efH and H\u22efO/O\u22efH, the distributions are slightly inclined towards -C\u22efH- (15.8%) and -O\u22efH- (13.4%) as compared to the corresponding counterparts at 11.7 and 11.8%, respectively. A detailed analysis of the di + de distances shows that the closest H\u22efO/O\u22efH and H\u22efC/C\u22efH contacts of \u223c1.95\u2005\u00c5 and \u223c2.62\u2005\u00c5, respectively, occur at distances shorter than the sum of the respective van der Waals radii of 2.61 and 2.79\u2005\u00c5, while the H\u22efH (\u223c2.20\u2005\u00c5) and N\u22efH/ H\u22efN (2.80\u2005\u00c5) contacts are longer than the sum of van der Waals radii of 2.18 and 2.64\u2005\u00c5, respectively.The major surface contacts for (I)4LH2 mol\u00adecule also displays a shield-like profile with asymmetric spikes which upon further decomposition could be delineated into H\u22efH (38.0%), H\u22efO/O\u22efH (25.6%), H\u22efC/C\u22efH (21.4%) and H\u22efN/N\u22efH (9.9%) contacts. The H\u22efO/O\u22efH contact exhibits a forceps-like profile with the distribution inclined towards inter\u00adnal-H\u22efO-external (15.2%) as compared to inter\u00adnal-O\u22efH-external (10.4%), and both with tips at di + de \u223c1.94\u2005\u00c5 which is indicative of significant hydrogen bonding. Similarly, the asymmetric, needle-like profile for the H\u22efN/N\u22efH contact is inclined towards the inter\u00adnal-N\u22efH-external (9.0%) with the tip at di + de = \u223c1.6\u2005\u00c5, while the remaining 0.9% is attributed to the inter\u00adnal-H\u22efN-external contact with di + de of \u223c2.94\u2005\u00c5 . The H\u22efC/C\u22efH contacts are evenly distributed on both sides of the contacts with the di + de of \u223c2.64\u2005\u00c5 which is slightly shorter than the sum of van der Waals radii. On the other hand, the H\u22efH contacts have little direct influence in sustaining the mol\u00adecular packing as shown from the shortest di + de value of \u223c2.2\u2005\u00c5, which is longer than the sum of the van der Waals radii despite the prominent contributions these make to the overall surfaceThe i.e. 31.9% for BA-I cf. 38.7% for BA-II. The discrepancy in the distribution for BA-I is compensated by the increase in O\u22efC/C\u22efO and C\u22efC contacts with the distribution being 4.8 and 2.9%, respectively. The distribution for H\u22efC/C\u22efH (29.0 vs 29.1%), H\u22efO/O\u22efH (23.8 vs 24.2%) and H\u22efN (6.7 vs 5.7%) contacts is approximately the same in both BA-I and BA-II, except that the H\u22efC/C\u22efH distribution for BA-II is significantly more inclined towards inter\u00adnal-C\u22efH-external (20.5%) than the inter\u00adnal-H\u22efC-external (8.6%) in contrast to the relatively balanced distribution for BA-I 15.5% for inter\u00adnal-C\u22efH-external vs 13.5% for inter\u00adnal-H\u22efC-external. In BA-I, the di + de values for H\u22efO/O\u22efH, H\u22efC/C\u22efH and H\u22efN/N\u22efH at the tips are \u223c2.26\u20132.70, 2.62 and 1.64\u2005\u00c5, respectively, while the equivalent values for the analogous contacts for BA-II have tips at 2.02\u20132.56, 2.62\u20132.86 and 1.58\u2005\u00c5, respectively. Among these contact distances, the O\u22efH, H\u22efC/C\u22efH and H\u22efN for BA-I as well as H\u22efO/O\u22efH, H\u22efC and H\u22efN for BA-II are shorter than the sum of van der Waals radii. As expected, the minimum di + de value for the H\u22efH contacts is longer than the sum of van der Waals radii, even if it is the most dominant contact for each mol\u00adecule. The aforementioned data for BA-I and BA-II clearly distinguishes the independent mol\u00adecules.As for the pair of BA mol\u00adecules, both BA-I and BA-II possess similar, claw-like profiles which differ in the diffuse region, with the former being the characteristic of H\u22efH contacts while the latter is due to H\u22efC/C\u22efH inter\u00adactions. Qu\u00adanti\u00adtatively, differences mainly relate to the percentage contribution by H\u22efH contacts, CrystalExplorer17  hydrogen bonds complemented by a pair of pyridyl-C13\u2014H13\u22efC1(pyrid\u00adyl) inter\u00adactions between two oxamide mol\u00adecules led to the greatest inter\u00adaction energy (Etot) of \u221275.2\u2005kJ\u2005mol\u22121. This value is comparable to Etot of \u221271.7\u2005kJ\u2005mol\u22121 calculated for the classical eight-membered {\u22efHOCO}2 inter\u00adaction  and pyridyl-C1\u2014H1\u22efO3(carbon\u00adyl) contacts, which combine to generate a seven-membered heterosynthon with Etot of \u221250.1\u2005kJ\u2005mol\u22121. A diminution in Etot is observed for the other pyridyl terminus, which only comprises a carb\u00adoxy\u00adlic-O6\u2014H6O\u22efN4(pyrid\u00adyl) hydrogen bond without a supporting pyridyl-C\u2014H\u22efO(carbon\u00adyl) inter\u00adaction, showing an energy of \u221243.9\u2005kJ\u2005mol\u22121 and ranked third strongest among all inter\u00adactions in (I)To assess the strength of the specified inter\u00adactions in the Hirshfeld surface analysis, the mol\u00adecules in (I)Etot of \u221236.3\u2005kJ\u2005mol\u22121 involves contributions from the amide-N3\u2014H3N\u22efO5(carb\u00adoxy\u00adlic acid) and phenyl-C28\u2014H28\u22efO1(amide) contacts. Other inter\u00adactions include the methyl\u00adene-C6\u2014H6B\u22efO1(amide) contacts (\u201325.1\u2005kJ\u2005mol\u22121), the combination of benzoic acid-C20\u2014H20\u22efC8(amide) and benzoic acid-C12\u22efC21(pyrid\u00adyl) (\u201321.0\u2005kJ\u2005mol\u22121), amide-C8\u22efC26(benzoic acid) (\u201319.4\u2005kJ\u2005mol\u22121), pyridyl-C2\u2014H2\u22efO5(carb\u00adoxy\u00adlic acid) (\u201315.6\u2005kJ\u2005mol\u22121), a combination of (pyridine meth\u00adyl)-C9\u2014H9B\u22efO3(carb\u00adoxy\u00adlic acid) and methyl\u00adene-C9\u2014H9B\u22efC17(benzoic acid) (\u221214.7\u2005kJ\u2005mol\u22121), as well as pyridyl-C12\u2014H12\u22efO3(carb\u00adoxy\u00adlic acid) (\u20138.3\u2005kJ\u2005mol\u22121). Some inconsistencies are observed between the calculated Etot and Hirshfeld surface analysis, particularly for C2\u2014H2\u22efO5 and C12\u2014H12\u22efO3. These inter\u00adactions can be considered weak even though they possess a relatively short contact distance compared to the sum of van der Waals radii, as indicated from the moderately intense red spots on the Hirshfeld surface. The contradiction could arise as a result of the relatively high repulsion terms, which weaken the inter\u00adaction energy.The next highest inter\u00adaction energy with 2O}2 synthon as well as the terminal inter\u00adactions between 4LN2 and BA mol\u00adecules, through hy\u00addroxy-O\u2014H4\u22efN(pyrid\u00adyl) hydrogen bonds, lead to a zigzag electrostatic energy framework, Fig.\u00a06a). The packing system is further stabilized by the dispersion forces contributed by the ten-membered {\u22efHNC2O}2 synthon complemented by other peripheral inter\u00adactions such the pairwise C20\u2014H20\u22efC8/C12\u22efC21, C8\u22efC26 and C6\u2014H6B\u22efO1 inter\u00adactions, which result in a dispersion energy framework resembling a spider web, Fig.\u00a06b). The combination of the electrostatic and dispersion forces leads to an overall energy framework that resembles a ladder, Fig.\u00a06c).Overall, the crystal of (I)Chemical context, 4LH2 mol\u00adecules have long been known to form co-crystals with carb\u00adoxy\u00adlic acids. A list of 4LH2/carb\u00adoxy\u00adlic acid co-crystals is given in Table\u00a044LH2, the length of the central C\u2014C bond, recognized as being long diazen\u00adyl]benzoic acid, carries a hydroxyl residue and this preferentially forms the hydrogen bonds to the pyridyl-N atoms. This observation is contrary to literature expectation where the carb\u00adoxy\u00adlic acid would be expected to form hydrogen bonds preferentially to pyridyl-N atom in instances where there is a competition with putative hydroxyl-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds  loop, in accord with Etter\u2019s rules, i.e. \u2018six-membered ring intra\u00admolecular hydrogen bonds form in preference to inter\u00admolecular hydrogen bonds\u2019 oxalamide (4LH2), was prepared according to the literature; M.p.: 486.3\u2013487.6\u2005K; lit. 486\u2013487\u2005K  was mixed with benzoic acid  and the physical mixture was then ground for 15\u2005min in the presence of a few drops of methanol. The procedures were repeated three times. Colourless blocks were obtained through careful layering of toluene (1\u2005ml) on an N,N-di\u00admethyl\u00adformamide (1\u2005ml) solution of the ground mixture. M.p.: 435.4\u2013436\u2005K. IR (cm\u22121): 3321 \u03bd(N\u2014H), 3070\u20132999 \u03bd(C\u2014H), 1702\u20131662 \u03bd(C=O), 1506 \u03bd(C=C), 1417 \u03bd(C\u2014N).The precursor, 4LH2:benzoic acid in molar ratios of 1:2, 1:3 and 1:4 were also attempted but only the 2:1 co-crystal (I)Similar experiments with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located from a difference Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019016840/hb7875sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019016840/hb7875Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016840/hb7875Isup3.cmlSupporting information file. DOI: 1972449CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-chromen-4-yl)\u00adoxy]acetic acid di\u00admethyl\u00adsulfoxide monosolvate is described and the inter\u00admolecular contacts in the crystal analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.The crystal structure of 2-[(2-oxo-2 11H8O5\u00b7(CH3)2SO, is a new coumarin derivative. The asymmetric unit contains two coumarin mol\u00adecules (A and B) and two di\u00admethyl\u00adsulfoxide solvent mol\u00adecules (A and B). The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56\u2005(2)\u00b0 for mol\u00adecule A and 1.83\u2005(2)\u00b0 for mol\u00adecule B. In mol\u00adecule A, the dimethyl sulfoxide sulfur atom is disordered over two positions with a refined occupancy ratio of 0.782\u2005(5):0.218\u2005(5). In the crystal, mol\u00adecules are linked by O\u2014H\u22efO hydrogen bonds, forming chains running along the c-axis direction. The chains are linked by C\u2014H\u22efO hydrogen bonds, forming layers parallel to the ac plane. In addition, there are also C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions present within the layers. The inter\u00admolecular contacts in the crystal have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots, which indicate that the most important contributions to the packing are from H\u22efH (33.9%) and O\u22efH/H\u22efO (41.2%) contacts.The title compound, C The synthesis, and pharmacological and other properties of coumarin derivatives have been studied intensively and reviewed  and atoms O2A and O2B deviate from this mean plane by 0.007\u2005(3) and 0.039\u2005(3)\u2005\u00c5, respectively. The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56\u2005(16)\u00b0 for mol\u00adecule A and 1.83\u2005(16)\u00b0 for mol\u00adecule B; this value is in agreement with those found in analogous coumarin derivatives  and 0.218\u2005(5).The 1H-chromen-4-yl)\u00adoxy]acet\u00adyl}piperazin-1-yl)acetamide -2-[(2-oxo-2H-chromen-4-yl)\u00adoxy]acetamide , Cg1\u22efCg4iv = 3.509\u2005(2) and Cg2\u22efCg3iv 3.572\u2005(2)\u2005\u00c5 where Cg1, Cg2, Cg3 and Cg4 are the centroids of rings O1A/C1A/C6A\u2013C9A, C1A\u2013C6A, O1B/C1B/C6B\u2013C9B, and C1B\u2013C6B, respectively; symmetry code: (iv) x, 1\u00a0+\u00a0y, z].The crystal structure features O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds Table\u00a01. In the \u03c0 Table\u00a01 and \u03c0\u2013\u03c0 et al., 2019et al., 2007CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of 0.774 (red) to 1.381 (blue) for the title compound, where the red spots indicate the inter\u00admolecular contacts involved in the hydrogen bonding.The Hirshfeld surface of the title compound mapped over b) and O\u22efH/H\u22efO at 41.2% , followed by the C\u22efH/H\u22efC contacts at 9.6% , C\u22efC contacts at 6.3%  and S\u22efH/H\u22efS contacts at 3.9% .The fingerprint plots are given in Fig.\u00a062% Fig.\u00a06c, follo6% Fig.\u00a06d, C\u22efC c3% Fig.\u00a06e and S\u22ef9% Fig.\u00a06f.et al., 2016et al., 2006H-furo-[1]-benzo\u00adpyran-7-one monohydrate -4,5-bis\u00ad(pyrrolidinylcarbon\u00adyl)-2,2-dimethyl-1,3-dioxolane cyclo\u00adpropyl sulfamate  acetate  in THF (10\u2005mL) at 273\u2005K and stirred at 273\u2005K for 1\u2005h. Completion of the reaction was confirmed by TLC (mobile phase ethyl acetate/hexa\u00adne) and THF was distilled off using a rotavapor. The obtained solution was washed with ethyl acetate (20\u2005mL). The aqueous layer was acidified with 2N HCl (pH 1.0\u20132.0) and the obtained solid was filtered, washed with hexane and dried under vacuum to give as white solid. The purified compound was recrystallized using dimethyl sulfoxide as solvent.A solution of lithium hydroxide  in water (4\u2005mL) was added to ethyl 2-(2-oxo-2Uiso(H) = 1.5Ueq(C-meth\u00adyl) or 1.2Ueq(C) for other H atoms. In mol\u00adecule A, the sulfur atom of the sulfinyldi\u00admethane group is disordered over two positions with refined occupancies of 0.782\u2005(5) and 0.218\u2005(5). In the final cycles of refinement, five outliers were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019009447/vm2218sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019009447/vm2218Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019009447/vm2218Isup3.cmlSupporting information file. DOI: 1891495CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, N\u2014H\u22efCl, O\u2013H\u22efCl and N\u2014H\u22efO hydrogen bonds connect the anions, cations and water mol\u00adecules, forming a three-dimensional network.In this hydrated 2,6,13,17-tetra\u00adazoniatri\u00adcyclo\u00ad[16.4.0.0 20H44N44+\u00b74Cl\u2212\u00b74H2O, has been determined using synchrotron radiation at 220\u2005K. The structure determination reveals that protonation has occurred at all four amine N atoms. The asymmetric unit contains one half-cation , two chloride anions and two water mol\u00adecules. There are two mol\u00adecules in the unit cell. The Cl\u2212 anions and hydrate mol\u00adecules are involved in hydrogen bonding. The crystal structure is stabilized by inter\u00admolecular hydrogen bonds involving the macrocycle N\u2014H groups and water O\u2014H groups as donors and the O atoms of the water mol\u00adecules and the Cl\u2212 anions as acceptors, giving rise to a three-dimensional network.The crystal structure of the title salt, C These di- or tetra\u00adammonium cations may be suitable for the removal of toxic heavy metal ions from water. The macrocycle L contains a cyclam backbone with two cyclo\u00adhexa\u00adne subunits. Methyl groups are attached to the 3 and 14 carbon atoms of the propyl chains that bridge opposite pairs of N atoms in the structure. Previously, we have reported the crystal structures of [Cu(L)](NO3)2\u00b73H2O, [Cu(L)](NO3)2, [Cu(L)](ClO4)2 and [Cu(L)(H2O)2](BF4)2\u00b72H2O together with [Zn(L)(OCOCH3)2]. In these structures, the copper(II) or zinc(II) cations have tetra\u00adgonally distorted octa\u00adhedral environments with the four N atoms of the macrocyclic ligand in equatorial positions and O atoms of counter-anions, water mol\u00adecules or acetato ligands in axial positions \u00b72MeOH The macrocycle 3,14-dimethyl-2,6,13,17-tetra\u00adaza\u00adtri\u00adcyclo\u00ad(16.4.0.0\u2212 anions and four solvent water mol\u00adecules and was characterized during studies of the macrocyclic ligand and its copper(II) complexes. An ellipsoid plot of the mol\u00adecular components in (I)anti with respect to the macrocyclic plane as a result of the mol\u00adecular inversion symmetry. The six-membered cyclo\u00adhexane ring is in a stable chair conformation. Within the centrosymmetric tetra-protonated amine unit [C20H44N4]4+, the C\u2014C and N\u2014C bond lengths vary from 1.522\u2005(2) to 1.542\u2005(2)\u2005\u00c5 and from 1.506\u2005(2) to 1.522\u2005(2)\u2005\u00c5, respectively. The ranges of N\u2014C\u2014C and C\u2014N\u2014C angles are 106.85\u2005(10) to 114.32\u2005(11)\u00b0 and 116.70\u2005(10) to 118.89\u2005(10)\u00b0, respectively. The bond lengths and angles within the [C20H44N4]4+ tetra-cation are comparable to those found in the free ligand or the di-cation in C20H40N4\u00b72C11H10O \u00b72MeOH 3}(CN)3]2\u00b72H2O\u00b72MeOH . The crystal structures of C20H40N4\u00b72C11H10O \u00b72MeOH 3}(CN)3]2\u00b72H2O\u00b72MeOH  were used as provided. All chemicals were reagent grade and used without further purification. As a starting material, the macrocycle 3,14-dimethyl-2,6,13,17-tetra\u00adaza\u00adtri\u00adcyclo\u00addocosane was prepared according to a published procedure  in water (15\u2005mL). The solution was heated for 1\u2005h at 338\u2005K. After cooling to 298\u2005K, the pH was adjusted to 3.0 with 1.0 M HCl. The solution was filtered and left at room temperature. Colourless crystals suitable for X-ray analysis were obtained unexpectedly from the solution over a period of a few days.Commercially available Uiso(H) values of 1.2Ueq and 1.5Ueq(C-meth\u00adyl). O-bound H atoms of the water mol\u00adecules were located in a difference-Fourier map, and the O\u2014H distances and the H\u2014O\u2014H angles were restrained using DFIX and DANG constraints (0.84 and 1.36\u2005\u00c5).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018009337/sj5559sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009337/sj5559Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018009337/sj5559Isup3.cmlSupporting information file. DOI: 1852146CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Cav1.2 is the pore\u2010forming subunit of L\u2010type voltage\u2010gated calcium channel (LTCC) that plays an important role in calcium overload and cell death in Alzheimer's disease. LTCC activity can be regulated by estrogen, a sex steroid hormone that is neuroprotective. Here, we investigated the potential mechanisms in estrogen\u2010mediated regulation of Cav1.2 protein. We found that in cultured primary neurons, 17\u03b2\u2010estradiol (E2) reduced Cav1.2 protein through estrogen receptor \u03b1 (ER\u03b1). This effect was offset by a proteasomal inhibitor MG132, indicating that ubiquitin\u2013proteasome system was involved. Consistently, the ubiquitin (UB) mutant at lysine 29 (K29R) or the K29\u2010deubiquitinating enzyme TRAF\u2010binding protein domain (TRABID) attenuated the effect of ER\u03b1 on Cav1.2. We further identified that the E3 ligase Mdm2 (double minute 2 protein) and the PEST sequence in Cav1.2 protein played a role, as Mdm2 overexpression and the membrane\u2010permeable PEST peptides prevented ER\u03b1\u2010mediated Cav1.2 reduction, and Mdm2 overexpression led to the reduced Cav1.2 protein and the increased colocalization of Cav1.2 with ubiquitin in cortical neurons in vivo. In ovariectomized (OVX) APP/PS1 mice, administration of ER\u03b1 agonist PPT reduced cerebral Cav1.2 protein, increased Cav1.2 ubiquitination, and improved cognitive performances. Taken together, ER\u03b1\u2010induced Cav1.2 degradation involved K29\u2010linked UB chains and the E3 ligase Mdm2, which might play a role in cognitive improvement in OVX APP/PS1 mice. This effect involved lysine 29\u2010linked ubiquitin chains and the E3 ligase Mdm2 (double minute 2 protein). In OVX APP/PS1 mice, systematic administration of E2 and ER\u03b1 agonist PPT (propylpyrazoletriol) led to the reduced Cav1.2 protein and the enhanced Cav1.2 ubiquitination in the brain, which were accompanied by the improved cognitive functions.22.1Ca2+density) were measured using whole\u2010cell patch recordings. As shown in Figure Ca2+density (pA/pF) was significantly decreased by E2 treatment (24\u00a0hr), whereas ICI attenuated this effect. These results indicated that E2 reduced Cav1.2 protein in cultured primary cortical neurons, which was mediated by ERs.As shown in Figure Ca2+ density  might mediate E2 effect on Cav1.2, we tested the effect of the selective ER\u03b1 agonist  or ER\u03b2 agonist  on Cav1.2 incubated in cortical neurons for 24\u00a0hr. As shown in Figure y Figure . As expe2.2Cav1.2 protein can be regulated at multiple levels  controls Cav1.2 degradation  protein contains seven lysine (K) residues at positions 6, 11, 27, 29, 33, 48, and 63, respectively. In addition, poly\u2010UB chain assembly can occur at any of these lysine residues   and CHIP  are reportedly associated with ER\u03b1 signaling   mice were significantly shorter than that in saline\u2010treated OVX APP/PS1 (AD) mice beginning on the third day Figure a\u2013c. In t3The efficacy of estrogen\u2010based hormone therapy (HT) in AD is not conclusive. Some studies reveal that HT may reduce the risk of AD in postmenopausal women  mediates proteasomal degradation of Cav1.2 in neuronal cells  were from Abcam  and Alomone, respectively, which produced identical Western blots. Those against \u03b2\u2010actin (ab6276), MAP\u20102 (ab32454), ER\u03b1 (ab3573), ER\u03b2 (ab104804), calcineurin (ab3673), Mdm2 (ab16895), and ubiquitin (ab19247) were purchased from Abcam. pSer1928\u2010Cav1.2 (A010\u201070) was from Badrilla (United Kingdom). 17\u03b2\u2010estradiol (E2758), propylpyrazoletriol , diarylprepionitrile , E2\u2010BSA (E5630), ICI 182,780 (V900926), nifedipine (N7630), FK506 (F4679), MG132 (C2211), ammonium chloride (A0171), chloroquine (C6628), carfilzomib (791938), and other reagents were purchased from Sigma . Lipid solvents were made in stock solutions in DMSO .4.2pCMV6\u2010Myc\u2010Mdm2 and pCMV6\u2010Myc\u2010p14ARF were purchased from OriGene (USA). TRABID (DU# 49067) and TRABID mutant C443A (DU# 49089) were purchased from MRC PPU Reagents and Services (University of Dundee). pRK5\u2010HA\u2010ubiquitin was obtained from Addgene. All ubiquitin mutants were made from pRK5\u2010HA\u2010ubiquitin plasmid by mutagenesis. pRK5\u2010HA\u2010Ubiquitin\u2010K0 (no lysine), pRK5\u2010HA\u2010Ubiquitin\u2010K6 (keep lysine at position 6), pRK5\u2010HA\u2010Ubiquitin\u2010K11, pRK5\u2010HA\u2010Ubiquitin\u2010K27, pRK5\u2010HA\u2010Ubiquitin\u2010K29, pRK5\u2010HA\u2010Ubiquitin\u2010K33, pRK5\u2010HA\u2010Ubiquitin\u2010K48, pRK5\u2010HA\u2010Ubiquitin\u2010K63, pRK5\u2010HA\u2010Ubiquitin\u2010K6R , pRK5\u2010HA\u2010Ubiquitin\u2010K29R, pRK5\u2010HA\u2010Ubiquitin\u2010K63R, CHIP with myc tag, and Derlin\u20101 with HA tag were cloned to pcDNA3, respectively.4.36\u00a0cells/ml for biochemical experiments and 0.5\u00a0\u00d7\u00a0106\u00a0cells/ml for molecular and immunohistochemistry experiments. Cultures were maintained in serum\u2010free neurobasal (NB) medium  at 37\u00b0C with 5% CO2. Fifty percent of the medium was exchanged with fresh medium every other day for 2\u00a0weeks. On the day before experiment, culture medium was completely replaced by fresh medium in the presence of accurate dilution of chemicals.Cortical neurons were extracted from prenatal pups on embryonic day 18. Cells were placed on poly\u2010L\u2010lysine (0.1\u00a0mg/ml)\u2010coated 6\u2010well plates, at a density of 2\u00a0\u00d7\u00a0104.42. At\u00a0~\u00a090% confluence, cells were transiently transfected with various plasmids or Mdm2 siRNA using the Lipofectamine 2000 reagent (Invitrogen) according to the manufacturer's instructions. A total of 2.5\u00a0\u03bcg of DNA in 100\u00a0\u03bcl Opti\u2010MEM (Invitrogen) were used in each of six wells. The following human Mdm2 siRNA sequences were used for transfection in SH\u2010SY5Y cells: sense CGUACGCGGAAUACUUCGATT, antisense AAUCGAAGUAUUCCGCGUACG; NC: sense CGUACGCGGAAUACUUCGATT, antisense AAUCGAAGUAUUCCGCGUACG (100\u00a0pM per six wells for 72\u00a0hr). The effectiveness of Mdm2 knockdown was verified by Western blotting analysis.HT22  and SH\u2010SY5Y (human neuroblastoma) cell lines were obtained from the Type Culture Collection of the Chinese Academy of Sciences . Cells were incubated in Dulbecco's modified Eagle's medium  containing 4.5\u00a0g glucose/L, supplemented with penicillin/streptomycin (50\u00a0units/mL), glutamate (2\u00a0mM), and 10% fetal bovine serum , and were maintained at 37\u00b0C with 10% CO4.5Western blotting of Cav1.2 was performed as previously described  assays, the cell or tissue extracts (0.5\u00a0mg) were pre\u2010incubated with protein A agarose beads  for 3\u00a0hr to reduce nonspecific reaction. The supernatants were then mixed with nonspecific IgG and appropriate antibodies for 1\u00a0hr. The mixtures were then incubated with protein A agarose beads  overnight at 4\u00b0C. Samples were washed two times with lysis buffer and two times with sterile PBS and denatured with SDS sampling buffer.4.6Brain sections were washed with ice\u2010cold PBS, then fixed in ice\u2010cold 4% paraformaldehyde for 10\u00a0min, permeabilized in 0.1% Triton X\u2010100 for 10\u00a0min, and blocked with 10% normal goat serum for 1\u00a0hr at 37\u00b0C with extensive PBS washings between each step. Specimens were incubated with appropriate primary antibodies (1:50 in PBS) at 4\u00b0C overnight. The sections were then washed 6\u00a0\u00d7\u00a02\u00a0min with PBS, followed by incubation with the secondary antibody Alexa 549 or Fluro 488 (1:100 in PBS) at 37\u00b0C for 1\u00a0hr. After sealing with a mixture of glycerol and PBS at a ratio of 1:1, the immunofluorescent\u2010labeled sections were examined using a laser scanning confocal microscope  with an Olympus IX 70 inverted microscope  equipped with a Fluoview FVX confocal scan head.4.72+) were recorded from cultured cortical neurons from 7 to 11\u00a0days in vitro (DIV), at room temperature using a MultiClamp 700B amplifier (Axon Instruments). The recording chamber was perfused with Tyrode's solution containing (in mM): NaCl 100, tetraethylammonium\u2010Cl 20, 4\u2010AP 5, KCl 4, MgCl2 1, BaCl210, glycine 0.01, HEPES 25, glucose 30, and TTX 0.001. The glass micropipettes had a resistance of 3\u20135\u00a0M\u03a9 when filled with internal solution containing (in mM): CsCl 135, MgCl2 4, HEPES 10, EGTA 10, MgATP 4, and Na3GTP 0.3. A prepulse protocol consists of 300\u2013700\u00a0ms to \u221230\u00a0mV followed by 50\u00a0ms to \u221250\u00a0mV, before each test pulse was used to inactivate T\u2010type Ca2+ channels and Na+ channels. ICa2+ was elicited by 300\u00a0ms test pulses of variable amplitude (\u221240 to +60\u00a0mV at a step of 10\u00a0mV) from a holding potential of \u221260\u00a0mV. The interval between test pulses was 10\u00a0s.Voltage\u2010dependent calcium\u2010mediated currents . The primer sequences for Cav1.2 were as follows: 5\u2032\u2010TACCGTCAGTTCCACACAGC\u20103\u2032 and 5\u2032\u2010CTTCAGAGTCAGGCAGAGCA\u20103\u2032. The threshold cycle (Ct) value of each sample was calculated, and the relative mRNA level was normalized to the GAPDH mRNA value.4.9ER\u03b1/\u03b2 shRNAs was produced by Shanghai GeneChem Co., Ltd. . At 10 DIV, ER\u2010related lentivirus was added to the culture for 72\u00a0hr according to the manufacturers\u2019 instruction , while transfection of Mdm2 was performed in HT22 cells.The target shRNAs against rat ER\u03b1/\u03b2 gene (NM_012689/NM_012754) were designed as follows: ER\u03b1\u20101: GATAAGAACCGGAGGAAGA, ER\u03b1\u20102: CCAGAATGGCCGAGAGAGA, and ER\u03b1\u20103: GTAAATGTGTAGAAGGCAT; ER\u03b2\u20101: TGAGCAAAGCCAAGAGAAA, ER\u03b2\u20102: TCACTAAGCTGGCGGACAA, and ER\u03b2\u20103: CCAAATGTGCTATGGCCAA. Negative control was the scrambled sequence with no homology to rat genes. The recombinant lentiviral vector bearing rat 4.10in utero electroporation was performed on pregnant C57/B6L mice on embryonic day 14.5 (E14.5) as previously described  and PEST3 (S840/861) were synthesized and purified by Pepmic Co. Ltd . The sequences were as follows: YGRKKRRQRRR\u2010DIDPENEDEGMDED\u2010GFP for TAT\u2010PEST1, YGRKKRRQRRR\u2010DIDKENEDEGKDED\u2010GFP (\u0394PEST1) for scrambled, YGRKKRRQRRR\u2010HSNPNTAGEEDEEEPEMPVGPR\u2010GFP for TAT\u2010PEST3, and YGRKKRRQRRR\u2010HSNPNPAGEEDKEEPAMPVGPR\u2010GFP (\u0394PEST3) for scrabbled control  were obtained from Nanjing University (China). Eight\u2010month\u2010old female APP/PS1 mice were bilaterally ovariectomized (OVX) for 14\u00a0days. Animals were subcutaneously injected daily with vehicle, 17\u03b2\u2010estradiol , PPT (1\u00a0mg/kg), and DPN (1\u00a0mg/kg) for two weeks. The dosage of E2 is thought to be within physiological range; and those of PPT and DPN are functional  were recorded by a video and analyzed by image analyzing software . For contextual and cued fear conditioning, mice were tested in a 3\u2010day paradigm. Behavior was recorded by video camera, and freezing data were measured using FreezeScan software.4.14SEM from at least three independent experiments. The statistical comparisons between two groups were tested using Student's t test. The comparisons among groups were tested using one\u2010way or two\u2010way ANOVA, and a post hoc pairwise comparison was used where it applied.Data were presented as means\u00a0\u00b1\u00a0None declared.G\u2010J Chen and Z Yan designed the research; Y\u2010J Lai performed the research and analyzed the data; B\u2010L Zhu, F Sun, D Luo, Y\u2010L Ma, B\u2010Luo, J Tang, M\u2010J Xiong, L Liu, X\u2010T Hu, L He, X\u2010J Deng, J\u2010H Zhang, and J Yang provided assistance with the research; G\u2010J Chen and Y\u2010J Lai wrote the paper. All authors read and approved the final manuscript.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file."}
{"text": "R)\u2010[11C]PK11195 was investigated. The synthesis of the reference compound was accomplished in six steps and 9\u2009% overall yield, and the precursor was prepared in eight steps and 8\u2009% overall yield. The chiral separation of the reference and precursor compounds was performed using supercritical fluid chromatography with >95\u2009%\u2005ee. The absolute configuration was determined by circular dichroism. Optimisation of reaction conditions for manual radiolabelling revealed acetonitrile as a preferred solvent at 100\u2009\u00b0C. Automation of this radiolabelling method provided R and S enantiomers in respective 21.3\u00b116.7 and 25.6\u00b17.1\u2009% decay\u2010corrected yields and molar activities of 55.8\u00b135.6 and 63.5\u00b139.5\u2005GBq\u2009\u03bcmol\u22121 (n=3). Injection of the racemic analogue into a healthy rat confirmed passage through the blood\u2013brain barrier.Translocator protein (TSPO) is a biomarker of neuroinflammation, which is a hallmark of many neurodegenerative diseases and has been exploited as a positron emission tomography (PET) target. Carbon\u201011\u2010labelled PK11195 remains the most applied agent for imaging TSPO, despite its short\u2010lived isotope and low brain permeability. Second\u2010generation radiotracers show variance in affinity amongst subjects  caused by the genetic polymorphism (rs6971) of the TSPO gene. To overcome these limitations, a new structural scaffold was explored based on the TSPO pharmacophore, and the analogue with a low\u2010affinity binder/high\u2010affinity binder (LAB/HAB) ratio similar (1.2 vs. 1.3) to that of ( R\u20101\u2010(2\u2010chlorophenyl)\u2010N\u2010methyl\u2010N\u2010(1\u2010methylpropyl)\u20103\u2010isoquinoline carboxamide ((R)\u2010[11C]PK11195, [11C]1, Figure\u2005m).R)\u2010[11C]1 has been used in PET imaging to show neuroinflammation in\u2005vivo in cases of stroke, neurodegeneration, traumatic brain injury, and neoplasia.11C]1 in research and clinical settings, such as low brain permeability,t1/2=20\u2005min), which restricts its use to PET centres that have a cyclotron on site.Neuroinflammation, an immune response to neuronal insult, is a core component of many disorders such as stroke, multiple sclerosis (MS), neurodegenerative disorders, and brain tumours.11C]1, multiple new TSPO radiotracers have been developed and studied; these have improved properties for application, including several that are labelled with the longer\u2010lived radioisotope fluorine\u201018 (t1/2=109.9\u2005min).N\u2010(2\u2010(methoxy\u201011C)benzyl)\u2010N\u2010(4\u2010phenoxypyridin\u20103\u2010yl)acetamide , and good clearance from striatum (region of low TSPO expression) in rats.In 2004, a study by Okubo et\u2005al. described a tetracyclic indole\u2010based pharmacophore .However, while 6 as well as the initial in\u2005vivo preclinical PET.Toward this objective informed by structure\u2013activity design features, a novel series of compounds based on the chemical scaffold18F]6, we proposed an SN2 nucleophilic substitution of a good leaving group with [18F]fluoride, for which reason tosylate 25 and mesylate 26 were envisioned as potential precursors. Reference compound 6  to give product 23. A second hydrogenation on crude 23 in the absence of triethylamine was performed to remove the benzyl protecting group to give crude 24 in quantitative yield. Using crude alcohol 24, we prepared both crude tosylate 25 and crude mesylate precursor 26 . However, the mesyl precursor 26 required purification by column chromatography, yielding a viscous oil (37\u2009%), thus making tosyl precursor 25 practically easier to purify and handle than the mesyl precursor 26.Analogously, 2\u2010chloro\u20105\u2010methoxyaniline hydrochloride 18F]6 by establishing the chiral separation of both reference compound 6 as well as its radiolabelling precursor (25). A clear choice for chiral separation was found in the preparation of diastereomeric mixture by application of a chiral derivatisation group. We identified an acid intermediate 21 for further functionalisation with several potential enantiomerically pure alcohols. The alcohols selected were l\u2010menthol, (R)\u2010(\u2212)\u20102\u2010butanol, and (R)\u20101\u2010phenyl\u20102\u2010propyn\u20101\u2010ol. The ester 28 with (R)\u2010(\u2212)\u20102\u2010butanol was formed in 53\u2009% yield using DBU as a base and a mesylate analogue 27 of the alcohol as an intermediate. However, a higher\u2010yielding and a more direct method of EDCI/DMAP coupling was used to form the esters with l\u2010menthol and (R)\u20101\u2010phenyl\u20102\u2010propyn\u20101\u2010ol, which afforded 29 and 30 in 54 and 31\u2009% yields, respectively \u20101\u2010phenyl\u20102\u2010propynyl analogues. Flash chromatography using diethyl ether and cyclohexane yielded two diasteriomerically enriched samples with both esters 29 (in 78 and 40\u2009% diastereomeric excess) and 30 (in 82 and 35\u2009% diastereomeric excess) \u201029, \u201029 and \u201030, \u201030). To demonstrate the presence of a single enantiomer in a mixture, the chiral l\u2010menthol functionality was first removed under a variety of basic conditions (Table\u20052O in EtOH (entry\u20051), which were the hydrolytic conditions used in the synthesis of the reference compound 6 and precursors 25 and 26. Reaction with LiOH in a mixture of THF/H2O (entry\u20052) gave a minor byproduct.While NMR analysis demonstrated the presence of two diastereomers in all three product mixtures, TLC analysis of the ester mixtures using a variety of solvent systems showed the two diastereomers could be separated readily by flash column chromatography in two cases, that of 2CO3 in MeOH (entry\u20053) gave an equal amount of the desired product and an unidentified byproduct,l\u2010menthol using EDCI/DMAP. To our disappointment, 1H\u2005NMR analysis indicated complete racemisation from all investigated hydrolytic reaction conditions. This was further confirmed by chiral HPLC analysis of the acid samples obtained from hydrolysis of diastereomerically enriched ester samples \u201021, Scheme\u200521 in a solution presumably due to the presence of a highly acidic proton is a likely explanation for such rapid racemisation of the stereocenter. In the case of the ester analogue 30, while we were able to obtain diastereomerically enriched samples through multiple rounds of flash column chromatography in diastereomeric excess \u201030, \u201030), a previously described CuCl hydrolysis protocol failed to give the enantiomerically enriched product 21 (Scheme\u20056 and tosylate 25 (see the Supporting Information for details).Using K6 was next determined by electronic circular dichroism (CD) spectroscopy whereby CD spectra of 6 were compared with that of 5, for which stereochemistry had already been established \u20105 was composed of a maximum positive Cotton effect at 200\u2005nm and a corresponding maximum negative Cotton effect at 226\u2005nm. The enantiomer of 6, which similarly exhibited a maximum positive Cotton effect at 204\u2005nm and a corresponding maximum negative Cotton effect at 228\u2005nm, was in analogy assigned as the S\u2005isomer. The other isomer showed the mirror image bisignate band in the CD spectrum and was therefore identified as R\u2005enantiomer.The absolute stereochemistry of enantiomers of d Figure\u2005. The speS\u2005enantiomer (Supporting Information).To correlate enantiomers obtained via SFC separation to CD data, the chiral HPLC separation was performed on a Whelk\u2010O1 column to unambiguously identify first eluting peak as the 5 was shown to bind to wild\u2010type TSPO with a higher affinity than compound 1, but lost affinity at A147T TSPO (Table\u2005S)\u20106 bound to wild\u2010type TSPO with a similar affinity to compound 1, and both compounds 1 and (S)\u20106 only showed minor loss in affinity at A147T TSPO \u20106: 36.3\u2005nm, while 1.04\u2005nm for rat TSPO.Using an assay based on human embryonic kidney cell lines stably overexpressing human TSPO wild\u2010type and TSPO A147TPO Table\u2005. Compoun18F]5, manual radiochemical reactions were performed first. Both precursors 25 and 26 were assessed and the effect of temperature, solvent, and time was investigated (Table\u200525 (entries\u20051\u20136), a single radiolabelled product formed which was identified as [18F]6 via co\u2010injection of reference compound 6. However, when using 26 (entries\u20057\u201312), a second unidentified radiolabelled product was formed during the reaction. The amount of this radiolabelled side product which formed immediately, did not change during the course of the reaction.To establish suitable reaction conditions for radiolabelling of [ed Table\u2005. For all18F]fluoride to [18F]6 was observed: the highest being 18\u2009% when MeCN was used as a solvent and mesylate 25 as a precursor. When the temperature was increased to 100\u2009\u00b0C or 120\u2009\u00b0C reactions performed in DMF similarly showed poor conversion (entries\u20056 and 12) after 20\u2005min. In DMSO, [18F]6 formed with 3\u2009% conversion after 20\u2005min (entry\u200510) when 26 was used as precursor, whereas tosylate 25 afforded 47\u2009% conversion into [18F]6 under analogous conditions (entry\u20054). The highest conversion in the case of both precursors 25 and 26 was observed after 20\u2005min in MeCN: 81 and 39\u2009%, respectively (entries\u20052 and 8).At 80\u2009\u00b0C, independent of solvent and precursor, low conversion of <20\u2009% of [25 was used for automated radiolabelling on a GE Healthcare FXFN TRACERlab instrument. [18F]Fluorination was achieved with cyclotron\u2010produced [18F]fluoride in MeCN at 100\u2009\u00b0C for 20\u2005min. Product [18F]6 was purified by semipreparative reversed\u2010phase HPLC.With this result in hand , next tosylate 18F]6 was 60\u2005min from end of bombardment (EOB). Radiochemical purity was over 99\u2009%, and radiolabelling yield was 20.8\u00b14.5\u2009% decay\u2010corrected to EOB or 13.6\u00b12.8\u2009% non\u2010decay\u2010corrected, and molar radioactivity 93.2\u00b150.6 GBq\u2009\u03bcmol\u22121 (n=9) at the end of synthesis (EOS). Furthermore, the same automated protocol was used for the radiosyntheses of (R)\u2010[18F]6 and (S)\u2010[18F]6 as follows: 21.3\u00b116.7 and 25.6\u00b17.1\u2009% decay\u2010corrected yields, radiochemical purity >98\u2009% and molar radioactivities 55.8\u00b135.6 and 63.5\u00b139.5\u2005GBq\u2009\u03bcmol\u22121 (n=3) at the EOS, respectively.Total radiosynthesis time for the preparation for [18F]6 enters the brain  was distilled over P2O5 and stored over KOH. Reported density values are for ambient temperature. Purity of compounds was \u226595\u2009% as determined by analytical HPLC on a Thermo Dionex 3000 HPLC system. Preparative chromatographic separations were performed on Material Harvest silica gel 60 (35\u201375\u2005\u03bcm) and reactions followed by TLC analysis using Sigma\u2013Aldrich silica gel 60 plates (2\u201325\u2005\u03bcm) with fluorescent indicator (254\u2005nm) and visualised with UV or potassium permanganate.All reactions requiring anhydrous conditions were conducted in oven\u2010dried glass apparatus under an atmosphere of inert gas. Reagents were purchased from Sigma\u2013Aldrich or Alfa Aesar. Reagents were used without further purification unless otherwise noted. Triethylamine =7.26\u2005ppm, \u03b4C=77.2\u2005ppm. Multiplicities in the 1H\u2005NMR spectra are described as: s=singlet, d=doublet, t=triplet, q=quartet, quint.=quintet, s=sextet, h=heptet, m=multiplet, b=broad; coupling constants are reported in Hz.18 1.7\u2005\u03bcm, 2.1\u00d750\u2005mm; flow rate: 0.6\u2005mL\u2009min\u22121, 4\u2005min method, 5\u201395\u2009% MeCN/H2O with 0.1\u2009% formic acid. HRMS data were obtained from the EPSRC Mass Spectrometry Service at the University of Swansea. Ion mass/charge (m/z) ratios are reported as values in atomic mass units.LC\u2013MS data were obtained using a Waters Acquity\u2010H/Xevo TQD LC\u2013MS instrument. Column: Acquity UPLC\u00ae BEH CFN TRACERlab. Semipreparative purification of radiolabelled material was performed on a Merck\u2010Hitachi L6200A system equipped with Knauer variable wavelength detector and an Eberline radiation detector using a reversed\u2010phase column  and eluting with 48\u2009% aq. MeCN at a flow rate of 5\u2005mL\u2009min\u22121. Analytical HPLC samples were analysed by an Agilent HPLC 1100 system equipped with UV multi\u2010wavelength detector and Raytest Gabi star radiation detector using reversed\u2010phase column (Phenomenex Luna 5\u2005\u03bcm C18 (2) 100\u2005\u00c5, 250\u00d74.6\u2005mm, 675295\u201011) and eluting with 0\u20133\u2005min isocratic 10\u2009% aq. MeCN, 3\u20135\u2005min gradient 10\u201380\u2009% aq. MeCN, 6\u201312\u2005min isocratic 80\u2009% aq. MeCN at a flow rate of 1.5\u2005mL\u2009min\u22121.The automated radiosynthesis was performed on a GE Healthcare FX2\u2010Fluoroethyl 4\u2010methylbenzenesulfonate (8). Commercially available 2\u2010fluoroethanol 7  was dissolved in pyridine (2.5\u2005mL) under nitrogen. The solution was stirred at 0\u2009\u00b0C and tosyl chloride  added portion\u2010wise to the solution over a period of 30\u2005min, keeping the temperature below 5\u2009\u00b0C. The reaction was stirred at RT for 18\u2005h. The reaction was then quenched by careful addition of ice followed by water (5\u2005mL). The reaction mixture was extracted into EtOAc (10\u2005mL) and washed with water (3\u00d710\u2005mL), 1\u2009m HCl solution (10\u2005mL), 1\u2009m aqueous sodium carbonate (10\u2005mL), and copper sulfate (2\u00d710\u2005mL). The organic layer was washed with brine (10\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give 8 as an oil . LC\u2013MS: Rf 1.86 (\u2212ESI) m/z 311.5 ([M+94]+); 1H\u2005NMR : \u03b4H=7.81 , 7.36 , 4.57 , 4.26 , and 2.45 . Characterization data for this compound are in complete agreement with previously published data.N\u2010(2\u2010fluoroethyl)\u20105\u2010methoxyaniline (10)2\u2010Chloro\u2010. Commercially available 2\u2010chloro\u20105\u2010methoxyaniline hydrochloride 9  was dissolved in DMF (60\u2005mL) and sodium hydride  was added. The reaction was stirred for 30\u2005min at RT under nitrogen. The tosylate 8  in DMF was then added dropwise and the reaction was stirred at RT for 2\u2005h. The reaction was then heated at 100\u2009\u00b0C for 18\u2005h. The reaction was allowed to cool and the solvent was removed under reduced pressure. The residue was dissolved in EtOAc (100\u2005mL) and washed with water (5\u00d7100\u2005mL). The organic layers were combined, dried (MgSO4) and concentrated in\u2005vacuo to give a brown oil. The crude mixture was then purified by silica flash chromatography eluting with a gradient of 5\u201330\u2009% EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to yield 10 as a yellow oil . LC\u2013MS: Rf 2.01 (+ESI) m/z 204.3 ([M+H]+); 1H\u2005NMR : \u03b4H=7.16 CHCH), 6.25\u20136.22 CHCH), 4.64 , 4.65\u20134.55 , 3.77 , and 3.48 . Characterization data for this compound are in complete agreement with an internal GE publication.Ethyl 3\u2010bromo\u20102\u2010hydroxycyclohex\u20101\u2010ene\u20101\u2010carboxylate (11). Ethyl 2\u2010oxocyclohexanecarboxylate S1 was dissolved in diethyl ether and cooled to 0\u2009\u00b0C under nitrogen. Bromine was added dropwise over 15\u2005min and the reaction mixture was allowed to warm to RT over 90\u2005min. The mixture was slowly poured into ice\u2010cold saturated aqueous potassium carbonate and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, concentrated in\u2005vacuo and dried on the vacuum line for 18\u2005h to afford 11 as a yellow oil. LC\u2013MS: Rf 2.17; 1H\u2005NMR : \u03b4H=11.92 , 4.93 ), 4.20 OCH2CH3), 2.53\u20132.46 , 2.12\u20132.03 , 1.79\u20131.67 , 1.24 OCH2CH3). Characterization data for this compound are in complete agreement with an internal GE publication.Ethyl\u20103\u2010((2\u2010chloro\u20105\u2010methoxyphenyl)(2\u2010fluoroethyl)amino)\u20102\u2010hydroxycyclohex\u20101\u2010ene\u20101\u2010carboxylate (12). A solution of the aniline 10  in THF (60\u2005mL) was cooled to \u221240\u2009\u00b0C. Potassium bis(trimethylsilyl)amide  was added dropwise and the reaction stirred for 30\u2005min at \u221240\u2009\u00b0C. The carboxylate 11  in THF (10\u2005mL) was added dropwise at \u221240\u2009\u00b0C. The cooling bath was removed and the reaction was stirred at RT for 4\u2005h. The reaction was quenched with brine (100\u2005mL) and extracted into EtOAc (2\u00d7200\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give 12 as a brown oil  which was used crude in the next step. LC\u2013MS: Rf 2.29 (+ESI) m/z 372.4 ([M+H]+). Characterization data for this compound are in complete agreement with an internal GE publication.H\u2010carbazole\u20104\u2010carboxylate (13)Ethyl 8\u2010chloro\u20109\u2010(2\u2010fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. The intermediate 12  was dissolved in Et2O (100\u2005mL) and zinc chloride  was added. The reaction was heated at reflux for 16\u2005h. EtOAc (300\u2005mL) was added to dissolve everything and was washed with 2\u2009m HCl (200\u2005mL), water (200\u2005mL), 10\u2009% aqueous potassium carbonate (200\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo. The crude material was purified by silica gel chromatography eluting with a gradient of 5\u201320\u2009% of EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to afford 13 as a yellow oil . Material could not be obtained in a pure form, but regardless, the reaction was progressed to the next step. LC\u2013MS: Rf 2.38 (+ESI) m/z 354.4 ([M+H]+); 1H\u2005NMR : \u03b4H=6.95 , 6.35 , 4.90\u20134.40 , 4.20\u20134.10 , 2.80\u20132.65 , 3.79 , 2.10\u20131.80 , and 1.30\u20131.20 . Characterization data for this compound are in complete agreement with an internal GE publication.H\u2010carbazole\u20104\u2010carboxylate (14)Ethyl 9\u2010(2\u2010fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. The chloro intermediate 13  was dissolved in methanol (50\u2005mL) and triethylamine  and 10\u2009% Pd/C (0.414\u2005g) were added. The mixture was stirred for 18\u2005h after purging twice (over 2\u2005h) with hydrogen gas under atmospheric pressure. The reaction was filtered through a pad of Celite under nitrogen atmosphere, washed with methanol (50\u2005mL), and the solvent was removed in\u2005vacuo. The residue was dissolved in EtOAc (100\u2005mL) and washed with 10\u2009% aqueous potassium carbonate (100\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give 14 as an oil . LC\u2013MS: Rf 2.18 (+ESI) m/z 320.5 , Rf 2.20 (\u2212ESI) m/z 318.4 ([M\u2212H]\u2212); 1H\u2005NMR : \u03b4H=7.04 , 6.84 , 6.46 , 4.64 , 4.40\u20134.00 , 3.82 , 2.90\u20132.60 , 2.20\u20131.80 , and 1.30\u20131.20 . Characterization data for this compound are in complete agreement with an internal GE publication.boxylate . The chlH\u2010carbazole\u20104\u2010carboxylic acid (15)9\u2010(2\u2010Fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. The ester 14  was dissolved in ethanol (10\u2005mL). A solution of sodium hydroxide  dissolved in 10\u2005mL of water, was added. The reaction mixture was heated at reflux for 18\u2005h. The solvent was removed in\u2005vacuo and the crude mixture diluted with water (30\u2005mL), acidified with 2\u2009m HCl dropwise until acidic, and washed with CH2Cl2 (50\u2005mL). The organic layers were combined and dried (MgSO4) and concentrated in\u2005vacuo to give 15 , which was used crude into the next step. LC\u2013MS: Rf 1.81 (+ESI) m/z 292.4 ([M+H]+).H\u2010carbazole\u20104\u2010carbonyl chloride (16)9\u2010(2\u2010Fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. A solution of 15  in anhydrous CH2Cl2 (5\u2005mL) was stirred under nitrogen. Oxalyl chloride  was added followed by a drop of DMF. The reaction mixture was stirred at RT under nitrogen for 2\u2005h then evaporated in\u2005vacuo to give 16  as an oil, which was used into the next step without purification.NN\u2010ethyl\u20109\u2010(2\u2010fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxamide (GE387) (6)\u2010Benzyl\u2010. The acid chloride 16  was dissolved in anhydrous CH2Cl2 (8\u2005mL) and cooled to 0\u2009\u00b0C. N\u2010Ethylbenzylamine  was then added and the reaction was stirred for 18\u2005h at RT. The reaction was quenched with 10\u2009% aqueous potassium carbonate (6\u2005mL). The CH2Cl2 layer was collected via a separatory funnel, dried (MgSO4), and then concentrated in\u2005vacuo. The crude material was purified by silica gel chromatography eluting with a gradient of 50\u2013100\u2009% EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to afford the crude product as a yellow oil. The oil was then recrystallised from EtOAc to afford 6 as a pale\u2010yellow solid . LC\u2013MS: Rf 2.30 (+ESI) m/z 409.6 , Rf 2.35 (+ESI) m/z 409.6 ([M+H]+); 1H\u2005NMR : \u03b4H=7.42\u20137.21 , 7.02 , 6.84 , 6.43 , 4.80\u20134.40 , 4.31 , 3.62 , 3.83\u20133.41 2), 2.88\u20132.61 , 2.20\u20131.80 , and 1.32 2).N\u2010(2\u2010(Benzyloxy)ethyl)\u20102\u2010chloro\u20105\u2010methoxyaniline (18). Commercially available 9  was converted into the free base with 1\u2009m aqueous sodium carbonate (300\u2005mL). The mixture was extracted with CH2Cl2 (2\u00d7200\u2005mL), the organic layer dried (MgSO4) and evaporated to give an oil. Compound 9 was then dissolved in CH2Cl2 (50\u2005mL), in a dry flask under nitrogen. Benzyloxyacetaldehyde 17  and acetic acid  were added. After 15\u2005min sodium triacetoxyborohydride  was added. The mixture was stirred for 18\u2005h at RT and then poured into saturated aqueous ammonium chloride solution (100\u2005mL) and extracted with CH2Cl2 (2\u00d7100\u2005mL). The combined organic layers were dried (MgSO4) and evaporated to give an oil. The crude product was purified via silica flash chromatography eluting with CH2Cl2 to yield 18 as an oil . Material could not be obtained in a pure form, but regardless, the reaction was progressed to the next step. LC\u2013MS: Rf 2.42 (+ESI) m/z 292.3 ([M+H]+); 1H\u2005NMR : \u03b4H=7.37\u20137.30 , 7.14 CHCH), 6.23\u20136.18 CHCH), 4.71 , 3.74 , 3.73 , and 3.35 . Characterization data for this compound are in complete agreement with an internal GE publication.Ethyl 3\u2010((2\u2010(benzyloxy)ethyl)(2\u2010chloro\u20105\u2010methoxyphenyl)amino)\u20102\u2010hydroxycyclohex\u20101\u2010ene\u20101\u2010carboxylate (19). The aniline 18  was stirred in dry THF (150\u2005mL) at \u221240\u2009\u00b0C under nitrogen and potassium bis(trimethylsilyl) amide  was added over 30\u2005min. The carboxylate 11  in dry THF (50\u2005mL) was then added and allowed to warm to RT over a period of 1.5\u2005h. Acetic acid was added (15\u2005mL) and concentrated in\u2005vacuo to remove the THF. EtOAc (200\u2005mL) and 10\u2009% aqueous potassium carbonate (200\u2005mL) was added and the mixture vigorously shaken. The EtOAc solution was separated, dried over (MgSO4) and concentrated in\u2005vacuo to afford 19 as an oil , which was used crude in the next step. LC\u2013MS: Rf 2.39 (\u2212ESI) m/z 458.5 ([M\u2212H]\u2212), Rf 2.53 (+ESI) m/z 460.5 ([M+H]+), Rf 2.39 (+ESI) m/z 460.5 ([M+H]+). Characterization data for this compound are in complete agreement with an internal GE publication.H\u2010carbazole\u20104\u2010carboxylate (20)Ethyl 9\u2010(2\u2010(benzyloxy)ethyl)\u20108\u2010chloro\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. Zinc chloride  was added to carboxylate 19  in dry Et2O (400\u2005mL) under nitrogen and heated at reflux for 5.5\u2005h. As the reaction was held at reflux, a thick brown dense oil formed in the reaction. The reaction was then cooled and the supernatant Et2O decanted off, EtOAc (300\u2005mL) was added, washed with 2\u2009m HCl (150\u2005mL) and with 10\u2009% aqueous potassium carbonate (150\u2005mL). The EtOAc layer was separated, dried (MgSO4) and concentrated in\u2005vacuo to afford an oil. The crude material was purified by silica gel chromatography eluting with a gradient of 10\u201340\u2009% EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to afford 20 as an oil . The thick dense brown layer was treated with EtOAc (300\u2005mL) and 2\u2009m HCl (150\u2005mL). The EtOAc layer was separated, washed with 10\u2009% aqueous potassium carbonate (150\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give an oil. Et2O (400\u2005mL) and anhydrous zinc chloride  were added. The mixture was heated at reflux for a further 5\u2005days. The Et2O layer and the dark gum were both diluted with EtOAc (200\u2005mL) and then washed with 2\u2009m HCl (150\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give a gum. This gum was purified by silica gel chromatography eluting with a gradient of 5\u201335\u2009% EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to afford 20 as an oil . LC\u2013MS: Rf 2.66 (+ESI) m/z 442.5 ([M+H]+); 1H\u2005NMR : \u03b4H=7.31\u20137.16 , 6.93 , 6.34 , 4.58 , 4.40 , 4.20\u20134.09 , 3.86\u20133.80 , 3.79 , 2.82\u20132.63 , 2.10\u20131.80 , and 1.23 . Characterization data for this compound are in complete agreement with an internal GE publication.H\u2010carbazole\u20104\u2010carboxylic acid (21)9\u2010(2\u2010(Benzyloxy)ethyl)\u20108\u2010chloro\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101. To the ester 20  in ethanol (12\u2005mL) was added sodium hydroxide  in water (1\u2005mL) and heated at 80\u2009\u00b0C for 18\u2005h. The ethanol was then removed by evaporation in\u2005vacuo and the residue partitioned between Et2O (30\u2005mL) and water (30\u2005mL). The Et2O layer was separated, dried (MgSO4) and concentrated in\u2005vacuo to give a gum. The aqueous layer was acidified to pH\u20051 with 2\u2009m HCl dropwise and extracted with CH2Cl2 (3\u00d720\u2005mL). The organic layers were dried (MgSO4) and concentrated in\u2005vacuo to afford 21 as a solid . LC\u2013MS: Rf 2.34 (+ESI) m/z 414.4 ([M+H]+); 1H\u2005NMR : \u03b4H=7.31\u20137.15 , 6.97 , 6.41 , 4.68\u20134.52 , 4.40 , 4.18 , 3.88 , 3.82 , 2.86\u20132.63 , and 2.27\u20131.86 . Characterization data for this compound are in complete agreement with an internal GE publication.NN\u2010ethyl\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxamide (22)\u2010Benzyl\u20109\u2010(2\u2010(benzyloxy)ethyl)\u20108\u2010chloro\u2010. The acid 21  was dissolved in THF (135\u2005mL) under N2 at RT. The solution was allowed to cool to 0\u2009\u00b0C and N\u2010ethylbenzylamine  was added followed by 1\u2010hydroxybenzotriazole hydrate  and N\u2010(3\u2010dimethylaminopropyl)\u2010N\u2032\u2010ethylcarbodiimide hydrochloride . Finally, triethylamine  was added via syringe and the mixture stirred under N2 and warmed to RT over 48\u2005h. The reaction was then diluted with EtOAc (100\u2005mL) and filtered through Celite. The Celite was washed with more EtOAc (2\u00d7100\u2005mL). The combined filtrates were washed with 1\u2009m aqueous HCl (2\u00d7150\u2005mL), H2O (2\u00d7150\u2005mL), brine (150\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo to give the product 22 as an oil , which was used crude in the next step. LC\u2013MS: Rf 2.74 (+ESI) m/z 531.6 ([M+H]+).NN\u2010ethyl\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxamide (23)\u2010Benzyl\u20109\u2010(2\u2010(benzyloxy)ethyl)\u2010. The carboxamide 22  in methanol (120\u2005mL) was shaken with 10\u2009% palladium on charcoal (1.5\u2005g), triethylamine  and stirred for 18\u2005h at RT after purging twice (over 2\u2005h) with hydrogen gas under atmospheric pressure. The reaction was then filtered through a pad of Celite under nitrogen atmosphere and the filtrate concentrated in\u2005vacuo. The concentrate was then taken up in CH2Cl2 (200\u2005mL) and washed with 5\u2009% aqueous potassium carbonate solution (200\u2005mL). The CH2Cl2 solution was then separated, dried (MgSO4) and concentrated in\u2005vacuo to afford 23 as an oil , which was used crude in the next step. LC\u2013MS: Rf 2.62 (+ESI) m/z 497.5 ([M+H]+).NN\u2010ethyl\u20109\u2010(2\u2010hydroxyethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxamide (24)\u2010Benzyl\u2010. The benzyl\u2010protected intermediate 23  in methanol (50\u2005mL) was shaken with 10\u2009% palladium on charcoal (0.333\u2005g) and stirred for 18\u2005h at RT after purging twice (over 2\u2005h) with hydrogen gas under atmospheric pressure. The reaction was then filtered through a pad of Celite under nitrogen atmosphere and the filtrate concentrated in\u2005vacuo to give 24 as an oil , which was used crude in the next step. LC\u2013MS: Rf 2.08 (+ESI) m/z 407.5 ([M+H]+).H\u2010carbazol\u20109\u2010yl)ethyl4\u2010methylbenzenesulfonate (25)2\u2010(4\u2010(Benzyl(ethyl)carbamoyl)\u20105\u2010methoxy\u20101,2,3,4\u2010tetrahydro\u20109. The alcohol 24  was dissolved in anhydrous pyridine (5\u2005mL) under N2. The solution was cooled to 0\u2009\u00b0C and 4\u2010toluenesulfonyl chloride  added potion\u2010wise to the solution over 30\u2005min. 4\u2010Dimethylaminopyridine  was then added, and the solution was stirred and warmed to RT for 18\u2005h. The reaction was then quenched by careful addition of ice followed by water (5\u2005mL). The mixture was then extracted into EtOAc and washed with water (3\u00d710\u2005mL). Excess pyridine was removed by washing with 1\u2009m HCl (2\u00d710\u2005mL) and aqueous copper sulfate (2\u00d710\u2005mL). Excess 4\u2010toluenesulfonyl chloride was removed by washing with 1\u2009m aqueous sodium carbonate (2\u00d710\u2005mL). The organic layer was washed with brine (10\u2005mL), dried (MgSO4) and concentrated in\u2005vacuo. The crude product was recrystallised from EtOAc to afford 25 as an off\u2010white solid . LC\u2013MS: Rf 2.46 (+ESI) m/z 561.6 ([M+H]+); 1H\u2005NMR : \u03b4H=7.51 (CH2)CH3), 7.35\u20137.15 , 7.09 (CH2)CH3), 6.91 , 6.62 , 6.37 , 4.70\u20134.50 , 4.30\u20134.15 , 3.61 , 3.80\u20133.40 2), 2.80\u20132.50 , 2.33 , 2.1\u20131.60 , and 1.30 .H\u2010carbazol\u20109\u2010yl)ethyl methanesulfonate (26)2\u2010(4\u2010(Benzyl(ethyl)carbamoyl)\u20105\u2010methoxy\u20101,2,3,4\u2010tetrahydro\u20109. The phenol 24  in CH2Cl2 (20\u2005mL) was cooled to 0\u2009\u00b0C and methanesulfonyl chloride  and triethylamine  were added and allowed to warm to RT for 18\u2005h. The reaction was diluted with CH2Cl2 (20\u2005mL) washed with 5\u2009% aqueous potassium carbonate solution (40\u2005mL). The layers were separated. The combined organic layers were dried (MgSO4) and concentrated in\u2005vacuo to give a gum. The crude material was purified by silica gel flash chromatography eluting with a gradient of 50\u2013100\u2009% EtOAc/petroleum ether (40\u201360\u2009\u00b0C) to afford 26 as an oil . LC\u2013MS: Rf 2.12 (+ESI) m/z 485.5 ([M+H]+). 1H\u2005NMR : \u03b4H=7.40\u20137.10 , 7.03 , 6.86 , 6.44 , 4.65\u20134.50 , 4.50\u20134.45 , 3.64 , 3.90\u20133.20 2), 2.90\u20132.60 , 2.51 , 2.30\u20131.70 , and 1.31 .R,2S,5R)\u20102\u2010Isopropyl\u20105\u2010methylcyclohexyl 9\u2010(2\u2010(benzyloxy)ethyl)\u20108\u2010chloro\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxylate (29) and l\u2010menthol in CH2Cl2 (40\u2005mL) at 0\u2009\u00b0C was added N\u2010(3\u2010Dimethylaminopropyl)\u2010N\u2032\u2010ethylcarbodiimide hydrochloride  and 4\u2010Dimethylaminopyridine . Stirring was continued at RT for 16\u2005h. After this period, H2O (100\u2005mL) and CH2Cl2 (100\u2005mL) were added. The organic layer was washed with 1\u2009m HCl, saturated NaHCO3 solution, and brine. The solution was dried (MgSO4), filtered, and concentrated. The crude racemic mixture 29  was separated into two diasteriomerically enriched samples via silica flash chromatography eluting with 30\u2009% Et2O/cyclohexane. LC\u2013MS: Rf 3.12 (+ESI) m/z 368.3 ; 1H\u2005NMR : \u03b4H=7.36\u20137.12 , 6.94 , 6.31 , 4.90 , 4.38 , 4.09 , 3.86\u20133.77 , 3.75 , 2.7\u20132.44 , 2.15\u20132.01 , 2.00\u20131.82 , 1.81\u20131.56 , 1.46\u20131.40 2, and 1.02\u20130.83 .R)\u20101\u2010Phenylprop\u20102\u2010yn\u20101\u2010yl 9\u2010(2\u2010(benzyloxy)ethyl)\u20108\u2010chloro\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxylate (30), N\u2010(3\u2010Dimethylaminopropyl)\u2010N\u2032\u2010ethylcarbodiimide hydrochloride  and 4\u2010Dimethylaminopyridine  in CH2Cl2 (5\u2005mL) was added (R)\u20101\u2010phenyl\u20102\u2010propyn\u20101\u2010ol  at RT. The reaction was stirred for 4\u2005h at RT. The reaction mixture was diluted with CH2Cl2 (20\u2005mL) and washed with H2O (5\u2005mL). The organic layer was dried (MgSO4) and concentrated. The crude mixture was purified via silica flash column chromatography eluting with a gradient of 20\u201340\u2009% Et2O/petroleum ether (40\u201360\u2009\u00b0C) to yield 30 as a racemate . Separation of the two diastereomer was done via silica flash column chromatography eluting with a gradient of 10\u201320\u2009% Et2O/cyclohexane. LC\u2013MS: Rf 2.72 (+ESI) m/z 528.5 , 2.73 (+ESI) m/z 528.5 ; 1H\u2005NMR : \u03b4H=7.60\u20137.14 , 6.90 , 6.25 , 4.71\u20134.53 , 4.39 , 4.15 , 3.81 , 3.40 , 2.85\u20132.51 , 2.60 , and 2.20\u20131.79 .NN\u2010ethyl\u20109\u2010(2\u2010fluoroethyl)\u20105\u2010methoxy\u20102,3,4,9\u2010tetrahydro\u20101H\u2010carbazole\u20104\u2010carboxamide (6)\u2010Benzyl\u2010. 49.8\u2005mg of a racemic mixture of 6 was sent to Reach Separations to be separated into the two enantiomers. They provided the following methods for separation and purification. The racemate 6 was dissolved to 12\u2005mg\u2009mL\u22121 in MeOH/CH2Cl2 (1:1) and was then purified by SFC using a Lux C1 column  at 40\u2009\u00b0C and eluting with isocratic 50:50 MeOH/CO2 with 0.2\u2009% v/v NH3 at a flow rate of 50\u2005mL\u2009min\u22121. The injection volume was 1500\u2005\u03bcL and peaks were detected at 223\u2005nm. Combined fractions of each of the two enantiomers were then evaporated to near dryness using a rotary evaporator, transferred into final vessels with CH2Cl2, which was removed under a stream of compressed air at 40\u2009\u00b0C before being stored in a vacuum oven at 40\u2009\u00b0C and 5\u2005mbar for 4\u2005h to afford the two enantiomers as yellow gums. Chiral purity of the enantiomers was analysed using a Lux C1 column  at 40\u2009\u00b0C and eluting with isocratic 50:50 MeOH/CO2 with 0.2\u2009% v/v NH3 at a flow rate of 4\u2005mL\u2009min\u22121. The injection volume was 1.0\u2005\u03bcL and the peaks were detected at 210\u2013400\u2005nm. Chemical purity of the enantiomers was analysed using an Acquity BEH C18 column  at 40\u2009\u00b0C and eluting with 0\u20134\u2005min gradient of 5\u201395\u2009% MeCN/H2O with 0.1\u2009% TFA, 4\u20104.02\u2005min gradient of 95\u2013100\u2009% MeCN/H2O with 0.1\u2009% TFA, 4.03\u2005min\u20134.5\u2005min isocratic 100\u2009% MeCN with 0.1\u2009% TFA, 4.5\u20134.52\u2005min gradient of 100\u20135\u2009% MeCN/H2O with 0.1\u2009% TFA, and 4.53\u20136\u2005min isocratic of 5\u2009% MeCN/H2O with 0.1\u2009% TFA at flow rate of 0.6\u2005mL\u2009min\u22121. The injection volume was 1.0\u2005\u03bcL and the peak was detected at 220\u2005nm. The final yield is 23.9\u2005mg of enantiomer (S)\u20106 with 98.02\u2009% chemical purity and in 100\u2009%\u2005ee, and 22.1\u2005mg of enantiomer (R)\u20106 with 100\u2009% chemical purity and in 98.8\u2009%\u2005ee.H\u2010carbazol\u20109\u2010yl)ethyl 4\u2010methylbenzenesulfonate (25)2\u2010(4\u2010(Benzyl(ethyl)carbamoyl)\u20105\u2010methoxy\u20101,2,3,4\u2010tetrahydro\u20109. 162.4\u2005mg of a racemic mixture of 25 was sent to Reach Separations to be separated into the two enantiomers. They provided the following methods for separation and purification. The racemate 25 was dissolved to 23\u2005mg\u2009mL\u22121 in MeOH/CH2Cl2 (1:1) and was then purified by SFC using a Lux C1 column  at 40\u2009\u00b0C and eluting with isocratic 50:50 MeOH/CO2 with 0.2\u2009% v/v NH3 at a flow rate of 50\u2005mL\u2009min\u22121. The injection volume was 1000\u2005\u03bcL and peaks were detected at 223\u2005nm. Combined fractions of each of the two enantiomers were then evaporated to near dryness using a rotary evaporator, transferred into final vessels with CH2Cl2, which was removed under a stream of compressed air at 40\u2009\u00b0C before being stored in a vacuum oven at 40\u2009\u00b0C and 5\u2005mbar for 4\u2005h to afford the two enantiomers as white solids. Chiral purity of the enantiomers was analysed using a Lux C1 column  at 40\u2009\u00b0C and eluting with isocratic 50:50 MeOH/CO2 with 0.2\u2009% v/v NH3 at a flow rate of 4\u2005mL\u2009min\u22121. The injection volume was 1.0\u2005\u03bcL and the peaks were detected at 210\u2013400\u2005nm. Chemical purity of the enantiomers was analysed using an Acquity BEH C18 column  at 40\u2009\u00b0C and eluting with 0\u20134\u2005min gradient of 5\u201395\u2009% MeCN/H2O with 0.1\u2009% TFA, 4\u20104.02\u2005min gradient of 95\u2013100\u2009% MeCN/H2O with 0.1\u2009% TFA, 4.03\u2005min\u20134.5\u2005min isocratic 100\u2009% MeCN with 0.1\u2009% TFA, 4.5\u20134.52\u2005min gradient of 100\u20105\u2009% MeCN/H2O with 0.1\u2009% TFA, and 4.53\u20136\u2005min isocratic of 5\u2009% MeCN/H2O with 0.1\u2009% TFA at flow rate 0.6\u2005mL\u2009min\u22121. The injection volume was 1.0\u2005\u03bcL and the peak was detected at 220\u2005nm. The final yield is 82.7\u2005mg of enantiomer (S)\u201025 with 97.42\u2009% chemical purity and in 98.2\u2009%\u2005ee, and 77.1\u2005mg of enantiomer (R)\u201025 with 98.75\u2009% chemical purity and in 99.6\u2009%\u2005ee.m Tris\u22c5HCl, pH\u20057.4) were incubated with \u2248Kd concentration of [3H]1  and test compounds (0.3\u2005nm\u201310\u2005\u03bcm) at 4\u2009\u00b0C for 90\u2005min. Reactions were terminated by filtration through a 96\u2010well glass\u2010fibre filter plate (Millipore), and washed eight times with ice\u2010cold 50\u2005mm Tris\u22c5HCl. Microscint\u20050 was added to the dry filters, and radioactivity read in a Microbeta2 2450 Microplate Counter (PerkinElmer). Data were analysed using GraphPad Prism 6.0, and a four\u2010parameter nonlinear regression curve fit was used to calculate Ki values. Data are expressed as the mean\u00b1SEM from at least three independent experiments.Binding affinities were measured as per our published protocol.Circular dichroism spectroscopy. Solutions of (S)\u20106, (R)\u20106, and (S)\u20105 were prepared in concentrations of 0.1\u20130.2\u2005mg\u2009mL\u22121 in acetonitrile and CD spectra were collected on an Aviv 410 instrument.Radioisotope production. No\u2010carrier\u2010added aqueous [18F]fluoride ion was produced on a GE PETtrace cyclotron by irradiation of a 2.3\u2010mL silver\u2010bodied water target with a 25\u2010mA current and a 16.5\u2010MeV proton beam on 95\u2009% enriched 18O\u2010H2O via the nuclear 18O18F reaction.18F]KF\u2010Kryptofix\u2010222 complexPreparation of the [. [18F]Fluoride in [18O]H2O was transferred and immediately trapped on an anion\u2010exchange resin (Waters Sep\u2010Pak Accell Light QMA cartridge in the carbonate form) under vacuum. Trapped 18F\u2010fluoride was eluted from the Sep\u2010Pak cartridge and transferred to the reaction vessel with an eluent solution containing 0.25\u2009% wild\u2010type Kryptofix\u2010222\u00ae solution (1\u2005mL) in basic (0.05\u2009% wild\u2010type K2CO3) aq. MeCN (75\u2009% v/v). The solvents were evaporated in\u2005vacuo (130\u2005mbar) with a stream of N2 gas at 95\u2009\u00b0C over 5\u2005min. Anhydrous MeCN (3\u00d70.7\u2005mL) was then added and the mixture was azeotropically dried in\u2005vacuo (130\u2005mbar) with a stream of N2 at 95\u2009\u00b0C.18F]6Manual preparation of fluoride solution (125\u2005\u03bcL) of equivalent solvent. The vials were heated in a heating block to the desired temperature  and a single vial was removed at each time point  and quenched with 1:1 MeCN/H2O (300\u2005\u03bcL) before analyzing directly by HPLC using a gradient method: (pre\u2010injection) 1\u2005min equilibration at 10:90 MeCN/H2O. (post\u2010injection) 1\u2005min isocratic at 10:90 MeCN/H2O, 2\u2005min gradient to 70:30 MeCN/H2O, 3\u2005min isocratic at 70:30 MeCN/H2O. Flow rate: 1.5\u2005mL\u2009min\u22121. Run time: 6\u2005min (7\u2005min including equilibration time). Column: ACE\u00ae UltraCore, Super C18, 2.5\u2005\u03bcm, 50\u00d74.6\u2005mm; Serial No. A133239. A portion of the sample from 20\u2005min was taken and used for co\u2010injection with reference compound 6 to confirm synthesis of desired product.18F]6Automated preparation and formulation of KF\u2010Kryptofix\u2010222 complex and heated at 100\u2009\u00b0C for 20\u2005min. The reaction mixture was then cooled with compressed air and diluted with anhydrous MeCN (1\u2005mL). The crude mixture was injected into an ACE 160433 C18 5\u2005\u03bcm (100\u00d710\u2005mm) semipreparative reversed\u2010phase HPLC column. With a mobile phase of 48\u2009% aq. MeCN at a flow rate of 5\u2005mL\u2009min\u22121. [18F]6 was collected (tR: 19.6\u2005min) and immediately diluted with H2O (10\u2005mL). The aqueous solution was passed through a C18 cartridge . The cartridge was washed with H2O (15\u2005mL) and the radiolabelled product was eluted with EtOH (0.5\u2005mL). The radiolabelled product was then formulated with 0.9\u2009% w/v aq. NaCl in a vial to afford the radiolabelled title compound.18F]6Quality control for 6 at a tR of 9.8\u2005min. The area of the UV absorbance peak at 220\u2005nm corresponding to the carrier product was measured (integrated) on the HPLC chromatogram and compared with a standard curve relating mass to UV absorbance. The identity of the radiolabelled product was confirmed by HPLC co\u2010injection of the reference compound 6.n=2; weight: 230 and 302\u2005g) were obtained from Charles River Laboratories, UK. The rats were housed in Techniplast 2000P IVC cages on a layer of Aspen bedding in a room with constant temperature (21\u00b12\u2009\u00b0C) and fixed 12\u2005h light\u2013dark regime (lights on at 7:00\u2005am). Food and water were available ad libitum. After arrival, the rats were allowed to acclimatise for at least seven days. This research was regulated under the Animals (Scientific Procedures) Act 1986 Amendment Regulations 2012 following ethical review by the University of Cambridge Animal Welfare and Ethical Review Body (AWERB).Male Wistar rats .68Ge point source was made for attenuation and scatter correction of 511\u2005keV photons. The radiotracer, formulated in saline, was injected to the rats and the emission scan was started with tracer injection. A list\u2010mode protocol was used with an acquisition time of 60\u2005min.Prior to scanning, the animals were anaesthetised using isofluorane at a concentration of 5\u2009% in OImage reconstructions were performed using microPET Manager 2.4.1.1, ASIPro 6.7.1.2 (Siemens). Acquisition data were then Fourier re\u2010binned in 22 time frames  and the data were reconstructed per timeframe employing an iterative reconstruction algorithm . The final datasets consisted of 95 slices with a slice thickness of 0.8\u2005mm, and an in\u2010plane image matrix of 128\u00d7128 pixels. Voxel size was 0.8\u00d70.8\u00d70.8\u2005mm. Data sets were corrected for decay, random coincidences, scatter and attenuation.\u22121 for brain tissue.Three\u2010dimensional regions of interest (ROIs) were drawn over the whole brain on an MRI template using PMOD software . PET images were then co\u2010registered with this MRI template and the regions of interest transferred from MRI to PET. Whole\u2010brain TACs were then obtained for each of the animals. The results were expressed as dimensionless standardised uptake values (SUV=[(tissue activity)\u00d7(body weight)]/injected dose). SUVs were calculated assuming a specific gravity of 1\u2005g\u2009mLThe authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re\u2010organized for online delivery, but are not copy\u2010edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file."}
{"text": "The propynyl substituent is nearly perpendicular to the plane formed by the rails of the boat. In the crystal, inversion dimers are formed by weak C\u2014H\u22efF hydrogen bonds with the dimers forming oblique stacks along the  18H12FNOS, is built up from a 4-fluoro\u00adbenzyl\u00adidene moiety and a di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit with a propynyl substituent, with the heterocyclic portion of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit adopting a shallow boat conformation with the propynyl substituent nearly perpendicular to it. The two benzene rings are oriented at a dihedral angle of 43.02\u2005(6)\u00b0. In the crystal, C\u2014HFlurphen\u22efFFlurphen (Flurphen = fluoro\u00adphen\u00adyl) hydrogen bonds link the mol\u00adecules into inversion dimers, enclosing R22(8) ring motifs, with the dimers forming oblique stacks along the a-axis direction. Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H\u22efH (33.9%), H\u22efC/C\u22efH (26.7%), H\u22efF/F\u22efH (10.9%) and C\u22efC (10.6%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C The propynyl substituent is nearly perpendicular to the plane defined by C1, C6, C7 and C8, as shown by the C6\u2014N1\u2014C9\u2014C10 torsion angle of 81.3\u2005(2)\u00b0. A puckering analysis of the heterocyclic ring  of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit shows that it adopts a shallow boat conformation with puckering parameters QT = 0.3759\u2005(14)\u2005\u00c5, q2 = 0.3639\u2005(15)\u2005\u00c5, q3 = \u22120.0938\u2005(17)\u2005\u00c5, \u03c6 = 173.6\u2005(3)\u00b0 and \u03b8 = 104.5\u2005(3)\u00b0. In the heterocyclic ring B, the C1\u2014S1\u2014C8 [101.73\u2005(8)\u00b0], S1\u2014C8\u2014C7 [119.93\u2005(12)\u00b0], C8\u2014C7\u2014N1 [119.23\u2005(14)\u00b0], C7\u2014N1\u2014C6 [125.59\u2005(14)\u00b0] and C6\u2014C1\u2014S1 [122.07\u2005(13)\u00b0] bond angles are enlarged, while the N1\u2014C6\u2014C1 [120.91\u2005(15)\u00b0] bond angle is narrowed when compared with the corresponding values in the closely related compounds 4-methyl-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (II) -one, (III) -2-(2-chloro\u00adbenzyl\u00adidene)-4-(prop-2-yn\u00adyl)-2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one, (IV), Flurphen\u22efFFlurphen (Flurphen = fluoro\u00adphen\u00adyl) hydrogen bonds  analysis  have a nearly symmetrical distribution of points, Fig.\u00a07c, with the thick edges at de + di \u223c2.70\u2005\u00c5. The pair of characteristic wings in the fingerprint plot delineated into H\u22efF/F\u22efH contacts  arises from the C\u2014H\u22efF hydrogen bonds  have an arrow-shaped distribution of points with the tip at de = di \u223c1.68\u2005\u00c5. The pair of characteristic wings in the fingerprint plot delineated into H\u22efO/O\u22efH contacts  have a pair of spikes with the tips at de + di = 2.54\u2005\u00c5. Finally, the H\u22efS/S\u22efH contacts  are viewed as A pair of wide spikes with the tips at de + di = 3.02\u2005\u00c5. The Hirshfeld surface representations with the function dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efF/F\u22efH, C\u22efC, H\u22efO/O\u22efH and H\u22efS/S\u22efH inter\u00adactions in Fig.\u00a08a\u2013f, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a07s Table\u00a01 as well s Table\u00a01 and is set al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6\u2013311G basis-set calculations -2-(4-fluoro\u00adbenzyl\u00adidene)-4-(prop-2-yn\u00adyl)-2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one ring. The energy band gap [\u0394E = ELUMO - EHOMO] of the mol\u00adecule was about 3.92\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO were \u22125.85 and \u22121.93\u2005eV, respectively.The optimized structure of the title compound, (I)II  in the Cambridge Crystallographic Database  to 36\u00b0 (IId). The other three  have the benzo\u00adthia\u00adzine unit nearly planar with the corresponding dihedral angle of ca 3\u20134\u00b0. In the case of IIa, the displacement ellipsoid for the sulfur atom shows a considerable elongation perpendicular to the mean plane of the heterocyclic ring, suggesting disorder, and a greater degree of non-planarity but for the other two, there is no obvious source for the near planarity.Using the search fragment Z)-2-(4-fluoro\u00adbenzyl\u00adidene)-2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one (1.6\u2005mmol), potassium carbonate (4\u2005mmol) and tetra-n-butyl ammonium bromide (0.15\u2005mmol) in DMF (20\u2005ml). Stirring was continued at room temperature for 24\u2005h. The salts were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate\u2013hexane (2/8) as eluent. The solid product obtained was recrystallized from ethanol to afford colourless crystals (yield: 89%).Propargyl bromide (4\u2005mmol) was added to a mixture of  I, global. DOI: 10.1107/S2056989019002354/lh5893Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019002354/lh5893Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019002354/lh5893Isup6.cmlSupporting information file. DOI: 1897371CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title hydrated azo dye, the benzene and thia\u00adzole make a dihedral angle of 4.69\u2005(17)\u00b0. In the crystal, hydrogen bonds, C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions resulting in the formation of a three-dimensional framework. 10H10N4OS\u00b7H2O, the benzene and thia\u00adzole, are nearly coplanar, with a dihedral angle between their mean planes of 4.69\u2005(17)\u00b0. The aromatic rings on the \u2013N=N\u2013 moiety exhibit a trans configuration. The crystal structure features many types of inter\u00admolecular inter\u00adactions involving all the functional groups \u2013 strong hydrogen bonds (N\u22efH and O\u22efH), weak hydrogen bonds (C\u2014H\u22efO and C\u2014H\u22efN), C\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions \u2013 resulting in the formation of a three-dimensional framework.In the title hydrated azo dye, C Azo dyes have wide range applications in the cosmetic, food, textile industry, chemical sensing, and pharmaceutical . The meth\u00adoxy and amino groups on the benzene ring are co-planar with the ring with atoms O1 and N4 deviating by \u22120.010\u2005(2) and \u22120.019\u2005(4)\u2005\u00c5, respectively. The dihedral angle between the thia\u00adzole and benzene rings is 4.69\u2005(17)\u00b0, nearly coplanar.The mol\u00adecular structure of (I)a, Table\u00a012), azo (\u2013N=N\u2013) and thia\u00adzole groups and the water mol\u00adecule of crystallization  are the primary inter\u00adactions responsible for the formation of the three dimensional structure. In addition, the crystal structure is supported by other inter\u00admolecular inter\u00adactions as a secondary weak inter\u00adactions, C\u2014H\u22efX (X = O and N), C\u2014H\u22ef\u03c0 and offset \u03c0\u2014\u03c0 inter\u00adactions. The weak hydrogen bonds are formed between the C\u2014H moieties in the benzene and thia\u00adzole rings with amine, azo, meth\u00adoxy groups of adjacent mol\u00adecules and water mol\u00adecules . On the shape index surface , convex blue regions represent hydrogen-donor groups and concave red regions represent hydrogen-acceptor groups. In addition, concave red regions represent C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions. The amino group behaves as both a donor and an acceptor. The methyl part of the meth\u00adoxy group acts as a donor while the oxygen atom is an acceptor.Hirshfeld surfaces and fingerprint plots were generated using ce Fig.\u00a03b, conveet al., 2007The two-dimensional fingerprint plots Fig.\u00a04 qu\u00adantifet al., 1992trans configuration and the phenolic oxygen atom is linked to an azo nitro\u00adgen atom by intra\u00admolecular hydrogen bonding. The crystal structure features only van der Waals inter\u00adactions. To form complexes with metal ions, both thia\u00adzole and naphthol rings are rotated by 180\u00b0 to coordinate to the metal through the phenolic oxygen atom, the azo nitro\u00adgen atom adjacent to the naphthol ring and the thia\u00adzole nitro\u00adgen atom, resulting the formation of five-membered chelate rings. Complexes of TAR and TAC are formed in a similar way due to the presence of a hydroxyl group in the structure M HCl (16\u2005ml), and 8.236\u2005mmol of sodium nitrate solution was added slowly under stirring at low temperature 268\u2013273\u2005K until the diazo\u00adnium salt was obtained. m-Anisidine (1.12\u2005ml in 40\u2005ml of 4\u2005M HCl) was slowly dropped into the mixture and stirred at a temperature between 268 and 273\u2005K for 1\u2005h. After the reaction was complete, conc. NH3 was dropped into the mixture (pH 6) until the red\u2013orange crude produce appeared. The products were filtered, washed with cold water, purified by column chromatography and recrystallized from an aceto\u00adnitrile\u2013water (1:1) mixture by vapour diffusion.2-Amino\u00adthia\u00adzole (9.986\u2005mmol) was dissolved in 6\u20051H NMR : \u03b4 3.806 , 6.364  , 6.374 , 7.546  ,7.629 , 7.697 , 7.883 . Mass spectroscopy: m/z 235.0654 [C10H11N4OS+], 205.0548 [C9H9N4S.+], 150.0662 [C7H8N3O.+], 122.0601 [C7H8NO.+]. IR (KBr cm\u22121): 3,413\u2005cm\u22121 ; 821\u2005cm\u22121 ; 1,617 ; 1,222\u2005cm\u22121 ; 1,103\u2005cm\u22121 ; 1,152\u2005cm\u22121 ; 1,541cm\u22121 ; 1,021\u2005cm\u22121 . Elemental analysis calculated for C10H10N4OS\u00b7H2O: C, 51.27; H, 4.30; N, 23.92. Found: C, 51.34; H, 4.20; N, 23.98.Uiso = 1.2 Ueq(C-aromatic) and 1.5Ueq (C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901900207X/dx2014sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901900207X/dx2014Isup2.hklStructure factors: contains datablock(s) I. DOI: 1895710CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structure has triclinic (P2(O2CCPh3-\u03bc-\u03baO:\u03baO\u2032)]2 is located about an inversion centre. The tri\u00adphenyl\u00adacetate ligand displays a \u03bc-\u03baO:\u03baO\u2032-bridging coordination mode, leading to the formation of an octa\u00adgonal Al2O4C2 core. The complex displays HPh\u22efCPh inter\u00admolecular inter\u00adactions.Single crystals of the title compound, [Al(iBu) The tri\u00adphenyl\u00adacetate ligand exhibits a \u03bc2-\u03baO:\u03baO\u2032-bridging coordination mode. The CPh\u2014CPh [1.3788\u2005(17)\u2005\u00c5 for C5\u2014C6 to 1.4016\u2005(14)\u2005\u00c5 for C15\u2014C16], CiBu\u2014CiBu [1.523\u2005(2)\u2005\u00c5 for C26\u2014C28 to 1.5381\u2005(16)\u2005\u00c5 for C21\u2014C22], C1\u2014C2 [1.5473\u2005(13)\u2005\u00c5] and C1\u2014Cipso [1.5425\u2005(14)\u2005\u00c5 for C2\u2014C9 to 1.5455\u2005(14)\u2005\u00c5 for C2\u2014C3] bond lengths inside the ligands are within the expected ranges. The complex has a nearly flat eight-membered Al2O4C2 core, with the greatest deviations from the plane being 0.0548\u2005(6)\u2005\u00c5 for the O2 and O2i atoms. The bond angles inside the core are 106.84\u2005(4) (O1\u2014Al\u2014O2i), 151.00\u2005(7) (Al\u2014O1\u2014C1), 123.64\u2005(9) (O1\u2014C1\u2014O2) and 156.79\u2005(8)\u00b0 (C1\u2014O2\u2014Ali), summing to a value of 1076.54\u00b0 for the entire core, which deviates from a flat octa\u00adgon by 3.46\u00b0. The Al\u2014X bond lengths are given in Table\u00a01R2(\u03bc-O2CR\u2032)]2 compounds (see \u00a74 below) having the Al2O4C2 core (23 independent core fragments) have Al\u2014X bond lengths varying from ca 1.77 to 1.86\u2005\u00c5 (average 1.82\u2005\u00c5) for Al\u2014O, 1.92\u20132.00\u2005\u00c5 (average 1.96\u2005\u00c5) for Al\u2014C and 1.23\u20131.29\u2005\u00c5 (average 1.26\u2005\u00c5) for C\u2014O bonds. The bond lengths in the title complex (Table\u00a012-bridging RO\u2212 ligands), but shorter than the Al\u2014O distances in complexes with either Al\u2013O=CR2  or Al\u2014Oether fragments  due to different types of Al\u2014O inter\u00adactions, changing from the ion\u2013ion type in the case of Al\u2014Oalk\u00adyl/ar\u00adyl bonds to the ion\u2013dipole one in the case of Al\u2014O=CR2 or Al\u2014Oether fragments.The title compound crystallizes in the triclinic space group ]2 Fig.\u00a02 located x Table\u00a01 are closA\u22efH20 and 2.30\u2005\u00c5 for H25A\u22efH12. Two inter\u00admolecular inter\u00adactions involving aromatic H atoms with the \u03c0-system of a arene group have been found, i.e. 2.89\u2005\u00c5 for H6\u22efC12 and 2.98\u2005\u00c5 for H7\u22efC11 (see Table S1 for details). Inter\u00adacting arene rings are located nearly perpendicular to one another, with the corresponding angle between the C3\u2013C8 and C9\u2013C14 planes being 82.83\u2005(3)\u00b0 .The crystal lattice exhibits weak inter\u00admolecular van der Waals contacts between methyl or methyl\u00adene and aromatic H atoms, with the distances being 2.49\u2005\u00c5 for H23)\u00b0 Fig.\u00a03. The laset al., 20162O4C2 core and having the [AlR2(\u03bc-O2CR\u2032)]2 motif, where R is alkyl or C6F5. Records for crystal structures with other R groups connected to Al via the C atom have not been found in the CSD. 14 complexes have bridging carboxyl\u00adate ligands, the others have a heteroatom in the \u03b1-position .According to the Cambridge Structural Database ]2 type are represented by structures with R = R\u2032 = Me and aryl = Ph 3 and aryl = 4-MeC6H4  and R = isobutyl (iBu)  ]2 complexes with a substituted acetate anion possess R = Et and CX3 = CPh3 ]2, with X = \u2013C4H(CH3)2Zr(\u03b75-C5Me5)2 2(\u03bc-O2CC6F5)]2 ]2 ]2, with R = iBu  depends greatly on various inter\u00adactions within the complex, including nonvalence ones. See also related ab initio calculations in the literature 3(THF)3] was prepared according to a previously published method  was added dropwise to a suspension of [Nd(Ph3CCOO)3(THF)3]  in 15\u2005ml of hexane at room temperature. The suspension dissolved within a few minutes upon addition. The resulting solution was stirred overnight at room temperature. Crystals of [Al(iBu)2(Ph3CCOO)]2 were isolated from the reaction mixture by crystallization at 243\u2005K for 2\u2005d. The mother liquor was deca\u00adnted and crystals were dried under dynamic vacuum. The yield was 56\u2005mg . Calculated for C56H66Al2O4 (%): C 78.48, H 7.76; found: C 78.17, H 8.01.A solution of Al(iBu)Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. A rotating group model was applied for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019003396/tx2010sup1.cifCrystal structure: contains datablock(s) global. DOI: 10.1107/S2056989019003396/tx2010sup4.pdfC...H interactions and packing plots. DOI: 1902149CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal. hydroxyl-O\u2014H\u22efO(hydrox\u00adyl) and hydroxyl-O\u2014H\u22efS(thione) hydrogen bonds give rise to a supra\u00admolecular layer in the ab plane.The title tri-substituted thio\u00adurea derivative is twisted with a dihedral angle of 72.12\u2005(9)\u00b0 between the planes through the CN 13H18N2O3S, the thione-S and carbonyl-O atoms lie, to a first approximation, to the same side of the mol\u00adecule [the S\u2014C\u2014N\u2014C torsion angle is \u221249.3\u2005(2)\u00b0]. The CN2S plane is almost planar (r.m.s. deviation = 0.018\u2005\u00c5) with the hy\u00addroxy\u00adethyl groups lying to either side of this plane. One hy\u00addroxy\u00adethyl group is orientated towards the thio\u00adamide functionality enabling the formation of an intra\u00admolecular N\u2014H\u22efO hydrogen bond leading to an S(7) loop. The dihedral angle [72.12\u2005(9)\u00b0] between the planes through the CN2S atoms and the 4-tolyl ring indicates the mol\u00adecule is twisted. The experimental mol\u00adecular structure is close to the gas-phase, geometry-optimized structure calculated by DFT methods. In the mol\u00adecular packing, hydroxyl-O\u2014H\u22efO(hydrox\u00adyl) and hydroxyl-O\u2014H\u22efS(thione) hydrogen bonds lead to the formation of a supra\u00admolecular layer in the ab plane; no directional inter\u00adactions are found between layers. The influence of the specified supra\u00admolecular inter\u00adactions is apparent in the calculated Hirshfeld surfaces and these are shown to be attractive in non-covalent inter\u00adaction plots; the inter\u00adaction energies point to the important stabilization provided by directional O\u2014H\u22efO hydrogen bonds.In the title tri-substituted thio\u00adurea derivative, C R1(R2)NC(=S)N(R3)R4 for R1\u20134 = alk\u00adyl/aryl. The present study concerns a tri-substituted example, i.e. an N,N\u2032-di-N\u2032-benzoyl\u00adthio\u00adurea derivative, notable for having a carbonyl group connected to the thio\u00adurea framework. Thio\u00adurea mol\u00adecules are of inter\u00adest in themselves and as ligands for metal ions 2, (I)The amine-H atoms in thio\u00adurea, Hsyn as the S1\u2014C1\u2014N2\u2014C6 torsion angle is \u221249.3\u2005(2)\u00b0; the O3\u2014C6\u2014N2\u2014C1 torsion angle is \u22126.8\u2005(3)\u00b0. The hy\u00addroxy\u00adethyl groups lie to either side of the CN2S plane (r.m.s. deviation = 0.018\u2005\u00c5). The O1-hy\u00addroxy\u00adethyl group is folded toward the thio\u00adamide part of the mol\u00adecule, an orientation that allows for the formation of an intra\u00admolecular N2\u2014H\u22efO1 hydrogen bond that closes an S(7) loop, Table\u00a022S atoms and the terminal aryl ring. The C1\u2014N1 bond length is considerably shorter than the C1\u2014N2 bond, which suggests some delocalization of \u03c0-electron density over the S1\u2014C1\u2014N1 atoms that does not extend over the C1\u2014N1\u2014C6 atoms, consistent with the large twist about the C1\u2014N2 bond (see above). The bond angles subtended at the C1 and C6 atoms follow the expected trends in that those involving the formally doubly bonded atoms are wider, by approximately 10\u00b0, compared with the other angles, Table\u00a01The title compound, (I)d,p) basis set  N1\u2014C2\u2014C3\u2014O1 and N1\u2014C4\u2014C5\u2014O2 torsion angles, which are disparate, by about 12\u00b0, in the experimental structure but are symmetric, i.e. \u00b169\u00b0, in the optimized structure.Compound (I)1 symmetry to generate helical chains along the b-axis direction. The O\u2014H\u22efS hydrogen bonding serves to connect translationally related chains along the a-axis direction and these contacts are reinforced by phenyl-C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions. In this way, a supra\u00admolecular layer in the ab plane is formed, Fig.\u00a03a). Layers stack along the c-axis direction without directional inter\u00adactions between them, Fig.\u00a03b).In the crystal of (I)Crystal Explorer 17  for (I)dnorm in Fig.\u00a05O atoms, Table\u00a03The Hirshfeld surface mapped over electrostatic potential in Fig.\u00a04ER) descriptor, which is derived from the analysis of the Hirshfeld surface , for a pair of elements  is defined as the ratio between proportion of actual contacts in the crystal to the theoretical proportion of random contacts. This ratio is greater than unity for a pair of elements having a high likelihood to form contacts in a crystal, while it is less than one for a pair which tends to avoid contacts with each other. A listing of ER values for (I)The inter\u00admolecular contacts in the crystal of (I)a)\u2013(e), respectively. A summary of the percentage contributions from the various contacts in the crystal are given in Table\u00a05b) and has an ER value of 0.92, i.e. close to unity. The contribution from O\u22efH/H\u22efO contacts is viewed as long spikes at de + di \u223c1.8\u2005\u00c5, with points scattered around different regions in the delineated fingerprint plot, Fig.\u00a06c). In the fingerprint delineated into C\u22efH/H\u22efC contacts in Fig.\u00a06d), a pair of small tips at de + di < 2.8\u2005\u00c5 is the result of short inter\u00adatomic contacts, Table\u00a03A\u22efO1). The percentage contribution from S\u22efH/H\u22efS contacts (13.1%) reflect the presence of O\u2014H\u22efS hydrogen bonds and are apparent through the appearance of asymmetric spikes at de + di \u223c2.1\u2005\u00c5 in Fig.\u00a06e).The overall fingerprint plots for (I)EBSSEint) listed in Table\u00a06\u22121 more stable than the O\u2014H\u22efS inter\u00adaction despite phenyl-C\u2014H being a weak hydrogen-bond donor and thione-S a weak acceptor, and that such inter\u00adactions are known to be dispersive in nature  of all pairwise inter\u00adactions sums to \u221236.11 kcal mol\u22121, while the total dispersion energy term (Edispersion) computes to \u221243.83 kcal mol\u22121.As the mol\u00adecular packing is governed directionally by hydrogen bonding between mol\u00adecules, the energy frameworks were simulated (Turner 2CH2OH)2, (II), has been reported twice i.e. of the type phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl), to sustain a three-dimensional architecture. The other closely related structure is that of 4-MePhC(=O)N(H)C(=S)N(Me)CH2CH2OH) N(H)C(=S)N. The optical absorption spectra were measured on 10 and 100\u2005\u00b5M ethanol:aceto\u00adnitrile (1:1) solutions in the range 190\u20131100\u2005nm on a double-beam Shimadzu UV 3600 Plus UV\u2013vis spectrophotometer. The thermogravimetric analysis (TGA) was performed on a Perkin Elmer STA 6000 Simultaneous Thermogravimetric Analyzer in the range of 35\u2013900\u00b0C under a nitro\u00adgen atmosphere at a flow rate of 10\u00b0C min\u22121. The experimental powder X-ray diffraction pattern was measured on a Rigaku MiniFlex diffractometer with Cu K\u03b11 radiation (\u03bb = 1.54056\u2005\u00c5) in the 2\u03b8 range of 5\u201370\u00b0 and a step size of 0.02\u00b0. The experimental PXRD patterns were compared to the simulated PXRD patterns calculated from the CIF using the Rigaku PDXL structure analysis software package. The patterns matched indicating that the reported crystal structure is representative of the bulk material.All chemicals and solvents were used as purchased without purification. The reactions were carried out under ambient conditions. The melting point was measured using a Hanon MP-450 melting point apparatus. The CHN elemental analysis was performed on a LECO TruSpec Micro analyser under helium atmosphere with glycine being used as the standard. The IR spectrum was measured on a Bruker Vertex 70v FT\u2013IR spectrophotometer from 4000 to 400\u2005cm13H18N2O3S, found : C 55.59 (55.30), H 6.57 (6.43), N 9.79 (9.92). IR : 3312 , 3158 , 3061 , 2955\u20132881 , 1686 , 1539 , 1250 , 1054 , 747 . UV : \u03bbmax nm  354.4 , 294.0 , 246.4 , 202.6 . 1H NMR , 7.76 , 7.31 , 5.66 , 4.87 , 3.98 , 3.76 , 3.70 , 2.37 . 13C{1H} NMR : \u03b4 180.63 (C1), 163.78 (C6), 141.88 (C7), 130.13 (C10), 128.47 , 127.28 , 58.58 (C5), 56.95 (C3), 54.42 (C4), 54.29 (C2), 20.42 (C13).Synthesis of (I)2O between 135 and 165\u00b0C, which corresponds to approximate 6% of the weight for (I)The pyrolytic processes for (I)Uiso(H) set to 1.2\u20131.5Ueq(C). The O- and N-bound H atoms were located from a difference map and refined with O\u2014H and N\u2014H = 0.84\u00b10.01 and 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989019012581/hb7854sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019012581/hb7854Isup2.hklStructure factors: contains datablock(s) I. DOI: 1919878CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The second, C8H11N9O2S, contains two azide groups with an average N\u03b1\u2014N\u03b2 distance of 1.249\u2005(2)\u2005\u00c5 and an average N\u03b2\u2014N\u03b3 distance of 1.132\u2005(2)\u2005\u00c5. Each compound contains a bulky protecting group.The structures of two azide containing imidazole derivatives are reported. The first, C 8H12N6O2S, contains one azide group with an N\u03b1\u2014N\u03b2 distance of 1.229\u2005(2)\u2005\u00c5 and an N\u03b2\u2014N\u03b3 distance of 1.128\u2005(2)\u2005\u00c5. The second, C8H11N9O2S, contains two azide groups with an average N\u03b1\u2014N\u03b2 distance of 1.249\u2005(2)\u2005\u00c5 and an average N\u03b2\u2014N\u03b3 distance of 1.132\u2005(2)\u2005\u00c5. Each compound contains a bulky protecting group (di\u00admethyl\u00adamino\u00adsulfon\u00adyl) which can be easily removed under mildly acidic conditions.The structures of two azide containing imidazole derivatives are reported. Allylic azides are fairly reactive making them attractive starting compounds to convert into amides. The first, C These compounds were synthesized in the previous study but the structures were not reported. Figs. 11 and 2, respectively.The efficient synthesis of nagelamide alkaloids  has garnered inter\u00adest \u2005\u00c5 and an N4\u2014N5 distance of 1.128\u2005(2)\u2005\u00c5. The N3\u2014N4\u2014N5 angle is 172.32\u2005(13)\u00b0. The azide groups in 2 show an N3\u2014N4 distance of 1.253\u2005(2)\u2005\u00c5, N4\u2014N5 distance of 1.129\u2005(2)\u2005\u00c5, N6\u2014N7 distance of 1.239\u2005(2)\u2005\u00c5, and N7\u2014N8 distance of 1.134\u2005(2)\u2005\u00c5. The N3\u2014N4\u2014N5 angle is 171.58\u2005(15)\u00b0 and the N6\u2014N7\u2014N8 angle is 173.95\u2005(15)\u00b0. All three azide moieties in both compounds show the same general trend of a longer N\u03b1\u2014N\u03b2 distance and shorter N\u03b2\u2014N\u03b3 distance with a quasilinear geometry. This is typical for covalent azides with terminal N\u03b2\u2014N\u03b3 demonstrating more triple-bond character. A previously reported covalent azide occurring in the compound ethyl-2-[(azido\u00adcarbon\u00adyl)amino]\u00adbenzoate demonstrated bond lengths N\u03b1\u2014N\u03b2 of 1.264\u2005(2)\u2005\u00c5 and N\u03b2\u2014N\u03b3 of 1.131\u2005(2)\u2005\u00c5 and an N\u03b1\u2014N\u03b2\u2014N\u03b1 angle of 174.7\u2005(2)\u00b0  in 1 was \u2212115.21\u2005(13)\u00b0 while the related torsion angle (C5\u2014C6\u2014N6\u2014N7) in 2 was 50.25\u2005(18)\u00b0. 2 contains one azide group bound to the imidazole at C2 and shows a torsion angle N1\u2014C2\u2014N3\u2014N4 of \u2212174.82\u2005(11)\u00b0. The allylic azides in both compounds exhibit a similar dihedral angle between the azide and the imidazole ring, 70.3\u2005(11)\u00b0 for 1 and 77.3\u2005(17)\u00b0 for 2. While the imidazole-bound azide in 2 shows a dihedral angle of 5.0\u2005(10)\u00b0. Indeed, the torsion angle and dihedral angle for this particular azide demonstrate the near planarity between the imidazole and its covalently bound azide. Figs. 31 and 2, respectively.The torsion angles for the azides and dihedral angles between the azides and imidazole rings for both compounds have been measured. The allylic azide torsion angles between sp3-hybrid\u00adized, as validated by the C\u2014N\u2014C bond angles C6\u2014N6\u2014C8 = 113.86\u2005(10)\u00b0 for 1 and C7\u2014N9\u2014C8 = 113.93\u2005(12)\u00b0 for 2. Both compounds also contain a double bond between C4 and C5. The measured bond distance is 1.333\u2005(2)\u2005\u00c5 for 1 and 1.340\u2005(2)\u2005\u00c5 for 2.Both title compounds contain a DMAS protecting group. The amine component of this protecting group is 1 is substituted at the N1 and C3 position with no substitution at C2. The N1\u2014C2 distance is 1.378\u2005(2)\u2005\u00c5 while the N2\u2014C2 distance is 1.301\u2005(2)\u2005\u00c5. However, in 2, the imidazole ring is substituted with an azide group at C2 but this seemingly has no effect on the ring bond distances. The measured bond distances for N1\u2014C2 and N2\u2014C2 in 2 are 1.385\u2005(2) and 1.310\u2005(2)\u2005\u00c5, respectively.The imidazole ring in 1 is 1.686\u2005(1)\u2005\u00c5 and 1.718\u2005(1)\u2005\u00c5 for 2. The disparity may be attributed to the presence of azide, which is substituted at the C2 position for 2.There is, however, a significant difference in the measured N1\u2014S1 distance for the two compounds. The imidazole ring is substituted at the N1 position for both compounds with DMAS. The N1\u2014S1 distance for 1 shows C1\u2014H1\u22efO1i and C2\u2014H2\u22efO2ii inter\u00adactions of 2.53 and 2.39\u2005\u00c5, respectively. There is also a C4\u2014H4\u22efN5iii inter\u00adaction of 2.70\u2005\u00c5 acrylate, was reported \u2005\u00c5 which is similar to the bond distances in 1 and 2 [1.333\u2005(2) and 1.340\u2005(2)\u2005\u00c5 respectively].A search of related compounds was conducted in the Cambridge Structural Database  = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details for 10.1107/S205698901900519X/zl2753sup1.cifCrystal structure: contains datablock(s) compound_1, compound_2. DOI: 10.1107/S205698901900519X/zl2753compound_1sup2.hklStructure factors: contains datablock(s) compound_1. DOI: 10.1107/S205698901900519X/zl2753compound_2sup3.hklStructure factors: contains datablock(s) compound_2. DOI: Click here for additional data file.10.1107/S205698901900519X/zl2753compound_1sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901900519X/zl2753compound_2sup5.cmlSupporting information file. DOI: 1910313, 1910312CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "CavCOOH-in, was synthesized and crystallized with acetic acid to evaluate its mol\u00adecular recognition properties towards this analyte in the solid state.Acetic acid is a by-product of peracetic acid with acute irritant properties when present in air. The cavitand 5,11,17,23-tetra\u00admethyl-4,24:6,10:12,16:18,22-tetra\u00adkis\u00ad(methyl\u00adenedi\u00adoxy)resorcin[4]arene functionalized at the upper rim with a carb\u00adoxy\u00adlic acid group,  CavCOOH-in, of chemical formula C37H32O10, was synthesized in order to study its supra\u00admolecular inter\u00adactions with acetic acid in the solid state. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a di\u00adchloro\u00admethane\u2013acetone solution of CavCOOH-in, to which glacial acetic acid had been added. The resulting compound, C37H32O10\u00b72C2H4O2 (1) crystallizes in the space group P1 is dominated by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonding due to the presence of acetic acid and of the carb\u00adoxy\u00adlic group functionalizing the upper rim. Further stabilization is provided by offset \u03c0\u2013\u03c0 stacking inter\u00adactions between the aromatic walls of adjacent cavitands [inter\u00adcentroid distance = 3.573\u2005(1)\u2005\u00c5].The cavitand 5,11,17,23-tetra\u00admethyl-4,24:6,10:12,16:18,22-tetra\u00adkis\u00ad(methyl\u00adenedi\u00adoxy)resorcin[4]arene functionalized at the upper rim with a carb\u00adoxy\u00adlic acid group,  It is therefore important to find an accurate method to measure acetic acid vapour in order to assess the environmental air quality. In the literature, only one example of the environmental monitoring of gaseous acetic acid has been reported  is also shown in Fig.\u00a011 crystallizes in the space group PC, while the methyl group of the acetic acid held inside the cavity forms C\u2014H\u22ef\u03c0 inter\u00adactions with the aromatic rings of the walls , as can be seen from the C3\u2014O1\u2014C9\u2014O2 torsion angles . This is probably due to the hydrogen bonding in which the carb\u00adoxy\u00adlic acid C9D/C10D/O3D/O4D is involved with adjacent cavitands, as will be described in Section 3.1 is dominated by hydrogen bonding. A chain which propagates along the c-axis direction is formed by strong O\u2014H\u22efO inter\u00adactions involving the hydroxyl group O3D\u2014H3D from the carb\u00adoxy\u00adlic acid at the methyl\u00adene bridge and the bridging resorcinol oxygen atom O2Bi of an adjacent cavitand  \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01; see Fig.\u00a04D-\u2013H7D1\u22efO1ii] and an intra\u00admolecular one with a methyl\u00adene bridge [C9A\u2014H9A1\u22efO1]. These sets of inter\u00adactions are completed by another inter\u00admolecular C\u2014H\u22efO hydrogen bond between methyl group C7C\u2014H7C2 and the carboxyl oxygen atom O4Dii. Finally, the ribbons  C1A\u2013C6A aromatic rings [Fig.\u00a05While the main supra\u00admolecular contacts at play for the encapsulation of acetic acid inside the cavitand are C\u2014H\u22ef\u03c0 inter\u00adactions Table\u00a01, the crynd Fig.\u00a03. Pairs o5H11 alkyl chains at the lower rim (XIDLEC) have been used to form supra\u00admolecular complexes with di\u00admethyl\u00admethyl\u00adphospho\u00adnate, DMMP, a nerve-gas simulant bearing a P=O group  has been used to form a heterodimeric capsule in a rim-to-rim fashion through the formation of four hydrogen bonds with a tetra\u00ad(3-pyrid\u00adyl)-cavitand. The previously cited cavitand A self-assembles into a one-dimensional chain (LOPKEG) or into dimeric capsules (KAHMOV) via hydrogen bonding with four 2-amino\u00adpyrimidine mol\u00adecules. Similarly, OSIYIA and OSIYOG consist of supra\u00admolecular self-assembled polymers or capsules between tetra\u00adcarb\u00adoxy\u00adlic acid functionalized cavitands and suitable N-heterocyclic linkers such as 4,4-bi\u00adpyridine and 2-amino-5-bromo-4-chloro-6-methyl\u00adpyrimidine.A resorcinarene-based cavitand in which one of the four methyl\u00adenic bridges is functionalized with a carb\u00adoxy\u00adlic acid is unique to the present day. An isomer of the title compound (XIDLIG) and its analogue with four \u2013CCavCOOH-in was carried out according to the procedure employed for the CavCOOH-out isomer  spectrometer. All chemical shifts (\u03b4) are reported in p.p.m. relative to the proton resonances resulting from incomplete deuteration of the NMR solvents. 1H NMR  d = 1.91 , 2.01 , 3.23 , 4.31 , 4.51 , 5.85 , 6.73 , 6.94 .The synthesis of cavitand 1 were obtained by slow evaporation of a solution prepared by dissolving 0.005\u2005mmol of the cavitand CavCOOH-in in 5\u2005ml of a 1:1 di\u00adchloro\u00admethane and acetone solution, to which 1.1\u2005\u00b5L (0.02\u2005mmol) of glacial acetic acid were added.Colourless crystals of the inclusion complex Uiso(H) set to 1.2\u20131.5Ueq(C/O), the only exception being atom H9D, which was located in a difference-Fourier map and refined freely. A DIFX instruction was employed to avoid a short H\u22efH contact between atoms H9D and H8D1. Atoms O1 and O2 were refined using the EADP command. The acetic acid guest is disordered over two positions with a refined occupancy ratio of 0.344\u2005(4):0.656\u2005(4).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019002512/su5481sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019002512/su5481Isup2.hklStructure factors: contains datablock(s) I. DOI: 1897735CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Cervical sagittal parameters were closely related with clinical outcomes after multi-level ACDF. Our purpose was to evaluate the clinical outcomes and cervical sagittal parameters in patients with MCSM after ACDF and to identify the risk factors of poor clinical outcomes.ACDF was performed in 89 patients with MCSM. Based on average JOA recovery rate, patients were divided good-outcome group (group GO) and poor-outcome group (group PO). The cervical sagittal parameters including Cobb angle, SVA, T1S, cranial tilt and cervical tilt were measured. Multivariate logistic regression was used to identify risk factors.p\u2009<\u20090.001). \u25b3Cobb angle (p\u2009=\u20090.008) and \u25b3SVA (p\u2009=\u20090.009) showed significantly statistical differences between two groups. Longer symptom duration, lower preoperative JOA score, smaller \u25b3Cobb angle and larger \u25b3SVA were identified as risk factors of poor clinical outcomes.Fifty-four patients (60.67%) were divided into group GO, while 35 patients (39.33%) were divided into group PO. Cobb angle, SVA and T1S was corrected from preoperative average 11.80\u00b0\u2009\u00b1\u20099.63\u00b0, 23.69\u2009mm\u2009\u00b1\u200911.69\u2009mm and 24.43\u00b0\u2009\u00b1\u200911.78\u00b0 to postoperative average 15.08\u00b0\u2009\u00b1\u20099.05\u00b0, 18.79\u2009mm\u2009\u00b1\u200910.78\u2009mm and 26.92\u00b0\u2009\u00b1\u200911.94\u00b0 respectively (Multi-level ACDF is an effective surgical method to treat patients with MCSM. However, long duration of preoperative symptoms, lower preoperative JOA score, smaller \u25b3Cobb angle and larger \u25b3SVA are risk factors for poor outcomes in patients with MCSM after ACDF. Sagittal parameters should be paid attention to in surgery. Cervical spondylotic myelopathy (CSM) is caused by spinal cord compression as a result of multiple pathological changes such as disc herniation, degeneration and/or osteophyte formation at the posterior margin of the vertebral body . Multi-lAs an anterior procedure surgery, multi-level ACDF was widely used in treating MCSM . AlthougAll protocols of the study were approved by the Ethics Committee of the Third Hospital of Hebei Medical University and informed consent was obtained from all individual participants for using their imaging data and questionnaire scores.From January 2010 to December 2015, 89 patients, including 40 men and 49 women, diagnosed as MCSM according to clinical manifestations and imaging scans underwent multi-level ACDF at the Department of Spinal Surgery, the Third Hospital of Hebei Medical University, were enrolled in this retrospective study. The inclusion criteria were the following: (1) MCSM required surgical treatment for equal to or more than three levels; (2) ineffective conservative treatment for more than 3\u00a0months or acute aggravated neurological deficit; (3) complete imaging and clinical date; (4) follow-up for at least 2\u2009years. Exclusion criteria were the following: (1) history of operation involving with cervical spine; (2) combined with trauma, spinal tumours, spinal tuberculosis or infections; (3) ossification of posterior longitudinal ligament; (4) combined with severe osteoporosis; (5) combined with neurological diseases, such as vitamin B deficiency or motor neuron diseases. The average age of all patients at operation was 58.97\u2009\u00b1\u20095.79\u2009years, range from 37 to 78\u2009years. Three-level ACDF (C3-C6 in 34 cases and C4-C7 in 41 cases) was performed in 75 patients and four-level ACDF (C3-C7) in 14 patients. The patients were followed up for an average of 2.57\u2009\u00b1\u20090.78\u2009years.Japanese Orthopaedic Association (JOA) scoring system (0\u201317 scores) was used for neurological function assessment before surgery and at last follow-up visit. Neurological function recovery rate was calculated on the basis of JOA scoring system: (postoperative score-preoperative score)/(17-preoperative score)\u2009\u00d7\u2009100%. According to average JOA scores, patients were divided into two groups: good-outcome group  and poor-outcome group .Cervical magnetic resonance imaging (MRI), CT (Computed Tomography) and posterior-anterior and lateral X-rays were taken preoperatively to diagnose and evaluate the disease and make surgical planning. Cervical posterior-anterior and lateral X-rays were also taken postoperatively and at each follow-up visit. Cervical sagittal parameters were measured on lateral radiographs on synapse system  with patients in a neutral position. The measurement methods of cervical sagittal parameters were as follows , duration of symptoms, follow-up period, preoperative JOA scores, number of operative segments, \u25b3Cobb angle, \u25b3SVA, \u25b3T1S, \u25b3cranial tilt and \u25b3cervical tilt were collected for potential risk factors of poor clinical outcomes in patients with MCSM after ACDF. Duration of symptoms was defined as the period from appearance of primary neurological clinical symptoms to surgery.p value <\u20090.05 was considered statistically significant. Quantitative dates were first tested its normality and homogeneity of variance and according to different situations, they were tested by Student\u2019s t test or Mann\u2013Whitney U test. Qualitative date was tested by chi-square test. The potential risk factors were tested by univariate analysis and if p\u2009<\u20090.05, the factor was selected into multivariate logistic model. Then, multivariate logistic regression analysis was used to identify the risk factors of poor clinical outcomes in patients with MCSM after ACDF with adjusted odds ratios (ORs) and 95% confidence intervals (CIs).Clinical and imaging date was evaluated by SPSS program . p\u2009<\u20090.001). The average recovery rate was 61.13%\u2009\u00b1\u200921.48%. Fifty-four patients (60.67%) whose recovery rate higher than the average were divided into group GO and their average recovery rate was 75.00%\u2009\u00b1\u20099.52%, while 35 patients (39.33%) whose recovery rate lower than the average were divided into group PO and their average recovery rate was 39.73%\u2009\u00b1\u200916.62%. There was significantly statistical difference in recovery rate between two groups (p\u2009<\u20090.001).For all patients, the mean duration of symptoms was 14.64\u2009\u00b1\u20098.02\u2009months. All the operations were completed successfully Fig.\u00a0. JOA scop\u2009=\u20090.114), sex (p\u2009=\u20090.450), BMI (p\u2009=\u20090.582), follow-up time (p\u2009=\u20090.159) and operative segment (p\u2009=\u20090.768) between two groups. The JOA scores were significantly improved at last follow-up visit comparing with the preoperative scores in both groups (p\u2009<\u20090.001). No matter preoperative JOA scores (p\u2009=\u20090.014) or last follow-up JOA scores (p\u2009<\u20090.001), group GO got significantly higher scores than group PO. In addition, patients in group PO complained of syndromes for a significantly longer period before surgery than patients in group GO (p\u2009<\u20090.001).The clinical dates between group GO and group PO were showed in Table\u00a0p\u00a0<\u20090. 001) and the average \u25b3Cobb angle was 3.28\u00b0\u2009\u00b1\u20093.88\u00b0. The average last follow-up SVA (18.79\u2009mm\u2009\u00b1\u200910.78\u2009mm) was significantly lower than the preoperative (23.69\u2009mm\u2009\u00b1\u200911.69\u2009mm) (p\u00a0<\u20090.001) and the average \u25b3SVA was \u2212\u20094.90\u2009mm\u2009\u00b1\u20096.30\u2009mm. Meanwhile, significantly significant difference was also found between preoperative T1S (24.43\u00b0\u2009\u00b1\u200911.78\u00b0) and last follow-up T1S (26.92\u00b0\u2009\u00b1\u200911.94\u00b0) (p\u00a0<\u20090.001) and the average \u25b3T1S was 2.49\u00b0\u2009\u00b1\u20094.19\u00b0. Significantly statistical difference (p\u00a0<\u20090.001) was found between preoperative (5.16\u00b0\u2009\u00b1\u20096.47\u00b0) and last follow-up cranial tilt (7.52\u00b0\u2009\u00b1\u20096.27\u00b0) and the average \u25b3cranial tilt was 2.36\u00b0\u2009\u00b1\u20092.25\u00b0.There was no significantly statistical difference (p\u00a0=\u20090.132) between preoperative (17.71\u00b0\u2009\u00b1\u20096.28\u00b0) and last follow-up cervical tilt (17.46\u00b0\u2009\u00b1\u20096.54\u00b0) and the average \u25b3cervical tilt was \u2212\u20090.25\u00b0\u2009\u00b1\u20091.53\u00b0.For all patients, Cobb angle was corrected from preoperative average 11.80\u00b0\u2009\u00b1\u20099.63\u00b0 to postoperative average 15.08\u2009\u00b1\u20099.05\u00b0 (p\u00a0=\u20090.467), preoperative SVA (p\u00a0=\u20090.868) and preoperative T1S (p\u00a0=\u20090.740) between two groups. However, last follow-up Cobb angle in group GO was greater than that in group PO (p\u00a0=\u20090.025) and significantly statistical difference was also found when comparing \u25b3Cobb angle (p\u00a0=\u20090.008). Last follow-up SVA showed the opposite result than the value in group PO was greater than that in group GO (p\u00a0=\u20090.030). \u25b3SVA in group PO was also greater than that in group GO (p\u00a0=\u20090.009). There was no significantly statistical difference in both last follow-up T1S (p\u00a0=\u20090.814) and \u25b3T1S (p\u00a0=\u20090. 826) between two groups. No significantly statistical difference was found in preoperative cranial tilt (p\u00a0=\u20090.740), last follow-up cranial tilt (p\u00a0=\u20090.653), \u25b3cranial tilt (p\u00a0=\u20090.952), preoperative cervical tilt (p\u00a0=\u20090.590), last follow-up cervical tilt (p\u00a0=\u20090.585) and \u25b3cervical tilt (p\u00a0=\u20090.946) between two groups.The comparison of cervical sagittal parameters between group GO and group PO is shown in Table\u00a0p\u2009<\u20090.001), preoperative JOA score (p\u2009=\u20090.009), \u25b3Cobb angle (p\u2009=\u20090.013) and \u25b3SVA (p\u2009=\u20090.001) showed significantly statistical difference in univariate analysis and the four factors were selected into multivariate logistic model (Table\u00a0p\u2009<\u20090.001), lower preoperative JOA score , smaller \u25b3Cobb angle  and larger \u25b3SVA  were identified as four risk factors of poor clinical outcomes in patients with MCSM after ACDF  is one of the most common diseases in orthopaedics and is one of the most harmful diseases, mostly in the elderly . It has The clinical outcomes of ACDF were limited by a variety of factors involving with preoperative condition and postoperative complications. Pumberger et al.  found thCervical sagittal parameters had been proved to be important in clinical recovery of patients with CMS after cervical surgery and preoperative cervical sagittal parameters had been proved to be predictors for clinical outcomes \u201324. CervThe similar result showed in the study of Basques et al.  that ACDMulti-level ACDF is an effective surgical method to treat patients with MCSM. Cervical sagittal parameters were changed after multi-level ACDF with larger Cobb angle, smaller SVA and greater T1S. However, long duration of preoperative symptoms, lower preoperative JOA score, smaller \u25b3Cobb angle and larger \u25b3SVA is risk factors for poor outcomes in patients with MCSM after ACDF. Sagittal parameters should be paid attention to in design of surgical plan for better clinical outcomes."}
{"text": "In the crystal, [010] polymeric chains are crosslinked by N\u2014H\u22efO hydrogen bonds to form sheets lying parallel to the (001) plane.The title com\u00adpound is one-dimensional coordination polymer built up of tetra\u00adgonally distorted CuN catena-poly[[[(perchlorato-\u03baO)copper(II)]-\u03bc-3-(3-carb\u00adoxy\u00adprop\u00adyl)-1,5,8,12-tetra\u00adaza-3-azonia\u00adcyclo\u00adtetra\u00addecane-\u03ba4N1,N5,N8,N12] bis\u00ad(per\u00adchlorate)], {[Cu(C13H30N5O2)(ClO4)](ClO4)2}n, (I), consists of a macrocyclic cation, one coordinated per\u00adchlorate anion and two per\u00adchlorate ions as counter-anions. The metal ion is coordinated in a tetra\u00adgonally distorted octa\u00adhedral geometry by the four secondary N atoms of the macrocyclic ligand, the mutually trans O atoms of the per\u00adchlorate anion and the carbonyl O atom of the protonated carb\u00adoxy\u00adlic acid group of a neighbouring cation. The average equatorial Cu\u2014N bond lengths [2.01\u2005(6)\u2005\u00c5] are significantly shorter than the axial Cu\u2014O bond lengths [2.379\u2005(8)\u2005\u00c5 for carboxyl\u00adate and average 2.62\u2005(7)\u2005\u00c5 for disordered per\u00adchlorate]. The coordinated macrocyclic ligand in (I) adopts the most energetically favourable trans-III conformation with an equatorial orientation of the substituent at the protonated distal 3-position N atom in a six-membered chelate ring. The coordination of the carb\u00adoxy\u00adlic acid group of the cation to a neighbouring com\u00adplex unit results in the formation of infinite chains running along the b-axis direction, which are cross\u00adlinked by N\u2014H\u22efO hydrogen bonds between the secondary amine groups of the macrocycle and O atoms of the per\u00adchlorate counter-anions to form sheets lying parallel to the (001) plane. Additionally, the extended structure of (I) is consolidated by numerous intra- and interchain C\u2014H\u22efO contacts.The asymmetric unit of the title com\u00adpound,  N3,N10-disubstituted 1,3,5,8,10,12-hexa\u00adaza\u00adcyclo\u00adtetra\u00addecane (di\u00adaza\u00adcyclam) and, to a lesser extent, N3-substituted 1,3,5,8,12-penta\u00adaza\u00adcyclo\u00adtetra\u00addecane (aza\u00adcyclam) are popular building units for the assembly of metal\u2013organic frameworks (MOFs), demonstrating many promising applications  or 3,7-di\u00adaza\u00adnonane-1,9-di\u00adamine com\u00adplexes, respectively, with formaldehyde and primary amines catena-poly[[[(perchlorato-\u03baO)copper(II)]-\u03bc-3-(3-carb\u00adoxy\u00adprop\u00adyl)-1,5,8,12-tetra\u00adaza-3-azonia\u00adcyclo\u00adtetra\u00addecane-\u03ba4N1,N5,N8,N12] bis\u00ad(per\u00adchlorate)], {[Cu(H2L)(ClO4)](ClO4)2}n, which is the first example of aza\u00adcyclam ligand with a carb\u00adoxy\u00adlic acid group.Herein, we describe the synthesis and the crystal structure of the title CuII ion in the com\u00adplex cation in (I)II ion is displaced by 0.075\u2005\u00c5 from the mean plane of the N4 donor atoms (r.m.s. deviation = 0.005\u2005\u00c5) towards the O2 atom of the carboxyl\u00adate group. The equatorial Cu\u2014N bond lengths are significantly shorter than the axial Cu\u2014O bond lengths  conformation \u00b0] and the six-membered chelate rings in chair [average bite angle = 93.6\u2005(2)\u00b0] conformations. The methyl\u00adene group of the substituent at the noncoordinated N3 atom in the six-membered chelate ring is oriented equatorially. Such an arrangement of the substituent, in contrast to an axial orientation, is relatively uncommon and only a few examples of such CuII com\u00adplexes with aza- and di\u00adaza\u00adcyclam ligands have been described so far + group in (I)sp3-hybridized N atom (ca 327\u00b0), thus indicating their partial sp2 character -substituted di\u00adaza\u00adcyclam polymeric com\u00adplex  and 1.198\u2005(13)\u2005\u00c5 for C13\u2014O1 and C13\u2014O2, respectively], thus confirming its protonated form and the lack of delocalization. Inter\u00adestingly, it is coordinated to the Cu4 anion is com\u00adpletely disordered over two positions with site occupancies of 50% and is weakly coordinated to the metal ion (Table\u00a014) and 78% (Cl3O4). Because of the low partial population, the minor com\u00adponents of these per\u00adchlorate anions were not considered further in the analysis of the hydrogen-bonding network.Three disordered per\u00adchlorate anions in the title com\u00adpound counterbalance the charge of the com\u00adplex cations. The Cl1On Table\u00a01. Two remb-axis direction ,O12(Cl3)], so that each per\u00adchlorate anion is fixed in a chain in a ditopic manner ], as well as between secondary amine groups of the macrocycle and an O atom of the carb\u00adoxy\u00adlic acid group as the proton acceptor [N2\u2014H2(N4\u2014H4)\u22efO1]. Hydrogen bonding of the secondary amine groups of the macrocycle and the O atoms of per\u00adchlorate anions not involved in above-mentioned intra\u00adchain inter\u00adactions [N1\u2014H1\u22efO7(Cl2)(x\u00a0\u2212\u00a0y\u00a0+\u00a0z) and N5\u2014H5\u22efO14(Cl3)(x\u00a0\u2212\u00a0y\u00a0+\u00a0z)] results in the formation of sheets lying parallel to the (001) plane  and many of them were investigated as building blocks for the construction of MOFs by using additional carboxyl\u00adate or metalocyanide linkers. At the same time, there are only two examples demonstrating self-polymerization , namely, those with di\u00adaza\u00adcyclam ligands containing 2-propio\u00adnitrile ](ClO4)2 , was prepared according to a published method ](ClO4)2 , 4-amino\u00adbutanoic acid  and 30% aqueous formaldehyde  in methanol (40\u2005ml) was refluxed for 24\u2005h. After cooling and filtration, the solution was kept in a refrigerator overnight. The violet crystalline precipitate was filtered off, washed with methanol (5\u2005ml) and recrystallized from a 1:1 (v/v) water\u2013ethanol solvent mixture (10\u2005ml) containing 0.5\u2005M perchloric acid . Analysis calculated (%) for C13H30Cl3CuN5O14: C 24.01, H 4.65, N 10.76; found: C 24.17, H 4.51, N 10.92. Violet blocks of (I)All chemicals and solvents used in this work were purchased from Sigma\u2013Aldrich and were used without further purification. The starting CuSafety note: per\u00adchlorate salts of metal com\u00adplexes are potentially explosive and should be handled with care.Uiso(H) values of 1.2 or 1.5Ueq of the parent atoms. The crystal of (I)Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901901377X/hb7857sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901901377X/hb7857Isup2.hklStructure factors: contains datablock(s) I. DOI: 1958285, 1958285CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "H-imidazol-3-ium) hepta\u00admolybdate 2-methyl-1H-imidazole disolvate dihydrate,(C4H7N2)6[Mo7O24]\u00b72C4H6N2\u00b72H2O, [Mo7O24]6\u2212 hepta\u00admolybdate anions, 2-methyl\u00adimidazolium cations, neutral 2-methyl\u00adimidazole mol\u00adecules and water mol\u00adecules are linked through hydrogen bonds into a three-dimensional network.In the crystal structure of hexa\u00adkis\u00ad(2-methyl-1 H-imidazol-3-ium) hepta\u00admolybdate 2-methyl-1H-imidazole disolvate dihydrate, (C4H7N2)6[Mo7O24]\u00b72C4H6N2\u00b72H2O, was prepared from 2-methyl\u00adimidazole and ammonium hepta\u00admolybdate tetra\u00adhydrate in acid solution. The [Mo7O24]6\u2212 hepta\u00admolybdate cluster anion is accompanied by six protonated (C4H7N2)+ 2-methyl\u00adimidazolium cations, two neutral C4H6N2 2-methyl\u00adimidazole mol\u00adecules and two water mol\u00adecules of crystallization. The cluster consists of seven distorted MoO6 octa\u00adhedra sharing edges or vertices. In the crystal, the components are linked by N\u2014H\u22efN, N\u2014H\u22efO, O\u2014H\u22efO, N\u2014H\u22ef and O\u2014H\u22ef hydrogen bonds, generating a three-dimensional network. Weak C\u2014H\u22efO inter\u00adactions consolidate the packing.The title compound, hexa\u00adkis\u00ad(2-methyl-1 M = V, Nb, Ta, Mo, W, \u22ef) and oxygen atoms with a structural and compositional diversity that lead to numerous applications because of their electrochemical, optical, catalytic and photochromic properties as well as their anti\u00adviral and anti\u00adtumor activities  are clusters of transition metals , \u03bc2-O (oxygen atoms bridging two molybdenum atoms), \u03bc3-O (oxygen atoms bridging three molybdenum atoms) and \u03bc4-O (oxygen atoms bridging four molybdenum atoms). All of the Mo atoms are bound to two terminal oxygen atoms except for Mo7, which is located in the \u2018core\u2019 of the cluster. The geometrical data for the cluster in (I)et al., 1992et al., 2008t, 1.754\u2005(2)\u20142.453\u2005(2)\u2005\u00c5 for \u03bc2-O, 1.8945\u2005(19)\u20132.3057\u2005(19)\u2005\u00c5 for \u03bc3-O and 2.1329\u2005(19)\u20132.3011\u2005(18)\u2005\u00c5 for \u03bc4-O. The variations of Mo\u2014O bond lengths and O\u2014Mo\u2014O angles indicate that all seven octa\u00adhedra (MoO6) within the cluster are highly distorted. As in the compound (H3dien)2[Mo7O24]\u00b74H2O . As well as the [Mo7O24]6\u2212 anion, six (C4H7N2)+ cations, two neutral C4H6N2 mol\u00adecules and two water mol\u00adecules of crystallization are present in the asymmetric unit + cations and/or neutral 2-methyl\u00adimidazole mol\u00adecules + cations to neutral mol\u00adecules. The packing is consolidated by weak C\u2014H\u22efO links , 2-methyl\u00adimidazole  and ammonium hepta\u00admolybdate tetra\u00adhydrate  in a ratio of 1:2:1/12 were dissolved in water (60\u2005ml). The solution was stirred for one\u2005h and evaporated in the oven at 333\u2005K to yield a whitish precipitate. The precipitate was recrystallized from methanol solution: after two weeks at room temperature, colourless prisms of (I)supporting information. The absorption bands at 3400 and 3395\u2005cm\u22121 corres\u00adpond to \u03bd(O\u2014H) stretches and indicate the presence of water mol\u00adecules and those at 1621 and 1564\u2005cm\u22121 to the deformation vibrations \u03b4(O\u2014H). The bands centered at 3132 and 1431\u2005cm\u22121 with shoulders are respectively attributed to the stretching and deformation vibrations of the N\u2014H bonds of the protonated and/or non-protonated entities of 2-methyl\u00adimidazole  deformation vibration  stretching vibrations while the bands between 838 and 650\u2005cm\u22121 are typical for the vibrations of \u03bd(Mo\u2014O\u2014Mo) and \u03bd[Mo\u2014(\u03bc-O)] groupings Uiso (H) = 1.2Ueq or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019008454/hb7831sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019008454/hb7831Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019008454/hb7831sup3.tifThe IR spectrum of compound (I). DOI: 1922927CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The structure of the pseudopolymorph of 3-(tri\u00adphenyl\u00adphospho\u00adranyl\u00adidene)-2,5-di\u00adhydro\u00adfuran-2,5-dione with a THF solvent mol\u00adecule is described. The compound has a hydrogen-bonded layer structure, and displays C\u2014H\u22efO hydrogen bonds connecting mol\u00adecules of the di\u00adhydro\u00adfuran-2,5-dione derivative into chains. viz. C22H17O3P\u00b7C4H8O. The succinic anhydride ring is approximately planar (r.m.s. deviation = 0.032\u2005\u00c5). The tetra\u00adhydro\u00adfuran mol\u00adecule is disordered over two orientations about a pseudo-twofold axis with refined occupancy ratio 0.718\u2005(4):0.282\u2005(4). In the crystal, C\u2014H\u22efO hydrogen bonds link mol\u00adecules of the di\u00adhydro\u00adfuran-2,5-dione derivative into chains parallel to the b axis and arranged into layers stacked along [100] alternating with hydrogen-bonded tetra\u00adhydro\u00adfuran layers.The title pseudo-polymorph of 3-(tri\u00adphenyl\u00adphospho\u00adranyl\u00adidene)-2,5-di\u00adhydro\u00adfuran-2,5-dione crystallizes with a tetra\u00adhydro\u00adfuran solvent mol\u00adecule,  The distribution histogram of the P=C distance [with a mean value of 1.729\u2005\u00c5 and a standard deviation of 0.030\u2005\u00c5] is shown in Fig.\u00a03et al., 19932Cl2 solvate : 1.78 , 3.14 , 3.67 , 7.44\u20137.72 . 31P{1H} NMR : +13.6 (s).To a stirred solution maleic anhydride  in tetra\u00adhydro\u00adfuran THF (5\u2005mL) was added tri\u00adphenyl\u00adphosphine  at room temperature. The reaction mixture was stirred at room temperature for 24\u2005h, then the solution was filtered and concentrated under reduced pressure. The reaction mixture was allowed to cool in the freezer  and yellowish crystals precipitated. The crystals were separated from solvent and dried to give 0.56\u2005g (90%) of the title compound. Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018011775/rz5234sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018011775/rz5234Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018011775/rz5234Isup3.cdxSupporting information file. DOI: 1862873CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Both mol\u00adecules feature an intra\u00admolecular N\u2014H\u22efN hydrogen bond. In the crystal, weak aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid\u2013centroid separation = 3.830\u2005(2)\u2005\u00c5] link the mol\u00adecules into dimers.In each of the two independent mol\u00adecules in the asymmetric unit of the title compound, [CdI For A, the Cd1\u2014I1 and Cd1\u2014I2 bond lengths are 2.7509\u2005(4) and 2.6917\u2005(4)\u2005\u00c5, respectively, and the Cd1\u2014N2 bond length is 2.342\u2005(3)\u2005\u00c5. For B, the Cd2\u2014I3 and Cd2\u2014I4 bond lengths are 2.7530\u2005(4) and 2.6732\u2005(4)\u2005\u00c5, respectively, and the Cd2\u2014N6 bond length is 2.344\u2005(3)\u2005\u00c5. Both mol\u00adecules feature an intra\u00admolecular N\u2014H\u22efN hydrogen bond with the pyridine-ring N atom as the acceptor \u00b0 for r Table\u00a02.A + B associations by aromatic \u03c0\u2013\u03c0 stacking inter\u00adactions  y] Fig.\u00a03.CrystalExplorer3.1 , H\u22efH (29.5%), C\u22efH / H\u22efC (13.3%), H\u22efO / O\u22efH (5.6%) and C\u22efI / I\u22efC (4.9%) are shown in Figs.\u00a04b\u2013f, respectively. The full list of percentage surface contributions in given in Table\u00a03The Hirshfeld surface analysis -4-hy\u00addroxy\u00adbenzyl\u00adidene]-pyridine-4-carbohydrazide-\u03baN1}di\u00adiodido\u00adcadmium methanol disolvate ethyl\u00adidene]picolinohydrazide-\u03ba2N\u2032,O}cadmium methyl\u00adidene]pyridine-2-carbohydrazide-\u03ba2N\u2032,O}cadmium) cadmium -4-(2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00adbenzoato-\u03ba2O,O\u2032]cadmium methyl\u00adidene]picolinohydrazide-\u03ba2N\u2032,O}cadmium N\u2032-[(E)-(pyridin-2-yl)methyl\u00adidene]pyridine-2-carbohydrazide ligand was synthesized according to the literature method  = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019008831/hb7823sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019008831/hb7823Isup2.hklStructure factors: contains datablock(s) I. DOI: 1935658CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title Schiff base compound, consisting of a cyclo\u00adhexane and a 2-hy\u00addroxy-3-methyl\u00adbenzyl\u00adidene ring bridged by a hydrazinecarbo\u00adthio\u00adamine moiety, crystallizes with two independent mol\u00adecules in the asymmetric unit. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efS hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, forming ribbons along the [010] direction. 15H21N3OS, comprises of two crystallographically independent mol\u00adecules (A and B). Each mol\u00adecule consists of a cyclo\u00adhexane ring and a 2-hy\u00addroxy-3-methyl\u00adbenzyl\u00adidene ring bridged by a hydrazinecarbo\u00adthio\u00adamine unit. Both mol\u00adecules exhibit an E configuration with respect to the azomethine C=N bond. There is an intra\u00admolecular O\u2014H\u22efN hydrogen bond in each mol\u00adecule forming an S(6) ring motif. The cyclo\u00adhexane ring in each mol\u00adecule has a chair conformation. The benzene ring is inclined to the mean plane of the cyclo\u00adhexane ring by 47.75\u2005(9)\u00b0 in mol\u00adecule A and 66.99\u2005(9)\u00b0 in mol\u00adecule B. The mean plane of the cyclo\u00adhexane ring is inclined to the mean plane of the thio\u00adurea moiety [N\u2014C(=S)\u2014N] by 55.69\u2005(9) and 58.50\u2005(8)\u00b0 in mol\u00adecules A and B, respectively. In the crystal, the A and B mol\u00adecules are linked by N\u2014H\u22efS hydrogen bonds, forming \u2018dimers\u2019. The A mol\u00adecules are further linked by a C\u2014H\u22ef\u03c0 inter\u00adaction, hence linking the A\u2013B units to form ribbons propagating along the b-axis direction. The conformation of a number of related cyclo\u00adhexa\u00adnehydrazinecarbo\u00adthio\u00adamides are compared to that of the title compound.The asymmetric unit of the title compound, C The benzene ring is inclined to the mean plane of the thio\u00adurea moiety by 10.95\u2005(8)\u00b0 in mol\u00adecule A and 9.80\u2005(8)\u00b0 in mol\u00adecule B.The cyclo\u00adhexane ring (C9\u2013C14) in each mol\u00adecule has a chair conformation. The mean plane of the four central C atoms (C10/C11/C13/C14) is inclined to the mean plane of the thio\u00adurea moiety [N2\u2014C8(=S1)\u2014N3] by 54.83\u2005(11) and 55.64\u2005(10)\u00b0 in mol\u00adecules i.e. \u03c41 (C1\u2014C6\u2014C7\u2014N1), \u03c42 (C7\u2014N1\u2014N2\u2014C8), \u03c43 (N1\u2014N2\u2014C8\u2014N3), \u03c44 (N2\u2014C8\u2014N3\u2014C9) and \u03c45 (C8\u2014N3\u2014C9\u2014C10), as illustrated in Fig.\u00a03\u03c41 between the benzyl\u00adidine ring and the azomethine double bond for both mol\u00adecules are approximately 0\u00b0 [3.0\u2005(2)\u00b0 in mol\u00adecule A and 1.9\u2005(2)\u00b0 in mol\u00adecule B], signifying the coplanarity between benzyl\u00adidine ring and the azomethine double bond (C7=N1). In mol\u00adecule B, the azomethine double bond is close to planar with the hydrazine moiety [\u03c42 = 177.23\u2005(14)\u00b0], whereas \u03c42 in mol\u00adecule A is slightly twisted [\u03c42 = 171.68\u2005(14)\u00b0]. In both mol\u00adecules, the torsion angle between the hydrazine moiety and the carbo\u00adthio group are also slight twisted with \u03c43 values in mol\u00adecules A and B of 7.4\u2005(2) and \u221210.2\u2005(2)\u00b0, respectively. Similarly to \u03c41, the carbo\u00adthio group is almost coplanar with the thio\u00adamide group for both mol\u00adecules, as implied by torsion angle \u03c44 [178.07\u2005(14)\u00b0 in mol\u00adecule A and 175.59\u2005(14)\u00b0 in mol\u00adecule B], which are approximately 180\u00b0. The thio\u00adamide group and the cyclo\u00adhexane ring are almost perpendicular to each other with \u03c45 torsion angles of 85.3\u2005(2) and \u221281.6\u2005(2)\u00b0 in mol\u00adecules A and B, respectively. This may arise from the steric repulsion between the cyclo\u00adhexane ring and adjacent sulfur atom.The unique mol\u00adecular conformations of the two mol\u00adecules can be characterized by five torsion angles, A and B mol\u00adecules are connected into \u2018dimers\u2019 with an via N2A\u2014H1N2\u22efS1Bi and N2B\u2014H2N2\u22efS1Ai hydrogen bonds -2-benzyl\u00adidene-N-cyclo\u00adhexyl\u00adhydrazine-1-carbo\u00adthio\u00adamide as the reference moiety resulted in nine structures containing a cyclo\u00adhexyl\u00adhydrazinecarbo\u00adthio\u00adamide moiety with different substituents (R). The different substituents (R) together with the torsion angles of the hydrazinecarbo\u00adthio\u00adamide connecting bridge are compiled in Table\u00a02cf. Fig.\u00a03\u03c42, \u03c43 and \u03c44 are in, respectively, anti-periplanar (153.5 to 179.3\u00b0), syn-periplanar (0.8 to 14.7\u00b0) and anti-periplanar (from 171.8 to 180.0\u00b0) conformations. The attached cyclo\u00adhexane ring is always close to perpendicular to the thio\u00adamide group and with a syn/anti-clinal (\u03c45 = 78.3 to 94.5\u00b0) conformation. Furthermore, torsion angle \u03c41 for most of these structures exists in a syn-periplanar conformation, ranging from 0 to 25.8\u00b0, but there is one outlier  conformation. The cyclo\u00adhexyl\u00adhydrazinecarbo\u00adthio\u00adamide moiety of this structure is substituted with an anthracen-9-yl\u00admethyl\u00adene ring system.A search of the Cambridge Structural Database  in 20\u2005ml methanol was added dropwise with stirring to the aldehyde solution. The resulting colourless solution was refluxed for 4\u2005h with stirring. A colourless precipitate was obtained on evaporation of the solvent. The crude product was washed with n-hexane (5\u2005ml). The recovered product was dissolved in aceto\u00adnitrile and purified by recrystallization. Colourless block-like crystals suitable for X-ray diffraction analysis were obtained on slow evaporation of the aceto\u00adnitrile solvent .2-Hy\u00addroxy-3-methyl\u00adbenzaldehyde  was dissolved in 20\u2005ml of methanol. Glacial acetic acid (0.20\u2005ml) was added and the mixture was refluxed for 30\u2005min. A solution of Spectroscopic and analytical data: 1H NMR : \u03b4 11.27 , \u03b4 9.51 , \u03b4 8.34 , \u03b4 8.05 , \u03b4 7.39\u20136.81 , \u03b4 2.20 , \u03b4 1.87\u20131.14  ppm. 13C NMR : \u03b4 175.79 (C=S), \u03b4 154.29 (C=N), \u03b4 143.76-119.17 (C-aromatic), \u03b4 15.93 (CH3), \u03b4 52.87\u201324.90 (C-cyclo\u00adhex\u00adyl) ppm. IR : 3364 (NH), 3148 (OH), 2989(CH3), 2931 and 2854 , 1620 (C=N), 1540 , 1268 (C=S), 1218 , 1122 (C\u2014O). 1075 (C\u2014N). Elemental analysis calculated for C15H21N3OS (Mr = 291.41\u2005g\u2005mol\u22121); C, 61.77; H, 7.21; N, 14.42%; found: C, 61.81; H, 7.19; N, 14.42%.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019008946/su5501sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019008946/su5501Isup2.hklStructure factors: contains datablock(s) I. DOI: 1480651CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the mol\u00adecular packing, methyl\u00adene-C\u2014H\u22efO(ring carbon\u00adyl) and N(pyridazin\u00adyl) inter\u00adactions result in the formation of a supra\u00admolecular tape along the  16H18N2O3, is constructed about a central oxopyridazinyl ring (r.m.s. deviation = 0.0047\u2005\u00c5), which is connected to an ethyl\u00adacetate group at the N atom closest to the carbonyl group, and benzyl and methyl groups second furthest and furthest from the carbonyl group, respectively. An approximately orthogonal relationship exists between the oxopyridazinyl ring and the best plane through the ethyl\u00adacetate group [dihedral angle = 77.48\u2005(3)\u00b0]; the latter lies to one side of the central plane [the Nr\u2014Nr\u2014Cm\u2014Cc  torsion angle being 104.34\u2005(9)\u00b0]. In the crystal, both H atoms of the N-bound methyl\u00adene group form methyl\u00adene-C\u2014H\u22efO(ring carbon\u00adyl) or N(pyridazin\u00adyl) inter\u00adactions, resulting in the formation of a supra\u00admolecular tape along the a-axis direction. The tapes are assembled into a three-dimensional architecture by methyl- and phenyl-C\u2014H\u22efO(ring carbon\u00adyl) and phenyl-C\u2014H\u22efO(ester carbon\u00adyl) inter\u00adactions. The analysis of the calculated Hirshfeld surface indicates the dominance of H\u22efH contacts to the overall surface (i.e. 52.2%). Reflecting other identified points of contact between mol\u00adecules noted above, O\u22efH/H\u22efO (23.3%), C\u22efH/H\u22efC (14.7%) and N\u22efH/H\u22efN (6.6%) contacts also make significant contributions to the surface.The title compound, C H)-ones are pyridazine derivatives, being constructed about a six-membered ring which contains two adjacent nitro\u00adgen atoms, at positions one and two, and with a carbonyl group at position three. The inter\u00adest in these nitro\u00adgen-rich heterocyclic derivatives arises from the fact that they exhibit a number of promising pharmacological and biological activities. These include anti-oxidant , the crystal and mol\u00adecular structures of the the title pyridazin-3(2H)-one derivative, (I)Pyridazin-3(2The mol\u00adecular structure of (I)2 and eight-membered {\u22efNNCH}2 synthons, respectively. The result is the formation of a supra\u00admolecular tape orientated along the a-axis direction, Fig.\u00a02a). Globally, the tapes assemble into layers in the ab plane and these stack along the c-axis direction as shown in Fig.\u00a02b). Weak inter\u00adactions contributing to the formation of the layers include methyl-C16\u2014H\u22efO1(ring carbon\u00adyl) contacts s Table\u00a02. Betweenet al., 2019dnorm in Fig.\u00a03a), the C\u2014H\u22efN contact involving the methyl\u00adene-H13A and pyridazinyl-N2 atoms are represented as bright-red spots on the surface. The diminutive red spots appearing near the methyl\u00adene-H13B and carbonyl-O1 atoms indicate the weak C\u2014H\u22efO contact, Fig.\u00a03a) and (b). The intense blue and red regions corresponding to positive and negative electrostatic potentials on the Hirshfeld surfaces mapped over electrostatic potential in Fig.\u00a04dnorm-mapped Hirshfeld surfaces in Fig.\u00a03dnorm mapped Hirshfeld surface illustrating weak inter\u00admolecular inter\u00adactions are shown in the views of Fig.\u00a05The Hirshfeld surfaces calculated for (I)a), and those delineated into H\u22efH, O\u22efH/H\u22efO, N\u22efH/H\u22efN and C\u22efH/H\u22efC and C\u22efC contacts \u2013(f); the percentage contribution from different inter\u00adatomic contacts to the Hirshfeld surfaces of (I)b), having the greatest contribution, i.e. 52.2%, to the Hirshfeld surface, a pair of beak-shaped tips at de + di \u223c2.3\u2005\u00c5 reflect the short inter\u00adatomic contact between the methyl-H5C and H16C atoms, Table\u00a02c) demonstrates two pairs of adjoining short tips at de + di \u223c2.5 and 2.6\u2005\u00c5, together with the green aligned points in the central region, which are indicative of weak C\u2014H\u22efO contacts present in the crystal. The pair of long spikes at de + di \u223c2.5\u2005\u00c5 in the fingerprint plot delineated into N\u22efH/H\u22efN contacts of Fig.\u00a06d), are the result of a potential C\u2014H\u22efN inter\u00adaction involving the methyl\u00adene-C13\u2014H13A and pyridazinyl-N2 atoms. The short inter\u00adatomic C\u22efH/H\u22efC contacts as summarized in Table\u00a02de + di \u223c2.7 and 2.8\u2005\u00c5, respectively in Fig.\u00a06e). The presence of a weak \u03c0\u2013\u03c0 contact between the oxopyridazinyl and phenyl rings is reflected in the thick arrow-like tip at de + di \u223c3.4\u2005\u00c5 in the fingerprint plot delineated into C\u22efC contacts of Fig.\u00a06f), specifically the short inter\u00adatomic C2\u22efC9 contact, Table\u00a02i.e. 2.3%, contribution from C\u22efN/N\u22efC contacts to the Hirshfeld surface.The overall two-dimensional fingerprint plot, Fig.\u00a06et al., 2007The most closely related structure to (I)H)-one precursor. To this pyridazine (0.05\u2005mol) was added potassium carbonate (0.1\u2005mmol), tetra\u00adbutyl\u00adammonium bromide (0.01\u2005mmol) and 2-ethyl bromo\u00adacetate (0.1\u2005mol) in di\u00admethyl\u00adformamide (20\u2005ml). The mixture was stirred for 24\u2005h at room temperature. At the end of the reaction, the solution was filtered and the solvent evaporated under reduced pressure. The residue was washed with water and methyl\u00adenechloride. The solvent was removed and colourless blocks of (I)A mixture of 3-benzyl\u00adidene-4-oxo\u00adpenta\u00adnoic acid (0.05\u2005mol) and hydrazine hydrate (0.1\u2005mol) in ethanol (100\u2005ml) was refluxed for 2\u2005h. The precipitate formed was filtered off and recrystallized from acetone to obtain the 5-benzyl-6-methyl\u00adpyridazin-3(2Uiso(H) set to 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698901900241X/hb7802sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901900241X/hb7802Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900241X/hb7802Isup3.cmlSupporting information file. DOI: 1897511CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Bnz\u22efNPrpnit  hydrogen bonds, are linked into stepped ribbons extending parallel to [110] by C\u2014HPrpnit\u22efOThz (Thz = thia\u00adzine) hydrogen bonds. The ribbons are joined into pairs by inversion-related C=O\u22efCl inter\u00adactions.In the title compound, the di\u00adhydro\u00adbenzo\u00adthia\u00adzine moiety is folded about the S1\u22efN1 axis. In the crystal, inversion dimers, generated by C\u2014H 18H12Cl2N2OS, consists of a di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit linked by a \u2013CH group to a 2,4-di\u00adchloro\u00adphenyl substituent, and to a propane\u00adnitrile unit is folded along the S\u22efN axis and adopts a flattened-boat conformation. The propane\u00adnitrile moiety is nearly perpendicular to the mean plane of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit. In the crystal, C\u2014HBnz\u22efNPrpnit and C\u2014HPrpnit\u22efOThz  hydrogen bonds link the mol\u00adecules into inversion dimers, enclosing R22(16) and R22(12) ring motifs, which are linked into stepped ribbons extending along [110]. The ribbons are linked in pairs by complementary C=O\u22efCl inter\u00adactions. \u03c0\u2013\u03c0 contacts between the benzene and phenyl rings, [centroid\u2013centroid distance = 3.974\u2005(1)\u2005\u00c5] may further stabilize the structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (23.4%), H\u22efCl/Cl\u22efH (19.5%), H\u22efC/C\u22efH (13.5%), H\u22efN/N\u22efH (13.3%), C\u22efC (10.4%) and H\u22efO/O\u22efH (5.1%) inter\u00adactions. Hydrogen bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry calculations indicate that the two independent C\u2014HBnz\u22efNPrpnit and C\u2014HPrpnit\u22efOThz hydrogen bonds in the crystal impart about the same energy (ca 43\u2005kJ\u2005mol\u22121). Density functional theory (DFT) optimized structures at the B3LYP/6\u2013311\u2005G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C These mol\u00adecules exhibit a wide range of biological applications indicating that the 1,4-benzo\u00adthia\u00adzine moiety is a potentially useful template in medicinal chemistry research and has therapeutic applications as anti-inflammatory (Trapani A (C1\u2013C6), is oriented at a dihedral angle of 1.89\u2005(6)\u00b0 with respect to the phenyl ring, C (C10\u2013C15). A puckering analysis of the heterocyclic ring B (S1/N1/C1/C6\u2013C8) of the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit gave the parameters QT = 0.1983\u2005(15)\u2005\u00c5, q2 = 0.1957\u2005(17)\u2005\u00c5, q3 = 0.0323\u2005(19)\u2005\u00c5, \u03c6 = 354.6\u2005(6)\u00b0 and \u03b8 = 80.8\u2005(5)\u00b0, indicating it adopts a flattened-boat conformation. The propane\u00adnitrile moiety is essentially perpendicular to the di\u00adhydro\u00adbenzo\u00adthia\u00adzine unit, as indicated by the C7\u2014N1\u2014C16\u2014C17 torsion angle of 88.6\u2005(2)\u00b0. In heterocyclic ring B, the C1\u2014S1\u2014C8 [103.69\u2005(9)\u00b0], S1\u2014C8\u2014C7 [121.12\u2005(14)\u00b0], C8\u2014C7\u2014N1 [120.59\u2005(17)\u00b0], C7\u2014N1\u2014C6 [126.27\u2005(16)\u00b0], C6\u2014C1\u2014S1 [123.84\u2005(15)\u00b0] and N1\u2014C6\u2014C1 [121.46\u2005(17)\u00b0] bond angles are enlarged when compared with the corresponding values in the closely related compounds, (2Z)-2-(4-chloro\u00adbenzyl\u00adidene)-4-[2-(2-oxooxazoliden-3-yl) eth\u00adyl]-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (II), -2-[(4-fluoro\u00adbenzyl\u00adidene]-4-(prop-2-yn-1-yl)-3,4 -di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (III), -4-[2-eth\u00adyl]-2(phenyl\u00admethyl\u00adidene)-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (IV), -2-[methyl\u00adidene]-4-[2-eth\u00adyl]3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-3-one, (V), Bnz\u22efNPrpnit (Bnz = benzene and Prpnit = propane\u00adnitrile) hydrogen bonds (Table\u00a01Prpnit\u22efOThz (Thz = thia\u00adzine) hydrogen bonds Cg1) and 2,4-dichlorophenyl rings  [Cg1\u22efCg3 = 3.974\u2005(1)\u2005\u00c5] may further stabilize the structure.In the crystal, inversion dimers are formed by C\u2014Hs Table\u00a01, enclosis Table\u00a01, enclosi)\u00b0 Fig.\u00a03. The conCrystalExplorer17.5  analysis  have a nearly symmetrical distribution of points, Fig.\u00a07c, with the thin edges at de + di = 2.82\u2005\u00c5. In the absence of C\u2014H\u22ef\u03c0 inter\u00adactions, the wings in the fingerprint plot delineated into H\u22efC/C\u22efH contacts (13.5%) also have a nearly symmetrical distribution of points, Fig.\u00a07d, with the thick edges at de + di \u223c2.90\u2005\u00c5. The wings in the fingerprint plot delineated into H\u22efN/N\u22efH contacts  have as pair of spikes with the tips at de + di = 2.30\u2005\u00c5. The C\u22efC contacts  have an arrow-shaped distribution of points with the tip at de = di \u223c1.78\u2005\u00c5. The H\u22efO/O\u22efH  and C\u22efCl/Cl\u22efC  contacts  and C\u22efS/S\u22efC  contacts are seen as pairs of wide spikes with the tips at de + di \u223c3.30 and 3.48\u2005\u00c5, respectively.The overall two-dimensional fingerprint plot, Fig.\u00a07H Table\u00a02, contribs Table\u00a02 are viewdnorm plotted onto the surface are shown for the H\u22efH, H\u22efCl/Cl\u22efH, H\u22efC/C\u22efH, H \u22ef N/N\u22efH, C\u22efC and H\u22efO/O\u22efH inter\u00adactions in Fig.\u00a08a\u2013f, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efCl/Cl\u22efH, H \u22ef C/C\u22efH and H\u22efN/N\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be \u221213.0 (Eele), \u22121.8 (Epol), \u221268.0 (Edis), 48.3 (Erep) and \u221244.4 (Etot) for the C\u2014HBnz\u22efNPrpnit hydrogen-bonding inter\u00adaction and \u221237.3 (Eele), \u22129.3 (Epol), \u221219.0 (Edis), 33.7 (Erep) and \u221242.0 (Etot) for C\u2014HPrpnit\u22efOThz.The inter\u00admolecular inter\u00adaction energies were calculated using the CE\u2013B3LYP/6\u201331G energy model available in via density functional theory (DFT) using standard B3LYP functional and 6\u2013311\u2005G basis-set calculations -2-[methyl\u00adidene]-3-oxo-3,4-di\u00adhydro-2H-1,4-benzo\u00adthia\u00adzin-4-yl]propane\u00adnitrile ring. The energy band gap [\u0394E = ELUMO\u00a0\u2212\u00a0EHOMO] of the mol\u00adecule is about 6.1979\u2005eV, and the frontier mol\u00adecular orbital energies, EHOMO and ELUMO are \u22127.1543 and \u22120.9564\u2005eV, respectively.The optimized structure of the title compound in the gas phase was generated theoretically et al., 2016R1 = Ph, R2 = C), gave 14 hits. With R1 = Ph and R2 = CH2C\u2261CH IIa  to 36\u00b0 (IIf). The other three  have the benzo\u00adthia\u00adzine unit nearly planar with a corresponding dihedral angle of ca 3\u20134\u00b0.A search in the Cambridge Structural Database (Groom Z)-2--2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one (1.8\u2005mmol), potassium carbonate (2.0\u2005mmol) and tetra n-butyl ammonium bromide (0.15\u2005mmol) in DMF (20\u2005ml). Stirring was continued at room temperature for 12 h. The salts were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate\u2013hexane (1/9) as eluent. The solid product obtained was recrystallized from ethanol to afford colourless crystals (yield: 82%).3-Bromo\u00adpropane\u00adnitrile (2.0\u2005mmol) was added to a mixture of (Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019005966/lh5901sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019005966/lh5901Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019005966/lh5901Isup3.cdxSupporting information file. DOI: 1913051CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E,1\u2032E)-bis\u00ad(methanylyl\u00adidene)}bis\u00ad[2-(tri\u00adfluoro\u00admeth\u00adoxy)phenol].In the title complex, the nickel(II) ion has a square-planar coordination sphere, being ligated by two N and two O atoms of the tetra\u00addentate Schiff base ligand 6,6\u2032-{-bis(methanylyl\u00adidene)}bis\u00ad[2-(tri\u00adfluoro\u00admeth\u00adoxy)phenol]-\u03ba4O,N,N\u2032,O\u2032)nickel(II), [Ni(C18H12F6N2O4)], the nickel(II) ion has a square-planar coordination sphere, being ligated by two N and two O atoms of the Schiff base ligand 6,6\u2032-{-bis\u00ad(methanylyl\u00adidene)}bis\u00ad[2-(tri\u00adfluoro\u00admeth\u00adoxy)phenol] (L). Inversion-related mol\u00adecules are linked by a short Ni\u22efNi inter\u00adaction of 3.2945\u2005(6)\u2005\u00c5 forming a dimer. In the crystal, the dimers stack up the a axis, with a closest Ni\u22efNi separation of ca 3.791\u2005\u00c5. There are no other significant inter\u00admolecular inter\u00adactions present. However, the Hirshfeld surface analysis and the two-dimensional fingerprint plots indicate that the packing is dominated by H\u22efF/F\u22efH, H\u22efH, O\u22efH/H\u22efO and C\u22efH/H\u22efC contacts.In the title complex, (6,6\u2032-{(1 Their \u2014OH and C=N groups are involved in the formation of covalent bonding with the metal atom; besides, these mol\u00adecules are known to be easy to synthesize giving a high yield under mild conditions by solvent or solvent-free methods \u2005\u00c5 . The nickel ion Ni1 is coordinated by two imine N atoms, N6 and N7, and by two phenoxo O atoms, O2 and O3, of the tetra\u00addentate Schiff base ligand L. The bond lengths, Ni\u2014O2 and Ni\u2014O3 , and Ni\u2014N6 and Ni\u2014N7  are close to the values observed for nickel complexes of similar ligands (see section Database survey). The coordinating atoms, N6, N7, O2, O3, are essentially planar with no atom deviating from its mean plane by more than 0.0325\u2005\u00c5. The \u03c44 factor for four-coordinated metal atoms is = 0.04, indicating an almost perfect square-planar coordination sphere for atom Ni1 a-axis direction with a Ni1i\u22efNi1ii separation of ca. 3.791\u2005\u00c5 . There are no other significant inter\u00admolecular inter\u00adactions present; both C\u2014H\u22efF and C\u2014H\u22efO inter\u00adactions exceed the sum of their van der Walls radii.In the crystal, the dimers stack up the et al., 2016et al. (1970supporting information files S1(H), S2(OMe) and S3(OEt)]. A common feature of these complexes is the dimer formation with an Ni\u22efNi separation of between ca 3.2 to 3.9\u2005\u00c5. The same dimeric arrangement is found in the title complex, where this separation is 3.2945\u2005(6)\u2005\u00c5. In the majority of these complexes, the Ni\u2014Nimine bond lengths vary from ca 1.837 to 1.956\u2005\u00c5 while the Ni\u2014Ophenoxo bond lengths vary from ca 1.834 to 1.936\u2005\u00c5. In the title complex, the Ni\u2014Nimine [1.839\u2005(3) and 1.843\u2005(3)\u2005\u00c5] and Ni\u2014Ophenoxo [1.840\u2005(2) and 1.845\u2005(2)\u2005\u00c5] bond lengths fall within these limits.A search of the Cambridge Structural Database , O\u22efH (12.4%) and C\u22efH (11.3%) contacts. The electrostatic potential energy in the range \u22120.031 to 0.256 a.u., obtained using the STO-3G basis set at the Hartree\u2013Fock level of theory, is illustrated in Fig.\u00a06The Hirshfeld surface analysis , was synthesized by condensation of 2-hy\u00addroxy-3-tri\u00adfluoro\u00admeth\u00adoxy\u00adbenzaldehyde (0.0095\u2005mmol) and 1,2-ethanedi\u00adamine (0.0095\u2005mmol) in ethanol under reflux for ca 18\u2005h. The yellow product obtained was washed with ether and dried at room temperature. Ni(CH3COO)2\u00b74H2O (0.0080\u2005mmol) dissolved in 20\u2005ml of ethanol was added slowly to an ethanol (20\u2005ml) solution of L (0.0080\u2005mmol) and the mixture was refluxed for ca 6\u2005h. The orange product obtained was filtered off and washed with toluene. Red rod-like crystals of the title complex were obtained by slow evaporation of a solution in ethanol at room temperature .The title Schiff base ligand (Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989019001919/su5478sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019001919/su5478Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019001919/su5478sup3.pdfCSD search S1. DOI: 10.1107/S2056989019001919/su5478sup4.pdfCSD search S2. DOI: 10.1107/S2056989019001919/su5478sup5.pdfCSD search S3. DOI: 1890705CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A new quinoxalin-derived ene-di\u00adthio\u00adcarbonate was synthesized and structurally analysed. The synthetic procedure and the compound\u2019s spectroscopic and analytical characterization are reported. I, C13H10N2O2S2, crystallizes in the monoclinic space group C2/c with eight mol\u00adecules in the unit cell. Excluding for the ethyl substituent, the mol\u00adecule of I adopts a nearly coplanar conformation (r.m.s. deviations is 0.058\u2005\u00c5), which is supported by the intra\u00admolecular C\u2014H\u22efO hydrogen-bonding inter\u00adaction between the two ring systems [C\u22efO = 2.859\u2005(3)\u2005\u00c5]. In the crystal, the mol\u00adecules form dimeric associates via two bifurcated C\u2014H\u22efO hydrogen-bonding inter\u00adactions between an ene hydrogen atom and a carbonyl functional group of an adjacent mol\u00adecule [C\u22efO = 3.133\u2005(3)\u2005\u00c5] and vice versa. The crystal structure is further stabilized by a three-dimensional network of weak hydrogen bonds between one mol\u00adecule and six adjacent mol\u00adecules as well as offset \u03c0\u2013\u03c0 stacking. The combination of the quinoxaline 2(1H)-one moiety with the di\u00adthio\u00adcarbonate moiety extends the aromaticity of the quinoxaline scaffold towards the substituent as well as influencing the \u03c0-system of the quinoxaline. The title compound is the direct precursor for a di\u00adthiol\u00adene ligand mimicking the natural cofactor ligand molybdopterin.The title compound  As a result of their unusual redox and structural characteristics and those of their metal complexes, they immediately attracted considerable scientific inter\u00adest \u2005\u00c5 for C5] and the di\u00adthiol\u00adene ring , which are connected by the C3\u2014C4 bond [length = 1.465\u2005(3)\u2005\u00c5], are essentially coplanar, with an angle of only 4.89\u2005(12)\u00b0 between the two planes \u2005\u00c5; Table\u00a01et al., 19952 bonds  and O2\u22efH2\u2014C2; D\u22efA = 3.133\u2005(3)\u2005\u00c5]. Here, the exact same atoms are involved as in the intra\u00admolecular hydrogen bond mentioned above. The respective hydrogen atom H2 is therefore bound to the ene carbon atom C2 and hydrogen bonded to the carbonyl oxygen (O2) of the quinoxaline moiety of the same mol\u00adecule as well as that of the adjacent mol\u00adecule , the quinoxalin substituent of the present mol\u00adecule is replaced by a coumarine , the ene-di\u00adthio\u00adcarbonate is replaced by an amino\u00adthia\u00adzole  an overall weaker resonance in A, in which the benzene ring C\u2014C distances are all very similar (i.e. strongly resonant) whereas all other distances are of more pronounced single- and double-bond character and of less aromatic character.By bidirectional inter\u00admolecular hydrogen bonding, the title compound crystallizes as dimeric associate with the same donor and acceptor roles for both monomers , C7 [C7\u2014H7\u22efO1\u2005\u00c5], C9 , C12  and acceptor inter\u00adactions involving S2 [S2\u22efH9\u2014C9(\u2212x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01)], O2  and O1 [O1\u22efH7\u2014C7 C\u2014H\u22efO and C\u2014H\u22efS hydrogen-bonding inter\u00adactions, forming a three-dimensional network Fig.\u00a02. In the H)-one was synthesized based on a reported literature procedure quinoxalin-2quinoxalin-2(1H)-one: To a solution of S-2--2-oxo-ethyl o-isopropyl carbonodi\u00adthio\u00adate  in 250\u2005ml DCM/Et2O 1:1 at ambient temperature, H2SO4 (25.50\u2005ml) was added. The reaction mixture was stirred at room temperature for 2h. After that, the reaction was quenched by addition of 250\u2005ml of ice and the mixture was stirred for 30\u2005min. The organic phase was washed with brine and water 3 \u00d7 250\u2005ml. The solvent was reduced to 10\u2005ml in vacuo and the greenish precipitate was filtered off and washed on the filter with cold acetone 3 \u00d7 50\u2005ml. The title compound was obtained as a greenish-white powder. Single crystals suitable for X-ray analysis were obtained by slow diffusion of solvents with chloro\u00adform and Et2O Yield: 1.85g (20%).1H NMR  \u03b4 8.79 ppm , 7.87 ppm , 7.61 ppm , 7.4 ppm , 4.39 ppm , 1.42 ppm . 13C NMR  \u03b4 152.54 ppm, 144.75 ppm, 133.25 ppm, 132.58 ppm, 131.14 ppm, 130.32 ppm, 126.98 ppm, 124.00 ppm, 113.47 ppm, 37.47 ppm, 12.20 ppm. IR (KBr pellet): (\u03bd cm\u22121) = 3495 (br), 1734 (w), 1646 (sst), 1601 (st), 1579 (st), 1535 (st), 1463 (st), 1383 (w), 1280 (st), 1248 (w), 1216 (w), 1173 (st), 1128 (w), 1087 (w), 1045 (w), 950 (w), 892 (st), 868 (w), 825 (st), 785 (w), 758 (st), 631 (w), 554 (w), 529 (w), 467 (w), 432 (w). APCI\u2013MS (m/s) = 291 (M+ + H+). Analysis calculated for C13H10N2O2S2: C, 53.78; H 3.47; N 9.65; S 22.09. Found: C, 53.41; H 3.25; N 9.86; S 22.32.Uiso(H) = 1.5Ueq(C) for the methyl group, C\u2014H = 0.99\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for the methyl\u00adene group and C\u2014H = 0.95\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for the aromatic atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018007892/kq2022sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018007892/kq2022Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018007892/kq2022Isup3.cmlSupporting information file. DOI: 1845671CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structure of the title mol\u00adecular solvate features O\u2014H\u22efO hydrogen bonds, Br\u22efO and \u03c0\u2013\u03c0 inter\u00adactions. Hirshfeld surface analysis and fingerprint plots helped to identify the major contributors to the inter\u00admolecular inter\u00adactions. 8H4Br2O4\u00b7C2H6O2, crystallizes with one-half of a 2,5-di\u00adbromo\u00adterephthalic acid (H2Br2tp) mol\u00adecule and one-half of an ethyl\u00adene glycol (EG) mol\u00adecule in the the asymmetric unit. The whole mol\u00adecules are generated by application of inversion symmetry. The H2Br2tp mol\u00adecule is not planar, with the di\u00adbromo\u00adbenzene ring system inclined by a dihedral angle of 18.62\u2005(3)\u00b0 to the carb\u00adoxy\u00adlic group. In the crystal, the H2Br2tp and EG mol\u00adecules are linked into sheets propagating parallel to (R44 (12) and R44 (28) graph-set motifs. Br\u22efO and weak \u03c0\u2013\u03c0 stacking inter\u00adactions are also observed. Hirshfeld surface analysis was used to confirm the existence of these inter\u00adactions.The title compound, C As a result of symmetry restrictions, the EG mol\u00adecule adopts an anti-conformation with an O3\u2014C5\u2014C5i\u2014O3i torsion angle of 180\u00b0 .The structures of the mol\u00adecular components in the title compound are shown in Fig.\u00a012Br2tp and EG mol\u00adecules are linked by strong-to-medium O\u2014H\u22efO hydrogen bonds between carb\u00adoxy\u00adlic acid and alcohol OH functions  to 0.9385 a.u. (blue) and the two-dimensional fingerprint plots are illustrated in Fig.\u00a04dnorm surface can be assigned to Br\u22efO contacts. Analysis of the two-dimensional fingerprint plots reveals that the H\u22efO/O\u22efH (28.8%) contacts are the dominant contributors to the Hirshfeld surface. The contribution of the Br\u22efH/H\u22efBr contacts is 22.1%, whereas Br\u22efBr contacts are negligible (0.9%). Other contacts viz. H\u22efH (17.7%), H\u22efC/C\u22efH (7.7%), Br\u22efC/C\u22efBr (7.2%), Br\u22efO/O\u22efBr (5.8%), C\u22efO/O\u22efC (4.5%), C\u22efC (3.3%) and O\u22efO (2.2%) also make significant contributions to the Hirshfeld surface.Hirshfeld surfaces ethyl\u00adidene]pyridine-4-carbohydrazonato-\u03ba2N\u2032,O}nickel(II)\u20132,5-di\u00adbromo\u00adterephthalic acid  in 5\u2005ml of EG was heated (333\u2005K) to reflux for 15\u2005min. The reaction solution was held for 2\u20133\u2005h and colourless block-shaped crystals suitable for single-crystal X-ray diffraction analysis were obtained.HUiso(H) = 1.2Ueq(C). The H atoms bound to O atoms were located from difference-Fourier maps but were refined with distance restraints of O\u2014H = 0.82 \u00b1 0.02\u2005\u00c5 and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019010260/wm5512sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019010260/wm5512Isup3.cdxSupporting information file. DOI: 10.1107/S2056989019010260/wm5512Isup4.hklStructure factors: contains datablock(s) I. DOI: 1941436CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "ANCA)\u2010associated vasculitis (AAV), S1P participated in MPO\u2010ANCA\u2010positive IgG\u2010induced glomerular endothelial cell (GEnC) activation via a S1P receptor (S1PR)\u2010dependent way. However, the downstream signalling pathways are not fully clear yet. In this study, we demonstrated that Rho guanosine triphosphatases (GTPases) signalling pathways, RhoA and Rac1 in particular, were implicated in MPO\u2010ANCA\u2010positive IgG\u2010mediated GEnCs activation enhanced by pathophysiological concentration of S1P in AAV. These results provide mechanistic insights into vascular barrier dysfunction in AAV, which may facilitate the development of effective therapies.Sphingosine\u20101\u2010phosphate (S1P) is a crucial regulator in vascular inflammation. Our recent study found that under pathophysiological concentration in active anti\u2010neutrophil cytoplasmic antibody ( S1P and its five G\u2010protein\u2010coupled receptors (GPCRs), S1PR1\u20105, are implicated in diverse vascular inflammatory conditions.Rho guanosine triphosphatases (GTPases) mediate diverse biological responses including morphogenesis, chemotaxis and cell cycle progression.22.1See the \u201cSupporting Information Data 2.2Primary human glomerular endothelial cells  were cultured according to the manufacturer's instructions.2.3MPO\u2010ANCA\u2010positive IgGs and normal IgGs were prepared as previously described2.4Rac1 and RhoA activation assays were performed following the manufacturer's instructions .2.5As biomarkers of endothelial cell activation, levels of soluble vascular cell adhesion molecule\u20101(sVCAM\u20101) and intercellular adhesion molecule\u20101 (sICAM\u20101) in the GEnC supernatants were tested with commercially available ELISA kits .2.6P\u00a0<\u00a0.05 . Differences were considered statistically significant if 33.1P\u00a0<\u00a0.001 by ANOVA; 140.1\u00a0\u00b1\u00a08.9% vs 100%, P\u00a0<\u00a0.001 by ANOVA)  Figure\u00a0,S3.3.2P\u00a0<\u00a0.001 by ANOVA; 113.9\u00a0\u00b1 9.4% vs 147.9\u00a0\u00b1\u00a05.2%, P\u00a0<\u00a0.001 by ANOVA; 124.7\u00a0\u00b1\u00a04.4% vs 147.9\u00a0\u00b1\u00a05.2%, P\u00a0<\u00a0.001 by ANOVA, respectively), while the S1PR5 agonist A97 up\u2010regulated the RhoA activity  . By contrast, the ICAM\u20101 and VCAM\u20101 levels in the supernatants of GEnCs stimulated by S1P combined with MPO\u2010ANCA\u2010positive IgG increased significantly upon pre\u2010incubation with Rac1 antagonist NSC  (Figure\u00a0Pre\u2010incubation of GEnCs with the RhoA antagonist CCG significantly decreased ICAM\u20101 and VCAM\u20101 levels in the supernatants of GEnCs stimulated by S1P plus MPO\u2010ANCA\u2010positive IgG (1352.33\u00a0\u00b1 \u00a0122.73\u00a0pg/mL vs 812.91\u00a0\u00b1\u00a025.12\u00a0pg/mL, 4In our present study, we demonstrated that under pathophysiological concentration in active AAV patients, S1P could activate both RhoA and Rac1 signalling pathways in MPO\u2010ANCA\u2010positive IgG\u2010treated GEnCs. According to Singleton et\u00a0al, RhoA and Rac1 play opposing roles in regulating endothelial barrier function in response to differential activation of S1PRs.In conclusion, our current study demonstrated that Rho GTPases signalling pathways were involved in S1P\u2010enhanced GEnCs activation with MPO\u2010ANCA\u2010positive IgG. RhoA activated by S1PR2\u20105 dominated the S1P\u2010induced GEnC activation in the presence of MPO\u2010ANCA\u2010positive IgG, while Rac1 activated by S1PR1 exerted opposite effect during this process. These findings provide us with more clues to determine the role of and Rho GTPases and S1P in the development of AAV.No conflict of interest to declare.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file.\u00a0Click here for additional data file."}
{"text": "The dihedral angles between the pyridine ring and its attached phenyl groups are 42.24\u2005(8) and 6.37\u2005(14)\u00b0. In the crystal, a system of classical O\u2014H\u22efO and O\u2014H\u22ef hydrogen bonds links the mol\u00adecules to form tube-like assemblies propagating parallel to the  23H20N2O4S, the sulfur atom is attached equatorially to the sugar ring with unequal S\u2014C bonds, viz.: S\u2014Cs = 1.808\u2005(2) and S\u2014Cp = 1.770\u2005(2)\u2005\u00c5 . The dihedral angles between the pyridine ring and its attached phenyl groups are 42.24\u2005(8) and 6.37\u2005(14)\u00b0. In the crystal, a system of classical O\u2014H\u22efO and O\u2014H\u22ef hydrogen bonds links the mol\u00adecules to form tube-like assemblies propagating parallel to the c-axis direction. Weak C\u2014H\u22efN inter\u00adactions are also observed.In the racemic title compound, C Thus, (1) reacted with (2) in KOH in acetone to give a product for which two isomeric N- or S-arabinoside structures were conceivable, corresponding to two possible modes of glycosyl\u00adation. The final deprotected product (see Scheme4) or its regioisomer pyridine-2-thione-N-arab\u00adinoside (5). Spectroscopic data cannot differentiate between these two structures.Here we report a one-step synthesis of the pyridine-2-thio\u00adarabinoside (4) as the only product in the solid state. We suggest that the 2,3,4-tri-O-acetyl-\u03b1-d-arabinopranosyl bromide (2) inter\u00adacts via a simple SN2 reaction to give the \u03b2-glycoside product (3), which after deprotection leads to the free 2-(\u03b2-d/l-arabino\u00adpyran\u00adosyl\u00adthio)-pyridine-3-carbo\u00adnitrile (4). This separates as a racemic mixture, presumably because of thermodynamic racemization during synthesis or crystallization  is shown in Fig.\u00a01et al., 2017s 1.808\u2005(2) and S\u2014Cp 1.770\u2005(2)\u2005\u00c5 . The phenyl ring at C31 is approximately coplanar with the pyridyl ring, but the ring at C21 is significantly rotated (inter\u00adplanar angles = 6.4\u2005(2) and 42.24\u2005(8)\u00b0, respectively). The relative orientation of the pyridyl ring and the sugar moiety is defined by the torsion angles N1\u2014C2\u2014S1\u2014C11 9.7\u2005(2) and C2\u2014S1\u2014C11\u2014C12 162.73\u2005(12)\u00b0. The intra\u00admolecular contact O1\u2014H01\u22efS1, with H\u22efS 2.79\u2005(4)\u2005\u00c5 and an angle of 109\u2005(3)\u00b0, is probably too long and has too narrow an angle to be considered a hydrogen bond.The mol\u00adecular structure of  contact of 3.2374\u2005(16)\u2005\u00c5  may play a supporting role, but is not shown explicitly.In the crystal, the mol\u00adecules are connected by two-centre O2\u2014H02\u22efO3d Table\u00a01, via thes Figs. 2 and 3 \u25b8.et al., 1993There is one other structure involving arabinose with a sulfur substituent at the C2 position; the arabinose is tri\u00adacetyl\u00adated and the sulfur atom, which is axially bonded to the sugar ring, acts as a bridge to a pyran\u00adopyrimidine ring system (Tomas H)-thione (1)  in aqueous potassium hydroxide  was added a solution of 2,3,4-tri-O-acetyl-\u03b1-d-arabino\u00adpyranosyl bromide (2)  in acetone (30\u2005ml). The reaction mixture was stirred at room temperature until the reaction was judged complete by TLC (30\u2005min to 2\u2005h). The mixture was evaporated under reduced pressure at 313\u2005K and the residue was washed with distilled water to remove the potassium bromide. The solid was collected by filtration and crystallized from ethanol to give compound (3) in 70% yield (m. p. 440\u2013442\u2005K). Dry gaseous ammonia was then passed through a solution of the protected thio\u00adglycoside (3) (0.5\u2005g) in dry methanol (20\u2005ml) at 273\u2005K for 15\u2005min, and the mixture was stirred at 273\u2005K until the reaction was complete . The mixture was evaporated at 313\u2005K to give a solid residue, which was recrystallized from methanol solution to give compound (4) in 60% yield (m.p. 479\u2013480\u2005K), IR (KBr): 3370\u20133480 (OH); 2222 (CN) cm\u22121. 1H NMR : \u03b4 3.10\u20133.70 ; 4.81\u20135.20 ; 5.52 , 7.05\u20137.78 , 7.99 . Analysis calculated for C23H20N2O4S (420.47): C, 65.60%; H, 4.76%; N, 6.66%. Found: C, 65.48%; H, 4.84%; N, 6.41%.To a solution of the pyridine-2- with Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018007284/hb7743sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018007284/hb7743Isup2.hklStructure factors: contains datablock(s) I. DOI: 1843269CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Protein\u2010polymer conjugates show improved pharmacokinetics but reduced bioactivity and tumor penetration as compared to native proteins, resulting in limited antitumor efficacy. To address this dilemma, genetic engineering of a body temperature\u2010responsive and matrix metalloproteinase (MMP)\u2010cleavable conjugate of interferon alpha (IFN\u03b1) and elastin\u2010like polypeptide (ELP) is reported with spatiotemporally programmed two\u2010step release kinetics for tumor therapy. Notably, the conjugate could phase separate to form a depot postsubcutaneous injection, leading to 1\u2010month zero\u2010order release kinetics. Furthermore, it could selectively be cleaved by MMPs that are overexpressed in tumors to release IFN\u03b1 from ELP and thus to recover the bioactivity of IFN\u03b1. Consequently, it exhibits dramatically enhanced tumor accumulation, tumor penetration, and antitumor efficacy as compared to free IFN\u03b1 in two mouse models of melanoma and ovarian tumor. These findings may provide an intelligent technology of thermoresponsive and protease\u2010cleavable protein\u2010polymer conjugates with spatiotemporally programmed two\u2010step release kinetics for tumor treatment. In this proof\u2010of\u2010concept study, a MMP substrate (MMPS) as a linker was genetically fused to the C\u2010terminal of IFN\u03b1 and the N\u2010terminal of a body temperature\u2010responsive elastin\u2010like polypeptide (ELP(V)) to form a body temperature\u2010responsive and MMP\u2010cleavable IFN\u03b1\u2010MMPS\u2010ELP(V) conjugate Schemea. IFN\u03b1 is Scheme b. Furthes Scheme c. Indeed22.1Tt values were genetically engineered (see Supporting Information). Simultaneously, two MMP\u2010noncleavable IFN\u03b1\u2010ELP conjugates of IFN\u03b1\u2010ELP(V) and IFN\u03b1\u2010ELP(A) with distinct Tt values were prepared as controls. Specifically, the sequence of MMPS was Pro\u2010Leu\u2010Gly\u2010Leu\u2010Ala\u2010Gly (PLGLAG). The A and V in ELP(A) and ELP(V) were the X in VPGXG repeat unit. The repeat unit number per ELP chain was 90. The conjugates were analyzed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS\u2010PAGE) and further confirmed by matrix\u2010assisted laser desorption/ionization time\u2010of\u2010flight mass spectrometry (MALDI\u2010TOF\u2010MS) to have the expected molecular weights  of the conjugates were determined by dynamic light scattering (DLS) to be around 11 nm, which were 3.8\u2010fold larger than that of IFN\u03b1 (2.9 nm)  and IFN\u03b1\u2010ELP(V) were below the body temperature of 37 \u00b0C when the concentrations were above 1 \u00d7 10\u22126m. These data suggested that IFN\u03b1\u2010MMPS\u2010ELP(V) and IFN\u03b1\u2010ELP(V) would in situ form depots upon subcutaneous injections at high concentrations and then would slowly liberate from the depots into circulatory system at low concentrations. By contrast, the Tt values of IFN\u03b1\u2010MMPS\u2010ELP(A) and IFN\u03b1\u2010ELP(A) were well above the body temperature even if the concentrations were as high as 1000 \u00d7 10\u22126m, suggesting that they could not in situ form depots upon subcutaneous injections. The antiproliferative activities of the conjugates , 53.8 pg mL\u22121 for IFN\u03b1\u2010MMPS\u2010ELP(A), 54.6 pg mL\u22121 for IFN\u03b1\u2010ELP(V), 56.9 pg mL\u22121 for IFN\u03b1\u2010ELP(A)) were nearly the same, which were around 37% of that of IFN\u03b1 (IC50 = 20.2 pg mL\u22121)  and IFN\u03b1\u2010MMPS\u2010ELP(A) with distinct s Figurea,b. The 2.2\u22121, IC50) and IFN\u03b1\u2010MMPS\u2010ELP(A)  were increased from 37% to about 91% of that of IFN\u03b1   and IFN\u03b1\u2010MMPS\u2010ELP(A), the conjugates were treated with MMP\u20102, followed by SDS\u2010PAGE analysis Figure g. As exp2.3Figuret1/2) of IFN\u03b1\u2010MMPS\u2010ELP(A) (8.9 \u00b1 1.0 h) and IFN\u03b1\u2010ELP(A) (9.6 \u00b1 2.7 h) were 6.4\u2010 and 6.9\u2010fold longer than that of free IFN\u03b1 (1.4 \u00b1 0.21 h), respectively. The area under the curves (AUCs) of IFN\u03b1\u2010MMPS\u2010ELP(A) (684.1 \u00b1 12.1 \u00b5g L\u22121\u00b7h) and IFN\u03b1\u2010ELP(A) (707.3 \u00b1 37.1 \u00b5g L\u22121 h) were 11.1\u2010 and 11.4\u2010fold larger than that of free IFN\u03b1 (61.8 \u00b1 1.7 \u00b5g L\u22121\u00b7h), respectively. Similarly, the biodistribution of IFN\u03b1\u2010MMPS\u2010ELP(A) was almost the same as that of IFN\u03b1\u2010ELP(A) but much superior to that of free IFN\u03b1 , respectively. These data indicated that the introduction of the MMPS linker into IFN\u03b1\u2010ELP(A) did not change the pharmacokinetics and biodistribution significantly. However, IFN\u03b1\u2010MMPS\u2010ELP(A) showed significantly enhanced tumor penetration as compared to both IFN\u03b1\u2010ELP(A) and free IFN\u03b1, as indicated by the more intense fluorescence (yellow) observed in the area that was distant from the vessels (red) for IFN\u03b1\u2010MMPS\u2010ELP(A) than for IFN\u03b1\u2010ELP(A) and free IFN\u03b1  on its in vivo properties in a mouse model of C8161 melanoma Figure. The pha2.4\u22121 body weight) for IFN\u03b1\u2010MMPS\u2010ELP(V) was the same as that for IFN\u03b1\u2010ELP(V), which was 5.0\u2010 and 6.7\u2010fold higher than those for IFN\u03b1\u2010MMPS\u2010ELP(A) (20 mg kg\u22121 body weight) and free IFN\u03b1 (15 mg kg\u22121 body weight), respectively . Interestingly, a bump in situ formed and gradually diminished over 40 d after subcutaneous injection of IFN\u03b1\u2010MMPS\u2010ELP(V) or IFN\u03b1\u2010ELP(V) at its MTD . This phenomenon suggested that both IFN\u03b1\u2010MMPS\u2010ELP(V) and IFN\u03b1\u2010ELP(V) could in situ form depots after subcutaneous injections at their MTDs because the Tt values of the two conjugates were far below the in vivo temperature  and IFN\u03b1 rapidly increased to 5878.7 \u00b1 187.1 \u00b5g L\u22121 at 4.0 h and 5456.9 \u00b1 758.5 \u00b5g L\u22121 at 2.8 h, respectively, and then decreased quickly. Representative pharmacokinetic parameters were generated by fitting the data with a one\u2010compartment model . Notably, The t1/2 of IFN\u03b1\u2010MMPS\u2010ELP(V) (422.2 \u00b1 13.7 h) was close to that of IFN\u03b1\u2010ELP(V) (491.8 \u00b1 38.1 h), but was 46.9\u2010 and 222.2\u2010fold longer than those for IFN\u03b1\u2010MMPS\u2010ELP(A) (9.0 \u00b1 0.87 h) and free IFN\u03b1 (1.9 \u00b1 0.08 h), respectively. The AUC of IFN\u03b1\u2010MMPS\u2010ELP(V) (2755.9 \u00b1 16.8 mg L\u22121\u00b7h) was close to that of IFN\u03b1\u2010ELP(V) (3102.0 \u00b1 269.8 mg L\u22121\u00b7h), but was 23.3\u2010 and 58.8\u2010fold larger than those for IFN\u03b1\u2010MMPS\u2010ELP(A) (118.3 \u00b1 15.1 mg L\u22121 h) and free IFN\u03b1 (46.9 \u00b1 7.8 mg L\u22121\u00b7h), respectively. Furthermore, the AUCs of IFN\u03b1\u2010MMPS\u2010ELP(V) and IFN\u03b1\u2010ELP(V) were correlated to time linearly , we further studied the in vivo properties of IFN\u03b1\u2010MMPS\u2010ELP(V) postsubcutaneous administration at its maximum tolerated dose (MTD). The MTD (100 mg kg\u22121 tissue) was nearly equal to that of IFN\u03b1\u2010ELP(V) (555.7 \u00b1 164.7 ng g\u22121 tissue), but was 18.0\u2010 and 317.2\u2010fold higher than those for IFN\u03b1\u2010MMPS\u2010ELP(A) (29.9 \u00b1 1.8 ng g\u22121 tissue) and free IFN\u03b1 (1.7 \u00b1 0.05 ng g\u22121 tissue) at 3 d postinjection, respectively  was studied after subcutaneous administration at the MTD. The biodistribution of IFN\u03b1\u2010MMPS\u2010ELP(V) was similar to that of IFN\u03b1\u2010ELP(V), but was much better than those of IFN\u03b1\u2010MMPS\u2010ELP(A) and free IFN\u03b1 . Notably, the tumor concentration of IFN\u03b1\u2010MMPS\u2010ELP(V)  was 3.5\u2010, 9.1\u2010, and 19.5\u2010fold smaller than those for IFN\u03b1\u2010ELP(V) (145.3 \u00b1 49.1 mm3), IFN\u03b1\u2010MMPS\u2010ELP(A) (376.8 \u00b1 121.7 mm3), and free IFN\u03b1 (808.2 \u00b1 226.1 mm3) at 30 d after the subcutaneous injections, respectively. Notably, 60% of the mice in the IFN\u03b1\u2010MMPS\u2010ELP(V) treatment group were tumor free, which was much higher than those for the treatments with IFN\u03b1\u2010ELP(V) (30%), IFN\u03b1\u2010MMPS\u2010ELP(A) (0%), and free IFN\u03b1 (0%)  was 3.4\u2010, 6.0\u2010, and 11.6\u2010fold smaller than those for IFN\u03b1\u2010ELP(V) (250.4 \u00b1 24.9 mm3), IFN\u03b1\u2010MMPS\u2010ELP(A) (434.9 \u00b1 119.9 mm3), and free IFN\u03b1 (847.9 \u00b1 248.2 mm3) at 33 d after the subcutaneous injections, respectively. Notably, 37.5% of the mice in the IFN\u03b1\u2010MMPS\u2010ELP(V) treatment group were tumor free, whereas the tumor cure percentages for the treatments with IFN\u03b1\u2010ELP(V), IFN\u03b1\u2010MMPS\u2010ELP(A), and free IFN\u03b1 were 0%  in a mouse model of melanoma. After subcutaneous injection at its MTD, IFN\u03b1\u2010MMPS\u2010ELP(V) suppressed melanoma growth more efficiently than IFN\u03b1\u2010ELP(V), IFN\u03b1\u2010MMPS\u2010ELP(A), and free IFN\u03b1 Figurea. The av2.6FigureAll the treatments did not cause obvious loss of body weight . As indicated by hematoxylin and eosin (H&E) staining, a more extensive degree of kidney damage was observed in the IFN\u03b1 treatment than in the other treatments, but no histological change in other major organs was observed in all the treatments Figure. This re3thuman = tmouse (Whuman/Wmouse)0.13 in which thuman and tmouse are the half\u2010lives of the conjugate in human and mouse, respectively, and Whuman and Whuman are the body weights of human and mouse, respectively.In conclusion, we have reported genetic engineering of a body\u2010temperature\u2010responsive and MMP\u2010cleavable protein\u2010polymer conjugate of IFN\u03b1\u2010MMPS\u2010ELP(V) with not only dramatically improved pharmacokinetics but also remarkably enhanced tumor accumulation and penetration, and antitumor efficacy. IFN\u03b1\u2010MMPS\u2010ELP(V) can be genetically engineered to own dual functions of body temperature responsiveness and MMP cleavability that enable spatiotemporally programmed two\u2010step release kinetics. The body temperature responsiveness can remarkably enhance the tolerability, pharmacokinetics, and tumor accumulation of the conjugate through the mechanism of body temperature\u2010responsive controlled release due to the concentration dependence of the phase transition temperature. Notably, in a mouse model, subcutaneous injection of the conjugate at its MTD offers an extremely prolonged circulation half\u2010life of 422.2 h. The half\u2010life of the conjugate in human is expected to be as long as 1195.5 h according to the empirical formulus of The authors declare no conflict of interest.SupplementaryClick here for additional data file."}
{"text": "The structure of a deca\u00adahydro\u00adacridine derivative with phenyl substituents at the 3- and 5-positions of the cyclo\u00adhexenone rings is reported. An extensive range of O\u2014H\u22efO, C\u2014H\u22efO hydrogen bonds augmented by C\u2014H\u22ef\u03c0(ring) hydrogen bonds an O\u22efBr halogen bond and an unusual Br\u22ef\u03c0(ring) contact stabilizes the crystal packing. 33H29BrClNO4, (I), the hexa\u00adhydro-2H-acridine ring system has a hy\u00addroxy\u00adethyl substituent on the N atom and a 3-bromo-6-chloro-2-hy\u00addroxy\u00adphenyl substituent on the central C atom at the 9-position. An unusual feature of the mol\u00adecule is that the substituents at the 3- and 5-positions of the outer cyclo\u00adhexenone rings are phenyl rings rather than the more common dimethyl substituents. C atoms on both of the cyclo\u00adhexenone rings are disordered over two sites. In the crystal structure, O\u2014H\u22efO, C\u2014H\u22efO and C\u2014H\u22ef\u03c0(ring) hydrogen bonds combine with an Br\u2014O and unusual C\u2014Br\u22ef\u03c0(ring) halogen bonds to generate a three dimensional network with mol\u00adecules stacked along the a-axis direction.In the structure of the title compound C These include compounds that are used as anti-infammatory  ring. The C2 and C3 atoms of one cyclo\u00adhexenone are disordered over two sites as is the C6 atom of the corresponding cyclo\u00adhexenone. Their occupancy ratios refine to 0.521\u2005(10):0.479\u2005(10) for C2,C3 and 0.746\u2005(9):0.254\u2005(9) for C6. Only details of the major disorder components will be considered here. The central C9,N10,C11\u2013C14 ring adopts a half-chair conformation and is inclined to the adjacent C1\u2013C4,C11,C12 and C5\u2013C8,C13,C14 rings at angles of 7.11\u2005(18) and 21.64\u2005(10)\u00b0, respectively, so the hexa\u00adhydro-2H-acridine unit is far from planar. The 3-bromo-6-chloro-2-hy\u00addroxy\u00adphenyl ring subtends an angle of 84.39\u2005(6)\u00b0 to this central ring. The C1\u2013C4,C11,C12 ring is best described as a severely flattened boat while the C5\u2013C8,C13,C14 system is in a distorted half-chair conformation. The phenyl substituents on these outer cyclo\u00adhexenone rings are inclined to their parent rings at angles of 76.87\u2005(12)\u00b0 for C31\u2013C36 and 86.27\u2005(8)\u00b0 for C61\u2013C66. The N-bound 2-hy\u00addroxy\u00adethyl substituent points away from the convex face of the hexa\u00adhydro-2H-acridine system as does the 3-bromo-6-chloro-2-hy\u00addroxy\u00adphenyl substituent.The title compound (I)ly Fig.\u00a01. The cenO\u22efO8 hydrogen bonds, Table\u00a01C(9) chains along the b-axis direction, linking the mol\u00adecules in a head-to-tail fashion, Fig.\u00a02a-axis direction through C65\u2014H65\u22efCg7 contacts, Fig.\u00a03A\u22efO16 hydrogen bonds form inversion dimers that enclose Cg8 inter\u00adactions. Adjacent dimers are linked by C34\u2014H34\u22efCl5\u2032 hydrogen bonds, forming double chains of mol\u00adecules along the ab diagonal, Fig.\u00a04v halogen bonds  \u2005\u00c5, C3\u2032\u2014Br3\u2032\u22efCg4 = 83.89\u2005(7)\u00b0; Cg4 is the centroid of the C1\u2032\u2013C6\u2032 benzene ring] et al. 2016H-acridine ring system, emphasizing the uniqueness of the structure reported here. Refining the search to structures with CH2CH substitution on the acridine N atom reduced the hits to seven, four of which have hy\u00addroxy\u00adethyl substituents on N10  = 0.95\u2005\u00c5 for aromatic, 0.99\u2005\u00c5 for methyl\u00adene and 1.00\u2005\u00c5 for methine H atoms, all with Uiso = 1.2Ueq(C). The C2 and C3 atoms in the C1\u2013C4,C11,C12 cyclo\u00adhexenone ring and atom, C6, in the corresponding C5\u2013C8,C13,C14 ring are disordered over two positions. Their occupancies were refined to sum to unity with the disordered atoms of the different rings allowed to refine separately. The occupancies converged to ratios of 0.521\u2005(10): 0.479\u2005(10) for C2 and C3 and 0.746\u2005(9): 0.254\u2005(9) for C6. Positions of the hydrogen atoms on adjacent methyl\u00adene groups and phenyl rings were assigned taking this disorder into account but a somewhat close H15A\u22efH5C contact was still observed. One reflection with Fo >>> Fc, was omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018010873/ff2154sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018010873/ff2154Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018010873/ff2154Isup3.cmlSupporting information file. DOI: 1859007CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C\u2014H\u22efO, C\u2014F\u22ef\u03c0 and F\u22efF inter\u00adactions are also observedThe title compound crystallizes with four mol\u00adecules in the unit cell (Z = 4) and one formula unit in the asymmetric unit. In the crystal, mol\u00adecules are linked in a head-to-tail fashion into dimers along the b-axis direction through weak C\u2014H\u22efBr and C\u2014O\u22efC 10H5BrF6O, synthesized via continuous stirring of 3,5-bis\u00ad(tri\u00adfluoro\u00admeth\u00adyl) aceto\u00adphenone with bromine in an acidic medium and concentrated under reduced pressure, crystallizes with four mol\u00adecules in the unit cell (Z = 4) and one formula unit in the asymmetric unit. In the crystal, mol\u00adecules are linked in a head-to-tail fashion into dimers along the b-axis direction through weak C\u2014H\u22efBr and C\u2014O\u22efCsp2 inter\u00adactions. C\u2014H\u22efO, C\u2014F\u22ef\u03c0 and F\u22efF inter\u00adactions are also observed.The title compound, C N-bromo\u00adsuccinimide . The torsion angle between the alkyl bromide unit and the phenyl ring (C3\u2014C2\u2014C1\u2014Br1) is \u2212179.6\u2005(3)\u00b0 whereas that between the alkyl bromide and carbonyl parts (O1\u2014C2\u2014C1\u2014Br1) is 0.3\u2005(5)\u00b0, which shows a preference for a syn orientation of the alkyl bromide unit with respect to the carbonyl group.A displacement ellipsoid plot of the title compound with the atom labelling is shown in Fig.\u00a01c-axis direction by C\u2014H\u22efO and C\u2014F\u22ef\u03c0 inter\u00adactions  [2.868\u2005(4)\u2005\u00c5] inter\u00adactions, resulting in a bilayer which further packs in parallel fashion along the a-axis direction  (O\u22ef\u03c0 = 3.252\u2005\u00c5) inter\u00adactions. The dimers are linked along the s Table\u00a01. The asson Fig.\u00a03.et al., 2016et al., 2011et al., 1991Z = 4, features two prominent hydrogen bonds involving the oxygen atom while in the second, also Z = 4, the oxygen atom forms a complex with anti\u00admony penta\u00adchloride.There are more than 1000 crystal structure of phenyl ethanone derivatives in the Cambridge Structural Database (CSD) : 8.44 , 8.13 , 4.48 ; 13C NMR: : 188.81, 135.31, 133.06, 132.83, 132.60, 128.99, 127.08, 127.06, 125.42, 123.61, 121.80, 120.00, 29.46.A stirred solution of 3,5-bis\u00ad(tri\u00adfluoro\u00admeth\u00adyl) aceto\u00adphenone  in acetic acid (5\u2005mL) was added dropwise to bromine  in acetic acid. The reaction medium was stirred at room temperature for 5\u2005h. To the resulting mixture, water (5\u2005mL) was added and the mixture was concentrated under reduced pressure. The residue obtained was diluted with ethyl\u00adacetate (10\u2005mL), the organic layer washed with water (10\u2005mL) and a sodium bicarbonate solution (5\u2005mL), and filtered through dried sodium sulfate and evaporated to obtain 1-phen\u00adyl)-2-bromo\u00adethanone as a light-yellow solid in 62% yield. m.p: 317\u2013318\u2005K. Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018007478/ds2250sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018007478/ds2250Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018007478/ds2250Isup3.cmlSupporting information file. DOI: 1843826CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One chain type, an unanchored NEDD8 trimer, specifically bound to the second zinc finger domain of PARP\u20101 and attenuated its activation. In cells in which Nedp1 is deleted, large amounts of tri\u2010NEDD8 constitutively form, resulting in inhibition of PARP\u20101 and protection from PARP\u20101\u2010dependent cell death. Surprisingly, these NEDD8 trimers are additionally acetylated, as shown by mass spectrometry analysis, and their binding to PARP\u20101 is reduced by the overexpression of histone de\u2010acetylases, which rescues PARP\u20101 activation. Our data suggest that trimeric, acetylated NEDD8 attenuates PARP\u20101 activation after oxidative stress, likely to delay the initiation of PARP\u20101\u2010dependent cell death.NEDD8 is a ubiquitin\u2010like protein that activates cullin\u2010RING E3 ubiquitin ligases (CRLs). Here, we identify a novel role for NEDD8 in regulating the activity of poly(ADP\u2010ribose) polymerase 1 (PARP\u20101) in response to oxidative stress. We show that treatment of cells with H UBLs are small proteins of approximately 8\u00a0kDa molecular mass that become covalently linked to other proteins via an isopeptide bond, usually on lysine residues  polymerase 1 (PARP\u20101) and attenuates its activation. PARP\u20101 overactivation mediates cell death after oxidative stress, and our data suggest that tri\u2010NEDD8 prevents PARP\u20101 hyperactivation to delay premature commitment to cell death.et\u00a0al, et\u00a0al, Nedp1 led to the accumulation of neddylated species that do not migrate at the ~\u00a0100\u00a0kDa size of neddylated cullins in both cell lines . When exposed to cell extract, this resin efficiently enriched neddylated proteins from both NEDP1 KO cells and from WT cells, but it did not enrich for ubiquitylated proteins  and the NEDD8 E2 enzyme, UBE2M, but in the absence of any NEDD8 E3. The smallest protein in these in\u00a0vitro reactions, aside from NEDD8 (8.5\u00a0kDa), was UBE2M, with a molecular mass of ~\u00a022\u00a0kDa. The smallest possible, non\u2010NEDD8\u2010NEDD8 conjugate in these reactions, a UBE2M\u2010NEDD8 linkage, would thus have a molecular mass of ~\u00a031\u00a0kDa. However, while this product was present in the reaction, conjugates were also formed at lower molecular masses that could only correspond to unanchored NEDD8 dimers, trimers and tetramers  inhibitor (MLN4924) alone, and not following treatment with the ubiquitin E1 enzyme (UBE) inhibitor (MLN7243) ation (PAR), including the poly(ADP\u2010ribose) polymerase PARP\u20101 Fig\u00a0. In factet\u00a0al, et\u00a0al, +) to covalently attach ADP\u2010ribose to various amino acids, including aspartic acid, glutamic acid, lysine, arginine and serine, that are present on itself and on its substrate proteins ation are known regulators of DNA repair and of the oxidative stress response. PARP\u20101 senses DNA damage caused by oxygen radicals and aids in the early steps of DNA repair , together with its substrate receptor Kelch\u2010like ECH\u2010associated protein 1 (Keap1), is involved in the cellular response to oxidative stress. Oxidative stress inhibits the Cul3/Keap1\u2010dependent degradation of the transcription factor nuclear factor erythroid 2\u2010related factor 2 (Nrf2), which drives gene expression that protects against cell death , but not to its automodification and catalytic domain  Fig\u00a0G. The DNet\u00a0al, In addition to its roles in DNA repair, PARP\u20101 also inhibits the transcription of some NF\u2010\u03baB\u2010responsive genes, including CXCL10, independently of its catalytic activity, but via its ability to directly bind to DNA  Fig\u00a0C to puriFrom these results, we hypothesized that the acetylation of NEDD8 may serve to mask the positively charged lysine residues of NEDD8 to facilitate its binding to the PARP\u20101 Zn2 domain. To confirm whether changes in acetylation influence the interaction of NEDD8 with PARP\u20101, we overexpressed the de\u2010acetylases HDAC1 or HDAC2 in NEDP1 KO cells, which indeed led to a decrease in the amount of NEDD8 trimer bound to exogenously expressed and precipitated GFP\u2010PARP\u20101 Zn1\u00a0+\u00a02 Fig\u00a0C. Likewiin\u00a0vitro NEDD8 chains by NEDP1 was strongly inhibited by the presence of even low amounts of H2O2  that occur following oxidation of DNA. Zn2 binds to DNA with the highest affinity , Sh \u03b1\u2010NEDP1 1:1,000 (DSTT S378D against AA1\u2013212), Ms \u03b1\u2010DCUN1D1 1:1,000 (Sigma Clone 3D7), Sh \u03b1\u2010DCUN1D2 1:1,000 (DSTT S995C against AA1\u201360) incubated with recombinant DCNL1 (AA 1\u201345) peptide to block cross reaction, Sh \u03b1\u2010DCUN1D3 1:2,000 (DSTT S996C against AA1\u201360), Sh \u03b1\u2010DCUN1D4 1:2,000 (DSTT S997C against AA1\u2013119), Sh \u03b1\u2010DCUN1D5 1:2,000 (DSTT S998C against AA1\u2013124), Rb \u03b1\u2010NEDD8 1:1,000 (Abcam ab81264), Sh \u03b1\u2010UBE2M 1:1,000 [DSTT S432D against full length (mouse)], Sh \u03b1\u2010UBE2F 1:1,000 (DSTT S438D against AA1\u201370), Ms \u03b1\u2010Actin 1:1,000 , Rb \u03b1\u2010RBX1 1:200 (Thermo PA5\u201016282), Rb \u03b1\u2010CAND1 1:1,000 (CST 7433S), Rb \u03b1\u2010CSN5 1:1,000 (Abcam ab12323), Rb \u03b1\u2010CSN8 1:1,000 (Abcam EPR5139), Rb \u03b1\u2010UBA3 1:1,000 (Epitomics 5157\u20101), Ms \u03b1\u2010AppBp1/ULA1 1:1,000 (BD 611865), Rb \u03b1\u2010Cul1 1:1,000 (Life Tech 718700), Rb \u03b1\u2010Cul2 1:5,000 (Life Tech 700179), Sh \u03b1\u2010Cul3 1:1,000 , Sh \u03b1\u2010Cul3 1:1,000 (DSTT S464D AA544\u2013768), Sh \u03b1\u2010Cul4A 1:3,500 (DSTT S087D AA1\u2013124), Rb \u03b1\u2010Cul4A 1:1,000 (CST 2699S), Sh \u03b1\u2010Cul4B 1:1,000 (DSTT S070D AA1\u2013162), Sh \u03b1\u2010Cul5 1:1,000 (DSTT S073D AA577\u2013689), Ms \u03b1\u2010I\u03baB\u03b1 1:1,000 (CST 4814), Ms \u03b1\u2010pI\u03baB\u03b1 1:1,000 (CST 9246 clone 5A5), Ms \u03b1\u2010PAR Polymer 1:1,000 (Enzo Lifescience ALX\u2010804\u2010220\u2010R100 clone 10H), Rb \u03b1\u2010PARP\u20101 1:1,000 (CST 9532), Rb \u03b1\u2010AIF 1:1,000 (Abcam ab 32516), Rb \u03b1\u2010NRF2 1:1,000 (Abcam ab62352), Rb \u03b1\u2010HIF\u20101\u03b1 1:1,000 , Ms \u03b1\u2010FLAG M2 1:2,000 (Sigma F3165), Ms \u03b1\u2010GFP 1:5,000 (Abcam ab184519); Rb \u03b1\u2010PARG 1:1,000 (CST 66564S); Rb \u03b1\u2010Keap1 1:1,000 (CST 8047).2O2, Sigma (216763); Camptothecin, Sigma (C9911); Cycloheximide, Sigma (C1988); DPQ, Calbiochem (300270); CellTiter\u2010Glo, Promega (G7570); Olaparib, Cambridge Biosciences (CAY10621); PARG inhibitor PDD 17273, Tocris (5952); Sodium Butyrate, Sigma (303410); GFP\u2010Trap_A, Chromotek (gta), PARP\u20101\u2010Trap_A, Chromotek (xta); phosSTOP, Sigma (4906845001); cOmplete EDTA\u2010free protease inhibitor cocktail (Roche\u201011836170001); Pepstatin A, Sigma (P5318), Bestatin hydrochloride, Sigma (B8385); Deoxyribonuclease I, Sigma (D5025); LDS Sample Buffer, Life Technologies (NP0007); Colloidal Coomassie, Expedeon (ISB1L); IPTG, Formedium (IPTG025); Micrococcal Nuclease, NEB (M0247S).TNF\u2010\u03b1, PeproTech (300\u201001A); HALO\u2010link resin, Promega (G1913); MLN7243, Active Biochemicals (A\u20101384); MLN4924, Active Biochemicals (A\u20101139); Hhis6\u2010HALO NEDP1(C163A) DSTT DU28042his6\u2010HALO NEDP1(C163A D29W A98K G99K) DSTT DU28008pCMV5\u2010NEDP1 DSTT DU28199GST\u2010NEDP1 DSTT DU23262Frt/TO N\u2010FLAG empty DSTT DU13236Frt/TO N\u2010GFP empty DSTT DU45825Frt/TO C\u2010GFP empty DSTT DU41574Frt/TO C\u2010FLAG empty DSTT DU43547GST empty DSTT DU49206et\u00a0al, gRNAs for NEDP1 and CAND1 were generated by mutagenesis PCR of pEsgRNA (Munoz NEDP1 gRNA F 5\u2032\u2010GGAAAGGACGAAACACCGCCCCGTAGTCTTGAGTTACAGTTTTAGAGCTAGAAAT\u20103\u2032NEDP1 gRNA R5\u2032\u2010ATTTCTAGCTCTAAAACTGTAACTCAAGACTACGGGGCGGTGTTTCGTCCTTTCC\u20103\u2032CAND1 gRNA F 5\u2032\u2010GGAAAGGACGAAACACCTCACCTAAAGTCCTTGTCGCGTTTTAGAGCTAGAAAT\u20103\u2032CAND1 gRNA R 5\u2032\u2010ATTTCTAGCTCTAAAACGCGACAAGGACTTTAGGTGAGGTGTTTCGTCCTTTCC\u20103\u2032Full\u2010length PARP\u20101 (NM_001618.3) was amplified from HUVEC cDNA and cloned into the N\u2010terminal GFP\u2010tagged vector. For domain mapping, individual zinc finger domains were cloned into the C\u2010terminal GFP vector and the catalytic domain was cloned into the N\u2010terminal GFP vector. GST\u2010PARP\u20101 ZN1\u00a0+\u00a02 was cloned in pGEX\u20106P\u20102 (GE Lifesciences). NSUN2 (NM_017755.5) was amplified from HUVEC cDNA and cloned into the N\u2010terminal FLAG empty vector. HDAC1 (NM_004964.2) and HDAC2 (NM_001527.3) were both amplified from HUVEC cDNA and cloned into the C\u2010terminal FLAG empty vector.PARP\u20101 Full(NM_001618.3) F 5\u2032\u2010ATGGCGGAGTCTTCGGATAAGCTCT\u20103\u2032PARP\u20101 Full(NM_001618.3) R 5\u2032\u2010TAGTACGCGGCCGCTTACCACAGGGAGGTCTTAAAATTGAATTTCAGTTTCAGC\u20103\u2032PARP\u20101 Zn1 (AA1\u201096) F 5\u2032\u2010ATGGCGGAGTCTTCGGATAAGCTCT\u20103\u2032PARP\u20101 Zn1 (AA1\u201096) R 5\u2032\u2010GTACTAGCGGCCGCGCCTGTCACTCCTCCAGCTTCCG\u20103\u2032PARP\u20101 Zn2 (AA97\u2010215) F 5\u2032\u2010TAGTACGGATCCAAAGGCCAGGATGGAATTGGTAGC\u20103\u2032PARP\u20101 Zn2 (AA97\u2010215) R stop 5\u2032\u2010GTACTAGCGGCCGCCTATCCATCCACCTCATCGCCTTTTCT\u20103\u2032PARP\u20101 Zn2 (AA97\u2010215) R no stop 5\u2032\u2010GTACTAGCGGCCGCTCCATCCACCTCATCGCCTTTTCT\u20103\u2032PARP\u20101 Zn3 (AA216\u2010336) F 5\u2032\u2010TAGTACGGATCCGTGGATGAAGTGGCGAAGAAGAAATCTA\u20103\u2032PARP\u20101 Zn3 (AA216\u2010336) R 5\u2032\u2010GTACTAGCGGCCGCTGGGGTTACCCACTCCTTCC\u20103\u2032PARP\u20101 C\u2010terminal (AA336\u20101014) F 5\u2032\u2010TAGTACCCCGGGAAGGAATTCCGAGAAATCTCTTACCTCAA\u20103\u2032PARP\u20101 C\u2010terminal (AA336\u20101014) R5\u2032\u2010TAGTACGCGGCCGCTTACCACAGGGAGGTCTTAAAATTGAATTTCAGTTTCAGC\u20103\u2032NSUN2(NM_017755.5) F 5\u2032\u2010AATAATAGAATTCATGGGGCGGCGGTCGCGGG\u20103\u2032NSUN2(NM_017755.5) R 5\u2032\u2010TATTATTGCGGCCGCTCACCGGGGTGGATGGACCCCC\u20103\u2032HDAC1(NM_004964.2) F 5\u2032\u2010AAAGGATCCATGGCGCAGACGCAGGGCACCCGGAGGAAAGT\u20103\u2032HDAC1(NM_004964.2) R 5\u2032\u2010TACGCGGCCGCGGCCAACTTGACCTCCTCCT\u20103\u2032HDAC2(NM_001527.3) F 5\u2032\u2010TACGGATCCATGGCGTACAGTCAAGGAGGCGGCAAAAAA\u20103\u2032HDAC2(NM_001527.3) R 5\u2032\u2010TACGCGGCCGCGGGGTTGCTGAGCTGTTCTGATTTGGTTC\u20103\u2032Ct\u2212\u2206\u2206 method  for 4\u00a0h at 37\u00b0C and harvested with RNeasy  following the manufacturer's protocol. Following RNA purification, RNA concentration was measured with a NanoDrop (Thermo Fisher Scientific) and 1\u00a0\u03bcg of RNA was used to generate cDNA using the High\u2010Capacity cDNA Reverse Transcription Kit (Invitrogen #4368814). qPCRs were performed with Brilliant III Ultra\u2010Fast SYBR Green qPCR master mix (Agilent 600882) on a Bio\u2010Rad CFX96. The 218S F 5\u2032\u2010GTAACCCGTTGAACCCCATT\u20103\u203218S R 5\u2032\u2010CCATCCAATCGGTAGTAGCG\u20103\u2032CXCL10 F 5\u2032\u2010GCTGATGCAGGTACAGCGT\u20103\u2032CXCL10 R 5\u2032\u2010CACCATGAATCAAACTGCGA\u20103\u2032I\u03baB\u03b1 F 5\u2032\u2010GATCCGCCAGGTGAAGGG\u20103\u2032I\u03baB\u03b1 R 5\u2032\u2010GCAATTTCTGGCTGGTTGG\u20103\u2032Nrf2 F 5\u2032\u2010AGACGGTATGCAACAGGACA\u20103\u2032Nrf2 R 5\u2032\u2010AGTTTGGCTTCTGGACTTGGA\u20103\u2032NQO1 F 5\u2032\u2010TCACCGAGAGCCTAGTTCCG\u20103\u2032NQO1 R 5\u2032\u2010TGGCATAGTTGAAGGACGTCC\u20103\u2032GAPDH F 5\u2032\u2010GAAATCCCATCACCATCTTCCAGG\u20103\u2032GAPDH R 5\u2032\u2010GTACCTCTTCCGACCCCGAG\u20103\u2032et\u00a0al . GST\u2010NEDP1 and GST vectors were transformed into BL21 cells and purified with Glutathione Sepharose 4B . His6\u2010USP1/UAF1 was obtained from the Division of Signal Transduction Therapy (DSTT)  product, DU23056. The plasmids encoding GST\u2010PARP\u20101 Zn1\u00a0+\u00a02, GST\u2010PARP\u20101 Zn1\u2010GFP and GST\u2010PARP\u20101 Zn2\u2010GFP were transformed into BL21 Rosetta 2 (DE3)\u2010competent cells (Novagen 71400). Cells were grown in 2YT media supplemented with 100\u00a0\u03bcM ZnSO4, and protein expression was induced with 0.2\u00a0mM IPTG at 16\u00b0C for 20\u00a0h. Cells were pelleted by centrifugation, and pellets were resuspended in lysis buffer . Pellets were sonicated; then, 5\u00a0mM MgCl2 and DNase I were added to 200\u00a0Kunitz/ml; and the cell suspension was incubated with rotation at 4\u00b0C for 1\u00a0h. Cell lysate was spun at 20,000\u00a0\u00d7\u00a0g for 30\u00a0min, and supernatant was collected. GST fusion proteins were then purified with Glutathione Sepharose 4B . The GST tag was cleaved from GST\u2010PARP\u20101 Zn1\u2010GFP and GST\u2010PARP\u20101 Zn2\u2010GFP with PreScission Protease . Bound DNA was removed from Zn1\u2010GFP and Zn2\u2010GFP via a Heparin column  as previously described  in a 37\u00b0C incubator with 5% CO2. Cell lines were routinely checked for\u00a0mycoplasma contamination. siRNA\u2010mediated knockdown of DCNL1\u20105 was carried out as previously described  supplemented with 10% FBS and 3\u00a0mM l, et\u00a0al  and Munol . To immunoprecipitate the FLAG\u2010tagged proteins, cells were harvested as above in buffer A. Supernatants were incubated with anti\u2010FLAG\u2010M2 magnetic beads (Sigma) for 3\u00a0h at 4\u00b0C. Beads were then washed three times with 0.5\u00a0ml of buffer A without inhibitors and then resuspended in reaction buffer . Beads were split evenly between three tubes, and either GST\u2010NEDP1, his6\u2010USP1/UAF1 or no protein was added to each tube. Reactions were then incubated at 30\u00b0C for 30\u00a0min before being stopped with LDS sample loading buffer. To immunoprecipitate endogenous PARP\u20101 and GFP fusion proteins, cells were harvested with buffer B: 50\u00a0mM Tris\u2013HCl pH 7.5, 150\u00a0mM NaCl, 5% glycerol, 0.5% NP\u201040, 5\u00a0mM MgCl2, 0.2\u00a0mM CaCl2, 1\u00a0\u03bcM pepstatin A, 1\u00a0\u03bcM bestatin supplemented with phosStop and cOmplete mini protease inhibitor. Lysates were sonicated for six pulses of 0.5\u00a0s. Subsequently, DNase I (200\u00a0Kunitz/ml) was added to lysates and incubated for 1\u00a0h at 4\u00b0C with rotation. Lysates were centrifuged at 4\u00b0C for 20\u00a0min at 17,000\u00a0\u00d7\u00a0g, and supernatants were collected. GFP\u2010Trap beads or PARP\u20101\u2010Trap beads were incubated with lysates for 3\u00a0h at 4\u00b0C with rotation. Next, agarose beads were washed three times with 0.5\u00a0ml of wash buffer . Bound proteins were eluted with LDS sample loading buffer and heated at 95\u00b0C for 5\u00a0min with 10\u00a0mM DTT. For GFP pulldown with HDAC overexpression, cells were lysed with buffer B with 2.7\u00a0mM KCL. For GFP pulldown after MNase treatment, cells were lysed with buffer B with 75\u00a0mM NaCl, 5\u00a0mM CaCl2, 15\u00a0mM IAA, 3\u00a0mM OPT and 4,000 units of MNase (NEB) per ml of lysate and incubated at 25\u00b0C for 30\u00a0min.Whole\u2010cell lysates were prepared with buffer A: 50\u00a0mM Tris\u2013HCl pH 7.5, 150\u00a0mM NaCl, 5% glycerol, 0.5% NP\u201040, 0.5% sodium deoxycholate, 0.1% SDS, 1\u00a0mM EDTA, 3\u00a0mM 1,10\u2010phenanthroline, and 15\u00a0mM iodoacetamide (IAA), supplemented with phosStop (Roche) and cOmplete mini protease inhibitor (Sigma). Lysates were sonicated and centrifuged at 4\u00b0C for 20\u00a0min at 17,000\u00a0\u00d7\u00a02O2, cells were lysed directly in sample loading buffer  and DNA was fragmented by passage through a homogenizer column (Omega Bio\u2010tek). Proteins were subsequently reduced with 10\u00a0mM DTT at 95\u00b0C for 5\u00a0min before loading onto SDS\u2013PAGE gels.For the analysis of Cullin neddylation, cells were lysed directly in urea loading buffer  and DNA was fragmented by passage through a homogenizer column (Omega Bio\u2010tek). Proteins were subsequently reduced with 10\u00a0mM DTT at 37\u00b0C for 10\u00a0min before loading onto SDS\u2013PAGE gels. For the analysis of PAR polymer formation after H2O2 continuously for 24\u00a0h. Where indicated, cells were treated with DMSO, olaparib, or DPQ for 1\u00a0h before treatment with H2O2, and continuously thereafter. After 24\u00a0h, cell viability was determined using the CellTiter\u2010Glo assay (Promega). To assess the viability of U2OS cell lines after treatment with camptothecin, cells were plated at 5,000 cells per well of a 96\u2010well plate and 24\u00a0h later were treated with the indicated concentration of camptothecin at 37\u00b0C. After 48\u00a0h, cell viability was measured using the CellTiter\u2010Glo Assay. To analyse cell death after TNF\u03b1\u00a0+\u00a0cycloheximide treatment, U2OS cells were plated at 10,000 cells per well of a 96\u2010well plate. Twenty\u2010four hours after plating, cells were treated with cycloheximide (10\u00a0\u03bcg/ml) for 1\u00a0h and then treated with the indicated amount of TNF\u2010\u03b1. Twenty\u2010four hours after treatment, cell viability was measured using the CellTiter\u2010Glo Assay (Promega).For cell viability analysis of U2OS cell lines, cells were plated at 15,000 cells per well of a 96\u2010well plate and 24\u00a0h later were treated with the indicated concentration of HCell lysates were resolved on Bis\u2010Tris gels (homemade or NuPAGE 4\u201312%) with MOPS buffer (Formedium MOPS\u2010SDS5000) and transferred to nitrocellulose or 0.2\u2010\u03bcm PVDF membranes. Membranes were blocked for 1\u00a0h at RT with 5% milk, or with 5% BSA in TBST, and then incubated with the indicated antibodies overnight at 4\u00b0C. Membranes were then washed 3\u00a0\u00d7\u00a010\u00a0min with TBST and incubated with HRP\u2010conjugated secondary antibodies for 1\u00a0h at RT and then washed 3\u00a0\u00d7\u00a010\u00a0min with TBST. Membranes were incubated with chemiluminescent substrate (EMD Millipore WBKLS0500) and exposed to Konica Blue X\u2010ray film or, for quantification, were imaged using a ChemiDoc Imaging system (Bio\u2010Rad). Images were quantified with ImageJ (NIH).All statistical analysis was performed with GraphPad Prism using the statistical tests indicated in the figure legends.d\u2010lysine (P6407\u20105\u00a0mg Sigma) and 24\u00a0h later were left untreated or treated with 600\u00a0\u03bcM H2O2 for 9\u00a0h at 37\u00b0C. Cells were then washed once with ice\u2010cold phosphate\u2010buffered saline (PBS) and then fixed with ice\u2010cold methanol for 1\u00a0min. Coverslips were washed three times with PBS and then blocked with 3% BSA in PBS for 1\u00a0h at room temperature. Next, coverslips were incubated with primary antibodies  diluted in PBS with 3% BSA for 1\u00a0h at room temperature. Coverslips were washed three times with PBS and then incubated with Alexa 488 conjugate anti\u2010rabbit secondary antibody  for 1\u00a0h at room temperature. DAPI  staining was performed for 5\u00a0min, followed by one wash with PBS. Coverslips were mounted onto slides with ProLong Gold Antifade reagent (Life Technologies) and imaged on a Zeiss LSM 710 confocal microscope. Quantification of nuclear AIF intensity was performed using ImageJ v1.50g .U2OS cells were plated on coverslips coated with 10\u00a0\u03bcg/ml Poly\u2010in\u00a0vitro by incubating NAE (0.15\u00a0\u03bcM), UBE2M/2F (10\u00a0\u03bcM) and NEDD8 (20\u00a0\u03bcM) in reaction buffer  for 3\u00a0h at 30\u00b0C. Reactions were stopped by the addition of LDS sample loading buffer.NEDD8 chains were made 2 plates, scraped in ice\u2010cold PBS, collected and centrifuged at 500\u00a0\u00d7\u00a0g for 5\u00a0min. Cell pellets were resuspended in buffer A without SDS, and lysates were spun at 17,000\u00a0\u00d7\u00a0g for 20\u00a0min. The supernatant was collected and incubated with HALO\u2010Link resin (Promega) conjugated to HALO\u2010NEDP1 C163A or DAGC mutant for 3\u00a0h at 4\u00b0C. HALO resin was washed three times with buffer A and three times with 50\u00a0mM Tris\u2013HCl without salt or detergent. Bound proteins were eluted with 100\u00a0\u03bcl of a 50:50 mixture of acetonitrile and 0.1% formic acid for a total of five elutions. Eluate was collected and dried in a speed vac (Thermo Scientific). Protein pellets were resuspended in LDS sample loading buffer and resolved by SDS\u2013PAGE on a 4\u201312% Bis\u2010Tris gel . Gels were stained with InstantBlue colloidal Coomassie (Expedeon). Bands were then excised, washed with water, dehydrated in acetonitrile and rehydrated in 50\u00a0mM Tris\u2013HCl pH 8.0. Gel slices were alkylated with 20\u00a0mM chloroacetamide, dehydrated in acetonitrile and then transferred to 50\u00a0mM triethylammonium bicarbonate. Gel bands were incubated with trypsin (5\u00a0\u03bcg/ml) overnight at 30\u00b0C. Peptides were extracted with acetonitrile, gel bands were incubated in 0.1% trifluoroacetic acid (TFA), and then, peptides were extracted two more times with acetonitrile. Extracted peptides were dried in a speed vac and then resuspended in 0.1% TFA/water. Samples were analysed on a LTQ Orbitrap Velos Pro mass spectrometer (Thermo Fisher Scientific) coupled to an Ultimate 3000 UHPLC system with 15\u2010cm Acclaim PepMap 100 analytical column  with an addition Pepmap trapping column . Acquisition settings were lockmass of 445.120024, MS1 with 60,000 resolution, top 20 CID MS/MS using rapid scan, monoisotopic precursor selection, unassigned charge states and z\u00a0=\u00a01 rejected, dynamic exclusion of 60s with repeat count of 1. One\u2010hour linear gradients were performed from 5% solvent B to 35% solvent B . Raw files were processed in Proteome Discoverer 2.0 (Thermo Scientific), with Mascot 2.4.1 (Matrix Science),and subsequently processed in Scaffold 4.4.6 (Proteome Software) Searches were performed with a peptide tolerance of 10\u00a0ppm (monoisotopic) and a fragment tolerance of 0.60\u00a0Da (monoisotopic) or with MaxQuant v1.5.7.4 for label\u2010free quantitative and iBAQ analysis. Settings were fixed modifications of carbamidomethyl (C), variable modifications of oxidation (M), dioxidation (M), LRGG (K) and GlyGly (K). Protein identifications were filtered with a 1% FDR. Raw files were re\u2010searched separately with variable modification for acetylated peptides acetyl (K) or phosphorylated peptides phospho (STY); both searches included the fixed modifications of carbamidomethyl (C), variable modifications of oxidation (M) and dioxidation (M).For HALO pulldown for mass spectrometry analysis, NEDP1 KO HEK 293 cells were grown on 150\u2010cmin\u00a0vitro neddylation reactions, the reactions were resolved on a 4\u201312% Bis\u2010Tris gel , stained with InstantBlue colloidal Coomassie (Expedeon), and processed for in\u2010gel trypsin digest, as described above.For analysis of g for 5\u00a0min. Cell pellets were washed two times with 10\u00a0ml of PBS and then lysed with 8\u00a0M urea and 0.5% CHAPS. Protein concentration was determined by BCA assay using the manufacturer's protocol . To remove salt and impurities, protein was precipitated with acetone. Four times the sample volume of \u221220\u00b0C acetone was added and the solution was incubated at \u221220 for 2\u00a0h. The sample was then centrifuged at 4\u00b0C for 20\u00a0min at 17,000\u00a0\u00d7\u00a0g. The supernatant was decanted, and the pellet was washed with four volumes of 80% acetone, followed by centrifugation at 4\u00b0C for 5\u00a0min at 17,000\u00a0\u00d7\u00a0g. The supernatant was decanted, the pellet was briefly centrifuged again, and residual acetone was removed. The pellet was dried at room temperature for 5\u00a0min. Pellets were resuspended with rehydration buffer . 65\u00a0mM DTT and trace bromophenol blue) to 30\u00a0\u03bcg/ml. Subsequently, 90\u00a0\u03bcg of protein was added to a 7\u00a0cm, pH 5\u20138 IPG strip (Bio\u2010Rad) and allowed to rehydrate on the strip for 14\u00a0h, followed by focusing for 12\u00a0h for a total of 22\u00a0kVhrs. For two\u2010dimensional electrophoresis, separation strips were equilibrated with equilibration buffer (Bio\u2010Rad) with 50\u00a0mM DTT for 15\u00a0min. The buffer was replaced and the strips equilibrated again for 15 additional minutes. IPG strips were loaded onto precast 4\u201020% TGX gels (Bio\u2010Rad) and processed for Western blot analysis.To prepare lysate from wild\u2010type U2OS cells, one T\u2010150 flask was harvested with 5\u00a0ml trypsin\u2010EDTA (Life Technologies). Detached cells were collected with fresh media and centrifuged at 500\u00a0\u00d7\u00a0For 2D gel electrophoresis analysis of GST pulldowns, USOS NEDP1 KO cells were harvested with lysis buffer B, as described above for the endogenous PARP\u20101 immunoprecipitation. Next, 20\u00a0mg of lysate was used for each pulldown with 100\u00a0\u03bcg GST or 100\u00a0\u03bcg GST\u2010PARP\u20101 Zn1\u00a0+\u00a02 preconjugated to Sepharose 4B beads. The beads and lysates were incubated at 4\u00b0C for 2\u00a0h with rotation. The beads were then washed four times with wash buffer , followed by three washes with salt\u2010free buffer (50\u00a0mM Tris\u2013HCl pH 7.5). Bound proteins were eluted with 8\u00a0M urea and 0.5% CHAPS and were processed for isoelectric focusing, as described above.MJK performed most experiments. RH designed NEDP1 constructs, performed HALO\u2010NEDP1 pulldowns and sample preparation for the HEK 293 mass spectrometry experiment and performed some cell viability experiments. OH performed microscopy of AIF translocation. RG processed mass spectrometry samples and performed database searches. RB performed 2D gel electrophoresis. MJK, RG, RH, MT and TK analysed mass spectrometry results. MJK, RH and TK designed experiments. MJK and TK wrote the manuscript with input from all authors. RH and TK conceived the project, and TK supervised the work.The authors declare that they have no conflict of interest.Expanded View Figures PDFClick here for additional data file.Table\u00a0EV1Click here for additional data file.Review Process FileClick here for additional data file."}
{"text": "L\u2032)FeCp*(CO)][PF6] [L\u2032 = S\u2014C(Me)=C(Me)\u2014S\u2014(CH2)3\u2014S\u2014C(Me)=C(Me)\u2014S] is reported.The new structural NiFe hydrogenase model PF6 or [Ni(L\u2032)FeCp*(CO)]PF6, is composed of the nickel complex fragment [Ni(L\u2032)] coordinated as a metalloligand (using S1 and S4) to the [FeCp*(CO)]+ fragment, where (L\u2032)2\u2212 is [S\u2014C(Me)=C(Me)\u2014S\u2014(CH2)3\u2014S\u2014C(Me)=C(Me)\u2014S]2\u2212 and where Cp*\u2212 is cyclo-C5(Me)5\u2212 (penta\u00admethyl\u00adcyclo\u00adpenta\u00addien\u00adyl). The ratio of hexa\u00adfluoro\u00adphosphate anion per complex cation is 1:1. The structure at 150\u2005K has ortho\u00adrhom\u00adbic (Pbcn) symmetry. The atoms of the complex cation are located on general positions (multiplicity = 8), whereas there are two independent hexa\u00adfluoro\u00adphosphate anions, each located on a twofold axis . The structure of the new dimetallic cation [Ni(L\u2032)FeCp*(CO)]+ can be described as containing a three-legged piano-stool environment for iron [Cp*Fe(CO)\u2018S2\u2019] and an approximately square-planar \u2018S4\u2019 environment for Ni. The NiS2Fe diamond-shaped substructure is notably folded at the S\u2014S hinge: the angle between the NiS2 plane and the FeS2 plane normals is 64.85\u2005(6)\u00b0. Largely because of this fold, the nickel\u2013iron distance is relatively short, at 2.9195\u2005(8)\u2005\u00c5. The structural data for the complex cation, which contains a new unsaturated \u2018S4\u2019 ligand (two C=C double bonds), provide an inter\u00adesting comparison with the known NiFe hydrogenase models containing a saturated \u2018S4\u2019-ligand analogue having the same number of carbon atoms in the ligand backbone, namely with the structures of [Ni(L)FeCp(CO)]+  and [Ni(L)FeCp*(CO)]+ , where (L)2\u2212 is [S\u2014CH2\u2014CH2\u2014S\u2014(CH2)3\u2014S\u2014CH2\u2014CH2\u2014S]2\u2212 and Cp\u2212 is cyclo\u00adpenta\u00addienyl. The saturated analogues [Ni(L)FeCp(CO)]+ and [Ni(L)FeCp*(CO)]+ have similar Ni\u2014Fe distances: 3.1727\u2005(6), 3.1529\u2005(7)\u2005\u00c5 (two independent mol\u00adecules in the unit cell) and 3.111\u2005(5)\u2005\u00c5, respectively, for the two complexes, whereas [Ni(L\u2032)FeCp*(CO)]+ described here stands out with a much shorter Ni\u2014Fe distance [2.9196\u2005(8)\u2005\u00c5]. Also, [Ni(L)FeCp(CO)]+ and [Ni(L)FeCp*(CO)]+ show inter\u00adplanar fold angles that are similar between the two: 39.56\u2005(5), 41.99\u2005(5) (independent mol\u00adecules in the unit cell) and 47.22\u2005(9) \u00b0, respectively, whereas [Ni(L\u2032)FeCp*(CO)]+ possesses a much more pronounced fold [64.85\u2005(6)\u00b0]. Given that larger fold angles and shorter Ni\u2014Fe distances are considered to be structurally closer to the enzyme, unsaturation in an \u2018S4\u2019-ligand of the type (S\u2014C2\u2014S\u2014C3\u2014S\u2014C2\u2014S)2\u2212 seems to increase structural resemblance to the enzyme for structural models of the type [Ni(\u2018S4\u2019)FeCpR(CO)]+ (CpR = Cp or Cp*).The complex cation in the title compound, (carbonyl-1\u03ba The first \u2018S4\u2019 ligand used in this capacity featured a saturated two\u2013three\u2013two carbon linker, in L2\u2212 = [S\u2014CH2\u2014CH2\u2014S\u2014(CH2)3\u2014S\u2014CH2\u2014CH2\u2014S]2\u2212 FeCpR(CO)]+ model based on an analogous but unsaturated \u2018S4\u2019 ligand, namely L\u20322\u2212 = [S\u2014C(Me)=C(Me)\u2014S\u2014(CH2)3\u2014S\u2014C(Me)=C(Me)\u2014S]2\u2212 Fe(CpR)(CO)]+ complex in which the \u2018S4\u2019 ligand has a four-carbon linker in the remote portion of the backbone FeCp*(CO)]+ was obtained as solvent-free crystals containing the PF6\u2212 counter-ion. A drawing showing both cation and anion in this salt is shown below (see Supramol\u00adecular features), and the intra\u00admolecular structural features of the cation are discussed first. The structure of [Ni(L\u2032)FeCp*(CO)]+ is shown in Fig.\u00a034\u2019 environment for Ni (sum of bond angles around Ni1 = 359.83\u00b0). Selected metal\u2013ligand distances are Ni1\u2014S1 = 2.1616\u2005(11), Ni1\u2014S2 = 2.1530\u2005(12), Ni1\u2014S3 = 2.1507\u2005(11), Ni1\u2014S4 = 2.1563\u2005(12)\u2005\u00c5, and Fe1\u2014S1 = 2.3309\u2005(12), Fe1\u2014S4 = 2.3602\u2005(12), Fe1\u2014C11 = 1.768\u2005(5), Fe1\u2014C1 = 2.080\u2005(4), Fe1\u2014C2 = 2.107\u2005(4), Fe1\u2014C3 = 2.126\u2005(4), Fe1\u2014C4 = 2.138\u2005(4), Fe1\u2014C5 = 2.098\u2005(4)\u2005\u00c5. The inter\u00admetallic (Ni1\u2014Fe1) distance is relatively short, i.e. 2.9195\u2005(8)\u2005\u00c5. The NiS2Fe diamond is markedly folded at the S\u2014S hinge: the angle between the NiS2 plane and the FeS2 plane normals  is 64.85\u2005(6)\u00b0, and this fold largely accounts for the short nickel\u2013iron distance.[Ni(L\u20322\u2212 with those of literature complexes using the saturated ligand L2\u2212. The structures of [Ni(L)FeCp(CO)]+, as the PF6\u2212 salt/ CH2Cl2 solvate FeCp*(CO)]+, as the PF6\u2212 salt FeCp(CO)]+ and [Ni(L)FeCp*(CO)]+ show Ni\u2014Fe distances that are similar for the two, 3.1727\u2005(6)/3.1529\u2005(7)\u2005\u00c5 (two independent mol\u00adecules in the unit cell) and 3.111\u2005(5)\u2005\u00c5, respectively, for the two complexes. The [Ni(L\u2032)FeCp*(CO)]+ complex, on the other hand, has a much shorter Ni\u2014Fe distance . Also, [Ni(L)FeCp(CO)]+ and [Ni(L)FeCp*(CO)]+ show inter\u00adplanar fold angles that are similar for the two, 39.56\u2005(5)/41.99\u2005(5)\u00b0 (two independent mol\u00adecules in the unit cell) and 47.22\u2005(9)\u00b0, respectively, while [Ni(L\u2032)FeCp*(CO)]+ has a much larger fold angle of 64.85\u2005(6)\u00b0 (see above). The large fold angle and short Ni\u2014Fe distance observed in the complex with the unsaturated ligand L\u2032 match the structure of the enzymatic active site more closely than the angles/distances of the complexes containing the saturated ligand L. For eight structurally characterized enzymes, the dihedral angles range from 59 to 99\u00b0 and the Ni\u2014Fe distances range from 2.53 to 2.97\u2005\u00c5 2\u2212 can increase structural resemblance to the enzyme in models of the type [Ni(\u2018S4\u2019)FeCpR(CO)]+. Structural similarity to the enzyme in models was, in alternative approaches, also favoured when additional donor atoms were incorporated into the ligand chain (such as \u2018S3N2\u2019) or where two bidentate chelate ligands were used instead of one large \u2018S4\u2019 ligand. FeCp*(CO)]+ model with four carbon atoms, instead of three, in the remote portion of the backbone \u2005\u00c5 and 62.48\u2005(4)\u00b0, respectively FeCp*(CO)]+ was shown to be active as a hydrogen-production catalyst Cp*(CO)]+ complex, with the unsat\u00adurated \u2018S4\u2019 ligand L\u2032, might warrant deeper investigation. We conclude that the introduction of unsaturation in the \u2018S4\u2019 ligand led to a better structural model relative to the unsaturated ligand, highlighting a new variant of the classic [Ni(\u2019S4\u2019)FeCpR(CO)]+-type hydrogenase model.In the following discussion, we compare the structural features obtained with the unsaturated ligand L\u2032)FeCp*(CO)]+ with hexa\u00adfluoro\u00adphosphate anions, without solvent mol\u00adecules and without any solvent-accessible void. The ratio of hexa\u00adfluoro\u00adphosphate anion per complex cation is 1:1. The atoms of the complex cation are situated on general positions (multiplicity = 8), whereas there are two independent hexa\u00adfluoro\u00adphosphate anions, each situated on a twofold axis . A picture of the packing is shown in Fig.\u00a04B\u22efF4 = 2.55\u2005\u00c5; C15\u2014H15B\u22efF3i = 2.55\u2005\u00c5; C21\u2014H21C\u22efF4ii = 2.48\u2005\u00c5; C22\u2014H22C\u22efF1iii = 2.52\u2005\u00c5) and a C\u2014H\u22efO short contact (C14\u2014H14A\u22efO1 = 2.41\u2005\u00c5) .The structure results from packing of discrete cations +, they are not discussed further. LAZVUE FeCp(CO)]+ , MUDXOA FeCp*(CO)]+ , and SUWWAJ FeCp*(CO)]+ . These three complex cations are discussed in detail above.The Cambridge Crystallographic Database .The syntheses were performed in dried solvents under an inert atmosphere  using standard glove-box (MBraun) and Schlenk techniques. Deuterated NMR solvents were from Cambridge Isotopes.  using 1,3-di\u00adbromo\u00adpropane. Na2[Ni(S2C2Me2)] was prepared from Ni(S2C2Me2)2 by reduction with excess sodium in THF , until the colour had changed from deep purple to brown\u2013yellow. The subsequent alkyl\u00adation of [Ni(S2C2Me2)]2\u2212 using 1,3-di\u00adbromo\u00adpropane was performed analogously to the procedure described by Schrauzer and co-workers for the closely related Ni(S\u2014C(Ph)=C(Ph)\u2014S\u2014(CH2)3\u2014S\u2014C(Ph)=C(Ph)\u2014S). ][PF6]: This precursor for the iron part of the complex was prepared according to the general procedure for [Cp*Fe(CO)2(solvent)]+ given by Catheline & Astruc (1984[PF6]: Crude [Cp*Fe(CO)2(NCMe)][PF6]  was combined with 6\u2005ml of aceto\u00adnitrile and filtered through a glass filter frit. While purging with argon, the reaction was irradiated with UV\u2013visible light  for 16\u2005h. Under an inert atmosphere, a solution of 155\u2005mg (0.46\u2005mmol) of Ni(L\u2032) in ca 7\u2005ml of di\u00adchloro\u00admethane was added. The reaction mixture was heated under active argon flow to 325\u2005K for 2\u2005h. After cooling to room temperature, the volatiles were slowly removed under vacuum. The solid was dried under vacuum and stored in the glove-box. Yield of crude product: 253\u2005mg (75%). 1H NMR  \u03b4 1.60 ; \u03b4 1.91 ; \u03b4 1.96 ; \u03b4 2.31 ; \u03b4 2.0\u20133.7 . Note that the sample thus prepared showed a 1H NMR signal for metal-coordinated aceto\u00adnitrile. The purpose of the prolonged photolysis was to remove all CO from iron, in order to selectively prepare [Ni(L\u2032)FeCp*(NCMe)][PF6]. However, the sample obtained appeared to be a mixture of [Ni(L\u2032)FeCp*(CO)][PF6] and [Ni(L\u2032)FeCp*(NCMe)][PF6] and is thus referred to as [Ni(L\u2032)FeCp*(CO/NCMe)][PF6]. Yet, crystallization from acetone yielded exclusively [Ni(L\u2032)FeCp*(CO)][PF6], in crystalline form.[Ni(L\u2032)FeCp*(CO)][PF6]: 11\u2005mg of [Ni(L\u2032)FeCp*(CO/NCMe)][PF6] were dissolved in 1.5\u2005ml of acetone and filtered through 1\u2005cm of Celite. Through solvent vapor diffusion, by placing the loosely capped vial into a larger vessel containing diethyl ether vapour (and some liquid), crystals of [Ni(L\u2032)FeCp*(CO)][PF6] were grown within two days at 308\u2005K.Crystallization of [Ni(Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989018010939/zl2735sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018010939/zl2735Isup2.hklStructure factors: contains datablock(s) I. DOI: 1859284CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked via O\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds, forming chains along [101].The title mol\u00adecule is comprised of two non-coplanar benzene rings connected by an imino group in a  16H17NO4, the dihedral angle between benzene rings is 72.7\u2005(2)\u00b0. The meth\u00adoxy groups are rotated by 2.4\u2005(2) and \u22124.9\u2005(2) (benzil\u00adidene moiety) and by 5.6\u2005(3)\u00b0 (aniline moiety) relative to the adjacent benzene ring. In the crystal, the mol\u00adecules are linked into chains along [101] through C\u2014H\u22efO and O\u2014H\u22efN hydrogen bonds.In the title compound, C The meth\u00adoxy groups are almost co-planar with the planes of the adjacent aromatic rings .The mol\u00adecular structure of the title molecule is shown on Fig.\u00a01via C7\u2014H7\u22efO2ii and O2\u2014H2\u22efN1i hydrogen bonding \u00admeth\u00adyl]phenol, (I)et al., 1992E)-5-meth\u00adoxy-2-[(4-meth\u00adoxy\u00adphenyl\u00adimino)\u00admeth\u00adyl]phenol, (II) \u00admeth\u00adyl]phenol, (IV)   and 50\u2005ml of distilled water. The reaction mixture was taken in a clean 250\u2005ml round-bottom flask and stirred well with a magnetic stirrer. It was then refluxed for 7\u2005h. The dark-yellow product that formed was separated by filtration, dried under vacuum and recrystallized from methanol solution upon slow evaporation for two days .4-Hy\u00addroxy-3,5-di\u00admeth\u00adoxy\u00adbenzaldehyde  (0.05\u2005mol) was added to a mixture of 50\u2005ml of methanol and Uiso(H) = 1.2Ueq(C) or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018013713/ld2146sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013713/ld2146Isup3.cmlSupporting information file. DOI: 10.1107/S2056989018013713/ld2146Isup3.hklStructure factors: contains datablock(s) I. DOI: 1843910CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the original publication, values of the doses of insulin glargine, the most commonly used basal insulin analogue under the \u2018Discussion\u2019 section was incorrectly published.The sentence \u201c\u2026was similar (3100.314 \u00b1 110.1298 U/kg body weight/day at baseline) to that in the Swedish study (0.33 \u00b1 0.16 U/kg body weight/day)\u201d.Should actually say \u201c\u2026was similar (0.31 \u00b1 0.12 U/kg body weight/day at baseline) to that in the Swedish study (0.33 \u00b1 0.16 U/kg body weight/day)\u201d."}
{"text": "The asymmetric unit of the title compound consists of two independent mol\u00adecules differing slightly in the conformations of the seven-membered rings and the butyl substituents. 16H20N2O2, consists of two independent mol\u00adecules differing slightly in the conformations of the seven-membered rings and the butyl substituents, where the benzene rings are oriented at a dihedral angle of 34.56\u2005(3)\u00b0. In the crystal, pairwise inter\u00admolecular C\u2014H\u22efO and complementary intra\u00admolecular C\u2014H\u22efO hydrogen bonds form twisted strips extending parallel to (012). These strips are connected into layers parallel to (111) by additional inter\u00admolecular C\u2014H\u22efO hydrogen bonds. The layers are further joined by C\u2014H\u22ef\u03c0 inter\u00adactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (65.5%), H\u22efC/C\u22efH (16.0%) and H\u22efO/O\u22efH (15.8%) inter\u00adactions.The asymmetric unit of the title compound, C Rings B and D have boat conformations with slightly different Cremer\u2013Pople puckering parameters . In the n-butyl substituents, the C13\u2014C14\u2014C15\u2014C16 [177.96\u2005(13)\u00b0] and C29\u2014C30\u2014C31\u2014C32 [174.97\u2005(12)\u00b0] chains also have slightly different torsion angles. The conformation of the 2-oxo\u00adpropyl\u00adidene units are partially determined by the intra\u00admolecular N\u2014H\u22efO hydrogen bonds (Table\u00a01The asymmetric unit of the title compound consists of two independent mol\u00adecules differing modestly in the conformations of the seven-membered s Table\u00a01 The r.m.Bnz\u22efOOxoprp (Bnz = Benzene and Oxoprp = 2-oxo\u00adpropyl\u00adidene) and complementary intra\u00admolecular C\u2014HBnz\u22efOBnzdzp  hydrogen bonds (Table\u00a01Bnz\u22efOOxoprp and C\u2014HBnzdzp\u22efOBnzdzp hydrogen bonds (Table\u00a01Bnzdzp\u22ef\u03c0 and C\u2014HBty\u22ef\u03c0 (Bty = n-but\u00adyl) inter\u00adactions  analysis  contacts -4-(2-oxo\u00adpropyl\u00adidene)-4,5-di\u00adhydro-1H-benzo[b]diazepin-2(3H)-one (2.38\u2005mmol) in 15\u2005ml of di\u00adchloro\u00admethane were added 1.5 eq of 1-bromo\u00adbutane, (3.57\u2005mmol) of potassium hydroxide dissolved in water and 0.23\u2005mmol of tetra-n-butyl ammonium bromide (BTBA). The mixture was kept under magnetic stirring at room temperature for 48\u2005h. A little water was added and then the organic phase was extracted. The mixture obtained was chromatographed on a column of silica gel (eluent hexa\u00adne/ethyl acetate 8/2) to give three products. The title compound was isolated as the major product in a yield of 77%.To a solution of (Uiso(H) = 1.5Ueq(C). The remaining H atoms were located in a difference-Fourier map and were freely refined. The crystal studied was twinned.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018014779/xu5946sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018014779/xu5946Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018014779/xu5946Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018014779/xu5946Isup4.cmlSupporting information file. DOI: 1874203CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II and AuI cations to form a one-dimensional polymeric compound with free di\u00adcyano\u00adaurate anions.Cyanide anions bridge Fe 2(C10H8N2)2(H2O)2][Au(CN)2]}n, the FeII ion, which is located on a twofold rotation axis, has a slightly distorted FeN4O2 octa\u00adhedral geometry. It is coordinated by two phenyl\u00adpyrazine mol\u00adecules, two water mol\u00adecules and two di\u00adcyano\u00adaurate anions, the Au atom also being located on a second twofold rotation axis. In the crystal, the coordinated di\u00adcyano\u00adaurate anions bridge the FeII ions to form polymeric chains propagating along the b-axis direction. In the crystal, the chains are linked by Owater\u2014H\u22efNdi\u00adcyano\u00adaurate anions hydrogen bonds and aurophillic inter\u00adactions [Au\u22efAu = 3.5661\u2005(3)\u2005\u00c5], forming layers parallel to the bc plane. The layers are linked by offset \u03c0\u2013\u03c0 stacking inter\u00adactions [inter\u00adcentroid distance = 3.643\u2005(3)\u2005\u00c5], forming a supra\u00admolecular metal\u2013organic framework.In the title polymeric complex, {[Fe(CN) Applying external stimuli, such as temperature, pressure, magnetic field, light irradiation or adding a guest can affect this kind of the compound and change their properties significantly , which consist of metal ions and organic ligand linkers, are studied intensively. Fe-based coordination polymers with N-donor bridging ligands are well known as compounds with switchable spin states \u2005\u00c5] in axial positions, and two N atoms of cyano bridges and two water O atoms of water mol\u00adecules [Fe1\u2014O1 = 2.122\u2005(4)\u2005\u00c5] in equatorial positions. The two CN\u2212 anions bridge the FeII and AuI cations [Fe1\u22efAu1 = 5.244\u2005(3)\u2005\u00c5] to form a one-dimensional polymeric structure with bond lengths Fe1\u2014N1 = 2.107\u2005(5)\u2005\u00c5 and Fe1\u2014\u2013N2 = 2.117\u2005(6)\u2005\u00c5  is \u03a3|90 - \u0398| = 8.53\u00b0, where \u0398 are the cis-N\u2014Fe\u2014O and cis-N\u2014Fe\u2014N angles in the coordination environment of the FeII atom.The structure of the title compound features a one-dimensional chain motif that runs parallel to the crystallographic s Figs. 1 and 2 \u25b8.water\u2014H\u22efN hydrogen bonds .The crystal packing features different types of weak inter\u00adactions  in water (2.5\u2005ml), the second was a mixture of water/aceto\u00adnitrile  and the third layer was a solution of 2-phenyl\u00adpyrazine  and [Fe(OTs)2]\u00b76H2O  (OTs = p-toluene\u00adsulfonate) in aceto\u00adnitrile (2.5\u2005ml) with 0.3\u2005ml of water. After two weeks, yellow crystals grew in the second layer; these were collected and maintained under the mother solution until measured.Crystals of the title compound were prepared by the slow diffusion method between three layers in a 10\u2005ml tube. The first layer was a solution of K[Au(CN)Uiso(H) = 1.2Uiso(C). The idealized OH2 group was fixed using an AFIX 7 command that allowed the H atoms to ride on the O atom and rotate around the bond.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019009678/su5503sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019009678/su5503Isup2.hklStructure factors: contains datablock(s) I. DOI: 1938914CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "C\u2014H\u22efO hydrogen bonds, weak C\u2014H\u22ef\u03c0 and weak offset \u03c0\u2013\u03c0 stacking inter\u00adactions stabilize the packing.In the title pyridazinone derivative, the unsubstituted phenyl ring and the pyridazine ring are inclined to each other, making a dihedral angle of 17.41\u2005(13)\u00b0, whereas the Cl-substituted phenyl ring is nearly orthogonal to the pyridazine ring [88.19\u2005(13)\u00b0], C 21H19ClN2O3, is not planar. The unsubstituted phenyl ring and the pyridazine ring are inclined to each other, making a dihedral angle of 17.41\u2005(13)\u00b0 whereas the Cl-substituted phenyl ring is nearly orthogonal to the pyridazine ring [88.19\u2005(13)\u00b0]. In the crystal, C\u2014H\u22efO hydrogen bonds generate dimers with R22(10) and R22(24) ring motifs which are linked by C\u2014H\u22efO inter\u00adactions, forming chains extending parallel to the c-axis direction. The inter\u00admolecular inter\u00adactions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most significant contributions to the crystal packing are from H\u22efH (44.5%), C\u22efH/H\u22efC (18.5%), H\u22efO/H\u22efO (15.6%), Cl\u22efH/H\u22efCl (10.6%) and C\u22efC (2.8%) contacts.The title pyridazinone derivative, C A weak n Table\u00a01. Weak aret al., 2016viz. 4-benzyl-6-p-tolyl\u00adpyridazin-3(2H)-one  to 1.1730 (blue) a.u. The three-dimensional dnorm surface of the title mol\u00adecule is illustrated in Fig.\u00a03a. The pale-red spots symbolize short contacts and negative dnorm values on the surface and correspond to the C\u2014H\u22efO inter\u00adactions . The convex blue regions symbolize hydrogen-donor groups and the concave red regions hydrogen-acceptor groups. \u03c0\u2013\u03c0 inter\u00adactions are generally indicated by adjacent red and blue triangles in the shape-index map, as is the case for the title mol\u00adecule.The shape-index map of the title mol\u00adecule was generated in the range \u22121 to 1\u2005\u00c5 Fig.\u00a03b. The cc). The curvedness plot of the title complex shows large regions of green with a relatively flat (i.e. planar) surface area, indicating the presence of \u03c0\u2013\u03c0 stacking inter\u00adactions, while the blue regions demonstrate areas of curvature.The curvedness map of the title complex was generated in the range \u22124.0 to 0.4\u2005\u00c5 Fig.\u00a03c. The ca, delineated into H\u22efH, H\u22efC/ C\u22efH, H\u22efO/O\u22efH, H\u22efCl/Cl\u22efH, C\u22efC contacts associated with their relative contributions to the Hirshfeld surface in Fig.\u00a04b\u2013f, respectively. The most important inter\u00admolecular inter\u00adaction is H\u22efH, contributing 44.5% to the overall crystal packing, with the centre of the peak de = di = 1.18\u2005\u00c5 . H\u22efC/ C\u22efH contacts, with a 18.5% contribution to the Hirshfeld surface, indicate the presence of the weak C\u2014H\u22ef\u03c0 inter\u00adaction . H\u22efO/O\u22efH contacts arising from inter\u00admolecular C\u2014H\u22efO hydrogen bonding make a 15.6% contribution to the Hirshfeld surface and are represented by a pair of sharp spikes in the region de + di \u223c2.35\u2005\u00c5 The C\u22efC contacts are a measure of \u03c0\u2013\\p stacking inter\u00adactions and contribute 2.8% of the Hirshfeld surface. They appear as an arrow-shaped distribution at de + di \u223c3.3\u2005\u00c5. Another contact to the Hirshfeld surface is from H\u22efCl/Cl\u22efH inter\u00adactions (10.6%).The overall two-dimensional fingerprint plot is illustrated in Fig.\u00a04\u2005\u00c5 Fig.\u00a04b. H\u22efC/ n Table\u00a01. Two paint Fig.\u00a04c. H\u22efO/OH)-one in 30\u2005ml of tetra\u00adhydro\u00adfuran (THF), potassium carbonate  was added. The mixture was refluxed for 1\u2005h. After cooling, ethyl bromo\u00adacetate  was added and the mixture was refluxed for 8\u2005h. The precipitated material was removed by filtration and the solvent evaporated under vacuum. The residue was purified through silica gel column chromatography using hexa\u00adne/ethyl acetate (4:6 v/v). Slow evaporation at room temperature led to formation of single crystals with a yield of 70%.To a solution  of 4-(3-di\u00adchloro\u00adbenz\u00adyl)-6-phenyl\u00adpyridazin-3(2Uiso(H) = 1.2Ueq(C)], C\u2014H = 0.96\u2005\u00c5 for methyl\u00adene [Uiso(H) = 1.5Ueq(C)], C\u2014H = 0.93\u2005\u00c5 for aromatic [Uiso(H) = 1.2Ueq(C)] and C\u2014H = 0.98\u2005\u00c5 for methine [Uiso(H) = 1.2Ueq(C)] H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019007424/wm5505sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019007424/wm5505Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019007424/wm5505Isup3.cmlSupporting information file. DOI: 1917654CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, the mol\u00adecules are linked by pairs of O\u2014H\u22efO hydrogen bonds, forming inversion dimers with an  15H15NO2, is a Schiff base that exists in the keto\u2013enamine tautomeric form and adopts a Z configuration. The mol\u00adecule is almost planar, with the two phenyl rings twisted relative to each other by 9.60\u2005(18)\u00b0. There is an intra\u00admolecular N\u2014H\u22efO hydrogen bond present forming an S(6) ring motif. In the crystal, pairs of O\u2014H\u22efO hydrogen bonds link adjacent mol\u00adecules into inversion dimers with an R22(18) ring motif. The dimers are linked by very weak \u03c0\u2013\u03c0 inter\u00adactions, forming layers parallel to (The title compound, C RCH=N\u2013R\u2032) and are prepared by condensation reactions between amines and active carbonyl compounds -6-{[(2-hy\u00addroxy-4-methyl\u00adphen\u00adyl)amino]\u00admethyl\u00adidene}-4-methyl\u00adcyclo\u00adhexa-2,4-dien-1-one, was obtained in crystalline form from the reaction of 2-amino-5-methyl\u00adphenol with 2-hy\u00addroxy-5-methyl\u00adbenz\u00adaldehyde. We report here its synthesis conditions and the mol\u00adecular and crystal structures, supplemented by Hirshfeld surface analysis.In the current study, a new Schiff base, . The mol\u00adecule is almost planar, with an r.m.s. deviation of 0.1061\u2005\u00c5 for the complete mol\u00adecule except the H atoms [largest deviation 0.176\u2005(3)\u2005\u00c5 for C8]. The two phenyl rings (C1\u2013C6 and C9\u2013C14) are inclined by 9.60\u2005(18)\u00b0. The C1\u2014O1 bond length [1.356\u2005(3)\u2005\u00c5] to the hy\u00addroxy group is in the normal range, while the C14=O2 bond length is comparatively elongated [1.302\u2005(4)\u2005\u00c5] due to the involvement of the carbonyl O atom in an intra\u00admolecular N\u2014H\u22efO hydrogen bond, forming an S(6) ring motif. The C6\u2014N1 and C8=N1 bond lengths are 1.404\u2005(4) and 1.310\u2005(4)\u2005\u00c5, respectively. Overall, the bond lengths in the title structure compare well with those of other keto\u2013enamine tautomers known from the literature (see: Database Survey).The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a01Cg1\u22efCg2 = 4.721\u2005(2)\u2005\u00c5; Cg1 and Cg2 are the centroids of the C1\u2013C6 and C9\u2013C14 rings, respectively], forming layers parallel to -2-[(2-hy\u00addroxy\u00adphenyl\u00adiminio)meth\u00adyl]phenolate fragment revealed 25 hits where this fragment adopts the keto\u2013enamine tautomeric form. Nearly all bond lengths in the title structure are the same within standard uncertainties as the corresponding bond lengths in the structures of 2,4-di\u00adchloro-6-{[(2-meth\u00adoxy\u00adphen\u00adyl)iminio]meth\u00adyl}phenolate hydrate -[(2-hy\u00addroxy\u00adphen\u00adyl)iminio]meth\u00adyl}-4-methyl\u00adphenolate -4-hy\u00addroxy-2-[(2-hy\u00addroxy\u00adphen\u00adyl)iminiometh\u00adyl]phenolate -[(2-hy\u00addroxy-5-methyl\u00adphen\u00adyl)iminio]meth\u00adyl}-4-(tri\u00adfluoro\u00admeth\u00adoxy)phenolate  surface resolution. Fig.\u00a04b shows the mol\u00adecular electrostatic potential plotted over the three-dimensional Hirshfeld surface using the STO-3G basis set in the range \u22120.0975 to 0.2197 a.u. within the Hartree\u2013Fock level of theory. The O\u2014H\u22efO hydrogen-bond donors and acceptors are shown as blue and red areas around the atoms related with positive (hydrogen-bond donors) and negative (hydrogen-bond acceptors) electrostatic potentials, respectively.A Hirshfeld surface analysis  points related to H\u22efH contacts that represent a 55.2% contribution in the title structure. In Fig.\u00a05c, two symmetrical wings on the left and right sides indicate C\u22efH/H\u22efC inter\u00adactions with a contribution of 22.3%. Furthermore, there are O\u22efH/H\u22efO , C\u22efC (4.9%) and C\u22efN/N\u22efC (2.6%) contacts.Fig.\u00a05Fig.\u00a06The title compound was prepared by refluxing a mixture of 2-hy\u00addroxy-5-methyl\u00adbenzaldehyde  in ethanol (15\u2005ml) and 2-amino-5-methyl\u00adphenol  in ethanol (15\u2005ml) for 5\u2005h. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.5Ueq. The C-bound H atoms were positioned geometrically and refined using a riding model with C\u2014H = 0.93 and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and with C\u2014H = 0.96\u2005\u00c5 and Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019006583/wm5504sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006583/wm5504Isup2.hklStructure factors: contains datablock(s) I. DOI: 1902148CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "BM) grafts in F1 hybrid recipients is due to natural killer (NK) cell\u2013mediated rejection triggered through \u201cmissing self\u201d recognition. \u201cHybrid resistance\u201d has usually been investigated in lethally irradiated F1 recipients in conjunction with pharmacological activation of NK cells. Here, we investigated BM\u2010directed NK\u2010cell alloreactivity in settings of reduced conditioning. Nonlethally irradiated (1\u20103\u00a0Gy) or nonirradiated F1 (C57BL6\u00a0\u00d7\u00a0BALB/c) recipient mice received titrated doses (5\u201020 x 106) of unseparated parental BALB/c BM without pharmacological NK cell activation. BM successfully engrafted in all mice and multilineage donor chimerism persisted long\u2010term (24\u00a0weeks), even in the absence of irradiation. Chimerism was associated with the rearrangement of the NK\u2010cell receptor repertoire suggestive of reduced reactivity to BALB/c. Chimerism levels were lower after transplantation with parental BALB/c than with syngeneic F1 BM, indicating partial NK\u2010mediated rejection of parental BM. Activation of NK cells with polyinosinic\u2013polycytidylic acid sodium salt poly(I:C), reduced parental chimerism in nonirradiated BM recipients but did not prevent hematopoietic stem cell engraftment. In contrast, equal numbers of parental lymph node cells were completely rejected. Hence, hybrid resistance leads to incomplete rejection of parental BM under reduced conditioning settings.Resistance to parental bone marrow ( Modifying conditioning in the hybrid resistance model reveals that lasting chimerism ensues after nonmyeloablative irradiation, even when no recipient irradiation is given, indicating that natural killer cell\u2013mediated bone marrow rejection is incomplete in reduced conditioning settings. BMbone marrowGvHDgraft versus host diseaseLNlymph nodeNKnatural killerpoly(I:C)polyinosinic\u2013polycytidylic acid sodium saltTBItotal body irradiationTLRtoll\u2010like receptor1Natural killer (NK) cells are large granular lymphocytes that serve as first\u2010line defense against pathogens and neoplastic cells.22.1CB6F1  and BALB/c (CD45.2) mice were purchased from Charles River and congenic B6.SJL\u2010Ptprca Pepcb/BoyJ (CD45.1) mice from Jackson Laboratory. F1 (CD45.1/CD45.2) mice were obtained by crossing male CD45.1 on C57BL/6 background with female CD45.2 BALB/c mice. All mice were housed under specific pathogen\u2010free conditions and female mice were used between 8 and 12\u00a0weeks of age. All animal experiments were approved by the internal review board of the Medical University of Vienna and by the Austrian Ministry of Science and Research (permission number GZ: BMWFW\u201066.009/0028\u2010WF/V/3b/2015).2.26) of unseparated BALB/c (CD45.2) or CB6F1 (CD45.2) BM cells (d0). Bones  were flushed with a syringe and BM cells were collected in M199 medium (Sigma Aldrich) supplemented with 10\u00a0mM Hepes Buffer  and 50\u00a0\u03bcg/ml gentamycin .F1 (CD45.1/CD45.2) recipient mice received titrated doses (5\u201020\u00a0\u00d7\u00a0102.36 BALB/c BM (d0) and poly(I:C) . Sixteen\u00a0weeks after transplantation, BM cells were recovered from primary recipients and transplanted into secondary F1 mice conditioned with 11\u00a0Gy TBI (2\u00a0\u00d7\u00a05.5\u00a0Gy). On the day of reconstitution, each secondary recipient was transplanted with 20\u00a0\u00d7\u00a0106 BM cells recovered from one chimera (i.v.).Primary recipients received 10\u00a0\u00d7\u00a0102.4Full\u2010thickness tail skin was grafted 4\u20106\u00a0weeks after BM transplantation and visually inspected thereafter at short intervals. Grafts were considered to be rejected when less than 10% remained viable, as described earlier.2.5\u2212 CD45.2+ cells among CD45.1+ CD45.2+ plus CD45.1\u2212 CD45.2+ leukocytes (CD45.1\u2212 CD45.2+/(CD45.1\u2212 CD45.2+ + CD45.1+ CD45.2+) \u00d7 100). APC anti\u2010mouse CD45.1 (A20), PE anti\u2010mouse CD45.2 (104), FITC anti\u2010mouse Mac\u20101 (M1/70), PE\u2010Cy7 anti\u2010mouse CD8 (53\u20106.7), APC\u2010Cy7 anti\u2010mouse CD4 (RM4\u20105), Pacific Blue anti\u2010mouse CD3 (17A2), FITC anti\u2010mouse CD49b (DX5), FITC anti\u2010mouse NK1.1 (PK136), PE anti\u2010mouse Ly49D (4E5), biotin anti\u2010mouse Ly49A (YE1/48.10.6) were purchased from Bio Legend. PE\u2010Cy7 anti\u2010mouse Ly49G2 (4D11) was purchased from eBioscience.The presence of donor cells was assessed at regular intervals by staining CD45.1 and CD45.2 on blood leukocytes. Donor chimerism was assessed as percentage of CD45.12.6t test with equal variances was used to compare chimerism levels. Total chimerism levels were compared between groups by using analysis of variance (ANOVA). The correlation between BM dose and chimerism level was assessed by a linear regression model. A P\u2010value below .05 was considered to denote statistical significance .Data were statistically analyzed with GraphPad Prism 5.0 . A 2\u2010sided Student's 36 BALB/c BM (d0). All recipients developed high levels of persistent multi\u2010lineage mixed chimerism   that bind the very same MHC molecule.+ Ly49A/G2\u2212 NK cells  male mice with BALB/c (CD45.2) female mice so that the resulting F1 generation coexpressed both CD45.1 and CD45.2, whereas donor BALB/c cells solely expressed CD45.2  7\u00a0days postinfusion by F1 recipient  is given.Irradiation promotes engraftment by creating space in the BM niche,So far the proliferation of recipient splenocytes shortly after BM transplantation served as surrogate marker for BM engraftment in hybrid resistance models using lethally irradiated mice.+ NK cells would obtain the expression of the inhibitory receptors Ly49A and/or Ly49G2. This adaptation extended over a period of 4\u00a0weeks, which approximately corresponds to the time of NK cell maturation in the BM.Even if allogeneic stem cells have sufficient space to engraft, one would expect NK cells to resist their engraftment unless very large BM doses are infused.Our data from the murine hybrid resistance setting suggest that NK\u2010mediated BM rejection is less potent in reduced conditioning settings than in lethal irradiation regimens, allowing stem cell engraftment with moderate BM doses even in nonirradiated recipients.American Journal of Transplantation.The authors of this manuscript have no conflicts of interest to disclose as described by the"}
{"text": "A qu\u00adanti\u00adfication of the inter\u00admolecular contacts in the crystal were estimated using Hirshfeld surface analysis and two-dimensional fingerprint plots.2-(4-Nitro\u00adphen\u00adyl)-2-oxoethyl picolinate was synthesized under mild conditions. The chemical and mol\u00adecular structure was confirmed by single-crystal X-ray diffraction studies. The mol\u00adecules are related by inversion into centrosymmetric dimers  14H10N2O5, was synthesized under mild conditions. The chemical and mol\u00adecular structures were confirmed by single-crystal X-ray diffraction analysis. The mol\u00adecules are linked by inversion into centrosymmetric dimers via weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions, forming R22(10) ring motifs, and further strengthened by weak \u03c0\u2013\u03c0 inter\u00adactions. Hirshfeld surface analyses, the dnorm surfaces, electrostatic potential and two-dimensional fingerprint (FP) plots were used to verify the contributions of the different inter\u00admolecular inter\u00adactions within the supra\u00admolecular structure. The shape-index surface shows that two sides of the mol\u00adecules are involved with the same contacts in neighbouring mol\u00adecules and curvedness plots show flat surface patches that are characteristic of planar stacking.2-(4-Nitro\u00adphen\u00adyl)-2-oxoethyl picolinate, C The torsion angle value of \u03c42 = \u2212147.02\u2005(11)\u00b0 between the two carbonyl groups indicates a \u2013anti\u00adclinal conformation. Likewise, owing to a substitution on the functional group, the title com\u00adpound experiences steric repulsion between the substituent and adjacent carbonyl groups, which can influence the torsion angle [\u03c43 = 2.4\u2005(2)%] and resulting in a +synclinal conformation. The bond lengths and angles are normal and the mol\u00adecular conformation is characterized by a dihedral angle of 31.58\u2005(8)\u00b0 between the mean planes of the two aromatic rings. The nitro group lies nearly in the plane of the phenyl ring, as indicated by the torsion angle values of \u22124.7\u2005(2) and \u22125.1\u2005(2)\u00b0 for C4\u2014C3\u2014N1\u2014O4 and C2\u2014C3\u2014N1\u2014O5, respectively.The mol\u00adecular structure of the title com\u00adpound is shown in Fig.\u00a01B\u22efO3 inter\u00adactions stabilize the supra\u00admolecular architecture by forming Cg, N\u2014O\u22efCg and Cg\u22efCg inter\u00adactions. The hydrogen-bond geometry and lone pair-\u03c0 inter\u00adactions are listed in Table\u00a02Cg\u22efCg inter\u00adactions, i.e.Cg1\u22efCg1  and Cg2\u22efCg2 . These weak inter\u00admolecular inter\u00adactions link the mol\u00adecules to form a one-dimensional chain along the c axis and the mol\u00adecules exhibit layered stacking  and shape-index (\u22121.0 to 1.0 a.u.), respectively. The calculated volume inside the Hirshfeld surface is 311.97\u2005\u00c53 in the area of 305.78\u2005\u00c53.Hirshfeld surfaces and fingerprint plots  = 1.2 or 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019014105/jj2216sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019014105/jj2216Isup2.hklStructure factors: contains datablock(s) I. DOI: 1449658, 1449658CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Quantum-mechanical (QM) calculations were performed at the MP2/aug-cc-pVDZ//B3LYP/6-311++G level in vacuum phase, along with Bader\u2019s quantum theory of Atoms in Molecules (QTAIM). These processes involve transition states (TSs) with quasi-orthogonal structures (symmetry C1), which are highly polar, tight ion pairs \u2219. Gibbs free energies of activation for the A\u2219T(WC) / A\u2219T(rWC) \u2194 A*\u2219\u0422(rwWC) / A*\u2219\u0422(wWC) tautomeric transitions  are lower than for the A\u2219T(H) / A\u2219T(rH) \u2194 A*N7\u2219\u0422(rwH) / A*N7\u2219\u0422(wH) tautomerisations  . The (T)N3+H\u22efN1-(A), (T)O4+H\u22efN1-(A) / (T)N3+H\u22efN1-(A) and (T)O2+H\u22efN1-(A) H-bonds are found in the transition states TSA-\u00b7T+A\u00b7T(WC)\u2194A*\u00b7T(rwWC) / TSA-\u00b7T+A\u00b7T(rWC)\u2194A*\u00b7T(wWC). However, in the transition state TSA-\u00b7T+A\u00b7\u0422(H)\u2194A*N7\u00b7T(rwH) / TSA-\u00b7T+A\u00b7\u0422(rH)\u2194A*N7\u00b7T(wH), the (T)N3+H\u22efN7-(A), (T)O4+H\u22efN7-(A) / (T)N3+H\u22efN7-(A) and (T)O2+H\u22efN7-(A) H-bonds are supplemented by the attractive (T)O4+/O2+\u22efN6-(A) van der Waals contacts. It was demonstrated that the products of the tautomerization of the classical A\u2219T DNA base pairs\u2014A*\u2219\u0422(rwWC), A*N7\u2219\u0422(rwH) and A*N7\u2219\u0422(wH) (symmetry Cs)\u2013further transform via double proton transfer into the energetically favorable wobble A\u2219T*(rwWC), A\u2219T*(rwH) and A\u2219T*O2(wH) base mispairs (symmetry Cs).In this paper we have theoretically predicted a novel pathway for the mutagenic tautomerization of the classical A\u2219T DNA base pairs in the free state, the Watson-Crick A\u00b7\u0422(WC), reverse Watson-Crick A\u00b7\u0422(rWC), Hoogsteen A\u00b7\u0422(H) and reverse Hoogsteen A\u00b7\u0422(rH) pairs,  Investigation of microstructural mechanisms for mutagenic tautomerization of the Watson-Crick DNA base pairs occupies an important place in molecular biophysics and molecular biology, enabling an understanding of the nature of genome instability \u20135. This N7 \u2013to N7 nitrogen atom; T*\u2013to O4 oxygen atom and T*O2 \u2013to O2 oxygen atom. L\u00f6wdin proposed that the A\u2219T(WC)\u2194A*\u2219T*(L) and G\u2219C(WC)\u2194G*\u2219C*(L) transitions occur by double proton transfer (DPT) along neighboring intermolecular hydrogen (H) bonds via proton tunneling. These ideas have been prominent in the field of quantum biology and attracted much theoretical study of the mechanisms of spontaneous transitions and transversions arising during DNA replication [L\u00f6wdin , 4 firstlication .kT  for the G\u2219C(WC) DNA base pair [Recently, it has become clear that L\u00f6wdin\u2019s mechanism does not provide the generation of sufficiently long-lived mutagenic tautomers of the DNA bases, which escape from the replicative DNA-polymerase transforming into their canonical tautomeric forms. The root cause of this observation is the absence of the reverse barrier of tautomerization \u0394\u0394G in the A\u2219T(WC) DNA base pair and its small value in comparison with ase pair , 15\u201318.vice versa, which mechanism obviates the above difficulties. The chief difference of our mechanism from the L\u00f6wdin mechanism is that, in the process of mutagenic tautomerization through sequential proton transfer, the DNA bases shift laterally relative each other into the DNA minor or major grooves, leading to the wobble configuration which contains the mutagenic tautomers [In previous papers \u201327 we prautomers . Moreoveautomers , pyrimidautomers , 23 and automers \u201327 DNA bvice versa, which is the key to understanding the microstructural mechanisms for spontaneous transitions and transversions during DNA biosynthesis [This allows us to assume that it is the intrapair tautomeric transition of the wobble pairs from the main tautomeric form into the rare one with a WC configuration or close to it, and ynthesis \u201327. Theoynthesis \u201331.1) which are highly polar tight ion pairs \u2219.This paper uses QM/QTAIM methods to explore new pathways for mutagenic tautomerization of the classical Watson-Crick A\u00b7\u0422(WC), reverse Watson-Crick A\u00b7\u0422(rWC), Hoogsteen A\u00b7\u0422(H) and reverse Hoogsteen A\u00b7\u0422(rH) base pairs with a remarkable biological meaning . TheThe geometries of all the investigated DNA base pairs and transition states (TSs) were optimized using the Gaussian\u201909 package . The B3LWe have performed investigations for the isolated H-bonded pairs of nucleotide bases, that adequately reflects the processes occurring in real duplex environment , 30, 31.el = electronic energy, while Ecorr = thermal correction to Gibbs free energy.The Gibbs free energy G for all structures was obtained in the following way:int were calculated at the MP2/6-311++G level of theory as the difference between the total energy of the base pair and energies of the monomers and corrected for the basis set superposition error (BSSE) [Electronic interaction energies \u0394Er (BSSE) ,87 throur (BSSE) ,89 withor (BSSE) .Bader\u2019s quantum theory of Atoms in Molecules (QTAIM) \u201396 was aThe energies of the attractive van der Waals contacts , 102 in Energies of conventional AH\u00b7\u00b7\u00b7B H-bonds were evaluated by the empirical Iogansen formula :EAH\u00b7\u00b7\u00b7Bsonances \u2013114.The atom numbering scheme for the DNA bases is as per convention .These novel pathways for the mutagenic tautomerization of four biologically important A\u2219T DNA base pairs\u2014Watson-Crick A\u00b7\u0422(WC), reverse Watson-Crick A\u00b7\u0422(rWC), Hoogsteen A\u00b7\u0422(H) and reverse Hoogsteen A\u00b7\u0422(rH) \u201349\u2013are pvia proton transfer along intermolecular H-bonds as per currently known mechanisms for mutagenic tautomerization of WC pairs [Conformers of the A\u2219T base pairs remain plane symmetric structures along the entire IRC of tautomerization. This also holds for base pairs tautomerising WC pairs , 19, 49.WC) / A*\u2219\u0422(wWC) / A*N7\u2219\u0422(rwH) / A*N7\u2219\u0422(wH) tautomerisation reactions occur via the initial migration of proton localized at the N6 atom of the N6H2 amino group, leading to the formation of the A+\u2219\u0422- ion pair and significant change of the mutual orientation of the bases within the pair, i.e. mutual transformation of the cys / trans\u2194trans / cys-orientation of the N1H and N9H bonds relative to each other (1). Further proton transfers to the N1/N7 nitrogen atom causing the rotation of the base and formation of the terminal wobble base mispair. Each of these tautomeric conversions is followed by the asynchronous DPT along the intermolecular H-bonds in the wobble base mispairs (The A\u2219T(WC) / A\u2219T(rWC) / A\u2219T(H) / A\u2219T(rH) \u2194 A*\u2219\u0422(rwch other . Our newmispairs .WC) / A*\u2219\u0422(wWC) / A*N7\u2219\u0422(rwH) / A*N7\u2219\u0422(wH) tautomerisation reactions, the TSs are highly polar (~ 6.8\u201312.7 D) tight ion pairs  \u2219 ion pairs. In the TSA-\u00b7T+A\u00b7T(WC)\u2194A*\u00b7T(rwWC) / TSA-\u00b7T+A\u00b7T(rWC)\u2194A*\u00b7T(wWC) transition states of tautomerisation the (T)N3+H\u22efN1-(A) (13.06 / 13.24) and (T)O4+ / O2+H\u22efN1-(A)  are observed, while for the TSA-\u00b7T+A\u00b7\u0422(H)\u2194A*N7\u00b7T(rwH) / TSA-\u00b7T+A\u00b7\u0422(rH)\u2194A*N7\u00b7T(wH) transition states, the (T)N3+H\u22efN7-(A) (8.98 / 8.46) and (T)O4+ / O2+H\u22efN7-(A) (5.18 / 4.38) H-bonds are supplemented by attractive (T)O4+/O2+\u22efN6-(A)  van der Waals contacts (+H\u22efN1-/N7-(A) H-bonds  are significantly stronger than other specific contacts with increased ellipticity. The weakest among them are the attractive (T)O4+/O2+\u22efN6-(A)  van der Waals contacts  / A\u2219T(rWC) / A\u2219T(H) / A\u2219T(rH) \u2194 A*\u2219\u0422(rwl\u2219mol-1) . These Tcontacts , Table 2A*\u00b7T(rwWC)\u2194A\u00b7T*(rwWC), TSA*\u00b7T(wWC)\u2194A\u00b7T*O2(wWC), TSA*N7\u00b7\u0422(rwH)\u2194A\u00b7\u0422*(rwH) and TSA*N7\u00b7\u0422(wH)\u2194A\u00b7\u0422*O2(wH) of the DPT reactions are stabilized by the N6-H-N3 covalent bridge and one-single intermolecular H-bond\u2014N1H\u22efO4 (11.61), N1H\u22efO2 (10.94), N7H\u22efO4 (13.76) and N7H\u22efO4 , accordingly , which are characterized by low energies ECH\u00b7\u00b7\u00b7O, estimated by the Espinose-Molins-Lecomte formula [C\u22efO and dH\u22efO) in comparison with the canonical H-bonds  BCPs of the intermolecular H-bonds range from 0.013 a.u. up to the 0.107 a.u.; the values of the Laplacian of the electron density \u0394\u03c1 at the  BCPs are positive for all intrapair H-bonds and lie within a wide range from 0.005 a.u. up to the 0.152 a.u., demonstrating that H-bonds are attractive closed-shell ineractions; the value of the ellipticity \u03b5 varies in the range 0.79\u20138.6\u00b710\u22123 .A\u00b7\u00b7\u00b7B (2.574\u20133.103 \u00c5), dH\u00b7\u00b7\u00b7B (1.442\u20132.293 \u00c5) and \u2220AH\u22efB (139.2\u2013179.3\u00b0)  .Interestingly, the energy of the intermolecular specific contacts  constitute only a minor part of the electronic energy of monomeric interactions for all these H-bonded structures ~14\u20130.87%) /A*\u2219\u0422(wWC) tautomerisations  is noticeably lower than for the A\u2219T(H)/A\u2219T(rH)\u2194A\u2219T*(rwH)/A\u2219T*O2(wH) tautomerisations  , achieving maximum values for each tautomeric transition at its TS  . The Gib2.65 D, aWC) reaction, occurs by participation of the dynamically unstable intermediate A*\u2219\u0422*(L) \u2194A*\u2219\u0422. TheWC), A*N7\u2219\u0422(rwH) and A*N7\u2219\u0422(wH) mispairs (s) tautomerise further via the DPT mechanism along neighboring intermolecular H-bonds into the energetically-favorable plane-symmetric A\u2219T*(rwWC), A\u2219T*(rwH) and A\u2219T*O2(wH) DNA base mispairs, respectively N3H\u22efN6(A) H-bonds, which, in fact, is a rate-limiting stage. It is noteworthy that the A*N7\u00b7\u0422(rwH)\u2192A\u00b7\u0422*(rwH) and A*N7\u00b7\u0422(wH)\u2192A\u00b7\u0422*O2(wH) tautomerisations are barrier-less  (WC)\u2194A\u2219T*(rwWC) (1.39) and A*\u00b7T(wWC)\u2194A\u00b7T*O2(wWC) (1.77) are significantly lower than for the novel tautomerisation reactions , but are comparable with the values for the other DPT reactions [syn\u2194A\u2219G*syn [-1 for A\u2219T\u2194A*\u2219T* [It should be noted that three out of four tautomerization processes of the A\u2219T base pairs do not complete with formation of the A*\u2219\u0422(rwmispairs . These pectively  and 2. Tl\u2219mol-1) , while teactions : from 2.\u2194A\u2219G*syn  to 10.29\u2219T\u2194A*\u2219T*  DPT taut\u041e2 [N7\u00b7\u0422(rwH)\u2194A\u00b7\u0422*(rwH) and A*N7\u00b7\u0422(wH)\u2194A\u00b7\u0422*O2(wH) tautomeric equilibria are completely shifted to the right. For the two other cases, the following proportions are observed: A*\u00b7\u0422(rwWC) (6.9%) \u2194 A\u00b7\u0422*(rwWC) (93.1%) and A*\u00b7\u0422(wWC) (83.6%) \u2194 A\u00b7\u0422*O2(wWC) (16.4%).It is thus possible to say that the tautomerization processes described here terminate with the mutagenic tautomerization of both T and A DNA bases with further formation of the classical mutagenic tautomers \u0422*, \u0422*\u041e2 , 106 and\u041e2 , 114, re-1) and populations of the investigated base mispairs yield the order: A\u00b7\u0422(H) (0.00) < A\u00b7\u0422(rH) (0.22/0.63) < A\u00b7\u0422(WC) (1.05/0.21) < A\u00b7\u0422(rWC) (1.31/0.16) < A\u2219T*(rwWC) (8.83/3.77\u221910\u22127) < A\u00b7\u0422*(rwH) (8.96/1.92\u221910\u22127) < A*\u2219T(rwWC) (10.07/2.47\u221910\u22128) < A*\u00b7T(wWC) (10.65/1.13\u221910\u22128) < A\u00b7T*O2(wWC) (12.31/2.07\u221910\u22129) < A\u00b7\u0422*O2(wH) (12.74/6.13\u221910\u221210) < A*\u2219T*(L) (13.51/1.95\u221910\u221210) < A*N7\u00b7\u0422(rwH) (24.69/1.08\u221910\u221218) < A*N7\u00b7\u0422(wH) (25.70/2.24\u221910\u221219). Notably, populations of the wobble A\u2219T*(rwWC), A\u00b7\u0422*(rwH), A*\u2219T(rwWC), A*\u00b7T(wWC), A\u00b7T*O2(wWC), A\u00b7\u0422*O2(wH) (12.74/6.13\u221910\u221210) and A*\u2219T*(L) tautomerised states, fitting into the range of the frequencies of the spontaneous point mutations observed experimentally (10\u221211\u201310\u22129) [Gibbs free energies  \u2013117, poiNotably, the methyl group of the T DNA base does not change its orientation during all these tautomerisation processes without exception. Moreover, the heterocycles of the DNA bases remain planar, despite their ability for out-of-plane bending \u2013120.+ base occurs only in the TSA-\u00b7T+A\u00b7T(WC)\u2194A*\u00b7T(rwWC), TSA-\u00b7T+A\u00b7T(rWC)\u2194A*\u00b7T(wWC), TSA-\u00b7T+A\u00b7\u0422(H)\u2194A*N7\u00b7T(rwH) and TSA-\u00b7T+A\u00b7\u0422(rH)\u2194A*N7\u00b7T(wH) transition states. The maximum value of the non-planar dihedral angle reaches 2.5\u00b0 (C2-N3-C4-C5), 3.1\u00b0 (N1-C2-N3-C4), 3.7\u00b0 (C2-N3-C4-C5) and 7.8\u00b0 (N1-C2-N3-C4), respectively. Another structural feature of the protonated T+ base in these TSs is the deviation of the \u041e4+H / \u041e2+H hydroxyl group from the plane of the pyrimidine ring   .1) are highly polar tight ion pairs \u2219. The tautomerization products\u2014the A*\u2219\u0422(rwWC), A*N7\u2219\u0422(rwH) and A*N7\u2219\u0422(wH) pairs\u2014further transform via concerted asynchronous double proton transfer into the energetically favorable wobble A\u2219T*(rwWC), A\u2219T*(rwH) and A\u2219T*O2(wH) mispairs (symmetry Cs), respectively. Moreover, it was established in our recent papers, that wobble A*\u2219T(rwWC) base mispair can also be formed from the reverse A\u2219T(rWC) base pair [N7\u00b7\u0422(wH) base mispair\u2014from the Hoogsteen A\u2219T(H) base pair [Novel pathways for mutagenic tautomerization of four classical A\u2219T DNA base pairs, followed by the significant changes of base orientation within the pair, have been predicted by these QM results. The transition states with quasi-orthogonal structure Click here for additional data file."}
{"text": "CSNK2A1 inhibited TGF\u03b2\u2010induced EMT. TGF\u03b2 signaling decreased CK2\u03b2 but did not affect CK2\u03b1 protein levels, resulting in a quantitative imbalance between the catalytic \u03b1 and regulatory \u03b2 subunits, thereby increasing CK2 activity. The decrease in CK2\u03b2 expression was dependent on TGFBRI kinase activity and the ubiquitin\u2013proteasome pathway. The E3 ubiquitin ligases responsible for TGF\u03b2\u2010induced CK2\u03b2 degradation were found to be CHIP and WWP1. Okadaic acid (OA) pretreatment protected CK2\u03b2 from TGF\u03b2\u2010induced degradation, suggesting that dephosphorylation of CK2\u03b2 by an OA\u2010sensitive phosphatase might be required for CK2 activation in TGF\u03b2\u2010induced EMT. Collectively, our results suggest CK2 as a therapeutic target for the prevention of EMT and metastasis of cancers.Transforming growth factor \u03b2 (TGF\u03b2) is overexpressed in advanced cancers and promotes tumorigenesis by inducing epithelial\u2013mesenchymal transition (EMT), which enhances invasiveness and metastasis. Although we previously reported that EMT could be induced by increasing CK2 activity alone, it is not known whether CK2 also plays an essential role in TGF\u03b2\u2010induced EMT. Therefore, in the present study, we investigated whether TGF\u03b2 signaling could activate CK2 and, if so, whether such activation is required for TGF\u03b2\u2010induced EMT. We found that CK2 is activated by TGF\u03b2 treatment, and that activity peaks at 48\u00a0h after treatment. CK2 activation is dependent on TGF\u03b2 receptor (TGFBR) I kinase activity, but independent of SMAD4. Inhibition of CK2 activation through the use of either a CK2 inhibitor or shRNA against  CHIPcarboxyl terminus of Hsc70\u2010interacting proteinCK2protein kinase CK2CKDCSNK2A1 knockdownEMTepithelial\u2013mesenchymal transitionHEKhuman embryonic kidneyNSCLCnon\u2010small cell lung cancerOAokadaic acidSKDSMAD4\u2010knockdownTGFBRIITGF\u03b2 type II receptorTGFBRITGF\u03b2 type I receptorTGF\u03b2transforming growth factor \u03b2WWP1WW domain containing E3 ubiquitin protein ligase 11et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., et\u00a0al., Transforming growth factor \u03b2 (TGF\u03b2) is a potent pleiotropic cytokine that regulates cell growth/differentiation, cell motility, extracellular matrix production, angiogenesis and cellular immune responses , and 100\u00a0U\u00b7mL\u22121 penicillin (Gibco). Human embryonic kidney (HEK) 293 cells were cultured in Dulbecco's modified Eagle's medium (Gibco). All cells were cultured at 37\u00a0\u00b0C in 5% CO2. The CK2 inhibitor, emodin , and the reversible cell\u2010permeable proteasome inhibitor, MG132 (Sigma\u2010Aldrich), were prepared in 20\u00a0mm stock with dimethylsulfoxide (Sigma\u2010Aldrich). The TGFBRI\u2010specific inhibitor, SB431542 (Sigma\u2010Aldrich), was prepared in 10\u00a0mm stock with dimethylsulfoxide. The protein phosphatase inhibitor, okadaic acid , was prepared in 10\u00a0\u03bcm stock with dimethylsulfoxide. TGF\u03b2  was prepared in 10\u00a0\u03bcg\u00b7mL\u22121 stock. pCMV5 TBRI\u2010His was a gift from Joan Massague (Addgene plasmid # 19161). pCMV5B\u2010TGF\u03b2 receptor I K232R was a gift from Jeff Wrana (Addgene plasmid # 11763). p3TP\u2010Lux  gene TGF\u03b2 response element and three collagenase I AP\u20101 repeats in front of luciferase, was a gift from Joan Massague & Jeff Wrana (Addgene plasmid # 11767). pCMV5B\u2010Flag\u2010Smurf1 wt was a gift from Jeff Wrana (Addgene plasmid # 11752), pCMV5B\u2010Flag\u2010Smurf2 wt was a gift from Jeff Wrana (Addgene plasmid # 11746), p4489 Flag\u2010betaTrCP was a gift from Peter Howley (Addgene plasmid # 10865), pcDNA3\u2010HA2\u2010ROC1 was a gift from Yue Xiong (Addgene plasmid # 19897) and pCI HA NEDD4 was a gift from Joan Massague (Addgene plasmid # 27002). pCMV\u2010Tag3B\u2010WWP1\u2010myc was kindly provided by Dr Ceshi Chen (Kunming Institute of Zoology). Flag\u2010tagged pCMV\u2010Tag2C\u2010WWP1 was kindly provided by Dr Hyeon Soo Kim  cell line, A549 was cultured in Roswell Park Memorial Institute 1640 medium , supplemented with 10% fetal bovine serum (Gibco), 100\u00a0\u03bcg\u00b7mL2.2et\u00a0al., Western blot analysis was performed as described previously . The beads were incubated with 100\u00a0\u03bcg of cell lysates in a final volume of 50\u00a0\u03bcL of kinase reaction buffer  of [\u03b3\u201032P]\u2010ATP]) for 20\u00a0min at 30\u00a0\u00b0C. The reactions were stopped by washing twice with 1\u00a0\u00d7\u00a0kinase buffer. The samples were resuspended with 30\u00a0\u03bcL of 2\u00a0\u00d7\u00a0SDS/PAGE sample\u2010loading buffer, subjected to 12% SDS/PAGE, stained with Coomassie Brilliant Blue, and dried on Whatman paper . 32P incorporation was detected by autoradiography.To evaluate intracellular CK2 activity, an 2.4CSNK2A1 . The shRNA sequences tested for SMAD4 knockdown were: sequence #1: TTCAGGTGGCTGGTCGGAAAGGATTTCCT; sequence #2: GCAGCCATAGTGAA GGACTGTTGCAGATA; sequence #3: CCAACATTCCTGTGGCTTCCACAAGTC AG; and sequence #4: GTCAGGTGCCTTAGTGACCACGCGGTCTT. We validated all constructs individually and found that constructs #1 and #2 were effective for SMAD4 knockdown. Subsequently, we used construct #1 for SMAD4 knockdown. Mission\u00ae esiRNA human STUB1 was purchased from Sigma\u2010Aldrich. Silencer\u00ae select pre\u2010designed siRNA targeting human WWP1  was purchased from Ambion (Thermo Fisher Scientific). The cells were transfected with siRNA using Lipofectamine\u00ae RNAiMAX  in accordance with the manufacturer's instructions.shRNA\u2010mediated knockdown of 2.5The cells were seeded in six\u2010well plates and cotransfected with p3TP\u2010Lux and pRL\u2010TK using ViaFect\u2122 . Twenty\u2010four hours after transfection, the cells were treated with TGF\u03b2 for 24\u00a0h, washed with PBS and harvested. Cell lysates were prepared with 200\u00a0\u03bcL of Passive Lysis buffer (Promega). Aliquots (20\u00a0\u03bcL) of cleared lysate were analyzed for luciferase activity using a Dual\u2010luciferase\u00ae reporter assay system (Promega). The luciferase activity of p3TP\u2010Lux was normalized to that of pRL\u2010TK.2.6m Hepes (pH 7.9), 10\u00a0mm KCl, 0.1\u00a0mm EDTA, 1\u00a0mm dithiothreiltol, 1\u00a0mm phenylmethanesulfonyl fluoride, 1\u00a0\u00d7\u00a0protease inhibitor cocktail and 1\u00a0mm sodium orthovanadate. The samples were adjusted to 0.6% Nonidet P\u201040 (NP\u201040), and vortexed vigorously for 10\u00a0s. Nuclei were pelleted by centrifugation at 10\u00a0000\u00a0\u00d7\u00a0g for 30\u00a0s at 4\u00a0\u00b0C. The supernatants were collected and used as the cytoplasmic fraction. After washing the pellets with PBS, they were lysed in buffer C comprising 20\u00a0mm Hepes, pH 7.9, 0.4\u00a0m NaCl, 0.1\u00a0mm EDTA, 1\u00a0mm dithiothreitol, 1\u00a0mm phenylmethanesulfonyl fluoride, 1\u00a0\u00d7\u00a0protease inhibitor cocktail and 1\u00a0mm sodium orthovanadate by sonication. The lysates were cleared by centrifugation at 10\u00a0000\u00a0\u00d7\u00a0g for 20\u00a0min at 4\u00a0\u00b0C. The supernatants were collected and used as the nuclear fraction.The cells were allowed to swell in buffer A comprising 10\u00a0m2.7m Tris\u2010HCl, pH 7.4, 150\u00a0mm NaCl, 0.5% NP\u201040) with cOmplete\u2122 protease inhibitor cocktail (Roche Diagnostics). The cell lysates were pre\u2010cleared and then incubated with the appropriate antibodies for 1\u00a0h at 4\u00a0\u00b0C. The antibody\u2013protein complexes were precipitated with Protein A/G\u2010Sepharose beads (Santa Cruz Biotechnology Inc.), washed, and resuspended in 40\u00a0\u03bcL of SDS/PAGE loading buffer.The cells were collected and lysed with 1\u00a0mL of immunoprecipitation lysis buffer  mutated to non\u2010phosphorylatable alanine residues or to phosphomimetic glutamic acids or to generate TGFBRI constitutively active (CA) mutant (threonine 204 is replaced with aspartic acid), mutagenesis was performed using a QuikChange site\u2010directed mutagenesis kit . All mutant constructs were confirmed by DNA sequencing. The mutagenic primer pairs used to generate mutants were: CK2\u03b2 3E (S2ES3ES4E): forward, 5\u2032\u2010GACGTGAAGATGGAAGAAGAAGAGGAGGTGTCC\u20103\u2032; reverse, 5\u2032\u2010GGACACCTCCTCTTCTTCTTCGATCTTCACGTC\u20103\u2032. CK2\u03b2 3A (S2A S3AS4A): forward, 5\u2032\u2010GACGTGAAGATGGCAGCAGCAGAGGAGGTGTCC\u20103\u2032; reverse, 5\u2032\u2010GGACACCTCCTCTGCTGCTGCCATCTTCACGTC\u20103\u2032. TGFBRI CA: forward, 5\u2032\u2010GAACAATTGCGAGAGATATTGTGTTACAAG\u20103\u2032; reverse, 5\u2032\u2010TCCGTA ACACAATATCTCTCGCAATTGTTC\u20103\u2032.2.9A cell migration assay was conducted using specific wound\u2010assay chambers purchased from ibidi GmbH . All experiments were performed in accordance with the manufacturer's instructions.2.10t\u2010test. P\u00a0<\u00a00.05 was considered statistically significant.Statistical comparisons of groups were performed using Student's 33.1et\u00a0al., et\u00a0al., in\u00a0vitro kinase assay and western blot analysis were performed. CK2 activity peaked at 48\u00a0h after TGF\u03b2 treatment and the E\u2010to N\u2010cadherin switch was observed 24\u00a0h after TGF\u03b2 treatment  A549 cells. Previously, we reported that CKD could decrease cellular CK2 activity  A549 cells using shRNA. When SKD cells were treated with TGF\u03b2, EMT was induced and CK2 was activated  A549 cells were generated using the CRISPR/Cas9 gene knockout system. Western blot analysis and in\u00a0vitro kinase assay showed that with \u03b2KO, the E\u2010 to N\u2010cadherin switch was induced . In the present study, we treated cells with 2\u00a0nm OA and thus PP2A could be completely inhibited; however, this might not be the case for PP1. OA treatment protected CK2\u03b2 from TGF\u03b2\u2010induced degradation . Further experiments, including the generation of PPP2CA and PPP2CB double knockout A549 cells, are required to identify the phosphatase involved in TGF\u03b2\u2010induced CK2\u03b2 dephosphorylation.In non\u2010canonical TGF\u03b2 signaling, TGFBRI kinase\u2010dependent activation and interaction of phosphatase 2A with p70\u2010S6 kinase could result in the dephosphorylation and inactivation of the kinase, thereby inducing G1 arrest  on motility.Click here for additional data file.Fig.\u00a0S2. Polyubiquitination of CK2\u03b2 by TGF\u03b2 signaling.Click here for additional data file.Fig.\u00a0S3. Screening of E3 ubiquitin ligases for CK2\u03b2 degradation.Click here for additional data file."}
{"text": "A, B, C and D). The conformations of the mol\u00adecules differ, as seen from the dihedral angles between the two pyridine rings in each mol\u00adecule. They vary from 5.51\u2005(9)\u00b0 for mol\u00adecule B to 25.25\u2005(8)\u00b0 for mol\u00adecule A.The asymmetric unit of the title disubstituted 2,3\u2032-bi\u00adpyridine, contains four independent mol\u00adecules  in the asymmetric unit. The dihedral angles between the two pyridine rings in each mol\u00adecule are 25.25\u2005(8)\u00b0 in A, 5.51\u2005(9)\u00b0 in B, 11.11\u2005(9)\u00b0 in C and 16.24\u2005(8)\u00b0 in D. In the crystal, mol\u00adecules A and B are linked by C\u2014H\u22efN hydrogen bonds to form layers extending parallel to the ab plane, while mol\u00adecules C and D are linked by C\u2014H\u22efN hydrogen bonds forming \u2013C\u2013D\u2013C\u2013D\u2013 chains propagating along the b-axis direction. The layers and the chains are stacked alternately along the c axis through offset \u03c0\u2013\u03c0 and C\u2261N\u22ef\u03c0 [N-to-pyridine-centroid distance = 3.882\u2005(2)\u2005\u00c5] inter\u00adactions, resulting in the formation of a supra\u00admolecular framework.The title compound, C T1) compared with phenyl\u00adpyridine-based CT1: 2.82\u2005eV) is larger than that of alk\u00adoxy-functionalized analogue, 2\u2032,6\u2032-dimeth\u00adoxy-2,3\u2032-bi\u00adpyridine (T1: 2.70 eV)  research area because developing blue phospho\u00adrescent materials remains a problem that has not been solved so far. Although there are a number of advantages in 2,3\u2032-bi\u00adpyridine ligands, incorporating the substituents into the ligand framework is difficult owing to the low selectivity and reactivity of the pyridine ring . The dihedral angles between the two pyridine rings in each mol\u00adecule are 25.25\u2005(8)\u00b0 in A, 5.51\u2005(9)\u00b0 in B, 11.11\u2005(9)\u00b0 in C and 16.24\u2005(8)\u00b0 in D. In order to investigate the conformational similarity between the four mol\u00adecules, the r.m.s. overlay fits of the 16 non-H atoms of each mol\u00adecule were calculated using the AutoMolFit routine in PLATON , forming layers extending parallel to the ab plane, while the C and D mol\u00adecules are connected through C\u2014H\u22efN hydrogen bonds  to from \u2013C\u2013D\u2013C\u2013D\u2013 chains propagating along the b-axis direction. The layers and chains stack alternately along the c axis, linked by inter\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions, resulting in the formation of a supra\u00admolecular framework, as shown in Fig.\u00a04Cg1\u22efCg2Di = 3.6741\u2005(9)\u2005\u00c5; Cg1\u22efCg2Div = 3.6546\u2005(9)\u2005\u00c5; Cg2\u22efCg1Div = 3.5888\u2005(9)\u2005\u00c5; Cg2B\u22efCg1Civ = 3.8196\u2005(10)\u2005\u00c5; Cg1 and Cg2 are the centroids of the N1/C1\u2013C5 and N2/C6-C10 rings. Atoms and centroids labelled with suffixes B, C and D represent those of the mol\u00adecules B, C and D, respectively]. In addition, inter\u00admolecular C\u2261N\u22ef\u03c0 inter\u00adactions between the cyano N atom of the D mol\u00adecule and the N1B-containing pyridine ring of mol\u00adecule B + .All experiments were performed under a dry NUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018011532/xu5937sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989018011532/xu5937Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018011532/xu5937Isup3.cmlSupporting information file. DOI: 1862117CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A and B) in the asymmetric unit. They differ essentially in the conformation of the pyrrolidine and cyclo\u00adpentene rings; respectively, twisted and flat in mol\u00adecule A, but envelope and twisted in mol\u00adecule B.The title compound crystallized with two independent mol\u00adecules  in the asymmetric unit. In both mol\u00adecules, the pyran and pyridine rings adopt envelope and chair conformations, respectively. The conformation of the pyrrolidine and cyclo\u00adpentene rings differ in the two mol\u00adecules; twisted and flat, respectively, in mol\u00adecule A, but envelope and twisted, respectively, in mol\u00adecule B. In both mol\u00adecules, there is a C\u2014H\u22efN intra\u00admolecular hydrogen bond present. In both mol\u00adecules, the oxygen atoms of the nitro groups are disordered as is the chlorine atom in mol\u00adecule B. In the crystal, the B mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming \u2013B\u2013B\u2013B\u2013 chains along [010], and by C\u2014H\u22ef\u03c0 inter\u00adactions. The A and B mol\u00adecules are also linked by a number of C\u2014H\u22ef\u03c0 inter\u00adactions, resulting in the formation a supra\u00admolecular three-dimensional structure. In mol\u00adecule A, the nitro group oxygen atoms are disordered over two positions with refined occupancy ratios of the nitro group oxygen atoms O3A and O4A in 0.59\u2005(2):0.41\u2005(2) while in molecule B one of the nitro O atoms is disordered over two positions with a refined occupancy ratio of 0.686\u2005(13):0.314\u2005(13) and the chlorine atoms is disordered over two positions with a refined occupancy ratio of 0.72\u2005(3):0.28\u2005(3).The title compound, C The mean plane of the five-membered pyrrolidine ring (N1/C12/C13/C21/C22) is inclined to the mean plane of the cyclo\u00adpentene ring (C1/C2/C10\u2013C12) by 87.30\u2005(13) and 88.41\u2005(11)\u00b0 in mol\u00adecules A and B, respectively. The benzene rings C27\u2013C32 and C14\u2013C19 are inclined to each other by 58.13\u2005(13)\u00b0 in mol\u00adecule A and 57.13\u2005(11)\u00b0 in mol\u00adecule B, while benzene rings C6\u2013C11 and C3\u2013C5/C33\u2013C35 are inclined to each other by 10.20\u2005(13)\u00b0 in mol\u00adecule A and 4.08\u2005(13)\u00b0 in mol\u00adecule B. The mean plane of the pyrrolidine ring (N1/C12/C13/C21/C22) makes a dihedral angle with the mean plane of the pyran ring (O2/C13/C14/C19\u2013C21) of 34.6\u2005(2)\u00b0 in mol\u00adecule A and 29.65\u2005(10)\u00b0 in mol\u00adecule B, and is inclined to the piperidine ring mean plane (N1/C22\u2013C26) by 15.69\u2005(12)\u00b0 in mol\u00adecule A and 12.36\u2005(11)\u00b0 in mol\u00adecule B. The mean planes of the pyran and piperidine rings are inclined to each other by 37.06\u2005(11) and 29.49\u2005(10)\u00b0 in mol\u00adecules A and B, respectively. The mean plane of the pyrazine ring (N3/N4/C1/C2/C3/C4) makes a dihedral angle with the mean plane of the pyran ring (O2/C13/C14/C19\u2013C21) of 63.42\u2005(19)\u00b0 in mol\u00adecule A and 72.64\u2005(10)\u00b0 in mol\u00adecule B. It is inclined to the pyrrolidine ring mean plane (N1/C12/C13/C21/C22) by 88.11\u2005(1)\u00b0 in mol\u00adecule A and 86.69\u2005(11)\u00b0 in mol\u00adecule B and is inclined to the piperidine ring mean plane (N1/C22\u2013C26) by 77.24\u2005(11)\u00b0 in mol\u00adecule A and 82.97\u2005(11)\u00b0 in mol\u00adecule B.Chlorine atoms Cl1B mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds, forming chains propagating along the b-axis direction -6a-nitro-6,6a,6\u2005b,7,8,9,10,12a-octa\u00adhydro\u00adspiro\u00adindolizine-12,3-indolin]-2-one  under a nitro\u00adgen atmosphere. The solution was refluxed for 20\u2005h in a Dean\u2013Stark apparatus to give the corresponding cyclo\u00adadduct. After completion of the reaction, as indicated by TLC, the solvent was evaporated under reduced pressure. The crude product obtained was purified by column chromatography using hexa\u00adne/EtOAc (6:4) as eluent (yield 86%). Colourless block-like crystals of the title compound were obtained by slow evaporation of a solution in ethanol.To a solution of indeno\u00adquinoxalinone (1.0\u2005mmol) and pipacolinic acid (1.5\u2005mmol) in dry toluene, was added 2-(4-chloro\u00adphen\u00adyl)-3-nitro-2Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a02A and O4A in A and O3B and O4B in B are disordered over two positions with refined occupancy ratios of O3A/O4A:O3A\u2032/O4A\u2032 = 0.59\u2005(2):0.41\u2005(2), and O3B/O4B:O3B\u2032/O4B\u2032 = 0.686\u2005(13):0.314\u2005(13). In mol\u00adecule B, the chlorine atom Cl2 is disordered over two positions with a refined occupancy ratio of Cl2:Cl2\u2032 = 0.72\u2005(3):0.28\u2005(3).In both mol\u00adecules, the nitro group oxygen atoms O310.1107/S2056989019000975/su5475sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019000975/su5475Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000975/su5475Isup3.cmlSupporting information file. DOI: 1024832CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Out-of-hospital electrocardiogram (ECG) shows a\u00a0sinus rhythm of 85\u00a0beats per minute (bpm), narrow QRS complex, and ST-segment elevations in leads V1\u2013V4 (coved morphology in V1\u2013V2), with a\u00a0terminal negative T\u00a0wave in V1\u2013V2 (Fig.\u00a0The patient met criteria for exertional heat stroke , and wasDiffuse ST-T deviations have been described in patients with heat stroke , but rigType\u00a01 Brugada-like ECG pattern induced by exertional heat stroke."}
{"text": "The benzo\u00adthia\u00adzine skeleton is not planar, with a maximum deviation of 0.3154\u2005(11)\u2005\u00c5 from the least-squares plane. The mol\u00adecule was expected to adopt mirror symmetry but slightly different conformational characteristics of the condensed benzo\u00adthia\u00adzine ring lead to point group symmetry 1. 19H14N2O6S2\u00b7C3H7NO. The mol\u00adecule was expected to adopt mirror symmetry but slightly different conformational characteristics of the condensed benzo\u00adthia\u00adzine ring lead to point group symmetry 1. In the crystal, mol\u00adecules form two types of stacking dimers with distances of 3.464\u2005(2)\u2005\u00c5 and 3.528\u2005(2)\u2005\u00c5 between \u03c0-systems. As a result, columns extending parallel to [100] are formed, which are connected to inter\u00admediate di\u00admethyl\u00adformamide solvent mol\u00adecules by C\u2014H\u22efO inter\u00adactions.The title mol\u00adecule crystallizes as a di\u00admethyl\u00adformamide monosolvate, C R-4-hy\u00addroxy-2-oxo-1,2-di\u00adhydro\u00adquinoline-3-carboxyl\u00adates are highly reactive compounds -one 6,6,8,8-tetroxide (I)H-2\u03bb6,1-benzo\u00adthia\u00adzine-3-carb\u00adoxyl\u00adate  and S = 0.48, \u03b8 = 50.0\u00b0, \u03a8 = 22.8\u00b0 for the C5\u2013C6\u2013C7\u2013C8\u2013N2\u2013S2 ring (2). The S1 and C1 atoms deviate by 0.669\u2005(2) and 0.207\u2005(2)\u2005\u00c5, respectively, from the mean-square plane of the remaining atoms in ring (1). The corresponding deviations in ring (2) are 0.668\u2005(2) and 0.270\u2005(2)\u2005\u00c5, respectively.Both thia\u00adzine rings adopt a twist-boat conformation Fig.\u00a01 with sliH-pyran-4-one ring (3) adopts a sofa conformation with puckering parameters S = 0.14, \u03b8 = 24.7\u00b0, \u03a8 = 22.6\u00b0. The deviation of C19 from the plane of the remaining atoms of (3) is 0.087\u2005(2)\u2005\u00c5. The C1=C2 and C5=C6 bonds [1.3571\u2005(17)\u2005\u00c5 and 1.3529\u2005(17)\u2005\u00c5] are slightly elongated as compared to the mean value of 1.329\u2005\u00c5 for a Csp2=Csp2 bond , H13\u22efH18B = 2.28\u2005\u00c5 (expected 2.34\u2005\u00c5), H13\u22efH18C = 2.31\u2005\u00c5 (expected 2.34\u2005\u00c5). These shortened contacts affect the very small pyramidalization of the nitro\u00adgen atoms; the sums of the bond angles centered at the N1 and N2 atoms are 354 and 356\u00b0, respectively.A further analysis of the mol\u00adecular structure revealed the presence of other shortened intra\u00admolecular contacts: H9\u22efH17In the crystal, mol\u00adecules of (I)Ai and C18\u2014H18B\u22efO1Aii  and diphenyl oxide (10\u2005ml) was maintained on a metal bath at 493\u2005K for 3\u2005h, then cooled and diluted with ethanol  = 1.5Ueq(C) for methyl groups and with C\u2014H = 0.93\u2005\u00c5, Uiso(H) = 1.2Ueq(C) for all other hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019008788/wm5508sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019008788/wm5508Isup2.hklStructure factors: contains datablock(s) I. DOI: 1935426CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Conventional O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding leads to a supra\u00admolecular layer in the crystal.A coordination geometry inter\u00admediate between square-planar and tetra\u00adhedral, defined by an N II complex, isolated as a dihydrate, [Cu(C21H14N3O3)2]\u00b72H2O, reveals a highly distorted coordination geometry inter\u00admediate between square-planar and tetra\u00adhedral defined by an N2O2 donor set derived from two mono-anionic bidentate ligands. Furthermore, each six-membered chelate ring adopts an envelope conformation with the Cu atom being the flap. In the crystal, imidazolyl-amine-N\u2014H\u22efO(water), water-O\u2014H\u22efO, phenyl-C\u2014H\u22efO(nitro) and \u03c0(imidazol\u00adyl)\u2013\u03c0(nitro\u00adbenzene) [inter-centroid distances = 3.7452\u2005(14) and 3.6647\u2005(13)\u2005\u00c5] contacts link the components into a supra\u00admolecular layer lying parallel to (101). The connections between layers forming a three-dimensional architecture are of the types nitro\u00adbenzene-C\u2014H\u22efO(nitro) and phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl). The distorted coordination geometry for the CuII atom is highlighted in an analysis of the Hirshfeld surface calculated for the metal centre alone. The significance of the inter\u00admolecular contacts is also revealed in a study of the calculated Hirshfeld surfaces; the dominant contacts in the crystal are H\u22efH (41.0%), O\u22efH/H\u22efO (27.1%) and C\u22efH/H\u22efC (19.6%).The crystal and mol\u00adecular structures of the title Cu Complex (I)via an analysis of the calculated Hirshfeld surfaces.The title copper(II) complex, (I)N,O-chelated by two 2--4-nitrophenolate mono-anions. The resulting N2O2 donor set defines a highly distorted coordination geometry, as seen in the angles included in Table\u00a014 is a geometric measure of the distortion of a four-coordinate geometry \u2005\u00c5 out of the plane. The comparable parameters for the O2-chelate ring are 0.033 and 0.354\u2005(3)\u2005\u00c5, respectively. The dihedral angle formed between the two planar regions of the chelate rings is 49.38\u2005(8)\u00b0. The dihedral angles between the best plane through the O1-chelate ring and each of the fused six- and five-membered rings are 9.18\u2005(12) and 5.54\u2005(14)\u00b0, respectively; the equivalent angles for the O2-chelate rings are 8.44\u2005(8) and 2.71\u2005(9)\u00b0, respectively. The N1-imidazol-2-yl ring forms dihedral angles of 41.20\u2005(11) and 37.46\u2005(10)\u00b0 with the C10- and C16-phenyl substituents, respectively, and the dihedral angle between the phenyl rings is 59.92\u2005(8)\u00b0, i.e. all indicating splayed relationships. A similar situation pertains to the N2-imidazol-2-yl ring, where the comparable dihedral angles formed with the C31- and C37-phenyl rings are 38.29\u2005(10), 48.5\u2005(9) and 50.84\u2005(7)\u00b0, respectively. Finally, the nitro groups are not strictly coplanar with the benzene rings to which they are connected, as seen in the dihedral angles of 14.2\u2005(4)\u00b0 for C1\u2013C6/N4/O3/O4 and 5.9\u2005(3)\u00b0 for C22\u2013C27/N6/O5/O6.The crystallographic asymmetric unit of (I)W water mol\u00adecule forms donor inter\u00adactions to the coordinated O2 atom and to a symmetry-related O2W water mol\u00adecule. The O2W water mol\u00adecule connects to the coordinated O1 atom as well as to a nitro-O3 atom. Hence, the O2W water mol\u00adecule is involved in four hydrogen-bonding inter\u00adactions. The fourth contact involving the O1W water mol\u00adecule, a C\u2014H\u22efO acceptor contact, is provided by the nitro\u00adbenzene ring. There is also a phenyl-C\u2014H\u22efO(nitro) contact of note, Table\u00a02a). There are also \u03c0\u2013\u03c0 stacking and C\u2014H\u22efO inter\u00adactions in the crystal, Fig.\u00a03b). Within layers, there are \u03c0\u2013\u03c0 inter\u00adactions occurring between the imidazolyl and nitro\u00adbenzene rings . The connections between layers along [010] are of the type nitro\u00adbenzene-C\u2014H\u22efO(nitro) and phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl), as detailed in Table\u00a02As each component of the asymmetric unit has hydrogen-bonding functionality, conventional hydrogen bonds are found in the crystal of (I)CrystalExplorer17 , and O2W-water, Fig.\u00a04b), mol\u00adecules. In addition, the presence of faint-red spots near the O1W, O2W and H1W atoms in Figs. 4a) and 4(b) are indicative of the other contacts of these atoms with those of the CuII complex mol\u00adecule (Table\u00a02c)\u2013(e).The Hirshfeld surface calculations for (I)e Table\u00a02. The dondnorm-mapped Hirshfeld surface in Fig.\u00a04c). The pair of faint-red spots appearing near the phenyl-C36 and H36 atoms, and also near the nitro-O5 atom on the surface indicating short inter\u00adatomic contacts that characterize the weak C\u2014H\u22efO inter\u00adaction, Table\u00a03e). The donors and acceptors of this inter\u00adaction are also evident as the blue bump and a bright-orange spot enclosed within the black circle on the Hirshfeld surface mapped with the shape-index property in Fig.\u00a05a). The bright-orange region enclosed within a black circle in Fig.\u00a05b) is also an indication of the O2W\u2014H4W\u22efCg(C16\u2013C21) contact. The Hirshfeld surfaces mapped over the calculated electrostatic potential for the water and complex mol\u00adecules in Fig.\u00a06dnorm illustrated in Figs.\u00a04c)\u2013(e), faint-red spots also appear near other atoms indicating their involvement in other short inter\u00adatomic contacts, as summarized in Table\u00a03The presence of a short inter\u00adatomic C\u22efC contact between atoms C22 and C28 Table\u00a03 arises f2O4 donor set about the copper(II) centre in the complex mol\u00adecule. This is performed by considering the Hirshfeld surface about the metal centre alone  and the small orange regions on the surface relatively far from the Cu\u2014N bonds in Fig.\u00a08b). The different curvature of the Hirshfeld surfaces coordinated by the N2O4 donor set in Figs.\u00a08c) and 8(d) also support this observation. The Cu\u2014O and Cu\u2014N bonds are rationalized in the two-dimensional fingerprint plot taking into account only the Hirshfeld surface for the copper atom shown in Fig.\u00a09de + di \u223c 2.0\u2005\u00c5 for the Cu\u2014N bonds (upper region) and the Cu\u2014O bonds (lower region) are indicative of the distorted geometry , and those delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC, C\u22efC and C\u22efO/O\u22efC contacts are illustrated in Figs.\u00a010b)\u2013(f), respectively. The percentage contribution from different inter\u00adatomic contacts to the Hirshfeld surfaces of the complex mol\u00adecule and for overall (I)de + di \u223c 1.9\u2005\u00c5 in the fingerprint plot delineated into H\u22efH contacts shown in Fig.\u00a010b) is the result of the involvement of the H12 atom in a short inter\u00adatomic H\u22efH contact, Table\u00a03W and H2W, Table\u00a03de\u00a0+ di \u223c 1.8\u2005\u00c5 in the plot delineated into O\u22efH/H\u22efO contacts, Fig.\u00a010c), arise from the N\u2014H\u22efO hydrogen bond, while the merged points correspond to other inter\u00adactions at greater inter\u00adatomic distances. The significant contribution from inter\u00adatomic C\u22efH/H\u22efC contacts (Table\u00a04d). The presence of short inter\u00adatomic C\u22efC contacts are evident as the points near a rocket shape tip at de + di \u223c 3.2\u2005\u00c5 in the respective delineated fingerprint plot, Fig.\u00a010e), while the points corresponding \u03c0\u2013\u03c0 stacking between the imidazole and nitro\u00adbenzene rings are distributed about de = di\u00a0= 1.7\u2005\u00c5 in the plot. The small, i.e. 2.7%, contribution from C\u22efN/N\u22efC contacts to the surface is also due to these \u03c0\u2013\u03c0 stacking inter\u00adactions (delineated plot not shown). The contribution of 3.2% from C\u22efO/O\u22efC contacts is due to the presence of short inter\u00adatomic contacts involving nitro-O atoms, Table\u00a02de + di \u223c 3.2\u2005\u00c5 in the delineated plot of Fig.\u00a010f). The contribution from other inter\u00adatomic contacts to the surface summarized in Table\u00a04The overall two-dimensional fingerprint plot for (I)s Table\u00a04 to the Hs Table\u00a04 and the H-imidazol-2-yl)phenolate ligands in the literature ; complex (IV) has crystallographic twofold symmetry. The final structure, a copper(II) complex \u2013(VI) of 0.48, 0.53, 0.44, 0.37, 0.47 and 0.35, respectively.There are five crystal structures of copper complexes with related 2-In a typical procedure, benzil , ammonium acetate , 2-hy\u00addroxy-5-nitro\u00adbenzalaldehyde  and copper(II) borate  were ground in an agate mortar with a pestle. To this mixture, about 1.5\u2005g of dried silica gel  was added and the reaction mixture was ground again for 30\u2005min. The whole reaction mixture was then transferred to a 100\u2005ml round-bottomed flask and heated at 130 \u00b0C with constant stirring for 4\u2005h. The reaction mixture was then extracted with dry acetone and dried over MgSOUiso(H) values set at 1.2Ueq(C). The O- and N-bound H atoms were located in a difference Fourier map but were refined with distance restraints of O\u2014H = 0.84\u2005\u00b1\u20050.01\u2005\u00c5 and N\u2014H = 0.88\u2005\u00b1\u20050.01\u2005\u00c5, respectively, and with Uiso(H) set at 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019013720/hb7859sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989019013720/hb7859Isup2.hklStructure factors: contains datablock(s) I. DOI: 1958158, 1958158CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the cation, the geometry around the Se atom is T-shaped, resulting from the coordination of Se by the C atom of the central aromatic ring and the N atoms of the benzimidazolyl moieties.In selenium} tetra\u00adkis\u00ad(seleno\u00adcyanato)\u00admercury, (C34H41N4Se)2[Hg(SeCN)4], the aryl\u00adselenenium cations, [C34H41N4Se]+, are linked through [Hg(SeCN)4]2\u2212 anions by C\u2014H\u22efN hydrogen bonds. In the cation, the geometry around the Se atom in the 5-tert-butyl-1,3-bis\u00ad(1-pentyl-1H-benzimidazol-2-yl)benzene scaffold is T-shaped, resulting from the coordination of Se by the C atom of the central aromatic ring and the N atoms of both of the benzimidazole moieties. The trans Se\u2014N bond lengths are almost equal [2.087\u2005(3) and 2.099\u2005(3)\u2005\u00c5] and the Se\u2014C bond length is 1.886\u2005(3)\u2005\u00c5. The N\u2014Se\u2014N angle is 159.29\u2005(11)\u00b0. The geometry around the HgII atom in the [Hg(SeCN)4]2\u2212 anion is distorted tetra\u00adhedral, with Se\u2014Hg\u2014Se angles ranging from 88.78\u2005(3) to 126.64\u2005(2)\u00b0. In [Hg(SeCN)4]2\u2212, the Hg\u2014Se bonds are unsymmetrical [2.5972\u2005(4) and 2.7242\u2005(5)\u2005\u00c5]. One of the pentyl substituents is disordered over two equivalent conformations, with occupancies of 0.852\u2005(8) and 0.148\u2005(8).In the title salt, bis\u00ad{[5- Some of these were investigated for their photoluminescence properties (Wang tert-but\u00adyl)-2,6-bis\u00ad(1-pentyl-1H-benzo[d]imidazol-2-yl)phen\u00adyl}(seleno\u00adcyanato)\u00admercury (3), mercury(II) chloride (1) was reacted with potassium seleno\u00adcyanate in 1,4-dioxane under reflux conditions. It was observed that, instead of the formation of the desired compound, the reaction leads to the isolation of an aryl\u00adselenenium(II) cation via auto-ionization 2 as by-products.In an attempt to synthesize {4-(2 reacts with an excess of KSeCN to form K2[Hg(SeCN)4] .HgCl2, crystallizes in the monoclinic space group C2/c. The asymmetric unit contains a selenenium cation along with half of a [Hg(SeCN)4]2\u2212 anion with the Hg atom located on a crystallographic twofold axis \u2005\u00c5, which is comparable with that found for a NCN pincer-based selenenium cation +[PF6]\u2212 C6H3Se]+[Br3]\u2212 (1.84\u2005\u00c5). The Se3\u2014N1 and Se3\u2014N2 bond lengths are almost equal [2.087\u2005(3) and 2.099\u2005(3)\u2005\u00c5]. The Se\u2014N distances are shorter than the sum of the van der Waals radii for Se and N [\u03a3rvdw 3.45\u2005\u00c5] and longer than the covalent radii [\u03a3rcov 1.91\u2005\u00c5]  form a plane (r.m.s deviation for fitted atoms of 0.0182\u2005\u00c5) with the Se in this plane [deviation from the plane of 0.011\u2005(2)\u2005\u00c5].The title compound, is Fig.\u00a01. In the 4]2\u2212 acts as a bridging moiety between two selenenium cationic units. The Se3\u22efSe2 distance is 4.189\u2005(2)\u2005\u00c5 and the C1\u2014Se3\u22efSe2 angle is 163.40\u2005(9)\u00b0, which indicates that there is a weak secondary inter\u00adaction between the two different kinds of Se atoms in the cation and anion (Se3 and Se2). In the [Hg(SeCN)4]2\u2212 anion, two sets of Hg\u2014Se bonds exist. One set is shorter [2.5972\u2005(4)\u2005\u00c5] and the other set is longer [2.7242\u2005(5)\u2005\u00c5]. The Hg\u2013SeCN moieties are not linear, with Hg\u2014Se\u2014C angles of 101.31\u2005(14) and 101.43\u2005(11)\u00b0.In the anion, the mercury atom is coordinated by four seleno\u00adcyanate anions  and the geometry around the mercury atom is distorted tetra\u00adhedral with Se\u2014Hg\u2014Se angles ranging from 88.78\u2005(3) to 126.64\u2005(2)\u00b0. The tetra\u00adcyano\u00adseleno\u00admercurate anion [Hg(SeCN)b-axis direction as shown in Fig.\u00a02A\u22efN1S and C18A\u2014H18C\u22efN2S inter\u00adactions ]selenenium cation. However, there have been several reports of structures containing [Hg(SeCN)1  in 1,4-dioxane (30\u2005ml) was added potassium seleno\u00adcyanate  dissolved in MeOH. The reaction mixture was stirred for 6\u2005h under a nitro\u00adgen atmosphere and refluxed. The reaction mixture was filtered and the precipitate was washed with dioxane. Colourless prism-shaped crystals of 2 were obtained by layering a MeOH solution with diethyl ether at room temperature.To a solution of \u22121): 3059 (w), 2957 (s), 2931 (s), 2869 (s), 2124 , 1614 (m), 1464 (s), 1458 (s), 1440 (s), 1330 (w), 1288 (w), 1273 (w), 1154 (w), 1137 (w), 1011 (w), 892 (w), 746 (s). ESI\u2013MS: m/z calculated for C34H41N4Se: 585.2496. Found: 585.2552.Yield 11% ; m. p. turned blackish after 423\u2005K was reached. FT\u2013IR (KBr) (cmUiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C-bound H atoms. One of the pentyl substituents is disordered with an occupancy ratio of 0.852\u2005(8):0.148\u2005(8). It was refined as two equivalent conformations using SAME and SIMU instructions (SAME 0.01 and SIMU 0.01).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018006394/zl2726sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018006394/zl2726Isup2.hklStructure factors: contains datablock(s) I. DOI: 1839609CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The copper(II) atom shows a typical Jahn\u2013Teller distorted [4\u00a0+\u00a02] octa\u00adhedral coordination sphere. H-benzotriazol-1-yl)acetic acid  and mono\u00adethano\u00adlamine  with CuCl2\u00b72H2O resulted in the formation of the title complex, [Cu(C8H6N3O2)2(C2H7NO)2] or [Cu(BTA)2(MEA)2]. Its asymmetric unit comprises one BTA anion coordin\u00adating to the Cu2+ cation (site symmetry R22(8) graph-set motif. The mol\u00adecules are further linked by C\u2014H\u22ef\u03c0 inter\u00adactions involving the triazole rings and methyl\u00adene groups of MEA, thus generating an overall three-dimensional supra\u00admolecular framework.The reaction of 2-(1 The Cu2+ cation is located on a center of inversion. Its coordination polyhedron is a distorted N2O4 octa\u00adhedron formed by two oxygen atoms (O2) of the carb\u00adoxy groups of symmetry-related BTA anions, by two nitro\u00adgen atoms (N4) of two symmetry-related MEA ligands in the equatorial plane and by two O atoms (O3) of the same set of MEA ligands in the axial positions. The Cu\u2014O2 and Cu\u2014N4 bond lengths are 2.029\u2005(1) and 1.980\u2005(2)\u2005\u00c5, respectively, whereas the length of the axial Cu\u2014O3 bond is 2.492\u2005(2)\u2005\u00c5, typical for Jahn\u2013Teller distortions. The MEA ligand is neutral and acts as a bidentate N- and O-donor ligand and forms CuNC2O five-membered chelate rings which have a twist conformation; the O3\u2014C10\u2014C9\u2014N4 torsion angle is \u221260.3\u2005(3)\u00b0. The planar benzotriazole ring system (N1\u2013N3/C1\u2013C6: r.m.s. deviation = 0.0064\u2005\u00c5) is co-planar with the methyl carbon atom C7 [deviation from the plane of 0.158\u2005(2)\u2005\u00c5], whereas the carboxyl\u00adate group is nearly normal to this plane [88.0\u2005(2)\u00b0]. The difference of the C8\u2014O distances of the carboxyl\u00adate group (\u0394 = 0.036\u2005\u00c5) is due to the monodentate coordination, with the longer C\u2014O distance involving the coordinating O2 atom.The mol\u00adecular structure of The mol\u00adecular structure is stabilized by an intra\u00admolecular O3\u2014H3\u22efO1 hydrogen bond between the OH group of the MEA ligand and the non-coordinating carboxyl\u00adate O atom Fig.\u00a01.A\u22efO1iii, N4\u2014H4A\u22efO2ii and N4\u2014H4B\u22efO3ii hydrogen bonds between the amino function and carboxyl\u00adate/hy\u00addroxy O-atom acceptors  generate a three-dimensional supra\u00admolecular framework.In the crystal structure of (I)s Table\u00a01, forming0) Fig.\u00a03. AdditioH-benzotriazol-1-yl)acetic acid and different metal cations in the CSD  was slowly added an ethanol solution (5\u2005ml) containing MEA  and HBTA  under constant stirring. Blue crystals of the product were obtained by solvent evaporation at room temperature after one week. Yield: 70%. Elemental analysis: Calc. for C20H26CuN8O6 (538.04): C, 44.65; H, 4.87\u2005N, 20.83%. Found: C, 44.73; H, 4.93; N, 20.88%.To an aqueous solution (2.5\u2005ml) of CuClUiso(H) = 1.2Ueq(C). The positions of the O- and N bound H atoms were located from a difference-Fourier map and were refined with soft distance restraints, 0.82\u2005\u00c5 for the hydroxyl group and 0.95\u2005\u00c5 for the primary amine group.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019000744/wm5481sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019000744/wm5481Isup2.hklStructure factors: contains datablock(s) I. DOI: 1891272CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion lies on a crystallographic twofold axis and has distorted tetra\u00adhedral coordination geometry. Two weak C\u2014H\u22efS intra\u00admolecular hydrogen bonds exist between the bipyridyl and thiol groups. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, forming a three-dimensional supra\u00admolecular architecture.The Zn 2N,N\u2032)bis\u00ad(2-meth\u00adoxy\u00adethyl xanthato-\u03baS)zinc(II), [Zn(C4H7O2S2)2(C10H8N2)], the ZnII ion is coordinated to two N atoms of the 2,2\u2032-bi\u00adpyridine ligand and two S atoms from two 2-meth\u00adoxy\u00adethyl xanthate ligands. The ZnII ion lies on a crystallographic twofold rotation axis and has distorted tetra\u00adhedral coordination geometry. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO hydrogen bonds, forming supramolecular chains propagating along the a-axis direction. Weak intra\u00admolecular C\u2014H\u22efS hydrogen bonds are also observed. The inter\u00admolecular contacts in the crystal were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are H\u22efH (36.3%), followed by S\u22efH/H\u22efS (24.7%), C\u22efH/H\u22efC (15.1%), O\u22efH/H\u22efO (14.4%), N\u22efH/H\u22efN (4.1%) and C\u22efC (2.9%).In the title compound, (2,2\u2032-bi\u00adpyridine-\u03ba ROCS2\u2212) have attracted the attention of scientific groups of researchers due to their diverse applications. Metal xanthates have been used as single-source precursors to metal sulfide materials  and 2.295\u2005(2)\u2005\u00c5, respectively, whereas the bond angles around the central ZnII ion are in the range 78.7\u2005(3)\u2013126.64\u2005(10)\u00b0 . The C\u2014O bond lengths range from 1.346\u2005(8) to 1.453\u2005(8)\u2005\u00c5 although all of the C\u2014O bonds show single-bond character. In the {S2C} part of the xanthate ligands, the C1\u2014S1 distance is 1.727\u2005(7)\u2005\u00c5, which is typical of a single bond whereas the C1\u2014S2 distance of 1.652\u2005(7)\u2005\u00c5 is typical of a carbon-to-sulfur double bond. The C\u2014N and C\u2014C bond lengths in 2,2\u2032-bi\u00adpyridine are normal for 2-substituted pyridine derivatives (O-n-propyl\u00addithio\u00adcarbonato-S)zinc(II) zinc(II) and \u00adbis\u00ad(O-iso\u00adbutyl\u00adxan\u00adth\u00adato)zinc(II) . 2H2O  in 2-meth\u00adoxy\u00adethanol, was added a hot solution of 2,2\u2032-bipy  in 2-meth\u00adoxy\u00adethanol. A hot solution of potassium 2-meth\u00adoxy\u00adethylxanthate  in 2-meth\u00adoxy\u00adethanol was added under stirring. Colourless crystals were formed after 30 minutes. The crystals were washed with small amounts of 2-meth\u00adoxy\u00adethanol and water and air-dried.To a hot solution of Zn(CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. The crystal was a weak diffractor (I/\u03c3 at 0.81 resolution was 5.1) and refinedas a two-component twin with HKLF 4 data (twin law \u22121 0 0 0\u00a0\u2212\u00a01 0 0 0\u00a0\u2212\u00a01) but this had little effect. The anisotropy of N1 was restrained with ISOR 0.01 0.02 in SHELXL  I. DOI: 10.1107/S2056989019014968/lh5934Isup2.hklStructure factors: contains datablock(s) I. DOI: 1424075, 1424075CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit contains two independent mol\u00adecules and two water mol\u00adecules. The central parts of both the mol\u00adecules are twisted as both mol\u00adecules are bent at both the S and N atoms. The crystal structure features N\u2014H\u22efN, N\u2014H\u22efO, C\u2014H\u22efO and O\u2014H\u22efO inter\u00admolecular inter\u00adactions. Two-dimensional fingerprint plots show that the largest contributions to the crystal stability come from O\u22efH/H\u22efO and H\u22efH inter\u00adactions. 9H8ClN3O3S2\u00b7H2O, consists of two independent mol\u00adecules and two water mol\u00adecules. The central parts of the mol\u00adecules are twisted as both the mol\u00adecules are bent at both the S and N atoms. In the crystal, N\u2014H\u22efN, N\u2014H\u22efO, C\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding inter\u00adactions connect the mol\u00adecules, forming layers parallel to the ab plane. Two-dimensional fingerprint plots associated with the Hirshfeld surface show that the largest contributions to the crystal packing come from O\u22efH/H\u22efO (32.9%) and H\u22efH (22.6%) inter\u00adactions.The asymmetric unit of the title thia\u00adzole derivative containing a sulfonyl\u00adhydrazinic moiety, C The sulfonyl\u00adhydrazide bond exists in the synclinal conformation preferred by aromatic sulfonamides benz\u00adene\u00adsulfono\u00adhydrazide -methyl 2-[(Z)-4-oxo-2-(2-tosyl\u00adhydrazono)thia\u00adzolidin-5-yl\u00adidene]acetate and (Z)-methyl-2-[(Z)-2-(ethyl\u00adimino)-4-oxo-3-(phenyl\u00adamino)\u00adthia\u00adzolidin-5-yl\u00adidene]acetate phen\u00adyl]-1,3-thia\u00adzol-2(3H)-yl\u00adidene}benzene\u00adsulfono\u00adhydrazide  and related fingerprint plots were generated using CrystalExplorer17.5 /rivdw\u00a0+\u00a0(de\u00a0\u2212\u00a0revdw)/revdw  with di + de \u223c 1.9\u2005\u00c5. The presence of water mol\u00adecules in the unit cell provides the largest contribution to the stability of the crystal packing. The next largest contrib\u00adutor is from H\u22efH inter\u00adactions, which contribute 22.6%. A single sharp spike can be seen in the middle region of the plot, at di = de = 0.9\u2005\u00c5 . The N\u22efH contacts, which refer to N\u2014H\u22efN inter\u00adactions, contribute 5.3% to the surface. Two sharp spikes having di + de = 1.8\u2005\u00c5  are observed. The C\u22efH contacts contribute 5.9% to the Hirshfeld surface, featuring a wide region with di + de = 3.1\u2005\u00c5 . The different inter\u00adatomic contacts and percentage contributions to the Hirshfeld surface are Cl\u22efH/H\u22efCl (8.3%), S\u22efH/H\u22efS (6.1%), Cl\u22efO/O\u22efCl (3.0%), Cl\u22efC/C\u22efCl (2.4%), S\u22efO/O\u22efS (1.7%), and C\u22efO/O\u22efC (1.6%) as depicted in the fingerprint plots .In order to explore the role of weak inter\u00admolecular inter\u00adactions in the crystal packing, Hirshfeld surfaces benzene-1-sulfono\u00adhydrazide was prepared by adding 4-chloro benzene\u00adsulfonyl chloride (0.02\u2005mol) under stirring to a solution of thio\u00adsemicarbazide (0.02\u2005mol) in 5% aqueous NaOH solution (20\u2005ml). The reaction mixture was stirred at room temperature for 1\u2005h, then diluted twofold with water and neutralized with glacial acetic acid. The solid 2-(4-chloro\u00adbenzene-1-sulfon\u00adyl)hydrazine-1-carbo\u00adthio\u00adamide (A) obtained was crystallized from acetic acid. Mono\u00adchloro\u00adacetic acid (0.01\u2005mol) and anhydrous sodium acetate (0.04\u2005mol) were added to A (0.01\u2005mol) in glacial acetic acid. The reaction mixture was refluxed for 8\u201310\u2005h and the completion of the reaction was checked by TLC. The reaction mixture was then poured into cold water. The resulted precipitate of the title compound was separated by vacuum filtration. Prismatic colourless single crystals of the title compound were grown from a mixture of aceto\u00adnitrile-DMF (5:1 v/v) by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by IR spectroscopy. The characteristic IR absorptions observed at 3095.9, 1639.5, 1458.7, 1343.2, 1139.4, and 1215.7\u2005cm\u22121 correspond to N\u2014H, C=O, C=N, S=O asymmetric and symmetric, and C\u2014S absorptions, respectively. The 1H and 13C spectra of the title compound are as follows: 1H ; \u03b4 3.45 , 7.68\u20137.86 , 10.01 , 11.96 . 13C NMR ; \u03b4 36.8, 128.4, 129.1, 131.1,132.5, 133.9, 137.2, 165.4, 185.5.4-Chloro-Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018013658/rz5243sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018013658/rz5243Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013658/rz5243Isup3.cmlSupporting information file. DOI: 1869597CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N(4)-morpholino\u00adthio\u00adsemicarbazone forms sheets parallel to (002) and consisting of two parallel chains running in the a-axis direction and formed by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds.In the crystalline state, salicyl\u00adaldehyde  N-{[(2-hy\u00addroxy\u00adphen\u00adyl)methyl\u00adidene]amino}\u00admorpholine-4-carbo\u00adthio\u00adamide), C12H15N3O2S, was prev\u00adiously determined \u00b0. In the crystal, the mol\u00adecules are connected into chains by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, which combine to generate sheets lying parallel to (002). The most prominent contribution to the surface contacts are H\u22efH contacts (51.6%), as concluded from a Hirshfeld surface analysis.The structure of the title compound (systematic name:  Cisplatin is well known as an effective therapy to prohibit the proliferation of tumor cells -substituted thio\u00adsemicarbazide. Many reports have demonstrated that N(4)-aromatic or heterocyclic substituted thio\u00adsemicarbazides are biologically more active than thio\u00adsemicarbazones without substituted groups -morpholino\u00adthio\u00adsemicarbazone was published previously -morpholino\u00adthio\u00adsemicarbazone (3) together with its structural characteristics and crystal structure redetermination using present-day technology.The crystal and mol\u00adecular structure of salicyl\u00adaldehyde Pna21 with one mol\u00adecule in the asymmetric unit \u00b0], which gives rise to an intra\u00admolecular O18\u2014H18\u22efN10 hydrogen bond with an ap conformation].The title compound crystallizes in the ortho\u00adrhom\u00adbic space group it Fig.\u00a01. The N9\u2014f Table\u00a01. The plaQ = 0.554\u2005(3)\u2005\u00c5, \u03b8 = 173.2\u2005(3)\u00b0 and \u03c6 = 214\u2005(3)\u00b0] with the thio\u00adsemicarbazone function in an equatorial position. The plane of the phenyl ring forms a dihedral angle of 43.44\u2005(17)\u00b0 with the best plane through the morpholino ring. A second intra\u00admolecular C6\u2014H6A\u22efS8 inter\u00adaction is observed (Table\u00a01The morpholino ring adopts a chair conformation .A search of the Cambridge Structural Database  and \u2212175.97\u2005(15)\u00b0] and \u03c42 [166.51\u2005(16) and \u2212174.99\u2005(16)\u00b0] are similar to those observed for the title compound. An intra\u00admolecular hydrogen bond similar to O18\u2014H18\u22efN10 is also observed.The most similar compound present in the CSD is the 2-hy\u00addroxy\u00adnaphthaldehyde-based thio\u00adsemicarbazone  is given in Fig.\u00a07The reaction scheme for the synthesis of (Synthesis of 2-((morpholine-4-carbono\u00adthio\u00adyl)thio)\u00adacetic acid (1):A mixture consisting of carbon di\u00adsulfide (0.2\u2005mol) and concentrated ammonia (25\u2005mL) was stirred to form a homogeneous solution at 278\u2005K. Then, morpholine (0.2\u2005mol) was added dropwise to this solution. The yellow solid that separated from the solution was filtered off and immediately dissolved in deionized water (300\u2005mL) at room temperature to generate a yellow solution. Sodium chloro\u00adacetate (0.2\u2005mol) was added to this solution and the reaction mixture maintained for 6\u2005h at room temperature. The yellowish solution was acidified with concentrated hydro\u00adchloric acid and the resulting white precipitate was filtered off and recrystallized from ethanol.Synthesis of N(4)-morpholino\u00adthio\u00adsemicarbazide (2):1) (50\u2005mmol), deionized water (10\u2005mL) and hydrazine hydrate (25\u2005mL) was refluxed for 30 minutes at 353\u2005K. The white solid which precipitated from the transparent solution was filtered off and recrystallized from ethanol to give (2).A mixture composed of -morpholino\u00adthio\u00adsemicarbazone (3):2) in hot ethanol, the solution was added to an equivalent amount of salicyl\u00adaldehyde. The final solution was refluxed at 353\u2005K for 2\u2005h in the presence of acetic acid as a catalyst. The resulting solution was gradually reduced in volume at room temperature overnight. The needle-shaped crystals that formed were filtered off and recrystallized from ethanol to give (3) in the form of transparent crystals (yield 60%), m.p. 461\u2013463\u2005K. FT\u2013IR (cm\u22121): 3436 (O\u2014H), 3279 (N\u2014H), 1617 (CAr\u2014H), 1540 (C=N), 1061 (N\u2014N), 1348 and 959 (C=S). 1H NMR : 3.67 ; 3.92 ; 6.90 ; 7.28 ; 7.41 ; 8.47 ; 11.49 ; 11.55 . 13C NMR : 49.4 (C2 and C6), 66.2 (C3 and C5), 117.0 (C14), 118.9 (C12), 119.5 (C16), 130.4 (C17), 131.3 (C15), 146.9 (C13), 157.6 (C11), 180.1 (C7). UV\u2013Vis : 200 (\u03c0\u2192\u03c0*); 300 and 350 (n\u2192\u03c0*).After dissolving (Uiso(H) values 1.2Ueq of the parent atoms, with C\u2014H distances of 0.93  and 0.97\u2005\u00c5 (CH2). In the final cycles of refinement, 4 outliers were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019011812/mw2147sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019011812/mw2147Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019011812/mw2147Isup3.cmlSupporting information file. DOI: 1949697CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "EVs). Three mouse melanoma B16 variants with distinct metastatic potentials show similar gene expression levels and enzymatic activities of glycosyltransferases involved in N\u2010glycosylation. All melanoma variants and EVs have nearly identical profiles of de\u2010sialylated N\u2010glycans. The major de\u2010sialylated N\u2010glycan structures of cells and EVs are core\u2010fucosylated, tetra\u2010antennary N\u2010glycans with \u03b21,6\u2010N\u2010acetylglucosamine branches. A few N\u2010glycans are extended by N\u2010acetyllactosamine repeats. Sialylation of these N\u2010glycans may generate cell\u2010type\u2010specific N\u2010glycomes on EVs. Taken together, melanoma\u2010derived EVs show high expression of tumor\u2010associated N\u2010glycans, and the core structure profile is inherited during multiple selection cycles of B16 melanomas and from tumor cells to EVs.We investigated the correlation between metastatic behaviors of tumor cells and asparagine\u2010linked glycosylation (N\u2010glycosylation) of tumor\u2010derived extracellular vesicles ( EVs, extracellular vesiclesPA, 2\u2010aminopyridineN\u2010acetylglucosamine (GlcNAc) may be fucosylated (core fucosylation) Most cell surface and secretory proteins are modified by asparagine\u2010linked glycans (N\u2010glycans) in\u00a0vivo and in\u00a0vitro selections have been performed to obtain mouse B16 malignant melanoma variants with distinct metastatic potentials. The B16\u2010F1 (poorly lung\u2010colonizing) and B16\u2010F10 (highly lung\u2010colonizing) variants are selected for their lung colonization abilities following intravenous injection of the parent B16 cells  in\u00a0vitro, resulting in a highly spontaneous metastatic variant Blood\u2010borne tumor metastasis is a complex process involving tumor cell invasion into normal tissues, intravasation to the circulation, extravasation, and colonization at distant organs Tumor cells secrete small vesicles, termed extracellular vesicles (EVs), that contain various cargo molecules including nucleic acids, soluble proteins, and membrane proteins in\u00a0vivo and in\u00a0vitro selection cycles of B16 variants and is copied from tumor cells to their EVs. It was suggested that sialylation of these N\u2010glycans probably generates cell\u2010type\u2010specific N\u2010glycome on EVs. This study establishes the N\u2010glycosylation landscapes of B16 variants and their EVs, and indicates that the bulk N\u2010glycosylation of melanoma EVs does not reflect the metastatic potentials of their secreting tumor cells in the B16 model.In the present study, we investigated the correlation between metastatic potentials of three B16 variants  and N\u2010glycosylation of their EVs by characterizing N\u2010glycan structures and gene expression, as well as enzymatic activity, of glycosyltransferases involved in N\u2010glycosylation. The results demonstrate that the core structure profile of N\u2010glycans is inherited at the genetic level during multiple \u22121 penicillin, and 100\u00a0\u03bcg\u00b7mL\u22121 streptomycin at 37\u00a0\u00b0C in a 5% CO2 atmosphere.Mouse B16\u2010F1 and B16\u2010F10 melanoma cells were purchased from the American Type Culture Collection . B16\u2010BL6 cells were purchased from RIKEN Bioresource Center. All cell lines were maintained in complete Dulbecco's modified Eagle's medium containing 10% fetal bovine serum, 100\u00a0U\u00b7mL6 cells/10\u2010cm dish) were cultured for 24\u00a0h, washed twice with PBS, and incubated for 48\u00a0h in EV\u2010depleted medium. The conditioned medium was sequentially centrifuged at 130\u00a0g for 5\u00a0min, 20\u00a0000\u00a0g for 20\u00a0min, and 100\u00a0000\u00a0g for 70\u00a0min. The final pellet containing EVs was washed once with PBS and measured for its protein concentration with a BCA protein assay kit , using bovine serum albumin as an external standard.Extracellular vesicles were prepared as described m Tris\u2010HCl (pH 7.4), 150\u00a0mm NaCl, 1% Triton X\u2010100, 1\u00a0mm EDTA, and protease inhibitor cocktail . The homogenate was centrifuged at 20\u00a0000\u00a0g for 10\u00a0min and the supernatant was recovered as the whole cell lysate.Cells were lysed for 15\u00a0min at 0\u00a0\u00b0C in lysis buffer comprising 10\u00a0mN4\u2010(N\u2010acetyl\u2010\u03b2\u2010glucosaminyl)asparagine amidase F (PNGase F)  according to the manufacturer's instructions. The released N\u2010glycans were purified and fluorescently labeled with 2\u2010aminopyridine (PA) using a BlotGlyco Kit  according to the manufacturer's instructions.N\u2010glycans were released from EVs and whole cell lysates by treatment with peptide\u2010Arthrobacter ureafaciens in 10\u00a0mm sodium acetate buffer (pH 5.5) for 16\u00a0h at 37\u00a0\u00b0C. The sialidase\u2010digested samples and the neutral fraction were desalted on PD\u201010 desalting columns  and subjected to reversed\u2010phase HPLC as described \u22121; Takara), as described PA\u2010labeled N\u2010glycans were initially separated into one neutral fraction and six sialidase\u2010sensitive fractions by anion\u2010exchange HPLC, as described PA\u2010labeled N\u2010glycans fractionated by reversed\u2010phase HPLC were subjected to matrix\u2010assisted laser desorption/ionization time\u2010of\u2010flight mass spectrometric analysis. PA\u2010glycans (1\u00a0\u03bcL) were mixed with 1\u00a0\u03bcL of 2,5\u2010dihydroxybenzoic acid (10\u00a0mg/mL in 50% acetonitrile/0.1% trifluoroacetic acid) on a target plate. After evaporation to dryness, spectra were obtained in the positive mode using an Autoflex mass spectrometer  operated in the reflector mode.http://www.glycoanalysis.info/galaxy2/ENG/index.jsp), using the masses and glucose units of individual glycans, the latter of which were calculated by the elution positions of PA\u2010glucose oligomers (degree of polymerization\u00a0=\u00a03\u201322) in the reversed\u2010phase and size\u2010fractionation chromatography The structures of PA\u2010labeled N\u2010glycans from melanoma EVs were determined by reference to a database, glycoanalysis by the three axes of MS and chromatography (GALAXY) Samples (10\u00a0\u03bcg protein) were denatured for 3\u00a0min at 100\u00a0\u00b0C, separated by SDS/PAGE, and analyzed by western blotting using an anti\u2010CD81 antibody .6 cells/10\u2010cm dish) that had been cultivated for 48\u00a0h using TRI Reagent  in accordance with the manufacturer's protocol, followed by treatment with DNase (Qiagen) and purification using RNeasy Mini kit . 1\u00a0\u03bcg total RNA was reverse\u2010transcribed using an R2 First Strand Kit (Qiagen) in a 40\u2010\u03bcL reaction mixture and then diluted with 182\u00a0\u03bcL RNase\u2010free water. The cDNA thus obtained was mixed with 2.7\u00a0mL RT2 SYBR Green qPCR Mastermix (Qiagen) and 2.496\u00a0mL water, and 25\u00a0\u03bcL of the mixture was applied to each well of a 96\u2010well plate that contained specific primers for glycotransferase mRNAs (Qiagen). Two types of 96\u2010well plates were used for quantification of 144 glycosyltransferase genes; a commercially available plate for Mouse Glycosylation (Cat. No. 330231 PAMM\u2010046ZA) covering 84 glyco\u2010related genes, and a 96\u2010Well Custom PCR Array in which we manually selected 86 glycosyltransferase genes, seven house keeping genes  and three primers for monitoring genomic contamination, cDNA synthesis and PCR reaction. cDNAs were amplified and analyzed using an ABI PRISM 7900HT thermocycler  according to the RT2 Profiler PCR Array Handbook (Qiagen). The abundance of glycotransferase mRNAs relative to that of housekeeping genes  was calculated using the \u0394Ct method. The values in Tables\u00a0Real\u2010time PCR for glycosyltransferases was performed as described previously m MES pH 6.2, 10\u00a0mm MnCl2, 10\u00a0mm UDP\u2010Gal at 37\u00a0\u00b0C overnight. The enzymes were mixed with various concentrations of a fluorescence\u2010labeled acceptor substrate  equipped with an ODS column  Enzymatic activity of mannosyl \u2010glycoprotein \u03b21,4\u2010GlcNAc transferase (Mgat3), \u03b1\u20101,3\u2010mannosyl\u2010glycoprotein 4\u2010\u03b2\u2010GlcNAc transferase (Mgat4), \u03b1\u20101,6\u2010mannosylglycoprotein 6\u2010\u03b2\u2010GlcNAc transferase (Mgat5), fucosyltransferase 8 (Fut8), \u03b12,3\u2010sialyltransferase and \u03b12,6\u2010sialyltransferase were measured as described previously cDNAs encoding the catalytic regions of human MGAT3, mouse Magt4a, human MGAT5, human FUT8, human ST3GAL4 and human ST6GAL1 were amplified by PCR with primers: human MGAT3, 5\u2032CGGAATTCGAGCCAGGAGGCCCTGACCT3\u2032 and 5\u2032CTAGACTTCCGCCTCGTCCA3\u2032; mouse Mgat4a, 5\u2032CGGAGCTAAACACCATTGTC3\u2032 and 5\u2032GTGCTCGAGTCTAAGCAGATCAACTGGTG3\u2032; human MGAT5, 5\u2032CTACAGCTGTTCCCAGCTTG3\u2032 and 5\u2032AGGCTCGAGCTATAGGCAGTCTTTGCAGA3\u2032; human FUT8, 5\u2032CGGAATTCCGGATACCAGAAGGCCCTAT3\u2032 and 5\u2032TTATTTCTCAGCCTCAGGAT3\u2032; human ST3GAL4, 5\u2032GAGGAATTCGAGCCGTGCCTCCAGGGTGA3\u2032 and 5\u2032TTGCTCGAGTCAGAAGGACGTGAGGTTCTTG3\u2032; and human ST6GAL1, 5\u2032GTGGAATTCAAGGACAGCTCTTCCAAAAA3\u2032 and 5\u2032AAACTCGAGTTAGCAGTGAATGGTCCGGAA3\u2032.2+\u2010column and desalted with NAP\u20105 gel filtration column .The PCR products were inserted into pcDNA\u2010IH as described previously Stt3a and Stt3b), protein quality control in the ER (Uggt1 and Uggt2), GlcNAc branch formation , lysosome targeting (Gnptab and Gnptg), galactosyltransferases , polylactosamine formation (B3gnt2 and B3gnt4), core fucosylation (Fut8), \u03b12,3\u2010sialyltransferases  and \u03b12,6\u2010sialyltransferase . The gene expression pattern of B16\u2010F1 and B16\u2010BL6 cells was similar to that of B16\u2010F10 cells, except that B4galt2 was undetectable in B16\u2010BL6 cells. We hardly detected expression of Mgat3 (bisecting GlcNAc formation), as well as Fut1\u20107 and Fut9 , in all three variants. In comparison of cells with different lung colonization ability (B16\u2010F1 and B16\u2010F10), B16\u2010F1 cells showed higher expression of Mgat5 (1.5\u2010fold), B4galt2 (3\u2010fold), B3gnt2 (1.5\u2010fold), St3gal4 (2.0\u2010fold) and St6gal1 (1.4\u2010fold) than B16\u2010F10 cells. In contrast, B16\u2010F1 cells expressed lower levels of Stt3a (0.8\u2010fold), B3galt2 (0.7\u2010fold) and Fut8 (0.8\u2010fold) than B16\u2010F10 cells. In comparison of cells with different invasiveness (B16\u2010F10 and B16\u2010BL6), B16\u2010BL6 cells showed higher levels of Uggt2 (1.8\u2010fold), Mgat4b (1.4\u2010fold), B4galt1 (1.2\u2010fold), B3galt2 (1.2\u2010fold), St3gal4 (1.3\u2010fold) and St6gal1 (1.9\u2010fold) than B16\u2010F10 cells. In contrast, B16\u2010BL6 cells showed lower expression of Uggt1 (0.7\u2010fold), Mgat4a (0.7\u2010fold) and Mgat5 (0.8\u2010fold) than B16\u2010F10 cells, suggesting that low expression of Uggt1 and Mgat4a is compensated by high expression of Uggt2 and Mgat4b in B16\u2010BL6 cells. Together, these results indicate that B16 variants with distinct metastatic potential have unique glycosyltransferase gene expression patterns. However, overall N\u2010glycosylation\u2010related gene profiles are inherited during multiple selection cycles of B16 variants.The cellular N\u2010glycome is regulated by multiple factors including the expression profiles of glycosyltransferase genes Mgat3 gene was rarely expressed in all three B16 variants  Among the three B16 variants, the B16\u2010F10 variant is positioned in the middle of the selection cycles N\u2010acetyllactosamine repeats (polylactosamine), which can serve as ligands for galactose\u2010binding lectins  As the sialylation of N\u2010glycans generated considerable structural heterogeneity, de\u2010sialylated N\u2010glycans were subjected to further structural analyses. Neutral and de\u2010sialylated Sia 1\u20106 fractions from anion\u2010exchange HPLC were further fractionated by reversed\u2010phase HPLC Fig.\u00a0C and subTo investigate whether characteristic core N\u2010glycan structures were enriched in EVs, we compared reversed\u2010phase HPLC profiles of de\u2010sialylated complex\u2010type glycans between F10\u2010EVs and B16\u2010F10 cells. For the comparison, we chose eight major peaks that contained nine N\u2010glycans Fig.\u00a0A and fouNext, we investigated whether the N\u2010glycosylation profiles of EVs differed among the B16 variants. Anion\u2010exchange HPLC analysis of sialylated glycans obtained from F1\u2010EVs, F10\u2010EVs, and BL6\u2010EVs revealed that although the number of sialic acids present on N\u2010glycans was similar among the three variants, the Sia 3 fraction showed distinct elution patterns , the Kodama Memorial Fund for Medical Research (YH), and MEXT/JSPS Grants\u2010in\u2010Aid for Scientific Research (JP17H06414 to HY and 17K07356 to YK).Fig.\u00a0S1. Relative gene expression levels of 144 glycosyltransferases in B16 variants.Click here for additional data file.Fig.\u00a0S2. Comparative analysis of sialylated N\u2010glycans from B16\u2010F10 cells and F10\u2010EVs.Click here for additional data file.Fig.\u00a0S3. Relative amounts of sialylated N\u2010glycans in the Sia 1\u20106 fractions of B16\u2010F10 cells and F10\u2010EVs.Click here for additional data file.Table\u00a0S1. mRNA abundances of glycosyltransferases relative to the mean abundance of four housekeeping genes  in B16 variants.Table\u00a0S2. Structural analysis of N\u2010glycans expressed on EVs from B16\u2010F10 cells.Click here for additional data file."}
{"text": "In the crystal structure, inter\u00admolecular N\u2014H\u22efN hydrogen bonds link the mol\u00adecules into infinite ribbons extending along the [100] direction. 12H10N6, at 100\u2005K has monoclinic (P21/n) symmetry. Crystals were obtained as a yellow solid by reduction of 3,6-bis\u00ad(pyridin-2-yl)-1,2,4,5-tetra\u00adzine. The structure displays inter\u00admolecular hydrogen bonding of the N\u2014H\u22efN type, ordering mol\u00adecules into infinite ribbons extending along the [100] direction.The structure of the title compound, C The substitution of four nitro\u00adgen atoms in a six-membered benzene-like ring results in strong \u03c0-electron deficiency and concentration of negative charge on the heteroatoms. As a result of these properties, s-tetra\u00adzines are used in organic synthesis  in ethanol solution -1,4-di\u00adhydro-1,2,4,5-tetra\u00adzine (I)on Fig.\u00a01.P21/n. The atomic labelling scheme is shown in Fig.\u00a02Compound (I)et al., 1987A) ring are of almost equal length, being 1.4285\u2005(15) and 1.4306\u2005(16)\u2005\u00c5. The C6\u2014N1 and C3\u2014N4 [1.3953\u2005(17) and 1.4051\u2005(17)\u2005\u00c5] bond lengths are longer than those for C6\u2014N5 and C3\u2014N2 , respectively. This is the result of the protonation of the N1 and N4 atoms. The C\u2014N bond lengths in the B and C rings are comparable within 3\u03c3, varying from 1.3384\u2005(18)\u2005\u00c5 to 1.3416\u2005(17)\u2005\u00c5.The C\u2014C bond lengths are within the expected values known for aromatic systems (Allen A) shows a boat conformation with pseudo-symmetry mirror planes passing through bonds N2\u2014C3 and N5\u2014C6 [\u0394Cs = 1.30\u2005(16)\u00b0] and atoms N1, N4 [\u0394Cs = 2.00\u2005(14)\u00b0]. In this conformation, hydrogen atoms are located in the equatorial positions of the ring and the N\u2014H bonds are directed to the bottom of the boat (compare torsion angles in Table\u00a01B and C) are not to parallel to each other. The dihedral angles between these rings and central tetra\u00adzine ring are 22.43\u2005(7)\u00b0 (A and B) and 25.71\u2005(6)\u00b0 (A and C). The dihedral angle between rings B and C is 27.13\u2005(7)\u00b0. The overall mol\u00adecular structure could be recognized as a butterfly-like conformation as shown in Fig.\u00a03The central tetra\u00adzine ring (R22(6) ring motif  = 3.2418\u2005(18)\u2005\u00c5 and C34\u22efC61 = 3.3334\u2005(19)\u2005\u00c5], as shown in Fig.\u00a05The crystal packing of (I)et al., 2016et al., 1998A search of the Cambridge Structure Database  were mixed in ethanol (4\u2005ml). The resulting solution was warmed to 343\u2005K and then kept at room temperature. Within two weeks, after slow evaporation of the solvent, two kinds of crystal were obtained in a crystallizer. X-ray studies confirmed that the pink crystals were of the known structure (II), while the yellow crystals were identified as being of a previously unreported structure, i.e. (I)Crystals suitable for X-ray measurements were obtained from a commercially available reagent  and used without further purification. 0.5\u2005mmol of 3,6-bis\u00ad(pyridin-2-yl)-1,2,4,5-tetra\u00adzine and 0.5\u2005mmol of 2-mercapto\u00adpyridine Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901801753X/ff2157sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901801753X/ff2157Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801753X/ff2157Isup3.cmlSupporting information file. DOI: 1884403CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One of these molecules exhibits excellent gelation behaviors in water, and the resultant hydrogels are found to display self-healing properties. Interestingly, the elasticity and strength of the resulting gel can be tuned by the addition of different kinds of Hofmeister salts. The gel formation mechanism was proposed based on the analysis of FT-IR,1HNMR, and XRD, indicating that the main driving force for the self-assembly was the \u03c0-\u03c0 stacking of the benzene rings in the aqueous solution system. Overall, our research provides an efficient approach for facilely tuning the properties of the d-gluconic acetal-based hydrogel.Physical gelation behaviors of a series of The online version of this article (10.1186/s11671-018-2823-8) contains supplementary material, which is available to authorized users. Gels composed of low molecular mass gelators (LMMGs) can be obtained from the self-assembly of LMMGs via supramolecular interactions such as hydrogen bonding, van der Waals interactions, \u03c0-\u03c0 stacking, and so on \u201313. Over4)2SO4 solutions at appropriate concentrations. However, it has only recently been appreciated in supramolecular chemistry and, more specifically, LWMGs-based hydrogels. For example, Mocerino et al. D2O, the signals of C\u2013H protons on the benzene ring of the G1 mixed with kosmotropes anions  moved upfield, which indicated that the \u03c0-\u03c0 stacking effects between benzene rings were enhanced. Correspondingly after the addition of I\u2212, ClO42\u2212, and SCN\u2212, the peaks of C\u2013H protons shifted to 7.993, 8.007, and 8.130\u00a0ppm, respectively. Compared with G1 in pure [d6]D2O, the signals of C\u2013H protons on the benzene ring of the G1 mixed with chaotropes anions  moved downfield, which suggested that the \u03c0-\u03c0 stacking effects between benzene rings were weakened. In Fig.\u00a0\u2212, Br\u2212, and NO3\u2212), the signals of C\u2013H protons on the benzene ring shifted slightly, indicating that the \u03c0-\u03c0 stacking effects between benzene rings were not influenced obviously.1H NMR spectra of the gelator G1 (2.5% . The result was consistent with the macro performance of the gelators (the changing trends of CGC and Tgel). It also reveals that the main driving force for the self-assembly is the \u03c0-\u03c0 stacking force of the benzene rings in the aqueous solution system.From kosmotropes to chaotropes, H-shift on the benzene ring gradually moved toward the low field and the \u03c0-\u03c0 stacking effect between benzene rings was gradually weakened42\u2212 , 2\u03b8\u2009=\u200928.262 (d\u2009=\u20090.31551\u00a0nm), 2\u03b8\u2009=\u200934.071 (d\u2009=\u20090.26292\u00a0nm), and 2\u03b8\u2009=\u200938.843 (d\u2009=\u20090.23165), and the ratio of d-spacing values is about 1:1/\u221a2:1:\u221a3 indicating that the self-assembly of the G1 xerogel from water is composed of hexagonal closs packing possibly [d\u2009=\u20090.38002\u00a0nm), and d\u2009=\u20090.38\u00a0nm is the characteristic of \u03c0-\u03c0 stacking force of the benzene rings. It reveals that the main driving force for the self-assembly is the \u03c0-\u03c0 stacking force of the benzene rings in the aqueous solution system [2SO4 aqueous solution (concentration is 0.5\u00a0M) exhibited four diffraction peaks centered at 2\u03b8\u2009=\u200919.084 (d\u2009=\u20090.46468\u00a0nm), 2\u03b8\u2009=\u200928.075 (d\u2009=\u20090.31757\u00a0nm), 2\u03b8\u2009=\u200933.901 (d\u2009=\u20090.26421\u00a0nm), and 2\u03b8\u2009=\u200938.683 (d\u2009=\u20090.23257\u00a0nm), and it proved that the addition of SO42\u2212 did not affect packing modes of the gelator molecules.While patterns of the G1 xerogel from NaSCN aqueous solution (concentration is 0.5\u00a0M) exhibited diffraction peaks centered at 2\u03b8\u2009=\u200926.184 (d\u2009=\u20090.34006\u00a0nm), 2\u03b8\u2009=\u200930.263 (d\u2009=\u20090.29508\u00a0nm), 2\u03b8\u2009=\u200938.904 (d\u2009=\u20090.23130\u00a0nm), and 2\u03b8\u2009=\u200938.683 (d\u2009=\u20090.23257\u00a0nm), and patterns of the G1 xerogel from aqueous solution  exhibited four diffraction peaks centered 2\u03b8\u2009=\u200923.076 (d\u2009=\u20090.38511\u00a0nm), 2\u03b8\u2009=\u200929.563 (d\u2009=\u20090.30191\u00a0nm), 2\u03b8\u2009=\u200932.101 (d\u2009=\u20090.27860\u00a0nm), and 2\u03b8\u2009=\u200939.165 (d\u2009=\u20090.22982\u00a0nm). The ratio of d-spacing values were all 1:1/\u221a2:1:\u221a3 indicating that the self-assembly of the G1 xerogel from water is mainly composed of hexagonal closs packing [To explore the possible packing modes of the gelator molecules in water with the addition of Hofmeister salts in particular, wide-angle XRD (WXRD) of the G1 xerogels were examined. As shown in Fig.\u00a0possibly . In addin system , 78. In Furthermore, the energy-minimized structure of G1  in in present of Hofmeister anions (concentration is 0.5\u00a0M): (a) Na2SO4, (b) Na2S2O3, (c) Na2HPO4, (d) NaF, (e) H2O, (f) NaCl, (g) NaBr, (h) NaNO3, (i) NaI, (j) NaClO4, (k) NaSCN at 25\u2009\u00b0C, demonstrating high G\u2019values , flowing point . The step-strain measurement shows the recovery ratios of G\u2019 after the first cycle . Figure S2. (a) Frequency sweep of hydrogels from G1  with Hofmeister salts (concentration is 0.5\u2009M) with a fixed strain (0.1%) at 25\u00a0\u00b0C; (b) Rheological data under oscillatory stress experiment on hydrogels from G1  with Hofmeister salts (concentration is 0.5\u2009M) with a fixed frequency (1\u2009Hz) at 25\u00a0\u00b0C; (c) Time scan tests under alternating strain of 0.1% and 100% of G1  with Hofmeister salts (concentration is 0.5\u00a0M) with a fixed frequency at 1\u2009Hz at 25\u00a0\u00b0C. Figure S3. SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in present of Na2SO4 aqueous solution(concentration is 0.5\u00a0M); (b) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v); (c) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in present of NaCl aqueous solution(concentration is 0.5\u00a0M); (d) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in presence of NaSCN aqueous solution (concentration is 0.5\u2009M). Figure S4. The energy-minimized mode of G1. The length of molecular PG16 is 14.6\u2009\u00c5. (DOCX 3013 kb)"}
{"text": "The title compound is built up from a planar quinoxalinone ring system linked through a methyl\u00adene bridge to a 1,2,3-triazole ring, which is inclined by 67.09\u2005(4)\u00b0 to the quinoxalinone ring plane. 16H19N5O, is built up from a planar quinoxalinone ring system linked through a methyl\u00adene bridge to a 1,2,3-triazole ring, which in turn carries an n-butyl substituent. The triazole ring is inclined by 67.09\u2005(4)\u00b0 to the quinoxalinone ring plane. In the crystal, the mol\u00adecules form oblique stacks along the a-axis direction through inter\u00admolecular C\u2014HTrz\u22efNTrz (Trz = triazole) hydrogen bonds, and offset \u03c0-stacking inter\u00adactions between quinoxalinone rings [centroid\u2013centroid distance = 3.9107\u2005(9)\u2005\u00c5] and \u03c0\u2013\u03c0 inter\u00adactions, which are associated pairwise by inversion-related C\u2014HDhydqn\u22ef\u03c0(ring)  inter\u00adactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (52.7%), H\u22efN/N\u22efH (18.9%) and H\u22efC/C\u22efH (17.0%) inter\u00adactions.The title compound, C Diversely substituted quinoxalines and their derivatives embedded with variety of functional groups are important biological agents and a significant amount of research activity has been directed towards this class of compounds. These mol\u00adecules exhibit a wide range of biological applications and are potentially useful in medicinal chemistry research and have therapeutic applications such as anti\u00admicrobial methyl substituent projecting well out of the mean plane of the di\u00adhydro\u00adquinxalone unit, as indicated by the C1\u2014N2\u2014C10\u2014C11 torsion angle of 90.85\u2005(16)\u00b0. The n-butyl group is oriented in the opposite direction as seen from the N4\u2014N3\u2014C13\u2014C14 torsion angle of \u221295.26\u2005(16)\u00b0 N3 Fig.\u00a01. The di\u00ad)\u00b0 Fig.\u00a02.a-axis direction through inter\u00admolecular C\u2014HTrz\u22efNTrz (Trz = triazole) hydrogen bonds (Table\u00a01A (C1\u2013C6) and B (N1/N2/C1/C6\u2013C8) rings  and \u03c0-inter\u00adactions between the C8=O1 carbonyl group and the B rings . Pairs of stacks are associated through C\u2014HDhydqn\u22ef\u03c0  inter\u00adactions, generating small, diamond-shaped channels along the a-axis direction  generated 37 hits. Of these, the ones most comparable to the title mol\u00adecule have R1 = CH3 and R = CH2C\u2261CH methyl methyl isomer shows that the latter has a U shape with the R group extending back over the bicyclic unit as the result of an intra\u00admolecular C\u2014H\u22efO hydrogen bond from the \u03b1 hydrogen of the butyl group while in the former, the more remote position of the butyl group on the triazole ring disfavours such an inter\u00adaction and the mol\u00adecule adopts a Z shape. This conformation is favoured by the opportunity for \u03c0-stacking and C\u2014H\u22ef\u03c0(ring) inter\u00adactions in the crystal.A search of the CSD , and those delineated into H\u22efH, H\u22efN/N\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efC, O\u22efC/C\u22efO, N\u22efC/C\u22efN and N\u22efN contacts \u2013(i), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH contributing 52.7% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule. The split spike with the tip at de = di = 1.13\u2005\u00c5 in Fig.\u00a06b) is due to the short inter\u00adatomic H\u22efH contacts (Table\u00a02c), contribute 18.9% to the HS (Table\u00a02de + di = 2.23\u2005\u00c5. In the presence of weak C\u2014H\u22ef\u03c0 inter\u00adactions (Table\u00a01d), with the tips at de + di = 2.65\u2005\u00c5 (Table\u00a02e)] contacts  analysis \u2013(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efN/N\u22efH, H\u22efC/C\u22efH and H\u22efO/O\u22efH inter\u00adactions suggests that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing (Hathwar H)-one (0.68\u2005mmol) in ethanol (15\u2005mL) was added 1-azido\u00adbutane (1.03\u2005mmol). The reaction mixture was stirred under reflux for 72\u2005h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue was purified by column chromatography on silica gel by using as eluent the mixture (hexa\u00adne/ethyl acetate 8:2). The solid product obtained was crystallized from ethanol to afford colourless crystals in 78% yield.To a solution of 3-methyl-1-(prop-2-yn\u00adyl)-3,4-di\u00adhydro\u00adquinoxalin-2 I, global. DOI: 10.1107/S205698901801589X/xu5949Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801589X/xu5949Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901801589X/xu5949Isup4.cmlSupporting information file. DOI: 1878133CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Parallel chains inter\u00adact through N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking of the tris\u00adubstituted phenyl rings.In the title pyrazoline derivative, the pyrazoline ring makes angles of 86.73\u2005(12) and 13.44\u2005(12)\u00b0 with the tris\u00adubstituted and disubstituted benzene rings, respectively. In the crystal structure, the mol\u00adecules are connected into chains running in the  16H16N2O3\u00b7H2O, the pyrazoline ring has an envelope conformation with the substituted sp2 C atom on the flap. The pyrazoline ring makes angles of 86.73\u2005(12) and 13.44\u2005(12)\u00b0 with the tris\u00adubstituted and disubstituted benzene rings, respectively. In the crystal structure, the mol\u00adecules are connected into chains running in the b-axis direction by O\u2014H\u22efN hydrogen bonding. Parallel chains inter\u00adact through N\u2014H\u22efO hydrogen bonds and \u03c0\u2013\u03c0 stacking of the tris\u00adubstituted phenyl rings. The major contribution to the surface contacts are H\u22efH contacts (44.3%) as concluded from a Hirshfeld surface analysis.In the title pyrazoline derivative, C There is a clear difference in both C\u2014N bond distances in the pyrazoline ring: N1=C5 shows double-bond character [1.287\u2005(3)\u2005\u00c5] while N2\u2014C3 [1.496\u2005(3)\u2005\u00c5] is a single bond. The dihedral angle between the two benzene rings is 80.66\u2005(11)\u00b0. The planes of the C6\u2013C11 benzene ring (r.m.s. deviation = 0.004\u2005\u00c5) and the pyrazoline ring make an angle of 86.73\u2005(12)\u00b0. For the C15\u2013C20 benzene ring (r.m.s. deviation = 0.006\u2005\u00c5), the dihedral angle with the pyrazoline ring is only 13.44\u2005(12)\u00b0. Both the hy\u00addroxy and meth\u00adoxy substituents of the C6\u2013C11 phenyl group are within the phenyl plane with deviations of 0.011\u2005(1) (O12), 0.166\u2005(2) (C13) and \u22120.057\u2005(2)\u2005\u00c5 (O14).The title compound crystallizes in the ortho\u00adrhom\u00adbic space group it Fig.\u00a01. The pyr2, the O22 water mol\u00adecule bridges three mol\u00adecules by O\u2014H\u22efN and O\u2014H\u22efO hydrogen-bonding inter\u00adactions with the N1 atom and the O21-hy\u00addroxy group  = 3.6627\u2005(11)\u2005\u00c5; slippage 1.442\u2005\u00c5; Cg1 is the centroid of the C6\u2013C11 ring]. In addition, a C\u2014H\u22efO inter\u00adaction is observed in the crystal packing . The associated two-dimensional fingerprint plots  followed by recip\u00adrocal C\u22efH/H\u22efC contacts . Significant contributions come from reciprocal O\u22efH/H\u22efO (20.7%) and N\u22efH/H\u22efN (7.0%) contacts, which appear as two symmetrical spikes at de + di = 1.65 and 1.80\u2005\u00c5, respectively . A further small contribution is from C\u22efC contacts .The Hirshfeld surface -4,5-di\u00adhydro-1H-pyrazol-5-yl]phenol \u00b0, that between the pyrazoline ring and the nitro\u00adphenyl ring is 9.7\u2005(1)\u00b0 and that between the pyrazoline ring and the meth\u00adoxy\u00adphenol ring is 56. 78\u2005(9)\u00b0. The second structure, 3-(2\u2032-hy\u00addroxy-5\u2032-meth\u00adoxy-phen\u00adyl)-5-(3-meth\u00adoxy-4-hy\u00addroxy\u00adphen\u00adyl)-4,5-di\u00adhydro-1H-pyrazole \u00b0, while the dihedral angles between the pyrazoline ring and the phenyl rings at atom C3 and C5 are 12.1\u2005(1) and 68.2\u2005(1)\u00b0, respectively.A search of the Cambridge Structural Database -3-(4-Hy\u00addroxy-3-meth\u00adoxy\u00adphen\u00adyl)-1-(4-hy\u00addroxy\u00adphen\u00adyl)prop-2-en-1-one, 1, was synthesized as described in a previous study -4,5-di\u00adhydro-1H-pyrazol-5-yl)-2-meth\u00adoxy\u00adphenol (2):1 (0.01\u2005mol), 2.5\u2005mL of hydrazine hydrate and 25\u2005mL of ethanol was refluxed at 353\u2005K for 2\u2005h. After pouring the reaction mixture into 200\u2005mL of ice\u2013water, the crude solid product was isolated by vacuum filtration, washed several times with cold water and recrystallized from ethanol:water (1:2) to give yellow crystals , m.p. 465\u2005K. 1H NMR [Bruker XL-500, 500\u2005MHz, d6-DMSO, \u03b4 (ppm), J (Hz), see Fig.\u00a06d, 1H, J = 8.0, H2); 3.75 ; 6.74 ; 6.95 , 4.67 ; 3.30 ; 2.76 , 7.45 ; 6.76 .A mixture of chalcone A and H22B were found in difference electron density maps and refined freely. The other H atoms were placed in idealized positions and included as riding contributions with Uiso(H) values of 1.2Ueq or 1.5Ueq of the parent atoms, with C\u2014H distances of 0.93 (aromatic), 0.98 (CH), 0.97 (CH2) and 0.96\u2005\u00c5 (CH3). In the final cycles of refinement, eight outliers were omitted.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019013379/sj5579sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019013379/sj5579Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013379/sj5579Isup3.cmlSupporting information file. DOI: 1956698, 1956698CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "S(6) ring motif. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming layers parallel to (011). \u03c0\u2013\u03c0 stacking inter\u00adactions complete the three-dimensional network.The asymmetric unit contains two crystallographically independent mol\u00adecules in which the dihedral angles between the benzene rings are 13.26\u2005(5) and 7.87\u2005(5)\u00b0. An intra\u00admolecular O\u2014H\u22efN hydrogen bonds results in the formation of an  15H12N2O2, contains two crystallographically independent mol\u00adecules in which the dihedral angles between the benzene rings in each are 13.26\u2005(5) and 7.87\u2005(5)\u00b0. An intra\u00admolecular O\u2014H\u22efN hydrogen bonds results in the formation of an S(6) ring motif. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds, forming layers parallel to (011). In addition, \u03c0\u2013\u03c0 stacking inter\u00adactions with centroid\u2013centroid distances in the range 3.693\u2005(2)\u20133.931\u2005(2)\u2005\u00c5 complete the three-dimensional network.The asymmetric unit of the title compound, C The title compound displays a trans configuration with respect to the C8=N1 and C23=N3 double bonds. In each independent mol\u00adecule, an intra\u00admolecular O\u2014H\u22efN hydrogen bond (Table\u00a01G (N1/H2/O2/C2/C7/C8) and H (O4/H4/N3/C23/C22/C17)]; these are oriented at dihedral angles of A/G = 1.31\u2005(5) and C/H = 0.42\u2005(5)\u00b0 with respect to the adjacent benzene rings.The asymmetric unit of the title compound contains two crystallographically independent mol\u00adecules  = 3.860\u2005(2)\u2005\u00c5, Cg2\u22efCg2 = 3.693\u2005(2)\u2005\u00c5 and Cg2\u22efCg4 = 3.931\u2005(2)\u2005\u00c5; where Cg1, Cg2, Cg3 and Cg4 are the centroids of the C2\u2013C7, C9\u2013C14, C17\u2013C22 and C24\u2013C29 rings, respectively  Fig.\u00a02. In addily Fig.\u00a03.\u03c0\u2013\u03c0* type transition. The frontier orbital gap helps to characterize the chemical reactivity and the kinetic stability of the mol\u00adecule. A mol\u00adecule with a small frontier orbital gap is generally associated with a high chemical reactivity, low kinetic stability and is also termed a soft mol\u00adecule. DFT quantum-chemical calculations for the title compound were performed at the B3LYP/6\u2013311G level  and the lowest lying unoccupied mol\u00adecular orbitals (LUMOs) are termed frontier mol\u00adecular orbitals (FMOs), which play an important role in the optical and electric properties of compounds, as well as in their quantum chemistry and UV\u2013vis spectra. According to mol\u00adecular orbital theory, an inter\u00adaction between HOMO and LUMO orbitals of a structure gives rise to a et al., 2002Mol\u00adecular electrostatic potential (MEP) surface analysis is a technique of mapping electrostatic potential onto the iso-electron density surface, providing information about the reactive sites. The surface simultaneously displays mol\u00adecular size and shape and the electrostatic potential value. In the colour scheme adopted, red indicates an electron-rich region with a partially negative charge and blue an electron-deficient region with partially positive charge, light blue indicates a slightly electron-deficient region, yellow a slightly electron-rich region and green a neutral region -2-[(2-hy\u00addroxy-5-meth\u00adoxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile moiety: (Z)-2-[(2-hy\u00addroxy-1-naphth\u00adyl)methyl\u00adene\u00adamino]\u00adbenzo\u00adnitrile -2-[(5-bromo-2-hy\u00addroxy\u00adbenzyl\u00adidene)amino]\u00adbenzo\u00adnitrile \u00adbenzo\u00adnitrile\u00ad-2-\u00adbenzo\u00adnitrile -2-(4-di\u00adethyl\u00adamino-2-hy\u00addroxy\u00adbenzyl\u00adidene\u00adamino)\u00adbenzo\u00adnitrile -2-[amino]\u00adbenzo\u00adnitrile  ring motif, similar to title compound.A search of the Cambridge Structural Database  in ethanol (15\u2005ml) and 2-amino\u00adbenzo\u00adnitrile  in ethanol (15\u2005ml). The reaction mixture was stirred for 5\u2005h under reflux. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2Ueq(C) or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019008077/lh5907sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019008077/lh5907Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019008077/lh5907Isup3.cmlSupporting information file. DOI: 1912294CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ribbons are connected into layers parallel to the bc plane by inversion-related C\u2014HBnz\u22ef\u03c0(ring) inter\u00adactions.The pyridazine ring deviates slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of mol\u00adecules extending along the  22H16N4O2, contains two pyridine rings and one meth\u00adoxy\u00adcarbonyl\u00adphenyl group attached to a pyridazine ring which deviates very slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of mol\u00adecules extending along the a-axis direction are formed by C\u2014HMthy\u22efOCarbx (Mthy = methyl and Carbx = carboxyl\u00adate) hydrogen bonds. The ribbons are connected into layers parallel to the bc plane by C\u2014HBnz\u22ef\u03c0(ring) (Bnz = benzene) inter\u00adactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (39.7%), H\u22efC/C\u22efH (27.5%), H\u22efN/N\u22efH (15.5%) and O\u22efH/H\u22efO (11.1%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, C\u2014HMthy\u22efOCarbx hydrogen-bond energies are 62.0 and 34.3\u2005kJ\u2005mol\u22121, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G level are com\u00adpared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title com\u00adpound, C O-triphosphate can be used as a potential substrate for fluorescence detection and imaging of DNA pyridazine derivatives are a versatile class of nitro\u00adgen-containing heterocyclic com\u00adpounds and they constitute useful inter\u00admediates in organic syntheses. Also, this nucleus is one of the important ligands in the field of coordination chemistry research. 5--2\u2032-de\u00adoxy\u00aduridine-5\u2032-B (atoms N2/N3/C6\u2013C9), deviates slightly from planarity by \u00b10.021\u2005(1)\u2005\u00c5 (r.m.s. deviation = 0.0134\u2005\u00c5)  and C (N4/C10\u2013C14), are inclined to the mean plane of the pyridazine ring, B, by 18.68\u2005(6) and 38.40\u2005(6)\u00b0, respectively, while the benzene ring, D (C15\u2013C20), is inclined to it by 62.59\u2005(5)\u00b0. The pyridine and benzene rings are oriented at dihedral angles of A/C = 25.16\u2005(4)\u00b0, A/D = 48.94\u2005(4)\u00b0 and C/D = 59.13\u2005(4)\u00b0. The plane of the carboxyl group (defined by atoms C18/C21/O1/O2) is twisted out of the plane of the benzene ring, D, by 22.88\u2005(5)\u00b0.The title com\u00adpund contains two pyridine rings and one meth\u00adoxy\u00adcarbonyl\u00adphenyl group attached to a pyridazine ring, where the central pyridazine ring, \u00c5) Fig.\u00a01. The plaa-axis direction are formed by C22\u2014H22C\u22efO1v hydrogen bonds  and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efN/N\u22efH, H\u22efO/O\u22efH, C\u22efC and C\u22efN/N\u22efC contacts \u2013(g), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH contributing 39.7% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule with the tip at de = di = 1.10\u2005\u00c5, due to the short inter\u00adatomic H\u22efH contacts (Table\u00a02c) with the tips at de + di = 2.75\u2005\u00c5. The pair of scattered points of wings resulting in the fingerprint plots delineated into H\u22efN/N\u22efH  contacts, with a 15.5% contribution to the HS, has a symmetrical distribution of points with the edges at de + di = 2.58\u2005\u00c5 (Table\u00a02e), with an 11.1% contribution to the HS, arises from the O\u22efH/H\u22efO contacts  have an arrow-shaped distribution of points with the tip at de = di = 13.50\u2005\u00c5. Finally, the tiny characteristic wings resulting in the fingerprint plots shown in Fig.\u00a06g, a 2.4% contribution to the HS, arises from the C\u22efN/N\u22efC contacts  analysis \u2013(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH, H\u22efN/N\u22efH and H\u22efO/O\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing   is the sum of the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange\u2013repulsion (Erep) energies  were calculated as \u221223.9 (Eele), \u22124.3 (Epol), \u221276.2 (Edis), 53.0 (Erep) and \u221262.0 (Etot) for the C22\u2014H22C\u22efO1 hydrogen-bonding inter\u00adaction, and \u221222.0 (Eele), \u22128.5 (Epol), \u221228.5 (Edis), 32.3 (Erep) and \u221234.3 (Etot) for the C22\u2014H22B\u22efO1 hydrogen-bonding inter\u00adaction.The inter\u00admolecular inter\u00adaction energies were calculated using the CE\u2013B3LYP/6-31G energy model available in via density functional theory (DFT) using the standard B3LYP functional and 6-311G basis-set calculations , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are all recorded in Table\u00a04E = ELUMO \u2212 EHOMO] of the mol\u00adecule is about 1.8908\u2005eV, and the frontier mol\u00adecular orbital (FMO) energies, i.e. EHOMO and ELUMO, are \u22124.3680 and \u22122.4772\u2005eV, respectively.The optimized structure of the title com\u00adpound, (I)et al., 2019a2N1,N6]copper(II) bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonate) pyridazine]bis\u00ad(\u03bc-2-azido)\u00addizaidodicopper monohydrate] meth\u00adyl]phenyl analogue has been reported  to afford colourless crystals .3,6-Bis(pyridin-2-yl)-1,2,4,5-tetra\u00adzine (4\u2005mmol) was dissolved in toluene (20\u2005ml), and then 1 equiv. of methyl 4-ethynylbenzoate was added and the reaction mixture was stirred and refluxed at temperatures between 413 and 453\u2005K. The solvent was then evaporated. The product obtained was separated by chromatography on a column of silica gel. The isolated solid was recrystallized from hexa\u00adne\u2013di\u00adchloro\u00admethane  I, global. DOI: 10.1107/S2056989019013732/lh5927Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013732/lh5927Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019013732/lh5927Isup4.cmlSupporting information file. DOI: 1958277, 1958277CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The pyrrolidine ring makes a dihedral angle of 14.83\u2005(12)\u00b0 with the 3,4-di\u00admeth\u00adoxy\u00adphenyl ring, which are attached to each other by an extended N\u2014CH2\u2014CH2\u2014Car bridge. In the crystal, the structure features C\u2014H\u22efO inter\u00admolecular hydrogen bonds, an offset \u03c0\u2013\u03c0 inter\u00adaction [inter\u00adcentroid distance = 3.564\u2005(1)\u2005\u00c5] and a C\u2014Cl\u22ef\u03c0 inter\u00adaction. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015PLATON. The solvent contribution was not included in the reported mol\u00adecular weight and density.In the title compound, CSpek 2015. Acta Cr The two five-membered rings, A (C2/C3/C5\u2013C7) and B (C5\u2013C9), have envelope conformations with atom C6 as the flap: puckering parameters and the smallest displacement asymmetric parameters are Q2 = 0.619\u2005(2)\u2005\u00c5, \u03c62 = 108.6\u2005(2)\u00b0 and \u0394s = 1.09\u00b0 for ring A, and Q2 = 0.582\u2005(2)\u2005\u00c5, \u03c62 = 215.5\u2005(2)\u00b0 and \u0394s = 0.74\u00b0 for ring B. Atom C6 is displaced from the mean plane through the other four atoms by 0.908\u2005(2)\u2005\u00c5 in ring A and 0.875\u2005(2)\u2005\u00c5 in ring B. The dihedral angle between the pyrrolidine ring (N1/C1\u2013C4) and the benzene ring (C12\u2013C17) is 14.83\u2005(12)\u00b0, with the torsion angle N1\u2014C10\u2014C11\u2014C12 being 175.8\u2005(3)\u00b0. The lengths of the C\u2014Cl bonds involving the chlorine atoms attached to the C8=C9 double bond are 1.692\u2005(2)\u2005\u00c5 for C8\u2014Cl2 and 1.692\u2005(2)\u2005\u00c5 for C9\u2014Cl3. The lengths of the bonds to chlorine atoms attached to the single C\u2014C bonds vary from 1.744\u2005(2) to 1.768\u2005(2)\u2005\u00c5. These value are close to those found in similar compounds; see \u00a74 Database survey.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01A\u22efO2i hydrogen bonds link the molecules to form a cyclic Cg1\u22efCg5iii of 3.564\u2005(1)\u2005\u00c5 dec-8-ene-3,5-dione \u00b0 compared to 175.8\u2005(3)\u00b0 in the title compound.A search of the Cambridge Structural Database \u20131.692\u2005(2)\u2005\u00c5 and 1.744\u2005(2)\u20131.768\u2005(2)\u2005\u00c5, respectively.In all 17 structures, the five-membered ring has envelope conformations and the six-membered ring a boat conformation. The bond lengths and bond angles are very similar to those reported here for the title compound. For example, the C2CO3 and dried over anhydrous Na2SO4. It was then filtered and the filtrate was concentrated under reduced pressure followed by silica gel column purification to afford the title compound in 82% yield. Colourless block-shaped crystals were obtained by slow evaporation of a solution in ethanol.2- ethanamine (1 equiv.) and 1,4,5,6,7,7-hexa\u00adchloro-5- norbornene \u22122,3-di\u00adcarb\u00adoxy\u00adlic anhydride (1 equiv.) were stirred at room temperature in dry ethyl acetate for 30\u2005min. The ethyl acetate was removed under reduced pressure and the resulting residue was dissolved in toluene. To this reaction mixture was added acetyl chloride (5 equiv.) and refluxed for 1\u2005h. The reaction mixture was brought to room temperature and washed with aqueous NaUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. The contribution of the disordered solvent to the scattering was removed using the SQUEEZE routine of PLATON  Global, I. DOI: 10.1107/S2056989019004109/su5485Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004109/su5485sup4.pdfCSD search S1. DOI: Click here for additional data file.10.1107/S2056989019004109/su5485Isup4.cmlSupporting information file. DOI: 1905872CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, C\u2014HOxqn\u22efOEthx and C\u2014HPh\u00adyl\u22efOCarbx  weak hydrogen bonds link the mol\u00adecules into a three-dimensional network sturucture. A \u03c0\u2013\u03c0 inter\u00adaction between the constituent rings of the oxo\u00adquinoline unit, with a centroid\u2013centroid distance of 3.675\u2005(1)\u2005\u00c5 may further stabilize the structure. Both terminal ethyl groups are disordered over two sets of sites. The ratios of the refined occupanies are 0.821\u2005(8):0.179\u2005(8) and 0.651\u2005(18):0.349\u2005(18). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (53.9%), H\u22efO/O\u22efH (28.5%) and H\u22efC/C\u22efH (11.8%) inter\u00adactions. Weak inter\u00admolecular hydrogen-bond inter\u00adactions and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Density functional theory (DFT) geometric optimized structures at the B3LYP/6-311G level are com\u00adpared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO mol\u00adecular orbital behaviour was elucidated to determine the energy gap.The title com\u00adpound, C Quinolone derivatives have constituted an important class of heterocyclic com\u00adpounds which, even when part of a com\u00adplex mol\u00adecule, possesses a wide spectrum of biological activities, such as anti\u00adcancer  and B (C4\u2013C9), of the oxo\u00adquinoline unit are oriented at a dihedral angle of 1.04\u2005(6)\u00b0. Thus, they are almost coplanar, with a maximum deviation of 0.017\u2005(3)\u2005\u00c5 for atom C7. Atoms O1 and C10 deviate only by 0.007\u2005(2) and 0.022\u2005(2)\u2005\u00c5 from that plane and so are essential coplanar. The acetate substituent is nearly perpendicular to that plane, with a torsion angle of C1\u2014N1\u2014C10\u2014C11 = \u2212104.8\u2005(2)\u00b0. The mean plane of the phenyl ring, C (C19\u2013C24), is oriented with respect to the oxo\u00adquinoline unit at a dihedral angle of 68.17\u2005(6)\u00b0. The carboxyl groups, O5/O6/C11 and O3/O4/C16, are twisted out of coplanarity with the best least-squares plane of the oxo\u00adquinoline unit and phenyl ring C by dihedral angles of 79.7\u2005(2) and 62.9\u2005(2)\u00b0, respectively.The title mol\u00adecule is com\u00adposed of ethyl 2-acetate and 4-[(2-eth\u00adoxy-2-oxoeth\u00adyl)(phen\u00adyl)carbomo\u00adyl] units Fig.\u00a01. The meaOxqn\u22efOEthx and C\u2014HPh\u00adyl\u22efOCarbx  hydrogen bonds (Table\u00a01i.e.A (N1/C1\u2013C4/C9) and B (C4\u2013C9), of the oxo\u00adquinoline unit, with Cg1\u22efCg2i = 3.675\u2005(1)\u2005\u00c5 , may further stabilize the structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for crystal packing are from H\u22efH (53.9%), H\u22efO/O\u22efH (28.5%) and H\u22efC/C\u22efH (11.8%) inter\u00adactions. Weak inter\u00admolecular hydrogen-bond inter\u00adactions and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.In the crystal, weak C\u2014Hs Table\u00a01 link thes Table\u00a01. A \u03c0\u2013\u03c0 cCrystalExplorer17.5  and those delineated into H\u22efH, H\u22efO/O\u22efH, H\u22efC/C\u22efH, C\u22efC and O\u22efC/C\u22efO contacts \u2013(f), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH, contributing 53.9% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule, with the tip at de = di = 1.05\u2005\u00c5, due to the short inter\u00adatomic H\u22efH contacts. The pair of characteristic wings resulting in the fingerprint plot delineated into H\u22efO/O\u22efH contacts  has a 28.5% contribution to the HS and is viewed as a pair of spikes with the tips at de + di = 2.30\u2005\u00c5. In the absence of weak C\u2014H\u22ef\u03c0 inter\u00adactions, the pair of characteristic wings resulting in the fingerprint plot delineated into H\u22efC/C\u22efH contacts , with a 11.8% contribution to the HS and are viewed as a pair of spikes with the tip at de + di = 2.83\u2005\u00c5. The C\u22efC contacts  have an arrow-shaped distribution of points with the tip at de = di = 1.81\u2005\u00c5. Finally, the pair of the scattered points of wings from the fingerprint plot are delineated into O\u22efC/C\u22efO  contacts, with a 1.1% contribution to the HS, and has a nearly symmetrical distribution of points with the edges at de + di = 3.15\u2005\u00c5.In order to visualize the inter\u00admolecular inter\u00adactions in the title com\u00adpound, a Hirshfeld surface (HS) analysis \u2013(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of weak H-atom contacts in establishing the packing structure. The large number of H\u22efH, H\u22efO/O\u22efH and H\u22efC/C\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and weak hydrogen-bond inter\u00admolecular inter\u00adactions play major roles in the crystal packing  com\u00adputational calculations using a standard B3LYP functional and a 6-311G basis set , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3), which are listed in Table\u00a03E = ELUMO \u2212 EHOMO] of the mol\u00adecule was about 4.2091\u2005eV, and the frontier mol\u00adecular orbital (FMO) energies, i.e. EHOMO and ELUMO, were \u22126.1141 and \u22121.9050\u2005eV, respectively.The geometry optimized structure of the title com\u00adpound in the gas phase was generated theoretically et al., 2016bet al., 2019aet al., 2014et al., 2012et al., 2018aet al., 2015A non-a\u00adlkylated analogue, namely quinoline and its derivatives, has been reported  in di\u00admethyl\u00adformamide  were added ethyl bromo\u00adacetate (4.16\u2005mmol), K2CO3 (5.67\u2005mmol) and tetra\u00adbutyl\u00adammonium bromide . The reaction mixture was stirred at room temperature for 6\u2005h. After removal of the salts by filtration, the DMF was evaporated under reduced pressure and the resulting residue was dissolved in di\u00adchloro\u00admethane. The organic phase was dried with Na2SO4 and then concentrated under reduced pressure. The pure com\u00adpound was obtained by column chromatography using as eluate hexa\u00adne/ethyl acetate (3:1 v/v). The isolated solid was recrystallized from hexa\u00adne\u2013diethyl acetate (1:1 v/v) to afford colourless crystals .To a solution of 2-oxo-2 and CH3 H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = kUeq(C), where k = 1.5 for CH3 H atoms and k = 1.2 for other H atoms. The terminal ethyl groups are disordered with an occupancy ratio of 0.821\u2005(8):0.179\u2005(8) for C12 and C13, and 0.651\u2005(18):0.349\u2005(18) for C17 and C18.The experimental details, including the crystal data, data collection and refinement, are summarized in Table\u00a0410.1107/S2056989019014154/lh5924sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019014154/lh5924Isup2.hklStructure factors: contains datablock(s) I. DOI: 1959642, 1959642CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Glycyrrhiza on the Diuretic Function of Euphorbia kansui: An Ascites Mouse Model\u201d [Y1 = 6.331\u2217X12\u2217X2 \u2212 4.16\u2217X12 \u2212 0.1637/X22 + 10.94 , displayed in Figure 3(a). Ascites volume/body weight of mice was defined as a dependent variable Y2 using the multivariate stepwise regression equation Y2 = 0.06416\u2217X1\u2217X22 \u2212 0.006046/X22 + 0.3062  as shown in Figure 4(a).\u201d should be corrected toIn the article titled \u201cEffect ofe Model\u201d , there wY1 = 6.331\u2217X12\u2217X2 \u2212 4.16\u2217X12 \u2212 0.1637/X22 + 11.62 , displayed in Figure 3(a). Ascites volume/body weight of mice was defined as a dependent variable Y2 using the multivariate stepwise regression equation Y2 = 0.06416\u2217X1\u2217X22 \u2212 0.006046/X22 + 0.4288  as shown in Figure 4(a).\u201d\u201cAscites volume was defined by the stepwise equation, In addition, the photograph of the renal pathological changes in the Furosemide group in Figure 7(b)-Furo was misplaced. The corrected version of the figure with its description is shown below:"}
{"text": "II atom bridging two six-coordinate ZnII atoms in which the two terminal ZnII cations adopt distorted octa\u00adhedral geometries and the central ZnII cation adopts a distorted tetra\u00adhedral geometry.The structure is reported of a complex containing a trinuclear Zn cation lying on a crystallographic twofold axis. It consists of a tetra\u00adhedral Zn 3(C14H11Br2N2O)4](ClO4)2\u00b72CH3CN, crystallizes as a symmetrical trinuclear cation with all three metal atoms being located on a twofold rotation axis. It contains a tetra\u00adhedral ZnII atom that bridges two six-coordinate ZnII atoms. The complex contains N- and O-donor atoms of four tridentate 2,4-di\u00adbromo-6-{[2-(pyridin-2-yl)eth\u00adyl]imino\u00admeth\u00adyl}phenolate ligands. The ratio of ZnII atoms to ligands is 3:4. The two terminal ZnII cations adopt distorted octa\u00adhedral geometries and the central ZnII cation adopts a distorted tetra\u00adhedral geometry. In the cation there are \u03c0\u2013\u03c0 inter\u00adactions between the di\u00adbromo\u00adphenyl rings, as well as halogen-bonding inter\u00adactions between the di\u00adbromo\u00adphenyl rings in the cation, which stabilize its conformation. In addition, there are C\u2014H\u22efO inter\u00adactions between the anions and both the cations and solvent mol\u00adecules as well as C\u2014H\u22efN inter\u00adactions between the cation and solvent mol\u00adecules. These inter\u00adspecies inter\u00adactions link the cations, anions and solvent mol\u00adecules into a complex three-dimensional arrayThe title compound, [Zn Some enzymes containing zinc(II) include carbonic anhydrase, carb\u00adoxy\u00adpeptidase, and phosphatase 4](ClO4)2\u00b72CH3CN, 1, contains a complex cation as well as perchlorate anions and aceto\u00adnitrile solvent mol\u00adecules and thus has an overall stoichiometry of [Zn3(L)4](ClO4)2.2CH3CN where L is 2,4-di\u00adbromo-6-{[(2-(pyridin-2-yl)eth\u00adyl]imino\u00admeth\u00adyl}phenolate. The compound crystallizes in the monoclinic space group C2/c and the cation consists of the four equivalent L ligands, uniformly coordin\u00adated to three ZnII cations.The crystal structure of the title compound, [Zn3(L)4]2+, lies on a crystallographic twofold axis  to 120.11\u2005(8)\u00b0 and Zn\u2014O bond lengths of 1.9512\u2005(19) and 1.9602\u2005(19)\u2005\u00c5. For the six-coordinate terminal zinc atoms, as is usual for complexes containing both Schiff base imine and pyridine N donors, the former form shorter bonds [Zn1\u2014N1 = 2.122\u2005(2)\u2005\u00c5 and Zn3\u2014-N3 = 2.067\u2005(2)\u2005\u00c5] while the latter form longer bonds [Zn1\u2014N2 = 2.148\u2005(2)\u2005\u00c5 and Zn3\u2014N4 = 2.177\u2005(2)\u2005\u00c5] to zinc. The metrical parameters involving the bridging phenolate O donors are significantly different. The bonds to the central Zn2 are considerably shorter than those to the terminal Zn1 and Zn3  and the bridging angles are Zn1\u2014O1\u2014Zn2 = 96.78\u2005(8)\u00b0 and Zn2\u2014O2\u2014Zn3 = 93.73\u2005(8)\u00b0. The distortion from an octa\u00adhedral geometry can be seen from the cis and trans angles which range from 77.49\u2005(10) to 98.19\u2005(9)\u00b0 and 160.47\u2005(13) to 173.41\u2005(12)\u00b0, respectively. Since all three Zn atoms lie on the twofold axis, the Zn1\u2014Zn2\u2014Zn3 bond angle is exactly 180\u00b0. These metrical parameters are similar to those found in the most closely similar complex  to 2.117\u2005(4)\u2005\u00c5 and 2.140\u2005(4) to 2.176\u2005(4)\u2005\u00c5, respectively. In this complex there is no crystallographically imposed symmetry; however, the Zn\u2014Zn\u2014Zn bond angle is still close to 180 at 172.51\u2005(3)\u00b0.The trinuclear complex cation,  as well as halogen-bonding inter\u00adactions  between the di\u00adbromo\u00adphenyl rings in the cation, which stabilize its conformation. In addition there C\u2013H\u22efO inter\u00adactions between the anions and both the cations and solvent mol\u00adecules as well as C\u2014H\u22efN inter\u00adactions between the cation and solvent mol\u00adecules (Table\u00a01In the cation there are \u03c0\u2013\u03c0 inter\u00adactions between the di\u00adbromo\u00adphenyl rings imino}\u00admeth\u00adyl)phenolato type ligands gave 26 hits of which only one was similar to the title compound in that it contained a trinuclear Zn complex where this ligand was acting as a bridging group to the central Zn atom 2\u00b76H2O  with no added base. The mixture was stirred at room temperature overnight. The methanol was removed by rotary evaporation. The product was crystallized by slow evaporation of a solution in acetonitrile giving pale-yellow to colorless crystals.2-(2-Pyrid\u00adyl)ethyl\u00adamine  was dissolved in 50\u2005mL of methanol. 3,5-Di\u00adbromo\u00adsalicyl\u00adaldehyde  was added to the solution and the mixture was refluxed for 5\u2005h. The zinc(II) complex was prepared by reacting the ligand in 50\u2005ml of methanol with Zn(ClOUiso(H) = 1.2Ueq(C) or 1.5Ueq(CH3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018012100/jj2202sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018012100/jj2202Isup2.hklStructure factors: contains datablock(s) I. DOI: 1863971CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Reaction of this complex with piperidine leads to partial decoordination of the 2-pyridyl\u00adphosphine in the product, [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br], which displays an intra\u00admolecular hydrogen bond between the piperidine aminic hydrogen atom and the uncoordinated pyridyl group, with D\u22efA = 2.992\u2005(9)\u2005\u00c5.The reaction of the ligand di\u00adpyridyl\u00adphosphine with (Re(CO) 2N,P]rhenium(I) chloro\u00adform disolvate, [ReBr(C17H14NP)(CO)3]\u00b72CHCl3 or \u00b72CHCl3, (I\u00b72CHCl3), is best described as a distorted octa\u00adhedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-di\u00adphenyl\u00adpyridyl\u00adphosphine ligand. Hirshfeld surface analysis shows that C\u2014Cl\u22efH inter\u00adactions contribute 26%, the distance of these inter\u00adactions are between 2.895 and 3.213\u2005\u00c5. The reaction between I and piperidine (C5H11N) at 313\u2005K in di\u00adchloro\u00admethane leads to the partial decoord\u00adination of the pyridyl\u00adphosphine ligand, whose pyridyl group is replaced by a piperidine mol\u00adecule, and the complex bromido\u00adtricarbon\u00adyl[diphen\u00adyl(pyridin-2-yl)phosphane-\u03baP](piperidine-\u03baN)rhenium(I), [ReBr(C5H11N)(C17H14NP)(CO)3] or [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II). The mol\u00adecule has an intra\u00admolecular N\u2014H\u22efN hydrogen bond between the non-coordinated pyridyl nitro\u00adgen atom and the amine hydrogen atom from piperidine with D\u22efA = 2.992\u2005(9)\u2005\u00c5. Thermogravimetry shows that I\u00b72CHCl3 losses 28% of its mass in a narrow range between 318 and 333\u2005K, which is completely consistent with two solvating chloro\u00adform mol\u00adecules very weakly bonded to I. The remaining I is stable at least to 573\u2005K. In contrast, II seems to lose solvent and piperidine (12% of mass) between 427 and 463\u2005K, while the additional 33% loss from this last temperature to 573\u2005K corresponds to the release of 2-pyridyl\u00adphosphine. The contribution to the scattering from highly disordered solvent mol\u00adecules in II was removed with the SQUEEZE routine [Spek phosphane-\u03baSpek 2015. Acta Cr The mol\u00adecule is a rigid bidentate ligand Br)2 in chloro\u00adform as solvent leads to the complex P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]\u00b72CHCl3 (I\u00b72CHCl3). It presents a similar structure to the widely studied [Re(CO)3(L)] complexes, which have inter\u00adesting photophysical and photochemical properties , leading to the complex [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II).The reaction of the di\u00adphenyl\u00adpyridyl\u00adphosphine ligand with the rhenium dimer (Re(CO)I complex I with a bidentate P,N (chelating) ligand crystallized from a chloro\u00adform solution in the monoclinic space P21/c. Selected geometrical data are summarized in Table\u00a01I\u00b72CHCl3 is given in Fig.\u00a012Py, a bromide atom in an apical position and three carbonyl carbon atoms in a fac correlation, generating a distorted octa\u00adhedral environment. Additionally, two chloro\u00adform mol\u00adecules crystallize together with the complex mol\u00adecule.The mononuclear ReI complex II, crystallized from a CH2Cl2/CH3CN (2:1) solution in the triclinic space group P2Py ligand, a piperidine C5H11N mol\u00adecule and a bromide anion. The piperidine ring displays a chair-like conformation. An intra\u00admolecular hydrogen bond is defined between the non-coordinated pyridyl nitro\u00adgen atom and the amine hydrogen atom from piperidine, N2\u2014H2N\u22efN1, with D\u22efA = 2.992\u2005(9)\u2005\u00c5 (Table\u00a04B) of the pypridine ring  vs 2119.2\u2005(3)\u2005\u00c53 . In this dnorm view , blue represents the longest distances while the shortest distances are depicted as red spots .Compound II Br)2 and (C6H5)2(C5H5N)P were used as provided from supplier (Aldrich), with no purification before use. Seccosolv\u2122 solvents were used without any further purification. Standard Schlenck techniques under argon atmosphere were used for all manipulations.The reagents, (Re(CO)Synthesis of I. 500\u2005mg of (Re(CO)3(OC4H8)Br)2 (0.590\u2005mmol) were dissolved in 5\u2005ml of chloro\u00adform. 312\u2005mg of diphenyl-2-pyridyl\u00adphosphine (1.18\u2005mmol) was dissolved in 10\u2005ml of chloro\u00adform. The two solutions were mixed, changing from colourless to a translucent yellow after 10 minutes of reaction. The reaction was left to continue for a further 2\u2005h. Addition of 2\u2005ml of pentane to the mixture and standing by one day lead to yellow diffraction-quality crystals of I\u00b72CHCl3 .Synthesis of II. The compound was prepared by direct reaction between I and an excess of piperidine (C5H11N) at 313\u2005K in CH2Cl2. 50.0\u2005mg of  (0.082\u2005mmol) were dissolved in 10\u2005ml of CH2Cl2 giving rise to a yellow solution. Then, 40\u2005\u00b5L of piperidine (0.51\u2005mmol) was slowly added. The reaction was allowed to continue for six days with constant agitation at 313\u2005K. After cooling, the reaction mixture was layered with aceto\u00adnitrile. Small orange\u2013yellow diffraction-quality crystals were obtained after one week.Uiso(H) = 1.2Ueq(C). For II, the amine hydrogen atom of the piperidine ring was located in a Fourier-difference map and then subsequently refined with a distant constraint of 0.82\u2005\u00c5. During the last stages of the refinement of II, a region of highly disordered electron density was detected within the crystal structure. As no meaningful model could be achieved, SQUEEZE  I-2CHCl3, II, Global. DOI: 10.1107/S2056989019008089/nk2249I-2CHCl3sup2.hklStructure factors: contains datablock(s) I-2CHCl3. DOI: 10.1107/S2056989019008089/nk2249IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1921165, 1921164CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Each Cu2(CN)2 unit is connected to six FeII centres via two bridging 2-ethyl\u00adpyrazine mol\u00adecules and four cyanido groups, resulting in the formation of a polymeric three-dimensional bimetallic metal\u2013organic framework, additionally stabilized by Cu\u22efCu contacts.In the title compound, {Fe(Etpz) 6H8N2)2{Cu(CN)2}2]n, the low-spin FeII ion lies at an inversion centre and displays an elongated octa\u00adhedral [FeN6] coordination environment. The axial positions are occupied by two symmetry-related bridging 2-ethyl\u00adpyrazine ligands, while the equatorial positions are occupied by four N atoms of two pairs of symmetry-related cyanide groups. The CuI centre is coordinated by three cyanide carbon atoms and one N atom of a bridging 2-ethyl\u00adpyrazine mol\u00adecule, which form a tetra\u00adhedral coordination environment. Two neighbouring Cu atoms have a short Cu\u22efCu contact [2.4662\u2005(7)\u2005\u00c5] and their coordination tetra\u00adhedra are connected through a common edge between two C atoms of cyanide groups. Each Cu2(CN)2 unit, formed by two neighbouring Cu atoms bridged by two carbons from a pair of \u03bc-CN groups, is connected to six FeII centres via two bridging 2-ethyl\u00adpyrazine mol\u00adecules and four cyanide groups, resulting in the formation of a polymeric three-dimensional metal\u2013organic coordination framework.In the title metal\u2013organic framework, [Fe(C The axial positions are occupied by the N atoms of two symmetry-related 2-ethyl\u00adpyrazine mol\u00adecules [Fe1\u2014N3 = 1.981\u2005(2)\u2005\u00c5]. The low-spin state of the FeII centre at the temperature of experiment (T = 173\u2005K) is confirmed by the Fe\u2014N bond lengths (i.e. < 2.0\u2005\u00c5). Each CuI ion (Cu1ii and Cu1iv) is coord\u00adinated by one bridging 2-ethyl\u00adpyrazine mol\u00adecule via the N atom and by the C atoms of three cyanido groups . The separation between two neighboring Cu atoms is 2.4662\u2005(7)\u2005\u00c5, which is significantly shorter than the sum of the corresponding van der Waals radii 2 pairs, in which two Cu atoms, centred about a twofold rotation axis, are inter\u00adconnected by two \u03bc-CN groups through C atoms. The resulting polymeric three-dimensional metal\u2013organic coordination framework is additionally stabilized by supra\u00admolecular Cu\u22efCu contacts in each Cu2(CN)2 unit.Fig.\u00a03et al., 20162(CN)2 unit, the majority of which are copper monometallic metal\u2013organic frameworks (MOFs). Several bimetallic MOFs are slightly similar to the title compound, namely catena-[bis\u00ad(\u03bc3-chloro)\u00adbis\u00ad(\u03bc3-cyano)\u00adtetra\u00adkis\u00ad(\u03bc2-cy\u00adano)bis\u00ad\u00addicadmium(II)dicopper(I)copper(II)] \u00adtetra\u00adkis\u00ad(\u03bc2-cyano)\u00adtetra\u00adkis\u00ad(di\u00admethyl\u00adformamide\u00adtetra\u00adcopper(I)zinc(II)] \u00adtris\u00ad(\u03bc2-cyano)\u00adbis(\u03bc2-2-ethyl\u00adpyrazine)\u00adtetra\u00adcopper(I)]  bridging 2-ethyl\u00adpyrazine mol\u00adecules and (ii) bridging cyano groups, thus forming one-dimensional {Cu(CN)}n chains and double-stranded {Cu(CN)}n ribbons, linked into a network by bridging ethyl\u00adpyrazine ligands.A search through the CSD for 2-ethyl\u00adpyrazine gave 20 hits, in most of which 2-ethyl\u00adpyrazine mol\u00adecule binds to Cu, Ag, Mn or Rh ions. In the majority of compounds containing copper, the 2-ethyl\u00adpyrazine serves as a bridging ligand between two Cu atoms in MOFs. An example closely related to the title structure is 2]  in 1\u2005ml of H2O; the second layer was an H2O/EtOH mixture ; the third layer was a solution of Fe(ClO4)2\u00b76H2O  and 2-ethyl\u00adpyrazine  in 0.5\u2005ml of EtOH. After two weeks, brown crystals were formed in the middle layer. The crystals were kept under the mother solution prior to measurement.Crystals of the title compound were obtained by a slow diffusion within three layers in a 3\u2005ml glass tube. The first layer was a solution of K[Cu(CN)Uiso(H) = 1.2Ueq(C) for aromatic hydrogens, C\u2014H = 0.99\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for CH2 groups and C\u2014H = 0.98\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for CH3 groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989019009496/rz5262sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019009496/rz5262Isup2.hklStructure factors: contains datablock(s) I. DOI: 1937912CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is constructed by a 4-hy\u00addroxy\u00adbenzyl ring, a 3,4-di\u00adhydroxy\u00adbenzyl\u00adidenyl ring and a hydrazide-connecting bridge. The overall conformation of the title compound are discussed and compared to the related structures. In the crystal, mol\u00adecules are connected by N\u2014H\u22efO, O\u2014H\u22efO and \u03c0\u2013\u03c0 inter\u00adactions. 14H12N2O4, the azomethine C=N double bond has an E configuration. The hydrazide connecting bridge, (C=O)\u2014(NH)\u2014N=(CH), is nearly planar with C\u2014C\u2014N\u2014N and C\u2014N\u2014N=C torsion angles of \u2212177.33\u2005(10) and \u2212174.98\u2005(12)\u00b0, respectively. The 4-hy\u00addroxy\u00adphenyl and 3,4-di\u00adhydroxy\u00adphenyl rings are slightly twisted, making a dihedral angle of 9.18\u2005(6)\u00b0. In the crystal, mol\u00adecules are connected by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds into a three-dimensional network, while further consolidated via \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.6480\u2005(8) and 3.7607\u2005(8)\u2005\u00c5]. The conformation is compared to those of related benzyl\u00adidene-4-hy\u00addroxy\u00adbenzohydrazide derivatives.In the title benzohydrazide derivative, C The bond lengths and angles of the central hydrazide connecting bridge are consistent with those in related structures \u00b0] and C7\u2014N1\u2014N2\u2014C8 [\u2212174.98\u2005(12)\u00b0] are both in an anti-periplanar conformation, the overall conformation for the hydrazide connecting bridge is almost planar. Furthermore, the 4-hy\u00addroxy\u00adphenyl and 3,4-di\u00adhydroxy\u00adphenyl rings are also coplanar to the corresponding azomethine and carbonyl double bonds, with torsion angles N2\u2014C8\u2014C9\u2014C10 [\u22120.76\u2005(19)\u00b0] and C5\u2014C6\u2014C7\u2014O2 [\u22121.18\u2005(19)\u00b0] both in a syn-periplanar conformation. Those torsion angles result in an overall flat shape of the title compound with the dihedral angle between the terminal benzene rings being 9.18\u2005(6)\u00b0.The title hydrazide derivative, (I), consists of a 4-hy\u00addroxy\u00adphenyl ring, a 3,4-di\u00adhydroxyphenyl ring and a hydrazide (C=O)\u2014(NH)\u2014N=(CH) connecting bridge Fig.\u00a01. The C6\u2014O4\u22efO1iii hydrogen bond and those chains are further connected into two-dimensional plates parallel to the ac plane via N1\u2014H1N1\u22efO3i and O1\u2014H1O1\u22efO2i hydrogen bonds with an aavia an O3\u2014H1O3\u22efO2ii hydrogen bond with an bbCg1\u22efCg2iv = 3.6480\u2005(8)\u2005\u00c5 and Cg1\u22efCg2v = 3.7607\u2005(8)\u2005\u00c5 In the crystal, mol\u00adecules are linked by N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds Table\u00a01 into a tet al., 2016E)-N\u2032-benzenyl\u00adidene-4-hy\u00addroxy\u00adbenzohydrazide as the reference moiety resulted in 31 structures with different substituents at the benzyl\u00adidenyl ring. The different substituent (R) together with selected torsion angles, \u03c41 (C5\u2014C6\u2014C7\u2014O2), \u03c42 (C6\u2014C7\u2014N1\u2014N2), \u03c43 (C7\u2014N1\u2014N2\u2014C8) and \u03c44 (N2\u2014C8\u2014C9\u2014C10) as shown in Fig.\u00a04\u03c42 and \u03c43 are anti-periplanar (151.7\u2013179.8\u00b0), showing that the hydrazide connecting bridges are nearly planar. As for the torsion angle \u03c44, all structures adopt a syn-periplanar conformation (0.6\u201319.6\u00b0). Similar to the title compound, the \u03c41 torsion angles for most of the structures are syn-periplanar (2.0\u201329.1\u00b0). However, there are three outliers  whose \u03c41 torsion angles are syn-clinal (34.9\u201350.9\u00b0). By comparing the dihedral angles, the structures can be divided into planar compounds  and non-planar compounds . In general, as the hydrazide-connecting bridges are nearly planar, relatively flat \u03c41 and \u03c44 torsion angles are observed in the former compounds, while relatively twisted \u03c41 and \u03c44 torsion angles are observed in the latter.A search of the Cambridge Structural Database max 213, 327\u2005nm; FT\u2013IR (KBr) \u03bd (cm\u22121): 3121 (O\u2014H stretching), 2800 (C\u2014H aromatic stretching), 1615 (amide C=O stretching), 1570 (C=N stretching), 1506 (C=C stretching of aromatic compound) cm\u22121; 1H NMR  \u03b4 11.39 , 10.10 , 8.23 , 7.77 , 6.84 , 9.33 , 7.22 , 6.90 , 6.77 .M.p. 572\u2013573\u2005K. UV\u2013Vis (MeOH) \u03bb. C-bound H atoms were positioned geometrically (C\u2014H = 0.93\u2005\u00c5) and refined using a riding model with Uiso(H) = 1.2Ueq(C). All O- and N-bound H atoms were located in a difference-Fourier map and refined freely [O\u2014H = 0.80\u2005(2)\u20130.88\u2005(2)\u2005\u00c5 and N\u2014H = 0.87\u2005(2)\u2005\u00c5].Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019010442/is5518sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019010442/is5518Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019010442/is5518Isup3.cmlSupporting information file. DOI: 1942396CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The best estimator of Eint is the kinetic energy density (Gb), which reasonably approximates the whole set of the structures as \u2212Eint = 0.128Gb2 \u2212 0.82Gb + 1.66  and demonstrates low dispersion. The potential and kinetic energy densities, electron density, and the d(X\u00b7\u00b7\u00b7X) distance behave similarly as estimators of Eint for the individual series Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I. A number of the Eint(property) correlations are recommended for the practical application in the express estimates of the strength of the homo-halogen bonds.Relationships between interaction energy (E Halogen bonds play a very important role in molecular recognition and crystal engineering, synthesis of functional solid materials \u2212 type  formed upon interaction of the neutral fragment (A)nZ\u2013Y and the halide anion X\u2212 were considered. It was shown that the Eint(property) correlations are different for each particular type of the Y\u00b7\u00b7\u00b7X\u2212 interaction and they are also different from Equations (1)\u2013(4). Several Eint(property) relationships practically important for express estimates of the interaction energy were recommended for each series of these structures.Recently, the author started the project aimed to establish the Ech cycle , the halint(property) relationships are analyzed for the homo-halogen bonds of the [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m] type formed upon the interaction of two neutral fragments (A)nY\u2013X and X\u2013Z(B)m . For the first time, the Eint(property) relationships were deduced for the Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I homo-XBs based on a large, statistically significant set of structures .In this work, the Eint(Vb) correlation for structures of the [(A)nZ\u2013Y\u00b7\u00b7\u00b7F]\u2212 type  at the M06-2X level of theory has similar parameters as that for the MP4, CCSD, and CCSD(T) methods .int and the electron density based properties of the [(A)nZ\u2013Y\u00b7\u00b7\u00b7F]\u2212 structures. Coefficients of the Eint(Vb) correlations obtained for these two basis sets are also similar . MeanwhThe Hessian matrix was calculated for all optimized structures to prove the location of correct minima. No symmetry operations were applied during the calculations. The stability test was performed and the stable solutions were achieved for all structures using the keyword STABLE(OPT). BSSE was corrected using the counterpoise (CP) method ,100. A dnY\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m]  bearing the homo-halogen bonds Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I and formed upon interaction of two neutral fragments (A)nY\u2013X and X\u2013Z(B)m were selected as computational models . In this work, the fragment (A)nY\u2013X (at the left side of the complex formula) corresponds to the XB donor and the fragment X\u2013Z(B)m (at the right side of the complex formula) corresponds to the XB acceptor.For this study, structures [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013F], [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013H], and [F\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m]. In the first two series, the XB donor part is variable while the XB acceptor part is fixed with the Z(B)m group being either a strong electron acceptor (Z(B)m = F) or an electron donor (Z(B)m = H). Series of the structures with even stronger electron donor groups Z(B)m = CMe3, CHMe2, or CH3 were also calculated. However, in most of cases, secondary X\u00b7\u00b7\u00b7H\u2013C interactions were found and, therefore, the individual X\u00b7\u00b7\u00b7X halogen bonds cannot be isolated for the analysis.For each type of halogen bonds, three series were considered, i.e., [(A)m], the XB acceptor part is variable whereas the XB donor part is fixed ((A)nY = F). Most of the attempts to calculate similar series with an electron donor group (A)nY = H failed because the \u03c3-hole at the terminal X atom of the XB donor is not sufficiently pronounced in this case, and other interactions prevail in the resulting structures.In the third series,  type with the X\u00b7\u00b7\u00b7Z contact shorter the sum of van der Waals radii but with \u03b82 \u2265 70\u00b0 and with no other weak interactions were included in the analysis since no BCPs for the X\u00b7\u00b7\u00b7Z contacts were found). Effect of the angle \u03b82 on the correlations under study is discussed in 2\u201d.Only structures which have no other contacts shorter than the sum of van der Waals radii between the (A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m], [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m], and [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] are called \u201clarge\u201d, while the series [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H], [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013F], [F\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m], [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013H], [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013F], [F\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m], [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013H], [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013F], and [F\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] are called \u201csmall\u201d series.Further in this work, the series [(A)int increases along the row X = Cl < Br < I . The Cl\u00b7\u00b7\u00b7Cl interaction is slightly weaker than the corresponding Br\u00b7\u00b7\u00b7Br and I\u00b7\u00b7\u00b7I bonds for the [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013H] and [F\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m] series (m] are the strongest ones while the XBs in the series [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013F] are typically the weakest bonds.The calculated X\u00b7\u00b7\u00b7X interaction energy with the BSSE correction in the whole set of the structures varies from 0.34 to \u22129.24 kcal/mol. All three types of halogen bonds, Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I, have comparable strengths. The dispersion of E] series . The halint(property) relationships are considered for each estimator  within the whole set and various series of the structures.In the next sections, the Eb).Potential energy density at BCP  correlations reported in literature obey a linear law. The R2 values (0.80) indicate that the correlations are of rather poor quality. Meanwhile, the mean absolute deviation (MAD) for these fittings is ~0.60 kcal/mol. This value is well within the typical accuracy of the DFT methods  and this is almost three times less than the average interaction energy for this structural set .ructures A. Very cnY\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m] with the homo-halogen bonds formed upon interaction of the neutral fragment, Eint may be roughly estimated from Vb using a single formula for all X = Cl, Br, and I. This situation is very different from that found recently for the set of anionic structures [(A)nZ\u2013Y\u00b7\u00b7\u00b7X]\u2212   which could describe the whole set of structures. At least two various dependencies are clearly visible on each Eint(property) plot (ty) plot D\u2013G.Potential energy density at BCP. The Eint(Vb) correlations for each specific type of the halogen bond are of significantly better quality than those for the whole set in terms of both R2 (0.92\u20130.96) and MAD  (nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m] and [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m] may be well approximated by a single quadratic or exponential function, the former performing slightly better with R2 = 0.92 and MAD = 0.32 kcal/mol. The [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] series lies below the series with the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br bonds on the \u2212Eint(\u2013Vb) plot.cal/mol) A. The ClKinetic energy density at BCP. The kinetic energy density behaves similarly to the potential energy density for the estimate of Eint within these series with the MAD values being only slightly worse   relationships for all series [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m], [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m] and [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] have similar parameters despite the application of different basis sets . Meanwhile, the Eint(Vb) relationship for the iodine halogen bonds is quite different from those for the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br structures. Thus, the application of Gb as an estimator of Eint is preferable over Vb also from this point of view.cal/mol) B. HoweveElectron density at BCP. The Eint(\u03c1b) relationships for these series are similar to Eint(Vb) and Eint(Gb) nY\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m] and [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] may be approximated by a single function , while the fitting for the [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m] series has quite different parameters.Eint(Gb) C. In conLaplacian and curvature of electron density distribution at BCP. Both Eint(\u22072\u03c1b) and Eint relationships for these series have similar features and are described by either quadratic or exponential function  relationships demonstrate different behavior for the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br series, on one side, and for the I\u00b7\u00b7\u00b7I series, on the other side . For the Br\u00b7\u00b7\u00b7Br series, the Eint(Hb) function is not well-defined. Finally, for the I\u00b7\u00b7\u00b7I structures, \u2212Eint increases with the decrease of Hb. The \u2212Eint(Hb) relationship is nearly linear with R2 = 0.93 and MAD = 0.42 kcal/mol and may be used for the estimate of Eint for this type of halogen bonds.her side F. For thInternuclear distance d(X\u00b7\u00b7\u00b7X). The \u2212Eint(d(X\u00b7\u00b7\u00b7X)) dependencies are exponential with rather different parameters for the Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and, in particular, I\u00b7\u00b7\u00b7I structures  plots. The best Eint(Gb) approximation was found for the [F\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m] series with R2 = 0.86 and MAD = 0.44 kcal/mol (int(\u03c1b) function also reasonably describes each of the pairs \u201c[(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013H] + [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013H] and \u201c[(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013F] + [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013F] (int(property) relationships significantly depend on the nature of the interacting atoms X.Typically, there are no statistically meaningful trends describing these series . Severalkcal/mol A. The EiI\u00b7\u00b7\u00b7I\u2013F] B but thePotential energy density at BCP. The Eint(Vb) relationship for each of nine \u201csmall\u201d series may be reasonably approximated by a linear function. The quadratic fitting is noticeably better than the linear one only for the [F\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m], [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013H], and [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013F] series (] series A\u2013C. The int(\u2212Vb) relationships for the [F\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m], [F\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m], and [F\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] series are significantly higher than for the other series, whereas those for the [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013F], [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013F], and [(A)nY\u2013I\u00b7\u00b7\u00b7I\u2013F] structures are the lowest.First, the slope and negative interception of the \u2212E2. However, the MAD values for the  \u201csmall\u201d series  are significantly lower than for the corresponding \u201clarge\u201d series . The estimate of Eint for the structures [F\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m] and [F\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] is preferable using equations for the \u201clarge\u201d series because both MAD and R2 parameters are worse for these \u201csmall\u201d series than for the corresponding \u201clarge\u201d ones.Second, quality of the dependencies for the \u201csmall\u201d series is usually worse than for the \u201clarge\u201d ones in terms of RnY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H], is described by an equation similar to the EML formula (Eint = 0.47Vb + 0.27). Equations (3)\u2013(5) obtained for the halogen bonds of the X\u00b7\u00b7\u00b7D type  [nY\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m] type discussed in this work (except the same [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H] series).Third, among all \u201csmall\u201d series, only one, , [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013F] and [F\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m]  relationship is of the same type for [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013H] and [(A)nY\u2013Br\u00b7\u00b7\u00b7Br\u2013F] m] and as a linear function for the I...I structures (int(Hb) dependencies for the \u201csmall\u201d series is worse than for the other estimators.l\u2013Z(B)m] D althoug\u00b7\u00b7\u00b7Br\u2013F] E. Howeveructures F. The quOther estimators. The main features of the Eint(Gb), Eint(\u03c1b), Eint(\u22072\u03c1b), Eint, and Eint(d(X\u00b7\u00b7\u00b7X)) relationships for the \u201csmall\u201d series are similar to the corresponding Eint(Vb) dependencies (m] particularly poor.ndencies . Laplacir) over IAS (r \u2208 IAS) may be a better estimator of Eint than the potential energy density at BCP (Vb). This result was obtained for a set of 50 structures with very different types of non-covalent interactions. Here, the quality of this estimator was verified for structures of the [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m] type. The calculations indicated that the IAS integral of electronic virial field behaves similarly as Vb for the [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H] and [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013F] series  and relatively high MAD . Correspondingly, the Eint(nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m] is also significantly worse than the Eint(Vb) relationship with R2 = 0.89 vs. 0.96 and MAD = 0.28 vs. 0.18 kcal/mol.Recently, Romanova, Lyssenko, and Ananyev  reported compare A. Howeveb against nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H] (R2 = 0.99), a quite good relationship for [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013F] (R2 = 0.96) but a poor dependence for [F\u2013Cl\u00b7\u00b7\u00b7Cl\u2013Z(B)m] (R2 = 0.75)  B. Thus, 1\u00b7\u00b7\u00b7Z contact in structures [(A)nY\u2013X1\u00b7\u00b7\u00b7X2\u2013Z(B)m] included in the analysis, some of them have the angleX1X2Z (\u03b82) lower than 90\u00b0. This may point out some interaction between the atoms X1 and Z. To verify if this possible interaction affects the Eint(property) dependencies, all structures were divided into three groups, i.e., those with \u03b82 \u2265 90\u00b0, 80\u00b0 \u2264 \u03b82 < 90\u00b0, and 70\u00b0 \u2264 \u03b82 < 80\u00b0. In the second and third groups, structures with the X1\u00b7\u00b7\u00b7Z distance shorter than the sum of van der Walls radii were also separated from those with the X1\u00b7\u00b7\u00b7Z distance longer than this sum.Although no BCP was found for the Xint(Vb) dependencies for all these groups of structures are shown in 2 and the X1\u00b7\u00b7\u00b7Z distance. If considering only structures with \u03b82 \u2265 90\u00b0, R2 and MAD values are similar to those for the complete structural series except the Br\u00b7\u00b7\u00b7Br structures  on the Eint(Vb) dependencies. Similar results were obtained for all other estimators.The E compare D. In theint(property) correlations were established and analyzed for the first time for the large statistically significant sets of the homo-halogen bonds Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I formed upon interaction of two neutral fragments at the M06-2X/6-31+G* (the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br bonds) and M06-2X/DZP (the I\u00b7\u00b7\u00b7I bond) levels of theory. Electron density, its Laplacian, curvature of the electron density distribution, potential, kinetic, and total energy densities at BCP, integral of electronic virial over IAS and the d(X\u00b7\u00b7\u00b7X) internuclear distance were examined as estimators of the interaction energy. The correlations obtained in this work have a significant practical potential since they lead to interaction energies of the entire classes of the halogen bonds with the electron density distribution or even only the d(X\u00b7\u00b7\u00b7X) internuclear distance being in the hands. This is particularly important for the systems with multiple intermolecular non-covalent interactions or those bearing intramolecular XBs because a direct determination or calculation of Eint for such systems is an extremely difficult or often even impossible task. The following conclusions can be made.In this work, the Eint = 0.128Gb2 \u2212 0.82Gb + 1.66 with R2 = 0.91 and MAD = 0.39 kcal/mol. For other estimators, no reasonable single correlation was found for the whole structural set.First, the whole set of structures can be reasonably approximated by a single quadratic function \u2212Eint(Vb), Eint(Gb), Eint(\u03c1b), Eint, and Eint(d(X\u00b7\u00b7\u00b7X)) relationships, all of them being nonlinear . Quality of these relationships is better for the Cl\u00b7\u00b7\u00b7Cl structures compared to the Br\u00b7\u00b7\u00b7Br and I\u00b7\u00b7\u00b7I ones. Total energy density behaves well only for the I\u00b7\u00b7\u00b7I structures while the \u2212Eint(Hb) function is not well-defined for the Br\u00b7\u00b7\u00b7Br structures. Laplacian \u22072\u03c1b works well for the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br series but not for the I\u00b7\u00b7\u00b7I one.Second, each of the series Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I can be well described individually by the Eint due to lower dispersion of the Eint(Gb) functions.Third, the kinetic energy density at BCP can be recommended as the best estimator of EnY\u2013X\u00b7\u00b7\u00b7X\u2013H], [(A)nY\u2013X\u00b7\u00b7\u00b7X\u2013F], and [F\u2013X\u00b7\u00b7\u00b7X\u2013Z(B)m].Fourth, typically, there are no statistically meaningful trends describing the series [(A)2 but it is better in terms of MAD (with exception of the [F\u2013Br\u00b7\u00b7\u00b7Br\u2013Z(B)m] and [F\u2013I\u00b7\u00b7\u00b7I\u2013Z(B)m] structures).Fifth, quality of correlations for the \u201csmall\u201d series is usually worse than that for the \u201clarge\u201d series Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I in terms of Rint(Vb) and Eint(Gb) relationships are close to Equations (1)\u2013(5) only for the [(A)nY\u2013Cl\u00b7\u00b7\u00b7Cl\u2013H] structures. Additionally, the Eint(property) correlations obtained here for the Cl\u00b7\u00b7\u00b7Cl and Br\u00b7\u00b7\u00b7Br bonds are significantly different from those found previously for the Cl\u00b7\u00b7\u00b7Cl\u2212 and Br\u00b7\u00b7\u00b7Br\u2212 interactions between the neutral fragments (A)nY\u2013Hal and the halide anion Hal\u2212 [Sixth, the obtained here Eion Hal\u2212 . This onint estimator at least for the Cl\u00b7\u00b7\u00b7Cl bond.Seventh, the IAS integral of electronic virial Eighth, the BSSE effect is insignificant for the Cl\u00b7\u00b7\u00b7Cl structures but becomes important for the I\u00b7\u00b7\u00b7I and, in particular, Br\u00b7\u00b7\u00b7Br structures.int(property) relationships recommended for the Cl\u00b7\u00b7\u00b7Cl, Br\u00b7\u00b7\u00b7Br, and I\u00b7\u00b7\u00b7I interactions are given in i) establishment of the Eint(property) relationships for the hetero-halogen bonds Hal1\u00b7\u00b7\u00b7Hal2  and other types of the non-covalent interactions  and (ii) analysis of the effect of computational method, basis set and effective core pseudopotentials on these correlations. The corresponding studies are currently underway.The E"}
{"text": "The title compound, the potassium salt of a benzo\u00adthia\u00adzol(methyl\u00adsulfan\u00adyl)pyriminidine, was obtained in a reaction designed to deliver a neutral 2-pyrimidylbenzo\u00adthia\u00adzole. It crystallized with two independent mol\u00adecular units in the asymmetric unit. +\u00b7C18H14N5O2S3\u2212\u00b7C3H7NO\u00b70.5H2O, was obtained in a reaction designed to deliver a neutral 2-pyrimidylbenzo\u00adthia\u00adzole. The anion is deprotonated at the sulfonamide nitro\u00adgen. The asymmetric unit of the title compound contains two potassium cations, two anions, two mol\u00adecules of DMF and one of water. The anions display some conformational differences but each contains an intra\u00admolecular N\u2014H\u22efNbenzo\u00adthia\u00adzole hydrogen bond. The potassium ions both display a highly irregular six-coordination, different for each potassium ion. The anions, together with the DMF and water mol\u00adecules, are linked by four classical hydrogen bonds to form chains parallel to the b-axis direction.The title compound, K The atom K2 is coordinated by N2\u2032, N5\u2032 and both DMF oxygen atoms within the asymmetric unit, plus O2 at  and O1 at . The angles subtended by the chelating anions via N2/N5 are particularly narrow. The bridging nature of O92 is shown in Fig.\u00a03The potassium ions both display a highly irregular six-coordination; all K\u2014N and K\u2014O contacts Table\u00a01 are < 2.S(6) ring motif. The anions display some differences in conformation; the angle between the benzo\u00adthia\u00adzole ring (seven atoms) and the pyrimidine ring plus immediate substituents (ten atoms) is 20.56\u2005(5)\u00b0 for anion 1 (unprimed atoms) but 42.20\u2005(2)\u00b0 for anion 2 (primed atoms). Comparing the torsion angles in Table\u00a01cf. torsion angle C10\u2014N5\u2014S3\u2014C13 is 62.49\u2005(11)\u00b0, and 65.28\u2005(11)\u00b0 in the non-inverted system.Each anion displays an intra\u00admolecular hydrogen bond -6-(methyl\u00adsulfan\u00adyl)pyrimidin-2-yl](phenyl\u00adsulfon\u00adyl)aza\u00adnide di\u00admeth\u00adyl\u00adformamide monosolvate hemihydrate (5):d]thia\u00adzole-2-yl)-3,3-bis\u00ad(methyl\u00adthio)\u00adacrylo\u00adnitrile (2) (0.01\u2005mol) was added to a stirred solution of the N-(di\u00adamino\u00admethyl\u00adene)benzene\u00adsulfonamide (3) (0.01\u2005mol) in dry dioxane (20\u2005ml) containing potassium hydroxide (0.01\u2005mol); the reaction mixture was refluxed for 2\u2005h. After completion of the reaction (TLC), the solid precipitate was filtered off, and then recrystallized from DMF/H2O to give colourless block-like crystals of compound 5, the potassium salt of compound 4, in 75% yield (m.p. = 517\u2005K). IR : \u03bd 3431 and 3874 . 1H NMR : \u03b4 2.19 , 7.32\u20137.39 , 7.46 , 7.83\u20137.85 , 7.92 , 8.01 , 8.49 , 11.50 .The reaction pathway is illustrated in Fig.\u00a01Uiso(H) = 1.5Ueq(C-meth\u00adyl)], and allowed to rotate but not to tip (AFIX 137). Other hydrogen atoms were included using a riding model starting from calculated positions: C\u2014Haromatic = 0.95\u2005\u00c5 with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019002275/su5477sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019002275/su5477Isup2.hklStructure factors: contains datablock(s) I. DOI: 1896740CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angles between the aromatic rings are 31.99\u2005(3) and 9.17\u2005(5)\u00b0 for 1 and 2, respectively. Compound 1 features an intra\u00admolecular bifurcated N\u2014H\u22ef link due to the presence of the ortho-Cl atom on the benzene ring, whereas 2 features an intra\u00admolecular N\u2014H\u22efO hydrogen bond. In the crystal of 1, inversion dimers linked by pairs of N\u2014H\u22efS hydrogen bonds generate R22(8) loops. The extended structure of 2 features the same motif but an additional weak C\u2014H\u22efS inter\u00adaction links the inversion dimers into [100] double columns. Hirshfeld surface analyses indicate that the most important contributors towards the crystal packing are H\u22efH (26.6%), S\u22efH/H.\u00b7S (13.8%) and Cl\u22efH/H\u22efCl (9.5%) contacts for 1 and H\u22efH (19.7%), C\u22efH/H\u22efC (14.8%) and Br\u22efH/H\u22efBr (12.4%) contacts for 2.The title compounds, C The biological activities of these compounds were previously reported by Khan et al. \u2005\u00c5] benzoyl ring linked to a ortho-chloro-substituted phenyl ring [C\u2014Cl = 1.7387\u2005(14)\u2005\u00c5] in while in 2 \u2005\u00c5] benzoyl ring is linked to a para-bromo-substituted phenyl ring [C\u2014Br = 1.8991\u2005(17)\u2005\u00c5] via a thio\u00adurea (S1/N1/N2/C8) linkage. The benzoyl (O1/C1\u2013C7) and phenyl rings (C9\u2013C14) are arranged about the thio\u00adurea moiety in an anti fashion having torsion angles C8\u2014N1\u2014C7\u2014C6 = \u2212170.22\u2005(13) and C9\u2014N2\u2014C8\u2014S1 = 4.5\u2005(2)\u00b0 in compound 1, with corresponding values of \u2212176.01\u2005(16) and 3.8\u2005(3)\u00b0, respectively, in compound 2. The dihedral angles between the phenyl rings are 31.99\u2005(3) and 9.17\u2005(5)\u00b0 in 1 and 2, respectively. Compound 1 features an intra\u00admoleclar bifurcated N\u2014H\u22ef hydrogen bond (Table\u00a01ortho-Cl atom whereas 2 has an intra\u00admolecular N\u2014H\u22efO link (Table\u00a02S(6) ring. These intra\u00admolecular hydrogen bonds may be responsible for the anti arrangement of the aromatic rings about the thio\u00adurea linker.Compound 1 Fig.\u00a01 is compo 2 Fig.\u00a02, a para-d Table\u00a01 due to tk Table\u00a02. Both st1, inversion dimers linked by pairwise N1\u2014H1A\u22efS1 hydrogen bonds phen\u00adyl]carbamo\u00adthio\u00adyl}-3-methyl\u00adbenzamide (CCDC deposition No. 1840069) and 4-chloro-N-{[4-chloro-3-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]carbamo\u00adthio\u00adyl}benzamide (CCDC 1587395)  for compounds related to 1 and 2, Hirshfeld surfaces   (26.6%) contacts, followed by S\u22efH/H\u22efS (13.8%), Cl\u22efH/H\u22efCl (9.5%) O\u22efH/H\u22efO (6.7%), F\u22efH/H\u22efF (6.6%), Cl\u22efF/F\u22efCl (3.7%) and F\u22efC/C\u22efF (3.1%) inter\u00adactions. In compound 2, H\u22efH (19.7%)  are the most significant, followed by C\u22efH/H\u22efC (14.8%), S\u22efH/H\u22efS (12.6%), Br\u22efH/H\u22efBr (12.4%), C\u22efC (9.9%) and O\u22efN/N\u22efO (7.9%) inter\u00adactions.In order to further analyse the close contacts and inter\u00admolecular inter\u00adactions in the crystals of x) Fig.\u00a05 and two-x) Fig.\u00a05 and 7 \u25b8 1 and 2 were synthesized by adopting a literature procedure  or 4-bromo\u00adphenyl aniline (for 2) were added to the mixture and refluxed at 343\u2005K. Hydro\u00adchloric acid  was added and the solution was filtered to obtain the desired products: 1 in 69% yield and 2 in 80% yield. For recrystallization, compound 1 was dissolved in a mixture of di\u00adchloro\u00admethane and methanol (1:1) while compound 2 was dissolved in di\u00adchloro\u00admethane and left for slow evaporation at room temperature to obtain colourless prisms of 1 and colourless plates of 2Compounds 1, the N-bound H atoms were located in difference-Fourier maps and their positions were freely refined; in 2, the N-bound H atoms were located in difference-Fourier maps and refined as riding atoms in their as-found relative positions. The constraint Uiso(H) = 1.2Ueq(carrier) was applied in all cases.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019008569/hb7804sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: Click here for additional data file.10.1107/S2056989019008569/hb78041sup4.cmlSupporting information file. DOI: 10.1107/S2056989019008569/hb78041sup4.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019008569/hb78042sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989019008569/hb78042sup5.cmlSupporting information file. DOI: 1923234, 1923233CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, extensive hydrogen bonding, with the di\u00admethyl\u00adammonium cation and the water mol\u00adecule linking the complex anions, results in the formation of a supra\u00admolecular framework.The title complex was synthesized sonochemically. The ligand was formed  3)2NH2][Cr(C6H10NO4)2Cl]\u00b7H2O, was synthesized sonochemically. The complex anion consists of a chromium(II) ion ligated by two 3-carb\u00adoxy-2-(di\u00admethyl\u00adamino)\u00adpropano\u00adate anions. They coordinate in a bidentate manner, with a carboxyl\u00adate oxygen atom and the nitro\u00adgen atom cis to each other in the equatorial plane, while the apical position is occupied by a Cl\u2212 ion. Hence, the chromium(II) ion is five-coordinate with a quasi-ideal square-pyramidal geometry; \u03c45 parameter = 0.01. The complex crystallizes as a monohydrate and in the crystal, the water mol\u00adecule and the di\u00admethyl\u00adammonium counter-ion link the complex cations via N\u2014H\u22efO, N\u2014H\u22efCl, Owater\u2014H\u22efO, O\u2014H\u22efOwater and O\u2014H\u22efO hydrogen bonds, forming a supra\u00admolecular framework. There are also a number of C\u2014H\u22efO hydrogen bonds present that reinforce the framework structure. The crystal studied was refined as a racemic twin.The title complex, [(CH The chloride anion, Cl1, occupies the apical position. The five-coordinate chromium ion is displaced by 0.3469\u2005(7)\u2005\u00c5 from the mean plane through atoms O1, N1, O5 and N2. The equatorial Cu\u2014O bond lengths are Cr1\u2014O1 = 1.960\u2005(5)\u2005\u00c5 and Cr1\u2014O5 = 1.954\u2005(5)\u2005\u00c5, while the equatorial Cu\u2014N bond lengths are slightly longer viz. Cr1\u2014N1 = 2.025\u2005(5)\u2005\u00c5 and Cr1\u2014N2 = 2.030\u2005(5)\u2005\u00c5. The axial Cr1\u2014Cl1 bond length is 2.5301\u2005(16)\u2005\u00c5. The C\u2014C, C\u2014O, and C\u2014N bond lengths of the ligands are close to those reported for similar compounds  to 100.88\u2005(16)\u00b0 and from 159.6\u2005(2) to 160.3\u2005(2)\u00b0, respectively. This leads to a quasi-ideal square-pyramidal geometry for atom Cr1 with a \u03c45 parameter of 0.01 -dimethyl 3-(di\u00adphenyl\u00adphosphino)-N,N-di\u00admethyl\u00adaspartate]di\u00adchloro\u00adpalla\u00addium(II)  in 10\u2005ml of water was added with magnetic stirring for a further 30\u2005min. The mixture was then put in an ultrasonic bath  for 2h. The solution was then left to evaporate slowly and blue prismatic crystals were collected after two months.A mixture of fumaric acid  and di\u00admethyl\u00adamine hydro\u00adchloride (0.09\u2005ml) dissolved in 20\u2005ml methanol was stirred for 1\u2005h. Chromium(II) acetate dihydrate [CrUiso(H) = 1.5Ueq(O). All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms: O\u2014H = 0.82\u2005\u00c5, N\u2014H = 0.89\u2005\u00c5, C\u2014H = 0.96\u20130.99\u2005\u00c5 with Uiso(H) = 1.5Ueq and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019004717/su5493sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019004717/su5493Isup2.hklStructure factors: contains datablock(s) I. DOI: 1892216CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is a host\u2013guest complex of the tris-urea receptor, 3-(4-nitro\u00adphen\u00adyl)-1,1-bis\u00ad{2-[3-(4-nitro\u00adphen\u00adyl)ureido]eth\u00adyl}urea, encapsulating a hydrogen-bonded chain of di\u00adhydrogen phosphate anions. 25H25N9O9\u00b7C16H36N+\u00b7H2PO4\u2212 (I) or (C25H25N9O9)\u00b7(n-Bu4N+)\u00b7(H2PO4\u2212) (systematic name: 3-(4-nitro\u00adphen\u00adyl)-1,1-bis\u00ad{2-[3-(4-nitro\u00adphen\u00adyl)ureido]eth\u00adyl}urea tetra\u00adbutyl\u00adammonium di\u00adhydrogen phosphate), comprises a tris-urea receptor (R), a di\u00adhydrogen phosphate anion and a tetra-n-butyl\u00adammonium cation. It crystallizes with two independent formula units in the asymmetric unit. The conformations of the two tris-urea receptors are stabilized by N\u2014H\u22efO and C\u2014H\u22efO intra\u00admolecular hydrogen bonds. Each di\u00adhydrogen phosphate anion has two O\u2014H\u22efO inter\u00admolecular hydrogen-bonding inter\u00adactions with the other di\u00adhydrogen phosphate anion. Inversion-related di-anion units are linked by further O\u2014H\u22efO hydrogen bonds, forming a chain propagating along the a-axis direction. Each di\u00adhydrogen phosphate anion makes a total of four N\u2014H\u22efO(H2PO4\u2212) hydrogen bonds with two ureido subunits from two different tris-urea receptors, hence each tris-urea receptor provides the two ureido subunits for the encapsulation of the H2PO4\u2212 hydrogen-bonded chain. There are numerous inter\u00admolecular C\u2014H\u22efO hydrogen bonds present involving both receptor mol\u00adecules and the tetra-n-butyl\u00adammonium cations, so forming a supra\u00admolecular three-dimensional structure. One of the butyl groups and one of the nitro groups are disordered over two positions of equal occupancy.The title compound, C Inter\u00adestingly, a one-dimensional hydrogen-bonded polymeric structure is formed via hydrogen bonds between di\u00adhydrogen phosphate anions, and this anionic polymer is surrounded by and linked to the tris-urea receptors through ureido N\u2014H\u22efO hydrogen bonds.Anions play an important role in many chemical, catalysis, environmental and biological systems (Sessler R1 and R2) and the di\u00adhydrogen phosphate anions (P1 and P2) are illustrated in Fig.\u00a01N\u22efO7 in R1 and N17\u2014H17N\u22efO16 in R2), each forming an S(9) ring motif,. Four intra\u00admolecular C\u2014H\u22efO hydrogen bonds are also present in receptor R1 and three in R2 . The urea subunits N5/N6 in R1 and N11/N12 in R2 are orientated towards the di\u00adhydrogen phosphate ions (P1 and P2) forming a 2:2 adduct via N\u2014H\u22efO hydrogen bonds with anion P1 and enclosing trans to the C=O group across the respective C\u2014N bond. Anions P1 and P2 inter\u00adact with each other via two O\u2014H\u22efO hydrogen bonds (O20\u2014H20O\u22efO24 and O23\u2014H23O\u22efO22), enclosing an R1 and from 6.87\u2005(14) to 13.82\u2005(14)\u00b0 in R2. The dihedral angle between the nitro group and the benzene ring to which it is attached also vary, from 7.1\u2005(3) to 13.4\u2005(4)\u00b0 in R1 and from 8.3\u2005(4) to 16.7\u2005(7)\u00b0 in R2.The title compound crystallizes with two independent formula units in the asymmetric unit. The mol\u00adecular structure of the two tris-urea receptors , that are linked by O\u2014H\u22efO hydrogen bonds O20\u2014H20O\u22efO24 and O23\u2014H23O\u22efO22, are further linked to inversion-related anions via hydrogen bonds O21\u2014H21O\u22efO19i and O25\u2014H25O\u22efO26ii amine (tren). One of these compounds, tetra-n-butyl\u00adammonium tris\u00ad(2-(N-perfluoro\u00adphenyl\u00adureaylato)eth\u00adyl)amine di\u00adhydrogen phosphate di\u00admethyl\u00adformamide monosolvate, encapsulates a dimer of H2PO4\u2212 anions forming a pseudo-dimeric cage via sixteen hydrogen bonds and two weak anion\u22ef\u03c0 inter\u00adactions ]tris\u00ad(N\u2032-phenyl\u00adurea) tetra-n-butyl\u00adammonium di\u00adhydrogen phosphate  bis\u00ad(di\u00adhydrogen phosphate) -1-(4-nitro\u00adphen\u00adyl)-3-{2-[3-(4-nitro\u00adphen\u00adyl)ureido]cyclo\u00adhex\u00adyl}urea aceto\u00adnitrile monosolvate \u20132.21\u2005(2)\u2005\u00c5 in the title compound. The O\u2014H\u22efO hydrogen bonds involving the H2PO4\u2212 anions are also very similar: 1.62\u2005(3) and 1.63\u2005(4)\u2005\u00c5 in DASNUH, while they vary from 1.59\u2005(2) to 1.66\u2005(2)\u2005\u00c5 in the title complex.Chiral anion receptors with two enanti\u00adomeric forms Synthesis of 3-(4-nitro\u00adphen\u00adyl)-1,1-bis\u00ad{2-[3-(4-nitro\u00adphen\u00adyl)ureido]eth\u00adyl}urea (R): In a 250\u2005ml round-bottom flask, di\u00adethyl\u00adenetri\u00adamine  dissolved in 100\u2005ml of dry CH2Cl2 was added dropwise under vigorous stirring to a solution of 20\u2005ml of dry CH2Cl2 containing p-nitro\u00adbenzene iso\u00adcyanate . Subsequently, the reaction mixture was allowed to reflux for 24\u2005h. A yellowish solid was collected by filtration and washed using sequentially CH2Cl2 (3 \u00d7 70\u2005ml), a solvent mixture  and diethyl ether (3 \u00d7 70\u2005ml). The solid was then dried in vacuo overnight to afford the receptor R as a light-brown powder . FT\u2013IR : 3339, 1679, 1606, 1559, 1501, 1330. 1H NMR  in ppm: \u03b4 = 9.42 , 9.23 , 8.10 , 7.76 , 7.59 , 6.60 , 3.51 . 13C NMR  in ppm: \u03b4 = 154.99, 154.67, 147.34, 146.94, 140.72, 140.48, 125.09, 124.70, 118.13, 116.95, 46.63, 40.15\u201338.89, 38.19. HRMS (ESI+): calculated for C25H25N9O9Na [M + Na]+ 618.1673 found 618.1678.Synthesis of the title complex (I) Tetra-n-butyl\u00adammonium di\u00adhydrogen phosphate (1.68\u2005mmol) was added to 5\u2005ml of a DMF solution of R (0.168\u2005mmol) and the mixture was stirred for 2\u2005h. After filtration the solution was left to evaporate slowly and yielded colourless prismatic crystals of the title complex within three weeks.Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The C-bound H atoms were positioned geometrically and refined using a riding model: C\u2014H = 0.95\u20130.99\u2005\u00c5, with Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a02A/C79B, C80A/C80B, C81A/C81B, and C82A/C82B atoms of the disordered fragment were restrained to be similar  is disordered over two positions with equal occupancies. The C\u2014C distances were refined with the restraint of 1.515\u2005(4)\u2005\u00c5. The displacement parameters of the C7910.1107/S2056989019001336/kq2020sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019001336/kq2020Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019001336/kq2020Isup3.cmlSupporting information file. DOI: 1893140CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked  15H12F3NO3, crystallizes with one mol\u00adecule in the asymmetric unit. The mean planes of the two phenyl rings of the Schiff base moiety, bearing the OH groups and the imine group, respectively, are inclined to each other by 4.91\u2005(1)\u00b0. In the crystal, mol\u00adecules are linked via pairs of bifurcated O\u2014H\u22efO hydrogen bonds between the phenol OH groups, forming inversion dimers with an R12(5) ring motif. The structure exhibits also intra\u00admolecular O\u2014H\u22efN and C\u2014H\u22efF hydrogen-bonding inter\u00adactions. Hirshfeld surfaces analysis and two-dimensional fingerprint plots were applied to qu\u00adantify the inter\u00admolecular inter\u00adactions. The three F atoms of the tri\u00adfluoro\u00admethyl group are disordered over two sets of sites, with occupancy factors of 0.578\u2005(8) and 0.422\u2005(8). The crystal studied was refined as an inversion twinThe title compound, C The synthesis involves an aromatic amine and an aldehyde -3-({[3-meth\u00adoxy-5-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]imino}\u00admeth\u00adyl)benzene-1,2-diol, was obtained in crystalline form from the reaction of 2,3-di\u00adhydroxy\u00adbenzaldehyde with 3-meth\u00adoxy-5-(tri\u00adfluoro\u00admeth\u00adyl)aniline.In general, Schiff bases display two possible tautomeric forms, T1(C1\u2014C6\u2014C7\u2014N1) and T2(C7\u2014N1\u2014C8\u2014C9). The respective values of = 2.0\u2005(10) and \u22125.5\u2005(11)\u00b0 indicate that the mol\u00adecule is not planar  ring motif, characteristic of o-hy\u00addroxy\u00adsalicyl\u00adidene systems. Other intra\u00admolecular hydrogen bonding inter\u00adactions involve the disordered \u2013CF3 group and adjacent aromatic H atoms bonded to C9 and C11 \u2005\u00c5] and the single bond character of O1\u2014C2 [1.368\u2005(6)\u2005\u00c5] in the phenol\u2013imine tautomer. These values and other bond lengths and angles Table\u00a01 are in g1 Table\u00a02. As a reBetween adjacent mol\u00adecules there are bifurcated inter\u00admolecular O1\u2014H\u22ef hydrogen bonds with an if Fig.\u00a02, leadinget al., 2016Z)-1-phenyl-N-[3-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl]methanimine skeleton yielded eight matches. Distinctive bond lengths  in the Schiff base structure are the same within standard uncertainties as those of the corresponding bond lengths in the structures of 4N--3-meth\u00adoxy\u00adsalicylaldimine -3-{[3-(tri\u00adfluoro\u00admeth\u00adyl)phenyl\u00adimino]\u00admeth\u00adyl}benzene-1,2-diol -5-(tri\u00adfluoro\u00admeth\u00adyl)aniline -2-methyl-6-[3-(tri\u00adfluoro\u00admeth\u00adyl)-phen\u00adyl\u00adimino\u00admeth\u00adyl]phenol -2-[(4-chloro\u00adphen\u00adyl)imino\u00admeth\u00adyl]-4-(tri\u00adfluoro\u00admeth\u00adoxy)phenol -4-methyl-2-[3-(tri\u00adfluoro\u00admeth\u00adyl)phen\u00adyl\u00adimino\u00admeth\u00adyl]phenol  plot with de and di for the title compound is shown in Fig.\u00a03de = di = 1.5\u2005\u00c5; Fig.\u00a04Hirshfeld surface analysis of the title compound was performed utilizing the The title compound was prepared by refluxing mixed solutions of 2,3-di\u00adhydroxy\u00adbenzaldehyde  in ethanol (15\u2005ml) and 3-meth\u00adoxy-5-(tri\u00adfluoro\u00admeth\u00adyl)aniline  in ethanol (15\u2005ml). The reaction mixture was stirred for 5\u2005h under reflux. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) set to 1.2\u20131.5Ueq(C), and with O\u2014H = 0.82\u2005\u00c5 and Uiso(H) = 1.5Ueq(O). The three F atoms of the tri\u00adfluoro\u00admethyl group are disordered over two sets of sites, with occupancy factors of 0.578\u2005(8) for F atoms with suffix A and 0.422\u2005(8) for those with suffix B  I, global. DOI: 10.1107/S2056989019003220/wm5488Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019003220/wm5488Isup3.cmlSupporting information file. DOI: 1892713CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "L as the dihedral angle between the pyridyl rings is 78.37\u2005(5)\u00b0. Linear supra\u00admolecular chains are found in the crystal mediated by weak carbonyl-C=O\u22ef\u03c0(triazol\u00adyl) inter\u00adactions.The title mol\u00adecule adopts the shape of the letter  16H15N5O2, adopts the shape of the letter L with the dihedral angle between the outer pyridyl rings being 78.37\u2005(5)\u00b0; the dihedral angles between the central pyrazolyl ring (r.m.s. deviation = 0.0023\u2005\u00c5) and the methyl\u00adene-bound pyridyl and methyoxypyridyl rings are 77.68\u2005(5) and 7.84\u2005(10)\u00b0, respectively. Intra\u00admolecular amide-N\u2014H\u22efN(pyrazol\u00adyl) and pyridyl-C\u2014H\u22efO(amide) inter\u00adactions are evident and these preclude the participation of the amide-N\u2014H and O atoms in inter\u00admolecular inter\u00adactions. The most notable feature of the mol\u00adecular packing is the formation of linear supra\u00admolecular chains aligned along the b-axis direction mediated by weak carbonyl-C=O\u22ef\u03c0(triazol\u00adyl) inter\u00adactions. An analysis of the calculated Hirshfeld surfaces point to the importance of H\u22efH (46.4%), C\u22efH (22.4%), O\u22efH (11.9%) and N\u22efH (11.1%) contacts in the crystal.The title compound, C The synthesis of amide bonds utilizing T3P offers high yields, low epimerization and avoids the use of haza\u00adrdous additives such as explosive hy\u00addroxy\u00adbenzotriazole (HOBt). Further, reactions occur with high yields and lead to the easy removal of the by-products with a simple work-up, overall resulting in the formation of high-quality product. In addition, it is noted that the T3P reagent is non-toxic and non-allergenic a, these lead to linear supra\u00admolecular chains aligned along the b-axis direction. The supra\u00admolecular chains pack without specific inter\u00adactions between them, Fig.\u00a02b.The mol\u00adecular packing of (I)et al., 2016dnorm in Fig.\u00a03B, pyridyl-N3 and pyridyl-H5 atoms are indicative of short inter\u00adatomic N\u22efH/H\u22efN contacts s Table\u00a02. In addis Table\u00a02 are highs Table\u00a03 between a, and those delineated into H\u22efH, N\u22efH/H\u22efN, O\u22efH/H\u22efO, C\u22efH/H\u22efC and C\u22efC contacts de + di \u223c 2.5\u2005\u00c5 and 2.7\u2005\u00c5, respectively, in the corresponding delineated fingerprint plots Fig.\u00a05c and e. The pair of spikes with the tips at de + di \u223c 2.6\u2005\u00c5 and the regions of green points aligned in the fingerprint plot delineated into N\u22efH/H\u22efN contacts, Fig.\u00a05d, are indicative of short N\u22efH inter\u00adatomic contacts  although the contribution from these contacts is relatively small. The notable percentage contributions from O\u22efN/N\u22efO and C\u22efO/O\u22efC contacts to the Hirshfeld surfaces s Table\u00a02. In the ms Fig.\u00a03b althous Table\u00a02 in the cet al., 2016The 1,3 N\u2014C and C\u2014C(=O)N(H)\u2014C substitution pattern observed in (I)H-Pyrazole-4-carb\u00adoxy\u00adlic acid (0.0446\u2005mol) was treated with diiso\u00adpropyl\u00adethyl amine (0.0669\u2005mol) and 1-propane phospho\u00adnic acid (T3P) (0.0669\u2005mol) in dimethyl formamide (10\u2005ml) at 273\u2005K for 15\u2005min. Then, 6-meth\u00adoxy\u00adpyridin-2-amine (0.0490\u2005mol) was added at 273\u2005K. The reaction mixture was heated at 353\u2005K for 3\u2005h. After completion of the reaction, the product was extracted with ethyl acetate and the excess solvent was removed under vacuum. The product was recrystallized using methanol as solvent to yield 1-(6-meth\u00adoxy\u00adpyridin-2-ylmeth\u00adyl)-1H-pyrazole-4-carb\u00adoxy\u00adlic acid. This product (0.0246\u2005mol) and 2-(chloro\u00admeth\u00adyl)pyridine (0.0295\u2005mol) were dissolved in acetone (10\u2005ml), potassium carbonate (0.0369) was added and the reaction mixture was heated at 329\u2005K for 5\u2005h. After completion of the reaction, the product was extracted with ethyl acetate twice (5\u2005ml) and the extract was concentrated under vacuum. The product was washed with diethyl ether (3\u2005ml) and recrystallized from methanol solution to obtain the title compound, (I)1Uiso(H) set to 1.2\u20131.5Ueq(C). The N-bound H atoms was refined with a distance restraint of 0.86\u00b10.01\u2005\u00c5, and with Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018011477/hb7767sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018011477/hb7767Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018011477/hb7767Isup3.cmlSupporting information file. DOI: 1861657CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Supra\u00admolecular chains arise in the crystal as a result of O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonding.The  17H17F6N2O+\u00b7C2ClF2O3\u2212 quinolin-4-yl](hy\u00addroxy)meth\u00adyl}piperidin-1-ium chloro\u00addifluoro\u00adacetate), the cation, which is protonated at the piperidine N atom, has the shape of the letter, L, with the piperidin-1-ium group being approximately orthogonal to the quinolinyl residue [the Cq\u2014Cm\u2014Cm\u2013Na  torsion angle is 177.79\u2005(18)\u00b0]. An intra\u00admolecular, charge-assisted ammonium-N\u2014H\u22efO(hydrox\u00adyl) hydrogen bond ensures the hy\u00addroxy-O and ammonium-N atoms lie to the same side of the mol\u00adecule [Oh\u2014Cm\u2014Cm\u2014Na (h = hydrox\u00adyl) = \u221259.7\u2005(2)\u00b0]. In the crystal, charge-assisted hydroxyl-O\u2014H\u22efO\u2212(carboxyl\u00adate) and ammonium-N+\u2014H\u22efO\u2212(carboxyl\u00adate) hydrogen bonds generate a supra\u00admolecular chain along [010]; the chain is consolidated by C\u2014H\u22efO inter\u00adactions. Links between chains to form supra\u00admolecular layers are of the type C\u2014Cl\u22ef\u03c0(quinolinyl-C6) and the layers thus formed stack along the a-axis direction without directional inter\u00adactions between them. The analysis of the calculated Hirshfeld surface points to the dominance of F\u22efH contacts to the surface (40.8%) with significant contributions from F\u22efF (10.5%) and C\u22efF (7.0%) contacts.In the racemic title mol\u00adecular salt, C R*,S*)-quinolin-4-yl](hy\u00addroxy\u00admeth\u00adyl)piperidin-1-ium chloride is an anti-malarial drug, being effective against the causative agent, Plasmodium falciparum . In a continuation of structural studies of Mefloquine derivatives quinolin-4-yl]-piperidin-2-yl\u00admethanol). This arises when the racemic compound is reacted with HCl: the resulting salt, [-erythro-mefloquinium] isomer. However, it should be noted that the centrosymmetric unit cell has equal numbers of the other S-,R- enanti\u00adomer, indicating that no resolution occurred during the crystallization experiment as has been observed in some of the earlier studies . The pattern of hydrogen-bonding inter\u00adactions involving the ammonium-N\u2014H H atoms (see Supra\u00admolecular features) provides confirmation of protonation at the N2 atom during crystallization and, therefore, the formation of a piperidin-1-ium cation. At the same time, delocalization of the \u03c0-electron density over the carboxyl\u00adate residue is confirmed by the equivalence of the C18\u2014O2, O3 bond lengths, i.e. 2 \u00d7 1.238\u2005(3)\u2005\u00c5.The ions comprising the asymmetric unit of (I)cf. with that of 177.79\u2005(18)\u00b0 for C3\u2014C12\u2014C13\u2014N2. The latter angle indicates the piperidin-1-ium residue is almost perpendicular to the quinolinyl residue with the methyl\u00adene-C17 group orientated towards the fused-ring system as seen in the gauche C3\u2014C12\u2014C13\u2014C17 torsion angle of \u221260.7\u2005(3)\u00b0. The observed conformation, whereby the hy\u00addroxy-O and ammonium-N atoms lie to the same side of the mol\u00adecule [the O1\u2014C12\u2014C13\u2014N2 torsion angle is \u221259.7\u2005(2)\u00b0], is stabilized by an intra\u00admolecular, charge-assisted ammonium-N2+\u2014H\u22efO1(hydrox\u00adyl) hydrogen bond, Table\u00a01L.The quinolinyl residue is not strictly planar with the r.m.s. deviation for the ten fitted non-H atoms being 0.0399\u2005\u00c5. This is also reflected in the dihedral angle formed between the  and (C4\u2013C9) rings of 3.95\u2005(15)\u2005\u00c5. This aspect of the structure notwithstanding, the hydroxyl-O and ammonium-N atoms lie to opposite sides of the plane through the quinolinyl residue. This is seen in the value of the C2\u2014C3\u2014C12\u2014O1 torsion angle of \u221220.3\u2005(3)\u00b0 2C2 plane [r.m.s. deviation = 0.0089\u2005\u00c5], with the O2\u2014C18\u2014C19\u2014Cl1 torsion angle being \u221293.3\u2005(2)\u00b0, and the F7 and F8 atoms lying to the other side, the O2\u2014C18\u2014C19\u2014F7, F8 torsion angles = 28.8\u2005(3) and 146.3\u2005(2)\u00b0, respectively. The conformation of the CClF2 residue in (I)et al., 1996e.g. with mono-protonated 1,4-di\u00adaza\u00adbicyclo\u00ad[2.2.2]octane (dabco), i.e. 4-aza-1-azoniabi\u00adcyclo\u00ad[2.2.2]octane, for which three independent ion pairs comprise the asymmetric unit \u2212(carb\u00adoxyl\u00adate) and ammonium-N+\u2014H\u22efO\u2212(carboxyl\u00adate) hydrogen bonding features prominently in the mol\u00adecular packing of (I)b-axis direction, Fig.\u00a01a and Table\u00a01+\u2014H\u22efO\u2212(carboxyl\u00adate) hydrogen bonds link two cations and two anions about a centre of inversion to form eight-membered {\u22efHNH\u22efO}2 synthons, Fig.\u00a02b. These are linked into a supra\u00admolecular chain via hydroxyl-O\u2014H\u22efO\u2212(carboxyl\u00adate) hydrogen bonding, which leads to 18-membered {\u22efOCO\u22efHNC2OH}2 synthons, Fig.\u00a02b. In this scheme, the carboxyl\u00adate-O2 atom forms two hydrogen bonds. Additional stability to the supra\u00admolecular chain is afforded by quinolinyl-C\u2014H\u22efO(carboxyl\u00adate) and methyl\u00adene-C\u2014H\u22efO(hydrox\u00adyl) inter\u00adactions, Table\u00a01via C\u2014Cl\u22ef\u03c0(C4\u2013C9) inter\u00adactions, Table\u00a01a-axis direction without directional inter\u00adactions between them, Fig.\u00a02c.The presence of charge-assisted hydroxyl-O\u2014H\u22efOet al., 2016dnorm in Fig.\u00a03a and b (labelled 1\u20133), corresponding to inter\u00admolecular O\u2014H\u22efO, N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions, Table\u00a01c and d, indicate the influence of short inter\u00adatomic H\u22efH, F\u22efH/H\u22efF and F\u22efF contacts [Table\u00a02CrystalExplorer3.1 et al., 2007i.e. 11.9%, contribution from H\u22efH contacts to the Hirshfeld surface. Conversely, the relative high number of fluorine atoms lying on the surfaces of both the cation and anion, largely participating in F\u22efH contacts, gives rise to their providing the greatest contribution, i.e. 40.8%, to the surface.The overall two-dimensional fingerprint plot and those delineated  and 3.0\u2005\u00c5 (Cl\u22efH), and an arrow-shaped tip at de + di \u223c2.8\u2005\u00c5 in the fingerprint plots delineated into F\u22efH/H\u22efF, Cl\u22efH/H\u22efCl and F\u22efF contacts, respectively. The involvement of chloride and fluoride atoms in C-halogen\u22ef\u03c0 contacts, Table\u00a01In the fingerprint plot delineated into H\u22efH contacts in Fig.\u00a06et al., 2016et al., 2016et al., 2016et al., 2016i.e. (+)-PhC(CF3)(OMe)CO2\u2212  \u03b4: 1.20\u20131.35 , 1.55\u20131.75 , 3.04 , 3.53 , 5.90 , 6.94 , 8.01 , 8.13 , 8.42 , 8.72 , 9.48 ; N\u2014H H not observed. 13C NMR (DMSO-d6) \u03b4: 21.43 (2\u00d7), 21.59, 44.51, 58.90, 67.85, 1135.50. 121.17 , 121.21 , 123.64 , 126.37, 127.93 , 128.32, 128.68. 129.9 , 142.78, 146.73 , 150.97, 159.82 . 19F NMR (DMSO-d6) \u03b4: \u221258.65, \u221258.84, \u221266.68. IR (cm\u22121) 3300\u20132400 , 1662 (s).A solution of mefloquinium chloride (1\u2005mmol) and sodium di\u00adfluoro\u00adchoro\u00adacetate (1\u2005mmol) in EtOH (10ml) was refluxed for 20 mins. The reaction mixture was left at room temperature and after two days, colourless crystals of the title salt, (I)Uiso(H) set to 1.2Ueq(C). The O- and N-bound H atoms were refined with the distance restraints O\u2014H = 0.84\u00b10.01 and 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N), respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018007703/hb7752sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018007703/hb7752Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018007703/hb7752Isup3.cmlSupporting information file. DOI: 1844854CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In this compound, C\u2014H\u22efO and C\u2014H\u22efI hydrogen-bonding inter\u00adactions, \u03c0\u2013\u03c0 inter\u00adactions, other short contacts and Pb octa\u00adhedral chains are present, extending the crystal structure into a three-dimensional supra\u00admolecular network.The compound tris\u00ad bis\u00ad(dimethyl sulfoxide)di-\u03bc 3-iodido-tetra-\u03bc2-iodido-octa\u00adiodido\u00adtetra\u00adlead(II) dimethyl sulfoxide di\u00adsolvate, (C18H26N2)3[Pb4I14(C2H6OS)2]\u00b72C2H6OS, belongs to a class of organic\u2013inorganic hybrid materials with novel functionalities. In this compound, C\u2014H\u22efO and C\u2014H\u22efI hydrogen-bonding inter\u00adactions, \u03c0\u2013\u03c0 inter\u00adactions, other short contacts and Pb octa\u00adhedral chains are present, extending the crystal structure into a three-dimensional supra\u00admolecular network.The title compound, tris\u00ad bis\u00ad(dimethyl sulfoxide)di-\u03bc Viologens show excellent redox and chemical stability. In addition, they can act as effective templates for the construction of various organic\u2013inorganic hybrids, charge-transfer complexes and supra\u00admolecular systems  halide-based organic\u2013inorganic hybrids possess a large radius, a flexible coordination environment, and variable stereochemical activities of the lead center ]6\u2212 trianion, one and a half BV2+  dications and two DMSO mol\u00adecules, as shown in Fig.\u00a012+ cation is located on a general position and adopts a non-planar structure, with a dihedral angle of 27.5\u2005(3)\u00b0 between the planes of the pyridinium rings. In the bipyridinium rings, C\u2014N bond lengths vary from 1.335\u2005(9) to 1.499\u2005(10)\u2005\u00c5 and C\u2014C bond lengths from 1.336\u2005(17) to 1.636\u2005(17)\u2005\u00c5. C\u2014N\u2014C bond angles are in the range 118.6\u2005(6)\u2013121.1\u2005(7)\u00b0 and C\u2014C\u2014C bond angles in the range 107.9\u2005(9)\u2013122.1\u2005(6)\u00b0. The inorganic anion can be considered as a set of mixed face-shared/edge-shared octa\u00adhedra  lone pairs ]6\u2212 and DMSO via C\u2014H\u22efI and C\u2014H\u22efO hydrogen bonds (Table\u00a014I14)]6\u2212 and organic species play an important role in stabilizing the crystal structure  to 4.796\u2005(4)\u2005\u00c5 (DMF)2(DPB)5] [Pb3I9] [Pb2I6]  iodide complexes have been reported whose structures include chains of face-sharing ideal PbI2  and 10\u2005ml of methanol were stirred under an argon atmosphere until dissolved. 1,1\u2032-Dibutyl-4,4\u2032-bipyridyl cation salt  dissolved in methanol (5\u2005ml) was added to the reaction mixture at room temperature. The resulting precipitate was dissolved in DMSO (3\u2005ml) and placed in a sealed jar of anhydrous ether. Red crystals were produced two weeks later under an argon-protected atmosphere. After filtering and drying under vacuum, red needle-shaped crystals of 0.73\u2005g (72.3%) with high quality were obtained. Analysis calculated for C62H102I14N6O4Pb4S4: C 19.97, H 2.70, N 2.25%. Found: C 19.80, H 2.82, N 2.25%. IR (cm\u22121): 3291 (w), 3108 (m), 3035 (s), 2931 (w), 2958 (w), 2857 (w), 944 (w), 1636 (m), 1634 (s), 1441 (m), 1060 (s), 833 (s).NaI , PbIUiso(H)= 1.2-1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018016584/ex2016sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018016584/ex2016Isup2.hklStructure factors: contains datablock(s) I. DOI: 1880239CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Bnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds form corrugated chains extending along the b-axis direction which are tied into layers parallel to the bc plane by inter\u00admolecular C\u2014HMethy\u22efSThz (Methy = methyl\u00adene) hydrogen bonds, enclosing The title compound contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00adchloro\u00adbenzyl\u00adidene units, where the di\u00adhydro\u00adthia\u00adzine ring adopts a screw-boat conformation. In the crystal, inter\u00admolecular C\u2014H 22H15Cl2NOS, contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00ad\u00adchloro\u00adbenzyl\u00adidene units, where the di\u00adhydro\u00adthia\u00adzine ring adopts a screw-boat conformation. In the crystal, inter\u00admolecular C\u2014HBnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds form corrugated chains extending along the b-axis direction which are connected into layers parallel to the bc plane by inter\u00admolecular C\u2014HMethy\u22efSThz (Methy = methyl\u00adene) hydrogen bonds, en\u00adclosing R44(22) ring motifs. Offset \u03c0-stacking inter\u00adactions between 2,4-di\u00ad\u00adchloro\u00adphenyl rings [centroid\u2013centroid = 3.7701\u2005(8)\u2005\u00c5] and \u03c0-inter\u00adactions which are associated by C\u2014HBnz\u22ef\u03c0(ring) and C\u2014HDchlphy\u22ef\u03c0(ring)  inter\u00adactions may be effective in the stabilization of the crystal structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (29.1%), H\u22efC/C\u22efH (27.5%), H\u22efCl/Cl\u22efH (20.6%) and O\u22efH/H\u22efO (7.0%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Computational chemistry indicates that in the crystal, the C\u2014HBnz\u22efOThz and C\u2014HMethy\u22efSThz hydrogen-bond energies are 55.0 and 27.1\u2005kJ\u2005mol\u22121, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G level are compared with the experimentally determined mol\u00adecular structure in the solid state. The HOMO\u2013LUMO behaviour was elucidated to determine the energy gap.The title compound, C The mol\u00adecular and crystal structures, together with the Hirshfeld surface analysis, the inter\u00admolecular inter\u00adaction energies and density functional theory (DFT) computational calculations were carried out at the B3LYP/6-311G and B3LYP/6-311G levels, respectively, for (I)1,4-Benzo\u00adthia\u00adzine derivatives constitute an important class of heterocyclic systems. These mol\u00adecules exhibit a wide range of biological applications, indicating the fact that the 1,4-benzo\u00adthia\u00adzine moiety is a template potentially useful in medicinal chemistry research and therapeutic applications, such as the anti-inflammatory (Trapani B (atoms S1/N1/C1/C6\u2013C8), adopts a screw-boat conformation with puckering parameters \u2005\u00c5, \u03b8 = 68.34\u2005(16)\u00b0 and \u03c6 = 333.95\u2005(17)\u00b0. The planar rings A (C1\u2013C6), C (C10\u2013C15) and D (C17\u2013C22) are oriented at dihedral angles of A/C = 60.49\u2005(4)\u00b0, A/D = 79.69\u2005(4)\u00b0 and C/D = 41.29\u2005(4)\u00b0. Atoms Cl1 and Cl2 are \u22120.0156\u2005(3) and 0.0499\u2005(4)\u2005\u00c5 from ring C and so are almost coplanar.The title compound, (I), contains 1,4-benzo\u00adthia\u00adzine and 2,4-di\u00adchloro\u00adbenzyl\u00adidene units Fig.\u00a01, where tBnz\u22efOThz (Bnz = benzene and Thz = thia\u00adzine) hydrogen bonds form corrugated chains extending along the b-axis direction which are connected into layers parallel to the bc plane by inter\u00admolecular C\u2014HMethy\u22efSThz (Methy = methyl\u00adene) hydrogen bonds, enclosing et al., 1995C , may further stabilize the structure, with a centroid\u2013centroid distance of 3.7701\u2005(8)\u2005\u00c5, together with \u03c0-inter\u00adactions, i.e. C\u2014HBnz\u22ef\u03c0(ring) and C\u2014HDchlphy\u22ef\u03c0(ring) . The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (29.1%), H\u22efC/C\u22efH (27.5%), H\u22efCl/Cl\u22efH (20.6%) and O\u22efH/H\u22efO (7.0%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.In the crystal, inter\u00admolecular C\u2014HCrystalExplorer  and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efCl/Cl\u22efH, O\u22efH/H\u22efO, C\u22efC, S\u22efH/H\u22efS and Cl\u22efC/C\u22efCl contacts \u2013(h), respectively, together with their relative contributions to the Hirshfeld surface. The most important inter\u00adaction is H\u22efH, contributing 29.1% to the overall crystal packing, which is reflected in Fig.\u00a06b) as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule with the tip at de = di = 1.17\u2005\u00c5, due to the short inter\u00adatomic H\u22efH contacts (Table\u00a02c), with a 27.5% contribution to the HS, arises from the H\u22efC/C\u22efH contacts , with a 20.6% contribution to the HS, has a symmetrical distribution of points with the edges at de + di = 2.78\u2005\u00c5 arising from the H\u22efCl/Cl\u22efH contacts (Table\u00a02e), with a 7.0% contribution to the HS, arises from the O\u22efH/H\u22efO contacts  have an arrow-shaped distribution of points with the tip at de = di = 1.7\u2005\u00c5. Finally, the characteristic wings resulting in the fingerprint plots delineated into S\u22efH/H\u22efS and Cl\u22efC/C\u22efCl contacts , with 4.0 and 2.2% contributions to the HS, arise from the S\u22efH/H\u22efS and Cl\u22efC/C\u22efCl contacts rm Fig.\u00a03, the whis Table\u00a02. In the s Table\u00a02c, with s Table\u00a02 and are \u22efH Fig.\u00a06d, with s Table\u00a02. The pais Table\u00a02e, with s Table\u00a02 and is vts Fig.\u00a06f have as Figs.\u00a06g and 6hs Table\u00a02 and are dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efCl/Cl\u22efH, O\u22efH/H\u22efO, C\u22efC and S\u22efH/H\u22efS inter\u00adactions in Figs.\u00a07a)\u2013(f), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH, H\u22efCl/Cl\u22efH and O\u22efH/H\u22efO inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the biggest roles in the crystal packing   is the sum of the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated as \u221220.3 (Eele), \u22122.6 (Epol), \u221279.4 (Edis), 60.7 (Erep) and \u221255.0 (Etot) for C\u2014HBnz\u22efOThz hydrogen-bonding inter\u00adactions, and \u22125.8 (Eele), \u22121.0 (Epol), \u221251.0 (Edis), 39.3 (Erep) and \u221227.1 (Etot) for C\u2014HMethy\u22efSThz hydrogen-bonding inter\u00adactions.The inter\u00admolecular inter\u00adaction energies are calculated using CE\u2013B3LYP/6-31G energy model available in via density functional theory (DFT) using standard B3LYP functional and 6-311G basis-set calculations , hardness (\u03b7), potential (\u03bc), electrophilicity (\u03c9) and softness (\u03c3) are recorded in Table\u00a04E = ELUMO \u2013 EHOMO) of the mol\u00adecule was about 5.3364\u2005eV, and the frontier mol\u00adecular orbital (FMO) energies, EHOMO and ELUMO, were \u22128.2479 and \u22122.9115\u2005eV, respectively.The optimized structure of (I)et al., 2016R1 = Ph and R2 = C; see Scheme\u00a02R1 = Ph and R2 = CH2C\u2261CH (IIa)        to 36\u00b0 (for IIf). The other two (IIa and IIc) have the benzo\u00adthia\u00adzine unit nearly planar, with corresponding dihedral angles of ca 3\u20134\u00b0.A search in the Cambridge Structural Database (Groom Z)-2--2H-1,4-benzo\u00adthia\u00adzin-3(4H)-one (3.21\u2005mmol), benzyl chloride (6.52\u2005mmol) and potassium carbonate (6.51\u2005mmol) in di\u00admethyl\u00adformamide  was added a catalytic amount of tetra-n-butyl\u00adammonium bromide (0.33\u2005mmol). The mixture was stirred for 24\u2005h. The solid material was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol to afford colourless crystals in 82% yield.To a solution of  I, global. DOI: 10.1107/S2056989019013586/lh5925Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013586/lh5925Isup3.cdxSupporting information file. DOI: 1957875, 1957875CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, offset \u03c0\u2013\u03c0 inter\u00adactions involving inversion-related pyridine rings [centroid-to-centroid distance = 3.4731\u2005(14)\u2005\u00c5] link the mol\u00adecules into columns along the  14H14ClNO3, there is an intra\u00admolecular C\u2014H\u22efO hydrogen bond forming an S(6) graph-set motif. The mol\u00adecule is essentially planar with the mean plane of the ethyl acetate group making a dihedral angle of 5.02\u2005(3)\u00b0 with the ethyl 6-chloro-2-eth\u00adoxy\u00adquinoline mean plane. In the crystal, offset \u03c0\u2013\u03c0 inter\u00adactions with a centroid-to-centroid distance of 3.4731\u2005(14)\u2005\u00c5 link inversion-related mol\u00adecules into columns along the c-axis direction. Hirshfeld surface analysis indicates that H\u22efH contacts make the largest contribution (50.8%) to the Hirshfeld surface.In the title quinoline derivative, C We report herein on its crystal and mol\u00adecular structures along with the Hirshfeld surface analysis.Quinoline derivatives represent an important class of bioactive heterocyclic compounds in the field of pharmaceuticals (Chu a. The mol\u00adecule consists of a quinoline fused-ring system (N1/C1\u2013C9) with meth\u00adoxy\u00adethane (O2/C10/C11), ethyl acetate (O3/O4/C13/C14) and a chlorine atom (Cl1) substituents. The intra\u00admolecular C5\u2014H5A\u22efO3 hydrogen bond (Table\u00a01S(6) graph-set motif, stabilizing the mol\u00adecular structure and preventing free rotation between the 6-chloro\u00adquinoline ring (Cl1/N1/C1\u2013C9) and the ethyl acetate (O3/O4/C12\u2013C14) moiety. Additionally, the presence of this intra\u00admolecular C\u2014H\u22efO inter\u00adaction leads to an essentially planar mol\u00adecular structure , where the ethyl acetate (O3/O4/C12\u2013C14) mean plane is twisted slightly at a dihedral angle of 5.02\u2005(3)\u00b0 with respect to the mean plane of the ethyl 6-chloro-2-eth\u00adoxy\u00adquinoline (Cl1/O2/C1\u2013C11) moiety. This essentially planar mol\u00adecular structure may be considered an important binding mode that can enhance biological activity . They are linked by offset \u03c0\u2013\u03c0 inter\u00adactions  involving inversion-related pyridine rings. These inter\u00adactions link the mol\u00adecules into columns up the c-axis direction with a centroid-to-centroid (Cg\u22efCgi) distance of 3.4731\u2005(14)\u2005\u00c5 .In the crystal, mol\u00adecules lie in a plane parallel to the  contact distances from the Hirshfeld surface to the nearest atom inside and outside enables the analysis of the inter\u00admolecular inter\u00adactions through the mapping of dnorm. The Hirshfeld surfaces (HS) mapped over the electrostatic potential (\u22120.0534 to 0.0319 atomic units) and dnorm (\u22120.0210 to 1.4779 arbitrary units) are shown in Fig.\u00a03a and 3b. The red spots on the Hirshfeld surface indicate inter\u00adactions involved in H\u22efO contacts. The \u03c0\u2013\u03c0 stacking is confirmed by the small blue regions surrounding bright red spots in the aromatic ring in Fig.\u00a03c, the Hirshfeld surface mapped over the shape-index, and by the flat regions around the aromatic regions in Fig.\u00a03d, the Hirshfeld surface mapped over the curvedness.The Hirshfeld surface analysis  points associated with the hydrogen atoms is shown in Fig.\u00a05b. It is characterized by an end point that points to the origin, indicating the presence of the H\u22efH contacts that contribution 50.8%. The Cl\u22efH/H\u22efCl contacts between the chlorine atoms inside the Hirshfeld surface and the hydrogen atoms outside the surface and vice versa contribute 16.0% . The O\u22efH/H\u22efO (10.3%) plot shows two symmetrical wings on the left and right sides . The C\u22efC contacts contribute 7.9% , the C\u22efH/H\u22efC contacts contribute 5.3% , followed by the C\u22efO contacts at 3.7%  and the C\u22efN contacts at 3.3% .There are no significant classical inter\u00admolecular contacts present in the crystal according to the analysis of the crystal structure using 0% Fig.\u00a05c. The Oes Fig.\u00a05d. The C9% Fig.\u00a05e, the C3% Fig.\u00a05e, follo7% Fig.\u00a05g and th3% Fig.\u00a03h.Gaussian 09 package  was also calculated using DFT methods at the B3LYP/6-311+G level of theory using the et al., 2016et al., 2010aet al., 2010bet al., 2010cet al., 2010det al., 2009et al., 2009A search of the Cambridge Structural Database  of tetra-n-butyl\u00adammonium bromide (TBAB). The reaction mixture was stirred at room temperature in DMF for 24\u2005h. After removal of salts by filtration, the DMF was evaporated under reduced pressure and the residue obtained was dissolved in di\u00adchloro\u00admethane\u00b7The organic phase was dried over Na2SO4 then concentrated in vacuo. The resulting mixture was chromatographed on a silica gel column [eluent: ethyl acetate/hexane (1:9 v/v)]. Colourless crystals were obtained when the solvent was allowed to evaporate (yield: 32%).A solution of 0.5\u2005g (1.99\u2005mmol) of ethyl 6-chloro-2-oxo-1,2-di\u00adhydro\u00adquinoline-4-carboxyl\u00adate in 25\u2005ml of DMF was mixed with 0.3\u2005ml (3.98\u2005mmol) of bromo\u00adethane, 0.55\u2005g (3.98\u2005mmol) of KUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms. A rotating group model was applied to the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019007473/mw2143sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019007473/mw2143Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019007473/mw2143Isup3.cmlSupporting information file. DOI: 1890687CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E) -meth\u00adoxy\u00adbenzaldehyde oxime derivatives, namely \u22efO(hy\u00addroxy) hydrogen bonds generate C(3) chains in 1 and 2. In contrast, in compound 3, the O\u2014H(oxime)\u22efO(hy\u00addroxy) hydrogen bonds generate symmetric 4 from the O\u2014H(oxime)\u22efO(hy\u00addroxy) and C\u2014H(2-meth\u00adoxy)\u22efO(hy\u00addroxy) hydrogen bonds.The crystal structures of four ( E)-meth\u00adoxy\u00adbenzaldehyde oxime derivatives, namely \u22efO(hy\u00addroxy) hydrogen bonds generate C(3) chains in 1 and 2. In contrast, in compound 3, the O\u2014H(oxime)\u22efO(hy\u00addroxy) hydrogen bonds generate symmetric R22(6) dimers. A more complex dimer is generated in 4 from the O\u2014H(oxime)\u22efO(hy\u00addroxy) and C\u2014H(2-meth\u00adoxy)\u22efO(hy\u00addroxy) hydrogen bonds. In all cases, further inter\u00adactions, C\u2014H\u22efO and C\u2014H\u22ef\u03c0 or \u03c0\u2013\u03c0, generate three-dimensional arrays. Hirshfeld surface and fingerprint analyses are discussed.The crystal structures of four ( The last survey of the classical hydrogen-bonding patterns in benzaldehyde oximes reported in 2010 . In compounds 1\u20133, the 2-meth\u00adoxy group and the hydrogen of the oxime moiety have an s-cis arrangement. In contrast, in both mol\u00adecules of compound 4, the 2-meth\u00adoxy group and the hydrogen atom of the oxime moiety have an s-trans arrangement. The s-trans arrangement of the 2-alk\u00adoxy group and hydrogen atom of the oxime units in compound 4 is very much rarer than the s-cis arrangement found in compounds 1\u20133 and other non-salicylaldoximes. A search of the Cambridge Structural Database -2-({2-[(E)-(hy\u00addroxy\u00adimino)\u00admeth\u00adyl]phen\u00adoxy}meth\u00adyl)-3-p-tolyl\u00adacryl\u00ado\u00adnitrile meth\u00adyl]phen\u00adoxy}meth\u00adyl)-3-(2-methyl\u00adphen\u00adyl)acrylo\u00adnitrile -2-({2-[(E)-(hy\u00addroxy\u00adimino)\u00admeth\u00adyl]phen\u00adoxy}meth\u00adyl)-3-phenyl\u00adacrylo\u00adnitrile  chains, illustrated in Fig.\u00a061 are two weaker hydrogen bonds, namely, C3\u2014H3\u22efO13ii and C21\u2014H21C\u22efO13iii, as well as a weak \u03c0\u2013\u03c0 stacking inter\u00adaction . These three inter\u00adactions generate the mol\u00adecular arrangement shown in Fig.\u00a07ii hydrogen bonds generate C7 chains in the c-axis direction, while the C21\u2014H21C\u22efO13iii hydrogen bonds form C(8) spiral chains along the a-axis direction: together these hydrogen bonds form c-axis direction. The involvement of the weaker C3\u2014H3\u22efO13ii, C21\u2014H21C\u22efO13iii and \u03c0\u2013\u03c0 inter\u00adactions, along with the stronger O13\u2014H13 \u22efN12i hydrogen bonds, creates the three-dimensional structure for 1.In the crystal of s Table\u00a02, forming1, mol\u00adecules of 2 are primarily linked by strong O13\u2014H13 \u22efN12i hydrogen bonds (Table\u00a03C(3) chains: as such chains are very similar to those in compound 1, see Fig.\u00a06C(3) chain in compound 2. Other inter\u00admolecular inter\u00adactions in 2 are the weaker C21\u2014H21B\u22efO31iii and C31\u2014H31B\u22efO13iv hydrogen bonds and a C31\u2014H31C\u22efCg1v inter\u00adaction involving the C1\u2013C6 ring. These three inter\u00adactions combine to form the arrangement illustrated in Fig.\u00a08B\u22efO31iii hydrogen bonds on their own generate C(6) chains, which propagate in the a-axis direction while the C31\u2014H31B\u22efO13iv hydrogen bonds generate spiral C(9) chains in the b-axis direction. Together these hydrogen bonds generate a network of C\u22efCg1v inter\u00adactions lead to chains along the a-axis direction. The involvement of the weaker C21\u2014H21B\u22efO31iii, C31\u2014H31B\u22efO13iv C and C\u2014H\u22ef\u03c0 inter\u00adactions, along with the stronger O13\u2014H13 \u22efN12i hydrogen bonds, creates a three-dimensional structure for 2. C4\u2014H4\u22efO12ii hydrogen bonds also occur.As in s Table\u00a03, forming3, i hydrogen bonds (Table\u00a04A(meth\u00adoxy)\u22efO13ii hydrogen bonds provide a two-mol\u00adecule-wide ribbon. Within the ribbons are 3 is the C41\u2014H41C\u22efCg1iii inter\u00adaction, which generates a tilted ladder assembly, propagating in the a-axis direction, with the C\u22efCg1iii inter\u00adactions as the supports.In compound s Table\u00a04, as illu4, each of the two independent mol\u00adecules forms symmetric dimers, see Fig.\u00a010i and O113\u2014H113\u22efO121i hydrogen bonds  chains, while in compounds 3 and 4, they are responsible for the creation of the dimers. In compound 3, the fins ending at de, di = 1.9,1.1\u2005\u00c5 are due to C(\u03c0)\u22efH/C(\u03c0)\u22efH contacts. The FP plots for Mol A and Mol B of compound 4 are asymmetric because of the different inter\u00adactions of each mol\u00adecule. The double wings in the FP plot for Mol A in the second quadrant are complementary to those displayed in the fourth quadrant by MolB and relate to C\u22efH close contacts connecting the two mol\u00adecules. The spike ending at di, de = 1.1\u2005\u00c5 in Mol A is due to H\u22efH contacts.Hirshfeld surfaces -chain-forming compounds 1 and 2 show higher percentages of H\u22efH and C\u22efC contacts, but a lower percentage of H\u22efC/C\u22efH contacts, than the dimer-forming compounds 3 and 4.The percentages of the various atom\u2013atom contacts, derived from the fingerprint plots, for the four compounds are shown in Table\u00a06et al., 20162 and 3. The classical hydrogen bonds in 3,5-di\u00admeth\u00adoxy\u00adbenzene oxime generate C(3) chains  in the CSD database with oxime 1, 371\u2013373\u2005K for 2, 378\u2013380\u2005K for 3 and 370\u2013371\u2005K for 4.The title compounds were prepared from hy\u00addroxy\u00adamine and the corresponding benzaldehyde in methanol in the presence of potassium carbonate and were recrystallized from methanol solutions, m.p. = 364\u2013365\u2005K for compound Uiso(H) = 1.2\u20131.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0710.1107/S2056989018014020/qm2129sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, 4, global. DOI: 10.1107/S2056989018014020/qm21291sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018014020/qm21292sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989018014020/qm21293sup4.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S2056989018014020/qm21294sup5.hklStructure factors: contains datablock(s) 4. DOI: Click here for additional data file.10.1107/S2056989018014020/qm21291sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018014020/qm21292sup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018014020/qm21293sup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018014020/qm21294sup9.cmlSupporting information file. DOI: 1871165, 1871164, 1871163, 1871162CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The supra\u00admolecular structure is mainly governed by C\u2014H\u22efN hydrogen-bonded centrosymmetric dimers, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and S\u22ef\u03c0 stacking inter\u00adactions, which together lead to the formation of a layered crystal packing.The mol\u00adecular conformation is stabilized  15H13N3O2S, crystallizes in the monoclinic space group P21/n and its mol\u00adecular conformation is stabilized via intra\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN contacts. The supra\u00admolecular structure is mainly governed by C\u2014H\u22efN hydrogen-bonded centrosymmetric dimers, C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds and S\u22ef\u03c0 and \u03c0\u2013\u03c0 stacking inter\u00adactions which, together, lead to the formation of a layered crystal packing. The inter\u00admolecular inter\u00adactions were further evaluated through the mol\u00adecular electrostatic potential map and Hirshfeld fingerprint analysis.The title compound, C N-heterocycles (having two carbon and three nitro\u00adgen atoms) because of their unique structural and chemical properties methanone (1).In general, the 1,2,3-triazole nucleus is the most fundamental heterocyclic component found in various pharmacologically active agents  in the asymmetric unit \u2005\u00c5] and C11\u2014H11\u22efN1 [C11\u22efN1 = 2.950\u2005(2)\u2005\u00c5] contacts  of the meth\u00adoxy group with the triazol nitro\u00adgen N3 [C15\u22efN3 = 3.490\u2005(3)\u2005\u00c5] and the thio\u00adphene hydrogen H12 (sp2) with the triazol nitro\u00adgen N1 [C12\u22efN1 = 3.768\u2005(2)\u2005\u00c5]. These are extended in an alternate fashion, forming ribbons along the [101] direction  [3.492\u2005(2)\u2005\u00c5] inter\u00adactions along the [010] direction, forming a corrugated sheet perpendicular to the (101) plane , and two-dimensional fingerprint plots (thio\u00adphen-2-yl)methanone subunit resulted in one hit  =1.5Ueq(C) for the methyl group and C\u2014H = 0.95\u00c5 with Uiso(H) = 1.2Ueq(C) for the aromatic C atoms.Crystal data, data collection and structure refinement details are given in Table\u00a0210.1107/S2056989018010654/xi2009sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018010654/xi2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018010654/xi2009Isup3.cmlSupporting information file. DOI: 1850683CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "While there are two C\u2014H\u22efO weak inter\u00admolecular inter\u00adactions present in both (I) and (II), the change of substituent from chlorine to methyl has given rise to an additional weak C\u2014H\u22efO inter\u00admolecular inter\u00adaction that is relatively stronger than the other two. However, the presence of the stronger C\u2014H\u22efO inter\u00adaction in (II) has not disrupted the validity of the chloro-methyl exchange rule. Details of the crystal structures and Hirshfeld analyses of the two compounds are presented.Instances of crystal structures that remain isomorphous in spite of some minor changes in their respective mol\u00adecules, such as change in a substituent atom/group, can provide insights into the factors that govern crystal packing. In this context, an accurate description of the crystal structures of an isomorphous pair that differ from each other only by a chlorine\u2013methyl substituent,  The prediction of crystal structures has emerged as an exciting field involving researchers from diverse fields primarily because of its challenging complexity, which is considered analogous to that of the protein-folding problem. Attempts made in the field of crystal-structure prediction, its present status and the challenges ahead were discussed in detail in a recent article et al., 2011et al., 2018et al., 2019et al., 2007et al., 2008From a pharmacological view point, the title compounds (I)The mol\u00adecular structures of (I)Q(2) = 0.4011\u2005(2)\u2005\u00c5 and \u03c6 = 180.3733\u2005(3)\u00b0 for (I)Q(2) = 0.4047\u2005(2)\u2005\u00c5 and \u03c6 = 180.3444\u2005(3)\u00b0 for (II)Q = 0.5572\u2005(16)\u2005\u00c5, \u03b8 = 138.9\u2005(2)\u00b0, \u03c6 = 219.8\u2005(3)\u00b0 in (I)Q = 0.5603\u2005(17)\u2005\u00c5, \u03b8 = 137.7\u2005(2)\u00b0, \u03c6 = 219.6\u2005(3)\u00b0 in (II)As expected, the conformational features of both compounds are nearly identical, as shown in a overlay diagram Fig.\u00a03. The fivThe dihedral angle between the mean planes of the two chloro\u00adphenyl groups in (I)viz. C10\u2014H10\u22efO2 and C16\u2014H16\u22efO2, which are identical in nature and characteristic of similar fundamental mol\u00adecular inter\u00adaction patterns are present (Tables 3b-axis direction in both (I)b-axis direction  Tables 3 and 4 \u25b8.viz. C36\u2014H36A\u22efO1, that is stronger than the two characteristic weak inter\u00admolecular inter\u00adactions and involves the replaced substituent methyl group (C36\u2014H36A) as a donor and the piperidinone O1 atom as an acceptor (see Table\u00a04In (II)B\u22ef\u03c0 inter\u00adaction observed in (I)Cg3\u22efCg3 distances of 3.7459\u2005(2)\u2005\u00c5 in (I)Cg3 is the centroid of the C14\u2013C19 ring. The shortest Cl\u22efCl distance observed [Cl1 \u22efCl1] is 4.088\u2005(1)\u2005\u00c5 and bears no structural significance.In addition, a weak C\u2014H\u22ef\u03c0 inter\u00adaction involving different donor groups and acceptor \u03c0-ring systems is present in both (I)et al., 2016R factors less than 0.05) gave only three hits: 5\u2032\u2032-(4-chloro\u00adbenzyl\u00adidene)-4\u2032-(4-chloro\u00adphen\u00adyl)-1\u2032,1\u2032\u2032-dimethyl-2H,4\u2032\u2032H-di\u00adspiro\u00ad-2,4\u2032\u2032-dione -pyridinone  analysis was used to investigate and visualize the weak inter\u00admolecular inter\u00adactions influential in the packing of the mol\u00adecules in the crystal. The visual representation of mol\u00adecular inter\u00adactions on this isosurface is determined using two parameters, CrystalExplorer3.0 E)-2-chloro\u00adphenyl\u00admethyl\u00adidene] tetra\u00adhydro-4(1H)- pyridinone (1\u2005mmol), acenaphthene\u00adquinone (1\u2005mmol) and sarcosine (1\u2005mmol) was dissolved in methanol (15\u2005mL) and refluxed for 30\u2005min. After completion of the reaction, as evident from TLC, the mixture was poured into water (50\u2005mL) and the precipitated solid was filtered and washed with water (100\u2005mL) to obtain pure (I)fR  0.40. Suitable crystals for single-crystal X-ray studies were obtained by recrystallization of the product from ethanol.For (I)E)-2-methyl\u00adphenyl\u00admethyl\u00adidene] tetra\u00adhydro-4(1H)-pyridinone (1\u2005mmol), acenaphthene\u00adquinone (1\u2005mmol) and sarcosine (1\u2005mmol) in methanol (15\u2005mL) to yield yellow crystals.A similar procedure for (II)Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise. The H atoms of the methyl atoms C35 and C36 in (II)Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019012428/jj2215sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989019012428/jj2215Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019012428/jj2215IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1951894, 1569029CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II ion is coordinated by two N atoms of the N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethylenedi\u00adamine ligand and two S atoms from two 2-meth\u00adoxy\u00adethyl xanthate ligands. Two C\u2014H\u22efO and two C\u2014H\u22efS intra\u00admolecular inter\u00adactions occur. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, forming a three-dimensional supra\u00admolecular architecture.In the title compound, the Zn S)zinc(II) acetone hemisolvate, [Zn(C4H7O2S2)2(C6H16N2)]\u00b70.5C3H6O, the ZnII ion is coordinated by two N atoms of the N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethylenedi\u00adamine ligand and two S atoms from two 2-meth\u00adoxy\u00adethyl xanthate ligands. The amine ligand is disordered over two orientations and was modelled with refined occupancies of 0.538\u2005(6) and 0.462\u2005(6). The mol\u00adecular structure features two C\u2014H\u22efO and two C\u2014H\u22efS intra\u00admolecular inter\u00adactions. In the crystal, mol\u00adecules are linked by weak C\u2014H\u22efO and C\u2014H\u22efS hydrogen bonds, forming a three-dimensional supra\u00admolecular architecture. The mol\u00adecular structure was optimized using density functional theory (DFT) at the B3LYP/6\u2013311\u2005G level. The smallest HOMO\u2013LUMO energy gap (3.19\u2005eV) indicates the suitability of this crystal for optoelectronic applications. The mol\u00adecular electrostatic potential (MEP) further identifies the positive, negative and neutral electrostatic potential regions of the mol\u00adecules. Half a mol\u00adecule of disordered acetone was removed with the solvent-mask procedure in OLEX2  and this contribition is included in the formula.In the title compound, bis\u00ad(2-meth\u00adoxy\u00adethyl xanthato-\u03ba al. 2009. J. Appl Xanthate is a bidentate monoanionic sulfur\u2013sulfur donor ligand. It stabilizes complexes of most of the transition elements and can bind metal centers in monodentate, isobidenate, anisobidenate or ionic modes. Xanthates have the ability to inhibit the replication of both RNA and DNA viruses II ion is coordinated by two N atoms of the N,N,N\u2032,N\u2032-tetra\u00admethyl\u00adethylenedi\u00adamine mol\u00adecule and two S atoms from two 2-meth\u00adoxy\u00adethylxanthate mol\u00adecules. The Zn1\u2014N1, Zn1\u2014N2, Zn1\u2014S1 and Zn1\u2014S3 bond lengths are 2.141\u2005(5), 2.123\u2005(5), 2.3107\u2005(9) and 2.3050\u2005(9)\u2005\u00c5, respectively \u2005\u00c5, which is typical of a single bond whereas the carbon-to-sulfur S2 distance of 1.647\u2005(3)\u2005\u00c5 is typical of a carbon-to-sulfur double bond. In the mol\u00adecule, weak C1\u2014H1C\u22efO8, C2A\u2014H2AB\u22efO11, C5A\u2014H5AA\u22efS1 and C6\u2014H6C\u22efS4 intra\u00admolecular inter\u00adactions are observed 2(bipy)] [CSD 2(C6H16N2)]  and [Ni(moexa)2phen] (benzene solvate), moexa = O-methoxy\u00adethyl\u00adxan\u00adthato-S,S\u2032 2]  and the lowest unoccupied mol\u00adecular orbitals (LUMOs) are named as frontier mol\u00adecular orbitals (FMOs). The FMOs play an important role in the optical and electric properties. The frontier orbital gap characterizes the chemical reactivity and the kinetic stability of the mol\u00adecule. A mol\u00adecule with a small frontier orbital gap is generally associated with a high chemical reactivity, low kinetic stability and is also termed a soft mol\u00adecule. The density functional theory (DFT) quantum-chemical calculations for the title compound were performed at the B3LYP/6\u2013311\u2005G level  level of theory and is illustrated in Fig.\u00a043CO2)\u00b72H2O  in 2-meth\u00adoxy\u00adethanol. A hot solution of potassium 2-meth\u00adoxy\u00adethylxanthate  in 2-meth\u00adoxy\u00adethanol was added and the mixture was stirred for 30\u2005min. Water was added to the mixture and a white precipitate was formed. The product was recrystallized from acetone.Tetra\u00admethyl\u00adethylenedi\u00adamine  was added to a hot solution of Zn(CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. All atoms of the amine ligand are disordered and were modelled as two orientations with relative occupancies of 0.538\u2005(6) and 0.462\u2005(6). The diffuse electron density of half an acetone solvent mol\u00adecule was removed with the solvent-mask procedure implemented in OLEX2  I. DOI: 10.1107/S2056989019013148/lh5921Isup2.hklStructure factors: contains datablock(s) I. DOI: 1420207CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The difference was ascribed to the HOMO of the amide group, which expands in the vertical direction (\u03c0O) rather than in the plane (nO). S\u00b7\u00b7\u00b7X interactions in four model proteins, phospholipase A2 (PLA2), ribonuclease A (RNase A), insulin, and lysozyme, have also been analyzed. The results suggested that S\u00b7\u00b7\u00b7X interactions would be important factors that control not only the three-dimensional structure of proteins but also their functions to some extent. Thus, S\u00b7\u00b7\u00b7X interactions will be useful tools for protein engineering and the ligand design.In organic molecules a divalent sulfur atom sometimes adopts weak coordination to a proximate heteroatom (X). Such hypervalent nonbonded S\u00b7\u00b7\u00b7X interactions can control the molecular structure and chemical reactivity of organic molecules, as well as their assembly and packing in the solid state. In the last decade, similar hypervalent interactions have been demonstrated by statistical database analysis to be present in protein structures. In this review, weak interactions between a divalent sulfur atom and an oxygen or nitrogen atom in proteins are highlighted with several examples. S\u00b7\u00b7\u00b7O interactions in proteins showed obviously different structural features from those in organic molecules ( Nagao ,33 reporives (3) , bis[2-(fide (4) , \u03b2-hydro (4) [5) , and thi [5) [6) .Weak nonbonded interactions are important physicochemical forces that control the structure of proteins . Ionic iet al. [The SSC and CSC groups involved in cystine and methionine residues, however, were usually considered just as hydrophobic moieties in folded protein structures until recently, except for S\u00b7\u00b7\u00b7C(\u03c0) interactions  and weaket al.  suggesteet al. ,28,51,52et al. ,47. Meanet al. , but the et al. [ etc.) atomic contacts involved in 604 high-resolution (\u22642.0 \u00c5) heterogeneous X-ray structures selected from the Protein Data Bank [d = rS\u00b7\u00b7\u00b7X \u2212 vdwS \u2212 vdwX), the directionality around the S and X atoms, and the location along the amino acid sequence revealed distinct structural features of the S\u00b7\u00b7\u00b7X interactions. In case of the most frequent S\u00b7\u00b7\u00b7O interactions, both SSC and CSC S atoms tend to approach a main-chain O atom perpendicularly to the amide plane (the \u03c0O direction), and the O atom tends to approach the S atom from the backside of the S\u2013S or S\u2013C covalent bonds (the \u03c3S* direction). Similar directionalities of the S(CSC)\u00b7\u00b7\u00b7O interactions were also reported by Pal and Chakrabarti [O orbital, not \u03c0O, is usually used to form the interaction.Nonbonded S\u00b7\u00b7\u00b7X interactions in proteins have recently been pursued by several research groups ,23,18,21 et al.  thoroughata Bank . Statistkrabarti . The strd \u2264 0.0 \u01fa), a probability of S\u00b7\u00b7\u00b7O contacts increases significantly, suggesting the presence of specific S\u00b7\u00b7\u00b7O interactions in proteins. According to the statistical analysis for the obtained data, four types of nonbonded S\u00b7\u00b7\u00b7X interactions have been clearly characterized, i.e., S\u2013S\u00b7\u00b7\u00b7O=C, C\u2013S\u00b7\u00b7\u00b7O=C, C\u2013S\u00b7\u00b7\u00b7N, and S\u2013S\u00b7\u00b7\u00b7S\u2013S interactions [ractions .O \u2192 \u03c3S* orbital interaction is obvious. The S\u2013S\u00b7\u00b7\u00b7O=C interactions are most frequently observed in helices, suggesting that the S\u00b7\u00b7\u00b7O interactions would support the stability. The C\u2013S\u00b7\u00b7\u00b7O=C interaction formed between a methionine side-chain and a main-chain peptide group has a similar character to the S\u2013S\u00b7\u00b7\u00b7O=C interaction, but the strength of the interaction is weaker with attenuated directionality. Similarly, the C\u2013S\u00b7\u00b7\u00b7N interaction between a methionine side-chain and a main-chain peptide group can also be characterized by the linear C\u2013S\u00b7\u00b7\u00b7N atomic alignment and the vertical access of the S atom to the amide plane, suggesting a contribution from the \u03c0N \u2192 \u03c3S* orbital interaction. On the other hand, most of close S\u00b7\u00b7\u00b7S contacts in proteins can be assigned to S\u2013S\u00b7\u00b7\u00b7S\u2013S interaction, which would be stabilized by the nS \u2192 \u03c3S* orbital interaction in a similar manner to that observed in organic crystals [A majority of close S\u00b7\u00b7\u00b7O contacts for an SSC group in proteins is assigned to S\u2013S\u00b7\u00b7\u00b7O=C interactions, which can be characterized by the linear S\u2013S\u00b7\u00b7\u00b7O atomic alignment and the vertical access of the S atom to the carbonyl plane as shown in crystals .Ab initio calculation was carried out for the model complexes (CH3SSCH3 + CH3CONHCH3 and CH3SCH3 + CH3CONHCH3) to investigate the nature of the S\u00b7\u00b7\u00b7X interactions observed in proteins [O \u2192 \u03c3S* orbital interaction  lying in the carbonyl plane rather than the \u03c0 orbital expanding perpendicular to the plane. The reason for the observed discrepancy in the directionality between the S\u00b7\u00b7\u00b7O interactions in proteins and organic molecules can be explained on the basis of the HOMO levels of various carbonyl compounds . As grapO level of amide CH3CONHCH3 is remarkably raised compared with other carbonyl compounds, while the nO level remains almost unchanged. The elevation of the \u03c0O orbital would be due to the conjugation between the N lone pair and the carbonyl group. Thus, inversion of the energy levels of nO and \u03c0O would be responsible for the observed directional preferences of the S\u00b7\u00b7\u00b7O interactions in proteins.However, the \u03c0 et al. [N-acetylglucosamine-thiazoline and \u03b2-hexosaminidase and between benzophenone and porcine odorant-binding protein [\u2212 ligand and the imidazole ring of His109 in lactoperoxidase [The importance of S\u00b7\u00b7\u00b7O interactions in the enzymatic function of proteins has been pointed out for some particular cases. Taylor and Markham  suggeste et al.  reported protein . Importa protein . More reroxidase  and betwroxidase  were sugAccording to the comparison between the results from database analyses and ab initio calculation, it was clear that the directional preferences of the S\u00b7\u00b7\u00b7O interactions observed in protein structures are in accord with the profiles of the potential surfaces calculated for the isolated model complexes . An examProtein structures are generally considered to be flexible because they are governed only by weak nonbonded interactions. Therefore, coincidence of the statistical conformational preference for the interaction of proteins with the potential surface calculated for the isolated model is to be noticed and would have important implications in protein architecture. The detailed analysis revealed the following features . The linThe directionality, however, is easily affected by crystal packing force for organic molecules. Thus, the order of the factors that control molecular structure of organic molecules and proteins in the solid state can be summarized as shown in S* direction), irrespective of the types of carbonyl groups. On the other hand, the S atom tends to approach the O atom either within the carbonyl plane (in the nO direction) or from the vertical direction (in the \u03c0O direction). In the case of S\u00b7\u00b7\u00b7O(amide) interactions, the vertical direction is significantly preferred, due probably to elevation of the \u03c0O orbital. The linearity of the S\u00b7\u00b7\u00b7O interactions in organic molecules would overcome the crystal packing force, whereas the vertical nature of the S\u00b7\u00b7\u00b7O(amide) interactions may be affected by the packing force. The verticality, however, would survive in protein structures. These structural features will be informative for protein engineering and molecular design of functional organic sulfur compounds.The O atom has strong tendency to approach the S atom from the backside of the S\u2013C or S\u2013S bond (in the \u03c32 (PLA2) was the first example of such proteins [2 family. The results are summarized in this section.With a success in characterization of S\u00b7\u00b7\u00b7X interactions in proteins, we subsequently sought out particular protein families or domains, for which specific S\u00b7\u00b7\u00b7X interactions are commonly present in a wide range of the structures registered in the Protein Data Bank . Phosphoproteins . We have2 [2 family; PLA2 and snake PLA2 (sPLA2). Comprehensive search for close S\u00b7\u00b7\u00b7X  contacts in the structures of the PLA2 domain, which were retrieved from protein data bank, revealed the presence of four common S\u00b7\u00b7\u00b7O interactions, i.e., S(C44)\u00b7\u00b7\u00b7O(D40), S(C61)\u00b7\u00b7\u00b7O(A55), S(C84)\u00b7\u00b7\u00b7O(C96), and S(C98)\u00b7\u00b7\u00b7O(F94), and one common S\u00b7\u00b7\u00b7N interaction, i.e., S(M8)\u00b7\u00b7\u00b7N(R100), as shown in 2 is decreased in the M8,20L mutant [PLA2 ,63, a smL mutant . This wo2 domain. For this domain group, the phylogenetic dendrogram was already analyzed by Ohno et al. [2 involved in venom of snakes inhabiting the southern islands of Japan. Mapping the common S\u00b7\u00b7\u00b7O and S\u00b7\u00b7\u00b7N interactions observed by the database analysis, we found that most of the S\u00b7\u00b7\u00b7X interactions make clusters on the dendrogram. The results suggested a possible role of S\u00b7\u00b7\u00b7X interactions in molecular evolution of proteins.On the other hand, an evolutional aspect of the S\u00b7\u00b7\u00b7X interactions was analyzed for the sPLAo et al.  using th i.e., S(C26)\u00b7\u00b7\u00b7O\u03b3(T99) and S(C65)\u00b7\u00b7\u00b7O(Q69), and one common S\u00b7\u00b7\u00b7N interaction, i.e., S(C58)\u00b7\u00b7\u00b7N(P117), were characterized. The locations along the amino acid sequence are shown in RNase A  is a typC65)\u00b7\u00b7\u00b7OQ, and oneIn some RNase A structures complexed with a substrate, close S\u00b7\u00b7\u00b7X contacts between the S atom of the C65 residue and the substrate were found. Examples are S(C65)\u00b7\u00b7\u00b7O(ADT) in 8RSA , S(C65)\u00b7i.e., S(C20)\u00b7\u00b7\u00b7O(E17) and S(C19)\u00b7\u00b7\u00b7O(L15), were found within A and B chains, respectively, among the 23 high-resolution (\u22642.0 \u00c5) structures. Insulin  is a pepi.e., S(C127)\u00b7\u00b7\u00b7O(I124), and three common S\u00b7\u00b7\u00b7N interactions, i.e., S(C30)\u00b7\u00b7\u00b7N\u03b5(W123), S(C80)\u00b7\u00b7\u00b7N(N65), and S(C127)\u00b7\u00b7\u00b7N\u03b7(R5), were characterized as shown in Lysozyme  consists2 and sPLA2 were described in reference [Details of the database analysis of the S\u00b7\u00b7\u00b7X interactions in PLAeference . SimilarThe three-dimensional structure, hence the function, of a protein is controlled by the interplay of a number of weak nonbonded interactions, such as hydrogen bond, van der Waals forces, and hydrophobic interaction. According to the results from the database analyses and theoretical calculation summarized in this review, it would be concluded that hypervalent S\u00b7\u00b7\u00b7X interactions are also a member of such weak interactions. ab initio calculation. For four particular proteins, i.e., PLA2, RNase A, insulin, and lysozyme, unique S\u00b7\u00b7\u00b7X interactions have been characterized, and some were suggested to play roles in the stability of the native structures and the functions to some extent.Sulfur-containing functional groups of cystine (an SSC group) and methionine (a CSC group) were previously considered to be just hydrophobic moieties in protein structures, but they are indeed able to form specific nonbonded interactions with nearby polar non-hydrogen atoms  in folded proteins. A unique directionality of the S\u00b7\u00b7\u00b7X interactions see  would bei.e., integration of the database analyses and theoretical calculation, will be useful for characterization of other weak nonbonded interactions hidden in molecules as well as protein structures. Finally, the statistical analyses using the both protein and organic molecule structure databases demonstrated that the order of the strength of the factors that control molecular structures in the solid state can be expressed as shown in"}
{"text": "The resulting compounds, bis\u00ad di\u00adsulfide, C8H6O2S4S2, and bis\u00ad diselenide, C8H6O2Se6, are isotypic.By  8H6O2S6 and C8H6O2S4Se2, are isotypic with very similar cell parameters. The complete mol\u00adecules constitute the asymmetric units, despite being chemically perfectly symmetric. The most prominant differences in the metrical parameters arise from the distinct sizes of sulfur and selenium in the dichalcogenide bridges, with C\u2014S\u2014S\u2014C and C\u2014Se\u2014Se\u2014C torsion angles of 70.70\u2005(5) and 68.88\u2005(3)\u00b0, respectively. The crystal packing is determined by weak non-classical hydrogen-bonding inter\u00adactions. One carbonyl oxygen but not the other participates in C\u2014H\u22efO inter\u00adactions zigzagging along the b axis, forming infinite chains. This is complemented by an intra\u00admolecular C\u2014H\u22efS inter\u00adaction and further inter\u00admolecular C\u2014H\u22efS (C\u2014H\u22efSe) inter\u00adactions, resulting in a three-dimensional network. The inter\u00adactions involving the bridging chalcogenides form chains protruding along the c axis.The two title compounds, C In related di\u00adsulfides they range from 52.08 to 109.82\u00b0  are essentially planar, with maximum deviations from the least-squares plane of 0.028 and 0.022\u2005\u00c5 for the di\u00adsulfide and for the diselenide, respectively, corresponding to the distances from atom S1 to the O1\u2014S1\u2014S2\u2014C1\u2014C2\u2014C3 plane in both cases. The dihedral angles between the O1\u2014S1\u2014S2\u2014C1\u2014C2\u2014C3 and the O2\u2014S5\u2014S6\u2014C6\u2014C7\u2014C8 planes are 33.8\u2005(2)\u00b0 for the di\u00adsulfide and 28.89\u2005(11)\u00b0 for the diselenide. Here, a smaller torsion angle around the dichalcogenide bridge is accompanied by a smaller angle between the two planes of the 1,3-ene-di\u00adthiol-2-one moieties.B\u22efO1i inter\u00adactions zigzagging along the b axis, forming infinite chains \u2005\u00c5 for the disufide and 3.369\u2005(5)\u2005\u00c5 for the diselenide. This is complemented by two intra\u00admolecular inter\u00adactions between the two chalcogens of the dichalcogenide bridges and the adjacent methyl substituents (C4\u2014H4A\u22efS3/Se1 and C5\u2014H5A\u22efS4/Se2) with D\u22efA distances of 3.244\u2005(2) for S3, of 3.234\u2005(2) for S4, of 3.354\u2005(4) for Se1, and of 3.341\u2005(4) for Se2. Further inter\u00admolecular C\u2014H\u22efS and C\u2014H\u22efSe inter\u00adactions contribute to the formation of a three-dimensional network. The inter\u00adactions involving the bridging chalcogenides form chains protruding along the c axis . The first such thione crystal structure was reported in 1999 by Cerrada et al., which comprises an S\u2014S-linked [C3S5\u2014C3S5]2\u2212 dianion 2Cp complexes by coordination of thiol\u00adate sulfur to iron  by Kumar et al. selenolothio\u00adphen-6-yl}diselenide was formed unexpectedly by the reaction of 2-[(tri\u00adphenyl\u00adphospho\u00adnio)meth\u00adyl] thio\u00adphene chloride with sodium hydrogen selenite , and LDA  was added dropwise over 5\u2005min. The mixture was allowed to stand for 35\u2005min, warmed to ice-bath temperature and after a further 10 minutes quenched with a saturated aqueous solution of NH4Cl (around 20\u2005ml). The organic phase was diluted with EtOAc, separated and the aqueous phase re-extracted with Et2O (2 \u00d7 15\u2005ml). The combined organic phases were washed with brine, dried and the solvent evaporated in vacuo to give a yellowish oil as crude product. This was purified by chromatography (silica gel), eluting with EtOAc/petroleum ether (40/60) 3:97 v/v to give 4-methyl-5-tri-n-butyl\u00adstannyl-1,3-di\u00adthiol-2-one as the major product. During purification, a yellowish oily fraction was isolated and subsequently stored at 253\u2005K, forming large yellow crystals. Crystallographic evaluation of these crystals reveals the formation of the side product bis\u00ad di\u00adsulfide.Preparation of bis\u00ad diselenide: The synthesis was carried out under an inert gas atmosphere of nitro\u00adgen, whereas the purification steps were carried out in air. To a solution of 4-methyl-5-tri-n-butyl\u00adstannyl-1,3-di\u00adthiol-2-one  in freshly distilled dioxane (5\u2005ml) was added freshly sublimed selenium dioxide . The reaction mixture was heated at reflux temperature for 6\u2005h. After cooling, the solution was filtered through celite. Solvent removal gave an orange solid . Yellow crystals suitable for crystallographic analysis were obtained by recrystallization from acetone.iUso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018007454/wm5446sup1.cifCrystal structure: contains datablock(s) CSV72a12, it14ii. DOI: 10.1107/S2056989018007454/wm5446CSV72a12sup2.hklStructure factors: contains datablock(s) CSV72a12. DOI: 10.1107/S2056989018007454/wm5446it14iisup3.hklStructure factors: contains datablock(s) it14ii. DOI: 1843766, 1843765CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the 1:1 cocrystal of nicotinamide and 2-chloro-5-nitro\u00adbenzoic acid, the mol\u00adecules form hydrogen bonds through O\u2014H\u22efN, N\u2014H\u22efO, and C\u2014H\u22efO inter\u00adactions along with N\u2014H\u22efO dimer hydrogen bonds of nicotinamide. Further additional weak \u03c0\u2013\u03c0 inter\u00adactions stabilize the mol\u00adecular assembly of this cocrystal. 7H4ClNO4\u00b7C6H6N2O, nicotinamide (NIC) and 2-chloro-5-nitro\u00adbenzoic acid (CNBA) cocrystallize with one mol\u00adecule each of NIC and CNBA in the asymmetric unit. In this structure, CNBA and NIC form hydrogen bonds through O\u2014H\u22efN, N\u2014H\u22efO and C\u2014H\u22efO inter\u00adactions along with N\u2014H\u22efO dimer hydrogen bonds of NIC. Further additional weak \u03c0\u2013\u03c0 inter\u00adactions stabilize the mol\u00adecular assembly of this cocrystal.In the title 1:1 cocrystal, C In the asymmetric unit, an (CNBA)O\u2013H\u22efN inter\u00adaction plays a prime role in the mol\u00adecular recognition of this cocrystal  crystallizes in the monoclinic space group al Fig.\u00a01.et al., 1990via C\u2014H\u22efO hydrogen bonding and form a tetra\u00admeric ring with two mol\u00adecules each of NIC and CNBA with et al., 1990bc plane O\u2014H\u22efN(NIC) hydrogen bond and additional (NIC)N\u2014H\u22efO(CNBA) and (NIC)C\u2014H\u22efO(CNBA) hydrogen bonds are observed Fig.\u00a02. In thisne Fig.\u00a03.CrystalExplorer  and nicotinamide  in a minimum amount of ethanol and made up to a volume of 10\u2005ml. Ten different combinations of the mixture were prepared using ethanol\u2013hexane as the solvent mixture over the ratio range 1:1 to 1:10. The mixture was kept in a 5\u2005ml beaker and covered with parafilm, with four to five small holes in it. These solutions were allowed to evaporate slowly at room temperature (27 \u00b0C) over several days to obtain single crystals. After a few days, colourless crystals were obtained from ethanol\u2013hexane solutions with concentration ratios of 1:10, 1:2 and 1:4. The melting point of the obtained crystal was 159.7 \u00b0C.Crystal data, data collection, and structure refinement details are summarized in Table\u00a0210.1107/S2056989019013859/eb2025sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019013859/eb2025Isup2.hklStructure factors: contains datablock(s) I. DOI: 1958621, 1958621CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Four 1,2,4-triazole groups of the ligand link two AgI atoms, as well as AgI and VV centres, forming the heterobimetallic coordination cluster {AgI2(VVO2F2)2(tr)4}. VV exists as a vanadium oxofluoride anion and possesses a distorted trigonal\u2013bipyramidal coordination environment [VO2F2N]. A carb\u00adoxy\u00adlic acid functional group of the ligand stays in a neutral form and is involved in hydrogen bonding with solvent water mol\u00adecules and VO2F2\u2212 ions of adjacent mol\u00adecules. The extended hydrogen-bonding network is responsible for the crystal packing in the structure.The crystal structure of the title mol\u00adecular complex, [Ag It has recently been shown 2(tr)2}2+ binuclear fragment, two N atoms remain uncoordinated and have potential for further inter\u00adactions. In aqueous reaction media, vanadium oxofluorides exist in anionic forms with weakly coordinated water mol\u00adecules that are very labile toward N-donor ligand substitution. Thus, a combination of an AgI\u2013triazole cation and VOF anions lead to the neutral tetra\u00adnuclear {AgI2(VVO2F2)2(tr)4} unit, which was found in the structure of the title [Ag2(VO2F2)2(tr-ad-COOH)4]\u00b74H2O complex I  bond lengths , while the other two 1,2,4-triazole groups combine the Ag and V centres [Ag\u22efV= 3.5376\u2005(6)\u2005\u00c5]. The VV atom possesses a distorted trigonal\u2013bipyramidal coordination environment [VO2F2N] with short V\u2014O bonds , V\u2014F bonds  and an elongated V\u2014N bond [2.152\u2005(3)\u2005\u00c5]. The polyhedra can be more precisely described by the Reedijk\u2019s factor \u03c4 2(tr)4} is formed. A search in the Cambridge Structural Database 2[Mo4O13]}\u00b72H2O \u2005\u00c5 , while another COOH group, as a hydrogen-bond acceptor, is directed toward the F atom of a {VO2F2} anion . Two water mol\u00adecules are inter\u00adbonded [O2W\u2014H3W\u22efO1W = 2.753\u2005(4)\u2005\u00c5] and additionally act as hydrogen-bond donors with O and F atoms from the neighboring {VO2F2} anions and as hydrogen-bond acceptor (in the case of O2W ) with the O3 atom from an adjacent carb\u00adoxy\u00adlic group. Some weak contacts between the triazole C\u2014H groups and F atoms of the VOF anions are also observed.The structure of k Figs. 2 and 3 \u25b8.tr-ad-COOH) was synthesized in 63% yield by refluxing 3-amino-adamantane-1-carb\u00adoxy\u00adlic acid , tr-ad-COOH , V2O5  and 5\u2005mL of water with aqueous HF  was added into a Teflon vessel. Then the components were heated at 423\u2005K for 24\u2005h and slowly cooled to room temperature over 50\u2005h, yielding light-yellow prisms of I .1--3-carb\u00adoxy\u00adadamantane (2), C\u2014H = 0.98\u2005\u00c5 (adamantane CH) and with Uiso(H) = 1.2Ueq(C). O-bound hydrogen atoms were located in a difference-Fourier map and then refined with O\u2014H = 0.82\u2005\u00c5 (carb\u00adoxy\u00adlic) or 0.85\u2005\u00c5 (H2O) with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019006844/zq2246sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006844/zq2246Isup2.hklStructure factors: contains datablock(s) I. DOI: 1915603CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of the title spiro derivatives are described and the analysis of the inter\u00admolecular contacts in the crystals using Hirshfeld surface analysis and two-dimensional fingerprint plots is reported. a-hexa\u00adhydro\u00adspiro\u00adpyrrolo\u00adthia\u00adzole-11,11\u2032-indeno\u00adquinoxaline], C37H26N4O3S, (I), and 6\u2032--6a\u2032-nitro-6\u2032,6a\u2032,6b\u2032,7\u2032,8\u2032,9\u2032,10\u2032,12a\u2032-octa\u00adhydro-2H-spiro\u00adindolizin]-2-one, C36H28N2O4, (II), are new spiro derivatives, in which both the pyrrolidine rings adopt twisted conformations. In (I), the five-membered thia\u00adzole ring adopts an envelope conformation, while the eight-membered pyrrolidine-thia\u00adzole ring adopts a boat conformation. An intra\u00admolecular C\u2014H\u22efN hydrogen bond occurs, involving a C atom of the pyran ring and an N atom of the pyrazine ring. In (II), the six-membered piperidine ring adopts a chair conformation. An intra\u00admolecular C\u2014H\u22efO hydrogen bond occurs, involving a C atom of the pyrrolidine ring and the keto O atom. For both compounds, the crystal structure is stabilized by inter\u00admolecular C\u2014H\u22efO hydrogen bonds. In (I), the C\u2014H\u22efO hydrogen bonds link adjacent mol\u00adecules, forming R22(16) loops propagating along the b-axis direction, while in (II) they form zigzag chains along the b-axis direction. In both compounds, C\u2014H\u22ef\u03c0 inter\u00adactions help to consolidate the structure, but no significant \u03c0\u2013\u03c0 inter\u00adactions with centroid\u2013centroid distances of less than 4\u2005\u00c5 are observed.The title compounds, 6--6a-nitro-6,6a,6\u2005b,7,9,11 The eight-membered pyrrolidine-thia\u00adzole ring (S1/C24\u2013C27/C1/C16/N3) adopts a boat conformation with a total puckering amplitude Q = 1.351\u2005(2)\u2005\u00c5 and \u03c6 = 321.43\u2005(8)\u00b0. The mean planes of the pyran and thia\u00adzole rings are inclined to each other by 77.5\u2005(2)\u00b0. The mean plane of the pyrazine ring (N1/N2/C8/C9/C14/C15) forms a dihedral angle of 57.1\u2005(2)\u00b0 with the mean plane of the pyran ring, while it is almost perpendicular with respect to the mean plane of the pyrrolidine ring, forming an angle of 89.8\u2005(2)\u00b0. The pyrazine ring is inclined by 51.9\u2005(2), 1.9\u2005(2) and 69.5\u2005(2)\u00b0 with respect to the mean planes of the thia\u00adzole and cyclo\u00adpentene ring and the naphthalene ring system, respectively. An intra\u00admolecular C23\u2013H23\u22efN1 hydrogen bond is formed ed Fig.\u00a01.q2 = 0.045\u2005(2)\u2005\u00c5, \u03b8 = 175.7\u2005(2)\u00b0 and \u03c6 = 22\u2005(3)\u00b0. The dihedral angle between the ace\u00adnaphthyl\u00adene (C1\u2013C12) and naphthalene (C27\u2013C36) ring systems is 63.8\u2005(6)\u00b0. Moreover, this moiety is inclined of 85.3\u2005(1), 36.1\u2005(1) and 89.4\u2005(2) \u00b0 with respect to the mean planes of the pyrrolidine (N1/C12/C17\u2013C19), pyran (O4/C18\u2013C20/C25/C26) and piperidine (N1/C13\u2013C17) rings, respectively. The keto atom O1 deviates from the mean plane of the ace\u00adnaphthyl\u00adene unit by 0.148\u2005(1)\u2005\u00c5. An intra\u00admolecular C17\u2014H17\u22efO1 hydrogen bond is present nt Fig.\u00a02.b-axis direction. The loops are linked by C\u2014H\u22efS hydrogen bonds, forming layers parallel to the (101) plane; C\u2014H\u22ef\u03c0 inter\u00adactions are present within the layers on Fig.\u00a04. A C\u2014H\u22ef\u03c0et al., 2007CrystalExplorer17  through white to blue . The red spots on the surface indicate the inter\u00admolecular contacts involved in hydrogen bonding.The Hirshfeld surfaces of (I)b), C\u22efH/H\u22efC , O\u22efH/H\u22efO , S\u22efH/H\u22efS  and N\u22efH/H\u22efN , followed by the C\u22efC contacts . For (II)b), C\u22efH/H\u22efC , O\u22efH/H\u22efO , followed by the C\u22efC contacts . In both compounds the H\u22efH inter\u00admolecular contacts predominate.The fingerprint plots for the two compounds are given in Figs. 9et al., 2016H,6\u2032H,6b\u2032H-spiro\u00adindolizin]-2-one skeleton yielded five hits: namely 6-(4- meth\u00adoxy\u00adphen\u00adyl)-6a-nitro-6,6a,6b,7,8,9,10,12a-octa\u00adhydro\u00adspiro-indolizine-12,3-indolin]-2-one  to a solution of indeno\u00adquinoxalinone  and thia\u00adzolidine-4-carb\u00adoxy\u00adlic acid  in dry toluene, 0.302\u2005g (1.0\u2005mmol) of 2--3-nitro-2H-chromene were added under a nitro\u00adgen atmosphere.Compound (II) to a solution of ace\u00adnaphtho\u00adquinone  and pipacolinic acid  in dry toluene,  of 2--3-nitro-2H-chromene were added under a nitro\u00adgen atmosphere.The solutions were refluxed for 18\u2005h in a Dean\u2013Stark apparatus to give the cyclo\u00adadducts. After completion of the reactions as indicated by TLC, the solvent was evaporated under reduced pressure. The crude products obtained were purified by column chromatography using hexa\u00adne/EtOAc (7:3) as eluent (yield 84%). Colourless block-like crystals of the title compounds, suitable for X-ray diffraction analysis, were obtained by slow evaporation of solutions in ethanol.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S205698901901291X/xi2018sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S205698901901291X/xi2018Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901901291X/xi2018IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S205698901901291X/xi2018Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698901901291X/xi2018IIsup5.cmlSupporting information file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The dihedral angle between the 4-bromo\u00adphenyl rings is 51.56\u2005(2)\u00b0. In the crystal, mol\u00adecules are linked into a zigzag chain propagating along [001] by weak C\u2014H\u22ef\u03c0 inter\u00adactions. The conformations of related bis\u00adchalcones are surveyed and a Hirshfeld surface analysis is used to investigate and qu\u00adantify the inter\u00admolecular contacts.In the title bis\u00adchalcone, C E,4E)-1,5-di\u00adphenyl\u00adpenta-1,4-dien-3-one] was first prepared by the base-catalyzed Aldol condensation of benzaldehyde and acetone \u2014C=C\u2014) moiety. Bischalcones have a number of uses including anti-inflammatory ; \u03c44 (C13\u2014C12\u2014C11\u2014C10)] and the carbonyl double bond  \u00b0; \u03c44 = \u22126.2\u2005(4)\u00b0] but the conformations of the olefinic double bonds are very different: one is in s-trans [\u03c42 = 160.7\u2005(3)\u00b0] conformation and in s-cis [\u03c43 = \u221215.2\u2005(4)\u00b0] conformation with the central C=O double bond. These torsions result in an overall twisted shape for (I)The asymmetric unit of (I))] Fig.\u00a02. The 4-bvia C1\u2014H1A\u22efCg1i . The C14\u2014H14A\u22efCg2ii  inter\u00adactions lead to a zigzag chain along the c-axis direction.No classical hydrogen bonding is possible in (I)1i Fig.\u00a03a. The Cii Fig.\u00a03b inter\u00adet al., 2016E,4E)-1,5-di\u00adphenyl\u00adpenta-1,4-dien-3-one as the main skeleton revealed the presence of 27 structures containing a similar bis\u00adchalcone moiety to the title compound but with different substituents on the terminal phenyl rings. The different substituents (1R and 2R) together with the torsion angles of the penta-4,4-dien-3-one connecting bridge are compiled in Table\u00a02s-cis or s-trans), the olefinic double bonds are close to coplanar with their attached phenyl rings as indicated by their \u03c41 and \u03c44 torsion angles, which fall in the range of 0.0\u201317.8\u00b0, except for the compounds AMEXUN and HUDLEY, which have somewhat larger \u03c41 and \u03c44 values of 22.5\u201327.4\u00b0. The olefinic double bonds for the symmetrical compounds are mostly in s-cis conformations with the carbonyl double bond (\u03c42/\u03c43 torsion angles of 0.1\u201321.9\u00b0). However, both the olefinic double bonds of compounds GOLGOD and GOLGOD02 are in s-trans conformations with the carbonyl double bond (\u03c42/\u03c43 = 152.2\u2013153.4\u00b0). Furthermore, it may be noted that the symmetrical conformation at the penta-4,4-dien-3-one connection bridge is not affected by the different substituents at the 1R and 2R positions in EDUSEE, SAFZOO and XOHVUN. Most of the unsymmetrical compounds (one C=C\u2014C=O bond s-cis and one s-trans) have \u03c41 and \u03c44 values of 0.5\u201317.2\u00b0, which indicates that the olefinic double bonds are close to coplanar to their attached phenyl ring. The outliers are MESXEQ and WIHBUL, which have \u03c41 and \u03c44 values of 18.2\u201351.8\u00b0 and 21.4\u201351.8\u00b0, respectively. The torsion angles \u03c42 and \u03c43 for the unsymmetrical compounds, including (I)s-trans and s-cis conformations between the olefinic double bonds and the carbonyl double bond.A survey of the Cambridge Structural Database CrystalExplorer17.5  correspond to the C14\u2014H14A\u22efCg2ii inter\u00adaction. Even through the C1\u2014H1A\u22efCg1i inter\u00adaction is not visible in the dnorm surface mapping, this inter\u00adaction can be seen as a unique pattern of a red \u2018circle\u2019 on the shape-index surface mapping . Besides the C\u2014H\u22ef\u03c0 inter\u00adactions, the dnorm surface mapping indicated a short contact between atom O1 and C5 with a distance of 0.06\u2005\u00c5 shorter than the sum of the van der Waals radii of O and C atoms . Together with this short contact, another weak C7\u2014H7A\u22efO1 inter\u00adaction was also revealed as light spots on the dnorm surface .The Hirshfeld surfaces mapped with normalized contact distance rm Fig.\u00a04a corresng Fig.\u00a04b. Besidce Fig.\u00a05b.de and di diagonal axes. The H\u22efC/C\u22efH contacts are the most populated contacts and contribute 34.1% to the total inter\u00admolecular contacts, followed by H\u22efH (22.1%), H\u22efBr/Br\u22efH (20.4%) and H\u22efO/O\u22efH (9.2%) contacts . The H\u22efH contacts appear in the central region of the fingerprint plots with de = di = 2.4\u2005\u00c5 . With the presence of relatively larger bromine atoms in the structure, the H\u22efBr/Br\u22efH contacts appear as symmetrical broad wing at diagonal axes of de + di \u2243 3.0\u2005\u00c5 . Two symmetric spikes in the fingerprint plots with a short spike at de + di \u2243 2.7\u2005\u00c5 represent the H\u22efO/O\u22efH contacts , indicating the presence of the weak C7\u2014H7A\u22efO1 inter\u00adaction. The percentage contributions for other contacts are less than 15% in the Hirshfeld surface mapping.As illustrated in Fig.\u00a06ts Fig.\u00a06. As the \u2005\u00c5 Fig.\u00a06b. The H\u2005\u00c5 Fig.\u00a06c. With \u2005\u00c5 Fig.\u00a06d. Two sts Fig.\u00a06e, indicA mixture of 4-bromo\u00adbenzaldehyde  and acetone  dissolved in absolute ethanol (30\u2005ml) was slowly added to an aqueous solution of potassium hydroxide (4.0\u2005g in 20\u2005ml water). The mixture was vigorously stirred at room temperature for two\u2005h and then 20\u2005ml chilled water was added. The resulting yellow precipitate was recovered by vacuum filtration and washed with cold water (100\u2005ml). The crude product was recrystallized from absolute ethanol solution as yellow blocks.-1,5-Bis\u00ad(4-bromo\u00adphen\u00adyl)penta-1,4-dien-3-one; pure yellow solid , m.p. 484\u2005K; IR \u03bdmax 594, 687, 813, 979, 1066, 1181, 1320, 1398, 1480, 1581, 1643\u2005cm\u22121, UV\u2013Vis \u03bbmax. 227 and 317\u2005nm, 1H NMR:\u03b4H  7.02 , 7.45 , 7.54 , 7.67 ; 13C NMR:\u03b4C  124.62, 125.69, 129.25, 131.74, 133.29, 141.83, 188.22; HRMS (ES): MH+, found: 392 C17H12Br2O+ requires: 391.92.Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019006480/hb7821sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006480/hb7821Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019006480/hb7821Isup3.cmlSupporting information file. DOI: 1914420CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the compound, the acid and base mol\u00adecules are linked by a short hydrogen bond [O\u22efO = 2.4393\u2005(15)\u2005\u00c5], in which the H atom is disordered over two positions with equal occupancies.The title compound was analysed as a disordered structure over two states,  9H7.5NO\u00b7C7H3.5ClNO4, was analysed as a disordered structure over two states, viz. co-crystal and salt, accompanied by a keto\u2013enol tautomerization in the base mol\u00adecule. The co-crystal is 4-chloro-2-nitro\u00adbenzoic acid\u2013quinolin-4(1H)-one (1/1), C7H4ClNO4\u00b7C9H7NO, and the salt is 4-hy\u00addroxy\u00adquinolinium 4-chloro-2-nitro\u00adbenzoate, C9H8NO+\u00b7C7H3ClNO4\u2212. In the compound, the acid and base mol\u00adecules are held together by a short hydrogen bond [O\u22efO = 2.4393\u2005(15)\u2005\u00c5], in which the H atom is disordered over two positions with equal occupancies. In the crystal, the hydrogen-bonded acid\u2013base units are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, forming a tape structure along the a-axis direction. The tapes are stacked into a layer parallel to the ab plane via \u03c0\u2013\u03c0 inter\u00adactions [centroid\u2013centroid distances = 3.5504\u2005(8)\u20133.9010\u2005(11)\u2005\u00c5]. The layers are further linked by another C\u2014H\u22efO hydrogen bond, forming a three-dimensional network. Hirshfeld surfaces for the title compound mapped over shape-index and dnorm were generated to visualize the inter\u00admolecular inter\u00adactions.The title compound, C D\u2014H\u22efA hydrogen bonding  in chloro- and nitro-substituted benzoic acid\u2013pyridine derivative systems, we have shown that several compounds, namely, three compounds of quinoline with 3-chloro-2-nitro\u00adbenzoic acid, 4-chloro-2-nitro\u00adbenzoic acid and 5-chloro-2-nitro\u00adbenzoic acid -quinolinone (1/1), and the salt, 4-hy\u00addroxy\u00adquinolinium 4-chloro-2-nitro\u00adbenzoate, accompanied by a keto\u2013enol tautomerization in the base mol\u00adecule. The C10\u2014O5 bond length [1.2956\u2005(18)\u2005\u00c5] is inter\u00admediate between a C\u2014O single bond [1.36\u2005\u00c5 in phenol] and a C=O double bond [1.23\u2005\u00c5 in ketones of the (Car)2\u2014C=O type]  of the acid mol\u00adecule and the quinoline ring system (N2/C8\u2013C16) of the base are slightly inclined to each other by a dihedral angle of 10.27\u2005(6)\u00b0, while the carb\u00adoxy group (O1/C7/O2) is twisted by 38.66\u2005(18) and 45.93\u2005(18)\u00b0, respectively, with respect to the C1\u2013C6 ring and the N2/C8\u2013C16 ring system. The dihedral angle between the C1\u2013C6 ring and the nitro group (O3/N1/O4) is 50.33\u2005(19)\u00b0.i, C8\u2014H8\u22efO5i and C9\u2014H9\u22efO1i; symmetry code as in Table\u00a01a axis  \u2212x\u00a0+\u00a0y\u00a0\u2212\u00a0z]. The layers are further linked by another C\u2014H\u22efO hydrogen bond \u2013(3)]. The \u03c0\u2013\u03c0 inter\u00adactions between the benzene rings of the acid mol\u00adecules [Cg1\u22efCg1iv] and between the quinoline ring systems of the base mol\u00adecules  are indicated by blue and red triangles on the shape-index surfaces [arrows (4) and (5)].In order to visualize the inter\u00admolecular inter\u00adactions, Hirshfeld surfaces for the acid and base mol\u00adecules of the title compound, mapped over shape-index and i Table\u00a01 are repret al., 2016H)-quinolinone (keto tautomer) showed one structure, namely, 4-amino-1-(2-(hy\u00addroxy\u00admeth\u00adyl)-1,3-oxa\u00adthio\u00adlan-5-yl)-2(1H)-pyrimidinone 4(1H)-quinolinone -quinolinone itself was reported by Nasiri et al.  of 4-hy\u00addroxy\u00adquinoline (0.075\u2005g) with 4-chloro-2-nitro\u00adbenzoic acid (0.106\u2005g) in a 1:1 molar ratio at room temperature.A (O1 site) and H1B (O5 site), respectively, with bond restraints of O\u2014H = 0.84\u2005(1)\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O). In the final refinement, the occupancies were fixed at 0.5, and one outlier  was omitted. The N-bound H atom was refined freely [refined distance: N2\u2014H2 = 0.89\u2005(2)\u2005\u00c5]. Other H atoms were positioned geometrically (C\u2014H = 0.95\u2005\u00c5) and treated as riding, with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901901497X/lh5935sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901901497X/lh5935Isup2.hklStructure factors: contains datablock(s) I. DOI: 1963942, 1963942CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The chains are linked into layers parallel to the bc plane by sets of four C\u2014H\u22efO hydrogen bonds and the layers are tied together by complementary \u03c0-stacking inter\u00adactions.The di\u00adhydro\u00adqinoxalinone portion of the mol\u00adecule is planar to within 0.0512\u2005(12)\u2005\u00c5. In the crystal, a combination of C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds together with slipped \u03c0-stacking and C\u2014H\u22ef\u03c0(ring) inter\u00adactions lead to the formation of chains extending along the  16H17N5O3, is build up from two fused six-membered rings linked to a 1,2,3-triazole ring, which is attached to an ethyl azido-acetate group. The di\u00adhydro\u00adqinoxalinone portion is planar to within 0.0512\u2005(12)\u2005\u00c5 and is oriented at a dihedral angle of 87.83\u2005(5)\u00b0 with respect to the pendant triazole ring. In the crystal, a combination of inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efN hydrogen bonds together with slipped \u03c0-stacking [centroid\u2013centroid distance = 3.7772\u2005(12)\u2005\u00c5] and C\u2014H\u22ef\u03c0 (ring) inter\u00adactions lead to the formation of chains extending along the c-axis direction. Additional C\u2014H\u22efO hydrogen bonds link these chains into layers parallel to the bc plane and the layers are tied together by complementary \u03c0-stacking [centroid\u2013centroid distance = 3.5444\u2005(12)\u2005\u00c5] inter\u00adactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (44.5%), H\u22efO/O\u22efH (18.8%), H\u22efN/N\u22efH (17.0%) and H\u22efC/C\u22efH (10.4%) inter\u00adactions.The mol\u00adecule of the title compound, C The pendant triazole ring is inclined to this plane by 87.83\u2005(5)\u00b0.Dhyqnx\u22efOEthazac, C\u2014HEthazac\u22efODhyqnx, C5\u2014HDhyqnx\u22efNEthazac and C\u2014HTrz\u22efNDhyqnx  hydrogen bonds  rings [centroid\u2013centroid distance = 3.7772\u2005(12)\u2005\u00c5] and by complementary C\u2014HDhyqnx\u22efCg3 inter\u00adactions [Cg3 is the centroid of the benzene ring B (C1\u2013C6)] (Table\u00a01bc plane by sets of four C\u2014HDhyqnx\u22efOEthazac hydrogen bonds (Table\u00a01a-axis direction by inversion-related slipped \u03c0-stacking inter\u00adactions between the A and B rings [centroid\u2013centroid distance = 3.5444\u2005(12)\u2005\u00c5]  analysis  contacts -one (0.65\u2005mmol) in ethanol (20\u2005mL) was added ethyl azido\u00adacetate (1.04\u2005mmol). The mixture was stirred under reflux for 24\u2005h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue was purified by column chromatography on silica gel by using as eluent a hexa\u00adne/ethyl acetate (9/1) mixture. Crystals were obtained when the solvent was allowed to evaporate. The solid product isolated was recrystallized from ethanol to afford yellow crystals in 75% yield.To a solution of 3-methyl-1-(prop-2-yn\u00adyl)-3,4-di\u00adhydro\u00adquinox\u00adalin-2 global, I. DOI: 10.1107/S2056989018014561/xu5945Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018014561/xu5945Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018014561/xu5945Isup4.cmlSupporting information file. DOI: 1873385CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In each of the title compounds, the packing is driven by C\u2014H\u22efF inter\u00adtactions, along with a variety of C\u2014H\u22efO, C\u2014O\u22ef\u03c0, and C\u2014F\u22ef\u03c0 contacts. Hirshfeld surface analyses were conducted to aid in the visualization of these various influences on the packing. 14H8F4N2O2 and C14H8F4N2O3, are reported. In each crystal, the packing is driven by C\u2014H\u22efF inter\u00adtactions, along with a variety of C\u2014H\u22efO, C\u2014O\u22ef\u03c0, and C\u2014F\u22ef\u03c0 contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing: they showed that the largest contributions to the surface contacts arise from H\u22efF/F\u22efH inter\u00adactions, followed by H\u22efH and O\u22efH/H\u22efO.The syntheses and crystal structures of the title compounds, C In mol\u00adecule A, the N1/C1\u2013C5 plane is rotated by 58.05\u2005(5)\u00b0 relative to the N2/C6/C7/C12/C13 plane and the corres\u00adponding dihedral angle for mol\u00adecule B is 61.65\u2005(7)\u00b0. The addition of an oxygen atom between N2 and C3 in II alleviates this steric restriction and only one 19F NMR peak in solution is observed for the ortho-F atoms; even so, the dihedral angle between the N1/C1\u2013C5 and N2/C6/C7/C12/C13 planes in the crystal of II of 84.01\u2005(5)\u00b0 is larger than those found in I.Compound it Fig.\u00a01. The synI and II are of the type C\u2014H\u22efO, C\u2014H\u22efF, C\u2014O\u22ef\u03c0, and C\u2014F\u22ef\u03c0  and the olefinic hydrogen atoms . A weak inter\u00adaction is also observed for a bridge hydrogen atom in II, C14\u2014H14B\u22efF4iii. The packing is further aided by \u03c0-inter\u00adactions with the pyridine ring .The main directional inter\u00adactions in the crystal structures of  Tables 1 and 2 \u25b8.CrystalExplorer17.5  to 1.3800 (blue) a.u. The pale-red spots symbolize short contacts and negative dnorm values on the corresponding surface plots shown in Fig.\u00a02Hirshfeld surface analysis  < 1.25\u2005\u00c5 in I and 1.10\u2005\u00c5 < (di + de) < 1.35\u2005\u00c5 in II. H\u22efH contacts make the second largest contribution (20.2% in I and 14.1% in II), shown in the middle region 1.10\u2005\u00c5 < (di + de) < 1.18\u2005\u00c5 in I and II. The third largest contribution is from O\u22efH/H\u22efO contacts. In I, the corresponding spike is partially overlapped with the spike representing F\u22efH/H\u22efF contacts, appearing at 1.05\u2005\u00c5 < (di + de) < 1.40\u2005\u00c5. The O\u22efH/H\u22efO spike is clearly visible in the fingerprint plot of II, shown in the region of 1.10\u2005\u00c5 < (di + de) < 1.40\u2005\u00c5.The largest contribution to the overall crystal packing in both compounds is from F\u22efH/H\u22efF inter\u00adactions -dione-based compounds with an aromatic substituent on the nitro\u00adgen atom yielded 58 results. The dihedral angle between the aromatic ring plane and the succinimide plane is bimodally distributed between 43 and 90\u00b0, with peaks near 60 and 75\u00b0.A search of the November 2018 release of the Cambridge Structure Database (Groom Synthesis of (I) penta\u00adfluoro\u00adpyridine , -3a,4,7,7a-tetra\u00adhydro-1H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione , and tri\u00adethyl\u00adamine  were combined in DMF (150\u2005ml). The resulting solution was stirred at room temperature for 24\u2005h. Diethyl ether (150\u2005ml) and saturated aqueous ammonium chloride (100\u2005ml) were added and the biphasic solution stirred vigorously for 2\u2005h. The organic layer was separated and the remaining aqueous portion extracted with diethyl ether (2 \u00d7 150\u2005ml). The combined organic fractions were washed with water (2 \u00d7 1\u2005l) and brine (2 \u00d7 300\u2005ml), dried over MgSO4, and the solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (20\u2005ml) and cooled to 278\u2005K for 12\u2005h. Vacuum filtration, washing with cold EtOH (20\u2005ml), and vacuum drying afforded the target compound as a white, crystalline solid . 1H NMR : 6.28 , 3.58 , 3.54 , 1.74 .19F NMR : \u221290.5 (2F), \u2212141.7 (1F), \u2212143.1 (1F).Synthesis of (II) to a stirred solution of potassium carbonate , -2-hy\u00addroxy-3a,4,7,7a-tetra\u00adhydro-1H-4,7-methano\u00adiso\u00adindole-1,3(2H)-dione , penta\u00adfluoro\u00adpyridine , and 140\u2005ml of DMF were added. The resulting solution was stirred at room temperature for 24\u2005h. Diethyl ether (150\u2005ml) and saturated aqueous ammonium chloride (100\u2005ml) were added and the biphasic solution stirred vigorously for 2\u2005h. The organic layer was separated and the remaining aqueous portion extracted with diethyl ether (2 \u00d7 150\u2005ml). The combined organic fractions were washed with water (2 \u00d7 1\u2005l) and brine (2 \u00d7 300\u2005ml), dried over MgSO4, and the solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (50\u2005ml) and cooled to 278\u2005K for 12\u2005h. Vacuum filtration, washing with cold EtOH (20\u2005ml) and vacuum drying afforded the target compound as a white, crystalline solid . 1H NMR : 6.23 , 3.50 , 3.34 , 1.68 .19F NMR : \u221287.4 (2F), \u2212156.3 (2F).Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019009769/hb7832sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989019009769/hb7832Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009769/hb7832IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019009769/hb7832Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019009769/hb7832IIsup5.cmlSupporting information file. DOI: 1879244, 1885019CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound crystallizes with two independent mol\u00adecules in the asymmetric unit. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds, C\u2014H\u22ef\u03c0, I\u22efS and I\u22efI inter\u00adactions into a three-dimensional network. A and B) are present in the asymmetric unit of the title compound, C11H9IN2OS, which differ mainly in the dihedral angle between the phenyl and thia\u00adzole rings . In the crystal, the mol\u00adecules form \u22efA\u22efB\u22efA\u22efB\u22ef chains along the [001] and [010] directions through moderate N\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adactions, respectively. The overall three-dimensional network is formed by I\u22efI and I\u22efS inter\u00adactions. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H\u22efC/C\u22efH (26.2%), H\u22efH (20.9%), H\u22efI/I\u22efH (19.4%) and H\u22efO/O\u22efH (6.8%) inter\u00adactions.Two crystallographically independent mol\u00adecules ( Unlike the related compound 2-acetamido-4-p-tolyl-1,3-thia\u00adzole .The title 2-aceto\u00adamido\u00adthia\u00adzole derivative crystallizes in the monoclinic space group it Fig.\u00a01. The privia a C(4) synthon  contacts [3.7758\u2005(9)\u2005\u00c5]  contacts of type I [\u03b81 = \u03b82 = 146.91\u2005(8)\u00b0] with a length of 3.8547\u2005(5)\u2005\u00c5.In the crystal, mol\u00adecules are linked by N1\u2014H1\u22efO2 and N3\u2014H3\u22efO1 moderate hydrogen bonds n Table\u00a01, forming\u00c5] Fig.\u00a03. AdditioCrystal Explorer17.5  to 1.3937 (blue) a.u. . The pair of characteristic wings in this fingerprint plot corresponds to the C\u2014H\u22ef\u03c0 inter\u00adactions between the phenyl groups . The H\u22efH and H\u22efI/I\u22efH contacts  make similar contributions to the total Hirshfeld surface of 20.9 and 19.4%, respectively. The reciprocal H\u22efO/O\u22efH inter\u00adactions (6.8%) are seen as sharp symmetrical spikes with tips at ed + id \u223c1.9\u2005\u00c5 and arising from the N\u2014H\u22efO hydrogen bond . Inter\u00admolecular I\u22efS/S\u22efI  and I\u22efI inter\u00adactions make smaller contributions to the Hirshfeld surface .A Hirshfeld surface analysis was carried out using u. Fig.\u00a04. The intps Fig.\u00a05b. The Hts Fig.\u00a05c and 5dnd Fig.\u00a05e. Inter\u22efI Fig.\u00a05f and I\u22efet al., 2016N--4-chloro\u00adbutanamide -1,3-thia\u00adzol-2-yl)-4-chloro\u00adbutanamide. In this compound the dihedral angle is smaller [8.8\u2005(3)\u00b0] as a result of an intra\u00admolecular C\u2014H\u22efBr hydrogen bond. In the crystals of these compounds, only 5,5\u2032-di\u00adbromo-4,4\u2032-bis(penta\u00adfluoro\u00adphen\u00adyl)-2,2\u2032-bi-1,3-thia\u00adzole exhibits a type II halogen\u2013halogen inter\u00adaction with a Br\u22efBr distance of 3.6777\u2005(3)\u2005\u00c5 and angles of 68.88\u2005(5) and 174.77\u2005(5)\u00b0.A search of the Cambridge Structural Database  acetamide  and iodine  was placed in an open vessel containing a Teflon-coated stir bar. The mixture was dissolved in 3\u2005mL of ethanol and the vessel was placed in the microwave cavity  and subjected to MW irradiation (150\u2005W) for 60\u2005min, at 363\u2005K and a pressure of 2\u2005psi. The reaction mixture was then cooled at room temperature and 5\u2005mL of NH4OH were added. The obtained mixture was dissolved in ethyl acetate (50\u2005mL) and washed with brine (3\u00d7). The organic layer was separated, dehydrated with Na2SO4, and evaporated in vacuo until dryness. The product was purified by flash column chromatography  with a mixture of petrol\u2013di\u00adchloro\u00admethane\u2013acetone (5:3:2). The title compound was obtained as pale-yellow needles in 30% yield . A diluted solution of the compound was prepared in hexane and kept on a dry and dark place at room temperature. Crystals were obtained after one week of slow evaporation. Spectroscopic data: 1H NMR : 11.37 , 7.80 , 7.43 , 1.62 . 13C NMR : 168.8 (s), 163.6 (s), 151.4 (s), 134.5 (s), 129.0 (d), 128.9 (d), 128.7 (d), 62.4 (s) 21.9 (c).A mixture of Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019004791/lh5897sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019004791/lh5897Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019004791/lh5897Isup3.cmlSupporting information file. DOI: 1908908CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I (HypSiBr), and II (TipSiBr), crystallized in the cubic space group PaPThe title compounds,  9H27BrSi4  and C27H63BrSi4 , are described. Compound I was prepared in 85% yield by free-radical bromination of 1,1,1,3,3,3-hexa\u00admethyl-2-(tri\u00admethyl\u00adsil\u00adyl)tris\u00adilane using bromo\u00adbutane and 2,2\u2032-azobis(2-methyl\u00adpropio\u00adnitrile) as a radical initiator at 333\u2005K. The mol\u00adecule possesses threefold rotational symmetry, with the central Si atom and the Br atom being located on the threefold rotation axis. The Si\u2014Br bond distance is 2.2990\u2005(12)\u2005\u00c5 and the Si\u2014Si bond lengths are 2.3477\u2005(8)\u2005\u00c5. The Br\u2014Si\u2014Si bond angles are 104.83\u2005(3)\u00b0 and the Si\u2014Si\u2014Si bond angles are 113.69\u2005(2)\u00b0, reflecting the steric hindrance inherent in the three tri\u00admethyl\u00adsilyl groups attached to the central Si atom. Compound II was prepared in 55% yield by free-radical bromination of 1,1,1,3,3,3-hexa\u00adisopropyl-2-(triiso\u00adpropyl\u00adsil\u00adyl)tris\u00adilane using N-bromo\u00adsuccinimide and 2,2\u2032-azobis(2-methyl\u00adpropio\u00adnitrile) as a radical initiator at 353\u2005K. Here the Si\u2014Br bond length is 2.3185\u2005(7)\u2005\u00c5 and the Si\u2014Si bond lengths range from 2.443\u2005(1) to 2.4628\u2005(9)\u2005\u00c5. The Br\u2014Si\u2014Si bond angles range from 98.44\u2005(3) to 103.77\u2005(3)\u00b0, indicating steric hindrance between the three triiso\u00adpropyl\u00adsilyl groups.The synthesis and crystal structures of two tris\u00adsilyl bromide compounds, C The Si1\u2014Br1 bond length is 2.2990\u2005(12)\u2005\u00c5. As for Si2, the C\u2014Si2\u2014C bond angles range from 107.1\u2005(2) to 110.55\u2005(17)\u00b0, while the C\u2014Si2\u2014Si1 bond angles range from 108.61\u2005(10) to 110.16\u2005(11)\u00b0.The mol\u00adecular structure of compound II (TipSiBr), is shown in Fig.\u00a02P4 descriptor for fourfold coordination of 0.90. The Br1\u2014Si1\u2014Si2/Si3/Si4 bond angles range from 98.44\u2005(3) to 103.77\u2005(3)\u00b0, and the Si1\u2014Br1 bond distance is 2.3185\u2005(7)\u2005\u00c5, which is longer than that of compound I [2.2990\u2005(12)\u2005\u00c5]. The \u03c44 descriptor values for atoms Si2, Si3 and Si4 (the silicon atoms of the triiso\u00adpropyl\u00adsilyl groups) are 0.96, 0.97 and 0.95, respectively, indicating that their coordination geometry is closest to an ideal tetra\u00adhedron.The asymmetric unit of compound I or II. Compound II, however, contains four intra\u00admolecular C\u2014H\u22efBr hydrogen bonds (Table\u00a02D\u22efA distances that range from from 3.584\u2005(3) to 3.726\u2005(3)\u2005\u00c5, and D\u2014H\u22efA bond angles that range from 131 to 155\u00b0.There are no significant inter\u00admolecular contacts, other than weak van der Waals inter\u00adactions, present in the crystals of compounds s Table\u00a02. These het al., 20163Si group. Of these, there are only 42 structures where the central silicon atom is bonded directly to a halogen.The Cambridge Structural Database  . The protio derivative (HypSiH) is a liquid at room temperature, and the structure of the iodo derivative (HypSiI) has not been deposited in the CSD.For compounds IV (TipSiH) was not found in the CSD, but the journal article 3SiBr, viz. compound II (TipSiBr). Like compounds I and III, compound IV crystallizes in the cubic space group PaiPr3)Si\u2013 groups to push further away from one another, resulting in Si2\u2014Si1\u2014Si2i,ii bond angles of 117.9\u2005(1)\u00b0 and Si2i,ii\u2014Si1\u2014H bond angles of 98.3\u2005(1)\u00b0 . In II, the corresponding Si\u2014Si\u2014Si bond angles range from 115.02\u2005(4) to 116.59\u2005(4)\u00b0 and the Si\u2014Si\u2014Br bond angles vary from 98.44\u2005(3) to 103.77\u2005(3)\u00b0.The X-ray data for compound Compound I: Tris(tri\u00admethyl\u00adsil\u00adyl)silane  was added to an oven-dried nitro\u00adgen-flushed 250\u2005ml Schlenk flask with a stir-bar. Bromo\u00adbutane  was filtered through a plug of silica gel in a Pasteur pipette and was transferred into the Schlenk flask. AIBN  was then added to the flask, and the reaction was heated to 333\u2005K using an oil bath and then heating was stopped. After stirring the reaction overnight at room temperature, GC\u2013MS analysis of a sample indicated incomplete reaction and more AIBN (11\u2005mg) was added to the flask. The reaction was heated once more to 333\u2005K for 1\u2005h. Analysis by GC\u2013MS now indicated that the reaction was complete. The flask was placed in a freezer at 243\u2005K and colourless block-like crystals of I formed overnight. Removal of the solvent in vacuo yielded 2.2\u2005g (85%). 1H NMR  \u03b4 0.24 ; 13C NMR  \u03b4 \u22120.51 ppm; GC\u2013MS: 11.24\u2005min, m/z = 328, base peak: 73.Compound II: Tris(triiso\u00adpropyl\u00adsil\u00adyl)silane  was dissolved in freshly distilled benzene (10\u2005ml) along with NBS (45\u2005mg) and AIBN . The mixture was heated using an oil bath at 333\u2005K for 30\u2005min, when GC\u2013MS analysis indicated that no reaction had occurred. At this point the solution was heated with a heat gun until the reaction mixture turned slightly yellow. The yellow colour dissipated in less than 1\u2005min. Analysis of the reaction mixture by 1H NMR indicated that only 60% of the starting material had been consumed. An additional amount of NBS  was added to the reaction flask, and the solution was again heated with a heat gun. The product was isolated by removing the solvent in vacuo and extracting the product from the crude reaction mixture with pentane. The pentane solution was filtered through glass wool, concentrated and weighed (135\u2005mg). Analysis of the product with 1H NMR indicated this was 90% pure. The product was further purified by dissolving this solid in 1\u2005ml pentane, cooling to 195\u2005K and isolating the colourless needle-like crystals of II by removing the solvent with a syringe, washing with pentane and drying in vacuo . 1H NMR  \u03b4 1.34 , 1.66 ; 13C NMR  \u03b4 16.4, 21.6; HRMS for C17H63BrSi4 calculated 535.2642 (M\u00a0\u2212\u00a0C3H7), found 535.2641.Uiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018009696/su5451sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989018009696/su5451Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018009696/su5451IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018009696/su5451Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018009696/su5451IIsup5.cmlSupporting information file. DOI: 1854536, 1854535CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound comprises four crystallographically different mol\u00adecules that are composed of a 1,5-bis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)penta-1,4-dien-3-ylidenyl group and a benzyl ring connected by a hydrazine-1-carbodi\u00adthio\u00adate bridge. In the crystal, mol\u00adecules are connected into a three-dimensional network through C\u2014H\u22efO, N\u2014H\u22efS and C\u2014H\u22ef\u03c0 inter\u00adactions. 27H26N2O2S2, the asymmetric unit is comprised of four mol\u00adecules (Z = 8 and Z\u2032 = 4). The 4-meth\u00adoxy\u00adphenyl rings are slightly twisted away from their attached olefinic double bonds [torsion angles = 5.9\u2005(4)\u201319.6\u2005(4)\u00b0]. The azomethine double bond has an s-trans configuration relative to one of the C=C bonds and an s-cis configuration relative to the other . The torsion angles between the azomethine C=N double bond and hydrazine-1-carbodi\u00adthio\u00adate moiety indicate only small deviations from planarity, with torsion angles ranging from 0.9\u2005(3) to 6.9\u2005(3)\u00b0 and from 174.9\u2005(3) to 179.7\u2005(2)\u00b0, respectively. The benzyl ring and the methyl\u00adenesulfanyl moiety are almost perpendicular to each other, as indicated by their torsion angles [range 93.7\u2005(3)\u2013114.6\u2005(2)\u00b0]. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO, N\u2014H\u22efS and C\u2014H\u22ef\u03c0(ring) hydrogen-bonding inter\u00adactions into a three-dimensional network. Structural details of related benzyl hydrazine-1-carbodi\u00adthio\u00adate are surveyed and compared with those of the title compound.In the title hydrazinecarbodi\u00adthio\u00adate derivative, C S-benzyl and S-alkyl di\u00adthio\u00adcarbaza\u00adtes are inter\u00adesting ligands in coordination chemistry because they can act as N,S-chelating agents because of the presence of soft sulfur and hard nitro\u00adgen donor atoms  than their transition-metal complexes . Structural details of (I) are compared with other hydrazinecarbodi\u00adthio\u00adates.Encouraged by previous findings on various properties of related Schiff base derivatives, we report herein the synthesis and structure determination of the title compound (I) consists of four mol\u00adecules, denoted as A, B, C and D. Orientational disorder of the 1,5-bis(phen\u00adyl)penta-1,4-dien-3-ylidenyl amine moiety in mol\u00adecule B and of the phenyl\u00admethyl moiety in mol\u00adecule D were observed. The mol\u00adecules are composed of a 1,5-bis\u00ad(4-meth\u00adoxy\u00adphen\u00adyl)penta-1,4-dien-3-ylidenyl moiety, connected to a benzyl ring by a hydrazine-1-carbodi\u00adthio\u00adate (\u2013C=N\u2014(NH)\u2014(C=S)\u2014S\u2014C\u2013) bridge ; \u03c46 (C16\u2014C15\u2014O2\u2014C27)], between the 4-meth\u00adoxy\u00adphenyl ring and the olefinic double bond , and between the olefinic double bond and the azomethine double bond . Torsion angles \u03c41 and \u03c46 are approximately 0\u00b0 or \u00b1180\u00b0 in the majority of the four mol\u00adecules, except mol\u00adecule C which has a \u03c41 of 20.9\u2005(3)\u00b0 (Table\u00a01\u03c42 = 5.9\u2005(4)\u201316.4\u2005(13)\u00b0; \u03c45 = 7.5\u2005(3)\u201319.6\u2005(4)\u00b0]. The orientations of the the azomethine double bond with its neighbouring olefinic double bonds relative to the inter\u00admediate C\u2014C bond  are different: one is in s-trans [\u03c43 = 147.4\u2005(6)\u2013175.7\u2005(2)\u00b0] conformation and the other in s-cis [\u03c44 = 15.3\u2005(3)\u201337.4\u2005(7)\u00b0] conformation. The dihedral angles between two 4-meth\u00adoxy\u00adphenyl rings in an individual mol\u00adecule are in the range 23.59\u2005(12)\u201389.6\u2005(5)\u00b0 (Table\u00a02\u03c47 (C9\u2014N1\u2014N2\u2014C18), \u03c48 (N1\u2014N2\u2014C18\u2014S1), \u03c49 (N2\u2014C18\u2014S1\u2014C19), \u03c410 (C18\u2014S1\u2014C19\u2014C20) and \u03c411 (S1\u2014C19\u2014C20\u2014C21). In all mol\u00adecules of (I), the hydrazine-1-carbo\u00adthio\u00adate bridges are more or less planar \u20136.9\u2005(3)\u00b0 and 174.9\u2005(3)\u2013179.7\u2005(2)\u00b0, respectively). The torsion angles between the sulfane moiety and the methyl\u00adene moiety indicate a slight twist [\u03c410 = 160.53\u2005(17)\u2013163.36\u2005(16)\u00b0]. These contortions are more severe between the benzyl ring and the methyl\u00adene sulfane moiety where \u03c411 is considerably smaller [\u03c411 = 93.7\u2005(3)\u2013114.6\u2005(2)\u00b0]. The dihedral angles between the benzyl ring and the two 4-meth\u00adoxy\u00adphenyl rings are in the range 31.6\u2005(5)\u201389.9\u2005(8)\u00b0 . In addition, mol\u00adecule C and mol\u00adecule D are connected through C17C\u2014H17C\u22efO1D hydrogen bonds . The four mol\u00adecules are linked into an endless chain parallel to [021] through the combination of these hydrogen bonds hydrazine-1-carbodi\u00adthio\u00adate as reference moiety resulted in 45 structures with different substituents. The reference moiety and relevant torsion angles are illus\u00adtrated in Fig.\u00a061R) together with the torsion angles for the benzyl hydrazine-1-carbo\u00adthio\u00adate moiety in these structures are collated in Table\u00a04\u03c47, \u03c48 and \u03c49; torsion angles \u03c47 and \u03c49 range from 165.1 to 180.0\u00b0 and indicate an anti-periplanar conformation whereas torsion angle \u03c48 is indicative of a syn-periplanar conformation (0.0\u2013 9.1\u00b0). With respect to torsion angle \u03c410, most of the structures adopt an anti-periplanar conformation ranging from 159.5 to 180.0\u00b0, but there are nine structures that adopt either a syn-clinal or an anti-clinal conformation (77.6\u2013110.4\u00b0). In most of the structures, the benzyl ring and the methyl\u00adene sulfane moiety are orientated almost perpendicular to each other, as indicated by torsion angle \u03c411. Here, either a syn-clinal (68.1\u201388.4\u00b0) or an anti-clinal (92.2\u2013141.1\u00b0) conformation is adopted. However, there is one outlier  was synthesized following a well-described literature protocol  was dissolved in absolute ethanol (50\u2005ml) under heating and stirring. The resulting solution was slowly added to a hot solution of di-p-meth\u00adoxy\u00adbenzalacetone  dissolved in absolute ethanol (50\u2005ml). 3-5 drops of concentrated hydro\u00adchloric acid were added to the mixture, which was subsequently heated and stirred for 5\u2005h : 3145, \u03bd(N\u2014H); 1630, \u03bd(C=N); 1244, \u03bd(N\u2014N); 1059, \u03bd(C=S); 3145. 1H NMR (CDCl3) \u03b4 (p.p.m.)= 6.55\u20137.68 (aromatic H); 3.85 (OCH3); 4.55 (\u2013CH2 benz\u00adyl); 10.20 (N\u2014H). 13C NMR (CDCl3) \u03b4(p.p.m.)= 114.35\u2013142.88 (aromatic C); 55.55 (OCH3); 39.34 (\u2013CH2 benz\u00adyl); 161.22 (C=N); 206.91 (C=S). m/z calculated for C27H26N2O2S2: 474, found 474.Yield: 57.3%. m.p.: 375-376\u2005K. Analysis calculated for CA, B, C or D. The N-bound H atoms were located in difference-Fourier maps and were refined freely [N\u2014H = 0.81\u2005(3)\u20130.91\u2005(4)\u2005\u00c5]. The C-bound H atoms were positioned geometrically (C\u2014H = 0.93\u20130.97\u2005\u00c5) and refined using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating-group model was applied to the methyl groups. The 1,5-bis\u00ad(phen\u00adyl)penta-1,4-dien-3-ylidenyl amine moiety in mol\u00adecule B and the phenyl\u00admethyl moiety in mol\u00adecule D display positional disorder, with refined site occupancy ratios of 0.667\u2005(7):0.333\u2005(7) and 0.653\u2005(15):0.347\u2005(15), respectively .Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019013458/wm5520sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019013458/wm5520Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013458/wm5520Isup3.cmlSupporting information file. DOI: 1902915, 1902915CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A third monoclinic polymorph of the title compound is described. In the crystal, it exhibits C\u2014H\u22efCl hydrogen bonds and face-on Cl\u22ef\u03c0 inter\u00adactions involving the chloro\u00adform disolvate mol\u00adecules. Inter\u00admolecular weak offset \u03c0\u2013\u03c0 inter\u00adactions are also present between the aromatic rings of the ligands. 2(C26H22P2)]\u00b72CHCl3 (I), is the third monoclinic polymorph of this platinum(II) complex involving the bidentate ligand cis-1,2-bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)ethyl\u00adene (cis-dppe) , linking the mol\u00adecules to form supra\u00admolecular sheets that lie in the bc plane.The title compound, [PtCll. 1998a. Inorg.  al. 1995. Inorg.  A selection of recent examples include complexes involving iron(II) (Song cis-dppe ligand and the title compound (I)II metal center with bidentate coordination by the phospho\u00adrus atoms of the cis-dppe ligand. The metal coordination sphere is completed by two chloride anions.The mol\u00adecular structures of the et al., 1998aP21/n without solvent in the unit cell, while structure ZOLYII As for the previously reported polymorphs of compound (I)II center of all three structures are, unsurprisingly, quite similar. The Pt\u2014P bond lengths range from 2.210\u2005(2) to 2.219\u2005(2)\u2005\u00c5, while the Pt\u2014Cl bond lengths range from 2.358\u2005(2) to 2.366\u2005(3)\u2005\u00c5. The P\u2014Pt\u2014P bond angles range from 86.66\u2005(11) to 87.08\u2005(5)\u00b0, while the Cl\u2014Pt\u2014Cl bond angles range from 90.33\u2005(7) to 91.03\u2005(5)\u00b0. The \u03c44 descriptor for fourfold coordination  to 3.789\u2005(10)\u2005\u00c5, while the D\u2014H\u22efA bond angles range from 132 to 158\u00b0. Three face-on Cl\u22ef\u03c0 inter\u00adactions nd Fig.\u00a02. The Cl\u22efbc plane, as shown in Fig.\u00a03Cg2\u22efCg2ii = 4.096\u2005(6)\u2005\u00c5 , and Cg3\u22efCg4iii = 3.770\u2005(6)\u2005\u00c5 [Cg3 and Cg4 are the centroids of rings C15\u2013C20 and C21\u2013C26, respectively, \u03b1 = 5.3\u2005(5)\u00b0, inter\u00adplanar distances are 3.326\u2005(4) and 3.439\u2005(4)\u2005\u00c5, slippage = 1.544\u2005\u00c5, symmetry code (iii) \u2212x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a0The complex mol\u00adecules are also linked by weak offset \u03c0\u2013\u03c0 inter\u00adactions, forming sheets that lie in the 2Cl2 solvent mol\u00adecule and one CHCl3 solvent mol\u00adecule in the unit cell, also shows Cl\u22ef\u03c0 inter\u00adactions. However, the methyl\u00adene chloride solvent mol\u00adecule is not engaged in a hydrogen bond with a chlorine atom of the PtII complex, and is disordered in the crystal lattice.The closely related polymorph ZOLYII, which contains one CHet al., 2016cis-dppe ligand is coordinated to a PtII center. In addition to the two polymorphs described above, the most similar cis-dppe\u2013PtII coordination complexes include AFEXEO . Another structure related to the title compound is KADQEL  in a NMR tube. This solution was left to stand at room temperature, and colorless needle-like crystals of compound (I)The title compound was prepared serendipitously by mixing 20.5\u2005mg of Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989018008836/su5444sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989018008836/su5444Isup2.hklStructure factors: contains datablock(s) I. DOI: 1849747CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The synthesis of a hybrid mol\u00adecule is reported. The crystal structure of the monohydrate was investigated using Hirshfeld surface analysis and enrichment contact ratios. Hydrogen bonds induced by guest water mol\u00adecules are the main driving force in crystal packing formation. 14H14N2OS2\u00b7H2O, the planar imidazopyridine ring system is linked to the 1,3-di\u00adthiol\u00adane moiety by an enone bridge. The atoms of the C\u2014C bond in the 1,3-di\u00adthiol\u00adane ring are disordered over two positions with occupancies of 0.579\u2005(14) and 0.421\u2005(14) and both disordered rings adopt a half-chair conformation. The oxygen atom of the enone bridge is involved in a weak intra\u00admolecular C\u2014H\u22efO hydrogen bond, which generates an S(6) graph-set motif. In the crystal, the hybrid mol\u00adecules are associated in R22(14) dimeric units by weak C\u2014H\u22efO inter\u00adactions. O\u2014H\u22efO hydrogen bonds link the water mol\u00adecules, forming infinite self-assembled chains along the b-axis direction to which the dimers are connected via O\u2014H\u22efN hydrogen bonding. Analysis of inter\u00admolecular contacts using Hirshfeld surface analysis and contact enrichment ratio descriptors indicate that hydrogen bonds induced by water mol\u00adecules are the main driving force in the crystal packing formation.In the title hydrated hybrid compound C Its geometrical parameters are similar to those found for 1--3,3-bis\u00ad(methyl\u00adsulfan\u00adyl)prop-2-enone  = 0.419\u2005(7)/0.443\u2005(9)\u2005\u00c5, \u03c6(2) = 303.2\u2005(9)/128.9\u2005(11)\u00b0 for the major and minor components, respectively]. The oxygen atom of the linker moiety is involved in a weak intra\u00admolecular C6\u2014H6\u22efO1 hydrogen bond (Table\u00a01S(6) graph-set motif.Fig.\u00a01d Table\u00a01, which gvia pairwise weak C\u2014H\u22efO inter\u00adactions [H5\u22efO1i = 2.71\u2005\u00c5; symmetry code as in Table\u00a01W\u2014H1W\u22efO2Wii hydrogen bonds, generating an infinite self-assembled chain of water mol\u00adecules in a helical fashion along the b axis around which the host mol\u00adecules are linked via O2W\u2014H2W\u22efN1 hydrogen bonds and weak C12\u2014H12D\u22efO2Wii inter\u00adactions .In the crystal, the host mol\u00adecules form inversion dimers ns Fig.\u00a04. The hoson Fig.\u00a05 and eachet al., 2007CrystalExplorer  are displayed in Figs. 6W\u2014H2W\u22efN1 hydrogen bond while the pale-red spot near H12B illustrates the weak C\u2014H\u22efO2W inter\u00adaction. The white spots represent H\u22efO, H\u22efS and H\u22efH contacts. On the shape-index surface, convex blue regions indicate hydrogen-donor groups, while concave red regions indicate hydrogen-acceptor groups and S\u22efN and S\u22efC contacts and O\u22efC inter\u00adactions. The fingerprint plots show the contribution of different types of inter\u00admolecular inter\u00adactions  is defined as the ratio between the proportion of actual crystal contacts between the different chemical species  and the theoretical proportion of random equiprobable contacts . The results obtained are summarized in Table\u00a02ECHc = 0.76 and correspond to weak C\u2014H\u22efC inter\u00adactions. These inter\u00adactions are under-represented because competition with the S\u22efHc, OW\u22efHc and weak O\u22efHc hydrogen bonds, the first two of which appear favoured with enrichment values of 1.35 and 1.14, respectively, and the last slightly under-represented with an enrichment ratio of 0.98. The C\u22efC contacts are privileged and display an enrichment value of 1.85, which highlight mol\u00adecules stacking one on top of the other as shown in Fig.\u00a05et al. -3,3-bis\u00ad(methyl\u00adsulfan\u00adyl)prop-2-\u220anone monohydrate ethanone (6.2\u2005mmol) was dissolved in distilled dimethyl sulfoxide (15\u2005ml), and the carbon di\u00adsulfide  was added. After cooling the mixture to 273\u2005K, sodium hydride  was added. After stirring for 30 min. at 273\u2005K, the mixture was stirred at ambient temperature for 4\u2005h. The solution was then cooled at 273\u2005K and 1,2-di\u00adchloro ethane  was added dropwise. The resulting mixture was then stirred for 24\u2005h and then poured into 50\u2005ml of ice-cold water. The precipitate was filtered and recrystallized from a mixture of water\u2013dioxane (2:1) to obtain brown single crystals of the title compound suitable for X-ray diffraction analysis .1- and were refined using a riding model with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-meth\u00adyl). In the 1,3-di\u00adthiol\u00adane ring, the carbon atoms of the C\u2014C bond are disordered over two positions with refined occupancy factors of 0.579\u2005(14) and 0.421\u2005(14). C\u2014C bond lengths in both disordered components were restrained to the target value of 1.513\u2005\u00c5  I. DOI: Click here for additional data file.10.1107/S2056989019015755/vm2224Isup2.cmlSupporting information file. DOI: 1967239CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "PTPN2 deletion in T cells enhances cancer immunosurveillance and the efficacy of adoptively transferred tumour\u2010specific T cells. T\u2010cell\u2010specific PTPN2 deficiency prevented tumours forming in aged mice heterozygous for the tumour suppressor p53. Adoptive transfer of PTPN2\u2010deficient CD8+ T cells markedly repressed tumour formation in mice bearing mammary tumours. Moreover, PTPN2 deletion in T cells expressing a chimeric antigen receptor (CAR) specific for the oncoprotein HER\u20102 increased the activation of the Src family kinase LCK and cytokine\u2010induced STAT\u20105 signalling, thereby enhancing both CAR T\u2010cell activation and homing to CXCL9/10\u2010expressing tumours to eradicate HER\u20102+ mammary tumours in\u00a0vivo. Our findings define PTPN2 as a target for bolstering T\u2010cell\u2010mediated anti\u2010tumour immunity and CAR T\u2010cell therapy against solid tumours.Although adoptive T\u2010cell therapy has shown remarkable clinical efficacy in haematological malignancies, its success in combating solid tumours has been limited. Here, we report that  Protein tyrosine phosphatase N2 inhibits tumour T\u2010cell infiltration and CAR T\u2010cell cytotoxicity and may thus be a therapeutic target to enhance solid\u2010tumour immunotherapy. Upon necropsy 15/28 (54%), Ptpn2fl/fl;p53+/\u2212 mice developed various tumours including thymomas, lymphomas, sarcomas, carcinomas and hepatomas  were evident in the thymi or peripheral lymphoid organs of 5/28 mice  developed any overt tumours, splenomegaly or abnormal lymphocytic populations as assessed by gross morphology or flow cytometry and lymphoid organ tissue architecture was normal \u2010expressing AT\u20103 (AT\u20103\u2010OVA) mammary carcinoma cells implanted into the inguinal mammary fat pads of Ptpn2fl/fl versus Lck\u2010Cre;Ptpn2fl/fl C57BL/6 mice  T cells into tumours  were increased rather than decreased in AT\u20103\u2010OVA tumours \u2010\u03b3 and tumour necrosis factor (TNF)  peptide SIINFEKL. Naive OT\u20101 T cells can undergo clonal expansion and develop effector function when they engage OVA\u2010expressing tumours, but thereon leave the tumour microenvironment, become tolerised and fail to control tumour growth  Ptpn2fl/fl OT\u20101 CD8+ T cells had no overt effect on the growth of AT\u20103\u2010OVA mammary tumours when compared to vehicle\u2010treated tumour\u2010bearing mice  by 25\u00a0days. Tumour re\u2010emergence in this setting was accompanied by decreased OVA and MHC class I (H2\u2010k1) gene expression, consistent with decreased antigen presentation; tumour re\u2010emergence was also accompanied by decreased PD\u2010L1 (Cd274) gene expression  cells that contribute to immunosurveillance and the suppression of solid tumour formation  subset  sarcoma cells, but importantly, not HER\u20102\u2010negative 24JK control cells  and central memory (CD44hiCD62Lhi) PTPN2\u2010deficient CD8+ HER\u20102 CAR T cells were more effective at specifically killing 24JK\u2010HER\u20102 cells but not 24JK cells in\u00a0vitro  of purified Ptpn2fl/fl versus Lck\u2010Cre;Ptpn2fl/fl central memory CD8+ HER\u20102 CAR T cells into sub\u2010lethally irradiated syngeneic recipients bearing established orthotopic tumours arising from the injection of HER\u20102\u2010expressing E0771 (HER\u20102\u2010E0771) mammary tumour cells  and IL\u201010 (Il10)  of the maximal ethically permissible mammary tumour burden prior to CAR T\u2010cell therapy  rather than the mixed central and effector/memory (CD44hiCD62Llo) phenotypes otherwise present on day 10 post\u2010adoptive transfer . When CD8+ T cells are activated by a strong TCR stimulus and subsequently stimulated with IL\u20102, they undergo differentiation into effectors and acquire CTL activity characterised by IFN\u03b3 and granzyme B expression . Since IL\u20102\u2010induced STAT\u20105 signalling was only partially corrected in Lck\u2010Cre;Ptpn2fl/fl;Lck+/\u2212 CAR T cells  being reduced to those in Ptpn2fl/fl control CAR T cells    Fig\u00a0B. To asset\u00a0al, et\u00a0al, Ptpn2 in murine CAR T cells by RNA interference using nuclease resistant siRNA duplexes (siSTABLE\u2122) that efficiently knockdown genes for prolonged periods   Fig\u00a0F. By conet\u00a0al, ex\u00a0vivo so that resultant CAR T cells do not overexpress Cas9 and do not elicit immunogenic responses post\u2010adoptive transfer. To this end, we transfected total CAR T cells with recombinant nuclear\u2010localised Cas9 pre\u2010complexed with short guide (sg) RNAs capable of directing Cas9 to the Ptpn2 locus  and the human melanoma cell line MDA\u2010MB\u2010435 (ATCC\u00aeHTB\u2010219\u2122) were obtained from the ATCC, Manassas, Virginia, USA. HER\u20102\u2010E0771 cells were engineered to inducibly overexpress murine PTPN2 (HER\u20102\u2010E0771\u2010PTPN2hi) in response to doxycycline using the Tet\u2010On 3G Inducible Expression System according to the manufacturer's instructions (Clontech). Tumour cells were cultured in RPMI 1640  or high\u2010glucose DMEM (AT3\u2010OVA) supplemented with 10% FBS, l\u2010glutamine (2\u00a0mM), penicillin (100 units/ml)/streptomycin (100\u00a0\u03bcg/ml), MEM non\u2010essential amino acids (0.1\u00a0mM), sodium\u2010pyruvate (1\u00a0mM), HEPES (10\u00a0mM) and 2\u2010mercaptoethanol (50\u00a0\u03bcM).The C57BL/6 mouse mammary carcinoma cell line E0771  (Johnstone PtprcaPepcb/BoyJ) and human HER\u20102 transgenic (TG) recipient mice and 6\u2010 to 8\u2010week\u2010old female donor mice were used for adoptive transfers. For ex\u00a0vivo experiments, either male or female mice were used. Aged\u2010 and sex\u2010matched littermates were used in all experiments. Ptpn2fl/fl and Lck\u2010Cre;Ptpn2fl/fl mice and the corresponding OT\u20101 TCR transgenic mice were described previously  mice have been described previously  with Lck\u2010Cre;Ptpn2fl/fl mice. B6.129S2\u2010Lck<tm1Mak>/J mice were a gift from Dr Andre Veillette  and were bred with Lck\u2010Cre;Ptpn2fl/fl mice to generate Lck\u2010Cre;Ptpn2fl/fl;Lck+/\u2212 mice. Ly5.1 and C57BL/6 mice were purchased from the WEHI Animal Facility , and human HER\u20102 (C57BL/6) transgenic (TG) mice were bred and maintained at the Peter MacCallum Cancer Centre.Mice were maintained on a 12\u2010h light\u2013dark cycle in a temperature\u2010controlled high barrier facility with free access to food and water. Six\u2010 to 10\u2010week\u2010old female Ly5.1  was purchased from Thermo Fisher Scientific. The mouse antibody against PTPN2 (clone 6F3) was provided by M. Tremblay (McGill University). For immunofluorescence staining and immunohistochemistry, rabbit anti\u2010CD3\u03b5 and mouse anti\u2010HER\u20102 from Abcam were used. Recombinant human IL\u20102, murine IL\u20107 and IL\u201015 used for T\u2010cell stimulation or IFN\u03b3 used for stimulating tumour cells were purchased from the NIH or PeproTech, respectively. RetroNectin was purchased from Takara, Dnase I and doxycycline from Sigma\u2010Aldrich. The mouse anti\u2010nuclear antibodies Ig's  ELISA Kit (Alpha Diagnostic Int.) and the Transaminase II Kit  were used according to the manufacturer's instructions. FBS was purchased from Thermo Scientific; Dulbecco\u2010Phosphate\u2010Buffered Saline (D\u2010PBS), RPMI 1640, DMEM, MEM non\u2010essential amino acids and sodium\u2010pyruvate were from Invitrogen, and collagenase type IV was purchased from Worthington Biochemical.For cell stimulation, anti\u2010CD3\u03b5 (clone 145\u20102C11) and anti\u2010CD28 (clone 37.51) antibodies were purchased from BD Biosciences. Antibodies against p\u2010(Y701) STAT1 (clone 58D6), p\u2010(Y694) STAT5 (D47E7) XPet\u00a0al, et\u00a0al, Single\u2010cell suspensions from spleen, lymph nodes and hepatic lymphocytes were obtained as previously described  or CyAn\u2122 ADP (Beckman Coulter).For FACS sorting, cells were stained in 15\u2010ml Falcon tubes (BD Biosciences) for 30\u00a0min on ice and purified using either a BD Influx cell sorter, or the BD FACSAria II, BD FACSAria Fusion 3 or BD FACSAria Fusion 5 instruments.Data were analysed using FlowJo8.7 or FlowJo10 (Tree Star Inc.) software. For cell quantification, a known number of Calibrite\u2122 Beads (BD Biosciences) or Nile Red Beads (ProsiTech) or Flow\u2010Count Fluorospheres (Beckman Coulter) were added to samples before analysis.The following antibodies from BD Biosciences, BioLegend or eBioscience were used for flow cytometry: Phycoerythrin (PE) or peridinin\u2013chlorophyll cyanine 5.5 (PerCP\u2010Cy5.5)\u2010conjugated CD3 (145\u20102C11); PerCP\u2010Cy5.5 or phycoerythrin\u2013cyanine 7 (PE\u2010Cy7)\u2010conjugated CD4 (RM4\u20105); BV711, Pacific Blue\u2010conjugated (PB), allophycocyanin (APC)\u2010Cy7 or APC\u2010conjugated CD8 (53\u20106.7); PerCP\u2010Cy5.5, PE or APC\u2010Cy7\u2010conjugated CD25 (P61); Fluorescein isothiocyanate (FITC), V450, Alexa Fluor 700 or PE\u2010Cy7\u2010conjugated CD44 (IM7); APC\u2010conjugated CD45 (30\u2010F11); V450, APC, Alexa Fluor 488 or PE\u2010conjugated CD45.1 ; FITC, PB or PerCP\u2010Cy5.5\u2010conjugated CD45.2 ; APC\u2010conjugated CD45R ; PE\u2010Cy7, APC or PE\u2010conjugated CD62L (Mel\u201014); PE\u2010conjugated CD122 (TM\u2010\u03b21); PE\u2010conjugated CD132 (4G3); Alexa Fluor 647\u2010conjugated CD183 (CXCR3\u2010173); PerCP\u2010eFluo710\u2010conjugated CD185 ; PE\u2010Cy7 conjugated CD197 ; PE\u2010conjugated CD223 ; PE\u2010Cy7\u2010conjugated CD279 ; FITC\u2010conjugated CD11b (M1/70); APC\u2010Cy7\u2010conjugated Ly6C (AL\u201021); PE\u2010conjugated Ly\u20106G (clone 1A8); APC\u2010conjugated F4/80 (BM8); PE\u2010conjugated IL\u201010 (JES5\u201016E3), PE\u2010conjugated Nur77 (12.14); PE\u2010Cy7\u2010conjugated IFN\u03b3 (XMG1.2); FITC or APC\u2010conjugated TNF (MP6\u2010XT22); Alexa Fluor 647\u2010conjugated Granzyme B (GB11); PE\u2010Cy7\u2010conjugated TCR\u2010V\u03b12 (B20.1); eFluor 660\u2010conjugated p(Y418)\u2010Src (SC1T2M3); Alexa Fluor 647\u2010conjugated T\u2010bet (4B10); and V450\u2010conjugated FoxP3 (clone MF23).The following antibodies from Miltenyi Biotec were used for flow cytometry: PE\u2010conjugated CD197 ; VioBright FITC\u2010conjugated CD8 (BW135/80); and VioBlue\u2010conjugated CD45RA (REA1047).7/ml) were cultured overnight with anti\u2010CD3\u03b5 (0.5\u00a0\u03bcg/ml) and anti\u2010CD28 (0.5\u00a0\u03bcg/ml) in the presence of 100\u00a0IU/ml human IL\u20102 and 0.2\u00a0ng/ml murine IL\u20107 in complete T\u2010cell medium . Dead cells were removed by Ficoll centrifugation  according to the manufacturer's instructions. Retrovirus encoding a second\u2010generation chimeric antibody receptor (CAR) consisting of an extracellular scFv\u2010anti\u2010human HER\u20102, a membrane proximal CD8 hinge region and the transmembrane and the cytoplasmic signalling domains of CD28 fused to the cytoplasmic region of CD3\u03b6 (scFv\u2010anti\u2010HER\u20102\u2010CD28\u2010\u03b6) was obtained from the supernatant of the GP+E86 packaging line as described previously  at room temperature and incubated overnight before the second viral transduction. T cells were maintained in IL\u20102\u2010 and IL\u20107\u2010containing media and cells used at days 7\u20138 after transduction.Splenocytes were isolated from murine spleens by mechanical disruption, and contaminating red blood cells were removed by incubation with 1\u00a0ml of Blood Cell Lysing Buffer Hybri\u2010Max\u2122 (Sigma\u2010Aldrich) for 7\u00a0min at room temperature per spleen. Lymphocytes  CAR T cells and expanded for up to 15\u00a0days in the presence of human IL\u20102. The expression of the chimeric receptor was determined by staining with Alexa Flour 647\u2010conjugated anti\u20103S193 idiotype [supplied by Ludwig Institute for Cancer Research (LICR)], and truncated CD34 was detected with PE\u2010conjugated anti\u2010human CD34 (BioLegend). Cell surface phenotyping of transduced cells was determined by staining with BV785\u2010conjugated anti\u2010human CD3 , BV605\u2010conjugated anti\u2010human CD4  and PE\u2010Cy7\u2010conjugated anti\u2010human CD8 .Human peripheral blood mononuclear cells (PBMCs) were isolated from normal donor buffy coats. PBMCs were stimulated with anti\u2010human CD3  and human IL\u20102 (600\u00a0IU/ml) in complete T\u2010cell medium. Retrovirus encoding a second\u2010generation chimeric antibody receptor (CAR) consisting of an extracellular scFv\u2010anti\u2010human LeY domain, a membrane proximal CD8 hinge region and the transmembrane and the cytoplasmic signalling domains of CD28 fused to the cytoplasmic region of CD3\u03b6 was obtained from the supernatant of the PG13 packaging cell line and has been described previously (Westwood 5) generated from human PBMC were incubated with Lewis Y\u2010expressing OVCAR\u20103 cells (1\u00a0\u00d7\u00a0105) or Lewis Y\u2010negative MDA\u2010MB\u2010435 cells (1\u00a0\u00d7\u00a0105) or plate\u2010bound anti\u2010LY  for 6\u00a0h at 37\u00b0C in complete T\u2010cell medium. GolgiPlug\u2122 and GolgiStop\u2122 were added 3\u00a0h before cells were processed for surface and intracellular staining for CD4 , CD8 , IFN\u03b3  and TNF  by flow cytometry.CAR T cells  or IL\u201015 (5 or 10\u00a0ng/ml) in 100\u00a0\u03bcl RPMI/1 %FBS. Cells were processed for intracellular p(Y694)\u2010STAT\u20105 detection by flow cytometry as previously described  dilution, purified CD8+CD44hiCD62Lhi CAR T cells were incubated with CTV in D\u2010PBS supplemented with 0.1% (v/v) BSA at a final concentration of 2\u00a0\u03bcM for 10\u00a0min at 37\u00b0C. Cells were then washed three times with D\u2010PBS supplemented with 10% (v/v) FBS. CAR T cells (2\u00a0\u00d7\u00a0105) were incubated with HER\u20102\u2010expressing or HER\u20102\u2010negative 24JK sarcoma cells (1\u00a0\u00d7\u00a0105) in complete T\u2010cell medium.CAR T cells generated from mouse splenocytes were stained with fluorochrome\u2010conjugated antibodies for CD8, CD62L and CD44 and sorted for CD8+CD44hiCD62Lhi CAR T cells were incubated with plate\u2010bound anti\u2010CD3\u03b5 for 24\u00a0h at 37\u00b0C in complete T\u2010cell medium. Pre\u2010activated CAR T Cells (2\u00a0\u00d7\u00a0105) were labelled with 5\u00a0\u03bcM CTV and incubated with HER\u20102\u2010expressing or HER\u20102\u2010negative 24JK sarcoma cells (1\u00a0\u00d7\u00a0105) in complete T\u2010cell medium. At various time points, proliferating cells were harvested and CTV dilution was monitored by flow cytometry. For cell quantification, Nile Red Beads (ProsiTech) or Flow\u2010Count Fluorospheres (Beckman Coulter) were added to samples before analysis.For the assessment of CAR T\u2010cell proliferation after anti\u2010CD3\u03b5 stimulation, purified CD8T cells were incubated rocking on an orbital shaker with PTPN2\u2010inhibitor compound 8 (100\u00a0nM) or vehicle (DMSO 1% v/v) in serum\u2010free RPMI 1640 for 1\u00a0h at 37\u00b0C. Cells were washed three times with complete T\u2010cell medium and processed for T\u2010cell activation studies.5 HER\u20102\u2010E0771 cells resuspended in 20\u00a0\u03bcl D\u2010PBS into the fourth mammary fat pad. At day 6 post\u2010tumour cell injection, human HER\u20102 TG mice were pre\u2010conditioned with total body irradiation (4\u00a0Gy) prior to the adoptive transfer of 6\u00a0\u00d7\u00a0106 FACS\u2010purified CD8+CD44hiCD62Lhi CAR T cells. Mice were treated with 50,000\u00a0IU IL\u20102 on days 0\u20134 after T\u2010cell transfer.Female human HER\u20102 TG mice were anaesthetised with Ketamine (100\u00a0mg/kg) and Xylazil (10\u00a0mg/kg) (Troy Laboratories) and injected orthotopically with 2\u00a0\u00d7\u00a0102) was abraded using a MultiPro Dremel with a grindstone attachment. B16.F10\u2010OVA\u2010expressing melanoma cells (1\u00a0\u00d7\u00a0105) were resuspended in 10\u00a0\u03bcl of Matrigel\u2122 (BD Biosciences) and orthotopically applied to the lesion. Set Matrigel was covered with a piece of Op\u2010site FlexigridTM (Smith and Nephew). The torsos of the mice were wrapped with a soft hypoallergenic MicroporeTM tape  and then by a stronger porous polyethylene TransporeTM tape  to protect the abraded site. Twenty\u2010four hours later, 2\u00a0\u00d7\u00a0105 FACS\u2010purified CD8+ naive CD44loCD62Lhi OT\u20101 T cells were adoptively transferred. Recipient mice were monitored daily until bandages were removed 6\u00a0days after tumour engraftment.Ly5.1 mice were anaesthetised with Ketamine (100\u00a0mg/kg) and Xylazil (10\u00a0mg/kg) (Troy Laboratories). The flanks of the mice were shaved using clippers and depilated with Veet (Reckitt Benckiser), and the skin  and Xylazil (10\u00a0mg/kg) (Troy Laboratories) and were injected orthotopically with 1\u00a0\u00d7\u00a0106/200\u00a0\u03bcl) were stimulated with PMA  and ionomycin  in the presence of GolgiPlug\u2122 and GolgiStop\u2122 (BD Biosciences) for 4\u00a0h at 37\u00b0C in complete T\u2010cell medium.Tumour\u2010bearing mice were sacrificed, and tumours were excised and digested at 37\u00b0C for 30\u00a0min using a cocktail of 1\u00a0mg/ml collagenase type IV  and 0.02\u00a0mg/ml DNase (Sigma\u2010Aldrich) in DMEM supplemented with 2% (v/v) FBS. Cells were passed through a 70\u2010\u03bcm cell strainer (BD Biosciences) twice and processed for flow cytometry. For the detection of intracellular cytokines in tumour\u2010infiltrating lymphocytes, cells  and 10\u00a0mM HEPES for 1\u00a0h at 37\u00b0C. Cells were passed through a 70\u2010\u03bcm cell strainer twice  and washed three times with 50\u00a0ml PBS. Cells were resuspended in DMEM supplemented with 10% FBS, 2\u00a0mM l\u2010glutamine, penicillin (100 units/ml), streptomycin (100\u00a0\u03bcg/ml) and seeded into 24\u2010well plates. Cells were incubated at 37\u00b0C until they reached 80% confluency. Tumour\u2010infiltrating T cells from AT\u20103\u2010OVA tumour\u2010bearing C57BL/6 mice Ptpn2fl/fl and Lck\u2010Cre;Ptpn2fl/fl mice were labelled with 2\u00a0\u03bcM CTV and incubated with adherent, 80% confluent AT\u20103\u2010OVA tumour cells overnight. GolgiPlug\u2122 and GolgiStop\u2122 were added 3\u00a0h before cells were processed for intracellular staining for IFN\u03b3 and TNF by flow cytometry.AT\u20103\u2010OVA tumour\u2010bearing C57BL/6 mice were sacrificed, and tumours were collected in ice\u2010cold D\u2010PBS and then digested with 50\u00a0\u03bcg/ml Liberase  in Hank's Balanced Salt Solution  or effector/memory (CD44hiCD62Llo) or total HER\u20102\u2010specific CAR T cells were added at different concentrations to the mix of HER\u20102\u2010expressing (5\u00a0\u00d7\u00a0104) and HER\u20102\u2010negative (5\u00a0\u00d7\u00a0104) 24JK sarcoma cells and incubated for 4\u00a0h at 37\u00b0C in complete T\u2010cell medium. Antigen\u2010specific target cell lysis (24JK\u2010HER\u20102 cell depletion) was monitored by flow cytometry.For the assessment of CAR T\u2010cell cytotoxicity, HER\u20102\u2010expressing 24JK sarcoma cells (5\u00a0\u03bcM CTV) and HER\u20102\u2010negative 24JK sarcoma cells (0.5\u00a0\u03bcM CTV) were labelled with CellTrace\u2122 Violet  in D\u2010PBS supplemented with 0.1% (v/v) BSA for 15\u00a0min at 37\u00b0C. Tumour cells were then washed three times with D\u2010PBS supplemented with 10% (v/v) FBS and mixed at a 1:1 ratio. FACS\u2010purified CD8For brain immunohistochemistry, mice were perfused transcardially with heparinised saline  followed by 4% (w/v) paraformaldehyde in phosphate buffer . Brains were post\u2010fixed overnight and then kept for 4\u00a0days in 30% (w/v) sucrose in 0.1\u00a0M phosphate buffer to cryoprotect the tissue, before freezing on dry ice. 30\u2010\u03bcm sections (120\u00a0\u03bcm apart) were cut in the coronal plane throughout the entire rostral\u2010caudal extent of the cerebellum. For detection of CD3\u03b5, sections were subjected to antigen retrieval in citrate acid buffer  at 85\u00b0C for 20\u00a0min. Sections were incubated at room temperature for 2\u00a0h in blocking buffer [0.1M phosphate buffer, 0.2% (v/v) Triton X\u2010100, 10% (v/v) normal goat serum (Sigma\u2010Aldrich) and then overnight at 4\u00b0C in rabbit anti\u2010CD3 (Dako) in 1% (v/v) blocking buffer. After washing with PBS, sections were incubated with goat anti\u2010rabbit Alexa Fluor 488\u2010conjugated secondary antibody (Life Technologies) in blocking buffer for 2\u00a0h at room temperature. Sections were mounted with Mowiol 4\u201088 mounting media and visualised using an Olympus Provis AX70 microscope. Images were captured with an Olympus DP70 digital camera and processed using AnalySIS (Olympus) software. To assess gross tissue morphology, a subset of sections throughout the entire rostral\u2010caudal extent of the cerebellum were stained with haematoxylin and eosin.For detection of HER\u20102, 30\u2010\u03bcm sections throughout the entire rostral\u2010caudal extent of the cerebellum from C57BL/6 or HER\u20102 TG C57BL/6 mice were subjected to antigen retrieval and incubated in blocking buffer (as described above). Sections were then incubated overnight in (4\u00b0C) with anti\u2010c\u2010ErbB2/c\u2010Neu (Ab\u20103) mouse mAb (3B5) . After washing with PBS, HER\u20102\u2010positive cells were visualised using rabbit IgG VECTORSTAIN ABC Elite and DAB  Peroxidase Substrate Kits  and visualised using a bright field microscope.For mammary fat pad tumour immunohistochemistry, animals were culled and mammary fat pad immediately dissected and fixed in buffered formalin solution for 48\u00a0h. Tissues were embedded in paraffin and 4\u2010\u03bcm sections of the entire block prepared. Every tenth to fourteenth section of the tissue was used to detect HER\u20102 and CD3 by immunohistochemistry. After deparaffinisation and rehydration, sections were subjected to antigen retrieval in Tris/EDTA buffer (pH 8.0) at 120\u00b0C for 10\u00a0min. Sections were blocked with 5% (v/v) bovine serum albumin in 0.1\u00a0M phosphate buffer for 1\u00a0h at room temperature and incubated overnight (4\u00b0C) with anti\u2010c\u2010ErbB2/c\u2010Neu (Ab\u20103) mouse mAb (3B5)  or anti\u2010CD3 . After washing with PBS, HER\u20102\u2010 and CD3\u2010positive cells were visualised using rabbit IgG VECTORSTAIN ABC Elite and DAB  Peroxidase Substrate Kits  and counterstained with haematoxylin. Sections were visualised on a Zeiss Axioskop 2 mot plus microscope .\u2122 SYBR\u00ae Green Assay  were utilised to perform quantitative PCR detecting Cxcl9, Cxcl10, Tgfb1, Cd274, H2\u2010K1 and Rps18. Primer sets for HER\u20102, Nono and SerpinB14  were purchased from Sigma\u2010Aldrich. Relative gene expression (\u0394Ct) was determined by normalisation to the house\u2010keeping gene Nono throughout the study except for Fig\u00a0Rps18 was used and \u0394\u0394Ct analysis performed.RNA was extracted with TRIzol reagent  and RNA quality and quantity determined using a NanoDrop 2000 (Thermo Fisher Scientific). mRNA was reverse transcribed using a High\u2010Capacity cDNA Reverse Transcription Kit  and processed for quantitative real\u2010time PCR either using the Fast SYBR\u2122 Green Master Mix . Primer sets from PrimePCRPtpn2 was knocked down transiently in HER\u20102 CAR T cells using nuclease resistant Ptpn2 siRNA duplexes  ; siRNA duplexes (siSTABLE\u2122) for enhanced green fluorescent protein  were used as a control. CAR T cells were transfected with Ptpn2 siRNA (300\u00a0nM) conjugated to FITC or GFP siRNA (300\u00a0nM) conjugated to FITC 2\u00a0days prior to adoptive T\u2010cell therapy using the Mouse T\u2010cell Nucleofector\u2122 Kit (Lonza Bioscience) according to the manufacturer's instructions.Ptpn2 was deleted in HER\u20102 CAR T cells using Cas9 ribonucleoprotein (RNP)\u2010mediated gene editing. Briefly, total CAR T cells were transfected with recombinant Cas9  pre\u2010complexed with short guide (sg) RNAs  targeting the Ptpn2 locus  or non\u2010targeting sgRNAs (GCACUACCAG AGCUAA CUCA) as a control 2\u00a0days prior to adoptive T\u2010cell therapy using the P3 Primary Cell 4D\u2010Nucleofector X\u2122 Kit (Lonza Bioscience) according to the manufacturer's instructions.hi cell line. Briefly, murine Ptpn2 cDNA from HER\u20102\u2010E0771 cells was reverse transcribed and amplified by PCR and cloned into the SmaI and EcoR1 restriction sites of Tre\u20103G plasmid (Clontech Laboratories) to generate the Tre\u20103G\u2010Ptpn2 construct; the fidelity of the cloned cDNA was confirmed by dideoxy sequencing. HEK293T cells were transfected with either the Tre\u20103G\u2010Ptpn2 or Tet\u2010On 3G constructs using the Lenti\u2010X Packing system (Clontech Laboratories) according to the manufacturer's instructions. HER\u20102\u2010E0771 mammary tumour cells were transduced first with Tet\u2010On 3G lentivirus and selected with G418 (0.8\u00a0mg/ml) and subsequently transduced with Tre\u20103G\u2010Ptpn2 lentivirus and selected with puromycin (1.5\u00a0\u03bcg/ml). Where indicated, the resultant HER\u20102\u2010E0771\u2010PTPN2hi cells were incubated with 2\u00a0mg/ml doxycycline (DOX) to induce the expression of PTPN2. Cells were serum starved in DMEM medium without FBS for 12\u00a0h and stimulated with 2\u00a0ng/ml IFN\u03b3 for the indicated times and processed for immunoblotting or incubated with 1\u00a0ng/ml IFN\u03b3 for 24\u00a0h and processed for quantitative real\u2010time PCR.The Tet\u2010on 3G inducible expression system (Clontech Laboratories) was used to generate the HER\u20102\u2010E0771\u2010PTPN2in\u00a0vivo studies, 2\u00a0\u00d7\u00a0105 HER\u20102\u2010E0771\u2010PTPN2hi cells were resuspended in 20\u00a0\u03bcl D\u2010PBS and injected orthotopically into the fourth mammary fat pad of female human HER\u20102 TG mice. At day 5 post\u2010tumour cell injection, mice were administered DOX (2\u00a0mg/ml) in the drinking water for the entirety of the experiment. At day 6 post\u2010tumour cell injection, human HER\u20102 TG mice were pre\u2010conditioned with total body irradiation (4\u00a0Gy) prior to the adoptive transfer of 6\u00a0\u00d7\u00a0106 FACS\u2010purified CD8+CD44hiCD62Lhi CAR T cells. Mice were treated with 50,000\u00a0IU IL\u20102 on days 0\u20134 after T\u2010cell transfer.For U\u2010test, the parametric 2\u2010tailed Student's t\u2010test, the 1\u2010way or 2\u2010way ANOVA test using Turkey or Sidak post hoc comparison or the log\u2010rank (Mantel\u2013Cox test) where indicated. *P\u00a0<\u00a00.05, **P\u00a0<\u00a00.01, ***P\u00a0<\u00a00.001 and ****P\u00a0<\u00a00.0001 were considered as significant.Statistical analyses were performed with GraphPad Prism software 7.0b using the non\u2010parametric using 2\u2010tailed Mann\u2013Whitney All experiments were performed in accordance with the NHMRC Australian Code of Practice for the Care and Use of Animals. All protocols were approved by the Monash University School of Biomedical Sciences Animal Ethics Committee (Ethics number: MARP/2012/124) or the Peter MacCallum Animal Ethics and Experimentation Committee .Conceptualisation: TT; Methodology: FW, K\u2010HL, XD, SL, KH, GTD, PKG, CK, DM, PAB, MAH, SLP, JW, SZ, Z\u2010YZ, JO, TG, PKD and TT; Data acquisition: FW, K\u2010HL, XD, SL, KH, GTD, PKG, MAH and SLP; Data analysis: FW, K\u2010HL, XD, SL, KH, GTD, PKG; MAH; TG, PKD and TT; Data interpretation: FW, K\u2010HL, XD, SL, KH, GTD, PKG, CK, DM, PAB, MAH, SLP, JW, SZ, Z\u2010YZ, JO, TG, PKD and TT; Writing\u2010Original Draft: TT; Writing\u2010Review and Editing: FW, K\u2010HL, XD, SL, KH, GTD, PKG, CK, DM, PAB, MAH, SLP, JW, SZ, Z\u2010YZ, JO, TG, PKD and TT. Funding acquisition: FW, PKD, TG and TT; Final approval for publishing: FW, K\u2010HL, XD, SL, KH, GTD, PKG, CK, DM, PAB, MAH, SLP, JW, SZ, Z\u2010YZ, JO, TG, PKD and TT.The authors declare that they have no conflict of interest.AppendixClick here for additional data file.Expanded View Figures PDFClick here for additional data file.Source Data for AppendixClick here for additional data file.Review Process FileClick here for additional data file."}
{"text": "The title compound, 2-(4-nitro\u00adphen\u00adyl)-2-oxoethyl 2-chloro\u00adbenzoate, is relatively planar with the two aromatic rings being inclined to each other by 3.56\u2005(11)\u00b0. 15H10ClNO5, is relatively planar with the two aromatic rings being inclined to each other by 3.56\u2005(11)\u00b0. The central \u2014C(=O)\u2014C\u2013O\u2014C(=O)\u2014 bridge is slightly twisted, with a C\u2014C\u2014O\u2014C torsion angle of 164.95\u2005(16)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO and C\u2014H\u22efCl hydrogen bonds, forming layers parallel to the (101) plane. The layers are linked by a further C\u2014H\u22efO hydrogen bond, forming a three-dimensional supra\u00admolecular structure. There are a number of offset \u03c0\u2013\u03c0 inter\u00adactions present between the layers [inter\u00adcentroid distances vary from 3.8264\u2005(15) to 3.9775\u2005(14)\u2005\u00c5]. Hirshfeld surface analyses, the dnorm surfaces, electrostatic potential and two-dimensional fingerprint plots were examined to verify the contributions of the different inter\u00admolecular contacts within the supra\u00admolecular structure. The shape-index surface shows that two sides of the mol\u00adecule are involved in the same contacts with neighbouring mol\u00adecules, and the curvedness plot shows flat surface patches that are characteristic of planar stacking.The title compound, C Torsion angle \u03c41 at \u221212.5\u2005(3)\u00b0 signifies a certain noncoplanarity between the benzene ring (C10\u2013C15) and the adjacent carbonyl group (C9=O3) as a result of steric repulsion between the substituent Cl1 and the adjacent carbonyl group C9=O3. This is also reflected in the torsion angle \u03c42 of \u2212164.95\u2005(16)\u00b0, between the two carbonyl groups, C7=O2 and C9=O3, which have a \u2013anti\u00adperiplanar conformation. Torsion angle \u03c43, involving the benzene ring (C1\u2013C6) and the adjacent carbonyl group (C7=O2), is \u22123.6\u2005(3)\u00b0 and indicates a \u2013synperiplanar conformation. A comparison of the torsion angles in I and II, indicates that the insertion of the Cl atom in I has the most significant influence on torsion \u03c42, which is \u2212164.95\u2005(16)\u00b0 in I compared to 174.08\u2005(9)\u00b0 in II. Torsion angles \u03c41 of \u221212.5\u2005(3)\u00b0 and \u03c43 of \u22123.6\u2005(3)\u00b0 are slightly larger than the values observed in II, viz. 9.60\u2005(16) and 1.88\u2005(15)\u00b0, respectively. Hence, compound I has a less planar conformation than unsubstituted compound II.The overall mol\u00adecular conformation of I is characterized by three torsion angles, i, C14\u2014H14\u22efO4i and C13\u2014H13\u22efCl1iii hydrogen bonds to form layers lying parallel to the (101) plane; see Fig.\u00a02A\u22efO3ii hydrogen bonds and offset \u03c0\u2013\u03c0 inter\u00adactions  shows the Hirshfeld surface mapped over dnorm (\u22120.154 to 1.305) and for Fig.\u00a04b) the electrostatic potential. The Hirshfeld surface illustrated in Fig.\u00a04a) reflects the involvement of different atoms with the inter\u00admolecular inter\u00adactions through the appearance of blue and red patches, which correspond to the regions of positive and negative electrostatic potential shown in Fig.\u00a04b). The shape-index surface  clearly shows that the two sides of the mol\u00adecule are involved in contacts with neighbouring mol\u00adecules and the curvedness plot  shows flat surface patches characteristic of planar stacking.The Hirshfeld surface analysis -2-oxoethyl 4-nitro\u00adbenzoate \u00b0 in the title compound. In the crystal structure of the recently published compound 2-(4-nitro\u00adphen\u00adyl)-2-oxoethyl benzoate (II)  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019014336/su5521sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019014336/su5521Isup2.hklStructure factors: contains datablock(s) I. DOI: 1449647, 1449647CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, phenyl-C\u2014H\u22efO(carbon\u00adyl) and carbonyl-O\u22efO(carbon\u00adyl) inter\u00adactions general a [111] supra\u00admolecular chain.In Ru 3(C19H17PS)(CO)11], comprises a triangle of Ru0 atoms, two of which are bonded to four carbonyl ligands. The third metal atom is bound to three carbonyl ligands and the phosphane-P atom of a dissymmetric phosphane ligand, PPh2(C6H4SMe-4); no Ru\u22efS inter\u00adactions are observed. The phosphane occupies an equatorial position and its proximity to an Ru\u2014Ru edge results in the elongation of this bond with respect to the others [2.8933\u2005(2)\u2005\u00c5 cf. 2.8575\u2005(2) and 2.8594\u2005(3)\u2005\u00c5]. In the crystal, phenyl-C\u2014H\u22efO(carbon\u00adyl) and carbonyl-O\u22efO(carbon\u00adyl) [2.817\u2005(2)\u2005\u00c5] inter\u00adactions combine to form a supra\u00admolecular chain propagating along [111]; the chains pack without directional inter\u00adactions between them. The carbonyl-O\u22efO(carbon\u00adyl) and other weak contacts have an influence upon the Hirshfeld surfaces with O\u22efH contacts making the greatest contribution, i.e. 37.4% cf. 15.8% for O\u22efO and 15.6% for H\u22efH contacts.The title cluster compound, [Ru R3) have played a major role in the formation and subsequent chemistry of metal carbonyl clusters, often relating to the promising catalytic activity of the products 12 with PR3 leads to Ru3(CO)n12\u00a0\u2013\u00a0(PR3)n, n = 1\u20134, cluster compounds 12, thereby making the cluser more reactive 10[PPh2(C6H4SMe)]8 cluster, only the P atom of the PPh2C6H4SMe ligand is coordinated to the metal centre while the thio\u00admethyl group remains uncoordinated  ligand are surprisingly few in number 11PPh2(C6H4SMe-4) (I)Tertiary phosphanes (P3(CO)11PPh2(C6H4SMe-4), (I)3 triangle with one Ru centre being bound, equatorially, by the phosphane ligand. The Ru\u2014Ru bond lengths in the Ru3 triangle are not equivalent with the Ru1\u2014Ru2 bond of 2.8933\u2005(2)\u2005\u00c5 being longer than the Ru1\u2014Ru3 and Ru2\u2014Ru3 bonds of 2.8575\u2005(2) and 2.8594\u2005(3)\u2005\u00c5, respectively. This disparity probably reflects the steric hindrance exerted by the phosphane ligand which occupies the region in the vicinity of the Ru1\u2014Ru2 bond. Some general trends in the geometric parameters involving the carbonyl ligands may be discerned, the relatively high errors in some of the parameters notwithstanding. Thus, the Ru\u2014C bond distances involving carbonyl groups lying in the plane of the Ru3 ring are generally shorter than those occupying positions perpendicular to the plane, with the respective ranges in Ru\u2014C bond lengths being 1.897\u2005(3)\u20131.930\u2005(3)\u2005\u00c5 and 1.937\u2005(2)\u20131.953\u2005(3)\u2005\u00c5. While the Ru\u2014C\u2261O angles are all close to linear, two distinctive ranges in angles are evident. The Ru\u2014C\u2261O angles involving carbonyl groups lying in the plane of the Ru3 ring lie in the range 177.3\u2005(2)\u2013178.7\u2005(2)\u00b0 while the range for the perpendicularly orientated carbonyl groups is 172.1\u2005(2)\u2013174.6\u2005(2)\u00b0. The trend for longer Ru\u2014C distances and greater deviations from linearity of the Ru\u2014C\u2261O angles for the axial carbonyl ligands, which occupy positions trans to other carbonyl ligands, is consistent with some semi-bridging character for these carbonyl ligands. Thus, the closest intra\u00admolecular Ru\u22efC(carbon\u00adyl) contact of 3.233\u2005(3)\u2005\u00c5 is formed by the C8-carbonyl ligand which exhibits the maximum deviation from linearity, i.e. 172.1\u2005(2)\u00b0.The mol\u00adecular structure of Rua. The O3\u22efO3i separation is 2.817\u2005(2)\u2005\u00c5, a distance less than the sum of the van der Waals radii of oxygen, i.e. 3.04\u2005\u00c5 : 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. Such inter\u00admolecular O\u22efO inter\u00adactions are examples of homoatomic chalcogen bonding which are rarest for the smaller oxygen atoms et al., 2017dnorm are shown in Fig.\u00a03a, results from the C21\u2014H\u22efO8 inter\u00adaction  contact is evident. Carbon\u00adyl\u22ef\u03c0(arene) inter\u00adactions are known to be important in the structural chemistry of metal carbonyls  separation is 3.850\u2005(3)\u2005\u00c5 and the angle subtended at the O4 atom is 90.1\u2005(2)\u00b0, indicating a side-on  approach between the residues. The environment about a reference mol\u00adecule, showing short inter\u00adatomic O\u22efO and C\u22efH/H\u22efC contacts significant in the mol\u00adecule packing of (I)The Hirshfeld surface calculations of (I)n Table\u00a01. The preet al., 2007i.e. 15.6%, contribution from these contacts to the Hirshfeld surfaces is due to the presence of the carbonyl groups on the Ru-cluster which leads to an increase in the contribution of O\u22efH/H\u22efO contacts to the Hirshfeld surface, i.e. 37.4%. The single tip at de + di \u223c2.4\u2005\u00c5 in the H\u22efH delineated fingerprint plot, which has a broad appearance, arises from a van der Waals contact between the methyl-H18B and phenyl-H20 atoms s Table\u00a02. The twoe Table\u00a01 and a she Table\u00a01, respecte Table\u00a01 and othee Table\u00a01 are views Table\u00a02 result iChemical context, there are two other Ru3 clusters in the literature having the same (4-methyl\u00adsulfanylphen\u00adyl)di\u00adphenyl\u00adphosphane ligand as in (I)3(CO)9PPh2(C6H4SMe-4)(Ph2PCH2PPh2) (II) 9PPh2(C6H4SMe-4)(Ph2AsCH2AsPh2) 11PRR\u2032R\u2032\u2032 and several examples where the phosphane ligand is bidentate bridging, i.e. Ru3(CO)11PR(R\u2032)\u2013R\u2032\u2032\u2013(R\u2032)RPRu3(CO)11 11PRR\u2032R\u2032\u2032.As mentioned in the 3(CO)12 was purchased from Aldrich and PPh2C6H4SMe was synthesized as reported previously 11P(C6H4SMe-4)Ph2 (I)3(CO)12  and PPh2(C6H4SMe)  in tetra\u00adhydro\u00adfuran (25\u2005ml). The reaction mixture was treated dropwise with sodium di\u00adphenyl\u00adketyl solution until the colour of the mixture turned from orange to dark red and then stirred for 30\u2005min. The solvent was evaporated under vacuum and the residue was chromatographed by preparative TLC. Elution with 7:3 n-hexa\u00adne/di\u00adchloro\u00admethane mixture gave four bands and the major orange fraction was characterized as (I)30H17O11PRu3S: C, 39.18; H, 1.86%. Found: C, 39.60; H, 1.90%. IR (C6H12): \u03bd(CO) 2097(m), 2059(w), 2046(m), 2015(s), 1989(w) cm\u22121. 1H NMR (CDCl3): \u03b4 7.45\u20137.23 , 2.48 . 13C NMR (CDCl3): \u03b4 204.24 (Ru\u2014CO), 135.19\u2013125.37 (Ph), 14.79 (Me). 31P NMR (CDCl3): \u03b4 34.28 (s).All reactions were carried out under an inert atmosphere of oxygen-free nitro\u00adgen (OFN) using standard Schlenk techniques. RuUiso(H) set to 1.2\u20131.5Ueq(C). Owing to poor agreement, four reflections, i.e. (1 7 14),  I, global. DOI: 10.1107/S2056989018006989/hb7749Isup2.hklStructure factors: contains datablock(s) I. DOI: 1842044CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title compound is constructed from two aromatic rings , which are linked by a C=C\u2014C(=O)\u2014C enone bridge and form a dihedral angle of 17.91\u2005(17)\u00b0. In the crystal, mol\u00adecules are linked by C\u2014H\u22efO hydrogen bonds enclosing rings of  17H14BrFO3, the aromatic rings are tilted with respect to the enone bridge by 13.63\u2005(14) and 4.27\u2005(15)\u00b0, and form a dihedral angle 17.91\u2005(17)\u00b0. In the crystal, centrosymmetrically related mol\u00adecules are linked by pairs of C\u2014H\u22efO hydrogen bonds into dimeric units, forming rings of R22(14) graph-set motif. The dimers are further connected by weak C\u2014H\u22efO hydrogen inter\u00adactions, forming layers parallel to (10In the mol\u00adecule of the title compound, C Chalcones, which are considered to be the precursors of flavonoids and isoflavonoids, are abundant in edible plants. They consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon \u03b1,\u03b2-unsaturated carbonyl system. These are coloured compounds because of the presence of the \u2013CO\u2014CH=CH\u2013 chromophore, the colour depending on the presence of other auxochromes. Accumulating evidence has shown that chalcones and their derivatives could inhibit tumor initiation and progression. In view of the above and in a continuation of our previous work on 3,4-dimeth\u00adoxy chalcones \u2005\u00c5 for C16 and \u22120.124\u2005(4)\u2005\u00c5 for C17. The bond lengths and angles are comparable with those found in the related compounds (2E)-3-(3-chloro\u00adphen\u00adyl)-1--prop-2-en-1-one -3--1-prop-2-en-1-one -1-(3-bromo\u00adphen\u00adyl)-3-prop-2-en-1-one -3-(2-bromo\u00adphen\u00adyl)-1-prop-2-en-1-one \u2005\u00c5, C14\u22efCg1i = 4.010\u2005(4)\u2005\u00c5, C14\u2014Br1\u22efCg1i = 82.54\u2005(11)\u00b0; symmetry code: (i) \u22121\u00a0+\u00a0x, y, z; Cg1 is the centroid of the C1\u2013C6 ring] and C\u2014F\u22ef\u03c0  inter\u00adactions help to stabilize the crystal structure.In addition, weak C\u2014Br\u22ef\u03c0 [C14\u2014Br1 = 1.877\u2005(3)\u2005\u00c5, Br1\u22efCrystalExplorer17.5 . The O\u22efH/H\u22efO, Br\u22efC/C\u22efBr and F\u22efC/C\u22efF contacts in the structure with 17.9, 5.6 and 5.0% contributions, respectively, to the Hirshfeld surface have a symmetrical distribution of points . The other Br\u22efC / C\u22efBr, F\u22efC / C\u22efF, C\u22efC, F\u22efO / O\u22efF and C\u22efO / O\u22efC contacts, having only small contributions to the Hirshfeld surface, have negligible directional impact on the mol\u00adecular packing.Mol\u00adecular Hirshfeld surfaces  = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018009416/rz5240sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009416/rz5240Isup2.hklStructure factors: contains datablock(s) I. DOI: 1852842CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, mol\u00adecules are linked via pairs of the weak inter\u00admolecular C\u2014H\u22efN hydrogen bonds, forming inversion dimers with b]pyridine ring systems.The imidazopyridine unit linked to phenyl and allyl substituents. The allyl substituent is rotated significantly out of the imidazopyridine plane, while the benzene ring is inclined by 3.84\u2005(6)\u00b0 to the ring system. In the crystal, mol\u00adecules are linked via a pair of weak inter\u00admolecular C\u2014H\u22efN hydrogen bonds, forming an inversion dimer with an R22(20) ring motif. The dimers are further connected by \u03c0\u2013\u03c0 stacking inter\u00adactions between the imidazopyridine ring systems [centroid\u2013centroid distances = 3.7161\u2005(13) and 3.8478\u2005(13)\u2005\u00c5]. The important contributions to the Hirshfeld surface are H\u22efH (35.9%), H\u22efCl/Cl\u22efH (15.0%), H\u22efC/C\u22efH (12.4%), H\u22efBr/Br\u22efH (10.8%), H\u22efN/N\u22efH (7.5%), C\u22efBr/Br\u22efC (5.9%), C\u22efC (5.5%) and C\u22efN/N\u22efC (4.0%) contacts.The title compound, C Their activities include anti\u00adcancer -4H-imidazopyridine in the presence of a catalytic qu\u00adantity of tetra-n-butyl\u00adammonium bromide under mild conditions.As a continuation of our research work devoted to the development of substituted imidazopyridine unit linked to phenyl and allyl substituents \u2005\u00c5 for atom C12. The ring system is inclined by 3.84\u2005(6)\u00b0 to the benzene C1\u2013C6 ring, with the N2\u2014C7\u2014C6\u2014C1 torsion angle being 3.3\u2005(3)\u00b0. The allyl substituent is nearly perpendicular to the imidazopyridine plane, as indicated by the C8\u2014N3\u2014C13\u2014C14 torsion angle of \u221297.3\u2005(2)\u00b0. Atoms C6 and C13 are 0.038\u2005(2) and 0.014\u2005(2)\u2005\u00c5, respectively, away from the imidazopyridine plane.The title compound is built up from an imidazopyridine ring systems. The centroid\u2013cen\u00adtroid distances, Cg1\u22efCg1ii and Cg1\u22efCg2i , are 3.7161\u2005(13) and 3.8478\u2005(13)\u2005\u00c5, respectively, where Cg1 and Cg2 are the centroids of the N1/N2/C7\u2013C9 and N3/C8\u2013C12 rings, respectively.In the crystal, mol\u00adecules are linked if Fig.\u00a02. The dimpara-substituated analogue, namely 4-allyl-6-bromo-2-phenyl-4H-imidazopyridine monohydrate, has been reported \u2013(l), together with their relative contributions to the Hirshfeld surface. The contributions are 35.9, 15.0, 12.4, 10.8, 7.5, 5.9, 5.5, 4.0, 1.5, 1.2 and 0.2%, respectively, for H\u22efH, H\u22efCl/Cl\u22efH, H\u22efC/C\u22efH, H\u22efBr/Br\u22efH, H\u22efN/N\u22efH, C\u22efBr/Br\u22efC, C\u22efC, C\u22efN/N\u22efC, C\u22efCl/Cl\u22efC, N\u22efBr/Br\u22efN and N\u22efN contacts. The most important inter\u00adaction is H\u22efH (35.9%), which is reflected as widely scattered points of high density due to the large hydrogen content of the mol\u00adecule [Fig.\u00a05b)]. The spike with the tip at de = di = 1.16\u2005\u00c5 is due to the short inter\u00adatomic H\u22efH contacts. The H\u22efCl/Cl\u22efH contacts (15.0%) have a nearly symmetrical distribution of points and a pair of spikes with tips at de + di = 2.67\u2005\u00c5 [Fig.\u00a05c)]. In the absence of C\u2014H \u22ef \u03c0 inter\u00adactions, the H\u22efC/C\u22efH contacts (12.4%) also have a nearly symmetrical distribution of points with tips at de + di = 2.79\u2005\u00c5 [Fig.\u00a05d)]. The H\u22efBr/Br\u22efH contacts (10.8%) have a symmetrical distribution of points and a pair of spikes with tips at de + di = 3.00\u2005\u00c5 [Fig.\u00a05e)]. A pair of spikes with tips at de + di\u00a0= 2.42\u2005\u00c5  in the H\u22efN/N\u22efH contacts (7.5%) arises from the C\u2014H\u22efN hydrogen bond ]. The C\u22efC contacts (5.5%) have an arrow-shaped distribution of points with the tip at de = di = 1.75\u2005\u00c5 [Fig.\u00a05h)]. The C\u22efN/N\u22efC contacts (4.0%) have wide spikes with tips at de + di = 3.44\u2005\u00c5 [Fig.\u00a05i)]. The HS representations with the function dnorm plotted onto the surface are shown for the H\u22efH, H\u22efCl/Cl\u22efH, H\u22efC/C\u22efH, H\u22efBr/Br\u22efH, H\u22efN/N\u22efH, C\u22efBr/Br\u22efC, C\u22efC and C\u22efN/N\u22efC contacts [Figs.\u00a06a)\u2013(h)].In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis  dissolved in 25\u2005ml of N,N-di\u00admethyl\u00adformamide (DMF) and potassium carbonate  was stirred for 5\u2005min, and then to a mixture of tetra-n-butyl\u00adammonium bromide  and allyl bromide  was added. Stirring was continued for 6\u2005h at room temperature. After removing the salts by filtration, DMF was evaporated under reduced pressure, and the solid obtained was dissolved in di\u00adchloro\u00admethane. The residue was extracted with distilled water and the resulting mixture was chromatographed on a silica-gel column . Brown single crystals suitable for X-ray diffraction were obtained by evaporation of an ethyl acetate\u2013hexane (1:3 v/v) solution.A mixture of 6-bromo-2-(4-chloro\u00adphen\u00adyl)-4Uiso(H) = 1.2Ueq(C).Crystal data, data collection and refinement details are summarized in Table\u00a0210.1107/S2056989018017322/is5505sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018017322/is5505Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017322/is5505Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018017322/is5505Isup4.cmlSupporting information file. DOI: 1883384CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Similarly, mol\u00adecule (2) presents the same bridging group, but it connects two nearly planar appendants, each comprising a phenyl ring bonded with a hydroxyl and two aldehyde groups. Compound (2) exhibits a strong visible luminescence when excited with ultraviolet radiation.The mol\u00adecule of , and 5,5\u2032-bis\u00ad, C19H16O6, (2), crystallize with one mol\u00adecule in the asymmetric unit. In mol\u00adecule (1), a >C(CH3)2 group bridges two nearly planar salicyl\u00adaldehyde groups [r.m.s deviations = 0.010\u2005(1) and 0.025\u2005(2)\u2005\u00c5], each comprising a planar phenyl ring bonded with a hydroxyl and an aldehyde group. Similarly, compound (2) has the same bridging group, but it connects two nearly planar appendants [r.m.s deviations = 0.034\u2005(1) and 0.035\u2005(1)\u2005\u00c5], each comprising a phenyl ring bonded with a hydroxyl and two aldehyde groups. Mol\u00adecule (1) exhibits a bridge angle of 109.5\u2005(2)\u00b0 with the salicyl\u00adaldehyde planes subtending a dihedral angle of 88.4\u2005(1)\u00b0. In contrast, mol\u00adecule (2) presents a bridge angle of 108.9\u2005(2)\u00b0 with its appendants subtending a dihedral angle of 79.6\u2005(3)\u00b0. Both mol\u00adecules exhibit two intra\u00admolecular O\u2014H\u22efO hydrogen bonds involving the phenolic H atoms and carboxyl O-atom acceptors. In the crystal of (2), O\u2014H\u22efO hydrogen bonds between one of the hydroxyl H atoms and a carboxyl O atom from a symmetry-related mol\u00adecule form a chain along [102) exhibits a strong visible luminescence when excited with ultraviolet radiation.The title compounds 5,5\u2032-bis\u00ad, C These precursor compounds present a >C(CH3)2 group that bridges two salicyl\u00adaldehyde moieties (1) or two phenyl groups with an hydroxyl and two aldehyde appendants (2). The various functional groups in these mol\u00adecules determine their chemical and physical properties, and the ability to modify them provides the title compounds with a wide versatility and the multifunctionality required for synthesizing safer and better performance materials for future civilian and military applications. For instance, the title compounds may be used for the non-toxic, iso\u00adcyanate-free synthesis of polyurethanes  is a new, solid-state photoluminescence material that emits radiation in the spectroscopic range between 490 and 590\u2005nm upon ultraviolet light excitation, with potential use as an organic light emitting diode, laser frequency harmonic generator, or photoelectric converter.As polymers play an undeniable role in our everyday lives, extensive resources and safety evaluations are devoted toward the development and marketing of the most suitable and effective polymer species for a given application , the salicyl\u00adaldehyde fragment containing atom C4 (S1A) is near planar [r.m.s. deviation = 0.010\u2005(1)\u2005\u00c5], with a maximum out-of-plane deviation of 0.020\u2005(2)\u2005\u00c5 for the O1 atom. Similarly, its companion salicyl\u00adaldehyde fragment (S1B) is near planar [r.m.s. deviation = 0.025\u2005(2)], with a maximum out-of-plane deviation of 0.050\u2005(2)\u2005\u00c5 for the O3 atom. The bridge angle C4\u2014C1\u2014C11 measures 109.5\u2005(2)\u00b0 and the S1A and S1B planes subtend a dihedral angle of 88.4\u2005(1)\u00b0. Mol\u00adecule (1) exhibits two intra\u00admolecular hydrogen bonds between the phenolic hydrogen atoms and carboxyl O-atom acceptors  presents two near planar appendants, denoted A1 and A2 for the appendants containing C4 and C11, respectively, . Each appendant comprises a hydroxyl and two aldehyde groups. Similar to (1), the salicyl\u00adaldehyde fragments with atoms C4\u2013C9/C11/O1/O2 (S2A) or C12\u2013C17/C18/O6/O5 (S2B) in (2) adopt a near planar geometry [r.m.s. deviation = 0.024\u2005(1)\u2005\u00c5 for S2A and 0.036\u2005(1)\u2005\u00c5 for S2B]. The additional carbonyl groups C10\u2014O3 and C18\u2014O4 on the phenyl rings are twisted slightly out of the S2A and S2B planes, respectively, as evidenced by their respective torsion angles C5\u2014C6\u2014C10\u2014O3 [\u22122.9\u2005(4)\u00b0] and C13\u2014C14\u2014C18\u2014O4 [\u2212179.1\u2005(3)\u00b0]. These additional groups increase the steric hindrance between the appendants and methyl bridge groups in (2), perhaps decreasing both the bridge angle C4\u2014C1\u2014C12 [108.9\u2005(2)\u00b0] and the dihedral angle between the A1 and A2 planes [88.4\u2005(1)\u00b0] relative to (1). Mol\u00adecule (2) presents two intra\u00admolecular hydrogen bonds involving the phenolic hydrogen atoms with the carboxyl O-atom acceptors (Table\u00a021).Mol\u00adecule  and (2) exhibit several intra\u00admolecular H\u22efH contacts that are shorter than the sum of the H-atom van der Waals radii. These contacts occur between the methyl group H atoms and adjacent phenyl group H atoms . Superimposition of the atoms C1/C2/C3/C4/C11 of (1) with the corresponding atoms of (2) \u00b0 and the S1B and S2B planes subtending an angle of 35.1\u2005(1)\u00b0.Both (1) along the a axis. van der Waals contacts between the O atoms and H atoms of adjacent mol\u00adecules  dominate the inter\u00admolecular inter\u00adactions. In addition, bifurcated contacts between atom C17 and atoms H3 and O3 of adjacent mol\u00adecules  contribute to the crystal packing. As in mol\u00adecule (1), O\u22efH contacts play a key role in the inter\u00admolecular inter\u00adactions of (2). However, unlike (1), these inter\u00adactions result mostly from hydrogen bonding between the phenolic hydrogen atoms and the carboxyl oxygen atoms of adjacent mol\u00adecules  Figs. 4 and 5 \u25b8.et al., 2016et al., 2009et al., 2012et al., 2005et al., 20173), a common chemical known also as bis\u00adphenol A,  and 5-[(3-formyl-4-hy\u00addroxy\u00adphen\u00adyl)meth\u00adyl]-2-hy\u00addroxy\u00adbenzaldehyde (4)  and (2) and further discussion. Mol\u00adecule (3) presents a submolecular structure of the title compounds, as it only lacks the aldehyde groups found in (1) or (2). In contrast, (4) exhibits a pair of salicyl\u00adaldehyde groups as (1) or (2), except that they are linked by a >CH2 bridge, instead of a >C(CH3)2 bridge.A search of the Cambridge Structural Database  crystallizes with three independent mol\u00adecules in the asymmetric unit. Each mol\u00adecule presents a pair of planar phenol fragments  subtending dihedral angles of 77.81\u2005(3), 86.15\u2005(4) and 84.34\u2005(4)\u00b0, respectively, and respective bridge angles of 109.2\u2005(1), 109.5\u2005(1), and 108.1\u2005(1)\u00b0. In general, both (1) and (2) have similar geometric parameters to (3), although their corresponding phenol groups are less planar than those of (3). This manifestation results most likely because the phenyl groups of the title compounds contain aldehyde groups in addition to the hydroxyl groups. The O atoms of these aldehyde groups participate in hydrogen bonding with the hydroxyl H atoms, thus partially displacing the hydroxyl O atoms away from the phenol planes. A superimposition of the atoms in (1) with the corresponding atoms of one of the three structures of (3) shows that the differences in the atom positions of the two structures are hardly discernible  and its counterpart of (3)]. An overlay of structure (1) onto either structure two or three of (3) yields comparable results. A similar analysis of structures (2) and (3) yields a r.m.s. deviation of 1.14\u2005\u00c5 with maximum displacement of 0.605\u2005(2)\u2005\u00c5 for the C6 atom of (2) and its counterpart in (3). Again, we obtain comparable results overlaying either structure two or three of (3) onto (1).Compound  exhibits a pair of near planar salicyl\u00adaldehyde fragments [r.m.s. deviation = 0.0153\u2005(2) and 0.0238\u2005(9)\u2005\u00c5] forming a dihedral angle of 85.96\u2005(4)\u00b0, similar to (1). Its bridge angle of 113.6\u2005(1)\u00b0 is much greater than that of (1) or (2), however. A superimposition of the salicyl\u00adaldehyde group atoms of (4)  with corresponding atoms of (1) reveals nearly identical atomic positions of the two groups [r.m.s. deviation = 0.0160\u2005\u00c5], with the companion salicyl\u00adaldehyde group planes [centroid-to-centroid distance measuring = 4.68\u2005(2)\u2005\u00c5] subtending a dihedral angle of 6.81\u00b0. A similar analysis for structures (2) and (4) yields a r.m.s. deviation = 0.027\u2005\u00c5 with companion salicyl\u00adaldehyde groups planes [centroid-to-centroid distance measuring = 4.21\u2005(1)\u2005\u00c5] forming a dihedral angle of 7.4\u2005(1)\u00b0.Mol\u00adecule  and (2), respectively).The title compounds were synthesized following modified literature procedures (\u00d6zdemir 1): A combination of compound (3) , paraformaldehyde , and magnesium(II) chloride  were suspended in tetra\u00adhydro\u00adfuran , placed under a stream of N2, and stirred. Then, tri\u00adethyl\u00adamine  was added dropwise to the reaction mixture at ambient temperature and stirred under reflux for 16\u2005h. At the conclusion of the reaction, the mixture was cooled to room temperature before the addition of diethyl ether (500\u2005mL). The organic solution was sequentially extracted with aqueous 1\u2005M HCl (3 \u00d7 500\u2005mL) and water (3 \u00d7 500\u2005mL), dried over Na2SO\u00ad4 or MgSO4, filtered, and the volatiles were removed under reduced pressure. The solid residue was purified with a series of hexane washes and then dried under vacuum to afford the desired product (1) as a white solid . Slow diffusion of hexa\u00adnes into a benzene solution saturated with (1) afforded single crystals of (1).Compound (2): A mixture of (3)  and hexa\u00admethyl\u00adene\u00adtetra\u00admine  was dissolved in tri\u00adfluoro\u00adacetic acid  under ambient conditions. The reaction mixture was stirred at 403\u2005K for 2.5\u2005h and subsequently cooled to room temperature before aqueous HCl  was added slowly. The reaction mixture was stirred at 383\u2005K for 16\u2005h, cooled to room temperature, and the resulting organic phase extracted with di\u00adchloro\u00admethane . Then, this organic phase was dried over MgSO4, filtered, and the volatiles were removed under reduced pressure. The resulting solid was purified with a series of hexa\u00adnes washes and dried under vacuum to afford the novel product (2) as a neon yellow solid . Slow evaporation of a DCM solution saturated with (2) afforded single crystals suitable for X-ray diffractometry.Compound (1) 1H NMR : \u03b4 1.70 , 6.92 , 7.35 , 7.43 , 9.86 , 10.93  ppm. 13C NMR : \u03b4 30.47, 41.86, 117.85, 120.15, 130.92, 136.20, 141.67, 160.10, 196.74 ppm. (2) 1H NMR : \u03b4 1.75 , 7.81 , 10.19 , 11.53  ppm. 13C NMR : \u03b4 30.31, 30.59, 42.08, 123.05, 135.53, 141.31, 162.20, 191.99 ppm; low-resolution mass spectrometry (atmospheric pressure ionization); Thermo Fisher Scientific (ISQ\u2013EC): m/z [M]+: calculated = 340.33; measured: 340; and luminescence spectrum (Horiba Jobin Yvon Fluoro\u00admax 3 Spectrofluorimeter): 10\u22125 \u2005M/aceto\u00adnitrile; \u03bbexc = 356\u2005nm; \u03bbem = 539\u2005nm .Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker 400\u2005MHz spectrometer. Chemical shifts (\u03b4) are given in ppm: (1) and most in (2) were refined in a riding-model approximation with C\u2014H = 0.93 or 0.96\u2005\u00c5, Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmeth\u00adyl) and O\u2014H = 0.82\u2005\u00c5 and Uiso(H) = 1.5Ueq(O). In (2), atoms H10, H11, H18, and H5A were refined independently with isotropic displacement parameters.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018016316/lh5885sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989018016316/lh58851sup4.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018016316/lh58852sup5.hklStructure factors: contains datablock(s) 2. DOI: 1879532, 1879531CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, two mol\u00adecules are associated into an inversion dimer via a pair of C\u2014H\u22ef\u03c0 inter\u00adactions. The dimers are linked by another pair of C\u2014H\u22ef\u03c0 inter\u00adactions, forming a ribbon along the c-axis direction.In the title compound, C 27H29BrN2, the carbazole ring system is essentially planar, with an r.m.s. deviation of 0.0781\u2005(16)\u2005\u00c5. An intra\u00admolecular N\u2014H\u22efN hydrogen bond forms an S(6) ring motif. One of the tert-butyl substituents shows rotational disorder over two sites with occupancies of 0.592\u2005(3) and 0.408\u2005(3). In the crystal, two mol\u00adecules are associated into an inversion dimer through a pair of C\u2014H\u22ef\u03c0 inter\u00adactions. The dimers are further linked by another pair of C\u2014H\u22ef\u03c0 inter\u00adactions, forming a ribbon along the c-axis direction. A C\u2014H\u22ef\u03c0 inter\u00adaction involving the minor disordered component and the carbazole ring system links the ribbons, generating a network sheet parallel to (100).In the title compound, C Thus, the title compound has two tert-butyl groups on the carbazole moiety. The title compound is a suitable model to investigate an intra\u00admolecular hydrogen bond between the heteroaromatic N\u2014H and the N atom of the imino group. We report herein on its mol\u00adecular and crystal structures.Carbazole derivatives have been widely applied in various fields such as pharmaceuticals \u2005\u00c5 at atom C8. There is an intra\u00admolecular N\u2014H\u22efN hydrogen bond involving the amino group (N3\u2014H3) in the carbazole ring and an imine N atom (N2), generating an S(6) ring motif  and 0.408\u2005(3).The mol\u00adecular structure of the title compound is shown in Fig.\u00a01f Table\u00a01. The dihA\u2014H22C\u22efCg1i in the major disorder component or C21B\u2014H21E\u22efCg1i in the minor disorder component; Cg1 is the centroid of the C25\u2013C30 ring; symmetry code as in Table\u00a01Cg2ii; Cg2 is the centroid of the C4\u2013C9 ring; symmetry code as in Table\u00a01c-axis direction bis\u00ad[N-methanimine]  and 4-bromo\u00adaniline  were treated in xylene (10\u2005ml) at 423\u2005K under inert gas overnight, followed by evaporation. The recrystallization of the residue from a solvent mixture of acetone and methanol  afforded single crystals of the title compound suitable for X-ray structure analysis . 1H NMR  \u03b4 = 1.47 , 1.49 , 7.22 , 7.47\u20137.58 , 7.67 , 8.13 , 8.26 , 8.72 , 10.55 . HR\u2013MS (m/z): calculated for [C27H30BrN2]+, m/z = 461.1587; found, 461.1627.3,6-Di-Uiso(H) = 1.2Ueq(C). Orientational disorder of the tert-butyl substituent (C20\u2013C23) around the C13\u2014C20 bond axis is observed and the occupancies refined to 0.592\u2005(3) and 0.408\u2005(3).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019012374/is5522sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019012374/is5522Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019012374/is5522Isup3.cmlSupporting information file. DOI: 1951647CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "R)- and (S)-camphor thio\u00adsemicarbazone, which crystallizes in the centrosymmetric space group C2/c, is reported.A racemic mixture of ( R)- and (S)-camphorquinone with thio\u00adsemicarbazide yielded the title compound, C11H17N3OS [common name: (R)- and (S)-camphor thio\u00adsemicarbazone], which maintains the chirality of the methyl\u00adated chiral carbon atoms and crystallizes in the centrosymmetric space group C2/c. There are two mol\u00adecules in general positions in the asymmetric unit, one of them being the (1R)-camphor thio\u00adsemicarbazone isomer and the second the (1S)- isomer. In the crystal, the mol\u00adecular units are linked by C\u2014H\u22efS, N\u2014H\u22efO and N\u2014H\u22efS inter\u00adactions, building a tape-like structure parallel to the (R21(7) and R22(8) graph-set motifs for the H\u22efS inter\u00adactions. The Hirshfeld surface analysis indicates that the major contributions for crystal cohesion are from H\u22efH (55.00%), H\u22efS (22.00%), H\u22efN (8.90%) and H\u22efO (8.40%) inter\u00adactions.The equimolar reaction between a racemic mixture of ( R1R2C=O group and it was pointed out that the R1R2C=N\u2014N(H)C(=S)NH2 compound was the main product of the condensation reaction  and soft (S) donor atoms in chain  chemistry can be traced back to the beginning of the 20th century, when thio\u00adsemicarbazide was used for the chemical characterization of the et al., 2009II, ZnII and FeII/III and reducing the bioavailability of these essential metals, which impacts the growth of tumor cells  inhibition in vitro, a key biological target for cancer research - and the other the (1S)-isomer. For the first mol\u00adecule, the 1R and the 4S chiral centers are labelled C2 and C5, and the thio\u00adsemicarbazone unit is nearly planar with a N1\u2014N2\u2014C11\u2014N3 torsion angle of \u22124.7\u2005(2)\u00b0 \u00b0 \u00b0 Fig.\u00a01. In the )\u00b0 Fig.\u00a02. The twoi, N3\u2014H17\u22efO1ii, C5\u2014H5\u22efS2i and N5\u2014H32\u22efS1iii inter\u00adactions  and di (x axis) values are the closest external and inter\u00adnal distances  from given points on the Hirshfeld surface contacts -camphor 4-phenyl\u00adthio\u00adsemi\u00adcarbazone -camphor 4-phen\u00adyl\u00adthio\u00adsemicarbazone. For the literature structure, the decrease of the contributions from other possible inter\u00adactions is assumed to be due to the geometric impediment of the phenyl ring. The impact of steric effects on the inter\u00admolecular inter\u00adactions sites can be seen in the graphical representation of the Hirshfeld surface in Fig.\u00a09R)-camphor 4-phenyl-TSC mol\u00adecules crystallize as discrete units, being connect by very weak inter\u00adactions. The most frequent inter\u00admolecular inter\u00adactions for the crystal cohesion of the phenyl-TSC derivative are (in %) H\u22efH = 55.9, H\u22efC/C\u22efH = 16.8, H\u22efS/S\u22efH = 11.0, H\u22efO/O\u22efH = 7.8 and H\u22efN/N\u22efH = 7.0. The replace\u00adment of one H atom by the phenyl group in the terminal amine entity strongly impacts on, for example, the contribution of the inter\u00admolecular H\u22efS/S\u22efH inter\u00adactions, which changed from 22.00% to 11.00%. Finally and remarkably, in the comparison mol\u00adecule, inter\u00admolecular H\u22efC/C\u22efH inter\u00adactions make the next highest contibution to the Hirshfeld surface; this inter\u00adaction is comparatively less relevant for the title compound (4.5%).To the best of pur knowledge and from using database tools such as R- and S-camphor was oxidized with SeO2 to the respective 1,2-diketone  = 1.2Ueq and C\u2014H bond distances of 0.98\u2005\u00c5 for tertiary carbon atoms and 0.97\u2005\u00c5 for secondary C atoms. The N\u2014H bond distances are 0.86\u2005\u00c5. Finally, Uiso(H) = 1.5Ueq(C) for the methyl groups, with C\u2014H bond distances of 0.96\u2005\u00c5. A rotating model was used for the latter H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019016980/rz5268sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989019016980/rz5268Isup2.hklStructure factors: contains datablock(s) I. DOI: 1973095CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Several O\u2014H\u22efN and N\u2014H\u22efO hydrogen-bonding inter\u00adactions exist between the [Zn(H 2O)6](NO3)2\u00b72C6H5N5, crystallizes in the space group P3\u2212 anion and one half of a [Zn(H2O)6]2+ cation (2O)6]2+ cation and the N atoms of the tetra\u00adzolide ring, and between the nitrate anions and the N\u2014H groups of the pyridinium ring, respectively, giving rise to a three-dimensional network. The 5-(pyridinium-3-yl)tetra\u00adzol-1-ide mol\u00adecules show parallel-displaced \u03c0\u2013\u03c0 stacking inter\u00adactions; the centroid\u2013centroid distance between adjacent tetra\u00adzolide rings is 3.6298\u2005(6)\u2005\u00c5 and that between the pyridinium and tetra\u00adzolide rings is 3.6120\u2005(5)\u2005\u00c5.Hexa\u00adaqua\u00adzinc(II) dinitrate 5-(pyridinium-3-yl)tetra\u00adzol-1-ide, [Zn(H The hexa\u00adaqua\u00adzinc(II) complex exhibits regular octa\u00adhedral geometry 6]X2  cocrystallized with 5-(pyridinium-3-yl)tetra\u00adzol-1-ide tetra\u00adzol-1-ide zwitterion, one NOy Table\u00a01, and they Table\u00a01. The geo2O)6]2+, through O\u2014H\u22efN hydrogen bonds, exhibiting D\u22efA distances in the range 2.7446\u2005(17)\u20132.8589\u2005(17)\u2005\u00c5. Additionally, the pyridinium ring is involved in N\u2014H\u22efO hydrogen bonding to nitrate atom O4, with an N\u22efO distance of 2.7384\u2005(18)\u2005\u00c5. These inter\u00adactions are shown in the crystal packing diagram  plane. These parallel-displaced \u03c0\u2013\u03c0 inter\u00adactions lead to inter\u00adplanar distances of 3.21\u2005(1) and 3.10\u2005(3)\u2005\u00c5, and two centroid\u2013centroid distances  com\u00adplex cations and nitrate ions serves to hold the structure together Table\u00a02. The N aam Fig.\u00a03. The strs Table\u00a03. The cens Table\u00a03.baab2O)6]X2\u00b72C6H5N5 structures, as more hexa\u00adaqua\u00adzinc(II) complexes can inter\u00adact with the N atoms of the tetra\u00adzole units. Parallel-displaced \u03c0\u2013\u03c0 stacking inter\u00adactions occur in the title compound and in [Mg(H2O)6]X2\u00b72C6H5N5. In [Mg(H2O)6]Cl2\u00b72C6H5N5, the pyridinium\u2013tetra\u00adzolide zwitterions have alternating orientations in the supra\u00admolecular arrangement, whereas in the title compound, the zwitterions are oriented in the same direction, allowing a possible coupling transition between dipole moments similar to J-aggregates  cation with a halide counter-ion [chloride  and ZnCl2 (2\u2005mmol) were dissolved in 6\u2005ml of distilled water. This mixture was transferred to a glass bottle and then heated at 378\u2005K for 24\u2005h. The pH was adjusted using a HNO3 (66%) solution immediately after mixing the reactants, and was monitored with a pH meter (pH2700 Oakton) until reaching a pH of 2.0. The reaction mixture was then cooled to 318\u2005K and kept at this temperature for 16\u2005h. The colourless block-shaped crystals obtained were washed with ethanol to give 353\u2005mg (yield 30%) of the title compound.All the reactants and chemicals were purchased from Sigma Aldrich and utilized without further purification. A mixture of 3-cyano\u00adpyridine (4\u2005mmol), NaNUiso(H) = 1.2Ueq(C). Moreover, all H atoms in the hexa\u00adaqua\u00adzinc(II) complex were refined with a distance restraint of O\u2014H = 0.85\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698901801112X/cq2025sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901801112X/cq2025Isup3.hklStructure factors: contains datablock(s) I. DOI: 1860162CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The ergogenic effect of \u03b2A has also been demonstrated for 2000-m rowing performance prompting interest in whether \u03b2A may be beneficial for sustained aerobic exercise. This study therefore investigated the effect of two \u03b2A dosing strategies on 30-min rowing and subsequent sprint performance.\u2212\u20091, \u03b2A1); ii) matched total \u03b2A ; or iii) cornflour placebo . Participants completed a laboratory 30-min rowing time-trial, followed by 3x30-seconds (s) maximal sprint efforts at days 0, 14 and 28 (T1-T3). Total distance (m), average power (W), relative average power (W\u00b7kg\u2212\u20091), cardio-respiratory measures and perceived exertion were assessed for each 10-min split. Blood lactate ([La-]b mmol\u00b7L\u2212\u20091) was monitored pre-post time-trial and following maximal sprint efforts. A 3-way repeated measures ANOVA was employed for main analyses, with Bonferonni post-hoc assessment (P\u2009\u2264\u20090.05).Following University Ethics approval, twenty-seven healthy, male rowers  were randomised in a double-blind manner to 4\u2009weeks of: i) \u03b2A , including absolute average power  and relative average power output . These findings were potentially explained by within-group significance for the same variables for the first 10\u2009min split (P\u2009\u2264\u20090.01), and for distance covered (P\u2009=\u20090.01) in the second 10-min split. However, no condition x time interactions were observed. No significant effects were found for sprint variables (P\u2009>\u20090.05) with comparable values at T3 for mean distance , average power  and lactate .Total 30-min time-trial distance significantly increased from T1-T3 within \u03b2A1 only  may be warranted based on within-group observations.Whilst daily \u03b2A may confer individual benefits, these results demonstrate limited impact of \u03b2A (irrespective of dosing strategy) on 30-min rowing or subsequent sprint performance. Further investigation of \u03b2A dosage >\u20092.4\u2009g\u00b7d Following a 5-min seated period, 2-min baseline expired air samples were collected via the Douglas bag method  and anal\u2212]b was assessed following the final collection period only.All time-trials were conducted on the same Concept 2 air braked rowing ergometer  with resistance set at 5 for standardisation. Participants undertook a self-paced, continuous warm-up at 100\u2009W for 5-min, after which the unit display was modified to display time remaining to minimise extraneous influences on pacing strategy . Partici\u2212]b, RPE and performance data (distance rowed (m), average power (W)) were recorded on completion of each sprint. At the mid-point of each sprint, standardised verbal encouragement was given to all participants to promote maximal engagement.Following a standardised 5-min inactive rest period, participants completed three 30-s maximal sprint efforts with 60-s inactive recovery in between. b (mmol\u00b7L\u2212\u20091) , absolute VO2 (L\u00b7min\u2212\u20091)  or relative VO2 (ml\u00b7kg\u2212\u20091\u00b7min\u2212\u20091) .Intervention groups were matched for age (yrs), rowing experience (yrs), body-height (m), body-mass (kg) and body-fat (%) at baseline Table . Non sigP\u2009=\u20090.22, \u03b7p2\u2009=\u20090.11). A significant effect was shown for time only , with \u03b2A1 distance increasing from 7397\u2009\u00b1\u2009195\u2009m at T1 to 7580\u2009\u00b1\u2009171\u2009m by T3 only .Data for distance rowed (m) during the 30-min time trial are shown as absolute a) and relative b) values in Fig. P\u00a0=\u20090.05, \u03b7p2\u2009=\u20090.12) with \u03b2A1 from 194.8\u00a0\u00b1\u00a018.3\u2009W (T1) to 204.2\u00a0\u00b1\u00a015.5 (T3) (P\u00a0=\u20090.04). No differences were reported within group for \u03b2A2 (200.3\u00a0\u00b1\u00a09.8\u2009W (T1) to 208.8\u00a0\u00b1\u00a08.0\u2009W (T3); P\u00a0>\u20090.05) or PL (173.0\u00a0\u00b1\u00a013.8\u2009W (T1) to 174.8\u00a0\u00b1\u00a013.7\u2009W (T3); P\u2009>\u20090.05). When adjusted for body-mass, average power output expressed as a) absolute and b) relative change is shown in Fig. \u2212\u20091) between T1 and T3  for \u03b2A1 only . A significant between group main effect was reported , with post-hoc analysis indicating an overall difference between \u03b2A2 and PL only (P\u2009=\u20090.04). However, no group x time interactions were shown for absolute changes in average power to weight ratio . When data was expressed as relative change in average power, no significant between group differences were observed ; despite small improvements of 0.13\u2009\u00b1\u20090.06\u2009W\u00b7kg\u2212\u20091 for \u03b2A1 and 0.11\u2009\u00b1\u20090.05\u2009W\u00b7kg\u2212\u20091 for \u03b2A2, in contrast to negligible changes of 0.01\u2009\u00b1\u20090.06\u2009W\u00b7kg\u2212\u20091 for PL.Similarly, mean power significantly increased for time only  for \u03b2A1 only , however RPE was maintained throughout the intervention (average RPE: 7.7\u00a0\u00b1\u00a00.2 (T1), 7.8\u00a0\u00b1\u00a00.2 (T2), 7.8\u00a0\u00b1\u00a00.3 (T3) P\u2009>\u20090.05). In contrast, average RPE significantly increased by T3  for both \u03b2A2 (7.1\u00a0\u00b1\u00a00.5 (T1) to 7.7\u00a0\u00b1\u00a00.4 (T3); P\u2009=\u20090.04) and PL (6.5\u00a0\u00b1\u00a00.4 (T1) to 7.3\u00a0\u00b1\u00a00.03 (T3); P\u2009=\u20090.01). Average VO2 was maintained across all trials with no group x time interactions reported (\u03b2A1: 3.12\u00a0\u00b1\u00a00.12\u2009L\u00b7min\u2212\u20091 (T1) to 3.14\u00a0\u00b1\u00a00.10 (T3); \u03b2A2: 3.17\u00a0\u00b1\u00a00.10\u2009L\u00b7min\u2212\u20091 (T1) to 3.24\u00a0\u00b1\u00a00.14 (T3); PL: 2.93\u00a0\u00b1\u00a00.13\u2009L\u00b7min\u2212\u20091 (T1) to 2.86\u00a0\u00b1\u00a00.14 (T3); P\u2009>\u20090.05).Average HR significantly increased by T3 , with \u03b2A1 significantly increasing between T1-T2 (P\u2009=\u20090.03), T1-T3 (P\u2009=\u20090.004) representing a 3.65% (T1-T2) and 4.52% (T1-T3) distance increase, respectively. Likewise, \u03b2A2 also increased distance covered significantly by 2.55% from T2-T3 (P\u2009=\u20090.01). Accompanying these effects for distance, time effects  for absolute power was observed in \u03b2A1 only between T1-T2 (P\u2009=\u20090.03) and T1-T3 (P\u2009=\u20090.01). These represented a 14.04 and 14.61% increase in watts, respectively. Time effects  for power to weight was observed in \u03b2A1 only, between T1-T2 (P\u2009=\u20090.02) and T1-T3 (P\u2009=\u20090.01). These represented a 6.20 and 6.75% increase in W\u00b7kg\u2212\u20091, respectively.No group x time interactions were shown for overall 0-10\u2009min time trial performance  between T1 and T3  for \u03b2A1  and \u03b2A2 , but not PL (P\u2009>\u20090.05). In contrast, average RPE , VE , VO2 , VCO2  and RER  were maintained across all trials with no significant interactions reported.A significant effect was observed for changes in HR , with \u03b2A1 increasing distance rowed by 54\u2009\u00b1\u200914\u2009m between T1-T3 (P\u2009=\u20090.01). Other performance variables such as absolute power  and power to weight  failed to reach significance overall. Average HR , VE , VO2 , VCO2 , RPE , and RER  were maintained across all trials with no significant interactions reported.No group x time interactions were shown during the second 10-min split  in distance covered or other performance variables (P\u2009>\u20090.05). Average HR , VE , VO2 , VCO2  RPE  and RER  were maintained across trials with no significant group x time interactions reported.No group x time interactions were shown for overall 21\u201330\u2009min time trial distance covered , or time  effects were observed at any time-point for distance covered. Likewise, power , power to weight , HR , RPE  and [La-]b  failed to reach significance.No significant between-group effects existed at T1 with all groups rowing 166.0\u2009\u00b1\u20092.5\u2009m , on 30-min rowing time trial and subsequent anaerobic sprint performance. A recent 2018 ISSN Position Stand  stated tThe findings from the current study support previous research on 10-km running performance , wherebymilieu interieur\u2019 from homeostatic perturbations caused by supra-maximal levels of intracellular acidosis. However, whilst the current cohorts [La\u2212]b were clearly elevated following each sprint bout, the mean [La\u2212]b post time trial and during associated sprint efforts for \u03b2A1 were not significantly affected by \u03b2A consumption compared to PL, possibly suggesting an absence of meaningful carnosine facilitated buffering at the current dosage.Regarding the anaerobic sprint data, no significant interaction effects were observed for any variables. This was unexpected as previously Suzuki et al.  noted a \u2212\u20091), it is feasible that one explanation for a lack of significant findings with \u03b2A2 may have been influenced as a result of variances in lean muscle mass.A novel aspect of this study was the inclusion of an alternate day dosing strategy . Previous research has suggested that the primary facilitator of muscle carnosine concentration is the total dose consumed, not factors such as baseline content or daily dose . The curOther reasons for variation caused by dosing may reside in the pharmacokinetics of \u03b2A, with previous research  exhibiti\u2212]b, RPE and HR were recorded throughout the test, blood pH was not. Subsequently, it must be conceded that the capacity to assess or infer whether effects were associated with carnosine directed (pH) buffering are limited. Additionally, due to a commonly reported side effect of \u03b2A , particesthesia , 48.\u2212\u20091 for four-weeks is not sufficient to maximise muscle carnosine content [\u2212\u20091 of \u03b2A each day for 24\u2009weeks, observing gene expression, muscle carnosine content and cycling capacity (CCT110%) [\u2212\u20091 [Beyond the delivery method of \u03b2A, previous research demonstrated that at an average daily dose of 5.2\u2009g\u00b7day content . More reCCT110%) . Interes0%) [\u2212\u20091 ) or dura0%) [\u2212\u20091  may be w\u2212\u20091) for longer periods (>\u200928\u2009days) should also be considered.In conclusion, regardless of dose strategy, when compared to placebo, \u03b2A does not enhance sustained aerobic performance or subsequent high intensity efforts. However, the within-group finding that daily \u03b2A use increased 30-min rowing time trial performance warrants further investigation. The inclusion of higher dosing strategies (>\u20092.4\u2009g\u00b7day"}
{"text": "In the crystal, the mol\u00adecules are joined by C\u2014H\u22efO contacts into infinite chains along the  18H23FO5, was synthesized by reacting diethyl malonate with 1-(4-fluoro\u00adphen\u00adyl)-3-methyl\u00adbut-2-en-1-one. The mol\u00adecule adopts a loose conformation stabilized by weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions. In the crystal, the mol\u00adecules are joined by C\u2014H\u22efO contacts into infinite chains along the b-axis direction with a C(6) graph-set motif. Hirshfeld surface analysis and fingerprint plots demonstrate the predominance of H\u22efH, O\u22efH and F\u22efH inter\u00admolecular inter\u00adactions in the crystal structure.The title compound, C The mol\u00adecular conformation is stabilized by an intra\u00admolecular C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 inter\u00adaction \u00b0; the dihedral angles formed by aromatic ring with adjacent and opposite ester groups are 56.66\u2005(4) and 16.08\u2005(4)\u00b0, respectively. The dihedral angle between aromatic ring and ketone carbonyl unit is 14.04\u2005(5)\u00b0.The title compound crystallizes in the monoclinic crystal system in the space group on Fig.\u00a01 and shorB\u22efO2, which join the mol\u00adecules into infinite chains with graph-set motif C(6) \u2014CH2 and C6H4\u2014C(=O)\u2014CH2\u2014CH2\u2014CH(COO)2 gave 102 and 62 hits, respectively. Among them, two hits, (S)-ethyl-2-(4-t-butyl\u00adbenzyl\u00adsulfan\u00adyl)-4-(4-fluoro\u00adphen\u00adyl)-4-oxo\u00adbutano\u00adate -2-(1-(4-nitro\u00adphen\u00adyl)-1,4-dioxo\u00adpentan-3-yl) malonate . Single crystals of the title compound were obtained by slow evaporation from acetone solvent at room temperature.To a stirred solution of diethyl malonate  in tetra\u00adhydro\u00adfuran (5\u2005ml), sodium hydride  was added at 273\u2005K. The reaction mixture was allowed to stir for 15\u2005min. A solution of 1-(4-fluoro\u00adphen\u00adyl)-3-methyl\u00adbut-2-en-1-one  in THF was added into the reaction mixture. The reaction mixture was then allowed to stir overnight at room temperature. The completion of the reaction was monitored by thin layer chromatography. The reaction mixture was quenched with saturated ammonium chloride and extracted with ethyl acetate (2 \u00d7 25\u2005ml). The combined organic layer was washed with water (2 \u00d7 25\u2005ml), brine (25\u2005ml), dried over sodium sulfate and evaporated under reduced pressure to obtain the crude product, which was purified by column chromatography using 60\u2013120 mesh silica gel with ethyl acetate and hexane eluent (Uiso = 1.2 or 1.5Ueq(C). The methyl groups were allowed to rotate.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018012094/yk2116sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018012094/yk2116Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018012094/yk2116Isup3.cmlSupporting information file. DOI: 1863914CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title pyridiniminium halide salt comprise of one cation and one anion. In the crystal, mol\u00adecules are linked by N\u2014H\u22efBr and C\u2014H\u22efO hydrogen bonds, C\u2014H\u22ef\u03c0 inter\u00adactions, and \u03c0\u2013\u03c0 inter\u00adactions into layers. The inter\u00admolecular inter\u00adactions in the crystal structure are qu\u00adanti\u00adfied by Hirshfeld surface analysis. 17H23N2O+\u00b7Br\u2212, the adamantyl moiety and the pyridiniminium ring are inclined to the ketone bridge by torsion angles of \u221278.1\u2005(2) (C\u2014C\u2014C=O) and 58.3\u2005(2)\u00b0 (C\u2014C\u2014N\u2014C), respectively, and the ketone bridge has a C\u2014C\u2014C\u2014N torsion angle of 174.80\u2005(15)\u00b0. In the crystal, the cations are connected into chains parallel to the c axis by C\u2014H\u22efO hydrogen bonds. The chains are further linked into layers parallel to the bc plane by N\u2014H\u22efBr and C\u2014H\u22efBr hydrogen bonds, C\u2014H\u22ef\u03c0 inter\u00adactions and \u03c0\u2013\u03c0 stacking inter\u00adactions [centroid-to-centroid distance = 3.5657\u2005(11)\u2005\u00c5]. A Hirshfeld surface analysis, which comprises the dnorm surface, electrostatic potential map and two-dimensional fingerprint plots, was carried out to verify the contribution of the various inter\u00admolecular inter\u00adactions.In the cation of the title salt, C The ketone bridge is in an anti\u00adperiplanar conformation [C1\u2014C11\u2014C12\u2014N1 = 174.80\u2005(15)\u00b0]. The dihedral angle formed by the pyrimidinium ring with the ketone bridge is 59.77\u2005(14)\u00b0. Bond lengths and angles in the cation are within normal ranges \u2005\u00c5], indicating partial double-bond character. Similar bond lengths are found in related compounds with an N+=C double bond \u2005\u00c5].In the crystal, the cations are linked into chains along the s Table\u00a01. The chaCrystalExplorer3.1  in the electrostatic potential map indicates hydrogen-acceptor potential, whereas the hydrogen donors are represented by positive electrostatic potential (blue region) . This observation is further confirmed by the respective electrostatic potential maps where Br1 shows negative electrostatic potential as a hydrogen acceptor . Beside those two short inter\u00admolecular contacts, the C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions are shown as light-red spots on the dnorm surface . The reciprocal H\u22efBr/Br\u22efH and H\u22efO/O\u22efH inter\u00adactions with 15.9% and 7.6% contributions, respectively are present as sharp symmetrical spikes at de + di \u2243 2.4 and 2.5\u2005\u00c5, respectively . The reciprocal H\u22efC/C\u22efH inter\u00adactions appear as two symmetrical narrow wings at de + di \u2243 2.5\u2005\u00c5 and contribute 7.8% to the Hirshfeld surface . The reciprocal N\u22efH/H\u22efN interactions appear as a symmetrical V-shaped wing in the FP map with de + di \u2243 2.7\u2005\u00c5 and contribute 2.7% to the Hirshfeld surface . The percentage contributions for other inter\u00admolecular contacts are less than 2.6%.A qu\u00adanti\u00adtative analysis of the inter\u00admolecular inter\u00adactions can be made by studying the fingerprint plots (FP); characteristic pseudo-symmetry wings in the FP Fig.\u00a06. The mos\u2005\u00c5 Fig.\u00a06b. The rly Fig.\u00a06c and 6ece Fig.\u00a06d. The rce Fig.\u00a06f. The pet al., 2017et al., 2018A mixture of 1-adamantly bromo\u00admethyl ketone  and 4-amino\u00adpyridine  was dissolved in 10\u2005ml of toluene at room temperature, followed by stirring at 358\u2005K for 18\u2005h. The completion of the reaction was marked by the amount of the separated solid from the initially clear and homogeneous mixture of the starting materials. The solid was filtered and washed by ethyl acetate. The final pyridiniminium salt was obtained after the solid had been dried under reduced pressure to remove all volatile organic compounds (Said Uiso(H) = 1.2Ueq(C). The N-bound H atoms were located in a difference-Fourier map and freely refined. One outlier (100) was omitted in the last cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018009131/rz5239sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009131/rz5239Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018009131/rz5239Isup3.cmlSupporting information file. DOI: 1851334CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "A weak C\u2014Hmeth\u00adoxy\u00admeth\u00adyl\u22ef\u03c0 inter\u00adaction is also observed.The title compound is built up by two dioxolo, two pyridine, one pyridazine and one pyran rings. The two dioxolo rings are in envelope conformations, while the pyran ring is in twisted-boat conformation. The pyradizine ring is oriented at dihedral angles of 9.23\u2005(6) and 12.98\u2005(9)\u00b0 with respect to the pyridine rings, while the dihedral angle between the two pyridine rings is 13.45\u2005(10)\u00b0. In the crystal, C\u2014H 27H30N4O6\u00b7H2O, the two dioxolo rings are in envelope conformations, while the pyran ring is in a twisted-boat conformation. The pyradizine ring is oriented at dihedral angles of 9.23\u2005(6) and 12.98\u2005(9)\u00b0 with respect to the pyridine rings, while the dihedral angle between the two pyridine rings is 13.45\u2005(10)\u00b0. In the crystal, O\u2014Hwater\u22efOpyran, O\u2014Hwater\u22efOmeth\u00adoxy\u00admeth\u00adyl and O\u2014Hwater\u22efNpyridazine hydrogen bonds link the mol\u00adecules into chains along [010]. In addition, weak C\u2014Hdioxolo\u22efOdioxolo hydrogen bonds and a weak C\u2014Hmeth\u00adoxy\u00admeth\u00adyl\u22ef\u03c0 inter\u00adaction complete the three-dimensional structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (55.7%), H\u22efC/C\u22efH (14.6%), H\u22efO/O\u22efH (14.5%) and H\u22efN/N\u22efH (9.6%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing. Electrochemical measurements are also reported.In the title compound, C O-triphosphate can be used as a potential substrate for fluorescence detection and imaging of DNA pyridazine and its derivatives has been a goal of chemists in recent years. 5--2\u2032-de\u00adoxy\u00aduridine-5\u2032-B (O2/O3/C2\u2013C4) and C (O4/O5/C5\u2013C7), are in envelope conformations. Atoms O3 and O4 are at the flap positions and are displaced by 0.442\u2005(2) and \u22120.397\u2005(2)\u2005\u00c5, respectively, from the least-squares planes of the four atoms. A puckering analysis of the pyran ring A (O1/C1/C2/C4\u2013C6), gave the parameters QT = 0.6508\u2005(25)\u2005\u00c5, q2 = 0.6451\u2005(25)\u2005\u00c5, q3 = \u22120.0865\u2005(26)\u2005\u00c5, \u03c6 = 214.6\u2005(2)\u00b0 and \u03b8 = 97.64\u2005(23)\u00b0, indicating a twisted-boat conformation. The pyradizine ring D (N1/N2/C14\u2013C17) is oriented at dihedral angles of 9.23\u2005(6) and 12.98\u2005(9)\u00b0, respectively, to the pyridine rings E (N3/C18\u2013C22) and F (N4/C23\u2013C27), while the dihedral angle between the two pyridine rings is 13.45\u2005(10)\u00b0. The meth\u00adoxy\u00admethyl moiety is nearly co-planar with the pyradizine ring, as indicated by the O6\u2014C13\u2014C14\u2014C15 torsion angle of \u2212172.8\u2005(2)\u00b0.The title mol\u00adecule contains two dioxolo, two pyridine, one pyridazine and one pyran rings Fig.\u00a01. The pyrwater\u22efOpyran, O\u2014Hwater\u22efOmeth\u00adoxy\u00admeth\u00adyl and O\u2014Hwater\u22efNpyridazine hydrogen bonds  analysis  have a symmetrical distribution of points, Fig.\u00a05c, with the thin and thick edges at de + di = 2.85 and 2.78\u2005\u00c5. The pair of characteristic wings in the fingerprint plot delineated into H\u22efO/O\u22efH contacts  arises from the O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds  arises from the O\u2014H\u22efN hydrogen bonds  have a wide spike with the tip at de = di = 1.75\u2005\u00c5.The most important inter\u00adaction is H\u22efH, contributing 55.7% to the overall crystal packing, which is reflected in Fig.\u00a05s Table\u00a01 as well s Table\u00a01 and has ts Fig.\u00a05e, 9.6% s Table\u00a01 as well ts Fig.\u00a05g, 2.4% dnorm plotted onto the surface are shown for the H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions in Fig.\u00a06a\u2013d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing  = [1 \u2212 Rt(HCl)/Rt(inh)] \u00d7 100, where Rt(inh) and Rt(HCl) are the charge-transfer resistances for MS immersed in HCl, with the title compound and without inhibitor. Nyquist representations of mild steel in 1 M HCl in the absence and presence of the inhibitor system are shown in Fig.\u00a07The effect of the title compound as an inhibitor of the corrosion of mild steel (MS) were studied using electrochemical impedance spectroscopy in the concentration range of 10M HCl without and with various concentrations of the inhibitor. The impedance diagrams obtained have an almost semicircular appearance. This indicates that the corrosion of mild steel in aqueous solution is mainly controlled by a charge-transfer process. The imp\u00adedance parameters are given in Fig.\u00a08Rct is increased to a maximum value of 185 \u03a9 cm2 for the inhibitor, showing a maximum inhibition efficiency of 91% at 10\u22123M. The decrease in Cdl from the HCl acid value of 200\u2005\u00b5F cm\u22122, may be due to the increase in the thickness of the electrical double layer or to a decrease in the local dielectric constant  specimens in 1 et al., 2008viz. aqua\u00adbis\u00adcopper(II) bis\u00ad(tri\u00adfluoro\u00admeth\u00adane\u00adsulfonate) pyridazine]bis\u00ad(\u03bc2-azido)\u00addiaza\u00adidodicopper monohydrate]  complexes coordinated by 3,6-di(pyridin-2-yl)pyridazine ligands have been reported  was added to a solution of 3,6-bis\u00ad(2-pyrid\u00adyl)-1,2,4,5-tetra\u00adzine (4\u2005mmol) in toluene (20\u2005ml). Stirring was continued at room temperature for 4\u2005h. The solvent was removed under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate/hexane (1:2) as eluent. Colourless crystals were isolated on evaporation of the solvent (yield: 82%).6-Uiso(H) = 1.5Ueq(C-meth\u00adyl) or 1.2Ueq(C) for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989019009848/lh5910sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019009848/lh5910Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019009848/lh5910Isup3.cdxSupporting information file. DOI: 1939591CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II and CoII cations to form a polymeric complex chain propagating along the b-axis direction.The pyridine-2,6-di\u00adcarboxyl\u00adate anions bridge the Ca 7H3NO4)2(H2O)4]\u00b72H2O}n (1), the CoII ion is N,O,O\u2032-chelated by two pyridine-2,6-di\u00adcarboxyl\u00adate anions in a distorted N2O4 octa\u00adhedral geometry, and two carboxyl\u00adate O atoms of pyridine-2,6-di\u00adcarboxyl\u00adate anions bridge tetra\u00adaqua\u00adcalcium(II) units to form polymeric chains propagating along the b-axis direction. In the crystal, O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, and offset \u03c0\u2013\u03c0 stacking inter\u00adactions [inter\u00adcentroid distances = 3.551\u2005(1) and 3.746\u2005(1)\u2005\u00c5] involving inversion-related pyridine rings link the polymeric chains and lattice water mol\u00adecules to form a supra\u00admolecular three-dimensional framework.In the crystal of the title polymeric complex, {[CoCa(C Firstly, the O and N atoms in these ligands made them easy to chelate or bridge metal ions. Secondly, they can be completely or partially deprotonated to generate Hpdc\u2212 or pyc2\u2212, displaying a variety of coordination modes. As a part of our ongoing studies on heterometallic frameworks, we describe here the synthesis and crystal structure of the title complex,1The controllable synthesis of heterometallic polymers, with their fascinating structures and outstanding properties, is still a challenge in crystal engineering \u2005\u00c5, inter\u00adplanar distance = 3.309\u2005(1)\u2005\u00c5, slippage = 1.755\u2005\u00c5; Cg6\u22efCg6viii = 3.551\u2005(1)\u2005\u00c5, inter\u00adplanar distance = 3.279\u2005(1)\u2005\u00c5, slippage = 1.363\u2005\u00c5; Cg5 and Cg6 are the centroids of pyridine rings N1/C1\u2013C5 and N2/C8\u2013C12, respectively; symmetry codes: (vii) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z; (viii) \u2212x\u00a0+\u00a01, \u2212y, \u2212z\u00a0+\u00a01.In the crystal of k Table\u00a02. Within et al., 2016+ and seven Na+, but no alkali earth metal heterometallic coordination polymers. Hence, the title compound 1 is the first reported heterometallic coordination polymer involving the ligand pyridine-2,6-di\u00adcarb\u00adoxy\u00adlic acid, CoII and an alkali earth metal (CaII).A search of the Cambridge Structural Database , Co(CH3COO)2\u00b74H2O  and CaCl2  in 15\u2005ml of distilled H2O was stirred for 10\u2005min in air. 0.5 M NaOH was added dropwise and the mixture was turned into a Parr Teflon-lined stainless steel vessel and heated at 423\u2005K for 3\u2005d. Blue [purple in CIF?] block-shaped crystals of 1 were obtained in a yield of 70% .A mixture of HUiso(H) = 1.5Ueq(O). C-bound H atoms atoms were included in calculated positions and refined as riding: C\u2014H = 0.93\u2005\u00c5 with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018007120/xu5921sup1.cifCrystal structure: contains datablock(s) 1, global. DOI: 1832782CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds into supra\u00admolecular chains propagating along the [101] direction. 16H20N2O6S2, the mid-point of the C\u2014C bond of the central ethane moiety is located on a twofold rotation axis. In the crystal, mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds into supra\u00admolecular chains propagating along the [101] direction. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H\u22efH (43.1%), O\u22efH/H\u22efO (40.9%), C\u22efH/H\u22efC (8.8%) and C\u22efC (5.5%) inter\u00adactions.In the mol\u00adecule of the title compound, C These effective drug mol\u00adecules have an important role in the medical field, including as promising chemotherapeutic agents, and have been used in the treatment of many bacterial infections due to their physical, chemical and biological properties ]bis\u00ad(4-methyl\u00adbenzene\u00adsulf\u00adon\u00ada\u00admide).Sulfonamides are synthetic mol\u00adecules which include the SO2vC (mm2) (H atoms excluded), with the twofold rotation axis bisecting the central C1\u2014C1i bond. The mol\u00adecule is Z-shaped with the N1\u2014S1\u2014C2\u2014C3 torsion angle being \u221260.6\u2005(3)\u00b0. The C1\u2014O1 bond length of 1.429\u2005(3)\u2005\u00c5 and the O1\u2014N1 bond length of 1.426\u2005(2)\u2005\u00c5 are close to the values reported for similar compounds (see the Database survey). The S1\u2014O2 and S1\u2014O3 distances are 1.4376\u2005(17) and 1.4168\u2005(19)\u2005\u00c5, respectively while the S1\u2014N1 and S1\u2014C2 distances are 1.647\u2005(3)\u2005\u00c5 and 1.747\u2005(3)\u2005\u00c5, respectively.The mol\u00adecular structure of the title compound is illustrated in Fig.\u00a013, ca 5% of the unit-cell volume.The crystal packing of the title compound features inter\u00admolecular N\u2014H\u22efO hydrogen bonds Table\u00a01, which cet al., 2016S,2S,4S,5S)-2,5-bis\u00ad[(p-toluene\u00adsulfon\u00adyl)amino]\u00adbicyclo\u00ad(2.2.1)heptane amino]-1-thio\u00adhexitol -1-(toluene\u00adsulfonyl\u00adamido)-3-(toluene\u00adsulfonyl\u00adamido\u00admeth\u00adyl)-3,5,5-tri\u00admethyl\u00adcyclo\u00adhexane   surface resolution with the three-dimensional dnorm surfaces mapped over a fixed colour scale of \u22120.464 (red) to 2.052 (blue) \u00c5 using the CrystalExplorer  points associated with hydrogen atoms. It is characterized by an end point that points to the origin and corresponds to di = de = 1.08\u2005\u00c5, which indicates the presence of the H\u22efH contacts in this study (43.1%). The C\u22efH/H\u22efC plot in Fig.\u00a07vice versa. There are two symmetrical wings on the left and right sides (8.8%). Furthermore, there are C\u22efC (5.5%), N\u22efH/H\u22efN (1.4%), O\u22efC/C\u22efO (0.1%) and S\u22efH/H\u22efS (0.1%) contacts in the title structure.The H\u22efH plot shown in Fig.\u00a07A view of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range \u22120.095 to 0.123 a.u. using the STO-3G basis set at the Hartree\u2013Fock level of theory is shown in Fig.\u00a08The title compound was synthesized according to the method of Bauer & Suresh 1963. Single Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The NH H atom was located in a difference-Fourier maps and freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018017437/xu5951sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018017437/xu5951Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017437/xu5951Isup3.cmlSupporting information file. DOI: 1884045CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are connected by weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22efF hydrogen bonds into sheets parallel to (104). Weak inter\u00admolecular \u03c0\u2013\u03c0 inter\u00adactions also occur.The mol\u00adecular structure of the title chalcone derivative is nearly planar and the mol\u00adecule adopts a  15H10FNO3, is nearly planar and the mol\u00adecule adopts a trans configuration with respect to the C=C double bond. The nitro group is nearly coplanar with the attached benzene ring, which is nearly parallel to the second benzene ring. In the crystal, mol\u00adecules are connected by pairs of weak inter\u00admolecular C\u2014H\u22efO hydrogen bonds into inversion dimers. The dimers are further linked by another C\u2014H\u22efO hydrogen bond and a C\u2014H\u22efF hydrogen bond into sheets parallel to (104). \u03c0\u2013\u03c0 inter\u00adactions occur between the sheets, with a centroid\u2013centroid distance of 3.8860\u2005(11)\u2005\u00c5. Hirshfeld surface analysis was used to investigate and qu\u00adantify the inter\u00admolecular inter\u00adactions.The mol\u00adecular structure of the title chalcone derivative, C This non-linearity leads to frequency-mixing processes , the optical Kerr effect para-substituted phenyl rings and an enone connecting bridge \u00b0. The C7=O3 carbonyl group adopts an s-cis configuration with respect to the C8=C9 double bond as indicated by O3\u2014C7\u2014C8\u2014C9 torsion angle of \u22120.8\u2005(3)\u00b0. The mol\u00adecule (excluding H atoms) is nearly planar with a maximum deviation of 0.103\u2005(2)\u2005\u00c5 at atom O1 of the terminal nitro group. The nitro group is nearly coplanar with the attached C1\u2013C6 benzene ring as indicated by the small dihedral angle of 7.9\u2005(2)\u00b0. The C1\u2013C6 and C10\u2013C15 benzene rings make a small dihedral angle of 4.27\u2005(8)\u00b0 with each other.The asymmetric unit of the title chalcone derivative consists of a unique mol\u00adecule, containing two ge Fig.\u00a01. The molA\u22efO3ii; symmetry code as in Table\u00a01A\u22efO1iii and C4\u2014H4A\u22efF1i; Table\u00a01Cg1\u22efCg1iv,v and Cg2\u22efCg2iv,v = 3.8860\u2005(11)\u2005\u00c5, where Cg1 and Cg2 are the centroids of C1\u2013C6 and C10\u2013C15 benzene rings, respectively; symmetry codes: (iv) x\u00a0\u2212\u00a01, y, z; (v) x\u00a0+\u00a01, y, z] ] correspond to the C11\u2014H11A\u22efO3 hydrogen bond. The C4\u2014H4A\u22efF1 and C15\u2014H15A\u22efO1 hydrogen bonds are indicated as two pairs of lighter red spots on the dnorm surface. The H12A\u22efF1 contact, with its H\u22efF distance shorter than the sum of van der Waals radii by 0.01\u2005\u00c5, appears as two tiny red spots on the dnorm surface. The donor and acceptor of a hydrogen bond with positive and negative electrostatic potentials, respectively, are represented as blue and red regions on the Hirshfeld surface mapped with electrostatic potential [Fig.\u00a04b)]. The electrostatic potential of the F atom is less negative as compared to the O atoms of nitro and carbonyl groups, as indicated by the lighter red region. The H\u22efO/O\u22efH contacts are the most populated contacts and contribute 30.2% of the total inter\u00admolecular contacts, followed by H\u22efH (20.6%), H\u22efC/C\u22efH (18.0%), H\u22efF/F\u22efH (13.1%) and C\u22efC (10.1%) contacts -1-(4-nitro\u00adphen\u00adyl)-3-phenyl\u00adprop-2-en-1-one -3-(4-fluoro\u00adphen\u00adyl)-1-phenyl\u00adprop-2-en-1-one  and 4-fluoro\u00adbenzaldehyde  were dissolved in methanol (20\u2005ml). A catalytic amount of NaOH was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 6\u2005h at room temperature. The progress of the reaction was monitored by TLC. The formed crude product was filtered, washed repeatedly with distilled water and recrystallized from ethanol to obtain the title chalcone derivative. Yellowish single-crystals suitable for X-ray diffraction were obtained from an acetone solution by slow evaporation at room temperature.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018017450/is5506sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018017450/is5506Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017450/is5506Isup3.cmlSupporting information file. DOI: 1036743CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, inversion-related mol\u00adecules form dimers through inter\u00admolecular N\u2014H\u22efO hydrogen bonds with the dimers associated along the  20H17N3O3 , is built up from a benzodiazepine ring system linked to pyridyl and pendant di\u00adhydro\u00adpyran rings, where the benzene and pyridyl rings are oriented at a dihedral angle of 43.36\u2005(6)\u00b0. The pendant di\u00adhydro\u00adpyran ring is rotationally disordered in a 90.899\u2005(3):0.101\u2005(3) ratio with the orientation of each component largely determined by intra\u00admolecular N\u2014HDiazp\u22efODhydp (Diazp = diazepine and Dhydp = di\u00adhydro\u00adpyran) hydrogen bonds. In the crystal, mol\u00adecules are linked via pairs of weak inter\u00admolecular N\u2014HDiazp\u22efODhydp hydrogen bonds, forming inversion-related dimers with R22(26) ring motifs. The dimers are further connected along the b-axis direction by \u03c0\u2013\u03c0 stacking inter\u00adactions between the pendant di\u00adhydro\u00adpyran and pyridyl rings with centroid\u2013centroid distances of 3.833\u2005(3)\u2005\u00c5 and a dihedral angle of 14.51\u2005(2)\u00b0. Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H\u22efH (50.1%), H\u22efC/C\u22efH (17.7%), H\u22efO/O\u22efH (16.8%), C\u22efC (7.7%) and H\u22efN/N\u22efH (5.3%) inter\u00adactions. Hydrogen-bonding and van der Waals inter\u00adactions are the dominant inter\u00adactions in the crystal packing.The title compound, C In fact, many 1,5-benzodiazepines are best known to possess biologically diverse activities such as anti-inflammatory, hypnotic, anti-HIV-1, anti\u00adconvulsant and anti\u00admicrobial (Roma A (C1\u2013C6) is oriented at a dihedral angle of 43.36\u2005(6)\u00b0 with respect to the pyridyl ring C (N3/C10\u2013C14). The pendant di\u00adhydro\u00adpyran ring D (O1/C15\u2013C19) shows a 90.899\u2005(3):0.101\u2005(3) disorder with the minor component rotated by 174.6\u2005(4)\u00b0 from the orientation of the major component. The orientation of both components is largely determined by intra\u00admolecular N2\u2014H2A\u22efO2 or N2\u2014H2A\u22efO3A hydrogen bonds (Table\u00a01D gave the parameters Q = 0.127\u2005(2)\u2005\u00c5, \u03b8 = 108.0\u2005(8)\u00b0 and \u03c6 = 79.6\u2005(8)\u00b0 while for the seven-membered diazepine ring B (N1/N2/C1/C6\u2013C9), the parameters are Q(2) = 0.8888\u2005(13)\u2005\u00c5, Q(3) = 0.2070\u2005(13)\u2005\u00c5, \u03c6(2) = 201.03\u2005(8)\u00b0 and \u03c6(3) = 293.9\u2005(4)\u00b0.The title compound, (I)s Table\u00a01. A puckeDiazp\u22efODhydp (Diazp = diazepine and Dhydp = di\u00adhydro\u00adpyran) hydrogen bonds  = 3.833\u2005(3)\u2005\u00c5 with a dihedral angle of 14.51\u2005(2)\u00b0; Cg1 and Cg2 are the centroids of rings D (O1/C15\u2013C19) and C (N3/C10\u2013C14), respectively].In the crystal, the mol\u00adecules are linked via pairs of weak inter\u00admolecular N\u2014Hs Table\u00a01, formingon Fig.\u00a02 by \u03c0\u2013\u03c0-sCrystalExplorer17.5 , and those delineated into H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH, C\u22efC, H\u22efN/N\u22efH, N\u22efC/C\u22efN, O\u22efC/C\u22efO, N\u22efN, N\u22efO/O\u22efN and O\u22efO contacts \u2013(k), respectively, together with their relative contributions to the Hirshfeld surface. H\u22efH inter\u00adactions are the most important, contributing 50.1% to the overall crystal packing, and are shown in Fig.\u00a05b) as widely scattered points of high density because of the large hydrogen content of the mol\u00adecule. The two pairs of thin and thick spikes with the tips at de + di \u223c2.27 and 1.95\u2005\u00c5, respectively, in Fig.\u00a05b) are due to the short inter\u00adatomic H\u22efH contacts (Table\u00a02c), with the tips at de + di \u223c2.82\u2005\u00c5. The two pairs of thin and thick spikes with the tips at de + di = 2.67 and 2.40\u2005\u00c5, respectively, in Fig.\u00a05d) are due to the N\u2014H\u22efO hydrogen bonds (Table\u00a01e)] contacts contribute 7.0% to the HS and have symmetrical distribution of points, with the tips at de + di = 3.24\u2005\u00c5. The pair of characteristic wings in the fingerprint plot delineated into H\u22efN/N\u22efH contacts  has a pair of spikes with the tips at de + di = 1.49\u2005\u00c5. Finally, the N\u22efC/C\u22efN contacts [Fig.\u00a05g)] contribute 1.5% to the HS and are viewed as a symmetrical distribution of points with pairs of thin edges at de + di = 3.36\u2005\u00c5.In order to visualize the inter\u00admolecular inter\u00adactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis \u2013(e), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH inter\u00adactions suggest that van der Waals inter\u00adactions and hydrogen bonding play the major roles in the crystal packing (Hathwar To a suspension of 3-[1-(2-amino\u00adphenyl\u00adimino)\u00adeth\u00adyl]-4-hy\u00addroxy-6-methyl\u00adpyran-2-one (4\u2005mmol) in ethanol (40\u2005ml) were added 1.5 equivalents of 2-pyridine\u00adcarboxaldehyde and three drops of tri\u00adfluoro\u00adacetic acid (TFA). The mixture was refluxed for 4\u2005h. Cooling to room temperature induced the precipitation of a yellow solid, which was filtered off and washed with 20\u2005ml of cold ethanol. Cooling to room temperature induced the precipitation of a yellow solid, which was filtered and washed with 20\u2005ml of cold ethanol. Crystals suitable for X-ray analysis were obrained by recrystallization of the product from ethanol solution.Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018017565/lh5888sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018017565/lh5888Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017565/lh5888Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018017565/lh5888Isup4.cmlSupporting information file. DOI: 1884597CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "TS3, have been confirmed by resonant scattering. The roles of the water mol\u00adecules and the C\u2014H\u22ef\u03c0 inter\u00adactions in the crystal packing are highlighted.The absolute configurations of the 10 asymmetric carbons involved in the structure of the title limonoid,  26H28O5\u00b70.5H2O (TS3) oxirenocyclo\u00adpenta\u00adphenanthrofuran-3(3aH)-one hemihydrate], crystallizes with two independent mol\u00adecules (1 and 2) in the asymmetric unit and one water mol\u00adecule. TS3 is composed of three six-membered rings , three five-membered rings  and two epoxide rings. A group of five fused rings (A\u2013E) is bonded to a furan ring (F) with a Csp3\u2014Csp2 bond [1.500\u2005(3)\u2005\u00c5 in mol\u00adecule 1 and 1.499\u2005(3)\u2005\u00c5 in mol\u00adecule 2]. The absolute structures of the mol\u00adecules in the crystal were determined by resonant scattering; Flack parameter = 0.05\u2005(5). In the crystal, the individual mol\u00adecules stack in columns along the b-axis direction. The water mol\u00adecule bridges mol\u00adecules 1 and 2 via Owater\u2014H\u22efO and C\u2014H\u22efOwater hydrogen bonds. Together with further C\u2014H\u22efO hydrogen bonds, linking mol\u00adecules 1 and 2, the columns are linked to form slabs parallel to the ab plane. Within each column, mol\u00adecules are also linked via C\u2014H\u22ef\u03c0 inter\u00adactions involving the five-membered furan (F) rings.The title limonoid compound, C Rings A to E are fused (first compartment), while ring F is bonded to this first moiety by a Csp3\u2014Csp2 bond, [C15\u2014C19 = 1.500\u2005(3)\u2005\u00c5 and C15B\u2014C19B = 1.499\u2005(3)\u2005\u00c5], as shown in Fig.\u00a01As previously reported, using one- and two-dimensional NMR techniques in combination with high-resolution mass spectroscopy studies /0.672\u2005(2)\u2005\u00c5 for atoms C11/C11B and by 0.654\u2005(2)/0.670\u2005(2)\u2005\u00c5 for atoms C16/C16B. The six-membered ring C has a half-chair conformation in both mol\u00adecules; the puckering parameters for mol\u00adecule 1 are amplitude Q = 0.474\u2005(2)\u2005\u00c5, \u03b8 = 131.7\u2005(2)\u00b0 and \u03c6 = 40.9\u2005(3)\u00b0, while for mol\u00adecule 2 Q = 0.479\u2005(2)\u2005\u00c5, \u03b8 = 127.5\u2005(2)\u00b0, \u03c6 = 42.9\u2005(3)\u00b0. The five-membered rings B and E have envelope conformations with atoms C4/C4B and C15/C15B, respectively, as the flaps, being displaced from the mean plane of the other four atoms by 0.689\u2005(2)/0.702\u2005(2)\u2005\u00c5 and 0.526\u2005(2)/0.454\u2005(2)\u2005\u00c5, respectively. The furan rings (F), are planar in both mol\u00adecules.The six-membered rings TS3 comes from ten asymmetric carbon atoms , refined using Cu K\u03b1 radiation.The chirality of TS3, and details are given in Table\u00a01via three weak hydrogen bonds  present in the structure of ds Fig.\u00a03. The indt Table\u00a01, stabilit Table\u00a01 are linket al., 2016TS3 gave no hits. The moieties having the rings E and F have been seen in three cytotoxic limonoids, viz. aphanastatine, amoorastatine and hydroxyl-12-ammorastatine , but having different substituents, are known. Most of these compounds are reported as hemisynthesis products, while TS3 was obtained from a natural source.A search in the Cambridge Structural Database  and needle-like crystals, suitable for single crystal X-ray diffraction analysis, were obtained by slow evaporation of the solvents at room temperature after three days.The title compound was isolated from the root bark of  al. 2016. A smallUiso(H) = 1.5Ueq(C-meth\u00adyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018009775/su5448sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018009775/su5448Isup2.hklStructure factors: contains datablock(s) I. DOI: 1854616CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the title mol\u00adecule, di-methyl\u00adhydroxy and 4-nitro\u00adbenzene groups cap a central di-substituted acetyl\u00adene residue. The extended structure features flattened, hexa\u00admeric clusters sustained by hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds. 11H11NO3, is capped at either end by di-methyl\u00adhydroxy and 4-nitro\u00adbenzene groups; the nitro substituent is close to co-planar with the ring to which it is attached [dihedral angle = 9.4\u2005(3)\u00b0]. The most prominent feature of the mol\u00adecular packing is the formation, via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds, of hexa\u00admeric clusters about a site of symmetry 6 synthons and have the shape of a flattened chair. The clusters are connected into a three-dimensional architecture by benzene-C\u2014H\u22efO(nitro) inter\u00adactions, involving both nitro-O atoms. The aforementioned inter\u00adactions are readily identified in the calculated Hirshfeld surface. Computational chemistry indicates there is a significant energy, primarily electrostatic in nature, associated with the hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds. Dispersion forces are more important in the other identified but, weaker inter\u00admolecular contacts.The di-substituted acetyl\u00adene residue in the title compound, C The aggregates are disposed about a site of symmetry b). The crystal also features weak benzene-C\u2014H\u22efO(nitro) inter\u00adactions, involving both nitro-O atoms. In essence, one nitro group of one mol\u00adecule forms two such inter\u00adactions with two symmetry-related mol\u00adecules to form a supra\u00admolecular chain along the c-axis direction with helical symmetry (31 screw axis), Fig.\u00a03a). An end-on view of the chain is shown in Fig.\u00a03b). These weak benzene-C\u2014H\u22efO(nitro) inter\u00adactions serve to link the six-mol\u00adecule aggregates into a three-dimensional architecture, Fig.\u00a04The spectacular feature of the mol\u00adecular packing of (I)et al., 2019Crystal Explorer 17 , the donors and acceptors of O\u2014H\u22efO hydrogen bond involving the atoms of the hydroxyl group are characterized as bright-red spots. The faint-red spots near the phenyl-H10, H11 and nitro-O2, O3 atoms on the dnorm-mapped Hirshfeld surface in Fig.\u00a05b) represent the effect of weak C\u2014H\u22efO inter\u00adactions as listed in Table\u00a01a), the C\u2014H\u22ef\u03c0/\u03c0\u22efH\u2014C contacts listed in Table\u00a02b) is an indication of the \u03c0\u2013\u03c0 stacking inter\u00adaction between them .The Hirshfeld surface calculations for (I)a), and those delineated into H\u22efH, O\u22efH/H\u22efO, C\u22efH/H\u22efC and C\u22efC contacts \u2013(e), respectively, and provide more information on the influence of short inter\u00adatomic contacts upon the mol\u00adecular packing. The percentage contributions from the different inter\u00adatomic contacts to the Hirshfeld surface are summarized in Table\u00a03de + di \u223c1.8\u2005\u00c5 in the fingerprint plot delineated into O\u22efH/H\u22efO contacts, Fig.\u00a08c), are due to the presence of the O\u2014H\u22efO hydrogen bond, whereas the points corresponding to comparatively weak inter\u00admolecular C\u2014H\u22efO inter\u00adactions, Table\u00a01C atom and the benzene (C6\u2013C11) ring, results in short inter\u00adatomic C\u22efH/H\u22efC contacts, Table\u00a02a), and by the pair of forceps-like tips at de + di \u223c2.8\u2005\u00c5 in Fig.\u00a08d). The points corresponding to other such short inter\u00adatomic contacts involving the acetyl\u00adene-C5 and methyl-C3\u2014H3c atoms at longer separations are merged within the plot. The arrow-shaped distribution of points around de + di \u223c3.6\u2005\u00c5 in the fingerprint plot delineated into C\u22efC contacts, Fig.\u00a08e), indicate \u03c0\u2013\u03c0 overlap between symmetry-related benzene (C6\u2013C11) rings, as illustrated in Fig.\u00a07b). The small percentage contributions from the other inter\u00adatomic contacts listed in Table\u00a03The overall two-dimensional fingerprint plot for (I)Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) terms after applying relevant scale factors \u03c1(r), where \u03c1 is the electron density and \u03bb2 is the second eigenvalue of the Hessian matrix of \u03c1. Crucially, through a three-colour scheme, a specific inter\u00adaction can be identified as being attractive or otherwise. Thus, a green isosurface indicates a weakly attractive inter\u00adaction whereas a blue isosurface indicates an attractive inter\u00adaction; a repulsive inter\u00adaction appears red. The isosurfaces for three identified inter\u00admolecular inter\u00adactions are given in the upper view of Fig.\u00a010a), a green isosurface is apparent for the conventional hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bond. Similarly, green isosurfaces are seen between the inter\u00adacting atoms involved in the phenyl-C\u2014H\u22efO(nitro), Fig.\u00a010b), and the methyl-C\u2014H\u22ef\u03c0(C11\u2013C16), Fig.\u00a010c), inter\u00adactions.Non-covalent inter\u00adaction plot (NCIplot) analyses provide a visual representation of the nature of the contact between specified species in crystals (Johnson versus sign(\u03bb2)\u03c1(r). The non-covalent inter\u00adaction peaks appear at density values less than 0.0 atomic units, consistent with their being weakly attractive inter\u00adactions.The lower views of Fig.\u00a010et al., 2010et al., 2016P21/c to form a hexa\u00admeric clusters via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds as seen in (I)a); intra\u00admolecular hy\u00addroxy-O\u2014H\u22efO(carbon\u00adyl) hydrogen bonds are also apparent. In (III), the two independent mol\u00adecules comprising the asymmetric unit associate about a centre of inversion in space group P21/n into a supra\u00admolecular dimer via pairs of hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) and hy\u00addroxy-O\u2014H\u22efN(cyano) hydrogen bonds as shown in Fig.\u00a011b). In this case, one independent hy\u00addroxy-oxygen atom and one cyano-nitro\u00adgen atom do not accept a hydrogen-bonding inter\u00adaction. Three crystallographically independent mol\u00adecules are also found in (II) (space group Pca21) and these self-associate to form a supra\u00admolecular chain via hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds with non-crystallographic threefold symmetry, Fig.\u00a011c). Finally, zigzag supra\u00admolecular chains sustained by hy\u00addroxy-O\u2014H\u22efO(hy\u00addroxy) hydrogen bonds are found in the crystal of (IV), Fig.\u00a011d) in space group Pbca.There are four literature precedents for (I)et al., 19981H NMR : \u03b4 = 8.16 , 7.54 , 2.24  and 1.63  ppm. 13C NMR : \u03b4 = 147.2, 132.5, 129.8, 123.6, 99.2, 80.5, 66.7 and 31.3 ppm. Irregular colourless crystals of (I)The title compound was prepared as per the literature procedure (Bleicher Uiso(H) set to 1.2\u20131.5Ueq(C). The O-bound H atom was refined with a distance restraint of 0.82\u00b10.01\u2005\u00c5, and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989019010284/hb7841sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019010284/hb7841Isup2.hklStructure factors: contains datablock(s) I. DOI: 1941466CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The manganese compound crystallized in the monoclinic space group 1/nP2 and exists as a centrosymmetric dimer.The title compound was prepared by a template method starting from manganese(II) nitrate with a Schiff base ligand. The product of condensation was between methyl carbazate and glyoxylic acid, and formed  2(C4H5N2O4)2(NCS)2(H2O)4]\u00b74H2O (I), exists as a centrosymmetric dimer. Each dimeric unit consists of tridentate -chelating Schiff bases with symmetry-maintained \u03bc-O-bridged carboxyl\u00adate anions, terminally bound thio\u00adcyanate anions, and ligated and solvated water mol\u00adecules. The complex exhibits a distorted octa\u00adhedron geometry and the centrosymmetric \u03bc-O-bridged carboxyl\u00adate anions connect the two manganese atoms to form an M2O2 ring. In the crystal, the mol\u00adecules are inter\u00adlinked via strong N\u2014H\u22efO and O\u2014H\u22efO hydrogen-bonding contacts and weak O\u2014H\u22efS inter\u00admolecular inter\u00adactions, forming a three-dimensional mol\u00adecular network.The title compound, [Mn Among them, carbaza\u00adtes  are inter\u00adesting as ligands in view of their variety of potential donor atoms such as oxygen and nitro\u00adgen. Inter\u00adestingly, these neutral mol\u00adecules can be expected to exhibit only one common coordination mode, i.e. N,O-chelating bidentate. This has been clearly observed in many metal complexes with a variety of anions such as formate benzaldehyde with ethyl carbazate  and the N-bonded NCS anion, whereas the \u03bc-O-bridged carboxyl\u00adate anions, azomethine nitro\u00adgen atom and a coordinated water mol\u00adecule (O1W) occupy the equatorial positions. The two manganese atoms are connected via centrosymmetrically related \u03bc-O-bridged carboxyl\u00adate anions, forming a rhomboidal Mn2O2 unit about an inversion centre.The manganese title compound crystallizes in the monoclinic space group er Fig.\u00a01. The asyO-bridged carboxyl\u00adate anions are 2.1448\u2005(9), 2.1905\u2005(9) and 2.2606\u2005(8), 2.2985\u2005(8)\u2005\u00c5, respectively. The Mn\u2014N\u2014C\u2014S torsion angle in the NCS moiety is 103.5\u2005(4)\u00b0 and the bond angles for the coordinated atoms vary from 68.99\u2005(3)\u2013132.57\u2005(4)\u00b0, indicating a distorted geometry.The separation of the Mn atoms is 3.645\u2005(3) \u00c5. The Mn\u2014N(iso\u00adthio\u00adcyanato) and Mn\u2014N(azomethine) distances are 2.1289\u2005(11) and 2.3388\u2005(10)\u2005\u00c5 and the Mn\u2014O distances involving the coordinated water mol\u00adecules and \u03bc-N\u22efO2v [2.7971\u2005(13)\u2005\u00c5] hydrogen bond between adjacent dimers forms chains extending along the ac diagonal. The weak O4W\u2014H4W1\u22efS1iv inter\u00adaction [3.3159\u2005(12)\u2005\u00c5] and O2W\u2014H2W1\u22efO4W hydrogen bond [2.7322\u2005(14)\u2005\u00c5] link the dimers, generating a two-dimensional network as shown in Fig.\u00a02W, O3W and O4W are involved in O\u2014H\u22efO hydrogen-bonding inter\u00adactions , 3206 (b) [\u03bd(N\u2014H)], 2096 (s) [\u03bd(C\u2261N)], 1705 (s) [\u03bd [\u03bdasym (C=O)], 1555 (s) [\u03bd(C=N)], 1397 (s) [\u03bdsym(C=O)], 1067 (s) [\u03bd(N\u2014N)].Stoichiometric qu\u00adanti\u00adties of glyoxylic acid , ethyl\u00adcarbazate  and ammonium thio\u00adcyanate  were dissolved in 30\u2005mL of double-distilled water. To this homogeneous solution, Mn values were set to a multiple of Ueq(C) with 1.5 for CH3 and 1.2 for C\u2014H groups, respectively. Positions and Uiso values of water and amine H atoms were freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018014871/jj2203sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014871/jj2203Isup2.hklStructure factors: contains datablock(s) I. DOI: 1870123CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The reaction of 2-methyl\u00adthio-5-amino-1,3,4-thia\u00addiazole with copper(II) acetate monohydrate resulted in the formation of the title binuclear compound 3H5N3S2) with copper(II) acetate monohydrate  resulted in the formation of the title binuclear compound, [Cu2(C2H3O2)4(C3H5N3S2)2] or [Cu2(OAc)4(Me-SNTD)2]. The structure has triclinic (PR22(12) ring motif. The mol\u00adecules are further linked by C\u2014H\u22ef\u03c0 inter\u00adactions between the thia\u00addiazole rings and the methyl groups of the acetate units.The reaction of 2-methyl\u00adthio-5-amino-1,3,4-thia\u00addiazole (Me-SNTD; C The Cu\u2014O bond lengths range from 1.962\u2005(2) to 2.001\u2005(2)\u2005\u00c5 and the Cu\u2014N distance is 2.180\u2005(3)\u2005\u00c5. The Cu\u22efCu distance is 2.6727\u2005(6)\u2005\u00c5 and each metal atom exhibits a Jahn\u2013Teller-distorted octa\u00adhedral geometry. The observed Cu\u2014O2 bond length of 1.983\u2005(2)\u2005\u00c5 is longer than the Cu\u2014O1 distance of 1.962\u2005(2)\u2005\u00c5. The elongation of this Cu\u2014O distance may be due to the intra\u00admolecular N3\u2014H\u22efO2 hydrogen bond (Table\u00a01Each copper atom is displaced by 0.754\u2005(3)\u2005\u00c5 from the plane defined by basal-plane atoms O1, O2, O3 and O4 towards the nitro\u00adgen atom, N2. The Cu1d Table\u00a01. The coni hydrogen bond, forming a six-membered ring. The dimers are connected through an inter\u00admolecular N3\u2014H3\u22efO4ii hydrogen bond between the NH (Me-SNTD) and the carboxyl\u00adate groups, forming chains propagating parallel to [001]. The above-mentioned hydrogen bonds give rise to \u03c0 inter\u00adactions between the thia\u00addiazole rings and the acetate methyl groups generate a three-dimensional supra\u00admolecular framework s Table\u00a01. Additiork Fig.\u00a03.et al., 20162(OAc)4L2], where L is a ligand with an oxygen or nitro\u00adgen ligator atom, have been well explored. The structures of 2-methyl\u00adthio-5-amino-1,3,4-thia\u00addiazole and a complex of this mol\u00adecule with cadmium have been deposited in the CSD [XUVPEK  and 2-methyl\u00adthio-5-amino-1,3,4-thia\u00addiazole  were dissolved separately in a mixture of methanol-di\u00adchloro\u00admethane , mixed together and stirred for 1.5\u2005h. The green solid that precipitated was dissolved in methanol to form a green solution. Single crystals of the complex suitable for X-ray analysis were obtained by slow evaporation of the solution over a period of 10\u2005d.Cu(OAc)Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019010272/cq2032sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019010272/cq2032Isup2.hklStructure factors: contains datablock(s) I. DOI: 1941461CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "This is correlated with the formation of carb\u00adoxy\u00adlic acid inversion dimers linked by pairwise O\u2014H\u22efO hydrogen bonds in the crystal of the title compound rather than an intra\u00admolecular O\u2014H\u22efO hydrogen bond.The \u2013COOH group of the title compound adopts a  11H8F3NO3, adopts a cis configuration across the \u2013C=C\u2013 double bond in the side chain and the dihedral angle between the phenyl ring and side chain is 47.35\u2005(1)\u00b0. The \u2013COOH group adopts a syn conformation (O=C\u2014O\u2014H = 0\u00b0), unlike the anti conformation observed in related maleamic acids. In the crystal, inversion dimers linked by pairs of O\u2014H\u22efO hydrogen bonds are connected via N\u2014H\u22efO hydrogen bonds and C\u2014H\u22efO inter\u00adactions into (100) sheets, which are cross-linked by another C\u2014H\u22efO inter\u00adaction to result in a three-dimensional network. The Hirshfeld surface fingerprint plots show that the highest contribution to surface contacts arises from O\u22efH/H\u22efO contacts (26.5%) followed by H\u22efF/F\u22efH (23.4%) and H\u22efH (17.3%).The title mol\u00adecule, C This disparity is a result of O\u2014Hc\u22efO=Ca  intra\u00admolecular hydrogen bonds present in related structures and not observed in (I)The mol\u00adecule of (I)in Fig.\u00a01, similarvia pairwise O2\u2014H2O\u22efO3 hydrogen bonds  chains  chain in its own right  chains runs down the b-axis direction, thereby cross-linking the sheets into a three-dimensional network.In the crystal of (I)ds Fig.\u00a02 forming ns Fig.\u00a02, resultins Fig.\u00a02. The N1\u2014ht Fig.\u00a02. In addiht Fig.\u00a02 forming dnorm surfaces and two-dimensional fingerprint plots (FP) were generated to further investigate the inter\u00admolecular inter\u00adactions in (I)et al., 2017N and H2O hydrogen atoms are due to their involvement as donors in stronger hydrogen bonds, while faint spots near H8 and H9 atoms are due to the weak C\u2014H\u22efO inter\u00adactions involving these atoms , F\u22efH/H\u22efF , H\u22efH , C\u22efH/H\u22efC , C\u22efF/F\u22efC  and F\u22efF  inter\u00adactions, with other contacts contributing the remaining 10.2%.In the Hirshfeld surface analysis, ms Fig.\u00a03. Analysims Fig.\u00a03 showed tN-(ar\u00adyl)-maleamic acids have been reported to date with varied substituents  on the phenyl ring. Three of these, namely N-(phen\u00adyl)maleamic acid (CCDC refcode: LOSJUZ) maleamic acid (QUYJUQ) maleamic acid (PILVAI) anti O=C\u2014O\u2014H conform\u00adation and an intra\u00admolecular O\u2014H\u22efO hydrogen bond, as noted above. In LOSJUZ, adjacent mol\u00adecules are linked by N\u2014H\u22efO hydrogen bonds into a flat ribbon, while in QUYJUQ, N\u2014H\u22efO hydrogen bonds link the mol\u00adecules into zigzag chains propagating parallel to [001] and these chains are further linked into sheets by weak \u03c0\u2013\u03c0 inter\u00adactions. In the crystal structure of PILVAI, symmetry-related mol\u00adecules are linked by N\u2014H\u22efN hydrogen bonds, forming centrosymmetric amine\u2013amide dimers. The dimers are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds and weak N\u2014H\u22ef\u03c0 and \u03c0\u2013\u03c0 inter\u00adactions into a three-dimensional network.Nineteen N-(2-methyl\u00adphen\u00adyl)maleamic acid  set to 1.2Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located from difference-Fourier maps and freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019006509/hb7816sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006509/hb7816Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019006509/hb7816Isup3.cmlSupporting information file. DOI: 1914411CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "I centre within a S4 donor set. The three-dimensional mol\u00adecular packing is sustained by amine-N\u2014H\u22efS(thione), N\u2014H\u22efN(triazol\u00adyl) and N\u2014H\u22efN(thio\u00adcyanate) hydrogen bonds.The centrosymmetric binuclear complex features a tetra\u00adhedral Ag H-1,2,4-triazole-5(4H)-thione-\u03ba2S:S]bis\u00ad{(thio\u00adcyanato-\u03baS)silver(I)}, [Ag2(SCN)2(C2H3N3S)4], is generated by crystallographic inversion symmetry. The independent triazole-3-thione ligands employ the exocyclic-S atoms exclusively in coordination. One acts as a terminal S-ligand and the other in a bidentate (\u03bc2) bridging mode to provide a link between two AgI centres. Each AgI atom is also coordinated by a terminal S-bound thio\u00adcyanate ligand, resulting in a distorted AgS4 tetra\u00adhedral coordination geometry. An intra\u00admolecular N\u2014H\u22efS(thio\u00adcyanate) hydrogen bond is noted. In the crystal, amine-N\u2014H\u22efS(thione), N\u2014H\u22efN(triazol\u00adyl) and N\u2014H\u22efN(thio\u00adcyanate) hydrogen bonds give rise to a three-dimensional architecture. The packing is consolidated by triazolyl-C\u2014H\u22efS(thio\u00adcyanate), triazolyl-C\u2014H\u22efN(thiocyanate) and S\u22efS [3.2463\u2005(9)\u2005\u00c5] inter\u00adactions as well as face-to-face \u03c0\u2013\u03c0 stacking between the independent triazolyl rings [inter-centroid separation = 3.4444\u2005(15)\u2005\u00c5]. An analysis of the calculated Hirshfeld surfaces shows the three major contributors are due to N\u22efH/H\u22efN, S\u22efH/H\u22efS and C\u22efH/H\u22efC contacts, at 35.8, 19.4 and 12.7%, respectively; H\u22efH contacts contribute only 7.6% to the overall surface.The complete mol\u00adecule of the binuclear title complex, bis\u00ad[\u03bc-1 I complex, (I)H-1,2,4-triazole-5(4H-thione) and thio\u00adcyanate ligands has been synthesized and its crystal and mol\u00adecular structures determined as part of our on-going studies in this area , the heterocyclic ligand in (I)et al., 201812(SCN)]2 (I)P21/n and is disposed about a crystallographic centre of inversion. The HtrzSH mol\u00adecules only employ their exocyclic thione-sulfur atoms in coordination, there being no Ag\u22efN contacts of note. Each AgI atom is coordinated by a terminally bound HtrzSH mol\u00adecule and by two thione-sulfur atoms derived from two \u03bc2-bridging HtrzSH mol\u00adecules. The coordination of each AgI atom is completed by a terminal, S-bound thio\u00adcyanate anion. The geometry around the silver centre defined by the S4 donor set is distorted tetra\u00adhedral with the S\u2014Ag\u2014S bond angles spanning about 25\u00b0, i.e. from a narrow 91.60\u2005(2)\u00b0 for S1\u2014Ag\u2014S1i, being subtended by the bridging S1 atoms, to a wide 127.43\u2005(2)\u00b0 for S2\u2014Ag\u2014S3; symmetry operation (i): 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z. The Ag2S2 core has the shape of a distorted rhombus as the Ag\u2014S1 bond length of 2.5596\u2005(7)\u2005\u00c5 is significantly shorter than the Ag\u2014S1i bond of 2.8188\u2005(7)\u2005\u00c5. The Ag\u2014S bond lengths fall in two distinct classes, with the Ag\u2014S1b and Ag\u2014St  bond lengths being similar and shorter than Ag\u2014S1ib b Table\u00a01. Despite2S2 core, with the dihedral angles between the core and the N1- and N4-rings being 88.99\u2005(11) and 85.16\u2005(11)\u00b0, respectively. The independent rings are close to being co-planar, exhibiting a dihedral angle of 8.38\u2005(16)\u00b0. Finally, the N1-amine is orientated to be in close proximity to the S3-thio\u00adcyanato atom, enabling the formation of an intra\u00admolecular amine-N\u2014H\u22efS(thio\u00adcyanato) hydrogen bond (Table\u00a02The five-membered rings lie prime to either side of the Agd Table\u00a02. While tii = 3.4444\u2005(15)\u2005\u00c5 and angle of inclination = 6.81\u2005(16)\u00b0 for (ii) x, y, z].The crystal of (I)et al., 2004et al., 2019Crystal Explorer 17  of the Hirshfeld surface plotted over dnorm for (I)i.e. S\u22efS contacts, are noted. The closest of these, i.e. S1\u22efS1iii = 3.2463\u2005(9)\u2005\u00c5 , link the binuclear mol\u00adecules into chains along the a-axis direction. On the Hirshfeld surface mapped over electrostatic potential (DFT 3-21G) shown in Fig.\u00a04b), the faint-red and light-blue regions correspond to negative and positive electrostatic potential, respectively,As seen in Fig.\u00a04a)\u2013(f), respectively. The N\u22efH/H\u22efN contacts, at 35.8%, are the major contributor to the Hirshfeld surface. The S\u22efH/H\u22efS contacts (19.4%) also make a significant contribution. Other significant contributions come from the C\u22efH/H\u22efC (12.7%) and S\u22efS (8.3%) contacts with H\u22efH contacts, occurring at distances beyond the sum of the van der Waals radii, contributing only 7.6%. The next most significant contribution is made by N\u22efC/C\u22efN contacts (6.7%) arising in the main from the \u03c0\u2013\u03c0 stacking inter\u00adactions between triazolyl rings.The full and delineated  two-dimensional fingerprint plots are shown in Fig.\u00a05et al., 2017et al., 2017i.e. electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange\u2013repulsion (Erep); these were obtained using the wave function calculated at the HF/3-21G level of theory. The results are summarized in Table\u00a03\u22121, having a major electrostatic contribution (\u2212142.4\u2005kJ\u2005mol\u22121), and is associated with the following inter\u00adatomic contacts: C2\u2014H2\u22efN7, C4\u2014H4\u22efN7 and \u03c0\u2013\u03c0 stacking of between triazole rings. The next most significant contribution, with a total energy of \u2212125.0\u2005kJ\u2005mol\u22121, arises from conventional hydrogen bonds, i.e. N1\u2014H1N\u22efN5, N4\u2014H4N\u22efN2 and N6\u2014H6N\u22efN7 as well as C2\u2014H2\u22efS3 inter\u00adactions. The next attractive inter\u00adaction, with Etot = \u221248.9 and Edis = \u2212120.3\u2005kJ\u2005mol\u22121, respectively, reflects the N3\u2014H3N\u22efS2 hydrogen bonding and S1\u22efS1 secondary bonding contact.The energy frameworks were simulated \u2013(c), respectively, by energy framework diagrams whereby the cylinders join the centroids of mol\u00adecular pairs using a red, green and blue colour scheme; the radius of the cylinder is proportional to the magnitude of inter\u00adaction energy.The magnitudes of inter\u00admolecular energies, NWChem package supporting information and their energies were calculated to be 3.011 and 6.173\u2005eV, respectively. The HOMO is delocalized across the thio\u00adcyanato groups and the bridging region between the two dimers. The LUMO includes the delocalization around the triazole rings.The HOMO and LUMO energies for the atom positions in the crystal structure of (I)et al., 2016via the thione-S atom, as in (I)3P)2Cu(HtrzSH)Cl]\u00b7CH3CN, ]\u00b7CH3OH ]\u00b7H2O 2(HtrzS)(HtrzSH)\u00b70.5H2O 2(HtrzSH)2]\u00b72H2O}n 2Cl2]n Cl]n (HtrzSH)\u00b70.5H2O 3Sn(HtrzS) (NO3)OH2]n 2(SO4)]n H-1,2,4-triazole-3-thiol  in distilled water (5\u2005ml) was added followed by heating for 4.3\u2005h during which time the precipitate slowly dissolved. The clear solution was filtered and kept to evaporate at ambient temperature. After a few days, colourless trapezoidal prisms of (I)in vacuo. M.p.: 413\u2013417\u2005K. IR : 2108 (s) (C\u2261N), 1479 (s) (C=N), 1248 (w) (C\u2013N), 1054 (m) (C\u2014S) + (C\u2014N).Silver nitrate  and potassium thio\u00adcyanate  were dissolved in acetro\u00adnitrile (25\u2005ml) and a white precipitate formed. This mixture was heated at 323\u2013325\u2005K for 30\u2005min. Then, a clear solution of 1Uiso(H) = 1.2Ueq. The maximum and minimum residual electron density peaks of 0.96 and 1.04 e\u2005\u00c5\u22123, respectively, were located 0.83 and 0.77\u2005\u00c5 from the N3 and Ag atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019016359/hb7868sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019016359/hb7868Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016359/hb7868sup3.tifFig. S1 Image of the calculated HOMO and LUMO's for (I). DOI: 1969873CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, two supra\u00admolecular tapes, each sustained by amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds and ten-membered {\u22efHNC 14H14N4O2\u00b7H2O, features a central C2N2O2 residue (r.m.s. deviation = 0.0205\u2005\u00c5) linked at each end to 3-pyridyl rings through methyl\u00adene groups. The pyridyl rings lie to the same side of the plane, i.e. have a syn-periplanar relationship, and form dihedral angles of 59.71\u2005(6) and 68.42\u2005(6)\u00b0 with the central plane. An almost orthogonal relationship between the pyridyl rings is indicated by the dihedral angle between them [87.86\u2005(5)\u00b0]. Owing to an anti disposition between the carbonyl-O atoms in the core, two intra\u00admolecular amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds are formed, each closing an S(5) loop. Supra\u00admolecular tapes are formed in the crystal via amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds and ten-membered {\u22efHNC2O}2 synthons. Two symmetry-related tapes are linked by a helical chain of hydrogen-bonded water mol\u00adecules via water-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds. The resulting aggregate is parallel to the b-axis direction. Links between these, via methyl\u00adene-C\u2014H\u22efO(water) and methyl\u00adene-C\u2014H\u22ef\u03c0(pyrid\u00adyl) inter\u00adactions, give rise to a layer parallel to (10The mol\u00adecular structure of the title bis-pyridyl substituted di\u00adamide hydrate, C In the same way, complexation to metals may also be envisaged. It is therefore not surprising that there is now a wealth of structural information for these mol\u00adecules occurring in co-crystals, salts and metal complexes, as has been reviewed recently Having both amide and pyridyl functionality, bis\u00ad\u2005\u00c5 for N3 and 0.0321\u2005(11)\u2005\u00c5 for C8. The N1- and N3-pyridyl rings form dihedral angles of 59.71\u2005(6) and 68.42\u2005(6)\u00b0, respectively, with the central plane and lie to the same side of the plane, having a syn-periplanar relationship. The dihedral angle formed between the pyridyl rings is 87.86\u2005(5)\u00b0, indicating an almost edge-to-face relationship. The carbonyl-O atoms have an anti disposition enabling the formation of intra\u00admolecular amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds that close S(5) loops, Table\u00a01The mol\u00adecular structures of the two constituents comprising the crystallographic asymmetric unit of (I)via amide-N\u2014H\u22efO(carbon\u00adyl) hydrogen bonds leading to a sequence of inter-connected ten-membered {\u22efHNC2O}2 synthons. Two such tapes are connected by hydrogen bonds provided by the water mol\u00adecule of crystallization. Thus, alternating water mol\u00adecules in helical chains of hydrogen-bonded water mol\u00adecules, being aligned along the b-axis direction and propagated by 21 symmetry, connect to 3LH2via water-O\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds to form the one-dimensional aggregate shown in Fig.\u00a02a). The presence of methyl\u00adene-C\u2014H\u22efO(water) and methyl\u00adene-C\u2014H\u22ef\u03c0(pyrid\u00adyl) contacts stabilizes a layer lying parallel to (10b).Significant conventional hydrogen bonding is noted in the crystal of (I)Crystal Explorer 17 dnorm mapping are electrostatic in nature as can be seen from the distinctive blue (electropositive) and red (electronegative) regions on the surface, albeit with varying intensity, Fig.\u00a04a) and (b). This indicates no charge complementarity consistent with the inter\u00adaction beings mainly dispersive in nature.To verify the nature of the aforementioned inter\u00adactions, the a), the overall fingerprint plot of (I)3LH2, with splitting of the spike in the inter\u00adnal region due to the formation of the O\u2014H\u22efN hydrogen bond, Fig.\u00a05e), suggesting a prominent role played by the water mol\u00adecule in influencing the overall contacts in (I)4LH2 in which the overall surface contacts for 4LH2 are not very much influenced by the benzene mol\u00adecule as demonstrated by the similar profiles for the solvate and individual 4LH2 mol\u00adecule , i.e. H\u22efH \u223c2.26\u2005\u00c5 [\u03a3(vdW) = 2.40\u2005\u00c5], O\u22efH/H\u22efO \u223c1.88\u2005\u00c5 [\u03a3(vdW) = 2.72\u2005\u00c5], C\u22efH/H\u22efC \u223c2.62\u2005\u00c5 [\u03a3(vdW) = 2.90\u2005\u00c5] and N\u22efH/H\u22efN \u223c2.50\u2005\u00c5 [\u03a3(vdW) = 2.75\u2005\u00c5].The qu\u00adanti\u00adfication of the close contacts to the Hirshfeld surface was performed through the analysis of the two-dimensional fingerprint plots for (I)3LH2 mol\u00adecule, the dominance of these contacts follows the order H\u22efH , C\u22efH/H\u22efC , O\u22efH/H\u22efO  and N\u22efH/H\u22efN . While the aforementioned inter\u00adactions are almost evenly distributed between the inter\u00adnal and external contacts for (I)3LH2 are found to either to be inclined towards the inter\u00adnal or external contact region compared with (I)versus -H\u22efO- (9.5%) and -N\u22efH- (8.8%) versus -H\u22efN- (4.6%), respectively, Fig.\u00a05c)\u2013(e).As for the individual di + de 2.26\u2005\u00c5), O\u22efH/H\u22efO  and H\u22efN . In particular, the second most dominant contacts are found to be heavily inclined toward -O\u22efH- (30.5%) as compared to -H\u22efO- (8.9%), presumably due to relatively large contact surface area.The hydrate mol\u00adecule exhibits a completely different fingerprint profile, which is dominated by three major contacts, namely H\u22efH 2 dimer connected by a ten-membered {\u22efHNC2O}2 synthon has the greatest Eint energy of \u221273.0\u2005kJ\u2005mol\u22121 which is comparable in energy to the classical eight-membered {\u22efHOCO}2 synthon , O1W\u2014H1W\u22efN1 (\u221228.6\u2005kJ\u2005mol\u22121), O1W\u2014H2W\u22efO1W (\u221226.2\u2005kJ\u2005mol\u22121), C7\u22efO1 (\u221220.7\u2005kJ\u2005mol\u22121), C5\u2014H5\u22efN4 (\u221213.0\u2005kJ\u2005mol\u22121) and C1\u2014H1\u22efO1W (\u221210.5\u2005kJ\u2005mol\u22121) inter\u00adactions. As expected, the N2\u2014H2N\u22efO1, N3\u2014H3N\u22efO2, O1W\u2014H1W\u22efN1 and O1W\u2014H2W\u22efO1W inter\u00adactions are associated with distinct electropositive and electronegative sites and therefore, are mainly governed by electrostatic forces, while the rest of the close contacts are dispersive in nature. The relatively stable nature of the C12\u2014H12\u22efC7 and C6\u2014H6A\u22efO2 inter\u00adactions as compared to the O1W\u2014H1W\u22efN1 and O1W\u2014H2W\u22efO1W inter\u00adactions could be due to the presence of low repulsion energies in the former as compared to the latter.All associations between mol\u00adecules in (I)N\u22efO1/ N3\u2014H3N\u22efO2, O1W\u2014H1W\u22efN1 and O1W\u2014H2W\u22efO1W hydrogen bonding leading to a barricade-like electrostatic energy framework parallel to (a). This is further stabilized by the dispersion forces arising from other supporting inter\u00adactions which result in another barricade-like dispersion energy framework parallel to (100), Fig.\u00a06b). The overall energy framework for (I)c).The crystal of (I)3LH2 mol\u00adecule in (I)i.e. Form I and Form II A comparison of the distribution of contacts on the Hirshfeld surfaces between the 3LH2 mol\u00adecule in (I)Mercury This conclusion is consistent with the analysis of the packing similarity in which a comparison of (I)3LH2 mol\u00adecule has been characterized in two polymorphs C(=O)N(H)CH2CO2H   to 84.61\u2005(9)\u00b0. The comparable range for the S-shaped mol\u00adecules, for which both dihedral angles are identical from symmetry, is 64.2\u2005(3) to 84.79\u2005(18)\u00b0.The N,N\u2032-bis\u00ad(pyridin-3-ylmeth\u00adyl)oxalamide, was prepared according to the literature : 3578 \u03bd(O\u2014H), 3321 \u03bd(N\u2014H), 3141\u20132804 \u03bd(C\u2014H), 1687\u20131649 \u03bd(C=O), 1524\u20131482 \u03bd(C=C), 1426 \u03bd(C\u2014N), 710 \u03bd(C=C).The precursor, Uiso(H) set to 1.2\u20131.5Ueq(C). The oxygen- and nitro\u00adgen-bound H atoms were located in a difference-Fourier map and refined with O\u2014H = 0.84\u00b10.01\u2005\u00c5 and N\u2014H = 0.88\u00b10.01\u2005\u00c5, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N). Owing to poor agreement, one reflection, i.e. (551), was omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table\u00a0610.1107/S2056989019016153/hb7869sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019016153/hb7869Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016153/hb7869Isup3.cmlSupporting information file. DOI: 1969282CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "CO2 can be eliminated by renal replacement therapy but studies are scarce and clinical relevance is unknown. We prospectively studied CO2 and O2 behavior at different sample points of continuous veno-venous hemofiltration (CVVH) and build a model to calculate CO2 removal bedside.Carbon dioxide (CO2 (tCO2), CO2 flow (V\u0307CO2) and O2 flow (V\u0307O2) were compared between different sample points. The effect of citrate on transmembrane tCO2 was evaluated. Wilcoxon matched-pairs signed rank test was performed to evaluate significance of difference between 2 data sets. Friedman test was used when more data sets were compared.In 10 patients receiving standard CVVH under citrate anticoagulation, blood gas analysis was performed at different sample points within the CVVH circuit. Citrate was then replaced by NaCl 0.9% and sampling was repeated. Total CO2 in the effluent (26.0\u2009ml/min) correlated significantly with transmembrane V\u0307CO2 (24.2\u2009ml/min). This represents 14% of the average expired V\u0307CO2 in ventilated patients. Only 1.3\u2009ml/min CO2 was removed in the de-aeration chamber, suggesting that CO2 was almost entirely cleared across the membrane filter. tCO2 values in effluent, before, and after the filter were not statistically different. Transmembrane tCO2 under citrate or NaCl 0.9% predilution also did not differ significantly. No changes in V\u0307O2 were observed throughout the CVVH circuit. Based on recorded data, formulas were constructed that allow bedside evaluation of CVVH-attributable CO2 removal.V\u0307CO2 is removed by CVVH and can be quantified by one simple blood gas analysis within the circuit. Future studies should assess the clinical impact of this observation.A relevant amount of COhttps://clinicaltrials.gov with trial registration number NCT03314363 on October 192,017.The trial was registered at The online version of this article (10.1186/s12882-019-1378-y) contains supplementary material, which is available to authorized users. Subsequently, citrate predilution was stopped and replaced for at least 20\u2009min by NaCl 0.9% at similar flow. Blood gas analysis was repeated according to the same protocol.Inclusion and exclusion criteria are listed in Additional file\u00a02 content (tO2) was calculated as Hb x Hb saturation \u00d7\u20091.35 . V\u0307CO2 dropped significantly between SP2 and SP3 [from 110.5\u2009\u00b1\u20099.6\u2009ml/min to 84.5\u2009\u00b1\u20096.5\u2009ml/min (p\u2009<\u20090.01)]. V\u0307CO2 at SP4 (26.0\u2009\u00b1\u20095.8\u2009ml/min) and transmembrane V\u0307CO2 at SP4 (24.2\u2009\u00b1\u20092.6\u2009ml/min) were not statistically different (p\u2009=\u20090.39).V\u0307CO2 (SP1) than V\u0307CO2 (SP5) [109.8\u2009\u00b1\u20097.1\u2009ml/min vs. 81.7\u2009\u00b1\u20095.8\u2009ml/min (p\u2009<\u20090.01)] and a 1.3\u2009ml/min difference between V\u0307CO2 (SP3) and V\u0307CO2 (SP5) [83.0\u2009\u00b1\u20094.9\u2009ml/min vs. 81.7\u2009\u00b1\u20095.8\u2009ml/min (p\u2009=\u20090.01)].Results for NaCl 0.9% postdilution were plotted in Fig.\u00a02 at SP5 (116.1\u2009\u00b1\u20099.7\u2009ml/min) and \u201cexpected V\u0307CO2 at SP5\u201d (94.4\u2009\u00b1\u20099.9\u2009ml/min) , SP3 (25.0\u2009\u00b1\u20092.6\u2009mmol/l) and SP4 (25.1\u2009\u00b1\u20092.6\u2009mmol/l) were not statistically different (p\u2009=\u20090.51). tCO2 decreased significantly between SP1 and SP2 from 30.6\u2009\u00b1\u20092.3\u2009mmol/l to 25.5\u2009\u00b1\u20092.8\u2009mmol/l (p\u2009<\u20090.01). At all SP, tCO2 consisted of CO2 in gas form (pCO2) and HCO3-   Fig.\u00a0.Fig. 6Ef2 at SP1, SP2, SP3 and SP5 was respectively 10.6\u2009\u00b1\u20093.7\u2009ml/min,10.9\u2009\u00b1\u20093.9\u2009ml/min, 10.3\u2009\u00b1\u20093.8\u2009ml/min, and 10.9\u2009\u00b1\u20093.7\u2009ml/min. V\u0307O2 at SP4 was 0\u2009ml/min as effluent contains no Hb. V\u0307O2 (SP1) and V\u0307O2 (SP5) were not different (p\u2009=\u20090.33)  was statistically different, probably because the set CVVH fluid flow at these SP did not correspond with real fluid flow . By adding predilution fluid, tCO2 decreased between SP1 and SP2.As suggested by in vitro hemodialysis, COas HCO3- . The CO22 extraction. Only the short term effect of citrate upon CO2 removal was evaluated as an influencer of acid-base homeostasis. Over a longer time period, citrate could possibly affect CO2 clearance because it preserves membrane porosity better than heparin. tCO2 in blood passing through the CVVH circuit decreased as it was diluted by bicarbonate-free solutions. CVVH had no impact on V\u0307O2 because values remained constant at the different SP.Citrate anticoagulation did not influence tCO2 removal by CVVH in a clinical setting with the use of only one blood gas analysis in the extracorporeal circuit at a preexisting sample point. As these are the first data that were acquired in a CVVH setting, formulas could not be compared to data from other articles [Based on previous findings, different formulas were constructed to calculate COarticles . Further2 influences expired CO2.Several limitations of our study must be emphasized. First, despite the high number of analyses per patient, the sample size remains small and future studies in more patients are needed to confirm our results. Second, assumptions were made based on \u201csnapshot\u201d blood gas analysis. Continuous monitoring would be more precise. Third, fluid flows as set on CVVH may not correlate with real flow . In-circ2, both as gas and bicarbonate and measurable in the effluent, is removed during CVVH under citrate anticoagulation. Pre-filter tCO2 is the major determinant for CO2 removal. Citrate does not influence CO2 elimination. To a certain extent, bicarbonate fluids influence blood gases but data are too limited to permit relevant conclusions. Oxygen flow is not influenced by CVVH. CO2 removal by CVVH in bicarbonate-free conditions can be calculated by multiplying effluent or blood flow with CO2 content at a preexisting sample point. Their clinical relevance requires confirmation.A significant amount of COAdditional file\u00a01:Inclusion and exclusion criteria that were used during the study. (DOCX 15 kb)Additional file\u00a02:CVVH settings and postdilution fluid per patients. (DOCX 14 kb)"}
{"text": "The asymmetric unit of the title co-crystal comprises two twisted mol\u00adecules of 2,2\u2032-thiodi\u00adbenzoic acid and four mol\u00adecules of tri\u00adphenyl\u00adphosphane oxide. The three-dimensional mol\u00adecular packing is stabilized by hy\u00addroxy-O\u2014H\u22efO(oxide) hydrogen bonds and TPPO-C\u2014H\u22efO and TDBA-C\u2014H\u22ef inter\u00adactions. 14H10O4S\u00b72C18H15OP, comprises two mol\u00adecules of 2,2\u2032-thiodi\u00adbenzoic acid benzoic acid] and four mol\u00adecules of tri\u00adphenyl\u00adphosphane oxide . The two TDBA mol\u00adecules are twisted about their di\u00adsulfide bonds and exhibit dihedral angles of 74.40\u2005(5) and 72.58\u2005(5)\u00b0 between the planes through the two SC6H4 residues. The carb\u00adoxy\u00adlic acid groups are tilted out of the planes of the rings to which they are attached forming a range of CO2/C6 dihedral angles of 19.87\u2005(6)\u201360.43\u2005(8)\u00b0. Minor conformational changes are exhibited in the TPPO mol\u00adecules with the range of dihedral angles between phenyl rings being \u22122.1\u2005(1) to \u221262.8\u2005(1)\u00b0. In the mol\u00adecular packing, each TDBA acid mol\u00adecule bridges two TPPO mol\u00adecules via hy\u00addroxy-O\u2014H\u22efO(oxide) hydrogen bonds to form two three-mol\u00adecule aggregates. These are connected into a three-dimensional architecture by TPPO-C\u2014H\u22efO and TDBA-C\u2014H\u22ef inter\u00adactions. The importance of H\u22efH, O\u22efH/H\u22efO and C\u22efH/H\u22efC contacts to the calculated Hirshfeld surfaces has been demonstrated. In terms of individual mol\u00adecules, O\u22efH/H\u22efO contacts are more important for the TDBA (ca 28%) than for the TPPO mol\u00adecules (ca 13%), as expected from the chemical composition of these species. Computational chemistry indicates the four independent hy\u00addroxy-O\u2014H\u22efO(oxide) hydrogen bonds in the crystal impart about the same energy (ca 52\u2005kJ\u2005mol\u22121), with DTBA-phenyl-C\u2014H\u22efO(oxide) inter\u00adactions being next most stabilizing (ca 40\u2005kJ\u2005mol\u22121).The asymmetric unit of the title co-crystal, 2,2\u2032-thiodi\u00adbenzoic acid\u2013tri\u00adphenyl\u00adphosphane oxide (1/2), C In medicine, is dianion is found in the salt Na to 1.5018\u2005(8)\u2005\u00c5 [P1=O1].The mol\u00adecular structures of the TPPO coformers are more rigid. This is seen in the O\u2014P\u2014C\u2014C torsion angles, which range from 17.7\u2005(1) to 61.6\u2005(1), 19.8\u2005(1) to 61.5\u2005(1), \u22122.1\u2005(1) to \u221262.8\u2005(1) and \u221219.2\u2005(1) to \u221244.5\u2005(1)\u00b0 for the P1\u2013P4-mol\u00adecules, respectively. In the same way, the P=O bond lengths span an experimentally equivalent range, PLATON; Spek, 20093SC3OH\u22efO} heterosynthon as illustrated in Fig.\u00a04i.e. TPPO-C47\u2014H\u22efO11(carbon\u00adyl) and TPPO-C71\u2014H\u22efO5(carbon\u00adyl), operate in concert with hy\u00addroxy-O12\u2014H\u22efO3(oxide) and hy\u00addroxy-O6\u2014H\u22efO4(oxide) hydrogen bonds, respectively, to close a nine-membered {HC2PO\u22efHOCO\u22ef} synthon. The C\u2014H\u22efO contacts are of the type TPPO-C\u2014H\u22efO and TDBA-C\u2014H\u22efO, Table\u00a01i.e. the O5 and O11 atoms, participates in two C\u2014H\u22efO(carbon\u00adyl) inter\u00adactions, leaving no formal role for the carbonyl-O7 and O9 atoms in the mol\u00adecular packing. A view of the unit-cell contents is shown in Fig.\u00a05Geometric parameters characterizing the identified \u2013(f), the pair of TDBA-S1 and -S2 mol\u00adecules, shown with the respective pairs of hydrogen bonded TPPO mol\u00adecules, as well as the TPPO-P1\u2013P4 mol\u00adecules exhibit some similarities especially on the prominent close contacts as represented by the intense red regions on the corresponding dnorm surface mappings, which are mainly dominated by hydroxy-O\u2014H\u22efO(oxide) inter\u00adactions.The independent 2,2\u2032-thiodi\u00adbenzoic acid (TDBA) and tri\u00adphenyl\u00adphosphane oxide (TPPO) mol\u00adecules of (I)et al., 2008Upon close inspection on the surface mapping, minor differences are observed between the pair of TDBA mol\u00adecules. Specifically, a diminutive red spot is observed near one of the terminal carb\u00adoxy\u00adlic groups of the S1-mol\u00adecule arising from a TPPO-phenyl-C\u2014H\u22efO(carbonyl) inter\u00adaction but, no such contact is apparent for the S2-mol\u00adecule. As for the two pairs of TPPO mol\u00adecules, the significant difference between the TPPO-P1 and -P4 mol\u00adecules, linked to S1-DTBA, and the TPPO-P2 and P3 mol\u00adecules, linked to the S2-TDBA, is the presence of additional red spots on the surface mapping of the phenyl rings for P1- and P2-mol\u00adecules in contrast to their P3- and P4-containing counterparts. This difference may be attributed to the complementary phenyl-C\u2014H\u22ef\u03c0(phen\u00adyl) inter\u00adactions between centrosymmetrically-related mol\u00adecules, as illustrated in Fig.\u00a07di and de  contact distances in inter\u00advals of 0.01\u2005\u00c5 gives the overall two-dimensional fingerprint plots for the entire asymmetric unit of (I)a), and each of the individual TDBA, Fig.\u00a09a), and TPPO, Fig.\u00a010a), mol\u00adecules. Further, these can be delineated into specific contacts \u2013(d) give fingerprint plots delineated into H\u22efH, O\u22efH/H\u22efO and C\u22efH/H\u22efC contacts. The relative contributions of these contacts to the surfaces is given in Table\u00a03Qu\u00adanti\u00adtative evaluation of the Hirshfeld surfaces by the combination of the a, is quite different for the individual components, Figs. 9a, as the former is a sum of all the individual surface contacts, which differ for the individual mol\u00adecules. As expected, the same is true for the corresponding decomposed fingerprint plots. The major contribution to the overall surface of (I)i.e. 49.4%, comes from H\u22efH contacts. The O\u22efH/H\u22efO contacts (de + di \u223c 2.34\u2005\u00c5) make a significant contribution at 13.7%, while the C\u22efH/H\u22efC inter\u00adactions (de + di \u223c 2.66\u2005\u00c5), at 30.1%, play a more prominent role.The overall fingerprint plot for (I)3SC3OH\u22efO} heterosynthon, Fig.\u00a04a), which exhibit an almost identical claw-like fingerprint profile but arranged in the exact reverse order, i.e. Fig.\u00a09a) cf. Fig.\u00a010a). Among all the close inter\u00adactions, H\u22efH contacts, Figs. 8b, represent the dominant inter\u00adactions to the individual surfaces, i.e. 41\u201342% for the TDBA mol\u00adecules and 49\u201351% for the DPPO mol\u00adecules, and exhibit de + di contact distances ranging from 2.24 to 2.38\u2005\u00c5 which is very close to the sum of van der Waals radii of 2.4\u2005\u00c5.The formation of the 13-membered {O\u22efHOCc). These feature two tips \u2013 one at relatively short de + di \u223c1.6\u2005\u00c5 that can be attributed to the hydroxy-H\u22efO(oxide) hydrogen bonds for the S1- and S2-TDBA mol\u00adecules, Fig.\u00a010c), or oxide-O\u22efH(hydrox\u00ady) hydrogen bonds for P1\u2013P4-TPPO. The other tip has a relatively long de + di value of \u223c2.4\u2005\u00c5 and arises as a result of hy\u00addroxy-O\u22efH(phen\u00adyl) contacts for S1- and S2-TDBA or phenyl-H\u22efO(hydrox\u00ady) for P1\u2013P4-TPPO. The O\u22efH/H\u22efO contacts constitute the second most dominant inter\u00adactions for the TDBA mol\u00adecules and third most for the TPPO mol\u00adecules, Table\u00a03The O\u22efH hydrogen bonds constitute the strongest among all inter\u00adactions present in the co-crystal and lead to formation of asymmetric, forceps-like profiles in the corresponding decomposed fingerprint plots, Figs. 9de + di distance range of 2.7\u20132.8\u2005\u00c5, i.e. close to the sum of van der Waals radii of 2.9\u2005\u00c5, despite the contacts constituting the third most dominant inter\u00adaction in the TDBA mol\u00adecules (ca 22%) and being the second most dominant for the TPPO mol\u00adecules (ca 32%). An exception to the trend is found for the P1- and P2-TPPO mol\u00adecules, which display relatively short contact distances at ca 2.6\u2005\u00c5 owing to the formation of C\u2014H\u22ef\u03c0 inter\u00adactions as discussed above.Similar to the H\u22efH contacts, the C\u22efH/H\u22efC inter\u00adactions contribute weakly to the mol\u00adecular packing of the co-crystal as evidenced from the et al., 2018In summary the Hirshfeld surface analysis on (I)d,p) available in Crystal Explorer  of the hy\u00addroxy-O\u2014H\u22efO(oxide) hydrogen bonds is consistent across the series and lies in the range \u221250.7 to \u221253.3\u2005kJ\u2005mol\u22121. The other close contacts which exerts a relatively strong influence in the energy frameworks of the co-crystal are DTBA-phenyl-C\u2014H\u22efO(oxide) inter\u00adactions, with the Etot amounting of ca \u221240\u2005kJ\u2005mol\u22121, Table\u00a04Selected results obtained from the inter\u00adaction energy calculations involving the DTBA mol\u00adecules as reference mol\u00adecules are tabulated in Table\u00a04et al., 2005The only other structure of 2,2\u2032-thiodi\u00adbenzoic acid in the literature is that of the pure compound H. The observed P=O bond lengths in (I)i.e. in the range 1.4975\u2005(8) to 1.5018\u2005(8)\u2005\u00c5 are at the lower end of the range of such bonds.A survey of the Cambridge Structural Database : 3062 \u03bd(C\u2014H), 1693 \u03bd(COO), 1236 \u03bd(P=O), 1116 \u03bd(P\u2014Ar), 719 \u03b4(P\u2014C), 617 \u03bd(C\u2014S).All chemical precursors were of reagent grade and used as received without purification. Thio\u00adsalicylic acid  and tri\u00adphenyl\u00adphosphane  were dissolved in aceto\u00adnitrile (40\u2005ml) and the mixture subsequently added into an aceto\u00adnitrile solution (25\u2005ml) of copper(I) iodide . The reaction mixture was stirred for 1\u2005h at room temperature before the white product was filtered, washed with cold ethanol and dried Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from difference Fourier maps and refined without constraint. Owing to poor agreement, three reflections, i.e.  global, I. DOI: 10.1107/S205698901801544X/hb7782Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801544X/hb7782Isup3.cmlSupporting information file. DOI: 1876525CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The title mol\u00adecule adopts a helical structure, in which two 2,3\u2032-bipyridyl units are twisted up and down relative to the plane of the central benzene ring. Weak inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions lead to formation of a two-dimensional supra\u00admolecular network. Hirshfeld surface analysis indicates that the mol\u00adecular packing in the title compound is mainly dominated by inter\u00admolecular H\u22efH and H\u22efC/C\u22efH inter\u00adactions. 38H42N4O4, displays a helical structure induced by the combination of the C\u2014C\u2014C\u2014C torsion angle [\u221210.8\u2005(2)\u00b0] between two 2,3\u2032-bipyridyl units attached to the 1,2-positions of the central benzene ring and consecutive connections between five aromatic rings through the meta- and ortho-positions. Intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions between an H atom of a pyridine ring and the centroid of a another pyridine ring contributes to the stabilization of the helical structure. In the crystal, weak C\u2014H\u22ef\u03c0 inter\u00adactions link the title mol\u00adecules into a two-dimensional supra\u00admolecular network extending parallel to the ac plane, in which the mol\u00adecules with right- and left-handed helical structures are alternately arranged. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the mol\u00adecular packing is dominated by van der Waals inter\u00adactions between neighbouring H atoms, as well as by C\u2014H\u22ef\u03c0 inter\u00adactions. One isopropoxyl group is disordered over two sets of sites [occupancy ratio 0.715\u2005(5):0.285\u2005(5)].The title mol\u00adecule, C An intra\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adaction between aromatic H3 and the centroid of the N3/C17\u2013C21 ring as well as C\u2014H\u22efN/O hydrogen bonds \u00b0, which is believed to reduce the steric hindrance between the two 2,3\u2032-bipyridyl units. In combination with this torsion angle, the consecutive connections of five aromatic rings in the title mol\u00adecule lead to a helical structure. The central benzene unit occupies A\u22efCg1i and between (meth\u00adyl)H37C\u22efCg2ii  was found to be disordered over two sets of sites [occupancy ratio 0.715\u2005(5):0.285\u2005(5)].Crystal data, data collection and crystal structure refinement details are summarized in Table\u00a0410.1107/S2056989018013002/wm5462sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989018013002/wm5462Isup2.hklStructure factors: contains datablock(s) I. DOI: 1867774CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "It consists of octa\u00adhedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetra\u00adhedral [ReVIIO4]\u2212 anions (Re1 site symmetry 1) and octa\u00adhedral [ReIVF6]2\u2212 anions ] tetroxidorhenate(VII) tetra\u00adkis\u00ad[hexa\u00adfluorido\u00adrhenate(IV)] hexa\u00adhydrate, arose unexpectedly due to possible contamination of the K 2ReF6 starting material with KReO4. It consists of octa\u00adhedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetra\u00adhedral [ReVIIO4]\u2212 anions (Re site symmetry 1) and octa\u00adhedral [ReIVF6]2\u2212 anions , [Co(NH3)6]3+ octa\u00adhedral cations (mean Co\u2014N = 1.962\u2005\u00c5), and the [ReO4]\u2212 tetra\u00adhedral anion (mean Re\u2014O = 1.719\u2005\u00c5) are slightly distorted. A network of N\u2014H\u22efF hydrogen bonds consolidates the structure. The crystal studied was refined as a two-component twin.The title hydrated salt, tris\u00ad[hexa\u00adamminecobalt(III)] tetraoxidorhenate(VII) tetra\u00adkis\u00ad[hexa\u00adfluorido\u00adrhenate(IV)] hexa\u00adhydrate, arose unexpectedly due to possible contamination of the K VII is dominated by the tetra\u00adhedral perrhenate anion, [ReO4]\u2212  anions  can be prepared in high yield by the reduction of a perrhenate starting material in the corresponding concentrated HX acid  with AHF2  followed by an aqueous work-up  salts as well as their X-ray single-crystal structures was recently reported , an unexpected mixed-valence rhenium(IV)\u2013rhenium(VII) salt arose in an effort to prepare [Co(NH3)6]2[ReF6]3 by metathesis from K2[ReF6] and Co(NH3)6Cl3 in water (353\u2005K). Yellow\u2013orange needle-like crystals of (I) were obtained within two hours by slow evaporation in water at room temperature. The crystals of (I) are air stable over short periods, but decompose to a black material after six months of storage at ambient temperature.In the process of exploring the coordination chemistry of hexa\u00adfluoro\u00adrhenate(IV) compounds, the title compound (I) 6]3+ cation, three distinct [ReF6]2\u2212 anions, one [ReO4]\u2212 anion, and two water mol\u00adecules of crystallization: these components are held together by electrostatic forces and hydrogen bonding. Site symmetries for the metal atoms are Co1: 1 (Wyckoff position 18f), Re1: 3 (Wyckoff position 6c), Re2: 1 (Wyckoff position 18f), Re3: a), and Re4: b).The structure of (I) Fig.\u00a01 is built3)6]3+ cation in (I) is slightly distorted; the average Co\u2014N bond length of 1.962\u2005\u00c5 is in agreement with the average Co\u2014N bond lengths of 1.963\u2005\u00c5 in [Co(NH3)6](ReO4)\u00b72H2O 6](TcO4)3 , the shortest Co\u22efCo and N\u22efN separations between nearby [Co(NH3)6]3+ cations are 7.035\u2005(1) and 4.473\u2005(1)\u2005\u00c5, respectively.The octa\u00adhedral [Co(NH4]\u2212 anion in (I), the average Re\u2014O bond length (1.719\u2005\u00c5) is in agreement with the average Re\u2014O bond length of 1.720\u2005\u00c5 in [Co(NH3)6](ReO4)\u00b72H2O  the values of three Re\u2014O bond lengths,  are slightly shorter than the fourth one [Re\u2014O1 = 1.748\u2005(14)\u2005\u00c5]. In (I), all O\u2014Re\u00ad\u2014O bond angles in the [ReO4]\u2212 anion are 109.5\u2005(3)\u00b0. However, in [Co(NH3)6](ReO4)\u00b72H2O, the [ReO4]\u2212 anion is slightly distorted by up to 2.7\u00b0 \u2005\u00c5 to 1.929\u2005(6)\u2005\u00c5. All the Re\u2014F bond lengths in the Re3- and Re4-centred anions are of equal distances of 1.952\u2005(6) and 1.950\u2005(6)\u2005\u00c5, respectively, by symmetry. Overall, the average Re\u2014F bond length (1.834\u2005\u00c5) in (I) is notably shorter than the average Re\u2014F bond length (1.951\u2005\u00c5) in A2[ReF6]  salts previously studied  and its component ions 6]3+) are shown in Fig.\u00a026]2\u2212 anions and the water mol\u00adecules (Table\u00a01A perspective view of the unit-cell plots for (s Table\u00a01.I) is the only reported hexa\u00adhalogenorhenate\u2013perrhenate structure containing both rhenium(IV) and rhenium(VII). It is noted that K2[ReF6] used for the preparation of (I) was not characterized before use and the presence of perrhenate in (I) may be due to the presence of K[ReO4] in the starting material. Efforts to isolate the technetium (Tc-99) derivative compound, [Co(NH3)6]3 [(Tc(vii)O4) (Tc(iv)F6)4] are in progress.To the best of our knowledge,  was dissolved in 2\u2005ml of hot water (353\u2005K), and [Co(NH3)6]Cl3  dissolved in 1\u2005ml of \u2005H2O was added. The solution was allowed to evaporate slowly at room temperature and yellow-orange needle-like crystals of (I) were obtained within two hours. The compound was washed with H2O (3 \u00d7 1\u2005ml), followed by iso\u00adpropanol (3 \u00d7 1\u2005ml) and then diethyl ether (3 \u00d7 1\u2005ml). Single crystals of (I) were grown in H2O by slow evaporation at room temperature. Yield: ca 91%. The presence of perrhenate in (I) is probably due to the presence of K[ReO4] in the starting material (i.e. K2ReF6).KCrystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019009757/hb7830sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019009757/hb7830Isup2.hklStructure factors: contains datablock(s) I. DOI: 1939234CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The anions are disordered and modelled in two orientations. The major conformations have occupancies of 57, 59, 60 and 79%The asymmetric unit of the title compound contains two di\u00adaqua\u00adbis\u00ad(ethyl\u00adenedi\u00adamine)\u00adcopper(II) cations and four nitro\u00adbenzoate anions. These are connected into three-mol\u00adecule aggregates  2N,N\u2032)copper(II) bis\u00ad(2-nitro\u00adbenzoate), [Cu(C2H8N2)2(H2O)2](C7H4NO4)2, two di\u00adaqua\u00adbis\u00ad(ethyl\u00adenedi\u00adamine)\u00adcopper(II) cations and four nitro\u00adbenzoate anions are present in the asymmetric unit. All four anions are \u2018whole-mol\u00adecule\u2019 disordered over two sets of sites. The major components have refined occupancies of 0.572\u2005(13), 0.591\u2005(9), 0.601\u2005(9) and 0.794\u2005(10). The CuII ions exhibit slightly distorted octa\u00adhedral geometries. In the crystal, cations and anions are connected to each other via N\u2014H\u22efO and O\u2014H\u22efO hydrogen bonds, forming a two-dimensional network parallel to (200). The inter\u00admolecular contacts in the crystal were further analysed using Hirshfeld surface analysis, which indicates that the most significant contacts are O\u22efH/H\u22efO (42.9%), followed by H\u22efH (35.7%), C\u22efH/H\u22efC (14.2%), C\u22efC (2.9%), C\u22efO/O\u22efC (2.2%), N\u22efH/H\u22efN (0.9%) and N\u22efO/O\u22efN (0.3%).In the title compound, di\u00adaqua\u00adbis\u00ad(ethyl\u00adenedi\u00adamine-\u03ba Copper(II) carboxyl\u00adates have been used as single precursors for the preparation of copper(II) oxide nanoparticles di\u00adaqua\u00adcopper(II) cations and four 2-nitro\u00adbenzoate anions. In both cations, the CuII ion is coordinated by four N atoms of the ethyl\u00adenedi\u00adamine ligands which chelate the metal in the equatorial plane, and two axially coordinated water mol\u00adecules forming a slightly distorted octa\u00adhedral geometry. The Cu\u2014N bond lengths range from 1.991\u2005(6) and 2.050\u2005(5)\u2005\u00c5 (Table\u00a012(H2O)2]2+ cations  and 2.564\u2005(5)\u2005\u00c5 for Cu1B] are noticeably longer than the equatorial Cu\u2014N distances  to 1.251\u2005(15)\u2005\u00c5] in the nitro group are close to the values observed for related compounds reported in the literature  and (C1A\u2013C6A) at . These inter\u00adactions consolidate the three-dimensional structure \u00adcopper(II) 2-nitro\u00adbenzoate  under stirring. The precipitate was filtered, dried and dissolved in a hot methanol solution containing ethyl\u00adenedi\u00adamine  under stirring. The mixture was filtered and single crystals were obtained after slow evaporation for one week.An aqueous solution of sodium 2-nitro\u00adbenzoate  was added to an aqueous solution of CuSOUiso(H) = 1.2Ueq(C) for all C-bound H atoms. The N-bound H atoms were located in a difference-Fourier map and refined with N\u2014H = 0.91\u2005\u00c5, and with Uiso(H) = 1.5Ueq(N). The H atoms bonded to O atoms  were located in a difference map and treated as part of a rigid group with oxygen as the pivot atom. All four anions are whole-mol\u00adecule disordered over two sets of sites. The major components have refined occupancies of 0.572\u2005(13), 0.591\u2005(9), 0.601\u2005(9) and 794\u2005(10). The major and minor components of disorder for each anion were constrained using the SAME command in SHELXL  I. DOI: 10.1107/S2056989019016669/lh5937Isup2.hklStructure factors: contains datablock(s) I. DOI: 1909170CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II atom in the title compound has a distorted trigonal\u2013bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N\u2032-diglycinate ligand. The dinuclear complex cations and the nitrate counter-anions as well as the solvate mol\u00adecules are linked by an intricate network of hydrogen bonds.The Cu 2(C12H10N2O6)(C12H8N2)4](NO3)2\u00b7C12H12N2O6\u00b78H2O, is composed of a CuII atom with a distorted trigonal\u2013bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N\u2032-diglycinate anion. The asymmetric unit is completed by one-half of the N,N\u2032-diglycine solvent mol\u00adecule, which is located on a centre of inversion, by one nitrate counter-anion and four water mol\u00adecules. In the crystal, the cationic complexes are linked via inter\u00admolecular \u03c0\u2013\u03c0 stacking and through lone-pair\u22ef\u03c0 inter\u00adactions involving the N,N\u2032-diglycinate anion and the phenanthroline ligands. The N,N\u2032-diglycine solvent mol\u00adecule is involved in classical and non-classical hydrogen-bonding inter\u00adactions, as well as \u03c0\u2013\u03c0 stacking inter\u00adactions. The centroid-to-centroid distances between aromatic entities are in the range 3.5402\u2005(5)\u20134.3673\u2005(4)\u2005\u00c5. The crystal structure is stabilized by further C\u2014H\u22efO contacts as well as by O\u2014H\u22efO and N\u2014H\u22efO hydrogen bonds between water mol\u00adecules, the nitrate anions, the N,N\u2032-diglycinate ligands, N,N\u2032-diglycine solvent mol\u00adecules and phenanthroline ligands, giving rise to a supra\u00admolecular framework. A Hirshfeld surface analysis was carried out to qu\u00adantify these inter\u00adactions.The centrosymmetric binuclear complex cation of the title compound, [Cu In the two structures, the embedded N,N\u2032-diglycate mol\u00adecule links the cationic buildings blocks by numerous supra\u00admolecular inter\u00adactions.In our synthetic approach, we employ such systems as electron-deficient bidentate aromatic ring systems such as phenanthroline or bi\u00adpyridine in order to block parts of the metal cation coordination sphere. Thus, the alternative assembly process lies in the use of the offered different \u03c0-inter\u00adaction possibilities, N,N\u2032-di\u00adglycine moiety is a bis-monodentate bridging anionic ligand in its deprotonated form, as well as a solvent mol\u00adecule in its neutral form in one crystal structure. The structural investigation and description of the supra\u00admolecular network is confirmed and discussed with the aid of a Hirshfeld surface analysis diglycine solvent mol\u00adecule.In a continuation of this work, we have now synthesized and determined the structure of a novel copper(II) coordination compound where the 2(C12H8N2)4(C12H10N2O6)](NO3)2\u00b7(C12H12N2O6)\u00b78H2O, comprises two bidentate phenanthroline ligands and one bridging monodentate N,N\u2032-diglycinate ligand for each CuII atom, defining a distorted trigonal\u2013bipyramidal coordination sphere. A crystallographic centre of inversion is located at the centroid of the bridging N,N\u2032-diglycinate anion as well as the neutral and non-coordinating N,N\u2032-diglycine solvent mol\u00adecule. The asymmetric unit is completed by one non-coordinating nitrate counter-anion and four water mol\u00adecules , 2.119\u2005(2) and 2.111\u2005(3)\u2005\u00c5, and the axial positions by N1 and N3 with shorter bonds each of 1.974\u2005(3)\u2005\u00c5, respectively. The bond angle N1\u2014Cu\u2014N3 is 174.71\u2005(11)\u00b0. The sum of the bond angles O1\u2014Cu\u2014N2 [136.69\u2005(11)\u00b0], O1\u2014Cu\u2014N4 [103.88\u2005(12)\u00b0] and N2\u2014Cu\u2014N4 [118.90\u2005(10)\u00b0] in the equatorial plane amounts to 359.47\u00b0, indicating only slight distortions. Distances and angles within the distorted trigonal\u2013bipyramidal coordination sphere of the CuII ion are similar to those found in the literature diglycine solvent mol\u00adecule [C36\u2014O4 = 1.205\u2005(6) and C36\u2014O5 = 1.316\u2005(5)\u2005\u00c5]. The O1\u2014C30\u2014O2 angle of 123.1\u2005(4)\u00b0 in the carboxyl\u00adate group is slightly smaller than in the carb\u00adoxy\u00adlic group [O4\u2014C36\u2014O5 = 124.3\u2005(4)\u00b0]. In the coordinating N,N\u2032-diglycate ligand, the deviations of atoms defining the central benzamido entity from its least-squares plane are 0.040\u2005(4)\u2005\u00c5 (C28), \u22120.084\u2005(3)\u2005\u00c5 (O3), 0.245\u2005(4)\u2005\u00c5 (N5) and 0.404\u2005(4)\u2005\u00c5 (C29), while in the N,N\u2032-diglycine solvent they are \u22120.018\u2005(4)\u2005\u00c5 (C34) , 0.102\u2005(3)\u2005\u00c5 (O6), \u22120.192\u2005(4)\u2005\u00c5 (N6) and \u22120.257\u2005(4)\u2005\u00c5 (C35). The angle between the amide group and the carboxyl\u00adate group connected through the sp3-hybridized methyl\u00adene carbon atom (N5\u2014C29\u2014C30) is 113.6\u2005(3)\u00b0, and for the neutral solvent mol\u00adecule it is (N6\u2014C35\u2014C36) 112.1\u2005(3)\u00b0. The dihedral angle between the planar carboxyl\u00adate group (O1/C30/O2) and the aromatic synthon (C25\u201327/C25\u2032\u2013C27\u2032) of the ligand is 84.1\u2005(3)\u00b0 and thus smaller than the value found in the free solvent mol\u00adecule of the aromatic synthon (C31\u2013C33/C31\u2032\u2013C33\u2018) and the planar carboxyl\u00adate group (O4/C36/O5) at 88.9\u2005(3)\u00b0. The dihedral angle between the mean planes of the two bidentate phenanthroline ligands is 61.71\u2005(5)\u00b0; the corresponding value between phenanthroline (N1/C1\u2013C12/N2) and the coordin\u00adating carboxyl\u00adate group (O1/C30/O2) is 79.9\u2005(4)\u00b0 and between phenanthroline (N3/C13\u2013C24/N4) and the carboxyl\u00adate group is 82.5\u2005(3)\u00b0, respectively.The equatorial plane of the Cuvia O\u2014H\u22efO, C\u2014H\u22efO and partly via N\u2014H\u22efO hydrogen bonds with water solvent mol\u00adecules, the phenanthroline ligands and the metal-coordinating N,N\u2032-di\u00adglycin\u00adate ligands diglycine solvent mol\u00adecule, as well as between phenanthroline ligands and the metal-coordinating N,N\u2032-diglycinate ligand stack these components along the different axes \u2005\u00c5 between Cg2\u22efCg4, 3.6686\u2005(5)\u2005\u00c5 between Cg3\u22efCg4, and 3.5402\u2005(5)\u2005\u00c5 between Cg5\u22efCg5, where Cg1, Cg2Cg, 3Cg, 4 and Cg5 are the centroids defined by the ring atoms N1/C1\u2013C4/C12, C4\u2013C7/C11\u2013C12, N2/C7\u2013C11, C31\u2013C33/C31\u2032\u2013C33\u2032 and C16\u2013C19/C23\u2013C24, respectively. These distances are in expected ranges diglycinate ligand leads to a longer Cg6\u22efCg7 separation of 4.3673\u2005(4)\u2005\u00c5 \u00b0 and is slightly increased in comparison with the lines through C26/Cg7 and the centroids Cg6/Cg7 with a value of 16.99\u2005(5)\u00b0. Distances shown in Fig.\u00a04Cg7 and C15/Cg7 are 3.4440\u2005(4) and 3.676\u2005(6)\u2005\u00c5 and between H26/Cg7 and C26/Cg7 are 3.5049\u2005(4) and 3.713\u2005(5)\u2005\u00c5 with observed angles of 96.8\u2005(3)\u00b0 (C15\u2014H15\u22efCg7) and 95.4\u2005(3)\u00b0 (C16\u2014H26\u22efCg7), respectively. Besides the previously mentioned forces, a lone-pair\u22ef\u03c0 inter\u00adaction between the O3 atom of the carboxyl\u00adate group of the metal-coordinating N,N\u2032-diglycinate ligand and the Cg5 centroid of a phenanthroline ligand are observed and associated with a distance of 3.739\u2005(4)\u2005\u00c5. This value is similar to those found in the literature  analysis diglycine solvent mol\u00adecule in the range \u22120.6806 to 1.9484 a.u. are shown in Fig.\u00a05de \u223c 1.19\u2005\u00c5/di \u223c 0.85\u2005\u00c5 and di \u223c 0.68\u2005\u00c5/de \u223c 1.02\u2005\u00c5 as well as de \u223c 1.05\u2005\u00c5/di \u223c 0.70\u2005\u00c5 and di \u223c 1.12\u2005\u00c5/de \u223c 0.78\u2005\u00c5, which comprise 27.9% and 42.2% of the total amount on the HS, respectively.The HS mapped over N,N\u2032-diglycine solvent mol\u00adecule involved in hydrogen bonding, the HS mapped over the electrostatic potentials were calculated using TONTO diglycine solvent mol\u00adecule as the second largest contribution within the HS. This high relevance for the HS is attributed to the high proportion of hydrogen atoms in the structure of these entities. The H\u22efN/N\u22efH contacts contribute 3.7% to the cationic complex and 3.4% to the solvent mol\u00adecule to the total HS, respectively. Short contacts of the solvent mol\u00adecule with a minor contribution to the lattice of O\u22efN/N\u22efO (0.4%) and O\u22efO (0.1%) are also observed. The contribution of the different \u03c0\u2013\u03c0 inter\u00adactions used for the stacking of the cationic complex subunits and the N,N\u2032-diglycine solvent mol\u00adecule along the different axes is also significant for both entities. Therefore, the close H\u22efC/C\u22efH (16.7%), C\u22efC (12.0%), O\u22efC/C\u22efO (2.1%) and N\u22efC/C\u22efN (1.2%) contacts of the cationic complex are assigned to C\u2014H\u22ef\u03c0 inter\u00adactions, \u03c0\u2013\u03c0 stacking (face-to-face) and lone-pair\u22ef\u03c0 inter\u00adactions of the carbonyl group and stacking between the phenanthroline ligands diglycine solvent mol\u00adecule, the close C\u22efC (11.1%), H\u22efC/C\u22efH (9.9%), N\u22efC/C\u22efN (1.8%) and O\u22efC/C\u22efO (1.2%) contacts are assigned to \u03c0\u2013\u03c0 stacking (face-to-face), C\u2014H\u22ef\u03c0 inter\u00adactions and stackings of the phenanthrolines and lone-pair\u22ef\u03c0 inter\u00adactions of the carbonyl group diglycinate ligand as well as the non-coordinating N,N\u2032-di\u00adglycine solvent mol\u00adecule in the HS mapped over the shape-index, which represent the face-to-face \u03c0\u2013\u03c0 stacking inter\u00adactions diglycine using SciFinder diglycine, and their structures show a number of non-classical inter\u00adactions  diglycine, was prepared by the method of Cleaver & Pratt (1955v/v) mixture of water and methanol (50\u2005ml) and refluxed for 30 minutes. The mixture was allowed to cool to room temperature, and a previously prepared aqueous solution of copper acetate (1\u2005mmol) was slowly added under continuous stirring. Pale-blue block-shaped crystals of the title compound were obtained by slow evaporation at room temperature.The starting material, ratt 1955. Cesium Uiso(H) = 1.2Ueq(C) and C\u2014H(aromatic) = 0.94\u2005\u00c5 and C\u2014H(methyl\u00adene) = 0.98\u2005\u00c5 using a riding model. The water H atoms were located in a difference-Fourier map and were refined with O\u2014H distances restrained to 0.82\u20130.87\u2005\u00c5 and with Uiso(H) = 1.5Ueq(O), except O11\u2014H11A with a fixed distance of 1.00\u2005\u00c5, which led to a stable and consolidated hydrogen-bonding network.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019005164/wm5501sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019005164/wm5501Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019005164/wm5501Isup3.cdxSupporting information file. DOI: 1910262CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal, the mol\u00adecules are linked by weak C\u2013H\u22efF hydrogen bonds into the supra\u00admolecular inversion dimers. 13H6Cl3FOS, the aromatic rings are inclined to one another by 12.9\u2005(2)\u00b0, and the thio\u00adphene ring is affected by \u03c0-conjugation. In the crystal, mol\u00adecules are linked by C\u2014H\u22efF hydrogen bonds, forming an R22(8) ring motif. A Hirshfeld surface analysis was conducted to verify the contribution of the different inter\u00admolecular inter\u00adactions. The shape-index surface clearly shows that the two sides of the mol\u00adecules are involved in the same contacts with neighbouring mol\u00adecules and the curvedness plots show flat surface patches characteristic of planar stacking.In the title chalcone\u2013thio\u00adphene derivative, C Chalcones, considered to be the precursor of flavonoids and isoflavonoids, are abundant in edible plants. Compounds with the 1,3-di\u00adphenyl\u00adprop-2-en-1-one framework are described by its generic term \u2018chalcone\u2019. They consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon \u03b1,\u03b2-unsaturated carbonyl system. These are coloured compounds because of the presence of the \u2013CO\u2014CH=CH\u2013 chromophore, which depends in the presence of other auxochromes. Accumulating evidence has shown that chalcones and their derivatives could inhibit tumor initiation and progression. In view of the above, and as a part of our ongoing research on chalcone derivatives \u00b0 for the atoms O1\u2014C5\u2014C6\u2014C7. The thio\u00adphene ring is affected by \u03c0 conjugation. This can be explained by the longer C=S values of 1.703\u2005(6) and 1.714\u2005(4)\u2005\u00c5 for S1=C2 and S1=C1, respectively. The bond-angle values O1\u2014C5\u2014C6 [121.9\u2005(4)\u00b0], O1\u2014C5\u2014C4 [118.2\u2005(4)\u00b0] and C5\u2014C6\u2014C7 = 125.14\u2005(4)\u00b0 about C5 indicate that the carbon atom is in a distorted trigonal\u2013planar configuration, which is due to steric hindrance of the oxygen atom. The mol\u00adecular structure is stabilized by an intra\u00admolecular C6\u2014-H6A\u22efCl1 hydrogen bond (Table\u00a01S(6) motif, as shown in Fig.\u00a01The mol\u00adecular structure of the title compound, shown in Fig.\u00a01d Table\u00a01 that cloCg1\u22efCg1 = 3.956\u2005(3)\u2005\u00c5  and Cg2\u22efCg2 = 3.957\u2005(3)\u2005\u00c5  where Cg1 and Cg2 are the centroids of the S1/C1\u2013C4 and C8\u2013C13 rings, respectively.In the crystal, the mol\u00adecules are linked by C\u2014H\u22efF hydrogen bonds, forming an et al., 2016E)-3-(phen\u00adyl)-1-prop-2-en-1-one as the main skeleton revealed the presence of three structures containing a similar 2,5-di\u00adchloro\u00adthio\u00adphene\u2013chalcone moiety to the title compound but with different substituents on the terminal phenyl rings, viz. [(E)-1--3-(X)prop-2-en-1-one], where X = 4-(di\u00admethyl\u00adamino)\u00adphenyl  and shape-index (\u22121.0 to 1.0 a.u.), respectively. The calculated volume inside the Hirshfeld surface is 325.37\u2005\u00c53 in the area of 310.17\u2005\u00c53.Hirshfeld surfaces and fingerprint plots were generated for the title compound based on the crystallographic information file (CIF) using A\u22efCl1 and C10\u2014H10A\u22efF1 inter\u00adactions, which play a significant role in the mol\u00adecular packing of the title compound. The Hirshfeld surfaces illustrated in Fig.\u00a04In Fig.\u00a04The overall two-dimensional fingerprint plot for the title compound and those delineated into Cl\u22efH/H\u22efCl, C\u22efC, Cl\u22efCl, Cl\u22efS/S\u22efCl, H\u22efH, F\u22efH/H\u22efF, C\u22efH/H\u22efC contacts are illustrated in Fig.\u00a05et al., 2013abet al., 2014et al., 2010bThe title compound was synthesized as per the procedure reported earlier (Kumar Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018010216/xu5930sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018010216/xu5930Isup2.hklStructure factors: contains datablock(s) I. DOI: 1036795CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Correction to: J Cardiovasc Magnhttps://doi.org/10.1186/s12968-019-0537-4In the original version of this article , publishGadoteriol) application (T1 native: 5\u2009s(3\u2009s)3\u2009s; T1 post-contrast: 4\u2009s(1\u2009s)3\u2009s(1\u2009s)2\u2009s; TE 1.1\u2009ms and slice thickness 6\u2009mm).A sampling protocol with reduced sensitivity to heart rate was applied [15] before and 15\u2009min after contrast media  application (T1 native: 5\u2009s(3\u2009s)3\u2009s; T1 post-contrast: 4\u2009s(1\u2009s)3\u2009s(1\u2009s)2\u2009s; TE 1.1\u2009ms and slice thickness 6\u2009mm).A sampling protocol with reduced sensitivity to heart rate was applied [15] before and 15\u2009min after contrast media (0.15\u2009mmol/kg body weight The corrected information is also repeated below:"}
{"text": "In the crystal, the only short inter\u00admolecular contacts are Cl\u22efO contacts [3.173\u2005(3)\u2005\u00c5] that link the mol\u00adecules to form a 21 helix propagating along the b-axis direction.In the title chalcone derivative, C 15H9BrCl2O, the aryl rings are inclined to each by 14.49\u2005(17)\u00b0, and the configuration about the C=C bond is E. There is a short intra\u00admolecular C\u2014H\u22efCl contact present resulting in the formation of an S(6) ring motif. In the crystal, the shortest inter\u00admolecular contacts are Cl\u22efO contacts [3.173\u2005(3)\u2005\u00c5] that link the mol\u00adecules to form a 21 helix propagating along the b-axis direction. The helices stack up the short crystallographic a axis, and are linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.983\u2005(1)\u2005\u00c5], forming layers lying parallel to the ab plane. A qu\u00adanti\u00adfication of the inter\u00admolecular contacts in the crystal were estimated using Hirshfeld surface analysis and two-dimensional fingerprint plots.In the title chalcone derivative, C Chemically they consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon, \u03b1-unsaturated carbonyl system and are described by the generic term \u2018chalcone\u2019. Chalcones are coloured compounds because of the presence of the \u2013CO\u2014CH=CH\u2013 chromophore, which depends on the presence of other auxochromes. Chalcones are finding applications as organic non-linear optical materials (NLO) because of their good SHG conversion efficiencies (Chandra Shekhara Shetty E configuration. There is a short intra\u00admolecular C\u2014H\u22efCl contact present resulting in the formation of an S(6) ring motif \u00b0. The trans conformation of the C=C double bond in the central enone group is confirmed by the C6\u2014C7\u2014C8=C9 torsion angle of \u2212179.8\u2005(3)\u00b0. The bond angles O1\u2014C9\u2014C10 [120.4\u2005(3)\u00b0], O1\u2014C9\u2014C8 [119.9\u2005(3)\u00b0] and C9\u2014C8\u2014C7 [123.9\u2005(4)\u00b0] about C9 indicate that this carbon atom is in a distorted trigonal\u2013planar conformation.The mol\u00adecular structure of the title compound is shown in Fig.\u00a01if Fig.\u00a01. The unsa axis. The shortest inter\u00admolecular contacts are Cl\u22efO1i contacts .In the crystal, the mol\u00adecules stack along the short crystallographic on Fig.\u00a02. The helCrystalExplorer  shows an extensive flat surface characteristic of planar stacking \u2013 see the Supra\u00admolecular features section above.Hirshfeld surfaces and fingerprint plots were generated for the title compound using d Figs. 2 and 3 \u25b8,et al., 2007The overall two-dimensional fingerprint plot , including 1-(3-bromo\u00adphen\u00adyl)-3-phenyl\u00adprop-2-en-1-one itself \u00b0 because of the presence of the intra\u00admolecular C\u2014H\u22efCl hydrogen bond, as shown in Fig.\u00a01A search of the Cambridge Structural Database  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S205698901900104X/qm2132sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901900104X/qm2132Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900104X/qm2132Isup3.cmlSupporting information file. DOI: 10.1107/S205698901900104X/qm2132sup4.pdfDetails of CSD search. DOI: 1036741CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "One showcases a novel (dppm)C(N2dppm) PCP pincer, the other contains a (dppm)C(N2) diazo\u00admethyl\u00adene\u00adphospho\u00adrane moiety.In this communication, two compounds and their respective crystal structures, obtained  2(C58H51N3P4)]Cl\u00b75.5CH3CN or Cl\u00b75.5CH3CN , resulting from an oxygen-mediated cleavage of a triazeneyl\u00adidene\u00adphospho\u00adrane ligand producing a diazo\u00admethyl\u00adene\u00adphospho\u00adrane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands. The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazo\u00adphospho\u00adrane. The chlorido ligands are positioned trans to the central carbon atom and to the phospho\u00adrus donor of the seven-membered ring of the pincer system, respectively. A chloride ion serves as counter-ion for the monocationic complex. The structure of [IrI(C26H22N2P2)(C26H22P2)(C6H7N)]I(I3)\u00b70.5I2\u00b7CH3OH\u00b70.5CH2Cl2 or I(I3)\u00b70.5I2\u00b7CH3OH\u00b70.5CH2Cl2 {4, systematic name: iodido(phenyl\u00admethanimine-\u03baN)iridium(III) iodide\u2013triiodide\u2013di\u00adchloro\u00admethane\u2013iodine\u2013methanol (2/2/1/1/2)}, accessed via treatment of the triazeneyl\u00adidene\u00adphospho\u00adrane complex Cl with hydro\u00adiodic acid, consists of a dicationic six-coordinate IrIII complex, coordinated by a bidentate diazo\u00admethyl\u00adene\u00adphospho\u00adrane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phospho\u00adrus atoms of the chelating dppm are trans to the central carbon atom of the diazo\u00admethyl\u00adene\u00adphospho\u00adrane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The aceto\u00adnitrile solvent mol\u00adecules in 3 are severely disordered in position and occupation. In 4, the I3\u2212 anion is positionally disordered (ratio roughly 1:1), as is the I\u2212 anion with a ratio of 9:1. The di\u00adchloro\u00admethane solvent mol\u00adecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a 1:1 ratio.The structure of [IrCl This substitution reaction results in the formation of a labile IrI inter\u00admediate, whose coordination sphere features the PCN pincer ligand (4-Cl-C6H4N3)C(dppm) and a monodentate dppm  are created by using benzyl azide, rather than 1-azido-4-chloro\u00adbenzene, under an inert atmosphere.In this contribution, we describe the fragmentation of a triazene into diazo and nitrene parts in the coordination sphere of iridium. Recently, we reported on the synthesis of Cl (2) with hydro\u00adiodic acid. It is apparent that a rupture of the N1\u2014N2 bond (numbering as in the structure of 4) of (BnN3)C(dppm) occurred again, resulting in the formation of a diazo\u00admethyl\u00adene\u00adphospho\u00adrane (dppm)C(N2) and a benzyl\u00adnitrene part. However, in this case, the diazo functionality remains unchanged, since in contrast to the formation of 3, no free phosphine functionality is available. The benzyl\u00adnitrene unit again undergoes a 1,2-hydride shift and, as a benzaldimine, coordinates to the Ir metal center.In a related fragmentation reaction, compound 2) moiety contains a central divalent carbon 2)(N2), X = Cl, Br, were obtained by addition of CX4 to P((NMe2)2)(CH(N2)) C ring and one five-membered IrC(dppm) ring. A benzaldimine ligand is positioned trans to the phospho\u00adrus donor of the five-membered ring, the remaining two coordination sites being occupied by chlorido ligands cis to each other. The deviations of the angles C1\u2014Ir1\u2014Cl1 = 170.06\u2005(13)\u00b0 and N3\u2014Ir1\u2014P1 = 169.02\u2005(11)\u00b0 from a regular octa\u00adhedral geometry indicate some strain in the pincer system. Both the N1\u2014C1 bond length [1.280\u2005(5)\u2005\u00c5] and the N1\u2014N2 bond length [1.445\u2005(5)\u2005\u00c5] are typical for a C=N double bond and an N\u2014N single bond, respectively. The P3\u2014N2 bond length [1.586\u2005(4)\u2005\u00c5] is in the range of P=N double bonds observed for imino\u00adphospho\u00adranes \u2005\u00c5] and a previously reported iridium benzaldimine complex [1.260\u2005(6)\u2005\u00c5] involving a phospho\u00adrus donor atom trans to the benzaldimine nitro\u00adgen donor \u2005\u00c5, D\u2014H\u22efA 138\u2005(4)\u00b0], while other intra\u00admolecular inter\u00adactions involve atoms N1 and Cl1 and the various phenyl rings , which forms a five-membered chelate ring via one C and one P donor atom. A four-membered ring is formed by a bidentate dppm ligand and is oriented perpendicular to the plane of the five-membered ring with one phospho\u00adrus donor trans to the carbon donor of the five-membered ring. The benzaldimine ligand is located trans to the phospho\u00adrus donor of the five-membered ring, the sixth coordination site is occupied by an iodido ligand. Deviations from the octa\u00adhedral symmetry around the Ir center are mainly due to the strained four-membered ring [P4\u2014Ir1\u2014P3 = 70.80\u2005(5)\u00b0] with consequences for the bond angles P4\u2014Ir1\u2013I1 [165.12\u2005(4)\u00b0] and C1\u2014Ir1\u2014P3 [170.90\u2005(17)\u00b0]. The C1\u2014Ir1\u2014P1 bond angle of the five-membered ring is 84.37\u2005(17)\u00b0. The environment around the ylidic carbon C1 is trigonal planar, with the bond angle N3\u2014C1\u2014P2 exhibiting the largest deviation from a regular symmetry [114.8\u2005(5)\u00b0]. Both the N3\u2014N2 [1.095\u2005(9)\u2005\u00c5] and the N3\u2014C1 [1.305\u2005(9)\u2005\u00c5] bond lengths are slightly shorter, compared to the corresponding mean values of ten previously reported structures of diazo compounds 2  and [CH(dppm)2]Cl , dissolved in acetone (0.6\u2005ml) and stirred for 3\u2005h. The resulting white precipitate of [IrCl2H(C(dppm)2)]  were added. After stirring for 1\u2005min, the deep-purple solution was stirred for 2\u2005h under atmospheric conditions, resulting in the slow precipitation of a white product. Colourless to pale-yellow prismatic crystals of 3 were obtained by allowing the purple inter\u00admediate solution to stand overnight under ambient conditions.31P{1H}-NMR (CHCl3/MeOH 1:1): \u03b4 = 0.7 ; 16.9 ; 6.9 ; \u221243.1  ppm. 13C{1H}-NMR (CHCl3/MeOH 1:1): \u03b4 =157.9  ppm.Synthesis and crystallization of complex 4: Under an inert atmosphere, a mixture of [IrCl(cod)]2 , [CH(dppm)2]Cl   were added. After heating to 333\u2005K for 15\u2005min, the volatiles were removed in vacuo. The residue was dissolved in CH2Cl2 and hydro\u00adiodic acid  was added whilst stirring. The orange\u2013brown precipitate that formed slowly was separated, washed with water and dried in vacuo. A solution of the residue in CH2Cl2/MeOH 2:1 (0.6\u2005ml) qu\u00adanti\u00adtatively contained an unidentified inter\u00admediate, which transformed to the product within 1\u2005h. Red prismatic crystals of 4 formed within a few hours, when a solution of the inter\u00admediate in CH2Cl2/MeOH (5:1) was kept at 254\u2005K for 24\u2005h and subsequently warmed to room temperature.31P{1H}-NMR (CH2Cl2/MeOH 2:1): \u03b4 = \u221215.8 ; 37.8 ; \u221272.1 ; \u221262.8  ppm. 13C{1H}-NMR (CH2Cl2/MeOH 2:1): \u03b4 = \u22123.0  ppm.3 are severely disordered in position and occupation. At least 5.5 mol\u00adecules in the asymmetric units were refined. Occupation values were varied to give a reasonable isotropic displacement factor. All C- and N-atoms of solvent mol\u00adecules were refined isotropically with bond restraints, the hydrogen atoms were omitted. The proton on N3 was freely refined.Crystal data, data collection and structure refinement details are summarized in Table\u00a044 was found and refined with a bond restraint of 0.87\u2005(2)\u2005\u00c5. The I3\u2212 anion (I4\u2013I6) is positionally disordered (ratio roughly 1:1), as is the I\u2212 anion with a ratio I2:I2A of 9:1. The di\u00adchloro\u00admethane solvent mol\u00adecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a ratio of 1:1. The C and O atoms of methanol were refined isotropically with bond restraints of 1.40\u2005\u00c5. The hydrogen atoms of methanol were calculated, those of di\u00adchloro\u00admethane omitted. All other H atoms were positioned geometrically (C\u2014H = 0.94\u20130.98\u2005\u00c5) and refined as riding with Uiso(H) = 1.2-1.5 Ueq(C).The hydrogen atom at N1 of 10.1107/S2056989019000136/su5470sup1.cifCrystal structure: contains datablock(s) global, 3, 4. DOI: 10.1107/S2056989019000136/su54703sup2.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S2056989019000136/su54704sup3.hklStructure factors: contains datablock(s) 4. DOI: 1885936, 1885935CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "II complex, the axial positions are occupied by a nitro\u00adgen atom from the ligand and an oxygen atom from the sulfate anion, whereas in the CdII complex they contain two nitro\u00adgen atoms from two different ligands and the sulfate anion only serves as the charge-balancing ion. \u03c0\u2013\u03c0 stacking between pyridine rings plays a crucial role in the mol\u00adecular self-assembly of the two structures.The title compounds both contain a central metal atom in a distorted octa\u00adhedral geometry coordinated equatorially by four oxygen atoms from water mol\u00adecules. In the Mn N,N\u2032-bis\u00ad(pyridin-4-yl)pyridine-2,6-dicar\u00adboxamide]\u00adsulfatomanganese(II) dihydrate, [Mn(SO4)(C17H13N5O2)(H2O)4]\u00b72H2O or [Mn(H2L1)(SO4)(H2O)4]\u00b72H2O, (I), and tetra\u00adaqua\u00adbiscadmium(II) sulfate tetra\u00adhydrate, [Cd(C17H13N5O2)2(H2O)4]SO4\u00b74H2O or [Cd(H2O)4(H2L1)2]\u00b7SO4\u00b74H2O, (II), both contain a central metal atom in a distorted octa\u00adhedral geometry coordinated equatorially by four oxygen atoms from water mol\u00adecules. In (I), the axial positions are occupied by a nitro\u00adgen atom from H2L1 and an oxygen atom from the sulfate anion, whereas in (II), the axial positions contain two nitro\u00adgen atoms from two different H2L1 ligands and the sulfate anion acts as the charge-balancing ion. \u03c0\u2013\u03c0 stacking between pyridine rings and a network of hydrogen bonds involving the water molecules and the sulfate anions play a crucial role in the mol\u00adecular self-assembly of the two structures.The molecular structures of tetra\u00adaqua\u00ad[ This bonding feature, when combined with the flexibility and length of mol\u00adecular backbone within these ligands, can lead to the construction of porous coordination compounds -1H-1,2,3-triazol-1-yl] acetic acid (SO4)(H2O)4]\u00b72H2O, (I)2L1)2(H2O)4]SO4\u00b74H2O, (II)N,N\u2032-bis\u00ad(pyridin-4-yl)pyridine-2,6-dicarboxamide (H2L1) as the heterocyclic nitro\u00adgen ligand.In recent years, the design of metal\u2013organic complexes constructed from heterocyclic nitro\u00adgen-derivative ligands has witnessed an upsurge in inter\u00adest due to their fascinating structures and potential applications in luminescence, catal\u00adysis, gas storage and separation (Perry 2L1) acts as a monodentate ligand. The results indicate that the rational design and selection of ligands with heterocyclic nitro\u00adgen systems is an effective synthetic strategy to construct complexes via self-assembly. The asymmetry of the [N,N\u2032-bis\u00ad(pyridin-4-yl)pyridine-2,6-dicarboxamide ligand has resulted in some novel structures PII ion exhibits an octa\u00adhedral geometry, arising from coordination to five water and one sulfate oxygen atoms  and to one nitro\u00adgen (N1) atom of a pyridine group of the H2L1 ligand (Table\u00a01II ion vary from 85.79\u2005(7) to 177.74\u2005(6)\u00b0. Intra\u00admolecular O4\u2014H4\u22efO8, N2\u2014H20\u22efN5 and N3\u2014H24\u22efN5 hydrogen bonds are also present (Table\u00a03The mononuclear complex (I)d Table\u00a01. The Mn\u2014t Table\u00a03.4\u00b7H2O is replaced by CdSO4\u00b78/3H2O, complex (II)C2/c. As illustrated in Fig.\u00a02II also shows an octahedral environment coordinating four oxygen atoms from four water molecules and two axial nitrogen atoms from two symmetry-related H2L1 ligands (Table\u00a02II cation lie in the range 82.63\u2005(14) to 175.09\u2005(10)\u00b0. Intra\u00admolecular N2\u2014H2B\u22efN3 and N4\u2014H4B\u22efN3 hydrogen bonds are also present (Table\u00a04When MnSOs Table\u00a02. In contt Table\u00a04.2L1) acts as a monodentate ligand. The results indicate that the rational design and selection of ligands with heterocyclic nitro\u00adgen systems is an effective synthetic strategy to construct complexes via self-assembly. The asymmetry of the [N,N\u2032-bis\u00ad(pyridin-4-yl)pyridine-2,6-dicarboxamide ligand has resulted in some novel structures. Further study is ongoing.In complexes (I)2L1 ligands play a crucial role in mol\u00adecular self-assembly, with centroid-to-centroid separations of 3.5808\u2005(13) and 3.6269\u2005(14)\u2005\u00c5. In addition, a number of O\u2014H\u22efN and O\u2014H\u22efO hydrogen-bonding inter\u00adactions (Table\u00a03In (I)s Table\u00a03 connect s Table\u00a03.via O\u2014H\u22efN and O\u2014H\u22efO hydrogen-bonding inter\u00adactions (Table\u00a042L1 ligand are important in molecular self-assembly.Complex (II)s Table\u00a04. In (II)et al., 20162L1 skeleton. These include the methyl pyridinium compound of H2L1  was prepared using a modified literature procedure  in N,N\u2032-di\u00admethyl\u00adformamide solution (4\u2005mL) was gradually added to MnSO4.H2O  in a mixed solution . After standing for 5\u2005min, the suspension was filtered and the filtrate was kept at room temperature in the dark. One week later, colourless single crystals suitable for X-ray diffraction were obtained. Complex (II)4.8/3H2O  was used instead of MnSO4.H2O.The heterocyclic nitro\u00adgen ligand (HUiso(H) = 1.2\u20131.5Ueq(C/N/O).Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989018007351/cq2024sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989018007351/cq2024Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018007351/cq2024IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1822492, 1822490CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two chalcones were synthesized in Claisen\u2013Schmidt condensation reactions. In the crystals, \u03c0\u2013\u03c0 inter\u00adactions and weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions are observed. The effect of these inter\u00admolecular inter\u00adactions in the solid state can be seen inthe difference between the experimental and theoretical optimized geometrical parameters. 31H23NO and C35H23NO, were synthesized via Claisen\u2013Schmidt condensation reactions. Both structures were solved and refined using single-crystal X-ray diffraction data and optimized at the ground state using the density functional theory (DFT) method with the B3LYP/6-311++G level. In the crystals, \u03c0\u2013\u03c0 inter\u00adations and weak C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions are observed. The effect of these inter\u00admolecular inter\u00adactions in the solid state can be seen by the difference between the experimental and theoretical optimized geometrical parameters. The structures have also been characterized by UV\u2013Vis spectroscopy. The smallest energy gaps of 2.86 and 2.96\u2005eV enhance the nonlinear responses of such mol\u00adecular systems. Hirshfeld surface analyses and 2D  fingerprint plots were used to qu\u00adantify the inter\u00admolecular inter\u00adactions present in the crystal, indicating that these are the most important contribution to the crystal packing.The title chalcones, C Additionally, the UV\u2013vis absorption and Hirshfeld surface analyses are discussed.Chalcones satisfy the criteria of three features essential for high nonlinear activity in an organic compound, which are: a strong electron donor, a highly polarizable \u03c0-conjugated bridge and a strong \u03c0-electron acceptor. A chalcone mol\u00adecule with a \u03c0-conjugated system provides a large charge-transfer axis with appropriate substituent groups on the terminal aromatic rings. Polyaromatic hydro\u00adcarbons or \u03c0-conjugated materials such as anthracenyl chalcone provide the significant property for conductivity that led to tremendous advances in the field of organic electronics . The C\u2014C distances in the central ring of the anthracene units show a little variations compared to the other rings , which are much shorter. These observations are consistent with an electronic structure for the anthracene units where a central ring displaying aromatic delocalization is flanked by two isolated diene units \u2005\u00c5 and DFT = 1.22\u2005\u00c5 in I; Exp = 1.213\u2005(3) (A) and 1.218\u2005(3)\u2005\u00c5 (B), and DFT\u00a0= 1.22\u2005\u00c5 in II] and C16=C17 . Both I and II (A and B) are twisted at the C14\u2014C15 bond, with C1\u2014C14\u2014C15\u2014C16 torsion angles of \u221292.6\u2005(2) (in I), 84.8\u2005(3) (in IIA) and 106.3\u2005(3)\u00b0 (in IIB). The corresponding torsion angles for DFT are \u221285.84 and 85.63\u00b0, respectively. Additionally, in compound II, rings Y and Z (A) and rings Y\u2032 and Z\u2032 (B) are also twisted at the C21\u2014N1 bond, with C20\u2014C21\u2014N1\u2014C24 torsion angles of Exp = 64.1\u2005(4)\u00b0 (A) and 46.2\u2005(4)\u00b0 (B), and DFT = 55.03\u00b0. The large twist angles are due to the bulkiness of the strong electron-donor anthracene ring system and substituent ring system \u00b0 and DFT\u00a0= \u22121.38 for compound I, and Exp = \u2212171.2\u2005(3)\u00b0 (A) and 11.4\u2005(5)\u00b0 (B), and DFT = \u22121.70\u00b0 for compound II. The slight differences in the torsion angles between the experimental and DFT results in both compounds are due to the formation of inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions involving all the fused-ring systems, which are not taken into consideration during the optimization process \u2005\u00c5 at atom C16] makes dihedral angles of 86.93\u2005(19) and 21.21\u2005(19)\u00b0 with the anthracene ring [maximum deviation = 0.0117\u2005(19)\u2005\u00c5 at C9] and ring X [maximum deviation = 0.0363\u2005(18)\u2005\u00c5 at C29], respectively. In compound II, the enone moiety  for mol\u00adecule A forms dihedral angles of 84.76\u2005(17), 87.61\u2005(17) and 72.35\u2005(17)\u00b0 with the anthracene ring [maximum deviation = 0.029\u2005(3)\u2005\u00c5 at C14A], ring Y [maximum deviation = 0.008\u2005(3)\u2005\u00c5 at C19A] and ring Z [maximum deviation = 0.043\u2005(3)\u2005\u00c5 at C34A], respectively. The anthracene ring forms dihedral angles of 89.63\u2005(11) and 62.11\u2005(7)\u00b0 with rings Y and Z, respectively, and the dihedral angle between rings Y and Z is 61.73\u2005(10)\u00b0. In addition, for mol\u00adecule B, the enone moiety  forms dihedral angles of 72.2\u2005(3), 13.5\u2005(3) and 87.2\u2005(3)\u00b0 with the anthracene ring [maximum deviation = 0.018\u2005(4)\u2005\u00c5 at C10B], ring Y\u2032 [maximum deviation = 0.010\u2005(3)\u2005\u00c5 at C20B] and ring Z\u2032 [maximum deviation = 1.441\u2005(2)\u2005\u00c5 at N1B], respectively. The anthracene ring forms dihedral angles of 61.46\u2005(11) and 54.80\u2005(7)\u00b0 with rings Y\u2032 and Z\u2032, respectively, and the dihedral angle between rings Y\u2032 and Z\u2032 is 48.92\u2005(11)\u00b0.The enone moiety in I shows weak \u03c0\u2013\u03c0 inter\u00adactions  involving Cg1\u22efCg5 = 3.7267\u2005(11)\u2005\u00c5 , Cg2\u22efCg4 = 3.6669\u2005(12)\u2005\u00c5 , Cg3\u22efCg3 = 3.6585\u2005(11)\u2005\u00c5  and Cg4\u22efCg4 = 3.6790\u2005(12)\u2005\u00c5 , where Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of rings N1/C20/C21/C26/C27, C1\u2013C6, C1/C6\u2013C8/C13/C14, C8\u2013C13, C18\u2013C20/C27-C29, respectively. The packing is further linked into an infinite three-dimensional supra\u00admolecular network.The crystal packing of ns Fig.\u00a02a involvII  shows weak C12B\u2014H12B\u22efO1 inter\u00admolecular hydrogen bonds connecting the mol\u00adecules into an infinite one-dimensional chain along the c axis. In addition, weak inter\u00admolecular C5B\u2014H5BA\u22efCg6, C27B\u2014H27B\u22efCg7, C28B\u2014H28B\u22efCg8, C11A\u2014H11A\u22efCg9 and C7B\u2014H7B\u22efCg10 inter\u00adactions are also observed in the crystal packing and further stabilize the crystal structure, where Cg6, Cg7, Cg8, Cg9 and Cg10 are the centroids of rings N1A/C24A/C29A/C30A/C35A, C1A\u2013C6A, C1A/C6A\u2013C8A/C13A/C14A, C18A\u2013C23A and C24A\u2013C29A, respectively. These weak inter\u00admolecular C\u2014H\u22efO and C\u2014H\u22ef\u03c0 inter\u00adactions bridge the mol\u00adecules into an infinite one-dimensional column along the c axis.Lists of weak hydrogen-bond inter\u00admolecular inter\u00adactions are shown in Table\u00a01II Fig.\u00a01b shows I and II have been calculated using time-dependent DFT at the B3LYP/6-311++G level in the gas phase and give values of 396 (I) and 383\u2005nm (II). The absorption characteristics of I and II are observed in the UV region at 393 and 388\u2005nm, as shown in Fig.\u00a03et al., 2017The electronic absorption spectra of I and II, respectively. Through an extrapolation of the linear trend observed in the optical spectra, the experimental energy band gaps in I and II are 2.86 and 2.96\u2005eV, respectively. These optical band-gap values indicate the suitability of this compound for optoelectronic applications, as was also reported previously for a chalcone structure by Tejkiran et al.  energy levels of the title compounds, the corresponding electronic transfer are found to happen between the HOMO and LUMO orbitals, as shown in Fig.\u00a04 al. 2016. In addi al. 2016 studied CrystalExplorer  show the HS mapped over dnorm, where the red spots indicate the regions of donor\u2013acceptor inter\u00adactions. The C\u2014H\u22efO contacts are only present in compound II. In addition, the presence of C\u2014H\u22ef\u03c0 inter\u00adactions only occurs in compound II, indicated through a combination of pale-orange bright-red spots which are present on the HS mapped over shape index surface, identified with black arrows . The large flat region delineated by a blue outline refers to the \u03c0\u2013\u03c0 stacking inter\u00adactions. The curved nature of the compound reveals that \u03c0\u2013\u03c0 stacking inter\u00adactions are present in compound I. Meanwhile, these inter\u00adactions are absent in compound II.The program ws Fig.\u00a05b. The lII. Meanwhile, there is no spike in the fingerprint of compound I. The 7.5% O\u22efH contribution shown in compound I is the average percentage interaction from the total interactions presence in I. In compound I, there are no interactions other than the \u03c0\u2013\u03c0 interactions, which makes the percentage of the O\u22efH contribution is slightly higher. Hence, a discussion on the percentage difference between I. and II. is invalid. The significant C\u2014H\u22ef\u03c0 inter\u00adactions for compound II are indicated by the wings de + di \u223c 2.6\u2005\u00c5.The fingerprint plot shown in Fig.\u00a06et al., 2016I and II. There are four compounds which have an anthrancene ketone subtituent on the chalcone, including 9-anthryl styryl ketone and 9,10-anthryl bis\u00ad(styryl ketone) reported by Harlow et al. (1975E)-1-(Anthracen-9-yl)-3-[4-(propan-2-yl)phen\u00adyl]prop-2-en-1-one was reported by Girisha et al. (2016E)-1-(anthracen-9-yl)-3-(2-chloro-6-fluoro\u00adphen\u00adyl)prop-2-en-1-one was reported by Abdullah et al. -1,3-bis\u00ad(anthracen-9-yl)prop-2-en-1-one. Other related compounds include 1-(anthracen-9-yl)-2-methyl\u00adprop-2-en-1-one -1-(anthracen-9-yl)-3-[4-(piperidin-1-yl)phen\u00adyl]prop-2-en-1-one and (E)-1-(anthracen-9-yl)-3-[4-(di\u00adphenyl\u00adamino)\u00adphen\u00adyl]prop-2-en-1-one -1- al. 2016, while benzaldehyde (0.5\u2005mmol) for compounds I and II, respectively, was dissolved in methanol (20\u2005ml). A catalytic amount of NaOH  was added to the solution dropwise under vigorous stirring. The reaction mixture was stirred for about 5\u20136\u2005h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50\u2005ml). The resultant crude products were filtered, washed successively with distilled water and recrystallized from acetone to give the corresponding chalcones (Scheme 1). Single crystals of I and II suitable for X-ray diffraction were obtained by slow evaporation from acetone solutions.A mixture of 9-acetyl\u00adanthrancene (0.5\u2005mmol) and 9-ethylcarbazole-3-carbaldehyde (0.5\u2005mmol) and 4- and refined using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating group model was applied to the methyl group in I.Crystal data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018011131/lh5878sup1.cifCrystal structure: contains datablock(s) mo_DA20_0m, mo_DA21e_0m, global. DOI: 10.1107/S2056989018011131/lh5878mo_DA20_0msup2.hklStructure factors: contains datablock(s) mo_DA20_0m. DOI: Click here for additional data file.10.1107/S2056989018011131/lh5878mo_DA20_0msup4.cmlSupporting information file. DOI: 10.1107/S2056989018011131/lh5878mo_DA21e_0msup3.hklStructure factors: contains datablock(s) mo_DA21e_0m. DOI: 10.1107/S2056989018011131/lh5878sup5.pdfSupporting information file. DOI: 1827021, 1827019CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The crystal structures of two multidentate CMPO-containing organic ligands are described. Both compounds feature N\u2014H\u22efO hydrogen bonds in the solid state. 36H34N2O4P2, (I), and diethyl [({2-[2-(di\u00adeth\u00adoxy\u00adphosphino\u00adyl)ethanamido]\u00adeth\u00adyl}carbamo\u00adyl)meth\u00adyl]phospho\u00adnate, C14H30N2O8P2, (II), were synthesized via nucleophilic acyl substitution reactions between an ester and a primary amine. Hydrogen-bonding inter\u00adactions are present in both crystals, but these inter\u00adactions are intra\u00admolecular in the case of compound (I) and inter\u00admolecular in compound (II). Intra\u00admolecular \u03c0\u2013\u03c0 stacking inter\u00adactions are also present in the crystal of compound (I) with a centroid\u2013centroid distance of 3.9479\u2005(12)\u2005\u00c5 and a dihedral angle of 9.56\u2005(12)\u00b0. Inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions  give rise to supra\u00admolecular sheets that lie in the ab plane. Key geometric features for compound (I) involve a nearly planar, trans-amide group with a C\u2014N\u2014C\u2014C torsion angle of 169.12\u2005(17)\u00b0, and a torsion angle of \u2212108.39\u2005(15)\u00b0 between the phosphine oxide phospho\u00adrus atom and the amide nitro\u00adgen atom. For compound (II), the electron density corresponding to the phosphoryl group was disordered, and was modeled as two parts with a 0.7387\u2005(19):0.2613\u2005(19) occupancy ratio. Compound (II) also boasts a trans-amide group that approaches planarity with a C\u2014N\u2014C\u2014C torsion angle of \u2212176.50\u2005(16)\u00b0. The hydrogen bonds in this structure are inter\u00admolecular, with a D\u22efA distance of 2.883\u2005(2)\u2005\u00c5 and a D\u2014H\u22efA angle of 175.0\u2005(18)\u00b0 between the amide hydrogen atom and the P=O oxygen atom. These non-covalent inter\u00adactions create ribbons that run along the b-axis direction.Two bis-carbamoyl\u00admethyl\u00adphosphine oxide compounds, namely {[(3-{[2-(di\u00adphen\u00adyl\u00adphosphino\u00adyl)ethanamido]\u00admeth\u00adyl}benz\u00adyl)carbamo\u00adyl]meth\u00adyl}di\u00adphenyl\u00adphos\u00adphine oxide, C Many researchers have attempted to mimic this solution stoichiometry by tethering two, three or four CMPO groups together via an organic scaffold 1H, 13C, and 31P NMR spectroscopy, and by X-ray crystallography.The carbamoyl\u00admethyl\u00adphosphine oxide (CMPO) moiety has found use as the chelating portion of a ligand in the TRUEX process for the remediation of nuclear waste 4 descriptor for fourfold coordination around the phospho\u00adrus atom P1 is 0.95, indicating a nearly perfect tetra\u00adhedral geometry of the phosphine oxide group \u00b0, and is staggered with respect to the plane of the C4\u2013C7 aromatic ring with a H1\u2014N1\u2014C3\u2014C4 torsion angle of 59.1\u2005(17)\u00b0.The structure of compound (I)x\u00a0+\u00a01, y, \u2212z\u00a0+\u00a0D\u22efA distance of 2.940\u2005(2)\u2005\u00c5 and a D\u2014H\u22efA angle of 168\u2005(2)\u00b0 )\u00b0 Fig.\u00a03. The C14Pbca. Since the mol\u00adecule lies on an inversion center , the asymmetric unit comprises one half of the mol\u00adecule. The electron density corresponding to the atoms of the phosphoryl group was disordered and was modeled over two positions with a 0.7387\u2005(19):0.2613\u2005(19) occupancy ratio (see the Refinement section for more details). The complete mol\u00adecular structure of the major component of compound (II)4 descriptor for fourfold coordination around the phospho\u00adrus atom of the major component, P1, is 0.93, indicating that the geometry of the phosphoryl group is slightly distorted from an ideal tetra\u00adhedron. The geometry between the amide nitro\u00adgen atom N1 and the \u03b2-phosphoryl group phospho\u00adrus atom P1 is defined by a N1\u2014C1\u2014C2\u2014P1 torsion angle of \u2212111.8\u2005(2)\u00b0. The amide group of this compound also adopts a nearly perfect trans geometry with a C3\u2014N1\u2014C1\u2014C2 torsion angle of \u2212176.50\u2005(16)\u00b0.Compound (II)A  with a C\u22efcentroid distance of 3.622\u2005(2)\u2005\u00c5 and a C\u2014H\u22efcentroid angle of 146\u00b0. These non-covalent inter\u00adactions create supra\u00admolecular sheets of compound (I)ab plane ne Fig.\u00a04.x\u00a0+\u00a0y\u00a0+\u00a0z\u00a0+\u00a01; Fig.\u00a05D\u22efA distance of 2.883\u2005(2)\u2005\u00c5 with a D\u2014H\u22efA angle of 175.0\u2005(18)\u00b0. This hydrogen bond forms ribbons of compound (I)b-axis direction on Fig.\u00a06.et al., 2016via an organic scaffold. The most similar structures to compound (I)et al., 2014et al., 2006via inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions. A structure closely related to compound (II)et al., 20023)3 has been reported in this journal  1,3-Bis(amino\u00admeth\u00adyl)benzene  and the p-nitro\u00adphenyl ester of di\u00adphenyl\u00adphosphono\u00adacetate  and the solution was stirred for 3.5\u2005h. The organic layer was separated, washed with brine (3 \u00d7 10\u2005mL), dried over solid magnesium sulfate and concentrated under reduced pressure. The crude product was triturated multiple times with ethyl acetate to give a white solid in 91% yield. X-ray quality crystals of compound (I)1H NMR : \u03b4 7.91 , 7.7\u20137.3 , 7.1\u20136.8 , 4.24 , 3.36 ; 13C NMR : \u03b4 164.7 , 138.3, 132.5, 131.9, 131.2\u2013130.5 (broad), 129.5\u2013128.3 (broad), 126.9\u2013126.1 (broad), 43.5, 38.6; 31P NMR : \u03b4 30.6.Compound (II) Ethyl\u00adene di\u00adamine  was dissolved in 8.3\u2005mL of methanol. The solution was cooled to 195\u2005K, and triethyl phosphono\u00adacetate  was added dropwise. The reaction mixture was allowed to warm to room temperature and stirred overnight. The product precipitated from the solution, was isolated by vacuum filtration and rinsed with ethyl acetate. Some of this solid was crystalline and suitable for analysis by X-ray diffraction. The remainder of the isolated product was purified by silica gel chromatography (10:1 di\u00adchloro\u00admethane\u2013methanol) to give compound (II)1H NMR : \u03b4 7.75 , 4.15 , 3.34 , 2.85 , 1.33 ; 13C NMR : \u03b4 165.4, 62.9, 35.8 , 16.5; 31P NMR : \u03b4 24.5.Uiso(H) = 1.2Ueq(C) for methyl\u00adene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups. For both compounds (I)SHELXL  were treated with SAME and EADP commands to produce bond lengths and angles that agree with known values, and to ensure physically reasonable displacement parameters.Crystal data, data collection and structure refinement details for both compounds are summarized in Table\u00a0310.1107/S205698901900820X/pk2617sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S205698901900820X/pk2617Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900820X/pk2617Isup4.cmlSupporting information file. DOI: 10.1107/S205698901900820X/pk2617IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S205698901900820X/pk2617IIsup5.cmlSupporting information file. DOI: 1921486, 1921485CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "In the crystal structure of the title compound, two half-mol\u00adecules are found in the asymmetric unit. The completed mol\u00adecules differ only slightly in bond lengths and torsion angles. 14H14N2S2, was obtained by transmetallation of 2,2\u2032-bis\u00ad(tri\u00admethyl\u00adstann\u00adyl)azo\u00adbenzene with methyl lithium, and subsequent quenching with dimethyl di\u00adsulfide. The asymmetric unit comprises two half-mol\u00adecules, the other halves being completed by inversion symmetry at the midpoint of the azo group. The two mol\u00adecules show only slight differences with respect to N=N, S\u2014N and aromatic C=C bonds or angles. Hirshfeld surface analysis reveals that except for one weak H\u22efS inter\u00adaction, inter\u00admolecular inter\u00adactions are dominated by van der Waals forces only.The title compound, C Azo\u00adbenzenes are common motifs in dyes because of their high thermal and photochemical stability 2, (I)The mol\u00adecular switch azo\u00adbenzene can undergo isomerization from its thermodynamically stable Ia and Ib), the other halves being completed by application of inversion symmetry. The midpoints of the N=N bonds are located on inversion centres, resulting in a trans-configuration for the central N=N bonds  \u2212x, 1\u00a0\u2212\u00a0y, \u2212z; (ii) 1\u00a0\u2212\u00a0x, 1\u00a0\u2212\u00a0y, 1\u00a0\u2212\u00a0z] torsion angles of 13.2\u2005(2) and \u22125.3\u2005(2)\u00b0, respectively, in both mol\u00adecules the phenyl rings are twisted slightly with respect to the azo unit. A weak distortion is also found for the N1\u2014C1\u2014C2\u2014S1 torsion angles of \u22123.06\u2005(16)\u00b0 for Ia and \u22122.06\u2005(15)\u00b0 for Ib. The N=N bond lengths differ marginally , as do comparable C\u2014C bonds. For example, the C1\u2014C2 bond in Ia is at 1.408\u2005(2)\u2005\u00c5 slightly shorter than Ib [1.415\u2005(2)\u2005\u00c5]. In comparison, this bond is longer than all other C\u2014C distances in the ring because of repulsion of the nitro\u00adgen and the sulfur atoms attached to C1 and C2, respectively. In both mol\u00adecules, the S\u22efN distances  are too long to be considered as attractive inter\u00adactions. Fig.\u00a02The asymmetric unit of the title compound consists of two half-mol\u00adecules  = 3.7525\u2005(8)\u2005\u00c5 with a slippage of 1.422\u2005\u00c5. To further investigate the inter\u00admolecular inter\u00adactions, Hirshfeld surfaces  of another mol\u00adecule of Ib (S\u22efH distance = 2.811\u2005\u00c5). The two-dimensional fingerprint plots for mol\u00adecule Ib for qu\u00adanti\u00adfication of the contributions of each type of non-covalent inter\u00adaction to the Hirshfeld surface azo\u00adbenzene was recently described  was purchased from Acros Organics. THF was purchased from VWR and was dried and degassed with a solvent purification system by Inert Technology.The synthesis of 2,2\u2032- al. 2015. Dimethy2,2\u2032-bis\u00ad(Methyl\u00adthio)\u00adazo\u00adbenzenebis(tri\u00admethyl\u00adstann\u00adyl)azo\u00adbenzene  was dissolved under Schlenk conditions in THF (12.5\u2005ml) and cooled to 195\u2005K. Then MeLi  was added within 5\u2005min and after 1.5\u2005h at this temperature, dimethyl di\u00adsulfide  was added in one ration. The reaction mixture was warmed to 298\u2005K over 14\u2005h and the solvent was removed under reduced pressure. The obtained orange solid was purified in a silica column  with a gradient of eluents from n-pentane to di\u00adchloro\u00admethane giving dark-orange crystals . Single crystals suitable for X-ray analysis were obtained by slow evaporation from a saturated n-heptane solution.In an inert reaction tube, 2,2-1H NMR : \u03b4 = 7.76 , 7.40 , 7.32 , 7.20 , 2.53  ppm.13C{1H} NMR : \u03b4 = 149.08 (C1), 141.00 (C2), 131.56 (C4), 124.81 (C3), 124.75 (C5), 118.02 (C6), 15.02 (C7) ppm.HRMS : m/z: calculated for C14H14N2S2+ 274.05929 found 274.05944.MS (EI): m/z 273.9 (5%) [M]+, 258.9 (100%) [M\u00a0\u2212\u00a0CH3]+, 243.9 (5%) [M\u00a0\u2212\u00a0C2H6]+, 107.9 (13%) [M\u00a0\u2212\u00a0C8H10N2S]+.IR (ATR): \u03bd = 3059 (w), 2986 (w), 2961 (w), 2918 (w), 2852 (w), 1575 (m), 1561 (w), 1457 (m), 1433 (s), 1298 (w), 1249 (w), 1217 (m), 1162 (m), 1065 (s), 1035 (m), 951 (m), 863 (w), 803 (w), 761 (s), 726 (s), 674 (s) cm\u22121.M.p.: 429\u2005KRf: (n-penta\u00adne: di\u00adchloro\u00admethane 3:1): 0.55.Uiso(H) = 1.5Ueq (C-meth\u00adyl) and 1.2Ueq(C) (C-phen\u00adyl).Crystal data, data collection and structure refinement details are summarized in Table\u00a0110.1107/S2056989019014592/wm5522sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019014592/wm5522Isup2.hklStructure factors: contains datablock(s) I. DOI: 1961741, 1961741CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "N\u2032,N\u2032\u2032\u2032--{[methyl\u00adenebis(\u00adoxy)]bis\u00ad}bis\u00ad(methane\u00adylyl\u00adidene))bis\u00ad(isonicotinohydrazide) dihydrate, (I), and N\u2032,N\u2032\u2032\u2032--{bis\u00ad}bis\u00ad(methane\u00adylyl\u00adidene))bis\u00ad(isonicotinohydrazide), (II), both crystallized with half a mol\u00adecule in the asymmetric unit. The whole mol\u00adecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bis\u00adecting the C atom of the \u2013O\u2014CH2\u2014O\u2013 bridge. The whole mol\u00adecule of (II) is generated by inversion symmetry, with the central CH2\u2014CH2 bond of the \u2013O\u2014(CH2)4\u2014O\u2013 bridge being located about a center of inversion.The title compounds,  27H20Br2N6O4\u00b72H2O, (I), and C30H28N6O4\u00b7[+ solvent], (II), both crystallize with one half-mol\u00adecule in the asymmetric unit. The whole mol\u00adecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bis\u00adecting the C atom of the \u2013O\u2014CH2\u2014O\u2013 bridge. This results in a folded or U-shaped conformation of the mol\u00adecule. The whole mol\u00adecule of (II) is generated by inversion symmetry, with the central CH2\u2014CH2 bond of the \u2013O\u2014(CH2)4\u2014O\u2013 bridge being located about a center of inversion. This results in a step-like conformation of the mol\u00adecule. The central C(=O)N\u2014N=C regions of the isonicotinohydrazide moieties in both compounds are planar and the configuration about the imine C=N bonds is E. In compound (I), the benzene and pyridine rings are inclined to each other by 37.60\u2005(6)\u00b0. The two symmetry-related pyridine rings are inclined to each other by 74.24\u2005(6)\u00b0, and the two symmetry-related benzene rings by 7.69\u2005(6)\u00b0. In compound (II), the benzene and pyridine rings are inclined to each other by 25.56\u2005(11)\u00b0. The symmetry-related pyridine rings are parallel, as are the two symmetry-related benzene rings. In the crystal of (I), a pair of water mol\u00adecules link the organic mol\u00adecules via Owater\u2014H\u22efO and Owater\u2014H\u22efN hydrogen bonds, forming chains along [001], and enclosing an R42(8) and two R12(5) ring motifs. The chains are linked by N\u2014H\u22efNpyridine hydrogen bonds, forming a supra\u00admolecular framework. There are also a number of C\u2014H\u22efO hydrogen bonds, and C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adplanar distance = 3.294\u2005(1)\u2005\u00c5] present reinforcing the framework. In the crystal of (II), mol\u00adecules are linked by N\u2014H\u22efNpyridine hydrogen bonds, forming a supra\u00admolecular framework. Here too there are also a number of C\u2014H\u22efO hydrogen bonds present, and a C\u2014H\u22ef\u03c0 inter\u00adaction, reinforcing the framework. For compound (II), a region of disordered electron density was corrected for using the SQUEEZE [Spek (2015PLATON. Their formula mass and unit-cell characteristics were not taken into account during refinement.The title compounds, CSpek 2015. Acta Cr The C6\u2014N2 and C7=N3 bond lengths differ by 0.068\u2005(2)\u2005\u00c5 in (I)et al., 2013et al., 2013et al., 2010The bond lengths and angles in the carbohydrazide group of the title compounds can be compared with the values reported for related structures \u2005\u00c5] present, reinforcing the framework  is 3.766\u2005(1)\u2005\u00c5, \u03b1 = 0.00\u2005(6)\u00b0, \u03b2 = 29\u00b0, inter\u00adplanar distance = 3.294\u2005(1)\u2005\u00c5, offset of 1.824\u2005\u00c5.In the crystal of (I)s Table\u00a03. The chak Table\u00a03. The offpyridine hydrogen bonds, forming a supra\u00admolecular framework k Table\u00a04. Here tok Table\u00a04, reinfor3 with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON et al., 2007CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of \u22120.512 (red) to 1.285 (blue) for compound (I)SQUEEZED out).The Hirshfeld surfaces of compounds (I)b), O\u22efH/H\u22efO at 13.8% , N\u22efH/H\u22efN at 11.3% , Br\u22efH/H\u22efBr at 14.3%  and C\u22efH/H\u22efC contacts at 13.6% . C\u22efC contacts account for 8.4%, while C\u22efBr are 3.0%, C\u22efN are 3.0%, and finally C\u22efO contacts amount to 1.4%.The fingerprint plots are given in Figs. 98% Fig.\u00a09c, N\u22efH/H3% Fig.\u00a09d, Br\u22efH/3% Fig.\u00a09e and C\u22ef6% Fig.\u00a09f. C\u22efC cb), O\u22efH/H\u22efO at 13.3% , N\u22efH/H\u22efN at 16.2% , and C\u22efH/H\u22efC at 33.6% . The remaining contacts are extremely weak, ca 1% each.For compound (II)% Fig.\u00a010c, N\u22efH/H% Fig.\u00a010d, and C% Fig.\u00a010e. The ret al., 2016i.e. (3-OR-benzyl\u00adidene)isonicotinohydrazide (R = C) skeleton gave 51 hits (supporting information file S1). The majority of these compounds were with an OMe or an OEt substituent.A search of the Cambridge Structural Database isonicotinohydrazide (R = C) skeleton gave 23 hits (supporting information file S2). Again, the majority of these compounds have an OMe or an OEt substituent. However, here the most inter\u00adesting and relevant compound concerns the ligand N\u2032,N\u2032\u2032-bis\u00ad(pyridine-4-carbohydrazide), in which a 1,2-di\u00adoxy\u00adethane bridge links two N\u2032-benzyl\u00adideneisonicotinohydrazide units. The crystal structures of two polymorphs have been described: a monoclinic P21 polymorph that crystallizes as a methanol disolvate ] bis(pyridine-4-carbohydrazide)})tetra\u00adkis\u00ad(iodo)\u00addimercury meth\u00adanol disolvate , in a 250\u2005ml round-bottom (RB) flask was added DMF (30\u2005ml) and potassium carbonate (12.5\u2005mmol). The mixture was stirred at room temperature and then 1,1-di\u00adiodo\u00adbutane (2.5\u2005mmol) was added dropwise and the reaction mixture was stirred for 12\u2005h. It was then partitioned between water and ethyl acetate. The ethyl acetate layer was collected and concentrated under reduced pressure. To 1,4-bis\u00adbutane (2\u2005mmol) and isonicotinic acid hydrazide (4\u2005mmol) in a 250\u2005ml RB flask was added 100\u2005ml of methanol and two drops of glacial acetic acid. The reaction mixture was stirred at room temperature and within 5\u2005min a white-coloured product had formed. The reaction was continued for a further 30\u2005min. The title compound was isolated by filtration and washed with methanol, then chloro\u00adform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (I)Compound I: To 5-bromo-2-hy\u00addroxy\u00adbenzaldehyde (5\u2005mmol), in a 250\u2005ml RB flask, was added 50\u2005ml of DMF and potassium carbonate (12.5\u2005mmol). The mixture was stirred at room temperature and then 1,1-di\u00adiodo\u00admethane (2.5\u2005mmol) was added dropwise. Then, the reaction mixture was stirred for 12\u2005h. The product obtained was extracted in ethyl acetate medium. Methanol (100\u2005ml) and two drops of glacial acetic acid were added to a mixture of 6,6\u2032-[methyl\u00adenebis(\u00adoxy)] bis\u00ad (2\u2005mmol) and isoniazid (4\u2005mmol) in a 250\u2005ml RB flask. The reaction mixture was stirred at room temperature and within 5\u2005min a white-coloured product had formed and the reaction was continued for a further 30\u2005min. The solid obtained was washed with methanol, then chloro\u00adform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (II)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a053 with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON 10.1107/S2056989019005048/su5495sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989019005048/su5495Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019005048/su5495IIsup5.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019005048/su5495Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019005048/su5495IIsup5.cmlSupporting information file. DOI: 10.1107/S2056989019005048/su5495sup6.pdfCSD search S1. DOI: 10.1107/S2056989019005048/su5495sup7.pdfCSD Search S2. DOI: 1907912, 1907913CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III atoms in the title structure have distorted octa\u00adhedral coordination spheres, being C,N-chelated by two main 2-phenyl\u00adpyridine ligands and N,O-chelated by one ancillary 2-[\u00admeth\u00adyl]phenolato ligand.The two Ir 11H8N)2(C15H14NO3)]\u00b72CH2Cl2, consists of two complex mol\u00adecules together with four di\u00adchloro\u00admethane solvent mol\u00adecules, one of which is disordered. In each complex mol\u00adecule, the IrIII ion has a distorted octa\u00adhedral coordination environment defined by two 2-phenyl\u00adpyridine ligands, through two phenyl C and two pyridine N atoms, and by one N,O-bidentate 2-[\u00admeth\u00adyl]phenolate anion. The IrIII ions lie almost in the equatorial planes with deviations of 0.0396\u2005(17) and 0.0237\u2005(17)\u2005\u00c5, respectively, for the two complex mol\u00adecules. In both complex mol\u00adecules, the two 2-phenyl\u00adpyridine ligands are nearly perpendicular to each other [dihedral angles between the least-squares-planes of 89.91\u2005(11) and 85.13\u2005(11)\u00b0]. In the crystal, inter\u00admolecular C\u2014H\u22efO inter\u00adactions as well as inter\u00admolecular C\u2014H\u22ef\u03c0 inter\u00adactions are present, leading to a three-dimensional network structure. One of the four dichlormethane solvent mol\u00adecules shows disorder over two sets of sites [occupancy ratio 0.79\u2005(2):0.21\u2005(2)].The asymmetric unit of the solvated title complex, [Ir(C The equatorial plane is formed by atoms O4/C49/C38/N6. The mean deviation from the least-squares plane is 0.055\u2005\u00c5 and the Ir2III ion is displaced by 0.0237\u2005(17)\u2005\u00c5 from the equatorial plane towards the axial N4 atom. The deviation from a perpendicular arrangement of the two 2-phenyl\u00adpyridine ligands is slightly higher than in complex 1 [the dihedral angle between the least-squares planes is 85.13\u2005(11)\u00b0], likewise the deviation from planarity with dihedral angles of 1.69\u2005(13)\u00b0 (between rings C49\u2013C54 and N5\u2013C59) and 3.36\u2005(13)\u00b0 (between rings C38\u2013C43 and N4\u2013C48), respectively.In complex mol\u00adecule 2 (Ir2), a similar bonding situation is observed, with the phenyl C atoms C38 and C49 Cg1 and H50 with Cg2 .The configurations in both complexes are stabilised by intra\u00admolecular C\u2014H\u22efO inter\u00adactions between the phenolic O1 and O4 atoms as acceptors and the phenyl C1\u2014H1 and C48\u2014H48 groups as donors Fig.\u00a01, as welle.g. for {(E)-2-[\u00admeth\u00adyl]phen\u00ado\u00adlato-\u03ba2N,O}bis\u00adiridium(III) -2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolato-\u03ba2N,O}bisiridium(III) -2-[(phenyl\u00adimino)\u00admeth\u00adyl]phenolato-\u03ba2N,O}bis\u00adiridium(III) , although the title compound is very similar to a previously reported compound  into a di\u00adchloro\u00admethane (5\u2005mL) solution of the title compound  at room temperature.The title compound was prepared according to a reported procedure (Goo sp2\u2014H and 0.99\u2005\u00c5 for methyl\u00adene C\u2014H with Uiso(H) = 1.2Ueq(C); C\u2014H = 0.98\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms. One of the four dichloro\u00admethane solvent mol\u00adecules shows disorder over two sets of sites [occupancy ratio 0.79\u2005(2):0.21\u2005(2)].Crystal data, data collection and structure refinement details are summarized in Table\u00a0310.1107/S2056989018009970/wm5449sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009970/wm5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 1846724CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "III{C(dppm)2-\u03ba3P,C,P\u2032}ClH(NH3C2)]Cl with ethyl diazo\u00adacetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, and reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodi\u00adphospho\u00adrane system to a phospho\u00adrus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand.The reaction of Cl with ethyl diazo\u00adacetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodi\u00adphospho\u00adrane system to a phospho\u00adrus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The phospho\u00adrus electron-donor atoms and the ylide carbon atom of the resulting (CF3O3S)2 complex, also termed as [bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane]({[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methanyl\u00adidene-\u03ba3P,C,O)hydridoiridium(III) bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonate), are in plane and the hydrido ligand and the carbonyl O atom are located trans to each other, perpendicular to the meridional plane. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand, thereby creating [bis\u00ad(di\u00adphenyl\u00adphosphan\u00adyl)methane]\u00adcarbon\u00adyl({[(di\u00adphenyl\u00adphosphan\u00adyl)meth\u00adyl]di\u00adphenyl\u00adphosphanyl\u00adidene}(eth\u00adoxy\u00adoxoethanyl\u00adidene)methanyl\u00adidene-\u03ba2P,C}hydridoiridium(III) bis\u00ad(tri\u00adfluoro\u00admethane\u00adsulfonate)\u2013di\u00adchloro\u00admethane\u2013ethyl acetate (6/2/3) or, more simply, (CF3O3S)2\u00b70.33CH2Cl2\u00b70.5C4H8O2. One tri\u00adfluoro\u00admeth\u00adane\u00adsulfonate counter-ion of 3 shows positional disorder in a 2:1 ratio. Complex 4 shows pseudo-merohedral twinning (matrix: The reaction of [Ir Addition of ethyl diazo\u00adacetate (EDA) to Cl complex 1 (Scheme 1) leads to a carbon\u2013carbon coupling reaction via extrusion of a dppm subunit, which is stabilized by two phospho\u00adrus\u2013iridium(III) electron donor\u2013acceptor inter\u00adactions under the formation of a four-membered chelate ring. This reaction sequence, produced by the inter\u00adaction of the doubly ylidic carbon atom with an electrophile containing the extraordinarily good di\u00adnitro\u00adgen withdrawing group, may be described as Wittig-type carbon\u2013carbon coupling reaction, which has rarely been reported in carbodi\u00adphospho\u00adrane chemistry  units, the iridium(III) center coordinates a hydrido and a chlorido ligand trans to each other. Reaction of the monocationic Cl complex 2 with two equivalents of thallium(I)tri\u00adfluoro\u00admethane\u00adsulfonate (TfOTl) causes the removal of the chlorido ligand and the chloride counter-ion with concomitant coordination of the acetate carbonyl oxygen atom in a facial manner, resulting in formation of the dicationic (CF3O3S)2 complex 3.Treatment of our PCP pincer ligand system [CH(dppm)et al. (CO)3(dppm)] complex at low temperature generates the corresponding vinyl\u00adidene [MnI(C=CH\u2014CO2Me)(CO)3(dppm)]BF4 complex, which rearranges via insertion of the vinyl\u00adidene ligand into the manganese\u2013phospho\u00adrus bond upon warming to room temperature to an [MnI{(dppm)C=CH(CO2Me)}(CO)3]BF4 complex. Exposure of complex 3 to carbon monoxide gas cleaves the iridium(III) carbonyl oxygen bond under coordination of a carbonyl ligand. Up to now, we have been unable to obtain suitable single crystals of complexes 1 and 2; however, it proved possible to crystallize the (CF3O3S)2 (3) and (CF3O3S)2 (4) products, the latter as a mixed di\u00adchloro\u00admethane\u2013ethyl acetate solvate.A similar ligand arrangement in the coordination sphere of manganese(I) was previously mentioned by Ruiz  al. 2005. Protona3 reveal an ortho\u00adrhom\u00adbic crystal system in space group P212121  centre is coordinated in a facial mode by the PCO pincer ligand system via a phosphine functionality, an ylidic carbon atom and a carbonyl oxygen atom of the ester group. The coordination sphere of the iridium(III) atom is completed by one bidentate dppm and one hydrido ligand. Furthermore, all phospho\u00adrus atoms and the iridium atom are positioned in a common plane and the carbonyl oxygen atom as well as the hydride anion are located perpendicularly to this plane, trans to each other. The iridium center creates with its coordination sphere a distorted octa\u00adhedral geometry and the deviations are caused by the presence of the strained four-membered dppm chelate ring [P3\u2014Ir1\u2014P4 = 70.2\u2005(1)\u00b0] and the tridentate PCO ligand . A C1\u2014C4 distance of 1.335\u2005(9)\u2005\u00c5 indicates a double bond and the sum of angles of 358.3\u00b0  permits the designation of the C1 surroundings as a planar surface. The Ir1\u2014O1 bond length of 2.239\u2005(4)\u2005\u00c5 is close to the value [2.262\u2005(4)\u2005\u00c5] in the related [Ir(CO2CH3){C(CO2CH3)CH(CO2CH3)}(PPh3)(2-Ph2PC6H4NH)] complex  complex, which is stabilized by two tri\u00adfluoro\u00admethane\u00adsulfonate counter-ions  metal atom shows a distorted octa\u00adhedral geometry. It coordinates a dppm unit and a PCO pincer ligand system in a meridional manner and, perpendicular to this plane, a hydrido ligand. The only difference is that the carbonyl oxygen atom of the PCO ligand system is uncoordinated and has been substituted by a carbonyl ligand. The carbonyl ligand reveals relatively long Ir1\u2014C8 [1.965\u2005(15)\u2005\u00c5] and C8\u2014O3 [1.116\u2005(14)\u2005\u00c5] distances, caused by the location trans to the hydrido ligand. Moreover, the substitution results in an overall lengthening of the Ir\u2014P and the Ir\u2014C separations  and 3.473\u2005(10)\u2005\u00c5 2-Synthesis of Cl (1): A mixture of 0.1\u2005ml MeCN, 20.4\u2005mg of [CH(dppm)2]Cl (0.0250\u2005mmol) and 8.4\u2005mg of [IrCl(cod)]2 (0.0125\u2005mmol) was stirred for 1\u2005min. The resulting solution contains predominantly the well known Cl2 ]Cl complex 1. 31P {1H} NMR : \u03b4 = 1.5 , 31.5  p.p.m.; 13C {1H} NMR : \u03b4 = \u221228.9  p.p.m.; 1H NMR : \u03b4 = \u221221.3  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{CH]Cl (2): While stirring the aforementioned MeCN solution of Cl2 and Cl (1), 0.26\u2005ml of CHCl3 and 0.24\u2005ml of a solution of ethyl diazo\u00adacetate in CHCl3  were added successively. The Cl2 by-product is slowly transformed to 1, which in turn reacts with ethyl diazo\u00adacetate. After standing for 24\u2005h, product 2 was generated almost qu\u00adanti\u00adtatively. 31P {1H} NMR : \u03b4 = 26.5 , 45.7 , \u221252.5 , \u221236.7  p.p.m.; 13C {1H} NMR : \u03b4 = 139.2  p.p.m.; 1H NMR : \u03b4 = \u221217.7  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{C2 (3):}(dppm)H] tri\u00adfluoro\u00admethane\u00adsulfonate (0.0597\u2005mmol) were dissolved in MeOH (0.1\u2005ml) and added to a solution of complex 2 (0.025\u2005mmol) in chloro\u00adform/aceto\u00adnitrile (5:1). After stirring for 15\u2005min the precipitated TlCl was separated, all solvents were removed and complex 3 was obtained . Single beige\u2013white crystals of complex 3 were grown slowly from acetone (0.5\u2005ml), covered with 0.3\u2005ml of hexane. 31P {1H} NMR : \u03b4 = 9.1 , 36.0 , \u221244.2 , \u221233.1  p.p.m.; 13C {1H} NMR (CDCl3): \u03b4 = 181.4  p.p.m.; 1H NMR (CDCl3): \u03b4 = \u221223.3  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{C2 (4):}(CO)(dppm)H](CF Complex 3 was dissolved in CHCl3 (0.6\u2005ml), the mixture was filtered and the solution was placed in an atmos\u00adphere of CO. After standing for 16\u2005h product 4 was formed and single crystals were obtained via layering of a solution of complex 4 dissolved in CH2Cl2 with EtOAc. 31P {1H} NMR (CHCl3/CH3OH): \u03b4 = 5.3 , 57.1 , \u221255.6 , \u221244. 7  p.p.m.; 13C {1H} NMR (CDCl3/CD3OD): \u03b4 = 134.8  p.p.m.; 1H NMR (CDCl3/CD3OD): \u03b4 = \u22128.8  p.p.m.3 and 4 were processed without absorption corrections. In relation to the structure determination of complex 3, the hydrido ligand was detected and refined isotropically. One tri\u00adfluoro\u00admethane\u00adsulfonate counter-ion shows positional disorder in a 2:1 ratio, caused by an overlying of the C9, O16 and F16 positions. These positions were also refined isotropically. The structure determination of complex 4 resulted in the detection of pseudo-merohedral twinning  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S205698901801455X/hb7757sup1.cifCrystal structure: contains datablock(s) global, 3, 4. DOI: 10.1107/S205698901801455X/hb77573sup2.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S205698901801455X/hb77574sup4.hklStructure factors: contains datablock(s) 4. DOI: 1849369, 1849368CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E configuration with respect to the C=N double bond. The benzene rings form a dihedral angle of 58.06\u2005(9)\u00b0. In the crystal, the mol\u00adecules are linked by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds into chains, which are further connected into a three-dimensional network by C\u2014H\u22ef\u03c0 inter\u00adactions.The title Schiff base compound displays an  15H13BrN2O2, displays an E configuration with respect to the C=N double bond, which forms a dihedral angle of 58.06\u2005(9)\u00b0 with the benzene ring. In the crystal, the mol\u00adecules are linked into chains parallel to the b axis by N\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds, giving rise to rings with an R21(6) graph-set motif. The chains are further linked into a three-dimensional network by C\u2014H\u22ef\u03c0 inter\u00adactions. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from C\u22efH (33.2%), H\u22efH (27.7%), Br\u22efH/H\u22efBr (14.2%) and O\u22efH/H\u22efO (13.6%) inter\u00adactions. The title compound has also been characterized by frontier mol\u00adecular orbital analysis.The title Schiff base compound, C Schiff bases are of great importance in the field of coordination chemistry because they are able to form stable complexes with metal ions -4-bromo-N\u2032-(4-meth\u00adoxy\u00adbenzyl\u00adidene)benzohydrazide is reported.Schiff bases are nitro\u00adgen-containing compounds that were first obtained by the condensation reactions of aromatic amines and aldehydes \u2005\u00c5] and C7=O2 [1.222\u2005(3)\u2005\u00c5] bond lengths confirm their double-bond character. The C7\u2014N1, N1\u2014N2 and C3\u2014Br1 bond lengths are 1.354\u2005(3), 1.379\u2005(3) and 1.894\u2005(3)\u2005\u00c5, respectively. The central O2/C7/N1/N2 fragment is approximately planar (r.m.s. deviation 0.0141\u2005\u00c5) and forms dihedral angles of 32.5\u2005(2) and 27.2\u2005(2)\u00b0 with the C1\u2013C6 and C9\u2013C14 rings, respectively. The dihedral angle formed by the aromatic rings is 58.06\u2005(9)\u00b0.The asymmetric unit of the title compound Fig.\u00a01 consistsb-axis direction by N1\u2014H1N\u22efO2 and C8\u2014H8\u22efO2 hydrogen-bonding inter\u00adactions  acts as an electron donor and the LUMO  acts as an electron acceptor. If the energy gap is small then the mol\u00adecule is highly polarizable and has high chemical reactivity. The energy levels were computed by the DFT-B3LYP/6-311G++ method benzohydrazide benzohydrazide benzohydrazide benzohydrazide methyl\u00adene)benzohydrazide methyl\u00adidenebenzohydrazine  of 4-bromo\u00adbenzohydrazide (0.213\u2005mg) and a hot ethano\u00adlic solution of 4-meth\u00adoxy\u00adbenzaldehyde (0.136\u2005mg). The mixture was refluxed for 8\u2005h, then it was cooled and kept at room temperature. The powder formed was recrystallized from DMSO. Colourless block-shaped crystals suitable for X-ray analysis were obtained after a few days on slow evaporation of the solvent.Uiso(H) = 1.2Ueq or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl H atoms. Three outliers  global, I, 1. DOI: 10.1107/S2056989018013373/rz5241Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013373/rz5241Isup3.cmlSupporting information file. DOI: 1587248CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The coordination sphere of each Sn atom is best described as a distorted trigonal bipyramid. Each stannic ion in the complex is in a C2O2N environment. The two homologous parts of the doubly deprotonated ligand are located in trans positions with respect to the C\u2014C bond of the oxalamide group. The oxalamide group exhibits an asymmetric coordination geometry, as seen by the slight difference between the C\u2014O and C\u2014N bond lengths. The three-dimensional network is a multilayer of complex mol\u00adecules with no strong supramolecular inter\u00adactions.The binuclear complex, [Sn The stannic units are connected by the doubly deprotonated ligand which play a bridging role in a trans conformation. Each stannic unit is coordinated to the ligand via an imino\u00adlate O atom, a phenolate O atom and an imine N atom. Each Sn atom is penta\u00adcoordinated. The Sn\u2014C bond lengths [2.158\u2005(3)\u20132.168\u2005(3)\u2005\u00c5] are slightly shorter than the values reported for complexes containing the [Sn(tBu)2]2+ unit  and 2.0979\u2005(18)\u2005\u00c5, respectively, for Sn1 and Sn2] are shorter than the Sn\u2014Oimino\u00adlate bond lengths  (Table\u00a01phenolate distances associated with the strong coordination [1.302\u2005(3)\u20131.308\u2005(3)\u2005\u00c5] are longer than the C\u2014Oimino\u00adlate bonds associated with the less strong coordination [1.283\u2005(3)\u20131.288\u2005(3)\u2005\u00c5]. The coordination sphere SnNC2O2 for each of the two Sn atoms can be characterized by the trigonality parameter \u03c4 = (\u03b2 \u2212 \u03b1)/60, with \u03b1 and \u03b2 being the two largest angles around Sn \u00b0 for Sn1 and 130.02\u2005(12)\u00b0 for Sn2] result in compression of the bond angles with the third atom which forms the equatorial plane with the two tert-butyl groups . The sum of the angles in the basal planes are, respectively, 359.99\u00b0 for Sn1 and 359.94\u00b0 for Sn2. The O atoms occupy the apical positions with comparable angles of 154.61\u2005(7)\u00b0 for Sn1 and 154.73\u2005(7)\u00b0 for Sn2. The angles between the apical O atoms and the atoms in the basal plane are in the range 72.35\u2005(7)\u201397.12\u2005(11)\u00b0 for Sn1 and between 72.39\u2005(6) and 96.48\u2005(9)\u00b0 for Sn2. The ligand, which acts in a tridentate fashion, forms two rings upon coordination with the tin centres, i.e. a five-membered OCNNSn ring and a six-membered OCCCNSn ring, sharing atom N1 for Sn1 and N4 for Sn2. The angles resulting from the five-membered ring [N1\u2014Sn1\u2014O2 = 72.35\u2005(7)\u00b0 and N4\u2014Sn2\u2014O3 = 72.39\u2005(6)\u00b0] are much smaller than the angles resulting from the six-membered ring [N1\u2014Sn1\u2014O1 = 82.32\u2005(8)\u00b0 and N4\u2014Sn2\u2014O4 = 82.39\u2005(7)\u00b0]. The better flexibility of the six-membered ring can explain this observed difference in values. The five- and six-membered rings obtained after coordination of the ligand are not planar, as indicated by the torsion angles for the two Sn atoms in the complex: Sn1\u2014N1\u2014N2\u2014C8 0.6, Sn1\u2014O2\u2014C8\u2014N2 0.5, Sn1\u2014O1\u2014C1\u2014C6 6.3, Sn1\u2014N1\u2014C7\u2014C6\u00a0\u2212\u00a02, Sn2\u2014N4\u2014N3\u2014C9 2.1, Sn2\u2014O3\u2014C9\u2014N3\u00a0\u2212\u00a01.2, Sn2\u2014O4\u2014C16\u2014C11\u00a0\u2212\u00a03.7 and Sn2\u2014N4\u2014C10\u2014C11\u00a0\u2212\u00a00.5\u00b0. For all four tBu groups, the angles around the central C atom (Sn\u2014C\u2014C and C\u2014C\u2014C) vary in the range from 106.0\u2005(3) to 112.3\u2005(4)\u00b0 and indicate a tetra\u00adhedral environment around the central C atom. Both tBu groups reveal an eclipsed conformation regarding the methyl groups. The C\u2014C bond lengths are in the range 1.81\u2005(5)\u20131.542\u2005(9)\u2005\u00c5 and are comparable to the values found in the literature  was added a solution of salicyl\u00adaldehyde (2\u2005mmol) in 10\u2005ml of the same mixture. A white precipitate appeared and the resulting mixture was stirred at room temperature for 24\u2005h. The suspension was filtered and the solid was washed with 2 \u00d7 10\u2005ml of water and 2 \u00d7 10\u2005ml of ether. The solid was recrystallized from a mixture of chloro\u00adform and methanol (1:1 v/v). The white powder collected was dried under P2O5. Yield 90% (H4L). Calculated for C16H14N4O4: C 58.89, H 4.32, N 17.17%; found: C 59.02, H 4.37, N 17.24%. IR (cm\u22121): 3277 (\u03bd O\u2014H), 1664 (\u03bd C=O), 1601 (\u03bd C=N), 1533, 1486, 1457, 1357, 1304, 1259, 1218, 1161 (\u03bd C\u2014O), 776, 673. 1H NMR: \u03b4 12.6 , 11.00 , 8.85 , 7.6\u20137.00 . 13C NMR: \u03b4 158.5, 156.8, 151.98, 148.00, 132.93, 130.27, 120.37, 119.54, 117.39. To a mixture of H4L (2\u2005mmol) and tri\u00adethyl\u00adamine (4\u2005mmol) in 10\u2005ml of ethanol was added SnCl2tBu2 (2\u2005mmol) in ethanol (10\u2005ml). The resulting yellow mixture was stirred under reflux for 120\u2005min and the resulting brown solution was filtered. The filtrate was kept at 298\u2005K and after one week yellow crystals suitable for X-ray analysis appeared and were collected by filtration. Yield 40%, m.p. 243\u00b0C. Calculated for C32H46N4Sn2O4: C 48.77, H 5.88, N 7.11%; found: C 48.64, H 5.96, N 7.09%. IR (cm\u22121): 1609, 1537, 1516, 1468, 1441, 1367, 1310, 1275, 1198, 1167, 1150, 870, 771, 754. 1H NMR: \u03b4 8.85 ; 7.13\u20136.69 ; 1.33 . 13C NMR: \u03b4 168.80, 163.68, 135.85, 134.72, 122.22, 116.99, 41.53, 29.96.To a solution of oxalyldihydrazine (1\u2005mmol) in a mixture of water and methanol (1:3 Uiso(H) = 1.2Ueq(C) (1.5 for CH3 groups).Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989018007077/ex2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018007077/ex2008Isup2.hklStructure factors: contains datablock(s) I. DOI: 1842349CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Two oxetanocin A derivatives have been synthesized stereospecifically. The crystal structures of both derivatives and a synthetic inter\u00admediate are reported on herein. 10H9ClN4O, 3-[(6-chloro-7H-purin-7-yl)meth\u00adyl]cyclo\u00adbutan-1-one (I), and two N-7 and N-9 regioisomeric oxetanocin nucleoside analogs, C10H13ClN4O, 3-[meth\u00adyl]cyclo\u00adbutan-1-ol (II) and C10H11ClN4O, 3-[(6-chloro-9H-purin-9-yl)meth\u00adyl]cyclo\u00adbutan-1-ol (IV), are reported. The crystal structures of the nucleoside analogs confirmed the reduction of the N-7- and N-9-substituted cyclo\u00adbutano\u00adnes with LiAl(OtBu)3 to occur with facial selectivity, yielding cis-nucleosides analogs similar to those found in nature. Reduction of the purine ring of the N-7 cyclo\u00adbutanone to a di\u00adhydro\u00adpurine was observed for compound (II) but not for the purine ring of the N-9 cyclo\u00adbutanone on formation of compound (IV). In the crystal of (I), mol\u00adecules are linked by a weak Cl\u22efO inter\u00adaction, forming a 21 helix along [010]. The helices are linked by offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.498\u2005(1)\u2005\u00c5], forming layers parallel to (101). In the crystal of (II), mol\u00adecules are linked by pairs of O\u2014H\u22efN hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked by O\u2014H\u22efN hydrogen bonds, forming chains along [001], which in turn are linked by C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.509\u2005(1)\u2005\u00c5], forming slabs parallel to the ac plane. In the crystal of (IV), mol\u00adecules are linked by O\u2014H\u22efN hydrogen bonds, forming chains along [101]. The chains are linked by C\u2014H\u22efN and C\u2014H\u22efO hydrogen bonds and C\u2014H\u22ef\u03c0 and offset \u03c0\u2013\u03c0 inter\u00adactions [inter\u00adcentroid distance = 3.364\u2005(1)\u2005\u00c5], forming a supra\u00admolecular framework.The crystal structures of an inter\u00admediate, C The mean plane of the cyclo\u00adbutane ring (A = C2\u2032\u2013C5\u2032) is inclined to the mean plane of the purine ring system (B = N1/N37N7/N9/C2/C4/C5/C6/C8) by 52.62\u2005(11)\u00b0, while the torsion angle N7\u2014C5\u2032\u2014C4\u2032\u22efC2\u2032 is ca 125.4\u00b0.In compound (I)tert-but\u00adoxy\u00adaluminum hydride lead to the formation of the oxetanocin derivative compound (II)A) is inclined to the mean plane of the purine ring system (B) by 26.37\u2005(15)\u00b0, while the torsion angle N7\u2014C5\u2032\u2014C4\u2032\u22efC2\u2032 is ca 120.0\u00b0. Atoms C6\u2032 and C4\u2032 are positionally disordered and were split giving a refined occupancy ratio for C6\u2032:C6\u2032B and C4\u2032:C4\u2032B of 0.858\u2005(4):0.142\u2005(4) 4) Fig.\u00a02.trans positioning of the cyclo\u00adbutanol unit, there are no intra\u00admolecular hydrogen bonds between the chlorine atom and the cyclo\u00adbutanol or methyl\u00adene connector as observed in compounds (I)A) is inclined to the mean plane of the purine ring system (B) by 71.20\u2005(13)\u00b0, and the torsion angle N7\u2014C5\u2032\u2014C4\u2032\u22efC2\u2032 is ca 144.8\u00b0.In compound (IV)4 to a di\u00adhydro\u00adpurine . This strained orientation is not observed for the N-9 ketone, hence the integrity of its purine ring is preserved.Reduction of the purine ring of the N-7 cyclo\u00adbutanone to a di\u00adhydro\u00adpurine was observed for compound (II)x\u00a0+\u00a01, y\u00a0\u2212\u00a0z\u00a0+\u00a01 helix along [010], see Fig.\u00a04CgB\u22efCgBi = 3.498\u2005(1)\u2005\u00c5, CgB is the centroid of the purine ring system, \u03b1 = 0.00\u2005(5)\u2005\u00c5, \u03b2 = 21.6\u00b0, inter\u00adplanar distance = 3.252\u2005(1)\u2005\u00c5, offset = 1.289\u2005\u00c5, symmetry code (i) \u2212x\u00a0+\u00a02, \u2212y\u00a0+\u00a01, \u2212z\u00a0+\u00a01.In the crystal of (I)ac plane. In the crystal of (II)f Table\u00a02. The dimf Table\u00a02 and offsCgB\u22efCgBvi = 3.534\u2005(1)\u2005\u00c5, CgB is the centroid of the purine ring system, \u03b1 = 0.02\u2005(10)\u2005\u00c5, \u03b2 = 17.8\u00b0, inter\u00adplanar distance = 3.364\u2005(1)\u2005\u00c5, offset = 1.08\u2005\u00c5, symmetry code (vi) \u2212x\u00a0+\u00a01, \u2212y\u00a0+\u00a01, \u2212z. ]In the crystal of (IV)et al., 2016viz. 6-chloro-9-(3-hy\u00addroxy\u00admethyl-3-hy\u00addroxy\u00adcyclo\u00adbut\u00adyl)purine cyclo\u00adbutanol  Potassium carbonate (12.0\u2005mmol) was added to a solution of (3-oxo\u00adcyclo\u00adbut\u00adyl)methyl benzoate (10.0\u2005mmol) in methanol (20\u2005ml) and stirred for 1\u2005h at room temperature. Saturated sodium bicarbonate (10.0\u2005ml) was added and stirring continued for an additional 15\u2005min. The solvent was evaporated under vacuum, followed by purification by flash column chromatography with ethyl acetate, resulting in 3-(hy\u00addroxy\u00admeth\u00adyl)cyclo\u00adbutan-1-one in 70% yield.3-(Hy\u00addroxy\u00admeth\u00adyl)cyclo\u00adbutan-1-one (1\u2005mmol) was dissolved in 10\u2005ml of dry di\u00adchloro\u00admethane and cooled to 195\u2005K. Hunig\u2019s base (3.2\u2005mmol) was added, followed by tri\u00adfluoro\u00admethane\u00adsulfonic anhydride (1\u2005mmol) and the mixture was stirred for 10\u2005min, cooled to 273\u2005K and stirred to obtain the qualitative conversion to (3-oxo\u00adcyclo\u00adbut\u00adyl)methyl tri\u00adfluoro\u00admethane\u00adsulfonate.H-purine (5.61\u2005mmol), potassium hydroxide (5.61\u2005mmol), tris\u00ad[2-(2-meth\u00adoxy\u00adeth\u00adoxy)eth\u00adyl]amine (0.28\u2005mmol), magnesium sulfate (2\u2005g) and anhydrous aceto\u00adnitrile (100\u2005ml), which was then heated to 333\u2005K for 5\u2005h and cooled to room temperature. The product was purified using 5% methanol and 5% tri\u00admethyl\u00adamine in chloro\u00adform, which yielded two UV-active compounds.The (3-oxo\u00adcyclo\u00adbut\u00adyl)methyl tri\u00adfluoro\u00admethane\u00adsulfonate (5.61\u2005mmol) was added to a mixture containing 6-chloro-7H-purin-9-yl)meth\u00adyl]cyclo\u00adbutan-1-one (III) and 37% of the N-7 alkyl\u00adated deriv\u00adative 3-[(6-chloro-7H-purin-7-yl)meth\u00adyl]cyclo\u00adbutan-1-one (I)The two UV-active compounds were separated using flash column chromatography with ethyl acetate, giving 51% of the N-9 alkyl\u00adated derivative; 3-[meth\u00adyl]cyclo\u00adbutan-1-ol (II) 3-[(6-Chloro-7H-purin-7-yl)meth\u00adyl]cyclo\u00adbutan-1-one (I)tert-but\u00adoxy\u00adaluminum hydride was added. The mixture was cooled to room temperature and sodium borohydride (0.32\u2005mmol) was added and the resulting mixture allowed to stir overnight. Methanol (2\u2005ml) was added and the mixture allowed to stir overnight to convert the over-reduced 3-[(6-chloro-7H-purin-7-yl]meth\u00adyl)cyclo\u00adbutanone(I) to 3-[meth\u00adyl]cyclo\u00adbutan-1-ol (II)Synthesis ofcis-3-[(6-chloro-9H-purin-9-yl)meth\u00adyl]cyclo\u00adbutan-1-ol (IV) 3-[(6-Chloro-9H-purin-9-yl)meth\u00adyl]cyclo\u00adbutan-1-one (III) (0.21\u2005mmol) was added to diethyl ether and cooled to 195\u2005K and lithium tri-tert-but\u00adoxy\u00adaluminum hydride (0.32\u2005mmol) was added. The reaction was allowed to warm to room temperature and left to stir overnight, which provided qu\u00adanti\u00adtative conversion to cis-3-[(6-chloro-9H-purin-9-yl)meth\u00adyl]cyclo\u00adbutan-1-ol (IV)Pale-yellow plate-like crystals of (I)Uiso(H) = 1.2Ueq(C). For compound (II)B and C4\u2032:C4\u2032B of 0.858\u2005(4):0.142\u2005(4). For the final refinement of compound (II)Crystal data, data collection and structure refinement details are summarized in Table\u00a0510.1107/S2056989019004432/zp2033sup1.cifCrystal structure: contains datablock(s) global, I, II, IV. DOI: 10.1107/S2056989019004432/zp2033Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004432/zp2033IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019004432/zp2033IIsup5.cmlSupporting information file. DOI: 1907200, 1907199, 1907198CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "E. In the crystal, O\u2014H\u22efO hydrogen-bond inter\u00adactions consolidate the crystal packing. A Hirshfeld surface analysis and fingerprint plots were used to further investigate the inter\u00admolecular inter\u00adactions in the solid state.In the title Schiff base derivative carrying a 2-bromo-3-methyl\u00adphenyl group, the conformation about the C=N bond is  14H12BrNO2, was synthesized by the condensation reaction of 2,3-di\u00adhydroxy\u00adbenzaldehyde and 2-bromo-3-methyl\u00adaniline. It crystallizes in the centrosymmetric triclinic space group PE. The dihedral angle between the planes of the 5-(2-bromo-3-methyl\u00adphenyl ring and the catechol ring is 2.80\u2005(17)\u00b0. In the crystal, O\u2014H\u22efO hydrogen-bond inter\u00adactions consolidate the crystal packing.The title compound, C Schiff PZ = 4 (Z\u2032 = 2). The two crystallographically independent mol\u00adecules have nearly the same geometrical parameters and the primary difference between them is the rotational orientation of H2 and H4A. The discussion will therefore be limited to that of the mol\u00adecule containing O1. The mol\u00adecular structure is constructed from two individually planar rings. The whole mol\u00adecule is approximately planar, with a maximum deviation of 0.117\u2005(3)\u2005\u00c5 from planarity for the hydroxyl O1 atom of the catechol ring. The dihedral angle between the two benzene ring planes is 2.80\u2005(17)\u00b0. The methyl C1 atom deviates from the plane of the C2\u2013C7 benzene ring by 0.039\u2005(2)\u2005\u00c5 while C9 deviates from the plane of the C9\u2013C14 benzene ring by 0.024\u2005(3)\u2005\u00c5. The C8\u2014N1\u2014C7\u2014C6 and C14\u2014 C9\u2014C8\u2014N1 torsion angles are \u22121.6\u2005(5) and \u22121.1\u2005(5)\u00b0, respectively. The planar mol\u00adecular conformation of each molecule is stabilized by an intra\u00admolecular O\u2014H\u22efN hydrogen bond  and Cg3\u22efCg4, where Cg1, Cg2, Cg3 and Cg4 are the centroids of the C2\u2013C7, C9\u2013C14, C16\u2013C21 and C23\u2013C28 rings, respectively.In the crystal, the Schiff base units are linked by O\u2014H\u22efO and C\u2014H\u22efO hydrogen bonds -N-(2-bromo\u00adphen\u00adyl)-1-phenyl\u00admethanimine skeleton yielded nine hits. The N1\u2014C8 bond in the title structure is the same length within standard uncertainties as those in the structures of 2-bromo-N-salicylideneaniline -1-(2-fluoro\u00adphen\u00adyl)methanimine -\u00admeth\u00adyl]-4-bromo\u00adphenol naphthaldimine -2-bromo\u00adaniline  plot with de and di for the title compound is shown in Fig.\u00a03de = di = 1.5\u2005\u00c5; Fig.\u00a04Hirshfeld surface analysis of the title compound was performed utilizing the A mixture of 2,3-di\u00adhydroxy\u00adbenzaldehyde  and 2-bromo-3-methyl\u00adaniline  was stirred with ethanol (30\u2005mL) at 377\u2005K for 5\u2005h, affording the title compound . Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.Uiso(H) = 1.5Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model: C\u2014H = 0.93\u2005\u00c5 with Uiso(H) = 1.2Ueq(C) for aromatic H atoms and C\u2014H = 0.96\u2005\u00c5 with Uiso(H) = 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table\u00a0210.1107/S2056989019015718/mw2151sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019015718/mw2151Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019015718/mw2151Isup3.cmlSupporting information file. DOI: 1967023CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "The asymmetric unit of the title solvate comprises a half mol\u00adecule of each component as both species are disposed about a centre of inversion. In the crystal, two-dimensional arrays are formed by amide-N\u2014H\u22efN(pyrid\u00adyl) hydrogen bonds, which are connected into a three-dimensional architecture by C\u2014H\u22ef\u03c0(benzene and pyrid\u00adyl) inter\u00adactions with benzene acting as the acceptor and donor, respectively. 14H14N4O2\u00b7C6H6 , comprises a half mol\u00adecule of each constituent as each is disposed about a centre of inversion. In the oxalamide mol\u00adecule, the central C2N2O2 atoms are planar (r.m.s. deviation = 0.0006\u2005\u00c5). An intra\u00admolecular amide-N\u2014H\u22efO(amide) hydrogen bond is evident, which gives rise to an S(5) loop. Overall, the mol\u00adecule adopts an anti\u00adperiplanar disposition of the pyridyl rings, and an orthogonal relationship is evident between the central plane and each terminal pyridyl ring [dihedral angle = 86.89\u2005(3)\u00b0]. In the crystal, supra\u00admolecular layers parallel to (10via methyl\u00adene-C\u2014H\u22ef\u03c0(benzene) and benzene-C\u2014H\u22ef\u03c0(pyrid\u00adyl) inter\u00adactions. The specified contacts are indicated in an analysis of the calculated Hirshfeld surfaces. The energy of stabilization provided by the conventional hydrogen bonding  is just over double that by the C\u2014H\u22ef\u03c0 contacts (dispersion forces).The asymmetric unit of the title 1:1 solvate, C The first of these arises from amide-N\u2014H\u22efO(amide) hydrogen bonding between the amide groups, on both sides of the 3LH2 mol\u00adecule, through ten-membered amide synthons {\u22efHNC2O}2 . Mol\u00adecules of nLH2 also featured prominently in early, systematic studies of halogen bonding. An illustrative example is found in the 1:1 co-crystal formed between 3LH2 and 1,4-di-iodo\u00adbuta-1,3-diyne, I\u2014C\u2261C\u2014C\u2261C\u2014C\u2014I  hydrogen bonding and these are linked into a two-dimensional array via amide-N\u2013H\u22efN(pyrid\u00adyl) hydrogen bonds  hydrogen bonds to generate a two-dimensional array. In this context, and in the context of recent work on 4LH2 in co-crystals via an analysis of the calculated Hirshfeld surfaces as well as a computational chemistry study.With a combination of centrally located amide and terminal pyridyl functional groups, the isomeric mol\u00adecules related to the title compound of the general formula \u2005\u00c5 to either side of the plane. An intra\u00admolecular amide-N\u2014H\u22efO(amide)i hydrogen bond, occurring between the symmetry related amide groups, gives rise to an S(5) loop, Table\u00a01x, 1\u00a0\u2212\u00a0y, \u2212 z. The crystallographic symmetry also implies an anti\u00adperiplanar disposition of the pyridyl rings. The dihedral angle between the central plane and terminal pyridyl ring is 86.89\u2005(3)\u00b0, indicating an orthogonal relationship.The title co-crystal (I)a), with dimensions defined by O10\u22efO10 and N8\u22efN8 separations of 9.6770\u2005(11) and 12.3255\u2005(11)\u2005\u00c5, respectively. The other notable contacts in the crystal are of the type C\u2014H\u22ef\u03c0, Table\u00a01i.e. two (as acceptor) and two (as donor), such inter\u00adactions, Fig.\u00a02b). The side-on view of Fig.\u00a02b) shown in Fig.\u00a02c) indicates the amide-N\u2014H and pyridyl-N project in all directions around the five-mol\u00adecule aggregate. Indeed, it is the C\u2014H\u22ef\u03c0 inter\u00adactions that connect the layers into a three-dimensional architecture, Fig.\u00a02d).The geometric parameters characterizing the inter\u00adatomic contacts identified in the crystal of (I)Mercury dnorm map of 4LH2 displays several red spots, that range from intense to weak, which reflect the inter\u00adactions identified in the crystal  inter\u00adactions, Fig.\u00a04a), with both indicative of contact distances shorter than the respective sum of the van der Waals radii. Reflecting the relatively long separation, the benzene-C11\u2014H11\u22ef\u03c0(pyrid\u00adyl) inter\u00adaction is reflected as only a white spot as the contact distance is only just within the sum of van der Waals radii, as shown in Fig.\u00a04b).The Hirshfeld surface mapped over B\u22ef\u03c0(benzene) contact is indeed electrostatic in nature as revealed by the distinct blue (i.e. electropositive) and red (i.e. electronegative) colour scheme on the surface of the contact points, Fig.\u00a05a). In contrast, the benzene-C11\u2014H11\u22ef\u03c0(pyrid\u00adyl) contact displays pale colouration around the contact zone suggesting that the inter\u00adaction could be attributed to weak dispersion forces, Fig.\u00a05b).The C\u2014H\u22ef\u03c0 inter\u00adactions were subjected to electrostatic potential mapping for verification purposes. The result shows that the methyl\u00adene-C7\u2014H7a)\u2013(e). As shown in the overall fingerprint plot in Fig.\u00a06a), (I)4LH2 mol\u00adecule, therefore indicating that the inter\u00admolecular inter\u00adactions in (I)4LH2 mol\u00adecules. Decomposition of the overall fingerprint plots of (I)di + de \u223c2.42\u2005\u00c5), H\u22efC/C\u22efH , H\u22efO/O\u22efH , H\u22efN/N\u22efH  and other contacts (0.8%). Except for the H\u22efH contacts, to differing extents, the remaining major contacts are shorter than the corresponding sum of van der Waals radii for H\u22efC (\u223c2.90\u2005\u00c5), H\u22efO (\u223c2.72\u2005\u00c5) and H\u22efN (\u223c2.75\u2005\u00c5).The two-dimensional fingerprint plots were generated for overall (I)4LH2 mol\u00adecule exhibits at similar distribution of the major contacts compared to overall (I)4LH2 these are either inclined towards the external or inter\u00adnal contacts presumably due to inter\u00adaction with the solvent benzene mol\u00adecule. For instance, the H\u22efC/C\u22efH contact in the individual 4LH2 mol\u00adecule comprises 9.9% -H\u22efC- and 14.6% -C\u22efH- contacts as compared to 12.0 and 14.6% for the equivalent contacts in overall (I)c). Similar observations pertain for the H\u22efO/ O\u22efH and H\u22efN/ N\u22efH inter\u00adactions, Fig.\u00a06d)\u2013(e).The individual i.e. 20.5% for -H\u22efC- and 21.4% for -C\u22efH- contacts. In addition, the solvent mol\u00adecules are sustained in the mol\u00adecular architecture through minor contributions from H\u22efO (5.6%) and H\u22efN (5.9%) contacts, respectively. These inter\u00adactions are at distances of \u223c2.52\u2005\u00c5 (H\u22efH), \u223c2.92\u2005\u00c5 (H\u22efC/C\u22efH), \u223c2.98\u2005\u00c5 (H\u22efO) and \u223c2.79\u2005\u00c5 (H\u22efN), which are greater than the corresponding sum of van der Waals radii, indicating the identified C\u2014H\u22ef\u03c0(benzene and pyrid\u00adyl) inter\u00adactions can largely be considered as localized inter\u00adactions.As for the benzene mol\u00adecule, an irregular fingerprint profile is noted with the distribution dominated by H\u22efH (46.4%) and H\u22efC/ C\u22efH (41.9%) surface contacts. The latter are almost equally distributed between the inter\u00adnal and external contacts, Crystal Explorer 17 based on the procedures as described previously  of \u221238.1\u2005kJ\u2005mol\u22121, Table\u00a02B\u22ef\u03c0(benzene) and benzene-C11\u2014H11\u22ef\u03c0(pyrid\u00adyl) contacts with a very similar Eint values of \u221218.9 and \u221216.9\u2005kJ\u2005mol\u22121, respectively, despite the dnorm contact distance being significantly greater for the latter. The calculation results reveal that the repulsion energy is greater in methyl\u00adene-C7\u2014H7B\u22ef\u03c0(benzene) compared with the benzene-C11\u2014H11\u22ef\u03c0(pyrid\u00adyl) contact, which contributes to the slight variation in their Eint values. In short, the N\u2014H\u22efN inter\u00adaction is stabilized largely by electrostatic forces while the C\u2014H\u22ef\u03c0 inter\u00adactions are stabilized largely by dispersion forces. Overall, the crystal of (I)a)\u2013(c).The calculation of inter\u00adaction energy was performed using 4LH2 available in the literature ; molecular inversions were enabled during calculation. The result shows that out of the 20 mol\u00adecules in the cluster, only one 4LH2 mol\u00adecule in each polymorph resembled the reference packing in (I)a) and (b). The result clearly demonstrates the influence of solvent mol\u00adecule upon the mol\u00adecular packing in (I)Calculations were also performed to compare the mol\u00adecular packing similarity of (I)4LH2 exhibit a close similarity in the distribution of mol\u00adecular contacts as judged from the percentage contribution of the corresponding contacts on the Hirshfeld surface. The maximum variation in the distribution of H\u22efH, H\u22efC/C\u22efH, H\u22efO/O\u22efH and H\u22efN/N\u22efH contacts ranged from 7.1, 4.9, 2.2 and 3.8%, respectively among the three crystals.Finally, and referring to Fig.\u00a09Chemical Context, there are two polymorphs available for 4LH2 CH2N(H)C(=S)C(=S)N(H)CH2(C5H4N-n), for n = 2, 3 and 4 oxalamide, was prepared in accordance with the literature procedure \u22121): 3322 \u03bd(N\u2014H), 3141\u20132804 \u03bd(C\u2014H), 1696\u20131661 \u03bd(C=O), 1563\u20131515 \u03bd(C=C), 1414 \u03bd(C\u2014N), 794 \u03b4(C=C).The precursor, Uiso(H) set to 1.2Ueq(C). The nitro\u00adgen-bound H atom was located from difference-Fourier maps and refined with N\u2014H = 0.88\u00b10.01\u2005\u00c5, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table\u00a0410.1107/S2056989019009551/hb7835sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019009551/hb7835Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019009551/hb7835Isup3.cmlSupporting information file. DOI: 1938031CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:"}
{"text": "Mature RNA (miRNeasy Mini kit) was reverse transcribed using RT2 First strand cDNA synthesis kit. The cDNA was used on the real\u2010time RT2 Profiler PCR Array  in combination with RT2 SYBR\u00ae Green qPCR Mastermix (Roche LightCycler\u00ae 480 Instrument). Threshold cycle (CT) values (excel file) were uploaded onto the data analysis centre web portal (http://www.qiagen.com/geneglobe). CT values were normalized based on a Manual Selection of reference genes. The fold change/regulation (2^(\u2010\u0394\u0394CT)) was calculated using \u0394\u0394CT method .The isolated hVFs were grouped into fibroblasts\u2010less differentiated (HF\u2010LD) and fibroblasts\u2010highly differentiated (HF\u2010HD) based on their \u03b1\u2010SMA expression (immunoblot), compared to the control hVFs Figure A,B. Poly2.2TFAP2A\u2014F:5\u2032\u2010GACCTCTCGATCCACTCCTTAC\u20103\u2032 R: 5\u2032\u2010GAGACGGCATTGCTGTTGGACT\u20103\u2032; \u03b2\u20102\u2010microglobulin (B2M)\u2010 F: 5\u2032\u2010CCACTGAAAAAGATGAGTATGCCT\u20103\u2032 and R: 5\u2032\u2010CCAATCCAAATGCGGCATCTTCA\u20103\u2032. The following PrimeTime qPCR mouse primer assays were used: \u03b1\u2010SMA (Mm.PT.58.16320644); COL1A1 (Mm.PT.58.7562513); COL2A1 (Mm.PT.58.5206680); COL3A1 (Mm.PT.58.13848686), TGFBR1 (Mm.PT.58.28402453), TGFBR2 (Mm.PT.58.6358355) and B2M (Mm.PT.39a.22214835). The cycling conditions were 95\u00b0C for 10\u00a0minutes, followed by 40 cycles at 95\u00b0C for 15\u00a0s, 1\u00a0minute at 60\u00b0C, and 72\u00b0C for 40\u00a0s. Melt curve analysis was performed by an additional dissociation step of 1 cycle at 95\u00b0C for 5\u00a0s followed by 65\u00b0C for 1\u00a0min and ramping data collection to 97\u00b0C. Relative expression values (\u0394Ct) were obtained by normalizing Ct values (Roche Lightcycler 480 Software v1.5.1.62) of the tested genes with that of B2M.Total RNA was isolated from hVFs (miRNeasy Mini kit) and reverse transcribed (miScript RT II kit) with the supplied HiFlex buffer. qPCR was performed on the LightCycler 480 Instrument II, using the Power SYBR Green PCR Master Mix and 10\u00a0ng diluted cDNA per well. The following human primers were used: 2.3Creative Biogene, Shirley, NY.The TFAP2A knockout cell line with NIH/3T3 fibroblasts (TFAP2A\u2010KO) was established using CRISPR/CAS9 technology through 2.42 with DMEM media (10% BCS) and incubated at 37\u00b0C under 5%CO2. Following 24\u00a0hours, hVFs were either treated with TGF\u2010\u03b21 (5\u00a0ng/mL), angiotensin II (100\u00a0nM) or kept as control in DMEM media (2.5% BCS). After 48\u201072\u00a0hours, the fibroblasts/myofibroblasts were rinsed with Dulbecco's PBS and assayed.Fibroblasts from wild\u2010type or TFAP2A\u2010KO groups were plated at 4000 cells/cm2.5Standard western protocols were followed2.6t\u00a0\u2212\u00a0t0]/{[log(Nt)\u2010log(N0)]/log(2)}, where t0 refers time , t represents time (second count), N0 refers count at time t0, and Nt represents count at time t.Both WT and KO fibroblasts were plated as stated before in triplicate (per time\u2010point) in 6\u2010well plates and counted by Cellometer Auto 2000  at 24, 48, and 72\u00a0hours post\u2010plating. Doubling time was calculated by [3TFAP2A expression, along with ELK1, was decreased with decrease in differentiation as visualized in the heat map   1A1  is increased in TFAP2A\u2010KO fibroblasts  compared to the wild\u2010type  and highly differentiated (HF\u2010HD) based on their \u03b1\u2010SMA expression, compared to control hVFs as shown in Figure There is no conflict of interest.GRR initiated, designed, executed, analysed the study and wrote the manuscript; SE executed the real\u2010time PCR and PCR array; CW and PH implemented the cell culture, immunoblotting and proliferation assays; FXD, LE, FR and AJ interpreted data and proof\u2010read the manuscript.\u00a0Click here for additional data file."}