The asymmetric unit of the title 2:1 co-crystal, 2C8H8O2·C14H14N4O2, comprises an acid mol-ecule in a general position and half a di-amide mol-ecule, the latter being located about a centre of inversion. In the acid, the carb-oxy-lic acid group is twisted out of the plane of the benzene ring to which it is attached [dihedral angle = 28.51 (8)°] and the carbonyl O atom and methyl group lie approximately to the same side of the mol-ecule [hy-droxy-O-C-C-C(H) torsion angle = -27.92 (17)°]. In the di-amide, the central C4N2O2 core is almost planar (r.m.s. deviation = 0.031 Å), and the pyridyl rings are perpendicular, lying to either side of the central plane [central residue/pyridyl dihedral angle = 88.60 (5)°]. In the mol-ecular packing, three-mol-ecule aggregates are formed via hy-droxy-O-H⋯N(pyrid-yl) hydrogen bonds. These are connected into a supra-molecular layer parallel to (12[Formula: see text]) via amide-N-H⋯O(carbon-yl) hydrogen bonds, as well as methyl-ene-C-H⋯O(amide) inter-actions. Significant π-π inter-actions occur between benzene/benzene, pyrid-yl/benzene and pyrid-yl/pyridyl rings within and between layers to consolidate the three-dimensional packing.
The title compound, [Au(C8H7ClNOS)(C18H15P)], is a monoclinic (P21/n, Z' = 1; form β) polymorph of the previously reported triclinic form (P-1, Z' = 1; form α) [Tadbuppa & Tiekink (2010 ▸). Acta Cryst. E66, m664]. The mol-ecular structures of both forms feature an almost linear gold(I) coordination geometry [P-Au-S = 175.62 (5)° in the title polymorph], being coordinated by thiol-ate S and phosphane P atoms, a Z conformation about the C=N bond and an intra-molecular Au⋯O contact. The major conformational difference relates to the relative orientations of the residues about the Au-S bond: the P-Au-S-C torsion angles are -8.4 (7) and 106.2 (7)° in forms α and β, respectively. The mol-ecular packing of form β features centrosymmetric aggregates sustained by aryl-C-H⋯O inter-actions, which are connected into a three-dimensional network by aryl-C-H⋯π contacts. The Hirshfeld analysis of forms α and β shows many similarities with the notable exception of the influence of C-H⋯O inter-actions in form β.
In the solid state, the title compound, C12H16BrNO5 [systematic name: 4-bromo-2-((1E)-{[1,3-dihy-droxy-2-(hy-droxy-meth-yl)propan-2-yl]iminium-yl}meth-yl)-6-meth-oxy-benzen-1-olate], C12H16BrNO5, is found in the keto-amine tautomeric form, with an intra-molecular iminium-N-H⋯O(phenolate) hydrogen bond and an E conformation about the C=N bond. Both gauche (two) and anti relationships are found for the methyl-hydroxy groups. In the crystal, a supra-molecular layer in the bc plane is formed via hy-droxy-O-H⋯O(hy-droxy) and charge-assisted hy-droxy-O-H⋯O(phenolate) hydrogen-bonding inter-actions; various C-H⋯O inter-actions provide additional cohesion to the layers, which stack along the a axis with no directional inter-actions between them. A Hirshfeld surface analysis confirms the lack of specific inter-actions in the inter-layer region.
The crystal and mol-ecular structures of two di-phenyl-tin bis-(di-thio-carbamate)s, [Sn(C6H5)2(C5H10NOS2)2], (I), and [Sn(C6H5)2(C7H14NO2S2)2], (II), are described. In (I), in which the metal atom lies on a twofold rotation axis, the di-thio-carbamate ligand coordinates with approximately equal Sn-S bond lengths and the ipso-C atoms of the Sn-bound phenyl groups occupy cis-positions in the resulting octa-hedral C2S4 donor set. A quite distinct coordination geometry is noted in (II), arising as a result of quite disparate Sn-S bond lengths. Here, the four S-donors define a trapezoidal plane with the ipso-C atoms lying over the weaker of the Sn-S bonds so that the C2S4 donor set defines a skewed trapezoidal bipyramid. The packing of (I) features supra-molecular layers in the ab plane sustained by methyl-ene-C-H⋯π(Sn-ar-yl) inter-actions; these stack along the c-axis direction with no specific inter-actions between them. In (II), supra-molecular chains along the b-axis direction are formed by methyl-ene-C-O(ether) inter-actions; these pack with no directional inter-actions between them. A Hirshfeld surface analysis was conducted on both (I) and (II) and revealed the dominance of H⋯H inter-actions contributing to the respective surfaces, i.e. >60% in each case, and other features consistent with the description of the mol-ecular packing above.
In the organic mol-ecule of the title hydrate, C11H15N3OS·H2O, {systematic name: 3-ethyl-1-{(E)-[1-(2-hy-droxy-phen-yl)ethyl-idene]amino}-thio-urea monohydrate}, a dihedral angle of 5.39 (2)° is formed between the hy-droxy-benzene ring and the non-H atoms comprising the side chain (r.m.s. deviation = 0.0625 Å), with the major deviation from planarity noted for the terminal ethyl group [the C-N-C-C torsion angle = -172.17 (13)°]. The N-H H atoms are syn and an intra-molecular hy-droxy-imine O-H⋯N hydrogen bond is noted. In the crystal, the N-bonded H atoms form hydrogen bonds to symmetry-related water mol-ecules, and the latter form donor inter-actions with the hy-droxy O atom and with a hy-droxy-benzene ring, forming a O-H⋯π inter-action. The hydrogen bonding leads to supra-molecular tubes aligned along the b axis. The tubes are connected into layers via C-H⋯O inter-actions, and these stack along the c axis with no directional inter-actions between them.
The asymmetric unit of the title salt, C17H17F6N2O(+)·C10H8F3O3 (-), comprises two piperidin-1-ium cations and two carboxyl-ate anions. The cations, each having an l-shaped conformation owing to the near orthogonal relationship between the quinolinyl and piperidin-1-ium residues, are pseudo-enanti-omeric. The anions have the same absolute configuration but differ in the relative orientations of the carboxyl-ate, meth-oxy and benzene groups. Arguably, the most prominent difference between the anions occurs about the Cq-Om bond as seen in the Cc-Cq-Om-Cm torsion angles of -176.1 (3) and -67.1 (4)°, respectively (q = quaternary, m = meth-oxy and c = carboxyl-ate). The presence of Oh-H⋯Oc and Np-H⋯Oc hydrogen bonds leads to the formation of a supra-molecular chain along the a axis (h = hy-droxy and p = piperidin-1-ium); weak intra-molecular Np-H⋯Oh hydrogen bonds are also noted. Chains are connected into a three-dimensional architecture by C-H⋯F inter-actions. Based on a literature survey, related mol-ecules/cations adopt a uniform conformation in the solid state based on the letter L.
The asymmetric unit of the title compound, [Cd2(C12H10N2)3(C6H12NOS2)4]·4C2H3N, comprises a Cd(II) atom, two di-thio-carbamate (dtc) anions, one and a half trans-1,2-dipyridin-4-yl-ethyl-ene (bpe) mol-ecules and two aceto-nitrile solvent mol-ecules. The full binuclear complex is generated by the application of a centre of inversion. The dtc ligands are chelating, one bpe mol-ecule coordinates in a monodentate mode while the other is bidentate bridging. The resulting cis-N2S4 coordination geometry is based on an octa-hedron. Supra-molecular layers, sustained by hy-droxy-O-H⋯O(hy-droxy) and hy-droxy-O-H⋯N(bpe) hydrogen bonding, inter-penetrate to form a three-dimensional architecture; voids in this arrangement are occupied by the aceto-nitrile solvent mol-ecules. Additional inter-molecular inter-actions falling within the specified framework have been analysed by Hirshfeld surface analysis, including π-π inter-actions.
The crystal structures of two ammonium salts of 2-amino-4-nitro-benzoic acid are described, namely di-methyl-aza-nium 2-amino-4-nitro-benzoate, C2H8N+·C7H5N2O4-, (I), and di-butyl-aza-nium 2-amino-4-nitro-benzoate, C8H20N+·C7H5N2O4-, (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl-ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti-periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl-ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra-molecular chain by charge-assisted amine-N-H⋯O(carboxyl-ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N-O⋯π(arene) and methyl-C-H⋯O(nitro) inter-actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N-H⋯O(carboxyl-ate) hydrogen bonding. The formation of ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds, involving all ammonium-N-H and carboxyl-ate O atoms leads to a three-dimensional architecture; additional C-H⋯O(nitro) inter-actions contribute to the packing. The Hirshfeld surface analysis confirms the importance of the hydrogen bonding in both crystal structures. Indeed, O⋯H/H⋯O inter-actions contribute nearly 50% to the entire Hirshfeld surface in (I).
The common feature of the mol-ecular structures of the title compounds, [Zn(C5H10NS2)2(C5H5NO)], (I), and [Zn(C4H8NOS2)2(C5H5NO)], (II), are NS4 donor sets derived from N-bound hy-droxy-pyridyl ligands and asymmetrically chelating di-thio-carbamate ligands. The resulting coordination geometries are highly distorted, being inter-mediate between square pyramidal and trigonal bipyramidal for both independent mol-ecules comprising the asymmetric unit of (I), and significantly closer towards square pyramidal in (II). The key feature of the mol-ecular packing in (I) is the formation of centrosymmetric, dimeric aggregates sustained by pairs of hy-droxy-O-H⋯S(di-thio-carbamate) hydrogen bonds. The aggregates are connected into a three-dimensional architecture by methyl-ene-C-H⋯O(hy-droxy) and methyl-C-H⋯π(chelate) inter-actions. With greater hydrogen-bonding potential, supra-molecular chains along the c axis are formed in the crystal of (II), sustained by hy-droxy-O-H⋯O(hy-droxy) hydrogen bonds, with ethyl-hydroxy and pyridyl-hydroxy groups as the donors, along with ethyl-hydroxy-O-H⋯S(di-thio-carbamate) hydrogen bonds. Chains are connected into layers in the ac plane by methyl-ene-C-H⋯π(chelate) inter-actions and these stack along the b axis, with no directional inter-actions between them. An analysis of the Hirshfeld surfaces clearly distinguished the independent mol-ecules of (I) and reveals the importance of the C-H⋯π(chelate) inter-actions in the packing of both (I) and (II).
The structure of the dinuclear title complex, [Cu(2)(C(5)H(9)O(2))(4)(C(5)H(5)N)(2)], represents a monoclinic polymorph of the previously reported triclinic form [Blewett et al. (2006 ▶). Acta Cryst. E62, m420-m422]. Each carboxyl-ate group is bidentate bridging and the distorted octa-hedral geometry about each Cu(II) atom is completed by a pyridine N atom and the other Cu atom [Cu⋯Cu = 2.6139 (7) Å]. In the crystal, mol-ecules are connected into supra-molecular chains via π-π inter-actions formed by the pyridine rings [centroid-centroid distance = 3.552 (3) Å] and these are connected into a two-dimensional array in the ac plane by C-H⋯π contacts. One of the tert-butyl groups is disordered over two orientations in a 0.734 (6):0.266 (6) ratio.
The title 2:1 co-crystal, 2C7H5NO4·C14H14N4O2, in which the complete di-amide mol-ecule is generated by crystallographic inversion symmetry, features a three-mol-ecule aggregate sustained by hydroxyl-O-H⋯N(pyrid-yl) hydrogen bonds. The p-nitro-benzoic acid mol-ecule is non-planar, exhibiting twists of both the carb-oxy-lic acid and nitro groups, which form dihedral angles of 10.16 (9) and 4.24 (4)°, respectively, with the benzene ring. The di-amide mol-ecule has a conformation approximating to a Z shape, with the pyridyl rings lying to either side of the central, almost planar di-amide residue (r.m.s. deviation of the eight atoms being 0.025 Å), and forming dihedral angles of 77.22 (6)° with it. In the crystal, three-mol-ecule aggregates are linked into a linear supra-molecular ladder sustained by amide-N-H⋯O(nitro) hydrogen bonds and orientated along [10-4]. The ladders are connected into a double layer via pyridyl- and benzene-C-H⋯O(amide) inter-actions, which, in turn, are connected into a three-dimensional architecture via π-π stacking inter-actions between pyridyl and benzene rings [inter-centroid distance = 3.6947 (8) Å]. An evaluation of the Hirshfeld surfaces confirm the importance of inter-molecular inter-actions involving oxygen atoms as well as the π-π inter-actions.
The asymmetric unit of the title salt, C14H16N4O2 (2+)·2C9H5O6 (-), comprises half a dication, being located about a centre of inversion, and one anion, in a general position. The central C4N2O2 group of atoms in the dication are almost planar (r.m.s. deviation = 0.009 Å), and the carbonyl groups lie in an anti disposition to enable the formation of intra-molecular amide-N-H⋯O(carbon-yl) hydrogen bonds. To a first approximation, the pyridinium and amide N atoms lie to the same side of the mol-ecule [Npy-C-C-Namide torsion angle = 34.8 (2)°], and the anti pyridinium rings are approximately perpendicular to the central part of the mol-ecule [dihedral angle = 68.21 (8)°]. In the anion, one carboxyl-ate group is almost coplanar with the ring to which it is connected [Cben-Cben-Cq-O torsion angle = 2.0 (3)°], whereas the other carboxyl-ate and carb-oxy-lic acid groups are twisted out of the plane [torsion angles = 16.4 (3) and 15.3 (3)°, respectively]. In the crystal, anions assemble into layers parallel to (10-4) via hy-droxy-O-H⋯O(carbon-yl) and charge-assisted hy-droxy-O-H⋯O(carboxyl-ate) hydrogen bonds. The dications are linked into supra-molecular tapes by amide-N-H⋯O(amide) hydrogen bonds, and thread through the voids in the anionic layers, being connected by charge-assisted pyridinium-N-O(carboxyl-ate) hydrogen bonds, so that a three-dimensional architecture ensues. An analysis of the Hirshfeld surface points to the importance of O-H⋯O hydrogen bonding in the crystal structure.
In the title thio-semicarbazone, C11H15N3S, the p-tolyl-N-H and imino-N-H groups are anti and syn, respectively, to the central thione-S atom. This allows for the formation of an intra-molecular p-tolyl-N-H⋯N(imino) hydrogen bond. The mol-ecule is twisted with the dihedral angle between the p-tolyl ring and the non-hydrogen atoms of the N=CMe2 residue being 29.27 (8)°. The crystal packing features supra-molecular layers lying in the bc plane whereby centrosymmetric aggregates sustained by eight-membered thio-amide {⋯HNCS}2 synthons are linked by further N-H⋯S hydrogen bonds. Layers are connected via methyl-C-H⋯π inter-actions. The supra-molecular aggregation was further investigated by an analysis of the Hirshfeld surface and comparison made to related structures.
In the title salt of an S-substituted di-thio-carbazate, C16H16N3S2 (+)·Cl(-), the dihedral angles between the almost planar (r.m.s deviation = 0.005 Å) central CN2S2 residue and the terminal pyridinium and phenyl rings are 80.09 (11) and 3.82 (11)°, respectively, indicating the cation has an L-shape; the amine H and thione S atoms are syn. The conformation about each of the imine [1.376 (3) Å] and ethene [1.333 (4) Å] bonds is E. The shortened C-C bond [1.444 (4) Å] linking the double bonds is consistent with conjugation in this part of the mol-ecule. In the crystal, supra-molecular layers with a jagged topology are formed by charged-assisted amine-H⋯Cl(-) and pyridinium-N(+)-H⋯Cl(-) hydrogen bonds. The layers stack along the a axis with no specific directional inter-actions between them.
In the title compound, C15H20BrNO2, there are two independent mol-ecules (A and B) comprising the asymmetric unit and these adopt very similar conformations. In A, the dihedral angle between the CO2 and MeC=CMe2 groups is 80.7 (3)°, and these make dihedral angles of 3.5 (3) and 84.09 (16)°, respectively, with the bromo-benzene ring. The equivalent dihedral angles for mol-ecule B are 78.4 (3), 2.1 (3) and 78.37 (12)°, respectively. The most prominent inter-actions in the crystal packing are amine-N-H⋯O(carbon-yl) hydrogen bonds between the two independent mol-ecules, resulting in non-centrosymmetric ten-membered {⋯OC2NH}2 synthons. Statistical disorder is noted for each of the terminal methyl groups of the ethyl residues.
In the title compound, C17H15NO4, the conformation about the C=C double bond [1.348 (2) Å] is E with the ketone group almost co-planar [C-C-C-C torsion angle = 7.2 (2)°] but the phenyl group twisted away [C-C-C-C = 160.93 (17)°]. The terminal aromatic rings are almost perpendicular to each other [dihedral angle = 81.61 (9)°] giving the mol-ecule an overall U-shape. The crystal packing feature benzene-C-H⋯O(ketone) contacts that lead to supra-molecular helical chains along the b axis. These are connected by π-π inter-actions between benzene and phenyl rings [inter-centroid distance = 3.6648 (14) Å], resulting in the formation of a supra-molecular layer in the bc plane.
In the title compound, C8H3N3O2 (systematic name: 4-nitro-benzene-1,2-dicarbo-nitrile), the nitro group is twisted out of the plane of the benzene ring to which it is attached [O-N-Cring-Cring torsion angle = 9.80 (13)°]. In the crystal packing, supra-molecular layers with a zigzag topology in the ac plane are sustained by C-H⋯N inter-actions.
In the title compound, C8H7N3O4 (systematic name: 4-nitro-benzene-1,2-dicarboxamide), each of the substituents is twisted out of the plane of the benzene ring to which it is attached [dihedral angles of 11.36 (2)° for the nitro group, and 60.89 (6) and 34.39 (6)° for the amide groups]. The amide groups are orientated to either side of the least-squares plane through the benzene ring with the amine groups being directed furthest apart. In the crystal, a three-dimensional architecture is established by a network of N-H⋯O hydrogen bonds.
In the title di-hydro-dioxin, C31H28O5, the dioxane ring has a chair conformation, whereas each of the pyran and dioxine rings has an envelope conformation with methyl-ene and quaternary C atoms, respectively, being the flap atoms. The phenyl rings are cis and form a dihedral angle of 82.11 (10)°. The molecular structure is stabilized by C-H⋯O contacts. In the crystal packing, supra-molecular layers parallel to (101) are sustained by C-H⋯π inter-actions.
In the title compound, C16H20O6, the conformation about the C=C double bond [1.344 (2) Å] is Z. With respect to this bond, the ketone is almost coplanar [C-C-C-O torsion angle = -179.60 (10)°] and the ester is almost perpendicular [C-C-C-O = 78.42 (13)°]. The meth-oxy substituents of the central benzene ring are either almost coplanar [C-C-O-C = 3.54 (15) and 177.70 (9)°] or perpendicular [C-C-O-C = 80.08 12)° for the central substituent]. In the crystal, the three-dimensional architecture features C-H⋯O and π-π [inter-centroid distance = 3.6283 (6) Å] inter-actions.