I complex, a discrete binuclear AgI complex, acetate anions, acetonitrile solvent molecules and water molecules. The molecular components are linked through O—H⋯O, N—H⋯O and O—H⋯S hydrogen bonds, forming a chain structure along [100].The title compound consists of a mononuclear Ag 2(C3H6N2S)4(C18H15P)2](C2H3O2)2·[Ag(C2H3O2)(C3H6N2S)(C18H15P)2]2·2C2H3N·4H2O, the AgI ion in the mononuclear neutral complex exhibits a distorted tetrahedral environment with coordination by two P atoms from triphenylphosphane (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–S–Ag–S 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 tetrahedral environment. In the crystal, the mononuclear complex is linked to lattice water molecules through O—H⋯O and N—H⋯O hydrogen bonds, forming a chain along [100]. In addition, the binuclear complex molecules are connected to acetate anions and lattice water molecules via O—H⋯O, N—H⋯O and O—H⋯S hydrogen bonds, also along [100].In the title compound, [Ag The molecule 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–S–Ag–S ring. Each AgI ion is in a distorted tetrahedral 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 molecular components of the title compound are shown in Fig. 1A⋯O6, O7—H7B⋯O6iv, N6—H6⋯O4 and N5—H5⋯O7iii hydrogen bonds   was added and the mixture was stirred for 3 h. Ethylenethiourea  was added and the new reaction mixture was heated under reflux for 5 h. 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.Triphenylphosphane  was dissolved in 30 cmUiso(H) = 1.2Ueq(C); 0.99 Å (CH2) and Uiso(H) = 1.2Ueq(C); 0.98 Å (CH3) and Uiso(H) = 1.5Ueq(C); 0.88 Å (NH) and Uiso(H) = 1.2Ueq(N). Water hydrogen atoms were located from a difference Fourier map and were refined with an O—H distance restraint of 0.84 (2) Å and Uiso(H) = 1.2Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/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:


The asymmetric unit of the title compound contains two crystallographically independent molecules with the similar conformation, the piperidine rings in both molecules adopt a similar distorted chair conformation and have pseudo mirror planes passing through the N—O bond. 22H25F2N4O2, contains two crystallographically independent molecules. In one molecule, the two benzene rings are oriented at a dihedral angle of 1.93 (10)° and in the other molecule the corresponding dihedral angle is 7.19 (9)°. The piperidine rings in the two molecules adopt a similar distorted chair conformation, and both have pseudo-mirror planes passing through the N—O bonds. An intramolecular O—H⋯N hydrogen bond between the hydroxy group and the imine N atom is observed in both molecules. In the crystal, weak C—H⋯O and C—H⋯F hydrogen bonds, enclosing R22(6) ring motifs, and weak π–π stacking interactions link the molecules into a three-dimensional supramolecular network, with centroid-to-centroid distances between the nearly parallel phenyl and benzene rings of adjacent molecules of 3.975 (2) and 3.782 (2) Å.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 (10) and 0.92 (9)°, respectively, to the adjacent benzene (B and E) rings.The phenyl [C (N4/C14–C18) and F (N8/C36–C40)] rings are in distorted chair conformations  having total puckering amplitudes QT of 0.491 (3) Å (for ring C) and 0.509 (3) Å (for ring F), and they have pseudo mirror planes passing through the N4—O2 (for ring C) and N8—O4 (for ring F) bonds.The piperidine , with centroid–centroid distances of 3.975 (2) and 3.782 (2) Å, respectively, may further stabilize the structure.In the crystal, strong intramolecular O—H⋯N and weak intermolecular C—H⋯O and C—H⋯F hydrogen bonds Table 2 link the3 (1:1) solution (70 ml) of 5-[diazenyl]-2-hydroxybenzaldehyde , and heated at 333 K for 2 h. 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. 473–475 K).The title compound was synthesized by the reaction of 5-[diazenyl]-2-hydroxybenzaldehyde , 0.97 Å (for CH2) and 0.98 Å (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 310.1107/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:


E conformation. An intramolecular C—H⋯F hydrogen bond generates an S(6) ring motif. In the crystal, molecules are arranged into centrosymmetric dimers via pairs of C—H⋯F hydrogen bonds. The crystal structure also features C—H⋯π and π–π interactions. Hirshfeld surface analysis was used to confirm the existence of intermolecular interactions.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 (8)° and an intramolecular C—H⋯F hydrogen bond generates an S(6) ring motif. In the crystal, molecules are arranged into centrosymmetric dimers via pairs of C—H⋯F hydrogen bonds. The crystal structure also features C—H⋯π and π–π interactions. Hirshfeld surface analysis was used to confirm the existence of intermolecular interactions.In the title compound, C The anthracene ring system (C10–C23) is twisted at the C9–C10 bond from the (E)-3-(2-chloro-6-fluorophenyl)acrylaldehyde moiety [maximum deviation = 0.193 (16) Å for atom O1] with a C8—C9—C10—C23 torsion angle of −61.4 (2)°. The terminal benzene and anthracene ring systems  form a dihedral angle of 63.42 (8)°. The least-squares plane through the enone moiety [O1/C7–C9) with a maximum deviation of 0.033 (2) Å for atom C9] makes dihedral angles of 5.62 (13) and 59.18 (12)° with the benzene (C1–C6) and anthracene (C10–C23) rings, respectively. An intramolecular C8—H8A⋯F1 hydrogen bond is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with those in previously reported structures  interactions .In the crystal Fig. 2, the mol1 Table 1 hydrogeng1 Fig. 3 and Cg1⋯et al., 2012dnorm are shown in Fig. 4The intermolecular interactions of the title compound can be visualized using Hirshfeld surface analysis .The C17—H17ed + id ∼2.6 Å on the fingerprint plot. The presence of π–π interactions is shown as C⋯C contacts, which contribute 8.9% of the Hirshfeld surfaces. The presence of these interactions can also be shown by the Hirshfeld surfaces mapped by shape index  can be also be seen, indicated by the wings of ex Fig. 6 and the ex Fig. 6.A mixture of 9-acetylanthracene  and 2-chloro-6-fluorobenzaldehyde  was dissolved in methanol (20 ml). A catalytic amount of NaOH  was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml) 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 (−1 − 2 4 and −1 1 0) were omitted from the final refinement.Crystal data collection and structure refinement details are summarized in Table 210.1107/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:


P21/n, the methyl acrylate and nitrovinyl 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 (9) and 75.65 (2)° for compounds (I) and (II), respectively. In the crystal of (I), chains along the b axis are formed via C—H⋯O hydrogen bonds. In the crystal of (II), molecules are linked by C—H⋯O 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 (2) Å for the methyl C atom, while in (II) this deviation is 0.0147 Å. The interplanar angles between the two aromatic rings are 74.87 (9) and 75.65 (2)° for compounds (I) and (II), respectively. In both compounds, the methyl acrylate and nitrovinyl groups each adopt an E conformation about the C=C bond. In the crystal of (I), molecules are linked by C—H⋯O hydrogen bonds forming chains along the b axis. The chains are linked via C—H⋯Cl hydrogen bonds, forming sheets parallel to the ab plane. The sheets are linked via C—H⋯π interactions, forming a three-dimensional structure. In the crystal of (II), molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(30) ring motif. The dimers are linked via C—H⋯O hydrogen bonds, forming sheets parallel to the ac plane and enclosing R44(28) ring motifs. The sheets are linked via parallel slipped π–π interactions (intercentroid distances are both ca 3.86 Å), forming a three-dimensional structure.The title compounds, C In (I)In both compounds, the nitrovinyl groups [C2=C1—N1], have an b-axis direction n Table 1. The chane Fig. 4. The shee Table 1.ac plane and enclosing via slipped parallel π–π interactions, forming a three-dimensional structure, Fig. 6Cg1⋯Cg1i = 3.863 (2) Å, inter-planar distance = 3.487 (1) Å, slippage 1.662 Å; Cg1 is the centroid of ring C3–C8; symmetry code: (i) −x + 1, −y, z + 1, and Cg2⋯Cg2ii = 3.861 (2) Å, inter-planar distance = 3.506 (2) Å, slippage = 1.617 Å; Cg2 is the centroid of ring C14–C19; symmetry code: (ii) −x + 1, −y, −z + 2].In compound (II)f Table 2. The dims Table 2. The sheE)-2-(phenoxymethyl)-3-phenylacrylate gave 12 hits. There is a great variety in the dihedral angle involving the two aromatic rings; from a minimum of ca 47.2° in (E)-methyl 2-({2-ethoxy-6-[(E)-(hydroxyimino)methyl]phenoxy}methyl)-3-phenylacrylate -2-[(2-nitrophenoxy)methyl]-3-phenylacrylate -3-(2-chlorophenyl)-2-{[2-phenoxy]methyl}acrylate (1 mmol) for compound (I)E)-2-{[4-chloro-2-phenoxy]methyl}-3-(2-chlorophenyl)acrylate (1 mol) for compound (II)tert-butyl dicarbonate (1.2 equiv) were added and the solutions of the corresponding crude products were stirred at 318–323 K for 2 h, 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-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


The packing features supramolecular layers sustained by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonding.A distorted octahedral  2(C12H10N2)3(C6H12NOS2)4]·4C2H3N, comprises a CdII atom, two dithiocarbamate (dtc) anions, one and a half trans-1,2-dipyridin-4-ylethylene (bpe) molecules and two acetonitrile solvent molecules. The full binuclear complex is generated by the application of a centre of inversion. The dtc ligands are chelating, one bpe molecule coordinates in a monodentate mode while the other is bidentate bridging. The resulting cis-N2S4 coordination geometry is based on an octahedron. Supramolecular layers, sustained by hydroxy-O—H⋯O(hydroxy) and hydroxy-O—H⋯N(bpe) hydrogen bonding, interpenetrate to form a three-dimensional architecture; voids in this arrangement are occupied by the acetonitrile solvent molecules. Additional intermolecular interactions falling within the specified framework have been analysed by Hirshfeld surface analysis, including π–π interactions.The asymmetric unit of the title compound, [Cd The dithiocarbamate ligands coordinate with significant differences in their Cd—S bond lengths, Table 1d(Cd—Slong) – d(Cd—Sshort) = 0.15 Å for the S1-dithiocarbamate ligand cf. 0.10 Å for the S3-ligand. Nevertheless, there is considerable delocalization of π-electron density in the CdS2C chelate rings as evidenced by the equivalence of the associated C—S bond lengths, Table 1trans [178.06 (3)°] and the less tightly bound sulfur atoms are trans to nitrogen atoms, Table 1cis. The distortions from the ideal geometry are readily related to the restricted bite angles of the chelating ligands, Table 1i and C22—C21—C24—C25 torsion angles of −12.2 (6) and 13.9 (5)° for the bi- and mono-dentate ligands, respectively; symmetry code: (i) 2 − x, −y, 1 − z.The molecular structure of the binuclear title compound, {Cdn TONTO  interactions  and pyridyl-C—H⋯N(acetonitrile) interactions. The presence of short intermolecular C⋯C and C⋯H contacts, Table 3A atoms in Fig. 3i link of the bridging bpe ligand can be viewed as a bright-red region around the C18 atom in the dnorm mapped surface, Fig. 3b; this arises as it is the asymmetric unit that has been investigated not the entire binuclear molecule. With respect to the acetonitrile molecule the dnorm mapped surfaces show only the acetonitrile-N7 to be involved in a significant intermolecular C—H⋯N interaction  Å, symmetry code: 3 − x, 1 − y, 2 − z] is reflected through the appearance of green points around de = di ∼1.8 Å, the red and blue triangle pairs on the Hirshfeld surface mapped with shape-index property identified with arrows in the image of Fig. 7g, with the tips at de + di ∼2.95 Å arising from the short interatomic S⋯H/H⋯S contacts listed in Table 3In the absence of C—H⋯π interactions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into C⋯H/H⋯C contacts with 15.9% contribution to the Hirshfeld surface, Fig. 6et al., 2014i.e. 0.97, is in accord with expectation , may be calculated on the basis of Hirshfeld surface analysis 2(μ-bpe)]n, which is a linear coordination polymer with a trans-N2S4 donor set  zinc atoms 2]2(μ-bpe) species still forms with non-coordinating bpe included in the structure 2]2(μ-bpe) and one-dimensional [Zn(S2COEt)2(μ-bpe)]n are formed with the dimensionality correlated with the steric bulk of the xanthate-bound R groups 2]2(μ-bpe)}n, R = iPr and Cy (μ2-NO3)(μ-bpe)(bpe)(OH2)]n 2(μ-bpe)(bpe)2(OH2)4]n (μ-bpe)(bpe)2(OH2)2]NO3(bpe)(H2O)4.45 i.e. 2:1, 1:1 or 1:2, between the precursor molecules. In a typical experiment, Cd[S2CN(iPr)CH2CH2OH]2  was dissolved in boiling acetonitrile (30 ml). trans-1,2-Dipyridin-4-ylethylene  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 quantitative based on Cd. M.p. = 463–465 K (uncorrected). IR : 1607 m, 1449 ms, 1407 s, 1170 s, 1037 s, 968 s, 954 s, 824 s. NMR: 1H δ (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 1.2–1.5Ueq(C). The oxygen-bound H atoms were located in a difference Fourier map but were refined with a distance restraint of O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/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:


In the crystal, the two independent molecules stack head-to-tail probably due to the presence of the dipole moment of the  11H12N6O2, a π-conjugated triazene, crystallized with two independent molecules (A and B) in the asymmetric unit. Both molecules have an E conformation about the –N=N– bond and have slightly twisted overall conformations. In molecule A, the imidazole ring is inclined to the benzene ring by 8.12 (4)°, while in molecule B the two rings are inclined to one another by 7.73 (4)°. In the crystal, the independent molecules are linked to each other by C—H⋯O hydrogen bonds, forming –A–A–A– and –B–B–B– chains along [100]. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming sheets lying parallel to (001). The sheets are linked by further C—H⋯N hydrogen bonds and π–π interactions , 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’s viewpoint. It was as early as 1862 that Griess described a suitable method for the synthesis of 1,3-diphenyltriazene  of the title compound are illustrated in Fig. 1E conformation about the –N5=N4– and –N11=N10– bonds and the bond lengths and angles of the π-conjugated triazene unit  are inclined to one another by 7.73 (4)°.The molecular structures of the two independent molecules ; see Fig. 2Cg1⋯Cg4i = 3.5243 (5) Å; Cg1 and Cg4 are the centroids of the imidazole ring of molecule A and the benzene ring of molecule B; symmetry code: (i) x, y, z − 1], forming a three-dimensional framework structure : δ 7.99 , 7.85–7.83 , 7.70–7.69 , 7.55–7.52 , 7.06  3.60 . 13C NMR : δ 154.4, 151.1, 149.0, 130.6, 126.9, 118.8, 118.3, 114.4, 35.7. UV/Vis : λ (∊) = 455 nm. HRMS : m/z calculated for C11H13N6O2 [M + H]+ 261.1095, found 261.1094.1-Azido-3-nitrobenzene 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 310.1107/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:


Supramolecular layers sustained by N—H⋯N and N—H⋯π interactions are found in the crystal packing; these are connected by π–π contacts.A pentacoordinated Zn 32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex molecules and three benzylamine solvent molecules. Each complex molecule features a pentacoordinated 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 benzylamine molecule; it is the relative orientations of the latter that differentiate between the independent complex molecules. The uncoordinated benzylamine molecules display different conformations in the structure, with syn-Car—Car—Cm—N  torsion angles spanning the range −28.7 (10) to 35.1 (14)°. In the crystal, N—H⋯N and N—H⋯π interactions lead to supramolecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzylamine molecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π–π interactions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.The asymmetric unit of the title compound, 2[Zn(C Recent interest has centered on their electronic, photoelectronic and catalytic properties for a diverse array of applications including photodynamic therapy  is still less than 7 mM 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 (3) Å [Zn1—N6] to 2.045 (3) [Zn1—N4] Å, suggesting extensive delocalization of π-electron density over the PC chromophore. Further, the Zn—N(PC) bond lengths are systematically shorter than the Zn—N(amino) bonds. The N5 donor set defines an approximately square-pyramidal geometry with the benzylamino-N atoms occupying the axial position. In this description, Zn1 lies 0.4670 (16) Å above the least-squares plane defined by the four PC-N atoms (r.m.s. deviation = 0.0104 Å) in the direction of the benzylamino-N atom [2.570 (4) Å above the plane]; the comparable values for the Zn2-containing molecule are 0.4365 (16), 0.0076 and 2.549 (4) Å, respectively. That the N5 donor set defines a square pyramid is quantified by the value of τ = 0.02 for each of the Zn1- and Zn2-containing molecules, which compares to the τ values of 0.0 and 1.0 for ideal square-pyramidal and trigonal–bipyramidal geometries, respectively  angles collated in Table 1The asymmetric unit of (I)As seen from the overlay diagram in Fig. 2Database survey.A discussion of the uncoordinated benzylamine molecules is found below in the PLATON  interaction. The second amine-H atom of the coordinating benzylamine molecule forms an N—H⋯π(phenyl) interaction with a non-coordinating N21-benzylamine molecule. For the Zn2-containing molecule, the coordinating N18-benzylamine forms a donor N—H⋯N hydrogen bond to a non-coordinating N20-benzylamine molecule which is folded to enable a donor N—H⋯N hydrogen bond to an exocyclic-N atom of the PC dianion. As seen from the lower view of Fig. 3ab plane. These have a zigzag topology and present the flat PC residues to the outside with the benzylamine molecules, both coordinating and non-coordinating, in the inter-layer region. The layers stack along the c axis being connected by π–π interactions between pyrrolyl and fused-phenyl rings [inter-centroid ⋯(C57–C62) distance = 3.593 (2) Å with an angle of inclination = 6.1 (2)°]. A view of the unit cell contents is shown in Fig. 4Based on the standard criteria incorporated within i.e. with 4-methylpridine 2L2 , syn and anti-C(phenyl)—C(phenyl)—C(benzyl)—N(amine) torsion-angle data collated in Table 4et al., 2010Finally, a few comments on the benzylamine molecule which has now been characterized in its uncoordinated form in five crystal structures. From the et al., 2007−1) ν 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—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(N). Each of three solvent benzylamine molecules suffered from high thermal motion. In the final refinement the benzene rings were constrained to be regular hexagons (C—C = 1.39 Å) and their ADP’s 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 510.1107/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:


Weak C—H⋯Cl intermolecular interactions result in a two-dimensional extended sheet structure normal to the b axis.The molecular structure of [Fe 4(C5H7O2)4(CH3O)6Cl2] or [Fe4(acac)4(μ2-OMe)4(μ3-OMe)2Cl2] (acac = acetylacetonate), crystallizes in the orthorhombic Pbca space group with one half of the molecule 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—H⋯Cl intermolecular interactions 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 tetranuclear iron(III) methanolate compound, Fe4(acac)4(μ2-OMe)4(μ3-OMe)2Cl2, (I)We have investigated the syntheses of metal methoxysilanolates III metal atoms. Both cations are in approximately octahedral coordination environments. The coordination sphere of Fe1 is filled by the O atoms of one κ2-acac ligand [Fe1—O1 = 1.9971 (13) Å and Fe1—O2 = 1.9934 (13) Å], two μ2-methanolate groups , one μ3-methanolate group [Fe1—O4 = 2.2135 (12) Å], and one terminal chloride ligand [Fe1—Cl1 = 2.2776 (5) Å]. The coordination sphere of Fe2 is filled by the O atoms of one κ2-acac ligand [Fe2—O6 = 1.9717 (13) Å and Fe2—O7 = 1.9692 (12) Å], two μ2-methanolate groups [Fe2—O3 = 1.9755 (12) Å and Fe2—O5 = 1.9823 (12) Å], and two μ3-methanolate groups [Fe2—O4 = 2.0815 (12) Å and Fe2—O4i = 2.0809 (12) Å]. The angles around both Fe1 and Fe2 distort significantly from the ideal values of 90 and 180° of a perfect octahedron. For Fe1, the cis angles range from 75.69 (5) to 98.40 (4)°, while the trans angles range from 164.47 (5) to 170.40 (3)°. The angles around Fe2 have narrower ranges, with cis being 78.95 (5)–96.48 (5)° and trans being 170.08 (5)–170.16 (5)°.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⋯Fe distances range from 3.1997 (4) to 3.2175 (6) Å, while the Fe1⋯Fe1i distance is 5.5702 (6) Å.The molecular structure of (I)− ion and an acac ligand on neighboring molecules s Table 1. Taking is Fig. 2.4(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—Oacac distance of 1.978 Å is quite close to the average Fe—Oacac distance of 1.982 Å in (I)2-OMe: 1.977 Å; μ3-OMe: 2.124 Å) are also comparable to those in (I)2-OMe: 1.983 Å; μ3-OMe: 2.125 Å).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 ml) 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 × 10 ml) left a yellow solid. The yellow solid was extracted into dry CH2Cl2 and filtered through Celite. The CH2Cl2 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—C bonds, with idealized C—H, R—H and H⋯H distances (C—H = 0.98 Å). The remaining H atoms were included as riding idealized contributors (C—H = 0.95 Å). 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 210.1107/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:


II atom in the title compound shows a slightly distorted octahedral coordination environment to four N atoms of the azamacrocylic ligand in the equatorial plane and two isonicotinate O atoms in axial positions. Intermolecular N—H⋯N hydrogen bonds and π–π interactions consolidate the crystal packing.The Ni 6H4NO2)2(C16H38N6)], was prepared through self-assembly of a nickel(II) azamacrocyclic complex with isonicotinic acid. The NiII atom is located on an inversion center and exhibits a distorted octahedral N4O2 coordination environment, with the four secondary N atoms of the azamacrocyclic ligand in the equatorial plane [average Ni—Neq = 2.064 (11) Å] and two O atoms of monodentate isonicotinate anions in axial positions [Ni—Oax = 2.137 (1) Å]. Intramolecular N—H⋯O hydrogen bonds between one of the secondary amine N atoms of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the anion stabilize the molecular structure. Intermolecular N—H⋯N hydrogen bonds, as well as π–π interactions between neighbouring pyridine rings, give rise to the formations of supramolecular ribbons extending parallel to [001].The title compound, [Ni(C The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand  adopts the expected chair conformation, whereas the five-membered NiC2N2 ring (Ni1–N1–C1–C4–N2) 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 acetonitrile solution (8 mL) containing isonicotinic acid  and excess triethylamine  at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (l)16H38N6)(ClO4)2] for several days. Yield: 0.167 g (52%). FT–IR : 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 210.1107/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:


In the crystal, the cations, anions, 4-hydroxy-3-methoxybenzaldehyde and water molecules of crystallization are linked by classical O—H⋯O hydrogen bonds and weak C—H⋯O and C—H⋯Cl hydrogen bonds into a three-dimensional supramolecular architecture. The crystal packing is further stabilized by weak C—H⋯π interactions involving pyrrole and benzene rings. π–π stacking between parallel benzene rings of adjacent 4-hydroxy-3-methoxybenzaldehyde molecules is also observed, the centroid–centroid distance being 3.8003 (13) Å. The three F atoms of the anion are disordered over two sets of sites, with a refined occupancy ratio 0.527 (12):0.473 (12). The O atom of one water molecule of crystallization is also disordered over two positions in an occupancy ratio of 0.68 (5):0.32 (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:


In the crystal, weak N—H⋯S hydrogen bonds between the amino groups and the thiocyanate anions form an R42(8) motif. The complex molecules are linked by O—H⋯O, O—H⋯S, and N—H⋯S hydrogen bonds into a three-dimensional supramolecular structure. Weak π–π interactions between the pyridine rings is also found [centroid–centroid distance = 3.8578 (14) Å].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:


In the crystal, molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers which are linked by O—H⋯O hydrogen bonds, involving the crystal water molecule, 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 (8)°, while the benzene rings are normal to one another, making a dihedral angle of 89.69 (9)°. In the crystal, the water molecule links three molecules through two O—H⋯O and one N—H⋯O hydrogen bonds. The molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(14) ring motif. The dimers are linked by O—H⋯O hydrogen bonds, involving two molecules of water, forming chains along [100], enclosing R22(14) and R22(18) ring motifs. The chains are linked through C—H⋯O interactions, forming sheets parallel to (010). Within the sheets, there are C—H⋯π and parallel slipped π–π stacking interactions present [inter-centroid distance = 3.6458 (12) Å].The title compound, C N-Acylhydrazones have been reported to be promising in terms of their future potential as antibacterial drugs  and the C—H(imine) bonds. The C9—O2 bond length of 1.2251 (19) Å indicates that the molecule exists in the keto form in the solid state, and the C10—N3 bond length of 1.271 (2) Å confirms its significant double-bond character. The C9—N2 and N2—N3 bond distances of 1.351 (2) and 1.3771 (18) Å, respectively, indicate a significant delocalization of the π-electron density over the hydrazone portion of the molecule. Variations in the C—N bond lengths of 1.330 (2), 1.442 (2) and 1.351 (2) Å for C7—N1, C8—N1 and C9—N2, respectively, characterize mobility of the bridge and the integral flexibility of the –C(=O)–NH–CH2C(=O)–NH–N=CH– group connecting the two benzene rings. The molecule is twisted at atom C8, the C7—N1—C8—C9 torsion angle being 79.8 (2)°. The hydrazone part of the molecule is almost planar, with C9—N2—N3—C10 and N2—N3—C10—C11 torsion angles of −177.07 (15) and 179.38 (14)°, respectively. Further, the dihedral angle between the almost planar hydrazone segment  Å for atom N2) and the attached benzene ring (C11–C16) is 8.17 (6)°. The two benzene rings (C1–C6 and C11–C16) are orthogonal to each other, making a dihedral angle of 89.69 (9)°. The planar amide segment  is inclined to the attached toluene ring (C1–C6) by 8.06 (9) Å.The title compound crystallizes as a monohydrate Fig. 1. The conN⋯O3). A pair of N2—H2N⋯O1 intermolecular hydrogen bonds link the molecules, forming inversion dimers, with an via hydrogen bonds involving the water molecule generating N⋯O1 and N1—H1N⋯O3 hydrogen bonds between the molecules of the main compound and water molecules translate into a-axis direction (Table 1Cg2⋯Cg2i = 3.6458 (12) Å; inter-planar distance = 3.4135 (8) Å, slippage = 1.281 Å; Cg2 is the centroid of ring C11–C16; symmetry code: (i) −x + 1, −y + 1, −z + 1] involving inversion-related chlorobenzene rings; see Fig. 3In the crystal of (I)n Table 1 The chai2–C(=O)–NH–N=CH–, yielded only one hit, namely N-(2-hydroxy-1-naphthylmethylene)-N′-(N-phenylglycyl)hydrazine -N-{2-[2-(3-chlorobenzylidene)hydrazinyl]-2-oxoethyl}-4-methylbenzenesulfonamide monohydrate (II) N1) and hydrazone segment (N2–N3=C10–C11) with respect to the glycinyl C8—C9 bond in (I)cis orientation of the sulfonamide and hydrazone segments, with respect to the glycinyl C—C 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 ml), dried with anhydrous Na2SO4 and evaporated to yield the corresponding ester, N-(4-methylbenzoyl)glycine ethyl ester (L1). L1 (0.01 mol) was added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol. The mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(4-methylbenzoyl)-glycinyl hydrazide (L2). 2-Chlorobenzaldehyde (0.01 mol) and two drops of glacial acetic acid were added to L2 (0.01 mol) in anhydrous methanol (30 ml). The reaction mixture was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (479–480 K). Prism-like colourless single crystals of the title compound were grown from a solution in DMF by slow evaporation of the solvent.Triethylamine (0.03 mol) and 4-methylbenzoyl chloride (0.01 mol) were added to a stirred suspension of glycine ethylester hydrochloride (0.01 mol) in dichloromethane (50 ml) in an ice bath. The reaction mixture was stirred at room temperature for 20 h. After completion of the reaction, 2−1 for the stretching bands of N—H (amide I), N—H (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 , 7.33–7.40 , 7.42–7.45 , 7.81 , 7.97–7.99 , 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 cmUiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined as riding atoms: C—H = 0.93–0.97 Å 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 210.1107/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:


S(6) graph-set motif. In the crystal, pairs of C—H⋯Cl hydrogen bonds link molecules into inversion dimers with an R22(26) motif. Weak C—H⋯O interactions further link these dimers into ribbons propagating in [100].The hydroxy group in this carbazole derivative is involved in an intramolecular O—H⋯O hydrogen bond, which generates an  25H15Cl2NO4S, the dichlorophenyl ring is twisted by 68.69 (11)° from the mean plane of the carbazole ring system [r.m.s. deviation = 0.084 (2)°]. The hydroxy group is involved in an intramolecular O—H⋯O hydrogen bond, which generates an S(6) graph-set motif. In the crystal, pairs of C—H⋯Cl hydrogen bonds link molecules into inversion dimers with an R22(26) motif. Weak C—H⋯O interactions further link these dimers into ribbons propagating in [100].In the title compound, C The widening of angle O1—S1—O2 [120.49 (11)°] and narrowing of angle N1—S1—C1 [105.36 (10)°] from the ideal tetrahedral values are attributed to the Thorpe–Ingold effect  graph-set motif. In the crystal, pairs of C—H⋯Cl hydrogen bonds link molecules into inversion dimers with an et al., 1995The hydroxy group is involved in an intramolecular O—H⋯O hydrogen bond Table 1, which g2  in dry DMF (20 ml) at reflux for 1 h under N2. The reaction mass was poured over crushed ice (50 ml) containing concentrated HCl (1 ml). 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 g as pale-yellow crystals suitable for X-ray analysis. Yield: 368 mg (78%); m.p.: 461–463 K.Enamine 16 g  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:


II complex coordinated by heptafluorobutanoic acid, 1,10-phenanthroline and a water molecule is described.The molecular structure of a mononuclear Cu 4F7O2)2(C12H8N2)(H2O)], is mononuclear and contains a pentacoordinated CuII ion. The geometry of CuII ion can be described as distorted square-pyramidal with two O atoms of two butanoate 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—H⋯ and O—H⋯ hydrogen bonds and π–π interactions [centroid-to-centroid distance 3.533 (2) Å] link the molecules into a three-dimensional supramolecular structure.The title compound, [Cu(C For perfect tetragonal symmetry, τ is zero, and for perfect trigonal–bipyramidal geometry, τ becomes 1.0  and 1.980 (3) Å] in the quadrilateral plane are shorter than the apical position [2.173 (3) Å]. The mean Cu—N(phen) distance of 2.043 Å and the bite angle N1—Cu1—N2 of 81.75 (12)° are close to the corresponding values observed in related copper–via atoms H5A and H5B, to oxygen atom O3 of one coordinating carboxylate group (−x + y + z) and to the dangling oxygen atom O2 of the other coordinating carboxylate group (−x + y + z), thus enclosing centrosymmetric et al., 1995b-axis direction  Å.  was added to a solution of o-phenanthroline  and heptafluorobutanoic acid  in methanol (7 ml). 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 mg, 86%.Cu(ClO4)·6HUiso(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 heptafluorobutanoate groups is disordered over two sets of sites in a 0.705 (9):0.955 (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 310.1107/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:


The hydrogen-bonded structures of both a (1:1) molecular adduct and a salt of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine with 4-nitrobenzoic acid and 3,5-dinitrosalicylic acid, respectively, have been determined. 8H6BrN3S·C7H5NO4, (I), and the salt C8H7BrN3S+·C7H3N2O7−, (II), obtained from the interaction of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine with 4-nitrobenzoic acid and 3,5-dinitrosalicylic acid, respectively, have been determined. The primary inter-species association in both (I) and (II) is through duplex R22(8) (N—H⋯O/O—H⋯O) or (N—H⋯O/N—H⋯O) hydrogen bonds, respectively, giving heterodimers. In (II), these are close to planar [the dihedral angles between the thiadiazole ring and the two phenyl rings are 2.1 (3) (intra) and 9.8 (2)° (inter)], while in (I) these angles are 22.11 (15) and 26.08 (18)°, respectively. In the crystal of (I), the heterodimers are extended into a chain along b through an amine N—H⋯Nthiadiazole hydrogen bond but in (II), a centrosymmetric cyclic heterotetramer structure is generated through N—H⋯O hydrogen bonds to phenol and nitro O-atom acceptors and features, together with the primary R22(8) interaction, conjoined R46(12), R21(6) and S(6) ring motifs. Also present in (I) are π–π interactions between thiadiazole rings [minimum ring-centroid separation = 3.4624 (16) Å], as well as short Br⋯Onitro interactions in both (I) and (II) .The structures of the 1:1 co-crystalline adduct C This ‘planar’ conformation is found in the parent acid benzoic acid  PNBA adduct with BATZ, (I)ed Fig. 1, in whicanti-related carboxylic acid H atom forming the common intramolecular S(6) hydrogen bond which is found in ca. 70% of DNSA salt structures °] whereas the second nitro group and the carboxylate group lie essentially in the plane [torsion angles: C6A—C5A— N5A—O51A = 179.5 (4) and C2A—C1A— C11A—O11A = −178.0 (4)°].In the DNSA salt (II)B—H21B⋯N4Bi hydrogen bonds s Table 1 forming 1b Fig. 3. This is1b Fig. 3 and the  Fig. 3b. A weak B) and the adjacent nitro-O atom (O31A) (Table 2S(6) motifs  Å]. However, unlike in the structure of (I)With (II)) Table 2 gives anfs Fig. 4. The hetnitro contacts are found: for (I)B⋯O42Aiii = 3.314 (4) Å, and for (II)B⋯ O52Aiv = 3.104 (3) Å .In both (I)The title compounds were prepared by the reaction of 1 mmol (260 mg) of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine with 1 mmol of either 4-nitrobenzoic acid (167 mg) [for (I)] or 3,5-dinitrosalicylic acid (228 mg) [for (II)] in 20 mL of 50% ethanol–water, with 10 min 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—H = 0.95 Å] and also treated as riding, with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


N6-benzoyladenine-adipic acid (1/0.5) is reported. The typical C=O⋯π and C—H⋯π interactions are also present in this structure.The supramolecular architecture in a co-crystal of N(7)—H tautomeric form of  12H9N5O·0.5C6H10O4, consists of one molecule of N6-benzoyladenine (BA) and one half-molecule 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 (7)°. The N6-benzoyladenine molecule crystallizes in the N(7)—H tautomeric form with three non-protonated N atoms. This tautomeric form is stabilized by intramolecular N—H⋯O hydrogen bonding between the carbonyl (C=O) group and the N(7)—H hydrogen atom on the Hoogsteen face of the purine ring, forming an S(7) ring motif. The two carboxyl groups of adipic acid interact with the Watson–Crick face of the BA molecules through O—H⋯N and N—H⋯O hydrogen bonds, generating an R22(8) ring motif. The latter units are linked by N—H⋯N hydrogen bonds, forming layers parallel to (10-5). A weak C—H⋯O hydrogen bond is also present, linking adipic acid molecules in neighbouring layers, enclosing R22(10) ring motifs and forming a three-dimensional structure. C=O⋯π and C—H⋯π interactions are also present in the structure.The asymmetric unit of the title co-crystal, C As evident from the angles at N7 [C8—N7—C5 = 106.82 (11)°] and N9 [C8—N9—C4 = 103.90 (11)°], the N6-benzoyladenine moiety exists in the N(7)—H tautomeric form with non-protonated N1, N3 and N9 atoms. In addition, the C8—N7 bond [1.3415 (17) Å)] is longer than C8—N9 [1.3175 (19) Å]. These values are similar to those in neutral N6-benzoyladenine  ring motif. The dihedral angle between the adenine and phenyl ring plane is 26.71 (7)° and the C6—N6—C10—C11 torsion angle is 173.08 (14)°. The bond lengths and bond angles of AA are in the range of values reported N6-benzyladenine , N6-benzoyladenine-dl-tartaric acid (1:1)  is also present (Table 1A functions as a bifurcated hydrogen-bond acceptor whereas N7—H is a bifurcated hydrogen-bond donor.Each of the two carboxyl groups of adipic acid interacts with the Watson–Crick face (atoms N1 and N6) of the corresponding BA through O—H⋯N and N—H⋯O hydrogen bonds, generating an if Fig. 1. Thus eas Table 1 forming t Table 1, linkinga) and C10=O1B⋯π interactions between the carbonyl oxygen O1B and the centroid of the (N1/C2/N3/C4/C5/C6) pyrimidine ring  , N6-benzoyladenine-dl-tartaric acid (1:1)  and adipic acid (19 mg) . 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 K).The title co-crystal was synthesized by mixing a DMF solution of Uiso(H) = kUeq, where k = 1.5 for hydroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/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:


The Zn—Cl bond lengths differ sligthly at 2.2310 (10) and 2.2396 (11) Å while the Zn—S bond lengths are equal at 2.3663 (9) and 2.3701 (10) Å. The Cl—Zn—Cl angle is 116.04 (4) and S—Zn—S is 101.98 (3)°. All other angles at the central Zn atom range from 108.108 (3) to 110.21 (4)°. The C—S—Zn angles are 100.75 (10) and 103.68 (11)°, the difference most probably resulting from packing effects, as both the C—S and both the S—Zn bonds are equal in each case. The two imidazole ring planes make a dihedral angle of 67.9 (1)°. The CH3 groups of one isopropyl moiety are disordered over two sets of sites with occupation factors of 0.567 (15) and 0.433 (15). It may be noteworthy that the isomolecular Cu complex shows a different crystal packing (group–subgroup relation) with the Cu atom lying on a twofold rotation axis. In the crystal, the shortest non-bonding contact is a C—H⋯Cl interaction. This leads to the formation of centrosymmetric dimers that are stacked along the c-axis.The molecular 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: Molecular 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:


In the crystal, the molecules are linked through weak C—H⋯Cl 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-phenylpyridine ligand, displaying a slightly distorted square-planar geometry. The dihedral angle between the imidazole ring and the pyridine ring is 34.53 (8)°. The Pd—C bond length between the NHC ligand and the PdII ion is 1.9532 (16) Å. In the crystal, weak non-classical C—H⋯Cl hydrogen bonds link the molecules into a tape structure along [101]. A weak π–π interaction is also observed [centroid–centroid distance = 3.9117 (11) Å]. The title compound, [PdCl The two mutually trans Cl ions fulfil the coordination sphere  and 65.78 (7)°, respectively. The C12—C13 bond length of the vinyl group is 1.299 (3) Å, corroborating the double-bond character. The same goes for the C2—C3 distance which is 1.330 (3) Å. The N2—C4—Pd1—N3, N1—C4—Pd1—Cl2, C18—N3—Pd1—Cl2 and C17—C16—C19—C24 torsion angles are −30 (7), 81.15 (15), −49.40 (15) and 32.42 (3)°, respectively. A Cambridge Structural Database (CSD) search to validate the Pd—Cl and Pd—N bonding was performed over 47 entries. The Cl—Pd—Cl and N—C—N angles range from 170 to 180° and from 104.8 to 106.2°, respectively; the Pd—Cl bond lengths are in the range 2.286–2.318 Å. The bond lengths and angles of the title compound 4 shows a π–π interaction between the C19–C24 phenyl rings of neighbouring molecules with a centroid–centroid distance of 3.9117 (11) Å  route, as shown in Fig. 42 gave the chlorido-bridged palladium dimer 3. Cleavage of the dimer with phenylpyridine 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-Phenylpyridine  was added to a 40 ml solution of 3  in dry CH3CN and stirred at ambient temperature for 24 h, 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 g (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 210.1107/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:


II, four aqua and two N-bound 2-chloropyrazine ligands, weak O—H⋯O as well as π–π interactions play important roles in the molecular self-assembly, resulting in the formation of a three-dimensional structure.Between the tosylate anions and the octahedral 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 hexacoordinated by four symmetry-related water and two N-bound 2-chloropyrazine molecules in a trans arrangement, forming a distorted FeN2O4 octahedron. The three-dimensional supramolecular structure is supported by intermolecular O—H⋯O hydrogen bonds between the complex cations and tosylate anions, and additional π–π interactions between benzene and pyrazine rings. The methyl H atoms of the tosylate anion are equally disordered over two positions.The title salt, [Fe Series of thiocyanato coordination polymers [M(NCS)2L2]∞  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-chloropyrazine and aqua ligands, and tosylate as an anion.In this paper, we report on the crystal structure of [Fe2(H2O)4]2+ and two tosylate 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-chloropyrazine ligands occupying the axial positions and four O atoms of four H2O molecules forming the equatorial plane  Å] of the H2O molecules are significantly shorter than those between FeII and N [2.200 (2) Å] atoms of the two 2-chloropyrazine ligands, hence the resulting FeO4N2 octahedron is distorted. The metal-to-ligand distances clearly signalize the high-spin nature of the complex described in here °; for symmetry codes see caption to Fig. 1ii—Fe1—N1 = 90.68 (5)°] indicate only a small angular distortion.The structure of the title compound consists of a complex cation [Fe(2-chloropyrazine)ne Fig. 1. The disA⋯O2 and O1—H1B⋯O3i hydrogen bonds  (OTs = p-toluenesulfonate) and ascorbic acid (0.001 g) in water (5 ml). After seven days this yielded colourless blocks of the title compound that were collected, washed with water and dried in air. Yield 0.090 g (64%).Crystals of the title compound were obtained by adding 2-chloropyrazine  to Fe(OTs)d(C—H) = 0.95 Å for aromatic and 0.98 Å 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 molecule were located from a difference Fourier map and were modelled with a common isotropic displacement parameter fixed at 0.08 Å2. The O—H bonds lengths were constrained to 0.82 Å. 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 310.1107/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:


The crystal structure consists of discrete tetrahedral complexes, that are linked by intermolecular N—H⋯O, C—H⋯O and N—H⋯O hydrogen bonding. 2(C6H6N2O)2], consists of one Zn2+ cation located on a twofold rotation axis, as well as of one thiocyanate anion and one neutral isonicotinamide ligand, both occupying general positions. The Zn2+ cation is tetrahedrally coordinated into a discrete complex by the N atoms of two symmetry-related thiocyanate anions and by the pyridine N atoms of two isonicotinamide ligands. The complexes are linked by intermolecular C—H⋯O and N—H⋯O, and weak intermolecular N—H⋯S hydrogen-bonding interactions 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 (2)°.The asymmetric unit of the title compound consists of one Znex Fig. 1. As expeex Fig. 1. The angc axis and are linked by intermolecular N—H⋯O 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 g Ba(NCS)2·3H2O (10 mmol) with 1.795 g ZnSO4·H2O (10 mmol) in 350 ml 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 mg Zn(NCS)2 (0.15 mmol) with 36.64 mg isonicotinamide (0.3 mmol) in methylcyanide (1.5 ml) within a few days.Ba(NCS)Uiso(H) = 1.2Ueq using a riding model with C—H = 0.95 Å for aromatic and N—H = 0.88 Å for the amide H atoms. The absolute structure was determined and is in agreement with the selected setting [Flack x parameter: 0.005 (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:


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–syn fashion. The axial chloride ligands together with the Re—Re quadruple bond [2.2330 (3) Å] complete an essentially octahedral geometry around each ReIII atom. There is little distortion, with an Re—Re—Cl bond angle of 176.18 (3)° and typical cis-O—Re—O bond angles ranging from 89.39 (11) to 90.68 (11)°. There are two molecules in the unit cell, and no significant intermolecular interactions were noticed between molecules 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 + 2, −y + 1, −z + 2.]The molecular 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) −Click 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:


Both complexes, crystallized from acetonitrile 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]·2CH3CN, (2), both exhibit paddlewheel structures with four carboxylate ligands bridging two ReIII atoms. The Re—Re distances are 2.2325 (2) and 2.2299 (3) Å, indicating quadruple bonds between the ReIII atoms in each complex. Both complexes contain an inversion center at the mid-point of the Re—Re bond. The Re—Br bond [2.6712 (3) Å] in (1) is 0.1656 (6) Å longer than the Re—Cl distance [2.5056 (5) Å] of (2). In (2), the N atom of each co-crystallized acetonitrile solvent molecule is nearly equidistant between and in close contact with two carboxylate C atoms.The title complexes, [Re The first compound discovered to contain a metal–metal 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 (3) Å, in ( Tables 1 and 2 ▸.2) also contains one co-crystallized acetonitrile solvent molecule in a general position, thus giving rise to twice that in the formula unit. The asymmetric unit of (X—Re—Re—X bonds in (1) and (2) are nearly linear, as can be seen in the Re—Re—Br [175.018 (7)°] and Re—Re—Cl [178.254 (11)°] bond angles, and are comparable to those observed in similar compounds  is similar to those of the previously published analog without co-crystallized acetonitrile 3)4], and [Re2Cl2(O2CC6H5)4]·2CHCl3  is slightly longer than the Re—Br bond [2.603 (1) Å] found in [Re2Br2(O2CC(CH3)3)4]  and (2) differ by 0.1656 (6) Å and those of Cotton and coworkers differ by 0.126 (3), both of which are consistent with the difference in covalent radii of Cl and Br (0.15 Å).The 1) is isotypic with the chlorido analog published by Thomson et al. (20142Cl2(O2CC3H7)4]. In compound (2), the C1—C2—C3—C4 torsion angle is −70.2 (2)°, comparable to −67.9 (2)° for C5—C6—C7—C8 4] without co-crystallizing solvent, the torsion angles vary more    Table 1.2) nitrogen atom N1 of the co-crystallized acetonitrile solvent molecule is located at distances of 3.197 (3) and 3.216 (3) Å from the carboxylate carbon atoms C1 and C5, respectively. This is just within the sum of the van der Waals radii of 3.25 Å  = 1.2Ueq(C) and methyl, C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


In the crystal, the acetate anion is connected to the complex molecule via a pair of N—H⋯O hydrogen bonds [graph-set motif R22(8)] and the solvent methanol molecule is connected to the anion via an O—H⋯O hydrogen bond. This aggregate is further connected through a weak C—H⋯O hydrogen bond, forming a chain along [100]. In addition, sixfold phenyl embraces with intermolecular distances of 6.6463 (13)–6.667 (2) Å are arranged in a chain along [001]. The combination of hydrogen bonding and phenyl⋯phenyl interactions 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)·CH4O = 0.053wR(F2) = 0.120S = 1.0016670 reflections653 parametersH-atom parameters constrainedmax = 1.23 e Å−3Δρmin = −1.13 e Å−3ΔρAPEX2  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:


The molecules associate through an intermolecular O—H⋯Nnitrile hydrogen bond and are interlinked through very weak C—H⋯N hydrogen bonds.In the crystal of the title substituted hemibiquinone derivative, the ring systems interact through an intramolecular O—H⋯O 16H11BrN2O4 or [BrHBQH2(CN)2], the substituted benzene rings are rotated about the central C—C bond, forming a dihedral angle of 53.59 (7)°. The ring systems interact through an intramolecular O—H⋯Omethoxy hydrogen bond, which induces a geometry quite different from those in previously reported hemibiquinone structures. In the crystal, the molecules associate through an intermolecular O—H⋯Nnitrile hydrogen bond, forming chains which extend along [100] and are interlinked through very weak C—H⋯N hydrogen bonds, giving a overall two-dimensional structure lying parallel to (010).In the crystal of the title substituted hemibiquinone derivative, C This bending of the molecule about its long axis may also be due to hydrogen bonding as it causes the methoxy group to approach the OH group more closely. The aromatic C—C bonds of both rings have a narrow range of distances [from 1.387 (2) to 1.412 (2) Å]. The C—C, C—O, C—N, and C N distances for the molecule are similar to the corresponding distances in 2,3,5,6-tetracyanohydroquinone °. As a result of the influence of other short contacts and supramolecular interactions (see below), the phenolic C—O—H bond angles deviate when compared to the methoxy C—O—C bond angles: C8—O3—H is 108 (2)°, C11—O4—H is 112.3 (2)°, C3—O2—C14 is 117.9 (1)°, and C6—O1—C13 is 117.2 (1)°. As in other structures, the methoxy groups are aligned mostly in-plane with the benzene ring, C5— C6—O1—C13 being bent out of plane by −4.5 (2)° and C2—C3—O2—C14 bent out of plane by −1.3 (2)°. The C12—C11—O4—H phenol group is also nearly planar, being bent out of plane by 1.3°. However, the hydrogen-bonded phenol is unsurprisingly bent out of plane, C7—C8—O3—H = 38 (2)°. The methoxy methyl groups point away from the sterically restricting groups a-axis direction. Both nitrile groups are involved in intermolecular hydrogen-bonding interactions, the first one (O4—H⋯N1) strong, the second one (C2—H⋯N2) weaker but still highly directional. For details, see Table 1a- and b-axis directions, respectively, forming sheets parallel to (010)  contacts to six neighboring molecules Fig. 3. As in p0) Fig. 4. The quib and stacking along c can be seen in Fig. 5ac plane.The remaining two molecules in the unit cell are oriented orthogonally to the central molecules. These molecules are antiparallel to each other, where the dimethoxybenzene rings stack with those of the central pair. Slightly repulsive π-interactions between molecules 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 h, 50 µL of concentrated HCl solution was added, changing the color of the mixture from purple to bright orange. The mixture was diluted with 50 mL of water and the acetonitrile was removed by rotary evaporation. A tan powder precipitated, which was recovered by filtration and washed with water to yield the crude product. This material was recrystallized from acetone giving 0.196 g (70.4%) of pure material as yellow–orange prisms. 1H NMR  δ = 10.02 , 8.75 , 7.34 , 7.24 , 7.05 , 3.88 , 3.82 .2-Bromo-5-cyclohexa-2,5-diene-1,4-dione, BrHBQBr,  was dissolved in 350 mL of acetonitrile. In a separate beaker, potassium cyanide  was dissolved in 50 mL of HUiso = 1.5Ueq(O). Hydrogen atoms bonded to carbon were placed in calculated positions with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and their coordinates 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 210.1107/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:


N-(4-methylphenyl)benzenesulfonamide and N-(4-fluorophenyl)-4-methoxybenzenesulfonamide, the supramolecular architecture of the former is controlled by C—H⋯πaryl interactions, forming a two-dimensional architecture, while in the latter, a pair of C—H⋯O intermolecular interactions lead to the formation of a three-dimensional architecture.In the crystal structures of 4-methoxy- N-(aryl)arylsulfonamides, namely, 4-methoxy-N-(4-methylphenyl)benzenesulfonamide, C14H15NO3S, (I), and N-(4-fluorophenyl)-4-methoxybenzenesulfonamide, C13H12FNO3S, (II), were determined and analyzed. In (I), the benzenesulfonamide ring is disordered over two orientations, in a 0.516 (7):0.484 (7) ratio, which are inclined to each other at 28.0 (1)°. In (I), the major component of the sulfonyl benzene ring and the aniline ring form a dihedral angle of 63.36 (19)°, while in (II), the planes of the two benzene rings form a dihedral angle of 44.26 (13)°. In the crystal structure of (I), N—H⋯O hydrogen bonds form infinite C(4) chains extended in [010], and intermolecular C—H⋯πaryl interactions link these chains into layers parallel to the ab plane. The crystal structure of (II) features N—H⋯O hydrogen bonds forming infinite one dimensional C(4) chains along [001]. Further, a pair of C—H⋯O intermolecular interactions consolidate the crystal packing of (II) into a three-dimensional supramolecular 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 (1)°. The dihedral angle between the sulfonyl benzene ring (considering the major component) and the aniline ring is 63.36 (19)°, and the N—C bond in the C—SO2—NH—C segment has a gauche torsion with respect to the S=O bonds. Further, the molecule is twisted at the S—N bond, with a C1—S1—N1—C7 torsion angle of 66.33 (19)°. The methoxy group in the sulfonylbenzene ring is in the same plane as that of the major component of the disordered sulfonylbenzene ring, the torsion angle C5A—C4—O3—C14 being −176.2 (4)°, while it deviates slightly from planarity with respect to the minor component, the C5B—C4—O3—C14 torsion angle being 165.9 (4)°.In (I)2—NH—C segment has a gauche torsion with respect to the S=O bonds. Further, the molecule is twisted at the S—N bond, with a C1—S1—N1—C7 torsion angle of 68.4 (2)°. Similar to (I)In (II)C(4) chains along [010]. Neighbouring C(4) chains are interconnected via C—H⋯πaryl interactions s Table 1 into lays Table 1 parallelC(4) chains along [001]. Further, weak intermolecular C—H⋯O interactions s Table 2 consolids Table 2.N-(4-substituted-phenyl)-4-methoxybenzenesulfonamides benzenesulfonamide, (III), 4-methoxy-N-(4-methoxyphenyl)benzenesulfonamide, (IV), and N-(4-chlorophenyl)-4-methoxybenzenesulfonamide, (V), have been reported previously. Compounds (IV) and (V) crystallize in monoclinic syngony, while compound (III) crystallizes in orthorhombic syngony. The dihedral angles between the two benzene rings in (III), (IV) and (V) are 55.1 (1), 56.3 (1) and 42.6 (1)°, respectively. Comparison of the dihedral angles between the two benzene rings in (I)–(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 supramolecular architecture is one-dimensional. In (IV), one N—H⋯O hydrogen bond and two alternating C—H⋯πaryl (centroid of aniline ring) interactions 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 intermolecular interactions, 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 benzenesulfonyl ring in (I)A) and 0.054 (1) Å (minor-component ring B). The disordered atoms  in both components were isotropically refined, and the C—C bond lengths were restrained to 1.391 (1) Å.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/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:


The SrII ion, situated on a C2 axis, is coordinated by four O atoms from four pydc2− ligands and four water molecules. The coordination geometry of the SrII atom can be best described as a distorted dodecahedron. Each SrII ion bridges four [Co(pydc)2(H2O)2]2− units by four COO− groups of four pydc2− ligands to form a three-dimensional network structure. Two additional solvent water molecules are observed in the crystal structure and are connected to the three-dimensional coordination polymer by O—H⋯O hydrogen bonds. Further intra- and intermolecular O—H⋯O 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 + 1,-z + 1; B: −x + y + z + 1; C: x − y + 1/2,z; G: −x,y,-z + x − y,z − 1/2.The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: A: −Click 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:


Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali–H groups. An X-ray structure of imidazolium-based scaffolds using Cali–H···A− interactions (A− = anion) shows that a halide anion is directly interacting with fifteen Cali–H 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–H···A− 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–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (C Because the Cali–H···A− interaction is weak, anion binding by the Cali–H groups is generally enhanced through the incorporation of additional binding sites to the anion. Indeed, though C–H···A− type interactionsali–H 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–H donors constitutes a useful opportunity to tailor molecular recognition phenomena4ali–H···A− interactions due to relatively low binding strengths, although there are some reports about interactions between anions and multi Cali–H donors67910− interactions. In comparison, the C–H 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–H···A− H-bondsali–H···A− 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–H groups activated by adjacent oxygen atomsali–H hydrogen bonding appear to be limited to a palladium complexali–H groups1516− 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–H groups. The methyl and methylene moieties in this host form Cali–H···A− 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–H···A− 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  = 1.2U. The Cl− anion appeared to be surrounded by multiple Cali–H groups  di-hexafluorophosphate (Cl)2 are not small .Then, in our crystal structures, we find that these H ≥ 100°) . It shou− in bis-tetramethylimidazolium complexes, we were pleasantly surprised to find that one of two kinds of Cl− 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  (−···C distances (dCl···C), twelve C atoms were within H-bond distance from Cl− (4.01–4.08 Å), in consideration that rvdWCl···(H)C: 4.01–4.08 Å , while additional two C atoms  were positioned at relatively long distances . The Cali–H···Cl− angles (θ) were measured to be in all circumstances greater than 148° except for the bidentate case (129/124° and 100/100° in X-ray/DFT) by the two H atoms  attached on the same C atom at dCl···C = 4.05 Å. 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–H···Cl− interactions with its two H atoms was considered to have weak H-bonding-like interactions (θ: 129° and 100°) because the dCl···H  distances are somewhat long even though dCl···C (= 4.05 Å) ≈ rvdWCl···(H) (= 4.01–4.08 Å). 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···C = 4.71/4.83 Å) but with favorable angles (θ: 153°/177°) 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–H groups in seven molecules of [1] surrounding the Cl− anion. Furthermore, each Cali–H···Cl− binding for the given dCl···H and θ shows adequate BEs  for all the fifteen cases due to the strong electrostatic interactions between negatively charged Cl− 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−, and thus, the fifteen H atoms directly bind Cl− as Voronoi nearest neighbors.From the analysis of binding sites for Cl 14, 15) . In term−···H-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−···H-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: ∆Etotal = −2.33; ∆Eelst = −0.36; ∆Eind = −0.95; ∆Eexch = −0.36 kcal/mol for dCl···H = 3.871 Å  than in the methane model (+0.218). All of the Cl−···H-Cali angles deviate slightly from 180° 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° to 100°, the Hx-C (Hx: hydrogen interacting with Cl−) bond distance decreases from 1.108 to 1.102 Å, while Cl−···Hx distance increases from 2.705 to 3.5 Å. Namely, as the angle is close to 180°, the Cl−···Hx 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−···H–Cali interactions in the CH4–Cl− and NH3CH3+···Cl− 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 (ρ(r) = 0.002–0.040 au and 1](Cl)2 crystal structure highlights that Cl− is stabilized by strong H-bonds as well as strong ionic electrostatic interactions (dCl···Hx ≤ 3.15 Å 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 +/− electrostatic potential shells are formed 13dCl···H = 2.88–3.13 Å, dCl···C = 3.65–3.75 Å, θCl···H–C = 121–132°; dI···H = 3.35–3.30 Å, dI···C = 3.88 Å, θI···H–C = 117–120°]. 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–H···A− interactions and contain alternating regions of +/− electrostatic potential.Such nearly centrospherical shell structures containing multiple C–H···A− anions in the bisimidazolium complex have pentadeca binding sites exclusively by Cali–H groups. The electrostatic potential maps feature nearly concentro-spherical shells with alternating +/− electrostatic interactions, quite different in structure from many well-known H-bond complexes for anions. These intriguing Cali–H···A− interactions have not been properly recognized previously. The positively charged hosts render the aliphatic C–H 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 +/− electrostatic potential for the Cali–H···A− 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 π interactions4748θ between two vectors constructed from any other atom to the coordinating site and the coordinated site. If any other atom has the angle θ > 90°, the assumed coordinating atom/site should be removed from the direct coordination. If all angles θ obtained for all other atoms are less than 90°, 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 – I]+ 389.298, found 388.914.1,2,4,5-Tetramethylimidazole  and diiodomethane  were heated at 110 °C 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 g, 83%. 1H NMR , δ 6.15 , 3.61 , 2.53 , 2.20 , 2.04 . 13CNMR , δ 145.83 (N = CCH3N), 129.44 (H3CN-CCH3 = C), 126.87 (-CH2N-CCH3 = C), 56.41 (CH2), 33.77 (NCH3), 11.88 (N = CCH3N), 9.50 (-CH2N-CCH3 = C), 9.12 (H3CN-CCH3 = C). HRMS , m/z calcd. for [2M – PF6]+ 959.3240, found 959.3247; m/z calcd. for [M – PF6]+ 407.1799, found 407.1828; m/z calcd. for [M – 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···Anion Interaction Sites. Sci. Rep.6, 30123; doi: 10.1038/srep30123 (2016).