Both tungsten atoms have a slightly distorted octahedral coordination.In the title complex two W(CO) 2P:P′]bis[pentacarbonyltungsten(0)], [W2(C26H24P2)(CO)10], consists of two W(CO)5 moieties bridged by a bis(diphenylphosphanyl)ethane (dppe) ligand. The W0 atom has a slightly distorted octahedral coordination environment consisting of 5 carbonyl ligands and one P atom from the bridging dppe ligand with the nearest W0 atom 5.625 (5) Å away. The complex resides on a center of symmetry.The centrosymmetric title complex, [μ-ethane-1,2-diylbis(diphenylphosphane)-κ 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[μ-Ph2P(CH2)n]PPh2)W(CO)5, whereas when n = 4 it was reported the chelated product is favored (W(CO)4[μ-Ph2P(CH2)4PPh2]. Tan et al. W(CO)5 )5 Fig. 1 consists5W(μ-dppe)W(CO)5 are bridged by a diphosphine approximately along the c axis and the molecules themselves are stacked along the a axis. No significant van der Waals-type interactions such as C—H⋯π or π–π contacts between adjacent molecules are observed.The two tungsten atoms in each of the molecules (OC)5W[μ-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 h, methanol was added to precipitate a yellow solid. The precipitate was collected and washed with methanol (3 x 20 mL). The resulting yellow solid was recrystallized from a 1:5 mixture of dichloromethane:methanol at 253 K.All synthesis and crystallization procedures were carried out using standard Schlenk techniques. Dichloromethane was added to a mixture of W(CO)Crystal data, data collection, and structure refinement details are summarized in Table 110.1107/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:


O—H⋯N hydrogen bonds link molecules into a supramolecular chain along  21H28N4O, consists of two unique molecules linked by an O—H⋯N 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 molecules. The dihedral angles between the two benzene rings are 83.14 (4) and 75.45 (4)°. The plane of the one of the N(CH3)2 units is twisted away from the benzene ring by 18.8 (2)°, indicating loss of conjugation between the lone electron pair and the benzene ring. In the crystal structure, O—H⋯N hydrogen bonds together with C—H⋯O hydrogen bonds link neighbouring supramolecular 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-diaminopropan-2-ol have been reported earlier  is shown in Fig. 2A and N2 positions can be described by the torsion angles N2A—C5A—C51A—C56A [−9.9 (11) in molecule A] and N2—C5—C51—C56 [−14.9 (11)° in molecule B]. The two outer aromatic rings (C11–C16 and C51–C56) are inclined to one another by 83.14 (4)° in molecule A and 75.45 (4)° in molecule B.The title compound crystallizes with two unique molecules in the asymmetric unit. The conformers, labeled et al., 2016bA and 1.271 (8) and 1.269 (8) Å in molecule B] and the corresponding internal angles at the nitrogen atom [C1A—N1A—C2A = 117.7 (6) and C5A—N2A—C4A = 117.7 (6) in molecule A and C1—N1—C2 = 117.5 (6) and C5—N2—C4 = 117.6 (6) in molecule B] also agree with those reported in the literature for similar compounds ° and C4A—N2A—C5A—C51A = 179.9 (6)° in molecule A and C2—N1—C1—C11 = 178.6 (6)° and C4—N2—C5—C51 = 177.0 (6) in molecule B.Bond distances and angles in the benzene rings are not unusual and compare well, both between the two independent molecules and with those observed in related systems ° and C57—N4—C54—C53 = −2.9 (11)° and with dihedral angles between the NMe2 plane and the benzene ring of 0.57 (2) and 4.60 (2)°, respectively, whilst in molecule A the corresponding torsional angles C17A—N3A—C14A—C13A and C57A—N4A—C54A—C53A are 2.2 (11) and 8.3 (10)°, respectively. The dihedral angles between the two dimethylamino groups (N3A and N4A) and the benzene rings are 5.09 (22) and 18.8 (2)° respectively, indicating that the lone electron pair of the N4A atom may not be completely conjugated with the benzene ring (C51A–C56A).The two dimethylamino substituents in molecule A—H1A and the nitrogen N2 (Table 1C(5) chains running along the a axis  Å] between O12 Table 1, the twois Fig. 3. The chas Table 1.et al., 2016N,N′-[bis]bis(4-methylbenzenesulfonamide) -(2-chlorobenzylidene)amino]propan-2-ol  = 1.5Ueq(O). The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.95 Å for aromatic and azomethine atoms, d(C—H) = 0.98 Å for methyl, d(C—H) = 0.99 Å for methylene, d(C—H) = 1.00 Å for tertiary CH. The Uiso(H) values were constrained to 1.5Ueq(Cmethyl) or 1.2Ueq(C) for the remaining H atoms. The structure shows signs of a superstructure. The two molecules 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:


III(DMC) acetylide complexes that take on a pseudo-octahedral symmetry and can be synthesized under weak-base conditions.The crystal structures presented herein consist of two positively charged Co III(DMC) . Chlorido(phenylethynyl)cobalt(III) chloride–acetonitrile–methanol (1/1/1), [Co(C8H5)Cl(C12H28N4)]Cl·CH3CN·CH3OH, 1, and bis(phenylethynyl)cobalt(III) trifluoromethanesulfonate–dichloromethane (2/1), [Co(C8H5)2(C12H28N4)]2(CF3SO3)2·CH2Cl2, 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-octahedral symmetry in which the Cl—Co—C angles of 1 and C—Co—C of 2 range from 177.7 (2) to 178.0 (2)° and from 177.67 (9) to 179.67 (9)°, respectively. In both structures, the CoIII metal center is coordinated in the equatorial plane by four N atoms, in which the N—Co—N angles range from 85.6 (3) to 94.4 (3)°. The structure of 1 features two crystallographically independent molecules in its triclinic cell (Z′ = 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 (3) to 0.202 (3). Both methanol solvent molecules in 1 are disordered, the major occupancy rates refined to 0.643 (16) and 0.357 (16). Compound 2 also contains two molecules in the asymmetric unit, together with two trifluoromethanesulfonate anions  and a disordered dichloromethane [occupancy values of 0.545 (12) and 0.455 (12)].Reported in this contribution are the synthesis and crystal structures of new mono- and bis-phenylacetylides based on Co Intere1 crystallizes in PIII(DMC)(C2Ph)(Cl)]+ cation, a chloride counter-ion, and one acetonitrile and methanol solvate molecule, for a total composition of C20H33ClCoN4·C2H3N·CH4O·Cl. The two unique moieties, labeled A and B, are related by a pseudo-glide plane (see the Supramolecular 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 molecules are disordered, with a common refined occupancy ratio of 0.643 (16):0.357 (16).Compound 2 crystallizes in P21, Fig. 21, 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 methylene chloride solvate molecule, yielding a formula of 2(C28H38CoN4)·2(CF3O3S)·CH2Cl2. One of the triflate anions as well as the methylene chloride molecule were refined as disordered, with occupancy rates of 0.503 (22) and 0.545 (12) for the major components.Compound 1 and 2 are similar  and 178.0 (2)°] and C—Co—C [177.67 (9) and 179.67 (9)°] units are close to normal to the equatorial plane created by the coordinated amines of the macrocyclic ligand, confirming octahedral geometries. The C—Co—N and Cl—Co—N angles are all tightly clustered around 90°. The actual values range from 87.1 (1) to 92.9 (1)° –CH2–CH2–N connections  to 174.2 (2)°, with the latter extreme value belonging to one of the Co—C≡C 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.  Å avg.] relative to compound 1. This effect is a result of the stronger π-donation from phenylacetylide compared to chloride. The C—C and C≡C bond lengths of the phenylacetylene ligands fall in the expected region for single and triple bonds respectively. The acetylides in compound 2 show a slightly cumulenic character with elongated C≡C and shortened C—C bond lengths with respect to compound 1, as was also seen by Shores and coworkers  and 1.905 (7) Å] for compound C-centered unit cell with parameters a = 34.721, b = 9.690, c = 15.668 Å, and β = 93.41°. The α and γ angles in the monoclinic cell deviate substantially from 90°, being 88.97 and 89.52° 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. 3A and B, of the surrounding chloride anions and solvate molecules 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 Å. For the surrounding solvate molecules, 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. 4SHELXL) resulted in a twinning ratio of 0.798 (3):0.202 (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 monoacetylide, the ammonium N—H units of the macrocycle form N—H⋯N hydrogen bonds with the acetonitrile nitrogen atom, N—H⋯O hydrogen bonds to the methanol oxygen, and N—H⋯Cl hydrogen bonds to both the interstitial chloride anions as well as the cobalt-bound chlorine. The chloride anions are also acceptors for O—H⋯Cl hydrogen bonds originating from the disordered methanol molecules and for a series of weaker C—H⋯Cl 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—H⋯N, N—H⋯O, and N—H⋯Cl hydrogen bonds, when combined, connect the cations, anions and solvate molecules 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 substantially between the ion pairs. The first of the two cations, involving nitrogen atoms N1 through N4, features each two N—H⋯O and N—H⋯F hydrogen bonds (not counting duplicates from triflate disorder), Fig. 9In the triflate salt ns Fig. 8. The twoIII(DMC)Cl2]Cl was synthesized according to literature procedures (C2Ph)Cl]Cl (1). [CoIII(DMC)Cl2]Cl  was dissolved in 40 mL of methanol. Phenylacetylene  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–methanol to afford 170 mg 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–MS: [M]+, 423.0. 1H NMR : 7.55–7.41 , 7.37–7.25 , 7.25–7.15 , 5.36 , 4.23 , 3.21–2.46 , 1.93–1.84 , 1.53–1.48 , 1.30 . Visible spectra, λmax : 256 , 493 (101); IR (cm−1): C≡C: 2122 (m).Data for [CoIII(DMC)(C2Ph)2]OTf (2). Compound 1  and AgOTf  were dissolved in 50 mL of CH3CN and refluxed for 48 h. The precipitate that formed was filtered out, and 3.1 mL (22 mmol) of Et3N and 0.20 mL (1.8 mmol) of phenylacetylene were added and the solution was refluxed for 48 h. 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–methanol to afford 102 mg of a yellow solid (47% based on 1). Single crystals were grown from slow diffusion of n-hexanes into a CH3OH/CH2Cl2  solution of 2.Preparation of [CoIII(DMC)(C2Ph)2]OTf (2). ESI–MS: [M]+, 489.0. 1H NMR : 7.58–7.42 , 7.36–7.24 , 7.22–7.13 , 4.90 , 3.84 , 3.30–3.01 , 2.81–2.78 , 2.68–2.63 , 2.50–2.43 , 1.83 , 1.38 , 1.27 . Visible spectra, λmax : 271 , 464 (64.5); IR (cm−1): C≡C: 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—O bond lengths were restrained to 1.427 (20) Å. Each minor occupancy component was restrained to be similar the respective major occupancy component . The Uij components for atoms within 2.0 Å 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 (16) and 0.357 (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 Å were restrained to be similar . Subject to these conditions, the occupancy factors refined to 0.503 (22) and 0.497 (22). The dichloromethane molecule 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 Å were restrained to be similar . Subject to these conditions, the occupancy factors refined to 0.545 (12) and 0.455 (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:


R,R,SFc,SFc)-[Fe2(C5H5)2(C38H36BrNP2)]·Br·CH2Cl2 has been determined by X-ray single-crystal diffraction.The absolute structure of -[Fe2(C5H5)2(C38H35NP2)] (1), single crystals of the dichloromethane monosolvate of the Br− salt of the protonated ligand 1H+ were obtained serendipitously, i.e. [Fe2(C5H5)2(C38H36NP2)]Br·CH2Cl2. The crystal structure of 1H·Br·CH2Cl2 was determined by single-crystal X-ray diffraction. The mean bond lengths in the ferrocene units are Fe—C = 2.049 (3) Å and C—C = 1.422 (4) Å within the cyclopentadienyl rings. The mean C—N bond length is 1.523 (4) Å. The interplanar angle between the two connected cyclopentadienyl rings is 49.2 (2)°. One ferrocene moiety adopts a staggered conformation, whereas the other is between staggered and eclipsed. The Br− ions and the CH2Cl2 molecules are located in channels extending along <100>. One ammonium H atom forms a hydrogen bond with the Br− ion [H⋯Br = 2.32 (4) Å and C—H⋯Br = 172 (3)°]. 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 210.1107/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:


The hig” should be replaced with “50 values of H2O2 were found for cell pretreated with 50 μg/mL BJLN (89.95 μM) and 100 μg/mL MR219 (143.90 μM) extracts when compared to negative control (271.00 μM) Significant decrements in the IC1.00 μM) . The hig.”In addition, in the “Results” (Section 3.3), the text reading “An incorrect version of μg/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 μg/mL) (grey dotted line).Accordingly,


In the crystal, the ASP anions are linked  14H16NO+·C4H6NO4−·H2O, crystallizes as a monohydrate. The 1,2-diphenylethyl 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—H⋯O hydrogen bonds to form a 21 helix along the b-axis direction. The helices are linked by the ADE cations via O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to the bc plane. There are channels in the layers that are occupied by water molecules, which link to both the anions and cations via Owater—H⋯O and N—H⋯Owater hydrogen bonds. There are also C—H⋯O and C—H⋯π interactions present within the layers.The title diastereomeric salt, formed between 2-amino-1,2-diphenylethanol (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 molecular 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-diphenylethanol (ADE)  is 48.71 (9)° and the torsion angle O1A—C1A—C2A—N1A is −65.0 (2)°. The hydroxy group adopts a gauche conformation [O1A—C1A—C2A—C9A = 60.1 (2)°] 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—C2B—C3B—C4B = −53.0 (2)°], which is the motif commonly found in l-ASP salts; for example l-His·l-ASP monohydrate  and 1.4 (3)°, respectively.S)-ASP anions correlated with crystallographic symmetry are linked via N1B—H1B3⋯O4Bii [2.868 (2) Å] hydrogen bonds into C(6) chains to form a right-handed 12-helix along the b-axis direction -cis-ADE cations via N—H⋯O hydrogen bonds [N1A—H1A2⋯O1B = 2.862 (2) Å and N1A—H1A1⋯O4Biii = 2.742 (3) Å] and O—H⋯O hydrogen bonds [O1A—H1O1⋯O2Bi = 2.752 (2) Å], forming layers parallel to the bc plane  Å and O1C—H1OA⋯O1Biv = 2.840 (2) Å] and N—H⋯Owater hydrogen bonds [N1B—H1B2⋯O1C = 2.938 (2) Å and N1A—H1A3⋯O1C = 2.926 (3) Å], shown in Fig. 4a-axis direction.In the crystal, the -cis-2-Amino-1,2-diphenylethanol (ADE) and aspartic acid (ASP) were purchased from Sigma–Aldrich Co. Ltd. The title molecular salt was obtained from an aqueous ethanol solution of racemic-ASP and -cis-ADE in a 2:1 molar ratio, heated to 333 K 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 310.1107/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:


The molecule has an almost planar geometry (r.m.s. deviation = 0.012 Å), and its molecular structure is stabilized by an intramolecular secondary Se⋯O interaction of 2.353 (3) Å, closing a four-membered N—C—Se⋯O ring. The title compound represents the first monomeric organoselenenyl chloride stabilized intramolecularly by an interaction of this type. The non-valent attractive Se⋯O interaction results in a substantial distortion of the geometry of the ipso-carbon atom. The endo-cyclic N—C—Se [102.1 (3)°] and exo-cyclic C—C—Se [136.9 (3)°] bond angles deviate significantly from the ideal value of 120° for an sp2-hybridized carbon atom, the former bond angle being much smaller than the latter. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains propagating along [010]. The chains, which stack along the a-axis direction, are linked by offset π–π interactions [intercentroid distance = 3.960 (3) Å], 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 biological activities °] and exo-cyclic C3—C2—Se1 [136.9 (3)°] bond angles deviate significantly from the ideal value of 120° 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 intramolecularly by an interaction of this type. Previously, the analogous stabilization of monomeric organoselenenyl chlorides by intramolecular secondary Se⋯S  Å, Cg is the centroid of the N1/C2–C6 ring, interplanar distances = 3.590 (2) Å, slippages = 1.671 Å, symmetry codes: (i) x − 1, y, z; (ii) x + 1, y, z].In the crystal, molecules are linked by C—H⋯O hydrogen bonds Table 1, forminget al.  of the title compound. Colourless prismatic crystals of the title compound were obtained after recrystallization of the crude product from dichloromethane (m.p. 433–435 K). IR , ν 1617, 1462, 1423, 1254, 1151, 836, 748, 621. 1H NMR : δ = 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. 3 2010ab,c ▸. A Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/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:


The 1:1 co-crystal comprising two fused-ring molecules features significant hydrogen bonding between the 1,8-dihydroxyanthraquinone coformers with the main links between the resulting dimeric aggregates and the bromonaphthoquinone coformer being of the type C—H⋯O. 10H5BrO2·C14H8O4 , features one molecule of each coformer. The 2-bromonaphthoquinone molecule is almost planar . The 1,8-dihydroxyanthraquinone molecule is planar (r.m.s. deviation for the 18 non-H atoms is 0.022 Å) and features two intramolecular hydroxy-O—H⋯O(carbonyl) hydrogen bonds. Dimeric aggregates of 1,8-dihydroxyanthraquinone molecules assemble through weak intermolecular hydroxy-O—H⋯O(carbonyl) hydrogen bonds. The molecular packing comprises stacks of molecules of 2-bromonaphthoquinone and dimeric assembles of 1,8-dihydroxyanthraquinone with the shortest π–π contact within a stack of 3.5760 (9) Å occurring between the different rings of 2-bromonaphthoquinone molecules. The analysis of the Hirshfeld surface reveals the importance of the interactions just indicated but, also the contribution of additional C—H⋯O contacts as well as C=O⋯π interactions to the molecular packing.The asymmetric unit of the title co-crystal, C The six carbon atoms comprising the cyclohexa-2,5-diene-1,4-dione ring of the naphthoquinone molecule are not strictly planar with the r.m.s. deviation being 0.030 Å; the maximum deviations are 0.025 (1) and −0.031 (2) Å for the C4a and C4 atoms, respectively. The appended Br1, O1 and O4 atoms lie, respectively, 0.077 (1), 0.078 (1) and −0.117 (1) Å 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 naphthoquinone molecule is 0.060 Å, with the maximum deviations being 0.093 (1) Å for atom Br1 and −0.099 (1) Å for the O4 atom, again with these atoms lying to opposite sides of the plane. With respect to the anthraquinone molecule, the r.m.s. deviation for the 18 non-H atoms is 0.022 Å with the maximum deviations being 0.039 (2) Å for C(13) and 0.026 (1) Å for the C19 and C23 atoms. As seen from Fig. 1b, the hydroxy-H atoms are orientated to be proximate to the centrally located carbonyl-O atom to form intramolecular hydroxy-O—H⋯O(carbonyl) hydrogen-bonds, Table 1The molecular structures of the constituents of (I)a, is connected by a centrosymmetric planar, eight-membered {⋯HO⋯O⋯H}2 synthon which incorporates two transannular hydroxy-O—H⋯O(carbonyl) hydrogen bonds. The dimeric aggregates stack along the b axis being surrounded by two columns of similar dimeric aggregates and six columns comprising naphthoquinone molecules, Fig. 2b. Connections between columns, leading to a three-dimensional architecture, are of the type sp2-C—H⋯O(carbonyl) and involve all the remaining carbonyl-O atoms with the O atom of the naphthoquinone-C4=O4 moiety forming two such contacts, Table 1i.e. between the  and  rings with the inter-centroid separation being 3.5760 (9) Å and the angle of inclination being 1.64 (7)° for symmetry operation x, −1 + y, z. The closest comparable interaction within the stack of anthraquinone molecules is 4.1013 (9) Å, i.e. between (C15–C21) and (C19–C24) rings; angle of inclination = 0.65 (7)° for symmetry operation: x, −1 + y, z.In addition to the intramolecular hydroxy-O—H⋯O(carbonyl) hydrogen-bonds in the anthraquinone molecule, both hydroxy-H atoms from weaker intermolecular hydrogen-bonds with a centrosymmetrically related molecule indicating each hydroxy-H atom is bifurcated, Table 1et al., 2016et al., 2016dnorm, Figs. 3The Hirshfeld surface analysis of title 1:1 co-crystal, (I)dnorm in Fig. 3a. On the Hirshfeld surface mapped over the calculated electrostatic potential, the respective donors and acceptors appear as the blue  and red regions  in Fig. 5a. The presence of faint-red spots near carbon atoms C11, C19, Fig. 3a, and near the atoms C15 and C20, Fig. 3b, also indicate the links between molecules through short inter-atomic C⋯C contacts, Table 2a. Links between the coformers involving their carbonyl-C4=O4 and C20=O20 groups through short interatomic C⋯O/O⋯C contacts, Table 2b and 4b. This is also illustrated by the black dashed lines on the Hirshfeld surface mapped over electrostatic potential in Fig. 6b. The donors and acceptors of intermolecular C—H⋯O(carbonyl) interactions can be viewed as bright-red spots having labels ‘3’–‘5’ in Figs. 3b and 4a, labelled with ‘6’. The immediate environments about reference anthraquinone and naphthoquinone molecules within shape-index-mapped Hirshfeld surfaces highlighting intermolecular O—H⋯O, C—H⋯O, π–π stacking and C—O⋯π interactions influential on the packing are illustrated in Figs. 7The donors and acceptors of intermolecular hydroxy-O—H⋯O(carbonyl) hydrogen-bonds between anthraquinone molecules are viewed as bright-red spots labelled with ‘1’ and ‘2’ on the Hirshfeld surfaces mapped over a. The plots delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C, C⋯C and C⋯O/O⋯C contacts  atoms are viewed as a pair of short spikes at de + di ∼ 2.4 Å in the donor and acceptor regions of their respective plots in Fig. 9c. The points corresponding to anthraquinone-C15—H15⋯O4(carbonyl) interactions and other short interatomic O⋯H contacts, Table 2The donors and acceptors of the naphthoquinone-H3 and anthraquinone-O20(carbonyl) atoms are viewed as a thin, long spike at de + di < 2.9 Å, i.e. less than sum of their van der Waals radii, in the fingerprint plot delineated into C⋯H/H⋯C contacts for anthraquinone, Fig. 9d, are indicative of short interatomic C⋯H contacts, Table 2e, having high density at around de = di ∼ 1.8 Å. The parabolic distribution of points with the peak at de = di ∼ 1.6 Å in the plot for the anthraquinone coformer, Fig. 9e, indicates links between these molecules through short interatomic C⋯C contacts along the b axis. The presence of C⋯C contacts in (I)A pair of short peaks at f, results from short, inter-atomic C⋯O/O⋯C contacts whereas the 11.9% contribution from C⋯O/O⋯C contacts for the anthraquinone molecule has a contribution from C=O⋯π interactions involving carbony-O19 and -O20 atoms and  and  rings, Table 4f.The 3.9% contribution from C⋯O/O⋯C contacts to the Hirshfeld surface for the naphthoquinone molecule, Fig. 9Although the naphthoquinone-bromide substituent makes a notable contribution to the Hirshfeld surface, Table 3et al., 2016cf. 0.060 Å 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–red crystals with yields of 78–85% based upon the quantity of 1,8-dihydroxyanthraquinone initially used. Notably, the substrates 2-bromonaphthoquinone and 1,8-dihydroxyanthraquinone could not be chromatographically distinguished as they ran with equivalent Rf’s 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 413–414 K, which is intermediate between the melting points of the pure components 2-bromonaphthoquinone, 405–406 K Uiso(H) set to 1.2Ueq(C). The O-bound H atoms were located from a difference map but refined with O—H = 0.84±0.01 Å and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/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:


I atom is surrounded by three μ3-iodide anions and one S atom, while the other is coordinated by three μ3-iodide ions an O atom. In the crystal, there are intermolecular C—H⋯I hydrogen bonds and C—H⋯π interactions 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 acetonitrile/dichloromethane results in a crystalline coordination polymer, namely poly[bis{μ2-1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1H)-one}tetra-μ3-iodidotetracopper(I)], [Cu4I4L2]n. The asymmetric unit comprises two ligand molecules, four copper(I) ions and four iodide ions. Interestingly, 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 molecules, forming a two-dimensional brick-wall structure. These two-dimensional networks are stacked alternately along [001]. Additionally, there are intermolecular C—H⋯I hydrogen bonds and C—H⋯π interactions between the ligands.The reaction of copper(I) iodide with 1-[2-(cyclohexylsulfanyl)ethyl]pyridin-2(1 CuI—O 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 μ3-iodide ions, and two L ligands as shown in Fig. 1A (identified by S1) and LB (identified by S2), the pyridyl and cyclohexyl rings are in anti and gauche conformations with torsion angles of −154.7 (6)° [C6—S1—C7—C8] and 62.3 (7)° [C19—S2—C20—C21], respectively. All of the CuI atoms (Cu1–Cu4) have distorted tetrahedral coordination geometries. The Cu1 and Cu2 atoms are bound by three μ3-iodide anions and one S atom, while Cu3 and Cu4 are coordinated by three μ3-iodide ions and one O atom. The ranges of interatomic distances in the title compound are 2.7082 (15)–2.7444 (14) Å, 2.297 (2)–2.314 (2) Å, 2.6210 (12)–2.7230 (12) Å, and 2.071 (6)–2.087 (6) Å for Cu—Cu, Cu—S, Cu—I, and Cu—O, respectively  as shown in Fig. 2A⋯I4ii, C12—H12⋯I1iii and C21—H21B⋯I3iv  hydrogen bonds between ligands. Red dashed lines display intermolecular C5—H5A⋯Cg1v [H⋯Cg1=3.00 Å] interactions between the ligands  complexes of N/S mixed donor atom ligands have been reported (Jeon Synthesis of 1-[2-(cyclohexylsulfanyl)ethyl]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 , 2.00–1.13 ; 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-(cyclohexylthio)ethanol  in chloroform. The mixture was stirred under reflux for 1 h then cooled to 253 K. Chloroform was removed, yielding crude 2-chloroethylcyclohexylsulfide. 2-Hydroxypyridine  and potassium hydroxide  were dissolved in 10 ml of tetrahydrofuran and 5 ml of water, and then the solution was added dropwise to the crude chloride. The solution was refluxed for 24 h and cooled. The crude product was extracted by dichloromethane. The dichloromethane layer was dried with anhydrous Na4I4Preparation of [CuL2]nL  was allowed to mix with an acetonitrile (5 ml) solution of CuI . The colourless precipitate was filtered and washed with a diethyl ether/acetonitrile (5/1 v/v) solution. Single crystals suitable for X-ray analysis were obtained by slow evaporation of dichloromethane from the reaction mixture.A dichloromethane (5 ml) solution of Uiso(H) = 1.2Ueq(C) for aromatic C—H groups, C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for CH2 groups, and C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for Csp3—H groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


The title compound was isolated as a by-product from a reaction incorporating 2,4,6-trimethylbenzoic acid under basic conditions. 20H22O3, was formed in the reaction between 2,4,6-trimethylbenzoic acid and N,N-diisopropylethylamine in the presence of 1,3-dichloro-1,3-bis(dimethylamino)propenium 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 molecule, the other half of which is generated by twofold rotation symmetry; the dihedral angle between the symmetry-related aromatic rings is 54.97 (3)°. The geometric parameters of the aromatic ring are typical of those for 2,4,6-trimethylphenyl substituted groups. The C=O and C—O bond lengths are 1.1934 (12) and 1.3958 (11) Å, respectively, and the angle between these three atoms (O=C—O) is 121.24 (9)°. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds and C—H⋯π interactions. The packing features wavy chains that extend parallel to [001].The title compound, C The C1—C2 distance is normal for an sp2–sp2 bond, with a length of 1.4873 (13) Å. The second half of the molecule, which is generated by rotation about the twofold axis passing through O1 , forms a dihedral angle of 54.97 (3)° between the equivalent aromatic rings. If the planes of the two overlapping CO2 groups are chosen instead, the dihedral angle becomes 59.30 (11)°. The C—C bonds in the aromatic ring are not all statistically equivalent. Unsurprisingly, the longest C—C bonds in the ring are adjacent to the electron-withdrawing anhydride group, C2—C3 [1.4032 (13) Å] and C2—C7 [1.4059 (13) Å]. The remaining C—C bonds are statistically equivalent, averaging 1.3942 (8) Å. All of the C—CH3 bond lengths are statistically equivalent with an average length of 1.5102 (8) Å.The molecular structure of the title compound is shown in Fig. 1a axis, forms wavy chains that run parallel to the c-axis direction  and H6 (2.39 Å to H10A), and the designated methyl H atoms, which close five-membered rings in the molecule.There are short intramolecular contacts between the aromatic H atoms H4  were added to a chloroform solution (25 ml) of 1,3-dichloro-1,3-bis(dimethylamino)propenium 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 h, clear and colourless thin plate-like crystals were obtained . Elemental analysis, calculated for C20H22O3 (%): C 77.39, 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 210.1107/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:


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 pentagonal–bipyramidal environment. Each dipyridyl-type ligand links the CoII atoms into polymeric zigzag chains, which are connected via intermolecular π–π stacking interactions and N/C—H⋯O hydrogen bonds.The Co 3)2L]n, L = N-(pyridine-2-ylmethyl)pyridine-3-amine (C11H11N3), contains one CoII centre, two nitrate anions and one L ligand in which the Cpy—C—N—Cpy moiety adopts a trans conformation with a torsion angle of −173.1 (3) Å. The coordination geometry of the CoII atom is a distorted pentagonal bipyramid. One amine N atom from the L ligand and four O atoms from two η2-nitrato ligands form the basal plane and two pyridyl N atoms from two symmetry-related L ligands occupy the apical positions [N—Co—N = 171.86 (11)°]. The displacement of the central CoII atom from the basal plane (r.m.s. deviation = 0.085 Å) is 0.1491 (12) Å. 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—H⋯O hydrogen bonds between the ligands and the nitrate anions are observed. Adjacent zigzag chains are connected via intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.844 (2) Å] between the pyridine rings together with N/C—H⋯O 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-ylmethyl)pyridine-3-amine ligand.Over the past few decades, the continuous efforts have been devoted to the design and development of metal–organic 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 °; symmetry code: (i) x, −y + z − II atom is displaced by 0.1491 (12) Å from the basal plane (r.m.s. deviation = 0.085 Å). The Co—N distances in apical positions  are slightly shorter than that of the basal [Co1—N2 = 2.191 (3) Å]. The largest deviations from the NO4 basal plane around the cobalt center involve the angles O2—Co1—O3 [55.81 (11)°] and N2—Co1—O5 [84.19 (9)°]. This distortion may reflect the narrow bite angles of the bidentate nitrate ions.The asymmetric unit of the title compound comprises one Co ] Fig. 1. The cenL ligand adopts a stretched trans conformation with the C5—C6—N2—C7 torsion angle being −173.1 (3) Å. The terminal pyridine rings of the L ligand are nearly perpendicular to each other, with the dihedral angle between their mean planes being 76.74 (12)°. Each bidentate nitrate group is bonded asymmetrically to the cobalt atom . Each L ligand is bridged by the CoII ions, forming –(Co-L)n– zigzag chains propagating along the c-axis direction  Å; Cg1 is the centroid of the N1/C1–C5 ring; symmetry code: (ii) −x, −y + 1, −z + 1] between the pyridine rings and C—H⋯O 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 2·6H2O in the molar ratio 1:1.The d(N—H) = 0.96 Å]. All other H atoms were positioned geometrically and refined as riding, with d(C—H) = 0.93 Å for Csp2—H and 0.97 Å for methylene C—H. For all H atoms, Uiso(H) = 1.2Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


The structure of a coumarin ester stabilized by C—H⋯O hydrogen bonds and C=O⋯π and π–π stacking interactions 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 (15)° relative to the coumarin plane (r.m.s deviation = 0.009 Å). This conformation of (I) is stabilized by an intramolecular C—H⋯O hydrogen bond, which closes a five-membering ring. In the crystal, molecules of (I) form infinite zigzag chains along the b-axis direction, linked by C—H⋯O hydrogen bonds. Furthermore, the crystal structure is supported by π–π stacking interactions between neighbouring pyrone and benzene or coumarin rings [centroid–centroid distances in the range 3.5758 (18)–3.6115 (16) Å], as well as C=O⋯π interactions [O⋯centroid distances in the range 3.266 (3)–3.567 (3) Å]. The theoretical data for (I) obtained from quantum chemical calculations are in good agreement with the observed structure, although the calculated C—O—C—C torsion angle between the coumarin fragment and the benzene ring (73.7°) is somewhat larger than the experimental value [63.4 (4)°]. Hirshfeld surface analysis has been used to confirm and quantify the supramolecular interactions.In the title compound, C They also form the core of several molecules of pharmaceutical importance. Coumarin and its derivatives have been reported to serve as anti-bacterial (Basanagouda S(5) ring motif arises from the intramolecular C16—H16⋯O3 hydrogen bond d Table 1, and gend Table 1. The couC(4) chains along the [010] direction  = 3.336 (5) Å] and C1=O2⋯π interactions are present . The resulting supramolecular aggregation is completed by the presence of π–π stacking between the pyrone and C4–C9 benzene rings or coumarin ring systems  = 3.5758 (18), Cg1⋯Cg4  = 3.6116 (16), Cg2⋯Cg4  = 3.6047 (16) Å, where Cg2 is the centroid of the C4–C9 benzene ring] are less than 3.8 Å, the maximum regarded as suitable for an effective π–π interaction  on ring J and distances between Cg(I) and perpendicular projection of Cg(J) on ring I (slippage) are summarized in Table 2In the crystal, the C2—H2⋯O2 hydrogen bond links molecules into infinite zigzag on Fig. 2. In addims Fig. 3. The cenet al., 2016et al., 1982et al., 1985et al., 2011et al., 2014meta-substituted coumarin esters  to 1.20 Å (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 interactions correspond to intermolecular C—H⋯O hydrogen bonds, C8⋯C5 , O⋯π and π–π stacking interactions 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 molecule  as predicted by the X-ray study. The most significant contribution to the Hirshfeld surface (27.7%) is from H⋯O/O⋯H contacts, which appear on the left-side as blue spikes with the tip at de + di = 2.4 Å, top and bottom . As expected in organic compounds, the H⋯H 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 Å  whereas the F⋯H/H⋯F 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⋯H/H⋯C plot (16.2%) reveals information on the intermolecular hydrogen bonds . Other visible spots in the Hirshfeld surfaces indicate the C⋯O/O⋯C, O⋯O, F⋯F and C⋯F/F⋯C contacts, which contribute only 6.6, 1.3, 1.2 and 1.1%, respectively .Molecular Hirshfeld surfaces and the associated two-dimensional fingerprint plots of (I)le Fig. 4. In the le Fig. 4, the adjns Fig. 6a as preom Fig. 6b. As ex Å Fig. 6c wherea Å Fig. 6d. The Cds Fig. 6e. Otherly Fig. 6f–6i.++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-fluorobenzoyl chloride  in dried tetrahydrofuran (40 mL) was added dried triethylamine  and 7-hydroxycoumarin  by small portions over 30 min. The mixture was then refluxed for 4 h and poured into 40 mL of chloroform. The solution was acidified with diluted hydrochloric acid until the pH was 2–3. 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 310.1107/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:


In the anion, the carboxylate group is twisted away from the attached benzene ring by 84.9 (2)°. The CoII atom is coordinated by two TMB anions and two water molecules in the basal plane, while another water molecule 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 octahedron. The coordinating and bridging water molecules link to the carboxylate groups via intra- and intermolecular O—H⋯O hydrogen bonds, enclosing S(6) ring motifs, while the coordinating, bridging and non-coordinating water molecules link to the carboxylate groups and the coordinating water molecules link to the non-coordinating water molecules via O—H⋯O hydrogen bonds, enclosing R22(8) and R33(8) ring motifs. Weak C—H⋯O and C—H⋯π interactions may further stabilize the crystal structure.The asymmetric unit of the title one-dimensional polymeric compound, {[Co(C The Co1 atom lies 0.2077 (1) Å above the carboxylate (O1/O2/C1) group, which makes a dihedral angle of 84.9 (2)° with the adjacent benzene (C2–C7) ring.The two carboxylate O atoms  hydrogen bonds (Table 1S(6) ring motifs  hydrogen bonds benzoato-1κO]manganese(II)]-μ-aqua]dihydrate], {[Mn(C11H14NO2)2(H2O)3]·2(H2O)}n, (II), benzoate (DEAB) anions and two water molecules in the basal plane, while another water molecule 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-·2H2O}n, , {[Mn(C10H11O2)2(H2O)3]·2H2O}n, (VIII), which had previously been reported by Chen et al.  anions and two water molecules in the basal plane, while another water molecule 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 (15) Å] across the chain °] in (I)M—ObrdW—M  bond angles increase, while the M—ObrdW bond lengths decrease with increasing atomic number, Z, of the transition metal(II) atoms and the M⋯M distances across the polymeric chains are almost the same, independent of the type of anion coordinating to the metal(II) atoms.The Co1⋯Co1in Fig. 2 and the 4·7H2O  with sodium 2,4,6-trimethylbenzoate  in H2O (150 ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for eight weeks, giving pink single crystals . FT–IR: 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 molecules are: O3—H31 = 0.806 (19), O3—H32 = 0.818 (18), O4—H41 = 0.827 (18), O5—H51 = 0.812 (10), O5—H52 = 0.820 (10) Å and H31—O3—H32 = 107 (4) and H51—O5—H52 = 107 (4)° The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k × 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 Å and 0.82 Å from Co1. The high residual electron density value of 2.178 e Å−1 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 210.1107/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:


A linear SP coordination geometry for the gold atom is found in the title structure, which also features a short intramolecular Au⋯O interaction, in contrast to a Au⋯π interaction 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  Å], in contrast to the aryl ring in the original polymorph. In the crystal, linear supramolecular chains along the a-axis direction mediated by C–H⋯π and nitro-O⋯π interactions are found. These pack with no directional interactions between them. The analysis of the Hirshfeld surfaces for both forms of [Au(C9H9N3O3S)(C21H21P)] indicates quite distinctive interaction profiles relating to the differences in intermolecular contacts found in their respective crystals.The title phosphanegold(I) thiolate compound, [Au(Ckink 2008. Acta Cr R3PAu[SC(OR′)=NR′′], for R, R′ = alkyl, aryl and R′′ = 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  thiolates of the general formula R3PAu[SC(OR′)=NR′′] display an intramolecular Au⋯O interaction. In an exercise in crystal engineering, it was argued that by moderating the electronic properties of the phosphane-bound and thiolate-N-bound groups, it was possible to direct a change in conformation so that an intramolecular Au⋯π(aryl) interaction formed instead of the Au⋯O contact =NPh], that was originally reported in a form with an intramolecular Au⋯O interaction =NC6H4NO2-4] is reported which was reported originally in space group Cc with a Au⋯π(aryl) interaction 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 molecule, i.e. EtOC(=S)N(H)C6H4NO2-4 Cc polymorph The central S1, O1, N1 and C1 atoms of the thiolate ligand are strictly (r.m.s. deviation of the fitted atoms = 0.0008 Å) planar. The plane through the nitrobenzene ligand is orthogonal to the former plane, forming a dihedral angle of 89.67 (12)°. Finally, the nitro group is essentially co-planar with the ring to which it is connected, forming a dihedral angle of 4.7 (4)°.Crystal Explorer a-axis direction, Fig. 3a. These are sustained by a combination of nitrobenzene-C—H⋯π(tolyl) interactions as well as nitro-O⋯π(tolyl) contacts, Fig. 3b. For the latter, the nitro group lies over the ring, with the two residues being almost parallel, forming a dihedral angle = 7.4 (2)°. While comparatively rare, the latter interactions have been discussed in the crystallographic literature dnorm for forms (I)a indicate the significance of short inter-atomic C⋯O/O⋯C contacts, Table 4a, b, and the dnorm-mapped surface for (II), Fig. 5c, are consistent with (I)a. The intermolecular nitro-O⋯π interaction involving both nitrobenzene-O2 and O3 atoms with the same symmetrically located tolyl ring (C17–C22) are viewed as two adjoining blue and bright-orange regions in Fig. 5b. The short inter-atomic S⋯H/H⋯S, C⋯H/H⋯C and O⋯H/H⋯O 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 thiolate ligands significantly impact upon the observed features in the plots. This is also visible from the fingerprints delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and S⋯H/H⋯S contacts c, wherein the half-arrows in (I)de + di ∼ 2.8 Å and 2.9 Å, respectively, arise as the result of distinctive intermolecular interactions in the two forms: the former has a C—H⋯π contact while the latter has short inter-atomic C⋯H/H⋯C contacts, Fig. 5c and Table 4b and Table 4c and d, reflects the different types of inter-atomic contacts they form. In the respective plots for the form (I)de + di ∼2.7 Å in the O⋯H/H⋯O delineated and the knife-edge tips at de + di ∼2.9 Å in the S⋯H/H⋯S delineated fingerprint plots for (II) are the result of short inter-atomic O⋯H/H⋯O and S⋯H/H⋯S contacts, Table 4The distinctive features of fingerprint plot delineated into C⋯H/H⋯C contacts, Fig. 62)CH2(Ph2)PAuCl. In the original form, intramolecular Au⋯Au interactions [3.34 Å] were observed CH2(Ph2)PAuCl imply that Au⋯π(aryl) interactions 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 intramolecular Au⋯π(aryl) contact was more than 5 kcal  mol−1 stable than the form with the intramolecular Au⋯O contact =N]2 indicated that each Au⋯π(aryl) interaction in the centrosymmetric molecule was more stable by more than 12 kcal mol−1 than each putative Au⋯O contact  interactions can be seen in the polymorphic structures of ClAuP solution of (I)1H NMR (δ): thiolate: 7.92 , 6.89 , 4.34 , 1.35 . Phosphane: 7.32–7.22 , 2.40 . 13C NMR (δ): Thiolate: 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 1.2–1.5Ueq(C). The maximum and minimum residual electron density peaks of 1.16 and 0.78 e Å−3, respectively, were located 0.81 and 1.28 Å from the Au atom. Owing to interference 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 610.1107/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:


In the title compound, the protonated piperazine ring adopts a chair conformation while the indole ring plane is nearly perpendicular to the benzofuran ring system. 26H28N5O2+·Cl−·CH3OH {systematic name: 4-(2-carbamoyl-1-benzofuran-5-yl)-1-[4-(5-cyano-1H-indol-3-yl)butyl]piperazin-1-ium chloride methanol monosolvate}, the protonated piperazine ring adopts a chair conformation. The indole ring plane is nearly perpendicular to the benzofuran ring system, with a dihedral angle of 85.77 (2)°. In the crystal, the organic cations, Cl− anions and methanol solvent molecules are linked by classical N—H⋯O and N—H⋯Cl hydrogen bonds, and weak C—H⋯O and C—H⋯π interactions into a three-dimensional supramolecular architecture.In the title compound, C Major depression disorder (MDD) currently ranks as the world’s 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− anion and one methanol molecule le Fig. 1.et al., 2011n-butyl linker to the piperazine ring. The conformation of the butyl chain is of some interest. Three C atoms of the butyl group  are coplanar with atom C9 of the indole, as confirmed by the C9—C10—C11—C12 torsion angle of 179.2 (2)°, meanwhile atoms C11, C12 and C13 are coplanar with piperazine atom N3. A dihedral angle of 80.9 (2)° is formed between the mean planes of N3/C11–C13 and C9–C12. The dihedral angle between the C9–C12 mean plane and the indole plane is 10.0 (2)°. The second piperazine N atom, N4, is bonded to the benzofuran ring. The formamide group is almost coplanar with the connected benzofuran ring, making a dihedral angle of 2.53 (2)°. The indole ring is almost perpendicular to the benzofuran ring, as indicated by the dihedral angle of 85.77 (2)° between them.The expected proton transfer from hydrochloric 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—C1—C2—C7 and N1—C1—C2—C3 . The conformation of the cyano group is similar to that of other drugs containing nitrile groups, such as bicalutamide and Febuxostat  1 − x, −y, 1 − z] hydrogen bonds  1 − x, 2 − y, 2 − z] and N3—H3A⋯Cl1 link another two neighbouring cations and the Cl− anion into a molecular sheet. As a result, 28-membered rings with the graph-set motif In the crystal, N3—H3s Table 1, connected Fig. 2.Vilazodone hydrochloride 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—H = 0.82, N—H = 0.86 and C—H = 0.93–0.98 Å, 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 210.1107/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:


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′-bis[methyl]biphenyl-κ2N4:N4′}bis(nitrato-κO)zinc(II)], [Zn(NO3)2(C18H16N6)2]n, is a two-dimensional zinc coordination polymer constructed from 4,4′-bis[methyl]-1,1′-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′-bis[methyl]-1,1′-biphenyl ligands, forming a distorted octahedral {ZnN4O2} coordination geometry. The linear 4,4′-bis[methyl]-1,1′-biphenyl ligand links two ZnII cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C—H⋯O, C—H⋯N, C—H⋯π and π–π stacking interactions, resulting in a three-dimensional supramolecular architecture.The title compound, poly[bis{μ H-1,2,4-triazol-1-ylmethyl)benzene benzene benzene benzene methyl]-1,1′-biphenyl methyl]biphenyl-κ2N4:N4′}bis(nitrato-κO)zinc], [Zn(NO3)2(C18H16N6)2]n, was synthesized under hydrothermal conditions by the reaction of Zn(NO3)2·6H2O and 4,4′-bis[methyl]-1,1′-biphenyl at 313 K for 48 h. We report here its crystal structure and its elemental analysis.Over the past few decades, the self-assembly of coordination polymers (CPs) or metal–organic frameworks (MOFs) based on metal ions or clusters and organic ligands has attracted much attention, owing to their intriguing molecular 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-bismethyl]-1,1′-biphenyl ligand.The title complex crystallizes in the triclinic space group II cation exhibits a slightly distorted octahedral {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 methyl]-1,1′-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⋯Zn distances are 18.397 (3) and 18.964 (3) Å methyl]-1,1′-biphenyl ligand lie nearly in one plane [dihedral angle = 0.00 (2)°]. The two triazole groups of the 4,4′-bis[methyl]-1,1′-biphenyl ligand are inclined to the plane of the central biphenyl groups, with dihedral angles of 80.050 (2) (C1/C2/N1/N2/N3) and 85.511 (2)° (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  Å and C12—H12⋯Cg2iii = 3.5252 (7) Å; Cg1 and Cg2 are the centroids of the triazole (C1/C2/N1/N2/N3) and phenyl (C4–C9) rings, respectively; symmetry codes: (ii) 2 − x, −y, −z; (iii) 1 − x, 1 − y, −z] contacts and π–π stacking interactions [Cg1⋯Cg1ii = 3.6296 (10) Å]. These interactions, together with the covalent interactions in the infinite two-dimensional polymeric-like layer, make up a three-dimensional supramolecular structure.Neighbouring layers are linked to each other by by weak interactions Table 1, includiet al., 2016H-1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl moiety gave eight hits. Seven of them are constructed by 4,4′-bis[methyl]-1,1′-biphenyl units and different carboxylate ligands. One example is a chain structure based on Zn and 4,4′-bis[methyl]-1,1′-biphenyl 2·6H2O (0.1 mmol), 4,4′-bis[methyl]-1,1′-biphenyl (0.1 mmol) and water (6 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413 K for 72 h. 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 (11) and 0.489 (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 210.1107/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:


The H atom of the oxime moiety is equally disordered over two positions, giving rise to two equivalent hydrogen bonds between adjacent molecules. 14H13NO2, is a commercially available material and can be used as a multidentate ligand. The molecule of the asymmetric unit has an R configuration, while the corresponding S-configured molecule of the racemic mixture is generated by a crystallographic centre of symmetry. Both hydroxy groups  are involved in hydrogen bonding, leading to the formation of chains extending parallel to [001].The title compound, C E)-2-hydroxy-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 molecules in the unit cell and one molecule in the asymmetric unit. As the compound possesses an asymmetric carbon atom (C2), the molecule of the asymmetric unit has an R-configuration while the corresponding S-configured molecule of the racemic mixture is generated by a crystallographic centre of symmetry. Both molecules 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 (2) Å for C2 and 1.484 (2) Å for C1, respectively. The hydroxy group attached to C2 shows a C—O bond length of 1.425 (2) Å, which also lies in the normal range (1.421–1.433 Å) of a C2–CH–OH group  Å] of the N=C double bond Table 1 is consiet al., 1987ar—Car. The mean value of the endocyclic bond angles within the phenyl rings is 120.0 (5)° with minima at the ipso carbon atoms C11 [118.3 (1)°] and C21 [119.1 (1)°]. The phenyl rings form an interplanar angle of 80.72 (5)°.The two phenyl groups exhibit a mean C—C bond length of 1.387 (5) Å [variation: 1.374 (3)–1.398 (2) Å], in excellent agreement with the literature value (Allen ii = 2.829 (2) Å, 〈O2—H3⋯O2ii = 164°; symmetry code: (ii) = −x + 1, −y, −z + 1] and a twofold rotation axis [O2⋯O2iii = 2.806 (2) Å, 〈O2—H4⋯O1iii = 175°; symmetry code (iii) = −x + 1, y, −z + i = 2.805 (2) Å, 〈O1—H1⋯ N1i = 144°; symmetry code: (i) = −x + 1, y, −z + The molecule possesses two hydroxy 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. 2 with itses Fig. 4. The twoα-benzoinoxime was refluxed with di-n-butyltin oxide, C8H18OSn, in ethanol for 2.5 h. Single crystals of the title compound suitable for X-ray diffraction were obtained from the ethanolic solution layered with n-hexane.In a typical experiment, sp3-hybridized and 0.95 Å for aromatic H atoms, and with Uiso(H) = 1.2Ueq(C). The H atoms of the two hydroxy groups were modelled with a common O—H distance of 0.96 Å before they were fixed and allowed to ride on the corresponding oxygen atom with Uiso(H) = 1.2Ueq(O). Disorder of the hydroxy 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 310.1107/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: